DD236445A5 - INSECTICIDES MEDIUM - Google Patents

Abstract

There are provided novel nitromethylene derivatives of the formula I in which R denotes a hydrogen atom or a lower alkyl group, X represents a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower alkenyl group, a lower alkynyl group, an aryl group, an aryloxy group which may be optionally substituted by a halogen atom, an arylthio group, which may optionally be substituted by a halogen atom, or denotes an aralkyl group, l is 1, 2, 3 or 4, m is 2, 3 or 4 and n is 0, 1, 2 or 3. The compounds of the formula (I) can be prepared by reacting compounds of the formula II with compound of the formula III, where R has the meaning given in the application text, and have very pronounced insecticidal properties. Formulas I, II, III

Description

Field of application of the invention

The invention relates to insecticidal compositions containing new nitromethylene derivatives and to processes for preparing these compounds.

The compositions according to the invention are used for controlling harmful insects in agriculture and in veterinary medicine.

Characteristic of the known technical solutions

From DE-OS 2514402 it is known that 2-nitromethylene-imidazoline derivatives and 2-nitromethylene-hexahydropyrimidine derivatives of the following general form

insecticidal activity. The above general formula includes cases where η = 2, R ₁ = phenyl (Ci-C ₂ ) -alkyl group and R ₂ = R ₃ = hydrogen, and the description of DE-OS 2514402 describes a compound of the following formula:

CHNO ₂

DE-OS 2732660 mentions that 1-substituted benzyl-2-nitromethylene-imidazolidine derivatives of the following general formula

- ί- / au like that

possess insecticidal activity. The latter German Offenlegungsschrift describes a compound of the following formula:

(BI)

Object of the invention

The aim of the invention is the provision of new agents with a stronger herbicidal action and good plant tolerance.

Explanation of the essence of the invention

The invention has for its object to find new compounds which have a stronger herbicidal activity and good plant tolerance compared to the known compounds and which are suitable as active ingredient in the new herbicidal compositions.

According to the invention, the active ingredients in the novel insecticides are new nitromethylene derivatives of the following general formula (I):

(CH ₂ J _n -

applied the

R denotes a hydrogen atom or a lower alkyl group,

X is a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a lower alkylsulfinyl group, a lower alkylsulfonyl group, a lower alkenyl group, a lower alkynyl group, an aryl Group, an aryloxy group which may be optionally substituted by a halogen atom, an arylthio group which may be optionally substituted by a halogen atom, or an aralkyl group,

I stands for 1,2, 3 or 4,

m stands for 2, 3 or 4 and

η is 0,1,2 or 3.

It should be noted that in cases I> 1, the substituents X may be the same or different from each other.

The nitromethylene derivatives of the formula (I) according to the present invention can be prepared by the following method i) to which the present invention also extends.

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Method i:

A process for producing the nitromethylene derivatives of the general formula (I) comprises the reaction of a compound of the general formula

1- (CH-) -NH- (CH-) -NH- (II)

/ ΠΔJR Δ

in which R, X, I, m and η have the meanings given above, with a compound of the general formula

R'-S

^ C = CHNO (III)

in which each R 'denotes a lower alkyl group or a benzyl group or the two R' groups together denote a lower alkylene group having at least 2 carbon atoms and can form a ring with the sulfur atoms adjacent to them.

In particular, the present invention relates to insecticides containing the nitromethylene derivatives of general formula (I) as active ingredients.

In the preparation of the novel nitromethylene derivatives of the general formula (I) according to the present invention, the compounds of the general formula (II) which are intermediates are novel compounds, and the present invention also relates to these compounds (intermediates).

The novel compounds of general formula (II) can be prepared by the following process ii), to which the present invention also extends.

Method ii:

A process for the preparation of the compounds of the general formula (II) comprises the reaction of a compound of the general formula

CH- (CH ₂ J _n -Y (IV)

in which R, X, I and η have the meanings given above and Y denotes a halogen atom or the group -OSO ₂ R ", in which R" represents a lower alkyl or an aryl group, with a compound the general formula

H ₂ N- (CH ₂ L-NH ₂ (V),

in which m has the meaning given above.

Compounds of general formula (IV) are either known or can be prepared by known preparation methods.

It has been found that the compounds of the present invention at a lower dosage have an excellent controlling effect as compared with the compounds (A-1) and (B-1) described in the above-cited German Offenlegungsschriften which are most similar to the compounds according to the present invention and that the compounds according to the present invention have a marked control effect against harmful insects that have developed against organophosphate-type and carbamate-type insecticides due to prolonged application of the latter resistance, especially to sucking insects typified by insects the

Order Hemiptera like aphides, lantern bearers and cicadas.

According to the invention therefore new nitromethylene derivatives of the general formula (I), intermediates for these.

Process for their preparation and their use as insecticides made available.

The active compounds according to the present invention exhibit a control activity against harmful insects without phytotoxicity to crops. In addition, the compounds of the present invention can be used to control and eradicate a wide range of pests, including sucking insects, biting insects and other plant parasites, livestock grain pests and harmful pests.

Examples of these pests are listed below:

Insects of the order Coleoptera

Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotesfuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabroticaspp., Monochamus alternatus, Lissorhoptus oryzophilus and Lyctus brunneus.

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Insects of the order Lepidoptera

Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilosuppressalis, Pyrausta nubilalis, Ephestiacautella, Adoxophyes orana, Carpocapsa pomonella, Agrotisfucosa, Galleria mellonella Plutella maculipennis and Phyllocnistis citrella.

Insects of the order Hemiptera

Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae.

Aphis pomi.

Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex lectularius, Trialeurodes vaporariorum and Psyllaspp ..

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, Culex pipiens, Anopheles sinensis and Culex tritaeniorhynchus.

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

insects

Gastrophilusspp.,

Stomoxys spp.,;

Trichodectes spp. : "

Rhodnius spp. and Ctenocephalidex canis

Substances having pesticidal activity against all of these pests are sometimes referred to simply as "insecticides" in the present application.

The nitromethylene derivatives of the general formula (I) according to the present invention can be easily prepared, for example, by the following method i).

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Method i)

'- (CH ₂ ) _n -NH- (CH ₂ ) _m -NH ₂ +

(II) R '-S.

TJ t _C ** ^^ ν - Lnnu- - H (III) ^l \ = CHNO -. ^R

(D

(In the formulas, R, X, I, m, η and R 'have the meanings given above).

In the above reaction scheme, R represents a hydrogen atom or a lower alkyl group such as methyl, ethyl, propyl, isopropyl and n- (iso-, see- or tert-butyl) -butyl.

X denotes a halogen atom, a lower alkyl group having preferably 1 to 6 carbon atoms, a lower alkoxy group, a lower alkylthio group preferably having 1 to 6 carbon atoms, a lower alkylsulfinyl group preferably having 1 to 6 carbon atoms, a lower alkylsulfonyl group preferably having 1 to 6 carbon atoms, a lower alkylsulfonyl group having preferably 1 to 6 carbon atoms, a lower alkenyl group having preferably 2 to 6 carbon atoms, a lower alkynyl Group having preferably 2 to 4 carbon atoms, an aryl group having preferably 6 to 12 ring carbon atoms, an aryloxy group which may be optionally substituted by a halogen atom, an arylthio group optionally substituted by a halogen atom may be substituted, or an aralkyl group. Specific examples of the halogen atom may include fluorine, chlorine, bromine and iodine. Specific examples of the lower alkyl group are the same as exemplified above. Specific examples of the lower alkoxy group, the lower alkylthio group, the lower alkylsulfinyl group and the lower alkylsulfonyl group may similarly be those containing the same lower alkyl groups as exemplified above. Specific examples of the lower alkenyl group may include vinyl, allyl-1-propenyl or 1- (2- or 3-butenyl). Specific examples of the lower alkynyl group may include ethynyl, 1-propynyl or propargyl. Specific examples of the aryl group include phenyl and a- (or / 3-) naphthyl. Specific examples of the aryloxy group and the arylthio group which may be optionally substituted by a halogen atom may be those containing the same aryl groups as exemplified above and optionally by one or two of the above Examples of halogen atoms may be substituted. Specific examples of the aralkyl group may include benzyl, phenethyl or α-naphthylmethyl.

I denotes 1, 2, 3 or 4

 m denotes 2,3 or 4

 η b denotes 0,1,2 or 3.

R 1 denotes a lower alkyl group having preferably 1 to 6 carbon atoms or a benzyl group, or the two R 'together denote a lower alkylene group having at least 2 carbon atoms. Specific examples of this lower alkyl group are the same as those exemplified above for R. The two groups R 'together denote a lower alkylene group having at least 2 carbon atoms and can form a ring together with their adjacent sulfur atoms. An ethylene group may be cited as an example of such an alkylene group.

In the process illustrated by the reaction scheme for the preparation of the compounds of the general formula (I) of the present invention, the following compounds are specific examples of the starting compound of the general formula (II):

11-1. N- (5-methyl-2-pyridylmethyl) ethylenediamine, II-2. N- (5-methyl-2-pyridylmethyltrimethylenediamine, II-3, N- (6-methyl-2-pyridylmethyl) ethylenediamine, II-4, N- (6-methyl-2-pyridylmethyl) trimethylenediamine, II- 5. N- (4-Methyl-2-pyridyl) methyl (ethylenediamine, II-6, N- (4-methyl-2-pyridylmethyl) trimethylenediamine, II-7, N- (5-ethyl-2-pyridylmethyl) ethylenediamine , MS, N- (5-butyl-2-pyridylmethyl) ethylenediamine,

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11-9. N- (4,6-dimethyl-2-pyridylmethyl) ethylenediamine,

11-10. N- (3-chloro-2-pyridylmethyl) ethylenediamine,

11-11. N-IB-chloro ^ -pyridylmethyDethylendiamin,

11-12. N- (5-chloro-2-pyridylmethyl) tnmethylendiamin,

ΙΓ-13th N- (3,5-dichloro-2-pyridylmethyl) ethylenediamine,

11-14. N- (5-F [uoro-2-pyridylmethyl) trimethylenediamine,

11-15. N- (6-Bromo-2-pyridylmethyl) ethylenediamine,

11-16. N- [2- (5-ethyl-2-pyridyl) ethyl] trimethylenediamine,

11-17. N-ie-chloro ^ -methyl ^ -pyridylmethyDethylendiamin,

11-18. N- (5-methyl-3-pyridylmethyl) ethylenediamine,

11-19. N- ethylenediamine (2-methyl-5-pyridylmethyl)

II-2 NC. N- trimethylenediamine (2-methyl-5-pyridylmethyl)

11-21. N- ethylenediamine (2-phenyl-5-pyridylmethyl)

li-22nd N- trimethylenediamine (2-phenyl-5-pyridylmethyl)

II-23rd N- ethylenediamine (2-benzyl-5-pyridylmethyl)

II 24th N- (2-Chloro-3-pyridylmethyl) ethylenediamine,

II 25th N- (2-Chloro-3-pyridylmethyl) trimethylenediamine,

II 26th N-t B-chloro-S-pyridylmethyOethylendiamin,

II 27th N-fB-chloro-S-pyridylmethylltrimethylendiamin,

II-28th N- (5-Bromo-3-pyridylmethyl) ethylenediamine,

II-29th N- (5-Bromo-3-pyridyliTiethyl) trimethylenediamine,

II 30th N- ethylenediamine (2-Bromo-5-pyridylmethyl)

11-31. N- trimethylenediamine (2-Bromo-5-pyridylmethyl)

II-32. N- (5-Fluoro-3-pyridylmethyl) ethylenediamine,

II-33. N- ethylenediamine (2-fluoro-5-pyridylmethyl)

II-34. N- (2-fluoro-5-pyridylmethyl (trimethylenediamine,

II-35th N- [1- (2-Fluoro-5-pyridyl) ethyl] ethylenediamine,

II-36. N- [2-methyl-1- (2-fluoro-5-pyridyl) propyl] -ethylenediamine,

II-37. N- [2- (2-fluoro-5-pyridyl) ethyl] ethylenediamine,

II 38th N- [3- (2-Bromo-5-pyridyl) propyl] trimethylenediamine,

II. 39 N- tetrarnethylendiamin (2-8rorno-5-pyridylmethyl)

II 40th N- [4- (2-Bromo-5-pyridyl) butyl] trimethylenediamine,

11-41. N- ethylenediamine (2-Chloro-6-methyl-3-pyridylmethyl)

II-42 .. N- (2,4-dichloro-5-pyridylmethyl) trimethylenediamine,

II-43rd N- (2,6-dichloro-3-pyridylmethyl) ethylenediamine,

II-44th N- (2,4-dibromo-5-pyridylmethyl) ethylenediamine,

II-45th N- (2,4-difluoro-5-pyridylmethyl) ethylenediamine,

II-46th N- (2,4,5,6-tetrafluoro-3-pyridylmethyl) ethylenediamine,

II-47. N- (2,4,5,6-tetrachloro-3-pyridyimethyl) ethylenediamine,

II-48. N- (2-methoxy-3-pyridylmethyl) trimethylenediamine,

II-49th N- ethylenediamine (2-methoxy-5-pyridylmethyl)

U-BO. N- trimethylenediamine (2-methoxy-5-pyridylmethyl)

11-51. N- ethylenediamine (2-ethoxy-5-pyridylmethyl)

II-52nd N- (2-ethoxy-5-pyridylmethyltrimethylenediamine,

II-53rd N- ethylenediamine (2-isopropoxy-5-pyridylmethyl)

II-54th N- ethylenediamine (2-phenoxy-5-pyridylmethyl)

II-55. N- trimethylenediamine (2-phenoxy-5-pyridylmethyl)

II-56th N- [2- (2,4-dichlorophenoxy) -5-pyridylmethyl] ethylenediamine,

I1-57. N- (2-methylthio-3-pyridylmethyl) ethylenediamine,

M-BS. N- ethylenediamine (2-methylthio-5-pyridylmethyl)

Ii-BS. N- (2-methylthio-5-pyridyl) methyltrimethylenediamine,

II 60th N- ethylenediamine (4-methyl-2-methylthio-5-pyridylmethyl)

11-61. N- ethylenediamine (2-phenylthio-5-pyridylmethyl)

II-62. N- [2- (4-Chlorophenylthio) -5-pyridylmethyl] ethylenediamine,

II-63rd N- ethylenediamine (2-ethylthio-5-pyridylmethyl)

II-64. N- ethylenediamine (2-methylsulfinyl-5-pyridylmethyl)

II 65th N- trimethylenediamine (2-methylsulfonyl-5-pyridylmethyl)

II-66. N- trimethylenediamine (4-Chloro-2-fluoro-5-pyridylmethyl)

II-67. N-fe-chloro ^ -methyl-S-pyridylmethyDethylendiamin,

II-68. N- ethylenediamine (2-Chloro-4-methyl-5-pyridylmethyl)

II 69th N- ethylenediamine (2-allyl-5-pyridylmethyl)

II 70th N- ethylenediamine (2-propargyl-5-pyridylmethyl)

11-71. N- (2,3-dichloro-5-pyridylmethyl) ethylenediamine,

II-72. N- [2- (1-propenyl) -5-pyridylmethyl] ethylenediamine,

II-73rd N- (2-Chloro-4-pyridylmethyl) ethylenediamine,

II-74. N- (2-Chloro-4-pyridylmethyl) trimethylenediamine,

II-75 miles. N- (2-Fluoro-4-pyridylmethyl) ethylenediamine,

II-76th N- (2-Fluoro-4-pyridylmethyl) trimethylenediamine,

II-77th N- (2,6-Dichloro-4-pyridylmethyl) ethylenediamine,

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11-78. N- (2,6-Difluoro-4-pyridylmethyl) trimethylenediamine in,

11-79. N- (2-methyl-4-pyridylmethyl) ethylenediamine,

11-80. N- (2-methyl-4-pyridylrnethyl) trimethylendiarnin,

11-81. N- ethylenediamine [l- (2-chloro-4-pyridyl) ethyl]

II-82nd N- ethylenediamine (2-Chloro-6-methyl-4-pyridylmethyl),

II-83rd N- trimethylenediamine (2-Chloro-6-methyl-4-pyridylmethyl),

II 84th N- (2,6-Dimethyl-4-pyridylmethyl) ethylenediamine,

II 85th N- (2-Bromo-4-pyridylmethyl) ethylenediamine,

II-86th N- (2,6-dibromo-4-pyridylmethyl) ethylenediamine,

II 87th N- (2,3,5,6-tetrafluoro-4-pyridylmethyl) ethylenediamine,

II 88th N- (2,3,5,6-tetrafluoro-4-pyridylmethyl) trimethylenediamine,

JJI-89th N- (2,6-Dichloro-4-pyridylmethyl) trimethylenediamine,

II-90. N-O-Chioro - ^ - fTuoro B pyridylmethyijethylendiamin,

11-91. N- (3-Bromo-2-fluoro-5-pyridylmethyl) ethylenediamine,

II-92nd N- ethylenediamine (2-Chloro-3-fluoro-5-pyridylmethyl)

II-93rd N- (2,3,4-trichloro-5-pyridylmethyl) ethylenediamine,

II-94. N-O-chloro ^ methylthio-B-pyridylmethyöethylendiamin,

II-95. N- ethylenediamine (2-chloro-5-pyridylmethyl)

II-96th N- [2- (2-chloro-5-pyridyl) ethyl] ethylenediamine,

II 97th N- trimethylenediamine (2-chloro-5-pyridylmethyl)

II-98th N- [2- (2-chloro-5-pyridyl) ethyl] trimethylenediamine,

II-99th N- [1- (2-chloro-5-pyridyl) ethyl] trimethylenediamine,

11-100. N- [3- (2-chloro-5-pyridyl) propyl] trimethylenediamine,

11-101. N- [1- (2-chloro-5-pyridyl) ethyl] ethylenediamine,

11-102. N- tetramethylenediamine (2-chloro-5-pyridylmethyl)

11-103. N- [4- (2-chloro-5-pyridyl) butyl] trimethylenediamine,

11-104. N- [1- (2-chloro-5-pyridyl) propyl] trimethylenediamine and

11-105. N- [2-methyl-1- (2-chloro-5-pyridyl) propyl] ethylenediamine.

Specific examples of the compound of the general formula (III) which is likewise a starting material include 1-nitro-2,2-bis (methylthio) ethylene,

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

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

2-Nitromethylen1,3-dithiolane

 The aforesaid process is described in detail by the following typical example:

Cl - // N) -CH - NH- (CH -), - NH, + (CH-S) -C = CHNO-

Ξ N

CNO

Cl

Conveniently, the above process for the preparation of the compounds according to the present invention may be carried out in a solvent or diluent. For this purpose, all inert solvents or diluents may be used.

Examples of such solvents or 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, di-isopropyl ether , Dibutyl ether, propylene oxide, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile, propionitrile and acrylonitrile, alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol, esters such as ethyl acetate and amyl acetate, acid amides such as dimethylformamide and dimethylacetamide , Sulfones and sulfoxides such as dimethyl sulfoxide and sulfolane, as well as bases such as pyridine. The above method can be performed within a wide temperature range. In general, it may be carried out at a temperature between about -2O ⁰ C and the boiling point of the mixture, preferably at a temperature between about 0 ° C and about 100 ⁰ C. Conveniently, the reaction is carried out under normal atmospheric pressure, but it is also possible to operate at elevated or reduced pressure.

The compounds of the general formula (I) according to the present invention can also be prepared by means of an alternative method schematically shown below.

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Alternative method 1

RX _n -V 44-CH- (CHO-Y +

CHNO ₂

(IV)

(VI)

(In the above formulas, R, X, I, m and η are as defined above, and Hal denotes a halogen atom).

The compounds of the general formula (II) according to the present invention can be prepared, for example, by the following method ii).

Method ii)

R ι

(IV) (V)

CH- (CH ₂ ) _n -NH- (CH ₂ ) _m -NH ₂

• (H)

(In the formulas, R, X, I, m, η and Y are as defined above).

In the above reaction scheme, R, X, I, m and η may have the same meanings as described above for the process

i). Y denotes a halogen atom such as fluorine, chlorine, bromine and iodine or the group -OSO ₂ R ", in which R" represents the same lower alkyl as exemplified above for the process, or an aryl group such as phenyl and p-tolyl.

In the process represented by the reaction scheme for producing the compound of the general formula (II) according to the present invention, specific examples of the starting compound of the general formula (IV) include IV-1. 5-methyl-2-pyridylmethyl chloride, IV-2. e-methyl-a-pyridylmethyl chloride, IV-3. 4-methyl-2-pyridylmethyl chloride, IV-4. 5-ethyl-2-pyridylmethyl chloride, IV-5. 5-butyl-2-pyridylmethyl chloride, IV-6. 4,6-dimethyl-2-pyridylmethyl chloride, IV-7. S-chloro-pyridylmethyl chloride, IV-8. δ-chloro-pyridyltiethyl chloride, IV-9. 3,5-dichloro-2-pyridylmethyl chloride, IV-10. 5-fluoro-2-pyridylmethyl chloride, IV-11. 6-bromo-2-pyridylmethyl chloride, IV-12. 2- (5-ethyl-2-pyridyl) ethyl chloride, IV-13. S-chloro-methyl-pyridylmethyl chloride, IV-14. ö-methyl-S-pyridylmethyl chloride, IV-15. 2-methyl-5-pyridylmethyl chloride, IV-16. 2-phenyl-5-pyridylmethyl,

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IV-17th 2-Benzyl-5-pyridylmethyl,

IV-18th 2-Chloro-3-pyridylmethyl,

IV-19th B-chloro-S-pyridylmethyl,

IV-20th B-Bromo-S-pyridylmethyl,

IV-21st 2-Bromo-5-pyridylmethyl,

IV-22nd B-fluoro-S-pyridylmethyl,

IV-23rd 2-fluoro-5-pyridylmethyl,

IV-24th 1- (2-Fluoro-5-pyridyl) ethyl chloride,

IV-25th 2- (Methyl-1- (2-fluoro-5-pyridyl) propyl,

IV-26th 2- (2-fluoro-5-pyridyl)! Arid ethylch,

IV-27th 3- (2-Bromo-5-pyridyl) propyl,

IV-28th 2-Bromo-4-pyridylmethyl,

IV-29th 4- (2-Bromo-5-pyridyl) butyl chloride,

IV-30th 2-Chloro-6-methyl-3-pyridylmethyl,

IV-31st 2,4-dichloro-5-pyridylmethyl,

IV-32. 2,6-dichloro-5-pyridylmethyl,

IV-33. 2,4-dibromo-5-pyridylmethyl,

IV-34. 2,4-difluoro-5-pyridylmethyl,

IV-35th 2,4,5,6-tetrafluoro-3-pyridylmethyl,

IV-36. 2,4,5,6-tetrachloro-3-pyridylmethyl,

IV-37. 2-IVIethoxy-3-pyridylmethyl,

IV-38th 2-methoxy-5-pyridylmethyl,

IV. 39 2-ethoxy-5-pyridylmethyl,

IV-40th 2-isopropoxy-5-pyridylmethyl chloride _r

IV-41. 2-phenoxy-5-pyridylmethyl,

IV-42nd 2- (2,4-dichlorophenoxy) -5-pyridylmethyl,

IV-43rd 2-methylthio-3-pyridylmethylchloΓid,

IV-44th 2-methylthio-5-pyridylmethyl,

IV-45th 4 - ^ / lethyl-2-methylthio-5-pyridylmethyl,

IV-46th 2-phenylthio-5-pyridylmethyl,

IV-47. 2- (4-Chlorophenylthio) -5-pyridylmethyl,

IV-48. 2-ethylthio-5-pyridylmethyl,

IV-49th 2-l \ / lethylsulfinyl-5-pyridylmethyl,

IV-50th 2-l ^ / lethylsulfonyl-5-pyridylmethyl,

IV-SI. 4-Chloro-2-fluoro-5-pyridylmethyl chloride _/

IV-52nd e-Chloro ^ -methyl-S-pyridylmethyl,

IV-53rd 2-Chloro-4-methyl-5-pyridylmethyl,

IV-54th 2-allyl-5-pyridylmethyl,

IV-55. ' 2-propargyl-5-pyridylmethyl,

IV-56th 2,3-dichloro-5-pyridylmethyl,

IV-57 Amendment. 2- (1-propenyl) -5-pyridylmethyl,

IV-58th 2-chloro-4-pyridylmethyl chloride,.

IV-59th 2-Fluoro-4-pyridylmethyl,

IV-60th 2,6-dichloro-4-pyridylmethyl,

IV-61. 2,6-difluoro-4-pyridylmethyl,

IV-62. 2-methyl-4-pyridylmethyl,

IV-63rd 1- (2-chloro-4-pyridyl) ethyl chloride,

IV-64. 2-Chloro-6-methyl-4-pyridylmethyl,

IV-65th 2,6-dimethyl-4-pyridylmethyl,

IV-66. 2-Bromo-4-pyridylmethyl,

IV-67. 2,6-dibromo-4-pyridylmethylene ion,

IV-68. 2,4,5,6-tetrafluoro-4-pyridylmethyl,

IV-69th S-chloro ^ -fluoro-B-pyridylmethyl,

IV-70th 3-Bromo-2-fluoro-5-pyridylmethyl,

IV-71st 2-Chloro-3-fluoro-5-pyridylmethyl,

IV-72. 2,3,4-trichloro-5-pyridylmethyl,

IV-73rd S-chloro ^ methylthio-B-pyridylmethyl,

IV-74. 2-chloro-5-pyridylmethyl,

IV-75 miles. 2- (2-chloro-5-pyridyl) ethyl chloride,

IV-76th 1- (2-Chloro-5-pyridyl) ethylchloridund

IV-77th 3- (2-chloro-5-pyridyl) propyl chloride.

The corresponding bromides and p-toluenesulfonates can also be cited instead of the above chlorides.

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Specific examples of the compound of the general formula (V), which is likewise a starting material, include ethylenediamine,

Trimethylenediamine and

Tetramethylenediamine min

 The foregoing method will be described in detail by the following typical example.

Cl - // Jy-CH ₂ -Cl + H ₂ N- (CH ₂ ) ₃ -

-O V) -CH-NH- (CH-,), -NH.

Vr / ^{2 2} ' ^{3 2}

The above process can be carried out using the same solvents or diluents as exemplified above for process i).

The above reaction can be carried out in the presence of an acid-binding agent. Examples of the acid-binding agent are the hydroxides, carbonates, bicarbonates and alkoxides of alkali metals, and tertiary amines such as triethylamine, diethylaniline and pyridine, which are generally used.

The above method can be carried out as in the case of the method i) within a wide range of the temperature. The reaction is conveniently carried out under normal atmospheric pressure, but it is also possible to operate at elevated or reduced pressure.

The compounds of general formula (II), provided that η 0 designates, in addition to the above process ii) can also be prepared by means of an alternative method 2 shown schematically below.

Alternative method 2

(VII) (V)

H-NH- (CH-) -NH_ ζ m 2

(II ·)

(In the formulas, X, R, and m have the meanings given above).

As the above reaction scheme shows, the compound of the general formula (ΙΓ) can be prepared by reacting a reducing agent such as sodium borohydride (NaBH ₄ ). And the like with the imines obtained by reacting the pyridine aldehyde derivatives or the pyridyl alkyl ketone derivatives of the general formula (II). VII) with the compound of the general formula (V).

In addition, provided that R stands for a hydrogen atom and denotes η 0, the compounds of the general formula (II) can also be prepared by means of the alternative method 3 shown schematically below.

Alternative method 3

-11- 750

+ H ₂ N- (CH ₂ ) _m -NH ₂

(VIII) (V)

(In the formulas, X and m have the meanings given above). As the above reaction scheme shows, the compound of the general formula (II ") can be prepared by reacting a reducing agent such as lithium aluminum hydride (LiAlH ₄ ) and the like with the nicotinic acid amide derivatives or picolinic acid amide derivatives obtained by reacting the pyridylcarbonyl derivatives of the general formula (VIII) can be obtained with the compound of general formula (V).

The compounds of the general formula (II), provided that R stands for a hydrogen atom, designated η 0 and denotes m 3, can also be prepared by means of the alternative method 4 shown schematically below.

Alternative method 4

CH-NH- + CH_ = CH-CN.

(IX)

00

(II '')

(In the formulas have X and the meanings given above). As the above reaction scheme shows, the compound of the general formula (H "') can be prepared by reduction according to the above-described alternative method 2, the adduct obtained by reacting acrylonitrile with a compound of the general formula (IX) For example, N- (2-chloro-5-pyridylmethyl) trimethylenediamine, compound 11-97 below, can also be prepared by the above alternative method.

The compounds of the general formula (II), provided that m denotes 2, can also be prepared by means of the alternative method 5 shown schematically below.

Alternative method 5

(X)

(II "")

-12- 750 98

(In the formulas, R, X, and η are as defined above).

As the above reaction scheme shows, the compound of the general formula (H "") can also be prepared by reacting the pyridylalkylamine derivative of the general formula (X) with ethyleneimine.

The compounds of the present invention may be present in the form of their salts. The salts may be, for example, inorganic salts, sulfonates, organic acid salts and metal salts. Specific examples of the compounds of the present invention in salt form include

1- (2-chloro-5-pyridylmethyl) -2-nitromethylenetetrahydropyrimidine hydrochloride, 1- (2-chloro-5-pyridylmethyl) -2-nitromethylenetetrahydropyrimidine p-toluenesulfonate, 1- (2-chloro-5-pyridylmethyl) - 2-nitromethylene-imidazolidine hydrochloride and 1- (2-chloro-5-pyridylmethyl) -2-nitromethylene-imidazolidine-copper (II) acetate; 1- (2-Bromo-5-pyridylmethyl) -2-nitromethylenetetrahydropyrimidine hydrochloride, 1- (2-IVethoxy-5-pyridylmethyl) -2-nitromethyleneimidazolidine hydrochloride, '1- (2-fluoro-5-pyridylmethyl) -2 -nitromethylene-imidazolidine p-toluenesulfonate, 1- (2-bromo-5-pyridylmethyl) -2-nitromethylene-tetrahydropyrimidine-copper (II) acetate, 1- (3-bromo-5-pyridylmethyl) -2-nitromethylene-imidazolidine-succinate.

As insecticides, the compounds of the present invention can be used immediately after dilution with water or in the form of various formulations as obtained using agriculturally acceptable excipients by methods generally used in the practical production of agrochemicals. In practical use, these various formulations are used either directly or after dilution with water to the desired concentration.

The agriculturally acceptable excipients mentioned herein include, for example, diluents (solvents, extenders, carriers), surfactants (solubilizers, emulsifiers, dispersants, wetting agents),

Stabilizers, adhesives, aerosol propellants and synergistic agents. ,

Examples of the solvents are water and organic solvents, for example, hydrocarbons (eg, n-hexane, petroleum ether, petroleum fractions [eg, paraffin waxes, kerosene, light oils, middle oils and heavy oils], benzene, toluene and xylene), halogenated Hydrocarbons (eg, methylene chloride, carbon tetrachloride, ethylene chloride, ethylene dibromide, chlorobenzene, and chloroform), alcohols (eg, methanol, ethanol, propanol, and ethylene glycol), ethers (eg, diethyl ether, ethylene oxide, and dioxane), alcohol ethers (e.g., ethylene glycol monomethyl ether), ketones (e.g., acetone and isophorone), esters (e.g., ethyl acetate and amyl acetate), amides (e.g., dimethylformamide and dimethylacetamide), and sulfoxides (e.g., dimethylsulfoxide ). Examples of extenders or carriers include inorganic powders, for example, hydrated lime, magnesium lime, gypsum, calcium carbonate, silica, perlite, pumice, calcite, diatomaceous earth, amorphous silica, alumina, zeolites, and clay minerals (eg, pyrophyllite, talc, montmorillonite, beidellite, Vermiculite, kaolinite and mica), vegetable powders such as cereal powders, starches, processed starches, sugars, glucose and crushed stems of plants, and powders of synthetic resins such as phenolic resins, urea resins and vinyl chloride resins.

Examples of the surfactants include anionic surfactants such as alkylsulfonic acid esters (e.g., sodium lauryl sulfate), arylsulfonic acids (e.g., alkylarylsulfonic acid salts and sodium alkylnaphthalenesulfonates), succinic acid salts and salts of sulfuric acid esters of polyethylene glycol-alkylaryl ethers, cationic surfactants such as alkylamines (U.S. laurylamine, stearyltrimethylammonium chloride and alkyldimethylbenzylammonium chlorides) and polyoxyethylenealkylamines, nonionic surfactants such as polyoxyethylene glycol ethers (e.g., polyoxyethylene alkylaryl ethers and their condensation products), polyoxyethylene glycol esters (e.g.

Polyoxyethylene fatty acid esters) and esters of polyhydric alcohols (e.g., polyoxyethylene sorbitan monolaurate) and amphoteric surfactants.

Examples of other adjuvants include stabilizers, adhesives (eg, agricultural soaps, casein-lime, sodium alginate, polyvinyl alcohol, vinyl acetate type adhesives, and acrylic adhesives), aerosol propellants (e.g., trichlorofluoromethane, dichlorofluoromethane, 1,2,2- Trichloro-i, 1,2-trifluoroethane, chlorobenzene, liquefied natural gas [LNG] and lower ethers), combustion control agents for fumigants (eg nitrites, zinc powders and dicyandiamide), oxygen-releasing agents (e.g. Chlorates), anti-caking agents, dispersion stabilizers (e.g., casein, tragacanth, carboxymethyl cellulose [CMC] and polyvinyl alcohol [PVA]) and synergistic agents.

The compounds of the present invention can be formulated into various preparations by the common methods common in the field of agrochemicals. Illustrative examples of such uses are emulsifiable concentrates, oil preparations, wettable powders, soluble powders, suspensions, dusts, granules, powdered preparations, fumigants, tablets, aerosols, pastes and capsules.

The insecticides according to the present invention may contain about 0.1 to about 95% by weight, preferably about 0.5 to about 90% by weight of the aforementioned active ingredient.

For practical use, the suitable amount of the active compound in the aforementioned various formulations and ready-to-use preparations is generally from about 0.0001 to about 20% by weight, preferably from about 0.005 to about 10% by weight.

The content of the active ingredient may be suitably varied depending on the kind of the formulation, the method, the purpose, the time and place of its use, and the state of occurrence of the harmful insects.

If necessary, the compounds according to the present invention may also be used in combination with other agrochemicals, for example with other insecticides, fungicides, other miticides, other nematicides, anti-viral agents, herbicides, plant growth regulators and attractants (eg organophosphate compounds, Carbamate compounds, dithio [oderthiol] carbamate compounds, organochlorine compounds, dinitro compounds, organic sulfur or organometallic compounds, antibiotics, substituted diphenyl ether compounds, urea compounds and triazine compounds) and / or fertilizers.

The various agents and ready-to-use preparations containing the active ingredient according to the invention described above can be applied by means of various methods commonly used for the application of agrochemicals, for example by spraying (spraying liquids, atomizing, atomizing, dusting, spreading granules, Water surface treatment, casting, etc.), smoking, soil treatment (mixing with the soil, spraying, steaming, casting, etc.), surface application (eg coating, application in the form of tapes,

-13- 750

Powder coating, covering, etc.), dipping and baiting. They can also be applied by means of the so-called ultra-low-volume spray method. According to this method, the active ingredient may even be incorporated at a concentration of 100%.

The application rate per unit area is, for example, about 0.03 to about 10 kg / ha, preferably about 0.3 to about 6 kg / ha. In special cases, even the application rates may or even should be outside the specified range.

According to the present invention, there can be provided an insecticidal agent containing as the active ingredient the compound of the general formula (I) and a diluent (a solvent and / or diluent and / or carrier) and / or a surfactant and, if further required, a stabilizer, an adhesive, a synergistic agent, etc. contains.

The present invention further provides a method for controlling harmful insects, which consists in that a compound of the general formula (I) alone or in the form of a mixture with a diluent (a solvent and / or an extender and / or a carrier) and / or a surfactant and, if necessary, a stabilizer, an adhesive, a synergistic agent, etc., are applied to harmful insects and / or their habitat or the location of their occurrence.

embodiment

The present invention is explained in detail by the following examples, but is not limited to these specific examples alone.

example 1

2-chloro-5-pyridylmethyl chloride (16.2g) in the form of a solution in acetonitrile (30ml) was added dropwise at room temperature over 1h to a solution of ethylenediamine (18g) in acetonitrile (100ml). The reaction mixture was stirred at room temperature for 1 h and then at 40 ^° C. for 2 h. After stirring, the acetonitrile was evaporated under reduced pressure. Ether was added to the residue and the insoluble salts were filtered off. Thereafter, the ethers and the excess ethylenediamine were evaporated under reduced pressure to give N- (2-chloro-5-pyridylmethyl ethylenediamine (16 g) represented by the following formula as a colorless oil: no ° 1.5627.

Cl - // \ y_CH ₂ NH (CH ₂

(Compound No. 11-95)

Example 2

2-Bromo-5-pyridylmethylbromide (25g) in the form of a solution in acetonitrile was added dropwise at ⁰ ° C to a solution of ethylenediamine (30g) in acetonitrile (80ml). After the reaction mixture had been stirred for some time at room temperature, the insoluble salts were filtered off and the filtrate was concentrated on a water bath at 4O ⁰ C, after which N- (2-Bromo-5-pyridylmethyl) was obtained ethylenediamine (22g); n. ⁶ 1,5586.

^Br - / ^CH 2 ^{NH (CH} 2 ⁾ 2 ^NH 2

(Compound Nos. 11-30)

Example 3

6-Methylpicolin-aydehyde (12.1 g) was added to a solution of ethylenediamine (24 g) in anhydrous dioxane (200 ml). The mixture was stirred for 3 h at room temperature. After stirring, the mixture was heated and a mixture (120 ml) of dioxane and water formed was distilled off to complete the reaction to the Schiff base. The contents of the vessel were cooled to room temperature and sodium borohydride (7.6 g) was added in small portions. After the addition, the mixture was stirred at room temperature for 8 hours. After distilling off the volatiles from the mixture in vacuo, ice water was added to the residue, and the product was extracted with chloroform. The extract was evaporated to give N- (2-methyl-6-pyridylmethyl) ethylenediamine (8.3g); Bp 127-129 ⁰ C / 0,13mbar (0,1mmHg).

(Compound No. 11-19)

-14- 750 98

Example 4

2-ethoxy-5-pyridylmethyl chloride hydrochloride (9.6 g) in the form of an aqueous solution was added dropwise at 0 ⁰ C to 5 ° C to the mixed solution of trimethylene diamine (11.1 g) and a 20% aqueous solution (22g) added by sodium hydroxide. After stirring the reaction mixture at room temperature for some time, water and excess trimethylenediamine were distilled off from the contents of the vessel under reduced pressure, and after filtering off the resulting inorganic salts, the viscous oily substance obtained was distilled under vacuum, after which N- (2-ethoxy) 5-pyridylmethyltrimethylenediamine (6.3 g), b.p. 134-135 ° C / 0.11 mbar (0.08mmHg).

(Compound No. 11-52)

Example 5 '.

Table 1 below shows the compounds of general formula (II) prepared in the same manner as in Examples 1, 2 or 4.

Table 1

Compound No. m η R Posi- X,

tion d. Subst.am pyridine

Physical constant

II - 1 2 0 H 2 5-CH ₃ £ £ 1.5397 II - 2 3 0 H 2 5-CH ₃ n £ ° 1.5348 II - 20 3 0 H 5 2-CH ₃ Sdp.134-135 ^e C / 0.13 mbar II - 24 2 0 H 3 2-Cl n £ ⁵ 1,5575 II - 31 3 0 H  5 2-Br njf 1.5581 II "33 2 0 H 5 2-F 8φ. 118-120 ° C / 0.13 mbar II - 34 3 0 H 5 2-F Bp 120-122 ° C / 0.13 mbar II - 51 2 0 H 5 2-OCH ₃ εφ. "142-144 ° C / 0.13 iribar II - 54 2 0 H 5 n ^ ⁷ 1,5845 II - 55 3 0 H 5 2-0 © n ^ ⁷ 1,5775 II - 58 2 0 H 5 2-SCH ₃ εφ. 130-131 ° C / 0.09 mbar II - 59 3 0 H 5 2-SCH ₃ εφ. 143-145 ° C / 0.13 mbar II - 97 3 0 H 5 2-Cl τξ ² 1,5562

-15- 750

Example 6

Table 2 below shows the compounds of the general formula (II) which were further prepared in the same manner as in the above Examples 1, 2 or 4 for the purpose of using for the synthesis of the compounds of the general formula (I).

Table 2 vi connection No. N II. 3 N II. 4 N II. 5 N II. 6 N II. 7 N II. 8 N II. 9 N 11-10. N 11-11. N 11-12. N 11-13. N 11-14. N 11-15. N 11-16. N 11-17. N 11-18. N 11-19. N II 20th N 11-21. N II-22nd N II-23rd N II 24th N II 25th N II 26th N II 27th N II-28th N II-29th N II 30th N 11-31. N II-32. N II-33. N II-34. N II-35th N II-36. N II-37. N II 38th N II. 39 N II 40th N 11-41. N II-42nd N II-43rd N II-44th N II-45th N II-46th N II-47. N II-48. N II-49th N H-BO. N 11-51. N II-52nd N II-53rd N II-54th N II-55. N II-56th N II-57 Amendment. N II 58th N II 59th N II 60th N 11-61.

Connection (product)

(6-methyl-2-pyridylmethyl) ethylenediamine, (6-methyl-2-pyridylmethyl) trimethylenediamine, (4-methyl-2-pyridylmethyl) ethylenediamine, (4-methyl-2-pyridylmethyl) trimethylenediamine, (5-ethyl-2 -pyridylmethyl) ethylenediamine, (5-butyl-2-pyridylmethyl) ethylenediamine, (4,6-dimethyl-2-pyridylmethyl) ethylenediamine (3-chloro-2-pyridylmethyl) ethylenediamine, (5-chloro-2-pyridylmethyl) ethylenediamine , (5-chloro-2-pyridylmethyl) trimethylenediamine, (3,5-dichloro-2-pyridylmethyl) ethylenediamine, (5-fluoro-2-pyridylmethyl) trimethylenediamine, (6-bromo-2-pyridylmethyl) ethylenediamine, [2- (5-ethyl-2-pyridyl) ethyl] trimethylenediamine, (6-chloro-4-methyl-2-pyridylmethyl) ethylenediamine, (5-methyl-3-pyridylmethyl) ethylenediamine, (2-methyl-5-pyridylmethyl) ethylenediamine, (2-Methyl-5-pyridylmethyl) trimethylenediamine, ^ -phenyl-δ-pyridylmethyldiylenediamine, ^ -phenyl-S-pyridylmethyldetrimethylenediamine, (2-benzyl-5-pyridylmethyl) ethylenediamine, ^ -chloro-S-pyridylmethyl-ethylenediamine, Ⓒ. S-pyridylmethyltrimethylenediamine, (B-chloro -S-pyridylmethyl ethylenediamine, (o-chloro-S-pyridylmethyltrimethylenediamine, (5-bromo-3-pyridylmethyl) ethylenediamine, (5-bromo-3-pyridylmethyl) trimethylenediamine, ^ -bromo-o-pyridylmethyl (ethylenediamine, (2- Bromo-5-pyridylmethyl) trimethylenediamine, (5-fluoro-3-pyridylmethyl) ethylenediamine, ^ -fluoro-S-pyridylmethyethylenediamine, ^ -fluoro-B-pyridylmethy-trimethylenediamine, [1- (2-fluoro-5-pyridyl) ethyl] ethylenediamine , - [2-Methyl-1- (2-fluoro-5-pyridyl) -propyl-ethylenediamine, - [2- (2-fluoro-5-pyridyl) -ethyl] -ethylenediamine, - [3- (2-bromo-5-pyridyl) propyl] trimethylenediamine, - (2-bromo-5-pyridylmethyl) tetramethylenediamine, - [4- (2-bromo-5-pyridyl) butyl] trimethylenediamine, - (2-chloro-6-methyl-3-pyridylmethyl! ethylenediamine, - (2,4-dichloro-5-pyridylmethyl) ethylenediamine, - (2,6-dichloro-3-pyridylmethyl) ethylenediamine, - (2,4-dibromo-5-pyridylmethyl (ethylenediamine, - (2,4-difluoro -5-pyridylmethyl) ethylenediamine, - (2,4,5,6-tetrafluoro-3-pyridylmethyl) ethylenediamine, - (2,4,5,6-tetrafluoro-3-pyridylmethyl) ethylenediamine n, - (2-methoxy-3-pyridylmethyl) trimethylenediamine, - (2-methoxy-5-pyridylmethyl) ethylenediamine, - (2-methoxy-5-pyridylmethyl) trimethylenediamine, - (2-ethoxy-5-pyridylmethyl) ethylenediamine, - (2-ethoxy-5-pyridylmethyl) trimethylenediamine, - (2-isopropoxy-5-pyridylmethyl) ethylenediamine, - (2-phenoxy-5-pyridylmethyl) ethylenediamine, - (2-phenoxy-5-pyridylmethyl) trimethylenediamine, - 2- (2,4-Dichlorophenoxy) -5-pyridylmethyl] ethylenediamine, - (2-methylthio-3-pyridylmethyl) ethylenediamine, (2-methylthio-5-pyridylmethyl) ethylenediamine, - (2-methylthio-5-pyridylmethyl) trimethylenediamine , - (4-methyl-2-methylthio-5-pyridylmethyl) ethylenediamine, - (2-phenylthio-5-pyridylmethyl) ethylenediamine,

-16- 750

Table 2 continuation

Compound compound (product) no.

II-62. N- [2- (4-Chlorophenylthio) -5-pyridylmethyl] ethylenediamine,

II-63rd N- ethylenediamine (2-ethylthio-5-pyridylmethyl)

II-64. N- ethylenediamine (2-methylsulfinyl-5-pyridylmethyl)

II 65th N- trimethylenediamine (2-methylsulfonyl-5-pyridylmethyl)

II-66. N- trimethylenediamine (4-Chloro-2-fluoro-5-pyridylmethyl)

II-67. N-fS-chloro-methyl-S-pyridylmethy-dimethyl-diamine, -.-

II-68. N- ethylenediamine (2-Chloro-4-methyl-5-pyridylmethyl)

II 69th N- ethylenediamine (2-allyl-5-pyridylmethyl)

II 70th N- ethylenediamine (2-propargyl-5-pyridylmethyl)

11-71. N- (2,3-dichloro-5-pyridylmethyl) ethylenediamine,

1I-72. N- [2- (1-propenyl) -5-pyridylmethyl] ethylenediamine,

II-73rd N- (2-Chloro-4-pyridylmethyl) ethylenediamine,

II-74. N- (2-Chloro-4-pyridylmethyl) trimethylenediamine,

II-75 miles. N- (2-Fluoro-4-pyridylmethyl) ethylenediamine,

II-76th N- (2-Fluoro-4-pyridylmethyl) trimethylenediamine,

II-77th N- (2,6-Dichloro-4-pyridylmethyl) ethylenediamine,

II 78th N- (2,6-difluoro-4-pyridylmethyl) trimethylenediamine,

II 79th N- (2-methyl-4-pyridylmethyl) ethylenediamine,

II 80th N- (2-methyl-4-pyridylmethyl) trimethylenediamine,

11-81. N- [1- (2TChloro-4-pyridyl) ethyl] ethylenediamine,

II-82nd N- (2-chloro-6-methyl-4-pyridylmethyl (ethylenediamine,

II-83rd N- trimethylenediamine (2-Chloro-6-methyl-4-pyridylmethyl),

II 84th N- (2,6-Dimethyl-4-pyridylmethyl) ethylenediamine,

II 85th N- (2-Bromo-4-pyridylmethyl) ethylenediamine,

II-86th N- (2,6-dibromo-4-pyridylmethyl) ethylenediamine,

II 87th N- (2,3,5,6-tetrafluoro-4-pyridylmethyl) ethylenediamine,

II 88th N- (2,3,5,6-tetrafluoro-4-pyridylmethyl) trimethylenediamine,

II 89th N- (2,6-Dichloro-4-pyridylmethyl) trimethylenediamine,

II-90. N- ethylenediamine (3-chloro-2-fluoro-5-pyridylmethyl)

11-91. N- (3-Bromo-2-fluoro-5-pyridylmethyl) ethylenediamine,

II-92nd N- ethylenediamine (2-0hloro-3-fluoro-5-pyndylrnethyl)

II-93rd N- (2,3,4-trichloro-5-pyridylmethyl) ethylenediamine,

II-94. N- ethylenediamine (3-chloro-2-methylthio-5-pyridylmethyl)

II-95. N- ethylenediamine (2-chloro-5-pyridylmethyl)

II-96th N- [2- (2-chloro-5-pyridyl) ethyl] ethylenediamine,

II 97th N- trimethylenediamine (2-chloro-5-pyridylmethyl)

II-98th N- [2- (2-chloro-5-pyridyl) ethyl] trimethylenediamine,

II-99th N- [1- (2-chloro-5-pyridyl) ethyl] trimethylenediamine,

11-100. N- [3- (2-chloro-5-pyridyl) propyl] trimethylenediamine,

11-101. N- [1- (2-chloro-5-pyridyl) ethyl] ethylenediamine,

11-102. ~ N- (2-Chlofo-5-pyridylmethyl) tetramethylenediamine,

11-103. N- [4- (2-chloro-5-pyridyl) butyl] trimethylenediamine,

11-104. N- [1- (2-chloro-5-pyridyl) propyl] trimethylenediamine,

11-105. N- [2-methyl-1- (2-chloro-5-pyridyl) propyl] ethylenediamine.

The following reference examples illustrate the syntheses of the compounds of the general formula (IV) which are intermediates in the preparation of the aforementioned compounds of the general formula (II) and of which a part is new.

Reference Example 1a!

15% methylmercaptan sodium salt (77 g) was added to 6-chloronicotinic acid (15.8 g) dissolved in 20% aqueous solution of sodium hydroxide (22 g). The reaction mixture was stirred at 70 ⁰ C to 80 ° C for 10 h. After cooling, the precipitate formed after neutralization was collected by filtration and recrystallized from chloroform to give 6-methylthionicotinic acid (15.3 g); M.p. 186-188 ⁰ C.

OQH

-17- 750 98

Reference Example 1 b

Thionyl chloride (23.8 g) was added to 6-methylthionicotinic acid (15.3 g) (from the above Reference Example 1 a). The reaction mixture was gradually heated with stirring and then refluxed until evolution of hydrogen chloride ceased. 6-Methylthionicotinoyl chloride was obtained in stoichiometric amount by distilling off the excess thionyl chloride under reduced pressure. In ether dissolved 6-Methylthionicotinoylchlorid was added dropwise at 0 ⁰ C to 10 ° C added to a 20% aqueous solution of sodium borohydride (6.5 g). After the addition, the mixture was stirred for 1 hour, and the ether layer was separated and dried. The ether layer was evaporated under reduced pressure to give 2-methylthiopyridine-5-methanol (9.6 g); n ^ ² 1,6084. Reference Example 1c

Thionyl chloride (7.7 g) was added to 2-methylthiopyridm-5-methanol (7.8 g) (from the above Reference Example 1b) in chloroform (30 ml) at room temperature. After stirring for some time, the volatiles were distilled off under reduced pressure to give 2-methylthio-5-chloromethylpyridine hydrochloride (10.4 g) in a stoichiometric amount; M.p. 127-13O ⁰ C.

CH-Cl 2

^H 3 ^CS · HCl

The compounds prepared in the same manner as in the above Reference Examples 1 a, 1 b and 1 c are exemplified below

 Process of Reference Example 1 a:

(Mp 167-168 ° C)

2 (synthesized · out

6-methoxy-nicotinic acid, a known compound) (bp 95-96 ° C / 0.67 mbar (0.5 mmHg))

(M.p. 187-190 ⁰ C) Method of Reference Example 1b:

H ₃ CO

H ₅ C ₂

|| - ^H 2 ^0H

(Bp 97-98 ° C / 0.53 mbar (0.4 mmHg))

(n

25

1.5960)

(synthesized from 2,6-dichloroisonicotinic acid, a known compound)

(Mp 135-136 ⁰ C)

-18- 750

(synthesized from 2-chloroisonicotinic acid, a known compound)

(Mp. 64-66 ° C) Method of Reference Example Ic:

H ₃ C

CH ₂ Cl

(Bp. 98-99 ⁰ C / 6.7 to 8 mbar (5 to 6 mniHg)) H ₅ C ₂

(Bp 68-70 ° C / l, 33 mbar (lnHg))

1.6088)

Cl (mp 52-53 ° C)

Cl (bp 129-130 ° C / 40 mbar (30 mmHg))

-19- 750 98

Example 7

N- (2-chloro-5-pyridylmethyl) ethylenediamine (18.6 g), 1-nitro-2,2-bis (methylthio) ethyl ether (16.5 g) and methanol (100 ml) were mixed together at room temperature. The mixture was gradually heated with stirring and further stirred at 50 ^° C until evolution of methylmercaptan was complete. After the reaction, the reaction mixture was cooled to room temperature, and the obtained crystals were collected by filtration, whereby 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazoline (19 g) represented by the following formula was obtained in the form of pale yellow crystals ; M.p. 165-166 ° C.

CHNO.

CH

2 \ _

(Compound No. 95)

Example 8

N- (2-Fluoro-5-pyridylmethyl) ethylenediamine (1.7g), 1-nitro-2,2-bis (methylthio) ethylene (1.7g) and ethanol (10ml) were mixed together at room temperature. The mixture was gradually heated with stirring and further refluxed until evolution of methylmercaptan was complete. After cooling to room temperature, the resulting crystals were collected by filtration and dried to give pale yellow crystals of 1- (2-fluoro-5-pyridylmethyl) -2- (nitromethylene) imidazoline (1.7 g); M.p. 139-142 ⁰ C.

HN

N Q = CHN

CHNO

CH.

(Compound no. 1)

Example 9

Table 3 below shows the compounds of general formula (I) prepared in the same manner as in Examples 7 and 8.

Table 3

Connection No. m

η R position d. Subst.am pyridine

Physical constant

2 3 4

2 0 H 2 3 0 H 2 2 0 H 2

5-CH

5-CH.

6-Br

Schrp. 130-132 ⁰ C Schrrp. 145-146 ⁰ C Schnp. 176-178 ⁰ C

-20- 750 98

Table 3- Continued

m η R H Posi + "T ΓΧΠ t 2-OC ₂ H ₅ Physical constant Connection no. H 2-OC ₂ H ₅ H Ui ₁ UIl U · Subst.am 2 0 H pyridine ² "°" (^) Schnap. 171-173 ⁰ C 5 3 0 H 5 2-F Schnapps 177-179 ⁰ C 6 2 0 H 5 2-Cl: Schnapps 179-18O ⁰ C 7 3 .0 H 5 - 5-Br Schnp. 185-187 ⁰ C 8th 3 0 H 5 S-Br Schnap. 149-151 ⁰ C 9 2 0 H 5 2-Br Schnp. 201-204 ⁰ C 10 2 0 H 3 2-Br Schnp. 180-182 ⁰ C 11 3 0 H 3 2-Cl Schnapps 192-195 ° C 12 2 0 H 3- ^ 2-Cl Schnp. 167-17O ⁰ C 13 3 0 H 2,6-Cl ₂ Schnp. 193-195 ⁰ C 14 2 0 H 5 6-CH ₃ Schnapps 177-179 ⁰ C 15 3 0 H 4 6-CH ₃ Schnp. 219-222 ⁰ C 16 2 0 H 4 5-Cl Schrrp. 258-26O ⁰ C 17 2 0 H 4 5-Cl Schnap. 191-194 ⁰ C 18 3 0 H 2 2-CH ₃ Schnp. 202-204 ⁰ C 19 2 ' 0 H 2 2-SCH ₃ Schnap. 145-147 ⁰ C 20 3 0 H 2 2-SCH ₃ Schnapps 161-162 ⁰ C 21 2 0 H 2 2-Cl Schnp. 120-124 ⁰ C 22 2 0 5 6-CH ₃ Schnp. 125-126 ⁰ C 24 3 0 H 5 2-OCH ₃ Schrrp. 137-139 ° C 25 2 0 H 5 ² ~ © Schnapps 228-230 ⁰ C 26 H A- 2-Cl 2 0 Schnp. 159-161 ⁰ C 29 2 0 5 Schnp. 196-198 ⁰ C 42 3 0 5 Schnp. 184-186 ⁰ C 97 5

-21- 750 98

example

Table 4 below shows the compounds of the general formula (I) which are obtained by reacting the compounds of the general formula (II) from the above Examples 1, 2, 3, 4, 5 and 6 with the substances Nos. D, (III-2), (III-3) and (III-4) were synthesized in the same manner as in Examples 7 and 8.

Fabric no.

(III-1): 1-nitro-2,2-bis (methylthio) ethylene,

(III-2): 1-nitro-2,2-bis (ethylthio) ethylene,

(III-3): 1-nitro-2,2-bis (benzylthio) ethylene,

(III-4): 2-Nitromethylene-1,3-dithiolane.

Table 4

Ξ N

Compound fabric material m η P r ο d u k t H No, R Posi tion d. Subst.am pyridine

23 27

28 30 31 32 33 34 35 37 38 39 40

11-20 11-84

III-III-2

11-25 IU-I 11-50 III-2 II- 5 HI-I II- 6 IH-I II- 7 III-2 II- 8 IH-I II- 9 IH-I 11-13 III-3 11-14 III-2 11-16 III-4 11-17 IH-I

3 0 3 0 3 0 3 0 2 0 3 0 2 0 2 0 2 0 2 0 3 0 3 1 2 0

H H

5-4-

H 3 H 5 H 2 H 2 H 2 H 2 H 2 H 2 H 2 H 2 H 2

2-CH ₃ 2-Cl, 6-CH ₃ 2-Cl

4-CH ₃

4-CH

5-C ₂ H ₅

3,5-Cl 5-F

6-Cl

Table 4 - Continued

-22- 750 98

Verbincäung fabric no.

material

product

m η

Position d. Subst.am pyridine

X.

41 II-18 43 11-22 44 11-23 45 11-26 46 11-27

47 Π-32 IH-I 48 11-35 HI-I 49 11-36 ΙΙΙ-2 50 ΙΙ-37 ΗΙ-2 51 ΙΙ-38 ΠΙ-3 52 Π-39 HI-I 53 Π-40 IH-I 54 11-41 ΙΙΙ-2 55 ΙΙ-42 ΙΙΙ-3 56 11-43 ΙΙΙ-1 57 11-44 ΙΗ-2 58 11-45 ΗΙ-2 59 11-46 ΙΙΙ-3 60 11-47 ΗΙ-2 61 11-48 IH-I

III-2 III-2 III-III III-3 IH-I

2 0 3 0 2 0 2 0 3 0

2 0 2 0 2 0 2 1 3 2 4 0 3 3 2 0 3 0 2 0 2 0 2 0 2 0 2 0 3 0

H H H H H

H H H Ξ H

H H H H H H3-5- 5-3-

3-3-

5

5

5-5- 5-5- 3-

5-3- 5-5- 3-3- 3-

5-Cl

5ΚΓ1

5-F

2-F

2-F

2-F

2-3r

2-Br

2-3r

2-Cl,

6-CH ₃

2,4-Cl

2,4-Br ₂

2,4-F ₂

2,4,5,6-F ₄

2-OCH

Table 4 - Continued

-23- 750 98

Compound substance no.

material

product

m η

Position d. Subst.ain pyridine

73

74 75 76

62 11-53 III-l 63 11-56 III-2 € 4 11-57 III-2 65 11-60 III-l 66 11-61 III-l 67 11-62 III-3 68 11-63 IH-2 69 11-64 III-2 70 II-65 III-2 71 11-66 HI-I 72 11-67 III-l

11-68

11-69 11-70 11-71

in-i

III-III-III-2

2 0 2 0 2 C

2 0 2 0 2 0 2 0 2 0 3 0 3 0 2 0 2 0 2 0 2 0 2 0

H H H H

5-5- 3-

5

5

5

5

5-:

5

5-3-

5

5-5-

5

2-C ₃ H ₇ -ISO

Cl. 2-0 - ^) - Cl

2-SCH ₃ 4-CH ₃ ,

2-SCH ₃ 2-SQ

2-S-CH ₃

O2-SHZi,

η -5 O

4-Cl, 2-F 6-Cl,

2-CH ₃ 2-C1, 4-CH,

2-CH ₂ CH = CH ₂

2-CH ₂ C = CH

2,3-Cl ₂

Table 4 - Continued

-24- 750 98

Compound substance no.

material

product

m η

Position d. Subst.am pyridine

TJ 11-72 III-2 2 0 0 H 5 2-CH = CH-CH ₃ 78 11-75 III-4 2 0 0 H A- 2-F 79 11-76 III-4 3 0 0 H A- I 2-F 80 11-78 HI-I 3 0 0 H 4 2,6-F ₂ 81 11-79 III-l 2 0 0 H 4 2-CH ₃ 82 11-80 HI-I 3 0 0 H A- 2-CH ₃ 83 II-81 III-2 2 0 0 -CH ₃ A- 2-Cl 84 11-84 III-2 2 0 H A- 2,6- (CH ₃ ) ₂ 85 11-85 III-2 2 0 1 H A- 2-fir 86 11-86 · " III-l 2 0 1 H A- 2,6-3r ₂ 87 11-87 HI-I 2 0 H A- 2,3,5,6-F ₄ 88 II-88 IH-I 3 H A- 2,3,5,6-F ₄ 89 11-89 ni-2 3 H A- 2,6-Cl ₂ 90 11-90 RRI i 2 H. 5 2-F, 3-Cl 91 11-91 III-l 2 H 5 2-F, 3-r 92 11-92 IH-I 2 H 5 2-Cl, 3-F 93 11-93 IH-I 2 Ξ 5 2,3,4-Cl ₃ 94 11-94 IH-I 2 H 5 2-SCH ₃ , 3-Cl 96 11-96 IH-I 2 H 5 2-Cl 98 11-98 III-2 3 H 5 2-Cl

Table 4- Continued

-25- 750 98

Compound substance no.

' Material

product

m η

Position d. Subst.am pyridine

99 11-99 HI-I 3 0 ^ 3 5 2-Cl 100 11-100 III-l 3 2 H 5 2-Cl 101 11-101 III-l 2 0 5 2-Cl 102 11-102 III-l 4 0 H 5 2-Cl 103 11-103 III-l 3 3 H 5 2-Cl 104 11-104 III-2 3 0 -C ₂ H ₅ 5 2-Cl 105 11-105 III-l 2 0 -C-H ^ iso 5 2-Cl

Example 11 (wettable powder)

Fifteen parts of Compound No. 95 of the invention, 80 parts of a mixture (1: 5) of powdery diatomaceous earth and clay powder, 2 parts of sodium alkylbenzenesulfonate and 3 parts of sodium alkylnaphthalenesulfonate / formaldehyde condensate are pulverized and mixed to form a wettable powder. This is diluted with water and sprayed on harmful insects and / or their habitat or the place of their appearance.

Example 12 (Emulsifiable concentrate)

Thirty parts of Compound No. 13 of the invention, 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed together under stirring to prepare an emulsifiable concentrate. This is diluted with water and sprayed on harmful insects and / or their habitat or the place of their appearance.

Example 13 (Dusts)

2 parts of Compound No. 5 of the invention and 98 parts of clay powder are pulverized and mixed, whereby a dust is prepared. This is spread over harmful insects and / or their habitat or the place of their occurrence.

Example 14 (Granules)

Water (25 parts) is added to a mixture of 10 parts of Compound No. 14 of the invention, 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of lignosulfonate, and the mixture is well kneaded. The mixture is processed by means of an extruder-granulator into granules having a particle size of 0.43 to 2.0 mm (1 to 40 mesh), which is then dried at 40 ° C to 50 ° C, whereby a granulate is formed. The granules are spread over harmful insects and / or their habitat or the place of their occurrence.

Example 15 (Granules)

A rotary mixer is charged with 95 parts of clay mineral particles having a particle size distribution between 0.2 and 2 mm, and while rotating the mixer, 5 parts of compound No. 51 of the invention are sprayed onto the particles to uniformly wet them. The moist mixture is dried at 4O ⁰ C to 50 ⁰ C, whereby a granulate is formed. The granules are spread over harmful insects and / or their habitat or the place of their occurrence.

Example 16 (oil preparation)

Compound No. 1 of the invention (0.5 parts) and 99.5 parts of kerosene are mixed together with stirring to form an oil preparation. This is sprayed on harmful insects, mites or nematodes and / or their habitat or the place of their occurrence.

-26- 75098

Example 17 (biological test) Test with organophosphorus resistant Nephotettix cincticeps: Preparation of a test preparation:

Solvent: 'Xylene 3Gew parts V

Emulsifier: polyoxyethylene alkyl 1 part by weight

phenyl ether

To prepare a suitable 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:

To rice plants of about 10 cm in height, each planted in 12-cm diameter pots, 10 ml of the water-diluted, predetermined-active-concentration solutions of each of the active compounds prepared as indicated above were sprayed. The sprayed chemical was allowed to dry and placed over the rice plantations was a wire basket 7 cm in diameter and 14 cm in height, under which 30 adult female specimens of Nephotettix cincticeps resistant to organophosphorus agents were exposed. 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

 The results are shown in Table 5.

Table 5

Connection no.

Active substance concentration (ppm)

Extermination ratio (%)

13 '14 22 24 29 '95 97

100 100 100 100 100 100 100 100 100

comparison - 40 65 A-1 40 55 BI

Annotation:

1) The connection numbers are the same as stated above.

2) Comparative Compounds A-1 and B-1 are the corresponding compounds described above having the following formulas:

(A-I)

(BI)

For example, in addition to the compounds exemplified in Example 17, Compound Nos. 48, 49, 50, 51, 55, 96 and 98 also showed excellent insecticidal effects in the same test as in Example 17.

-27- 750

Example 18 (Biological Test) Lantern Test

Test methods:

An aqueous dilution having a predetermined concentration of the active compound prepared as in Example 17 was sprayed on about 10 cm high rice plants grown in pots with a diameter of 12 cm in an amount of 10 ml per pot. The sprayed chemical was allowed to dry and a wire basket of 7cm diameter and 14cm height was placed over the rice plants. 30 adult female specimens of Nilaparvata lugens Stal. of a strain showing resistance to organophosphorus agents were exposed under the wire basket. The pots were stored in a constant temperature room and 2 days later the number of dead insects was determined. The annihilation ratio was calculated afterwards.

In the same way, the destruction ratio of Sogatellafurcifera Horvath and organophosphorus resistant Laodelphaxstriatella traps was calculated

 These results are shown in Table 6.

Table 6

Compound No. Active substance concentration (ppm) Exposure ratio (%) N. lugens L. striatellus S.furcifera

1 40

7 40

9 40

13 40

14 40 29 40 50 40 95 40 97 40

100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

comparison 40 50 40 40 A-1 40 30 30 30 B-1

Annotation:

1) The connection numbers are the same as stated above.

2) The comparative compounds A-1 and B-1 are the same as those indicated in the footnote of Table 5.

Example 19 (biological test)

Test against organophosphorus chemicals and carbamate chemicals resistant Myzodes persicae (green peach aphids):

Test methods:

Cultured green peach aphids showing resistance to organophosphorus chemicals and carbamate chemicals were exposed to eggplant (black elongated eggplant) seedlings about 20 cm high that had been grown in 15 cm unglazed pots (about 200 aphids each) Seedling). One day after exposure, an aqueous dilution prepared as in Example 17 of each of the active compounds at a predetermined concentration was sprayed onto 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. The results are shown in Table 7.

Table 7

-28- 750

Connection no.

Active substance concentration (ppm)

Extermination ratio (%)

1 9 13 14 25 30 95 97

200 200 200 200 200 200 200 200

100 100 100 100 100 100 100 100

Comparison A-1

B-1

1000 200

1000 200

80 30 60 10

E stox (commercial product)

1000 200

100 20

Annotation:

1) The connection numbers and the comparison compounds A-1 and B-1 are the same as mentioned above.

2) Estox: S-2-ethylsulfinyl-i-methylethyl dimethyl phosphorothiolate (45% emulsifiable concentrate).

Claims (4)

-1- 750 98 Invention claim: 1. Insecticidal agent, characterized by a content of at least one nitromethylene derivative of the formula: H in the R denotes a hydrogen atom or a lower alkyl group, X is halogen, lower alkyl, lower alkoxy, lower alkylthio, lower alkylsulfinyl, lower alkylsulfonyl, lower alkenyl, lower alkynyl, aryl Group, an aryloxy group which may be optionally substituted by a halogen atom, an arylthio group which may be optionally substituted by a halogen atom, or an aralkyl group, I stands for 1,2,3 or 4, m stands for 2,3, or 4 and η is 0,1,2 or 3, or salt thereof, in addition to extenders and / or surfactants. 2. A method for controlling insects, characterized by allowing nitromethylene derivatives of the formula (I) to act on insects or their habitat. 3. Use of nitromethylene derivatives of the formula (I), characterized in that they are used for controlling insects. 4. A process for the preparation of insecticidal agents, characterized by mixing nitromethylene derivatives of the formula (I) with extenders and / or surface-active agents.