6-aryl-4-aminopicolinates and their use as herbicides

Details 6-aryl-4-aminopicolinates and their use as herbicides 6-aryl-4-aminopicolinates and their use as herbicides

2002-07-30

2004-08-31

Pryor, Alton N. (Department: 1616)

Plant protecting and regulating compositions

Plant growth regulating compositions

Organic active compound containing

C504S251000, C504S252000, C504S254000, C504S255000, C504S260000, C546S250000, C546S268400, C546S268100, C546S255000, C546S280400, C546S281700, C546S283400

Reexamination Certificate

active

06784137

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention relates to certain novel 6-aryl-4-aminopicolinates and their derivatives and to the use of these compounds as herbicides.
A number of picolinic acids and their pesticidal properties have been described in the art. For example, U.S. Pat. No. 3,285,925 discloses 4-amino-3,5,6-trichloropicolinic acid derivatives and their use as plant growth control agents and herbicides. U.S. Pat. No. 3,325,272 discloses 4-amino-3,5-dichloropicolinic acid derivatives and their use for the control of plant growth. U.S. Pat. No. 3,317,549 discloses 3,6-dichloropicolinic acid derivatives and their use as plant growth control agents. U.S. Pat. No. 3,334,108 discloses chlorinated dithiopicolinic acid derivatives and their use as parasiticides. U.S. Pat. No. 3,234,229 discloses 4-amino-polychloro-2-trichloromethylpyridines and their use as herbicides. U.S. Pat. No. 3,755,338 discloses 4-amino-3,5-dichloro-6-bromopicolinates as fungicides. Belgian patent 788 756 discloses 6-alkyl-4-amino-3,5-dihalopicolinic acids as herbicides. In
Applied and Environmental Microbiology
, Vol. 59, No. 7, July 1993, pp. 2251-2256, 4-amino-3,6-dichloropicolinic acid is identified as a product of the anaerobic degradation of 4-amino-3,5,6-trichloropicolinic acid, the commercially available herbicide picloram. U.S. Pat. No. 6,297,197 B1 describes certain 4-aminopicolinates and their use as herbicides. U.S. Pat. No. 5,783,522 discloses certain 6-phenyl picolinic acids and their use as herbicides, desiccants and defoliating agents. WO 9821199 discloses 6-pyrazolylpyridines and their use as herbicides. U.S. Pat. No. 5,958,837 discloses the synthesis of 6-arylpicolinic acids and their use as herbicides, desiccants and defoliating agents. U.S. Pat. No. 6,077,650 discloses the use of 6-phenylpicolinic acids as photographic bleaching agents, and European Patent EP 0 972 765 A1 discloses the synthesis of 2-, 3- or 4-arylpyridines.
SUMMARY OF THE INVENTION
It has now been found that certain 6-aryl- or heteroaryl-4-aminopicolinic acids and their derivatives are potent herbicides with a broad spectrum of weed control against woody plants, grasses and sedges as well as broadleafs and with excellent crop selectivity. The compounds further possess excellent toxicological or environmental profiles.
The invention includes compounds of Formula I:
wherein
X represents H, halogen, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
alkylthio, aryloxy, nitro, C
1
-C
6
haloalkyl, C
1
-C
6
haloalkoxy, thiocyanide, or cyano;
Y represents aryl or heteroaryl;
Z represents halogen, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
alkylthio, aryloxy, nitro, C
1
-C
6
haloalkyl, C
1
-C
6
haloalkoxy, thiocyanide, or cyano; and
W represents —NO
2
, —N
3
, —NR
1
R
2
, —N═CR
3
R
4
or —NHN═CR
3
R
4
wherein
R
1
and R
2
independently represent H, C
1
-C
6
alkyl, C
3
-C
6
alkenyl, C
3
-C
6
alkynyl, aryl, heteroaryl, hydroxy, C
1
-C
6
alkoxy, amino, C
1
-C
6
acyl, C
1
-C
6
carboalkoxy, C
1
-C
6
alkylcarbamyl, C
1
-C
6
alkylsulfonyl, C
1
-C
6
trialkylsilyl or C
1
-C
6
dialkyl phosphonyl or R
1
and R
2
taken together with N represent a 5- or 6-membered saturated or unsaturated ring which may contain additional O, S or N heteroatoms; and
R
3
and R
4
independently represent H, C
1
-C
6
alkyl, C
3
-C
6
alkenyl, C
3
-C
6
alkynyl, aryl or heteroaryl or R
3
and R
4
taken together with ═C represent a 5- or 6-membered saturated ring; and
agriculturally acceptable derivatives of the carboxylic acid group.
Compounds of Formula I wherein X represents H or F wherein Y represents para-substituted phenyl with or without other substituents, wherein Z represents Cl, wherein W represents NR
1
R
2
and R
1
and R
2
represent H or C
1
-C
6
alkyl, are independently preferred. Also preferred are compounds wherein Y represents
wherein A represents O or CH
2
and at least one of A is O. The aryl and heteroaryl groups which are represented by Y are preferably substituted with one or two groups independently selected from halogen, C
1
-C
2
alkyl and C
1
-C
2
haloalkyl.
The invention includes herbicidal compositions comprising a herbicidally effective amount of a compound of Formula I and agriculturally acceptable derivatives of the carboxylic acid group in admixture with an agriculturally acceptable adjuvant or carrier. The invention also includes a method of use of the compounds and compositions of the present invention to kill or control undesirable vegetation by application of an herbicidal amount of the compound to the vegetation or to the locus of the vegetation as well as to the soil prior to emergence of the vegetation.
DETAILED DESCRIPTION OF THE INVENTION
The herbicidal compounds of the present invention are derivatives of 4-aminopicolinic acids of Formula II:
These compounds are characterized by possessing halogen, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
alkylthio, aryloxy, nitro, C
1
-C
6
haloalkyl, C
1
-C
6
haloalkoxy, thiocyanide, or cyano substituents in the 3-position with halogen being preferred and chlorine being most preferred; by possessing hydrogen, halogen, C
1
-C
6
alkyl, C
1
-C
6
alkoxy, C
1
-C
6
alkylthio, aryloxy, nitro, C
1
-C
6
haloalkyl, C
1
-C
6
haloalkoxy, thiocyanide, or cyano substituents in the 5-position with hydrogen and fluorine being preferred; and by possessing aryl and heteroaryl substituents in the 6-position with halogen, C
1
-C
2
alkyl and C
1
-C
2
haloalkyl substituted phenyl, pyridinyl, benzofuranyl, benzothienyl, thienyl and thiazoyl being preferred.
The amino group at the 4-position can be unsubstituted or substituted with one or more C
1
-C
6
alkyl, C
3
-C
6
alkenyl, C
3
-C
6
alkynyl, aryl, heteroaryl, hydroxy, C
1
-C
6
alkoxy or amino substituents. The amino group can be further derivatized as an amide, a carbamate, a urea, a sulfonamide, a silylamine, a phosphoramidate, an imine or a hydrazone. Such derivatives are capable of breaking down into the amine. An unsubstituted amino group or one substituted with one or two alkyl substituents is preferred.
The carboxylic acids of Formula I are believed to be the compounds that actually kill or control undesirable vegetation and are typically preferred. Analogs of these compounds in which the acid group of the picolinic acid is derivatized to form a related substituent that can be transformed within plants or the environment to a acid group possess essentially the same herbicidal effect and are within the scope of the invention. Therefore, an “agriculturally acceptable derivative”, when used to describe the carboxylic acid functionality at the 2-position, is defined as any salt, ester, acylhydrazide, imidate, thioimidate, amidine, amide, orthoester, acylcyanide, acyl halide, thioester, thionoester, dithiolester, nitrile or any other acid derivative well known in the art which (a) does not substantially affect the herbicidal activity of the active ingredient, i.e., the 6-aryl or heteroaryl-4-aminopicolinic acid, and (b) is or can be hydrolyzed, oxidized or metabolized in plants or soil to the picolinic acid of Formula I that, depending upon the pH, is in the dissociated or the undissociated form. The preferred agriculturally acceptable derivatives of the carboxylic acid are agriculturally acceptable salts, esters and amides. Likewise, an “agriculturally acceptable derivative”, when used to describe the amine functionality at the 4-position, is defined as any salt, silylamine, phosphorylamine, phosphinimine, phosphoramidate, sulfonamide, sulfilimine, sulfoximine, aminal, hemiaminal, amide, thioamide, carbamate, thiocarbamate, amidine, urea, imine, nitro, nitroso, azide, or any other nitrogen containing derivative well known in the art which (a) does not substantially affect the herbicidal activity of the active ingredient, i.e., the 6-aryl or heteroaryl-4-aminopicolinic acid, and (b) is or can be hydrolyzed in plants or soil to a free amine of Formula II. N-Oxides which are also capable of breaking into the parent pyridine of Formula II are also covered by the scope of this invention.
Suitable salts

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