WO1991015478A1

WO1991015478A1 - Crop-selective herbicidal sulfonamides

Info

Publication number: WO1991015478A1
Application number: PCT/US1991/001075
Authority: WO
Inventors: Marcus P. Moon
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1990-04-02
Filing date: 1991-02-26
Publication date: 1991-10-17
Also published as: JP2799246B2; JPH05505796A; CA2079589A1; BR9106301A; EP0523067A1

Abstract

This invention relates to novel sulfonamides and their use as crop selective herbicides. Compounds of the instant invention have demonstrated excellent control of weeds coupled with corn safety.

Description

TITLE

CROP-SELECTIVE HERBICIDAL SULFONAMIDES

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of application Serial No. 07/503,182, filed April 4 , 1990.

BACKGROUND OF THE INVENTION

This invention relates to novel sulfonamides and their use as crop selective herbicides.

Compounds of the instant invention have demonstrated excellent control of weeds coupled with corn safety.

EP-A-120,814 discloses herbicidal sulfonylureas of the formula

wherein :

A is C₁-C₆ haloalkyl;

R¹ is H, halogen, NO₂, CN, C₁-C₄ alkyl,

C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, COR⁶, NR⁷R⁸, CONR⁹R¹⁰ or

SO₂NR¹¹R¹²; and

R⁶ is C₁-C₄ alkoxy, C₁-C₄ haloalkoxy,

C₁-C₄ alkylthio, C₂-C₆ alkoxyalkoxy, hydrogen, C₁-C₄ alkyl or C₁-C₄ haloalkyl. Although this reference broadly embraces compounds of the instant invention, it does not teach or suggest these particular compounds or their herbicidal utility. Additionally, a need still exists for

herbicides because of world-wide food shortages. In addition, herbicides which are selective to important crops such as corn are particularly necessary.

According to the instant invention, such compounds have been found.

SUMMARY OF THE INVENTION

More specifically, this invention comprises novel compounds of Formula I, agriculturally suitable compositions containing them, and their method-of-use as preemergence and/or postemergence herbicides or plant growth regulants:

wherein:

A is OR¹ or N(CH₃)₂;

R¹ is C₁-C₃ alkyl, CH₂CH=CH₂, CH₂CΞCH, CH₂CH₂Cl or CH₂CH₂OCH₃;

R² is CH₂F, CHF₂, CHFCH₃ or CH₂CN;

X is CH₃ or OCH₃; and

Y is H, Cl, CH₃, C₂H₅, OCH₃ or OCF₂H;

and their agriculturally suitable salts; provided that when Y is Cl, then X is OCH₃.

In the above definitions, the term "alkyl" denotes straight chain or branched alkyl, e.g. methyl, ethyl, n-propyl or isopropyl. The total number of carbon atoms in a substituent group is indicated by the C_i-C_j prefix where i and j are numbers 1 to 3. For example, C₁-C₃ alkyl would designate methyl through propyl (both n-propyl and isopropyl).

Preferred for reasons of increased ease of synthesis and/or greater herbicidal efficacy and/or crop safety are:

1. Compounds of Formula I wherein

A is OR¹; and

R¹ is CH₃, CH₂CH₃ or CH(CH₃)₂.

2. Compounds of Preferred 1 where

when one of X and Y is CH₃, then the other of X and Y is other than OCH₃.

Specifically preferred for reason of greatest safety to corn (maize) is:

• Methyl 3-(cyanomethyl)-2-[[[[(4,6- dimethyl-2-pyrimidinyl)amino]carbonyl]- amino]sulfonyl]benzoate (Formula I: A is OR¹, R¹ is CH₃, R² is CH₂CN, X and Y are CH₃.

Specifically Preferred for reason of greatest safety to corn, wheat and barley are:

• Methyl 2-[[[[(4-chloro-6-methoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-3- (cyanomethyl)benzoate (Formula I: A is OR¹, R¹ is CH₃, R² is CH₂CN, X is OCH₃ , Y is Cl);

• Methyl 3-(cyanomethyl)-2-[[[[[(4-

(difluoromethoxy)-6-methoxy-2-pyrimidinyl]- amino]carbonyl]amino]sulfonyl]benzoate

(Formula I: A is OR¹, R¹ is CH₃, R² is

CH₂CN, X is OCH₃, Y is OCF₂H);

• Methyl 3-(difluoromethyl)-2-[[[[(4-methoxy- 2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]- benzoate (Formula I: A is OR¹, R¹ is CH₃, R² is CHF₂ X is OCH₃, Y is H);

• Methyl 3-(fluoromethyl)-2-[[[[(4-methoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]- benzoate (Formula I: A is OR¹, R¹ is CH₃, R² is CH₂F, X is OCH₃, Y is H).

Specifically preferred for reason of greatest safety to wheat and barley is:

• Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)- amino]carbonyl]amino]sulfonyl]-3-

(fluoromethyl)benzoate (Formula I: A is OR¹, R¹ is CH₃, R² is CH₂F, X and Y are

OCH₃).

Specifically preferred for reason of greatest safety to corn, wheat, barley and rice is:

• Ethyl 2-[[[[(4-chloro-6-methoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-3- (fluoromethyl)benzoate (Formula I:

A is OR¹, R¹ is CH₂CH₃, R² is CH₂F, X is OCH₃, Y is Cl).

This invention also comprises novel compounds, such as the sulfonyl benzoates of Formula II, useful as intermediates for preparation of the compounds of Formula I:

wherein:

A is OR¹ or N(CH₃)₂;

R² is CH₂F, CHF₂, CHFCH₃ or CH₂CN; and

Z¹ is Cl or NHSiR³R⁴R⁵;

R³ is C₁-C₄ alkyl;

R⁴ is C₁-C₄ alkyl; and

R⁵ is C₁-C₄ alkyl.

Preferred for reason of increased herbicidal activity of final products of Formula I, are

intermediates of Formula II wherein A is OR¹ and R¹ is C₁-C₂ alkyl.

Preferred for reason of increased ease of synthesis are intermediates of the above preferred wherein R³ and R⁴ are CH₃ and R⁵ is C(CH₃)₃.

DETAILED DESCRIPTION OF THE INVENTION

SYNTHESIS

The compounds of Formula (1), which corresponds to Formula I, can be prepared by one or more of the methods described below. The proper choice of reaction sequences for a given compound will be known to one skilled in the art. As shown in Equation 1, many of the compounds of Formula (1) are prepared by reacting a silyl sulfonamide of Formula (2) with a pyrimidine

carbamate of Formula (3). R³, R⁴, and R⁵ are

independently C₁ to C₄ alkyl.

Equation 1

The reaction is carried out at 0°C to 50°C in a solvent such as acetonitrile, dioxane, or

tetrahydrofuran; in the presence of a fluoride ion source such as cesium fluoride, or tetrabutylammonium fluoride for 0.1 to 2 hours. A catalytic amount of base, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), increases the reaction rate.

Alternatively, some of the sulfonamides of Formula (4) can be prepared and reacted with

pyrimidine carbamates of Formula (3) to give

compounds of Formula (1) as shown in Equation 2. The reaction is carried out at 0°C to 50°C in a solvent, such as acetonitrile, dioxane, or tetrahydrofuran, in the presence of a non-nucleophilic base, such as DBU for 0.2 to 2 hours. U.S. Patent 4,604,131 discloses details for similar reactions and is herein

incorporated by reference. Equation 2

Sulfonyl chlorides of Formula (5) may be reacted with cyanate anion in the presence of

pyrimidine amines of Formula (6) to give compounds of Formula (1) as shown in Equation 3.

Equation 3

The reaction is carried out by mixing one equivalent of sulfonyl chloride (5), pyrimidine amine (6), a metal cyanate, such as potassium cyanate, and a catalytic amount of an amine base, such as Aliquat^® 336 (Tricaprylymethylammonium chloride), in a solvent such as acetonitrile for 0.2 to 10 days. Alternatively, one can use a tetraalkylammonium cyanate, such as tetraethylammonium cyanate, to effect this reaction by the method described in U.S. Patent 4,604,131 herein incorporated by reference.

Silyl sulfonamides of Formula (2) are prepared by reacting sulfonyl chlorides of Formula (5) with a trialkylsilyl amine of Formula (7), such as

t-butyldimethylsilyl amine, as shown in Equation 4. Equation 4

The reaction is carried out at 0°C to 30°C in a solvent, such as dichloromethane, in the presence of

1 to 2 equivalents of the amine and 1 equivalent of a bicarbonate. J. R. Bowser et. al. describe methods to prepare silyl amines of Formula (7) in Inorganic

Chemistry 17, 1882 (1978).

The sulfonyl chlorides of Formula (5) and the silyl sulfonamides of Formula (2) correspond to the intermediates of Formula II.

Sulfonyl chlorides of Formula (5) can be reacted with no more than 2 equivalents of ammonia or, alternatively, 1 equivalent of ammonia and 1 equivalent of a base to give sulfonamides of Formula

(4) as outlined in Equation 5. Equation 5

Sulfonamides of Formula (4) tend to be unstable and can be difficult to isolate.

Sulfonyl chlorides of Formula (5) are prepared by the methods shown in Equations 6 and 7.

Sulfur-containing compounds of Formula (8) are oxidized with chlorine as shown in Equation 6. R⁶ is

H, alkyl, benzyl or carbamoyl.

Equation 6

The reaction of Equation 6 is carried out by contacting compounds of Formula (8) in a solvent, such as acetic acid or propionic acid, with at least 3.0 equivalents of chlorine in the presence of at least 2.5 equivalents of water for 0.2 to 5 hours at -20°C to 30°C. A. Wagenaar teaches specific reaction conditions for related compounds in Reel. Trav. Chim.

Pays-Bas 101, 91 (1982).

Alternatively, reaction of compounds of Formula

(8), where R⁶ is H or benzyl, with a hypochlorite solution, such as 5% NaOCl, can provide sulfonyl chlorides of Formula (5). Reaction conditions for similar reactions are obvious to one skilled in the art and are described in EP-A-142,152.

As shown in Equation 7 , below, sulfonyl

chlorides of Formula (5) may be prepared from the corresponding anilines of Formula (9) by a Meerwein reaction.

Equation 7

The aniline is diazotized and then reacted with sulfur dioxide and cupric chloride analogous to the teachings of Yale and Sowinski, J. Org. Chem. 25 , 1824 (1960). Alternatively, the hydrochloride salts of anilines of Formula (9) can be diazotized in an organic solvent with an alkyl nitrite and reacted with sulfur dioxide to give sulfonyl chlorides (5) analogous to the teachings of M. Doyle, J. Org. Chem. 42, 2426,2431 (1977). The pyrimidine carbamates of Formula (3) and the pyrimidine amines of Formula (6) are prepared by the methods described and referenced in EP-A-72,347, EP-A-164,269, EP-A-173,498, U.S. Patent 4,540,782, and U.S. Patent 4,666,506, herein incorporated by reference.

Agriculturally suitable salts of compounds of Formula I are also useful herbicides and can be prepared in a number of ways known to the art. For example, metal salts can be made by contacting

compounds of Formula I with a solution of an alkali or alkaline earth metal salt having a sufficiently basic anion (e.g., hydroxide, alkoxide, carbonate or hydroxide). Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of one cation for another.

Cationic exchange can be effected by direct contact of an aqueous solution of a salt of a compound of Formula I (e.g., alkali or quaternary amine salt) with a solution containing the cation to be

exchanged. This method is most effective when the desired salt containing the exchanged cation is insoluble in water and can be separated by filtration,

Exchange may also be effected by passing an aqueous solution of a salt of a compound of Formula I (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to be exchanged for that of the original salt and the desired product is eluted from the column. This method is particularly useful when the desired salt is water-soluble, e.g., a potassium, sodium or calcium salt.

Acid addition salts, useful in this invention, can be obtained by reacting a compound of Formula I with a suitable acid, e.g., p-toluenesulfonic acid, trichloroacetic acid or the like.

The preparation of the compounds of this invention is further illustrated by the following specific examples. Temperatures are reported in degrees Celsius; abbreviations for nuclear magnetic resonance (NMR) are: s = singlet, d = doublet, t = triplet, m = multiplet, and peak positions are reported as parts per million downfield from internal tetramethylsilane. Infrared (IR) peak positions are given in reciprocal centimeters (cm^-1) and sh denotes a shoulder.

EXAMPLE 1

Methyl 3-(Cyanomethyl)-2-nitrobenzoate To a stirred solution of potassium cyanide (6.2 g) in methanol (100 mL) and water (150 mL) at 0°C was added an acetonitrile solution of methyl

3-(bromomethyl)-2-nitrobenzoate (24.9 g). A

catalytic amount of 18-crown-6 ether was then added. After stirring overnight at room temperature, the reaction was extracted with ethyl acetate. The combined extracts were washed with a brine solution, dried over magnesium sulfate, filtered, concentrated, and chromatographed on silica gel eluting with 20% ethyl acetate in hexanes to give 8.5 g of the title compound as a white solid.

90 MHz NMR (CDCl₃) δ: 3.83 (s, 2H, CH₂);

3.93 (s, 3H, CH₃); and

7.9 (m, 3H, arom.)

EXAMPLE 2

2-(Methoxycarbonyl)-6-(cyanomethyl)- benzenesulfonyl Chloride

To a stirred suspension of dry tetrahydrofuran (150 mL) and 26% potassium hydride in oil (6.66 g) was slowly added benzyl mercaptan (4.82 mL) at 0°C under a nitrogen atmosphere. After 15 minutes, methyl 3-(cyanomethyl)-2-nitrobenzoate (8.5 g) was added and the resulting mixture was stirred at room temperature overnight. The reaction was contacted with 6N sodium hydroxide (25 mL) and extracted with ethyl acetate . The extracts were washed with a brine solution, dried over magnesium sulfate, filtered, and concentrated to give 9.0 g of crude methyl 3-(cyanomethyl)-2- (phenylmethylthio)benzoate as a purple oil.

The crude thioether was stirred in a mixture of dichloromethane (200 mL) and 6N hydrochloric acid (25 mL) at 0°C, as 5% sodium hypochlorite (180 mL) was slowly added. The reaction mixture was then stirred at 0°C for 2 hours. The dichloromethane layer was washed with water, dried over magnesium sulfate, filtered, concentrated, and chromatographed on silica gel eluting with 25% ethyl acetate in hexanes to give 1.7 g of the title compound as a yellow solid.

90 MHz NMR (CDCl₃) δ: 3.98 (s, 3H, CH₃);

4.41 (s, 2H, CH₂); and

7.83 (m, 3H, arom.).

EXAMPLE 3

Methyl 3-(Cyanomethyl)-2-[[[(1,1-dimethylethyl)- dimethylsilyllamino]sulfonyl]benzoate

A suspension of 2-(methoxycarbonyl)-6- (cyanomethyl)benzenesulfonyl chloride (10.7 g), amino-t-butyldimethylsilane (10.3 g), and sodium bicarbonate (3.36 g) in dichloromethane (200 mL) was stirred at room temperature in a stoppered flask for 4 days. The organic phase was washed with with water, dried over magnesium sulfate, filtered, concentrated, and chromatographed on silica gel eluting with 30% ethyl acetate in hexanes to give 5.0 g of the title compound as a yellow solid, m.p.

113-115°C.

90 MHz NMR (CDCl₃) δ: 0.32 (s, 6H, SiCH₃);

0.95 (s, 9H, C(CH₃)₃); 3.99 (s, 3H, OCH₃);

4.42 (s, 2H, CH₂CN);

5.91 (s, 1H, NH);

7.6 (m, 2H, arom.); and 7.8 (m, 1H, arom.).

IR (mineral oil) 3290, 2250, and 1710 cm^-1.

EXAMPLE 4

Methyl 3-(Cyanomethyl)-2-[[[[(4,6-dimethyl-

2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate A mixture of methyl 3-(cyanomethyl)- 2- [[[(1,1-dimethylethyl)dimethylsilyl]amino]- sulfonyl]benzoate (0.34 g), O-phenyl-N-(4,6-dimethyl- 2-pyrimidinyl)carbamate (0.24 g), and acetonitrile (2.5 mL) were stirred and cooled in an ice-acetone bath. A stock solution of 1 M tetrabutylammonium fluoride containing 8 mole % 1,8-diazabicyclo- [5.4.0]undec-7-ene (1.0 mL) was added and the

reaction was stirred under a nitrogen atmosphere for 45 minutes. The reaction was added to water (30 mL) and acidified to pH 5 with 1N hydrochloric acid. The resulting precipitate was filtered, washed with water and hexanes, and air dried to give 0.23 g of the title compound as a yellow solid, m.p. 182-185°C. 200 MHz NMR (DMSO) δ: 2.40 (s, 6H, CH₃);

3.79 (s, 3H, OCH₃);

4.67 (s, 2H, CH₂CN);

7.04 (s, 1H, pyrim. H);

7.64 (m, 1H, arom.);

7.82 (m, 2H, arom.);

10.8 (s, 1H, NH); and

13.7 (s, 1H, NH).

IR (mineral oil) 2240, 1740 cm^-1.

EXAMPLE 5

Methyl 3-Formyl-2-nitrobenzoate Methyl 3-(dibromomethyl)-2-nitrobenzoate (62.6 g), silver nitrate (109 g), 1,2-dimethoxyethane (500 mL), and water (400 mL) were heated at reflux

overnight. The undissolved salts were filtered off and the filtrate was extracted with ethyl acetate.

The extracts were washed with a brine solution, dried over magnesium sulfate, filtered, and concentrated to give a crude solid. Recrystallization from

chlorobutane gave 20.9 g of the title compound as an orange solid.

90 MHz NMR (CDCl₃) δ: 3.98 (S, 3H, OCH₃);

7.8 (m, 1H, arom.);

8.3 (m, 2H, arom.); and

10.0 (s, 1H, HCO).

EXAMPLE 6

Methyl 3-(Difluoromethyl)-2-nitrobenzoate To a solution of diethylaminosulfur trifluoride (11 mL) in dichloromethane (75 mL) stirred at -70°C under a nitrogen atmosphere, was added a

dichloromethane solution of methyl 3-formyl-2- nitrobenzoate (5.9 g). The reaction was allowed to warm to room temperature. After 3 hours it was poured onto ice (300 mL) and extracted with

dichloromethane. The extracts were washed with water, dried over magnesium sulfate, filtered, and concentrated to give a crude solid. Recrystallization from hexanes-chlorobutane gave 3.94 g of the title compound as a peach-colored solid, m.p. 66-69°C. 90 MHz NMR (CDCl₃) δ: 3.94 (s, 3H, OCH₃);

6.87 (t, 1H, CHF₂); and

7.9 (m, 3H, arom.).

EXAMPLE 7

2-(Methoxycarbonyl)-6-(difluoromethyl)- benzenesulfonyl Chloride

To a stirred suspension of dry tetrahydrofuran (250 mL) and 26% potassium hydride in oil (6.17 g) was slowly added benzyl mercaptan (4.63 mL) at 0°C under a nitrogen atmosphere. After 15 minutes. methyl 3-(difluoromethyl)-2-nitrobenzoate (7.5 g) was added, and the resulting mixture was stirred at room temperature overnight. The reaction was contacted with aqueous sodium bicarbonate (50 mL) and extracted with ethyl acetate. The extracts were dried over magnesium sulfate, filtered, and concentrated to give 10.8 g of crude methyl 3-(difluoromethyl)- 2-(phenylmethylthio)benzoate as a brown oil.

The crude thioether was stirred in a mixture of dichloromethane (400 mL) and 6N hydrochloric acid (28 mL) at 0°C, as 5% sodium hypochlorite (204 mL) was slowly added. The reaction mixture was stirred at 0°C for 2.5 hours. The dichloromethane layer was washed with water, dried over magnesium sulfate, filtered, concentrated, and triturated with hexanes to give 5.17 g of the title compound as a yellow solid.

90 MHz NMR (CDCl₃) δ: 4.13 (s, 3H, OCH₃); and

7.1 - 8.3 (m, 4H, CHF₂ and

arom.).

EXAMPLE 8

Methyl 3-(Difluoromethyl)-2-[[[(1,1-dimethyl- ethyl)dimethylsilyl]amino]sulfonyl]benzoate

A suspension of 2-(methoxycarbonyl)-6-(difluoromethyl)benzenesulfonyl chloride (5.17 g),

amino-t-butyldimethylsilane (4.9 g), and sodium bicarbonate (1.5 g) in dichloromethane (150 mL) was stirred at room temperature in a stoppered flask for 4 days. The organic phase was washed with water, dried over magnesium sulfate, filtered, concentrated, and chromatographed on silica gel eluting with 10 % ethyl acetate in hexanes to give 2.23 g of the title compound as a white solid.

90 MHz NMR (CDCl₃) δ: 0.2 (s, 6H, SiCH₃);

0.87 (s, 9H, C(CH₃)₃);

3.90 (s, 3H, OCH₃); 5.88 (s, 1H, NH); and

7.20 - 8.36 (m, 4H, CHF₂ and arom.).

EXAMPLE 9

Methyl 3-(Difluoromethyl)-2-[[[[(4-methoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate A mixture of methyl 3-(difluoromethyl)-2- [[[(1,1-dimethylethyl)dimethylsilyl]amino]sulfonyl]- benzoate (0.22 g), O-phenyl-N-(4-methoxy- 2-pyrimidinyl)carbamate (0.15 g), and acetonitrile (2.0 mL) were stirred and cooled in an ice-acetone bath. A stock solution of 1 M tetrabutylammonium fluoride containing 8 mol % 1,8-diazabicyclo-

[5.4.0]undec-7-ene (0.61 mL) was added, and the reaction was stirred under a nitrogen atmosphere for 1 hour. The reaction was added to water (30 mL) and acidified to pH 5 with 1N hydrochloric acid. The resulting precipitate was filtered, washed with water and hexanes, and air dried to give 0.06 g of the title compound as a white solid, m.p. 178-180°C

(decomposition).

200 MHz NMR (DMSO) δ: 3.94 (s, 3H, OCH₃);

4.14 (s, 3H, OCH₃);

6.87 (d, 1H, pyrim. H);

7.8 - 8.2 (m, 3H, arom.);

8.43 (d, 1H, pyrim. H);

11.46 (s, 1H, NH); and

13.90 (s, 1H, NH).

IR (mineral oil) 1730, 1720 cm^-1.

EXAMPLE 10

Methyl 3-(1-Hydroxyethyl)-2-nitrobenzoate

Titanium tetrachloride (6.25 mL) was added to dry diethylether ( 250 mL) at -78°C and was sti rred under a nitrogen atmosphere. The resulting yellow suspension was allowed to warm to -50°C and was recooled to -78°C prior to adding 1.4 oolar methyllithium in diethylether (41.6 mL). The mixture was warmed to -30°C and the resulting purple mixture was cooled to -60°C and transferred by cannula into an adj acent f lask containing methyl 3-formyl- 2-nitrobenzoate (11.6 g) and dry tetrahydrofuran (250 mL). The resulting mixture was allowed to warm to room temperature and was stirred under a nitrogen atmosphere for about 18 hours. The reaction was poured onto a mixture of ice (100 mL) and 3N

hydrochloric acid (100 mL) and extracted with ethyl acetate. The extracts were washed with saturated sodium bicarbonate and brine, dried over magnesium sulfate, filtered, and concentrated to a crude oil. Flash column chromatography on silica gel, eluting with dichloromethane gave 9.8 g of the title compound as a yellow oil, n_D 1.5309.

90 MHz NMR (CDCl₃) δ: 1.47 (d, 3H, CH₃);

2.58 (s, 1H, OH);

3.92 (s, 3H, OCH₃);

4.93 (m, 1H, CH); and

7.8 (m, 3H, arom.).

IR (neat) 3431, 1735 cm^-1.

EXAMPLE 11

Methyl 3-(1-Fluoroethyl)-2-nitrobenzoate To a solution of diethylamino sulfur

trifluoride (18 mL), in dichloromethane (100 mL), stirred at -74°C under a nitrogen atmosphere was added a dichloromethane solution of methyl 3-(1- hydroxyethyl)-2-nitrobenzoate (14.6 g). The reaction was allowed to warm to room temperature and was briefly warmed to 35°C. After a 4 hour reaction period, the reaction was poured onto ice and water (200 mL) and extracted with dichloromethane. The combined extracts were washed with a 1:1 mixture of IN NaOH and saturated sodium bicarbonate, dried over magnesium sulfate, filtered, and concentrated to give 11.3 g of the title compound as a dark amber oil, n_D 1.5151.

90 MHz NMR (CDCI₃) δ: 1.67 (d of d, 3H, CH₃);

3.93 (s, 3H, OCH₃);

5.7 (d of q, 1H, CHF); and 7.9 (m, 3H, arom.).

IR (neat) 1736 cm^-1.

EXAMPLE 12

Methyl 3-(1-Fluoroethyl)-2- (phenylmethylthio)benzoate

Following the procedure described in Example 2, methyl 3-(1-fluoroethyl)-2-nitrobenzoate (15 g) was reacted to give 17.55 g of the unpurified title compound as a brown oil.

EXAMPLE 13

2-(Methoxycarbonyl)-6-(1-fluoroethyl)- benzene sulfonyl Chloride

Following the procedure described in Example 2, methyl 3-(1-fluoroethyl)-2-(phenyImethylthio)benzoate (8.8 g) was reacted and chromatographed on silica eluting with 10% ethyl acetate in hexanes to give 1.7 g of the title compound as an orange oil.

90 MHZ NMR (CDCl₃) δ: 1.8 (d of d, 3H, CH₃);

4.0 (s, 3H, OCH₃);

6.6 (d of q, 1H, CHF); and 7.8 (m, 3H, arom.).

EXAMPLE 14

Methyl 3-(1-Fluoroethyl)-2-[[[(1,1-dimethyl- ethyl)dimethylsilyl]amino]sulfonyl]benzoate

Following the procedure described in Example 3, 2-(methoxycarbonyl)-6-(1-fluoroethyl)benzene sulfonyl chloride (2.4 g) was reacted and chromatographed on silica eluting with 15% ethyl acetate in hexanes to give 1.3 g of the title compount as an orange oil. 90 MHZ NMR (CDCI₃) δ: 0.17 (s, 3H, SiCH₃);

0.24 (s, 3H, SiCH₃);

0.84 (s, 9H, C(CH₃)₃);

1.57 (d of d, 3H, CH₃);

3.88 (s, 3H, OCH₃);

5.83 (s, 1H, NH);

6.6 (d of q, 1H, CHF); and 7.6 (m, 3H, arom.).

EXAMPLE 15

Methyl 3-(1-Fluoroethyl)-2-[[[[(4,6-dimethoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate Following the procedure described in Example 4, methyl 3-(1-fluoroethyl)-2-[[[(1,1-dimethylethyl)- dimethylsilyl]amino]sulfonyl]benzoate (0.26 g) and O-phenyl-N-(4,6-dimethoxy-2-pyrimidinyl)carbamate (0.2 g) were reacted to give 0.16 g of the title compound as a pink solid, m.p. 155-158°C

(decomposition).

200 MHz NMR (DMSO) δ: 1.64 (d of d, 3H, CH₃);

3.85 (s, 3H, CO₂CH₃);

3.98 (s, 6H, OCH₃);

6.08 (s, 1H, pyrim. H);

7.04 (d of q, 1H, CHF);

7.72 (m, 1H, arom.);

7.96 (m, 2H, arom.);

10.85 (s, 1H, NH); and

12.75 (s, 1H, NH).

IR (mineral oil) 3281, 1738, 1722 cm^-1.

By applying the procedures of Equations 1 through 7 and Examples 1 through 15, the compounds in Tables 1 through 4 can be readily prepared by one skilled in the art.

Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable

concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of

(a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

Weight Percent*

Active

Ingredient Diluent(s) Surfactant(s)

Wettable Powders 20-90 0-74 1-10 Oil Suspensions, 3-50 40-95 0-15

Emulsions, Solutions,

(including Emulsifiable

Concentrates)

Aqueous Suspension 10-50 40-84 1-20 Dusts 1-25 70-99 0-5

Granules and Pellets 0. 1-95 5-99 .9 0-15

High Strength 90-99 0-10 0-2

Compositions * Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent. Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New

Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Ed.,

Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and

Emulsifiers Annual", MC Publishing Corp., Kidgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent

3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering,

December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1963, pp. 8-57ff.

For further information regarding the art of formulation, see for example:

H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Patent 3,309,192,

March 14, 1967, 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;

H. Gysin and E. Knusli, U.S. Patent

2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwise indicated .

Example A

High Strength Concentrate

Methyl 3-(cyanomethyl)-2-[[[[(4,6-dimethyl- 2-pyrimidinyl)amino]carbonyl]amino]- sulfonyl]benzoate 99% trimethylnonyl polyethylene glycol ether 1%

The surfactant is sprayed upon the active ingredient in a blender and the mixture sifted through a U. S. S. No. 40 sieve (0.42 mm openings) prior to packaging. The concentrate may be formulated further for practical use. Example B

Wettable Powder

Methyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)- amino]carbonyl]amino]sulfonyl]-3-(cyanomethyl)- benzoate 65% dodecylphenol polyethylene glycol ether 2% sodium ligninsulfonate 4% sodium silicoaluminate 6% montmorillonite (calcined) 23%

The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid ingredients in the blender. After grinding in a hammer mill to produce particles essentially all below 100 microns, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

Example C

Aqueous Suspension

Methyl 3-(cyanomethyl)-2-[[[[(4-(difluoro- methoxy)-6-methoxy-2-pyrimidinyl]amino]- carbonyl]amino]sulfonyl]benzoate 50.0% polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7%

The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.

Example D

Oil Suspension

Methyl 3-(difluoromethyl)-2-[[[[(4-methoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]- benzoate 35% blend of polyalcohol carboxylic esters

and oil soluble petroleum sulfonates 6% xylene 59%

The ingredients are combined and ground together in a sand mill to produce particles essentially all below 3 microns. The product can be used directly, extended with oils, or emulsified in water.

Example E

Oil Suspension

Methyl 3-(fluoromethyl)-2-[[[[(4-methoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]- benzoate 25% polyoxyethylene sorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70%

The ingredients are ground together in a sand mi l l unti l the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

Example F

Aqueous Suspension

Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]- carbonyl]amino]sulfonyl]-3-(fluoromethyl)- benzoate 25% hydrated attapulgite 3% crude calcium ligninsulfonate 10% sodium dihydrogen phosphate 0.5% water 61.5%

The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 microns.

Example G

Wettable Powder

Ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)- amino]carbonyl]amino]sulfonyl]-3-(fluoromethyl)- benzoate 40.0% dioctyl sodium sulfosuccinate 1.5% sodium ligninsulfonate 3% low viscosity methyl cellulose 1.5% attapulgite 54%

The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.

All compounds of the invention may be formulated in the same manner.

Example H

Granule

wettable powder of Example G 15% gypsum 69% potassium sulfate 16%

The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 cm (U.S.S. #18 to 40 sieves), the granules are removed, dried, and screened. Oversized material is crushed to produce additional material in the desired range. These granules contain % active ingredient.

Example I

Wettable Powder

Methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]- carbonyl]amino]sulfonyl]-3-(fluoromethyl)- benzoate 50% sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% diatomaceous earth 46%

The ingredients are blended, coarsely hammermilled and the air milled to produce particles of active essentially all below 10 microns in diameter. The product is reblended before packaging. Example J

Extruded Pellet

Methyl 3-(fluoromethyl)-2-[[[[(4-methoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]- benzoate 25% anhydrous sodium sulfate 10% crude calcium ligninsulfonate 5% sodium alkylnaphthalenesulfonate 1% calcium/magnesium bentonite 59%

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.

Example K

Wettable Powder

Methyl 3-(difluoromethyl)-2-[[[[(4-methoxy- 2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]- benzoate 80% sodium alkylnaphthalenesulfonate 2% sodium ligninsulfonate 2% synthetic amorphous silica 3% kaolinite 13%

The ingredients are blended and then ground in a hammermill to produce particles with an average particle size less than 25 microns in diameter. The material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before being packaged. Example L

High Strength Concentrate

Methyl 3-(cyanomethyl)-2-[[[[(4-(difluoromethoxy)- 6-methoxy-2-pyrimidinyl]amino]carbonyl]amino]- sulfonyl]benzoate 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%

The ingredients are blended and ground in a hammer mill to produce a high strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm openings). This material may then be formulated in a variety of ways.

Example M

Solution

Methyl 3-(cyanomethyl)-2-[[[[(4,6-dimethyl-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]- benzoate, sodium salt 5% water 95%

The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use. UTILITY

Test results indicate that compounds of this invention are active postemergence and preemergence herbicides. Many compounds of this invention are useful for the control of selected grass and broad- leaf weeds with tolerance to important argonomic crops such as barley (Hordeum vulgare), corn (Zea mays), rice (Orysa sativa), and wheat (Triticum aestivum).

Grass weeds controlled include, but are not limited to, barnyardgrass (Echinochloa crus-galli), black- grass (Alopecurus myosuroides), Bromus spp., foxtail

(Setaria spp.), johnsongrass (Sorghum halepense), panicum (Panicum spp.), and wild oat (Avena fatua).

Broadleaf weeds controlled include, but are not limited to, cocklebur (Xanthium pensylvanicum), jimsonweed (Datura stramonium), lambsquarters

(Chenopodium album), morningglory (Ipomoea spp.), pigweed (Amaranthus spp.), Polygonum spp., sicklepod (Cassia obtusifolia), and velvetleaf (Abutilon

theophrasti). Many compounds in this invention also control nutsedge (Cyperus spp.). Several compounds from this invention are particularly useful for weed control in cereal crops such as barley and wheat. A select few of these compounds are particularly useful for weed control in corn.

Several compounds in this invention have utility in non-crop areas where selected or complete control of plants or weeds is desired, such as around storage tanks, parking lots, billboards, highways, and

railroad structures. These compounds are also useful in fallow areas of crop production such as in wheat and barley and in plantation crops such as palm, banana, citrus, rubber, etc. Alternatively, these compounds may be useful to modify plant growth or as citrus harvest aid abscission agents.

Rates of application for compounds of this invention are determined by a number of factors.

These factors include: formulation selected, method of application, amount of vegetation present, growing conditions, etc. In general terms, the subject compounds should be applied at rates from 0.001 to 20 kg/ha with a preferred rate range of from 0.004 to 0.25 kg/ha. One skilled in the art can easily

determine rates needed for the desired level of weed control.

Compounds of this invention may be used alone or in combination with other commercial herbicides, insecticides, or fungicides. The following list exemplifies some of the herbicides suitable for use in mixtures. A combination of compounds from this invention with one or more of the following herbicides may be particularly useful for weed control.

Common Name Chemical Name

acetochlor 2-chloro-N-(ethoxymethyl)-N-

(2-ethyl-6-methylphenyl)acetamide acifluorfen 5- [2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitrobenzoic acid alachlor 2-chloro-N-(2,6-diethylphenyl)-N- (methoxymethyl)acetamide

anilofos S-4-chloro-N-isopropylcarbaniloyl- methyl-0,0-dimethyl phosphorodithioate

ametryn N-ethyl-N'-(1-methylethyl)-6-

(methylthio)-1,3,5-triazine-2,4- diamine

amitrole 1H-1,2,4-triazol-3-amine

AMS ammonium sulfamate

asulam methyl [(4-aminophenyl)sulfonyl]- carbamate

atrazine 6-chloro-N-ethyl-N'-(1-methylethyl)- 1,3,5-triazine-2,4-diamine

barban 4-chloro-2-butynyl 3-chlorocarbamate benefin N-butyl-N-ethyl-2,6-dinitro-4-(tri- fluoromethyl)benzenamine

bensulfuron 2-[[[[[(4,6-dimethoxy-2-pyrimimethyl dinyl)amino]carbonyl]- amino]sulfonyl]methyl]benzoic acid, methyl ester

bensulide 0,0-bis(1-methylethyl) S-[2- [(phenylsulfonyl)amino]- ethyl]phosphorodithioate

bentazon 3-(1-methylethyl)-(1H)-2,1,3- benzothiadiazin-4(3H)-one,

2,2-dioxide Common Name Chemical Name benzofluor N-[4-(ethylthio)-2-(trifluoromethyl)phenyljmethanesulfonamide benzoylprop N-benzoyl-N-(3,4-dichlorophenyl)-DL- alanine

bifenox methyl 5-(2,4-dichlorophenoxy)-2- nitrobenzoate

bromacil 5-bromo-6-methyl-3-(1-methylpropyl)- 2,4(1H,3H)pyrimidinedione

bromoxynil 3,5-dibromo-4-hydroxybenzonitrile butachlor N-(butoxymethyl)-2-chloro-N-(2,6- diethylphenyl)acetamide

buthidazole 3-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-4-hydroxy-1-methyl-2- imidazolidinone

butralin 4-(1,1-dimethylethyl)-N-(1-methyl- propyl)-2,6-dinitrobenzenamine butylate S-ethyl bis(2-methylpropyl)- carbamothioate

cacodylic dimethyl arsinic oxide

acid

CDAA 2-chloro-N,N-di-2-propenylacetamide

CDEC 2-chloroallyl diethyldithiocarbamate

CGA 142,464 3-(4,6-dimethoxy-1,3,5-triazin-2-yl)- 1-[2-(2-methoxyethoxy)-phenyl- sulfonyl]-urea

chloramben 3-amino-2,5-dichlorobenzoic acid chlorbromuron 3-(4-bromo-3-chlorophenyl)-1-methoxy-1- methylurea

chlofimuron 2-[[[[(4-chloro-6-methoxy-2-pyrimiethyl dinyl)amino]carbonyl]- amino]sulfonyl]benzoic

acid, ethyl ester

chlormethoxy- 2,4-dichlorophenyl 4-nitro-3- nil methoxyphenyl ether Common Name Chemical Name chlornitrofen 2,4,6-trichlorophenyl-4-nitro- phenyl ether

chloroxuron N'-[4-(4-chlorophenoxy)phenyl]-N,N- dimethylurea

chlorpropham 1-methylethyl 3-chlorophenylcarbamate chlorsulfuron 2-chloro-N-[[(4-methoxy-6-methyl-1,3,5- triazin-2-yl)amino]carbonyl]benzene- sulfonamide

chlortoluron N'-(3-chloro-4-methylphenyl)-N,N- dimethylurea

cinmethylin exo-1-methyl-4-(1-methylethyl)-2-[(2- methylphenyl)methoxy]-7-oxabicyclo- [2.2.1]heptane

clethodim (E,E)-(±)-2-[1-[[(3-chloro-2-propenyl)- oxy]imino]propyl]-5-[2-(ethylthio)- propyl]-3-hydroxy-2-cyclohexen-1-one clomazone 2-[(2-chlorophenyl)methyl]-4,4-dimethyl- 3-isoxazolidinone

cloproxydim (E,E)-2-[1-[[(3-chloro-2-propenyl)oxy)- imino]butyl]-5-[2-(ethylthio)propyl]- 3-hydroxy-2-cyclohexen-1-one

clopyralid 3,6-dichloro-2-pyridinecarboxylic acid

CMA calcium salt of MAA

cyanazine 2-[[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino]-2-methylpropanenitrile cycloate S-ethyl cyclohexylethylcarbamothioate cycluron 3-cyclooctyl-1,1-dimethylurea

cyperquat 1-methyl-4-phenylpyridinium

cyprazine 2-chloro-4-(cyclopropylamino)-6-(iso- propylamino)-s-triazine Common Fame Chemical Name cyprazole N-[5-(2-chloro-1,1-dimethylethyl)-1,3,4- thiadiazol-2-yl]cyclopropanecarbox- amide

cypromid 3',4'-dichlorocyclopropanecarboxanilide dalapon 2,2-dichloropropanoic acid

dazomet tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione

DCPA dimethyl 2,3,5,6-tetrachloro-1,4-benzene- dicarboxylate

desmediphan ethyl [3-[[(phenylamino)carbonyl]oxy]- phenyl]carbamate

desmetryn 2-(isopropylamino)-4-(methylamino)-6- (methylthio)-s-triazine

diallate S-(2,3-dichloro-2-propenyl)bis(1- methylethyl)carbamothioate

dicamba 3,6-dichloro-2-methoxybenzoic acid dichlobenil 2,6-dichlorobenzonitrile

dichlorprop (±)-2-(2,4-dichlorophenoxy)propanoic

acid

dichlofop (±)-2-[4-(2,4-dichlorophenoxy)phenoxy]- propanoic acid, methyl ester

diethatyl N-(chloroacetyl)-N-(2,6-diethylphenyl)- glycine

difenzoquat 1,2-dimethyl-3,5-diphenyl-1H-pyrazolium dimepiperate S-1-methyl-1-phenylethylpiperidine- 1-carbothioate

dinitramine N³,N³-diethyl-2,4-dinitro-6-(trifluoromethyl)-1,3-benzenediamine dinoseb 2-(1-methylpropyl)-4,6-dinitrophenol diphenamid N,N-dimethyl-α-phenylbenzeneacetamide Common Name Chemical Name dipropetryn 6-(ethylthio)-N,N'-bis(1-methylethyl)- 1,3,5-triazine-2,4-diamine

diquat 6,7-dihydrodipyrido[1,2-a:2',1'-c]- pyrazinedium ion

diuron N'-(3,4-dichlorophenyl)-N,N-dimethylurea

DNOC 2-methyl-4,6-dinitrophenol

DPX-M6316 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin- 2-yl)amino]carbonyl]amino]sulfonyl]- 2-thiophenecarboxylic acid, methyl ester

DSMA disodium salt of MAA

dymron N-(4-methylphenyl)-N'-(1-methyl- 1-phenylethyl)urea

endothall 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid

EPTC S-ethyl dipropylcarbamothioate

esprocarb S-benzyl-N-ethyl-N-(1,2-dimethyl)- (SC2957) propyl)thiolearbamate

ethalfluralin N-ethyl-N-(2-methyl-2-propenyl)-2,6- dinitro-4-(trifluoromethyl)- benzenamine

ethofumesate (±)-2-ethoxy-2,3-dihydro-3,3-dimethyl- 5-benzofuranyl methanesulfonate fenac 2,3,6-trichlorobenzeneacetic acid fenoxaprop (±)-2-[4-[(6-chloro-2-benzoxazolyl)oxy]- phenoxy]propanoic acid

fenuron N,N-dimethyl-N'-phenylurea

fenuron TCA Salt of fenuron and TCA

flamprop N-benzoyl-N-(3-chloro-4-fluorophenyl)- DL-alanine Common Name Chemical Name. fluazifop (±)-2-[4-[[5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propanoic acid fluazifop-P (R) -2- [4- [ [5-(trif luoromethyl) -2-pyridinyl]oxy]phenoxy]propanoic acid fluchloralin N-(2-chloroethyl)-2,6-dinitro-N-propyl- 4-(trifluoromethyl)benzenamine

fluometuron N,N-dimethyl-N'-[3-(trifluoromethyl)- phenyl]urea

fluorochlor- 3-chloro-4-(chloromethyl)-1-[3-(triidone fluoromethyl)phenyl]-2-pyrrolidinone fluorodifen p-nitrophenyl α,α,α-trifluoro-2-nitro- p-tolyl ether

fluorogly- carboxymethyl 5-[2-chloro-4-(tricofen fluoromethyl)phenoxy]-2-nitrobenzoate fluridone 1-methyl-3-phenyl-5-[3-(trifluoromethyl)phenyl]-4(1H)-pyridinone fomesafen 5-[2-chloro-4-(trifluoromethyl)phenoxy]- N-(methylsulfonyl)-2-nitrobenzamide fosamine ethyl hydrogen (aminocarbonyl)- phosphate

glyphosate N-(phosphonomethyl)glycine

haloxyfop 2-[4-[[3-chloro-5-(trifluoromethyl)-2- pyridinyl]oxy]phenoxy]propanoic acid hexaflurate potassium hexafluoroarsenate

hexazinone 3-cyclohexyl-6-(dimethylamino)-1-methyl- 1,3,5-triazine-2,4(1H,3H)-dione imazametha- 6-(4-isopropyl-4-methyl-5-oxo-2- benz imidazolin-2-yl)-m-toluic acid,

methyl ester and 6-(4-isopropyl- 4-methyl-5-oxo-2-imidazolin-2-yl)- p-toluic acid, methyl ester Common Name Chemical Name imazapyr (±)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3- pyridinecarboxylic acid

imazaquin 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3- quinolinecarboxylic acid

imazethapyr (±)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5- ethyl-3-pyridinecarboxylic acid ioxynil 4-hydroxy-3,5-diiodobenzonitrile

isopropalin 4-(1-methylethyl)-2,6-dinitro-N,N- dipropylbenzenamine

isoproturon N-(4-isopropylphenyl)-N',N'-dimethylurea isouron N'-[5-(1,1-dimethylethyl)-3-isoxazolyl]- N,N-dimethylurea

isoxaben N-[3-(l-ethyl-1-methylpropyl)-5- isoxazolyl]-2,6-dimethoxybenzamide karbutilate 3-[[(dimethylamino)carbonyl]amino]- phenyl-(1,1-dimethylethy1)carbamate lactofen (±)-2-ethoxy-1-methyl-2-oxoethyl 5-[2- chloro-4-(trifluoromethyl)phenoxy]- 2-nitrobenzoate

lenacil 3-cyclohexyl-6,7-dihydro-1H-cyclopenta- pyrimidine-2,4(3H,5H)-dione

linuron N'-(3,4-dichlorophenyl)-N-methoxy-N- methylurea

MAA methylarsonic acid

MAMA monoammonium salt of MAA

MCPA (4-chloro-2-methylphenoxy) acetic acid MCPB 4-(4-chloro-2-methylphenoxy)butanoic

acid Common Name Chemical Name

MON 7200 S,S-dimethyl-2-(difluoromethyl)-4-

(2-methylpropyl)-6-(trifluoromethyl)- 3,5-pyridinedicarbothionate

mecoprop (±)-2-(4-chloro-2-methylphenoxy)- propanoic acid

mefenacet 2-(2-benzothiazolyloxy-N-methyl-N- phenylacetamide

mefluidide N-[2,4-dimethyl-5-[[(trifluoromethyl)- sulfonyl]amino]phenyl]acetamide methal- N-(2-methyl-2-propenyl)-2,6-dinitro-N- propalin propyl-4- (trif luoromethyl ) benzenamide methabenz- 1, 3-dimethyl-3-(2-benzothiazolyl)urea thiazuron

metham methylcarbamodithioic acid

methazole 2-(3,4-dichlorophenyl)-4-methyl-1,2,4- oxadiazolidine-3,5-dione

methoxuron N'-(3-chloro-4-methoxyphenyl)-N,N- dimethylurea

metolachlor 2-chloro-N-(2-ethyl-6-methylphenyl)-N- (2-methoxy-1-methylethyl)acetamide metribuzin 4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one

metsulfuron 2-[[[[(4-methoxy-6-methyl-1,3,5-trimethyl azin-2-yl)amino]carbonyl]- amino]sulfonyl]benzoic acid,

methyl ester

MH 1,2-dihydro-3,6-pyridazinedione

molinate S-ethyl hexahydro-1H-azepine-1-carbothioate Common Name Chemical Name monolinuron 3-(p-chlorophenyl)-1-methoxy-1-methyl- urea

monuron N'-(4-chlorophenyl)-N,N-dimethylurea monuron TCA Salt of monuron and TCA

MSMA monosodium salt of MAA

napropamide N,N-diethyl-2-(1-naphthalenyloxy)- propanamide

naptalam 2- 1(1-naphthalenylamino)carbonyl]- benzoic acid

neburon 1-butyl-3-(3,4-dichlorophenyl)-1-methyl- urea

nitralin 4-(methylsulfonyl)-2,6-dinitro-N,N- dipropylaniline

nitrofen 2,4-dichloro-1-(4-nitrophenoxy)benzene nitrofluorfen 2-chloro-1-(4-nitrophenoxy)-4-(trifluoromethyl)benzene

norea N,N-dimethyl-N'-(octahydro-4,7-methano- 1H-inden-5-yl)urea 3aα,- 4α,5α,7α,7aα-isomer

norflurazon 4-chloro-5-(methylamino)-2-[3-(trifluoromethyl)phenyl]-3(2H)- pyridazinone

oryzalin 4-(dipropylamino)-3,5-dinitro- benzenesulfonamide

oxadiazon 3-[2,4-dichloro-5-(1-methylethoxy)- phenyl]-5-(1,1-dimethylethyl)- 1,3,4-oxadiazol-2(3H)-one

oxyfluorfen 2-chloro-1-(3-ethoxy-4-nitroρhenoxy)-4- (trifluoromethyl)benzene

paraquat 1,1'-dimethyl-4,4'-dipyridinium ion Common Name Chemical Name pebulate S-propyl butylethylcarbamothioate pendimethalin N-(1-ethylpropyl)-3,4-dimethyl-2,6- dinitrobenzenamine

perfluidone 1,1,1-trifluoror-N-[2-methyl-4-(phenylsulfonyl)phenyl]methanesulfonamide phenmedipham 3-[(methoxycarbonyl)amino]phenyl (3- methylphenyl)carbamate

picloram 4-amino-3,5,6-trichloro-2-pyridine- carboxylic acid

PPG-1013 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitroacetophenone

oxime-0-acetic acid, methyl ester pretilachlor α-chloro-2,6-diethyl-N-(2-propoxy- ethyl)acetanilide

procyazine 2-[[4-chloro-6-(cyclopropylamino)-1,3,5- triazine-2-yl]amino]-2-methylpropane- nitrile

profluralin N-(cyclopropylmethyl)-2,6-dinitro-N- propyl-4-(trifluoromethyl)benzenamine prometon 6-methoxy-N,N'-bis(1-methylethyl)-1,3,5- triazine-2,4-diamine

prometryn N,N'-bis(1-methylethyl)-6-(methylthio)- 1,3,5-triazine-2,4-diamine

pronamide 3,5-dichloro-N-(1,1-dimethyl-2-propynyl)benzamide

propachlor 2-chloro-N-(1-methylethyl)-N- phenylacetamide

propanil N-(3,4-dichlorophenyl)propanamide propazine 6-chloro-N,N'-bis(1-methylethyl)- 1,3,5-triazine-2,4-diamine

propham 1-methylethyl phenylcarbamate Common Name Chemical Name prosulfalin N-[[4-(dipropylamino)-3,5-dinitrophenyl]sulfonyl]-S,S-dimethylsulfilimine

prynachlor 2-chloro-N-(1-methyl-2-propynyl)acetanilide

pyrazolate 4-(2,4-dichlorobenzoyl)-1,3-dimethyl- pyrazol-5-yl-p-toluenesulphonate pyrazon 5-amino-4-chloro-2-phenyl-3(2H)- pyridazinone

pyrazosulfuron ethyl 5-[3-(4,6-dimethoxypyrimidin-2- ethyl yl)ureadosulfonyl]-1-methylpyrazole- 4-carboxylate

quinclorac 3,7-dichloro-8-quinoline carboxylic acid quizalofop (±)-2-[4-[(6-chloro-2-quinoxalinyl)- ethyl oxy]phenoxy]propanoic acid, ethyl

ester

secbumeton N-ethyl-6-methoxy-N'-(1-methylpropyl)- 1,3,5-triazine-2,4-diamine

sethoxydim 2-[1-(ethoxyimino)butyl]-5-[2-(ethyl- thio)propyl]-3-hydroxy-2-cyclohexen- 1-one

siduron N-(2-methylcyclohexyl)-N'-phenylurea simazine 6-chloro-N,N'-diethyl-1,3,5-triazine- 2,4-diamine

SK-233 1-(α,α-dimethylbenzyl)-3-(4-methyl- phenyl)urea

sulfometuron 2-[[[[(4,6-dimethyl-2-pyrimidinyl)- methyl amino]carbonyl]amino]sulfonyl]- benzoic acid, methyl ester

TCA trichloroacetic acid

tebuthiuron N-[5-(1,1-dimethylethyl)-1,3,4-thiadiazol-2-yl]-N,N'-dimethylurea

terbacil 5-chloro-3-(1,1-dimethylethyl)-6- methyl-2,4(1H,3H)-pyrimidinedione Common Name Chemical Name terbuchlor N-(butoxymethyl)-2-chloro-N-[2-(1,1- dimethylethyl)-6-methylphenyl]- acetamide

terbuthyl- 2-(tert-butylamino)-4-chloro-6-(ethyl- azine amino)-s-triazine

terbutol 2,6-di-tert-butyl-p-tolyl methylcarbamate

terbutryn N-(1,1-dimethylethyl)-N'-ethyl-6- (methylthio)-1,3,5-triazine- 2,4-diamine

thiobencarb S-[(4-chlorophenyl)methyl] diethylcarbamothioate

triallate S-(2,3,3-trichloro-2-propenyl) bis(1- methylethyl)carbamothioate

tribenuron 2-[[[[N-(4-methoxy-6-methyl-1,3,5- methyl triazine-2-yl)-N-methylamino]- carbonyl]amino]sulfonyl]benzoic acid, methyl ester

triclopyr [(3,5,6-trichloro-2-pyridinyl)- oxy]acetic acid

tridiphane 2-(3,5-dichlorophenyl)-2-(2,2,2- trichloroethyl)oxirane

trifluralin 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzenamine

trimeturon 1-(p-chlorophenyl)-2,3,3-trimethylpseudourea

2,4-D (2,4-dichlorophenoxy) acetic acid

2,4-DB 4-(2,4-dichlorophenoxy)butanoic acid vernolate S-propyl dipropylcarbamothioate

xylachlor 2-chloro-N-(2,3-dimethylphenyl)-N- (1-methylethyl) acetamide

Herbicidal properties of the subject compounds were discovered in a series of greenhouse tests.

Test procedures and results follow.

TEST A

Seeds of barley (Hordeum vulgare),

barnyardgrass (Echinochloa crus-galli), cheatgrass (Bromus secalinus), cocklebur (Xanthium

pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.), giant foxtail (Setaria faberi), morningglory (Ipomoea spp.), rice (Orvza sativa), sorghum (Sorohum bicolor), soybean

(Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), 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 (two to three leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for approximately sixteen days, after which all species were compared to controls and visually evaluated.

Plant iresponse 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

Seeds of barley (Hordeum vulgare),

barnyardgrass (Echinochloa crus-galli), blackgrass (Alopecurus myosuroides), cheatgrass (Promus

secalinus), chickweed (Stellaria media), cocklebur (Xanthium pensyivanicum), corn (zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.), bedstraw (Galium aparine), giant foxtail (Setaria faberii), lambsguarters (Chenopodium album),

morningglory (Ipomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sorghum (Sorohum

bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestiyum), wild buckwheat (Polygonum convolyulus), and wild oat (Ayena 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 B, 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 C

Seeds of barley (Hordeum vuloare),

barnyardgrass (Echinochloa crus-galli), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium pensylyanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass

(Dioitaria spp.), downy brome (Bromus tectorum), giant foxtail (Setaria faberi), green foxtail

(Setaria viridis ) , j imsonweed (Datura Stramonium), johnsongrass (Sorghum halepense), lambsquarters

(Chenopodium album), morningglory (Ipomoea spp.), rape (Brassica naous), rice (Oryza sativa), sicklepod (Cassia obtusifolia), soybean (Glycine max), sugar beet (Beta vulgaris), teaweed (Sida spinosa),

velvetleaf (AbutiIon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum conyolvulus), 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 (two to three leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for approximately 24 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 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test result.

TEST D

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 (paddy 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 paddy test. Water depth was approximately 2.5 cm for the paddy 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 (AbutiIon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum

conyolvulus), 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

postemergence portion of the test. Plant species in the paddy test consisted of barnyardgrass (Echinochloa crus-galli), rice (Oryza sativa), and umbrella sedge (Cyperus difformis).

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 D, were recorded on a 0 to 10 scale where 0 is no injury and 10 is complete control. A dash (-) response means no test result.

TEST E

Seeds of barnyardgrass (Echinochloa

crus-galli), cocklebur (Xanthium pensylvanicum), corn (Zea mays) (soil surface exposed and soil surface covered with perlite), crabgrass (Digitaria spp.), fall panicum (Panicum dichotomiflorum), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), ivyleaf morningglory (Ipomoea hederacea), jimsonweed (Datura stramonium), johnsongrass (Sorghum

halepense), ladysthumb smartweed (Polygonum

persicaria), lambsquarters (Chenopodium album), redroot pigweed (Amaranthus retroflexus), sorghum (Sorghum bicolor), soybean (Glycine max), and

velvetleaf (Abutilon theophrasti) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals dissolved in a non-phytotoxic solvent. These crop and weed species were also treated with postemergence applications of test compounds. Plants ranged in height from two to twenty-five cm for postemergence treatments.

Treated plants and controls were maintained in a greenhouse for approximately 24 days, after which all species were compared to controls and visually evaluated. The ratings, summarized in Table E, 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 F

Plastic pots were partially filled with silt loam soil. The soil was then saturated with water. Indica and Japonica rice (Oryza sativa) seedlings at the 2.0 to 2.5 leaf stage, seeds selected from barnyardgrass (Echinochloa crus-galli), bulrush

(Scirpus mucronatus), duck salad (Heteranthera

Bimosa), umbrella sedge (cyperus difformis) and tubers selected from 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 F, are reported on a 0 to 10 scale where 0 is no effect and 10 is complete

control. A dash (-) response means no test result.

TEST G

Compounds evaluated in this test were

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

(preemergence application) and to plants that were in the one-to-four leaf stage (postemergence

application). A sandy loam soil was used for the preemergence test while a mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Test compounds were applied within approximately one day after planting seeds for the preemergence test. Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include winter barley (Hordeum vulgare cv. 'Igri'), bedstraw (Galium aparine), blackgrass (Alopecurus

myosuroides), chickweed (Stellaria media), downy brome (Bromus tectorum), field violet (Viola

arvensis), green foxtail (Setaria viridis), kochia (Kochia scoparia), lambsquarters (Chenopodium album), Persian speedwell (Veronica persica), rape (Brassica napus cv. 'Jet Neuf'), ryegrass (Lolium multiflorum), sugar beet (Beta vulgaris cv. 'USl'), sunflower

(Helianthus annuus cv. 'Russian Giant'), spring wheat (Triticum aestivum cv. 'ERA'), winter wheat (Triticum aestivum cv. 'Talent'), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avena fatua), and wild radish (Raphanus

raphanistrum). Blackgrass and wild oat were treated postemergence at two growth stages. The first stage (1) was when the plants had two to three leaves. The second stage (2) was when the plants had approximately four leaves or in the initial stages of tillering. Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which all treated plants were compared to untreated controls and visually

evaluated. Plant response ratings, summarized in Table G, are based upon a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash response (-) means no test result.

TEST H

Seeds of alfalfa (Medicago sativa), bean (Phaseolus vulgaris), bluegrass (Poa pratensis), cabbage (Brassica rape), carrot (Daucus sativa), corn (Zea mays), flax (Linum usitatissimum), lettuce

(Lactuca sativa), lupine (Lupinus albus), oats (Avena sativa), onion (Allium cepa), pea (sativum), peanut (Arachis hypogaea), potato (Solanum tuberosum), rye

(Secale cereal), sorghum (Sorghum bicolor), sunflower (Helianthus annuus), and tomato (Lycopersicon

esculentum) were planted and treated preemergence with a test chemical dissolved in a non-phytotoxic solvent. These crop species were also treated with postemergence applications of the test chemical.

Plants ranged in height from four to twenty cm (two to three leaf stage) when post-emergence applications were applied. Treated plants and controls were grown under greenhouse conditions for approximately

twenty-four days, after which all plants treated with the test chemical were compared to untreated controls and visually evaluated for injury response.

Application rates for the test chemical are shown in Table H. Plant response ratings, summarized in Table H, are from 0 to 10 where 0 is no injury and 10 is complete control. A dash (-) response means no test result.

Claims

CLAIMS What is claimed is:

1. A compound selected from

wherein:

A is OR¹ or N(CH₃)₂;

R¹ is C₁-C₃ alkyl, CH₂CH=CH₂, CH₂C=CH, CH₂CH₂Cl or CH₂CH₂OCH₃;

R² is CH₂F, CHF₂, CHFCH₃ or CH₂CN;

X is CH₃ or OCH₃; and

Y is H, Cl, CH₃, C₂H₅, OCH₃ or OCF₂H;

2. A compound of Claim 1 wherein

A is OR¹; and

R¹ is CH₃, CH₂CH₃ or CH(CH₃)₂.

3. A compound of Claim 2 where

when one of X and Y is CH₃, then the other of X and Y is other than OCH₃.

4. The compound of Claim 1,

methyl 3-(cyanomethyl)-2-[[[[(4,6- dimethyl-2-pyrimidinyl)amino]carbonyl]- amino]sulfonyl]benzoate.

5. The compound of Claim 1,

methyl 2-[[[[(4-chloro-6-methoxy-2- pyrimidinyl)amino]carbonyl]amino]- sulfonyl]-3-(cyanomethyl)benzoate.

6. The compound of Claim 1,

methyl 3-(cyanomethyl)-2-[[[[[(4- (difluoromethoxy)-6-methoxy-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]- benzoate.

7. The compound of Claim 1,

methyl 3-(difluoromethyl)-2-[[[[(4- methoxy-2-pyrimidinyl)amino]carbonyl]- amino]sulfonyl]benzoate.

8. The compound of Claim 1,

methyl 3-(fluoromethyl)-2-[[[[(4- methoxy-2-pyrimidinyl)amino]carbonyl]- amino]sulfonyl]benzoate.

9. The compound of Claim 1,

methyl 2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-3- (fluoromethyl)benzoate.

10. The compound of Claim 1,

ethyl 2-[[[[(4-chloro-6-methoxy-2- pyrimidinyl)amino]carbonyl]amino]- sulfonyl]-3-(fluoromethyl)benzoate.

11. A compound selected from

wherein:

A is OR¹ or N(CH₃)₂;

R¹ is C₁-C₃ alkyl, CH₂CH=CH₂, CH₂CΞCH,

CH₂CH₂Cl or CH₂CH₂OCH₃;

R² is CH₂F, CHF₂, CHFCH₃ or CH₂CN; and

Z¹ is Cl or NHSiR³R⁴R⁵;

R³ is C₁-C₄ alkyl;

R⁴ is C₁-C₄ alkyl; and

R⁵ is C₁-C₄ alkyl.

12. A compound of Claim 11 wherein A is OR¹ and R¹ is C₁-C₂ alkyl.

13. A compound of Claim 12 wherein R³ and R⁴ are CH₃ and R⁵ is C(CH₃)₃.

14. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 1 and at least one of the following: surfactant, solid diluent or liquid diluent.

15. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 2 and at least one of the following: surfactant, solid diluent or liquid diluent.

16. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 3 and at least one of the following: surfactant, solid diluent or liquid diluent.

17. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 4 and at least one of the following: surfactant, solid diluent or liquid diluent.

18. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of Claim 5 and at least one of the following: surfactant, solid diluent or liquid diluent.

19. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of Claim 1.

20. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of Claim 2.

21. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of Claim 3.

22. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of Claim 4.

23. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of the compound of Claim 5.

24. The method of Claim 22 wherein the locus to be protected is corn.

25. A method for controlling the growth of undesired vegetation in wheat or barley which

comprises applying to the wheat or barley an

effective amount of the compound of Claim 9.