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US 5,334,576 AGranted
5 (and/or 6) substituted 2-(2-imidazolin-2-yl)nicotinic acids, esters and salts, useful as herbicidal agents and novel intermediates for the preparation of said nicotinic acids, esters and salts
AssigneeAmerican Cyanamid Company
InventorsRobert F. Doehner, Jr., David W. Ladner, John M. Finn
Life of this patent
Estimating the term…
Abstract
There are provided novel 5(and/or 6)substituted 2-(2-imidazolin-2-yl) and 2-(2-imidazolidinyl)nicotinic acids, esters and salts, which are useful as herbicidal agents. There are also provided novel substituted pyrrolopyridine acetonitriles, pyrrolopyridine acetamides, imidazopyrrolopyridinediones and carbamoylnicotinic acid esters, that are useful as intermediates for the preparation of the above said herbicidal agents.
Claims30
A compound having the structure:
- ##STR146## wherein R.sub.1 is C.sub.1 -C.sub.4 alkyl;
- R.sub.2 is C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.6 cycloalkyl;
- and when R.sub.1 and R.sub.2 are taken together with the carbon to which they are attached they may represent C.sub.3 -C.sub.6 cycloalkyl optionally substituted with methyl;
- A is COOR.sub.3, CONHR.sub.6, CHO, CH.sub.2 OH, COCH.sub.3, COC.sub.6 H.sub.5, CN, CH.sub.3, CH.dbd.NOH, CH.sub.2 COOH, CONHOH, CH.sub.2 CH.sub.2 COOH, CHR.sub.8 OH, ##STR147## R.sub.3 is hydrogen, ##STR148## C.sub.1 -C.sub.12 alkyl optionally substituted with one of the following groups:
- C.sub.1 -C.sub.3 alkoxy, C.sub.1 -C.sub.3 alkylthio, halogen, hydroxy, C.sub.3 -C.sub.6 cycloalkyl, benzyloxy, furyl, phenyl, halophenyl, loweralkylphenyl, loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano or triloweralkylammonium halide;
- C.sub.3 -C.sub.12 alkenyl optionally substituted with one of the following groups:
- C.sub.1 -C.sub.3 alkoxy, phenyl, halogen or loweralkoxycarbonyl or with two C.sub.1 -C.sub.3 alkoxy groups or two halogen groups;
- C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one or two C.sub.1 -C.sub.3 alkyl groups;
- C.sub.3 -C.sub.16 alkynyl optionally substituted with one or two C.sub.1 -C.sub.3 alkyl groups;
- or a cation;
- R.sub.6 is hydrogen, hydroxyl, C.sub.3 -alkenyl, C.sub.3 -alkynyl or C.sub.1 -C.sub.4 alkyl optionally substituted with one hydroxyl or one chlorine group;
- B is H, COR.sub.4 or SO.sub.2 R.sub.5 ;
- R.sub.4 is C.sub.1 -C.sub.11 alkyl, chloromethyl or phenyl optionally substituted with one chloro, one nitro or one methoxy group;
- R.sub.5 is C.sub.1 -C.sub.4 alkyl or phenyl optionally substituted with one methyl group;
- W is O or S;
- R.sub.8 is C.sub.1 -C.sub.4 alkyl or phenyl;
- Y and Z may independently be selected from the group consisting of hydrogen, halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.4 alkylthio, phenoxy, C.sub.1 -C.sub.4 haloalkyl, nitro, cyano, C.sub.1 -C.sub.4 alkylamino, di-C.sub.1 -C.sub.4 alkylamino, C.sub.1 -C.sub.4 alkylsulfonyl, difluoromethoxy, trifluoromethoxy, 1,1,2,2,-tetrafluoroethoxy, phenyl optionally substituted with one C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen;
- C.sub.3 -C.sub.8 straight or branched alkenyloxy optionally substituted with 1 to 3 halogens;
- C.sub.3 -C.sub.8 straight or branched alkynyloxy optionally substituted with 1 to 3 halogens;
- C.sub.2 -C.sub.6 straight or branched alkynyl substituted with hydroxy;
- C.sub.3 -C.sub.6 cycloalkyl interrupted by 1 oxygen, sulfur, amino or C.sub.1 -C.sub.4 alkylamino;
- and oxiranyl optionally substituted by one or two C.sub.1 -C.sub.4 alkyl;
- And at least one member of Y and Z must be selected from the group consisting of:
- C.sub.2 -C.sub.6 straight or branched alkenyl optionally substituted with phenyl, C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.2 -C.sub.6 straight or branched alkynyl optionally substituted with phenyl, C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.3 -C.sub.6 cycloalkyl optionally substituted with methyl, halogen or C.sub.1 -C.sub.4 alkoxy;
- C.sub.1 -C.sub.4 alkylcarbonyl optionally substituted with C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylcarbonylamino optionally substituted on nitrogen with C.sub.1 -C.sub.2 alkyl or C.sub.1 -C.sub.4 alkoxy and on carbon with C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylcarbonyloxy optionally substituted with C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkyl substituted with one or more of the following groups:
- C.sub.1 -C.sub.4 alkoxy optionally substituted with phenyl, thienyl, furyl, cyclopropyl, tetrahydrofuryl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 dialkylamino, C.sub.1 -C.sub.4 alkylamino, C.sub.1 -C.sub.4 trialkylammonium or 1 to 3 halogens;
- with the proviso that when the substituent on the C.sub.1 -C.sub.4 alkoxy group is C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylamino, C.sub.1 -C.sub.4 dialkylamino or
- C.sub.1 -C.sub.4 trialkylammonium, the respective heteroatoms are separated by at least 2 carbon atoms;
- C.sub.1 -C.sub.4 alkenyloxy optionally substituted with 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkynyloxy optionally substituted with 1 to 3 halogens;
- C.sub.3 -C.sub.6 cycloalkoxy;
- phenylthio;
- C.sub.1 -C.sub.4 alkylthio optionally substituted with phenyl or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylsulfinyl optionally substituted with phenyl or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylsulfonyl optionally substituted with phenyl or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylamino optionally substituted on carbon by phenyl or 1 to 3 halogens;
- C.sub.1 -C.sub.4 dialkylamino;
- C.sub.1 -C.sub.4 trialkylammonium;
- C.sub.1 -C.sub.4 alkylcarbonyloxy;
- cyano;
- phenylamino, optionally substituted in the ring by 1 to 3 halogens, C.sub.1 -C.sub.4 alkyl, or C.sub.1 -C.sub.4 alkoxy;
- phenoxy, optionally substituted in the ring by 1 to 3 halogens, C.sub.1 -C.sub.4 alkyl, or C.sub.1 -C.sub.4 alkoxy;
- 2(or 3)-furyl optionally substituted with halogen or C.sub.1 -C.sub.3 alkyl;
- 2(or 3)-thienyl optionally substituted with halogen or C.sub.1 -C.sub.3 alkyl;
- N-methyl-2(or 3)-pyrrolyl;
- hydroxy;
- formyl;
- amino optionally substituted with C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.1 -C.sub.2 alkyl and C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylsulfonyl and C.sub.1 -C.sub.2 alkyl, amino, C.sub.1 -C.sub.4 monoalkylamino, or C.sub.1 -C.sub.4 dialkylamino;
- 2(or 4)-pyridyloxy optionally substituted with C.sub.1 -C.sub.4 alkyl, trifluoromethyl or 1 or 2 halogens;
- C.sub.1 -C.sub.4 mono or dialkylaminocarbonylamino, optionally substituted on the nitrogen attached to the ring with C.sub.1 -C.sub.2 alkyl or C.sub.1 -C.sub.4 alkoxy;
- C.sub.1 -C.sub.4 alkoxycarbonylamino, optionally substituted on nitrogen with C.sub.1 -C.sub.2 alkyl or C.sub.1 -C.sub.4 alkoxy;
- and C.sub.1 -C.sub.4 mono or dialkylaminocarbonyloxy;
- Provided also that when Y is hydroxy, Z cannot be hydrogen;
- Provided also that when B is COR.sub.4 or SO.sub.2 R.sub.5, A is CH.sub.3, CN or COOR.sub.3 in which R.sub.3 is other than H or a cation and W is O, then Y and Z cannot be alkylamino, hydroxyl or hydroxyloweralkyl;
- an N-oxide thereof when W is O, provided that R.sub.3 cannot be unsaturated alkyl and Y and Z cannot be alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, trialkylammoniumalkyl, amino, 2(or 4)-pyridyloxy, alkoxyamino or unsaturated alkyl;
- an optical isomer thereof when R.sub.1 and R.sub.2 are not the same;
- a tautomer thereof;
- or an agronomically acceptable acid addition salt thereof except when R.sub.3 is a cation.
60 more elements
The compound according to claim 2, 5-isopropenyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid or an agronomically acceptable salt or ester thereof.
A method for the control of undesirable plant species comprising:
- applying to the foliage of said plants or to soil or water containing seeds or other propagating organs thereof, a herbicidally effective amount of a compound having the structure:
- ##STR151## wherein R.sub.1 is C.sub.1 -C.sub.4 alkyl;
- R.sub.2 is C.sub.1 -C.sub.4 alkyl or C.sub.3 -C.sub.6 cycloalkyl;
- and when R.sub.1 and R.sub.2 are taken together with the carbon to which they are attached they may represent C.sub.3 -C.sub.6 cycloalkyl optionally substituted with methyl;
- A is COOR.sub.3, CONHR.sub.6, CHO, CH.sub.2 OH, COCH.sub.3, COC.sub.6 H.sub.5, CN, CH.sub.3, CH.dbd.NOH, CH.sub.2 COOH, CONHOH, CH.sub.2 CH.sub.2 COOH, CHR.sub.8 OH, ##STR152## R.sub.3 is hydrogen, ##STR153## C.sub.1 -C.sub.12 alkyl optionally substituted with one of the following groups:
- C.sub.1 -C.sub.3 alkoxy, C.sub.1 -C.sub.3 alkylthio, halogen, hydroxyl, C.sub.3 -C.sub.6 cycloalkyl, benzyloxy, furyl, phenyl, halophenyl, loweralkylphenyl, loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano or triloweralkylammonium halide;
- C.sub.3 -C.sub.12 alkenyl optionally substituted with one of the following groups:
- C.sub.1 -C.sub.3 alkoxy, phenyl, halogen or loweralkoxycarbonyl or with two C.sub.1 -C.sub.3 alkoxy groups or two halogen groups;
- C.sub.3 -C.sub.6 cycloalkyl optionally substituted with one or two C.sub.1 -C.sub.3 alkyl groups;
- C.sub.3 -C.sub.16 alkynyl optionally substituted with one or two C.sub.1 -C.sub.3 alkyl groups;
- or a cation;
- R.sub.6 is hydrogen, hydroxyl, C.sub.3 -alkenyl, C.sub.3 -alkynyl or C.sub.1 -C.sub.4 alkyl optionally substituted with one hydroxyl or one chlorine group;
- B is H, COR.sub.4 or SO.sub.2 R.sub.5 ;
- R.sub.4 is C.sub.1 -C.sub.11 alkyl, chloromethyl or phenyl optionally substituted with one chloro, one nitro or one methoxy group;
- R.sub.5 is C.sub.1 -C.sub.4 alkyl or phenyl optionally substituted with one methyl group;
- W is O or S;
- R.sub.8 is C.sub.1 -C.sub.4 alkyl or phenyl;
- Y and Z may independently be selected from the group consisting of hydrogen, halogen, C.sub.1 -C.sub.6 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl, C.sub.1 -C.sub.6 alkoxy, C.sub.1 -C.sub.4 alkylthio, phenoxy, C.sub.1 -C.sub.4 haloalkyl, nitro, cyano, C.sub.1 -C.sub.4 alkylamino, di-C.sub.1 -C.sub.4 alkylamino, C.sub.1 -C.sub.4 alkylsulfonyl, difluoromethoxy, trifluoromethoxy, 1,1,2,2,-tetrafluoroethoxy, phenyl optionally substituted with one C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen;
- C.sub.3 -C.sub.8 straight or branched alkenyloxy optionally substituted with 1 to 3 halogens;
- C.sub.3 -C.sub.8 straight or branched alkynyloxy optionally substituted with 1 to 3 halogens;
- C.sub.2 -C.sub.6 straight or branched alkynyl substituted with hydroxy;
- C.sub.3 -C.sub.6 cycloalkyl interrupted by 1 oxygen, sulfur, amino or C.sub.1 -C.sub.4 alkylamino;
- and oxiranyl optionally substituted by one or two C.sub.1 -C.sub.4 alkyl;
- And at least one member of Y and Z must be selected from the group consisting of:
- C.sub.2 -C.sub.6 straight or branched alkenyl optionally substituted with phenyl, C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.2 -C.sub.6 straight or branched alkynyl optionally substituted with phenyl, C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.3 -C.sub.6 cycloalkyl optionally substituted with methyl, halogen or C.sub.1 -C.sub.4 alkoxy;
- C.sub.1 -C.sub.4 alkylcarbonyl optionally substituted with C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylcarbonylamino optionally substituted on nitrogen with C.sub.1 -C.sub.2 alkyl or C.sub.1 -C.sub.4 alkoxy and on carbon with C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylcarbonyloxy optionally substituted with C.sub.1 -C.sub.4 alkoxy or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkyl substituted with one or more of the following groups:
- C.sub.1 -C.sub.4 alkoxy optionally substituted with phenyl, thienyl, furyl, cyclopropyl, tetrahydrofuryl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 dialkylamino, C.sub.1 -C.sub.4 alkylamino, C.sub.1 -C.sub.4 trialkylammonium or 1 to 3 halogens;
- with the proviso that when the substituent on the C.sub.1 -C.sub.4 alkoxy group is C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylamino, C.sub.1 -C.sub.4 dialkylamino or C.sub.1 -C.sub.4 trialkylammonium, the respective heteroatoms are separated by at least 2 carbon atoms;
- C.sub.1 -C.sub.4 alkenyloxy optionally substituted with 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkynyloxy optionally substituted with 1 to 3 halogens;
- C.sub.3 -C.sub.6 cycloalkoxy;
- C.sub.3 -C.sub.6 cycloalkoxy;
- phenylthio;
- C.sub.1 -C.sub.4 alkylthio optionally substituted with phenyl or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylsulfinyl optionally substituted with phenyl or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylsulfonyl optionally substituted with phenyl or 1 to 3 halogens;
- C.sub.1 -C.sub.4 alkylamino optionally substituted on carbon by phenyl or 1 to 3 halogens;
- C.sub.1 -C.sub.4 dialkylamino;
- C.sub.1 -C.sub.4 trialkylammonium;
- C.sub.1 -C.sub.4 alkylcarbonyloxy;
- cyano;
- phenylamino, optionally substituted in the ring by 1 to 3 halogens, C.sub.1 -C.sub.4 alkyl, or C.sub.1 -C.sub.4 alkoxy;
- phenoxy, optionally substituted in the ring by 1 to 3 halogens, C.sub.1 -C.sub.4 alkyl, or C.sub.1 -C.sub.4 alkoxy;
- 2(or 3)-furyl optionally substituted with halogen or C.sub.1 -C.sub.3 alkyl;
- 2(or 3)-thienyl optionally substituted with halogen or C.sub.1 -C.sub.3 alkyl;
- N-methyl-2(or 3)-pyrrolyl;
- hydroxy;
- formyl;
- amino optionally substituted with C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylsulfonyl, C.sub.1 -C.sub.2 alkyl and C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 alkylsulfonyl and C.sub.1 -C.sub.2 alkyl, amino, C.sub.1 -C.sub.4 monoalkylamino, or C.sub.1 -C.sub.4 dialkylamino;
- 2(or 4)-pyridyloxy optionally substituted with C.sub.1 -C.sub.4 alkyl, trifluoromethyl or 1 or 2 halogens;
- C.sub.1 -C.sub.4 mono or dialkylaminocarbonylamino, optionally substituted on the nitrogen attached to the ring with C.sub.1 -C.sub.2 alkyl or C.sub.1 -C.sub.4 alkoxy;
- C.sub.1 -C.sub.4 alkoxycarbonylamino, optionally substituted on nitrogen with C.sub.1 -C.sub.2 alkyl or C.sub.1 -C.sub.4 alkoxy;
- and C.sub.1 -C.sub.4 mono or dialkylaminocarbonyloxy;
- Provided that when Y is hydroxy, Z cannot be hydrogen;
- Provided also that when B is COR.sub.4 or SO.sub.2 R.sub.5, A is CH.sub.3, CN or COOR.sub.3 in which R.sub.3 is other than H or a cation and W is O, then Y and Z cannot be alkylamino, hydroxyl or hydroxyloweralkyl;
- an N-oxide thereof when W is O, provided that R.sub.3 cannot be unsaturated alkyl and Y and Z cannot be alkylthioalkyl, alkylaminoalkyl, dialkylaminoalkyl, trialkylammoniumalkyl, amino, 2(or 4)-pyridyloxy, alkoxyamino or unsaturated alkyl;
- an optical isomer thereof when R.sub.1 and R.sub.2 are not the same;
- a tautomer thereof;
- or an agronomically acceptable acid addition salt thereof except when R.sub.3 is a cation.
61 more elements
Dependencies are inferred from the claim text.