JPH03157308A - Guanidine derivative, production thereof and insecticide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is substitutive homocyclic or heterocyclic group; n is 0 or 1; R<2> is H or substitutive hydrocarbon group; R<3> is primary, secondary or tertiary amino group; X is electron attractive group, provided that R<1> is other than pyridyl when X is CN or R<1> is substitutive heterocyclic group when n is 0) or salts thereof. EXAMPLE:1-(6-Chloro-3-pyridylmethyl)-2-cyano-1-ethyl-3-methylguanidine. USE:A safe insecticide with low toxicity to humans and animals, fishes and natural enemies and excellent controlling effects on insect pests. PREPARATION:A compound expressed by formula II (R<3a> is R<3>; X<a> is NO2 or trifluoroalkyl; Y is leaving group) or salt thereof is reacted with a compound expressed by formula III (R<1a> is substitutive heterocyclic group; R<2a> is R<2>) to afford the corresponding compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a guanidine derivative or a salt thereof useful as an insecticide, a method for producing the same, and an insecticide containing the same.

Conventional technology A large number of synthetic compounds with pest control effects have been used as insecticides, but most of them belong to the organic phosphate esters, carbamate esters, organic chlorine-containing compounds, or pyrethroid compounds. ing.

It is well known that the frequent use of such a limited range of compounds causes harmful effects such as increased insecticide resistance in pests, which is currently a problem in various places. Furthermore, even though some of the above insecticides have high insecticidal power, they are highly toxic to humans and fish, and are sometimes toxic to the natural enemies of pests, and their persistence in soil is too strong. The current situation is that satisfactory effects are not necessarily achieved in practical terms.

On the other hand, regarding guanidine derivatives or salts thereof, for example, 3-nitro-1-(3-pyridylmethyl)guanidine is available from Chemical and Pharmacy Co., Ltd. (Chem, Pharm, Bull).

23.2744 (1975), and
A group of compounds having anti-inflammatory action, typified by cimetidine, have been described in numerous documents and patents. However, there are no reports of guanidine derivatives or their salts as insecticides.

Problems to be Solved by the Invention Under these circumstances, the present invention aims to develop an insecticide using a guanidine derivative or its salt, which has low toxicity to humans and animals, toxicity to fish, and toxicity to natural enemies, is safe, and has an excellent control effect against pests. Provided as.

Means for Solving the Problems In order to solve the above problems, the present inventors have been conducting intensive research for many years in order to find an insecticide that has a completely different structure from the insecticides that have been conventionally used.

As a result, the formula [wherein R1 is an optionally substituted homologous or heterocyclic group, n is O or 1, R3 is hydrogen or an optionally substituted hydrocarbon group, and R3 is a first, A secondary or tertiary amino group, and X represents an electron-withdrawing group. However, when X is a cyano group, R and I are optionally substituted homocyclic or heterocyclic groups other than pyridyl, and when n is 0, R1 is an optionally substituted heterocyclic group. shows. It was discovered that the guanidine derivative and its salt represented by the following surprisingly have a very strong insecticidal effect, and also that it has low toxicity.Based on these findings, the present invention was completed.

That is, the present invention provides (1) an insecticide composition or insecticide containing a guanidine derivative [1] or a salt thereof, (2) the formula % formula % [1] [wherein R1'' may be substituted a heterocyclic group, R
! 11 represents hydrogen or an optionally substituted hydrocarbon group, R3'' represents a primary, secondary or tertiary amino group, R*
When a is hydrogen, R3a is a secondary or tertiary amino group, and X a represents a nitro or trifluoroacetyl group. ] A guanidine derivative or a salt thereof, represented by the formula (3) [wherein R1a%R11 and Xa have the same meanings as above, Y
indicates a leaving group. Guanidine derivative [1''] characterized by reacting the compound represented by or a salt thereof with ammonia, a primary or secondary amine, or a salt thereof.
or a method for producing a salt thereof, (4) Formula % Formula % [[] [Symbols in the formula have the same meanings as above. ] or a salt thereof and the formula [The symbols in the formula have the same meanings as above. A method for producing a guanidine derivative [I''] or a salt thereof, which is characterized by reacting a compound represented by [I''] or a salt thereof, with the formula (5) (the symbols in the formula have the same meanings as above). A guanidine derivative [1''] or a salt thereof, characterized by reacting a compound represented by the formula % or a salt thereof with a compound represented by the formula %[] [The symbols in the formula have the same meanings as above. A manufacturing method of formula (6) [wherein R1'' and Xa have the same meanings as above, R15 represents hydrogen or an optionally substituted hydrocarbon group, R3b
represents a tertiary amino group, and when R3'' is a tertiary amino group, R''1 is hydrogen. ] or a salt thereof and the formula % formula % [] A guanidine derivative [I'] or a salt thereof, characterized in that it is reacted with a compound represented by the formula [wherein Y has the same meaning as above and R represents an optionally substituted hydrocarbon group] A method for producing (7) a compound or a salt thereof represented by the formula [the symbols in the formula have the same meanings as above] or a salt thereof and the formula %[the symbols in the formula have the same meanings as above]. The present invention relates to a method for producing a guanidine derivative [I'] or a salt thereof, which is characterized by reacting the represented compound or a nitrating agent.

In the above formula, R1 represents an optionally substituted homocyclic or heterocyclic group. However, when X is a cyano group, R1 is an optionally substituted homocyclic or heterocyclic group other than a pyridyl group, preferably a halogenopyridyl or a halogenothiazolyl group, more preferably a halogenothiazolyl group. shows. The homocyclic or heterocyclic group represented by R1 is a cyclic group containing only the same atoms or a cyclic group containing two or more different atoms, and means a cyclic hydrocarbon group or a heterocyclic group. . Rla represents an optionally substituted heterocyclic group, and the one described for R1 above is used.

Examples of the cyclic hydrocarbon group represented by R1 include C3-11 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, tatoehacyclobrobenyl, 1-cyclopentenyl, 1-cyclohexenyl, 2- C3-! such as cyclohexenyl, l,4-cyclohexagenyl, etc. Cycloalkenyl groups such as phenyl, 1- or 2-naphthyl, 1-. 2- or 9
-Antril.

1-. 2-. 3-. 4- or 9-phenanthryl, l
C11 such as -, 2-, 4-, 5- or 6-azulenyl
-14 aryl group etc. are used. Preferred cyclic hydrocarbon groups are, for example, aromatic, such as phenyl, etc.
11-14 aryl group, etc.

The heterocyclic group represented by R1 or R1'' includes, for example, one heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom.
A 5- to 8-membered ring containing 5 to 5 members or a condensed ring thereof is used, and specific examples thereof include 2- or 3-thienyl, 2- or 3-furyl, 2- or 3-pyrrolyl,
2-. 3- or 4-pyridyl, 2-. 4- or 5-
Oxacylyl, 2-. 4- or 5-thiazolyl, 3
-, 4- or 5-pyrazolyl, 2-. 4- or 5
-imidazolyl, 3-. 4- or 5-isoxacylyl, 3-. 4- or 5-isothiazolyl.

3- or 5-(1,2,4-oxadiazolyl).

1.3.4-oxadiazolyl, 3- or 5-(1,
2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4- or 5-(1,2,3-thiadiazolyl),
1,2,5-thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl 11H- or 2H-tetrazolyl, N-oxide-2-3- or 4-pyridyl, 2-. 4- or 5-pyrimidinyl, N-oxide-2-24- or 5-pyrimidinyl, 3- or 4-
Pyridazinyl.

Pyrazinyl, N-oxide-3- or 4-pyridazinyl, benzofuryl, benzothiazolyl, benzoxacylyl, triazinyl, oxotriazinyl, tetraclo[1,5-b]biviridacinyl.

triazolo[4,5-b]pyridazinyl, oxoimidazinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 14-oxazinyl, morpholinyl, ■, 4-thiazinyl, l, 3-thiazinyl, piperazinyl, benzimidazolyl, quinolyl,
inquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, intridinyl, quinarinyl,
■.

8-Naphthyridinyl, purinyl, pteridinyl.

Dibenzofuranyl, carbazolyl, acridinylphenanthridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc. are used. Preferred heterocyclic groups are, for example, 2-13- or 4-pyridyl, 2-.
It is a 5= or 6-membered nitrogen-containing heterocyclic group such as 4- or 5-thiazolyl.

The same or heterocyclic group represented by R1 and the heterocyclic group represented by R1'' may have 1 to 5 (preferably 1) the same or different substituents. Examples of substituents include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, S-butyl, (-butyl,
Alkyl groups having 1 to 15 carbon atoms such as pentyl, hexyl, heptyl, octyl, nonyl, de/l, undecyl, dodecyl, tridecyl, tetradecyl, bentatecyl, and 3 to 15 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. 10 cycloalkyl groups, such as vinyl, allyl, 2-methylallyl, 2-
2 or more carbon atoms such as butenyl, 3-butenyl, 3-octenyl, etc.
10 alkenyl groups, such as ethynyl, 2-propynyl, 3-hexynyl, etc. 1 to 10 alkynyl groups,
For example, cycloalkenyl groups having 3 to 10 carbon atoms such as cyclopropenyl, cyclopentenyl, cyclohexenyl,
For example, aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl, aralkyl groups having 7 to 10 carbon atoms such as benzyl and phenylethyl, nitro, hydroxyl, mercapto, oxo, thioxo, cya/, carbamoyl, carboxyl, such as methoxy C, -4 alkoxy-carbonyl such as carbonyl, ethoxycarbonyl, sulfo, ・
For example, halogens such as fluorine, chlorine, bromine, and iodine, C,-4 alkoxys such as methoxy, ethoxy, propoxy, impropoxy, butoxy, isobutoxy, S-butoxy, t-butoxy, and 06-8° aryls such as phenoxy. Oxy, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-
CI-4furkylthio such as butylthio, t-butylthio, C@-IQ arylthio such as phenylthio,
For example, CI-4furkylsulfinyl such as methylsulfinyl and ethylsulfinyl, Cl-107lylsulfinyl such as tatoehaphenylsulfinyl, C1□alkylsulfonyl such as methylsulfonyl and ethylsulfonyl, C such as tatoehaphenylsulfonyl,
-8゜Arylsulfonyl, amino, such as acetylamino, Ct-s acylamino such as propionylamino 7, mono- such as methylamine, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, etc. Or G C1-
C3-8 cycloalkylamino, such as 4-alkylamino, eg cyclohexylamino, eg CS-+, such as anilino. C such as arylamino, e.g. acetyl
! -4 acyl, for example C, , □, such as benzoyl. Aryl-carbonyl, such as 2- or 3-thienyl, 2- or 3-furyl, 3-14- or 5-pyrazolyl, 2-14- or 5-thiazolyl, 3,4- or 5-isothiazolyl, 2-14- or 5-oxacylyl, 3-14- or 5-isooxasolyl, 2-14-
or 5-imidazolyl, 1.2.3- or 1.2.
4-triazolyl, IH or 2H-tetrazolyl, 2
-5 to 6 containing 1 to 4 heteroatoms selected from oxygen, sulfur, and nitrogen, such as 13 or 4-pyridyl, 2-14- or 5-pyrimidinyl, 3- or 4-pyridanidyl, quinolyl, isoquinolyl, indolyl, etc. 1 to 5 members selected from membered heterocyclic groups are used.

These substituents are, for example, C,-1°aryl, C7
□. Aralkyl, C3-1°cycloalkyl, C8.

Cycloalkenyl, ca-1゜aryl soxy, Ca-
to arylsulfinyl, C@-IQ arylsulfinyl,
In the case of C8-1゜arylsulfonyl, ca-1゜arylamino, heterocyclic group, etc., the above-mentioned halogen, hydroxyl group, such as methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, S-butyl, [-
01-4 alkyl such as butyl, C! such as vinyl, alinobe 2-methylallyl, etc. -4 fulkenyl, e.g. 01-4 alkynyl such as ethynyl, 2-propynyl, C
a-to aryl, CI-4 alcohol, phenoxy,
Cl-4 may be substituted with 1 to 5 groups such as furkylthio, phenylthio, etc., and the substituent may be Cl-+salkyl,
C2-1゜alkenyl, ct-1゜alkynyl, Cl-
4 alkoxy, C1-4 alkylthio, Cl-4 alkylsulfinyl, C1,□4 alkylsulfonyl, amino, mono- or di-C1-, alkylamino, C3-8
In the case of cycloalkylamino + Cl-1゜arylamine 7, etc., the above-mentioned halogen, hydroxyl group,
1 to 5 with C8,4 alkoxy, Cl-4 alkylthio, etc.
may be replaced.

A preferred example of R1 is a 5- or 6-membered nitrogen-containing heterocycle such as pyridyl or thiazolyl which may be substituted with 1 or 2 halogens.

n represents O or 1, preferably l.

The hydrocarbon group of the [optionally substituted hydrocarbon group] represented by R′, R″a, Rlb, and R includes the alkyl group having 1 to 15 carbon atoms and the above-mentioned alkyl group having 3 to 10 carbon atoms for R1. Cycloalkyl group, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, cycloalkenyl group having 3 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, 7 carbon atoms
~10 aralkyl groups, etc. are used. Further, as the substituent for the "optionally substituted hydrocarbon group", those mentioned above as the substituent for the isocyclic or heterocyclic group represented by R1 can be used.

Preferred examples of R″, R1 and Rlb include hydrogen,
For example, C1,□4 alkyl groups such as methyl, ethyl, propyl, etc., and preferred examples of R include C1, □4 alkyl groups such as methyl, ethyl, propyl, etc.
I-4 is an alkyl group.

R3, R311 and R3b represent a primary, secondary or tertiary amine group, for example, the formula [wherein R4 and R5 are the same or different and represent hydrogen or an optionally substituted hydrocarbon group, Alternatively, R4 and R8 together represent a cyclic amino group with the adjacent nitrogen. (Here, the primary amino group is an unsubstituted amino group in which R' and R5 are hydrogen in the above formula, and the tertiary amino group is an unsubstituted amino group in which R' and R5 are hydrogen.) A mono-substituted amino group in which either of R4 and R5 is hydrogen, and a tertiary amino group refers to a di-substituted amino group in which neither R4 nor R5 is hydrogen. Examples of the "optionally substituted hydrocarbon group" represented by R4 and R5 include the above R
”, Ro, Rlb, and R are used. In addition, examples of the cyclic amine group in which R' and R5 together represent an adjacent nitrogen include aziridino, azetidino, pyrrolidino, morpholino, thiomorpholif group, etc. Preferred examples of R3゜23m and R3b include unsubstituted amine groups, such as methylamino,
Mono〇, -4 alkylamino groups such as ethylamino, propylamino, etc., di-01-4 fulkylamino groups such as dimethylamino, ethylmethylamino, etc., CI-4 acylamino groups such as formamide, N-methylformamide, acetamide, etc. be.

Examples of the electron-withdrawing group represented by carbonyl, etc.), heterocyclic oxycarbonyl (the above-mentioned ones are used as the heterocyclic group, for example, pyridyloxycarbonyl, thienyloxycarbonyl, etc.), and may be substituted with toehahalogen (CI2.Br, etc.). C,-
, alkylsulfonyl (e.g. methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, etc.),
Sulfamoyl, diC,-, alkoxyphosphoryl (e.g. jetoxyphosphoryl, etc.), e.g. (CI
2. CI-, which may be substituted with Br, F, etc.)
4-acyl (e.g., acetyl, trichloroacetyl, trifluoroacetyl, etc.), C*-1°aryl-carbonyl (e.g., benzoyl, etc.), carbamoyl, CI-
. Alkylsulfonylthiocarbamoyl (eg, methylsulfonylthiocarbamoyl, etc.) and the like are used. Preferred electron-withdrawing groups include, for example, nitro. X& represents a nitro or trifluoroacetyl group.

Examples of the leaving group represented by Y include halogens such as chlorine, bromine, iodine, and fluorine, and halogens (CQSBr, F, etc.) such as ethanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy, trifluoromethanesulfonyloxy, etc. C1-4 alkylsulfonyloxy which may be substituted with ~3, such as benzenesulfonyloxy, p-toluenesulfonyloxy,
1 with halogens (CI2SBr, F, etc.) such as p-bromobenzenesulfonyloxy and mesitylenesulfonyloxy.
co-to arylsulfonyloxy which may be substituted with ~4, such as halogen (Of
f, Br%F, etc.), etc.).
C such as +-a acyloxy, for example benzoyloxy
, -1°aryl-carbonyloxy, hydroxyl group, e.g. methoxy, ethoxy, etc. 01□alfoxy, e.g. CI-4 alkylthio group, e.g. methylthio, ethylthio, etc.
For example, C+-t-alkylsulfinyl such as methylsulfinyl, Cl-4furkylsulfonyl such as methylsulfonyl, halogen (CQ) such as phenoxy, p-chlorophenoxy, p-nitrophenoxy, etc.

Br, F, etc.), C6,1° aryloxy which may be substituted 1 to 3 times with nitro, etc., such as heterocyclic oxy such as 2-pyridyloxy, 2-benzoxasilyloxy, etc., such as phenylthio, p-nitro C1-1゜Arylthio, which may be substituted 1 to 2 times with nitro such as phenylthio, C1-1゜Arylthio, which may be substituted 1 to 2 times with nidotetra, such as benzylthio, ρ-nitrobenzylthio, etc.
? -1! Aralkylthio, such as 2-pyridylthio,
Heterocyclic thio such as 2-benzothiazolylthio, amino such as mono- or di-C7-4 alkylamino such as methylamino, ethylamino, dimethylamino, such as l
Nitrogen-containing 5-membered brorocyclic groups such as -imidazolyl and 1,2.4-1 riazol-1-yl are used.

Preferred examples of Y include compounds [11] and [III]
For example, C1- such as methylthio, ethylthio, etc.
C?4 alkylthio, such as benzylthio? -, aralkylthio, such as methoxy, ethoxy, etc. 01-
4-alkoxy, amino, such as mono- or di-C1-4 alkylamides 7 such as methylamine and dimethylamino, and in the compounds [V[], [■J and [X], halogens such as chloro and bromo, For example, C may be substituted with 1 to 3 halogens such as methanesulfonyloxy, trifluoromethanesulfonyloxy, etc.
8. Alkylsulfonyloxy, such as benzenesulfonyloxy, p-toluenesulfonyloxy, etc.
, □+oT'J-rusulfonyluoquine, water ML ta,!
:C1-4 which may be substituted with 1 to 3 halogens such as acetyloxy, trifluoroacetyloxy, etc.
Acyloquine and the like are used.

Preferred examples of the guanidine derivative [1] or a salt thereof include, for example, 1c [wherein R1'' represents a pyridyl group, a halogenpyridyl group, or a halogenothiazolyl group; R2C, R4aRsa
are the same or different and represent hydrogen, methyl group, ethyl group, formyl group or acetyl group. ] or its salts. In formula [I5], Rlb
is, for example, a 3-pyridyl group, for example, a 6-chloro-3
-pyridyl, 6-bromo-3-pyridyl, 5-bromo-
a halogenopyridyl group such as 3-pyridyl, or 2-1
represents a halogenothiazolyl group such as 4-5-thiazolyl and 2-bromo-5-thiazolyl.

The guanidine derivative [1] or a salt thereof gives rise to cis and trans stereoisomers with respect to the X position, and when R1 is hydrogen and R3 is a 7-th or near-7th group, theoretically they are mutually compatible. Mutants are generated, and any of these isomers are included in the compound of the present invention [N or a salt thereof.

R” 1 (cis)-[1] (trans)-[1]
(Margins below) -NHX 7/ R'-Pi [Symbols in the formula have the same meanings as above. ] Furthermore, examples of the salts of the guanidine derivatives [L], "l'", and [1b] include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, sulfuric acid,
Inorganic acids such as perchloric acid, such as formic acid, acetic acid, tartaric acid, malic acid, citric acid.

Salts with organic acids such as silicic acid, succinic acid, benzoic acid, picric acid, and p-toluenesulfonic acid may also be used.

When using the guanidine derivative [1] or its salt as an insecticide, one or more types of compound [1] or its salt can be used in a suitable liquid carrier depending on the purpose of use. Emulsions,
It is used in the following dosage forms: oil, wettable powder, powder, two tablets, spray, and ointment. These preparations may include, if necessary, emulsifying agents, suspending agents, spreading agents, penetrating agents, wetting agents, and mucilage agents.

A stabilizer or the like may be added, and it can be prepared by a method known per se.

The proportion of active ingredients in insecticides varies depending on the purpose of use, but for emulsions, wettable powders, etc., 10 to 90% by weight is appropriate, and for oils, powders, etc., 0.1 to 10% by weight is appropriate. The appropriate concentration for granules is about 1 to 20% by weight, but these concentrations may be changed as appropriate depending on the purpose of use. When using emulsions, wettable powders, etc., dilute them with water as appropriate (for example, 100 to 100,000
(double) and disperse.

Examples of liquid carriers (solvents) used include water, alcohols (for example, methyl alcohol, ethyl alcohol, n-7' alcohol, isopropyl alcohol, ethylene glycol), ketones (for example,
acetone, 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, 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).

Solvents such as butyl acetate, fatty acid glycerin ester, etc.) and nitriles (e.g., acetonitrile, propionitrile, etc.) are suitable, and these can be used as appropriate by mixing one or more of them in an appropriate ratio. can.

Examples of solid carriers (diluents and bulking agents) include vegetable powders (e.g., soybean flour, tobacco flour, wheat flour, wood flour, etc.), mineral powders (e.g., kaolin, bentonite, clays such as acid clay, talc powder, Talcs such as waxite powder, silicas such as diatomaceous earth 2M mother powder, etc.), alumina, sulfur powder, activated carbon, etc. are used, and these can be used as appropriate by mixing one or more of them in an appropriate ratio. can.

Examples of ointment bases include polyethylene glycol, pectin, polyalcohol esters of higher fatty acids such as glyceryl monostearate, cellulose derivatives such as methylcellulose, sodium alginate, bentonite, higher alcohols, and polyhydric alcohols such as glycerin. Alcohol, petrolatum, white petrolatum.

Liquid paraffin, lard, various vegetable oils, lanolin.

One or more of dehydrated lanolin, hardened oil, resins, etc., or a mixture of these with various surfactants shown below may be used as appropriate.

Surfactants used as emulsifiers, spreaders, penetrants, dispersants, etc. may include stone soaps, polyoxyethylene alkyl aryl ethers [eg, Neugen 0.01], etc. E-nee 142 (E-A 142)” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Nonal 0 manufactured by Toho Chemical Co., Ltd.],
Alkyl sulfates [e.g. Emar 10o, Emar 40
[F]; manufactured by Kao Corporation], alkyl sulfonic acid salts [e.g., Neogen ■, Neogen T■; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.,
Neoperex: Polyethylene glycol ethers manufactured by Kao Corporation [e.g., Noball 85o, / Nipol 1
Nonionic and anionic surfactants such as 00'' Nonipol 160o; manufactured by Sanyo Kasei Co., Ltd.], polyhydric alcohol esters [eg, Tween 20 and Tween 80o; and Kao (Katsugetsu) are used as appropriate.

In addition, guanidine derivatives [1] or its salts can be used with other types of insecticides (pyrethroid insecticides, organophosphate insecticides, carbamate insecticides, natural insecticides, etc.), acaricides, nematicides, herbicides, etc. agents, plant hormones, plant growth regulators, fungicides (e.g. copper fungicides, organochlorine fungicides, organic sulfur fungicides, phenolic fungicides, etc.), synergists, attractants, repellents, pigments It is also possible to mix and use as appropriate with , fertilizer, etc.

Guanidine derivatives [I] and their salts are effective in controlling sanitary pests and parasitic insects on plants and animals, and show strong insecticidal effects when brought into direct contact with insects, such as by spraying directly on plants and animals infested with pests. The characteristic property is that once the drug is absorbed into the plant through roots, leaves, stems, etc.
This plant exhibits a strong insecticidal effect when pests absorb sweat, chew on it, or even come into contact with it. Such properties are advantageous for exterminating sweat-absorbing and biting insects. In addition, compound [1] and its salts have safe and advantageous properties as pest control agents for hygiene, horticulture, and especially agriculture, such as low phytotoxicity to plants and low toxicity to fish.

Specifically, the preparation containing the guanidine derivative [I] or a salt thereof is, for example, Eurydel Ila.
rugosum), rice black stink bug (Egao Wataruhaha 1)
urida), Hon-heli stink bug (Riptortus
clavatus), Nasigunbai (Stephan)
itis nashi), Laodhopper (Laod.
elphax 5triatellus), brown planthopper (Nilaparvata lugens),
Tsumakuro Yoko/ <I (Nephotettix c
incticeps), Brevi
coryne brassicae), cotton aphids (Aphis gossypii), hemiptera pests such as Spodoptera
1itura), diamondback moth (Plutella xyl
ostella), cabbage butterfly (Pieris)
rapae crucivora), Nikamay moth (A
utographa nigrisigna), tobacco moth ('He1icoverpaassulta), fall armyworm (Pseudaletia 5eparata)
), armyworm (Mamestra brassica)
e>, Apple-Kokakumonhamaki (Adoxophyes)
orana fasciata), Notarcha derogata, and Cnaphalocrocis medina
lis), potatoes (Phthorimaea
Lepidopteran pests such as Epi lachnavi
gintioctopunctata), cucumber beetle (
Aulacophora f'emoralis), Phyflotretastriot
ata), rice black stink bug (Oulema ory
zae), rice weevil (Echinocnemus)
Coleopteran pests such as Musca domestica, Culex pipiens pallens,
Tabanus trigonus, onion fly (Tabanus antiqua), seed fly (De
Diptera pests such as the locust locust (Locustamigratoria)
), Gryllotalpa arrican
a), such as the German cockroach (B.
lattella germanica), black cockroach (Periplaneta f'uligino)
sa), etc., Tetranychus
kanzawai), false namino mite (Tetr)
anychus cinnabarinus), apple spider mite (Panonychus ulmi),
Citrus rust mite (Aculops Pelekassi)
spider mites, such as the rice nematode (A
It is particularly effective for controlling nematodes such as phelenchoides besseyi).

The insecticide of the present invention thus obtained is safe and has extremely low toxicity, and is an excellent agricultural chemical. The insecticide of the present invention can be used in the same manner as conventional insecticides, and as a result, it can exhibit superior effects compared to conventional products. For example, the insecticide of the present invention can be used against target pests by, for example, spraying on leaves of crops treated with seedling boxes, spraying insect bodies, applying in water to rice fields, or treating soil. The amount of application depends on the time of application, location of application,
It can vary widely depending on the method of application etc.
Generally, it is desirable to apply the active ingredient (guanidine derivative [1] or its salt) in an amount of 0.3 g to 3,000 g, preferably 50 g to 1,000 g per hectare. When the insecticide is a hydrating agent, the final concentration of the active ingredient is between 0.1 and 1.OOpp
(preferably c) 10 to 5001) It may be used after diluting to a pH range of 10 to 5001).

The guanidine derivative [1a] or a salt thereof can be produced by the following methods (A) to (F). When compound [1''] is obtained in the form of a free compound by the following production method, it can be converted into a salt as described above, and when it is obtained in the form of a salt, it can be converted into a free compound according to a conventional method. In addition, when the compound contained in compound [1''] is used as a raw material for producing other types of compound [1''], it may be used as a free form or as a salt. Similarly, when it is present, it can be used not only in its free form but also as a salt.

As for the raw material compounds and products used in the following manufacturing method, their salts (for example, salts with acids as described in the above compound [1], etc.) are also included.

(A) In the present invention, the guanidine derivative [1'
] or its salts can be produced.

Ammonia, a primary or secondary amine, or a salt thereof used in the present invention has the formula % [[ ] [wherein R34 has the same meaning as above. ] or a salt thereof. In this reaction, the compound [
[II] is particularly preferably 01-4 alkylthio such as methylthio, amino, or the like. Compound [X[] or its salt is about 0.8 to
It is preferable to use 2.0 equivalents, but if there is no problem with the reaction, about 2.0 to 20 equivalents may be used.

Although the reaction may be carried out without a solvent, it is usually carried out in a suitable solvent. Such solvents include, for example, water, alcohols such as methanol, ethanol, n-propertool, inpropertool, etc., benzene,
Aromatic hydrocarbons such as toluene, xylene, etc., such as dichloromethane.

Halogenated hydrocarbons such as chloroform, saturated hydrocarbons such as hexane, heptane, cyclohexane,
For example, ethers such as diethyl ether, tetrahydrofuran (hereinafter abbreviated as THF), and dioxane, ketones such as acetone, nitrites such as acetonitrile, sulfoxides such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), For example, NN-dimethylformamide (hereinafter abbreviated as DMF).

), esters such as ethyl acetate, and carboxylic acids such as acetic acid and propionic acid. These solvents can be used alone, or two or more of them can be used as a mixture in an appropriate ratio, for example, from 1:1 to 1:10, if necessary. If the reaction mixture is not homogeneous, phase transfer catalysts such as quaternary ammonium salts such as triethylbenzylammonium chloride, tri-n-octylmethylammonium chloride, trimethyldecylammonium chloride, and tetramethylammonium bromide or crown ethers may be used. The reaction may be carried out in the presence of

This reaction may be accelerated by adding a base or a metal salt in an amount of 0.01 to 10 equivalents, preferably 0.1 to 3 equivalents. Such bases include, for example, sodium bicarbonate,
Potassium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide,
Inorganic bases such as phenyllithium, butyllithium, sodium hydride, potassium hydride, sodium methoxide, sodium ethoxide, metallic sodium, metallic potassium, such as triethylamine, tributylamine, N,
N-dimethylaniline, pyridine.

Organic bases such as lutidine, collidine, 4-(dimethylamino)pyridine, and DBU (1,8-diazabicyclo[5,4,O]undecene-7) can be used. The organic bases mentioned above can also be used themselves as solvents.

Metal salts such as copper chloride, copper bromide 1 copper acetate,
Copper salts such as copper sulfate, mercury salts such as mercury chloride, mercury nitrate, and mercury acetate can be used.

The reaction temperature of this reaction is usually -20°C to 150'C.

The reaction time is usually 10 minutes to 50 hours, preferably 1 to 20 hours at 000 to 100°C.

(B) Raw material compound [I11] or its salt and compound [r
Compound [1] by reacting with [V] or a salt thereof
”] or a salt thereof. Preferred examples of Y and reaction conditions in this reaction are the same as those described in method (A).

(C) Also, compound [V] or a salt thereof and compound [VI]
The guanidine derivative [1″′
] or its salts can also be produced.

The leaving group represented by Y in compound [VI] includes, for example, halogen such as chlorobromo, C1,□4 alkylsulfonyloxy such as methanesulfonyloxy,
For example, 06. such as p-toluenesulfonyloxy. ,.

Arylsulfonyloxy, such as acetyloxy,
Particularly preferred are C1-4 acyloxy which may be substituted with 1 to 3 halogens such as trifluoroacetyloxy.

The ratio of compound [VI] to compound [V] is about 0.8 to 1.
It is preferable to use 5 equivalents, but a large excess amount may be used if there is no problem with the reaction. This reaction may be carried out in the presence of a base to promote the reaction, and as such a base, for example, those mentioned in the method (A) can be used. The base can be used in an amount of 0.5 equivalent to large excess, preferably about 0.8 to 1.5 equivalent, relative to compound [V]. Further, when an organic base is used as the base, it can also be used as a solvent itself.

This reaction is usually preferably carried out in a solvent as described in method (A), and if the reaction system is not homogeneous, method (A) is preferred.
A phase transfer catalyst as described in A) may also be used. The reaction temperature is usually -20 to 150°C, preferably 0 to 80°C.
It is. The reaction time is usually 10 minutes to 50 hours, preferably 2 hours to 20 hours.

(D) Compound [1'] or a salt thereof can be produced by reacting raw material compound [■] or a salt thereof with compound [■].

Preferred examples of Y and reaction conditions in this reaction are the same as those described in the above method (C).

(E) Raw material compound [IX] or its salt and compound [X]
Compound [11] or a salt thereof can be produced by reacting with. In this reaction, Y is a halogen such as bromo or chloro, or a halogen such as acetyloxy or trifluoroacetyloxy.
Cl-4 acyloxy which may be substituted with 3 units, for example, C1-, alkylsulfonyloxy which may be substituted with 1 to 3 (flit) with halogens such as trifluoromethanesulfonyloxy are particularly preferred.This reaction is carried out by the method [Cl This can be done under the same conditions as described above.

Compound El'] in which Xa is a nitro group, that is, [wherein Rla, R1m and R3a have the same meanings as above. ] The compound represented by or a salt thereof can be produced by the methods (A) to (E) already described,
In addition, manufacturing is also possible by the following method.

(F) Compound [1a] or a salt thereof can be produced by nitrating compound [IX] or a salt thereof.

As the nitrating agent, 60 to 100% nitric acid is often used, but alkali metal nitrates such as sodium nitrate and potassium nitrate, nitrate alkyl esters such as ethyl nitrate and amyl nitrate, nitronium tetrafluoroborate (FIOfBF4), nitro Nitrifluoromethanesulfonate (NO, CF, 5O3) or the like may also be used. The nitrating agent can be used in an amount of about 1.0 to 20 equivalents based on Compound [IX] or its salt, but preferably 2.0 to 10 equivalents when nitric acid is used.

Although this reaction may be carried out without a solvent, it is usually carried out using sulfuric acid, acetic acid, acetic anhydride, trifluoroacetic anhydride, trifluoromethanesulfonic acid, or the like as a solvent. In some cases, solvents such as those mentioned in method (A) or mixtures thereof may be used. The reaction temperature of this reaction is -50°C to 1
The reaction time at 00°C is 10 minutes to 10 hours, preferably 130 minutes to 2 hours at 120°C to 60°C.

The thus obtained compound [1'] or a salt thereof can be concentrated by known means such as concentration 2, vacuum concentration, and distillation.

It can be isolated and purified by fractional distillation, solvent extraction, liquid conversion, dissolution, chromatography, crystallization, recrystallization, etc.

Compound [1] used as a raw material for the above method of the present invention
1] and [I[I] or their salts are some known compounds, for example, in the Journal of Medicinal Chemistry (J, Wed, Chet l 2 (
L901 (1977) and Chemical and Pharmacy Pharm.
, Bull, ).

23.2744 (1975), Japanese Patent Publication No. 63-2
33903, or a similar method thereto.

Primary or secondary amine [X
I] and compounds [] or their salts, for example, "New Experimental Chemistry Course" (Maruzen), 14-I [Volume 1.

It can be produced by the method described on pages 1332 to 1399 or similar methods.

Compounds [V] and [IX] or salts thereof are available from, for example, Rodd'S Chemistry of Carbon Compounds.
Carbon Compounds), Volume 1 Bart C
, pages 341-353 and chemical review s - (Ch
eIl, Reviews), 51!301 (19
It can be produced by the method described in 52) or similar methods. Since compound [■] or its salt is included in compound [I'] or its salt, it can be produced, for example, by the methods (A), (B), (C), (E), (F), etc. already described. .

Compounds [VI], [■] and [X] can be prepared by the method described in, for example, "New Experimental Chemistry Course" (Maruzen), Volume 14-1, pages 307-450, Volume 14-■, Pages 1104-1133, etc. It can be manufactured by a similar method.

Effect: The guanidine derivative [1] and its salt have excellent insecticidal activity, and this is clear from the following test examples.

Test Example 1 Brown planthopper (Nilaparvata)
5 ng of the test compound (indicated by the No. of the compound obtained in the example below) was added to the stems and leaves of two-leaf stage rice seedlings grown in a seedling box. Mel 0d/paper pot was dissolved in acetone, diluted 3000 times with Dyne (spreading agent, manufactured by Ota Pharmaceutical Co., Ltd.) water to a predetermined concentration (500 ppm), and sprayed with a spray gun. After pouring water into the bottom of a test tube and placing the treated rice seedlings there, 10 3rd instar brown planthopper larvae were released and the tube was capped with an aluminum stopper. This test tube was placed in a constant temperature room at 25°C, and dead insects were counted 7 days after release. The mortality rate is calculated using the following formula,
The results are shown in Table 1.

Table 1 below reveals that guanidine derivative 1 or its salt has an excellent insecticidal effect against brown planthoppers.

Test Example 2 Spodoptera
Effect on soybean seedlings (single leaf development stage), 1 g of the test compound (indicated by the compound number obtained in the example below) t + I was dissolved in 0.5 d of acetone containing Tween 20 O,
The chemical solution was adjusted to a predetermined concentration (500 ppm) using dyne water diluted 1:00 and sprayed with a spray gun at 20 d/bottle. After the chemical solution had dried, two single leaves of soybean were cut, placed in an ice cream cup, and 10 3rd instar larvae of Spodoptera were released. After adults, the cup was placed indoors (25°C), and dead insects were counted after 2 days. Ta. The mortality rate was calculated using the formula shown in Test Example 1, and the results are shown in Table-2.

Table 2 5IIIg of each test compound (indicated by the compound number obtained in the example below) was applied to cucumber stems and leaves at the first leaf development stage on which 10 adult female cotton aphids were released one day before spraying.
was dissolved in 0.5 g of acetone containing 20 μm of Tween, adjusted to a predetermined concentration (100 ppm) with 3000 times diluted dyne water, and sprayed with a spray gun at 10 d/pot of the chemical solution. Test plants at 27°C
Two days after treatment, the number of surviving female adults was counted. The mortality rate was calculated using the following formula, and the results are shown in Table 3.

This Table-2 proves that the guanidine derivative [I] or its salt has an excellent insecticidal effect against Spodoptera communis.

Test Example 3 Cotton aphid (Aphis gossy)
Table 3 shows that the guanidine derivative [1] or its salt has an excellent insecticidal effect on cotton aphids.

Next, the present invention will be explained in more detail with reference to Examples and Reference Examples, but the present invention should not be construed as being limited to these Examples.

The elution in column chromatography of Examples and Reference Examples was performed using TLC (Thin Layer Chr.
The analysis was carried out under observation using omato-graphy+ (thin layer chromatography). In TLC observation, Merck's Kigozel Gel 60F (70-230 mesh) was used as a TLC plate.
The solvent used as the elution solvent in column chromatography was used as the developing solvent, and a UV detector was used as the detection method. The silica gel for the column is also manufactured by Merck.
Zelgel 60 (70 to 230 mesh) was used. N.M.
R spectra show proton NMR, VARIAN EM3 using tetramethylsilane as internal standard.
Measurement was performed using a 90 (90 MHz) type spectrometer, and all δ values were expressed in ppm. When a mixed solvent is used as a developing solvent, the values shown in parentheses are the volumetric mixing ratio of each solvent.

In addition, the abbreviations used in the following Examples, Reference Examples, and Table 4 have the following meanings.

Me: methyl group, Et: ethyl group, Ph: phenyl group.

S: singlet, br: broad (wide), d
: doublet, 2) replet, q: quartet.

111 = multiplet, dd: doublet doublet.

J: Coupling constant, H2: Hell, CDCl23
: Weight ooho At1h, DMSO-da: Heavy DMSO
, %: weight % + l1lp: melting point Room temperature means about 15 to 25°C.

Reference example 1 Thionyl chloride 87.4g, 1,2-dichloroethane 10
In a water bath at 5-20°C, add 2-chloro-5 to the mixture of
A mixed solution of 703 g of -(hydroxymethyl)pyridine and 50 g of 1,2-dichloroethane was added dropwise over 30 minutes, followed by stirring at room temperature for 1 hour and 30 minutes and then under heating under reflux for 4 hours and 30 minutes. After concentration, the residue contains 200% chloroform! d,
60 g of water was added, and 20 g of sodium hydrogen carbonate was added little by little while stirring. The organic layer was separated, treated with activated carbon and concentrated to yield 75.9 g of 2-chloro-5-(chloromethyl)pyridine as a tan solid.

'HNMR (CDC+23): 4.57 (2) 1. s
), 7.34 (LH, d.

J-8,5Hz), 7.72(tH,dd, J=I1
1.5, 2.5Hz), 8.40 (IH, d, J
= 2.5) 1z) 5-(chloromethyl)thiazole, 5-(chloromethyl)-2-methylthiazole and 5-(chloromethyl)-2-phenylthiazole were obtained in the same manner.

Reference Example 2 A mixture of 60 ml of 2-chloro-5-(chloromethyl)hira 2F 1499 nitrile was placed in a stainless steel pressure-resistant reaction vessel and stirred in an oil bath at 80°C for 2 hours. 12.3 g of a 30% aqueous sodium hydroxide solution was added to the reaction mixture and concentrated. 200 g of ethanol was added to the residue, which was dried over anhydrous magnesium sulfate, and the insoluble matter was filtered out. After concentrating the furnace solution, it was purified by column chromatography (developing solvent: dichloromethane-methanol (4:1)), and 7.66 g
5-(aminomethyl)-2-chloropyridine was obtained as a yellow solid.

H NMR (CDC(23): 1.60(
2H,sun, 3.90(2H,s)7, 28(
1.11, d, J=8. 5Hz), 7. 8
7 (IH, dd, J= 8.5, 2.5Hz
), 8. 33 (LH. d, J= 2.5Hz
) Similarly, 5-(aminomethyl)-2-bromopyridine, 5-(aminomethyl)-2-chlorothiazole, 3
-7 amebenzylamine, 5-(aminomethyl)thiazole, 5-aminomethyl)-2methylthiazole, 5
-(aminomethyl)-2-phenylthiazole and 5-
(Aminomethyl)-2-(trifluoromethyl)thiazole was obtained.

Reference example 3 36g of 40% methylamine aqueous solution and 20g of acetonitrile
0rn1. Add 15.05g of 2-chloro5-(chloromethyl)pyridine and 5g of acetonitrile to the mixed solution of
A mixed solution of 0.0% was added dropwise over 1 hour, and the mixture was further stirred for 1 hour and 30 minutes. Concentrate the reaction mixture and add 100% water to the residue.
The organic layer was dried over anhydrous magnesium sulfate, concentrated, and the residue was subjected to column chromatography (developing solvent: dichloromethane). - methanol (41)) and purified with 8.77 g of 2-chloro-
5-(Methylaminomethyl)pyridine was obtained as a tan liquid.

H NMR (CDC+2a)+ 1.30 (ltl.
br. s), 2.44 (3Hs), 3.75 (2H
, s), 7.30 (lH.d, J=8.4Hz),
7.68 (ltl, dd, J= 8.4, 2.
4) 1z), 8. 35 (LH. d, J= 2
．． 4Hz) Reference Example 4 315 g of s,s'-dimethyl dithioiminocarbonate hydrochloride.
6.30 g of trifluoroacetic anhydride was added dropwise to a mixture of 30 parts of pyridine in a water bath at 20'C over 30 minutes, followed by stirring for 5 hours. The reaction mixture was concentrated, 20 d of water was added to the residue, and the mixture was extracted with dichloromethane (30 d). The organic layer was dried over anhydrous magnesium sulfate and then condensed, and the residue was purified by column chromatography (developing solvent: dichloromethane) using purified IL. obtained as.

H NMR (CDC123): 2.66 (s) Reference Example 5 N-cyanodithioiminocarbonate s,s'-dimethyl 1,0
5-(aminomethyl)-2-chloropyridine 0
．． 89 g of isopropyl alcohol 5d solution was added dropwise over 30 minutes, and the mixture was further heated under reflux for 1 hour and 30 minutes. The reaction mixture was cooled with water, the resulting white solid was collected in the furnace, and 1. , 3
5 g of 1-(6-chloro-3-pyridylmethyl)-
3-Noano2-methylisothiourea was obtained.

'H NMR (CDC&s) + 2.63 (3H,s)
4.51 (211, dJ=6Hz), 7.51
(IH.d, J=8Hz), 7.83 (IH, dd
．． J=8, 3Hz), 8. 38 (IH, d,
J=3Hz), 8. 95 (IH, br.s)
Similarly, 1-(6-chloro-3-pyridylmethyl)
-2-Methyl-3-trifluoroacetylisothiourea, 1-(6-chloro-3-pyridylmethyl)-1.2-
Dimethyl-3-trifluoroacetylisothiourea and 1-(2-chloro-5thiazolylmethyl)-3-cyano-2-methylisothiourea were obtained.

Reference Example 6 After washing 0.80 g of 60% sodium hydride (oil-based) with petroleum ether, 20 d of DMF was added. Add 2.5 ml of 3-cyano-1,2-dimethylisothiourea to this suspension at room temperature.
8 g of DMFIO-solution was added dropwise over a period of 10 minutes. After stirring for 1 hour, 3.24 g of 2-chloro-5-(chloromethyl)pyridine was added over 5 minutes, and the mixture was further stirred at room temperature for 15 hours.

DMF was distilled off under reduced pressure, and the residue was dichloromethane 100-
was added, washed with water, and the organic layer was dried over anhydrous magnesium sulfate. After concentration, column chromatography < developing solution ts
; chloroform-ethanol (20:1)) to obtain 3.50 g of 1-(6-chloro-3-pyridylmethyl)-3-cyano-1,2-dimethylisothiourea as a yellow liquid.

'HNMR(CDC(23)+2.84(3H,s)
, 3.20 (3H, s).

4,82(2H,s), 7.35(IH,d, J
= 8Hz), 7.63(IH, dd.

J=8.2Hz), 8Jl(1B, d, J=2)1z
) Similarly, 1-(6-chloro-3-pyridylmethyl)
-3-cyano-1-ethyl-2-methylisothiourea,
1-(6-chloro-3-pyridylmethyl)-1,2-dimethyl-3-ditroisothiourea, 1-(6-chloro-
3-pyridylmethyl)-1-ethyl-2-methyl-3-
Ditroisothiourea, 1-(2-chloro-5-thiazolylmethyl)-1-ethyl-2-methyl-3-ditroisothiourea and 1-(2-chloro-5-thiazolylmethyl)-1゜2-dimethyl-3- Ditroisothiourea was obtained.

Reference example 7 4.07 g of 2-chloro-5-aminopyridine.

Methyl isothiocyanate 2.55g, acetonitrile 3
After the mixture of 0d was heated under reflux for 13.5 hours, 0.70 g of methyl inthiocyanate was added, and the mixture was further heated under reflux for 3.5 hours. The reaction mixture was concentrated, and the residue was purified by column chromatography (developing solvent: dichloromethane-ethyl acetate (1:1)) to obtain 4.51 g of 1-(6-
Chloro-3-pyridyl)-3-methylthiourea was obtained.

mp164-164.5°C (recrystallized from acetonitrile)'HNMR (CDC123): 3.12 (3H, d
, Jl, 8Hz) 6, 86 (IH, br, q, J=
4.8Hz), 7.33 (IH, d, J= 8
．． 5Hz), 7.86 (IH, dd, J=8.5,
2.8Hz), 8.31 (IH, d, J=2゜8Hz
), 8.63 (IH, br, s) Reference Example 8 2-bromo-5-methylthiazole 4.45 g.

A mixture of 4.89 g of N-bromosuccinimide, 0.2 g of benzoyl peroxide, and 50 d of carbon tetrachloride was
After heating and refluxing for 0 minutes, 1. It was allowed to cool to room temperature. After separating the insoluble matter in the furnace, the furnace liquid was concentrated. The residue was purified by column chromatography (developing solvent: hexane-dichloromethane (2
: 3)) to give 4.53 g of 2-bromo-5-(
Bromomethyl)thiazole was obtained as a yellow solid.

'HNMR (CD C123): 4.64 (2B
, s), 7.54 (IH, s) Similarly, 5-(bromomethyl)-3-(difluoromethyl)-2-thiazolone was obtained.

Reference example 9 Potassium phthalimide 1.85g, dry IDMF20-
2.57 g of 2-bromo-5-(bromomethyl)thiazole was added portionwise over 20 minutes to the mixture at room temperature.
It was then stirred for 1 hour. After separating the insoluble matter in a furnace and concentrating the furnace liquid, 30% of ethanol was added, and 0.60 g of hydrazine hydrate was added dropwise over 2 minutes in an oil bath at 20°C. The reaction mixture was heated under reflux for 1 hour, concentrated, water 20- and concentrated hydrobromic acid 10- were added, and the mixture was further heated under reflux for 30 minutes.

After neutralizing with a 20% aqueous sodium hydroxide solution while cold, the mixture was concentrated, 50 d of acetonitrile was added to the residue, and insoluble matter was removed by furnace. After concentrating the furnace solution, it was purified by column chromatography (developing solvent: dichloromethane-methanol (5:1)) to obtain 0.76 g of 5-(aminomethyl)-2-bromothiazole as a brown oil.

'HNMR (CDCQ3): 1.59 (2H, s),
4.06 (2H, d, J=1.2Hz), 7.40 (
IH, t, J = 1.2 Hz) Reference Example 1O 0.88 g of diethylamine was added to a mixture of 1.35 g of 8-methyl-N-nitroisothiourea and 5 volumes of acetonitrile, and the mixture was stirred in an oil bath at 60'C for 6 hours. . After concentrating the reaction mixture, the residue was purified by column chromatography (developing solvent: dichloromethane-methanol (20:1) to obtain 0.85 g of N,N-diethyl-N'-nitroguanidine as a white solid. .

mp, 96-97°C 'HNMR (CDC'3): 1.23 (6H, t, J
'7.2Hz).

:1.47 (4H, q, J, 7.2Hz), 7.9
3 (2H, br, s) Reference Example 11 Add 0.61 g of pyrrolidine to a mixture of 1.0 g of S-methyl-N-ditroisothiourea and 15 acetonitrile at room temperature.
g was added dropwise over 2 minutes, followed by stirring for 30 minutes. The reaction mixture was concentrated, the remaining solid was washed with ether, and 1
．． 09 g of 1-(N nitroamidino)pyrrolidine was obtained as white crystals.

mp, 188-19 pC HNMR (DMSO-de): 1.7-2.1 (4H
, l11), 3.2-3, 5 (4tl, m), 8
．． 19 (2H, br, s) Similarly, N-ethyl-
N-methyl-N'nitroguanidine (mp, 124-1
25°C) was obtained.

Reference Example 12 11.3 g of acetic anhydride was added to a mixture of 5.0 g of S-methyl-N-nitroisothiourea and 25 g of pyridine at room temperature.
It was dripped in minutes. After the addition, the mixture was stirred at room temperature for 5 hours, and the reaction mixture was concentrated. Pour the residue into 50ml of 2N hydrochloric acid,
The resulting solid was collected in a furnace and dried to give N-acetyl-8-methyl-N'-ditroisothiourea5. 1 g was obtained as white crystals.

mp, 109-110°C HNMR (CD CQz'): 2.30 (3H, s)
, 2.42 (3H, 5) 11, 20 ~ f2.00 (I
H, br, ) Reference Example 13 2-Hydroxy-5-methylthiazole (5-methyl-
2-thiazolone) 11.5g, dioxane 100d
, to a mixture of 100 g of 40% aqueous sodium hydroxide solution,
Chloronfluoromethane (gaseous) was bubbled in for 1 hour in an 80°C oil bath. 500 ml of reaction mixture
1n1. of water and extracted twice with ether. The ether layer was dried over anhydrous magnesium sulfate, concentrated, and the residue was separated by column chromatography (developing solvent: dichloromethane-hexane (1:1)).
g of 2=(difluoromethoxy)-5-methylthiazole ('HNMR(CDC(!3): 2.35(
3f(,d, J=1.5Hz).

6, 88 (IH, br, q, J=1.5Hz),
7.18 (IH, t, J=72.OHzno and 4.
3-(difluoromethyl)-5-methyl-2-thiazolone ('HNMR (CDC): 2.16 (3H
,d, J=1.5Hz), 6.51(IH,br,
q, J=1. '5Hz), 7.07(11(,t
, J・60.0Hz)) was obtained. Both are pale yellow liquids.

Reference example 14 2.2.2-trifluorothioacetamide 1122g
, 114 g of ethyl 2-chloro-2-formylacetate in a 70° C. bath for 30 minutes.

1 hour and 30 minutes in an oil bath at 100°C (after washing,
Dichloromethane food was added to remove insoluble matter. After concentration, it was purified by column chromatography (developing solvent: hexane-ethyl acetate (10:1)), and 3.74 g of 2
Ethyl -(trifluoromethyl)5-thiazolecarboxylate was obtained as a yellow liquid. 'HN M R (CD C
Q=)A, 41 (3H, t, J・7.2Hz),
4.43 (28,q, J=7.2t(z), 8.5
0(IH,s).

Lithium aluminum hydride 0.50g, dry THF8
A solution of 2.51 g of the above ethyl thiazolecarboxylate in THFIOd was added dropwise to the 0M mixture at room temperature over 45 minutes, and the mixture was further stirred for 30 minutes. 0.0% water was added to the reaction mixture cooled with a cryogen. ! M.

10% sodium hydroxide aqueous solution 0.5M1. Water 1.5-
were added dropwise in this order. After stirring in a water bath for 10 minutes and further stirring at room temperature for 30 minutes, insoluble matter was separated on Celite. After concentrating the furnace liquid, add chloroform 100-
By drying with anhydrous magnesium sulfate and concentrating,
124 g of 5-(hydroxymethyl)-2-(1-lifluoromethyl)thiazole was obtained as a brown liquid. 'H
NMR (CD6g 3 units 3.45 (IH, br, s),
4.93 (211, s), 7.77 (18, s) 0.80 g of the above thiazole was added to a mixture of 0.4 thionyl chloride and 1 d of 1,2-dichloroethane in an oil bath at 40'C.
A dichloroethane solution of 1,2-dichloroethane was added dropwise over 10 minutes, and the mixture was further stirred at the same temperature for 1 hour. Dichloromethane 2Tn1. After adding 2 volumes of water, and stirring, heavy soybean paste was added to adjust the pH of the aqueous layer to 7. The organic layer was separated and the aqueous layer was extracted with dichloromethane. The organic layers were combined, the insoluble materials were filtered out, washed with saturated brine, and then dried over anhydrous magnesium sulfate. After concentration, 0.74
g of 5-(chloromethyl)-2-(trifluoromethyl)thiazole was obtained as a reddish-brown liquid.

'HNMR (CDCI23): 4.84 (2H, s)
, '7, 90 (11, s) Example 1 l-(6-chloro-3-pyridylmethyl)-3-cyano-1-ethyl-2-methylisothiourea 0°42g and acetonitrile 5M! , to a mixture of 40% under heating reflux.
0.5 g of methylamine aqueous solution was added every hour for 6 times (total of 3.
The reaction mixture was stirred for 6 hours while adding 0g). The reaction mixture was concentrated and 0.32 g of 1-(6-chloro-3
-pyridylmethyl)-2=cyano-1-ethyl-3-methylguanidine (compound No. 3) was obtained. mp1
22-123℃'HNMR (DMSOda): 1.0
7 (3H, t, J=7Hz).

3.00 (3H, d, J=5Hz), 3J5 (2tl
, q, J=7Hz), 4.62 (2B, s), 7
．． 23(1)(,br,s), 7.50(IH,d
, J = 8Hz).

7, 78 (IH, dd, J= 8.3!Iz), 8
．． 33 (ltl, d, J = 3■2) Example 2 60% sodium hydride (oil-based) 0.44 g, dry DM
1.32 g of N,N-dimethyl-N'-nitroguanidine was added to the suspension of FIO- at room temperature between 2C1. After stirring for 10 minutes, 1.62 g of 2-chloro-5(chloromethyl)pyridine was added over 5 minutes, and then at room temperature for 2 hours.
The mixture was stirred in an oil bath at 60°C for 4 hours. After separating the insoluble matter in a furnace and concentrating the furnace liquid, the residue was subjected to column chromatography (developing solvent: dichloromethane-ethyl acetate 5:1 to 3:
1) to obtain 0.82 g of 1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2-nitroguanidine (Compound No. 6).

mp160.5~162.5℃ Elemental analysis (C, H,, N, O, Cg) Calculated value C:
41.95 H: 4.69 N: 27. t
g Actual value C: 41.73 H: 4.59 N
:26.94HNMR (CDCf2s): 3.10(
6H, s), 4.49 (2Hbr, s), 7.27
(lH, d, J=8.5Hz), 7.70 (IFI
dd, J=8, 5.2.5Hz), 8.2~8.5(
2H, m) Example 3 ■, 045 g of 2-dimethyl-3-ditroisothiourea,
5-(aminomethyl)-2-chloropyridine 0.43g
A mixture of 25 parts of ethanol was heated under reflux for 6 hours, and then concentrated. The residue was subjected to column chromatography (developing solvent;
Chloroform-ethanol (5:1) was purified to yield 0.25 gc)1-(6-liter).

Rho-3-pyridylmethyl)-3-methyl-2-nitroguanidine (compound No. 5) was obtained.

n+p150~152℃ Elemental analysis (c IHION 50 pc (calculated value C: 39.44 H: 4.14 N: 28
．． 74 actual measurement value C: 39.92 H: 4.12
N228.91'HNMR (CD0g3-DMSO-
d, ): 2.94 (3H.

d, J-5Hz), 4.51 (2Ld, J=5FIz
), 7J2 (IH, d.

J=8Hz), 7.75(ltl, dd, J=8.
2Hz), 7.82 (IH, br.

s), 8J7 (IH, d, J=2Hz), 8.
90 (IH, br, s) Example 4 S-methyl-N-ditroisothiourea 0.676 g, 2
-Chloro-5-(methylaminomethyl)pyridine 0.7
A mixture of 83g of acetonitrile and 61n1 of acetonitrile was heated under reflux for 17 hours, and then the reaction mixture was concentrated. By recrystallizing the residue from ethanol, 0.38 g of 1-(
6-chloro-3-pyridylmethyl)-1-methyl-2-
Nitroguanidine (compound No. 7) was obtained. mp
167-170°C elemental analysis (C, H,, N so
tC (l>calculated value C: 39.44 H: 4.14
N: 28.74 Actual value C: 39.39
H:4.07 N:28.85'HNMR(DM
SOds): 3.01 (3H, s), 4.70 (2
1,s), 7.48(IH,d, J=8.4[
1z), 7.78 (IH, dd, J=8.4,2
．． 2H2), 8.37 (18, d, J=2.2Hz
), 8.56 (2Hbr, s) Example 5 0.82 g of l-(6-chloro-3-pyridylmethyl)-1°2-dimethyl-3-ditroisothiourea.

A mixture of 0.464 g of a 40% aqueous methylamine solution and 10 d of acetonitrile was stirred at 70° C. for 2 hours. After concentrating the reaction mixture, it was purified by column chromatography (open medium dichloromethane-methanol (10:l)) to obtain 0.56 g of 1-(6-chloro-3-pyridylmethyl)-1,3-dimethyl. -2-nitroguanidine (compound No. 8) was obtained.

mp136-137°C Elemental analysis value (CeH+2N So , c Q) Calculated value C: 41.95 H: 4.69 N: 27.
1g actual value C-41,89H: 4.75 N: 2
7.15HNMR (CDC(2a): 2.96(3)
1. d, J=4.8Hz) 3.05 (3B, s), 4
．． 87 (2H, s), 7.33 (lH, d, J-'8
．． 3Hz), 7°68 (IH, dd, J = 8.3
．． 2.4Hz), 7.96 (1B, br, q,
J=4.8Hz), 8.30(ltl, d,
J = 2.4 Hz) Example 6 A mixture of 0.53 g of nitroguanidine, 0.61 g of 3-(aminomethyl)pyridine, and 10 ml of water was heated at 70 to 80°.
The mixture was stirred at C for 1.5 hours. After standing overnight at room temperature, the precipitate was collected, washed with ethanol, and 0.488 N-
Nitro-N'-(3-pyridylmethyl)guanidine (compound No. I2) was obtained.

mp, 185-190'c HNMR (DMSOds): 4.47 (28,d, J
=5Hz).

7.40 (IH, dd, J=6.4Hz), 7.6
7-7.35 (ILm), finished, 85-8.30 (2
H, br, s), 8.47-8.67 (2H, m) Example 7 l-(6-chloro-3-pyridylmethyl)-3°3-dimethyl-2-nitroguanidine (compound no.

6) Add 60 g to a mixture of 0.24 g and dry THF6d at room temperature.
After adding 0.045 g of % sodium hydride (oil-based), the mixture was stirred for 30 minutes. Add 0.1 iodomethane to the reaction mixture.
After adding 6 g of THF1d solution and reacting for 3 days,
0.1 fart of acetic acid was added, insoluble matter was separated by furnace, and the furnace liquid was concentrated. The residue was purified by column chromatography (developing solvent dichloromethane-methanol (20:I)) to give a 0.
17 g of 1=(6-chloro-3-pyridylmethyl)-
1,3,3-trimethyl-2-nitroguanidine (compound N014) was obtained as a white solid.

Elemental analysis value (CIoIJl, N, 02CC) calculated value
C:44.21. H: 5.19 N: 25.7
8 Actual value C carp 4.14 H: 5.14. N
: 25.61mp, 99-1OpiC HNMR (CDCe3): 2.90 (3H, s),
3.02(6t(,s)4,03(2H,s),7.
38 (ltl, d, J = 8.5Hz), 7.7
9 (IHdd, J=8.5., 2.7Hz), 8
．． 37 (IH, d, J = 2.7 Hz) Example 8 l-(6-chloro-3-pyridylmethyl)-313-dimethyl-2-nitroguanidine (compound no.

6) Add a mixture of 0.26g and dry THF at 20°C.
0.08 g of 60% sodium hydride (oil-based) in a water bath of
was added and stirred for 30 minutes. A solution of 0.26 g of formic acid acetic anhydride in THFo, 5d was added to the reaction mixture over 1 minute, the bath was removed, and the mixture was further stirred for 12 hours. 0 acetic acid in the reaction mixture
．． After adding 57n1, it was concentrated, and the residue was purified by column chromatography (developing solvent: dichloromethane-meth/-ol (30:l)) to obtain 010 g of 1-(6-chloro-3-pyridylmethyl)-1. -Formyl-3,3-dimethyl 2-nitroguanidine (Compound No. 22) was obtained as a syrupy liquid.

'HNMR(CDC(!3): 3.03(6H,s)
, 4.70 (2H.

s), 7J6 (11, d, J=8.7Hz), 7.
74 (IH, dd, J=8, 7.2.7Hz), 8.
40 (LH, d, J= 2.7FIz), 8.44
(IH.

S) Example 9 l-(6-chloro-3-pyridylmethyl)-3+3-dimethyl-2-nitroguanidine (compound no.

6) A mixture of 0.20 g, acetic anhydride, 0.095 g, and dry pyridine 1- was stirred at 60°C for 2 hours and at 100°C for 5 hours, and then concentrated. The residue was subjected to column chromatography (developing solvent: dichloromethane 97-methanol (40:
1)) to give 0.12 g of 1-acetyl-1-(
6-chloro-3-pyridylmethyl)-3,3-dimethyl-2-nitroguanidine (Compound No. 23) was obtained as a syrupy liquid (mixture of cis and trans forms).

HNMR (CDCe3) + 2.10 + 2.1.6 (
3H, S+S).

2.6-3J (6t1.m), 4. I~5.2 (2t
(, m'), 7.23-7.45 (11 (, m),
7.67-7.90 (IH, m), 8.30-8.5
0 (18, m).

Example 10 ■ A mixture of 1.03 g of -(6-chloro-3-pyridyl)-3-methylthiourea, 0.32 g of cyanamide, 1.58 g of dicyclohexylcarbodiimide, 3 drops of ethyldiisopropylamine, and the 10 commandments of acetonitrile was After stirring at room temperature for an hour, the insoluble matter was collected for γ months. This insoluble material was first recrystallized from a mixed solvent of acetonitrile and methanol, and then further recrystallized from acetonitrile. N
o, 24) Got it.

mp, 227-228°C Elemental analysis value CC, HsN, C (1) Calculated value: C: 45.84 H: 3.85 N: 33
．． 41 actual measurements: C: 46.12 H: 3. eg
N: 33.37'HNMR (DMSOda): 2
．． 85(3)], d, 4, UZ).

7.2-7.65 (2H, m), 7.83 (LH, d
d, J = 8.5.3.0flz).

8, 36 (1)! , d, J= 3.0Hz), 9
．． 06 (18, br, s) Example 11 5-(aminomethyl)-2-bromothiazole 0°39
g, 1,2-dimethyl-3-ditroisothiourea 0.3
0g, cuprous bromide 0.58g, anhydrous potassium carbonate 0.5
After stirring a mixture of 5 g and dry acetonitrile for 45 minutes in an oil bath at 60°C, the reaction mixture was purified by column chromatography (developing solvent: dichloromethane-methanol (10:1)). 27g of 1-(
2-Bromo-5-thiazolylmethyl)-3-methyl-2
-Nitroguanidine (Compound No. 37) was obtained as a white solid.

mp170°C Elemental analysis value (CeH, N 50 , S B r) Calculated value C; 24.50 H: 2.74 N: 23.8
1 Actual value C: 24.47 H: 2.73 N:
23.73HNMR (DMSO-d, ): 2.81 (
3)1. d, J=5.0Hz).

4, 51 (2H, s), 7.60 (IH, s), 8
．． 08 (IH, br, s), 8.93 (IH, br
, s) Example 12 0.5 g of N-acetyl-8-methyl-N'-ditroisothiourea and 5 rn of acetonitrile! 0.4 of 5-(amino/methyl)-2-chloropyridine was added to 1 of the warm mixture under water cooling.
4 g of acetonitrile solution was added dropwise, and the mixture was further stirred for 30 minutes under water cooling. After concentrating the reaction mixture, the residue was recrystallized from ethanol to give 0.59 g of N-acetyl-N'-(6-chloro-3-pyridylmethyl)-N'-
Nitroguanidine (compound No. 42) was obtained as white crystals. mp.

125-126℃ Elemental analysis value (C,H,.N5OsCQ) Calculated value C:
39.79 H: 3.71 N: 25.78 Actual value C: 39.71 H: 3.69 N +25.
51'HNMR (CDCQ3): 2.33(3)1
．． s), 4.60 (2H, d.

J=6.0H2), 7.33(IH,d, J=7.8
Hz), ? , 50-7.87 (II(.

m), 8.37 (11, d, J=2.5Hz),
9.70 (LH, br, s), 11.85 (br,
s) According to the above Examples 1 to 12 and the manufacturing method of the present invention, the following table -
The compound shown in 4 was obtained. The compounds obtained in the above examples are also shown in Table 4.

(Left below) Example 13 Compound No. 1 (20% by weight), xylene (75% by weight)
) and polyoxyethylene glycol ether (Nonipol 85(8)) (5% by weight) were thoroughly mixed to prepare an emulsion.

Example 14 Compound No. 6 (30% by weight), sodium ligninsulfonate (5% by weight) 1 Polyoxyethylene glycol ether (Nonipol 85'') (5% by weight).

White carbon (30i% by weight), clay (30% by weight)
) were mixed well to produce a wettable powder.

Example 15 Compound No. 7 (3% by weight), white carbon (3% by weight), and clay (94% by weight) were thoroughly mixed to produce a powder.

Example 16 Compound No. 8 (10% by weight), sodium ligninsulfonate (5% by weight), and clay (85% by weight) were thoroughly ground and mixed, water was added, and the mixture was thoroughly kneaded, then granulated and dried to form granules. The drug was manufactured.

Effects of the Invention The present invention contributes to agriculture by providing an excellent insecticide.

Claims (9)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 is an optionally substituted homologous or heterocyclic group, n is 0 or 1, and R^2 is hydrogen or a substituted R^3 represents a primary, secondary or tertiary amino group, and X represents an electron-withdrawing group. However, when X is a cyano group, R^1 is an optionally substituted homocyclic or heterocyclic group excluding a pyridyl group, and when n is 0,
R^1 represents an optionally substituted heterocyclic group. ] An insecticide composition containing a guanidine derivative or a salt thereof. (2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 is an optionally substituted homologous or heterocyclic group, n is 0 or 1, and R^2 is hydrogen or a substituted R^3 represents a primary, secondary or tertiary amino group, and X represents an electron-withdrawing group. However, when X is a cyano group, R^1 represents a halogenopyridyl group or a halogenothiazolyl group, and when n is 0, R^1 represents an optionally substituted heterocyclic group. ] An insecticide containing a guanidine derivative or a salt thereof. (3) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 is an optionally substituted homologous or heterocyclic group, n is 0 or 1, and R^2 is hydrogen or a substituted R^3 represents a primary, secondary or tertiary amino group, and X represents an electron-withdrawing group. However, when X is a cyano group, R^1 is a halogenothiazolyl group,
When n is 0, R^1 represents an optionally substituted heterocyclic group. ] An insecticide containing a guanidine derivative or a salt thereof. (4) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1^a is an optionally substituted heterocyclic group, and R^2^a is hydrogen or an optionally substituted carbon group. A hydrogen group, R^3^a represents a primary, secondary or tertiary amino group, and when R^2^a is hydrogen, R^3^a is a secondary or tertiary amino group, X^ a represents a nitro or trifluoroacetyl group. ] A guanidine derivative or a salt thereof. (5) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1^a, R^2^a and X^a are the claims (
4) Same meaning as described, Y represents a leaving group. ] There are formulas, chemical formulas, tables, etc. that are characterized by reacting a compound represented by or a salt thereof with ammonia, a primary or secondary amine, or a salt thereof. 4) Indicate the same meaning as the description. ] A method for producing a guanidine derivative or a salt thereof. (6) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^3^a and X^a have the same meanings as described in claim (4), and Y represents a leaving group. ] or its salt and the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [The symbols in the formula have the same meaning as described in claim (4). ] There are formulas, mathematical formulas, chemical formulas, tables, etc., which are characterized by reacting with a compound represented by or a salt thereof. [The symbols in the formula have the same meanings as those described in claim (4). ] A method for producing a guanidine derivative or a salt thereof. (7) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Symbols in the formula indicate the same meaning as described in claim (4). ] or a salt thereof and the formula R^1^a-CH_2-Y [wherein R^1^a has the same meaning as described in claim (4), Y
indicates a leaving group. ] There are formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [Symbols in the formulas have the same meanings as described in claim (4). ] A method for producing a guanidine derivative or a salt thereof. (8) Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1^a and X^a have the same meaning as stated in claim (4), and R^2^b is hydrogen or substituted. R^3^b represents a primary, secondary or tertiary amino group, and when R^3^b is a tertiary amino group, R^2^
b is hydrogen. ] or a salt thereof and the formula Y-R [wherein R represents an optionally substituted hydrocarbon group and Y represents a leaving group. ] There are formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [Symbols in the formulas have the same meanings as described in claim (4). ] A method for producing a guanidine derivative or a salt thereof. (9) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Symbols in the formula indicate the same meaning as described in claim (4). ] or a salt thereof and the formula Y-X^a [wherein X^a has the same meaning as described in claim (4), and Y represents a leaving group. ] There are formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [The symbols in the formulas have the same meanings as those described in claim (4). ] A method for producing a guanidine derivative or a salt thereof.