JPS6042376A - N-(2,3-epoxypropylene) sulfonamide derivative and selective herbicide containing the same as an active ingredient - Google Patents

Abstract

NEW MATERIAL:An N-(2,3-epoxypropylene) sulfonamide derivative shown by the formula I (R<1> and R<2> are alkyl, haloalkyl, amino which may have substituent group, aralkyl, or aryl which may have substituent group). EXAMPLE:N-(2,3-Epoxypropylene)-N-phenylsulfonyl-4-bromobenzene-sulfona mide. USE:A selective herbicide. Controoling strongly germination of Echinochloa crus- galli Beauv. Var. praticola Ohwi., extremely harmful annual weed in a paddy field, providing paddy rice plant with no phytotoxicity at all. PREPARATION:A compound shown by the formula II is oxidized in the presence of an oxidizing agent such as chromic acid or hypohalogenous acid in the absence of a solvent or in a solvent to give a compound shown by the formula I . The compound shown by the formula II is obtained by reacting a compound shown by the formula III with a compound shown by the formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides physiological selectivity between Noviea, which is a serious weed in paddy fields and annual weeds, and paddy rice, that is, selection that strongly suppresses the germination of Novvies and does not cause any chemical damage to paddy rice. The present invention relates to an N-(co,3-epoxypropylene) sulponamide fat conductor that exhibits herbicidal activity and a selective herbicide containing the same as an active ingredient.

Until now, a number of compounds have been proposed and put into practical use as herbicides for paddy fields, but most of them are
It has not been applied based on the physiological selective activity between wildflowers, which are annual grains, and paddy rice. In other words, these conventional herbicides for rice fields are used during the rice growing season (
This method is used to control wild plants that germinate by treating them (including transplanting), and takes advantage of the difference in drug resistance between wild plants and paddy rice due to their different growth stages. In addition to this, there is an application method based on so-called physical selectivity, which takes advantage of the fact that the roots of transplanted paddy rice are located in the chemical treatment layer m1 due to the soil adsorption principle of the drug, and therefore the absorption of the drug is small. Currently, these two methods are the most common.

However, the currently applied herbicides for paddy fields are not based on physiological selectivity between wild grasses and paddy rice, so they are not suitable for young rice, which has expanded rapidly in recent years with the introduction of machinery. In the field of seedling transfer 416 fields and direct sowing cultivation, paddy rice seedlings are weak and there is a risk of chemical damage, so it is extremely difficult to apply iQ to conventional herbicides for paddy fields. There is a strong need for the development of herbicides, ie compounds that have physiological selective activity between wild grass and rice.

In order to meet such demands, the present inventors continued to study compounds that have physiological selective activity between wild grass and paddy rice. The present inventors have discovered that the '4-isomer has the above-mentioned excellent selective activity, and have completed the present invention. That is, the gist of the present invention is to provide a compound having the general formula (1. R1 and R1 are alkyl A groups) - a loalkyl group, an amine group which may have a substituent, an aralkyl group, or a substituent. represents an aryl group which may be the same or different from each other. ) and a selective herbicide containing the same as an active ingredient.

The IJ-(2,3-epoxypropylene) sulfonamide compound according to the present invention (hereinafter referred to as the compound of the present invention) is a novel compound represented by the above general formula [l], and has excellent selective herbicidal activity. This is the biggest feature.

In the general formula (1), preferably R1 and Ht are C11
, a straight-chain or branched alkyl group, 0.
~． haloalkyl group, C7~, amino group which may have an alkyl substituent, alkyl moiety is 01~. (However, X is a button-like or branched alkyl group of 01-@,...Rogen atom% c, -.

represents an alkoxy group or a nitro group, m represents 1' [of θ~7], a tetrahydronaphthyl-substituted phenyl group (
However, %Y FiO+~, a linear or branched alkyl group, C9~, cycloalkyl-JLO
represents a haloalkyl group of I~, an alkoxy group of 01-3, a halogen atom or a nitro group, n tri O-
(representing an integer of k).

Particularly preferably, R1 and R1 are a linear or optionally branched alkyl group of 01-@, a haloalkyl S of C8~, a dialkyl-substituted amine group of a+~,
7. Substitution in which the alkyl moiety is a straight chain of C6~. thyl group (XI′i0+~, which may be a chain or branched alkyl group, or a halogen atom, m represents an integer of O-), a tetrahydronaphthyl group, or a straight chain of ~ an optionally branched alkyl group, a, ~6 cycloalkyl group%01~. haloalkyl group, <01~.

represents an alkoxy group, a halogen atom, or a nitro group, and represents an integer from nI'iθ to ).

R1 and R may be the same or different from each other,
It is preferable that at least one of the groups is a 7-el group which may have a substituent.

In the above description, halo and halogen atoms represent fluorine, chlorine, bromine, and iodine.

The compound of the present invention is produced by the following method.

(IJ (wherein R' and R'' have the same meanings as above) The above reaction is preferably carried out without a solvent or in a solvent in the presence of an oxidizing agent. Only one solvent involved in the reaction is used. If not, there is no particular limitation, and hydrocarbons such as benzene, toluene, xylene, chlorobenzene, methylene chloride, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride, ethers such as diethyl ether, tetrahydrofuran, dioxane,
Methyl alcohol, ethyl alcohol 1,4-,?
Alcohols such as 7'' alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, nitriles such as acetonitrile, dimethylpolamide, water, etc. can be used.

As the oxidizing agent, chromic acid, hypohalous acid, potassium permanganate, monoperpentatalic acid, methachloroperbenzoic acid, peracetic acid, hydrogen peroxide, etc. are used. In addition, if necessary, a suitable reaction aid, such as hydroxide) 17
um, alkali metal hydroxides such as potassium hydroxide, alkali metal organic acids such as sodium acetate, alkali metal inorganic acid salts such as sodium phosphate, acid salt hydrates such as iron (1) acetylacetone or acetic anhydride, etc. is used. reaction(
The temperature of 1'1A can be carried out at any temperature from the freezing point to the boiling point of the solvent, and heating and cooling can be carried out as necessary.

Incidentally, the starting material represented by the above general formula (1) is produced by the following method.

[11] (In the formula, R1 and R have the same meanings as above or represent a halogen atom) The above reaction is suitably carried out without a solvent or in the presence of a solvent. The solvent to be used is not particularly limited as long as it is not related to this reaction, and includes hydrocarbons such as evaporate, benzene, toluene, and xylene, chlorobenzene, methylene chloride,
Chloroform, carbon tetrachloride and other chloroformed hydrocarbons, diethyl ether, tetrahydrofuran, dioxane and other ethers, acetone, methyl ethyl ketone and other ketones, acetic acid (ethyl and other esters, dimethylformamide, dimethyl sulfoxide, etc.) Water, pyridine, etc. Also, if necessary, appropriate reaction aids, such as hydroxide, alkali metal hydroxides such as IJium, potassium hydroxide, -&M sodium, sodium hydride, potassium hydride, etc. metal hydride, pyridine,
Organic bases such as triethylamine can be used.

The reaction temperature can be any temperature from the freezing point to the boiling point of the solvent, and heating or cooling can be performed as necessary.

In addition, in the general formula [river], the compound represented by the general formula [river] can also be produced by the following reaction at the platform of R1-=R1.

JR'OO, O/ +H, N Nor/-+ (R'SO West N
(In the formula, R' has the same meaning as above.) Note that the reaction conditions in this case are similar to the production method of the general formula [ff].

2) (In the formula, R1, R1 and XI'i have the same meanings as above)
The above reaction is suitably carried out without a solvent or in the presence of clear 'Il\:'. The baths used include hydrocarbons such as benzene, toluene, and xylene, chlorobenzene% methylene chloride, chloroform, carbon tetrachloride, and other hydrocarbons, diethyl ether, tetrahydro-7rane,
Examples include ethers such as dioxane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, dimethylformamide, dimethyl sulfoxide, pyridine, and water. In addition, if necessary, suitable reaction aids such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate,
Alkali metal hydrogen carbonates such as potassium hydrogen carbonate, alkali metals such as metallic sodium and total potassium hydride, total hydride such as sodium hydride and potassium hydride, and organic bases such as pyridine and triethylamine can be used. Is the reaction temperature based on the freezing point of the solvent? It is any temperature up to point j.

(In the formula, R1, ul and Ketones such as methyl ethyl ketone, dissolved or concentrated in dimethylformamide, dimethyl sulfoxide, water, pyridine, etc., or in the presence of a suitable reaction aid without a solvent, such as an alkali metal hydride such as sodium hydroxide. In addition, the reaction can be carried out at any temperature from the freezing point to the boiling point of the solvent, and if necessary, heating or cooling can be carried out.

Next, the production of the compound of the present invention is specifically shown as Synthesis 1 (.1j).

Synthesis example/Synthesis of N-(J,,7-epoxypropylene)-N-phenylsulfonyl-gubromo\benzenesulfonamide The chloroform solution was diluted with metachloroperbenzoic acid, 6I to
After reacting for 3 hours, the saturated sodium bicarbonate solution (t%) was washed with an acid sodium aqueous solution, the chloroform was distilled off under reduced pressure F, and the resulting crystalline visceral ethanol was recrystallized. Then, the object is θI
(Compound 100 in Table 17 below) was obtained. The melting point of the obtained compound was /3, θ~t3q, 0°C.

Synthesis Example Synthesis of N-(j,,?-epoxybrobylene-N-phenylsulfonyl-n-propylbenzenesulfonamide) Add sθ% sodium hydride to a solution of sulfonamide λ, og in anhydrous dimethylformamide.
, oqg was gradually added. After the generation of hydrogen had ceased, a solution of 84 tg of benzenesulfonyl chloride in hot water dimethylformamide/θml was added dropwise. The mixture was left to drain for 1 hour, then poured into a drain and extracted with ethyl acetate. The organic layer was thoroughly washed with water and diluted hydrochloric acid, dried over anhydrous magnesium sulfate, concentrated, and subjected to 4'ff silica gel column chromatography to obtain the desired product, SI (Compound Shop Tough).

The refractive index of the compound trinD = i, s
It was strung with str 4.

Synthesis Example 3 Synthesis of N-(co,3-epoxypropylene-di-p-toluenesulfonylimitono) In benzene, in the presence of triethylamine, p-toluenesulfonychloride and amine, 1)
To a 10 ml chloroporum solution of the obtained N-teryrouzy p-)rue yx sulfonylimido, OI was added metachloroperbenzoic acid, daI, g.

The reaction was carried out at ℃ for 3 hours. After the reaction was completed, it was washed with a saturated aqueous sodium bicarbonate solution and a trivalent aqueous sodium thiosulfate solution, chloroform was distilled off under reduced pressure, and the obtained crystals were recrystallized from ethanol to obtain the target compound/, 71/ (compound A 4I4I). . The melting point of the obtained compound is //3.0~/13. It was θ°C.

Synthesis Example DA Synthesis of H-(j,,?-Epoxypropylene)-diphenylsulfonylimide Diphenylsulfonylimide, θg of anhydrous shimedylformamide loml solution with sodium thihydride O,
JA 9 was added gradually. After the generation of hydrogen had stopped, 49 g of epichlorohydrin O was added dropwise. After reacting for 3θ minutes at room temperature, it was poured into water and extracted with vinegar Q (2 ethyl).The organic layer was thoroughly washed with water and diluted hydrochloric acid, dried over anhydrous magnesium sulfate, condensed 1, and purified by silica gel column chromatography. , the target compound a, og was obtained (compound A/). The melting point of the obtained compound was g/, 0-13.0"C.

Compounds of the present invention obtained in the same manner are shown in Table 1. still,
Table 1.1 shows the compounds obtained by the present invention, corresponding synthesis examples, and physical property values. Among the compounds of the present invention shown in Tables 1 and 1, those with the same ul and R1 can also be produced according to Synthesis Example 3 or It can also be synthesized by the following method.

Note that the present invention is not limited to the compounds listed in Table 1.

Table 1 Regarding the physiological activity of the compounds of the present invention, specifically, as shown in the test example below, compound Jf6.2 of Table 1-7
6 and A//! When r was treated with 3I to /are, the growth of wild grass was completely inhibited, but paddy rice during the germination stage was not affected at all even when treated with the same compound at 10'OI, is normal as in the untreated area.

This shows that the compound of the present invention does not cause any harm to the growth of paddy rice even when treated at 60 times the dose that completely inhibits the growth of wild grass. This is because it has extremely high inter-region selectivity.

Therefore, the basic principle of the compound of the present invention is essential selectivity between wild grasses and paddy rice, and this is not possible with conventional herbicides! It can be applied from the germination period of paddy rice,
The greatest feature is that it can be safely applied, especially to flooded and directly sown rice.

Furthermore, the compound of the present invention can be mixed with paddy rice seeds and sprayed at the same time, completely eliminating the need for herbicide spraying and having extremely innovative properties.

Although the physiological activity of the compounds of the present invention varies depending on the type and position of the modified functional group, a common characteristic of the compounds of the present invention is that they are significantly less toxic than water 4111.

In addition, the herbicidal spectrum of the compound of the present invention is highest in wild grasses, and the second highest sensitivity is in grasshoppers, Japanese grasshoppers, Japanese grasshoppers, yellowtail grasses, fireflies, and the like.

In order to apply the compound of the present invention as a herbicide, it can be formulated into wettable powders, emulsions, granules, flowables, etc. according to conventional herbicide formulation methods using carriers or surfactants that are generally used in pesticide formulations. It can take a form.

Furthermore, the herbicide containing the compound of the present invention can be applied at the same time as other agricultural chemicals used in WI, such as herbicides, insecticides, fungicides, insecticides, growth regulators, or fertilizers.

Next, examples of formulations using the compound of the present invention will be described. In addition, "department" and "department" below refer to "heavy punishment department" and "department" respectively.
It means "M-ochi".

Formulation example/(Water 111 drug) 40 parts of Compound S of the present invention compound shown in Table 17.

Carplex 4#1tO (Shionogi Pharmaceutical Co., Ltd., trade name),
247 parts of N,N kaolin clay (trademark name of Ueya Kaolin Co., Ltd.) and 5 parts of a crystalline alcohol sulfate ester surfactant Nluball 11070 (trade name of Toho Kagakusha Co., Ltd.) were mixed and ground uniformly. A hydrating powder containing 10% of the active ingredient was obtained.

Formulation Example, 2 (Granules) 5 parts of the compound of the present invention shown in Table 1, clay (
Manufactured by Nippon Talc Co., Ltd.),? 1 part, bentonite (-nJ
55 parts of r1 (manufactured by Yoko Co., Ltd.) and a part of the succinate-based surfactant Eyarol OT-/ (Toho Kagaku Co., Ltd., commercial 1'L name) were mixed and ground, then 70 parts of water was added and stirred uniformly. did. This was extruded through a hole with a diameter of 0.6 mm using a kneading and granulating machine.

After drying at 6θ to 6s°C for 2 hours, the mixture was cut into lengths of approximately 1 to λ to obtain granules containing 3% of the active ingredient.

Formulation Example 3 (Emulsion) Compound Notification 3 of the present invention compound shown in Tables 1 and 1 was dissolved in a mixed solvent consisting of 3 parts of xylene, 30 parts of xylene, and 123 parts of dimethylformamide, and the polyoxyethylene surfactant Tsurupol 3003M was added. (Toho Kagyosha, trade name) is part was added to obtain an emulsion containing 30 active ingredients.

Next, a test example of herbicidal activity using the compound of the present invention will be described. In addition, the compound of the present invention is suitable as a skin-repelling active ingredient, especially at low doses, for flooded soil treatment and upland soil before and during weed germination, and its use 4. is the amount of active ingredient/per are. S to SOW, preferably 3 to 1 g.

Hereinafter, the present invention will be explained based on test examples, but the present invention is not limited to the above-mentioned tooth 1 table f L table, formulation examples, and the following test examples. .

Test Example 1 Light-exposed young fruits and transplanted young seedlings in the half-year period when paddy field weeds have not appeared.
Phytotoxicity test for K. A porcelain pot with a size of 1/3 ggso was filled with paddy alluvial clay loam, and after fertilization, an appropriate amount of water was added and plowed.
M seeds of weeds such as Japanese grasshopper, Japanese cypress, Kikashigusa, and Heraomoguriki were prepared/ζ. Transfer these seeds to the soil surface/IZ
It is evenly mixed in the rice, and the paddy rice awakens at the ko and θ leaf stages (variety: Akinishiki, plant height: about 7.5cm; CrrL's seedling quality: good)
Shallow planting was carried out using 3 bots per row with an insertion depth of 1crrL.

After that, the flooded state was maintained at a depth of about JcTL, and the next day,
Compound A obtained in the same manner as Formulation Example 1 and Formulation Example 1
N-allyl-N-(α,α- Irrigation agent containing dimethylhensyl)benzenesulfonamide (hereinafter abbreviated as Comparative Agent A) and 5-(Q-10 lobenzyl)-N,N-diethylthiocarbamate (hereinafter abbreviated as Comparative Agent 0). Prepare the agent by diluting it with water and use it as the amount of active ingredient. ;, Ko left, so.

A dropwise treatment was performed on a predetermined scenic water surface so that the amount of water was 100Ii.

After chemical treatment and treatment, carry out water leakage for -days CrrL/day,
The plants were cultivated in a reheating house, and the herbicidal effect and phytotoxicity were investigated on the day after treatment with the binder, and the results are shown in Table 11.

Furthermore, the evaluation of the herbicidal effect is was expressed as a herbicidal effect coefficient based on the following criteria.

In addition, the degree of phytotoxicity to transplanted paddy rice seedlings was expressed as a phytotoxicity coefficient according to the following criteria.

/7・' / Test Example: Herbicidal effect during the initial stage of weed emergence in paddy fields and chemical damage test on paddy rice at the germination stage 8110 minutes (7) Placed in a porcelain pot in a paddy field off the coast of a paddy field
R' was filled with clay soil, and after fertilization, an appropriate amount of water was added and puddling was performed, and various hybrid seeds of Japanese millet, Japanese cyperus, and Kikashigusa were sown. The seeds are grown at soil surface vI/cm
After being mixed uniformly into the interior, it is approximately 2 cm deep. l'l'! watery k
, (kept 1.

Meanwhile, weed miko was placed in a pot made in the same manner as above.
Without iK seeds, water was drained at about -a 7, and 10 plants of Mizuna Kamiko (Shinbai Nihonbare) in the germination stage were transplanted per pot.

Preparation pl/at the time of weed germination and the day after transplanting paddy rice seeds
Wettable powder and formulation example of Compound 5.23 of the compound of the present invention obtained by Compound Q4 Aλ to Koro, 33 to Hiroj, ? , to lda0. /97 to /l
, / as a hydrating agent and comparative agent as active ingredients Formulation Example 1
N-allyl-N-(α-methylbenzyl)benzenesulfonamide obtained in the same manner as (Comparison 7i1.l B below)
It is abbreviated as ) and Comparative Agent C as active ingredients were diluted with water and removed as active ingredients. g, 72.5125 per FJ/R in drug damage test
A predetermined amount of the solution was dropped onto the flooded surface so that %3Q1/θop was achieved.

Thereafter, the plants were cultivated in a greenhouse, and the herbicidal effects and chemical damage were examined on the second day after chemical treatment, and the results are shown in Table 3.

In addition, the fF value of the herbicidal effect was expressed by the herbicidal effect coefficient as in Test Example No. 1, and the phytotoxicity against germinating paddy rice was also expressed by the Nori-11 damage coefficient as in the Test Example.

Kasumi'τ1 Test Do IJ j Weeding effect and postcard test in field soil treatment, light-filling field black soil into a resin vat of 2 soo l are;
After fertilizing, 10 soybean and cotton crops were planted at 1'+1 seedlings, and about 2 heaps of soil was covered. On this soil surface, evenly add soil mixed with the weeds of crabgrass and Japanese cypress.
Formulation Example/Compound jFa of the compound of the present invention prepared by
Irrigation agent and formulation example / Same as formulation example / with hydration ratio 11 using the obtained compounds 20% S6 to 6A, chestnut to tg as active ingredients and comparative agent. a)),7-(,?,4(-dichlorophenyl)
-/, /-Dimethylurea (hereinafter abbreviated as comparative agent) and comparative agents A and B were uniformly sprayed using a small power pressurized spray machine.

After that, the cultivation was managed in a greenhouse, and the weeding effect and kuwakichi were investigated on the first day after the mulberry treatment. The herbicidal effect coefficient was expressed as a herbicidal effect coefficient, and the accumulation 't'f on crops was also expressed as a phytotoxicity coefficient similar to the standard in Test Example 1.

6 Table continued from page 1 0 Inventor Ushinohama - Line Kamoshihi Research Institute, Midori Ward, Yokohama City

Claims (1)

[Claims] (11 General formula (wherein R' and R'' are an alkyl group, a haloalkyl group,
An amino group that may have a 11τ substituent, an aralgyl group, or an aryl group that may have a substituent,
They may be the same or different. ) denoted by N−(
3-epoxypropylene) sulfonamide fatty conductor. (2) General formula (wherein RI and R are an alkyl group, a haloalkyl group,
It represents an amino group that may have a substituent, an aralkyl group, or an aryl group that may have a substituent, and may be the same or different from each other. ) denoted by N-(,
A selective herbicide containing 84 2, J-epoxypropylene sulfonamides as an active ingredient.