WO1993021164A1

WO1993021164A1 - Herbicidal triazolesulfonates

Info

Publication number: WO1993021164A1
Application number: PCT/US1993/003187
Authority: WO
Inventors: Morris Padgett Rorer
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1992-04-10
Filing date: 1993-04-06
Publication date: 1993-10-28
Also published as: AU4025893A

Abstract

Substituted triazolesulfonates of formula (I) useful as herbicides, their agriculturally suitable compositions, as well as methods for their use as preemergent or postemergent herbicides or plant growth regulants are disclosed.

Description

TITLE

HERBICIDAL TRIAZOLESULFONATES

CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part of U.S. Serial No. 07/924,632, filed August 4, 1992.

BACKGROUND OF THE INVENTION

This invention relates to certain substituted triazolesulfonates which are useful as herbicides and their agriculturally suitable compositions as well as methods for their use as general or selective

preemergent or postemergent herbicides or as plant growth regulants.

New compounds effective for controlling the growth of undesired vegetation are in constant demand. In the most common situation, such compounds are sought to selectively control the growth of weeds in useful crops such as cotton, rice, corn, wheat and soybeans, to name a few. Unchecked weed growth in such crops can cause significant losses, reducing profit to the farmer and increasing costs to the consumer. In other situations, herbicides are desired which will control all plant growth. Examples of areas in which complete control of all vegetation is desired are areas around railroad tracks, storage tanks and industrial storage areas. There are many products commercially available for these purposes, but the search continues for products which are more effective, less costly and

environmentally safe.

U.S. 4,889,553 discloses herbicidal sulfonamides of the formula

wherein, inter alia

R¹ is (in part) aminocarbonyl;

R² is (in part) H;

R³ is a substituted or unsubstituted heterocyclic, benzoheterocyclic, aryl or aralkyl group; and

R⁴ is (in part) H, a substituted or unsubstituted alkyl or aralkyl.

SUMMARY OF THE INVENTION

This invention comprises novel compounds of

Formula I, agriculturally suitable compositions

containing them, and their method-of-use as preemergent and/or postemergent herbicides and/or plant growth regulants.

wherein

A is C₁-C₅ alkyl substituted with 1 to 7 halogens; phenyl optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; pyridine, pyrimidine, pyrazine or triazine, each ring optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; or a

5-membered heterocyclic ring containing 1 to 3 heteroatoms selected from the group 0-3 nitrogens, 0-1 oxygen and 0-1 sulfur, each ring substituted with 1 to 4 substituents selected from R³, R⁴, R⁵ and R⁶;

Z is O; R¹ is H; C₁-C₆ alkyl optionally substituted with C₁-C₃ alkoxy or 1 to 5 halogens; C₃-C₆

cycloalkyl; C₂-C₆ alkenyl optionally

substituted with 1 to 3 halogens; C₃-C₆

alkynyl; or C₁-C₃ alkoxy;

R² is C₁-C₆ alkyl optionally substituted with C₁-C₃ alkoxy or 1 to 5 halogens; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl optionally substituted with 1 to 3 halogens; or C₃-C₆ alkynyl;

R¹ and R² may be taken together to form -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or -(CH₂)₆-, each ring optionally substituted with 1 to 3 substituents selected from halogen and C₁-C₃ alkyl;

R³ is H; halogen; C₁-C₆ alkyl optionally

substituted with one or more halogen, C₁-C₆ alkoxy, CN, CO₂R⁷, S(O)_mR⁸, C(O)NR⁹R¹⁰ or

SO₂NR¹³R¹⁴; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl;

C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; C₁-C₃ alkoxy; CN; CO₂R¹¹; S(O)_pR¹²; C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C(OR²⁰) (OR²¹)R²²; CR²³=NOR²⁴; NO₂;

NR²⁵R²⁶; or phenyl or benzyl, each ring

optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy;

R⁴ and R⁵ are independently H; halogen; C₁-C₆ alkyl optionally substituted with one or more

halogen, C₁-C₆ alkoxy, CN, CO₂R⁷, S(O)_mR⁸,

C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; C₁-C₆ alkoxy; CN; CO₂R¹¹; S(O)_pR¹²; C(O)NR¹⁵R¹⁶;

SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C (OR²⁰) (OR²¹) R²²; CR²³=NOR²⁴; NR²⁵R²⁶; or phenyl or benzyl, each ring

optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy; R⁶ is H; C₁-C₆ alkyl optionally substituted with one or more halogen, C₁-C₆ alkoxy, CN, CO₂R⁷, S(O)_mR⁸, C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; CN; CO₂R¹¹; SO₂R¹²; C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; or phenyl or benzyl, each ring optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy; R⁷ and R¹¹ are independently H, C₁-C₃ alkyl or

allyl;

R⁸ and R¹² are independently C₁-C₃ alkyl;

R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are

independently H or C₁-C₃ alkyl; R⁹ and R¹⁰ may be taken together as piperidine or pyrrolidine; R¹³ and R¹⁴ may be taken together as piperidine or pyrrolidine; R¹⁵ and R¹⁶ may be taken together as piperidine or pyrrolidine; and R¹⁷ and R¹⁸ may be taken together as piperidine or pyrro1idine;

R¹⁹, R²² and R²³ are independently H or C₁-C₃ alkyl; R²⁰ and R²¹ are independently C₁-C₃ alkyl or may be taken together to form a 5- or 6-membered ring; R²⁴ is C₁-C₃ alkyl;

R²⁵ and R²⁶ are independently H, C₁-C₃ alkyl or may be taken together as piperidine or pyrrolidine; m and p are independently 0, 1 or 2;

n is 0 or 1;

and their agriculturally suitable salts;

provided that

1) R³, R⁴ and R⁵ are independently bonded to

carbon, and R⁶ is bonded to nitrogen;

2) when A is a 5-membered heterocyclic ring and n is 0, then Z is bonded to a carbon atom in A;

3) when A is triazine then n is 1; 4) when A is phenyl optionally substituted with R³, R⁴, and R⁵, then n is 1.

In the above definitions, the term "alkyl" includes straight chain or branched alkyl, e.g., methyl, ethyl, i--propyl, isopropyl or the different butyl isomers. Alkoxy includes methoxy, ethoxy, n-propyloxy,

isopropyloxy etc. Alkenyl includes straight chain or branched alkenes, e.g., 1-propenyl, 2-propenyl,

3-propenyl and the different butenyl isomers. Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "halogen", either alone or in compound words such as "haloalkenyl" or "haloalkyl", means fluorine, chlorine, bromine or iodine. Further, when used in compound words, said alkyl or alkenyl may be partially or fully substituted with halogen atoms, which may be the same or different. Examples of haloalkyl include CH₂CH₂F, CF₂CF₃ and CH₂CHFCl.

Compounds of Formula I may exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be the more active. One skilled in the art knows how to separate said enantiomers, diasteriomers and geometric isomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures.

Preferred for reasons including ease of synthesis and or greater herbicidal efficacy are:

1. A compound of Formula I wherein

A is C₁-C₅ alkyl substituted with 1 to 7 halogens; phenyl optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; pyridine, pyrimidine, pyrazine or triazine, each ring optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; or a 5-membered heterocyclic ring containing 1 to 3 heteroatoms selected from the group 0-3 nitrogens, 0-1 oxygen and 0-1 sulfur, each ring substituted with 1 to 4 substituents selected from R³, R⁴, R⁵ and

R⁶;

R¹ is H; C₁-C₆ alkyl; C₂-C₃ haloalkyl; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl; C₃-C₆ alkynyl; or C₁-C₃ a-lkoxy;

R² is C₁-C₃ alkyl; C₂-C₃ haloalkyl; C₃-C₆

cycloalkyl; C₂-C₆ alkenyl; or C₃-C₆ alkynyl; R¹ and R² may be taken together to form

-(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or -(CH₂)₆-;

R³ is H; halogen; C₁-C₆ alkyl optionally

substituted with one or more halogen, C₁-C₆ alkoxy, CN, CO₂R⁷, S(O)_mR⁸, C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; C₁-C₆ alkoxy; CN; CO₂R¹¹;

S(O)_pR¹²; C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C(OR²⁰) (OR²¹)R²²; CR²³=NOR²⁴; NO₂; NR²⁵R²⁶; or phenyl or benzyl, each ring optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy;

R⁴ and R⁵ are independently H; halogen; C₁-C₆ alkyl optionally substituted with one or more halogen, C₁-C₆ alkoxy, CN, CO₂R⁷,

S(O)_mR⁸, C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl; C₂-C₆

haloalkenyl; C₂-C₆ alkynyl; C₁-C₃ alkoxy;

CN; CO₂R¹¹; S(O)_pR¹²; C (O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C(OR²⁰) (OR²¹)R²²; CR²³=NOR²⁴;

NR²⁵R²⁶; or phenyl or benzyl, each ring optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl and C₁-C₃ alkoxy;

R⁶ is H; C₁-C₆ alkyl optionally substituted with one or more halogen, C₁-C₃ alkoxy, CN, CO₂R⁷, S(O)_mR⁸, C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; CN; CO₂R¹¹; SO₂R¹²; C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; or phenyl or benzyl, each ring optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl and C₁-C₃ alkoxy.

A compound of Formula I wherein

A is C₁-C₃ alkyl substituted with 1 to 8 halogens; phenyl or pyridine, each ring optionally substituted with 1 to 3 substituents selected from R³, R⁴ or R⁵; or

wherein

X is NR⁶, O or S.

3. A compound of Preferred 2 wherein

n is 0; and

R¹ and R² are independently C₁-C₃ alkyl or C₂-C₃ alkenyl.

4. A compound of Preferred 3 wherein

R³, R⁴ and R⁵ are independently H; F, Cl; Br;

C₁-C₃ alkyl optionally substituted with one or more F, Cl, Br or C₁-C₃ alkoxy; cyclopropyl; C₂-C₃ alkenyl; C₂-C₃ haloalkenyl; C₂-C₃ alkynyl; C₁-C₃ alkoxy; CN; CO₂ (C₁-C₂ alkyl), S(O)_p(C₁-C₂ alkyl); C(O)NR¹⁵R¹⁶;

SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C(OR²⁰) (OR²¹)R²²;

CR²³=NOR²⁴; NR²⁵R²⁶; or phenyl optionally substituted with 1 to 3 substituents

selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy;

R⁶ is H, C₁-C₄ alkyl optionally substituted

with one or more F, Cl, Br, C₁-C₃ alkoxy, CN, CO₂(C₁-C₂ alkyl), S(O)_m(C₁-C₂ alkyl), C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₂-C₄ alkenyl; C₂-C₄ haloalkenyl; C₂-C₄ alkynyl; CO₂R¹¹; SO₂ (C₁-C₂ alkyl); C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; or phenyl or benzyl, each ring optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy;

R⁹, R¹⁰, R¹³ and R¹⁴ are independently C₁-C₂

alkyl;

R¹¹ is C₁-C₂ alkyl or allyl;

R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁵ and R²⁶ are independently C₁-C₃ alkyl; and

R¹⁹, R²² and R²³ are independently H or C₁-C₂ alkyl.

5. A compound of Preferred 4 wherein

A is C₁-C₅ alkyl substituted with 1 to 7 halogens; pyridine, optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; A-3; A-4; or A-5;

R¹ and R² are independently ethyl or allyl; and R⁵ is H, Cl, CH₃, C₂H₅ or CF₃.

6. A compound of Preferred 5 wherein

R³ and R⁴ are independently H, Cl, C₁-C₃ alkyl,

CF₃, C₁-C₂ alkoxy, C₂-C₃ alkenyl or CN; and R⁶ is C₁-C₃ alkyl optionally substituted with 1 to 3 F, Cl, Br, C₁-C₂ alkoxy, CN, CO₂ (C₁-C₂ alkyl) or C(O)NR⁹R¹⁰; allyl; propargyl;

C(O)NR¹⁵R¹⁶; phenyl; or benzyl.

Specifically preferred for reasons of greatest herbicidal efficacy are the compounds of Preferred 6 which are:

● 2,2,2-trifluoroethyl 1-[[ethyl(1-methylethyl)- amino]carbonyl]-1H-1,2,4-triazole-3-sulfonate; and

● 2,2,2-trifluoroethyl 1-[(diethylamino)carbonyl]- 1H-1,2,4-triazole-3-sulfonate. This invention also comprises novel intermediates of Formula II

wherein

R¹ is H, C₁-C₆ alkyl, C₂-C₃ haloalkyl, C₃-C₆

cycloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl or C₁-C₃ alkoxy;

R² is C₁-C₆ alkyl, C₂-C₃ haloalkyl, C₃-C₆

cycloalkyl, C₂-C₆ alkenyl or C₃-C₆ alkynyl;

R¹ and R² may be taken together as -(CH₂)₃-,

-(CH₂)₄-, -(CH₂)₅- or -(CH₂)₆-, each ring optionally substituted with C₁-C₃ alkyl; and Y is F or Cl.

Preferred intermediates are the compounds of

Formula II wherein R¹ and R² are independently C₁-C₃ alkyl and Y is Cl.

DETAILED DESCRIPTION OF THE INVENTION

Compounds of the invention of Formula I can be prepared by one or more of the following methods

described in Schemes 1 to 3 or variations obvious to one skilled in the art. In cases where the substituent of a starting material is not compatible with the reaction conditions described for any of the reaction Schemes 1 to 6, it can be assumed that the substituent is converted to a protected form prior to the described reaction scheme and then deprotected after the reaction using commonly accepted protecting/deprotecting

techniques (see e.g., T. W. Green and P. G. M. Weets, Protective Groups in Organic Synthesis; 2nd ed., John Wiley and Sons: New York, 1989).

Scheme 1 depicts a preferred method of preparation of sulfonates of Formula la (which are compounds of Formula I wherein Z is O, and A, R¹, R² and n are as defined above originally).

SCHEME 1

In this reaction, sulfonyl chloride IIa is

preferably contacted with the preformed alkali salt of alcohol 1 in an inert solvent to provide la. The reaction temperature can be from about -50° to about 110°C, preferably from about 0° to about 35°C, and the reaction time about 1 to 24 hours. Suitable bases for generating the alkali salt of 1 include sodium hydride, butyl lithium, potassium hydroxide and sodium

methoxide, with sodium hydride being preferred.

Suitable solvents include tetrahydrofuran, pyridine, methylene chloride, toluene, acetone and acetonitrile, with tetrahydrofuran being preferred.

Alternatively, sulfonate Ia can be prepared by contacting sulfonyl chloride IIa with alcohol 2. and a hydrogen halide removing base in an inert solvent, using reaction conditions similar to those described above. Suitable solvents include those described above, with tetrahydrofuran being preferred. Bases for use in the reaction include tertiary amines such as triethylamine and pyridine, and sodium or potassium carbonate, with triethylamine being preferred.

Upon completion of reaction, the reaction mixture is concentrated in vacuo and water is added to the residue. The aqueous layer is extracted with organic solvent and the organic extract is dried (e.g., MgSO₄) and concentrated in vacuo. The crude product can be further purified by flash chromatography, or

recrystallization if a solid. Alternatively, the reaction mixture can be concentrated and the residue purified directly by flash chromatography to provide la.

Scheme 2 depicts a method to prepare many

sulfonates of Formula lb (which are compounds of

Formula I wherein Z is O, and A, R¹, R² and n are as defined originally above, except R¹ is other than H).

SCHEME 2

In this reaction, carbamyl chloride 2. is contacted with sulfonate 2. (Z=O) and a suitable hydrogen halide removing base in an inert solvent to provide sulfonate Ib (Z=O). The reaction temperature can be from about 0° to about 110°C, preferably from about 0° to about 60°C, and the reaction time about 0.5 to 24 hours.

Suitable bases include sodium hydride and tertiary amine bases such as triethylamine and pyridine.

Suitable solvents include tetrahydrofuran, pyridine, acetonitrile, acetone and toluene, with tetrahydrofuran being preferred. Sulfonate lb can be isolated and purified by methods described in Scheme 1.

Scheme 3 depicts a method for the preparation of sulfonates of Formula Ic (which are compounds of

Formula I wherein Z is O, and A, R² and n are as defined originally above and R¹ is hydrogen).

SCHEME 3

In this reaction, triazole 2. (Z=O) is contacted with isocyanate A in an inert solvent and, optionally, a tertiary amine catalyst to provide sulfonate Ic

(Z=0). The reaction is carried out under anhydrous conditions with a reaction temperature of between from about 0° to about 110°C, preferably from about 20° to about 60°C, for about 1 to 24 hours. Suitable solvents include tetrahydrofuran, toluene, acetonitrile, methylene chloride and acetone, with tetrahydrofuran or toluene being preferred. Suitable catalysts include triethylamine and 1,4-diazabicyclo [2.2.2] octane. After completion of the reaction, the reaction mixture is concentrated in vacuo to provide crude Ic, which can be further purified by flash chromatography, or

recrystallization if a solid.

Intermediate sulfonato-triazole 2. (Z=O) in

Schemes 2 and 3 can be prepared by the reaction of 3-sulfonylchloride-1H-1,2,4-triazole (prepared as in U.S. Patent 3,952,001] with alcohols 1, using analogous reaction conditions described in Scheme 1.

Intermediate sulfonyl chlorides of Formula IIa (which are compounds of Formula II wherein Y is Cl, and R¹ and R² are as defined originally) can be prepared as depicted hereinafter in Scheme 4.

SCHEME 4

In this reaction, hypochlorite solution, i.e., NaOCl, is contacted with thioether ϋ in a two-phase solvent system buffered with a suitable inorganic acid such as aqueous hydrochloric acid to provide IIa. The reaction temperature can be from about -10° to about 10°C, preferably from about -5° to about 5°C, and the reaction time from about 0.5 to 3 hours, preferably from 0.5 to 1 hour. Suitable solvents are water and an inert organic solvent such as methylene chloride or 1, 2-dichlorobenzene, with methylene chloride being preferred. Following completion of the reaction, the organic phase is isolated, washed with aqueous sodium bisulfite solution, dried (e.g., MgSO₄) and

concentrated in vacuo at about 25° to 35°C to provide a residue containing Ila. The impure residue containing Ila can be further purified by slurrying with hexane and/or flash chromatography on silica gel, and/or recrystallization if a solid. For further details, see analogous reactions in South African Patent Application No. 84/8845 and 84/8844.

Intermediate sulfonyl fluorides of Formula IIb (which are compounds of Formula II where Y is F, and R¹ and R² are as defined originally) can be prepared as depicted in Scheme 5.

SCHEME 5

In this reaction, a heated solution containing sulfonyl chloride Ila in an inert organic solvent is contacted with an aqueous solution of potassium

fluoride to provide lib. The reaction temperature can be from about 25° to about 100°C, preferably from about 70° to about 100°C, and the reaction time from about 0.5 to 5 hours. Preferably, excess potassium fluoride is used, about 0.1 to 3 mole excess. Following

completion of the reaction, the reaction mixture is poured into ice water and extracted with an organic solvent. The organic extract is dried (e.g., MgSO₄) and concentrated in vacuo to provide IIb. The compound can be further purified by flash chromatography on silica gel, or recrystallization if a solid.

Reaction procedures taught by Ichihara, J., et al., J. Chem. Soc. Chem. Commun., 1986, No. 10, 793; by Liu, H. G., et al., J. Fluorine Chem., 1989. 43(3), 429, by Borders, C. L., et al., J. Org. Chem., 1972, 37, 3549; by Blanchi, T. A., Cate, L. A., J. Org.

Chem., 1977. 42, 2031; and by Kitazume, T.,

Ishikawa, N., Chem. Lett., 1978 , 283, or slight

modifications thereof, can also be used for the

reaction of Scheme 7.

Sulfonyl fluorides IIb can be used to prepare compounds of Formula la (Scheme 1) using analogous conditions described in Scheme 1, or obvious

modifications thereof, by one skilled in the art.

Intermediate thioether 5a (which is the thioether of Formula 5 wherein R¹ is other than H) can be

prepared as depicted in Scheme 6.

SCHEME 6

The reaction of Scheme 6 can be carried out

according to the teachings of U.S. Patent 4,280,831, DE 3,929,673 Al and U.S. Patent 3,952,001. Thus, 5a can be obtained by contacting thioether 6 with carbamyl chloride 3 in excess pyridine at from about 20° to about 30°C; or by contacting 6 with 3 and a tertiary amine base such as triethylamine in an inert organic solvent such as tetrahydrofuran at about 25°C to reflux. Intermediate carbamyl chloride 3 can be prepared by contacting appropriate secondary amines with phosgene in an inert organic solvent such as refluxing ethyl acetate, according to the teachings of U.S. Patent 3,952,001. The preparation of 3-benzylthio-1,2,4-triazole 6 is taught in U.S. Patent 4,280,831.

Alternatively, thioethers 5 can be prepared

according to the teachings of U.S. Patent 3,952,001. Thus, contacting triazole 6 with phosgene and a

tertiary amine base such as pyridine or triethylamine in an inert organic solvent such as tetrahydrofuran at from about 0° to about 30°C can provide the

corresponding carbamyl chloride. Subsequent reaction of the carbamyl chloride with an appropriate primary or secondary amine in the presence of a suitable base such as pyridine or triethylamine in an inert organic solvent such as tetrahydrofuran at from about 0° to about 30°C can provide 5. Appropriate primary or secondary amines are known or can be prepared by methods generally known to those skilled in the art; see, e.g., U.S. Patent 3,952,001.

In addition, thioether 5 , wherein R¹ is H, can be prepared by generally known methods by the reaction of triazole 6 with appropriate isocyanates.

Also, alcohols of Formula 1 are either known or can be prepared by generally known methods by those skilled in the art.

The preparation of the compounds of this invention is further illustrated by the following specific examples. Temperatures are reported in degrees

Celsius. Proton nuclear magnetic resonance (¹H-NMR) peak positions are reported in parts per million downfield from tetramethylsilane, and abbreviations for splitting patterns are: s = singlet, d = doublet, t = triplet, q = quartet, bs = broad singlet and m = multiplet, with coupling (J) reported in hertz (Hz). Infrared (IR) peak positions are given in reciprocal centimeters (cm^-1).

EXAMPLE 1

Preparation of 3-[[phenylmethyl]thio]-N,N- diethyl-1H-1,2,4-triazole-1-carboxamide To a solution of 3-benzylthio-1H-1,2,4-triazole (98.4 g, 0.52 mol) (U.S. Patent 4,280,831) in pyridine (350 mL) was added dropwise diethylcarbamyl chloride (73.5 g, 0.54 mol) at ambient temperature. The solution was stirred overnight (ca. 16 h), then poured into excess water (1500 mL). The suspension was stirred until a precipitate formed, then filtered, and the residue was suction-dried overnight to provide the title compound (98.0 g) as a solid melting at 50-55°C. IR (mineral oil): 1690 cm^-1; ¹H-NMR (CDCl₃): δ 1.25 (t, 6H), 3.6 (bs, 4H), 4.4 (s, 2H), 7.2-7.4 (m, 5H), 8.75 (s, 1H).

EXAMPLE 2

Preparation of 1-[(diethylamino)carbonyl]-1H- 1,2,4-triazole-3-sulfonyl chloride To a solution containing the product of Example 1 (40.0 g, 0.14 mol) in methylene chloride (606 mL) was added water (318 mL), and the suspension was cooled with external cooling to about 0° to 5°C. Concentrated hydrochloric acid (41 mL) was added followed by

dropwise addition of Clorox^® (658 mL, active ingredient 5.25% sodium hypochlorite) while maintaining the reaction temperature at 0° to 5°C with external cooling and occasional addition of wet ice to the reaction suspension. After stirring at 0° to 5°C for 1 h, the organic layer was separated, washed with saturated aqueous sodium bisulfite (150-175 mL), then dried

(MgSO₄) and concentrated in vacuo (25-35°C) to an oil. On standing overnight the oil partially crystallized. The suspension was slurried with hexane (75 mL), filtered and the residue suction-dried to provide the title compound as a solid (26.0 g). The solid was further purified by flash chromatography (silica gel with 1:1 hexane: ethyl acetate) to provide the title compound (23.0 g), melting at 44-47°C. IR (mineral oil): 1160, 1270-1290, 1720 cm^-1; ¹H-NMR (CDCl₃): δ 1.35 (t, 6H), 3.6 (bs, 4H), 9.0 (s, 1H).

EXAMPLE 3

Preparation of 1-[(diethylamino)carbonyl]-1H- 1,2,4-triazole-3-sulfonyl fluoride A solution of 1-[(diethylamino)carbonyl]-1H-1,2,4-triazole-3-sulfonyl chloride (5.0 g, 0.019 mol) in p-dioxane (ca. 24 mL) was heated to reflux. At reflux, a hot solution of potassium fluoride (1.7 g, 0.029 mol) in water (ca. 7 mL) was added and the suspension was refluxed for 3 h. The reaction mixture was then concentrated in vacuo, ice water was added to the residue, the formed suspension was filtered and the isolated solid was suction-dried. The isolated solid was further purified by flash chromatography (silica gel with ethyl acetate) to provide the title compound (2.3 g) as a solid, melting at 50-52°C. IR (mineral oil): 1710 cm^-1; ¹H-NMR (CDC1₃) : δ 1.3 (t, 6H), 3.6 (bs, 4H), 9.0 (s, 1H); ¹⁹F-NMR (CDCl₃): δ 204.732.

EXAMPLE 4

Preparation of 2,2,2-trifluoroethyl 1-[(diethylamino)carbonyl]-1H-1,2,4-triazole-3-sulfonate

Under nitrogen, 2, 2, 2-trifluoroethanol (1.03 g, 0.01 mol) was added to a suspension of sodium hydride (60%, 0.41 g, 0.01 mol) in tetrahydrofuran (30 mL). After stirring 1 h, 1-[(diethylamino)carbonyl]-1H-1,2,4-triazole-3-sulfonyl chloride (2.5 g, 0.0094 mol) was added at 20° to 25°C. After stirring at room temperature for 48 h, the mixture was concentrated in vacuo, and the residual gum was purified by flash chromatography (silica gel with 2:1 hexane:ethyl acetate) to provide the title compound (0.2 g) as an oil. IR (neat): 1725 cm^-1; ¹H-NMR (CDCl₃): δ 1.3 (t, 6H), 3.6 (q, 4H), 4.7 (q, 2H), 8.9 (s, 1H).

By the general procedures described in Schemes 1-6 and Examples 1-4 or obvious modifications thereof, one skilled in the art can prepare the compounds of

Tables 1-5.

TABLES

The following Tables 1-5 pertain to compounds of Formula I:

wherein A is :

Formulations

Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Use formulations include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and

environmental factors such as soil type, moisture and temperature. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and

Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.

Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New

York, 1950. McCutcheon 's Detergents and Emulsifiers

Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active

Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.

Solutions are prepared by simply mixing the

ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259. Suspensions are prepared by wet-milling; see, for example,

U.S. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can also be prepared as taught in DE 3,246,493.

For further information regarding the art of formulation, see U.S. 3,235,361, col. 6, line 16 through col. 7, line 19 and Examples 10-41;

U.S. 3,309,192, col. 5, line 43 through col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132,

138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, col. 3, line 66 through col. 5, line 17 and

Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al.. Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.

In the following Examples, all percentages are by weight and all formulations are worked up in

conventional ways. Compound numbers refer to compounds in Index Table A.

UTILITY

Test results indicate compounds of this invention are active postemergence and, in particular,

preemergence herbicides. Many compounds in this invention are useful for the control of selected grass and broadleaf weeds with tolerance to important

agronomic crops such as barley (Hordeum vulgare) , corn (Zea mays) , cotton ( Gossypium hirsutum) , rape (Brassica napus) , rice ( Oryza sativa), sorghum {Sorghum bicolor) , soybean ( Glycine max)- , sugar beet (Beta vulgaris), and wheat ( Triticum aestivum), and to vegetable crops.

Grass and broadleaf weed species controlled include, but are not limited to, barnyardgrass (Echinochloa crus-galli) , blackgrass (Alopecurus myosuroides) , chickweed (Stellaria media), crabgrass (Digitaria spp.), foxtail (Setaria spp.), lambsquarters

( Chenopodium spp.), and wild oats (Avena fatua).

These compounds also have utility for weed control of selected vegetation in specified areas such as around storage tanks, parking lots, highways, and railways; in fallow crop areas; and in citrus and plantation crops such as banana, coffee, oil palm, and rubber. Alternatively, these compounds are useful to modify plant growth.

Effective rates of application for compounds of this invention are determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general terms, the subject compounds should be applied at rates from 0.03 to

20 kg/ha with a preferred rate range of 0.05 to

2 kg/ha. One skilled in the art can easily determine effective application rates necessary for desired level of weed control.

Compounds of this invention can be used alone or in combination with other commercial herbicides,

insecticides or fungicides. A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control. Examples of other herbicides with which compounds of this invention can be formulated are: acetochlor, acifluorfen, acrolein, 2-propenal, alachlor, ametryn, amidosulfuron, ammonium sulfamate, amitrole, anilofos, asulam, atrazine, barban, benefin, bensulfuron methyl, bensulide, bentazon, benzofluor, benzoylprop, bifenox, bromacil, bromoxynil, bromoxynil heptanoate, bromoxynil octanoate, butachlor, buthidazole, butralin, butylate, cacodylic acid, 2-chloro-N, N-di-2-propenylacetamide, 2-chloroallyl diethyldithiocarbamate, chloramben, chlorbromuron, chloridazon, chlorimuron ethyl, chlormethoxynil, chlornitrofen, chloroxuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clomazone, cloproxydim, clopyralid, calcium salt of methylarsonic acid, cyanazine, cycloate, cycluron, cyperquat, cyprazine, cyprazole, cypromid, dalapon, dazomet, dimethyl 2,3,5,6-tetr6chloro-1,4-benzenedic4rboxylate, desmedipham, desmetryn, dicamba, dichlobenil, dichlorprop, diclofop, diethatyl, difenzoquat, diflufenican, dimepiperate, dinitramine, dinoseb, diphenamid, dipropetryn, diquat, diuron, 2-methyl-4,6-dinitrophenol, disodium salt of methylarsonic acid, dymron, endothall, S-ethyl dipropylcarbamothioate, esprocarb, ethalfluralin, ethametsulfuron methyl, ethofumesate, fenac, fenoxaprop, fenuron, salt of fenuron and trichloroacetic acid, flamprop, fluazifop, fluazifop-P, fluchloralin, flumesulam, flumipropyn, fluometuron, fluorochloridone, fluorodifen, fluoroglycofen, flupoxam, fluridone, fluroxypyr, fluzasulfuron, fomesafen, fosamine, glyphosate, haloxyfop, hexaflurate, hexazinone, imazamethabenz, imazapyr, imazaquin, imazamethabenz methyl, imazethapyr,

imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, karbutilate, lactofen, lenacil, linuron, metobenzuron, metsulfuron methyl, methylarsonic acid, monoammonium salt of methylarsonic acid, (4-chloro-2-methylphenoxy) acetic acid, S, S'-dimethy1-2- (difluoromethyl)-4-(2-methylpropyl)-6-(trifluoromethyl)-3,5-pyridinedicarbothioate, mecoprop,

mefenacet, mefluidide, methalpropalin, methabenzthiazuron, metham, methazole, methoxuron, metolachlor, metribuzin, 1,2-dihydropyridazine-3,6-dione, molinate, monolinuron, monuron, monuron salt and trichloroacetic acid, monosodium salt of methylarsonic acid,

napropamide, naptalam, neburon, nicosulfuron, nitralin, nitrofen, nitrofluorfen, norea, norflurazon, oryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate,

pendimethalin, perfluidone, phenmedipham, picloram,

5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitroacetophenone oxime-O-acetic acid methyl ester, pretilachlor, primisulfuron, procyazine, profluralin, prometon, prometryn, pronamide, propachlor, propanil, propazine, propham, prosulfalin, prynachlor, pyrazolate, pyrazon, pyrazosulfuron ethyl, quinchlorac, quizalofop ethyl, rimsulfuron, secbumeton, sethoxydim, siduron, simazine, 1-(a,a-dimethylbenzyl)-3-(4-methylphenyl) urea, sulfometuron methyl, trichloroacetic acid, tebuthiuron, terbacil, terbuchlor, terbuthylazine, terbutol,

terbutryn, thifensulfuron methyl, thiobencarb,

triallate, trialkoxydim, triasulfuron, tribenuron methyl, triclopyr, tridiphane, trifluralin, trimeturon, (2,4-dichlorophenoxy) acetic acid, 4-(2,4-dichlorophenoxy)butanoic acid, vernolate, and xylachlor.

In certain instances, combinations with other herbicides having a similiar spectrum of control but a different mode of action will be particularly

advantageous for resistance management.

Selected herbicidal properties of the subject compounds were discovered in greenhouse tests as described below.

TEST A

Seeds of barley (Hordeum vulgare) , barnyardgrass (Echinochloa crus-galli) , bedstraw ( Galium aparine) , blackgrass (Alopecurus myosuroides), cheatgrass (Bromus secalinus) , chickweed (Stellaria media), cocklebur (Xanthium pensylvanicum) , corn (Zea mays) , cotton

(Gossypium hirsutum), crabgrass (Digitaria spp.), giant foxtail (Setaria faberii) , lambsquarters ( Chenopodium album) , morningglory ( Ipomoea hederacea) , rape

(Brassica napus), rice (Oryza sativa), sorghum (Sorghum bicolor) , soybean (Glycine max) , sugar beet (Beta vulgaris) , velvetleaf (Abutilon theophrasti) , wheat ( Triticum aestivum) , wild buckwheat (Polygonum

convolvulus) , and wild oat (Avena fatua) and purple nutsedge ( Cyperus rotundus) tubers were planted and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species were also treated with postemergence applications of test chemicals. Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TEST B

The compounds evaluated in this test were

formulated in a non-phytoxic solvent and applied to the soil surface before plant seedlings emerged

(preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one-to-four leaf stage (postemergence application). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depth was approximately 2.5 cm for the flood test and was

maintained at this level for the duration of the test.

Plant species in the preemergence and postemergence tests consisted of barley (Hordeum vulgare) , bedstraw (Galium aparine) , blackgrass (Alopecurus myosuroides) , chickweed (Stellaria media) , corn (Zea mays) , cotton (Gossypium hirsutum) , crabgrass (Digitaria

sanguinalis) , downy brome (Bromus tectorum), giant foxtail (Setaria faberii) , lambsquarters (Chenopodium album) , morningglory ( Ipomoea hederacea) , pigweed

(Amaranthusretroflexus) , rape (Brassica napus) ,

ryegrass (Lolium multiflorum) , sorghum (Sorghum

bicolor) , soybean (Glycine max) , speedwell (Veronica persica) , sugar beet (Beta vulgaris) , velvetleaf

(Abutilon theophrasti) , wheat (Triticum aestivum) , wild buckwheat (Polygonum convolvulus) , and wild oat (Avena fatua) . All plant species were planted one day before application of the compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the post-emergence portion of the test. Plant species in the flood test consisted of rice (Oryza sativa) , umbrella sedge ( Cyperus difformis) , duck salad

(Heteranthera limosa) and barnyardgrass (Echinochloa crus-galli) grown to the 1 and 2 leaf stage for

testing.

All plant species were grown using normal greenhouse practices. Visual evaluations of injury

expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response ratings, summarized in Table B, were recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

TEST C

Plastic pots were partially filled with silt loam soil. The soil was then saturated with water.

Japonica rice ( Oryza sativa) seedlings at the 2.0 to 2.5 leaf stage, seeds selected from barnyardgrass

(Echinochloa crus-galli) , duck salad (Heteranthera limosa) , umbrella sedge ( Cyperus difformis) , and tubers selected from arrowhead (Sagittaria spp.), and

waterchestnut (Eleocharis spp.), were planted into this soil. After planting, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were

formulated in a non-phytotoxic solvent and applied directly to the paddy water. Treated plants and controls were maintained in a greenhouse for

approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

TEST D

Plastic pots were partially filled with silt loam soil then saturated with water. Japonica rice ( Oryza sativa) seedlings, barnyardgrass (Echinochloa crus- galli) and watergrass (Echinochloa walteri) were grown to the 1 and 2 leaf stages and planted. After

planting, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent and applied directly to the paddy water. Treated plants and controls were

maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table D, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.

TEST E

Seeds of barnyardgrass (Echinochloa crus-galli) , black nightshade (Solanum ptycanthum dunal) , common ragweed (Ambrosia elatior) , corn (Zea mays) , cotton (Gossypium hirsutam) , crabgrass (Digitaria spp.), fall panicum (Panicum dicholomiflorum) , giant foxtail

(Setaria faberii) , green foxtail (Setaria vividis) , Johnson grass (Sorghum halepense), lambsquarter

(Chenopodium album), pigweed (Amaranthus retroflexus) , signalgrass (Brachiaria platyphylla) , smartweed

(Polygonum pensylvanicum) , soybean (Glycine max) , wild proso (Pancium miliaceum) and wooly cupgrass (Eriochloa villosa) were planted into a silt loam soil. Test chemicals, dissolved in. a non-phytotoxic solvent, were then applied to the soil surface within one day after the seeds were planted.

Treated plants and untreated controls were

maintained in the greenhouse approximately 21 days, treated plants were then compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table E, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control.

Claims

WHAT IS CLAIMED IS:

1. A compound of Formula I

wherein

A is C₁-C₅ alkyl substituted with 1 to 7 halogens; phenyl optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; pyridine, pyrimidine, pyrazine or triazine, each ring optionally substituted with 1 to 3 substituents selected from R³, R⁴ and ^R5; or a

Z is O;

. R¹ is H; C₁-C₆ alkyl optionally substituted with C₁-C₃ alkoxy or 1 to 5 halogens; C₃-C₆

cycloalkyl; C₂-C₆ alkenyl optionally

substituted with 1 to 3 halogens; C₃-C₆ alkynyl; or C₁-C₃ alkoxy;

R³ is H; halogen; C₁-C₆ alkyl optionally

SO₂NR¹³R¹⁴; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl;

C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; C₁-C₆ alkoxy; CN; CO₂R¹¹; S(O)_pR¹²; C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C(OR²⁰) (OR²¹)R²²; CR²³=NOR²⁴; NO₂;

NR²⁵R²⁶; or phenyl or benzyl, each ring

optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₂-C₃ haloalkyl and C₁-C₃ alkoxy;

halogen, C₁-C₆ alkoxy, CN, CO₂R⁷, S(O)_mR⁸,

SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C(OR²⁰) (OR²¹)R²²; CR²³=NOR²⁴;

NR²⁵R²⁶; or phenyl or benzyl, each ring

R⁶ is H; C₁-C₆ alkyl optionally substituted with one or more halogen, C₁-C₆ alkoxy, CN, CO₂R⁷, S(O)_mR⁸, C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; CN; CO₂R¹¹; SO₂R¹²; C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; or phenyl or benzyl, each ring optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy;

R⁷ and R¹¹ are independently H, C₁-C₃ alkyl or

allyl;

R⁸ and R¹² are independently C₁-C₃ alkyl; R⁹, R¹⁰, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are

independently H or C₁-C₃ alkyl; R⁹ and R¹⁰ may be taken together as piperidine or pyrrolidine; R¹³ and R¹⁴ may be taken together as piperidine or pyrrolidine; R¹⁵ and R¹⁶ may be taken together as piperidine or pyrrolidine; and R¹⁷ and R¹⁸ may be taken together as piperidine or pyrrolidine;

n is 0 or 1;

and their agriculturally suitable salts;

provided that

1) R³, R⁴ and R⁵ are independently bonded to

carbon, and R⁶ is bonded to nitrogen;

3) when A is triazine then n is 1; and

4) when A is phenyl optionally substituted with R³, R⁴, and R⁵, then n is 1.

2. A compound of Claim 1 wherein

A is C₁-C₅ alkyl substituted with 1 to 7 halogens; phenyl optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; pyridine, pyrimidine, pyrazine or triazine, each ring optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; or a 5-membered heterocyclic ring containing 1 to 3 heteroatoms selected from the group 0-3 nitrogens, 0-1 oxygen and 0-1 sulfur, each ring substituted with 1 to 4 substituents selected from R³, R⁴, R⁵ and R⁶;

R¹ is H; C₁-C₆ alkyl; C₂-C₃ haloalkyl; C₃-C₆

cycloalkyl; C₂-C₆ alkenyl; C₃-C₆ alkynyl; or C₁-C₃ alkoxy;

R² is C₁-C₆ alkyl; C₂-C₃ haloalkyl; C₃-C₆ cycloalkyl; C₂-C₆ alkenyl; or C₃-C₆ alkynyl;

R¹ and R² may be taken together to form -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅- or -(CH₂)₆-;

R³ is H; halogen; C₁-C₆ alkyl optionally

substituted with one or more halogen, C₁-C₆ alkoxy, CN, CO₂R⁷, S(O)_mR⁸; C(O)NR⁹R¹⁰ or

SO₂NR¹³R¹⁴; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; C₁-C₆ alkoxy; CN; CO₂R¹¹;

S(O)_pR¹²; C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; C(O)R¹⁹,

C(OR²⁰) (OR²¹)R²²; CR²³=NOR²⁴; NO₂; NR²⁵R²⁶; or phenyl or benzyl, each ring optionally

substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy;

halogen, Ci-Cg alkoxy, CN, CO₂R⁷, S(O)_mR⁸,

SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C(OR²⁰) (OR²¹)R²²; CR²³=NOR²⁴; NR²⁵R²⁶; or phenyl or benzyl, each ring

optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₅ alkyl and C₁-C₃ alkoxy;

R⁶ is H; C₁-C₆ alkyl optionally substituted with one or more halogen, C₁-C₆ alkoxy, CN, CO₂R⁷, S(O)_mR⁸, C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; C₂-C₆ alkynyl; CN; CO₂R¹¹; SO₂R¹²; C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; or phenyl or benzyl, each ring optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl and C₁-C₃ alkoxy.

3. A compound of Claim 1 wherein:

A is C₁-C₅ alkyl substituted with 1 to 8 halogens; phenyl or pyridine, each ring optionally substituted with 1 to 3 substituents selected from R³, R⁴ or R⁵; or

or

wherein

X is NR⁶, O or S.

4. A compound of Claim 3 wherein:

n is 0; and

R¹ and R² are independently C₁-C₃ alkyl or C₂-C₃ alkenyl.

5. A compound of Claim 4 wherein:

R³, R⁴ and R⁵ are independently H; F; Cl; Br; C₁-C₃ alkyl optionally substituted with one or more

F, Cl, Br or C₁-C₃ alkoxy; cyclopropyl; C₂-C₃ alkenyl; C₂-C₃ haloalkenyl; C₂-C₃ alkynyl; C₁-C₃ alkoxy; CN; CO₂ (C₁-C₂ alkyl), S(O)_p(C₁-C₂ alkyl); C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; C(O)R¹⁹, C(OR²⁰) (OR²¹)R²²; CR²³=NOR²⁴; NR²⁵R²⁶; or phenyl optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy;

R⁶ is H, C₁-C₄ alkyl optionally substituted with one or more F, Cl, Br, C₁-C₃ alkoxy, CN,

CO₂(C₁-C₂ alkyl), S(O)_m(C₁-C₂ alkyl), C(O)NR⁹R¹⁰ or SO₂NR¹³R¹⁴; C₂-C₄ alkenyl; C₂-C₄ haloalkenyl; C₂-C₄ alkynyl; CO₂R¹¹; SO₂(C₁-C₂ alkyl); C(O)NR¹⁵R¹⁶; SO₂NR¹⁷R¹⁸; or phenyl or benzyl, each ring optionally substituted with 1 to 3 substituents selected from halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl and C₁-C₃ alkoxy; R⁹, R¹⁰, R¹³ and R¹⁴ are independently C₁-C₂ alkyl; R¹¹ is C₁-C₂ alkyl or allyl; R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²⁵ and R²⁶ are independently

C₁-C₃ alkyl; and

R¹⁹, R²² and R²³ are independently H or C₁-C₂ alkyl.

6. A compound of Claim 5 wherein:

A is C₁-C₅ alkyl substituted with 1 to 7 halogens; pyridine optionally substituted with 1 to 3 substituents selected from R³, R⁴ and R⁵; A-3; A-4; or A-5;

7. A compound of Claim 6 wherein:

R³ and R⁴ are independently H, Cl, C₁-C₃ alkyl, CF₃, C₁-C₂ alkoxy, C₂-C₃ alkenyl or CN; and

R⁶ is C₁-C₃ alkyl optionally substituted with 1 to 3 F, Cl, Br, C₁-C₂ alkoxy, CN, CO₂(C₁-C₂ alkyl) or C(O)NR⁹R¹⁰; allyl; propargyl; C(O)NR¹⁵R¹⁶; phenyl; or benzyl.

8. A compound which is 2, 2, 2-trifluoroethyl 1-[[ethyl(1-methylethyl)amino]carbonyl]-1H-1,2,4-triazole-3-sulfonate; and 2,2,2-trifluoroethyl

1-[(diethylamino)carbonyl]-1H-1,2,4-triazole-3-sulfonate.

9. A composition consisting essentially of a herbicidally effective amount of a compound of Claim 1 and at least one of the following: surfactant, solid or liquid diluent.

10. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a

compound or composition of any one of Claims 1 through 9.

11. A compound of a structure of Formula II

wherein:

R¹ is H, C₁-C₆ alkyl, C₂-C₃ haloalkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl or

C₁-C₃ alkoxy;

R² is C₁-C₆ alkyl, C₂-C₃ haloalkyl, C₃-C₆

cycloalkyl, C₂-C₆ alkenyl or C₃-C₆ alkynyl; R¹ and R² may be taken together as -(CH₂)₃-,

-(CH₂)₄-, -(CH₂)₅- or -(CH₂)₆-; and Y is F or Cl.