JP2799246B2 - Crop-selective herbicidal sulfonamides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Reference is made to before and after related applications. This is the application number 07/50, filed on April 4, 1990.
3,182 partially filed applications.

BACKGROUND OF THE INVENTION The present invention relates to novel sulfonamides and their use as crop-selective herbicides. The compounds of the present invention exhibit excellent control of weeds while also combining corn safety.

WO89 / 09214 has the formula: Wherein R is, inter alia, C ₁ -C ₄ alkyl; R ₁ is, inter alia, C ₁ -C ₂ haloalkyl, CH ₂ CN or CH _2
2 OCH ₃ , and X is NCH ₃ , N (CH ₃ ) ₂ or N (CH ₃ ) OCH ₃ ].

This reference does not teach or suggest the compounds of the present invention.

European patent application 120,814 has the formula Wherein A is C ₁ -C ₆ haloalkyl, R ¹ is H, halogen, NO ₂ , CN, C ₁ -C ₄ alkyl, C ₁ -C ₄
Haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio,
C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, COR ⁶ , NR ⁷ R ⁸ , CONR ⁹ R ¹⁰ or SO ₂ NR ¹¹ R ¹² ,
And R ⁶ is C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy, C ₁
-C ₄ alkylthio, C ₂ -C ₆ alkoxyalkoxy, hydrogen,
C ₁ -C ₄ alkyl or C ₁ -C ₄ haloalkyl].

Although this reference broadly covers the compounds of the present invention, it does not teach or suggest these particular compounds or their herbicidal uses.

Moreover, there is still a need for herbicides due to global food shortages. In addition, there is a particular need for herbicides that are selective for important crops such as, for example, corn. According to the present invention, such compounds have been found.

SUMMARY OF THE INVENTION More particularly, the present invention relates to novel compounds of formula I, agriculturally suitable compositions containing them and their use as pre- and / or post-emergence herbicides or plant growth regulators. Includes usage: Wherein A is OR ¹ or N (CH ₃ ) ₂ , R ¹ is C ₁ -C ₃ alkyl, CH ₂ CH = CH ₂ , CH ₂ C≡CH, CH ₂ CH ₂ C
l 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, where X is OCH ₃ when Y is Cl] and their agriculturally suitable salts.

In the above definitions, the term "alkyl" refers to straight or branched chain alkyl, such as methyl, ethyl, n
-Propyl or isopropyl. The total number of carbon atoms in the substituent is indicated by the Ci-Cj suffix, where i and j are numbers 1-3. For example, a C ₁ -C ₃ alkyl would represent methyl to propyl (both n -propyl and isopropyl).

Preferred for reasons of increased ease of synthesis and / or relatively large herbicide efficacy and / or crop safety are: 1.A is OR ¹ and R ¹ is CH ₃ , CH ₂ CH ₃ Metropolitan or CH (CH _{3) 2,} the compound of formula I, when one of the 2.X and Y is CH _3, the other of X and Y is other than OCH _3, with compounds of the preferred term 1 is there.

Particularly preferred for reasons of maximum safety against corn are: 3- (cyanomethyl) -2-[[[[[(4,6-dimethyl-2-pyrimidinyl) amino] carbonyl] amino]
Sulfonyl] methyl benzoate (Formula I: A is OR ¹ and R ¹ is
CH ₃ , R ² is CH ₂ CN, and X and Y are CH ₃ ).

Particularly preferred for reasons of maximum safety against corn, wheat and barley are: 2-[[[[(4-Chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl]
Methyl-3- (cyanomethyl) benzoate (Formula I: A is OR ¹ , R ¹ is CH ₃ , R ² is CH ₂ CN, X is OCH ₃ , and Y is Cl ), 3- (cyanomethyl) -2-[[[[[(4- (difluoromethoxy) -6-methoxy-2-pyrimidinyl]
Amino] carbonyl] amino] sulfonyl] methyl benzoate (Formula I: A is OR ¹ , R ¹ is CH ₃ , R ² is CH ₂ CN, X is OCH ₃ , and Y is OCF ₂ is H), · 3- (difluoromethyl) -2 - [[[[(4-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] - benzoate (formula I: a is at OR ¹ R ¹ is CH ₃ , R ² is CHF ₂ , X is OCH ₃ and Y is H), 3- (fluoromethyl) -2-[[[[(4-methoxy -2-pyrimidinyl) amino] carbonyl] amino]
Sulfonyl] methyl benzoate (Formula I: A is OR ¹ and R ¹ is
CH ₃ , R ² is CH ₂ F, X is OCH ₃ , Y is H
Is).

Particularly preferred for reasons of maximum safety against wheat and barley are: 2-[[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -3-
(Fluoromethyl) methyl benzoate (Formula I: A is OR ¹ , R ¹ is CH ₃ , R ² is CH ₂ F, X and Y are OCH
₃ )

Particularly preferred for reasons of maximum safety against corn, wheat, barley and rice are: 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl ]
Ethyl-3- (fluoromethyl) benzoate (Formula I: A is OR ¹
R ¹ is CH ₂ CH ₃ , R ² is CH ₂ F, and X is OCH ₃
And Y is Cl).

The present invention also encompasses novel compounds, such as sulfonyl benzoates of formula II, which are useful as intermediates for the preparation of compounds of formula I: Wherein A is OR ¹ or N (CH ₃ ) ₂ , R ¹ is C ₁ -C ₃ alkyl, CH ₂ CH = CH ₂ , CH ₂ C≡CH, CH ₂ CH ₂ C
a l 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, and R ³ is C ₁ -C is ₄ alkyl, R ⁴ is C ₁ -C ₄ alkyl and R ⁵ is C ₁ -C ₄ alkyl, with the proviso, Z ¹ when a is OR ¹ is NHSiR ³ R ⁴ R ⁵ and R ³ , R ⁴ and R ⁵ are C ₁ -C ₃ alkyl].

Preferred for reasons of increased herbicidal activity of the end product of formula I are intermediate products of formula II wherein A is OR ¹ and R ¹ is C ₁ -C ₂ alkyl.

Preferred for reasons of increased ease of synthesis are:
Preferred are those described above wherein R ³ and R ⁴ are CH ₃ and R ⁵ is C (CH ₃ ) ₃ ).

Detailed description of the invention Synthesis The compounds of formula (1) corresponding to formula I can be prepared by one or more of the following methods. The appropriate choice of reaction sequence for a given compound will be known to those skilled in the art.

As shown in Scheme 1, many of the compounds of formula (I) are prepared by reacting a silyl sulfonamide of formula (2) with a pyrimidine carbamate of formula (3). R ³ , R ⁴ , and R ⁵ are independently C ₁ -C ₄ alkyl.

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

Alternatively, certain sulfonamides of formula (4) may be prepared as shown in Scheme 2 and reacted with a pyrimidine carbamate of formula (3) to give a compound of formula (1). it can. 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 4,6
04,131 discloses details on a similar reaction.

Reaction of the sulfonyl chloride of formula (5) with a cyanate anion in the presence of a pyrimidineamine of formula (6) as shown in Scheme 3 gives a compound of formula (1).

The reaction comprises one equivalent of a sulfonyl chloride (5), a pyrimidineamine (6), a metal cyanate such as sodium cyanate, and a catalytic amount of an amine base such as Aliquat.
It is carried out by mixing ^R 336 (tricaprilmethylammonium chloride) in a solvent such as acetonitrile for 0.2 to 10 days. Meanwhile, U.S. Patent 4,60
It is also possible to use tetraalkylammonium cyanates, for example tetraethylammonium cyanate, to carry out this reaction according to the method described in 4,131.

As shown in Scheme 4, the sulfonyl chlorides of formula (5) are converted to trialkylsilylamines of formula (7), for example t
-Butyldimethylsilylamine to produce silylsulfonamides of formula (2).

The reaction is carried out at 0 ° C. to 30 ° C. in a solvent such as dichloromethane in the presence of 1-2 equivalents of amine and 1 equivalent of bicarbonate. JR Bowser and others are Inorganic Chemistr
y), 17 , 1882 (1978) describe a process for preparing silylamines of formula (7).

The sulfonyl chlorides of formula (5) and the silylsulfonamides of formula (2) correspond to intermediates of formula II.

Reaction of the sulfonyl chlorides of formula (5) with no more than 2 equivalents of ammonia or with 1 equivalent of ammonia and 1 equivalent of base as outlined in Scheme 5 gives the sulfonamides of formula (4). it can.

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

The sulfonyl chlorides of formula (5) are prepared by the methods shown in Schemes 6 and 7. As shown in Scheme 6, the sulfur-containing compound of Formula (8) is oxidized using chlorine. R ⁶ is H, alkyl, benzyl or carbamoyl.

The reaction of Scheme 6 comprises reacting a compound of formula (8) with at least 3.0 equivalents of chlorine in a solvent such as acetic acid or propionic acid in the presence of at least 2.5 equivalents of water at -20 ° C to 30 ° C for 0.2 to 5 hours. It is carried out by contacting at. A. Wagenaar is Recl.Trav.Chi
m. Pays-Bas, 101 , 91 (1982) teaches specific reaction conditions for related compounds.

Alternatively, reaction of a compound of formula (8) wherein R ⁶ is H or benzyl with a hypochlorite solution such as, for example, 5% NaOCl can provide sulfonyl chlorides of formula (5). Reaction conditions for similar reactions will be apparent to those skilled in the art and are set forth in European Patent Application 142,152.

As shown in Reaction Scheme 7 below, sulfonyl chlorides of formula (5) can be prepared from the corresponding anilines of formula (9) by a Meirwein reaction.

Yale and Sowinski,
The aniline is diazotized and then reacted with sulfur dioxide and cupric chloride in a manner analogous to the teachings of The Journal of the Organic Chemistry (J. Org. Chem.), 25 , 1824 (1960). Meanwhile, M. Doyle,
The hydrochlorides of anilines of formula (9) can be prepared using sulfur dioxide in a manner similar to the teaching of The Journal of the Organic Chemistry (J. Org. Chem.), 42 , 2426, 2431 (1977). It can be diazotized to give the sulfonyl chlorides (5).

Pyrimidine carbamates of the formula (3) and pyrimidineamines of the formula (6) are described in European Patent Application 72,347, European Patent Application 164,269, European Patent Application 173,49.
8, manufactured by methods described and referenced in U.S. Pat. Nos. 4,540,782 and 4,666,506.

Agriculturally suitable salts of the compounds of formula I are also useful herbicides and can be prepared in a number of ways known in the art. For example, metal salts can be prepared by contacting a compound of formula I with an alkali or alkaline earth metal salt having sufficient basic anion (eg, hydroxide, alkoxide, carbonate or hydroxide). . Quaternary amine salts can be produced by a similar technique.

Salts of the compounds of formula I may also be prepared by exchanging one cation for another. Cation exchange can be carried out by direct contact with an aqueous solution of a salt of a compound of Formula I (eg, an alkali or quaternary amine salt) with a solution containing the cation to be exchanged.
This method is most effective when the salt containing the desired exchanged cation is insoluble in water and can be separated by filtration.

The exchange may be carried out in a column packed with a cation exchange resin containing a cation to be exchanged for an aqueous solution of a salt of a compound of formula I (eg, an alkali metal or quaternary amine salt) with that of the original salt. And the desired product is eluted from the column. This method is useful when the desired salt is water-soluble, for example when it is a potassium, sodium or calcium salt.
Especially useful for:

Acid addition salts useful in the present invention are obtained by reacting a compound of formula I with a suitable acid, for example, p-toluenesulfonic acid, trichloroacetic acid.

The preparation of the compounds of the present 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 the peak position is the internal tetramethyl Reported as ppm from silane. Infrared (IR) peak position is reciprocal centimeter (cm)
^-1 ), and sh indicates the shoulder.

Example 1 Methyl 3- (cyanomethyl) -2-nitrobenzoate Potassium cyanide (6.2 g) in a stirred solution of methanol (100 mL) and water (150 mL) at 0 ° C. with 3- (bromomethyl) -2. -A solution of methyl nitrobenzoate in acetonitrile (24.9 g) was added. Next, 1
8-Crown-6 ether was added. After stirring overnight at room temperature, the reaction was extracted with ethyl acetate. Wash the combined extracts with brine solution, dry over magnesium sulfate, filter, concentrate and chromatograph on silica gel eluting with 20% ethyl acetate in hexane to give 8.5 g of the title compound as a white solid. Given in the form.

_{90MHz NMR (CDCl 3) δ:} 3.83 (s, 2H, CH 2), 3.93 (s, 3H, CH 3), and 7.9 (m, 3H, aromatic).

Example 2 2- (methoxycarbonyl) -6- (cyanomethyl) -benzenesulfonyl chloride To a stirred suspension of dry tetrahydrofuran (150 mL) and 26% potassium hydride in an oil (6.66 g) was added benzyl mercaptan (4.82 g). mL) was added slowly 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 overnight at room temperature. 6N reaction
Contacted with sodium hydroxide (25 mL) and extracted with ethyl acetate. The extract was washed with 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 solid. Was.

The crude thioether was diluted with dichloromethane (200 mL) and 6
While stirring at 0 ° C. in a mixture of N hydrochloric acid (25 mL), 5% sodium hypochlorite (180 mL) was added slowly. 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 hexane to give 1.7 g of the title compound as a yellow solid. .

_{90MHz NMR (CDCl 3) δ:} 3.98 (s, 3H, CH 3), 4.41 (s, 2H, CH 2), and 7.83 (m, 3H, aromatic).

Example 3 Methyl 3- (cyanomethyl) -2-[[[(1,1-dimethylethyl) -dimethylsilyl] amino] sulfonyl] benzoate 2- (methoxycarbonyl) -6- (cyanomethyl) benzenesulfonyl (10.7 g), a suspension of 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 is washed with water, dried over magnesium sulfate, filtered,
Concentrate and chromatograph on silica gel eluting with 30% ethyl acetate in hexane to give 5.0 g of the title compound as a yellow solid, mp 113-115 ° C.

90 MHz NMR (CDCl ₃ ) δ: 0.32 (s, 6H, SiCH ₃ ), 0.95 (s, 9H, C (CH ₃ ) ₃ ), 3.99 (s, 2H, OCH ₃ ), 4.42 (s, 2H, CH ₂₎ CN), 5.91 (s, 1H, NH), 7.6 (m, 2H, aromatic), and 7.8 (m, 1H, aromatic).

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 3- (cyanomethyl) -2-[[[(1 , 1-Dimethylethyl) -dimethylsilyl] amino] sulfonyl] methyl benzoate (0.34 g), O-phenyl-N- (4,6-dimethyl-2-pyrimidinyl) carbamate (0.24 g), and acetonitrile (2.5 mL) ) Was stirred and cooled in an ice-acetone bath. A stock solution of 1 M tetrabutylammonium fluoride containing 8 mol% of 1,8-diazabicyclo- [5.4.0] undec-7-one (1.0 mL) was added and the reaction was allowed to proceed under a nitrogen atmosphere for 45 minutes. Stirred. The reaction was added to water (3 mL) and acidified 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, mp 113-115 ° C.

200 MHz NMR (DMSO) δ: 2.40 (s, 6H, CH ₃ ), 3.79 (s, 3H, OCH ₃ ), 4.67 (s, 2H, CH ₂ CN), 7.04 (s, 1H, pyrimidinyl.H), 7.64 (M, 1H, aromatic), 7.82 (m, 2H, aromatic), 10.8 (s, 1H, NH), and 13.7 (s, 1H, NH).

IR (mineral oil) 2240, 1740cm ^-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) ) Was heated under reflux overnight. Undissolved salts were filtered off and the filtrate was extracted with ethyl acetate. The extract was washed with brine, 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.

_{90MHz NMR (CDCl 3) δ:} 3.98 (s, 3H, OCH 3), 7.8 (m, 1H, aromatic), 8.3 (m, 2H, aromatic), and 10.0 (s, 1H, HCO) .

Example 6 Methyl 3- (difluoromethyl) -2-nitrobenzoate Methyl 3-formyl-2-nitrobenzoate in a solution of diethylaminosulfur trifluoride (11 mL) in dichloromethane (75 mL) at -70 ° C under a nitrogen atmosphere. (5.9 g) in dichloromethane was added. The reaction was allowed to warm to room temperature naturally. After 3 hours, it was poured on ice (300 mL) and extracted with dichloromethane. The extract was washed with water, dried over magnesium sulfate, filtered, and concentrated to give a crude solid. Hexanes-by recrystallization from cyclobutane
3.94 g of the title compound were obtained as a pink solid, mp 66-69.
° C.

_{90MHz NMR (CDCl 3) δ:} 3.94 (s, 3H, OCH 3), 6.87 (t, 1H, CHF 2), and 7.9 (m, 3H, aromatic).

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 added benzyl mercaptan (4.63 g). mL) was added slowly 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 extract was 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 added with dichloromethane (400 mL) and 6
While stirring at 0 ° C. in a mixture of N hydrochloric acid (28 mL), 5% sodium hypochlorite (204 mL) was added slowly. 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.

_{90MHz NMR (CDCl 3) δ:} 4.13 (s, 3H, OCH 3), and 7.1-8.3 (m, 4H, CHF ₂ and aromatic).

Example 8 Methyl 3- (difluoromethyl) -2-[[[(1,1-dimethylethyl) dimethylsilyl] amino] sulfonyl] benzoate 2- (methoxycarbonyl) -6- (difluoromethyl) benzenesulfonyl chloride 5.17 g), amino-t-
A suspension of 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 hexane 2.22.
g of the title compound were obtained as a white solid.

90 MHz NMR (CDCl ₃ ) δ: 0.2 (s, 6H, SiCH ₃ ), 0.87 (s, 9H, C (CH ₃ ) ₃ ), 3.90 (s, 3H, OCH ₃ ), 5.88 (s, 1H, NH) , and 7.20-8.36 (m, 4H, CHF ₂ and aromatic).

Example 9 3- (difluoromethyl) -2-[[[[(4-methoxy-2-pyrimidinyl) amino] carbonyl] amino]
Methyl sulfonyl] benzoate 3- (difluoromethyl) -2-[[[(1,1-dimethylethyl) dimethylsilyl] amino] sulfonyl] methyl benzoate (0.22 g), O-phenyl-N- (4-methoxy -2-pyrimidinyl) carbamate (0.15 g),
And a mixture of acetonitrile (2.0 mL) was stirred and cooled in an ice-acetone bath. 8 mol% of 1,8-diazabicyclo- [5.4.0] undec-7-one (0.61 mL)
A stock solution of 1 M tetrabutylammonium fluoride containing was added and the reaction was stirred under a nitrogen atmosphere for 1 hour. Add the reaction to water (30 mL) and use 1N hydrochloric acid to pH
Acidified to 5. 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, mp 178-180 ° C (dec).

200 MHz NMR (DMSO) δ: 3.94 (s, 3H, OCH ₃ ), 4.14 (s, 3H, OCH ₃ ), 6.87 (d, 1H, pyrimidinyl.H), 7.8-8.2 (m, 3H, aromatic), 8.43 (d, 1H, pyrimidinyl.H), 11.46 (s, 1H, NH), and 13.90 (s, 1H, NH).

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

Example 10 Methyl 3- (1-hydroxyethyl) -2-nitrobenzoate Titanium tetrachloride (6.25 mL) was added to dry diethyl ether (25
0 mL) at -78 ° C and stirred under a nitrogen atmosphere. The resulting yellow suspension was spontaneously warmed to -50 ° C and re-cooled to -78 ° C, after which 1.
4 mol of methyl lithium (41.6 mL) was added. The mixture was warmed to −30 ° C., and the resulting purple mixture was cooled to −60 ° C. and an adjacent flask containing methyl 3-formyl-2-nitrobenzoate (11.6 g) and dry tetrahydrofuran (250 mL) Transferred by cannula inside.
The resulting mixture was allowed to warm to room temperature and 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 extract was 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.

_{90MHz NMR (CDCl 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, aromatic).

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

Example 11 Methyl 3- (1-fluoroethyl) -2-nitrobenzoate A solution of diethylaminosulfur trifluoride (18 mL) in dichloromethane (100 mL) at −74 ° C. under a nitrogen atmosphere was added under a nitrogen atmosphere.
A solution of methyl (1-hydroxyethyl) -2-nitrobenzoate in dichloromethane (14.6 g) was added. The reaction was allowed to warm to room temperature on its own and briefly to 35 ° C. After a 4 hour reaction period, the reaction was poured over ice and water (200 mL) and extracted with dichloromethane. The combined extracts were washed with a 1: 1 mixture of 1N 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 (CDCl ₃ ) δ: 1.67 (d d, 3H, CH ₃ ), 3.93 (s, 3H, OCH ₃ ), 5.7 (q d, 1H, CHF), and 7.9 (m, 3H, aromatic ).

IR (neat) 1736 cm ^-1 .

Example 12 Methyl 3- (1-fluoroethyl) -2- (phenylmethylthio) benzoate Methyl 3- (1-fluoroethyl) -2-nitrobenzoate (15 g) according to the procedure described in Example 2. To give 17.55 g of the unpurified title compound as a brown oil.

Example 13 2- (Methoxycarbonyl) -6- (1-fluoroethyl) -benzenesulfonyl chloride Following the procedure described in Example 2, 3- (1-fluoroethyl) -2- (phenylmethylthio) benzoic acid Methyl (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 (CDCl ₃ ) δ: 1.8 (d d, 3H, CH ₃ ), 4.0 (s, 3H, OCH ₃ ), 6.6 (q d, 1H, CHF), and 7.8 (m, 3H, aromatic ).

Example 14 Methyl 3- (1-fluoroethyl) -2-[[[(1,1-dimethylethyl) dimethylsilyl] amino] sulfonyl] benzoate According to the procedure described in Example 3, chloride 2- ( (Methoxycarbonyl) -6- (1-fluoroethyl) benzenesulfonyl (2.4 g) was reacted and chromatographed on silica eluting with 15% ethyl acetate in hexanes to give 1.3 g of the title compound as an orange oil. Was.

90MHz NMR (CDCl ₃ ) 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 (s, 1H, NH), 6.6 (q of d, 1H, CHF), and 7.6 (m, 3H, aromatic).

Example 15 Methyl 3- (1-fluoroethyl) -2-[[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate According to the procedure described in Example 4. , 3- (1-Fluoroethyl) -2-[[[(1,1-dimethylethyl)-
Dimethylsilyl] amino] sulfonyl] methyl 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 in pink. Given in solid form,
155-158 ° C.

200 MHz NMR (DMSO) δ: 1.64 (d, 3H, CH ₃ ), 3.85 (s, 3H, CO ₂ CH ₃ ), 3.98 (s, 6H, OCH ₃ ), 6.08 (s, 1H, pyrimidinyl.H ), 7.04 (q, d, 1H, CHF), 7.72 (m, 1H, aromatic), 7.96 (m, 2H, aromatic), 10.85 (s, 1H, NH), and 12.75 (s, 1H, NH) ).

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

By applying the steps of Reaction Schemes 1-7 and Examples 1-15, those skilled in the art can readily prepare the compounds of Tables 1-4.

Formulations Useful formulations of compounds of formula I can be prepared in conventional manner. They include powders, granules, tablets, suspensions, emulsions, wettable powders, concentrated emulsions. Many of these can be applied directly. Spray formulations can be extended in suitable media and used in spray volumes of a few liters to a few hundred liters per hectare. High strength compositions are mainly used as intermediate products for further formulation. Briefly, the formulation is about 0.1-99% by weight
And at least one of (a) about 0.1% to 20% of a surfactant (s) and (b) about 1% to 99.9% of a solid or liquid diluent. More particularly,
They will contain these components in approximately the following proportions:

Of course, lower or higher amounts of the active ingredient may be present, depending on the intended use and the physical properties of the compound. High ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents include Watkins
Others, "Handbook of Insecticide Dust Diluents and Carrie
rs), 2nd edition, Drand Books, Caldwell, NJ, but other solids, which may be refined or manufactured, may be used. For wettable powders, relatively adsorptive diluents are preferred, and for powders, relatively thick diluents are preferred.
A typical liquid diluent and solvent is Marsde
n), "Solvents guide", 2nd edition, Interscience, New York, 1950. A solubility of less than 0.1% is suitable for concentrated suspensions, and the concentrated solutions are preferably stable to phase separation at 0 ° C. "McCutche Detergent and Emulsifier Yearbook (McCutche
on's Detergents and Emulsifiers Annual, "Al-Aled Publishers Corporation, New Jersey, and Sisely and Wood," Encyclopedia of Surfactants. "
Surface Active Agents ", Chemical Publishers Company, Inc., New York, 1964, lists surfactants and their recommended uses. All formulations can contain small amounts of additives to reduce foaming, caking, corrosion, and microbial growth.

The preparation of such compositions is well known. Solutions are made by simply mixing the components. Fine solid compositions are manufactured by mixing and generally grinding using a hammer mill or fluid energy mill. Suspensions are prepared by wet milling (see, for example, U.S. Pat. No. 3,060,084 to Littler). Granules and tablets can be prepared by spraying the active substance onto a preformed granular carrier or by the agglomeration method. JE Browning,
"Agglomeration", Chemical Engineering, December 4, 1967, 147f
Page f and Perr's Chemical Engineer's Handboo
k) 5th edition, McGraw Hill, New York, 196
See pages 3, 8-57ff.

For further literature on formulating techniques see, for example, HM Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, column 6, line 16-column 7, line 19 and Examples 10-41. RW Luckenbaugh, US Patent 3,309,1
92, March 14, 1967, column 5, line 43-column 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-
164, 166, 167, 169-182, H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, column 3, line 66-5, column 17, line 17 and Examples 1-4. GC Klingman, "Weed Control as a Science", Joan Willie and Sons, Inc., New York, 1961, pages 81-96, and JD Flyer (Frye).
r) and SA Evans, "Weed Control Handbook", 5th edition, Blackwell Scientific Pullikations,
Oxford, 1968, pp. 101-103.

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

Example A High-strength thickener 3- (cyanomethyl) -2-[[[[(4,6-dimethyl-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] methyl benzoate 99% Trimethylnonyl polyethylene glycol ether 1% The surfactant was sprayed on the active ingredient in a compounder and the mixture was passed through a US Standard No. 40 sieve (0.42 mm opening) before packaging. Thickeners can be further formulated for actual use.

Example B Wetting agent 2-[[[[(4-Chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -3- (cyanomethyl) -methyl benzoate 65% dodecylphenol polyethylene glycol Ether 2% Sodium lignin sulfonate 4% Sodium silicoaluminate 6% Montmorillonite (calcined) 23% The liquid surfactant was added by spraying the solid components in the compounder. After milling in a hammer mill to produce essentially all sub-100 micron particles, the material was reformulated and passed through a US Standard 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] methyl 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% Compound the ingredients in a sand mill and grind together to essentially all dimensions Produced particles less than 5 microns.

Example D Oil Suspension 3- (Difluoromethyl) -2-[[[[(4-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -methyl benzoate 35% Polyalcoholcarboxylic acid esters and Blends of Oil-Soluble Petroleum Sulfonates 6% Xylene 59% The components were blended in a sand mill and milled together to produce particles of essentially all sizes less than 3 microns. The product can be used directly, spread with oil, or emulsified in water.

Example E Oil Suspension 3- (Fluoromethyl) -2-[[[[(4-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl]-Methyl Benzoate 25% Polyoxyethylene Sorbitol Hexaoleate The ingredients were milled together in a 5% higher aliphatic hydrocarbon oil 70% sand mill until the solid particles were reduced to about 5 microns or less. The resulting thick suspension can be applied directly, but is preferably applied after spreading with oil or emulsifying in water.

Example F aqueous suspension 2-[[[[(4,6-dimethoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -3- (fluoromethyl) -methyl benzoate 25% hydrated attapulgite 3% The crude calcium lignin sulfonate 10% sodium dihydrogen phosphate 0.5% water 61.5% The ingredients were milled together in a ball or roller mill until the solid particles were reduced to a diameter of 10 microns or less.

Example G wettable powder ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl) -amino] carbonyl] amino] sulfonyl] -3- (fluoromethyl) -benzoate 40.0% sodium sulfoamber Dioctyl Acid 1.5% Sodium Lignin Sulfonate 3% Low Viscosity Methylcellulose 1.5% Attapulgite 54% Ingredients are thoroughly compounded, passed through an air mill to produce an average particle size of 15 microns or less, remixed, and Passed through a .50 sieve (30 mm opening) and then packaged.

All compounds of the invention can be prepared in the same way.

Example H Granules The wettable powder of Example G 15% gypsum 69% potassium sulfate 16% The ingredients were blended in a rotary mixer and granulated by spraying with water. Most of the material is 1.0-0.42cm (US standard #
When the desired range of (18-40 sieve) was reached, the granules were removed, dried and sieved. The oversized material was crushed to produce the desired range of additional material. These granules contained a% active ingredient.

Example I wettable powder 2-[[[[(4,6-ditomex-2-pyrimidinyl)
Amino] -carbonyl] amino] sulfonyl] -3- (fluoromethyl) -methyl benzoate 50% Sodium alkylnaphthalenesulfonate 2% Low viscosity methylcellulose 2% Diatomaceous earth 46% Combined ingredients, coarsely hammer milled, and Air milling produced active particles of essentially all diameters less than 10 microns. The product was reformulated and then packaged.

Example J Extruded Tablets 3- (Fluoromethyl) -2-[[[[(4-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl]-Methyl Benzoate 25% Sodium sulfate anhydrous 10% Crude lignin sulfonic acid Calcium 5% Sodium alkylnaphthalenesulfonate 1% Calcium / magnesium bentonite 59% Combined formulation, hammer milled, and then about
Wet with 12% water. The mixture was extruded in a cylinder about 3 mm in diameter and cut into tablets about 3 mm in length. These can be used directly after drying, or the dried tablets can be crushed and crushed to a US standard No. 20 sieve (0.8
4mm opening). The particles remaining on the U.S. Standard No. 40 sieve (0.42 mm opening) could be packaged for use and the fines could be recycled.

Example K wettable powder 3- (difluoromethyl) -2-[[[[(4-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] -methyl benzoate 80% sodium alkylnaphthalenesulfonate 2% lignin Sodium sulfonate 2% Synthetic amorphous silica 3% Kaolinite 13% The composition was compounded and then ground in a hammer mill to produce particles having an average particle size of less than 25 microns in diameter. The material was reconstituted and passed through a US Standard No. 50 sieve (0.3 mm opening) before packaging.

Example L High Strength Thickener Methyl 3- (cyanomethyl) -2-[[[[(4-difluoromethoxy) -6-methoxy-2-pyrimidinyl] amino] carbonyl] amino] sulfonyl] benzoate 98.5% silica airgel 0.5% synthetic amorphous fine silica 1.0% synthetic compound was formulated and then milled in a hammer mill to produce particles having an average particle size of less than 25 microns in diameter. This material could then be prepared in various ways.

Example M solvent 3- (cyanomethyl) -2-[[[[(4,6-dimethyl-2-pyrimidinyl] amino] carbonyl] amino] sulfonyl] methyl benzoate, sodium salt 5% water 95% salt is stirred. While adding the solvent directly to water, which was then packaged for use.

Uses The test results show that the compounds of the invention are active postemergence and preemergence herbicides. Many compounds of the present invention are useful in important agronomic crops such as barley (Hordeum vulg).
are), corn (Zea mays), rice (Oryza sativ)
a), and wheat (Triticum aestivum), while useful for controlling selected turfgrass and broadleaf weeds. Regulated turfgrass weeds include dog millet (Echinochlo
a crusgalli), Blackgrass (Alopecurus myosuroi)
des), Sparrow Butterfly (Bromus ssp.) Enokorogosa (Setaria ssp.), Johnsongrass (Sorghum helepe)
nse), panicum (Panicum spp.), and oats (Avena fatua), but are not limited thereto. Regulated broadleaf weeds include the fir (Xa
nthium pensylvanicum, Datura (Datura)
stramonium, Ramsquarters (Chenopodium alb)
um) and morning glory (Ipomoea spp.)
spp.), backwheat (Polygonum spp.) sickle pod (Cassia obtusifolia), and velvet leaf (Abutilon theophrasti), but are not limited thereto. Many compounds in the present invention also modulate nutsedge (Cyperus spp.). Certain compounds from the present invention are particularly useful for controlling weeds in cereal crops such as barley and wheat. Several selections of these compounds are particularly useful for controlling weeds in corn.

Some compounds according to the invention may be used in non-crop areas where selective or complete control of all plants is expected, such as around fuel storage tanks, around ammunition storage, industrial storage areas, parking lots, outdoor theaters, advertising. It has utility around boards, highways and railway structures. These compounds are also useful in fallow areas for the production of crops such as wheat and barley and in orchard crops such as palm, banana, citrus, rubber. On the other hand, these compounds are also useful for modifying plant growth or as citrus harvest assisting cutting agents.

The application rate of the compounds of the present invention will depend on many factors. These factors include the formulation selected, method of application, coexisting crop species, growth conditions, and the like. Generally speaking, the compounds should be applied in an amount of 0.001-20 kg / ha, with a preferred rate range being 0.004-0.25 kg / ha. Those skilled in the art can easily determine the required proportions for the desired level of weed control.

The compounds of the present invention can be used alone or with other commercial herbicides,
It can be used in combination with insecticides or fungicides. The following list illustrates some of the herbicides that are suitable for use in the mixture. Combinations of a compound from the present invention and one or more of the following herbicides may be particularly useful for weed control.

The weed properties of the compounds were discovered in a series of greenhouse tests. The test process and results are described below.

Test A Barley (Hordeum vulgare), Barnyardgrass (Echinochloac)
rusgalli), Sparrow Butterfly (Bromus secalinus),
Anemone fir (Xanthium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.)
i), morning glory (Ipomoea spp.) rice (Oryza sativa),
Sorghum (Sorghum bicolor), soy (Glycine max),
Sugar beet (Beta vulgaris), velvet leaf (Abutilon theophrasti), wheat (Triticum aestivu)
m), oats (Avena fatua) and nutsedge (Cype)
(Rus rotundus) seeds were planted and treated with test chemicals dissolved in a non-toxic solvent before germination. At the same time, these crops and weed species were also treated with a post-emergence application of the test chemical. For post-emergence treatment, the plants ranged in height from 2-18 cm (2-3 leaf stage). The treated plants and controls were kept at room temperature for about 16 days, after which all species were compared and visually assessed. The plant response ratings summarized in Table A are based on a scale of 0-10, where 0 is no effect and 10 is complete control. A dash (-) means no test result.

Test B Barley (Hordeum vulgare), Barnyardgrass (Echinochloac)
rusgalli), blackgrass (Alopecurus myosuroide)
s), Sparrow-leaf cypress (Bromus secalinus), Southern flora (Stellaria media), Long-tailed fir (Xanthium pensyl)
vanicum), corn (Zea mays), cotton (Gossypium)
hirsutum), crabgrass (Digitaria spp.), bed straw (Galium aparine), giant croaker (Setari)
a faberi), Ramsquarters (Chenopodium albu)
m), morning glory (Ipomoea spp.), oilseed rape (Brassica
napus), rice (Oryza sativa), sorghum (Sorghum bic)
olor), soybean (Glycine max), sugar beet (Beta)
vulgaris), velvet leaf (Abutilon theophrast)
i), wheat (Triticum aestivum), wild back wheat (Polygonum convolvulus), oats (Avena f)
(atua) and nutsedge (Cyperus rotundus) seeds were planted and treated before germination with test chemicals dissolved in a non-toxic solvent. At the same time, these crops and weed species were also treated with a post-emergence application of the test chemical. For post-emergence treatments, plants are in the range of 2-18cm height (1-4 leaf stage)
Met. Treated plants and controls at room temperature for about 12
-16 days, after which all species were compared to controls and evaluated visually. The plant response ratings summarized in Table B are based on a scale of 0-10, where 0 is no effect and 10 is complete control. A dash (-) means no test result.

Test C Barley (Hordeum vulgare), Barnyardgrass (Echinochloac)
rusgalli), blackgrass (Alopecurus myosuroide)
s), seaweed (Stellaria media), and sea fir (Xant
hium pensylvanicum), corn (Zea mays), cotton (Gossypium hirsutum), and crabgrass (Digitaria sp.)
p.), Downy brom (Bromus tectorum), Blue-tailed dwarf (Setaria faberi), Green foxtail (Setaria viridis), Datura morning glory (Datur)
a stramonium, Johnson grass (Sorghum halepens)
e), Ramsquarters (Chenopodium album), morning glory (Ipomoea spp.), oilseed rape (Brassica napus),
Rice (Oryza sativa), Sickle pod (Cassia obtusif)
olia), soybeans (Glycine max), sugar beet (Beta)
vulgaris), teaweed (Sida spinosa), velvet leaf (Abutilon theophrasti), wheat (Triticum)
aestivum), wild back wheat (Polygonum con)
volvulus), oats (Avena fatua) and nutsedge (Cyperus rotundus) seeds were planted and treated before germination with test chemicals dissolved in a non-toxic solvent. At the same time, these crops and weed species were also treated with a post-emergence application of the test chemical. For post-emergence treatment, plant is 2-
The height range was 18 cm (2-3 leaf stage). Keep the treated plants and controls in a greenhouse for about 24 days, after which
All species were compared to controls and evaluated visually. The plant response ratings summarized in Table C are based on a scale of 0-10, where 0 is no effect and 10 is complete control. A dash (-) means no test result.

Test D The compounds evaluated in this test were formulated in a non-toxic solvent and before the plant seedlings emerged soil (pre-emergence application), water covering the soil surface (paddy application) and 2
-4 Applied to leaf stage plants (post-emergence application). Sandy loam soil was used for pre-emergence and post-emergence tests,
In the paddy field test, Syltrome soil was used. The depth of the water was about 2.5 cm for paddy field tests and was kept at this level throughout the test period.

The plant species in the pre-emergence and post-emergence tests were barley (Ho
rdeum vulgare), bed straw (Galium aparin)
e), blackgrass (Alopecurus myosuroides), southern grass (Stellaria media), corn (Zea may)
s), cotton (Gossypium hirsutum), crabgrass (Digitaria)
sanguinalis, Downy Brome (Bromus tectoru)
m), Pterodactyla (Setaria faberi), Ramsquarters (Chenopodium album), Morning Glory (Ipomoea)
spp.), Amaranthus retroflexus, Brassica napus, Lolium multifl
orum), sorghum (Sorghum bicolor), speedwell (Veronica persica), sugar beet (Beta vulga)
ris), velvet leaf (Abutilon theophrasti),
Wheat (Triticum aestivum), wildback wheat (Polygonum convolvulus), and oat (Avena)
fatua). All plant species were planted and the compound was applied one day later for the pre-emergence part of the test.
The planting of these seeds was adjusted to produce plants of suitable dimensions for the post-emergence part of the test. The plant species in the paddy field test were dog millet (Echinochloa crusgalli) and rice (Oryza
sativa) and umbrella sage (Cyperus difform)
is).

All plant species were grown using normal greenhouse practices. Visual assessment of the damage that appeared on the treated plants when compared to the untreated control was recorded approximately 14-21 days after application of the test compound. The plant-related evaluation summarized in Table D is 0-
Based on a scale of 10, where 0 is no damage and 10 is complete control. A dash (-) means no test result.

Test E Dog millet (Echinochloa crusgalli)
thium pensylvanicum), corn (Zea mays)
(Exposed soil surface and perlite covered soil surface), crabgrass (Digitaria spp.), Fall panicum (Panicum dichotomiflorum),
etaria faberi), Green Foxtail (Setaria)
viridis), Ivy Leaf Morning Glory (Ip
omoea hederacea), Korean morning glory (Datura stra)
monium), Johnson grass (Sorghum halepense),
Ladies Sam Smartweed (Polygonum persicar)
ia), Ramsquarters (Chenopodium album), Red Root Pigweed (Amaranthus retroflexu)
s), sorghum (Sorghum bicolor), soybean (Glycine ma
x), velvet leaf (Abutilon theophrasti) and nutsedge (Cyperus rotundus) seeds were planted and treated with test chemicals dissolved in a non-toxic solvent before germination. At the same time, these crops and weed species were also treated with a post-emergence application of the test chemical. For post-emergence treatment, the plants ranged in height from 2-25 cm (2-3 leaf stage).

The treated plants and controls were kept in the greenhouse for approximately 24 days, after which all species were compared and visually evaluated. The plant response assessments summarized in Table E are 0-10
Where 0 is no effect and 10 is complete control. A dash (-) means no test result.

Test F A plastic container was partially filled with Syltrome soil. The soil was then saturated with water. 2.0-2.5 leaf stage indica and japonica rice (Oryza sativa) seedlings, rice millet (Echinochloa crusgalli), bull rush (Sci
rpus mucronatus), duck salad (Heteranthera Bimo)
sa), seeds selected from umbrella sage (Cyperus difformis), and water chestnut (Eleoch)
ris spp.) were planted in this soil. After planting, the water level was raised to 3 cm above the soil surface and kept at this level during the test. Chemical treatment materials were formulated in non-toxic solvents and applied directly to paddy water. The treated plants and controls were kept in the greenhouse for about 21 days, after which all species were compared to controls and evaluated visually. The plant response table summarized in Table F is 0-10
Where 0 is no effect and 10 is complete control. A dash (-) means no test result.

Test G The compounds evaluated in this test are formulated in a non-toxic solvent and applied to soil (preemergence application) and 1-4 leaf stage plants (postemergence application) before plant seedlings develop. Was done. Sandy loam soil was used for the pre-emergence test,
For postemergence tests, use sandy loam soil and greenhouse container mixtures.
A mixture in a 60:40 ratio was used. For pre-emergence tests, the test compound was applied within about one day after seeding. The planting of these crops and weed species was adjusted to produce plants of suitable dimensions for postemergence testing. All plant species were grown using normal greenhouse practices. Crops and weed species include winter barley (Hordeum vulgare cv, 'Igri'),
Bed straws (Galium aparine), blackgrass (Alopecurus myosuroides), southern grass (Stellaria)
media), downy brome (Bromus tectorum), field violet (Viola arvensis), green foxtail (Setaria viridis), ramsquarters (Chenopodium album), Persian speedwell (Veronica persica), oilseed rape (Brassica napus c)
v. 'Jet Neuf'), rat (Lolium multifloru)
m), sugar beet (Betavulgaris cv. 'US1'), sunflower (Helianthus annuus cv. 'Russian Giant'),
Spring wheat (Triticum aestivum cv. 'ERA'), winter wheat (Tr
iticum aestivum cv. Talent '), wild back wheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), oat (Avena fatua)
And wild radish (Raphanus raphanistru)
m) was included. Blackgrass and oats were treated at two growth stages after germination. The first stage (1) was when the plants had 2-3 leaves. Second
Stage (2) was when the plants had about 4 leaves or were in the early stages of young leaves. Treated plants and untreated controls were kept in the greenhouse for about 21-28 days, after which all treated plants were compared to untreated controls and evaluated visually. The plant response ratings summarized in Table G are based on a scale of 0-10, where 0 is no effect and 10 is complete control. A dash (-) means no test result.

Test H Alfalfa (Medicago sativa), kidney beans (Phaseolus vulgaris), bluegrass (Poa pratensi)
s), cabbage (Brassica rapa), carrot (Daucus sativ)
a), corn (Zea mays), flax (Linum usitati)
ssimum), lettuce (Lactuca sativa), lupine (Lupi)
nus albus), oats (Avena sativa), onions (A
llium cepa), peas (sativa), peanuts (Arac)
his hypogaea), potato (Solanum tuberosum), rye (Secale cereal), sorghum (Sorghum bicolor),
Sunflower (Helianthus annuus) and tomato (Lycop)
ersicon esculentum) were seeded and treated before germination with test chemicals dissolved in a non-toxic solvent. These crop species were also treated with a post-emergence application of the test chemical. For post-emergence treatments, plants should be 4-20 cm high (2
-3 leaf stage). The treated plants and controls were kept under greenhouse conditions for about 24 days, after which all plants treated with the test compound were compared to untreated controls and visually assessed for damage response. The application rates for the test chemicals are shown in Table H. The plant response ratings summarized in Table H are based on a scale of 0-10, where 0 is no damage and 10 is complete control. A dash (-) means no test result.

The main features and aspects of the present invention are as follows.

1. Wherein A is OR ¹ or N (CH ₃ ) ₂ , R ¹ is C ₁ -C ₃ alkyl, CH ₂ CH = CH ₂ , CH ₂ C≡CH, CH ₂ CH ₂ C
l 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, wherein X is OCH ₃ when Y is Cl] and their agriculturally suitable salts.

2. The compound according to ^{1 above} , wherein A is OR ¹ and R ¹ is CH ₃ , CH ₂ CH ₃ or CH (CH ₃ ) ₂ .

3. The compound of claim 2, wherein when one of X and Y is CH ₃ , the other of X and Y is other than OCH ₃ .

4.3. The compound of the above 1, which is methyl 4- (cyanomethyl) -2-[[[[(4,6-dimethyl-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate.

5.2-[[[[[(4-Chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl]
The above 1 which is methyl-3- (cyanomethyl) benzoate;
Compound.

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

7.3. The compound of the above 1, which is methyl 3- (difluoromethyl) -2-[[[[(4-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl] benzoate.

8.3- (Fluoromethyl) -2-[[[[(4-methoxy-2-pyrimidinyl) amino] carbonyl] amino]
Sulfonyl] methyl benzoate.

9.2-[[[[(4,6-dimethoxy-2-pyrimidinyl)
The compound of the above 1, which is methyl amino [carbonyl] amino] sulfonyl] -3- (fluoromethyl) benzoate.

10.2-[[[[(4-Chloro-6-methoxy-2-pyrimidinyl) amino] carbonyl] amino] sulfonyl]
The compound of 1 above, which is ethyl-3- (fluoromethyl) benzoate.

11. Wherein A is OR ¹ or N (CH ₃ ) ₂ , R ¹ is C ₁ -C ₃ alkyl, CH ₂ CH = CH ₂ , CH ₂ C≡CH, CH ₂ CH ₂ C
l 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 and R ³ is C ₁ -C ₄ alkyl, R ⁴ is C ₁ -C ₄ alkyl and R ⁵ is C ₁ -C ₄ alkyl, with the proviso, Z ¹ when a is OR ¹ is NHSiR ³ R ⁴ R ⁵ And R ³ , R ⁴ and R ⁵ are C ₁ -C ₃ alkyl].

12. The compound of claim 11, wherein A is OR ¹ and R ¹ is C ₁ -C ₂ alkyl.

13.R ³ and R ⁴ are CH ₃ and R ⁵ is C (CH ₃ ) ₃
12. The compound of the above item 12.

14. A composition suitable for controlling unwanted plant growth, comprising an effective amount of one of the above compounds and at least one of the following: a surfactant, a solid diluent or a liquid diluent.

15. A composition suitable for controlling unwanted plant growth, comprising an effective amount of the above two compounds and at least one of the following: a surfactant, a solid diluent or a liquid diluent.

16. A composition suitable for controlling unwanted plant growth, comprising an effective amount of the above three compounds and at least one of the following: a surfactant, a solid diluent or a liquid diluent.

17. A composition suitable for controlling unwanted plant growth, comprising an effective amount of a compound of the above 4 and at least one of the following: a surfactant, a solid diluent or a liquid diluent.

18. A composition suitable for controlling unwanted plant growth, comprising an effective amount of a compound of the above 5 and at least one of the following: a surfactant, a solid diluent or a liquid diluent.

19. A method for inhibiting undesired plant growth, comprising applying an effective amount of a compound of the above 1 to the site to be protected.

20. A method for inhibiting undesired plant growth, comprising applying an effective amount of a compound of the above 2 to the site to be protected.

21. A method for inhibiting undesired plant growth, comprising applying an effective amount of a compound of the above 3 to the site to be protected.

22. A method for inhibiting undesired plant growth, comprising applying an effective amount of the compound of 4 above to the site to be protected.

23. A method for inhibiting undesired plant growth, comprising applying an effective amount of the compound of 5 above to the site to be protected.

24. The place to be protected is corn, 2 above
2 ways.

25. A method for inhibiting the growth of undesired plants in wheat or barley, comprising applying an effective amount of the compound of 9 to wheat or barley.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI C07F 7/10 C07F 7/10 A (58) Field surveyed (Int.Cl. ⁶ , DB name) C07D 239/42 H C07D 239/47 A C07D 239/52 C07C 309/89 C07F 7/10 A A01N 47/36 101 E CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (4)

(57) [Claims] (1) Wherein A is OR ¹ or N (CH ₃ ) ₂ , R ¹ is C ₁ -C ₃ alkyl, CH ₂ CH = CH ₂ , CH ₂ C≡CH, CH ₂ CH ₂ Cl
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, a OCH ₃ or OCF ₂ H, where, Y is when a Cl X is OCH _3] and a compound selected from those agriculturally suitable salts. 2. The compound according to claim ¹ , wherein A is OR ¹ and R ¹ is CH ₃ , CH ₂ CH ₃ or CH (CH ₃ ) ₂ . (3) Wherein A is OR ¹ or N (CH ₃ ) ₂ , R ¹ is C ₁ -C ₃ alkyl, CH ₂ CH = CH ₂ , CH ₂ C≡CH, CH ₂ CH ₂ Cl
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 and R ³ is C _1- C ₄ alkyl, R ⁴ is C ₁ -C ₄ alkyl, and R ⁵ is C ₁ -C ₄ alkyl, provided that when A is OR ¹ , Z ¹ is NHSiR ³ R ⁴ R ⁵ And R ³ , R ⁴ and R ⁵ are C ₁ -C ₃ alkyl]. 4. An undesired vegetation growth inhibitor comprising the compound according to claim 1 as an active ingredient.