JPS60197676A - Substituted thiophenesulfonamide compound and herbicide containing the same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (one of X and Y is 1,2,3,3,3-pentafluoro-1-propenyl and the other is group of formula II; R<1> and R<2> are methyl or methoxy) and its salt. EXAMPLE:N-[( 4,6-dimethoxypyrimidin-2-yl )-aminocarbonyl]3-(1,2,3,3,3-pentafluoropropen-1-yl)-2-thiophenesulfon amide. USE:Herbicide capable of control harmful weeds grown on especially paddy field selectively at a low rate of application. The weed of relatively grown stage can also be controlled. PREPARATION:The compound of formula I can be prepared by reacting the compound of formula III (one of Z<1> and Z<2> is 1,2,3,3,3-pentafluoro-1-propenyl and the other is aminosulfonyl) with the compound of formula IV (R is alkyl, alkenyl or phenyl).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to substituted thiophene sulfonamide compounds or herbicides containing them as active ingredients.

More specifically, the present invention relates to substituted thiophene sulfonamide compounds represented by general formula (I) or herbicides containing them as active ingredients.

The substituted thiophene sulfonamide compound of the present invention can also form an alkali metal salt such as sodium or potassium, an alkaline earth metal salt such as magnesium or calcium, or an amine salt such as dimethylamine or triethylamine.

The compound of the present invention represented by the general formula (I) can be produced, for example, by the following method.

(In the formula, one of 71 and Z2 is a 7minosulfonyl group, and the other is a 1,2.3,3.3-pentafluoro-1-
It is a propenyl group. One of Z3 and Z4 is incyanatosulfonyl group, and the other is 1,2,3,3.3
-pentafluoro-1-propenyl group. R is an alkyl group, alkenyl group or phenyl group, X%Y,
R' and R2 are as described above. ) The above reaction is carried out in the presence of a solvent, if necessary.

Solvents include aromatic hydrocarbons such as benzene, F-luene, xylene, and chlorobenzene; cyclic or non-cyclic aliphatic hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, hexane, and cyclohexane; Ethers such as ether, methyl ethyl ether, dioxane, and tetrahydro-7rane; acetone, methyl ethyl ketone; nitriles such as acetonitrile, propionitrile, and acrylonitrile; M dimethyl sulfoxide;
Examples include aprotic polar solvents such as sulfolane.

In the [A1 reaction, 1,8-diazabicyclo(5,4.0)
-7-Undecene may be added. *The above [B]
At the center of gravity, 1,4-diazabicyclo[2,2.2] is used as a catalyst to promote the reaction if necessary.
Octane may also be added.

The starting compound represented by (II) in the reaction formula of [A] above is - It ends with what you do.

(In the formula, R is methyl, ethyl, n-propyl, isopropyl, lobutyl, isobutyl, 5ec-butyl, ter
It is an alkyl group such as t-butyl. ) Reaction conditions such as reaction temperature, reaction time, solvent used as necessary, alkaline substance, etc. for each reaction in the method for producing raw material compounds can usually be appropriately selected from reaction conditions for similar reactions. In addition, some of the compounds of the present invention can also be produced by, for example, the following method in addition to the above-mentioned method.

(In the formula, HAL is a halogen atom, and R1 and R2 are as described above.) Next, a synthesis example of the compound of the present invention will be described.

Synthesis example N-((4,6-simethoxypyrimidine-2-
yl)-ami7carbonyl)3-(1,2,3,3,3
-Synthesis of -pentafluoropropen-1-yl)-2-thiophene sulfonamide [1] In a nitrogen stream, 6.5 g of N(ert-butyl-2-thiophene sulfonamide was added to 100 g of tetrahydro-7 run
32 mg of n-hexane solution (1,6M) of n-butyllithium was added dropwise to 10 °C.
Stir for hours. Thereafter, 5.56 g of trimethylsilyl chloride was added dropwise at 0 to 5°C, and the mixture was reacted for 17 hours with stirring at room temperature. After the reaction was completed, the product was poured into water, acidified with hydrochloric acid, and extracted with ether.

The extracted layer was washed with water, dried over anhydrous sodium sulfate, the ether was distilled off under reduced pressure, and purified by silica gel column chromatography. The crystals were washed with n-hexane and dried to give a melting point of 1.
2.7 g of N-tert-butyl-5-trimethylsilyl-2-thiophenesulfonamide at a temperature of 02 to 104°C was obtained.

[2] N-te obtained by the method [1] above in a nitrogen stream
I-
Drop 1.5 ml of hexane solution (1.6M),
The mixture was stirred at room temperature for 4 hours. After that, attach a dry ice condenser and heat the hexafluoropropene at 0 to 10℃.
0 g was introduced, and the reaction was allowed to proceed for 3 hours with stirring.

After the reaction is complete, the product is poured into water and made acidic with hydrochloric acid.
Ether extraction, water washing, drying, ether distillation under reduced pressure, purification by silica gel column chromatography, melting point 9
N-tert-butyl-3-(1,2,3
,3,3-pentafluoropropen-1-yl)-5-
) trimethylsilyl-2-thiophenesulfonamide 1.
6g was obtained.

[3] N-tert-butyl-3- obtained in [2] above
(1,2,3,3,3-pentafluoropropene-1-
yl)-5-)dimethylsilyl-2-thousene sulfonamide and 4 mQ of trifluoroacetic acid were reacted at room temperature for 13 hours with stirring. After the reaction, the product was poured into water and diluted with methylene chloride. Extracted. Wash the extract layer with water,
After drying, methylene chloride was distilled off under reduced pressure and purified by silica gel column chromatography to obtain a solution with a melting point of 129-140.
0.93 Fl of 3-(1,2,3,3,3-pentafluoropropenyl-1-yl)-5-)tumethylsilyl-2-thiophenesulfonamide was obtained.

[4] 3-(1,2,3,3,3-
1 g of pentafluoropropen-1-yl)-5-)dimethylsilyl-2-thousandene sulfonamide and 4-trifluoromethanesulfonic acid were reacted under stirring at room temperature for 2 hours. After the reaction was completed, the product was poured into water and extracted with methylene chloride. The extracted layer was washed with water, dried, methylene chloride was distilled off under reduced pressure, and purified by silica gel column chromatography to obtain 3-(1,2
,3,3,3-pentafluoropropen-1-yl)-
0.67 g of 2-thiophenesulfonamide was obtained.

[5] 3-(1,2,3,3,3-
0.17 g of pentafluoropropen-1-yl)-2-thiophenesulfonamide and phenyl-N-4,6-
Cymethoxypyrimidin-2-ylcarbame) 0.18
Dissolve g in 4 mρ of acetonitrile and add 1.8-
Diazabicyclo[5,4,0]-]7-undecene0.
10 was added dropwise, and the mixture was reacted at room temperature for 2.5 hours with stirring.

After the reaction, the product was poured into water, acidified with hydrochloric acid, and the precipitated crystals were filtered, washed with water, and dried to give a melting point of 129-1.
0.210 g of the target product was obtained at 33°C.

Specific examples of the present invention produced according to the general production method and the synthesis examples described above will be described.

Compound No. 1: N-((4,6-Simethoxypyrimidin-2-yl)ami7carbonyl)-3-(1,2
゜3.3.3-pentafluoropropen-1-yl)-
2-thiophene sulfonamide system, 129-133
°C Compound No. 2: N-((4-methyl-6-medoxypyrimicin-2-yl)ami7carbonyl]-3-(
1,2,3,3,3-pentafluoropropen-1-yl)-2-thiophenesulfonamide m, p, 171
-175°C Compound No. 3: N-((4,6-dimethylpyrimidin-2-yl)ami7carbonyl)-3-(1,2°3.3.3-pentafluoropropen-1-yl )-2
-thiophene sulfonamide m, p, 142-145
°C Compound No. 4: N-((4,6-Simethoxypyrimidin-2-yl)ami7carbonyl)-2-(1,2
゜3.3.3-pentafluoropropen-1-yl)-
3-thiophene sulfonamide m, p, 183-185
°C The present invention encompasses cis and trans stereoisomers.

As shown in the test examples described later, the substituted thiophene sulfonamide compound of the present invention exhibits excellent herbicidal effects when used as an active ingredient of a herbicide. In particular, noxious weeds that grow in rice fields can be controlled selectively and at low doses without causing chemical damage to rice. Furthermore, since it can control even those harmful weeds that have relatively advanced growth, it is suitable as a herbicide for paddy fields. Furthermore, it is preferable because it can also control harmful weeds in fields.

The herbicide of the present invention can be applied to a wide variety of areas, including orchards, mulberry orchards, mountain forests, farm roads, grounds, and factory sites, in addition to the above-mentioned agricultural land, and the application method can be appropriately selected from soil treatment and foliage treatment.

When the herbicide of the present invention is applied, it is usually mixed with a carrier and, if necessary, various auxiliary agents such as diluents, solvents, emulsifiers, spreading agents, and surfactants, to form granules, water concentrators, emulsions, and solutions. It is used in formulations. The appropriate blending weight ratio of the active ingredient compound and the pesticide adjuvant is generally 0.05:99.95 to 9.
0:10, preferably 0.1:99.9 to 60:40
It is. The appropriate amount of the active ingredient compound to be used cannot be determined unconditionally due to differences in weather conditions, soil conditions, drug formulation, type of target weed, application period, etc., but in general, the amount of the active ingredient to be applied per are is 0. 1-100g, preferably 0.5-50g. It is.

The herbicide of the present invention can be mixed or used in combination with other agricultural chemicals, fertilizers, soil, phytotoxicity reducers, etc., and in this case may exhibit even better effects and action. When mixed or used in combination with other herbicides, examples of the active ingredients of the herbicides to be mixed include the following.

2.4-dichlorophenyl-3'-me)'? sea 4'
- = a phenyl ether, 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitrophenyl ether, 2-90o-2', 6'-diethyl-N-(
butoxymethyl)acetanilide, 2-chloro-2'
, 6'-diethyl-N-(propoxyethyl)acetanilide, 4-ethoxymethoxybenz-2', 3'
-cycloanilide, 5-(2-methyl-1-piperidyl-carbonylmethyl)-0,0-di-n-propyldithiophosphate, 5-(4-chlorobenzyl)N,
N-diethylthiol carbamate, S-ethyl-hexahydro-IH-7 zevin-1-carbothioate, 5
-(1-methyl-1-7enethyl)biperidine-1-carbothio-1,0,0-diisopropyl-8-(2-
Benzene sulfate 7-ethylate, 5-Lerj-butyl-3-(2,4-cyclo-5-impropoxyphenyl H, 3,4-oxadiazolin-2-one, benzthiazol-2-yloxy-
Acetic acid N-methylanilide, 〇-ethyl〇-(3-methyl-6-diF-phenyl)sec-butylphosphoramidothioate, 4-(2,4-dichlorobenzoyl)-
1,3-dimethyl-5-7enacyloxypyrazole,
4-(2,4-dichlorobenzoyl)-1, 3-
Dimethylpyrazol-5-yl-p-toluenesulfonate, 4-(2,4-dichloro-3-methylbenzoyl)-1,3-dimethyl-5-7enacyloxypyrazole, 4-ami/-f3-tert- Butyl-3-methylthio-1.2.4-triazin-5(4H)-one, 2-(2-chloro-4-ethylamino-S-triazin-6-ylamino)-2-methylpropionitrile,
2-chloro-4-ethylamino-6-inpropylami/-S-)riazine, 3-(3,4-dichloro7j-nyl)-1-methoxy-1-methylurea, α-[
11-Butyl 4-(54lyfluoromethyl-2-pyridyloxy)phenoxypropionate, Q-C4-<
Methyl 2.4-dichloro7ethoxy)phenoxypropionate, 2-(1-(ethoxyimino)-butyl)
-5-(2-ethylthiopropyl)-3-hydroxy-
2-cyclohexen-1-one, 3,4-dimethyl-2
．． 6-sinitro N-1-ethylpropylaniline, α
,α,a-trifluoro2,6-sinitroN,N-
Dipropyl-D-)luidine, 2-chloro-2', 6
'-Diethyl-N-(methoxymethyl)acetanilide, 2-chloro-N-(2-ethyl-6-methyl7enyl)-N-(2-me[xy-1-methylethyl)acetamide, 2- Methoxy-3,6-dichlorobenzoic acid dimethylamine, 2-Sec-butyl-4,6-sinitro7emale, S-ethyl-N. Test examples of two herbicides of the present invention, N-di-doprobyl thiol carbamate and S-ethyl-N,N-dibutyl thiol carbamate, will be described.

Test Example 1 A 1/2,000-acre pot was filled with paddy soil, and seeds of Japanese cypress, Japanese cypress, firefly, and azalea, as well as tubers of Japanese azalea were sown, and kept in a moist state. Firefly is 1
After the plants grew to the leaf stage, they were irrigated to about 5 CI11, and a predetermined amount of an aquarium containing the compound of the present invention diluted with water was added dropwise with a pipette. The growth condition was visually observed 21 days after the drug treatment, and the degree of growth inhibition was evaluated based on the following criteria (5-point scale from 1 to 5), and the results shown in Table 1 were obtained.

Test Example 4 Tests were conducted in the same manner as in Test Example 3, except that when the wild plants reached the two-leaf stage, each drug shown in Table 4 was treated, and the results shown in Table 4 were obtained.

Table 4 Compound C: S-ethyl-hexahydro-IH-7zepine-1-carbothioate Compound D: 5-(2-methyl-1-piperidyl-carbonylmethyl)-0,0-di-n-propyldithiophosphate compound 11 & IE: 5-(4Chlorbenzyl)N,N-diethylthiol carbamate Test Example 5 A 1/1,000 Ahlbond was filled with field soil, and seeds of various plants were sown. After that, when the plants reach a certain growth stage (wheat at the 4.5-leaf stage, Japanese fir at the 3-leaf stage, morning glory at the 1.5-leaf stage, goldenrod at the 1-leaf stage, Japanese knotweed at the 2-leaf stage, At the first leaf stage), the hydrating powder of the herbicide of the present invention was diluted with water in an amount of 5000/l+a, and the foliage was treated with a small sprayer so that the active ingredient was in a predetermined amount. On day 30 after the treatment, the growth conditions of the various plants were observed with the naked eye, and the degree of growth inhibition was evaluated on a scale of 10 (1: same as untreated area to 10: completely inhibited), and the results shown in Table 5 were obtained.

Table 5 Next, formulation examples of the herbicide of the present invention will be described.

Formulation Example 1 (1) Bentonite 61 parts by weight (2) Zikrite 33 parts by weight (3) Lignosulfonate 5fE 11 parts (4
) Compound No. 1 I parts by weight or more of each component were added with an appropriate amount of water required for granulation, mixed, and granulated to obtain granules.

Formulation Example 2 (1) Seecrite 78 parts by weight (2) Labelin S (trade name: manufactured by Dai-Kogyo Seiyaku) 2 parts by weight (3) Tsurupol 5039 (trade name: manufactured by Toho Chemical Industries) 5 parts by weight (4) Car Plex (product name: Shionogi & Co., Ltd.) 15
A mixture of components (1) to (4) in parts by weight or more and compound No. 2
A wettable powder was obtained by mixing the following in a weight ratio of 4:1.

Patent applicant: Ishihara Sangyo Co., Ltd. Procedural amendment (method) % formula % 1. Indication of case: Patent application No. 51582 of 1982 2.
Title of the invention Substituted thiophene sulfonamide compounds and herbicides containing them 3, Relationship with the case of the person making the amendment Patent applicant Address: 3-22-4 Edobori-chome, Nishi-ku, Osaka 550 Nishikku Edbori Date of amendment order Showa June 26, 1959 (shipment date) 5. Subject of amendment Full text of application and full text of specification 6. Contents of amendment As attached (type-printed version, no corrections to written content)

Claims (1)

[Scope of Claims] Substituted thio-sulfonamide system 4 represented by
Hypoallergenic compounds and their salts. A herbicide characterized by containing as an active ingredient at least one of the substituted thio7enesulfonamide derivatives represented by the following formula and its salts: . (In the formula, Z1 and Z2 are one of 1., 2, 3, 3
, a 3-pentafluoro-1-propenyl group, and the other is an aminosulfony group (wherein R1 and R2 are a methyl group or meth)oxy group, and R is an alkyl group, an alkenyl group, or a phenyl group). 1. A method for producing a substituted thiophene sulfonamide compound, the method comprising reacting with a substituted thiophene sulfonamide compound. 4, a compound represented by the general formula (in the formula, one of Z3 and Z4 is a 1.2,3.3.3-pentafluoro-1-propenyl group and the other is an isocyanatosulfonyl group);
A general method for producing a substituted thiophene sulfonamide compound, which comprises reacting a compound represented by the general formula (wherein R1 and R2 are a methyl group or a methoxy group).