JPS5835103A - Herbicide composition - Google Patents

Abstract

PURPOSE:The titled composition that is made by mixing a substituted phenyl thionocarbamate with 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl p-toluenesulfonate, thus showing herbicidal activity against annual and prennial weeds with no chemical injury to crops. CONSTITUTION:The objective composition contains, as an active ingredient, a mixture of a substituted phenyl thionocarbamate of the formula (X is O, S, vinylene; l, m are 1-4; n is 0, 1; the heterocyclic ring that is formed with the N atom, two alkylene chains and is X 5-7 membered and the two alkylene chains may be branched; R<1> is H, lower alkyl; R<2>, R<3> are H, lower alkyl, phenyl) with 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl p-toluenesulfonate or 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-phenacyloxypyrazole.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel substituted phenylthionocarbamate represented by general formula (1) % formula % and 4
-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl p-toluenesulfo*-) or t
The present invention relates to a herbicidal composition containing a mixture of f4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-7enacyloxyvirazole as an active ingredient.

However, in the above general formula (1), X represents an oxygen atom, a sulfur atom, or a vinylene group. 1 and mFi mean an integer of 1 to 4, and n means an integer of O or 1. In addition, the number of members of the heterocycle formed by the nitrogen atom, two alkylene chains, and X is 5 to 7, and the two alkylene chains may be separated.

From the viewpoint of herbicidal activity, the substituted phenylthiotcarbamate heterocycle t'i5M ring or 6-membered ring represented by the general formula (1) is preferred. 1lFi represents a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, a globyl group, a butyl group, and R2 and R3 are the same or different and each is a hydrogen atom; a methyl group, an ether group, a propyl group.

Represents a lower alkyl group such as a butyl group or a phenyl group.

Recently, weed control using % herbicides has become commonplace, and until now it has been
While some live weeds such as wild weeds, which have been neglected, die when treated with herbicides, perennial weeds such as Japanese grass and cypress, which were not so common in the past, are becoming relatively more common due to ecological characteristics that make it difficult for herbicides to be effective. It survives or regenerates and proliferates repeatedly in a short period of time in fields where there are fewer competitors, and it has come to dominate. In particular, the Japanese cypress occurs in nearly 30% of the paddy rice cultivation area in Japan, and its weed count is enormous. The water cyperus deprives paddy rice of fertilizer throughout its growing period, causing a delay in the ripening period of paddy rice, and
It remains dormant during the ripening period of paddy rice.

It also creates factors that cause the outbreak of potato disease and the damage caused by Japanese rat. Moreover, the Japanese cypress is the toughest weed in paddy fields, and in order to completely control it with herbicide treatment after transplanting the paddy rice, chemical damage to the paddy rice cannot be avoided.

The present inventors have discovered that the substituted phenylthionocarbamate represented by the general formula (1) has a control effect on various weeds, and it has been found that the substituted phenylthionocarbamate shown by the general formula (1) has a control effect on various weeds, including annual broad-leaved weeds and annual weeds of the Poaceae and Cyperaceae families. To be highly effective against
Moreover, we found that it causes almost no chemical damage to useful crops such as paddy rice, but we also searched for a synergist that would enhance its control efficacy against perennial weeds. The present invention has been completed to be able to control perennial weeds such as staghorn cyperus and urticaria with extremely low dosages compared to when each is applied alone, and to cause no phytotoxicity to paddy rice.

4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yl p-toluenesulfonate C, hereinafter referred to as compound 4tj(a)] 4- (2,4-dichlorobenzoyl) -1 , 3-dimethyl-5-7 enacyloxyvirazole [hereinafter referred to as Compound (B)] Compound (A) and Compound (B) do not cause chemical damage to paddy rice, and are effective against -year-old grass weeds and It is known to exterminate broad-leaved weeds as well as perennial weeds such as Japanese cypress and gourd.
0 and JP-A-54-41872). Among them, compound (a) has already been commercialized and is being applied as a herbicide for paddy fields;
When treated before and after rice planting during the heat treatment period at an application rate of 1 oao,
Broad-leafed weeds such as Japanese oak, Japanese oak, and azalea, as well as perennial weeds such as Japanese grasshopper, Japanese cypress, and black porgy, often remain without being completely eradicated. Furthermore, in actual fields, soil conditions, weed growth conditions, weather conditions, etc. vary widely, and in order to achieve stable effects under these complex conditions, a special method characterized by a relatively high application rate is required. Kaisho 55-1924
See Publication No. 8 mA).

By using a substituted phenylthionocarbamate represented by general formula (1) in combination with compound (a) or compound (b), various annual and perennial weeds can be effectively controlled with a low dosage. . The substituted phenylthionocarbamate represented by the general formula (1) and the compound (a) or the compound (b) act synergistically with each other, and each agent alone has an extremely insufficient herbicidal effect. Even a mixture of both compounds in mixed amounts can exhibit significantly high herbicidal effects against various weeds. Compound (a) and compound (b) have the effect of killing urikawa.

From the onset of its action to the time when it caused the aphrodisiac to wither and die.
It takes a long period of time for fi phase. However, if a substituted phenylthionocarbamate represented by the general formula (1) is applied to these O compounds under warm conditions, the period until the weeds die can be significantly shortened.〇The herbicide of the present invention The composition contains weeds that grow and proliferate in undesired places such as paddy fields and fields, in addition to Nzugayari Nakaurikawa, such as chickweed; Japanese chickweed, Japanese knotweed, Japanese knotweed; Japanese knotweed; Japanese parsley; Japanese knotweed, Japanese knotweed, taninpa; Dicotyledonous weeds such as red capsicum, stinging pear, tochuwahaze, mutsut kosagi moss; Monocotyledonous weeds such as , Japanese cyperus, Japanese cyperus, Japanese cyperus, zezuhenabi, Japanese cyperus, kawarasgana, harii, black guinea, Japanese cyperus, Japanese cyperus, firefly, hyderico, Japanese cyperus, Japanese cyperus, Japanese cyperus, black-and-white grass, and other monocot weeds. Among them, it has a high control effect against annual broad-leaved weeds and annual weeds of the Poaceae and Cyperaceae families.

Examples of typical substituted phenylthionocarbamate compounds represented by the general formula (letter) include the following.

0-[4-chloro-3-((2,2-dichlorocyclopropyl)methoxy)phenyl] 1-pyrrolidinecarbothioate 0-[4-chloro-3-((2,2-dichloro-1-methyl cyclopropyl)methoxy)phenyl] 1-pyrrolidinecarbothioate 0-[4-chloro-3-((2,2-dichloro-3,3
-dimethylcycloprobyl)methoxy)phenyl]1-
Pyrrolidine carbothioate 0-[4-chloro-3-((2,2-dichloro-cis-
3-Methylcyclopropyl)methoxy)phenyl]l-
Pyrrolidinecarbothioate 0-[4-chloro-3-((2,2-dichronotrans-3-methylcyclopropyl)methoxy)phenyl]
l-pyrrolidinecarbothioate 0-[4-chloro-3-(2,2-dichloro-3-phenylcycloprobyl)methoxy)phenyl)1-pyrrolidinecarbothioate 0-[4-chloro-3-(( 2,2-dichlorocyclopropyl)methoxy)phenyl] 3-thiazolidinecarbothiony〇-[4-chloro-3-((2,2-dichlorocyclopropyl)methoxy)phenyl) 1-(2-methyl piperidine)carbothioate 0-[4-chloro-3-((2,2-dichlorocyclopropyl)methoxy)phenyl] l-piperidinecarbothioate O-[4-chloro-3-((2,2- dichlorocyclopropyl)methine)phenyl) 1-perhydroazepinecarbotheoate 0-[4-chloro-3-((2,2-dichlorocyclopropyl)methquin)phenyl] 4-morpholinecarbothioate 0-[4-chloro-3-(2,2-dichlorocyclopropyl)methquin)phenyl] 1-(3-hyroline)carbothioate This substituted phenylthionocarbamate is shown in the reference example below, for example. It can be manufactured by a method.

Among the herbicide compositions of the present invention, the following general formula () % formula % () [wherein, X, J, m, n and t have the same meaning as the general formula (1) ic & ker, The number of members of the heterocycle formed by the nitrogen atom, two alkylene chains, and X is 5 to 60
] A herbicidal composition containing a mixture of the compound represented by the above and compound (a) or compound (b) as an active ingredient is preferable from the viewpoint of herbicidal activity against various weeds. It contains a substituted phenylteonocano (mate) represented by formula (L) and compound (a) or compound (b) as active ingredients.

When the herbicide composition of the present invention is applied to other plants, a mixture of these active ingredient compounds can be used alone, but
To make it easier to use as a herbicide, it is common to mix it with a carrier to form a preparation, which is then diluted as necessary before application. The formulation is carried out by mixing the above-mentioned mixture of active ingredient compounds with liquid or solid extender carriers (optionally using surfactants, i.e. emulsifiers and/or dispersants and/or foaming agents) according to the customary techniques for the preparation of pickled vegetables. It is also possible to use a wettable powder, an emulsion, or a wettable powder.

It can be made of rigid material such as granules. Alternatively, the active ingredient compounds can be prepared separately and mixed at the time of use.

As liquid carrier raw aromatic hydrocarbons, e.g.
silene, toluene, benzene, alkylnaphthalene; chlorinated aromatic or aliphatic hydrocarbons, such as chlorobenzene, chloroethylene;

Methylene chloride; aliphatic or cycloaliphatic hydrocarbons such as cyclohexane, paraffins (eg mineral oil fractions); alcohols such as butanol, ethylene glycol and their ethers and esters; ketones.

For example, acetone, methyl cellulose, methyl isobutyl ketone, cyclohexanone and isophorone are suitable.

Solid carriers include ground natural minerals such as kaolin, clay, talc, bentonite, gicrite, chalk, quartz, attapulgite.

Preference is given to using montmorillonite, cane earth; and ground synthetic minerals 1, such as alumina, silicates, white carbon.

Preferred examples of emulsifiers and foaming agents include nonionic and anionic emulsifiers, such as polyoxyethylene-aliphatic carboxylic acid esters; polyoxy7-etherene-aliphatic alcohol ethers, such as alkylaryl polyglycol ethers; alkyl sulfonates, alkyl sulfonates, etc. and aryl sulfonates and albumin hydrolysates. Preferred examples of dispersants include lignin sulfite waste liquor and methylcellulose.

The blending ratio of substituted phenylthionocarbamate represented by general formula (1,) and compound (a) or compound (b) in the herbicidal composition of the present invention is suitably in the range of 1:0.02 to 50. is preferably in the range of 0.1 to 20 to 1%.

In preparing the herbicide composition of the present invention, the general formula (1
It is also possible to combine two or more substituted phenylthionocarbamates shown in ) with compound (a) and/or compound (b), and furthermore, fertilizers, insecticides, fungicides, It can also be mixed with herbicides or plant growth regulators to form multi-purpose compositions.

The formulations generally contain a total of at least 1.times.1 O. weight ts1, preferably 0.000. O1~951~9
It is contained in an amount of 5% by weight or 0.1 to 80% by weight.

The herbicidal composition of the present invention may be used in the form of the above-mentioned preparations, or these preparations may be further formulated into usage forms. The total content of active ingredient compounds in the usage form can be appropriately selected within a very wide range such as 1 x 10 to 100% by weight, but preferably FilXlO to 30% by weight.
Weight -.

The herbicidal compositions of the invention are used in the customary manner appropriate to the particular use form. The total amount of active ingredient compounds used is at least If/10m, preferably 5
~100CI/10m, more preferably 20~
The range is 400 F/10 m.

The method for producing the substituted phenylthionocarbamate used in the present invention, the preparation and effects of the herbicidal composition will be explained below with reference examples, formulation examples, and effect examples.

Reference Example 1 Dissolve 4-chlorresorcin 1814iN in N-dimethylformand 700-, and add (2,2-dichlorocyclopropyl)methyl bromide 283f, anhydrous sodium carbonate 207f and sodium iodide 4ftp to a solution of
Add and stir at 90"C for 15 hours. Reaction mixture etc.
The mixture was poured into ice water and extracted with diethyl ether. After washing the ether layer with water, drying with anhydrous magnesium sulfate, -m
The medium was distilled off.

The residual oil was separated and purified using a preparative high-performance liquid chroma dog 2 filter to obtain 931% of 4-chloro-3-CC2,2-dichlorocyclocyclovir)methoxy]phenol.
and 5f of 2-chloro-5-((2<2-dichlorocyclopropyl)methoxy]phenol were obtained.

Synthesis of compound (1)] 4-chloro-3-1:(2,2-dichlorocyclopropyl)methoxy]phenol 5Ot (methanol 200d
58 ff of a 28-timethanol solution of sodium methane was added to this solution.

Then methanol was completely distilled off to give 4-chloro-3-(
The sodium salt of (2,2-dichlorocyclopropyl)methoxy]phenol was obtained. This sodium salt is N,N
-Dissolved in dimethylformamide 500d, 1-pyrrolidinethiocarbonyl chloride 56F was added to this solution, and the mixture was stirred at 60°C for 10 hours. The reaction mixture was poured into ice water and extracted with diethyl ether. The solvent was distilled off from the ether layer, and the + residue was purified by silica gel column chromatography to obtain 0-[4-chloro-3-(
(2,2-dichlorocyclopropyl)methoxy)phenyl] 1-pyrrolidinecarbothioate [Compound (1)
] t 47 F was obtained. Product melting point: 84-90°C
.

Compounds (2) to (6) t- were obtained in a similar manner. The melting point or refractive index of each compound is as described above.

Reference Example 2 4-chloro-3-[(2,2-dichlorocyclopropyl)methoxytaphenol 9.72% and sodium methylate produced from 1i7t of 28 timeethanol solution fC,4-
Dissolve the sodium salt of chloro-3-[(2,2-dichlor7chlorobrobyl)methoxytafphenol in water 300117, and add this solution to a solution of 3.2 yal thiophosgene in 100 m/chloroform so that the reaction temperature is below 10°C. dripped into. After separating the resulting reaction solution, the chloroform layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off to give chlorothioformic acid 0-[4-chloro-3-(
11.2f of (2,2-dichlorocyclopropyl)methoxy)phenyl]ester was obtained.

Chloruteoformate 0-[4-chloro-3-((2゜2-dichlorocyclopropyl)methoxy)phenyl]ester 1.00 ft-diethyl ether 2 (bathed in 1+j,
Thiazolidine 0.31F and triethylamine 0.35F were added to this solution, and the mixture was stirred at 0 to -5°C for 1 hour. The reaction mixture was washed with water, and ether was distilled off from the ether layer. The obtained oil was subjected to silica gel column chromatography to obtain 0-[4-chloro-3-(
(2,2-dichlorocyclopropyl)methoxy)phenyl]3-thiazolidinecarbothioate [compound (7)] was obtained at 1.11F. Melting point of product = 84-93.5°C
Compounds (8) to (b) were obtained in a similar manner. The melting point or refractive index of each compound is as described above.

Formulation Example 1 Prepare 15 parts of emulsion compound (1) and 15 parts of compound (a),
To this mixture was added 60 parts of a compound of xylene and inholon, and the surfactant Tsurupol 800A (trade name).

Toho Chemical Industry Co., Ltd.) 10 parts were added, and these were thoroughly stirred and mixed to obtain 100 parts of an emulsion. Formulation Example 2: 20 parts of irrigation compound (2), 20 parts of compound (b), 20 parts of white carbon. , sodium ligninsulfonate 5 parts 1
)'7 2 parts of sodium silpenbensulfonate and 133 parts of Kane 9 were mixed and ground to obtain 100 parts of a wettable powder.

Formulation Example 3 Granule Compound (1) 4 parts, Compound (A) 6 parts, Merck and bentonite mixed in a ratio of 1:3 to 80 parts, white carbon 5 parts, and surfactant Tsurupol 800A (same as above) ) After mixing 5 parts, 10 parts of water was added and kneaded to form a paste, which was extruded through a simple hole with a diameter of 0.7 cm. After drying, it was cut into lengths of 0.5 to 1 sIl, and 100 parts of granules were prepared. I lost my job.

Effect example 1 Flooded soil treatment effect test Paddy soil decorated in a porcelain pot with a diameter of 12 cln was placed.
Water was added and plowing was performed. Nobie on this.

Japanese cypress, Japanese cypress, Japanese cypress, and firefly were sown, and the germinated tubers of cypress and tubers were transplanted. Furthermore, two paddy rice seedlings (Nipponbare) at the two-leaf stage were used at a value of one plant, and watered twice.

On day 3 of transplanting paddy rice seedlings, predetermined amounts of each of the test compounds were dropped onto the water surface. After 1122 days of chemical treatment, the herbicidal effect and paddy rice chemical damage (inhibition of growth of the above-ground parts of paddy rice) were determined using the following criteria. The results are summarized in Table 1. 0 Herbicidal effect judgment criterion 5: Weed suppression rate or weed death rate compared to no treatment 80-1
00chi 4:
Less than 60 to 80 inches〃 3: #
Less than 40-60% 2:
Less than 20 to 40% l: l ~2
Less than 0%0:
0%〃Paddy rice phytotoxicity judgment standard 5: Paddy rice suppression rate compared to no treatment 80~]0
0chi 4: #
Less than 60-80% 3:
Less than 40-60% 2:
Less than 20-40-1:
〃 - Less than 20 inches O: 〃OtIA The control effects against the Japanese cypress and the control effect against the Japanese cypress are extracted from Table 1 and shown in Tables 1-1 and 1-2, respectively.

Table 1-1 (Prevention effect on water pyre) Part 1-2
Table (Prevention effect on Paddy grass) Effect example 2 Warm water earthen treatment effect test A porcelain bottle made of 12 countries in diameter) Pour K sieve into the paddy field, add water and plow through. 1.
Kika/gusa, tafugayari, and hotarui were sown, and the germinated tubers of Mizugayatsu and Urikawa tubers were transplanted.Furthermore, two paddy rice seedlings (Nipponbare) at the two-leaf stage were planted, and zm
o Flooding was carried out.

On the 3rd day after transplanting paddy rice seedlings, a predetermined amount of each test compound was dropped onto the water surface. After 22 days of chemical treatment, the herbicidal effect and paddy rice chemical damage (suppression of growth of above-ground parts of paddy rice) is 5J! Judgment was made using the criteria shown in Example IK. The results are shown in Table 2. ○ In addition, the control effect on the Japanese cypress and the control effect on the Japanese cypress were extracted from Table 2 and are shown in Table 2-1 and 2-2m1, respectively! Shown below.

Table 2-1 (Prevention effect on water cyperus) Part 2-2
Table (Preventing effect on Paddy grass) Effect example 3 Flood soil treatment effect test The sieved paddy soil was placed in a porcelain pot with a diameter of 115 m, water was added, and plowing was performed. In addition to this, weeds, broad-leaved weeds (
The tubers of Cyperus japonica and tubers of Cyperus japonica, which had sprouted 1gA, were transplanted. Furthermore, two paddy rice seedlings (Nipponbare) at the two-leaf stage were planted and flooded 23 times. A predetermined amount of each of the test compounds was dropped onto the water surface at the third mound after transplanting the rice seedlings. 20 days after the chemical treatment, the herbicidal effect and paddy rice chemical damage (inhibition of growth of the above-ground parts of paddy rice) were determined using the criteria shown in Effect Example 1. The results are shown in Table 3.

Claims (1)

[Claims] General formula (wherein, , a double 1m member formed by a nitrogen atom, two alkylene chains, and are the same or different and each represents a hydrogen atom, a lower alkyl group or a phenyl group.
,4-dichlorobenzoyl)-1,3-dimethylhyrasol-5-yl p-toluenesulfonate or 4-(
2,4-dichlorobenzoyl)-1,3=dimethyl-5
-7 A herbicidal composition comprising a mixture with enacyloxypyrazole as an active ingredient.