JPS626705B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel benzylsulfonylureas. The compounds of the invention and their agriculturally acceptable salts are useful as agricultural chemicals, such as herbicides. Dutch patent published on September 15, 1966
121788 discloses the preparation of compounds of the formula and their use as general or selective herbicides: [In the formula, R ₁ and R ₂ independently have 1 to 4 carbon atoms
and R ₃ and R ₄ are independently hydrogen, chlorine, or alkyl having 1 to 4 carbon atoms]. U.S. Patent 3,637,366 is a formula Disclosed are compounds having the formula: wherein R ₁ is hydrogen or lower saturated aliphatic acyl and R ₂ is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl. It is stated that the disclosed compounds inhibit crabgrass, orchids, arborvitae, clover, and sycamore. French patent 1468747 discloses that the following para-substituted phenyl sulfonamides are useful as antidiabetic agents: [wherein R is H, halogen, CF ₃ or alkyl]. Chem. Ab. 53 of Logemann et al.
18052g (1959) is a uracil derivative and formula [In the formula, R is butyl, phenyl or

A number of sulfonamides are disclosed, including those having the formula: and R ₁ is hydrogen or methyl. When tested for hypoglycemic effects in mice (25mg/100g oral dose),
Compounds in which R is butyl and phenyl were the most effective. Others were less effective or inactive. Wojciechowski's J.
Acta. Polon. Pharm. 19 , pp. 121-5 (1962)
[Chem.Ab. 59 1633e] is N-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]
-4-methylbenzenesulfonamide It describes the synthesis of Based on similarities with known compounds, the authors speculated that said compound would have hypoglycemic activity. Substituted -pyrimidinylsulfonylureas of the general formula below, which are also para-substituted on the phenyl ring, are produced by Farmo Ed.Sco. 12 , 586 (1957) [Chem.
Ab. 53 , 18052g (1959)]: [wherein R is H or _CH3 ]. U.S. Pat. No. 4,127,405 discloses a formula useful for controlling weeds in wheat. [In the formula, R ₁ is

【formula】

【formula】

[Formula] or

[Formula], R ₃ and R ₃ are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, nitro, trifluoromethyl, cyano , CH ₃ S (O) _o - or CH ₃ CH ₂ S
(O) _o -, R ₄ is hydrogen, fluorine, chlorine, bromine or methyl, R ₅ is hydrogen, fluorine, chlorine, bromine, methyl or methoxy, R ₇ is hydrogen, fluorine, chlorine, bromine , carbon number is 1~
2 is alkyl or alkoxy having 1 to 2 carbon atoms, R ₈ is hydrogen, methyl, chlorine or bromine, R ₉ and R ₁₀ are independently hydrogen, methyl, chlorine or bromine, W and Q are independently oxygen or sulfur, n is 0, 1 or 2, X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy having 1 to 3 carbon atoms, trifluoromethyl,
CH ₃ S— or CH ₃ OCH ₂ —, and Y is methyl or methoxy, provided that (a) when R ₅ is other than hydrogen, R ₃ , R ₄ , R ₆
and at least one of R ₇ is other than hydrogen,
and at least two of R ₃ , R ₄ , R ₆ and R ₇ should be hydrogen; (b) R ₅ is hydrogen; and R ₃ , R ₄ , R ₆ and R ₇
When all of are other than hydrogen, R ₃ , R ₄ ,
All of R ₆ and R ₇ should be chlorine or methyl, and (c) when R ₃ and R ₇ are both hydrogen,
at least one of R ₄ , R ₅ or R ₆ should be hydrogen] and agriculturally suitable salts thereof. The presence of undesirable plants causes substantial damage to useful crops, especially agricultural products that meet the basic food and fiber needs of humans, such as cotton, rice, maize, wheat, etc. The recent population explosion and the resulting global food and fiber shortages require improvements in the production efficiency of these crops. Preventing or minimizing the loss of such valuable crop parts by killing or inhibiting the growth of undesirable plants is one way to improve this efficiency. A wide variety of substances are available that are useful for killing or inhibiting the growth of unwanted plants, and such substances are commonly referred to as herbicides. However, there remains a need for more effective herbicides. The present invention relates to compounds of the formula and their agriculturally acceptable salts, suitable agricultural compositions containing them and as general and selective pre- and/or post-emergent herbicides and plant growth inhibitors. and their use as agents. [In the formula, _R1 is F, Cl, Br, _CF3 , _C1 to _C3 alkoxy, _C1 to _C3 alkyl, _{NO2 , CO2R4} ,
_SO2R5 , _{SO2NR6R7 , SO2N ( OCH3 ) CH3} ,
SO ₂ OCH ₂ CF ₃ , OSO ₂ R ₅ or CH ₂ L, where L is SO ₂ NR ₆ R ₇ , OCH ₃ , OC ₂ H ₅ , CO ₂ CH ₃ or
_CO2C2H5 , _R2 is H, Cl, Br, F, _{CF3 or OCH3} , _R4 is _C1 - _C3 alkyl _{, CH2CH} = _{CH2 , CH2CH2Cl} or _CH2CH2OCH3 , _R5 is _C1 - _C3 alkyl _{or CF3} , _R6 and _R7 are independently _{C1 - C3} alkyl, and _R8 is H or _CH3 , R ₉ is H or C ₁ -C ₃ alkyl, and R ₃ is

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] or

[Formula], W is O or S, X is CH ₃ , OCH ₃ or Cl, Y is CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , CH ₂ OCH ₃ , NH ₂ , _NHCH3 or N( _CH3 ) ₂ , Z is CH _or N, _X1 is H, Cl, _CH3 , _OCH3 or _OC2H5 , _X2 is _CH3 , _C2 H ₅ , OCH ₃ or OC ₂ H ₅ , X ₃ is CH ₃ or OCH ₃ , and Y ₁ is CH ₃ or OCH ₃ , provided that (1) when W is S, R ₈ is H, (2) the total carbon number of R ₆ and R ₇ is 4 or less, and (3) when X is Cl, Z is CH and Y is NH ₂ , NHCH ₃ , N ( _CH3 ) ₂ or _OCH3 ] and agriculturally suitable salts thereof. In the present invention, in the formula (), particularly, in the formula, R _{1
is Cl} , _{CH3 , NO2} , _CO2R4 , _{SO2R5 , SO2NR6R7}
or _OSO2R5 , _R2 is H _{, R4} is _C1 - _C2 alkyl, _R5 is _C1 - _C3 alkyl, _R6 and _R7 are _CH3 , R ₈ is H, R ₉ is H or CH ₃ , R ₃ is

[Formula], where X and Y are independently CH ₃ or OCH ₃ and Z is CH
or N, and W is O, provided that in the formula, R ₉ is H, Z is CH, X is OCH ₃ , and Y is OCH ₃ , then R ₁ is other than CO ₂ CH ₃ The present invention relates to compounds of the following and agriculturally acceptable salts thereof. In particular, the following are suitable. N-[(4,6-dimethoxy-pyrimidine-2
-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide, melting point 207-208
°C, N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-
(2-Nitrophenyl)-methanesulfonamide, melting point 185-188°, N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)-methanesulfonamide, melting point
194-195゜, N-[(4-methoxy-6-methyl-1,3,
5-triazin-2-yl)aminocarbonyl]
-1-(2-nitrophenyl)methanesulfonamide, melting point 165-168°, N-[(4,6-dimethyl-pyrimidine-2-
yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide, melting point 192-194
°, 2-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester, melting point 154-156°, 2-[[(4- Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester, melting point 162~
165゜, 2-[[(4-methoxy-6-methyl-1,3,
5-triazin-2-yl)aminocarbonyl]
Aminosulfonylmethyl]benzoic acid methyl ester, melting point 135-140°, 2-[[(4,6-dimethyl-pyrimidine-2-
yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester, melting point 165-167°, 2-[[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl] Benzoic acid methyl ester, melting point
125-130°, and N-[(4,6-dimethoxy-pyrimidine-2
-yl)aminocarbonyl]-1-(2-methylsulfonyloxyphenyl)methanesulfonamide, melting point 202-204° (decomposition). Compounds of the formula, including the compounds of the present invention, can be designated as useful intermediates for the preparation of compounds of the formula: [Here, _R1 is F, Cl, Br, _CF3 , _C1 - _C3 alkoxy, _C1 - _C3 alkyl, _NO2 , _{CO2R4 ,
SO2R5} , _{SO2NR6R7 , SO2N ( OCH3 ) CH3} ,
SO ₂ OCH ₂ CF ₃ , OSO ₂ R ₅ or CH ₂ L, where L is SO ₂ NR ₆ R ₇ , OCH ₃ , OC ₂ H ₅ , CO ₂ CH ₃ or
_CO2C2H5 , _R2 is H, Cl, Br, F, _{CF3 or OCH3} , _R4 is _C1 - _C3 alkyl _{, CH2CH} = _{CH2 , CH2CH2Cl} or _CH2CH2OCH3 , _R5 is _{C1 - C3} alkyl _or CF3, _R6 and _R7 are independently _{C1 - C3} alkyl,
and R ₉ is H or C ₁ -C ₃ alkyl, provided that the total number of carbon atoms in R ₆ and R ₇ is 4 or less]. Among the compounds of the present invention, compounds of the following formula are particularly suitable as selective herbicides for rice: [wherein R ₁ is NO ₂ or OSO ₂ CH ₃ ]. Synthesis Compounds of the formula W=O can be prepared by reaction of a suitable benzenemethanesulfonyl isocyanate with a suitable amino heterocycle, as shown in Scheme 1 below. Reaction formula 1 [wherein R ₁ , R ₂ , R ₃ , R ₈ and R ₉ are as defined above]. The reaction of Scheme 1 is best carried out in an inert aprotic solvent such as methylene chloride, tetrahydrofuran or acetonitrile at temperatures between 20 DEG and 80 DEG. To accelerate the reaction,
A catalytic amount of 1,4-diaza-bicyclo[2,2,
2] Octane (DABCO) can be used. If the products are insoluble in the reaction solvent, they can be isolated by simple filtration. When the products are soluble, they can be isolated by evaporating the solvent and trituring the residue with a solvent such as 1-chlorobutane, diethyl ether or methanol and filtering. Compounds of the formula where W=S and R ₈ =H can be prepared by the reaction shown in Scheme 2. Reaction formula 2 [wherein R ₁ , R ₂ , R ₃ and R ₉ are as defined above] The reaction of Scheme 2 involves the reaction of a sulfonamide, an isothiocyanate, and one equivalent of a base such as anhydrous potassium carbonate. It is best carried out by suspension in a solvent such as, for example, acetone, methyl ethyl ketone, acetonitrile or ethyl acetate. The reaction is stirred at 25-80° for 1-24 hours. In some cases, the product precipitates from the reaction mixture and can be separated, suspended in dilute mineral acid, filtered again and washed with cold water. If the product does not precipitate, it can be isolated by evaporating the solvent, trituring the residue with dilute mineral acid, and filtering off the insoluble product. The heterocyclic isothiocyanate used in the step of Reaction Scheme 2 is disclosed in Japanese Patent Application Publication No. 51-
143686, method of June 5, 1976 or W. Abraham and G. Barnikow
Tetrahedron 29 , G91-7 (1973). Both of these documents are cited herein by reference. Benzenemethanesulfonyl isocyanate of the formula can be prepared by phosgenation of a sulfonamide of the formula in the presence of butyl isocyanate as shown in Scheme 3. As shown in Reaction Scheme 4, the sulfonylisocyanate of the formula
It can also be produced by phosgenation of butyl urea of the formula. Reaction formula 3 [wherein R ₁ , R ₂ and R ₉ are as defined above] The above reaction can be carried out using a suitable sulfonamide (),
A mixture of an alkyl isocyanate, such as butyl isocyanate, and a catalytic amount of a tertiary amine, such as 1,4-diazabicyclo[2,2,2]octane, in xylene or other inert solvent with a boiling point of > 135° It is carried out by heating to 135°. Phosgene is then added to the mixture over a period of 1 to 6 hours at 125 DEG to 135 DEG until an excess of phosgene is present as indicated by a permanent drop in the boiling point below 130 DEG.
The mixture is cooled and filtered to remove small amounts of insoluble by-products. Distillation of the solvent and alkyl isocyanate under reduced pressure leaves a residue of crude sulfonyl isocyanate, which can be used without further purification. Reaction formula 4 [wherein R ₁ , R ₂ and R ₉ are as defined above] A compound of the formula is prepared by adding a mixture of a sulfonamide, anhydrous potassium carbonate and n-butyl isocyanate in acetone or methyl ethyl ketone for 25-800 min. It is conveniently produced by stirring at 20°C until all the isocyanate has reacted. The product is isolated by quenching in dilute mineral acid and recrystallizing the solid product. The compound is treated with phosgene and a catalytic amount of DABCO in refluxing xylene or chlorobenzene in a manner similar to that described in Scheme 3. The sulfonamide of the formula can be prepared from an appropriately substituted benzyl chloride or benzyl bromide according to the following reaction scheme 5.
It can be prepared by the reaction sequence described therein. Reaction formula 5 [wherein A is chlorine or bromine, and
R ₁ , R ₂ and R ₉ are as defined above.] Reaction Scheme (5a) In Reaction Scheme (5a), a benzyl halide of formula Alternatively, it can be reacted with thiourea in an aprotic solvent such as benzene. Temperatures of 40-80° are typically required for 1/2-4 hours to complete the reaction. The product salt is isolated by cooling and filtering or by concentrating to remove the solvent. The salt is generally of sufficient purity to be fed directly to step (5b) without further purification. Reaction Scheme (5b) In Reaction Scheme (5b), the hydrochloride salt (A=chlorine) is suspended in water and contacted with at least 3 equivalents of chlorine between 5 and 20°. When using the corresponding hydrobromide salt (A=bromine), it is generally advantageous to exchange the bromide ions for nitrate ions by treatment with an aqueous solution of 1 equivalent of silver nitrate before chlorination. The silver is removed by filtration and the liquor treated as described above.
The product sulfonyl chloride of formula is isolated by filtration and washing with water. No further purification of the sulfonyl chloride is necessary. Scheme (5c) In scheme (5c), a sulfonyl chloride of the formula is suspended in an aprotic solvent such as diethyl ether, 1-chlorobutane, methylene chloride or tetrahydrofuran and heated in excess at a temperature between 0 and 25°. Contact with anhydrous ammonia. The product sulfonamide of formula is isolated by filtering, washing with water to remove the by-product ammonium chloride, and concentrating the organic solution.
Often, the crude sulfonamide can be used directly for the preparation of the sulfonyl isocyanate of formula. However, they can also be purified first by recrystallization from suitable organic solvents such as ethanol, acetonitrile or chloroform. The synthesis of heterocyclic amine derivatives, such as those shown by the formula, is described in the "Chemistry of Heterocyclic Compounds" series published by Interscience Publications, New York and London. has been done. Aminopyrimidine is DJ Brown
“Pyrimidine” in the above series of volumes
It is written inside. The synthesis of bicyclic pyrimidines of the formula is described in the following references: Braker, Sheehan;
Spitzmiller and Lott, J.Am.Chem.Sco. 69 , 3072 (1947), Mitter and Bhattacharya, Quart.J.Indian Chem.Soc.
4 , 152 (1927), Shrage and Hitchings, J.Org.Chem. 16 , 1153.
(1951), E. Bisayni et al., Bull.Soc.Chem.
Fr. 803 (1969), Kaldwell, Kornfeld and Donnell, J.Am.
Chem.Soc. 63 , 2188 (1941), and Fissekis, Myles and Brown, J.Org.Chem. 29 , 2670 (1964). All of the above are incorporated herein by reference. Agriculturally acceptable salts of compounds of formula are also useful herbicides, and they can be prepared by a number of methods known in the art. For example, a metal salt may be an alkali or alkaline earth metal salt with an anion that is sufficiently basic (e.g. hydroxide,
alkoxides, carbonates or hydrides); quaternary amine salts can also be prepared by similar teachings. A detailed example of such a technique is shown in US Pat. No. 4,127,405, the disclosure of which is incorporated herein by reference. The compounds of the present invention and their preparation are further illustrated by the following Examples and Reference Examples. Temperatures herein are given in degrees Celsius and all parts are by weight unless otherwise indicated. Reference example 1 2-nitrophenylmethylcarbamimidothioate hydrochloride 153.9g of o-nitrobenzyl chloride and
A solution of 68.5 g of thiourea in 900 ml of #2B ethanol was stirred at reflux temperature (80°) for 11/4 hours. Cool the solution to 60° and 1.1
-Chlorobutane was added. Further cooling to 15° produced a heavy precipitate. The precipitate was filtered, washed with 1-chlorobutane, and dried, yielding 185.9 g.
2-nitrophenylmethylcarbamimidothioate hydrochloride, melting point 190-192°, was produced. NMR (DMSO-d ₆ ) δ: 4.85 (s, 1.84, -CH ₂ ); 7.4-8.4 (m, 4.2H, 4 aromatic); 9.7 (broad singlet, 4.0H, 4NH's) Reference example 2 2-Nitrophenylmethanesulfonyl chloride To a suspension of 34.7 g of the product of Example 1 in 300 ml of water, 24.0 ml of liquid chlorine was added over 45 minutes at 10-15°. After stirring for a further 30 minutes at 10-12°, the product is separated, washed with water and
It was then air dried in a steam hood to give 31.6 g of 2-nitrophenylmethanesulfonyl chloride, mp 62.5-64.0°. Reference Example 3 2-Nitrophenylmethanesulfonamide To a suspension of 29.4 g of the product of Reference Example 2 in 250 ml of diethyl ether was added 6.5 ml of anhydrous ammonia for 50 minutes.
Added at ~15°. After stirring for 1 hour at 15-25°, the product is separated, washed with ether and water, and oven dried at 60° to give 20.5 g of 2-nitrophenylmethanesulfonamide, mp = 134.
~136° was given. NMR (DMSO-d ₆ ) δ: 4.7 (s, 1.8H, -CH ₂ -); 6.8-7.3 (broad singlet, 1.8H, -SO ₂ NH ₂ ); 7.5-8.3 (m, 4.4H, 4 Aromatic) Reference Example 4 2-Nitrophenylmethanesulfonyl isocyanate A solution of 9.0 g of the product of Reference Example 3, 4.2 g of butyl isocyanate and 0.1 g of DABCO in 80 ml of dry xylene was heated to 136°. 3.0ml to this solution
of liquid phosgene was added at a rate to maintain the temperature between 125-136°. This addition took approximately 21/2 hours. The solution was cooled to 25°, filtered under nitrogen, and stripped under reduced pressure to give crude 2-nitrophenyl methanesulfonyl isocyanate as a viscous, water-sensitive oil that was observed in the infrared at 2230 cm ^-1 It showed a sulfonylisocyanate peak. Example 1 N-[(4,6-dimethoxypyrimidine-2-
yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide Under nitrogen atmosphere, 2.2 g of the product of Reference Example 4,
A mixture of 0.9 g of 4,6-dimethoxy-2-aminopyrimidine and 2-3 crystals of DABCO was added to 15
1 at 50-55° in ml of dry acetonitrile.
Heat for an hour and then stir at room temperature overnight. The product was filtered, washed first with acetonitrile and then with 1-chlorobutane, and oven dried at 60° under reduced pressure to yield 1.8 g of N-[(4,6-dimethoxypyrimidin-2-yl)amino carbonyl]
-1-(2-nitrophenyl)methanesulfonamide, melting point = 207-208° (d). NMR (DMSO-d ₆ ) δ: 3.8 (s, 6.1H, Het-OCH ₃ 's); 5.3 (s, 1.8H, -CH ₂ -); 6.0 (s, 1.0H, Het-H); 7.7 -8.3 (m, 4.1H, 4 aromatic); 10.9 (s, 1.0H, NH); ~12.5 (broad singlet, 0.9H, NH). Analysis for C ₁₄ H ₁₅ N ₅ O ₇ S Calculated value: C, 42.31; H, 3.80; N, 17.63 Actual value: C, 42.6, 42.6; H, 3.9, 3.9; and N, 17.7, 17.8 Reference example 5 2 -(Methylsulfonyl)phenylmethylcarbamimidothioate hydrobromide A solution of 36.5 g of 2-(methylsulfonyl)benzyl bromide and 11.4 g of thiourea in 500 ml of absolute ethanol at reflux temperature for 11/2 hours. Stir for several minutes and then allow to cool to room temperature. When left to stand, the solution forms white feather-like crystals;
It was collected by filtration, washed with cold 1-chlorobutane, and dried under vacuum. Yield of 2-(methylsulfonyl)phenylmethyl carbamimidothioate hydrobromide, melting point 203-206°C, is 36.3
It was hot at g. NMR (DMSO-d ₆ ) δ: 3.3 (s, 3H, -CH ₃ ); 4.9 (s, 2H, -CH ₂ -); 7.6-8.1 (m, 4H, aromatic); 9.4 (broad singlet, 4H, NH′s). Reference Example 6 2-(Methylsulfonyl)phenylmethanesulfonyl chloride A solution of 29.5 g of the product from reference example 5 in 450 ml of water was reacted with 15.5 g of silver nitrate in 45 ml of water. The produced silver bromide precipitate was removed by filtration,
It was then washed with 50 ml of water. Aqueous liquid then 180
ml of glacial acetic acid and reacted at 0°-5°C with 15 ml of liquid chlorine added over 30 minutes. While allowing the temperature to rise naturally to 25℃,
The reaction mixture was stirred for an additional 13/4 hours. The pale yellow solid was collected by filtration, washed with water, and air dried in a steam hood overnight.
22 g of 2-(methylsulfonyl)phenylmethanesulfonyl chloride was produced, which was used without further purification. NMR (DMSO-d ₆ ) δ: 3.4 (s, 3H, -CH ₃ ); 4.4 (s, 2H, -CH ₂ -); 7.5-7.9 (m, 4H, aromatic) Reference example 7 2-(methyl Sulfonyl)phenylmethanesulfonamide To a suspension of 22 g of the product from reference example 6 in 500 ml of dry diethyl ether was added 25 ml of anhydrous ammonia at 0-5°C. The reaction mixture was heated to 5°~
Stirred for 45 minutes at 15°C and then allowed to warm to room temperature over 1 hour. The solvent was removed under vacuum and the resulting solid was washed with water and ether.
Further evaporation of the solvent under vacuum gave 4.6 g of (2-methylsulfonyl)phenylmethanesulfonamide, mp 124-127°C, as a tan solid. NMR (DMSO-d ₆ ) δ: 3.3 (s, 3H, -CH ₃ ); 5.0 (s, 2H, -CH ₂ -); 7.6-7.8 (m, 3H, aromatic); 8.0 (m, 1H, Aromatic) IR (KBr): 3320, 3260, 1340, 1300, 1150cm ^-1 . Reference example 8 N-[(n-butyl)aminocarbonyl]-2
-(Methylsulfonyl)phenylmethanesulfonamide A mixture of 5.0 g of the product from Reference Example 7, 4.2 g of anhydrous potassium carbonate and 3.4 ml of n-butyl isocyanate was brought to reflux temperature in 60 ml of methyl ethyl ketone for 5 hours. It was heated. After cooling to room temperature, the solution was poured into 200 ml of ice water. This aqueous solution was acidified to approximately pH 1 by slow addition of concentrated hydrochloric acid, resulting in a white precipitate. The solid is filtered, washed with water and 1-chlorobutane, and then dried in a vacuum oven to yield 6.2 g of N-[(n-butyl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide. was obtained as a tan solid, mp 149-151°C (decomposition). NMR (DMSO-d ₆ ) δ: 0.9-1.6 (m, 7H, -CH ₂ CH ₂ CH ₃ ); 3.0-3.2 (m, 2H, -CH ₂ -); 3.4 (s, 3H, -CH ₃ ) ; 5.4 (s, 2H, —CH ₂ —); 6.6 (br s, 1H, N—H); 7.6—7.9 (m, 3H, aromatic); 8.0—8.2 (m, 1H, aromatic). IR (KBr): 3350, 3250, 1700, 1320, 1150 cm ^-1 Reference Example 9 2-(Methylsulfonyl)phenylmethanesulfonyl isocyanate 5.5 g of the product from Reference Example 8 and 0.1 g of 1,
A suspension of 4-diazabicyclo[2.2.2]octane (DABCO) in 100 ml of dry xylene was heated to 125°-130°C under a nitrogen atmosphere. At this temperature, 2.5 ml of phosgene was added dropwise at such a rate as to keep the temperature above 120°C. After the addition was complete (approximately 1 hour), the solution was heated at 125° C. for an additional 2 hours. After cooling to room temperature, the mixture was filtered under nitrogen and concentrated in vacuo to give crude 2-(methylsulfonyl)phenylmethanesulfonyl isocyanate as a yellow semi-solid. It was sent to the next stage without refining. The IR spectrum of this intermediate product showed a characteristic isocyanate absorption at 2240 cm ^-1 . Example 2 N-[(4,6-dimethoxypyrimidine-2-
yl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide To a solution of 3.0 g of the product from Reference Example 9 in 30 ml of dry dichloromethane is added 1.2 g of 4,6-dimethoxy-2-aminopyrimidine. , and the yellow homogeneous solution was stirred at room temperature overnight. The precipitated desired product was collected by filtration, washed with 1-chlorobutane, and dried in vacuo. N- [(4,
The yield of 6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(methylsulfonyl)phenylmethanesulfonamide, melting point 180 DEG -182 DEG C., was 2.4 g of a white solid. NMR (DMSO-d ₆ ) δ: 3.8 (s, 6H, heterocyclic OCH ₃ ); 5.4 (s, 2H, -CH ₂ -); 6.0 (s, 1H, heterocyclic H); 7.6-8.0 ( m, 4H, aromatic); 10.6 (br s, 1H, NH). IR (KBr): 1730, 1610, 1580, 1370, 1350, 1150cm ^-1 . Reference Example 10 1-(2-nitrophenyl)ethylcarbamimidothioate hydrobromide A solution of 33.5 g of 1-(2-nitrophenyl)ethyl bromide and 11.4 g of thiourea in 375 ml of absolute ethanol at reflux temperature Stirred for 31/2 hours. The reaction mixture was allowed to cool to room temperature and concentrated in vacuo to 1/2 volume. The solution was then cooled to about -60°C and 1-chlorobutane was added until a gummy solid formed. The supernatant was decanted and the residue was dried in vacuo to give 38 g of 1-(2-nitrophenyl)ethylcarbamimidothioate hydrobromide as a pale orange solid, which was not purified further. . NMR (DMSO- _d6 ) δ: 3.7 (wide d, J=7Hz, 3H, _-CH3 ); 5.5 (wide q, J=7Hz, 1H,

[Formula]); 7.5-8.0 (m, 4H, aromatic); 9.4 (broad s, 4H, N-H′s). Reference Example 11 1-(2-Nitrophenyl)ethanesulfonyl chloride A solution of 37.6 g of the product from Reference Example 10 in 700 ml of water was reacted with 21.9 g of silver nitrate in 60 ml of water. The produced silver bromide precipitate was removed by filtration,
And washed with water. Glacial acetic acid (250 ml) was added to the aqueous solution, the solution was cooled to 0°C and
Treated with 23 ml of liquid chlorine added over a period of minutes. After stirring for 1 hour at 0°-5°C, the reaction mixture was allowed to warm to room temperature over an additional hour. The solid that formed was filtered and washed with water. Air drying in a steam hood overnight provided 27.5 g of 1-(2-nitrophenyl)ethanesulfonyl chloride as a pale yellow solid. NMR (DMSO- _d6 ) δ: 1.7 (d, J=7Hz, 3H, _-CH3 ); 5.0 (q, J=7Hz, 1H,

[Formula]); 7.0 (br s, 2H, NH ₂ ); 7.4-8.0 (m, 4H, aromatic). IR (KBr): 3340, 3260, 1350, 1310, 1160cm ^-1 . Reference Example 12 1-(2-Nitrophenyl)ethanesulfonamide To a stirred suspension of the product from Reference Example 11 in 350 ml of dry diethyl ether was added liquid anhydrous ammonia (10 ml) at 0° to 5°C. Added over 20 minutes. The reaction mixture was stirred for 30 minutes at 0°-5°C and allowed to warm to room temperature over 2 hours. The solids were filtered and washed with diethyl ether. The liquid was concentrated in vacuo to give a yellow solid, which was washed with water and 1-chlorobutane and then dried under vacuum to give 17 g of 1-chlorobutane.
(2-Nitrophenyl)ethanesulfonamide was formed as a pale yellow solid, melting point 107°-109°C. NMR (DMSO- _d6 ) δ: 2.1 (d, J=7Hz, 3H, _-CH3 ); 6.2 (q, J=7Hz, 1H,

[Formula]); 7.6-8.1 (m, 4H, aromatic). IR (KBr): 1530, 1350, 1160 cm ^-1 . Reference example 13 1-(2-nitrophenyl)ethanesulfonyl isocyanate A mixture of 16 g of the product from reference example 12, 8.0 ml n-butyl isocyanate and 0.2 g 1,4-diazabicyclo[2.2.2]octane (DABCO) 11/2 to 130°-135°C in 125 ml of dry xylene.
Heated for an hour. To this solution 6 ml of phosgene were added at such a rate as to keep the temperature above 130°C. After the addition was complete (approximately 1 hour), the solution was cooled and passed under nitrogen. The liquid was concentrated in vacuo to give crude 1-(2-nitrophenyl)ethanesulfonyl isocyanate as a sticky orange oil. The IR spectrum of this compound showed a characteristic isocyanate absorption at 2240 cm ^-1 . Example 3 N-[(4,6-dimethoxypyrimidine-2-
yl)aminocarbonyl]-1-2-nitrophenyl)ethanesulfonamide 4.0 g of the product from Reference Example 13 and 2.2 g of 4,
A solution of 6-dimethoxy-2-aminopyrimidine in 29 ml of dry acetonitrile was heated to about 60° C. for about 11/2 hours and then stirred at room temperature overnight.
The precipitated product was collected, washed with 1-chlorobutane, and then dried under vacuum. The yield of N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)ethanesulfonamide was 3.1 g of white solid, melting point 168~
It was 170℃. NMR (DMSO-d ₆ ) δ: 1.8 (d, J = 7Hz, 3H, -CH ₃ ); 3.8 (s, 6H, heterocyclic OCH ₃ ); 5.6 (q, J = 7Hz, 1H,

[Formula]); 5.8 (s, 1H, heterocyclic H); 7.6-8.0 (m, 4H, aromatic); 10.6 (broad s, 1H, N--H). IR (KBr): 1720, 1610, 1580, 1360, 1200, 1150cm ^-1 . Using the steps and examples described above and selecting the appropriate amino heterocycle and sulfonyl isocyanate, the compounds listed in Tables 1-2 were prepared. The sulfonylisocyanate intermediates listed in Table 3 were also prepared using the above process and reference examples.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

Table: Preparations Useful preparations of compounds of formula may be prepared in conventional manner. They include powders, granules, tablets, suspensions, emulsions, wettable powders, concentrated emulsions, and the like. Many of these can be applied directly. The spray preparations can be bulked up in a suitable medium and used in spray volumes of a few liters to a few hundred liters/ha. High thickeners are primarily used as intermediates for further formulation. Broadly speaking, the preparation contains the active ingredient approx.
0.1-99% by weight, and a) about 0.1-20% surfactant.
and b) about 1 to 99.9% of at least one solid or liquid diluent. More particularly the preparation will contain these ingredients in approximately the proportions indicated below:

Table of Contents Of course, lower or higher amounts of active ingredient than those shown in the table may be present depending on the intended use and physical properties of the compound. A high proportion of surface-active to active ingredients is particularly desirable and is achieved by incorporation into the formulation or by mixing in a tank. Typical solid diluents are described in “Handbook of Insecticide” by Watkins et al.
Dust Diluents and Carriers”, 2nd edition, Dorland Books, Caldwell, NJ
), but other solids, both natural and synthetic, may also be used. Adsorptive diluents are also suitable for wettable powders and powder concentrates. Typical liquid diluents and solvents are described by Marsden,
"Solvents guide", 2nd edition, Intersience, NY, 1950. Solubility below 0.1% is suitable for concentrated suspensions; concentrated solutions are preferably stable to phase separation at 0°C. “McCutcheon’s Detergents and
Emulsifiers Annual”, Allured Publ. Corp., NJ, and by Sisely and Wood.
“Encyclopedia of Surface Active Agents”, Chemical Publ.Co.Inc., NY,
1964 indicates surface activity and its recommended uses. All preparations may contain small amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc. Methods for producing such compositions are well known.
Solutions are prepared by simply mixing the components. Finely divided solid compositions are produced by mixing and commonly grinding using a hammer mill or fluid energy mill. Suspensions are made by wet milling (see Littler, US Pat. No. 3,060,084). Granules and tablets may be produced by spraying the active substance onto preformed granular carriers or by agglomeration methods. References, by J.E. Browning,
“Agglomeration”, Chemical Engineering, December 4, p. 147 (1967), and Perry.
Author, Chemical Engineer's Handbook, 4th edition,
pp. 8-59, McGraw-Hill, Inc.
Hill, NY), 1963. For further literature on preparation techniques see, for example: HM Loux, US Pat. No. 3,235,361
No. 6, column 6, line 16 to column 7, line 19, and Examples 10 to 41. RW Luckenbaugh, U.S. Patent No. 3,309,192, column 5, line 43 to 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, column 3, line 66 to column 5, line 17 and Examples 1-4. GC Klingman, “Weed
Contral as a Science”, John Willy
John Wiley and Sons, Inc.
, NY), 1961, pp. 81-96. JD Fryer and SA Evans, “Weed Control Handbook”, No. 5
Edition, Blackwell Scientific Publications
Publications, Oxford), 1968, pp. 101-103. The disclosures of the above-mentioned documents are incorporated herein by reference. In the following formulation examples, all parts are by weight unless otherwise specified. In addition, in the following formulation examples, formulation example 7 is a reference example, and other formulation examples 1 to 6 and 8 to 16 are examples. Preparation example 1 Wettable powder N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide 80% Sodium alkylnaphthalenesulfonate 2% Sodium ligninsulfonate 2% Synthetic amorphous silica 3% Kaolinite 13% The above ingredients were mixed, hammer milled to an average particle size of less than 50 microns, remixed and packaged. Preparation example 2 Wettable powder N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-
(2-nitrophenyl)methanesulfonamide
50% Sodium alkylnaphthalene sulfonate 2% Low viscosity methyl cellulose 2% Diatomaceous earth 46% The above ingredients were mixed and coarsely ground with a hammer mill.
It was then air milled to produce particles that were essentially all 10 microns or less in diameter. The product was remixed and packaged. Preparation Example 3 Granules Wettable powder of Preparation Example 2 5% Attapulgift granules 95% (American standard sieve, 20-40 mesh; 0.84-
0.42 mm) A slurry of wettable powder containing 25% solids was sprayed onto the attapulgite granules in a double cone mixer. The granules were dried and packaged. Preparation example 4 Extruded tablet N-[(4-methoxy-6-methylpyrimidine-
2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide 25% Anhydrous sodium sulfate 10% Crude calcium ligninsulfonate 5% Sodium alkylnaphthalenesulfonate 1% Calcium/magnesium bentonite 59% Mix the above ingredients. , processed in a hammer mill and then moistened with approximately 12% water. This mixture was extruded into cylinders with a diameter of about 3 mm, which were cut into tablets with a length of 3 mm. It could be used directly after drying, or the dried tablets could be crushed and passed through a No. 20 US standard sieve (0.84 mm opening). It was packaged for use with particles that fit through a No. 40 US standard sieve (0.42 mm opening), and the area under the sieve was circulated. Preparation Example 5 Oily suspension N-[(4-methoxy-6-methyl-1,3,5
-triazin-2-yl)aminocarbonyl]-
1-(2-nitrophenyl)methanesulfonamide 25% Polyoxyethylene sorbitol hexaoleate 5% Higher aliphatic hydrocarbon oil 70% The above ingredients were ground together in a sand mill to reduce solid particles to about 5 microns or less. . The resulting suspension was applied directly, preferably after being extended with oil or emulsified in water. Preparation example 6 Wettable powder N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide 20% Sodium alkylnaphthalenesulfonate 4% Sodium ligninsulfonate 4% Low viscosity methylcellulose 3% Attapulgite 69% The above components were thoroughly mixed. After milling in a hammer mill to produce particles essentially all under 100 microns, the material was remixed, passed through a No. 50 US standard sieve (0.3 mm opening), and packaged. Preparation Example 7 (Reference Example) Low strength granules 2-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]amino-sulfonylmethyl]benzoic acid, methyl ester 1% N,N-dimethylformamide 9% Attapulgite Granules 90% (US Standard Sieve No. 20-40) The above ingredients were dissolved in a solvent and the solution was sprayed onto the dedusted granules in a double cone mixer. After the spraying of the solution was completed, the mixer was run for a while and then the granules were packaged. Preparation Example 8 Aqueous suspension N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-methylsulfonyloxyphenyl)methanesulfonamide
40% polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether 0.5% disodium phosphate 1% monosodium phosphate 0.5% polyvinyl alcohol 1.0% water 56.7% The above ingredients were mixed and essentially all the particles were ground together in a sand mill until the dimensions of the particles were less than 5 microns to produce particles with essentially all dimensions less than 5 microns. Preparation Example 9 Solvent 2 - [[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester 5% Water 95% Stir the salt directly into water The solvent was then added and packaged for subsequent use. Preparation example 10 Low strength granules 2-[[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester 0.1% Attapulgite granules 99.9% (US standard The active ingredient was dissolved in the solvent and the solution was sprayed onto the dedusted granules in a double cone mixer. After spraying the solution was complete, the material was warmed to evaporate the solvent. Leave the substance as it is and cool it.
Then it was packaged. Preparation example 11 Granules Agent N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide 80% Wetting agent 1% Crude lignin sulfonate 10% (5~ 20% natural sugar content) Attapulgite clay 9% The above ingredients were mixed and ground through a 100 mesh screen. This material was then added to a fluidized bed granulator, the air flow was adjusted to gently fluidize the material, and fine mist droplets of water were sprayed onto the fluidized material. Fluidization and atomization continued until granules of the desired size range were produced. Although spraying was stopped, fluidization was continued, optionally with heating, until the water content was reduced to the desired level, generally below 1%. The seeds were then removed, sieved to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use. Preparation example 12 Highly concentrated agent N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide 99% Silica aerosol 0.5% Synthetic amorphous silica 0.5% Above ingredients were mixed and ground in a hammer mill to produce a material that essentially all passed through a US Variable Sieve No. 50 screen (0.3 mm aperture).
This thickener can be further formulated if necessary. Preparation example 13 Wettable powder N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-1-
(2-nitrophenyl)methanesulfonamide
90% Sodium sulfonate Dioctyl citrate 0.1% Synthetic finely divided silica 9.9% The above ingredients were mixed and ground in a hammer mill to produce particles that were essentially all under 100 microns. The material was fitted into a US Standard Sieve No. 50 screen and then packaged. Preparation example 14 Hydrating agent 2-[(4-methoxy-6-methylpyrimidine-
2-yl)aminocarbonyl]-aminosulfonylmethyl]benzoic acid methyl ester 40% Sodium ligninsulfonate 20% Montmorillonite clay 40% The above ingredients were thoroughly mixed, coarsely ground in a hammer mill, and then ground in an air mill. to produce particles with essentially all dimensions less than 10 microns. The material was remixed and then packaged. Preparation example 15 Oil-based suspension 2-[[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester 35% Combination of polyalcohol carboxylic acid ester and oil-soluble petroleum sulfonate Mixture 6% Xylene 59% The above ingredients were combined and ground together in a sand mill to produce particles that were essentially all 5 microns or less. The product could be used directly, spread in oil or emulsified in water. Preparation Example 6 Powder Preparation 2-[[(4-methoxy-6-methyl-1,3,5
-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester
10% Attapulgite 10% Pyrophyllite 80% The active ingredients were mixed with attapulgite and then passed through a hammer mill to produce particles substantially all of which were less than 200 microns. The ground concentrate was then mixed with powdered pyrophyllite to form a mass. Uses The compounds of the invention are potent herbicides. Areas where they expect complete eradication of all plants;
Shows wide-ranging utility for pre- and/or post-emergence control of weeds, e.g. around fuel storage tanks, ammunition depots, industrial storage areas, car parks, amphitheaters, billboard areas, highways and railway areas. . Additionally, the compounds are useful for selectively controlling weeds in fields of crops such as wheat and soybean plants, pre- and/or post-emergence. The rate of use of the compounds of the invention will depend on their use as selective or systemic herbicides, the coexisting crop species, the weed species to be controlled, the weather and climate, the formulation chosen,
Determined by many factors including application method, amount of foliage present, etc. Generally speaking, the compounds are approximately
Should be used in amounts of 0.01-10Kg/ha. In this case, lower doses in the above range may be used when applied to light soils and/or soils with low organic matter content, when selectively controlling weeds, or when only short-term persistence is required. Ru. The compounds of the invention can also be used in combination with other commercially available herbicides, such as those of the triazine, triazole, uracil, urea, amide, diphenyl ether, carbamate and bipyridylium types. Particularly useful are compounds of the invention and S-
(4-Chlorobenzyl)-N,N-diethylthiol carbamate, 2-chloro-2',6'-diethyl-N-(butoxymethyl)acetanilide, S
-Ethyl-N,N-hexamethylenethiol carbamate, 1-α,α-dimethylbenzyl-3-
It is a composition of p-tolylurea and 1-(α,α-dimethylbenzyl)-3-methyl-3-phenylurea. The herbicidal properties of this compound have been demonstrated in a number of greenhouse tests. The test method and results are as follows. Test A Digitaria spp., Echinochloa crusgalli, Avenafatua, Cassia tora, Ipomoea spp., Xanthium
spp.), sorghum, maize, soybean, rice, and wheat seeds and tubers of sorghum were planted in a growth medium and subjected to pre-emergence treatment with chemicals dissolved in a solvent that was harmless to the plants. . At the same time, cotton with five leaves (including cotyledons), kidney bean with the third leaflet spreading out, crabgrass with two leaves, goldenberry with two leaves, oat with two leaves, and three leaves with three leaves. Ebisugusa with leaves (including cotyledons), morning glory with four leaves (including cotyledons), Japanese sorghum with four leaves (including cotyledons), four-leaf sorghum, four-leaf corn, soybean with two cotyledons, trifoliate of rice, one leaf of wheat, and 3 to 5 leaves of red sedge were sprayed. Treated and control plants were kept in the greenhouse for 16 days and all species were compared to the control and the response to treatment was visually assessed.
The evaluation method used was based on a scale from 0 (no effect) to 10 (maximum effect). The accompanying letter symbols have the following meanings. C = yellowing/decay D = defoliation E = germination inhibition G = growth retardation H = influence of formation S = pigment deficiency U = abnormal pigment formation 6Y = abscessed bud or flower. The evaluation of compounds tested by this method is shown in Section A.
Shown in the table. Some of the compounds tested were found to be useful in the selective control of post-emergent weeds in corn, rice and wheat.

【table】

【table】

TABLE It should be noted that certain compounds tested had no activity at the levels tested, but may have activity at higher levels. Test B Two plastic bulb pans were filled with fertilized and limed Fallsington silt loam soil.
In one pan, add corn, sorghum, and Kentucky bluegrass.
blueglass) and various herbaceous plants. Other pans were planted with cotton, soybeans, Cyperus rotundus, and various broadleaf weeds. The following herbaceous plants and broad-leaved weeds were planted.
Scrubgrass (Digitaria sanguinalis), Golden millet (Echinochloacrus galli), Oat (Avena)
fatua), Jiyeonson Grass (Sorghum)
halepense), dallis grass (Paspalum
dilatatum), Setaria
faberii), Bromus
secalinus), mustard (Brassica arvensis), onus (Xanthium pennsylvanicum), blueberry (Amaranthus retroflexus), morning glory (Ipomoea)
hederacea), Cassiatora, Sidaspinosa, Abutilon theophrasti, and Datura stramoninm. Furthermore, the diameter is 12.5cm
Prepared soil was placed in two pots, and rice and wheat were planted. The other 12.5cm pot was planted with sugar beets. The above four containers were pre-emergent treated with several test compounds falling within the scope of the invention. After 28 days of treatment, the response of the plants to the chemical treatment was visually evaluated using the evaluation system described above in Test A. This data is shown in Table B. Certain compounds have been found to be useful for pre-emergence treatment of weeds in crops such as soybeans and wheat.

[Table] Test C Soybean, cotton, alfa, maize, rice, wheat, sorghum, velvet leaf (Abutilon theophrasti), and sesbania in 25 cm diameter plastic pots filled with Fallsington manure. (Sesbania
exaltata), Cassiatora, Ipomoea sp., Datura
stramonium), Onamomi (Xanthium
pennsylvanicum), crabgrass (Digitaria sp.),
Cyperus rotundus, Echinochloa crusgalli, Setaria faberii, and Avena
fatua) was planted. Approximately 2-1/2 weeks after planting, the young plants and all surrounding soil were sprayed with test chemicals dissolved in a solvent that is non-toxic to the plants. Fourteen days after treatment, all species were visually evaluated for response to treatment compared to untreated controls. The rating system was as described above with respect to Table A. The data are shown in Table C. It is clear that the test compounds have high post-emergence activity.

【table】

【table】

Table: Test D A 20 inch diameter plastic pan lined with polyethylene was filled with formulated Falsington silt loam soil. In one pan, add wheat (Triticum aestivum) and barley (Hordeum).
Avenafatua, Bromus tectrum, Bromus secalinus, Alopecurus myosuroides, Poa annua, Setaria viridis, Agropyron repens ), Italian ryegrass (Lolium multiflorum), and Bromus rigidus. In other pans, Russian shitsul (Salsola kali),
tansy mustard (Descuraina pinnata),
Smart Weed (Polygonum)
pensylvanicum), tumble mustard (Sisymbrium altissium), Kochia (Kochia
scoparia), Seafarers Perth (Capsella)
bursapastoris), Matricaria indora, Black nightshade (Sclanum nigrum), Yellow rocket (Barbarea vulgaris), Brassica kaber and Polygonum
convolvulus) seeds. The two pans described above were treated before germination. At the same time, two pans in which the above plant species were growing were treated post-emergence. The height of the plant at the time of treatment depends on the type of plant, but 1
It was in the range of ~15cm. dilute the applied compound with a non-phytotoxic solvent;
Then sprayed from the top of the pan. An untreated control and a solvent-only control were also included for comparison. All treatments were kept in the greenhouse for 20 days, at which time treatments were compared to controls and efficacy visually assessed. The recorded data is shown in Table D. Compound 1
The seeds were useful for pre- and/or post-emergent weed control in wheat and barley.

[Table] Test E A series of simulated rice paddy tests were conducted in a greenhouse.
formulating a compound selected from within the scope of the invention;
It was then applied directly to the paddy field 3 days after transplanting the rice. "Early" plant response evaluations (within one week after application were performed in some trials and "late" plant response evaluations (5-6 weeks after application) were performed in all trials.

【table】

Table: Several of the compounds tested gave excellent control of weeds in rice without causing damage to the rice.

Claims (1)

[Claims] 1 formula [In the formula, R ₁ is Cl, CH ₃ , NO ₂ , CO ₂ R ₄ ,
_{SO2R5 , SO2NR6R7} or _OSO2R5 , _{R2 is} H _{, R4} is _C1 - _{C2 alkyl} , _R5 is _C1 - _C3 alkyl, R ₆ and R ₇ are CH ₃ , R ₈ is H, R ₉ is H or CH ₃ , and R ₃ is [Formula], where X and Y are independently CH ₃ or OCH ₃ and Z is CH
or N, and W is O, provided that in the formula, R ₉ is H, Z is CH, X is OCH ₃ , and Y is OCH ₃ , then R ₁ is other than CO ₂ CH ₃ and agriculturally acceptable salts thereof. 2 N-[(4,6-dimethoxy-pyrimidine-
2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide. 3 N-[(4,6-dimethoxy-1,3,5-
triazin-2-yl)aminocarbonyl)-1
The compound according to claim 1, which is -(2-nitrophenyl)-methanesulfonamide. 4 N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-(2-
The compound according to claim 1, which is (nitrophenyl)-methanesulfonamide. 5 N-[(4-methoxy-6-methyl-1,
The compound according to claim 1, which is 3,5-triazin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide. 6 N-[(4,6-dimethyl-pyrimidine-2
-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide. 7 2-[[(4,6-dimethoxy-1,3,5-
The compound according to claim 1, which is triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester. 8. The compound according to claim 1, which is 2-[[(4-methoxy-5-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester. 9 2-[[(4-methoxy-6-methyl-1,
The compound according to claim 1, which is 3,5-triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester. 10 2-[[(4,6-dimethyl-pyrimidine-
2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester. 11 2-[[(4,6-dimethyl-1,3,5-
The compound according to claim 1, which is triazin-2-yl)aminocarbonyl]aminosulfonylmethyl]benzoic acid methyl ester. 12 The compound according to claim 1, which is N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-1-(2-methylsulfonyloxyphenyl)methanesulfonamide. 13 formula [In the formula, R ₁ is Cl, CH ₃ , NO ₂ , CO ₂ R ₄ ,
_{SO2R5 , SO2NR6R7} or _OSO2R5 , _{R2 is} H _{, R4} is _C1 - _{C2 alkyl} , _R5 is _C1 - _C3 alkyl, R ₆ and R ₇ are CH ₃ , R ₈ is H, R ₉ is H or CH ₃ , and R ₃ is [Formula], where X and Y are independently CH ₃ or OCH ₃ and Z is CH
or N, and W is O, provided that in the formula, R ₉ is H, Z is CH, X is OCH ₃ , and Y is OCH ₃ , then R ₁ is other than CO ₂ CH ₃ An agent for inhibiting undesirable plant growth, characterized in that it contains as an active ingredient a compound selected from the compounds and agriculturally acceptable salts thereof. 14. Claim 13 comprising an effective amount of an active ingredient selected from a compound of the formula and agriculturally acceptable salts thereof, at least one surfactant and a solid or liquid diluent. agent. 15. Claim 13 or 14, wherein the active compound is N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-1-(2-nitrophenyl)methanesulfonamide. agent. 16 Into paddy fields, an effective amount of A method for inhibiting undesirable plant growth in rice, comprising applying a compound selected from [where R ₁ is NO ₂ or OSO ₂ CH ₃ ].