I∑∑LE CROP-SELECTIVE HERBICIDAL SULFONA IDES 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 C _j^ -Cg haloalkyl;

R ¹ is H, halogen, N0 ₂ , CN, C _j^ -C _ή alkyl, ^c l~ ^c 4 haloalkyl, C _j -C^ alkoxy, C _j -C _ή alkylthio, C _j -^ alkylsulfinyl, C _j -C _ή alkylsulfonyl, COR ⁶ , NR ⁷ R ⁸ , CONR ⁹ R ¹⁰ or

SO _j NR ^{13 12} ; and R ⁶ is C _j -C^ alkoxy, C _j -C _ή haloalkoxy, ^c l" 4 alkylthio, C ₂ -C ₆ alkoxyalkoxy, hydrogen, C ₁ -C ₄ alkyl or C _χ -C ₄ 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 poste ergence herbicides or plant growth regulants:

₂ NHCNH (Q/

wherein:

A is OR ¹ or N(CH ₃ ) ₂ ;

R ¹ is Cj^Cg alkyl, CH ₂ CH-CH ₂ , CH ₂ C=CH, CH ₂ CH ₂ C1 or CH ₂ CH ₂ OCH ₃ ;

R ² is CH ₂ F, CHF ₂ , CHFCH ₃ or CH ₂ CN; X is CH ₃ or OCH ₃ ; and

Y is H, Cl, CH ₃ , C ₂ H ₅ , OCH ₃ or OCF ₂ H; and their agriculturally suitable salts; provided that when Y is Cl, then X is OCH ₃ .

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 _j -Cj prefix where i and j are numbers 1 to 3. For example, C ₁ -C ₃ 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 OR ¹ ; and

R ¹ is CH ₃ , CH ₂ CH ₃ or CH(CH ₃ ) ₂ . 2. Compounds of Preferred 1 where when one of X and Y is CH ₃ , then the other of X and Y is other than OCH ₃ . 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 OR ¹ , R ¹ is CH ₃ , R ² is CH ₂ CN, X and Y are CH ₃ . 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 OR ¹ , R ¹ is CH ₃ , R ² is CH ₂ CN, X is OCH ₃ , Y is Cl);

• Methyl 3-(cyanomethyl)-2-[[[[[(4-

(difluoromethoxy)-6-methoxy-2-pyrimidinyl]- a ino]carbonyl]amino]sulfonyl]benzoate (Formula I: A is OR ¹ , R ¹ is CH ₃ , R ² is CH ₂ CN, X is OCH ₃ , Y is OCF ₂ H) ;

• Methyl 3-(difluoromethyl)-2-[ [[ [(4-methoxy- 2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-

benzoate (Formula I: A is OR ¹ , R ¹ is CH ₃ , R ² is CHF ₂ X is OCH ₃ , Y is H) ; • Methyl 3-(fluoromethyl)-2-[[[[(4-methoxy-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]- benzoate (Formula I: A is OR ¹ , R ¹ is CH ₃ , R ² is CH ₂ F, X is OCH ₃ , 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 OR ¹ , R ¹ is CH ₃ , R ² is CH ₂ F, X and Y are OCH ₃ ).

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 OR ¹ , R ¹ is CH ₂ CH ₃ , R ² is CH ₂ F, X is OCH ₃ , 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:

II

wherein:

A is OR ¹ or N(CH ₃ ) ₂ ; R ¹ is C!^ alkyl, CH ₂ CH-CH ₂ , CH ₂ C=CH, CH ₂ CH ₂ C1 or CH ₂ CH ₂ OCH ₃ ; R ² is CH ₂ F, CHF ₂ , CHFCH ₃ or CH ₂ CN; and Z ¹ is Cl or NHSiR ³ R ⁴ R ⁵ ; R ³ is Ci-C _ή alkyl; R ⁴ is C _j -C ₄ alkyl; and R ⁵ is Ci-C _ή alkyl.

Preferred for reason of increased herbicidal activity of final products of Formula I, are intermediates of Formula II wherein A is OR ¹ and R ¹ is C ₁ -C ₂ alkyl.

Preferred for reason of increased ease of synthesis are intermediates of the above preferred wherein R ³ and R ⁴ are CH ₃ and R ⁵ is C(CH ₃ ) ₃ .

DETAILED DESCRIPTION OF THE INVENTION

C

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 εilyl sulfonamide of Formula (2) with a pyrimidine carbamate of Formula (3). R ³ , R ⁴ , and R^ are independently C _j to C ₄ alkyl. Equation 1

C2) C3)

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 l,8-diazabicyclo[5. .0]undec-7-ene (DBU), increases the reaction rate.

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

(4) (3)

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

5) C6)

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 11, 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 sulfonamideε of Formula

(4) as outlined in Equation 5.

Equation 5

C4)

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. R ⁶ is

H, alkyl, benzyl or carbamoyl.

Equation 6

CB)

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 1Q1, 91 (1982).

Alternatively, reaction of compounds of Formula

(8), where R ⁶ 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

SO

The aniline is diazotized and then reacted with sulfur dioxide and cupric chloride analogous to the teachings of Yale and Sowinski, J. Org. Chem. 2 ., 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. A2., 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

Methvl 3-(Cvanomethvlι-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 (CDC1 ₃ ) δ: 3.83 (s, 2H, CH ₂ ); 3.93 (s, 3H, CH ₃ ); and

7.9 (m, 3H, aro .) EXAMPLE 2 2-(Methoxycarbonyl)-6-(cyanomethyl)- benzenesulfonvl 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 (CDC1 ₃ ) δ: 3.98 (s, 3H, CH.,);

4.41 (s, 2H, CH ₂ ); and 7.83 (m, 3H, arom.). EXAMPLE 3 Methyl 3-(Cyanomethy1)-2-[[[(1,1-dimethyleth 1)- di ethvlsilvllaminolsulfonvllbenzoate

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 (CDC1 ₃ ) δ: 0.32 (s, 6H, SiCH ₃ );

0.95 (s, 9H, C(CH ₃ ) ₃ );

3.99 (s, 3H, OCH ₃ ); 4.42 (s, 2H, CH ₂ CN); 5.91 (s, 1H, NH);

7.6 (m, 2H, aro .); and 7.8 (m, 1H, arom.). IR (mineral oil) 3290, 2250, and 1710 cm" ¹ .

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

2-pyrimidinyl)amino1carbonyl1amino1sulfonyllbenzoate A mixture of methyl 3-(cyanomethyl)- 2- 1t[(1,1-dimethylethyl)dimethylsilyl]amino]- sulfonyl]benzoate (0.34 g) , 0-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. .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 IN 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, CH ₃ ); 4.67 (s, 2H, CH ₂ CN); 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 . E-XAMP E 5

Methvl 3-Formvl-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 (CDC1 ₃ ) δ: 3.98 (S, 3H, OCH3);

7.8 (m, 1H, arom.); 8.3 (m, 2H, arom.); and 10.0 (s, 1H, HCO) . EXAMPLE 6

Methvl 3-(Di luoromethyl>-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. Recrystalli¬ zation from hexanes-chlorobutane gave 3.94 g of the title compound as a peach-colored solid, m.p. 66-69°C. 90 MHz NMR (CDC1 ₃ ) δ: 3.94 (s, 3H, OCH ₃ ); 6.87 (t, 1H, CHF ₂ ); and

7.9 (m, 3H, arom.). EXAMPLE 7 2-(Methoxycarbonyl)-6-(difluoromethyl)- benzenesulfonvl 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 (CDC1 ₃ ) δ: 4.13 (s, 3H, OCH ₃ ); and

7.1 - 8.3 (m, 4H, CHF ₂ and arom.) . EXAMPLE 8 Methyl 3-(Difluoromethyl)-2-[[[(1,1-dimethyl- ethvl)dimethvlsilvnamino1sulfonyllbenzoate

A suspension of 2-(methoxycarbonyl)-6-(difluoro¬ methyl)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 (CDClg) δ: 0.2 (s, 6H, SiCH ₃ );

0.87 (s, 9H, C(CH ₃ ) ₃ ); 3.90 (ε, 3H, OCH ₃ );

5.88 (s, 1H, NH); and 7.20 - 8.36 (m, 4H, CHF ₂ and arom.).

EXAMPLE 9 Methyl 3-(Difluoromethyl)-2-[[[[(4-methoxy-2- pyrimidinvDaminolcarbonvnaminolsulfonyllbenzoate A mixture of methyl 3-(difluoromethyl)-2- 1 [t(l,l-dimethylethyl)dimethylsilyl]amino]sulfonyl]- benzoate (0.22 g), 0-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 IN 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, OCH ₃ ); 4.14 (s, 3H, OCH ₃ );

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 Methvl 3-(l-Hvdroxvethvl)-2-nitrobenzoate Titanium tetrachloride (6.25 mL) was added to dry diethylether (250 mL) at -78°C and was stirred 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 molar

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 adjacent flask 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 (CDC1 ₃ ) δ: 1.47 (d, 3H, CH ₃ ); 2.58 (s, 1H, OH);

3.92 (s, 3H, OCH ₃ );

4.93 (m, 1H, CH) ; and 7.8 (m, 3H, arom.) .

IR (neat) 3431, 1735 cm ^-1 . EXAMPLE 11

Methvl 3-(1-Fluoroethvn-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-(l- 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, OCH ₃ ); 5.7 (d of q, 1H, CHF); and 7.9 (m, 3H, arom.). IR (neat) 1736 cm" ¹ . EXAMPLE 12

Methyl 3-(l-Fluoroethyl)-2- (phenylmethylthio)benzoate Following the procedure described in Example 2, methyl 3-(l-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-(l-fluoroethyl)- benzene sulfonvl Chloride Following the procedure described in Example 2, methyl 3-(l-fluoroethy1)-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 (CDC1 ₃ ) δ: 1.8 (d of d, 3H, CH ₃ );

4.0 (s, 3H, OCH ₃ ); 6.6 (d of q, 1H, CHF); and 7.8 (m, 3H, arom.). EXAMPLE 14 Methyl 3-(l-Fluoroethyl)-2-[ [[(1,1-dimethyl- ethvDdimethvlsilvnaminolsulfonyl1benzoate 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, SiCH ₃ );

0.24 (s, 3H, SiCH ₃ ); 0.84 (s, 9H, C(CH ₃ ) ₃ ); 1.57 (d of d, 3H, CH ₃ ); 3.88 (s, 3H, OCH ₃ ); 5.83 (ε, 1H, NH); 6.6 (d of q, 1H, CHF); and 7.6 (m, 3H, arom.). EXAMPLE 15 Methyl 3-(l-Fluoroethyl)-2-[[[[(4,6-dimethoxy-2- pyrimidinvDaminolcarbonyllaminolsulfonyllbenzoate Following the procedure described in Example 4, methyl 3-(l-fluoroethyl)-2-[[[(1,1-dimethylethyl)- dimethylεilyl]amino]εulfonyl]benzoate (0.26 g) and 0-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, CH ₃ );

3.85 (s, 3H, C0 ₂ CH ₃ ); 3.98 (s, 6H, OCH ₃ ); 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 (ε, 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.

TABLE 1

is CH- R ¹ is CH ₂ CH ₃

R ¹ is CH ₂ CH ₂ CH ₃ R ¹ is CH(CH ₃ ) ₂

in X x ΓuH uΓM

ΓO ΓO ΓO X X X u u υ O O O z z z U U U CM CM CM X X X u u u

CN CM in ro fa ro fa ro X X X X x CM υ υ •-* u u H x u u o o x u o o x x υ

ΓO ΓO ΓO ΓO ΓO ΓO ΓO ΓO ΓO ΓO ΓO ΓO ΓO ΓO X X X X ΓO ΓO ΓO ΓO ΓO X X X X ΓO ΓO ΓO ΓO ΓO X X ►o x ΓO u υx ux υx ux uo υo υo uo ux ux ux ux ux uo uo uo uo ux ux ux ux ux uo υo

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Formulations

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dustε, granuleε, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrateε and the like. Many of theεe may be applied directly. Sprayable formulationε can be extended in εuitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositionε are primarily uεed aε intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(ε) and at least one of

(a) about 0.1% to 20% surfactant(ε) and (b) about 1% to 99.9% solid or liquid inert diluent(ε). More εpecifically, they will contain theεe ingredients in the following approximate proportions: Weight Percent*

Active Ingredient Pilvent(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 Dustε

Granuleε and Pellets

High Strength

Compoεitions

* 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 propertieε of the compound. Higher ratios of surfactant to active ingredient are some¬ times desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical εolid diluentε are deεcribed in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufac¬ tured, may be used. The more absorptive diluents are preferred for wettable powderε and the denεer 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 εuspenεion concentrateε; solution concentrateε are preferably stable against phase separation at 0°C. "McCutcheon's Detergentε and

Emulεifierε Annual", MC Publiεhiπg Corp., Kidgewood, New Jerεey, aε well as Sisely and Wood, "Encyclopedia of Surface Active Agentε", Chemical Publiεhing Co., Inc., New York, 1964, liεt 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 compositionε are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositionε are made by blending and, usually, grinding aε in a hammer or fluid energy mill. Suεpenεionε are prepared by wet milling (εee, for example, Littler, U.S. Patent 3,060,084). Granuleε and pellets may be made by εpraying the active material upon preformed granular carrierε or by agglomeration techniqueε. See J. E. Browning, "Agglomeration", Chemical Engineering. December 4, 1967, pp. 147ff. and "Perry*ε 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. Gyεin 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 Publicationε, Oxford, 1968, pp. 101-103. In the following examples, all parts are by weight unless otherwise indicated.

Example A Hioh Strength Concentrate

Methyl 3-(cyanomethyl)-2-[[[[(4,6-dimethyl- 2-pyrimidinyl)amino]carbonyl]amino]- εulfonyl]benzoate 99% trimethylnonyl polyethylene glycol ether 1% The εurfactant 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]εulfonyl]-3-(cyanomethyl)- benzoate 65% dodecylphenol polyethylene glycol ether 2% sodium ligninεulfonate 4% εodium εilicoaluminate 6% montmorillonite (calcined) 23%

The ingredientε are thoroughly blended. The liquid εurfactant 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 Aσueous Suspension

Methyl 3-(cyanomethyl)-2-[[[[(4-(difluoro- ethoxy)-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% monoεodium 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]εulfonyl]- benzoate 35%

blend of polyalcohol carboxylic eεterε and oil soluble petroleum sulfonateε 6% xylene 59%

The ingredientε are combined and ground together in a sand mill to produce particles esεentially 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] ulfonyl]- benzoate 25% polyoxyethylene εorbitol hexaoleate 5% highly aliphatic hydrocarbon oil 70%

The ingredientε are ground together in a εand mill until the εolid particles have been reduced to under about 5 microns. The resulting thick εuεpension may be applied directly, but preferably after being extended with oils or emulsified in water.

Example F Aqueous Suspension Methyl 2-t[[[(4,6-dimethoxy-2-ρyrimidinyl)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 diameterε under 10 micronε.

Example G Wettable Powder

Ethyl 2-[ [ [[(4-chloro-6-methoxy-2-pyrimidinyl)- amino]carbonyl]amino]εulfonyl]-3-(fluoromethyl)- benzoate 40.0%

dioctyl εodium εulfoεuccinate 1.5% sodium ligninεulfonate 3% low viscosity methyl cellulose 1.5% attapulgite 54%

The ingredientε are thoroughly blended, passed through an air mill, to produce an average particle size under 15 micronε, reblended, and εifted through a U.S.S. No. 50 εieve (0.3 mm opening) before packaging. All compoundε of the invention may be formulated in the εame manner.

Example H Granule wettable powder of Example G 15% gypεum 69% potassium sulfate 16%

The ingredientε are blended in a rotating mixer and water εprayed 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 εieveε), the granules are removed, dried, and screened. Oversized material is cruεhed to produce additional material in the desired range. Theεe granuleε contain % active ingredient.

Example I Wettable Powder

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

The ingredients are blended, coarsely hammer- milled 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]εulfonyl]- benzoate 25% anhydrouε εodium εulfate 10% crude calcium ligninεulfonate 5% εodium alkylnaphthalenesulfonate 1% calcium/magneεium bentonite 59%

The ingredientε 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. Theεe may be uεed directly after drying, or the dried pelletε may be cruεhed to pass a U.S.S. No. 20 εieve (0.84 mm openingε). 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 owder

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 lesε than 25 micronε in diameter. The material iε reblended and εifted through a U.S.S. No. 50 εieve (0.3 mm opening) before being packaged.

Example L

Hioh Strength Concentrate Methyl 3-(cyanomethyl)-2-[[[[(4-(difluoromethoxy)- 6-methoxy-2-pyrimidinyl]amino]carbonyl]amino]- εulfonyl]benzoate 98.5% εilica aerogel 0.5% εynthetic amorphouε fine εilica 1.0% The ingredientε are blended and ground in a hammer mill to produce a high εtrength 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]εulfonyl]- benzoate, εodium εalt 5% water 95%

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

IZXI IIX

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 graεε and broad- leaf weeds with tolerance to important argonomic crops such as barley ⁽ Hordeum vuloare) . corn (Z_ea mavs) . rice (Qrysa sativa) , and wheat ⁽ Triticum aestivum) .

Grass weeds controlled include, but are not limited to, barnyardgrasε (Echinochloa . black- grass (AlOPecurus myosuroides) Bromus spp., foxtail

(Setaria spp.), johnsongrass (Sorghum haleoense) . panicu (Panicum εpp.), and wild oat (Avena jjaina) .

Broadleaf weedε controlled include, but are not

limited to, cocklebur (Xanthium pensylvanicum) , jimsonweed (Datura stramonium) . lambsquarterε (Chenopodium album), morningglory (Ipomoea spp.), pigweed (A aranthus spp.), Polvoonum spp., sicklepod (Cassia obtusifolia) . and velvetleaf (Abut lon theophrasti) . Many compoundε in thiε invention alεo control nutεedge (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 weedε iε deεired, such as around storage tanks, parking lots, billboards, highwayε, and railroad εtructureε. Theεe compoundε are alεo uεeful in fallow areas of crop production such as in wheat and barley and in plantation crops such aε palm, banana, citruε, rubber, etc. Alternatively, theεe compounds may be useful to modify plant growth or as citrus harvest aid absciεεion agentε.

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

These factors include: formulation selected, method of application, amount of vegetation present, growing conditionε, 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 deεired level of weed control.

Compounds of this invention may be uεed 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)acetami e acifluorfen 5-t2-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 phoεphorodi- thioate a etryn N-ethy1-N*-(1-methylethy1)-6-

(methylthio)-l,3,5-triazine-2,4- diamine amitrole lH-l,2,4-triazol-3-amine

AMS ammonium εulfamate aεula methyl [(4-aminophenyl)εulfonyl]- carbamate atrazine 6-chloro-N-ethyl-N ^• -(1-methylethy1)- 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 benεulfuron 2-t[[[[(4,6-dimethoxy-2-pyrimi- methyl dinyl)amino]carbonyl]- amino]sulfonyl]methyl]benzoic acid, methyl ester bensulide 0,0-bis(l-methylethyl) S-[2- t(phenylsulfonyl)amino]- ethyl]phoεphorodithioate bentazon 3-(l-methylethyl)-(lH)-2,l,3- benzothiadiazin-4(3H)-one, 2,2-dioxide

Common Name Chemical Name

benzofluor N-[4-(ethylthio)-2-(trifluoro¬ methyl)phenyljmethaneεulfonamide benzoylprop N-benzoyl-N-(3,4-dichlorophenyl)-DL- alanine bifenox methyl 5-(2,4-dichloroρhenoxy)-2- nitrobenzoate bromacil 5-bromo-6-methyl-3-(l-methylproρyl)- 2,4(1H,3H)pyrimidinedione bromoxynil 3,5-dibromo-4-hydroxybenzonitrile butachlor N-(butoxymethyl)-2-chloro-N-(2,6- diethylphenyl)acetamide buthidazole 3-[5-(l,l-dimethylethyl)-l,3,4-thia- diazol-2-yl]-4-hydroxy-l-methyl-2- imidazolidinone butralin 4-(1,1-dimethylethy1)-N-(1-methyl- propyl)-2,6-dinitrobenzenamine butylate S-ethyl biε(2-methylpropyl)- carbamothioate cacodylic dimethyl arεinic oxide acid

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

CDEC 2-chloroallyl diethyldithiocarbamate

CGA 142,464 3-(4,6-dimethoxy-l,3,5-triazin-2-yl)- l-[2-(2-methoxyethoxy)-phenyl- εulfonyl]-urea chloramben 3-amino-2,5-dichlorobenzoic acid chlorbromuron 3-(4-bromo-3-chlorophenyl)-l-methoxy-l- methylurea chlofi uron 2-[[[t(4-chloro-6-methoxy-2-pyrimi- ethyl 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 chlorεulfuron 2-chloro-N-[t(4-methoxy-6-methyl-l,3,5- triazin-2-yl)amino]carbonylJbenzene- sulfonamide chlortoluron N'-(3-chloro-4-methylphenyl)-N,N- dimethylurea cinmethylin exo-1-methy1-4-(1-methylethyl)-2-[(2- methylphenyl)methoxy]-7-oxabicyclo- [2.2.l]heρtane clethodim (E,E)-(±)-2-[l-[[(3-chloro-2-ρropenyl)- oxy]imino]propyl]-5- [2-(ethylthio)- propyl]-3-hydroxy-2-cyclohexen-l-one clomazone 2-t(2-ch?orophenyl)methyl]-4,4-dimethyl- 3-iεoxazolidinone cloproxydim (E,E)-2-[l-[ t(3-chloro-2-propenyl)oxy)- imino]butyl]-5-[2-(ethylthio)propyl]- 3-hydroxy-2-cyclohexen-l-one clopyralid 3,6-dichloro-2-pyridinecarboxylic acid

CMA calcium εalt of MAA cyanazine 2-[[4-chloro-6-(ethylamino)-l,3,5-tri- azin-2-yl]amino]-2-methylpropanenitrile cycloate S-ethyl cyclohexylethylcarbamothioate cycluron 3-cyclooctyl-l,1-dimethylurea cyperquat 1-methy1-4-phenylpyridinium cyprazine 2-chloro-4-(cyclopropylamino)-6-(iso- propylamino)-s-triazine

Common Fame Chemical Name

cyprazole N-[5-(2-chloro-l,l-dimethylethyl)-l,3,4- thiadiazol-2-yl]cyclopropanecarbox- amide cypromid 3' ,4'-dichlorocyclopropanecarboxanilide dalapon 2,2-dichloropropanoic acid dazomet tetrahydro-3,5-dimethyl-2H-l,3,5-thia- diazine-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)biε(l- 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-diethylpheny1)- glycine difenzoquat l,2-dimethyl-3,5-diphenyl-lH-pyrazolium dimepiperate S-1-methyl-l-phenylethylρiperidine- 1-carbothioate dinitramine N ³ ,N ³ -diethyl-2,4-dinitro-6-(trifluoro¬ methyl)-!,3-benzenediamine dinoseb 2-(l-methylpropyl)-4,6-dinitrophenol diphena id , -dimeth l-α-phenylbenzeneacetamide

Common Name Chemical Name

dipropetryn 6-(ethylthio)-N,N'-biε(1-methylethyl)- l,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-l,3,5-triazin- 2-yl)amino]carbonyl]amino]sulfonyl]- 2-thiophenecarboxylic acid, methyl ester

DSMA diεodium εalt of MAA dymron N-(4-methylphenyl)- ^• -(1-methyl- 1-ρhenylethyl)urea endothall 7-oxabicyclo[2.2.l]heptane-2,3-dicarbox- ylic acid

EPTC S-ethyl dipropylcarbamothioate esprocarb S-benzy1-N-ethy1-N-(1,2-dimethyl)- (SC2957) propyl)thiolearbamate ethalfluralin N-ethyl-N-(2-methyl-2-propenyl)-2,6- dinitro-4-(trifluoromethyl)- benzenamine ethofumeεate (±)-2-ethoxy-2,3-dihydro-3,3-dimethyl- 5-benzofuranyl methaneεulfonate fenac 2,3,6-trichlorobenzeneacetic acid fenoxaprop (+)-2-[4-[(6-chloro-2-benzoxazolyl)oxyJ- ρhenoxy]proρanoic acid fenuron ,N-dimethy1-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-pyri- dinyl]oxy]phenoxy]propanoic acid fluazifop-P (R)-2-[4-[[5-(trifluoromethyl)-2-pyri- dinyl]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)-l-[3-(tri- idone fluoromethyl)phenyl]-2-pyrrolidinone fluorodifen p_-nitrophenyl α,α,α-trifluoro-2-nitro- E-tolyl ether fluorogly- carboxymethyl 5-[2-chloro-4-(tri- cofen fluoromethyl)phenoxy]-2-nitrobenzoate fluridone l-methyl-3-phenyl-5-[3-(trifluoro¬ methyl)phenyl]-4(1H)-pyridinone fo esafen 5-[2-chloro-4-(trifluoromethyl)phenoxy]- N-(methylεulfonyl)-2-nitrobenzamide fosamine ethyl hydrogen (aminocarbonyl)- phoεphate glyphoεate N-(phoεphonomethy1)glycine haloxyfop 2-[4-[[3-chloro-5-(trifluoromethyl)-2- pyridinyl]oxy]phenoxy]propanoic acid hexaflurate potaεεium hexafluoroarεenate hexazinone 3-cyclohexyl-6-(dimethylamino)-l-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-isoρropyl- 4-meth l-5-oxo-2-imidazolin-2-yl)- E-toluic acid, methyl ester

Common Name Chemical Name

imazapyr (±)-2-[4,5-dihydro-4-methyl-4-(1-methyl¬ ethyl)-5-oxo-lH-imidazol-2-yl]-3- pyridinecarboxylic acid imazaquin 2-[4,5-dihydro-4-methyl-4-(1-methyl¬ ethyl)-5-oxo-lH-imidazo1-2-yl]-3- quinolinecarboxylic acid imazethapyr (±)-2-[4,5-dihydro-4-methyl-4-(1-methyl¬ ethyl)-5-oxo-lH-imidazol-2-yl]-5- ethyl-3-pyridinecarboxylic acid ioxynil 4-hydroxy-3,5-diiodobenzonitrile iεopropalin ^* 4-(l-methylethyl)-2,6-dinitro-N,N- dipropylbenzenamine iεoproturon N-(4-isopropylphenyl)-N* ,N'-dimethylurea isouron N'-[5-(l,l-dimethylethyl)-3-iεoxazolyl]- N,N-dimethylurea isoxaben N-[3-(l-ethyl-l-methylρroρyl)-5- iεoxazolyl]-2,6-dimethoxybenzamide karbutilate 3-[t(dimethylamino)carbonyl]amino]- phenyl-(1,1-dimethylethy1)carbamate lactofen (±)-2-ethoxy-l-methyl-2-oxoethyl 5-[2- chloro-4-(trifluoromethyl)phenoxy]- 2-nitrobenzoate lenacil 3-cyclohexyl-6,7-dihydro-lH-cyclopenta- pyrimidine-2,4(3H,5H)-dione linuron N'-(3,4-dichloroρhenyl)-N-methoxy-N- methylurea

MAA methylarεσnic acid MAMA monoammonium εalt of MAA MCPA (4-chloro-2-methylphenoxy)acetic acid MCPB 4-(4-chloro-2-methylphenoxy)bu anoic 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)- εulfonyl]amino]phenyl]acetamide methal- N-(2-methyl-2-propenyl)-2,6-dinitro-N- propalin propyl-4-(trifluoromethyl)benzenamide methabenz- l, 3-dimethyl-3-(2-benzothiazolyl)urea thiazuron metham methylcarbamodithioic acid methazole 2-(3,4-dichlorophenyl)-4-methy1-1,2,4- oxadiazolidine-3,5-dione methoxuron N'-(3-chloro-4-methoxyphenyl)-N,N- dimethylurea metolachlor 2-chloro-N-(2-ethyl-6-methylphenyl)-N- (2-methoxy-l-methylethyl)acetamide metribuzin 4-amino-6-(1,1-dimethylethyl)-3-(methyl- thio)-l,2,4-triazin-5(4H)-one metεulfuron 2-[[[t(4-methoxy-6-methyl-l,3,5-tri- methyl azin-2-yl)amino]carbonyl]- amino] ulfonyl]benzoic acid, methyl eεter

MH 1,2-dihydro-3,6-pyridazinedione molinate S-ethyl hexahydro-lH-azepine-1-carbo- thioate

Common Name Chemical Name

monolinuron 3-(p_-chlorophenyl)-1-methoxy-l-methy1- urea monuron N'-(4-chlorophenyl)-N,N-dimethylurea monuron TCA Salt of monuron and TCA MSMA monoεodium εalt of MAA napropamide N,N-diethyl-2-(l-naphthalenyloxy)- propanamide naptalam 2- 1(1-naphthalenylamino)carbonyl]- benzoic acid neburon 1-buty1-3-(3,4-dichlorophenyl)-l-methy1- urea nitralin 4-(methylεulfonyl)-2,6-dinitro-N,N- dipropylaniline nitrofen 2,4-dichloro-l-(4-nitrophenoxy)benzene nitrofluorfen 2-chloro-3.-(4-nitrcphenoxy)-4-(tri- fluoromethyl)benzene norea N,N-dimethyl-N'-(octahydro-4,7-methano- lH-inden-5-yl)urea 3ao,- 4α,5α,7α,7aα-iεomer norflurazon 4-chloro-5-(methylamino)-2-[3-(tri- fluoromethyl)phenyl]-3(2H)- pyridazinone oryzalin 4-(dipropylamino)-3,5-dinitro- benzeneεulfonamide oxadiazon 3-[2,4-dichloro-5-(l-methylethoxy)- phenyl]-5-(l,1-dimethylethyl)- l,3,4-oxadiazol-2(3H)-one oxyfluorfen 2-chloro-l-(3-etho^y-4-nitroρhenoxy)-4- (trifluoromethy1)benzene paraquat 1,1'-dimethy1- , '-dipyridinium ion

Common Name Chemical Name

pebulate S-propyl butylethylcarbamothioate pendimethalin N-(l-ethylpropyl)-3,4-dimethyl-2,6- dinitrobenzenamine perfluidone l,l,l-trifluoror-N-[2-methyl-4-(phenyl- εulfonyl)phenyl]methaneεulfonamide phenmedipham 3-[(methoxycarbonyl)amino]phenyl (3- methylphenyl)carbamate picloram 4-amino-3,5,6-trichloro-2-ρyridine- carboxylic acid

PPG-1013 5-[2-chloro-4-(trifluoromethyl)- phenoxy]-2-nitroacetophenone oxime-O-acetic acid, methyl ester pretilachlor α-chloro-2,6-diethyl-N-(2-propoxy- ethyl)acetanilide procyazine 2-[[4-chloro-6-(cyclopropylamino)-l,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 ^• -biε(1-methylethyl)-1,3,5- triazine-2,4-diamine prometryn N,N'-biε(1-methylethyl)-6-(methylthio)- 1,3,5-triazine-2,4-diamine pronamide 3,5-dichloro-N-(l,l-dimethyl-2-propyn- yl)benzamide propachlor 2-chloro-N-(1-methylethyl)-N- phenylacetamide propanil N-(3,4-dichlorophenyl)propanamide propazine 6-chloro- ,N'-biε(1-methylethyl)- 1,3,5-triazine-2,4-diamine propham 1-methylethyl phenylcarbamate

Common Name Chemical Name

proεulfalin N-[[4-(dipropylamino)-3,5-dinitro- phenyl]εulfonyl]-S,S-dimethylεulfil- imine prynachlor 2-chloro-N-(l-methyl-2-propynyl)acet- anilide pyrazolate 4-(2,4-dichlorobenzoyl)-l,3-dimethyl- pyrazol-5-yl-p.-tolueneεulphonate pyrazon 5-amino-4-chloro-2-phenyl-3(2H)- pyridazinone pyrazosulfuron ethyl 5-[3-(4,6-dimethoxypyrimidin-2- ethyl yl)ureadoεulfonyl]-l-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-methylpropy1)- 1,3,5-triazine-2,4-diamine εethoxydim 2-[l-(ethoxyimino)butyl]-5-[2-(ethyl- thio)propyl]-3-hydroxy-2-cyclohexen- 1-one εiduron N-(2-methylcyclohexy1)-N'-phenylurea εimazine 6-chloro-N,N'-diethyl-l,3,5-triazine- 2,4-diamine

SK-233 1-(α,α-dimethylbenzy1)-3-(4-methyl- phenyl)urea εulfometuron 2-tt[[( ,6-dimethyl-2-pyrimidinyl)- methyl a ino]carbonyl]amino]sulfonyl]- benzoic acid, methyl ester

TCA trichloroacetic acid tebuthiuron N-[5-(1,1-dimethylethyl)-1,3, -thiadi- azol-2-yl]-N,N'-dimethylurea terbacil 5-chloro-3-(1,1-dimethylethyl)-6- methyl-2,4(lH,3H)-pyrimidinedione

Common Name Chemical Name

terbuchlor N-(butoxymethyl)-2-chloro-N-[2-(l,l- dimethylethyl)-6-methylphenyl]- acetamide terbuthyl- 2-(ieχt-butylamino)-4-chloro-6-(ethyl- azine amino)-_s.-triazine terbutol 2,6-di-t£ii-butyl-E-tolyl methylcar- bamate terbutryn N-(1,1-dimethylethyl)- '-ethy1-6- (methylthio)-1,3,5-triazine- 2,4-diamine thiobencarb S-t(4-chlorophenyl)methyl] diethylcar- bamothioate triallate S-(2,3,3-trichloro-2-propenyl) biε(1- methylethyl)carbamothioate tribenuron 2-[t[[N-(4-methoxy-6-methyl-l,3,5- methyl triazine-2-yl)-N-methylamino]- carbonyl]amino]εulfonyl]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-(tri- fluoromethyl)benzenamine trimeturon 1-(E-chlorophenyl)-2,3,3-trimethylpεeu- dourea

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-dimethylpheny1)-N- (1-methylethyl)acetamide

Herbicidal properties of the subject compounds were diεcovered in a εeries of greenhouse tests. Test procedures and results follow.

COMPOUND TABLE

A = OR ¹

¹

CH ₃

CH ₃

OCH _:

OCH _;

CH ₃

CH ₃

OCH;

OCH;

OCH _;

OCH,

OCH _;

OCH _;

CH ₃

OCH,

OCH,

CH ₃ OCH-

42 N(CH ₃ ) ₂ CHFCH ₃ OCH ₃ OCH- 156-158

IESI Δ

Seeds of barley (Hordeum vuloare.. barnyardgrasε (Echinochloa crus-oalli). cheatgrasε (£r2mu£ secalinusϊ. cocklebur (Xanthium pensylvanicum) . corn (Z^i πiaϊ_i), cotton (Gossypium hirsutum) . crabgraεε (Digitaria spp.), giant foxtail (Setaria faberi) . morningglory (Ioomoea spp.), rice (Orvza sativaϊ , sorghum (Sorohum bicolor) , soybean

⁽ Glvcine maz) , sugar beet (fijeta. VUlgaris), velvetleaf ⁽ Abutilon theoohrasti ⁾ , wheat (Triticum aestivum) , and wild oat (Avena fatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals disεolved in a non-phytotoxic solvent. At the same time, theεe crop and weed εpecies 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 εpecies were compared to controls and visually evaluated. Plant iresponεe ratingε, 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.

Table A

CO.MPOUND

Rate (50 g/ha) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 36

POSTEMERGENCE

Barley 9 9 8 3 9 9 9 8 7 0 2 5 9 0 6 9 2 7 9 8 0 9 3 0 9 0 0 8 9 8 6 0

Barnyardgrass 9 9 9 9 , 10 9 9 9 9 8 9 9 10 9 9 10 7 9 9 8 1 9 9 7 9 7 8 9 9 9 7 7

Cheatgrass 9 10 10 9 9 9 9 9 9 3 9 9 9 10 9 9 8 9 9 8 0 9 9 9 9 8 7 9 9 6 6 9

Cocklebur 10 10 10 10 9 10 10 10 9 9 9 10 10 9 10 10 9 10 10 10 9 10 10 9 10 9 10 9 10 10 10 9

Corn 9 9 9 6 5 9 9 3 6 0 9 9 9 7 7 10 4 9 9 8 2 10 9 0 9 0 5 10 9 8 3 2

Cotton 10 9 9 9 9 10 9 9 9 9 10 9 10 9 9 10 10 9 9 9 9 10 9 9 9 9 9 10 9 9 9 10

Crabgrass - 9 8 5 9 10 6 8 7 2 9 8 6 8 6 9 0 6 3 1 0 3 1 4 9 0 0 9 4 5 4 0

Giant foxtail 9 9 9 8 9 10 9 9 6 5 5 9 8 3 8 9 3 9 9 3 0 10 6 4 9 0 2 8 7 8 6 1

Morningglory 9 10 10 10 8 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 9 10 10 10 9 10 10 9 10 10 10 9

Nutsedge 9 10 10 10 - 10 10 10 10 6 10 - 10 10 10 10 9 9 10 - - 10 10 9 10 9 8 9 9 10 10 0

Rice 9 9 9 9 9 9 9 9 9 4 9 9 8 7 9 9 4 9 9 9 5 9 9 8 9 4 3 8 9 8 7 5

Sorghum 9 9 9 9 9 9 10 9 9 9 9 9 9 8 9 9 9 9 9 9 8 9 - 9 - 6 4 9 9 6 7 6

Soybean 9 9 9 7 9 9 9 9 9 9 9 9 9 6 9 9 9 9 9 7 9 9 9 9 9 9 9 9 9 9 7 9

Sugar beet 9 9 10 10 9 10 9 9 10 10 10 9 10 9 9 9 9 10 10 9 9 10 10 10 9 10 10 10 10 9 9 10

Velvetleaf 10 10 10 9 10 10 9 10 10 9 9 10 10 9 9 10 9 9 9 - - - 9 9 10 9 9 - 9 9 10 9

Wheat 9 9 9 7 9 9 9 9 7 2 7 5 9 2 8 9 0 9 9 3 0 9 3 0 9 0 0 8 6 2 0 0

Wild oat 9 9 7 5 9 9 7 8 6 4 3 3 8 4 6 9 2 8 5 3 0 7 4 2 9 0 0 6 5 0 3 3

TEST B

Seeds of barley (Hordeum vulqare)/ barnyardgrasε (Echinochloa crus-oalli). blackgrass (Alopecurus mvosuroides) . cheatgrass (Promus secalinus), chickweed (Stellaria media.), cocklebur (Xanthiu pensvivanicum), corn (zea mays) cotton (Gossvpjum hirsutum) . crabgrass (Pigitaria spp.), bedεtraw (Galium aparine) . giant foxtail (Setaria faberii) . lambsguarters (Chenopodium album), morningglory (Ipomoea hederacea) . rape (Brassica naPUS) , rice (Orvza sativa) , sorghum (Sorohum b color), soybean (Glvcine max) . sugar beet (Beta vulgarjs) , velvetleaf (Abutilon theophrasti) . wheat (Triticum aestivum)/ wild buckwheat ⁽ Polvoonu convolvulus) . and wild oat (Avena jLaJtua.) and purple nutsedge (Cyperus rotunduε) tuberε were planted and treated preemergence with teεt chemicalε diεεolved in a non-phytotoxic εolvent. At the εa e time, theεe crop and weed εpecies 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 treatmentε. Treated plantε and controlε were maintained in a greenhouse for twelve to sixteen days, after which all specieε were compared to controlε and viεually 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-αalli) . blackgraεε (Alopecurus mvosuroides) , chickweed (Stellaria media.) , cocklebur (Xanthium pensvlvanicum) , corn (Zea ays) cotton (Gossvoium hirsutum) . crabgrass (Dioitaria spp.), downy brome (finaπu≤. tectorum)/ giant foxtail (Setaria faberi). green foxtail

(Setaria viridis) . jimsonweed (Datura Stramonium)/ johnεongraεs (Sorghum halepense) . lambsquarters (Chenopodiu aU≥um) / morningglory (Ipomoea spp.), rape (Brassica naous) . rice (Orvza sativa) . sicklepod (£≤__£J__2. obtusifolia ⁾ , soybean (Glycine max) , sugar beet (Beta vulgaris ⁾ , teaweed (fijjla. spinosa), velvetleaf (AbutiIon theoohrasti) . wheat (Triticum aest vum)/ wild buckwheat (Polygonum convolvulus) . and wild oat (Avena fatua) and purple nutsedge (Cvperus rotundus) tubers were planted and treated preemergence with test chemicalε diεεolved in a non-phytotoxic εolvent. At the εame time, theεe crop and weed εpecies were alεo treated with postemergence applications of test chemicals. Plantε ranged in height from two to eighteen cm (two to three leaf εtage) for poεtemergence treatmentε. Treated plantε and controlε were maintained in a greenhouse for approximately 24 days, after which all specieε were compared to controlε and viεually evaluated. Plant reεponse 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.

Table C

COMPOUND

Rate (62 g/ha) 1 2 3 4 5 6 7 8 9 10 11 12 13 15 16 17 18 19 20 22 23 24 25 26 27 28 29 3031 36

Table C

COMPOUND

Table C

COMPOUND

Table C

COMPOUND

Table C

COMPOUND

Table C

COMPOUND

Table C

Table C

COMPOUND

Rate (1 g/ha) 1 2 3 5 6 7 8 9 11 12 13 15 16 17 18 19 20 22 23 24 25 26 27 28 29 30 31 36

PREEMERGENCE

Barley 2 3 0 O 2 O 0 O O O 2 O 3 O 3 O O O 0 O O 0 O 0 2 O 0 0

Blackgrass 5 5 3 3 3 0 0 - 0 0 4 0 4 0 6 3 3 0 0 0 0 0 2 0 0 0 0 0

Chickweed 5 5 4 0 5 7 0 5 0 6 6 0 7 0 4 0 0 7 5 0 3 0 0 0 3 3 0 0

Cocklebur 0 3 3 8 2 0 0 0 3 6 7 3 5 0 7 7 6 6 3 0 5 0 - 4 - 3 7 0

Corn - 2 0 0 0 0 0 0 0 0 2 0 0 0 2 0 2 2 0 0 5 0 4 0 0 0 0 0

Cotton 3 0 0 0 0 0 0 0 0 4 4 4 3 0 2 0 0 5 3 3 6 0 0 3 0 0 0 0

Crabgrass 7 5 4 3 5 3 0 8 3 3 0 5 5 0 0 0 0 3 0 0 5 0 0 0 3 4 3 2

Downy brome 4 3 0 0 2 0 0 0 0 0 0 0 J 0 3 0 0 0 0 0 0 0 0 0 3 0 0 0

Giant foxtail 4 3 0 5 4 2 4 0 0 0 0 0 0 0 4 0 0 0 0 0 3 0 0 0 0 0 0 0

Green foxtail 3 4 0 2 4 0 0 0 0 2 0 0 0 5 0 0 5 3 0 4 0 0 0 0 0 0 0

Jimsonweed 0 0 0 3 2 3 0 4 0 4 4 4 6 0 2 2 0 6 3 3 7 0 0 0 3 2 3 3

Johnsongrass 2 3 0 0 2 2 0 0 0 0 6 5 b 0 3 0 0 5 0 0 6 0 0 0 0 0 0 0

Lambsquarters 5 8 9 7 3 8 5 - - - - - - - - - - - - - - - 8 - - - - 4

Morningglory 0 3 3 0 0 0 3 3 3 6 4 6 5 0 3 0 0 4 4 3 6 2 0 3 4 4 3 0

Nutsedge 6 5 0 8 3 2 0 0 3 3 4 0 0 0 3 3 0 6 3 0 5 3 - 0 2 3 3 6

Rape 7 8 7 8 7 7 2 3 3 0 5 3 3 0 8 7 5 3 0 0 8 0 3 4 5 0 3 5

Rice Dry Seed 8 4 4 3 4 2 2 3 0 0 3 0 6 0 6 3 0 3 3 0 9 0 0 0 3 0 0 0

Sicklepod 2 0 5 0 0 0 0 0 5 3 5 3 5 0 0 0 - 5 4 5 8 0 0 0 0 0 0 0

Soybean 0 0 0 2 0 0 0 0 0 0 0 0 4 0 2 0 0 3 - 0 2 0 0 0 0 0 0 0

Sugar beet 7 7 7 9 8 9 0 6 3 5 8 6 4 0 6 6 6 8 5 3 7 0 4 5 5 4 6 2

Teaweed 0 0 0 0 2 0 0 0 0 5 3 8 8 0 3 0 3 3 0 4 3 0 0 - 0 0 0 0

Velvetleaf 5 3 0 0 3 3 2 10 3 6 6 3 7 0 5 4 - 7 6 7 8 0 0 - 3 7 3 4

Wheat 3 3 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0

Wild buckwheat 7 3 8 2 7 2 3 3 3 5 6 3 5 0 5 4 3 5 5 0 8 3 0 4 3 0 0 0

Wild oat 4 3 0 0 3 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 2 0 0 0 0

Barnyardgrass 2 0 0 0 2 2 3 0 0 4 7 0 6 0 5 0 0 5 0 0 6 0 2 0 0 0 0 0

TJESI_β

The compounds evaluated in this test were formulated in a non-phytoxic solvent and applied to the soil εurface before plant εeedlingε emerged (preemergence application), to water that covered the εoil 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 poεtemergence 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 teεt, Plant εpecieε in the preemergence and poεtemergence teεtε conεiεted of barley (Hordeu vvlqare) , bedstraw (gal um SPar ne) , blackgrass (Alopecurus myosu OJfles) , chickweed (Stellaria media) corn (Zea mavs) . cotton (Gossvpium hirsutum) . crabgrasε (Dioitaria sanαuinalis) . downy brome

(Bromus tectorum)/ giant foxtail (Setaria faberii) . lambεquarterε (Chenopodium album) . morningglory (Ipomoea deracea) , pigweed (A aranthusretrofleτus. , rape (Brassica nSPUS) , ryegraεε (Lolium multiflorum) , εorghum (Sorghum bicolor) ♦ soybean (Glycine max), εpeedwell (Veronica persica sugar beet (Beta VUlgaris) , velvetleaf (AbutiIon theoohrasti ⁾ , wheat (Triticum aestivum) , wild buckwheat (Polvoonum convolvulus) . and wild oat (Avena fatua) . All plant species were planted one day before application of the compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test. Plant species in the paddy test consisted of barnyardgrass

(Echinochloa crus-qalli) , rice Q ZA sativa) , and umbrella sedge (Cvoerus 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 teεt reεult.

Table D

COMPOUND

Rate (62 g/ha) 32 35 40 41 42 43 PREEMERGENCE

Barley Igri 9 5 4 2 9 2

Bedεtraw 9 9 10 10 10 10

Blackgraεs 9 7 9 7 9 10

Chickweed 10 - 10 9 9 9

Corn 8 10 2 3 7 3

Cotton 6 9 9 10 10 7

Crabgrass 8 10 7 8 5 7

Downy brome 10 7 7 7 10 7

Giant foxtail 7 9 4 6 7 7

Lambsquarterε 10 - 10 9 10 10

Morningglory 8 8 10 10 9 8

Pigweed 10 10 10 9 10 9

Rape 10 9 10 10 9 10

Ryegrass 10 10 6 6 7 8

Sorghum 9 10 9 7 10 9

Soybean 7 9 7 0 9 4

Speedwell 10 9 10 9 10 9

Sugar beet 10 9 9 10 10 10

Velvetleaf 8 9 9 8 9 9

Wheat 9 7 4 2 9 4

Wild buckwheat 9 8 9 8 9 9

Wild oat 6 5 5 3 3 3

Table D

COMPOUND

Rate (31 g/ha) 32 33 34 35 37 38 39 40 41 42 43 POSTEMERGENCE

Barley Igri 9 9 9 10 6 10 4 9 4 9 5

Bedεtraw 10 10 10 10 10 10 10 10 10 10 10

Blackgraεε 9 9 9 10 10 10 9 10 9 10 10

Chickweed 10 10 10 10 10 10 10 10 10 10 10

Corn 10 10 10 10 8 10 7 10 8 10 7

Cotton 10 10 10 10 10 10 10 10 10 10 9

Crabgraεε 6 7 10 10 0 8 0 5 0 0 3

Downy brome 8 10 10 10 5 10 4 9 5 10 7

Duck εalad - - - - ... - ... - v β -

Giant foxtail 8 10 10 10 6 10 6 10 5 7 8

Lambεquarterε 10 10 10 10 10 10 - 10 10 10 10

Morningglory 10 8 8 10 10 10 10 10 10 10 10

Pigweed 10 10 10 10 10 10 0 10 8 10 9

Rape 10 10 10 10 10 10 10 10 10 10 10

Ryegrass 9 10 10 10 0 10 4 10 2 4 7

Sorghum 10 10 10 10 10 10 7 10 6 10 10

Soybean 10 10 10 10 10 10 10 10 7 10 9

Speedwell 9 8 8 10 5 8 9 9 10 8 8

Sugar beet 10 10 10 10 10 10 10 10 10 10 10

Velvetleaf 10 10 10 10 8 10 10 10 10 9 10

Wheat 9 9 9 9 4 9 2 9 0 8 7

Wild buckwheat 10 10 10 10 10 10 9 10 10 9 7

Wild oat 8 9 10 7 3 9 4 5 4 4 6

Barnyardgrass 9 8 9 9 8 9 7 9 8 9 9

Rice Japonica 8 8 9 8 7 9 8 8 8 8 9

Umbrella sedge 10 9 10 10 9 9 9 9 9 9 9

IE£I_E

Seeds of barnyardgrass (Echinochloa crus-σalli), cocklebur (Xanthium pensylvan cuπi), 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 VJridis)/ ivyleaf morningglory (Ipomoea hederacea) . jimsonweed (Datura stramonium) . johnεongraεs (Sorαhum halepense) . ladysthumb smartweed (Polγgonum perslcaria) , lambsquarterε (Chenopodium aUaum) , redroot pigweed (Amaranthus retroflexus) , sorghum (Sorghum bicolor ⁾ , soybean (Glvcine ma ) , and velvetleaf (Abutilon theophrasti) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals disεolved in a non-phytotoxic εolvent. Theεe crop and weed εpecies were also treated with postemergence applications of test compounds. Plants ranged in height from two to twenty-five cm for postemergence treatmentε.

Treated plantε and controlε 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 baεed on a scale of 0 to 10 where 0 iε no effect and 10 iε complete control. A daεh (-) reεponεe means no teεt result.

Table E

COMPOUND Rate (64 g/ha) 5 7 8 9 10 24 POSTEMERGENCE

Barnyardgraεε 10 10 10 10 8 9 Cocklebur 10 10 10 10 10 10 Corn

Crabgraεε Fall panicum Giant foxtail Green foxtail Ivlf mrninglory Jimsonweed Johnsongraεε Ladyεthmb εmtwd Lambsquarters Perlite corn Purple nutεedge Redroot pigweed Sorghum Soybean Velvetleaf

Table E

Table E

COMPOUND

TEST F

Plastic potε were partially filled with silt loam εoil. The soil waε then saturated with water. Indica and Japonica rice (Oryza sativa) seedlingε at the 2.0 to 2.5 leaf stage, seeds selected from barnyardgrasε (Echinochloa crus-σalli), bulruεh (Scirpus mucronatus). duck salad (Heteranthera Pi osa) umbrella sedge (cvoerus difformis) and tubers selected from waterchestnut (Eleocharis εpp.), 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 greenhouεe for approximately 21 dayε, after which all species were compared to controls and visually evaluated. Plant response ratingε, εummarized in Table F, are reported on a 0 to 10 εcale where 0 iε no effect and 10 iε complete control. A daεh (-) response meanε no teεt reεult.

Table F

Table F

Table F

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 εoil waε uεed 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 adjuεted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practiceε. Crop and weed εpecieε include winter barley (Hordeum vuloare cv. 'Igri'), bedεtraw (Galium aparine) . blackgraεε (Alopecuru≤ mvosuroides) , chickweed (Stellaria media) , downy brome (Broirius tectorum) , field violet ⁽ Viola arvensis)/ green foxtail (Setaria viridis) . kochia (Kochia SCQparia)/ lambεquarterε (Chenopodium album) . Perεian εpeedwell (Veronica persica) . rape (Brassica n jElli cv. 'Jet Neuf), ryegrasε (Loliu multiflorum) . sugar beet (fie±a vulqaris cv. *US1'), sunflower (Helianthus jωnilllfi cv. 'Rusεian Giant'), spring wheat (Triticu aestivum cv. 'ERA'), winter wheat (Triticum aestivum cv. 'Talent'), wild buckwheat (Polvαonum convolvulus) . wild mustard (SinapJS arvensis) . wild oat (Avena fatua) . and wild radish (Raohanus raphanistru ) . 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 stageε of tillering. Treated plantε and untreated controlε were maintained in a greenhouεe for approximately 21 to 28 dayε, after which all treated plantε were compared to untreated controls and visually evaluated. Plant responεe ratingε, εummarized in Table G, are baεed upon a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash responεe (-) meanε no teεt reεult.

Table G

Table G

COMPOUND

Rate (64 g/ha) 34 35 37 39 POSTEMERGENCE

Bedstraw 10 8 10 10

Blackgrass (1) 4 8 6 4

Blackgrass (2) 5 8 5 4

Chickweed 10 10 10 10

Downy brome 9 10 6 5

Field violet 6 5 8 5

Green foxtail 10 9 5 2

Kochia - 9 - -

Lambsquarters 10 8 - -

Perεn Speedwell 7 3 3 6

Rape 10 10 10 10

Ryegraεε 10 10 0 0

Sugar beet 10 10 10 10

Sunflower 10 10 10 10

Wheat (Spring) 9 10 2 2

Wheat (Winter) 9 10 1 2

Wild buckwheat 10 9 9 8

Wild mustard 10 10 10 10

Wild oat (1) 10 10 0 2

Wild oat (2) 10 10 0 2

Wild radish 10 10 10 10

Winter Barley 10 10 2 2

Table G

COMPOUND

Rate (32 g/ha) 34 35 37 39

PREEMERGENCE Bedstraw 10 8 7 6 Blackgrasε (1) 2 7 0 0 Blackgraεε (2) 2 7 0 0 Chickweed 10 10 9 5 Downy brome 5 10 0 0 Field violet 8 10 9 4 Green foxtail 10 10 0 0 Kochia - 8 - -

Lambsquarters - 10 - - Persn Speedwell 10 8 8 5 Rape 10 10 10 9 Ryegrass 4 10 0 0 Sugar beet 10 10 10 10 Sunflower 6 9 4 2 Wheat (Spring) 2 7 0 0 Wheat (Winter) 1 6 0 0 Wild buckwheat 3 6 4 2 Wild mustard 10 10 10 9 Wild oat (1) 2 4 0 0 Wild oat (2) 2 5 0 0 Wild radish 7 10 7 4 Winter Barley 4 10 0 0

Table G

COMPOUND

Rate (16 g/ha) 34 35 37 39 POSTEMERGENCE

Bedstraw 8 4 6 5

Blackgrass (1) 2 3 2 0

Blackgrass (2) 2 4 2 0

Chickweed 9 9 10 7

Downy brome 6 8 0 0

Field violet 4 2 3 2

Green foxtail 10 8 2 0

Kochia 4

Lambsquarters 9 3 -

Perεn Speedwell 3 0 0 2

Rape 10 10 10 10

Ryegraεε 10 8 0 0

Sugar beet 9 9 10 10

Sunflower 10 10 10 10

Wheat (Spring) 5 5 0 0

Wheat (Winter) 5 4 0 0

Wild buckwheat 7 3 4 5

Wild muεtard 10 10 10 10

Wild oat (1) 7 7 0 0

Wild oat (2) 6 7 0 0

Wild radiεh 10 10 10 10

Winter Barley 10 9 0 0

Table G

Table G

Table G

Table G

Seeds of alfalfa (Medicaαo sativa) . bean ⁽ Phaseolus vulgaris) , bluegrass (Efia pfBtensis) , cabbage (Brassica raoa.. carrot (Daucus sativa)/ corn (Z≤.a mays) , flax (itiaum vsitatissirouπ.)/ lettuce ⁽ Lactuca sativa). lupine (LuPJnuS aUau≤.)/ oats (ftvena sativa), onion f-Alliu csEa) pea (sativum) , peanut (Arachis hvooαaea) . potato (Solanum tuberosum.. rye

(Secale cereal) . εorghum (Sorαhum bicolor) . εunflower (Helianthvs annuus), and tomato (Lycopersicon eεculentum) were planted and treated preemergence with a test chemical disεolved in a non-phytotoxic εolvent. Theεe crop species were also treated with poεtemergence applicationε 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 controlε 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.