WO1998028280A1

WO1998028280A1 - Certain 3-[2,4-disubstituted-5-(substituted amino)phenyl]-1-substituted-6-trifluoromethyl-2,4-(1h,3h)-pyrimidinedione derivatives as herbicides

Info

Publication number: WO1998028280A1
Application number: PCT/US1997/023546
Authority: WO
Inventors: Lester L. Maravetz; Scott D. Crawford; George Theodoridis
Original assignee: Fmc Corporation
Priority date: 1996-12-23
Filing date: 1997-12-22
Publication date: 1998-07-02
Also published as: AU5710898A

Abstract

Herbicidal compounds having structure (a) are disclosed, in which: X and Y are independently selected from hydrogen, halogen, and alkyl; R is alkyl or amino; R1 is hydrogen, alkyl, cyanoalkylsulfonyl, acyl, acyloxyacyl, alkoxycarbonyl, or represents the negative charge of the anion of a salt; R2 is: (1) alkyl, cyanoalkyl, cyanoalkoxycarbonylalkyl, alkenoxycarbonylalkyl, alkynoxycarbonylalkyl, arylalkyl, aryloxyalkyl, arylalkoxycarbonylalkyl, heterocyclyl, amino, aminocarbonylalkyl; (2) -W-R3 in which W is alkyl, and R3 is aminocarbonyl, alkoxycarbonyl, hydroxycarbonyl, arylalkylthiocarbonyl, nitro, alkylthiocarbonyl, or heterocyclylalkoxycarbonyl; (3) -CH(C N)R4 in which R4 is hydrogen, alkyl, arylalkyl, or arylhaloalkyl; or (4) -C(C N)=CHR5; in which R5 is aryl or heterocyclyl; with the proviso that an amino group may be substituted with alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, acyloxyacyl, aryl, arylalkyl, aryloxyalkyl, or heterocyclylalkyl; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with halogen; and heterocyclyl is selected from 2,3-dihydro-2,2-dimethylbenzofuran-7-yl and 1,3-dioxolan-2-yl. The sodium, potassium or 1-8 carbon amine salts of the compounds are also herbicidal.

Description

CERTAIN 3-[2,4-DISUBSTITUTED-5-(SUBSTITUTED AMINO)PHENYL]- 1 -SUBSTITUTED-6-TRIFLUOROMETHYL-2,4-(1 H,ZH)- PYRIMIDINEDIONE DERIVATIVES AS HERBICIDES

This invention relates to methods for controlling unwanted plant species in agriculture. In particular, it is the control by application of certain 3-[2,4-disubstituted-5-(substituted amino)phenyl]-1-substituted-6- trifluoromethyl-2,4-(1 H,3H)-pyrimidinedione derivatives to a locus where herbicidal control is desired. While some 3- phenyl-1-substituted-6-trifluoro- methyl-2,4-(1 - ,3rV)-pyrimidinedione derivatives are known to have herbicidal activity, the use of the class of compounds of this invention as herbicides is heretofore unknown. It has now been found that certain 3-[2,4-disubstituted-5-(substituted amino)phenyl]-1-substituted-6-trifluoromethyl-2,4-(1fτ',3 -/)-pyrimidinedione derivatives are highly active herbicides. The novel compounds of the present invention are defined by the following generic structure:

in which:

X and Y are independently selected from hydrogen, halogen, and alkyl;

R is alkyl or amino;

R is hydrogen, alkyl, cyanoalkylsulfonyl, acyl, acyloxyacyl, alkoxycarbonyl, or represents the negative charge of the anion of a salt; R² is:

(1) alkyl, cyanoalkyl, cyanoalkoxycarbonylalkyl, alkenoxycarbonylalkyl, alkynoxycarbonylalkyl, arylalkyl, aryloxyalkyi, arylalkoxycarbonylalkyl, heterocyclyl, amino, aminocarbonylalkyl; (2) — W— R³ in which W is alkyl, and R³ is aminocarbonyl, alkoxycarbonyl, hydroxycarbonyl, arylalkylthiocarbonyl, nitro, alkylthiocarbonyl, or heterocyclylalkoxycarbonyl;

(3) — CH(C≡N)R⁴, in which R⁴ is hydrogen, alkyl, arylalkyl, or arylhalo- alkyl; or (4) — C(C≡N)=CHR⁵; in which R⁵ is aryl or heterocyclyl; with the proviso that an amino group may be substituted with one or two substituents independently selected from alkyl, cyanoalkyl, alkoxy, alkoxy- carbonylalkyl, acyloxyacyl, aryl, arylalkyl, aryloxyalkyi, and heterocyclylalkyl; halogen is chlorine, bromine, or fluorine; the alkyl and acyl moieties may each contain 1-6 carbon atoms, the alkenyl and alkynyl moieties may each contain 2-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in any R¹, R², R³, or R⁴ does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with halogen; and heterocyclyl is selected from 2,3-dihydro-2,2-dimethylbenzo- furan-7-yl and 1,3-dioxolan-2-yl;. with the further proviso that when R² is amino, alkylamino, dialkylamino, arylamino, or arylalkylamino, and R is alkyl, R¹ is not hydrogen, alkyl, alkylcarbonyl, or alkoxycarbonyl; and when R² is aryl arylalkyl, or alkoxycarbonylalkyl, and R is alkyl, R¹ cannot be hydrogen, alkyl, alkylcarbonyl, or alkoxycarbonyl, but R² may be alkyl only when R¹ is cyanoalkylsulfonyl or acyloxyacyl; or the sodium, potassium or 1-8 carbon amine salts thereof.

O in which :

R³ is selected from arylhaloalkyl, substituted or disubstituted aminocarbonyl, arylalkoxycarbonylalkyl, and (arylalkylthio)carbonyl; and Q is hydrogen or alkyl; with the proviso that the amino substituents are independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, aryl, arylalkyl, and aryloxyalkyi; the alkyl, alkoxy, and acyl moieties may each contain 1-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in R³ does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with chlorine, bromine, or fluorine.

Preferred are those compounds in which:

R is alkyl or amino;

R¹ is hydrogen, alkyl, acyl, acyloxyacyl, or represents the negative charge of the anion of a salt;

R² is (1) cyanoalkyl, aryloxyalkyi, amino, or aminocarbonylalkyl, in which an amino group may be substituted with one or two substituents independently selected from alkyl, cyanoalkyl, or alkoxy; with the proviso that when R² is amino, alkylamino, or dialkylamino, and R is alkyl, R¹ is not hydrogen or alkyl; or (2) —CH(C≡N)R⁴, in which R⁴ is hydrogen or alkyl; with the proviso that the alkyl, alkoxy, and acyl moieties may each contain 1-4 carbon atoms; each may be straight or branched; the total number of carbon atoms in any R¹, R², or R⁴ is does not exceed 8; and aryl is selected from phenyl or furanyl. Particularly preferred are those compounds in which X is chlorine or bromine; Y is hydrogen or fluorine; R is methyl or amino; R¹ is hydrogen, acetyl, or acetoxyacetyl; R² is (1) 1-cyanoethyl, 2-cyanopropyl, phenoxyethyl, dimethylamino, (2-cyanoethyl)(methyl)amino, or aminocarboxymethyl, in which an amino group may be substituted with one or two substituents independently selected from methyl, methoxy, phenyl, or benzyl; with the proviso that when R² is dimethylamino, and R is methyl, R¹ is not hydrogen; or (2) — CH(C≡N)R⁴, in which R⁴ is hydrogen or alkyl. Novel intermediates useful in the preparation of the compounds of this invention include the following :

(1)

O in which: R³ is selected from arylhaloalkyl, substituted or disubstituted aminocarbonyl, arylalkoxycarbonylalkyl, and (arylalkylthio)carbonyl; and Q is hydrogen or alkyl; with the proviso that the amino substituents are independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, aryl, aryllkyl, and arylxyalkyl; the alkyl, alkoxy, and acyl moieties may each contain 1-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in R³ does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with chlorine, bromine, or fluorine;

(2)

in which: X and Y are independently selected from hydrogen, halogen, and alkyl; Z is nitro, amino, or isocyanato; R² is arylalkyl, aryloxyalkyi, cyanoalkyl, substituted or disubstituted aminocarbonylalkyl, arylalkoxycarbonyl-alkyl, (arylalkylthio)carbonylalkyl, or mono- or disubstituted amino; with the proviso that the amino substituents are independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, acyloxyacyl, aryl, arylalkyl, and aryloxyalkyi; the alkyl, alkoxy, and acyl moieties may each contain 1-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in R² does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with chlorine, bromine, or fluorine;

(3)

in which: X and Y are independently selected from hydrogen, halogen and alkyl; R² is arylalkyl, aryloxyalkyi, cyanoalkyl, substituted or disubstituted aminocarbonylalkyl, arylalkoxycarbonylalkyl, (arylalkylthio)carbonylalkyl, or disubstituted amino; with the proviso that the amino substituents are independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, acyloxyacyl, aryl, arylalkyl, and aryloxyalkyi; the alkyl, alkoxy, and acyl moieties may each contain 1-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in R² is does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with chlorine, bromine, or fluorine; and

(4)

in which: X and Y are independently selected from hydrogen, halogen, or alkyl; and R² is arylalkyl, aryloxyalkyi, cyanoalkyl, substituted or disubstituted aminocarbonylalkyl, arylalkoxycarbonylalkyl, (arylalkylthio)- carbonyl-alkyl, or mono- or disubstituted amino; with the proviso that the amino substituents are independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, acyloxyacyl, aryl, arylalkyl, and aryloxyalkyi; the alkyl, alkoxy, and acyl moieties may each contain 1-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in R² does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with chlorine, bromine, or fluorine.

The compounds of the present invention were prepared by methods known to one skilled in the art. A number of synthesis routes were employed in obtaining the targeted compounds.

Generally, the 3-[2,4-disubstituted-5-(substituted amino)phenyl]-1- substituted-6-trifIuoromethyl-2,4-(1H,3rτ)-pyrimidinedione compounds were prepared by one of two routes, depending on whether the substitution at the five position of the phenyl ring occurs prior to, or after, the formation of 2,4- (1H,3H)-pyrimidinedione ring.

As depicted in Schema 1, compounds in which the substitution at the five position of the phenyl ring occurs after the formation of the 2,4-(1 H,3H)- pyrimidinedione ring are prepared by reacting the appropriate 3-(2,4- disubstituted-5-aminophenyl)-1-substituted-6-trifluoromethyl-2,4(1H,3r )- pyrimidinedione (AA) with a substituted sulfonyl chloride (BJB) in essentially equimolar-molar proportions to form the targeted 3-[2,4-disubstituted-5- (substituted sulfonylamino)phenyl]-1 -(substituted or unsubstituted)-6- trifluoromethyl-2,4-(1 - ,3 -/)-pyrimidinedione (I), for example 3-[4-chloro-2- fluoro-5-(2,3-dihydro-2,2-dimethylbenzofuran-7-ylsulfonylamino)phenyl]-1- methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione. The reaction is facilitated by the use of solvents such as hydrocarbons, methylene chloride, chloroform, toluene, acetonitrile, diethyl ether, dioxane, pyridine, tetrahydrofuran, and by the addition of bases, such as triethylamine or pyridine. These bases act as hydrogen chloride scavengers for the hydrogen chloride by-product of these reactions. Examples 4, 7, 8, and 9 provide detailed procedures for this route. In other cases, the above reaction may be run in the prescribed solvents, such as acetonitrile, with two equivalents of the pyrimidinedione (AA) and one equivalent of the sulfonyl chloride (BB), which allows the pyrimidinedione (AA) to serve as the hydrogen chloride scavenger. Examples 1 , 3, and 5 provide detailed procedures for this route. In still other cases, particularly where the reactivity of the sulfonyl chloride (BB) is relatively low, the pyrimidinedione (AA) can be reacted in a large stoichiometric excess of the sulfonyl chloride (BB). without the use of a solvent and with a base such as 4-dimethylaminopyridine (DMAP). Example 13 provides a detailed procedure for this route. Certain 3-[2,4-disubstituted-5-(substituted sulfonylamino)phenyl]-1- substituted-6-trifluoromethyl-2,4-(1H,3 -/)-pyrimidinedione (I), where R² is cyanomethyl, are susceptible to reaction with certain aryl or heterocyclic aldehydes, such as benzaldehyde or furfuraldehyde, under base-catalyzed dehydration, affording the targeted 3-[2,4-disubstituted-5- (arylethenesulfonylamino)phenyl]-1 -substituted-6-trifluoromethyl-2,4(1 H,3H)- pyrimidinedione (II). Example 2 provides a detailed procedure for this route.

Certain 3-[2,4-disubstituted-5-(substituted sulfonylamino)phenyl]-1 - substituted-6-trifluoromethyl-2,4-(1 - ,3H)-pyrimidinedione (I) or (II) are also subject to salt formation by reaction of the sulfonamido group with bases, such as sodium methoxide, sodium hydroxide, potassium hydroxide, potassium carbonate, or with organic alkylamines, such as isopropylamine, in a suitable solvent system. Example 6 provides a detailed procedure for this route.

The aminating agent can be prepared at this point. For example, 2,4,6-trimethylbenzene-sulfonyl chloride is reacted with f-butyl N- hydroxycarbamate under basic conditions to yield f-butyl N-(2,4,6- trimethylphenylsulfonyloxy)carbamate (CO. The f-butyl carbamate (CC) is hydrolyzed under basic conditions, yielding 1-aminooxysulfonyl-2,4,6- trimethylbenzene (DP). Other aminating agents that could have utility include, but are not limited to, 2,4-dinitrophenoxyamine and hydroxylamine- O-sulfonic acid. The 1-aminooxysulfonyl-2,4,6-trimethylbenzene (DP) aminating agent is then reacted with the appropriate 3-[2,4-disubstituted-5- (substituted sulfonylamino)phenyl]-6-trifluoromethyl-2,4-(1H,3H)- pyrimidinedione (I) where R is hydrogen, under basic conditions, affording the targeted 3-[2,4-disubstituted-5-(substituted sulfonylamino)phenyl]-1- amino-6-trifluoromethyl-2,4(1H,3 -/)-pyrimidinedione (HI). Examples 10,11 and 14 provide detailed procedures for this route.

The 3-[2,4-disubstituted-5-(substituted sulfonylamino)phenyl]-1 - substituted-6-trifluoromethyl-2,4(1H,3r7>pyrimidinedione (I) can be alkylated or acylated at the nitrogen atom of the sulfonamido group with such reagents as alkyl halides, acyl halides, acyloxyacyl halides, alkoxycarbonyl halides, with suitable solvents, such as methylene chloride, tetrahydrofuran, toluene, and diethyl ether, as well as bases, such as triethylamine or pyridine. Example 12 provides a detailed procedure for this route. As depicted in Schema 2, those compounds in which the substitution at the five position of the phenyl ring occurs prior to the formation of 2,4- (1H,3H)-pyrimidinedione ring were prepared by reacting a substituted 5- aminophenylcarbmate ester (EE) with a sulfonyl chloride (BB) in the manner described previously to yield the corresponding ethyl N-[substituted 5- (substituted sulfonylamino)phenyi]carbamate (FF). At this point additional substituents may be added to the ethyl N-[substituted 5-(substituted sulfonylamino)phenyl]carbamate (FF). For example, the carbamate (FF) can be chlorinated by exposing it to an excess of chlorine gas in the presence of acetic acid and water, affording the ethyl N-[4-chloro-5-(substituted sulfonyamino)phenyl]carbamate. The carbamate (FF) is then reacted with ethyl S-amino^^^-trifluorocrotonate in the presence of a base, such as sodium hydride, sodium methoxide, or alkaline earth metals, such as barium hydroxide, barium oxide, calcium hydroxide, calcium hydride, or strontium oxide, and then worked up with acid to form the corresponding 3-[2,4- disubstituted-5-[(alkylamino or aryl)sulfonylamino]phenyl]-6-trifluoromethyl- 2,4(1 /-/,3H)-pyrimidinedione (GG). The pyrimidinedione (GG) is in turn alkylated with methyl iodide or aminated with an aminating agent, for example, 1-aminooxysulfonyl-2,4,6-trimethylbenzene (DP), in the manner disclosed previously, affording the targeted 3-[2,4-disubstituted-5-(substituted sulfonylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1/- ,3rV)-pyrimidinedione (I) or 3-[2,4-disubstituted-5-(substituted sulfonylamino)phenyl]-1-amino-6- trifluoromethyl-2,4(1/- ,3rV)-pyrimidinedione (III), respectively. Example 11 describes a detailed procedure for this route. Examples 10 and 14 also describe detailed procedures for this route, although with some variations that are known to those skilled in the art.

The substituted sulfonyl chlorides (BB) used to prepare the appropriate 5-sulfonamidophenyl derivatives of the present invention may be prepared by methods taught in the literature and known to those skilled in the art. Thus, a chloroacetamide can be converted to a sodium sulfonate with sodium sulfite in the presence of water and ethanol, followed by conversion to the sulfonyl chloride via phosphorous oxychloride in toluene. Example 9 describes a detailed procedure for preparing a substituted sulfonyl chloride (BB) by this route. Examples 7 and 8 describe similar reactions to yield other substituted sulfonyl chlorides (BB). Similarly, a substituted dialkylaminosulfonyl chloride derivative (BB) can be prepared by reacting a secondary amine with sulfuryl chloride in chloroform. Example 13 describes a detailed procedure for preparing a sulfonyl chloride (BB) by this route. Schema 1

^R"^CH° ^{+ [}

DD

where

Schema 2

C- OCHjCH

KoCO,

GG

CH₃I Acetone

Δ or

DMF/CH3I R.T.

GG + DD K?CQ_?

III

THF

Δ

EXAMPLE 1

SYNTHESIS OF 3-[4-CHLORO-5-(CYANOMETHYLSULFONYLAMINO)-

PHENYL]-1-METHYL-6-TRIFLUOROMETHYL-2,4(1H,3H)-

PYRIMIDINEDIONE (COMPOUND 63)

A stirred solution of 1.0 gram (0.003 mole) of 3-(5-amino-4-chloro- phenyl)-1 -methyl-6-trifluoromethyl-2,4(1 /-/,3/-/)-pyrimidinedione in about 13 ml_ of acetonitrile was cooled to -10 to 0 °C, and a solution of 0.2 gram (0.002 mole) of cyanomethylsulfonyl chloride in 3 ml_ of acetonitrile was added slowly. Upon completion of the addition the reaction mixture was allowed to warm to ambient temperature, where it stirred for about three hours. After this time the reaction mixture was concentrated under reduced pressure, yielding 1.1 grams of a tan solid, which was taken up in about 20 mL of chloroform. The remaining solid was collected by filtration, yielding 0.1 gram of a gray solid. After an additional amount of chloroform was added to bring the total volume to about 20-25 ml_, the above filtrate was re-filtered. The filter cake was dried, yielding 0.2 gram of 3-[4-chloro-5- (cyanomethylsulfonylamino)-phenyl]-1 -methyl-6-trifluoromethyl-2,4(1 H,3H)- pyrimidinedione, m.p. 220-223° C. The NMR spectrum was consistent with the proposed structure. The filtrate from the second filtering was concentrated under reduced pressure, yielding 0.8 gram of a solid. This solid was combined with the 0.1 gram of the above gray solid to yield a total of 0.9 gram of solid. The combined solid was taken up in a minimal amount of acetone, and the resulting solution was subjected to column chromatography on silica gel. Elution was accomplished with 1:1 ethyl acetate and hexane followed by pure ethyl acetate as eluants. The product-containing fractions were combined and concentrated under reduced pressure, yielding 0.4 gram of 3-[4-chloro-5-(cyanomethylsulfonylamino)-phenyl]-1-methyl-6- trifluoromethyl-2,4(1H,3rV)-pyrimidinedione. The NMR spectrum was consistent with the proposed structure. This 0.4 gram of product was combined with the previous 0.2 gram of product to yield a total of 0.6 gram of 3-[4-chloro-5-(cyanomethylsulfonylamino)-phenyl]-1-methyl-6-trifluoromethyl- 2,4(1 H,3H)-pyrimidinedione.

EXAMPLE 2

SYNTHESIS OF 3-[4-CHLORO-5-(1-CYANO-2-PHENYLETHENE- SULFONYLAMINO)PHENYL]-1-METHYL-6-TRIFLUOROMETHYL- 2,4(1H,3H)-PYRIMIDINEDIONE (COMPOUND 83)

A stirred solution of 0.4 gram (0.0009 mole) of 3-[4-chloro-5-(cyano- methylsulfonylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1 - ,3H)- pyrimidinedione (as prepared in Example 1), 0.1 gram (0.0009 mole) of benzaldehyde, about 0.01 gram (0.0002 mole) of acetic acid, and 2-3 drops of piperidine in 15 mL of toluene was heated at reflux for two hours in the presence of 3A molecular sieves. At the conclusion of this period the reaction mixture was analyzed by TLC, which indicated that no starting material remained. The reaction mixture was decanted from the molecular sieves, diluted with more toluene, and then washed with one portion of 2N aqueous hydrochloric acid, followed by water. The resulting precipitate was collected by filtration, yielding 0.14 gram of 3-[4-chloro-5-(1-cyano-2- phenylethenesulfonylamino)-phenyl]-1-methyl-6-trifluoromethyl-2,4(1H,3H)- pyrimidinedione, m.p. 241-243° C. The NMR spectrum was consistent with the proposed structure. The filtrate was washed with water, dried with magnesium sulfate, and re-filtered. This filtrate was concentrated under reduced pressure, yielding a moist solid. The toluene in the solid was extracted with two portions of petroleum ether to yield an additional 0.13 gram of 3-[4-chloro-5-(1 -cyano-2-phenylethenesulfonylamino)phenyl]-1 - methyl-6-trifluoromethyl-2,4(1H,3rV)-pyrimidinedione. The NMR spectrum was consistent with the proposed structure. This 0.13 gram of product was combined with the 0.14 gram of product isolated previously to yield a total of 0.27 gram of 3-[4-chloro-5-(1-cyano-2-phenylethenesulfonylamino)phenyl]-1- methyl-6-trifluoromethyl-2,4(1H,3 -/)-pyrimidinedione.

EXAMPLE 3

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-(1-CYANOETHYL-

SULFONYLAMINO)PHENYL]-1-METHYL-6-TRIFLUOROMETHYL-

2,4(1 H,3W)-PYRIMIDINEDIONE (COMPOUND 68)

This compound was prepared in the manner of Example 1 , with 0.7 gram (0.002 mole) of 3-(5-amino-4-chloro-2-fluorophenyl)-1-methyl-6- trifluoromethyl-2,4(1H,3/- -pyrimidinedione and 0.2 gram (0.001 mole) of 1- cyanoethylsulfonyl chloride in 10.0 mL of acetonitrile as reagents. The yield of 3-[4-chloro-2-fluoro-5-(1-cyanoethylsulfonylamino)phenyl]-1-methyl-6- trifluoromethyl-2,4(1H,3r7)-pyrimidinedione was 0.2 gram, m.p. 107-110° C. The NMR spectrum was consistent with the proposed structure. EXAMPLE 4

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-(2,3-DIHYDRO-2,2- DIMETHYLBENZOFURAN-7-YLSULFONYLAMINO)PHENYL]-1-METHYL-6- TRIFLUOROMETHYL-2,4(1H,3fV)-PYRIMIDINEDIONE (COMPOUND 1)

A stirred solution of 0.5 gram (0.001 mole) of the 3-(5-amino-4-chloro- 2-fluorophenyl)-1-methyl-6-trifIuoromethyl-2,4(1H,3H)-pyrimidinedione and 0.04 gram (0.0003 mole) of 4-dimethylaminopyridine in about 3 mL of pyridine was cooled to -5 to 5° C, and 0.4 gram (0.002 mole) of 2,3-dihydro- 2,2-dimethylbenzofuran-7-ylsulfonyl chloride was added in small portions during a ten minute period. Upon completion of the addition the reaction mixture was allowed to warm to ambient temperature,, where it stirred for one hour. After this time the reaction mixture was analyzed by TLC, which indicated the reaction was complete. The reaction mixture was quenched with about 60 mL of aqueous 10% hydrochloric acid, and the resulting solid was collected by filtration. The solid was washed with water and dried on a clay plate to yield 0.7 gram of material, which was recrystallized from diethyl ether and water, yielding 0.3 grams of 3-[4-chloro-2-fluoro-5-(2,3-dihydro-2,2- dimethylbenzofuran-7-ylsulfonylamino)phenyl]-1-methyl-6-trifluoromethyl- 2,4(1 H,3H)-pyrimidinedione, m.p. 202-204° C. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 5

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-(1-CYANOPROPYL- SULFONYLAMINO)PHENYL]-1-METHYL-6-TRIFLUOROMETHYL- 2,4(1 H,3H)-PYRIMIDINEDIONE (COMPOUND 71)

This compound was prepared in the manner of Example 1 , with 1.0 gram

(0.003 mole) of 3-(5-amino-4-chloro-2-fluorophenyl)-1-methyl-6- trifluoromethyl-2,4(1H,3H)-pyrimidinedione and 0.2 gram (0.001 mole) of 1- cyanopropylsulfonyl chloride in 18 mL of acetonitrile as reagents. The yield of 3-[4-chloro-2-fluoro-5-(1 -cyanopropylsulfonylamino)phenyl]-1 -methyl-6- trifluoromethyl-2,4(1H,3/ )-pyrimidinedione was 0.2 gram, m.p. 94-98° C.

The NMR spectrum was consistent with the proposed structure.

EXAMPLE 6 SYNTHESIS OF THE SODIUM SALT OF 3-[4-CHLORO-2-FLUORO-5-(1- CYANOETHYLSULFONYLAMINO)PHENYL]-1-METHYL-6-TRIFLUORO- METHYL-2,4(1H,3H)-PYRIMIDINEDIONE (COMPOUND 80)

A stirred solution of 1.2 grams (0.003 mole) of 3-[4-chloro-2-fluoro-5- (1-cyanoethylsulfonylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1r7^,,3 -/)- pyrimidinedione (as prepared in Example 3) and 0.1 gram (0.003 mole) of sodium methoxide in 25 mL of absolute methanol was heated to 40° C, where it stirred for five minutes. At the end of this period the reaction mixture was allowed to cool to ambient temperature during a 45 minute period, after which the absolute methanol was removed, yielding 1.3 grams of a tan solid. The solid was triturated with about 20 mL of diethyl ether, and the resulting supernatant liquid was decanted. To the remaining precipitate was added an additional 20 mL of diethyl ether, and again the supernatant liquid was decanted. The residual solid was dried, yielding 0.6 gram of the sodium salt of 3-[4-chloro-2-fluoro-5-(1-cyanoethylsulfonylamino)phenyl]-1-methyl-6- trifluoromethyl-2,4(1H,3H)-pyrimidinedione. The NMR spectrum was consistent with the proposed structure. The diethyl ether supernatant liquids were combined and concentrated under reduced pressure, yielding an additional 0.7 gram of the sodium salt of 3-[4-chloro-2-fluoro-5-(1- cyanoethylsulfonylamino)phenyl]-1-methyl-6-trifluoromethyl-2,4(1 - ,3 -/)- pyrimidinedione.

EXAMPLE 7

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-[(2-CHLORO-2-PHENYL-1-

CYANO)ETHYLSULFONYLAMINO]PHENYL]-1-METHYL-6-TRIFLUORO-

METHYL-2,4(1H,3tf)-PYRIMIDINEDIONE (COMPOUND 77)

Step A Synthesis of sodium 2-phenyl-1 -cyanoethylsulfonate and sodium chloride mixture as an intermediate

To a stirred slurry of 4.2 grams (0.033 mole) sodium sulfite in 15 mL of water was added 4.2 grams (0.025 mole) of 1 -chloro-2-phenylpropionitrile during a 30 minute period. Upon completion of the addition the reaction mixture was stirred at ambient temperature for one hour. After this time the reaction mixture was heated to 85° C, where it stirred for about 18 hours and then to 98-103° C, where it stirred for 1.5 hours. At the conclusion of this period the water was removed under reduced pressure, yielding a white residue, which was air dried, yielding 8.1 grams of organic product and sodium chloride. The NMR spectrum indicated the organic product to be sodium 2-phenyl-1 -cyanoethylsulfonate. The material was used as is in the next step. Step B Synthesis of 2-chloro-2-phenyl-1-cyanoethylsulfonyl chloride as an intermediate

To stirred phosphorus oxychloride, 41.1 grams (0.27 moles), was added in portions 8.0 grams (0.01 mole) of the sodium 2-phenyl-1- cyanoethylsulfonate and sodium chloride mixture during a five minute period followed by 15.0 grams (0.07 mole) of phosphorus pentachloride during a ten minute period. Upon completion of the addition the reaction mixture was heated at 66-81 ° C for three hours, the cooled to ambient temperature and filtered. The filtrate was concentrated under reduced pressure, yielding 3.0 grams of crude product. This crude product was combined with 4.0 grams of crude product prepared by a similar route to yield a total of 7.0 grams of crude product, which were purified by distillation, yielding 2.4 grams of 2- chloro-2-phenyl-1-cyanoethylsulfonyl chloride. The IR spectrum was consistent with the proposed structure.

Step C Synthesis of 3-[4-chloro-2-fluoro-5-[(2-chloro-2-phenyl-1- cyano)-ethylsulfonylamino]phenyl]-1-methyl-6-trifluoromethyl- 2,4(1 H,3H)-pyrimidinedione (Compound 77)

A stirred solution of 0.5 gram (0.002 mole) of 3-(5-amino-4-chloro-2- fluorophenyl)-1-methyl-6-trifluoromethyl-2,4(1r ,3 -/)-pyrimidinedione and 0.2 gram (0.002 mole) of triethylamine in 10 mL of tetrahydrofuran was cooled to 0° C, and a solution of 0.4 gram (0.002 mole) of 2-chloro-2-phenyl-1-cyano- ethylsulfonyl chloride in 5 mL of tetrahydrofuran was added dropwise. Upon completion of the addition, the reaction mixture was allowed to warm to ambient temperature, where it stirred for one hour. After this time the reaction mixture was analyzed by TLC, which indicated that some starting material remained. The reaction mixture was again cooled to 0° C, and an additional 0.2 gram (0.002 mole) of triethylamine and 0.4 gram (0.002 mole) of 2-chloro-2-phenyl-1-cyanoethylsulfonyl chloride were added. Upon completion of this addition the reaction mixture was again allowed to warm to ambient temperature, where it stirred for about 18 hours. At the conclusion of this period the reaction mixture was again analyzed by TLC, which indicated that most of the starting material had reacted. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to a brown oil, which was subjected to column chromatography on silica gel. Elution was accomplished with 2:5 methanol and methylene chloride followed by 1:1 ethyl acetate and hexane as eluants. The product-containing fractions were combined and concentrated under reduced pressure, yielding 0.1 gram of 3-[4-chloro-2-fluoro-5-[(2-chloro-2-phenyl-1 - cyano)ethylsulfonylamino]phenyl]-1-methyl-6-trifluoromethyl-2,4(1H,3/- - pyrimidinedione, m.p. 188-190° C. The NMR spectrum was consistent with the proposed structure. EXAMPLE 8

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-[(1-BENZYLTHIO-

CARBONYL)ETHYLSULFONYLAMINO]PHENYL]-1-METHYL-6-

TRIFLUOROMETHYL-2,4(1H,3rV)-PYRIMIDINEDIONE (COMPOUND 53)

Step A Synthesis of 1-benzylthiocarbonyl-1-bromoethane as an intermediate

To a stirred solution of 7.6 grams (0.05 mole) of triethylamine in 100 mL of chloroform was added 5.3 mL of benzyl mercaptan in one portion. Upon completion of the addition the mixture was stirred for ten minutes, and then a solution of 5.0 mL (0.04 mole) of 2-bromopropionyl chloride in 100 mL of chloroform was added dropwise. The reaction mixture was stirred for about 18 hours, then poured into 50 mL of an aqueous saturated sodium chloride solution and washed with water. The resulting mixture was poured into water and washed with one 50 mL portion of water followed by one 50 mL portion of aqueous 2N hydrochloric acid. The organic layer was separated from the aqueous layer, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 12.8 grams of 1-benzylthiocarbonyl-1-bromoethane. The NMR spectrum was consistent with the proposed structure.

Step B Synthesis of sodium 1-(benzylthiocarbonyl)ethylsulfonate and sodium bromide mixture as an intermediate

A stirred mixture of 2.4 grams (0.02 mole) sodium sulfite, 5.0 grams (0.02 mole) of 1-benzylthiocarbonyl-1-bromoethane [!], 10 mL of water, and 5 mL of ethanol was heated to 80° C during a two hour period. At the conclusion of this period the reaction mixture was analyzed by TLC, which indicated that some starting material remained. An additional 5 mL of ethanol was added, and the reaction mixture was stirred at 80° C for an additional 45 minutes. After this time the reaction mixture was analyzed by NMR, which indicated the reaction was incomplete. An additional 25 mL of ethanol and 15 mL of water were added and the reaction mixture was stirred at 80° C for about 72 hours. The reaction mixture was again analyzed by TLC, which again indicated that some of the starting material remained. The reaction mixture was allowed to cool to ambient temperature, where it stood for 22 days. At the conclusion of this period, the water and ethanol were removed, yielding about 8.9 grams of a moist white solid, which was taken up in 100 mL of water. The resulting mixture was heated to 90° C, where it stirred for about 18 hours. After this time the heat was removed, and additional water was added. The mixture was extracted with two portions of methylene chloride. The combined methylene chloride extracts were dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, yielding 1.4 grams of total product. The NMR spectrum was consistent with the proposed structure. The aqueous phase from the above extraction was concentrated under reduced pressure, dried under vacuum at 40° C for three hours, yielding 4.8 grams of sodium 1- (benzylthiocarbonyl)ethylsulfonate. The NMR spectrum was consistent with the proposed structure.

Step C Synthesis of 1-(benzylthiocarbonyl)ethylsulfonyl chloride as an intermediate

This compound was prepared in the manner of Step B, Example 7, with 8.0 mL (0.09 mole) of phosphorus oxychloride, 4.8 grams (0.02 mole) of sodium 1-(benzylthiocarbonyl)ethylsulfonate, and 50 mL of toluene as reagents. This preparation differed in that toluene was used in place of phosphorus pentachloride. The yield of 1-(benzylthiocarbonyl)ethylsulfonyl chloride was 2.8 grams. The NMR spectrum was consistent with the proposed structure. Step D Synthesis of 3-[4-chloro-2-fluoro-5-[(1-benzylthiocarbonyl)- ethylsulfonylamino]phenyl]-1-methyl-6-trifluoromethyl- 2,4(1 H,3 -/)-pyrimidinedione (Compound 53)

This compound was prepared in the manner of Step C, Example 7, with 1.0 gram (0.003 mole) of 3-(5-amino-4-chloro-2-fluorophenyl)-1-methyl- 6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, 0.5 mL (0.004 mole) of triethylamine, and 1.0 gram (0.004 mole) of 1-(benzylthiocarbonyl)ethyl- sulfonyl chloride in 10 mL of tetrahydrofuran as reagents. This preparation differed in that the reaction mixture was cooled to -70° C rather than 0° C. The yield of 3-[4-chloro-2-fluoro-5-[(1-benzylthiocarbonyl)ethyl- sulfonylamino]phenyl]-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione was 0.4 gram, m.p. 73-78° C. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 9

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-(N-METHOXY-N- METHYLAMINOCARBONYLMETHYLSULFONYLAMINO)PHENYL]-1-

METHYL-6-TRIFLUOROMETHYL-2,4(1H,3H)-PYRIMIDINEDIONE

(COMPOUND 17)

Step A Synthesis of sodium N-methoxy-N-methylaminocarbonyl- methylsulfonate and sodium chloride mixture as an intermediate

To stirred sodium sulfite, 10.0 grams (0.08 mole), was added 50 mL of water followed by 10.0 grams (0.07 mole) of 2-chloro-N-methoxy-N-methyl- acetamide. Upon completion of the addition the reaction mixture was stirred for 15 minutes and then heated to reflux, where it stirred for about 18 hours. After this time the reaction mixture was allowed to cool to ambient temperature and then poured into 500 mL of ethanol. The resulting mixture was cooled in the refrigerator for about 18 hours and then filtered through diatomaceous earth. The filtrate was concentrated under reduced pressure, and the water remaining in the concentrate was removed by azeotroping with two 100 mL portions of ethanol, yielding 18.9 grams of organic product and sodium chloride. The NMR spectrum indicated the organic product to be sodium N-methoxy-N-methylaminocarbonylmethylsulfonate with a small amount of 2-chloro-N-methoxy-N-methylacetamide. The material was used in the next step without further purification.

Step B Synthesis of N-methoxy-N-methylaminocarbonylmethylsulfonyl chloride as an intermediate

This compound was prepared in the manner of Step B, Example 7, with 30.0 mL (0.32 mole) of phosphorus oxychloride, 18.9 grams (0.06 mole) of sodium N-methoxy-N-methylaminocarbonylmethylsulfonate and sodium chloride mixture, and 100 mL of toluene. This preparation differed in that toluene was used in place of phosphorus pentachloride. The yield of N- methoxy-N-methylaminocarbonylmethylsulfonyl chloride was 7.5 grams. The

NMR spectrum was consistent with the proposed structure.

Step C Synthesis of 3-[4-chloro-2-fluoro-5-(N-methoxy-N- methylaminocarbonylmethylsulfonylamino)phenyl]-1-methyl-6- trifiuoromethyl-2,4(1H,3H)-pyrimidinedione (Compound 17)

This compound was prepared in the manner of Step C, Example 7, with 1.0 gram (0.003 mole) of 3-(5-amino-4-chloro-2-fluorophenyl)-1-methyl- 6-trifluoromethyl-2,4(1H,3/- )-pyrimidinedione, 0.5 mL (0.004 mole) of triethylamine, and 0.7 gram (0.004 mole) of N-methoxy-N- methylaminocarbonylmethylsulfonyl chloride in 15 mL of tetrahydrofuran as reagents. This preparation differed in that the reaction mixture was cooled to -70° C rather than 0° C. The yield of 3-[4-chloro-2-fluoro-5-(N-methoxy-N- methylaminocarbonylmethylsulfonylamino)phenyl]-1-methyl-6-trifluoromethyl- 2,4(1 H,3H)-pyrimidinedione was 1.0 gram, m.p. 189-192° C. The NMR spectrum was consistent with the proposed structure. EXAMPLE 10

SYNTHESIS OF 3-[4-CHLORO-5-(N,N-DIMETHYLAMINOSULFONYL- AMINO)PHENYL]-1-AMINO-6-TRIFLUOROMETHYL-2,4(1H,3H)- PYRIMIDINEDIONE (COMPOUND 8)

Step A Synthesis of 4-chloro-5-(N,N-dimethylaminosulfonylamino)- nitrobenzene as an intermediate

A stirred solution of about 1.0 grams (0.008 mole) of 4-dimethylamino- pyridine and 15.0 (0.09 mole) of 5-amino-2-chloronitrobenzene in 60 mL of pyridine was cooled to -10° C to 0° C, and 10.0 mL (0.09 mole) of N,N- dimethylaminosulfonyl chloride was added dropwise during a 20-25 minute period. Upon completion of the addition the reaction mixture was allowed to warm to ambient temperature and then was heated to reflux, where it stirred for about two hours. After this time the reaction mixture was analyzed by TLC, which indicated that the reaction was incomplete. The reaction mixture was stirred at reflux for about an additional 2.5 hours, after which the reaction mixture was again analyzed by TLC, which again indicated that the reaction was incomplete. The reaction mixture was stirred at reflux for an additional 15 minutes and then an additional 3.0 mL (0.03 mole) of 4- dimethylaminopyridine was added. Upon completion of this addition the reaction mixture was stirred at reflux for about an additional 18 hours. The reaction mixture was then analyzed by TLC for a third time, which indicated that only a small amount of starting material remained. The reaction mixture was allowed to cool to ambient temperature and then poured into about 400 mL of aqueous 10% hydrochloric acid. The resulting solids were collected by filtration. The filter cake was washed with water and then with acetone, which dissolved some of the cake into the filtrate. The remaining filter cake was air-dried, yielding 9.2 grams of 4-chloro-5-(N,N-dimethylaminosulfonyl- amino)nitrobenzene. The NMR spectrum was consistent with the proposed spectrum. The acetone was removed from the filtrate, and the resulting precipitate was collected by filtration. The filter cake was washed with water and dried, yielding an 3.1 grams of crude product. This crude product was combined with 2.3 grams of crude product prepared by a similar route to yield a total of 5.4 grams of crude product.

Step B Synthesis of 4-chloro-5-(N,N-dimethylaminosulfonylamino)- aniline as an intermediate

A solution of 8.2 grams (0.03 mole) of 4-chloro-5-(N,N-dimethylamino- suifonylamino)nitrobenzene, 1.9 grams (0.04 mole) of ammonium chloride, 155 mL of ethanol, and 77 mL of water was stirred for ten minutes, and 10.7 grams (0.19 mole) of iron powder was added in one portion. Upon completion of the addition the reaction mixture was heated to reflux, where it stirred for one hour. After this time the reaction mixture was cooled to ambient temperature and analyzed by TLC, which indicated the reaction was complete. The reaction mixture was filtered through diatomaceous earth, and the filtrate was concentrated under reduced pressure to a residue. The residue was taken up in ethyl acetate, washed with two 75 mL portions of water, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 5.9 grams of 4-chloro-5-(N,N- dimethylaminosulfonylamino)aniline. An additional 3.6 grams of 4-chloro-5-(N,N- dimethylaminosulfonylamino)aniline was prepared in the same manner. The NMR spectrum was consistent with the proposed structure.

Step C Synthesis of ethyl N-[4-chloro-5-(N,N-dimethylamino- sulfonylamino)phenyl]carbamate as an intermediate

A stirred solution of 9.0 grams (0.04 mole) of 4-chloro-5-(N,N- dimethylaminosulfonylamino)aniline and 2.9 mL (0.04 mole) of pyridine in about 80 mL of methylene chloride was cooled to -15° C to -10° C, and 3.9 grams (0.04 mole) of ethyl chloroformate was added during about a 20 minute period. Upon completion of the addition the reaction mixture was allowed to warm to ambient temperature, where it stirred for 45 minutes. After this time the reaction mixture was analyzed by TLC, which indicated the reaction was complete. The reaction mixture was stirred at ambient temperature for an additional 18 hours. At the conclusion of this period the reaction mixture was transferred to a separatory funnel and washed with two portions of water. The organic layer was separated from the aqueous layer, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 11.3 grams of a very tacky oil. This oil was triturated with pentane while warm, yielding 11.1 grams of ethyl N-[4-chloro-

5-(N,N-dimethylaminosulfonylamino)phenyl]carbamate. The NMR spectrum was consistent with the proposed structure. Step D Synthesis of 3-[4-chloro-5-(N, N-dimethylaminosulfonylamino)- phenyl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione as an intermediate

Under a nitrogen atmosphere, a stirred solution of 0.8 grams (0.02 mole) of sodium hydride (60%) in 6 mL of N,N-dimethylformamide (DMF) was cooled to -3_ C in an ice-bath, and 0.9 grams (0.005 mole) of ethyl 3-amino- 4,4,4-trifluorocrotonate in 4 mL of DMF was added dropwise. The resulting mixture was allowed to warm to ambient temperature, and a solution of 1.5 grams (0.005 mole) of ethyl N-[4-chloro-5-(N,N-dimethylaminosulfonylamino)- phenyljcarbamate in 4 mL of DMF was added dropwise. Upon completion of the addition the reaction mixture was stirred for 15 minutes at ambient temperature and then heated to 125° C, where it stirred for an additional two hours. The reaction mixture was concentrated under reduced pressure to a residue, which was purified by column chromatography on silica gel. Elution was with a gradient of pure methylene chloride to 1 :19 methanol and methylene chloride. The product-containing fractions were combined and concentrated under reduced pressure, yielding 1.0 gram of 3-[4-chloro-5- (N,N-dimethylaminosulfonyiamino) phenyl]-6-trifluoromethyl-2,4(1 - ,3rV)- pyrimidinedione, m.p. > 206° C. The NMR spectrum was consistent with the proposed structure. An additional 2.9 grams of 3-[4-chloro-5-(N,N-dimethylaminosulfonylamino)- phenyl]-6-trifluoromethyl-2,4(1 - ,3 - -pyrimidinedione was prepared in the same manner.

Step E Synthesis of 3-[4-chloro-5-(N,N-dimethylaminosulfonylamino)- phenyl]-1 -amino-6-trifluoromethyl-2,4(1 H,3H)-pyrimidinedione

(Compound 8)

In order to effect solution a mixture of 0.8 gram (0.002 mole) of 3-[4- chloro-5-(N,N-dimethylaminosulfonylamino)phenyl]-6-trifluoromethyl-2,4- (1H,3 -/)-pyrimidinedione and 0.5 gram (0.004 mole) of potassium carbonate in 25 mL of tetrahydrofuran was stirred at ambient temperature, and then 0.8 gram (0.004 mole) of 1-aminooxysulfonyl-2,4,6-trimethylbenzene was added in one portion. Upon completion of the addition the reaction mixture was stirred at ambient temperature for 1.5 hours. At the conclusion of this period the reaction mixture was poured into 75 mL of an aqueous saturated sodium chloride solution, and the resulting mixture was extracted with two 50 mL portions of ethyl acetate. The combined ethyl acetate extracts were washed with two portions of an aqueous saturated sodium chloride solution, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 0.5 gram of 3-[4-chloro-5-(N,N- dimethylaminosulfonylamino)phenyl]-1-amino-6-trifluoromethyl-2,4(1H,3H)- pyrimidinedione, m.p. 203-204° C. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 11 SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-(N,N-DIMETHYLAMINO-

SULFONYLAMINO)PHENYL]-1-AMINO-6-TRIFLUOROMETHYL-2,4(1H,3H)- PYRIMIDINEDIONE (COMPOUND 10)

Step A Synthesis of ethyl N-[2-fluoro-5-(N,N-dimethylaminosulfonyl- amino)phenyl]carbamate as an intermediate

This compound was prepared in the manner of Step A, Example 10, with 10.0 grams (0.05 mole) ethyl N-(5-amino-2-fluorophenyl)carbamate and 5.8 mL (0.05 mole) of N,N-dimethylsulfonyl chloride in 60 mL of pyridine as reagents. This preparation differed in that 4-dimethylaminopyridine was not used. The yield of ethyl N-[2-fluoro-5-(N,N-dimethylaminosulfonylamino)- phenyljcarbamate was 10.9 grams, m.p. 106.5-107.5° C. The NMR spectrum was consistent with the proposed structure.

Step B Synthesis of ethyl N-[4-chloro-2-fluoro-5-(N,N-dimethylamino- sulfonylamino)phenyl]carbamate as an intermediate

A stirred solution of 4.6 grams (0.02 mole) of ethyl N-[2-fluoro-5-(N,N- dimethylaminosulfonylamino)phenyl]carbamate in 60 mL of acetic acid and 6 mL of water was exposed to chlorine gas for five minutes. At the end of this period the reaction mixture was exposed to a nitrogen atmosphere for ten minutes, then analyzed by TLC, which indicated the reaction was complete.

The reaction mixture was poured into 200 mL of water. The resulting solid was collected by filtration, yielding 4.1 grams of crude product. The crude product was purified by column chromatography on silica gel. Elution was accomplished with 1:1 hexane and ethyl acetate. The product-containing fractions were concentrated under reduced pressure, yielding 2.1 grams of ethyl N-[4-chloro-2-fluoro-5-(N,N-dimethylaminosulfonylamino) phenylj- carbamate. The NMR spectrum was consistent with the proposed structure.

Step C Synthesis of 3-[4-chloro-2-fluoro-5-(N,N-dimethylamino- sulfonylamino)phenyl]-6-trifluoromethyl-2,4(1H,3 -/)- pyrimidinedione as an intermediate

This compound was prepared in the manner of Step C, Example 10, with 2.4 grams (0.007 mole) of ethyl N-[4-chloro-2-fluoro-5-(N,N- dimethylamino-sulfonylamino)phenyl]carbamate, 1.2 grams (0.03 mole) of sodium hydride (60%), and 1.4 grams (0.008 mole) of ethyl 3-amino-4,4,4- trifluorocrotonate in 30 mL of N,N-dimethylformamide as reagents. The yield of 3-[4-chloro-2-fluoro-5-(N,N-dimethylaminosulfonylamino)phenyl]-6- trifluoromethyl-2,4(1H,3rV)-pyrimidinedione was 0.9 gram, m.p. 79-81° C. The NMR spectrum was consistent with the proposed structure. Step D Synthesis of 3-[4-chloro-2-fluoro-5-(N,N-dimethylamino- sulfonylamino)phenyl]-1-amino-6-trifluoromethyl-2,4(1H,3r )- pyrimidinedione (Compound 10)

This compound was prepared in the manner of Step E, Example 10, with 0.8 gram (0.002 mole) of 3-[4-chloro-2-fluoro-5-(N,N- dimethylaminosulfonylamino)phenyl]-6-trifluoromethyl-2,4(1 - ,3H)- pyrimidinedione, 0.5 gram (0.004 mole) of potassium carbonate, and 0.8 gram (0.004 mole) of 1-aminooxysulfonyl-2,4,6-trimethylbenzene in 25 mL of tetrahydrofuran as reagents. The yield of 3-[4-chloro-2-fluoro-5-(N,N- dimethylaminosulfonyl-amino)phenyl]-6-trifluoromethyl-2,4(1H,3/-/)- pyrimidinedione was 0.1 gram. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 12

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-[N-ACETOXYACETYL-N-[N'-

ACETOXYACETYL-N'-METHYLAMINOSULFONYL]AMINO]PHENYL]-1-

METHYL-6-TRIFLUOROMETHYL-2,4(1H,3 )-PYRIMIDINEDIONE

(COMPOUND 5)

This compound was prepared in the manner of Step C, Example 7, with 0.8 gram (0.002 mole) of 3-[4-chloro-2-fluoro-5-(N-methylaminosulfonylamino)- phenyl]-1-methyl-6-trifluoromethyl-2,4(1 - ,3H)-pyrimidinedione, 0.2 gram

(0.002 mole) of triethylamine, and 0.4 gram (0.004 mole) of acetoxyacetyl chloride in 25 mL of tetrahydrofuran as reagents. The yield of 3-[4-chloro-2- fluoro-5-[N-acetoxyacetyl-N-[N'-acetoxyacetyl-N'-methylaminosulfonyl]- amino]phenyl]-1-methyl-6-trifluoromethyl-2,4(1H,3ry)-pyrimidinedione was 0.7 gram, m.p. 93-105° C. The NMR spectrum was consistent with the proposed structure. EXAMPLE 13

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-[(N-2-CYANOETHYL-N- METHYLAMINO)SULFONYLAMINO]PHENYL]-1-METHYL-6-TRIFLUORO- METHYL-2,4(1 H,3H)-PYRIMIDINEDIONE (COMPOUND 2)

Step A Synthesis of N-2-cyanoethyl-N-methylaminosulfonyl chloride as an intermediate

A stirred solution of 4.0 mL (0.05 mole) of sulfuryl chloride in 15 mL of chloroform was cooled to -5° C, and 8.2 grams (0.10 mole) of 3- methylaminopropionitrile in 10 mL of chloroform was added dropwise at a rate to maintain the temperature below 0° C. Upon completion of addition, the reaction mixture was stirred for one hour and then allowed to warm to ambient temperature where it stirred for about 18 hours. After this time, the reaction mixture was filtered and washed with chloroform. The filtrate was concentrated under reduced pressure, yielding 4.8 grams of N-2-cyanoethyl-

N-methylaminosulfonyl chloride. The NMR spectrum was consistent with the proposed structure. Step B Synthesis of 3-[4-chloro-2-fluoro-5-[(N-2-cyanoethyl-N-methyl- amino)sulfonylamino]phenyl]-1-methyl-6-trifluoromethyl- 2,4-(1H,3rV)-pyrimidinedione (Compound 2)

This compound was prepared in the manner of Example 4, with 0.6 gram (0.002 mole) of 3-(5-amino-4-chloro-2-fluorophenyl)-1-methyl-6- trifluoromethyl-2,4(1H,3H -pyrimidinedione, 0.2 gram (0.002 mole) of 4- dimethylaminopyridine, and 1.5 grams (0.008 mole) of N-2-cyanoethyl-N- methylaminosulfonyl chloride. The yield of 3-[4-chloro-2-fluoro-5-[(N-2- cyanoethyl-N-methylamino)sulfonylamino]phenyl]-1-methyl-6-trifluoromethyl- 2,4(1 H,3H)-pyrimidinedione was 0.3 gram, m.p. 123-126° C. The NMR spectrum was consistent with the proposed structure. EXAMPLE 14

SYNTHESIS OF 3-[4-CHLORO-2-FLUORO-5-(BENZYLSULFONYLAMINO)- PHENYL]-1-AMINO-6-TRIFLUOROMETHYL-2,4(1H,3H)- PYRIMIDINEDIONE (COMPOUND 19)

Step A Synthesis of 4-chloro-2-fluoro-5-N,N-di(benzylsulfonyl)amino- nitrobenzene as an intermediate

This compound was prepared in the manner of Step C, Example 7, with 5.0 grams (0.03 mole) of 5-amino-4-chloro-2-fluoronitrobenzene, about 12.3 mL (0.09 mole) of triethylamine, and 15.7 grams (0.08 mole) of α- toluenesulfonyl chloride in 135 mL of tetrahydrofuran as reagents. This preparation differed in that the reaction mixture was cooled to -55° C to -50° C rather than 0° C. The yield of 4-chloro-2-fluoro-5-N,N-di(benzylsulfonyl)- aminonitrobenzene was 11.6 grams. The NMR spectrum was consistent with the proposed structure.

Step B Synthesis of 4-chloro-2-fluoro-5-(benzylsulfonylamino)nitro- benzene as an intermediate

To a stirred solution of 11.6 grams (0.02 mole) of 4-chloro-2-fluoro-5- N,N-di(benzylsulfonyl)aminonitrobenzene in 150 mL dioxane was added 30.0 mL (0.03 mole) of a 1 N aqueous sodium hydroxide solution in one portion. Upon completion of the addition the reaction mixture was heated to 66° C, and an additional 17.0 mL (0.02 mole) of aqueous 1N sodium hydroxide solution was added. The reaction mixture was heated to 70° C during a 50 minute period, after which it was analyzed by TLC, which indicated the reaction was complete. The reaction mixture was allowed to cool to 25° C, and 25 mL of aqueous 2N hydrochloric acid was added. The resulting mixture was stirred at 25° C for 35 minutes, and then the acid and solvent were removed under reduced pressure to yield a residue, which was taken up in water and methylene chloride. The organic layer was separated, washed with two portions of aqueous 2N hydrochloric acid and one portion of water, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 7.5 grams of 4-chloro-2- fluoro-5-(benzylsulfonylamino)nitrobenzene, m.p. 136-141° C. The NMR spectrum was consistent with the proposed structure. An additional 0.3 gram of 4-chloro-2-fluoro-5-(benzylsulfonylamino)- nitrobenzene was obtained by a similar route.

Step C Synthesis of 4-chloro-2-fluoro-5-(benzylsulfonylamino)aniline as an intermediate

This compound was prepared in the manner of Step B, Example 10, with 0.6 gram (0.002 mole) of 4-chloro-2-fluoro-5-(benzylsulfonylamino)nitro- benzene, 0.1 gram (0.002 mole) of ammonium chloride, 0.6 gram (0.008 mole) of iron powder, 8 mL of ethanol, and 5 mL of water as reagents. The yield of 4-chloro-2-fluoro-5-(benzylsulfonylamino)aniline was 0.4 gram, m.p. 106-110° C. The NMR spectrum was consistent with the proposed structure. An additional 4.0 grams of 4-chloro-2-fluoro-5- (benzylsulfonylamino)aniline was similarly prepared.

Step D Synthesis of ethyl N-[4-chloro-2-fluoro-5-(benzylsulfonyl- amino)-phenyl]carbamate as an intermediate

This compound was prepared in the manner of Step C, Example 10, with 3.2 grams (0.01 mole) of 4-chloro-2-fluoro-5-

(benzylsulfonylamino)aniline, 0.9 mL (0.01 mole) of pyridine, and 1.1 grams

(0.01 mole) of ethyl chloroformate in 305 mL of methylene chloride as reagents. The yield of ethyl N-[4-chloro-2-fluoro-5-

(benzylsulfonylamino)phenyl]carbamate was 3.6 grams. The NMR spectrum was consistent with the proposed structure.

An additional 1.2 grams of ethyl N-[4-chloro-2-fluoro-5-(benzylsulfonyl- amino) phenyljcarbamate was prepared by a similar route. Step E Synthesis of 3-[4-chloro-2-fluoro-5-(benzylsulfonylamino)- phenyl]-6-trifluoromethyl-2,4(1H,3 -/)-pyrimidinedione as an intermediate

This compound was prepared in the manner of Step D, Example 10, with 2.6 grams (0.007 mole) of ethyl N-[4-chloro-2-fluoro-5-(benzylsulfonyl- amino) phenyljcarbamate, 0.5 gram (0.02 mole) of sodium hydride (60%), and 1.3 gram (0.008 mole) of ethyl 3-amino-4,4,4-trifluorocrotonate in 20 mL of N,N-dimethylformamide as reagents. The yield of 3-[4-chloro-2-fluoro-5- (benzylsulfonylamino)phenyl]-6-trifluoromethyl-2,4(1 -/,3H)-pyrimidinedione was 1.0 gram. The NMR spectrum was consistent with the proposed structure.

Step F Synthesis of 3-[4-chloro-2-fluoro-5-(benzylsulfonylamino)- phenyl]-1-amino-6-trifluoromethyl-2,4(1r7^,,3 -/)-pyrimidinedione (Compound 19)

This compound was prepared in the manner of Step E, Example 10, with 1.0 gram (0.002 mole) of 3-[4-chloro-2-fluoro-5-(benzylsulfonylamino)- phenyl]-6-trifluoromethyl-2,4(1H,3 -/)-pyrimidinedione, 0.3 gram (0.002 mole) of potassium carbonate, and 0.9 gram (0.004 mole) of 1-aminooxysulfonyl- 2,4,6-trimethylbenzene in 25 mL of tetrahydrofuran as reagents. The yield of 3-[4-chloro-2-fluoro-5-(benzylsulfonylamino)phenyl]-6-trifluoromethyl- 2,4(1 H,3/-/)-pyrimidinedione was 0.3 gram. The NMR spectrum was consistent with the proposed structure.

HERBICIDAL ACTIVITY

The 3-[2,4-disubstituted-5-(substituted amino)phenyl]-1 -substituted-6- trifluoromethyl-2,4-(1H,3rτ pyrimidinediones of the present invention were tested for pre- and postemergence herbicidal activity on a variety of crops and weeds. The test plants included soybean (Glycine var. Winchester), field corn (Zea mays var. Pioneer 3732), wheat (Triticum aestivum var. Lew), morning-glory (Ipomea lacunosa or Ipomea hederacea). velvetleaf (Abutilon theophrasti). green foxtail (Setaria viridis). Johnsongrass (Sorghum halepense). blackgrass (Aloepecurus mvosuroides). common chickweed (Stellaria media), and common cocklebur (Xanthium strumarium L.).

For preemergence testing two disposable fiber flats (8 cm x 15 cm x 25 cm) for each rate of application of each candidate herbicide were filled to an approximate depth of 6.5 cm with steam-sterilized sandy loam soil. The soil was leveled and impressed with a template to provide five evenly spaced furrows 13 cm long and 0.5 cm deep in each flat. Seeds of soybean, wheat, corn, green foxtail, and Johnsongrass were planted in the furrows of the first flat, and seeds of velvetleaf, morning-glory, common chickweed, cocklebur, and blackgrass were planted in the furrows of the second flat. The five-row template was employed to firmly press the seeds into place. A topping soil of equal portions of sand and sandy loam soil was placed uniformly on top of each flat to a depth of approximately 0.5 cm. Flats for postemergence testing were prepared in the same manner except that they were planted 9- 14 days prior to the preemergence flats and were placed in a greenhouse and watered, thus allowing the seeds to germinate and the foliage to develop.

In both pre- and postemergence tests a stock solution of the candidate herbicide was prepared by dissolving 0.27g of the compound in 20 mL of water/acetone (50/50) containing 0.5% v/v sorbitan monolaurate. For an application rate of 3000 g/ha of herbicide a 10 mL portion of the stock solution was diluted with water/acetone (50/50) to 45 mL. The volumes of stock solution and diluent used to prepare solutions for lower application rates are shown in the following table: Application Volume of Volume of Total Volume

Rate Stock Solution Acetone/Water of Spray Solution

(q/ha) (mL). (mL) (mL)

3000 10 35 45

1000 3 42 45

300 1 44 45

100 0.3 45 45.3

30 0.1 45 45.1

10 0.03 45 45.03

3 0.01 45 45.01

The preemergence flats were initially subjected to a light water spray. The four flats were placed two by two along a conveyor belt (i.e., the two preemergence followed by the two postemergence flats). The conveyor belt fed under a spray nozzle mounted about ten inches above the postemergent foliage. The preemergence flats were elevated on the belt so that the soil surface was at the same level below the spray nozzle as the foliage canopy of the postemergent plants. The spray of herbicidal solution was turned on, and once it had stabilized the flats were passed under the spray at such a rate that they received a coverage equivalent of 10OOL/ha. At this coverage the application rates are those shown in the above table for the individual herbicidal solutions. The preemergence flats were watered immediately thereafter, placed in the greenhouse, and watered regularly at the soil surface. The postemergence flats were immediately placed in the greenhouse and not watered until 24 hours after treatment with the test solution. Thereafter they were regularly watered at ground level. After 12-17 days the plants were examined and the phytotoxicity data were recorded. Herbicidal activity data at selected application rates are given for various compounds of the present invention in Table 3 and Table 4. The test compounds are identified by numbers that correspond to those in Table 1.

Phytotoxicity data are taken as percent control. Percent control is determined by a method similar to the 0 to 100 rating system disclosed in "Research Methods in Weed Science," 2nd ed., B. Truelove, Ed.; Southern Weed Science Society; Auburn University, Auburn, Alabama, 1977. The rating system is as follows:

Herbicide Rating System

Rating Description

Percent of Main Crop Weed

Control Cateqories Description Description

0 No effect No crop No weed reduction control or injury

10 Slight disVery poor weed coloration control or stunting

20 Slight Some disPoor weed effect coloration, control stunting or stand loss

30 Crop injury Poor to defimore pronounced cient weed but not lasting control

40 Moderate injury, Deficient weed crop usually control recovers

50 Moderate Crop injury Deficient to effect more lasting, moderate weed recovery doubtful control

60 Lasting crop Moderate weed injury, no control recovery

70 Heavy injury and Control somestand loss what less than satisfactory

80 Severe Crop nearly desSatisfactory troyed, a few to good weed survivors control

90 Only occasional Very good to live plants left excellent control

100 Complete Complete crop Complete weed effect destruction destruction For herbicidal application, the 3-[2,4-disubstituted-5-(substituted amino)phenyl]-1-substituted-6-trifluoromethyl-2,4-(1H,3rV)-pyrimidinediones are formulated into herbicidal compositions by admixture in herbicidally effective amounts with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application. Thus, for agricultural use the present herbicidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application.

These herbicidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of vegetation is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful herein is one containing 1.0 part or less of the herbicidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for both pre- and post- emergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wettable inorganic diluents. Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, 1.0 part of sodium lignosulfonate, and 0.3 part of sulfonated aliphatic polyester as wetting agents. Frequently, additional wetting agent and/or oil will be added to the tank mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant. Other useful formulations for herbicidal applications are emulsifiable concentrates (ECs) which are homogeneous liquid compositions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent. For herbicidal application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition. Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water. Flowables, like ECs, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition. For application, flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated. Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of long-chain mercaptans and ethylene oxide. Many other types of useful surface-active agents are available in commerce. The surface-active agent, when used, normally comprises from 1 to 15% by weight of the composition. Other useful formulations include suspensions of the active ingredient in a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents.

Still other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy. Pressurized sprays, typically aerosols wherein the active ingredient is dispersed in finely divided form by a propellant, such as carbon dioxide, propane or butane, may also be used. Water-soluble or water-dispersible granules are also useful formulations for herbicidal application of the present compounds. Such granular formulations are free-flowing, non-dusty, and readily water- soluble or water-miscible. The soluble or dispersible granular formulations described in U.S. patent No. 3,920,442 are useful herein with the present herbicidal compounds. In use by the farmer on the field, the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc., may be diluted with water to give a concentration of active ingredient in the range of say 0.1 % or 0.2% to 1.5% or 2%. The 3-[2,4-disubstituted-5-(substituted amino)phenyl]-1-substituted-6- trifluoromethyl-2,4-(1H,3fV)-pyrimidinediones of this invention may be formulated and/or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture. In applying an active compound of this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of course employed; the amount may be as low as, for example, about 3 to 3000 g/ha to, preferably, about 10 to 30 g/ha. For field use, where there are losses of herbicide, higher application rates (for example, four times the rates mentioned above) may be employed.

The 3-[2,4-disubstituted-5-(substituted amino)phenylJ-1 -substituted-6- trifluoromethyl-2,4-(1H,3rV)-pyrimidinediones of this invention may be used in combination with other herbicides, for example they may be mixed with, say, an equal or larger amount of a known herbicide such as aryloxyalkanoic acid herbicides such as (2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chloro-2- methylphenoxy)acetic acid (MCPA), (+/-)-2-(4-chloro-2-methylphenoxy) propanoic acid (MCPP); urea herbicides, such as N,N-dimethyl-N'-[4-(1- methylethyl)phenyl]urea (isoproturon); imidazolinone herbicides, such as 2- [4 , 5-d ihyd ro-4-methyl-4-( 1 -methylethyl)-5-oxo- 1 H-imidazol-2-y l]-3- pyridinecarboxylic acid (imazapyr), a reaction product comprising (+/-)-2-[4,5- dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2-yl]-4-methylbenzoic acid and (+/-)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H-imidazol-2- yl]-5-methylbenzoic acid (imazamethabenz), (+/-)-2-[4, 5-d ihyd ro-4-methyl-4- (1 -methylethyl)-5-oxo-1 H-imidazol-2-yl]-5-ethyl-3-pyridinecarboxylic acid (imazethapyr),and (+/-)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1 H- imidazol-2-yl]-3-quinolinecarboxylic acid (imazaquin); diphenyl ether herbicides, such as 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid (acifiuorfen), methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (bifenox), and 5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenz- amide (fomasafen); hydroxybenzonitrile herbicides, such as 4-hydroxy-3,5- diiodobenzonitrile (ioxynil), and 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil); sulfonylurea herbicides, such as 2-[[[[(4-chloro-6-methoxy-2- pyrimidinyl)-amino]carbonyl]amino]sulfonyl]benzoic acid (chlorimuron), 2- chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2- yl)amino]carbonyl]benzenesulfonamide (chlorsulfuron), 2-[[[[[(4,6-dimethoxy- 2-pyrimidinyl)aminocarbonylJamino]-sulfonyl]methyl]benzoic acid (bensulfuron), 2-[[[[(4,6-dimethoxy-2-pyrimidin-yl)amino]carbonyl]amino]- sulfonyl]-1-methyl-1H-pyrazol-4-carboxylic acid (pyrazosulfuron), 3-[[[[(4- methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]-amino]sulfonyl]-2- thiophenecarboxylic acid (thifensulfuron), and 2-(2-chloroethoxy)-N-[[(4- methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]-benzene-sulfonamide (triasulfuron); 2-(4-aryloxyphenoxy)alkanoic acid herbicides, such as (+/-)-2- [4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy]propanoic acid (fenoxaprop), (+/-)- 2-[4-[[5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propanoic acid (fluazifop), (+/-)-2-[4-(6-chloro-2-quinoxalinyl)oxy]phenoxy]propanoic acid (quizalofop), and (+/-)-2-[-(2,4-dichlorophenoxy)phenoxy]propanoic acid (diclofop); benzothiadiazinone herbicides, such as 3-(1-methylethyl)-1H-2,1,3- benzothiadiazin-4(3H)-one 2,2-dioxide (bentazone); 2-chloroacetanilide herbicides, such as N-(butoxymethyl)-2-chloro-2',6'-diethylacetanilide (butachlor); arenecarboxylic acid herbicides, such as 3,6-dichloro-2- methoxybenzoic acid (dicamba); and pyridyloxyacetic acid herbicides, such as [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]-acetic acid (fluroxypyr).

It is apparent that various modifications may be made in the formulation and application of the compounds of this invention without departing from the inventive concepts herein as defined in the claims.

Table 1

3-[2,4-Disubstituted-5-(substituted amino)phenyl]-1-substituted-6- trifluoromethyl-2,4-(1 - ,3H)-pyrimidinediones as Herbicides

Cmpd. No. R R^{2^} Y

-CH, H -N(CH₃)CH₂CH₂C_≡N Cl

-CH, H -N(CH₃)₂ -CH₃ F

-CH₃ -C(0)CH₂OC(0)CH₃ -N(CH₃)₂ Cl

-CH₃ -C(0)CH₂OC(0)CH₃ - Cl

N(CH₃)C(0)CH₂OC(0)CH₃ -CH₃ -C(0)CH₂OC(0)CH₃ -CH(CH₃)C≡N Cl

-NH, H -CH(CH₃)C=N Cl H

-NH, H -N(CH₃)₂ Cl H Table 1 (continued)

Cmpd. No. R R¹ R² X Ϋ~

9 -NH₂ H -CH(CH₃)C≡N Cl F

10 -NH₂ H -N(CH₃)₂ Cl F

11 -CH₃ H -CH₂CH₂OC₆H₅ Cl F

12 -CH₃ H -CH₂CH₂CH₂OC₆H₅ Cl F

13 -CH₃ H -CH₂CH(CH₃)CsN Cl F

14 -CH₃ H -CH₂CH₂CH₂C≡N Cl F

15 -CH₃ S(0)2CH₂CH2CH₂C≡N -CH₂CH₂CH₂C≡N Cl F

16 -CH₃ H -CH₂C(0)N(C₂H₅)₂ Cl F

17 -CH₃ H -CH₂C(0)N(CH₃)0CH₃ Cl F

18 -CH₃ H -CH₂C(0)OCH₂C₆H₅ Cl F

19 -NH₂ H -CH₂C₆H₅ Cl F

20 -CH₃ H ' -NHCH₂C0₂C₂H₅ Cl F

21 -CH₃ H -N(CH₃)CH₂C0₂C₂H_S Cl F

N

\

22 -CH₃ H CH-C=N _c, p

CHa

23 -CH₃ H -N(CH₃)CH₂CH₂0C₆H₅ Cl F Table 1 (continued)

Cmpd. No. R R^1"

24 -CH, H -N(CH₂C≡N)CH₂C0₂C₂H₅ Cl

25 -CH, H ^■N-CH-C≡N Cl H

26 -NH, H -N(C₂H₅)₂ Cl

27 -CH, H -CHoCONH, Cl

28 -CH, H -CH₂CONHCH₃ Cl

29 -CH, H -CH₂CON(CH₃)₂ Cl

30 -CH₃ H -CH₂C(0)NHCH₂C₆H₅ Cl

31 -CH, H -CH₂C(CH₃)₂C≡N Cl

32 -CH₃ H -CH₂C0₂CH(CH₃)₂ Cl

33 -CH, H -CH,CO,CH,C≡N Cl

34 -CH, H -CH₂C0₂CH₂C≡CH Cl

35 -CH, H -CH₂C0₂CH₂C(CH₃)=CH₂ Cl

36 -CH₃ H -CH₂CH(CH₃)CON(CH₃)₂ Cl

37 -CH₃ -CH₃ -N(CH₃)C₂H₄C≡N Cl

38 -CH₃ -C(0)CH₃ -N(CH₃)C₂H₄C=N Cl Table 1 (continued)

Cmpd. No. R R¹ R² X Ϋ~

39 -CH₃ -C(0)OCH₃ -N(CH₃)C₂H₄C≡N Cl F

40 -CH₃ -C(0)CH₂OC(0)CH₃ -N(CH₃)C₂H₄C≡N Cl F

41 -CH₃ -C(0)CH₂OC(0)CH₃ -C₂H₅ Cl F

42 -CH₃ -C(0)CH₂OC(0)CH₃ -CH₂C₆H₅ Cl F

43 -CH₃ -C(0)CH₃ -CH₂C(0)N(CH₃)0CH₃ Cl F

44 -CH₃ -S(0)₂CH₂CH₂C≡N -CH₂CH₂C≡N Cl F

45 -CH₃ H -CH₂CH₂C≡N Cl F

46 -CH₃ H -N(CH₃)CH₂CH₂C≡N Cl H

47 -CH₃ H -N(CH₃)C(0)CH₂0C(0)CH₃ Cl F

49 -CH₃ H 2-(2-chlorophenoxy)ethyl Cl F

50 -CH₃ H 2-(4-chlorophenoxy)ethyl Cl F 10 H0θ(^εH0)N(θ)0- ^ZHN- 39

d 10 ^SH^Z0^Z00- ^ZHN- 1-9

d 10 ^sH^z0S00- ^εH0- 69

10 ^z(^εH0)NO0- ^εHO- 89

^EH0HNO0- ^εH0- 19

^zHNO0" ^εH0" 99

H^z00- ^εH0- 99

H⁹0^zH0S(O)0- ^εH0- εg

H00(^εH0)N(0)0- ^εH0- 1.9

ΓH y O pdu^jo

(panurjuoo) , 9|qει

Qϊ PS£Z/L6Sa/ΣDd 08Z8Z/86 OΛV N

Table 1 (continued)

Cmpd. No. R' R"

63 H H Cl H

64 H H Cl

65 H H Br

66 H -CH, Cl H

67 H -CH₃ Cl Cl

68 H -CH₃ Cl

69 H -CH₃ Br

70 H -C₂H₅ Cl H

71 H -C₂H₅ Cl Table 1 (continued)

Cmpd. No. Y

72 H -C₂ ₂Hπ₅ Br

73 H -CH(CH₃)₂ Cl H

74 H -CH(CH₃)₂ Cl

75 H -CH(CH₃)₂ Br

76 H -C₃H₇ Cl

77 H -CHCICβ 6H^π5 Cl

78 -CH, -CH, Cl

79 -C(0)CH₃ -CH, Cl

Table 1 (continued)

Cmpd. No. R"

80 -CH₃ Cl (Sodium Salt)

81 -CH₃ Cl (Isopropylamine Salt)

82 -C₂H₅ Cl (Sodium Salt)

Cmpd. No. P⁵ X Ϋ~

83 phenyl Cl H

84 furan-2-yl Cl F

Cmpd. No. R° Y

85 -CO, Cl

(Sodium Salt)

Table 2

CHARACTERIZING DATA

Cmpd No Melting Point/Physical State Cmod No Melting Point/Phvsical State

1 202-204 °C 48 RESIN

2 123-126 °C 49 67-72 °C w/prior sintering

3 SOLID 50 73-76 °C w/prior sintering

4 80-81 C becomes resin 51 95-96 °C

5 SOLID 52 127-128 °C

6 100-106 °C 53 73-78 C

7 > 207 °C 58 92-98 C

8 203-204 °C 62 96-99 °C w/prior sintering

9 124-125 °C becomes resin 63 220-223 °C

10 SOLID 64 100-102 °C

11 70-73 °C 65 119-120 °C

12 80-83 °C becomes resin 66 solid

13 79-80 °C 67 105-108 °C

14 SOLID 68 97-105 °

15 217-220 °C 69 108-110 °C

16 190-193 °C 70 114-115 °C

17 SOLID 71 94-98 °C

18 64-69 °C 72 87-88 °C

19 SOLID 73 95-100 °C

21 WAXY RESIN 74 SOLID

29 206-208 °C 75 95-97 °C

37 65-68 °C w/prior sintering 76 86-87 °C

38 SOLID 77 188-190 °C

39 SOLID 78 SOLID

40 SOLID 79 108-112 °C

41 160-161 °C w/prior sintering 80 SOLID 2 174-175 °C 81 SOLID 3 91-92 °C becomes resin 82 SOLID 4 125-126 °C 83 SOLID 5 91-92 °C 84 72-73 °C 6 170-172 °C 7 SOLID Table 3 PREEMERGENCE HERBICIDAL ACTIVITY (% CONTROL)

Cmpd

No. Rate Soy Wht Crn Abuth Iposs Sterne Xanpe Alomy Setvi Sorha

1 0.3 40 10 20 100 100 70 20 60 60 40

2 0.3 75 40 50 100 100 100 100 60 50 55

3 0.3 100 60 80 100 100 100 60 55 100 80

4 0.3 100 90 90 100 100 100 100 80 100 80

5 0.3 60 60 80 100 100 100 80 60 80 80

6 0.3 50 60 50 100 100 100 100 65 60 75

7 0.3 100 10 0 100 100 100 90 20 100 30

8 0.3 100 75 90 100 100 100 100 70 100 75

9 0.3 100 60 60 100 100 100 100 75 100 65

10 0.3 100 80 90 100 100 100 100 80 100 85

11 0.3 80 20 40 100 100 100 90 80 90 50

12 0.3 100 25 10 100 100 100 90 60 70 70

13 0.3 30 20 20 100 100 100 100 70 90 40

14 0.3 80 50 60 100 100 100 100 90 90 70

15 0.3 40 0 10 100 100 90 100 70 60 55

16 0.3 60 0 20 100 100 ND 70 50 0 30

17 0.3 90 30 60 100 100 100 100 80 40 75

18 0.3 25 10 20 100 100 100 50 30 20 50

19 0.3 100 80 90 100 100 ND 100 90 100 85

21 0.3 95 50 50 100 100 100 100 75 90 75

29 0.3 60 20 60 100 100 100 100 80 40 80

37 0.3 100 100 80 100 100 100 100 100 100 80

38 0.3 100 40 80 100 100 100 100 95 90 75

39 0.3 100 100 100 100 100 100 100 100 100 100 0 0.3 100 30 60 100 100 100 100 80 100 65 1 0.3 80 80 80 100 100 100 ND ND 100 100 2 0.3 20 50 70 100 100 100 ND ND 50 50 4 0.3 95 30 60 100 100 100 100 ND 80 80 5 0.3 80 30 40 100 100 100 100 ND 90 80 6 0.3 80 0 30 100 100 100 100 ND 70 30 7 0.3 30 50 75 100 100 90 ND ND 80 70 8 0.3 100 70 90 100 95 100 100 ND 95 90 Table 3 (continued) Cmpd

No. Rate Soy Wht Cm Abuth Iposs Sterne Xanpe Alomv Setvi Sorha

49 0.3 100 40 10 100 100 ND 80 90 80 60

50 0.3 20 40 0 100 100 ND 100 100 70 25

51 0.3 60 60 60 100 100 70 90 80 65 65

52 0.3 100 10 20 100 100 100 100 50 40 25

53 0.3 60 10 25 100 100 100 80 60 95 70

58 0.3 95 80 80 100 100 100 100 80 95 90

62 0.3 100 80 90 100 100 100 100 ND 100 100

63 0.3 10 10 10 100 100 100 100 60 60 20

64 0.3 100 70 60 100 100 100 100 75 80 75

65 0.3 50 25 20 100 100 80 90 ND 80 70

66 0.3 0 10 0 100 100 ND 100 ND 25 30

67 0.3 40 10 20 90 100 50 50 20 30 50

68 0.3 70 60 40 100 100 100 100 ND 65 65

69 0.3 20 40 20 100 100 100 100 ND 80 70

70 0.3 10 0 25 100 100 100 100 40 70 50

71 0.3 80 50 60 100 100 ND 100 ND 60 90

72 0.3 40 60 25 100 100 100 100 80 100 75

73 0.3 0 0 10 100 100 95 100 30 0 30

74 0.3 35 10 20 100 100 90 100 50 25 60

75 0.3 0 30 10 100 100 100 100 10 10 40

76 0.3 80 60 40 100 100 100 100 75 100 80

77 0.3 20 10 20 100 100 55 60 25 50 40

78 0.3 100 70 90 100 100 80 100 75 100 100

79 0.3 95 50 10 100 100 100 100 80 90 80

80 0.3 70 30 20 100 100 100 100 80 100 60

81 0.3 90 50 30 100 100 100 100 90 100 90

82 0.3 5 50 15 100 100 ND 100 ND 70 40

83 0.3 0 40 10 100 100 100 100 40 25 20

84 0.3 50 30 10 100 100 ND 80 ND 70 60

Rate is in kg/hectare. Soy is soybean; Wht, wheat; Cm, corn; Abuth, velveltleaf; Iposs, morning-glory; Steme, chickweed; Xanpe, cocklebur; Alomy, blackgrass; Setvi, green foxtail; Sorha, Johnsongrass

ND = NO DATA Table 4 POSTEMERGENCE HERBICIDAL ACTIVITY (% CONTROL)

Cmpd

No. Rate Soy Wht Cm Abuth Iposs Sterne Xanpe Alomy Setvi Sorha

1 0.3 70 30 50 100 100 25 40 20 70 40

2 0.3 90 35 70 100 100 100 100 60 70 60

3 0.3 80 50 75 100 80 75 100 50 80 70

4 0.3 90 70 80 100 100 100 100 90 70 70

5 0.3 80 60 60 100 100 80 95 40 80 60

6 0.3 75 40 80 100 100 100 100 60 80 60

7 0.3 80 40 65 100 100 100 100 50 100 60

8 0.3 90 70 80 100 100 100 100 70 100 80

9 0.3 85 40 80 100 100 100 100 70 100 70

10 0.3 90 100 90 100 100 100 100 100 100 95

11 0.3 95 35 70 100 100 100 100 60 70 65

12 0.3 80 30 70 100 100 100 100 50 70 60

13 0.3 80 35 80 100 100 100 100 70 70 75

14 0.3 90 40 70 100 100 100 100 80 80 90

15 0.3 80 25 60 100 100 100 100 40 60 30

16 0.3 70 40 70 100 100 100 100 70 70 5

17 0.3 70 35 75 100 100 100 100 65 70 80

18 0.3 70 40 50 100 100 30 50 30 60 50

19 0.3 80 80 80 100 100 100 100 90 100 90 1 0.3 90 40 70 100 100 70 100 60 100 60 9 0.3 70 50 60 100 100 95 100 50 90 60 7 0.3 90 40 70 100 100 100 ND 80 90 70 8 0.3 95 50 70 100 100 100 ND 80 70 50 9 0.3 95 80 90 100 100 100 100 80 100 100 0 0.3 80 40 70 100 100 100 ND 75 80 45 1 0.3 70 80 75 100 100 100 100 ND 100 90 2 0.3 70 50 70 100 100 100 100 ND 60 40 4 0.3 90 30 70 100 100 100 ND ND 60 50 5 0.3 90 60 80 100 100 100 100 ND 100 70 6 0.3 90 35 60 100 100 100 95 ND 40 20 7 0.3 70 40 70 100 100 95 100 ND 40 50 8 0.3 95 60 80 100 100 100 95 ND 80 70 Table 4 (continued) Cmpd

No. Rate Soy Wht Cm Abuth Iposs Sterne Xanpe Alomy Setvi Sorha

49 0.3 90 30 80 100 100 ND ND 60 100 40

50 0.3 95 25 75 100 100 ND 100 ND 100 40

51 0.3 80 60 80 100 100 100 100 75 80 95

52 0.3 80 40 80 100 100 90 100 40 60 70

53 0.3 65 20 60 100 100 90 100 40 90 70

58 0.3 90 60 60 100 100 100 100 100 95 80

62 0.3 100 70 90 100 100 100 100 95 100 100

63 0.3 70 50 60 100 100 100 95 50 50 60

64 0.3 75 50 70 100 100 100 100 50 50 60

65 0.3 75 50 70 100 100 100 100 ND 90 70

66 0.3 70 40 50 100 100 100 100 ND 75 50

67 0.3 60 50 80 80 100 20 95 10 20 40

68 0.3 80 40 80 100 100 100 100 ND 75 70

69 0.3 80 50 80 100 100 100 100 ND 60 60

70 0.3 70 20 70 100 100 100 100 60 80 50

71 0.3 80 40 80 100 100 100 100 ND 80 70

72 0.3 75 40 80 100 100 ND 100 70 100 80

73 0.3 70 40 70 100 100 100 100 20 ND 40

74 0.3 70 40 70 100 100 100 100 40 ND 60

75 0.3 70 30 80 100 100 100 100 50 ND 60

76 0.3 70 30 80 100 100 100 100 70 100 90

77 0.3 60 40 90 100 100 50 80 50 100 60

78 0.3 90 40 70 100 100 80 80 60 100 80

79 0.3 80 50 90 100 100 100 100 70 75 90

80 0.3 75 40 70 100 100 100 100 40 80 70

81 0.3 75 30 70 100 100 100 100 70 90 70

82 0.3 75 40 70 100 100 100 100 ND 50 50

83 0.3 50 20 40 70 90 60 70 30 20 30

84 0.3 70 30 60 100 100 ND 90 ND 80 40

Rate is in kg/hectare. Soy is soybean; Wht, wheat; Crn, corn; Abuth, velveltleaf; Iposs, morning-glory; Steme, chickweed; Xanpe, cocklebur; Alomy, blackgrass; Setvi, green foxtail; Sorha, Johnsongrass

ND = NO DATA

Claims

Claims:

1. A compound of the formula

in which:

X and Y are independently selected from hydrogen, halogen, and alkyl;

R is alkyl or amino;

R¹ is hydrogen, alkyl, cyanoalkylsulfonyl, acyl, acyloxyacyl, alkoxycarbonyl, or represents the negative charge of the anion of a salt; R² is:

(1) alkyl, cyanoalkyl, cyanoalkoxycarbonylalkyl, alkenoxycarbonylalkyl, alkynoxycarbonylalkyl, arylalkyl, aryloxyalkyi, arylalkoxycarbonylalkyl, heterocyclyl, amino, aminocarbonylalkyl; (2) ΓÇö WΓÇö R³ in which W is alkyl, and R³ is aminocarbonyl, alkoxycarbonyl, hydroxycarbonyl, arylalkylthiocarbonyl, nitro, alkylthiocarbonyl, or heterocyclylalkoxycarbonyl;

(3) ΓÇö- CH(CΓëíN)R⁴, in which R⁴ is hydrogen, alkyl, arylalkyl, or arylhaloalkyl; or (4) ΓÇö C(CΓëíN)=CHR⁵; in which R⁵ is aryl or heterocyclyl; with the proviso that an amino group may be substituted with one or two substituents independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, acyloxyacyl, aryl, arylalkyl, aryloxyalkyi, and heterocyclylalkyi; halogen is chlorine, bromine, or fluorine; the alkyl and acyl moieties may each contain 1-6 carbon atoms, the alkenyl and alkynyl moieties may each contain 2-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in any R¹, R², R³, or R⁴ does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with halogen; and heterocyclyl is selected from 2,3- dihydro-2,2-dimethylbenzofuran-7-yl and 1 ,3-dioxolan-2-yl;. with the further proviso that when R² is amino, alkylamino, dialkylamino, arylamino, or arylalkylamino, and R is alkyl, R¹ is not hydrogen, alkyl, alkylcarbonyl, or alkoxycarbonyl; and when R² is arylalkyl, or alkoxycarbonylalkyl, and R is alkyl, R¹ cannot be hydrogen, alkyl, alkylcarbonyl, or alkoxycarbonyl, but may be alkyl only when is cyanoalkylsulfonyl or acyloxyacyl; or the sodium, potassium or 1-8 carbon amine salts thereof.

2. A compound of claim 1 in which: R is alkyl or amino;

R¹ is hydrogen, alkyl, acyl, acyloxyacyl, or represents the negative charge of the anion of a salt; R² is

(1) cyanoalkyl, aryloxyalkyi, amino, or aminocarbonylalkyl, in which an amino group may be substituted with one or two substituents independently selected from alkyl, cyanoalkyl, or alkoxy; with the proviso that when R² is amino, alkylamino, or dialkylamino, and R is alkyl, R¹ is not hydrogen or alkyl; or

(2) ΓÇö CH(CΓëíN)R⁴, in which R⁴ is hydrogen or alkyl; with the proviso that the alkyl, alkoxy, and acyl moieties may each contain 1- 4 carbon atoms; each may be straight or branched; the total number of carbon atoms in any R¹, R², or R⁴ is does not exceed 8; and aryl is selected from phenyl or furanyl.

3. A compound of claim 2 in which X is chlorine or bromine;

Y is hydrogen or fluorine; R is methyl or amino; R¹ is hydrogen, acetyl, or acetoxyacetyl;

R² is

(1) 1-cyanoethyl, 2-cyanopropyl, phenoxyethyl, dimethylamino, (2-cyanoethyl)(methyl)amino, or aminocarboxymethyl, in which an amino group may be substituted with one or two substituents independently selected from methyl, methoxy, phenyl, or benzyl; with the proviso that when R² is dimethylamino, and R is methyl, R¹ is not hydrogen; or

(2) ΓÇö CH(CΓëíN)R⁴, in which R⁴ is hydrogen or alkyl.

4. A compound of claim 3 in which R is methyl, and R¹ is hydrogen.

5. The compound of claim 4 in which X is chloro, Y is fluoro, and R² is (2-cyanoethyl)(methyl)amino.

6. The compound of claim 4 in which X is chloro, Y is fluoro, and R² is 2-phenoxyethyl.

7. The compound of claim 4 in which X is chloro, Y is fluoro, and R² is 2-cyanopropyl.

8. The compound of claim 4 in which X is chloro, Y is fluoro, and R² is (methoxy)(methyl)aminocarbonylmethyl.

9. The compound of claim 4 in which X is chloro, Y is fluoro, and R⁴ is methyl.

10. The compound of claim 4 in which X is bromo, Y is fluoro, and R⁴ is methyl.

11. A compound of claim 3 in which R is methyl, and R¹ is acetoxyacetyl.

12. The compound of claim 11 in which X is chloro, Y is fluoro, and R² is dimethylamino.

13. The compound of claim 11 in which X is chloro, Y is fluoro, and R² is (2-cyanoethyl)(methyl)amino.

14. A compound of claim 3 in which R is amino, and R¹ is hydrogen.

15. The compound of claim 14 in which X is chloro, Y is hydrogen, and R² is 1-cyanoethyl.

16. The compound of claim 14 in which X is chloro, Y is fluoro, and R² is 1-cyanoethyl.

17. The compound of claim 14 in which X is chloro, Y is fluoro, and R² is dimethylamino.

18. A compound of claim 3 in which R is methyl, and R¹ is acetyl.

19. The compound of claim 18 in which X is chloro, Y is fluoro, R² is ΓÇö CH(CΓëíN)R⁴, and R⁴ is methyl.

20. A herbicidal composition comprising an herbicidally effective amount of a compound of claim 1 in admixture with at least one agriculturally acceptable carrier.

21. The method of controlling undesired plant growth which comprises applying to the locus where control is desired a herbicidally effective amount of a composition of claim 20.

22. A compound of the formula

Q O

I II _R3-C-S-CI H II O in which :

23. A compound of the formula

in which:

X and Y are independently selected from hydrogen, halogen, and alkyl; Z is nitro, amino, or isocyanato;

R² is arylalkyl, aryloxyalkyi, cyanoalkyl, substituted or disubstituted aminocarbonylalkyl, arylalkoxycarbonylalkyl, (arylalkylthio)carbonylalkyl, or mono- or disubstituted amino; with the proviso that the amino substituents are independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, acyloxyacyl, aryl, arylalkyl, and aryloxyalkyi; the alkyl, alkoxy, and acyl moieties may each contain 1-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in R²does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with chlorine, bromine, or fluorine.

24. A compound of the formula

in which:

X and Y are independently selected from hydrogen, halogen and alkyl; R² is arylalkyl, aryloxyalkyi, cyanoalkyl, substituted or disubstituted aminocarbonylalkyl, arylalkoxycarbonylalkyl, (arylalkylthio)carbonylalkyl, or disubstituted amino; with the proviso that the amino substituents are independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, acyloxyacyl, aryl, arylalkyl, and aryloxyalkyi; the alkyl, alkoxy, and acyl moieties may each contain 1-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in R² is does not exceed -12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with chlorine, bromine, or fluorine.

25. A compound of the formula

in which:

X and Y are independently selected from hydrogen, halogen, or alkyl; and

R² is arylalkyl, aryloxyalkyi, cyanoalkyl, substituted or disubstituted aminocarbonylalkyl, arylalkoxycarbonylalkyl, (arylalkylthio)carbonylalkyl, or mono- or disubstituted amino, with the proviso that the amino substituents are independently selected from alkyl, cyanoalkyl, alkoxy, alkoxycarbonylalkyl, acyloxyacyl, aryl, arylalkyl, and aryloxyalkyi; the alkyl, alkoxy, and acyl moieties may each contain 1-6 carbon atoms, each may be straight or branched, and the total number of carbon atoms in R²does not exceed 12; aryl is selected from phenyl, furanyl, and thienyl, each optionally substituted with chlorine, bromine, or fluorine.