JPS6391376A - Sulfonylisothiourea derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [R1 is (substituted)phenyl, (substituted)benzyl or (substituted)pyrazole group; R2 and R3 are lower alkyl or lower alkoxy; Z is CH or N] or its salt. EXAMPLE:N<1>,N<3>-bis(4, 6-dimethoxy-2-pyrimidinyl)-N<2>,N<4>-bis[(2-methoxycarbonyl benzyl)sulfonyl]-alpha,alpha'-dithio-bisformamidine. USE:A herbicide having low toxicity. PREPARATION:The compound of formula III [e.g. N-(4,6-dimethoxy-2- pyrimidinyl))-N'-(2-methoxycarbonylbenzylsulfonyl)thiourea] is made to contact with an oxidizing agent (e.g. halogen) preferably in an inert solvent to effect dehydrogenation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel sulfonylisothiourea derivative having low toxicity and excellent herbicidal activity.

The sulfonylisothiourea derivatives of the present invention (see below) are used as herbicides.

Prior Art Until now, sulfonylisothiourea derivatives having herbicidal activity have been reported (for example, Japanese Patent Application Laid-Open No. 56-65886).
, No. 54-157579, etc.), but the sulfonylisothiourea derivative of the present invention is not described at all.

While many chemicals have been used as spot herbicides, they are still not sufficient in terms of toxicity to mammals, fish and shellfish, herbicidal effects on weeds, and environmental pollution. Therefore, there is a desire for the emergence of so-called low-toxicity herbicides that are less toxic and exhibit herbicidal effects against weeds.

Means for Solving the Problems The present invention provides a benzyl group or an optionally substituted pyrazole group having low toxicity and excellent herbicidal activity with the general formula %, Rs, Rs represents a lower alkyl group or a lower alkoxy group, and Z represents CH or N, respectively] or a salt thereof.

The compound [1] of the present invention or a salt thereof has a structural feature in that it has a structure in which two molecules of sulfonylisothiourea are condensed on the sulfur atom of the isothiourea skeleton, and based on this specific chemical structure, it has a low It is toxic and exhibits excellent herbicidal effects against weeds in rice fields, fields, non-agricultural lands, etc.

The present invention provides a compound [T] having such excellent characteristics.
or its salt.

In the above general formula, the optionally substituted phenyl group and the optionally substituted benzyl group represented by R3 are 1 to 5, preferably 1 to 3, optional substituents at any position on the benzene ring. Indicates an optionally substituted phenyl group or benzyl group.

The substituent on the phenyl group or benzyl group is preferably, for example, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a lower alkoxy group.

Aryl group, aryloxy group, aralkyl group, aralkyloxy group, acyl group, acyloxy group, acylamino group, carbamoyl group, thiocarbamoyl group, carbamoyloxy group, sulfamoyl group, sulfamoyloxy group, halogen, carboxyl group.

Hydroxy group, mercapto group, lower alkylamino group,
Arylamino group, aralkylamino group, lower alkyl-arylamino group, nitro group, cyano group.

Amino group, sulfo group.

R4 represents an organic residue, m represents 0, 1.2], and the lower alkyl group is a linear, 9-branched or cyclic alkyl group having 1 to 6 carbon atoms. means a group such as methyl, ethyl, n-propyl,
Isopropyl, n-butyl, isobutyl, 5ec-butyl, tert-butyl, n-pentyl.

5ec-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, etc. are used, and the lower alkenyl group has one double bond.
means a linear, monobranched or cyclic alkenyl group having 3 to 6 carbon atoms, such as allyl, isopropenyl, -butenyl, 2-pentenyl, 2-hexenyl, and cyclopentenyl.

Cyclopentadienyl, cyclohexenyl, etc. are used, and the lower alkynyl group means an alkynyl group having 3 to 6 carbon atoms, such as propargyl, 2-butynyl, 3-butynyl, 3-pentynyl, 3-hexynyl, etc. The lower alkoxy group means a linear monobranched or cyclic alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-
Butoxy.

Isobutoxy, 5ec-butoxy, tert-butoxy, n-pentyloxy, n-hexyloxy, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy, etc. are used, and the aryl group has 6 to 14 carbon atoms.
An aryl group such as phenyl, naphthyl, biphenylyl, etc. is used, an aryloxy group refers to an aryl group having 6 to 14 carbon atoms, and an aralkyl group refers to an aralkyl group having 7 to 19 carbon atoms. For example, benzyl, phenethyl, phenylprobyl, trityl groups, etc. are used, and the aralkyloxy group has 7 to 1 carbon atoms.
9 aralkyloxy group, such as benzyloxy, phenethyloxy, 2. Phenylpropyloxy, trityloxy, etc. are used, and the acyl group means an acyl group derived from an organic carboxylic acid, such as lower alkylcarbonyl group, lower alkenylcarbonyl group, arylcarbonyl group, aralkylcarbonyl group, lower alkoxy Carbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, lower alkoxycarbonyl-carbonyl group (here, lower alkyl, lower alkenyl, aryl, lower alkoxy, and aralkyl group have the same meanings as above), heterocyclic oxycarbonyl group, or heterocycle Carbonyl group (Heterocyclic group here includes, for example, chenyl, benzothenyl, pyrrolyl, oxasilyl, piperazinyl, thiazolyl 2-thiadiazolyl).

At least a sulfur atom (optionally oxidized).

A 5- to 6-membered heterocyclic group containing either an oxygen atom or a nitrogen atom (which may be oxidized) is used, specifically, for example, acetyl, propionyl,
butyryl, pentanoyl, hexanoyl, benzoyl,
naphthoyl, benzylcarbonyl.

Phenethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, chenylcarbonyl, benzochenylcarbonyl, chenyloxycarbonyl, etc. are used, and the acyloxy group has the formula A-0-
(A represents the above-mentioned acyl group), specifically acetoxy, propionyloxy, butyryloxy.

Pentanoyloxy, hexanoyloxy, benzylcarbonyloxy, phenethylcarbonyloxy, benzoyloxy, naphthoyloxy, thenylcarbonyloxy, benzothenylcarbonyloxy, etc. are used,
The term acylamino group refers to an amino group substituted with one or two of the above acyl groups, specifically acetylamino, propionylamino, butyrylamino, benzoylamino, benzylcarbonylamino, and thenylcarbonylamino.

Diacetylamino, methoxycarbonylamino, ethoxycarbonylamino, methoxycarbonylcarbonylamino, ethoxycarbonylcarbonylamino, benzyloxycarbonylamino, etc. are used, and the halogens include, for example, fluorine, chlorine, and bromine.

A lower alkylamino group means an amino group substituted with one or two lower alkyl groups as described above, such as methylamino, ethylamino, n-butylamino, dimethylamino, diethylamino, dimethylamino, etc. (n-
butyl) amino, cyclohexylamino, etc. are used,
An arylamino group is one or two of the above-mentioned aryl groups.
The term "aralkylamino group" refers to an amino group substituted with one or two aralkyl groups, such as phenylamino, phenylmethylamino, etc.; -Phenylethylamino, 2-phenylmethylamino, benzhydrylamino, tritylamino, etc. are used, and the lower alkyl-arylamino group means an amino group substituted with the above-mentioned lower alkyl group and the above-mentioned aryl group. ,
For example, N-phenyl-N-methylamino, N-phenyl-N-ethylamino, etc. are used, and the organic residue represented by R4 is, for example, the above-mentioned lower alkyl group, lower alkenyl group, lower alkoxy group, or aryl group. , aryloxy group, aralkyl group, aralkyloxy group.

It means an acyl group, an acyloxy group, an acylamino group, a lower alkylamino group, an arylamino group, an aralkylamino group, a lower alkyl-arylamino group, a heterocyclic group, and the like.

The above lower alkyl group, lower alkenyl group, lower alkynyl group, and lower alkoxy group may further include, for example, an alkylthio group having 1 to 4 carbon atoms (e.g., methylthio, ethylthio,
n-propylthio, isobutylthio, etc.), arylthio groups having 6 to 14 carbon atoms (e.g., phenylthio, etc.), aralkylthio groups having 7 to 19 carbon atoms (e.g., benzylthio W:
l Halogen (Example 7 ++, chlorine, bromine, iodine, etc.),
Alkoxy groups having 1 to 6 carbon atoms (eg, methoxy, ethoxy, n-propoxy).

tert-butoxy, n-hexyloxy, etc.), nitro group.

Carbamoyl group, carbamoyloxy group, cyano group.

It may be substituted with 1 to 3 sulfamoyl groups, sulfamoyloxy groups, carboxyl groups, hydroxy groups, the same acylamino groups as mentioned above, or the like.

The above aryl group, aryloxy group, aralkyl group, and aralkyloxy group further include, for example, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy group, an acyl group, an acyloxy group, a nitro group, a cyano group, on the aromatic ring. It may be substituted with 1 to 3 halogens, acylamino groups, alkylthio groups having 1 to 4 carbon atoms (eg, methylthio, ethylthio, n-propylthio, tert-butylthio), or the like.

Here, lower alkyl group, lower alkenyl group.

Lower alkynyl group, lower alkoxy group, acyl group.

As the acyloxy group, halogen, and acylamino group, the same ones as above are used.

The above carbamoyl group, thiocarbamoyl group, carbamoyloxy group, sulfamoyl group, and sulfamoyloxy group further include, for example, a lower alkyl group.

It may be substituted with 1 or 2 lower alkoxy groups, aryl groups, or aralkyl groups. Here too, lower alkyl groups, lower alkoxy groups, and aryl groups.

As the aralkyl group, the same ones as above are used.

Among the substituents in the substituted phenyl group and substituted benzyl group represented by R, preferred are an acylamino group and a lower alkoxycarbonyl group.

Lower alkyl group optionally substituted with 1 to 3 halogens, sulfamoyl group optionally substituted with 1 to 2 lower alkyl groups, lower alkoxy group optionally substituted with 1 to 3 halogens, cyano group, halogen, nitro group, and lower alkylsulfonyl group.

[In the formula, RA is an acylamino group, a lower alkoxycarbonyl group, a lower alkyl group optionally substituted with 1 to 3 halogens, a sulfamoyl group optionally substituted with 1 to 2 lower alkyl groups, or a halogen RB is a hydrogen atom, halogen, lower alkyl group, or nitro group; n is 0 or It is a group represented by co indicating l, most preferably when nh<O, RA represents a halogen and RB represents a hydrogen atom, when n is 1, R^ represents a lower alkoxycarbonyl group or a halogen, and RB represents hydrogen. Indicates an atom.

Here, an acylamino group represented by RA.

Rabbit lower alkoxycarbonyl group, lower alkyl group optionally substituted with 1 to 3 halogens, sulfamoyl group optionally substituted with 1 to 2 lower alkyl groups, optionally substituted with 1 to 3 grams of halogen The lower alkoxy group, halogen, lower alkylsulfonyl group or acyl group, and the halogen and lower alkyl group represented by RB are defined by R and the same ones as those defined in R are used.

The pyrazole group in the optionally substituted pyrazole group represented by RI includes pyrazol-3-yl group,
pyrazol-4-yl group or pyrazol-5-yl group,
Preferably, pyrazole-5-yl groups are used, and these pyrazole groups may be substituted with 1 to 3 arbitrary substituents at any positions.

As the substituent for these pyrazole bases, the same substituents as those for the substituted phenyl group or substituted benzyl group shown in R1 above are used, but preferably lower alkyl groups and lower alkyl groups with 1 or 2-substituted carbamoyl group, lower alkoxycarbonyl group, carboxyl group or halogen, more preferably lower alkyl group or lower alkoxycarbonyl group. Among these, particularly preferred are, for example, methyl,
Ethyl, n-propyl, n-propyl, isopropyl,
Straight chain or branched lower alkyl groups having 1 to 4 carbon atoms such as n-butyl and t-butyl, or lower alkoxycarbonyl groups having 1 to 4 carbon atoms such as loboxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, etc. etc.

The lower alkyl group and lower alkoxy group represented by R3 or Ro are the same as those defined for R1. Among these, 1. Preferably each has 1 to 4 carbon atoms.
lower alkyl groups (e.g., methyl, ethyl.

n-propyl, isopropyl, n-butyl, tert
-butyl) or a lower alkoxy group having 1 to 4 carbon atoms (
For example, preferably R, , R3 are each a methyl group or a methoxy group. Z is preferably CH.

When compound [1] has a basic group such as an amino group in the molecule, for example, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid.

It may form an acid addition salt with an organic acid such as formic acid or an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid.

Compound [1] has a mercapto group in the molecule, a hydrocarbon, for example, an alkali metal (e.g. sodium, potassium, etc.)
, inorganic bases such as alkaline earth metals (e.g. calcium), trimethylamine, triethylamine, ter
t-butyldimethylamine, dibenzylmethylamine,
Benzyldimethylamine, N.

It may form a salt with an organic base such as N-dimethylaniline, pyridine, or quinoline.

Compound [1] or a salt thereof can be applied to a wide range of weeds at extremely low dosages, such as Japanese millet grass and Japanese cypress.

Paddy field weeds such as Japanese firefly, Japanese cypress, Japanese cypress, Japanese cypress, Japanese black bream, Japanese yellowtail, Japanese yellowtail, Japanese yamai, Japanese azalea, Japanese staghorn grass, Japanese cypress, clove knotweed, and Japanese chickweed, Japanese knotweed, Japanese foxtail grass, Japanese blueberry, Japanese thornweed, Japanese knotweed, Japanese knotweed.

Common purslane, American king moth, white 2 (natura morning glory, mulva morning glory, Japanese sorghum, Japanese sorghum 1, Japanese sorghum, Japanese commonweed, oat, black grass, Japanese sorghum.

It has excellent herbicidal activity against upland weeds such as chickweed, mustard, snail weed, and snail weed, and has extremely low toxicity to mammals, fish, and shellfish. It also shows high safety with little phytotoxicity to crops such as rice, wheat, barley, corn, and soybeans.

Compound [1] or a salt thereof exhibits an excellent herbicidal effect on paddy field weeds and is suitable as a herbicide for paddy fields.It also exhibits an excellent herbicidal effect on upland weeds and is suitable as a herbicide for upland fields. Useful.

Compound [I] or a salt thereof exhibits excellent herbicidal effects on various weeds, and has low toxicity to mammals, fish and shellfish,
Paddy fields without polluting the environment.

It can be used extremely safely as a herbicide in fields, orchards, or non-agricultural fields.

When using compound [I] or a salt thereof as a herbicide, the compound
1] or one or more of its salts can be dissolved or dispersed in a suitable liquid carrier depending on the purpose of use, or mixed or adsorbed with a suitable solid carrier to form emulsions, oils, sprays, and wettable powders. , powder, DL type powder 8 grains, fine granules, fine granules F, agent II, etc. These preparations may contain emulsifiers, dispersants, spreading agents, penetrating agents, wetting agents, mucilage agents, stabilizers, etc., as required, and can be prepared by methods known per se. Liquid carrier (solvent) used
For example, water, alcohols (e.g. methanol,
ethanol, n-propanol, isopropanol, ethylene glycol, etc.), ketones (e.g., acetone 1-methyl ethyl ketone, etc.), ethers (e.g., dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.) ), aliphatic hydrocarbons (e.g. kerosene).

kerosene, fuel oil 1 machine oil, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent naphtha).

methylnaphthalene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride, etc.), acid amides (e.g., dimethylformamide, dimethylacetamide, etc.), esters (e.g., ethyl acetate, butyl acetate, Fatty acid glycerin 1 t, t,)
-klt+L Haku11? -) y), 2 kl propionitrile, etc.), and these solvents may be used alone or in combination of two or more in an appropriate ratio.

Solid carriers (diluents and bulking agents) include vegetable powders (e.g.
(soybean powder, tobacco powder, wheat flour, wood flour, etc.), mineral powders (e.g., clays such as kaolin, bentonite, acid clay, talcs such as talc powder, waxite powder, silicas such as diatomaceous earth, mica powder, etc.) ), alumina, sulfur powder, activated carbon, etc., and these may be used alone or in a mixture of two or more in an appropriate ratio.

As surfactants used as emulsifiers, spreading agents, penetrating agents, dispersants, etc., soaps, polyoxyethylene alkylaryl ethers (e.g., Neugen, E.N. 142 (E, A142)) may be used as necessary. o Daiichi Kogyo Seiyaku (
Co., Ltd.), polyoxyethylene aryl 7. Eyute 7. (e.g., 7ner 2.■, manufactured by Toho Chemical Co., Ltd.), alkyl sulfates (e.g., Emar 0 ■ 10, Emar 40, manufactured by Kao Soap (Aji)), A■, IL Achi IL? +1/7 ・Nokanaka H Go'M
(Bara 1 Soil F゛) Sunaro FnTO
No. 9 - Neopelle Kusu manufactured by Kogyo Seiyaku Co., Ltd. ■Kao Soap (
Co., Ltd.), polyethylene glycol ethers (e.g. Noni Ball 85, Noni Ball 100 tons) = Ball 160
■, manufactured by Sanyo Kasei Co., Ltd.), polyhydric alcohol esters (
For example, Tween 20o,) Vienna 800. Kao soap (
For non-ionic agents such as those manufactured by Co., Ltd., it is appropriate to use 1 to 90% by weight, and for oils, powders, DL type powders, etc., it is appropriate to use 0.01 to 10% by weight, and for fine granules, fine particles, etc. The appropriate concentration for Agent F1 granules is about 0.05 to 10% by weight, but these concentrations may be changed as appropriate depending on the purpose of use. Emulsions, wettable powders, etc., are suitably diluted and increased in volume (for example, 100 to 100,000 times) with water before use, and then sprayed.

When using Compound [1] or its salt as a herbicide, the amount to be used depends on the application situation, application period, and application method.

There are differences depending on the target grass species, cultivated crops, etc., but in general, the active ingredient (compound [1,] or its salt) is about 0.05 to 50 g per 1 are of paddy field, preferably 0.1 to 50 g.
The amount is about 0.05 to 20 g, preferably about 0.1 to 5 g per 1 are of farmland.

Compound [I] or a salt thereof is suitable for use as a pre-emergence soil treatment or a post-emergence foliage and soil treatment agent for paddy field weeds.

For example, the herbicide of the present invention can be safely used immediately after rice transplantation or even 2 to 3 weeks after rice transplantation, and remains effective over a long period of time.

When compound [I] or a salt thereof is used for upland weeds, it is appropriate to treat it with soil before germination or with foliage after germination.

The herbicide of the present invention may include other types of herbicides, plant growth regulators, fungicides (e.g., organochlorine fungicides, organic sulfur fungicides, azole fungicides, antibiotics, etc.), and insecticides ( For example, pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides, etc.), other acaricides, nematicides, synergists, attractants, repellents, pigments, fertilizers, etc. are mixed and used. can do.

Compound [1] or a salt thereof can be prepared by a method known per se, for example, Journal of the Society of Organic Synthetic Chemistry, Vol. 26, p. 674 (1968).
It can be produced according to the method described in 7 Nippon Kagaku Zasshi Vol. 91, p. 270 (1970). For example, compound CI] or a salt thereof is produced by subjecting a compound represented by the general formula [where the symbols are as defined above] or a salt thereof to an oxidative dehydrogenation reaction. As the salt of compound [11], the same salt as that of compound [1] can be used.

This reaction is carried out by bringing the compound [n] or a salt thereof into contact with an oxidizing agent. Suitable oxidizing agents include, for example, halogens (e.g., chlorine, bromine, iodine), N-halogenosuccinimides (e.g., N-chlorosuccinimide,
N-bromosuccinimide).

N-halogenoacetamides (e.g., N-chloragelphthalimides (e.g., N-chlorphthalimide, N-bromphthalimide), chloramine T1 hypohalite (
e.g., halogenating agents such as sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, sodium hypobromite), arylsulfonyl halides (e.g., benzenesulfonyl chloride, p-toluenesulfonyl chloride), alkyl Sulfonyl halides (eg, methanesulfonyl chloride, ethanesulfonyl chloride), sulfonyl halides such as sulfuryl chloride, hydrogen peroxide.

Peracids such as performic acid, peracetic acid, perpropionic acid, perbenzoic acid, monoperphthalic acid, trifluoroperacetic acid, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, selenium dioxide, manganese dioxide, Metal-containing oxidizing agents such as silver oxide, lead dioxide, mercury oxide, ferric chloride, lead tetraacetate, potassium ferricyanide, permanganates and monobichromates, as well as nitric acid, oxygen, air, and the like can also be used.

The amount of oxidizing agent used in this reaction is 2-? l
GonayjlLner Akira☆fko, Moon J Shigo,
卍;Hebyou 1-? It is sufficient to use an amount that generates 0.25 mol of active oxygen per 1 mol of compound [II] or its salt, but it usually generates about 0.01 mol to 0.8 mol of active oxygen. If the oxidizing agent does not generate oxygen, it is sufficient to use an amount that can remove 0.5 mol of hydrogen per 1 mol of compound [n] or its salt, but it is usually about 0.2 to 1 mol. An amount that can remove .6 moles of hydrogen is used.Using an excess of the oxidizing agent is generally undesirable as it induces side reactions.

The reaction is generally carried out in a solvent that does not inhibit the reaction. Suitable solvents include solvents inert to the reaction, such as water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol, benzene, toluene, xylene, nitrobenzene, Aromatic hydrocarbons such as chlorobenzene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, ethyl ether, dioxane, isopropyl ether.

Ethers such as tetrahydrofuran (hereinafter abbreviated as THF), ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide (hereinafter abbreviated as DMAC), hexamethyl phosphoric acid Amides such as triamide (hereinafter abbreviated as HMP A), methyl acetate, and ethyl acetate.

Esters such as butyl acetate, dimethyl sulfoxide (
Sulfoxides such as DMSO), aliphatic carboxylic acids such as formic acid, acetic acid, and propionic acid, pyridine, γ
-collidine, quinoline, triethylamine, tri-n-
Tertiary organic amines such as propylamine and N,N-dimethylaniline are used.

These solvents may be used alone or in a mixture of two or more in any proportion as required.

This reaction may be carried out in the presence of a base to facilitate the reaction. Suitable bases include, for example, ammonia, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, potassium hydrogen carbonate, Inorganic bases such as alkali metal bicarbonates such as sodium bicarbonate, alkaline earth metal carbonates such as calcium carbonate, pyridine, collidine, and quinoline.

Triethylamine, tri-n-propylamine, N.

N-dimethylbenzylamine, N,N-dimethylaniline, l,8-diazabicyclo[5,4,0-7-undecene (hereinafter abbreviated as DBU), 1,4-diazabicyclo[2,2,2]octane ( (hereinafter abbreviated as DBO)
, 1,5-diazabicyclo[4,3,0] non-base is
It may be used in an amount of about 0.5 to 3 times the mole of the starting compound [1] or its salt. Any of the above-mentioned oxidizing agents can be used, but among them, chlorine, bromine, iodine, N-
Chlorsuccinimide.

N-bromosuccinimide, N-bromoacetamide,
N-bromphthalimide, halogenating agents such as chloramine T, sulfuryl chloride, benzenesulfonyl chloride,
p-) Sulfonyl chloride, methanesulfonyl chloride, etc. When the main reaction is carried out in the presence of a base, the solubility of the starting compound [II] or its salt in the solvent increases, the reaction proceeds more smoothly, and the reaction proceeds more smoothly. There are also fewer products.

The reaction temperature can be selected from a range of about -60 to 100°C at which the reaction proceeds, but generally about -20 to 50°C is suitable. The reaction time is relatively short, about 5 minutes to 2 hours, but in most cases the reaction is almost complete upon completion of the addition of the oxidizing agent.

Completion of the reaction can be easily confirmed by thin layer chromatography, high performance liquid chromatography, etc.

The raw material compound [11] or a salt thereof is isomerized in the presence of a base to form the general formula [wherein M+ is an alkali metal, an ion, 1/2
(X represents an alkaline earth metal) or an ammonium ion, and the two bones of Shin represent Maero P and Doryuhi], or as salts thereof.

In the above formula, the alkali metal in the alkali metal ion represented by M+ is, for example, lithium, sodium, potassium, etc., and the alkaline earth metal in l/2X++ (X represents an alkaline earth metal) is, for example, magnesium. , calcium, barium, etc., and as the ammonium ion, for example, an ammonium ion in which a proton is bonded to the above-mentioned organic tertiary amine is used. Compound [II[] or a salt thereof may be isolated according to a method known per se and then used as a raw material compound for this reaction.

In addition, when the obtained compound is a free acid or free base, it may be converted to the corresponding salt according to a conventional method, and when the obtained compound is a salt, it may be converted to the corresponding free acid or free base according to a conventional method. May be converted.

The thus obtained compound [II or a salt thereof can be purified by isolation and purification methods known per se, such as concentration, vacuum concentration, vacuum distillation, liquid conversion, dissolution transfer, salting out, solvent extraction, crystallization, recrystallization, chromatography, etc. It can be isolated and purified by atography or the like.

The raw material compound [11] or its salt can be used, for example, in Japanese Patent Application No. 1983.
0-240258. It can be easily produced by the method described in Japanese Patent Application No. 61-67821 or similar methods. For example, compound [II] or a salt thereof is a compound represented by the general formula % [%] or a salt thereof [in the above formula, one of Y' and Y'' is an amino group and the other is an amino group. is a group represented by the formula -NH-C-OR (wherein R represents a hydrocarbon residue I) or a group represented by the formula -N=C=S, and other symbols have the same meanings as above. The hydrocarbon residue represented by R is linear, monobranched, or cyclic.

It means an aliphatic group, an aryl group, or an aralkyl group that may have a double bond or triple bond.

Here, the hydrocarbon residue is specifically a lower alkyl group, a lower alkenyl group, or a lower alkynyl group.

It means an aryl group or an aralkyl group, and a lower alkyl group means a linear, monobranched or cyclic alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl. , isobutyl, 5ec-butyl, tert-butyl, n-pentyl.

5ec-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, etc. are used, and the lower alkenyl group has one double bond.
means a linear, monobranched or cyclic alkenyl group having 3 to 6 carbon atoms, such as allyl, isopropenyl, 1-butenyl, 2-pentenyl, 2-hexenyl, and cyclopentenyl.

Cyclopentadienyl, cyclohexenyl, etc. mean alkynyl groups, such as propargyl, 2-butynyl,
3-butynyl, 3-pentynyl, 3-hexynyl, etc. are used, and the aryl group means an aryl group having 6 to 14 carbon atoms, such as phenyl, naphthyl, biphenylyl, etc., and the aralkyl group means an aryl group having 7 to 14 carbon atoms. to 1-9 aralkyl group, such as benzyl, phenethyl, phenylpropyl, trityl group, etc. These may be substituted with 1 to 3 suitable substituents.

Among such substituents, nitro is preferred.

Halogens (eg, chlorine, bromine, etc.), etc.

Compound [II] or a salt thereof can be produced by any of Production Methods 1 to 5 below.

In addition, the compounds shown below [1\'], [IV''], [V
″].

As the salts of [Va″], [■“′], [■], and [■], the same salts as those of the above-mentioned compound [+] can be used.

Production method l ↓ Compound [■3 [Symbols in the above formula have the same meanings as above] In this reaction, compound [V'] is compound [IV'] or its salt 1
About 0.8 to 3 moles per mole, preferably about 0.9
1.3 mol is used.

This reaction is usually carried out in a solvent that is inert to the reaction. Suitable solvents include, for example, benzene.

Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane and THF, nitriles such as acetonitrile and propionitrile, Esters such as ethyl acetate, hydrocarbons such as petroleum ether, petroleum benzene, and hexane, and ketones such as acetone and methyl ethyl ketone are used alone or in combination.

This reaction may be carried out in the presence of a base. Suitable bases include, for example, tri(alkyl having 1 to 6 carbon atoms) substituted amines such as trimethylamine and triethylamine, pyridine, γ-collidine, and DBU.

Organic bases such as tertiary amines such as DBO and DBN, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, potassium carbonate, sodium carbonate, etc. Alkali metal carbonate, potassium bicarbonate.

Inorganic bases such as alkali metal hydrogen carbonate such as sodium hydrogen carbonate, alkaline earth metal carbonate such as calcium carbonate, etc. are used. The amount of base is about 0.8 per mole of compound [V']
From 1.2 mol may be used.

The reaction temperature can be selected from a range of about 0 to 150°C, but generally about 10 to 60°C is suitable. The reaction is completed in about 30 minutes to 10 hours, and is completed by thin layer chromatography.

This can be confirmed by high performance liquid chromatography or the like.

Production method 2 + Compound [I[] [Symbols in the formula have the same meanings as above] The hydrocarbon residue represented by R preferably has 1 to 3 carbon atoms.
Lower alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl), aryl groups having 6 to 12 carbon atoms (e.g., phenyl, chlorophenyl, tolyl, biphenylyl)
etc. This reaction can be carried out in the same manner as in Production Method 1 above.

In this reaction, a compound of the general formula may be used instead of the starting compound [V'']. The reaction can be carried out in the same manner as when using the compound [V''].

Production method 3 ↓ Compound [n] [Symbols in the above formula have the same meanings as above] Compound [■″
'] is, for example, trifluoroacetic acid, methanesulfonic acid,
Acid addition salts may be formed with organic acids such as p-toluenesulfonic acid and formic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid.

In this reaction, the compound [■''] is used in an amount of about 0.8 to 3 mol, preferably about 0.9 to 1.3 mol, per 1 mol of the compound [v'''] or its salt.

This reaction is usually carried out in a solvent that is inert to the reaction. Suitable solvents include, for example, benzene.

10 Genated hydrocarbons such as lolomethane, chloroform, and carbon tetrachloride; ethers such as ethyl ether, isopropyl ether, dioxane, and THP; nitriles such as acetonitrile and propionitrile; esters such as ethyl acetate; petroleum ether Hydrocarbons such as , petroleum benzine and hexane, and ketones such as acetone and methyl ethyl ketone are used alone or in combination. This reaction may be carried out in the presence of a base. A suitable base is, for example, DBU.

DBO, DBN,) diethylamine. tri-n-propylamine, organic bases such as pyridine, sodium amide,
Inorganic bases such as sodium hydride are used. The base is usually used in an amount of 0.0% per mole of compound [V'''] or its salt.
8 to 2.5 moles may be used.

The reaction temperature can be selected from a range of about 0 to 150°C at which the reaction proceeds, but generally about 10 to 100°C is suitable. The reaction is completed in about 30 minutes to 10 hours, and is completed by thin layer chromatography.

This can be confirmed by high performance liquid chromatography or the like.

Manufacturing method 4 [The symbols in the formula are symbols that have the same meaning as above. This reaction can be carried out in the same manner as Production Method 3.

Production method 5 (represents a lower alkoxy group) In the above formula, R1 has the same meaning as above, Hal is, for example, chlorine,
Indicates halogen such as bromine.

The first step of the reaction is a step of producing compound [■] or a salt thereof by reacting compound [■'] or a salt thereof with compound [VI].

The raw material compound [VI] is compound [■'] or its salt 1
About 0.8 to 2 moles are used per mole. This reaction is usually carried out in a solvent inert to the reaction.

Suitable solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane, and THF, and acetonitrile. , nitriles such as propionitrile, esters such as ethyl acetate, hydrocarbons such as petroleum ether, petroleum benzene, hexane, etc. are used alone or in combination.

This reaction may be carried out in the presence of a base. Suitable bases include, for example, trimethylamine, tolyl-substituted amines, pyridine, γ-collidine, DBU.

Organic bases such as tertiary amines such as DBO and DBN, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, potassium carbonate, sodium carbonate, etc. Alkali metal carbonate, potassium bicarbonate.

Inorganic bases such as alkali metal hydrogen carbonate such as sodium hydrogen carbonate, alkaline earth metal carbonate such as calcium carbonate, etc. are used. The amount of base is approximately 0.8 per mole of compound [■]
1.2 moles may be used.

The reaction temperature is about 0 to 100°C. The reaction time is from 1 to 10 hours.

The compound [■] or a salt thereof thus obtained may be subjected to the next reaction as a reaction solution, or may be used as a raw material for the next reaction after being isolated and purified by means known per se.

The second step of the reaction is to form a compound [■] by reacting the compound [■] or a salt thereof with a lower alcohol (where R1 has the same meaning as above, Rt and Rs are each a lower alkyl in the main reaction, and the lower alcohol is: Methanol, ethanol, n-propanol, tert-butanol, n-
Alcohols having 1 to 6 carbon atoms such as hexanol are used.

The lower alcohol is used in an amount of about 2 to 10 moles per mole of the compound [■] or its salt, but it may be used in large excess, and a solvent may also be used.

This reaction may be carried out in a solvent inert to the reaction. Suitable solvents include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride, ethers such as ethyl ether, dioxane and THE, acetone,
Ketones such as methyl ethyl ketone, nonitriles such as acetonitrile and propionitrile, DMF', DMAC,
Amides such as HMPA, esters such as methyl acetate and ethyl acetate, and sulfoxides such as DMSO may be used alone or in combination.

The reaction temperature is about room temperature to 120°C. Reaction time is 30
It takes about 10 minutes to 10 hours.

Compound [11] or a salt thereof thus obtained can be isolated and purified by known isolation and purification means, such as concentration, vacuum concentration, vacuum distillation, liquid conversion, dissolution, salting out, and solvent extraction.

It can be isolated and purified by crystallization, recrystallization, chromatography, etc.

The compound obtained by the reaction of Production Methods 1 to 5 [I[]≠TA≠*# has an acidic group (5OyNHC-) in the molecule,
Therefore, when a base is used in the reaction, it may exist as a salt with the base. In such cases, if necessary, for example, inorganic acids such as hydrochloric acid, @acid, phosphoric acid, and nitric acid, and organic acids such as formic acid, acetic acid, trifluoroacetic acid, and p-toluenesulfonic acid can be added to release the When compound [IL] is obtained in free form, it can be made into a base salt by adding the above-mentioned base,
Moreover, the above-mentioned inorganic acids and organic acids can be added to form acid addition salts.

Compound "■'", which is a raw material compound for the above-mentioned compound [II] or a salt thereof, or a salt thereof can be easily produced by a method known per se or a method analogous thereto.

For example, compound [■'] or a salt thereof can be easily produced by the method shown in the following scheme.

R1-8o, -Hat-''b-1 ÷ Compound [■'] [■] [Symbols in the above formula have the same meanings as above. This reaction involves reacting the compound [■] or a salt thereof with ammonia. This is done by

Ammonia is used in an amount of about 1 to 100 mol, preferably about 2 to 30 mol, per 1 mol of the compound [1].

The reaction is usually carried out in a solvent. A suitable solvent is
For example, water, methanol, propenol.

Alcohols such as butanol, dimethyl sulfoxide,
DMF1DMA'C, methyl cellosolve, dimethyl cellosolve, glymes such as diethylene glycol dimethyl ether, dioxane, THF'.

mixed solvent or these polar solvents and chloroform,
Mixtures with non-polar solvents such as dichloromethane can be used. The reaction temperature is not particularly limited, but is usually -40
This is done by heating the temperature to about 50'C. The reaction time is usually about several minutes to 24 hours.

Compounds [■ or salts thereof] can be prepared by methods known per se [e.g.
rnal ofThe Chemical 5ocie
ty) 1958, 2903 pages; Journal Saibu
Organic Chemistry (Journal of
Organic Chemistry) Volume 25, 182
Page 4 (1960): Organic Functional Group Preparations
Functional Group Preparation
ions) Vol. 1, p. 516 (1972), Academic Press, New York and London; JP-A-60-4556゜ Journal of the American Chemical Society, Vol. 58, p. 1348 (1936)] or a method similar thereto. Ru.

l Rem Ah rX7'1 rtz #] rNl-
#1TLyc'-J-1, 127C at Mu
For example, JP-A-51-143686. Tetrahedron (T
etrahedron) Volume 29, page 691 (1973
Year).

It can be easily produced by the method described in Japanese Patent Application No. 60-240258 or similar methods.

The compound [■″] is the Angewandte Chemie International Edition (Angewandte Chemie International Edition).
mie.

International Edition) No. 4
Volume 430 (1965); Archiv der Pharmazie
Vol. 299, p. 174 (1966); Chemical Abstracts No. 6
Volume 4 15783e (1966); Chemische Berichte No. 99
It is easily produced by the method described in Vol. 2885 (1986) or a similar method. Compound [V''' or a salt thereof is produced by a method known per se.

The following symbols used in the following Reference Examples and Examples have the following meanings.

S: Singlet d: Doublet t Nitriplet q: Cultite m: Multiplet br, : Broad reference example 1 4.6-Simethoxy 2-isothiocyanatopyrimidine 300 ml of acetonitrile to 4.6-Simethoxy 2-
Add 45.0 g of trimethylsilylaminopyrimidine and 35.0 g of phenyl chlorothionocarbonate,
Heat to reflux for an hour. After concentrating the reaction solution under reduced pressure and distilling off acetonitrile, 300 g of toluene was added to the residue. Insoluble matter was removed by filtration, the filtrate was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (elution solvent,
Purify with ethyl acetate:hexane=1:1 (V/V).

17.0 g of 4,6-simethoxy 2-isothiocyanatopyrimidine are obtained from the first eluate.

mp, 85-86°C IRν (liquid film) cm-': 1995 3.5 g of 2-[N,N-bis(phenoxythiocarbonyl)amino]-4,6-cymethoxypyrimidine was obtained from the subsequent eluate. It will be done.

mp, 127-128°C IRJ/(nujoluru m-': 1600, 1295.
1190 Reference Example 2 S-(2-methoxycarbonylbenzyl)thiourea hydrochloride 196 g of methyl 2-chloromethylbenzoate and 8 thiourea
Dissolve 3.7g in 500ml of ethanol and heat under reflux for 4 hours. The reaction solution was concentrated under reduced pressure, 300 td of isopropyl alcohol was added to the resulting residue, and the precipitated crystals were collected by filtration and dried to obtain 112.8 g of the title compound.

mp, 196-198°C NMR(daDMSO)δppm,
3.86 (3H, s), 4.77 (2H, s), 7
．． 3-8.2 (48, m), 9.34 (4H, br,
s) Reference Example 3 125 g of 5-(2-methoxycarbonylbenzyl)isothiourea hydrochloride obtained in Reference Example 2 was dissolved in a mixture of 2.4 e of 2-methoxycarbonylbenzyl sulfonamide water and 0.8 ρ of acetic acid, and - While stirring at 5-0°C, chlorine gas is blown into the mixture until it becomes saturated.

80.6 g of the crystals were dissolved in 300 °C of dichloromethane, and aqueous ammonia (a mixed solution of 70 parts of concentrated ammonia water and 70 parts of water, hereinafter the same) was added dropwise at -5 to 0°C, and the mixture was stirred for 2.5 hours under cooling. Add 150 d of water to the reaction solution, separate the organic layer, wash with cold water, and dry over anhydrous sodium sulfate.

Dichloromethane is distilled off to obtain 45.7 g of the title compound.

mp, 79-81°C NMR (CDCl2) δppm, 3.92 (3H,
s), 4.74 (2H.

s), 4.90 (2H, s), 7.2-8.5 (4
H, +++) Reference Example 4 S-(2-chlorobenzyl)isothiourea hydrochloride Reference Example 2 using 2-chlorobenzyl chloride and thiourea
The title compound is obtained in a similar manner.

mp, 185-187°C IRν (liquid film) cm-': 3300, 3050, 16
30.14202-Chlorobenzylsulfonamide The title compound is obtained in the same manner as in Reference Example 3 from 5-(2-chlorobenzyl)isothiourea hydrochloride.

mp, 108-109℃ IRν (liquid film) cm-': 3350, 3270.11
2ON MR(da-DMSO)δppt
4.43 (2H, s), 6.88 (2H, s), 7
．． 10-7.52 (4H, m) Reference Example 6 Ethyl 5-chloro-1,3-dimethylpyrazole-4-carboxylate 5-amino-1, 16.6 g of ethyl 3-dimethylpyrazole-4-carboxylate is dissolved and cooled to -4 to -5°C. While stirring, 9 g of sodium nitrite dissolved in water was added dropwise over 40 minutes to prepare a diazonium salt solution (diazotization reaction). On the other hand, concentrated hydrochloric acid 1
While cooling to 001R1 at 3 to 5° C., sodium bisulfite tt,tg dissolved in 23.5° of water is added dropwise, and then 2.5 g of copper sulfate pentahydrate is added. Add this liquid from 0 to 3
℃ and the previously prepared diazonium salt solution and water 24
1n1. At the same time, 4.0 g of sodium bisulfite dissolved in water was added dropwise. Stir at the same temperature for 1 hour, then pour the reaction solution into ice water 1 (2) and extract with chloroform. The extract is washed successively with saturated brine, saturated sodium bicarbonate water, and saturated brine, and then dried over anhydrous sodium sulfate. After distilling off the chloroform, 18.6 g of a yellow-orange oil is obtained.

This is distilled under reduced pressure to obtain the title compound as a colorless oil.

bp, 97-98℃10.3IIIIIIHgIR1J
(Liquid film) cm-': 170g, 152g, 12
95.1242°1122, 1085 Reference Example 7 5-benzylthio-1,3-dimethylpyrazole-4-
2.3 g of ethyl carboxylate 60% (Y/W) oily sodium hydride was added to n-
After washing with pentane, add DMF30-. 7.2 g of benzyl mercaptan was added dropwise while cooling to below 10°C, and then 11.7 g of ethyl 5-chloro-1,3-dimethylpyrazole-4-carboxylate was added in DMF while keeping the temperature between 0 and 8°C.
The solution dissolved in 10 liters was added dropwise over 50 minutes. 1 at the same temperature
After stirring for 30 minutes at room temperature, the mixture was poured into 300M1 water. The precipitated crystals are collected by filtration, washed with water, and dried to obtain 15.7 g of the title compound.

mp, 51-53°C. When recrystallized from n-hexane, colorless crystals with mp, 57-58°C are obtained.

I R1/(nujol) cm-': 1700,15
05,1250.1130 Reference Example 8 5-Chlorsulfonyl-1,3-dimethylpyrazole-
Ethyl 4-carboxylate 31.5 g of ethyl 5-benzylthio-1,3-dimethylpyrazole-4-carboxylate obtained in Reference Example 7 was dissolved in 200 g of acetic acid, and 125 g of water was added. Chlorine gas is blown into the mixture for 50 minutes while stirring and cooling to 1 to 4°C. Thereafter, the mixture was stirred at 0°C for 40 minutes, and the reaction solution was diluted with ice water (l1).
Open on 2. After extraction with ethyl acetate and washing with saturated brine, the anhydrous sulfuric acid residue was distilled under reduced pressure to obtain bp, 115-119.
℃70゜25-0.3mmHgQ Title compound 26.4g
is obtained.

IRν (liquid film) clll-': 1724, 1392,
1255,1190.1115 Reference Example 9 Ethyl 5-aminosulfonyl-1,3-dimethylpyrazole-4-carboxylate 5-chlorosulfonyl-1° water obtained in Reference Example 8 25
- dropwise at 5 to 7°C. After stirring at the same temperature for 1 hour, the mixture was concentrated to dryness under reduced pressure, ethyl acetate was added, insoluble matter was filtered off, and the filtrate was concentrated under reduced pressure. When diluted with n-hexane and cooled with water, crystals are precipitated. When this is collected by filtration and dried, the title compound 3 is obtained.
．． 6g is obtained.

mp, 112~113°C ■Rν(Nujia-ru>cm-': 3350,3240
, 1690, 1513° Reference Example 1O 訃-ding-/Q-#+-++1. -7--11. ”yll
, -1--+1. 'lx+〆-(A-methoxy6-methyl-2-pyrimidinyl)thiourea methyl N-(2-chlorophenylsulfonyl) dithiocarbamate (5.0 g) was dissolved in 20 g of xylene,
Heat and stir at 5°C for 3.5 hours.

During this time, methyl mercaptan gas is generated. After the reaction is completed, xylene is removed under reduced pressure to obtain a pale yellow oil (2-chlorophenylsulfonyl isothiocyanate). (I
R: Shows strong -3O,NC3 absorption at 1900 cm-'. ) Dissolve this oil in acetonitrile 50-
2-amino-4-methoxy-6-methylpyrimidine2.
Add 8g and stir at 50°C for 30 minutes. The precipitated crystals were collected by filtration and recrystallized from acetonitrile to obtain 5.6 g of the title compound in the form of white prismatic crystals.

mp, 186.5-187.5°C IRν (nujirol) cm″″, 3180. 1
610. 1525° 1460, 1350 Reference Example 11 N-(2-methoxycarbonylbenzyl)sulfonyl-
25 g of 2-methoxycarbonylbenzylsulfonamide, 21.5 g of 4,6-simethoxy 2-isothiocyanatopyrimidine and 15.1 g of anhydrous potassium carbonate were added to 400n+1 of N'-(4,6-simethoxy2-°pyrimidinyl)thiourea acetone. After stirring at 55° C. for 8.5 hours, the precipitated crystals were collected by filtration. After adding 2 g of anhydrous potassium carbonate to the filtrate and stirring at 60° C. for 2 hours, the precipitated crystals were collected by filtration. This crystal, together with the previous crystal, is suspended in 1.512 water, adjusted to pH 2 with acetic acid, stirred for 1 hour, and then the crystal is collected by filtration, washed with water, and dried. Recrystallization from acetonitrile gives 35.9 g of the title compound in the form of a white powder.

mp, 167-168°C IRvc Nujol) cm-'; 3180.171
G, 1610°1455, 1360, Reference Example 12 N-(1,3-dimethyl-4-ethoxycarbonyl-5
1.5 g of ethyl 5-aminosulfonyl-1,3-dimethylpyrazole-4-carboxylate, 2-[N.

N-bis(phenoxythiocarbonyl)amino]-4,
A mixture of 2.6 g of 6-simethoxypyrimidine and 0.8 g of anhydrous potassium carbonate in 351 n1 of acetone is heated under reflux for 4 hours. After cooling to room temperature, insoluble materials are removed by filtration, and the filtrate is concentrated to dryness under reduced pressure. When this is dissolved in a mixed solvent of ethyl acetate and toluene and left to stand, crystals will precipitate. This was filtered and dissolved in 50% water. Then, the crystals are converted to 1) H2 with hydrochloric acid, and the precipitated crystals are collected by filtration, washed with water, and dried to obtain 0.4 g of the title compound. mp.

127-128°C I R1/(Nugidyl)Cm-': 3200,17
15.1605.1528゜1362.1205.11
92.1183 Compounds obtained in the same manner as Reference Example 10 are shown in Table 1.

The present invention will be explained in more detail by showing examples below (although the present invention is not limited to these in any way).

Example 1 N',N'-bis(4,6-simethoxy2-pyrimidinyl)-N*,N4-bis[(2-methoxycarbonylbenzyl)sulfonyl]-α,α'-dithiobisformamidine (compound No, 1)N-(4
,6-Simethoxy2-pyrimidinyl)-N'-(2-
methoxycarbonylbenzylsulfonyl)thiourea1.
5 g was suspended in methanol 20-28% (W/
W) Add 0.68 g of sodium methoxide. Then, 0.28% of bromine was added to this solution while cooling to -5 to -10°C.
A solution prepared by dissolving g in methanol (1 ml) is added dropwise. After stirring at the same temperature for 1 hour, the precipitated crystals were collected by filtration and washed with water and methanol to obtain 1.1 g of the title compound as white crystals.

mp, 187-189°C Elemental analysis value Calculated value as C5tH34NsOttS+ (%') C,45,1'7; H,4,03: N
, 13.02 Actual value (%) C, 45,08; H,
3.9L N, 12.92I Rν cm
-': 32G0.1715.1550°850, 76
0 Example 2 N1. N3-bis(4,6-simethoxy2-pyrimidinyl)-N*, N4-bis(1,3-dimethyl-4-
Ethoxycarbonyl-5-pyrazolesulfonyl)-α
, α′-dithiobis-formamidine (compound No.
2) N-(4,6-simethoxy2-pyrimidinyl)-N'
-(1,3-dimethyl-4-ethoxycarbonyl-5-
1.1 g of pyrazolesulfonyl)thiourea is suspended in 20-methanol and 0.47 g of 28% (Y/W) sodium methoxide is added at room temperature. A solution prepared by dissolving 0.23 g of bromine in 1M methanol is added dropwise to this solution while cooling at -5 to -10°C. After the dropwise addition, the temperature of the reaction solution is gradually raised to room temperature. The precipitated crystals were collected by filtration and recrystallized from acetonitrile to give 0.6 g of the title compound as white crystals.
is obtained.

+11p, 147-148℃ Elemental analysis value C,. Calculated value (%) as N3゜N,,O□S4 C,40,62,H,4,32,N,18
．． 95 Actual value (%) C, 40, 48, H, 4, 18, N
, 19.15I Rν (nujol) cm=': 17
10.1625.1560°1350, 1260.
860 Compounds obtained in the same manner as in Example 1 are shown in Table 2.

General formula xylene 75% by weight dimethylformamide 18% by weight polyethylene glycol ether (Noniball 85■)
An emulsion made by mixing 5 weight. (Used after diluting appropriately with water) Formulation Example 2 Wettable powder Compound No. 2 30% by weight Sodium ligninsulfonate 5% by weight Polyoxyethylene glycol ether (Noniball 850)
5 wt% clay
55% by weight white carbon
A wettable powder made by mixing and pulverizing 5% by weight. (Used after appropriately diluting with water) Formulation example 3 Granule compound N083 0.5% by weight Sodium ligninsulfonate 2% by weight Bentonite
57.5% by weight talc
Granules made by adding water to a 40% by weight mixture and kneading and granulating it.

Effect test example 1 of the invention 1/10,000 are Wagner pot was filled with paddy soil and sown cypress, and after about one week of cultivation, paddy rice seedlings 2
Transplant the stock. In another pot, seeds of Inuhotarui are sown, and in another pot, paddy soil containing overwintering stems of Pinus vulgare is sown, and after planting the sprouted tubers of Cyperus japonica, the buds of the sprouted tubers of Cyperus japonica are planted on the ground. Each pot was flooded with 3 cm of water, and granules containing 0.2% by weight of Compound [1] produced in the same manner as Formulation Example 3 were added to the active ingredient [Compound [1
]] is applied in flooded water so that the amount is 0.5 g per are.

As a control drug, Shift 922.5% granules were used as an active ingredient.
Apply at a rate of 5.0g per area. Chemical application 21
After a day, the herbicidal effect of each test compound is investigated.

The herbicidal effect is expressed using the following index (the same applies to the test examples below).

Index Effect Suppression rate (weed killing rate)%0
None O 1 Small 0.1~50 2 Medium 50.1~753
Large 75.1~87.54 Maximum
87.6-99.95 Complete withering 100 The results are shown in Table 3.

Table 3 1 Control drug From the above results, it is clear that the compound [1] of the present invention has higher herbicidal activity compared to known herbicidal compounds.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 is an optionally substituted phenyl group, an optionally substituted benzyl group, or an optionally substituted pyrazole group , R_2 and R_3 represent a lower alkyl group or a lower alkoxy group, and Z represents CH or N, respectively] or a salt thereof.