(2-Imidazolin-2-yl)thieno and furo(2,3-b) and (3,2-b) pyridines and intermediates for the preparation thereof, and use of said compounds as herbicidal agents.

Claim 1

A compound having the structure: or wherein - - represents a single or a double bond; R 1 is C 1 -C 4 alkyl; R 2 is C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl; and when R 1 and R 2 are taken together with the carbon to which they are attached they may represent C 3 -C 6 cycloalkyl optionally substituted with methyl; A is COOR 3 , CHO, CH 2 0H, COCH 2 0H, CONHCH 2 CH 2 0H, CONHOH, or R 3 is hydrogen, C 1 -C 12 alkyl, which may be interrupted by one or more 0 or S and is optionally substituted with one of the following groups: C l -C 3 alkoxy, halogen, hydroxy, C 3 -C 6 cycloalkyl, benzyloxy, furyl, phenyl, furfuryl, halophenyl, loweralkylphenyl, loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano, C l -C 4 alkylthio or triloweralkylammonium, C 3 -C 6 alkenyl optionally substituted with one of the following groups: C l -C 3 alkoxy, phenyl, halogen or with two C 1 -C 3 alkox y groups or two halogen groups: C 3 -C6 cycloalkyl optionally substituted with one or two C l -C 3 alkyl groups; C 3 -C 10 alkynyl optionally substituted with phenyl, halogen or CH 2 0H; or a cation of alkali metals, alkaline earth metals, (Ca, Ba) manganese, copper, iron, ammonium or organic ammonium; R C and R D are H or CH 3 ; B is H, COR 4 or SO 2 R 5 , provided that when B is COR 4 or SO 2 R 5 , and A is COOR 3 , R 3 cannot be hydrogen or a salt-forming cation; R 4 is C 1 -C 11 alkyl, chloromethyl or phenyl optionally substituted with one chloro, one nitro, one methyl, or one methoxy group; R 5 is C 1 -C 5 alkyl or phenyl optionally substituted with one methyl group, chloro or nitro; W is 0 or S; X is 0, S, or, where - - is a single bond, -S=O; Y and Y', Z and Z' are hydrogen, halogen, C l -C 6 alkyl, C l -C 4 hydroxyloweralkyl, C 1 -C 6 alkoxy, C 1 -C 6 acyloxy, benzoyloxy optionally substituted with one or two C l -C 4 alkyl, C l -C 4 alkoxy, halogen; C l - C 4 alkylthio, phenoxy, C l -C 4 haloalkyl, C l -C 4 haloalkoxy, nitro, cyano, C 1 -C 4 alkylamino, C 1 -C 4 dialkylamino, C 1 -C 4 alkylsulfonyl or phenyl optionally substituted with one or two C 1 -C 4 alkyl, C l -C 4 alkoxy, halogen, or any combination of two of these groups and wherein Y and Z are the same group provided that Y and Z are H, halogen, alkyl or alkoxy, and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure -(CH 2 ) n -, where n is an integer selected from 3 or 4; or where L, M, Q and R 7 each represent hydrogen, halogen, nitro, C 1 -C 4 loweralkyl, C 1 -C 4 loweralkoxy, methoxy, phenyl and phenoxy, with the proviso that only one of L, M, Q or R 7 , may represent a substituent other than hydrogen, halogen, C l -C 4 alkyl or C 1 -C 4 alkoxy; or the pyridine N-oxides thereof, when W is 0 or S and A is COOR 3 ; and when R 1 and R 2 are not the same, the optical isomers thereof, and, except when R 3 is a salt-forming cation, the acid addition salts thereof.

Claim 9

A method for the control of monocotyledonous and dicotyledonous annual, perennial and aquatic plant species comprising: applying to the foliage of said plants or to soil or water containing seeds or other prcpogating organs thereof, a herbicidally effective amount of a compound having a structure: wherein - - represents a single or a double bond; R 1 is C 1 -C 4 alkyl; R 2 is C l -C 4 alkyl or C 3 -C 6 cycloalkyl; and when R 1 and R 2 are taken together with the carbon to which they are attached they may represent C 3 -C 6 cycloalkyl optionally substituted with methyl; A is COOR 3 , CHO, CH 2 0H, COCH 2 0H, CONHCH 2 CH 2 0H, CONHOH, or R 3 is hydrogen, C 1 -C 12 alkyl optionally substituted with one of the following groups: C 1 -C 3 alkoxy, halogen, hydroxy, C 3 -C 6 cycloalkyl, benzyloxy, furyl, phenyl, furfuryl, halophenyl, loweralkylphenyl, loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano, C l -C 4 alkylthio or triloweralkylammonium, in addition the alkyl chain may be interrupted by one or more 0 or S; C 3 -C 6 alkenyl optionally substituted with one of the following groups: C 1 -C 3 alkoxy, phenyl, halogen or with two C l -C 3 alkoxy groups or two halogen groups: C 3 -C 6 cycloalkyl optionally substituted with one or two C l -C 3 alkyl groups; C 3 -C 10 alkynyl optionally substituted with phenyl, halogen or CH 2 0H; or a cation of alkali metals, alkaline earth metals, (Ca, Ba) manganese, copper, iron, ammonium or organic ammonium; R C and R D are H, or CH 3 ; B is H, COR 4 or S0 2 R 5 , provided that when B is COR 4 or S0 2 R 5 , and A is COOR 3 , R 3 cannot be hydrogen or a salt-forming cation; R4 is C 1 -C 11 alkyl, chloromethyl or phenyl optionally substituted with one chloro, one nitro, one methyl, or one methoxy group; R 5 is Ci-C 5 alkyl or phenyl optionally substituted with one methyl group, chloro or nitro; W is 0 or S; X is 0, S, or -S=O; Y and Y', Z and Z' are hydrogen, halogen, C 1 -C 6 alkyl, C l -C 4 hydroxyloweralkyl, C 1 -C 6 alkoxy, C 1 -C 6 acyloxy, benzoyloxy optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; C 1 - C 4 alkylthio, phenoxy, C 1 -C 4 haloalkyl, C l -C 4 haloalkoxy, nitro, cyano, C l -C 4 alkylamino, C 1 -C 4 dialkylamino, C l -C 4 alkylsulfonyl or phenyl optionally substituted with one or two C l -C 4 alkyl, C 1 -C 4 alkoxy, halogen, or any combination of two of these groups and wherein Y and Z are the same group provided that Y and Z are H, halogen, alkyl or alkoxy, and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure -(CH 2 ) n -, where n is an integer selected from 3 or 4; or , where L, M, Q and R 7 each represent hydrogen, halogen, nitro, C l -C 4 loweralkyl, C 1 -C 4 loweralkoxy, methoxy, phenyl and phenoxy, with the proviso that only one of L, M, Q or R 7 , may represent a substituent other than hydrogen, halogen, C 1 -C 4 alkyl or C l -C 4 alkoxy; or the pyridine N-oxides thereof, when W is 0 or S and A is COOR 3 ; and when R 1 and R 2 are not the same, the optical isomers thereof, and, except when R 3 is a salt-forming cation, the acid addition salts thereof.

Claim 10

A method for the control of monocotyledonous and dicotyledonous annual, perennial and aquatic plant species comprising: applying to the foliage of said plants or to soil or water containing seeds or other prcpogating organs thereof, a herbicidally effective amount of a compound having a structure: wherein - - represents a single or a double bond; R 1 is C 1 -C 4 alkyl; R 2 is C l -C 4 alkyl or C 3 -C 6 cycloalkyl; and when R 1 and R 2 are taken together with the carbon to which they are attached they may represent C 3 -C 6 cycloalkyl optionally substituted with methyl; A is COOR 3 , CHO, CH 2 0H, COCH 2 0H, CONHCH 2 CH 2 0H, CONHOH, or R 3 is hydrogen, C 1 -C 12 alkyl optionally substituted with one of the following groups: C 1 -C 3 alkoxy, halogen, hydroxy, C 3 -C 6 cycloalkyl, benzyloxy, furyl, phenyl, furfuryl, halophenyl, loweralkylphenyl, loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano, C l -C 4 alkylthio or triloweralkylammonium, in addition the alkyl chain may be interrupted by one or more 0 or S; C 3 -C 6 alkenyl optionally substituted with one of the following groups: C 1 -C 3 alkoxy, phenyl, halogen or with two C l -C 3 alkoxy groups or two halogen groups: C 3 -C 6 cycloalkyl optionally substituted with one or two C l -C 3 alkyl groups; C 3 -C 10 alkynyl optionally substituted with phenyl, halogen or CH 2 0H; or a cation of alkali metals, alkaline earth metals, (Ca, Ba) manganese, copper, iron, ammonium or organic ammonium; R C and R D are H, or CH 3 ; B is H, COR 4 or S0 2 R 5 , provided that when B is COR 4 or S0 2 R 5 , and A is COOR 3 , R 3 cannot be hydrogen or a salt-forming cation; R4 is C 1 -C 11 alkyl, chloromethyl or phenyl optionally substituted with one chloro, one nitro, one methyl, or one methoxy group; R 5 is Ci-C 5 alkyl or phenyl optionally substituted with one methyl group, chloro or nitro; W is 0 or S; X is 0, S, or -S=O; Y and Y', Z and Z' are hydrogen, halogen, C 1 -C 6 alkyl, C l -C 4 hydroxyloweralkyl, C 1 -C 6 alkoxy, C 1 -C 6 acyloxy, benzoyloxy optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; C 1 - C 4 alkylthio, phenoxy, C 1 -C 4 haloalkyl, C l -C 4 haloalkoxy, nitro, cyano, C l -C 4 alkylamino, C 1 -C 4 dialkylamino, C l -C 4 alkylsulfonyl or phenyl optionally substituted with one or two C l -C 4 alkyl, C 1 -C 4 alkoxy, halogen, or any combination of two of these groups and wherein Y and Z are the same group provided that Y and Z are H, halogen, alkyl or alkoxy, and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure -(CH 2 ) n -, where n is an integer selected from 3 or 4; or , where L, M, Q and R 7 each represent hydrogen, halogen, nitro, C l -C 4 loweralkyl, C 1 -C 4 loweralkoxy, methoxy, phenyl and phenoxy, with the proviso that only one of L, M, Q or R 7 , may represent a substituent other than hydrogen, halogen, C 1 -C 4 alkyl or C l -C 4 alkoxy; or the pyridine N-oxides thereof, when W is 0 or S and A is COOR 3 ; and when R 1 and R 2 are not the same, the optical isomers thereof, and, except when R 3 is a salt-forming cation, the acid addition salts thereof.

Claim 11

A method for regulating the growth of plants and increasing the yield of gramineacous and liguminous crops, comprising applying to the foliage of said plants an effective amount of a compound selected from the compounds having the structures: and wherein - - represents a single or a double bond; R 3 is hydrogen, C 1 -C 12 alkyl optionally substituted with one of the following groups: C 1 -C 3 alkoxy, halogen, hydroxy, C 3 -C 6 cycloalkyl, benzyloxy, furyl, phenyl, furfuryl, halophenyl, loweralkylphenyl, loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano, C l -C 4 alkylthio or triloweralkylammonium, in addition the alkyl chain may be interrupted by one or more 0 or S; C 3 -C 6 alkenyl optionally substituted with one of the following groups: C 1 -C 3 alkoxy, phenyl, halogen or with two C ] -C 3 alkoxy groups or two halogen groups: C 3 -C 6 cycloalkyl optionally substituted with one or two C l -C 3 alkyl groups; C 3 -C 10 alkynyl optionally substituted with phenyl, halogen or CH 2 0H; or a cation of alkali metals, alkaline earth metals, (Ca, Ba) maganese, copper, iron, ammonium or organic ammonium; X is 0, S, or -S=O; Y and Y', Z and Z' are hydrogen, halogen, Cl - C6 alkyl, C l -C 4 hydroxyloweralkyl, C I -C6 alkoxy, C 1 -C 6 acyloxy, benzoyloxy optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; C 1 - C 4 alkylthio, phenoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, nitro, cyano, C l -C 4 alkylamino, C 1 -C 4 dialkylamino, C 1 -C 4 alkylsulfonyl or phenyl optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, or any combination of two of these groups and wherein Y and Z are the same group provided that Y and Z are H, halogen, alkyl or alkoxy, and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure -(CH 2 ) n -, where n is an integer selected from 3 or 4; or where L, M, Q and R 7 each represent hydrogen, halogen, nitro, C 1 -C 4 loweralkyl, C 1 -C 4 loweralkoxy, methoxy, phenyl and phenoxy, with the proviso that only one of L, M, Q or R 7 , may represent a substituent other than hydrogen, halogen, C l -C 4 alkyl or C 1 -C 4 alkoxy; or the pyridine N-oxides thereof, and the optical isomers thereof, and, except when R 3 is a salt-forming cation, the acid addition salts thereof.

Claim 12

A method for regulating the growth of plants and increasing the yield of gramineacous and liguminous crops, comprising applying to the foliage of said plants an effective amount of a compound selected from the compounds having the structures: and wherein - - represents a single or a double bond; R 3 is hydrogen, C 1 -C 12 alkyl optionally substituted with one of the following groups: C 1 -C 3 alkoxy, halogen, hydroxy, C 3 -C 6 cycloalkyl, benzyloxy, furyl, phenyl, furfuryl, halophenyl, loweralkylphenyl, loweralkoxyphenyl, nitrophenyl, carboxyl, loweralkoxycarbonyl, cyano, C l -C 4 alkylthio or triloweralkylammonium, in addition the alkyl chain may be interrupted by one or more 0 or S; C 3 -C 6 alkenyl optionally substituted with one of the following groups: C 1 -C 3 alkoxy, phenyl, halogen or with two C ] -C 3 alkoxy groups or two halogen groups: C 3 -C 6 cycloalkyl optionally substituted with one or two C l -C 3 alkyl groups; C 3 -C 10 alkynyl optionally substituted with phenyl, halogen or CH 2 0H; or a cation of alkali metals, alkaline earth metals, (Ca, Ba) maganese, copper, iron, ammonium or organic ammonium; X is 0, S, or -S=O; Y and Y', Z and Z' are hydrogen, halogen, Cl - C6 alkyl, C l -C 4 hydroxyloweralkyl, C I -C6 alkoxy, C 1 -C 6 acyloxy, benzoyloxy optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; C 1 - C 4 alkylthio, phenoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, nitro, cyano, C l -C 4 alkylamino, C 1 -C 4 dialkylamino, C 1 -C 4 alkylsulfonyl or phenyl optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, or any combination of two of these groups and wherein Y and Z are the same group provided that Y and Z are H, halogen, alkyl or alkoxy, and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure -(CH 2 ) n -, where n is an integer selected from 3 or 4; or where L, M, Q and R 7 each represent hydrogen, halogen, nitro, C 1 -C 4 loweralkyl, C 1 -C 4 loweralkoxy, methoxy, phenyl and phenoxy, with the proviso that only one of L, M, Q or R 7 , may represent a substituent other than hydrogen, halogen, C l -C 4 alkyl or C 1 -C 4 alkoxy; or the pyridine N-oxides thereof, and the optical isomers thereof, and, except when R 3 is a salt-forming cation, the acid addition salts thereof.

Claim 13

A method for the preparation of a compound having the structure: or wherein - - represents a single or a double bond; R 1 is C 1- C 4 alkyl; R2 is C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl; and when R 1 and R 2 are taken together with the carbon to which they are attached they may represent C 3 -C 6 cycloalkyl optionally substituted with methyl; W is 0 or S; X is 0, S, or -S=0; Y and Y', Z and Z' are hydrogen, halogen, C 1 -C 6 alkyl, C l -C 4 hydroxyloweralkyl, C 1 -C 6 alkoxy, C l -C 6 acyloxy, benzoyloxy optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; C l - C 4 alkylthio, phenoxy, C I -C 4 haloalkyl, C l -C 4 haloalkox y, nitro, cyano, C 1 -C 4 alkylamino, C l -C 4 dialkylamino, C 1 -C 4 alkylsulfonyl or phenyl optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, or any combination of two of these groups and wherein Y and Z are the same group provided that Y and Z are H, halogen, alkyl or alkoxy and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure -(CH 2 ) n -, where n is an integer selected from 3 or 4; or where L, M, Q and R 7 each represent hydrogen, halogen, nitro, C 1 -C 4 loweralkyl, C 1 -C 4 loweralkoxy, methoxy, phenyl and phenoxy, with the proviso that only one of L, M, Q or R 7 , may represent a substituent other than hydrogen, halogen, C l -C 4 alkyl or C 1 -C 4 alkoxy; or the pyridine N-oxides thereof, and when R 1 and R 2 are not the same, the optical isomers thereof, and the acid addition salts thereof; comprising reacting a compound having a structure selected from: and wherein X, Y, Z, W, R 1 and R 2 are as described above, with from 2 to 20 molar equivalents of an aqueous or aqueous alcoholic sodium or potassium hydroxide at a temperature of from 25 to 100°C and thereafter acidifying the thus-formed reaction mixture to a pH between 2 and 4 with a strong mineral acid.

Claim 14

A method for the preparation of a compound having the structure: or wherein - - represents a single or a double bond; R 1 is C 1- C 4 alkyl; R2 is C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl; and when R 1 and R 2 are taken together with the carbon to which they are attached they may represent C 3 -C 6 cycloalkyl optionally substituted with methyl; W is 0 or S; X is 0, S, or -S=0; Y and Y', Z and Z' are hydrogen, halogen, C 1 -C 6 alkyl, C l -C 4 hydroxyloweralkyl, C 1 -C 6 alkoxy, C l -C 6 acyloxy, benzoyloxy optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen; C l - C 4 alkylthio, phenoxy, C I -C 4 haloalkyl, C l -C 4 haloalkox y, nitro, cyano, C 1 -C 4 alkylamino, C l -C 4 dialkylamino, C 1 -C 4 alkylsulfonyl or phenyl optionally substituted with one or two C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, or any combination of two of these groups and wherein Y and Z are the same group provided that Y and Z are H, halogen, alkyl or alkoxy and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and, when taken together, Y and Z may form a ring in which YZ are represented by the structure -(CH 2 ) n -, where n is an integer selected from 3 or 4; or where L, M, Q and R 7 each represent hydrogen, halogen, nitro, C 1 -C 4 loweralkyl, C 1 -C 4 loweralkoxy, methoxy, phenyl and phenoxy, with the proviso that only one of L, M, Q or R 7 , may represent a substituent other than hydrogen, halogen, C l -C 4 alkyl or C 1 -C 4 alkoxy; or the pyridine N-oxides thereof, and when R 1 and R 2 are not the same, the optical isomers thereof, and the acid addition salts thereof; comprising reacting a compound having a structure selected from: and wherein X, Y, Z, W, R 1 and R 2 are as described above, with from 2 to 20 molar equivalents of an aqueous or aqueous alcoholic sodium or potassium hydroxide at a temperature of from 25 to 100°C and thereafter acidifying the thus-formed reaction mixture to a pH between 2 and 4 with a strong mineral acid.