DD242742A5 - INSECTICIDES MEDIUM - Google Patents

Abstract

The invention relates to insecticidal agents for use in agriculture, storage and in the veterinary and hygiene sector. The aim of the invention is the provision of new agents with a strong insecticidal effect for the fight against even such pests, which have become resistant to known insecticides. According to the invention, the novel agents contain as active ingredient at least one heterocyclic compound of the formula (I) in which, for example: n is 0 or 1; R 1, R 2 and R 6 independently of one another represent a hydrogen atom or an alkyl group; R 3 and R 4 independently of one another represent a hydrogen atom, a hydroxy group or an alkyl group; X is a sulfur atom or one of NR7 or CHR8; R7 represents a hydrogen atom, a hydroxy group, an alkoxy group, a benzyloxy group and the like; al .; Z is a 5- to 6-membered heterocyclic group which may be substituted with at least one substituent; u. al .; Y is a nitrogen atom or the group CR9; R 9 represents a hydrogen atom, a halogen atom, a hydroxy group and the like; a. formula

Description

Field of application of the invention

The invention relates to insecticidal compositions containing new heterocyclic compounds, to processes for their preparation and their use for pest control in agriculture, in the storage industry and in the hygiene and veterinary sector.

Characteristic of the known technical solutions

It has already been disclosed that not only certain nitromethylene derivatives have insecticidal function, for example i-benzyl-2-nitromethylene-tetrahydropyrimidine (see DE-OS 2514402), but that certain triazolidine derivatives have anti-tumor activity against tumors of the gastrointestinal tract Have-tract (see the JP-OS 196877/1984). Furthermore, i-benzyl-2-nitroiminoimidazolidine is in Can. J. Chem., Vol. 39, pages 1787-1796.

Object of the invention

The aim of the invention is the provision of agents with superior insecticidal activity, which are particularly effective against such noxious insects that have become resistant to known insecticidal compounds.

Explanation of the essence of the invention

The invention has for its object to find new heterocyclic compounds having the desired properties, which are suitable as active ingredient in insecticidal agents.

According to the invention in the new insecticides agents new heterocyclic compounds of the formula (I). R ⁴ R ³ ·

R ⁵ V "2

Z-CH'k R ¹

II

Y-NO ₂

applied in the

η denotes O or 1,

R ¹ , R ² , R ⁵ and R ⁶ independently of one another denote a hydrogen atom or an alkyl group,

R 1 and R ⁴ independently of one another denote a hydrogen atom, a hydroxy group or an alkyl group,

η 1 denotes that R ² is able to form a single bond together with R ⁵ ,

X denotes a sulfur atom, an oxygen atom or one of the following group NR ⁷ or CH-R ⁸ , wherein

R ^{7 is} a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a benzyloxy group, an alkyl group which may be substituted by at least one substituent selected from among alkoxy groups , Alkylthio groups, a cyano group, halogen atoms, dialkylamino groups and trialkylsilyl, an alkenyl group which may be substituted by a halogen atom, an alkynyl group substituted by a halogen atom a benzyl group which may be substituted by at least one substituent selected from the group consisting of methyl, a methoxy group, halogen atoms, halomethyl groups, halomethoxy groups and a nitro group, a formyl group, an alkenylcarbonyl group, an alkylcarbonyl group which may be substituted by at least one substituent may be selected from the group consisting of alkoxy groups, a phenoxy group, alkylthio groups and halogen atoms, a benzoyl group which may be substituted by at least one substituent selected from the group consisting of halogen Atoms, alkyl groups, halomethyl groups, alkoxy groups, haloalkoxy groups and a nitro group, a benzylcarbonyl group which may be substituted by an alkyl group and / or a halogen atom, an alkoxycarbonyl Group which may be substituted by a halogen atom, an alkylthiocarbonyl group, a phenoxycarbonyl group which may be substituted by at least one substituent selected from a methyl group, a methoxy group, halomethyl groups , Halomethoxy groups, halogen atoms and a nitro group, a phenylthiocarbonyl group which may be substituted by a halogen atom and / or an alkyl group, a benzylox ycarbonyl group, a monoalkyl or dialkylaminocarbonyl group, a phenylaminocarbonyl group which may be substituted by at least one substituent selected from the class consisting of alkyl groups, haloalkyl groups and halogen atoms, a benzoylaminocarbonyl group which may be substituted by an alkyl group and / or a halogen atom, a phenylsulphonylaminocarbonyl group which may be substituted by an alkyl group and / or a halogen atom, a phenylthio group which may be substituted by an alkyl group and / or a halogen atom; A group and / or a halogen atom may be substituted, an alkylsulfonyl group which may be substituted by a halogen atom, a phenylsulfonyl group which may be substituted by at least one substituent selected from among alkyl groups, Halogen atoms and a class consisting of nitro group, an alkylcarbonylmethyl group, a phenacyl group substituted by a halogen atom and / or an alkyl group may be an organophosphono group, an organothiophosphono group, the following groups -CH ₂ -W or -CO-W, wherein W denotes a 5- to 6-membered heterocyclic group, the at least one of the oxygen atoms, sulfur Atoms and nitrogen atoms containing class selected hetero atom and may be substituted by at least one substituent selected from the class consisting of halogen atoms, alkyl groups and haloalkyl groups,

R ^{8 represents} a hydrogen atom, an alkyl group, an aryl group or a benzyl group, Y denotes a nitrogen atom or the following group = CR ⁹ , wherein

R ^{9 is} hydrogen, halogen, hydroxy, alkoxy, benzyloxy, alkyl, which may be substituted by at least one substituent selected from halogen atoms, a hydroxy group, alkoxy groups, alkylthio groups, a cyano group, mono or dialkylamino groups, alkylcarbonyl groups, alkoxycarbonyl groups and phenoxycarbonyl groups, an alkenyl group represented by a Halogen atom, an alkynyl group, a phenyl group which may be substituted by an alkyl group and / or a halogen atom, an alkylcarbonyl group which may be substituted by a halogen atom, an alkenylcarbonyl Group, a benzoyl group which may be substituted by at least one substituent selected from the group consisting of halogen atoms, alkyl groups and alkoxy groups, an alkoxycarbonyl group substituted by a halogen atom se in, an alkylthiocarbonyl group, a phenoxycarbonyl group which may be substituted by at least one substituent selected from the class consisting of halogen atoms, alkyl groups, alkoxy groups and a nitro group, a phenylthiocarbonyl group A benzyloxycarbonyl group, a benzoylaminocarbonyl group which may be substituted by an alkyl group and / or a halogen atom, a phenylsulfonylaminocarbonyl group, which may be substituted by an alkyl group and / or a halogen atom, an alkylsulfonylaminocarbonyl group, an alkylthio group, an alkylsulfonyl group substituted by a halogenated azo

may be a phenylthio group which may be substituted by an alkyl group and / or a halogen atom, a phenylsulfonyl group which may be substituted by an alkyl group and / or a halogen atom, and also

R ⁹ is able to form a bis-form of the formula (I) via a methylene group, R represents a hydrogen atom or an alkyl group and

Z denotes a 5- to 6-membered heterocyclic group containing at least one hetero-atom selected from the class consisting of oxygen atoms, sulfur atoms and nitrogen atoms and which may be substituted by at least one substituent selected from halogen Atoms, alkyl groups, haloalkyl groups, a nitro group, a cyano group, alkoxy groups, alkylthio groups, alkylsulfinyl _: groups, alkylsulfonyl groups, alkenyl group, haloalkoxy groups, haloalkylthio group, haloalkenyl Groups, acylamino groups, haloacylamino groups, alkoxycarbonyl groups, a thiocyanato group, alkynyl group, an amino group, alkylamino groups, dialkylamino groups, a carboxy group, a hydroxy group, a mercapto Group.cycloalkyl groups, an oxo group, a thioxo group, alogenoalkenylthio groups, alkoxyalkyl groups, alkoxycarbonylamino groups, a carbamoyl group, acyl groups, alkylaminocarbonyl group n, dialkylaminocarbonyl groups, a formyl group, aryl groups optionally substituted with one selected from the group consisting of halogen atoms, alkyl groups, haloalkyl groups, alkoxy groups, a nitro group and a cyano group Substituents are substituted, aryloxy groups which are optionally substituted by a substituent, as indicated for the above aryl groups, and aralkyl groups, which are optionally substituted by one of the same substituents, as indicated for the aryl groups is, existing class, with the proviso that if

R ¹ , R ² , R ³ , R ^4, R ⁵ and R ^{6 are} simultaneously hydrogen atoms,

X denotes -NH and

Y = CH, then

Z is not for the pyridyl group.

In the case where compounds of the formula (I) have the following formula (I a)

(Ia)

have, in the

n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, R ⁹ and Z have the meanings given above, X ^{1 is} a sulfur atom, an oxygen atom or the following group -NR ¹⁰ denotes R ¹⁰ in the definition of R ⁷ denotes groups other than acyl groups including sulfonyl groups and phosphono groups,

the compounds of formula (Ia) are obtained when

(a) the compounds of the formula (II)

R ⁴ R ²

-X ¹ H. (I ₁ )

in which n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, X ¹ and Z have the meanings given above, with the compounds of the formula (III)

R'-S. R ⁹

C = C-NO ₂ (III)

in which R 'denotes a lower alkyl or benzyl group or the two R' together with the two sulfur atoms to which they are attached can form a ring, and R ^{9 has} the same meaning as above if appropriate in the presence of inert solvents, (b) the compounds of the above formula (II) are reacted with compounds of the formula (IV)

R "(Hal) ₂ C = C-NO ₂ (IV)

in which Hal is a halogen atom and R "is a hydrogen atom, a halogen atom or a lower alkyl group, optionally in the presence of inert solvents and in the presence of acid acceptors, or

(c) the compounds of the above formula (II) with compounds of the formula (V)

R "(Hal) ₃ CCH-NO ₂ (V)

in which Hal and R "have the same meanings as stated above, optionally in the presence of inert solvents and in the presence of acid acceptors In the case where compounds of formula (I) have the following formula (Ib )

Z-CH

have, in the

n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, X ¹ and Z have the meanings given above, the compounds of formula (I b) are obtained, if

(d) the compounds of the above formula (II) with nitroguanidine of the following formula

C-NH-NO ₂

HN

be reacted, optionally in the presence of inert solvents. In the case where the compound of the formula (I) has the following formula (Ic)

(Ic)

have, in the

n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, R and Z have the meanings given above, the compounds of formula (Ic) are obtained, if

(e) the compounds of the above formula (VI)

(VI)

H.

in the

n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, R and Z have the meanings given above, are reacted with fuming nitric acid, optionally in the presence of inert solvents.

The compounds of formula (I) are obtained when

(f) the compounds of the formula (VII)

in the

η, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , X and Y have the meanings given above, with the compounds of the formula (VIII)

R Z-CH-M-

in which R and Z have the meanings given above, M denotes a halogen atom or the following group-OSO 2 T and T represents a lower alkyl group, a phenyl group or a ToIyI group, optionally in the presence of inert solvents and in the presence of acid acceptors.

The new heterocyclic compounds show potent insecticidal properties.

Surprisingly, the heterocyclic compounds according to the invention show a significantly stronger and by far more superior insecticidal activity than the closest compounds of the above-mentioned prior art.

In addition, the heterocyclic compounds of the present invention also exhibit remarkable insecticidal activity against noxious insects, especially sucking insects typically represented by insects of the genus Hemiptera, such as aphids, lantern carriers and grasshoppers due to the long-term use of organic phosphate insecticides and carbamates Have acquired resistance to these remedies.

Among the novel heterocyclic compounds of the formula (I) according to the present invention, preferred compounds are those in which

η denotes O or 1,

R ¹ , R ² , R ⁵ and R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms

R ³ and R ⁴ independently of one another denote a hydrogen atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms,

X denotes a sulfur atom, an oxygen atom or one of the following groups -NR ⁷ or -CH-R ⁸ , R ⁷ denotes a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl atom A group, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, an alkyl group having 1 to 4 carbon atoms, which may be substituted by at least one substituent selected from the group consisting of alkoxy Groups having 1 to 4 carbon atoms, alkylthio groups having 1 to 4 carbon atoms, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, a dimethylamino group and trimethylsilyl class, an alkenyl Group having 2 to 3 carbon atoms which may be substituted by a chlorine atom, an alkynyl group having 2 to 3 carbon atoms, a benzyl group which may be substituted by at least one substituent selected from consisting of a methyl group, a methoxy group, a fluorine atom, a chlorine atom om, a bromine atom and a nitro group existing class, a formyl group, an alkenylcarbonyl group having an alkenyl part with 2 to 3 carbon atoms, an alkyl group having 1 to 5 carbon atoms by at least one substituent selected from the group consisting of a methoxy group, a phenoxy group, a fluorine atom, a chlorine atom and a bromine atom, a benzoyl group represented by at least one substituent which is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group, a difluoromethoxy group, a trifluoromethoxy group and a nitro Group, a benzylcarbonyl group which may be substituted by at least one substituent selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom, an alkoxycarbonyl group e with an alkyl of 1 to 4 carbon atoms, which may be substituted by a fluorine atom and / or a chlorine atom, an alkylthiocarbonyl group with an alkyl having 1 to 4 carbon atoms, a phenoxycarbonyl group, the may be substituted by at least one substituent selected from the class consisting of a methyl group, a fruor atom, a chlorine atom and a bromine atom, a phenylthiocarbonyl group which may be substituted by at least one substituent, which is selected from the group consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, a benzyloxycarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbonyl group which may be at least one substituent which is selected from the group consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, a benzoylaminocarbonyl group represented by at least one substituent n may be substituted, which is selected from the group consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, a phenylsulfonylaminocarbonyl group which may be substituted by at least one substituent which is selected a phenylthio group, an alkylsulfonyl group which may be substituted by a fluorine atom and / or a chlorine atom, a phenylsulfonyl group A group which may be substituted by at least one substituent selected from the group consisting of a methyl group, a fluorine atom, a chlorine atom, a bromine atom and a nitro group, a methylcarbonylmethyl group, a Phenacyl group which may be substituted by a fluorine atom and / or a chlorine atom, an organophosphono group, an organothiophosphono group, the following group-CH ₂ -W or -CO-W,

W denotes a 5- to 6-membered heterocyclic group containing one or two of oxygen atoms. Sulfur atoms and Stinkstnff breaths are the mainstays of the class Hppm Atnmp contains iinrl Hiorlnri-h

at least one substituent selected from the class consisting of a fluorine atom, a chlorine atom, a bromine atom and alkyl groups having 1 to 4 carbon atoms,

R ^{8 represents} a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a benzyl group,

Y denotes a nitrogen atom or the following group = CR ⁹ ,

R ^{9 is} a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, an alkyl group having 1 to 4 carbon atoms, which may be substituted by at least one substituent selected from among fluorine, chlorine, hydroxy, alkoxy, 1 to 2 carbon atoms, alkylthio Groups having 1 to 2 carbon atoms, a cyano group, a dimethylamino group, alkylcarbonyl groups having an alkyl of 1 to 2 carbon atoms, and alkoxycarbonyl groups having an alkyl of 1 to 2 carbon atoms, a Alkenyl group having 2 to 3 carbon atoms, a phenyl group, an alkylcarbonyl group having an alkyl of 1 to 4 carbon atoms, which may be substituted by at least one substituent selected from the group consisting of methoxy group , a chlorine atom and a fluorine atom existing Class, an alkenylcarbonyl group having an alkenyl having 2 to 3 carbon atoms, a benzoyl group which may be substituted by at least one substituent selected from among a fluorine atom, a chlorine atom, a bromine Atom, a methoxy group and a methyl group, an alkoxycarbonyl group which may be substituted by a fluorine atom and / or a chlorine atom, an alkylthiocarbonyl group having an alkyl of 1 to 4 carbon Atom, a phenoxycarbonyl group which may be substituted by at least one substituent selected from among fluorine, chlorine, bromine, methyl, methoxy, and nitro Group, a phenylthiocarbonyl group, a benzyloxycarbonyl group, a benzoylaminocarbonyl group which may be substituted by at least one substituent selected from the group consisting of a methyl group, a fluoro-At om, a chlorine atom and a bromine atom class, a Phenylsulfonylaminocarbonyl group which may be substituted by at least one substituent selected from the group consisting of a methyl group, a fluorine atom, a chlorine atom and a Bromine atom, an alkylsulfonylaminocarbonyl group having an alkyl of 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylsulfonyl group represented by a fluorine atom and / or a chlorine atom Atom, a phenylthio group which may be substituted by at least one substituent selected from the group consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, or a phenylsulfonyl Group which may be substituted by at least one substituent selected from the class consisting of a methyl group, a fluorine atom, a chlorine atom and a bromine atom, in addition

R ⁹ is able to form a bis-form of the formula (I) via a methylene group,

R represents a hydrogen atom or a methyl group and

Z denotes a 5- to 6-membered heterocyclic group containing one bts of three heteroatoms selected from the class consisting of oxygen atoms, sulfur atoms and nitrogen atom, at least one of which is a nitrogen atom, and which is characterized by at least may be substituted by a substituent selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, alkyl groups having 1 to 4 carbon atoms, which is represented by a fluorine atom and / or a chlorine Atom, a nitro group, a cyano group, alkylsulfinyl groups having 1 to 4 carbon atoms, alkylsulfonyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, the may be substituted by a fluorine atom and / or a chlorine atom, alkylthio groups having 1 to 4 carbon atoms which may be substituted by a fluorine atom and / or a chlorine atom, alkenyl groups having 2 to 3 carbon atoms, subunit by a chlorine atom may be substituted, an acetamide group which may be substituted by a fluorine atom and / or a chlorine atom, alkoxycarbonyl groups having an alkyl having 1 to 4 carbon atoms, a thiocyanato group, alkynyl groups having 2 to 4 carbon atoms, an amino group, a methylamino group, a dimethylamino group, an acetyl group, a formyl group, a carboxy group, a hydroxy group, a mercapto ^ ^ cycloalkyl groups with 3 to 7 carbon atoms, an oxo group, a thioxo group, alkenylthio groups which are substituted by a fluorine atom, a chlorine atom and / or a bromine atom, alkoxyalkyl groups having a total of 2 to 4 carbon atoms Atoms, alkylaminocarbonyl groups having an alkyl of 1 to 2 carbon atoms, dialkylaminocarbonyl groups having an alkyl of 1 to 2 carbon atoms, a phenyl group, a phenoxy group and a benzyl group, with the proviso in that when R ¹ , R ² , R ³ , R ⁴ R ⁵ , and R ⁶ simultaneously represent hydrogen atoms, X denotes -NH and Y denotes CH, then Z may not stand for the pyridyl group.

Very particularly preferred heterocyclic compounds of the formula (I) are those in which η denotes 0 or 1,

R ¹ , R ² , R ⁵ and R ⁸ independently of one another denote a hydrogen atom or a methyl group, R ³ and R ⁴ independently of one another denote a hydrogen atom or a methyl group, X denotes a sulfur atom, an oxygen Atom or one of the following group NR ⁷ or CH-R ⁸ ,

R ^{7 is} a hydrogen atom, an alkyl group which may be substituted by at least one substituent selected from the group consisting of a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a cyano group, Group, a fluorine atom, a chlorine atom and a trimethylsilyl group, an allyl group which may be substituted by a chlorine atom,

a propargyl group,.

a benzyl group which may be substituted by a methyl group and / or a chlorine atom, a formyl group, a vinylcarbonyl group,

an alkylcarbonyl group having an alkyl of 1 to 3 carbon atoms which may be substituted by at least one substituent selected from the class consisting of a methoxy group, a phenoxy group and a chlorine atom,

a benzoyl group which may be substituted by at least one substituent selected from the class consisting of a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group and a nitro group .

a benzylcarburyl group which may be substituted by a chlorine atom, an alkoxycarbonyl group having an alkyl having 1 to 2 carbon atoms, which may be substituted by a fluorine atom and / or a chlorine atom,

an alkylthiocarbonyl group having an alkyl of 1 to 2 carbon atoms, a phenoxycarbonyl group which may be substituted by a methyl group and / or a chlorine atom, a phenylthiocarbonyl group substituted by a chlorine atom may be a benzyloxycarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbonyl group, a benzoylaminocarbonyl group,

a phenylsulfonylaminocarbonyl group which may be substituted by a methyl group and / or a chlorine atom, a phenylthio group,

a methylsulfonyl group which may be substituted by a chlorine atom, a phenylsulfonyl group which may be substituted by a methyl group, a methylcarbonylmethyl group,

a phenacyl group which may be substituted by a chlorine atom, a 0,0-diethylthionophosphono group, an O-ethyl-Sn-propylthiolophosphono group, the following group-CH ₂ -W or -CO-W,

W denotes a 5- to 6-membered heterocyclic group containing one or two selected from the class of oxygen atoms, sulfur atoms and nitrogen atoms selected hetero-atoms and by a fluorine atom, a chlorine atom, a bromine Atom and a methyl group may be substituted,

R ^{8 represents} a hydrogen atom, a methyl group, a phenyl group or a benzyl group,

Y denotes a nitrogen atom or the following group = CR ⁹ ,

R ^{9 is} hydrogen, chlorine, bromine, hydroxy, methoxy, benzyloxy, alkyl, which may be substituted by at least one substituent selected from the group consisting of a fluorine atom, a chlorine atom, a hydroxy group, a methoxy group, a cyano group, a dimethylamino group, an acetyl group and a methoxycarbonyl group, an allyl group, a phenyl group,

an acetyl group which may be substituted by a chlorine atom, a vinylcarbonyl group, an allylcarbonyl group, a benzoyl group, an alkoxycarbonyl group having an alkyl having 1 to 2 carbon atoms, which may be replaced by a fluoro Atom can be substituted,

an n-butylthiocarbonyl group, a phenoxycarbonyl group which may be substituted by a chlorine atom and / or a methyl group, a phenylthiocarbonyl group, a benzyloxycarbonyl group, a benzoylaminocarbonyl group represented by a chlorine atom a phenylsulfonylamino carbonyl group which may be substituted by a methyl group, a methylsulfonylaminocarbonyl group

a propylthio group, a methylsulfonyl group which may be substituted by a fluorine atom and / or a chlorine atom, a phenylthio group which may be substituted by a chlorine atom, or a phenylsulfonyl group in addition

R ⁹ is able to form a bis-form of the formula (I) via a methylene group,

R represents a hydrogen atom or a methyl group and

Z denotes a 5- to 6-membered heterocyclic group containing one to three heteroatoms selected from the class consisting of oxygen atoms, sulfur atoms and nitrogen atoms, at least one of which is a nitrogen atom, and which is characterized by at least may be substituted by a substituent selected from among fluorine atom, chlorine atom, bromine atom, methyl group, fluoroalkyl groups having 1 to 2 carbon atoms, methoxy group, methylthio Group, a methylsulfinyl group, a methylsulforiyl group, a nitro group, a cyano group, a trifluoromethoxy group, a trifluoromethylthio group, an allyl group, an acetamide group, a methoxycarbonyl group, an acetyl Group, a formyl group and a carboxy group existing class, with the proviso that when

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} simultaneously hydrogen atoms,

X denotes -NH and

Y = CH, then

Z may not stand for the pyridyl group,.

Specifically mentioned are the following compounds:

3- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) tetrahydro-2H-1,3-thiazine,

3- (2-chloro-5-pyridylmethyl) -2- (nitromethy4en) -thiazolidine,

3- (2-Flupro-5-pyridylmethy |) -2- (nitromethylene) tetrahydro-2H-1,3-thiazine,

3- {2-fluoro-5-pyridylmethyl) -2- (nitromethylene) thiazolidine,

3- (2-Bromo-5-pyridylmethyl) -2- (nitromethylene) -tetrahydro-2H-1,3-thiazine,. , ·

3- (2-Bromo-5-pyridylmethyl) -2- (nitromethylene) thiazolidine,

3- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) thiazolidine,

3- (2-methyl-5-pyridylmethyl) -2- (nitromethylene) tetrahydro-2H-1,3-thiazine,

3- (2-ethyl-5-pyridylmethyl) -2- (nitromethylene) thiazolidine,

3- (2-trifluoromethyl-5-pyridylmethyl) -2- (nitromethylene) -tetrahydro-2H-1,3-thiazine, 3- (3-pyridylmethyl) -2- (nitromethylene) -thiazolidine,

3- (3-pyridylmethyl) -2- (nitromethylene) tetrahydro-2H-1,3-thiazine,

3- (2-trifluoromethyl-5-pyridylmethyl) -2- (nitromethylene) thiazolidine,

1- (5-pyrazolylmethyl) -2- (nitromethylene) imidazoline,

i-IS-Chloro-i-methyl-S ^ pyrazolylmethyD -fnitromethylenlimidazolidin,

1- (1-methyl-4-pyrazolylrnethyl) -2- (nitromethylene) tetrahydropyrimidine,

1- (1-methyl-4-pyrazolylmethyl) -2- (nitromethylene) imidazolidine,

1- (3-trifluoromethyl-5-isoxazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine,

1- (3-Methyl-5-isoxazolylmethyl) -2- (nitromethylene) imidazolidine, 1- (3-methyl-5-isoxazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (5-isoxazolylmethyl) -2- (nitromethylene ) imidazolidine, 1- (2-methyl-5-thiazolylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-chloro-5-thiazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2-trifluoromethyl-5-) thiazolylmethyl) -2- (nitromethylene) imidazolidine, 1- (1,2,5-thiadiazol-3-ylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (1,2,3-thiadiazol-5-ylmethyl) -2 - (nitromethylene) tetrahydropyrimidine, 1- (2-methyl-5-thiazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (2-chloro-5-thiazolylmethyl) -2- (nitromethylene) imidazolidine, 1- (1,2 , 5-thiadiazol-3-ylmethyl) - (nitromethylene) imidazolidine, 1- (5-thiazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 1- (5-pyrimidinylmethyl) -2- (nitromethyl) imidazolidine, 1- (2- Methyl 5-pyrimidinylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-pyrazinylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-methyl-5-pyrazinylmethyl) -2- (nitromethyl n) imidazolidine, 1- (2-chloro-5-pyrimidinylmethyl) -2- (nitromethylene) -tetrahydropyrimidine, 1- {2-chloro-5-pyrimidinylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-fluoro) 5-pyrimidinylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-trifluoromethyl-5-pyrimidinylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-chloro-5-pyrazinylmethyl) -2- (nitromethylene) imidazolidine, 1- [1- (2-fluoro-5-pyrimidinyl) ethyl] -2- (nitromethylene) imidazoline, 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) tetrahydropyrimidine, 1- (2-chloro) 5-pyridylmethyl-2- (nitroimino) imidazolidine, 1- (2-trifluoromethyl-5-pyridylmethyl) -2- (nitroimino) -tetrahydropyrimidine, 1- (2-trifluoromethyl-5-pyridylmethyl) -2- (nitroimino) -imidazolidine , 1- (2-Fluoro-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2-bromo-5-pyridylmethyl) -2- (nitroimino) imidazolidine, 1- (2-methyl-5-pyridylmethyl) 2- (nitroimino) imidazolidine, 1- (2-methoxy-5-pyridylmethyl-2- (nitroimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) pyrrolidine, 1- (2-chloro -5-thiazoIylmethyl) -2- (nitroi mino) tetrahydropyrimidine, 1- (2-chloro-5-pyrimidinylmethyl) -2- (nitroimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -4-methyl-2- (nitromethylene) imidazolidine, i - ^ - Chloro-B-pyridylmethyD-SO-pyridylmethyD1-initromethylenelimidazolidine, 1- (2-chloro-5-pyridylmethyl-2- (bromonitromethylene) -imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (1-nitro 2-oxopentylidene) imidazolidine, ethyl nitro [3- (2-chloro-5-pyridylmethyl) thiazolidin-2-ylidene] acetate, 1-acetyl-3- (2-chloro-5-pyridylmethyl) -2- (nitroimino ) -imidazolidine and N-phenylsulfonyl-nitro [1- (2-chloro-5-pyridylmethyl) imidazolidin-2-ylidene] acetamide.

For example, when N- (1-methyl-4-pyrazolylmethyl) trimethylenediamine and 1-nitro-2,2-bis (methylthio) ethylene are used as starting materials in the process (a), the reaction can be represented by the following equation:

(CH ₃ S) ₂ C = CHNO ₂

When, for example, 2- (2-methyl-5-pyrazinylmethylamino) ethanethiol and 2,2-dichloronitroethane are used as starting materials in process (b), the course of the reaction can be represented by the following equation:

^H 3 ^C ~ ^C 3 ~ ^CH 2 ^NHCH 2 ^CH 2 ^{SH +} Cl ₂ C = CH-NO-

= CHNO

When, for example, 2- (2-chloro-5-thiazolylmethylamino) ethanethiol and 1,2,2,2-tetrachloro-1-nitroethane are used as starting materials in process (c), the course of the reaction can be represented by the following equation:

CH ₂ NHCH ₂ CH ₂ SH + Cl

e Cl

Cl

For example, when N- (2-chloro-5-pyridylmethyl) trimethylenediamine and nitroguanidine are used as starting materials in process (d), the reaction can be represented by the following equation:

- (CH ₂ ) ₃ -

NH

For example, when 1- (2-chloro-5-pyridylmethyl) -2-iminoimidazolidine and fuming nitric acid are used as starting materials in the process (e), the reaction can be represented by the following equation:

H H

H ₁₁ Q ₃ -> 1 / -H-NO ₂

^CH 2 "v3 ~ ^{C1 CH} 2" \ l3 ^"C1

For example, when 2-nitromethylenthiazolidine and 2-chloro-5-pyridylmethyl chloride are used as the starting materials in the process (f), the reaction can be represented by the following equation:

O-

CHNO ₂

Formula (II) gives a general definition of the compounds required as starting materials in process (a), with the meanings of n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, Z and X ^{1 are} referred to.

In the formula (II), n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, Z and X ¹ preferably have the meanings already described above.

The compounds of the formula (II) that can be used according to the invention include both known and novel compounds.

The known examples have already been described in, for example, Japanese Patent Application Laid-Open Nos. 26020/1984, 72966/1984 and 132943/1984, Z. Anorg. AIIg. Chem. 312, p.282-286, Khim. Geterotsikl. Soedin. 1974, no. 1, pp. 122-123, Metody Poluch. Khim.

Reactivon Prep. No. 17, p. 172-173, Issled. OBI. Geterotsikl. Soedin. 1971, p.39-44, U.S. Patent 4,018,931, Arch. Pharm. 1982, Vol.

315, p.212-221, Metody Poluch. Khim. Reactivon Prep. 1967, pp. 133-134, and Zh. Obshch. Khim. 33, pp. 1130-1135.

As examples, the following compounds may be mentioned:

N- (2-chloro-5-pyridylmethyl) -2-aminoethanethiol, N- (2-chloro-5-pyridylmethyl-3-aminopropanethiol, N- (2-bromo-6-pyridylmethyl) -2-aminoethanethiol, N = - (2-Bromo-5-pyridylmethyl) -3-aminopropanethiol, N- (2-fluoro-5-pyridylmethyl) -2-aminoethanethiol, N- (2-fluoro-5-pyridylmethyl) -3-aminopropanethiol, N- [1 - (2-chloropyridyl) ethyl] -2-aminoethanethiol, N- (2,3-dichloro-5-pyridylmethyl) -2-aminopethanethiol, N- (3-chloro-2-fluoro-5-pyridylmethyl) -2 -aminoethanethiol, N- (2-chloro-4-pyridylmethyl) -2-aminoethanethiol ,.

N- (3-chloro-2-pyridylmethyl) -2-aminoethanethiol, N -fB-chloro -pyridylmethoxy-S-aminopropanethiol, N- (3,5-dichloro-2-pyridylmethyl) -2-aminoethanethiol, N- ( 5-fluoro-2-pyridylmethyl) -3-aminopropanethiol, N- (6-bromo-2-pyridylmethyl) -2-aminoethanethiol, N- (2-chloro-3-pyridylmethyl) -3-aminopropanethiol, N-fB-chloro -S-pyridylmethyD-S-aminopropanethiol, N- (5-bromo-3-pyridylmethyl) -2-aminoethanethiol, N- (5-fluoro-3-pyridylmethyl) -2-aminoethanethiol, N- [1- (2-fluoro 5-pyridyl) ethyl] -2-aminoethanethiol, N- (2,4-dichloro-5-pyridylmethyl) -3-aminopropanethiol, N- (2,4-dibromo-5-pyridylmethyl) -2-aminoethanethiol, N- (2,6-difluoro-4-pyridylmethyl) -2-aminoethanethiol, N- (2-fluoro-4-pyridylmethyl) -3-aminopropanethiol, N- (2,6-dibromo-4-pyridylmethyl) -2-aminoethanethiol, N- (3-bromo-2-fluoro-5-pyridylmethyl) -2-aminoethanethiol, N- (2-chloro-3-fluoro-5-pyridylmethyl) -2-aminoethanethiol, N- [1- (2-chloro) 5-pyridyl) propyl] -2-aminoethanethiol, N- (3-pyridylmethyl) -2-aminoethanethiol, N- (3-pyridylmethyl) -2-aminopropanethiol, N- (4-pyridyl thyl) -2-aminoethanethiol,

N- (4-pyridylmethyl) -2-aminopropanethiol,.

N- (2-methyl-5-pyridylmethyl-2-aminoethanethiol, N- (2-methyl-5-pyridylmethyl) -3-aminopropanethiol, N- (2-ethyl-5-pyridylmethyl) -2-aminoethanethiol, N- ( 2-allyl-5-pyridylmethyl) -2-aminoethanethiol, N- (2-propargyl-5-pyridylmethyl) -2-aminoethanethiol, N- (2-methoxy-5-pyridylmethyl) -3-aminopropanethiol, N- (2- Methylthio-5-pyridylmethyl) -2-aminopropanethiol, N- (2-methylsulfonyl-5-pyridylmethyl) -2-aminoethanethiol, N- (2-chloro-3-methyl-5-pyridylmethyl) -2-aminoethanethiol, N- [ 1- (3-pyridyl) ethyl] -3-aminopropanethiol, N- (2-trifluoromethyl-5-pyridylmethyl) -2 ⁱ aminoethanethiol,

N- (2-trifluoromethyl-5-pyridylmethyl) -3-aminopropanethiol, N- (2-nitro-5-pyridylmethyl) -2-aminoethanethiol, N- (2-nitro-5-pyridylmethyl) -3-aminopropanethiol, N- (2-cyano-5-pyridylmethyl) -2-aminoethanethiol, N- (2-cyano-5-pyridylmethyl) -3-aminopropanethiol, N- (2-cyano-5-pyridylmethyl) -3-aminopropanethiol, N- (2 -Methylsulfinyl-5-pyridylmethyl) -2-aminoethanethiol, N- (2-phenyl-5-pyridylmethyl) -2-aminoethanethiol, N- (2-benzyl-5-pyridylmethyl) -2-aminoethanethiol, N- (2-phenoxy 5-pyridylmethyl) -3-aminopropanethiol, 'N- (2-trichloromethyl-5-pyridylmethyl) -2-aminoethanethiol, N- [2- (2-ethoxyethyl) - (pyridylmethyl] -3-aminopropanethio (, N- ( 2-methoxymethyl-5-pyridylmethyl) -2-aminoethanethiol, N- (2-difluoromethoxy-5-pyridylmethyl) -2-aminoethanethiol, N- (2-trifluoromethoxy-5-pyridylmethyl) -2-aminoethanethiol "N - [- 2 - (2,2,2-trifluoroethoxy) -5- (pyridylmethyl) -2-aminoethanethiol, N- (2-chlorodifluoromethylthio-5-pyridylmethyl) -3-aminopropanethiol, N- (2-trifluoromethylthio-5-pyridylmethyl) -2 aminoethanethiol, N- (2-difluoromethyl- 5-pyridylmethyl) -2-aminoethanethiol, N- (2-trifluoromethylsulfonyl-5-pyridylmethyl) -2-aminoethanethiol, N- (2-trifluoromethylsulfinyl-5-pyridylmethyl) -2-aminoethanethiol, N- [2- (2,2 Dichlorovinyl) -5- (pyridylmethyl) -2-aminoethanethiol, N- (4-pyrimidinylmethyl) ethylenediamine, N- (2-methyl-4-pyrimidinylmethyl) ethylenediamine,

N- (2-methyl-6-oxo-1H, 6H-dihydropyrimidine-4-ylmethyl) trimethylenediamine,

N- (5-pyrimidinylmethyl) ethylenediamine, N- (2-methyl-5-pyrimidinylmethyl) ethylenediamine, N- (2-dimethylamino-5-pyrimidinylmethyl) ethylenediamine, N- (2-dimethylamino-5-pyrimidinylmethyl (ethylenediamine, N-) (2-Dimethylamino-5-pyrimidinylmethyl) trimethylenediamine, N- (2,4,6-trichloro-5-pyrimidinylmethyl) ethylenediamine, N- (4-pyrazinylmethyl) ethylenediamine, N- [1- (pyrazinyl) ethyl] ethylenediamine, N - (2-methyl-5-pyrazinylmethyl) ethylenediamine, N- (3-pyridazinylmethyl) ethylenediamine, N- (2-chloro-4-pyrimidinylmethyl) ethylenediamine, N- (4-chloro-6-pyrimidinylmethyl) ethylenediamine, N- ( 4-methyl-6-pyrimidinylmethyl) trimethylenediamine, N- (2-fluoro-5-pyrimidinylmethyl) ethylenediamine, N- [1- (2-fluoro-5-pyrimidinyl) ethyl] ethylenediamine, N- (2-chloro-5- pyrimidinylmethyl) ethylenediamine, N- (2-chloro-5-pyrimidinylmethyl) trimethylenediamine, N- (2-isopropyl-5-pyrimidinylmethyl) ethylenediamine, N- (2-chlorodifluoromethyl-5-pyrimidinylmethyl) ethylenediamine, N- (2-trifluoromethyl- 5-pyrimidinylmethyl) ethylenediamine, N- (2-bromomodifluoromethyl-5-pyri midinylmethyl) ethylenediamine, N- (2-methoxy-5-pyrimidinylmethyl) ethylenediamine, N- (2-difluoromethoxy-5-pyrimidinylmethyl) ethylenediamine, N- (2-trifluoromethoxy-5-pyrimidinylmethyl) ethylenediamine, N- [2- (2 , 2,2-t -fluoroethoxy) -5-pyrimidinylmethyl] -trimethylenediamine, N- (2-methylthio-5-pyrimidinylmethyl) ethylenediamine, N- (2-ethylthio-5-pyrimidinylmethyl) ethylenediamine, N- (2-difluoroethylthio-5- pyrimidinylmethyl) ethylenediamine, N- (2-trifluoromethylthio-5-pyrimidinylmethyl) ethylenediamine, N- [2- (2,2,2-trifluoroethylthio) -5-pyrimidinylmethyl] ethylenediamine, N- (2-nitro-5-pyrazinylmethyl) ethylenediamine, N- (2-cyano-5-pyrazinylmethyl) trimethylenediamine, N- (2-chloro-5-pyrazinylmethyl) ethylenediamine, N- (2-trifluoromethyl-5-pyrazinylmethyl) ethylenediamine, N- (3-fluoro-6- pyridazinylmethyl) ethylenediamine, N- (3-methyl-6-pyridazinylmethyl) trimethylenediamine, N- (4-pyridazinylmethyl) ethylenediamine, NO-chloro-e-pyridazinylmethylethylenediamine, N- (4-pyridazinylmethyl) trimethylenediamine, N- (3-trifluoromethyl- 6-pyrida ^ inylmethy l) ethylenediamine, N- (1,3,5-triazin-2-ylmethyl) ethylenediamine, N- (3-chloro-1-methyl-triazine-e-ylmethyl-ethylenediamine, NO.B-dichloro-1,2,3-triazine e-ylmethyllethylendiamin,

NO-chloro-1-AB-tetrazine-e-ylmethoxyethylenediamine, N- (3-furylmethyl) ethylenediamine or -trimethylenediamine, N- (furfuryl) -ethylenediamine or -trimethylenediamine, N- (5-methylfurfuryl) -ethylenediamine or -trimethylenediamine, N- (2-thienylmethyl) ethylenediamine or trimethylenediamine, N- (4-imidazolylmethyl) ethylenediamine or trimethylenediamine, N- (4-methyl-5-imidazolylmethyl) ethylenediamine or trimethylenediamine, N- (tetrahydrofurfuryl) ethylenediamine or trimethylenediamine, N- (5-methyltetrahydrofurfuryl) ethylenediamine or trimethylenediamine, N- (3-thienylmethyl) ethylenediamine or trimethylenediamine, N- (2-pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-2-pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (5-methyl-2-thienylmethyl) ethylenediamine or trimethylenediamine, N- (5-bromo-2-thienylmethyl) ethylenediamine or trimethylenediamine, N- (5-cyanofurfuryl) ethylenediamine or trimethylenediamine, N- (5-trifluoromethylthio 2-thienylmethyl) ethylenediamine or trimethylenediamine, N- [1- (2-thienyl) ethyl] ethylenediamine or trimethylenediamine, N- (5-methyl-3-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (4-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- ( 3-methyl-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-trifluoromethyl-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-chloro-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (5- isothiazolylmethyl) ethylenediamine or trimethylenediamine, N- (5-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (4-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-4-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N - [1- (1-methyl-4-pyrazolyl) ethyl] ethylenediamine or trimethylenediamine, N- (1-ethyl-4-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-isopropyl-4-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-allyl-4-pyrazolylmethyl) ethylenediamine or trimethylenediamine,

N- (1-tert-butyl-4-pyrazolylmethyl) ethylenediamine or trimethylenediamine,

N- [1- (2,2,2-trifluoroethyl) -5-pyrazolylmethyl] ethylenediamine or trimethylenediamine, N- (3-methyl-5-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- {3-chloro-2- methyl-5-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (2,3,5-trimethyl-4-pyrazolylmethyl) ethylenediamine or -trimethylenediamine, N- (5-oxazolylmethyl) ethylenediamine or -trimethylenediamine, N- (4-methyl- 5-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- (4-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N - (2-chloro-4-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-chloro-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoromethyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- ( 2-bromo-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2,4-dichloro-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (4-imidazolylmethyl) ethyl endiamine or trimethylenediamine, N- (1-methyl-2-imidazolylmethyl) ethylenediamine or trimethylenediamine, N- (1,2,4-triazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-1, 2,4-triazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,2,5-thiadiazol-4-ylmethyl) -ethylenediamine or -trimethylenediamine, N- (1,2,3-thiadiazol-5-ylmethyl ) ethylenediamine or trimethylenediamine, N- (3-methyl-1,2,4-oxadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,3-dioxolan-2-ylmethyl) ethylenediamine or trimethylenediamine, N- (2,2-dimethyl-1,3-dioxolan-4-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-2-oxazolin-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoromethyl-2 oxazolin-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-pyrrolymethyl) ethylenediamine or trimethylenediamine, N- (1-ethyl-2-pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-3 -pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (5-methyl-3-thienyl) ethylenediamine or trimethyls ndiamine, N- (5-methyl-3-pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (1,5-dimethyl-3-pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (2,5-dimethyl-3-furylmethyl) ethylenediamine or trimethylene diamine, N- (2,5-dimethyl-3-thienylmethyl) ethylenediamine or trimethylenediamine, N- (5-fluoro-3-furylmethyl) ethylenediamine or trimethylenediamine, N- (4-chlorofurfuryl) ethylenediamine or trimethylenediamine, · N-fB-chlorofurfuryl-ethylenediamine or -trimethylenediamine, N- (5-chloro-3-furylmethyl) ethylenediamine or -trimethylenediamine.

N- (5-chloro-3-thienylmethyl) ethylenediamine or trimethylenediamine, N-fB-chloro-i-methyl-S-pyrrolylmethyl-ethylenediamine or -trimethylenediamine, N- (5-bromo-3-furylmethyl) -ethylenediamine or -trimethylenediamine, N - (5-nitrofurfuryl) ethylenediamine or trimethylenediamine, N- (4-nitro-2-thienylmethyl) ethylenediamine or trimethylenediamine, N- (5-nitro-2-thienylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl- 5-nitro-3-pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (5-cyano-3-furylmethyl) ethylenediamine or trimethylenediamine, N- (5-cyano-3-thienylmethyl) ethylenediamine or trimethylenediamine, N- (5- Cyano-1-methyl-3-pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (5-trifluoromethylfurfuryl) ethylenediamine or trimethylenediamine, N- (5-difluoromethylfurfuryl) ethylenediamine or trimethylenediamine, N- (5-trifluoromethyl-3-thienylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-5-trifluoromethyl-3-pyrrolylmethyl) ethylenediamine or trimethylenediamine, N- (5-methoxy-2-thienylmethyl) eth ylendiamine or trimethylenediamine, N- (5-methylthiofurfuryl) ethylenediamine or trimethylenediamine, N- (2,5-dimethylthio-3-thienylmethyl (ethylenediamine or trimethylenediamine, N- (5-trifluoromethylthiofurfuryl) ethylenediamine or trimethylenediamine, N- [5- (2,2-dichlorovinyl) -2-thienylmethyl] ethylenediamine or trimethylenediamine, N- (5-ethoxycarbonylfurfuryl) ethylenediamine or trimethylenediamine, N- (5-formyl-2-thienylmethyl) ethylenediamine or trimethylenediamine, N- (3-isoxazolylmethyl) ethylenediamine or ^ trimethylenediamine, N- (4-isoxazolylmethyl) ethylenediamine or -trimethylenediamine, N- (3-ethyl-5-isoxazolylmethyl) ethylenediamine or -trimethylenediamine, N- (3-isopropyl-5-isoxazolylmethyl) ethylenediamine or trimethylene diamine, N- (3-fluoro-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-bromo-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-hydroxy-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-nitro-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (3- Cyano-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-difluoromethyl-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, NO-chloromethyl-B-isoxazolylmethyl-ethylenediamine or -trimethylenediamine, N- (3-methoxymethyl-5-isoxazolylmethyl) ethylenediamine or -trimethylenediamine, N- (3-isopropoxymethyl-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, NO-trichloromethyl-o-isoxazolylmethyethylenediamine or -trimethylenediamine, N- (3-methoxy-5-isoxazolylmethyl) ethylenediamine or -trimethylenediamine, N- ( 3-trifluoromethoxy-5-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (2,5-dimethyl-4-isoxazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-isothiazolylmethyl) ethylenediamine or trimethylenediamine, N- (4-isothiazolylmethyl) ethylenediamine or trimethylenediamine, N- (3- (pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- [1- (4-pyrazolyl) ethyl] ethylenediamine or trimethylenediamine, N- (1-methyl-3-pyrazolylmethyl) ethylenediamine or trimethylenediamine , N- (1-methyl-5 pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-propyl-4-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- [1- (2,2,2-trifluoroethyl) -3-pyrazolylmethyl] ethylenediamine or trimethylenediamine, N- fB-chloro-i-ethyl-S-pyrazolylmethy-dimethyl-diamine or -trimethylenediamine, N -fB-chloro-i-isopropyl-S-pyrazolylmethyl-ethylenediamine or -trimethylenediamine, NO-chloro-i-methyl-S-pyrazolylmethyethylenediamine or -trimethylenediamine, N- ( 5-trifluoromethyl-3-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-5-trifluoromethyl-3-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-3-trifluoromethyl-5-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (4-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-4-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-5-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- ( 2-fluoro-5-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-chloro-5-oxazolylmethyl) ethylenediamine or trim thylenediamine, N- (2-trifluoromethyl-5-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylthio-5-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoromethoxy-5-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- (2,4-dimethyl-5-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- (5-ethoxycarbonyl-2-oxazolylmethyl) ethylenediamine or trimethylenediamine, N - [. 1- (5-thiazolyl) ethyl] ethylenediamine or trimethylenediamine, N- (2-methyl-4-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- [1- (2-methyl-5-thiazolyl) ethyl] ethylenediamine or trimethylenediamine, N- (2-ethyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-isopropyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (4-methyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-fluoro-4-thiazolylmethyl) ethylenediamine or -trimethylenediamine,

N- (2-fluoro-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- [1- (2-chloro-5-thiazolylmethyl) ethyl] ethylenediamine or trimethylenediamine, N- (2-nitro-4-thiazolylmethyl) ethylenediamine or trimethylene diamine, N- (2-nitro-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-cyano-4-thiazolylmethyl) ethylenediamine or trimethylgndiamine, N- (2-cyano-5-thiazolylmethyl) ethylenediamine or trimethylenediamine , N- (2-methylthio-4-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-mercapto-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylthio-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N - (2-Difluoromethylthio-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoromethylthio-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-chlorodifluoromethylthio-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- [ 2- (2,2,2-trifluoroethylthio) -5-thiazolylmethyl] ethylenediamine or trimethylenediamine, N- [2- [2- (2,3,3-trichloro) propenyl thio] -5-thiazolylmethyl] ethylenediamine or trimethylenediamine, N- (2-thiocyanato-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-amino-4-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-acetamino 4-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methoxy-4-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methoxy-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoromethoxy-5 -thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-difluoromethoxy-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-chloromethyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-difluoromethyl-5-thiazolylmethyl ) ethylenediamine or trimethylenediamine, N- (2-trifluoromethyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- [2- (1,1,2,2-tetrafluoroethylthio) -5-thiazolylmethyl] ethylenediamine or trimethylenediamine, N- (2-cyclopropyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-imidazolylmethyl) ethylenediamine or -trimethylenediamine, N- (1-methyl-5-imidazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-fluoro-4-imidazolylmethyl) ethylenediarnine or -trimethylenediamine, N- (2-chloro-4-imidazolylmethyl) ethylenediamine or trimethylenediamine , N- (4-nitro-2-imidazolylmethyl) ethylenediamine or trimethylenediamine,

N- (4-trifluoromethylthio-2-imidazolylmethyl) ethylenediamine or trimethylenediamine,

N- (1,2-dimethyl-4-imidazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-2-trifluoromethylthio-4-imidazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-methyl-1,2, 3-triazol-4-ylmethyl) ethylenediamine or trimethylenediamine, N - [(1-methyl-1,2,3-triazol-4-yl) ethyl] -ethylenediamine or -trimethylenediamine, N- (3-methyl-1,2 , 4-triazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-trifluoromethyl-1,2,4-triazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,2,4-oxadiazole-4 -methyl) ethylenediamine or trimethylenediamine, N- (1,3,4-oxadiazol-2-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,2,3-oxadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-trifluoromethyl-1,2,4-oxadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-1,3,4-oxadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2 Trifluoromethyl-1,3,4-oxadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- [2- (2,2,2-trifluoroethyl) -1,3,4-oxadiazol-5-ylmethyl] ethylenediamine o trimethylene diamine, N- (1,2,4-thiadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,2,3-thiadiazol-4-ylmethyl) ethylenediamine or trimethylenediamine, N- [1- ( 1,2,3-thiadiazol-5-yl) ethyl] ethylenediamine or trimethylenediamine, N- (1,3,4-thiadiazol-2-yl) ethylenediamine or trimethylenediamine, N- [1- (1,3,4 Thiadiazol-2-yl) ethyl] ethylenediamine or trimethylenediamine, N- (1,2,5-thiadiazol-3-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-methyl-1,2,4-thiadiazole-5 -ylmethyl) ethylenediamine or trimethylenediamine, N- (4-methyl-1,2,3-thiadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-1,3,4-thiadiazol-5-ylmethyl ) ethylenediamine or trimethylenediamine, N- (2-trifluoromethyl-1,3,4-thiadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-fluoro-1,3,4-thiadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-chloro-1,3,4-thiadiazol-5-ylme'thyl) ethylenediamine or trimethylenediamine, N- (3-chloro-1,2,5-thiadiazol-4-ylmethyl) ethylenediamine or trimethylenediamine, N- [1- ( 3-tetrahydrofuryl) ethyl] ethylenediamine or trimethylenediamine, N- (3-tetrahydrothienylmethyl) ethylenediamine or trimethylenediamine, N- [1- (3-tetrahydrothienyl) ethyl] ethylenediamine or trimethylenediamine, N- (1-methyl-3-pyrrolidinylmethyl ) ethylenediamine or trimethylenediamine, N- (1,3-oxathiolan-2-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,3-dioxolan-4-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,3-oxathiolane 4-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,3-dithiolan-4-ylmethyl) ethylenediamine or trimethylenediamine, N- (thiazolidin-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (4-methyl-1 , 3-dioxolan-2-ylmethyl) ethylenediamine or trimethylenediamine,

N- (2-methyl-1,3-oxathiolan-4-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-chloromethyl-1,3-dioxolan-4-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoromethyl -1,3-dioxolan-4-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-oxo-1,3-dioxolan-4-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-formyl-thiazolidin-5-ylmethyl ) ethylenediamine or trimethylenediamine, N- (3-acetyl-thiazolidin-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-thiolen-2-ylmethyl) ethylenediamine or trimethylenediamine, N- (1,1-dioxo-3 -thiolen-3-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-isoxazolin-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-methyl-2-isoxazolin-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-trifluoromethyl-2-isoxazolin-5-ylmethyl) ethylenediamine or trimethylenediamine, N- [3- (2,2,2-trifluoroethyl) -2-isoxazolin-5-ylmethyl] -ethylenediamine or -trimethylenediamine, N- ( 2,4-dimethyl-2-isoxazolin-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-2-thi azolin-4-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-oxazolidinon-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (3-methyl-2-oxo-1,3-oxazolan-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylamino-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoroacetamido-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-methyl-2-thiooxothiazolidine-5 ylmethyl) ethylenediamine or trimethylenediamine, N- (3-chloro-1,2,4-oxadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (5-carboxy-2-oxazolylmethyl) ethylenediamine or trimethylenediamine, N- ( 2-dimethylamino-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (5-phenoxyfurfuryl) ethylenediamine or trimethylenediamine, N- (1-phenyl-4-pyrazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-benzyl-4-) pyrazolylmethyl) ethyleridiamine or trimethylenediamine, N- (2-phenyl-4-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (1-benzyl-2-imidazolylmethyl) ethylenediamine or -trimethylenediamine, N- (2-methylsulfinyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylsulfonyl-5-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylthio-1,3,4-thiadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylsulfonyl-1,3,4-thiadiazol-5-ylmethyl) ethylenediamine or trimethylenediamine,

N - (- 2-dimethylamino-5-thiazolylmethyl) ethylenediamine or trimethylenediamine; N- (5-carbamoyl-2-thiazolylmethyl) ethylenediamine or trimethylenediamine; N-1-B-methylaminocarbonyl-thiazolylmethyl ethylenediamine or trimethylenediamine, N- (5-dimethylaminocarbonyl-2-thiazolylmethyl) ethylenediamine or trimethylenediamine, N- (3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- [1- (3- Pyridyl) ethyl] ethylenediamine or trimethylenediamine, N- [1- (3-pyridyl) propyl] ethylenediamine or triethylenediamine, N- [2-methyl-1- (3-pyridyl) propyl] ethylenediamine or trimethylenediamine, N- (4 Pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-chloro-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-fluoro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-chloro-5-pyridylmethyl ) ethylenediamine or trimethylenediamine, N- [1- (2-chloro-5-pyridyl) ethyl] ethylenediamine or trimethylenediamine, N- (2-nitro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-cyano) 5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-amino-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-acetamido-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-dimethylamino-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-ethoxycarbonyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-acetyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-chloro-3-methyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-difluoromethyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-trifluoromethyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoromethyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-bromomodifluoromethyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-chlorodifluoromethyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (Trichloromethyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- [2- (2-chloroethyl) -5-pyridylmethyl] ethylenediamine or trimethylenediamine, N- [2- (2-fluoroethyl) -5-pyridylmethyl] ethylenediamine or trimethylenediamine, N- [2- (2,2,2-trifluoroethyl) -5-pyridylmethyl] ethylenediamine or trimethylenediamine, N- (2-difluoroethoxy-5- pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-trifluoromethoxy-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- [2- (2,2,2-trifluoroethoxy) -5-pyridylmethyl] ethylenediamine or trimethylenediamine, N- [ 2- (trifluoromethylthio) -5-pyridylmethyl] ethylenediamine or trimethylenediamine, N- (2-formyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-chlorodifluoromethylthio-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- [ 2- (2,2-dichlorovinyl) -5-pyridylmethyl] ethylenediamine or trimethylenediamine.

N- (5-trifluoromethyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-methyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (6-methyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (4-methyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-ethyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-butyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (4 , 6-dimethyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (3-chloro-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (3,5-dichloro-2-pyridylmethyl) ethylenediamine or -trimethylenediamine, N- (5-Fluoro-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (6-bromo-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- [2- (5-ethyl-2-pyridyl) ethyl] ethylenediamine or trimethylenediamine , N- (6-chloro-4-methyl-2-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-methyl-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-5-pyridylmethyl) ethylenediamine or - trimethylenediamine, N- (2-chloro-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-chloro-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-bromo-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-bromo-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (5-fluoro-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-fluoro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- [1- (2-fluoro-5-pyridyl) ethyl] ethylenediamine or trimethylenediamine, N- [2-methyl-1- (2-fluoro-5-pyridyl) -propyl] -ethylenediamine or -trimethylenediamine, N- (2-chloro -6-methyl-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2,4-dichloro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2,6-dichloro-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2,4-dibromo-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2,4-difluoro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-methoxy-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-methoxy-5 -pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-ethoxy-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-isopropoxy-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylthio-5-pyridylmethyl ) ethylenediamine or trimethylenediamine, N- (4-methyl-2-methylthio-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-ethylthio-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylsulfinyl-5 -pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-methylsulfonyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (4-chloro-2-fluoro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (6-chloro 2-methyl-3-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-chloro-4-methyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-allyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-propargyl-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2,3-dichloro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- [2- (1-propenyl ) -5-pyridylmethyl] ethylenediamine or trimethylenediamine, N- (2-chloro-4-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-fluoro-4-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2,6- Dichloro-4-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-methyl-4-pyridylmethyl) ethylenediamine or trimethylenediamine, N- [1- (2-chloro-4-pyridyl) ethyl] ethylenediamine or trimethylenediamine, N- (2-chloro-6-methyl-4-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2,6-dimethyl-4-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2-bromo-4-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (2,6-dibromo-4-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (3-chloro-2-fluoro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (3-bromo-2-) fluoro-5-pyridylmethyl) ethylenediamine or trimethylbenediamine, N- (2-chloro-3-fluoro-5-pyridylmethyl) ethylenediamine or trimethylenediamine, N- (3-chloro-2-methylthio-5-pyridylmethyl) ethylenediamine or trimethylenediamine, '2-amino-1- (4-pyridy 1-methylamino) propane, 2-amino-2-methyl- (3-pyridylmethylamino) propane, N- (4-pyridylmethyl) -2,2-dimethyltrimethylenediamine, 2-amino-1- {2-chloro-5-pyridylmethylamino) propane, N- (2-chloro-5-pyridylmethyl) -2-methyltrimethylenediamine, N- (3-pyridylmethyl) -N'-methylethylenediamine, N- (2-chloro-5-pyridylmethyl) -N'-methylethylenediamine or -trimethylenediamine, N - (2-fluoro-5-pyridylmethyl) -N'-isopropylethylenediamine, N- (2-chloro-5-pyridylmethyl) -N'-benzylethylenediamine, N- (2-chloro-5-pyridylmethyl) -N '- (3 -pyridylmethyl) ethylenediamine, N- (2-chloro-5-pyridylmethyl) -N '- (1-methyl-4-pyrazolylmethyl) ethylenediamine, 2-methyl-2- (2-methyl-5-pyridylmethylamino) ethanethiol, 1- methyl-2- (2-chloro-5-pyridylmethylamino) ethanethiol,

2- (4-pyridylmethylamino) ethanol, 2- (3-pyridylmethylamino) ethanol, 3- (2-methyl-3-pyridylmethyl) propanol, 2- (2-methyl-5-pyridylmethyl) ethanol, 2- (2-chloro -5-pyridylmethyl) ethanol, 2- (2-trifluoromethyl-5-pyridylmethyl) propanol, N- (1-methyl-4-pyrazolylmethyl) -2,2-dimethyltrimethylenediamine, N, N'-bis (5-methyl-2 -furfuryl) ethylenediamine, N- (3-methyl-5-isoxazolylmethyl) -N '- (1-methyl-4-pyrazol-ylmethyl) ethylenediamine or trimethylenediamine, 2- (3-methyl-5-isoxazolylmethylamino) ethanethiol, 3 - (1-isopropyl-4-pyrazolylmethylamino) propanethiol, 2- (1,2,5-thiadiazol-3-ylmethylamino) ethanethiol, 2- (2-trifluoromethyl-5-thiazolylmethylamino) ethanethiol, 2- (3-methyl-5 -isoxazolylmethylamino) ethanol, 2- (4-isothiazolylmethylamino) ethanol, 2- (5-oxazolylmethylamino) ethanol, 2- (3-trifluoromethyl-5-isoxazolylmethylamino) ethanol, 2- (5-pyrimidinylmethylamino) ethanethiol, 2- (3- Trifluoromethyl-6-pyridazinylmethylamino) ethanethiol, 2- (2-methyl-5-pyrazinylmethylamino) ethanethiol, 2- (3-pyrazinylmethylamino) ethanol, 2- (3-chloro-6 -pyridazinylmethylamino) ethanol, 2-amino-1- (2-pyrazinylmethyl) aminopropane, N- (5-pyrimidinylmethyl) -N '- (1-methyl-4-pyrazolylmethyl) ethylenediamine and NO-chloro-e-pyridazinylmethyl I-N' -methylethylendiamin.

As indicated above, formula (II) comprises novel compounds.

In the case of the compounds of formula (II) falling under formula (II)

-X ² H (ua)

i, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R and Z have the meanings given above and X 2 denotes an oxygen atom or -NR ¹⁰ , where R ¹⁰ is as defined above The compounds of the formula (HA) can be obtained if (g) the compounds of the above-indicated formula (VIII) are reacted with the compounds of the formula (IX)

(IX)

in which n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ and X ² have the meanings given above, are reacted, optionally in the presence of inert solvents and in the presence of acid acceptors.

For example, when pyrazinylmethyl chloride and ethylenediamine are used as starting materials in the process (g), the reaction can be represented by the following equation:

The compounds of the formula (II) can be obtained if (h) the compounds of the formula (X)

Il

Z-C-R in which Z and R have the meanings given above, with the compounds of the formula (XI)

-19- Z4Z742

in which R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁶ and X ¹ have the meanings given above, are reacted and the resulting products are reduced, optionally in the presence of inert solvents.

When, for example, 6-chloronicotinaldehyde and 3-aminopropanethiol are used as starting materials in process (h), the course of the reaction can be represented by the following equation:

Cl - // MCH + H ₂ N - (CH ₂ J ₃ -SH

H> Cl - // V) -CH, -NH- (CH-), -SH

^l 2'3

On the other hand, in the method (h), when, for example, 5-pyrimidinecarbaldehyde and ethylenediamine are used as starting materials, the course of the reaction can be represented by the following equation:

N.

7-CH = N- (CH,) - NH

} ('y -CH ₂ -NH- (CH ₂ J ₂ -NH ₂

The compounds of the formula (VIII) in the method (g), hereinafter referred to as examples, are the same as the starting materials in the above-mentioned method (f).

The compounds of formula (IX), including both known and novel compounds, can be readily prepared by known methods.

As examples of compounds of formula (IX) may be

Ethylene diamine and trimethylene diamine

mentioned (see DE-OS 2732660 and FR-PS 1499785). Further to mention are also

2-aminoethanol and 3-aminopropanol,

which are well-known compounds in organic chemistry.

Also included are N-benzylethylenediamine or trimethylenediamine (see Japanese Patent Laid-Open No. 78971/1985 and German Laid-Open Nos. 2514402 and 2732660 and Japanese Patent Application No. 68551/1985) and N-substituted alkylethylenediamines or trimethylenediamines which are ethylenediamines or trimethylenediamines in the above Formula (II), for examples of compounds of formula (IX).

In process (g), the desired compounds of formula (II) can be readily obtained by reacting the compounds of formula (VII) with the compounds of formula (IX) in inert solvents, as illustrated by process (a), which will be described in detail later.

The process (g) can be carried out in a simple manner by adding more than 1 mol, for example about 5 mol, of the compounds of the formula (IX) to 1 mol of the compounds of the formula (VIII) at a reaction temperature in the range of, for example, 0 ° C to 50 ° C to the action brings.

The compounds of the formula (X) used as starting materials in the process (h) comprise mostly known compounds. Examples include:

6-chloronicotinaldehyde,.

6-Bromohicotinaldehyd,

6-Fluoronicotinaldehyd,

B-acetyl ^ -chloropyridine, B ^ -dichloronicotinaldehyde, δ-chloro-δ-fluoronicotinaldehyde, 2-chloro-4-pyridylcarbaldehyde, S-chloro ^ -pyridinecarbaldehyde, 3,5-dichloro-2-pyridinecarbaldehyde, B-fluoro ^ - pyridinecarbaldehyde, G-bromo-pyridinecarbaldehyde, 2-chloronicotinaldehyde, S-chloronicotinaldehyde, 5-bromonicotinaldehyde, 5-fluoronicotinaldehyde, B-acetyl-4-fluoropyridine, 4,6-dichloronicotinaldehyde, S-dibromonicotinaldehyde, 2,6-difluoro- 4-pyridinecarbaldehyde, 2-fluoro-4-pyridinecarbaldehyde, 2,6-dibromo-4-pyridinecarbaldehyde, S-bromo-e-fluoronicotinaldehyde, G-chloro-S-fluoronicotinaldehyde,

Nicotinaldehyde, 4-pyridinecarbaldehyde, 6-methylnicotinaldehyde, 6-ethylnicotinaldehyde, 6-allylnicotinaldehyde, 6-propargylnicotinaldehyde, 6-methoxynicotinaldehyde, 6-methylthionicotinaldehyde, 6-methylsulfonylnicotinaldehyde, S-chloro ^ -methylnicotinaldehyde, 3-acetylpyridine, 6-nitronicotinaldehyde, 6 Cyanonicotinaidehyde, e-methylsulfinylnicotinaldehyde, 6-phenylnicotinaldehyde, 6-benzylnicotinaldehyde, 6-phenoxynicotinaldehyde, 6- (2-ethoxyethyl) nicotinaldehyde, e-trichloromethylnicotinaldehyde, e-methoxymethylnicotinaldehyde, 6-difluoromethoxynicotinaldehyde, 6-trifluoromethoxynicotinaldehyde, 6- (2,2 , 2-trifluoroethoxy) nicotinaldehyde, e-chlorodifluoromethylthionicotinaldehyde, e-trifluoromethylthionicotinaldehyde, B-difluoromethylthionicotinaldehyde, e-trifluoromethylsulfonylnicotinaldehyde, e-trifluoromethylsulfinylnicotinaldehyde, 6- (2,2-dichlorovinyl) nicotinaldehyde, 4-pyrimidinecarbaldehyde, 2-methyl-4-pyrimidinecarbaldehyde, 2-methyl-6-oxo-1H, 6H-dihydropyrimidine-4-carbaldehyde, 5-pyrimidinecarbaldehyde, 2-methyl l ⁱ 5-pyrimidinecarbaldehyde, 2-dimethylamino-5-pyrimidinecarbaldehyde, 2,4,6-trichloro-5-pyrimidinecarbaldehyde, pyrazylcarbaldehyde, acetylpyrazine,

2-methyl-5-pyrazinecarbaldehyde, 3-pyridazinecarbaldehyde, 2-chloro-4-pyrimidinecarbaldehyde _/ 4-chloro-6-pyrimidinecarbaldehyde, 4-methyl-6-pyrimidinecarbaldehyde, 2-fluoro-5-pyrimidinecarbaldehyde, B-acetyl-fluoropyrimidine , 2-chloro-5-pyrimidinecarbaldehyde, 2-isopropyl-5-pyrimidinecarbaldehyde, 2-chlorodifluoromethyl-5-pyrimidinecarbaldehyde _/

-II ^] _A U. -I

2-Bromodifluoromethyl-5-pyrimidine carbaldehyde,

2-Methoxy-5-pyrimidine carbaldehyde,

2-difluoromethoxy-5-pyrimidine carbaldehyde,

2-trifluoromethoxy-5-pyrimidiπcarbaldehyde, '

2- (2,2,2-trifluoroethoxy) -5-pyrimidine carbaldehyde,

2-methylthio-5-pyrimidine carbaldehyde,

2-ethylthio-5-pyrimidine carbaldehyde,

2-Difluoroethylthio-5-pyrimidine carbaldehyde,

2-trifluoromethylthio-5-pyrimidine carbaldehyde,

2-nitro-5-pyrazincarbaldehyd,

2-cyano-5-pyrazincarbaldehyd,

2-Chloro-5-pyrazincarbaldehyd,

S-trifluoromethyl-ö-pyrazincarbaldehyd,

S-fluoro-e-pyridazincarbaldehyd,

S-methyl-ö-pyridazincarbaldehyd,

4-Pyridazincarbaldehyd,

S-chloro-s-pyridazincarbaldehyd,

S-trifluoromethyl-e-pyridazincarbaldehyd,

1,3,5-triazine-2-carbaldehyde

S-chloro-Î Atriazin-G-carbaldehyde

Sjö-dichloro-i ^^ - triazine-G-carbaldehyde and S-chloro-I ^ Aö-tetrazine-e-carbaldehyde.

The compounds of formula (X) can be prepared by various conventional procedures. These are specifically described below.

For example, the pyridine carbaldehydes of formula (X) can be prepared by reacting the corresponding vinylpyridines in an ozonolysis reaction (see J. Org. Chem. 26, 4912-4914), and according to GBPS 2002368, G 1 can be chloronicotinaldehyde from 2 Chloro-5-pyridylcarbonitrile be obtained.

Moreover, the compounds of formula (X) can generally be prepared without difficulty according to conventional methods by reduction of the corresponding carboxylic acids or their esters or by means of the Vilsmeyer reaction. For example, pyridine carbaldehydes can also be prepared by reduction of the corresponding pyridinecarboxylic acids and their esters (see Org. React, Vol. 8.218-257).

The compounds of formula (X) can also be prepared directly by ring formation. For example, with respect to 4-pyrimidinecarbaldehyde, the corresponding 2-methylthio-4-methyl-6-pyrimidinecarbaldehyde-acetyl is obtained by reacting diethoxyacetylacetone with S-methylisothiourea. Subsequent reduction and treatment with hydrochloric acid yields 4-ethyl-6-pyrimidinecarbaldehyde. The use of diethoxyacetylacetone derivatives may lead to the synthesis of similar compounds such as 4-pyrimidinecarbaldehyde, 2-methyl-4-pyrimidinecarbaldehyde and 2-trifluoromethyl-4-pyrimidine-carbaldehyde (described in Chem. Ber. 97, pp.3407-3417). There are many known methods in the field of organic chemistry for the synthesis of 5-pyrimidine carbaldehydes.

For example, 5-pyrimidinecarbaldehyde can be synthesized by introducing a formyl group to the 5-position of 4-hydroxy-6-oxodihydropyrimidine by Vilsmeyer reaction, halogenating the product to 4,6-dichloro-5-formylpyrimidine, and obtaining the Compound dehalogenated (Liebigs Ann. Chem. 766, p.73-83; and Monatsh. Chem. 96, pp. 1567-1572). By using this reaction, 2-alkyl-substituted and 2-haloalkyl-substituted 5-pyrimidinecarbaldehydes can be synthesized. 5-Pyrimidincarbaldehyde with other substituents in the 2-position are described in JP-A 59669/1984.

For example, 5-pyrimidine carbaldehydes having such substituents as alkyl, alkoxy, alkylthio or alkylamino in the 2-position are obtained by reaction of .alpha.j2 - [(dimethylamino) methylene] propanediylidene ^ to [(dimethylamino-perchlorate] (described in Collect Comm., 30, p.2125) with suitable amidine hydrochlorides.

As regards 5-pyrimidine carbaldehydes having halogen in the 2-position, for example, 2-chloro-5-pyrimidinecarbaldehyde may be prepared by chlorinating ethyl 2-oxo-1,2-dihydro-5-pyrimidinecarboxylate with phosphorus oxychloride to give ethyl 2-chloro S-pyrimidinecarboxylate (Chem. Pharm. Bull. 12, pp. 804-808; a similar example can be found in J. Org. Chem. 29, pp. 1740-1743) and reducing the compound obtained in the usual way. As the chlorine _; Atom in the 2-position has activity, it can be converted into other substituents, for example in 2-fluorine with the aid of potassium fluoride. As for pyridazine carbaldehyde, 3- and 4-pyridazine carbaldehydes are on page 213 of the month. Chem., Vol. 108, and methyl-substituted pyridazine carbaldehydes in J. Heterocycl. Chem. 17, p. 1501.

Incidentally, the 5-membered heterocyclic carbaldehydes will be described in detail below. FurfuraList is a known compound and can easily allow the introduction of a halogen atom on the furan ring. For example, 5-chlorofurfural and 4,5-dichlorofurfural can be synthesized from furfural (Zh. Org. Khim. 11, pp. 1955-1958). 5-Nitrofurfural is also an easily available known compound, 5-cyanofurfural is a compound described in Tetrahedron 39, p. 3881, and 5-phenoxyfurfural is a compound described in Chem. Pharm. Bull. 28 (No.9 ), P. 2846. Furancarbaldehydes other than furfural, alkyl-substituted, in particular methyl-substituted furfurals and other furancarbaldehydes are also known compounds and can be obtained in a simple manner. Thiophenecarbonaldehyde is a known compound and a halogen atom is easily introduced on the thiophene ring. For example, 2,3-dichloro-4-thiophenecarbaldehyde can be synthesized from 3-thiophenecarbaldehyde (Tetrahedron 32, pp. 1403-1406). 2,3-Dibromo-5-thiophenecarbaldehyde can be synthesized from 2-thiophenecarbaldehyde (J. Org. Chem. 41, p. 2835). Alkyl-substituted, in particular methyl-substituted, thiophenecarbaldehydes are likewise known compounds. Alkylthio-substituted or haloalkylthio-substituted thiophenecarbaldehydes can be obtained by alkylating or haloalkylating mercapto-substituted thiophenecarbaldehyde. For example, 2-methylthio-5-thiophenecarbaldehyde is a known compound described in Zh. Obshch. Khim., 34, pp. 4010-4015. Generally, alkylthio-substituted or haloalkylthio-substituted heterocyclic carbaldehydes can be prepared by the above methods.

Nitrosubstituted thiophenecarbaldehydes can be easily synthesized by nitration of the thiophene ring. For example, 4-nitro-2-thiophenecarbaldehyde and 2-nitro-4-thiophenecarbaldehyde are known compounds disclosed in Bull. Soc. Chim. France 1963, pp. 47 & -484.

Pyrrole carbaldehyde are known compounds. i-methyl-2-pyrrolecarbaldehyde can be prepared from 1-methylpyrrole by Vilsmeier reaction or by methylating 2-pyrrolecarbaldehyde (Beilstein, vol. 21, page 279).

4-isothiazolecarbaldehyde can be synthesized from 4-isothiazolylcarboxylic acid (J.Medicine.Chem.13, p.1208-1212), and 5-isothiazolecarbaldehyde can be synthesized from 5-isothiazolyl-lithium (J.Chem.Soc.

5-pyrazolecarbaldehyde and 3-methyl-5-pyrazolecarbaldehyde can be prepared by direct ring synthesis (Chem. Ber.

97, pp. 3407-3417). By a similar method, 3-trifluoromethyl-5-pyrazolecarbaldehyde can be synthesized.

A formyl group may be introduced to the 4-position of an N-alkyl or N-arylpyrazole by the Vilsmeier reaction. 4-Pyrazolecarbaldehyde can be obtained by eliminating the benzyl residue from N-benzyl-4-pyrazolecarbaldehyde

(J. Chem. Soc. 1957, p.3314 and 3315).

4-methyl-5-imidazole carbaldehyde and 1-methyl-5-imidazole carbaldehyde are known compounds (J. Pharm. Soc., Japan, 60, p.184-188; J. Amer ).

Many substituted thiazolecarbaldehydes are known (Japanese Laid-Open Patent Publication No. 206370/1984, Chem. Abstr., 62, 7764d, Chem. Ber., 101, p.3872).

For example, 2-chlorothiazole-5-carbaldehyde can be synthesized by lithiation with the aid of butyllithium and subsequent formylation. Substituted 1,3,4-thiadiazolecarbaldehydes are also known compounds (Japanese Laid-Open Patent Publication No. 206370/1984). 1,2,3-thiadiazole-5-carbaldehyde is also a known compound (GB-PS 1113705).

The compounds of the formula (XI) in the process (h) include the compounds of the above-mentioned formula (IX).

Besides, 2-aminoethanethiol and 3-aminopropanethiol are exemplified (see J. Org. Chem. 27, 4712-4713), and also the aminoalkane thiols constituting them are among these examples.

For example, when X ^{3 is} a sulfur atom, the above process (h) can be carried out in the same manner as described in J. Org. Chem. 27, 2452-2457 and 4712-4713.

In carrying out the process (c), in the first step, the thiazolidines or the tetrahydrothiazines can be prepared as intermediates by reacting the compounds of the formula (X) with the compounds of the formula (XI) in the presence of an inert solvent such as benzene, and in the next step, the intermediates can be reduced by means of a reducing agent such as sodium borohydride, lithium aluminum hydride, aluminum borohydride, potassium borohydride, etc., to produce the compounds of formula (Hb).

When practicing process (h) in practice, the thiazolidines or tetrahydrothiazines as intermediates can be prepared not only by distilling off the volatile material after the reaction of the first step under reduced pressure, for example at 1.33 mbar (1 mmHg) at 50 ^° C to 80 ° C ⁰ C, but they can also be immediately subjected to reduction without isolation.

In the case where X ³ -N. Is ¹⁰ , according to process (h), the desired compound of formula (Mb) can be obtained by refluxing the starting materials in an inert solvent (such as benzene) and then refluxing the reaction mixture, usually immediately without separation of the boat base or amine is reduced, as shown in detail in a working example given below.

In carrying out the process (h), it is preferable to use an amount of more than 1 mole, for example, about 5 moles, of the compounds of the formula (XI) per 1 mole of the compounds of the formula (X), and the reaction becomes atmospheric a temperature in the range of usually O ⁰ C to 100 ° C performed.

In addition, as an alternative process for the preparation of compounds of formula (II) in which X ^{1 is} a sulfur atom, it is possible to cite a process in which the compounds of formula (II) in which X ^{1 is} an oxygen atom, are halogenated with a halogenating agent such as thionyl chloride and then the resulting products are reacted with potassium hydrogen sulfide.

The compounds of formula (III) in process (a) include both known and novel compounds.

As examples of known compounds may be mentioned (see, for example, Chem. Ber. 100, 591-604):

1-Nitro-2,2-bis ethylene (methylthio),

1-Nitro-2,2-bis ethylene (ethylthio)

1-nitro-2,2-bis (benzylthio) ethylene and

2-nitromethylene-1,3-dithiolane.

The above compounds can be prepared usually by reacting nitromethane with carbon disulfide in the presence of a base and alkylating the resulting product.

If other nitroalkanes are used in place of nitromethane in the process in question, similar compounds corresponding to formula (III) can be readily prepared.

In addition, when using acyl-substituted nitromethanes in place of nitromethane in the process in question other desired compounds of formula (III) can be prepared.

For example, when benzoylnitromethane is used, 1-benzoyl-1-nitro-2,2-bis (methylthio) ethylene, a new compound, can be prepared, and when acetylnitromethane is used, 1-acetyl-1-nitro-2,2 -bis (methylthio) ethylene, a new compound.

The compounds of the formula (IV) in the process (b) are known compounds (see Chem. Abstr. 44, 1011 f., Japanese Patent Laid-Open No. 137473/1984). As examples may be mentioned:

2,2-Dichloronitroethylen,

1,2,2-Trichloronitroethylen,

1-Fluoro-2,2-dichloronitroethylen,

1-methyl-2,2-dichloronitroethylen,

The compounds of formula (V) in process (c) are known compounds (see J. Org. Chem. 25, 1312; ibid. 28, 1281-1283; Chem. Ber. 758, 1323-1330; Japanese Patent Laid-Open No. 48978) / 1985). As examples may be mentioned:

2,2,2-trichloro-1-nitroethane,

1,2,2,2-tetrachloro-i-nitroethane,

2,2,2-trifluoro-1-nitroethane.

The formula (VI) provides a general definition of the starting materials in the process (e) compounds required, wherein the defined hereinabove respective meanings of n, R ^1, R ^2, R ^3, R ^4, R ^5, R ⁶ X, R and Z are referred to. In the formula (VI), n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, R and Z preferably have the meanings already described above. Compounds of formula (VI) include both known and novel compounds. For example, 2-imino-3- (4-pyridylmethythiazolidine is disclosed in J. Med. Chem. 22, 237-247.

Other compounds corresponding to the formula (VI) can be prepared in the same manner as mentioned in the above reference.

The compounds of the formula (VI) can be prepared, for example, by reaction of the above-mentioned compounds with cyano halides.

The reaction can be easily accomplished by mixing the reactants with stirring in inert solvents, and the resulting products can be obtained in the form of their hydrohalides. As specific examples of the compounds of the formula (VI) (in the form of a hydrohalide), mention may be made of the following compounds:

Hydrobromides or hydrochlorides of 1- (2-chloro-5-pyridylmethyl) -2-iminoimidazolidine, 1- (2-chloro-5-pyridylmethyl) -2-iminotetrahydropyrimidine, 1- (2-fluoro-5-pyridylmethyl) -2- iminoimidazolidine, 1- (2-bromo-5-pyridylmethyl) -2-iminoimidazolidine, 1- (2-trifluoromethyl-5-pyridylmethyl) -2-iminoimidazolidine, 1- (2-methyl-5-pyridylmethyl) -2-iminoimidazolidine, 1- (3-pyridylmethyl) -2-iminoimidazolidine, 1- (3-pyridylmethyl) -2-iminotetrahydropyrimidine, 1- (2-trifluoromethoxy-5-pyridylmethyl) -2-iminoimidazolidine and 1- (2-methoxy-5-pyridylmethyl ) -2-iminoimidazolidine.

The formula (VII) provides a general definition of the starting material in process (f) required connections, wherein, to the details given in the foregoing respective meanings of n, R ^1, R ^2, R ^3, R ^4, R ^5, R ⁶ X and Y are referred to. In the formula (VII), n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X and Y preferably have the meanings already described above. The compounds of formula (VII) are most often known compounds. As examples there may be mentioned: 2-nitromethylene-imidazolidine, 2-nitromethylene-tetrahydropyrimidine, 4,4-dimethyl-2-nitromethylene-imidazolidine, 3-methyl-2-nitromethylene-imidazolidine, 3-allyl-2-nitromethylene-imidazolidine, 3-propargyl-2-nitromethylene-imidazolidine, 3-chloro-3-allyl ) -2-nitromethylene-imidazo-1-ol, 3-acetyl-2-nitromethylene-imidazolidine, S-chloroacetyl-1-nitromethylene-imidazolidine, 3-benzoyl-2-nitromethylene-imidazolidine, 3-p-tosyl-2-nitromethylene-imidazolidine, 2-nitromethyl-thiazolidine, 2 ^: Nitr-5-methyl-tetrahydro-2H -1,3-thiazine, 2-nitromethylene-5-methyl-thiazolidine, 2-nitromethylene-oxazolidine, 2-1-litromethylene-4-methyloxazolidine, 2-1-litromethylene-tetrahydro-2H-1,3-oxazine, 2-nitromethylene-pyrrolidine, 2-nitromethylenepiperidine , 2- (1-nitroethylidene) imidazolidine, 2- (1-nitro-2-fluoroethylidene) imidazolidine,

2- (phenylnitromethylene) imidazolidine, *

2- (1-nitro-2,2,2-trifluoroethylidene) imidazolidine, ethylnitro (imidazolidin-2-ylidene) acetate, n-butyl-nitro (tetrahydropyrimidin-2-ylidene) acetate, o-tolyl-nitro ( imidazolidin-2-ylidene) acetate, p-chlorophenyl nitro (imidazolidin-2-ylidene) acetate, p-nitrophenyl nitro (imidazolidin-2-ylidene) acetate, 2- (methylthionitromethylene) imidazolidine, 2- (propylthionitromethylene) imidazolidine, 2 - [(4-chlorophenylthio) nitromethylene] imidazolidine, 2- (acetylnitromethylene) imidazolidine, 2- (dinitromethylene) imidazolidine, 2- (benzoylnitromethylene) imidazolidine, ethyl nitro-fi-ethoxycarbonyl-imidazolidine-1-ylidene diacetate, phenyl-nitro (1) phenylthiocarbonylimidazolidin-2-ylidene) acetate, 2- (phenylthionitromethylene) -1-phenylthioimidazolidine, 2- (1-nitroethylidene) tetrahydro-2H-1,3-thiazine, 2- (1-nitro-3-butylidene) thiazolidine, 2 - (1-nitro-3-butylidene) tetrahydro-2H-1,3-thiazine,

2- (1-nitro-2-phenylethylidene) thiazolidine, 2- (3-acetyl-1-nitropropylidene) tetrahydro-2H-1,3-thiazine, 2- (3-cyano-1-nitropropylidene) -tetrahydro-2H 1,3-thiazine, methyl 4-nitro-4- (thiazolidin-2-ylidene) butoxide, 2- (2-ethylthio-1-nitroethylidene) -tetrahydro-2H-1,3-thiazine, 2- (2 -Dimethylamino-1-nitroethylidene) thiazolidine, ethyl-nitro (tetrahydro-2H-1,3-thiazin-2-ylidene) acetate, phenyl-nitro (tetrahydro-2H-1,3-thiazin-2-ylidene) acetate , 2-formylnitromethylenthiazolidine, 2-acetylnitomomethylene-tetrahydro-2H-1,3-thiazine, 2-benzoylnitromethylene-tetrahydro-2H-1,3-thiazine, 2-phenylthionitromethylene-tetrahydro-2H-1,3-thiazine, ethyl-nitro - (oxazolidin-2-ylidene) -acetate, ethyl-nitro- (tetrahydro-2H-1,3-oxazin-2-ylidene) -acetate, S-methyl -nitromethylene-pyrrolidine, S-fluoro -nitromethylene-piperidine, methyl-nitro- ( pyrrolidin-2-ylidene) acetate, 3-methylthio-2-nitromethylene-piperidine, ethyl-nitro (thiazolidin-2-ylidene) -acetate, 2-nitro-imino-imidazolidine, ^^ dimethyl -nitroimino-imidazolidine, 2-nitro -iminotetrahydropyrimidine, S Methyl ^ -nitroiminoimidazolidin,

S-isopropyl-nitroiminoimidazolidine, "

3- (2-ethoxyethyl) -2-nitroiminoimidazolidine, S-ethoxycarbonyl-nitroiminoimidazolidine, S-phenylthio-nitroiminoimidazolidine, S-formyl-nitroiminoimidazolidine, S-acetyl-nitroiminotetrahydropyrimidine, 3- (2-bromo-3,3 -dimethylbutyryl) -2-nitroiminoimidazolidine, 3- (2-trifluoromethylbenzoyl) -2-nitroiminoimidazolidine, 3- (2,4-dichloro-3-methylbenzoyl) -2-nitroiminoimidazolidine, 3- (4-methoxybenzoyl) -2-nitroiminoimidazolidine,

3- (3-chloropropylsulfonyl) -2-nitroiminoimidazolidine,

3- (2-Difluoromethoxybenzoyl) -2-nitroiminotetrahydropyrimidine, 3-Phenoxycarbonyl-2-nito-iminoimidazolidine,

3- (2-Formyl) -2-nitroiminotetrahydropyrimidine, 3- (2-Methylthiazol-5-ylcarbonyl) -2-nitroiminoimidazolidine, 3- (Diethoxyphosphono) -2-nitroiminoimidazolidine, 3- (5-nitro-2-methylbenzenesulfonyl) - 2-nitroiminoimidazolidine, 2-nitroiminothiazolidine, 2-nitroinninotetrahydro-2H-1,3-thiazine, 2-nitroiminooxazolidine, 4-methyl-2-nitroiminooxazolidine, 2-nitroiminopyrrolidine, 2-nitroiminopiperidine, 3-methyl-2-nitroiminopyrrolidine and 2- Nitroiminotetrahydro-2H-1,3-oxazine.

2-Nitromethylene-imidazolidines (or -tetrahydropyrimidines) of the above-mentioned formula (VII) are known compounds (see / example, Chem. Ber. 100, 591-604, the BE-PS 821 281 and the US-PS 3971774). In addition, N-acyl derivatives of 2-nitromethylene-imidazolidines (or tetrahydropyrimidines) can be prepared by known methods (see Japanese Patent Laid-Open Nos. 67473/1985 and 61 575/1985).

In addition, compounds of the formula (VII) in which, in addition to a nitro group, another group to the methylene. Group of 2-nitromethylene-imidazolidines (or tetrahydropyrimidines) are prepared by known methods described in US-PS 3996372,4002765,4042 696,4052411, 4053619,4053622 and 4053623, JP-OS 151727/1977 and the BE-PS 821282 are described.

2-Nitromethylene-thiazolidines (or tetrahydro-2H-1,3-thiazines) are also for the most part well-known compounds that can be easily prepared, for example, by reaction of aminoalkanethiols with compounds of the above formula (III) represented by those of above formula (IV) or formula (V) can be replaced.

In addition, the 2-position of 2-nitromethylene-thiazolidines (or tetrahydro-2H-1,3-thiazines) can be substituted by various known methods to give desired starting materials of formula (VII) (see U.S. Patent 3,962,234 , 4022775, 4024254, 4044128, 4045434 and 4076813, as well as JP-OS 151 882/1975).

2-Nitromethylene-oxazolidines (or tetrahydro-2H-1,3-oxazines) are also largely known compounds that can be readily prepared, for example, by reaction of aminoalkanols with compounds of the above formula (III) by those of the above Formula (IV) or Formula (V) may be replaced [see Adv. Pestic. Sei., Plenary Lect. Symp. Pap. Int. Congr. Pestic. Chem. 4-th., 1978, 206-217 (Chem. Abstr. 91, 103654), US Pat. No. 3,907,790 and Japanese Patent Laid-Open Nos. 151882/1975 and 151727/1977].

2-Nitromethylene-pyrrolidines (or -piperidines) are also known compounds which can be prepared, for example, by reacting 2-methoxypyrroline-1 with nitroalkanes (see NL-PS 7306020 and 7306145). 2-Nitroimino derivatives of formula (VII) are also known compounds.

For example, 2-nitroiminooxazolidines are described in J. Amer. Chem. Soc. 73, 2213-2216.

2-Nitroiminoimidazolidines, 2-Nitroiminotetrahydropyrimidines and their N-acetyl derivatives are described in J. Amer. Chem. Soc. 73, 2201-2205 and in GB-PS 2055796.

N-acyl derivatives excluding N-acetyl derivatives, N-sulfinyl derivatives, N-sulfonyl derivatives and N-phosphono derivatives are novel compounds which can be prepared in the same manner as described in British Patent 2,055,796 ,

2-nitroimino-thiazolidines (or -tetrahydro-2H-1,3-thiazines) and 2-nitro-imino-pyrrolidines (or -piperidines) obtained by reaction of nitroguanidine with the diamines, the aminoalkanols or the aminoalkanethiols or by reaction of the Lmino compound can be prepared with nitric acid in the presence of sulfuric acid, are also described in the above GB-PS.

The formula (VIII) gives a general definition of the compounds required as starting materials in the process (f), referring to the respective Z and R mentioned in the foregoing.

In the formula (VIII), Z and R preferably have the meanings already described above.

The compounds of the formula (VIII) which can be used according to the present invention comprise known compounds which have already been described, for example, in J. Org. Ghem. 34.3547; J. Medicin. Chem. 14, 211-213 and 557-558 (1971); US Pat. No. 4,332,944 and US Pat

J. Heterocycl. Chem. 1979, 16, 333-337.

As examples may be mentioned:

3-picolyl chloride,

1- (3-pyridyl) ethyl chloride, 1- (3-pyridyl) propyl chloride, 2-methyl-1- (3-pyridyl) propyl chloride, 4-picolyl chloride,

5-chloro-2-pyridylmethyl chloride, 2-fluoro-5-pyridylmethyl chloride, 2-chloro-5-pyridylmethyl chloride, 1- (2-chloro-5-pyridyl) ethyl chloride, 2-nitro-5-pyridylmethyl chloride, 2-cyano-5 -pyridylmethyl chloride, 2-amino-5-pyridylmethyl chloride, 2-acetamido-5-pyridylmethyl chloride, 2-dimethylamino-5-pyridylmethyl chloride, 2-ethoxycarbonyl-5-pyridylmethyl chloride,

2-acetyl-5-pyridylmethyl chloride ^;

2-chloro-3-methyl-5-pyridylmethyl chloride, 2-difluoromethyl-5-pyridylmethyl chloride,

5-trifluoromethyl-2-pyridylmethyl chloride, ·

2-Bromodifluoromethyl-5-pyridylmethyl chloride, 2-chlorodifluoromethyl-5-pyridylmethyl chloride, 2-trichloromethyl-5-pyridylmethyl chloride, 2- (2-chloroethyl) -5-pyridylmethyl chloride, 2- (2-fluoroethyl) -5-pyridylmethylchloride, 2- (2,2,2-trifluoroethyl) -5-pyridylmethyl chloride, 2-difluoroethoxy-5-pyridylmethyl chloride, 2-trifluoroethoxy-5-pyridylmethyl chloride, 2- (2,2,2-trifluoroethoxy) -5-pyridylmethyl chloride, 2- (trifluoromethylthio ) -5-pyridylmethyl chloride, 2-formyl-5-pyridylmethyl chloride, 2-chlorodifluoromethylthio-5-pyridylmethyl chloride, 2- (2,2-dichlorovinyl) -5-pyridylmethyl chloride, S-trifluoromethyl-pyridylmethyl chloride, 5-methyl-2 -pyridylmethyl chloride, 6-methyl-2-pyridylmethyl chloride, 4-methyl-2-pyridylmethyl chloride, 5-ethyl-2-pyridylmethyl chloride, δ-butyl-pyridylmethyl chloride, 4,6-dimethyl-2-pyridylmethyl chloride, S-chloro -pyridylmethyl chloride , SS-dichloro ^ -pyridylmethyl chloride, S-fluoro ^ -pyridylmethyl chloride, 6-bromo-2-pyridylmethyl chloride, e-chloro ^ -methyl ^ -pyridylmethyl chloride, ö-methyl 1-pyridylmethyl chloride, 2-methyl-5-pyridylmethyl chloride, 2-chloro-3-pyridylmethyl chloride, 6-chloro-S-pyridylmethyl chloride, 8-bromo-S-pyridylmethyl chloride, 2-bromo-5-pyridylmethyl chloride, 6-fluoro-S- pyridylmethyl chloride, 2-fluoro-5-pyridylmethyl chloride, 1- (2-fluoro-5-pyridyl) ethyl chloride,

2-methyl-1- (2-fluoro-5-pyridyl) propyl chloride, 2-chloro-6-methyl-3-pyridylmethyl chloride, 2,4-dichloro-5-pyridylmethyl chloride, 2,6-dichloro-5-pyridylmethyl chloride, 2 , 4-dibromo-5-pyridylmethyl chloride, 2,4-difluoro-5-pyridylmethyl chloride, 2-methoxy-3-pyridylmethyl chloride, 2-IVethoxy-5-pyridylmethyl chloride, 2-ethoxy-5-pyridylmethyl chloride _/ 2-isopropoxy-5-pyridylmethyl chloride , 2-methylthio-3-pyridylmethyl chloride, 2-methylthio-5-pyridylmethyl chloride, 4-methyl-2-methylthio-5-pyridylmethyl chloride, 2-ethylthio-5-pyridylmethyl chloride, 2-methylsulfinyl-5-pyridylmethyl chloride, 2-methylsulfonyl 5-pyridylmethyl chloride, 4-chloro-2-fluoro ^: 5-pyridylmethyl chloride, e-chloro-methyl-S-pyridylmethyl chloride, 2-chloro-4-methyl-5-pyridylmethyl chloride,. 2-allyl-5-pyridylmethyl chloride, 2-propargyl-5-pyridylmethyl chloride, 2,3-dichloro-5-pyridylmethylchloride, 2- (1-propenyl) -5-pyridylmethyl chloride, Z-chloro -pyridylmethyl chloride, 2-fluoro-4 pyridylmethyl chloride, 2,6-dichloro-4-pyridylmethyl chloride, 2,6-difluoro-4-pyridylmethyl chloride, 2-methyl-4-pyridylmethylchloride, 1- (2-chloro-4-pyridyl) ethyl chloride, 2-chloro-6- methyl 4-pyridylmethylchloride, 2 _/ 6-dimethyl-4-pyridylmethylchloride _/ 2-bromo-4-pyridylmethylchloride, 2,6-dibromo-4-pyridylmethylchloride, 3-chloro-2-fluoro-5-pyridylmethylchloride, 3-bromo- 2-fluoro-5-pyridylmethyl chloride, 2-CRIoro-3-fluoro-5-pyridylmethyl chloride, 3-chloro-O-2-methylthio-5-pyridylmethyl chloride, 2-ethyl-5-pyridylmethyl chloride, 2-phenyl-5-pyridylmethyl chloride, 2 Benzyl 5-pyidylmethyl chloride, 2-phenoxy-5-pyridylmethyl chloride, 2- (2-ethoxyethyl) -5-pyridylmethyl chloride, 2-methoxymethyl-5-pyridylmethyl chloride, 2-difluoromethoxy-5-pyridylmethyl chloride, 2- (2,2,2 Trifluoroethoxy) -5-pyridylmethyl chloride, 2-trifluoromethyl sulfonyl-5-pyridylmethyl chloride _/ 2-trifluoromethylsulfinyl-5-pyridylmethyl chloride, 3-furylmethyl chloride, furfuryl chloride, 5-methylfurfuryl chloride, 2-thienylmethyl chloride, 4-imidazolylmethyl chloride, 4-methyl-5-imidazolylmethyl chloride, tetrahydrofurfuryl chloride, B-methyltetrahydrofurfuryl chloride, 3-thienylmethyl chloride, 2-Pyrrolylmethyl chloride, i-methyl-2-pyrrolylmethyl chloride, S-methyl-thienylmethylchloro.d, 5-bromo-2-thienylmethyl chloride, S-cyanofurfuryl chloride, 5-trifluoromethylthio-2-thienylmethyl chloride, 1- (2-thienyl) ethyl chloride, B-methyl-S-isoxazolylmethyl chloride, 5-isoxazolylmethyl chloride, 4-isoxazolylmethyl chloride, S-methyl-B-isoxazolylmethyl chloride, S-trifluoromethyl-B-isoxazolylmethyl chloride, S-chloro-B-isoxazolylmethyl chloride, 5-isothiazolylmethyl chloride,

5-pyrazolylmethyl chloride, 4-pyrazolylmethyl chloride, i-methyl-4-pyrazolylmethyl chloride, 1- (1-methyl-4-pyrazolyl) ethyl chloride, i-ethyl-4-pyrazolylmethyl chloride, i-isopropyl-4-pyrazolylmethyl chloride, i-allyl-4 pyrazolylmethyl chloride, i-tert-butyl-4-pyrazolylmethyl chloride, 1- (2,2,2-trifluoroethyl) -5-pyrazolylmethyl chloride, S-methyl-S-pyrazolylmethyl chloride, S-chloro-methyl-B-pyrazolylmethyl chloride, 2, 3,5-trimethyl-4-pyrazolylmethyl chloride, 5-oxazolylmethyl chloride, 4-methyl-5-oxazolylmethyl chloride, 4-thiazoylmethyl chloride, 5-thiazoylmethyl chloride> 2-methyl-5-thiazoylmethyl chloride, 2-chloro-4-thiazoylmethyl chloride, 2-chloro 5-thiazoylmethyl chloride, 2-trifluoromethyl-5-thiazolylmethyl chloride, 2-bromo-5-thiazolylmethyl chloride _/ 2,4-dichloro-5-thiazolylmethyl chloride, 4-imidazolylmethyl chloride, i-methyl-2-imidazolylmethyl chloride, i ^^ - triazole-B- ylmethyl chloride, i-methyl-i ^^ - triazol-o-ylnethylchlorid, i ^^ - Thiadiazol ^ -ylmethyl chloride, l ^ S-thiadiazol-B-ylmethylchlorid, S-methyl-i ^^ - oxadiazol-B-ylm ethyl chloride,!, S-dioxolane ^ -ylmethyl chloride, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl chloride _/ 2-methyl-2-oxazolin-5-ylmethyl chloride, 2-trifluoromethyl-2-oxazolin-5-ylmethyl chloride , 3-Pyrrolylmethyl chloride, i-ethyl-2-pyrrolylmethyl chloride, i-methyl-3-pyrrolylmethyl chloride, B-methyl-S-thienyl chloride, B-methyl-S-pyrrolylmethyl chloride,!, S-dimethyl-S-pyrrolylmethyl chloride, 2.5 -Dimethyl-3-furylmethyl chloride, 2,5-dimethyl-3-thienylmethyl chloride, S-fluoro-S-furylmethyl chloride, 4-chlorofurfuryl chloride, ot-chlorofurfuryl chloride, B-chloro-S-furylmethyl chloride, B-chloro-S-thienylmethyl chloride, B Chloro-1-methyl-S-pyrrolylmethyl chloride, B-bromo-S-furylmethyl chloride, 5-nitrofurfuryl chloride, 4-nitro-2-thienylmethyl chloride, B-nitro-thienylmethyl chloride, i-methyl-S-nitro-S-pyrrolylmethyl chloride, ö-cyano-S-furylmethyl chloride, B-cyano-S-thienylmethyl chloride, B-cyano-i-methyl-S-pyrrolylmethyl chloride, 5-trifluoromethylfurfuryl chloride, 5-difluoromethylfurfuryl chloride, B-trifluoromethyl-S-thienylmethylchloro id, i-methyl-B-trifluoromethyl-S-pyrrolylmethyl chloride, 5-methoxy-2-thienylmethyl chloride, 5-methylfurfuryl chloride, 2,5-dimethylthio-3-thienylmethyl chloride, S-trifluoromethylthiofurfuryl chloride, 5- (2,2-dichlorovinyl) - 2-thienylmethyl chloride, 5-ethoxycarbonylfurfuryl chloride, S-formyl-thienylmethyl chloride, S-isoxazolylmethyl chloride, 4-isoxazolylmethyl chloride, S-ethyl-6-isoxazolylmethyl chloride, S-isopropyl-B-isoxazolylmethyl chloride,

S-fluoro-O-isoxazolylmethyl chloride, S-bromo-B-isoxazolylmethyl chloride, S-hydroxy-B-isoxazolylmethyl chloride, S-nitro-S-isoxazolylmethyl chloride, S-cyano-B-isoxazolylmethyl chloride, S-difluoromethyl-S-isoxazolylmethyl chloride, S- Chlorodifluoromethyl-S-isoxazolylmethyl chloride, S-methoxymethyl-B-isoxazolylmethyl chloride, S-isopropoxymethyl-B-isoxazolylmethyl chloride, S-trichloromethyl-O-isoxazolylmethyl chloride, S-methoxy-B-isoxazolylmethyl chloride, S-trifluoromethoxy-B-isoxazolylmethylchloride, 2.5- Dimethyl 4-isoxazolylmethylchloride, 3-isothiazolylmethylchloride, 4-isothiazolylmethylchloride, 3-pyrazolylmethylchloride, 1 - (^ pyrazolylethylchloride, i-methyl-S-pyrazolylmethylchloride, i-methyl-5-pyrazolylmethylchloride, i-propyl-4-pyrazolylmethylchloride, 1 (2,2,2-trifluoroethyl) -3-pyrazolylmethyl chloride, S-chloro-i-ethyl-S-pyrazolylmethyl chloride, S-chloro-i-isopropyl-S-pyrazolylmethyl chloride, S-chloro-i-methyl-B-pyrazolylmethyl chloride, S-trifluoromethyl-S-pyrazolylmethyl chloride, i-methyl-B-trifluoro romethyl-S-pyrazolylmethyl chloride, i-methyl-S-trifluoromethyl-B-pyrazoiylmethyl chloride, 4-oxazolylmethyl chloride, 2-methyl-4-oxazolylmethyl chloride, 2-methyl-5-oxazolylmethyl chloride, 2-fluoro-5-oxazolylmethyl chloride, 2-chloro 5-oxazolylmethylchlorid,

2-methylthio-5-oxazolylmethyl chloride, 2-trifluoromethoxy-5-oxazolylmethyl chloride, 2,4-dimethyl-5-oxazolylmethyl chloride, ö-ethoxycarbonyl ^ -oxazolylmethyl chloride, 1- (5-thiazolyl) ethyl chloride, 2-methyl-4-thiazolylmethyl chloride, i ^ -methyl-B-thiazoly-dimethyl chloride, 2-ethyl-5-thiazolylmethyl chloride,

2-isopropyl-5-thiazolylmethyl chloride, 4-methyl-5-thiazolylmethyl chloride, 2-fluoro-4-thiazolylmethyl chloride,

1- (2-chloro-5-thiazolyl) ethyl chloride, 2-nito-4-thiazolylmethyl chloride, 2-nitro-5-thiazolylmethyl chloride, 2-cyano-4-thiazolylmethyl chloride, 2-cyano-5-thiazolylmethyl chloride,

2-methyl-5-thiazolylmethyl chloride

2-chlorodifluoromethylthio-5-thiazolylmethyl chloride, 2- (2,2,2-trifluoroethylthio) -5-thiazolylmethyl chloride, 2- [2- (2,3,3-trichloro) propenylthio] thiazolylmethyl chloride, 2-thiocyanato-5-thiazolylmethyl chloride , 2-Amino-4-thiazolylmethyl chloride, 2-acetamino-4-thiazolylmethyl chloride, 2-methoxy-4-thiazolylmethyl chloride, 2-methoxy-5-thiazolylmethyl chloride, 2-trifluoromethoxy-5-thiazolylmethyl chloride, 2-difluoromethoxy-5-thiazolylmethyl chloride , 2-chloromethyl-5-thiazolylmethyl chloride, 2-difluoromethyl-5-thiazolylmethyl chloride, 2-trifluoromethyl-5-thiazolylmethyl chloride, 2- (l, 1,2,2-tetrafluoroethyl) -5-thiazolylmethyl chloride,

2-Cyclopropyl-5-thiazolylmethyl chloride, 2-imidazolylmethyl chloride, i-methyl-B-imidazolemethylchloride, 2-fluoro-4-imidazolemethylchloride, 2-chloro-4-imidazolemethylchloride, 4-nitro-2-imidazolemethylchloride, 2-trifluoromethylthio-4- imidazolemethylchloride, i-dimethyl-imidazolemethylchloride, 1-methyl-2-trifluoromethyl-4-imidazolemethylchloride, i-methyl-1,2,3-triazolyl-1-methylmethyl chloride, 1- (1-methyl-1,2,3-triazole) 4-yl) ethyl chloride, S-methyl-i ^^ triazol-B-ylmethyl chloride, S-trifluoromethyl-i ^ -triazol-S-ylmethylchlorid, i ^^ - oxadiazol-S-ylmethylchlorid, "!, S ^ -oxadiazol -B-ylmethyl chloride, "^, S -oxadiazol-B-ylmethyl chloride, S-trifluoromethyl-1-aoxadiazol-S-ylmethyl chloride, 2-methyl-1,3,4-oxadiazol-5-ylmethyl chloride, 2-trifluoromethyl-1 , 3,4-oxadiazol-5-ylmethyl chloride, 2- (2,2,2-trifluoroethyl) -1,3,4-oxadiazol-5-ylmethyl chloride, i-thiadiazol-B-ylmethyl chloride,

id ^ S-thiadiazol-S-y-ethyl chloride, 1,3,4-thiadiazol-2-yl-trimethyl chloride, 1- (1,3,4-thiadiazol-2-yl) -ethyl chloride, i-thiadiazol-S-ylmethyl chloride, 3 -Methyl-1,2,4-thiadiazol-5-yl) ethyl chloride, 4-methyl-1,2,3-thiadiazol-5-yl) ethyl chloride, 2-methyl-1,3,4-thiadiazol-5-yl ) ethyl chloride, 2-trifluoromethyl-1,3,4-thiadiazol-5-yl) ethyl chloride, 2-fluoro-1,3,4-thiadiazol-5-yl) ethyl chloride, 2-chloro-1,3,4-thiadiazole -5-yl) ethyl chloride, S-chloro-1: 5-thiadiazol-1-ylethyl chloride, 1- (3-tetrahydrofuryl) -ethyl chloride, 3-tetrahydrothiadiylmethyl chloride, 1- (3-tetrahydrothienyl) ethyl chloride, T-methyl-S-pyrrolidinylmethyl chloride, 1, S-Oxathiolan ^ -ylmethyl chloride,!, S-dioxolane ^ -ylmethyl chloride, "!, S-Oxathiolan ^ -ylmethyl chloride,!, S-Dithiolan ^ -ylmethyl chloride, thiazolidin-S-ylmethyl chloride, 4-methyl-1,3 dioxolan-2-ylmethyl chloride, 2-methyl-1,3-oxathiolan-4-ylmethyl chloride, 2-chloromethyl-1,3-dioxolan-4-ylmethyl chloride, 2-trifluoromethyl-1,3-dioxolan-4-ylmethyl chloride, 2 -Oxo-i, S-dioxolane ^ -ylmethyl chloride, S-form yl-thiazolidin-B-ylmethyl chloride, S-acetyl-thiazolidin-o-ylmethyl chloride, S-thiol-B-ylmethyl chloride, 2H, 5H-1,1-dioxo-3-thiolen-3-ylmethyl chloride, 2-isoxazolin-5-yl ylmethyl chloride, S-methyl ^ -isoxazolin-B-ylmethyl chloride, 3-trifluoromethyl-2-isoxazolin-5-ylmethyl chloride, 3- (2,2,2-trifluoroethyl) -2-isoxazolin-5-ylmethyl chloride, 2,4-dimethyl 2-oxazolin-4-ylmethyl chloride, 2-methyl-1,3-thiazolin-4-ylmethyl chloride, 2-oxazolidolin-5-ylmethyl chloride, S-methyl-thiazolidinone-6-ylmethyl chloride,

2-trifluoroacetamido-5-thiazolylmethyl chloride, 3 - ^ / ethyl-2-thiooxothiazolidin-5-ylmethyl chloride, S-chloro-1-aoxadiazol-B-ylmethyl chloride, B-carboxy ^ -oxazolylmethyl chloride, 2-dimethylamino-5-thiazolylmethylchloride , 5-phenoxyfurfuryl chloride, i-phenyl-4-pyrazolylmethyl chloride, i-benzyl-4-pyrazolylmethyl chloride, 2-phenyl-4-thiazolylmethyl chloride, i-benzyl-2-imidazolylmethyl chloride,

2-Methylsulfinyl [-5-thiazolylmethyl chloride, 2-methylsulfonyl-5-thiazolylmethyl chloride, 2-carbamoyl-5-thiazolylmethyl chloride, 2-methylaminocarbonyl: 5-thiazolylmethyl chloride, 2-dimethylaminocarbonyl-5-thiazolylmethyl chloride, 2-methylthio-1,3 , 4-thiadiazolylmethyl chloride, 2-methylsulfonyl-1, SA-thiadiazol-1-methylmethyl chloride, 4-pyrimidinylmethyl chloride, 2-methyl-6-pxo-1H _/ 6H-dihydropyrimidin-4-ylmethyl chloride, 5-pyrimidinylmethyl chloride, 2-methyl- 5-pyrimidinylmethyl chloride, 2-dimethylamino-5-pyrimidinylmethyl chloride, 2,4 _/ 6-trichloro-5-pyrimidinylmethyl chloride, pyrazinylmethyl chloride, 1- (pyrazinylethyl) chloride, 2-methyl-5-pyrazinylmethyl chloride, 3-pyridazinylmethylchloride, 2-chloro-4 pyrimidinylmethyl chloride, 4-chloro-6-pyrimidinylmethyl chloride, 4-ethyl-6-pyrimidinylmethyl chloride, 2-fluoro-5-pyrimidinylmethyl chloride, 1- (2-fluoro-5-pyrimidinyl) ethyl chloride, 2-chloro-5-pyrimidinylmethyl chloride , 2-isopropyl-5-pyrimidinylmethyl chloride or bromide, 2-chlorodifluoromethyl-5-pyrimidinylmeth yl chloride, 2-trifluoromethyl-5-pymidinylmethyl chloride, 2-bromomodifluoromethyl-5-pyrimidinylmethyl chloride, 2-methoxy-5-pyrimidinylmethyl chloride, 2-difluoromethoxy-5-pyrimidinylmethyl chloride, 2-trifluoromethoxy-5-pyrimidinylmethyl chloride, 2- (2,2,2 Trifluoroethoxy) -5-pyrimidinylmethyl chloride, 2-methylthio-5-pyrimidinylmethyl chloride, 2-ethylthio-5-pyrimidinylmethyl chloride, 2-difluoroethylthio-5-pyrimidinylmethyl chloride, 2-trifluoromethylthio-5-pyrimidinylmethyl chloride, 2-nitro-5-pyrazinylmethyl chloride, 2-cyano-5-pyrazinylmethyl chloride, 2-chloro-5-pyrazinylmethyl chloride, 2-trifluoromethyl-5-pyrazinylmethyl chloride, S-fluoro-e-pyridazinylmethyl chloride, S-methyl-e-pyridazinylmethyl chloride, 4-pyridazinylmethyl chloride, S-chloro-e- pyridazinylmethyl chloride, S-trifluoromethyl-e-pyridazinylmethyl chloride, 1,3,5-triazin-2-ylmethyl chloride, S-chloro-l ^. S-triazin-e-ylmethyl chloride,

and

In place of the chlorides listed above, the bromides or the p-toluenesulfonates may also be mentioned by way of example. They are specifically described below.

The above halides, for example the chlorides, can be readily prepared by chlorinating the corresponding alcohols with thionyl chloride.

For example, 2-chloro-5-pyridylmethyl chloride can be obtained by chlorination of 2-chloropyridylmethyl alcohol with thionyl chloride (see J. Org. Chem. 34, 3547).

The bromides can also be prepared by bromination of a methyl group in the side chain with N-bromosuccinimide.

Some of the trifluoromethyl-substituted or trifluoromethoxy-substituted pyridyl alcohols are described in J. Med. Chem. 13, pp. 1124-1130. Using these techniques of synthesis, 2-methyl-5-trifluoromethyl-pyridine obtained by reaction of 6-methylnicotinic acid with hydrofluoric acid and sulfur tetrafluoride is converted to the N-oxide, and the rearrangement reaction of the N-oxide is capable of 5-trifluoromethyl To provide 2-pyridylmethyl alcohol.

This reaction can also be applied to the synthesis of 5-methyl-2-trifluoromethylpyridine from 5-methylpicolinic acid.

2-trifluoromethyl-5-pyridylmethyl bromide (or chloride), the desired starting material, can be synthesized by mono-halogenating the above-mentioned 5-methyl-2-trifluoromethylpyridine with N-bromosuccinimide or N-chlorosuccinimide.

2-trifluoromethoxy-5-pyridylmethylbromide (or chloride) can be similarly obtained by the reaction of 5-methyl-2-trifluoromethoxypyridine derived from 2-hydroxy-5-methylpyridine with N-bromosuccinimide or N-chlorosuccinimide.

Since the halogen is active in the ortho position of the pyridine ring, a 2-haloalkoxy-5-pyridylmethyl alcohol can be synthesized, for example, by the reaction of 6-chloronicotinic acid with an excess of sodium alkoxide.

Reduction of this compound can afford the starting material, 2-haloalkoxy-5-pyridylmethyl alcohol.

Halogenomethyl-substituted furans and thiophenes are known compounds. For example, 2-ethoxycarbonyl-5-chloromethylfuran is a known compound described in Liebigs Annalen der Chemie 580, p. 176. 2-Bromomethyl-5-trifluoromethylfuran is obtained by halogenating the side chain of 2-methyl-5-trifluoromethylfuran with a halogenating agent such as N-bromosuccinimide (NBS) (US Pat. No. 3,442,913).

Many bromine-substituted heterocyclic compounds can be obtained by bromination of the corresponding methyl-substituted heterocyclic compounds with N-bromosuccinimide.

Halogenomethyl-substituted isoxazoles can be obtained by halogenation of methylisoxazoles with NBS, or hydroxymethylisoxazole can be easily converted into chloromethylisoxazole with the aid of thionyl chloride. For example, 5-bromomethylisoxazole is a compound described in DE-OS 2716687, and 4-bromomethylisoxazole is a in Chem.

Abstr. 65, 2242 h, described compound.

Chloromethyl-substituted heterocyclic compounds can be synthesized by a chloromethylation reaction. 4-chloromethylisoxazole and 4-chloromethyl-3,5-dimethylisoxazole described in Zh. Obshch. Khim. 34, pp. 4010-4015, are good examples thereof. Furthermore, halomethyl-substituted isoxazoles can also be prepared by direct ring synthesis. 3-Bromo-5-bromomethylisoxazole (Rend., Lombaro, S.I., I. I. Classe, M. Mat., Nat., 94: 729-740) and 5-bromomethyl-3-methylisoxazole (Japanese Patent Laid-Open No. 59156/1977 ) are good examples of this.

5-chloro-3-trifluoromethylisoxazole can be prepared by synthesizing 3-trifluoromethyl-5-hydroxymethylisoxazole and chlorinating it with thionyl chloride as described in Bull. Chem. Soc. Japan 57, pp. 2184-2187. The use of other haloalkyls instead of trifluoromethyl in the above reaction may lead to the synthesis of the corresponding haloalkyl isoxazoles. As indicated above, haloalkyl heterocyclic compounds can be readily obtained generally by treating the corresponding alcohols with halogenating agents, for which thionyl chloride is a typical example.

5-Chloromethyl-3-hydroxyisoxazole is described as described in Tetrahedron Letters 1965, no. 25, pp. 2077-2079.

Chlorination thereof with phosphonyl chloride, etc. is able to provide S-chloro-O-chloromethylisoxazole.

Halogen-substituted halomethyl-substituted isothiazoles can be obtained, for example, by converting halogen-substituted methyl-substituted isothiazoles with halogenating agents such as NBS into halogen-substituted bromomethyl-substituted isothiazoles. 5-bromo-3-bromomethylisothiazole (described in J. Chem. Soc. 1965,

P. 7274-7276) is a good example.

4-Chloromethylpyrazole can be easily obtained by chlorinating 4-hydroxymethylpyrazole with thionyl chloride (J. Amer.

Chem. Soc. 71, p. 3994-4000).

As regards halo-halomethylpyrazoles, for example, S-ethoxycarbonyl-S-hydroxy-i-methylpyrazole is synthesized as described in Chem. Pharm. Bull. 31, No.4, pp. 1228-1234. Subsequent chlorination with phosphonyl chloride gives δ-chloro-i-methyl-S-pyrazolylcarbonyl chloride. Reduction of the chloride with sodium borohydride provides o-chloro-S-hydroxymethyl-T-methylpyrazole. Chlorination of this product in the usual way can lead to 5-chloro-3-chloromethyl-1-methylpyrazole.

As for the halogenomethyl-substituted oxazoles, chloromethyloxazole can be obtained by chlorinating hydroxymethyloxazole with thionyl chloride, etc. The subject compounds can also be prepared by direct ring synthesis.

For example, 5-bromomethyl-2-methyloxazole is a known compound (J.Amer.Chem.Soc.104, p.4461-4465), and 2-bromoethyl-5-ethoxycarbonyloxazole is also a known compound (Japanese Patent Laid-Open No. 108771/1984 ).

4-halomethylthiazoles can be synthesized directly, for example, by reacting dihaloacetones with thioacylamides such as thioacetamide (J.Amer.Chem.Soc 56, p.470-471 and ibid.73, p.2936).

5-Halogenomethylthiazole can be obtained by reaction of a Thioacylamids with a-chloro-a-formyle'thylacetat, reduction of the resulting 5-Ethoxycarbonylthiazols with lithium aluminum hydride in the usual manner and halogenation of the resulting 5-Hydroxymethylthiazqls. ö-chloromethyl-methylthiazole described in Zh. Obshch. Khim. 32, pp. 570-575, and J. Amer.

Chem. Soc. 104, pp. 4461-4465, is a good example.

The reaction of thiourea in place of the thioacylamide is capable of providing 2-amino-4-chloromethyl or 2-amino-5-chloromethylthiazole, and further diazotization may be used to introduce a halogen atom, etc. This halogen is active and can be converted into a 2-alkoxy group with the aid of a sodium alkoxide (Japanese Patent Laid-Open Nos. 5972/1979 and

J. Chem. Soc. Perkin 1,1982, pp. 159-164).

2-halo-4- or -5-bromomethylthiazole can be prepared by bromination of the 2-halo-4- or -5-methylthiazole with NBS

be synthesized. '·

The use of ammonium dithiocarbamate (Org. Synthesis, Coll. Vol. Ill, p. 763) on SteHe of the above-mentioned thioacetamide can afford 4- or 5-halomethyl-2-mercaptothiazoles. Their alkylation or halogenoalkylation can lead to the 2-alkylthio-4- or -5-halomethylthiazoles or 2-substituted 4- or 5-halomethylthiazoles (J. Amer.

Chem. Soc. 75, pp. 102-103).

A halomethylimidazole, for example, chloromethylimidazole, can be obtained by hydroxymethylation of an N-alkylimidazole with formaldehyde, optionally dealkylation to form a hydroxymethylimidazole and chlorination with thionyl chloride, etc. in commonly (described in J. Amer. Chem. Soc., 71, pp. 383-386 ). 4-hydroxymethylimidazole as an example of the hydroxymethylimidazoles can be synthesized directly from fructose, formaldehyde and ammonia (described in Org. Synthesis, Coll. Vol. Ill, p.460).

Hydroxymethyltriazole can be prepared, for example, according to the method described in J. Amer. Chem. Soc. 77, pp. 1538-1540, and by chlorination thereof, chloromethyltriazole can be obtained.

Halogenomethyloxazoles and halomethylthiazoles can each be synthesized by bromination of methyl-substituted oxazoles or methyl-substituted thiazoles with NBS. 3-Bromomethyl-1,2,5-thiazole described in Japanese Laid-Open Patent Publication No. 24963/1974 and 3-bromomethyl-4-chloro-1,2,5-thiazole are good examples thereof. The halomethyloxadiazoles and halomethylthiadiazoles can be synthesized by direct ring synthesis. Among others, 5-chloro-3-chloromethyl-1,2,4-thiadiazole described in J. Org. Chem. 27, pp. 2589-2592, 3-chloro-5-chloromethyl-1,2, 4-oxadiazole, which is described in DE-OS 2054342, and 5-chloromethyl-3-methyl-1,2,4-oxadiazole, which is described in Bull. Soc. Chim. Beiges 73, pp. 793-798, good examples of this. The 5-chloromethyl-1,3,4-oxadiazole or thiadiazole substituted in the 2-position described in FR-PS 1 373290 is another good example.

Chloromethyl-substituted heterocyclic compounds can be synthesized by reduction of carboxylic acids or ester derivatives thereof with lithium aluminum hydride for their conversion into alcohol derivatives and subsequent chlorination of the alcohol derivatives with thionyl chloride, etc. As examples thereof, JP-OS 89633/1984 describes 5-chloromethyl- I ^ S-thiadiazol-1-chloromethyl-1-methyl-1-yl-tetrazole and 1-chloromethyl-1-methyl-1-triazole.

Haloalkyl-substituted saturated or partially unsaturated heterocyclic compounds can be converted to chloromethyl-substituted products by, for example, chlorination of their alcohol derivatives in a conventional manner.

Bromomethyldioxolane and bromomethyloxothiolane can be synthesized by reacting dimethylbromoacetal with ethylene glycol or by reacting dimethylbromoacetal with 2-mercaptoethanol or by reacting an alcohol or ketone with epibromohydrin. For example, 2-bromomethyl-1,3-dioxolane in Beilstein, Volume 19, II, p 8, described.

As regards chloromethyl-substituted oxazoline compounds, δ-chloromethyl-S-methyl-1-oxazoline may be prepared as described in Pak. J. Sei. Res. 30, pp. 91-94. 5-Chloromethyl-3-trifluoro-ethyl-2-isoxazoline can be prepared by chlorinating 3-trifluoromethyl-5-hydroxymethyl-2-isoxazoline described in Bull. Chem. Soc. Japan 57, p.2184-2187, are prepared in a conventional manner. 5-chloromethyl-2-methyloxazoline is a compound described in Tetrahedron 34, pp. 3537-3544.

4-chloromethyl-2-methyl-2-thiazoline can be synthesized by chlorinating 4-hydroxymethyl-2-methyl-2-thiazoline described in Heterocycles 4, pp. 1687-1692. 5-chloromethyl-3-methyl-2-oxazolidin-2-one is a compound which is described in DE-OS 1 932219. 3-Bromomethyl-1,1-dioxo-3-thiols is a compound described in US Pat. No. 4,561,764 and can be prepared by bromination with NBS.

5-Pyrimidinylmethyl alcohol is obtained from 5-pyrimidinecarbaldehyde, and 2-chloro-5-pyrimidinylmethylalcohol is obtained from 2-chloro-5-pyrimidinecarbaldehyde. 3-Pyridazinylmethyl alcohol can be synthesized from furfuryl acetate (Acta Chem. Scand. 1, p. 619). As for pyrazinylalkyl halides, methylpyrazine or dimethylpyrazine, which is readily available, can be converted to chloromethylpyrazine with the aid of N-chlorosuccinimidine (Synthesis 1984, pp. 676-679). This reaction can also be applied to methylpyrazines having other substituents and to halogen-substituted methylpyridazines such as 3-chloro-6-methylpyridazine (described in J. Chem. Soc. 1947, p.242), and by means of this reaction 3-chloro-6- Pyridazinylmethylchlorid be synthesized. Furthermore, 2-chloro-5-pyrimidinylmethyl bromide can be obtained from 2-chloro-5-methylpyrimidine (Reacts, Sposobnost, Org Soedin, 5, pp. 824-837) and N-bromosuccinimide.

As in J. Heterocycl. Chem. 19, p.407, and described in Chem. Pharm. Bull. 28, pp. 3057 and 3063, ethyl-2-chloropyrazine-5-carboxylate can be synthesized and reduced to the corresponding methanol (DE-OS 2910824) ,

As regards triazinylalkyl halides, for example, 1,3,5-triazin-2-ylmethyl chloride can be obtained by reaction of 2-methyl-1,3,5-triazine with N-chlorosuccinimide (J. Org. Chem. 29, p. 1527- 1537). 3,5-dichloro-6-methyl-1,2,4-triazine (described in J. Med. Chem. 10, pp. 883-887) and 3-chloro-6-methyl-1,2,4,5 Tetrazine (J. Org. Chem. 46, p.5102-5109) can be similarly chlorinated by reaction with N-chlorosuccinimide.

In the compound of the formula (I) in which X is an -NH group or Y is a = CH group and which are prepared by means of the above processes (a), (b), (c), (d), (e) or (f), each hydrogen atom of the -NH group and the = CH group may be substituted by other groups or added to other groups.

As specific examples, some compounds having active olefinic bonds, such as methyl vinyl ketone, ethyl acrylate and acrylonitrile, can be attached to the hydrogen atom of the = CH group by Michael reaction (see Japanese Patent Laid Open No. 151882 /).

In addition, by a Mannich reaction or similar reactions, specifically a dialkylaminomethyl group can be introduced at the α-carbon atom of the nitromethylene group, and also active aldehydes such as formaldehyde and chloral can be added (see Japanese Patent Laid-Open No. 151882/1975 ).

Incidentally, each hydrogen atom of the above -NH group and = CH group can also be halogenated by halogenating agents such as N-chlorosuccinimide, N-bromosuccinimide, perchloryl fluoride and halogen per se (see U.S. Patents Nos. 3,933,809 and 3,962,233 and Japanese Patent Laid-Open Nos. OS 54532/1974).

In the above cases, formula (I) may have the following form. "

L-C-NO, shark

in which n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^e , R, Z and Hal have the meanings given above and L is a halogen atom, a. Phenylthio group or an alkoxycarbonyl group.

Glyoxalic acid and dimethylformaldehyde dimethyl acetal may also be reacted with the α-carbon atom of the nitromethylene group, and the formula (I) may take the following forms

- (H-C) -N-HC NO-

ί / JI &

wherein η, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R and Z have the otien given meanings.

The nitrogen atom of the above -NH group and the a-carbon atom of the nitromethylene group can be independently acylated, sulfinylated or sulfonylated (see NL-PS 7306145, US-PS 3985736,3996372,4020061,4022775, 4052411 , 4053662 and 4076813).

Acyl isocyanates and sulfonyl isocyanates can be reacted with the a-carbon atom of the nitromethylene group (see US Pat. Nos. 4,013,766, 4,025,634, 4,029,791 and 4,03,409).

The nitrogen atom of the above -NH group can also be alkylated (see BE-PS 821282), and with the aid of this reaction, the 3-position of imidazolidines or tetrahydropyrimidines can be alkylated to the corresponding compounds of formula (I) receive.

In carrying out the process (a), suitable diluents may be any inert organic solvent.

Examples of such diluents include water; aliphatic, alicyclic and aromatic hydrocarbons (which may optionally be chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene; Ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, propylene oxide, dioxane and tetrahydrofuran; Nitriles such as acetonitrile, propionitrile and acrylonitrile; Alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; Acid amides such as dimethylformamide and dimethylacetamide; Sulfones and sulfoxides such as dimethylsulfoxide and sulfolane; and bases such as pyridine. The process (a) can be carried out in a wide temperature range. In general, it can at a temperature between about - 20 ⁰ C and are performed to the boiling point of the mixture, preferably about 50 ⁰ C and about 120 ⁰ C. The reaction is conveniently carried out under normal atmospheric pressure, but it is also possible to operate under elevated or reduced pressure.

In the process (a), the desired novel compounds of the formula (I) can be obtained, for example, by reacting the compounds of the formula (II) with 1 to about 1.2 mol, preferably 1 to about 1.1 mol, of the compound of Formula (III) are heated to 1 mol of the compound of formula (II) in an inert solvent such as an alcohol (eg methanol or ethanol) under reflux until the mercaptan evolution is complete.

In carrying out processes (b) and (c), suitable diluents may be the inert solvent exemplified above for process (a). Examples of bases which may be mentioned are hydroxides, carbonates, bicarbonates and alkoxides of alkali metals, and also tertiary amines such as triethylamine, diethylamine and pyridine. The methods (b) and (c) can be carried out in a wide temperature range, generally at a temperature between about -20 ⁰ C and the boiling point of the mixture, preferably between about ⁰ ° C and about 5O ⁰ C. -The reaction is preferably under normal atmospheric pressure, but it is also possible to operate under elevated or reduced pressure.

In the above processes (b) and (c), for example, about 1 to 5 moles, preferably about 2 to about 4 moles of a base and about 0.9 to about 4 moles, preferably about 1 to about 3 moles, of the compounds of formulas (IV) and (V) to 1 mole of the compound of formula (II).

In carrying out process (d), suitable diluents may be the inert solvent exemplified above for process (a).

According to process (d), the desired compounds of formula (I) can be obtained in a simple manner, for example by reacting 1 mol of the compounds of formula (II) with 1 to about 1.2 mol, preferably 1 to about. 1.1 mol, nitroguanidine with heating in a water solvent.

The process (d) can be up to about 8O ⁰ C, carried out for example at a temperature of about 0 ° C to about 100 ⁰ C, preferably about 30 ⁰ C. The reaction is preferably carried out under normal atmospheric pressure, but it may be carried out under elevated or reduced pressure.

In the practice of process (e), the compounds of formula (VI) are usually prepared prior to reaction in an acid such as conc. Sulfuric acid dissolved.

In the practice of the method, the compounds of formula (VI) and fuming nitric acid (having a purity of at least 98%) are reacted to obtain the desired compounds of formula (I) at low temperatures, preferably at or below ⁰ ° C (using the procedure GB patent application 2055796). The compound of formula (VI) used in the above process is generally in the form of a hydrohalide salt as a result of its synthesis as a result of its synthesis, and usually becomes conventional prior to its use in the above process (e) Manner neutralized.

In the practice of process (f), suitable diluents may be the inert organic solvents exemplified above for process (a). Examples of bases which may be mentioned are hydrides such as sodium hydride and potassium hydride and also hydroxides and carbonates of alkali metals.

The process (f) can be carried out in a wide temperature range, generally at a temperature between about 0 ^° C. and about 100 ^° C., preferably between about 10 ^° C. and about 80 ^° C.

The reaction (f) is preferably carried out under normal atmospheric pressure, but it is also possible to operate under elevated or reduced pressure.

In the process (f), the desired compounds of the formula (I) can be obtained, for example, by reacting the compounds of the formula (VII) in the presence of 1.1 to about 1.2 mol of sodium hydride as the base per 1 mol of the compound (VII ), with 1 to about 1.2 mol, preferably 1 to about 1.1 mol, of the compounds of formula (VIII) per 1 mol of compound (VII) in an inert solvent such as dimethylformamide. In the process (f), it is preferable for the reaction to convert the compound of the formula (VII) into its sodium salt before the reaction with the aid of sodium hydride. In view of the properties of the sodium hydride, such a reaction is conveniently carried out under an atmosphere of nitrogen gas. The compounds of formula (I) according to the present invention include tautomers as represented by the following formulas: In the case where X is NH and Y is CH:

Z-CH

For the case where X is NH and Y is N:

Z-CH

Z-CH

N-NO.

NH-NO.

In addition, those compounds of formula (I) in the cases where Y is CR ⁹ , the corresponding E and

Include Z isomers. , - '

The compounds of formula (I) may also be in the form of a salt. Examples of such salts are inorganic acid salts, sulfonate salts, organic acid salts and metal salts.

The active compounds of the invention show potent insecticidal properties. They can therefore be used as insecticides. The active compounds can be used to control and eradicate a wide range of pests, including sucking insects, biting insects and other plant parasites, pests in grain stores and stored grain crops and harmful pests.

Examples of the pests to be controlled are given below.

Insects of the order Coleoptera

Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptus oryzophilus and

Lyctusbrunneus; Insects of the order Lepidoptera

Lymantria dispar, Malacosoma neustria, Pieris rapae,

Spodoptera litura, Mamestra brassicae, Chilosuppressa jis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana,

Carpocapsa pomonella, '

Agrotis fucosa, Galleria mellonella, Plutella maculipennis and Phyllocnistiscitrella;

Insects of the order Hemiptera

Nephotettix cincticeps,

Nilaparvata lugens,

Pseudococcus comstocki,

Unaspis yanonensis,

Myzus persicae,

Aphis pomi.

Aphis gossypii,

Rhopalosiphum pseudobrassicae,

Stephanitisnashi,

Nazaraspp.,

Cimex lectularius,

Trialeurodes vaporariorum and

Psyllassp .; Insects of the order Orthoptera

Blatella germanica,

Periplaneta americana,

Gryllotalpa africana and

Locusta migratoria migratoriodes; Insects of the order Isoptera -

Deucotermes speratus and

Coptotermes formosanus; Insects of the order Diptera

Musca domestica,

Aedes aegypti,

Hylemia platura

Culexpipiens,

Anopheles sinensis and

Culextritaeniorhynchus.

In the field of veterinary medicine, the novel compounds according to the present invention are effective against various harmful animal parasites (internal and external parasites) such as insects and worms. Examples of such animal parasites are given below

insects

Gastrophilusspp.,

Stomoxys spp.,

Trichodectes spp.,

Rhodniusspp. and

Ctenocephalides canis.

Substances with pesticidal activity against pests, including all of the species exemplified above, may occasionally simply be referred to in the present application as "insecticides".

The active compounds may be converted into common formulations such as solutions, emulsions, suspension powders, foams, pastes, granules, aerosols, natural or synthetic substances impregnated with the active compound, very fine capsules in polymeric substances, coating compositions for use on seed (mordant) as well as formulations for use with incinerators such as smoke cartridges, smoke cans and smoking snakes, as well as for cold fogging and warm atomization using the ultra-low-volume method. These formulations can be prepared in a known manner, for example by mixing the active compounds with extenders, that is with liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surfactants, that is emulsifiers and / or dispersants and / or foam-forming agents , When using water as an extender, organic solvents may be used, for example, as auxiliary solvents.

As liquid solvents, diluents or carriers are mainly suitable aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions, alcohol ^ as Butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone or strongly polar LösungsmitteLwie dimethylformamide and dimethyl sulfoxide and water.

By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and pressure, for example aerosol propellants ₍ such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

Solid carriers used include ground natural minerals ₍ such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and ground synthetic minerals such as finely divided silica, alumina and silicates.) As solid carriers for granules, crushed and fractionated natural stone materials may be used calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corncobs and tobacco stalks Polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example, alkylarylpolyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and albumin hydrolysis products. Dispersants include, for example, lignosulfite waste liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices ₍ such as gum arabic, polyvinyl alcohol and polyvinyl acetate may be used in the formulation.

It is also possible to use coloring agents such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, as well as trace nutrients such as salts of iron, manganese, boron, copper. Cobalt, molybdenum and zinc. The formulations generally contain from 0.1% to 95% by weight, preferably from 0.5% to 90% by weight of the active compound. The active compounds according to the invention may be present in their commercial formulations or in the formulations derived from these formulations in admixture with other active compounds, such as insecticides, baits, sterilizing agents, acaricides, nematicides, fungicides, growth regulators or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms.

The active compounds according to the present invention can furthermore be present in their commercial formulations or in the forms of application produced from these formulations in admixture with synergistic agents. Synergistic agents are compounds that enhance the action of the active compounds without the need for the added synergistic agent to be active itself.

The content of the active compound in the applications derived from the commercially available formulations may vary within wide limits. The concentration of the active compound in the use forms may be 0.0000001 to 100% by weight and is preferably between 0.0001 and 1% by weight. The compounds are usually applied in a form appropriate to the application forms. When used against hygiene pests and pests in product stocks, the active compounds are characterized by excellent resistance to wood and clay, as well as good resistance to alkalis on limed substrates.

embodiment

The following examples illustrate the present invention in detail. It should be understood, however, that the present invention is not limited solely to these specific examples.

Preparation Examples example 1

(Connection No. * 1)

A mixture of N- (2-chloro-5-pyridylmethyl) -3-aminopropanethiol (4.3g), 1-nitro-2,2-bis (methylthio) ethylene (3.3g) and ethanol (40ml) was added in 10h Nitrogen stream heated to reflux. After the reaction, about ² hours of the ² hours of the ethanol was distilled off under reduced pressure. Step by step, ether was added to the reaction mixture to precipitate crystals. The crystals were collected by filtration and washed with a mixture of ethanol and ether, whereupon the desired 3- (2-chloro-5-pyridylmethyl) -2-nitromethylenetetrahydro-2H-1,3-thiazine (1.3g) as yellow Crystals was obtained. Mp 164-166 ° C.

Example 2

Γ V

(Compound no. 2)

2-Nitromethylenthiazolidine (2.9g) was dissolved in dry acetonitrile (30ml) and 60% sodium hydride (0.9g) was added at room temperature in a stream of nitrogen. Subsequently, the mixture was stirred at room temperature until hydrogen evolution ceased. Then a solution of 2-chloro-5-pyridylmethyl chloride (3.2 g) in dry acetonitrile (5 ml) was added and the mixture was stirred for 1 d at room temperature. Thereafter, the acetonitrile was distilled off under reduced pressure, and to the residue was added dichloromethane. The mixture was then washed with water. Dichloromethane was distilled off from the dichloromethane layer. The residual oil was purified by chromatography on a silica gel acid to give the desired 3- (2-chloro-5-pyridylmethyl) -2-nitromethyl-thiazolidine (1.6 g). M.p. 177-179 ⁰ C.

Example 3

= CHNÖ

2 CH-

(Compound No. 3)

A mixture of N- (3-pyridylmethyl) -3-aniopropanethiol (1.8 g), 1-nitro-2,2-bis (methylthio) ethylene (1.7 g) and ethanol (40 ml) was placed under nitrogen flow for 5 hours Reflux heated. After the reaction, about ¹ μl of the ethanol volume was distilled off under reduced pressure. Step by step, ether was added to the reaction mixture to precipitate crystals. The crystals were collected by filtration and washed with a mixture of ethanol and ether to give the desired 3- (3-pyridylmethyl) -2-nitromethylene-tetrahydro-2H-1,3-thiazine (1.2 g). M.p. 143-146 ⁰ C.

Example 4

, -S.

= CHNO

(Compound No. 4)

2-Nitromethylenthiazolidine (2.9g) was suspended in dry acetonitrile (30ml) and 60% sodium hydride (0.9g) added in a stream of nitrogen. Subsequently, the mixture was stirred at room temperature until hydrogen evolution ceased. Then, a solution of 3-picolyl chloride (3.2 g) in dry acetonitrile (5 ml) was added, and the mixture was stirred at room temperature for 3 hours. Thereafter, the acetonitrile was distilled off under reduced pressure. To the residue was added dichloromethane. The mixture was then washed with water. Dichloromethane was then distilled off from the dichloromethane layer. The residual oil was purified by column chromatography to give the desired 3- (3-pyridylmethyl) -2-nitromethylthiazolidine (0.5 g). M.p. 96-100 ⁰ Q,

Example 5

V ^s CHHO-

CH-

"" N. 3

(Compound No. 5)

A mixture of 16.8 g of N- (1-methyl-4-pyrazolylmethyl) trirnethylenediamine, 16.5 g of 1-nitro-2,2-bis (methylthio) ethylene and 200 ml of ethanol was refluxed until the evolution of methylmercaptan ceased. The mixture was cooled and the precipitated crystals were collected by filtration. Washing with methanol afforded 16.6 g of the desired 1- (1-methyl-4-pyrazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine in the form of pale yellow crystals. M.p. 186-190 ° C.

Examples

'3

(Compound No. 6)

A mixture of 15.5 g of N- (3-methyl-5-isoxazolylmethyl) ethylenediamine, 16.5 g of 1-nitro-2,2-bis (methylthio) ethylene and 200 mL of ethanol was refluxed until evolution of methylmercaptan ceased. This required a period of about 3 hours. The mixture was then cooled to room temperature whereupon the desired product precipitated in the form of crystals. The crystals were collected by filtration. Washing with ethanol provided 12.5 g of the desired 1- (3-methyl-5-isoxazolylmethyl) -2- (nitromethylene) imidazolidine as pale yellow crystals. M.p. 168-170 ° C.

Example 7

) = CHNO, I O-N

(Compound No. 7)

2-Nitromethylene-imidazolidine (12.9g) was dissolved in 60ml of dry dimethylformamide and 4.4g of 60% sodium hydride (0.9g) was added little by little at room temperature in a stream of nitrogen. Then, to form the sodium salt of the imidazolidine compound, the mixture was stirred at room temperature to 30 ° C for 3 hours. Then, 11.8 g of 5-isoxazolylmethyl chloride was added at room temperature, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was poured cautiously into 150 ml of ice-water and extracted twice with dichloromethane. Dichloromethane was distilled off from the dichloromethane layers to give 12 g of the desired 1- (5-isoxazolylmethyl) -2- (nitromethylene) imidazolidine in the form of brown crystals. Mp 156-158 ° C.

Example 8

(Compound no. 8)

N- (2-methyl-5-thiazolylmethyl) trimethylenediamine

(18.5 g) was dissolved in 10 μl of acetonitrile and 1-nitro-2,2-bis (methylthio) ethylene (16.5 g) was added. The mixture was heated to reflux with stirring for 6 hours. After the reaction, the reaction mixture was cooled to room temperature. The resulting crystals were collected by filtration and washed with methanol to give 10.2 g of the desired 1- (2-methyl-5-thiazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine. Schmp.204-207 ° C.

Example 9

(Compound No.9)

A mixture of 2-fluoro-5-pyridylmethylbromide (9.5g), 2- (nitroimino) imidazolidine (6.5g), potassium carbonate (7.6g) and acetonitrile (100ml) was refluxed for 2h. After the reaction, the reaction mixture was cooled to room temperature, and cold water (100 ml) was added. The obtained crystals were collected by filtration and washed with ether to give pale-colored 1- (2-fluoro-5-pyridylmethyl) -2- (nitroimino) imidazolidine (6.0 g) as the desired compound. Mp 121-124 ° C.

Example .10

= N-NO ₂

(Compound no. 10)

A solution consisting of N- (2-chloro-5-pyridylmethyl) trimethylenediamine (10g), nitroguanidine (5.7g) and water (80ml) was heated at 80 ° C for 3 hours. The reaction mixture was cooled to room temperature and extracted twice with 50 ml portions of dichloromethane. Dichloromethane was distilled off from the extracts and the tarry residue was purified by column chromatography on silica gel to give almost colorless 1- (2-chloro-5-pyridylmethyl) -2-nitroimino) tetrahydropyrimidine (6.1 g). M.p. 113-117 ° C.

Example 11-i

A solution of N- (2-chloro-5-pyridylmethyl) ethylenediamine (18.6g) in toluene (200ml) was stirred at room temperature and cyanogen bromide (10.6g) was added portionwise. Thereafter, the mixture was further stirred. Since the desired 1- (2-chloro-5-pyridylmethyl) -2-iminoimidazolidine precipitated as the hydrobromide, the reaction mixture was filtered and the residue was washed with ether. Mp 202-205 ° C.

Example 11-ii

H-

(Connection No. 11)

The hydrobromide (5.8g) synthesized in Example 11-i was added at 0 ° C to 98% sulfuric acid (30ml). Then, at 0 ° C with stirring, 2 ml of fuming nitric acid was added dropwise thereto. After the addition, the mixture was stirred at ⁰ ° C. for 2 h. The reaction mixture was poured into ice-water (100 g) and extracted with dichloromethane. Dichloromethane was distilled off from the extract under reduced pressure, whereupon pale yellow crystals were obtained. The crystals were washed with ether to give 1- (2-chloro-5-pyridylmethyl) -2-iminoimidazolidine (1.5 g). M.p. 136-139 ° C.

Example 12

_r ».

(Connection No. 12)

Sodium hydride (0.48g) was added to a solution of 2,2,2-trifluoroethanol (2.4g) in toluene (30ml) and the mixture was stirred until hydrogen evolution ceased. As a product while the 2,2,2-trifluoroethanol sodium salt was prepared. To the product were added 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine (5.1 g) prepared according to the procedure of Example 3 and a catalytic amount of 4-dimethylaminopyridine. The mixture was heated to 8O ⁰ C with stirring for 10h. After cooling the reaction mixture, the precipitated crystals were collected by filtration, washed with water and with ether, and then purified by silica gel chromatography, whereby 1- [2- (2,2,2-trifluoroethoxy) -5-pyridylmethyl] -2- ( nitroimino) imidazolidine (1.5 g). M.p. 109-122 ° C.

Example 13

₂ C

(Compound no. 13)

A mixture of N- (1-pyrimidinylmethyl) ethylenediamine (15.2g), 1-nitro-2,2-bis (methylthio) ethylene (14.9g) and ethanol (100g) was heated to reflux with stirring until evolution methylmercaptan ceased (about 3 hours). The mixture was cooled to room temperature, and the resulting crystals were collected by filtration. The crystals were washed with ethanol and dried to give 1- (5-pyridinylmethyl) -2- (nitromethylene) imidazolidine (12.7 g) in the form of pale gold crystals. This product decomposes at 236 ° C.

Example 14

c>

(Compound No. 14),

2-Nitromethylene-imidazolidine (12.9g) was dissolved in dry dimethylformamide (100ml) and 60% sodium hydride in oil (4.4g) was added at room temperature. The mixture was stirred at room temperature until hydrogen evolution ceased. Then 2-methyl-5-pyrazinylmethylchlorid (14.3 g) was added at room temperature, and the mixture was stirred at 4O ⁰ C for 8 h. After cooling to room temperature, the reaction mixture was added with 200 ml of water and extracted with dichloromethane. After distilling off the dichloromethane from the organic layer under reduced pressure, 1- (2-methyl-5-pyrazinylmethyl) -2- (nitromethylene) imidazolidine (5.4 g) was obtained in the form of yellow crystals having a melting point of 163-166 ° C ,

Example 15

-Cl

(Connection No. 15)

A mixture of 2 g of 2-amino-1- (2-chloro-5-pyridylmethylamino) propane, 1.6 g of 1-nitro-2,2-bis (methylthio) -ethylene and 20 ml of methanol was refluxed for 5 hours with stirring. Upon standing at room temperature, a crystalline product separated. The product was filtered off with suction, washed with methanol and then dried in vacuo. 1.9 g of 1- (2-chloro-5-pyridylmethyl) -4-methyl-2- (nitromethylene) imidazolidine were obtained as pale yellow crystals. M.p. 170-174 ⁰ C.

Example 16

CH-NO ₂

(Connection No. 16)

A mixture of 2.6 g of N- (3-methyl-5-isoxazolylmethyl) -N '- (1-methyl-4-pyrazolyl) trimethylenediamine, 1.6 g of 1-nitro-2,2-bis (methylthio) ethylene and 10 ml Ethanol was heated to reflux for 15h with stirring. After the reaction, the ethanol was removed by vacuum distillation. The tarry residue was purified by chromatography on a silica gel column. The product, 0.7 g of 1- (3-methyl-5-isoxazolylmethyl) -3- (1-methyl-4-pyrazolyl) -2-nitromethylene) tetrahydropyrimidine was obtained in the form of a viscous oil. no ^c 1.5670.

Example 17

= CH-N0

L>

Cl

(Connection No. 17)

6.6 g of finely powdered 1-nitro-2,2-bis (methylthio) ethylene were mixed well with 7.5 g of 2- (2-chloro-5-pyridylmethylamino) ethanol. The mixture was heated to 110 ^° C. to 120 ^° C. for 30 minutes or until the formation of methylmercaptan ceased. The resulting oil was cooled to room temperature and purified by chromatography on a silica gel column. The product, 3- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) oxazolidine, weighed 1.7g. M.p. 123-124 ⁰ C.

Example 18

ZH-NO ₂

(Connection No. 18)

2.6 g of potassium hydroxide were dissolved in 20 ml of anhydrous ethanol. To the solution was added 3.7 g of 2- (2-methyl-5-pyrazinylmethylamino) ethanethiol under a nitrogen atmosphere. The solution was then cooled to 0 ⁰ C, and C were 3.0 g of 2,2-dichloro-1-nitroethylene dropwise at 0 ° C to 10 ° thereto After the addition the mixture for 1 h at 10 ° C was stirred. The ethanol was removed by vacuum distillation, chloroform was added to the residue, and the chloroform layer was washed with a 1% sodium hydroxide solution and with water. The chloroform layer was treated in a conventional manner to give pale yellow crystals of 3- (2-methyl-5-pyrazinylmethyl) -2- (nitromethylene) thiazolidine weighing 2.0 g. M.p. 147-15O ⁰ C.

Example 19

(Compound no. 19)

A mixture of 4.7 g of N- (1,2,5-thiadiazol-3-ylmethyl) ethylenediamine, 3.4 g of nitroguanidine and 20 ml of water was 1 h at 50 ° C to 6O ⁰ C and then 20 min at 7O ⁰ C stirred. The resulting solution was cooled slowly to 5 ^° C, whereby the product precipitated. The crystalline product was collected by filtration, washed with water and methanol and dried. The yield of 1- (1,2,5-thiadiazol-3-ylmethyl) -2- (nitroimino) imidazolidine was 2.9 g. Mp 162-165 ⁰ C.

Example 20

= N-NO

L>

CH ₂

(Connection No. 20)

A mixture of 2.9 g of 2-nitroiminothiazolidine, 2.9 g of anhydrous potassium carbonate, 2.3 g of 2-chloro-5-pyridylmethyl chloride and 50 ml of acetonitrile was heated to reflux with vigorous stirring for 5 hours. After the reaction, most of the acetonitrile was removed by distillation, and water was added to the residue. After a solid product separated, it was collected by filtration. The crude material was recrystallized from ethanol to give the desired 3- (2-chloro-5-pyridylmethyl) -2- (nitroiminö) thiazolidine. Yield 3,8g. M.p. 137-138 ° C.

Example 21

Π N = N-NO.

  α

(Connection No. 21)

To a mixture of 1.3 g of finely powdered 2-nitroiminoimidazolidine and 30 mL of dry acetonitrile was added portionwise 0.4 g of sodium hydride (60% in oil) at room temperature, and the mixture was stirred until evolution of hydrogen glass ceased. A solution of 1,7g2-chloro-5-thiazolylmethyl chloride in 10 ml of acetonitrile was then added dropwise at room temperature. After the addition, the mixture was stirred at room temperature for 3 hours and then poured into ice-water. The organic layer was extracted with dichloromethane, and the dichloromethane extract was washed with 1% sodium hydroxide solution and with water. The product solidified upon evaporation of the dichloromethane and was washed with water and dried. The desired 1- (2-chloro-5-thiazolylmethyl) -2- (nitroimino) imidazolidine weighed 1.4g. M.p. 147-15O ⁰ C.

Example 22

CH.

(Connection No. 22)

According to the procedure described in Example 7, a gummy substance was obtained from 2.3 g of ethyl nitro (tetrahydro-2H-1,3-thiazin-2-ylidene) acetate and 1.6 g of 2-chloro-5-pyridylmethyl chloride. The substance was triturated with ethanol. The insoluble material was washed with hexane and then purified by chromatography on a silica gel acid. The desired ethyl [3- (2-chloro-5-pyridylmethyl) tetrahydro-2H-1,3-thiazi.n-2-ylidene] acetate weighed 0.2g. M.p. 180-184 ⁰ C.

Example 23

N-NO.

(Connection No. 23)

5.8 g of 2-imino-3- (4-pyridylmethyl) thiazolidine were added dropwise at -5 ⁰ C to ⁰ ° C to 20ml. Added sulfuric acid. 6 ml of fuming nitric acid were then added dropwise to the solution at the same temperature. After stirring for 30 minutes at 0 ⁰ C to 5 ⁰ C, the mixture was poured onto crushed ice. Extraction twice with dichloromethane and subsequent treatment usually yielded 1.4 g of the desired 2-nitroimino-3- (4-pyridylmethyl) thiazolidine. M.p. 151-152 ° C.

Example 24

(Connection No. 24)

A mixture aus2,7g 3- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) thiazolidine, 3.5 g of methyl vinyl ketone and 30 ml of chloroform was stirred for 2 d at 40 ⁰ C under a nitrogen atmosphere. Thereafter, 3.5 g of methyl vinyl ketone was added to the reaction mixture, and it was stirred for further 2d at the same temperature. After removal of the volatiles in vacuo, the residue was purified by chromatography on a silica gel column. The desired 3- (2-chloro-5-pyridylmethyl) -2- (1-nitro-4-oxopentylidene) thiazolidine weighed 0.1 g. Schmp.75-80 ° C.

Example 25

(Connection No. 25)

A mixture of 2.3 g of 1- (4-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine, 0.5 g of paraformaldehyde and 30ml of dioxane was stirred vigorously for 2 h at 70 ⁰ C to 80 ⁰ C. After the reaction, the dioxane was evaporated under reduced pressure to about ^1/3 of its volume. The crystallized product was filtered and dried. The yield of the desired bis [a-nitro-1- (4-pyridylmethyl) tetrahydropyrimidin-2-ylidene-methyl] methane was 1.8 g. Mp 222-223 ° C

Example 26

CH

(Connection No. 26)

To a solution of 2.4 g of 1- (3-methyl-5-isoxazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine and 30 mL of dry dichloromethane was added 1.6 g of trichloroacetaldehyde at room temperature. After three hours of stirring at 25 ° C to 30 ° C, the crystallized product was filtered off, washed with ether and dried. The desired 1- (3-methyl-5-nitro isoxazolylmethyD ^ -d ^ -hydroxy-SAS trichloropropylidenltetrahydropyrimidin weighed 3.1 g. Mp. 128-130 ⁰ C (dec.).

Example 27

vci

(Connection No. 27)

2.5 g of 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine were dissolved in 40 mL of dry dichloromethane and 10 mL of water was added. A solution of 1.6 g of bromine in 10 ml dichloromethane was good stirring at 0 ^o Cbis5 ° C within lOminhinzugefügt. After lOminütigem stirring at ⁰ C to 5 ⁰ C, the crystallized product was filtered, washed with cold water and a small amount of dichloromethane and dried. The yield of 1- (2-chloro-5-pyridylmethyl) -2- (bromonitromethylene) imidazolidine was 2.5g. M. 110-115 ⁰ C (Zers.).

-45- Z4Z74Z

Example 28

CHCOH

(Compound no. 28)

To a mixture of 1.2 g of finely powdered 1- (4-pyridylmethyl) -2- (nitromethylene) tetrahydropyrimidine in 20 ml of methanol, 2 drops of conc. Sulfuric acid and then added 1.6 g of 25% aqueous glyoxylic acid. The mixture was stirred for 3 h at room temperature. After adjusting to pH 7, the deposited product was filtered, washed with water, methanol and ether and dried. The desired 3- [1- (4-pyridylmethyl) -1H, 4H, 5H, 6H-tetrahydropyrimidin-4-yl] -3-nitroacrylic acid weighed 1.1 g. M.p. 150-155 ⁰ C (Zers.).

Example 29

(Connection No. 29) ·

3.1 g of phenyl chloroformate were added below von.O ⁰ C to a solution of 1.6 g methylimidazole in 50 ml of dichloromethane. After stirring at the same temperature for 30 minutes, 2.5 g of 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazoline was added to the mixture, and the resulting mixture was stirred at room temperature for 24 hours. The mixture was then washed in each case with water, 1% hydrochloric acid and 1% sodium hydroxide solution. Removal of the dichloromethane by distillation yields glassy phenyl-nitro [1- (2-chloro-5-pyridylmethyl) -3-phenoxycarbonylimidazolidin-2-ylidene] acetate (3.2g). This was dissolved in 20 ml of dimethylformamide. 1.7 g of sodium carbonate was added to the solution and the mixture was stirred at room temperature for 3 d. Thereafter, water was added and the organic layer was extracted with dichloromethane. The extract was washed with 1% sodium hydroxide solution and with water. After evaporation of the dichloromethane, the residue was purified by chromatography on a silica gel acid. The desired product, phenylnitro [1- (2-chloro-5-pyridylmethyl) imidazolidin-2-ylidene] acetate, weighed 0.2g. Mp. 224-228 ° C (decomp.).

Example 30

-so

N-NO

NO-

(Compound No. 30) '

0.2 g of sodium hydride (60% in oil) was added to a solution of 1.1 g of 1- (3-methylisoxazol-5-ylmethyl) -2-nitroiminoimidazolidine in 15 mL of dry dimethylformamide, and the mixture was stirred until the evolution of Hydrogen gas was finished. 1.2 g of 2-methyl-5-nitrobenzenesulfonyl chloride was then added to the mixture. After stirring at room temperature, the mixture was poured into ice-water and the organic layer was extracted with dichloromethane. The dichloromethane was removed by distillation, whereupon a crystalline product was obtained. This was washed with ether. The desired 1- (2-methyl-5-nitrobenzenesulfonyl) -3- (3-methylisoxazol-5-ylmethyl) -2-nitroiminoimidazolidine weighed 1.1 g. Mp 154-156 ° C.

Example 31

(Connection No. 31)

0.2 g of sodium hydride (60% in oil) was added to a solution of 1.3 g of 1- (2-chloro-5-pyridylmethyl) -2-nitromethylene-imidazolidine in 15 mL of dry dimethylformamide, and the mixture was stirred at room temperature until the evolution of Hydrogen gas was finished. 0.9 g of 4-chlorobenzenesulfenyl chloride was then added dropwise to the solution at 0 ° C with stirring. After stirring for 1 hour at room temperature, the reaction mixture was poured into ice-water. The deposited crystals were filtered and ethyl acetate was recrystallized to give 1- (2-chloro-5-pyridylmethyl) -2- [C4-chlorophenylthio) nitromethylene] imidazolidine. The yield was 1.3 g. M.p. 159-161 ⁰ C.

Example 32

CONHSO ₂

(Compound No. 32)

A solution of 0.9 g of benzenesulfonyl isocyanate in 10 ml of dry dichloromethane was added dropwise at room temperature to a solution of 1.3 g of 1- (2-chloro-5-pyridylmethyl) -2-nitromethylene-imidazoline in 25 ml of dry dichloromethane. The solution was stirred for 2 hours at the same temperature and then about half of the dichloromethane volume was evaporated under reduced pressure. The product which crystallized was filtered and washed with ether. The desired N-benzenesulfonyl-2- [1- (2-chloro-5-pyridylmethyl) imidazolidin-2-ylidene] -2-nitroacetamide weighed 1 g. M.p. 95-100 ° C.

Example 33

(Compound No. 33)

A mixture of 2.2 g of 2-nitroimino-1- (3-pyridylmethyl) imidazolidine, 1.6 g of 2-chloro-5-chloromethylpyridine and 1.4 g of anhydrous potassium carbonate in 30 ml of acetonitrile was heated to reflux for 16 h with stirring. Then the acetonitrile was removed under reduced pressure. Dichloromethane was added to the residue, and the mixture was washed with water and with 1% sodium hydroxide solution. After removing the dichloromethane under reduced pressure, the residue was purified by chromatography on a silica gel column to give 1- (2-chloro-5-pyridylmethyl) -2-nitroimino-3- (3-pyridylmethyl) imidazolidine. The yield was 2.1 g. Mp 143-144 ° C.

Example 34

Γ ~ \

(Connection No. 34)

0.4 g of sodium hydride (60% in oil) was added portionwise to a solution of 2.6 g of 1- (2-chloro-5-pyridylmethyl) -2-nitroiminoimidazolidine in 20 mL of dry dimethylformamide. The mixture was stirred at room temperature until evolution of hydrogen ceased. A solution of 1.5 g of isopropyl bromide in 5 ml of dry dimethylformamide was added dropwise to the mixture at room temperature, and after the addition, the mixture was stirred at room temperature for 3 hours. The reaction mixture was then poured into ice-water and the precipitated crystals were filtered. They were recrystallized from ethanol to give 1- (2-chloro-5-pyridylmethyl) -3-isopropyl-2-nitroiminoimi'dazolidine. The yield was 1.5g. M.p. 138-142 ° C.

Example 35

C ₃ H ₇ CO

(Connection No. 35)

A mixture of 2.7 g of 3- (2-chloro-5-pyridylmethyl) -2-n1tromethylenthiazolidin and 8ml of butyric anhydride was stirred under a nitrogen atmosphere at 6O ⁰ C for 8 h. The volatiles were then removed by distillation at 1.33mbar (1mmHg) keeping the bath temperature below 6Q ° C. The residue was dissolved in dichloromethane and washed with 1% sodium hydroxide solution. The dichloromethane layer was then purified by chromatography on a silica gel column to give viscous oily 1- [3- (2-chloro-5-pyridylmethyl) thiazolidin-2-ylidene] -1-nitro-2-pentanone ,

The yield was 0.15 g. no ° 1.6342.

By the same procedures as described in the above Examples, the compounds of the formula (I) shown in the Tables below were obtained.

In the Tables, the designation "-" for R ³ and R ^{4 means} that η is 0, and in this case, the corresponding ring structure denotes a 5-membered heterocyclic ring.

Table 1 covers the case where X is a sulfur atom and the compounds of formula (I) are represented by the following formula:

Table 1

(CH,) m

R-C

Connection no. m R Binding position of the pyridine ring Qi 36 2 H 5 2-F 37 3 B 5 2-F 38 2 -CH ₃ 5 2-Cl 39 2 H 5 2-Br 40 2 Ξ 5 2,3-Cl ₂ 41 2 Ξ 5 2,3,4,6-F ₄ 42nd 2 B 4 · 2-Cl 43 3 B 5   2-Br 44 2 H 5 2-F, 3-Cl 45 2 H 2 3-Cl 46 3 H 2 -T-Cl 47 2 B 2 3,5-Cl ₂ 48 3 B 5-F 49 2 B 2 6-Br 50 3 B 3 2-Cl 51 3 B 3 5-Cl 52 2 B 3 5-Br 53 2 B 3 5-F

Table 1 - continued

54 2 -CH ₃ , 5 2-F 55 3 Ξ 5 2,4-Cl ₂ 56 2 e 5 2,4-Br ₂ 57 2 B 4 2,6-F ₂ 58 3 H 4 2-F · 59 2 B 4 2,6-Br ₂ 60 2 B 5 2-F, 3-3r 61 2 B 5 2-Cl, 3-F 62 2 - ^C 2 ^H 5 5 2-Cl ₃ 63 2 B 4 - 64 3 B 4 - 65 2 B 5 2-CH ₃ 66 3 B , 5 2-CH ₃ 67 2 B 5 2-C ₂ H ₅ 68 Z B 5 2-CH ₂ CH = CH ₂ 69 2 B 5 2-CH ₂ C = CH 70 3 B 5 2-OCH ₃ 71 2 e 5 2-SCH ₃ 0 72 2 B 5 2-S-CH 0 73 2 B 5 2-Cl, 3-CH ₃ 74 2 -CH ₃ 3 - 75 2 B 5 2-CF ₃ 76 3 B 5 2-CF ₃ 77 2 B 5 2-NO ₂ 78 3 B 5 2-NO ₂ 79 2 B 5 2-CN

Table 1 - continued

80

81 82 83 84

85 86 87 88 89 90 91 92 93

94

95 96

3 e 2 B 2 H 2 Ξ 3 e 2 Ξ 3 Ξ 2 Ξ 2 H 2 H 2 • Η 3 e 2 H 2 e 2 B 2 H 2 Ξ

5

5-5- 5-5-

5-5- 5-5- 5-5- 5-5- .5-

5

5

2-CN

2-CCl ₃ 2-C ₂ B ₄ OC ₂ E ₅ 2 -CH ₂ OCH ₃ 2-0CHF "

2 OCF.

2-OCH ₂ CF ₃ 2-SCClF ₂ 2-SCF,

2-CHF ₂

0 2-S-CF.

2-S-CF ₃

2-CH = CCl

In addition to Table 1, Table 2 covers the case where X is a sulfur atom.

Table 2

Z R IRR ⁶ "" Z-CH R ² R ³ R ³ · R ⁵ R ⁶ η Y Schrrp. 143-145 ^e C Q- B R ¹ B - B H 0 N Verb no. F ^ ~ \ V B e B - R ⁴ B B 0 N 97 B B B - - B B 0 N 98 FCl ₂ Cg> - B H e B - e B 1 N 99 H B B - - e B 0 N 100 B B B - e e B 0 N 101 B B B B - B H 1 N 102 CHzC-CH - J * -, V-N-Jj B B H H B -   - B E B B 0 0 N N 103 _ci j> B B B B - B B B 0 N 104 105 B B B B - B B 1 N 106 B B B - - B e 0 N 107 ' ³ D B H B - B e B 0 N 108 Eh B H B e - H B 1 N 109 H B B - - B B 0 N 110 B B B - H B B 0 CH 111 H - 112 -

Table 2- continued

Verb no.

R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η H H H - , - B B 0 H H B B B B B 1 H H H - - B B 0 H H B - - B B 0 H B H - - H H 0 H H H - - B H 0 B B B - - B B 0 H H H B B B B 1 H H B , - - H B 0 H H B - - B H 0 H H H - ' - B B 0 H H B - - H H 0 Ξ B B B B B B 1 H B H B B B B 1 H B B - - B B 0 H B B - - H B 0 H H B - - H B 0 B B H B H H H 1 H H H - - H B 0 H H H B H B B 1

113 114

115 116 117 118 119 120 121 122 123 124 125 126 127

128 129 130 131 132

B.

Cl

qr

^H 3 - \ -

r ₃ e </

Cl

Cl

Cl - // V)

B ₃ C

Cl - //

Cl

-qt

CH

CH

CH

C-CH.

C-CF.

C-CH ₂ OCH ₃ C-CH ₂ SC ₂ H ₅ C-CH ₂ N (CH ₃ J ₂ C-CH ₂ CH = CH ₂

C- (CH ₂ J ₂ COOCH ₃

OH

C-CHCCl ₃

C-COCH

C-COCH ₂ OCH ₃

25

¹ D 1.6358

Table 2 - continued

Verb no.

133

134 135 136 137 138

139 140 141 142 i ⁴³ 144 145 146 147 14b 149 150 151 152

B.

el

ci-ΓΛ

H ₃ C.

V-O

H B B B

B B B H B B B

B B B B B B

B B B

B B B B H B B B

C-COCCl.

C-CO-fVSr C-COOCH.

C-COOC ₂ H ₅

C-COOC ₂ H ₅

C-COO- / y -Cl CS- (CH ₂ J ₃ CH ₃

"Ο

C-CONHCO C-CONHSO.

C-COOC ₂ H ₅ C-COCH ₃ C-COOCH.

C-COOCH ₂ CF ₃

CHCHC

24

1.5978

Table 2- continued

Verb no. ζ R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η Y 153 CH ₂ -CH-CH ₂ -J- H B H - - B B 0 CH 154 B B H B B B H 1 CH 155 B B H B H B B 1 CH 156 B B B B B B H 1 CH 157 Cl ₃ CCONH- ¹ - ⁵ H H B - - H H 0 CH 158 J * B H B - B H 0 CH 159 D- " H H e - - B H 0 CH 160 H B B H H B H 1 CH

Table 3 covers the case where X is CH-R ⁸ .

-bb-

Table 3

ζ R R ¹ RZ-CH R ⁴ R ³ ·> R ³ R ⁴ I R ⁵ R ⁶ η R ⁸ Y nj ° l, 5995 O CH ₃ B N ^^ CH-R ⁸ H - - B 0 H CH H H R ² Y-NO. B B B H 1 H CH Verb no. ^F - £> H B H - - H H 0 B CH 161 B B B - - H H. 0 H CH 162 ^F 2 ^HC O B H H - - B H 0 H CH 163 F cJ ~ \ - 3 ^ tL / B H B - - B H 0 B CH 164 F ₃ CO ^ y B B H - - H B 0 H CH 165 ^H 3 ^C- O B B H - - B B 0 B CH 166 ^C1 O H B B - - H H 0 H N 167. B H B B B B B 1 H N 168 ^BE -O H B B - - B H 0 B N 169 B H B - - B B 0 H N 170 ^CH 3 H B - - H H 0 B CH 171 ^H3 > B H B - - B B 0 B CH 172 ^F2HC iv H H H H B H H 1 e CH 173 ci Ji B H H - - H H 0 B CH 174 _aco j> B H B - - H H 0 B CH 175 B B B H H H H 1 B CH 176 H 177 H 178

Table 3 - continued

Verb no.

R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁸ B B B - - B B O e B B B - , - B H O B B B B B B B B 1 H B B B - - B B O B B H B - - B H O  ο B B B - - B B O S B B B B B B H O B B H B - - B B O H CH ₃ B H - '- B B O H • Β H - - B B O B B B H - - B B O B H B H - - B H O B B B H - -   B B O B ' B B H - - B B O H B B B B B B B 1 ^CH 3 B B B   - -, B B O B H H B - - B B O B H B B - - B B O B H H B B B H H 1 B H H B - - H B O CH ₃

179 180

181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198

D-

H ₃ C- '

91

Cl ₂ C = C-CH ₂ -

H ₃ C

Cl

Ö

IV D

Q-

E, C

 Ö

Egg / Λ

CH N N N

CH

CHCH

CH

CH

C-COOC ₂ H ₅

C-S-f \\ C-Br

Table 4 covers the case where X is an oxygen atom.

Table 4

ζ R P R ¹ R ^{2 5} \ / R ² V ^ V ι R ³ R ⁴ R ⁵ R ⁶ η Y M.p. 137-140 ⁰ C B ^R B Z-CH- H B - - B B 0 CH B B B Y-NO B B B B 1 CH Verb no. B B B - - B B 0 CH 199 B B B - - B B 0 CH 200 F, C - / "V B B B - - B B 0 CH 201 B • B H - - - B H" 0 N 202 B B B - - B B 0 N 203 F ₃ cs ^ y B B B - - B B 0 N 204 B ₃ ChQ- B E. B _ _ B B 0 N 205 B B B - - H B 0 CH 206 ^H 3 ^c "fy B H H - - B B 0 CH 207 ^B3C B H B B - - H B 0 CH 208 B B B - - H B 0 CH 209 N-, S ₃ CS- Li B B B H H H B 1 CH 210 HC-iD " H H B H H H B 1 CH 211 H H H - - B H 0 CH 212 213 214

Table 4 - Continued

Verb no.

215 216 217 218 219 220 221 222 223 224

Cl

CV

H B B E B

B E B

CB. H

th

CH

CH

CH

CH

C-CH

CH

cc oo-

C-CO- (CH ₂ J ₂ CH ₃

Table 5 covers the case in which the compounds of formula (I) are represented by the following formula:

table

H "N.

R-

m R Binding position - M.p. 90-94 ° C (Zers.) Connection no. 2 U on the pyridine ring - 225 3 e 3 - 226 2 -CH ₃ 3 - 227 2 -C ₂ H ₅ 3 - 228 2 -CH (CH ₃ V ₂ 3 - Scljnp. 154-157 ° C 229 2 H 3 - M.p. 163-165 ° C 230 3 H 4 5-Cl 231 2 H 4 2-P 232 3 H 2 2-Cl 233 2 -CH ₃ 5 2-Br 234 2 H 5 2-CH ₃ M.p. 157-160 ⁰ C 235 2 B 5 2-CH ₃ Size 155 _r 5- 236 3 B 5 2-C ₂ H ₅ 158.5 ° C 237 2 B 5 2-OCH ₃ 238 2 e 5 2-OC ₂ H ₅ 239 2 B 5 2-SCH ₃ 240 2 H 5 241 5

Table 5 - continued

242 2 H 5 2-NOj - 2-CF ₃ mp 134-14 6 ⁰ C 243 2 H 5 2-CN 2-CF ₃ 244 2 H 5 2-NHY 2-CCl ₃ 245 3 H 5 O 2 -NBCCH ₃ 2-CFjCl 246 2 B 5 2-N (CH ₃ ) j 2-CHjCHjF O 2-CHjCHjCl 247 2 H 5 2-C-OCjH ₅ 2-CHjCF ₃ 248 2 H 5 2-C-CB, 2-OCHFj Il · * 0 2-OCF ₃ O 249 2 H 5 2-S-CH ₃ 250 2 H 5 0 2-S-CB ₃ 0 251 2 H 5 2-CHFj 252 2 H 5 253 3 e 5 254 2 B 5 255 2 B 5 * 256 2 e 5 257 2 B 5 258 2 H 5 259 3 H 5 260 2 B 5

Table 5 - continued

261 3 H 5 2-OCH ₂ CF ₃ Schnp. 198-201 ⁰ C 262 2 H 5 2-SCF ₃ 263 2 H 5 2-SCF ₂ Cl 264 2 B 5 '3-Br 265 2 Ξ 2 5-CF ₃ 266 2 H 5 2-CH ₂ C = CB 267 2 Ξ 5 2-CH ₂ CB = CB ₂ 268 2 H 5 2-CH = C (Cl) ₂ 269 2 B 5 2,3-Cl ₂ 270 2 B 5 2-Cl, 3-CH ₃ 271 2 B 4 2,3,5,6-F ₄ 272 2 B 5 2-CHO 273 2 B 5 2-CF ₂ Br

Table 6 covers the case where Z is an optionally substituted pyridyl group and X is NR ⁷ ; the compounds of formula (I) are represented by the following formula:

^ ζΗ ⁸ -

V * "* ⁷

Y-NO.

In Table 6, the designation "-" for Q _{e means} the absence of a substituent and the designation "-" for R ² and R ^{5 in} common means that R ² together with R ^{5 forms} a single bond.

Table 6

Qi Binding position on the pyridine ring > R Y-NO ₂ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y M.p. 184-187 ° C i i M.p. 107-110 ^e C - 4-position R t -CH- CH ₃ - - B H 0 H CH _ 3 position R CH ₃ B B 0 B CH M.p. 177-180 ° C, Verb no. 3 position H R ¹ CH ₃ B B 0 B CH Schmp. 190-191 ° C 274 4- position CH ₃ H H CH ₃ CH ₃ B B 1 H CH M.p. 209-212 ^C C 275 - 4- position B B H OH B B B 1 H CH 276 2-F S position H CH ₃ .CH ₃ - - H B 0 B CH 277 2-Cl 5- position .H H B B CH ₃ B B 1 fl CH 278 2-Cl 5- position H H C ₂ H ₅ - - B B 0 B CH 279 2-Cl 5- position B H CH ₃ - - CH ₃ H 0 B CH 280 2-Br 5- position B B ^CH 3 - - B H 0 B CH 281 2-CF ₃ 5- position H B CH ₃ - • - B B 0 B CH 282 2-CH ₃ 5- position B B CH ₃ - - H B 0 B CH 283 2-CF ₃ 5- position H H CH ₃ - - B B 0 B CH 284 2-NO ₂ , 3-OCH ₃ 5- position 3- position B B CK ₃ H - - H H H B 0 0 H CH ₃ CH CH 285 B B 286 H H B 287 283 H B

Table 6- Continued

Verb no. Qi Binding position on the pyridine ring R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y Mp. 128-13O ⁰ C 289 2-F S position H B B _ B B 0 CH (CH ₃ J ₂ CH 290 2-Cl S position H H B - - B B 0 CH 291 2-Cl 5- position B B B B H B B 1 CH 292 2-Cl 5- position H H B. - - B B 0 OH CH 293 2-Cl 5_Position H H B - B B 0 OC ₂ H ₅ CH 294 2-Cl 5-position B B B - - B B 0 OCH ₂ -Q CH 295 2-Cl 5-position H H B - - B B 0 CH ₂ OC ₂ H ₅ CH 296 2-Cl 5_Position H H B - - B B 0 CH ₂ CH ₂ CC ₄ H ₉ CH 297 2-Cl 5_Position H H H - B B 0 CH ₂ CH ₂ SC ₂ H ₅ CH 298 2-il. 5-position H H B - - B B- 0 CH ₂ CH = CH ₂ CH M.p. 175-178 ⁰ C 299 2-Cl S-TOsition H H B - - H B 0 CH ₂ CH ₂ CN CH Mp 176-18O ⁰ C 300 3_Position H H B _ B B 0 "2-Q CH 301 - 4 - position B B B - - B B 0 CH Schmp. 152-153 ⁰ C 302 2-F 5-position B B B B B B B 1 CH M.p. 158-160 ⁰ C 303 2-Cl 5-position B H B mm B B 0 CH ₂ -Q CH 304 2-Cl 5-position H H B - - B B 0 ^CH 2 ^r O ~ ^Cl CH 305 2-Cl S position H H H - - B B 0 CH np ⁰ l, 6495 306 2-CH ₃ 5-position B H B - - B B 0 CH Schmp. 154-156 C 307 2-Cl 5-position B H B - - B B 0 CB ₂ -Q CH 308 2-Cl 5-position H H B - - B H 0 CH

Table 6 - continued

Verb no.  ι Binding position on the pyridine ring R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y B C-OH n ^2O l _f 648 ( 309 2-F .5 position H B B - - B B 0 CH 310 2-Cl 5-position H H B - - B B 0 CH 311 2-Br 5-position B H B - - B B 0 CH 312 2-Cl 5 "position H H B - - B B 0 ^ CH ₃ CH 313 2-Cl 5-position B B B - B B 0 CH 314 - 3-position H B B - - B B 0 B C-Cl 315 2-Cl 5-position H B H - - B B 0 B C-F 316 2-Cl 5- position B H ^CH 3 - - B B 0 B C-Br 317 - - 4- position ^ B H B B B B B 1 B C-CH ₃ 318 2-Cl 5- position H H H - - B B 0 B C-CH ₃ 319 2-Cl 5- position B H H - - B B 0 B C-CH ₂ F 320 2-Cl S *. position H H B - - B B 0 B C-CF ₃ 321 3 position H B B _ _ B B 0 B C-CH ₂ OH OH Mp. 135-14O ⁰ C 322 2-F 5- position B B B B B B H 1 H C-CHCCl ₃ 323 2-Cl 5-position B B H - - B B 0 B OH C-CHCCl ₃ Schrftp. 155-158 ⁰ C 324 2-Cl 5-position B H H B H 0 Hh Λ "^ -H ₂ C NO ₂ 325 - 3-position H H B H B H H 1

Table 6 - continued

Verb no. Q ₁ Binding position on the pyridine ring R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y Schnapps 102-105 ° C 326 2-Cl 5-position H H H - - H H 0 H C-OCH ₃ Schirp. 213-215 ⁰ C 327 2-Cl 5-position H H H - - B B 0 H C-OCH ₂ - £ ^ 328 - 4-position H H H - - H B 0 B CSC ₃ H ₇ 329 2-CH ₃ 5- position H H B - - B B 0 B c-s - ^^ 0 M. 159-171 ⁰ C 330 - 3-position H H H - - H H 0 H CS-CH ₂ Cl OO 331 2-Cl 5-position H H H - - H B 0 B 00 332 2-CF ₃ 5-position H H H - - H H 0 B δ 333 2-Cl 5-position H H H - - B B 0 B C-COCH ₃ . 334 2-F 5-position H H H - - B B 0th B C-COCCl ₃ 335 2-NO ₂ 5-position H H H - - B H 0 B C-COCH = CH ₂ 336 2-Cl 5- position H H H H H 0 H C-COC ₃ H ₇ 337 2-Cl 5-position H H H _ B H 0 B C-C0 / ₃ ~ VcH OCH ₃ 338 - 3-position H H H B B B B 1 H c-co-O 339 - 4-position CH ₃ H H - - B B 0 H C-COOCH ₃ 340 2-Cl 5- position H H Ξ - - B B 0 B C-COOC ₂ H ₅ 341 2-CN 5- position H H H - - B H 0 B C-COOC ₄ H ₉ 342 2-F 5-position H R H - - H H 0 H C-COO-VcH ₃ 343 2-Cl 5- position H H H - - B B 0 H C-COO- ^ VnO ₂ 344 2-Cl 5- position H B H - - H H 0 H C-COS-C ₄ H ₉

Table 6 - continued

Verb no. 2-Cl Binding position on the pyridine ring R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y Mp. 89-94 ° C • Glass 345 2-CF ₃ 5-position H H H H H 0 e Cl C-CONHCO - / "^ (Dec.) 346 2,3-Cl ₂ 5-position B B H - - H H 0 B \ C-CONHCO - / "" ^ 34 7 5-position H B H - _ B H 0 B C-CONHS-CH ₃ 2-CHF ₂ Ö :H 348 5- position Ξ H e - - B H 0 e 0 C-CONHS- <f ~ V < 349 2-Cl ₃ _position H B H H B 0 CH ₃ 0 C-COCH ₃ M.p. 100-105 ^C C 350 2-Cl 5_Position H B H - - B B 0 CH ₃ C-COC ₃ H ₇ 351 2-CH ₃ 5_ position H B B - - B H 0 COCH ₃ C-COCH ₃ 352 - 5_Position B B H -. - B B 0 , Cl C-Cl 353 2-Cl 2- position H B H H B B B 1 COOC ₂ H ₅ C-COOC ₂ H ₅ 354 2-CF ₃ 5- position H B H - - H B 0 COO - / "^ C-COO-Z j ^ 355 -. 5-position B H B - - H B 0 c-COO- ^ 3 356 2-Cl 4-position B H B - - H e 0 COS / 3 ^C0S "C3 357 - 5-position B H H - - B B 0 c-s-O 358 2-Cl 3-position. H H H CH ₃ H B B 1 H N 359 2-Cl 5-position B B CH ₃ - - B H 0 H N 360 2-Cl 5-position B CH ₃ CH ₃ - - H B 0 e N 361 2-SCN 5-position B H H - - H H 0 CH ₃ N 362 5-position H H H - - H B U CH (CH ₃ J ₂ N

Table 6- Continued

Verb no. 2-F Binding position on the pyridine ring R R ¹ R ² R ³ R ⁴ R ⁵ R ^S η R ⁷ Y 1 ^ 1.5854 363 2-Cl 5 · Position H B B - - B B 0 CHjCBjCl N 364 2-Cl 5- position H H H - - B H 0 CHjCH = CHj N 365 2-Cl 5- position H H B - H B 0 CHjCCI = CCIj N 366 2-F 5- position H H H - - H H 0 CHjCH ₂ CN N 367 2-CF ₃ 5- position H B B - - H B 0 CH ₂ CsCH N 368 2-Cl 5- position B H B - - B B 0 CHjCH ₂ N (CjH ₅ ) J N 369 - 5- position B B H H H B B 1 CHjOCH ₃ N 370 2-CHjF 3 position H H B - - B B 0 CHjCH ₂ SC ₂ H ₅ N 371 2-Cl 5- position H H B - - H B 0 CH ₂ SC ₄ H ₉ N 372 2-Cl 5- position H H H - - B B 0 CH ₂ CN N 373 5-CF ₃ 5- position H H H - - H Ξ 0 CHjSi (CH ₃ ) ₃ N 374 2-Cl 2- position H H H - - Ξ H 0 CHjSi (CH ₃ J ₃ N 375 2-NOj 5- position H B B H B B B 1 -ο N 376 5- position B H B _ - B H 0 CH ₂ -Q N 377 2-Cl 3 position B B Ξ H H 0 N 37ö 5-OCF ₃ 5- position B B H H H 0 Cl ^CH2 "C3" ^C1 N M.p. 126-128 ⁰ C 379 2-Cl 2- position B B B H H 0 N M.p. 146-148 ° C 380 2-Cl 5 "position H H H - - B B 0 -, ρ N Mp 128-131 ° C 381 2-Cl 5- position H H H - - H B 0 CH ₂ O N 382 5- position H H H - - H B 0 C 1 -C ₁ N

Table 6- Continued

Verb no. - Binding position on the pyridine ring R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y M.p. 144.5-146 C & 383 2-CH ₃ 3-position B B B - - B B 0 N 384 2-Cl 5- position H B B B B B B 1 N 385 2-Cl S position H H B B B B B 1 ^ ₂ -CT ³ N 386 2-F 5- position B H B B B H B 1 N 387 2-Cl 5- position B B B - - B B 0 N 388 2-Cl 5- position B B H - - B B 0 CH ₂ -Qr * N 389 2-CH ₃ 5-position B B B - - B B 0 N 390 2-F 5-position B H B - - B H 0 N 391 2-Cl 5-; Position H B B - - H B 0 CH ₂ COCH ₃ N 392 2-Cl 5-position B B B - - H B 0 CH ₂ CO-O-Cl N 393 - 5 "position B H B - - B B 0 OCH ₂ - / 3 N 394 2-Cl 3- r-position CH ₃ B H - - H B 0 COCH ₃ N 395 2-Cl 5-position B B B - - H B 0 CHO N 396 2-Cl 5-position B B B - - B B 0 COCH ₃ N 397 2-F 5-position B B B B B B B 1 COCH ₃ N 398 2-Cl, 4-F 5-position B B B - - B B. 0 COCCl ₃ N 399 ² " ^C 2 ^H 5 5-position H B H - - H B 0 COC ₃ H ₇ N 400 2-Cl 5 "position B B B - - H B. 0 COCH ₃ N 401 2-CH ₃ 5-position H H H - - B B 0 COC (CH ₃ J ₃ N 402 5-position H H B H B 0 br N CCCH-C (CH ₃ J ₃

Table 6 - continued

Verb no.  ι Binding position on the pyridine ring 403 2,3-F ₂ ^ position 404 2-Br 5_Position 405 2-Cl 5_Position 406 - 3_Position 407 - 4_Position 408 2-Cl 5_ position 409 2-F 5-position 410 2-Cl 5-position 411 2-Cl 5- position 412 - 3 position

2-CH = CO ₂ 5-position

414 2-CF ₃ 415 2-CH ₃ 416 2-Cl 417 2-Cl 418 2-Cl 419 - 420 2-F 421 2-CH ₃ 422 2-Cl

5-position

5-position

5- position

5- P'osition

5- position

3- Position H 5- Position H

5-position 5-position

COCB «= CH

COCH ₂ O- (J) -Cl

CO

co ^ l

Schmp. 146-15O ⁰ C

M.p. 149-152C

Table 6 - continued

O binding R R ¹ R ² R ³ - B R ⁶ η R ⁷ Y M.p. 118-122 ⁰ C is verb Position at the - B No. pyridine - B 2,6-Cl ₂ ring H, ¹ B B - CB ₃ B B 0 N 423 2-Cl 4- position H B B - - B B 0 CO-Q-Cl N Mp. 4 24 2-Cl 5-position B B B - B 0 co-Q-ci N 125-126 C 425 - 5- position B B B B - B B 1 COOCH ₃ N 426 2-F 3-position H H B - - B B 0 COOC ₂ H ₅ N 427 5- position - B M.p. 135-140 C 2-Cl H B B - - B B 0 COOC ₂ H ₅ N 428 2-CH ₃ 5- position H B B - - B B 0 COOC ₄ H ₉ N 429 2-Cl 5- position B B B - B 0 COOCH ₂ CF ₃ N 430 2-Cl 5-position H B B - - B B 0 COO-Q N 431 2-Cl 5-position CH ₃ B B - B B 0 C ₀₀ -QKH ₃ N 432 5-position - B Cl 2-Cl B B B - B 0 _C oo Qm: i N 433 2-CHF ₂ 5-position H H B - - B B 0 CCCCH ₂ "O ^ ¹ N 434 2-Cl 5- position B B B - H 0 COSC ₂ H ₅ N 435 5- position - B CH ₃ . 2-Cl B B B - B 0 COS-Q N Mp. 436 5- position 0 191-192 C 2,3-F ₂ B B B - - B B 0 S-CH ₃ N 437 5-position Ö U 0 2-Cl B B B - - H B 0 S-CH, It ™ N 438 5-position 0 O 2-Cl B B H - B B 0 S-CH-Cl N 439 5-position 0 6 2-Cl H B B B 0 S-CH ₂ CB ₂ Cl Ö N 440 5-position

Table 6 - continued

Verb, no. ^Q t Binding position on the pyridine ring R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ α Y M. 186-188 ⁰ C ό M.p. 120-123 C 441 2- CCCCH ₃ 6-position H B B - - H B 0 0 N C - # "/ ^ t 442 2-Cl 5-position H B B - - H B 0 ό O CH? N S-Q 443 2-Cl 5 "position B B B - - H H 0 0 CON (CH ₃ J ₂ N 444 2-Cl 5_ position B B Π _ B B 0 CONH ΖΛ N 445 2-Cl 5-position H B H - - B B 0 CONF CH ₃ N 446 2-F "5 position Ξ B B · - - B B 0 CONHCO-I ^ Clv N 447 2-Cl, 6-F S position B a B - - B B 0 CONHCO-ΖΛ N 448 2-CN 5-position B H B   - - B B σ 0 he N CONHS-CH ₃ 449 - 4 · Position B B H B B B H 1 δ N 0 nJ ⁴ l _t 5760 CONHS - / "Λ 450 2-Cl 5- position H B B - - B B 0 Ö N OCl CONHS- / 3 451 2-Cl 5th position B B H - - B H 0 ο δ N P (OCH ₃ J ₂ 452 3.Position H B B - - e B 0 ^N SC ₃ H ₇ S N 453 2-Cl 5-position H B B - - B H 0 P (OC ₂ H ₅ J ₂ N 454 2-Cl   5- position B B H - - H H 0 S <> C1 N 455 2-Cl 5-position H B B - - H B 0 H N 456 2-Cl 5-position H B - H H - H 1 CH

In addition to Table 5, Table 7 covers the case in which the compounds of the formula (I) are represented by the following formula:

> CHNO N

3 · »

(CH ₂ )

et ι

Table 8 shows the case in which the compounds of the formula (I) are represented by the following formula:

»Ν,

(CH.

VCHNO

• Ν

Table 9 shows the case in which the compounds of the formula (I) are represented by the following formula:

R-CH

lei

and Table 10 shows the case where the compounds of the formula (I) are represented by the following formula:

H • N

 N

R-CH-Z

Table 7

R -CHL-f.

Ett

Connection no. Et t Bonding position of the heterocycle -. R m Schnp.l 9 4 ~ 1 9 6 * C 457 O 2 - ii 2 458 O 2 - B 3 459 O 3 - H 3 1 8 9 ~ 1 9 0 "C 460 S 2 - B 2 Mp. J 9 6-wi s s * C 461 S 2 - B 3 \ 462 S 3 - H i 3 2 0 1 - 2 0 S ¹ C 463 S 3 1 -Β -CE, 2 App. 1 8 3-1 8 5 * C 464 · N 2 1 -H B \ 2 1 465 N 2 1 -J? B 3 Schrnp. 2 0 7-2 1 3 * C 466 N 3 1 -CE, 1 -CE _t e 3 467 468 N N 2 2 1-C ₁ E, B B 2 3 Size l 5 1 - 1 5 2Ό 469 N 2 1 -CE, 5 -CJ, B 2 470,471 N O 3 2 5 -CE ₃ U B 3 2 472 O 2 5 -CjF, B 3 473 O 3 5 -CE ₁ B 2 474 S 2 S -CJ, B 2 475 S 3 B 3

Table 7 - continued

476 N 477 N 478 O 479 S 480 O 4 81 0 4 82 O 483 O 484 S 485 N 486 O 487 S 488   O 489 S 490 S 491 O 492 S 493 S 494 N 495 O 496 0 497 S 498 N 499 0 500 O 501 S

1 - E , 5 - CE ₁ IH, Z-CE ₁ 2.5- {CE, J ₁

2 _f 5 - ( CEJ _t

S 'F A -CI 5-CJ S-Ci 5 -C I

1 - CEi, 5-Cl

5 -Br S-Br

4. 5 -Ci ₁

4, 5-Ci ₁

i, 5-Br ₁ 5 -NO ₁ i -NO ₁ S -NO ₁

X-CE ^ S-NO ₁ 5 -CN S-CN S-CN

1 - CE, S- CNS -CFi 5 -CEF ₁ 5 -CF ₁

2 3 3 2 2 2 3

.i 3 0-1 3 l * C

3 scftmp. g

~ i 8 S * C

2 shots 2 1 2-2 1 5 * C

Table 7 - continued

502 N 3 1 -CE ₁ , S-CF _x \ m 2 M.p. 1 4 3-1 4 4 * C m.p. 12 0-12 4 * C 503 S 2 S - OCE _x e 2 504 O 2 5-SCE _x e 3 M.p. 1 2 7-1 2 9 * C 505 506 507 S 0 0 3 2 2 2.5- [SCE _x ) ι S-SCF _x S-SCF _x e e e 2 2 3 508 S 2 S-CE = CCl ₂ e 2 Schmp · 4 7 0-17L5 * C 509 0 2 s-o-f ~ \ B 2 510 0 2 5 -COOC ₂ Ef e 2 511 512 S S 2 2 S CEO A-CE _x e -CE _x 2 2

Table 8

R - CM

Connection no. S 4 t Binding position of the hetero cvclus, - R 171 Snap 1 8 6 ~ 1 8 8 * 0 Schnp. 2 0 0 ~ 2 0 1 * C i Schinp. 17 7 ~ 1 8 0 * C 513 O 3 - e 3 514 O 4 - e 2 515 O 4 S-CSi ' Z-CS ₁ e »: 516 517 518 519 O O O O 4 ί 5 3 5 3-C ₁ F ₃ -CSI e , e H ω ta ta ν 520 O 5 3 - CtS ₁ - is ο 2 521 O S Z-F e 2 522 O S Z-Cl H 3 523 O 5 Z-Br e 2 524 O 5 Z-OS e 2 525 O 5 '· Z-NO ₁ e 2 526 O 5 Z - CN e 3 527 O 5 Z-CFi Z-CFi e 3 528 52y O O 5 5 3 - CS F _t ta ta 2 3 530 O S e 2

Table 8- continued

531 O S Z-CF ₁ Cl • S-CiT ₃ B 2 - 9 0-1 9 1 3 "C 532 O S 3 - CE ₁ CI 3 - CEt ZF Yes 2 j 533 O 5 Z-CE ₁ OCE ₁ S-Cl B ² 9 p. 1 9 1 8 IC 534 O 5 Z-CE ₁ OCE [CHJ ₁ Z-Cl B 535 O 5 Z-CCl ₃ S -Br ' e 2 2 2 - 2 2 536 O 5 Z-OCE ₁ Z-NO ₁ B 3 1 2-2 1 j .-C 537 O 5 Z-OCF ₁ Z-SCFj B 2 Matches 1 7 9 - 1 8th O-C 538 O 4 2. S (CEt) ₁ 1-B B 2 539 S 3 1-B B 3 Matches 1 I I 1 540 S 4 - 1-B • B ! ί 2 ί 541 S 5 1-B ί ^& \ 2 2 ! 542! S 3 1-B B ^! ! 3 2 543 j 544 1 S S -5 p 1-CEt I if. ! ! * 2 2 Matches 1 I 1 I 545 j S 3 1-CEt ι B \\ 2 i ! 546 ί S 5 1-CEt ! if i • 2 547 S ³ B 2 548 S 5 B 3 549 S 5 B 2 550   N 5 B 2 551 N 5 * 3 552 'N 4 ² .553 N 4 CB, 2 554 N 4 3 555 I i n 3. 2 556 N 4 B . 557 ' N 4 l-CEt 3

Table 8 - Continued

558 559 560 561 562 563 564 565 566 567

568 569 570 571

572 573 574 575 576 577 578 579 580 581

N N N N N N N N N N

N N N

N N N N N N N N N JV

1-CE ₃ 1-C ₁ E,

1 -C ₁ H ₁ - is o

ι - C ₃ R ₁ -% s ο

1 -CE ₁ CE = CE ₁ 1 - CEf = CE 1 - CiR, - tert 1 -CiSf- rt

H B B

B B B

1 -

1-CF ₁

1 - CE CF _{1 1} 1-B, Z-CE ₁ IB, Z-CE ₁ lB, S-Cl \ -CE _3, 5-F I-CE _1, SC I 1 - CE _1, 5-Cl f, SC I

! H B B B B B B B B B

3!

Mp.

1 4 5 ~ 1 4 8 * C

Mp.

9 9 - 1 0 1 * C

Mp.

1 3 6-1 3 7 * C

Mp.

1 0 9 - 1 1 2 "C

Mp.

1 2 6-12 8 * C

Mp.

1 S 3 - 1 5 6 * C

mp ·

1 5 1 -1 5 3 * C

Mp.

  1 7 7-1 S 0 "C i

I Ί

Mp.

1 1 1 - 1 1 3 * C

ι Schmp.

H \ 3! 15 9 -16 3 ¹ C

2 2 2 2 3 2 2 2 3

Mp.

1 8 3-1 8 5 * C

Mp.

1 9 5 - 1 9 8 "C

Mp.

2 2 2-2 2 4 * C

Table 8- continued

582 N 1-C ₃ E ₁ -iso, S-CI i I i B ι 2 ! M. 1 9 2 ~ 1 9 4 * C m. 1 6 s ~ l 6 8 * c 583 N 3 1-CE ₃ , S-Cl B 2 584 N 3 XB, S-CF ₃ B 2 585 N- 5 4 5 1-CEj , 5-C /, B 2 586 587 588 N 1 -CE ₃ , S-CF ₃ 1, 3, 5 - ( CE ₃ ) , 1-CE ₁ CF ₃ B B 2 3 2

- ου - c ~ te ι ic

CM cm η CM cm cn P P I CM I CM , ^ r ες ft * * sej O CJ CM CM s is I ι I I i co ' O CM I I i , CM • CM I! CM CM CM υ Ü CM, cn. cn W CM it ss O e? to to M! Β O Ui . I O VO c] "Ti O cn in -P rH • Η Π O O O O O O ο; Pos ocy cn O f-l CN rn * r r '' cn tu SO σ * σ \ σ \ σ \ M (Ti ' Cn + J in in in in in in in ' HS I I J c cn  H O) CQ ¹ p " O i-i C 2 -i-l tn CTi OS in > TJ

Table 9 - Continued

ppp

CJ

P P

C4

CQ

«4th CJ. 1-

a »

- - fe,

I

I

CJ CJ CVI

BT ⁶ I

CJ

I!

04

to in w

IO IO · «·

CO σ. O iH <N η rr in VO r- co σ " O σ " σ * O O O O O O O O O O fH in in VO VO VO VO VO VO VO VO VO VO VO

VO

VO

Table 9 - Continued

P P P P 113 "r CM in "0 cn O O "-4 rl _ CM ι } ι ? CM O "0 "Ο ca ca O

CM

« Cm to tn

CVI

I Ife;

Cj * ICM

Cj I

cj fe. cj cj - cj cj O. ψ - · I I I I cj I I O cj CM CM CM CM I CM I I CM - CM I CM CM CM

IO

in

VOiH VO

VO

co

VO

O i-H CM cn CM CM CM CM VO VO VO VO

VD

in

VO

VO CM co σ " CM VO CM CM VO VO vo

Table 9 continuation

SS fej Sj ^

CM CM CM C I ^m CM CM tt CM C? CM C M CM M CM

Cj 1 to I a; "ς fc. -fc, ~ * fa, cj I oil I CJ to I β? cj cj cj cj I to ι cj to I "c ft; U I approx to I I C4 cj cj cj I CM «O 1 "O ^ I 1 CM cj Cj I "ο I Cvl I CM

- Cj

Cj O

"ο

I I ι

"Ο" ο

to to

to

O »Η cn PO ^ * in VO ^. co PO ro PO PO PO PO PO PO PO VO VO VO VO VO VO VO VO VO

σι vo

VO

CM

VO

PO

VO

Table 9 - Continued

P I υ P P I P υ CM cn CB ο cn in t _ CM ^, ι ι ι ? ca co CB cn "Β in • 0 (O

tr)

CM

CM

CM

crt

CM

CM

fc B;

"J. · 5y

O O

I i

CM CM

CM

fc,

cj

a; s; I 1

inea ^ r ^

"Ο

ιη VO Γ " 00 ^ * "τ VO VO VO VO

σ "

O ι-! CM ιη ιη ιη VO Γ- ιη ιη VO VO ιη ιη ID VO VO VO VO VO VO

Table 9 - Continued

P P CJ in CJ ι ι OO

ta «ο

CJ CM

N (O CJ CJ CM CM O) CO CJ "CJ

a5B5tea; ia; a; a; a; a:

a? a? a

Cj Cj

cj

I i

I i

et «« m cj a;   I * cj Cj j O L O I O = Cj I CJ ! ζ {j OJ O a; a · cj I Cj I cj I I I I in I CJ CJ CJ I I • be ". CJ Cj ι I CJ a; I ^ * **? I I I

Cl 10 OJ

CM M

fe fe fe;>; fe; ^^ iÄ f e f e O

V)

CO cn O r-i CM η ^ * in VO r » co σ " in in VO VO VO VD VO VD VO VO VO VO VD VD VD VD VO VO VO VD VO VO VO

O rK

v * ~ r-

VO VO

Table 9 - Continued

4 OJ η Oil m P I m P υ Oil to O co t; «1 sec m cj IO cj cj O cj SC a; to I ^ cj I β) α O O O CJ I in cj V- cj cj "O ta Oil to ca I I I to η I I CM in Oil Oil O) η Γ- OO M IO to "Ο VO P ^ co  " in vo VO σ " β · O St! r "- X) VO VO vo VO VO C5 cj I m Oil cn VO

Table 10

K-CE-Z

Connection no. Z E _i C ^/ R m Schrrp. 681 iy 2 Yes 682 O e 3 Schitip. 2 6 5 ~ 2 6 7t 683 rV Ji-N E ₃ C £ 2 6ö4 / τ- ¹ , " ¹ Pf e 2 685 Nz = N e 3 - 686 -CEi 2

Table 10 - Continued

E ₃ C.Yy T ~ y M 2 2 2 1 - 2 2 S'C 687 NN '/ Λ S ₃ C 2 688 NO NO NN _a / Λ 2 6ö9 N-N 3 Mp. 690 N. 2 691 SiC 2 692 F ₁ C e 2 693 2 694 3 695

Table 10 - Continued

696

697

698

699

700

701

702 703 704 705

N-N

JY

N-N

F _t CB ₁ C

rV

s'

N N

1!

N.

N,

N-N

N-N

KX

S-N

I i

-cbA

-CE ₁

Mp.

1 8 8-1 9

Table 10 - continued

706 KX e 3 M.p. 2 0 7 ~ 2 1 OTC • 707 e 2 - 708 709 TF JV e 2 2 710 N N H 3 711 _F xi JJ 2 712 e 2 713 e 2 714 . "U B 2

Table 10 continuation

715 N.- , V / A B ₁ CS e 2 M.p. 1 6 3 - 1 6 6 'C 716 ι « TX B ₁ CS - <5 ^ Il O e 2 717 N = N e 2 • 718 B 2 719 B 2 720 Cf B 3 721 -CB ₁ 3 722 B 2 723 -CE ₃ 2 724 G 2 CE ₁ 725 B 3 I

Table 10 - Continued

726 D- B 3 M.p. 1 A 4 - 1 727 cx * 2 728 ζχ e 3 729 e 2 730 e 3 731 'U e 2 - - 732 "η-   e 2 733 MC O e 2 734 ^S ' ^C <X S 2 M.p. 1 A 2 ~ 1 735 <^ <Χ Ή 2 736 "<Χ β 3 737 e 2

Table 10 - <X S continuation - 738 OEC ^ AT """" ^ n S 2 739 O II CE, C P. e 2 740 Φ- e 3 741 e 2 M. 2 1 2 ~ 2 1 5 * C 742 O O 2 P- e 743 e 2 .744 S 2 745 e 3 746 ^F ' ^cs ' ^c Xk e 2 747 e ' 2 748 3

Table 10 - Continued

749 EN 1 e 2 750 ³ \ e 2 751 ' ^N -1 e 2 752 e 2 753 e 2 754 - -E - - 2

Table 10 - Continued

755 756

757

75ö

759

760

761

762

763

> H ₃ C

N Cl

Cl

N v

H 2 H 2 H 3 Ξ 2 H 2 H 3 B 2 e 2 -CH ₃ 2

Mp 185-187 ° C mp 216-217 ° C

Schirp. 188-189 ° C Schrrp. 200-203 C Schirp. 219-222 ° C

Schrnp. 259-260 ⁰ C

Schitp. 173-174 ° C

Table 10 - continued

764 765 Ν-Ν ¹ P "Cl H H K) K) Schmp. 216-218 ⁰ C Cl 766 H 2 767 H 3 768 H 2 769 H 3 770 B 2 771 Ηί> H 3 772 ^{3 2} N = / H 2 773 ^F 3 ^C t ^ - H 2 774 H 2

Table 10 - continued

775 H-HCO-V / - * N = ¹⁷ H 2 776 F ₃ CO-J ^ - H 2 777 F ₃ CH ₂ CO-JJ) - H 3 778 ^H 3 ^CS t> H 2 779 H ₅ C ₂ S- | 3- H 2 780 F.BCS-jg »- H 2 , 781 F ₁ CS -? "^ - ^J U = / H 2 782 ^P 3 ^CH 2 ^CS -f3 " Ξ 2 783 H 2 784 785 \ -N Ν.-λ C ₁ - ^ Q- H H K) U) 786 _F 3C- ^ V H 2

Table 10 - Continued

787 -Q- B 2 Schirp.l72-175 ° C 788 ^ "^ il B 3 789 B 2 790 N = N B 2 791 O B 3 792 ³ N = N B 2 793 «Rf. B 2 794 B 2 795 N = N B 2 796 N = N H 2 797 N. -V P ₂ Cl C- ^ ⁷ ^ - B 2 798 ² N = ^ B 2

In addition to Tables 5 to 10 11 Table includes the case where X is NR. ⁷

Table 11

ζ R R ¹ Z-CH R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y 149-150 ° C D- H B B - - B B 0 B N Verb. Kr. _a P- CH ₃ H B - - B B O H N 799 B B H B B B B 1 B  Ν 800 "Τ> H B B B B B B 1 B N 801 H B B B B B B 1 H N 802 B H H H H H B B B H B H 1 O u m N N 803 H B H - - B H O B N 804 805 B B B - - B B 0 H N Schirp. 123-128 ° C 806 Vt B H B B H B B 1 B N 807 H B B - - B H O B N 808 _C1 J> - H B B - - H H 0 H. N 809 D- H B B B B B B 1 B 'N 810 H B B - - B H O H N 811 C ₁ ^ H H H H H H H 1 B N 812 H ₃ CS " ^L ~ ^ H H H H H H H 1 H N 813 814

Table 11 - Continued

Verb. No. ζ R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y Schnnp. 141-145 ⁰ C 815 B B B B B B B 1 B M 816 P ₂ HCsJ-S B B B B B B H 1 B M 817 818 IV F ₂ HCO - ^ - ^S ci-Us B B tn ta td td B B B B B B 1 0 B B N N 819 B B B B B B B 1 B N 820 H B B B H B H 1 B N 821 B B B B H B B 1 B M 822 B B B B B B B 1 B N 823 B B H - - B H 0 H N 824 CH ₃ H H - - B B 0 B N Schmp · 181-183 C 825 H H B - - H B 0 H N 826 ^T -O- B B B - - B B 0 B N 827 B B B - - B B 0 B M 828 "-0- B B B B B B B 1 B K Schmp. 142-144 ° C 829 Ö H B B - - B B 0 B M 830 Q- B B B - - H B .0 B- N Mp. 216-219 ° C 831 B H H - - H B 0 .B N 832 ^cl - \ 3 ~ B B B - - B H 0 B N 833 B H B - - H H 0 B N 834 B H B - - B H 0 H N

Table 11 - Continued

Verb no.

835 836 837 838 839 840 841-842 843

844 845 846 847 848 849 850 851 852

853

EV

D-

D-

JV

B-

H-B H B

CH

H CH,

^C 2 ^H 5

B B B B B

CH CH CH CH CH CH CH CH CH

M.p. 21O-213 ° C

Mp. 154-156 ⁰ C

Glass

CH

CH

CH

CH

C-COOC ₂ H ₅ C-COO-

c-coo - (3: -co (CH ₂ ) ₃ CH ₃

Schnp. 153-155 C

Table 11 - Continued

Verb no. ζ R R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ η R ⁷ Y M.p. 134-136 ⁰ C 854 ci -'- s B B H - - B B 0 C (CH ₃ J ₃ N 855 ci-Π "- H H H B H B B 1 CH ₂ SCH ₃ N 856 ^Η3 ° Ί> H B B B H B B 1 CH ₂ CH ₂ OC ₂ H ₅ N 857 CH ₃ CONH-I / H H B - - B B 0 CH ₂ COCH ₃ N 858 H H B - - B B 0 COCH ₃ N 859 _FC J> H H H H H B B 1 CHO N Mp 156-158 ° C 860 Ξ B B B B B B 1 COCH ₃ N 861 H B Ή - - B B 0 CON (C ₂ H ₅ J ₂ N 862 ⁰ D H H H - - B H 0 ^CO "£ 3 ~ ^NO 2 N 863 ^H3C i> B B H - - H B 0 COCH ₃ - N 864 H B B _ _ B B 0 ^C0 "Ö N 865 H B H - - H B 0 ^co \ 3 ~ ^ci N 866 H H B - - H H 0 COCH ₂ -OCl N 867 ei ΐ> B H B - - H B 0 COOC ₂ H ₅ N 868 B H B B B H B 1 COS - ^^ - Cl N 869 870 | £> H H H H H H • B H B B 0 0 O-S-CH ₃ N N N-O ό O 871 H H H H B B H 1 -S-CH ₂ Cl N O

Table 11 - Continued

Verb no.

R ³ R ⁴

872 873 874 875 876 877 878 879 880 881

Q-

CH.

CH

C-S-TVCH.

CH.

COCH ₂ OCH ₃

Br CCCH-C (CH ₃ J ₃

N N

CCH ₃ ,

co-f%

H '

Ξ H

Table 12 covers the case in which the compounds of formula (I) are represented by the following formula: R << R ³ . "

Z-CH

L-C-NO shark

Table 12

ζ R * R ² Λ / * ³ . R ³ R ⁴ R ⁵ 2 R ⁶ η L EAI Schrnp. 14O-143 ° C Ο- H R Z-CH- B - - B H 0 Cl Cl (Dec.) H B L-C-NO, I * - - e B 0 Cl Cl H B I EaI - e H 0 br br Verb no. H R ¹ H - - B Ξ 0 Cl br 882 H 883 B 884 B 885 e

Table 13 covers the case where the compounds of the formula (I) are represented by the following formula:

Table 13

Verb no. links , 170-175 ° C 886 , I ¹ I C1 -f_VcH 2 " ¹ S ^ A (Dec.) BOOC-HC NO ₂ 887 (CH -) - N-HC NO.

Typical examples of the synthesis of the intermediate compounds of the formula (II) are shown below. Example 36

CH ₂ -NH

Trimethylene (37 g) was dissolved in 120 ml of acetonitrile, and a solution of 14.8 g 5-chloromethyl-2-methylthiazole in 30 ml of acetonitrile was added thereto dropwise at 10 ° C to 15 ⁰ C. After the addition the mixture for a while at 30 ° C to 4O ⁰ C was stirred, and thereafter 8g of a 50% aqueous sodium hydroxide solution were added. Subsequently, the volatile materials were removed at a bath temperature of less than 50 ° C below 6,67 mbar (5 mmHg). The inorganics were removed from the residue by filtration to give 16.7 g of N- (2-methyl-5-thiazolylmethyl) trimethylenediamine (purity about 90%) as a colorless oil, ηq ¹ = 1.5126.

Example 37

CH, -NH (CH -), NH, NO ' ² 2 2 2

Ethylene diamine (30g) was dissolved in 120 g of acetonitrile, and a solution of 17.6 g 5-bromomethyl-3-methylisoxazole in 30 ml of acetonitrile was added dropwise at 5 ⁰ C to 1O ⁰ C. After the addition, the mixture was stirred for one hour, taking care that the temperature of the reaction system did not rise above 20 ° C. Thereafter, the bulk of the volatiles was removed under vacuum (less than 2.67 mbar [2 mm Hg]), the bath temperature was maintained at 2O ⁰ C. Ice water was added to the residue, and the mixture was extracted with dichloromethane. The dichloromethane layer was dewatered, and the dichloromethane was distilled off under reduced pressure to give 10.0 g of N- (3-methyl-5-isoxazolylmethy O-ethylenediamine (purity about 95%) as a colorless oil NMR spectrum (δ in CDCl ₃ ): NH, NH ₂ : 1.47 (ppm); -CH ₂ CH ₂ -: 2.23; -CH ₃ : 2.7; -CH ₂ : 5.8; hetero-H: 5, 9th

Example 38 '

H ₃ C

At room temperature, 11 g of 1-methyl-4-pyrazolecarbaldehyde was added slowly to 37 g of ethylenediamine in 150 ml of dry acetonitrile. Molecular sieve 4 A (a product of Wako Pure Chemicals, Co.) was added as a dehydrating agent to the solution. The mixture was stirred for 2 h at room temperature and then filtered. The acetonitrile was distilled off from the filtrate under reduced pressure. To the residue was added 100 ml of ethanol, and then 4 g of sodium borohydride was gradually added at room temperature. The mixture was stirred at room temperature for 2 hours, and the ethanol was distilled off under reduced pressure. Water was added to the residue, and the mixture was extracted with dichloromethane. The solvent was distilled off from the dichloromethane layer, and the residue was distilled in vacuo to give 10 g of N- (1-methyl-4-pyrazolylmethyl) trimethylenediamine as a colorless oil. Sdp.120-125 ° C / 1,07mbar (0,8mmHg).

Example 39

-CH-NH

A solution of 12.6 g of 3-acetylthiophene, 30 g of ethylenediamine and 150 ml of benzene was heated to reflux with stirring to remove the water as an azeotrope. When no more water formation was observed, the benzene was distilled off under reduced pressure. Ethanol (100 ml) was added to the residue and then 4 g of sodium borohydride was gradually added. The mixture was then stirred for 2 hours at 4O ⁰ C. The ethanol was distilled off under reduced pressure. A small amount of inorganic material was removed from the residue. Subsequent vacuum distillation yielded 8.2 g of N- [1- (3-thienyl) ethyl] ethylenediamine. Bp 102-105X / 4.67 mbar (3.5 mmHg). New compounds of formula (II) obtained by the same procedures as described in Examples 36 to 39 are listed below.

E ₁ N- [CE ₁ ] ^ NE-CE Z

Table 14- continued

Z R m n ^ 1,5523 e 3 n ^ ⁰ I ₁ S 4 9 5 e 2 a. Oi E e 3 e 3 Bp 108-ΠΟΐ / 5.3 mbar (4 nmHg) • ν Sdp. 1 3. 5 ~ 1 4 0 * C / 0.67 mbar (0.5 iranHg) e 2 1 1 Br ^ S ^ e 3 n * £ I ₁ 4 7 7 5 XX e 2 ny 1.4 75 2 xl e 2 XJ F _t CS ^s e 3 e 3 P- E ₁ S e 3 L

Table 14-continued

e 3 ft «L | 4 6 8 3 e 3 e 3 e 2 * »" 1, 5 3 3 5 e 3 »^ L, 5 2 3 O e 2 £ X e 3 e 2 Sap. 1 2 5 - 1 2 7 * C / 1,33 mbar (1 mmHg) £ second e 3 5άΡ · 1 3 3-1 3 5 ¹ C / i, 6 mbar (1.2 mmHg) e 2 _B M -VE ₁ 2

Table 14- continued

E ₁ C = ECE ₁ C

N ^ fK

CE ₁ CF ₃

E ₁ C,

3 J7 3 B 3 e 2 e 2 e 2 e 2 e 3 e 3 B 2

I _n 5 2 5 1

»» 2.5 045

1.4 65 1

n * 3 ^ 4940

, ie

π "1, 4 9 0 4

n '£ I ₁ S 0 0 3

Table 14- continued

B 3 n ¹ ^ 1.5 1 (0 gr e 2 n ¹ ^ 1.5 1 3 0 B 3 n ¹ ^ L ₁ S 7 2 2 N -ϊΓ B 2 χι e 2 B 3 η ¹ ^ 1.5205 B ₁ (T ^ ST * B 2 n ¹ ^ 1,56Sl e 2 B 3 e 2 XX 2 n * JI ₁ 5 7 8 8 2

Table 14- continued

BK -j e 3 Sdp. 9 0 * C / 3,33 mbar (2,5 itimHg) CB ₁ »" LU15 D ⁿ .Ο- ' e 2 - E Ν-Ν * - N e 2 B 2 e 2 ξι β 2 e 3 ' ¹ Yv NO e 2 e 3 e 2 e 2 Ν-, e 2

Example 40

/ ΓΛ

H ₂ NH- (CH ₂ ) ₃ -f

A solution of 6-chloronicotinaldehyde (14.2g), 2-aminoethanethiol (7.7g) and benzene (80ml) was heated with stirring for 5 hours to remove the water as an azeotrope. After the reaction, the benzene was distilled off under reduced pressure, and other volatiles were removed under 1,33mbar (1 mmHg) and 70 ⁰ C, after which 2- (2-Chloro-5-pyridyl) thiazolidine was obtained (18g) as a residue , 10 g of 2- (2-chloro-5-pyridyl) thiazolidine were dissolved in 100 ml of ethanol and sodium borohydride was added. While stirring, the mixture was gradually warmed and then refluxed for one hour. The ethanol was distilled off under reduced pressure, and the residue was added with chloroform. Insoluble matters were separated by filtration, and the chloroform layer was washed with water and dehydrated. The chloroform was distilled off under reduced pressure, after which the desired N- (2-chloro-5-pyridylmethyl-2-aminoethanethiol (8.3 g) was obtained, ng ⁴ : 1.5917.

Example 41

_N -CH NH- (CH -) - SH

A solution of 6-methylnicotinaldehyde (12.1 g), 3-aminopropanethiol (9.1 g) and benzene (120 ml) was heated with stirring for 5 h, with the water being removed as an azeotrope. After the reaction, the benzene was distilled off under reduced pressure and volatile substances were removed under 1,33mbar (1 mmHg) and 7O ⁰ C. As a residue, 3-pyridyltetrahydrothiazine (16.5 g) was obtained. Then, 3-pyridyltetrahydrothiazine (10 g) was dissolved in 100 ml of ethanol, and sodium borohydride was added. The mixture was gradually heated with stirring and then heated at reflux for 1 h. The ethanol was distilled off under reduced pressure. The residue was added with chloroform, and insoluble matters were separated by filtration. The chloroform layer was washed with water and dehydrated. After distilling off the chloroform under reduced pressure, the desired N- (3-pyridyl) -3-aminopropanethiol (6.2 g) was obtained, no. ⁴ : 1.5733. Compounds of formula (II) having the formulas below were prepared according to the same procedure as in Examples 40 and 41:

N- (2-chloro-5-pyridylmethyl) -3-aminopropanethiol (ng ² : 1.5890).

) - SH nj °: 1.5748 (No. II-4)

H ₀ -NH- (CH,), -SH 23

'tfZJ ^{2 Z} D

Example 42

-NH ₂

Ethylenediamine (60g) was dissolved in benzene (200ml) and 5-formylpyrimidine (21.6g) was added at room temperature. The mixture was then heated and refluxed for 3 h, with the water removed as an azeotrope. After the reaction, the benzene and the excess ethylenediamine were distilled off under reduced pressure. The residue was dissolved in ethanol (200 ml). Sodium borohydride (8.4 g) was added portionwise to this solution at room temperature, and then the mixture was stirred at room temperature for 5 hours. The ethanol was distilled off under reduced pressure. Dichloromethane (100 ml) was added to the residue, and the dichloromethane-soluble portion was separated. From the dichloromethane layer, the dichloromethane 1.5532 ⁶ was distilled under reduced pressure to give N- (5-pyrimidinylmethyl) was obtained ethylenediamine (25,8g) as a colorless oil, = ng.

Example 43

Ethylenediamine (30 g) was dissolved in acetonitrile (200 ml), and pyrazinylmethyl chloride (12.9 g) was added dropwise at ¹ ° C. to this solution at 5 ° C. After the addition, the mixture was stirred at room temperature for 1 h. Then one became

50% aqueous solution of sodium hydroxide (8 g) was added followed by removal of volatiles at a bath temperature of 60 ° C below 6,67 mbar (5 mmHg). The inorganic salt was then removed by filtration. In this way, N- (pyrazinylmethyl) ethylenediamine (14.1 g) was obtained as a colorless oil. ηρ ° = 1.5359.

Example 44

Z ^ - (CH ₂ ) ₂ -NH ₂

A solution of 2-cyano-5-pyridylmethyl chloride (4.6 g) in acetonitrile (20 ml) was added dropwise at ⁰ ° C to 5 ° C to a solution of ethylenediamine (9 g) in acetonitrile (50 ml). After the addition, the mixture was stirred at room temperature for 3 hours. Acetonitrile and the excess ethylenediamine were distilled off from the reaction mixture under reduced pressure. Dichloromethane was added to the residue, and the dichloromethane-soluble portion was separated. The dichloromethane was distilled off under reduced pressure. The volatiles were at 5O ⁰ C and 1.33 mbar (1 mmHg), after which N- (2-cyano-5-pyridylmethyl) ethylenediamine was obtained (4.5 g) as a colorless oil, n ^ = 1.5718.

Example 45

₂ NH ₂ - (CH ₂ J ₃ -NH ₂

5-Trifluoromethylpicolinaldehyde (3.5g) was added dropwise at room temperature to a solution of trimethylenediamine (7.4g) in benzene (70ml). After the addition, the mixture was gradually heated with stirring and then heated to reflux for 2 hours to separate water as an azeotrope. The benzene was distilled off under reduced pressure, and then the residue was dissolved in ethanol (100 ml). While stirring, sodium borohydride (0.9g) was gradually added at 10 ° C to 15 ° C. The mixture was then stirred for 2 h at room temperature. Ethanol was distilled off at less than 30 ⁰ C. Dichloromethane was added to the residue, and the dichloromethane-soluble portion was separated. The dichloromethane was distilled off under reduced pressure, and the volatiles were at 1.33 mbar (1 mmHg) and less than 60 ⁰ C removed, after which N- (5-trifluoromethyl-2-pyridylmethyl) trimethylenediamine (3.5 g) as a colorless Oil was obtained, ng ⁰ = 1.4651.

Example 46

CH ₂ NHCH ₂ CHNH ₂ ',,

A solution of 8.1 g of 2-chloro-5-chloromethylpyridine in 30 ml of acetonitrile was added dropwise over 2 h at ⁰ ° C. with vigorous stirring to a mixture of 14.8 g of 1,2-diaminopropane, 5 g of a 40% strength Sodium hydroxide solution and 100ml acetonitrile added. After being stirred at room temperature for a short time, the water, acetonitrile and excess 1,2-diaminopropane were removed under reduced pressure. The inorganic salt was filtered off with suction from the residue. The filtrate was the desired product, 2-amino-1- (2-chloro-5-pyridylmethylamino) propane (9.3g). ηέ ⁷ = 1.5450.

In the same manner as in Example 46, the following compounds were prepared: N-methyl-N'-3-pyridylmethylethylenediamine, b.p. 140 ° C / 3.33 mbar (2.5 mmHg); 2-amino-2-methyl-1- (3-pyridylmethylamino) propane, b.p.. 115 ° C / 2.0 mbar (1.5 mmHg); 2-Aminomethyl-2-methyl-1- (1-methyl-4-pyrazolylmethyl) -propane, n ^ ⁵ = 1.5109.

Example 47

A solution of 18.6 g of N- (2-chloro-5-pyridylmethyl) ethylenediamine and 11 g of 1-methylpyrazole-4-carbaldehyde in 150 ml of benzene was stirred on a heated water bath. After a short time water separated from the solution, which meant that the Schiff's base had been preserved. Benzene and water were then removed under reduced pressure, and 100 ml of ethanol was added to the residue. To the solution, 3.8 g of sodium borohydride was added portionwise at room temperature, and the mixture was stirred for 1 day. After removing the ethanol under reduced pressure, the residue was dissolved in dichloromethane and washed with water. Treatment of the dichloromethane solution in the usual manner gave the desired intermediate, N- (2-chloro-5-pyridylmethyl) -N '- (1-methyl-4-pyrazolylmethyl) ethylenediamine, as a viscous oil. The yield was 23.5 g. no ° = 1.5655.

For example, in the same manner as in Example 47, the following compounds were prepared: N- (3-pyridylmethyl) -N '- (2-chloro-5-pyridylmethyl) ethylenediamine, ng ⁰ = 1.5846. N- (3-methyl-5-isoxazolylmethyl) -N '- (1-methyl-4-pyrazolylmethyl) trimethylenediamine, n ^ ⁰ = 1.5224.

Example 48

! U ^ ₀ J) -CH ₂ NHCH ₂ CH ₂ OH

A solution of 7g ö-bromomethyl-S-methylisoxazole in 20 ml of acetonitrile was added dropwise below 10 ⁰ C to a solution of 12.2 g of 2-aminoethanol in 100 ml of acetonitrile. After stirring at room temperature for a while, the acetonitrile and the excess 2-aminoethanol were removed under reduced pressure. Chloroform was added to the residue and the mixture was washed with a small amount of water. Treatment of the chloroform solution in the usual manner afforded the desired 2- (3-methyl-5-isoxazolylmethylamino) ethanol. The yield was 4.4g.

nf? = 1.5130.

For example, in the same manner as in Example 48, the following compounds were prepared:

N- (2-chloro-5-pyridylmethylamino) propanol,

n ^ ⁷ = 1.5391.

N- (4-pyridylmethyl) ethanolamine, bp 148-150 ° C / 4mbar (3mmHg).

Example 49

^CH 3 \.

1! ^ ₀ JI-CH ₂ NHCH ₂ CH ₂ Sh

To a solution of 15.6 g of 2- (3-methyl-5-isoxazolyl-methylamino) ethanol in 100 ml of chloroform was added a catalytic amount of pyridine and then 15 g of thionyl chloride at room temperature. After the addition, the mixture was refluxed for 30 minutes, and evaporation of the volatile material in vacuo gave the crude chlorinated compound in the form of its hydrochlorides. M.p. 136-139 ⁰ C.

An ethanolic potassium hydrogensulfide solution was prepared by saturating a solution of 13.4 g of potassium hydroxide in 120 ml of ethanol with hydrogen sulfide gas. To the obtained solution, the above chloride hydrochloride at 25 ⁰ C was added portionwise to 3O ⁰ C with stirring. The reaction mixture warmed slowly and was then stirred for ² h at 60 ° C. After cooling to room temperature, the inorganic salt was rapidly filtered off with suction. The solvent was removed from the filtrate under reduced pressure to give 2- (3-methyl-5-isoxazolylmethylamino) ethanethiol (12.9g) as an oil, ng ⁵ = 1.5490.

In the same manner as in Example 49, for example, the following compound was prepared. 2- (2-methyl-5-pyrazinylamino) ethylmercaptan, no ⁸ = 1.5581.

Example 50

- c πτ

L>

"

2.72 g ethylene trithiocarbonate and 2.52 g of dimethyl sulphate were mixed together and heated for 1 Freq 100 ⁰ C. 10 ml of acetic acid and 2.02 g of triethylamine were added to the resulting 2-methylmercapto-1,3-dithiolanium methylsulfate. Thereafter, 2.6 g of 2,2,2-trifluoronitroethane was added to the mixture with cooling in an ice bath. The entire mixture was slowly heated to 100 ⁰ C and held at this temperature for 4h. After standing at room temperature overnight, 100 ml of water was added to the reaction mixture. The precipitated crystals were filtered off and recrystallized from ethanol to give i-nitro ^^ -ethylenedimercapto-i-trifluoromethylethylene. The yield was 4.35 g. M.p. 130-133 ⁰ C.

Example 51

H ₃ CS NO ₂

C = C

H ₃ CS ^ ^ COC ₃ H ₇

To a solution of 13.1 g of 1-nitro-2-pentanone in 200 ml of dimethyl sulfoxide in 100 ml of chloroform at 10 ° C to 20 ⁰ C dropwise 44g of a 20 percent strength. Added sodium hydroxide solution. Thereafter, 12 g of carbon disulfide was added dropwise at 10 ^° C. to the solution, and the mixture was heated at 0 ^° C. to 10 ^° C. for 2 hours. Into the mixture was added dropwise 57 g of methyl iodide under ice-cooling, and then the reaction mixture was allowed to stand overnight at room temperature. Thereafter, it was poured into ice-water, and the organic layer was extracted with dichloromethane. The extract was washed several times with water, and after removing the solvent, the residue was purified by chromatography on a silica gel column to give the desired 1-butyroyl-1-nitro-2,2-bis (methylthio) ethylene. The yield was 3.0 g. n "= 1.5880.

For example, in the same manner as in Example 51, the following compound was prepared: 1-benzenesulfonyl-1-hitro-2,2-bis (methylthio) ethylene, ng ⁰ = 1.5868.

Example 52

2.5g of sodium hydride (60% in oil) was added in small portions to a solution of 3.9g of 2-nitroiminoimidazolidine in dry dimethylformamide. After the addition, the mixture was stirred until evolution of hydrogen gas was completed. The mixture was cooled to -5 ° C, and 4.7 g of phenyl chloroformate were added dropwise below 0 ⁰ C. After stirring at room temperature for 1 hour, the reaction mixture was poured into ice water, adjusted to pH7 and extracted with dichloromethane. The white crystals remaining after removal of the dichloromethane were washed with ether to give 1- (phenoxycarbonyl) -2-ni-tropinoimidazolidine, 5.1 g. M.p. 171-175 ° C.

193-197 ⁰ 1- (2-methyl-5-nitrobenzenesulfonyl) -2- (nitroimino) imidazolidine, mp C; in the same manner as in Example 52, for example, the following compounds were prepared. 1- (2,4-dichlorobenzoyl) -2- (nitroimino) imidazolidine, mp 184-186 ° C. '

Example 53

HN N-CONH- /

N-NO.

A solution of 3.9 g of 2-nitroimidazolidine and 4.6 g of 3-chlorophenyl isocyanate in 80m of dry acetonitrile was refluxed for 3 hours. After cooling to room temperature, the precipitated crystals were filtered and washed with ether to give the desired 1- (3-chlorophenylcarbamoyl-2-nitroiminoimidazolidine, the yield being 4.7g of Sm.214-216 ° C.

use Examples

Comparative Attachment A-1:

(the compound described in DE-OS 2514402); Comparative Compound A-2:

(the compound described in Japanese Laid-Open Patent Publication No. 196877/1984; Comparative Compound A-3:

(the compound described in the same patent document as above); Comparative Compound A-4:

^ N-NO ₂

(the compound described in Can. J. Chem. 38, pp. 1787-1796).

Example 54 Test for Organophosphorus-resistant Nephotettix cincticeps: Preparation of a test preparation:

Solvent: Xylene 3Gew parts

Emulsifier: polyoxyethylene 1 part by weight

alkylphenyl

To prepare a suitable test preparation, 1 part by weight of the active compound was mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier. The mixture was diluted with water to a predetermined concentration

Test methods:

On rice plants about 10 cm high, each planted in pots of 12 cm diameter, 10 ml of the water-diluted, predetermined-active-concentration solutions prepared as indicated above were sprayed per pot. The sprayed chemical was allowed to dry, and over each pot was placed a wire basket 7 cm in diameter and 14 cm in height; 30 adult female specimens of Nephotettfx cincticeps resistant to organophosphorus insecticides were exposed under each wire basket. The pots were each kept in a constant temperature room, and 2 days later, the number of dead insects was determined and the destruction ratio was calculated.

As a result, it was found that, for example, Compound Nos. 1,2,3,4,5,7,7,8,9,10,11,13,14,15,16,17,19,20,22,26 , 27,31,32,33,34,35,36,39,65,66,75,76,105,164,290,304,323,336,340,396,409,431,444,453,518,556,612,623,624,705, 706,755,762,813,827, 831,884 showed a coating ratio of 100% at an active ingredient concentration of 8 ppm. In contrast, in comparison showed

compound A-1 has an annihilation ratio of 65% at an active ingredient concentration of 40 ppm, compound A-2 has a composition ratio of 40% at an active ingredient concentration of 200 ppm and an annihilation ratio of 0% at an active ingredient concentration of 40 ppm, compound A-3 has a composition ratio of 0% at an active ingredient concentration of 200 ppm and compound A-4 has a destruction ratio of 30% at an active ingredient concentration of 200 ppm,

Example 55

Test on lantern carriers. ·

A water-diluted, predetermined-agent concentration solution prepared as in Example 54 was sprayed in an amount of 10 ml per pot onto rice plants about 10 cm high which had been grown in 12 cm diameter pots. The sprayed chemical was allowed to dry, and over each pot was placed a wire basket 7 cm in diameter and 14 cm in height. 30 adult females of Nilaparvata lugens Stal of a strain showing resistance to organophosphorus chemicals were exposed under each wire basket. The pots were each kept in a constant temperature room, and 2 days later, the number of dead insects was determined. The ratio was calculated.

In the same way, the ratio was calculated for Sogatella furcifera Horvath and organophosphorus resistant Laodelphax stratellus traps.

As a result, it was found that, for example, Compound Nos. 1,2,3,4,5,7,7,9,10,11,12,13,14,15,16,17,18,19,20 , 22,29,35, 37,39,43, 65,70,75,79,146,164, 230,303,308, 324,331,350, 396,409,424,453, 518, 529, 550,556,579, 612,623, 624,701,705,706,755,756,758, 848 show a composition ratio of 100% at a drug concentration of 40 ppm against each of the litter carriers.

In contrast, in comparison showed

the compound A-1 at a drug concentration of 40 ppm, a destruction ratio of 50% against N. Lugens and

of 40% against S.furcifera and L. striatellus,

the compound A-2 at a drug concentration of 200 ppm, a destruction ratio of 30% against N. Lugens,

of 20% against L. striatella and

of 50% against S.furcifera

and at an active ingredient concentration of 40 ppm, a destruction ratio of 0% to each of the litter carriers, the compound A-3 at a drug concentration of 200 ppm, a destruction ratio of 0% against each of the litter carriers and

the compound A-4 at a drug concentration of 200 ppm, a ratio of 100% against N. Lugens and

of 0% against S.furcifera and L.Striatellus.

Example 56 Test for organophosphorus resistant Myzodes persicae (green peach aphids): Test methods:

Cultured green peach aphids, which showed resistance to organophosphorus chemicals and carbamate chemicals, were exposed to eggplant (black elongated eggplant) seedlings about 20 cm high that had been grown in unglazed 15 cm diameter pots (about 200 aphids per seedling ). One day after exposure, an aqueous dilution prepared as in Example 54 of each of the active compounds at a predetermined concentration was sprayed on the plants in sufficient quantity by means of a spray gun. After spraying, the pots were allowed to stand in a greenhouse at 28 ° C. 24 hours after spraying, the annihilation ratio was calculated. For each compound, the test was performed as a duplicate.

As a result, it was found that, for example, the compounds Nos. 1,2,3,4, 5,6,7,8, 9,10,11,12,13,14,15,16,17,18,19, 20 , 21,22,23, 24, 25,26 ,. 27,28, 29, 30,31,32,33,35,71,74,75,98,105,164,230, 231,373,396,409, 518, 529, 550, 556, 579, 612, 623, 624, 649,705,706,755,756,758,763, 831 an annihilation ratio of 100% at a drug concentration of 200ppm.

In contrast, in comparison showed

Compound A-1 has an annihilation ratio of 80% at an active ingredient concentration of 1000 ppm and of 30% at an active ingredient concentration of 200 ppm. Compound A-3 has an annihilation ratio of 60% at an active ingredient concentration of 1000 ppm and of 0% at an active ingredient concentration of 200 ppm and the compound A-4 an annihilation ratio of 60% at an active ingredient concentration of 1,000 ppm and 0% at an active ingredient concentration of 200 ppm.

Examples 54, 55, and 56 are typical examples of insecticidal uses, and the compounds of the present invention which have been exemplified therefor are also typical examples. However, the present invention is not limited to these examples alone.

Claims (4)

Invention claim: 1. Insecticidal agents, characterized in that they contain at least one heterocyclic compound of the formula (I) 3 (I) Z-CH contain. in the η denotes 0 or 1. R ¹ , R ² , R ⁵ and R ⁶ independently denote a hydrogen atom or an alkyl group, R ³ and R ⁴ independently of one another denote a hydrogen atom, a hydroxy group or an alkyl group η 1, R ^{2 can form} a single bond together with R ⁵ , X denotes a sulfur atom, an oxygen atom or one of the following group-NR ⁷ or -CH-R ⁸ , wherein R ^{7 is} a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a benzyloxy group, an alkyl group which may be substituted by at least one substituent selected from among alkoxy groups , Alkylthio groups, a cyano group, halogen atoms, dialkylamino groups and trialkylsilyl class, an alkenyl group which may be substituted by a halogen atom, an alkynyl group which may be substituted by a halogen atom, a phenyl group which may be substituted by an alkyl group and / or a halogen atom, a benzyl group which may be substituted by at least one substituent selected from the group consisting of a methyl group, a methoxy group and group, halogen-Atömen7Häiög- _enom ethyl-Gfupperi, Halogenomethoxy groups and a nitro group existing class, a formyl group, an alkenylcarbonyl group, an alkylcarbonyl group that may be substituted by at least one substituent may be selected from the group consisting of alkoxy groups, a phenoxy group, alkylthio groups and halogen atoms, a benzoyl group which may be substituted by at least one substituent selected from among halogen atoms, Alkyl group ^ halomethyl group ^ alkoxy groups ^ halogenoalkoxy groups and a nitro group _s existing class, a benzylcarbonyl group which may be substituted by an alkyl group and / or a halogen atom, an alkoxycarbonyl group, which may be substituted by a halogen atom, an alkylthiocarbonyl group, a phenoxycarbonyl group which may be substituted by at least one substituent selected from among methyl, methoxy, halomethyl, halomethoxy Groups, halogen atoms and a nitro group-existing class, a phenylthiocarbonyl group which may be substituted by a halogen atom and / or an alkyl group, a benzyloxy carbonyl group, a monoalkyl or dialkylaminocarbonyl group, a phenylaminocarbonyl group which may be substituted by at least one substituent selected from the class consisting of alkyl groups, haloalkyl groups and halogen atoms, a benzoylaminocarbonyl group , which may be substituted by an alkyl group and / or a halogen atom, a phenylsulfonylaminocarbonyl group which may be substituted by an alkyl group and / or a halogen atom, a phenylthio group which is substituted by an alkyl group And / or a halogen atom, an alkylsulfonyl group which may be substituted by a halogen atom, a phenylsulfonyl group which may be substituted by at least one substituent selected from among alkyl groups , Halogen atoms and a class consisting of nitro group, an alkylcarbonylmethyl group, a phenacyl group substituted by a halogen atom and / or an alkyl group may be an organophosphono group, an organothiophosphono group, the following group CH ₂ -W or CO-W, wherein W denotes a 5- to 5-membered heterocyclic group containing at least one of oxygen atoms, sulfur Atoms and nitrogen atoms containing class selected hetero atom and may be substituted by at least one substituent selected from the class consisting of halogen atoms, alkyl groups and haloalkyl groups, R ^{8 represents} a hydrogen atom, an alkyl group, an aryl group or a benzyl group, Y denotes a nitrogen atom or the following group = CR ⁹ , wherein R ^{9 is} hydrogen, halogen, hydroxy, alkoxy, benzyloxy, alkyl, which may be substituted by at least one substituent selected from halogen , a hydroxy group, alkoxy groups, alkylthio groups, a cyano group, mono- or dialkylamino groups. alkylcarbonyl groups, alkoxycarbonyl groups and phenoxycarbonyl groups, an alkenyl group substituted by a halogen atom may be an alkynyl group, a phenyl group that may be substituted by an alkyl group and / or a halogen atom, an alkylcarbonyl group which may be substituted by a halogen atom, an alkenylcarbonyl group, a benzoyl group which may be substituted by at least one substituent, which is selected from the group consisting of halogen atoms, alkyl groups and alkoxy groups, an alkoxycarbonyl group which may be substituted by a halogen atom, an alkylthiocarbonyl group, a phenoxycarbonyl group represented by at least one substituent may be substituted, which is selected from the group consisting of halogen atoms, alkyl groups, alkoxy groups and a nitro group, a phenylthiocarbonyl group which may be substituted by an alkyl group and / or a halogen atom a benzyloxycarbonyl group, a benzoylaminocarbonyl group which may be substituted by an alkyl group and / or a halogen atom, a phenylsulfonylaminocarbonyl group represented by ei an alkyl group and / or a halogen atom, an alkylsulfonylaminocarbonyl group, an alkylthio group, an alkylsulfonyl group which may be substituted by a halogen atom, a phenylthio group which is substituted by an alkyl Group and / or a halogen atom may be substituted, a phenylsulfonyl group which may be substituted by an alkyl group and / or a halogen atom, and also R ⁹ is able to form a bis-form of the formula (I) via a methylene group, R represents a hydrogen atom or an alkyl group and Z denotes a 5- to 6-membered heterocyclic group containing at least one heteroatom selected from oxygen atoms, sulfur atoms and nitrogen atoms and which may be substituted by at least one substituent selected from among halo atoms, alkyl Groups, haloalkyl groups, a nitro group, a cyano group, alkoxy groups, alkylthio groups, alkylsulfinyl groups, alkylsulfonyl groups, alkenyl groups, haloalkoxy group, haloalkylthio group, haloalkenyl groups , Acylamino groups, halogeno-acylamino groups, alkoxycarbonyl groups, a thiocyanato group, alkynyl groups, an amino group, alkylamino groups, dialkylamino groups, a carboxy group, a hydroxy group, a mercapto group, cycloalkyl groups, Groups, an oxo group, a thioxo group, haloalkenylthio group, alkoxyalkyl groups, alkoxycarbonylamino groups, a carbamoyl group, acyl groups, alkylaminocarbonyl groups, dialkylamino-carbonyl groups, and the like aryl groups which are optionally substituted by a substituent selected from the group consisting of halogen atoms, alkyl groups, haloalkyl groups, alkoxy groups, a nitro group and a cyano group, a formyl group, Aryloxy groups optionally substituted by a substituent as claimed in the above aryl groups, and aralkyl groups optionally substituted by one of the same substituents as given for the aryl groups; with the proviso that if R ¹ , R ² , R ³ , R ⁴ and R ⁵ and R ^{6 are} simultaneously hydrogen atoms, X denotes -NH and, Y = CH, then Z may not stand for the pyridyl group,. * in addition to extenders and / or surfactants. 2. A method for controlling noxious insects, characterized in that is allowed to act new heterocyclic compounds of formula (I) according to item 1 on the harmful insects and / or their habitat. 3. Use of novel heterocyclic compounds of the formula (I) according to item I, characterized in that they are used for controlling noxious insects. 4. Process for the preparation of insecticidal agents, characterized in that new heterocyclic compounds of the formula (I) according to item 1 are mixed with extenders and / or surface-active agents.