JPH01275576A - 1,3-dithain derivative, production and composition thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is alkyl or halo-lower alkyl; R<2> and R<3> are H, hydrocarbon group or heterocyclic group which may have a substituent group or R<2> and R<3> together with the adjacent N may form a ring) or salts thereof. EXAMPLE:2-Cyano-2-(N,N-dimethylcarbamoyl)-5-isopropylthio-1,3-di-thian. USE:An industrially and advantageously producible insecticide and acaricide having excellent effects on plant damaging insects, animal or plant parasitic mites, sanitary insect pests, etc., with low phytotoxicity to plants and low toxicity to humans, cattle and fishes. PREPARATION:A compound expressed by formula II (R<4> is hydrocarbon group which may have a substituent group or OH) is reacted with a compound expressed by formula III or salt thereof or a compound expressed by formula IV (Y is halogen) or salt thereof is reacted with a compound expressed by the formula R<1>SM' (M' is alkaline metal ion or quaternary ammonium ion) to afford the aimed compound expressed by formula I or salt thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to rT-1,3-dithiane derivatives which exhibit excellent efficacy against insects that damage plants, mites that parasitic animals and plants, sanitary pests, etc. Regarding drugs.

BACKGROUND OF THE INVENTION Conventionally, synthetic compounds having various pest control effects have been used as insecticides, but most of them belong to the organic phosphate esters, carbamate esters, or organic chlorine compounds.

It is well known that the frequent use of such a limited range of compounds causes harmful effects such as increased insecticide resistance in insect pests, and some of the above insecticides Even though they have great insecticidal power, they are highly toxic to humans and animals, and are sometimes toxic to the natural enemies of pests, resulting in unexpected outbreaks of pests, so the current situation is that they do not always have satisfactory effects in practical terms. .

On the other hand, insecticides of a different type from the mainstream insecticides mentioned above have been studied.
91 and Japanese Patent Publication No. 38-6881, 1,3-diane compounds having a di-substituted amino group or an optionally substituted amino group at the 5-position, respectively, have been proposed.

Problems to be Solved by the Invention The purpose of the present invention is to develop a system that is different from the mainstream of conventional insecticides such as organic phosphate esters, carbamate esters, and organic chlorine compounds, which can avoid the increase in insecticide resistance of insect pests. The object of the present invention is to provide a new insecticide and acaricide that has a new and different structure and has low drug toxicity to plants, toxicity to humans and animals, and toxicity to fish.

Means for Solving the Problems The present inventors have developed an insecticide and acaricide that can be industrially advantageously produced, has no phytotoxicity to mustard plants, has low toxicity to warm-blooded animals and fish, and can be used safely. As a result of intensive research, we succeeded in creating the compound shown in Formation (1) below.
It was discovered that it has excellent insecticidal and acaricidal effects against parasitic mites of animals and plants, sanitary pests, etc., has low toxicity to warm-blooded animals and fish, and can be obtained industrially advantageously. As a result of various studies based on the findings, the present invention has been completed.

That is, the present invention relates to a compound of formula (1) [wherein R1 represents an alkyl group or a halo-lower alkyl group, and R1 and R3 each represent a hydrogen atom or a hydrocarbon group or compound group that may have a substituent] It may represent a cyclic group, or R1 and R3 may be taken together to form a ring with the adjacent nitrogen atom. 1 represented by ]
, 3-dithiane derivative or salt thereof, (2) Formula [wherein E1 has the same meaning as above, and R4 represents a hydrocarbon group or a hydroxyl group which may have a substituent.

] and a compound represented by the formula [wherein R1 and R3 are as defined above]. A method for producing a 1,3-dithiane derivative represented by the above formula (1) or a salt thereof, which is characterized by reacting with a compound represented by the formula (3) [wherein Y is a halogen It represents an atom, and R2 and R3 are as defined in Q above. ] or a salt thereof and the formula % Formula % () 1 In the formula, R1 has the same meaning as α described in ``2'', and M' represents an alkali metal ion or an ammonium ion.

] A method for producing a 1,3-didian derivative represented by the above formula (1) or a salt thereof, and (4) a method for producing a 1,3-didiane derivative represented by the above formula (1), which is characterized by avoiding the reaction with a compound represented by the following formula (1): The present invention relates to an insecticidal and acaricidal composition characterized in that it is impregnated with a 1,3-didian derivative or a salt thereof.

The compound of the present invention represented by the formula (1) is a compound of the known formula (1).
．． Unlike 3-diane compounds, it has an alkylthio group or a halo-lower alkylthio group at the 5th position of the 1.3-diane skeleton, and a specific group called a carbamoyl group, which may be substituted with a cyano group, at the 2nd position. It is a compound with a novel structure characterized by points. Furthermore, the compounds of the present invention having these specific substituents at the 2- and 5-positions are effective in controlling various pests, as described later, and are particularly effective against Hemiptera pests such as planthoppers.

In the above general formula (1), the alkyl group represented by R1 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 5ec-butyl, ter
t-butyl, n-pendel, 5ec-pendel, isopentyl, neopendel, n-hexyl, isohegicyl,
Straight-chain or branched lower alkyl groups having 1 to 10 carbon atoms such as n-octyl and n-decyl are preferred; is preferable,
Alternatively, R1 represents lower alkyl such as trifluoromethyl and tetrafluoroethyl. In the above general formula (1), R2 and R3 are the same or different and represent a hydrogen atom or a hydrocarbon group or a heterocyclic group which may have a substituent, or R2 and R3 together represent It may form a fence together with adjacent nitrogen atoms. Examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 5ec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, allyl, undecyl, dodecyl,
1 carbon number such as tridecyl, tetradecyl, pentadecyl, etc.
-15 alkyl, cycloalkyl having 3 to 6 carbon atoms such as cyclopropane, cyclobutane, cyclobencune, cyclobutane, such as vinyl, allyl, 2-methallyl, 3-
Alkenyl having 2 to 4 carbon atoms such as methallyl and 3-butenyl; cycloalkenyl having 3 to 6 carbon atoms such as cyclopropenyl, cyclopentenyl, and cyclohexenyl; aryl having 6 to 10 carbon atoms such as phenyl and naphthyl, e.g. Aralkyls having 7 to 10 carbon atoms such as benzyl and phenylethyl are preferably used. The heterocyclic group is preferably a 5- to 6-membered heterocyclic group containing at least one heteroatom selected from oxygen, sulfur, and nitrogen;
It may be fused with a 5- to 6-membered ring which may contain oxygen, sulfur, nitrogen, etc. Examples of these optionally fused multiple rings include dienyl, furyl, pyrazolyl, thiazolyl, isothiazolyl, oxasilyl, isoquinolyl, noazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidyl, pyridazinyl, quinolyl, isoquinolyl, indolyl, and the like. These hydrocarbon groups or polycyclic groups! It may have one to several, preferably one to three substituents, and examples of the substituents include nitro, amino, hydroxyl, cyano, carbamoyl, carboxyl, sulfonyl, halogens such as chlorine, bromine, and iodine, such as methoxy, Lower alkokino having 1 to 4 carbon atoms such as ethoxy, butoxy, isopropoxy, butquine, isobutoxy, 5ec-butoxy, tert-butoxy, fenoquine,
In addition to benzoyl, etc., aryl, aralkyl, cycloalkyl, and heterocyclic groups may be substituted with lower alkyl having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, pentyl, hexyl, phenyl, etc. good. R2 and R3 may be hydrogen atoms. R', R
Examples of the ring formed by 3 together with the adjacent nitrogen atom include 5-60q-shaped amino groups such as piperazino, morpholino, and pyrrolidino. may be substituted with a lower alkyl group, halogen, hydroxyl group, etc.

The object of the present application (1) produces isomers when the 2-position carbon of the 1,3-dithiane skeleton is an asymmetric carbon, but the compound of the present invention includes not only each isomer alone but also a mixture thereof. Both are within the scope of the present invention.

In addition, as a salt of compound (1), substituted 7 of R2 and R3
．． (with an acidic group (e.g. c o o t-t, etc.)
When these groups have, for example, sodium 11
, magnesium A, salts formed with alkali metals and alkaline earth metals such as potassium and calcium, or R2,
Mineral acids such as hydrochloric acid, phosphoric acid, sulfuric acid, etc. formed in the basic group in the substituent of R3, such as oxalic acid,
Examples include salts with organic acids such as acetic acid and benzoic acid.

The object compound (1) of the present application can be produced by a method known per se, but furthermore, for example, the following method (
It can also be produced by A) or (B).

Method (A) Formula (It) 1”t's C11(C1-LX)t (Ij)[
In the formula, R1 has the same meaning as above, and X represents a halogen atom. A compound represented by the formula % Formula % (1) [wherein R4 represents a hydrocarbon group or a hydroxyl group which may have a substituent, and M represents an alkali metal ion or a quaternary ammonium ion. ] The compound represented by the formula ([V) obtained by reacting with the compound represented by the formula ([V]) and the compound represented by the formula ([V]
Compound (1) or a salt thereof is produced by reacting with the compound represented by V).

More specifically, first, in order to produce compound (1), compound (II) and compound (III) are usually reacted without a solvent or in a suitable solvent. Suitable solvents include alcohols such as methyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, methylene chloride, Halogenated hydrocarbons such as chloroform and carbon tetrachloride, ethers such as ethyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide and dimethylacetamide, etc. Amides, esters such as methyl acetate, ethyl acetate, and butyl acetate are used alone or in combination.

' In this reaction, the compound ('[) is about 1.1 to 4 times the mole of compound ([1), preferably about 2 to 2.5 times
Use double the mole. This reaction may be carried out in a chamber or tray, but may be carried out at a temperature of about 30 to 100°C to prevent the reaction from proceeding smoothly.

The reaction time varies depending on the reaction temperature, etc., but it is normal! 5 minutes ~ I5
The time is preferably about 30 minutes to 8 hours. Compound (IV) thus obtained can be isolated and purified by means known per se such as silica gel chromatography.

Compound (IV) and compound (V) obtained in this way
are reacted in a suitable solvent to obtain compound (1).

Suitable solvents include alcohols such as methyl alcohol, methyl alcohol, and isopropyl alcohol, ethyl ether, dioxane, tetrahydrofuran,
Ethers such as ethylene glycol dimethyl ether,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; nitrides such as acetonitrile; acid amides such as dimethylacetamide; esters such as ethyl acetate;
Sulfoxides such as dimethyl sulfoxide can be used. If necessary, a combination of water and aromatic hydrocarbons or halogenated hydrocarbons can also be used. The reaction can also be accelerated by adding a base to such a solvent.

Such bases include, for example, triethylamine,
Pyridine, DBU (1,8-diazabicyclo[5,4,
0] tertiary amines such as undec-7-ene) or alkali metal and alkaline earth metal hydroxides such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium alcoholade, etc. Organic metal salts such as carbonates, carbonates, bicarbonates as well as alkali metal alcolades and n-butylridium are preferably used.

Compound (V) is usually 1 mole per 1 mole of compound (IV).
~3 mol, preferably 1.1 to 1.5 mol is used. When a base is further added, it is convenient to use about 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of compound (IV).

This reaction usually proceeds at room temperature, but it may be carried out with heating to make the reaction proceed smoothly, for example, from 40 to 1
It can be carried out at 00°C. The reaction time varies depending on the reaction temperature, etc., but is usually about 15 minutes to 24 hours, preferably 30 minutes.
It takes about 5 minutes to 5 hours.

Compound (1) thus obtained can be isolated and purified by known means such as filtration, recrystallization, solvent extraction, dissolution, salting out, and silica gel chromatography. When obtained as a free base, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, or acetic acid, benzenesulfonic acid,
It may also be used as an addition salt with YT organic acids such as p-toluenesulfonic acid, methanesulfonic acid, citric acid, tartaric acid, oxalic acid, propionic acid, maleic acid, malic acid, malonic acid, fumaric acid, mandelic acid, and ascorbic acid. Also, R2, R3
When a carboxyl group or the like is present as a substituent, it can be converted into a salt with an alkali metal or alkaline earth metal as described above according to a conventional method.

Furthermore, when compound (1) is isolated and purified as such a salt, it can be converted into a free base (compound (+) itself) according to a conventional method.

Method (B) A 1,3-notiane derivative (I) or a salt thereof can be produced by alkylthiolating the compound (V[) or a salt thereof.

As the salt of compound (Vl), salts such as those described for object (1) can be used as appropriate. In this reaction, compound (Vl)
or preferably 1 to 1 o mol per 1 mol of its salt
This is done by reacting ~5 moles of an alkylthiolating agent. The reaction can also advantageously be carried out in the presence of a base. Any alkylthiolating agent may be used as long as it does not interfere with the reaction. Generally, a compound represented by the above formula (■) is preferably used, such as methyl mercaptan sodium salt, ethyl mercaptan sodium salt, propyl mercaptan sodium salt, 1so-propyl mercaptan sodium salt, etc.

It is generally advantageous to carry out this reaction in a solvent, and examples of the solvent include water, alcohols such as methanol and ethanol, nitriles such as acetonitrile, methyl iodide,
Halogenated hydrocarbons such as ethyl bromide and 10-form, aromatic hydrocarbons such as benzene, toluene, and xylene are used.

The reaction temperature varies depending on the alkylthiolating agent and solvent used, but is usually -70 to 100°C, preferably -50 to 100°C.
The temperature is 80°C. In general, the reaction is completed in 5 to 48 hours at 0°, preferably 1.0 to 10 hours. The resulting compound (1) may be isolated by known methods as the free base or as a salt thereof as described in method (A).

Compounds (n), ([1), (V), (Vl) used as raw materials in the above methods (A) and (R3) are:
For example, Journal of Organic Chemistry (J, O, C,), vol. 48, p. 4393 (1983).
; Journal of American Chemical Society (, ■, Δ, C, S,), vol. 63, p. 852 (+9/
II), Journal of Organic Chemistry (J, O, C,), vol. 26, p. 2507 (1961)
；Cyanide in Organila reaction a
It is synthesized by a known method described in a review or similar method.

The compound (+) of the present invention or a salt thereof produced as described above has a strong insecticidal and acaricidal effect against plant-damaging insects, parasitic mites on animals and plants, sanitary pests, etc., and is effective in controlling these pests. . Control of these pests can be achieved by direct contact with the insects, such as by directly spraying them on the plants and animals infested by the pests. Once absorbed by the plant, pests absorb the sweat and sing! It exhibits a strong insecticidal effect even when exposed to water or in contact with it. Such properties are advantageous for exterminating sweat-absorbing and evaporative insects or mites. Furthermore, the compound of the present invention has both safe and well-documented properties as an agricultural pest control agent, such as having little phytotoxicity to plants and low toxicity to fish.

More specifically, the compound (1) of the present invention and a compound containing it
For example, preparations for preparing the planthopper (Laodel
phax 5tiatelluss), black leafhopper (NephotetLix cincticep)
s), IJn33piSyano
nensis), Aphis g.
lycines), Japanese radish abramun (Lipa
phis pseudobrassicaee), radish aphid (Brevicoryne bra
ssicae), cotton aphid (Aphis go
Hemiptera pests such as Spodoptera ssypii, Spodoptera 1itura, and the diamondback moth (Spodoptera 1itura).
Plutella xylostella), Pierisrape crucivor
a), Chil.

5uppressalis), Kumanaginuwaba (Pl
usianigrisigna), Tobacco moth (Eeli)
coverpa assulta), fall armyworm (I
eucania 5eparata), armyworm (M
amesLra brassicae), Adoxophyes orana, Syllcptcdcrogata, Cnaphalocroc ismedin
alis), potato moth (Phthorimaeao)
Lepidopteran pests such as Epilachna vi
gintioctopun -ctaLa), cucumber beetle (Aulacophora femoralis)
, pHyllotreta 5L
riolata), rice beetle (Oulema
orgzae), inezomun (Ishichinocn)
emus squameus), e.g.
, Culex pipiens pal
lens), Tabanustrigonu
s), onion fly (Ilylemya antiq
ua), seed fly (Ilylemya platur)
a) and other Diptera pests, such as the locust (Loc
usta migratoria).

Gryllotalpa arricana
Orthoptera pests such as the German cockroach (Blat
tella german -Ica), black cockroach (Periplaneta fuliginosa)
) and other pests of the order Cockroaches, such as the two-spotted spider mite (TeLr
anychus urticae), citrus spider mite (
Panonychus citri), Kanzawa spider mite (Tetranychus kanzawai),
Tet ranychuscinna
barinus), apple spider mite (Panonychu)
sulmi), orange spider mite (Aculus p.
Spider mites such as Aphel-cnchoides (Aphel-cnchoides)
It is especially f1 effective for controlling nematodes such as Besseyi).

When using the compound (1) of the present invention or a salt thereof as an insecticide and acaricide, one or more types of the compound (I) of the present invention or a salt thereof may be used in the form that general agricultural chemicals can take, depending on the purpose of use. Emulsions, oils, sprays, wettable powders, powders, granules, tablets, ointments, etc. by conventional methods such as dissolving or dispersing in a suitable liquid carrier, or mixing or adsorbing with a suitable solid carrier. It is desirable to use it as a preparation. Additionally, these preparations may contain
Emulsifiers, suspending agents, spreading agents, penetrating agents, wetting agents, thickeners, stabilizers, etc. may be added. These formulations can be prepared by methods known per se.

The appropriate content of the compound (1) of the present invention or its salt in insecticides and acaricides is approximately 10% to 90% by weight for emulsions, wettable powders, etc., and approximately 31% to 10% by weight for oils, powders, etc. The appropriate concentration is about 1% to 20% by weight for granules, but these concentrations may be changed as appropriate depending on the purpose of use. When using emulsions, hydrating agents, etc.
Dilute with water, etc. to increase the amount (e.g. +00-100000)
(double) and disperse.

Liquid carriers (solvents) used include, for example, water, alcohols (e.g., methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, etc.), ethers (e.g.,
Dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), ketones (e.g., acetone, methyl alcohol, etc.), aliphatic hydrocarbons (e.g., keronone, kerosene, fuel oil, machine oil) ), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (e.g., methylene chloride, chloroform, carbon tetrachloride, etc.), acid amides (e.g., Suitable solvents include dimethylpolamide, dimethylacetamide, etc.), esters (e.g., ethyl acetate, butyl acetate, fatty acid glycerin ester, etc.), and nitriles (e.g., acetonitrile, propionitrile, etc.). One type or a mixture of two or more types in an appropriate ratio may be used.

Solid carriers (diluents and bulking agents) include vegetable powders (e.g., soybean flour, tobacco flour, wheat flour, wood flour, etc.), mineral powders (e.g., kaolin, bentonite, clays such as acid clay, talc, wax, etc.). Talc such as stone powder, silica such as diatom powder, mica powder, etc.), alumina, sulfur powder,
Activated carbon and the like can be used, and these can be used alone or in a mixture of two or more in an appropriate ratio.

Examples of ointments include polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate, cellulose derivatives such as methyl cellulose,
Sodium alginate, bentonite, higher alcohols such as polyhydric alcohols such as glycerin, vaseline,
White petrolatum, liquid paraffin, lard, various hamonoura,
One or more of lanolin, dehydrated lanolin, curing agents, resins, etc., or a combination thereof with various surfactants shown below may be used as appropriate.

As surfactants used as emulsifiers, spreading agents, penetrants, dispersants, etc., petroleum products, polyoxyethylene alkylaryl ethers (e.g., Neugen,
E-nee 142 (E-AI42) 0. Daiichi Kogyo Seiyaku (
(manufactured by Kao Soap Co., Ltd.), polyoxyethylene aryl esters (e.g., Nonal 0, manufactured by Toho Chemical Co., Ltd.), alkyl sulfates (e.g., Emar 100, Emar 40, manufactured by Kao Soap Co., Ltd.), alkyl sulfonates (e.g., Neogen■, Neogen'r■, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.; manufactured by Neoperecdo Kao Soap Co., Ltd.), polyethylene glycol ethers (e.g., Noniball 850, Nonipol 10p, Noniball 160■, Sanyo Chemical (manufactured by Kao Soap Co., Ltd.), Nonionic and anionic surfactants such as Tween 2p, Tween 80o, and Kao Soap Co., Ltd.) and polyvalent anodil esters (eg, Tween 2p, Tween 80o, Kao Soap Co., Ltd.) are used.

When using the compound (1) of the present invention or a salt thereof as an agricultural chemical, compound CI) or a salt thereof should be combined with other types of insecticides (e.g., pyrethrin insecticides, carbamate insecticides, organophosphorus insecticides, natural Insecticides, etc.), mites, nematicides, displacers, plant hormones, plant growth regulators, synergists, attractants, repellents, pigments, fertilizers, etc. are mixed in appropriate proportions. , can also be used.

Among the preparations containing the compound (1) of the present invention or a salt thereof, emulsions and wettable powders usually have a concentration of the compound (1) of the present invention of 20 to 5000 ppm, preferably about 50 to 11
It is preferable to use it after diluting it to about 00Qpp.

When the compound (1) of the present invention or a salt thereof is used as an agricultural insecticide, the m used is about 10 g to 1 Kg1 per 10 are, preferably about 30 g in terms of compound (1).
About 500g is appropriate. A preparation containing the compound (1) of the present invention can be applied to plants by a known method, for example, by directly spraying the leaves and stems, or by applying it to the roots of hrL plants.

The spray may be sprayed as is using a suitable sprayer, but it may also be made into a so-called insecticidal aerosol by adding a propellant such as fluorocarbon, liquefied fossil i+b gas, dimethyl ether, carbon dioxide, or the like.

Effects of the Invention The compound (1) of the present invention or its salt can be used for vegetables (e.g., cabbage, Chinese cabbage, cucumber, potato, etc.), fruit trees (e.g., mandarin oranges, pears, etc.), flowers (e.g., roses, chrysanthemums, etc.)
, various pests such as tobacco (e.g. armyworm, green caterpillar,
It is effective in controlling diamondback moths, aphids, lady beetle larvae, potato moths, red leaf beetles, green leaf beetles, horn beetles, leaf beetles, tobacco caterpillars, etc.).

In addition, the compound of the present invention also has the effect of having low phytotoxicity to plants, toxicity to humans and animals, and toxicity to fish.

EXAMPLES Next, the present invention will be explained in more detail by examples.
The invention should not be limited to these examples.

The silica gel used in silica gel chromatography in the following examples was Kieselgel 6 manufactured by Merck & Co.
0 was used. Also, for N M n data, the δ value is p
Shown in pm. Each abbreviation has the following Q meaning.

S: singlet, d: doublet 1m: multiplet + J coupling constant, r[z: Hertz.

CDCρ3: weight o roform, Me: methyl group, Et
: ethyl group, nPr: n-propyl group, 'Pr:i
Pr: Mepropyl Bu: tert-butyl group Amy
l: i-amyl group Reference example Sodium benzenesulfinate 40g (0.2 mol)
and 1,3-dibromo-2-isopropylthiopropane 2
Add 2 g (0; 1 mol) to 100 mol of acetonitrile,
React under heating under reflux for 4 hours.

After the reaction is completed, the mixture is cooled to room temperature and concentrated under reduced pressure.

Add 20 (L, 1. chloroform) to the concentrate and wash with water.

The chloroform layer is dried (MgSO, ) and concentrated. Purified by silica gel column chromatography (elution solvent: chloroform) to obtain 1,3-bis(benzenesulfonylthio)-2-isopropylthiopropane as an oil.
7. Ig (yield 80.1%) is obtained.

Example I 1.12 g of N,N-dimethylcyanoacetamide (0,
01 mol) and 1,3-bis(benzenesulfonylthio)
4.6 g (0.01 mol) of -2-isopropylthiopropane was added to 2Od of chloroform and 1.8-diazabicyclo[4,4,0]undec-7-nin 3.1
g (0.02 mol) is added. 50℃ after addition
React for 4 hours. After the reaction is completed, wash twice with 20 J of water. After drying with anhydrous magnesium sulfate, it is concentrated to dryness. Recrystallized from ethyl ether to give 2-cyano-2-(N,N-dimethylcarbamoyl)-5=isobrobildione-1,3-nodian (compound No.) as crystals at m, p, 78-9°C.

5) 1.92g (66.1%) was changed.

11'NM1? (CDCI2+)・1.31(611,
d, J=611z), 3.0-3.6 (6tl, m)
, 3.10(611,s) Example 2 N-methylpiperazinecarbonylacetonitrile I,
52 g (0.01 mol) and 4.6 g of 1,3-bis(benzenesulfonylthio)-2-isopropylthiopropane
(0.01 mol) in Chloroporm 201d and 2.1 g (0.02 mol) of triethylamine are added at room temperature. After the addition is complete, react at 40°C for 4 hours. After the reaction is completed, wash twice with 20 rJ of water. After drying with anhydrous magnesium sulfate, it is concentrated to dryness. The residue was dissolved by heating with 2 LJ of ether and left overnight in a cool place. When the precipitated crystals are collected by filtration, m and p are obtained.

2-cyano-2-(4-methylpiperazin-■-yl)-5-isobrovirdiol 1 as crystals at 94-5°C.
．． 3-dithiane (Compound No. 8)
'2.54 g (77.5%) was obtained.

II' NMR (CD C123): 1.28 (61
1,dj=6.311z), 2゜30(311,s)
, 3.0-3.9 (611, m), 2.49 (41
1, m), 3.67 (211, m), 3.91 (2
11, m).

Example 1 Blood Example 3 N-Methyl biverazinotriponyl acetonitrile 1.5
2 g (0.01 mol) and 4.7 g (
0.01 mol) into 20 mol of chloroporm, and 2.1 g (0.02 mol) of triethylamine are added at room temperature. After the addition is complete, react at 40°C for 4 hours. After the reaction is completed, wash twice with 20 d of water. After drying with anhydrous magnesium sulfate, it is concentrated to dryness. The residue was dissolved by heating with 20% ether and left overnight in a cool place. When the precipitated crystals are collected by filtration, m and p are obtained.

2-cyano-2-(4-
methylpiverazin-1-yl)-5-isopenderthio-1,3-dithiane (Compound No. +2) 2
．． 6 g (69.5%) were obtained.

II' NMR (CD CQ3): 0.95 (311
,dj=6.311z), 1°27(3tl,d),
1.85 (III, m), 2.85 (lIl, m)
, 3.0-3.5 (411, m), 2.32 (31
1,s), 2.5(411,m), 3.85(41
1, m).

3.92 (411, m).

Dissolve the dithiane obtained here in acetonitrile,
Add methanol-hydrochloric acid, collect the precipitated crystals by filtration, m
, p, to obtain the hydrochloride salt at 190°C (sublimation).

Example 4 2-cyano-2-(N,N-dimethylcarbamoyl)-
2.5 g (0.01 mol) of 5-chloro-1,3-dithiane was dissolved in 20 turns of acetonitrile. 1.0 g (0.01 mol) of isopropyl mercaptan sodium salt is added at room temperature. After the addition is complete, the reaction is carried out under heating and reflux for 6 hours. After the reaction is complete, the solvent is removed under pressure, 50 volumes of chloroform is added, and the mixture is washed with water and dried over anhydrous magnesium sulfate.

It was purified by silica gel column chromatography (elution solvent: chloroform). 2-cyano-2-(N,N-dimethylcarbamoyl) as crystals at m, p, 78-9°C
-5-isobropyldio1,3-dithiane (corresponds to the above compound No. 5)1. Og (35.5%) is obtained.

Representative examples of Compound (1) or its salt obtained in Examples 1 to 4 are shown in Table 1 below along with their melting points or boiling points and yields.

(Left below) Compound numbers in the following examples and test examples are shown in Table 1.
It means compound No. Of course, the objects of the present invention are not limited to these.

Example 5 Compound No. 5 20% by weight xylene 75% by weight polyoxyethylene glycol ether (Noniball 85■)
An emulsion was prepared by mixing 5% by weight or more of the components.

Example 6 Compound No. 8 30% by weight sodium lignin sulfonate 5% by weight polyoxyethylene glycol ether (Noniball 85■)
5% by weight white carbon
30% by weight clay 3
Wettable powders were prepared by adjusting the components to be equal to or greater than 0% by weight.

Example 7 Compound No. 6 3% by weight white carbon 3% by weight clay
A powder was prepared by mixing 94% by weight or more of the ingredients.

Example 8 Compound No. 5 10% by weight Sodium ligninsulfonate 5% by weight Clay
Granules were obtained by mixing and granulating 85% by weight or more of the components.

Test Example 1 Brown Planthopper (Niraparvata rugc)
ns) The test compound was made into an emulsion according to the formulation of Example 7, and diluted with water to prepare a 50 ppm treatment solution. Add this treatment solution to 1
After immersing 3 sprouted seedlings (70 days after germination) in 00yJ of beer for 10 minutes, the soaked seedlings were transferred to a test tube with 1d of water in the bottom, and 2 -5 3rd instar larvae were released. Store the test tube indoors (20°C)
) for 24 hours, and the mortality rate was determined. The test was conducted twice, and the test results are shown in Table 2 as mortality rate (average of the two tests).

Test Example 2 Culex pipiens mole
The test compound was made into an emulsion according to the formulation of Example 7, and diluted with water to prepare a 50 ppm treatment solution. Add this treatment solution to 5
01 difference in bee power, and 10 test insects (3rd to 4th instar larvae) were released into this. The test was repeated twice, and the mortality weight was determined 24 hours after treatment. The test results are shown in Table 3 as mortality rate (average of two tests).

Test Example 3 Tetranychus urtica
Effect on e) The test compound was made into an emulsion according to the formulation of Example 4, and water was added so that the spreading agent Dyne 0 was diluted 3000 times.
An aqueous solution of Oppm was prepared. Ten female adult red spider mites were inoculated into green bean seedlings grown hydroponic in an ice cream cup, placed in a glass room (28°C) for 24 hours, and 20 mff of an aqueous solution was sprayed on the green beans. After spraying, the cup was returned to the glass chamber, and two days after spraying, the number of young adults living on the leaves was determined.

The test is conducted in two repetitions, and the test result is the true/incorrect rate (average of the two times).
was calculated using the following formula. The results are shown in Table-4.

The results of the two tests show that the compound of the present invention exhibits excellent insecticidal and acaricidal effects against various pests. In particular, it was shown that the control effect against planthoppers was significant.

Agent Patent Attorney Iwa 1) Buddhist Studies Itotane City 5:E Stop (spontaneous) June 9, 1988 I, Incident Indication 1988 Patent Application No. 105079 2, Name of the Invention 1.3-Zidian Derivatives, their manufacturing methods and compositions 3, and their relationship to the amended person's case Patent applicant address 2-27 Doshomachi, Higashi-ku, Osaka Name (29)
3) Takeda Pharmaceutical Co., Ltd. Representative: Junmasa Umemoto 4, Agent address: 2-17-85-5, Jusohonmachi, Yodoyo-ku, Osaka City, ?
+lf Positive Target 6, Contents of Amendment (1) From the fourth line to the third line from the bottom of page 35 of the specification, "The test tube was placed indoors (20°C) for 24 hours, and the number of fatal man-hours was investigated." This should be corrected to ``The test tube was placed indoors (20°C), and the number of man-hours killed was examined 1 day and 6 days after release.''

(2) "Table-2" in the second line from the bottom of the same page in the same book as "Table-3"
Correct.

(3) "Table-3" on page 36, line 8 of the same book is corrected to "Table-2."

that's all

Claims (4)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents an alkyl group or a halo-lower alkyl group, and R^2 and R^3 each have a hydrogen atom or a substituent. may represent a hydrocarbon group or a heterocyclic group, or R^2 and R^3 may be taken together to form a ring with the adjacent nitrogen atom. ] A 1,3-dithiane derivative or a salt thereof. (2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 has the meaning as stated in claim 1, and R^4
represents a hydrocarbon group or a hydroxyl group which may have a substituent. ] and the formula ▲ mathematical formula, chemical formula, table, etc. ▼ [In the formula, R^2 and R^3 are as defined in claim 1. 2. The method for producing a 1,3-dithiane derivative or a salt thereof according to claim 1, characterized in that the 1,3-dithiane derivative or a salt thereof is reacted with a compound represented by: (3) Formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Y represents a halogen atom, and R^2 and R^3 are as defined in claim 1. ] or a salt thereof and the formula R^1SM' [wherein R^1 has the meaning as defined in claim 1, and M' represents an alkali metal ion or a quaternary ammonium ion. ] The method for producing a 1,3-dithiane derivative or a salt thereof according to claim 1, which comprises reacting a compound represented by the following. (4) An insecticidal and acaricidal composition comprising the 1,3-dithiane derivative or its salt according to claim 1.