JPH0649699B2 - Nitromethylene derivative, its manufacturing method and insecticide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel nitromethylene derivatives, processes for their preparation and insecticides.

More specifically, the present invention relates to a nitromethylene derivative represented by the following formula (I).

General formula: In the formula, R represents a hydrogen atom or an alkyl group, X represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylsulfinyl group, an alkenyl group or an alkynyl group, wherein these groups are substituted with halogen. Or a halogen atom, a nitro group, a cyano group, an aryl group, an aralkyl group, an alkoxyalkyl group or an aryloxy group, 1 represents 0, 1, 2, 3 or 4, and m represents 2, 3 or 4, and in the above formula, the bonding position of the pyridine ring is the 3-position or 4-position, provided that when l is 1, X does not represent a halogen atom, and l is 2, 3 or Alternatively, when X is 4, all Xs do not simultaneously represent a halogen atom.

The compound of the above general formula (I) can be produced by the following method, and the present invention also relates to the method.

Manufacturing method a):-General formula In the formula, R, X, l and m are the same as defined above, and a compound represented by the general formula: Wherein R ′ represents a lower alkyl group or a benzyl group, or two R ′ together represent a C ₂ or higher lower alkylene group, which may form a ring with the adjacent sulfur atom, A method for producing a nitromethylene derivative represented by the general formula (I), which comprises reacting with a compound represented by:

Production method b):-General formula: In the formula, m is the same as the above, and a compound represented by the following general formula: In the formula, R, X and l are the same as above, and Hal is a halogen atom. The method for producing the nitromethylene derivative of the general formula (I) is characterized by reacting with a compound represented by the formula:

The present invention also relates to an insecticide containing the nitromethylene derivative represented by the general formula (I) as an active ingredient.

In the proposal of Japanese Patent Laid-Open No. 59-196877 known before the filing date of the present application, the following formula: It is described that the compound of formula (A) has antitumor activity for gastrointestinal ulcer. In the formula (A), Ar is a 2-furyl, phenyl, naphthyl or pyridyl group [these are optionally one or more C _1-4 alkyl, C
_1-6 alkoxy, halogen-C _1-4 alkoxy, di- or trihalomethyl, hydroxy and / or nitro groups or of the formula Optionally substituted by Y], Y = nitrogen or CH, and when Y = nitrogen, Z = cyano or carbamoyl; and when Y = CH, Z = nitro group. And in the specification, for example, 2-cyanoimino-3- (6-
Methyl-2-pyridylmethyl) -thiazolidine, 3-benzyl-2-nitromethylene-thiazolidine are described.

The definition of the group Ar in the compound of the formula (A) in the proposal of the above-mentioned JP-A-59-196877 and the portion corresponding to the group Ar specified in the compound of the formula (I) of the present invention. As is clear from the definition of the above, in the compound of formula (I) of the present invention, some of the compounds can be included in the general concept of the above-mentioned proposed general formula (A).

However, the proposal does not specifically describe any compound overlapping with the compound of formula (I) of the present invention.

The present inventors have conducted research on nitromethylene derivatives and their insecticidal activity.

As a result, some compounds which can be included in the general concept of the general formula (A) proposed in JP-A-59-196877 but which are not specifically described in the proposal are included in the formula (I). The invention compound was successfully synthesized. And, the compound represented by the formula (I), which has not been described in the publicly known document, is extremely useful for solving a new technical problem completely different from the antitumor activity of controlling pests, which the proposal does not mention at all. It was discovered to be a compound. According to the study by the present inventors,
As shown for many of the example compounds in contrast to the analogous comparative compounds described in the above proposal, the compounds of formula (I)
The compound has an insecticidal activity and effect belonging to an activity completely different from the antitumor activity disclosed in the above proposal,
It was discovered to have a totally unexpected and extremely good effect.

Furthermore, in addition to the above-mentioned strong insecticidal activity, the compound of the formula (I) of the present invention is resistant to these insecticides resulting from the use of organophosphorus and carbamate insecticides over the years. It has been discovered that pests, particularly puncture-absorptive pests represented by Hemiptera, such as aphids, planthoppers, leafhoppers, etc., exhibit a remarkable control effect.

Therefore, an object of the present invention is to provide a novel nitromethylene derivative represented by the general formula (I), a process for producing the same, and use thereof as an insecticide.

These and many other objects and advantages of the present invention will become more apparent from the description below.

In the general formula (I) of the compound of the present invention, preferably R
Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. Alkylsulfonyl group, C1-C4 alkylsulfinyl group, C2-C3 alkenyl group or C2-C3
Alkynyl group, wherein these groups may be substituted with 1 to 3 fluoro or chloro, or a fluoro atom, a chloro atom, a bromine atom, a nitro group, a cyano group, an aryl group having 6 to 10 carbon atoms, a carbon atom An aralkyl group having 7 to 8 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms or an aryloxy group having 6 to 10 carbon atoms, 1 represents 0, 1 or 2, and m represents 2 or 3. When l is 1, X does not represent a fluoro atom, a chloro atom or a bromine atom, and when 1 is 2, two Xs are fluor atom, chloro atom and / or bromine atom at the same time. Is not shown.

Furthermore, in the general formula (I), particularly preferably, R
Represents a hydrogen atom or a methyl group, X represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxy group, a methylthio group, a methylsulfonyl group, a methylsulfinyl group, a vinyl group, an allyl group, an ethynyl group, Propargyl group,
A methoxymethyl group, a 2-ethoxyethyl group, a trifluoromethyl group, a nitro group, a cyano group, a difluoromethoxy group, a trifluoromethoxy group, a chlorodifluoromethylthio group or a trifluoromethylthio group, and l is 0
Or 1 and m represents 2 or 3.

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

Then, as specific examples of the compound of the general formula (I) of the present invention, the following compounds can be specifically exemplified. That is, 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.

The compound of the general formula (I) of the present invention can be produced, for example, by the following method.

Manufacturing method a): (In the formula, R, X, l, and m are the same as above.) In the above production method a), for example, N- (2
When -methyl-5-pyridylmethyl) 3-aminopropanethiol and 1-nitro-2,2-bis (methylthio) ethylene are used, they are represented by the reaction formulas shown below.

Manufacturing method b):- (In the formula, R, X, l and m are the same as above.) In the above production method b), for example, when 2-nitromethylene thiazolidine and 3-picolyl chloride are used as raw materials, the reaction formulas shown below. It is represented by.

In the above-mentioned production method a), the compound of the general formula (II) which is a raw material means one based on the above definition of each of R, X, l and m, and preferably R, X, l and m are as described above. ,
Synonymous with the preferred definition.

The compound of the general formula (II) is a compound including both known and novel compounds. Then, as specific examples thereof, for example, N- (3-pyridylmethyl) 2-aminoethanethiol, N- (3-pyridylmethyl) 3-aminopropanethiol, N- (4-pyridylmethyl) 2-aminoethane Thiol, N- (4-pyridylmethyl) 3-aminopropanethiol, N- (2-methyl-5-pyridylmethyl) 2-aminoethanethiol, N- (2-methyl-5-pyridylmethyl) 3-aminopropane Thiol, 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-methyl Thio-5-pyridylmethyl) 2-amino-propanethiol, 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-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-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) -5-pyridylmethyl] 3-aminopropanethiol, 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 Examples include-[2- (2,2-dichlorovinyl) -5-pyridylmethyl) 2-aminoethanethiol and the like.

The compound of the general formula (II) exemplified above can be produced by the following method.

Manufacturing method c): (In the formula, R, X, l, and m are the same as above.) A typical example of the above production method c) is shown below, and the above production method will be specifically described.

The compound of the general formula (VI) can be easily produced by a known method, and specific examples thereof include nicotinaldehyde, 4-pyridinecarbaldehyde, 6-methylnicotinaldehyde, 6-ethylnicotinaldehyde, 6-allyl. Nicotinaldehyde, 6-propargyl nicotinaldehyde, 6-methoxynicotinaldehyde, 6-methylthionicotinaldehyde, 6-methylsulfonylnicotinaldehyde, 6-chloro-5-methylnicotinaldehyde, 3-acetylpyridine, 6-trifluoromethylnicotinaldehyde , 6-nitronicotinaldehyde, 6-cyanonicotinaldehyde, 6-methylsulfinylnicotinaldehyde, 6-phenylnicotinaldehyde, 6-benzylnicotinaldehyde, 6-phenoxyni Cotinaldehyde, 6- (2-ethoxyethyl) nicotinaldehyde, 6-trichloromethylnicotinaldehyde, 6-methoxymethylnicotinaldehyde, 6-difluoromethoxynicotinaldehyde, 6-trifluoromethoxynicotinaldehyde, 6- (2,2,2 2-trifluoroethoxy) nicotinaldehyde, 6-chlorodifluoromethylthionicotinaldehyde, 6-trifluoromethylthionicotinaldehyde, 6-difluoromethylnicotinaldehyde, 6-trifluoromethylsulfonylnicotinaldehyde, 6-trifluoromethylsulfinylnicotine Examples thereof include aldehydes, 6- (2,2-dichlorovinyl) nicotinaldehyde, and the like.

The compound of the general formula (VI) exemplified above is, for example, J.Org.Che.
m., 26, 4912-4914, it can be synthesized by an ozonolysis reaction.
Mention may be made of methylnicotinaldehyde.

Further, more generally, an aldehyde is easily synthesized by utilizing a reaction (Org. Reacton, Vol. 8, pages 218 to 257) for reducing the corresponding pyridinecarboxylic acid and its derivative into an aldehyde by a conventional method. be able to.

The compound of the general formula (VII) is a known publication before the filing date of the present application, for example, J. Org. Chem., Vol. 27, 4712 to 471.
It is the compound described on page 3, and specific examples thereof include 2-aminoethanethiol and 3-aminopropanethiol.

The production method c) is described in J.Org.Chem., Vol. 27, 2452-2.
It can be carried out by a method similar to the method described on pages 457 and 4712 to 4713.

Then, as a first step of the reaction, thiazolidine is obtained by reacting the compound of general formula (VI) with the compound of general formula (VII) in the presence of an inert solvent such as benzene. Alternatively, an intermediate product of a tetrahydrothiazine derivative is synthesized, and then an exemplary reducing agent such as sodium borohydride, lithium aluminum hydride, aluminum borohydride, potassium borohydride, etc.,
It can be done by reducing.

In carrying out the above reaction, the intermediate thiazolidine or tetrahydrothiazine derivative is treated under reduced pressure, eg about 1
It can be obtained by distilling off the volatiles accompanying the first step reaction at mmHg, about 50 to 80 ° C., but it can also be directly reduced without isolation.

The compound of the general formula (III), which is a raw material in the production method a), is a known compound, for example, Chem. Ber., 1
Vol. 00, pp. 591-604. And
Specific examples thereof include 1-nitro-2,2-bis (methylthio) ethylene, 1-nitro-2,2-bis (ethylthio) ethylene, 1-nitro-2,2-bis (benzylthio) ethylene, 2-nitromethylene-1,3-dithiolane etc. can be illustrated.

In the above production method (b), the compound of the general formula (IV) means a compound based on the above definition of m. In the general formula (IV), m preferably has the same meaning as defined above.

According to the present invention, the starting compound of the general formula (IV) is
Compounds described in West German Patent Publication No. 2,734,070 and US Pat. No. 3,933,809. Then, specific examples thereof include 2-nitromethylene thiazolidine and 2-nitromethylene tetrahydro-2H-1,3-thiazine.

Similarly, the compound of the general formula (V), which is a raw material in the production method (b), means one based on the above definition of each of X, l and Hal, and preferably X and l have the same meanings as defined above. And Hal preferably represents chlor or bromine.

According to the present invention, the starting compound of the general formula (V) is
It can be synthesized by a known method.

Specific examples thereof include, for example, 3-picolyl chloride, 4-picolyl chloride, 2-methyl-5-pyridylmethyl chloride, 2-ethyl-5-pyridylmethyl chloride, 2-allyl-5-pyridylmethyl chloride, 2-Propargyl-5-pyridylmethyl chloride, 2-methoxy-5-pyridylmethyl chloride, 2-methylthio-5-pyridylmethyl chloride, 2-methylsulfonyl-5-pyridylmethyl chloride, 2-chloro-3-methyl-5 -Pyridylmethyl chloride, 1- (3-pyridyl) ethyl chloride, 2-trifluoromethyl-5-pyridylmethyl chloride, 2-nitro-5-pyridylmethyl chloride, 2-cyano-5-pyridylmethyl chloride, 2-methyl Sulfinyl-5-pyridylme L-chloride, 2-phenyl-5-pyridylmethyl chloride, 2-benzyl-5-pyridylmethyl chloride, 2-phenoxy-5-pyridylmethyl chloride, 2-trichloromethyl-5-pyridylmethyl chloride, 2- (2-ethoxy) Ethyl) -5-pyridylmethyl chloride, 2-methoxymethyl-5-pyridylmethyl chloride, 2-difluoromethoxy-5-pyridylmethyl chloride, 2-trifluoromethoxy-5-pyridylmethyl chloride, 2- (2,2, 2-trifluoroethoxy) -5-pyridylmethyl chloride, 2-chlorodifluoromethylthio-5-pyridylmethyl chloride, 2-trifluoromethylthio-5-pyridylmethyl chloride, 2-difluoromethyl-5-pyridylmethyl chloride And 2-trifluoromethylsulfonyl-5-pyridylmethyl chloride, 2-trifluoromethylsulfinyl-5-pyridylmethyl chloride, 2- (2,2-dichlorovinyl) -5-pyridylmethyl chloride and the like. It is also possible to use bromide form instead of chloride form.

The halides exemplified above can be easily synthesized by chlorinating the corresponding alcohol with thionyl chloride.

In carrying out the process (a) mentioned above, use may be made, as suitable diluent, of any inert solvent.

Examples of such diluents are water; aliphatic, cycloaliphatic 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 and trichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide, dioxane,
Tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl-iso-propyl ketone, methyl-iso-butyl ketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol Ester, for example, ethyl acetate, amyl acetate; acid amide, for example, dimethylformamide, dimethylacetamide; sulfone, sulfoxide, for example, dimethylsulfoxide, sulfolane; and base, for example, pyridine.

The above method can be carried out within a wide temperature range. Generally it can be carried out between about -20 ° C and the boiling point of the mixture, preferably between about 0 and about 100 ° C. Also, it is desirable to carry out the reaction under normal pressure,
It is also possible to operate under pressure or reduced pressure.

In carrying out the above production method, for example, the compound represented by the general formula (II)
1 mole of the compound of formula (III), equimolar amount to about 1.2 times molar amount, preferably equimolar amount to about 1.1 times molar amount, inert solvent such as alcohol (eg methanol, ethanol) solvent Among them, the desired novel compound of the general formula (I) can be obtained by refluxing under a nitrogen gas stream.

In carrying out the above production method (b), as a suitable diluent,
Among the examples of the production method (a), water and all inert organic solvents except alcohols can be mentioned, and further examples of the base include hydrides such as sodium hydride and potassium hydride.

The above-mentioned production method (b) can be carried out within a wide temperature range, generally between about 0 ° C and about 100 ° C, preferably between about 10 ° C and about 50 ° C.

Further, the reaction is preferably carried out under normal pressure, but it may be carried out under pressure or reduced pressure.

In carrying out the above production method, for example, the compound represented by the general formula (IV)
As a base, sodium hydride is used in an amount of about 1.1 to 1.2 times, and the compound of the general formula (V) is used in an equimolar amount to about 1.2 times, and preferably an equimolar amount to 1 mol of the compound of.
By reacting about 1.1 times the molar amount in an inert solvent such as dimethylformamide, the desired compound of general formula (I)
Can be obtained. In the above production method, it is preferable in view of the reaction that the compound of the general formula (IV) is previously formed into a sodium salt form with sodium hydride. In addition, the reaction is carried out in a nitrogen gas atmosphere from the characteristics of sodium hydride. It is desirable to do it below.

The compound of the general formula (I) of the present invention can exist in the form of a salt, and examples of the salt include inorganic acid salts, sulfonic acid salts, organic acid salts, metal salts and the like. Therefore, in the present invention, the nitromethylene derivative of the formula (I) is a name including its salt form.

The active compounds of formula (I) according to the invention exhibit a strong insecticidal action. Therefore, they can be used as insecticides. Then, the active compound of formula (I) of the present invention exerts a proper controlling effect against harmful insects without giving phytotoxicity to cultivated plants. Further, the compound of the present invention 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. As insects, pests of the order Coleoptera, for example, adzuki bean weevil (Callosobruchus chinensis), weevil (Sitophilus zeamais), and peanut tribe (Triboli)
um castaneum), Epilachn
a vigitioc tomaculate), a vigitioc tomaculate)
riotes fuscicollis), Japanese beetle (Anomala rufocupre)
a), Colorado potato beetle (Leptinotarsa decemkinea
ta), diablotheca (Diabrotica spp.), pine wilt beetle (Monochamus alternatu), rice weevil (L)
issorhoptrus oryzophilus), Japanese beetle (Lyctus)
bruneus); Lepidoptera, for example, gypsy moth (Lymantria dispar), Ume beetle (Malacosam)
a neustria), caterpillar (Pieris rapae), Spodoptera litura (Spodoptera litura), Spodoptera litura (Mamestra brassica)
e), Nikameichiyu (Chilo suppressalis), Awanomeiga (Pyrausta nubilalis), Koadamadameiga (Ephestia)
cautella), Red-faced Monkfish (Adoxophyes orana), Codling moth (Carpocapsa pomonella), Kaburagaga (Agrotis)
fucosa), Honey honey (Galleria mellonella), diamondback moth
(Plutella maculipennis), mandarin orange moth (Phyllocn
istis citrella); Hemiptera, such as leafhoppers (Nephotettix cincticeps), brown planthoppers (Nilaparvata lugens), stag beetles (P)
seudococcus comstocki), the scale bug (Unaspis)
yanonensis), green peach aphid (Myzus persicae),
Apple Aphid (Aphis pomi), Cotton Aphid (Aphis pomi)
gossypii), Japanese radish aphid (Rhopalosiphum p.
seudobrassicas), Nasi Gumbai (Stephanitis nashi),
Blue bug (Nazara spp.), Bed bug (Cimex lectul)
arius), whitefly (Trialeurodes vapoparior)
um), Psyllidae (Psylla spp.); Orthoptera, for example, German cockroaches (Blatella germanica), American cockroaches (Periplaneta americana), kerula (Gryllotalpa africa)
na), locusts (Locusta migratoria migratoriodes); Isoptera, for example, Yamato termites (deucotermes speratus), house termites
(Coptotermes formosanus); Diptera, such as housefly (Musca domestica) and Aedes ae
gypti), Fly (Hylemia platura), Culex pipiens (Cule)
x pipiens), Chinese anopheles (Anopheles slnensis), Culex tritaeniorhynchus, and the like.

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

Examples of insects include a fly (Gastrophilus spp.) And a sand fly (Stomoxys spp.).
p.), halibut (Trichodectes spp.), and reed turtle (Rhodniu)
s spp.), dog flea (Ctenocephalides canis) and the like.

In the present invention, a substance having an insecticidal action against insects including all of them may be called an insecticide.

The active compound of formula (I) of the present invention can be made into a usual pharmaceutical form. And as such a form, a liquid preparation, an emulsion, a suspension, a powder, a foam, a paste, a granule, an aerosol, an active compound infiltrating-natural and synthetic product, a microcapsule, a seed coating, and a preparation provided with a combustion device. (For example, as a combustion device, fumigation and fumigation cartridges, cans and coils), and ULV (cold mist)
st), warm mist].

These preparations can be manufactured by a known method. Such a process comprises, for example, applying an active compound to a developing agent, ie a liquid diluent; a liquefied gas diluent; a solid diluent, or a carrier, optionally a surfactant, ie an emulsifier and / or dispersant and And / or by using a foam forming agent and mixing. If water is used as the spreading agent, organic solvents, for example, can also be used as auxiliary solvents.

Liquid diluents or carriers generally include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chloride, chlorides). Methylene etc.), aliphatic hydrocarbons [eg cyclohexane etc., paraffins (eg mineral oil fraction etc.)], alcohols (eg butanol, glycol and their ethers, esters etc.), ketones (eg acetone,
Mention may also be made of methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), strongly polar solvents (eg dimethylformamide, dimethylsulfoxide etc.) and water.

The liquefied gas diluent or carrier is a gas at room temperature and atmospheric pressure, examples of which include aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, and halogenated hydrocarbons.

As the solid diluent, soil natural minerals (for example, kaolin, clay, talc, chiyoke, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.) Can be mentioned.

Solid carriers for granules include crushed and fractionated rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic and organic powders, and fine particles or organic materials ( For example, garlic, coconut fruit, corn cob, tobacco stem and the like) can be mentioned.

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (eg, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate, aryl sulfone). Acid salt, etc.)], and albumin hydrolysis products.

Dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Adhesives may also be used in the formulation (powder, granules, emulsions), such adhesives including carboxymethyl cellulose and natural and synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinyl acetate). You can

Colorants can also be used, such as inorganic pigments (for example iron oxide, titanium oxide and Prussian blue) and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and also iron. , Manganese, boron, copper, cobalt, molybdenum, salts thereof such as zinc.

The formulation may generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight, of the active ingredient.

The formula (I) active compounds of the present invention are in their commercially useful formulations and use forms prepared according to these formulations other active compounds, such as insecticides, baits, fungicides,
It can also be present as a mixture with acaricides, centrifuges, fungicides, growth regulators or herbicides. Here, examples of the insecticide include organic phosphorus agents, carbamate agents, carboxylate agents, chlorinated hydrocarbon agents, and insecticidal substances produced by microorganisms.

Furthermore, the active compound of formula (I) of the present invention can be present as a mixture with a synergist, and such preparations and use forms can be those which are commercially useful. The synergist is a compound which amplifies the action of the active compound, which need not be active in and of itself.

The content of the active compounds of the formula (I) according to the invention in the commercially useful use forms can be varied within wide limits.

Useful concentrations of the active compounds of formula (I) according to the invention are, for example:
0.0000001 to 100% by weight, preferably 0.000
It is 1 to 1% by weight.

The compound of the formula (I) of the present invention can be used in a usual method suitable for the use form.

When used as hygiene pests, pests on stored materials, the active compounds are notable for their good stability against alkali on lime substances, as well as their excellent residual efficacy in wood and soil. Has been done.

Next, the contents of the present invention will be specifically described with reference to Examples.
The present invention should not be limited to this.

Manufacturing Example: -Example 1 (Compound No. 1) A mixture of N- (3-pyridylmethyl) 3-aminopropanethiol (1.8 g), 1-nitro-2,2-bis (methylthio) ethylene (1.7 g) and ethanol (40 m) was added with nitrogen. Heat under reflux for 5 hours. After the reaction, about 2/3 volume of ethanol is distilled off under reduced pressure, and ether is gradually added to the contents to precipitate crystals. The crystals are collected and washed with a mixed solution of ethanol and ether to obtain the desired 3- (3-pyridylmethyl) 2-nitromethylenetetrahydro-2H-1,3-thiazine (1.2 g).

mp. 143-146 ° C Example 2 (Compound No. 2) 2-Nitromethylene thiazolidine (2.9 g) was suspended in dry acetonitrile (30 m), 60% sodium hydride (0.9 g) was added with nitrogen under a nitrogen stream, and then hydrogen was generated at room temperature. Stir until no more. Then, a solution of 3-picolyl chloride (3.2 g) in 5 m of dry acetonitrile is added at room temperature, the contents are stirred at room temperature for 3 hours, acetonitrile is distilled off under reduced pressure, dichloromethane is added to the residue, and the mixture is washed with water. Dichloromethane was distilled off from the dichloromethane layer, and the oily residue was purified by column chromatography to give the desired 3- (3-pyridinemethyl) 2-
Nitromethylene thiazolidine (0.5 g) is obtained.

mp. 96 to 100 ° C. Compounds of the general formula (I) of the present invention synthesized by the same method as in Example 1 or 2 are shown in Table 1 below.

Reference example- (Compound No. II-6) 6-methylnicotinaldehyde (12.1 g), 3-aminopropanethiol (9.1 g), and benzene (120 m
The solution of 1) is stirred and refluxed for 5 hours while removing azeotropic water. After completion of the reaction, benzene was distilled off under reduced pressure,
Further, if the volatile matter is collected at 1 mmHg and 70 ° C., 3-pyridyltetrahydrothiazine (16.5 g) is obtained as a residue. The 3-pyridyltetrahydrothiazine (10 g) is then dissolved in 100 m 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, insoluble materials are separated, and chloroform is washed with water. After dehydrating the chloroform layer, the chloroform was distilled off under reduced pressure to obtain the desired N- (3
-Pyridyl) 3-aminopropanethiol (6.2 g) is obtained.

▲ n ²⁰ _D ▼ 1.5733 Compound No. II-1 and No. II by the same method as the above reference example.
II-2 is shown below.

Table 2 below shows compounds of the general formula (II) other than those exemplified above by the same method as in the above reference example.

Biological test: -Comparative compound A-1: (Described in JP-A-59-196877) A-2: (Same as above) A-3: (Same as above) Example 3 (Biological test) Test against organic phosphorus agent-resistant green leafhoppers Preparation of reagent solution Solvent: 3 parts by weight of xylol Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether A formulation of a suitable active compound is prepared. 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 planted in a pot having a diameter of 12 cm and having a plant height of about 10 cm, 1 part of a water-diluted solution of a predetermined concentration of the active compound prepared as described above was used.
Sprayed 10m per pot. After the sprayed drug solution was dried, it was covered with a wire net with a diameter of 7 cm and a height of 14 cm, and 30 adult females of the leafhopper leafhopper, which is resistant to organophosphorus agents, were placed in it.
The insect was killed by leaving it on its head and placing it in a thermostatic chamber two days later to calculate the insecticidal rate.

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

Example 4 (Biological test) Test method for planthoppers Test method: To a rice plant having a plant height of about 10 cm planted in a pot having a diameter of 12 cm, a diluted solution of the active compound in water having a predetermined concentration prepared in the same manner as in Example 3 was used per pot. Sprayed 10m. After spraying the chemical solution, cover it with a wire net with a diameter of 7 cm and a height of 14 cm, and release 30 female adult planthoppers of the strain that are resistant to the organophosphorus agent, and place them in a temperature-controlled room for 2 days. Insect kill rates were calculated.

In the same manner as the above-mentioned method, the insecticidal rate for Sedro-loquan plant and organophosphorus-resistant Spodoptera frugiperda was calculated. The results are shown in Table 4 with a representative example.

Example 5 (Biological test) Organophosphorus agent and test for carbamate-resistant peach aphid Test method: Organophosphorus agent bred on eggplant seedlings (genuine long eggplant) having a height of about 20 cm planted in a clay pot with a diameter of 15 cm. , And about 200 head peach aphids resistant to carbamate per seedling, and one day after the inoculation, a sufficient amount of a water-diluted solution of a predetermined concentration of the active compound prepared as in Example 3 was sprayed using a spray gun. Sprayed. After spraying, it was left in a greenhouse at 28 ° C., and 24 hours after spraying, the insecticidal rate was calculated. The test was repeated twice.

The results are shown in Table 5 with representative examples.

Claims (11)

[Claims] 1. A general formula: In the formula, R represents a hydrogen atom or an alkyl group, X represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylsulfinyl group, an alkenyl group or an alkynyl group, wherein these groups are substituted with halogen. Or a halogen atom, a nitro group, a cyano group, an aryl group, an aralkyl group, an alkoxyalkyl group or an aryloxy group, 1 represents 0, 1, 2, 3 or 4, m represents 2, 3 or 4 and in the above formula, the bonding position of the pyridine ring is 3-position or 4-position, provided that when l is 1, X does not represent a halogen atom, and l is 2, 3 or A nitromethylene derivative represented by the formula (4) wherein all X's do not simultaneously represent a halogen atom. 2. R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, and carbon. An alkylsulfonyl group having 1 to 4 carbon atoms, an alkylsulfinyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 3 carbon atoms or an alkynyl group having 2 to 3 carbon atoms, wherein these groups are fluoro of 1 to 3 or It may be substituted with chloro, or a fluoro atom, a chloro atom, a bromine atom, a nitro group, a cyano group, an aryl group having 6 to 10 carbon atoms, and a carbon number 7
~ 8 aralkyl groups, total C2-4 alkoxyalkyl groups or C6-10 aryloxy groups,
Is 0, 1 or 2, m is 2 or 3, and the bonding position of the pyridine ring is 3-position or 4-position.
The compound according to the item. 3. R is hydrogen atom or methyl group, X is methyl group, ethyl group, propyl group, isopropyl group, methoxy group, methylthio group, methylsulfonyl group, methylsulfinyl group, vinyl group, allyl group, Ethynyl group, propargyl group, methoxymethyl group, 2-ethoxyethyl group, trifluoromethyl group, nitro group, cyano group, difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethylthio group or trifluoromethylthio group, 1 being 0
The compound according to claim 1, which is 1 or 1, m is 2 or 3, and the bonding position of the pyridine ring is 3-position or 4-position. 4. The formula: 3- (2-methyl-5-pyridylmethyl)-according to claim 1, claim 2 or claim 3 represented by
2- (nitromethylene) thiazolidine. 5. The formula: 3- (2-methyl-5-pyridylmethyl)-according to claim 1, claim 2 or claim 3 represented by
2- (nitromethylene) tetrahydro-2H-1,3-
Thiazine. 6. The formula: The 3- (2-trifluoromethyl-5-pyridylmethyl) -2- (nitromethylene) thiazolidine according to claim 1, claim 2, or claim 3. 7. The formula: 3- (2-ethyl-5-pyridylmethyl)-according to claim 1, claim 2 or claim 3 represented by
2- (nitromethylene) thiazolidine. 8. The formula: The 3- (3-pyridylmethyl) -2- (nitromethylene) tetrahydro-2H-1,3-thiazine according to claim 1, claim 2 or claim 3 represented by the formula. 9. A general formula: In the formula, R represents a hydrogen atom or an alkyl group, X represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylsulfinyl group, an alkenyl group or an alkynyl group, wherein these groups are substituted with halogen. Or a halogen atom, a nitro group, a cyano group, an aryl group, an aralkyl group, an alkoxyalkyl group or an aryloxy group, 1 represents 0, 1, 2, 3 or 4, m represents 2, 3 or 4 and in the above formula, the bonding position of the pyridine ring is 3-position or 4-position, provided that when l is 1, X does not represent a halogen atom, and l is 2, 3 or 4, when not all X's represent a halogen atom at the same time, a compound represented by: Wherein R ′ represents a lower alkyl group or a benzyl group, or two R ′ together represent a C ₂ or lower alkylene group, which may form a ring together with the adjacent sulfur atom, A compound represented by the general formula: In the formula, R, X, l and m are the same as defined above, and a method for producing a nitromethylene derivative represented by: 10. A general formula: In the formula, m is 2, 3 or 4, and a compound represented by the following formula: In the formula, R represents a hydrogen atom or an alkyl group, X represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylsulfinyl group, an alkenyl group or an alkynyl group, wherein these groups are substituted with halogen. Or may represent a halogen atom, a nitro group, a cyano group, an aryl group, an aralkyl group, an alkoxyalkyl group or an aryloxy group, l represents 0, 1, 2, 3 or 4, and Hal represents a halogen atom. And in the above formula, the bonding position of the pyridine ring is 3-position or 4-position, provided that when l is 1, X does not represent a halogen atom, and when l is 2, 3 or 4. , Not all Xs at the same time represent a halogen atom, characterized by reacting with a compound represented by: In the formula, R, X, l and m are the same as defined above, and a method for producing a nitromethylene derivative represented by: 11. A general formula: In the formula, R represents a hydrogen atom or an alkyl group, X represents an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylsulfinyl group, an alkenyl group or an alkynyl group, wherein these groups are substituted with halogen. Or may represent a halogen atom, a nitro group, a cyano group, an aryl group, an aralkyl group, an alkoxyalkyl group or an aryloxy group, l represents 0, 1, 2, 3 or 4, m is 2, 3 or 4 and in the above formula, the bonding position of the pyridine ring is 3-position or 4-position, provided that when l is 1, X does not represent a halogen atom, and l is 2, 3 or In the case of 4, all the Xs do not simultaneously represent a halogen atom, and the insecticide containing the nitromethylene derivative represented by: as an active ingredient.