JPS5970670A - N-oxypyridyl sulfimide derivative, its preparation and herbicidal and plant growth regulating agent - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is H or lower alkyl; R<1> is alkyl or lower alkyl substituted by halogen; R<2> is lower alkyl, lower alkyl susbstituted by halogen, phenyl, phenyl substituted by lower alkyl, etc. or naphthyl). EXAMPLE:S-Ethyl S-(N-oxy-2-pyridyl) N-p-toluenesulfonyl sulfimide. USE:A herbicide and plant growth regulating agent capable of exhibiting improved herbicidal action on gramineous weeds and weeds of the family Cyperaceae, etc. particularly by the soil treatment without giving phytotoxicity to broadleaf crops, e.g. cotton, soybean, AZUKI bean, beet, potato, etc. and further showing improved growth regulating action on gramineous plants. PROCESS:An N-oxypyridazyl sulfide compound expressed by formula II is reacted with an N-chloro-N-sodiosulfonamide compound expressed by formula III in an aprotic solvent, e.g. acetanilide, to give easily the aimed compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention 1J relates to a novel N-oxypyridyl sulfimide derivative, a method for producing the same, and a herbicide, 4-product growth agent, and a 1-determinant containing the conductor as an active ingredient.

More specifically, the present invention is as follows.

[In the formula, or a hydrogen atom is a lower alkyl group [Z]
Alkyl group or... Roge 7)) Lower alkyl group substituted with 4 λ atoms @If lower alkyl group,...lower aryal group substituted with rogene atom, phenyl group, 1
(c) A phenyl group substituted with 5 substituents (however, 1ρ
The substituent is selected from the group consisting of a lower alkyl group, a rogen atom, an alkyloxy group, an alkyl group, and an alkoxycarbonyl group, and when there are 2 to 5 substituents, they are the same or different from each other. It's okay. ) or defthyl group W. ] The present invention relates to a 1q-oxypyridylsulfimide derivative represented by the above formula, a method for producing the same, and a herbicide and a plant growth regulator containing one or more of the derivatives as an active ingredient.

The compound of the present invention represented by the general formula (1) is a novel compound having a herbicidal action and a growth-inhibiting plant growth regulating action on grass crops.

Regarding herbicidal activity, it has excellent herbicidal activity especially against weeds of the Poaceae family and Cyperaceae family when treated with soil.

Talented. Cotton, big brother, red bean, cabbage, beet, rapeseed.

It has the characteristic of having almost no chemical damage to broad-leaved crops such as peanuts, sunflowers, radish, citrus orchid, potatoes, and eggplants, and has excellent practical use as an active ingredient in soil treatment agents or soil admixtures for broad-leaved crops. It is a compound with Accordingly, the compound of the present invention is applicable to the field of agriculture and horticulture.

It is particularly suitable as a herbicide for upland fields for the selective control of grass and Cyperaceae weeds during the cultivation of broad-leaved crops.

In addition, the compound of the present invention can be applied to control various weeds in non-agricultural fields such as playgrounds, open spaces, and railway edges, in addition to agricultural and horticultural fields such as fields, paddy fields, and orchards, and the amount of application tj is the application situation. Although there are differences depending on the application period, application method, control grass species, cultivated crops, etc., in general, 0.05 to 9 in 10 seedlings per hectare is appropriate for M juvenile enrichment.

On the other hand, two of the compounds of the present invention (+1 r-I) exhibit a pickled growth nodal effect on gramineous plants in soil treatment and vegetable leaf treatment.
As a growth regulator for grasses such as wheat, barley, and grass, 1' 3! It is fir.

Although there are differences depending on the applied dosage, purpose of use, type of target plant, and other conditions, generally the active ingredient concentration is preferably 10 to 500 Ll r + pm, preferably about 50 to 20 D Or + pm. It is appropriate to use.

Conventionally, the general formula (■): [In the formula, R1 and R' represent a lower alkyl group. ] It is described in US Pat. No. 3,909,235 that the dinitroaniline derivative represented by the following formula has herbicidal activity.

Further, general formula (V): [In the formula, Rtts represents a low R alkyl group, an alkylphenyl group, or a 7-phenylalkylene group. ] to the pyridylsulfimide derivative represented by.

JP-A No. 57-48964 describes that it exhibits antitumor activity, but does not disclose herbicidal activity or the like at all.

However, one of the compounds of the present invention, that is, the N-oxypyridyl sulfimide derivative represented by the above general formula (1), is a novel compound not described in any literature that is different from the prior art represented by the above general formulas (■) and (V). It has immediate herbicidal activity and stalk growth regulating action.

The compound of the present invention generally includes an N-oxypyridyl sulfide compound represented by 9 general formula (n) and an N-chloro-N-sodiosulfonamide compound represented by general formula (■) as shown in the following reaction formula. It can be easily synthesized by reacting with (U) in a non-punitive solvent.

[In the formula, X, R'' and R' have the same meanings as above.]

As an aprotic solvent, acetonitrile.

methylene chloride, chloroform, chloroethane.

Ethyl acetate, benzene, toluene, etc. are preferred, and the reaction temperature is not particularly limited, but it is generally appropriate to carry out the reaction at a temperature of 10°C to 50°C. The reaction time varies depending on the degree of reactivity of the reactant 1 and is usually from 1 hour to 24 hours. After the completion of the reaction, the desired product is isolated according to a conventional method, and the N-oxypyridylsulfimide derivative represented by the general formula (1) can be obtained with good purity and good yield.

This compound can be further purified by column chromatography, recrystallization, etc., if necessary. General formula (+N represented by old) which is the starting material
-Chlor-N-sodiosulfonamide can be easily synthesized by heating the corresponding sulf;J]namide with an equivalent amount of monosodium hypochlorite [Journal of Chemical Society] ;+l C)f
T! br;+ni+:alnnciaty).

0, p. 2089, 1970], or by dissolving the corresponding sulfonamide, chlorination reagent, and organic chlorine in aprotic min.

As the chlorination reagent, an alkoxide base such as 5O3C4.mu.ethoxide is preferred. Although it is preferable to synthesize and isolate N-chloro-N-sodiosulfonamide before use in the reaction, good results can also be obtained by using the synthesis reaction bath itself in the next step of the synthesis reaction without isolation. .

Conventionally, general methods for synthesizing sulfimide compounds are as follows.

It is synthesized by dissolving and heating the N-chloro-N-sodiosulfonamide and the corresponding sulfide in a protic solvent such as methanol. (
(Reference: Chapter 7 of "Organic Sulfur Chemistry - Synthetic Reaction Edition" edited by Taiyo, Kagaku Dojin, 1982) The method for synthesizing N-oxypyridyl sulfimide of the present invention has the following two advantages compared to the conventional sulfimide bond synthesis method. It has excellent characteristics.

1) The starting material N-chloro-N-sodiosulfonamide compound can be synthesized in an aprotic solvent without isolation, and the reaction solution itself can be used for the next step of the synthesis reaction. (One-pot synthesis method) 2) Since sulfimide synthesis can be easily performed in an aprotic solvent, it is suitable for the synthesis of sulfimide compounds that are unstable in protic mortar.

Various compounds of the present invention can be produced according to the reactions shown in the above reaction formula. Specific examples thereof are listed in Table 1. However, for two compounds of the present invention.

It is not limited to these.

Table 1 General formula (1) Synthesis of the compound shown in Compound A of the present invention in Table 1 is the following synthesis example.

Reference is made to formulation examples and test examples.

Next, one compound of the present invention will be explained by giving some specific synthesis examples. However, it is not limited to these only.

Synthesis Example 1 S-enal 5-(N-oxy-2-pyridyl)Np-
) Synthesis of luenesulfonylsulfimide (Compounds of the Invention Part 2) Chloramine-T (
3r) and B-xtilS-(N-oxy-2-
Add at once a common acetonitrile solution containing 1.6 fl pyridyl sulfide.

Further, the reaction solution was continued to be stirred at room temperature for 2 hours.

The end point of the reaction was determined by monitoring alumina thin layer chromatography (developing solution - ethyl acetate) of the reaction solution. After the reaction was completed, most of the reaction solvent was distilled off, and cold water was added to the remaining amount. The generated crystals are sufficiently washed with water and dried to obtain white crystals (3,27) fc, and the crude product is recrystallized from ethyl acetate-hexane to obtain 2.9f of white crystals of the present compound A2. I was able to do that.

White crystal Melting point 144-145t' (decomposition) Synthesis example 2 S-ether 5-(N-oxy-2-pyridyl)N-(2
-Synthesis of nitrobenzenesulfonyl) sulfimide (inventive compound A17) To an acetonitrile solution in which 2-nitrobenzenesulfonamide (tsy) was dissolved, monobutylhypochloride (0,7f) was added dropwise under water cooling. After stirring the reaction solution at room temperature, powdered sodium ethoxide (0.44r
11 S-ethyl 5-(N-oxy-2-pyridyl) sulfide was added to 4 solutions of acetonitrile containing N-chloro-N-fusio-2-nitrobenzenesulfonamide. acetonitrile solution
+sj and heated for about 1 hour.

1.69 f of white crystals of the compound A17 of the present invention were obtained by the same post-treatment method as that for the synthesized product.

White crystals Melting point 146-148°C (decomposed) Synthesis Example 3 Synthesis of S-methyl 5-(N-oxy-2-pyridyl)N-methylsulfonylsulfimide Methanesulfonamide (12) and 10 parts hypochlorous acid ) IJium aqueous solution (
7,8y) f. After mixing and heating, the water was distilled off under reduced pressure to obtain white m crystals of N-chloro-N-enediomethanesulfonate. The crude crystals were mixed with acetonitrile 100-
S-methyl B-(y-oxy-2-pyridyl) sulfide (1,27) was suspended in acetonate) I
After mixing the Jul bath solution, the mixture was left stirring at room temperature all day and night. After the completion of the reaction, the reaction solvent was distilled under reduced pressure, and the resulting residue was subjected to column chromatography <'yv-h gel, developing solvent: chloroporm/methanol (20/1'J/vl).
When separated and purified, white crystals of the present compound 41 were obtained.
I got 59.

White crystalline melting point: 150-155°C (min M) When applying the compound of the present invention as a herbicide or plant growth regulator, it is generally necessary to use a solid carrier such as clay, talc, bentonite, diatom, etc. Water, alcohol fi (methanol, ethanol, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.),! It can be used in combination with a liquid carrier such as hydrogenated hydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), amides (dimethylformamide, etc.), and if desired, an emulsifier and two dispersants.

Suspending agents, penetrating agents, spreading agents, stabilizers, etc. f: Enriched liquid preparations, emulsions, water consolation agents, powders, etc. E+: Can be put to practical use in the dosage form of X.

In addition, depending on necessity, 1113 types of herbicides, various insecticides, fungicides, planting agents, synergists, etc. may be mixed and applied when spraying the formulation.

Other types of herbicides mentioned above include 2, for example, Farm Chemicals Hibiki Handbook (t+'arm (1bemic)).
aLsth r+ndhnok), vJ68 edition (19
There are compounds listed in 82) that are 2t.

Next, two formulation examples of herbicides containing the compounds of the present invention as active ingredients are excluded. In addition, in the following formulation examples, "part" means sub-mackerel part. However, it is not limited to these only.

Formulation example 1 Wettable powder Compound A1 of the present invention ・・・・・・・・・・・・
50 parts Sieglite A ・・・・・・・・・・・・
... 46 parts (kaolin clay powder, Sieglite Eko Co., Ltd. product name) Tsurupol 5 L] 39 songs...
Part 2 (Nonionic/Anionic surfactant, Toho Chemical Co., Ltd. product name) Horn Flex ・Open・・Open・・
2 parts (Anti-caking agent made by combining 6 parts of interfacial viscosity agent and white carbon, simple product name of Shionogi & Co., Ltd.) The above ingredients are uniformly mixed and pulverized to make an irrigation agent.

Formulation Example 2 Emulsion Compound A of the present invention; 2 parts... 2 parts
Shin ・・・・・・・・・・・・
・・75 part crane pole 268o・・
-Song...Song... 5 parts (mixture of nonionic surfactant and anionic surfactant.

Toho Chemical Co., Ltd. Product name) The above components are mixed uniformly to form an emulsion.

Formulation example 3 Granules Compound of the present invention A3 ・・beating・・5 parts bent length・・・old・・・・ 55
Part talc declension...listen/4
0 Sound 13 After uniformly mixing and grinding, add a small amount of water to 11. The mixture is stirred and kneaded, granulated using an extrusion granulator, and dried to form granules.

Next, the usefulness of one of the compounds of the present invention as a herbicide will be specifically explained in the following test examples.

Test VjlJ 1 Weeding effect test by soil treatment Vertical 1
Sterilized diluvial soil was placed in a plastic box measuring 5 ctn, width 22 Crn, and depth 60, and rice, wild grass, crabgrass,
Cyperus kULfFi and about I, s crn covering I
After that, the amount of active ingredient was uniformly spread on the soil surface in a predetermined ratio.

The medicinal solution used for spraying was the irrigation agent or emulsion of the formulation example described above diluted with water and sprayed over the entire surface with a small sprayer. Chemical spraying 3
After a week, the herbicidal effect on each weed was evaluated according to the following criteria.

The results are shown in Table 2.

Judgment Criterion 5...Weed killing rate 90X or higher (total death of all weeds) 4...
・Weed killing rate 70-90% 3... Weed killing rate 40-70X 2... Weed killing rate 20-40% 1... Killing #L rate 5-2 ON O... Weed killing rate 5% or less (None) However, the above-mentioned weed killing rate was determined by the following formula by measuring the above-ground fresh grass weight in the chemically treated plot and the above-ground fresh grass weight in the non-treated plot.

Table 2 Comparative compounds in Table 8! [It is described in Japanese Patent Publication No. 48964/1983 and has the following structural formula.

Test Example 2 Phytotoxicity test on cultivated plants by soil treatment Sterilized diluvial soil was placed in a plastic box of M 15 on, width 2 zan, depth 6 m, and beet, rapeseed,
Soybeans and cotton #1 were found, and after covering with soil of about 1.5 ml, the amount of active ingredients was uniformly spread over the soil surface at a predetermined ratio. The chemical solution used for spraying was the wettable powder or emulsion of the formulation example described above diluted with water and sprayed over the entire surface with a small sprayer. Three weeks after spraying the active agent, the crops were investigated for phytotoxicity according to the following criteria. The results are shown in Table 3.

Criterion 5: Crops are almost completely dead 4... Significant phytotoxicity against 6... 1 No phytotoxicity observed 2...
#l Slight chemical damage is observed 1...l
I Drug damage #1 I don't have a lot of advice 0...
・L l Plant damage is not 8% Table 3 Test Example 3 Growth circle test on wheat sterilized diluvial soil was placed in a 115,000 are cotton pot, and seeds of Kono and Giardia were sown in spots. .5 cm of soil was deposited. When the kono and gi reached the 3rd to 4th leaf stage, the active ingredient was uniformly sprayed onto the violet leaves so that the amount of the active ingredient was at a predetermined ratio.

2. Dilute the hydrating powder or emulsion obtained in the above formulation example with water in the chemical solution for spraying. It was applied to the entire surface of the violet leaves of wheat using a small sprayer.

Two months after the treatment, the growth status of the wheat was inspected. The results are shown in Table 4.

Test Example 4 Rice growth regulation test 1 under flooded conditions /
Alluvial soil was filled in an I O,00 [1 rrn]・r barael pot, and water was added and mixed at t1 to create a flooding condition of water depth of 2 rrn.

25-leaf stage rice (variety:
Japan 1'f! ') After transplanting two of each into the above Neubauerbot at three locations, they were treated on the specified R'i surface of the granules prepared according to formulation fl13. Two months after the treatment, the growth status of the rice was completely investigated. result? l - Shown in Table 5.

Table 4 Table 5 Table 1 The individual items in Tables 4 and 5 represent relative values when the untreated area is set as 100.

Patent applicant: Nissan Chemical Industries, Ltd.

Claims (2)

[Claims] (1) General formula (I): ↓ [In the formula, X is a hydrogen atom or a lower alkyl group, R1 is an alkyl group or a lower alkyl group substituted with a halogen atom t, Fi"t; j a lower alkyl group,... Lower alkyl group, phenyl group, directly substituted with rogene atom, 1-5
A phenyl group substituted with 2 to 5 substituents (provided that the substituents are selected from the group consisting of lower alkyl groups, halogen atoms, alkyloxy groups, nitro groups, and alkoxycarbonyl groups, and the substituents are 2 to 5 substituents) may be the same or different from each other in the case of ) or naphthyl foundation. ]
An N-oxypyridyl sulfide compound represented by n. (2) General formula (■): ↓ (wherein, X is a hydrogen atom or a lower alkyl group, and R1 is an alkyl group or a lower alkyl substituted with a halogen atom) and. General formula 0ff): [In the formula, d" is a lower alkyl group,) - a lower alkyl group substituted with a rogen atom, a phenyl group substituted with 91 to 5 substituents (however, a phenyl group substituted with 91 to 5 substituents) The group consists of a lower alkyl group, ), a rogen atom, an alkyloxy group, a nitro group, and an alkoxycarbonyl group, and in the case of 2 to 5 substituents, they may be the same or different from each other. ) or containing a naphthyl group] General formula (I) in which X , R' and R1 have the same meanings as above.] A method for producing an N-oxypyridyl sulfimide derivative represented by: ○ [In the formula, X is a hydrogen atom or a lower alkyl group; R1 is an alkyl group or a halogen atom; A substituted lower alkyl group, R' is a lower alkyl group, a lower alkyl group substituted with a halogen atom, a phenyl group, a phenyl group substituted with 1 to 5 substituents (however, 1 substituent is a lower alkyl group) A substituent selected from the group consisting of an alkyl group, a halogen atom, an alkyloxy group, a nitro group, and an alkoxycarbonyl group, and when one substituent is 2 to 5, they may be the same or different from each other.) Or indicate the Naphthyl Fund.]
A herbicidal/plant growth regulator comprising one or more N-oxypyridyl sulfimide derivatives represented by fL as an active ingredient.