U.S. patent application number 09/733554 was filed with the patent office on 2001-10-18 for substituted 3-phenyluracils.
Invention is credited to Gerber, Matthias, Grossmann, Klaus, Hamprecht, Gerhard, Heistracher, Elisabeth, Kardorff, Uwe, Klintz, Ralf, Schaefer, Peter, Walter, Helmut, Westphalen, Karl-Otto, Wolf, Hans-Josef.
Application Number | 20010031865 09/733554 |
Document ID | / |
Family ID | 6440891 |
Filed Date | 2001-10-18 |
United States Patent
Application |
20010031865 |
Kind Code |
A1 |
Klintz, Ralf ; et
al. |
October 18, 2001 |
Substituted 3-phenyluracils
Abstract
1 where X.sup.1-X.sup.4 are each O or S; W is unsubstituted or
substituted --CH.dbd.O, --CH.dbd.S, --CH.dbd.NH,
--CH(X.sup.3R.sup.6)(X.sup.4R.sup.7)- , 2 R.sup.6 and R.sup.7 are
each C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkynyl or
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl or together form a
carbon chain; R.sup.10 is H, OH, SH, an ether or thioether group,
unsubstituted or substituted C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.7-cycloalkyl, unsubstituted or substituted amino or
unsubstituted or substituted phenyl; R.sup.1 is halogen, CN,
NO.sub.2 or CF.sub.3; R.sup.2 is H or halogen; R.sup.3 is H,
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloalkyl,
C.sub.3-C.sub.8-cycloalkylcarbonyl, C.sub.1-C.sub.6-cyanoalkyl,
C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, CHO,
C.sub.1-C.sub.6-alkanoyl, C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-haloalkylcarbonyl, unsubstituted or substituted
amino, unsubstituted or substituted phenyl or
phenyl-C.sub.1-C.sub.6-alkyl; R.sup.4 and R.sup.5 are each H, CN,
halogen, unsubstituted or substituted C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl,
C.sub.3-C.sub.7-cycloalkyl or unsubstituted or substituted phenyl;
R.sup.5 may additionally be NO.sub.21 CHO,
C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-haloalkylcarbonyl,
C.sub.1-C.sub.6-alkoxycarbonyl or unsubstituted or substituted
amino, or R.sup.4 and R.sup.5 together form an unsubstituted or
substituted carbon chain, with the proviso that R.sup.4 is not
CF.sub.3 at the same time as R.sup.5 is H when W is
--CH.dbd.CH--CO--R.sup.10 where R.sup.10 is C.sub.1-C.sub.6-alkoxy
or C.sub.3-C.sub.7-cycloalkoxy, and the salts and enol eithers of I
in which R.sup.3 is H, are used for the desication and defoliation
of plants and as insecticides and herbicidees.
Inventors: |
Klintz, Ralf;
(Dannstadt-Schauernheim, DE) ; Schaefer, Peter;
(Bad Duerkheim, DE) ; Hamprecht, Gerhard;
(Weinheim, DE) ; Heistracher, Elisabeth;
(Ludwigshafen, DE) ; Wolf, Hans-Josef; (Maxdorf,
DE) ; Westphalen, Karl-Otto; (Speyer, DE) ;
Gerber, Matthias; (Mutterstadt, DE) ; Kardorff,
Uwe; (Mannheim 1, DE) ; Walter, Helmut;
(Obrigheim, DE) ; Grossmann, Klaus; (Limburgerhof,
DE) |
Correspondence
Address: |
Herbert B. Keil
KEIL & WEINKAUF
1101 Connecticut Avenue, N.W.
Washington
DC
20036
US
|
Family ID: |
6440891 |
Appl. No.: |
09/733554 |
Filed: |
December 4, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09733554 |
Dec 4, 2000 |
|
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08774722 |
Jan 3, 1997 |
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Current U.S.
Class: |
544/124 |
Current CPC
Class: |
C07D 239/54 20130101;
C07C 271/22 20130101; C07C 275/40 20130101; C07D 317/28 20130101;
C07C 265/12 20130101; C07C 275/32 20130101; A01N 43/54 20130101;
C07D 405/04 20130101; C07C 275/38 20130101; C07C 271/04 20130101;
C07C 275/42 20130101 |
Class at
Publication: |
544/124 |
International
Class: |
C07D 413/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 20, 1991 |
DE |
P 41 31 038.1 |
Claims
We claim:
1. Substituted 3-phenyluracils of the general formula I 89where
X.sup.1 and X.sup.2 are each oxygen or sulfur; W is
--C(R.sup.8).dbd.X.sup.5,
--C(R.sup.8)(X.sup.3R.sup.6)(X.sup.4R.sup.7),
--C(Rs).dbd.C(R.sup.9)--CN, --C(R.sup.8).dbd.C(R.sup.9)
--CO--R.sup.10, --CH(R.sup.8) --CH(R.sup.9) --CO--R.sup.10,
--C(R.sup.8).dbd.C(R.sup.9)--CH.sub.2-CO-R.sup.10,
--C(R).dbd.C(R.sup.9)--C(R.sup.11).dbd.C(R) --CO--R.sup.10 or
--C(R.sup.8).dbd.C(R.sup.9)--CH.sub.2-CH(R.sup.13)--CO--R.sup.10
where X.sup.3 and X.sup.4 are each oxygen or sulfur; X.sup.5 is
oxygen, sulfur or a radical-NR.sup.14; R.sup.14 is hydrogen,
hydroxyl, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.7-cycloalkyl,
C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-alkenyloxy,
C.sub.3-C.sub.6-alkynyloxy, C.sub.5-C.sub.7-cycloalkoxy,
C.sub.5-C.sub.7-cycloalkenyloxy, C.sub.1-C.sub.6-haloalkoxy,
C.sub.3-C.sub.6-haloalkenyloxy, hydroxy-C.sub.1-C.sub.6-alkoxy,
cyano-C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.7-cycloalkyl-C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkoxy- C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkoxy-C.- sub.3-C.sub.6-alkenyloxy,
C.sub.1-C.sub.6-alkylcarbonyloxy,
C.sub.2-C.sub.6-haloalkylcarbonyloxy,
C.sub.1-C.sub.6-alkylcarbamoyloxy,
C.sub.1-C.sub.6-haloalkylcarbamoyloxy,
C.sub.1-C.sub.6-alkoxycarbonyl-C.s- ub.2-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkoxy,
di-C.sub.1-C.sub.6-alkylamino-C.sub.1-C.sub.6-alkoxy, phenyl which
may carry from one to three of the following substituents: cyano,
nitro, halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl, phenyl-C.sub.3-C.sub.6-alkoxy,
phenyl-C.sub.3-C.sub.6-alkenyloxy or
phenyl-C.sub.3-C.sub.6-alkynyloxy, where one or two methylene
groups of each of the carbon chains may be replaced with --O--,
--S-- or --N(C.sub.1-C.sub.6-alkyl)- and each phenyl ring may carry
from one to three of the following substituents: cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkoxycarbonyl, heterocyclyl,
heterocyclyl--C.sub.1-C.sub- .6-alkoxy,
heterocyclyl-C.sub.3-C.sub.6-alkenyloxy or
heterocyclyl-C.sub.3-C.sub.6-alkynyloxy, where one or two methylene
groups of each of the carbon chains may be replaced with --O--,
--S-- or --N(C.sub.1-C.sub.6-alkyl)- and the heterocyclyl ring may
be from three-membered to seven-membered and saturated, unsaturated
or aromatic and may contain from one to four hetero atoms selected
from a group consisting of one or two oxygen or sulfur atoms and up
to four nitrogen atoms and furthermore may carry from one to three
of the following substituents: cyano, nitro, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkoxycarbonyl, or --N(R.sup.15)R.sup.16, where
R.sup.15 and R.sup.16 are each hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy- C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylcarbo- nyl, C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.- 1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.2-C.sub.6-alkenyl, where the
alkenyl chain may additionally carry from one to three of the
following radicals: halogen and cyano or phenyl which may carry
from one to three of the following substituents: cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.3-C.sub.6-alkenyl- , C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl, or R.sup.15 and R.sup.16 together
with the common nitrogen atom form a saturated or unsaturated
4-membered to .sub.7-membered heterocyclic structure, where one
ring member may be replaced with --O--, --S--, --N.dbd., --NH-- or
--N(C.sub.1-C.sub.6-alkyl)-; R.sup.6 and R.sup.7 are each
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-alkynyl,
C.sub.1-C.sub.6-alkoxy- C.sub.1--C.sub.6-alkyl, or R.sup.6 and
R.sup.7 together form a saturated or unsaturated, two-membered to
four-membered carbon chain which may carry an oxo substituent,
where one member of this chain may be replaced with an oxygen,
sulfur or nitrogen atom which is not adjacent to X.sup.3 and
X.sup.4, and where the chain may carry from one to three of the
following radicals: cyano, nitro, amino, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenylo- xy,
C.sub.2-C.sub.6-alkynyloxy, C.sub.1-C.sub.6-haloalkyl,
cyano-C.sub.1-C.sub.6-alkyl, hydroxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyloxy-- C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkynyloxy-C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.7-cycloalkyl, C.sub.3-C.sub.7-cycloalkoxy, carboxyl,
C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkylcarbonyloxy-C.sub.1-- C.sub.6-alkyl and phenyl
which may carry from one to three of the following radicals:
halogen, cyano, nitro, amino, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl, and where the chain may furthermore
be substituted by a fused-on or spiral-bonded three-membered to
seven-membered ring, and one or two carbon atoms of this ring may
be replaced with oxygen, sulfur and unsubstituted or
C.sub.1-C.sub.6-alkyl-s- ubstituted nitrogen atoms and this ring
may carry one or two of the following substituents: cyano,
C,--C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl- ,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-cyanoalkyl,
C.sub.1-C.sub.6-haloalkyl and C.sub.1-C.sub.6-alkoxycarbonyl;
R.sup.8 is hydrogen, cyano, 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-haloalkyl, C.sub.3-C.sub.7-cycloalkyl,
C.sub.1-C.sub.6-alkoxy- C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.9 and R.sup.12 are each
hydrogen, cyano, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, halo-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylcarbonyl or C.sub.1-C.sub.6-alkoxycarbonyl;
R.sup.10 is hydrogen, O--R.sup.17, S--R.sup.17,
C.sub.1-C.sub.3-alkyl which may furthermore carry one or two
C.sub.1-C.sub.6-alkoxy substituents or R.sup.10 is
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl,
C.sub.1-C.sub.6-haloalk- yl, C.sub.3-C.sub.7-cycloalkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.l-C.sub.6-- alkyl,
C.sub.1-C.sub.6-alkyliminooxy, --N(R.sup.15)R.sup.16 or phenyl
which may carry from one to three of the following substituents:
cyano, nitro, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-alkoxycarbonyl, R.sub.17
is hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.7-cycloalkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-haloalkenyl,
cyano--C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy-
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkylthio--
C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkyl-oximino-C.sub.1-C.sub.6-alk- yl,
C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkylcarbonyl-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1-C.sub.6-alkyl, phenyl or
phenyl-C.sub.1-C.sub.6-alkyl, where each of the phenyl radicals in
turn may carry from one to three of the following substituents:
cyano, nitro, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.11
is hydrogen, cyano, halogen, 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- C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkylcarbo- nyl, C.sub.1-C.sub.6-alkoxycarbonyl,
--NR.sup.18R.sup.19, where R.sub.18 and R.sup.19 have the same
meanings as R.sup.15 and R.sup.16, or phenyl which may furthermore
carry from one to three of the following substituents: cyano,
nitro, halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.13 is hydrogen, cyano,
C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxycarbonyl; or R.sup.9
and R.sup.10 together form a two-membered to five-membered carbon
chain in which one carbon atom may be replaced with oxygen, sulfur
or unsubstituted or C.sub.1-C.sub.6-alkyl-substituted nitrogen;
R.sup.1 is halogen, cyano, nitro or trifluoromethyl; R.sup.2 is
hydrogen or halogen; R.sup.3 is hydrogen, nitro,
C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.3-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloal- kyl,
C.sub.3-C.sub.8-cycloalkylcarbonyl, cyano-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, formyl,
C.sub.1-C.sub.6-alkanoyl, C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-haloalkylcarbonyl,
C.sub.1-C.sub.6-alkylcarbonyl-C.sub.1-- C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1-C.sub.6-alkyl; a group
--N(R.sup.20)R.sup.21, where R.sup.20 and R.sup.21 have one of the
meanings of R.sup.15 and R.sup.16; phenyl or
phenyl--C.sub.1-C.sub.6-alky- l, where each phenyl ring may carry
from one to three of the following radicals: cyano, nitro, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.4 is hydrogen, cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.8-cycloal- kyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-hydroxyalkyl,
cyano-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkoxy-
C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl or phenyl which may
carry from one to three of the following radicals: cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl- , C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.5 is hydrogen, cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.7-cycloal- kyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-hydroxyalkyl,
cyano-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy-
C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl, formyl,
C.sub.1-C.sub.6-alkyl-carbonyl, C.sub.1-C.sub.6-haloalkylcarbonyl-
, C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.2-C- .sub.6-alkenyl,
--N(R.sup.22 )R.sup.23, where R.sup.22 and R.sup.23 have one of the
meanings of R.sup.15 and R.sup.16, or phenyl which may carry from
one to three of the following radicals: cyano, nitro, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl- , C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxy-carbonyl, or R.sup.4 and R.sub.5 together
form a saturated or unsaturated 3-membered or 4-membered carbon
chain which may contain from one to three of the following hetero
atoms: 1 or 2 oxygen atoms, 1 or 2 sulfur atoms and from 1 to 3
nitrogen atoms, and the chain may furthermore carry from one to
three of the following radicals: cyano, nitro, amino, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio and
C.sub.1-C.sub.6-alkoxycarbonyl; with the proviso that R.sup.4 may
not be trifluoromethyl at the same time as R.sup.5 is hydrogen when
W is --CH.dbd.CH--CO--R.sup.10 where R.sup.10 is
C.sub.1-C.sub.6-alkoxy or C.sub.3-C.sub.7-cycloalkoxy, and with the
proviso that R.sup.4 and R.sup.5 are not simultaneously hydrogen
when W is CH(R.sup.8)--CH(R.sup.9)--CO--R.sup.10 and R.sup.9 is not
halogen, and the salts and enol ethers of those compounds I in
which R.sup.3 is hydrogen.
2. Compounds of the general formula Ia or Ib 90where the variables
R.sup.1, R.sub.2, R.sup.4, R.sup.5, X.sup.1, X.sup.2 and W have the
meanings stated in claim 1 and R.sup.3' is one of the following
groups: C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-alkenyl or
C.sub.3-C.sub.6-alkynyl- , with the proviso that R.sup.4 may not be
trifluoromethyl at the same time as R.sup.5 is hydrogen when W is
--CH.dbd.CH--CO--R.sup.10 where R.sup.10 is C.sub.1-C.sub.6-alkoxy
or C.sub.3-C.sub.6-cycloalkoxy.
3. A compound as claimed in claim 1 or 2, wherein W is
--C(R.sup.8).dbd.X.sup.5,
--C(R.sup.8)(X.sup.3R.sup.6)(X.sup.4R.sup.7)--C-
(R.sup.8).dbd.C(R.sup.9) --CO--R.sup.10 or --CH(R.sup.8)
--CH(R.sup.9) --CO--R.sup.10.
4. A compound as claimed in claim 1 or 2, wherein R.sup.3 is
C.sub.1-C.sub.6-alkyl.
5. A compound as claimed in claim 1 or 2, wherein R.sup.2 is
hydrogen or fluorine.
6. A compound as claimed in claim 1 or 2, wherein R.sup.1 is
chlorine or bromine.
7. A compound as claimed in claim 1 or 2, wherein R.sup.4 is
C.sub.1-C.sub.6-haloalkyl.
8. Enamine esters of the general formula II 91where R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, X.sup.1 and W have the meanings
stated in claim 1 and L.sup.1 is C.sub.1-C.sub.6-alkyl or
phenyl.
9. Enamine-carboxylates of the general formula III 92where the
variables R.sup.1, R.sub.2, R.sup.3, R.sub.4, R.sup.5, X.sup.2 and
W have the meanings stated in claim 1 and L.sup.1 is
C.sub.1-C.sub.6-alkyl or phenyl.
10. Pyrimidinone derivatives of the general formula IVa or IVb
93where the variables R.sup.1, R.sup.2, R.sup.4, R.sup.5, X.sup.1,
X.sup.2 and W have the meanings stated in claim 1 and Hal is
halogen.
11. Enamine-amides of the formula VIII 94where the variables
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X.sup.2 and W have the
meanings stated in claim 1.
12. A herbicide containing an inert liquid or solid carrier and a
herbicidal amount of at least one substituted 3-phenyluracil of the
formula I as claimed in claim 1 or of the formula Ia or Ib as
claimed in claim 2 or a salt or an enol ether of those compounds I
in which R.sup.3 is hydrogen.
13. A method for controlling undesirable plant growth, wherein a
herbicidal amount of a substituted 3-phenyluracil of the formula I
as claimed in claim 1 or of the formula Ia or Ib as claimed in
claim 2 or a salt or an enol ether of those compounds I in which
R.sup.3 is hydrogen is allowed to act on plants, on their habitat
or on seed.
14. An agent for the desiccation and defoliation of plants,
containing, in addition to conventional additives, an amount,
having a defoliant or desiccant effect, of at least one substituted
3-phenyluracil of the formula I as claimed in claim 1 or of the
formula Ia or Ib as claimed in claim 2 or a salt or an enol ether
of those compounds I in which R.sup.3 is hydrogen.
15. A method for the desiccation and defoliation of plants, wherein
an amount, having a defoliant and/or desiccant effect, of a
substituted 3-phenyluracil I as claimed in claim 1 or Ia or Ib as
claimed in claim 2 is allowed to act on the plants.
16. A method as claimed in claim 15, wherein cotton is
defoliated.
17. A pesticide containing inert carriers and a pesticidal amount
of at least one substituted 3-phenyluracil of the formula I as
claimed in claim 1 or of the formula Ia or Ib as claimed in claim 2
or of a salt or of an enol ether of those compounds I in which R is
hydrogen.
18. A method for controlling pests, wherein a pesticidal amount of
a substituted 3-phenyluracil of the formula I as claimed in claim 1
or of the formula Ia or Ib as claimed in claim 2 or of a salt of an
enol ether of those compounds I in which R.sup.3 is hydrogen is
allowed to act on pests or their habitat.
19. A process for the preparation of a substituted 3-phenyluracil I
as claimed in claim 1 or Ia or Ib as claimed in claim 2, wherein a)
an enamine ester of the formula II or an enaminecarboxylate of the
formula III 95where L.sup.1 is C.sub.1-C.sub.6-alkyl or phenyl, is
cyclized and, if desired, the substituted 3-phenyluracil I in which
R.sup.3 is hydrogen is liberated from the resulting metal salt by
means of an acid, or b) a 3-phenyluracil I in which R.sup.3 is
hydrogen is alkylated or acylated or c) a 3-phenyluracil I in which
R.sup.3 is halogen is reacted with a metal cyanide or d) a
pyrimidinone derivative of the formula IVa or IVb 96where Hal is
halogen is reacted with a compound HO--R.sup.3, H.sub.5--R.sup.3'
Me.sup..sym. .sup..crclbar.OR.sup.3' or Me.sup..sym.
.sup..sym.SR.sup.3', where Me.sup..sym. is one equivalent of a
metal ion, or e) a 3-phenyluracil I in which W is --CO--R.sup.8 is
acetalated with a compound H--X.sup.3R.sub.6, H--X.sub.4R.sup.7 or
H--X.sup.3(R.sup.6R.sup.- 7)X.sup.4--H or f) a 3-phenyluracil I in
which W is --C(R) (X.sup.3R.sup.6) (X.sup.4R.sub.7) is subjected to
acetal cleavage or g) a 3-phenyluracil I in which W is
--C(R.sub.8).dbd.O is reacted with a phosphorylide of the formulae
Va to Vd R.sub.3P.dbd.CR.sup.9--CO--R.sup.1- 0 I Va,
R.sub.3P.dbd.C(R.sup.9)--CH.sub.2--CO--R.sup.10 l Vb,
R.sub.3P.dbd.C(R.sup.9)--C(R.sup.11).dbd.C(R.sup.12)--CO--R.sup.10
Vc, R.sub.3P.dbd.C(R.sup.9)--CH.sub.2--CHR.sup.13--CO--R.sup.10 Vd,
where R is a C-organic substituent, or with a phosphonium salt of
the formulae VIa to VId
R.sub.3P.sup..sym.--CH(R.sup.9)--CO--R.sup.10 Hal.sup..crclbar.
VIa, R.sub.3P.sup..sym.--CH(R.sup.9)--CH.sub.2--CO--R.s- up.10
Hal.sup..crclbar. VIb,
R.sub.3P.sup..sym.--CH(R.sup.9)--CR.sup.11.db-
d.CR.sub.12--CO--R.sup.10 Hal.sup..crclbar. VIc,
R.sub.3P.sup..sym.--CH(R.-
sup.9)--CH.sub.2--CHR.sup.13--CO--R.sup.10 Hal.sup..crclbar. VId,
where Hal is halogen, or with a phosphonate of the formulae VIIa to
VIId (RO).sub.2PO--CH(R.sup.9)--CO--R.sup.10 VIIa,
(RO).sub.2PO--CH(R.sup.9)--- CH.sub.2--CO--R.sup.10 VIIb,
(RO).sub.2PO--CH(R.sup.9)--CR.sup.11.dbd.CR.s- ub.12--CO--R.sup.10
VIIc, (RO).sub.2PO--CH(R.sup.9)--CH.sub.2--CHR.sup.13--
-CO--R.sup.10 VlId, or h) a 3-phenyluracil I in which W is
--C(R.sup.8).dbd.O is reacted with an amine, hydroxylamine or
hydrazine H.sub.2N--R.sup.14 or i) a 3-phenyluracil I in which W is
--C(R.sup.8).dbd.N--R.sup.14 is cleaved to give a compound I in
which W is --C(R.sub.8).dbd.O or k) a 3-phenyluracil I in which
X.sup.2 is oxygen is reacted with a sulfurization reagent or l) a
3-phenyluracil I in which R.sup.5 is hydrogen is halogenated or m)
a 3-phenyluracil I in which W is cyano is reduced to a compound I
in which W is formyl or n) an enamide VIII as claimed in claim 11
is cyclized with a phosgenating or thiophosgenating agent or o) a
3-phenyluracil I as claimed in claim 1, in which W is amino, is
alkylated by the Meerwein method or p) a 3-phenyluracil I as
claimed in claim 1, in which W is bromine, iodine or
O--SO.sub.2CF.sub.3, is coupled with an olefin under metal
catalysis.
Description
[0001] The present invention relates to novel substituted
3-phenyluracils of the general formula I 3
[0002] where
[0003] X.sup.1 and X.sup.2 are each oxygen or sulfur;
[0004] W is --C(R.sup.8).dbd.X.sup.5,
--C(R.sup.8)(X.sup.3R.sup.6)(X.sup.4- R.sup.7),
--C(R.sup.8).dbd.C(R.sup.9) --CN, --C(R.sup.8).dbd.C(R.sup.9)
--CO--R.sup.10, --CH(R.sup.8) --CH(R.sup.9)--CO--R.sup.10,
--C(R.sup.8).dbd.C(R.sup.9)--CH.sub.2--CO--R.sup.10,
--C(R.sup.8).dbd.C(R.sup.9)--C(R.sup.11).dbd.C(R.sup.12)
--CO--R.sup.10 or --C(R.sup.8).dbd.C(R.sup.9)
--CH.sub.2--CH(R.sup.13)--CO--R.sup.10 where
[0005] X.sup.3 and X.sup.4 are each oxygen or sulfur;
[0006] X.sup.5 is oxygen, sulfur or a radical --NR.sup.14;
[0007] R.sup.14 is hydrogen, hydroxyl, C.sub.l-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl ,
C.sub.3-C.sub.7-cycloalkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-alkenyloxy,
C.sub.3-C.sub.6-alkynyloxy, C.sub.5-C.sub.7-cycloalkoxy,
C.sub.5-C.sub.7-cyclo-alkenyloxy, C.sub.1-C.sub.6-haloalkoxy,
C.sub.3-C.sub.6-haloalkenyloxy, hydroxy-C.sub.1-C.sub.6-alkoxy,
cyano-C.sub.1-C.sub.6-alkoxy,
C.sub.3-C.sub.7-cyclo-alkyl-C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkoxy-C.s- ub.3-C.sub.6-alkenyloxy,
C.sub.1-C.sub.6-alkylcarbonyloxy,
C.sub.1-C.sub.6-haloalkylcarbonyloxy,
C.sub.1-C.sub.6-alkylcarbamoyloxy,
C.sub.1-C.sub.6-haloalkylcarbamoyloxy-C.sub.1-C.sub.6-alkoxycarbonyl-C.su-
b.2-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkoxy,
di-C.sub.1-C.sub.6-alkyl-amino-C.sub.1-C.sub.6-alkoxy, phenyl which
may carry from one to three of the following substituents: cyano,
nitro, halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl, phenyl-C.sub.1-C.sub.6-alkoxy,
phenyl-C.sub.3-C.sub.6-alkenyloxy or
phenyl-C.sub.3-C.sub.6-alkynyloxy, where one or two methylene
groups of each of the carbon chains may be replaced with --O--,
--S-- or --N(C.sub.1-C.sub.6-alkyl)- and each phenyl ring may carry
from one to three of the following substituents: cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl, heterocyclyl,
heterocyclyl-C.sub.3-C.sub.- 6-alkoxy,
heterocyclyl-C.sub.3-C.sub.6-alkenyloxy or
heterocyclyl-C.sub.1-C.sub.6-alkynyloxy, where one or two methylene
groups of each of the carbon chains may be replaced with --O--,
--S-- or --N(C.sub.1-C.sub.6-alkyl)- and the heterocyclyl ring may
be from three-membered to seven-membered and saturated, unsaturated
or aromatic and may contain from one to four hetero atoms selected
from the group consisting of one or two oxygen or sulfur atoms and
up to four nitrogen atoms and furthermore may carry from one to
three of the following substituents: cyano, nitro, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy or
C.sub.1-C.sub.6-alkoxycarbonyl, or --N(R.sup.15)R.sup.16, where
R.sup.15 and R.sup.16 are each hydrogen, C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylcarbon- yl, C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1- -C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.2-C.sub.6-alkenyl, where the
alkenyl chain may additionally carry from one to three of the
following radicals: halogen and cyano or phenyl which may carry
from one to three of the following substituents: cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.3-C.sub.6-alkenyl- , C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl, or R.sup.15 and R.sup.16 together
with the common nitrogen atom form a saturated or unsaturated
4-membered to 7-membered heterocyclic structure, where one ring
member may be replaced with --O--, --S--, --N.dbd., --NH-- or --N
(C.sub.1-C.sub.6-alkyl)-;
[0008] R.sup.6 and R.sup.7 are each 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-alkynyl or
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, or
[0009] R.sup.6 and R.sup.7 together form a saturated or
unsaturated, two-membered to four-membered carbon chain which may
carry an oxo substituent, where one member of this chain may -be
replaced with an -oxygen, sulfur or nitrogen atom which is not
adjacent to X.sup.3 and X.sup.4, and where the chain may carry from
one to three of the following radicals: cyano, nitro, amino,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenylo- xy,
C.sub.2-C.sub.6-alkynyloxy, C.sub.1-C.sub.6-haloalkyl,
cyano-C.sub.1-C.sub.6-alkyl, hydroxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyloxy-- C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkynyloxy-C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.7-cycloalkyl, C.sub.3-C.sub.7-cycloalkoxy, carboxyl,
C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkylcarbonyloxy-C.sub.1-- C.sub.6-alkyl and phenyl
which may carry from one to three of the following radicals:
halogen, cyano, nitro, amino, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl, and where the chain may furthermore
be substituted by a fused-on or spiral-bonded three-membered to
seven-membered ring, and one or two carbon atoms of this ring may
be replaced with oxygen, sulfur and unsubstituted or
C.sub.1-C.sub.6-alkyl-s- ubstituted nitrogen atoms and this ring
may carry one or two of the following substituents: cyano,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cyanoalk- yl,
C.sub.1-C.sub.6-haloalkyl and C.sub.1-C.sub.6-alkoxycarbonyl;
[0010] R.sup.8 is hydrogen, cyano, 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-haloalk- yl, C.sub.3-C.sub.7-cycloalkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alk- yl or
C.sub.1-C.sub.6-alkoxycarbonyl;
[0011] R.sup.9 and R.sup.12 are each hydrogen, cyano, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
halo-C.sub.1-C.sub.6-alkyl- , C.sub.1-C.sub.6-alkylcarbonyl or
C.sub.1-C.sub.6-alkoxycarbonyl;
[0012] R.sup.10 is hydrogen, O--R.sup.17, S--R.sup.17 or
C.sub.1-C.sub.6-alkyl which may furthermore carry one or two
C.sub.1-C.sub.6-alkoxy substituents or R.sup.10 is
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl,
C.sub.1-C.sub.6-haloalk- yl, C.sub.3-C.sub.7-cycloalkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-- alkyl,
C.sub.1-C.sub.6-alkyliminooxy, --N(R.sup.15)R.sup.16 or phenyl
which may carry from one to three of the following substituents:
cyano, nitro, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.2-C.sub.6-alkenyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-alkoxycarbonyl;
[0013] R.sup.17 is hydrogen, C.sub.1-C.sub.61-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.7-cycloal- kyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.3-C.sub.6-haloalkenyl, cyano-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl- ,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkyl-o- ximino-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylcarbonyl, c.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkylcarbonyl-C.sub.1-C.s- ub.6-alkyl,
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1-C.sub.6-alkyl, phenyl or
phenyl-C.sub.1-C.sub.6-alkyl, where each of the phenyl radicals in
turn may carry from one to three of the following substituents:
cyano, nitro, halogen, C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy and C.sub.1-C.sub.6-alkoxycarbonyl;
[0014] R.sup.11 is hydrogen, cyano, halogen, 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-- C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylcarbonyl, C.sub.1-C.sub.6-alkoxycarbonyl,
--NR.sup.18R.sup.19, where R.sup.18 and R.sup.19 have the same
meanings as R.sup.15 and R.sup.16, or phenyl which may furthermore
carry from one to three of the following substituents: cyano,
nitro, halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl;
[0015] R.sup.13 is hydrogen, cyano, C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxycarbonyl; or R.sup.9 and R.sup.10 together
form a two-membered to five-membered carbon chain in which one
carbon atom may be replaced with oxygen, sulfur or unsubstituted or
C.sub.1-C.sub.6-alkyl-substituted nitrogen;
[0016] R.sup.1 is halogen, cyano, nitro or trifluoromethyl;
[0017] R.sup.2 is hydrogen or halogen;
[0018] R.sup.3 is hydrogen, nitro, C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl, C.sub.3-C.sub.6-alkynyl,
C.sub.3-C.sub.6-cycloal- kyl, C.sup.3-C.sub.8-cycloalkylcarbonyl,
cyano-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl, formyl,
C.sub.1-C.sub.6-alkanoyl, C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-haloalkylcarbonyl,
C.sub.1-C.sub.6-alkylcarbonyl-C.sub.1-- C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1-C.sub.6-alkyl; a group
--N(R.sup.20)R.sup.21, where R.sup.20 and R.sup.21 have one of the
meanings of R.sup.15 and R.sup.16; phenyl or
phenyl-C.sub.1-C.sub.6-alkyl- , where each phenyl ring may carry
from one to three of the following radicals: cyano, nitro, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.4 is hydrogen, cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.6-cycloal- kyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-hydroxyalkyl,
cyano-C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy,
C.sub.1-C.sub.6-alkylthio,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl or phenyl which may
carry from one to three of the following radicals: cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl- , C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl; R.sup.5 is hydrogen, cyano, nitro,
halogen, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.2-C.sub.6-alkynyl, C.sub.3-C.sub.7-cycloal- kyl,
C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-hydroxyalkyl,
cyano-C.sub.1C.sub.6-alkyl,
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl,
C.sub.1-C.sub.6-alkylthio-C.sub.1-C.sub.6-alkyl, formyl,
C.sub.1-C.sub.6-alkyl-carbonyl, C.sub.1-C.sub.6-haloalkylcarbonyl,
C.sub.1-C.sub.6-alkoxycarbonyl,
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.2-C.- sub.6-alkenyl,
--N(R.sup.22)R.sup.23, where R.sup.22 and R.sup.23 have one of the
meanings of R.sup.15 and R.sup.16, or phenyl which may carry from
one to three of the following radicals: cyano, nitro, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-haloalkyl- , C.sub.1-C.sub.6-alkoxy and
C.sub.1-C.sub.6-alkoxycarbonyl, or R.sup.4 and Rs together form a
saturated or unsaturated 3-membered or 4-membered carbon chain
which may contain from one to three of the following hetero atoms:
1 or 2 oxygen atoms, 1 or 2 sulfur atoms and from 1 to 3 nitrogen
atoms, and the chain may furthermore carry from one to three of the
following radicals: cyano, nitro, amino, halogen,
C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl,
C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthi- o and
C.sub.1-C.sub.6-alkoxycarbonyl; with the proviso that R.sup.4 may
not be trifluoromethyl at the same time as R.sup.5 is hydrogen when
W is --CH.dbd.CH--CO--R.sup.10 where R.sup.10 is
C.sub.1-C.sub.6-alkoxy or C.sub.3-C.sub.7-cycloalkoxy, and with the
proviso that R.sup.4 and R.sup.5 are not simultaneously hydrogen
when W is CH(R.sup.8)--CH(R.sup.9- )--CO--R.sup.10 and R.sup.9 is
not halogen, and the salts and enol ethers of those compounds I in
which R.sup.3 is hydrogen.
[0019] The present invention furthermore relates to herbicidal
3-phenyluracils of the general formulae Ia and Ib 4
[0020] in which R.sup.3' is C.sub.1-C.sub.6-alkyl,
C.sub.3-C.sub.6-alkenyl or C.sub.3-C.sub.6-alkynyl.
[0021] The present invention furthermore relates to herbicides,
pesticides and plant growth-regulating agents which contain these
compounds as active ingredients.
[0022] U.S. Pat. No. 4,979,982 discloses herbicidal 3-phenyluracils
of the formula I' 5
[0023] where R.sup.a is hydrogen or halogen, R.sup.b is
C.sub.1-C.sub.12-alkyl or cycloalkyl and R.sup.c is
C.sub.1-C.sub.12-alkyl or C.sub.3-C.sub.12-alkenyl.
[0024] Furthermore, EP-A 408 382 describes, inter alia, structures
of the formula I" 6
[0025] where R.sup.d is hydrogen, alkyl, hydroxymethyl or
haloalkyl, R.sup.e is haloalkyl, R.sup.f is hydrogen, alkyl,
haloalkyl, hydroxymethyl, halogen or nitro, X.sup.1 is oxygen or
sulfur, R.sup.g is hydrogen, alkyl, alkoxy or alkoxyalkyl and
R.sup.h is hydrogen, alkyl, cycloalkyl, haloalkyl, phenyl or benzyl
and R.sup.i is halogen, nitro or cyano.
[0026] Moreover, Swiss Patent 482,402 relates to weed killers which
contain as active ingredients, inter alia, substituted uracils and
thiouracils of the formula II'" 7
[0027] where Aryl is aryl which is unsubstituted or substituted by
fluorine, chlorine, bromine, hydroxyl, alkoxy, cyano, alkylthio,
alkyl or nitro, R.sup.k is dialkylphosphoryl, alkyl, alkenyl,
cyano, hydrogen, unsubstituted or substitituted alkyl,
unsubstituted or substituted carbamoyl, unsubstituted or
substituted thiocarbamoyl, unsubstituted or substituted mercapto or
acyl, R.sup.l is alkyl, alkoxy, hydrogen, chlorine or bromine and
R.sup.m is alkylthio, alkoxy, alkylthioalkyl, alkenyl, cyano,
thiocyano, nitro, halogen, hydrogen or unsubstituted or substituted
alkyl or R.sup.l and R.sup.m together form a tri-, tetra- or
pentamethylene chain.
[0028] Furthermore, WO-A 87/07 602 describes, inter alia, compounds
of the formula I.sup.IV 8
[0029] where R.sup.p and R.sup.q are each alkyl, alkenyl, alkynyl
or halogen and R.sup.a is, inter alia, cyano or a substituted
alkylcarbonyl-, carbonyl- or alkoxycarbonyl-alkyl group and R.sup.o
is hydrogen, alkyl, alkylcarbonyl, alkenyl or alkynyl.
[0030] Other 3-aryluracils of the same type as compounds I are
disclosed, for example, in the following publications: EP-A 195
346, EP-A 260 621,- EP-A 438 209, WO 88/10254, WO 89/02891 and WO
89/03825, EP-A 473 551, WO 91/00278, WO 90/15057, EP-A 255 047,
EP-A 438 209, EP-A 408 382, EP-A 476 697, EP-A 420 194, U.S. Pat.
No. 4,981,508, WO 91/07393, U.S. Pat. No. 3,981,715 and DE-A 37 12
782.
[0031] The selectivity of these known herbicides with respect to
the weeds is, however, satisfactory only to a limited extent, so
that it is an object of the present invention to provide novel
herbicidal compounds with which the weeds can be selectively
controlled more effectively than in the past (and which are well
tolerated by the crops).
[0032] We have found that this object is achieved by the
substituted 3-phenyluracils I, Ia and Ib defined at the outset.
[0033] We have also found herbicides which contain these substances
and have a good herbicidal action. They are tolerated and hence
selective in broad-leaved crops and in monocotyledon plants which
are not members of the Gramineae.
[0034] The novel compounds I, Ia and Ib are also suitable as
defoliants or desiccants in, for example, cotton, potato, rape,
sunflower, soybean or field beans. Some compounds I can also be
used for controlling pests, in particular insects.
[0035] The meanings stated above for R.sup.1 to R.sup.17 are
general terms for an individual list of the specific group members.
All alkyl, alkenyl, alkynyl, haloalkyl and haloalkoxy moieties may
be straight-chain or branched. The haloalkyl and haloalkoxy
radicals may carry identical or different halogen atoms.
[0036] Examples of specific meanings are as follows: halogen:
fluorine, chlorine, bromine and iodine, preferably fluorine and
chlorine; C.sub.1-C.sub.6-alkyl: methyl, ethyl, n-propyl,
1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl,
1,1-dimethyl-ethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl,
3-methyl-butyl, 2,2-dimethylpropyl, 1-ethylpropyl,
1,1-dimethyl-propyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl,
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,
1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,
2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl,
1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl, preferably
methyl, ethyl, isopropyl, n-butyl and tert-butyl;
C.sub.2-C.sub.6-alkenyl: vinyl and C.sub.3-C.sub.6-alkenyl, such as
prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, n-buten-1-yl,
n-buten-2-yl, n-buten-3-yl, 1-methylprop-1-en-1-yl,
2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl,
2-methyl-prop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl,
n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en-1-yl,
2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl,
1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl,
3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl,
2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl,
1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl,
1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl,
1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl,
n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl,
1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl,
3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl,
1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl,
3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl,
1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl,
3-methyl-pent-3-en-1-yl, 4-methylpent-3-en-1-yl,
1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl,
3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl,
1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl,
1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl,
1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl,
1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl,
2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl,
2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl,
3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl,
1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl,
2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl,
1, 1, 2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl,
1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl,
preferably vinyl, prop-2-en-1-yl and but-2-en-2-yl;
C.sub.2-C.sub.6-alkynyl: ethynyl and C.sub.3-C.sub.6-alkynyl, such
as prop-1-yn-1-yl, prop-2-yn-3-yl, n-but-1-yn-1-yl,
n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-1-yl,
n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pentyn-5-yl, pent-2-yn-1-yl,
pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-1-yl,
3-methyl-but-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1-yl,
n-hex-1-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl,
n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl,
n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl,
3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl,
3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl,
4-methylpent-2-yn-4-yl an d 4-methylpent-2-yn-5-yl, preferably
prop-2-ynyl; C.sub.3-C.sub.5-cycloalky- l: cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, preferably
cyclopropyl, cyclopentyl and cyclohexyl; C.sub.1-C.sub.6-haloalkyl:
chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl,
difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorof
luoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl,
2,2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl,
2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2, 2,
2-trichloroethyl, pentafluoroethyl and 3-chloropropyl, preferably
trifluoromethyl; hydroxy-C.sub.1-C.sub.6-alkyl- : hydroxymethyl,
1-hydroxyeth-1-yl, 2-hydroxyeth-1-yl, 1-hydroxyprop-1-yl,
2-hydroxyprop-1-yl, 3-hydroxyprop-1-yl, 1-hydroxyprop-2-yl,
2-hydroxyprop-2-yl, 1-hydroxybut-1-yl, 2-hydroxybut-1-yl,
3-hydroxybut-1-yl, 4-hydroxybut-1-yl, 1-hydroxybut-2-yl,
2-hydroxybut-2-yl, 1-hydroxybut-3-yl, 2-hydroxybut-3-yl,
1-hydroxy-2-methylprop-3-yl, 2-hydroxy-2-methylprop-3-yl,
3-hydroxy-2-methylprop-3-yl and 2-hydroxymethylprop-2-yl,
preferably hydroxymethyl; cyano-C.sub.1-C.sub.6-alkyl: cyanomethyl,
1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyanoprop-1-yl,
2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanoprop-2-yl,
2-cyanoprop-2-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl,
3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyano-but-2-yl,
2-cyanobut-2-yl, 1-cyanobut-3-yl, 2-cyanobut-3-yl,
1-cyano-2-methylprop-3-yl, 2-cyano-2-methylprop-3-yl,
3-cyano-2-methylprop-3-yl and 2-cyanomethylprop-2-yl, preferably
cyanomethyl; amino-C.sub.1-C.sub.6-alk- yl: aminomethyl,
1-aminoethyl, 2-aminoethyl, 1-aminoprop-1-yl, 2-aminoprop-1-yl,
3-aminoprop-1-yl, 1-aminobut-1-yl, 2-aminobut-1-yl,
3-aminobut-1-yl, 4-aminobut-1-yl, 1-aminobut-2-yl, 2-aminobut-2-yl,
3-aminobut-2-yl, 4-aminobut-2-yl, 1-(aminomethyl)-eth-1-yl,
1-(aminomethyl)-1-(methyl)-eth-1-yl and 1-(aminomethyl)-prop-1-yl,
preferably aminomethyl; phenyl-C.sub.l-C.sub.6-alkyl: benzyl,
1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl,
3-phenylprop-1-yl, 1-phenylbut-1-yl, 2-phenylbut-1-yl,
3-phenylbut-1-yl, 4-phenylbut-1-yl, 1-phenylbut-2-yl,
2-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl,
1-(phenylmethyl)-eth-1-yl, 1-(phenylmethyl)-1-(methyl)-- eth-1-yl
and 1-(phenyl-methyl)-prop-1-yl, preferably benzyl;
C.sub.1-C.sub.6-alkoxy: methoxy, ethoxy, n-propoxy, 1-methylethoxy,
n-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy,
n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy,
1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy,
1-ethylpropoxy, n-hexyloxy, 1-methylpentyloxy, 2-methylpentyloxy,
3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutoxy,
1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy,
2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy,
2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy,
1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy, preferably
C.sub.1-C.sub.4-alkoxy, such as methoxy and ethoxy;
C.sub.1-C.sub.6-haloalkoxy: 2-fluoroethoxy, 2,2-difluoroethoxy, 2,
2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,
2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2, 2,
2-trichloroethoxy and 3-bromoprop-1-yloxy;
C.sub.1-C.sub.6-alkylthio: methylthio, ethylthio, n-propylthio,
1-methylethylthio, n-butylthio, 1-methylpropylthio,
2-methylpropylthio, 1,1-dimethylethylthio, n-pentylthio,
1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio,
1,1-dimethylpropylthio, 1,2-dimethylpropylthio,
2,2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio,
1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio
4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio,
1,3-dimethylbutylthio, 2,2-dimethylbutylthio,
2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio,
2-ethylbutylthio, 1, 1, 2-trimethylpropylthio, 1, 2,
2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and
1-ethyl-2-methylpropylthio, preferably C.sub.1-C.sub.4-alkylthio,
such as methylthio and ethylthio;
C.sub.1-C.sub.6-alkoxy-C.sub.1-C.sub.6-alkyl: methoxymethyl,
ethoxymethyl, n-propoxymethyl, (1-methylethoxy)-methyl,
n-butoxymethyl, (1-methylpropoxy)-methyl, (2-methylpropoxy)-methyl,
(1,1-dimethylethoxy)-methyl, methoxyethyl, ethoxyethyl,
n-propoxyethyl, (1-methylethoxy)-ethyl, n-butoxyethyl,
(1-methylpropoxy)-ethyl, (2-methylpropoxy)-ethyl,
(1,1-dimethylethoxy)-ethyl, 3-methoxypropyl, 2-methoxypropyl and
2-ethoxypropyl, preferably C.sub.1-C.sub.4-alkoxy-C.s- ub.1- or
-C.sub.2-alkyl, such as methoxymethyl, ethoxymethyl,
2-methoxy-ethyl and 2-ethoxyethyl; C.sub.1-C.sub.6-alkylamino:
methylamino, ethylamino, n-propylamino, 1-methylethylamino,
n-butylamino, 1-methylpropylamino, 2-methylpropylamino,
1,1-dimethylethylamino, n-pentylamino, 1-methylbutylamino,
2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropylamino,
1-ethylpropylamino, n-hexylamino, 1,1-dimethylpropylamino,
1,2-dimethylpropylamino, 1-methylpentylamino, 2-methylpentylamino,
3-methylpentylamino, 4-methylpentylamino, 1,1-dimethylbutylamino,
1,2-dimethylbutylamino, 1,3-dimethylbutylamino,
2,2-dimethylbutylamino, 2,3-dimethylbutylamino,
3,3-dimethylbutylamino, 1-ethylbutylamino, 2-ethylbutylamino, 1, 1,
2-trimethylpropylamino, 1, 2, 2-trimethylpropylamino,
1-ethyl-1-methylpropylamino and 1-ethyl-2-methylpropylamino,
preferably C.sub.1-C.sub.4-alkylamino, such as methylamino and
ethylamino; di-C.sub.1-C.sub.6-alkylamino: N,N-dimethylamino,
N,N-diethylamino, N,N-dipropylamino, N,N-di-(1-methylethyl)-amino,
N,N-dibutylamino, N,N-di-(1-methylpropyl)-amino,
N,N-di-(2-methylpropyl)-amino, N,N-di- (1,1-dimethylethyl)-amino,
N-ethyl-N-methylamino, N-methyl-N-propylamino,
N-methyl-N-(1-methylethyl)-amino, N-butyl-N-methylamino,
N-methyl-N-(1-methylpropyl)-amino,
N-methyl-N-(2-methylpropyl)-amino,
N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino,
N-ethyl-N-(1-methylethyl)-amino, N-butyl-N-ethylamino,
N-ethyl-N-(1-methylpropyl)-amino, N-ethyl-N-(2-methylpropyl)-amino,
N-ethyl-N-(1,1-dimethylethyl)-amino,
N-(1-methylethyl)-N-propylamino, N-butyl-N-propyl-amino,
N-(1-methylpropyl)-N-propylamino,
N-(2-methyl-propyl)-N-propylamino,
N-(1,1-dimethylethyl)-N-propyl-amino,
N-butyl-N-(l-methylethyl)-amino,
N-(1-methyl-ethyl)-N-(1-methylpropyl)-am- ino,
N-(1-methylethyl)-N-(2-methylpropyl)-amino,
N-(1,1-dimethylethyl)-N-(- 1-methyl-ethyl)-amino,
N-butyl-N-(1-methylpropyl)-amino, N-butyl-N-(2-methylpropyl)-amino,
N-butyl-N-(1,1-dimethyl-ethyl)-amino,
N-(1-methylpropyl)-N-(2-methylpropyl)-amino,
N-(1,1-dimethylethyl)-N-(1-m- ethylpropyl)-amino and N-
(1,1-dimethylethyl)-N-(2-methylpropyl)-amino, preferably
dimethylamino and diethylamino; C.sub.1-C.sub.6-alkylcarbonyl:
methylcarbonyl, ethylcarbonyl, propylcarbonyl,
1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl,
2-methylpropylcarbonyl, 1,1-dimethylethylcarbonyl, pentylcarbonyl,
1-methylbutyl-carbonyl, 2-methylbutylcarbonyl,
3-methylbutylcarbonyl, 1,1-dimethylpropylcarbonyl,
1,2-dimethylpropylcarbonyl, 2,2-dimethylpropylcarbonyl,
1-ethylpropylcarbonyl, hexylcarbonyl, 1-methylpentylcarbonyl,
2-methylpentyl-carbonyl, 3-methylpentylcarbonyl,
4-methylpentylcarbonyl, 1,1-dimethylbutylcarbonyl,
1,2-dimethylbutylcarbonyl, 1,3-dimethylbutylcarbonyl,
2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl,
3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl,
2-ethylbutylcarbonyl, 1, 1, 2-tri-methylpropylcarbo- nyl, 1, 2,
2-trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl and
1-ethyl-2-methylpropyl-carbonyl, preferably
C.sub.1-C.sub.4-alkylcarbonyl- , such as methyl-carbonyl and
ethylcarbonyl; C.sub.1-C.sub.6-alkylcarbonyl- oxy:
methylcarbonyloxy, ethylcarbonyl-oxy, n-propylcarbonyloxy,
1-methylethylcarbonyloxy, n-butylcarbonyloxy,
1-methylpropylcarbonyloxy, 2-methyl-propylcarbonyloxy,
1,1-dimethylethylcarbonyloxy, n-pentylcarbonyloxy,
1-methylbutylcarbonyloxy, 2-methyl-butylcarbonyloxy,
3-methylbutylcarbonyloxy,, 1,1-dimethyl-propylcarbonyloxy,
1,2-dimethylpropylcarbonyloxy, 2,2-dimethylpropylcarbonyloxy,
1-ethylpropylcarbonyloxy, n-hexylcarbonyloxy,
1-methylpentylcarbonyloxy, 2-methyl-pentylcarbonyloxy,
3-methylpentylcarbonyloxy, 4-methyl-pentylcarbonyloxy,
1,1-dimethylbutylcarbonyloxy, 1,2-dimethylbutylcarbonyloxy,
1,3-dimethylbutylcarbonyloxy, 2,2-dimethylbutylcarbonyloxy,
2,3-dimethylbutylcarbonyloxy, 3,3-dimethylbutylcarbonyloxy,
1-ethylbutylcarbonyloxy, 2-ethylbutylcarbonyloxy, 1, 1,
2-trimethylpropyl-carbonyloxy, 1, 2, 2-trimethylpropylcarbonyloxy,
1-ethyl-1-methylpropylcarbonyloxy and
1-ethyl-2-methylpropyl-carbonyloxy, preferably
C.sub.1-C.sub.4-alkylcarbo- nyloxy, such as methylcarbonyloxy and
ethylcarbonyloxy; C.sub.1-C.sub.6-alkylcarbamoyloxy, such as
methylcarbamoyloxy, ethylcarbamoyloxy, propylcarbamoyloxy,
1-methylethyl-carbamoyloxy, butylcarbamoyloxy,
1-methylpropylcarbamoyloxy, 2-methylpropylcarbamoyloxy- ,
1,1-dimethylethyl-carbamoyloxy, pentylcarbamoyloxy,
1-methylbutylcarbamoyloxy, 2-methylbutylcarbamoyloxy,
3-methylbutylcarbamoyloxy, 1,1-dimethylpropylcarbamoyloxy,
1,2-dimethylpropyl-carbamoyloxy, 2,2-dimethylpropylcarbamoyloxy,
1-ethyl-propylcarbamoyloxy, hexylcarbamoyloxy,
1-methylpentyl-carbamoylox- y, 2-methylpentylcarbamoyloxy,
3-methylpentylcarbamoyloxy, 4-methylpentylcarbamoyloxy,
1,1-dimethylbutylcarbamoyloxy, 1,2-dimethylbutylcarbamoyloxy,
1,3-dimethylbutylcarbamoyloxy, 2,2-dimethylbutylcarbamoyloxy,
2,3-dimethylbutylcarbamoyloxy, 3,3-dimethylbutyl-carbamoyloxy,
1-ethylbutylcarbamoyloxy, 2-ethylbutyl-carbamoyloxy, 1, 1,
2-trimethylpropylcarbamoyloxy, 1, 2, 2-trimethylpropylcarbamoyloxy,
1-ethyl-1-methylpropylcarbamoyloxy and
1-ethyl-2-methylpropylcarbamoyloxy, preferably
C.sub.1-C.sub.4-alkylcarba- moyloxy, in particular
methyl-carbamoyloxy and ethylcarbamoyloxy;
C.sub.1-C.sub.6-haloalkylcarbamoyloxy, in particular C.sub.1- or
C.sub.2-haloalkylcarbamoyloxy, such as chloromethylcarbamoyloxy,
dichloromethylcarbamoyloxy, trichloromethylcarbamoyloxy,
fluoromethylcarbamoyloxy, difcluoromethylcarbamoyloxy,
trifluoromethylcarbamoyloxy, chlorofluoromethylcarbamoyloxy,
dichlorofluoromethylcarbamoyloxy,
chlorodifluoro-methylcarbamoyloxy, 1-fluoroethylcarbamoyloxy,
2-fluoro-ethylcarbamoyloxy, 2,2-difluoroethylcarbamoyloxy, 2, 2,
2-trifluoroethylcarbamoyloxy, 2-chloro-2-fluoroethylcarbamoyloxy,
2-chloro-2,2-difluoroethylcarbamoylox- y,
2,2-dichloro-2-fluoroethylcarbamoyloxy, 2, 2,
2-trichloro-ethylcarbamoy- loxy and pentafluoroethylcarbamoyloxy;
C.sub.1- or C.sub.2-haloalkylcarbon- yloxy: chloroacetyl,
dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl,
trifluoroacetyl, chlorofluoroacetyl, dichlorofluoroacetyl,
chlorodifluoroacetyl, .alpha.-fluoropropionyl,
.beta.-fluoropropionyl, .beta., .beta., .beta.-difluoropropionyl,
.beta., .beta., .beta.-tri-fluoropropionyl,
.beta.-chloro-.beta.-fluoropropionyl,
.beta.-chloro-.beta.,.beta.-difluoropropionyl,
.beta.,.beta.-dichloro-.be- ta.-fluoropropionyl, .beta., .beta.,
.beta.-trichloropropionyl and pentafluoropropionyl, preferably
trichloroacetyl and trifluoroacetyl;
C.sub.1-C.sub.6-alkoxycarbonyl-C.sub.1-C.sub.6-alkyl:
methoxycarbonylmethyl, ethoxycarbonylmethyl,
n-propoxycarbonylmethyl, (1-methylethoxycarbonyl)-methyl,
n-butoxycarbonylmethyl,(1-methylpropoxyc- arbonyl)-methyl,
(2-methylpropoxycarbonyl)-methyl, (1,1-dimethylethoxycarb-
onyl)-methyl, methoxy-carbonylethyl, ethoxycarbonylethyl,
n-propoxycarbonylethyl, (1-methylethoxycarbonyl)-ethyl-,
n-butoxycarbonyl-ethyl, (1-methylpropoxycarbonyl)-ethyl,
(2-methylpropoxy-carbonyl)-ethyl,
(1,1-dimethylethoxycarbonyl)-ethyl, 3-(methoxycarbonyl)-propyl,
2-(methoxycarbonyl)-propyl and 2-(ethoxycarbonyl)-propyl,
preferably C.sub.1-C.sub.4-alkoxy-carbonyl-C.s- ub.1- or
-C.sub.2-alkyl, such as methoxycarbonylmethyl,
ethoxycarbonylmethyl, 2-methoxycarbonylethyl and
2-ethoxycarbonylethyl;
di-C.sub.1-C.sub.6-alkylamino-C.sub.1-C.sub.6-alkoxy:
N,N-dimethylaminoethoxy, N,N-diethylaminoethoxy,
N,N-di(n-propyl)-aminoet- hoxy, N,N-di-(1-methylethyl)-aminoethoxy,
N,N-dibutylamino-ethoxy, N,N-di-(1-methylpropyl)-aminoethoxy,
N,N-di-(2-methylpropyl)-aminoethoxy,
N,N-di-(1,1-dimethylethyl)-aminoethoxy,
N-ethyl-N-methylaminoethoxy, N-methyl-N-propylaminoethoxy,
N-methyl-N-(l-methylethyl)-aminoethoxy,
N-butyl-N-methylaminoethoxy,
N-methyl-N-(1-methylpropyl)-aminoethoxy,
N-methyl-N-(2-methylpropyl)-aminoethoxy,
N-(1,1-dimethylethyl)-N-methylam- inoethoxy,
N-ethyl-N-propylaminoethoxy, N-ethyl-N-(1-methylethyl)-aminoeth-
oxy, N-butyl-N-ethylaminoethoxy,
N-ethyl-N-(1-methylpropyl)-aminoethoxy,
N-ethyl-N-(2-methylpropyl)-aminoethoxy,
N-ethyl-N-(1,1-dimethylethyl)-ami- noethoxy,
N-(1-methylethyl)-N-propylaminoethoxy, N-butyl-N-propyl-aminoeth-
oxy, N-(l-methylpropyl)-N-propylaminoethoxy,
N-(2-methylpropyl)-N-propylam- inoethoxy,
N-(1,1-dimethylethyl)-N-propylaminoethoxy,
N-butyl-N-(1-methyl-ethyl)-aminoethoxy,
N-(1-methylethyl)-N-(1-methylprop- yl)-aminoethoxy,
N-(1-methylethyl)-N-(2-methylpropyl)-aminoethoxy,
N-(1,1-dimethylethyl)-N-(1-methylethyl)-aminoethoxy,
N-butyl-N-(1-methylpropyl)-aminoethoxy,
N-butyl-N-(2-methylpropyl)-aminoe- thoxy, N-butyl-N-
(1,1-dimethyl-ethyl)-aminoethoxy,
N-(l-methylpropyl)-N-(2-methyl-propyl)-aminoethoxy,
N-(1,1-dimethylethyl)-N-(1-methyl-propyl)-aminoethoxy and
N-(1,1-dimethylethyl)-N-(2-methylpropyl)-aminoethoxy.
[0037] The substituted phenyluracils I may be in the form of their
agriculturally useful salts or enol ethers where R.sup.3 is
hydrogen.
[0038] Suitable agriculturally useful salts are in general the
salts of bases which do not adversely affect the herbicidal action
of I.
[0039] Particularly suitable basic salts are those of the alkali
metals, preferably the sodium and potassium salts, those of the
alkaline earth metals, preferably calcium, magnesium and barium
salts, and those of the transition metals, preferably manganese,
copper, zinc and iron salts, as well as the ammonium salts, which
may carry from one to three C.sub.1-C.sub.4-alkyl or
hydroxy-C.sub.1-C.sub.4-alkyl substituents and/or one phenyl or
benzyl substituent, preferably diisopropylammonium,
tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium
and tri-methyl-2-hydroxyethylammonium salts, the phosphonium salts,
the sulfonium salts, preferably tri-C.sub.1-C.sub.4-alkyl-sulfonium
salts, and the sulfoxonium salts, preferably
tri-C.sub.1-C.sub.4-alkylsulfoxoniu- m salts.
[0040] With regard to the use of the novel 3-phenyl-uracils I, Ia
and lb as herbicidal, plant growth-regulating and insecticidal
compounds, the variables preferably have the following meanings:
9
[0041] where X.sup.1 and X.sup.2 independently of one another are
each sulfur or oxygen and X, W, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.23, R.sup.5 and R.sup.56 may be freely combined with one
another, with the proviso that R.sup.4 cannot be 4.27 if at the
same time R.sup.5 is 5.01 and W is
--C(R).dbd.C(R.sup.9)--CO--R.sup.10, where R.sup.8 is 8.01, R.sup.9
is 9.01 and R.sup.10 is 10.03-10.12 or 10.20-10.23.
[0042] R.sup.1 is particularly preferably a radical selected from
the group consisting of 1.01-1.07, R.sup.2 is particularly
preferably a radical selected from the group consisting of
2.01-2.05, R.sup.3 is particularly preferably a radical selected
from the group consisting of 3.01-3.97, R.sup.3is particularly
preferably a radical selected from the group consisting of 3.01-3'.
17, R.sup.4 is particularly preferably a radical selected from the
group consisting of 4.01-4.72, R.sup.5 is particularly preferably a
radical selected from the group consisting of 5.001-5.105 or
R.sup.4 and R.sup.5 together particularly preferably form a radical
selected from the group consisting of 45.01-45.54 and W is
particularly preferably one of the following radicals W1-W7:
[0043] W1 --C(R.sup.8)(X.sup.3R.sup.6)(R.sup.4R.sup.7)
[0044] W2 --C(R.sup.8).dbd.X.sup.5,
[0045] W3 --C(R.sup.8).dbd.C(R.sup.9)--CO--R.sup.10,
[0046] W4 --C(R.sup.8).dbd.CR.sup.9--CH.sub.2--CO--R.sup.10,
[0047] W5
--C(R.sup.8.dbd.CR.sup.9--CR.sup.11.dbd.CR.sup.12--CO--R.sup.10,
[0048] W6
--CR.sup.8.dbd.CR.sup.9--CH.sub.2--CHR.sup.13--CO--R.sup.10;
[0049] W7 --CR.sup.8.dbd.CR.sup.9--CN;
[0050] where X.sup.3 and X.sup.4 independently of one another are
each O or S, X.sup.5 is O, S or NR.sup.14, R.sup.6 and R.sup.7
independently of one another are each a radical selected from the
group consisting of 6.01-6.19, or R.sup.6 and R.sup.7 together form
a radical selected from the group consisting of 67.01-67.63,
R.sup.8 is a radical selected from the group consisting of
8.01-8.22, R.sup.9 and R.sup.12 are each a radical selected from
the group consisting of 9.01-9.23, R.sup.10 is a radical selected
from the group consisting of 10.01-10.144, R.sup.11 is a radical
selected from the group consisting of 11.01-11.25, R.sup.13 is a
radical selected from the group consisting of 13.01-13.08 and
R.sup.14 is a radical selected from the group consisting of
14.001-14.162, and all these radicals may be combined freely with
one another.
1TABLE 1 No. R.sup.1 1.01 F 1.02 Cl 1.03 Br 1.04 I 1.05 CN 1.06
NO.sub.2 1.07 CF.sub.3
[0051]
2TABLE 2 No. R.sup.2 2.01 H 2.02 F 2.03 Cl 2.04 Br 2.05 I
[0052]
3TABLE 3 No. R.sup.3 3.01 H 3.02 CH.sub.3 3.03 C.sub.2H.sub.5 3.04
n-C.sub.3H.sub.7 3.05 i-C.sub.3H.sub.7 3.06 n-C.sub.4H.sub.9 3.07
i-C.sub.4H.sub.9 3.08 s-C.sub.4H.sub.9 3.09 tert.-C.sub.4H.sub.9
3.10 cyclopropyl 3.11 cyclobutyl 3.12 cyclopentyl 3.13 cyclohexyl
3.14 cycloheptyl 3.15 cyclooctyl 3.16 CH.sub.2--CN 3.17
CH.sub.2CH.sub.2--CN 3.18 CH(CH.sub.3)CH.sub.2--CN 3.19
C(CH.sub.3).sub.2--CN 3.20 C(CH.sub.3).sub.2CH.sub.2--CN 3.21
CH.sub.2Cl 3.22 CH.sub.2--CH.sub.2Cl 3.23 CH(CH.sub.3)--CH.sub.2Cl
3.24 C(CH.sub.3).sub.2Cl 3.25 CHCl.sub.2 3.26 CF.sub.2Cl 3.27
CF.sub.3 3.28 C.sub.2F.sub.5 3.29 CF.sub.2H 3.30
CH.sub.2--CH.dbd.CH.sub.2 3.31 CH(CH.sub.3)CH.dbd.CH.sub.2 3.32
CH.sub.2--CH.dbd.CH--CH.sub.3 3.34 CH.sub.2-phenyl 3.35
CH.sub.2--C.ident.CH 3.36 CH(CH.sub.3)C.ident.CH 3.37
C(CH.sub.3).sub.2C.ident.CH 3.38 phenyl 3.39 2-F-phenyl 3.40
3-F-phenyl 3.41 4-F-phenyl 3.42 2-Cl-phenyl 3.43 3-Cl-phenyl 3.44
4-Cl-phenyl 3.45 2-CH.sub.3-phenyl 3.46 3-CH.sub.3-phenyl 3.47
4-CH.sub.3-phenyl 3.48 2-CF.sub.3-phenyl 3.49 3-CF.sub.3-phenyl
3.50 4-CF.sub.3-phenyl 3.51 2-OCH.sub.3-phenyl 3.52
3-OCH.sub.3-phenyl 3.53 4-OCH.sub.3-phenyl 3.54
4-COOCH.sub.3-phenyl 3.56 4-COOC.sub.2H.sub.5-phenyl 3.57
4-NO.sub.2-phenyl 3.58 4-CN-phenyl 3.59 2,4-Cl.sub.2-phenyl 3.60
2,4-(CH.sub.3).sub.2-phenyl 3.61 CHO 3.62 CO--CH.sub.3 3.63
CO--C.sub.2H.sub.5 3.64 CO-n-C.sub.3H.sub.7 3.65
CO-i-C.sub.3H.sub.7 3.66 CO-n-C.sub.4H.sub.9 3.67
CO-i-C.sub.4H.sub.9 3.68 CO-s-C.sub.4H.sub.9 3.69
CO-tert.-C.sub.4H.sub.9 3.70 CO-cyclopropyl 3.71 CO-cyclopentyl
3.72 CO-cyclohexyl 3.73 CO--CF.sub.3 3.74 CO--CCl.sub.3 3.75
CO--OCH.sub.3 3.76 CO--OC.sub.2H.sub.5 3.77 COO-n-C.sub.3H.sub.7
3.78 COO-i-C.sub.3H.sub.7 3.79 COO-n-C.sub.4H.sub.9 3.80
COO-i-C.sub.4H.sub.9 3.81 COO-s-C.sub.4H.sub.9 3.82
COO-tert.-C.sub.4H.sub.9 3.83 CH.sub.2--OCH.sub.3 3.84
CH(CH.sub.3)--OCH.sub.3 3.85 CH(CH.sub.3)--OC.sub.2H.sub.5 3.86
CH(CH.sub.3)CH.sub.2--OCH.sub.3 3.87 CH.sub.2OC.sub.2H.sub.5 3.88
NH.sub.2 3.89 NHCH.sub.3 3.90 NHC.sub.2H.sub.5 3.91
N(CH.sub.3).sub.2 3.92 N(CH.sub.3)C.sub.2H.sub.5 3.93
NH--CH--CH.dbd.CH.sub.2 3.94 NH--CH.sub.2C.ident.CH 3.95
NH-cyclopropyl 3.96 NH-cyclopentyl 3.97 NH-cyclohexyl
[0053]
4TABLE 4 No. R.sup.4 4.01 H 4.02 F 4.03 Cl 4.04 Br 4.05 I 4.06
CH.sub.3 4.07 C.sub.2H.sub.5 4.08 n-C.sub.3H.sub.7 4.09
i-C.sub.3H.sub.7 4.10 n-C.sub.4H.sub.9 4.11 i-C.sub.4H.sub.9 4.12
s-C.sub.4H.sub.9 4.13 tert.-C.sub.4H.sub.9 4.14 cyclopropyl 4.15
cyclobutyl 4.16 cyclopentyl 4.17 cyclohexyl 4.18 cycloheptyl 4.19
cyclooctyl 4.20 CN 4.21 CH.sub.2Cl 4.22 CH.sub.2CH.sub.2Cl 4.23
CH(CH.sub.3)CH.sub.2Cl 4.24 CHCl.sub.2 4.25 CCl.sub.3 4.26
CF.sub.2Cl 4.27 CF.sub.3 4.28 C.sub.2F.sub.5 4.29 CF.sub.2H 4.30
CH.dbd.CH.sub.2 4.31 CH.sub.2--CH.dbd.CH.sub.2 4.32
CH.sub.2--CH.dbd.CH--CH.sub.3 4.33 C.ident.CH 4.34
CH.sub.2--C.ident.CH 4.35 CH(CH.sub.3)--C.ident.CH 4.36 phenyl 4.37
2-F-phenyl 4.38 3-F-phenyl 4.39 4-F-phenyl 4.40 2-Cl-phenyl 4.41
3-Cl-phenyl 4.42 4-Cl-phenyl 4.43 2-CH.sub.3-phenyl 4.44
3-CH.sub.3-phenyl 4.45 4-CH.sub.3-phenyl 4.46 2-CF.sub.3-phenyl
4.47 3-CF.sub.3-phenyl 4.48 4-CF.sub.3-phenyl 4.49
2-OCH.sub.3-phenyl 4.50 3-OCH.sub.3-phenyl 4.51 4-OCH.sub.3-phenyl
4.52 4-COOCH.sub.3-phenyl 4.53 4-COOC.sub.2H.sub.5-phenyl 4.54
4-NO.sub.2-phenyl 4.55 4-CN-phenyl 4.56 2,4-Cl.sub.2-phenyl 4.57
2,6-Cl.sub.2-phenyl 4.58 2,4-(CH.sub.3).sub.2-phenyl 4.59
CH.sub.2--OCH.sub.3 4.60 CH.sub.2--OC.sub.2H.sub.5 4.61
CH.sub.2CH.sub.2--OCH.sub.2 4.62 CH.sub.2CH.sub.2--OC.sub.2H.sub.5
4.63 CH(CH.sub.3)--OCH.sub.3 4.64 CH.sub.2--OH 4.65
CH.sub.2CH.sub.2--OH 4.66 CH.sub.2CN 4.67 CH.sub.2CH.sub.2--CN 4.68
CH.sub.2SCH.sub.3 4.69 CH.sub.2CH.sub.2--SCH.sub.3 4.70
CH.sub.2CH.sub.2--SC.sub.2H.sub.5 4.71
CH.sub.2CH.sub.2--S-i-C.sub.3H.sub.7 4.72
CH.sub.2--SC.sub.2H.sub.5
[0054]
5TABLE 5 No. R.sup.5 5.001 H 5.002 F 5.003 Cl 5.004 Br 5.005 I
5.006 CH.sub.3 5.007 C.sub.2H.sub.5 5.008 n-C.sub.3H.sub.7 5.009
i-C.sub.3H.sub.7 5.010 n-C.sub.4H.sub.9 5.011 i-C.sub.4H.sub.9
5.012 s-C.sub.4H.sub.9 5.013 tert.-C.sub.4H.sub.9 5.014
n-C.sub.5H.sub.11 5.015 n-C.sub.6H.sub.13 5.016 cyclopropyl 5.017
cyclobutyl 5.018 cyclopentyl 5.019 cyclohexyl 5.020 cycloheptyl
5.021 cyclooctyl 5.022 CN 5.023 CH.sub.2Cl 5.024
CH.sub.2CH.sub.2--Cl 5.025 CH(CH.sub.3)CH.sub.2--Cl 5.026
CHCl.sub.2 5.027 CCl.sub.3 5.028 CF.sub.2Cl 5.029 CF.sub.3 5.030
C.sub.2F.sub.5 5.031 CF.sub.2H 5.032 CH.dbd.CH.sub.2 5.033
CH.sub.2--CH.dbd.CH.sub.2 5.034 CH.sub.2--CH.dbd.CH--CH.sub.3 5.035
C.ident.CH 5.036 CH.sub.2--C.ident.CH 5.037
CH(CH.sub.3)--C.ident.CH 5.038 phenyl 5.039 2-F-phenyl 5.040
3-F-phenyl 5.041 4-F-phenyl 5.042 2-Cl-phenyl 5.043 3-Cl-phenyl
5.044 4-Cl-phenyl 5.045 2-CH.sub.3-phenyl 5.046 3-CH.sub.3-phenyl
5.047 4-CH.sub.3-phenyl 5.048 2-CF.sub.3-phenyl 5.049
3-CF.sub.3-phenyl 5.050 4-CF.sub.3-phenyl 5.051 2-OCH.sub.3-phenyl
5.052 3-OCH.sub.3-phenyl 5.053 4-COOCH.sub.3-phenyl 5.054
4-COOC.sub.2H.sub.5-phenyl 5.055 4-SCF.sub.3-phenyl 5.056
4-NO.sub.2-phenyl 5.057 4-CN-phenyl 5.058 2,4-Cl.sub.2-phenyl 5.059
2,6-Cl.sub.2-phenyl 5.060 2,4-(CH.sub.3).sub.2-phenyl 5.061 CHO
5.062 CO--CH.sub.3 5.063 CO--C.sub.2H.sub.5 5.064
CO-n-C.sub.3H.sub.7 5.065 CO-i-C.sub.3H.sub.7 5.066
CO-n-C.sub.4H.sub.9 5.067 CO-i-C.sub.4H.sub.9 5.068
CO-s-C.sub.4H.sub.9 5.069 CO-tert.-C.sub.4H.sub.9 5.070
CO--C.sub.5H.sub.11 5.071 CO--C.sub.6H.sub.13 5.073 CO--CF.sub.3
5.074 CO--CCl.sub.3 5.075 COO--CH.sub.3 5.076 COO--C.sub.2H.sub.5
5.077 COO-n-C.sub.3H.sub.7 5.078 COO-i-C.sub.3H.sub.7 5.079
COO-n-C.sub.4H.sub.9 5.080 COO-i-C.sub.4H.sub.9 5.081
COO-s-C.sub.4H.sub.9 5.082 COO-tert.-C.sub.4H.sub.9 5.083
CH.sub.2--OCH.sub.3 5.084 CH.sub.2--OC.sub.2H.sub.5 5.085
CH.sub.2CH.sub.2--OCH.sub.3 5.086 CH.sub.2CH.sub.2--OC.sub.2H.sub.5
5.087 CH(CH.sub.3)--OCH.sub.3 5.088 CH.sub.2OH 5.089
CH.sub.2CH.sub.2--OH 5.090 CH.sub.2CN 5.091 CH.sub.2CH.sub.2--CN
5.092 CH.sub.2--SCH.sub.3 5.093 CH.sub.2CH.sub.2--SCH.sub.3 5.094
CH.sub.2CH.sub.2--SC.sub.2H.sub.- 5 5.095
CH.sub.2CH.sub.2--S-i-C.sub.3H.sub.7 5.096
CH.sub.2--SC.sub.2H.sub.5 5.097 NO.sub.2 5.098 NH.sub.2 5.099
NH(CH.sub.3) 5.100 N(CH.sub.3).sub.2 5.101 NH(C.sub.2H.sub.5) 5.102
N(C.sub.2H.sub.5) 5.103 N(CH.sub.3)(C.sub.2H.sub.5) 5.104
CH.dbd.CH--CO.sub.2CH.sub.3 5.105
CH.dbd.CH--CO.sub.2CH.sub.2CH.sub.3
[0055]
6TABLE 6 No. R.sup.4 + R.sup.5 45.01 --(CH.sub.2).sub.3-- 45.02
--(CH.sub.2).sub.4-- 45.03 --CH(CH.sub.3)--(CH.sub.2).sub.3-- 45.04
--CH.sub.2--CH(CH.sub.3)-- -(CH.sub.2).sub.2 45.05
--(CH.sub.2).sub.2--CH(CH.sub.3)--CH.sub.2-- - 45.06
--(CH.sub.2).sub.3--CH(CH.sub.3)-- 45.07 --CH.sub.2--O--CH.sub.2--
45.08 --(CH.sub.2).sub.2--O-- 45.09
--CH.sub.2--O--(CH.sub.2).sub.2-- 45.10
--(CH.sub.2).sub.2--O--CH.sub.2-- 45.11 --S--(CH.sub.2).sub.2--
45.12 --CH.sub.2--S--CH.sub.2-- 45.13 --(CH.sub.2).sub.2--S-- 45.14
--S--(CH.sub.2).sub.3-- 45.15 --CH.sub.2--S--(CH.sub.- 2).sub.2--
45.16 --(CH.sub.2).sub.2--S--CH.sub.2-- 45.17
--(CH.sub.2).sub.3--S-- 45.18 --O--CH.dbd.CH-- 45.19
--CH.dbd.CH--O-- 45.20 --S--CH.dbd.CH-- 45.21 --CH.dbd.CH--S--
45.22 --NH--CH.dbd.CH-- 45.23 --NCH.sub.3--CH.dbd.CH-- 45.24
--CH.dbd.CH--NH-- 45.25 --CH.dbd.CH--NCH.sub.3-- 45.26
--N.dbd.CH--CH.dbd.CH-- 45.27 --CH.dbd.N--CH.dbd.CH-- 45.28
--CH.dbd.CH--N.dbd.CH-- 45.29 --CH.dbd.CH--CH.dbd.N-- 45.30
--CH.dbd.N--O-- 45.31 --O--N.dbd.CH-- 45.32 --O--CH.dbd.N-- 45.33
--N.dbd.CH--O-- 45.34 --CH.dbd.N--S-- 45.35 --S--N.dbd.CH-- 45.36
--S--CH.dbd.N-- 45.37 --N.dbd.CH--S-- 45.38 --N.dbd.CH--NH-- 45.39
--N.dbd.CH--NCH.sub.3-- 45.40 --NH--CH.dbd.N-- 45.41
--N(CH.sub.3)--CH.dbd.N-- 45.42 --CH.dbd.CH--CH.dbd.CH-- 45.43
--NH--CH.dbd.CH--NH-- 45.44 --N.dbd.N--CH.dbd.CH-- 45.45
--S--C(CH.sub.3).dbd.N-- 45.46 --C(NO.sub.2).dbd.CH--S-- 45.47
--C(CN).dbd.CH--S-- 45.48 --C(NO.sub.2).dbd.CH--O-- 45.49
--C(CN).dbd.CH--O-- 45.50 --N(CH.sub.3)--CH.dbd.CH--N(CH.sub.3)--
45.51 --CH.dbd.CH--N.dbd.N-- 45.52 --N.dbd.N--NH-- 45.53
--N.dbd.N--N(CH.sub.3)-- 45.54 .dbd.CH--S--CH.dbd.
[0056]
7TABLE 7 No. R.sup.6 or R.sup.7 6.01 CH.sub.3 6.02 C.sub.2H.sub.5
6.03 n-C.sub.3H.sub.7 6.04 i-C.sub.3H.sub.7 6.05 n-C.sub.4H.sub.9
6.06 i-C.sub.4H.sub.9 6.07 s-C.sub.4H.sub.9 6.08
tert.-C.sub.4H.sub.9 6.09 n-C.sub.5H.sub.11 6.10 n-C.sub.6H.sub.13
6.11 CH.sub.2CH.dbd.CH.sub.2 6.12 CH(CH.sub.3)--CH.dbd.CH.sub.2
6.13 CH.sub.2C.ident.CH 6.14 CH(CH.sub.3)C.ident.CH 6.15
CH.sub.2OCH.sub.3 6.16 C.sub.2H.sub.4OCH.sub.3 6.17
C.sub.2H.sub.4OC.sub.2H.sub.5 6.18 (CH.sub.2).sub.3--Cl 6.19
CH.sub.2CH.sub.2--Cl
[0057]
8TABLE 8 No. R.sup.6 + R.sup.7 67.01 --(CH.sub.2).sub.2-- 67.02
--CH(CH.sub.3)--CH.sub.2-- 67.03 --CH(C.sub.2H.sub.5)--CH.sub.2--
67.04 --CH(CH.sub.3)--CH--(CH.sub- .3)-- 67.05
--C(CH.sub.3).sub.2--CH.sub.2-- 67.06
--CH(CH.dbd.CH.sub.2)--CH.sub.2-- 67.07 --CH(CH.sub.2Cl)--CH.sub.2-
-- 67.08 --CH(CH.sub.2Br)--CH.sub.2-- 67.09
--CH(CH.sub.2OH)--CH.sub.2-- 67.10 --CH(CH.sub.2OCH.sub.3)--CH.sub-
.2-- 67.11 --CH(CH.sub.2OC.sub.2H.sub.5)--CH.sub.2-- 67.12
--CH(CH.sub.2OCH.sub.2CH.dbd.CH.sub.2)--CH.sub.2-- 67.13
--CH(CH.sub.2OCH.sub.2C.ident.CH)--CH.sub.2-- 67.14
--CH(COOH)--CH.sub.2-- 67.15 --CH(COOCH.sub.3)--CH.sub.2-- 67.16
--CH(COOC.sub.2H.sub.5)--CH.sub.2-- 67.17
--CH(COO-n-C.sub.3H.sub.7)--CH.sub.2-- 67.18
--CH(COO-i-C.sub.3H.sub.7)--CH.sub.2-- 67.19
--CH(COO-n-C.sub.4H.sub.9)--CH.sub.2-- 67.20
--CH(COO-n-C.sub.5H.sub.11)--CH.sub.2-- 67.21
--CH(COO-n-C.sub.6H.sub.13)--CH.sub.2-- 67.22 --(CH.sub.2).sub.3--
67.23 --CH(CH.sub.3)--(CH.sub.2).sub.2-- 67.24
--CH.sub.2--CH(CH.sub.3)--CH.sub.2-- 67.25 --CH(C.sub.2H.sub.5)--(-
CH.sub.2).sub.2-- 67.26 --CH.sub.2--CH(C.sub.2H.sub.5)--CH.sub.2--
67.27 --CH(CH.sub.3)--CH.sub.2--CH(CH.sub.3)-- 67.28
--CH.sub.2--C(CH.sub.3).sub.2'CH.sub.2-- 67.29
--CH(CH.sub.2OH)--(CH.sub.2).sub.2-- 67.30 --CH.sub.2--CH(CH.sub.2-
OH)--CH.sub.2 67.31 --CH(CH.sub.2OCH.sub.3)--(CH.sub.2).sub.2--
67.32 --CH(CH.sub.2OCH.sub.2CH.dbd.CH.sub.2)--(CH.sub.2).sub.2--
67.33 --CH(CH.sub.2O--CO--CH.sub.3)--CH.sub.2-- 67.33
--CH(CH.sub.2OCH.sub.2C.ident.CH)--(CH.sub.2).sub.2-- 67.34
--CH(CH.sub.2OC(O)CH.sub.3)--(CH.sub.2).sub.2 67.35
--CH.sub.2--CH(CH.sub.2OCH.sub.3)--CH.sub.2-- 67.36
--CH.sub.2--CH(CH.sub.2OCH.sub.2CH.dbd.CH.sub.2)--CH.sub.2-- 67.37
--CH.sub.2--CH(CH.sub.2OCH.sub.2C.ident.CH)--CH.sub.2-- 67.38
--CH.sub.2--CH(CH.sub.2OC(O)CH.sub.3)--CH.sub.2-- 67.39
--CH(CH.sub.2Cl)--(CH.sub.2).sub.2 67.40 --CH.sub.2--CH(CH.sub.2Cl-
)--CH.sub.2-- 67.41 --C(CH.sub.3)--(COOCH.sub.3)--CH.sub.2-- 67.42
--C(CH.sub.3)--(COOC.sub.2H.sub.5)--CH.sub.2-- 67.43
--C(CH.sub.3)(COO-n-C.sub.3H.sub.7)--CH.sub.2-- 67.44
--C(CH.sub.3)(COO-n-C.sub.4H.sub.6)--CH.sub.2-- 67.45
--CH(CH.sub.2CN)--CH.sub.2-- 67.46 --CH(CH.sub.2CN)--(CH.sub.2).su-
b.2-- 67.47 --CH.sub.2CH(CH.sub.2CN)--CH.sub.2-- 67.48
--CH.sub.2--O--CH.sub.2-- 67.49 --CH.sub.2--NH--CH.sub.2-- 67.50
--CH.sub.2--N(CH.sub.3)--CH.sub.2 67.51 --(CH.sub.2).sub.4-- 67.52
--CH.sub.2--CH.dbd.CH--CH.sub.2-- 67.53
--CH.sub.2--O--(CH.sub.2).sub.2-- 67.54 --CO--CH.sub.2-- 67.55
--CO--(CH.sub.2).sub.2-- 67.56 --CH.sub.2--CO--CH.sub.2-- 67.57
--CO--C(CH.sub.3).sub.2-- 67.58 --CO--O--CH.sub.2-- 67.59
--CH.sub.2--S--CH.sub.2-- 67.60 --CH(CH.sub.2O--CO--CH.sub-
.2)--CH.sub.2-- 67.61 10 67.62 11 67.63 12 (a bonding valency)
[0058]
9TABLE 9 No. R.sup.8 8.01 H 8.02 CH.sub.3 8.03 C.sub.2H.sub.5 8.04
n-C.sub.3H.sub.7 8.05 i-C.sub.3H.sub.7 8.06 n-C.sub.4H.sub.9 8.07
i-C.sub.4H.sub.9 8.08 s-C.sub.4H.sub.9 8.09 tert.-C.sub.4H.sub.9
8.10 n-C.sub.5H.sub.11 8.11 n-C.sub.6H.sub.13 8.12
CH.sub.2--CH.dbd.CH.sub.2 8.13 CH.sub.2--C.ident.CH 8.14 CF.sub.3
8.15 CCl.sub.3 8.16 cyclopropyl 8.17 cyclobutyl 8.18 cyclopentyl
8.19 cyclohexyl 8.20 CN 8.21 CO--OCH.sub.3 8.22
CO--OC.sub.2H.sub.5
[0059]
10TABLE 10 No. R.sup.9 and R.sup.12 9.01 H 9.02 F 9.03 Cl 9.04 Br
9.05 I 9.06 CN 9.07 CH.sub.3 9.08 C.sub.2H.sub.5 9.09
n-C.sub.3H.sub.7 9.10 i-C.sub.3H.sub.7 9.11 n-C.sub.4H.sub.9 9.12
i-C.sub.4H.sub.9 9.13 s-C.sub.4H.sub.9 9.14 tert.-C.sub.4H.sub.9
9.15 n-C.sub.5H.sub.11 9.16 OCH.sub.3 9.17 OC.sub.2H.sub.5 9.18
CF.sub.3 9.19 CO--CH.sub.3 9.20 CO--C.sub.2H.sub.5 9.21 COOCH.sub.3
9.22 COOC.sub.2H.sub.5 9.23 COO-n-C.sub.3H.sub.7
[0060]
11TABLE 12 No. R.sup.11 11.01 H 11.02 F 11.03 Cl 11.04 Br 11.05 I
11.06 CN 11.07 CH.sub.3 11.08 C.sub.2H.sub.5 11.09 n-C.sub.3H.sub.7
11.10 i-C.sub.3H.sub.7 11.11 n-C.sub.4H.sub.9 11.12
i-C.sub.4H.sub.9 11.13 s-C.sub.4H.sub.9 11.14 tert.-C.sub.4H.sub.9
11.15 CH.sub.2--CH.dbd.CH.sub.2 11.16 CH.sub.2--C.ident.CH 11.17
phenyl 11.18 4-Cl-phenyl 11.19 N(CH.sub.3).sub.2 11.20 COOCH.sub.3
11.21 COOC.sub.2H.sub.5 11.22 COCH.sub.3 11.23 COC.sub.2H.sub.5
11.24 CH.sub.2OCH.sub.3 11.25 (CH.sub.2).sub.2OCH.sub.3
[0061]
12TABLE 13 No. R.sup.13 13.01 H 13.02 CN 13.03 CH.sub.3 13.04
C.sub.2H.sub.5 13.05 n-C.sub.3H.sub.7 13.06 i-C.sub.3H.sub.7 13.07
COOCH.sub.3 13.08 COOC.sub.2H.sub.5
[0062]
13TABLE 14 No. R.sup.14 14.01 H 14.02 CH.sub.3 14.03 C.sub.2H.sub.5
14.04 n-C.sub.3H.sub.7 14.05 i-C.sub.3H.sub.7 14.06
n-C.sub.4H.sub.9 14.07 n-C.sub.5H.sub.11 14.08 n-C.sub.6H.sub.13
14.10 CH.sub.2CH.dbd.CH.sub.2 14.11 CH(CH.sub.3)--CH.dbd.CH.sub.2
14.12 CH.sub.2--CH.dbd.CH--CH.sub.2 14.13 CH.sub.2--C.ident.CH
14.14 CH(CH.sub.3)--C.ident.CH 14.15 CH.sub.2--C.ident.C--CH.sub.3
14.16 cyclopropyl 14.17 cyclobutyl 14.18 cyclopentyl 14.19
cyclohexyl 14.20 cycloheptyl 14.22 (CH.sub.2).sub.2Cl 14.23
CH.sub.2Cl 14.25 phenyl 14.26 2-F-phenyl 14.27 3-F-phenyl 14.28
4-F-phenyl 14.29 2-Cl-phenyl 14.30 3-Cl-phenyl 14.31 4-Cl-phenyl
14.32 2-Br-phenyl 14.33 3-Br-phenyl 14.34 4-Br-phenyl 14.35
2-CH.sub.3-phenyl 14.36 3-CH.sub.3-phenyl 14.37 4-CH.sub.3-phenyl
14.38 2-CF.sub.3-phenyl 14.39 3-CF.sub.3-phenyl 14.40
4-CF.sub.3-phenyl 14.41 2-OCH.sub.3-phenyl 14.42 3-OCH.sub.3-phenyl
14.43 4-OCH.sub.3-phenyl 14.44 4-NO.sub.2-phenyl 14.45 4-CN-phenyl
14.46 2,4-Cl.sub.2-phenyl 14.47 2,4-(CH.sub.3).sub.2-phenyl 14.48
CH.sub.2--OCH.sub.3 14.49 (CH.sub.2).sub.2--OC.sub.2H.sub.5 14.50
OH 14.51 OCH.sub.3 14.52 OC.sub.2H.sub.5 14.53 O-n-C.sub.3H.sub.7
14.54 O-i-C.sub.3H.sub.7 14.55 O-n-C.sub.4H.sub.9 14.56
O-i-C.sub.4H.sub.9 14.57 O-s-C.sub.4H.sub.9 14.58
O-tert.-C.sub.4H.sub.9 14.59 O--CH.sub.2CH.dbd.CH.sub.2 14.60
O--CH(CH.sub.3)CH.dbd.CH.sub.2 14.61 O--CH.sub.2C.ident.CH 14.62
O--CH(CH.sub.3)--C.ident.CH 14.63 O--CH.sub.2--C.ident.C--CH.sub.3
14.64 O--CH.sub.2--CH.dbd.CH--CH.sub.3 14.65 O-cyclopentyl 14.66
O-cyclohexyl 14.67 O-cyclopent-3-enyl 14.68 O-cyclohex-3-enyl 14.69
O--(CH.sub.2).sub.2--Cl 14.70 O--(CH.sub.2).sub.2--Cl 14.71
O--(CH.sub.2)--F 14.72 O--CH.sub.2--CF.sub.3 14.73
O--(CH.sub.2).sub.2--Br 14.74 O--CH.sub.2--CH.dbd.CHCl 14.75
O--CH.sub.2--C(Cl).dbd.CH.sub.2 14.76
O--CH.sub.2--C(Br).dbd.CH.sub.2 14.77
O--CH.sub.2--CH.dbd.C(Cl)--CH.sub.3 14.78 O--CH.sub.2--C(Cl).dbd.C-
Cl.sub.2 14.79 O--CH.sub.2-cyclopropyl 14.80 O--CH.sub.2-cyclobutyl
14.81 O--CH.sub.2-cyclopentyl 14.82 O--CH.sub.2-cyclohexyl 14.83
O--CH.sub.2-cycloheptyl 14.84 O--CO--CH.sub.3 14.85
O--CO--C.sub.2H.sub.5 14.86 O--CH.sub.2--CN 14.87
O--(CH.sub.2).sub.3--CN 14.88 O--CH.sub.2--OCH.sub.3 14.89
O--CH.sub.2--OC.sub.2H.sub.5 14.90 O--(CH.sub.2).sub.2--OCH.sub.3
14.91 O--(CH.sub.2).sub.2--OC- .sub.2H.sub.5 14.92
O--(CH.sub.2).sub.3--OC.sub.2H.sub.5 14.93
O--(CH.sub.2).sub.2--CO--OCH.sub.3 14.94
O--(CH.sub.2).sub.2--CO--OC.sub.2H.sub.5 14.95
O--C(CH.sub.3)--CO--OCH.sub.3 14.96 O--C(CH.sub.3)--CO--OC.sub.2H.-
sub.5 14.97 O--(CH.sub.2).sub.2--OH 14.98 O--CH.sub.2--SCH.sub.3
14.99 O--(CH.sub.2).sub.2--N(CH.sub.3).sub.- 2 14.100
O--(CH.sub.2).sub.2--N(C.sub.2H.sub.5).sub.2 14.101
O--CH.sub.2-phenyl 14.102 O--(CH.sub.2).sub.2-phenyl 14.103
O--(CH.sub.2).sub.3-phenyl 14.104 O--(CH.sub.2)4-phenyl 14.105
O--(CH.sub.2).sub.4-(4-Cl-phenyl) 14.106
O--(CH.sub.2).sub.4-(4-CH.sub.3-phenyl) 14.107
O--(CH.sub.2).sub.4-(4-CH.sub.3-phenyl) 14.108
O--(CH.sub.2).sub.4-(4-F-phenyl) 14.109 O--CH.sub.2CH.dbd.CH-pheny-
l 14.110 O--CH.sub.2CH.dbd.CH-(4-F-phenyl) 14.111
O--CH.sub.2CH.dbd.CH-(4-Cl-phenyl) 14.112 O--CH.sub.2CH.dbd.CH-(3--
OCH.sub.3-phenyl) 14.113
O--(CH.sub.2).sub.2--CH.dbd.CH-(4-F-phenyl- ) 14.114
O--(CH.sub.2).sub.2--CH.dbd.CH-(4-Cl-phenyl) 14.115
O--(CH.sub.2)--CH.dbd.CH-(3,4-Cl.sub.2-phenyl) 14.116
O--CH.sub.2--CH.dbd.C(CH.sub.3)-(4-F-phenyl) 14.117
O--CH.sub.2--C.ident.C--CH.sub.2-phenyl 14.119
O--(CH.sub.2).sub.2--O-phenyl 14.120 O--(CH.sub.2).sub.2--OCH.sub.-
2-phenyl 14.121 O--(CH.sub.2).sub.2--OCH.sub.2-(4-F-phenyl) 14.122
O--CH.sub.2CH.dbd.CH--CH.sub.2--O-phenyl 14.123
O--CH.sub.2--C.ident.C--CH.sub.2--O-phenyl 14.124
O--CH.sub.2--C.ident.C--CH.sub.2--O-(4-F-phenyl) 14.125
O--(CH.sub.2).sub.2--SCH.sub.2-phenyl 14.126
O--(CH.sub.2).sub.2--SCH.sub.2-(4-Cl-phenyl) 14.127
O--(CH.sub.2).sub.2--N(CH.sub.3)--CH.sub.2-phenyl 14.128 NH.sub.2
14.129 NHCH.sub.3 14.130 NH--C.sub.2H.sub.5 14.131
NH-n-C.sub.3H.sub.7 14.132 NH-i-C.sub.3H.sub.7 14.133
NH-n-C.sub.4H.sub.9 14.134 NH-i-C.sub.4H.sub.9 14.135
NH-s-C.sub.4H.sub.9 14.136 NH-tert.-C.sub.4H.sub.9 14.137
NH-cyclopropyl 14.138 NH-cyclobutyl 14.139 NH-cyclopentyl 14.140
NH-cyclohexyl 14.141 NH-cycloheptyl 14.142 N(CH.sub.3).sub.2 14.143
N(C.sub.2H.sub.5).sub.2 14.144 NH--CH.sub.2CH.dbd.CH.sub.2 14.145
NH--CH.sub.2C.ident.CH 14.146 NH--CH.sub.2--CF.sub.3 14.147
NH--CO--CH.sub.3 14.148 NH--COC.sub.2H.sub.5 14.149
NH--CO--OCH.sub.3 14.150 NH--CO--OC.sub.2H.sub.5 14.151
NH--COO-tert.-C.sub.4H.sub.9 14.152 N-pyrrolidinyl 14.153
N-piperdinyl 14.154 N-morpholino 14.155 N-piperazinyl 14.156
NH-phenyl 14.157 NH-(4-Cl-phenyl) 14.158 NH-(4-F-phenyl) 14.159
NH-(4-OCH.sub.3-phenyl) 14.160 NH-(2,4-Cl.sub.2-phenyl) 14.161
CH.sub.2--OCH.sub.3 14.162 (CH.sub.2).sub.2--OCH.sub.3
[0063]
14TABLE 15 No. R.sup.3' 3'.01 CH.sub.3 3'.02 C.sub.2H.sub.5 3'.03
n-C.sub.3H.sub.7 3'.04 i-C.sub.3H.sub.7 3'.05 n-C.sub.4H.sub.9
3'.06 i-C.sub.4H.sub.9 3'.07 s-C.sub.4H.sub.9 3'.08
tert.-C.sub.4H.sub.9 3'.09 n-C.sub.5H.sub.11 3'.10
i-C.sub.5H.sub.11 3'.11 n-C.sub.6H.sub.13 3'.12 i-C.sub.6H.sub.13
3'.13 CH.sub.2CH.dbd.CH.sub.2 3'.14 --CH(CH.sub.3)--CH.dbd.CH.sub.2
3'.15 --CH.sub.2--C.dbd.CH--CH.sub- .3 3'.16
--CH(CH.sub.3)--C.ident.CH 3'.17
--CH.sub.2--C.ident.C--CH.sub.3
[0064] The following 3-phenyluracils I-1 to I-24 are particularly
preferred: 13
[0065] where W in each of the abovementioned formulae I-1 to I-24
has one of the following meanings: --CHO, --COCH.sub.3,
--COC.sub.2H.sub.5, --CO-n-C.sub.3H.sub.7, --CO-i-C.sub.3H.sub.7,
--CO-n-C.sub.4H.sub.9, --CO-i-C.sub.4H.sub.9,
--CO-s-C.sub.4H.sub.9, --CO-tert.-C.sub.4H.sub.9,
--CO--CH.sub.2CH.dbd.CH.sub.2, --CO--CF.sub.3, --COCCl.sub.3,
--COCH.sub.2C.ident.CH, --CO-cyclopropyl, --CO-cyclobutyl,
--CO-cyclo-pentyl, --CO-cyclohexyl, --CO--CN, --CO--COOCH.sub.3,
--CO--COOC.sub.2H.sub.5, --CH.dbd.NH, --CH.dbd.NCH.sub.3,
--CH.dbd.NC.sub.2H.sub.5, --CH.dbd.N-n-C.sub.3H.sub.5,
--CH.dbd.N-i-C.sub.3H.sub.5, --CH.dbd.N-n-C.sub.4H.sub.9,
--CH.dbd.NCH .sub.2CH.dbd.CH.sub.2,
--CH.dbd.NCH.sub.2CH.dbd.CH.sub.2--CH.sub.3,
--CH.dbd.NCH.sub.2C.ident.CH,
--CH.dbd.NCH.sub.2C.ident.C--CH.sub.3, --CH.dbd.N-cyclopropyl,
--CH.dbd.N-cyclobutyl, --CH.dbd.N-cyclopentyl,
--CH.dbd.N-cyclohexyl, --CH.dbd.N-cycloheptyl,
--CH.dbd.N--CH.sub.2--CH.s- ub.2Cl, --CH.dbd.N--CH.sub.2Cl,
--CH.dbd.N--C.sub.6H.sub.5, --CH.dbd.N-4-Br--C.sub.6H.sub.4,
--CH.dbd.N-3-F--C.sub.6H.sub.4, --CH.dbd.N-4-F--C.sub.6H.sub.4,
--CH.dbd.N-2-Cl--C.sub.6H.sub.4, --CH.dbd.N-3-Cl--C.sub.6H.sub.4,
--CH.dbd.N-4-Cl--C.sub.6H.sub.4, --CH.dbd.N-2-Br--C.sub.6H.sub.4,
--CH.dbd.N-2-F--C.sub.6H.sub.4,
--CH.dbd.N-2-CH.sub.3-C.sub.6H.sub.4,
--CH.dbd.N-3-CH.sub.3-C.sub.6H.sub.- 4,
--CH.dbd.N-4-CH.sub.3-C.sub.6H.sub.4,
--CH.dbd.N-2-CF.sub.3-C.sub.6H.su- b.4,
--CH--N-3-CF.sub.3-C.sub.6H.sub.4,
--CH.dbd.N-4--CF.sub.3-C.sub.6H.su- b.4,
--CH.dbd.N-2-OCH.sub.3--C.sub.6H.sub.4,
--CH.dbd.N-3-OCH.sub.3--C.sub- .6H.sub.4,
--CH.dbd.N-4--OCH.sub.3--C.sub.6H.sub.4,
--CH.dbd.N-4-NO.sub.2--C.sub.6H.sub.4,
--CH.dbd.N-4-CN--C.sub.6H.sub.4,
--CH.dbd.N-2,4--(Cl,Cl)--C.sub.6H.sub.4,
--CH.dbd.N-2,4-(CH.sub.3,CH.sub.- 3)--C.sub.6H.sub.4,
--CH.dbd.N--CH.sub.2OCH.sub.3, --CH.dbd.N--CH.sub.2OC.-
sub.2H.sub.5, --CH.dbd.N--CH.sub.2CH.sub.2OCH.sub.3,
--CH.dbd.N--CH.sub.2CH.sub.2OC.sub.2H.sub.5, --CH.dbd.N--OH,
--CH.dbd.N--OCH.sub.3, --CH.dbd.N--OC.sub.2H.sub.5,
--CH.dbd.N--O-n-C.sub.3H.sub.7, --CH.dbd.N--O-i-C.sub.3H.sub.7,
--CH.dbd.N--O-n-C.sub.4H.sub.9, --CH.dbd.N--O-i-C.sub.4H.sub.9,
--CH.dbd.N--O--S--C.sub.4H.sub.9,
--CH.dbd.N--O-tert.-C.sub.4H.sub.9,
--CH.dbd.N--O--CH.sub.2CH.dbd.CH.sub.2, --CH--N--O--CH(CH.sub.3)
CH.dbd.CH.sub.2, --CH.dbd.N--O--CH.sub.2C.ident.CH,
--CH.dbd.N--O--CH(CH.sub.3)--C.ident.CH,
--CH.dbd.N--O--CH.sub.2--CH.dbd.- CH--CH.sub.3,
--CH.dbd.N--O--CH.sub.2--CH.sub.2--Cl,
--CH.dbd.N--O--CH.sub.2--CH.sub.2--F,
--CH.dbd.N--O--CH.sub.2--CF.sub.3,
--CH.dbd.N--O--CH.sub.2--CH.dbd.CHCl,
--CH.dbd.N--O--CH.sub.2--CCl.dbd.CH- .sub.2,
--CH.dbd.N--O--CH.sub.2--CBr.dbd.CH.sub.2, --CH.dbd.N--O--CH.sub.2-
--CH.dbd.CCl--CH.sub.3, --CH.dbd.N--OC(O) CH.sub.3,
--CH.dbd.N--OC(O)C.sub.2H.sub.5, --CH.dbd.N--O--CH.sub.2--CN,
--CH.dbd.N--O--CH.sub.2--CH.dbd.CH--CH.sub.2--O--CH.sub.3,
--CH.dbd.N--O--,CH.sub.2--CH.dbd.CH--CH.sub.2--O-tert.-C.sub.4H.sub.9,
--CH.dbd.N--O--(CH.sub.2).sub.3--C.sub.6H.sub.5,
--CH.dbd.N--O--(CH.sub.2- ).sub.4-,C.sub.6H.sub.5,
--CH.dbd.N--O--(CH.sub.2).sub.4-4-Cl--C.sub.6H.su- b.4,
--CH.dbd.N--O--(CH.sub.2).sub.4-4--OCH.sub.3--C.sub.6H.sub.4,
--CH.dbd.N--O--(CH.sub.2).sub.4-4-CH.sub.3-C.sub.6H.sub.4,
--CH.dbd.N--O--(CH.sub.2).sub.4-4-F--C.sub.6H.sub.4--CH.dbd.N--O--CH.sub.-
2CH.sub.2CH--C.sub.6H.sub.5,
--CH.dbd.N--O--CH.sub.2CH.dbd.CH-4-F-C.sub.6H- .sub.4,
--CH.dbd.N--O--CH.sub.2CH.dbd.CH-4-Cl--C.sub.6H.sub.4,
--CH.dbd.N--O--CH.sub.2CH--CH-.sub.3--OCH.sub.3-C.sub.6H.sub.4,
--CH.dbd.N--O--(CH.sub.2).sub.2CH.dbd.CH-4-F-C.sub.6H.sub.4,
--CH.dbd.N--O--(CH.sub.2)CH.dbd.CH-4-Cl--C.sub.5H.sub.4,
--CH.dbd.N--O--CH.sub.2CH.dbd.CHCH.sub.2-4--OCH.sub.3-C.sub.6H.sub.4,
--CH.dbd.N--O--CH.sub.2--CH.dbd.C(CH.sub.3)--C.sub.6H.sub.5
--CH.dbd.N--O--(CH.sub.2).sub.2CH.dbd.CH-3,4(Cl,Cl)-C.sub.6H.sub.3,
--CH.dbd.N--O--(CH.sub.2).sub.3C.ident.C-4-F--C.sub.6H.sub.4,
--CH.sub.2.dbd.N--OCHOCH.sub.3,
--CH.dbd.N--OC.sub.2H.sub.4OCH.sub.3,
--CH.dbd.N--OCH.sub.2OC.sub.2H.sub.5,
--CH.dbd.N--OCH(CH.sub.3)OCH.sub.3,
--CH.dbd.N--OCH(CH.sub.3)COOCH.sub.3,
--CH.dbd.N--OCH(CH.sub.3)COO-n-C.su- b.4H.sub.9,
--CH.dbd.N--NH.sub.2, --CH.dbd.N--NHCH.sub.3,
--CH.dbd.N--NHC.sub.2H.sub.5, --CH.dbd.N--NH-n-C.sub.3H.sub.7,
--CH.dbd.N--NH-i-C.sub.3H.sub.7, --CH.dbd.N--NH-n-C.sub.4H.sub.9,
--CH.dbd.N--NH-i-C.sub.4H.sub.9, --CH.dbd.N--NH-s-C.sub.4H.sub.9,
--CH--N--NH-tert.-C.sub.4H.sub.9, --CH.dbd.N--NH-cyclopropyl,
--CH.dbd.N--NH-cyclobutyl, --CH.dbd.N--NH-cyclopentyl,
--CH.dbd.N--NH-cyclohexyl, --CH.dbd.N--NH-cycloheptyl,
--CH.dbd.N--N(CH.sub.3).sub.2, --CH.dbd.N--N(C.sub.2H.sub.9).sub.2,
--CH.dbd.N--N(C.sub.3H.sub.7).sub.2,
--CH.dbd.N--N(i-C.sub.3H.sub.7)(CH.s- ub.3),
--CH.dbd.N--NHCH.sub.2--C.dbd.CH,
--CH.dbd.N--NHCH.sub.2--C.ident.C- H,
--CH.dbd.N--N(CH.sub.3)--CH.sub.2--C.ident.CH,
--CH.dbd.N--NHCH.sub.2CF- .sub.3, --CH.dbd.N--NH--CO--CH.sub.3,
--CH.dbd.N--NH--CO--CH.sub.2H.sub.5, --CH.dbd.N--NH--COOCH.sub.3,
--CH.dbd.N--NH--COOC.sub.2H.sub.5,
--CH.dbd.N--NH--COO-tert.-C.sub.4H.sub.9,
--CH.dbd.N-pyrrolidin-1-yl, --CH.dbd.N-piperidin-1-yl,
--CH.dbd.N-morpholin-4-yl, --CH.dbd.N--NH--C.sub.6H.sub.5,
--CH.dbd.N--NH--(4-Cl--C.sub.6H.sub.4),
--CH.dbd.N--NH--(4-NO.sub.2--C.sub.6H.sub.4),
--CH.dbd.N--NH--(4-F--C.sub- .6H.sub.4),
--CH.dbd.N--NH--(4-CH.sub.3O--C.sub.6H.sub.4),
--CH.dbd.N--NH--(2,4-Cl.sub.2-C.sub.6H.sub.3),
--CH.dbd.N--NH--(.sub.2,4-- (NO.sub.2).sub.2--C.sub.6H.sub.3),
--CH.dbd.N--NH--CO--NH.sub.2, --CH.dbd.N--NH--CO--NHCH.sub.3,
--CH.dbd.N--NH--CO--NHC.sub.2H.sub.5,
--CH.dbd.N--NH--CO--N(CH.sub.3).sub.2, --CH.dbd.CH--COOH,
--CH.dbd.CH--CO--OCH.sub.3, --CH.dbd.CH--CO--OC.sub.2H.sub.5,
--CH.dbd.CH--CO--O-n-C.sub.3H .sub.7,
--CH.dbd.CH--CO--O-i-C.sub.3H.sub.7- ,
--CH.dbd.CH--CO--O-n-C.sub.4H.sub.9,
--CH.dbd.CH--CO--O-tert.-C.sub.4H.s- ub.9,
--CH.dbd.CH--CO--O-cyclopropyl, --CH.dbd.CH--CO--O-cyclobutyl,
--CH.dbd.CH--CO--O-cyclopentyl, --CH.dbd.CH--CO--O-cyclohexyl,
--CH.dbd.CH--CO--O-cycloheptyl, --CH.dbd.C(CH.sub.3)--COOH,
--CH.dbd.C(CH.sub.3)--CO--OCH.sub.3,
--CH.dbd.C(CH.sub.3)--CO--OC.sub.2H.- sub.5,
--CH.dbd.C(CH.sub.3)--CO--O-n-C.sub.3H,
--CH.dbd.C(CH.sub.3)--CO--O- -i-C.sub.3H.sub.7,
--CH.dbd.C(CH.sub.3)--CO--O-n-C.sub.4H.sub.9,
--CH.dbd.C(CH.sub.3)--CO--O-tert.-C.sub.4H.sub.9,
--CH.dbd.C(CH.sub.3)--C- O--O-cyclopropyl,
--CH.dbd.C(CH.sub.3)--CO--O-cyclobutyl,
--CH.dbd.C(CH.sub.3)--CO--O-cyclopentyl,
--CH.dbd.C(CH.sub.3)--CO--O-cycl- ohexyl,
--CH.dbd.C(CH.sub.3)--CO-.sub.0-cycloheptyl,
--CH.dbd.C(C.sub.2H.sub.5)--COOH,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub- .3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O-n-C.sub.3H.sub.7,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O-i-C.sub.3H.sub.7,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O-n-C.H.sub.9,
--CH.dbd.C(C.sub.2H.sub.5)- --CO--O-tert--C.sub.4H.sub.9,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O-cyclopropy- l,
-CH.dbd.C(C.sub.2H.sub.5)--CO--O-cyclobutyl,
--CH.dbd.C(C.sub.2H.sub.5)- --CO--O-cyclopentyl,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O-cyclohexyl,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O-cycloheptyl,
--CH.dbd.C(Cl)--COOH, --CH.dbd.C(Cl)--CO--OCH.sub.3,
--CH.dbd.C(Cl)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(Cl)--CO--O-n-C.sub.3H.sub.7,
--CH.dbd.C(Cl)--CO--O-i-C.sub.3H.- sub.7,
--CH.dbd.C(Cl)--CO--O-n-C.sub.4H.sub.9,
--CH.dbd.C(Cl)--CO--O-tert.- -C.sub.4H.sub.9,
--CH.dbd.C(Cl)--CO--O-cyclopropyl,
--CH.dbd.C(Cl)--CO--O-cyclobutyl,
--CH.dbd.C(Cl)--CO--O-cyclopentyl,
--CH.dbd.C(Cl)--CO--O-cyclohexyl,
--CH.dbd.C(Cl)--CO--O-cycloheptyl, --CH.dbd.C(Br)--COOH,
--CH.dbd.C(Br)--CO--OCH.sub.3, --CH.dbd.C(Br)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(Br)--CO--O-n-C.sub.3H.sub- .7,
--CH.dbd.C(Br)--CO--O-i-C.sub.3H.sub.7,
--CH.dbd.C(Br)--CO--O-n-C.sub.- 4H.sub.9,
--CH.dbd.C(Br)--CO--O-tert.-C.sub.4H.sub.9,
--CH.dbd.C(Br)--CO--O-cyclopropyl,
--CH.dbd.C(Br)--CO--O-cyclobutyl,
--CH.dbd.C(Br)--CO--O-cyclopentyl,
--CH.dbd.C(Br)--CO--O-cyclohexyl,
--CH.dbd.C(Br)--CO--O-cycloheptyl, --CH.dbd.C(CN)--COOH,
--CH.dbd.C(CN)--CO--OCH.sub.3, --CH.dbd.C(CN)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(CN)--CO--O-n-C.sub.3H.sub.7,
--CH.dbd.C(CN)--CO--O-i-C.sub.3H.- sub.7,
--CH.dbd.C(CN)--CO--O-n-C.sub.4H.sub.9,
--CH.dbd.C(CN)--CO--O-tert.- -C.sub.4H.sub.9,
--CH.dbd.C(CN)--CO--O-cyclopropyl,
--CH.dbd.C(CN)--CO--O-cyclobutyl,
--CH.dbd.C(CN)--CO--O-cyclopentyl,
--CH.dbd.C(CN)--CO--O-cyclohexyl,
--CH.dbd.C(CN)--CO--O-cycloheptyl,
--CH.dbd.CH--CO--OCH.sub.2--OCH.sub.3,
--CH.dbd.CH--CO--OCH.sub.2--OC.sub- .2H.sub.5,
--CH.dbd.CH--CO--OCH.sub.2--O-n-C.sub.3H.sub.5,
--CH.dbd.CH--CO--OCH.sub.2--O-i-C.sub.3H.sub.5,
--CH.dbd.CH--CO--OCH(CH.s- ub.3)--OCH.sub.3,
--CH.dbd.CH--CO--OCH(CH.sub.3)--OC.sub.2H.sub.5,
--CH.dbd.CH--CO--O--CH.sub.2CH.sub.2--OCH.sub.3,
--CH.dbd.CH--CO--O--CH.s- ub.2CH.sub.2--OC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CO--OCH.sub.2--OCH.su- b.3,
--CH.dbd.C(CH.sub.3)--CO--OCH.sub.2--OC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CO--OCH.sub.2--O-n-C.sub.3H.sub.5,
--CH.dbd.C(CH.sub.3)--CO--OCH.sub.2--O-i-C.sub.3H.sub.5,
--CH.dbd.C(CH.sub.3)--CO--OCH(CH.sub.3)--OCH.sub.3,
--CH.dbd.C(CH.sub.3)--CO--OCH(CH.sub.3)--OC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CO--O--CH.sub.2CH.sub.2--OCH.sub.3,
--CH.dbd.C (CH.sub.3) --CO--O--CH.sub.2CH.sub.2--OC.sub.2H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--OCH.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--OC.sub.2H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--O-n-C.sub.3H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--O-i-C.sub.3H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH(CH.sub.3)--OCH.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH(CH.sub.3)--OC.sub.2H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O--CH.sub.2CH.sub.2--OCH.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O--CH.sub.2CH.sub.2--OC.sub.2H.sub.5,
--CH.dbd.C(Cl)--CO--OCH.sub.2--OCH.sub.3,
--CH.dbd.C(Cl)--CO--OCH.sub.2--- OC.sub.2H.sub.5,
--CH.dbd.C(Cl)--CO--OCH.sub.2--O-n-C.sub.3H.sub.5,
--CH.dbd.C(Cl)--CO--OCH.sub.2-O-i-C.sub.3H.sub.5,
--CH.dbd.C(Cl)--CO--OCH- (CH.sub.3)--OCH.sub.3,
--CH.dbd.C(Cl)--CO--OCH(CH.sub.3)--OC.sub.2H.sub.5,
--CH.dbd.C(Cl)--CO--O--CH.sub.2CH.sub.2--OCH.sub.3,
--CH.dbd.C(Cl)--CO--O--CH.sub.2CH.sub.2--OC.sub.2H.sub.5,
--CH.dbd.C(Br)--CO--OCH .sub.2--OCH.sub.3,
--CH.dbd.C(Br)--CO--OCH.sub.2-- -OC.sub.2H.sub.5,
--CH.dbd.C(Br)--CO--OCH.sub.2-O-n-C.sub.3H.sub.5,
--CH.dbd.C(Br)--CO--OCH.sub.2-.degree.-i-C.sub.3H.sub.5,
--CH.dbd.C(Br)--CO--OCH(CH.sub.3)--OCH.sub.3,
--CH.dbd.C(Br)--CO--OCH(CH.- sub.3)--OC.sub.2H.sub.5,
--CH.dbd.C(Br)--CO--O--CH.sub.2CH.sub.2--OCH.sub.- 3, --CH.dbd.C
(Br)--CO--O--CH.sub.2CH.sub.2--OC.sub.2H.sub.5, --CH.dbd.C(CN)
--CO--OCH.sub.2--OCH .sub.3, --CH.dbd.C(CN)--CO--OCH.sub.2-
--OC.sub.2H.sub.5,
--CH.dbd.C(CN)--CO--OCH.sub.2--O-n-C.sub.3H.sub.5,
--CH.dbd.C(CN)--CO--OCH.sub.2-O-i-C.sub.3H.sub.5,
--CH.dbd.C(CN)--CO--OCH- (CH.sub.3)--OCH.sub.3,
--CH.dbd.C(CN)--CO--OCH(CH.sub.3)--OC.sub.2H.sub.5,
--CH.dbd.C(CN)--CO--O--CH .sub.2CH.sub.2--OCH .sub.3,
--CH.dbd.C(CN)--CO--O--CH.sub.2CH.sub.2--OC.sub.2H.sub.5,
--CH.dbd.CH--CO--OCH.sub.2--CF.sub.3,
--CH.dbd.CH--CO--OCH.sub.2--CCl.sub- .3,
--CH.dbd.CH--CO--OCH.sub.2-oxiranyl,
--CH.dbd.CH--CO--O(CH.sub.2).sub.- 3-Br,
--CH.dbd.CH--CO--OCH.sub.2--CH.dbd.CH.sub.2,
--CH.dbd.CH--CO--OCH.su- b.2--C.ident.CH,
--CH.dbd.CH--CO--OCH.sub.2--CN, --CH.dbd.CH--CO--O(CH.sub-
.2).sub.2--CN, --CH.dbd.C(CH.sub.3)--CO--OCH .sub.2--CF.sub.3,
--CH.dbd.C(CH.sub.3)--CO--OCH.sub.2-CCl.sub.3,
--CH.dbd.C(CH.sub.3)--CO--- OCH.sub.2-oxiranyl,
--CH.dbd.C(CH.sub.3)--CO--O(CH.sub.2).sub.3-Br,
--CH.dbd.C(CH.sub.3)--CO--OCH.sub.2--CH.dbd.CH.sub.2,
--CH.dbd.C(CH.sub.3)--CO--OCH.sub.2--C.ident.CH,
--CH.dbd.C(CH.sub.3)--CO- --OCH.sub.2--CN,
--CH.dbd.C(CH.sub.3)--CO--O(CH .sub.2).sub.2--CN,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--CF.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2-CCl.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2-oxiranyl,
--CH.dbd.C(C.sub.2H.sub.5)--CO--O(CH .sub.2).sub.3-Br,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--CH.dbd.CH .sub.2,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2-C.ident.CH,
--CH.dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--CN,
--CH.dbd.C(C.sub.2H.sub.5)- --CO--O(CH.sub.2).sub.2--CN,
--CH.dbd.C(Cl)--CO--OCH.sub.2--CF.sub.3,
--CH.dbd.C(Cl)--CO--OCH.sub.2--CCl.sub.3,
--CH.dbd.C(Cl)--CO--OCH.sub.2-o- xiranyl,
--CH.dbd.C(Cl)--CO--O(CH.sub.2).sub.3-Br, --CH.dbd.C(Cl)--CO--OCH-
.sub.2--CH.dbd.CH.sub.2, --CH.dbd.C(Cl)--CO--OCH.sub.2--C.ident.CH,
--CH.dbd.C(Cl)--CO--OCH.sub.2--CN,
--CH.dbd.C(Cl)--CO--O(CH.sub.2).sub.2-- -CN,
--CH.dbd.C(Br)--CO--OCH.sub.2--CF.sub.3,
--CH.dbd.C(Br)--CO--OCH.sub.- 2-CC.sub.13,
--CH.dbd.C(Br)--CO--OCH.sub.2-oxiranyl,
--CH.dbd.C(Br)--CO--O(CH.sub.2) .sub.3-Br,
--CH.dbd.C(Br)--CO--OCH.sub.2-- -CH.dbd.CH.sub.2,
--CH.dbd.C(Br)--CO--OCH.sub.2-C.ident.CH,
--CH.dbd.C(Br)--CO--OCH.sub.2--CN,
--CH.dbd.C(Br)--CO--O(CH.sub.2).sub.2-- -CN,
--CH.dbd.C(CN)--CO--OCH.sub.2--CF.sub.3,
--CH.dbd.C(CN)--CO--OCH.sub.- 2--CCl.sub.3,
--CH.dbd.C(CN)--CO--OCH.sub.2-oxiranyl,
--CH.dbd.C(CN)--CO--O(CH.sub.2).sub.3-Br,
--CH.dbd.C(CN)--CO--OCH.sub.2--- CH.dbd.CH.sub.2,
--CH.dbd.C(CN)--CO--OCH.sub.2-C.ident.CH,
--CH.dbd.C(CN)--CO--OCH.sub.2--CN,
--CH.dbd.C(CN)--CO--O(CH.sub.2).sub.2-- -CN,
--CH.dbd.CH--CO--CH.sub.3, --CH.dbd.CH--CO--C.sub.2H.sub.5,
--CH.dbd.CH--CO-n-C.sub.3H.sub.7, --CH.dbd.CH--CO-i-C.sub.3H.sub.7,
--CH.dbd.CH--CO-n-C.sub.4H.sub.9,
--CH.dbd.CH--CO-tert.-C.sub.4H.sub.9, --CH.dbd.CH--CO--CH.sub.2Cl,
--CH.dbd.CH--CO--CH.sub.2Br, --CH.dbd.CH--CO--CHCl.sub.2,
--CH.dbd.CH--CO--CH.sub.2--OCH.sub.3,
--CH.dbd.CH--CO--CH(OCH.sub.3) .sub.2,
--CH.dbd.CH--CO--CH.sub.2--SCH.sub- .3,
--CH.dbd.C(CH.sub.3)--CO--CH.sub.3,
--CH.dbd.C(CH.sub.3)--CO--C.sub.2H- .sub.5,
--CH.dbd.C(CH.sub.3)--CO-n-C.sub.3H.sub.7, --CH.dbd.C(CH.sub.3)--C-
O-i-C.sub.3H.sub.7, --CH.dbd.C(CH.sub.3)--CO-n-C.sub.4H.sub.9,
--CH.dbd.C(CH.sub.3)--CO-tert.-C.sub.4H.sub.9,
--CH.dbd.C(CH.sub.3)--CO--- CH.sub.2Cl,
--CH.dbd.C(CH.sub.3)--CO--CH.sub.2Br, --CH.dbd.C(CH .sub.3)
--CO--CHCl.sub.2, --CH.dbd.C(CH.sub.3)--CO--CH .sub.2--OCH .sub.3,
--CH.dbd.C(CH.sub.3)--CO--CH(OCH.sub.3) .sub.2,
--CH.dbd.C(CH.sub.3)--CO-- -CH.sub.2--SCH.sub.3,
CH.dbd.C(C.sub.2H.sub.5)--CO--CH.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--C.sub.2H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5- )--CO-n-C.sub.3H.sub.7,
--CH.dbd.C(C.sub.2H.sub.5)--CO-i-C.sub.3H.sub.7,
--CH.dbd.C(C.sub.2H.sub.5)--CO-n-C.sub.4H.sub.9,
--CH.dbd.C(C.sub.2H.sub.- 5)--CO-tert.-C.sub.4H.sub.9,
--CH.dbd.C(C.sub.2H.sub.5)--CO--CH.sub.2Cl,
--CH.dbd.C(C.sub.2H.sub.9)--CO--CH.sub.2Br,
--CH.dbd.C(C.sub.2H.sub.5)--C- O--CHCl.sub.2,
--CH.dbd.C(C.sub.2H.sub.5)--CO--CH.sub.2--OCH.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--CH(OCH.sub.3).sub.2,
--CH.dbd.C(C.sub.2H.sub.5)--CO--CH.sub.2--SCH.sub.3,
--CH.dbd.C(Cl)--CO--CH.sub.3, --CH.dbd.C(Cl)--CO--C.sub.2H.sub.5,
--CH.dbd.C(Cl)--CO-n-C.sub.3H.sub.7,
--CH.dbd.C(Cl)--CO-i-C.sub.3H.sub.7,
--CH.dbd.C(Cl)--CO-n-C.sub.4H.sub.9,
--CH.dbd.C(Cl)--CO-tert.-C.sub.4H.su- b.9,
--CH.dbd.C(Cl)--CO--CH.sub.2Cl, --CH.dbd.C(Cl)--CO--CH.sub.2Br,
--CH.dbd.C(Cl)--CO--CHCl.sub.2,
--CH.dbd.C(Cl)--CO--CH.sub.2--OCH.sub.3,
--CH.dbd.C(Cl)--CO--CH(OCH.sub.3).sub.2,
--CH.dbd.C(Cl)--CO--CH.sub.2--SC- H.sub.3,
--CH.dbd.C(Br)--CO--CH.sub.3, --CH.dbd.C(Br)--CO--C.sub.2H.sub.5,
--CH.dbd.C(Br)--CO-n-C.sub.3H.sub.7,
--CH.dbd.C(Br)--CO-i-C.sub.3H.sub.7,
--CH.dbd.C(Br)--CO-n-C.sub.4H.sub.9,
--CH.dbd.C(Br)--CO-tert.-C.sub.4H.su- b.9,
--CH.dbd.C(Br)--CO--CH.sub.2Cl, --CH.dbd.C(Br)--CO--CH.sub.2Br,
--CH.dbd.C(Br)--CO--CHCl.sub.2,
--CH.dbd.C(Br)--CO--CH.sub.2--OCH.sub.3,
--CH.dbd.C(Br)--CO--CH(OCH.sub.3).sub.2,
--CH.dbd.C(Br)--CO--CH.sub.2--SC- H.sub.3,
--CH.dbd.C(CN)--CO--CH.sub.3, --CH.dbd.C(CN)--CO--C.sub.2H.sub.5,
--CH.dbd.C(CN)--CO-n-C.sub.3H.sub.7,
--CH.dbd.C(CN)--CO-i-C.sub.3H.sub.7,
--CH.dbd.C(CN)--CO-n-C.sub.4H.sub.9,
--CH.dbd.C(CN)--CO-tert.-C.sub.4H.su- b.9,
--CH.dbd.C(CN)--CO--CH.sub.2Cl, --CH.dbd.C(CN)--CO--CH.sub.2Br,
--CH.dbd.C(CN)--CO--CHCl.sub.2,
--CH.dbd.C(CN)--CO--CH.sub.2--OCH.sub.3,
--CH.dbd.C(CN)--CO--CH(OCH.sub.3).sub.2,
--CH.dbd.C(CN)--CO--CH.sub.2--SC- H.sub.3,
--CH.dbd.CH--CO--C.sub.6H.sub.5, --CH.dbd.CH--CO-(4-Cl--C.sub.6H.-
sub.4), --CH.dbd.C(CH.sub.3)--CO--C.sub.6H.sub.5,
--CH.dbd.C(CH.sub.3)--CO- -(4-Cl-C.sub.6H.sub.4),
--CH--C(C.sub.2H.sub.5)--CO--C.sub.6H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO-(4-Cl--C.sub.6H.sub.4),
--CH.dbd.C(Cl)--CO--C.sub.6H.sub.5,
--CH.dbd.C(Br)--CO--C.sub.5H.sub.5,
--CH.dbd.C(CN)--CO--C.sub.6H.sub.5--CH.dbd.CH--CO--NH.sub.2,
--CH.dbd.CH--CO--NHCH.sub.3, --CH.dbd.CH--CO--N(CH.sub.3).sub.2,
--CH.dbd.CH--CO--NH--C.sub.2H.sub.5,
--CH.dbd.CH--CO--N(C.sub.2H.sub.5).s- ub.2,
--CH.dbd.CH--CO--NH-n-C.sub.3H.sub.7,
--CH.dbd.CH--CO--NH-i-C.sub.3H- .sub.7,
--CH.dbd.CH--CO--NH-tert.-C.sub.4H.sub.5, --CH.dbd.CH--CO--NH-cycl-
opropyl, CH.dbd.CH--CO--NH-cyclobutyl,
--CH.dbd.CH--CO--NH-cyclopentyl, --CH.dbd.CH--CO--NH-cyclohexyl,
--CH.dbd.CH--C--NH-cycloheptyl, --CH.dbd.CH--CO--NH-cyclooctyl,
--CH.dbd.CH--CO-pyrrolidin-1-yl, --CH.dbd.CH--CO-piperidin-1-yl,
--CH.dbd.CH--CO-morpholin-4-yl,
--CH.dbd.CH--CO--NH--CH.sub.2CH.dbd.CH.sub.2,
--CH.dbd.CH--CO--NH--CH.sub- .2C.ident.CH,
--CH.dbd.CH--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--CH.dbd.CH--CO--NH--(CH.sub.2).sub.2Cl,
--CH.dbd.CH--CO--NH--C.sub.6H.su- b.5,
--CH.dbd.C(CH.sub.3)--CO--NH.sub.2, --CH.dbd.C(CH.sub.3)
--CO--NHCH.sub.3, --CH.dbd.C(CH.sub.3)--CO--N(CH.sub.3).sub.2,
--CH.dbd.C(CH.sub.3)--CO--NH--C.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CO--N- (C.sub.2H.sub.5).sub.2,
--CH.dbd.C(CH.sub.3)--CO--NH-n-C.sub.3H.sub.7,
--CH.dbd.C(CH.sub.3)--CO--NH-i-C.sub.3H.sub.7,
--CH.dbd.C(CH.sub.3)--CO--- NH-tert.-C.sub.4H.sub.9,
--CH.dbd.C(CH.sub.3)--CO--NH-cyclopropyl,
--CH.dbd.C(CH.sub.3)--CO--NH-cyclobutyl,
--CH.dbd.C(CH.sub.3)--CO--NH-cyc- lopentyl,
--CH.dbd.C(CH.sub.3)--CO--NH-cyclohexyl, --CH.dbd.C(CH.sub.3)--C-
O--NH-cycloheptyl, --CH.dbd.C(CH.sub.3)--CO--NH-cyclooctyl,
--CH.dbd.C(CH.sub.3)--CO-pyrrolidin-1-yl,
--CH.dbd.C(CH.sub.3)--CO-piperi- din-1-yl,
--CH.dbd.C(CH.sub.3)--CO-morpholin-4-yl, --CH.dbd.C(CH.sub.3)--C-
O--NH--CH.sub.2CH.dbd.C(CH.sub.3).sub.2,
--CH.dbd.C(CH.sub.3)--CO--NH--CH.- sub.2C.ident.CH,
--CH.dbd.C(CH.sub.3)--CO--N(CH.sub.3)--CH.sub.2C.ident.CH- ,
--CH.dbd.C(CH.sub.3)--CO--NH-(CH.sub.2).sub.2Cl,
--CH.dbd.C(CH.sub.3)--C- O--NH--C.sub.6H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH.sub.2,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NHCH.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--C- O--N(CH .sub.3)
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH--C.sub.2H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--N(C.sub.2H.sub.5).sub.2,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH-n-C.sub.3H.sub.7,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH-i-C.sub.3H.sub.7,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH-tert.-C.sub.4H.sub.9,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH--cyclopropyl,
--CH.dbd.C(C.sub.2H.sub.- 5)--CO--NH-cyclobutyl,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH-cyclopentyl,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH-cyclohexyl,
--CH.dbd.C(C.sub.2H.sub.5)- --CO--NH-cycloheptyl,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH-cyclooctyl,
--CH.dbd.C(C.sub.2H.sub.5)--CO-pyrrolidin-1-yl,
--CH.dbd.C(C.sub.2H.sub.5- )--CO-piperidin-1-yl,
--CH.dbd.C(C.sub.2H.sub.5)--CO-morpholin-4-yl,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH--CH.sub.2CH.dbd.C(C.sub.2H.sub.5)
.sub.2, --CH.dbd.C(C.sub.2H.sub.5)--CO--NH--CH.sub.2C.ident.CH,
--CH.dbd.C(C.sub.2H.sub.5)--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH--(CH.sub.2).sub.2Cl,
--CH.dbd.C(C.sub.2H.sub.5)--CO--NH--C.sub.6H.sub.5,
--CH.dbd.C(Cl)--CO--NH.sub.2, --CH.dbd.C(Cl)--CO--NHCH.sub.3,
--CH.dbd.C(Cl)--CO--N(CH.sub.3).sub.2,
--CH.dbd.C(C.sub.1)--CO--NH--C.sub- .2H.sub.5,
--CH.dbd.C(Cl)--CO--N(C.sub.2H.sub.5).sub.2,
--CH.dbd.C(Cl)--CO--NH-n-C.sub.3H.sub.7,
--CH.dbd.C(Cl)--CO--NH-i-C.sub.3- H.sub.7,
--CH.dbd.C(Cl)--CO--NH-tert.-C.sub.4H.sub.9,
--CH.dbd.C(Cl)--CO--NH-cyclopropyt,
--CH.dbd.C(Ct)--CO--NH-cyclobutyl,
--CH.dbd.C(Cl)--CO--NH-cyclopentyl,
--CH.dbd.C(Cl)--CO--NH-cyclohexyl,
--CH.dbd.C(Cl)--CO--NH-cycloheptyl,
--CH.dbd.C(Cl)--CO--NH-cyclooctyl,
--CH.dbd.C(Cl)--CO-pyrrolidin-1-yl,
--CH.dbd.C(Cl)--CO-piperidin-1-yl,
--CH.dbd.C(Cl)--CO-morpholin-4-yl,
--CH.dbd.C(Cl)--CO--NH--CH.sub.2CH.dbd- .C(Cl).sub.2,
--CH.dbd.C(Cl)--CO--NH--CH.sub.2C.ident.CH,
--CH.dbd.C(Cl)--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--CH.dbd.C(Cl)--CO--NH--(CH.sub.2).sub.2Cl,
--CH.dbd.C(Cl)--CO--NH--C.sub- .6H.sub.5,
--CH.dbd.C(Br)--CO--NH.sub.2, --CH.dbd.C(Br)--CO--NHCH.sub.3,
--CH.dbd.C(Br)--CO--N(CH.sub.3).sub.2,
--CH.dbd.C(Br)--CO--NH--C.sub.2H.s- ub.5,
--CH.dbd.C(Br)--CO--N(C.sub.2HK.sub.5).sub.2,
--CH.dbd.C(Br)--CO--NH-n-C.sub.3H.sub.7,
--CH.dbd.C(Br)--CO--NH-i-C.sub.3- H.sub.7,
--CH.dbd.C(Br)--CO--NH-tert.-C.sub.4H.sub.9,
--CH.dbd.C(Br)--CO--NH-cyclopropyl,
--CH.dbd.C(Br)--CO--NH-cyclobutyl,
--CH.dbd.C(Br)--CO--NH-cyclopentyl,
--CH.dbd.C(Br)--CO--NH-cyclohexyl,
--CH.dbd.C(Br)--CO--NH-cycloheptyl,
--CH.dbd.C(Br)--CO--NH-cyclooctyl,
--CH.dbd.C(Br)--CO-pyrrolidin-1-yl,
--CH.dbd.C(Br)--CO-piperidin-1-yl,
--CH.dbd.C(Br)--CO-morpholin-4-y.sub.1,
--CH.dbd.C(Br)--CO--NH--CH.sub.2C- H.dbd.C(Br) .sub.2,
--CH.dbd.C(Br)--CO--NH--CH.sub.2C-.ident.CH,
--CH.dbd.C(Br)--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--CH.dbd.C(Br)--CO--NH--(CH.sub.2).sub.2Cl,
--CH.dbd.C(Br)--CO--NH--C.sub- .6H.sub.5,
--CH.dbd.C(CN)--CO--NH.sub.2, --CH.dbd.C(CN)--CO--NHCH.sub.3,
--CH.dbd.C(CN)--CO--N(CH.sub.3).sub.2,
--CH.dbd.C(CN)--CO--NH--C.sub.2H.s- ub.5,
--CH.dbd.C(CN)--CO--N(C.sub.2H.sub.5).sub.2,
--CH--C(CN)--CO--NH-n-C- .sub.3H.sub.7,
--CH.dbd.C(CN)--CO--NH-i-C.sub.3H.sub.7,
--CH.dbd.C(CN)--CO--NH-tert.-C.sub.4H.sub.9,
--CH.dbd.C(CN)--CO--NH-cyclo- propyl,
--CH.dbd.C(CN)--CO--NH-cyclobutyl, --CH.dbd.C(CN)--CO--NH-cyclopen-
tyl, --CH.dbd.C(CN)--CO--NH-cyclohexyl,
--CH.dbd.C(CN)--CO--NH-cycloheptyl- ,
--CH.dbd.C(CN)--CO--NH-cyclooctyl,
--CH.dbd.C(CN)--CO-pyrrolidin-1-yl,
--CH.dbd.C(CN)--CO-piperidin-1-yl,
--CH.dbd.C(CN)--CO-morpholin-4-yl,
--CH.dbd.C(CN)--CO--NH--CH.sub.2CH.dbd.C(CN).sub.2,
--CH.dbd.C(CN)--CO--NH--CH.sub.2C.ident.CH,
--CH.dbd.C(CN)--CO--N(CH.sub.- 3)--CH.sub.2C.ident.CH,
--CH.dbd.C(CN)--CO--NH--(CH.sub.2).sub.2Cl,
--CH.dbd.C(CN)--CO--NH--C.sub.6H.sub.5, --CH.dbd.CH--CO--SCH.sub.3,
--CH--CH--CO--SC.sub.2H.sub.5, --CH.dbd.CH--CO--S-n-C.sub.3H.sub.7,
--CH.dbd.CH--CO--S-i-C.sub.3H, --CH.dbd.CH--CO--S-n-C.sub.4H.sub.9,
--CH.dbd.CH--CO--S-tert.-C.sub.4H.sub.9, --CH.dbd.C
(CH.sub.3)--CO--SCH.sub.3,
--CH.dbd.C(CH.sub.3)--CO--SC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CO--S-n-C .sub.3H.sub.7,
--CH.dbd.C(CH.sub.3)--CO--- S-i-C.sub.3H.sub.7,
--CH.dbd.C(CH.sub.3)--CO--S-n-C.sub.4H.sub.9,
--CH.dbd.C(CH.sub.3)--CO--S-tert.-C.sub.4H.sub.9,
--CH.dbd.C(C.sub.2H.sub- .5)--CO--SCH.sub.3,
--CH.dbd.C(C.sub.2H.sub.5)--CO--SC.sub.2H.sub.5,
--CH.dbd.C(C.sub.2H.sub.5)--CO--S-n-CH.sub.7,
--CH.dbd.C(C.sub.2H.sub.5)-- -CO--S-i-C.sub.3H.sub.7,
--CH.dbd.C(C.sub.2H.sub.5)--CO--S-n-C.sub.4H.sub.- 9,
--CH.dbd.C(C.sub.2H.sub.5)--CO--S-tert.-C.sub.4H.sub.9,
--CH.dbd.C(Cl)--CO--SCH.sub.3, --CH.dbd.C(Cl)--CO--SC.sub.2H.sub.5,
--CH.dbd.C(Cl)--CO--S-n-C.sub.3H.sub.7,
--CH.dbd.C(Cl)--CO--S-i-C.sub.3H.- sub.7,
--CH.dbd.C(Cl)--CO--S-n-C.sub.4H.sub.9,
--CH.dbd.C(Cl)--CO--S-tert.- -C.sub.4H.sub.9,
--CH.dbd.C(Br)--CO--SCH.sub.3, --CH.dbd.C(Br)--CO--SC.sub-
.2H.sub.5, --CH.dbd.C(Br)--CO--S-n-C.sub.3H.sub.7,
--CH.dbd.C(Br)--CO--S-i- -C.sub.3H.sub.7,
--CH.dbd.C(Br)--CO--S-n-C.sub.4H.sub.9,
--CH.dbd.C(Br)--CO--S-tert.-C.sub.4H.sub.9,
--CH.dbd.C(CN)--CO--SCH.sub.3- ,
--CH.dbd.C(CN)--CO--SC.sub.2H.sub.5,
--CH.dbd.C(CN)--CO--S-n-C.sub.3H.su- b.7,
--CH--C(CN)--CO--S-i-C.sub.3H.sub.7,
--CH.dbd.C(CN)--CO--S-n-C.sub.4H- .sub.9,
--CH.dbd.C(CN)--CO--S-tert.-C.sub.4H.sub.9,
--CH.dbd.C(COCH.sub.3)--CO--OCH.sub.3,
--CH.dbd.C(COC.sub.2H.sub.5)--CO--- OCH.sub.3,
--CH.dbd.C(CO-n-C.sub.3H.sub.7)--CO--OCH.sub.3,
--CH.dbd.C(COCH.sub.3)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(COC.sub.2H.sub.5)- --CO--OC.sub.2H.sub.5,
--CH.dbd.C(CO-n-C.sub.3H.sub.7)--CO--OC.sub.2H.sub.- 5,
--CH.dbd.C(COCH.sub.3)--CO--O-n-C.sub.3H.sub.7,
--CH.dbd.C(COC.sub.2H.s- ub.5)--CO--O-n-C.sub.3H.sub.7,
--CH.dbd.C(CO-n-C.sub.3H.sub.7)--CO--O-n-C.- sub.3H.sub.7,
--CH.dbd.C(CF.sub.3)--CO--OCH.sub.3, --CH.dbd.C(CF.sub.3)--C-
O--OC.sub.2H.sub.5, --CH.dbd.C(CF.sub.3)--CO--O-n-C.sub.3H.sub.7,
--CH.dbd.C(CF.sub.3)--CO--O-i-C.sub.3H.sub.7,
--CH.dbd.C(CF.sub.3)--CO-.s- ub.0-n-C.sub.4H.sub.9,
--CH.dbd.C(CF.sub.3)--CO--O-tert.-C.sub.4H.sub.9,
--CH.dbd.C(COOCH.sub.3).sub.2, --CH.dbd.C(COOC.sub.2H.sub.5).sub.2,
--CH--C(COOCH.sub.3)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(COO-n-C.sub.3H.sub.- 7)--CO--OCH.sub.3,
--CH.dbd.C(COO-n-C.sub.3H.sub.7)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(COO-n-C.sub.3H)).sub.2, --CH.dbd.CH--CH.dbd.CH--COOH,
--CH.dbd.CH--CH.dbd.CH--CO--OCH.sub.3,
--CH.dbd.CH--CH.dbd.CH--CO--OC.sub- .2H .sub.5,
--CH.dbd.CH--CH.dbd.C(COOCH.sub.3).sub.2,
--CH.dbd.CH--CH.dbd.C(CN)--CO--OCH.sub.3,
--CH.dbd.CH--CH.dbd.C(CN)--CO--- OC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(CN)--CO--OCH.sub.3,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(CN)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(CH.sub.3)--CO--OCH.sub.3,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(Cl)--CO--OCH.sub.3,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(Br)--CO--OCH.sub.3,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(CH.sub.3)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(Cl)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(Br)--CO--OC.sub.2H.sub.5,
--CH.dbd.C(CH.sub.3)--CH.dbd.C(CN)--CO--NH.sub.2,
--CH.dbd.C(CH.sub.3)--C- H.dbd.C(CN)--CO--NH--CH.sub.3,
--CH.dbd.CH-(CH.sub.2).sub.2--COOH,
--CH.dbd.CH--(CH.sub.2).sub.2--CO--OCH.sub.3,
--CH.dbd.CH-(CH.sub.2).sub.- 2--CO--OC .sub.2H.sub.5,
--CH.dbd.CH--CH.sub.2--CH(COOCH.sub.3).sub.2,
--CH.dbd.CH--CH.sub.2--CH (COOC .sub.2H.sub.5) .sub.2,
--CH.dbd.CH--CH.sub.2--CH(CN)--CO--OCH.sub.3,
--CH--CH--CH.sub.2--CH(CN)-- -CO--OC.sub.2H.sub.5, --CH.dbd.CH--CH
.sub.2--CH(CH.sub.3)--CO--OCH.sub.3,
--CH.dbd.CH-CM.sub.2--CH(CH.sub.3)--CO--OC.sub.2H.sub.5,
--CH.dbd.CH-(CH.sub.2).sub.2--CO--NH.sub.2,
--CH.dbd.CH-(CH.sub.2).sub.2-- -CO--NH--CH.sub.3,
--CH.dbd.CH--CH.sub.2--COOH, --CH.dbd.CH--CH.sub.2--CO--
-OCH.sub.3, --CH.dbd.CH--CH.sub.2--CO--OC.sub.2H.sub.5,
--CH.dbd.C(COOCH.sub.3)--CH.sub.2--CO--OCH.sub.3,
--CH.dbd.C(COOCH.sub.3)- --CH.sub.2--CO--OC.sub.2H.sub.5,
--CH.dbd.CH--CH .sub.2--CO--NH.sub.2, --CH.dbd.CH--CH
.sub.2--CO--NH--CH .sub.3, --CH.dbd.CH--CH .sub.2--CO--N(CH
.sub.3).sub.2, --CH(OCH.sub.3).sub.2, --CH(SCH.sub.3).sub.2, --CH
(OC.sub.2H.sub.5).sub.2, --CH(SC.sub.2H.sub.5).sub.2,
--CH(O-n-C.sub.3H.sub.7).sub.2, --CH(O-i-C.sub.3H.sub.7).sub.2,
--CH(S-n-C.sub.3H.sub.7).sub.2, --CH(S-i-C.sub.3H.sub.7).sub.2,
--CH(O-n-C.sub.4H.sub.9).sub.2, --CH(O-i-C.sub.4H.sub.9).sub.2,
--CH(O--S--C.sub.4H.sub.9).sub.2,
--CH(O-tert.-C.sub.4H.sub.9).sub.2, --CH(S-n-C,H.sub.9) .sub.2,
--CH(S-i-C.sub.4H.sub.9).sub.2, --CH(S-s-C.sub.4H.sub.9).sub.2,
--CH(S-tert.-C.sub.4H.sub.9).sub.2, --CH(OC.sub.5H.sub.11).sub.2,
1,3-dioxolan-2-yl, 1,3-dithiolan-2-yl, 1,3-oxathiolan-2-yl,
4-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dithiolan-2-yl,
4-methyl-1,3-oxathiolan-2-yl, 5-methyl-1,3-oxathiolan-2-yl,
4-ethyl-1,3-dioxolan-2-yl, 4-ethyl-1,4-dithiolan-2-yl,
4-ethyl-1,3-oxathiolan-2-yl, 5-ethyl-1,3-oxathiolan-2-yl,
4,5-dimethyl-1,3-dioxolan-2-yl, 4,4-dimethyl-1,3-dioxolan-2-yl,
4,5-dimethyl-1,3-dithiolan-2-yl, 5,5-dimethyl-1,3-dithiolan-2-yl,
4,5-dimethyl-1,3-oxathiolan-2-yl, 5,5-dimethyl-1,3-oxathiolan-2-yl,
4,4-dimethyl-1,3-oxathiolan-2-yl, 4-vinyl-1,3-dioxolan-2-yl,
4-vinyl-1,3-dithiolan-2-yl, 4-vinyl-1,3-oxathiolan-2-yl,
5-vinyl-1,3-oxathiolan-2-yl, 4-chloromethyl-1,3-dioxolan-2-yl,
4-chloromethyl-1,3-dithiolan-2-yl,
4-chloromethyl-3-oxathiolan-2-yl,
5-chloromethyl-1,3-oxathiolan-2-yl,
4-hydroxymethyl-1,3-dioxolan-2-yl,
4-hydroxymethyl-1,3-dithiolan-2-yl,
4-hydroxymethyl-1,3-oxathiolan-2-yl,
5-hydroxymethyl-1,3-oxathiolan-2-yl,
4-methoxymethyl-1,3-dioxolan-2-yl,
4-allyloxymethyl-1,3-dioxolan-2-yl,
4-propargyloxymethyl-1,3-dioxolan-2-y- l,
4-acetoxymethyl-1,3-dioxolan-2-yl,
4-methoxymethyl-1,3-dithiolan-2-yl,
4-allyloxymethyl-1,3-dithiolan-2-yl,
4-propargyloxymethyl-1,3-dithiolan-2- -yl,
4-acetoxymethyl-1,3-dithiolan-2-yl,
4-methylthiomethyl-1,3-dithiolan-- 2-yl,
4-methoxymethyl-1,3-oxathiolan-2-yl,
5-methoxymethyl-1,3-oxathiolan-- 2-yl,
4-allyloxymethyl-1,3-oxathiolan-2-yl,
5-allyloxymethyl-1,3-oxathiola- n-2-yl,
4-propargyloxymethyl-1,3-oxathiolan-2-yl, 5-propargyloxymethyl-1,3-
-oxathiolan-2-yl, 4-acetoxymethyl-1,3-oxathiolan-2-yl,
5-acetoxymethyl-1,3-oxathiolan-2-yl,
4-methylthiomethyl-1,3-dioxolan-2-yl- ,
4-carboxy-1,3-dithiolan-2-yl, 4-methoxycarbonyl-1,3-dioxolan-2-yl,
4-ethoxycarbonyl-1,3-dioxolan-2-yl,
4-n-butoxycarbonyl-1,3-dioxolan-2-yl,
4-methoxycarbonyl-1,3-dithiolan-2-yl,
4-ethoxycarbonyl-1,3-dithiolan-2-yl- ,
4-n-butoxycarbonyl-1,3-dithiolan-2-yl,
4-methoxycarbonyl-4-methyl-1,3-di- oxolan-2-yl,
4-methoxycarbonyl-4-methyl-1,3-dithiolan-2-yl,
4-ethoxycarbonyl-4-methyl-1,3-dioxolan-2-yl,
4-ethoxycarbonyl-4-methyl-1,- 3-dithiolan-2-yl,
4-n-butoxycarbonyl-4-methyl-1,3-dioxolan-2-yl,
4-n-butoxycarbonyl-4-methyl-1,3-dithiolan-2-yl,
4-cyanomethyl-1,3-dioxola- n-2-yl,
4-cyanomethyl-1,3-dithiolan-2-yl, 1,3-dioxan-2-yl,
1,3-dithian-2-yl, 1,3-oxathian-2-yl, 5-methyl-1,3-dioxan-2-yl,
5-methyl-1,3-dithian-2-yl, 5-methyl-1,3-oxathian-2-yl,
5,5-dimethyl-1,3-dioxan-2-yl, 4,6-dimethyl-1,3-dioxan-2-yl,
4,4-dimethyl-1,3-dioxan-2-yl, 5,5-dimethyl-1,3-dithian-2-yl,
4,6-dimethyl-1,3-dithian-2-yl, 4,4-dimethyl-1,3-dithian-2-yl,
5,5-dimethyl-1,3-oxathian-2-yl, 4,4-dimethyl-1,3-oxathian-2-yl,
6,6-dimethyl-1,3-oxathian-2-yl, 4-hydroxy-methyl-1,3-dioxan-2-yl,
4-methoxymethyl-1,3-dioxan-2-yl, 4-allyloxymethyl-1,3-dioxan-2-yl,
4-acetoxymethyl-1,3-dioxan-2-yl, 4-hydroxymethyl-1,3-dithian-2-yl,
4-methoxy-methyl-1,3-dithian-2-yl,
4-allyloxymethyl-1,3-dithian-2-yl,
4-acetoxymethyl-1,3-dithian-2-yl, 4-chloromethyl-1,3-dioxan-2-yl,
4-chloromethyl-1,3-dithian-2-yl, 1,3-dioxepan-2-yl,
1,3-dithiepan-2-yl, 1,3-dioxep-5-en-2-yl,
4-methoxycarbonyl-1,3-dioxan-2-yl,
4-ethoxycarbonyl-1,3-dioxan-2-yl,
4-n-butoxycarbonyl-1,3-dioxan-2-yl,
4-methoxycarbonyl-1,3-dithian-2-yl,
4-ethoxycarbonyl-1,3-dithian-2-yl,
4-n-butoxycarbonyl-1,3-dithian-2-yl,
4-methoxycarbonyl-4-methyl-1,3-dioxa- n-2-yl,
4-ethoxy-carbonyl-4-methyl-1,3-dioxan-2-yl,
4-n-butoxycarbonyl-4-methyl-1,3-dioxan-2-yl,
4-methoxycarbonyl-4-methyl-1- ,3-dithian-2-yl,
4-ethoxycarbonyl-4-methyl-1,3-dithian-2-yl,
4-n-butoxycarbonyl-4-methyl-1,3-dithian-2-yl, --C(CH.sub.3)
(OCH.sub.3).sub.2, --C(CH.sub.3) (SCH.sub.3) 2, --C(CH.sub.3)
(OC2H.sub.5)2, --C(CH.sub.3) (SC.sub.2H.sub.5),
--C(CH.sub.3)(O-n-C.sub.3- H.sub.7)2,
--C(CH.sub.3)(O-i-C.sub.3H.sub.7)2, --C(CH.sub.3)(S-n-C.sub.3H.-
sub.7).sub.2, --C(CH.sub.3)(S-i-C.sub.3H.sub.7).sub.2,
--C(CH.sub.3)O-n-C.sub.4H.sub.9).sub.2--C(CH.sub.3)(O-i-C.sub.4H.sub.9).s-
ub.2, --C(CH.sub.3)(O--S--C.sub.4H.sub.9).sub.2,
--C(CH.sub.3)(O-tert.-C.s- ub.4H.sub.9).sub.2,
--C(CH.sub.3)(S-n-C.sub.4H.sub.9).sub.2,
--C(CH.sub.3)(S-i-C.sub.4H.sub.9).sub.2,
--C(CH.sub.3)(S-s-C.sub.4H.sub.9- ).sub.2,
--C(CH.sub.3)(S-tert.-C.sub.4H.sub.9).sub.2, --C(CH.sub.3)
(O-n-C.sub.5H.sub.11)", --C(CH.sub.3) (O-n-C.sub.5H.sub.11).sub.2,
2-methyl-1, 3-dioxolan-2-yl, 2-methyl-1,3-dithiolan-2-yl,
2-methyl-1,3-oxathiolan-2-yl, 2,4-dimethyl-1,3-dicxolan-2-yl,
2,4-dimethyl-1,3-dithiolan-2-yl, 2,4-dimethyl-1,3-oxathiolan-2-yl,
2,5-dimethyl-1,3-oxathiolan-2-yl,
4-ethyl-2-methyl-1,3-dioxolan-2-yl,
4-ethyl-2-methyl-1,3-dithiolan-2-yl,
4-ethyl-2-methyl-1,3-oxathiolan-2-yl- ,
5-ethyl-2-methyl-1,3-oxathiolan-2-yl, 2, 4,
5-trimethyl-1,3-dioxolan-2-y- l, 2, 4,
4-trimethyl-1,3-dioxolan-2-yl, 2, 4, 5-trimethyl-1,3-dithiolan-2--
yl, 2,4,4-trimethyl-1,3-dithiolan-2-yl, 2, 4,
5-trimethyl-1,3-oxathiolan-2- -yl, 2, 4,
4-trimethyl-1,3-oxathiolan-2-yl, 2-methyl-4-vinyl-1,3-dioxolan--
2-yl, 2-methyl-4-vinyl-1,3-dithiolan-2-yl,
2-methyl-4-vinyl-1,3-oxathiolan- -2-yl,
2-methyl-5-vinyl-1,3-oxathiolan-2-yl,
4-chloromethyl-2-methyl-1,3-d- ioxolan-2-yl,
4-chloromethyl-2-methyl-1,3-dithiolan-2-yl,
4-chloromethyl-2-methyl-1,3-oxathiolan-2-yl,
5-chloromethyl-2-methyl-1,3-- oxathiolan-2-yl,
4-hydroxymethyl-2-methyl-1,3-dioxolan-2-yl,
4-hydroxymethyl-2-methyl-1,3-dithiolan-2-yl,
4-hydroxymethyl-2-methyl-1,3- -oxathiolan-2-yl,
5-hydroxymethyl-2-methyl-1,3-oxathiolan-2-yl,
4-methoxymethyl-2-methyl-1,3-dioxolan-2-yl,
4-allyloxymethyl-2-methyl-1,3- -dioxolan-2-yl,
2-methyl-4-propargyloxymethyl-1,3-dioxolan-2-yl,
4-acetoxy-2-methyl-1,3-dioxolan-2-yl,
4-methoxymethyl-2-methyl-1,3-dithio- lan-2-yl,
4-allyloxymethyl-2-methyl-1,3-dithiolan-2-yl,
2-methyl-4-propargyloxymethyl-1,3-dithiolan-2-yl,
4-acetoxy-2-methyl-1,3-- dithiolan-2-yl,
4-methoxymethyl-2-methyl-1,3-oxathiolan-2-yl,
5-methoxymethyl-2-methyl-1,3-oxathiolan-2-yl,
4-allyloxymethyl-2-methyl-1- ,3-oxathiolan-2-yl,
5-allyloxymethyl-2-methyl-1,3-oxathiolan-2-yl,
2-methyl-4-propargyloxymethyl-1,3-oxathiolan-2-yl,
2-methyl-5-propargyloxymethyl-1,3-oxathiolan-2-yl,
4-acetoxy-2-methyl-1,3-oxathiolan-2-yl,
5-acetoxy-2-methyl-1,3-oxathiolan- -2-yl,
2-methyl-4-methylthiomethyl-1,3-dioxolan-2-yl,
2-methyl-4-methylthiomethyl-1,3-dithiolan-2-yl,
4-carboxy-2-methyl-1,3-di- oxolan-2-yl,
4-carboxy-2-methyl-1,3-dithiolan-2-yl,
4-methoxycarbonyl-2-methyl-1,3-dioxolan-2-yl,
4-ethoxycarbonyl-2-methyl-1- ,3-dioxolan-2-yl,
4-n-butoxycarbonyl-2-methyl-1,3-dioxolan-2-yl,
4-methoxycarbonyl-2-methyl-1,3-dithiolan-2-yl,
4-ethoxycarbonyl-2-methyl-- 1,3-dithiolan-2-yl,
4-n-butoxycarbonyl-2-methyl-1,3-dithiolan-2-yl,
2,4-dimethyl-4-methoxycarbonyl-1,3-dioxolan-2-yl,
2,4-dimethyl-4-methoxyc- arbonyl-1,3-dithiolan-2-yl,
2,4-dimethyl-4-ethoxycarbonyl-1,3-dioxolan-2-y- l,
2,4-dimethyl-4-ethoxy-carbonyl-1,3-dithiolan-2-yl,
2,4-dimethyl-4-n-butoxycarbonyl-1,3-dioxolan-2-yl,
2,4-dimethyl-4-n-butoxycarbonyl-1,3-dithiolan-2-yl,
4-cyanomethyl-2-methyl-1,3-dioxolan-2-yl,
4-cyanomethyl-2-methyl-1,3-dith- iolan-2-yl,
2-methyl-1,3-dioxan-2-yl, 2-methyl-1,3-dithian-2-yl,
2-methyl-1,3-oxathian-2-yl, 2,5-dimethyl-1,3-dioxan-2-yl,
2,5-dimethyl-1,3-dithian-2-yl, 2,5-dimethyl-1,3-oxathian-2-yl, 2,
5, 5-trimethyl-1,3-dioxan-2-yl, 2, 4, 6-trimethyl-1,3-dioxan-2-yl,
2, 4, 4-trimethyl-1,3-dioxan-2-yl, 2, 5,
5-trimethyl-1,3-dithian-2-yl, 2, 4, 6-trimethyl-1,3-dithian-2-yl,
2, 4, 4-trimethyl-1,3-dithian-2-yl, 2, 5,
5-trimethyl-1,3-oxathian-2-yl, 2, 4, 4-trimethyl-1,3-oxathian-2-yl,
2, 6,
6-trimethyl-1,3-oxathian-2-yl,
4-hydroxymethyl-2-methyl-1,3-dioxan-2-yl,
4-methoxymethyl-2-methyl-1,3-dioxan-2-yl,
4-allyloxymethyl-2-methyl-1,3-d- ioxan-2-yl,
4-acetoxymethyl-2-methyl-1,3-dioxan-2-yl,
4-hydroxymethyl-2-methyl-1,3-dithian-2-yl,
4-methoxymethyl-2-methyl-1,3-d- ithian-2-yl,
4-allyloxymethyl-2-methyl-1,3-dithian-2-yl,
4-acetoxymethyl-2-methyl-1,3-dithian-2-yl,
4-chloromethyl-2-methyl-1,3-di- oxan-2-yl,
4-chloromethyl-2-methyl-1,3-dithian-2-yl, --C(CH.sub.3).dbd.NH,
--C(CH.sub.3).dbd.N--CH.sub.3, --C(CH.sub.3).dbd.N--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.N-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.N-i-C.sub.3H.sub.- 7,
--C(CH.sub.3).dbd.N-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.N--CH.sub.2CH.d- bd.CH.sub.2,
--C(CH.sub.3).dbd.N--CH.sub.2CH.dbd.CH.sub.2--CH.sub.3,
--C(CH.sub.3).dbd.N--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.N--CH.sub.2C.i- dent.C--CH.sub.3,
--C(CH.sub.3).dbd.N-cyclopropyl, --C(CH.sub.3).dbd.N-cyc- lobutyl,
--C(CH.sub.3).dbd.N-cyclo-pentyl, --C(CH.sub.3).dbd.N-cyclohexyl,
--C(CH.sub.3).dbd.N-cycloheptyl,
--C(CH.sub.3).dbd.N--CH.sub.2--CH.sub.2C- l,
--C(CH.sub.3).dbd.N--CH.sub.2Cl,
--C(CH.sub.3).dbd.N--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.N-(2-F--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(3-F--C.su- b.6H.sub.4),
--C(CH.sub.3).dbd.N-(4-F--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(2-Cl--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(3-Cl--C.- sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(4--Cl--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(2-CH.sub.3--C.sub.6H-.sub.4),
--C(CH.sub.3).dbd.N-(3--CH.sub.3--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(4-CH.sub.3--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(2-- -CF.sub.3--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(3-CF.sub.3--C.sub.6H.sub.- 4),
--C(CH.sub.3).dbd.N-(4--CF.sub.3--C.sub.6H.sub.4),
--C(CM.sub.3).dbd.N-(2-OCH.sub.3--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(3--OCH.sub.3--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(4-OCH.sub.3--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(4--NO.sub.2--C.sub.6H.sub.4), --C
(CH.sub.3).dbd.N-(4-CN--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N-(2,4--C.sub.- 12--C.sub.6H.sub.3),
--C(CM.sub.3).dbd.N-(2,4-(CH.sub.3).sub.2-C.sub.6H.su- b.3),
--C(CH.sub.3).dbd.N--CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.N--CH.su- b.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.N--CH.sub.2CH.sub.2--OCH--,
--C(CH.sub.3).dbd.N--CH.sub.2CH.sub.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.N--OH, --C(CH.sub.3).dbd.N--OCH.sub.3,
--C(CH.sub.3).dbd.N--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.N-.sub.0-n-C.sub.- 3H.sub.7,
--C(CH.sub.3).dbd.N--O-i-C.sub.3H.sub.7, --C(CH.sub.3).dbd.N--O--
n-C.sub.4H.sub.9, --C(CH.sub.3).dbd.N-.sub.0-i-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.N--O-s--C.sub.4H.sub.9,
--C(CH.sub.3).dbd.N--O-tert.-C.- sub.4H.sub.9,
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.CH.sub.2,
--C(CH.sub.3).dbd.N--OCH(CH.sub.3)--CH.dbd.CH.sub.2,
--C(CH.sub.3).dbd.N--OCH.sub.2--C.ident.CH,
--C(CH.sub.3).dbd.N--CH(CH.su- b.3)--C.ident.CH,
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.C--CH.sub.3,
--C(CH.sub.3).dbd.N--OCH.sub.2CH.sub.2--Cl,
--C(CH.sub.3).dbd.N--OCH.sub.- 2CH.sub.2--F,
--C(CH.sub.3).dbd.N--OCH.sub.2--CF.sub.3,
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.CHCl,
--C(CH.sub.3).dbd.N--OCH.sub- .2--C(Cl).dbd.CH.sub.2,
--C(CH.sub.3).dbd.N--OCH.sub.2--C(Br).dbd.CH.sub.2- ,
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.C(Cl)--CH.sub.3,
--C(CH.sub.3).dbd.N--O--CO--CH.sub.3,
--C(CH.sub.3).dbd.N--O--CO--C.sub.2- H.sub.5,
--C(CH.sub.3).dbd.N--OCH.sub.2--CN, --C(CH.sub.3).dbd.N--OCH.sub.-
2--CH.dbd.CH--CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.-
CH--CH.sub.2O-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub- .3--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub.4--C.sub.6H.sub- .5,
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub.4-(4-Cl--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub.4-(4-CH.sub.3O--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--O-(CH.sub.2).sub.4-(4-CH.sub.3-C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub.4-(4-F--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.CH--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.CH(4-F--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.CH-(4--Cl--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.CH(3-CH.sub.3O--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub.2--CH.dbd.CH-(4-F--C.sub.6H.sub.4)-
,
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub.2--CH.dbd.CH-(4-C--C.sub.6H.sub.4-
),
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.CH--CH.sub.2-(4-CH.sub.3O--C.sub-
.6H.sub.4),
--C(CH.sub.3).dbd.N--OCH.sub.2--CH.dbd.C(CH.sub.3)--C.sub.6H.s-
ub.5,
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub.2--CH.dbd.CH-(3,4-Cl.sub.2--C-
.sub.6H.sub.3),
--C(CH.sub.3).dbd.N--O--(CH.sub.2).sub.3--C.ident.C-(4-F---
C.sub.6H.sub.4), --C(CH.sub.3).dbd.N--OCH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.N--OCH.sub.2CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.N--OCH.sub.2--OC.sub.2H.sub.9,
--C(CH.sub.3).dbd.N--OCH- (CH.sub.3)--OCH.sub.3, --C
(CH.sub.3).dbd.N--OCH(CH.sub.3)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.N--OCH(CH.sub.3)--CO--O-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.N--NH.sub.2, --C(CH.sub.3).dbd.N--NH--CH.sub.3,
--C(CH.sub.3).dbd.N--NH--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.N--NH-n-q.sub.- 3H.sub.7,
--C(CH.sub.3).dbd.N--NH-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.N--NH-n-C.sub.4H.sub.9, --C (CH.sub.3).dbd.N--NH
i-C.sub.4H.sub.9, --C(CH.sub.3).dbd.N--NH--s-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.N--NH-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.N--NH-cyc- lopropyl,
--C(CH.sub.3).dbd.N--NH-cyclobutyl, --C(CH.sub.3).dbd.N--NH-cycl-
opentyl, --C(CH.sub.3).dbd.N--NH-cyclohexyl,
--C(CH.sub.3).dbd.N--NH-cyclo- heptyl,
--C(CH.sub.3).dbd.N--N(CH.sub.3).sub.2, --C(CH.sub.3).dbd.N--N(C.s-
ub.2H.sub.5).sub.2, --C(CH.sub.3).dbd.N--N(n-C.sub.3H.sub.7).sub.2,
--C(CH.sub.3).dbd.N-N(i-C.sub.3H.sub.7).sub.2,
--C(CH.sub.3).dbd.N--NH--C- H.sub.2--C.dbd.CH,
--C(CH.sub.3).dbd.N--NH--CH.sub.2--C.ident.CH,
--C(CH.sub.3).dbd.N--N(CH.sub.3)--CH.sub.2--C.ident.CH,
--C(CH.sub.3).dbd.N--NH--CH.sub.2CF.sub.3,
--C(CH.sub.3).dbd.N--NH--CO--C- H.sub.3,
--C(CH.sub.3).dbd.N--NH--CO--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.N--NH--CO--OCH .sub.3,
--C(CH.sub.3).dbd.N--NH--CO--OC.- sub.2H.sub.5,
--C(CH.sub.3).dbd.N--NH--CO--O-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.N-pyrrolidin-1-yl,
--C(CH.sub.3).dbd.N-piperidin-1-yl,
--C(CH.sub.3).dbd.N-morpholin-4-yl,
--C(CH.sub.3).dbd.N--NH--C.sub.6H.sub- .5, --C
(CH.sub.3).dbd.N--NH-(4-Cl--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--NH-(4-NO.sub.2--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--NH-(4-F--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--NH-(4- -CHl.sub.3--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.N--NH-(2,4-Cl.sub.2--C.sub.- 6H.sub.3),
--C(CH.sub.3).dbd.N--NH-(2,4-(NO.sub.2).sub.2--C.sub.6H.sub.3),
--C(CH.sub.3).dbd.N--NH--CO--NH.sub.2,
--C(CH.sub.3).dbd.N--NH--CO--NHCH.- sub.3,
--C(CH.sub.3).dbd.N--NH--CO--NHC.sub.2H.sub.5,
--C(CH.sub.3).dbd.N--NH--CO--N(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.CH--COO- H, --C(CH.sub.3).dbd.CH--CO--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CO--OC.sub.2- H.sub.5,
--C(CH.sub.3).dbd.CH--CO--O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO--O-n-- C.sub.4H.sub.9,
--C(CH.sub.3).dbd.CH--CO-o-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.CH--CO--O-cyclopropyl,
--C(CH.sub.3).dbd.CH--CO--O-cycl- obutyl,
--C(CH.sub.3).dbd.CH--CO--O-cyclopentyl, --C(CH.sub.3).dbd.CH--CO--
-O-cyclohexyl, --C(CH.sub.3).dbd.CH--CO--O-cycloheptyl,
--C(CH.sub.3).dbd.C(CH.sub.3)--COOH,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O- CH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O-cyclopropyl,
--C(CH.sub.3).dbd.C(CH.- sub.3)--CO--O-cyclobutyl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O-cyclopentyl- ,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O-cyclohexyl,
--C(CH.sub.3).dbd.C(CH.- sub.3)--CO--O-cycloheptyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--COOH,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-O-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--O-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--O-cyclo-propyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--O-cyclobutyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-O-cyclopentyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--O-cyclohexyt,
--C(CH.sub.3).dbd.C(C.sub.2H)--CO--O-cycloheptyl,
--C(CH.sub.3).dbd.CH--C- OOH, --C(CH.sub.3).dbd.CH--CO--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CO--OC.sub- .2H.sub.5,
--C(CH.sub.3).dbd.C(Cl)--CO--O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)--CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)--CO- --O-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Cl)--CO--O-tert.--C.sub.4H.sub.9- ,
--C(CH.sub.3).dbd.C(Cl)--CO--O-cyclopropyl,
--C(CH.sub.3).dbd.C(Cl)--CO-- -O-cyclobutyl,
--C(CH.sub.3).dbd.C(Cl)--CO--O-cyclopentyl,
--C(CH.sub.3).dbd.C(Cl)--CO--O-cyclohexyl,
--C(CH.sub.3).dbd.C(Cl)--CO--O- -cycloheptyl,
--C(CH.sub.3).dbd.C(Br)--COOH, --C(CH.sub.3).dbd.C(Br)--CO---
OCH.sub.3, --C(CH.sub.3).dbd.C(Br)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Br)--CO--O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Br)-- -CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Br)--CO--O-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Br)--CO--O-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Br)--CO--O-cyclopropyl,
--C(CH.sub.3).dbd.C(Br)--CO--- O-cyclobutyl,
--C(CH.sub.3).dbd.C(Br)--CO--O-cyclopentyl,
--C(CH.sub.3).dbd.C(Br)--CO--O-cyclohexyl,
--C(CH.sub.3).dbd.C(Br)--CO--O- -cycloheptyl,
--C(CH.sub.3).dbd.C(CN)--COOH, --C(CH.sub.3).dbd.C(CN)--CO---
OCH.sub.3, --C(CH.sub.3).dbd.C(CN)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CN)--CO--O-n-C.sub.3H.sub.7, --C
(CH.sub.3).dbd.C (CN) --CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CN)--CO--O-n-C.sub.4H.sub- .9,
--C(CH.sub.3).dbd.C(CN)--CO--O-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CN)--CO--O-cyclopropyl,
--C(CH.sub.3).dbd.C(CN)--CO--- O-cyclobutyl,
--C(CH.sub.3).dbd.C(CN)--CO--O-cyclopentyl,
--C(CH.sub.3).dbd.C(CN)--CO--O-cyclohexyl,
--C(CH.sub.3).dbd.C(CN)--CO--O- -cycloheptyl,
--C(CH.sub.3).dbd.CH--CO--OCH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CO--OCH.sub.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.CH--CO--OCH.sub.2-O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO--O-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO--O- CH(CH.sub.3)--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CO--OCH(CH.sub.3)--OC.sub.2- H.sub.5,
--C(CH.sub.3).dbd.CH--CO--OCH.sub.2CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CO--OCH.sub.2CH.sub.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2-O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH(CH.sub.3)--OCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH(CH.sub.3)--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2CH.sub.2--OC.sub.2H.sub.5
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--OC.sub.2H.sub.5,
--C (CH.sub.3).dbd.C
(C.sub.2H.sub.5)--CO--OCH.sub.2-O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--O-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH(CH.sub.3)--OCH.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH(CH.sub.3)--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2CH.sub.2--OC.sub.2H.sub-
.5, --C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2-O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)--CO--O-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)-- -CO--OCH(CH.sub.3)--OCH.sub.3,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH(CH.sub.3)-- -OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2CH.sub.2--OCH.sub.- 3,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2CH.sub.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2-O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Br)--CO--O-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Br)-- -CO--OCH(CH.sub.3)--OCH.sub.3,
--C(CH.sub.3).dbd.C(Br)--CO--OCH(CH.sub.3)-- -OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2CH.sub.2--OCH .sub.3,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2CH.sub.2--OC.sub.2Hz,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2-O-n-C .sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CN)--CO--O-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CN)-- -CO--OCH(CH.sub.3)--OCH.sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--OCH(CH.sub.3)-- -OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2CH.sub.2--OCH .sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2CH.sub.2--OC.sub.2H.sub.5,
--C (CH.sub.3).dbd.CH--CO--OCH.sub.2--CF.sub.3,
--C(CH.sub.3).dbd.CH--CO-- -OCH.sub.2--CCl.sub.3,
--C(CH.sub.3).dbd.CH--CO--OCH.sub.2-oxiranyl,
--C(CH.sub.3).dbd.CH--CO--O--(CH.sub.2).sub.3-Br,
--C(CH.sub.3).dbd.CH--C- O--OCH.sub.2--CH.dbd.CH.sub.2,
--C(CH.sub.3).dbd.CH--CO--OCH.sub.2--C.iden- t.CH,
--C(CH.sub.3).dbd.CH--CO--OCH.sub.2--CN,
--C(CH.sub.3).dbd.CH--CO--O- CH.sub.2CH.sub.2--CN,
--C(CH.sub.3).dbd.C(CH .sub.3)--CO--OCH.sub.2--CF.su- b.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2--CCl.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2-oxiranyl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--O--(CH.sub.2).sub.3-Br,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2--CH.dbd.CH.sub.2,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2--C.ident.CH,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--OCH.sub.2--CN,
--C(CH.sub.3).dbd.C(CH.- sub.3)--CO--OCH.sub.2CH.sub.2--CN,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO- --OCH.sub.2--CF.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2-- -CCl.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2-oxiranyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--O--(CH.sub.2) .sub.3-Br,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--CH.dbd.CH.sub.2,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--C.dbd.CH,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2--CN,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--OCH.sub.2CH.sub.2--CN,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2--CF.sub.3,
--C(CH.sub.3).dbd.C(Cl)- --CO--OCH.sub.2--CCl.sub.3,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2-oxirany- l,
--C(CH.sub.3).dbd.C(Cl)--CO--O--(CH.sub.2).sub.3-Br,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2--CH.dbd.CH.sub.2,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2--C.ident.CH,
--C(CH.sub.3).dbd.C(Cl)--CO--OCH.sub.2--CN,
--C(CH.sub.3).dbd.C(Cl)--CO--- OCH.sub.2CH.sub.2--CN,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2--CF.sub.3,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2--CCl.sub.3,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2-oxiranyl,
--C(CH.sub.3).dbd.C(Br)-- -CO--O--(CH.sub.2).sub.3-Br,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2--CH.db- d.CH.sub.2,
--C(CH.sub.3).dbd.C(Br)--CO--OCH.sub.2--C.ident.CH,
--C(CH.sub.3).dbd.C(BR)--CO--OCH.sub.2--CN,
--C(CH.sub.3).dbd.C(Br)--CO--- OCH.sub.2CH.sub.2--CN,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2--CF.sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2--CCl.sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2-oxiranyl,
--C(CH.sub.3).dbd.C(CN)-- -CO--O--(CH.sub.2) .sub.3-Br,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2--CH.d- bd.CH.sub.2,
--C(CH.sub.3).dbd.C(CN)--CO--OCH.sub.2--C.ident.CH,
--C(CH.sub.3)--C(CN)--CO--OCH.sub.2--CN,
--C(CH.sub.3).dbd.C(CN)--CO--OCH- .sub.2CH.sub.2--CN,
--C(CH.sub.3).dbd.CH--CO--CH.sub.3,
--C(CH.sub.3).dbd.CH--CO--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.CH--CO-n-C.su- b.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.CH--CO-tert.- -C.sub.4H.sub.9,
--C(CH.sub.3).dbd.CH--CO--CH.sub.2Cl,
--C(CH.sub.3).dbd.CH--CO--CH.sub.2Br,
--C(CH.sub.3).dbd.CH--CO--CHCl.sub.- 2,
--C(CH.sub.3).dbd.CH--CO--CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CO- --CH(OCH.sub.3).sub.2,
--C(CH.sub.3).dbd.CH--CO--CH.sub.2--SCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--CH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3- )--CO--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--CH.sub.2Cl,
--C(CH.sub.3).dbd.C(CH.sub- .3)--CO--CH.sub.2Br,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--CHCl.sub.2,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--CH(OCH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--CH.sub.2--SCH.sub.3, --C
(CH.sub.3).dbd.C(C .sub.2H.sub.5)--CO--CH.sub.3,
--C(CH.sub.3).dbd.C(C.su-
b.2H.sub.5)--CO--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-n- -C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-i-C .sub.3H.sub.7,
--C(cH.sub.3).dbd.c(c.sub.2H.sub.5)-CO-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--CH.sub.2Cl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--CH.sub.2Br,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--CHCl.sub.2,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2CH.sub.5)--CO--CH(OCH.sub.3) .sub.2,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--CH.sub.2--SCH.sub.3,
--C(CH.sub.3).dbd.C(Cl)--CO--CH.sub.3,
--C(CH.sub.3).dbd.C(Cl)--CO--C.sub- .2H.sub.5,
--C(CH.sub.3).dbd.C(Cl)--CO-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)--CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)--CO- -n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Cl)--CO-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Cl)--CO--CH.sub.2Cl,
--C(CH.sub.3).dbd.C(Cl)--CO--CHC- l.sub.2,
--C(CH.sub.3).dbd.C(Cl)--CO--CH.sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(Cl)--CO--CH(OCH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(Cl)- --CO--CH.sub.2--SCH.sub.3,
--C(CH.sub.3).dbd.C(Br)--CO--CH.sub.3, --C(CH.sub.3)
.dbd.C(Br)--CO--C.sub.2H.sub.5, --C(CH.sub.3).dbd.C(Br)--CO-
-n-C.sub.3H.sub.7, --C (CH.sub.3).dbd.C(Br)--CO-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Br)--CO-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Br)--CO- -tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Br)--CO--CH.sub.2Cl,
--C(CH.sub.3).dbd.C(Br)--CO--CH.sub.2Br,
--C(CH.sub.3).dbd.C(Br)--CO--CH.- sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(Br)--CO--CH(OCH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(Br)--CO--CH.sub.2--SCH.sub.3,
--C(CH.sub.3).dbd.C(CN)- --CO--CH.sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--C.sub.2H.sub.5, --C(CH.sub.3).dbd.C
(CN)--CO-n-C.sub.3H.sub.7, --C(CH.sub.3).dbd.C(CN)--C-
O-i--C.sub.3H.sub.7, --C(CH.sub.3).dbd.C (CN)
--CO-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CN)--CO-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CN)- --CO--CH.sub.2Cl,
--C(CH.sub.3).dbd.C(CN)--CO--CH.sub.2Br,
--C(CH.sub.3).dbd.C(CN)--CO--CHCl.sub.2,
--C(CH.sub.3).dbd.C(CN)--CO--CH.- sub.2--OCH.sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--CH(OCH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(CN)--CO--CH.sub.2--SCH.sub.3,
--C(CH.sub.3).dbd.CH--C- O--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.CH--CO-(4--Cl--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO-(.sub.4--Cl--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-(.sub.4--Cl--C.sub.6H.sub.4),
--C(CH.sub.3).dbd.C(Cl)--CO--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.C(Br)--CO-- -C.sub.6H.sub.5,
--C(CH.sub.3).dbd.C(CN)--CO--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.CH--CO--NH.sub.2,
--C(CH.sub.3).dbd.CH--CO--NHCH.sub.3,
--C(CH.sub.3).dbd.CH--CO--N(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.CH--CO--NH- --C.sub.2H.sub.5,
--C(CH.sub.3).dbd.CH--CO--N(C.sub.2H.sub.5).sub.2,
--C(CH.sub.3).dbd.CH--CO--NH-n-C.sub.3H.sub.7, --C
(CH.sub.3).dbd.CH--CO--NH-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO--NH-- tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.CH--CO--NH-cyclopropyl,
--C(CH.sub.3).dbd.CH--CO--NH-cyclobutyl,
--C(CH.sub.3).dbd.CH--CO--NH-cyc- lopentyl,
--C(CH.sub.3).dbd.CH--CO--NH-cyclohexyl, --C(CH.sub.3).dbd.CH--C-
O--NH-cycloheptyl, --C(CH.sub.3).dbd.CH--CO--NH-cyclooctyl,
--C(CH.sub.3).dbd.CH--CO-pyrrolidin-1-yl,
--C(CH.sub.3).dbd.CH--CO-piperi- din-1-yl,
--C(CH.sub.3).dbd.CH--CO-morpholin-4-yl, --C(CH.sub.3).dbd.CH--C-
O--NH--CH.sub.2CH.dbd.CH.sub.2,
--C(CH.sub.3).dbd.CH--CO--NH--CH.sub.2C.id- ent.CH,
--C(CH.sub.3).dbd.CH--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.CH--CO--NH--(CH.sub.2).sub.2Cl,
--C(CH.sub.3).dbd.CH--C- O--NH--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH.sub.2,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NHCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub- .3)--CO--N(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH--C.sub.2- H.sub.5,
--O(CH.sub.3)--C(CH.sub.3)--CO--N(C.sub.2H.sub.5).sub.2,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH-cyclopropyl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH-cyclobutyl,
--C(CH.sub.3).dbd.C(CH.- sub.3)--CO--NH-cyclopentyl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH-cyclohex- yl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH--cycloheptyl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH-cyclooctyl,
--C(OH.sub.3).dbd.O(OH.- sub.3)--CO-pyrrolidin-1-yl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO-piperidin-1-- yl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO-morpholin-4-yl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH--CH.sub.2CH.dbd.C(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH--(CH.sub.2).sub.2Cl,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--NH--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH.sub.2,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NHCH.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--N(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--N(C.sub.2H.sub.5).sub.2,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH-i-C.sub.7H.sub.7,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH-cyclopropyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH--cyclobutyl,
--C(CH.sub.3).dbd.C(CO.sub.2H.sub.5)--CO--NH-cyclopentyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH-cyclohexyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH--cycloheptyl,
--C(CH.sub.3).dbd.C (C.sub.2H.sub.5)--CO--NH-cyclooctyl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-pyrrolidin-1-yl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-piperidin-1-yl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO-morpholin-4-yl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH--CH.sub.2CH.dbd.C(C.sub.2H.su-
b.5).sub.2,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH--CH.sub.2C.ident.C- H,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--N(CH.sub.3)--CH.sub.2C.ident.C-
H, --C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH--(CH.sub.2)
.sub.2Cl,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--NH--C.sub.5H.sub.5,
--C(CH.sub.3).dbd.C(Cl)--CO--NH.sub.2,
--C(CH.sub.3).dbd.C(Cl)--C.sub.3--- NHCH.sub.3,
--C(CH.sub.3).dbd.C(Cl)--CO--N(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(Cl)--CO--NH--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Cl)-- -CO--N(C.sub.2H.sub.5).sub.2,
--C(CH.sub.3).dbd.C(Cl)--CO--NH-n-C.sub.3H.s- ub.7,
--C(CH.sub.3).dbd.C(Cl)--CO--NH-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)--CO--NH-tert.---CH.sub.9,
--C(CH.sub.3).dbd.C(Cl)- --CO--NH-cyclopropyl,
--C(CH.sub.3).dbd.C(Cl)--CO--NH-cyclobutyl,
--C(CH.sub.3).dbd.C(Cl)--CO--NH-cyclopentyl,
--C(CH.sub.3).dbd.C(Cl)--CO-- -NH-cyclohexyl,
--C(CH.sub.3).dbd.C(Cl)--CO--NH-cycloheptyl,
--C(CH.sub.3).dbd.C(Cl)--CO--NH-cyclooctyl,
--C(CH.sub.3).dbd.C(Cl)--CO-p- yrrolidin-1-yl,
--C(CH.sub.3).dbd.C(Cl)--CO-piperidin-1-yl,
--C(CH.sub.3).dbd.C(Cl)--CO-morpholin-4-yl,
--C(CH.sub.3).dbd.C(Cl)--CO--- NH--CH.sub.2CH.dbd.C(Cl).sub.2,
--C(CH.sub.3).dbd.C(Cl)--CO--NH--CH.sub.2C- .ident.CH,
--C(CH.sub.3).dbd.C(Cl)--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.C(Cl)--CO--NH--(CH.sub.2).sub.2Cl,
--C(CH.sub.3).dbd.C(Cl)--CO--NH--CrH.sub.5,
--C(CH.sub.3).dbd.C(Br)--CO--- NH.sub.2,
--C(CH.sub.3).dbd.C(Br)--CO--NHCH.sub.3, --C(CH.sub.3).dbd.C(Br)-
--CO--N(CH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(Br)--CO--NH--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Br)--CO--N(C.sub.2H.sub.5).sub.2,
--C(CH.sub.3).dbd.C(Br)--CO--NH-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Br)- --CO--NH-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Br)--CO--NH-tert.-C.sub.4H.- sub.9,
--C(CH.sub.3).dbd.C(Br)--CO--NH-cyclopropyl,
--C(CH.sub.3).dbd.C(Br)--CO--NH-cyclobutyl,
--C(CH.sub.3).dbd.C(Br)--CO--- NH-cyclopentyl,
--C(CH.sub.3).dbd.C(Br)--CO--NH-cyclohexyl,
--C(CH.sub.3).dbd.C(Br)--CO--NH-cycloheptyl,
--C(CH.sub.3).dbd.C(Br)--CO-- -NH-cyclooctyl,
--C(CH.sub.3).dbd.C(Br)--CO-pyrrolidin-1-yl,
--C(CH.sub.3).dbd.C(Br)--CO-piperidin-1-yl,
--C(CH.sub.3).dbd.C(Br)--CO-m- orpholin-4-yl,
--C(CH.sub.3).dbd.C(Br)--CO--NH--CH.sub.2CH.dbd.C(Br).sub.2- ,
--C(CH.sub.3).dbd.C(Br)--CO--NH--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.C(Br)--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.C(Br)--CO--NH--(CH.sub.2).sub.2Cl,
--C(CH.sub.3).dbd.C (Br)--CO--NH--C.sub.6H.sub.5, --C
(CH.sub.3).dbd.C(CN)--CO--NH.sub.2,
--C(CH.sub.3).dbd.C(CN)--CO--NHCH.sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--N(C- H.sub.3).sub.2,
--C(CH.sub.3).dbd.C(CN)--CO--NH--C.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CN)--CO--N(C.sub.2H.sub.5).sub.2,
--C(CH.sub.3).dbd.C(CN)--CO--NH-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CN)- --CO--NH-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CN)--CO--NH-tert.-C&H.sub.9- ,
--C(CH.sub.3).dbd.C(CN)--CO--NH-cyclopropyl,
--C(CH.sub.3).dbd.C(CN)--CO- --NH-cyclobutyl,
--C(CH.sub.3).dbd.C(CN)--CO--NH-cyclopentyl,
--C(CH.sub.3).dbd.C(CN)--CO--NH-cyclohexyl,
--C(CH.sub.3).dbd.C(CN)--CO--- NH-cycloheptyl,
--C(CH.sub.3).dbd.C(CN)--CO--NH-cyclooctyl,
--C(CH.sub.3).dbd.C(CN)--CO-pyrrolidin-1-yl,
--C(CH.sub.3).dbd.C(CN)--CO-- piperidin-1-yl,
--C(CH.sub.3).dbd.C(CN)--CO-morpholin-4-yl,
--C(CH.sub.3).dbd.C(CN)--CO--NH--CH.sub.2CH.dbd.C(CN).sub.2,
--C(CH.sub.3).dbd.C(CN)--CO--NH--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.C(CN)--CO--N(CH.sub.3)--CH.sub.2C.ident.CH,
--C(CH.sub.3).dbd.C(CN)--CO--NH--(CH.sub.2).sub.2Cl,
--C(CH.sub.3).dbd.C(CN)--CO--NH--C.sub.6H.sub.5,
--C(CH.sub.3).dbd.CH--CO- --SCH.sub.3,
--C(CH.sub.3).dbd.CH--CO--SC.sub.2H.sub.5,
--C(CH.sub.3).dbd.CH--CO--S-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO--S- -i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.CH--CO--S-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.CH--CO--S-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CH.- sub.3)--CO--SCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--SC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--S-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--S-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--S-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CH.sub.3)--CO--S-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--SCH.sub.3,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--SC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--S-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(C.sub.2H.sub.5)--CO--S-i-C.sub.3H.sub.7,
--C(CH.sub.3)--C(C.sub.2H.sub.5)--CO--S-n-C.sub.4H.sub.9,
--C(C.sub.3).dbd.C(C.sub.2H.sub.5)--CO--S-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Cl)--CO--SCH.sub.3,
--C(CH.sub.3).dbd.C(Cl)--CO--SC.s- ub.2H.sub.5,
--C(CH.sub.3).dbd.C(Cl)--CO--S-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)--CO--S-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Cl)-- -CO--S-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(C.sub.1)--CO--S-tert.-C.sub.4- H.sub.9,
--C(CH.sub.3).dbd.C(Br)--CO--SCH.sub.3, --C(CH.sub.3).dbd.C(Br)---
CO--SC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(Br)--CO--S-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C (Br)--CO--S-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(Br)- --CO--S-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(Br)--CO--S-tert.-C.sub.4H.su- b.9,
--C(CH.sub.3).dbd.C(CN)--CO--SCH.sub.3,
--C(CH.sub.3).dbd.C(CN)--CO--- SC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CN)--CO--S-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CN)--CO--S-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CN)-- -CO--S-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CN)--CO--S-tert.-C.sub.4H.sub- .9,
--C(CH.sub.3)--C(COCH.sub.3)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(COC.s- ub.2H.sub.5)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(CO-n-C.sub.3H.sub.7)--CO-- -OCH.sub.3,
--C(CH.sub.3).dbd.C(COCH.sub.3)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(COC.sub.2H.sub.5)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CO-n-C.sub.3H.sub.7)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(COCH.sub.3)--CO--O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(COC.sub.2H.sub.5)--CO--O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CO-n-C.sub.3H.sub.7)--CO--O-n-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CF.sub.3)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(CF.sub.- 3)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CF.sub.3)--CO--O-n-C.sub.3H.s- ub.7,
--C(CH.sub.3)--C(CF.sub.3)--CO--O-i-C.sub.3H.sub.7,
--C(CH.sub.3).dbd.C(CF.sub.3)--CO--O-n-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(CF.sub.3)--CO--O-tert.-C.sub.4H.sub.9,
--C(CH.sub.3).dbd.C(COOCH.sub.3).sub.2,
--C(CH.sub.3).dbd.C(COOC.sub.2H.s- ub.5).sub.2,
--C(CH.sub.3).dbd.C(COOCH.sub.3)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(COO-n-C.sub.3H.sub.7)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(COO-n-C.sub.3H.sub.7)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(COO-n-C.sub.3H.sub.7).sub.2,
--C(CH.sub.3).dbd.CH--CH- .dbd.CH--COOH,
--C(CH.sub.3).dbd.CH--CH.dbd.CH--CO--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CH.dbd.CH--CO--OC.sub.2H.sub.5,
--C(CH.sub.3)--CH--CH.dbd.C(COOCH.sub.3).sub.2,
--C(CH.sub.3).dbd.CH--CH.- dbd.C(CN)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CH.dbd.C(CN)--CO--OC.sub.2- H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(CN)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(CN)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(CH.sub.3)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(Cl)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(Br)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(CH.sub.3)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(Cl)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(Br)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(CN)--CO--NH.sub.2,
--C(CH.sub.3).dbd.C(CH.sub.3)--CH.dbd.C(CN)--CO--NH--CH.sub.3,
--C(CH.sub.3).dbd.CH--(CH.sub.2).sub.2--COOH,
--C(CH.sub.3).dbd.CH--(CH.s- ub.2).sub.2--CO--OCH.sub.3,
--C(CH.sub.3).dbd.CH--(CH.sub.2).sub.2--CO--OC- .sub.2H.sub.5,
--C(CH.sub.3).dbd.CH--CH.sub.2--CH(COOCH.sub.3).sub.2,
--C(CH.sub.3).dbd.CH--CH.sub.2--CH(COOC.sub.2H.sub.5).sub.2,
--C(CH.sub.3).dbd.CH--CH.sub.2--CH(CN)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CH.sub.2--CH(CN)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.CH--CH.sub.2--CH(CH.sub.3)--CO--OCH.sub.3,
--C(CH.sub.3).dbd.CH--CH.sub.2--CH(CH.sub.3)--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.CH--(CH.sub.2).sub.2--CO--NH.sub.2,
--C(CH.sub.3).dbd.CH--(CH.sub.2).sub.2--CO--NH--CH.sub.3,
--C(CH.sub.3).dbd.CH--CH.sub.2--COOH,
--C(CH.sub.3).dbd.CH--CH.sub.2--CO-- -OCH.sub.3,
--C(CH.sub.3).dbd.CH--CH.sub.2--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.C(COOCH.sub.3)--CH.sub.2--CO--OCH.sub.3,
--C(CH.sub.3).dbd.C(COOCH.sub.3) --CH.sub.2--CO--OC.sub.2H.sub.5,
--C(CH.sub.3).dbd.CH--CH.sub.2--CO--NH.sub.2,
--C(CH.sub.3).dbd.CH--CH.su- b.2--CO--NH--CH.sub.3,
--C(CH.sub.3).dbd.CH--CH.sub.2--CO--N(CH.sub.3).sub- .2.
[0066] Compounds I in which X.sup.1 and X.sup.2 are each oxygen,
R.sup.1 is halogen, R.sup.2 is hydrogen or fluorine, R.sup.3 and
R.sup.4 are each C.sub.1-C.sub.6-alkyl or partially or completely-
halogenated C.sub.1- or C.sub.2-alkyl and R.sup.5 is hydrogen, or
R.sup.4 and R.sup.5 together form a tetramethylene chain, are very
particularly preferred.
[0067] The substituted .sub.3-phenyluracils are obtainable by
various methods, preferably by one of the following processes:
[0068] a) Cyclization of an enamine ester of the formula II or of
an enamine-carboxylate of the formula III 14
[0069] L.sup.1 is low molecular weight alkyl, preferably
C.sub.1-C.sub.4-alkyl, or phenyl.
[0070] As a rule, the reaction is carried out in an inert solvent
or diluent, preferably in the presence of a base.
[0071] Suitable solvents or diluents are inert aprotic organic
solvents, for example aliphatic or cyclic ethers, such as
1,2-dimethoxyethane, tetrahydrofuran and dioxane, aromatic
hydrocarbons, such as benzene, toluene and xylenes, and inert polar
organic solvents, such as dimethylformamide or dimethyl sulfoxide,
or water, and the polar solvents may also be used as a mixture with
a nonpolar hydrocarbon, such as n-hexane.
[0072] Preferred bases are alkali metal alcoholates, in particular
sodium alcoholates, such as sodium methylate, and sodium ethylate,
alkali metal hydroxides, in particular sodium hydroxide and
potassium hydroxide, alkali metal carbonates, in particular sodium
carbonate and potassium carbonate, and alkali metal hydrides, in
particular sodium hydride.
[0073] When sodium hydride is used, the solvent is particularly
preferably an aliphatic or cyclic ether, such as tetrahydrofuran,
as well as dimethylformamide and dimethyl sulfoxide.
[0074] The amount of base is preferably from 0.5 to 2 times the
molar amount, based on the amount of II or III.
[0075] In general, a reaction temperature of -78.degree. C. to the
boiling point of the reaction mixture, in particular from -60 to
60.degree. C., is advisable.
[0076] Depending on the nature of the base used, products I in
which R.sup.3 is hydrogen are present, after the cyclization, in
the form of the corresponding metal salt of the general formula Ic
15
[0077] (M.sup..sym.=one equivalent of a metal ion, in particular an
alkali metal ion, such as sodium), for example in the form of the
corresponding alkali metal salt in the case of the abovementioned
preferred bases containing an alkali metal. The salt can be
isolated and purified in a conventional manner, for example by
recrystallization.
[0078] Products I in which R.sup.3 is hydrogen are obtained by
acidifying the reaction mixture obtained after the cyclization, for
example with hydrochloric acid.
[0079] b) Alkylation or acylation of a substituted 3-phenyl-uracil
I in which R.sup.3 is hydrogen 16
[0080] The alkylation is usually carried out with a halide,
preferably with the chloride or bromide, or with the sulfate of an
alkane, of an alkene, of an alkyne, of a cycloalkane, of a
cyanoalkane, of a haloalkane, of a phenylalkane or of an
alkoxyalkane.
[0081] Examples of suitable acylating agents are formyl halides,
alkanecarbonyl halides or alkoxycarbonyl halides, the chlorides and
bromides being preferred in each case.
[0082] The alkylation is advantageously carried out in the presence
of an inert organic solvent and of a base, for example in a protic
solvent, such as a lower alcohol, preferably ethanol, if necessary
as a mixture with water, or in an aprotic solvent, such as an
aliphatic or cyclic ether, preferably 1,2-dimethoxyethane,
tetrahydrofuran or dioxane, an aliphatic ketone, preferably
acetone, an amide, preferably dimethylformamide, or a sulfoxide,
preferably dimethyl sulfoxide.
[0083] Examples of suitable bases are alcoholates, such as sodium
methylate, sodium ethylate and potassium tert-butylate, hydroxides,
such as sodium hydroxide, potassium hydroxide and calcium
hydroxide, carbonates, such as sodium carbonate and potassium
carbonate, and alkali metal hydrides, such as sodium hydride.
[0084] In a particularly preferred embodiment, the cyclization
product (method a) present as a salt is alkylated without prior
isolation from the reaction mixture, and in this case excess base,
for example sodium hydride, a sodium alcoholate or sodium
carbonate, originating from the cyclization of the compound II or
III may also be present. However, this base has no adverse effect;
if desired, a further amount of the diluent which was also used for
the cyclization of the compound II or III may also be added.
[0085] The acylation with a halide can be carried out in a similar
manner, the reaction particularly preferably being carried out in
this case in an aprotic solvent and in the presence of sodium
hydride as base.
[0086] The reaction temperature is in general from 0 to about
100.degree. C., preferably from 0 to 40.degree. C.
[0087] If they cannot be prepared directly by the cyclization under
basic conditions, described as method
[0088] a), the salts of the compounds I in which R.sup.3 is
hydrogen can also be obtained in a conventional manner from the
products of the present method d). For this purpose, for example,
the substituted 3-phenyluracil I in which R.sup.3 is hydrogen is
added to the aqueous solution of an inorganic or an organic base.
The salt formation usually takes place at a sufficient rate at as
low as 20-25.degree. C.
[0089] It is particularly advantageous to prepare the sodium salt
by dissolving the 3-phenyluracil I (R.sup.3=hydrogen) in aqueous
sodium hydroxide solution at 20-25.degree. C., equivalent amounts
of 3-phenyluracil and sodium hydroxide being used. The salt of the
3-phenyluracil can then be isolated, for example, by precipitation
with a suitable inert solvent or by evaporating off the
solvent.
[0090] Salts of the 3-phenyluracils whose metal ion is not an
alkali metal ion can usually be prepared by double decomposition of
the corresponding alkali metal salt in aqueous solution.
Water-insoluble metal salts of 3-phenyluracil can generally be
prepared in this manner.
[0091] c) Substitution of a halogen atom in the phenyl moiety of
the substituted 3-phenyluracils I (Rl .dbd.halogen) by the cyano
group 17
[0092] Hal is halogen, preferably chlorine or bromine.
[0093] The reaction is advantageously carried out in the presence
of an aprotic, polar solvent, for example of an alkylnitrile, such
as acetonitrile, propionitrile or butyronitrile, of an alkylurea
such as N, N, N', N'-tetra-methylurea, of a dialkylamide, such as
dimethylformamide, or of a dialkyl sulfoxide, such as dimethyl
sulfoxide, or in N-methyl-2-pyrrolidone,
1,2-dimethylimidazolidin-2-one, 1,2-dimethyl-3, 4, 5,
6-tetrahydro-2(1H)-pyrimidinone or hexamethylphosphorotriamide.
[0094] The reaction is usually carried out using a metal cyanide,
in particular a transition metal cyanide, such as copper(I)
cyanide, at elevated temperatures, preferably at from 150 to
250.degree. C.
[0095] The starting materials are advantageously used in
stoichiometric amounts, but an excess of metal cyanide, for example
up to 4 times the molar amount (based on the amount of starting
material I in which R.sup.1 is halogen), may also be
advantageous.
[0096] d) Conversion of a pyrimidinone derivate of the formula IVa
or IVb into an enol ether Ia or Ib 18
[0097] Hal is chlorine or bromine;
[0098] Me.sup..sym. is one equivalent of a metal ion, in particular
of a transition metal ion, of an alkali metal ion, such as sodium
or potassium, or of an alkaline earth metal ion, such as potassium
or magnesium. Sodium is particularly preferred.
[0099] The reaction of the pyrimidinone derivatives IVa or IVb with
alkanols, alkenols, alkynols (R.sup.3'--OH) or alkanethiols,
alkenethiols or alkynethiols (R.sup.3'--SH) is advantageously
carried out in the presence of an organic base, pyridine being
particularly preferred.
[0100] The amount of base is not critical; usually, from 0.5 to 2
times the molar amount, based on the amount of IVa or IVb, is
sufficient.
[0101] The reactions of IVa with H--X.sup.1--R.sup.3' and of IVb
with H--X.sup.2--R.sup.3' can be carried out either in the absence
of a solvent in an excess of R.sup.3'--OH or R.sup.3'--SH or in a
suitable inert organic solvent, for example in an aromatic, such as
toluene or xylene, in an ether, such as diethyl ether,
tetrahydrofuran or 1,2-dimethoxyethane, or in a halo-hydrocarbon,
such as dichloromethane or chlorobenzene.
[0102] When the compound R.sup.3'--OH is used, the reaction is
preferably carried out in the absence of a solvent, using from 1 to
about 150 times the amount, based on the amount of pyrimidinone
derivative IVa or IVb, of R.sup.3'--OH.
[0103] In the reaction with a salt of the formula M.sup..sym.
.sup..crclbar.O--R.sup.3' or M.sup..sym. .sup..crclbar.S--R.sup.3',
it is advisable to use equimolar amounts of pyrimidinone derivative
and salt, but an excess of the salt of up to about 20 mol % (based
on the amount of pyrimidinone derivative) may also be
advantageous.
[0104] A reaction temperature of from 0 to 50.degree. C.,
preferably from 10 to 30.degree. C., is usually sufficient.
[0105] e) Acetalation of a compound I in which W is
--C(.dbd.O)--R.sup.8 19
[0106] The acetalation is generally carried out in an inert aprotic
organic solvent, for example in an aliphatic or cyclic ether, such
as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or dioxane,
in an aromatic hydrocarbon, such as benzene or toluene, o-, m-or
p-xylene or mesitylene, or in a chlorohydrocarbon, such as
methylene chloride, chloroform or chlorobenzene, unless it is
effected in the absence of a solvent in an excess of
H--X.sub.3R.sup.6, H--X.sup.4R.sub.7 or
H--X.sup.3(R.sup.6R.sup.7)X.sup.4--H.
[0107] Any water of reaction formed can be removed in a
conventional manner from the reaction mixture, for example by means
of a water separator.
[0108] The acetalation is preferably carried out in the presence of
an organic acid, such as p-toluenesulfonic acid, and/or of a Lewis
acid, such as tin tetrachloride, tin(II) chloride, iron(III)
chloride, tellurium tetrachloride or boron trifluoroetherate, or of
a suitable catalyst, such as montmorillonite K .sub.10, the amount
of acid usually being from .sub.0.5 to 100 mol %, based on the
amount of starting material to be acetalated.
[0109] The ratios are not critical. For complete conversion, all
reactants are used in about a stoichiometric ratio, but an excess
of H--X.sup.3R.sup.6 and H--X.sup.4R.sup.7 or H--X.sup.3
(R.sup.6R.sup.7)X.sup.4--H is preferably used.
[0110] If the starting materials H--X.sup.3R.sup.6 and
H--X.sup.4R.sup.7 or H--X.sup.3 (R.sub.6R.sup.7)X.sup.4--H are used
simultaneously as diluents, they are present in a larger
excess.
[0111] The reactions are carried out in general at from -78 to
180.degree. C., preferably from -40 to 150.degree. C.
[0112] If product mixtures are obtained, for example when R.sup.6
and R.sup.7 do not form a common radical and X.sup.3R.sup.6 and
X.sup.4R.sup.7 are not identical, they can, if desired, be purified
and separated by conventional methods, such as crystallization and
chromatography.
[0113] In particular, compounds of the formula I where W is
--C(R.sup.8)(X.sup.3R.sup.6)(X.sup.4R.sup.7), R.sup.6 and R.sup.7
do not form a common radical and X.sup.3R.sup.6 and X.sup.4R.sup.7
are not identical can also be prepared by other methods known from
the literature (cf. for example Tetrahedron Lett. 32 (1991),
467-470, and the literature cited there).
[0114] In some cases it may also be advantageous to carry out the
acetalation via the circuitous route of acetalation to give the
dialkyl acetal, preferably dimethyl acetal, and subsequent
transacetalation in the presence of a suitable catalyst. The
solvents used for the transacetalation, the catalysts and other
reaction conditions correspond to those already mentioned above for
the acetalation.
[0115] A further novel variant is the reaction of a compound I
(W.dbd.CHO) with a reactive derivative R.sup.2C(X.sup.3R.sup.6)
(X.sup.4R.sup.7) under transacetalation conditions (for conditions
see above). Examples of suitable reactive derivatives are acetals
and ortho-esters.
[0116] f) Acetal cleavage of a compound I in which W is
--C(R.sup.8) (X.sup.3R.sup.6) (X.sup.4R.sup.7) 20
[0117] The acetal cleavage can be carried out without the addition
of an acid, in the presence of an acid, for example of a mineral
acid, such as hydrochloric acid and sulfuric acid, or of an organic
carboxylic acid, such as formic acid, acetic acid, oxalic acid or
trifluoroacetic acid, in the presence of an acidic ion exchanger,
such as Amberlite.RTM. (trade mark of Aldrich) IR120 or IRC84, or
in the presence of a transition metal salt, such as mercury(II)
oxide, copper(I) oxide or iron(III) chloride.
[0118] Examples of suitable solvents or diluents are aromatics,
such as benzene, toluene and o-, m- and p-xylene, aliphatic or
cyclic ethers, such as 1,2-dimethoxyethane, diethyl ether,
tetrahydrofuran and dioxane, alcohols, such as methanol, ethanol
and iso-propanol, polar organic solvents, such as
dimethylformamide, dimethyl sulfoxide and acetonitrile, ketones,
such as acetone and butanone, and water.
[0119] The reaction is preferably carried out in the absence of a
solvent in an excess of the acid used for the acetal cleavage,
formic acid being particularly preferred.
[0120] For complete conversion, the starting materials I, in which
W is --C(R.sup.8) (X.sup.3R.sup.6) (X.sup.4R.sup.7) and
H.sub.2X.sup.5 are used in at least a stoichiometric ratio, but an
excess of H.sub.2X.sup.5 of up to about .sub.200 mol % is also
possible.
[0121] The amount of acid, ion exchanger or transition metal salt
is not critical. In general, up to about 300 mol %, based on the
amount of H.sub.2X.sup.5, is sufficient.
[0122] As a rule, the reaction temperature is from -78 to
180.degree. C., preferably from 0.degree. C. to the boiling point
of the particular diluent.
[0123] Further methods which can be used for the preparation of the
substituted 3-phenyluracils I are described in Houben-Weyl,
Handbuch der Org. Chemie, 4th Edition, Vol. E3, page .sub.362 et
seq.
[0124] g) Olefination of compounds I (W.ident.C(R.sup.8).dbd.O)
21
[0125] The reaction can be carried out using the following
phosphorylides Va to Vd, phosphonium salts VIa to VId and
phosphonates VIIa to VIId:
15 Phospho- R.sup.3P.dbd.C(R.sup.9)--CO--R.sup.10 Va, rylides V:
R.sup.3P.dbd.C(R.sup.9)--CH.sub.2--CO--R.sup.10 Vb,
R.sup.3P.dbd.C(R.sup.9)--C(R.sup.11).dbd.C(R.sup.12)--CO--R.sup.10
Vc, R.sup.3P.dbd.C(R.sup.9)--CH.sub.2--CH(R.sup.13)--CO--R.sup.10
Vd; Phospho- R.sub.3P.sup..sym.--CH(R.sup.9)--CO--R.sup.10
Hal.sup..crclbar. VIa, nium R.sub.3P.sup..sym.--CH(R.sup.9)--CH.su-
b.2--CO--R.sup.10 Hal.sup..crclbar. VIb, salts VI:
R.sub.3P.sup..sym.--CH(R.sup.9)--CR.sup.11.dbd.CR.sup.12--CO--R.sup.10
Hal.sup..crclbar. VIc, R.sub.3P.sup..sym.--CH(R.sup.9)--CH.sub.2--
-CHR.sup.13--CO--R.sup.10 Hal.sup..crclbar. VId; Phospho-
(RO).sub.2PO--CH(R.sup.9)--CO--R.sup.10 VIIa, nates VII:
(RO).sub.2PO--CH(R.sup.9)--CH.sub.2--CO--R.sup.10 VIIb,
(RO).sub.2PO--CH(R.sup.9)--CR.sup.11.dbd.CR.sup.12--CO--R.sup.10
VIIc, (RO).sub.2PO--CH(R.sup.9)--CH.sub.2--CHR.sup.13--CO--R.sup.10
VIId.
[0126] Those phosphorylides Vb and Vd, phosphonium salts VIb and
VId and phosphonates VIlb and VIId in which R.sup.10 is hydrogen,
alkyl or cycloalkyl are not very suitable.
[0127] The radicals R on the phosphorus may be identical or
different and are, for example, branched or straight-chain
C.sub.1--C.sub.8-alkyl, C.sub.5- or C.sub.6-cycloalkyl and in
particular phenyl which may carry further substituents which are
inert for the reaction, for example C.sub.1-C.sub.4-alkyl, such as
methyl, ethyl or tert-butyl, C.sub.1-C.sub.4-alkoxy, such as
methoxy, or halogen, such as fluorine, chlorine or bromine.
Unsubstituted phenyl radicals are preferred since the starting
material triphenylphosphine used for the preparation of the
phosphorylides V and phosphonium salts VI is particularly
economical and furthermore the very unreactive, solid
triphenylphosphine oxide which can be readily separated off is
formed in the reactions.
[0128] For example, the methods described in Houben-Weyl, Methoden
der Organischen Chemie, Volume E2, 1982, page 345 et seq. are
suitable for the preparation of the phosphonates VII.
[0129] Suitable solvents are inert organic solvents, for example
aromatics, such as toluene and o-, m- and p-xylene, ethers, such as
1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane,
polar organic solvents, such as dimethylformamide and dimethyl
sulfoxide, or alcohols, such as methanol, ethanol and
isopropanol.
[0130] In the olefination of I where W is --C(R.sup.8).dbd.O with a
phosphonium salt VI or a phosphonate VII, the reaction is carried
out in the presence of a base, alkali metal alkyls, such as
n-butyllithium, alkali metal hydrides and alcoholates, such as
sodium hydride, sodium ethylate and potassium tert-butylate, and
alkali metal and alkaline earth metal hydroxides, such as calcium
hydroxide, being particularly suitable.
[0131] For complete conversion, all reactants are used in about a
stoichiometric ratio, but an excess of base of about 10 mol % is
preferably used.
[0132] In general, the reaction temperature is from -40 to
150.degree. C.
[0133] The compounds of the formulae V, VI and VII are known or can
be prepared by known methods (cf. for example Houben-Weyl, Methoden
d. Org. Chemie, Vol. E1, page 636 et seq., Georg Thieme Verlag,
Stuttgart, 1982, ibid. Vol. E2, page 345 et seq. and Chem. Ber. 95
(1962), 3993).
[0134] A further possibility for the preparation of 3-phenyluracils
I where W is --CR.sup.8.dbd.CR.sup.9--CO--R.sup.10 and R.sup.10 is
hydrogen, alkyl, alkenyl, haloalkyl, cycloalkyl, phenyl or
alkoxyalkyl is the conventional aldol condensation. Suitable
conditions for this purpose are described in, for example, Nielsen,
Org. React. 16 (1968), 1 et seq.
[0135] Suitable further methods for synthesizing compounds of the
formula I where W is --C(R.sup.8).dbd.C(R.sup.9)--CO--R.sup.10,
--CH (R.sup.8).dbd.CH (R.sup.9)--CO--R.sup.10,
--CR.sup.8.dbd.CR.sup.11--CH.su- b.2--CO--R.sup.12,
--CR.sup.8.dbd.CR.sup.11--CR.sup.13.dbd.CR.sup.14--CO--- R.sup.10
or --CR.sup.8.dbd.CR.sup.11--CH.sub.2--CHR.sup.15--CO--R.sup.12,
and R.sup.9 or R.sup.11 is hydrogen, cyano, alkoxycarbonyl or
alkylcarbonyl are both the Knoevenagel condensation and the Perkin
condensation. Suitable conditions are described in, for example,
Org. React. 15 (1967), 204 et seq. (Knoevenagel) or Johnson, Org.
React. 1 (1942), 210 et seq. (Perkin).
[0136] Compounds in which R.sup.10 is --NR.sup.8R.sup.9 or
--SR.sup.17 can be prepared, for example, in a conventional manner
by converting compounds in which R.sup.10 is hydroxyl into the
corresponding acyl halides (R.sup.10 is halogen) and subsequently
reacting the products with a corresponding amine
H--NR.sup.18R.sup.19 or thiol H--SR.sup.17 or with a reactive
derivative of these compounds.
[0137] h) Reaction of compounds I (W.ident.C(R.sup.8).dbd.O) with
amines, hydroxylamines or hydrazines 22
[0138] The reaction is usually carried out in an inert organic
solvent or diluent, for example in an aromatic, such as toluene or
xylene, in a chlorohydrocarbon, such as dichloromethane, chloroform
or chlorobenzene, in an ether, such as diethyl ether,
1,2-dimethoxyethane or tetrahydrofuran, in an alcohol, such as
methanol or ethanol, or in a mixture of the stated solvents.
[0139] If the amines H.sub.2N--R.sup.4 are in the form of salts,
for example as hydrochlorides or oxalates, the addition of a base,
preferably sodium carbonate, potassium carbonate, sodium
bicarbonate, triethylamine or pyridine, is preferable for their
liberation.
[0140] The resulting water of reaction can, if desired, be removed
from the reaction mixture by distillation or with the aid of a
water separator.
[0141] The reaction temperature is usually from -30 to 150.degree.
C., preferably from 0 to 130.degree. C.
[0142] i) Cleavage of compounds I where W is
--C(R.sup.8).dbd.N--R.sup.14 23
[0143] The cleavage reaction is carried out in the absence of a
solvent or in an inert solvent or diluent with water or a reactive
derivative of water.
[0144] The reaction can be carried out by hydrolysis or under
oxidative conditions, a reaction temperature of from -78 to
180.degree. C., preferably from 0.degree. C. to the boiling point
of the diluent being preferable.
[0145] Examples of suitable solvents or diluents are aromatics,
such as benzene, toluene and o-, m- and p-xylene, chlorinated
hydrocarbons, such as dichloromethane, chloroform and
chlorobenzene, ethers, such as dialkyl ether, 1,2-dimethoxyethane,
tetrahydrofuran and dioxane, alcohols, such as methanol and
ethanol, ketones, such as acetone, esters of organic acids, such as
ethyl acetate, or water and mixtures of the stated solvents.
[0146] The reaction is advantageously carried out in the presence
of a mineral acid, such as hydrochloric acid, hydrobromic acid or
sulfuric acid, of a carboxylic acid, such as acetic acid or
trifluoroacetic acid, or of a sulfonic acid, such as
p-toluenesulfonic acid.
[0147] To trap the H.sub.2N--R.sup.14 obtained in the hydrolysis or
to remove it from the equilibrium, it may be advantageous to carry
out the reaction in the presence of another carbonyl compound, for
example acetone, formaldehyde, glyoxylic acid or phenylglyoxylic
acid, preferably formaldehyde, which forms a more stable compound
with H.sub.2N--R.sup.14 than I (W.dbd.CHO).
[0148] In the procedure under oxidative conditions, oxidizing
agents such as lead tetraacetate, sodium hypochloride and hydrogen
peroxide are particularly suitable.
[0149] If desired, the reaction may additionally be carried out in
the presence of a catalyst, such as copper(II) sulfate, titanium
tetrachloride or boron trifluoroetherate.
[0150] The amounts of acid, oxidizing agent and catalyst may be
varied within wide limits. Usually, both the amount of acid and the
amount of catalyst are from 5 to 200 mol % and the amount of
oxidizing agent is from 25 to 400 mol %, based on the amount of the
compound to be oxidized, but they may also be used in a
considerably larger excess.
[0151] k) Reaction of a substituted 3-phenyluracil I in which
X.sup.2 is oxygen with a sulfurization reagent 24
[0152] The reaction is carried out as a rule in an inert solvent,
for example in an aromatic hydrocarbon, such as toluene or o-, m-
or p-xylene, in an ether, such as diethyl ether,
1,2-dimethoxyethane or tetrahydrofuran, or in an organic amine,
such as pyridine.
[0153] Particularly suitable sulfurization reagents are
phosphorus(V) sulfide and 2,4-bis-(4-methoxyphenyl)-1, 3, 2,
4-dithiadiphosphetane-2,4-- dithione (Lawesson's reagent).
[0154] The amount of sulfurization reagent is not critical; from 1
to 5 times the molar amount, based on the 3-phenyluracil to be
sulfurized, is usually used.
[0155] The reaction temperature is usually from 20 to 200.degree.
C., preferably from 40.degree. C. to the boiling point of the
solvent.
[0156] l) Halogenation of a substituted 3-phenyluracil I in which
R.sup.5 is hydrogen 25
[0157] The halogenation is carried out as a rule in an inert
organic solvent or diluent. For example, aliphatic carboxylic
acids, such as acetic acid, or chlorinated aliphatic hydrocarbons,
such as methylene chloride, chloroform and carbon tetrachloride,
are suitable for the chlorination and bromination. Low boiling
aliphatic carboxylic acids, such as acetic acid, are particularly
preferred for the iodination.
[0158] Elemental chlorine or bromine and sulfuryl chloride or
sulfuryl bromide are particularly suitable for the chlorination and
bromination, a reaction temperature of from 0 to 60.degree. C.,
preferably from 10 to 30.degree. C., being preferable.
[0159] If desired, the chlorination and bromination can be carried
out in the presence of an acid acceptor, sodium acetate and
tertiary amines, such as triethylamine, dimethylaniline and
pyridine, being particularly preferred.
[0160] Elemental iodine is a particularly preferred iodinating
agent, and in this case the reaction temperature is from 0 to
110.degree. C., preferably from 10 to 30.degree. C.
[0161] The iodination is particularly advantageously carried out in
the presence of a mineral acid, such as fuming nitric acid.
[0162] The amount of halogenating agent is not critical; equimolar
amounts of halogenating agent or an excess of up to about 200 mol
%, based on the starting material to be halogenated, are usually
used.
[0163] Excess iodine can be removed by means of saturated aqueous
sodium bisulfite solution, for example after the reaction.
[0164] m) Reduction of a substituted 3-phenyluracil I in which W is
cyano 26
[0165] The reaction is advantageously carried out in an inert
organic solvent, for example an aromatic, such as toluene or o-, m-
or p-xylene, an aliphatic or cyclic ether, such as diethyl ether,
tert-butyl methyl ether, tetrahydrofuran or dioxane, a
chlorohydrocarbon, such as methylene chloride, chloroform or
chlorobenzene, or in an organic carboxylic acid, such as formic
acid.
[0166] Examples of suitable reducing agents are hydrogen or metal
salts, such as tin(II) chloride, metal hydrides, such as
diisobutylaluminum hydride, diisopropylaluminum hyride,
lithiumtrisethoxyaluminum hydride and lithiumbisethoxyaluminum
hyride, or triethylsilane. Diisobutylaluminum hydride, formic acid
or hydrogen is preferably used.
[0167] If desired, the reduction can be carried out in the presence
of a catalyst, such as triethyloxonium tetrafluoroborate or Raney
nickel.
[0168] If the reaction is carried out in the absence of a diluent
in formic acid as a reducing agent, the latter may also be present
in a relatively large excess.
[0169] The most advantageous reaction temperature is dependent on
the particular reducing agent but is in general from -78 to
150.degree. C.
[0170] n) Phosgenation or thiophosgenation of an enamine amide of
the formula VIII 27
[0171] The process can be carried out in an inert organic solvent
with the aid of a suitable phosgenating or thiophosgenating agent,
eg. phosgene, thiophosgene, trichloromethyl chloroformate or
1,1'-carbonyldiimidazole, in the presence or absence of a base,
such as an organic nitrogen base, eg. triethylamine, pyridine or
2,6-lutidine, at from -20 to 130.degree. C., preferably from
0.degree. C. to the reflux temperature of the solvent used.
[0172] Particularly suitable solvents or diluents are aprotic,
organic solvents, for example aromatics, such as toluene and o-, m-
and p-xylene, halohydrocarbons, such as methylene chloride,
chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or
cyclic ethers, such as 1,2-dimethoxyethane, tetrahydrofuran and
dioxane, or esters, such as ethyl acetate, and, particularly where
X.sup.1 is sulfur, water, as well as mixtures of these
solvents.
[0173] The amount of the phosgenating or thiophosgenating agent is
not critical and is usually from 0.9 to 1.3 times the molar amount
(based on VIII), but may also be substantially higher (200-500 mol
%) in certain cases.
[0174] o) Meerwein alkylation of a diazonium salt IXb 28
[0175] The reaction conditions of the Meerwein reaction are known
to the skilled worker (cf. for example M. P. Doyle et al., J. Org.
Chem. 42 (1977), 2431; G. Theodoridis et al., J. Heterocyclic Chem.
28 (1991), 849; C. S. Rondestvedt Jr., Org. React. 24 (1976), 225
and the literature cited there) and can be applied to the novel
compounds I in analogy to the compounds described in the
literature.
[0176] p) Metal-catalyzed olef in coupling with a phenyl halide of
the formula IXc 29
[0177] The conditions of this Heck or Heck-like reaction are known
to the skilled worker and can be applied to the novel compounds I
in analogy to the compounds described in the literature (cf. for
example Comprehensive Organic Chemistry).
[0178] The enamine esters of the formula II which are required as
starting materials are novel unless W is --CH.dbd.CH--CO--OR.sup.14
where R.sup.14 is C.sub.1-C.sub.6-alkyl or C.sub.3--C.sub.6-alkenyl
when R.sup.4 is trifluoromethyl and R is hydrogen (cf. U.S. Pat.
No. 4,979,982). They can likewise be used as herbicides.
[0179] The enamine esters II can be prepared by known methods, for
example by one of the following processes: 30
[0180] The reaction is preferably carried out under essentially
anhydrous conditions in an inert solvent or diluent, particularly
preferably in the presence of an acidic or basic catalyst.
[0181] Particularly suitable solvents or diluents are organic
solvents which form an azeotropic mixture with water, for example
aromatics, such as benzene, toluene and o-, m- and p-xylene,
halohydrocarbons, such as methylene chloride, chloroform, carbon
tetrachloride and chlorobenzene, aliphatic and cyclic ethers, such
as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or
cyclohexane, as well as alcohols, such as methanol and ethanol.
[0182] Preferred acidic catalysts are strong mineral acids, such as
sulfuric acid and hydrochloric acid, phosphorus-containing acids,
such as orthophosphoric acid and polyphosphoric acid, organic
acids, such as p-toluenesulfonic acid, and acidic cation
exchangers, such as Amberlyst 15 (Fluka).
[0183] Examples of suitable basic catalysts are metal hydrides,
such as sodium hydride, and particularly preferably metal
alcoholates, such as sodium methylate and ethylate.
[0184] The .beta.-ketoester XI and the phenylurea XII are
advantageously used in a stoichiometric ratio, or a slight excess
of up to 10 mol % of one or other component is used.
[0185] From 0.5 to 100 mol %, based on the amount of a starting
material, of a catalyst is usually sufficient.
[0186] In general, the reaction is carried out at from 60 to
120.degree. C., or preferably at the boiling point of the reaction
mixture for rapid removal of water formed. 31
[0187] L.sup.3 is C.sub.1-C.sub.4-alkyl or phenyl.
[0188] This reaction can be carried out, for example, in an inert,
water-miscible, organic solvent, for example an aliphatic or cyclic
ether, such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran
or dioxane, or a lower alcohol, in particular ethanol, the reaction
temperature usually being from 50 to 150.degree. C., preferably the
boiling point of the reaction mixture.
[0189] The reaction can, however, also be carried out in an
aromatic diluent, such as benzene, toluene or o-, m-or p-xylene, in
which case the addition of either an acidic catalyst, such as
hydrochloric acid or p-toluene-sulfonic acid, or of a base, for
example of an alkali metal alcoholate, such as sodium methylate and
sodium ethylate, is preferable. In this process variant too, the
reaction temperature is usually from 50 to 150.degree. C.,
preferably from 60 to 80.degree. C. 32
[0190] The reaction is advantageously carried out in the presence
of an essentially anhydrous, aprotic, organic solvent or diluent,
for example of an aliphatic or cyclic ether, such as diethyl ether,
1,2-dimethoxyethane, tetrahydrofuran or dioxane, of an aliphatic or
aromatic hydrocarbon, such as n-hexane, benzene, toluene or o-,
m-or p-xylene, of a halogenated, aliphatic hydrocarbon, such as
methylene chloride, chloroform, carbon tetrachloride,
1,2-dichloroethane or chlorobenzene, of an aprotic, polar solvent,
such as dimethylformamide, hexamethylphosphorotriamide or dimethyl
sulfoxide, or of a mixture of the stated solvents.
[0191] If desired, the reaction can also be carried out in the
presence of a metal hydride base, such as sodium hydride or
potassium hydride, of an alkali metal or alkaline earth metal
alcoholate, such as sodium methylate, sodium ethylate or potassium
tert-butylate, or of an organic tertiary base, such as
triethylamine or pyridine, and the organic base may simultaneously
serve as a solvent.
[0192] The starting materials are advantageously used in a
stoichiometric ratio, or a slight excess of up to about 20 mol % of
one or other component is used. If the reaction is carried out in
the absence of a solvent and in the presence of an organic base,
the latter is present in a relatively large excess.
[0193] The reaction temperature is preferably from -80 to
50.degree. C., particularly preferably from -60 to 30.degree.
C.
[0194] In a particularly preferred variant of this process, the II
obtained is converted with excess base directly (ie. in situ)
into.the corresponding compound I by process variant a).
[0195] Byproducts which may occur (for example C-alkylation
products in the case of compounds in which R.sup.5 is hydrogen) can
be removed by conventional separation methods such as
crystallization and chromatography. 33
[0196] L.sup.1 and L.sup.4 are each C.sub.1-C.sub.4-alkyl or
phenyl.
[0197] This reaction is advantageously carried out in an aprotic,
polar solvent or diluent, such as dimethylformamide, 2-butanone,
dimethyl sulfoxide or acetonitrile, and advantageously in the
presence of a base, for example of an alkali metal or alkaline
earth metal alcoholate, in particular of a sodium alkanolate, such
as sodium methylate, of an alkali metal or alkaline earth metal
carbonate, in particular sodium carbonate, or of an alkali metal
hydride, such as lithium hydride or sodium hydride.
[0198] Usually, from 1 to 2 times the molar amount, based on the
amount of starting material, of base is sufficient.
[0199] The reaction temperature is in general from 80 to
180.degree. C., preferably the boiling point of the reaction
mixture.
[0200] Regarding the ratios of the starting materials, the
statements made for method q) are applicable.
[0201] In a particularly preferred embodiment, a sodium alcoholate
is used as the base, and the alcohol formed in the course of the
reaction is distilled off continuously. The enamine esters of the
formula II prepared in this manner can be cyclized to a salt of the
substituted 3-phenyluracils I by process variant a) without
isolation from the reaction mixture. 34
[0202] This reaction is advantageously carried out in the presence
of an essentially anhydrous, aprotic, organic solvent or diluent,
if desired in the presence of a metal hydride base, such as sodium
hydride and potassium hydride, or of an organic tertiary base, such
as triethylamine or pyridine, and the organic base may also serve
as the solvent.
[0203] Regarding the suitable solvents and ratios, the statements
made for method r) are applicable.
[0204] The reaction temperature is as a rule from -80 to
150.degree. C., preferably from -60.degree. C. to the particular
boiling point of the solvent. 35
[0205] The reaction is advantageously carried out in the presence
of an essentially anhydrous, aprotic organic solvent or diluent,
for example of an aliphatic or cyclic ether, such as diethyl ether,
1,2-dimethoxyethane, tetrahydrofuran and dioxane, of an aliphatic
or aromatic hydrocarbon, such as n-hexane, benzene, toluene or o-,
m-or p-xylene, of a halogenated, aliphatic hydrocarbon, such as
methylene chloride, chloroform, carbon tetrachloride,
1,2-dichloroethane or chlorobenzene, of an aprotic, polar solvent,
such as dimethylformamide, hexamethylphosphorotriamide or dimethyl
sulfoxide, or of a mixture of the stated solvents.
[0206] If desired, the reaction may also be carried out in the
presence of a metal hydride base, such as sodium hydride or
potassium hydride, of an alkali metal or alkaline earth metal
alcoholate, such as sodium methylate, sodium ethylate or potassium
tert-butylate, or of an organic tertiary base, such as
triethylamine or pyridine, and the organic base may simultaneously
serve as the solvent.
[0207] The starting materials are advantageously used in a
stoichiometric ratio, or a slight excess of up to about 20 mol % of
one or other component is used. If the reaction is carried out in
the absence of a solvent and in the presence of an organic base,
the latter is present in a relatively large excess.
[0208] The reaction temperature is preferably from -80 to
150.degree. C., particularly preferably from -30 to the reflux
temperature of the solvent used.
[0209] The enamine-carboxylates of the formula III are likewise
novel and can be used as herbicides. They can be prepared by
conventional processes, for example from an aniline derivative of
the formula XVI according to the following reaction scheme: 36
[0210] In equation (G11), R.sup.4' and R.sup.5' are each hydrogen
or C.sub.1-C.sub.4-alkyl.
[0211] The reactions according to equations 1 and 2 are preferably
carried out in an anhydrous inert aprotic solvent, for example in a
halohydrocarbon, such as methylene chloride, chloroform, carbon
tetrachloride or chlorobenzene, an aromatic hydrocarbon, such as
benzene, toluene or o-, m- or p-xylene, or an aliphatic or cyclic
ether, such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane,
tetrahydrofuran and dioxane.
[0212] For the reaction of the lactone XX with the aniline
derivative XIX according to equation (G11), it is preferable to add
a basic catalyst, eg. 4-pyrrolidinopyridine,
4-dimethylaminopyridine, 1,2-diazabicyclo-[2. 2. 2]octane,
1,5-diazabicyclo[4. 3. 0]non-5-ene, 1,8-diazabicyclo[5. 4.
0]undec-7-ene or diethylamine.
[0213] Since the reaction is exothermic, a reaction temperature of
from -10 to 50.degree. C., preferably from 10 to 30.degree. C., is
generally sufficient.
[0214] For the reaction of the compounds of the formulae XXII and
XIX with one another according to equation (G12), on the other
hand, higher temperatures, for example from 70 to 140.degree. C.,
in particular from 100 to 120.degree. C., are advantageous.
[0215] The reaction according to equation (G13) is an aminolysis,
which, as a rule, is carried out either in the absence of a solvent
(cf. for example J. Soc. Dyes Col. 42 (1926), 81, Ber. 64 (1931),
970; Org. Synth., Coll. Vol. IV (1963), 80 and J. Am. Chem. Soc. 70
(1948), 2402] or in an inert anhydrous solvent or diluent, in
partiuclar in an aprotic solvent, for example in an aromatic or
haloaromatic, such as toluene, o-, m- or p-xylene or
chlorobenzene.
[0216] It is advisable here to carry out the reaction in the
presence of a basic catalyst, for example of a relatively high
boiling amine (cf. for example Helv. Chim. Acta 11 (1928), 779 and
U.S. Pat. No. 2,416,738] or pyridine.
[0217] The reaction temperature is preferably from about 20 to
160.degree. C.
[0218] In all three preparation variants, the starting materials
are advantageously used in a stoichiometric ratio, or a slight
excess of up to about 10 mol % of one or other component is used.
If the reaction is carried out in the presence of a basic catalyst,
from 0.5 to 200 mol %, based on the amount of a starting material,
is generally sufficient.
[0219] The subsequent reaction of the resulting compounds of the
formula XXI with the compound H.sub.2N--COOL.sup.1 is
advantageously carried out in a substantially anhydrous solvent or
diluent at atmospheric pressure, particularly preferably in the
presence of an acidic catalyst.
[0220] Particularly suitable solvents or diluents are organic
liquids which form azeotropic mixtures with water, for example
aromatics, such as benzene, toluene and o-, m- and p-xylene, and
halohydrocarbons, such as carbon tetrachloride and
chlorobenzene.
[0221] Particularly suitable catalysts are strong mineral acids,
such as sulfuric acid, organic acids, such as p-toluenesulfonic
acid, phosphorus-containing acids, such as orthophosphoric acid and
polyphosphoric acid, and acidic cation exchangers, such as
Amberlyst 15 (Fluka).
[0222] In general, the reaction temperature is from about 70 to
150.degree. C.; for rapid removal of the resulting water of
reaction, however, the reaction is advantageously carried out at
the boiling point of the solvent.
[0223] w) The pyrimidinone derivatives IVa and IVb, which are used
as starting materials in method d), can be obtained by
halogenation, preferably chlorination or bromination, of
3-phenyluracils I in which R.sup.3 is hydrogen, in the absence of a
solvent or in the presence of an inert solvent or diluent.
[0224] Particularly suitable solvents or diluents are aprotic
organic liquids, for example aliphatic or aromatic hydrocarbons,
such as n-hexane, benzene, toluene and o-, m- and p-xylene,
halogenated aliphatic hydrocarbons, such as methylene chloride,
chloroform and 1,2-dichloroethane, halogenated aromatic
hydrocarbons, such as chlorobenzene, or tertiary amines, such as
N,N-dimethylaniline.
[0225] Particularly suitable halogenating agents are thionyl
chloride, phosphorus pentachloride, phosphoryl chloride, phosphorus
pentabromide and phosphoryl bromide. A mixture of phosphorus
pentachloride and phosphoryl chloride or of phosphorus pentabromide
and phosphoryl bromide can also be particularly advantageous.
[0226] In most cases, it is preferable to add a catalytic amount of
dimethylformamide or of an alkylated aniline derivative.
[0227] The amount of halogenating agent is not critical; for
complete conversion, at least equimolar amounts of halogenating
agent and of the educt to be halogenated are required. However, a
1-fold to 8-fold molar excess of halogenating agent may also be
advantageous.
[0228] The reaction temperatures are in general from 0.degree. C.
to the reflux temperature of the reaction mixture, preferably from
20 to 120.degree. C.
[0229] x) C-Acylation of an enamine of the formula XXIV with an
isocyanate or isothiocyanate of the formula XII 37
[0230] The reaction is advantageously carried out in the presence
of an essentially anhydrous, aprotic organic solvent or diluent,
for example of an aliphatic or cyclic ether, such as diethyl ether,
1,2-dimethoxyethane, tetrahydrofuran and dioxane, of an aliphatic
or aromatic hydrocarbon, such as n-hexane, benzene, toluene or o-,
m-or p-xylene, of a halogenated, aliphatic hydrocarbon, such as
methylene chloride, chloroform, carbon tetrachloride,
1,2-dichloroethane or chlorobenzene, of an aprotic, polar solvent,
such as dimethylformamide, hexamethylphosphorotriamide or dimethyl
sulfoxide, or of a mixture of the stated solvents.
[0231] If desired, the reaction can also be carried out in the
presence of an organic tertiary base, such as triethylamine or
pyridine, and the organic base may simultaneously serve as the
solvent.
[0232] The starting materials are advantageously used in a
stoichiometric ratio, or a slight excess of up to about 20 mol % of
one or other component is used. If the reaction is carried out in
the absence of a solvent and in the presence of an organic base,
the latter is present in a relatively large excess.
[0233] The reaction temperature is preferably from -80 to
150.degree. C., particularly preferably from -30.degree. C. to the
reflux temperature of the solvent used.
[0234] The byproduct frequently obtained in this reaction
(acylation at the nitrogen, cf. process variant s)) can be
separated off in a conventional manner, for example by
crystallization or chromatography.
[0235] The compounds of the formulae IX, XII, XIII and XIV are
likewise novel. They can be prepared by conventional methods,
particularly advantageously from compounds of the formula XVI: By
phosgenation and hydrolysis of the products with ammonia 38
[0236] The process can be carried out in an inert, essentially
anhydrous solvent or diluent or in the absence of a solvent, the
compounds XIX preferably being reacted with phosgene or
trichloromethyl chloroformate.
[0237] Particularly suitable solvents or diluents are aprotic,
organic solvents, for example aromatics, such as toluene and o-, m-
and p-xylene, halohydrocarbons, such as methylene chloride,
chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or
cyclic ethers, such as 1,2-dimethoxyethane, tetrahydrofuran and
dioxane, and esters, such as ethyl acetate, as well as mixtures of
these solvents.
[0238] Depending on the aniline derivative XIX used, the addition
of a base, such as triethylamine, may be advantageous, for example
in from 0.5 to 2 times the molar amount, based on the amount of
XIX.
[0239] By choosing suitable reaction conditions, both the carbamoyl
chlorides XVII and the phenylisocyanates XIV can be obtained: Thus,
the carbamoyl chlorides XVII are usually obtained at low
temperatures of from about -40 to 50.degree. C., whereas a further
increase in the temperature up to the boiling point of the reaction
mixture leads predominantly to the formation of the
phenylisocyanates XIV, which can be reacted with ammonia or with a
reactive derivative of ammonia to give the phenylurea derivatives
XII.
[0240] By reaction with alkali metal cyanates 39
[0241] M.sup..sym. is one equivalent of a metal ion, in particular
an alkali metal ion, such as sodium or potassium.
[0242] The reaction is carried out in an inert solvent or diluent,
for example in an aromatic hydrocarbon, such as toluene or o-, m-
or p-toluene, in an aliphatic or cyclic ether, such as
tetrahydrofuran or dioxane, in a lower alcohol, such as methanol or
ethanol, in water or in a mixture of the stated solvents.
[0243] The amount of cyanate is not critical; at least equimolar
amounts of aniline derivative XIX and cyanate are required for
complete conversion, but an excess of cyanate of up to about 100
mol % may also be advantageous.
[0244] The reaction temperature is in general from 0.degree. C. to
the reflux temperature of the reaction mixture.
[0245] By reaction with esters XX 40
[0246] L.sup.4 is C.sub.1-C.sub.4-alkyl or phenyl and L.sup.5 is
halogen, preferably chlorine or bromine, C.sub.1-C.sub.4-alkoxy or
phenoxy.
[0247] Examples of suitable solvents or diluents are aromatic
hydrocarbons, such as toluene and o-, m- and p-xylene,
halohydrocarbons, such as methylene chloride, chloroform,
1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers,
such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, esters,
such as ethyl acetate, alcohols, such as methanol and ethanol, and
water or two-phase mixtures of an organic solvent and water.
[0248] The reaction is advantageously carried out in the presence
of a base, for example of an alkali metal hydroxide, carbonate or
alcoholate, such as sodium hydroxide, sodium carbonate, sodium
methylate or sodium ethylate, or of a tertiary amine, such as
pyridine or triethylamine.
[0249] If desired, a catalyst, for example a Lewis acid, such as
antimony trichloride, may also be added.
[0250] The starting compounds and the base are advantageously used
in a stoichiometric ratio, but one or other component may also be
present in an excess of up to about 100 mol %.
[0251] As a rule, the amount of catalyst is from 1 to 50,
preferably from 2 to 30, mol %, based on the amount of aniline
derivative XIX used.
[0252] The reaction temperature is in general from -40.degree. C.
to the boiling point of the reaction mixture.
[0253] The starting compounds of the formula XIX and their
preparation and all other compounds whose preparation is not
described explicitly are known from the literature or said
compounds can be prepared by conventional methods.
[0254] In the abovementioned processes for the synthesis of
substituted 3-phenyluracils I, their salts, enol ethers or
intermediates, atmospheric pressure or the autogenous pressure of
the particular solvent is advantageously used. Lower or higher
pressure is possible but usually has no advantages.
[0255] Unless stated otherwise, the reagents and starting materials
required for the preparation of the substituted 3-phenyluracils I,
Ia and Ib are known or can be prepared by conventional methods.
[0256] The particular reaction mixtures are worked up, as a rule,
by conventional methods, for example by removing the solvent,
distributing the residue in a mixture of water and a suitable
organic solvent and isolating the product from the organic
phase.
[0257] The substituted 3-phenyluracils I, Ia and Ib may be obtained
in the preparation as isomer mixtures, which however can, if
desired, be separated into the pure isomers by conventional
methods, for example by crystallization or chromatography (if
necessary, over an optically active adsorbate). Pure optically
active isomers can be synthesized, for example, from corresponding
optically active starting materials.
[0258] As a rule, the compounds of the formulae I, Ia and Ib can be
prepared by the methods described above. However, in individual
cases certain compounds I can also advantageously be prepared from
other compounds I by ester hydrolysis, amidation, esterification,
transetherification, esterification, ether cleavage, olefination,
reduction, oxidation or a cyclization reaction at the positions of
the radicals R.sup.4, R.sup.5 and W.
[0259] The substituted 3-phenyluracils I, Ia and Ib are suitable as
herbicides both in the form of isomer mixtures and in the form of
the pure isomers. In general they are well tolerated and therefore
selective in broad-leaved crops and in monocotyledon plants.
[0260] Depending on the particular application method, the
substituted phenyluracils Ia and Ib or the agents containing them
can be used in a large number of crop plants for eliminating
undesirable plants, the following crops being mentioned as
examples:
16 Botanical name Common name Allium cepa onions Ananas comosus
pineapples Arachis hypogaea peanuts (groundnuts) Asparagus
officinalis asparagus Beta vulgaris spp. altissima sugarbeets Beta
vulgaris spp. rapa fodder beets Brassica napus var. napus rapeseed
Brassica napus var. napobrassica swedes Brassica rapa var.
silvestris beets Camellia sinensis tea plants Carthamus tinctorius
safflower Carya illinoinensis pecan trees Citrus limon lemons
Citrus sinensis orange trees Coffea arabica (Coffea canephora,
coffee plants Coffea liberica) Cucumis sativus cucumbers Cynodon
dactylon Bermudagrass in turf and lawns Daucus carota carrots
Elaeis guineensis oil palms Fragaria vesca strawberries Glycine max
soybeans Gossypium hirsutum cotton (Gossypium arboreum, Gossypium
herbaceum, Gossypium vitifolium) Helianthus annuus sunflowers Hevea
brasiliensis rubber plants Hordeum vulgare barley Humulus lupulus
hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lens
culinaris lentils Linum usitatissimum flax Lycopersicon
lycopersicum tomatoes Malus spp. apple trees Manihot esculenta
cassava Medicago sativa alfalfa (lucerne) Musa spp. banana plants
Nicotiana tabacum tobacco (N. rustica) Olea europaea olive trees
Oryza sativa rice Phaseolus lunatus limabeans Phaseolus vulgaris
snapbeans, green beans, dry beans Picea abies Norway spruce Pinus
spp. pine trees Pisum sativum English peas Prunus avium cherry
trees Prunus persica peach trees Pyrus communis pear trees Ribes
sylvestre redcurrants Ricinus communis castor-oil plants Saccharum
officinarum sugar cane Secale cereale rye Solanum tuberosum Irish
potatoes Sorghum bicolor (S. vulgare) sorghum Theobroma cacao cacao
plants Trifolium pratense red clover Triticum aestivum wheat
Triticum durum durum wheat Vicia faba tick beans Vitis vinifera
grapes Zea mays Indian corn, sweet corn, maize
[0261] The substituted 3-phenyluracils I, Ia and Ib are also
suitable for the desiccation and defoliation of plants. As
desiccants, they are particularly suitable for drying out the
above-ground parts of crop plants, such as potatoes, rape,
sunflower and soybean. This permits completely mechanical
harvesting of these important crop plants.
[0262] Also of commercial interest is the facilitation of
harvesting, which is permitted by concentrated dropping or a
reduction in the adhesion to the tree in the case of citrus fruits,
olives or other species and varieties of pomes, drupes and
hard-shelled fruit. The same mechanism, ie. promotion of the
formation of abscission tissue between the fruit or leaf part and
the shoot part of the plant, is also essential for readily
controllable defoliation of crops, for example cotton.
[0263] Furthermore, the shortening of the time interval in which
the individual cotton plants ripen leads to higher fiber quality
after harvesting.
[0264] Apart from their herbicidal and defoliant activity, some of
the substituted 3-phenyluracils of the formuale I, Ia and lb can
also be used as growth regulators or for controlling pests from the
class consisting of the insects, arachnids and nematodes. They can
be used for controlling pests in crop protection and in the
hygiene, stored materials and veterinary sectors.
[0265] The insect pests include, from the order of the butterflies
(Lepidoptera), for example Agrotis ypsilon, Agrotis segetum,
Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella,
Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua
reticulana, Cheimatobia brumata, Choristoneura fumiferana,
Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella,
Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella,
Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella,
Evetria bouliana, Feltia subterranea, Galleria mellonella,
Grapholita funebrana, Grapholita molesta, Heliothis armigera,
Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia
defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia
lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera
coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia
botrana, Loxostege sticticalis, Lymantria dispar, Lymantria
monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra
brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis
flamea, Pectinophora gossypiella, Peridroma saucia, Phalera
bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris
brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia
includens, Phyacionia frustrana, Scrobipalpula absoluta, Sitotroga
cerelella, Sparganothis pilleriana, Spodoptera frugiperda,
Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa,
Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis; from
the order of the beetles (Coleoptera), for example Agrilus
sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus
solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus
pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga
undata, Bruchus ruf imanus, Bruchus pisorum, Bruchus lentis,
Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata,
Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema
tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica
longicornis, Diabrotica 12-punctata, Diabrotica virgifera,
Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus
brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera
postica, Ips typographus, Lema bilineata, Lema melanopus,
Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus
oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha
hippocastani, Melolontha melolontha, Onlema oryzae, Ortiorrhynchus
sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta
chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta
nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus
and Sitophilus granaria; from the order of the Diptera, for example
Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles
maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya
hominivorax, Chrysomya macellaria, Contarinia sorghicola,
Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus
oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus
intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis
equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae,
Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia
sericata, Lycoria pectoralis, Mayetiola destructor, Musca
domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya
hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata,
Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula
oleracea and Tipula paludosa; from the order of the Thysanoptera,
for example Frankliniella fusca, Frankliniella occidentalis,
Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips
palmi and Thrips tabaci; from the order of the Hymenoptera, for
example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana,
Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis,
Solenopsis geminata and Solenopsis invicta; from the order of the
Heteroptera, for example Acrosternum hilare, Blissus leucopterus,
Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius,
Eurygaster integriceps, Euchistus impictiventris, Leptoglossus
phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula,
Piesma quadrata, Solubea insularis and Thyanta perditor; from the
order of the Homoptera, for example Acyrthosiphon onobrychis,
Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis
sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha
gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dyasphis
radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum
avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae,
Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata
lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon
humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus,
Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis
graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum and
Viteus vitifolii; from the order of the Isoptera, for example
Calotermes flavicollis, Leucotermes flavipes, Reticulitermes
lucifugus and Termes natalensis; from the order of the Orthoptera,
for example Acheta domestica, Blatta orientalis, Blatella
germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta
migratoria, Melanoplus birittatus, Melanoplus femurrubrum,
Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus,
Nomadacris septemfasciata, Periplaneta americana, Schistocerca
americana, Schistocerca peregrina, Stauronotus maroccanus and
Tachycines asynamorus; from the class of the Arachnoidea, for
example Acarina, such as Amblyomma americanum, Amblyomma
variegatum, Argas persicus, Boophilus annulatus, Boophilus
decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia
praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes
sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus,
Ornithodorus moubata, Otobins megnini, Paratetranychus pilosus,
Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus
latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus
evertsi, Saccoptes scabiei, Tetranychus cinnabarinus, Tetranychus
kanzawai, Tetranychus pacificus, Tetranychus telarius and
Tetranychus urticae; from the class of the nematodes, for example
root gall nematodes, eg. Meloidogyne hapla, Meloidogyne incognita
and Meloidogyne javanica, cyst-forming nematodes, eg. Globodera
rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera
schatii, Heterodera trifolii, and stem and leaf eelworms, eg.
Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus
dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus,
Radopholus similis, Rotylenchus robustus, Trichodorus primitivus,
Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus
neglectus, Pratylenchus penetrans, Pratylenchus curvitatus and
Pratylenchus goodeyi.
[0266] The active ingredients can be used as such, in the form of
their formulations or in the application forms prepared therefrom,
for example in the form of directly sprayable solutions, powders,
suspensions or dispersions, emulsions, oil dispersions, pastes,
dusting agents, broadcasting agents or granules, by spraying,
nebulizing, dusting, broadcasting and pouring. The application
forms depend entirely on the intended uses; they should in any case
ensure a very fine distribution of the novel active
ingredients.
[0267] The formulations are prepared in a known manner, for example
by extending the active ingredient with solvents and/or carriers,
if desired with the use of emulsifiers and dispersants; where water
is used as a diluent, other organic solvents may also be used as
auxiliary solvents. Suitable inert assistants for this purpose are
essentially mineral oil fractions having a medium to high boiling
point, such as kerosene and diesel oil, as well as coal tar oils
and oils with vegetable or animal origin, solvents, such as
aromatics (eg. toluene or xylene), chlorinated aromatics (eg.
chlorobenzenes), paraffins (eg. mineral oil fractions), alcohols
(eg. methanol, ethanol, butanol or cyclohexanol), ketones (eg.
cyclohexanone and isophorone), amines (eg. ethanolamine,
N,N-dimethylformamide or N-methylpyrrolidone) and water; carriers
such as ground natural minerals (eg. kaolins, aluminas, talc or
chalk) and ground synthetic minerals (eg. finely divided silica or
silicates); emulsifiers, such as nonionic and anionic emulsifiers
(eg. polyoxyethylene fatty alcohol ethers, alkylsulfonates and
arylsulfonates) and dispersants, such as ligninsulfite waste
liquors and methylcellulose.
[0268] Aqueous application forms can be prepared from emulsion
concentrates, dispersions, pastes, wettable powders or
water-dispersible granules by adding water. For the preparation of
emulsions, pastes or oil dispersions, the substrates, as such or
dissolved in an oil or solvent, can be homogenized in water by
means of wetting agents, adherents, dispersants or emulsifiers.
However, concentrates which consist of active ingredient, wetting
agents, adherents, dispersants or emulsifiers and possibly solvents
or oil and which are suitable for dilution with water can also be
prepared.
[0269] Suitable surfactants are alkali metal, alkaline earth metal
and ammonium salts of aromatic sulfonic acids, for example lignin-,
phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of
fatty acids, alkyl- and alkylarylsulfonates, alkylsulfates, lauryl
ether sulfates and fatty alcohol sulfates and salts of sulfated
hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers,
condensates of sulfonated naphthalene and its derivatives with
formaldehyde, condensates of naphthalene or of naphthalenesulfonic
acids with phenol and formaldehyde, polyoxyethylene octylphenol
ethers, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol
polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl
polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene
oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetal,
sorbitol esters, ligninsulfite waste liquors or
methylcellulose.
[0270] Powders, broadcasting agents and dusting agents can be
prepared by mixing or milling the active ingredients together with
a solid carrier.
[0271] Granules, for example coated, impregnated and homogeneous
granules, can be prepared by binding the active ingredients to
solid carriers. Solid carriers are mineral earths, such as silica
gel, silicas, silicates, talc, kaolin, limestone, lime, chalk,
bole, loess, clay, dolomite, kieselguhr, calcium sulfate, magnesium
sulfate, magnesium oxide, milled plastics, fertilizers, such as
ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas,
and vegetable products, such as grain flours, bark meal, wood meal
and nutshell meal, cellulosic powders and other solid carriers.
[0272] The concentrations of the active ingredients I, Ia and Ib in
the ready-to-use formulations can be varied within wide ranges, for
example from 0.0001 to 95% by weight. For use as herbicides or
plant growth-regulating agents, concentrations of from 0.01 to 95,
preferably from 0.5 to 90, % by weight of active ingredient are
preferable. Formulations containing from 0.0001 to 10, preferably
from 0.01 to 1, % by weight of active ingredient are suitable for
use as insecticides. The active ingredients are used in a purity of
from 90 to 100%, preferably from 95 to 100% (according to NMR
spectrum).
[0273] Examples of such formulations are:
[0274] I. A solution of 90 parts by weight of compound No. 1.1 and
10 parts by weight of N-methyl-.alpha.-pyrrolidone, which is
suitable for use in the form of very small drops.
[0275] II. A mixture of 20 parts by weight of compound No. 1.2, 80
parts by weight of xylene, 10 parts by weight of the adduct of 8 to
10 mol of ethylene oxide with 1 mol of N-monoethanololeamide, 5
parts by weight of the calcium salt of dodecylbenzenesulfonic acid
and 5 parts by weight of the adduct of 40 mol of ethylene oxide
with 1 mol of castor oil. By finely distributing the mixture in
100,000 parts by weight of water, a dispersion which contains 0.02%
by weight of the active ingredient is obtained.
[0276] III. An aqueous dispersion of 20 parts by weight of compound
No. 3.1, 40 parts by weight of cyclohexanone, 30 parts by weight of
isobutanol and 20 parts by weight of the adduct of 40 mol of
ethylene oxide with 1 mol of castor oil. The mixture of this
dispersion with 100,000 parts by weight of water contains 0.02% by
weight of the active ingredient.
[0277] IV. An aqueous dispersion of 20 parts by weight of compound
No. 2.1, 25 parts by weight of cyclohexanol, 65 parts by weight of
a mineral oil fraction boiling within a range of 210 to 280.degree.
C. and 10 parts by weight of the adduct of 40 mol of ethylene oxide
with 1 mol of castor oil. The mixture of this dispersion with
100,000 parts by weight of water contains 0.02% of the active
ingredient.
[0278] V. A mixture milled in a hammer mill and consisting of 80
parts by weight of compound No. 3.1, 3 parts by weight of the
sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid, 10
parts by weight of the sodium salt of a ligninsulfonic acid
obtained from a sulfite waste liquor and 7 parts by weight of
silica gel powder. By finely distributing the mixture in 20,000
parts by weight of water, a spray liquor which contains 0.1% by
weight of the active ingredient is obtained.
[0279] VI. An intimate mixture of 3 parts by weight of compound No.
3.2 and 97 parts by weight of finely divided kaolin. This dusting
agent contains 3% by weight of active ingredient.
[0280] VII. An intimate mixture of 30 parts by weight of compound
No. 3.3, 92 parts by weight of silica gel powder and 8 parts by
weight of liquid paraffin which has been sprayed onto the surface
of the silica gel. This formulation gives the active ingredient
good adhesion.
[0281] VIII. A stable aqueous dispersion of 40 parts by weight of
compound No. 4.1, 10 parts by weight of the sodium salt of a
phenolsulfonic acid/urea/formaldehyde condensate, 2 parts by weight
of silica gel and 48 parts by weight of water, which can be further
diluted.
[0282] IX. A stable oily dispersion of 20 parts by weight of
compound No. 1.1, 2 parts by weight of the calcium salt of
dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol
polyglycol ether, 20 parts by weight of the sodium salt of a
phenolsulfonic acid/urea/formaldehyde condensate and 68 parts by
weight of a paraffinic mineral oil.
[0283] X. A mixture milled in a hammer mill and consisting of 10
parts by weight of compound No. 2.1, 4 parts by weight of the
sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid, 20
parts by weight of the sodium salt of a ligninsulfonic acid
obtained from a sulfite waste liquor, 38 parts by weight of silica
gel and 38 parts by weight of kaolin. By finely distributing the
mixture in 10,000 parts by weight of water, a spray liquor which
contains 0.1% by weight of the active ingredient is obtained.
[0284] The active ingredients or the herbicidal and plant
growth-regulating agents can be applied by the preemergence or
postemergence method. The plants are usually sprayed or dusted with
the active ingredients or the seeds of the test plants are treated
with the active ingredients. If the active ingredients are less
well tolerated by certain crop plants, it is possible to use
application methods in which the herbicides are sprayed with the
aid of the sprayers in such a way that the leaves of the sensitive
crop plants are as far as possible not affected while the active
ingredients reach the leaves of undesirable plants growing
underneath or the uncovered oil surface (post-directed,
lay-by).
[0285] The application rates of active ingredient are from 0.001 to
5.0, preferably from 0.01 to 2, kg/ha of active ingredient,
depending on the aim of control, the season, the target plants and
the stage of growth.
[0286] To broaden the action spectrum and to achieve synergistic
effects, the substituted 3-phenyluracils I, Ia and Ib can be mixed
and applied together with a large number of members of other groups
of herbicidal or growth-regulating active ingredients. For example,
diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones,
2,6-dinitroanilines, N-phenylcarbamates, thiocarbamates,
halocarboxylic acids, triazines, amides, ureas, diphenyl ethers,
triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione
derivatives which carry in the 2-position, for example, a carboxyl
or carbimino, or quinolinecarboxylic acid derivatives,
imidazolinones, sulfonamides, sulfonylureas, aryloxy- and
hetaryloxyphenoxypropionic acids and their salts, esters and amides
and others are suitable components for the mixture.
[0287] The substituted 3-phenyluracils I, Ia and Ib can also be
applied together with other crop protection agents, such as
herbicides, growth regulators, pesticides, fungicides and
bactericides. These agents may be mixed with the novel agents in a
weight ratio of from 1:100 to 100:1, if desired also directly
before application (tank mix). Also of interest is the miscibility
with mineral salt solutions which are used for eliminating nutrient
and trace element deficiencies. Nonphytotoxic oils and oil
concentrates may also be added.
PREPARATION EXAMPLES
Example 1
3-[4-Chloro-3-(ethoximinomethyl)-phenyl]-2,4-dioxo-6-trifluoromethyl-1,
2, 3, 4-tetrahydropyrimidine (compound 1.4)
[0288] 41
[0289] 100.7 g of ethyl 3-amino-4, 4, 4-trifluorocrotonate in 150
ml of dimethylformamide were added dropwise to a suspension of 18.2
g of 80% strength sodium hydride in 550 ml of dimethylformamide at
0-5.degree. C., and stirring was carried out for one hour at
0-5.degree. C. Thereafter, 123.6 g of
4-chloro-3-ethoximinomethylphenyl isocyanate in 150 ml of
tetrahydrofuran were added dropwise at from -30 to -35.degree. C.
and stirring was continued for 20 hours at 25.degree. C. At
0-5.degree. C., 1.7 1 of water were stirred into the reaction
mixture and the resulting precipitate was removed. The filtrate was
brought to pH 5 with 60 ml of 6N HCl and the precipitate which had
separated out was isolated, washed with water and petroleum ether
and dried. mp.: 219-220.degree. C.
Example 2
3-[4-Chloro-3-(ethoximinomethyl)-phenyl]-2,4-dioxo-6-methyl-1, 2,
3, 4-tetrahydropyrimidine (compound 1.75)
[0290] 42
[0291] 3 g of
N-(4-chloro-3-ethoximinomethylphenyl)-N'-(1-ethoxycarbonylpr-
open-2-yl)-urea in 20 ml of dimethylformamide were added dropwise
to a suspension of 0.24 g of 80% strength sodium hydride in 550 ml
of dimethylformamide at room temperature, and stirring was carried
out for 3 hours at room temperature. At 10-15.degree. C., 100 ml of
water were added, the pH was brought to 5 with 10% strength HCl and
stirring was continued for 30 minutes at 10-15.degree. C. The
precipitate which had separated out was isolated, washed with water
and dried. mp.: >280.degree. C.
Example 3
3-[4-Chloro-3-(ethoximinomethyl)-phenyl]-2,4-dioxo-1-methyl-6-trifluoromet-
hyl-1, 2, 3, 4-tetrahydropyrimidine (compound 1.5)
[0292] 43
[0293] 26.3 ml of methyl iodide in 100 ml of dimethylformamide were
added dropwise, in the course of one hour, to a suspension of 137.5
g of
3-(4-chloro-3-ethoximinomethylphenyl)-2,4-dioxo-6-trifluoromethyl-1,
2, 3, 4-tetra-hydropyrimidine and 57.8 g of potassium carbonate in
600 ml of dimethylformamide, the temperature increasing to
30.degree. C. After stirring had been carried out for 20 hours, 700
ml of water were added dropwise at 5-10.degree. C. and the
precipitate which had separated out was isolated, washed with water
and petroleum ether and dried. mp.: 133-134.degree. C.
Example 4
3-(4-Chloro-3-formylphenyl)-2,4-dioxo-1-methyl-6-trifluoromethyl-1,
2, 3, 4-tetrahydropyrimidine (compound 1.1)
[0294] 44
[0295] 5 ml of water were added to a solution of 1.9 g of
3-(4-chloro-3-(1,3-dioxolan-2-yl)-phenyl)-2,4-dioxo-1-methyl-6-trifluorom-
ethyl-1, 2, 3, 4-tetrahydropyrimidine in 45 ml of glacial acetic
acid. After stirring had been carried out for 12 hours at about
20-25.degree. C. and for a further 5 hours at 40-50.degree. C., 150
ml of water were stirred into the mixture. Thereafter, the
precipitate formed was isolated, washed with water and petroleum
ether and dried. mp.: 151-153.degree. C.
Example 5
3-[4-Chloro-6-fluoro-3-formylphenyl)-2,4-dioxo-1-methyl-6-trifluoromethyl--
1, 2, 3, 4-tetrahydropyrimidine (compound 1.67)
[0296] 45
[0297] 50 ml of concentrated hydrochloric acid and 50 ml of 37%
strength formaldehyde solution were added to a solution of 58.5 g
of
3-[4-chloro-6-fluoro-3-(ethoximino-methyl)-phenyl]-2,4-dioxo-1-methyl-6-t-
rifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine in 350 ml of glacial
acetic acid, and the mixture was refluxed for 2 hours. After
cooling, the reaction mixture was evaporated down, the oily residue
was stirred with water and the resulting crystalline precipitate
was isolated, washed with water and petroleum ether and dried. mp.:
172-174.degree. C.
Example 6
3-[4-Chloro-3-(2-chloro-2-butoxycarbonylethen-1-yl)-phenyl]-2,4-dioxo-1-me-
thyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine (compound
1.15)
[0298] 46
[0299] 50 ml of a sodium n-butylate solution in n-butanol (prepared
from 0.3 g of 80% strength sodium hydride and 50 ml of n-butanol)
were added to a solution of 4.4 g of
3-[4-chloro-3-(2-chloro-2-ethoxycarbonylethen-1-
-yl)-phenyl]-2,4-dioxo-1-methyl-6-trifluoromethyl-1, 2, 3,
4-tetrahydropyrimidine in 50 ml of n-butanol, and stirring was
carried out for 5 hours at room temperature. Thereafter, the
mixture was neutralized with 10% strength hydrochloric acid at
0-5.degree. C. and the resulting solution was stirred into 100 ml
of water at 0-5.degree. C. The aqueous phase was extracted with 100
ml of toluene, and the combined organic phases were washed with
three times 50 ml of water, dried over sodium sulfate and
evaporated down. The oil obtained was chromatographed over silica
gel (dichloromethane), and the oil obtained therefrom was stirred
with petroleum ether. The resulting solid was filtered off, washed
with petroleum ether and dried. mp.: 109-110.degree. C.
Example 7
3-[4-Chloro-3-(4-chloro-3-oxobut-1-enyl)-phenyll-2,4-dioxo-1-methyl-6-trif-
luoromethyl-1, 2, 3, 4-tetrahydropyrimidine (compound 1.29)
[0300] 47
[0301] 4.6 g of chloroacetylmethylenetriphenyl-phosphorane were
added to a solution of 3.3 g of
3-[4-chloro-3-formylphenyl]-2,4-dioxo-1-methyl-6-tri-
fluoromethyl-1, 2, 3, 4-tetrahydropyrimidine in 100 ml of methanol,
and stirring was carried out for 10 hours at room temperature. The
precipitate which had separated out was isolated, washed with
petroleum ether and dried. mp.: 188-189.degree. C.
Example 8
3-[4-Chloro-3-(2-cyanoethenyl)-phenyl]-2,4-dioxo-1-methyl-6-trifluoromethy-
l-1, 2, 3, 4-tetrahydropyrimidine (compound 1.34)
[0302] 48
[0303] 3.3 g of
3-(4-chloro-3-formylphenyl)-2,4-dioxo-1-methyl-6-trifluoro-
methyl-1, 2, 3, 4-tetrahydropyrimidine in 30 ml of
dimethylformamide were added dropwise to a suspension of 1.8 g of
diethyl cyanomethylphosphonate and 1.5 g of potassium carbonate in
120 ml of dimethylformamide, and stirring was carried out for 20
hours at room temperature. Thereafter, 150 ml of water were added
and the precipitate which had separated out was isolated, washed
with water and petroleum ether and dried. mp.: 263-265.degree.
C.
Example 9
3-[4-Chloro-3-(2-cyano-2-methoxycarbonylethenyl)-phenyl]-2,4-dioxo-1-methy-
l-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine (compound
1.22)
[0304] 49
[0305] 0.97 ml of methyl cyanoacetate and 0.3 ml of piperidine were
added to a solution of 3.3 g of
3-(4-chloro-3-formylphenyl)-2,4-dioxo-1-methyl--
6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine in 100 ml of
tetrahydrofuran. After the mixture had been stirred for 5 hours at
the reflux temperature, a further 0.97 ml of methyl cyanoacetate
was added and refluxing was continued for a further 5 hours. The
reaction mixture was evaporated down and the oil obtained was
chromatographed (dichloromethane). The solid obtained was stirred
with diisopropyl ether, isolated, washed with petroleum ether and
dried. mp.: 187-188.degree. C.
Example 10
5-Chloro-3-[4-chloro-(2-chloro-2-ethoxycarbonylethenyl)-phenyl]-2,4-dioxo--
1-methyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine
(compound 1.42)
[0306] 50
[0307] 1.5 g of sulfuryl chloride were added dropwise to a solution
of 4.4 g of
3-[4-chloro-3-(2-chloro-2-ethoxy-carbonylethenyl)-phenyl]-2,4-dioxo--
1-methyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine in 50 ml
of glacial acetic acid. Stirring was carried out for 20 hours at
room temperature and for 12 hours under reflux, a further 2.6 ml of
sulfuryl chloride being added in two portions. The reaction mixture
was evaporated down and stirred with water and the precipitate was
isolated, washed with water and petroleum ether and dried. mp.:
160-164.degree. C.
Example 11
3-[4-Chloro-3-(2-(2, 2,
2-trifluoroethoxycarbonyl)-ethenyl)-phenyl]-2,4-di-
oxo-1-methyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine
(compound 1.85)
[0308] 51
[0309] A suspension of 5.0 g of
3-[4-chloro-3-iodo-phenyl]-2,4-dioxo-1-met-
hyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine, 2.0 g of
2,2,2-trifluoroethyl acrylate, 0.5 mg of palladium acetate and 1.1
g of sodium acetate in 50 ml of dimethylformamide was stirred for 4
hours at 120.degree. C., after which further palladium acetate and
2, 2, 2-trifluoromethyl acrylate were added and stirring was
continued for a further 2 hours at 120.degree. C. The cooled
reaction mixture was added to 200 ml of water and the precipitate
was isolated, washed with petroleum ether and dried under greatly
reduced pressure. mp.: 170-172.degree. C.
Example 12
3-[4-Chloro-3-(2-chloro-2-methoxycarbonylethyl]-phenyl-2,4-dioxo-1-methyl--
6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine (compound
1.86)
[0310] 52
[0311] 5.4 g of tert-butyl nitrite in 200 ml of acetonitrile were
initially taken at 0.degree. C. 30.1 g of methyl acrylate and 5.9 g
of CuCl.sub.2 were added in succession. Thereafter, a solution of
11.2 g of
3-[3-amino-4-chloro-phenyl]-2,4-dioxo-1-methyl-6-trifluoromethyl-1,
2, 3, 4-tetrahydropyrimidine in 100 ml of acetonitrile was slowly
added dropwise and the mixture was stirred overnight at 25.degree.
C. For working up, the solvent was stripped off under reduced
pressure and the residue was chromatographed over silica gel (8:1
cyclohexane/ethyl acetate). The title compound was obtained as an
oil.
Example 13
3-[4-Chloro-3-(1,3-dioxan-2-yl)-phenyl]-2,4-dioxo-1-methyl-6-trifluorometh-
yl-1, 2, 3, 4-tetrahydropyrimidine (compound 2.1)
[0312] 53
[0313] A solution of 3.5 g of
3-[4-chloro-3-formyl-phenyl]-2,4-dioxo-1-met-
hyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine, 0.8 g of
1,3-propanediol and 0.2 g of p-toluenesulfonic acid in 100 ml of
anhydrous dichloromethane was boiled for 5 hours under a water
separator. The solution was washed with 10% strength sodium
bicarbonate solution and water, dried over sodium sulfate and
evaporated down. The residue was chromatographed over silica gel
(7:3 cyclohexane/ethyl acetate). mp.: 87-92.degree. C.
Example 14
3-[4-Chloro-3-dimethoxymethylphenyl]-2,4-dioxo-1-methyl-6-trifluoromethyl--
1, 2, 3, 4-tetrahydropyrimidine (compound 2.22)
[0314] 54
[0315] 170 ml of trimethyl orthoformate were added to a thoroughly
stirred suspension of 136 g of montmorillonite K10 in 700 ml of
anhydrous toluene, and stirring was carried out for 30 minutes.
Thereafter, 68.0 g of
3-(4-chloro-3-formylphenyl)-2,4-dioxo-1-methyl-6-trifluoro-methyl-1,
2, 3, 4-tetrahydropyrimidine were added dropwise while cooling with
ice, and the batch was stirred overnight at 25.degree. C. The
montmorillonite K10 was filtered off and washed thoroughly with
toluene. The solvent, excess ortho-ester and methyl formate were
distilled off under reduced pressure from the combined filtrates.
The remaining oil was crystallized with petroleum ether. mp.:
92-94.degree. C.
Example 15
3-[4-Chloro-3-(4,5-dimethyl-1,3-dioxolan-2-yl)-phenyl]-2,4-dioxo-1-methyl--
6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine (compound
2.17)
[0316] 55
[0317] 30 g of
3-(4-chloro-3-dimethoxymethylphenyl)-2,4-dioxo-1-methyl-6-t-
rifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine, 2.1 g of
2,3-dihydroxybutane and 0.3 g of p-toluenesulfonic acid were
dissolved in 100 ml of anhydrous toluene, and the stirred solution
was refluxed for 7 hours in the absence of water. For working up,
the solution was washed in succession with water and 10% strength
NaHCO.sub.3 solution, dried over Na.sub.2SO.sub.4 and evaporated
down. mp.: 149-151.degree. C.
Example 16
3-[4-Chloro-3-(1,3-oxothiolan-2-yl)-phenyl]-2,4-dioxo-1-methyl-6-trifluoro-
methyl-1, 2, 3, 4-tetrahydropyrimidine (compound 2.32)
[0318] 56
[0319] A mixture of 3.0 g of
3-(4-chloro-3-formylphenyl)-2,4-dioxo-1-methy-
l-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine, 0.8 g of
2-mercaptoethanol and 0.12 g of tellurium tetrachloride in 100 ml
of 1,2-dichloroethane was stirred for 16 hours at room temperature.
0.2 g of sodium bicarbonate was added, the mixture was thoroughly
stirred and the precipitate was filtered off and washed with
dichloromethane. The combined organic filtrates were dried over
sodium sulfate and evaporated down. The residue was chromatographed
(diethyl ether) and was stirred in toluene/petroleum ether. The
crystalline precipitate obtained was washed with petroleum ether
and dried. mp.: 168-170.degree. C.
Example 17
3-(4-Chloro-3-(2-carboxy-2-chloroethenyl)-phenyl]-2,4-dioxo-6-trifluoromet-
hyl-1, 2, 3, 4-tetrahydropyrimidine (compound 1.41)
[0320] 57
[0321] 4.4 g of
3-(4-chloro-3-(2-chloro-2-ethoxy-carbonylethenyl)-phenyl]--
2,4-dioxo-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine were
added to a suspension of 0.8 g of sodium hydroxide in 100 ml of
ethanol and stirring was carried out for 20 hours at room
temperature. The reaction mixture was evaporated down, the residue
was taken up in water and the solution was brought to pH 3 with 10%
strength HCl. The precipitate which had separated out was isolated,
washed with water and petroleum ether and dried under reduced
pressure. mp.: >250.degree. C.
Example 18
3-(4-Chloro-3-cyanomethoximinomethylphenyl]-2,4-dioxo-1-methyl-6-trifluoro-
methyl-1, 2, 3, 4-tetrahydropyrimidine (compound 1.53)
[0322] 58
[0323] 1.3 g of O-cyanomethylhydroxylamine hydrochloride were added
to a suspension of 3.3 g of
3-(4-chloro-3-formylphenyl)-2,4-dioxo-1-methyl-6-t-
rifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine and 1.3 g of sodium
carbonate in 150 ml of toluene and stirring was carried out for 20
hours. The reaction mixture was washed with three times 50 ml of
water, dried over sodium sulfate and evaporated down. The solid
residue was stirred with petroleum ether, isolated, washed with
petroleum ether and dried. mp.: 171-174.degree. C.
Example 19
3-[4-Chloro-3-(2-chloro-2-methoxycarbonylethenyl)-phenyl]-2-methoxy-4-oxo--
6-trifluoromethyl-3,4-dihydro-pyrimidine (compound 3.1)
[0324] 59
[0325] 0.9 g of sodium methylate solution (30% strength in
methanol) in 10 ml of methanol was added dropwise to a solution of
2.2 g of
2-chloro-3-[4-chloro-3-(2-chloro-ethoxycarbonylethenyl)-phenyl]-4-oxo-6-t-
rifluoromethyl-3,4-dihydropyrimidine in 40 ml of methanol, and
stirring was carried out for 2 hours at room temperature. The
precipitate was isolated, washed with water and petroleum ether and
dried. mp.: 151-152.degree. C.
Example 20
3-[4-Chloro-3-(2-chloro-2-ethoxycarbonylethenyl)-phenyl]-4-oxo-2-thioxo-1,
2, 3, 4-tetrahydrothieno[3,4-d]pyrimidine (compound 1.90)
[0326] 60
[0327] 1.8 g of
N-[4-chloro-3-(2-chloro-2-ethoxy-carbonylethenyl)-phenyl]--
N'-(4-methoxycarbonylthien-3-yl)-urea in 10 ml of dimethylformamide
were added to a suspension of 0.11 g of sodium hydride (80%
strength) in 50 ml of dimethylformamide at room temperature, and
stirring was carried out for 3 hours at room temperature and for 8
hours at 50.degree. C. The reaction mixture was cooled is to
10-15.degree. C., 100 ml of water were added, neutralization was
effected with 10% strength hydrochloric acid and stirring was
carried out for 1 hour. The precipitate obtained was isolated and
was dissolved in dichloromethane. The solution obtained was washed
twice with water, dried over sodium sulfate and evaporated down.
The residue was stirred with duisopropyl ether, isolated and dried.
mp.: 278-280.dbd.C.
Example 21
3-
(4-Chloro-3-ethoxycarbonylhydrazonomethylphenyl)-2,4-dioxo-1-methyl-6-t-
rifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine (compound 1.91)
[0328] 61
[0329] 1.0 g of ethyl hydrazinecarboxylate was added to a solution
of 3.3 g of
3-[4-chloro-3-formylphenyl]-2,4-dioxo-1-methyl-6-trifluoromethyl-1,
2, 3, 4-tetrahydropyrimidine and 0.1 g of p-toluenesulfonic acid in
150 ml of toluene. After 2 hours, the solution was washed once with
water, the organic phase was dried over sodium sulfate and
evaporated down and the residue was stirred with petroleum ether.
The precipitate was isolated, washed with petroleum ether and
dried. mp.: 111-116.degree. C.
Example 22
3-[4-Chloro-3-(2-carboxy-2-chloroethenyl)-phenyl]-2,4-dioxo-1-methyl-6-tri-
fluoromethyl-1, 2, 3, 4-tetrahydropyrimidine (compound 1.92)
[0330] 62
[0331] 25 ml of trifluoroacetic acid were added to a solution of
4.7 g of
3-[4-chloro-3-(2-tert-butoxy-carbonyl-2-chloroethenylphenyl]-2,4-dioxo-1--
methyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine in 25 ml
of dichloromethane at 25.degree. C., and stirring was carried out
for 2 hours. The reaction mixture was evaporated down, the oily
residue was stirred with water and the precipitate was isolated,
washed with water and petroleum ether and dried. mp.:
216-217.degree. C.
Example 23
3-(4-Chloro-3-ethoximinomethylphenyl]-1-methyl-2-oxo-4-thioxo-6-trifluorom-
ethyl-1, 2, 3, 4-tetrahydropyrimidine (compound 4.1)
[0332] 63
[0333] 2.4 g of
2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane
2,4-disulfide (Lawesson's reagent) were added to a solution of 3.8
g of
3-[4-chloro-3-ethoximinomethylphenyl]-2,4-dioxo-1-methyl-6-trifluoromethy-
l-1, 2, 3, 4-tetrahydropyrimidine in 100 ml of toluene, and the
stirred mixture was ref luxed for 10 hours. After cooling and flash
chromatography (silica gel, toluene), the solid residue obtained
was stirred with petroleum ether, isolated, washed with petroleum
ether and dried. mp.: 129-130.degree. C.
Example 24
3-[3-(2-Bromo-2-methoxyethoxycarbonylethenyl)-4-chlorophenyl)-2,4-dioxo-1--
methyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine (compound
1.104)
[0334] 64
[0335] 0.52 ml of methoxyethyl bromide was added to a solution of
2.27 g of
3-[3-(2-bromo-2-carboxyethenyl)-4-chlorophenyl]-2,4-dioxo-1-methyl-6-t-
rifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine and 0.76 g of
potassium carbonate in dimethylformamide, and the resulting
solution was stirred for 17 hours. Thereafter, 100 ml of water were
added and the aqueous phase was extracted with twice 100 ml of
dichloromethane. The combined organic phases were washed with three
times 50 ml of water, dried over sodium sulfate and evaporated
down. After flash chromatography (dichloromethane .fwdarw.9 : 1
dichloromethane/ethyl acetate), the title compound was obtained as
an oil.
Example 25
3-[3-(2-Bromo-2-ethylthioethoxycarbonylethenyl)-4-chlorophenyl]-2,4-dioxo--
1-methyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine
(compound 1.105)
[0336] 65
[0337] 2.36 g of
3-(3-(2-bromo-2-chlorocarbonylethenyl)-4-chlorophenyl-2,4-
-dioxo-1-methyl-6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine
in 20 ml of tetrahydrofuran were added dropwise to a solution of
0.58 g of 2-ethyl-mercaptoethanol and 0.56 g of triethylamine in 30
ml of tetrahydrof uran, and stirring was carried out for 5 hours.
100 ml of water were added and the aqueous phase was extracted with
twice 100 ml of dichloromethane. The combined organic phases were
washed three times with water, dried with sodium sulfate and
evaporated down. The solid residue was stirred with duisopropyl
ether, removed, washed with duisopropyl ether and petroleum ether
and dried. mp.: 118-120.degree. C.
Example 26
3-
(4--Chloro-3-ethoximinomethylphenyl)-2,4-dioxo-5-ethoxy-carbonyl-6-meth-
yl-1, 2, 3, 4-tetrahydropyrimidine
[0338] 66
[0339] 1.8 ml of trichloromethyl chloroformate in 10 ml of
dichloromethane were added dropwise to a solution of 7 g of
N-(4-chloro-3-ethoximinomethy-
lphenyl)-3-amino-2-ethoxycarbonylcrotonamide and 4.8 g of pyridine
in 250 ml of dichloromethane. Stirring was carried out for 15
hours, after which a further 0.8 ml of trichloromethyl
chloroformate was added. After stirring had been carried out for 2
days at 25.degree. C. and for 3 hours under reflux, the reaction
mixture was washed three times with 150 ml of water, dried over
sodium sulfate and evaporated down. After chromatography
(dichloromethane/ethyl acetate), the title compound was obtained.
mp.: 232-234.degree. C.
Example 27
3-[4--Chloro-3-(2-chloro-2-ethoxycarbonylethenyl)-phenyl]-2-methylthio-4-o-
xo-3,4-dihydrothieno[3,4-dipyrimidine (compound 3.2)
[0340] 67
[0341] 0.28 g of methyl iodide in 5 ml of dimethylformamide was
added to a solution of 0.8 g of
3-l4-chloro-3-(2-chloro-2-ethoxycarbonylethenyl)-phe-
nyl]-4-oxo-2-thioxo-1, 2, 3, 4-tetrahydrothieno[3,4-d]pyrimidine
and 0.27 g of potassium carbonate in 40 ml of dimethylformamide.
Stirring was carried out for 2 days, after which the mixture was
cooled to 10.degree. C., 80 ml of water were added and stirring was
effected for a further 2 hours. The resulting precipitate was
removed, washed with water and dried. mp.: 142-145.degree. C.
[0342] Further compounds were prepared by methods similar to those
described in the Examples. These are shown, together with their
melting point, in the Tables below, alongside the compounds
described in the Examples.
17 Active Substance Table 1 68 No. R.sup.1 R.sup.2 R.sup.3 R.sup.4
R.sup.5 W m.p. [.degree. C.] 1.1 Cl H CH.sub.3 CF.sub.3 H CHO
151-153 1.2 Cl H H CF.sub.3 H CH.dbd.N--OCH.sub.3 207-208 1.3 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.N--OCH.sub.3 140-141 1.4 Cl H H CF.sub.3
H CH.dbd.N--OC.sub.2H.sub.5 221-223 1.5 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.N--OC.sub.2H.sub.5 132-134 1.6 Cl H C.sub.2H.sub.5 CF.sub.3
H CH.dbd.N--OC.sub.2H.sub.5 121-122 1.7 Cl H
CH.sub.2CH.dbd.CH.sub.2 CF.sub.3 H CH.dbd.N--OC.sub.2H.sub.5
113-114 1.8 Cl H CH.sub.2C.ident.CH CF.sub.3 H
CH.dbd.N--OC.sub.2H.sub.5 151-152 1.9 Cl H CH.sub.2C.sub.6H.sub.5
CF.sub.3 H CH.dbd.N--OC.sub.2H.sub.5 164-165 1.10 Cl H H CF.sub.3 H
CH.dbd.CCl--COOC.sub.2H.sub.5 202-206 1.11 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.CCl--COOC.sub.2H.sub.5 159-160 1.12 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.CCl--COOCH.sub.3 160-161 1.13 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.CCl--COOiC.sub.3H.sub.7 159-160 1.14 Cl H CH.sub.3 CF.sub.3
H CH.dbd.CCl--COOnC.sub.3H.sub.7 130-131 1.15 Cl H CH.sub.3
CF.sub.3 H CH.dbd.CCl--COOnC.sub.4H.sub.9 109-110 1.16 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.CCl--COOtC.sub.4H.sub.9 154-155 1.17 Cl
H CH.sub.3 CF.sub.3 H CH.dbd.CBr--COOCH.sub.3 162-163 1.18 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.CBr--COOC.sub.2H.sub.5 147-148 1.19 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.CBr--COOiC.sub.3H.sub.7 153-154 1.20 Cl
H CH.sub.3 CF.sub.3 H CH.dbd.CBr--COOtC.sub.4H.sub.9 150-151 1.21
Cl H CH.sub.3 CF.sub.3 H CH.dbd.CI--COOCH.sub.3 178-179 1.22 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.C(CN)--COOCH.sub.3 187-188 1.23 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.C(CH.sub.3)--COOCH.sub.3 159-160 1.24 Cl
H CH.sub.3 CF.sub.3 H CH.dbd.C(CH.sub.3)--COOC.sub.2H.sub.5 Oil
1.25 Cl H CH.sub.3 CF.sub.3 H CH.dbd.C(CH.sub.3)--CHO 154-155 1.26
Cl H CH.sub.3 CF.sub.3 H CH.dbd.CH--CO--CH.sub.3 227-228 1.27 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.CH--CO-iC.sub.3H.sub.7 135-136 1.28 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.CH--CO-4Cl--C.sub.6H.sub.4 246-247 1.29
Cl H CH.sub.3 CF.sub.3 H CH.dbd.CH--CO--CH.sub.2Cl 188-189 1.30 Cl
H CH.sub.3 CF.sub.3 H CH.dbd.CH--CO--CH.sub.2OCH.s- ub.3 189-190
1.31 Cl H CH.sub.3 CF.sub.3 H CH.dbd.CH--CO--CH.sub.2O-
C.sub.2H.sub.5 184-185 1.32 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.CH--CO--CHCl.sub.2 181-182 1.33 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.CH--CO--CH(OC.sub.2H.sub.5).sub.2 118-119 1.34 Cl H CH.sub.3
CF.sub.3 H CH.dbd.CH--CN 263-265 (9:1).sup.b) 1.35 Cl H CH.sub.3
CF.sub.3 H CH.dbd.CH--CH.dbd.C(CH.sub.3)--COOC.sub.2H.sub.5 229-231
(1:2).sup.b) 1.36 Cl H C.sub.2H.sub.5 CF.sub.3 H
CH.dbd.CCl--COOC.sub.2H.sub.5 137-138 1.37 Cl H
CH.sub.2CH.dbd.CH.sub.2 CF.sub.3 H CH.dbd.CCl--COOC.sub.2H.sub.3
134-135 1.38 Cl H CH.sub.2C.ident.CH CF.sub.3 H
CH.dbd.CCl--COOC.sub.2H.su- b.3 158-159 1.39 Cl H CH.sub.2CN
CF.sub.3 H CH.dbd.CCl--COOC.sub.2H- .sub.3 150-151 1.40 Cl H
CH.sub.2COOC.sub.2H.sub.5 CF.sub.3 H CH.dbd.CCl--COOC.sub.2H.sub.3
179-180 1.41 Cl H H CF.sub.3 H CH.dbd.CCl--COOH >250 1.42 Cl H
CH.sub.3 CF.sub.3 Cl CH.dbd.CCl--COOC.sub.2H.sub.5 160-164 1.43 Cl
H CH.sub.3 CF.sub.3 H CH.dbd.N--OH 94-98 1.44 Cl H CH.sub.3
CF.sub.3 H CH.dbd.N--O-n-C.sub.3H.sub.7 87-88 1.45 Cl H CH.sub.3
CF.sub.3 H CH.dbd.N--OCH.sub.2CH.dbd.CH.sub.2 82-83 1.46 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.N--O-n-C.sub.4H.sub.9 83-84 1.47 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.N--O-i-C.sub.4H.sub.9 96-97 1.48 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.N--O(CH.sub.2).sub.2CH(CH.sub.3).sub.2
77-79 1.49 Cl H CH.sub.3 CF.sub.3 H CH.dbd.N--O-n-C.sub.6H.sub.13
75-76 1.50 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.N--OCH.sub.2--CCl.dbd.CH.sub.2 108-110 1.51 Cl H CH.sub.3
CF.sub.3 H CH.dbd.N--O(CH.sub.2).sub.2-- -CCl.dbd.CH.sub.2 127-129
1.52 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.N.dbd.OCH.sub.2CH.dbd.CH--CH.sub.2OtC.sub.4H.sub.9 86-88
1.53 Cl H CH.sub.3 CF.sub.3 H CH.dbd.N--O--CH.sub.2CN 171-174 1.54
Cl H CH.sub.3 OC.sub.2H.sub.5 H CH.dbd.N--OC.sub.2H.sub.5 115-118
1.55 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.N--OCH(CH.sub.3)COOC.sub.2H.sub.5 Oil 1.56 Cl H CH.sub.3
CF.sub.3 H CH.dbd.N--OCH.sub.2-cyclo-C.sub.- 6H.sub.11 111-113 1.57
Cl H CH.sub.3 CF.sub.3 H 69 96-98 1.58 Cl H CH.sub.3 CF.sub.3 H 70
105-107 1.59 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.N--O--CH.sub.2-4Cl--C.sub.6H.sub.4 117-121 1.60 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.N--O--(CH.sub.2).sub.-
2-2F--C.sub.6H.sub.4 95-98 1.61 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.N--O(CH.sub.2).sub.2--CH.dbd.CH-4Cl--C.sub.6H.sub.4 130-131
1.63 Cl H H CF.sub.2Cl H CH.dbd.CCl--CO.sub.2C.sub.2H.sub.5 182-183
1.64 Cl H CH.sub.3 CF.sub.2Cl H CH.dbd.CCl--COOC.sub.2H.sub.5
111-113 1.65 Cl H H CH.sub.3 CH.sub.3 CH.dbd.CCl--COOC.sub.2H.sub.5
236-238 1.66 Cl H CH.sub.3 CH.sub.3 CH.sub.3
CH.dbd.CCl--COOC.sub.2H.sub.5 193-194 1.67 Cl F CH.sub.3 CF.sub.3 H
CHO 172-174 1.68 Cl F CH.sub.3 CF.sub.3 H CH.dbd.N--OCH.sub.3
135-137 (85:15).sup.b) 1.69 Cl F H CF.sub.3 H
CH.dbd.N--OC.sub.2H.sub.5 175-178 1.70 Cl F CH.sub.3 CF.sub.3 H
CH.dbd.N--OC.sub.2H.sub.5 103-105 1.71 Cl F CH.sub.3 CF.sub.3 H
CH.dbd.CBr--COOCH.sub.3 125-126 1.72 Cl F CH.sub.3 CF.sub.3 H
CH.dbd.CBR--COOC.sub.2H.sub.5 115-117 1.73 Cl F CH.sub.3 CF.sub.3 H
CH.dbd.CCl--COOCH.sub.3 116-117 1.74 Cl F CH.sub.3 CF.sub.3 H
CH.dbd.CCl--COOC.sub.2H.sub.5 133-134 1.75 Cl H H CH.sub.3 H
CH.dbd.N--OC.sub.2H.sub.5 >280 1.76 Cl H H CH.sub.3 H
CH.dbd.N--OC.sub.2H.sub.5 65-67 1.77 Cl H CH.sub.3 CH.sub.3 H
CH.dbd.N--OC.sub.2H.sub.5 111-112 1.78 Cl H CH.sub.3 CF.sub.2Cl H
CH.dbd.N--OC.sub.2H.sub.5 108-109 1.79 Cl H H --(CH.sub.2).sub.4--
CH.dbd.CCl--COOC.sub.2H.sub.5 218-220 1.80 Cl H H
--(CH.sub.2).sub.4-- CH.dbd.CH--COOCH.sub.3 261-276 1.81 Cl H
CH.sub.3 --(CH.sub.2).sub.4-- CH.dbd.CCl--COOC.sub.2H.sub.5 169-170
1.82 Cl H H --(CH.dbd.CH).sub.2-- CH.dbd.CCl--COOC.sub.2H.sub.5
245-246 1.83 Cl H CH.sub.3 --(CH.dbd.CH).sub.2--
CH.dbd.CCl--COOC.sub.2H.s- ub.5 204-205 1.84 Cl H H CF.sub.3 H
1,3-dioxolan-2-yl 180-182 1.85 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.CH--COOCH.sub.2CF.sub.3 170-172 1.86 Cl H CH.sub.3 CF.sub.3
H CH.sub.2--CH(Cl)--COOCH.sub.3 Oil 1.87 Cl H H C.sub.6H.sub.5 H
CH.dbd.N--OEt 198-200 1.88 Cl H CH.sub.3 C.sub.6H.sub.5 H
CH.dbd.N--OEt 173-175 1.89 Cl H H .dbd.CHSCH.dbd. CH.dbd.CCl--COOEt
278-280 1.90 Cl H CH.sub.3 CF.sub.3 H CH.dbd.NH--COOEt 111-116 1.91
Cl H CH.sub.3 CF.sub.3 H CH.dbd.N--NH--CH.dbd.C(CN)--COOCH.sub.3
219-221 1.92 Cl H CH.sub.3 CF.sub.3 H CH.dbd.CCl--COOH 216-217 1.93
Cl H CH.sub.3 CF.sub.3 H CH.dbd.CBr--COOH 193-195 1.94 Cl H H
4OCH.sub.3--C.sub.6H.sub.4 H CH.dbd.N--OC.sub.2H.sub.5 246-247 1.95
Cl H H 4Cl--C.sub.6H.sub.4 H CH.dbd.N--OC.sub.2H.sub.5 270-272 1.96
Cl H CH.sub.3 4OCH.sub.3--C.sub.6H.sub.4 H
CH.dbd.N--OC.sub.2H.sub.5 157-159 1.97 Cl H CH.sub.3
4Cl--C.sub.6H.sub.4 H CH.dbd.N--OC.sub.2H.sub.5 193-195 1.98 Cl H H
C.sub.6H.sub.5 COOCH.sub.3 CH.dbd.N--OC.sub.2H.sub.5 225-232 1.99
Cl H CH.sub.3 C.sub.6H.sub.5 COOCH.sub.3 CH.dbd.N--OC.sub.2H.sub.5
166-168 1.100 Cl H H CH.sub.3 COOC.sub.2H.sub.5
CH.dbd.N--OC.sub.2H.sub.5 232-234 1.101 Cl H CH.sub.3 CH.sub.3
COOC.sub.2H.sub.5 CH.dbd.N--OC.sub.2H.sub.5 105 1.102 Cl H CH.sub.3
CF.sub.3 H CH.dbd.CBr--COOCH.sub.2C.ident.- CH 128-130 1.103 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.CBr--COOCH.sub.2CO- OCH.sub.3 152-154
1.104 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.CBr--COO(CH.sub.2).sub.2OCH.sub.3 Oil 1.105 Cl H CH.sub.3
CF.sub.3 H CH.dbd.CBr--COO(CH.sub.2).sub.2SC.sub.2H.sub.5 118-120
1.106 Cl H CH.sub.3 CF.sub.3 H
CH.dbd.CBr--COOCH.sub.2C.sub.6H.sub.5 178-179 1.107 Cl H CH.sub.3
CF.sub.3 H CH.dbd.CBr--COO--N.dbd.C(CH- .sub.3).sub.2 155-156 1.108
Cl H CH.sub.3 CF.sub.3 H CH.dbd.CBr--CO--N-morpholino 159-160 1.109
Cl H CH.sub.3 CF.sub.3 H CH.dbd.CCl--CO--CH.sub.3 157-158 1.110 Cl
F CH.sub.3 CF.sub.3 H CH.dbd.C(CH.sub.3)--CHO 52-55 1.111 Cl H H
OC.sub.2H.sub.5 H CH.dbd.N--OC.sub.2H.sub.5 >260 1.112 Cl H H
CH.sub.3 H CH.dbd.CHCOOC.sub.2H.sub.5 213-215 1.113 Cl H H CF.sub.3
H C(CH.sub.3).dbd.N--OC.sub.2H.sub.5 157-159 1.114 Cl H CH.sub.3
CF.sub.3 H C(CH.sub.3).dbd.N--OC.sub.2H.sub.5 96-98 1.115 Cl H H
SC.sub.2H.sub.5 H CH.dbd.N--OC.sub.2H.sub.5 212-215 1.116 Cl H
CH.sub.3 CF.sub.3 H CH.dbd.N--OCH.sub.2--CH(CH.sub.3)--OH 89-96
[0343]
18 Active Substance Table 2 71 No. R.sup.2 W m.p. 2.1 H
1,3-dioxan-2-yl 87-92 2.2 H 5,5-dimethyl-1,3-dioxan-2-yl 120-123
2.3 H 5-methoxy-5-methyl-1,3-dioxan-2-yl 192-196 2.4 H
5-cyclohexyloxy-5-methyl-1,3- 64-68.sup.b) dioxan-2-yl 2.5 H
5,5-(diethoxycarbonyl)-1,3-dioxan- 65-68 2-yl 2.6 H 72 201-204 2.7
H 5-cyclohexyl-5-methyl-1,3-di- oxan- 87-91 (2:1).sup.b) 2-yl 2.8 H
5-butyl-5-ethyl-1,3-dioxan-2-yl 55-58 (1:1).sup.b 2.9 H
5-methyl-5-phenyl-1,3-dioxan-2-yl 95-98 (2:1).sup.b) 2.10 H
4-methoxycarbonyl-5-methyl-1,3- Oil (1:1).sup.b) dioxolan-2-yl 2.11
H 4-methoxycarbonyl-4-methyl-1,3- Oil (1:1).sup.b) dioxolan-2-yl
2.12 H 4-ethoxycarbonyl-4-methyl-1,3- Oil (1:1).sup.b)
dioxolan-2-yl 2.13 H 4-methyl-1,3-dioxolan-2- -yl Oil (1:1).sup.b)
2.14 H 4-n-propyl-1,3-dioxolan-2-yl Oil (1:1).sup.b) 2.15 H
4-vinyl-1,3-dioxolan-2-yl Oil (1:1).sup.b) 2.16 H
2-ethyl-1,3-dioxolan-2-yl Oil (1:1).sup.b) 2.17 H
4,5-dimethyl-1,3-dioxolan-2-yl 149-151.sup.c) 2.18 H 73 Oil
(1:1).sup.b) 2.19 H 4-tert.-butyl-1,3-dioxolan-2-yl Oil
(1:1).sup.b) 2.20 H 4,4,5-trimethyl-1,3-dioxolan-2-yl Oil
(1:1).sup.b) 2.21 H 4-trichlormethyl-1,3-dioxolan-2-yl 114-116
(6:4).sup.b) 2.22 H dimethoxymethyl 92-94 2.23 H
4-i-butoxycarbonyl-4-methyl-1,3- Oil (1:1).sup.b) dioxolan-2-yl
2.24 H 4-n-butoxycarbonyl-4-methyl-1.3- Oil (1:1).sup.b)
dioxolan-2-yl 2.25 F 4-n-butoxycarbonyl-4-methyl-1,3- Oil
(1:1).sup.b) dioxolan-2-yl 2.26 F 4-methyl-1,3-dithiolan-- 2-yl
67-69 (1:1).sup.b) 2.27 H 1,3-dioxolan-2-yl 58-60 2.28 H
di-(2-chlor-ethoxy)-methyl Oil 2.29 H 1,3-dithian-2-yl 176-177 2.30
H 1,3-dithiolan-2-yl 177-178 2.31 H 4-methyl-1,3-dithiolan-2-yl
115-118 (1:1).sup.b) 2.32 H 1,3-oxathiolan-2-yl 168-170 2.33 H
diethoxymethyl Oil 2.34 H 1,3-oxathian-2-yl Oil 2.35 H
4-methyl-1,3-dithian Oil (9:1).sup.b) 2.36 H di-n-propoxy-methyl
Oil 2.37 H 4-methyl-1,3-oxathiolan-2-yl Oil (7:3).sup.b) Remark:
.sup.a)Still contains 15% of isomeric allyloxime .sup.b)Isomer
mixture .sup.c)trans-isomer
[0344]
19 Active Substance Table 3 74 No. R.sup.1 R.sup.2 R.sup.31 X.sup.1
R.sup.4 R.sup.5 W m.p. 3.1 Cl H CH.sub.3 O CF.sub.3 H
CH.dbd.CCl--COOCH.sub.3 151-152 3.2 Cl H CH.sub.3 S
.dbd.CH--S--CH.dbd. CH.dbd.CCl--COOC.sub.2H.sub.5 142-145
[0345]
20 Active Substance Table 4 75 No. X.sup.1 X.sup.2 R.sup.2 W m.p.
4.1 O S H CH.dbd.N--OC.sub.2H.sub.5 129-130 4.2 O S H
CH.dbd.CCl--COOC.sub.2H.sub.5 129-132
[0346] Those compounds which were obtained as oils could be
characterized unambiguously with the aid of their IR data, which
are shown in the Table below.
21 Compound No. Characteristic IR Data/cm.sup.-1 (Film) 1.24 .nu. =
1731, 1685, 1474, 1372, 1272, 1231, 1185, 1152, 1069, 1050 1.55
.nu. = 1750, 1732, 1685, 1469, 1372, 1272, 1232, 1135, 1148, 1049
1.70 .nu. = 1736, 1691, 1492, 1408, 1369, 1271, 1185, 1151, 1069,
1050 1.86 .nu. = 1747, 1730, 1685, 1479, 1373, 1274, 1258, 1237,
1185, 1150 2.10 .nu. = 1758, 1732, 1684, 1480, 1373, 1273, 1233,
1186, 1150, 1104 2.11 .nu. = 1731, 1685, 1476, 1373, 1272, 1233,
1185, 1150, 1070, 1047 2.12 .nu. = 1731, 1686, 1476, 1373, 1272,
1233, 1185, 1151, 1070, 1047 2.13 .nu. = 1730, 1685, 1476, 1373,
1272, 1232, 1186, 1151, 1070, 1044 2.14 .nu. = 1731, 1683, 1475,
1372, 1271, 1232, 1185, 1150, 1070, 1044 2.15 .nu. = 1730, 1685,
1475, 1372, 1271, 1232, 1185, 1151, 1070, 1046 2.16 .nu. = 1730,
1685, 1476, 1372, 1272, 1232, 1186, 1151, 1070, 1045 2.18 .nu. =
1731, 1686, 1474, 1371, 1271, 1231, 1185, 1151, 1091, 1046 2.19
.nu. = 1731, 1686, 1478, 1372, 1271, 1232, 1185, 1151, 1070, 1044
2.20 .nu. = 1731, 1686, 1474, 1371, 1271, 1231, 1185, 1151, 1102,
1045 2.23 .nu. = 1732, 1687, 1474, 1373, 1272, 1185, 1151, 1047
2.24 .nu. = 1731, 1686, 1476, 1373, 1272, 1233, 1185, 1151, 1047
2.25 .nu. = 1736, 1691, 1497, 1370, 1273, 1213, 1185, 1151, 1084,
1069 2.28 .nu. = 1730, 1684, 1475, 1373, 1272, 1233, 1185, 1152,
1072, 1046 2.33 .nu. = 1731, 1686, 1474, 1372, 1272, 1231, 1185,
1151, 1070, 1049 2.34 .nu. = 1731, 1686, 1477, 1372, 1272, 1241,
1184, 1148, 1072, 1047 2.35 .nu. = 1731, 1685, 1478, 1372, 1271,
1257, 1184, 1149, 1045 2.36 .nu. = 1732, 1688, 1474, 1371, 1279,
1231, 1185, 1151, 1070, 1045 2.37 .nu. = 1732, 1685, 1476, 1372,
1271, 1234, 1184, 1148, 1070, 1043
[0347] Intermediates:
Intermediate Example 1
2--Chloro-3-(4-chloro-3-(2-chloro-2-ethoxycarbonyl-ethenyl)-phenyl]-4-oxo--
6-trifluoromethyl-3,4-dihydro-pyrimidine
[0348] 76
[0349] 13.8 ml of phosphoryl chloride were added dropwise to 12.6 g
of
3-[4-chloro-3-(2-chloro-2-ethoxy-carbonylethenyl)-phenyl]-2,4-dioxo-6-tri-
fluoromethyl-1, 2, 3, 4-tetrahydropyrimidine, and stirring was
carried out for 2 hours at room temperature. Thereafter, 2.1 ml of
dimethylformamide were added and stirring was continued for 15
hours at 110-115.degree. C. The reaction mixture was evaporated
down under reduced pressure, the residue was added to 150 ml of ice
water and the mixture was extracted with twice 100 ml of
dichloromethane. The combined organic phases were washed with
water, 10% strength sodium bicarbonate and again with water, dried
over sodium sulfate and evaporated down. The oil obtained was
subjected to flash chromatography (dichloromethane), and the
crystalline solid obtained therefrom was stirred with petroleum
ether, removed, washed with a little petroleum ether and dried.
mp.: 114-115.degree. C.
Intermediate Example 2
[0350] Reaction of 4-chloro-3-ethoximinophenyl isocyanate with
ethyl 3-aminocrotonate
[0351] 22.5 g of 4-chloro-3-ethoximinophenyl isocyanate in 100 ml
of toluene were added dropwise to a solution of 14.2 g of ethyl
3-aminocrotonate in 450 ml of toluene under reflux, and the
reaction mixture was stirred under reflux for 4 hours and at room
temperature for 2 days. Removing and drying the resulting
precipitate gave
N-(4-chloro-3-ethoximinomethylphenyl)-3-amino-2-ethoxy-carbonylcrotonamid-
e 77
[0352] The filtrate was evaporated down and the residue
chromatographed (dichloromethane). Trituration with cold petroleum
ether, removal and drying gave
N-(4-chloro-3-ethoximinomethylphenyl)-N'-(1-ethoxycarbonylpro-
pen-2-yl)-urea. 78
[0353] The following intermediates were prepared in a similar
manner:
22 79 No. L.sup.1 R.sup.1 R.sup.4 R.sup.5 W m.p. II.1
C.sub.2H.sub.5 Cl H H CH.dbd.N--OC.sub.2H.sub.5 126- 127 II.2
C.sub.2H.sub.5 Cl CH.sub.3 H CH.dbd.CCl--COOC.sub.2H.sub.5 136- 137
II.3 CH.sub.3 Cl H COOCH.sub.3 CH.dbd.CCl--COOC.sub.2H.sub.- 5 198-
200 II.4 C.sub.2H.sub.5 Cl --(CH.sub.2).sub.4--
CH.dbd.CCl--COOC.sub.2H.sub.5 129- 131 II.5 C.sub.2H.sub.5 Cl
--(CH.dbd.CH).sub.2-- CH.dbd.CCl--COOC.sub.2H.sub.5 141- 142 II.6
C.sub.2H.sub.5 Cl CH.sub.3 CH.sub.3 CH.dbd.CCl--COOC.sub.2H.sub.5
127- 130 II.7 C.sub.2H.sub.5 Cl OC.sub.2H.sub.5 H
CH.dbd.N--OC.sub.2H.sub.5 Oil
Intermediates Example 3
3-Amino-4-chloro-4,4-difluorocrotonates
[0354] 80
[0355] Ammonia was passed into ethyl
4-chloro-4,4-difluoroacetoacetate at 60.degree. C. until saturation
had been reached and stirring was carried out for 5 hours at
70.degree. C., after which gaseous ammonia was passed in again for
one hour and stirring was again carried out for 2 hours at
70.degree. C. The product was obtained after distillation over a 10
cm Vigreux column under reduced pressure from a 10 water pump. bp.:
129-130.degree. C./140 hPa.
[0356] Ethyl 3-amino-4, 4, 4-trifluorocrotonate was prepared in the
same manner.
Intermediate Example 4
4-Chloro-3-(1,3-dioxolan-2-yl)-phenyl isocyanate
[0357] 81
[0358] 2.0 g of 4-chloro-3-(1,3-dioxolan-2-yl)-aniline in 25 ml of
ethyl acetate were added to a solution of 3.0 g of trichloromethyl
chloroformate in 50 ml of toluene at about 20-25.degree. C. This
mixture was stirred for 2 hours at 20-25.degree. C. and then for a
further 5 hours at the reflux temperature. Thereafter, the reaction
mixture was evaporated down and the residue was dried under greatly
reduced pressure. Yield: 2.0 g (oil).
Intermediate Example 5
4-Chloro-3-(.alpha.-chloroethoxycarbonylethenyl)-phenyl
isocyanate
[0359] 82
[0360] 108.8 g of trichloromethyl chloroformate were added to a
suspension of 130 g of
4-chloro-3-(.alpha.-chloro-ethoxycarbonylethenyl)-aniline in 1200
ml of toluene. The stirred mixture was refluxed for 16 hours. After
the resulting precipitate had been separated off, the solvent was
removed under reduced pressure, the residue was stirred with
petroleum ether and the precipitate was removed and dried. mp.:
48-50.degree. C.
[0361] 4-Chloro-3-(ethoximinomethyl)-phenyl isocyanate, an oil,
[0362] 4-chloro-3-(ethoximinomethyl)-6-fluorophenyl isocyanate, an
oil, and
[0363] 4-chloro-3- (methoximinomethyl)-phenyl isocyanate, an oil,
were prepared in the same manner.
Intermediate Example 6
N-[4-Chloro-3-(2-chloro-2-ethoxycarbonylethenyl)-phenyl]-urea
[0364] 83
[0365] Gaseous ammonia was passed into a solution of 14.3 g of
4-chloro-3-(2-chloro-2-ethoxycarbonylethenyl)-phenyl isocyanate in
200 ml of tetrahydrofuran at 20.degree. C. in the course of 1.5
hours until saturation had been reached, and stirring was carried
out for 1 hour. The precipitate was removed and washed with ether.
The filtrate was evaporated down, the residue was stirred with
ether and the product was removed. The solids were combined. mp.:
209-210.degree. C.
Intermediate Example 7
4-Chloro-3-(2-chloro-2-ethoxycarbonylethenyl)-N-ethoxy-carbonylaniline
[0366] 84
[0367] 6.0 g of ethyl chloroformate were added dropwise to a
solution of 13 g of
4-chloro-3-(2-chloro-2-ethoxy-carbonylethenyl)-aniline in 150 g of
toluene and 5.6 g of triethylamine at 20-40.degree. C., and
stirring was carried out for 5 hours at room temperature. The
reaction mixture was washed three times with water, dried over
sodium sulfate and evaporated down and the residue was stirred with
petroleum ether, removed, washed with petroleum ether and dried.
mp.: 102-104.degree. C.
Intermediate Example 8
Methyl .beta.-aminocinnamate
[0368] 85
[0369] 47 g of bromobenzene in 90 ml of ether were added dropwise
to 7.2 g of magnesium in 20 ml of ether under reflux, and the
stirred mixture was refluxed for 1 hour. Thereafter, 9.9 g of
methyl cyanoacetate were added dropwise while cooling with ice, and
stirring was carried out for 1 hour at room temperature, for 5
hours under reflux and again for 15 hours at room temperature. 300
ml of ammonium chloride were carefully added to the reaction
mixture and the aqueous phase was extracted twice with ether and
the combined organic phases were washed three times with water,
dried over sodium sulfate and evaporated down. The residue was
distilled under greatly reduced pressure. 13 g of methyl
.beta.-aminocinnamate were obtained (110-112.degree. C., 10.15
mbar).
[0370] Methyl .beta.-amino-4-chlorocinnamate (from
1-bromo-4-chlorobenzene- , amorphous solid) and methyl
.beta.-amino-4-methoxycinnamate (bp.: 165-167.degree. C., 0.15 hPa)
were obtained in the same manner.
Intermediate Example 9
Methyl 4-isothiocyanatothiophen-3-carboxylate
[0371] 86
[0372] 19.4 g of methyl 4-aminothiophen-3-carboxylate hydrochloride
were added to a suspension of 7.7 ml of thiophosgene and 18.5 g of
sodium bicarbonate in 70 ml of water and 200 ml of dichloromethane
at room temperature in the course of 30 minutes, and stirring was
carried out for 1 hour at room temperature. After separation of the
phases, the aqueous phase was extracted once with dichloromethane
and the combined organic phases were washed once with water, dried
over sodium sulfate and evaporated down. mp.: 93-95.degree. C.
Intermediate Example 10
N-[4-Chloro-3-(2-chloro-2-ethoxycarbonylethenyl)-phenyl)-N-(4-methoxycarbo-
nylthien-3-yl)-thiourea
[0373] 87
[0374] 4 g of methyl 4-isothiocyanatothiophen-3-carboxylate in 50
ml of toluene were added dropwise to a solution of 5.2 g of
4-chloro-(2-chloro-2-ethoxycarbonyl-ethenyl)-aniline in 50 ml of
toluene. The reaction mixture was stirred for a total of 78 hours
at room temperature and 9 hours at 90.degree. C. The precipitate
obtained was removed, washed with toluene and then recrystallized
from ethanol. mp.: 158-160.degree. C.
Intermediate Example 11
3-(3-(2-Bromo-2-chlorocarbonylethenyl)-4-chlorophenyl3-2,4-dioxo-1-methyl--
6-trifluoromethyl-1, 2, 3, 4-tetrahydropyrimidine
[0375] 88
[0376] 1.6 g of thionyl chloride were added to a solution of 4.5 g
of 3- [3-
(2-bromo-2-carboxyethenyl)-4-chlorophenyl]-2,4-dioxo-1-methyl-6-trifl-
uoromethyl-1, 2, 3, 4-tetrahydropyrimidine and 0.1 ml of
dimethylformamide in 100 ml of toluene. The reaction mixture was
heated slowly to the reflux temperature, stirred under reflux for 5
hours and evaporated down, and the residue was dried under greatly
reduced pressure. mp.: 125-127.degree. C.
[0377] Use Examples (herbicidal activity)
[0378] The herbicidal activity of the substituted phenyluracils I,
Ia and Ib could be demonstrated by greenhouse experiments:
[0379] The culture vessels used were plastic flower pots containing
loamy sand with about 3.0% of humus as the substrate. The seeds of
the test plants were sown separately according to species.
[0380] In the preemergence treatment, the active ingredients
suspended or emulsified in water were applied, directly after
sowing, by means of finely distributing nozzles. The vessels were
lightly watered in order to promote germination and growth and were
then covered with transparent plastic covers until the plants had
begun to grow. This covering ensures uniform germination of the
test plants, unless this has been adversely affected by the active
ingredients.
[0381] For the purpose of the postemergence treatment, the test
plants were grown in the test vessels themselves or were planted in
the test vessels a few days beforehand. The active ingredients
suspended or emulsified in water were not applied until a height of
growth of from 3 to 15 cm, depending on the form of growth.
[0382] The plants were kept at 10-25.degree. C. or 20-35.degree.
C., according to species. The test periods extended over from 2 to
4 weeks. During this time, the plants were tended and their
reaction to the individual treatments was evaluated.
[0383] Rating was based on a scale from 0 to 100. 100 means no
emergence of the plants or complete destruction of at least the
above-ground parts and 0 means no damage on normal growth.
[0384] The plants used in the greenhouse experiments consisted of
the following species:
23 Botanical name Common name Abutilon theophrasti velvet leaf
Amaranthus retroflexus redroot pigweed Centaurea cyanus cornflower
Echinochloa crus-galli barnyard grass Ipomoea spp. morning glory
Solanum nigrum black nightshade
[0385] At application rates of 0.06 and 0.03 kg/ha, undesirable
broad-leaved plants can be very readily controlled with compound
No. 3.1 by the postemergence method.
[0386] Furthermore, undesirable broad-leaved plants and grasses can
be very readily controlled by the postemergence use of 0.5 kg/ha of
compounds 1.1, 1.3, 1.5, 1.11, 1.12, 1.13, 1.14, 1.15, 1.21, 1.22,
1.23, 1.24, 1.25, 1.26, 1.27, 1.36, 1.44, 2.1, 2.2, 2.3, 2.4, 2.7
and 2.27 in the greenhouse.
[0387] Use Examples (defoliation activity)
[0388] The comparative agent used was
[0389] A 6,7-dihydrodipyrido[1,2-alpha:2', 1'-c]pyridilium as the
dibromide monohydrate salt (common name: Diquat.RTM.).
[0390] The comparative agent was used in the form-of the
preformulated commercial product.
[0391] The test plants used were young, 4-leaved cotton plants
(without cotyledons) of the Stoneville 825 variety, which were
grown under greenhouse conditions (relative humidity from 50 to
70%; day/night temperature 27/20.degree. C.).
USE EXAMPLE 1
[0392] The leaves of the young cotton plants were treated to
run-off with aqueous formulations of the stated active ingredients
(with the addition of 0.15% by weight, based on the spray liquor,
of fatty alcohol alkoxylate Plurafac LF 700). The amount of water
applied was equivalent to 1000 l/h. After 13 days, the number of
dropped leaves and the degree of defoliation in % were determined.
In the case of the untreated control plants, no dropping of leaves
occurred.
24 Agent containing Converted applica- active ingredient No. tion
rate [kg/ha] Defoliation 3.1 0.05 53 0.10 73 A 0.10 0
[0393] The result shows that the novel substituted 3-phenyluracils
I have a very good defoliant effect and are superior to the
commercial product A in this respect.
[0394] Use Examples (insecticidal activity)
[0395] The insecticidal activity of the compounds of the general
formulae I, Ia and Ib could be demonstrated by the following
experiments:
[0396] The active ingredients were formulated
[0397] a) as a 0.1% strength solution in acetone or
[0398] b) as a 10% strength emulsion in a mixture of 70% by weight
of cyclohexanol, 20% by weight of Nekanile.RTM. LN (Lutensol.RTM.
AP6, wetting agent having an emulsifying and dispersing effect and
based on ethoxylated alkylphenols) and 10% by weight of
Emulphore.RTM. EL (Emulan.RTM. EL, emulsifier based on ethoxylated
fatty alcohols)
[0399] and were diluted to the desired concentration with acetone
in the case of a) and with water in the case of b).
[0400] After completion of the experiments, the lowest
concentration in each case at which the compounds still caused
80-100% inhibition or mortality (activity threshold or minimum
concentration) in comparison with untreated control experiments was
determined.
* * * * *