JPH07278094A - Guanidine derivative, method for producing the same and insecticide - Google Patents

Abstract

PURPOSE:To obtain a safe guanidine derivative low in toxicity against men, livestock, fishes and natural enemies, and useful as an insecticide by reacting specific compounds with each other. CONSTITUTION:This derivative of formula I [R<1> is a homogeneous ring consisting of a 3-8C cycloalkyl, a 3-8C cycloalkenyl or a 6-14C aryl, or a five- seven membered heterocyclic ring containing 1-5 heteroatoms selected from O, S and N; R<2> is H or a hydrocarbon such as 1-15C alkyl, 3-10C cyclcoalkyl, 2-10C alkenyl or alkynyl; R<3> is a group of formula II (R<4>, R<5> are H, (substituted) hydrocarbon, etc.); X is cyano, nitro, 1-4C alkoxy-carbonyl, etc.] is obtained by reacting a compound of formula III (Y is a releasable group) with a compound of formula IV. The objective derivative includes 1-(6-chloro-3- pyridylmethyl)-2-cyano-1-ethyl-3-methylguanidine.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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.

[0002]

2. Description of the Related Art Conventionally, many synthetic compounds having a pest controlling effect have been used as insecticides, but most of them are organic phosphoric acid esters, carbamate esters, organic chlorine-containing compounds or pyrethroid compounds. Belong to. It is well known that the heavy use of such a compound in a limited range causes harmful effects such as an increase in pesticide resistance of pests, and is a problem in many places. In addition, some of the above insecticides have high insecticidal activity, but are highly toxic to humans and fish, and sometimes show toxicity to natural enemies of pests, and are too persistent in soil etc. In reality, it is not always possible to obtain a satisfactory effect.

On the other hand, regarding the guanidine derivative or its salt, for example, 3-nitro-1- (3-pyridylmethyl) guanidine is Chemical and Pharmaceutical Bulletin (Chem. Pharm. Bull.), 23 , 2744.
In addition to those described in (1975), compounds having an anti-ulcer activity represented by cimetidine are known.

[0004]

Under such circumstances, the present invention provides a guanidine derivative or a salt thereof which has low animal and animal toxicity, fish toxicity and natural enemies toxicity, and is safe and has an excellent controlling effect against pests. It is intended to be provided as an insecticide.

[0005]

In order to solve the above problems, the inventors of the present invention have conducted extensive studies for many years in order to find an insecticide having a completely different structure from the conventionally used insecticides. As a result, the expression

[Chemical formula 23] [Wherein R ¹ is an optionally substituted homologous or heterocyclic group, n is 0 or 1, R ² is hydrogen or an optionally substituted hydrocarbon group, and R ³ is a primary, A 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 except for a pyridyl group, and when n is 0, R ¹ is an optionally substituted heterocyclic group. Indicates. ] It was found that the guanidine derivative represented by the formula [1] and a salt thereof surprisingly have a very strong insecticidal action, and it was also found that the toxicity was low, and based on these, the present invention was completed.

That is, the present invention includes (1) the general formula [I]

[Chemical formula 24][In the formula, R¹Is C_3-8Cycloalkyl, C_3-8Cycloal
Kenil, C_6-14A homocyclic group selected from aryl,
Is selected from oxygen atom, sulfur atom and nitrogen atom.
5 to 8 membered heterocyclic group containing 1 to 5 terror atoms is shown.
An allomorphic or heterocyclic group is C_1-15Alkyl, C_3-10Shiku
Lower alkyl, C_2-10Alkenyl, C_2-10Alkynyl, C
_3-10Cycloalkenyl, C_6-10Aryl, C_7-10Aral
Kill, nitro, hydroxyl group, mercapto, oxo, thioki
So, cyano, carbamoyl, carboxyl, C_1-4Al
Coxy-carbonyl, sulfo, halogen, C_1-4Arco
Kish, C_6-10Aryloxy, C_1-4Alkylthio, C
_6-10Arylthio, C_1-4Alkylsulfinyl, C
_6-10Arylsulfinyl, C_1-4Alkyl sulfoni
Le, C_6-10Arylsulfonyl, amino, C_2-6Acyl
Amino, mono- or di-C_1-4Alkylamino, C_3-6Shi
Chloroalkylamino, C_6-10Arylamino, C_2-4A
Sill, C_6-10Aryl-carbonyl, and oxygen, sulfur
And 5 including 1 to 4 heteroatoms selected from nitrogen
Having 1 to 5 substituents (A) selected from 6-membered heterocyclic groups
And the substituent (A) is C_6-10Aryl, C_7-10
Aralkyl, C_3-10Cycloalkyl, C_3-10Cycloal
Kenil, C_6-10Aryloxy, C_6-10Arylthio,
C_6-10Arylsulfinyl, C_6-10Aryl sulfoni
Le, C_6-10When it is an arylamino or a heterocyclic group,
1 to 5 halogens, hydroxyl groups, C_{1- Four}Alkyl,
C_2-4Alkenyl, C_2-4Alkynyl, C_6-10Aryl,
C_1-4Alkoxy, phenoxy, C_1-4Alkylthio again
May be substituted with a phenylthio group.
The substituent is C_1-15Alkyl, C_2-10Alkenyl, C_2-10Al
Quinyl, C_1-4Alkoxy, C_1-4Alkylthio, C_1-4
Alkylsulfinyl, C_1-4Alkylsulfonyl, a
Mino, Mono- or Di-C_1-4Alkylamino, C_3-6Shiku
Lower alkylamino or C_6-10It is an arylamino group
In the case of 1 to 5 halogens, hydroxyl groups, C_1-4Al
Coxy or C_1-4Even if it is substituted with an alkylthio group
Good.

R ² is a hydrogen atom, or C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10
Represents a hydrocarbon group selected from alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, which hydrocarbon group has ¹ to 5 substituents similar to R ^1. May be.

R ³ is the formula

[Chemical 25] (In the formula, R ⁴ and R ⁵ are the same or different and represent hydrogen or a hydrocarbon group which may have a substituent, or R ⁴ and R ⁵ are taken together to form a cyclic amino group together with an adjacent nitrogen. The hydrocarbon group may be a C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C group.
_2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the hydrocarbon group has a substituent similar to the substituent in the heterocyclic group of R ^1. You may have. The cyclic amino group is selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. ) Represents an amino group. X is cyano, nitro, C _1-4 alkoxy-carbonyl, hydroxycarbonyl, C _6-10 aryl-oxycarbonyl, heterocyclic oxycarbonyl, C _1-4 alkylsulfonyl optionally substituted with halogen, sulfamoyl,
It represents di-C _1-4 alkoxyphosphoryl, C _1-4 acyl optionally substituted with halogen, C _6-10 aryl-carbonyl, carbamoyl or C _1-4 alkylsulfonylthiocarbamoyl.

However, when (i) n is 0, R ¹ represents a heterocyclic group which may have a substituent, and (ii) when X is a nitro group, R ¹ is the same as above. The same meaning or a homocyclic or heterocyclic group which may have a substituent is shown, n is 0 or 1, and R ² is a C _1-4 alkyl having a substituent, or has a substituent. _Optionally C _5-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl,
C _3-10 cycloalkenyl, C _6-10 aryl or C _7-10
An aralkyl group, these substituents have the same meanings as the above-mentioned substituents for R ² , R ³ has the same meaning as the above, and (iii) when X is a nitro group, R ¹ represents a homologous or heterocyclic group which may have a substituent having the same meaning as that described above, n represents 0 or 1, R ² represents a hydrogen atom or C _1-4 alkyl, and R ³ is the formula

[Chemical formula 26](In the formula, R^FourAnd R^FiveOne of them is a hydrogen atom or
A hydrocarbon group which may have a substituent is shown.
The base is C_1-15Alkyl, C_3-10Cycloalkyl, C_2-10A
Lucenil, C_2-10Alkynyl, C_3-10Cycloalkeni
Le, C_6-10Aryl and C_7-10Select from aralkyl group
And the substituent of the hydrocarbon group is the above R¹To the heterocyclic group
Shows a substituent similar to the above, the other has a substituent
C_1-4Carbonization which may have alkyl or substituents
A hydrogen group, wherein the hydrocarbon group is C_5-15Alkyl, C_3-10
Cycloalkyl, C_2-10Alkenyl, C_2-10Alkini
Le, C_{3- Ten}Cycloalkenyl, C_6-10Aryl and C
_7-10Selected from aralkyl groups, said C_1-4Alkyl hydrocarbon
The substituent of the elementary group and the substituent of the hydrocarbon group are the same as the above R.¹of
Is the same as the substituent on the heterocyclic group, or is it
Is R^FourAnd R^FiveTogether with the adjacent nitrogen
No, azetidino, pyrrolidino, morpholino and thiomo
It forms a cyclic amino group selected from a ruforino group. )so
And (iv) X is a cyano group
R¹Is a heterocyclic group which may have a substituent.
, Excluding pyridyl groups that do not have substituents
You ] Contains guanidine derivative or its salt
Insecticide composition,

(2) The general formula [I ^a ]

[Chemical 27] [In the formula, R ^1a represents a 5- to 8-membered heterocyclic group containing 1 to 5 heteroatoms selected from oxygen atom, sulfur atom and nitrogen atom, and the heterocyclic group is C _1-15 alkyl, C _{3 -10} cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10
Cycloalkenyl, C _6-10 aryl, C _7-10 aralkyl, nitro, hydroxyl group, mercapto, oxo, thioxo,
Cyano, carbamoyl, carboxyl, C _1-4 alkoxycarbonyl, sulfo, halogen, C _1-4 alkoxy,
C _6-10 aryloxy, C _1-4 alkylthio, C _6-10 arylthio, C _1-4 alkylsulfinyl, C _6-10 arylsulfinyl, C _1-4 alkylsulfonyl, C _6-10
Arylsulfonyl, amino, C _2-6 acylamino, mono- or di-C _1-4 alkylamino, C _3-6 cycloalkylamino, C _6-10 arylamino, C _2-4 acyl, C
_6-10 arylcarbonyl and _optionally 1 to 5 substituents (A) selected from 5 to 6 membered heterocyclic groups containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen , Wherein the substituent (A) is C _6-10 aryl, C
_7-10 aralkyl, C _3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio, C _6-10 arylsulfinyl, C _6-10 arylsulfonyl, C _6-10 When it is an arylamino or a heterocyclic group, it further has 1 to 5 halogens, a hydroxyl group, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _6-10 aryl, C _1-4 alkoxy, It may be substituted with a phenoxy, C _1-4 alkylthio or phenylthio group, and the above substituents are C _1-15 alkyl, C _2-10 alkenyl, C
_2-10 alkynyl, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C _3-6 cyclo When it is an alkylamino or C _6-10 arylamino group, it may be further substituted with 1 to 5 halogens, hydroxyl groups, C _1-4 alkoxy or C _1-4 alkylthio groups.

R ^2a is a hydrogen atom or C _1-15 alkyl,
_Represents a hydrocarbon group selected from C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl group,
These hydrocarbon groups may have 1 to 5 substituents similar to R ^1a .

R ^3a is the formula

[Chemical 28] (In the formula, R ⁴ and R ⁵ are the same or different and represent hydrogen or a hydrocarbon group which may have a substituent, or R ⁴ and R ⁵ are taken together to form a cyclic amino group together with an adjacent nitrogen. The hydrocarbon group may be a C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _{2-10 group.}
Selected from alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, the hydrocarbon group having a substituent similar to the substituent in the heterocyclic group of R ^1a Good. The cyclic amino group is selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. ) Represents an amino group. X ^a represents a nitro, cyano or trifluoroacetyl group.

However, when (i) X ^a is a nitro group, R ^1a represents a heterocyclic group which may have a substituent of the same meaning as described above, and R ^2a represents a C _1- having a substituent. ₄ alkyl or optionally substituted C _5-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl or a C _7-10 aralkyl group, the substituents R ^2a represents those similar to the substituents of the above R ^2a, R ^3a represents the same meaning as those described above, (ii)
When X ^a is a nitro group, R ^1a represents the above-mentioned optionally substituted heterocyclic group, R ^2a represents hydrogen or C _1-4.
Alkyl, R ^3a is of the formula

[Chemical 29] (In the formula, one of R ⁴ and R ⁵ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the hydrocarbon group is a C _1-15 alkyl group or a C _3-10 cycloalkyl group. , C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the hydrocarbon group is a heterocyclic group of R ^1a . The same as the substituent on the ring group is shown, and the other is C having a substituent.
_1-4 represents a hydrocarbon group which may have an alkyl or a substituent, and the hydrocarbon group is C _5-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the C _1-4 alkyl and the substituent of the hydrocarbon group are the substituents on the heterocyclic group of R ^1a. shows what the same group, or R ⁴ and R ⁵ are aziridino together with the adjacent nitrogen together, azetidino, pyrrolidino, may form a cyclic amino group selected from morpholino and thiomorpholino groups. ) Is an amino group, and (iii) X ^a is a cyano group, R ^1a is
(a) a pyridyl group having 1 to 5 substituents in the above R ^1a , or (b) a halogenated thiazolyl group, wherein R ^2a has a hydrogen atom or a substituent similar to the above R ^2a. And R ^3a has the same meaning as defined above. ] The guanidine derivative represented by or its salt,

(3), formula

[Chemical 30] [In the formula, R ^1a , R ^2a and X ^a have the same meanings as described above, and Y represents a leaving group. ] Or a salt thereof represented by the formula

[Chemical 31] (The symbols in the formula have the same meanings as described above.) A method for producing ^a guanidine derivative [I ^a ] or ^a salt thereof, which comprises reacting the compound or a salt thereof.

(4), formula

[Chemical 32] [The symbols in the formulas have the same meanings as described above. ] Or a salt thereof represented by the formula

[Chemical 33] [The symbols in the formulas have the same meanings as described above. ] A compound represented by or a salt thereof is reacted, a method for producing ^a guanidine derivative [I ^a ] or a salt thereof,

(5), formula

[Chemical 34] [The symbols in the formulas have the same meanings as described above. ] Or a salt thereof represented by the formula

[Chemical 35] [The symbols in the formulas have the same meanings as described above. ] A guanidine derivative characterized by reacting with a compound represented by
[I ^a ] or ^a method for producing a salt thereof,

(6), formula

[Chemical 36] [Wherein R ^1a and X ^a have the same meanings as described above, R ^2b is hydrogen or an optionally substituted hydrocarbon group, and R ^3b is

[Chemical 37] (The symbols in the formulas have the same meanings as defined above.) The primary, secondary or tertiary amino group is represented by the formula, and when R ^3b is a tertiary amino group, R ^2b is hydrogen. ] Or a salt thereof represented by the formula

[Chemical 38] [In the formula, R represents the same as the optionally substituted hydrocarbon group in R ^2a or the optionally substituted hydrocarbon group in R ⁴ and R ⁵ , and Y represents a leaving group. ], A guanidine derivative [ ^Ia ] or a salt thereof, characterized by reacting with a compound represented by

(7) Equation

[Chemical Formula 39] [The symbols in the formulas have the same meanings as described above. ] Or a salt thereof represented by the formula

[Chemical 40] [The symbols in the formulas have the same meanings as described above. ] Reacting a compound represented by or a nitrating agent,
The present invention relates to a method for producing ^a guanidine derivative [I ^a ] or a salt thereof.

In the above formula, R ¹ represents an optionally substituted homologous or heterocyclic group. However, when X is a cyano group, R ¹ is an optionally substituted homologous or heterocyclic group excluding a pyridyl group, preferably a halogenopyridyl or halogenothiazolyl group, and more preferably a halogenothiazolyl group. Indicates a group. The homologous or heterocyclic group represented by R ¹ is a cyclic group containing only the same atom or a cyclic group containing two or more different atoms, and means a cyclic hydrocarbon group or a heterocyclic group. R ^1a represents an ^optionally substituted heterocyclic group, and those mentioned above for R ¹ are used.
Examples of the cyclic hydrocarbon group represented by R ¹ include C _3-8 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., such as cyclopropenyl, 1-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, C _3-8 cycloalkenyl groups such as 1,4-cyclohexadienyl, for example phenyl, 1- or 2-naphthyl, 1-, 2- or 9-anthryl, 1-, 2-, 3-, 4- or 9 A C _6-14 aryl group such as -phenanthryl, 1-, 2-, 4-, 5- or 6-azulenyl is used. Preferred cyclic hydrocarbon groups are, for example, aromatic ones, such as C _6-14 aryl groups such as phenyl. As the heterocyclic group represented by R ¹ or R ^1a , for example, a 5- to 8-membered ring containing 1 to 5 heteroatoms such as oxygen atom, sulfur atom, nitrogen atom or a condensed ring thereof is used, and specific examples thereof Are, for example, 2- or 3-thienyl, 2- or 3-furyl, 2- or 3-pyrrolyl, 2-, 3- or 4-pyridyl, 2-, 4- or 5-oxazolyl, 2-, 4
-Or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-imidazolyl, 3-, 4-
Or 5-isoxazolyl, 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, 1H- or 2H-tetrazolyl, N-oxide-2-, 3- or 4-pyridyl,
2-, 4- or 5-pyrimidinyl, N-oxide-2
-, 4- or 5-pyrimidinyl, 3- or 4-pyridazinyl, pyrazinyl, N-oxide-3- or 4-
Pyridazinyl, benzofuryl, benzothiazolyl, benzoxazolyl, triazinyl, oxotriazinyl,
Tetrazolo [1,5-b] pyridazinyl, triazolo [4,
5-b] pyridazinyl, oxoimidazolinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4-oxazinyl, morpholinyl, 1,4-thiazinyl, 1,3-thiazinyl, piperazinyl, benzimidazolyl, Quinolyl, isoquinolyl,
Cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolizinyl, quinolidinyl, 1,8-naphthyridinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like are used. A preferable heterocyclic group is a 5- or 6-membered nitrogen-containing heterocyclic group such as 2-, 3- or 4-pyridyl, 2-, 4- or 5-thiazolyl. Homocyclic or heterocyclic group represented by these R ^1, the heterocyclic group represented by R ^1a is the same or different substituents from 1 to 5
It may have one (preferably one), and examples of such a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl,
C1-C15 alkyl groups such as pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc., such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. Alkyl groups such as vinyl, allyl, 2-methylallyl, 2
-C2-10 alkenyl groups such as butenyl, 3-butenyl, 3-octenyl, etc., such as ethynyl, 2-propynyl, 3-hexynyl, etc. alkynyl groups, such as cyclopropenyl, cyclopentenyl,
Cycloalkenyl group having 3 to 10 carbon atoms such as cyclohexenyl, for example, 6 to 10 carbon atoms such as phenyl and naphthyl.
Aryl groups such as benzyl, phenylethyl and the like, aralkyl groups having 7 to 10 carbon atoms, nitro, hydroxyl group, mercapto, oxo, thioxo, cyano, carbamoyl, carboxyl, such as C _1-4 alkoxy-, such as methoxycarbonyl and ethoxycarbonyl. Carbonyl, sulfo,
For example, halogen such as fluorine, chlorine, bromine and iodine, for example, C _1-4 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy and t-butoxy, for example C such as phenoxy.
_6-10 aryloxy, for example, C _1-4 alkylthio such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, t-butylthio, etc., C _6-10 arylthio such as phenylthio, for example methylsulfinyl, ethylsulfinyl, etc. C _1-4 alkylsulfinyl, for example C such as phenylsulfinyl
_6-10 arylsulfinyl, for example, C _1-4 alkylsulfonyl such as methylsulfonyl and ethylsulfonyl,
For example, C _6-10 arylsulfonyl such as phenylsulfonyl, amino, C _2-6 acylamino such as acetylamino, propionylamino, etc., such as methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino. , Mono- or di-C _1-4 alkylamino such as diethylamino, C _3-6 cycloalkylamino such as cyclohexylamino, C _6-10 arylamino such as anilino, C _2-4 acyl such as acetyl, C _6-10 aryl-carbonyl such as benzoyl, for example 2- or 3-thienyl, 2- or 3-furyl, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 4-
Or 5-oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-imidazolyl, 1,
2,3- or 1,2,4-triazolyl, 1H or 2
H-tetrazolyl, 2-, 3- or 4-pyridyl, 2
-, 4- or 5-pyrimidinyl, 3- or 4-pyridanidyl, quinolyl, isoquinolyl, indolyl, etc., selected from 5 to 6-membered heterocyclic groups containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen. 1 to 5 are used.
These substituents are, for example, C _6-10 aryl, C _7-10
Aralkyl, C _3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio, C _6-10 arylsulfinyl, C _6-10 arylsulfonyl, C _6-10 arylamino, When it is a heterocyclic group or the like, further halogen, hydroxyl group as described above, for example, C _1-4 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl or t-butyl,
For example, C _2-4 such as vinyl, allyl, 2-methylallyl, etc.
Alkenyl, for example C such as ethynyl and 2-propynyl
_2-4 alkynyl, C _6-10 aryl, C _1-4 alkoxy, phenoxy, C _1-4 alkylthio, phenylthio, etc.
Five may be substituted, and the substituents are C _1-15 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C _3-6 cycloalkylamino,
When it is C _6-10 arylamino or the like, it may be further substituted with 1 to 5 halogens, hydroxyl groups, C _1-4 alkoxy, C _1-4 alkylthio or the like as described above. Preferred examples of R ¹ are 5- or 6-membered nitrogen-containing heterocycles such as pyridyl and thiazolyl which may be substituted with 1 or 2 halogens.

N represents 0 or 1, but is preferably 1.

The hydrocarbon group of the "optionally substituted hydrocarbon group" represented by R ² , R ^2a , R ^2b and R is:
The alkyl group having 1 to 15 carbon atoms described above for R ¹ , and the carbon number 3
-10 cycloalkyl group, C2-C10 alkenyl group, C2-C10 alkynyl group, C3-C10
A cycloalkenyl group, an aryl group having 6 to 10 carbon atoms,
An aralkyl group having 7 to 10 carbon atoms or the like is used. Further, as the substituent of the “hydrocarbon group which may be substituted”, those mentioned above as the substituent of the homologous or heterocyclic group represented by R ¹ are used. Preferred examples of R ² , R ^2a and R ^2b are eg hydrogen, eg methyl, ethyl,
It is a C _1-4 alkyl group such as propyl, and preferable examples of R are the above-mentioned C _1-4 alkyl groups. In addition,
In the above reaction [invention (6)], the case where the group R ^2b and the group R ^2a are different is included.

R ³ , R ^3a and R ^3b represent a primary, secondary or tertiary amino group, eg of the formula

[Chemical 41] [Wherein R ⁴ and R ⁵ are the same or different and each represents hydrogen or an optionally substituted hydrocarbon group, or R ⁴ and R ⁵
Taken together represent a cyclic amino group with the adjacent nitrogen. ]
And the like. (Here, the primary amino group is an unsubstituted amino group in which R ⁴ and R ⁵ are hydrogen in the above formula, and the secondary amino group is R ⁴ or R ^5). And a tertiary amino group means a di-substituted amino group in which neither R ⁴ nor R ⁵ is hydrogen). Examples of the “optionally substituted hydrocarbon group” represented by R ⁴ and R ⁵ include the above R ² , R ^2a and R
^Those described in ^2b and R are used. Also, R
Examples of the cyclic amino group represented by ⁴ and R ⁵ together with the adjacent nitrogen include an aziridino, azetidino, pyrrolidino, morpholino, thiomorpholino group and the like.
Preferred examples of R ³ , R ^3a and R ^3b are, for example, unsubstituted amino groups, for example, mono-C _1-4 alkylamino groups such as methylamino, ethylamino, propylamino and the like, diamines such as dimethylamino, ethylmethylamino and the like. —C _1-4 alkylamino group, for example, C _1-4 acylamino group such as formamide, N-methylformamide, acetamide and the like. In the above reaction [invention (6)], the group R ^3b
And R ^3a are different from each other.

Examples of the electron withdrawing group represented by X include cyano, nitro, alkoxycarbonyl (for example, C _1-4 alkoxy-carbonyl such as methoxycarbonyl and ethoxycarbonyl), hydroxycarbonyl, C
_6-10 aryl-oxycarbonyl (eg phenoxycarbonyl etc.), heterocyclic oxycarbonyl (heterocyclic groups such as those mentioned above are used, eg pyridyloxycarbonyl, thienyloxycarbonyl etc.), eg halogen (Cl, Br etc.) ) And the like, which may be substituted with C _1-4
Alkylsulfonyl (eg methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl etc.), sulfamoyl, di-C _1-4 alkoxyphosphoryl (eg diethoxyphosphoryl etc.), eg (Cl, Br, F
Etc.) etc. may be substituted with C _1-4 acyl (eg acetyl, trichloroacetyl, trifluoroacetyl etc.), C _6-10 aryl-carbonyl (eg benzoyl etc.), carbamoyl, C _1-4 alkylsulfonylthio. Carbamoyl (eg, methylsulfonylthiocarbamoyl etc.) and the like are used. Preferred electron withdrawing groups are, for example, nitro and the like. X ^a represents a nitro or trifluoroacetyl group. Further, X ^a may sometimes represent cyano.

Examples of the leaving group represented by Y include halogen such as chlorine, bromine, iodine and fluorine, and halogen such as methanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy and trifluoromethanesulfonyloxy (Cl, Br, C _1-4 alkylsulfonyloxy which may be substituted by 1 to 3 groups (eg, F, etc.), such as benzenesulfonyloxy, p-toluenesulfonyloxy, p-bromobenzenesulfonyloxy, mesitylenesulfonyloxy, etc. , F, etc.) 1
Up to 4 optionally substituted C _6-10 arylsulfonyloxy, such as acetyloxy, propionyloxy, trifluoroacetyloxy, and other halogens (Cl, B
1 to 3 C _1-6 acyloxy optionally substituted by R, F etc., etc., eg C _6-10 aryl-carbonyloxy such as benzoyloxy, hydroxyl group, eg C _1-4 alkoxy such as methoxy, ethoxy etc. , for example methylthio, C _1-4 alkylthio group ethylthio, e.g. C _1-4 alkylsulfinyl such as methylsulfinyl, for example C _1-4 alkylsulfonyl such as methylsulfonyl, for example phenoxy, p- chlorophenoxy, p- nitrophenoxy 1 for halogen (Cl, Br, F, etc.), nitro, etc.
1 to 3 optionally substituted C _6-10 aryloxy, for example, heterocyclic oxy such as 2-pyridyloxy and 2-benzoxazolyloxy, and nitro such as phenylthio and p-nitrophenylthio. An optionally substituted C _6-10 arylthio, such as benzylthio,
C _7-12 aralkylthio optionally substituted by 1 to 2 nitro such as p-nitrobenzylthio, heterocyclic thio such as 2-pyridylthio, 2-benzothiazolylthio, amino, such as methylamino, A mono- or di-C _1-4 alkylamino such as ethylamino and dimethylamino, and a nitrogen-containing 5-membered heterocyclic group such as 1-imidazolyl and 1,2,4-triazol-1-yl are used.

Preferred examples of Y include compounds [II] and [I
II], for example, C such as methylthio, ethylthio, etc.
_1-4 Alkylthio, such as C _7-12 aralkylthio, such as benzylthio, and C _1-4 , such as methoxy and ethoxy.
Alkoxy, amino, for example, mono- or di-C _1-4 alkylamino such as methylamino, dimethylamino and the like are used, and in the compounds [VI], [VIII] and [X], halogen such as chloro and bromo, For example, C _1-4 alkylsulfonyloxy optionally substituted with 1 to 3 halogen (s) such as methanesulfonyloxy, trifluoromethanesulfonyloxy, etc., for example, C _6-10 arylsulfonyl such as benzenesulfonyloxy, p-toluenesulfonyloxy, etc. Oxy, hydroxyl group, halogen such as acetyloxy, trifluoroacetyloxy, etc.
C _1-4 acyloxy which may be substituted with 3 or the like is used.

Preferred examples of the guanidine derivative [I] or a salt thereof include, for example,

[Chemical 42] [In the formula, R ^1b represents a pyridyl group, a halogenopyridyl group or a halogenothiazolyl group, and R ^2c , R ^4a and R ^5a are the same or different and each represent hydrogen, a methyl group, an ethyl group, a formyl group or an acetyl group. Show. ] Or a salt thereof represented by In the formula [I ^b ], R ^1b is, for example, a 3-pyridyl group, for example, a halogenopyridyl group such as 6-chloro-3-pyridyl, 6-bromo-3-pyridyl, 5-bromo-3-pyridyl, or 2 -Chloro-5
-Shows a halogenothiazolyl group such as thiazolyl and 2-bromo-5-thiazolyl.

The guanidine derivative [I] or a salt thereof produces cis and trans stereoisomers at the X position,
Further, when R ² is hydrogen and when R ³ is a primary or secondary amino group, tautomers are theoretically produced, and any of these isomers can be converted to the compound [I] of the present invention or a salt thereof. included.

[Chemical 43] [The symbols in the formulas have the same meanings as described above. ] Examples of the salts of guanidine derivatives [I], [ ^Ia ], and [ ^Ib ] include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid,
Salts with inorganic acids such as sulfuric acid and perchloric acid, for example, organic acids such as formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, benzoic acid, picric acid and p-toluenesulfonic acid are used. May be.

When the guanidine derivative [I] or a salt thereof is used as an insecticide, a form which can be taken by general pesticides, that is, one or two or more of the compound [I] or a salt thereof is suitable depending on the purpose of use. Dissolved or dispersed in a liquid carrier, or mixed or adsorbed with a suitable solid carrier to give emulsions, oils, wettable powders, powders, granules, tablets, sprays,
Used as a formulation such as ointment. These formulations may be added with, for example, emulsifiers, suspensions, spreading agents, penetrants, wetting agents, mucilages, stabilizers, etc., and can be prepared by a method known per se.

The content ratio of the active ingredient in the insecticide depends on the purpose of use, but an emulsion, a wettable powder or the like is suitable in an amount of about 10 to 90% by weight, and an oil or powder is 0.1 to 0.1% by weight.
About 10% by weight is suitable, and about 1 to 20% by weight is suitable for the granule, but these concentrations may be appropriately changed depending on the purpose of use. Emulsions, wettable powders, etc. should be diluted appropriately with water before use (eg 100 to 1).
And spread it.

The liquid carrier (solvent) used is, for example, water, alcohols (eg, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.). , Ethers (eg dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether etc.), aliphatic hydrocarbons (eg kerosene, kerosene, fuel oil, machine oil etc.), aromatic hydrocarbons Kind
(Eg, benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, etc.), acid amides (eg, dimethylformamide, dimethylacetamide, etc.), esters Solvents such as ethyl acetate, butyl acetate, fatty acid glycerin ester, etc., nitriles (eg, acetonitrile, propionitrile etc.) are suitable, and these are mixed singly or in a suitable ratio. And can be used appropriately.

As the solid carrier (diluting / extending agent), vegetable powder (for example, soybean powder, tobacco powder, wheat flour, wood powder, etc.), mineral powder (for example, kaolin, bentonite,
Clays such as acid clay, talc such as talc powder, wax stone powder, silicas such as diatomaceous earth and mica powder), alumina, sulfur powder, activated carbon, etc. are used, and one or more kinds of these are suitable. It can be mixed and used as appropriate.

As the ointment base, for example, polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate, cellulose derivatives such as methyl cellulose, sodium alginate, bentonite, higher alcohols such as glycerin. Polyhydric alcohol such as petroleum jelly, petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hydrogenated oil, resins and the like, or one or more kinds thereof, or various surfactants shown below. Those added are appropriately used.

Surfactants used as emulsifiers, spreading agents, penetrants, dispersants, etc. may be soaps, polyoxyethylene alkylaryl ethers [eg Neugen (TM: trade name, The same applies), E-A142 (E-A142) (TM); Dai-ichi Kogyo Seiyaku Co., Ltd., Nonal (TM); Toho Chemical Co., Ltd.], alkyl sulfates [eg, Emar 10 (TM)] , Emar 40 (TM); manufactured by Kao Corporation], alkyl sulfonates [eg, Neogen (TM), Neogen T]
(TM); manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neoperex (TM); Kao
Co., Ltd.], polyethylene glycol ethers [eg, Nonipol 85 (TM), Nonipol 100 (TM), Nonipol 160 (TM); Sanyo Chemical Co., Ltd.], polyhydric alcohol esters [eg, Tween 20 ( TM), Tween 80 (TM);
Nonionic and anionic surfactants such as Kao Corporation are appropriately used.

In addition, the guanidine derivative [I] or a salt thereof and other insecticides (pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides, natural insecticides, etc.), acaricides, nematicides, etc. Agents, herbicides, phytohormonal agents,
Combined with plant growth regulators, bactericides (eg copper bactericides, organochlorine bactericides, organic sulfur bactericides, phenolic bactericides, etc.), synergists, attractants, repellents, pigments, fertilizers, etc. However, it is also possible to appropriately mix and use them.

The guanidine derivative [I] and its salt are effective in controlling hygienic pests and parasitic insects of plants and animals, and exhibit a strong insecticidal action by direct contact with insects, such as direct spraying on plants and animals parasitic on the pests. However, as a more characteristic property, after the drug is once absorbed from the roots, leaves, stems, etc. into the plant, pests sucking, chewing or contacting this plant also show a strong insecticidal action. is there.
Such properties are advantageous for controlling sucking and biting insects. In addition, compound [I] and its salt have both safe and advantageous properties as a pest control agent for hygiene, horticulture, and particularly for agriculture, such as low phytotoxicity to plants and low toxicity to fish.

The preparation containing the guanidine derivative [I] or a salt thereof is specifically described, for example, in the turtle ( Eurydema ru
gosum ), rice black stink bug ( Scotinophara l urida ), long- billed stink bug ( Riptortus clavatus ), nasi gumbai ( S
tephanitis nashi ), Greater Planthopper ( Laodelphax stria
tellus ), brown planthopper ( Nilaparv ata lugens ), leafhopper leafhopper ( Nephotet tix cincticeps ), scale insect ( Unaspi s yanon ensis), soybean aphid ( Aphis )
glycines ), Japanese aphid ( Lipahph is erysi)
mi), radish aphid (Brevico ryne brassicae), cotton aphid (A phis gossypii) Hemiptera such as, for example, common cutworm (Spodoptera litura), diamondback moth (Plutel
l a xylostella ), Pieris rapae cruciv
ora ), Nikameiga ( Chilo s uppressalis ), Tamanaginuwawa ( Autographa nigrisigna ), Tobacco moth ( Helicoverpa
assulta), armyworm (Pseud aletia separata), cabbage armyworm (Mamestra brassicae), apple Coca summer fruit moth (Ado
xophyes orana fasciata ), cotton bollworm ( Notarcha der )
ogata), leaf roller (Cnaphalocrocis medinalis), potato moth (Phthorimaea operculella) lepidopteran pests such as, for example, the beetle, Epilachna Ya-spotted ladybird (Epilachna v
igintioctopunctata ), corn rootworm ( Aulacophor a femora
lis ), Phyllotreta striolata , Phylotreta striolata , Oedema beetle ( Oulema oryzae ), Weevil ( Echino )
Cnemus sq uameus ) and other beetle pests such as the housefly ( M
usc a domestica ), Culex pipiens pallen
s ), bullfly ( Tabanus trigonus ), onion fly ( Delia
antiqua ), fly ( Delia pl atur a) and other dipteran pests,
For example, locust grasshopper ( Locusta migratoria ), kerula ( G
ryll otalpa africana) Orthoptera pests such as, for example, German cockroach (Blattellagerm anica), black cockroach (P er
iplaneta fuliginosa ) etc.
( Tetranychus urticae ), citrus red mite ( Panonychus cit
ri ), kanzawa mites ( Tetranychus ka nzawai ), spider mites ( Tetranychus cinnabarinus ), apple mites ( P
anonychus ulmi ), citrus dust mite ( Aculops p elekassi ).
Spider mites, such as rice garlic nematode ( Aphe
lencho ides besseyi) are particularly effective for the control of nematodes such as.

The pesticide of the present invention thus obtained is an excellent pesticide with very little toxicity and safety. Then, 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 as compared with conventional products. For example, the insecticide of the present invention can be used for target pests by, for example, seedling raising box treatment, foliage application of crops, insect body application, underwater application of paddy fields, or soil treatment. The application rate can be varied over a wide range according to application time, application site, application method, etc., but generally 0.3 g or more of the active ingredient (guanidine derivative [I] or its salt) per hectare. 3,000
g It is desirable to apply it so that it is preferably 50 g to 1,000 g. When the insecticide of the present invention is a wettable powder, the final concentration of the active ingredient is 0.1 to 1,000 pp.
m It may be used by diluting it preferably in the range of 10 to 500 ppm.

The guanidine derivative [ ^Ia ] or its salt can be produced by the following methods (A) to (F). When compound [I ^a ] is obtained as a free compound by the following production method, it can be converted into a salt as described above, or when it is obtained in the form of a salt, to a free compound according to a conventional method. Further, when a compound contained in the compound [I ^a] is used as a raw material for producing other types of compounds [I ^a] can be used as a free left or salts. Similarly, when the other raw material can be a salt as described above, it can be used not only as a free salt but also as a salt. Thus, regarding the raw material compounds and products used in the following production methods,
The salts (for example, salts with acids as described in the above compound [I]) are also included. (A) In the present invention, a guanidine derivative [I ^a ] or a salt thereof can be produced by reacting a compound [II] or a salt thereof with ammonia, a primary amine or a secondary amine or a salt thereof. .

The ammonia, primary or secondary amines or salts thereof used in the present invention have the formula

[Chemical 44] [In the formula, R ^3a has the same meaning as described above. ] The amines or salts thereof represented by In this reaction, Y of the compound [II] is particularly preferably C _1-4 alkylthio such as methylthio, amino or the like. For compound [II] or a salt thereof,
The compound [XI] or a salt thereof is preferably used in an amount of about 0.8 to 2.0 equivalents, but about 2.0 to 2 if the reaction is not hindered.
You may use about 0 equivalent.

The reaction may be carried out without solvent, but it is usually carried out in a suitable solvent. Examples of such a solvent include water, alcohols such as methanol, ethanol, n-propanol and isopropanol, aromatic hydrocarbons such as benzene, toluene and xylene, and the like.
For example, halogenated hydrocarbons such as dichloromethane and chloroform, saturated hydrocarbons such as hexane, heptane, and cyclohexane, such as diethyl ether,
Tetrahydrofuran (hereinafter abbreviated as THF), ethers such as dioxane, ketones such as acetone,
For example, nitriles such as acetonitrile, for example, sulfoxides such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), for example, N, N-dimethylformamide.
Acid amides such as (hereinafter abbreviated as DMF), esters such as ethyl acetate, and carboxylic acids such as acetic acid and propionic acid are used. These solvents may be used alone, or if necessary, two or more kinds may be used in an appropriate ratio, for example, 1: 1 to 1:10.
You may mix and use at the ratio of. When the reaction mixture is not in a homogeneous phase, for example, the presence of a phase transfer catalyst such as quaternary ammonium salts such as triethylbenzylammonium chloride, tri-n-octylmethylammonium chloride, trimethyldecylammonium chloride, tetramethylammonium bromide and crown ethers. The reaction may be carried out below.

In this reaction, 0.01 to 1 of a base or a metal salt is used.
It may be promoted by adding 0 equivalent, preferably 0.1 to 3 equivalents. Examples of such a base include sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, phenyl lithium, butyl lithium, sodium hydride, potassium hydride, sodium methoxide. , Sodium ethoxide, metallic sodium, metallic potassium, and other inorganic bases such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, lutidine, collidine, 4- (dimethylamino) pyridine, DB
U (1,8-diazabicyclo [5,4,0] undecene-7)
An organic base such as can be used. The organic base may be used as a solvent itself. As the metal salt, for example, a copper salt such as copper chloride, copper bromide, copper acetate, copper sulfate, or a mercury salt such as mercury chloride, mercury nitrate, or mercury acetate can be used.

The reaction temperature for this reaction is usually from -20 ° C to 150 ° C.
The reaction temperature is usually 10 minutes to 50 hours, preferably 0 to 100 ° C. and 1 to 20 hours, respectively. (B) Compound [ ^Ia ] or a salt thereof can be produced by reacting raw material compound [III] or a salt thereof with compound [IV] or a salt thereof. Preferred examples of Y and reaction conditions in this reaction are the same as those described in method (A). (C) Further, the compound [V] or a salt thereof can be reacted with the compound [VI] to produce a guanidine derivative [I ^a ] or a salt thereof.

Examples of the leaving group represented by Y in the compound [VI] include halogen such as chloro and bromo, C _1-4 alkylsulfonyloxy such as methanesulfonyloxy and C such as p-toluenesulfonyloxy and the like.
_6-10 arylsulfonyloxy, for example, halogen such as acetyloxy, trifluoroacetyloxy, etc.
Particularly preferred is C _1-4 acyloxy which may be substituted with three or the like.

Compound [VI] is about 0.8 to compound [V].
It is preferable to use 1.5 equivalents, but a large excess amount may be used if the reaction is not hindered. 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 a large excess amount, preferably about 0.8 to 1.5 equivalents, relative to compound [V]. When an organic base is used as the base, it can be used as a solvent itself.

This reaction is usually preferably carried out in a solvent as described in method (A), and when the reaction system is not a homogeneous phase, a phase transfer catalyst as described in method (A) may be used. Good. The reaction temperature is generally -20 to 150 ° C, preferably 0 to
It is 80 ° C. The reaction time is usually 10 minutes to 50 hours, preferably 2 hours to 20 hours. (D) Compound [ ^Ia ] or a salt thereof can be produced by reacting raw material compound [VII] or a salt thereof with compound [VIII].

Preferred examples of Y and reaction conditions in this reaction are the same as those described in the above method (C). (E) The compound [ ^Ia ] or its salt can be produced by reacting the starting compound [IX] or its salt with the compound [X]. In this reaction, Y is, for example, C _1-4 acyloxy which may be substituted with 1 to 3 halogens such as bromo and chloro, such as acetyloxy and trifluoroacetyloxy, such as trifluoromethanesulfonyloxy. Particularly preferred is C _1-4 alkylsulfonyloxy which may be substituted with 1 to 3 halogens and the like. This reaction can be carried out under the same conditions as described in Method [C].

A compound of the formula [I ^a ] in which X ^a is a nitro group, that is, a compound of the formula

[Chemical formula 45] [In the formula, R ^1a , R ^2a and R ^3a have the same meanings as described above. ] The compound or salt thereof represented by the above method (A) to
Although it can be manufactured by (E), it can also be manufactured by the following method. (F) The compound [ ^Ia ] or a salt thereof can be produced by nitrating the compound [IX] or a salt thereof.

As the nitrating agent, 60 to 100% nitric acid is commonly used. Alkali metal nitrates such as sodium nitrate and potassium nitrate, alkyl nitrates such as ethyl nitrate and amyl nitrate, nitronium tetrafluoroborate ( NO ₂ BF ₄ ), nitronium trifluoromethanesulfonate (NO ₂ CF ₃ SO ₃ ) or the like may be used. The nitrating agent is 1.0 to 2 with respect to the compound [IX] or its salt.
It can be used in an amount of about 0 equivalent, but it is preferably 2.0 to 10 equivalents when nitric acid is used.

This reaction may be carried out without solvent, but is usually carried out using sulfuric acid, acetic acid, acetic anhydride, trifluoroacetic anhydride, trifluoromethanesulfonic acid or the like as a solvent.
Depending on the case, the solvent as described in the method (A) or a mixture thereof may be used. The reaction temperature of this reaction is -5.
The reaction time is 0 minutes to 100 ° C and the reaction time is 10 minutes to 10 hours, but preferably -20 ° C to 60 ° C and 30 minutes to 2 respectively.
It's time.

The compound [I ^a ] or a salt thereof thus obtained can be prepared by known means such as concentration, concentration under reduced pressure, distillation, fractional distillation, solvent extraction, liquid conversion, phase transfer, chromatography,
It can be isolated and purified by crystallization, recrystallization and the like.

The compounds [II] and [III] or salts thereof used as raw materials for the above-mentioned method of the present invention are partially known compounds, for example, Journal of Medicinal Chemistry (J. Med. Chem.), 20 , 901 (19
77) and Chemical and Pharmaceutical Bulletin (Chem. Pharm. Bull.), 23 , 2744 (197).
5), the method described in Japanese Patent Laid-Open No. 63-233903 or the like, or a method similar thereto, and the like.

The primary or secondary amine [XI] and the compound [IV] or salts thereof used in the above method (A) are described, for example, in "New Experimental Chemistry Course" (Maruzen), Vol. 14-III, 1332.
It can be produced by the method described on page 1399 or the like or a method similar thereto.

The compounds [V] and [IX] or their salts are
For example, Rods'S Chemistry of Carbon Compound
s), Volume 1, Part C, pages 341-353 and chemicals
Review (Chem. Reviews), can be prepared in 5 1,301 (1952) method or a process analogous to that of described in such like. Since compound [VII] or a salt thereof is included in compound [I ^a ] or a salt thereof, for example, the method described above.
It can be manufactured by (A), (B), (C), (E), (F) or the like.

The compounds [VI], [VIII] and [X] are described, for example, in "New Experimental Chemistry Course" (Maruzen), Volume 14-I, 307-45.
It can be manufactured by the method described on page 0, the same volume 14-II, pages 1104 to 1133 or the like.

[0055] Operation for guanidine derivative [I] and salts thereof have an excellent insecticidal effect and this is obvious from the following test examples.

Test Example 1 Black planthopper ( Nilaparvata l
effect on ugens ): The stem and leaves of the two-leaf stage rice seedlings grown in a nursery box containing 5 mg of the test compound (denoted by No. of the compound obtained in the following Examples) in a tween 20 (TM) ratio of 0. Dissolve with 5 ml of acetone,
Dyne diluted by 3000 times (spreading agent, manufactured by Takeda Pharmaceutical Co., Ltd.)
A prescribed concentration (500ppm) with water and a spray gun
0 ml / paper pot was sprinkled. Water was poured into the bottom of the test tube, and the treated rice seedlings were put therein, then, 10 third-instar larvae of the brown planthopper were released, and an aluminum stopper was placed. 25 this test tube
It was housed in a thermostatic chamber at 0 ° C., and dead insects were counted 7 days after the release.
The mortality rate was calculated from the following formula ([Equation 1]), and the results are shown in [Table 1].
And [Table 2].

[Equation 1]

[Table 1]

[Table 2] The [Table 1] and [Table 2] show the guanidine derivative [I].
Moreover, it has been clarified that the salt has an excellent insecticidal action against the brown planthopper.

Test Example 2 Spodoptera li
tura ): To a soybean seedling (single leaf development stage), 1 mg of a test compound (denoted by the No. of the compound obtained in the following examples) was added to Tween 20 (T).
The solution was dissolved in 0.5 ml of acetone containing M), and a predetermined concentration (500 ppm) was obtained with 3000 times diluted dyne water, and 20 ml / pot of a chemical solution was sprayed with a spray gun. After the drug solution dries, cut 2 single leaves of soybean, put them in an ice cream cup, release 10 third-instar larvae of Spodoptera litura, put the cup in the room (25 ° C) after the release, and count the dead insects after 2 days. It was
The mortality was calculated from the formula shown in Test Example 1, and the results are shown in [Table 3].

[Table 3] This [Table 3] demonstrates that the guanidine derivative [I] or a salt thereof has an excellent insecticidal action against Spodoptera litura.

Test Example 3 Aphis gossypi
Effect on i ): Each of the test compounds (denoted by No. of the compound obtained in the following Examples) was added to the foliage of cucumber in the first leaf development stage of the true leaf, which had 10 adult female aphids released 1 day before the application. Dissolve 5 mg with 0.5 ml of acetone containing Tween 20 (TM) and then use 3000 times diluted dyne water to obtain a predetermined concentration (100 p).
pm) and sprayed 10 ml / pot of the drug solution with a spray gun. The test plants were housed in a glass constant temperature chamber at 27 ° C., and the number of surviving female adults was counted 2 days after the treatment. The mortality was calculated by the following formula ([Equation 2]), and the results are shown in [Table 4] and [Table 5].

[Equation 2]

[Table 4]

[Table 5] The [Table 4] and [Table 5] show the guanidine derivative [I].
Also, it has been clarified that the salt has an excellent insecticidal action against cotton aphids.

[0059]

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

Elution by column chromatography in Examples and Reference Examples was carried out by TLC (Thin Layer Chromatograp).
hy, thin layer chromatography). In the TLC observation, as the TLC plate Merck (Merck) manufactured Kieselgel 60F ₂₅₄ (70-230
Mesh), a solvent used as an elution solvent in column chromatography as a developing solvent, and a UV detector as a detection method. As the silica gel for the column, Kieselgel 60 (70 to 230 mesh) also manufactured by Merck was used. The NMR spectrum shows proton NMR, using tetramethylsilane as an internal standard, and VARIA.
It was measured with a NEM390 (90 MHz) type spectrometer and all δ values are shown in ppm. When a mixed solvent is used as the developing solvent, the value shown in parentheses is the volume mixing ratio of each solvent.

The abbreviations used in the following examples, reference examples and [Table 6] have the following meanings.

Me: methyl group, Et: ethyl group, Ph: phenyl group, s: singlet, br: broad (wide), d: doublet, t: triplet, q: quartet, m: multiplet, dd: doublet doublet , J: Coupling constant, Hz: Hertz, CDCl ₃ : deuterated chloroform,
DMSO-d _6: heavy DMSO,%: weight%, mp: melting point Further Room temperature refers to about 15-25 ° C..

Reference Example 1 87.4 g of thionyl chloride, 100 of 1,2-dichloroethane
2-chloro-5-to 5 ml of the mixture in a water bath at 5-20 ° C.
A mixture of 70.3 g of (hydroxymethyl) pyridine and 50 ml of 1,2-dichloroethane was added dropwise over 30 minutes, and then the mixture was stirred at room temperature for 1 hour and 30 minutes and heated under reflux for 4 hours and 30 minutes. After concentration, 200 ml of chloroform and 60 ml of water were added to the residue.
Add 20 ml of sodium hydrogen carbonate with stirring and stir
Was added little by little. The organic layer was separated, treated with activated carbon and concentrated to give 75.9 g of 2-chloro-5- (chloromethyl) pyridine as a tan solid. ¹ H NMR (CDCl ₃ ): 4.57 (2H, s), 7.34 (1H, d, J = 8.5
Hz), 7.72 (1H, dd, J = 8.5,2.5Hz), 8.40 (1H, d, J = 2.5Hz) Similarly, 5- (chloromethyl) thiazole, 5- (chloromethyl) -2-methylthiazole And 5- (chloromethyl) -2-phenylthiazole were obtained.

Reference Example 2 2-chloro-5- (chloromethyl) pyridine 14.99 g,
25% ammonia water 63.01 g, acetonitrile 60 ml
The mixture was placed in a pressure resistant reaction vessel made of stainless steel and stirred in an oil bath at 80 ° C. for 2 hours. To the reaction mixture was added 30% aqueous sodium hydroxide solution (12.3 g) and the mixture was concentrated. 200 ml of ethanol was added to the residue, dried over anhydrous magnesium sulfate, and the insoluble material was filtered off. After concentration of the filtrate, column chromatography (developing solvent; dichloromethane-methanol)
(4: 1)) and 7.66 g of 5- (aminomethyl)-
2-Chloropyridine was obtained as a yellow solid. ¹ H NMR (CDCl ₃ ): 1.60 (2H, s), 3.90 (2H, s), 7.2
8 (1H, d, J = 8.5Hz), 7.67 (1H, dd, J = 8.5,2.5Hz), 8.33
(1H, d, J = 2.5Hz) Similarly, 5- (aminomethyl) -2-bromopyridine,
5- (aminomethyl) -2-chlorothiazole, 3-cyanobenzylamine, 5- (aminomethyl) thiazole, 5
-(Aminomethyl) -2-methylthiazole, 5- (aminomethyl) -2-phenylthiazole and 5- (aminomethyl) -2- (trifluoromethyl) thiazole were obtained.

Reference Example 3 36 g of 40% aqueous methylamine solution and 20% of acetonitrile
A mixed solution of 15.05 g of 2-chloro-5- (chloromethyl) pyridine and 50 ml of acetonitrile was added dropwise to the mixed solution of 0 ml at room temperature over 1 hour, and the mixture was further stirred for 1 hour and 30 minutes. The reaction mixture was concentrated, 100 ml of water was added to the residue, the mixture was neutralized with sodium chloride, saturated with sodium chloride, extracted with dichloromethane (200 ml × 2), and the organic layer was dried over anhydrous magnesium sulfate and concentrated. Column chromatography
(Developing solvent; dichloromethane-methanol (4: 1)) to give 8.77 g of 2-chloro-5- (methylaminomethyl) pyridine as a tan liquid. ¹ H NMR (CDCl ₃ ): 1.30 (1H.br.s), 2.44 (3H, s),
3.75 (2H, s), 7.30 (1H, d, J = 8.4Hz), 7.68 (1H, dd, J = 8.
4,2.4Hz), 8.35 (1H, d, J = 2.4Hz)

Reference Example 4 6.30 g of trifluoroacetic anhydride was added dropwise to a mixture of 3.15 g of dithioiminocarbonic acid S, S'-dimethyl hydrochloride and 30 ml of pyridine in a water bath at 20 ° C. for 30 minutes, and then stirred for 5 hours. did. The reaction mixture was concentrated, 20 ml of water was added to the residue, and the mixture was extracted with dichloromethane (30 ml). The organic layer was dried over anhydrous magnesium sulfate and concentrated, and the residue was purified by column chromatography (developing solvent: dichloromethane), and 2.33 g of N-trifluoroacetyldithioiminocarbonate S, S'-dimethyl as a yellow liquid. Obtained. ¹ H NMR (CDCl ₃ ): 2.66 (s)

Reference Example 5 N-cyanodithioiminocarbonate S, S'-dimethyl 1.0 g,
To a mixture of 15 ml of isopropyl alcohol, 0.89 g of 5- (aminomethyl) -2-chloropyridine was heated under reflux.
5 ml of isopropyl alcohol was added dropwise over 30 minutes, and the mixture was heated under reflux for 1 hour and 30 minutes. The reaction mixture was ice-cooled, the resulting white solid was collected by filtration, and 1.35 g of 1- (6
-Chloro-3-pyridylmethyl) -3-cyano-2-methylisothiourea was obtained. ¹ H NMR (CDCl ₃ ): 2.63 (3H, s), 4.51 (2H, d, J = 6H
z), 7.51 (1H, d, J = 8Hz), 7.83 (1H, dd, J = 8,3Hz), 8.38 (1
H, d, J = 3Hz), 8.95 (1H, 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-5-thiazolylmethyl) -3-cyano-2
-Methylisothiourea was obtained.

Reference Example 6 After washing 0.80 g of 60% sodium hydride (oil-based) with petroleum ether, 20 ml of DMF was added. A solution of 2.58 g of 3-cyano-1,2-dimethylisothiourea in 10 ml of DMF was added dropwise to this suspension at room temperature over 10 minutes. After stirring for 1 hour, 2-chloro-5- (chloromethyl) pyridine 3.2
4 g 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 dichloromethane 10 was added to the residue.
0 ml was added and washed with water, and the organic layer was dried over anhydrous magnesium sulfate. After concentration, purification by column chromatography (developing solvent; chloroform-ethanol (20: 1)),
3.50 g of 1- (6-chloro-3-pyridylmethyl) -3
-Cyano-1,2-dimethylisothiourea was obtained as a yellow liquid. ¹ H NMR (CDCl ₃ ): 2.84 (3H, s), 3.20 (3H, s), 4.82
(2H, s), 7.35 (1H, d, J = 8Hz), 7.63 (1H, dd, J = 8.2Hz),
8.31 (1H, d, J = 2Hz) Similarly, 1- (6-chloro-3-pyridylmethyl) -3
-Cyano-1-ethyl-2-methylisothiourea, 1-
(6-chloro-3-pyridylmethyl) -1,2-dimethyl-3-nitroisothiourea, 1- (6-chloro-3-pyridylmethyl) -1-ethyl-2-methyl-3-nitroisothiourea, 1- (2-chloro-5-thiazolylmethyl) -1-ethyl-2-methyl-3-nitroisothiourea and 1- (2-chloro-5-thiazolylmethyl) -1,
2-Dimethyl-3-nitroisothiourea was obtained.

Reference Example 7 2-Chloro-5-aminopyridine 4.07 g, isothiol
A mixture of 2.55 g of methyl cyanate and 30 ml of acetonitrile
The mixture was heated under reflux for 13.5 hours and then isothiocyanate was added.
Add 0.70 g of methyl acidate and heat to reflux for another 3.5 hours.
did. The reaction mixture is concentrated and the residue is subjected to column chromatography.
Raffy (developing solvent; dichloromethane-ethyl acetate (1:
1)) and 4.51 g of 1- (6-chloro-3-pyrrole).
Zil) -3-methylthiourea was obtained. mp.164-16
4.5 ° C (recrystallized from acetonitrile) ¹ 1 H NMR (CDCl₃): 3.12 (3H, d, J = 4.8Hz), 6.86 (1H,
br.q, J = 4.8Hz), 7.33 (1H, d, J = 8.5Hz), 7.86 (1H, dd, J
= 8.5,2.8Hz), 8.31 (1H, d, J = 2.8Hz), 8.63 (1H, br.s)

Reference Example 8 A mixture of 4.45 g of 2-bromo-5-methylthiazole, 4.89 g of N-bromosuccinimide, 0.2 g of benzoyl peroxide and 50 ml of carbon tetrachloride was heated and refluxed for 50 minutes, then at room temperature. Let it cool down. After the insoluble matter was filtered off, the filtrate was concentrated. The residue was purified by column chromatography (developing solvent; hexane-dichloromethane (2: 3)) to obtain 4.53 g of 2-bromo-5- (bromomethyl) thiazole as a yellow solid. ¹ H NMR (CDCl ₃ ): 4.64 (2H, s), 7.54 (1H, s) In the same manner, 5- (bromomethyl) -3- (difluoromethyl) -2-thiazolone was obtained.

Reference Example 9 To a mixture of 1.85 g of potassium phthalimide and 20 ml of dry DMF, 2.57 g of 2-bromo-5- (bromomethyl) thiazole was added little by little over 20 minutes at room temperature, followed by stirring for 1 hour. The insoluble matter was filtered off, the filtrate was concentrated, 30 ml of ethanol was added, and 0.60 g of hydrazine hydrate was added dropwise in an oil bath at 20 ° C. over 2 minutes. The reaction mixture was heated under reflux for 1 hour, concentrated, 20 ml of water and 10 ml of concentrated hydrobromic acid were added, and the mixture was heated under reflux for 30 minutes. After neutralizing with a 20% aqueous sodium hydroxide solution in the cold, the mixture was concentrated, 50 ml of acetonitrile was added to the residue, and the insoluble material was filtered off. The filtrate was concentrated and then purified by column chromatography (developing solvent; dichloromethane-methanol (5: 1)) to obtain 0.76 g of 5- (aminomethyl) -2-bromothiazole as a brown oil. ¹ H NMR (CDCl ₃ ): 1.59 (2H, s), 4.06 (2H, d, J = 1.2
Hz), 7.40 (1H, t, J = 1.2Hz)

Reference Example 10 0.88 g of diethylamine was added to a mixture of 1.35 g of S-methyl-N-nitroisothiourea and 5 ml 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 ¹ H NMR (CDCl ₃ ): 1.23 (6H, t, J = 7.2Hz), 3.47 (4H,
q, J = 7.2Hz), 7.93 (2H, br.s)

Reference Example 11 Pyrrolidine (0.61) was added to a mixture of 1.0 g of S-methyl-N-nitroisothiourea and 15 ml of acetonitrile at room temperature.
g was added dropwise over 2 minutes and then stirred for 30 minutes. The reaction mixture is concentrated, the residual solid is washed with ether,
1.09 g of 1- (N-nitroamidino) pyrrolidine was obtained as white crystals. mp. 188 to 191 ° C. ¹ H NMR (DMSO-d ₆ ): 1.7 to 2.1 (4 H, m), 3.2 to 3.5 (4
H, m), 8.19 (2H, br.s) In a similar manner, N-ethyl-N-methyl-N'-nitroguanidine (mp. 124-125 ° C) was obtained.

Reference Example 12 A mixture of 5.0 g of S-methyl-N-nitroisothiourea and 25 ml of pyridine was mixed with 10% of 11.3 g of acetic anhydride at room temperature.
Dropped in minutes. After the dropwise addition, the mixture was stirred at room temperature for 5 hours, and the reaction mixture was concentrated. The residue is poured into 50 ml of 2N hydrochloric acid,
The resulting solid was collected by filtration and dried to obtain 5.1 g of N-acetyl-S-methyl-N'-nitroisothiourea as white crystals. mp. 109-110 ° C ¹ H NMR (CDCl ₃ ): 2.30 (3H, s), 2.42 (3H, s), 11.2
0 ~ 12.00 (1H, br.)

Reference Example 13 2-hydroxy-5-methylthiazole (5-methyl-
2-thiazolone) 11.5 g, dioxane 100 ml, 40
To a mixture of 100% aqueous sodium hydroxide solution at 80 ° C.
Chlorodifluoromethane (gaseous) was bubbled in for 1 hour in an oil bath. The reaction mixture was poured into 500 ml of water and extracted twice with ether. The ether layer was dried over anhydrous magnesium sulfate and then concentrated, and the residue was subjected to column chromatography (developing solvent; dichloromethane-hexane (1:
1)) to give 2.0 g of 2- (difluoromethoxy) -5-methylthiazole ( ¹ H NMR (CDCl
₃ ): 2.35 (3H, d, J = 1.5Hz), 6.88 (1H, br.q, J = 1.5Hz), 7.1
8 (1H, t, J = 72.0Hz)) and 4.0g of 3- (difluoromethyl) -5-methyl-2- thiazolones ⁽¹ H NMR (CDCl
₃ ): 2.16 (3H, d, J = 1.5Hz), 6.51 (1H, br.q, J = 1.5Hz), 7.0
7 (1H, t, J = 60.0Hz)) was obtained. Both are pale yellow liquids.

Reference Example 14 2,2,2-trifluorothioacetamide 11.22
g, 2-chloro-2-formyl ethyl acetate 10.14 g
The mixture was stirred in an oil bath at 70 ° C. for 30 minutes and then in an oil bath at 100 ° C. for 1 hour and 30 minutes, and then dichloromethane 1
00 ml was added to remove insoluble matter. After concentration, column chromatography (developing solvent; hexane-ethyl acetate (1
0: 1)) to give 3.74 g of ethyl 2- (trifluoromethyl) -5-thiazolecarboxylate as a yellow liquid. ¹ H NMR (CDCl ₃ ): 1.41 (3H, t, J = 7.2Hz),
4.43 (2H, q, J = 7.2Hz), 8.50 (1H, s). Lithium aluminum hydride 0.50g, dry THF8
To 0 ml of the mixture was added dropwise at room temperature a solution of 2.51 g of ethyl thiazolecarboxylate in 10 ml of THF over 45 minutes,
Stirred for another 30 minutes. To the reaction mixture cooled with a freezing medium, 0.5 ml of water and 0.5% of 10% aqueous sodium hydroxide solution were added.
ml and 1.5 ml of water were added dropwise in this order. After further stirring in an ice bath for 10 minutes and room temperature for 30 minutes, the insoluble matter was filtered off on Celite. After concentrating the filtrate, chloroform 1
00 ml was added, dried over anhydrous magnesium sulfate, and concentrated to give 1.24 g of 5- (hydroxymethyl)-.
2- (Trifluoromethyl) thiazole was obtained as a brown liquid. ¹ H NMR (CDCl ₃ ): 3.45 (1H, br.s), 4.93 (2H,
s), 7.77 (1H, s) To a mixture of 0.4 ml of thionyl chloride and 1 ml of 1,2-dichloroethane, a solution of 0.80 g of thiazole in 2 ml of 1,2-dichloroethane was added dropwise over 10 minutes in an oil bath at 40 ° C. Then
The mixture was stirred at the same temperature for another hour. Dichloromethane (2 ml) and water (2 ml) were added to the reaction mixture, and then a heavy tank was added while stirring 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 material was filtered off, washed with saturated brine, and dried over anhydrous magnesium sulfate. After concentration, 0.74 g of 5-
(Chloromethyl) -2- (trifluoromethyl) thiazole was obtained as a reddish brown liquid. ¹ H NMR (CDCl ₃ ): 4.84 (2H, s), 7.90 (1H, s)

Example 1 1- (6-chloro-3-pyridylmethyl) -3-cyano-
To a mixture of 0.42 g of 1-ethyl-2-methylisothiourea and 5 ml of acetonitrile, 0.5 g of a 40% methylamine aqueous solution was added under heating and refluxing 6 times every hour (total 3.0 g), and the reaction mixture was mixed with 6 I stirred it for a while. 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. mp 122-123 ° C ¹ H NMR (DMSO-d ₆ ): 1.07 (3H, t, J = 7Hz), 3.00
(3H, d, J = 5Hz), 3.35 (2H, q, J = 7Hz), 4.62 (2H, s), 7.23
(1H, br.s), 7.50 (1H, d, J = 8Hz), 7.78 (1H, dd, J = 8,3H
z), 8.33 (1H, d, J = 3Hz)

Example 2 0.44 g of 60% sodium hydride (oil), dry DMF1
1.32 g of N, N-dimethyl-N'-nitroguanidine were added to 0 ml of the suspension at room temperature over 20 minutes. After stirring for 10 minutes, 2-chloro-5- (chloromethyl) pyridine 1.6
2 g was added over 5 minutes and then stirred for 2 hours at room temperature and 4 hours in an oil bath at 60 ° C. The insoluble material was filtered off, the filtrate was concentrated, and the residue was purified by column chromatography (developing solvent; dichloromethane-ethyl acetate 5: 1 to 3: 1) to give 0.82 g of 1- (6-chloro-3. -Pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound N
o.6) was obtained. mp 160.5 to 162.5 ° C Elemental analysis (C ₉ H ₁₂ N ₅ O ₂ Cl) Calculated value C: 41.95 H: 4.69 N: 27.18 Measured value C: 41.73 H: 4.59 N: 26.94 ¹ H NMR (CDCl ₃ ): 3.10 (6H, s), 4.49 (2H, br.s),
7.27 (1H, d, J = 8.5Hz), 7.70 (1H, dd, J = 8.5,2.5Hz), 8.2
~ 8.5 (2H, m)

Example 3 0.45 g of 1,2-dimethyl-3-nitroisothiourea
A mixture of 0.43 g of 5- (aminomethyl) -2-chloropyridine and 25 ml of ethanol was heated under reflux for 6 hours and then concentrated. The residue was purified by column chromatography (developing solvent; chloroform-ethanol (5: 1)) to give 0.25 g.
1- (6-chloro-3-pyridylmethyl) -3-methyl-2-nitroguanidine (Compound No. 5) was obtained. mp 150 to 152 ° C. Elemental analysis _{(C 8 H 10 N 5 O} 2 Cl) Calculated C: 39.44 H: 4.14 N: 28.74 Found C: 39.92 H: 4.12 N: 28.91 1 H NMR (CDCl 3 -DMSO-d ₆ ): 2.94 (3H, d, J = 5
Hz), 4.51 (2H, d, J = 5Hz), 7.32 (1H, d, J = 8Hz), 7.75 (1
H, dd, J = 8,2Hz), 7.82 (1H, br.s), 8.37 (1H, d, J = 2Hz),
8.90 (1H, br.s)

Example 4 S-Methyl-N-nitroisothiourea 0.676 g, 2-
Chloro-5- (methylaminomethyl) pyridine 0.783
The mixture of g and 6 ml 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 8 H 10 N 5 O} 2 Cl) Calculated C: 39.44 H: 4.14 N: 28.74 Found C: 39.89 H: 4.07 N: 28.85 1 H NMR (DMSO-d 6): 3.01 (3H, s), 4.70 (2H, s),
7.48 (1H, d, J = 8.4Hz), 7.78 (1H, dd, J = 8.4,2.2Hz), 8.3
7 (1H, d, J = 2.2Hz), 8.56 (2H, br.s)

Example 5 A mixture of 0.82 g of 1- (6-chloro-3-pyridylmethyl) -1,2-dimethyl-3-nitroisothiourea, 0.464 g of 40% aqueous methylamine solution and 10 ml of acetonitrile at 70 ° C. Stirred for 2 hours. The reaction mixture was concentrated and then purified by column chromatography (developing solvent; dichloromethane-methanol (10: 1)) to give 0.56 g of 1
-(6-Chloro-3-pyridylmethyl) -1,3-dimethyl-2-nitroguanidine (Compound No. 8) was obtained. mp
One hundred thirty-six to one hundred and thirty-seven ° C. Elemental analysis _{(C 9 H 12 N 5 O} 2 Cl) Calculated C: 41.95 H: 4.69 N: 27.18 Found C: 41.89 H: 4.75 N: 27.15 1 H NMR (CDCl 3): 2.96 ( 3H, d, J = 4.8Hz), 3.05 (3
H, s), 4.67 (2H, s), 7.33 (1H, d, J = 8.3Hz), 7.68 (1H, dd,
J = 8.3,2.4Hz), 7.96 (1H, br.q, J = 4.8Hz), 8.30 (1H, d, J
= 2.4Hz)

Example 6 A mixture of 0.53 g of nitroguanidine, 0.61 g of 3- (aminomethyl) pyridine and 10 ml of water at 70-80 ° C.
Stir for 5 hours. After standing overnight at room temperature, the deposited precipitate was collected by filtration, washed with ethanol, and 0.48 g of N-nitro-
N '-(3-pyridylmethyl) guanidine (Compound No. 12)
Got mp. 185-190 ° C ¹ H NMR (DMSO-d ₆ ): 4.47 (2H, d, J = 5Hz), 7.40 (1H, d
d, J = 6,4Hz), 7.67 ~ 7.85 (1H, m), 7.85 ~ 8.30 (2H, br.
s), 8.47 ~ 8.67 (2H, m)

Example 7 60% hydrogenation at room temperature in a mixture of 0.24 g of 1- (6-chloro-3-pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound No. 6) and 6 ml of dry THF at room temperature. After adding 0.045 g of sodium (oil), the mixture was stirred for 30 minutes. To the reaction mixture, 0.16 g of iodomethane in 1 ml of THF
After adding the solution and reacting for 3 days, 0.1 ml of acetic acid was added, the insoluble matter was filtered off, and the filtrate was concentrated. The residue was purified by column chromatography (developing solvent; dichloromethane-methanol (20: 1)) and 0.17 g of 1- (6-chloro-3-pyridylmethyl) -1,3,3-trimethyl-
2-Nitroguanidine (Compound No. 14) was obtained as a white solid. Elemental analysis _{(C 10 H 14 N 5 O} 2 Cl) Calculated C: 44.21 H: 5.19 N: 25.78 Found C: 44.14 H: 5.14 N: . 25.61 mp 99~101 ℃ 1 H NMR (CDCl 3): 2.90 (3H, s), 3.02 (6H, s), 4.03
(2H, s), 7.38 (1H, d, J = 8.5Hz), 7.79 (1H, dd, J = 8.5,2.
7Hz), 8.37 (1H, d, J = 2.7Hz)

Example 8 A mixture of 0.26 g of 1- (6-chloro-3-pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound No. 6) and 3 ml of dry THF was placed in a water bath at 20 ° C. At 60%, 0.08 g of sodium hydride (oil-based) was added, and the mixture was stirred for 30 minutes. Formic acid acetic anhydride 0.26 g of THF was added to the reaction mixture.
A 0.5 ml solution was added over 1 minute, the bath removed and stirring continued for a further 12 hours. After adding 0.5 ml of acetic acid to the reaction mixture, the mixture was concentrated, and the residue was subjected to column chromatography (developing solvent;
Purify with dichloromethane-methanol (30: 1)) and
10 g of 1- (6-chloro-3-pyridylmethyl) -1-
Formyl-3,3-dimethyl-2-nitroguanidine (Compound No. 22) was obtained as a syrup-like liquid. ¹ H NMR (CDCl ₃ ): 3.03 (6H, s), 4.70 (2H, s), 7.3
6 (1H, d, J = 8.7Hz), 7.74 (1H, dd, J = 8.7,2.7Hz), 8.40 (1
H, d, J = 2.7Hz), 8.44 (1H, s)

Example 9 0.20 g of 1- (6-chloro-3-pyridylmethyl) -3,3-dimethyl-2-nitroguanidine (Compound No. 6),
A mixture of 0.095 g of acetic anhydride and 1 ml of dry pyridine was added to 6 parts.
The mixture was stirred at 0 ° C for 2 hours and at 100 ° C for 5 hours, and then concentrated. The residue was purified by column chromatography (developing solvent; dichloromethane-methanol (40: 1)) to give 0.1
2 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 isomers). It was ¹ H NMR (CDCl ₃ ): 2.10 + 2.16 (3H, S + S), 2.6-
3.3 (6H, m), 4.1 ~ 5.2 (2H, m), 7.23 ~ 7.45 (1H, m), 7.67
~ 7.90 (1H, m), 8.30 ~ 8.50 (1H, m)

Example 10 A mixture of 1.03 g of 1- (6-chloro-3-pyridyl) -3-methylthiourea, 0.32 g of cyanamide, 1.58 g of dicyclohexylcarbodiimide, 3 drops of ethyldiisopropylamine and 10 ml of acetonitrile for 34 hours. After stirring at room temperature, insoluble matter was collected by filtration. This insoluble material was first recrystallized from a mixed solvent of acetonitrile: methanol and then recrystallized from acetonitrile to give 0.31 g of 1- (6-chloro-3-pyridyl) -2-cyano-3-methylguanidine (compound No. 24) was obtained. mp. 227-
228 ° C. Elemental analysis value (C ₈ H ₈ N ₅ Cl) Calculated value: C: 45.84 H: 3.85 N: 33.41 Measured value: C: 46.12 H: 3.68 N: 33.37 ¹ H NMR (DMSO-d ₆ ): 2.85 ( 3H, d, 4.8Hz), 7.2〜
7.65 (2H, m), 7.83 (1H, dd, J = 8.5,3.0Hz), 8.36 (1H, d, J
= 3.0Hz), 9.06 (1H, br.s)

Example 11 5- (Aminomethyl) -2-bromothiazole 0.39
g, 1,2-dimethyl-3-nitroisothiourea 0.30
g, cuprous bromide 0.58 g, anhydrous potassium carbonate 0.55
g, 4 ml of dry acetonitrile was stirred in an oil bath at 60 ° C. for 45 minutes, and the reaction mixture was purified by column chromatography (developing solvent: dichloromethane-methanol (10: 1)) to give 0.27 g of 1- (2-Bromo-5-thiazolylmethyl) -3-methyl-2-nitroguanidine (Compound No. 39) was obtained as a white solid. mp
170 ° C. Elemental analysis value (C ₆ H ₈ N ₅ O ₂ SBr) Calculated value C: 24.50 H: 2.74 N: 23.81 Measured value C: 24.47 H: 2.73 N: 23.73 ¹ H NMR (DMSO-d ₆ ): 2.81 ( 3H, d, J = 5.0Hz), 4.51
(2H, s), 7.60 (1H, s), 8.08 (1H, br.s), 8.93 (1H, br.s)

Example 12 A mixture of N-acetyl-S-methyl-N'-nitroisothiourea (0.5 g) and acetonitrile (5 ml) was cooled with ice to give 5
A solution of 0.44 g of-(aminomethyl) -2-chloropyridine in 3 ml of acetonitrile was added dropwise, and the mixture was further stirred for 30 minutes under ice 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.
25 to 126 ° C. Elemental analysis value (C ₉ H ₁₀ N ₅ O ₃ Cl) Calculated value C: 39.79 H: 3.71 N: 25.78 Measured value C: 39.71 H: 3.69 N: 25.51 ¹ H NMR (CDCl ₃ ): 2.33 ( 3H, s), 4.60 (2H, d, J = 6.0
Hz), 7.33 (1H, d, J = 7.8Hz), 7.50 ~ 7.87 (1H, m), 8.37 (1H,
d, J = 2.5Hz), 9.70 (1H, br.s), 11.85 (br.s) The compounds shown in the following [Table 6] to [Table 15] according to the above Examples 1 to 12 and the production method of the present invention. Got The compounds obtained in the above Examples are shown in [Table 6] to [Table 15].

[0089]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

Example 13 Compound No. 1 (20% by weight), xylene (75% by weight), polyoxyethylene glycol ether (Nonipol 85)
(TM)) (5% by weight) was mixed well to prepare an emulsion.

Example 14 Compound No. 6 (30% by weight), sodium ligninsulfonate (5% by weight), polyoxyethylene glycol ether (Nonipol 85 (TM)) (5% by weight), white carbon
(30% by weight) and clay (30% by weight) were mixed well to prepare a wettable powder.

Example 15 A powder was prepared by thoroughly mixing Compound No. 7 (3% by weight), white carbon (3% by weight) and clay (94% by weight).

Example 16 Compound No. 8 (10% by weight), sodium ligninsulfonate (5% by weight) and clay (85% by weight) were well pulverized and mixed, and water was added to the mixture, which was well kneaded, and then granulated and dried. To produce granules.

[0094]

INDUSTRIAL APPLICABILITY The present invention contributes to agriculture by providing an excellent insecticide.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C07D 241/12 277/28 277/32 521/00 (72) Inventor Isao Minanda Inagawa, Kawabe-gun, Hyogo 2-chome, Fushimidai 91 (72) Inventor Tetsuo Okauchi 10-11 Tsutsumicho, Hirakata-shi, Osaka

Claims (11)

[Claims] 1. A general formula [I]: [In the formula, R ¹ is C _3-8 cycloalkyl, C _3-8 cycloalkenyl, homocyclic group selected from C _6-14 aryl, or an oxygen atom, a hetero atom selected from sulfur atom and a nitrogen atom 5 to 8-membered heterocyclic groups containing 1 to 5 are shown. These homologous or heterocyclic groups are C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C
_3-10 cycloalkenyl, C _6-10 aryl, C _7-10 aralkyl, nitro, hydroxyl group, mercapto, oxo, thioxo, cyano, carbamoyl, carboxyl, C _1-4 alkoxy-carbonyl, sulfo, halogen, C _1-4 Alkoxy, C _6-10 aryloxy, C _1-4 alkylthio, C
_6-10 arylthio, C _1-4 alkylsulfinyl, C
_6-10 arylsulfinyl, C _1-4 alkylsulfonyl, C _6-10 arylsulfonyl, amino, C _2-6 acylamino, mono- or di-C _1-4 alkylamino, C _3-6 cycloalkylamino, C _{6 -10} arylamino, C _2-4 acyl, C _6-10 aryl-carbonyl, and 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen 5
It may have 1 to 5 substituents (A) selected from 6-membered heterocyclic groups, and the substituents (A) are C _6-10 aryl, C _7-10
Aralkyl, C _3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio,
In the case of C _6-10 arylsulfinyl, C _6-10 arylsulfonyl, C _6-10 arylamino or a heterocyclic group, 1 to 5 halogens, hydroxyl group, C _1-4 alkyl,
C _2-4 alkenyl, C _2-4 alkynyl, C _6-10 aryl,
It may be substituted with a C _1-4 alkoxy, phenoxy, C _1-4 alkylthio or phenylthio group, and the above substituents are C _1-15 alkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _{1- 4} Alkoxy, C _1-4 alkylthio, C _1-4
Alkylsulfinyl, C _1-4 alkylsulphonyl, amino, mono- or di-C _1-4 alkylamino, C _3-6 cycloalkylamino or C _6-10 arylamino groups having 1 to 5 halogens. , Hydroxyl group, C _1-4 alkoxy or C _1-4 alkylthio group. R ² is a hydrogen atom, C _1-15 alkyl, C
A hydrocarbon group selected from _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups is shown. May have 1 to 5 substituents similar to R ¹ . R ³ is the formula: (In the formula, R ⁴ and R ⁵ are the same or different and represent hydrogen or a hydrocarbon group which may have a substituent, or R ⁴ and R ⁵ are taken together to form a cyclic amino group together with an adjacent nitrogen. The hydrocarbon group may be a C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C group.
_2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the hydrocarbon group has a substituent similar to the substituent in the heterocyclic group of R ^1. You may have. The cyclic amino group is selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. ) Represents an amino group. X
Is cyano, nitro, C _1-4 alkoxy-carbonyl,
Hydroxycarbonyl, C _6-10 aryl-oxycarbonyl, heterocyclic oxycarbonyl, C _1-4 alkylsulfonyl optionally substituted with halogen, sulfamoyl, di-C _1-4 alkoxyphosphoryl, optionally substituted with halogen _{Represents a} good C _1-4 acyl, C _6-10 aryl-carbonyl, carbamoyl or C _1-4 alkylsulfonylthiocarbamoyl. However, when (i) n is 0,
R ¹ represents a heterocyclic group which may have a substituent, and (ii) when X is a nitro group, R ¹ has the same meaning as the above, which may have a substituent. Or a heterocyclic group, n is 0 or 1, R ² is a C _1-4 alkyl having a substituent, or C optionally having a substituent.
_5-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C
_6-10 aryl or C _7-10 aralkyl group, and these substituents are the same as the above-mentioned substituents of R ² , R ³
Represents the same meaning as above, and (iii) when X is a nitro group, R ¹ represents a homologous or heterocyclic group which may have a substituent having the same meaning as above. , N is 0 or 1, R ² is a hydrogen atom or C
_{1-4 is} alkyl, and R ³ is of the formula: (In the formula, one of R ⁴ and R ⁵ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the hydrocarbon group is a C _1-15 alkyl group or a C _3-10 cycloalkyl group. , C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the hydrocarbon group is the above-mentioned R ¹ heterocycle. The same as the substituents on the ring group are shown, the other is a C _1-4 alkyl having a substituent or a hydrocarbon group which may have a substituent, and the hydrocarbon group is a C _5-15 alkyl. , C _3-10
Cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C
Selected from a _7-10 aralkyl group, and the substituent of the C _1-4 alkyl hydrocarbon group and the substituent of the hydrocarbon group are the same as the above-mentioned substituents in the heterocyclic group of R ¹ , or R ⁴ and R ⁵ together with the adjacent nitrogen form a cyclic amino group selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. And (iv) when X is a cyano group, R ¹ is a heterocyclic group which may have a substituent and which does not have a substituent. Except for. ] The insecticide composition containing the guanidine derivative or its salt represented by these. 2. The insecticide composition according to claim 1, wherein X in the general formula [I] is a nitro group. 3. The insecticide composition according to claim 1, wherein X in the general formula [I] is a cyano group. 4. A compound represented by the general formula [I ^a ] [In the formula, R ^1a represents a 5- to 8-membered heterocyclic group containing 1 to 5 heteroatoms selected from oxygen atom, sulfur atom and nitrogen atom, and the heterocyclic group is C _1-15 alkyl, C _{3 -10} cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10
Cycloalkenyl, C _6-10 aryl, C _7-10 aralkyl, nitro, hydroxyl group, mercapto, oxo, thioxo,
Cyano, carbamoyl, carboxyl, C _1-4 alkoxycarbonyl, sulfo, halogen, C _1-4 alkoxy,
C _6-10 aryloxy, C _1-4 alkylthio, C _6-10 arylthio, C _1-4 alkylsulfinyl, C _6-10 arylsulfinyl, C _1-4 alkylsulfonyl, C _6-10
Arylsulfonyl, amino, C _2-6 acylamino, mono- or di-C _1-4 alkylamino, C _3-6 cycloalkylamino, C _6-10 arylamino, C _2-4 acyl, C
_6-10 arylcarbonyl and _optionally 1 to 5 substituents (A) selected from 5 to 6 membered heterocyclic groups containing 1 to 4 heteroatoms selected from oxygen, sulfur and nitrogen , Wherein the substituent (A) is C _6-10 aryl, C
_7-10 aralkyl, C _3-10 cycloalkyl, C _3-10 cycloalkenyl, C _6-10 aryloxy, C _6-10 arylthio, C _6-10 arylsulfinyl, C _6-10 arylsulfonyl, C _6-10 When it is an arylamino or a heterocyclic group, it further has 1 to 5 halogens, a hydroxyl group, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _6-10 aryl, C _1-4 alkoxy, It may be substituted with a phenoxy, C _1-4 alkylthio or phenylthio group, and the above substituents are C _1-15 alkyl, C _2-10 alkenyl, C
_2-10 alkynyl, C _1-4 alkoxy, C _1-4 alkylthio, C _1-4 alkylsulfinyl, C _1-4 alkylsulfonyl, amino, mono- or di-C _1-4 alkylamino, C _3-6 cyclo When it is an alkylamino or C _6-10 arylamino group, it may be further substituted with 1 to 5 halogens, hydroxyl groups, C _1-4 alkoxy or C _1-4 alkylthio groups. R ^2a is a hydrogen atom, C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C
_2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl, and a hydrocarbon group selected from C _7-10 aralkyl group. These hydrocarbon groups have the same substituents as R ^1a .
You may have five. R ^3a has the formula: (In the formula, R ⁴ and R ⁵ are the same or different and represent hydrogen or a hydrocarbon group which may have a substituent, or R ⁴ and R ⁵ are taken together to form a cyclic amino group together with an adjacent nitrogen. The hydrocarbon group may be a C _1-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _{2-10 group.}
Selected from alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, the hydrocarbon group having a substituent similar to the substituent in the heterocyclic group of R ^1a Good. The cyclic amino group is selected from aziridino, azetidino, pyrrolidino, morpholino and thiomorpholino groups. ) Represents an amino group. X ^a represents a nitro, cyano or trifluoroacetyl group. However, when (i) X ^a is a nitro group, R ^1a represents a heterocyclic group which may have a substituent of the same meaning as described above, and R ^2a represents a C _1-4 alkyl having a substituent or Optionally substituted C _5-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl or C _{7- 10 is an} aralkyl group,
Substituents R ^2a represents those similar to the substituents of the above R ^2a, R ^3a represents the same meaning as that described above, when (ii) X ^a is a nitro group, R ^1a is a substituted of the Represents a heterocyclic group which may have a group, R ^2a is hydrogen or C
_1-4 alkyl, R ^3a is of the formula: (In the formula, one of R ⁴ and R ⁵ represents a hydrogen atom or a hydrocarbon group which may have a substituent, and the hydrocarbon group is a C _1-15 alkyl group or a C _3-10 cycloalkyl group. , C _2-10 alkenyl, C _2-10 alkynyl, C _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the hydrocarbon group is a heterocyclic group of R ^1a . The same as the substituent on the ring group is shown, and the other is C having a substituent.
_1-4 represents a hydrocarbon group which may have an alkyl or a substituent, and the hydrocarbon group is C _5-15 alkyl, C _3-10 cycloalkyl, C _2-10 alkenyl, C _2-10 alkynyl, C
Selected from _3-10 cycloalkenyl, C _6-10 aryl and C _7-10 aralkyl groups, wherein the substituent of the C _1-4 alkyl and the substituent of the hydrocarbon group are the substituents on the heterocyclic group of R ^1a. shows what the same group, or R ⁴ and R ⁵ are aziridino together with the adjacent nitrogen together, azetidino, pyrrolidino, may form a cyclic amino group selected from morpholino and thiomorpholino groups. And (iii) X ^a is a cyano group, R ^1a is (a) the above R ^1a.
A pyridyl group having 1 to 5 substituents in, or (b) a halogenated thiazolyl group, wherein R ^2a is a hydrogen atom or a hydrocarbon which may have the same substituent as the above R ^2a. And R ^3a has the same meaning as defined above. ]
A guanidine derivative represented by or a salt thereof. 5. The guanidine derivative or a salt thereof according to claim 4, wherein X ^{a in the} general formula [I ^a ] is ^a nitro group. 6. The guanidine derivative or a salt thereof according to claim 4, wherein X ^{a in the} general formula [I ^a ] is ^a cyano group. 7. The formula: [Wherein, R ^1a , R ^2a and X ^a have the same meanings as those in claim 4, and Y represents a leaving group. ] Or a salt thereof and a compound of the formula: [The symbols in the formulas have the same meanings as those in claim 4. ] The compound of the formula [I ^a ] embedded image characterized by reacting with a compound represented by the formula or a salt thereof. [The symbols in the formulas have the same meanings as those in claim 4. ] The manufacturing method of the guanidine derivative or its salt represented by these. 8. The formula: [In the formula, R ^3a and X ^a have the same meanings as those in claim 4, and Y represents a leaving group. ] Or a salt thereof and a compound of the formula: [The symbols in the formulas have the same meanings as those in claim 4. ] The compound of the formula [I ^a ] embedded image characterized by reacting with a compound represented by the formula or a salt thereof. [The symbols in the formulas have the same meanings as those in claim 4. ] The manufacturing method of the guanidine derivative or its salt represented by these. 9. The formula: [The symbols in the formulas have the same meanings as those in claim 4. ] Or a salt thereof and a compound of the formula: [In the formula, R ^1a has the same meaning as that in claim 4, and Y represents a leaving group. ] The compound of the formula [I ^a ] embedded image characterized by reacting with a compound represented by [The symbols in the formulas have the same meanings as those in claim 4. ] The manufacturing method of the guanidine derivative or its salt represented by these. 10. The formula: [Wherein R ^1a and X ^a have the same meanings as those described in claim 4, R ^2b represents hydrogen or an optionally substituted hydrocarbon group, and R ^3b represents a compound represented by the formula: [The symbols in the formulas have the same meanings as those in claim 4. ] A primary, secondary or tertiary amino group represented by the formula] is shown, and when R ^3b is a tertiary amino group, R ^2b is hydrogen. ] Or a salt thereof and a compound of the formula: [In the formula, R has the same meaning as the optionally substituted hydrocarbon group in R ^2a or the optionally substituted hydrocarbon group in R ⁴ and R ⁵ , and Y represents a leaving group. Show. ] The compound of the formula [I ^a ] embedded image characterized by reacting with a compound represented by [The symbols in the formulas have the same meanings as those in claim 4. ] The manufacturing method of the guanidine derivative or its salt represented by these. 11. The formula: [The symbols in the formulas have the same meanings as those in claim 4. ] Or a salt thereof and a compound of the formula: [In the formula, X ^a has the same meaning as in claim 4, and Y represents a leaving group. ] Represented by the formula [I ^a ] embedded image characterized by reacting with a compound represented by [The symbols in the formulas have the same meanings as those in claim 4. ] The manufacturing method of the guanidine derivative or its salt represented by these.