U.S. patent application number 13/747497 was filed with the patent office on 2013-08-08 for pesticidal compositions and processes related thereto.
This patent application is currently assigned to Dow AgroSciences LLC. The applicant listed for this patent is Dow AgroSciences LLC. Invention is credited to ERICH W. BAUM, Lawrence C. Creemer, Gary D. Crouse, William Hunter Dent, III, Thomas C. Sparks.
Application Number | 20130203593 13/747497 |
Document ID | / |
Family ID | 48903407 |
Filed Date | 2013-08-08 |
United States Patent
Application |
20130203593 |
Kind Code |
A1 |
BAUM; ERICH W. ; et
al. |
August 8, 2013 |
PESTICIDAL COMPOSITIONS AND PROCESSES RELATED THERETO
Abstract
This document discloses molecules having the following formulas
("Formula One" & "Formula Two" and "Formula Three")
##STR00001## The Ar.sub.1, Het, Ar.sub.2, R1, R2, R3, R4, and R5
are further described herein.
Inventors: |
BAUM; ERICH W.; (Greenwood,
IN) ; Crouse; Gary D.; (Noblesville, IN) ;
Dent, III; William Hunter; (Indianapolis, IN) ;
Sparks; Thomas C.; (Greenfield, IN) ; Creemer;
Lawrence C.; (Greenfield, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow AgroSciences LLC; |
Indianapolis |
IN |
US |
|
|
Assignee: |
Dow AgroSciences LLC
Indianapolis
IN
|
Family ID: |
48903407 |
Appl. No.: |
13/747497 |
Filed: |
January 23, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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61594054 |
Feb 2, 2012 |
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Current U.S.
Class: |
504/100 ;
514/210.2; 514/211.15; 514/227.2; 514/254.05; 514/326; 514/362;
514/374; 514/378; 514/383; 514/63; 540/544; 544/366; 544/54;
544/55; 546/210; 548/110; 548/126; 548/235; 548/247; 548/265.8 |
Current CPC
Class: |
A01N 43/80 20130101;
C07D 495/04 20130101; C07F 7/10 20130101; A01N 43/78 20130101; A01N
43/72 20130101; C07D 417/14 20130101; C07D 405/12 20130101; C07D
417/12 20130101; C07D 413/12 20130101; A01N 47/42 20130101; C07D
401/12 20130101; A01N 43/653 20130101; A01N 43/82 20130101; A01N
43/90 20130101; C07D 249/08 20130101; A01N 43/86 20130101; A01N
43/76 20130101; A01N 55/00 20130101 |
Class at
Publication: |
504/100 ;
548/265.8; 514/383; 548/110; 514/63; 548/126; 514/362; 548/235;
514/374; 548/247; 514/378; 546/210; 514/326; 544/366; 514/254.05;
544/55; 514/227.2; 544/54; 540/544; 514/211.15; 514/210.2 |
International
Class: |
A01N 55/00 20060101
A01N055/00; A01N 43/653 20060101 A01N043/653; C07F 7/10 20060101
C07F007/10; C07D 417/12 20060101 C07D417/12; A01N 43/82 20060101
A01N043/82; C07D 413/12 20060101 C07D413/12; A01N 43/76 20060101
A01N043/76; C07D 405/12 20060101 C07D405/12; C07D 495/04 20060101
C07D495/04; A01N 43/90 20060101 A01N043/90; A01N 43/80 20060101
A01N043/80; C07D 401/12 20060101 C07D401/12; A01N 43/86 20060101
A01N043/86; A01N 43/72 20060101 A01N043/72; C07D 249/08 20060101
C07D249/08 |
Claims
1. A composition comprising a molecule according to Formulas Two or
Three ##STR00357## wherein: (a) Ar.sub.1 is (1) furanyl, phenyl,
pyridazinyl, pyridyl, pyrimidinyl, thienyl, or (2) substituted
furanyl, substituted phenyl, substituted pyridazinyl, substituted
pyridyl, substituted pyrimidinyl, or substituted thienyl, wherein
said substituted furanyl, substituted phenyl, substituted
pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and
substituted thienyl, have one or more substituents independently
selected from H, F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy,
substituted phenyl, and substituted phenoxy, wherein such
substituted phenyl and substituted phenoxy have one or more
substituents independently selected from H, F, Cl, Br, I, CN,
NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl) phenyl, and phenoxy; (b)
Het is a 5 or 6 membered, saturated or unsaturated, heterocyclic
ring, containing one or more heteroatoms independently selected
from nitrogen, sulfur, or oxygen, and where Ar.sub.1 and Ar.sub.2
are not ortho to each other (but may be meta or para, such as, for
a five membered ring they are 1,3 and for a 6 membered ring they
are either 1, 3 or 1,4), and where said heterocyclic ring may also
be substituted with one or more substituents independently selected
from H, F, Cl, Br, I, CN, NO.sub.2, oxo, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy,
substituted phenyl and substituted phenoxy, wherein such
substituted phenyl and substituted phenoxy have one or more
substituents independently selected from H, F, Cl, Br, I, CN,
NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, and phenoxy; (c)
Ar.sub.2 is (1) furanyl, phenyl, pyridazinyl, pyridyl, pyrimidinyl,
thienyl, or (2) substituted furanyl, substituted phenyl,
substituted pyridazinyl, substituted pyridyl, substituted
pyrimidinyl, or substituted thienyl, wherein said substituted
furanyl, substituted phenyl, substituted pyridazinyl, substituted
pyridyl, substituted pyrimidinyl, and substituted thienyl, have one
or more substituents independently selected from H, F, Cl, Br, I,
CN, NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy,
substituted phenyl and substituted phenoxy, wherein such
substituted phenyl and substituted phenoxy have one or more
substituents independently selected from H, F, Cl, Br, I, CN,
NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.2-C.sub.6 alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6
alkenyl), (C.sub.1-C.sub.6 alkyl)O(C.sub.1-C.sub.6 alkyl),
(C.sub.1-C.sub.6 alkyl)S(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
phenyl, and phenoxy; (d) R1 is selected from H, CN, F, Cl, Br, I,
C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6
cycloalkoxy, C.sub.1-C.sub.6 alkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), C(.dbd.O)NR.sub.xR.sub.y,
(C.sub.1-C.sub.6 alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, or phenoxy,
wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,
alkynyl, phenyl, and phenoxy, are optionally substituted with one
or more substituents independently selected from F, Cl, Br, I, CN,
NO.sub.2, oxo, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, and phenoxy; (g)
R4 is H, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C(.dbd.O)H,
C(.dbd.O)(C.sub.1-C.sub.6 alkyl), C(.dbd.O)O(C.sub.1-C.sub.6
alkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, C.sub.1-C.sub.6
alkylphenyl, C.sub.1-C.sub.6 alkyl-O-phenyl, C(.dbd.O)Het-1, Het-1,
C.sub.1-C.sub.6 alkylHet-1, or C.sub.1-C.sub.6 alkyl-.beta.-Het-1,
wherein each alkyl, cycloalkyl, alkenyl, alkynyl, phenyl, and Het-1
are optionally substituted with one or more substituents
independently selected from F, Cl, Br, I, CN, NO.sub.2,
NR.sub.xR.sub.y, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy, and
Het-1; (h) R5 is a 1 membered saturated hydrocarbyl linkage where
said linkage may also be substituted with F, Cl, Br, I, CN,
NO.sub.2, oxo, NR.sub.xR.sub.y, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)OH, C(.dbd.O)NR.sub.xR.sub.y,
(C.sub.1-C.sub.6 alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy, and
Het-1, wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy,
alkenyl, alkynyl, phenyl, phenoxy, and Het-1, are optionally
substituted with one or more substituents independently selected
from F, Cl, Br, I, CN, NO.sub.2, oxo, NR.sub.xR.sub.y,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6
cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6
cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6
alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)OH, C(.dbd.O)NR.sub.xR.sub.y,
(C.sub.1-C.sub.6 alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, halophenyl,
phenoxy, and Het-1; (i) n=0, 1, or 2; (j) R.sub.x and R.sub.y are
independently selected from H, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.2-C.sub.6 alkenyl,
C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl), C(
.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), and phenyl, wherein each
alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl, phenyl,
phenoxy, and Het-1, are optionally substituted with one or more
substituents independently selected from F, Cl, Br, I, CN,
NO.sub.2, oxo, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)OH, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, halophenyl,
phenoxy, and Het-1, or R.sub.x and R.sub.y together can optionally
form a 5- to 7-membered saturated or unsaturated cyclic group which
may contain one or more heteroatoms selected from nitrogen, sulfur,
and oxygen, and where said cyclic group can contain>C.dbd.O or
>C.dbd.S, and where said cyclic group may be substituted with F,
Cl, Br, I, CN, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, substituted
phenyl, phenoxy, and Het-1; and (k) Het-1 is a 5- or 6-membered,
saturated or unsaturated, heterocyclic ring, containing one or more
heteroatoms independently selected from nitrogen, sulfur or
oxygen.
2. A molecule according to claim 1 wherein Ar.sub.1 is a
substituted phenyl wherein said substituted phenyl has one or more
substituents independently selected from C.sub.1-C.sub.6 haloalkyl
and C.sub.1-C.sub.6 haloalkoxy.
3. A molecule according to claim 1 wherein Ar.sub.1 is a
substituted phenyl wherein said substituted phenyl, has one or more
substituents independently selected from CF.sub.3, OCF.sub.3, and
OCF.sub.2CF.sub.3.
4. A molecule according to claim 1 wherein Het is selected from
triazolyl, imidazolyl, or pyrazolyl, which can be substituted or
unsubstituted.
5. A molecule according to claim 1 wherein Het is a 1,2,4-triazolyl
##STR00358##
6. A molecule according to claim 1 wherein Het is a 1,4-imidazolyl
##STR00359##
7. A molecule according to claim 1 wherein Het is a 1,3-pyrazolyl
##STR00360##
8. A molecule according to claim 1 wherein Het is a substituted
1,3-pyrazolyl.
9. A molecule according to claim 1 wherein Het is a 1,4-pyrazolyl
##STR00361##
10. A molecule according to claim 1 wherein Ar.sub.2 is a
phenyl.
11. A molecule according to claim 1 wherein R1 is H or
C.sub.1-C.sub.6 alkyl.
12. A molecule according to claim 1 wherein R1 is H or
CH.sub.3.
13. A molecule according to claim 1 wherein R4 is phenyl,
C.sub.1-C.sub.6 alkylphenyl, or C.sub.1-C.sub.6 alkyl-O-phenyl,
wherein each alkyl and phenyl are optionally substituted with one
or more substituents independently selected from F, Cl,
NR.sub.xR.sub.y, C.sub.1-C.sub.6 alkyl, or C.sub.1-C.sub.6
alkoxy.
14. A molecule according to claim 1 wherein R5 is
unsubstituted.
15. A molecule according to claim 1 wherein R.sub.x and R.sub.y are
independently selected from H and phenyl, wherein said phenyl, may
be optionally substituted with one or more substituents
independently selected from F and Cl.
16. A molecule according to claim 1 wherein Het-1 is selected from
benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl,
benzothienyl, benzothiazolyl cinnolinyl, furanyl, indazolyl,
indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl,
isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl,
pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl,
pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl,
tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, triazolyl,
piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl,
tetrahydrofuranyl, tetrahydropyranyl,
1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,
4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and
2,3-dihydro-[1,3,4]-oxadiazolyl.
17. A molecule according to claim 1 wherein Het is selected
benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl,
benzothienyl, benzothiazolyl cinnolinyl, furanyl, indazolyl,
indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl,
isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl,
pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl,
pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl,
tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, triazolyl,
piperazinyl, piperidinyl, morpholinyl, pyrrolidinyl,
tetrahydrofuranyl, tetrahydropyranyl,
1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,
4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and
2,3-dihydro-[1,3,4]-oxadiazolyl.
18. A molecule according to claim 1 wherein Het-1 is selected from
benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl,
benzothienyl, benzothiazolyl, benzothiadizolyl, cinnolinyl,
furanyl, indazolyl, indolyl, imidazolyl, isoindolyl, isoquinolinyl,
isothiazolyl, isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl,
phthalazinyl, pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl,
pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl,
quinoxalinyl, tetrazolyl, thiazolinyl, thiazolyl, thienyl,
thienylpyrazolyl, triazinyl, triazolyl, piperazinyl, piperidinyl,
morpholinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl,
1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,
4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and
2,3-dihydro-[1,3,4]-oxadiazolyl.
19. A molecule according to claim 1 wherein Het-1 is selected from
benzothiadizolyl, furanyl, oxazolyl, and thienylpyrazolyl.
20. A molecule according to claim 1 wherein said molecule is
selected from ##STR00362## ##STR00363## ##STR00364##
21. A process to apply a composition according to claim 1 said
process comprising applying a composition according to claim 1, to
an area to control a pest, in an amount sufficient to control such
pest.
22. A process according to claim 21 wherein said molecule is
selected from ##STR00365## and said pest is BAW, CEW, or GPA.
23. A process according to claim 21 wherein said area is an area
where apples, corn, cotton, soybeans, canola, wheat, rice, sorghum,
barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries,
tomatoes, peppers, crucifers, pears, tobacco, almonds, sugar beets,
or beans, are growing, or the seeds thereof are going to be
planted
24. A composition according to claim 1 comprising a pesticidally
acceptable acid addition salt, a salt derivative, a solvate, or an
ester derivative, of a molecule according to claim 1.
25. A composition according to claim 1 comprising a polymorph of a
molecule according to claim 1.
26. A composition according to claim 1 comprising a molecule
according to claim 1 wherein at least one H is .sup.2H or at least
one C is .sup.14C.
27. A composition comprising a molecule according to claim 1 and at
least one other compound selected from the Insecticide Group,
Acaricide Group, Nematicide Group, Fungicide Group, Herbicide
Group, AI Group, or Synergist Group.
28. A composition comprising a composition according to claim 1 and
a seed.
29. A composition according to claim 28 wherein said seed has been
genetically modified to express one or more specialized traits.
30. A composition according to claim 1 and at least one compound
that has a mode of action selected from acetylcholinesterase
inhibitor, sodium channel modulator, chitin biosynthesis inhibitor,
GABA-gated chloride channel antagonist, GABA and glutamate-gated
chloride channel agonist, acetylcholine receptor agonist, MET I
inhibitor, Mg-stimulated ATPase inhibitor, nicotinic acetylcholine
receptor, Midgut membrane disrupter, oxidative phosphorylation
disrupter, and ryanodine receptor (RyRs).
31. A process comprising applying a composition according to claim
1 to a genetically modified plant that has been genetically
modified to express one or more specialized traits.
32. A process comprising: orally administering; or topically
applying; a composition according to claim 1, to a non-human
animal, to control endoparasites, ectoparasites, or both.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from U.S. provisional
application 61/594,054 filed on Feb. 2, 2012. The entire content of
this provisional application is hereby incorporated by reference
into this Application.
FIELD OF THE INVENTION
[0002] The invention disclosed in this document is related to the
field of processes to produce molecules that are useful as
pesticides (e.g., acaricides, insecticides, molluscicides, and
nematicides), such molecules, and processes of using such molecules
to control pests.
BACKGROUND OF THE INVENTION
[0003] Pests cause millions of human deaths around the world each
year. Furthermore, there are more than ten thousand species of
pests that cause losses in agriculture. The world-wide agricultural
losses amount to billions of U.S. dollars each year.
[0004] Termites cause damage to all kinds of private and public
structures. The world-wide termite damage losses amount to billions
of U.S. dollars each year.
[0005] Stored food pests eat and adulterate stored food. The
world-wide stored food losses amount to billions of U.S. dollars
each year, but more importantly, deprive people of needed food.
[0006] There is an acute need for new pesticides. Certain pests are
developing resistance to pesticides in current use. Hundreds of
pest species are resistant to one or more pesticides. The
development of resistance to some of the older pesticides, such as
DDT, the carbamates, and the organophosphates, is well known, but
resistance has even developed to some of the newer pesticides.
[0007] Therefore, for many reasons, including the above reasons, a
need exists for new pesticides.
DEFINITIONS
[0008] The examples given in the definitions are generally
non-exhaustive and must not be construed as limiting the invention
disclosed in this document. It is understood that a substituent
should comply with chemical bonding rules and steric compatibility
constraints in relation to the particular molecule to which it is
attached.
[0009] "Acaricide Group" is defined under the heading
"ACARICIDES".
[0010] "AI Group" is defined after the place in this document where
the "Herbicide Group" is defined.
[0011] "Alkenyl" means an acyclic, unsaturated (at least one
carbon-carbon double bond), branched or unbranched, substituent
consisting of carbon and hydrogen, for example, vinyl, allyl,
butenyl, pentenyl, and hexenyl.
[0012] "Alkenyloxy" means an alkenyl further consisting of a
carbon-oxygen single bond, for example, allyloxy, butenyloxy,
pentenyloxy, hexenyloxy.
[0013] "Alkoxy" means an alkyl further consisting of a
carbon-oxygen single bond, for example, methoxy, ethoxy, propoxy,
isopropoxy, butoxy, isobutoxy, and tert-butoxy.
[0014] "Alkyl" means an acyclic, saturated, branched or unbranched,
substituent consisting of carbon and hydrogen, for example, methyl,
ethyl, propyl, isopropyl, butyl, and tert-butyl.
[0015] "Alkynyl" means an acyclic, unsaturated (at least one
carbon-carbon triple bond), branched or unbranched, substituent
consisting of carbon and hydrogen, for example, ethynyl, propargyl,
butynyl, and pentynyl.
[0016] "Alkynyloxy" means an alkynyl further consisting of a
carbon-oxygen single bond, for example, pentynyloxy, hexynyloxy,
heptynyloxy, and octynyloxy.
[0017] "Aryl" means a cyclic, aromatic substituent consisting of
hydrogen and carbon, for example, phenyl, naphthyl, and
biphenyl.
[0018] "Cycloalkenyl" means a monocyclic or polycyclic, unsaturated
(at least one carbon-carbon double bond) substituent consisting of
carbon and hydrogen, for example, cyclobutenyl, cyclopentenyl,
cyclohexenyl, norbornenyl, bicyclo[2.2.2]octenyl,
tetrahydronaphthyl, hexahydronaphthyl, and octahydronaphthyl.
[0019] "Cycloalkenyloxy" means a cycloalkenyl further consisting of
a carbon-oxygen single bond, for example, cyclobutenyloxy,
cyclopentenyloxy, norbornenyloxy, and bicyclo[2.2.2]octenyloxy.
[0020] "Cycloalkyl" means a monocyclic or polycyclic, saturated
substituent consisting of carbon and hydrogen, for example,
cyclopropyl, cyclobutyl, cyclopentyl, norbornyl,
bicyclo[2.2.2]octyl, and decahydronaphthyl.
[0021] "Cycloalkoxy" means a cycloalkyl further consisting of a
carbon-oxygen single bond, for example, cyclopropyloxy,
cyclobutyloxy, cyclopentyloxy, norbornyloxy, and
bicyclo[2.2.2]octyloxy.
[0022] "Fungicide Group" is defined under the heading
"FUNGICIDES."
[0023] "Halo" means fluoro, chloro, bromo, and iodo.
[0024] "Haloalkoxy" means an alkoxy further consisting of, from one
to the maximum possible number of identical or different, halos,
for example, fluoromethoxy, trifluoromethoxy, 2,2-difluoropropoxy,
chloromethoxy, trichloromethoxy, 1,1,2,2-tetrafluoroethoxy, and
pentafluoroethoxy.
[0025] "Haloalkyl" means an alkyl further consisting of, from one
to the maximum possible number of, identical or different, halos,
for example, fluoromethyl, trifluoromethyl, 2,2-difluoropropyl,
chloromethyl, trichloromethyl, and 1,1,2,2-tetrafluoroethyl.
[0026] "Herbicide Group" is defined under the heading
"HERBICIDES."
[0027] "Heterocyclyl" means a cyclic substituent that may be fully
saturated, partially unsaturated, or fully unsaturated, where the
cyclic structure contains at least one carbon and at least one
heteroatom, where said heteroatom is nitrogen, sulfur, or oxygen.
Examples of aromatic heterocyclyls include, but are not limited to,
benzofuranyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl,
benzothienyl, benzothiazolyl cinnolinyl, furanyl, indazolyl,
indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl,
isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl,
pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl,
pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl,
tetrazolyl, thiazolinyl, thiazolyl, thienyl, triazinyl, and
triazolyl. Examples of fully saturated heterocyclyls include, but
are not limited to, piperazinyl, piperidinyl, morpholinyl,
pyrrolidinyl, tetrahydrofuranyl, and tetrahydropyranyl. Examples of
partially unsaturated heterocyclyls include, but are not limited
to, 1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,
4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and
2,3-dihydro-[1,3,4]-oxadiazolyl.
[0028] "Insecticide Group" is defined under the heading
"INSECTICIDES."
[0029] "Nematicide Group" is defined under the heading
"NEMATICIDES"
[0030] "Synergist Group" is defined under the heading "SYNERGISTIC
MIXTURES AND SYNERGISTS"
DETAILED DESCRIPTION OF THE INVENTION
[0031] This document discloses molecules having the following
formulas ("Formula One" &"Formula Two" and "Formula Three"):
(In the following formulas the nitrogens are numbered 1, 2, and 3,
solely for the purpose of identifying them and being able to refer
to them throughout this document for clarity purposes)
##STR00002##
wherein:
[0032] (a) Ar.sub.1 is [0033] (1) furanyl, phenyl, pyridazinyl,
pyridyl, pyrimidinyl, thienyl, or [0034] (2) substituted furanyl,
substituted phenyl, substituted pyridazinyl, substituted pyridyl,
substituted pyrimidinyl, or substituted thienyl, [0035] wherein
said substituted furanyl, substituted phenyl, substituted
pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and
substituted thienyl, have one or more substituents independently
selected from H, F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy,
substituted phenyl, and substituted phenoxy, [0036] wherein such
substituted phenyl and substituted phenoxy have one or more
substituents independently selected from H, F, Cl, Br, I, CN,
NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl) phenyl, and phenoxy;
[0037] (b) Het is a 5 or 6 membered, saturated or unsaturated,
heterocyclic ring, containing one or more heteroatoms independently
selected from nitrogen, sulfur, or oxygen, and where Ar.sub.1 and
Ar.sub.2 are not ortho to each other (but may be meta or para, such
as, for a five membered ring they are 1,3 and for a 6 membered ring
they are either 1, 3 or 1,4), and where said heterocyclic ring may
also be substituted with one or more substituents independently
selected from H, F, Cl, Br, I, CN, NO.sub.2, oxo, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy,
substituted phenyl and substituted phenoxy, [0038] wherein such
substituted phenyl and substituted phenoxy have one or more
substituents independently selected from H, F, Cl, Br, I, CN,
NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, and phenoxy;
[0039] (c) Ar.sub.2 is [0040] (1) furanyl, phenyl, pyridazinyl,
pyridyl, pyrimidinyl, thienyl, or [0041] (2) substituted furanyl,
substituted phenyl, substituted pyridazinyl, substituted pyridyl,
substituted pyrimidinyl, or substituted thienyl, [0042] wherein
said substituted furanyl, substituted phenyl, substituted
pyridazinyl, substituted pyridyl, substituted pyrimidinyl, and
substituted thienyl, have one or more substituents independently
selected from H, F, Cl, Br, I, CN, NO.sub.2, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy,
substituted phenyl and substituted phenoxy, [0043] wherein such
substituted phenyl and substituted phenoxy have one or more
substituents independently selected from H, F, Cl, Br, I, CN,
NO.sub.2, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.2-C.sub.6 alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6
alkenyl), (C.sub.1-C.sub.6 alkyl)O(C.sub.1-C.sub.6 alkyl),
(C.sub.1-C.sub.6 alkyl)S(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
phenyl, and phenoxy;
[0044] (d) R1 is selected from H, CN, F, Cl, Br, I, C.sub.1-C.sub.6
alkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6
alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), C(.dbd.O)NR.sub.xR.sub.y,
(C.sub.1-C.sub.6 alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, or phenoxy, [0045]
wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl,
alkynyl, phenyl, and phenoxy, are optionally substituted with one
or more substituents independently selected from F, Cl, Br, I, CN,
NO.sub.2, oxo, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, and phenoxy;
[0046] (e) R2 is H, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
cycloalkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl,
C(.dbd.O)H, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)(C.sub.2-C.sub.6 alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6
alkenyl), (C.sub.1-C.sub.6 alkyl)O(C.sub.1-C.sub.6 alkyl),
(C.sub.1-C.sub.6 alkyl)S(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
phenyl, C.sub.1-C.sub.6 alkylphenyl, C.sub.1-C.sub.6
alkyl-O-phenyl, C(.dbd.O)Het-1, Het-1, C.sub.1-C.sub.6 alkylHet-1,
or C.sub.1-C.sub.6 alkyl-O-Het-1, [0047] wherein each alkyl,
cycloalkyl, alkenyl, alkynyl, phenyl, and Het-1 are optionally
substituted with one or more substituents independently selected
from F, Cl, Br, I, CN, NO.sub.2, NR.sub.xR.sub.y, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy, and
Het-1;
[0048] (f) R3 is C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl, C(.dbd.O)H,
C(.dbd.O)(C.sub.1-C.sub.6 alkyl), C(.dbd.O)O(C.sub.1-C.sub.6
alkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, C.sub.1-C.sub.6
alkylphenyl, C.sub.1-C.sub.6 alkyl-O-phenyl, C(.dbd.O)Het-1, Het-1,
C.sub.1-C.sub.6 alkylHet-1,
C.sub.1-C.sub.6alkyl-O--C(.dbd.O)C.sub.1-C.sub.6
alkyl-O--C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkyl-O--C(.dbd.O)C.sub.1-C.sub.6 alkyl-O--C.sub.1-C.sub.6
alkyl-O--C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkyl-O--C(.dbd.O)C.sub.1-C.sub.6 alkyl-O--C.sub.1-C.sub.6
haloalkyl, C.sub.1-C.sub.6 alkyl-O--C(.dbd.O)C.sub.1-C.sub.6
alkyl-N(R.sub.x)C(.dbd.O)--O-phenyl, C.sub.1-C.sub.6
alkyl-O--C(.dbd.O)C.sub.1-C.sub.6
alkyl-N(R.sub.x)C(.dbd.O)--O--C.sub.1-C.sub.6 alkylphenyl,
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkylHet-1C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6 alkylHet-1,
C.sub.1-C.sub.6alkylC(.dbd.O)Het-1, C.sub.1-C.sub.6
alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkyl(N(R.sub.x)(R.sub.y))(C(.dbd.O)OH),
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkylN(R.sub.x)(R.sub.y),
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkylN(R.sub.x)C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkyl(N(R.sub.x)C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl)(C(.dbd.O)OH),
C.sub.1-C.sub.6alkylC(.dbd.O)Het-1C(.dbd.O)--O--C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6alkyl-O--C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkyl-O--C(.dbd.O)C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkyl-O--C(.dbd.O)C.sub.3-C.sub.6 cycloalkyl,
C.sub.1-C.sub.6alkyl-O--C(.dbd.O)Het-1,
C.sub.1-C.sub.6alkyl-O--C(.dbd.O)C.sub.1-C.sub.6
alkyl-N(R.sub.x)C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkyl-NR.sub.xR.sub.y, or C.sub.1-C.sub.6
alkyl-O-Het-1, [0049] wherein each alkyl, cycloalkyl, alkenyl,
alkynyl, phenyl, and Het-1 are optionally substituted with one or
more substituents independently selected from F, Cl, Br, I, CN,
NO.sub.2, NR.sub.xR.sub.y, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6
halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6
halocycloalkoxy, C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6
haloalkoxy, C.sub.2-C.sub.6 alkenyl, C.sub.3-C.sub.6 cycloalkenyl,
C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)OH, C(.dbd.O)NR.sub.xR.sub.y,
(C.sub.1-C.sub.6 alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy,
Si(C.sub.1-C.sub.6 alkyl).sub.3, S(.dbd.O).sub.nNR.sub.xR.sub.y,
and Het-1;
[0050] (g) R4 is H, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
cycloalkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl,
C(.dbd.O)H, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)(C.sub.2-C.sub.6 alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6
alkenyl), (C.sub.1-C.sub.6 alkyl)O(C.sub.1-C.sub.6 alkyl),
(C.sub.1-C.sub.6 alkyl)S(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
phenyl, C.sub.1-C.sub.6 alkylphenyl, C.sub.1-C.sub.6
alkyl-O-phenyl, C(.dbd.O)Het-1, Het-1, C.sub.1-C.sub.6 alkylHet-1,
or C.sub.1-C.sub.6 alkyl-O-Het-1, [0051] wherein each alkyl,
cycloalkyl, alkenyl, alkynyl, phenyl, and Het-1 are optionally
substituted with one or more substituents independently selected
from F, Cl, Br, I, CN, NO.sub.2, NR.sub.xR.sub.y, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)NR.sub.xR.sub.y, (C.sub.1-C.sub.6
alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy, and
Het-1;
[0052] (h) R5 is a 1 membered saturated or a 2 to 4 membered
saturated or unsaturated hydrocarbyl linkage where said linkage may
also be substituted with F, Cl, Br, I, CN, NO.sub.2, oxo,
NR.sub.xR.sub.y, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)OH, C(.dbd.O)NR.sub.xR.sub.y,
(C.sub.1-C.sub.6 alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, phenoxy, and
Het-1, [0053] wherein each alkyl, cycloalkyl, cycloalkoxy, alkoxy,
alkenyl, alkynyl, phenyl, phenoxy, and Het-1, are optionally
substituted with one or more substituents independently selected
from F, Cl, Br, I, CN, NO.sub.2, oxo, NR.sub.xR.sub.y,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6
cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6
cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6
alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)OH, C(.dbd.O)NR.sub.xR.sub.y,
(C.sub.1-C.sub.6 alkyl)NR.sub.xR.sub.y, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, halophenyl,
phenoxy, and Het-1;
[0054] (i) n=0, 1, or 2;
[0055] (j) R.sub.x and R.sub.y are independently selected from H,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6
cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl, C.sub.2-C.sub.6
alkenyl, C.sub.2-C.sub.6 alkynyl, S(.dbd.O).sub.n(C.sub.1-C.sub.6
alkyl), S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), and phenyl, [0056] wherein
each alkyl, cycloalkyl, cycloalkoxy, alkoxy, alkenyl, alkynyl,
phenyl, phenoxy, and Het-1, are optionally substituted with one or
more substituents independently selected from F, Cl, Br, I, CN,
NO.sub.2, oxo, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 cycloalkyl, C.sub.3-C.sub.6 halocycloalkyl,
C.sub.3-C.sub.6 cycloalkoxy, C.sub.3-C.sub.6 halocycloalkoxy,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6
alkenyl, C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6 haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)H, C(.dbd.O)OH, C(.dbd.O)(C.sub.1-C.sub.6
alkyl), C(.dbd.O)O(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)(C.sub.1-C.sub.6 haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl),
C(.dbd.O)O(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6
alkenyl), C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, halophenyl,
phenoxy, and Het-1, [0057] or R.sub.x and R.sub.y together can
optionally form a 5- to 7-membered saturated or unsaturated cyclic
group which may contain one or more heteroatoms selected from
nitrogen, sulfur, and oxygen, and where said cyclic group can
contain>C.dbd.O or >C.dbd.S, and where said cyclic group may
be substituted with F, Cl, Br, I, CN, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.3-C.sub.6 halocycloalkyl, C.sub.3-C.sub.6 cycloalkoxy,
C.sub.3-C.sub.6 halocycloalkoxy, C.sub.1-C.sub.6 alkoxy,
C.sub.1-C.sub.6 haloalkoxy, C.sub.2-C.sub.6 alkenyl,
C.sub.3-C.sub.6 cycloalkenyl, C.sub.2-C.sub.6 alkynyl,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
S(.dbd.O).sub.n(C.sub.1-C.sub.6haloalkyl),
OSO.sub.2(C.sub.1-C.sub.6 alkyl), OSO.sub.2(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
haloalkyl), C(.dbd.O)O(C.sub.1-C.sub.6 haloalkyl),
C(.dbd.O)(C.sub.3-C.sub.6 cycloalkyl), C(.dbd.O)O(C.sub.3-C.sub.6
cycloalkyl), C(.dbd.O)(C.sub.2-C.sub.6 alkenyl),
C(.dbd.O)O(C.sub.2-C.sub.6 alkenyl), (C.sub.1-C.sub.6
alkyl)O(C.sub.1-C.sub.6 alkyl), (C.sub.1-C.sub.6
alkyl)S(C.sub.1-C.sub.6 alkyl), C(.dbd.O)(C.sub.1-C.sub.6
alkyl)C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, substituted
phenyl, phenoxy, and Het-1; and
[0058] (k) Het-1 is a 5- or 6-membered, saturated or unsaturated,
heterocyclic ring, containing one or more heteroatoms independently
selected from nitrogen, sulfur or oxygen.
[0059] It is understood that in Formula 1, when R2 is H, the
compounds may exist in more than one tautomeric or isomeric form,
wherein the hydrogen is attached to either of the nitrogen atoms;
further, both E and Z isomers may exist. Any and all isomeric forms
of the compounds of this invention are claimed.
[0060] In another embodiment Ar.sub.1 is a substituted phenyl,
wherein said substituted phenyl has one or more substituents
independently selected from C.sub.1-C.sub.6 haloalkyl and
C.sub.1-C.sub.6 haloalkoxy.
[0061] In another embodiment Ar.sub.1 is a substituted phenyl,
wherein said substituted phenyl has one or more substituents
independently selected from CF.sub.3, OCF.sub.3, and
OCF.sub.2CF.sub.3.
[0062] In another embodiment Het is selected from triazolyl,
imidazolyl, or pyrazolyl, which can be substituted or
unsubstituted.
[0063] In another embodiment Het is a 1,2,4-triazolyl
##STR00003##
[0064] In another embodiment Het is 1,4-imidazolyl
##STR00004##
[0065] In another embodiment Het is 1,3-pyrazolyl
##STR00005##
[0066] In another embodiment Het is a substituted
1,3-pyrazolyl.
[0067] In another embodiment Het is 1,4-pyrazolyl
##STR00006##
[0068] In another embodiment Ar.sub.2 is a phenyl.
[0069] In another embodiment R1 is H or C.sub.1-C.sub.6 alkyl.
[0070] In another embodiment R1 is H or CH.sub.3.
[0071] In another embodiment R2 is H.
[0072] In another embodiment R3 is selected from C.sub.1-C.sub.6
alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.2-C.sub.6 alkynyl,
C.sub.1-C.sub.6 alkylphenyl, C.sub.1-C.sub.6 alkylHet-1,
C.sub.1-C.sub.6alkyl-O--C(.dbd.O)C.sub.1-C.sub.6
alkyl-O--C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkyl-O--C(.dbd.O)C.sub.1-C.sub.6 alkyl-O--C.sub.1-C.sub.6
alkyl-O--C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkyl-O--C(.dbd.O)C.sub.1-C.sub.6 alkyl-O--C.sub.1-C.sub.6
haloalkyl, C.sub.1-C.sub.6 alkyl-O--C(.dbd.O)C.sub.1-C.sub.6
alkyl-N(R.sub.x)C(.dbd.O)--O-phenyl,
C.sub.1-C.sub.6alkyl-O--C(.dbd.O)C.sub.1-C.sub.6
alkyl-N(R.sub.x)C(.dbd.O)--O--C.sub.1-C.sub.6 alkylphenyl,
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkylHet-1C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6 alkylHet-1,
C.sub.1-C.sub.6 alkylC(.dbd.O)Het-1,
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkyl(N(R.sub.x)(R.sub.y))(C(.dbd.O)OH),
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkylN(R.sub.x)(R.sub.y), C.sub.1-C.sub.6
alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkylN(R.sub.x)C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6alkylC(.dbd.O)N(R.sub.x)C.sub.1-C.sub.6
alkyl(N(R.sub.x)C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl)(C(.dbd.O)OH),
C.sub.1-C.sub.6alkylC(.dbd.O)Het-1C(.dbd.O)--O--C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6alkyl-O--C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6alkyl-O--C(.dbd.O)C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkyl-O--C(.dbd.O)C.sub.3-C.sub.6 cycloalkyl,
C.sub.1-C.sub.6alkyl-O--C(.dbd.O)Het-1, or C.sub.1-C.sub.6
alkyl-O--C(.dbd.O)C.sub.1-C.sub.6
alkyl-N(R.sub.x)C(.dbd.O)--O--C.sub.1-C.sub.6 alkyl, wherein each
alkyl, alkenyl, alkynyl, phenyl, and Het-1 are optionally
substituted with one or more substituents independently selected
from F, Cl, Br, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.1-C.sub.6 haloalkoxy, S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl),
C(.dbd.O)OH, C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl,
Si(C.sub.1-C.sub.6 alkyl).sub.3, and
S(.dbd.O).sub.nNR.sub.xR.sub.y.
[0073] In another embodiment R4 is phenyl, C.sub.1-C.sub.6
alkylphenyl, Het-1, or C.sub.1-C.sub.6 alkyl-O-phenyl, wherein each
alkyl, Het-1, and phenyl are optionally substituted with one or
more substituents independently selected from F, Cl,
NR.sub.xR.sub.y, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6 cycloalkyl,
C.sub.1-C.sub.6 haloalkoxy, C(.dbd.O)O C.sub.1-C.sub.6 alkyl, or
C.sub.1-C.sub.6 alkoxy.
[0074] In another embodiment R5 is substituted with oxo,
C(.dbd.O)OH, phenyl, and Het-1, wherein each phenyl and Het-1, may
be optionally substituted with one or more substituents
independently selected from oxo, C.sub.1-C.sub.6 haloalkyl,
C.sub.1-C.sub.6 haloalkoxy, C(.dbd.O)OH, and halophenyl.
[0075] In another embodiment R.sub.x and R.sub.y are independently
selected from H and phenyl, wherein said phenyl, may be optionally
substituted with one or more substituents independently selected
from F and Cl.
[0076] In another embodiment: [0077] Ar.sub.1 is a substituted
phenyl wherein said substituted phenyl, has one or more
C.sub.1-C.sub.6 haloalkoxy; [0078] Het is a triazolyl; [0079]
Ar.sub.2 is a phenyl; [0080] R1 is H; [0081] R2 is H; [0082] R3 is
C.sub.1-C.sub.6 alkylHet-1 wherein said alkyl and Het-1 are
optionally substituted with one or more substituents independently
selected from F, Cl, Br, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.1-C.sub.6 haloalkoxy,
S(.dbd.O).sub.n(C.sub.1-C.sub.6 alkyl), C(.dbd.O)OH,
C(.dbd.O)O(C.sub.1-C.sub.6 alkyl), phenyl, Si(C.sub.1-C.sub.6
alkyl).sub.3, and S(.dbd.O).sub.nNR.sub.xR.sub.y; [0083] R4 is
phenyl, wherein said phenyl is optionally substituted with one or
more substituents independently selected from F, Cl,
NR.sub.xR.sub.y, C.sub.1-C.sub.6 alkyl, or C.sub.1-C.sub.6 alkoxy;
and [0084] n=0, 1, or 2; [0085] R.sub.x and R.sub.y are
independently selected from H and phenyl, wherein said phenyl, may
be optionally substituted with one or more substituents
independently selected from F and Cl; and [0086] Het-1 is a 5- or
6-membered, saturated or unsaturated, heterocyclic ring, containing
one or more heteroatoms independently selected from nitrogen,
sulfur or oxygen.
[0087] In another embodiment Het-1 is selected from benzofuranyl,
benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl,
benzothiazolyl cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl,
isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl,
oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl,
pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl,
quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl,
thiazolyl, thienyl, triazinyl, triazolyl, piperazinyl, piperidinyl,
morpholinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl,
1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,
4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and
2,3-dihydro-[1,3,4]-oxadiazolyl.
[0088] In another embodiment Het is selected benzofuranyl,
benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl,
benzothiazolyl cinnolinyl, furanyl, indazolyl, indolyl, imidazolyl,
isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, oxadiazolyl,
oxazolinyl, oxazolyl, phthalazinyl, pyrazinyl, pyrazolinyl,
pyrazolyl, pyridazinyl, pyridyl, pyrimidinyl, pyrrolyl,
quinazolinyl, quinolinyl, quinoxalinyl, tetrazolyl, thiazolinyl,
thiazolyl, thienyl, triazinyl, triazolyl, piperazinyl, piperidinyl,
morpholinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl,
1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,
4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and
2,3-dihydro-[1,3,4]-oxadiazolyl.
[0089] In another embodiment Het-1 is selected from benzofuranyl,
benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, benzothienyl,
benzothiazolyl, benzothiadizolyl, cinnolinyl, furanyl, indazolyl,
indolyl, imidazolyl, isoindolyl, isoquinolinyl, isothiazolyl,
isoxazolyl, oxadiazolyl, oxazolinyl, oxazolyl, phthalazinyl,
pyrazinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridyl,
pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl,
tetrazolyl, thiazolinyl, thiazolyl, thienyl, thienylpyrazolyl,
triazinyl, triazolyl, piperazinyl, piperidinyl, morpholinyl,
pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl,
1,2,3,4-tetrahydro-quinolinyl, 4,5-dihydro-oxazolyl,
4,5-dihydro-1H-pyrazolyl, 4,5-dihydro-isoxazolyl, and
2,3-dihydro-[1,3,4]-oxadiazolyl.
[0090] In another embodiment Het-1 is selected from
benzothiadizolyl, furanyl, oxazolyl, and thienylpyrazolyl.
[0091] While these embodiments have been expressed, other
embodiments and combinations of these expressed embodiments and
other embodiments are possible.
[0092] The Molecules of Formulae One, Two and Three will generally
have a molecular mass of about 100 Daltons to about 1200 Daltons.
However, it is generally preferred if the molecular mass is from
about 120 Daltons to about 900 Daltons, and it is even more
generally preferred if the molecular mass is from about 400 Daltons
to about 800 Daltons.
Preparation of Triaryl Intermediates
[0093] Compounds of this invention can be prepared by making a
triaryl intermediate, Ar.sub.1-Het-Ar.sub.2, and then linking it to
the desired intermediate to form the desired compound. A wide
variety of triaryl intermediates can be used to prepare compounds
of this invention, provided that such triaryl intermediates contain
a suitable functional group on Ar.sub.2 to which the rest of the
desired intermediate can be attached. Suitable functional groups
include an oxoalkyl or a formyl group. These triaryl intermediates
can be prepared by methods previously described in the chemical
literature, including Crouse et al. PCT Int. Appl. Publ.
WO2009/102736 A1.
Preparation of Hydrazone-Linked Compounds
[0094] Hydrazone-linked compounds can be prepared from the
corresponding aryl aldehydes or ketones by one of three methods:
(1) by reaction with a hydrazine, followed by reaction with an aryl
isothiocyanate in tetrahydrofuran (THF), at temperatures between 0
and 100.degree. C. (Reaction A); (2) by reaction with methyl
hydrazinecarbodithioate, followed by reaction with an aniline in a
polar aprotic solvent such as N,N-dimethylformamide (DMF), at
temperatures between 25 and 150.degree. C. (Reaction B); or (3) by
reaction with an aryl thiosemicarbazide, that is either
commercially available or can be prepared by one who is skilled in
the art, in a polar protic solvent such as ethyl alcohol (EtOH), at
temperatures between 0 and 100.degree. C. (Reaction C).
##STR00007##
Preparation of Alkylated Hydrazone-Linked Compounds
[0095] Alkylated hydrazone-linked compounds can be prepared from
the corresponding hydrazone-linked compounds by one of two methods:
(1) by reaction with an alkylating agent in EtOH or acetone, at
temperatures between 0 and 100.degree. C. for from 1 to 24 h or (2)
by reaction with an alkylating agent in chloroform (CHCl.sub.3),
dichloromethane (CH.sub.2Cl.sub.2), or other halocarbon solvent,
with or without a base such as sodium bicarbonate, at from 20 to
60.degree. C.
##STR00008##
[0096] Compounds of Formula Two, wherein R5 forms a ring with
N.sub.3 (see Scheme below) or of Formula Three, wherein R5 forms a
ring with N.sub.2, can be prepared from a suitable acyclic
precursor by using .alpha.-halo acids, acid halides, esters, or
ketones (F or G or H). For example, treatment of the
thiosemicarbazone with a slight excess of an .alpha.-halo ester, in
a protic solvent such as EtOH or methyl alcohol (CH.sub.3OH)
results in S-alkylation and subsequent ring closure exclusively
onto N.sub.3 (Reaction F; see for example, J. Indian Chemical
Society 1966, 43, 275-276, or J. Heterocycl. Chem. 1978, 15,
335-336). When an aprotic solvent such as CH.sub.2Cl.sub.2 or
dichloroethane (ClCH.sub.2CH.sub.2Cl) is used at temperatures from
30.degree. C. to 80.degree. C., the orientation of addition of
.alpha. halo ketones also favors closure onto N.sub.3, with
subsequent dehydration to form an imino thiazoline (Reaction G).
With .alpha.-halo acids or acid halides or esters in a halocarbon
solvent such as CH.sub.2Cl.sub.2 or ClCH.sub.2CH.sub.2Cl, ring
closure onto both N.sub.2 (Reaction H) and N.sub.3 is observed.
Though these reactions often proceed in the absence of added base,
a base such as sodium bicarbonate, sodium carbonate or sodium
acetate, or an amine base such as pyridine or triethylamine, can be
added.
##STR00009##
[0097] Alternatively, 3-arylidineimino-2-aryliminothiazolin-4-ones
can be prepared by treating an aldehyde or ketone, wherein R1 is as
previously described, with a 3-amino-2-(arylimino)thiazolidin-4-one
in acetic acid at from 30 to 70.degree. C. as shown in the
following scheme (I). The intermediate
1-amino-2-aryliminothiazolin-5-one, wherein R4 is phenyl, has been
described (see for example, J. Org. Chem. 1962, 27, 2878); it was
prepared in 80% yield by treatment of 4-phenyl thiosemicarbazide
with ethyl 2-chloroacetate and sodium acetate in hot EtOH.
##STR00010##
[0098] Alternatively, compounds of Formula 2 and Formula 3 may be
formed by heating a thiosemicarbazone precursor with a di-halo
group Hal1-R5-Hal2 such as 1-bromo-2-chloro ethane or
diiodomethane, in acetone or 2-butanone or other suitable solvent,
using a base such as potassium carbonate or triethylamine, at
temperatures between ambient and 100.degree. C. for from 1 to 72
hours. The S-alkylated intermediate undergoes cyclization at N2 or
N3 to generate compounds of Formula Two or Formula Three (Reaction
J). In some cases, addition of KI may be required to accelerate the
cyclization of the intermediate S-alkylated derivatives to the
ring-closed products.
##STR00011##
An alternative method of preparing compounds of this invention is
by treatment of a thiosemicarbazone precursor with an unsaturated
ester or acid chloride (Reaction L).
##STR00012##
[0099] Substituted hydrazinecarbothioamide intermediates, such as
those utilized in Method C above, can be prepared by a number
methods known in the chemical literature. Alternatively, compounds
wherein R.sub.a, R.sub.b, and R.sub.c are not derived from a
commercially available aniline can be prepared according to the
scheme below. For example, a 2-halo nitrobenzene, such as
2-bromonitrobenzene, substituted with one or multiple R.sub.c
substituents, wherein R.sub.c can be H, alkyl, alkoxy, or halo,
such as fluoro, can be reacted with a boronic acid or boronate
ester, such as the substituted
4,4,5,5-tetramethyl-1,3,2-dioxaborolane, wherein R.sub.a and
R.sub.b are H, in the presence of a base, for example sodium
carbonate, and a palladium catalyst, such as
bis(triphenylphosphine)palladium(II)chloride, in an aqueous solvent
system, such as 4:1 dioxane/water, at an elevated temperature, for
example 80.degree. C., affords the olefinic substituted
nitrobenzene compounds. Alternatively, R.sub.a and R.sub.b can be
taken together to form a ring, such as a cyclopentene, to give the
corresponding
2-(cyclopent-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,
which under the conditions described above affords the cyclic
alkene substituted nitrobenzene. Treatment a solution of the
olefinic nitrobenzenes in an aprotic solvent, such as ethyl
acetate, wherein R.sub.a, R.sub.b, and R.sub.c, are as defined
above, with hydrogen gas in the presence of a catalyst, for example
palladium on carbon (Pd/C), affords the corresponding alkyl or
cycloalkyl substituted anilines. Treating a biphasic solution of
the anilines, wherein R.sub.a, R.sub.b, and R.sub.c, are as
defined, in a mixture of halogenated solvent and water, such as 2:1
dichloromethane/water, with a base, such as sodium
hydrogencarbonate, followed by thiophosgene affords the
intermediate isothiocyanatobenzenes. Separation of the phases,
followed by drying and evaporation of the organic solvent affords
the crude intermediate which is immediately dissolved in an
alcohol, such as ethanol, and treated with hydrazine hydrate to
give the hydrazinecarbothioamide intermediates, wherein R.sub.a,
R.sub.b, and R.sub.c, are as defined.
##STR00013##
EXAMPLES
[0100] The examples are for illustration purposes and are not to be
construed as limiting the invention disclosed in this document to
only the embodiments disclosed in these examples.
[0101] Starting materials, reagents, and solvents that were
obtained from commercial sources were used without further
purification. Anhydrous solvents were purchased as Sure/Seal.TM.
from Aldrich and were used as received. Melting points were
obtained on a Thomas Hoover Unimelt capillary melting point
apparatus or an OptiMelt Automated Melting Point System from
Stanford Research Systems and are uncorrected. Molecules are given
their known names, named according to naming programs within MDL
ISIS.TM./Draw 2.5, ChemBioDraw Ultra 12.0 or ACD Name Pro. If such
programs are unable to name a molecule, the molecule is named using
conventional naming rules. .sup.1H NMR spectral data are in ppm
(.delta.) and were recorded at 300, 400 or 600 MHz, and .sup.13C
NMR spectral data are in ppm (.delta.) and were recorded at 75, 100
or 150 MHz, unless otherwise stated.
Example 1
Preparation of
(E)-N-(4-dimethylamino)phenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,-
2,4-triazol-3-yl)benzylidene)hydrazine-carbothioamide (Compound
I-1) [Synthesis Method A]
##STR00014##
[0102] Step 1.
(E)-3-(4-(Hydrazonomethyl)phenyl)-1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-
-triazole
[0103] To a 250 milliliter (mL) round-bottomed flask containing
hydrazine hydrate (64% aqueous (aq) solution; 7.27 mL, 15.0
millimoles (mmol)) in EtOH (100 mL) at 80.degree. C. was added
4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzaldehyde
(5.00 grams (g), 1.50 mmol) portionwise over 5 minutes (min) The
solution was stirred at reflux for an additional 3 hours (h) before
being diluted with water (H.sub.2O; 300 mL) and cooled to 0.degree.
C. The precipitated product was collected by vacuum filtration as a
white solid (4.89 g, 93%): mp 222-226.degree. C.; .sup.1H NMR (400
MHz, DMSO-d.sub.6) .delta. 8.59 (s, 1H), 8.22 (d, J=8.2 Hz, 2H),
7.84-7.79 (m, 3H), 7.66 (d, J=8.3 Hz, 2H), 7.41 (d, J=8.2 Hz, 2H),
7.29 (s, 1H), 5.63 (br s, 2H); ESIMS m/z 348 (M+H).
Step 2
[0104] To a 25 mL round-bottomed flask containing
(E)-3-(4-(hydrazonomethyl)
-phenyl)-1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazole (250 mg,
0.720 mmol) in THF (10 mL) was added
4-isothiocyanato-N,N-dimethylaniline (385 mg, 2.16 mmol). The
contents were heated at 65.degree. C. with stirring for 2 h before
the solvent was removed under reduced pressure. The residue was
slurried in CH.sub.2Cl.sub.2 (10 mL) resulting in precipitation of
product material. The desired product was obtained as a yellow
solid via vacuum filtration (350 mg, 93%): mp 205-208.degree. C.;
.sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 11.78 (s, 1H), 10.02
(s, 1H), 9.42 (s, 1H), 8.19-7.99 (m, 6H), 7.64 (d, J=8.3 Hz, 2H),
7.28 (d, J=8.3 Hz, 2H), 7.73 (d, J=8.3 Hz, 2H), 2.92 (s, 6H); ESIMS
m/z 526 (M+H).
Example 2
Preparation of
N-(3-(dimethylamino)phenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-
-triazol-3-yl)benzylidene)hydrazinecarbothioamide (Compound I-2)
[Synthesis Method B]
##STR00015##
[0105] Step 1. (E)-Methyl
2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hy-
drazinecarbodithioate
[0106] To a 250 mL round-bottom flask containing
hydrazinecarbodithioic acid methyl ester (2.38 g, 1.95 mmol) in
EtOH (100 mL) was added
4-[1-(4-trifluoromethoxyphenyl)-1H-[1,2,4]triazol-3-yl]-benzaldehyde
(5.00 g, 1.50 mmol). The vessel was heated at 80.degree. C. for 3 h
before being diluted with H.sub.2O (300 mL) and cooled to 0.degree.
C. The precipitated product was collected by vacuum filtration as
an off-white solid (6.13 g, 93%): mp 204-206.degree. C.; .sup.1H
NMR (400 MHz, DMSO-d.sub.6) .delta. 13.39 (s, 1H), 9.43 (s, 1H),
8.38 (s, 1H), 8.21 (d, J=8.3 Hz, 2H), 8.09 (d, J=8.4 Hz, 2H), 7.88
(d, J=8.4 Hz, 2H), 7.62 (d, J=8.3 Hz, 2H), 2.57 (s, 3H); ESIMS m/z
438 (M+H).
Step 2
[0107] To a 50 mL round-bottomed flask containing (E)-methyl
2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hy-
drazinecarbodithioate (250 mg, 0.571 mmol) in DMF (3 mL) was added
N1,N1-dimethylbenzene-1,3-diamine (195 mg, 1.43 mmol). The contents
were heated at 150.degree. C. with stirring for 5 h before the
solution was allowed to cool overnight. The mixture was filtered,
and the filtrate was purified via RP-HPLC to afford the desired
material (235 mg, 78%) as an off-white solid: mp 192-194.degree.
C.; .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 11.82 (s, 1H),
10.04 (s, 1H), 9.41 (s, 1H), 8.19 (s, 1H), 8.16-7.99 (m, 6H), 7.61
(d, J=8.3 Hz, 2H), 7.16 (t, J=7.2 Hz, 1H), 7.01 (m, 1H), 6.87 (m,
1H), 6.58 (m, 1H), 2.88 (s, 6H); ESIMS m/z 526 ([M+H].sup.+).
Example 3
Preparation of
N-benzyl-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzy-
lidene)hydrazinecarbothioamide (Compound I-3) [Synthesis Method
C]
##STR00016##
[0109] To a 50 mL round-bottomed flask containing
4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]benzaldehyde
(500 mg, 1.5 mmol) in EtOH (3 mL) was added
4-benzylthiosemicarbazide (650 mg, 3.6 mmol). The reaction mixture
was heated at 80.degree. C. overnight. H.sub.2O was added upon
completion of the reaction, and the crude product material was
isolated by vacuum filtration. The title compound was isolated via
RP-HPLC as a white solid (390 mg, 52%): mp 220-224.degree. C.;
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 9.29 (s, 1H), 8.59 (s,
1H), 8.21 (d, J=8.4 Hz, 2H), 7.85-7.79 (m, 3H), 7.71 (d, J=8.4 Hz,
2H), 7.46-7.30 (m, 8H), 5.01 (d, J=5.8 Hz, 2H); ESIMS m/z 497.2
(M+H).
[0110] Compounds I-4 through I-31 in Table 1 were synthesized in
accordance with the examples above. Other intermediates used in the
preparation of compounds of this invention were prepared in
accordance with the procedures described in Brown, et al, WO
2011017504 A1, or by other known routes.
Example 4
Preparation of
N-(4-dimethylaminophenyl)-S-methyl-2-{4-[1-(4-trifluoromethoxyphenyl)-1H--
[1,2,4]-triazol-3-yl]-benzylidene}-hydrazine-carbothioamide
(Compound 1C) (Synthesis Method D)
##STR00017##
[0112] A solution containing
(E)-N-(4-(dimethylamino)phenyl)-2-(4-(1-(4-(trifluoromethoxy)-phenyl)-1H--
1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (150 mg,
0.285 mmol) and iodomethane (0.054 mL, 0.856 mmol) in EtOH (5 mL)
was heated at 80.degree. C. for 3 h before the solvent was removed
under reduced pressure. The residue was purified via normal phase
flash chromatography (gradient elution with hexanes/EtOAc) to
afford the title compound as an orange foam (93 milligrams (mg),
60%): .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 8.61 (s, 1H),
8.48 (s, 1H), 8.22 (d, J=8.24 Hz, 2H), 8.17 (s, 1H), 7.89 (d,
J=8.24 Hz, 2H), 7.80 (d, J=8.28 Hz, 2H), 7.41 (d, J=8.28 Hz, 2H),
7.19 (d, J=8.24 Hz, 2H), 6.71 (d, J=8.24 Hz, 2H), 2.99 (s, 6H),
2.42 (s, 3H); EIMS m/z 540 (M.sup.+).
Example 5
General procedure for S-alkylation of triaryl thiosemicarbazones
(Synthesis Method E)
[0113] A stirred solution of the thiosemicarbazone and alkylating
reagent in CH.sub.2Cl.sub.2 or chloroform (CHCl.sub.3) was heated
at from 35 to 50.degree. C. for from 10 to 24 h. The cooled
solution was concentrated under reduced pressure. The residue was
generally purified via chromatography using a chloroform/methanol
(CHCl.sub.3/CH.sub.3OH) or EtOAc-hexane solution as the eluent to
afford the S-alkylated products.
Example 6
Preparation of (S)-tert-butyl
3-((2-((Z)-(2,6-dimethylphenylimino)-((E)-2-(4-(1-(4-(trifluoromethoxy)ph-
enyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinyl)-methylthio)acetamido)m-
ethyl)piperidine-1-carboxylate (Compound 56C) (Synthesis Method
E)
##STR00018##
[0115] To a solution of bromoacetyl bromide (26 microliters
(.mu.L), 0.299 mmol) in dichloroethane (3 mL) was added dropwise a
solution of (S)-tert-butyl 3-(aminomethyl)piperidine-1-carboxylate
(63.9 mg, 0.298 mmol) in dichloromethane (1 mL), followed by
N-ethyl-N-isopropylpropan-2-amine (76 mg, 0.588 mmol). This mixture
was stirred at room temperature for 30 min, then
(E)-N-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4--
triazol-3-yl)benzylidene)hydrazine-carbothioamide (100 mg, 0.196
mmol) was added as a solid and the mixture was heated to 40.degree.
C. for 90 min. It was then allowed to cool to room temperature and
evaporated under reduced pressure, giving a light yellow glass,
which was dissolved in acetonitrile (2 mL) and allowed to stand at
room temperature. The resulting precipitate was isolated by
centrifuge and decanting, washing with fresh acetonitrile. The
solid was dried under a nitrogen stream and then under high vacuum.
The crude product was recrystallized from acetone-isopropyl
alcohol. The title compound was isolated as a white solid (36.5 mg,
24%): mp 148-151.degree. C.; .sup.1H NMR (400 MHz,
methanol-d.sub.4) .delta. 9.18 (s, 1H), 8.59 (s, 1H), 8.30 (d,
J=8.1 Hz, 2H), 8.12 (m, 2H), 8.07-8.00 (m, 2H), 7.58-7.43 (m, 2H),
7.33 (dd, J=8.6, 6.5 Hz, 1H), 7.25 (d, J=7.6 Hz, 2H), 4.02 (m, 2H),
3.97-3.75 (m, 2H), 3.21 (d, J=6.9 Hz, 2H), 2.90 (m, 1H), 2.59 (m,
1H), 2.35 (s, 6H), 1.84 (m, 2H), 1.78-1.63 (m, 2H), 1.44 (s, 9H),
1.29 (m, 3H); ESIMS m/z 765 (M+H).
Example 7
Preparation of
(1Z,2E)-2-oxo-2-(((R)-piperidin-3-ylmethyl)amino)ethyl
N-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-tria-
zol-3-yl)benzylidene)hydrazinecarbimidothioate trifluoroacetic acid
(Compound 62C) (Synthesis Method K)
##STR00019##
[0117] A solution of (S)-tert-butyl
3-((2-((Z)-(2,6-dimethylphenylimino)-((E)-2-(4-(1-(4-(trifluoromethoxy)ph-
enyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinyl)methylthio)-acetamido)m-
ethyl)piperidine-1-carboxylate (32.0 mg, 0.042 mmol) in TFA (250
.mu.L, 3.24 mmol) was stirred at room temperature for 10 min
Et.sub.2O (10 mL) was then added giving a white precipitate, which
was isolated by centrifuge and decanting, then rinsing with fresh
Et.sub.2O (5 mL). The solid was dried under nitrogen stream and
then under high vacuum giving the title compound as a white solid
(19.8 mg, 60%): mp 110-120.degree. C.; .sup.1H NMR (400 MHz,
methanol-d.sub.4) .delta. 9.18 (s, 1H), 8.56 (m, 1H), 8.26 (m, 2H),
8.16-7.84 (m, 4H), 7.52 (m, 2H), 7.27 (m, 1H), 7.22 (m, 2H), 4.00
(s, 2H), 3.28 (m, 3H), 3.06-2.83 (m, 1H), 2.75 (t, J=12.2 Hz, 1H),
2.34 (s, 6H), 2.21-1.83 (m, 4H), 1.72 (m, 1H), 1.47-1.19 (m, 2H);
ESIMS m/z 665 (M+H).
Example 8
Preparation of
2-(((Z)-((4-methoxy-2,6-dimethylphenyl)imino)((E)-2-(4-(1-(4-(trifluorome-
thoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinyl)methyl)-thio)ac-
etic acid sodium salt (Compound 68C)
##STR00020##
[0119] To a solution of
2-((Z)-(4-methoxy-2,6-dimethylphenylimino)((E)-2-(4-(1-(4-(trifluorometho-
xy)phenyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinyl)methylthio)acetic
acid (77.7 mg, 0.130 mmol) in THF (10 mL) was added slowly sodium
methanolate (0.5 M in methanol; 260 .mu.L, 0.130 mmol) at room
temperature. The mixture immediately turned a darker yellow and was
then evaporated at room temperature under vacuum giving a light
orange solid. This material was triturated with Et.sub.2O
(2.times.) and isolated by decanting using a centrifuge and drying
under a nitrogen stream and then under high vacuum. The title
compound was isolated as a light orange solid (32 mg, 39%). mp
146-154.degree. C.; .sup.1H NMR (400 MHz, methanol-d.sub.4) .delta.
9.11 (s, 1H), 8.64-7.68 (m, 7H), 7.51 (m, 2H), 6.70 (s, 2H),
3.85-3.70 (m, 4H), 3.61 (m, 1H), 2.29 (s, 6H); ESIMS m/z 599
(M+H).
Example 9
Preparation of
(Z)-3-(4-methoxy-2,6-dimethylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)ph-
enyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-one
(Compound 69C) (Synthesis Method F)
##STR00021##
[0121] To a solution of
(E)-N-(4-methoxy-2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-
-1H-1,2,4-triazol-3-yl)benzylidene)hydrazine-carbothioamide (250
mg, 0.462 mmol) in EtOH (5 mL) was added methyl bromoacetate (100
mg, 0.65 mmol), and the mixture was heated to 70.degree. C. for 4
h. The mixture was allowed to cool to room temperature and diluted
with water (1 mL). The precipitate was vacuum filtered, giving the
title compound as a white solid (204 mg, 76%): mp 188-190.degree.
C.; .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.56 (s, 1H), 8.33
(s, 1H), 8.22 (d, J=8.1 Hz, 2H), 7.90-7.70 (m, 4H), 7.39 (d, J=8.7
Hz, 2H), 6.72 (s, 2H), 4.01 (s, 2H), 3.87-3.73 (s, 3H), 2.18 (s,
6H); ESIMS m/z 581 (M+H).
Example 10
Preparation of
4-((2Z)-3-(2,6-dimethylphenyl)-2-((4-(1-(4-(trifluoromethoxy)phenyl)-1H-1-
,2,4-triazol-3-yl)benzylidene)hydrazono)-2,3-dihydrothiazol-4-yl)-N,N-diet-
hylaniline (Compound 74C) (Synthesis Method G)
##STR00022##
[0123] To a solution of
(E)-N-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4--
triazol-3-yl)benzylidene)hydrazine-carbothioamide (74.7 mg, 0.144
mmol) in dichloroethane (5 mL), was added
.alpha.-bromo-4-diethylamino)acetophenone (53.9 mg, 0.199 mmol),
and the mixture was heated to 40.degree. C. for 4 h. The mixture
was then cooled to room temperature and evaporated under vacuum.
The crude material was triturated with acetonitrile and decanted
(2.times.). The resulting solid was dried under a stream of
nitrogen, giving the title compound as a pale yellow solid (25 mg,
25%): mp 190-193.degree. C. dec; .sup.1H NMR (400 MHz,
methanol-d.sub.4) .delta. 9.20 (s, 1H), 8.38 (s, 1H), 8.31-8.24 (m,
2H), 8.08-8.00 (m, 2H), 7.95-7.88 (m, 2H), 7.55-7.48 (m, 3H),
7.48-7.36 (m, 5H), 7.31 (d, J=7.7 Hz, 2H), 3.60 (q, J=7.2 Hz, 4H),
2.20 (s, 6H), 1.07 (t, J=7.2 Hz, 6H); ESIMS m/z 682 (M+H).
Example 11
Preparation of
(Z)-2-(2,6-dimethylphenylimino)-3-((E)-4-(1-(4-(trifluoromethoxy)phenyl)--
1H-1,2,4-triazol-3-yl)benzylideneamino)thiazolidin-4-one (Compound
81C) (Synthesis Method I)
##STR00023##
[0125] To a solution of 1-(2,6-dimethylphenyl)thiourea (1.0 g, 5.55
mmol) in EtOH (10 mL) was added methyl 2-bromoacetate (1.0 g, 6.5
mmol) and sodium acetate (1.0 g, 12.2 mmol). The solution was
stirred and heated to reflux for 1 h, then it was cooled and the
liquid was decanted from a small amount of solid material and the
liquid was then diluted with water (10 mL). The precipitate was
isolated by filtration to give (1.1 g, 83%) of
(Z)-3-amino-2-(2,6-dimethylphenylimino)thiazolidin-4-one: mp
149-152.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.06
(d, J=7.2 Hz, 2H), 6.98 (m, 1H), 4.75 (s, 2H), 3.80 (s, 2H), 2.12
(s, 6H); ESIMS m/z 236 (M+H).
[0126] A portion of this material (0.07 g, 0.3 mmol) was dissolved
in glacial acetic acid (3 mL) and treated with
4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzaldehyde
(0.10 g, 0.30 mmol), and the solution was heated to 60.degree. C.
for 2 h. The solution was then cooled and diluted with water (1
mL), and the resulting solid was filtered and air-dried to give the
title compound (0.12 g, 67%): mp 209-213.degree. C.; .sup.1H NMR
(400 MHz, CDCl.sub.3) .delta. 9.42 (s, 1H), 8.59 (s, 1H), 8.28 (d,
J=8.4 Hz, 2H), 8.01 (d, J=8.3 Hz, 2H), 7.80-7.77 (m, 2H), 7.43-7.34
(m, 2H), 7.07 (d, J=7.5 Hz, 2H), 6.98 (dd, J=8.2, 6.7 Hz, 1H), 3.90
(s, 2H), 2.17 (s, 6H); ESIMS m/z 551 (M+H).
Example 12
Preparation of
(2Z,NE)-2-((2-isopropylphenyl)imino)-N-(4-(1-(4-(trifluoromethyl)phenyl)--
1H-1,2,4-triazol-3-yl)benzylidene)-1,3-thiazinan-3-amine and
(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethyl)phenyl)-1H-1,2-
,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazinane (Compound 87C
and 179C) (Synthesis Method J)
##STR00024##
[0128] To
(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethyl)phenyl)-1H-
-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (200 mg,
0.393 mmol) and potassium carbonate (217 mg, 1.57 mmol) in butanone
(10 ml) in a 25 mL vial equipped with a stir bar and vigruex column
was added 1-bromo-3-chloropropane (0.047 ml, 0.472 mmol). The
reaction was heated to 60.degree. C. overnight. The reaction was
determined to be complete by LCMS. The reaction mixture was diluted
with DCM and washed with water. The aqueous layer was extracted
with DCM. The organic layers were poured through a phase separator
and concentrated. Purification by flash column chromatography
provided two compounds. The minor compound was dried overnight
under house vacuum providing the title compound 87C
(2Z,NE)-2-((2-isopropylphenyl)imino)-N-(4-(1-(4-(trifluoromethyl)phenyl)--
1H-1,2,4-triazol-3-yl)benzylidene)-1,3-thiazinan-3-amine (28.5 mg,
13%) as a yellow solid: mp 187-189.degree. C.; .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.81 (s, 1H), 8.66 (s, 1H), 8.21 (d, J=8.3
Hz, 2H), 7.92 (d, J=8.4 Hz, 2H), 7.81 (t, J=10.2 Hz, 4H), 7.30-7.26
(m, 2H), 7.17-7.04 (m, 1H), 6.83 (d, J=6.4 Hz, 1H), 3.96 (t, J=6.1
Hz, 2H), 3.13 (heptet, J=6.9 Hz, 1H), 2.97-2.90 (m, 2H), 2.47-2.38
(m, 2H), 1.25 (d, J=7.5 Hz, 6H); ESIMS m/z 550 (M+H). The major
compound was recrystallized with MeOH. The solid was filtered,
washed with MeOH and dried at 50.degree. C. under vacuum. The solid
was then azeotroped with acetone (3.times.) and the resultant solid
was dried at 50.degree. C. under vacuum providing the title
compound 179C
(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethyl)phenyl)-1H-1,2-
,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazinane as a yellow
solid (92.3 mg, 0.168 mmol, 43%): mp 212-213.degree. C.; .sup.1H
NMR (400 MHz, CDCl.sub.3) .delta. 8.64 (s, 1H), 8.15 (d, J=8.4 Hz,
2H), 8.06 (s, 1H), 7.91 (d, J=8.5 Hz, 2H), 7.79 (d, J=8.6 Hz, 2H),
7.75 (d, J=8.4 Hz, 2H), 7.38 (dd, J=7.8, 1.6 Hz, 1H), 7.33 (td,
J=7.5, 1.4 Hz, 1H), 7.29-7.23 (m, 1H), 7.18 (dd, J=7.8, 1.4 Hz,
1H), 3.78-3.72 (m, 1H), 3.59-3.48 (m, 1H), 3.18-3.04 (m, 3H),
2.40-2.30 (m, 2H), 1.26-1.20 (m, 6H); ESIMS m/z 550 (M+H).
Example 13
Preparation of
(Z)-3-(2-cyclopropylphenyl)-5-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)ph-
enyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidin-4-one
(Compound 127C) (Synthesis Method F)
##STR00025##
[0130] To
(E)-N-(2-cyclopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-
-1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (100 mg,
0.191 mmol) and sodium acetate (63.0 mg, 0.765 mmol) in EtOH (4 mL)
was added methyl 2-bromopropanoate (0.026 mL, 0.230 mmol). The
reaction was heated to 60.degree. C. overnight. The reaction was
then heated to 85.degree. C. for 72 hours. The reaction mixture was
diluted with DCM and washed with water. The aqueous layer was
extracted with DCM. The organic layers were poured through a phase
separator and concentrated. Purification by flash column
chromatography provided the title compound as a white solid (32.5
mg, 0.056 mmol, 30%): mp 112-115.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.58 (s, 1H), 8.32 (s, 1H), 8.22 (d, J=8.3 Hz,
2H), 7.87-7.75 (m, 4H), 7.43-7.32 (m, 4H), 7.26-7.24 (m, 2H), 4.23
(q, J=7.3 Hz, 1H), 1.85-1.78 (m, 4H), 0.90-0.78 (m, 2H), 0.78-0.69
(m, 1H), 0.65-0.55 (m, 1H); ESIMS m/z 578 (M+H).
Example 14
Preparation of
(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,-
2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidine (Compound 132C)
(Synthesis Method J)
##STR00026##
[0132] To
(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1-
H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (214 mg,
0.407 mmol) and potassium carbonate (225 mg, 1.63 mmol) in butanone
(4 ml) was added 1-bromo-2-chloroethane (70.0 mg, 0.489 mmol). The
reaction was heated to 90.degree. C. overnight. The reaction was
determined to be complete by LCMS. The reaction mixture was cooled,
diluted with DCM and washed with water. The aqueous layer was
extracted with DCM. The organic layers were filtered through a
phase separator and concentrated. Separation by flash column
chromatography and drying the recovered solid at 55.degree. C.
under vacuum provided the title compound as a white solid (137 mg,
0.249 mmol, 61%): mp 193-196.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.56 (s, 1H), 8.22 (s, 1H), 8.17 (d, J=8.4 Hz,
2H), 7.80 (ddd, J=9.5, 6.9, 4.9 Hz, 4H), 7.43-7.33 (m, 4H),
7.31-7.21 (m, 2H), 4.05 (td, J=9.4, 7.1 Hz, 1H), 3.97-3.87 (m, 1H),
3.42-3.33 (m, 1H), 3.33-3.24 (m, 1H), 3.12 (heptet, J=6.8 Hz, 1H),
1.27 (d, J=6.8 Hz, 3H), 1.22 (d, J=6.9 Hz, 3H); ESIMS m/z 552
(M+H).
Example 15
Preparation of
(Z)-3-(2-isopropylphenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phen-
yl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)thiazolidine
(Compound 155C) (Synthesis Method J)
##STR00027##
[0134] To
(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1-
H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (300 mg,
0.572 mmol) and potassium carbonate (316 mg, 2.29 mmol) in butanone
(4 ml) was added 1,2-dibromopropane (0.072 ml, 0.686 mmol). The
reaction was heated to 85.degree. C. overnight. The reaction was
determined to be complete by LCMS. The reaction mixture was diluted
with DCM and washed with water. The aqueous layer was extracted
with DCM. The organic layers were poured through a phase separator
and concentrated. Purification by flash column chromatography
provided a yellow solid. The solid was recrystallized from MeOH.
The solid was filtered, washed with MeOH, and dried to provide the
title compound as a yellow solid which was dissolved in acetone and
concentrated (3.times.). The light yellow solid was collected and
dried under to provide the title compound as a 1:1 mixture of
rotational diastereoisomers (75.1 mg, 0.133 mmol, 23%): mp
201-204.degree. C.; .sup.1H NMR of mixture (400 MHz, CDCl.sub.3)
.delta. 8.56 (s, 2H), 8.18 (dd, J=10.8, 7.4 Hz, 6H), 7.84-7.73 (m,
8H), 7.45-7.30 (m, 8H), 7.30-7.23 (m, 2H), 7.20 (d, J=6.7 Hz, 1H),
7.12 (dd, J=7.8, 1.2 Hz, 1H), 4.43-4.33 (m, 1H), 4.16 (dd, J=12.6,
6.3 Hz, 1H), 3.48 (dt, J=13.3, 6.7 Hz, 1H), 3.37 (dd, J=10.8, 6.2
Hz, 1H), 3.24 (dt, J=13.7, 6.9 Hz, 1H), 3.08-2.92 (m, 3H),
1.33-1.16 (m, 18H); ESIMS m/z 566 (M+H).
Example 16
Preparation of
(Z)-3-(2,6-dimethylphenyl)-4-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phe-
nyl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-2,3-dihydrothiazole
(Compound 173C) (Synthesis Method G)
##STR00028##
[0135] To a solution of
(E)-N-(o-tolyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-y-
l)benzylidene)hydrazinecarbothioamide (257 mg, 0.520 mmol) in
butanone (5 mL) was added triethylamine (0.14 mL, 1.0 mmol) and
chloroacetone (0.06 mL, 0.73 mmol) and refluxed at 75.degree. C.
for 15 h. The mixture was allowed to cool to room temperature and
then transferred to a separatory funnel containing water (5 mL) and
extracted twice with dichloromethane. The organic layers were
filtered through a phase separator, adsorbed onto silica gel, and
purified by flash column chromatography to afford the title
compound as a yellow solid (229 mg, 83%): mp 87.degree. C. (dec);
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.56 (s, 1H), 8.19-8.15
(m, 3H), 7.82-7.75 (m, 4H), 7.43-7.30 (m, 5H), 7.24 (d, J=7.3 Hz,
1H), 5.88 (d, J=1.3 Hz, 1H), 2.21 (s, 3H), 1.80 (d, J=1.2 Hz, 3H);
ESIMS m/z 536 (M+H).
Example 17
Preparation of
(Z)-3-(2-isopropylphenyl)-5-methyl-2-((E)-(4-(1-(4-(trifluoromethoxy)phen-
yl)-1H-1,2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazinane
(Compound 178C) (Synthesis Method J)
##STR00029##
[0137] To
(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1-
H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (100 mg,
0.191 mmol) and potassium carbonate (105 mg, 0.763 mmol) in
butanone (4 ml) was added 1-bromo-3-chloro-2-methylpropane (39.0
mg, 0.229 mmol). The reaction was heated to 80.degree. C.
overnight. The reaction mixture was then diluted with DCM and
washed with water. The aqueous layer was extracted with DCM. The
organic layers were poured through a phase separator and
concentrated. Purification by flash column chromatography provided
the title compound as a light yellow solid as a mixture of
rotational diastereoisomers: mp 186-190.degree. C.; .sup.1H NMR
(400 MHz, CDCl.sub.3) .delta. 8.55 (d, J=3.6 Hz, 1H), 8.14 (d,
J=8.4 Hz, 2H), 8.06 (s, 1H), 7.84-7.77 (m, 2H), 7.74 (d, J=8.4 Hz,
2H), 7.38 (d, J=9.0 Hz, 3H), 7.32 (td, J=7.5, 1.4 Hz, 1H), 7.26 (s,
1H), 7.17 (t, J=7.1 Hz, 1H), 3.69-3.26 (m, 1H), 3.55-3.37 (m, 1H),
3.18-2.98 (m, 2H), 2.93-2.80 (m, 1H), 2.47 (d, J=35.9 Hz, 1H),
1.31-1.12 (m, 9H); ESIMS m/z 580 (M+H).
Example 18
Preparation of
(Z)-3-(2,6-dimethylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1-
,2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazepane (Compound
211C) (Synthesis Method J)
##STR00030##
[0139] To
(E)-N-(2,6-dimethylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)--
1H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (500 mg,
0.979 mmol) and potassium carbonate (541 mg, 3.92 mmol) in acetone
(4 ml) was added 1-bromo-4-chlorobutane (0.135 ml, 1.18 mmol). The
reaction was heated to 60.degree. C. overnight. The alkylation was
determined to be complete by ultra performance liquid
chromatography ("UPLC"). The reaction mixture was diluted with DCM
and washed with water. The aqueous layer was extracted with DCM.
The organic layers were poured through a phase separator and
concentrated. Purification by flash column chromatography provided
(1Z,N'E)-4-chlorobutyl
N-(2,6-dimethylphenyl)-N'-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-tri-
azol-3-yl)benzylidene)carbamohydrazonothioate (427 mg, 0.710 mmol,
73%) as a yellow gum which was used without further purification.
To (1Z,N'E)-4-chlorobutyl
N-(2,6-dimethylphenyl)-N'-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-tri-
azol-3-yl)benzylidene)-carbamohydrazonothioate (427 mg, 0.710
mmol), potassium iodide (236 mg, 1.42 mmol) and potassium carbonate
(393 mg, 2.84 mmol) was added acetone (7 ml). The reaction was
heated to 65.degree. C. for 72 h. The reaction was cooled to room
temperature, diluted with DCM and washed with water. The aqueous
layer was extracted with DCM. The organic layers were poured
through a phase separator and concentrated. Purification by flash
column chromatography provided a yellow oil. The yellow oil was
recrystallized from MeOH, filtered, washed with MeOH and dried to
provide the title compound as a yellow solid (100 mg, 0.177 mmol,
25%): mp 100-106.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.55 (s, 1H), 8.15 (d, J=8.4 Hz, 2H), 8.10 (s, 1H), 7.79
(dt, J=10.4, 5.8 Hz, 4H), 7.38 (d, J=8.3 Hz, 2H), 7.11 (s, 3H),
3.85-3.78 (m, 2H), 3.20-3.12 (m, 2H), 2.30 (s, 6H), 2.13-2.07 (m,
2H), 1.87-1.82 (m, 2H); ESIMS m/z 566 (M+H).
Example 19
Preparation of
(Z)-3-(2-isopropylphenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,-
2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazinan-4-one
(Compound 224C) (Synthesis Method L)
##STR00031##
[0141] To
(E)-N-(2-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1-
H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (500 mg,
0.953 mmol) in butanone (9.5 ml) was added acryloyl chloride (0.077
ml, 0.953 mmol). The reaction was stirred at ambient temperature
for 10 min followed by 50.degree. C. for 2 h. The reaction was
cooled to 40.degree. C. overnight. The reaction was determined to
be complete by LCMS. The reaction mixture was diluted with DCM and
washed with saturated sodium bicarbonate. The aqueous layer was
extracted with DCM. The organic layers were poured through a phase
separator and concentrated. Purification by flash column
chromatography provided a yellow oil. The oil was recrystallized
with diethyl ether/hexanes to provide the title compound as a light
yellow solid (125 mg, 0.217 mmol, 23%): mp 118.degree. C. (dec);
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.57 (s, 1H), 8.21 (d,
J=8.4 Hz, 2H), 8.16 (s, 1H), 7.85-7.75 (m, 4H), 7.46-7.36 (m, 4H),
7.33-7.26 (m, 1H), 7.10 (d, J=7.6 Hz, 1H), 3.26-3.14 (m, 4H), 2.81
(heptet, J=6.9 Hz, 1H), 1.21 (t, J=7.2 Hz, 6H); ESIMS m/z 580
(M+H).
Example 20
Preparation of
(Z)-3-(2,6-difluorophenyl)-2-((E)-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1-
,2,4-triazol-3-yl)benzylidene)hydrazono)-1,3-thiazetidine (Compound
245C) (Synthesis Method J)
##STR00032##
[0143] To a mixture of
(E)-N-(2,6-difluorophenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4--
triazol-3-yl)benzylidene)hydrazinecarbothioamide (0.50 g, 0.96
mmol) and potassium carbonate (0.53 g, 3.9 mmol) in butanone (10
mL) in a 25 mL vial equipped with a magnetic stir bar was added
diiodomethane (0.093 ml, 1.2 mmol). The reaction was heated to
55.degree. C. and stirred for two days. The reaction mixture was
diluted with DCM, washed with water, and the phases separated. The
aqueous phase was extracted with DCM and the combined organic
phases were dried by passing through a phase separator cartridge
and then concentrated. Purification by flash column chromatography
provided a yellow oil which crystallized upon standing. The solid
was slurried in diethyl ether and hexanes and collected by vacuum
filtration. The solid was washed with hexanes and dried to provide
the title compound (0.086 g, 0.16 mmol, 17%) as a light yellow
solid: mp 144-146.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.58 (s, 1H), 8.34 (s, 1H), 8.20 (d, J=8.3 Hz, 2H), 7.81
(d, J=8.8 Hz, 4H), 7.40 (d, J=8.3 Hz, 2H), 7.31-7.23 (m, 1H),
7.03-6.97 (m, 2H), 5.05 (s, 2H); ESIMS m/z 532 (M+H).
[0144] Compounds 240-244 and 246-261, shown in Table 3, were
prepared according to the method described in Example 20 from the
appropriately substituted intermediates disclosed in Table 1.
Characterization data for these compounds is reported in Table
4.
Example 21
Separation of Rotationally Stable Atropisomers from Racemic
Mixtures
[0145] Separation of constituent isomers from racemic mixtures can
be carried out utilizing one of the following chiral HPLC
methods.
Separation Method A:
[0146] The column used for separation was a Chiral Technologies INC
Chiral Pak 1A 5 .mu.m, 4.6.times.250 mm column (Part number 80325).
The method consists of a 1.0 mL/min flow rate from 0 to 30 min with
an isocratic hold at 25% B for the duration of the run. The A
eluent is n-hexane, the B eluent is iso-propyl alcohol.
Separation Method B:
[0147] The column used for separation was a Chiral Technologies INC
Chiral Pak 1B 5 .mu.m, 4.6.times.250 mm column (Part number 81325).
The method consists of a 1.0 mL/min flow rate from 0 to 30 min with
an isocratic hold at 15% B for the duration of the run. The A
eluent is n-pentane, the B eluent is n-butyl alcohol.
Example 22
Preparation of
(E)-N-(2-fluoro-6-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1-
H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (Compound
I-40; Synthesis Method C)
##STR00033##
[0148] Step 1: Preparation of
1-fluoro-2-nitro-3-(prop-1-en-2-yl)benzene (1-37, Method M)
[0149] To a mixture of 1-bromo-3-fluoro-2-nitrobenzene (0.953 g,
4.33 mmol) in a 100 mL round-bottomed flask equipped with a
magnetic stir bar and nitrogen inlet were added dioxane (17.3 mL),
sodium carbonate (0.551 g, 5.20 mmol), water (4.33 mL), and
4,4,5,5-tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolane (0.977
mL, 5.20 mmol). To this mixture was added
bis(triphenyl-phosphine)palladium(II)chloride (0.243 g, 0.347
mmol). The flask was evacuated and purged with nitrogen (3.times.)
and then heated to 80.degree. C. and stirred overnight. The
reaction was cooled to room temperature, filtered through
Celite.RTM., and the pad was washed with ethyl acetate. The phases
were separated and the organic phase was concentrated. Purification
by flash column chromatography provided the title compound (0.590
g, 3.26 mmol, 75% yield) as a light yellow oil: .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 7.48-7.36 (m, 1H), 7.21-7.06 (m, 2H), 5.23
(p, J=1.5 Hz, 1H), 5.05 (q, J=1.1 Hz, 1H), 2.09 (s, 3H); .sup.13C
NMR (101 MHz, CDCl.sub.3) .delta. 153.56 (d, J.sub.CF=257.5 Hz),
139.62, 139.60, 138.83, 131.48 (d, T.sub.CF=8.6 Hz), 124.47 (d,
J.sub.CF=3.6 Hz), 117.60, 115.51 (d, J.sub.CF=19.1 Hz), 23.18.
Step 2: Preparation of 2-fluoro-6-isopropylaniline (1-38, Method
M)
[0150] To a solution of 1-fluoro-2-nitro-3-(prop-1-en-2-yl)benzene
(0.590 g, 3.26 mmol) in ethyl acetate (32.6 mL) in a 250 mL
round-bottomed flask equipped with a magnetic stir bar and nitrogen
inlet was added palladium on carbon (5% Pd/C, 0.693 g, 0.326 mmol).
The reaction flask was evacuated and purged with hydrogen
(2.times.) and then placed under 1 atmosphere (atm) of hydrogen and
stirred at room temperature overnight. The reaction was filtered
through Celite.RTM. and the pad was washed with ethyl acetate. The
filtrate was concentrated to give the title compound (0.423 g, 2.76
mmol, 85% yield) as clear and colorless oil: IR (neat) 3476 (m),
3392 (m), 2966 (m), 2872 (m), 1628 (s), 1474 (s), 1270 (m)
cm.sup.-1; .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 6.92 (dt,
J=7.7, 1.2 Hz, 1H), 6.86 (ddd, J=10.8, 8.1, 1.4 Hz, 1H), 6.69 (td,
J=8.0, 5.6 Hz, 1H), 3.71 (bs, 2H), 2.92 (hept, J=6.8 Hz, 1H), 1.26
(d, J=6.8 Hz, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) .delta.
151.91 (d, J=237.6 Hz), 135.10 (d, J=2.3 Hz), 131.60 (d, J=11.8
Hz), 120.52 (d, J=3.0 Hz), 117.99 (d, J=8.0 Hz), 112.28 (d, J=19.6
Hz), 27.77 (d, J=2.9 Hz), 22.22.
Step 3: Preparation of
N-(2-fluoro-6-isopropylphenyl)hydrazinecarbothioamide (I-39, Method
M)
[0151] To a 100 mL round-bottomed flask equipped with a stir bar
and nitrogen inlet were added 2-fluoro-6-isopropylaniline (0.415 g,
2.71 mmol), dichloromethane (13.6 mL), water (6.78 mL), and sodium
bicarbonate (0.683 g, 8.13 mmol). To this biphasic mixture was
added thiophosgene (0.199 mL, 2.60 mmol) and the reaction was
stirred vigorously for 2 hours. The suspension was filtered through
a phase separator cartridge and the organic phase was concentrated
in a 100 mL round-bottomed flask. The flask was equipped with a
magnetic stir bar and nitrogen inlet and the residue was dissolved
in ethanol (6.78 mL). To the resulting solution was added hydrazine
hydrate (0.131 mL, 2.71 mmol) and the reaction was stirred at room
temperature for 2 days. The solution was concentrated and the
resulting residue was suspended in a mixture of diethyl ether and
hexanes and re-concentrated to give a solid. The solid was
suspended in a minimal amount of diethyl ether and the mixture was
diluted with hexanes. The majority of the diethyl ether was
evaporated and the resulting solid was collected by vacuum
filtration, washed with hexanes and then dried under house vacuum
to provide the title compound (0.518 g, 2.28 mmol, 84% yield) as a
white solid: mp 122-124.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.56 (bs, 1H), 7.52 (bs, 1H), 7.32 (td, J=8.1,
5.6 Hz, 1H), 7.17-7.12 (m, 1H), 7.00 (ddd, J=9.5, 8.2, 1.4 Hz, 1H),
4.07 (bs, 2H), 3.15 (hept, J=7.0 Hz, 1H), 1.24 (d, J=6.9 Hz, 6H);
ESIMS m/z 229 ([M+H].sup.+).
Step 4: Preparation of
(E)-N-(2-fluoro-6-isopropylphenyl)-2-(4-(1-(4-(trifluoromethoxy)phenyl)-1-
H-1,2,4-triazol-3-yl)benzylidene)hydrazinecarbothioamide (I-40,
Method C)
[0152] To a solution of
4-(1-(4-(trifluoromethoxy)phenyl)-1H-1,2,4-triazol-3-yl)-benzaldehyde
(0.760 g, 2.28 mmol) in methanol (22.8 mL) in a 100 mL
round-bottomed flask equipped with a magnetic stir bar and reflux
condenser was added
N-(2-fluoro-6-isopropylphenyl)hydrazinecarbothioamide (0.518 g,
2.28 mmol), and the reaction was heated to 65.degree. C. and
stirred for 6 hours. The temperature was lowered to 50.degree. C.
and the reaction was stirred overnight. The reaction was cooled to
room temperature and the resulting solid was filtered, washed with
methanol, and dried under vacuum (25 in Hg) at 55.degree. C. to
give the title compound (0.907 g, 1.67 mmol, 73% yield) as a white
solid: mp 210-212.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 9.54 (s, 1H), 8.60 (s, 1H), 8.56 (s, 1H), 8.30-8.22 (m,
2H), 7.92 (s, 1H), 7.86-7.76 (m, 4H), 7.44-7.38 (m, 2H), 7.35 (dd,
J=8.1, 5.6 Hz, 1H), 7.18 (d, J=7.9 Hz, 1H), 7.04 (ddd, J=9.4, 8.2,
1.3 Hz, 1H), 3.22 (p, J=6.9 Hz, 1H), 1.29 (d, J=6.9 Hz, 6H); ESIMS
m/z 544 ([M+H].sup.+).
[0153] Intermediate compounds I-32-I-36 and I-41-I-65, shown in
Table 1, were prepared according to the methods outlined in Example
22, Steps I-4. Characterization data for these intermediates is
shown in Table 2.
Example 23
Bioassays on Beet Armyworm ("BAW") and Corn Earworm ("CEW")
[0154] BAW has few effective parasites, diseases, or predators to
lower its population. BAW infests many weeds, trees, grasses,
legumes, and field crops. In various places, it is of economic
concern upon asparagus, cotton, corn, soybeans, tobacco, alfalfa,
sugar beets, peppers, tomatoes, potatoes, onions, peas, sunflowers,
and citrus, among other plants. CEW is known to attack corn and
tomatoes, but it also attacks artichoke, asparagus, cabbage,
cantaloupe, collards, cowpeas, cucumbers, eggplant, lettuce, lima
beans, melon, okra, peas, peppers, potatoes, pumpkin, snap beans,
spinach, squash, sweet potatoes, and watermelon, among other
plants. CEW is also known to be resistant to certain insecticides.
Consequently, because of the above factors control of these pests
is important. Furthermore, molecules that control these pests are
useful in controlling other pests.
[0155] Certain molecules disclosed in this document were tested
against BAW and CEW using procedures described in the following
examples. In the reporting of the results, the "BAW & CEW
Rating Table" was used (See Table Section).
Bioassays on BAW (spodoptera exigua)
[0156] Bioassays on BAW were conducted using a 128-well diet tray
assay. One to five second instar BAW larvae were placed in each
well (3 mL) of the diet tray that had been previously filled with 1
mL of artificial diet to which 50 .mu.g/cm.sup.2 of the test
compound (dissolved in 50 .mu.L of 90:10 acetone-water mixture) had
been applied (to each of eight wells) and then allowed to dry.
Trays were covered with a clear self-adhesive cover and held at
25.degree. C., 14:10 light-dark for five to seven days. Percent
mortality was recorded for the larvae in each well; activity in the
eight wells was then averaged. The results are indicated in the
table entitled "Table 5: Biological Results" (See Table
Section).
Bioassays on CEW (Helicoverpa zea)
[0157] Bioassays on CEW were conducted using a 128-well diet tray
assay. One to five second instar CEW larvae were placed in each
well (3 mL) of the diet tray that had been previously filled with 1
mL of artificial diet to which 50 .mu.g/cm.sup.2 of the test
compound (dissolved in 50 .mu.L of 90:10 acetone-water mixture) had
been applied (to each of eight wells) and then allowed to dry.
Trays were covered with a clear self-adhesive cover and held at
25.degree. C., 14:10 light-dark for five to seven days. Percent
mortality was recorded for the larvae in each well; activity in the
eight wells was then averaged. The results are indicated in the
table entitled "Table 5: Biological Results" (See Table
Section).
Example 24
Bioassays on green peach aphid ("GPA") (myzus persicae)
[0158] GPA is the most significant aphid pest of peach trees,
causing decreased growth, shriveling of the leaves, and the death
of various tissues. It is also hazardous because it acts as a
vector for the transport of plant viruses, such as potato virus Y
and potato leafroll virus to members of the nightshade/potato
family Solanaceae, and various mosaic viruses to many other food
crops. GPA attacks such plants as broccoli, burdock, cabbage,
carrot, cauliflower, daikon, eggplant, green beans, lettuce,
macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress,
and zucchini, among other plants. GPA also attacks many ornamental
crops such as carnation, chrysanthemum, flowering white cabbage,
poinsettia, and roses. GPA has developed resistance to many
pesticides.
[0159] Certain molecules disclosed in this document were tested
against GPA using procedures described in the following example. In
the reporting of the results, the "GPA Rating Table" was used (See
Table Section).
[0160] Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5
cm) true leaves, were used as test substrate. The seedlings were
infested with 20-50 GPA (wingless adult and nymph stages) one day
prior to chemical application. Four pots with individual seedlings
were used for each treatment. Test compounds (2 mg) were dissolved
in 2 mL of acetone/methanol (1:1) solvent, forming stock solutions
of 1000 ppm test compound. The stock solutions were diluted
5.times. with 0.025% Tween 20 in H.sub.2O to obtain the solution at
200 ppm test compound. A hand-held aspirator-type sprayer was used
for spraying a solution to both sides of cabbage leaves until
runoff. Reference plants (solvent check) were sprayed with the
diluent only containing 20% by volume of acetone/methanol (1:1)
solvent. Treated plants were held in a holding room for three days
at approximately 25.degree. C. and ambient relative humidity (RH)
prior to grading. Evaluation was conducted by counting the number
of live aphids per plant under a microscope. Percent Control was
measured by using Abbott's correction formula (W. S. Abbott, "A
Method of Computing the Effectiveness of an Insecticide" J. Econ.
Entomol. 18 (1925), pp. 265-267) as follows.
Corrected % Control=100*(X-Y)/X [0161] where [0162] X=No. of live
aphids on solvent check plants and [0163] Y=No. of live aphids on
treated plants
[0164] The results are indicated in the table entitled "Table 5:
Biological Results" (See Table Section).
Pesticidally Acceptable Acid Addition Salts, Salt Derivatives,
Solvates, Ester Derivatives, Polymorphs, Isotopes and
Radionuclides
[0165] Molecules of Formulas One, Two and Three may be formulated
into pesticidally acceptable acid addition salts. By way of a
non-limiting example, an amine function can form salts with
hydrochloric, hydrobromic, sulfuric, phosphoric, acetic, benzoic,
citric, malonic, salicylic, malic, fumaric, oxalic, succinic,
tartaric, lactic, gluconic, ascorbic, maleic, aspartic,
benzenesulfonic, methanesulfonic, ethanesulfonic,
hydroxymethanesulfonic, and hydroxyethanesulfonic acids.
Additionally, by way of a non-limiting example, an acid function
can form salts including those derived from alkali or alkaline
earth metals and those derived from ammonia and amines. Examples of
preferred cations include sodium, potassium, and magnesium.
[0166] Molecules of Formulas One, Two and Three may be formulated
into salt derivatives. By way of a non-limiting example, a salt
derivative can be prepared by contacting a free base with a
sufficient amount of the desired acid to produce a salt. A free
base may be regenerated by treating the salt with a suitable dilute
aqueous base solution such as dilute aqueous sodium hydroxide
(NaOH), potassium carbonate, ammonia, and sodium bicarbonate. As an
example, in many cases, a pesticide, such as 2,4-D, is made more
water-soluble by converting it to its dimethylamine salt.
[0167] Molecules of Formulas One, Two and Three may be formulated
into stable complexes with a solvent, such that the complex remains
intact after the non-complexed solvent is removed. These complexes
are often referred to as "solvates." However, it is particularly
desirable to form stable hydrates with water as the solvent.
[0168] Molecules of Formulas One, Two and Three may be made into
ester derivatives. These ester derivatives can then be applied in
the same manner as the invention disclosed in this document is
applied.
[0169] Molecules of Formulas One, Two and Three may be made as
various crystal polymorphs. Polymorphism is important in the
development of agrochemicals since different crystal polymorphs or
structures of the same molecule can have vastly different physical
properties and biological performances.
[0170] Molecules of Formulas One, Two and Three may be made with
different isotopes. Of particular importance are molecules having
.sup.2H (also known as deuterium) in place of .sup.1H.
[0171] Molecules of Formulas One, Two and Three may be made with
different radionuclides. Of particular importance are molecules
having .sup.14C.
Stereoisomers
[0172] Molecules of Formulas One, Two and Three may exist as one or
more stereoisomers. Thus, certain molecules can be produced as
racemic mixtures. It will be appreciated by those skilled in the
art that one stereoisomer may be more active than the other
stereoisomers. Individual stereoisomers may be obtained by known
selective synthetic procedures, by conventional synthetic
procedures using resolved starting materials, or by conventional
resolution procedures.
Insecticides
[0173] Molecules of Formulas One, Two and Three may also be used in
combination (such as, in a compositional mixture, or a simultaneous
or sequential application) with one or more of the following
insecticides--1,2-dichloropropane, abamectin, acephate,
acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile,
alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin,
allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan,
amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine,
athidathion, azadirachtin, azamethiphos, azinphos-ethyl,
azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin,
bendiocarb, benfuracarb, bensultap, beta-cyfluthrin,
beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin,
biopermethrin, bistrifluoron, borax, boric acid, bromfenvinfos,
bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb,
buprofezin, butacarb, butathiofos, butocarboxim, butonate,
butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide,
camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide,
carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap
hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane,
chlordecone, chlordimeform, chlordimeform hydrochloride,
chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,
chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos,
chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide,
cinerin I, cinerin II, cinerins, cismethrin, cloethocarb,
closantel, clothianidin, copper acetoarsenite, copper arsenate,
copper naphthenate, copper oleate, coumaphos, coumithoate,
crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos,
cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin,
cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cypropen,
cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion,
demephion-O, demephion-S, demeton, demeton-methyl, demeton-O,
demeton-O-methyl, demeton-S, demeton-S-methyl,
demeton-S-methylsulphon, diafenthiuron, dialifos, diatomaceous
earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl,
dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor,
dimefluthrin, dimefox, dimetan, dimethoate, dimethrin,
dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop,
dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb,
dioxathion, disulfoton, dithicrofos, d-limonene, DNOC,
DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin,
ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin,
endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin,
esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion,
ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD,
ethylene dibromide, ethylene dichloride, ethylene oxide,
etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,
fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,
fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,
fenthion, fenthion-ethyl, fenvalerate, fipronil, flometoquin,
flonicamid, flubendiamide (additionally resolved isomers thereof),
flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron,
flufenprox, flufiprole, flupyradifurone, fluvalinate, fonofos,
formetanate, formetanate hydrochloride, formothion, formparanate,
formparanate hydrochloride, fosmethilan, fospirate, fosthietan,
fufenozide, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH,
halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos,
heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide,
hydroprene, hyquincarb, imidacloprid, imidaclothiz, imiprothrin,
indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos,
isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane,
isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II,
jodfenphos, juvenile hormone I, juvenile hormone II, juvenile
hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate,
lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion,
malathion, malonoben, mazidox, ME-5343, MEB-5343, mecarbam,
mecarphon, menazon, meperfluthrin, mephosfolan, mercurous chloride,
mesulfenfos, metaflumizone, methacrifos, methamidophos,
methidathion, methiocarb, methocrotophos, methomyl, methoprene,
methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl
isothiocyanate, methylchloroform, methylene chloride, metofluthrin,
metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin,
milbemycin oxime, mipafox, mirex, molosultap, monocrotophos,
monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled,
naphthalene, nicotine, nifluridide, nitenpyram, nithiazine,
nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,
oxydemeton-methyl, oxydeprofos, oxydisulfoton,
para-dichlorobenzene, parathion, parathion-methyl, penfluoron,
pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate,
phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon,
phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb,
pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite, potassium
thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II,
precocene III, primidophos, profenofos, profluralin, profluthrin,
promacyl, promecarb, propaphos, propetamphos, propoxur,
prothidathion, prothiofos, prothoate, protrifenbute, pymetrozine,
pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I,
pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion,
pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen,
quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide,
resmethrin, rotenone, ryania, sabadilla, schradan, selamectin,
silafluofen, silica gel, sodium arsenite, sodium fluoride, sodium
hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram,
spinosad, spiromesifen, spirotetramat, sulcofuron,
sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl
fluoride, sulprofos, tasmanone, tau-fluvalinate, tazimcarb, TDE,
tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,
tefluthrin, temephos, TEPP, terallethrin, terbufos,
tetrachloroethane, tetrachlorvinphos, tetramethrin,
tetramethylfluthrin, theta-cypermethrin, thiacloprid, thiamethoxam,
thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate,
thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium,
thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin,
transfluthrin, transpermethrin, triarathene, triazamate,
triazophos, trichlorfon, trichlormetaphos-3, trichloronat,
trifenofos, triflumuron, trimethacarb, triprene, vamidothion,
vaniliprole, XMC, xylylcarb, zeta-cypermethrin, and zolaprofos
(collectively these commonly named insecticides are defined as the
"Insecticide Group").
Acaricides
[0174] Molecules of Formulas One, Two and Three may also be used in
combination (such as, in a compositional mixture, or a simultaneous
or sequential application) with one or more of the following
acaricides--acequinocyl, amidoflumet, arsenous oxide, azobenzene,
azocyclotin, benomyl, benoxafos, benzoximate, benzyl benzoate,
bifenazate, binapacryl, bromopropylate, chinomethionat,
chlorbenside, chlorfenethol, chlorfenson, chlorfensulphide,
chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate,
clofentezine, cyenopyrafen, cyflumetofen, cyhexatin, dichlofluanid,
dicofol, dienochlor, diflovidazin, dinobuton, dinocap, dinocap-4,
dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenyl
sulfone, disulfuram, dofenapyn, etoxazole, fenazaquin, fenbutatin
oxide, fenothiocarb, fenpyroximate, fenson, fentrifanil,
fluacrypyrim, fluazuron, flubenzimine, fluenetil, flumethrin,
fluorbenside, hexythiazox, mesulfen, MNAF, nikkomycins, proclonol,
propargite, quintiofos, spirodiclofen, sulfuram, sulfur,
tetradifon, tetranactin, tetrasul, and thioquinox (collectively
these commonly named acaricides are defined as the "Acaricide
Group").
Nematicides
[0175] Molecules of Formulas One, Two and Three may also be used in
combination (such as, in a compositional mixture, or a simultaneous
or sequential application) with one or more of the following
nematicides--1,3-dichloropropene, benclothiaz, dazomet,
dazomet-sodium, DBCP, DCIP, diamidafos, fluensulfone, fosthiazate,
furfural, imicyafos, isamidofos, isazofos, metam, metam-ammonium,
metam-potassium, metam-sodium, phosphocarb, and thionazin
(collectively these commonly named nematicides are defined as the
"Nematicide Group")
Fungicides
[0176] Molecules of Formulas One, Two and Three may also be used in
combination (such as, in a compositional mixture, or a simultaneous
or sequential application) with one or more of the following
fungicides--(3-ethoxypropyl)mercury bromide, 2-methoxyethylmercury
chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate,
8-phenylmercurioxyquinoline, acibenzolar, acibenzolar-S-methyl,
acypetacs, acypetacs-copper, acypetacs-zinc, aldimorph, allyl
alcohol, ametoctradin, amisulbrom, ampropylfos, anilazine,
aureofungin, azaconazole, azithiram, azoxystrobin, barium
polysulfide, benalaxyl, benalaxyl-M, benodanil, benomyl, benquinox,
bentaluron, benthiavalicarb, benthiavalicarb-isopropyl,
benzalkonium chloride, benzamacril, benzamacril-isobutyl,
benzamorf, benzohydroxamic acid, bethoxazin, binapacryl, biphenyl,
bitertanol, bithionol, bixafen, blasticidin-S, Bordeaux mixture,
boscalid, bromuconazole, bupirimate, Burgundy mixture, buthiobate,
butylamine, calcium polysulfide, captafol, captan, carbamorph,
carbendazim, carboxin, carpropamid, carvone, Cheshunt mixture,
chinomethionat, chlobenthiazone, chloraniformethan, chloranil,
chlorfenazole, chlorodinitronaphthalene, chloroneb, chloropicrin,
chlorothalonil, chlorquinox, chlozolinate, climbazole,
clotrimazole, copper acetate, copper carbonate, basic, copper
hydroxide, copper naphthenate, copper oleate, copper oxychloride,
copper silicate, copper sulfate, copper zinc chromate, cresol,
cufraneb, cuprobam, cuprous oxide, cyazofamid, cyclafuramid,
cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole,
cyprodinil, dazomet, dazomet-sodium, DBCP, debacarb, decafentin,
dehydroacetic acid, dichlofluanid, dichlone, dichlorophen,
dichlozoline, diclobutrazol, diclocymet, diclomezine,
diclomezine-sodium, dicloran, diethofencarb, diethyl pyrocarbonate,
difenoconazole, diflumetorim, dimethirimol, dimethomorph,
dimoxystrobin, diniconazole, diniconazole-M, dinobuton, dinocap,
dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon,
diphenylamine, dipyrithione, disulfuram, ditalimfos, dithianon,
DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph,
dodemorph acetate, dodemorph benzoate, dodicin, dodicin-sodium,
dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, etem,
ethaboxam, ethirimol, ethoxyquin, ethylmercury 2,3-dihydroxypropyl
mercaptide, ethylmercury acetate, ethylmercury bromide,
ethylmercury chloride, ethylmercury phosphate, etridiazole,
famoxadone, fenamidone, fenaminosulf, fenapanil, fenarimol,
fenbuconazole, fenfuram, fenhexamid, fenitropan, fenoxanil,
fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin chloride,
fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,
flumetover, flumorph, fluopicolide, fluopyram, fluoroimide,
fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole,
flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad,
folpet, formaldehyde, fosetyl, fosetyl-aluminium, fuberidazole,
furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cis,
furfural, furmecyclox, furophanate, glyodin, griseofulvin,
guazatine, halacrinate, hexachlorobenzene, hexachlorobutadiene,
hexaconazole, hexylthiofos, hydrargaphen, hymexazol, imazalil,
imazalil nitrate, imazalil sulfate, imibenconazole, iminoctadine,
iminoctadine triacetate, iminoctadine trialbesilate, iodomethane,
ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane,
isopyrazam, isotianil, isovaledione, kasugamycin, kresoxim-methyl,
mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid,
mepanipyrim, mepronil, meptyldinocap, mercuric chloride, mercuric
oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,
metam-ammonium, metam-potassium, metam-sodium, metazoxolon,
metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl
isothiocyanate, methylmercury benzoate, methylmercury
dicyandiamide, methylmercury pentachlorophenoxide, metiram,
metominostrobin, metrafenone, metsulfovax, milneb, myclobutanil,
myclozolin, N-(ethylmercury)-p-toluenesulphonanilide, nabam,
natamycin, nitrostyrene, nitrothal-isopropyl, nuarimol, OCH,
octhilinone, ofurace, orysastrobin, oxadixyl, oxine-copper,
oxpoconazole, oxpoconazole fumarate, oxycarboxin, pefurazoate,
penconazole, pencycuron, penflufen, pentachlorophenol,
penthiopyrad, phenylmercuriurea, phenylmercury acetate,
phenylmercury chloride, phenylmercury derivative of pyrocatechol,
phenylmercury nitrate, phenylmercury salicylate, phosdiphen,
phthalide, picoxystrobin, piperalin, polycarbamate, polyoxins,
polyoxorim, polyoxorim-zinc, potassium azide, potassium
polysulfide, potassium thiocyanate, probenazole, prochloraz,
procymidone, propamocarb, propamocarb hydrochloride, propiconazole,
propineb, proquinazid, prothiocarb, prothiocarb hydrochloride,
prothioconazole, pyracarbolid, pyraclostrobin, pyraclostrobin,
pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb,
pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyroquilon,
pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid,
quinconazole, quinoxyfen, quintozene, rabenzazole, salicylanilide,
sedaxane, silthiofam, simeconazole, sodium azide, sodium
orthophenylphenoxide, sodium pentachlorophenoxide, sodium
polysulfide, spiroxamine, streptomycin, sulfur, sultropen, TCMTB,
tebuconazole, tebufloquin, tecloftalam, tecnazene, tecoram,
tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide,
thiochlorfenphim, thiomersal, thiophanate, thiophanate-methyl,
thioquinox, thiram, tiadinil, tioxymid, tolclofos-methyl,
tolylfluanid, tolylmercury acetate, triadimefon, triadimenol,
triamiphos, triarimol, triazbutil, triazoxide, tributyltin oxide,
trichlamide, tricyclazole, tridemorph, trifloxystrobin,
triflumizole, triforine, triticonazole, uniconazole, uniconazole-P,
validamycin, valifenalate, vinclozolin, zarilamid, zinc
naphthenate, zineb, ziram, zoxamide (collectively these commonly
named fungicides are defined as the "Fungicide Group").
Herbicides
[0177] Molecules of Formulas One, Two and Three may also be used in
combination (such as, in a compositional mixture, or a simultaneous
or sequential application) with one or more of the following
herbicides--2,3,6-TBA, 2,3,6-TBA-dimethylammonium,
2,3,6-TBA-sodium, 2,4,5-T, 2,4,5-T-2-butoxypropyl,
2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl, 2,4,5-TB,
2,4,5-T-butomethyl, 2,4,5-T-butotyl, 2,4,5-T-butyl,
2,4,5-T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl,
2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium,
2,4,5-T-triethylammonium, 2,4,5-T-trolamine, 2,4-D,
2,4-D-2-butoxypropyl, 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl,
2,4-D-ammonium, 2,4-DB, 2,4-DB-butyl, 2,4-DB-dimethylammonium,
2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4-D-butotyl,
2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium,
2,4-D-diolamine, 2,4-D-dodecylammonium, 2,4-DEB, 2,4-DEP,
2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D-isobutyl, 2,4-D-isoctyl,
2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium,
2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl,
2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium, 2,4-D-tefuryl,
2,4-D-tetradecylammonium, 2,4-D-triethylammonium,
2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-trolamine, 3,4-DA,
3,4-DB, 3,4-DP, 4-CPA, 4-CPB, 4-CPP, acetochlor, acifluorfen,
acifluorfen-methyl, acifluorfen-sodium, aclonifen, acrolein,
alachlor, allidochlor, alloxydim, alloxydim-sodium, allyl alcohol,
alorac, ametridione, ametryn, amibuzin, amicarbazone,
amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor-methyl,
aminocyclopyrachlor-potassium, aminopyralid,
aminopyralid-potassium, aminopyralid-tris(2-hydroxypropyl)ammonium,
amiprofos-methyl, amitrole, ammonium sulfamate, anilofos, anisuron,
asulam, asulam-potassium, asulam-sodium, atraton, atrazine,
azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid,
benazolin, benazolin-dimethylammonium, benazolin-ethyl,
benazolin-potassium, bencarbazone, benfluralin, benfuresate,
bensulfuron, bensulfuron-methyl, bensulide, bentazone,
bentazone-sodium, benzadox, benzadox-ammonium, benzfendizone,
benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop,
benzoylprop-ethyl, benzthiazuron, bicyclopyrone, bifenox,
bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, borax,
bromacil, bromacil-lithium, bromacil-sodium, bromobonil,
bromobutide, bromofenoxim, bromoxynil, bromoxynil butyrate,
bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium,
brompyrazon, butachlor, butafenacil, butamifos, butenachlor,
buthidazole, buthiuron, butralin, butroxydim, buturon, butylate,
cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide,
cambendichlor, carbasulam, carbetamide, carboxazole, carfentrazone,
carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, chloramben,
chloramben-ammonium, chloramben-diolamine, chloramben-methyl,
chloramben-methylammonium, chloramben-sodium, chloranocryl,
chlorazifop, chlorazifop-propargyl, chlorazine, chlorbromuron,
chlorbufam, chloreturon, chlorfenac, chlorfenac-sodium,
chlorfenprop, chlorfenprop-methyl, chlorflurazole, chlorflurenol,
chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl,
chlomitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil,
chlorprocarb, chlorpropham, chlorsulfuron, chlorthal,
chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid,
cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clethodim,
cliodinate, clodinafop, clodinafop-propargyl, clofop,
clofop-isobutyl, clomazone, clomeprop, cloprop, cloproxydim,
clopyralid, clopyralid-methyl, clopyralid-olamine,
clopyralid-potassium, clopyralid-tris(2-hydroxypropyl)ammonium,
cloransulam, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC,
credazine, cresol, cumyluron, cyanamide, cyanatryn, cyanazine,
cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop,
cyhalofop-butyl, cyperquat, cyperquat chloride, cyprazine,
cyprazole, cypromid, daimuron, dalapon, dalapon-calcium,
dalapon-magnesium, dalapon-sodium, dazomet, dazomet-sodium,
delachlor, desmedipham, desmetryn, di-allate, dicamba,
dicamba-dimethylammonium, dicamba-diolamine,
dicamba-isopropylammonium, dicamba-methyl, dicamba-olamine,
dicamba-potassium, dicamba-sodium, dicamba-trolamine, dichlobenil,
dichloralurea, dichlormate, dichlorprop, dichlorprop-2-ethylhexyl,
dichlorprop-butotyl, dichlorprop-dimethylammonium,
dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl,
dichlorprop-P, dichlorprop-P-dimethylammonium,
dichlorprop-potassium, dichlorprop-sodium, diclofop,
diclofop-methyl, diclosulam, diethamquat, diethamquat dichloride,
diethatyl, diethatyl-ethyl, difenopenten, difenopenten-ethyl,
difenoxuron, difenzoquat, difenzoquat metilsulfate, diflufenican,
diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate,
dimethachlor, dimethametryn, dimethenamid, dimethenamid-P,
dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam,
dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine,
dinoseb-sodium, dinoseb-trolamine, dinoterb, dinoterb acetate,
diphacinone-sodium, diphenamid, dipropetryn, diquat, diquat
dibromide, disul, disul-sodium, dithiopyr, diuron, DMPA, DNOC,
DNOC-ammonium, DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine,
eglinazine-ethyl, endothal, endothal-diammonium,
endothal-dipotassium, endothal-disodium, epronaz, EPTC, erbon,
esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl,
ethidimuron, ethiolate, ethofumesate, ethoxyfen, ethoxyfen-ethyl,
ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam,
fenoprop, fenoprop-3-butoxypropyl, fenoprop-butomethyl,
fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl,
fenoprop-methyl, fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl,
fenoxaprop-P, fenoxaprop-P-ethyl, fenoxasulfone, fenteracol,
fenthiaprop, fenthiaprop-ethyl, fentrazamide, fenuron, fenuron TCA,
ferrous sulfate, flamprop, flamprop-isopropyl, flamprop-M,
flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl,
flazasulfuron, florasulam, fluazifop, fluazifop-butyl,
fluazifop-methyl, fluazifop-P, fluazifop-P-butyl, fluazolate,
flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin,
flufenacet, flufenican, flufenpyr, flufenpyr-ethyl, flumetsulam,
flumezin, flumiclorac, flumiclorac-pentyl, flumioxazin,
flumipropyn, fluometuron, fluorodifen, fluoroglycofen,
fluoroglycofen-ethyl, fluoromidine, fluoronitrofen, fluothiuron,
flupoxam, flupropacil, flupropanate, flupropanate-sodium,
flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone,
fluorochloridone, fluoroxypyr, fluoroxypyr-butomethyl,
fluoroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl,
fomesafen, fomesafen-sodium, foramsulfuron, fosamine,
fosamine-ammonium, furyloxyfen, glufosinate, glufosinate-ammonium,
glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium,
glyphosate, glyphosate-diammonium, glyphosate-dimethylammonium,
glyphosate-isopropylammonium, glyphosate-monoammonium,
glyphosate-potassium, glyphosate-sesquisodium,
glyphosate-trimesium, halosafen, halosulfuron, halosulfuron-methyl,
haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl,
haloxyfop-P, haloxyfop-P-etotyl, haloxyfop-P-methyl,
haloxyfop-sodium, hexachloroacetone, hexaflurate, hexazinone,
imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium,
imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium,
imazaquin, imazaquin-ammonium, imazaquin-methyl, imazaquin-sodium,
imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan,
indaziflam, iodobonil, iodomethane, iodosulfuron,
iodosulfuron-methyl-sodium, ioxynil, ioxynil octanoate,
ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone,
iprymidam, isocarbamid, isocil, isomethiozin, isonoruron,
isopolinate, isopropalin, isoproturon, isouron, isoxaben,
isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate,
ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA,
MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium,
MCPA-diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl,
MCPA-isopropyl, MCPA-methyl, MCPA-olamine, MCPA-potassium,
MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl,
MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl,
mecoprop-dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl,
mecoprop-isoctyl, mecoprop-methyl, mecoprop-P,
mecoprop-P-dimethylammonium, mecoprop-P-isobutyl,
mecoprop-potassium, mecoprop-P-potassium, mecoprop-sodium,
mecoprop-trolamine, medinoterb, medinoterb acetate, mefenacet,
mefluidide, mefluidide-diolamine, mefluidide-potassium,
mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotrione, metam,
metam-ammonium, metamifop, metamitron, metam-potassium,
metam-sodium, metazachlor, metazosulfuron, metflurazon,
methabenzthiazuron, methalpropalin, methazole, methiobencarb,
methiozolin, methiuron, methometon, methoprotryne, methyl bromide,
methyl isothiocyanate, methyldymron, metobenzuron, metolachlor,
metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl,
molinate, monalide, monisouron, monochloroacetic acid, monolinuron,
monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA,
naproanilide, napropamide, naptalam, naptalam-sodium, neburon,
nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,
norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,
orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,
oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron,
oxaziclomefone, oxyfluorfen, parafluoron, paraquat, paraquat
dichloride, paraquat dimetilsulfate, pebulate, pelargonic acid,
pendimethalin, penoxsulam, pentachlorophenol, pentanochlor,
pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham,
phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram,
picloram-2-ethylhexyl, picloram-isoctyl, picloram-methyl,
picloram-olamine, picloram-potassium, picloram-triethylammonium,
picloram-tris(2-hydroxypropyl)ammonium, picolinafen, pinoxaden,
piperophos, potassium arsenite, potassium azide, potassium cyanate,
pretilachlor, primisulfuron, primisulfuron-methyl, procyazine,
prodiamine, profluazol, profluralin, profoxydim, proglinazine,
proglinazine-ethyl, prometon, prometryn, propachlor, propanil,
propaquizafop, propazine, propham, propisochlor, propoxycarbazone,
propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfalin,
prosulfocarb, prosulfuron, proxan, proxan-sodium, prynachlor,
pydanon, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole,
pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen,
pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate,
pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan,
pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam,
quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop,
quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl,
quizalofop-P-tefuryl, rhodethanil, rimsulfuron, saflufenacil,
sebuthylazine, secbumeton, sethoxydim, siduron, simazine, simeton,
simetryn, SMA, S-metolachlor, sodium arsenite, sodium azide, sodium
chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron,
sulfometuron-methyl, sulfosulfuron, sulfuric acid, sulglycapin,
swep, TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA-magnesium,
TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione,
tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton,
terbuthylazine, terbutryn, tetrafluoron, thenylchlor,
thiazafluoron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone,
thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl,
thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim,
tri-allate, triasulfuron, triaziflam, tribenuron,
tribenuron-methyl, tricamba, triclopyr, triclopyr-butotyl,
triclopyr-ethyl, triclopyr-triethylammonium, tridiphane,
trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin,
triflusulfuron, triflusulfuron-methyl, trifop, trifop-methyl,
trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac,
tritosulfuron, vernolate, xylachlor, (collectively these commonly
named herbicides are defined as the "Herbicide Group").
Biopesticides
[0178] Molecules of Formulas One, Two and Three may also be used in
combination (such as in a compositional mixture, or a simultaneous
or sequential application) with one or more biopesticides. The term
"biopesticide" is used for microbial biological pest control agents
that are applied in a similar manner to chemical pesticides.
Commonly these are bacterial, but there are also examples of fungal
control agents, including Trichoderma spp. and Ampelomyces
quisqualis (a control agent for grape powdery mildew). Bacillus
subtilis are used to control plant pathogens. Weeds and rodents
have also been controlled with microbial agents. One well-known
insecticide example is Bacillus thuringiensis, a bacterial disease
of Lepidoptera, Coleoptera, and Diptera. Because it has little
effect on other organisms, it is considered more environmentally
friendly than synthetic pesticides. Biological insecticides include
products based on:
[0179] 1. entomopathogenic fungi (e.g. Metarhizium anisopliae);
[0180] 2. entomopathogenic nematodes (e.g. Steinemema feltiae);
and
[0181] 3. entomopathogenic viruses (e.g. Cydia pomonella
granulovirus).
[0182] Other examples of entomopathogenic organisms include, but
are not limited to, baculoviruses, bacteria and other prokaryotic
organisms, fungi, protozoa and Microsproridia. Biologically derived
insecticides include, but not limited to, rotenone, veratridine, as
well as microbial toxins; insect tolerant or resistant plant
varieties; and organisms modified by recombinant DNA technology to
either produce insecticides or to convey an insect resistant
property to the genetically modified organism. In one embodiment,
the Molecules of Formula One, Two or Three may be used with one or
more biopesticides in the area of seed treatments and soil
amendments. The Manual of Biocontrol Agents gives a review of the
available biological insecticide (and other biology-based control)
products. Copping L. G. (ed.) (2004). The Manual of Biocontrol
Agents (formerly the Biopesticide Manual) 3rd Edition. British Crop
Production Council (BCPC), Farnham, Surrey UK.
Other Active Compounds
[0183] Molecules of Formulas One, Two and Three may also be used in
combination (such as in a compositional mixture, or a simultaneous
or sequential application) with one or more of the following:
[0184] 1.
3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-oxa-1-azaspiro[4,5]dec-3-en-2-
-one; [0185] 2.
3-(4'-chloro-2,4-dimethyl[1,1'-biphenyl]-3-yl)-4-hydroxy-8-oxa-1-azaspiro-
[4,5]dec-3-en-2-one; [0186] 3.
4-[[(6-chloro-3-pyridinyl)methyl]methylamino]-2(5H)-furanone;
[0187] 4.
4-[[(6-chloro-3-pyridinyl)methyl]cyclopropylamino]-2(5H)-furanone;
[0188] 5.
3-chloro-N2-[(1S)-1-methyl-2-(methylsulfonyl)ethyl]-N1-[2-methyl-4-[1,-
2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]-1,2-benzenedicarboxamid-
e; [0189] 6. 2-cyano-N-ethyl-4-fluoro-3-methoxy-benenesulfonamide;
[0190] 7. 2-cyano-N-ethyl-3-methoxy-benzenesulfonamide; [0191] 8.
2-cyano-3-difluoromethoxy-N-ethyl-4-fluoro-benzenesulfonamide;
[0192] 9. 2-cyano-3-fluoromethoxy-N-ethyl-benzenesulfonamide;
[0193] 10.
2-cyano-6-fluoro-3-methoxy-N,N-dimethyl-benzenesulfonamide; [0194]
11. 2-cyano-N-ethyl-6-fluoro-3-methoxy-N-methyl-benzenesulfonamide;
[0195] 12.
2-cyano-3-difluoromethoxy-N,N-dimethylbenzenesulfon-amide; [0196]
13.
3-(difluoromethyl)-N-[2-(3,3-dimethylbutyl)phenyl]-1-methyl-1H-pyrazole-4-
-carboxamide; [0197] 14.
N-ethyl-2,2-dimethylpropionamide-2-(2,6-dichloro-.alpha.,.alpha.,.alpha.--
trifluoro-p-tolyl) hydrazone; [0198] 15.
N-ethyl-2,2-dichloro-1-methylcyclopropane-carboxamide-2-(2,6-dichloro-.al-
pha.,.alpha.,.alpha.-trifluoro-p-tolyl) hydrazone nicotine; [0199]
16.
O-{(E-)-[2-(4-chloro-phenyl)-2-cyano-1-(2-trifluoromethylphenyl)-vinyl]}
S-methyl thiocarbonate; [0200] 17.
(E)-N1-[(2-chloro-1,3-thiazol-5-ylmethyl)]-N2-cyano-N1-methylacetamidine;
[0201] 18.
1-(6-chloropyridin-3-ylmethyl)-7-methyl-8-nitro-1,2,3,5,6,7-hexahydro-imi-
dazo[1,2-a]pyridin-5-ol; [0202] 19.
4-[4-chlorophenyl-(2-butylidine-hydrazono)methyl)]phenyl mesylate;
and [0203] 20.
N-Ethyl-2,2-dichloro-1-methylcyclopropanecarboxamide-2-(2,6-dichloro-alph-
a,alpha,alpha-trifluoro-p-tolyl)hydrazone.
[0204] Molecules of Formulas One, Two and Three may also be used in
combination (such as in a compositional mixture, or a simultaneous
or sequential application) with one or more compounds in the
following groups: algicides, antifeedants, avicides, bactericides,
bird repellents, chemosterilants, herbicide safeners, insect
attractants, insect repellents, mammal repellents, mating
disrupters, molluscicides, plant activators, plant growth
regulators, rodenticides, and/or virucides (collectively these
commonly named groups are defined as the "AI Group"). It should be
noted that compounds falling within the AI Group, Insecticide
Group, Fungicide Group, Herbicide Group, Acaricide Group, or
Nematicide Group might be in more than one group, because of
multiple activities the compound has. For more information consult
the "COMPENDIUM OF PESTICIDE COMMON NAMES" located at
http://www.alanwood.net/pesticides/index.html. Also consult "THE
PESTICIDE MANUAL" 14th Edition, edited by C D S Tomlin, copyright
2006 by British Crop Production Council, or its prior or more
recent editions.
Synergistic Mixtures and Synergists
[0205] Molecules of Formulas One, Two and Three may be used with
the compounds in the Insecticide Group to form synergistic mixtures
where the mode of action of such compounds compared to the mode of
action of the Molecules of Formula One and Two are the same,
similar, or different. Examples of modes of action include, but are
not limited to: acetylcholinesterase inhibitor; sodium channel
modulator; chitin biosynthesis inhibitor; GABA-gated chloride
channel antagonist; GABA and glutamate-gated chloride channel
agonist; acetylcholine receptor agonist; MET I inhibitor;
Mg-stimulated ATPase inhibitor; nicotinic acetylcholine receptor;
Midgut membrane disrupter; oxidative phosphorylation disrupter, and
ryanodine receptor (RyRs). Additionally, Molecules of Formula One
and Two may be used with compounds in the Fungicide Group,
Acaricide Group, Herbicide Group, or Nematicide Group to form
synergistic mixtures. Furthermore, Molecules of Formulas One, Two
and Three may be used with other active compounds, such as the
compounds under the heading "OTHER ACTIVE COMPOUNDS", algicides,
avicides, bactericides, molluscicides, rodenticides, virucides,
herbicide safeners, adjuvants, and/or surfactants to form
synergistic mixtures. Generally, weight ratios of the Molecules of
Formulas One, Two and Three in a synergistic mixture with another
compound are from about 10:1 to about 1:10, preferably from about
5:1 to about 1:5, and more preferably from about 3:1, and even more
preferably about 1:1. Additionally, the following compounds are
known as synergists and may be used with the molecules disclosed in
Formula One: piperonyl butoxide, piprotal, propyl isome, sesamex,
sesamolin, sulfoxide, and tribufos (collectively these synergists
are defined as the "Synergists Group").
Formulations
[0206] A pesticide is rarely suitable for application in its pure
form. It is usually necessary to add other substances so that the
pesticide can be used at the required concentration and in an
appropriate form, permitting ease of application, handling,
transportation, storage, and maximum pesticide activity. Thus,
pesticides are formulated into, for example, baits, concentrated
emulsions, dusts, emulsifiable concentrates, fumigants, gels,
granules, microencapsulations, seed treatments, suspension
concentrates, suspoemulsions, tablets, water soluble liquids, water
dispersible granules or dry flowables, wettable powders, and ultra
low volume solutions. For further information on formulation types
see "Catalogue of Pesticide Formulation Types and International
Coding System" Technical Monograph n.degree. 2, 5th Edition by
CropLife International (2002).
[0207] Pesticides are applied most often as aqueous suspensions or
emulsions prepared from concentrated formulations of such
pesticides. Such water-soluble, water-suspendable, or emulsifiable
formulations are either solids, usually known as wettable powders,
or water dispersible granules, or liquids usually known as
emulsifiable concentrates, or aqueous suspensions. Wettable
powders, which may be compacted to form water dispersible granules,
comprise an intimate mixture of the pesticide, a carrier, and
surfactants. The concentration of the pesticide is usually from
about 10% to about 90% by weight. The carrier is usually chosen
from among the attapulgite clays, the montmorillonite clays, the
diatomaceous earths, or the purified silicates. Effective
surfactants, comprising from about 0.5% to about 10% of the
wettable powder, are found among sulfonated lignins, condensed
naphthalenesulfonates, naphthalenesulfonates,
alkylbenzenesulfonates, alkyl sulfates, and non-ionic surfactants
such as ethylene oxide adducts of alkyl phenols.
[0208] Emulsifiable concentrates of pesticides comprise a
convenient concentration of a pesticide, such as from about 50 to
about 500 grams per liter of liquid dissolved in a carrier that is
either a water miscible solvent or a mixture of water-immiscible
organic solvent and emulsifiers. Useful organic solvents include
aromatics, especially xylenes and petroleum fractions, especially
the high-boiling naphthalenic and olefinic portions of petroleum
such as heavy aromatic naphtha. Other organic solvents may also be
used, such as the terpenic solvents including rosin derivatives,
aliphatic ketones such as cyclohexanone, and complex alcohols such
as 2-ethoxyethanol. Suitable emulsifiers for emulsifiable
concentrates are chosen from conventional anionic and non-ionic
surfactants.
[0209] Aqueous suspensions comprise suspensions of water-insoluble
pesticides dispersed in an aqueous carrier at a concentration in
the range from about 5% to about 50% by weight. Suspensions are
prepared by finely grinding the pesticide and vigorously mixing it
into a carrier comprised of water and surfactants. Ingredients,
such as inorganic salts and synthetic or natural gums may also be
added, to increase the density and viscosity of the aqueous
carrier. It is often most effective to grind and mix the pesticide
at the same time by preparing the aqueous mixture and homogenizing
it in an implement such as a sand mill, ball mill, or piston-type
homogenizer.
[0210] Pesticides may also be applied as granular compositions that
are particularly useful for applications to the soil. Granular
compositions usually contain from about 0.5% to about 10% by weight
of the pesticide, dispersed in a carrier that comprises clay or a
similar substance. Such compositions are usually prepared by
dissolving the pesticide in a suitable solvent and applying it to a
granular carrier which has been pre-formed to the appropriate
particle size, in the range of from about 0.5 to about 3 mm. Such
compositions may also be formulated by making a dough or paste of
the carrier and compound and crushing and drying to obtain the
desired granular particle size.
[0211] Dusts containing a pesticide are prepared by intimately
mixing the pesticide in powdered form with a suitable dusty
agricultural carrier, such as kaolin clay, ground volcanic rock,
and the like. Dusts can suitably contain from about 1% to about 10%
of the pesticide. They can be applied as a seed dressing or as a
foliage application with a dust blower machine.
[0212] It is equally practical to apply a pesticide in the form of
a solution in an appropriate organic solvent, usually petroleum
oil, such as the spray oils, which are widely used in agricultural
chemistry.
[0213] Pesticides can also be applied in the form of an aerosol
composition. In such compositions the pesticide is dissolved or
dispersed in a carrier, which is a pressure-generating propellant
mixture. The aerosol composition is packaged in a container from
which the mixture is dispensed through an atomizing valve.
[0214] Pesticide baits are formed when the pesticide is mixed with
food or an attractant or both. When the pests eat the bait they
also consume the pesticide. Baits may take the form of granules,
gels, flowable powders, liquids, or solids. They can be used in
pest harborages.
[0215] Fumigants are pesticides that have a relatively high vapor
pressure and hence can exist as a gas in sufficient concentrations
to kill pests in soil or enclosed spaces. The toxicity of the
fumigant is proportional to its concentration and the exposure
time. They are characterized by a good capacity for diffusion and
act by penetrating the pest's respiratory system or being absorbed
through the pest's cuticle. Fumigants are applied to control stored
product pests under gas proof sheets, in gas sealed rooms or
buildings or in special chambers.
[0216] Pesticides can be microencapsulated by suspending the
pesticide particles or droplets in plastic polymers of various
types. By altering the chemistry of the polymer or by changing
factors in the processing, microcapsules can be formed of various
sizes, solubility, wall thicknesses, and degrees of penetrability.
These factors govern the speed with which the active ingredient
within is released, which in turn, affects the residual
performance, speed of action, and odor of the product.
[0217] Oil solution concentrates are made by dissolving pesticide
in a solvent that will hold the pesticide in solution. Oil
solutions of a pesticide usually provide faster knockdown and kill
of pests than other formulations due to the solvents themselves
having pesticidal action and the dissolution of the waxy covering
of the integument increasing the speed of uptake of the pesticide.
Other advantages of oil solutions include better storage stability,
better penetration of crevices, and better adhesion to greasy
surfaces.
[0218] Another embodiment is an oil-in-water emulsion, wherein the
emulsion comprises oily globules which are each provided with a
lamellar liquid crystal coating and are dispersed in an aqueous
phase, wherein each oily globule comprises at least one compound
which is agriculturally active, and is individually coated with a
monolamellar or oligolamellar layer comprising: (1) at least one
non-ionic lipophilic surface-active agent, (2) at least one
non-ionic hydrophilic surface-active agent and (3) at least one
ionic surface-active agent, wherein the globules having a mean
particle diameter of less than 800 nanometers. Further information
on the embodiment is disclosed in U.S. patent publication
20070027034 published Feb. 1, 2007, having patent application Ser.
No. 11/495,228. For ease of use, this embodiment will be referred
to as "OIWE".
[0219] For further information consult "Insect Pest Management" 2nd
Edition by D. Dent, copyright CAB International (2000).
Additionally, for more detailed information consult "Handbook of
Pest Control--The Behavior, Life History, and Control of Household
Pests" by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media
Inc.
Other Formulation Components
[0220] Generally, when the molecules disclosed in Formulas One, Two
and Three are used in a formulation, such formulation can also
contain other components. These components include, but are not
limited to, (this is a non-exhaustive and non-mutually exclusive
list) wetters, spreaders, stickers, penetrants, buffers,
sequestering agents, drift reduction agents, compatibility agents,
anti-foam agents, cleaning agents, and emulsifiers. A few
components are described forthwith.
[0221] A wetting agent is a substance that when added to a liquid
increases the spreading or penetration power of the liquid by
reducing the interfacial tension between the liquid and the surface
on which it is spreading. Wetting agents are used for two main
functions in agrochemical formulations: during processing and
manufacture to increase the rate of wetting of powders in water to
make concentrates for soluble liquids or suspension concentrates;
and during mixing of a product with water in a spray tank to reduce
the wetting time of wettable powders and to improve the penetration
of water into water-dispersible granules. Examples of wetting
agents used in wettable powder, suspension concentrate, and
water-dispersible granule formulations are: sodium lauryl sulfate;
sodium dioctyl sulfosuccinate; alkyl phenol ethoxylates; and
aliphatic alcohol ethoxylates.
[0222] A dispersing agent is a substance which adsorbs onto the
surface of particles and helps to preserve the state of dispersion
of the particles and prevents them from reaggregating. Dispersing
agents are added to agrochemical formulations to facilitate
dispersion and suspension during manufacture, and to ensure the
particles redisperse into water in a spray tank. They are widely
used in wettable powders, suspension concentrates and
water-dispersible granules. Surfactants that are used as dispersing
agents have the ability to adsorb strongly onto a particle surface
and provide a charged or steric barrier to reaggregation of
particles. The most commonly used surfactants are anionic,
non-ionic, or mixtures of the two types. For wettable powder
formulations, the most common dispersing agents are sodium
lignosulfonates. For suspension concentrates, very good adsorption
and stabilization are obtained using polyelectrolytes, such as
sodium naphthalene sulfonate formaldehyde condensates.
Tristyrylphenol ethoxylate phosphate esters are also used.
Non-ionics such as alkylarylethylene oxide condensates and EO-PO
block copolymers are sometimes combined with anionics as dispersing
agents for suspension concentrates. In recent years, new types of
very high molecular weight polymeric surfactants have been
developed as dispersing agents. These have very long hydrophobic
`backbones` and a large number of ethylene oxide chains forming the
`teeth` of a `comb` surfactant. These high molecular weight
polymers can give very good long-term stability to suspension
concentrates because the hydrophobic backbones have many anchoring
points onto the particle surfaces. Examples of dispersing agents
used in agrochemical formulations are: sodium lignosulfonates;
sodium naphthalene sulfonate formaldehyde condensates;
tristyrylphenol ethoxylate phosphate esters; aliphatic alcohol
ethoxylates; alkyl ethoxylates; EO-PO block copolymers; and graft
copolymers.
[0223] An emulsifying agent is a substance which stabilizes a
suspension of droplets of one liquid phase in another liquid phase.
Without the emulsifying agent the two liquids would separate into
two immiscible liquid phases. The most commonly used emulsifier
blends contain alkylphenol or aliphatic alcohol with twelve or more
ethylene oxide units and the oil-soluble calcium salt of
dodecylbenzenesulfonic acid. A range of hydrophile-lipophile
balance ("HLB") values from 8 to 18 will normally provide good
stable emulsions. Emulsion stability can sometimes be improved by
the addition of a small amount of an EO-PO block copolymer
surfactant.
[0224] A solubilizing agent is a surfactant which will form
micelles in water at concentrations above the critical micelle
concentration. The micelles are then able to dissolve or solubilize
water-insoluble materials inside the hydrophobic part of the
micelle. The types of surfactants usually used for solubilization
are non-ionics, sorbitan monooleates, sorbitan monooleate
ethoxylates, and methyl oleate esters.
[0225] Surfactants are sometimes used, either alone or with other
additives such as mineral or vegetable oils as adjuvants to
spray-tank mixes to improve the biological performance of the
pesticide on the target. The types of surfactants used for
bioenhancement depend generally on the nature and mode of action of
the pesticide. However, they are often non-ionics such as: alkyl
ethoxylates; linear aliphatic alcohol ethoxylates; aliphatic amine
ethoxylates.
[0226] A carrier or diluent in an agricultural formulation is a
material added to the pesticide to give a product of the required
strength. Carriers are usually materials with high absorptive
capacities, while diluents are usually materials with low
absorptive capacities. Carriers and diluents are used in the
formulation of dusts, wettable powders, granules and
water-dispersible granules.
[0227] Organic solvents are used mainly in the formulation of
emulsifiable concentrates, oil-in-water emulsions, suspoemulsions,
and ultra low volume formulations, and to a lesser extent, granular
formulations. Sometimes mixtures of solvents are used. The first
main groups of solvents are aliphatic paraffinic oils such as
kerosene or refined paraffins. The second main group (and the most
common) comprises the aromatic solvents such as xylene and higher
molecular weight fractions of C9 and C10 aromatic solvents.
Chlorinated hydrocarbons are useful as cosolvents to prevent
crystallization of pesticides when the formulation is emulsified
into water. Alcohols are sometimes used as cosolvents to increase
solvent power. Other solvents may include vegetable oils, seed
oils, and esters of vegetable and seed oils.
[0228] Thickeners or gelling agents are used mainly in the
formulation of suspension concentrates, emulsions and
suspoemulsions to modify the rheology or flow properties of the
liquid and to prevent separation and settling of the dispersed
particles or droplets. Thickening, gelling, and anti-settling
agents generally fall into two categories, namely water-insoluble
particulates and water-soluble polymers. It is possible to produce
suspension concentrate formulations using clays and silicas.
Examples of these types of materials, include, but are not limited
to, montmorillonite, bentonite, magnesium aluminum silicate, and
attapulgite. Water-soluble polysaccharides have been used as
thickening-gelling agents for many years. The types of
polysaccharides most commonly used are natural extracts of seeds
and seaweeds or are synthetic derivatives of cellulose. Examples of
these types of materials include, but are not limited to, guar gum;
locust bean gum; carrageenam; alginates; methyl cellulose; sodium
carboxymethyl cellulose (SCMC); hydroxyethyl cellulose (HEC). Other
types of anti-settling agents are based on modified starches,
polyacrylates, polyvinyl alcohol and polyethylene oxide. Another
good anti-settling agent is xanthan gum.
[0229] Microorganisms can cause spoilage of formulated products.
Therefore preservation agents are used to eliminate or reduce their
effect. Examples of such agents include, but are not limited to:
propionic acid and its sodium salt; sorbic acid and its sodium or
potassium salts; benzoic acid and its sodium salt; p-hydroxybenzoic
acid sodium salt; methyl p-hydroxybenzoate; and
1,2-benzisothiazolin-3-one (BIT).
[0230] The presence of surfactants often causes water-based
formulations to foam during mixing operations in production and in
application through a spray tank. In order to reduce the tendency
to foam, anti-foam agents are often added either during the
production stage or before filling into bottles. Generally, there
are two types of anti-foam agents, namely silicones and
non-silicones. Silicones are usually aqueous emulsions of dimethyl
polysiloxane, while the non-silicone anti-foam agents are
water-insoluble oils, such as octanol and nonanol, or silica. In
both cases, the function of the anti-foam agent is to displace the
surfactant from the air-water interface.
[0231] "Green" agents (e.g., adjuvants, surfactants, solvents) can
reduce the overall environmental footprint of crop protection
formulations. Green agents are biodegradable and generally derived
from natural and/or sustainable sources, e.g. plant and animal
sources. Specific examples are: vegetable oils, seed oils, and
esters thereof, also alkoxylated alkyl polyglucosides.
[0232] For further information, see "Chemistry and Technology of
Agrochemical Formulations" edited by D. A. Knowles, copyright 1998
by Kluwer Academic Publishers. Also see "Insecticides in
Agriculture and Environment--Retrospects and Prospects" by A. S.
Perry, I. Yamamoto, I. Ishaaya, and R. Perry, copyright 1998 by
Springer-Verlag.
Pests
[0233] In general, the Molecules of Formula Formulas One, Two and
Three may be used to control pests e.g. beetles, earwigs,
cockroaches, flies. aphids, scales, whiteflies, leafhoppers, ants,
wasps, termites, moths, butterflies, lice, grasshoppers, locusts,
crickets, fleas, thrips, bristletails, mites, ticks, nematodes, and
symphylans.
[0234] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests in the Phyla Nematoda and/or
Arthropoda.
[0235] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests in the Subphyla Chelicerata,
Myriapoda, and/or Hexapoda.
[0236] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests in the Classes of Arachnida,
Symphyla, and/or Insecta.
[0237] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Anoplura. A
non-exhaustive list of particular genera includes, but is not
limited to, Haematopinus spp., Hoplopleura spp., Linognathus spp.,
Pediculus spp., and Polyplax spp. A non-exhaustive list of
particular species includes, but is not limited to, Haematopinus
asini, Haematopinus suis, Linognathus setosus, Linognathus ovillus,
Pediculus humanus capitis, Pediculus humanus humanus, and Pthirus
pubis.
[0238] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests in the Order Coleoptera. A
non-exhaustive list of particular genera includes, but is not
limited to, Acanthoscelides spp., Agriotes spp., Anthonomus spp.,
Apion spp., Apogonia spp., Aulacophora spp., Bruchus spp.,
Cerosterna spp., Cerotoma spp., Ceutorhynchus spp., Chaetocnema
spp., Colaspis spp., Ctenicera spp., Curculio spp., Cyclocephala
spp., Diabrotica spp., Hypera spp., Ips spp., Lyctus spp.,
Megascelis spp., Meligethes spp., Otiorhynchus spp., Pantomorus
spp., Phyllophaga spp., Phyllotreta spp., Rhizotrogus spp.,
Rhynchites spp., Rhynchophorus spp., Scolytus spp., Sphenophorus
spp., Sitophilus spp., and Tribolium spp. A non-exhaustive list of
particular species includes, but is not limited to, Acanthoscelides
obtectus, Agrilus planipennis, Anoplophora glabripennis, Anthonomus
grandis, Ataenius spretulus, Atomaria linearis, Bothynoderes
punctiventris, Bruchus pisorum, Callosobruchus maculatus,
Carpophilus hemipterus, Cassida vittata, Cerotoma trifurcata,
Ceutorhynchus assimilis, Ceutorhynchus napi, Conoderus scalaris,
Conoderus stigmosus, Conotrachelus nenuphar, Cotinis nitida,
Crioceris asparagi, Cryptolestes ferrugineus, Cryptolestes
pusillus, Cryptolestes turcicus, Cylindrocopturus adspersus,
Deporaus marginatus, Dermestes lardarius, Dermestes maculatus,
Epilachna varivestis, Faustinus cubae, Hylobius pales, Hypera
postica, Hypothenemus hampei, Lasioderma serricorne, Leptinotarsa
decemlineata, Liogenys fuscus, Liogenys suturalis, Lissorhoptrus
oryzophilus, Maecolaspis joliveti, Melanotus communis, Meligethes
aeneus, Melolontha melolontha, Oberea brevis, Oberea linearis,
Oryctes rhinoceros, Oryzaephilus mercator, Oryzaephilus
surinamensis, Oulema melanopus, Oulema oryzae, Phyllophaga
cuyabana, Popillia japonica, Prostephanus truncatus, Rhyzopertha
dominica, Sitona lineatus, Sitophilus granarius, Sitophilus oryzae,
Sitophilus zeamais, Stegobium paniceum, Tribolium castaneum,
Tribolium confusum, Trogoderma variabile, and Zabrus
tenebrioides.
[0239] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Dermaptera.
[0240] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Blattaria. A
non-exhaustive list of particular species includes, but is not
limited to, Blattella germanica, Blatta orientalis, Parcoblatta
pennsylvanica, Periplaneta americana, Periplaneta australasiae,
Periplaneta brunnea, Periplaneta fuliginosa, Pycnoscelus
surinamensis, and Supella longipalpa.
[0241] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Diptera. A
non-exhaustive list of particular genera includes, but is not
limited to, Aedes spp., Agromyza spp., Anastrepha spp., Anopheles
spp., Bactrocera spp., Ceratitis spp., Chrysops spp., Cochliomyia
spp., Contarinia spp., Culex spp., Dasineura spp., Delia spp.,
Drosophila spp., Fannia spp., Hylemyia spp., Liriomyza spp., Musca
spp., Phorbia spp., Tabanus spp., and Tipula spp. A non-exhaustive
list of particular species includes, but is not limited to,
Agromyza frontella, Anastrepha suspensa, Anastrepha ludens,
Anastrepha obliqa, Bactrocera cucurbitae, Bactrocera dorsalis,
Bactrocera invadens, Bactrocera zonata, Ceratitis capitata,
Dasineura brassicae, Delia platura, Fannia canicularis, Fannia
scalaris, Gasterophilus intestinalis, Gracillia perseae, Haematobia
irritans, Hypoderma lineatum, Liriomyza brassicae, Melophagus
ovinus, Musca autumnalis, Musca domestica, Oestrus ovis, Oscinella
frit, Pegomya betae, Psila rosae, Rhagoletis cerasi, Rhagoletis
pomonella, Rhagoletis mendax, Sitodiplosis mosellana, and Stomoxys
calcitrans.
[0242] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Hemiptera. A
non-exhaustive list of particular genera includes, but is not
limited to, Adelges spp., Aulacaspis spp., Aphrophora spp., Aphis
spp., Bemisia spp., Ceroplastes spp., Chionaspis spp.,
Chrysomphalus spp., Coccus spp., Empoasca spp., Lepidosaphes spp.,
Lagynotomus spp., Lygus spp., Macrosiphum spp., Nephotettix spp.,
Nezara spp., Philaenus spp., Phytocoris spp., Piezodorus spp.,
Planococcus spp., Pseudococcus spp., Rhopalosiphum spp., Saissetia
spp., Therioaphis spp., Toumeyella spp., Toxoptera spp.,
Trialeurodes spp., Triatoma spp. and Unaspis spp. A non-exhaustive
list of particular species includes, but is not limited to,
Acrosternum hilare, Acyrthosiphon pisum, Aleyrodes proletella,
Aleurodicus dispersus, Aleurothrixus floccosus, Amrasca biguttula
biguttula, Aonidiella aurantii, Aphis gossypii, Aphis glycines,
Aphis pomi, Aulacorthum solani, Bemisia argentifolii, Bemisia
tabaci, Blissus leucopterus, Brachycorynella asparagi, Brevennia
rehi, Brevicoryne brassicae, Calocoris norvegicus, Ceroplastes
rubens, Cimex hemipterus, Cimex lectularius, Dagbertus fasciatus,
Dichelops furcatus, Diuraphis noxia, Diaphorina citri, Dysaphis
plantaginea, Dysdercus suturellus, Edessa meditabunda, Eriosoma
lanigerum, Eurygaster maura, Euschistus heros, Euschistus servus,
Helopeltis antonii, Helopeltis theivora, Icerya purchasi,
Idioscopus nitidulus, Laodelphax striatellus, Leptocorisa
oratorius, Leptocorisa varicornis, Lygus hesperus, Maconellicoccus
hirsutus, Macrosiphum euphorbiae, Macrosiphum granarium,
Macrosiphum rosae, Macrosteles quadrilineatus, Mahanarva
frimbiolata, Metopolophium dirhodum, Mictis longicornis, Myzus
persicae, Nephotettix cinctipes, Neurocolpus longirostris, Nezara
viridula, Nilaparvata lugens, Parlatoria pergandii, Parlatoria
ziziphi, Peregrinus maidis, Phylloxera vitifoliae, Physokermes
piceae, Phytocoris californicus, Phytocoris relativus, Piezodorus
guildinii, Poecilocapsus lineatus, Psallus vaccinicola, Pseudacysta
perseae, Pseudococcus brevipes, Quadraspidiotus perniciosus,
Rhopalosiphum maidis, Rhopalosiphum padi, Saissetia oleae,
Scaptocoris castanea, Schizaphis graminum, Sitobion avenae,
Sogatella furcifera, Trialeurodes vaporariorum, Trialeurodes
abutiloneus, Unaspis yanonensis, and Zulia entrerriana.
[0243] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Hymenoptera. A
non-exhaustive list of particular genera includes, but is not
limited to, Acromyrmex spp., Atta spp., Camponotus spp., Diprion
spp., Formica spp., Monomorium spp., Neodiprion spp., Pogonomyrmex
spp., Polistes spp., Solenopsis spp., Vespula spp., and Xylocopa
spp. A non-exhaustive list of particular species includes, but is
not limited to, Athalia rosae, Atta texana, Iridomyrmex humilis,
Monomorium minimum, Monomorium pharaonis, Solenopsis invicta,
Solenopsis geminata, Solenopsis molesta, Solenopsis richtery,
Solenopsis xyloni, and Tapinoma sessile.
[0244] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Isoptera. A
non-exhaustive list of particular genera includes, but is not
limited to, Coptotermes spp., Cornitermes spp., Cryptotermes spp.,
Heterotermes spp., Kalotermes spp., Incisitermes spp., Macrotermes
spp., Marginitermes spp., Microcerotermes spp., Procornitermes
spp., Reticulitermes spp., Schedorhinotermes spp., and Zootermopsis
spp. A non-exhaustive list of particular species includes, but is
not limited to, Coptotermes curvignathus, Coptotermes frenchi,
Coptotermes formosanus, Heterotermes aureus, Microtermes obesi,
Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermes
flavipes, Reticulitermes hageni, Reticulitermes hesperus,
Reticulitermes santonensis, Reticulitermes speratus, Reticulitermes
tibialis, and Reticulitermes virginicus.
[0245] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Lepidoptera. A
non-exhaustive list of particular genera includes, but is not
limited to, Adoxophyes spp., Agrotis spp., Argyrotaenia spp.,
Cacoecia spp., Caloptilia spp., Chilo spp., Chrysodeixis spp.,
Colias spp., Crambus spp., Diaphania spp., Diatraea spp., Earias
spp., Ephestia spp., Epimecis spp., Feltia spp., Gortyna spp.,
Helicoverpa spp., Heliothis spp., Indarbela spp., Lithocolletis
spp., Loxagrotis spp., Malacosoma spp., Peridroma spp.,
Phyllonorycter spp., Pseudaletia spp., Sesamia spp., Spodoptera
spp., Synanthedon spp., and Yponomeuta spp. A non-exhaustive list
of particular species includes, but is not limited to, Achaea
janata, Adoxophyes orana, Agrotis ipsilon, Alabama argillacea,
Amorbia cuneana, Amyelois transitella, Anacamptodes defectaria,
Anarsia lineatella, Anomis sabulifera, Anticarsia gemmatalis,
Archips argyrospila, Archips rosana, Argyrotaenia citrana,
Autographa gamma, Bonagota cranaodes, Borbo cinnara, Bucculatrix
thurberiella, Capua reticulana, Carposina niponensis, Chlumetia
transversa, Choristoneura rosaceana, Cnaphalocrocis medinalis,
Conopomorpha cramerella, Cossus cossus, Cydia caryana, Cydia
funebrana, Cydia molesta, Cydia nigricana, Cydia pomonella, Darna
diducta, Diatraea saccharalis, Diatraea grandiosella, Earias
insulana, Earias vittella, Ecdytolopha aurantianum, Elasmopalpus
lignosellus, Ephestia cautella, Ephestia elutella, Ephestia
kuehniella, Epinotia aporema, Epiphyas postvittana, Erionota thrax,
Eupoecilia ambiguella, Euxoa auxiliaris, Grapholita molesta,
Hedylepta indicata, Helicoverpa armigera, Helicoverpa zea,
Heliothis virescens, Hellula undalis, Keiferia lycopersicella,
Leucinodes orbonalis, Leucoptera coffeella, Leucoptera
malifoliella, Lobesia botrana, Loxagrotis albicosta, Lymantria
dispar, Lyonetia clerkella, Mahasena corbetti, Mamestra brassicae,
Maruca testulalis, Metisa plana, Mythimna unipuncta, Neoleucinodes
elegantalis, Nymphula depunctalis, Operophtera brumata, Ostrinia
nubilalis, Oxydia vesulia, Pandemis cerasana, Pandemis heparana,
Papilio demodocus, Pectinophora gossypiella, Peridroma saucia,
Perileucoptera coffeella, Phthorimaea operculella, Phyllocnistis
citrella, Pieris rapae, Plathypena scabra, Plodia interpunctella,
Plutella xylostella, Polychrosis viteana, Prays endocarpa, Prays
oleae, Pseudaletia unipuncta, Pseudoplusia includens, Rachiplusia
nu, Scirpophaga incertulas, Sesamia inferens, Sesamia nonagrioides,
Setora nitens, Sitotroga cerealella, Sparganothis pilleriana,
Spodoptera exigua, Spodoptera frugiperda, Spodoptera eridania,
Thecla basilides, Tineola bisselliella, Trichoplusia ni, Tuta
absoluta, Zeuzera coffeae, and Zeuzera pyrina.
[0246] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Mallophaga. A
non-exhaustive list of particular genera includes, but is not
limited to, Anaticola spp., Bovicola spp., Chelopistes spp.,
Goniodes spp., Menacanthus spp., and Trichodectes spp. A
non-exhaustive list of particular species includes, but is not
limited to, Bovicola bovis, Bovicola caprae, Bovicola ovis,
Chelopistes meleagridis, Goniodes dissimilis, Goniodes gigas,
Menacanthus stramineus, Menopon gallinae, and Trichodectes
canis.
[0247] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Orthoptera. A
non-exhaustive list of particular genera includes, but is not
limited to, Melanoplus spp., and Pterophylla spp. A non-exhaustive
list of particular species includes, but is not limited to, Anabrus
simplex, Gryllotalpa africana, Gryllotalpa australis, Gryllotalpa
brachyptera, Gryllotalpa hexadactyla, Locusta migratoria,
Microcentrum retinerve, Schistocerca gregaria, and Scudderia
furcata.
[0248] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Siphonaptera. A
non-exhaustive list of particular species includes, but is not
limited to, Ceratophyllus gallinae, Ceratophyllus niger,
Ctenocephalides canis, Ctenocephalides felis, and Pulex
irritans.
[0249] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Thysanoptera. A
non-exhaustive list of particular genera includes, but is not
limited to, Caliothrips spp., Frankliniella spp., Scirtothrips
spp., and Thrips spp. A non-exhaustive list of particular sp.
includes, but is not limited to, Frankliniella fusca, Frankliniella
occidentalis, Frankliniella schultzei, Frankliniella williamsi,
Heliothrips haemorrhoidalis, Rhipiphorothrips cruentatus,
Scirtothrips citri, Scirtothrips dorsalis, and Taeniothrips
rhopalantennalis, Thrips hawaiiensis, Thrips nigropilosus, Thrips
orientalis, Thrips tabaci.
[0250] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Thysanura. A
non-exhaustive list of particular genera includes, but is not
limited to, Lepisma spp. and Thermobia spp.
[0251] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Order Acarina. A
non-exhaustive list of particular genera includes, but is not
limited to, Acarus spp., Aculops spp., Boophilus spp., Demodex
spp., Dermacentor spp., Epitrimerus spp., Eriophyes spp., Ixodes
spp., Oligonychus spp., Panonychus spp., Rhizoglyphus spp., and
Tetranychus spp. A non-exhaustive list of particular species
includes, but is not limited to, Acarapis woodi, Acarus siro,
Aceria mangiferae, Aculops lycopersici, Aculus pelekassi, Aculus
schlechtendali, Amblyomma americanum, Brevipalpus obovatus,
Brevipalpus phoenicis, Dermacentor variabilis, Dermatophagoides
pteronyssinus, Eotetranychus carpini, Notoedres cati, Oligonychus
coffeae, Oligonychus ilicis, Panonychus citri, Panonychus ulmi,
Phyllocoptruta oleivora, Polyphagotarsonemus latus, Rhipicephalus
sanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychus
urticae, and Varroa destructor.
[0252] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pest of the Order Symphyla. A
non-exhaustive list of particular sp. includes, but is not limited
to, Scutigerella immaculata.
[0253] In another embodiment, the Molecules of Formulas One, Two
and Three may be used to control pests of the Phylum Nematoda. A
non-exhaustive list of particular genera includes, but is not
limited to, Aphelenchoides spp., Belonolaimus spp., Criconemella
spp., Ditylenchus spp., Heterodera spp., Hirschmanniella spp.,
Hoplolaimus spp., Meloidogyne spp., Pratylenchus spp., and
Radopholus spp. A non-exhaustive list of particular sp. includes,
but is not limited to, Dirofilaria immitis, Heterodera zeae,
Meloidogyne incognita, Meloidogyne javanica, Onchocerca volvulus,
Radopholus similis, and Rotylenchulus reniformis.
[0254] For additional information consult "HANDBOOK OF PEST
CONTROL--THE BEHAVIOR, LIFE HISTORY, AND CONTROL OF HOUSEHOLD
PESTS" by Arnold Mallis, 9th Edition, copyright 2004 by GIE Media
Inc.
Applications
[0255] Molecules of Formulas One, Two and Three are generally used
in amounts from about 0.01 grams per hectare to about 5000 grams
per hectare to provide control. Amounts from about 0.1 grams per
hectare to about 500 grams per hectare are generally preferred, and
amounts from about 1 gram per hectare to about 50 grams per hectare
are generally more preferred.
[0256] The area to which a molecule of Formulas One, Two and Three
is applied can be any area inhabited (or maybe inhabited, or
traversed by) a pest, for example: where crops, trees, fruits,
cereals, fodder species, vines, turf and ornamental plants, are
growing; where domesticated animals are residing; the interior or
exterior surfaces of buildings (such as places where grains are
stored), the materials of construction used in building (such as
impregnated wood), and the soil around buildings. Particular crop
areas to use a molecule of Formula One include areas where apples,
corn, sunflowers, cotton, soybeans, canola, wheat, rice, sorghum,
barley, oats, potatoes, oranges, alfalfa, lettuce, strawberries,
tomatoes, peppers, crucifers, pears, tobacco, almonds, sugar beets,
beans and other valuable crops are growing or the seeds thereof are
going to be planted. It is also advantageous to use aluminum
sulfate with a molecule of Formula One when growing various
plants.
[0257] Controlling pests generally means that pest populations,
pest activity, or both, are reduced in an area. This can come about
when: pest populations are repulsed from an area; when pests are
incapacitated in or around an area; or pests are exterminated, in
whole, or in part, in or around an area. Of course, a combination
of these results can occur. Generally, pest populations, activity,
or both are desirably reduced more than fifty percent, preferably
more than 90 percent. Generally, the area is not in or on a human;
consequently, the locus is generally a non-human area.
[0258] The Molecules of Formulas One, Two and Three may be used in
mixtures, applied simultaneously or sequentially, alone or with
other compounds to enhance plant vigor (e.g. to grow a better root
system, to better withstand stressful growing conditions). Such
other compounds are, for example, compounds that modulate plant
ethylene receptors, most notably 1-methylcyclopropene (also known
as 1-MCP).
[0259] The Molecules of Formulas One, Two and Three can be applied
to the foliar and fruiting portions of plants to control pests. The
molecules will either come in direct contact with the pest, or the
pest will consume the pesticide when eating leaf, fruit mass, or
extracting sap, that contains the pesticide. The Molecules of
Formulas One, Two and Three can also be applied to the soil, and
when applied in this manner, root and stem feeding pests can be
controlled. The roots can absorb a molecule taking it up into the
foliar portions of the plant to control above ground chewing and
sap feeding pests.
[0260] Generally, with baits, the baits are placed in the ground
where, for example, termites can come into contact with, and/or be
attracted to, the bait. Baits can also be applied to a surface of a
building, (horizontal, vertical, or slant surface) where, for
example, ants, termites, cockroaches, and flies, can come into
contact with, and/or be attracted to, the bait. Baits can comprise
a molecule of Formula One, Two or Three.
[0261] The Molecules of Formulas One, Two and Three can be
encapsulated inside, or placed on the surface of a capsule. The
size of the capsules can range from nanometer size (about 100-900
nanometers in diameter) to micrometer size (about 10-900 microns in
diameter).
[0262] Because of the unique ability of the eggs of some pests to
resist certain pesticides, repeated applications of the Formula
One, Two or Three may be desirable to control newly emerged
larvae.
[0263] Systemic movement of pesticides in plants may be utilized to
control pests on one portion of the plant by applying (for example
by spraying an area) the Molecules of Formula One, Two or Three to
a different portion of the plant. For example, control of
foliar-feeding insects can be achieved by drip irrigation or furrow
application, by treating the soil with for example pre- or
post-planting soil drench, or by treating the seeds of a plant
before planting.
[0264] Seed treatment can be applied to all types of seeds,
including those from which plants genetically modified to express
specialized traits will germinate. Representative examples include
those expressing proteins toxic to invertebrate pests, such as
Bacillus thuringiensis or other insecticidal toxins, those
expressing herbicide resistance, such as "Roundup Ready" seed, or
those with "stacked" foreign genes expressing insecticidal toxins,
herbicide resistance, nutrition-enhancement, drought resistance, or
any other beneficial traits. Furthermore, such seed treatments with
the Molecules of Formula One, Two or Three may further enhance the
ability of a plant to better withstand stressful growing
conditions. This results in a healthier, more vigorous plant, which
can lead to higher yields at harvest time. Generally, about 1 gram
of the Molecules of Formula One, Two or Three to about 500 grams
per 100,000 seeds is expected to provide good benefits, amounts
from about 10 grams to about 100 grams per 100,000 seeds is
expected to provide better benefits, and amounts from about 25
grams to about 75 grams per 100,000 seeds is expected to provide
even better benefits.
[0265] It should be readily apparent that the Molecules of Formulas
One, Two and Three may be used on, in, or around plants genetically
modified to express specialized traits, such as Bacillus
thuringiensis or other insecticidal toxins, or those expressing
herbicide resistance, or those with "stacked" foreign genes
expressing insecticidal toxins, herbicide resistance,
nutrition-enhancement, or any other beneficial traits.
[0266] The Molecules of Formulas One, Two and Three may be used for
controlling endoparasites and ectoparasites in the veterinary
medicine sector or in the field of non-human animal keeping. The
Molecules of Formulas One, Two and Three are applied, such as by
oral administration in the form of, for example, tablets, capsules,
drinks, granules, by dermal application in the form of, for
example, dipping, spraying, pouring on, spotting on, and dusting,
and by parenteral administration in the form of, for example, an
injection.
[0267] The Molecules of Formulas One, Two and Three may also be
employed advantageously in livestock keeping, for example, cattle,
sheep, pigs, chickens, and geese. They may also be employed
advantageously in pets such as, horses, dogs, and cats. Particular
pests to control would be fleas and ticks that are bothersome to
such animals. Suitable formulations are administered orally to the
animals with the drinking water or feed. The dosages and
formulations that are suitable depend on the species.
[0268] The Molecules of Formulas One, Two and Three may also be
used for controlling parasitic worms, especially of the intestine,
in the animals listed above.
[0269] The Molecules of Formula One, Two, and Three may also be
employed in therapeutic methods for human health care. Such methods
include, but are limited to, oral administration in the form of,
for example, tablets, capsules, drinks, granules, and by dermal
application.
[0270] Pests around the world have been migrating to new
environments (for such pest) and thereafter becoming a new invasive
species in such new environment. The Molecules of Formula One and
Two may also be used on such new invasive species to control them
in such new environment.
[0271] The Molecules of Formula One, Two, and Three may also be
used in an area where plants, such as crops, are growing (e.g.
pre-planting, planting, pre-harvesting) and where there are low
levels (even no actual presence) of pests that can commercially
damage such plants. The use of such molecules in such area is to
benefit the plants being grown in the area. Such benefits, may
include, but are not limited to, improving the health of a plant,
improving the yield of a plant (e.g. increased biomass and/or
increased content of valuable ingredients), improving the vigor of
a plant (e.g. improved plant growth and/or greener leaves),
improving the quality of a plant (e.g. improved content or
composition of certain ingredients), and improving the tolerance to
abiotic and/or biotic stress of the plant.
[0272] Before a pesticide can be used or sold commercially, such
pesticide undergoes lengthy evaluation processes by various
governmental authorities (local, regional, state, national, and
international). Voluminous data requirements are specified by
regulatory authorities and must be addressed through data
generation and submission by the product registrant or by a third
party on the product registrant's behalf, often using a computer
with a connection to the World Wide Web. These governmental
authorities then review such data and if a determination of safety
is concluded, provide the potential user or seller with product
registration approval. Thereafter, in that locality where the
product registration is granted and supported, such user or seller
may use or sell such pesticide.
[0273] A molecule according to Formula One, Two, and Three can be
tested to determine its efficacy against pests. Furthermore, mode
of action studies can be conducted to determine if said molecule
has a different mode of action than other pesticides. Thereafter,
such acquired data can be disseminated, such as by the internet, to
third parties.
[0274] The headings in this document are for convenience only and
must not be used to interpret any portion hereof.
TABLE-US-00001 TABLE SECTION % Control (or Mortality) Rating BAW
& CEW Rating Table 50-100 A More than 0-Less than 50 B Not
Tested C No activity noticed in this bioassay D GPA Rating Table
80-100 A More than 0-Less than 80 B Not Tested C No activity
noticed in this bioassay D
TABLE-US-00002 TABLE 1 Structures for Compounds ID Structure I-4
##STR00034## I-5 ##STR00035## I-6 ##STR00036## I-7 ##STR00037## I-8
##STR00038## I-9 ##STR00039## I-10 ##STR00040## I-11 ##STR00041##
I-12 ##STR00042## I-13 ##STR00043## I-14 ##STR00044## I-15
##STR00045## I-16 ##STR00046## I-17 ##STR00047## I-18 ##STR00048##
I-19 ##STR00049## I-20 ##STR00050## I-21 ##STR00051## I-22
##STR00052## I-23 ##STR00053## I-24 ##STR00054## I-25 ##STR00055##
I-26 ##STR00056## I-27 ##STR00057## I-28 ##STR00058## I-29
##STR00059## I-30 ##STR00060## I-31 ##STR00061## I-32 ##STR00062##
I-33 ##STR00063## I-34 ##STR00064## I-35 ##STR00065## I-36
##STR00066## I-37 ##STR00067## I-38 ##STR00068## I-39 ##STR00069##
I-40 ##STR00070## I-41 ##STR00071## I-42 ##STR00072## I-43
##STR00073## I-44 ##STR00074## I-45 ##STR00075## I-46 ##STR00076##
I-47 ##STR00077## I-48 ##STR00078## I-49 ##STR00079## I-50
##STR00080## I-51 ##STR00081## I-52 ##STR00082## I-53 ##STR00083##
I-54 ##STR00084## I-55 ##STR00085## I-56 ##STR00086## I-57
##STR00087## I-58 ##STR00088## I-59 ##STR00089## I-60 ##STR00090##
I-61 ##STR00091## I-62 ##STR00092## I-63 ##STR00093## I-64
##STR00094## I-65 ##STR00095##
TABLE-US-00003 TABLE 2 Analytical Data for Compounds in Table 1.
Synthesis mp .sup.1H, .sup.13C, or .sup.19F NMR ID Method MS
(.degree. C.) (.delta.).sup.1 I-4 A 551 (M + 1) 209-211
(DMSO-d.sub.6) 12.06 (s, 1H), 10.19 (s, 1H), 9.42 (s, 1H), 8.22 (s,
1H), 8.17-8.03 (m, 5H), 7.66-7.57 (m, 4H), 7.42-7.38 (m, 2H) I-5 C
511 (M + 1) 220-225 (CDCl.sub.3) 9.30 (s, 1H), 8.69 (s, 1H), 8.60
(s, 1H), 8.26 (d, J = 8.4 Hz, 2H), 7.89 (s, 1H), 7.81 (m, 4H), 7.41
(d, J = 8.4 Hz, 2H), 7.19 (m, 3H), 2.35 (s, 6H) I-6 C 555 (M + H)
206-209 (CDCl.sub.3) 8.90 (s, 1H), 8.80 (s, 1H), 8.6 (s, 1H), 8.28
(d, J = 8.4 Hz, 2H), 8.9-8.7 (m, 4H), 7.4 (d, J = 8.6 Hz, 2H), 6.7
(s, 2H), 3.80 (s, 3H), 2.39 (s, 3H), 2.32 (s, 6H) I-7 C 541 (M + H)
202-210 (CDCl.sub.3) 9.88 (s, 1H), 8.61 (s, 1H), 8.60 (s, 1H), 8.27
(d, J = 8.4 Hz, 2H), 7.9 (s, 1H), 7.9-7.7 (m, 4H), 7.4 (d, J = 8.6
Hz, 2H), 6.7 (s, 2H), 3.81 (s, 3H), 2.33 (s, 6H) I-8 B 581 195-199
(CDCl.sub.3) 10.2 (s, 1H), 8.7 (s, 1H), 8.6 (s, 1H), 8.25 (d, J =
8.4 Hz, 2H), 8.0 (s, 1H), 7.82 (m, 4H), 7.4 (d, J = 8.4 Hz, 2H),
7.0 (s, 2H), 3.82 (s, 3H) I-9 C 591 (M + H) 233-236 (CDCl.sub.3)
9.89 (s, 1H), 8.60 (s, 2H), 8.25 (d, J = 8.5 Hz, 2H), 7.95 (s, 1H),
7.88-7.70 (m, 4H), 7.41 (d, J = 9.0 Hz, 2H), 6.70 (s, 2H), 3.81 (s,
3H), 2.31 (s, 6H) I-10 C 525 (M + H) 230-240 (CDCl.sub.3) 9.93 (s,
1H), 8.69 (s, 1H), 8.60 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H), 7.93 (d,
J = 9.5 Hz, 2H), 7.95 (s, 1H), 7.86-7.75 (m, 4H), 6.69 (s, 2H),
3.81 (s, 3H), 2.31 (s, 6H) I-11 C 561 (M + H) 234-238 (CDCl.sub.3)
9.62 (s, 1H), 8.70 (s, 1H), 8.60 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H),
7.92 (s, 1H), 7.86-7.75 (m, 4H), 7.41 (d, J = 9.0 Hz, 2H), 7.18 (m,
3H), 2.35 (s, 6H) I-12 C 577 (M + H) 197-200 (CDCl.sub.3) 10.2 (s,
1H), 8.90 (s, 1H), 8.62 (s, 1H), 8.25 (d, J = 8.4 Hz, 2H), 7.98 (s,
1H), 7.9-7.7 (m, 4H), 7.4 (m, 3H), 6.8 (m, 2H), 3.82 (s, 3H), 2.37
(s, 3H) I-13 B 541 (M + H) 180-186 (CDCl.sub.3) 9.9 (s, 1H), 8.6
(s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.9 (s, 1H), 7.8 (d, J = 8.6 Hz,
2H), 7.75 (d, J = 8.4 Hz, 2H), 7.7 (d, J = 7 Hz, 1H), 7.45-7.35 (m,
4H), 6.91 (d, J = 8 Hz, 2H), 5.73 (m, 1H), 3.80 (s, 3H), 1.65 (d, J
= 7.2 Hz, 3H) I-14 B 559 (M + H) 196-203 (CDCl.sub.3) 9.32 (s, 1H),
8.6 (s, 1H), 8.22 (d, J = 8.4 Hz, 2H), 7.85-7.7 (m, 5H), 7.6 (d, J
= 6 Hz, 1H), 7.4 (d, J = 8.5 Hz, 2H), 7.25-7.15 (m, 2H), 6.93 (m,
1H), 5.7 (m, 1H), 3.89 (s, 3H), 1.67 (d, J = 6 Hz, 3H) I-15 B 511
(M + H) 201-206 (CDCl.sub.3) 9.32 (s, 1H), 8.61 (s, 1H), 8.27 (d, J
= 8.4 Hz, 2H), 7.9-7.7 (m, 6H), 7.5-7.3 (m, 7H), 5.76 (m, 1H), 1.67
(d, J = 7 Hz, 3H) I-16 C 525 (M + 1) 218-225 (CDCl.sub.3) 9.37 (s,
1H), 8.63 (s, 1H), 8.60 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H), 7.89 (s,
1H), 7.85-7.76 (m, 4H), 7.41 (d, J = 8.4 Hz, 2H), 6.97 (s, 2H),
2.32 (s, 3H), 2.30 (s, 6H) I-17 C 525 (M + H) 168-180 (CDCl.sub.3)
10.2 (s, 1H), 9.07 (s, 1H), 8.63 (s, 1H), 8.25 (d, J = 8.4 Hz, 2H),
8.0 (s, 1H), 7.9-7.7 (m, 4H), 7.65 (d, J = 8 Hz, 1H), 7.4-7.25 (m,
5H), 3.25 (heptet, J = 7 Hz, 1H), 1.35 (d, J = 7 Hz, 6H) I-18 C 539
(M + 1) 216-221 (CDCl.sub.3) .delta. 9.29 (s, 1H), 8.87 (s, 1H),
8.59 (s, 1H), 8.31-8.19 (m, 2H), 7.90-7.84 (m, 2H), 7.85-7.79 (m,
2H), 7.73 (dd, J = 7.5, 1.7 Hz, 1H), 7.39 (dd, J = 12.6, 5.1 Hz,
3H), 7.35-7.27 (m, 2H), 3.37-3.04 (m, 1H), 2.40 (s, 3H), 1.29 (d, J
= 7.5 Hz, 6H) I-19 C 509 (M + 1) 223-225 (CDCl.sub.3) .delta. 9.74
(s, 1H), 9.06 (s, 1H), 8.69 (s, 1H), 8.31-8.20 (m, 2H), 7.98-7.84
(m, 3H), 7.80 (m, 4H), 7.65 (d, J = 1.4 Hz, 1H), 7.43-7.28 (m, 3H),
3.19 (heptet, J = 6.9 Hz, 1H), 1.32 (d, J = 6.9 Hz, 6H) I-20 C 538
(M + H) 220 (dec) (CDCl.sub.3) .delta. 9.52 (s, 1H), 9.31 (s, 1H),
8.66 (d, J = 8.2 Hz, 1H), 8.60 (s, 1H), 8.25 (d, J = 8.4 Hz, 2H),
7.87 (s, 1H), 7.86-7.80 (m, 2H), 7.77 (d, J = 8.4 Hz, 2H), 7.41 (d,
J = 8.3 Hz, 2H), 7.32 (ddd, J = 13.9, z 7.2, 4.3 Hz, 1H), 7.24-7.15
(m, 2H), 6.27 (s, 1H), 2.03 (d, J = 1.3 Hz, 3H), 1.73 (d, J = 1.1
Hz, 3H) I-21 C 540 (M + H) 207-210; (CDCl.sub.3) .delta. 9.48 (s,
1H), 9.14 (s, 1H), 215-218 8.60 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H),
7.92 (s, 1H), 7.87 (d, J = 7.7 Hz, 1H), 7.84-7.76 (m, 4H), 7.40 (d,
J = 8.3 Hz, 2H), 7.30 (dt, J = 8.2, 3.7 Hz, 1H), 7.28-7.23 (m, 2H),
2.57 (d, J = 7.2 Hz, 2H), 1.93 (dq, J = 13.6, 6.7 Hz, 1H), 0.98 (d,
J = 6.6 Hz, 6H) I-22 C 540 (M + H) 210-215 (CDCl.sub.3) .delta.
9.46 (s, 1H), 9.05 (s, 1H), 8.60 (s, 1H), 8.26 (d, J = 8.4 Hz, 2H),
7.91 (s, 1H), 7.84-7.74 (m, 4H), 7.69 (d, J = 7.4 Hz, 1H), 7.40 (d,
J = 8.3 Hz, 2H), 7.36-7.27 (m, 3H), 2.91 (dt, J = 13.9, 6.9 Hz,
1H), 1.75-1.58 (m, 2H), 1.30 (d, J = 6.9 Hz, 3H), 0.92 (t, J = 7.4
Hz, 3H). I-23 C 560 (M + H) 213-216 (CDCl.sub.3) .delta. 9.41 (s,
1H), 9.01 (s, 1H), 8.74 (d, J = 7.7 Hz, 1H), 8.60 (s, 1H), 8.15 (d,
J = 8.4 Hz, 2H), 7.86-7.78 (m, 2H), 7.69 (s, 1H), 7.57-7.44 (m,
6H), 7.42 (d, J = 9.1 Hz, 2H), 7.37-7.27 (m, 4H). I-24 C 524 (M +
H) 200-206; (CDCl.sub.3) .delta. 9.65 (d, J = 17.9 Hz, 1H), 210-211
9.20 (s, 1H), 8.60 (s, 1H), 8.27 (dd, J = 8.0, 4.5 Hz, 3H), 7.89
(s, 1H), 7.86-7.75 (m, 4H), 7.41 (d, J = 8.3 Hz, 2H), 7.30-7.27 (m,
1H), 7.18 (q, J = 7.8 Hz, 2H), 2.00-1.90 (m, 1H), 1.09-1.01 (m,
2H), 0.81-0.73 (m, 2H). I-25 C 550 (M + H) 221-223 (DMSO-d.sub.6)
.delta. 12.13 (s, 1H), 10.07 (s, 1H), 9.44 (s, 1H), 8.23 (s, 1H),
8.16 (d, J = 8.4 Hz, 2H), 8.13-8.06 (m, 2H), 8.01-7.98 (m, 3H),
7.63 (d, J = 8.4 Hz, 2H), 7.38-7.26 (m, 3H), 7.23 (t, J.sub.HF =
74.1 Hz, 1H) I-26 C 590 (M + H) 230-231 (CDCl.sub.3) .delta. 9.37
(s, 1H), 8.60 (s, 1H), 8.57 (s, 1H), 8.27 (d, J = 8.4 Hz, 2H), 7.90
(s, 1H), 7.81 (dt, J = 8.5, 4.8 Hz, 4H), 7.41 (d, J = 8.3 Hz, 2H),
7.31 (s, 2H), 2.31 (s, 6H) I-27 C 556 (M + H) 190-192 (CDCl.sub.3)
.delta. 9.39 (s, 1H), 9.15 (s, 1H), 8.61 (s, 1H), 8.29 (d, J = 8.4
Hz, 2H), 8.16-8.05 (m, 2H), 7.95-7.85 (m, 3H), 7.85-7.76 (m, 4H),
7.41 (d, J = 8.3 Hz, 2H), 4.39 (q, J = 7.1 Hz, 2H), 1.41 (t, J =
7.1 Hz, 3H) I-28 C 528 (M + H) 219-221 (300 MHz, CDCl.sub.3)
.delta. 10.17 (s, 1H), 9.09 (s, 1H), 9.03 (t, J = 5.4 Hz, 1H), 8.60
(s, 1H), 8.23 (t, J = 8.9 Hz, 2H), 7.89-7.76 (m, 5H), 7.39 (t, J =
7.2 Hz, 2H), 7.17-7.07 (m, 1H), 7.03 (d, J = 7.8 Hz, 1H), 6.94 (d,
J = 6.9 Hz, 1H), 4.18 (q, J = 7.1 Hz, 2H), 1.61 (t, J = 7.0 Hz, 3H)
I-29 C 499 (M + 1) 195-200 (DMSO-d.sub.6) .delta. 9.44 (s, 1H),
8.49 (s, 1H), 8.42 (d, J = 5.2 Hz, 1H), 8.29-8.21 (m, 2H), 8.16 (d,
J = 8.5 Hz, 2H), 8.10 (d, J = 2.3 Hz, 1H), 8.08 (d, J = 3.0 Hz,
1H), 8.04 (t, J = 6.5 Hz, 2H), 7.63 (d, J = 8.3 Hz, 3H), 2.29 (s,
3H). I-30 C 499 (M + 1) 114-118 (CDCl.sub.3) .delta. 8.60 (s, 1H),
8.31 (s, 1H), 8.24 (d, J = 8.4 Hz, 2H), 8.16 (d, J = 3.9 Hz, 1H),
7.95 (d, J = 8.4 Hz, 2H), 7.82 (d, J = 9.0 Hz, 2H), 7.55 (d, J =
6.7 Hz, 1H), 7.41 (s, 2H), 6.99 (dd, J = 7.4, 5.1 Hz, 1H), 2.35 (s,
3H). I-31 C 513 (M + 1) 122-125 (CDCl.sub.3) .delta. 8.60 (s, 1H),
8.32 (s, 1H), 8.25 (d, J = 8.4 Hz, 2H), 8.19-8.16 (m, 1H), 7.97 (d,
J = 8.4 Hz, 2H), 7.84-7.81 (m, 2H), 7.58 (d, J = 7.5 Hz, 1H), 7.40
(d, J = 8.3 Hz, 2H), 7.03 (dd, J = 7.5, 5.1 Hz, 1H), 2.67 (s, 2H),
1.35 (t, J = 7.5 Hz, 3H). I-32 M 210 ([M + H].sup.+) --
(CDCl.sub.3) .delta. 8.97 (bs, 1H), 7.74-7.11 (m, 5H), 4.06 (bs,
2H), 3.11 (hept, J = 6.9 Hz, 1H), 1.24 (d, J = 6.9 Hz, 6H) I-33 C
575 ([M + H].sup.+) 214-216 (DMSO-d.sub.6) .delta. 11.87 (s, 1H),
10.08 (s, 1H), 9.44 (s, 1H), 8.20 (s, 1H), 8.17-8.02 (m, 6H), 7.63
(d, J = 9.0 Hz, 2H), 7.39-7.35 (m, 1H), 7.35-7.28 (m, 1H),
7.27-7.18 (m, 2H), 3.19-3.05 (m, 1H), 1.20 (d, J = 6.9 Hz, 6H);
.sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -85.20, -86.94 I-34 P*
317 ([M + H].sup.+) -- (CDCl.sub.3) .delta. 8.50 (s, 1H), 8.07 (d,
J = 8.1 Hz, 2H), 7.56 (d, J = 2.1 Hz, 1H), 7.44 (dd, J = 8.6, 2.2
Hz, 1H), 7.29 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.6 Hz, 1H), 2.42
(s, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -49.69 I-35 P*
330 ([M + H].sup.+) -- (CDCl.sub.3) .delta. 10.09 (s, 1H), 8.55 (m,
1H), 8.37 (m, 1H), 8.22 (m, 1H), 8.00 (m, 1H), 7.57 (dd, J = 5.3,
2.2 Hz, 1H), 7.51 (m, 1H), 7.46 (m, 1H), 7.21 (m, 1H); .sup.19F NMR
(376 MHz, CDCl.sub.3) .delta. -49.61 I-36 C 521 ([M + H].sup.+) 200
(dec.) (CDCl.sub.3) .delta. 9.47 (s, 1H), 9.05 (s, 1H), 8.54 (s,
1H), 8.25 (d, J = 8.4 Hz, 2H), 7.92 (s, 1H), 7.78 (d, J = 8.4 Hz,
2H), 7.71-7.62 (m, 1H), 7.57 (t, J = 2.7 Hz, 1H), 7.46 (dd, J =
8.6, 2.2 Hz, 1H), 7.41-7.29 (m, 3H), 7.21 (d, J = 8.6 Hz, 1H), 3.19
(dt, J = 13.8, 6.9 Hz, 1H), 1.32 (d, J = 6.9 Hz, 6H); .sup.19F NMR
(376 MHz, CDCl.sub.3) .delta. -49.62 I-37 M -- -- (CDCl.sub.3)
.delta. 7.48-7.36 (m, 1H), 7.21-7.06 (m, 2H), 5.23 (p, J = 1.5 Hz,
1H), 5.05 (q, J = 1.1 Hz, 1H), 2.09 (s, 3H); .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 153.56 (d, J.sub.CF = 257.5 Hz), 139.62,
139.60, 138.83, 131.48 (d, J.sub.CF = 8.6 Hz), 124.47 (d, J.sub.CF
= 3.6 Hz), 117.60, 115.51 (d, J.sub.CF = 19.1 Hz), 23.18 I-38 M --
-- (CDCl.sub.3) .delta. 6.92 (dt, J = 7.7, 1.2 Hz, 1H), 6.86 (ddd,
J = 10.8, 8.1, 1.4 Hz, 1H), 6.69 (td, J = 8.0, 5.6 Hz, 1H), 3.71
(bs, 2H), 2.92 (hept, J = 6.8 Hz, 1H), 1.26 (d, J = 6.8 Hz, 6H);
.sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 151.91 (d, J = 237.6
Hz), 135.10 (d, J = 2.3 Hz), 131.60 (d, J = 11.8 Hz), 120.52 (d, J
= 3.0 Hz), 117.99 (d, J = 8.0 Hz), 112.28 (d, J = 19.6 Hz), 27.77
(d, J = 2.9 Hz), 22.22 I-39 M 229 ([M + H].sup.+) 122-124
(CDCl.sub.3) .delta. 8.56 (bs, 1H), 7.54 (bs, 1H), 7.32 (td, J =
8.1, 5.6 Hz, 1H), 7.17-7.09 (m, 1H), 7.00 (ddd, J = 9.5, 8.2, 1.4
Hz, 1H), 4.07 (bs, 2H), 3.15 (hept, J = 7.0 Hz, 1H), 1.24 (d, J =
6.9 Hz, 6H), 7.78-7.39 (m, 1H) I-40 C 544 ([M + H].sup.+) 210-212
(CDCl.sub.3) .delta. 9.54 (s, 1H), 8.60 (s, 1H), 8.56 (s, 1H),
8.30-8.22 (m, 2H), 7.92 (s, 1H), 7.86-7.76 (m, 4H), 7.44-7.38 (m,
2H), 7.35 (dd, J = 8.1, 5.6 Hz, 1H), 7.18 (d, J = 7.9 Hz, 1H), 7.04
(ddd, J = 9.4, 8.2, 1.3 Hz, 1H), 3.22 (p, J = 6.9 Hz, 1H), 1.29 (d,
J = 6.9 Hz, 6H); I-41 M -- -- (CDCl.sub.3) .delta. 7.60 (dd, J =
8.2, 2.5 Hz, 1H), 7.37-7.21 (m, 2H), 5.19 (p, J = 1.5 Hz, 1H),
4.97-4.89 (m, 1H), 2.11-2.04 (m, 3H); .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 160.96 (d, J = 250.8 Hz), 148.46, 141.88,
135.18 (d, J = 4.1 Hz),
132.09 (d, J = 7.8 Hz), 119.98 (d, J = 20.9 Hz), 115.99, 111.63 (d,
J = 26.4 Hz), 23.35 I-42 M -- -- (CDCl.sub.3) .delta. 7.05 (dd, J =
8.5, 6.4 Hz, 1H), 6.45 (td, J = 8.5, 2.6 Hz, 1H), 6.37 (dd, J =
10.6, 2.6 Hz, 1H), 3.74 (bs, 2H), 2.83 (hept, J = 6.8 Hz, 1H), 1.24
(d, J = 6.8 Hz, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) .delta.
161.75 (d, J = 241.3 Hz), 144.76 (d, J = 10.3 Hz), 128.11 (d, J =
2.8 Hz), 126.53 (d, J = 9.6 Hz), 105.06 (d, J = 20.7 Hz), 102.26
(d, J = 24.2 Hz), 27.27, 22.35 I-43 M 226 ([M - H].sup.+) 133-135
(CDCl.sub.3) .delta. 9.11 (bs, 1H), 7.44 (bs, 2H), 7.35-7.27 (m,
1H), 6.99 (s, 1H), 4.03 (bs, 2H), 3.05 (hept, J = 6.9 Hz, 1H), 1.23
(d, J = 6.9 Hz, 6H) I-44 C 544 ([M + H].sup.+) 217-222 (CDCl.sub.3)
.delta. 9.45 (s, 1H), 9.13 (s, 1H), 8.60 (s, 1H), 8.32-8.21 (m,
2H), 7.92 (s, 1H), 7.87-7.75 (m, 4H), 7.64 (dd, J = 9.9, 2.7 Hz,
1H), 7.46-7.37 (m, 2H), 7.32 (dd, J = 8.8, 6.2 Hz, 1H), 7.02 (td, J
= 8.3, 2.8 Hz, 1H), 3.14 (hept, J = 6.9 Hz, 1H), 1.31 (d, J = 6.9
Hz, 6H) I-45 M -- -- (CDCl.sub.3) .delta. 7.96 (dd, J = 9.0, 5.1
Hz, 1H), 7.08 (ddd, J = 9.0, 7.4, 2.8 Hz, 1H), 7.02 (dd, J = 8.7,
2.8 Hz, 1H), 5.20 (p, J = 1.5 Hz, 1H), 4.96 (p, J = 1.0 Hz, 1H),
2.11-2.06 (m, 3H) I-46 M -- -- CDCl.sub.3) .delta. 6.85 (dd, J =
10.3, 2.9 Hz, 1H), 6.72 (td, J = 8.3, 2.9 Hz, 1H), 6.60 (dd, J =
8.6, 5.1 Hz, 1H), 3.49 (bs, 2H), 2.88 (hept, J = 6.8 1H), 1.24 (d,
J = 6.8 Hz, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 156.92
(d, J.sub.CF = 235.0 Hz), 139.17 (d, J.sub.CF = 2.1 Hz), 134.61 (d,
J.sub.CF = 6.2 Hz), 116.55 (d, J.sub.CF = 7.5 Hz), 112.69 (d,
J.sub.CF = 22.5 Hz), 112.17 (d, J.sub.CF = 22.4 Hz), 27.90, 22.11
I-47 M 228 ([M + H].sup.+) 163-17 (CDCl.sub.3) .delta. 8.88 (bs,
1H) 7.42 (bs, 1H), 7.03 (dd, J = 10.0, 2.9 Hz, 1H), 6.93 (ddd, J =
8.7, 7.7, 3.0 Hz, 1H), 4.03 (bs, 2H), 3.14-3.00 (m, 1H), 1.23 (d, J
= 6.9 Hz, 6H) I-48 C 544 ([M + H].sup.+) 219-221 (300 MHz,
CDCl.sub.3) .delta. 9.55 (s, 1H), 8.90 (s, 1H), 8.59 (s, 1H),
8.30-8.21 (m, 2H), 7.92 (s, 1H), 7.85-7.74 (m, 4H), 7.54 (dd, J =
8.8, 5.5 Hz, 1H), 7.40 (d, J = 8.6 Hz, 2H), 7.07 (dd, J = 10.0, 2.9
Hz, 1H), 6.97 (td, J = 8.2, 2.9 Hz, 1H), 3.24-3.08 (m, 1H), 1.29
(d, J = 6.9 Hz, 6H) I-49 M -- -- (CDCl.sub.3) .delta. 7.64 (dt, J =
8.1, 1.2 Hz, 1H), 7.39 (td, J = 8.2, 5.4 Hz, 1H), 7.31 (td, J =
8.5, 1.2 Hz, 1H), 5.28 (p, J = 1.5 Hz, 1H), 4.91 (p, J = 1.0 Hz,
1H), 2.16 (t, J = 1.3 Hz, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3)
.delta. 159.59 (d, J = 249.3 Hz), 149.81, 136.14, 128.57 (d, J =
9.0 Hz), 127.02 (d, J = 22.0 Hz), 119.84 (d, J = 23.4 Hz), 119.41
(d, J = 3.6 Hz), 117.25, 23.10 (d, J = 1.9 Hz) I-50 M -- --
CDCl.sub.3) .delta. 6.92 (td, J = 8.1, 6.1 Hz, 1H), 6.44 (ddd, J =
10.4, 8.1, 1.1 Hz, 2H), 3.72 (bs, 2H), 3.06 (heptd, J = 7.1, 1.3
Hz, 1H), 1.35 (dd, J = 7.1, 1.5 Hz, 6H); .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 162.83 (d, J = 243.4 Hz), 145.29 (d, J = 8.8
Hz), 127.08 (d, J = 11.2 Hz), 119.64 (d, J = 16.1 Hz), 111.77 (d, J
= 2.3 Hz), 106.47 (d, J = 24.2 Hz), 25.65, 20.97 (d, J = 3.8 Hz)
I-51 M 228 ([M + H].sup.+) 158-160 (CDCl.sub.3) .delta. 8.91 (bs,
1H), 7.42 (bs, 1H), 7.25-7.08 (m, 2H), 7.02 (d, J = 10.0 Hz, 1H),
4.04 (bs, 2H), 3.18 (hept, J = 7.0 Hz, 1H), 1.44-1.24 (m, 6H) I-52
C 544 ([M + H].sup.+) 220-223 (CDCl.sub.3) .delta. 10.05 (s, 1H),
8.95 (s, 1H), 8.60 (s, 1H), 8.30-8.21 (m, 2H), 7.99 (s, 1H),
7.85-7.73 (m, 4H), 7.44-7.37 (m, 2H), 7.34 (d, J = 7.9 Hz, 1H),
7.24 (td, J = 8.1, 5.8 Hz, 1H), 7.05 (ddd, J = 11.1, 8.2, 1.3 Hz,
1H), 3.37-3.21 (m, 1H), 1.41 (dd, J = 7.1, 1.2 Hz, 6H) I-53 C 527
([M + H].sup.+) -- (DMSO-d.sub.6) .delta. 11.98 (s, 1H), 10.11 (s,
1H), 9.57 (s, 1H), 8.24-8.19 (m, 3H), 8.19-8.14 (m, 2H), 8.09-8.03
(m, 2H), 8.03-7.96 (m, 2H), 7.39 (dd, J = 8.7, 6.4 Hz, 1H),
7.22-7.08 (m, 2H), 3.12 (hept, J = 7.1 Hz, 1H), 1.19 (d, J = 6.8
Hz, 6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -60.81,
-117.72 I-54 C 593 ([M + H].sup.+) -- (DMSO-d.sub.6) .delta.
12.07-11.88 (m, 1H), 10.11 (s, 1H), 9.45 (s, 1H), 8.21 (s, 1H),
8.18-8.13 (m, 2H), 8.13-8.08 (m, 2H), 8.08-8.03 (m, 2H), 7.67-7.59
(m, 2H), 7.39 (dd, J = 8.7, 6.5 Hz, 1H), 7.22-7.08 (m, 2H), 3.12
(hept, J = 7.0 Hz, 1H), 1.19 (d, J = 6.8 Hz, 6H); .sup.19F NMR (376
MHz, DMSO-d.sub.6) .delta. -85.19, -86.92, -117.73 I-55 P* 402 [M -
H].sup.-) -- (CDCl.sub.3) .delta. 8.64 (d, J = 1.1 Hz, 1H), 8.09
(m, 3H), 7.93 (m, 3H), 7.78 (d, J = 8.5 Hz, 3H), 7.30 (d, J = 7.9
Hz, 3H), 2.42 (s, 4H); .sup.19F NMR (376 MHz, CDCl.sub.3) .delta.
-75.61, -75.63, -75.63, -182.14, -182.17, -182.18 I-56 P* 418 ([M +
H].sup.+) -- (CDCl.sub.3) .delta. 10.09 (s, 1H), 8.71 (s, 1H), 8.39
(d, J = 8.3 Hz, 2H), 8.01 (d, J = 8.3 Hz, 2H), 7.95 (m, 2H), 7.82
(d, J = 8.6 Hz, 2H); .sup.19F NMR (376 MHz, CDCl.sub.3) .delta.
-75.57, -75.59, -182.14, -182.16, -182.18 I-57 C 627 ([M +
H].sup.+) -- (DMSO-d.sub.6) .delta. 11.98 (s, 1H), 10.11 (s, 1H),
9.54 (s, 1H), 8.30-8.20 (m, 3H), 8.19-8.13 (m, 2H), 8.10-8.03 (m,
2H), 7.93 (d, J = 8.5 Hz, 2H), 7.39 (dd, J = 8.7, 6.4 Hz, 1H),
7.21-7.08 (m, 2H), 3.12 (hept, J = 6.7 Hz, 1H), 1.19 (d, J = 6.8
Hz, 6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -75.08 (d, J
= 7.4 Hz), -117.73, -179.04--182.36 (m) I-58 P* 454 ([M + H].sup.+)
-- (CDCl.sub.3) .delta. 8.65 (s, 1H), 8.10 (m, 2H), 7.93 (m, 2H),
7.77 (d, J = 8.3 Hz, 2H), 7.30 (m, 2H), 2.42 (s, 3H); .sup.19F NMR
(376 MHz, CDCl.sub.3) .delta. -73.89, -73.91, -73.92, -73.93,
-73.94, -73.95, -73.95, -73.97, -73.97, -79.19, -79.22, -121.15,
-121.18, -121.41, -121.43, -121.44, -121.46, -182.85, -182.87,
-182.89, -182.90 I-59 P* 468 ([M + H].sup.+) -- (CDCl.sub.3)
.delta. 10.09 (s, 1H), 8.72 (s, 1H), 8.39 (m, 2H), 8.01 (m, 2H),
7.95 (m, 2H), 7.80 (d, J = 8.3 Hz, 2H); .sup.19F NMR (376 MHz,
CDCl.sub.3) .delta. -73.84, -79.18, -121.08, -182.84 I-60 C 677 ([M
+ H].sup.+) -- (DMSO-d.sub.6) .delta. 11.98 (s, 1H), 10.11 (s, 1H),
9.55 (s, 1H), 8.31-8.20 (m, 3H), 8.20-8.13 (m, 2H), 8.11-8.03 (m,
2H), 7.92 (d, J = 8.5 Hz, 2H), 7.39 (dd, J = 8.7, 6.5 Hz, 1H),
7.23-7.07 (m, 2H), 3.12 (hept, J = 6.7 Hz, 1H), 1.19 (d, J = 6.9
Hz, 6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -73.44 (dtd,
J = 15.4, 8.1, 7.5, 3.0 Hz), -78.73 (d, J = 12.8 Hz), -117.73,
-120.00--122.33 (m), -182.26 (tt, J = 12.8, 6.4 Hz) I-61 P* 302 ([M
+ H].sup.+) -- (CDCl.sub.3) .delta. 8.61 (s, 1H), 8.11 (d, J = 8.16
Hz, 2H), 7.84 (d, J = 8.68 Hz, 2H), 7.67 (d, J = 8.68 Hz, 2H), 7.30
(d, J = 7.96 Hz, 2H), 2.43 (s, 3H), 1.98 (t, J = 18.12 Hz, 3H) I-62
P* 314 ([M + H].sup.+) 139-141 (CDCl.sub.3) .delta. 10.11 (s, 1H),
8.69 (s, 1H), 8.41 (d, J = 8.28 Hz, 2H), 8.02 (d, J = 8.28 Hz, 2H),
7.87 (d, J = 8.56 Hz, 2H), 7.71 (d, J = 8.56 Hz, 2H), 2.00 (t, J =
18.12 Hz, 3H) I-63 C 523 ([M + H].sup.+) -- (DMSO-d.sub.6) .delta.
11.98 (s, 1H), 10.11 (s, 1H), 9.49 (s, 1H), 8.21 (d, J = 0.8 Hz,
1H), 8.16 (d, J = 8.4 Hz, 2H), 8.12-8.03 (m, 4H), 7.85-7.76 (m,
2H), 7.39 (dd, J = 8.7, 6.4 Hz, 1H), 7.22-7.08 (m, 2H), 3.12 (hept,
J = 6.6 Hz, 1H), 2.04 (t, J = 18.9 Hz, 3H), 1.19 (d, J = 6.8 Hz,
6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -84.18, -117.72
I-64 C 577 ([M + H].sup.+) -- (DMSO-d.sub.6) .delta. 12.04 (s, 1H),
10.17 (s, 1H), 9.62 (s, 1H), 8.30 (d, J = 1.6 Hz, 1H), 8.28 (d, J =
4.6 Hz, 2H), 8.25-8.19 (m, 2H), 8.17-8.08 (m, 2H), 8.01 (d, J = 8.6
Hz, 2H), 7.45 (dd, J = 8.7, 6.4 Hz, 1H), 7.27-7.12 (m, 2H), 3.17
(hept, J = 6.9 Hz, 1H), 1.24 (d, J = 6.8 Hz, 6H); .sup.19F NMR (376
MHz, DMSO-d.sub.6) .delta. -84.03 (d, J = 2.6 Hz), -113.43, -117.72
I-65 C 527 ([M + H].sup.+) (DMSO-d.sub.6) .delta. 11.92 (s, 1H),
10.05 (s, 1H), 9.57 (s, 1H), 8.29-7.94 (m, 9H), 7.20 (ddd, J =
20.5, 9.6, 4.3 Hz, 2H), 7.06 (td, J = 8.4, 3.0 Hz, 1H), 3.18-3.03
(m, 1H), 1.19 (d, J = 6.8 Hz, 6H); .sup.19F NMR (376 MHz,
DMSO-d.sub.6) .delta. -60.81, -114.66 NMR spectral data were
acquired using a 400 MHz instrument unless otherwise noted.
P*--Prepared according to methods described in Crouse et al. PCT
Int. Appl. Publ. WO2009/102736 A1 and Brown, et al, WO 2011017504
A1.
TABLE-US-00004 TABLE 3 Structures for Compounds ID Structure 1C
##STR00096## 2C ##STR00097## 3C ##STR00098## 4C ##STR00099## 5C
##STR00100## 6C ##STR00101## 7C ##STR00102## 8C ##STR00103## 9C
##STR00104## 10C ##STR00105## 11C ##STR00106## 12C ##STR00107## 13C
##STR00108## 14C ##STR00109## 15C ##STR00110## 16C ##STR00111## 17C
##STR00112## 18C ##STR00113## 19C ##STR00114## 20C ##STR00115## 21C
##STR00116## 22C ##STR00117## 23C ##STR00118## 24C ##STR00119## 25C
##STR00120## 26C ##STR00121## 27C ##STR00122## 28C ##STR00123## 29C
##STR00124## 30C ##STR00125## 31C ##STR00126## 32C ##STR00127## 33C
##STR00128## 34C ##STR00129## 35C ##STR00130## 36C ##STR00131## 37C
##STR00132## 38C ##STR00133## 39C ##STR00134## 40C ##STR00135## 41C
##STR00136## 42C ##STR00137## 43C ##STR00138## 44C ##STR00139## 45C
##STR00140## 46C ##STR00141## 47C ##STR00142## 48C ##STR00143## 49C
##STR00144## 50C ##STR00145## 51C ##STR00146## 52C ##STR00147## 53C
##STR00148## 54C ##STR00149## 55C ##STR00150## 56C ##STR00151## 57C
##STR00152## 58C ##STR00153## 59C ##STR00154## 60C ##STR00155## 61C
##STR00156## 62C ##STR00157## 63C ##STR00158## 64C ##STR00159## 65C
##STR00160## 66C ##STR00161## 67C ##STR00162## 68C ##STR00163## 69C
##STR00164## 70C ##STR00165## 71C ##STR00166## 72C ##STR00167## 73C
##STR00168## 74C ##STR00169## 75C ##STR00170## 76C ##STR00171## 77C
##STR00172## 78C ##STR00173## 79C ##STR00174## 80C ##STR00175## 81C
##STR00176## 82C ##STR00177## 83C ##STR00178## 84C ##STR00179## 85C
##STR00180## 86C ##STR00181## 87C ##STR00182## 88C ##STR00183## 89C
##STR00184## 90C ##STR00185## 91C ##STR00186## 92C ##STR00187## 93C
##STR00188## 94C ##STR00189## 95C ##STR00190## 96C ##STR00191## 97C
##STR00192## 98C ##STR00193## 99C ##STR00194## 100C ##STR00195##
101C ##STR00196## 102C ##STR00197## 103C ##STR00198## 104C
##STR00199## 105C ##STR00200## 106C ##STR00201## 107C ##STR00202##
108C ##STR00203## 109C ##STR00204## 110C ##STR00205## 111C
##STR00206## 112C ##STR00207## 113C ##STR00208## 114C ##STR00209##
115C ##STR00210## 116C ##STR00211## 117C ##STR00212## 118C
##STR00213## 119C ##STR00214## 120C ##STR00215## 121C ##STR00216##
122C ##STR00217## 123C ##STR00218##
124C ##STR00219## 125C ##STR00220## 126C ##STR00221## 127C
##STR00222## 128C ##STR00223## 129C ##STR00224## 130C ##STR00225##
131C ##STR00226## 132C ##STR00227## 133C ##STR00228## 134C
##STR00229## 135C ##STR00230## 136C ##STR00231## 137C ##STR00232##
138C ##STR00233## 139C ##STR00234## 140C ##STR00235## 141C
##STR00236## 142C ##STR00237## 143C ##STR00238## 144C ##STR00239##
145C ##STR00240## 146C ##STR00241## 147C ##STR00242## 148C
##STR00243## 149C ##STR00244## 150C ##STR00245## 151C ##STR00246##
152C ##STR00247## 153C ##STR00248## 154C ##STR00249## 155C
##STR00250## 156C ##STR00251## 157C ##STR00252## 158C ##STR00253##
159C ##STR00254## 160C ##STR00255## 161C ##STR00256## 162C
##STR00257## 163C ##STR00258## 164C ##STR00259## 165C ##STR00260##
166C ##STR00261## 167C ##STR00262## 168C ##STR00263## 169C
##STR00264## 170C ##STR00265## 171C ##STR00266## 172C ##STR00267##
173C ##STR00268## 174C ##STR00269## 175C ##STR00270## 176C
##STR00271## 177C ##STR00272## 178C ##STR00273## 179C ##STR00274##
180C ##STR00275## 181C ##STR00276## 182C ##STR00277## 183C
##STR00278## 184C ##STR00279## 185C ##STR00280## 186C ##STR00281##
187C ##STR00282## 188C ##STR00283## 189C ##STR00284## 190C
##STR00285## 191C ##STR00286## 192C ##STR00287## 193C ##STR00288##
194C ##STR00289## 195C ##STR00290## 196C ##STR00291## 197C
##STR00292## 198C ##STR00293## 199C ##STR00294## 200C ##STR00295##
201C ##STR00296## 202C ##STR00297## 203C ##STR00298## 204C
##STR00299## 205C ##STR00300## 206C ##STR00301## 207C ##STR00302##
208C ##STR00303## 209C ##STR00304## 210C ##STR00305## 211C
##STR00306## 212C ##STR00307## 213C ##STR00308## 214C ##STR00309##
215C ##STR00310## 216C ##STR00311## 217C ##STR00312## 218C
##STR00313## 219C ##STR00314## 220C ##STR00315## 221C ##STR00316##
222C ##STR00317## 223C ##STR00318## 224C ##STR00319## 225C
##STR00320## 226C ##STR00321## 227C ##STR00322## 228C ##STR00323##
229C ##STR00324## 230C ##STR00325## 231C ##STR00326## 232C
##STR00327## 233C ##STR00328## 234C ##STR00329## 235C ##STR00330##
236C ##STR00331## 237C ##STR00332## 238C ##STR00333## 239C
##STR00334## 240C ##STR00335## 241C ##STR00336## 242C ##STR00337##
243C ##STR00338## 244C ##STR00339## 245C ##STR00340## 246C
##STR00341## 247C ##STR00342## 248C ##STR00343##
249C ##STR00344## 250C ##STR00345## 251C ##STR00346## 252C
##STR00347## 253C ##STR00348## 254C ##STR00349## 255C ##STR00350##
256C ##STR00351## 257C ##STR00352## 258C ##STR00353## 259C
##STR00354## 260C ##STR00355## 261C ##STR00356##
TABLE-US-00005 TABLE 4 Analytical Data for Compounds in Table 3
Synthesis ID Method MS mp (.degree. C.) .sup.1H NMR (.delta.).sup.1
1C D 540 (M+) -- (DMSO-d.sub.6) 8.61 (s, 1H), 8.48 (s, 1H), 8.22
(d, J = 8.24 Hz, 2H), 8.17 (s, 1H), 7.89 (d, J = 8.24 Hz, 2H), 7.80
(d, J = 8.28 Hz, 2H), 7.41 (d, J = 8.28 Hz, 2H), 7.19 (d, J = 8.24
Hz, 2H), 6.71 (d, J = 8.24 Hz, 2H), 2.99 (s, 6H), 2.42 (s, 3H) 2C D
580 (M+) 168-171 (DMSO-d.sub.6) 9.42 (s, 1H), 8.18-8.03 (m, 5H),
7.78-7.69 (m, 2H), 7.61 (d, J = 8.26 Hz, 2H), 7.44 (d, J = 8.24 Hz,
2H), 7.18 (m, 1H), 3.09-2.99 (m, 2H), 1.39-1.32 (m, 3H) 3C D 594
180-182 (DMSO-d.sub.6) 9.42 (s, 1H), 8.18-8.04 (m, 5H), 7.78-7.69
(m, 2H), 7.61 (d, J = 8.26 Hz, 2H), 7.48 (d, J = 8.24 Hz, 2H), 7.19
(m, 1H), 3.06-3.02 (m, 2H), 1.78-1.64 (m, 2H), 1.04-0.96 (m, 3H) 4C
D 629 (M+) (DMSO-d.sub.6) 8.57 (s, 1H), 8.48 (d, J = 5.5 Hz, 1H),
8.22 (d, J = 8.2 Hz, 2H), 7.91-7.75 (m, 5H), 7.38 (d, J = 8.7 Hz,
2H), 7.22-7.07 (m, 3H), 6.50-6.19 (m, 2H), 3.85 (d, J = 7.2 Hz,
1H), 3.75-3.64 (m, 1H), 2.33 (s, 6H) 5C E 636 (M+) (300 MHz,
CDCl.sub.3) 8.56 (s, 1H), 8.54 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),
7.89 (d, J = 8.2 Hz, 3H), 7.79 (d, J = 9.0 Hz, 2H), 7.38 (d, J =
8.7 Hz, 2H), 7.23-7.00 (m, 4H), 6.88-6.74 (m, 2H), 4.44 (s, 2H),
2.33 (s, 6H) 6C D 645 (M + H) 196-198 (methanol-d.sub.4) 9.16 (s,
1H), 8.46 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H), 8.03 (m, 6H), 7.52 (d,
J = 8.3 Hz, 4H), 7.28-6.91 (m, 3H), 4.39 (s, 2H), 2.08 (s, 6H) 7C E
636 (M+) (300 MHz, CDCl.sub.3) 8.56 (m, 2H), 8.23 (d, J = 8.3 Hz,
2H), 7.88 (d, J = 8.3 Hz, 3H), 7.79 (d, J = 9.0 Hz, 2H), 7.55-7.42
(m, 1H), 7.37 (d, J = 9.0 Hz, 2H), 7.20-7.01 (m, 3H), 6.89-6.68 (m,
2H), 4.30 (s, 2H), 2.28 (s, 6H) 8C E 684 (M+) (CDCl.sub.3) 8.57 (s,
1H), 8.52 (s, 1H), 8.24 (d, J = 8.3 Hz, 2H), 7.91-7.84 (m, 3H),
7.80 (d, J = 9.1 Hz, 2H), 7.39 (d, J = 8.6 Hz, 4H), 7.18-7.03 (m,
5H), 4.32 (s, 2H), 2.29 (s, 6H) 9C E 620 (M+) (CDCl.sub.3) 8.57 (s,
1H), 8.47 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz,
2H), 7.80 (m, 3H), 7.39 (d, J = 8.4 Hz, 2H), 7.21-7.10 (m, 3H),
3.93 (s, 2H), 2.35 (s, 6H), 0.13 (s, 9H) 10C D 600 (M+)
(DMSO-d.sub.6) 8.57 (s, 1H), 8.54 (s, 1H), 8.23 (d, J = 8.3 Hz,
2H), 7.89 (d, J = 8.3 Hz, 2H), 7.87 (s, 1H), 7.80 (d, J = 9.0 Hz,
2H), 7.44-7.32 (m, 4H), 7.31-7.19 (m, 3H), 7.19-7.00 (m, 3H), 4.34
(s, 2H), 2.31 (s, 6H) 11C D 618 (M+) (DMSO-d.sub.6) 8.57 (s, 1H),
8.55 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.89 (d, J = 8.3 Hz, 2H),
7.86 (s, 1H), 7.83-7.73 (m, 2H), 7.48 (td, J = 7.6, 1.7 Hz, 1H),
7.38 (d, J = 8.5 Hz, 2H), 7.23-6.91 (m, 6H), 4.39 (s, 2H), 2.30 (s,
6H) 12C D 658 (M+) (DMSO-d.sub.6) 8.57 (s, 1H), 8.51 (s, 1H), 8.23
(d, J = 8.3 Hz, 2H), 7.94 (d, J = 8.3 Hz, 2H), 7.88 (d, J = 8.2 Hz,
2H), 7.86 (s, 1H), 7.79 (d, J = 9.0 Hz, 2H), 7.44 (d, J = 8.3 Hz,
2H), 7.38 (d, J = 8.6 Hz, 2H), 7.20-7.05 (m, 3H), 4.35 (s, 2H),
3.88 (s, 3H), 2.28 (s, 6H) 13C E 679 (M+) (DMSO-d.sub.6) 8.59 (s,
1H), 8.51 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.93-7.76 (m, 7H),
7.53 (d, J = 8.2 Hz, 2H), 7.39 (d, J = 8.7 Hz, 2H), 7.20-7.06 (m,
3H), 4.88 (s, 2H), 4.36 (s, 2H), 2.28 (s, 6H) 14C E 658 (M+)
(CDCl.sub.3) 8.57 (s, 1H), 8.52 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),
7.91-7.85 (m, 4H), 7.80 (d, J = 9.1 Hz, 2H), 7.73 (d, J = 6.8 Hz,
1H), 7.52 (dd, J = 8.8, 6.9 Hz, 1H), 7.39 (d, J = 9.0 Hz, 2H),
7.13-7.01 (m, 3H), 4.88 (s, 2H), 2.27 (s, 6H) 15C E 667 (M+)
(CDCl.sub.3) 8.57 (s, 1H), 8.25-8.14 (m, 3H), 7.94-7.66 (m, 7H),
7.52-7.35 (m, 6H), 7.16-7.03 (m, 3H), 4.54 (s, 2H), 2.32 (s, 6H)
16C E 658 (M+) (CDCl.sub.3) 8.57 (s, 1H), 8.49 (s, 1H), 8.24 (d, J
= 8.4 Hz, 2H), 7.88 (d, J = 8.3 Hz, 2H), 7.83-7.77 (m, 3H), 7.39
(d, J = 8.3 Hz, 2H), 7.19-7.07 (m, 3H), 6.69-6.65 (m, 1H),
6.39-6.35 (m, 1H), 4.36 (s, 2H), 2.29 (s, 6H) 17C E 678 (M+)
(CDCl.sub.3) 8.58 (s, 1H), 8.50 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),
7.94-7.74 (m, 7H), 7.59 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz,
2H), 7.20-7.04 (m, 3H), 4.37 (s, 2H), 3.01 (s, 3H), 2.29 (s, 6H)
18C E 773 (M+) (CDCl.sub.3) 8.59 (s, 1H), 8.46 (s, 1H), 8.22 (d, J
= 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H), 7.83-7.75 (m, 3H), 7.63
(d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.4 Hz,
2H), 7.17-7.05 (m, 3H), 7.03-6.98 (m, 3H), 6.89 (t, J = 8.6 Hz,
2H), 4.30 (s, 2H), 2.24 (s, 6H) 19C E 728 (M+) (CDCl.sub.3) 8.59
(s, 2H), 8.26 (d, J = 8.3 Hz, 2H), 7.93 (d, J = 8.3 Hz, 2H), 7.89
(s, 1H), 7.82 (d, J = 9.1 Hz, 2H), 7.40 (d, J = 8.3 Hz, 2H),
7.20-7.05 (m, 3H), 6.86 (s, 1H), 4.49 (s, 2H), 3.98 (s, 3H), 2.31
(s, 6H) 20C E 681 (M+) (CDCl.sub.3) 8.58 (s, 1H), 8.38 (s, 1H),
8.23 (d, J = 8.3 Hz, 2H), 7.86 (d, J = 8.3 Hz, 3H), 7.81 (d, J =
9.1 Hz, 2H), 7.67-7.63 (m, 2H), 7.46-7.36 (m, 5H), 7.18-7.05 (m,
3H), 4.24 (s, 2H), 2.47 (s, 3H), 2.29 (s, 6H) 21C E 596 (M+)
(DMSO-d.sub.6) 8.58 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 7.80 (d, J =
9.0 Hz, 2H), 7.47-7.35 (m, 4H), 7.21-6.93 (m, 5H), 3.68 (t, J = 5.4
Hz, 2H), 3.35 (s, 3H), 2.65 (t, J = 6.2 Hz, 2H), 2.29 (s, 6H) 22C E
626 (M+) (DMSO-d.sub.6) 8.59 (s, 1H), 8.52 (s, 1H), 8.23 (d, J =
8.3 Hz, 2H), 7.95-7.75 (m, 5H), 7.39 (d, J = 8.4 Hz, 2H), 7.21-7.06
(m, 3H), 5.80 (s, 2H), 4.12 (s, 2H), 3.69-3.50 (m, 2H), 2.31 (s,
6H), 1.35-1.11 (m, 3H) 23C E 731 (M+) (DMSO-d.sub.6) 8.58 (s, 1H),
8.50 (s, 1H), 8.22 (d, J = 8.2 Hz, 2H), 7.93-7.70 (m, 5H),
7.45-7.28 (m, 8H), 7.23-7.03 (m, 3H), 5.79 (s, 2H), 5.38-5.27 (m,
1H), 5.11 (s, 2H), 4.07-3.98 (m, 2H), 2.30 (s, 6H) 24C E 626 (M+)
(DMSO-d.sub.6) 8.58 (s, 1H), 8.51 (s, 1H), 8.22 (d, J = 8.3 Hz,
2H), 7.93-7.73 (m, 5H), 7.39 (d, J = 8.9 Hz, 2H), 7.21-7.07 (m,
3H), 5.76 (s, 2H), 5.05-4.70 (m, 1H), 2.32 (s, 6H), 1.38-1.17 (m,
6H) 25C E 610 (M+) (DMSO-d.sub.6) 8.59 (s, 1H), 8.52 (s, 1H), 8.23
(d, J = 8.3 Hz, 2H), 7.91-7.79 (m, 5H), 7.40 (d, J = 8.5 Hz, 2H),
7.18-7.06 (m, 3H), 5.73 (s, 2H), 2.70-2.45 (m, 1H), 2.32 (s, 6H),
1.15 (s, 6H) 26C E 654 (M+) (DMSO-d.sub.6) 8.58 (s, 1H), 8.21 (d, J
= 8.4 Hz, 2H), 7.98 (d, J = 8.4 Hz, 2H), 7.81 (d, J = 6.9 Hz, 2H),
7.69 (s, 1H), 7.40 (d, J = 8.8 Hz, 2H), 6.63 (s, 2H), 5.73 (s, 2H),
3.80 (s, 3H), 2.64-2.53 (m, 1H), 2.58 (s, 3H), 2.28 (s, 6H), 1.17
(d, J = 7.0 Hz, 6H) 27C E 640 (M+) (DMSO-d.sub.6) 8.58 (s, 1H),
8.50 (s, 1H), 8.23 (d, J = 8.2 Hz, 2H), 7.88 (d, J = 8.3 Hz, 2H),
7.81 (d, J = 9.0 Hz, 2H), 7.74 (s, 1H), 7.39 (d, J = 8.6 Hz, 2H),
6.63 (s, 2H), 5.71 (s, 2H), 3.79 (s, 3H), 2.74-2.43 (m, 1H), 2.27
(s, 6H), 1.16 (d, J = 7.0 Hz, 6H) 28C E 761 (M+) (300 MHz,
CDCl.sub.3) 8.58 (s, 1H), 8.48 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H),
7.87 (d, J = 8.4 Hz, 2H), 7.80 (d, J = 9.0 Hz, 2H), 7.74 (s, 1H),
7.45-7.28 (m, 7H), 6.63 (s, 2H), 5.78 (s, 2H), 5.29 (m, 1H), 5.12
(s, 2H), 4.03 (d, J = 5.6 Hz, 2H), 3.79 (s, 3H), 2.27 (s, 6H) 29C E
656 (M+) (300 MHz, CDCl.sub.3) 8.58 (s, 1H), 8.49 (s, 1H), 8.23 (d,
J = 8.3 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 7.81 (d, J = 9.0 Hz,
2H), 7.72 (s, 1H), 7.40 (d, J = 8.7 Hz, 2H), 6.63 (s, 2H), 5.78 (s,
2H), 4.11 (s, 2H), 3.80 (s, 3H), 3.59 (q, J = 7.0 Hz, 2H), 2.27 (s,
6H), 1.24 (t, J = 7.1 Hz, 3H) 30C E 697 (M+) (300 MHz, CDCl.sub.3)
8.60 (s, 1H), 8.50 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.88 (d, J =
8.2 Hz, 2H), 7.82 (s, 1H), 7.80 (d, J = 9.0 Hz, 2H), 7.38 (d, J =
8.8 Hz, 3H), 7.23-7.02 (m, 3H), 5.78 (s, 2H), 3.96 (s, 2H), 2.31
(s, 6H), 1.44 (s, 9H) 31C E 582 (M+) (300 MHz, CDCl.sub.3) 8.58 (s,
1H), 8.52 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.88 (m, 3H), 7.80 (d,
J = 9.0 Hz, 2H), 7.38 (d, J = 8.6 Hz, 2H), 7.14 (m, 3H), 5.72 (s,
2H), 2.32 (s, 6H), 2.09 (s, 3H) 32C E 697 (M+) (CDCl.sub.3)
(Mixture of atropisomers) [8.61 (s), 8.58 (s), 8.56 (s), 8.51 (s),
8.37 (d, J = 8.3 Hz), 8.23 (d, J = 8.4 Hz), 8.21-8.14 (m), 8.00 (d,
J = 8.4 Hz), 7.89 (d, J = 8.2 Hz), 7.84-7.77 (m), 7.45-7.35 (m);
11H], 6.94 (s, 2H), [5.87 (s), 5.80 (s); 2H], [4.12 (s), 4.11 (s);
2H], 3.83 (s, 3H), 3.69-3.44 (m, 2H), 1.38-1.10 (m, 3H) 33C E 697
(M+) (CDCl.sub.3) 8.57 (s, 1H), 8.51 (s, 1H), 8.23 (d, J = 8.3 Hz,
2H), 7.88 (d, J = 8.4 Hz, 2H), 7.83-7.77 (m, 3H), 7.39 (d, J = 8.4
Hz, 2H), 6.94 (s, 2H), 5.76 (s, 2H), 4.96-4.77 (m, 1H), 3.82 (s,
3H), 1.30 (d, J = 6.3 Hz, 6H) 34C E 681 (M+) (CDCl.sub.3) 8.57 (s,
1H), 8.51 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.92-7.76 (m, 5H),
7.39 (d, J = 8.4 Hz, 2H), 6.93 (s, 2H), 5.73 (s, 2H), 3.82 (s, 3H),
2.59 (m, 1H), 1.17 (d, J = 7.0 Hz, 6H) 35C E 636 (M+) (CDCl.sub.3)
8.57 (s, 1H), 8.50 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.92-7.73 (m,
5H), 7.38 (d, J = 8.3 Hz, 2H), 7.20-6.92 (m, 3H), 5.72 (s, 2H),
2.94-2.63 (m, 1H), 2.31 (s, 6H), 2.02-1.38 (m, 8H) 36C E 624 (M+)
(CDCl.sub.3) 8.56 (s, 1H), 8.49 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),
7.87 (d, J = 8.3 Hz, 2H), 7.84 (s, 1H), 7.79 (d, J = 9.0 Hz, 2H),
7.38 (d, J = 8.4 Hz, 2H), 7.19-7.05 (m, 3H), 5.71 (s, 2H), 2.31 (s,
6H), 1.20 (s, 9H) 37C E 691 (M + H) (CDCl.sub.3) 8.59 (s, 1H), 8.50
(s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.93-7.77 (m, 4H), 7.72 (s, 1H),
7.40 (d, J = 9.0 Hz, 2H), 6.63 (s, 2H), 5.71 (s, 2H), 3.80 (s, 3H),
2.68-2.48 (m, 1H), 2.28 (s, 6H), 1.16 (d, J = 7.0 Hz, 6H) 38C E 724
(M+) (CDCl.sub.3) 8.58 (s, 1H), 8.47 (s, 1H), 8.23 (d, J = 8.3 Hz,
2H), 7.87 (d, J = 8.3 Hz, 2H), 7.81 (d, J = 9.1 Hz, 2H), 7.71 (s,
1H), 7.39 (d, J = 9.0 Hz, 2H), 6.64 (s, 2H), 5.76 (dd, J = 37.3,
11.0 Hz, 2H), 4.19 (q, J = 6.9 Hz, 1H), 4.14-3.97 (m, 1H), 3.80 (s,
3H), 3.79-3.68 (m, 1H), 2.27 (s, 6H), 1.47 (d, J = 6.9 Hz, 3H) 39C
E 694 (M+) (CDCl.sub.3) 8.58 (s, 1H), 8.48 (s, 1H), 8.24 (d, J =
8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.83 (s, 1H), 7.81 (d, J =
9.1 Hz, 2H), 7.39 (d, J = 8.3 Hz, 2H), 7.23-6.99 (m, 3H), 5.77 (dd,
J = 36.4, 11.0 Hz, 2H), 4.19 (q, J = 6.9 Hz, 1H), 4.14-3.97 (m,
1H), 3.84-3.65 (m, 1H), 2.31 (s, 6H), 1.47 (d, J = 6.9 Hz, 3H) 40C
E 654 (M+) (CDCl.sub.3) 8.57 (s, 1H), 8.48 (s, 1H), 8.23 (d, J =
8.3 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.80 (d, J = 9.0 Hz, 2H),
7.72 (s, 1H), 7.38 (d, J = 8.4 Hz, 2H), 6.62 (s, 2H), 5.70 (s, 2H),
3.79 (s, 3H), 2.27 (s, 6H), 1.20 (s, 9H) 41C E 670 (M+)
(CDCl.sub.3) 8.58 (s, 1H), 8.49 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),
7.87 (d, J = 8.3 Hz, 2H), 7.84 (s, 1H), 7.80 (d, J = 9.0 Hz, 2H),
7.38 (d, J = 8.4 Hz, 2H), 7.23-6.96 (m, 3H), 5.77 (dd, J = 27.4,
10.9 Hz, 2H), 4.07 (q, J = 6.9 Hz, 1H), 3.78-3.70 (m, 1H),
3.66-3.39 (m, 3H), 3.35 (s, 3H), 2.31 (s, 6H), 1.42 (d, J = 6.9 Hz,
3H) 42C E 700 (M+) (CDCl.sub.3) 8.58 (s, 1H), 8.48 (s, 1H), 8.23
(d, J = 8.4 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.80 (d, J = 9.1 Hz,
2H), 7.71 (s, 1H), 7.39 (d, J = 8.3 Hz, 2H), 6.63 (s, 2H), 5.76
(dd, J = 27.8, 10.9 Hz, 2H), 4.07 (q, J = 6.9 Hz, 1H),
3.79 (s, 3H), 3.79-3.70 (m, 1H), 3.63-3.45 (m, 3H), 3.35 (s, 3H),
2.27 (s, 6H), 1.42 (d, J = 6.9 Hz, 3H) 43C E 666 (M+) (CDCl.sub.3)
8.57 (s, 1H), 8.49 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.87 (d, J =
8.3 Hz, 2H), 7.79 (d, J = 9.1 Hz, 2H), 7.74 (s, 1H), 7.38 (d, J =
8.3 Hz, 2H), 6.62 (s, 2H), 5.71 (s, 2H), 3.79 (s, 3H), 2.85-2.65
(m, 1H), 2.27 (s, 6H), 1.98-1.51 (m, 8H) 44C E 668 (M+)
(CDCl.sub.3) 8.59 (s, 1H), 8.55 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H),
7.87 (d, J = 8.3 Hz, 2H), 7.84-7.74 (m, 3H), 7.38 (d, J = 8.4 Hz,
2H), 6.63 (s, 2H), 5.85-5.73 (m, 2H), 4.54-4.47 (m, 1H), 4.03 (dd,
J = 14.7, 6.9 Hz, 1H), 3.91 (dd, J = 13.8, 7.4 Hz, 1H), 3.79 (s,
3H), 2.27 (s, 6H), 2.09-1.83 (m, 4H) 45C E 746 (M + H) 132-137
(CDCl.sub.3) 8.68 (s, 1H), 8.49 (s, 1H), 8.24 (d, J = 8.3 Hz, 2H),
7.93 (d, J = 8.4 Hz, 2H), 7.88 (d, J = 8.3 Hz, 2H), 7.81 (d, J =
8.5 Hz, 2H), 7.73 (s, 1H), 7.35 (s, 5H), 6.64 (s, 2H), 5.78 (s,
2H), 5.24 (s, 1H), 5.12 (s, 2H), 4.04 (d, J = 5.5 Hz, 2H), 3.80 (s,
3H), 2.28 (s, 6H) 46C E 624 108-113 (CDCl.sub.3) 8.68 (s, 1H), 8.50
(s, 1H), 8.24 (d, J = 8.3 Hz, 2H), 7.98-7.69 (m, 7H), 6.63 (s, 2H),
5.71 (s, 2H), 3.80 (s, 3H), 2.59 (heptet, J = 7.0 Hz, 1H), 2.29 (d,
J = 6.9 Hz, 6H), 1.16 (d, J = 7.0 Hz, 6H) 47C E 149-151
(acetone-d.sub.6) 9.20 (s, 1H), 8.52 (s, 1H), 8.40-8.21 (m, 2H),
8.21-8.01 (m, 4H), 7.61 (d, J = 8.3 Hz, 2H), 7.32-6.94 (m, 3H),
3.83 (s, 2H), 2.34 (s, 6H) 48C E 599 (M + H) 128-137
(acetone-d.sub.6) 9.18 (s, 1H), 8.83 (s, 1H), 8.67-7.82 (m, 8H),
7.60 (d, J = 8.4 Hz, 2H), 6.78 (s, 2H), 3.99-3.72 (m, 3H),
2.41-2.20 (m, 6H) 49C E 619 (M + H) 177-185 (methanol-d.sub.4) 9.23
(s, 1H), 8.62 (s, 1H), 8.29 (m, 2H), 8.17-7.98 (m, 4H), 7.60-7.45
(m, 2H), 7.41-7.19 (m, 3H), 4.22 (s, 2H), 2.34 (s, 6H) 50C E 635 (M
+ H) 193-196 (methanol-d.sub.4) 9.23 (s, 1H), 8.57 (s, 1H), 8.28
(m, 3H), 8.09-7.98 (m, 4H), 7.50 (m, 4H), 4.19-4.11 (m, 2H), 3.85
(s, 3H), 2.36 (s, 3H) 51C E 649 (M + H) 176-179 (methanol-d.sub.4)
9.23 (s, 1H), 8.60 (s, 1H), 8.30 (m, 2H), 8.14-8.00 (m, 4H), 7.52
(m, 2H), 6.81 (s, 2H), 4.22 (s, 2H), 3.84-3.81 (m, 3H), 2.33 (s,
6H) 52C E 599 (M + H) 168-178 (methanol-d.sub.4) 9.21 (s, 1H), 8.44
(s, 1H), 8.27 (d, J = 8.1 Hz, 2H), 8.09-7.98 (m, 4H), 7.52 (d, J =
8.3 Hz, 2H), 7.40 (d, J = 8.7 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H),
5.40 (s, 1H), 4.37-4.13 (m, 2H), 3.79 (s, 3H), 1.79 (m, 3H) 53C E
617 (M + H) 168-170 (methanol-d.sub.4) 9.21 (s, 1H), 8.44 (m, 1H),
8.28 (d, J = 8.2 Hz, 2H), 8.11-7.99 (m, 4H), 7.52 (d, J = 8.4 Hz,
2H), 7.25 (m, 2H), 7.14 (t, J = 8.5 Hz, 1H), 5.42 (m, 1H), 4.25 (m,
2H), 3.88 (s, 3H), 1.75 (m, 3H) 54C E 569 (M + H) 167-170
(methanol-d.sub.4) 9.23 (s, 1H), 8.46 (s, 1H), 8.27 (m, 2H), 8.05
(m, 4H), 7.57-7.39 (m, 7H), 5.41 (m, 1H), 4.24 (m, 2H), 1.79 (m,
3H) 55C E 624 (M + H) 90-97 (methanol-d.sub.4) 9.12 (s, 1H), 8.46
(s, 1H), 8.14 (m, 2H), 7.99 (m, 3H), 7.78 (s, 1H), 7.49 (d, J = 8.5
Hz, 2H), 7.12 (m, 3H), 3.69 (s, 2H), 3.22-2.80 (m, 2H), 2.25 (s,
6H), 2.03 (s, 2H), 1.93-1.66 (m, 1H), 0.92 (m, J = 9.7 Hz, 6H) 56C
E 765 (M + H) 148-151 (methanol-d.sub.4) 9.18 (s, 1H), 8.59 (s,
1H), 8.30 (d, J = 8.1 Hz, 2H), 8.12 (m, 2H), 8.07-8.00 (m, 2H),
7.58-7.43 (m, 2H), 7.33 (dd, J = 8.6, 6.5 Hz, 1H), 7.25 (d, J = 7.6
Hz, 2H), 4.02 (m, 2H), 3.97-3.75 (m, 2H), 3.21 (d, J = 6.9 Hz, 2H),
2.90 (m, 1H), 2.59 (m, 1H), 2.35 (s, 6H), 1.84 (m, 2H), 1.78-1.63
(m, 2H), 1.44 (s, 9H), 1.29 (m, 3H) 57C E 737 (M + H) 151-153
(methanol-d.sub.4) 9.20 (s, 1H), 8.65 (s, 1H), 8.30 (m, 2H),
8.21-7.96 (m, 4H), 7.53 (d, J = 8.4 Hz, 2H), 7.35 (dd, J = 8.5, 6.5
Hz, 1H), 7.28 (d, J = 7.5 Hz, 2H), 4.44 (s, 2H), 3.91-3.40 (m, 9H),
2.38 (s, 6H), 1.50 (s, 9H) 58C E 725 (M + H) 125-127
(methanol-d.sub.4) 9.18 (s, 1H), 8.61 (s, 1H), 8.31 (m, 2H), 8.14
(m, 2H), 8.06 (d, J = 9.0 Hz, 2H), 7.53 (d, J = 8.5 Hz, 2H), 7.32
(dt, J = 26.0, 7.0 Hz, 3H), 4.02 (s, 2H), 3.38-3.34 (m, 2H),
3.22-3.03 (m, 2H), 2.37 (s, 6H), 1.74 (m, 2H), 1.45 (s, 9H) 59C E
755 (M + H) 147-149 (methanol-d.sub.4) 9.18 (s, 1H), 8.62 (s, 1H),
8.38-7.97 (m, 6H), 7.51 (d, J = 8.4 Hz, 2H), 7.32 (dd, J = 8.5, 6.6
Hz, 1H), 7.25 (d, J = 7.6 Hz, 2H), 4.40 (s, 1H), 4.06 (m, 2H),
3.91-3.74 (m, 2H), 3.56-3.41 (m, 1H), 2.36 (s, 6H), 1.44 (s, 9H)
60C E 755 (M + H) 136-139 (methanol-d.sub.4) 9.16 (s, 1H), 8.58 (s,
1H), 8.28 (d, J = 7.4 Hz, 2H), 8.16-7.76 (m, 4H), 7.52 (p, J = 8.8
Hz, 2H), 6.83 (m, 2H), 4.04 (d, J = 8.5 Hz, 2H), 3.90-3.73 (m, 3H),
3.55-3.37 (m, 2H), 3.14-2.75 (m, 3H), 2.30 (s, 6H), 1.99-1.80 (m,
2H), 1.43-1.31 (m, 2H) 61C E 738 (M + H) 70-79 (methanol-d.sub.4)
9.12 (s, 1H), 8.12-8.07 (m, dec 2H), 8.02-7.96 (m, 2H), 7.55-7.50
(m, 2H), 7.50-7.45 (m, 2H), 7.43 (d, J = 7.7 Hz, 1H), 7.31 (d, J =
7.6 Hz, 2H), 4.03 (s, 2H), 3.25 (dt, J = 15.5, 7.0 Hz, 4H), 2.84
(s, 3H), 2.04 (s, 6H), 1.81-1.66 (m, 2H), 1.44 (s, 9H) 62C K 665 (M
+ H) 110-120 (methanol-d.sub.4) .delta. 9.18 (s, 1H), 8.56 (m, 1H),
8.26 (m, 2H), 8.16-7.84 (m, 4H), 7.52 (m, 2H), 7.27 (m, 1H), 7.22
(m, 2H), 4.00 (s, 2H), 3.28 (m, 3H), 3.06-2.83 (m, 1H), 2.75 (t, J
= 12.2 Hz, 1H), 2.34 (s, 6H), 2.21-1.83 (m, 4H), 1.72 (m, 1H),
1.47-1.19 (m, 2H) 63C K 655 (M + H) 98-110 (methanol-d.sub.4) 9.18
(s, 1H), 8.63 (s, 1H), 8.28 (m, 2H), 8.13-7.97 (m, 4H), 7.51 (d, J
= 8.3 Hz, 2H), 7.31 (dd, J = 8.5, 6.5 Hz, 1H), 7.24 (d, J = 7.6 Hz,
2H), 4.32-4.07 (m, 3H), 3.98-3.81 (m, 1H), 3.72 (s, 1H), 2.35 (s,
6H) 64C K 655 (M + H) 83-112 (methanol-d.sub.4) 9.19 (s, 1H), 8.58
(s, 1H), 8.28 (m, 2H), 8.14-7.97 (m, 4H), 7.51 (m, 2H), 6.78 (s,
2H), 4.00 (m, 2H), 3.81 (s, 3H), 3.10-2.93 (m, 4H), 2.30 (s, 6H),
1.91 (m, 2H) 65C K 667 (M + H) 128 dec (methanol-d.sub.4) 9.20 (s,
1H), 8.65 (s, 1H), 8.27 (m 2H), 8.11-7.99 (m, 4H), 7.52 (d, J = 8.3
Hz, 2H), 6.78 (s, 2H), 4.40 (s, 2H), 3.87 (m, 4H), 3.53 (s, 3H),
2.32 (s, 6H), 1.33 (m, 4H) 66C K 625 (M + H) 100-105
(methanol-d.sub.4) 9.20 (s, 1H), 8.56 (s, 1H), 8.27 (m, 2H),
8.12-7.99 (m, 3H), 7.53 (d, J = 8.4 Hz, 2H), 7.24 (m, 4H), 3.99 (s,
2H), 3.42 (m, 2H), 3.05 (m, 2H), 2.36 (s, 6H), 1.99-1.88 (m, 2H)
67C K 636 (M + H) 237-240 (methanol-d.sub.4) 9.20 (s, 1H), 8.74 (s,
1H), dec 8.33-8.25 (m, 2H), 8.12-7.98 (m, 4H), 7.53 (d, J = 8.3 Hz,
2H), 7.33 (dd, J = 8.5, 6.4 Hz, 1H), 7.26 (d, J = 7.5 Hz, 2H), 4.55
(s, 2H), 3.92 (m, 4H), 3.37 (m, 2H), 3.31 (m, 2H), 2.38 (s, 6H) 69C
F 581 (M + H) 188-190 (CDCl.sub.3) 8.56 (s, 1H), 8.33 (s, 1H), 8.22
(d, J = 8.1 Hz, 2H), 7.90-7.70 (m, 4H), 7.39 (d, J = 8.7 Hz, 2H),
6.72 (s, 2H), 4.01 (s, 2H), 3.87-3.73 (s, 3H), 2.18 (s, 6H) 70C F
592 (M+) 134-138 (CDCl.sub.3) 8.65 (s, 1H), 8.31 (s, 1H), 8.23 (d,
J = 8.3 Hz, 2H), 7.83 (m, 4H), 7.50 (d, J = 8.1 Hz, 2H), 7.45-7.38
(m, 3H), 4.05 (s, 2H) 71C F 551 (M + H) 104-111 (CDCl.sub.3) 8.62
(s, 1H), 8.32 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.88-7.74 (m, 4H),
7.40 (d, J = 8.3 Hz, 2H), 7.34-7.26 (m, 1H), 7.20 (d, J = 7.5 Hz,
2H), 4.02 (s, 2H), 2.22 (s, 6H) 72C F 565 (M + H) 118-121
(CDCl.sub.3) 8.58 (s, 1H), 8.33 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),
7.81 (m, 4H), 7.40 (d, J = 8.3 Hz, 2H), 7.01 (d, J = 0.4 Hz, 2H),
4.01 (s, 2H), 2.34 (s, 3H), 2.17 (s, 6H) 73C F 565 (M + H) 145-150
(CDCl.sub.3) 8.58 (s, 1H), 8.30 (s, 1H), 8.23 (d, J = 8.3 Hz, 1H),
7.81 (m, 2H), 7.49 (d, J = 4.0 Hz, 1H), 7.40 (d, J = 8.4 Hz, 1H),
7.34 (s, 1H), 7.18 (d, J = 7.8 Hz, 1H), 4.01 (d, J = 1.4 Hz, 1H),
2.83 (heptet, J = 6.8 Hz, 1H), 1.23 (t, J = 6.6 Hz, 3H). 74C G 682
(M + H) 190-193 (methanol-d.sub.4) 9.20 (s, 1H), 8.38 (s, 1H),
8.31-8.24 (m, 2H), 8.08-8.00 (m, 2H), 7.95-7.88 (m, 2H), 7.55-7.48
(m, 3H), 7.48-7.36 (m, 5H), 7.31 (d, J = 7.7 Hz, 2H), 3.60 (q, J =
7.2 Hz, 4H), 2.20 (s, 6H), 1.07 (t, J = 7.2 Hz, 6H); 75C G 617 (M+)
(CDCl.sub.3) 8.56 (s, 1H), 8.23 (s, 1H), 8.19 (d, J = 8.4 Hz, 2H),
7.84-7.73 (m, 5H), 7.41-7.33 (m, 3H), 7.21 (d, J = 7.2 Hz, 2H),
7.16 (s, 1H), 7.12 (d, J = 3.2 Hz, 1H), 2.20 (s, 6H). 76C G 711
(M+) (CDCl.sub.3) 8.56 (s, 1H), 8.25 (s, 1H), 8.20 (d, J = 8.4 Hz,
2H), 7.80 (dd, J = 8.7, 5.6 Hz, 4H), 7.48-7.34 (m, 8H), 7.26 (d, J
= 7.7 Hz, 2H), 7.08 (s, 1H), 2.20 (s, 6H) 77C G 655 (M + H) 261-263
(methanol-d.sub.4) 9.14 (s, 1H), 8.21-8.13 (m, 3H), 8.06-7.99 (m,
2H), 7.86-7.75 (m, 4H), 7.50 (d, J = 8.3 Hz, 2H), 7.28-7.18 (m,
3H), 7.14 (d, J = 7.9 Hz, 2H), 6.72 (s, 1H), 0.09--0.09 (m, 6H) 78C
G 694 (M + H) (CDCl.sub.3) 8.55 (s, 1H), 8.22 (s, 1H), 8.18 (d, J =
8.3 Hz, 2H), 7.79 (dd, J = 8.7, 5.1 Hz, 4H), 7.37 (d, J = 9.0 Hz,
2H), 7.23-6.94 (m, 7H), 6.26 (s, 1H), 2.17 (s, 6H) 79C G 678 (M +
H) (CDCl.sub.3) 8.55 (s, 1H), 8.23 (s, 1H), 8.19 (d, J = 8.3 Hz,
2H), 7.79 (d, J = 8.7 Hz, 4H), 7.43 (d, J = 8.3 Hz, 2H), 7.37 (d, J
= 8.9 Hz, 2H), 7.23-7.16 (m, 3H), 7.08 (d, J = 7.4 Hz, 2H), 6.35
(s, 1H), 2.18 (s, 6H) 80C G 609 (M + H) 215-219 (methanol-d.sub.4)
9.23 (s, 1H), 8.40 (s, 1H), 8.26 (m, 2H), 8.22 (s, 1H), 8.07-8.00
(m, 3H), 7.91 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.3 Hz, 2H), 6.90
(s, 1H), 3.88 (s, 3H), 2.13 (s, 6H) 81C I 551 (M + H) 209-213
(CDCl.sub.3) 9.42 (s, 1H), 8.59 (s, 1H), 8.28 (d, J = 8.4 Hz, 2H),
8.01 (d, J = 8.3 Hz, 2H), 7.80-7.77 (m, 2H), 7.43-7.34 (m, 2H),
7.07 (d, J = 7.5 Hz, 2H), 6.98 (dd, J = 8.2, 6.7 Hz, 1H), 3.90 (s,
2H), 2.17 (s, 6H) 82C I 565 (M + H) 225-232 (CDCl.sub.3) 9.46 (s,
1H), 8.60 (s, 1H), 8.29 (d, J = 8.4 Hz, 2H), 8.02 (d, J = 8.4 Hz,
2H), 7.89-7.76 (m, 2H), 7.40 (d, J = 8.3 Hz, 2H), 6.88 (s, 2H),
3.90 (s, 2H), 2.28 (s, 3H), 2.13 (s, 6H). 83C I 581 (M + H) 211-215
(CDCl.sub.3) 9.44 (s, 1H), 8.60 (s, 1H), 8.30 (d, J = 8.4 Hz, 2H),
8.02 (d, J = 8.4 Hz, 2H), 7.82 (d, J = 9.1 Hz, 2H), 7.40 (d, J =
8.3 Hz, 2H), 6.63 (s, 2H), 3.90 (s, 2H), 3.78 (s, 3H), 2.15 (s, 6H)
84C I 591 250 dec (CDCl.sub.3) 9.42 (s, 1H), 8.40 (s, 1H), 8.18 (d,
J = 8.24 Hz, 2H), 8.07 (d, J = 8.28 Hz, 2H), 7.89 (d, J = 8.24 Hz,
2H), 7.76 (d, J = 8.28 Hz, 2H), 7.64-7.58 (m, 3H), 4.42 (s, 2H) 85C
I 551 (M + H) 146-149 (CDCl.sub.3) .delta. 9.36 (s, 1H), 8.60 (s,
1H), 8.30 (d, J = 8.4 Hz, 2H), 8.01 (d, J = 8.4 Hz, 2H), 7.86-7.77
(m, 2H), 7.40 (d, J = 8.3 Hz, 2H), 7.32 (dd, J = 6.9, 2.3 Hz, 1H),
7.24-7.12 (m, 2H), 6.91 (dd, J = 7.1, 2.0 Hz, 1H), 3.93 (s, 2H),
3.15-2.97 (m, 1H), 1.21 (d, J = 6.9 Hz, 6H) 86C J 566 (M + H)
163-169 (CDCl.sub.3) .delta. 8.81 (bs, 1H), 8.57 (s, 1H), 8.20 (d,
J = 8.3 Hz, 2H), 7.87-7.75 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H),
7.32-7.25 (m, 1H), 7.10 (2dt, J = 7.4, 1.5 Hz, 2H), 6.83 (d, J =
6.5 Hz, 1H), 3.96 (t, J = 6.1 Hz, 2H), 3.13 (heptet, J = 6.9 Hz,
1H), 2.99-2.88 (m, 2H), 2.49-2.36 (m, 2H), 1.29-1.21 (m, 6H). 87C J
550 (M + H) 187-189 (CDCl.sub.3) .delta. 8.81 (s, 1H), 8.66 (s,
1H), 8.21 (d, J = 8.3 Hz, 2H), 7.92 (d, J = 8.4 Hz, 2H), 7.81 (t, J
= 10.2 Hz, 4H), 7.30-7.26 (m, 2H), 7.17-7.04 (m, 1H), 6.83 (d, J =
6.4 Hz, 1H), 3.96 (t, J = 6.1 Hz, 2H), 3.13 (heptet, J = 6.9 Hz,
1H), 2.97-2.90 (m, 2H), 2.47-2.38 (m, 2H), 1.25 (d, J = 7.5 Hz,
6H). 88C F 579.2 (M + H) 178-182 (CDCl.sub.3) .delta. 8.58 (s, 1H),
8.30 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.82 (dd, J = 8.7, 7.2 Hz,
4H), 7.48 (dd, J = 4.1, 1.3 Hz, 2H), 7.40 (d, J = 8.3 Hz, 2H),
7.37-7.30 (m, 1H), 7.17 (m, 1H), 4.23 (dq, J = 14.5, 7.2 Hz, 1H),
2.83 (dd, J = 14.6, 6.9 Hz, 1H), 1.79 (d, J = 7.2 Hz, 3H), 1.22
(ddd, J = 12.1, 6.9, 1.9 Hz, 6H). 89C F 559 (M + H) 205-206
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.32 (s, 1H), 8.23 (d, J = 8.4
Hz, 2H), 7.90-7.75 (m, 4H), 7.52-7.44 (m, 1H), 7.40 (d, J = 8.3 Hz,
2H), 7.10 (dd, J = 8.6, 7.4 Hz, 2H), 4.04 (s, 2H). 90C F 566 (M +
H) 148-151 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.31 (s, 1H), 8.23
(d, J = 8.3 Hz, 2H), 7.82 (t, J = 8.5 Hz, 4H), 7.46-7.31 (m, 3H),
7.25-7.18 (m, 2H), 4.02 (s, 2H), 2.53 (q, J = 7.6 Hz, 2H), 2.21 (s,
3H), 1.26-1.16 (m, 3H). 91C F 554 (M + H) 227-235 (CDCl.sub.3)
.delta. 8.58 (s, 1H), 8.36 (s, 1H), 8.23 (d, J = 8.3 Hz, 2H),
7.88-7.76 (m, 4H), 7.49-7.35 (m, 3H), 7.01 (dd, J = 8.5, 2.5 Hz,
1H), 6.96 (dd, J = 7.8, 1.0 Hz, 1H), 6.91 (t, J = 2.2 Hz, 1H), 3.98
(s, 2H), 3.85 (s, 3H). 92C F 554 (M + H) 104-108 (CDCl.sub.3)
.delta. 8.58 (s, 1H), 8.32 (s, 1H), 8.22 (d, J = 8.4 Hz, 2H),
7.86-7.77 (m, 4H), 7.50-7.43 (m, 1H), 7.40 (d, J = 8.3 Hz, 2H),
7.32-7.27 (m, 1H), 7.14-7.04 (m, 2H), 4.01 (d, J = 17.2 Hz, 1H),
3.94 (d, J = 17.3 Hz, 1H), 3.84 (s, 3H). 93C F 572 (M + H) 183-186
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.31 (s, 1H), 8.27-8.18 (m, 2H),
7.88-7.77 (m, 4H), 7.43-7.37 (m, 3H), 7.34 (t, J = 7.8 Hz, 1H),
7.30-7.26 (m, 1H), 4.07 (d, J = 17.4 Hz, 1H), 4.00 (d, J = 17.4 Hz,
1H), 2.29 (s, 3H). 94C F 552 (M + H) 134-136 (CDCl.sub.3) .delta.
8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.86-7.78 (m,
4H), 7.49-7.32 (m, 5H), 7.24-7.18 (m, 1H), 4.06-3.94 (m, 2H), 2.56
(q, J = 7.6 Hz, 2H), 1.26-1.18 (m, 3H). 95C F 576.1 (M + H) 195-201
(CDCl.sub.3) .delta. 8.59 (d, J = 4.8 Hz, 1H), 8.26 (m, 3H),
7.89-7.74 (m, 4H), 7.52-7.31 (m, 4H), 7.24-7.13 (m, 1H), 4.05 (d, J
= 0.9 Hz, 2H). 96C F 600 (M + H) 182-185 (300 MHz, CDCl.sub.3)
.delta. 8.58 (s, 1H), 8.33 (d, J = 7.9 Hz, 1H), 8.24 (s, 1H), 8.21
(s, 1H), 7.86-7.76 (m, 4H), 7.53 (t, J = 5.9 Hz, 3H), 7.44-7.29 (m,
8H), 3.80-3.73 (m, 1H), 3.59-3.51 (m, 1H). 97C F 567 (M + H)
234-236 (CDCl.sub.3) .delta. 8.57 (s, 1H), 8.37 (s, 1H), 8.23 (d, J
= 8.4 Hz, 2H), 7.89-7.73 (m, 4H), 7.45-7.29 (m, 3H), 6.79 (dd, J =
8.2, 2.2 Hz, 1H), 6.70 (d, 1H), 6.57 (s, 1H), 3.96 (s, 2H), 2.98
(s, 6H) 98C F 612 (M + H) 225-226 (CDCl.sub.3) .delta. 8.55 (s,
1H), 8.29 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 7.86-7.71 (m, 4H),
7.42-7.23 (m, 3H), 6.63 (d, J = 8.5 Hz, 2H), 4.07 (q, J = 7.0 Hz,
4H), 3.94 (s, 2H), 1.31 (t, J = 7.0 Hz, 6H) 99C F 679 (M - H)
230-231 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.32 (s, 1H), 8.23 (d, J
= 8.4 Hz, 2H), 7.89-7.77 (m, 4H), 7.70 (d, J = 8.1 Hz, 2H), 7.40
(d, J = 8.3 Hz, 2H), 7.29-7.20 (m, 1H), 4.04 (s, 2H) 100C F 602 (M
+ H) 118-120 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.30 (s, 1H), 8.22
(d, J = 8.4 Hz, 2H), 7.93-7.70 (m, 4H), 7.39 (d, J = 9.0 Hz, 2H),
7.28 (t, 1H), 7.19 (d, J = 7.7 Hz, 2H), 4.01 (s, 2H), 2.21 (s, 6H).
101C F 583 (M + H) 106-107 (CDCl.sub.3) .delta. 8.60 (s, 1H), 8.32
(s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.89-7.74 (m, 4H), 7.39 (d, J =
8.3 Hz, 2H), 6.56 (s, 1H), 4.01 (s, 2H), 3.94 (s, 3H), 2.32 (s,
3H), 2.16 (s, 3H) 102C F 589 (M - H) 123-126 (CDCl.sub.3) .delta.
8.27 (s, 1H), 7.95-7.71 (m, 5H), 7.60 (d, J = 1.3 Hz, 1H),
7.53-7.43 (m, 4H), 7.45-7.32 (m, 3H), 4.04 (s, 2H) 103C F 551 (M +
H) 194-196 (CDCl.sub.3) .delta. 8.28 (s, 1H), 7.93 (dd, J = 5.4,
4.1 Hz, 3H), 7.78 (m, 4H), 7.36-7.23 (m, 3H), 7.19 (d, J = 7.6 Hz,
2H), 6.81 (d, J = 2.5 Hz, 1H), 4.00 (s, 2H), 2.21 (s, 6H) 104C F
551 (M + H) 100-102 (CDCl.sub.3) .delta. 8.27 (s, 1H), 8.16 (s,
1H), 8.03 (s, 1H), 7.80-7.71 (m, 4H), 7.57 (d, J = 8.3 Hz, 2H),
7.30 (dd, J = 28.7, 5.8 Hz, 3H), 7.19 (d, J = 7.6 Hz, 2H), 4.01 (s,
2H), 2.21 (s, 6H) 105C F 586 (M + H) 209-211 (CDCl.sub.3) .delta.
8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 7.8 Hz, 2H), 7.82 (m, 4H),
7.39 (d, J = 8.0 Hz, 2H), 7.19 (s, 2H), 4.01 (s, 2H), 2.19 (s, 6H)
106C F 558 (M + H) 180-182 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.30
(s, 1H), 8.22 (d, J = 8.2 Hz, 2H), 7.81 (m, 4H), 7.58 (dd, J = 6.0,
3.3 Hz, 1H), 7.43 (ddd, J = 23.4, 11.3, 5.5 Hz, 5H), 4.02 (dd, J =
29.9, 17.4 Hz, 2H) 107C F 596 (M + H) 227-232 (CDCl.sub.3) .delta.
8.58 (s, 1H), 8.32 (s, 1H), 8.22 (dd, J = 10.0, 8.6 Hz, 4H), 7.82
(m, 4H), 7.49 (d, J = 8.5 Hz, 2H), 7.40 (d, J = 8.6 Hz, 2H), 4.42
(q, J = 7.1 Hz, 2H), 4.00 (s, 2H), 1.41 (t, J = 7.1 Hz, 3H) 108C F
580 (M + H) 167-171 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.28 (d, J =
15.0 Hz, 1H), 8.23 (d, J = 8.3 Hz, 2H), 7.87-7.76 (m, 4H),
7.53-7.30 (m, 5H), 7.18 (ddd, J = 7.8, 4.2, 1.2 Hz, 1H), 4.03-3.98
(m, 2H), 2.53 (dd, J = 14.1, 7.0 Hz, 1H), 1.77-1.56 (m, 2H),
1.26-1.16 (m, 3H), 0.78 (td, J = 7.4, 2.3 Hz, 3H). 109C F 652 (M +
H) 105-111 (CDCl.sub.3) .delta. 8.25 (s, 1H), 7.73 (d, J = 7.4 Hz,
4H), 7.55-7.43 (m, 2H), 7.43-7.36 (m, 1H), 7.10 (t, J = 11.6 Hz,
4H), 4.90-4.79 (m, 1H), 4.04 (s, 2H), 3.76 (s, 3H), 3.73-3.62 (m,
1H), 3.52-3.35 (m, 1H) 110C F 611 (M + H) Oil (CDCl.sub.3) .delta.
8.25 (s, 1H), 7.82-7.64 (m, 4H), 7.30 (t, 1H), 7.22-6.99 (m, 6H),
4.83 (dd, J = 12.8, 6.5 Hz, 1H), 4.00 (s, 2H), 3.89-3.59 (m, 4H),
3.44 (dd, J = 17.2, 6.5 Hz, 1H), 2.20 (s, 6H). 111C F 580 (M + H)
209-210 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.30 (s, 1H), 8.23 (d, J
= 8.4 Hz, 2H), 7.86-7.77 (m, 4H), 7.39 (t, J = 7.8 Hz, 3H),
7.34-7.27 (m, 1H), 7.20 (d, J = 7.4 Hz, 1H), 4.03 (s, 2H),
2.86-2.71 (m, 1H), 2.21 (s, 3H), 1.21 (2d, J = 6.7 Hz, 6H). 112C F
564 (M + H) 154-158 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.32 (s,
1H), 8.23 (d, J = 8.4 Hz, 2H), 7.87-7.75 (m, 4H), 7.43-7.33 (m,
4H), 7.26-7.19 (m, 2H), 4.02 (s, 2H), 1.86-1.77 (m, 1H), 0.90-0.83
(m, 2H), 0.77-0.68 (m, 1H), 0.67-0.59 (m, 1H). 113C F 538 (M + H)
111-116; (Acetone-D.sub.6) .delta. 9.20 (s, 1H), 8.28 (d, J = 8.2
Hz, 210-212 3H), 8.13 (d, J = 9.0 Hz, 2H), 7.94 (d, J = 8.2 Hz,
2H), 7.60 (d, J = 8.8 Hz, 2H), 7.39 (t, J = 17.1 Hz, 4H), 4.15 (q,
J = 17.3 Hz, 2H), 2.23 (s, 3H) 114C F 568 (M + H) 203-205
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.33 (s, 1H), 8.22 (d, J = 8.3
Hz, 2H), 7.88-7.67 (m, 4H), 7.38 (d, J = 8.4 Hz, 2H), 7.14 (d, J =
8.3 Hz, 1H), 6.87 (d, J = 8.9 Hz, 2H), 3.98 (s, 2H), 3.83 (s, 3H),
2.20 (s, 3H) 115C F 554 (M + H) 261-264 (CDCl.sub.3) .delta. 8.58
(s, 1H), 8.35 (s, 1H), 8.23 (d, J = 8.2 Hz, 2H), 7.82 (m, 4H), 7.40
(d, J = 8.6 Hz, 2H), 7.30 (d, 2H), 7.03 (d, J = 8.8 Hz, 2H), 3.97
(s, 2H), 3.86 (s, 3H) 116C F 568 (M + H) 92-97 (CDCl.sub.3) .delta.
8.58 (s, 1H), 8.31 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.88-7.72 (m,
4H), 7.48-7.32 (m, 3H), 7.31-7.20 (m, 1H), 7.13-6.97 (m, 2H), 4.09
(q, J = 7.0 Hz, 2H), 3.95 (t, J = 11.7 Hz, 2H), 1.33 (t, J = 7.0
Hz, 3H). 117C F 539 (M + H) 127-132 (CDCl.sub.3) .delta. 8.59 (s,
1H), 8.54 (dd, J = 4.8, 1.3 Hz, 1H), 8.28 (s, 1H), 8.22 (d, J = 8.4
Hz, 2H), 7.84-7.77 (m, 4H), 7.77-7.72 (m, 1H), 7.38 (dd, J = 7.7,
5.0 Hz, 3H), 4.02 (d, J = 1.2 Hz, 2H), 2.30 (s, 3H) 118C F 539 (M +
H) 215 (dec) (CDCl.sub.3) .delta. 8.67 (s, 1H), 8.59 (s, 1H), 8.24
(d, J = 8.4 Hz, 2H), 7.99 (d, J = 8.4 Hz, 1H), 7.84 (dd, J = 8.3,
3.8 Hz, 4H), 7.80 (s, 1H), 7.42-7.39 (m, 3H), 4.03 (d, J = 1.3 Hz,
2H), 2.26 (s, 3H). 119C F 580 (M + H) 124-138 (CDCl.sub.3) .delta.
8.58 (s, 1H), 8.29 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.88-7.77 (m,
4H), 7.48-7.34 (m, 5H), 7.23-7.18 (m, 1H), 4.06-3.93 (m, 2H), 2.40
(qd, J = 14.2, 7.3 Hz, 2H), 1.94-1.81 (m, 1H), 0.89 (d, J = 6.6 Hz,
6H). 120C F 549.7 (M + H) 153-159 (CDCl.sub.3) .delta. 8.67 (s,
1H), 8.30 (s, 1H), 8.24 (d, J = 8.3 Hz, 2H), 7.92 (d, J = 8.5 Hz,
2H), 7.82 (m, 3H), 4.01 (d, J = 1.5 Hz, 2H), 3.80-3.64 (m, 2H),
2.91-2.76 (m, 2H), 1.30-1.14 (m, 6H) 121C F 578 (M + H) 143-147;
(CDCl.sub.3) .delta. 8.57 (d, J = 7.4 Hz, 1H), 8.30 (s, 148-151
1H), 8.23 (d, J = 8.4 Hz, 2H), 7.87-7.78 (m, 4H), 7.49-7.33 (m,
5H), 7.29-7.26 (m, 1H), 6.03 (s, 1H), 3.95 (s, 2H), 1.84 (d, J =
1.3 Hz, 3H), 1.71 (d, J = 1.2 Hz, 3H). 122C F 579.3 (M + 1) 169-171
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.24-8.18 (m, 2H), 7.99-7.94 (m,
2H), 7.84-7.78 (m, 2H), 7.47 (dd, J = 5.0, 1.1 Hz, 2H), 7.40 (d, J
= 8.3 Hz, 2H), 7.34 (ddd, J = 7.9, 5.1, 3.7 Hz, 1H), 7.18 (d, J =
7.6 Hz, 1H), 4.00 (d, J = 1.5 Hz, 2H), 3.72 (dd, J = 7.0, 5.1 Hz,
2H), 2.94-2.80 (m, 1H), 2.22 (s, 3H), 1.23 (m, 9H). 123C F 553 (M +
H) 130-135 (CDCl.sub.3) .delta. 8.62 (s, 1H), 8.54 (d, J = 3.2 Hz,
1H), 8.28-8.19 (m, 3H), 7.82 (d, J = 8.8 Hz, 5H), 7.43-7.37 (m,
3H), 4.02 (s, 2H), 2.63 (d, J = 7.6 Hz, 2H), 1.22 (s, 3H) 124C F
608 (M + H) 140-145 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.29 (s,
1H), 8.23 (d, J = 8.4 Hz, 2H), 7.89-7.75 (m, 4H), 7.58-7.51 (m,
1H), 7.49-7.36 (m, 5H), 4.04 (d, J = 17.4 Hz, 1H), 3.97 (d, J =
17.4 Hz, 1H). 125C F 580 (M + H) 130-140 (CDCl.sub.3) .delta. 8.58
(s, 1H), 8.31 (s, 1H), 8.22 (d, J = 8.4 Hz, 2H), 7.86-7.78 (m, 4H),
7.65 (dd, J = 8.1, 1.4 Hz, 1H), 7.49-7.42 (m, 1H), 7.40 (d, J = 8.3
Hz, 2H), 7.35 (dt, J = 7.6, 1.5 Hz, 1H), 7.05 (dd, J = 7.8, 1.5 Hz,
1H), 3.95 (s, 2H), 1.38 (s, 9H). 126C F 590 (M + H) 175-177
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.29 (s, 1H), 8.23 (d, J = 8.4
Hz, 2H), 7.87-7.77 (m, 4H), 7.52 (ddd, J = 8.1, 6.0, 3.4 Hz, 1H),
7.44-7.34 (m, 5H), 6.46 (t, J.sub.HF = 73.5 Hz, 1H), 4.05-3.95 (m,
2H). 127C F 578 (M + H) 112-115 (CDCl.sub.3) .delta. 8.58 (s, 1H),
8.32 (s, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.87-7.75 (m, 4H),
7.43-7.32 (m, 4H), 7.26-7.24 (m, 2H), 4.23 (q, J = 7.3 Hz, 1H),
1.85-1.78 (m, 4H), 0.90-0.78 (m, 2H), 0.78-0.69 (m, 1H), 0.65-0.55
(m, 1H). 128C F 580 (M + H) 164-171 (CDCl.sub.3) .delta. 8.58 (s,
1H), 8.29 (d, J = 7.8 Hz, 1H), 8.22 (d, J = 8.3 Hz, 2H), 7.88-7.74
(m, 4H), 7.48-7.30 (m, 5H), 7.20 (t, J = 11.1 Hz, 1H), 4.26-4.14
(m, 1H), 2.50-2.46 (m, 2H), 1.79 (d, J = 7.3 Hz, 3H), 1.69-1.56 (m,
2H), 0.93 (t, J = 7.3 Hz, 3H). 129C F 606 (M + H) 140-142
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.30 (s, 1H), 8.22 (d, J = 8.4
Hz, 2H), 7.87-7.76 (m, 4H), 7.53-7.47 (m, 2H), 7.44-7.35 (m, 3H),
4.27 (q, J = 7.3 Hz, 1H), 1.82 (d, J = 7.3 Hz, 3H). 130C F 590 (M +
H) 93-97; (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.31 (s, 1H), 191-194
8.22 (d, J = 8.4 Hz, 2H), 7.88-7.76 (m, 4H), 7.48-7.34 (m, 4H),
7.20 (tt, J = 12.4, 6.1 Hz, 1H), 4.35-4.18 (m, 1H), 1.81 (2d, J =
7.3 Hz, 3H). 131C F 572 (M - H) 93-98; (CDCl.sub.3) .delta. 8.58
(s, 1H), 8.32 (s, 1H), 185-186 8.26-8.20 (m, 2H), 7.86-7.78 (m,
4H), 7.53-7.42 (m, 1H), 7.40 (d, J = 8.3 Hz, 2H), 7.09 (t, J = 8.1
Hz, 2H), 4.26 (q, J = 7.3 Hz, 1H), 1.80 (d, J = 7.3 Hz, 3H). 132C J
552 (M + H) 193-196 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.22 (s,
1H), 8.17 (d, J = 8.4 Hz, 2H), 7.80 (ddd, J = 9.5, 6.9, 4.9 Hz,
4H), 7.43-7.33 (m, 4H), 7.31-7.21 (m, 2H), 4.05 (td, J = 9.4, 7.1
Hz, 1H), 3.97-3.87 (m, 1H), 3.42-3.33 (m, 1H), 3.33-3.24 (m, 1H),
3.12 (heptet, J = 6.8 Hz, 1H), 1.27 (d, J = 6.8 Hz, 3H), 1.22 (d, J
= 6.9 Hz, 3H). 133C J 538 (M + H) 167-169 (CDCl.sub.3) .delta. 8.55
(d, J = 7.1 Hz, 1H), 8.23 (s, 1H), 8.17 (d, J = 8.4 Hz, 2H), 7.80
(dt, J = 11.4, 6.2 Hz, 4H), 7.43-7.23 (m, 6H), 4.00 (s, 2H), 3.32
(s, 2H), 2.67 (q, J = 7.6 Hz, 2H), 1.25 (dd, J = 9.6, 5.5 Hz, 3H).
134C J 536 (M + H) 217-220; (CDCl.sub.3) .delta. 8.65 (s, 1H), 8.22
(s, 1H), 230-232 8.18 (d, J = 8.4 Hz, 2H), 7.94-7.88 (m, 2H),
7.81-7.78 (m, 4H), 7.41 (dd, J = 7.8, 1.5 Hz, 1H), 7.39-7.33 (m,
1H), 7.30-7.24 (m, 1H), 7.23 (dd, J = 7.8, 1.5 Hz, 1H), 4.09-4.02
(m, 1H), 3.98-3.88 (m, 1H), 3.43-3.24 (m, 2H), 3.12 (heptet, J =
6.9 Hz, 1H), 1.27 (d, J = 6.8 Hz, 3H), 1.22 (d, J = 6.9 Hz, 3H).
135C J 566 (M + H) 167-169 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.19
(dd, J = 12.7, 9.0 Hz, 3H), 7.84-7.74 (m, 4H), 7.37 (dd, J = 14.9,
6.1 Hz, 4H), 7.26 (s, 1H), 7.21 (d, J = 7.6 Hz, 1H), 4.17-3.85 (m,
2H), 3.42-3.22 (m, 2H), 2.82 (d, J = 23.6 Hz, 1H), 1.80-1.55 (m,
2H), 1.23 (2d, J = 6.9 Hz, 3H), 0.82 (2t, J = 7.4 Hz, 3H). 136C J
552 (M + H) 143-147 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.22 (s,
1H), 8.17 (d, J = 8.4 Hz, 2H), 7.84-7.74 (m, 4H), 7.39 (d, J = 8.3
Hz, 2H), 7.24 (d, J = 7.5 Hz, 1H), 7.19 (d, J = 6.4 Hz, 1H), 7.15
(d, J = 7.3 Hz, 1H), 3.92 (qt, J = 10.1, 7.3 Hz, 2H), 3.43-3.28 (m,
2H), 2.72-2.51 (m, 2H), 2.27 (s, 3H), 1.25 (t, J = 7.6 Hz, 3H).
137C J 554 (M + H) 183-186 (CDCl.sub.3) .delta. 8.56 (d, J = 5.3
Hz, 1H), 8.26 (s, 1H), 8.17 (d, J = 8.4 Hz, 2H), 7.84-7.74 (m, 4H),
7.39 (d, J = 8.3 Hz, 2H), 7.18 (d, J = 8.5 Hz, 1H), 6.81 (dt, J =
8.4, 2.9 Hz, 2H), 3.96 (t, J = 6.6 Hz, 2H), 3.81 (s, 3H), 3.30 (t,
J = 6.9 Hz, 2H), 2.28 (s, 3H). 138C J 568 (M + H) 231-233
(CDCl.sub.3) .delta. 8.56 (d, J = 5.4 Hz, 1H), 8.25 (s, 1H), 8.17
(d, J = 8.4 Hz, 2H), 7.84-7.72 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H),
6.67 (s, 2H), 3.92-3.85 (m, 2H), 3.79 (s, 3H), 3.34 (t, J = 7.1 Hz,
2H), 2.25 (s, 6H). 139C J 552 (M + H) 195-197 (CDCl.sub.3) .delta.
8.56 (s, 1H), 8.24 (s, 1H), 8.17 (d, J = 8.3 Hz, 2H), 7.83-7.73 (m,
4H), 7.39 (d, J = 8.3 Hz, 2H), 6.95 (s, 2H), 3.90 (t, J = 7.1 Hz,
2H), 3.35 (t, J = 7.1 Hz, 2H), 2.30 (s, 3H), 2.23 (s, 6H). 140C J
540 (M + H) 181-184 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.24 (s,
1H), 8.17 (d, J = 8.3 Hz, 2H), 7.84-7.75 (m, 4H), 7.43-7.36 (m,
3H), 7.30 (ddd, J = 12.6, 6.9, 3.1 Hz, 1H), 7.06-6.97 (m, 2H), 4.04
(t, J = 7.0 Hz, 2H), 3.86 (s, 3H), 3.29 (t, J = 7.0 Hz, 2H). 141C J
524 (M + H) 173-176 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.25 (s,
1H), 8.18 (d, J = 8.4 Hz, 2H), 7.83-7.75 (m, 4H), 7.39 (d, J = 8.3
Hz, 2H), 7.34-7.23 (m, 4H), 4.01 (t, J = 6.9 Hz, 2H), 3.32 (t, J =
6.9 Hz, 2H), 2.31 (s, 3H). 142C J 538 (M + H) 210-213 (CDCl.sub.3)
.delta. 8.56 (s, 1H), 8.23 (s, 1H), 8.17 (d, J = 8.4 Hz, 2H),
7.84-7.74 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.22-7.10 (m, 3H),
3.92 (t, J = 7.1 Hz, 2H), 3.36 (t, J = 7.1 Hz, 2H), 2.28 (s, 6H).
143C J 562 (M + H) 221-224 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.23
(s, 1H), 8.18 (d, J = 8.4 Hz, 2H), 7.83-7.74 (m, 4H), 7.38 (d, J =
8.3 Hz, 2H), 7.30 (dt, J = 7.4, 4.8 Hz, 2H), 7.15-7.09 (m, 1H),
4.05 (ddd, J = 9.4, 7.3, 5.2 Hz, 1H), 4.00-3.89 (m, 1H), 3.46-3.30
(m, 2H). 144C J 586 (M + H) 117-123; (300 MHz, CDCl.sub.3) .delta.
8.56 (d, J = 4.3 Hz, 134-138 1H), 8.34 (s, 1H), 8.21 (s, 1H), 8.18
(s, 1H), 7.81 (dd, J = 8.9, 2.3 Hz, 4H), 7.52 (d, J = 6.7 Hz, 1H),
7.50-7.31 (m, 10H), 3.53-3.49 (m, 2H), 2.95-2.90 (d, J = 6.8 Hz,
2H). 145C J 550 (M + H) 207-209 (CDCl.sub.3) .delta. 8.56 (s, 1H),
8.26 (s, 1H), 8.18 (d, J = 8.3 Hz, 2H), 7.84-7.74 (m, 4H), 7.39 (d,
J = 8.3 Hz, 2H), 7.32-7.21 (m, 3H), 7.01 (dd, J = 8.9, 2.5 Hz, 1H),
4.12-4.04 (s, 2H), 3.34 (t, J = 6.9 Hz, 2H), 2.09-1.98 (m, 1H),
0.95 (dd, J = 8.5, 1.7 Hz, 2H), 0.72 (bs, 2H). 146C J 554 (M + H)
141-144 (CDCl.sub.3) .delta. 8.56 (d, J = 5.2 Hz, 1H), 8.24 (s,
1H), 8.17 (d, J = 8.3 Hz, 2H), 7.80 (dt, J = 8.2, 4.6 Hz, 4H),
7.45-7.36 (m, 3H), 7.30-7.24 (m, 1H), 7.05-6.95 (m, 2H), 4.13-4.02
(m, 4H), 3.28 (t, J = 7.0 Hz, 2H), 1.44-1.35 (m, 3H). 147C J 540 (M
+ H) 168-170 (CDCl.sub.3) .delta. 8.57 (s, 1H), 8.37 (s, 1H), 8.21
(d, J = 8.3 Hz, 2H), 7.87-7.76 (m, 4H), 7.40 (d, J = 8.4 Hz, 2H),
7.29 (dd, J = 14.2, 6.0 Hz, 1H), 7.24 (d, J = 2.3 Hz, 1H),
7.09-7.02 (m, 1H), 6.72 (dd, J = 8.0, 2.1 Hz, 1H), 4.20 (t, J = 6.9
Hz, 2H), 3.83 (d, J = 8.7 Hz, 3H), 3.24 (t, J = 6.9 Hz, 2H). 148C J
546 (M + H) 213-216 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.24 (s,
1H), 8.18 (d, J = 8.3 Hz, 2H), 7.80 (dt, J = 4.0, 2.5 Hz, 4H), 7.39
(d, J = 8.3 Hz, 2H), 7.30 (ddd, J = 8.5, 7.4, 4.2 Hz, 1H),
7.05-6.97 (m, 2H), 4.02 (t, J = 6.9 Hz, 2H), 3.36 (t, J = 6.9 Hz,
2H). 149C J 612 (M + H) 200-203 (CDCl.sub.3) .delta. 8.56 (s, 1H),
8.18 (d, J = 2.6 Hz, 2H), 8.16 (s, 1H), 7.80 (dt, J = 8.3, 4.7 Hz,
4H), 7.71 (t, J = 8.6 Hz, 2H), 7.47 (t, J = 7.7 Hz, 1H), 7.39 (d, J
= 8.3 Hz, 2H), 4.18-4.07 (m, 1H), 3.93-3.84 (m, 1H), 3.46 (td, J =
10.7, 7.3 Hz, 1H), 3.35-3.25 (m, 1H). 150C J 566 (M + H) 169-172
(CDCl.sub.3) .delta. 8.56 (s, 1H), 8.22 (s, 1H), 8.17 (d, J = 8.4
Hz, 2H), 7.80 (dt, J = 11.5, 6.2 Hz, 4H), 7.39 (d, J = 8.3 Hz, 2H),
7.31-7.27 (m, 3H), 7.26-7.24 (m, 1H), 4.10-3.89 (m, 2H), 3.38-3.32
(m, 2H), 2.48 (s, 2H), 2.01-1.84 (m, 1H), 0.91 (d, J = 6.2 Hz, 6H).
151C J 564 (M + H) 149-153 (CDCl.sub.3) .delta. 8.57 (s, 1H), 8.25
(s, 1H), 8.18 (d, J = 8.3 Hz, 2H), 7.99 (s, 1H), 7.81 (dt, J = 8.3,
4.5 Hz, 4H), 7.39 (dd, J = 6.1, 3.5 Hz, 3H), 7.33-7.27 (m, 2H),
6.21 (s, 1H), 3.92 (t, J = 6.9 Hz, 2H), 3.26 (t, J = 6.8 Hz, 2H),
1.89 (d, J = 1.1 Hz, 3H), 1.79 (d, J = 1.1 Hz, 3H). 152C J 576 (M +
H) 161-163 (CDCl.sub.3) .delta. 8.57 (s, 1H), 8.23-8.16 (m, 3H),
7.83-7.77 (m, 4H), 7.48 (dd, J = 7.5, 2.0 Hz, 1H), 7.39 (d, J = 8.3
Hz, 2H), 7.33 (dt, J = 7.2, 2.1 Hz, 2H), 7.28 (dd, J = 9.8, 1.9 Hz,
1H), 6.52 (t, J.sub.HF = 74.1 Hz, 1H), 4.06 (t, J = 6.9 Hz, 2H),
3.33 (t, J = 6.9 Hz, 2H). 153C J 594 (M + H) 195-197 (CDCl.sub.3)
.delta. 8.57 (s, 1H), 8.25 (s, 1H), 8.19 (d, J = 8.4 Hz, 2H), 7.81
(dt, J = 4.1, 2.6 Hz, 4H), 7.58-7.52 (m, 1H), 7.42-7.33 (m, 5H),
4.05 (t, J = 6.9 Hz, 2H), 3.31 (t, J = 6.9 Hz, 2H). 154C J 538 (M +
H) 164-167 CDCl.sub.3) .delta. 8.56 (s, 1H), 8.23 (d, J = 9.8 Hz,
1H), 8.17 (d, J = 8.3 Hz, 2H), 7.84-7.74 (m, 4H), 7.39 (d, J = 8.3
Hz, 2H), 7.35-7.27 (m, 3H), 7.19 (s, 1H), 3.54-3.31 (m, 1H),
3.07-2.93 (m, 1H), 2.31 (d, J = 9.0 Hz, 3H), 1.62-1.56 (m, 1H),
1.31-1.19 (m, 3H). 155C J 566 (M + H) 201-204 Two Isomers
(CDCl.sub.3) .delta. 8.56 (s, 2H), 8.18 (dd, J = 10.8, 7.4 Hz, 6H),
7.84-7.73 (m, 8H), 7.45-7.30 (m, 8H), 7.30-7.23 (m, 2H), 7.20 (d, J
= 6.7 Hz, 1H), 7.12 (dd, J = 7.8, 1.2 Hz, 1H), 4.43-4.33 (m, 1H),
4.16 (dd, J = 12.6, 6.3 Hz, 1H), 3.48 (dt, J = 13.3, 6.7 Hz, 1H),
3.37 (dd, J = 10.8, 6.2 Hz, 1H), 3.24 (dt, J = 13.7, 6.9 Hz, 1H),
3.08-2.92 (m, 3H), 1.33-1.16 (m, 18H). 156C J 566 (M + H) 105-110
(CDCl.sub.3) .delta. 8.56 (s, 1H), 8.20 (d, J = 3.4 Hz, 1H), 8.16
(d, J = 8.4 Hz, 2H), 7.84-7.73 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H),
7.25-7.09 (m, 3H), 4.39-4.23 (m, 1H), 3.53-3.35 (m, 1H), 3.04-3.00
(m, 1H), 2.78-2.49 (m, 2H), 2.28 (2s, 3H), 1.34-1.08 (m, 6H). 157C
J 592 (M + H) 175-176 (CDCl.sub.3) .delta. 8.56 (d, J = 0.6 Hz,
1H), 8.21 (s, 1H), 8.17 (d, J = 8.2 Hz, 2H), 7.82-7.77 (m, 4H),
7.49-7.35 (m, 4H), 7.30-7.28 (m, 1H), 4.64-4.57 (m, 1H), 3.44 (dd,
J = 10.2, 6.3 Hz, 1H), 3.16-3.01 (m, 1H), 1.27 (d, J = 6.3 Hz, 3H).
158C J 572 (M + H) 99-102 Two Isomers (CDCl.sub.3) .delta. 8.56 (s,
2H), 8.20 (s, 2H), 8.19-8.12 (m, 4H), 7.84-7.73 (m, 8H), 7.39 (d, J
= 8.3 Hz, 4H), 7.36-7.29 (m, 2H), 7.25-7.17 (m, 4H), 4.78-4.55 (m,
1H), 4.35 (dt, J = 9.4, 6.3 Hz, 1H), 3.48 (dd, J = 10.7, 6.5 Hz,
1H), 3.38 (dd, J = 10.7, 6.2 Hz, 1H), 3.11 (dd, J = 10.7, 9.4 Hz,
1H), 3.01 (dd, J = 10.7, 8.3 Hz, 1H), 2.35 (s, 3H), 2.30 (s, 3H),
1.26 (d, J = 6.3 Hz, 3H), 1.21 (d, J = 6.4 Hz, 3H) 159C J 607 (M +
H) 85 (dec) (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.18 (dd, J = 11.9,
5.3 Hz, 3H), 7.79 (dd, J = 8.7, 6.5 Hz, 4H), 7.47 (dd, J = 7.8, 2.3
Hz, 1H), 7.42-7.32 (m, 5H), 4.48-4.29 (m, 1H), 3.45 (dd, J = 10.7,
6.4 Hz, 1H), 2.98 (dd, J = 10.7, 7.1 Hz, 1H), 1.26 (d, J = 6.3 Hz,
3H) 160C J 626 (M + H) 93 (dec) Two Isomers (CDCl3) .delta. 8.56
(s, 2H), 8.19-8.12 (m, 6H), 7.84-7.73 (m, 10H), 7.71 (d, J = 8.2
Hz, 2H), 7.47 (t, J = 8.0 Hz, 2H), 7.39 (d, J = 8.3 Hz, 4H),
4.76-4.64 (m, 1H), 4.48 (dd, J = 14.6, 6.3 Hz, 1H), 3.43 (dd, J =
10.6, 6.2 Hz, 1H), 3.29 (dd, J = 10.5, 5.5 Hz, 1H), 3.16-3.00 (m,
2H), 1.27 (d, J = 6.4 Hz, 3H), 1.17 (d, J = 6.4 Hz, 3H) 161C J 566
(M + H) 105 (dec) (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.22 (s, 1H),
8.16 (d, J = 8.4 Hz, 2H), 7.83-7.70 (m, 4H), 7.39 (d, J = 8.3 Hz,
2H), 6.94 (d, J = 9.3 Hz, 2H), 4.43-4.22 (m, 1H), 3.42 (dd, J =
10.8, 6.5 Hz, 1H), 3.00 (dd, J = 10.8, 8.5 Hz, 1H),
2.30 (s, 3H), 2.25 (s, 3H), 2.21 (s, 3H), 1.20 (d, J = 6.3 Hz, 3H)
162C J 568 (M + H) 100 (dec) (CDCl.sub.3) .delta. 8.56 (s, 1H),
8.24 (s, 1H), 8.17 (d, J = 8.4 Hz, 2H), 7.83-7.73 (m, 4H), 7.39 (d,
J = 8.3 Hz, 2H), 7.18-7.09 (m, 1H), 6.86-6.76 (m, 2H), 4.33-4.19
(m, 1H), 3.82 (s, 3H), 3.47-3.38 (m, 1H), 3.00-2.99 (m, 1H),
2.29-2.27 (m, 3H), 1.33-1.15 (m, 3H) 163C J 580 (M + H) 92-102
(CDCl.sub.3) .delta. 8.56 (s, 2H), 8.18 (dd, J = 10.7, 5.3 Hz, 6H),
7.84-7.74 (m, 8H), 7.42-7.30 (m, 8H), 7.23-7.10 (m, 2H), 4.37 (dd,
J = 19.5, 13.6 Hz, 1H), 4.16 (dd, J = 13.1, 6.6 Hz, 1H), 3.56-3.42
(m, 1H), 3.34 (dd, J = 10.8, 6.0 Hz, 1H), 3.08-2.87 (m, 3H), 2.70
(dd, J = 16.0, 7.0 Hz, 1H), 1.71-1.56 (m, 4H), 1.34-1.25 (m, 6H),
1.24-1.14 (m, 6H), 0.93-0.73 (m, 6H) 164C J 589 (M + H) 80 (dec)
(CDCl.sub.3) .delta. 8.56 (s, 1H), 8.22-8.14 (m, 3H), 7.84-7.76 (m,
4H), 7.42-7.27 (m, 6H), 6.51 (t, J.sub.HF = 74.3 Hz, 1H), 4.52-4.31
(m, 1H), 3.44 (dd, J = 10.8, 6.5 Hz, 1H), 2.99 (dd, J = 10.8, 7.6
Hz, 1H), 1.25 (d, J = 6.3 Hz, 3H) 165C J 580 (M + H) 143 (dec) Two
Isomers (CDCl.sub.3) .delta. 8.56 (s, 2H), 8.22 (s, 1H), 8.20 (s,
1H), 8.16 (d, J = 8.3 Hz, 4H), 7.84-7.74 (m, 8H), 7.58 (ddd, J =
9.7, 8.0, 1.7 Hz, 2H), 7.39 (d, J = 8.4 Hz, 4H), 7.36-7.27 (m, 4H),
7.15 (dd, J = 7.7, 1.6 Hz, 1H), 7.09 (dd, J = 7.6, 1.7 Hz, 1H),
4.38-4.22 (m, 2H), 3.61 (dd, J = 10.8, 7.0 Hz, 1H), 3.24 (dd, J =
10.7, 5.6 Hz, 1H), 3.07-2.94 (m, 1H), 2.91 (dd, J = 10.8, 1.5 Hz,
1H), 1.47-1.38 (m, 24H) 166C J 552 (M + H) 93 (dec) (CDCl.sub.3)
.delta. 8.56 (s, 1H), 8.21 (s, 1H), 8.16 (d, J = 8.4 Hz, 2H),
7.84-7.73 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.32-7.28 (m, 3H),
7.20 (s, 1H), 4.20-4.06 (m, 1H), 3.41 (s, 1H), 3.05 (dd, J = 10.8,
8.2 Hz, 1H), 2.31-32.30 (m, 3H), 1.66 (s, 2H), 0.90-0.88 (m, 3H)
167C J 586 (M + H) 105 (dec) Two Isomers (CDCl.sub.3) .delta. 8.56
(s, 2H), 8.20 (s, 2H), 8.16 (d, J = 8.3 Hz, 4H), 7.83-7.74 (m, 8H),
7.43-7.28 (m, 6H), 7.21 (dd, J = 5.4, 3.3 Hz, 4H), 4.49-4.36 (m,
1H), 4.17-4.05 (m, 1H), 3.49 (dd, J = 10.7, 6.6 Hz, 1H), 3.40 (dd,
J = 10.7, 6.3 Hz, 1H), 3.10 (dd, J = 10.7, 9.4 Hz, 1H), 3.04 (dd, J
= 10.8, 8.2 Hz, 1H), 2.34 (s, 3H), 2.30 (s, 3H), 1.73-1.48 (m, 4H),
0.91 (m, 6H) 168C J 560 (M + H) 199-200 (CDCl.sub.3) .delta. 8.56
(s, 1H), 8.18 (m,, 2H), 7.79 (m, 4H), 7.47 (dd, J = 7.8, 2.3 Hz,
1H), 7.42-7.32 (m, 5H), 4.48-4.29 (m, 1H), 3.45 (dd, J = 10.7, 6.4
Hz, 1H), 2.98 (dd, J = 10.7, 7.1 Hz, 1H), 1.26 (d, J = 6.3 Hz, 3H)
169C G 623 (M + H) Oil (CDCl.sub.3) .delta. 10.45 (s, 1H), 8.59 (s,
1H), 8.25 (d, J = 8.3 Hz, 2H), 7.88 (d, J = 8.3 Hz, 2H), 7.81 (d, J
= 8.9 Hz, 2H), 7.61 (t, J = 7.5 Hz, 2H), 7.40 (d, J = 8.7 Hz, 2H),
7.11 (t, J = 8.0 Hz, 1H), 5.71 (d, J = 1.1 Hz, 1H), 2.35 (s, 3H)
.sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -58.02, -62.31 170C G
606 (M + H) 157-159 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.19-8.14
(m, 3H), 7.79 (m, 4H), 7.56-7.46 (m, 2H), 7.46-7.43 (m, 2H), 7.39
(d, J = 8.3 Hz, 2H), 5.88 (d, J = 1.3 Hz, 1H), 1.86 (d, J = 1.2 Hz,
3H) 171C G 558 (M + H) 236-237 (CDCl.sub.3) .delta. 8.56 (s, 1H),
8.19 (d, J = 5.9 Hz, 2H), 8.16 (s, 1H), 7.83-7.76 (m, 4H), 7.45
(tt, J = 8.4, 6.1 Hz, 1H), 7.39 (d, J = 8.3 Hz, 2H), 7.10 (dd, J =
8.5, 7.3 Hz, 2H), 5.90 (d, J = 1.3 Hz, 1H), 1.92 (s, 3H) 172C G 580
(M + H) 103-108 (CDCl.sub.3) .delta. 8.56 (d, J = 3.7 Hz, 1H), 8.21
(s, 1H), 8.16 (d, J = 8.4 Hz, 2H), 7.84-7.72 (m, 4H), 7.39 (d, J =
8.3 Hz, 2H), 6.72 (s, 2H), 5.89 (d, J = 1.3 Hz, 1H), 3.82 (s, 3H),
2.14 (s, 6H), 1.75 (d, J = 1.2 Hz, 3H). 173C G 536 (M + H) 87 (dec)
(CDCl.sub.3) .delta. 8.56 (s, 1H), 8.19-8.15 (m, 3H), 7.82-7.75 (m,
4H), 7.43-7.30 (m, 5H), 7.24 (d, J = 7.3 Hz, 1H), 5.88 (s, 1H),
2.21 (s, 3H), 1.80 (d, J = 1.2 Hz, 3H) 174C G 570 (M + H) 95 (dec)
(CDCl.sub.3) .delta. 8.56 (s, 1H), 8.20-8.12 (m, 3H), 7.83-7.74 (m,
4H), 7.43-7.36 (m, 3H), 7.32 (t, J = 7.7 Hz, 1H), 7.29-7.27 (m,
1H), 5.92 (d, J = 1.3 Hz, 1H), 2.26 (s, 3H), 1.81 (d, J = 1.2 Hz,
3H) 175C G 550 (M + H) 132-136 (CDCl.sub.3) .delta. 8.56 (d, J =
5.0 Hz, 1H), 8.21-8.13 (m, 3H), 7.83-7.74 (m, 4H), 7.39 (d, J = 8.2
Hz, 2H), 7.29-7.23 (m, 1H), 7.19 (d, J = 7.7 Hz, 2H), 5.92 (d, J =
1.3 Hz, 1H), 2.18 (s, 6H), 1.75 (d, J = 1.2 Hz, 3H). 176C G 564 (M
+ H) 123-138 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.19-8.14 (m, 3H),
7.83-7.75 (m, 4H), 7.49-7.43 (m, 2H), 7.39 (d, J = 8.3 Hz, 2H),
7.33 (ddd, J = 7.8, 5.9, 3.0 Hz, 1H), 7.19-7.17 (m, 1H), 5.88 (d, J
= 1.3 Hz, 1H), 2.96-2.76 (m, 1H), 1.81 (d, J = 1.2 Hz, 3H), 1.24
(t, J = 6.4 Hz, 3H), 1.22-1.16 (m, 3H). 177C J 566 (M + H) 185-187
(CDCl.sub.3) .delta. 8.55 (s, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.05
(s, 1H), 7.84-7.77 (m, 2H), 7.74 (d, J = 8.3 Hz, 2H), 7.42-7.35 (m,
3H), 7.32 (dd, J = 10.6, 4.3 Hz, 1H), 7.28-7.24 (m, 1H), 7.18 (dd,
J = 7.8, 1.4 Hz, 1H), 3.80-3.69 (m, 1H), 3.59-3.48 (m, 1H), 3.11
(dd, J = 13.2, 6.8 Hz, 3H), 2.41-2.27 (m, 2H), 1.22 (t, J = 5.6 Hz,
6H). 178C J 580 (M + H) 186-190 (CDCl.sub.3) .delta. 8.55 (d, J =
3.6 Hz, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.06 (s, 1H), 7.84-7.77 (m,
2H), 7.74 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 9.0 Hz, 3H), 7.32 (td,
J = 7.5, 1.4 Hz, 1H), 7.26 (s, 1H), 7.17 (t, J = 7.1 Hz, 1H),
3.69-3.26 (m, 1H), 3.55-3.37 (m, 1H), 3.18-2.98 (m, 2H), 2.93-2.80
(m, 1H), 2.47 (d, J = 35.9 Hz, 1H), 1.31-1.12 (m, 9H). 179C J 550
(M + H) 212-213 (CDCl.sub.3) .delta. 8.64 (s, 1H), 8.15 (d, J = 8.4
Hz, 2H), 8.06 (s, 1H), 7.91 (d, J = 8.5 Hz, 2H), 7.79 (d, J = 8.6
Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.38 (dd, J = 7.8, 1.6 Hz, 1H),
7.33 (td, J = 7.5, 1.4 Hz, 1H), 7.29-7.23 (m, 1H), 7.18 (dd, J =
7.8, 1.4 Hz, 1H), 3.78-3.72 (m, 1H), 3.59-3.48 (m, 1H), 3.18-3.04
(m, 3H), 2.40-2.30 (m, 2H), 1.26-1.20 (m, 6H). 180C J 566 (M + H)
127-133 (300 MHz, CDCl.sub.3) .delta. 8.55 (s, 1H), 8.13 (d, J =
8.3 Hz, 2H), 8.05 (s, 1H), 7.76 (dd, J = 17.0, 8.7 Hz, 4H), 7.37
(t, J = 8.4 Hz, 2H), 7.18 (dd, J = 12.7, 9.6 Hz, 3H), 3.54-3.49 (m,
2H), 3.12-3.08 (m, 2H), 2.70-2.55 (m, 2H), 2.39-2.31 (m, 2H), 2.28
(s, 3H), 1.25 (t, J = 7.6 Hz, 3H). 181C J 582 (M + H) 170-174
(CDCl.sub.3) .delta. 8.55 (s, 1H), 8.14 (d, J = 8.3 Hz, 2H), 8.08
(s, 1H), 7.84-7.76 (m, 2H), 7.74 (d, J = 8.3 Hz, 2H), 7.38 (d, J =
8.3 Hz, 2H), 6.65 (s, 2H), 3.79 (s, 3H), 3.52-3.45 (m, 2H),
3.10-3.07 (m, 2H), 2.38-2.31 (d, J = 5.7 Hz, 2H), 2.25 (s, 6H).
182C J 552 (M + H) 148-155; (300 MHz, CDCl.sub.3) .delta. 8.55 (d,
J = 1.0 Hz, 166-168 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.05 (s, 1H),
7.83-7.76 (m, 2H), 7.74 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 9.0 Hz,
2H), 7.14-7.09 (m, 3H), 3.51 (dd, J = 9.1, 3.5 Hz, 2H), 3.15-3.03
(m, 2H), 2.36 (s, 2H), 2.28 (s, 6H). 183C J 580 (M + H) 159-162
(CDCl.sub.3) .delta. 8.55 (d, J = 3.7 Hz, 1H), 8.14 (d, J = 8.4 Hz,
2H), 8.03 (d, J = 19.3 Hz, 1H), 7.84-7.77 (m, 2H), 7.74 (d, J = 8.4
Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 3.8 Hz, 2H), 7.25
(d, J = 6.6 Hz, 1H), 7.19 (t, J = 8.0 Hz, 1H), 3.76 (ddd, J = 24.2,
12.0, 5.9 Hz, 1H), 3.58-3.46 (m, 1H), 3.11 (dd, J = 15.3, 6.1 Hz,
2H), 2.82 (dd, J = 14.6, 7.2 Hz, 1H), 2.41-2.29 (m, 2H), 1.71-1.55
(m, 2H), 1.20 (d, J = 6.8 Hz, 3H), 0.87-0.76 (m, 3H). 184C J 566 (M
+ H) 194-198 (CDCl.sub.3) .delta. 8.55 (s, 1H), 8.14 (d, J = 8.4
Hz, 2H), 8.07 (s, 1H), 7.83-7.76 (m, 2H), 7.74 (d, J = 8.4 Hz, 2H),
7.40 (t, J = 10.1 Hz, 2H), 6.93 (s, 2H), 3.53-3.47 (m, 2H),
3.12-3.05 (m, 2H), 2.34 (dt, J = 11.7, 5.8 Hz, 2H), 2.30 (s, 3H),
2.23 (s, 6H). 185C J 552 (M + H) 157-160 (CDCl.sub.3) .delta. 8.55
(s, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.06 (s, 1H), 7.83-7.77 (m, 2H),
7.74 (d, J = 8.3 Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H), 7.36-7.27 (m,
3H), 7.23-7.19 (m, 1H), 3.74 (m, 1H), 3.50 (m, 1H), 3.10 (d, J =
5.9 Hz, 2H), 2.64 (q, J = 7.6 Hz, 2H), 2.40-2.29 (m, 2H), 1.28-1.21
(m, 3H). 186C J 564 (M + H) 173-177 (CDCl.sub.3) .delta. 8.55 (s,
1H), 8.14 (d, J = 8.4 Hz, 2H), 8.09 (s, 1H), 7.83-7.77 (m, 2H),
7.81-7.77 (m, 2H), 7.38 (d, J = 8.3 Hz, 2H), 7.24-7.22 (m, 3H),
7.05-6.95 (m, 1H), 3.77-3.63 (m, 2H), 3.14-3.07 (m, 2H), 2.45-2.29
(m, 2H), 2.09-1.92 (m, 1H), 0.97-0.82 (m, 3H), 0.53 (bs, 1H). 187C
J 593 (M + H) 180-182 (300 MHz, CDCl.sub.3) .delta. 8.55 (s, 1H),
8.14 (d, J = 8.4 Hz, 2H), 8.05 (d, J = 4.9 Hz, 1H), 7.77 (dd, J =
11.4, 8.6 Hz, 4H), 7.39 (t, J = 8.1 Hz, 4H), 7.21 (dd, J = 13.2,
5.6 Hz, 1H), 3.65-3.58 (m, 2H), 3.09 (t, J = 5.5 Hz, 2H), 2.45-2.35
(m, 2H). 188C J 576 (M + H) 209-212 (CDCl.sub.3) .delta. 8.56 (s,
1H), 8.15 (d, J = 8.4 Hz, 2H), 8.07 (s, 1H), 7.79 (ddd, J = 15.8,
7.8, 5.8 Hz, 4H), 7.38 (d, J = 8.3 Hz, 2H), 7.31-7.21 (m, 2H), 7.10
(ddd, J = 9.7, 7.8, 2.0 Hz, 1H), 3.64 (t, J = 5.4 Hz, 2H), 3.11 (t,
J = 6.0 Hz, 2H), 2.46-2.33 (m, 2H). 189C J 560 (M + H) 217-219
(CDCl.sub.3) .delta. 8.56 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.08
(s, 1H), 7.83-7.74 (m, 4H), 7.38 (d, J = 8.3 Hz, 2H), 7.31-7.21 (m,
1H), 7.03-6.94 (m, 2H), 3.72-3.62 (m, 2H), 3.15-3.07 (m, 2H),
2.40-2.34 (m, 2H). 190C J 626 (M + H) 190-193 (CDCl.sub.3) .delta.
8.55 (s, 1H), 8.14 (d, J = 8.3 Hz, 2H), 8.00 (s, 1H), 7.83-7.73 (m,
4H), 7.71 (d, J = 8.1 Hz, 1H), 7.67 (d, J = 7.7 Hz, 1H), 7.40 (dd,
J = 15.8, 8.2 Hz, 3H), 3.79-3.69 (m, 1H), 3.55-3.49 (m, 1H),
3.16-3.04 (m, 2H), 2.47-2.31 (m, 2H). 191C J 554 (M + H) 150-155
(CDCl.sub.3) .delta. 8.54 (d, J = 4.3 Hz, 1H), 8.13 (d, J = 8.3 Hz,
2H), 8.05 (d, J = 6.3 Hz, 1H), 7.77 (dd, J = 15.4, 8.7 Hz, 4H),
7.38 (d, J = 8.3 Hz, 2H), 7.29 (dd, J = 8.0, 4.8 Hz, 2H), 7.04-6.93
(m, 2H), 3.85 (s, 3H), 3.65-3.61 (m, 2H), 3.10-3.06 (m, 2H),
2.36-2.28 (s, 2H). 192C J 568 (M + H) 164-167; (CDCl.sub.3) .delta.
8.55 (s, 1H), 8.14 (d, J = 8.4 Hz, 168-173 2H), 8.09 (s, 1H),
7.82-7.77 (m, 2H), 7.74 (d, J = 6.7 Hz, 2H), 7.38 (d, J = 8.3 Hz,
2H), 7.13 (d, J = 8.3 Hz, 1H), 6.79 (dd, J = 11.9, 3.3 Hz, 2H),
3.81 (s, 3H), 3.74-3.66 (m, 1H), 3.57-3.48 (m, 1H), 3.12-3.04 (m,
2H), 2.36-2.30 (m, 2H), 2.25 (s, 3H). 193C J 580 (M + H) 155-158
(CDCl.sub.3) .delta. 8.55 (s, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.04
(s, 1H), 7.83-7.77 (m, 2H), 7.74 (d, J = 8.4 Hz, 2H), 7.38 (d, J =
8.3 Hz, 2H), 7.31-7.24 (m, 3H), 7.23-7.20 (m, 1H), 3.82-3.71 (m,
1H), 3.56-3.47 (m, 1H), 3.17-3.02 (m, 2H), 2.46 (t, J = 6.7 Hz,
2H), 2.39-2.27 (m, 2H), 1.99 (heptet, J = 6.8 Hz, 1H), 0.95-0.92
(m, 6H). 194C J 600 (M + H) 102-108 (CDCl.sub.3) .delta. 8.56 (s,
1H), 8.17 (m 3H), 7.80 (m, 4H), 7.52-7.47 (m, 2H), 7.47-7.31 (m,
9H), 3.42-3.05 (m, 2H), 2.86 (bs, 2H),
2.04-1.71 (m, 2H). 195C J 538 (M + H) 159-162 (CDCl.sub.3) .delta.
8.55 (s, 1H), 8.14 (d, J = 8.3 Hz, 2H), 8.08 (s, 1H), 7.84-7.77 (m,
2H), 7.75 (d, J = 8.4 Hz, 2H), 7.38 (d, J = 8.5 Hz, 2H), 7.31-7.19
(m, 4H), 3.81-3.47 (m, 2H), 3.20-3.00 (m, 2H), 2.35 (dt, J = 11.7,
5.8 Hz, 2H), 2.28 (s, 3H). 196C J 572 (M + H) 140-143 (CDCl.sub.3)
.delta. 8.55 (s, 1H), 8.14 (d, J = 8.1 Hz, 2H), 8.05 (s, 1H), 7.80
(d, J = 8.9 Hz, 2H), 7.75 (d, J = 8.2 Hz, 2H), 7.38 (d, J = 8.8 Hz,
2H), 7.33 (dd, J = 6.1, 3.4 Hz, 1H), 7.21-7.15 (m, 2H), 3.72-3.66
(m, 1H), 3.55-3.41 (m, 1H), 3.16-3.05 (m, 2H), 2.48-2.34 (m, 2H),
2.32 (s, 3H). 197C J 578 (M + H) 151-155 (CDCl.sub.3) .delta. 8.55
(s, 1H), 8.14 (d, J = 8.2 Hz, 2H), 8.06 (s, 1H), 7.80 (d, J = 8.9
Hz, 2H), 7.75 (d, J = 8.2 Hz, 2H), 7.38 (d, J = 8.8 Hz, 2H), 7.29
(dd, J = 10.7, 4.6 Hz, 4H), 6.20 (s, 1H), 3.59-3.48 (m, 2H),
3.10-3.01 (m, 2H), 2.34-2.20 (m, 2H), 1.90 (s, 3H), 1.78 (s, 3H).
198C J 539 (M + H) 186-189 (CDCl.sub.3) .delta. 8.56 (s, 1H), 8.36
(dd, J = 4.8, 1.3 Hz, 1H), 8.15 (d, J = 8.3 Hz, 2H), 8.09 (s, 1H),
7.78 (m, 4H), 7.54 (dd, J = 7.5, 0.9 Hz, 1H), 7.37 (d, J = 8.5 Hz,
2H), 7.13 (dd, J = 7.4, 4.8 Hz, 1H), 3.87 (t, J = 5.7 Hz, 2H),
3.12-3.03 (m, 2H), 2.40-2.32 (m, 2H), 2.24 (s, 3H). 199C J 608 (M +
H) 207-208 (CDCl.sub.3) .delta. 8.55 (s, 1H), 8.15 (d, J = 8.4 Hz,
2H), 8.05 (s, 1H), 7.83-7.78 (m, 2H), 7.76 (d, J = 8.4 Hz, 2H),
7.43-7.36 (m, 3H), 7.34 (t, J = 4.7 Hz, 3H), 3.71-3.64 (m, 2H),
3.12-3.06 (m, 2H), 2.39-2.30 (m, 2H). 200C J 590 (M + H) 170-172
(CDCl.sub.3) .delta. 8.56 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.03
(s, 1H), 7.83-7.77 (m, 2H), 7.76 (d, J = 8.3 Hz, 2H), 7.42-7.27 (m,
6H), 6.74-6.29 (m, 1H), 3.70-3.64 (m, 2H), 3.13-3.06 (m, 2H),
2.40-2.31 (m, 2H). 201C J 626 (M + H) 190-193 (CDCl.sub.3) .delta.
8.55 (s, 1H), 8.14 (d, J = 8.3 Hz, 2H), 8.00 (s, 1H), 7.83-7.73 (m,
4H), 7.71 (d, J = 8.1 Hz, 1H), 7.67 (d, J = 7.7 Hz, 1H), 7.40 (dd,
J = 15.8, 8.2 Hz, 3H), 3.79-3.69 (m, 1H), 3.55-3.49 (m, 1H),
3.16-3.04 (m, 2H), 2.47-2.31 (m, 2H). 202C J 554 (M + H) 231-234
(CDCl.sub.3) .delta. 8.56 (s, 1H), 8.19-8.08 (m, 3H), 7.84-7.72 (m,
4H), 7.39 (d, J = 8.4 Hz, 2H), 7.25-7.20 (m, 2H), 6.96-6.88 (m,
2H), 3.83 (s, 3H), 3.76-3.68 (m, 2H), 3.13-3.03 (m, 2H), 2.39-2.27
(m, 2H). 203C J 631 (M + H) 200-201 (CDCl.sub.3) .delta. 8.56 (s,
1H), 8.15 (d, J = 8.2 Hz, 2H), 8.06 (s, 1H), 7.83-7.77 (m, 2H),
7.75 (d, J = 8.2 Hz, 2H), 7.39 (d, J = 8.5 Hz, 2H), 7.28-7.25 (m,
2H), 3.51-3.42 (m, 2H), 3.14-3.05 (m, 2H), 2.35 (s, 2H), 2.25 (s,
6H). 204C J 568 (M + H) 193-196 (CDCl.sub.3) .delta. 8.55 (s, 1H),
8.14 (d, J = 8.4 Hz, 2H), 8.09 (s, 1H), 7.84-7.77 (m, 2H), 7.75 (d,
J = 8.4 Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H), 7.08 (t, J = 4.0 Hz,
2H), 6.88 (d, J = 8.6 Hz, 1H), 3.82 (s, 3H), 3.66-3.58 (m, 2H),
3.11-3.03 (m, 2H), 2.36-2.27 (m, 5H). 205C J 539 (M + H) Oil
(CDCl.sub.3) .delta. 8.55 (s, 1H), 8.45 (dd, J = 4.8, 1.6 Hz, 1H),
8.18-8.12 (m, 2H), 8.06 (s, 1H), 7.82-7.72 (m, 4H), 7.53 (dd, J =
7.9, 1.6 Hz, 1H), 7.40-7.33 (m, 2H), 7.24-7.18 (m, 1H), 3.63 (br s,
2H), 3.18-3.03 (m, 2H), 2.51 (s 3H), 2.35 (dt, J = 11.7, 5.7 Hz,
2H) 206C J 554 (M + H) 177-178 (CDCl.sub.3) .delta. 8.56 (s, 1H),
8.16 (d, J = 8.9 Hz, 3H), 7.84-7.73 (m, 4H), 7.39 (d, J = 8.8 Hz,
2H), 7.30 (t, J = 8.1 Hz, 1H), 6.95-6.85 (m, 2H), 6.78 (dt, J =
11.1, 5.5 Hz, 1H), 3.81 (s, 3H), 3.79-3.73 (m, 2H), 3.12-3.04 (m,
2H), 2.38-2.28 (m, 2H). 207C J 596 (M + H) 171-173 (CDCl.sub.3)
.delta. 8.57 (s, 1H), 8.23-8.13 (m, 3H), 8.06 (d, J = 8.5 Hz, 2H),
7.80 (dd, J = 8.5, 4.5 Hz, 4H), 7.39 (d, J = 8.5 Hz, 4H), 4.38 (q,
J = 7.2 Hz, 2H), 3.82 (t, J = 6.0 Hz, 2H), 3.14-3.03 (m, 2H), 2.37
(s, 2H), 1.40 (t, J = 7.1 Hz, 3H). 208C J 568 (M + H) 171-173
(CDCl.sub.3) .delta. 8.55 (s, 1H), 8.14 (d, J = 8.3 Hz, 2H), 8.07
(s, 1H), 7.84-7.77 (m, 2H), 7.75 (d, J = 8.3 Hz, 2H), 7.38 (d, J =
8.3 Hz, 2H), 7.32-7.23 (m, 2H), 6.99 (ddd, J = 8.3, 5.5, 1.4 Hz,
2H), 4.08 (q, J = 7.0 Hz, 2H), 3.69-3.57 (m, 2H), 3.16-3.02 (m,
2H), 2.32 (dt, J = 11.7, 5.9 Hz, 2H), 1.39 (t, J = 7.0 Hz, 3H).
209C J 550 (M + H) 212-213 (CDCl.sub.3) .delta. 8.64 (s, 1H), 8.15
(d, J = 8.4 Hz, 2H), 8.06 (s, 1H), 7.91 (d, J = 8.5 Hz, 2H), 7.79
(d, J = 8.6 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.38 (dd, J = 7.8,
1.6 Hz, 1H), 7.33 (td, J = 7.5, 1.4 Hz, 1H), 7.29-7.23 (m, 1H),
7.18 (dd, J = 7.8, 1.4 Hz, 1H), 3.78-3.72 (m, 1H), 3.59-3.48 (m,
1H), 3.18-3.04 (m, 3H), 2.40-2.30 (m, 2H), 1.26-1.20 (m, 6H). 210C
J 580 (M + H) 136-139 (CDCl.sub.3) .delta. 8.55 (s, 1H), 8.14 (d, J
= 8.4 Hz, 2H), 8.07 (s, 1H), 7.83-7.77 (m, 2H), 7.75 (d, J = 8.4
Hz, 2H), 7.55-7.49 (m, 1H), 7.38 (d, J = 8.3 Hz, 2H), 7.32-7.26 (m,
2H), 7.19-7.13 (m, 1H), 3.72 (ddd, J = 12.9, 9.3, 3.8 Hz, 1H),
3.60-3.51 (m, 1H), 3.15 (ddd, J = 13.3, 9.4, 4.0 Hz, 1H), 3.10-3.01
(m, 1H), 2.51-2.36 (m, 1H), 2.36-2.22 (m, 1H), 1.43 (s, 9H). 211C J
566 (M + H) 100-106 (CDCl.sub.3) .delta. 8.55 (s, 1H), 8.15 (d, J =
8.4 Hz, 2H), 8.10 (s, 1H), 7.79 (dt, J = 10.4, 5.8 Hz, 4H), 7.38
(d, J = 8.3 Hz, 2H), 7.11 (s, 3H), 3.85-3.78 (m, 2H), 3.20-3.12 (m,
2H), 2.30 (s, 6H), 2.13-2.07 (m, 2H), 1.87-1.82 (m, 2H). 212C J 580
(M + H) 186-188 (CDCl.sub.3) .delta. 8.55 (s, 1H), 8.19-8.10 (m,
3H), 7.79 (dt, J = 10.7, 5.9 Hz, 4H), 7.38 (dd, J = 8.5, 2.6 Hz,
3H), 7.30 (td, J = 7.5, 1.4 Hz, 1H), 7.23 (td, J = 7.5, 1.7 Hz,
1H), 7.13 (dd, J = 7.8, 1.4 Hz, 1H), 3.94 (bs, 2H), 3.24-3.02 (m,
3H), 2.13-2.05 (m, 2H), 1.84-1.73 (m, 2H), 1.24 (t, J = 10.5 Hz,
6H). 213C J 580 (M + H) 123-127 (CDCl.sub.3) .delta. 8.55 (s, 1H),
8.13 (d, J = 8.4 Hz, 2H), 8.03 (d, J = 4.4 Hz, 1H), 7.83-7.76 (m,
2H), 7.74 (d, J = 8.0 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.24-7.15
(m, 2H), 7.12 (dd, J = 11.9, 4.6 Hz, 1H), 3.82-3.71 (m, 1H),
3.30-3.18 (m, 1H), 3.07-2.94 (m, 1H), 2.72-2.40 (m, 3H), 2.30-2.16
(m, 4H), 1.30-1.12 (m, 6H). 214C J 622 (M + H) 160-162 (CDCl.sub.3)
.delta. 8.55 (s, 1H), 8.15 (d, J = 8.4 Hz, 2H), 8.06 (s, 1H),
7.83-7.72 (m, 4H), 7.38 (m, 3H), 7.34 (dd, J = 2.9, 1.5 Hz, 3H),
3.58 (ddd, J = 12.3, 3.9, 1.4 Hz, 1H), 3.39 (dd, J = 12.2, 9.2 Hz,
1H), 3.04 (ddd, J = 12.2, 3.9, 1.4 Hz, 1H), 2.84 (dd, J = 12.2, 9.5
Hz, 1H), 2.61-2.42 (m, 1H), 1.18 (d, J = 6.7 Hz, 3H) 215C J 640 (M
+ H) 116 (dec) (CDCl.sub.3) .delta. 8.55 (s, 1H), 8.14 (dd, J =
8.3, 1.5 Hz, 2H), 8.00 (d, J = 4.0 Hz, 1H), 7.84-7.72 (m, 4H),
7.72-7.63 (m, 2H), 7.45-7.32 (m, 3H), 3.60-3.44 (m, 1H), 3.37-3.27
(m, 1H), 3.03-2.92 (m, 1H), 2.92-2.82 (m, 1H), 2.69-2.54 (m, 1H),
1.19-1.12 (m, 3H) 216C J 622 (M + H) 132-135 (CDCl.sub.3) .delta.
8.55 (s, 1H), 8.14 (d, J = 8.4 Hz, 2H), 8.02 (s, 1H), 7.82-7.71 (m,
4H), 7.44-7.30 (m, 6H), 3.87 (d, J = 6.3 Hz, 1H), 3.23 (td, J =
11.9, 3.8 Hz, 1H), 3.07-2.94 (m, 1H), 2.54-2.43 (m, 1H), 2.19 (ddd,
J = 13.9, 9.0, 5.0 Hz, 1H), 1.31 (d, J = 6.6 Hz, 3H) 217C J 640 (M
+ H) 93 (dec) Two isomers (CDCl.sub.3) .delta. 8.55 (s, 2H), 8.14
(dd, J = 8.4, 2.7 Hz, 4H), 7.98 (d, J = 4.2 Hz, 2H), 7.83-7.72 (m,
8H), 7.67 (dt, J = 12.9, 7.4 Hz, 4H), 7.40 (dd, J = 15.3, 8.1 Hz,
6H), 4.17 (s, 1H), 3.96 (td, J = 6.6, 3.1 Hz, 1H), 3.24-3.12 (m,
2H), 3.12-3.01 (m, 2H), 2.41 (dddd, J = 10.8, 10.0, 8.9, 4.2 Hz,
2H), 2.30-2.15 (m, 2H), 1.24 (d, J = 6.7 Hz, 3H), 1.04 (d, J = 6.7
Hz, 3H) 218C J 580 (M + H) 95 (dec) (CDCl.sub.3) .delta. 8.55 (s,
1H), 8.18-8.10 (m, 2H), 8.05 (s, 1H), 7.83-7.76 (m, 2H), 7.73 (d, J
= 8.4 Hz, 2H), 7.41-7.37 (m, 2H), 6.93 (d, J = 9.4 Hz, 2H), 3.76
(dd, J = 10.8, 4.6 Hz, 1H), 3.29-3.16 (m, 1H), 2.99 (ddd, J = 12.2,
5.9, 3.9 Hz, 1H), 2.54-2.37 (m, 1H), 2.31 (s, 3H), 2.22 (d, J = 6.4
Hz, 7H), 1.19 (d, J = 6.7 Hz, 3H) 219C J 592 (M + H) 100 (dec)
(CDCl.sub.3) .delta. 8.55 (s, 1H), 8.14-8.06 (m, 3H), 7.91-7.65 (m,
4H), 7.44-7.37 (m, 2H), 7.16-7.09 (m, 1H), 6.93-6.77 (m, 2H),
4.06-3.64 (m, 4H), 3.31-3.16 (m, 1H), 3.02-2.92 (m, 1H), 2.51-2.40
(m, 1H), 2.25-2.17 (m, 4H), 1.41-1.14 (m, 3H) 220C J 593 (M + H) 95
(dec) Two isomers: (CDCl.sub.3) .delta. 8.55 (s, 1H), 8.16-8.09 (m,
2H), 8.01 (m, 1H), 7.86-7.76 (m, 2H), 7.76-7.70 (m, 2H), 7.64-7.28
(m, 4H), 7.24-7.14 (m, 2H), 4.08-3.65 (m, 1H), 3.37-3.15 (m, 1H),
3.09-2.92 (m, 1H), 2.80 (td, J = 14.2, 6.8 Hz, 1H), 2.45 m, 1H),
2.35-2.09 (m, 1H), 1.76-1.58 (m, 1H), 1.48-1.35 (m, 2H), 1.27-1.19
(m, 2H), 1.19-1.13 (m, 2H), 1.06-0.92 (m, 1H), 0.92-0.72 (m, 3H)
221C J 603 (M + H) 113 (dec) (400 MHz, CDCl.sub.3) .delta. 8.56 (s,
1H), 8.20-8.10 (m, 2H), 8.00 (s, 1H), 7.83-7.77 (m, 2H), 7.75 (d, J
= 8.4 Hz, 2H), 7.42-7.28 (m, 6H), 6.72-6.25 (m, 1H), 3.90 (d, J =
6.4 Hz, 1H), 3.24 (td, J = 12.0, 3.6 Hz, 1H), 3.05-2.93 (m, 1H),
2.49 (tt, J = 11.7, 4.0 Hz, 1H), 2.21 (td, J = 8.7, 4.4 Hz, 1H),
1.29 (d, J = 6.6 Hz, 3H) 222C J 594 (M + H) 124 (dec) (CDCl.sub.3)
.delta. 8.55 (s, 1H), 8.14 (dd, J = 8.4, 2.1 Hz, 2H), 8.05 (d, J =
2.8 Hz, 1H), 7.87-7.72 (m, 4H), 7.61-7.49 (m, 1H), 7.38 (d, J = 8.3
Hz, 2H), 7.33-7.21 (m, 2H), 7.15-7.05 (m, 1H), 3.79-3.68 (m, 1H),
3.51-3.29 (m, 1H), 3.12-2.93 (m, 1H), 2.66-2.52 (m, 1H), 2.18-2.12
(m, 1H), 1.43 (m, 12H) 223C L 566 (M + H) 75-87 (CDCl.sub.3)
.delta. 8.58 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 8.16 (s, 1H),
7.85-7.77 (m, 4H), 7.40 (d, J = 8.3 Hz, 2H), 7.23 (dd, J = 8.4, 6.6
Hz, 1H), 7.15 (d, J = 7.5 Hz, 2H), 3.24-3.14 (m, 4H), 2.18 (s, 6H).
224C L 580 (M + H) 118 (dec) (CDCl.sub.3) .delta. 8.57 (s, 1H),
8.21 (d, J = 8.4 Hz, 2H), 8.16 (s, 1H), 7.85-7.75 (m, 4H),
7.46-7.36 (m, 4H), 7.33-7.26 (m, 1H), 7.10 (d, J = 7.6 Hz, 1H),
3.26-3.14 (m, 4H), 2.81 (sept, J = 6.9 Hz, 1H), 1.21 (t, J = 7.2
Hz, 6H). 225C L 580 (M + H) 111 (dec) (CDCl.sub.3) .delta. 8.57 (s,
1H), 8.21 (d, J = 8.4 Hz, 2H), 8.15 (s, 1H), 7.86-7.76 (m, 4H),
7.39 (d, J = 8.3 Hz, 2H), 7.29 (t, J = 7.6 Hz, 1H), 7.21-7.15 (m,
2H), 3.27-3.10 (m, 4H), 2.50 (q, J = 7.5 Hz, 2H), 2.18 (s, 3H),
1.20 (t, J = 7.6 Hz, 3H). 226C L 573 (M + H) 196-200 (CDCl.sub.3)
.delta. 8.57 (s, 1H), 8.24-8.16 (m, 3H), 7.85-7.76 (m, 4H),
7.43-7.34 (m, 3H), 7.03 (dd, J = 8.5, 7.4 Hz, 2H), 3.21 (s, 4H)
227C L 586 (M + H) Oil (CDCl.sub.3) .delta. 8.57 (s, 1H), 8.21 (d,
J = 8.3
Hz, 2H), 8.15 (s, 1H), 7.81 (t, J = 9.1 Hz, 4H), 7.43-7.31 (m, 3H),
7.28-7.21 (m, 2H), 3.36-3.07 (m, 4H), 2.24 (s, 3H); .sup.19F NMR
(376 MHz, CDCl.sub.3) .delta. -58.02 228C L 640 (M + H) 99 (dec)
(CDCl.sub.3) .delta. 8.57 (s, 1H), 8.21 (d, J = 8.3 Hz, 2H), 8.11
(s, 1H), 7.81 (dd, J = 11.5, 4.7 Hz, 4H), 7.72 (dd, J = 17.3, 8.0
Hz, 2H), 7.51 (dd, J = 10.0, 5.4 Hz, 1H), 7.39 (d, J = 8.3 Hz, 2H),
3.36-3.03 (m, 4H) 229C L 622 (M + H) 95 (dec) (CDCl.sub.3) .delta.
8.57 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 8.13 (s, 1H), 7.80 (dt, J =
5.5, 4.9 Hz, 4H), 7.44-7.34 (m, 6H), 3.29-3.10 (m, 4H) 230C L 594
(M + H) 94 (dec) (CDCl.sub.3) .delta. 8.57 (s, 1H), 8.21 (d, J =
8.3 Hz, 2H), 8.14 (d, J = 15.4 Hz, 1H), 7.83-7.76 (m, 4H),
7.43-7.37 (m, 4H), 7.32-7.26 (m, 1H), 7.16-7.09 (m, 1H), 3.24-3.12
(m, 4H), 2.61-2.44 (m, 1H), 1.75-1.50 (m, 2H), 1.17 (dd, J = 6.9,
3.3 Hz, 3H), 0.87-0.73 (m, 3H) 231C L 582 (M + H) 105 (dec)
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.22 (s, 1H), 8.19 (d, J = 5.0
Hz, 2H), 7.81 (dd, J = 8.7, 5.5 Hz, 4H), 7.40 (d, J = 8.3 Hz, 2H),
7.05 (d, J = 8.3 Hz, 1H), 6.90-6.76 (m, 2H), 3.83 (s, 3H),
3.22-3.11 (m, 4H), 2.16 (s, 3H) 232C L 593 (M + H) 120 (dec)
(CDCl.sub.3) .delta. 8.57 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H), 8.16
(s, 1H), 7.81 (dd, J = 8.7, 5.3 Hz, 4H), 7.58 (dd, J = 8.1, 1.5 Hz,
1H), 7.38 (dd, J = 13.2, 5.1 Hz, 3H), 7.33-7.27 (m, 1H), 7.02-6.96
(m, 1H), 3.37-3.01 (m, 4H), 1.36 (s, 9H) 233C L 604 (M + H) 92
(dec) (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.21 (d, J = 8.4 Hz, 2H),
8.14 (s, 1H), 7.86-7.72 (m, 4H), 7.48-7.28 (m, 6H), 6.40 (t,
J.sub.HF = 74.3 Hz, 1H), 3.25-3.11 (m, 4H) 240C J 538 (M + H)
113-116 (300 MHz, CDCl.sub.3) .delta. 8.57 (s, 1H), 8.31 (s, 1H),
8.21 (s, 1H), 8.18 (s, 1H), 7.86-7.76 (m, 4H), 7.48-7.31 (m, 4H),
7.31-7.20 (m, 2H), 4.92 (s, 2H), 3.42-3.27 (m, 1H), 1.31 (s, 3H),
1.28 (s, 3H) 241C J 524 (M + H) Oil (CDCl.sub.3) .delta. 8.56 (s,
1H), 8.29 (s, 1H), 8.19 (d, J = 8.4 Hz, 2H), 7.83-7.76 (m, 4H),
7.39 (d, J = 8.3 Hz, 2H), 7.18 (dd, J = 8.4, 6.6 Hz, 1H), 7.09 (d,
J = 7.7 Hz, 2H), 4.87 (s, 2H), 2.40 (s, 6H); .sup.19F NMR (376 MHz,
CDCl.sub.3) .delta. -58.04 242C J 554 (M + H) 147-159 (CDCl.sub.3)
.delta. 8.57 (s, 1H), 8.30 (s, 1H), 8.19 (d, J = 8.3 Hz, 2H),
7.84-7.76 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 6.62 (s, 2H), 4.84 (s,
2H), 3.78 (s, 3H), 2.37 (s, 6H) 243C J 538 (M + H) 131-135
(CDCl.sub.3) .delta. 8.57 (s, 1H), 8.29 (s, 1H), 8.19 (d, J = 8.4
Hz, 2H), 7.85-7.76 (m, 4H), 7.39 (d, J = 8.3 Hz, 2H), 7.23 (d, J =
7.6 Hz, 1H), 7.17-7.08 (m, 2H), 4.88 (q, J = 4.1 Hz, 2H), 2.87-2.65
(m, 2H), 2.40 (s, 3H), 1.28 (t, J = 7.5 Hz, 3H) 244C J 564 (M + H)
145-146 (CDCl.sub.3) .delta. 8.57 (s, 1H), 8.31 (s, 1H), 8.19 (d, J
= 8.3 Hz, 2H), 7.83-7.79 (m, 4H), 7.42-7.38 (m, 4H), 7.31-7.27 (m,
1H), 5.02 (s, 2H) 245C J 532 (M + H) 144-146 (CDCl.sub.3) .delta.
8.58 (s, 1H), 8.34 (s, 1H), 8.20 (d, J = 8.3 Hz, 2H), 7.81 (d, J =
8.8 Hz, 4H), 7.40 (d, J = 8.3 Hz, 2H), 7.31-7.23 (m, 1H), 7.03-6.97
(m, 2H), 5.05 (s, 2H) 246C J 544 (M + H) 157-160 (CDCl.sub.3)
.delta. 8.57 (s, 1H), 8.30 (s, 1H), 8.19 (d, J = 8.3 Hz, 2H),
7.84-7.77 (m, 4H), 7.39 (d, J = 8.2 Hz, 2H), 7.34-7.28 (m, 1H),
7.25-7.15 (m, 2H), 5.19 (s, 1H), 4.81 (s, 1H), 2.46 (s, 3H) 247C J
587 ([M + H].sup.+) 79-85 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.31
(s, 1H), 8.20 (d, J = 8.4 Hz, 2H), 7.86-7.78 (m, 4H), 7.49-7.28 (m,
5H), 7.26-7.21 (m, 1H), 4.93 (s, 2H), 3.35 (dt, J = 13.7, 6.9 Hz,
1H), 1.30 (d, J = 6.9 Hz, 6H); .sup.19F NMR (376 MHz, CDCl3)
.delta. -85.90, -87.84 248C J 551 ([M + H].sup.+) -- (CDCl.sub.3)
.delta. 8.60-8.58 (m, 1H), 8.28-8.14 (m, 2H), 8.00-7.91 (m, 2H),
7.82 (tdd, J = 5.5, 3.5, 1.7 Hz, 2H), 7.53-7.25 (m, 4H), 7.11-6.91
(m, 2H), 4.94 (s, 2H), 3.26 (dt, J = 13.8, 6.9 Hz, 1H), 2.60-2.37
(m, 3H), 1.31-1.17 (m, 6H); .sup.19F NMR (376 MHz, CDCl.sub.3)
.delta. -58.02 249C J 533 ([M + H].sup.+) 73-90 (CDCl.sub.3)
.delta. 8.53 (s, 1H), 8.31 (s, 1H), 8.18 (d, J = 8.3 Hz, 2H), 7.80
(d, J = 8.3 Hz, 2H), 7.57 (d, J = 2.1 Hz, 1H), 7.50-7.43 (m, 3H),
7.33 (dtd, J = 9.1, 7.8, 1.5 Hz, 2H), 7.21 (ddd, J = 13.8, 7.9, 3.5
Hz, 2H), 4.93 (s, 2H), 3.41-3.27 (m, 1H), 1.30 (d, J = 6.9 Hz, 6H);
.sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -49.65 250C J 555 ([M +
H].sup.+) -- (DMSO-d.sub.6) .delta. 9.44 (s, 1H), 8.27 (s, 1H),
8.21-8.12 (m, 2H), 8.13-8.06 (m, 2H), 7.85-7.75 (m, 2H), 7.67-7.60
(m, 2H), 7.46 (td, J = 8.1, 5.8 Hz, 1H), 7.18-7.31 (m, 2H), 5.05
(s, 2H), 3.22-3.32 (m, 1H), 1.25 (d, J = 6.8 Hz, 6H); .sup.19F NMR
(376 MHz, DMSO-d.sub.6) .delta. -56.95, -120.51 251C J 555 ([M +
H].sup.+) -- (DMSO-d.sub.6) .delta. 9.44 (s, 1H), 8.32 (s, 1H),
8.21-8.13 (m, 2H), 8.13-8.05 (m, 2H), 7.89-7.79 (m, 2H), 7.70-7.59
(m, 2H), 7.54-7.40 (m, 2H), 7.19 (td, J = 8.5, 2.8 Hz, 1H), 5.16
(s, 2H), 3.29 (hept, J = 6.9 Hz, 1H), 1.23 (d, J = 6.8 Hz, 6H);
.sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -56.97, -115.87 252C J
555 ([M + H].sup.+) -- (DMSO-d.sub.6) .delta. 9.44 (s, 1H), 8.28
(s, 1H), 8.21-8.13 (m, 2H), 8.13-8.05 (m, 2H), 7.85-7.78 (m, 2H),
7.67-7.61 (m, 2H), 7.58 (dd, J = 8.8, 5.6 Hz, 1H), 7.26 (dd, J =
10.4, 3.0 Hz, 1H), 7.12 (ddd, J = 8.8, 8.0, 3.0 Hz, 1H), 5.10 (s,
2H), 3.32-3.21 (m, 1H), 1.24 (d, J = 6.8 Hz, 6H); .sup.19F NMR (376
MHz, DMSO-d.sub.6) .delta. -56.96, -112.55 253C J 555 ([M +
H].sup.+) -- (DMSO-d.sub.6) .delta. 9.43 (s, 1H), 8.30 (s, 1H),
8.18-8.12 (m, 2H), 8.12-8.05 (m, 2H), 7.85-7.77 (m, 2H), 7.68-7.58
(m, 2H), 7.40 (dd, J = 8.0, 1.3 Hz, 1H), 7.32 (td, J = 8.1, 5.9 Hz,
1H), 7.17 (ddd, J = 11.7, 8.2, 1.3 Hz, 1H), 5.13 (s, 2H), 3.32-3.23
(m, 1H), 1.35 (dd, J = 7.0, 1.3 Hz, 6H); .sup.19F NMR (376 MHz,
DMSO-d.sub.6) .delta. -56.96, -112.92 254C J 523 ([M + H].sup.+) --
(DMSO-d.sub.6) .delta. 9.46 (s, 1H), 8.34 (s, 1H), 8.22-8.15 (m,
2H), 8.15-8.06 (m, 2H), 7.90-7.80 (m, 2H), 7.70-7.62 (m, 2H),
7.63-7.55 (m, 1H), 7.42-7.24 (m, 3H), 5.16 (s, 2H), 2.79 (q, J =
7.5 Hz, 2H), 1.24 (t, J = 7.5 Hz, 3H); .sup.19F NMR (376 MHz,
DMSO-d.sub.6) .delta. -56.95 255C J 539 ([M + H].sup.+) --
(DMSO-d.sub.6) .delta. 9.57 (s, 1H), 8.33 (s, 1H), 8.26-8.12 (m,
4H), 8.05-7.95 (m, 2H), 7.89-7.79 (m, 2H), 7.55-7.39 (m, 2H), 7.19
(td, J = 8.5, 2.8 Hz, 1H), 5.16 (s, 2H), 3.23-3.32 (m, 1H), 1.23
(d, J = 6.8 Hz, 6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta.
-60.81, -115.86 256C J 605 ([M + H].sup.+) -- (DMSO-d.sub.6)
.delta. 9.45 (s, 1H), 8.32 (s, 1H), 8.20-8.14 (m, 2H), 8.14-8.07
(m, 2H), 7.91-7.78 (m, 2H), 7.68-7.59 (m, 2H), 7.47 (ddd, J = 15.2,
9.4, 4.6 Hz, 2H), 7.19 (td, J = 8.5, 2.8 Hz, 1H), 5.16 (s, 2H),
3.32-3.24 (m, 1H), 1.23 (d, J = 6.8 Hz, 6H); .sup.19F NMR (376 MHz,
DMSO-d.sub.6) .delta. -85.18, -86.91, -115.87 257C J 639 ([M +
H].sup.+) -- (DMSO-d.sub.6) .delta. 9.54 (s, 1H), 8.33 (s, 1H),
8.29-8.21 (m, 2H), 8.21-8.15 (m, 2H), 7.93 (d, J = 8.5 Hz, 2H),
7-89-7.79 (m, 2H), 7.47 (ddd, J = 15.1, 9.4, 4.6 Hz, 2H), 7.19 (td,
J = 8.5, 2.8 Hz, 1H), 5.16 (s, 2H), 3.32-3.23 (m, 1H), 1.23 (d, J =
6.8 Hz, 6H; .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -75.06 (d,
J = 7.5 Hz), -115.87, -181.30 (p, J = 7.8 Hz) 258C J 689 ([M +
H].sup.+) -- (DMSO-d.sub.6) .delta. 9.55 (s, 1H), 8.33 (s, 1H),
8.28-8.20 (m, 2H), 8.21-8.15 (m, 2H), 7.98-7.89 (m, 2H), 7.88-7.80
(m, 2H), 7.47 (ddd, J = 15.2, 9.4, 4.6 Hz, 2H), 7.19 (td, J = 8.5,
2.8 Hz, 1H), 5.16 (s, 2H), 3.31-3.25 (m, 1H), 1.23 (d, J = 6.8 Hz,
6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -72.98--73.71
(m), -78.73 (d, J = 12.8 Hz), -115.87, -120.53--121.42 (m), -182.23
(dt, J = 25.7, 15.5 Hz) 259C J 535 ([M + H].sup.+) --
(DMSO-d.sub.6) .delta. 9.49 (s, 1H), 8.32 (s, 1H), 8.24-8.13 (m,
2H), 8.12-8.03 (m, 2H), 7.91-7.75 (m, 4H), 7.47 (ddd, J = 15.2,
9.4, 4.6 Hz, 2H), 7.19 (td, J = 8.5, 2.8 Hz, 1H), 5.16 (s, 2H),
3.31-3.23 (m, 1H), 2.04 (t, J = 18.9 Hz, 3H), 1.23 (d, J = 6.8 Hz,
6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -84.17, -115.86
260C J 589 ([M + H].sup.+) -- (DMSO-d.sub.6) .delta. 9.57 (s, 1H),
8.33 (s, 1H), 8.24 (d, J = 8.5 Hz, 2H), 8.20-8.15 (m, 2H), 7.96 (d,
J = 8.6 Hz, 2H), 7.90-7.78 (m, 2H), 7.54-7.39 (m, 2H), 7.19 (td, J
= 8.5, 2.8 Hz, 1H), 5.16 (s, 2H), 3.32-3.23 (m, 1H), 1.24 (d, J =
6.8 Hz, 6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta. -84.02
(t, J = 2.3 Hz), -113.41, -115.87 261C J 539 ([M + H].sup.+) --
(DMSO-d.sub.6) .delta. 9.57 (s, 1H), 8.28 (s, 1H), 8.23-8.15 (m,
4H), 8.01-7.98 (m, 2H), 7.86-7.78 (m, 2H), 7.58 (dd, J = 8.8, 5.6
Hz, 1H), 7.26 (dd, J = 10.4, 3.0 Hz, 1H), 7.13 (ddd, J = 8.7, 8.0,
3.0 Hz, 1H), 5.10 (s, 2H), 3.28 (td, J = 6.8, 1.8 Hz, 1H), 1.24 (d,
J = 6.8 Hz, 6H); .sup.19F NMR (376 MHz, DMSO-d.sub.6) .delta.
-60.81, -112.54 NMR spectral data were acquired using a 400 MHz
instrument unless otherwise noted.
TABLE-US-00006 TABLE 4A Analytical Data for Optically Active
Compounds in Table 3 Chiral Separation Purity ID Method MS (%)
.sup.1H NMR (.delta.).sup.1 234C A 571 (M + H) 98.73 (CDCl.sub.3)
.delta. 8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.4 Hz, 2H),
7.87-7.78 (m, 4H), 7.41 (t, J = 6.3 Hz, 3H), 7.37-7.31 (m, 1H),
7.28 (d, J = 7.0 Hz, 1H), 4.09-3.98 (m, 2H), 2.29 (s, 3H) 235C A
571 (M + H) 95.75 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.31 (s, 1H),
8.23 (d, J = 8.3 Hz, 2H), 7.87-7.78 (m, 4H), 7.41 (dd, J = 7.0, 5.6
Hz, 3H), 7.34 (t, J = 7.8 Hz, 1H), 7.28 (d, J = 6.0 Hz, 1H),
4.09-3.98 (m, 2H), 2.29 (s, 3H) 236C A 565 (M + H) 96.32
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.31 (s, 1H), 8.23 (d, J = 8.4
Hz, 2H), 7.81 (dd, J = 11.7, 5.1 Hz, 4H), 7.40 (d, J = 8.4 Hz, 2H),
7.35 (t, J = 7.7 Hz, 1H), 7.24-7.18 (m, 2H), 4.02 (s, 2H), 2.53 (q,
J = 7.5 Hz, 2H), 2.21 (s, 3H), 1.21 (t, J = 7.6 Hz, 3H) 237C A 565
(M + H) 92.33 (CDCl.sub.3) .delta. 8.58 (s, 1H), 8.31 (s, 1H), 8.23
(d, J = 8.4 Hz, 2H), 7.81 (dd, J = 11.7, 5.1 Hz, 4H), 7.40 (d, J =
8.3 Hz, 2H), 7.35 (dd, J = 10.4, 4.9 Hz, 1H), 7.24-7.20 (m, 2H),
4.02 (s, 2H), 2.59-2.45 (m, 2H), 2.21 (s, 3H), 1.21 (t, J = 7.6 Hz,
3H) 238C B 579 (M + H) 95.41 (CDCl.sub.3) .delta. 8.58 (s, 1H),
8.29 (d, J = 3.9 Hz, 1H), 8.23 (d, J = 8.4 Hz, 2H), 7.82 (t, J =
8.8 Hz, 4H), 7.40 (d, J = 8.3 Hz, 3H), 7.31 (d, J = 6.9 Hz, 1H),
7.19 (dd, J = 7.6, 5.2 Hz, 1H), 4.03 (s, 2H), 2.83-2.73 (m, 1H),
2.21 (s, 3H), 1.25-1.18 (m, 6H) 239C B 579 (M + H) 92.68
(CDCl.sub.3) .delta. 8.58 (s, 1H), 8.30 (s, 1H), 8.22 (t, J = 8.7
Hz, 2H), 7.82 (t, J = 8.7 Hz, 4H), 7.40 (d, J = 8.2 Hz, 3H), 7.31
(d, J = 8.0 Hz, 1H), 7.20 (d, J = 7.3 Hz, 1H), 4.03 (s, 2H),
2.83-2.73 (m, 1H), 2.21 (s, 3H), 1.25-1.18 (m, 6H) NMR spectral
data were acquired using a 400 MHz instrument unless otherwise
noted.
TABLE-US-00007 TABLE 5 Biological Results % % % Mortality Mortality
Mortality Compound CEW 50 BAW 50 GPA 200 Number .mu.g/cm.sup.2
.mu.g/cm.sup.2 ppm 1C A A D 2C A A D 3C A A D 4C A A B 5C A A B 6C
A A D 7C A D D 8C A A B 9C A A D 10C A A D 11C A A D 12C A A B 13C
A A B 14C A A B 15C A A A 16C A A D 17C A A B 18C A A B 19C A A B
20C A A D 21C C C D 22C A A B 23C A A D 24C A A B 25C A A D 26C C C
D 27C A A B 28C A A B 29C A A B 30C A A B 31C A A B 32C C C B 33C A
A B 34C C C B 35C A A B 36C A A D 37C A A D 38C A A D 39C C C D 40C
A A B 41C A A D 42C A A D 43C A A B 44C A A D 45C A A C 46C A A D
47C A A B 48C A A C 49C A A B 50C A A C 51C A A D 52C D B B 53C D B
B 54C A A D 55C A A D 56C A A C 57C A A B 58C A A B 59C A A B 60C A
A D 61C A A C 62C A A B 63C A A D 64C A A D 65C A A B 66C A A B 67C
A A D 68C A A B 69C A A C 70C A A D 71C A A D 72C A A B 73C A A B
74C A A D 75C A A B 76C A A B 77C A A B 78C A A B 79C A A B 80C A A
D 81C A A D 82C A A C 83C A A C 84C A A D 85C A A B 86C A A D 87C C
C B 88C A A B 89C A A D 90C A A B 91C D D C 92C A A B 93C A A D 94C
A A D 95C A A B 96C A A B 97C A A C 98C C A C 99C A A C 100C A A C
101C A A C 102C A A C 103C A A C 104C A A C 105C A A C 106C A A C
107C D D C 108C A A D 109C A A C 110C A A C 111C A A B 112C A A B
113C A A C 114C A A C 115C D B C 116C A A C 117C A A D 118C A A D
119C A A D 120C A A C 121C A A B 122C A A C 123C A A C 124C A A C
125C A A C 126C A A C 127C A A C 128C A A C 129C A A C 130C A A C
131C A A D 132C A A B 133C A A B 134C A A C 135C A A D 136C A A D
137C A A D 138C A A B 139C A A B 140C A A B 141C A A D 142C A A D
143C A A C 144C A A C 145C A A B 146C A A B 147C A A B 148C A A C
149C A A D 150C A A D 151C A A B 152C A A C 153C A D C 154C A A B
155C A A D 156C A A B 157C A A B 158C A A B 159C A A C 160C A A C
161C A A C 162C A A C 163C A A C 164C A A C 165C A A C 166C A A C
167C A A C 168C A A D 169C A A C 170C A A C 171C A A C 172C A A D
173C A A D 174C A A B 175C A A D 176C A A C 177C A A D 178C A A D
179C A A D 180C A A B 181C A A B 182C A A B 183C A A D 184C A A D
185C A A D 186C A A B 187C A A D 188C A A B 189C A A B 190C A A B
191C A A D 192C A A B 193C A A B 194C A A B 195C A A B 196C A A D
197C A A D 198C A A D 199C A A C 200C A A C 201C A A B 202C A A B
203C A A B 204C A A B 205C A A B 206C A A D 207C d D C 208C A A D
209C A A D 210C A A C 211C A A D 212C A A D 213C A A B 214C A A C
215C A A C 216C A A C 217C A A C 218C A A C 219C A A C 220C A A C
221C A A C 222C A A C 223C A A C 224C A A B 225C A A C 226C A A C
227C A A C 228C A A C 229C A A C 230C A A C 231C A A C 232C A A C
233C A A C 234C A A C 235C A A C 236C A A C 237C A A C 238C A A C
239C A A C 240C A A C 241C A A C 242C A A C
243C A A D 244C A A D 245C A A D 246C A A C 247C A A C 248C A A C
249C A A C 250C A A C 251C A A C 252C A A C 253C A A C 254C A A C
255C A A C 256C A A C 257C A A C 258C A B C 259C A A C 260C A A C
261C A A C
* * * * *
References