JPH0672138B2 - Novel aminoalkanethiols and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel aminoalkanethiols, which are intermediates for producing insecticidal nitromethylene derivatives, and a process for producing the same.

[0002]

2. Description of the Related Art Japanese Unexamined Patent Application Publication No. 59-196
For the proposal of No. 877, the following formula:

[0003]

[Chemical 5]

It is described that the thiazolidine derivative represented by the formula (A) has the antitumor activity for gastrointestinal ulcer. Then, At a formula (A), Ar is 2-furyl, phenyl, naphthyl or pyridyl group [these optionally one or more C ₁ ~ ₄ alkyl, C ₁ ~ ₆ alkoxy, halogen -C ₁ - ₄ alkoxy,
By a di- or trihalomethyl, hydroxy and / or nitro group or a formula

[0005]

[Chemical 6]

, Which may be substituted by
Y = indicating nitrogen or CH, and when Y = nitrogen, Z = cyano or carbamoyl; when Y = CH, Z =
It is a nitro group. And in the specification, for example, 2-cyanoimino-3- (6-methyl-
2-pyridylmethyl) -thiazolidine, 3-benzyl-
2-Nitromethylene-thiazolidine is described.

[0007]

[Chemical 7]

However, as is clear from the above definition of Ar, this proposal includes a portion corresponding to the Ar specified in the compound of the formula (I).

[0009]

[Chemical 8]

Compounds in which (X is a halogen atom and 1 is 1, 2, 3 or 4) may not be included, and the presence of such compounds, as well as the insecticidal activity, is not mentioned in the proposal at all. It has not been suggested.

[0011]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The inventors of the present invention have studied the nitromethylene derivative and its insecticidal activity, succeeded in synthesizing an insecticidal nitromethylene derivative of the following formula (I), and proposed it separately. did.

General formula

[0013]

[Chemical 9]

In the formula, R represents a hydrogen atom or an alkyl group, X represents a halogen atom, l represents 1, 2, 3 or 4, and m represents 2, 3 or 4.

The compound of the above formula (I) can be represented, for example, by the general formula:

[0016]

[Chemical 10]

Wherein R, X, l and m are the same as defined above, and a compound of the general formula

[0018]

[Chemical 11]

In the formula, R'represents a lower alkyl group or a benzyl group, or two R'in combination represent a C ₂ or lower alkylene group, which together with an adjacent sulfur atom form a ring. Or may be obtained by reacting with a compound represented by

The above-mentioned aminoalkanethiols of the formula (II) are novel compounds which have not been described in the publicly known documents and the present invention relates to the compounds. The compound of the general formula (II) can be produced by the following method, and the present invention also relates to the production method.

Production method : -General formula:

[0022]

[Chemical 12]

In the formula, R, X and l are the same as defined above, and a compound represented by the general formula:

[0024]

[Image Omitted] H ₂ N- (CH ₂ ) _m- SH (V) In the formula, m is the same as the above, and a reduction reaction is then carried out. A method for producing a compound of formula (II).

In addition to their strong insecticidal activity, the compounds of formula (I) are pests resistant to these insecticides resulting from the use of organophosphorus and carbamate insecticides for many years, in particular: It shows a remarkable controlling effect on puncture-absorptive pests typified by Hemiptera, such as aphids, planthoppers, leafhoppers and the like.

The compound of the general formula (II) of the present invention, which is an intermediate for producing the compound of the general formula (I), is a novel compound which has never been described in any prior art document, As described above, the compound is useful as an intermediate for the production of the compound of general formula (I) which is industrially useful.

In the general formula (II) of the compound of the present invention,
Preferably, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents fluoro, chloro or bromine, and l
Represents 1 or 2, and m represents 2 or 3.

Further, in the general formula (II), particularly preferably, R represents a hydrogen atom or a methyl group, X represents fluoro, chloro or bromo, l represents 1, and m represents 2 or 3. Show.

In addition to the above preferred definitions, in the general formula (II), most preferably, the bonding position of the pyridine ring is the 3-position or 4-position. However, here, the 3-position indicates the same position as the 5-position of the pyridine ring, and therefore, the 3-position and the 5-position are synonymous with each other from above the bonding position of the pyridine ring.

Specific examples of the compound of the general formula (II) include: N- (2-chloro-5-pyridylmethyl)
2-aminoethanethiol, N- (2-chloro-5-pyridylmethyl) 3-aminopropanethiol, N- (2
-Bromo-5-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-chloro-5-pyridyl) ethyl] 2-aminoethanethiol, N- (2,3-dichloro-5) -Pyridylmethyl) 2-aminoethanethiol,
N- (3-chloro-2-fluoro-5-pyridylmethyl) 2-aminoethanethiol, N- (2-chloro-4
-Pyridylmethyl) 2-aminoethanethiol, N-
(3-Chloro-2-pyridylmethyl) 2-aminoethanethiol, N- (5-chloro-2-pyridylmethyl) 3
-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-
(5-chloro-3-pyridylmethyl) 3-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
Examples include -pyridyl) propyl] 2-aminoethanethiol and the like.

A method for producing the above-exemplified compound of the general formula (II) is shown by the following reaction formula.

[0032]

[Chemical 14]

(In the formula, R, X, l and m are the same as above.) In the above-mentioned production method, for example, when 6-chloronicotinaldehyde and 3-aminopropanethiol are used as raw materials, they are shown below. It is represented by the reaction formula.

[0034]

[Chemical 15]

The compounds of the general formula (IV) include both known and novel compounds. Specific examples thereof include 6-chloronicotinaldehyde, 6-bromonicotinaldehyde, 6-fluoronicotinaldehyde and 5
-Acetyl-2-chloropyridine, 5,6-dichloronicotinaldehyde, 5-chloro-6-fluoronicotinaldehyde, 2-chloro-4-pyridinecarboxaldehyde, 3-chloro-2-pyridinecarboxaldehyde, 3,
5-dichloro-2-pyridinecarboxaldehyde, 5-fluoro-2-pyridinecarboxaldehyde, 6-bromo-
2-pyridinecarbaldehyde, 2-chloronicotinaldehyde, 5-chloronicotinaldehyde, 5-bromonicotinaldehyde, 5-fluoronicotinaldehyde, 5-acetyl-2-fluoropyridine, 4,6-dichloronicotinaldehyde, 4,6 -Dibromonicotinaldehyde, 2,6-difluoro-4-pyridinecarboxaldehyde, 2-fluoro-4-pyridinecarboxaldehyde, 2,6-dibromo-4-pyridinecarboxaldehyde, 5-bromo-6-fluoronicotinaldehyde, 6
Examples include -chloro-5-fluoronicotinaldehyde and 2-chloro-5-propionylpyridine.

The above-exemplified compounds of the general formula (IV) can be synthesized by various known methods. Org. Ch
em. 26, 4912-4914,
It can be synthesized by an ozonolysis reaction of vinylpyridines, and as described in British Patent No. 2,002,368,
6-chloronicotinaldehyde can be synthesized from 2-chloro-5-pyridylcarbonitrile. Further, generally, a reaction of reducing the corresponding pyridinecarboxylic acid and its derivative into an aldehyde by a conventional method (Org.Reation, Vol. 8, 218-257).
The aldehyde can be easily synthesized by utilizing

The compounds of the above-mentioned general formula (V) can be produced by publicly known publications prior to the filing date of the present application, such as J. Org. Chem. , 27
Vol. 4712-4713, and specific examples thereof include 2-aminoethanethiol and 3-aminopropanethiol.

The above manufacturing method is described in J. Org. Chem. , 2
It can be carried out by a method similar to the method described in Volume 7, pages 2452 to 2457 and pages 4712 to 4713.

Then, in the first step of the reaction, the compound of the general formula (IV) is reacted with the compound of the general formula (V) in the presence of an inert solvent such as benzene. It is carried out by synthesizing an intermediate product of a thiazolidine or tetrahydrothiazine derivative, and then reducing it with an exemplary reducing agent such as sodium borohydride, lithium aluminum hydride, aluminum borohydride, potassium borohydride and the like. be able to.

In carrying out the above-mentioned reaction, the thiazolidine or tetrahydrothiazine derivative as an intermediate product is subjected to distillation under reduced pressure, for example, at about 1 mmHg and about 50 to 80 ° C. to distill off the volatiles accompanying the first step reaction. Although it can be obtained, it can also be directly reduced without isolation.

The insecticidal nitromethylene derivative of the general formula (I) prepared from the compound of the general formula (II) of the present invention is
It exerts an accurate control effect against harmful insects without giving any phytotoxicity to cultivated plants. Further, the compound can be used for controlling a wide variety of pests, harmful sucking insects, biting insects and other plant parasitic pests, storage pests, sanitary pests and the like, and can be applied for exterminating and eradicating them.

Examples of such pests include the following pests. Insects include pests of the order Coleoptera, for example, Callosobruchus chi
nensis), weevil (Sitophilus zeamais), stag beetle (Tribolium castaneum), red-spotted beetle (Epilachna vigintioctomaculata), red-spotted beetle (Agriotes fuscicollis), black-spotted beetle cup (Anomala ru), Anomala ru
(Leptinotarsa decemkineata), Diabroteika (Diabro
tica spp.), pine woodpecker (Monochamus alter)
natus), rice weevil (Lissorhoptrus oryzophilu)
s), the flat beetle (Lyctus bruneus); Lepidoptera,
For example, the gypsy moth (Lymantria dispar), the plum bug
(Malacosoma neustria), Caterpillars (Pieris rapae), Lotus Monk Spodoptera (Spodoptera litura), Spodoptera litura (Mamestra)
brassicae), Nikameiyu (Chilo suppressalis),
Red-tailed squirrel (Pyrausta nubilalis), Red-spotted moth (Ephestia cautella), Red-tailed squirrel (Adoxophye)
s orana), codling moth (Carpocapsa pomonella), cabbage moth (Agrotis fucosa), honey moth (Galleria mellon)
ella), diamondback moth (Plutella maculipennis), citrus fruit moth (Phyllocnistis citrella); hemiptera, for example, leafhopper leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), stag beetle (Pseudoconya) (Pseudoconcus), Aphids, Myzus
persicae), apple aphid (Aphis pomi), cotton aphid (Aphis gossypii), rainbow radish aphid
(Rhopalosiphum pseudobrassicas), Nasi Gumbai (Ste
phanitis nashi), blue stink bug (Nazara spp.), bed bug (Cimex lectularius), whitefly whitefly (Tria)
leurodes vaporariorum), Psyllidae (Psylla spp.); Orthoptera, for example, German cockroach (Blatella germani)
ca), American cockroach (Periplaneta americana), Kera
(Gryllotalpa africana), grasshopper (Locusta migratoria
migratoriodes); Isoptera, for example, Termite
(Deucotermes speratus), Termite (Coptotermes)
formosanus); Diptera, such as the housefly (Musca dom)
estica), Aedes aegypti, Aedes aegypti
(Hylemia platura), Culex pipiens, Culex pipiens, Anopheles slnensis, Culex tritaeniorhynchus, and the like.

Furthermore, in the field of veterinary medicine, the novel compounds of the present invention are effective when used against various harmful animal parasites (internal and ectoparasites), such as insects and helminths. . Examples of such animal parasites include the following pests.

Examples of insects include the horsefly (Gastro)
philus spp.), fly (Stomoxys spp.), hazel (Tr)
ichodectes spp.), tortoises (Rhodnius spp.), dog fleas (Ctenocephalides canis) and the like.

Next, the contents of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

[0046]

【Example】

 Example 1

[0047]

[Chemical 16]

(Compound No. II-1) A solution of 6-chloronicotinaldehyde (14.2 g), 2-aminoethanethiol (7.7 g) and benzene (80 ml) was added while removing azeotropic water. Heat and stir for 5 hours. After completion of the reaction, benzene was distilled off under reduced pressure, and further 1 mmH
g, if the volatile matter was taken at 70 ° C., the residue was 2- (2-
Chloro-5-pyridyl) thiazolidine (18 g) is obtained. The 2- (2-chloro-5-pyridyl) thiazolidine (10 g) is then dissolved in 100 ml of ethanol, sodium borohydride is added and the mixture is heated slowly with stirring, followed by reflux for 1 hour. After ethanol is distilled off under reduced pressure, chloroform is added to the residue, the insoluble matter is filtered off, and the chloroform layer is washed with water. After the chloroform layer was dehydrated, chloroform was distilled off under reduced pressure to obtain the desired N- (2-chloro-5-pyridylmethyl) 2-aminoethanethiol (8.3 g).

N _D ²⁴ 1.5917 Compound No. ^{24 was} prepared by the same method as in Example 1 above. II-
2 is shown below.

[0050]

[Chemical 17]

(No. II-2) N- (2-chloro-5-pyridylmethyl) 3-aminopropanethiol (n _D ²² 1.5890) The same procedure as in Example 1 above is shown in Table 1 below. Compounds of general formula (II) other than those exemplified above are shown.

[0052]

[Table 1]

[0053]

[Table 2]

Synthesis Reference Example (Synthesis Example of Compound of Formula (I))

[0055]

[Chemical 18]

(Compound No. 1) N- (2-chloro-5)
-Pyridylmethyl) 3-aminopropanethiol (4.
A mixture of 3 g), 1-nitro-2,2-bis (methylthio) ethylene (3.3 g) and ethanol (40 ml) is heated under reflux for 10 hours under a nitrogen stream. After the reaction, was distilled off to about _^2/3 volumes of ethanol at reduced pressure, ether was added in portions to the contents, to precipitate crystals. The crystals were collected by filtration and washed with a mixture of ethanol and ether to give yellow crystals of the desired product 3- (2-chloro-5-pyridylmethyl) 2-nitromethylenetetrahydro-2H-1,3-thiazine (1.3 g). ) Is obtained.

M. p. 164 to 166 ° C. Table 2 below shows insecticidal nitromethylene derivatives that can be synthesized by the same method as in the above synthesis reference example.

[0058]

[Table 3]

[0059]

[Table 4]

Example 2 (Biological test) Test against organic phosphorus-resistant leafhopper, preparation of reagent solution Solvent: 3 parts by weight of xylol Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether Prepare a formulation of a suitable active compound For this purpose, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the mixture was diluted with water to the given concentration.

Test method: To a rice plant having a plant height of about 10 cm planted in a pot having a diameter of 12 cm, 10 ml of a diluted solution of the active compound prepared above having a predetermined concentration was sprayed per pot. After the sprayed chemical solution was dried, a wire net with a diameter of 7 cm and a height of 14 cm was covered, and 30 female adults of the leafhopper leafhopper, which is a strain that is resistant to the organophosphorus agent, were released in it and placed in a temperature-controlled room for 2 days to determine the number of dead insects. Insect kill rates were calculated.

The results are shown in Table 3 with a representative example.

[0063]

[Table 5]

[0064]

[Chemical 19]

Example 3 (Biological test) Test for planthoppers Test method: Plant height 10 cm planted in pot with diameter 12 cm
10 ml of a pot of a diluted solution of the active compound in water prepared in the same manner as in Example 2 was sprayed on the rice at the top.
After spraying the chemical solution, cover it with a wire net with a diameter of 7 cm and a height of 14 cm, release 30 female adult planthoppers of the strain resistant to the organophosphorus agent, and place them in a temperature-controlled room for 2 days to determine the number of dead insects. Insect kill rates were calculated.

In the same manner as the above method, the insecticidal rate for the sedge loach and the organophosphorus drug-resistant scutellaria baicalensis was calculated. The results are shown in Table 4 with a representative example.

[0067]

[Table 6]

Example 4 (Biological test) Test for organic phosphoric acid and carbamate-resistant peach aphid Test method: Height about 20c planted in a clay pot with a diameter of 15 cm
Approximately 200 heads of the organic phosphorus agent and carbamate-resistant peach aphid, which had been bred to the eggplant seedlings (genuine black eggplant) of m, were inoculated per seedling, and one day after the inoculation, the active compound prepared as in Example 4 was used. A sufficient amount of a diluted solution of water having a predetermined concentration was sprayed using a spray gun. After spraying, leave it in a greenhouse at 28 ° C,
The insecticidal rate was calculated 24 hours after the application. The test was repeated twice.

The results are shown in Table 5 with a representative example.

[0070]

[Table 7]

Claims (4)

[Claims] 1. A general formula: In the formula, R represents a hydrogen atom or an alkyl group, X represents a halogen atom, l represents 1, 2, 3 or 4, and m represents 2, 3 or 4.
A novel aminoalkanethiol represented by 2. The compound according to claim 1, wherein R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is fluoro, chlorine or bromine, 1 is 1 or 2, and m is 2 or 3. . 3. The compound according to claim 1, wherein R is a hydrogen atom or a methyl group, X is fluoro, chloro or bromo, l is 1 and m is 2 or 3. 4. A general formula: In the formula, R represents a hydrogen atom or an alkyl group, X represents a halogen atom, and l represents 1, 2, 3 or 4
And a compound represented by the general formula: H ₂ N- (CH ₂ ) _m -SH, wherein m is 2, 3 or 4, and then reacted. General formula characterized by carrying out a reduction reaction: In the formula, R, X, 1 and m are the same as defined above, and a method for producing the compound.