KR830002771B1 - Method for preparing sulfonamide - Google Patents

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Description

Method for preparing sulfonamide

The present invention provides N- (heterocyclic aminocarbonyl) aryl sulfonamides and N- (heterocyclic aminocarbonyl) thienyl sulfonamides and agricultural products thereof of the following general formula (I) useful as plant growth regulators and herbicides It relates to a method for preparing a salt useful as.

In the above formula

또는

이고R is

or

ego

R ₁ and R ₂ are each hydrogen or CH ₃ ;

R ₄ is Cl, Br, F, NO ₂ , CH ₃ , OCH ₃ , CF ₃ or R ₃ S (O) n ′ wherein R ₃ is alkyl of 1 to 6 carbon atoms or alkenyl of 3 to 4 carbon atoms ego;

R ₅ is H, Cl, Br, F, CH ₃ or -OCH ₃ ;

W is O or S;

n is 0, 1 or 2;

X is CH ₃ or -OCH ₃ ;

Y is alkyl having 3 to 4 carbon atoms; Alkyl of 2 to 4 carbon atoms substituted with CH ₃ O; Alkyl of 2 to 4 carbon atoms substituted with 1 to 3 atoms of Cl, Br, F; Alkyl of 1 to 4 carbon atoms substituted with C ₂ H ₅ O, CN, CO ₂ H, CO ₂ CH ₃ or CO ₂ C ₂ H ₅ ; CH ₂ F; CH ₂ Cl; CH ₂ Br; Alkenyl having 2 to 4 carbon atoms; Alkynyl having 2 to 4 carbon atoms; SCN; N ₃ ; A (CH ₂ ) m A ₁ R ₇ wherein m is 2 or 3, R ₇ is alkyl having 1 to 3 carbon atoms, A1 is O or S, and A is O or S (O) n;

(여기서 A₂및 W₁은 각각 O 또는 S이고, R₁₅는 F, Cl, Br 중 1 내지 3개로 임의적으로 치환된 탄소수 1 내지 3의 알킬 또는 R₁₅는 N(CH₃)OCH₃또는 NR₈R₉이다);

Wherein A ₂ and W ₁ are each O or S, and R ₁₅ is C 1 to C 3 alkyl optionally substituted with 1 to 3 of F, Cl, Br or R ₁₅ is N (CH ₃ ) OCH ₃ or NR ₈ R ₉ );

또는 F, Cl, Br 중 1 내지 3원자로 치환된 탄소수 2 내지 4의 알킬이다) ; SR₁₄(여기서 R₁₄는)탄소수 1 내지 2의 사아노 알킬, 알릴 또는 프로팔길이다)이다]이고 ;[Where L is N (CH ₃ ) OCH ₃ or NR ₈ R ₉ and R ₈ and R ₉ are each H, CH ₃ or -C ₂ H ₅ , or L is OR ₁₀ (where R ₁₀ is H or carbon number) 1 to 4 alkyl); NR ₁₁ R ₁₂ where R ₁₁ is H or CH ₃ and R ₁₂ is alkenyl having 3 to 4 carbon atoms, OCH ₃ or alkyl having 2 to 3 carbon atoms substituted with OC ₂ H ₅ ; cyclopropyl or CN, CO ₂ CH ₃ or C 1 -C 2 alkyl substituted with CO ₂ C ₂ H ₅ ; OR ₁₃ (wherein R 13 is alkyl having 4 to 6 carbons, cyanoalkyl having 1 to 4 carbons, alkenyl having 3 to 4 carbons, alkynyl having 3 to 4 carbon atoms,

Or F 2, C 2 -C 4 alkyl substituted with 1 to 3 atoms in F, Cl, Br); SR ₁₄ , wherein R ₁₄ is saano alkyl, allyl or propargyl having 1 to 2 carbon atoms;

Z is CH or N;

However, when R ₁ and R ₂ are both CH ₃ or one of them is CH ₃ , Y cannot be OCH ₂ CH ₂ OCH ₃ .

United States Patent Application No. 824,805, filed Aug. 15, 1977 and No. 840,389, filed Oct. 6, 1977, describe compounds of the following general formula as herbicides.

In the above formula,

이며;E r

Is;

이고;The latter R is

ego;

Each patent is R ₁

또는

이며;

or

Is;

이고;R ₃ is chlorine, bromine, fluorine, nitro, methyl, methoxy or trifluoromethyl or

ego;

n is 0, 1 or 2;

R ₄ , R ₅ , R ₆ and R ₇ may each be hydrogen, fluorine, chlorine, bromine or methyl, and in each patent application R ₅ , R ₆ and R ₇ may be methoxy,

X is alkoxy, trifluoromethyl, CH ₃ S- or CH ₃ OCH ₂ -having 1 to 3 carbon atoms in each patent application;

Z is methyl or methoxy;

W is oxygen or sulfur.

United States Patent Application No. 840,167, filed October 6, 1977, describes a compound of the general formula:

In the above formula,

R ₁ and R ₂ may each be hydrogen or methyl;

또는

이고 ;R ₃ is

or

ego ;

X is alkoxy having 1 to 3 carbon atoms, CF ₃ , CH ₃ S—, CH ₃ OCH ₂ — or CH ₃ OCH ₂ CH ₂ O—;

Y is CH ₃ or OCH ₃ ;

Z is CH or N.

United States Patent Application No. 910,965, filed May 30, 1978, describes compounds of the following general formula as herbicides.

In the above formula,

은 산, 염, 에스테르 또는 아미드이며;

Is an acid, salt, ester or amide;

이고;R ₁ is

ego;

R ₂ is hydrogen, chlorine, bromine, fluorine, nitro, methyl, methoxy or methylthio;

R ₃ is hydrogen, chlorine, bromine or methyl;

R ₄ and R ₅ are independently hydrogen or methyl;

W is oxygen or sulfur;

X is methyl or methoxy;

,

, -O(CH₂)₂CO₂CH₃, -O(CH₂)₂CO₂C₂H₅, -S(CH₂)₂OCH₃, -S(CH₂)₂OC₂H₅, -SCH₂CO₂CH₃, -SCH₂CO₂C₂H₅,

,

-S(CH₂)₂CO₂CH₂또는 S(CH₂)₂CO₂C₂H₅이며 ;Y is -OCH ₂ CF ₃ , -O (CH ₂ ) ₂ OCH ₃ , -O (CH ₂ ) ₂ OC ₂ H ₅ , -O (CH ₂ ) ₃ OCH ₃ , -O (CH ₂ ) ₃ OCH ₂ H ₅ , -OCH ₂ CO ₂ CH ₃ , -OCH ₂ CO ₂ C ₂ H ₅ ,

,

, -O (CH ₂ ) ₂ CO ₂ CH ₃ , -O (CH ₂ ) ₂ CO ₂ C ₂ H ₅ , -S (CH ₂ ) ₂ OCH ₃ , -S (CH ₂ ) ₂ OC ₂ H ₅ ,- SCH ₂ CO ₂ CH ₃ , -SCH ₂ CO ₂ C ₂ H ₅ ,

,

—S (CH ₂ ) ₂ CO ₂ CH ₂ or S (CH ₂ ) ₂ CO ₂ C ₂ H ₅ ;

Z is CH or N.

In the absence of undesirable plants, there is substantial damage to agricultural products, in particular human basic foods and fibers, such as cotton, rice, corn, wheat and the like. Recently, there is an urgent need for improved cultivation of these farms due to population explosion, air pollution, and fiber storage loss. Preventing or minimizing the loss of the desired crops by killing or inhibiting growth of undesirable plants is an effective improvement. Substances effective for killing undesirable plants or inhibiting growth are commonly known as herbicides. However, there is a continuing need for more effective herbicides.

[여기서 A는 O 또는 S이고, L은 N(CH₃)OCH₃또는 NR₈R₉(여기서 R₈및 R₉는 각각 H, CH₃, 또는 C₂H₅이다), 또는 L 은OR₁₀(여기서 R₁₀은 탄소수 1 내지 4의 알킬이다) ; NR₁₁R₁₂(여기서 R₁₁은 수소 또는 CH₃이고 R₁₂는 탄소수 3 내지 4의 알케닐, OCH₃또는 OC₂H₅로 치환된 탄소수 2 내지 3의 알킬, 또는 CN, CO₂CH₃또는 CO₂C₂H₅로 치환된 탄소수 1 내지 2의 알킬이다) ; OR₁₃(여기서 R₁₃은 탄소수 1 내지 4의 시아노알킬, 탄소수 3 내지 4의 알케닐, 탄소수 3 내지 4의 알키닐,

또는 F, Cl, Br 중 1 내지 3 원자로 치환된 탄소수 2 내지 4의 알킬이다) ; SR₁₄(여기서 R₁₄는 탄소수 1 내지 2의 시아노알킬, 알릴 또는 프로팔길이다.)이다]을 나타내는 화합물이 바람직하다.Compounds of general formula (I) are preferred for their biological activity or ease of synthesis, or both advantages, wherein Y is alkyl having 1 to 4 carbon atoms substituted with CN, CO ₂ CH ₃ or CO ₂ C ₂ H ₅ ; Alkenyl having 2 to 4 carbon atoms; Alkynyl having 2 to 4 carbon atoms; SCN, N ₃ ; A (CH ₂ ) mA ₁ R ₇ , wherein m is 2 or 3, R ₇ is alkyl having 1 to 3 carbon atoms, and A ₁ is O or S (O) n;

Wherein A is O or S and L is N (CH ₃ ) OCH ₃ or NR ₈ R ₉ , wherein R ₈ and R ₉ are each H, CH ₃ , or C ₂ H ₅ , or L is OR ₁₀ (Wherein R ₁₀ is alkyl having 1 to 4 carbon atoms); NR ₁₁ R ₁₂ wherein R ₁₁ is hydrogen or CH ₃ and R ₁₂ is alkenyl having 3 to 4 carbon atoms, OCH ₃ or alkyl having 2 to 3 carbon atoms substituted with OC ₂ H ₅ , or CN, CO ₂ CH ₃ or C 1 -C 2 alkyl substituted with CO ₂ C ₂ H ₅ ; OR ₁₃ where R ₁₃ is cyanoalkyl having 1 to 4 carbon atoms, alkenyl having 3 to 4 carbon atoms, alkynyl having 3 to 4 carbon atoms,

Or C 2-4 alkyl substituted with 1 to 3 atoms in F, Cl, Br); Preference is given to compounds which represent SR ₁₄ , wherein R ₁₄ is cyanoalkyl, allyl or propargyl having 1 to 2 carbon atoms.

More preferred are increased activity and / or low cost as follows.

(1) a preferred range of compounds in which R ₁ and R ₂ are H and W is O;

(2) Y is AR ₁₆ where R ₁₆ is CH ₂ CF ₃ , CH ₂ CH ₂ OR ₁₇ , CH (CH ₃ ) CO ₂ R ₁₇ , (CH ₂ ) ₃ OR ₁₇ or CH ₂ CH ₂ CO ₂ R ₁₇ And A is oxygen or sulfur and R ₁₇ is CH ₃ , -C ₂ H ₅ or iC ₃ H ₇ .

(3) A more preferred compound (2) in which A is oxygen and R ₁₆ is not CH ₂ CH ₂ CO ₂ R ₁₇ ;

인 좀 더 바람직한 (3)의 화합물 ;(4) R is

More preferable compound of (3);

(5) More preferred compound of (4), wherein R ₅ is hydrogen or chlorine;

(6) the more preferable compound of (5), wherein R ₄ is chlorine or NO ₂ ;

(7) The more preferable compound of (6), wherein R ₅ is hydrogen.

Particularly preferred are marked herbicidal, or very advantageous ease of synthesis, or both:

2-[[6-methyl-2-) [2-nitrophenylsulfonylamino) carbonyl-amino] pyrimidin-4-yloxy] acetic acid methylester; 2-chloro-[[6-methyl-4 -(2,2,2-triphylouroethoxy) -1,3,5-triazin-2-yl] aminocarbonyl] benzenesulfon amide; N-[[4-methoxy-6- (2 , 2,2-trifluoroethoxy) -1,3,5-triazin-2-yl) aminocarbonyl] -2-yl) aminocarbonyl] -2-nitrobenzenesulfonamide; 2 [[2 -[(2-chlorophenylsulfonyl amino) carbonylamino] -6-methylpyrimidin-4-yloxy] propanoic acid methyl ester; and 2-[[6-methyl-2-[(2nitrophenyl) Sulfonylaminocarbonyl amino] -4-pininitro benzenesulfoamide; 2 [[2-[(2-chlorophenylsulfonyl amino) carbonylamino] -6-methylpyrimidin-4-yloxy] propanoic acid methyl ester; And 2-[(6-methyl-2-[(2-nitrophenyl) sulfonylaminocarbonyl amino] -4-pyrimidinyloxy] propanoic acid methyl ester.

synthesis

As in Scheme 1, the compound of formula (I) is suitably substituted sulfonyl isocyanate or isothiocyanate of formula (II) with 2-aminopyrimidine or 2-amino-1 of formula (III), Can be prepared by reacting 3,5-triazine; R, W, X, Y and Z are as described above.

Scheme 1

The reaction of Scheme 1 works best in an inert aprotic organic solvent (eg methylenecloroid, tetra hydrofuran or acetonitrile) at atmospheric pressure and temperature. The addition method is the same as the conventional method, but it is convenient to add sulfonyl isocyanate or isothiocyanate (II) while stirring the suspension of heterocyclic amine (III). Since isocyanates and isothiocyanates are usually liquids, their addition can be easily controlled. This reaction is usually exothermic. In many cases, the preferred product is crystallized in insoluble and pure form in a warm reaction medium. The soluble product in the reaction medium may be separated by treating the solid residue with a solvent such as 1-chlorobutane or ethyl ether and evaporating the solvent.

As in Scheme 2, a compound of formula (I) wherein R ₁ is H and R ₂ is CH ₃ is a suitable substituted sulfonylisocyanate or isothiocyanate of formula (II). It can be prepared by reaction with -methylaminopyrimidine or 2-methylamino-1,3,5-triazine, wherein R ₁ , R ₂ , W, X, Y and Z are as described above.

Scheme 2

The reaction is carried out as described in Scheme 1.

Compounds of formula (I) wherein R ₁ is methyl, as in Scheme 3, R ₁ is hydrogen, R, R ₂ , R ₁ , W, X, Y and Z are as described above and M is a metal cation Q can be prepared by methylating a salt of a compound of formula (I) that is an anion (eg halide or methylsulfate).

Scheme 3

The reaction of Scheme 3 works best in aprotic organic solvents (eg tetrahydrofuran, dimethylformamide or dimethyl acetamide) at ambient temperature and pressure. Alkylating agents (eg dimethyl sulfate, methyliomide) can be used. Preferred products can be separated by pouring the reaction mixture into water and filtering off the precipitated solids.

Other compounds of formula (I) wherein R ₁ is methyl are suitably substituted sulfonyl-N-methylcarbamyl chloride or sulfonyl-N-methylcarbamyl thioic chloride of formula (IV) as in Scheme 4. It can be prepared by reacting with 2-aminopyrimidine or 2-amino-1,3,5-triazine of general formula (III). (Wherein R ₁ , R ₂ , R, X, Y, W and Z are as described above).

Scheme 4

It is known to prepare urea from amines and carbanyl chlorides or carbamylthioic chlorides. The reaction is carried out at 20 to 130 ° C. in the presence of an acidic solvent (e.g. triethylamine, pyridine, or sodium carbonate) to give the same amount of chloride (IV) and amine (III) inert organic solvent (e.g. tetrahydrofuran , Xylene, methylene chloride). Soluble products can be separated by filtering the precipitated salts to concentrate the filtrate. Insoluble products can be removed by filtration and washing the free salt with water.

The intermediate chloride (IV) can be prepared by phosphogenating or thiophosphogenation of the N-methylsulfonamide salt. Sulfonamide salts are added to excess phosgene or thiophosgene in an inert organic solvent (e.g., tetrahydrofuran, toluene, xylene), while chloride (IV) is isolated or removed in excess of phosgene or thiophosgene in situ React with amine (III).

Heterocyclic amine synthesis is described in "The chemistry of Heterocyclic Compounds", a series published by Interscience Publ. New York and London. 2-aminopyrimidine is the class of the literature [D.J. Brown in "The Pyrimidines," Vol. XVI. 2-amino-1,3,5-triazines are described in E.M. Smolin and L. Rapoport, "S-Triazines and Derivatives," Vol. XIII]. 2-amino-1,3,5-triazines are described in K.R. Huffmann and F.C. Schaefer, J. Org. Chem. 28, 1812-1815 and 1816-1821 (1963).

Preparation of starting materials and intermediates of the compounds of the present invention as well as commercially useful salts of compounds of general formula (1) are described in U. S. Patent Nos. 824,805, filed on August 5, 1977 and 840,389, filed on 1977.10.6. The contents are described here for reference.

The compounds of the present invention and their preparation are described in the following examples and expressed in degrees Celsius.

Example 1

N-[[4- (2-methoxyethoxy) -6-methylpyrimidin-2-yl] amino-carbonyl] -2-chlorobenzenesulfonamide

To anhydrous stirring solution of 18.3 parts of 2-amino-4- (2-methoxyethoxy) -6-methylpyrimidine in 300 parts of methylene chloride was added 22 parts of 2-colobenzenesulfonyl isocyanate under atmospheric temperature and pressure. The mixture is stirred for 2 hours and the methylene chloride is removed under reduced pressure. The resulting solid was triturated with 1-chlorobutane and filtered to give N-[[4- (2-methoxyethoxy) -6-methylpyrimidin-2-yl] amino carbonyl] -2-chlorobenzenesulfonamide ( Melting point 130-140 degreeC) 35 parts are obtained. The product exhibits a unique absorption band in the infrared absorption spectrum.

The compounds of Table 1 can be prepared by the method of Example 1 using 2-amino pyrimidine or 2-amino-1,3,5-triazine and the appropriately substituted benzenesulfonyl isocyanate or isothiocyanate equivalents have.

Table 1-A

TABLE 1-B

Table 1-C

Table 1-D

Example 2

Methyl [6-methyl-2-[(2-thienylsulfonyl) aminocarbonylamino] pyrimidin-4-yloxy] acetate

20 parts of 2-thiophenesulfonyl isocyanate is added to 18 parts of anhydrous stirring solutions of 300 parts of methylene chlorides at 300 degreeC of atmospheric temperature. Leave the solution for 3 hours and pour into ice. Sodium hydroxide is added to adjust the aqueous layer to pH 11 and the methylene chloride layer is separated. The aqueous layer is neutralized with hydrochloric acid solution and extracted with methylene chloride. After drying the extract and removing the solvent, 8 parts of methyl [6-methyl-2-[(2-thienyl-sulfonyl) aminocarbonylamino] pyrimidin-4-yloxy] acetate (melting point 114 to 120 ° C.) was obtained. Is generated.

The conjugates of Table 2 can be prepared by the method of Example 2 using 2-aminopyrimidine or 2-amino-1,3,5-triazine and 2-thiophensulfonylisocyanate or isothiocyanate equivalents have.

Table 2-A

TABLE 2-B

TABLE 2-C

Table 2-D

Compounds of Table 3 are prepared by the method of Scheme 2 using 2-methylamino-pyrimidine or 2-methylamino-1,3,5-triazine and an appropriately substituted benzenesulfonyl isocyanate or isothiocyanate equivalent can do. For example, 12.8 parts of 2-methylamino-4- (2-methoxyethylthio) -6-methylpyrimidine in 300 parts of methylene chloride were added 22.8 parts of 2-nitro-benzenesulfonyl isocyanate at atmospheric temperature. do. The mixture is refluxed with stirring for 4 hours, and then methyl chloride is removed under reduced pressure. The resulting solid was triturated with 1-chlorobutane to give N- [N- [4 (2-methoxyethylthio) -6-methylpyrimidin-2-yl] -N-methylamino carbonyl] -2-nitrobenzene Sulfonamide is obtained.

Table 3-A

Table 3-D

Table 3-C

Table 3-D

Example 3

N- [N- [4 (2,2,2-trifluoroethoxy) -6-methylpyrimidin-2-yl] -N-methylaminocarbonyl] -2-thiophenesulfonamide

18.9 parts of 2-thiophenesulfonyl isocyanate was added to 22.1 parts of 2-methylamino-4- (2,2,2-trifluoro ethoxy) -6-methyl pyrimidines in 250 parts of methylene chlorides at atmospheric temperature. do. The mixture is stirred and refluxed for 2 hours. The methylene chloride was removed under reduced pressure and the resulting solid was polished with toluene to give N- [N- [4- (2,2,2-tri-fluoroethoxy) -6-methylpyrimidin-2-yl] -N 19 parts of -methyl-amino carbonyl] -2-thiophene sulfonamide is obtained.

The compound of Table 4 is prepared by the method of Example 3 using 2-methylaminopyrimidine or 2-methylamino-1,3,5-triazine and 2-thiophene sulfonyl isocyanate or isothiocyanate equivalent can do.

Table 4-A

Table 4-B

Table 4-C

Table 4-D

The N-methyl compound of this invention can be manufactured by the said method. For example, the methylation of Scheme 3 can be used as follows:

An equivalent of sodium hydroxide (50% mineral oil dispersion) was added to N-[[4- (2-methoxyethylthio) -6-methylpyrimidin-2-yl] amino carbonyl] -2 in dimethylformamide under nitrogen atmosphere. To 5-dichlorobenzene sulfonamide solution. The number of hydrogen generations completed and the same amount of dimethyl sulfate are added. After stirring for 12 hours the resulting mixture is poured into a large amount of water. The resulting precipitate was filtered to give N-[[4- (2-methoxyethylthio) -6-methylpyrimidin-2-yl] amino-carbonyl] -2,5-dichloro-N-methylbenzenesulfonamide. Get

Similarly, the compounds of the present invention in which all of the urea nitrogen is methylated can be prepared by the method of Scheme 4 as follows.

2-methylamino-4- (2,2,2-tri 18 parts N-[(2-chlorophenyl) sulfonyl] -N-methylcarbamylchloride in 300 parts of tetrahydrofuran containing 10 parts of triethylamine A 22 part solution of fluoro ethoxy) -6-methyl-pyrimidine is added. After stirring for 10 hours under reflux, the precipitated salts were filtered off and the filtrate was concentrated to give N-[(2,2,2-trifluoroethoxy) -6-methyl pyrimidin-2-yl] -N-methyl Amino carbonyl] -2-chloro-N-methylbenzenesulfonamide is obtained.

The compounds of Table 5 can be prepared using N-heterocyclic-N-aminocarbonyl benzenesulfonamides by the methylation process described above. The compounds of Table 5 can also be prepared using the appropriate carbamyl chloride and the appropriate methylamino heterocycle in the manner described above.

Table 5-A

Table 5-B

Table 6 by the above-described example method using suitably substituted N-methyl-N-phenylsulfonylthio carbamyl chloride and appropriately substituted 2-aminopyrimidine or 2-amino-1,3,5-triazine The compound of can be prepared.

Table 6-A

Table 6-B

N-[(1,3,5-triazin-2-yl) amino carbonyl] -2-thiophene sulfonamide; N-[(pyrimidin-2-yl) amino carbonyl] -2-thiophenesulfone amide; N-[(1,3,5-triazin-2-yl) -amino thiooxo methyl] -2-thiophene sulfonamide or N-[(pyrimidin-2-yl) aminothiooxomethyl] -2- Compounds of Table 7 can be prepared by the stated methylation using thiophene sulfonamides. Other appropriately substituted N-methyl-N- (2-thienylsulfonyl) carbamyl chloride or thiocarbamyl chloride and appropriately substituted 2-amino pyrimidine or 2-amino-1,3,5-triazine By the above method, the compounds of Table 7 may be prepared.

Table 7-A

Table 7-B

Table 7-C

Table 7-D

Article

Useful formulations of compounds of formula (I) can be prepared by conventional methods. These formulations include powders, granules, pellets, suspensions, emulsions, hydrating agents, emulsifiable concentrates and the like. Many of them can be used directly. Spray formulations can be expanded to a suitable medium and can be used in spray volumes from several liters to several hundred liters per hectare. High-strength compositions are used beforehand as a thickener to be diluted before use. Broadly, the formulation contains up to about 0.1 to 99% by weight of the active ingredient and at least one of a) about 0.1 to 20% by weight of surfactant and b) 1 to 99.9% by weight of solid or liquid diluent. They specifically contain these components in the proportions shown in Table 8.

TABLE 8

* Make 100% by weight of active ingredient with at least one of surfactant or diluent.

Of course, low or high concentrations of the active ingredient are made depending on the physical properties of the compound and the purpose of use. High proportions of the surfactant relative to the active ingredient are sometimes preferred and may be mixed into the formulation or tank mixed.

Some conventional solid diluents are described in Watkins et al. “Hand book of Insecticide dust diluents and Carriers” 2nd Ed., Dorland books, Caldwell, New Jersey. Other solids can be used as such or in the form prepared. Can be. A water absorbent large diluent is preferable as a water-soluble powder and a powder concentrate. Conventional liquid diluents and solvents are described in Marsden, “Solvent Guide”, 2nd Ed., Interscience, New York 1950. Solubility up to 0.1% is preferred as suspension concentrate, and solution concentrate is preferably stable to phase separation at 0 °. McCutcheon's Detergents and Emulsifiers Annual, McPublishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, “Encyclopedia of Surface Active Agents,” Chemical Publishing Co., Inc., New York, 1964, Active agents are listed and recommended for use All formulations may contain trace amounts of additives to reduce bubbles, caking, corrosion, microbial growth, and the like.

Methods for preparing such compositions are known. Solutions can be prepared by simply mixing the components. The fine solid composition is mixed and ground with a hammer or a fluid energy mill. Suspensions can be prepared by wet milling (cf. Littleler, US Pat. No. 3,060,084). Granules or pellets can be prepared by spraying the active substance on a preformed granular carrier or by agglomeration techniques. (J.E. Browning, “Agglomeration” Chemical Engineering, Dec. 4, 1967, pp. 147ff. And “Perry's Chemical Engineer's Handbook”, 4th Ed., McCraw-Hill New Yo, 1963, pp. 8-59ff)

For information on formulation techniques, refer to the following:

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

R.W. Luckenbaugh, U.S. Patent 3,309,192,8,12,15,39,41,52,53,58,132,138-140, 162-164,166,167,169-182.

H. Gysin and E. Knsli, U.S. Patnet 2, 891, 855, Col, 3, line 66 through Col. 5, line 17 and Examples 1-4.

G.C. Klingman, “Weed Control as a Science”, John Wiley & Sons, Inc., New York, 1961, pp-81-96.

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

Unless otherwise stated, all parts in the following examples are parts by weight.

Example 4

Water-soluble powder

N-[[4- (2,2,2-trifluoro ethoxy) -6-methyl-pyrimidin-2-yl] aminocarbonyl] -2-nitrobenzenesulfonamide 90%

Dioctyl Sodium Sulfosuccinate 0.1%

Sodium Lignin Sulfonate 1%

Microsynthetic Silica 8.9%

Each component is mixed and ground with a Hammer Mill to make all particles less than 100 microns. Packed in 50 U.S.S.No.

Example 5

Granule

10% water-soluble powder of Example 4

Aterfiltrite Granule 90%

(U.S.S. # 20-40; 0.84-0.42)

The mixing of the hydrating agent containing 50% solids is sprayed onto the surface of the aterfiltrite granules in a double cone mixer. Dry the granules and pack.

Example 6

Water-soluble powder

N-[[4- (2-methoxyethoxy) -6-methylpyrimidin-2-yl) aminocarbonyl] _2-nitrobenzenesulfonamide 40%

Dioctyl Sodium Sulfosuccinate 1.5%

Sodium Lignin Sulfonate 3%

Low Viscosity Methyl Cellulose 1.5%

Atterfil Zite 54%

Thoroughly mix the ingredients, pass through the air mill to re-mix them so that the average particle size is 15 microns or less, and sift with U.S.S.No 50 sieves (0.3mm) before packing.

Example 7

Granule

Water-soluble powder of Example 6 25% potassium sulfate 11%

Gypsum high 64%

The ingredients are mixed by rotary mixing and sprayed onto the mixture to granulate water. When most granules are between 1.0 and 0.42 mm (40 in U.S.S. # 18), they are removed, dried and screened. Large material is broken to make the desired range of additives. The resulting granules contain 10% active ingredient.

Example 8

Water-soluble powder

N-[[4- (2,2,2-trifluoro ethoxy) -6-methyl-pyrimidin-2-yl] aminocarbonyl] -2-nitrobenzene sulfonamide 80%

Sodium Alkyl Naphthalene Sulfonate 2% Amorphous Silica 3%

Sodium Lignin Sulfonate 2% Kaolinate 13%

The ingredients are ground into a hamma mill to make particles of 100 microns or less and then thoroughly mixed and remixed with the U.S.S. Pass through No 50 sieves and pack.

Example 9

Water-soluble powder

N-[[4-(-2-methoxyethoxy) -6-methylpyrimidin-2-yl] -aminocarbonyl] -2-nitrobenzene sulfonamide 65%

Dodesulphenol Polyethylene Glycol Ether 2% Sodium Silico Aluminate 6%

Sodium Lignin Sulfonate 4% Montmorillonite 23%

Mix the ingredients thoroughly. Liquid surfactant is sprayed onto the solid components in the mixer. After grinding all of the particles with a hammer mill to make them less than 100 microns in size, the materials are remixed and U.S.S. # Sieve into 50 sieves (0.3mm) and pack.

Example 10

Oil suspension

N-[[4- (2,2,2-trifluoroethoxy) -6-methyl-pyrimidin-2-yl] amino carbonyl] -2-nitrobenzene sulfonamide 25% polyoxyethylene sorbitol hexaol Rate 5%

High Aliphatic Hydrocarbon Oil 70%

The ingredients are ground in a sand mill until the solid particles are about 5 microns or less. The product suspending agent may be used directly, but is preferably diffused with oil or emulsified in water.

Example 11

Aqueous suspensions

N-[[4- (2-methoxyethoxy) -6-methylpyrimidin-2-yl] -aminocarbonyl] -2-nitrobenzene sulfonamide 25%

Hydrated Atterfilite 3%

Crude calcium ligninsulfonate 10%

Sodium Hydrogen Phosphate 0.5%

61.5% of water

The ingredients are ground and packaged in a ball or roller mill to make the solid particles less than 10 microns in size.

Example 12

Extruded Pellets

N-[[4- (2,2,2-trifluoro ethoxy) -6-methyl-pyrimidin-2-yl] aminocarbonyl] -2-nitrobenzene sulfonamide 25%

Anhydrous sodium sulfate 10%

Crude calcium lignin sulfonate 5%

Sodium Alkyl Naphthalene Sulfonate 1%

Calcium / Magnesium Bentonite 59%

Mix the ingredients, grind with a hammer and moisten with water to about 12%. The mixture is extruded into a silinda form of about 3 mm in diameter and cut into pellets of about 3 mm in length. Pellets can be used directly after drying, dry pellets are U.S.S. Crush it through No 20 body (0.84mm). U.S.S. Granules made from No 40 sieves (0.42mm) are packaged and the fine powder is recycled.

Example 13

Solution

N-[[4- (2,2,2-solution trifluoroethoxy) -6-methyl-pyrimidin-2-yl] aminocarbonyl] -2-nitrobenzene sulfonamide

Sulfonamide 5%

Dimethylformamide 95%

The ingredients are mixed and stirred to make a solution, and the ingredients can be used for low volume use.

use

The compound of the present invention is a highly active herbicide. It is preferable to be used as a weed preventive agent before or after germination in a wide range of fields where all plants are to be completely controlled, that is, around fuel storage tanks, ammunition warehouses, industrial storage areas, oil wells, outdoor theaters, billboards, elevated roads and railways. By appropriately selecting the ratio and time of use, the compounds of the present invention can also be used to advantageously modify plant growth.

The exact amount of Formula (I) compound used in a given environment will vary depending on the particularly desirable end result, the amount of leaves present, the weeds that can be controlled, the species of grain, the soil type, the type of formulation and application, and weather conditions. Can be. As they play a variety of roles, it is not possible to mention application rates in all situations. Generally, the compounds of the present invention are used at about 0.005 to 20 kg / ha, with a preferred range of 0.125 to 10 kg / ha. In general, a high rate of application within this range will be reverse conditions or continuous persistence in the soil will be desirable.

Formula (I) compounds may also be mixed with other herbicides, in particular 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1-methoxy- Ureas such as 1-methylurea and 1,1-dimethyl-3- (α, α, α-trifluoro-M-tolyl) urea; Triazines such as 2-chloro-4- (ethylamino) -6- (isopropylamino) -S-triazine; Uracil, such as 5-bromo-3-secondary butyl-6-methyluracil; N- (phosphono-methyl) glycine; 3-cyclohexyl-1-methyl-6-dimethyl-amino-S-triazine-2,4- (1H, 3H) -dione; N, N-dimethyl-2,2-diphenylacetamide; 2,4-dichlorophenoxy-acetic acid (a closely related compound); 4-chloro-2-butynyl-3-chlorophenylcarbamate; Esters with diisopropyl thiolcarbamic acid and 2,3-dichloroallyl alcohol; Diisopropyl thiol carbamic acid, S- (2,3,3-trichloroallyl) ester; Ethyl-N-benzoyl-N- (3,4-dichlorophenyl) -2-aminopropionate; 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate; Methyl 2- [4- (2,4-dichlorophenoxy) -phenoxy] propanoate; 4-amino-6-tert-butyl-3- (methylthio) -1,2,4-triazine-5 (4H) -silver; 3-isopropyl-1H-1,2,3-benzothiodia Jin- (4) -3H-one--2,2-dioxide; α, α, α-trifluoro-2,6-dinitro-N, N-dipropyl-P-toluidine; 1,1'-dimethyl-4,4'-bipyridinium ion; Monosodium methane alsonate; And 2-chloro-2 ', 6'-diethyl (methoxymethyl) acetanilide and the like.

The activity of this compound was found in greenhouse tests. This test is described and the results from the test are as follows.

0: no effect D: defoliation

10: maximum effect E: germination inhibition

B: burn G: growth inhibition

C: Yellowish whitening or necrosis H: Formation effect

S: Pigment deficiency 6Y: Unnormal shoots or flowers

U: strange coloring

exam

Digitaria Spp., Echinochloa crusgalli, Oven (Avena fatua), Cinnamon tora, Ipomoes Spp., Xanthium Spp., Sorghum, Corn, Soybean, Rice, Wheat And seeds of Cyperus rotundus were transplanted into growth media and treated with pre-germination with pesticides dissolved in non-toxic solvents in the compounds of Table 9. Seeds and tubers of all the aforementioned weeds and crops were transplanted simultaneously with the control. The control food was not treated, i.e. no compound or solvent was used. At the same time, cotton with 5 leaves (including 1 cotyledons), kidney beans with 3 broad leaves, barley with 2 leaves, blood with 2 leaves, wild oats with 2 leaves, 3 (1 cotyledons) Cinnamon with leaves), morning glory with four leaves (including one cotyledons), corn with four leaves, beans with two cotyledons, rice with three leaves, wheat with one leaf, Persimmons with 3 to 5 leaves were sprayed with pesticides dissolved in non-toxic solvents in the compounds of Table 9. At the same time, control plants of the weed and crop group were sprayed with pesticides dissolved in the same non-toxic solvent. Pre- and post-emergence plants and control plants are placed in a greenhouse for 16 hours, and then all treated plants are visually evaluated for comparison with each control. As shown in Table 9, the compound of the present invention was shown to be effective in selectively removing weeds after germination in wheat.

TABLE 9

Exam B

Two globular plates are filled with fertile calcareous Fallsington sandy soil. In one pan, corn, sorghum, Kentucky bluegrass and some herbaceous weeds are planted. In another pan, beans, cyperus rotundus and some broadleaf weeds are planted. Digitaria sanguinalis, Echinochloa crusgalli, Avena fatua, Sorghum halepense, Setaria faberii, Paspalum dilatatum, Bromus secalinus , Mustard (Brassica arvensis), Xanthium Pennsylvanicum, Amaranthus retroflezus, Ipomoes hederacea, Cassia tora, Sida spinosa, Velvet reef (Abutilion theamohrasti) and Jimson tweed (Datura) Cultivate herbaceous and broadleaf weeds. Fill a small pot with pre-prepared soil and plant rice and wheat seeds. Plant sugarcane seeds in another small pot.

Plant sugarcane seeds in another small pot. The four containers are treated prior to germination with pesticides dissolved in nontoxic solvents of the compounds of the present invention Table 10 (the already mentioned compound solution is sprayed onto the soil surface before seed germination). The two container-planted containers described above are used as a control without treatment.

After 28 days of treatment, treated and control plants were evaluated and the data evaluated visually as described in Table 10. The compounds of the present invention have been shown to be useful for weed removal in cereals such as soybeans and wheat.

TABLE 10

Exam C

Soy, cotton, corn, rice, wheat, sorghum, alfalfa, avutulon theophrasti, sesbania exaltata, cassia tora, and morning glory (Ipomoes) in pots filled with Fallsingt3n silt loam spp.), Datura stramonium, Xanthium pennsylvanicum, Digitaria spp., Cyperus rotunda, Echinochloa crusgalli, Setian faberii, and Avena fatua Plant) 2-1 / 2 weeks after transplantation, young plants and the soil around them are sprayed entirely with the compounds in Table 11 dissolved in non-toxic solvents. The same other group of weeds and crops is sprayed with pesticides dissolved in the same non-toxic solvent and used as a control. At 14 days post-treatment, all treated plants were compared to the control plants treated with pesticides dissolved in non-toxic solvents and visually observed the reactivity of the treated plants to obtain the data shown in Table 11. Several compounds tested in this process have been shown to be effective for weed control after germination in wheat.

TABLE 11

Claims (1)

A process for preparing a compound of formula (I) and an agriculturally suitable salt thereof, characterized by reacting a compound of formula (III) with a compound of formula (II):

Wherein R is

or

R ₄ is Cl, Br, F, NO ₂ , CH ₃ , OCH ₃ , CF ₃ , or R ₃ S (O) n where R ₃ is alkyl of 1 to 6 carbon atoms or alkenyl of 3 to 4 carbon atoms Is; R ₅ is H, Cl, Br, F, CH ₃ or -OCH ₃ ; W is O; n is 0, 1 or 2; X is CH ₃ or -OCH ₃ ; Y is C3-C4 alkyl; Alkyl having 2 to 4 carbon atoms substituted with CH ₃ O; Alkyl having 2 to 4 carbons substituted with 1 to 3 atoms in Cl, Br, or F; Alkyl having 1 to 4 carbon atoms substituted with C ₂ H ₅ O, CN, CO ₂ H, CO ₂ CH ₃ or CO ₂ C ₂ H ₅ ; CH ₂ F; CH ₂ Cl; CH ₂ Br; Alkenyl having 2 to 4 carbon atoms; Alkynyl having 2 to 4 carbon atoms; SCN; N ₃ ; A (CH ₂ ) mA ₁ R ₇ wherein m is 2 or 3, R ₇ is alkyl of 1 to 3 carbon atoms, A ₁ is O or S, and A is O or S (O) n];

[Wherein A ₂ and W ₁ are each independently O or S, R ₁₅ is alkyl having 1 to 3 carbon atoms optionally substituted with 1 to 3 of F, Cl, Br or R ₁₅ is N (CH ₃ ) OCH ₃ or NR8R9.];

[Where L is N (CH ₃ ) OCH ₃ or NR ₈ R ₉ (where R ₈ and R ₉ are each independently H, CH ₃ or C ₂ H ₅ ) or L is OR ₁₀ where R ₁₀ is H Or alkyl having 1 to 4 carbon atoms.); NR ₁₁ R ₁₂ , wherein R ₁₁ is H or CH ₃ , R ₁₂ is alkenyl having 3 to 4 carbon atoms; alkyl having 2 to 3 carbon atoms substituted with OCH ₃ or OC ₂ H ₅ ; cyclopropyl; or CN, CO Alkyl having 1 to 2 carbon atoms substituted with ₂ CH ₃ or CO ₂ C ₂ H ₅ ; OR ₁₃ (wherein R ₁₃ is alkyl having 4 to 6 carbons, cyanoalkyl having 1 to 4 carbon atoms, alkenyl having 3 to 4 carbon atoms, alkynyl having 3 to 4 carbon atoms,

; Or alkyl having 2 to 4 carbons substituted with 1 to 3 atoms in F, Cl, or Br.); Or SR ₁₄ , wherein R ₁₄ is cyanoalkyl, allyl or propargyl having 1 to 2 carbon atoms; and Z is CH or N.