U.S. patent application number 14/738313 was filed with the patent office on 2015-10-01 for 4-amino-6-(heterocyclic)picolinates and 6-amino-2-(heterocyclic)pyrimidine-4-carboxylates and their use as herbicides.
The applicant listed for this patent is Dow AgroSciences, LLC. Invention is credited to Joseph D. Eckelbarger, Jeffrey B. Epp, Stephen Craig Fields, Lindsey G. Fischer, Natalie C. Giampietro, Katherine A. Guenthenspberger, Christian T. Lowe, Jeff Petkus, Joshua Roth, Norbet M. Satchivi, Paul R. Schmitzer, Thomas L. Siddall, Nick X. Wang.
Application Number | 20150274756 14/738313 |
Document ID | / |
Family ID | 51529777 |
Filed Date | 2015-10-01 |
United States Patent
Application |
20150274756 |
Kind Code |
A1 |
Eckelbarger; Joseph D. ; et
al. |
October 1, 2015 |
4-AMINO-6-(HETEROCYCLIC)PICOLINATES AND
6-AMINO-2-(HETEROCYCLIC)PYRIMIDINE-4-CARBOXYLATES AND THEIR USE AS
HERBICIDES
Abstract
4-Amino-6-(heterocyclic)picolinic acids and their derivatives;
6-amino-2-(heterocyclic)pyrimidine-4-carboxylates and their
derivatives; and methods of using the same as herbicides.
Inventors: |
Eckelbarger; Joseph D.;
(Carmel, IN) ; Epp; Jeffrey B.; (Noblesville,
IN) ; Fields; Stephen Craig; (Indianapolis, IN)
; Fischer; Lindsey G.; (Indianapolis, IN) ;
Giampietro; Natalie C.; (Carmel, IN) ;
Guenthenspberger; Katherine A.; (Daleville, IN) ;
Lowe; Christian T.; (Westfield, IN) ; Petkus;
Jeff; (Indianapolis, IN) ; Roth; Joshua;
(Carmel, IN) ; Satchivi; Norbet M.; (Carmel,
IN) ; Schmitzer; Paul R.; (Indianapolis, IN) ;
Siddall; Thomas L.; (Zionsville, IN) ; Wang; Nick
X.; (Westfield, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow AgroSciences, LLC |
Indianapolis |
IN |
US |
|
|
Family ID: |
51529777 |
Appl. No.: |
14/738313 |
Filed: |
June 12, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14540679 |
Nov 13, 2014 |
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14738313 |
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13839000 |
Mar 15, 2013 |
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14540679 |
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Current U.S.
Class: |
504/103 ;
504/193; 504/239; 504/251; 504/252; 504/253; 544/298; 544/328;
546/14; 546/270.1; 546/275.7; 546/277.4; 546/281.1; 546/284.1 |
Current CPC
Class: |
C07D 405/04 20130101;
C07D 401/04 20130101; C07D 403/04 20130101; A01N 43/52 20130101;
C07D 417/04 20130101; C07F 7/0803 20130101; A01N 43/647 20130101;
A01N 43/40 20130101; A01N 55/00 20130101; C07D 413/04 20130101;
A01N 43/54 20130101; A01N 43/78 20130101; A01N 43/56 20130101; C07D
409/04 20130101; A01N 43/80 20130101; A01N 43/76 20130101 |
International
Class: |
C07F 7/08 20060101
C07F007/08; A01N 43/40 20060101 A01N043/40; A01N 43/78 20060101
A01N043/78; A01N 43/54 20060101 A01N043/54; C07D 405/04 20060101
C07D405/04; A01N 55/00 20060101 A01N055/00; C07D 403/04 20060101
C07D403/04; C07D 401/04 20060101 C07D401/04; C07D 409/04 20060101
C07D409/04 |
Claims
1-32. (canceled)
33. A compound of the Formula (I): ##STR00237## wherein X is N or
CY, wherein Y is hydrogen, halogen, C.sub.1-C.sub.3 alkyl,
C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1'' or
NR.sup.1''R.sup.1''', wherein R.sup.1' is hydrogen, C.sub.1-C.sub.8
alkyl, or C.sub.7-C.sub.10 arylalkyl, and R.sup.1'' and R.sup.1'''
are independently hydrogen, C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is one of groups A1 to A36 ##STR00238## ##STR00239## ##STR00240##
##STR00241## ##STR00242## ##STR00243## R.sup.5 is hydrogen,
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
cyclopropyl, halocyclopropyl, C.sub.2-C.sub.4 alkenyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3
alkylthio, C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4
alkylamino, C.sub.2-C.sub.4 haloalkylamino, OH, or CN; R.sup.6,
R.sup.6', and R.sup.6'' are independently hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or
C.sub.2-C.sub.4 haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and
R.sup.7' are independently hydrogen, halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl,
C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylcarbamyl,
C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 trialkylsilyl, or
phenyl; or an N-oxide or agriculturally acceptable salt thereof,
with the proviso that the compound is not a compound of Formula
(I): ##STR00244## wherein X is N, CH, CF, CCl, or CBr; R.sup.1 is
OR.sup.1', wherein R.sup.1' is hydrogen or C.sub.1-C.sub.4 alkyl;
R.sup.2 is chlorine; R.sup.3 and R.sup.4 are hydrogen; A is A1, A2,
A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15, A16, A17,
A18, A19, or A20; R.sup.5 is hydrogen, halogen, OH, amino, CN,
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
alkylamino, or cyclopropyl; R.sup.6, R.sup.6', and R.sup.6'' are
independently hydrogen, halogen, OH, NH.sub.2, CN, C.sub.1-C.sub.3
alkyl, C.sub.1-C.sub.3 alkoxy, cyclopropyl, or vinyl; R.sup.7 and
R.sup.7' are independently hydrogen, halogen, C.sub.1-C.sub.3
alkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio,
cyclopropyl, or C.sub.1-C.sub.3 alkylamino, or phenyl; and R.sup.8
is hydrogen, C.sub.1-C.sub.3 alkyl, phenyl, or C.sub.1-C.sub.3
alkylcarbonyl; or an N-oxide or agriculturally acceptable salt
thereof.
34. The compound of claim 33, wherein X is CY, wherein Y is
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3
alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 alkylthio, or C.sub.1-C.sub.3 haloalkylthio;
R.sup.1 is OR.sup.1' or NR.sup.1''R.sup.1''', wherein R.sup.1' is
hydrogen, C.sub.1-C.sub.8 alkyl, or C.sub.7-C.sub.10 arylalkyl, and
R.sup.1'' and R.sup.1''' are independently hydrogen,
C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 alkenyl, or
C.sub.3-C.sub.12 alkynyl; R.sup.2 is halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.2-C.sub.4 alkenyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4 haloalkoxy, C.sub.1-C.sub.4
alkylthio, C.sub.1-C.sub.4 haloalkylthio, amino, C.sub.1-C.sub.4
alkylamino, C.sub.2-C.sub.4 haloalkylamino, formyl, C.sub.1-C.sub.3
alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group
of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14,
A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27,
A28, A29, A30, A31, A32, A33, A34, A35, or A36; R.sup.5 is
hydrogen, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
haloalkyl, cyclopropyl, halocyclopropyl, C.sub.2-C.sub.4 alkenyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3
alkylthio, C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4
alkylamino, C.sub.2-C.sub.4 haloalkylamino, OH, or CN; R.sup.6,
R.sup.6', and R.sup.6'' are independently hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or
C.sub.2-C.sub.4 haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and
R.sup.7' are independently hydrogen, halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl,
C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylcarbamyl,
C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 trialkylsilyl, or
phenyl; or an N-oxide or agriculturally acceptable salt
thereof.
35. The compound of claim 33, wherein X is N or CY, wherein Y is
hydrogen, halogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1' or
NR.sup.1''R.sup.1''', wherein R.sup.1' is C.sub.5-C.sub.8 alkyl, or
C.sub.7-C.sub.10 arylalkyl, and R.sup.1'' and R.sup.1''' are
independently hydrogen, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12
alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.2-C.sub.4
alkenyl, C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4 haloalkoxy, C.sub.1-C.sub.4
alkylthio, C.sub.1-C.sub.4 haloalkylthio, amino, C.sub.1-C.sub.4
alkylamino, C.sub.2-C.sub.4 haloalkylamino, formyl, C.sub.1-C.sub.3
alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group
of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14,
A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27,
A28, A29, A30, A31, A32, A33, A34, A35, or A36; R.sup.5 is
hydrogen, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
haloalkyl, cyclopropyl, halocyclopropyl, C.sub.2-C.sub.4 alkenyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3
alkylthio, C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4
alkylamino, C.sub.2-C.sub.4 haloalkylamino, OH, or CN; R.sup.6,
R.sup.6', and R.sup.6'' are independently hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or
C.sub.2-C.sub.4 haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and
R.sup.7' are independently hydrogen, halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl,
C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylcarbamyl,
C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 trialkylsilyl, or
phenyl; or an N-oxide or agriculturally acceptable salt
thereof.
36. The compound of claim 33, wherein X is N or CY, wherein Y is
hydrogen, halogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1' or
NR.sup.1''R.sup.1'''", wherein R.sup.1' is hydrogen,
C.sub.1-C.sub.8 alkyl, or C.sub.7-C.sub.10 arylalkyl, and R" and
R.sup.1''' are independently hydrogen, C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is
F, Br, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14,
A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27,
A28, A29, A30, A31, A32, A33, A34, A35, or A36; R.sup.5 is
hydrogen, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
haloalkyl, cyclopropyl, halocyclopropyl, C.sub.2-C.sub.4 alkenyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3
alkylthio, C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4
alkylamino, C.sub.2-C.sub.4 haloalkylamino, OH, or CN; R.sup.6,
R.sup.6', and R.sup.6'' are independently hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or
C.sub.2-C.sub.4 haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and
R.sup.7' are independently hydrogen, halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl,
C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylcarbamyl,
C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 trialkylsilyl, or
phenyl; or an N-oxide or agriculturally acceptable salt
thereof.
37. The compound of claim 33, wherein X is N or CY, wherein Y is
hydrogen, halogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1' or
NR.sup.1''R.sup.1''', wherein R.sup.1' is hydrogen, C.sub.1-C.sub.8
alkyl, or C.sub.7-C.sub.10 arylalkyl, and R.sup.1'' and R.sup.1'''
are independently hydrogen, C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14,
A15, A16, A17, A18, A19, A20, A21, A22, A23, A24, A25, A26, A27,
A28, A29, A30, A31, A32, A33, A34, A35, or A36; R.sup.5 is
hydrogen, halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
haloalkyl, cyclopropyl, halocyclopropyl, C.sub.2-C.sub.4 alkenyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3
alkylthio, C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4
alkylamino, C.sub.2-C.sub.4 haloalkylamino, OH, or CN; R.sup.6,
R.sup.6', and R.sup.6'' are independently hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or
C.sub.2-C.sub.4 haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and
R.sup.7' are independently hydrogen, halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl,
C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylcarbamyl,
C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 trialkylsilyl, or
phenyl; or an N-oxide or agriculturally acceptable salt
thereof.
38. The compound of claim 33, wherein X is N or CY, wherein Y is
hydrogen, halogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1' or
NR.sup.1''R.sup.1''', wherein R.sup.1' is hydrogen, C.sub.1-C.sub.8
alkyl, or C.sub.7-C.sub.10 arylalkyl, and R.sup.1'' and R.sup.1'''
are independently hydrogen, C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A21, A22, A23, A24, A25, A26, A27, A28, A29, A30, A31, A32, A33,
A34, A35, or A36; R.sup.5 is hydrogen, halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, OH, or CN; R.sup.6, R.sup.6', and R.sup.6'' are
independently hydrogen, halogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or C.sub.2-C.sub.4
haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and R.sup.7' are
independently hydrogen, halogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl,
C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylcarbamyl,
C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 trialkylsilyl, or
phenyl; or an N-oxide or agriculturally acceptable salt
thereof.
39. The compound of claim 33, wherein X is N or CY, wherein Y is
hydrogen, halogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1' or
NR.sup.1''R.sup.1''', wherein R.sup.1' is hydrogen, C.sub.1-C.sub.8
alkyl, or C.sub.7-C.sub.10 arylalkyl, and R.sup.1'' and R.sup.1'''
are independently hydrogen, C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R'.sup.7 is hydrogen, F, or Cl; le is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14,
A15, A16, A17, A18, A19, or A20; R.sup.5 is C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, halocyclopropyl, C.sub.2-C.sub.4
alkenyl, C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, C.sub.4 alkylamino, or
C.sub.2-C.sub.4 haloalkylamino; R.sup.6, R.sup.6', and R.sup.6''
are independently hydrogen, halogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or C.sub.2-C.sub.4
haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and R.sup.7' are
independently hydrogen, halogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl,
C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylcarbamyl,
C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 trialkylsilyl, or
phenyl; or an N-oxide or agriculturally acceptable salt
thereof.
40. The compound of claim 33, wherein X is N or CY, wherein Y is
hydrogen, halogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1' or
NR.sup.1''R.sup.1''', wherein R.sup.1' is hydrogen, C.sub.1-C.sub.8
alkyl, or C.sub.7-C.sub.10 arylalkyl, and R.sup.1'' and R.sup.1'''
are independently hydrogen, C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14,
A15, A16, A17, A18, A19, or A20; R.sup.5 is hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino,
C.sub.2-C.sub.4 haloalkylamino, OH, or CN; R.sup.6, R.sup.6', and
R.sup.6'' are independently C.sub.4 alkyl, C.sub.1-C.sub.4
haloalkyl, halocyclopropyl, C.sub.3-C.sub.4 alkenyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, C.sub.1-C.sub.4 alkylamino or
C.sub.2-C.sub.4 haloalkylamino, or NO.sub.2; R.sup.7 and R.sup.7'
are independently hydrogen, halogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is hydrogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl,
C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3 haloalkylcarbonyl,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 alkylcarbamyl,
C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6 trialkylsilyl, or
phenyl; or an N-oxide or agriculturally acceptable salt
thereof.
41. The compound of claim 33, wherein X is N or CY, wherein Y is
hydrogen, halogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1'' or
NR.sup.1''R.sup.1''', wherein R.sup.1' is hydrogen, C.sub.1-C.sub.8
alkyl, or C.sub.7-C.sub.10 arylalkyl, and R.sup.1'' and R.sup.1'''
are independently hydrogen, C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14,
A15, A16, A17, or A18; R.sup.5 is hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino,
C.sub.2-C.sub.4 haloalkylamino, OH, or CN; R.sup.6, R.sup.6', and
R.sup.6'' are independently hydrogen, halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or C.sub.2-C.sub.4
haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and R.sup.7' are
independently C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.4 alkylamino, or
C.sub.2-C.sub.4 haloalkylamino; R.sup.8 is hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alkynyl,
formyl, C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3
haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6
alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6
trialkylsilyl, or phenyl; or an N-oxide or agriculturally
acceptable salt thereof.
42. The compound of claim 33, wherein X is N or CY, wherein Y is
hydrogen, halogen, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 alkylthio, or
C.sub.1-C.sub.3 haloalkylthio; R.sup.1 is OR.sup.1' or
NR.sup.1''R.sup.1''', wherein R.sup.1' is hydrogen, C.sub.1-C.sub.8
alkyl, or C.sub.7-C.sub.10 arylalkyl, and R.sup.1'' and R.sup.1'''
are independently hydrogen, C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl, or C.sub.3-C.sub.12 alkynyl; R.sup.2 is
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the formula
--CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21, wherein
R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F, Cl,
C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and R.sup.19,
R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10 alkyl,
C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH; R.sup.3 and R.sup.4 are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl,
or R.sup.3 and R.sup.4 taken together with N is a 5- or 6-membered
saturated ring, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alkynyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated ring; A
is A3, A6, A11, A12, A15, A18, A19, or A20; R.sup.5 is hydrogen,
halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl,
cyclopropyl, halocyclopropyl, C.sub.2-C.sub.4 alkenyl,
C.sub.2-C.sub.4 haloalkenyl, C.sub.2-C.sub.4 alkynyl,
C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3
alkylthio, C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4
alkylamino, C.sub.2-C.sub.4 haloalkylamino, OH, or CN; R.sup.6,
R.sup.6', and R.sup.6'' are independently hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or
C.sub.2-C.sub.4 haloalkylamino, OH, CN, or NO.sub.2; R.sup.7 and
R.sup.7' are independently hydrogen, halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, or phenyl; R.sup.8 is C.sub.3-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6
haloalkenyl, C.sub.3-C.sub.6 alkynyl, formyl, C.sub.1-C.sub.3
haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6
alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl, or C.sub.1-C.sub.6
trialkylsilyl; or an N-oxide or agriculturally acceptable salt
thereof.
43. The compound of claim 33, wherein W is OR.sup.1.
44. The compound of claim 33, wherein X is CF.
45. The compound of claim 33, wherein A is A15
46. The compound of any of claim 33, wherein R.sup.5 is F.
47. A herbicidal composition comprising a compound of claim 33 and
an agriculturally acceptable adjuvant or carrier.
48. The composition of claim 47, further comprising an additional
pesticide.
49. The composition of claim 47, further comprising a herbicidal
safener.
50. A method of controlling undesirable vegetation which comprises
applying to vegetation or an area adjacent the vegetation or
applying to soil or water to prevent the emergence or growth of
vegetation a compound of claim 33.
51. A method of controlling undesirable vegetation which comprises
applying to vegetation or an area adjacent the vegetation or
applying to soil or water to prevent the emergence or growth of
vegetation a herbicidal composition of claim 47.
Description
FIELD
[0001] The invention relates to herbicidal compounds and
compositions and to methods for controlling undesirable
vegetation.
BACKGROUND
[0002] The occurrence of undesirable vegetation, e.g., weeds, is a
constant problem facing famers in crops, pasture, and other
settings. Weeds compete with crops and negatively impact crop
yield. The use of chemical herbicides is an important tool in
controlling undesirable vegetation.
[0003] There remains a need for new chemical herbicides that offer
a broader spectrum of weed control, selectivity, minimal crop
damage, storage stability, ease of handling, higher activity
against weeds, and/or a means to address herbicide-tolerance that
develops with respect to herbicides currently in use.
SUMMARY OF THE INVENTION
[0004] Provided herein are compounds of Formula (I):
##STR00001##
wherein
[0005] X is N or CY, wherein Y is hydrogen, halogen,
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 haloalkyl, C.sub.1-C.sub.3
alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 alkylthio or C.sub.1-C.sub.3 haloalkylthio;
[0006] R.sup.1 is OR.sup.1' or NR.sup.1''R.sup.1''', wherein
R.sup.1' is hydrogen, C.sub.1-C.sub.8 alkyl, or C.sub.7-C.sub.10
arylalkyl, and R.sup.1'' and R.sup.1'' are independently hydrogen,
C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 alkenyl, or
C.sub.3-C.sub.12 alkynyl;
[0007] R.sup.2 is halogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
haloalkyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4
haloalkoxy, C.sub.1-C.sub.4 alkylthio, C.sub.1-C.sub.4
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino, C.sub.2-C.sub.4
haloalkylamino, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, cyano, or a group of the
formula-CR.sup.17.dbd.CR.sup.18--SiR.sup.19R.sup.20R.sup.21,
wherein R.sup.17 is hydrogen, F, or Cl; R.sup.18 is hydrogen, F,
Cl, C.sub.1-C.sub.4 alkyl, or C.sub.1-C.sub.4 haloalkyl; and
R.sup.19, R.sup.20, and R.sup.21 are independently C.sub.1-C.sub.10
alkyl, C.sub.3-C.sub.6 cycloalkyl, phenyl, substituted phenyl,
C.sub.1-C.sub.10 alkoxy, or OH;
[0008] R.sup.3 and R.sup.4 are independently hydrogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 haloalkenyl, C.sub.3-C.sub.6 alknyl,
formyl, C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3
haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6
alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6
trialkylsilyl, C.sub.1-C.sub.6 dialkylphosphonyl, or R.sup.3 and
R.sup.4 taken together with N is a 5- or 6-membered saturated ring,
or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, C.sub.3-C.sub.6 alknyl, C.sub.1-C.sub.6 alkoxy or
C.sub.1-C.sub.6 alkylamino, or, R.sup.3' and R.sup.4' taken
together with .dbd.C represent a 5- or 6-membered saturated
ring;
[0009] A is one of groups A1 to A36
##STR00002## ##STR00003## ##STR00004## ##STR00005## ##STR00006##
##STR00007##
[0010] R.sup.5, if applicable to the A group, is hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino,
C.sub.2-C.sub.4 haloalkylamino, OH, or CN;
[0011] R.sup.6, R.sup.6', and R.sup.6'', if applicable to the A
group, are independently hydrogen, halogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, cyclopropyl, halocyclopropyl,
C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4 haloalkenyl,
C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, C.sub.1-C.sub.3 alkylthio, C.sub.1-C.sub.3
haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino or C.sub.2-C.sub.4
haloalkylamino, OH, CN, or NO.sub.2;
[0012] R.sup.7 and R.sup.7' are independently hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino,
C.sub.1-C.sub.4 haloalkylamino, or phenyl;
[0013] R.sup.8 is hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alknyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, or phenyl;
[0014] or an N-oxide or agriculturally acceptable salt thereof.
[0015] Also provided are methods of controlling undesirable
vegetation comprising (a) contacting the undesirable vegetation or
area adjacent to the undesirable vegetation or (b) pre-emergently
contacting soil or water a herbicidally effective amount of at
least one compound of Formula (I) or agriculturally acceptable
derivative thereof.
[0016] Also provided are novel precursors of Formula (II):
##STR00008##
wherein:
[0017] R.sup.7 and R.sup.7' are independently hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
halocyclopropyl, C.sub.2-C.sub.4 alkenyl, C.sub.2-C.sub.4
haloalkenyl, C.sub.2-C.sub.4 alkynyl, C.sub.1-C.sub.3 alkoxy,
C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, amino, C.sub.1-C.sub.4 alkylamino,
C.sub.2-C.sub.4 haloalkylamino, or phenyl;
[0018] R.sup.8 is hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alknyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, C.sub.1-C.sub.6 alkylsulfonyl,
C.sub.1-C.sub.6 trialkylsilyl, or phenyl;
[0019] Z is B(OR.sup.22).sub.2, BF.sub.3M, or Sn(R.sup.23).sub.3,
wherein each R.sup.22 is independently hydrogen or C.sub.1-C.sub.4
alkyl, or the two OR.sup.22 moieties combine to form
--O--C(CH.sub.3).sub.2--C(CH.sub.3).sub.2--O-- or
--O--CH.sub.2--C(CH.sub.3).sub.2--CH.sub.2--O--; M is a metal
cation, e.g. sodium or potassium, and R.sup.23 is C.sub.1-C.sub.4
alkyl; provided the following compound is excluded:
##STR00009##
DETAILED DESCRIPTION
Definitions
[0020] As used herein, herbicide and herbicidal active ingredient
mean a compound that controls undesirable vegetation when applied
in an appropriate amount.
[0021] As used herein, control of or controlling undesirable
vegetation means killing or preventing the vegetation, or causing
some other adverse modifying effect to the vegetation e.g.,
deviations from natural growth or development, regulation,
desiccation, retardation, and the like.
[0022] As used herein, a herbicidally effective or vegetation
controlling amount is an amount of herbicidal active ingredient the
application of which controls the relevant undesirable
vegetation.
[0023] As used herein, applying an herbicide or herbicidal
composition means delivering it directly to the targeted vegetation
or to the locus thereof or to the area where control of undesired
vegetation is desired. Methods of application include, but are not
limited to pre-emergently contacting soil or water, post-emergently
contacting the undesirable vegetation or area adjacent to the
undesirable vegetation.
[0024] As used herein, plants and vegetation include, but are not
limited to, dormant seeds, germinant seeds, emerging seedlings,
plants emerging from vegetative propagules, immature vegetation,
and established vegetation.
[0025] As used herein, agriculturally acceptable salts and esters
refer to salts and esters that exhibit herbicidal activity, or that
are or can be converted in plants, water, or soil to the referenced
herbicide. Exemplary agriculturally acceptable esters are those
that are or can by hydrolyzed, oxidized, metabolized, or otherwise
converted, e.g., in plants, water, or soil, to the corresponding
carboxylic acid which, depending on the pH, may be in the
dissociated or undissociated form.
[0026] Suitable salts include those derived from alkali or alkaline
earth metals and those derived from ammonia and amines. Preferred
cations include sodium, potassium, magnesium, and aminium cations
of the formula:
R.sup.13R.sup.14R.sup.15R.sup.16N.sup.+
wherein R.sup.13, R.sup.14, R.sup.15 and R.sup.16 each,
independently represents hydrogen or C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.12 alkenyl or C.sub.3-C.sub.12 alkynyl, each of which
is optionally substituted by one or more hydroxy, C.sub.1-C.sub.4
alkoxy, C.sub.1-C.sub.4 alkylthio or phenyl groups, provided that
R.sup.13, R.sup.14, R.sup.15 and R.sup.16 are sterically
compatible. Additionally, any two R.sup.13, R.sup.14, R.sup.15 and
R.sup.16 together may represent an aliphatic difunctional moiety
containing one to twelve carbon atoms and up to two oxygen or
sulfur atoms. Salts of the compounds of Formula I can be prepared
by treatment of compounds of Formula I with a metal hydroxide, such
as sodium hydroxide, with an amine, such as ammonia,
trimethylamine, diethanolamine, 2-methylthiopropylamine,
bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine,
or benzylamine or with a tetraalkylammonium hydroxide, such as
tetramethylammonium hydroxide or choline hydroxide. Amine salts are
often preferred forms of the compounds of Formula I because they
are water-soluble and lend themselves to the preparation of
desirable aqueous based herbicidal compositions.
[0027] Compounds of the formula (I) include N-oxides. Pyridine
N-oxides can be obtained by oxidation of the corresponding
pyridines. Suitable oxidation methods are described, for example,
in Houben-Weyl, Methoden der organischen Chemie [Methods in organic
chemistry], expanded and subsequent volumes to the 4th edition,
volume E 7b, p. 565 f.
[0028] As used herein, unless otherwise specified, acyl refers to
formyl, C.sub.1-C.sub.3 alkylcarbonyl, and C.sub.1-C.sub.3
haloalkylcarbonyl. C.sub.1-C.sub.6 acyl refers to formyl,
C.sub.1-C.sub.5 alkylcarbonyl, and C.sub.1-C.sub.5
haloalkylcarbonyl (the group contains a total of 1 to 6 carbon
atoms).
[0029] As used herein, alkyl refers to saturated, straight-chained
or branched saturated hydrocarbon moieties. Unless otherwise
specified, C.sub.1-C.sub.10 alkyl groups are intended. Examples
include methyl, ethyl, propyl, 1-methyl-ethyl, butyl,
1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, pentyl,
1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl,
2,2-dimethyl-propyl, 1-ethyl-propyl, hexyl, 1,1-dimethyl-propyl,
1,2-dimethyl-propyl, 1-methyl-pentyl, 2-methyl-pentyl,
3-methyl-pentyl, 4-methyl-pentyl, 1,1-dimethyl-butyl,
1,2-dimethyl-butyl, 1,3-dimethyl-butyl, 2,2-dimethyl-butyl,
2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 1-ethyl-butyl,
2-ethyl-butyl, 1,1,2-trimethyl-propyl, 1,2,2-trimethyl-propyl,
1-ethyl-1-methyl-propyl, and 1-ethyl-2-methyl-propyl.
[0030] As used herein, "haloalkyl" refers to straight-chained or
branched alkyl groups, where in these groups the hydrogen atoms may
partially or entirely be substituted with halogen atoms. Unless
otherwise specified, C.sub.1-C.sub.8 groups are intended. Examples
include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl,
fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl,
dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl,
1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,
2-chloro-2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,
2,2,2-trichloroethyl, pentafluoroethyl, and
1,1,1-trifluoroprop-2-yl.
[0031] As used herein, alkenyl refers to unsaturated,
straight-chained, or branched hydrocarbon moieties containing a
double bond. Unless otherwise specified, C.sub.2-C.sub.8 alkynyl
are intended. Alkynyl groups may contain more than one unsaturated
bond. Examples include ethenyl, 1-propenyl, 2-propenyl,
1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,
1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,
2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl,
4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl,
3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl,
3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl,
3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl,
1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl,
1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl,
3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl,
2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl,
1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl,
4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl,
3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl,
2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl,
1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,
1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl,
1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl,
1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,
2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,
2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl,
3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl,
1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,
1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, and
1-ethyl-2-methyl-2-propenyl. Vinyl refers to a group having the
structure --CH.dbd.CH.sub.2, 1-propenyl refers to a group with the
structure-CH.dbd.CH--CH.sub.3; and 2-propenyl refers to a group
with the structure --CH.sub.2--CH.dbd.CH.sub.2.
[0032] As used herein, alkynyl represents straight-chained or
branched hydrocarbon moieties containing a triple bond. Unless
otherwise specified, C.sub.2-C.sub.8 alkynyl groups are intended.
Alkynyl groups may contain more than one unstaturated bond.
Examples include C.sub.2-C.sub.6-alkyynyl, such as ethynyl,
1-propynyl, 2-propynyl (or propargyl), 1-butyynyl, 2-butynyl,
3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl,
4-pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl,
1-methyl-3-butinyul, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl,
1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl,
5-hexynyl, 3-methyl-1-pentynyl, 4-methyl-1-pentynyl,
1-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl,
2-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl,
3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl,
1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,
2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl,
1-ethyl-3-butynyl, 2-ethyl-3-butynyl, and
1-ethyl-1-methyl-2-propynyl.
[0033] As used herein, alkoxy refers to a group of the formula
R--O--, where R is alkyl as defined above. Unless otherwise
specified, alkoxy groups wherein R is a C.sub.1-C.sub.8 alkyl group
are intended. Examples include methoxy, ethoxy, propoxy,
1-methyl-ethoxy, butoxy, 1-methyl-propoxy, 2-methyl-propoxy,
1,1-dimethyl-ethoxy, pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy,
3-methyl-butoxy, 2,2-di-methyl-propoxy, 1-ethyl-propoxy, hexoxy,
1,1-dimethyl-propoxy, 1,2-dimethyl-propoxy, 1-methyl-pentoxy,
2-methyl-pentoxy, 3-methyl-pentoxy, 4-methyl-penoxy,
1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3-dimethyl-butoxy,
2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy,
1-ethyl-butoxy, 2-ethylbutoxy, 1,1,2-trimethyl-propoxy,
1,2,2-trimethyl-propoxy, 1-ethyl-1-methyl-propoxy, and
1-ethyl-2-methyl-propoxy.
[0034] As used herein, haloalkoxy refers to a group of the formula
R--O--, where R is haloalkyl as defined above. Unless otherwise
specified, haloalkoxy groups wherein R is a C.sub.1-C.sub.8 alkyl
group are intended. Examples include chloromethoxy, bromomethoxy,
dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy,
trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy,
chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy,
1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,
2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro,
2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,
2,2,2-trichloroethoxy, pentafluoroethoxy, and
1,1,1-trifluoroprop-2-oxy.
[0035] As used herein, alkylthio refers to a group of the formula
R--S-- where R is alkyl as defined above. Unless otherwise
specified, alkylthio groups wherein R is a C.sub.1-C.sub.8 alkyl
group are intended. Examples include methylthio, ethylthio,
propylthio, 1-methylethylthio, butylthio, 1-methyl-propylthio,
2-methylpropylthio, 1,1-dimethylethylthio, pentylthio,
1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio,
2,2-dio-methylpropylthio, 1-ethylpropylthio, hexylthio,
1,1-dimethyl propylthio, 1,2-dimethyl propylthio,
1-methylpentylthio, 2-methylpentylthio, 3-methyl-pentylthio,
4-methyl-pentylthio, 1,1-dimethyl butylthio,
1,2-dimethyl-butylthio, 1,3-dimethyl-butylthio, 2,2-dimethyl
butylthio, 2,3-dimethyl butylthio, 3,3-dimethylbutylthio,
1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethyl propylthio,
1,2,2-trimethyl propylthio, 1-ethyl-1-methyl propylthio, and
1-ethyl-2-methylpropylthio.
[0036] As used herein, haloalkylthio refers to an alkylthio group
as defined above wherein the carbon atoms are partially or entirely
substituted with halogen atoms. Unless otherwise specified,
haloalkylthio groups wherein R is a C.sub.1-C.sub.8 alkyl group are
intended. Examples include chloromethylthio, bromomethylthio,
dichloromethylthio, trichloromethylthio, fluoromethylthio,
difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio,
dichlorofluoro-methylthio, chlorodifluoromethylthio,
1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio,
2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio,
2-chloro-2-fluoroethylthio, 2-chloro-2-difluoroethylthio,
2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio,
pentafluoroethylthio, and 1,1,1-trifluoroprop-2-ylthio.
[0037] As used herein, aryl, as well as derivative terms such as
aryloxy, refers to a phenyl, indanyl or naphthyl group with phenyl
being preferred. The term "heteroaryl", as well as derivative terms
such as "heteroaryloxy", refers to a 5- or 6-membered aromatic ring
containing one or more heteroatoms, viz., N, O or S; these
heteroaromatic rings may be fused to other aromatic systems. The
aryl or heteroaryl substituents may be unsubstituted or substituted
with one or more substituents selected from halogen, hydroxy,
nitro, cyano, formyl, 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 alkoxy,
C.sub.1-C.sub.6 haloalkyl, C.sub.1-C.sub.6 haloalkoxy,
C.sub.1-C.sub.6 acyl, C.sub.1-C.sub.6 alkylthio, C.sub.1-C.sub.6
alkylsulfinyl, C.sub.1-C.sub.6 alkylsulfonyl, C.sub.1-C.sub.6
alkoxycarbonyl, C.sub.1-C.sub.6 carbamoyl, hydroxycarbonyl,
C.sub.1-C.sub.6 alkylcarbonyl, aminocarbonyl, C.sub.1-C.sub.6
alkylaminocarbonyl, C.sub.1-C.sub.6 dialkylaminocarbonyl, provided
that the substituents are sterically compatible and the rules of
chemical bonding and strain energy are satisfied. Preferred
substituents include halogen, C.sub.1-C.sub.2 alkyl and
C.sub.1-C.sub.2 haloalkyl.
[0038] As used herein alkylcarbonyl refers to an alkyl group bonded
to a carbonyl group. C.sub.1-C.sub.3 alkylcarbonyl and
C.sub.1-C.sub.3 haloalkylcarbonyl refer to groups wherein a
C.sub.1-C.sub.3 alkyl group is bonded to a carbonyl group (the
group contains a total of 2 to 4 carbon atoms).
[0039] As used herein, alkoxycarbonyl refers to a group of the
formula
##STR00010##
wherein R is alkyl.
[0040] As used herein, arylalkyl refers to an alkyl group
substituted with an aryl group. C.sub.7-C.sub.10 arylalkyl refers
to a group wherein the total number of carbon atoms in the group is
7 to 10.
[0041] As used herein alkylamino refers to an amino group
substituted with one or two alkyl groups, which may be the same or
different.
[0042] As used herein haloalkylamino refers to an alkylamino group
wherein the alkyl carbon atoms are partially or entirely
substituted with halogen atoms.
[0043] As used herein, C.sub.1-C.sub.6 alkylaminocarbonyl refers to
a group of the formula RNHC(O)-- wherein R is C.sub.1-C.sub.6
alkyl, and C.sub.1-C.sub.6 dialkylaminocarbonyl refers to a group
of the formula R.sub.2NC(O)-- wherein each R is independently
C.sub.1-C.sub.6 alkyl.
[0044] As used herein alkylcarbamyl refers to a carbamyl group
substituted on the nitrogen with an alkyl group.
[0045] As used herein alkylsulfonyl refers to a group of the
formula
##STR00011##
where R is alkyl
[0046] As used herein carbamyl (also referred to as carbamoyl and
aminocarbonyl) refers to a group of the formula
##STR00012##
[0047] As used herein dialkylphosponyl refers to a group of the
formula
##STR00013##
where R is independently alkyl in each occurrence.
[0048] As used herein, C.sub.1-C.sub.6 trialkylsilyl refers to a
group of the formula --SiR.sub.3 wherein each R is independently a
C.sub.1-C.sub.6 alkyl group (the group contains a total of 3 to 18
carbon atoms).
[0049] As used herein Me refers to a methyl group; OMe refers to a
methoxy group; i-Pr refers to an isopropyl group.
[0050] As used herein, the term "halogen" including derivative
terms such as "halo" refers to fluorine, chlorine, bromine and
iodine.
[0051] As used herein, plants and vegetation include, but are not
limited to, germinant seeds, emerging seedlings, plants emerging
from vegetative propagules, immature vegetation, and established
vegetation.
Compounds of Formula (I)
[0052] The invention provides compounds of Formula (I) as defined
above and N-oxides and agriculturally acceptable salts thereof.
[0053] In some embodiments, the compound is the carboxylic acid or
an agriculturally acceptable ester or salt. In some embodiments,
the compound is the carboxylic acid or its methyl ester.
[0054] In some embodiments:
[0055] A is one of groups A1 to A20; [0056] R.sup.1 is OR.sup.1',
wherein R.sup.1' is hydrogen or C.sub.1-C.sub.4 alkyl; [0057]
R.sup.2 is chlorine; [0058] R.sup.3 and R.sup.4 are hydrogen;
[0059] X is N, CH, CF, CCl, or CBr; [0060] R.sup.5 is hydrogen,
halogen, OH, NH2, CN, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
alkoxy, C.sub.1-C.sub.3 alkylamino, or cyclopropyl;
[0061] R.sup.6, R.sup.6', and R.sup.6'' are independently hydrogen,
halogen, OH, NH.sub.2, CN, C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3
alkoxy, cyclopropyl, or vinyl;
[0062] R.sup.7 and R.sup.7' are independently hydrogen, halogen,
C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
alkylthio, cyclopropyl, or C.sub.1-C.sub.3 alkylamino, or phenyl;
and
[0063] R.sup.8 is hydrogen, C.sub.1-C.sub.3 alkyl, phenyl, or
C.sub.1-C.sub.3 alkylcarbonyl.
[0064] In some embodiments, R.sup.1 is OR.sup.1', wherein R.sup.1'
is hydrogen, C.sub.1-C.sub.8 alkyl, or C.sub.7-C.sub.10 arylalkyl.
In some embodiments, R.sup.1' is hydrogen or C.sub.1-C.sub.8 alkyl.
In some embodiments, R.sup.1' is hydrogen.
[0065] In some embodiments, R.sup.2 is halogen, C.sub.1-C.sub.4
alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.2-C.sub.4 alkynyl,
C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4 haloalkenyl, or
C.sub.1-C.sub.4-alkoxy, or C.sub.1-C.sub.4 haloalkoxy. In some
embodiments, R.sup.2 is halogen, C.sub.2-C.sub.4-alkenyl,
C.sub.2-C.sub.4 haloalkenyl, or C.sub.1-C.sub.4-alkoxy. In some
embodiments, R.sup.2 is halogen. In some embodiments, R.sup.2 is
C.sub.2-C.sub.4-alkenyl or C.sub.2-C.sub.4 haloalkenyl. In some
embodiments, R.sup.2 is C.sub.1-C.sub.4 alkoxy. In some
embodiments, R.sup.2 is Cl, OMe, vinyl, or 1-propenyl. In some
embodiments, R.sup.2 is Cl. In some embodiments, R.sup.2 is OMe. In
some embodiments, R.sup.2 is vinyl or 1-propenyl.
[0066] In some embodiments, R.sup.3 and R.sup.4 are independently
hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 haloalkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 haloalkenyl,
C.sub.3-C.sub.6 alknyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl,
C.sub.1-C.sub.3 haloalkylcarbonyl, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 alkylcarbamyl, or R.sup.3 and R.sup.4 taken
together represent .dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and
R.sup.4' are independently hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6 alknyl, C.sub.1-C.sub.6
alkoxy, or C.sub.1-C.sub.6 alkylamino. In some embodiments, R.sup.3
and R.sup.4 are independently hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6
haloalkenyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl, C.sub.1-C.sub.3
haloalkylcarbonyl, or R.sup.3 and R.sup.4 taken together represent
.dbd.CR.sup.3'(R.sup.4'), wherein R.sup.3' and R.sup.4' are
independently hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6
alkoxy or C.sub.1-C.sub.6 alkylamino. In some embodiments, R.sup.3
and R.sup.4 are independently hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 haloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.3-C.sub.6
haloalkenyl, formyl, C.sub.1-C.sub.3 alkylcarbonyl, or
C.sub.1-C.sub.3 haloalkylcarbonyl. In some embodiments, at least
one of R.sup.3 and R.sup.4 are hydrogen. In some embodiments,
R.sup.3 and R.sup.4 are both hydrogen.
[0067] In some embodiments, X is N, CH or CF. In some embodiments,
X is N. In some embodiments, X is CH. In some embodiments, X is
CF.
[0068] In some embodiments, A is A1, A2, A3, A4, A5, A6, A7, A8,
A9, A10, A11, A12, A13, A14, A15, A16, A17, A18, A19, or A20.
[0069] In some embodiments, A is one of A21, A22, A23, A24, A25,
A26, A27, A28, A29, A30, A31, A32, A33, A34, A35, and A36.
[0070] In some embodiments, A is one of groups A1, A2, A3, A7, A8,
A9, A10, A13, A14, and A15. In some embodiments, A is one of groups
A1, A2, A3, A13, A14, and A15. In some embodiments, A is one of
groups A13, A14, and A15. In some embodiments, A is A15.
[0071] In some embodiments, R.sup.5 is hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.3
alkoxy, C.sub.1-C.sub.3 haloalkoxy, C.sub.1-C.sub.3 alkylthio,
C.sub.1-C.sub.3 haloalkylthio, or amino. In some embodiments,
R.sup.5 is hydrogen, halogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.3 alkoxy, C.sub.1-C.sub.3
haloalkoxy, or amino. In some embodiments, R.sup.5 is hydrogen,
halogen, C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4 alkoxy. In some
embodiments, R.sup.5 is hydrogen or F. In some embodiments, R.sup.5
is hydrogen. In some embodiments, R.sup.5 is F.
[0072] In some embodiments, R.sup.6 is hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, C.sub.1-C.sub.3
alkoxy, or C.sub.1-C.sub.3 haloalkoxy. In some embodiments, R.sup.6
is hydrogen or fluorine. In some embodiments, R.sup.6 is hydrogen.
In some embodiments, R.sup.6 is fluorine.
[0073] In some embodiments, R.sup.6' is hydrogen or halogen. In
some embodiments, R.sup.6' is hydrogen, F, or Cl. In some
embodiments, R.sup.6' is hydrogen or F. In some embodiments,
R.sup.6' is hydrogen.
[0074] In some embodiments, R.sup.6'' is hydrogen, halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 haloalkyl, cyclopropyl,
C.sub.2-C.sub.4 alkynyl, CN, or NO.sub.2. In some embodiments,
R.sup.6'' is hydrogen. In some embodiments, R.sup.6'' is halogen.
In some embodiments, R.sup.6'' is C.sub.1-C.sub.4 alkyl. In some
embodiments, R.sup.6'' is C.sub.1-C.sub.4 haloalkyl. In some
embodiments, R.sup.6'' is cyclopropyl. In some embodiments,
R.sup.6'' is C.sub.2-C.sub.4 alkynyl. In some embodiments,
R.sup.6'' is CN. In some embodiments, R.sup.6'' is NO.sub.2.
[0075] In some embodiments:
[0076] R.sup.2 is halogen, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4
haloalkenyl, or C.sub.1-C.sub.4-alkoxy;
[0077] R.sup.3 and R.sup.4 are both hydrogen; and
[0078] X is N, CH, or CF.
[0079] In some embodiments:
[0080] R.sup.2 is halogen;
[0081] R.sup.3 and R.sup.4 are both hydrogen; and
[0082] X is N, CH, or CF.
[0083] In some embodiments:
[0084] R.sup.2 is C.sub.2-C.sub.4-alkenyl or C.sub.2-C.sub.4
haloalkenyl;
[0085] R.sup.3 and R.sup.4 are both hydrogen; and
[0086] X is N, CH, or CF.
[0087] In some embodiments:
[0088] R.sup.2 is C.sub.1-C.sub.4-alkoxy;
[0089] R.sup.3 and R.sup.4 are both hydrogen; and
[0090] X is N, CH, or CF.
[0091] In some embodiments:
[0092] R.sup.2 is halogen, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4
haloalkenyl, or C.sub.1-C.sub.4-alkoxy;
[0093] R.sup.3 and R.sup.4 are both hydrogen;
[0094] X is N, CH, or CF;
[0095] R.sup.5 is hydrogen or F;
[0096] R.sup.6 is hydrogen or F;
[0097] R.sup.6' is hydrogen;
[0098] R.sup.6'', if applicable to the relevant A group, is
hydrogen or halogen; and
[0099] R.sup.7 and R.sup.7', if applicable to the relevant A group,
are independently hydrogen or halogen.
[0100] In some embodiments:
[0101] R.sup.2 is halogen, C.sub.1-C.sub.4-alkoxy, or
C.sub.2-C.sub.4-alkenyl;
[0102] R.sup.3 and R.sup.4 are hydrogen;
[0103] X is N, CH, or CF; and
[0104] A is one of groups A1 to A20;
[0105] In some embodiments:
[0106] R.sup.2 is chlorine;
[0107] R.sup.3 and R.sup.4 are hydrogen;
[0108] X is N, CH, or CF;
[0109] A is one of groups A1 to A20;
[0110] R.sup.5 is hydrogen or F;
[0111] R.sup.6 and R.sup.6' are independently hydrogen or F;
and
[0112] R.sup.7 and R.sup.7', if applicable to the relevant A group,
are independently hydrogen, halogen, C.sub.1-C.sub.4 alkyl, or
C.sub.1-C.sub.4 haloalkyl.
[0113] In some embodiments:
[0114] R.sup.2 is chlorine, methoxy, vinyl, or 1-propenyl;
[0115] R.sup.3 and R.sup.4 are hydrogen; and
[0116] X is N, CH, or CF.
[0117] In some embodiments:
[0118] R.sup.2 is chlorine;
[0119] R.sup.3 and R.sup.4 are hydrogen; and
[0120] X is N, CH, or CF.
[0121] In some embodiments:
[0122] R.sup.2 is vinyl or 1-propenyl;
[0123] R.sup.3 and R.sup.4 are hydrogen; and
[0124] X is N, CH, or CF.
[0125] In some embodiments:
[0126] R.sup.2 is methoxy;
[0127] R.sup.3 and R.sup.4 are hydrogen; and
[0128] X is N, CH, or CF.
[0129] In some embodiments:
[0130] R.sup.2 is chlorine;
[0131] R.sup.3 and R.sup.4 are hydrogen; and
[0132] X is N.
[0133] In some embodiments:
[0134] R.sup.2 is chlorine;
[0135] R.sup.3 and R.sup.4 are hydrogen; and
[0136] X is CH.
[0137] In some embodiments:
[0138] R.sup.2 is chlorine;
[0139] R.sup.3 and R.sup.4 are hydrogen; and
[0140] X is CF.
[0141] In some embodiments:
[0142] R.sup.2 is chlorine;
[0143] R.sup.3 and R.sup.4 are hydrogen;
[0144] X is CF;
[0145] A is one of A1, A2, A3, A7, A8, A9, A10, A13, A14, or
A15;
[0146] R.sup.5 is F; and
[0147] R.sup.6 is H.
[0148] In some embodiments:
[0149] R.sup.2 is chlorine, methoxy, vinyl, or 1-propenyl;
[0150] R.sup.3 and R.sup.4 are hydrogen;
[0151] X is N, CH, or CF; and
[0152] A is one of A21-A36.
[0153] In some embodiments:
[0154] R.sup.2 is chlorine, methoxy, vinyl, or 1-propenyl;
[0155] R.sup.3 and R.sup.4 are hydrogen;
[0156] X is CF; and
[0157] A is one of
##STR00014##
wherein R.sup.5 is hydrogen or F.
[0158] In some embodiments:
[0159] R.sup.2 is chlorine, methoxy, vinyl, or 1-propenyl;
[0160] R.sup.3 and R.sup.4 are hydrogen;
[0161] X is N, CH, or CF; and
[0162] A is
##STR00015##
where R.sup.5 is hydrogen or F.
[0163] In some embodiments:
[0164] R.sup.2 is chlorine, methoxy, vinyl, or 1-propenyl;
[0165] R.sup.3 and R.sup.4 are hydrogen;
[0166] X is N, CH, or CF; and
[0167] A is
##STR00016##
[0168] In some embodiments:
[0169] R.sup.2 is chlorine, methoxy, vinyl, or 1-propenyl;
[0170] R.sup.3 and R.sup.4 are hydrogen;
[0171] X is CF; and
[0172] A is
##STR00017##
[0173] It is particularly noteworthy that compounds of Formula (I)
wherein A is, e.g. A15, exhibit a significant increase in activity
when X is CF. This is demonstrated by comparing the activity of
Compounds 1.21 and 1.22 (wherein X is CH) with that of 1.08 and
1.09 (wherein X is CF). It is also demonstrated by comparing the
activity of Compounds 1.23 and 1.24 (wherein X is CH) with that of
Compounds 1.15 and 1.16 (wherein X is CF). The increased activity
is further enhanced when R.sup.5 is F.
Exemplary Compounds
[0174] The following Tables 1-9 describe exemplary compounds of
Formula (I')
##STR00018##
Table 10 sets forth the structure, appearance, preparation method,
and precursor(s) used in synthesis of the exemplary compounds.
Table 11 sets forth physical data for each of the exemplary
compounds.
[0175] Blank spaces in compound tables herein indicate hydrogen, or
that for the A group indicated in a particular row the column in
which the blank occurs is not relevant
TABLE-US-00001 TABLE 1 Compounds of Formula (I') with indolyl tails
A3 ##STR00019## A15 ##STR00020## A27 ##STR00021## A28 ##STR00022##
C. No. R.sup.1' R.sup.2 X A R.sup.5 R.sup.6 R.sup.6' R.sup.6''
R.sup.7 R.sup.7' R.sup.8 1.01 H Cl CF A03 Me 1.02 Me Cl CF A03 1.03
Me Cl CF A03 Me 1.04 H Cl CF A03 1.05 Me Cl CCl A15 1.06 H Cl CCl
A15 1.07 Me Cl CCl A15 F 1.08 Me Cl CF A15 1.09 H Cl CF A15 1.10 Me
Cl CF A15 Me 1.11 H Cl CF A15 Me 1.12 Me Cl CF A15 F Si(i-Pr).sub.3
1.13 Me Cl CF A15 F 1.14 H Cl CF A15 F 1.15 Me Cl CF A15 F 1.16 H
Cl CF A15 F 1.17 H OMe CF A15 F 1.18 Me vinyl CF A15 F 1.19 H vinyl
CF A15 F 1.20 Me OMe CF A15 F 1.21 Me Cl CH A15 1.22 H Cl CH A15
1.23 Me Cl CH A15 F 1.24 H Cl CH A15 F 1.25 Me Cl CH A15 F 1.26 H
Cl CH A15 F 1.27 Me Cl CH A15 F F 1.28 Me Cl CMe A15 1.29 H Cl CMe
A15 1.30 Me Cl N A15 1.31 Me Cl N A15 F 1.32 Me OMe N A15 1.33 H
OMe N A15 1.34 Me OMe N A15 F 1.35 H OMe N A15 F 1.36 Me OMe N A15
F 1.37 H OMe N A15 F 1.38 Me vinyl N A15 F 1.39 H vinyl N A15 F
1.40 Me Cl CF A27 1.41 Me Cl CF A27 Me 1.42 H Cl CF A27 Me 1.43 Me
Cl CF A27 Cl 1.44 Me Cl CH A27 Cl 1.45 Me OMe N A27 Cl 1.46 Me Cl
CF A28 Cl 1.47 Me Cl CF A28 1.48 H Cl CF A28 1.49 Me Cl CH A28 Cl
1.50 Me OMe N A28 Cl A is A3, A15, A27, or A28
TABLE-US-00002 TABLE 2 Compounds of Formula (I') with bernzofuranyl
tails A1 ##STR00023## A13 ##STR00024## A21 ##STR00025## A22
##STR00026## C. No. R.sup.1' R.sup.2 X A R.sup.5 R.sup.6 R.sup.6'
R.sup.6'' R.sup.7 R.sup.7'' R.sup.8 2.01 Me Cl CF A01 2.02 H Cl CF
A01 2.03 Me Cl CH A01 2.04 Me Cl CH A01 F 2.05 Me OMe N A01 F 2.06
Me OMe N A01 2.07 Me Cl CF A13 2.08 H Cl CF A13 2.09 Me Cl CF A13 F
2.10 Me Cl CF A13 F 2.11 Me Cl CH A13 F 2.12 Me Cl CH A13 F 2.13 Me
OMe N A13 F 2.14 Me OMe N A13 F 2.15 Me Cl CF A21 2.16 Me Cl CF A21
Cl 2.17 H Cl CF A21 2.18 H Cl CF A21 Cl 2.19 Me Cl CH A21 Cl 2.20
Me Cl N A21 Cl 2.21 Me OMe N A21 Cl 2.22 H OMe N A21 Cl 2.23 H Cl N
A21 Cl 2.24 Me Cl CF A22 Cl 2.25 Me Cl CH A22 Cl 2.26 Me OMe N A22
Cl A is Al, A13, A21, or A22
TABLE-US-00003 TABLE 3 Compounds of Formula (I') with
benzothiofuranyl tails A2 ##STR00027## A14 ##STR00028## A23
##STR00029## A24 ##STR00030## C.No. R.sup.1' R.sup.2 X A R.sup.5
R.sup.6 R.sup.6' R.sup.6'' R.sup.7 R.sup.7' R.sup.8 3.01 Me Cl CC1
A02 3.02 H Cl CC1 A02 3.03 Me Cl CF A02 3.04 H Cl CF A02 3.05 Me Cl
CH A02 3.06 Me Cl CMe A02 3.07 H Cl CMe A02 3.08 Me OMe N A02 3.09
H OMe N A02 3.10 Me Cl CC1 A14 3.11 H Cl CC1 A14 3.12 Me Cl CF A14
3.13 H Cl CF A14 3.14 Me Cl CF A14 F 3.15 Me Cl CH A14 3.16 H Cl CH
A14 3.17 Me Cl CH A14 F 3.18 Me Cl CMe A14 3.19 H Cl CMe A14 3.20
Me OMe N A14 3.21 H OMe N A14 3.22 Me OMe N A14 F 3.23 Me Cl CF A23
3.24 Me Cl CF A24 3.25 H Cl CF A24 3.26 Me Cl CF A24 Br 3.27 Me Cl
CH A24 A is A2, A14, A23, or A24:
TABLE-US-00004 TABLE 4 Compounds of Formula (I') with IH-indazolyl
tails C. No. R.sup.1' R.sup.2 X A R.sup.5 R.sup.6 R.sup.6'
R.sup.6'' R.sup.7 R.sup.7' R.sup.8 4.01 Me Cl CF A06 4.02 H Cl CF
A06 4.03 Me Cl CF A06 Me 4.04 H Cl CF A06 Me 4.05 Me Cl CF A18 4.06
H Cl CF A18 4.07 Me Cl CF A18 Me 4.08 H Cl CF A18 Me 4.09 Me Cl CH
A18 4.10 Me Cl CF A25 Me 4.11 H Cl CF A25 Me 4.12 Me Cl CF A25 4.13
Me Cl CF A26 A is one of groups A6, A18, A25, and A26: ##STR00031##
##STR00032##
TABLE-US-00005 TABLE 5 Compounds of Formula (I') with benzoxazolyl
tails C. No. R.sup.1' R.sup.2 X A R.sup.5 R.sup.6 R.sup.6'
R.sup.6'' R.sup.7 R.sup.7' R.sup.8 5.01 Me Cl CF A09 A is A7, A9,
A29, or A30: ##STR00033## ##STR00034##
TABLE-US-00006 TABLE 6 Compounds of Formula (I') with
benzothiazolyl tails C. No. R.sup.1' R.sup.2 X A R.sup.5 R.sup.6
R.sup.6' R.sup.6'' R.sup.7 R.sup.7' R.sup.8 6.01 Me Cl CF A08 6.02
H Cl CF A08 A is A8, A10, A31, or A32: ##STR00035##
##STR00036##
TABLE-US-00007 TABLE 7 Compounds of Formula (I') with
1H-benzimidazolyl tails C. No. R.sup.1' R.sup.2 X A R.sup.5 R.sup.6
R.sup.6' R.sup.6'' R.sup.7 R.sup.7' R.sup.8 7.01 Me Cl CF A12 7.02
Me Cl CF A12 Me 7.03 H Cl CF A12 Me A is one of groups A11 and A12:
##STR00037##
TABLE-US-00008 TABLE 8 Compounds of Formula (I') with indoxazinyl
tails C. No. R.sup.1' R.sup.2 X A R.sup.5 R.sup.6 R.sup.6'
R.sup.6'' R.sup.7 R.sup.7' R.sup.8 8.01 Me Cl CF A16 NMe.sub.2 A is
A4, A16, A33, or A34: ##STR00038## ##STR00039##
TABLE-US-00009 TABLE 9 Compounds of Formula (I') with
1H-benzotriazolyl tails C. No. R.sup.1' R.sup.2 X A R.sup.5 R.sup.6
R.sup.6' R.sup.6'' R.sup.7 R.sup.7' R.sup.8 9.01 Me Cl CH A20 A is
A19 or A20: ##STR00040##
Methods of Preparing the Compounds
[0176] Exemplary procedures to synthesize the compounds of Formula
(I) are provided below.
[0177] The 4-amino-6-(heterocyclic)picolinic acids of Formula (I)
can be prepared in a number of ways. As depicted in Scheme I, the
4-amino-6-chloropicolinates of Formula (II) can be converted to the
4-amino-6-substituted-picolinates of Formula (III), wherein Ar is
as herein defined, via Suzuki coupling with a boronic acid or
ester, in the presence of a base, such as potassium fluoride, and a
catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride,
in a polar, protic solvent mixture, such as acetonitrile-water, at
a temperature, such as 110.degree. C., e.g., in a microwave reactor
(reaction a.sub.1). 4-Amino-6-substituted-picolinates of Formula
(III) can be transformed into the
5-iodo-4-amino-6-substituted-picolinates of Formula (IV) via a
reaction with iodinating reagents, such as periodic acid and
iodine, in a polar, protic solvent, such as methyl alcohol
(reaction b.sub.1). Stille coupling of the
5-iodo-4-amino-6-substituted-picolinates of Formula (IV) with a
stannane, such as tetramethyltin, in the presence of a catalyst,
such as bis(triphenylphosphine)-palladium(II) dichloride, in a
non-reactive solvent, such as 1,2-dichloroethane, at a temperature,
such as 120-130.degree. C., e.g., in a microwave reactor, provides
5-(substituted)-4-amino-6-substituted-picolinates of Formula (I-A),
wherein Z.sub.1 is alkyl, alkenyl, alkynyl, haloalkenyl and
alkylthio (reaction c.sub.1).
[0178] Alternatively, 4-amino-6-chloropicolinates of Formula (II)
can be transformed to the 5-iodo-4-amino-6-chloropicolinates of
Formula (V) via a reaction with iodinating reagents, such as
periodic acid and iodine, in a polar, protic solvent, such as
methyl alcohol (reaction b.sub.2). Stille coupling of the
5-iodo-4-amino-6-chloropicolinates of Formula (V) with a stannane,
such as tetramethyltin, in the presence of a catalyst, such as
bis(triphenylphosphine)-palladium(II) dichloride, in a non-reactive
solvent, such as 1,2-dichloroethane, at a temperature, such as
120-130.degree. C., e.g., in a microwave reactor, provides
5-(substituted)-4-amino-6-chloropicolinates of Formula (VI),
wherein Z.sub.1 is alkyl, alkenyl, alkynyl, haloalkenyl and
alkylthio (reaction c.sub.2). The
5-substituted-4-amino-6-chloropicolinates of Formula (VI) can be
converted to the 5-substituted-4-amino-6-substituted-picolinates of
Formula (I-A), wherein Ar is as herein defined, via Suzuki coupling
with a boronic acid or ester, in the presence of a base, such as
potassium fluoride, and a catalyst, such as
bis(triphenylphosphine)-palladium(II) dichloride, in a polar,
protic solvent mixture, such as acetonitrile-water, at a
temperature, such as 110.degree. C., e.g., in a microwave reactor
(reaction a.sub.2).
##STR00041##
[0179] As depicted in Scheme II, the 4,5,6-trichloropicolinate of
Formula (VII) can be converted to the corresponding isopropyl ester
of Formula (VIII), via a reaction with isopropyl alcohol and
concentrated sulfuric acid, e.g., at reflux temperature under
Dean-Stark conditions (reaction d). The isopropyl ester of Formula
(VIII) can be reacted with a fluoride ion source, such as cesium
fluoride, in a polar, aprotic solvent, such as dimethyl sulfoxide,
at a temperature, such as 80.degree. C., under Dean-Stark
conditions, to yield the isopropyl 4,5,6-trifluoropicolinate of
Formula (IX) (reaction e). The isopropyl 4,5,6-trifluoropicolinate
of Formula (IX) can be aminated with a nitrogen source, such as
ammonia, in a polar, aprotic solvent, such as dimethyl sulfoxide,
to produce a 4-amino-5,6-difluoropicolinate of Formula (X)
(reaction f). The fluoro substituent in the 6-position of the
4-amino-5,6-difluoropicolinate of Formula (X) can be exchanged with
a chloro substituent by treatment with a chloride source, such as
hydrogen chloride, e.g., in dioxane, in a Parr reactor, at a
temperature, such as 100.degree. C., to produce a
4-amino-5-fluoro-6-chloro-picolinate of Formula (XI) (reaction g).
The 4-amino-5-fluoro-6-chloropicolinate of Formula (XI) can be
transesterified to the corresponding methyl ester of Formula (XII)
by reaction with titanium(IV) isopropoxide in methyl alcohol at
reflux temperature (reaction h).
##STR00042##
[0180] As depicted in Scheme III, the
4-amino-5-fluoro-6-chloropicolinate of Formula (XII) can be
transformed into the 3-iodo-4-amino-5-fluoro-6-chloropicolinate of
Formula (XIII) via reaction with iodinating reagents, such as
periodic acid and iodine, in a polar, protic solvent, such as
methyl alcohol (reaction b.sub.3). Stille coupling of the
3-iodo-4-amino-5-fluoro-6-chloropicolinates of Formula (XIII) with
a stannane, such as tributyl(vinyl)stannane, in the presence of a
catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride,
in a non-reactive solvent, such as 1,2-dichloroethane, at a
temperature, such as 120-130.degree. C., e.g., in a microwave
reactor, provides
3-(substituted)-4-amino-5-fluoro-6-chloropicolinates of Formula
(XIV), wherein R.sup.2 is alkyl, alkenyl, alkynyl, haloalkenyl and
alkylthio (reaction c.sub.3). Alternatively, the
3-iodo-4-amino-5-fluoro-6-chloropicolinates of Formula (XIII) can
be treated with cesium carbonate and a catalytic amount of both
copper(I) iodide and 1,10-phenanthroline in the presence of a
polar, protic solvent, such as methyl alcohol, at a temperature,
such as 65.degree. C., to provide a
3-(substituted)-4-amino-5-fluoro-6-chloropicolinic acids of Formula
(XIV), wherein R.sup.2 is alkoxy or haloalkoxy (reaction i.sub.1),
which can be esterified to the methyl esters, e.g., by treatment
with hydrogen chloride (gas) and methyl alcohol at 50.degree. C.
(reaction j.sub.1). The
3-(substituted)-4-amino-5-fluoro-6-chloropicolinates of Formula
(XIV) can be converted to the 4-amino-6-substituted-picolinates of
Formula (I-B), wherein Ar is as herein defined, via Suzuki coupling
with a boronic acid or ester, in the presence of a base, such as
potassium fluoride, and a catalyst, such as
bis(triphenylphosphine)-palladium(II) dichloride, in a polar,
protic solvent mixture, such as acetonitrile-water, at a
temperature, such as 110.degree. C., e.g., in a microwave reactor
(reaction a.sub.3).
[0181] Alternatively, the 4-amino-5-fluoro-6-chloropicolinates of
Formula (XII) can be converted to the
4-amino-5-fluoro-6-substituted-picolinates of Formula (XV), wherein
Ar is as herein defined, via Suzuki coupling with a boronic acid or
ester, in the presence of a base, such as potassium fluoride, and a
catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride,
in a polar, protic solvent mixture, such as acetonitrile-water, at
a temperature, such as 110.degree. C., e.g., in a microwave reactor
(reaction a.sub.4). The 4-amino-5-fluoro-6-substituted-picolinates
of Formula (XV) can be transformed into the
3-iodo-4-amino-5-fluoro-6-substituted-picolinates of Formula (XVI)
via reaction with iodinating reagents, such as periodic acid and
iodine, in a polar, protic solvent, such as methyl alcohol
(reaction b.sub.4). Stille coupling of the
3-iodo-4-amino-5-fluoro-6-substituted-picolinates of Formula (XVI)
with a stannane, such as tributyl(vinyl)stannane, in the presence
of a catalyst, such as bis(triphenylphosphine)-palladium(II)
dichloride, in a non-reactive solvent, such as 1,2-dichloroethane,
at a temperature, such as 120-130.degree. C., e.g., in a microwave
reactor, provides
3-(substituted)-4-amino-5-fluoro-6-substituted-picolinates of
Formula (I-B), wherein R.sup.2 is alkyl, alkenyl, alkynyl,
haloalkenyl and alkylthio (reaction c.sub.4). Alternatively, the
3-iodo-4-amino-5-fluoro-6-substituted-picolinates of Formula (XVI)
can be treated with cesium carbonate and a catalytic amount of both
copper(I) iodide and 1,10-phenanthroline in the presence of a
polar, protic solvent, such as methyl alcohol, at a temperature,
such as 65.degree. C., to provide a
3-(substituted)-4-amino-5-fluoro-6-substituted-picolinic acids of
Formula (I-B), wherein R.sup.2 is alkoxy or haloalkoxy (reaction
i.sub.2), which can be esterified to the methyl esters, e.g., by
treatment with hydrogen chloride (gas) and methyl alcohol, at a
temperature, such as 50.degree. C. (reaction j.sub.2).
##STR00043##
[0182] As depicted in Scheme IV, the
4-acetamido-6-(trimethylstannyl)picolinates of Formula (XVII) can
be converted to the 4-acetamido-6-substituted-picolinates of
Formula (XVIII), wherein Ar is as herein defined, via Still
coupling with an aryl bromide or aryl iodide, in the presence of a
catalyst, such as bis(triphenylphosphine)-palladium(II) dichloride,
in a solvent, such as dichloroethane, e.g., at reflux temperature
(reaction k). 4-Amino-6-substituted-picolinates of Formula (I-C),
wherein Ar is as herein defined, can be synthesized from
4-acetamido-6-substituted-picolinates of Formula (XVIII) via
standard deprotecting methods, such as hydrochloric acid gas in
methanol (reaction 1).
##STR00044##
[0183] As depicted in Scheme V, 2,4-dichloro-5-methoxypyrimidine
(XIX) can be transformed into
2,4-dichloro-5-methoxy-6-vinylpyrimidine (XX) via a reaction with
vinyl magnesium bromide, in a polar, aprotic solvent, such as
tetrahydrofuran (reaction m).
2,4-Dichloro-5-methoxy-6-vinylpyrimidine (XX) can be transformed
into 2,6-dichloro-5-methoxypyrimidine-4-carboxaldehyde (XXI) via
treatment with ozone, e.g., in a dichloromethane:methanol solvent
mixture (reaction n).
2,6-Dichloro-5-methoxypyrimidine-4-carboxaldehyde (XXI) can be
transformed into methyl
2,6-dichloro-5-methoxypyrimidine-4-carboxylate (XXII) via treatment
with bromine, e.g., in a methanol:water solvent mixture (reaction
o). Methyl 2,6-dichloro-5-methoxypyrimidine-4-carboxylate (XXII)
can be transformed into methyl
6-amino-2-chloro-5-methoxypyrimidine-4-carboxylate (XXIII) via
treatment with ammonia (e.g., 2 equivalents) in a solvent, such as
DMSO (reaction p). Finally,
6-amino-2-substituted-5-methoxypyrimidine-4-carboxylates of Formula
(I-D), wherein Ar is as herein defined, can be prepared via Suzuki
coupling with a boronic acid or ester, with
6-amino-2-chloro-5-methoxypyrimidine-4-carboxylate (XXIII), in the
presence of a base, such as potassium fluoride, and a catalyst,
such as bis(triphenylphosphine)-palladium(II) dichloride, in a
polar, protic solvent mixture, such as acetonitrile-water, at a
temperature, such as 110.degree. C., e.g., in a microwave reactor
(reaction a.sub.5).
##STR00045##
[0184] The compounds of Formulae I-A, I-B, I-C, and I-D obtained by
any of these processes, can be recovered by conventional means and
purified by standard procedures, such as by recrystallization or
chromatography. The compounds of Formula (I) can be prepared from
compounds of Formulae I-A, I-B, I-C, and I-D using standard methods
well known in the art.
Compositions and Methods
[0185] In some embodiments, the compounds provided herein are
employed in mixtures containing an herbicidally effective amount of
the compound along with at least one agriculturally acceptable
adjuvant or carrier. Exemplary adjuvants or carriers include those
that are not phytotoxic or significantly phytotoxic to valuable
crops, e.g., at the concentrations employed in applying the
compositions for selective weed control in the presence of crops,
and/or do not react or significantly react chemically with the
compounds of provided herein or other composition ingredients. Such
mixtures can be designed for application directly to weeds or their
locus or can be concentrates or formulations that are \diluted with
additional carriers and adjuvants before application. They can be
solids, such as, for example, dusts, granules, water dispersible
granules, or wettable powders, or liquids, such as, and for
example, emulsifiable concentrates, solutions, emulsions or
suspensions. They can also be provided as a pre-mix or
tank-mixed.
[0186] Suitable agricultural adjuvants and carriers that are useful
in preparing the herbicidal mixtures of the disclosure are well
known to those skilled in the art. Some of these adjuvants include,
but are not limited to, crop oil concentrate (mineral oil
(85%)+emulsifiers (15%)); nonylphenol ethoxylate;
benzylcocoalkyldimethyl quaternary ammonium salt; blend of
petroleum hydrocarbon, alkyl esters, organic acid, and anionic
surfactant; C.sub.9-C.sub.11 alkylpolyglycoside; phosphated alcohol
ethoxylate; natural primary alcohol (C.sub.12-C.sub.16) ethoxylate;
di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap;
nonylphenol ethoxylate+urea ammonium nitrrate; emulsified
methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO);
tallow amine ethoxylate (15 EO); PEG(400) dioleate-99.
[0187] Liquid carriers that can be employed include water and
organic solvents. The organic solvents typically used include, but
are not limited to, petroleum fractions or hydrocarbons such as
mineral oil, aromatic solvents, paraffinic oils, and the like;
vegetable oils such as soybean oil, rapeseed oil, olive oil, castor
oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil,
linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung
oil and the like; esters of the above vegetable oils; esters of
monoalcohols or dihydric, trihydric, or other lower polyalcohols
(4-6 hydroxy containing), such as 2-ethylhexyl stearate, n-butyl
oleate, isopropyl myristate, propylene glycol dioleate, di-octyl
succinate, di-butyl adipate, di-octyl phthalate and the like;
esters of mono-, di- and poly-carboxylic acids and the like.
Specific organic solvents include toluene, xylene, petroleum
naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone,
trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate,
butyl acetate, propylene glycol monomethyl ether and diethylene
glycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropyl
alcohol, amyl alcohol, ethylene glycol, propylene glycol,
glycerine, N-methyl-2-pyrrolidinone, N,N-dimethyl alkylamides,
dimethyl sulfoxide, liquid fertilizers, and the like. In some
embodiments, water is the carrier for the dilution of
concentrates.
[0188] Suitable solid carriers include talc, pyrophyllite clay,
silica, attapulgus clay, kaolin clay, kieselguhr, chalk,
diatomaceous earth, lime, calcium carbonate, bentonite clay,
Fuller's earth, cottonseed hulls, wheat flour, soybean flour,
pumice, wood flour, walnut shell flour, lignin, and the like.
[0189] In some embodiments, one or more surface-active agents are
utilized in the compositions of the present disclosure. Such
surface-active agents are, in some embodiments, employed in both
solid and liquid compositions, e.g., those designed to be diluted
with carrier before application. The surface-active agents can be
anionic, cationic or nonionic in character and can be employed as
emulsifying agents, wetting agents, suspending agents, or for other
purposes. Surfactants conventionally used in the art of formulation
and which may also be used in the present formulations are
described, inter alia, in McCutcheon's Detergents and Emulsifiers
Annual, MC Publishing Corp., Ridgewood, N.J., 1998, and in
Encyclopedia of Surfactants, Vol. I-III, Chemical Publishing Co.,
New York, 1980-81. Typical surface-active agents include salts of
alkyl sulfates, such as diethanolammonium lauryl sulfate;
alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate;
alkylphenol-alkylene oxide addition products, such as
nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition
products, such as tridecyl alcohol-C.sub.16 ethoxylate; soaps, such
as sodium stearate; alkylnaphthalene-sulfonate salts, such as
sodium dibutylnaphthalenesulfonate; dialkyl esters of
sulfosuccinate salts, such as sodium di(2-ethylhexyl)
sulfosuccinate; sorbitol esters, such as sorbitol oleate;
quaternary amines, such as lauryl trimethylammonium chloride;
polyethylene glycol esters of fatty acids, such as polyethylene
glycol stearate; block copolymers of ethylene oxide and propylene
oxide; salts of mono- and dialkyl phosphate esters; vegetable or
seed oils such as soybean oil, rapeseed/canola oil, olive oil,
castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed
oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil,
tung oil and the like; and esters of the above vegetable oils,
e.g., methyl esters.
[0190] Oftentimes, some of these materials, such as vegetable or
seed oils and their esters, can be used interchangeably as an
agricultural adjuvant, as a liquid carrier or as a surface active
agent.
[0191] Other adjuvants commonly used in agricultural compositions
include compatibilizing agents, antifoam agents, sequestering
agents, neutralizing agents and buffers, corrosion inhibitors,
dyes, odorants, spreading agents, penetration aids, sticking
agents, dispersing agents, thickening agents, freezing point
depressants, antimicrobial agents, and the like. The compositions
may also contain other compatible components, for example, other
herbicides, plant growth regulants, fungicides, insecticides, and
the like and can be formulated with liquid fertilizers or solid,
particulate fertilizer carriers such as ammonium nitrate, urea and
the like.
[0192] The concentration of the active ingredients in the
herbicidal compositions of this disclosure is generally from about
0.001 to about 98 percent by weight. Concentrations from about 0.01
to about 90 percent by weight are often employed. In compositions
designed to be employed as concentrates, the active ingredient is
generally present in a concentration from about 5 to about 98
weight percent, preferably about 10 to about 90 weight percent.
Such compositions are typically diluted with an inert carrier, such
as water, before application. The diluted compositions usually
applied to weeds or the locus of weeds generally contain about
0.0001 to about 1 weight percent active ingredient and preferably
contain about 0.001 to about 0.05 weight percent.
[0193] The present compositions can be applied to weeds or their
locus by the use of conventional ground or aerial dusters,
sprayers, and granule applicators, by addition to irrigation or
flood water, and by other conventional means known to those skilled
in the art.
[0194] In some embodiments, the compounds and compositions
described herein are applied as a post-emergence application,
pre-emergence application, in-water application to flooded paddy
rice or water bodies (e.g., ponds, lakes and streams), or burn-down
application.
[0195] In some embodiments, the compounds and compositions provided
herein are utilized to control weeds in crops, including but not
limited to citrus, apple, rubber, oild palm, forestry,
direct-seeded, water-seeded and transplanted rice, wheat, barley,
oats, rye, sorghum, corn/maize, pastures, grasslands, rangelands,
fallowland, turf, tree and vine orchards, aquatics, or row-crops,
as well as non-crop settings, e.g., industrial vegetation
management or rights of way. In some embodiments, the compounds and
compositions are used to control woody plants, broadleaf and grass
weeds, or sedges.
[0196] In some embodiments, the compounds and compositions provided
herein are utilized to control undesirable vegetation in rice. In
certain embodiments, the undesirable vegetation is Brachiaria
platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP),
Digitaria sanguinalis (L.) Scop. (large crabgrass, DIGSA),
Echinochloa crus-galli (L.) P. Beauv. (barnyardgrass, ECHCG),
Echinochloa colonum (L.) LINK (junglerice, ECHCO), Echinochloa
oryzoides (Ard.) Fritsch (early watergrass, ECHOR), Echinochloa
oryzicola (Vasinger) Vasinger (late watergrass, ECHPH), Ischaemum
rugosum Salisb. (saramollagrass, ISCRU), Leptochloa chinensis (L.)
Nees (Chinese sprangletop, LEFCH), Leptochloa fascicularis (Lam.)
Gray (bearded sprangletop, LEFFA), Leptochloa panicoides (Presl.)
Hitchc. (Amazon sprangletop, LEFPA), Panicum dichotomiflorum (L.)
Michx. (fall panicum, PANDI), Paspalum dilatatum Poir.
(dallisgrass, PASDI), Cyperus difformis L. (smallflower flatsedge,
CYPDI), Cyperus esculentus L. (yellow nutsedge, CYPES), Cyperus
iria L. (rice flatsedge, CYPIR), Cyperus rotundus L. (purple
nutsedge, CYPRO), Eleocharis species (ELOSS), Fimbristylis miliacea
(L.) Vahl (globe fringerush, FIMMI), Schoenoplectus juncoides Roxb.
(Japanese bulrush, SPCJU), Schoenoplectus maritimus L. (sea
clubrush, SCPMA), Schoenoplectus mucronatus L. (ricefield bulrush,
SCPMU), Aeschynomene species, (jointvetch, AESSS), Alternanthera
philoxeroides (Mart.) Griseb. (alligatorweed, ALRPH), Alisma
plantago-aquatica L. (common waterplantain, ALSPA), Amaranthus
species, (pigweeds and amaranths, AMASS), Ammannia coccinea Rottb.
(redstem, AMMCO), Eclipta alba (L.) Hassk. (American false daisy,
ECLAL), Heteranthera limosa (SW.) Willd./Vahl (ducksalad, HETLI),
Heteranthera reniformis R. & P. (roundleaf mudplantain, HETRE),
Ipomoea hederacea (L.) Jacq. (ivyleaf morningglory, IPOHE),
Lindernia dubia (L.) Pennell (low false pimpernel, LIDDU),
Monochoria korsakowii Regel & Maack (monochoria, MOOKA),
Monochoria vaginalis (Burnt F.) C. Presl ex Kuhth, (monochoria,
MOOVA), Murdannia nudiflora (L.) Brenan (doveweed, MUDNU),
Polygonum pensylvanicum L., (Pennsylvania smartweed, POLPY),
Polygonum persicaria L. (ladysthumb, POLPE), Polygonum
hydropiperoides Michx. (POLHP, mild smartweed), Rotala indica
(Willd.) Koehne (Indian toothcup, ROTIN), Sagittaria species,
(arrowhead, SAGSS), Sesbania exaltata (Raf.) Cory/Rydb. Ex Hill
(hemp sesbania, SEBEX), or Sphenoclea zeylanica Gaertn. (gooseweed,
SPDZE).
[0197] In some embodiments, the compounds and compositions provided
herein are utilized to control undesirable vegetation in cereals.
In certain embodiments, the undesirable vegetation is Alopecurus
myosuroides Huds. (blackgrass, ALOMY), Apera spica-venti (L.)
Beauv. (windgrass, APESV), Avena fatua L. (wild oat, AVEFA), Bromus
tectorum L. (downy brome, BROTE), Lolium multiflorum Lam. (Italian
ryegrass, LOLMU), Phalaris minor Retz. (littleseed canarygrass,
PHAMI), Poa annua L. (annual bluegrass, POANN), Setaria pumila
(Poir.) Roemer & J. A. Schultes (yellow foxtail, SETLU),
Setaria viridis (L.) Beauv. (green foxtail, SETVI), Cirsium arvense
(L.) Scop. (Canada thistle, CIRAR), Galium aparine L. (catchweed
bedstraw, GALAP), Kochia scoparia (L.) Schrad. (kochia, KCHSC),
Lamium purpureum L. (purple deadnettle, LAMPU), Matricaria recutita
L. (wild chamomile, MATCH), Matricaria matricarioides (Less.)
Porter (pineappleweed, MATMT), Papaver rhoeas L. (common poppy,
PAPRH), Polygonum convolvulus L. (wild buckwheat, POLCO), Salsola
tragus L. (Russian thistle, SASKR), Stellaria media (L.) Vill.
(common chickweed, STEME), Veronica persica Poir. (Persian
speedwell, VERPE), Viola arvensis Murr. (field violet, VIOAR), or
Viola tricolor L. (wild violet, VIOTR).
[0198] In some embodiments, the compounds and compostions provided
herein are utilized to control undesirable vegetation in range and
pasture. In certain embodiments, the undesirable vegetation is
Ambrosia artemisiifolia L. (common ragweed, AMBEL), Cassia
obtusifolia (sickle pod, CASOB), Centaurea maculosa auct. non Lam.
(spotted knapweed, CENMA), Cirsium arvense (L.) Scop. (Canada
thistle, CIRAR), Convolvulus arvensis L. (field bindweed, CONAR),
Euphorbia esula L. (leafy spurge, EPHES), Lactuca serriola L./Torn.
(prickly lettuce, LACSE), Plantago lanceolata L. (buckhorn
plantain, PLALA), Rumex obtusifolius L. (broadleaf dock, RUMOB),
Sida spinosa L. (prickly sida, SIDSP), Sinapis arvensis L. (wild
mustard, SINAR), Sonchus arvensis L. (perennial sowthistle, SONAR),
Solidago species (goldenrod, SOOSS), Taraxacum officinale G. H.
Weber ex Wiggers (dandelion, TAROF), Trifolium repens L. (white
clover, TRFRE), or Urtica dioica L. (common nettle, URTDI).
[0199] In some embodiments, the compounds and compositions provided
herein are utilized to control undesirable vegetation found in row
crops. In certain embodiments, the undesirable vegetation is
Alopecurus myosuroides Huds. (blackgrass, ALOMY), Avena fatua L.
(wild oat, AVEFA), Brachiaria platyphylla (Groseb.) Nash (broadleaf
signalgrass, BRAPP), Digitaria sanguinalis (L.) Scop. (large
crabgrass, DIGSA), Echinochloa crus-galli (L.) P. Beauv.
(barnyardgrass, ECHCG), Echinochloa colonum (L.) Link (junglerice,
ECHCO), Lolium multiflorum Lam. (Italian ryegrass, LOLMU), Panicum
dichotomiflorum Michx. (fall panicum, PANDI), Panicum miliaceum L.
(wild-proso millet, PANMI), Setaria faberi Herrm. (giant foxtail,
SETFA), Setaria viridis (L.) Beauv. (green foxtail, SETVI), Sorghum
halepense (L.) Pers. (Johnsongrass, SORHA), Sorghum bicolor (L.)
Moench ssp. Arundinaceum (shattercane, SORVU), Cyperus esculentus
L. (yellow nutsedge, CYPES), Cyperus rotundus L. (purple nutsedge,
CYPRO), Abutilon theophrasti Medik. (velvetleaf, ABUTH), Amaranthus
species (pigweeds and amaranths, AMASS), Ambrosia artemisiifolia L.
(common ragweed, AMBEL), Ambrosia psilostachya DC. (western
ragweed, AMBPS), Ambrosia trifida L. (giant ragweed, AMBTR),
Asclepias syriaca L. (common milkweed, ASCSY), Chenopodium album L.
(common lambsquarters, CHEAL), Cirsium arvense (L.) Scop. (Canada
thistle, CIRAR), Commelina benghalensis L. (tropical spiderwort,
COMBE), Datura stramonium L. (jimsonweed, DATST), Daucus carota L.
(wild carrot, DAUCA), Euphorbia heterophylla L. (wild poinsettia,
EPHHL), Erigeron bonariensis L. (hairy fleabane, ERIBO), Erigeron
canadensis L. (Canadian fleabane, ERICA), Helianthus annuus L.
(common sunflower, HELAN), Jacquemontia tamnifolia (L.) Griseb.
(smallflower morningglory, IAQTA), Ipomoea hederacea (L.) Jacq.
(ivyleaf morningglory, IPOHE), Ipomoea lacunosa L. (white
morningglory, IPOLA), Lactuca serriola L./Torn. (prickly lettuce,
LACSE), Portulaca oleracea L. (common purslane, POROL), Sida
spinosa L. (prickly sida, SIDSP), Sinapis arvensis L. (wild
mustard, SINAR), Solanum ptychanthum Dunal (eastern black
nightshade, SOLPT), or Xanthium strumarium L. (common cocklebur,
XANST).
[0200] In some embodiments, application rates of about 1 to about
4,000 grams/hectare (g/ha) are employed in post-emergence
operations. In some embodiments, rates of about 1 to about 4,000
g/ha are employed in pre-emergence operations.
[0201] In some embodiments, the compounds, compositions, and
methods provided herein are used in conjunction with one or more
other herbicides to control a wider variety of undesirable
vegetation When used in conjunction with other herbicides, the
presently claimed compounds can be formulated with the other
herbicide or herbicides, tank-mixed with the other herbicide or
herbicides or applied sequentially with the other herbicide or
herbicides. Some of the herbicides that can be employed in
conjunction with the compounds of the present disclosure include:
4-CPA; 4-CPB; 4-CPP; 2,4-D; 2,4-D choline salt, 2,4-D esters and
amines; 2,4-DB; 3,4-DA; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP;
2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen,
acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac,
ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron,
aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole,
ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine,
azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid,
benazolin, bencarbazone, benfluralin, benfuresate,
bensulfuron-methyl, bensulide, benthiocarb, bentazon-sodium,
benzadox, benzfendizone, benzipram, benzobicyclon, benzofenap,
benzofluor, benzoylprop, benzthiazuron, bicyclopyrone, bifenox,
bilanafos, bispyribac-sodium, borax, bromacil, bromobonil,
bromobutide, bromofenoxim, bromoxynil, brompyrazon, butachlor,
butafenacil, butamifos, butenachlor, buthidazole, buthiuron,
butralin, butroxydim, buturon, butylate, cacodylic acid,
cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor,
carbasulam, carbetamide, carboxazole chlorprocarb,
carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, chloramben,
chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam,
chloreturon, chlorfenac, chlorfenprop, chlorflurazole,
chlorflurenol, chloridazon, chlorimuron, chlornitrofen, chloropon,
chlorotoluron, chloroxuron, chloroxynil, chlorpropham,
chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin,
cinosulfuron, cisanilide, clethodim, cliodinate,
clodinafop-propargyl, clofop, clomazone, clomeprop, cloprop,
cloproxydim, clopyralid, cloransulam-methyl, CMA, copper sulfate,
CPMF, CPPC, credazine, cresol, cumyluron, cyanatryn, cyanazine,
cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop-butyl,
cyperquat, cyprazine, cyprazole, cypromid, daimuron, dalapon,
dazomet, delachlor, desmedipham, desmetryn, di-allate, dicamba,
dichlobenil, dichloralurea, dichlormate, dichlorprop,
dichlorprop-P, diclofop, diclosulam, diethamquat, diethatyl,
difenopenten, difenoxuron, difenzoquat, diflufenican,
diflufenzopyr, dimefuron, dimepiperate, dimethachlor,
dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon,
dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb,
diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA,
DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon,
esprocarb, ethalfluralin, ethbenzamide, ethametsulfuron,
ethidimuron, ethiolate, ethobenzamid, etobenzamid, ethofumesate,
ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD,
fenasulam, fenoprop, fenoxaprop, fenoxaprop-P-ethyl,
fenoxaprop-P-ethyl+isoxadifen-ethyl, fenoxasulfone, fenteracol,
fenthiaprop, fentrazamide, fenuron, ferrous sulfate, flamprop,
flamprop-M, flazasulfuron, florasulam, fluazifop,
fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron,
fluchloralin, flufenacet, flufenican, flufenpyr-ethyl, flumetsulam,
flumezin, flumiclorac-pentyl, flumioxazin, flumipropyn,
fluometuron, fluorodifen, fluoroglycofen, fluoromidine,
fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate,
flupyrsulfuron, fluridone, flurochloridone, fluroxypyr, flurtamone,
fluthiacet, fomesafen, foramsulfuron, fosamine, furyloxyfen,
glufosinate, glufosinate-ammonium, glyphosate, halosafen,
halosulfuron-methyl, haloxydine, haloxyfop-methyl,
haloxyfop-P-methyl, halauxifen-methyl, hexachloroacetone,
hexaflurate, hexazinone, imazamethabenz, imazamox, imazapic,
imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan,
indaziflam, iodobonil, iodomethane, iodosulfuron, iofensulfuron,
ioxynil, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil,
isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon,
isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop,
karbutilate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA,
MCPA, esters and amines, MCPA-thioethyl, MCPB, mecoprop,
mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine,
mesosulfuron, mesotrione, metam, metamifop, metamitron,
metazachlor, metazosulfuron, metflurazon, methabenzthiazuron,
methalpropalin, methazole, methiobencarb, methiozolin, methiuron,
methometon, methoprotryne, methyl bromide, methyl isothiocyanate,
methyldymron, metobenzuron, metobromuron, metolachlor, metosulam,
metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron,
monochloroacetic acid, monolinuron, monuron, morfamquat, MSMA,
naproanilide, napropamide, naptalam, neburon, nicosulfuron,
nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon,
noruron, OCH, orbencarb, ortho-dichlorobenzene, orthosulfamuron,
oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxasulfuron,
oxaziclomefone, oxyfluorfen, paraflufen-ethyl, parafluron,
paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam,
pentachlorophenol, pentanochlor, pentoxazone, perfluidone,
pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl,
phenobenzuron, phenylmercury acetate, picloram, picolinafen,
pinoxaden, piperophos, potassium arsenite, potassium azide,
potassium cyanate, pretilachlor, primisulfuron-methyl, procyazine,
prodiamine, profluazol, profluralin, profoxydim, proglinazine,
prohexadione-calcium, prometon, prometryn, propachlor, propanil,
propaquizafop, propazine, propham, propisochlor, propoxycarbazone,
propyrisulfuron, propyzamide, prosulfalin, prosulfocarb,
prosulfuron, proxan, prynachlor, pydanon, pyraclonil, pyraflufen,
pyrasulfotole, pyrazogyl, pyrazolynate, pyrazosulfuron-ethyl,
pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor, pyridafol,
pyridate, pyriftalid, pyriminobac, pyrimisulfan,
pyrithiobac-methyl, pyroxasulfone, pyroxsulam, quinclorac,
quinmerac, quinoclamine, quinonamid, quizalofop,
quizalofop-P-ethyl, rhodethanil, rimsulfuron, saflufenacil,
S-metolachlor, sebuthylazine, secbumeton, sethoxydim, siduron,
simazine, simeton, simetryn, SMA, sodium arsenite, sodium azide,
sodium chlorate, sulcotrione, sulfallate, sulfentrazone,
sulfometuron, sulfosate, sulfosulfuron, sulfuric acid, sulglycapin,
swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione,
tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton,
terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron,
thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl,
thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone,
tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam,
tribenuron, tricamba, triclopyr esters and amines, tridiphane,
trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop,
trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac,
tritosulfuron, vernolate and xylachlor.
[0202] The compounds and compositions of the present disclosure can
generally be employed in combination with known herbicide safeners,
such as benoxacor, benthiocarb, brassinolide, cloquintocet (e.g.,
mexyl), cyometrinil, daimuron, dichlormid, dicyclonon,
dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim,
flurazole, fluxofenim, furilazole, harpin proteins,
isoxadifen-ethyl, mefenpyr-diethyl, MG 191, MON 4660, naphthalic
anhydride (NA), oxabetrinil, R29148 and N-phenylsulfonylbenzoic
acid amides, to enhance their selectivity.
[0203] The compounds, compositions, and methods described herein be
used to control undesirable vegetation on glyphosate-tolerant-,
glufosinate-tolerant-, dicamba-tolerant-, phenoxy auxin-tolerant-,
pyridyloxy auxin-tolerant-, aryloxyphenoxypropionate-tolerant-,
acetyl CoA carboxylase (ACCase) inhibitor-tolerant-,
imidazolinone-tolerant-, acetolactate synthase (ALS)
inhibitor-tolerant-, 4-hydroxyphenyl-pyruvate dioxygenase (HPPD)
inhibitor-tolerant-, protoporphyrinogen oxidase (PPO)
inhibitor-tolerant-, triazine-tolerant-, bromoxynil-tolerant-crops
(such as, but not limited to, soybean, cotton, canola/oilseed rape,
rice, cereals, corn, turf, etc), for example, in conjunction with
glyphosate, glufosinate, dicamba, phenoxy auxins, pyridyloxy
auxins, aryloxyphenoxypropionates, ACCase inhibitors,
imidazolinones, ALS inhibitors, HPPD inhibitors, PPO inhibitors,
triazines, and bromoxynil The compositions and methods may be used
in controlling undesirable vegetation in crops possessing multiple
or stacked traits conferring tolerance to multiple chemistries
and/or inhibitors of multiple modes of action.
[0204] The compounds and compositions provided herein may also be
employed to control herbicide resistant or tolerant weeds.
Exemplary resistant or tolerant weeds include, but are not limited
to, biotypes resistant or tolerant to acetolactate synthase (ALS)
inhibitors, photosystem II inhibitors, acetyl CoA carboxylase
(ACCase) inhibitors, synthetic auxins, photosystem I inhibitors,
5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors,
microtubule assembly inhibitors, lipid synthesis inhibitors,
protoporphyrinogen oxidase (PPO) inhibitors, carotenoid
biosynthesis inhibitors, very long chain fatty acid (VLCFA)
inhibitors, phytoene desaturase (PDS) inhibitors, glutamine
synthetase inhibitors, 4-hydroxyphenyl-pyruvate-dioxygenase (HPPD)
inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors,
herbicides with multiple modes-of-action such as quinclorac, and
unclassified herbicides such as arylaminopropionic acids,
difenzoquat, endothall, and organoarsenicals. Exemplary resistant
or tolerant weeds include, but are not limited to, biotypes with
resistance or tolerance to multiple herbicides, multiple chemical
classes, and multiple herbicide modes-of-action.
[0205] The described embodiments and following examples are for
illustrative purposes and are not intended to limit the scope of
the claims. Other modifications, uses, or combinations with respect
to the compositions described herein will be apparent to a person
of ordinary skill in the art without departing from the spirit and
scope of the claimed subject matter.
Synthesis of Precursers
Preparation 1: Methyl 4-amino-3,6-dichloropicolinate (Head A)
##STR00046##
[0207] Prepared as described in Fields et al., WO 2001051468
A1.
Preparation 2: Methyl 4-amino-3,6-dichloro-5-fluoropicolinate (Head
B)
##STR00047##
[0209] Prepared as described in Fields et al., Tetrahedron Letters
(2010), 51(1), 79-81.
Preparation 3: 2,6-Dichloro-5-methoxy-4-vinyl pyrimidine
##STR00048##
[0211] To a solution of commercially available
2,6-dichloro-5-methoxy pyrimidine (100 g, 0.55 mol) in dry
tetrahydrofuran was added, dropwise, 1M vinyl magnesium bromide in
tetrahydrofuran solvent (124 g, 0.94 mol) over one hour (h) at room
temperature. The mixture was then stirred for 4 h at room
temperature. Excess Grignard reagent was quenched by addition of
acetone (200 mL) while the temperature of the mixture was
maintained at a temperature below 20.degree. C. Thereafter,
2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) (151 g, 0.67 mol) was
added at once and stirred overnight. A yellow solid precipitated
out. The solid was filtered and washed with ethyl acetate (500 mL).
The filtrate was concentrated under reduced pressure and the
resulting crude compound was diluted with ethyl acetate (2 L). The
resulting undissolved, dark, semi-solid was separated by filtration
using ethyl acetate. It was further concentrated under reduced
pressure to provide a crude compound, which was purified by column
chromatography. The compound was eluted with 5% to 10% ethyl
acetate in hexane mixture to provide the title compound (70 g,
60%): mp 60-61.degree. C.; .sup.1H NMR (CDCl.sub.3) .delta. 3.99
(s, 3H), 5.85 (d, 1H), 6.75 (d, 1H), 6.95 (dd, 1H).
Preparation 4: 2,6-Dichloro-5-methoxy-pyrimidine-4-carbaldehyde
##STR00049##
[0213] A solution of 2,6-dichloro-5-methoxy-4-vinyl pyrimidine (50
g, 0.24 mol) in dichloromethane:methanol (4:1, 2 L) was cooled to
-78.degree. C. Ozone gas was bubbled therethrough for 5 h. The
reaction was quenched with dimethyl sulfide (50 mL). The mixture
was slowly warmed to room temperature and concentrated under
reduced pressure at 40.degree. C. to provide the title compound
(50.5 g, 100%); HPLC (85% acetonitrile buffered with 0.1% v/v
acetic acid).
Preparation 5: Methyl
2,6-dichloro-5-methoxy-pyrimidine-4-carboxylate
##STR00050##
[0215] A solution of
2,6-dichloro-5-methoxy-pyrimidine-4-carbaldehyde (50 g, 0.24 mol)
in methanol (1 L) and water (60 mL) was prepared. To the solution,
sodium bicarbonate (400 g) was added. A 2 M solution of bromine
(192 g, 1.2 mol) in methanol/water (600 mL, 9:1 was added,
dropwise, to the pyrimidine solution for 45 minutes (min) at
0.degree. C. while stirring the mixture. The stirring was continued
at the same temperature for 1 h. Later, the mixture was stirred at
room temperature for 4 h. While stirring, the reaction mixture was
thereafter poured onto a mixture of crushed ice (2 L), sodium
bisulfite (50 g), and sodium chloride (200 g). The product was
extracted with ethyl acetate (1 L x 2), and the combined organic
layer was dried over sodium sulfate and filtered. Evaporation of
the solvent under reduced pressure produced a thick material, which
solidified on long standing to afford the title compound (50.8 g,
87%); ESIMS m/z 238 ([M+H].sup.+).
Preparation 6: Methyl
6-amino-2-chloro-5-methoxy-pyrimidine-4-carboxylate (Head C)
##STR00051##
[0217] A solution of methyl
2,6-dichloro-5-methoxy-pyrimidine-4-carboxylate (25 g, 0.1 mol) and
dimethyl sulfoxide (DMSO) was prepared. To this solution was added,
at 0-5.degree. C., a solution of ammonia (2 eq) in DMSO. This
mixture was stirred at the same 0-5.degree. C. temperature for 10
to 15 min Later, the mixture was diluted with ethyl acetate, and
the resulting solid was filtered off. The ethyl acetate filtrate
was washed with a brine solution and dried over sodium sulfate.
Upon concentration, the crude product was obtained. The crude
product was stirred in a minimum amount of ethyl acetate and
filtered to obtain the pure compound. Additional pure compound was
obtained from the filtrate which, after concentration, was purified
by flash chromatography. This produced the title compound (11 g,
50%): mp 158.degree. C.; .sup.1H NMR (DMSO-d.sub.6) .delta. 3.71
(s, 3H), 3.86 (s, 3H), 7.65 (brs, 1H), 8.01 (brs, 1H).
Preparation 7: Methyl 4-amino-3,6-dichloro-5-iodopicolinate
##STR00052##
[0219] Methyl 4-amino-3,6-dichloropicolinate (10.0 g, 45.2 mmol),
periodic acid (3.93 g, 17.2 mmol), and iodine (11.44 g, 45.1 mmol)
were dissolved in methanol (30 mL) and refluxed at 60.degree. C.
for 27 h. The reaction mixture was concentrated, diluted with
diethyl ether, and washed twice with saturated aqueous sodium
bisulfite. The aqueous layers were extracted once with diethyl
ether, and the combined organic layers were dried over anhydrous
sodium sulfate. The product was concentrated and purified by flash
chromatography (silica gel, 0-50% ethyl acetate/hexanes) to provide
the title compound as a pale yellow solid (12.44 g, 35.9 mmol,
79%): mp 130.0-131.5.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 5.56 (s, 2H), 3.97 (s, 3H); .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 163.80, 153.00, 152.75, 145.63, 112.12, 83.91,
53.21; EIMS m/z 346.
Preparation 8: Methyl 4-amino-3,6-dichloro-5-methylpicolinate (Head
D)
##STR00053##
[0221] A mixture of methyl 4-amino-3,6-dichloro-5-iodopicolinate
(8.1 g, 23.4 mmol), tetramethylstannane (8.35 g, 46.7 mmol), and
bis(triphenylphosphine)palladium(II) chloride (2.5 g, 3.5 mmol) in
1,2-dichloroethane (40 mL) was irradiated in a Biotage Initiator
microwave at 120.degree. C. for 30 min, with external IR-sensor
temperature monitoring from the side. The reaction mixture was
loaded directly onto a silica gel cartridge and purified by flash
chromatography (silica gel, 0-50% ethyl acetate/hexanes) to provide
the title compound as an orange solid (4.53 g, 19.27 mmol, 83%): mp
133-136.degree. C.; .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 4.92
(s, 2H), 3.96 (s, 3H), 2.29 (s, 3H); .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 164.34, 150.24, 148.69, 143.94, 117.01, 114.60,
53.02, 14.40; ESIMS m/z 236 ([M+H].sup.+), 234 ([M-H].sup.-).
Preparation 9: Methyl 6-amino-2,5-dichloropyrimidine-4-carboxylate
(Head E)
##STR00054##
[0223] Prepared as described in Epp et al., WO 2007082076 A1.
Preparation 10: Methyl
4-amino-6-chloro-5-fluoro-3-methoxypicolinate (Head F)
##STR00055##
[0224] Prepared as described in Epp et al., WO 2013003740 A1.
Preparation 11: Methyl 4-amino-6-chloro-5-fluoro-3-vinylpicolinate
(Head G)
##STR00056##
[0226] Methyl 4-amino-6-chloro-5-fluoro-3-iodopicolinate (7.05 g,
21.33 mmol, prepared as described in Epp et al., WO 2013003740 A1)
and vinyltri-n-butyltin (7.52 mL, 25.6 mmol) were suspended in
dichloroethane (71.1 mL) and the mixture was degassed with Argon
for 10 min bis(triphenylphosphine)palladium(II) chloride (1.497 g,
2.133 mmol) was then added and the reaction mixture was stirred at
70.degree. C. overnight (clear orange solution). The reaction was
monitored by GCMS. After 20 h, the reaction mixture was
concentrated, adsorbed onto Celite, and purified by column
chromatography (SiO2, hexanes/ethyl acetate gradient) to afford the
title compound as a light brown solid (3.23 g, 65.7%) as a light
brown solid: mp 99-100.degree. C.; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 6.87 (dd, J=18.1, 11.6 Hz, 1H), 5.72 (dd,
J=11.5, 1.3 Hz, 1H), 5.52 (dd, J=18.2, 1.3 Hz, 1H), 4.79 (s, 2H),
3.91 (s, 3H); .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -138.79
(s); EIMS m/z 230.
Preparation 12: Methyl 4-amino-3,5,6-trichloropicolinate (Head
H)
##STR00057##
[0228] Prepared as described in Finkelstein et al., WO 2006062979
A1.
Preparation 13: Methyl 4-amino-6-bromo-3-chloro-5-fluoropicolinate
(Head I)
##STR00058##
[0230] Prepared as described in Arndt et al., US 20120190857
A1.
Preparation 14: Methyl
4-amino-3-chloro-5-fluoro-6-(trimethylstannyl)picolinate (Head
J)
##STR00059##
[0232] Methyl 4-amino-6-bromo-3-chloro-5-fluoropicolinate (500 mg,
1.8 mmol), 1,1,1,2,2,2-hexamethyldistannane (580 mg, 1.8 mmol) and
bis(triphenylphosphine)-palladium(II) chloride (120 mg, 0.18 mmol)
were combined in 6 mL dry dioxane, sparged with a stream of
nitrogen for 10 min and then heated to 80.degree. C. for 2 h. The
cooled mixture was stirred with 25 mL ethyl acetate and 25 mL
saturated NaCl for 15 min. The organic phase was separated,
filtered through diatomaceous earth, dried (Na.sub.2SO.sub.4) and
evaporated. The residue was taken up in 4 mL ethyl acetate, stirred
and treated in portions with 15 mL hexane. The milky white solution
was decanted from any solids produced, filtered through glass wool
and evaporated to give the title compound as an off-white solid
(660 mg, 100%): .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 4.63 (d,
J=29.1 Hz, 1H), 3.97 (s, 2H), 0.39 (s, 4H); .sup.19F NMR (376 MHz,
CDCl.sub.3) .delta.-130.28; EIMS m/z 366.
Preparation 15: Methyl
4-acetamido-3-chloro-6-(trimethylstannyl)-picolinate (Head K)
##STR00060##
[0234] Prepared as described in Balko et al., WO 2003011853 A1.
Preparation 16: Methyl 4-acetamido-3,6-dichloropicolinate (Head
L)
##STR00061##
[0236] Prepared as described in Fields et al., WO 2001051468
A1.
Preparation 17: Methyl 4-amino-3-chloro-6-iodopicolinate (Head
M)
##STR00062##
[0238] Prepared as described in Balko et al., WO 2007082098 A2.
Preparation 18: Methyl 4-acetamido-3-chloro-6-iodopicolinate (Head
N)
##STR00063##
[0240] Prepared as described in Balko et al., WO 2007082098 A2.
Preparation 19: Methyl 4-amino-6-bromo-3,5-difluoropicolinate (Head
O)
##STR00064##
[0242] Prepared as described in Fields et al., WO 2001051468
A1.
Preparation 20: Methyl
6-amino-2-chloro-5-vinylpyrimidine-4-carboxylate (Head P)
##STR00065##
[0244] Prepared as described in Epp et al., US20090088322.
Preparation 21: 1-Bromo-4-(2,2-diethoxyethoxy)-2-fluorobenzene
##STR00066##
[0246] 4-Bromo-3-fluorophenol (7 g, 0.03665 mol) and potassium
carbonate (7.6 g, 0.055 mol) were dissolved in
N,N-dimethylformamide (9 mL). 2-Bromo-1,1-diethoxyethane (8.5 mL,
0.055 mol) was added and the reaction mixture was stirred and
heated to 135.degree. C. for 7 h. The solvent was removed after the
reaction was completed. The residue was dissolved in ethyl acetate
and washed with 2M NaOH solution. The organic phase was dried over
Na.sub.2SO.sub.4. The solvent was evaporated to yield
1-bromo-4-(2,2-diethoxyethoxy)-2-fluorobenzene as an oil (11.4 g,
100%).
Preparation 22: 1-Bromo-3-(2,2-diethoxyethoxy)-2-fluorobenzene
##STR00067##
[0248] 1-bromo-3-(2,2-diethoxyethoxy)-2-fluorobenzene was prepared
from 3-bromo-2-fluorophenol as described in Preparation 81.
Preparation 23: 2-Bromo-4-(2,2-diethoxyethoxy)-1-fluorobenzene
##STR00068##
[0250] 2-bromo-4-(2,2-diethoxyethoxy)-1-fluorobenzene was prepared
from 3-bromo-4-fluorophenol as described in Preparation 81.
Preparation 24: 1-Bromo-4-chloro-2-(2,2-diethoxyethoxyl)benzene
##STR00069##
[0252] 1-bromo-4-chloro-2-(2,2-diethoxyethoxyl)benzene was prepared
from 2-bromo-5-chlorophenol as described in Preparation 81.
Preparation 25:
(4-Bromo-3-fluorophenyl)(2,2-diethoxyethyl)sulfane
##STR00070##
[0254] (4-bromo-3-fluorophenyl)(2,2-diethoxyethyl)sulfane was
prepared from 4-bromo-3-fluorobenzenethiol as described in
Preparation 81.
Preparation 26: 4-Bromo-7-chlorobenzofuran
##STR00071##
[0256] To 80 mL of benzene was added polyphosphoric acid (3.47 g,
36.9 mmol) and commercially available
2-(5-bromo-2-chlorophenoxy)acetaldehyde (9.2 g, 36.9 mmol) and
separated into eight 20 mL vials containing equal amounts. The
vials were heated with an external temperature of 90.degree. C. for
4 days. Upon cooling of the reaction, the benzene was removed by
decanting. Celite (50 g) was added to the organic solution and the
solvent was removed using a rotary evaporator. The impregnated
Celite was loaded onto a Teledyne-Isco purification system and
purified by silica gel chromatography using 0-30% ethyl
acetate:hexanes to give 4-bromo-7-chlorobenzofuran as a white solid
(2.7 g, 32%): .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.73 (d,
J=2.2 Hz, 1H), 7.33 (d, J=8.3 Hz, 1H), 7.18 (d, J=8.3 Hz, 1H), 6.85
(d, J=2.2 Hz, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) .delta.
150.38 (s), 146.14 (s), 130.27 (s), 126.56 (s), 125.32 (s), 116.44
(s), 112.49 (s), 107.71 (s); ESIMS m/z 232 ([M+H].sup.+), 230
([M-H].sup.-).
Preparation 27: 6-Bromobenzofuran and 4-bromobenzofuran
##STR00072##
[0258] 6-Bromobenzofuran and 4-bromobenzofuran were prepared as
described in US20040147559 from
1-bromo-3-(2,2-diethoxyethoxyl)benzene.
Preparation 28: 5-Bromo-6-fluorobenzofuran and
5-bromo-4-fluorobenzofuran
##STR00073##
[0260] 1-Bromo-4-(2,2-diethoxyethoxy)-2-fluorobenzene (11.4 g,
0.037 mol) was dissolved in toluene (78 mL). Polyphosphoric acid
(11.9 g) was added and the mixture was heated to reflux for 5 h.
The solvent was removed and the residue was diluted with water and
ethyl acetate. The organic phase was washed with 2M NaOH solution
and then dried over Na.sub.2SO.sub.4. A mixture of
5-bromo-6-fluorobenzofuran and 5-bromo-4-fluorobenzofuran (4.8 g,
60.3%) were obtained as a mixture after purification via column
chromatography.
Preparation 29: 6-Bromo-7-fluorobenzofuran
##STR00074##
[0262] 6-Bromo-7-fluorobenzofuran was prepared from
1-bromo-3-(2,2-diethoxyethoxy)-2-fluorobenzene as described in
Preparation 88; ESIMS m/z 216 ([M+H].sup.+).
Preparation 30: 6-Bromo-5-fluorobenzofuran
##STR00075##
[0264] 6-Bromo-5-fluorobenzofuran was prepared from
2-bromo-4-(2,2-diethoxyethoxy)-1-fluorobenzene as described in
Preparation 88: ESIMS m/z 216 ([M+H].sup.+).
Preparation 31: 7-Bromo-4-chlorobenzofuran
##STR00076##
[0266] 7-Bromo-4-chlorobenzofuran was prepared from
1-bromo-4-chloro-2-(2,2-diethoxyethoxyl)benzene as described in
Preparation 88; ESIMS m/z 232 ([M+H].sup.+).
Preparation 32: 5-Bromo-4-fluorobenzo[b]thiophene and
5-bromo-6-fluorobenzo[b]thiophene
##STR00077##
[0268] Polyphosphoric acid (13.9 g) was stirred in chlorobenzene
(50 mL) at 130.degree. C.
(4-bromo-3-fluorophenyl)(2,2-diethoxyethyl)sulfane (7.7 g, 0.0238
mol) in chlorobenzene (15.4 mL) was added dropwise at 130.degree.
C. The mixture was then stirred at 130.degree. C. for 10 h. The
solvent was removed and the residue was extracted with toluene,
hexane, and then water. The organic phase was combined and washed
with saturated NaHCO.sub.3 solution and brine, and then dried over
Na.sub.2SO.sub.4. The products 5-bromo-4-fluorobenzo[b]thiophene
and 5-bromo-6-fluorobenzo[b]thiophene were obtained after
purification via column chromatography (3.6 g, 65.5%).
Preparation 33: Bromo-5-fluorobenzo[b]thiophene and
4-bromo-5-fluorobenzo[b]thiophene
##STR00078##
[0270] 6-Bromo-5-fluorobenzo[b]thiophene and
4-bromo-5-fluorobenzo[b]thiophene were prepared from
(3-bromo-4-fluorophenyl)(2,2-diethoxyethyl)sulfane as described in
Preparation 81: ESIMS m/z 232 ([M+H].sup.+).
Preparation 34:
2-(7-Chlorobenzofuran-4-yl)-5,5-dimethyl-1,3,2-dioxaborinane
##STR00079##
[0272] 2-(7-Chlorobenzofuran-4-yl)-5,5-dimethyl-1,3,2-dioxaborinane
was prepared as described in Preparation 94 from
4-bromo-7-chlorobenzofuran (prepared as described in WO2005056015)
to afford a white solid (66%): IR (cm.sup.-1) 669.18, 701.26,
741.33, 792.08, 773.25, 842.53, 811.66, 863.44, 876.27, 884.51,
953.31, 993.58, 1027.34, 1132.28, 1059.34, 1157.92, 1217.21,
1207.86, 1253.95, 1238.65, 1302.38, 1266.72, 1359.16, 1335.94,
1370.05, 1422.73, 1438.38, 1480.37, 1577.30, 1602.05, 2903.59,
2871.91, 2940.30, 2955.31, 3140.15, 3161.21; .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 7.69 (d, J=2.1 Hz, 1H), 7.63 (d, J=7.8 Hz, 1H),
7.28 (dd, J=6.7, 2.6 Hz, 1H), 7.27 (d, J=2.2 Hz, 1H), 3.82 (s, 4H),
1.05 (s, 6H); ESIMS m/z 265 ([M+H].sup.+), 263 ([M-H].sup.-).
Preparation 35:
2-(Benzofuran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and
2-(benzofuran-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
##STR00080##
[0274] 2-(Benzofuran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
and 2-(benzofuran-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
were prepared as described in Preparation 94 from 4-bromobenzofuran
and 6-bromobenzofuran to afford the mixture as a clear oil (48%):
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.97 (s, 1H), 7.72-7.68
(m, 1H), 7.66 (dd, J=4.9, 2.6 Hz, 2H), 7.60 (dd, J=8.0, 5.2 Hz,
2H), 7.30 (dd, J=7.1, 6.2 Hz, 1H), 7.28-7.21 (m, 2H), 6.77 (dd,
J=2.1, 0.8 Hz, 1H), 1.37 (d, J=6.2 Hz, 22H), 1.29-1.22 (m, 8H);
.sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 146.01, 145.21, 130.19,
130.11, 128.76, 123.56, 120.60, 117.60, 114.05, 108.45, 106.63,
83.82, 83.69, 83.50, 25.02, 24.98, 24.88; ESIMS m/z 245
([M+H].sup.+), 243 ([M-H].sup.+).
Preparation 36:
2-(6-Fluorobenzofuran-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
and
2-(4-fluorobenzofuran-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
##STR00081##
[0276] A mixture of 5-bromo-6-fluorobenzofuran and
5-bromo-4-fluorobenzofuran (1 combined equivalent), KOAc (3 eq) and
bis(pinacolato) diboron (1.2 eq) were stirred in dioxane (0.1M with
respect to 5-bromo-6-fluorobenzofuran and
5-bromo-4-fluorobenzofuran mixture) under nitrogen flow for 30 min.
The catalyst PdCl.sub.2(dppf) 0.15 eq) was added and the nitrogen
flow was maintained for 10 min. The reaction mixture was heated to
85.degree. C. overnight. The solvent was removed, the residue was
dissolved in methylene dichloride, and the solid was filtered. The
filtrate was concentrated and purified through a column to give a
mixture of
2-(6-fluorobenzofuran-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
and
2-(4-fluorobenzofuran-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(63%): .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.98 (d, J=5.7 Hz,
1H), 7.59 (d, J=2.1 Hz, 1H), 7.18 (d, J=9.4 Hz, 1H), 6.73 (d, J=1.3
Hz, 1H), 1.38 (s, 12H); .sup.1H NMR (400 MHz, CDCl.sub.3) .delta.
7.81 (d, J=7.0 Hz, 1H), 7.37 (t, J=7.4 Hz, 1H), 7.30 (d, J=8.4 Hz,
1H), 6.87 (s, 1H), 1.38 (s, 12H); .sup.19F NMR (376 MHz,
CDCl.sub.3) .delta. -107.80, -107.81, -107.82, -107.84, -108.47,
-108.48; ESIMS m/z 262 ([M+H].sup.+).
Preparation 37:
2-(4-Chlorobenzofuran-7-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
##STR00082##
[0278]
2-(4-Chlorobenzofuran-7-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
was prepared as described in Preparation 98 from
7-bromo-4-chlorobenzofuran: .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 7.75 (d, J=2.2 Hz, 1H), 7.67 (d, J=7.8 Hz, 1H), 7.24 (d,
J=7.8 Hz, 1H), 6.86 (d, J=2.2 Hz, 1H), 1.41 (s, 12H); ESIMS m/z 278
([M+H].sup.+).
Preparation 38:
2-(5-Fluorobenzofuran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
##STR00083##
[0280]
2-(5-Fluorobenzofuran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
was prepared as described in Preparation 98 from
6-bromo-5-fluorobenzofuran: .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 7.85 (d, J=4.3 Hz, 1H), 7.68 (d, J=2.2 Hz, 1H), 7.24-7.20
(m, 1H), 6.75-6.70 (m, 1H), 1.38 (s, 12H); .sup.19F NMR (376 MHz,
CDCl.sub.3) .delta. -110.23 (dd, J=9.6, 4.1 Hz); ESIMS m/z 262
([M+H].sup.+).
Preparation 39:
2-(7-Fluorobenzofuran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
##STR00084##
[0282]
2-(7-Fluorobenzofuran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
was prepared as described in Preparation 98 from
6-bromo-7-fluorobenzofuran. .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 7.68 (t, J=3.1 Hz, 1H), 7.55 (dd, J=7.8, 4.5 Hz, 1H), 7.34
(t, J=6.5 Hz, 1H), 6.80 (dd, J=2.9, 2.2 Hz, 1H), 1.38 (s, 12H);
.sup.19F NMR (376 MHz, CDCl.sub.3) .delta.-127.62 (dd, J=4.2, 3.1
Hz); ESIMS m/z 262 ([M+H].sup.+).
Preparation 40:
2-(6-Fluorobenzo[b]thiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
and
2-(4-fluorobenzo[b]thiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-
lane
##STR00085##
[0284]
2-(6-Fluorobenzo[b]thiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxabo-
rolane and
2-(4-fluorobenzo[b]thiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dio-
xaborolane were prepared as described in Preparation 98 from
5-bromo-4-fluorobenzo[b]thiophene and
5-bromo-6-fluorobenzo[b]thiophene: .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.20 (d, J=5.5 Hz, 1H), 7.53 (d, J=9.3 Hz, 1H),
7.35 (d, J=5.5 Hz, 1H), 7.30 (d, J=5.5 Hz, 1H), 1.39 (s, 12H);
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.69-7.61 (m, 2H), 7.47
(d, J=5.6 Hz, 1H), 7.39 (d, J=5.6 Hz, 1H), 1.39 (s, 12H); .sup.19F
NMR (376 MHz, CDCl.sub.3) .delta. -107.24, -109.56; ESIMS m/z 278
([M+H].sup.+).
Preparation 41:
2-(5-Fluorobenzo[b]thiophen-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
and
2-(5-fluorobenzo[b]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaboro-
lane
##STR00086##
[0286]
2-(5-Fluorobenzo[b]thiophen-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxabo-
rolane and
2-(5-fluorobenzo[b]thiophen-4-yl)-4,4,5,5-tetramethyl-1,3,2-dio-
xaborolane were prepared as described in Preparation 98 from
6-bromo-5-fluorobenzo[b]thiophene and
4-bromo-5-fluorobenzo[b]thiophene: .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.26 (d, J=5.1 Hz, 1H), 7.59 (d, J=5.4 Hz, 1H),
7.45 (d, J=9.9 Hz, 1H), 7.28 (d, J=5.4 Hz, 1H), 1.39 (s, 12H);
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.92 (d, J=5.5 Hz, 1H),
7.88 (dd, J=8.8, 4.9 Hz, 1H), 7.55 (d, J=5.5 Hz, 1H), 7.07 (t,
J=9.1 Hz, 1H), 1.42 (s, 12H); .sup.19F NMR (376 MHz, CDCl.sub.3)
.delta. -107.32, -107.34, -107.35, -107.36, -111.00, -111.02,
-111.02, -111.03, -111.04, -111.04; ESIMS m/z 278
([M+H].sup.+).
Preparation 42:
2-(Benzo[b]thiophen-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
##STR00087##
[0288] 6-Bromobenzo[b]thiophene (3.09 g, 14.5 mmol),
4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (4.42
g, 17.4 mmol), [1,1'-bis(diphenylphosphino)ferrocene]-palladium(II)
chloride (0.54 g, 0.74 mmol), and potassium acetate (2.89 g, 29.4
mmol) in anhydrous dioxane (48 mL) was refluxed at 80.degree. C.
for 4 h. The reaction was cooled and diluted with ethyl acetate,
filtered through a pad of Celite, and washed with brine. The
aqueous layer was extracted with ethyl acetate. The organic layers
were dried, filtered, and adsorbed onto silica gel. Purification by
flash chromatography (0-30% ethyl acetate/hexanes) provided
2-(benzo[b]thiophen-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
as a yellow oily solid: (3.266 g, 87%): .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.38 (d, J=0.7 Hz, 1H), 7.79 (ddd, J=20.2, 8.0,
0.8 Hz, 2H), 7.51 (d, J=5.5 Hz, 1H), 7.34 (dd, J=5.4, 0.7 Hz, 1H),
1.37 (s, 12H); .sup.13C NMR (101 MHz, CDCl.sub.3) .delta. 141.78,
129.75, 129.58, 128.18, 123.87, 122.94, 83.89, 24.92; EIMS m/z
260.
Preparation 43:
5-Fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
##STR00088##
[0290] To a round bottom flask,
4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (1.424
g, 5.61 mmol),
[1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.342
g, 0.467 mmol), and potassium acetate (0.917 g, 9.34 mmol) were
charged as solids. The flask was sealed, and pumped and purged
3.times. with inert gas. Then 6-bromo-5-fluoro-1H-indole (1.0 g,
4.67 mmol) in dioxane (15.57 mL) was added. The reaction was
stirred and warmed to an internal temperature of 85.degree. C.
After 18 h the reaction mixture was cooled and filtered through a
pad of Celite, washing with excess ethyl acetate. The filtrate was
diluted with water and partitioned. The aqueous layer was extracted
with ethyl acetate (3.times.15 mL). The combined organics were
dried over MgSO.sub.4, filtered and concentrated in vacuo. The
crude product was purified using a Teledyne ISCO purification
system with a gradient eluent system of ethyl acetate and hexanes
to yield the title compound as a peach-colored solid (656 mg, 54%):
.sup.1H NMR (400 MHz, DMSO-d-.sub.6) .delta. 1.31 (s, 12H), 6.42
(ddd, J=2.9, 1.9, 0.9 Hz, 1H), 7.22 (d, J=10.5 Hz, 1H), 7.52 (t,
J=2.8 Hz, 1H), 7.69 (d, J=4.8 Hz, 1H), 11.24 (s, 1H); .sup.19F NMR
(376 MHz, DMSO-d.sub.6) .delta. -116.07; ESIMS m/z 262.0
([M+H].sup.+), 260.0 ([M-H].sup.-).
Preparation 44: 7-Bromo-4-chloro-1H-indole
##STR00089##
[0292] To a solution of 1-bromo-4-chloro-2-nitrobenzene (932 mg,
3.95 mmol) in tetrahydrofuran (10 mL), vinylmagnesium bromide (0.7
M in tetrahydrofuran) (12 mmol) in tetrahydrofuran (15 mL) was
added drop wise at -40.degree. C. After 1 h the reaction mixture
was poured into saturated NH.sub.4Cl. The resulting organic layer
was concentrated. The resulting residue was purified using a
Teledyne ISCO chromatography system with a gradient eluent system
of 2% ethyl acetate in hexane to yield the title compound (400 mg,
44%): .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 6.73 (t, J=2.8 Hz,
1H), 7.02 (d, J=8.1 Hz, 1H), 7.19-7.39 (m, 2H), 8.43 (s, 1H).
Preparation 45: 4-Bromo-7-chloro-1H-indole
##STR00090##
[0294] 4-Bromo-7-chloro-1H-indole was prepared from
4-bromo-1-chloro-2-nitrobenzene as described in Preparation 114:
.sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 6.49-6.74 (m, 1H), 7.07
(d, J=8.1 Hz, 1H), 7.15-7.42 (m, 2H), 8.49 (s, 1H).
Preparation 46: 6-Bromo-7-fluoro-1H-indole
##STR00091##
[0296] 6-Bromo-7-fluoro-1H-indole was prepared from
1-bromo-2-fluoro-3-nitrobenzene as described in Preparation 114
(250 mg, 25.2%): .sup.1H NMR (300 MHz, CDCl.sub.3) .delta.
6.52-6.62 (m, 1H), 7.13-7.34 (m, 3H), 8.38 (s, 1H); ESIMS m/z 215.0
([M+H].sup.+).
Preparation 47
Precursor Example 1
4-Chloro-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
##STR00092##
[0298] To a solution of 7-bromo-4-chloro-1H-indole (8 g, 0.03 mol)
in dioxane; KOAc (9.8 g, 0.1 mol),
dichloro[1,1'-bis(diphenylphosphino)ferrocene]-palladium(II) (2.19
g, 0.003 mol),
4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (13.2
g, 0.052 mol) were charged as solids. The reaction was placed under
inert atmosphere and the flask was sealed. The reaction was heated
to 100.degree. C. for 16 h. The reaction was then treated with
H.sub.2O and extracted with ethyl acetate. The organic layer was
partitioned and concentrated. The resulting residue was purfied
using a Teledyne ISCO chromatography system with a gradient eluent
system of ethyl acetate in Hexane to yield the title compound (1.3
g, 15.6%): .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 1.40 (s, 24H),
6.58-6.73 (m, 1H), 7.14 (d, J=7.6 Hz, 1H), 7.28-7.36 (m, 1H), 7.56
(d, J=7.6 Hz, 1H), 9.34 (s, 1H).
Preparation 48:
7-Chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
##STR00093##
[0300]
7-Chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
was prepared as described in Preparation 117 from
4-bromo-7-chloro-1H-indole (4.2 g, 43.7%): .sup.1H NMR (300 MHz,
CDCl.sub.3) .delta. 1.38 (s, 26H), 7.08 (dd, J=3.2, 2.2 Hz, 1H),
7.20 (d, J=7.6 Hz, 1H), 7.30 (t, J=2.8 Hz, 1H), 7.56 (d, J=7.6 Hz,
1H), 8.40 (s, 1H).
Preparation 49
Precursor Example 2
7-Fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
##STR00094##
[0302]
7-fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
was prepared as described in Preparation 117 from
6-bromo-7-fluoro-1H-indole (150 mg, 45.5%): .sup.1H NMR (300 MHz,
CDCl.sub.3) .delta. 1.26 (s, 25H), 1.39 (s, 24H), 7.27 (d, J=4.5
Hz, 2H), 7.40 (d, J=2.6 Hz, 2H), 8.43 (s, 1H); .sup.19F NMR (282
MHz, CDCl.sub.3) .delta. -124.52; .sup.13C NMR (101 MHz,
CDCl.sub.3) .delta. 24.87 (d, J=15.9 Hz), 77.30, 83.49 (d, J=6.9
Hz), 103.25, 115.98 (d, J=3.3 Hz), 126.08 (d, J=7.7 Hz).
Preparation 50
Precursor Example 3
7-Fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(triisopropylsi-
lyl)-1H-indole
##STR00095##
[0304] 7-Fluoro-1-(triisopropylsilyl)-1H-indole (4.0 g, 14 mmol)
(Prepared according to M. Schlosser, et al, Eur. J. Org. Chem.
2006, 2956-2969) was dissolved in 30 mL dry THF, cooled to
-75.degree. C., treated in portions with sec-butyl lithium (10 mL,
1.4 M, 14 mmol) and stirred for 2 h at -75.degree. C.
2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.0 mL, 2.7
g, 14 mmol) was added in portions and the mixture was stirred for 1
h at -75.degree. C. The cooling was removed and the temperature was
allowed to rise to 5.degree. C. over 30 min. The reaction was
quenched by addition of 5 mL sat. NH.sub.4Cl and partitioned
between ethyl acetate and water. The organic phase was washed with
sat. NaCl, dried (Na.sub.2SO.sub.4), evaporated onto silica gel,
and purified by flash chromatography (SiO.sub.2; eluting with
hexanes) to give 4.2 g of the title compound as a thick oil (4.2 g,
73%): .sup.1H NMR (400 MHz, CDCl3) .delta. 7.43 (dd, J=7.9, 4.6 Hz,
1H), 7.38 (m, 2H), 1.75 (m, 3H), 1.38 (s, 12H), 1.13 (d, J=7.6 Hz,
18H). .sup.19F NMR (376 MHz, CDCl3) .delta. -113.07. EIMS m/z
417.
Preparation 51: 2-Ethynyl-4,6-difluoroaniline
##STR00096##
[0306] Step 1:
[0307] 2-Bromo-4,6-difluoroaniline (10 g, 48 mmol), copper (I)
iodide (180 mg, 0.96 mmol), bis(triphenylphosphine)palladium(II)
chloride (680 mg, 0.96 mmol) and ethynyltrimethylsilane (7.1 g, 72
mmol) were combined with 10 ml dry DMF and heated to 50.degree. C.
for 18 h. An additional 2 mL ethynyltrimethylsilane, 200 mg
bis(triphenylphosphine)palladium(II) chloride, and 60 mg CuI were
added and heating was continued for 4 h. After cooling, the mixture
was diluted with ethyl acetate and stirred with 1 N HCl. The dark
mixture was filtered through Celite to remove fine solids. The
organic phase was washed with water, sat. NaCl, dried and
concentrated. Purification by flash chromatography (SiO.sub.2,
eluting with 0-20% EtOAc in hexanes) afforded 9 g of material that
consisted of a 70/30 ratio of the TMS alkyne derivative and the
starting bromide.
[0308] Step 2:
[0309] The mixture was carried in to the desilylation without
further purification. The TMS derivative was dissolved in methanol
(500 mL) and treated with 8.5 g KF. A clear solution formed which
was stirred overnight at RT. Most of the volatiles were removed
under vacuum, the residue was taken up in ethyl acetate and washed
water and with sat. NaCl. The solution was dried, evaporated and
purified by flash chromatography (SiO.sub.2, eluting with 0-10%
ethyl acetate in hexanes) to provide the title compound (4.2 g, 70
area % pure by FID-GC): .sup.1H NMR (400 MHz, CDCl3) .delta. 6.83
(m, 1H), 4.13 (m, 1H), 3.46 (s, 1H). .sup.19F NMR (376 MHz, CDCl3)
.delta. -124.04, -124.88, -126.94, -130.08. EIMS m/z 153. This
material was carried through to the cyclization step without
further purification.
Preparation 52: 5,7-Difluoro-1H-indole
##STR00097##
[0311] The impure 2-ethynyl-4,6-difluoroaniline (4.2 g, 19 mmol)
from the previous example was dissolved in ethanol (75 mL), treated
with sodium gold(III) chloride dihydrate (310 mg, 0.77 mmol) and
stirred for 3 h under an atmosphere of nitrogen. The mixture was
concentrated, taken up in ethyl acetate, washed with water, washed
with sat. NaCl, dried over sodium sulfate (Na.sub.2SO.sub.4) and
evaporated. Purification by flash chromatography (SiO.sub.2,
100-200 mesh; eluting with 0-15% EtOAc in hexanes containing 2%
acetic acid) provided of the title product (2.0 g, ca 85% purity):
.sup.1H NMR (400 MHz, CDCl3) .delta. 8.32 (s, 1H), 7.26 (dd, J=4.8,
2.0 Hz, 1H), 7.09 (dd, J=9.1, 2.2 Hz, 1H), 6.74 (ddd, J=11.2, 9.3,
2.0 Hz, 1H), 6.55 (td, J=3.3, 2.2 Hz, 1H). .sup.19F NMR (376 MHz,
CDCl3) .delta.-122.11, -131.96. EIMS m/z 153.
Preparation 53: 5,7-Difluoro-1-(triisopropylsilyl)-1H-indole
##STR00098##
[0313] N-butyl lithium (2.7 ml, 2.5 M, 6.9 mmol) was added to 10 mL
dry THF at -70.degree. C. 5,7-difluoro-1H-indole (1.0 g, 6.5 mmol)
in 5 mL THF was added in portions to the this solution and the
mixture was stirred for 30 min at -75.degree. C.
Triisopropylchlorosilane (1.5 mL, 1.3 g, 6.9 mmol) was added,
stirring was continued for 1 h at -75.degree. C. and then the
mixture was allowed to warm to -5.degree. C. over 2 h. After
treatment with 5 mL sat. NH.sub.4Cl, the mixture was mixed with 30
mL ether and the organic phase was washed with 5 mL sat. NaCl,
dried (Na.sub.2SO.sub.4) and evaporated. The product was purified
by flash chromatography (SiO.sub.2; hexanes) to provide the title
compound as a clear oil (1.5 g; 74%): .sup.1H NMR (400 MHz, CDCl3)
.delta. 7.35 (d, J=3.1 Hz, 1H), 7.07 (dd, J=8.7, 2.3 Hz, 1H), 6.69
(m, 1H), 6.59 (t, J=3.1 Hz, 1H), 1.67 (m, 3H), 1.13 (d, J=7.6 Hz,
18H). 19F NMR (376 MHz, CDCl3) .delta.-120.64, -120.65, -122.49,
-122.49. ELMS m/z 309.
Preparation 54:
5,7-Difluoro-6-iodo-1-(triisopropylsilyl)-1H-indole
##STR00099##
[0315] 5,7-difluoro-1-(triisopropylsilyl)-1H-indole (1.4 g, 4.5
mmol) and pentamethyldiethylene-triamine (830 mg, 4.8 mmol) were
combined in 10 mL dry THF, cooled to -70.degree. C. and treated in
portions with sec-butyl lithium (3.4 mL, 1.4 M, 4.8 mmol) and
stirred for 3 h at this temperature. Iodine (1.3 g, 5.0 mmol) in 5
mL THF was added, the mixture was stirred for 50 min, quenched by
addition of 3 mL sat. NH.sub.4Cl and partitioned between diethyl
ether and water. The organic phase was washed with sat. NaCl, dried
(Na.sub.2SO.sub.4), evaporated and purified by flash chromatography
(SiO.sub.2; hexanes) the title compound as a clear oil which
solidified on standing (1.9 g, 90%). .sup.1H NMR (400 MHz, CDCl3)
.delta. 7.34 (d, J=3.1 Hz, 1H), 7.14 (dd, J=7.7, 0.9 Hz, 1H), 6.60
(t, J=3.1 Hz, 1H), 1.67 (m, 3H), 1.13 (d, J=7.6 Hz, 18H). .sup.19F
NMR (376 MHz, CDCl3) .delta.-101.37, -105.33. MP: 74-76.degree.
C.
EXAMPLES OF SYNTHESIS OF COMPOUNDS OF FORMULA (I)
Example 1
Methyl
4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinate
(Compound No. 1.14)
##STR00100##
[0317] Methyl 4-amino-3,6-dichloro-5-fluoropicolinate (0.650 g,
2.72 mmol),
7-fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
(0.817 g, 3.13 mmol), bis(triphenylphosphine)palladium(II) chloride
(0.191 g, 0.272 mmol), and cesium fluoride (0.826 g, 5.44 mmol,
Note: potassium fluoride replaced cesium fluoride in some examples
that refer to this particular example) were combined in
acetonitrile (4.53 mL) and water (4.53 mL). The reaction mixture
was irradiated in a Biotage Initiator microwave at 110.degree. C.
in a sealed vial for 30 min. The cooled reaction mixture was
partitioned between ethyl acetate and water. The organic phase was
dried and concentrated. The product was purified by flash
chromatography (SiO.sub.2; eluting with 5-40% ethyl acetate in
hexanes) to provide the title compound as an white solid (0.517 g,
52.4% yield).
[0318] The preparation method used in this example is referred to
in Table 11 as "Coupling 1."
Example 2
Methyl 4-amino-3-chloro-5-fluoro-6-(1H-indol-5-yl)picolinate
(Compound No. 1.2)
##STR00101##
[0320] 1H-Indol-5-ylboronic acid (220 mg, 1.4 mmol, 1.1 equiv) and
methyl 4-amino-3,6-dichloro-5-fluoropicolinate (300 mg, 1.3 mmol,
1.0 equiv) were sequentially added to a 5 mL Biotage microwave
vessel, followed by cesium fluoride (380 mg, 2.5 mmol, 2.0 equiv),
palladium(II) acetate (14 mg, 0.063 mmol, 0.05 equiv), and sodium
3,3',3''-phosphinetriyltribenzenesulfonate (71 mg, 0.13 mmol, 0.10
equiv). A 3:1 mixture of water:acetonitrile (2.5 mL) was added and
the resulting dark brown mixture was placed in a Biotage microwave
and heated to 150.degree. C. for 5 m, with external IR-sensor
temperature monitoring from the side of the vessel. The cooled
reaction mixture was diluted with water (50 mL) and extracted with
dichloromethane (15.times.30 mL). The combined organic layers were
dried (sodium sulfate), gravity filtered, and concentrated by
rotary evaporation. The residue was purified by reverse phase
column chromatography (5% acetonitrile to 100% acetonitrile
gradient) to yield the title compound as a tan powder (290 mg,
73%).
[0321] The preparation method used in this example is referred to
in Table 11 as "Coupling 2."
Example 3
Methyl 4-amino-6-(benzo[d]thiazol-5-yl)-3-chloro-5-fluoropicolinate
(Compound No. 6.1)
##STR00102##
[0323] To a 5 mL microwave vial was added methyl
4-amino-6-bromo-3-chloro-5-fluoropicolinate (200 mg, 1.0 mmol),
benzo[d]thiazol-5-ylboronic acid (237 mg, 1.35 mmol), potassium
fluoride (KF; 122 mg, 2.12 mmol), TPPTS-Na
(tris-(3-sulfornatophenyl)-phosphine4-hydrate sodium salt, 67 mg,
0.106 mmol) and Pd(OAc).sub.2 (11 mg, 0.053 mmol). Subsequently,
CH.sub.3CN (1.0 mL) and H.sub.2O (3.0 mL) were added, and the
reaction vial was sealed and heated in a Biotage microwave at
150.degree. C. for 5 min, with external IR-sensor temperature
monitoring from the side of the vessel. The reaction mixture was
cooled to room temperature and diluted with dicloromethane, and
washed with water. The organic extracts were combined, dried
(Na.sub.2SO.sub.4), filtered, and concentrated in vacuo. The crude
product was purified by triturating with Et.sub.2O to yield the
title compound as a brown solid (172 mg, 51%).
[0324] The preparation method used in this example is referred to
in Table 11 as "Coupling 3."
Example 4
Methyl 4-amino-6-(benzo[b]thiophenyl-5-yl)-3,5-dichloropicolinate
(Compound No. 3.1)
##STR00103##
[0326] To a 5 mL microwave vial was added methyl
4-amino-3,5,6-trichloropicolinate (0.232 g, 0.909 mmol),
2-(benzo[b]thiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
(0.260 g, 0.999 mmol), cesium fluoride (0.276 g, 1.817 mmol) and
(PPh.sub.3).sub.2PdCl.sub.2 (0.064 g, 0.091 mmol). The reaction
vial was then sealed and placed under inert atmosphere.
Subsequently, Dioxane (4.0 mL) and H.sub.2O (1.0 mL) were added and
the reaction mixture was heated in a Biotage microwave at
120.degree. C. for 60 min, with external IR-sensor temperature
monitoring from the side of the vessel. The reaction mixture was
cooled to room temperature and diluted with ethyl acetate (5 mL)
and poured into brine solution. The layers were separated and the
aqueous phase was extracted with ethyl acetate (3.times.10 mL). The
organic extracts were combined, dried (MgSO.sub.4), filtered, and
concentrated in vacuo. The crude product was purified using a
Teledyne ISCO purification system with a gradient eluent system of
ethyl acetate and hexanes. Further purification was performed, as
needed, using a Teledyne ISCO reverse phase system with a gradient
eluent system of acetonitrile and H.sub.2O to yield the title
compound as a white solid.
[0327] The preparation method used in this example is referred to
in Table 11 as "Coupling 4."
Example 5
Methyl
4-amino-3-chloro-6-(7-chlorobenzofuran-4-yl)-5-fluoropicolinate
(Compound No. 2.16)
##STR00104##
[0329] Combined potassium fluoride (0.365 g, 6.28 mmol),
diacetoxypalladium (0.047 g, 0.209 mmol), and
2-(7-chlorobenzofuran-4-yl)-5,5-dimethyl-1,3,2-dioxaborinane (0.609
g, 2.301 mmol), sodium 3,3',3''-phosphinetriyltribenzenesulfonate
tetrahydrate (0.134 g, 0.209 mmol), methyl
4-amino-3,6-dichloro-5-fluoropicolinate (0.5 g, 2.092 mmol). Added
water (3 mL) and acetonitrile (1 mL). Heated reaction mixture at
150.degree. C. in a microwave reactor for 6 minutes. Diluted cooled
reaction mixture with ethyl acetate and water and filtered through
cotton plug. Dried organic phase (Na.sub.2SO.sub.4) and
concentrated under vacuum. Purified by reverse phase chromatography
to provide the title compound as a white solid (127 mg, 12.5%
yield).
[0330] The preparation method used in this example is referred to
in Table 11 as "Coupling 5."
Example 6
Methyl 4-amino-3-chloro-6-(7-fluoro-1H-indol-6-yl)picolinate
(Compound No. 1.22)
##STR00105##
[0332] Methyl 4-acetamido-3,6-dichloropicolinate (400 mg, 1.520
mmol),
7-fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole
(437 mg, 1.673 mmol), cesium fluoride (462 mg, 3.04 mmol), and
(PPh.sub.3).sub.2PdCl.sub.2 (107 mg, 0.152 mmol) were charged as
solids into a microwave reaction vessel and dioxane (4 mL) and
water (1 mL) were added. The reaction vessel sealed and irradiated
in a Biotage Initiator microwave at 110.degree. C. for 2 h, with
external IR-sensor temperature monitoring from the side. The
reaction mixture was partitioned between ethyl acetate and water.
The organic phase was filtered and concentrated. The intermediate
product was purified by flash chromatography (ISCO 40 g silica
10-75% EtOAc: Hex 16 CV). Fractions containing product were
combined and concentrated to give 524 mg of a white solid
intermediate methyl
4-acetamido-3-chloro-6-(7-fluoro-1H-indol-6-yl)picolinate (0.524 g,
1.448 mmol) which was subsequently diluted with methanol (10.0 mL).
Then acetyl chloride (0.725 mL, 10.20 mmol) was added. The reaction
mixture was allowed to stir at room temperature for 18 h. The
reaction was concentrated to dryness. The resulting residue was
dissolved in ethyl acetate and poured into saturated NaHCO.sub.3
solution. The layers were partitioned and the aqueous layer was
extracted with ethyl acetate (3.times.15 mL). The organic extracts
were combined, washed with saturated NaCl solution, dried
(MgSO.sub.4), filtered and concentrated in vacuo. The crude product
was purified using a Teledyne ISCO purification system with a
gradient eluent system of ethyl acetate and hexanes to yield the
title compound as a white solid (365 mg, 79%).
[0333] The preparation method used in this example is referred to
in Table 11 as "Coupling 6."
Example 7
Methyl 4-amino-3-chloro-6-(5,7-difluoro-1H-indol-6-yl)picolinate
(Compound No. 1.26)
##STR00106##
[0335] 5,7-difluoro-6-iodo-1-(triisopropylsilyl)-1H-indole (450 mg,
1.0 mmol), methyl
4-acetamido-3-chloro-6-(trimethylstannyl)picolinate (450 mg, 1.1
mmol) were combined in 7 mL dry DMF, deaerated with a stream of
nitrogen for 15 min, treated with
bis(triphenylphosphine)palladium(II) chloride (72 mg, 0.10 mmol)
and copper (I) iodide and heated to 60.degree. C. for 2 h. The
mixture was partitioned between ethyl acetate and water. The
organic phase was washed with water, washed with sat. NaCl, dried
(Na.sub.2SO.sub.4), and evaporated. Purification by flash
chromatography (SiO.sub.2, 100-200 mesh; eluting with 0-30% EtOAc
in hexanes) provide 200 mg of the silylated N-acetamide product.
This material was slurried in methanol (15 mL), treated with 2 mL
acetyl chloride and heated at reflux for 2 h. The volatiles were
removed under vacuum and the residue was purified by flash
chromatography (SiO.sub.2; 0-40% ethyl acetate in hexanes) to
provide 30 mg of the title compound plus 60 mg of title compound
that was still protected by the TIPS group on the indole nitrogen.
The TIPS derivative was dissolved in 5 mL dry THF, treated with
tetrabutylammonium fluoride hydrate (140 mg, 0.5 mmol) and stirred
for 1 h at 20.degree. C. The mixture was partitioned between 20 ml
ethyl acetate and sat. NaCl. The organic phase was dried
(Na.sub.2SO.sub.4) and evaporated. Purification by flash
chromatography (SiO.sub.2; 0-50% ethyl acetate in hexanes) provide
another 30 mg of the title compound as a white solid (60 mg,
16%).
[0336] The preparation method used in this example is referred to
in Table 11 as "Coupling 7."
Example 8
Methyl
4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinate
(Compound No. 1.14)
##STR00107##
[0338]
7-fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(triisop-
ropylsilyl)-1H-indole (500 mg, 1.2 mmol), methyl
4-amino-3,6-dichloro-5-fluoropicolinate (290 mg, 1.2 mmol), cesium
fluoride (360 mg, 2.4 mmol) and
bis(triphenylphosphine)palladium(II) chloride (84 mg, 0.12 mmol)
were combined in 4 mL of a 1:1 v/v acetonitrile-water and heated at
115.degree. C. for 25 min in a Biotage Initiator microwave reactor.
The mixture was partitioned between ethyl acetate and sat. NaCl and
the organic phase was dried and evaporated. Purification by flash
chromatography (SiO.sub.2; eluting with 0-20% ethyl acetate in
dichloromethane) provided impure product. The material was purified
by flash chromatography again (SiO.sub.2; eluting with 0-30% ethyl
acetate in hexanes) to provide the title compound as a white solid
(220 mg, 52%).
[0339] The preparation method used in this example is referred to
in Table 11 as "Coupling 8."
Example 9
Methyl
4-amino-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-3-vinylpicolinate
(Compound No. 1.17)
##STR00108##
[0341]
7-Fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(triisop-
ropylsilyl)-1H-indole (320 mg, 0.77 mmol), methyl
4-amino-6-chloro-5-fluoro-3-vinylpicolinate (190 mg, 0.84 mmol),
sodium carbonate (81 mg, 0.77 mmol) and
bis(triphenylphosphine)palladium(II) chloride (54 mg, 0.08 mmol)
were combined in 4 mL of a 1:1 v/v acetonitrile-water and heated to
115.degree. C. for 30 min in a Biotage Initiator microwave reactor.
The mixture was partitioned between ethyl acetate and water. The
organic phase was washed with sat. NaCl, dried (Na.sub.2SO.sub.4),
and evaporated. Purification by flash chromatography (SiO.sub.2;
eluting with 0-20% ethyl acetate in hexanes) provided 220 mg of the
TIPS protected product. This material was dissolved in 10 mL THF,
treated with tetrabutylammonium fluoride hydrate (260 mg, 1.0 mmol)
and stirred for 1 h. The mixture was partitioned between sat. NaCl
and ethyl acetate. The organic phase was washed with sat. NaCl,
dried (Na.sub.2SO.sub.4), and evaporated. Purification by flash
chromatography (SiO.sub.2; eluting with 0-20% ethyl acetate in
hexanes) provided to give 100 mg of the title compound as a white
solid (100 mg, 37%).
[0342] The preparation method used in this example is referred to
in Table 11 as "Coupling 9."
Example 10
Preparation of methyl
4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-(triisopropylsilyl)-1H-indol-6-yl-
)picolinate (Compound 1.12)
##STR00109##
[0344]
7-Fluoro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-(triisop-
ropylsilyl)-1H-indole (1.0 g, 2.4 mmol), methyl
4-amino-3,6-dichloro-5-fluoropicolinate (630 mg, 2.6 mmol), sodium
carbonate (250 mg, 2.4 mmol) and with
bis(triphenylphosphine)palladium(II) chloride (170 mg, 0.24 mmol)
were combined in 10 mL of 1:1 v/v acetonitrile-water and heated at
110.degree. C. for 30 min in a Biotage Initiator microwave reactor.
The mixture was stirred with 30 mL ethyl acetate and 20 mL water
and filtered through glass wool to remove dark solids. The organic
phase was washed with sat. NaCl, dried (Na.sub.2SO.sub.4), and
evaporated. Purification by flash chromatography (SiO.sub.2;
eluting with 0-30% ethyl acetate in hexanes) provided 520 mg of the
title compound as a white solid (520 mg; 42).
[0345] The preparation method used in this example is referred to
in Table 11 as "Coupling 10."
Example 11
Methyl
4-amino-6-(3-bromobenzo[b]thiophen-7-yl)-3-chloro-5-fluoropicolinat-
e (Compound No. 3.26)
##STR00110##
[0347] Methyl
4-amino-6-(benzo[b]thiophen-7-yl)-3-chloro-5-fluoropicolinate
(0.500 g, 1.485 mmol) was dissolved in dichloromethane (9.90 mL)
and cooled to -5.degree. C. in a acetone bath to which was added a
few pieces of dry ice. Bromine (114 mL, 2.227 mmol) was dissolved
in dichloromethane (9.90 mL) and added dropwise. The reaction
mixture was stirred overnight, and then partitioned between ethyl
acetate and water. The organic phase was dried and concentrated and
the product purified by flash chromatography (SiO.sub.2, 5-40%
ethyl acetate/hexane gradient) followed by a second purification by
reverse phase chromatography to provide the title compound as a
grey solid (0.278 g, 45).
Example 12
4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid
(Compound 1.38)
##STR00111##
[0349] To a reaction vessel containing methyl
4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinate
(0.500 g, 1.481 mmol) was added methanol (14.81 ml) and sodium
hydroxide (2.96 ml, 5.92 mmol). The reaction mixture was stirred
overnight at rt then acidified by adding a slight excess of 2N HCl.
The mixture was concentrated and the precipitate that formed was
washed with water and dried under vacuum to provide
4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid
(0.400 g, 1.174 mmol, 79% yield) as an off-white solid:
[0350] The preparation method used in this example is referred to
in Table 11 as "Hydrolysis 1."
Example 13
4-Amino-6-(benzo[b]thiophen-5-yl)-3,5-dichloropicolinic acid
(Compound 3.2)
##STR00112##
[0352] In a 100 mL round bottom flask, methyl
4-amino-6-(benzo[b]thiophen-5-yl)-3,5-dichloropicolinate (210 mg,
0.595 mmol) was dissolved in methanol (2.3 mL), tetrahydrofuran
(2.3 mL), and H.sub.2O (1.2 mL). Lithium hydroxide hydrate (74.8
mg, 1.784 mmol) was added as a solid. The reaction was stirred at
room temperature until complete. The reaction mixture was
concentrated to dryness. The resulting residue was dissolved in
H.sub.2O (2.0 mL) and 1 N HCl was used to adjust the pH to 3.0,
causing a precipitate to form. This suspension was extracted with
ethyl acetate (3.times.15 mL). The organic extracts were combined,
washed with Saturated NaCl solution, dried (MgSO.sub.4), filtered
and concentrated. Additional purification of the resulting solid
was performed, as needed, using a Teledyne ISCO reverse phase
system with a gradient eluent system of acetonitrile and H.sub.2O
to yield the title compound as a white solid (110 mg, 55.
[0353] The preparation method used in this example is referred to
in Table 11 as "Hydrolysis 2."
TABLE-US-00010 TABLE 10 Compound Number, Structure, Appearance, and
Preparation Method Com- pound Preparation Number Structure
Appearance Method: Precursor(s) 1.01 ##STR00113## White Powder
Hydrolysis 1 Compound 1.03 1.02 ##STR00114## Tan Powder Coupling 2
As described 1.03 ##STR00115## White Powder Coupling 2 Head B;
1-Methyl-1H- indol-5- ylboronic acid 1.04 ##STR00116## Tan Powder
Hydrolysis 1 Compound 1.02 1.05 ##STR00117## Yellow Solid Coupling
1 Head H; (1H-indol-6- yl)boronic acid 1.06 ##STR00118## Yellow
Solid Hydrolysis 1 Compound 1.05 1.07 ##STR00119## White solid
Coupling 9 Head H 1.08 ##STR00120## Off-White Foam Coupling 2 Head
B; 1H-Indol-6- ylboronic acid 1.09 ##STR00121## White Powder
Hydrolysis 1 Compound 1.08 1.10 ##STR00122## Tan Powder Coupling 2
Head B; 1-Methyl-6- (4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-
yl)-1H-indole 1.11 ##STR00123## Pale Yellow Powder Hydrolysis 1
Compound 1.10 1.12 ##STR00124## White solid Coupling 10 Head B 1.13
##STR00125## Off White Solid Coupling 4 Head B; 5-fluoro-6-
(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2- yl)-1H-indole 1.14
##STR00126## Tan Solid Hydrolysis 2 Compound 1.13 1.15 ##STR00127##
White Solid Coupling 4 Head B; 7-fluoro-6- (4,4,5,5-
tetramethyl-1,3,2- dioxaborolan-2- yl)-1H-indole 1.16 ##STR00128##
Tan Solid Hydrolysis 2 Compound 1.15 1.17 ##STR00129## White solid
Hydrolysis 1 Compound 1.20 1.18 ##STR00130## White solid Coupling 9
Head G 1.19 ##STR00131## Tan solid Hydrolysis 1 Compound 1.18 1.20
##STR00132## White solid Coupling 8 Head F 1.21 ##STR00133## White
Solid Coupling 1 Head A, (1H-indole-6- yl)boronic acid 1.22
##STR00134## Orange Solid Hydrolysis 1 Compound 1.21 1.23
##STR00135## White Solid Coupling 6 As described 1.24 ##STR00136##
Yellow Solid Hydrolysis 2 Compound 1.23 1.25 ##STR00137## White
Solid Coupling 6 Head L; 5-fluoro-6- (4,4,5,5-tetramethyl-
1,3,2-dioxaborolan- 2-yl)-1H-indole 1.26 ##STR00138## White Solid
Hydrolysis 2 Compound 1.25 1.27 ##STR00139## White solid Coupling 7
Head K 1.28 ##STR00140## Yellow Powder Coupling 1 Head D;
(1H-indole-6- yl)boronic acid 1.29 ##STR00141## Pale Pink Flaky
Solid Hydrolysis 1 Compound 1.28 1.30 ##STR00142## White solid
Coupling 1 Head E 1.31 ##STR00143## Yellow solid Coupling 8 Head E
1.32 ##STR00144## White Solid Coupling 4 Head C; 6-(4,4,5,5-
tetramethyl-1,3,2- dioxaborolan-2-yl)- 1H-indole 1.33 ##STR00145##
Yellow Solid Hydrolysis 2 Compound 1.32 1.34 ##STR00146## White
Solid Coupling 4 Head C; 7-fluoro-6-(4,4,5,5- tetramethyl-1,3,2-
dioxaborolan-2-yl)- 1H-indole 1.35 ##STR00147## Yellow Solid
Hydrolysis 2 Compound 1.34 1.36 ##STR00148## White Solid Coupling 4
Head C; 5-fluoro-6-(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-yl)-
1H-indole 1.37 ##STR00149## Yellow Solid Hydrolysis 2 Compound 1.36
1.38 ##STR00150## Tan solid Coupling 8 Head P 1.39 ##STR00151##
Hydrolysis 1 Compound 1.38 1.40 ##STR00152## White Solid Coupling 1
Head B; 4-(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-yl)-
1H-indole 1.41 ##STR00153## White Solid Coupling 1 Head B;
1-methyl-4-(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-yl)-
1H-indole 1.42 ##STR00154## Off-White Solid Hydrolysis 1 Compound
1.41 1.43 ##STR00155## White Solid Coupling 4 Head B;
7-chloro-4-(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-yl)-
1H-indole 1.44 ##STR00156## Off White Solid Bottom of Form Coupling
6 Head L; 7-chloro-4- (4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-
2-yl)-1H-indole 1.45 ##STR00157## Off White Solid Coupling 4 Head
C; 7-chloro-4-(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-yl)-
1H-indole 1.46 ##STR00158## White Solid Coupling 4 Head B;
4-chloro-7-(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-yl)-
1H-indole 1.47 ##STR00159## Off-White Solid Coupling 1 Head B;
7-(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-yl)- 1H-indole 1.48
##STR00160## Tan Solid Hydrolysis 1 Compound 1.47 1.49 ##STR00161##
Off White Solid Coupling 6 Head L; 4-chloro-7-
(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan- 2-yl)-1H-indole 1.50
##STR00162## Off White Solid Coupling 4 Head C;
4-chloro-7-(4,4,5,5- tetramethyl-1,3,2- dioxaborolan-2-yl)-
1H-indole 2.01 ##STR00163## Yellow Solid 134 Head B; 2-
(benzofuran-5-yl)- 4,4,5,5-tetramethyl- 1,3,2-dioxaborolane 2.02
##STR00164## White Solid Hydrolysis 1 Compound 2.01 2.03
##STR00165## yellow solid Coupling 1 Head L; benzofuran-5-
ylboronic acid 2.04 ##STR00166## Off-White Solid Coupling 1 Head A;
2-(6- fluorobenzofuran- 5-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 2.05 ##STR00167## White Solid Coupling 1 Head C;
2-(6- fluorobenzofuran- 5-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 2.06 ##STR00168## Lt Yellow Oil At RoomTemp Coupling
1 Head C; benzofuran-5- boronic acid 2.07 ##STR00169## White Solid
134 Head B; 2- (benzofuran-6-yl)- 4,4,5,5-tetramethyl-
1,3,2-dioxaborolane 2.08 ##STR00170## Off White Solid Hydrolysis 1
Compound 2.07 2.09 ##STR00171## Light Yellow Solid Coupling 1 Head
B; 2-(7- fluorobenzofuran- 6-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 2.10 ##STR00172## White Solid Coupling 1 Head B;
2-(5- fluorobenzofuran- 6-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 2.11 ##STR00173## Off-White Solid Coupling 1 Head A;
2-(7- fluorobenzofuran- 6-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 2.12 ##STR00174## Beige Solid Coupling 1 Head A;
2-(5- fluorobenzofuran- 6-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 2.13 ##STR00175## White Solid Coupling 1 Head C;
2-(7- fluorobenzofuran- 6-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 2.14 ##STR00176## Off-White Solid Coupling 1 Head C;
2-(5- fluorobenzofuran- 6-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 2.15 ##STR00177## White Solid Coupling 5 Head B; 2-
(benzofuran-4-yl)- 4,4,5,5-tetramethyl- 1,3,2-dioxaborolane 2.16
##STR00178## White Solid Coupling 5 Head B; 2-(7- chlorobenzofuran-
4-yl)-5,5-dimethyl- 1,3,2-dioxaborinane 2.17 ##STR00179## Tan Solid
Hydrolysis 1 Compound 2.15 2.18 ##STR00180## Off White Solid
Hydrolysis 1 Compound 2.16 2.19 ##STR00181## Light Yellow Solid
Coupling 5 Head M; 2-(7- chlorobenzofuran- 4-yl)-5,5-dimethyl-
1,3,2-dioxaborinane 2.20 ##STR00182## Tan Solid Coupling 5 Head E;
2-(7- chlorobenzofuran-4- yl)-5,5-dimethyl- 1,3,2-dioxaborinane
2.21 ##STR00183## Tan Solid Coupling 5 Head C; 2-(7-
chlorobenzofuran-4- yl)-5,5-dimethyl- 1,3,2-dioxaborinane 2.22
##STR00184## Tan Solid Hydrolysis 1 Compound 2.21 2.23 ##STR00185##
Tan Solid Hydrolysis 1 Compound 2.20 2.24 ##STR00186## Off-White
Solid Coupling 1 Head B; 2-(4- chlorobenzofuran- 7-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 2.25 ##STR00187## Off-White Solid
Coupling 1 Head A; 2-(4- chlorobenzofuran- 7-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 2.26 ##STR00188## Off-White Solid
Coupling 1 Head C; 2-(4- chlorobenzofuran- 7-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 3.01 ##STR00189## White Solid
Coupling 4 Head H; 2- (benzo[b]thiophen- 5-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 3.02 ##STR00190## White Solid
Hydrolysis 2 Head H; 2- (benzo[b]thiophen- 5-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 3.03 ##STR00191## White Solid
Coupling 2 Head B; 2- (benzo[b]thiophen- 5-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 3.04 ##STR00192## Tan Solid
Hydrolysis 1 Compound 3.03 3.05 ##STR00193## yellow solid Coupling
1 Head L; 2- (benzo[b]thiophen- 5-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 3.06 ##STR00194## Off-White Solid Coupling 1 Head D;
2- (benzo[b]thiophen- 5-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 3.07 ##STR00195## Off-White Solid Hydrolysis 1
Compound 3.06 3.08 ##STR00196## White Solid Coupling 4 Head C; 2-
(benzo[b]thiophen- 5-yl)-4,4,5,5- tetramethyl-1,3,2- dioxaborolane
3.09 ##STR00197## White Solid Hydrolysis 2 Compound 3.08 3.10
##STR00198## White Solid Coupling 1 Head H; 2- (benzo[b]thiophen-
6-yl)-4,4,5,5- tetramethyl-1,3,2- dioxaborolane 3.11 ##STR00199##
Yellow Solid Hydrolysis 1 Compound 3.10 3.12 ##STR00200## Light
Yellow Solid Coupling 5 Head B; 2- (benzothiophen-6- yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 3.13 ##STR00201## Tan Solid
Hydrolysis 1 Compound 3.12 3.14 ##STR00202## Light Yellow Solid
Coupling 1 Head B; 2-(5- fluorobenzothiophen- 6-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 3.15 ##STR00203## Off-White
Brittle Solid Coupling 1 Head A; 2- (benzo[b]thiophen-
6-yl)-4,4,5,5- tetramethyl-1,3,2- dioxaborolane 3.16 ##STR00204##
White Solid Hydrolysis 1 Compound 3.15 3.17 ##STR00205## White
Solid Coupling 1 Head A; 2-(5- fluorobenzothiophen- 6-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 3.18 ##STR00206## Yellow Solid
Coupling 1 Head D; 2- (benzo[b]thiophen- 6-yl)-4,4,5,5-
tetramethyl-1,3,2- dioxaborolane 3.19 ##STR00207## Off-White Solid
Hydrolysis 1 Compound 3.18
3.20 ##STR00208## Light Yellow Solid Coupling 4 Head C; 2-
(benzo[b]thiophen- 6-yl)-4,4,5,5- tetramethyl-1,3,2- dioxaborolane
3.21 ##STR00209## White Solid Hydrolysis 2 Compound 3.20 3.22
##STR00210## Off-White Solid Coupling 1 Head C; 2-(5-
fluorobenzothiophen- 6-yl)-4,4,5,5- tetramethyl-1,3,2-
dioxaborolane 3.23 ##STR00211## White Solid Coupling 1 Head B;
benzo[b]thiophen-4- ylboronic acid 3.24 ##STR00212## White Solid
Coupling 1 Head B; benzo[b]thiophen-7- ylboronic acid 3.25
##STR00213## White Solid Hydrolysis 1 Compound 3.24 3.26
##STR00214## Grey Solid 140 As described 3.27 ##STR00215## yellow
oil Coupling 1 Head L; benzo[b]thiophen-7- ylboronic acid 4.01
##STR00216## White Powder Coupling 2 Head B; 1H-indazol-5-
ylboronic acid 4.02 ##STR00217## White Powder Hydrolysis 1 Compound
4.01 4.03 ##STR00218## White Powder Coupling 2 Head B; 1-Methyl-1H-
indazol-5-ylboronic acid 4.04 ##STR00219## White Powder Hydrolysis
1 Compound 4.03 4.05 ##STR00220## White Powder Coupling 2 Head B;
1H-Indazol-6- ylboronic acid 4.06 ##STR00221## Off-White Powder
Hydrolysis 1 Compound 4.05 4.07 ##STR00222## White Powder Coupling
2 Head B; 1-Methyl-1H- indazol-6-ylboronic acid 4.08 ##STR00223##
White Powder Hydrolysis 1 Compound 4.07 4.09 ##STR00224## White
Solid Coupling 1 Head A, (1H-indazol-6- yl)boronic acid 4.10
##STR00225## Yellow Solid Coupling 1 Head B; 1-methyl-4-(4,4,5,5-
tetrameth.sup.yl-1,3,2- dioxabor.sup.olan-2-yl)- 1H-indazole 4.11
##STR00226## Off-White Solid Hydrolysis 1 Compound 4.10 4.12
##STR00227## White Solid Coupling 1 Head B; 1H-indazol-4- ylboronic
acid 4.13 ##STR00228## White Solid Coupling 1 Head B; 7-(4,4,5,5-
tetramethyl-1,3,2- dioxaborolan-2-yl)- 1H-indazole 5.01
##STR00229## Off White Solid Coupling 5 Head B; BENZOOXAZOLE-
5-BORONIC ACID PINACOL ESTER 6.01 ##STR00230## Light Brown Solid
Coupling 3 As described 6.02 ##STR00231## Light Brown Solid
Hydrolysis 1 Compound 6.01 7.01 ##STR00232## Off-White Powder
Coupling 2 Head B; 6-(4,4,5,5- Tetramethyl-1,3,2-
dioxaborolan-2-yl)- 1H-benzo[d] imidazole 7.02 ##STR00233## White
Powder Coupling 2 Head B; 1-Methyl-1H- benzo[d]imidazol-
6-ylboronic acid 7.03 ##STR00234## White Powder Hydrolysis 1
Compound 7.02 8.01 ##STR00235## Yellow Solid Coupling 1 Head B;
N,N-dimethyl-6- (4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-
2-yl)benzo[d] isoxazol-3-amine 9.01 ##STR00236## White Solid
Coupling 7 Head K; 6-bromo-1H- benzo[d][1,2,3] triazole
TABLE-US-00011 TABLE 11 Analytical Data for Compounds in Table 1 C.
No. MP (.degree. C.) HNMR 1.01 166-168 .sup.1H NMR (300 MHz,
DMSO-d.sub.6) .delta. 8.06 (s, 1H), 7.67 (br d, J = 8 Hz, 1H), 7.53
(d, J = 8 Hz, 1H), 7.39 (d, J = 3 Hz, 1H), 6.77 (br s, 2H), 6.54
(d, J = 3 Hz, 1H), 3.83 (s, 3H) 1.02 221-224 .sup.1H NMR (300 MHz,
DMSO-d.sub.6) .delta. 8.04 (s, 1H), 7.59 (dt, J = 7, 1.5 Hz, 1H),
7.48 (d, J = 7 Hz, 1H), 7.41 (t, J = 3 Hz, 1H), 6.85 (br s, 2H),
6.54 (m, 1H), 3.89 (s, 3H) 1.03 125-127 .sup.1H NMR (300 MHz,
DMSO-d.sub.6) .delta. 8.21 (s, 1H), 7.82 (dt, J = 9, 1.5 Hz, 1H),
7.39 (d, J = 9 Hz, 1H), 7.08 (d, J = 3 Hz, 1H), 6.56 (d, J = 3 Hz,
1H), 4.84 (br s, 2H), 3.99 (s, 3H), 3.82 (s, 3H) 1.04 180-182
.sup.1H NMR (300 MHz, DMSO-d.sub.6) .delta. 11.26 (br s, 1H), 8.05
(s, 1H), 7.61 (dt, J = 9, 1.5 Hz, 1H), 7.48 (d, J = 9 Hz, 1H), 7.41
(t, J = 3 Hz, 1H), 7.67 (br s, 2H), 6.54 (m, 1H) 1.05 174-179
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.50 (s, 1H), 7.65 (d, J
= 8.2 Hz, 2H), 7.40 (dd, J = 8.3, 1.4 Hz, 1H), 7.23-7.17 (m, 1H),
6.54-6.48 (m, 1H), 5.30 (d, J = 3.9 Hz, 2H), 3.94 (s, 3H) 1.06
160-164 .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 13.64 (s, 1H),
11.26 (s, 1H), 7.67-7.63 (m, 1H), 7.60 (d, J = 8.3 Hz, 1H),
7.48-7.41 (m, 1H), 7.25 (dd, J = 8.2, 1.5 Hz, 1H), 6.89 (s, 2H),
6.48 (dd, J = 2.5, 1.5 Hz, 1H) 1.07 185-190 .sup.1H NMR (400 MHz,
DMSO) .delta. 11.79 (s, 1H), 7.94 (s, 2H), 7.55 (m, 1H), 7.52 (m,
1H), 7.40 (d, J = 8.4 Hz, 1H), 6.55 (m, 1H), 3.93 (s, 3H). .sup.19F
NMR (376 MHz, DMSO) .delta. -132.43. MP 185-190.degree. C. ESIMS
m/z 321 [(M + H)+]. 1.08 66-69 .sup.1H NMR (300 MHz, CDCl.sub.3)
.delta. 8.31 (br s, 1H), 8.02 (s, 1H), 7.71 (s, 2H), 7.29 (t, J = 3
Hz, 1H), 6.58 (m, 1H), 4.86 (br s, 2H), 3.99 (s, 3H) 1.09 138-140
.sup.1H NMR (300 MHz, DMSO-d.sub.6) .delta. 7.95 (s, 1H), 7.63 (d,
J = 8 Hz, 1H), 7.54 (dt, J = 8, 2 Hz, 1H), 7.47 (t, J = 3 Hz, 1H),
6.79 (br s, 2H), 6.48 (m, 1H) 1.10 116-119 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 7.94 (t, J = 1 Hz, 1H), 7.69 (br s, 2H), 7.13
(d, J = 3 Hz, 1H), 6.50 (dd, J = 3, 1 Hz, 1H), 4.85 (br s, 2H),
3.99 (s, 3H), 3.84 (s, 3H) 1.11 173-176 .sup.1H NMR (400 MHz,
DMSO-d.sub.6) .delta. 7.93 (s, 1H), 7.66 (d, J = 8.5 Hz, 1H), 7.59
(d, J = 8.5 Hz, 1H), 7.46 (d, J = 3 Hz, 1H), 6.50 (d, J = 3 Hz,
1H), 6.37 (br s, 2H), 3.87 (s, 3H) 1.12 .sup.1H NMR (400 MHz,
CDCl3) .delta. 7.49 (d, J = 8.1 Hz, 1H), 7.40 (d, J = 3.2 Hz, 1H),
7.29 (dd, J = 8.1, 5.9 Hz, 1H), 4.90 (s, 2H), 3.98 (s, 3H), 1.68
(m, 3H), 1.14 (d, J = 7.6 Hz, 18H). .sup.19F NMR (376 MHz, CDCl3)
.delta. -124.55, -124.65, -136.90, -137.00. MP: 181-182.degree. C.
ESIMS m/z 492 [(M - H)-]. 1.13 .sup.1H NMR (DMSO-d.sub.6) .delta.
3.88 (s, 3H), 6.49 (ddd, J = 2.9, 1.9, 0.8 Hz, 1H), 6.96 (s, 2H),
7.43 (d, J = 11.1 Hz, 1H), 7.50 (d, J = 6.0 Hz, 1H), 7.54 (t, J =
2.8 Hz, 1H), 11.32 (s, 1H). 1.14 .sup.1H NMR (DMSO-d.sub.6) .delta.
6.46-6.52 (m, 1H), 6.88 (s, 2H), 7.42 (d, J = 11.1 Hz, 1H),
7.49-7.56 (m, 2H), 11.33 (s, 1H), 13.56 (s, 1H). 1.15 .sup.1H NMR
(DMSO-d.sub.6) .delta. 3.88 (s, 3H), 6.59 (td, J = 3.2, 1.9 Hz,
1H), 6.99 (s, 2H), 7.08 (dd, J = 8.2, 6.2 Hz, 1H), 7.47 (d, J = 8.2
Hz, 1H), 7.52 (t, J = 2.8 Hz, 1H), 11.82 (t, J = 2.2 Hz, 1H). 1.16
.sup.1H NMR (DMSO-d.sub.6) .delta. 6.59 (td, J = 3.2, 1.9 Hz, 1H),
6.90 (s, 2H), 7.10 (dd, J = 8.2, 6.2 Hz, 1H), 7.47 (d, J = 8.1 Hz,
1H), 7.51 (t, J = 2.8 Hz, 1H), 11.81 (s, 1H), 13.57 (s, 1H). 1.17
133-140 .sup.1H NMR (400 MHz, DMSO-d6) .delta. 11.76 (s, 1H), 7.49
(dd, J = 3.0, 2.5 Hz, 1H), 7.44 (d, J = 7.9 Hz, 1H), 7.09 (dd, J =
8.2, 6.2 Hz, 1H), 6.57 (td, J = 3.3, 1.9 Hz, 1H), 6.41 (s, 2H),
3.80 (s, 3H). .sup.19F NMR (376 MHz, DMSO) .delta. -134.66,
-134.73. 133-140.degree. C. ESIMS m/z 320 [(M + H)+]. 1.18 164-166
.sup.1H NMR (400 MHz, Chloroform-d) .delta. 8.45 (s, 1H), 7.49 (dd,
J = 8.2, 0.8 Hz, 1H), 7.35-7.28 (m, 2H), 6.94 (dd, J = 18.1, 11.5
Hz, 1H), 6.61 (td, J = 3.4, 2.1 Hz, 1H), 5.72 (dd, J = 11.5, 1.5
Hz, 1H), 5.60 (dd, J = 18.1, 1.5 Hz, 1H), 4.72 (s, 2H), 3.91 (s,
2H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -135.79, -135.87,
-140.98, -141.07. MP 164-166.degree. C. ESIMS m/z 330 [(M + H)+].
1.19 .sup.1H NMR (400 MHz, DMSO) .delta. 11.76 (d, J = 16.4 Hz,
1H), 7.48 (m, 1H), 7.11 (dd, J = 8.2, 6.2 Hz, 1H), 6.79 (dd, J =
17.8, 11.5 Hz, 1H), 6.58 (dd, J = 5.1, 3.2 Hz, 1H), 6.38 (s, 1H),
5.56 (m, 1H). .sup.19F NMR (376 MHz, DMSO) .delta. -134.07,
-134.15, -143.26, -143.34. ESIMS m/z 316 [(M + H)+]. 1.20 203-205
.sup.1H NMR (400 MHz, DMSO) .delta. 11.76 (s, 1H), 7.49 (dd, J =
6.0, 3.3 Hz, 1H), 7.44 (d, J = 8.2 Hz, 1H), 7.05 (dd, J = 8.1, 6.3
Hz, 1H), 6.57 (m, 1H), 6.49 (s, 2H), 3.84 (s, 3H), 3.79 (s, 3H).
.sup.19F NMR (376 MHz, DMSO) .delta. -134.75, -134.82, -138.34,
-138.42. MP 203-205.degree. C. ESIMS m/z 334 [(M + H)+]. 1.21 83-85
.sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 11.20 (s, 1H), 8.00 (m,
1H), 7.59 (m, 1H), 7.53 (m, 1H), 7.43 (dd, J = 3.1, 2.4 Hz, 1H),
7.32 (s, 1H), 6.61 (s, 2H), 6.45 (s, 1H), 3.91 (s, 3H) 1.22 172-174
.sup.1H NMR (400 MHz, DMSO-d6) .delta. 11.47 (s, 1H), 7.94 (d, J =
1.2 Hz, 1H), 7.67 (d, J = 8.3 Hz, 2H), 7.52 (t, J = 2.8 Hz, 1H),
7.46 (dd, J = 8.4, 1.7 Hz, 1H), 6.51 (t, J = 2.5 Hz, 1H), NaN (m,
2H) 1.23 .sup.1H NMR (DMSO-d.sub.6) .delta. 3.89 (s, 3H), 6.54 (td,
J = 3.4, 1.9 Hz, 1H), 6.75 (s, 2H), 7.31 (d, J = 1.5 Hz, 1H),
7.37-7.52 (m, 3H), 11.76 (s, 1H). 1.24 .sup.1H NMR (DMSO-d.sub.6)
.delta. 6.50-6.62 (m, 1H), 6.71 (s, 2H), 7.27 (d, J = 1.5 Hz, 1H),
7.41 (d, J = 8.3 Hz, 1H), 7.45-7.53 (m, 2H), 11.76 (d, J = 2.4 Hz,
1H), 13.48 (s, 1H). 1.25 .sup.1H NMR (DMSO-d.sub.6) .delta. 3.90
(s, 3H), 6.45 (ddd, J = 2.9, 1.9, 0.9 Hz, 1H), 6.75 (s, 2H), 7.29
(d, J = 1.7 Hz, 1H), 7.40 (d, J = 12.7 Hz, 1H), 7.52 (t, J = 2.8
Hz, 1H), 7.93 (dd, J = 6.8, 0.8 Hz, 1H), 11.27 (t, J = 2.3 Hz, 1H).
1.26 .sup.1H NMR (DMSO-d.sub.6) .delta. 6.45 (t, J = 2.4 Hz, 1H),
6.68 (s, 2H), 7.24 (d, J = 1.6 Hz, 1H), 7.40 (d, J = 12.8 Hz, 1H),
7.52 (t, J = 2.8 Hz, 1H), 7.95 (d, J = 6.7 Hz, 1H), 11.29 (s, 1H),
13.54 (s, 1H). 1.27 169-171 .sup.1H NMR (400 MHz, CDCl3) .delta.
8.45 (s, 1H), 7.29 (t, J = 2.7 Hz, 1H), 7.16 (d, J = 10.0 Hz, 1H),
6.93 (dd, J = 1.5, 0.8 Hz, 1H), 6.54 (s, 1H), 4.82 (s, 2H), 3.98
(s, 3H). .sup.19F NMR (376 MHz, CDCl.sub.3) .delta. -126.04,
-135.41. MP: 169-171.degree. C. ESIMS m/z 336 [(M - H)-]. 1.28
231-234 .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 11.15 (s, 1H),
7.57 (d, J = 8.1 Hz, 1H), 7.42 (dd, J = 6.3, 3.6 Hz, 2H), 7.05 (dd,
J = 8.2, 1.5 Hz, 1H), 6.47 (dd, J = 2.5, 1.6 Hz, 1H), 6.39 (s, 2H),
3.85 (s, 3H), 2.14 (s, 3H). 1.29 168-175 .sup.1H NMR (400 MHz,
DMSO-d.sub.6) .delta. 11.31 (s, 1H), 7.66-7.60 (m, 1H), 7.49 (s,
1H), 7.48-7.43 (m, 1H), 7.07 (dt, J = 15.8, 7.9 Hz, 3H), 6.53-6.48
(m, 1H), 2.13 (s, 3H) 1.30 240-242 .sup.1H NMR (400 MHz,
DMSO-d.sub.6) .delta. 11.33 (s, 1H), 8.37 (s, 1H), 7.96 (dd, J =
8.4, 1.5 Hz, 1H), 7.58 (d, J = 8.4 Hz, 1H), 7.50 (m, 1H), 6.47 (d,
J = 1.1 Hz, 1H), 3.94 (s, 3H); ESIMS m/z 303 [(M + H)+]. 1.31
185-190 .sup.1H NMR (400 MHz, DMSO) .delta. 11.79 (s, 1H), 7.94 (s,
2H), 7.55 (m, 1H), 7.52 (m, 1H), 7.40 (d, J = 8.4 Hz, 1H), 6.55 (m,
1H), 3.93 (s, 3H). .sup.19F NMR (376 MHz, DMSO) .delta. -132.43. MP
185-190.degree. C. ESIMS m/z 321 [(M + H)+]. 1.32 190-191 .sup.1H
NMR (DMSO-d.sub.6) .delta. 3.74 (s, 3H), 3.92 (s, 3H), 6.46 (ddd, J
= 3.0, 1.9, 0.9 Hz, 1H), 7.27 (s, 2H), 7.46 (t, J = 2.7 Hz, 1H),
7.56 (d, J = 8.4 Hz, 1H), 7.94 (dd, J = 8.4, 1.5 Hz, 1H), 8.33 (d,
J = 1.1 Hz, 1H), 11.26 (d, J = 2.3 Hz, 1H). 1.33 154-157 .sup.1H
NMR (DMSO-d.sub.6) .delta. 3.75 (s, 3H), 6.41-6.50 (m, 1H), 7.20
(s, 2H), 7.46 (t, J = 2.7 Hz, 1H), 7.56 (d, J = 8.4 Hz, 1H), 7.96
(dd, J = 8.4, 1.5 Hz, 1H), 8.25-8.46 (m, 1H), 11.27 (s, 1H). 1.34
.sup.1H NMR (DMSO-d.sub.6) .delta. 3.75 (s, 3H), 3.90 (s, 3H), 6.53
(td, J = 3.2, 1.9 Hz, 1H), 7.37 (d, J = 8.3 Hz, 3H), 7.44-7.54 (m,
2H), 11.71 (s, 1H). 1.35 .sup.1H NMR (DMSO-d.sub.6) .delta. 3.77
(s, 3H), 6.53 (td, J = 3.2, 1.9 Hz, 1H), 7.12- 7.35 (m, 2H), 7.37
(d, J = 8.3 Hz, 1H), 7.46-7.58 (m, 2H), 11.72 (t, J = 2.2 Hz, 1H),
13.49 (s, 1H). 1.36 .sup.1H NMR (DMSO-d.sub.6) .delta. 3.76 (s,
3H), 3.89 (s, 3H), 6.44 (ddd, J = 3.0, 1.8, 0.9 Hz, 1H), 7.32 (d, J
= 11.9 Hz, 3H), 7.51 (t, J = 2.8 Hz, 1H), 7.85 (d, J = 6.5 Hz, 1H),
11.30 (s, 1H). 1.37 .sup.1H NMR (DMSO-d.sub.6) .delta. 3.75 (s,
3H), 6.43 (ddd, J = 2.9, 1.9, 0.8 Hz, 1H), 7.10-7.46 (m, 3H), 7.50
(t, J = 2.7 Hz, 1H), 7.85 (dd, J = 6.4, 0.8 Hz, 1H), 11.29 (t, J =
2.3 Hz, 1H), 13.48 (s, 1H). 1.38 181-182 .sup.1H NMR (400 MHz,
DMSO) .delta. 11.75 (s, 1H), 7.55 (dd, J = 8.3, 6.7 Hz, 1H), 7.50
(m, 1H), 7.38 (d, J = 8.4 Hz, 1H), 7.21 (s, 1H), 6.67 (dd, J =
17.6, 11.5 Hz, 1H), 6.54 (dd, J = 5.1, 3.2 Hz, 1H), 5.48 (ddd, J =
11.4, 7.3, 1.1 Hz, 1H), 3.83 (s, 1H), 3.33 (s, 1H). .sup.19F NMR
(376 MHz, DMSO) .delta. -132.89. MP 172-173.degree. C. ESIMS m/z
313 [(M + H)+]. 1.39 209-211 .sup.1H NMR (400 MHz, DMSO) .delta.
13.51 (s, 1H), 11.75 (s, 1H), 7.56 (m, 1H), 7.50 (t, J = 2.5 Hz,
1H), 7.38 (d, J = 8.3 Hz, 1H), 7.14 (s, 1H), 6.67 (dd, J = 17.7,
11.5 Hz, 1H), 6.54 (s, 1H), 5.60 (d, J = 17.8 Hz, 1H), 5.49 (d, J =
11.4 Hz, 1H). .sup.19F NMR (376 MHz, DMSO) .delta. -132.98. MP:
209-211.degree. C. . ESIMS m/z 299 [(M + H)+]. 1.40 233-236 .sup.1H
NMR (400 MHz, CDCl.sub.3) .delta. 8.27 (s, 1H), 7.51-7.45 (m, 2H),
7.32- 7.28 (m, 2H), 6.93-6.79 (m, 1H), 4.90 (s, 2H), 3.98 (s, 3H)
1.41 167-169 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.46 (ddd, J
= 7.3, 2.1, 0.8 Hz, 1H), 7.41 (d, J = 8.2 Hz, 1H), 7.33-7.28 (m,
1H), 7.13 (d, J = 3.1 Hz, 1H), 6.79-6.68 (m, 1H), 4.89 (s, 2H),
3.98 (s, 3H), 3.83 (s, 3H) 1.42 158-160 .sup.1H NMR (400 MHz,
DMSO-d.sub.6) .delta. 7.55 (d, J = 7.5 Hz, 1H), 7.38 (d, J = 3.1
Hz, 1H), 7.32-7.22 (m, 2H), 6.77 (s, 2H), 6.50 (t, J = 2.3 Hz, 1H),
3.84 (s, 3H) 1.43 .sup.1H NMR (DMSO-d.sub.6) .delta. 3.88 (s, 3H),
6.61 (dt, J = 3.1, 2.0 Hz, 1H), 6.95 (s, 2H), 7.22-7.35 (m, 2H),
7.49 (t, J = 2.8 Hz, 1H), 11.65 (s, 1H). 1.44 116 .sup.1H NMR
(DMSO-d.sub.6) .delta. 3.91 (s, 3H), 6.74 (s, 2H), 6.97 (dd, J =
3.2, 1.8 Hz, 1H), 7.28 (d, J = 8.0 Hz, 1H), 7.36 (s, 1H), 7.43 (d,
J = 8.0 Hz, 1H), 7.54 (t, J = 2.8 Hz, 1H), 11.65 (s, 1H). 1.45 226
.sup.1H NMR (DMSO-d.sub.6) .delta. 3.76 (s, 3H), 3.93 (s, 3H), 7.25
(d, J = 8.1 Hz, 1H), 7.34 (s, 2H), 7.49 (t, J = 2.8 Hz, 1H), 7.59
(dd, J = 3.0, 2.0 Hz, 1H), 7.99 (d, J = 8.2 Hz, 1H), 11.55 (s, 1H).
1.46 .sup.1H NMR (DMSO-d.sub.6) .delta. 3.93 (s, 3H), 6.60 (dd, J =
3.2, 2.0 Hz, 1H), 7.03 (s, 2H), 7.24 (d, J = 8.0 Hz, 1H), 7.50 (dd,
J = 8.0, 0.9 Hz, 1H), 7.55 (t, J = 2.8 Hz, 1H), 11.44 (s, 1H). 1.47
96-100 .sup.1H NMR (300 MHz, CDCl.sub.3) .delta. 11.33 (s, 1H),
7.97 (d, J = 7.7 Hz, 1H), 7.76 (d, J = 7.8 Hz, 1H), 7.37-7.29 (m,
1H), 7.18 (t, J = 7.7 Hz, 1H), 6.65- 6.55 (m, 1H), 4.83 (s, 2H),
4.03 (s, 3H) 1.48 171-175 .sup.1H NMR (400 MHz, DMSO-d.sub.6)
.delta. 11.12 (s, 1H), 7.68 (d, J = 7.8 Hz, 1H), 7.5l (d, J = 7.4
Hz, 1H), 7.41 (t, J = 2.8 Hz, 1H), 7.13 (t, J = 7.6 Hz, 1H), 6.89
(s, 2H), 6.53 (dd, J = 3.0, 2.1 Hz, 1H) 1.49 186-188 .sup.1H NMR
(DMSO-d.sub.6) .delta. 3.96 (s, 3H), 6.57 (dd, J = 3.2, 2.2 Hz,
1H), 6.81 (s, 2H), 7.23 (d, J = 8.0 Hz, 1H), 7.45 (s, 1H), 7.53 (d,
J = 8.1 Hz, 1H),
7.55- 7.59 (m, 1H), 11.51 (s, 1H). 1.50 147-149 .sup.1H NMR
(DMSO-d.sub.6) .delta. 3.78 (s, 3H), 3.94 (s, 3H), 6.60 (dd, J =
3.2, 2.2 Hz, 1H), 7.20 (d, J = 8.1 Hz, 1H), 7.29-7.88 (m, 3H), 8.09
(d, J = 8.2 Hz, 1H), 11.75 (s, 1H). 2.01 114-117 .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 8.16 (t, J = 1.4 Hz, 1H), 7.87 (dt, J =
8.7, 1.8 Hz, 1H), 7.66 (d, J = 2.2 Hz, 1H), 7.61-7.54 (m, 1H),
6.86-6.81 (m, 1H), 4.90 (s, 2H), 4.00 (s, 3H). 2.02 165-167 .sup.1H
NMR (400 MHz, DMSO-d.sub.6) .delta. 13.60 (s, 1H), 8.13 (s, 1H),
8.07 (d, J = 2.2 Hz, 1H), 7.80 (d, J = 8.7 Hz, 1H), 7.75-7.64 (m,
1H), 7.07 (dd, J = 7.9, 6.5 Hz, 1H), 6.88 (s, 2H). 2.03 84-87
.sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 3.90 (d, J = 3.3 Hz,
3H), 6.75 (d, J = 19.2 Hz, 2H), 6.92-8.22 (m, 6H) 2.04 98 .sup.1H
NMR (400 MHz, CDCl.sub.3) .delta. 8.19 (d, J = 7.7 Hz, 1H), 7.63
(d, J = 2.2 Hz, 1H), 7.28 (d, J = 11.2 Hz, 1H), 7.22 (d, J = 2.0
Hz, 1H), 6.79 (dd, J = 2.2, 0.9 Hz, 1H), 4.80 (s, 2H), 4.01 (s,
3H). 2.05 160 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.11 (d, J
= 7.4 Hz, 1H), 7.63 (d, J = 2.2 Hz, 1H), 7.29 (d, J = 10.6 Hz, 1H),
6.78 (dd, J = 2.2, 0.9 Hz, 1H), 5.40 (s, 2H), 4.01 (s, 3H), 3.95
(s, 3H). 2.06 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.20 (dd, J
= 7.7, 0.8 Hz, 1H), 7.79 (dd, J = 2.1, 0.9 Hz, 1H), 7.69 (d, J =
2.2 Hz, 1H), 7.62 (d, J = 8.2 Hz, 1H), 6.79 (dd, J = 2.1, 1.0 Hz,
1H), 5.32 (s, 2H), 3.95 (s, 3H), 3.93 (s, 3H). 2.07 .sup.1H NMR
(400 MHz, CDCl.sub.3) .delta. 8.10 (s, 1H), 7.88-7.83 (m, 1H), 7.70
(t, J = 2.5 Hz, 1H), 7.69-7.66 (m, 1H), 6.81 (dd, J = 2.2, 1.0 Hz,
1H), 4.91 (s, 2H), 4.00 (d, J = 1.5 Hz, 3H). 2.08 168-170 .sup.1H
NMR (400 MHz, DMSO-d.sub.6) .delta. 13.59 (s, 1H), 8.11 (d, J = 2.2
Hz, 1H), 8.03 (s, 1H), 7.77 (s, 2H), 7.04 (dd, J = 2.1, 0.9 Hz,
1H), 6.90 (s, 2H). 2.09 151 .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 7.73 (d, J = 2.1 Hz, 1H), 7.48-7.41 (m, 2H), 6.85 (s, 1H),
4.94 (s, 2H), 3.97 (d, J = 5.6 Hz, 3H). 2.10 109 .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 7.72 (t, J = 3.3 Hz, 2H), 7.34 (dd, J =
9.5, 5.3 Hz, 1H), 6.79 (dd, J = 2.2, 0.9 Hz, 1H), 4.93 (s, 2H),
3.98 (s, 3H). 2.11 148 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta.
7.87 (dd, J = 8.2, 6.5 Hz, 1H), 7.71 (d, J = 2.1 Hz, 1H), 7.42 (d,
J = 8.2 Hz, 1H), 7.29 (d, J = 1.6 Hz, 1H), 6.82 (dd, J = 3.0, 2.2
Hz, 1H), 4.82 (s, 2H), 4.01 (s, 3H). 2.12 130 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.15 (d, J = 5.7 Hz, 1H), 7.70 (d, J = 2.2 Hz,
1H), 7.35-7.28 (m, 2H), 6.75 (dd, J = 2.2, 0.9 Hz, 1H), 4.80 (s,
2H), 4.01 (s, 3H). 2.13 178 .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 7.82 (dd, J = 8.2, 6.3 Hz, 1H), 7.71 (d, J = 2.1 Hz, 1H),
7.39 (d, J = 8.2 Hz, 1H), 6.84-6.75 (m, 1H), 5.40 (s, 2H), 4.01 (s,
3H), 3.95 (s, 3H). 2.14 153 .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.06 (d, J = 5.9 Hz, 1H), 7.70 (t, J = 3.4 Hz, 1H), 7.32
(d, J = 10.6 Hz, 1H), 6.75 (dd, J = 2.2, 0.9 Hz, 1H), 5.39 (s, 2H),
4.01 (s, 3H), 3.96 (s, 3H). 2.15 100-103 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 7.72-7.69 (m, 1H), 7.68-7.63 (m, 1H), 7.59 (d,
J = 8.3 Hz, 1H), 7.42-7.36 (m, 1H), 7.20-7.15 (m, 1H), 4.94 (s,
2H), 4.00 (d, J = 1. 5 Hz, 3H). 2.16 184-186 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 7.76 (d, J = 2.2 Hz, 1H), 7.61 (dd, J = 8.2,
2.1 Hz, 1H), 7.42-7.38 (m, 1H), 7.26-7.24 (m, 1H), 4.96 (s, 2H),
4.00 (s, 3H). 2.17 170-173 .sup.1H NMR (400 MHz, DMSO-d.sub.6)
.delta. 13.63 (s, 1H), 8.07 (d, J = 2.2 Hz, 1H), 7.72 (d, J = 8.2
Hz, 1H), 7.57 (d, J = 7.5 Hz, 1H), 7.44 (t, J = 7.9 Hz, 1H), 7.09
(s, 1H), 6.93 (s, 2H). 2.18 .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 7.81 (d, J = 2.3 Hz, 1H), 7.54 (d, J = 8.0 Hz, 2H), 7.45
(d, J = 8.2 Hz, 1H), 6.96 (s, 1H), 5.20 (s, 2H). 2.19 158-159
.sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 8.24 (d, J = 2.1 Hz,
1H), 7.68 (d, J = 8.2 Hz, 1H), 7.55 (d, J = 8.2 Hz, 1H), 7.50 (d, J
= 2.1 Hz, 1H), 7.37 (s, 1H), 6.83 (s, 2H), 3.93 (s, 3H). 2.20
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.22 (d, J = 8.3 Hz, 1H),
7.79 (dd, J = 12.0, 2.1 Hz, 2H), 7.38 (d, J = 8.3 Hz, 1H), 5.61 (s,
2H), 4.05 (s, 3H). 2.21 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta.
8.22-8.09 (m, 1H), 7.86 (d, J = 2.1 Hz, 1H), 7.77 (d, J = 2.1 Hz,
1H), 7.42-7.34 (m, 1H), 5.39 (s, 2H), 4.04 (s, 3H), 3.95 (s, 3H).
2.22 204-206 .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 8.22 (d, J
= 2.1 Hz, 1H), 8.20 (d, J = 8.3 Hz, 1H), 8.00 (d, J = 2.1 Hz, 1H),
7.52 (d, J = 8.3 Hz, 1H), 7.42 (s, 1H), 3.78 (s, 3H). 2.23 .sup.
173-174.5 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.76 (d, J =
2.2 Hz, 1H), 7.61 (dd, J = 8.2, 2.1 Hz, 1H), 7.42-7.38 (m, 1H),
7.26-7.24 (m, 1H), 4.96 (s, 2H), 4.00 (s, 3H). 2.24 167 .sup.1H NMR
(400 MHz, CDCl.sub.3) .delta. 7.68 (d, J = 2.2 Hz, 1H), 7.54 (d, J
= 8.1 Hz, 1H), 7.37-7.34 (m, 1H), 6.93 (d, J = 2.2 Hz, 1H), 4.95
(s, 2H) 3.99 (d, J = 4.7 Hz, 3H). 2.25 169 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.14 (d, J = 8.2 Hz, 1H), 7.75 (d, J = 10.0 Hz,
2H), 7.34 (d, J = 8.3 Hz, 1H), 6.97 (t, J = 8.0 Hz, 1H), 4.86 (s,
2H), 4.02 (s, 3H). 2.26 178 .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.09 (d, J = 8.2 Hz, 1H), 7.79 (d, J = 2.1 Hz, 1H), 7.32
(d, J = 8.3 Hz, 1H), 6.92 (d, J = 2.2 Hz, 1H), 5.44 (s, 2H), 4.04
(s, 3H), 3.96 (s, 3H). 3.01 50-56 .sup.1H NMR (DMSO-d.sub.6)
.delta. 3.89 (s, 3H), 7.09 (s, 2H), 7.52-7.63 (m, 2H), 7.86 (d, J =
5.4 Hz, 1H), 8.07-8.17 (m, 2H). 3.02 157-159 .sup.1H NMR
(DMSO-d.sub.6) .delta. 6.98 (s, 2H), 7.53-7.61 (m, 2H), 7.84 (d, J
= 5.5 Hz, 1H), 8.06-8.13 (m, 2H), 13.70 (s, 1H). 3.03 84-85 .sup.1H
NMR (400 MHz, DMSO-d.sub.6) .delta. 8.34 (s, 1H), 8.12 (d, J = 8.5
Hz, 1H), 7.87-7.78 (m, 2H), 7.60 (dd, J = 5.5, 0.6 Hz, 1H), 6.95
(s, 2H), 3.90 (s, 3H) 3.04 149-150 .sup.1H NMR (400 MHz,
DMSO-d.sub.6) .delta. 8.36 (s, 1H), 8.11 (d, J = 8.5 Hz, 1H), 7.83
(t, J = 6.1 Hz, 2H), 7.58 (d, J = 5.4 Hz, 1H), 6.71 (s, 2H); 3.05
142-144 .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 8.41 (d, J =
1.7 Hz, 1H), 8.11 (d, J = 8.5 Hz, 1H), 7.82-7.88 (m, 2H), 7.51-7.72
(m, 3H), 7.39 (s, 1H), 3.92 (s, 3H) 3.06 155-159 .sup.1H NMR (400
MHz, CDCl.sub.3) .delta. 7.94-7.88 (m, 2H), 7.48 (d, J = 5.4 Hz,
1H), 7.41 (dd, J = 8.3, 1.7 Hz, 1H), 7.36 (dd, J = 5.4, 0.6 Hz,
1H), 4.83 (s, 2H), 3.96 (s, 3H), 2.19 (s, 3H) 3.07 159-165 .sup.1H
NMR (400 MHz, DMSO-d.sub.6) .delta. 8.10 (d, J = 8.3 Hz, 1H), 7.97
(s, 1H), 7.85 (d, J = 5.4 Hz, 1H), 7.54 (d, J = 5.5 Hz, 1H), 7.44
(d, J = 8.3 Hz, 1H), 6.81 (s, 2H), 2.12 (s, 3H) 3.08 125-127
.sup.1H NMR (DMSO-d.sub.6) .delta. 3.76 (s, 3H), 3.92 (s, 3H), 7.40
(s, 2H), 7.60 (dd, J = 5.4, 0.7 Hz, 1H), 7.81 (d, J = 5.4 Hz, 1H),
8.06 (d, J = 8.6 Hz, 1H), 8.24 (dd, J = 8.5, 1.7 Hz, 1H), 8.73 (d,
J = 1.5 Hz, 1H). 3.09 137-139 .sup.1H NMR (DMSO-d.sub.6) .delta.
3.76 (s, 3H), 7.31 (s, 2H), 7.59 (d, J = 5.4 Hz, 1H), 7.81 (d, J =
5.4 Hz, 1H), 8.06 (d, J = 8.5 Hz, 1H), 8.26 (dd, J = 8.5, 1.7 Hz,
1H), 8.76 (d, J = 1.5 Hz, 1H), 13.54 (s, 1H). 3.10 134-135 .sup.1H
NMR (400 MHz, CDCl.sub.3) .delta. 8.22-8.09 (m, 1H), 7.87 (d, J =
8.2 Hz, 1H), 7.66 (dd, J = 8.3, 1.6 Hz, 1H), 7.52 (d, J = 5.5 Hz,
1H), 7.36 (dd, J = 5.5, 0.6 Hz, 1H), 5.34 (s, 2H), 3.97 (s, 3H)
3.11 239 .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 8.22 (d, J =
0.7 Hz, 1H), 7.96 (d, J = 8.2 (dec) Hz, 1H), 7.88 (d, J = 5.4 Hz,
1H), 7.59 (dd, J = 8.3, 1.6 Hz, 1H), 7.53 (d, J = 5.4 Hz, 1H), 7.02
(s, 2H) 3.12 185-189 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.48
(s, 1H), 7.95 (dt, J = 8.4, 1.6 Hz, 1H), 7.90 (d, J = 8.3 Hz, 1H),
7.54 (d, J = 5.4 Hz, 1H), 7.37 (d, J = 5.4 Hz, 1H), 4.91 (s, 2H),
4.01 (s, 3H). 3.13 165-167 .sup.1H NMR (400 MHz, DMSO-d.sub.6)
.delta. 13.60 (s, 1H), 8.45 (d, J = 6.7 Hz, 1H), 7.99 (t, J = 7.0
Hz, 1H), 7.88 (dd, J = 13.5, 6.4 Hz, 2H), 7.52 (t, J = 4.7 Hz, 1H),
6.83 (d, J = 64.9 Hz, 2H). 3.14 112 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.08 (d, J = 6.2 Hz, 1H), 7.60 (d, J = 5.5 Hz,
1H), 7.56 (s, 1H), 7.33 (s, 1H), 4.94 (s, 2H), 3.99 (s, 3H). 3.15
.sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 8.55-8.44 (m, 1H),
7.92-7.79 (m, 2H), 7.50 (d, J = 5.4 Hz, 1H), 7.34 (dd, J = 5.4, 0.7
Hz, 1H), 7.17 (s, 1H), 4.82 (s, 2H), 4.02 (s, 3H). 3.16 176-177
.sup.1H NMR (400 MHz, DMSO-d6) .delta. 13.51 (s, 1H), 8.60-8.51 (m,
1H), 7.97 (d, J = 8.3 Hz, 1H), 7.91 (dd, J = 8.4, 1.6 Hz, 1H), 7.85
(d, J = 5.4 Hz, 1H), 7.51 (dd, J = 5.4, 0.6 Hz, 1H), 7.35 (s, 1H),
6.69 (s, 2H). 3.17 70 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta.
8.53 (d, J = 7.0 Hz, 1H), 7.58 (d, J = 5.5 Hz, 1H), 7.55 (d, J =
7.1 Hz, 1H), 7.52 (s, 1H), 7.29 (d, J = 5.5 Hz, 1H), 4.81 (s, 2H),
4.02 (s, 3H). 3.18 143-146 .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.01-7.94 (m, 1H), 7.85 (d, J = 8.2 Hz, 1H), 7.49 (d, J =
5.4 Hz, 1H), 7.43 (dd, J = 8.2, 1.5 Hz, 1H), 7.36 (dd, J = 5.5, 0.6
Hz, 1H), 4.84 (s, 2H), 3.96 (s, 3H), 2.19 (s, 3H) 3.19 157-162
.sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 8.11 (s, 1H), 7.97 (d,
J = 8.2 Hz, 1H), 7.87 (d, J = 5.5 Hz, 1H), 7.54 (d, J = 5.4 Hz,
1H), 7.46 (dd, J = 8.2, 1.5 Hz, 1H), 6.86 (s, 2H), 2.12 (s, 3H)
3.20 143-145 .sup.1H NMR (DMSO-d.sub.6) .delta. 3.76 (s, 3H), 3.92
(s, 3H), 7.40 (s, 2H), 7.51 (d, J = 5.5 Hz, 1H), 7.88 (d, J = 5.4
Hz, 1H), 7.95 (d, J = 8.4 Hz, 1H), 8.26 (dd, J = 8.5, 1.5 Hz, 1H),
8.79 (d, J = 1.1 Hz, 1H). 3.21 134-136 .sup.1H NMR (DMSO-d.sub.6)
.delta. 3.77 (s, 3H), 7.32 (s, 1H), 7.51 (dd, J = 5.4, 0.8 Hz, 1H),
7.88 (d, J = 5.4 Hz, 1H), 7.94 (d, J = 8.4 Hz, 1H), 8.28 (dd, J =
8.4, 1.5 Hz, 1H), 8.81-8.86 (m, 1H). 3.22 168 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.44 (d, J = 6.8 Hz, 1H), 7.58 (t, J = 4.0 Hz,
1H), 7.54-7.52 (m, 1H), 7.30 (d, J = 5.4 Hz, 1H), 5.41 (s, 2H),
4.02 (s, 3H), 3.96 (s, 3H). 3.23 219-221 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.01 (d, J = 1.7 Hz, 1H), 7.85 (ddt, J = 9.5,
7.3, 3.6 Hz, 2H), 7.43-7.33 (m, 2H), 4.93 (s, 2H), 4.02 (s, 3H)
3.24 121-123 .sup.1H NMR (400 MHz, CDCl.sub.3) .delta. 7.97-7.85
(m, 2H), 7.54 (d, J = 5.6 Hz, 1H), 7.47 (t, J = 7.7 Hz, 1H), 7.39
(d, J = 5.6 Hz, 1H), 4.96 (s, 2H), 4.04 (s, 3H) 3.25 183-185
.sup.1H NMR (300 MHz, DMSO-d.sub.6) .delta. 8.00 (dd, J = 7.9, 0.8
Hz, 1H), 7.87- 7.82 (m, 1H), 7.80 (d, J = 5.5 Hz, 1H), 7.56-7.50
(m, 2H), 6.97 (s, 2H) 3.26 181-184 .sup.1H NMR (600 MHz,
CDCl.sub.3) .delta. 8.05 (d, J = 7.5 Hz, 1H), 7.95 (d, J = 8.0 Hz,
1H), 7.58 (t, J = 7.8 Hz, 1H), 7.56 (s, 1H), 4.98 (s, 2H), 4.05 (s,
3H) 3.27 .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 7.96 (dd, J =
7.8, 1.0 Hz, 1H), 7.76- 7.84 (m, 2H), 7.53 (d, J = 7.7 Hz, 1H),
7.47-7.51 (m, 2H), 6.82 (s, 2H), 3.94 (s, 3H) 4.01 188-190 .sup.1H
NMR (300 MHz, CDCl.sub.3) .delta. 10.09 (br s, 1H), 8.36 (s, 1H),
8.16 (s, 1H), 8.03 (dt, J = 9, 1.5 Hz, 1H), 7.57 (d, J = 9 Hz, 1H),
4.90 (br s, 2H), 4.00 (s, 3H) 4.02 284-287 .sup.1H NMR (300 MHz,
DMSO-d.sub.6) .delta. 13.49 (br s, 1H), 13.19 (br s, 1H), 8.28 (s,
1H), 8.21 (s, 1H), 7.89 (dt, J = 9, 1 Hz, 1H), 7.66 (dt, J = 9, 1
Hz, 1H), 6.82 (br s, 2H) 4.03 156-159 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.34 (m, 1H), 8.07 (d, J = 1 Hz, 1H), 8.03 (dt,
J = 9, 1.5 Hz, 1H), 7.47 (dt, J = 9, 1 Hz, 1H), 4.89 (br s, 2H),
4.10 (s, 3H), 3.99 (s, 3H) 4.04 186-188 .sup.1H NMR (400 MHz,
DMSO-d.sub.6) .delta. 13.53 (br s, 1H), 8.28 (s, 1H), 8.19 (s, 1H),
7.92 (d, J = 9 Hz, 1H), 7.75 (d, J = 9 Hz, 1H), 6.81 (br s, 2H),
4.10 (s, 3H) 4.05 185-187 .sup.1H NMR (400 MHz, DMSO-d.sub.6)
.delta. 13.21 (br s, 1H),
8.16 (s, 1H), 8.01 (s, 1H), 7.88 (dd, J = 9, 1 Hz, 1H), 7.61 (dt, J
= 9, 1.5 Hz, 1H), 6.96 (br s, 2H), 3.91 (s, 3H) 4.06 >300
.sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 13.20 (br s, 1H), 8.15
(s, 1H), 8.03 (s, 1H), 7.87 (d, J = 9 Hz, 1H), 7.64 (dt, J = 9, 1.5
Hz, 1H), 6.66 (br s, 2H) 4.07 187-190 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.03 (d, J = 1 Hz, 1H), 8.00 (t, J = 1 Hz, 1H),
7.82 (dd, J = 9, 1 Hz, 1H), 7.72 (m, 1H), 4.94 (br s, 2H), 4.15 (s,
3H), 4.01 (s, 3H) 4.08 182-184 .sup.1H NMR (400 MHz, DMSO-d.sub.6)
.delta. 13.68 (br s, 1H), 8.14 (d, J = 1 Hz, 1H), 8.06 (s, 1H),
7.89 (dd, J = 9, 0.5 Hz, 1H), 7.62 (dt, J = 9, 1 Hz, 1H), 6.88 (br
s, 2H), 4.13(s, 3H) 4.09 191-193 .sup.1H NMR (400 MHz,
DMSO-d.sub.6) .delta. 13.19 (s, 1H), 8.08 (d, J = 21.7 Hz, 2H),
7.84 (d, J = 8.5 Hz, 1H), 7.63 (d, J = 8.5 Hz, 1H), 7.38 (s, 1H),
6.76 (s, 2H), 3.91 (s, 3H) 4.10 170-175 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 8.42 (s, 1H), 7.63 (dt, J = 5.8, 2.2 Hz, 1H),
7.53-7.45 (m, 2H), 4.96 (s, 2H), 4.12 (s, 3H), 4.01 (s, 3H) 4.11
173-175 .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 13.62 (s, 1H),
8.23 (s, 1H), 7.88-7.70 (m, 1H), 7.63-7.45 (m, 2H), 6.93 (s, 2H),
4.11 (d, J = 10.3 Hz, 4H) 4.12 212-215 .sup.1H NMR (400 MHz,
CDCl.sub.3) .delta. 10.10 (s, 1H), 8.55 (s, 1H), 7.66 (dd, J = 7.2,
1.5 Hz, 1H), 7.59 (d, J = 8.4 Hz, 1H), 7.54-7.45 (m, 1H), 4.97 (s,
2H), 4.02 (s, 3H) 4.13 207-210 .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 12.67 (s, 1H), 8.23 (d, J = 7.5 Hz, 1H), 8.15 (d, J = 1.9
Hz, 1H), 7.89 (d, J = 8.0 Hz, 1H), 7.29 (d, J = 7.7 Hz, 1H), 5.02
(s, 2H), 4.12 (s, 3H) 5.01 .sup.1H NMR (400 MHz, CDCl.sub.3)
.delta. 8.36 (d, J = 1.5 Hz, 1H), 8.16 (s, 1H), 8.06- 7.98 (m, 1H),
7.68 (d, J = 8.6 Hz, 1H), 4.95 (s, 2H), 4.00 (s, 3H). 6.01 216
.sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta. 9.48 (s, 1H), 8.49 (s,
1H), 8.30 (d, J = 8.8 Hz, 1H), 7.95 (d, J = 8.5 Hz, 1H), 6.99 (s,
2H), 3.91 (s, 3H) 6.02 186-187 .sup.1H NMR (400 MHz, DMSO-d.sub.6)
.delta. 13.54 (s, 1H), 9.47 (s, 1H), 8.52 (s, 1H), 8.30 (d, J = 8.5
Hz, 1H), 7.98 (d, J = 8.5 Hz, 1H), 6.91 (s, 2H) 7.01 219-221
.sup.1H NMR (300 MHz, DMSO-d.sub.6) .delta. 8.31 (s, 1H), 8.04 (br
s, 1H), 7.70 (br s, 2H), 6.92 (br s, 2H), 3.89 (s, 3H) 7.02 218-220
.sup.1H NMR (300 MHz, DMSO-d.sub.6) .delta. 8.28 (s, 1H), 7.97 (br
s, 1H), 7.75 (d, J = 9 Hz, 1H), 7.68 (dt, J = 9, 1.5 Hz, 1H), 6.94
(br s, 2H), 3.90 (s, 6H) 7.03 230-235 .sup.1H NMR (300 MHz,
DMSO-d.sub.6) .delta. 8.76 (s, 1H), 8.13 (s, 1H), 7.83 (s, 2H), dec
6.92 (br s, 2H), 3.98 (s, 3H) 8.01 .sup.1H NMR (400 MHz,
DMSO-d.sub.6) .delta. 8.10 (t, J = 9.8 Hz, 1H), 7.89 (s, 1H), 7.70
(t, J = 8.2 Hz, 1H), 7.08 (s, 2H), 3.94-3.85 (m, 3H), 3.16 (s, 6H)
9.01 129-33 .sup.1H NMR (400 MHz, DMSO-d.sub.6) .delta.) 15.84 (s,
1H), 8.35 (s, 1H), 7.98 (s, 2H), 7.41 (s, 1H), 6.79 (s, 2H), 3.91
(s, 3H).
TABLE-US-00012 TABLE 12 Percent Control Rating Conversion Table
Rating % Control A 95-100 B 85-94 C 75-84 D 60-74 E 45-59 F 30-44 G
0-29
Example A
Evaluation of Postemergent Herbicidal Activity
[0354] Post-Emergent Test I
[0355] Seeds test species were obtained from commercial suppliers
and planted into a 5''-round pot containing soil-less media mix
(metro-mix 360.RTM., Sun Gro Horticulture). Postemergence
treatments were planted 8-12 days prior to application and cultured
in a greenhouse equipped with supplemental light sources to provide
a 16 h photoperiod at 24-29.degree. C. All pots were surface
irrigated.
[0356] Approximately 10 milligrams (mg) of each compound were
dissolved in 1.3 mL acetone-DMSO (97:3, v/v) and diluted with 4.1
mL water-isopropanol-crop oil concentrate (78:20:2, v/v/v)
containing 0.02% Triton X-155. Treatments were serial diluted with
the above formulation solvent to provide 1.85, 0.926, 0.462 and
0.231 mg/mL of test compound delivered in 2.7 mL/pot (roughly
equivalent to 4.0, 2.0, 1.0, and 0.5 kg/ha, respectively).
[0357] Formulated compounds were applied using a DeVilbiss.RTM.
compressed air sprayer at 2-4 psi. Following treatment, pots were
returned to the greenhouse for the duration of the experiment. All
pots were sub-irrigated as need to provide optimum growing
conditions. All pots were fertilized one time per week by
subirrigating with Peters Peat-Lite Special fertilizer
(20-10-20).
[0358] Phytotoxicity ratings were obtained 10 days after treatment
postemergence applications. All evaluations were made visually on a
scale of 0 to 100 where 0 represents no activity and 100 represents
complete plant death. Visual assessments of plant injury were made
based on growth reduction, discoloration, leaf deformity and
necrosis
[0359] Some of the compounds tested, application rates employed,
plant species tested, and results are given in Table 13.
TABLE-US-00013 TABLE 13 Post-emergent Test I Herbicidal Activity on
Key Broadleaf and Grass Weed as well as Crop Species Application
Visual Growth Reduction (%) 10 Days Compound Rate (Kg After
Application Number ai/ha) AVEFA ECHCG HELAN IPOHE SETFA 1.10 3.96 G
G A F G 1.48 4 G G C n/a G 3.05 4 C A B B A AVEFA: wild oats (Avena
fatua) ECHCG: barnyardgrass (Echinochloa crus-galli) HELAN:
sunflower (Helianthus annuus) IPOHE: ivyleaf momingglory (Ipomoea
hederecea) SETFA: giant foxtail (Setaria faberi) g ai/ha: grams
active ingredient per hectare
Example B
Evaluation of Preemergent Herbicidal Activity
[0360] Pre-Emergent Test I
[0361] Seeds of test species were planted into round plastic pots
(5-inch diameter) containing sandy loam soil. After planting, all
pots were sub-irrigated 16 h prior to compound application.
[0362] Compounds were dissolved in a 97:3 v/v (volume/volume)
mixture of acetone and dimethyl sulfoxide (DMSO) and diluted to the
appropriate concentration in a final application solution
containing water, acetone, isopropanol, DMSO and Agri-dex (crop oil
concentrate) in a 59:23:15:1.0:1.5 v/v ratio and 0.02% w/v
(weight/volume) of Triton X-155 to obtain the spray solution
containing the highest application rate. The high application rate
was serial diluted with the above application solution to provide
delivery of the compound at rates 1/2.times., 1/4.times. and
1/8.times. of the highest rate (equivalent to 4.0, 2.0, 1.0, and
0.5 kg/ha, respectively).
[0363] Formulated compound (2.7 mL) was applied pipetted evenly
over the soil surface followed by incorporation with water (15 mL).
Following treatment, pots were returned to the greenhouse for the
duration of the experiment. The greenhouse was programmed for an
approximate 15 h photoperiod which was maintained at about
23-29.degree. C. during the day and 22-28.degree. C. during the
night. Nutrients and water were added on a regular basis through
surface irrigation and supplemental lighting was provided with
overhead metal halide 1000-Watt lamps as necessary.
[0364] Herbicidal effect ratings were obtained 14 days after
treatment. All evaluations were made relative to appropriate
controls on a scale of 0 to 100 where 0 represents no herbicidal
effect and 100 represents plant death or lack of emergence from the
soil. Some of the compounds tested, application rates employed,
plant species tested, and results are given in Table 14.
TABLE-US-00014 TABLE 14 Pre-emergent Test I Herbicidal Activity on
Key Broadleaf and Grass Weed as well as Crop Species Application
Visual Growth Reduction (%) 14 Days Compound Rate (Kg After
Application Number ai/ha) AVEFA ECHCG HELAN IPOHE SETFA 1.10 3.96 G
F G G G 1.48 4 G G C D G 3.05 4 F A F A A AVEFA: wild oats (Avena
fatua) ECHCG: barnyardgrass (Echinochloa crs-galli) HELAN:
sunflower (Helianthus annuus) IPOHE: ivyleaf momingglory (Ipomoea
hederecea) SETFA: giant foxtail (Setaria faberi) g ai/ha: grams
active ingredient per hectare
Example C
Evaluation of Postemergent Herbicidal Activity
[0365] Post-Emergent Test II:
[0366] Seeds or nutlets of the desired test plant species were
planted in Sun Gro Metro-Mix 360 planting mixture, which typically
has a pH of 6.0 to 6.8 and an organic matter content of about 30
percent, in plastic pots with a surface area of 64 square
centimeters. When required to ensure good germination and healthy
plants, a fungicide treatment and/or other chemical or physical
treatment was applied. The plants were grown for 7-21 d in a
greenhouse with an approximate 15 h photoperiod which was
maintained at about 23-29.degree. C. during the day and
22-28.degree. C. during the night. Nutrients and water were added
on a regular basis and supplemental lighting was provided with
overhead metal halide 1000-Watt lamps as necessary. The plants were
employed for testing when they reached the first or second true
leaf stage.
[0367] A weighed amount, determined by the highest rate to be
tested, of each test compound was placed in a 25 mL glass vial and
was dissolved in 4 mL of a 97:3 v/v mixture of acetone and DMSO to
obtain concentrated stock solutions. If the test compound did not
dissolve readily, the mixture was warmed and/or sonicated. The
concentrated stock solutions obtained were diluted with 20 mL of an
aqueous mixture containing acetone, water, isopropyl alcohol, DMSO,
Atplus 411F crop oil concentrate, and Triton X-155 surfactant in a
48.5:39:10:1.5:1.0:0.02 v/v ratio to obtain spray solutions
containing the highest application rates. Additional application
rates were obtained by serial dilution of 12 mL of the high rate
solution into a solution containing 2 mL of 97:3 v/v mixture of
acetone and DMSO and 10 mL of an aqueous mixture containing
acetone, water, isopropyl alcohol, DMSO, Atplus 411F crop oil
concentrate, and Triton X-155 surfactant in a
48.5:39:10:1.5:1.0:0.02 v/v ratio to obtain 1/2.times., 1/4.times.,
1/8.times. and 1/16.times. rates of the high rate. Compound
requirements are based upon a 12 mL application volume at a rate of
187 liters per hectare (L/ha). Formulated compounds were applied to
the plant material with an overhead Mandel track sprayer equipped
with 8002E nozzles calibrated to deliver 187 L/ha over an
application area of 0.503 square meters at a spray height of 18
inches (43 cm) above the average plant canopy height. Control
plants were sprayed in the same manner with the solvent blank.
[0368] The treated plants and control plants were placed in a
greenhouse as described above and watered by subirrigation to
prevent wash-off of the test compounds. After 14 d, the condition
of the test plants as compared with that of the untreated plants
was determined visually and scored on a scale of 0 to 100 percent
where 0 corresponds to no injury and 100 corresponds to complete
kill. Some of the compounds tested, application rates employed,
plant species tested, and results are given in Tables 15 and
16.
TABLE-US-00015 TABLE 15 Post-emergent Test II Herbicidal Activity
on Key Broadleaf Weed and Crop Species Application Rate (g Visual
Growth Reduction (%) 14 Days After Application C. No. ai/ha) ABUTH
AMARE BRSNN CHEAL EPHHL HELAN 1.01 35 G n/a G G A G 70 G G G G A C
140 F E G G A C 1.02 35 G n/a G C E E 70 G B G B E D 140 G B G A D
D 1.03 35 G n/a G B A G 70 G n/a G B A G 140 C B G A B E 1.04 35 E
D F E A E 70 G D E D A E 140 G D E D A B 1.05 35 E D F B F A 70 A C
E A F A 140 B A D A E A 1.06 35 G A C B G G 70 G B B A G G 140 G C
B A G G 1.07 35 G B G B D A 70 G A G B D A 140 G A G B D A 1.08 35
B A E A A B 70 A A C A A A 140 A A B A A A 1.09 35 A A A A B A 70 A
A A A A A 140 A A A A A A 1.10 35 G G G A G G 70 G B G A G G 140 G
A G A G E 1.13 35 G G G D G E 70 G F G C G D 140 G F F B F D 1.14
35 G C E D G D 70 G B D D G C 140 G B C C D C 1.15 35 A A C A A A
70 A A A A A A 140 A A A A A A 1.16 35 B A A A A A 70 A A A A A A
140 A A A A A B 1.17 35 E A A A A A 70 E A A A A A 140 D A A A A A
1.19 35 A A A A A D 70 A A A A A C 140 A A A A A A 1.20 35 E C A A
A A 70 D B A A A A 140 D A A A A A 1.21 35 D G G E C E 70 D G G B B
C 140 D E D B A C 140 G G G G G G 1.22 35 G C E G E C 70 G C D G C
B 140 G B D G B B 1.23 35 A A D A A D 70 A A C A A C 140 A A B A A
B 1.24 35 B A B B A D 70 A A E A A C 140 A A A A A B 1.25 35 G C D
G G G 70 G B C D G G 140 F A B D F G 1.26 35 G C B G G G 70 G B A F
F G 140 G A A F E G 1.27 35 D D B B A G 70 B A A B A G 140 B A A B
A G 1.28 35 B G C E G A 70 B G B D G A 140 A D B D G A 1.29 35 G E
C E G D 70 G G C E G D 140 G G B C G C 1.30 35 G G E F G G 70 G C E
F E G 140 C D D E D G 1.31 35 E D B A A F 70 D A A A A E 140 D A A
A A D 1.32 35 G G F G G E 70 G F E G D D 140 G D D C B C 1.33 35 G
D A G E D 70 G D A E D D 140 G C A D C C 1.34 35 G G C G G B 70 G G
B E G A 140 G F A D D A 1.35 35 G C A G C F 70 G B A G C D 140 G A
A B B A 1.37 35 G G F G G G 70 G G D G G G 140 G G C G G G 1.39 35
G A C A B G 70 G A B C C G 1.40 35 G n/a G G G G 70 G A G G G F 140
G n/a G G G E 1.43 35 G A G C G D 70 G A G B G C 140 D A G B F C
1.44 35 G B G B E G 70 C A G B C G 140 B A F A B G 1.45 35 G G G G
G G 70 G G G G G G 140 G E G G G F 1.46 35 G G G C G G 70 G G G B G
F 140 G D G A G E 1.47 35 G G G C G G 70 G G G C G G 140 G F G B G
E 1.48 140 G G G D G C 1.49 35 B G G B G G 70 B F G B G G 140 B G G
A G E 2.02 35 E C G A C C 70 B A F A A B 140 B A F A A A 2.03 35 A
D G B E G 70 A B G A C D 140 A B G A C C 280 A A F A B B 2.04 35 C
A G A A G 70 B A G A A G 140 A A F A A F 2.05 35 G B G G F G 70 G C
G G F G 140 G A G E E F 2.06 35 G C F D F D 70 G A D C C C 140 C A
B B A B 2.09 35 B B D A A D 70 B A C A A C 140 B A B A A B 2.10 35
D B F B A C 70 D A D A A B 140 B A C B A A 2.11 35 A A C A A E 70 A
A B A A D 140 A A A A A C 2.12 35 B A C A A F 70 A A B A A D 140 A
A A A A D 2.13 35 A D A A A C 70 A A A A A B 140 A A A A A A 2.14
35 G A A B B D 70 G A A A A B 140 G A A A A A 2.15 35 E A E A G E
70 C A C A G C 140 A A B A G C 2.16 35 B A E A G A 70 A A D A G A
140 A A D A G A 2.17 140 C A C A A B 2.18 35 G A E B G C 70 G A D B
G C 140 G A D B G B 2.19 35 A A G A G G 70 A A D A G C 140 A A D A
G C 2.20 35 E A G B G B 70 D A G A G A 140 D A F A G A 2.21 35 F A
F B G D 70 D A F B G C 140 D A E A G C 2.22 35 F A G A G C 70 F A E
A G B 140 E A D A G A 2.23 35 G A G A G B 70 G A G A G A 140 G A G
A G A 2.24 35 C A D A D C 70 C A C A C C 140 A A C A C B 2.25 35 C
A G A G G 70 C A E A C F 140 A A C A B B 2.26 35 E A E A E C 70 D A
D A D A 140 D A D A C A 3.01 35 D B G A G C 70 D A G A G C 140 C A
G A G B 3.02 35 G A G B G D 70 G A G B G C 140 G A G B G B 3.03 35
A A G A A A 70 A A D A A A 140 A A D A A A 3.05 35 B F G C D G 70 B
E G B D G 140 A D G B C F 140 E A A A G B 280 A B G B B E 3.06 35 E
B F F G A 70 D B F D G A 140 B A E D F A 3.07 35 G G E G G B 70 G D
D G G B 140 G C D C G B 3.08 35 G G G B D D 70 F F G B C C 140 F D
F B B B 3.09 35 G F E B A D 70 G C B B A C 140 E B A A A B 3.10 35
G A G C G B 70 G A G C G B 140 G A G C G B 3.11 35 G n/a G B G B 70
G n/a G B G B 140 G n/a G B G B 3.12 35 D D G A D B 70 A D G A D B
140 A B F A B B 3.13 35 G A G B G B 70 G A G A G B 140 C A D A D B
3.14 35 G B G B F B 70 G A G B F B 140 G A G A D A 3.15 35 B A F B
C D 70 A A E B C D 140 A A E A B B 3.16 35 D B G B D G 70 D A G B D
G 140 C B E B D G 3.17 35 G C G B E G 70 E A G A D G 140 D A D A C
F
3.18 35 D D G F E A 70 C C G D G A 140 C A G D F A 3.19 35 G D G D
G B 70 G A G D G B 140 D C G C G B 3.20 35 G G F B C C 70 G D D A A
B 140 G D D A A B 3.21 35 G A C B C D 70 F A B B B D 140 E A A A A
C 3.22 35 G D G D A C 70 G A F C A B 140 G A D B A B 3.23 35 G G G
G G G 70 G G G E G G 140 G G G B G G 3.24 35 G B E B G D 70 G B E A
G D 140 G A E A G B 3.25 140 G A C A G E 3.27 35 G B E C G E 70 G A
D B G D 140 E A D A G C 280 C A B A G B 4.01 35 G G G G G G 70 G E
G D G G 140 G D G D G G 4.03 35 G G G A E G 70 G E G A D E 140 G C
G A C D 4.05 35 G G G B D D 70 G A G B A D 140 E A E A A A 4.06 35
G C D G E E 70 G A C E D D 140 G A B A B C 4.07 140 E n/a E G D A
4.08 140 G n/a D A G B 4.09 35 G G G E G G 70 G E G C G F 140 G B D
B G E 4.10 35 G G G G G G 70 G A G G G G 140 G A G G G E 4.13 35 G
n/a G G G G 70 G n/a G G G G 140 G n/a G D G G 5.01 35 D C B D n/a
B 70 D B A B A B 140 D B A B n/a A 6.01 35 B B A A G B 70 B A A A B
B 140 B A A A A B 6.02 35 B A A A A A 70 B A A A A A 140 B A A A A
A 7.02 35 G G G G G G 70 G G G C G G 140 G G G A G G 8.01 35 G G G
G G G 70 G G G G G G 70 A E G B A A 140 G G G G G G 140 A D G A A A
ABUTH: velvetleaf (Abutilon theophrasti) AMARE: redroot pigweed
(Amaranthus retroflexus) BRSNN: oilseed rape, canola (Brassica
napus) CHEAL: lambsquarters (Chenopodium album) EPHHL: wild
poinsettia (Euphorbia heterophylla) HELAN: sunflower (Helianthus
annuus) g ai/ha: grams active ingredient per hectare
TABLE-US-00016 TABLE 16 Post-emergent Test II Herbicidal Activity
on Key Grass and Sedge Weeds as well as Grass Crops Application
Rate (g Visual Growth Reduction (%) 14 Days After Application C.
No. ai/ha) CYPES ECHCG SETFA ORYSA TRZAS ZEAMX 1.01 35 G G G G G G
70 G n/a G G G A 140 G C G G G B 1.02 35 G G G G G G 70 G G G G G G
140 G E G G G G 1.03 35 G G G G G G 70 G G G G G G 140 G D G G G G
1.04 35 G G G G G G 70 G n/a G G G G 140 G B G G G G 1.05 35 G G F
G G G 70 G G E G F F 140 G D D G E E 106 35 G G G G G G 70 G D G G
G G 140 G C G G G G 1.07 35 G G D G G G 70 G G C G G G 140 G G C G
G G 1.08 35 G B G G G E 70 G A D G G C 140 G A C G F B 1.09 35 F A
B G G D 70 C A B G G C 140 B A B G G C 1.10 35 G G G G G G 70 G G G
G G G 140 G G G G G G 1.12 35 G G C G E G 70 G G D G G G 140 G B C
G G G 1.13 35 G G G G G G 70 G G G G G G 140 G G G G G G 1.14 35 G
G G G G G 70 G G G G G G 140 G G G G G G 1.15 35 G C D G E G 70 D B
D G D F 140 E A B F D D 1.16 35 G C D F F G 70 D B C D D F 140 B A
B D D D 1.17 35 E B C G D D 70 E B B G D C 140 E B B G D C 1.19 35
B B D F D D 70 C B C E C D 140 A A B D C B 1.20 35 G G E G G F 70 G
D C G E E 140 G C B G D D 1.21 35 G G n/a G G G 70 G G n/a G G G
140 G G n/a G G G 140 G C G G G G 1.22 35 G G G G G G 70 G G D G G
G 140 G G B G G G 1.23 35 G G G G G G 70 G G G G G G 140 G D D G F
G 1.24 35 G G G G G G 70 G G E G F G 140 G G D G E G 1.25 35 G G G
G G G 70 G G G G G G 140 G G G G G G 1.26 35 G G G G G G 70 G G G G
G G 140 G G G G G G 1.27 35 G G G G G G 70 G G G G G G 140 G G G G
G G 1.28 35 G G G G G G 70 G G G G F G 140 G G G G F G 1.29 35 G G
G G G G 70 G G G G G G 140 F G G G G G 1.30 35 G G G G G G 70 G G G
G G G 140 G G G G G G 1.31 35 G C D G C G 70 G C C G G G 140 G B B
G F G 1.32 35 G G G G G G 70 G G G G G G 140 G G G G G G 1.33 35 G
G G G G n/a 70 G G G G G n/a 140 G G G G F n/a 1.34 35 G G G G G G
70 G G G G G G 140 G G D G F G 1.35 35 G G G G G G 70 G G G G F G
140 G G G G E G 1.37 35 G G G G G G 70 G G G G G G 140 G G G G G G
1.39 35 G G G G G G 70 G G G G G G 1.40 35 G G G G G G 70 G G G G G
G 140 G G G G G G 1.43 35 G G G G G G 70 G G G G G G 140 G G G G G
G 1.44 35 G G G G G G 70 G G G G G G 140 G G G G G G 1.45 35 G G G
G G G 70 G G G G G G 140 G G G G G G 1.46 35 G G G G G G 70 G G G G
G G 140 G G G G G G 1.47 35 G G G G G G 70 G G G G G G 140 G G G G
G G 1.48 140 G G G G G G 35 G G G G G G 70 G G G G G G 140 G G G G
G G 2.02 35 G B D G G A 70 G B D G F A 140 G A C G E A 2.03 35 G F
G G G G 70 G D G G G G 140 G B F G G G 280 G A F G G D 2.04 35 G D
D G G D 70 G A C G F C 140 F A B G E B 2.05 35 G G G G G G 70 G G G
G G G 140 G G G G G G 2.06 35 G G G G G G 70 G E G G G G 140 G A G
G G G 2.08 35 G B E G G E 70 G B D F G D 140 G A B F G D 2.09 35 G
D E G G E 70 G B D F G D 140 G B D F G D 2.10 35 G D D G G G 70 G D
D F F F 140 F B C F D E 2.11 35 G B E G G E 70 G A D G G D 140 F A
C G F B 2.12 35 G A E G G G 70 G A D G G F 140 G A D G G D 2.13 35
F C G G G G 70 B A E F E F 140 B A D F E E 2.14 35 G G G G G G 70 G
G G G G G 140 G C G G G G 2.15 35 G G G G G A 70 G E G G G A 140 G
C G G G A 2.16 35 G G G G G E 70 G G G G G A 140 G G G G G A 2.17
140 A C G G G F 2.18 35 G G G G G G 70 G G G G G G 140 G G G G G G
2.19 35 G G n/a G G G 70 G G n/a G G G 140 G G n/a G G G 2.20 35 G
n/a G G G G 70 G n/a F G G G 140 G n/a D G G G 2.21 35 G n/a G G G
G 70 G n/a G G G G 140 G n/a G G G G 2.22 35 G G G G G G 70 G G G G
G G 140 G G G G G G 2.23 35 G G G G G G 70 G G G G G G 140 G G G G
G G 2.24 35 D G G G G G 70 C G G G G F 140 B G G G G D 2.25 35 G G
G G G G 70 F G G G G G 140 C G G G G E 2.26 35 G G G G G G 70 G G G
G G G 140 G G G G G G 3.01 35 G G G G G G 70 G G G G G E 140 G G G
G G D 3.02 35 G G G G G G 70 G G G G G D 140 G G G G G D 3.03 35 E
B G G G A 70 E A B G F A 140 E A B G E A 3.05 35 G E G G G G 70 G C
G G G G 140 G B F G G E 280 G B D G G D 3.06 35 G G G G G G 70 G G
G G G G 140 G G G G G G 3.07 35 G G G G G G 70 G G G G G G 140 G G
G G G G 3.08 35 G G G G E F 70 G G G G D D 140 F C G G D C 3.09 35
G B G G D D 70 G B G G C C 140 G B G G B B 3.10 35 G G G G G D 70 G
G G G G D 140 G G G G G D 3.11 35 G G G G G G 70 G G G G G G 140 G
G G G G G 3.12 35 G B G G G A 70 G B G G G A 140 G B G G G A 3.13
35 G D n/a G G D 70 G D n/a G G D 140 G C n/a G G D 3.14 35 G G G G
G G 70 G G G G G F 140 G G G G G D 3.15 35 G C G G G D 70 G C G G G
D 140 G A G G G D
3.16 35 G C G G G D 70 G C G G G D 140 E C G G G C 3.17 35 G E G G
G F 70 G D G G G D 140 G A F G G C 3.18 35 G G G G G G 70 G G G G G
G 140 G G G G G G 3.19 35 G G G G G G 70 G G G G G G 140 G G G G G
G 3.20 35 F G G G G G 70 F E G G G C 140 B D D G F B 3.21 35 G C G
G F F 70 G B F F F D 140 G B D F E C 3.22 35 G G G G G G 70 G G G G
G G 140 G G G G G G 3.23 35 G G G G G G 70 G G G G G G 140 G G G G
G G 3.24 35 G G G G G G 70 G G G G G G 140 G G G G G G 3.25 140 G G
G G G G 3.27 35 G G G G G G 70 G G G G G G 140 G G G G G G 280 G G
G G G G 4.01 35 G G G G G G 70 G G G G G G 140 G G G G G G 4.03 35
G D n/a G G G 70 G C n/a G G G 140 G C n/a G G G 4.05 35 G n/a n/a
G G G 70 G n/a n/a G G D 140 G B A G G D 4.06 35 G G G G G G 70 G E
G G G G 140 G C E G G G 4.07 140 G G G G G G 4.08 140 G G G G G G
4.09 35 G G G G G G 70 G G G G G G 140 G G G G G G 4.10 35 G G G G
G G 70 G G G G G G 140 G G G G G G 4.13 35 G G G G G G 70 G G G G G
G 140 G G G G G G 5.01 35 n/a C G G G G 70 n/a C G G G G 140 n/a B
G G G G 6.01 35 E G G G G G 70 E E G G G G 140 E D G G G G 6.02 35
E C G G G G 70 E C E G G G 140 E B D G F G 7.02 35 G G n/a G G G 70
G G n/a G G G 140 G G n/a G G G 8.01 35 G G G G G G 70 G G G G G G
140 G G G G G G 9.01 140 A A G G G D ECHCG: barnyardgrass
(Echinochloa crus-galli) CYPES: yellow nutsedge (Cyperus
esculentus) ORYSA: rice (Oryza sativa) SETFA: giant foxtail
(Setaria faberi) TRZAS: wheat, spring (Triticum aestivum) ZEAMX:
maize, corn (Zea mays) g ai/ha: grams active ingredient per
hectare
Example D
Evaluation of Postemergent Herbicidal Activity in Wheat and
Barley
[0369] Post-Emergent Test III.
[0370] Seeds of the desired test plant species were planted in Sun
Gro MetroMix.RTM. 306 planting mixture, which typically has a pH of
6.0 to 6.8 and an organic matter content of about 30 percent, in
plastic pots with a surface area of 103.2 square centimeters
(cm.sup.2). When required to ensure good germination and healthy
plants, a fungicide treatment and/or other chemical or physical
treatment was applied. The plants were grown for 7-36 days (d) in a
greenhouse with an approximate 14 hour (h) photoperiod which was
maintained at about 18.degree. C. during the day and 17.degree. C.
during the night. Nutrients and water were added on a regular basis
and supplemental lighting was provided with overhead metal halide
1000-Watt lamps as necessary. The plants were employed for testing
when they reached the second or third true leaf stage.
[0371] A weighed amount, determined by the highest rate to be
tested, of each test compound was placed in a 25 mL glass vial and
was dissolved in 4 mL of a 97:3 v/v mixture of acetone and DMSO to
obtain concentrated stock solutions. If the test compound did not
dissolve readily, the mixture was warmed and/or sonicated. The
concentrated stock solutions obtained were diluted with 20 mL of an
aqueous mixture containing acetone, water, isopropyl alcohol, DMSO,
Agri-Dex crop oil concentrate, and X-77 surfactant in a
48:39:10:1.5:1.5:0.02 v/v ratio to obtain spray solutions
containing the highest application rates. Additional application
rates were obtained by serial dilution of 12 mL of the high rate
solution into a solution containing 2 mL of 97:3 v/v mixture of
acetone and DMSO and 10 mL of an aqueous mixture containing
acetone, water, isopropyl alcohol, DMSO, Agri-Dex crop oil
concentrate, and X-77 surfactant in a 48:39:10:1.5:1.5:0.02 v/v
ratio to obtain 1/2.times., 1/4.times., 1/8.times. and 1/16.times.
rates of the high rate. Compound requirements are based upon a 12
mL application volume at a rate of 187 liters per hectare (L/ha).
Formulated compounds were applied to the plant material with an
overhead Mandel track sprayer equipped with 8002E nozzles
calibrated to deliver 187 L/ha over an application area of 0.503
square meters at a spray height of 18 inches (43 cm) above the
average plant canopy height. Control plants were sprayed in the
same manner with the solvent blank.
[0372] The treated plants and control plants were placed in a
greenhouse as described above and watered by subirrigation to
prevent wash-off of the test compounds. After 21 d, the condition
of the test plants as compared with that of the untreated plants
was determined visually and scored on a scale of 0 to 100 percent
where 0 corresponds to no injury and 100 corresponds to complete
kill. By applying the well-accepted probit analysis as described by
J. Berkson in Journal of the American Statistical Society, 48, 565
(1953) and by D. Finney in "Probit Analysis" Cambridge University
Press (1952), the above data can be used to calculate GR.sub.20,
GR.sub.50, GR.sub.80 and GR.sub.90 values, which are defined as
growth reduction factors that correspond to the effective dose of
herbicide required to kill or control 20 percent, 50 percent, 80
percent or 90 percent, respectively, of a target plant.
[0373] Some of the compounds tested, application rates employed,
plant species tested, and results are given in Table 17.
TABLE-US-00017 TABLE 17 Activity of Herbicidal Compounds in Wheat
and Barley Application Compound Rate (g Visual Growth Reduction (%)
21 Days After Application No. ai/ha) HORVS TRZAS CIRAR GALAP KCHSC
LAMPU MATCH PAPRH SASKR SINAR VERPE VIOTR 1.15 17.5 F F F D D A F A
C A A E 35 E E D B B A E A C A A D 70 E D C A B A D A B A A C GR20
8 13 -- -- -- -- -- -- -- -- -- -- GR50 -- -- 30 9 6 0.10 45 0.06 7
4 0.28 22 GR80 -- -- 70 23 28 1 >140 1 30 8 2 63 GR90 -- -- 109
37 67 2 >140 2 95 12 6 111 1.16 17.5 G G D F C C B A D B A E 35
G G B E B A A A C A A D 70 F F A A A A A A B A A C GR20 44 41 -- --
-- -- -- -- -- -- -- -- GR50 -- -- 9 26 7 3 3 0.0004 10 5 0.0004 19
GR80 -- -- 25 34 20 10 9 0.0004 28 11 0.05 56 GR90 -- -- 43 40 39
19 16 0.0004 78 17 1 99 1.23 17.5 G G G A F B G D F C B G 35 G G G
A E A G A E C B E 70 G G G A D A G A C A A D GR20 >140 66 -- --
-- -- -- -- -- -- -- -- GR50 -- -- >140 1 35 3 0 11 29 3 1 44
GR80 -- -- >140 4 110 6 0 17 90 14 8 119 GR90 -- -- >140 7
>140 9 0 22 >140 32 21 >140 2.24 17.5 G G D D D E G D D B
F E 35 G G C B C D G D B A D D 70 G F B B B C G C B A C C GR20 66
52 -- -- -- -- -- -- -- -- -- -- GR50 -- -- 14 7 4 15 114 24 3 6 30
24 GR80 -- -- 35 23 33 93 >140 52 28 13 66 78 GR90 -- -- 57 44
103 >140 >140 77 95 19 100 >140
* * * * *