JPH03197474A - New thiadiazine-based compound, its production and insecticide and acaricide containing the same compound - Google Patents

Abstract

NEW MATERIAL:Tetrahydro-1,3,5-thiadiazine-4-ones expressed by formula I (R<1> is 1-4C alkyl; R<2> is 1-4C alkyl, 1-4C haloalkyloxy, 1-4C haloalkylthio, etc.) or salts thereof. EXAMPLE:2-(2,2,2-Trifluoroethylimino)-3-(4-tert-butylbenzyl)-5-(4-meth oxyphenyl)- tetrahydro-1,3,5-thiadiazine-4-one. USE:An insecticide and acaricide, capable of exhibiting a wide insecticidal spectrum and having excellent insecticidal activity even against insect pests of the order Lepidoptera. PREPARATION:A carbamoyl chloride derivative expressed by formula II is made to react with a thiourea derivative expressed by formula III in a solvent such as toluene at 30-250 deg.C for 0.1-30hr to afford the compounds expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is based on the general formula (I) (wherein R' represents an alkyl group having 1 to 4 carbon atoms, and R2 represents an alkyl group having 1 to 4 carbon atoms; 4 alkyl group, a haloalkyloxy group having 1 to 4 carbon atoms, a haloalkylthio group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms
4 shows a haloalkenyl group. ) Tetrahydro-1,3,5thiadiazin-4-one cervix or its salts, their production methods, and one or two thereof
The present invention relates to an insecticide and acaricide characterized by containing at least one species as an active ingredient.

The compounds of the present invention are useful in various industrial fields, and are particularly useful in the agricultural field as insecticides and acaricides.

[Conventional technology]

Conventionally, tetrahydro-L 3,5-thiadiazine-4
- The fact that ons have insecticidal and acaricidal effects is disclosed in Japanese Patent Publication No. 54-3083 and Japanese Patent Publication No. 54-12399.
No. 54-154780.

Among these, 2-tert-butylimino-3isopropyl-5-phenyl-tetrahydro 1.3.5-thiadiazin-4-one (-ship name: buprofezin: Bu
profezin) is in practical use as an insecticide. Furthermore, in Japanese Patent Publication No. 140577/1987, a tetrahydro, -1,3 , 5-thiadiazin-4-ones are new compounds that have insecticidal and acaricidal effects, especially tetrahydro compounds in which at least one or more of the 2-imino group or the 3-position is substituted with a certain substituted phenylalkyl group. There is a description that -1,3,5-thiadiazin-4-ones exhibited more pronounced insecticidal and acaricidal effects than the known compound buprofezin. However, these insecticides and acaricides have insecticidal activity against Hemiptera pests and Coleoptera pests, but do not have sufficient insecticidal activity against Lepidoptera pests. There is a need for the development of a new drug that has similar effects to these insecticides and acaricides and has excellent insecticidal activity against Lepidoptera pests.

[Problems to be solved by the present invention]

An object of the present invention is to provide an excellent insecticidal compound, insecticide, and acaricide having a new structure, a wide insecticidal spectrum, and high insecticidal activity, which solve the problems of the prior art, and a simple method for producing the same. do.

[Means and effects for solving the problem] In order to solve the above problem, the present inventors conducted intensive studies on tetrahydro-1,3,''5-thiadiazin-4-ones, and found that 2
-(2,2,1-)Lifluoroethylimino)-tetrahydro-1,3,5-thiadiazin-4-ones or their salts have a wide insecticidal spectrum, and known related compounds do not show sufficient insecticidal activity. We have completed the present invention by discovering that it has high insecticidal activity even against harmful Lepidoptera pests.

That is, the present invention relates to the general formula (1) (wherein, R1 represents an alkyl group having 1 to 4 carbon atoms, and R
2 is an alkyl group having 1 to 4 carbon atoms, a haloalkyloxy group having 1 to 4 carbon atoms, a haloalkylthio group having DI to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkenyl group having 1 to 4 carbon atoms; show. ) Tetrahydro-1,3,5=thiadiazin-4-ones or salts thereof represented by -form (n) (wherein R1 has the above meaning), a compound represented by -form (III) In formula C, R2 has the above meaning. ) A method for producing tetrahydro-1,3,5-thiadiazin-4-ones represented by general formula (I) or salts thereof, which is characterized by reacting with a compound represented by general formula (I), and tetrahydro1.3.5--thiadiazine-4
The amount of active ingredients is one or more of -ones and salts thereof.

Tetrahydro-1゜3.5- represented by general formula (1)
Thiadiazin-4-ones and their salts have not been described in any literature and are new compounds.

In the compound of the present invention represented by general formula (I), when the 4-position substituent of the 3-position henzyl group, which is a substituent of the thiadiazine ring, is an alkyl group, normal-propyl group, iso-propyl group, normal A -butyl group, an iso-butyl group or a tert-butyl group is preferred, and a tert-butyl group is particularly preferred. When the 4-position substituent is a haloalkyloxy group, the halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom, with a fluorine atom being particularly preferred. As a haloalkyloxy group,
Difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethoxy group, bromodifluoromethoxy group, 2,2.2-trifluoroethoxy group, 1,1,2.
2-tetrafluoroethoxy group, 2.2,3.3-tetrafluoropropyloxy group or 2. 2. 3.
3. 4. 4.4-hexafluorobutoxy group is preferred, and trifluoromethoxy group is preferred. When the 4-position substituent is a haloalkylthio group, the halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom, with a fluorine atom being particularly preferred.

As the haloalkylthio group, difluoromethoxy group,
Trifluoromethylthio group, chlorodifluoromethylthio group, bromodifluoromethylthio group, 2,2.2-trifluoroethylthio group, 1.1,2.2-tetrafluoroethylthio group, 2, . 2.3. ．． 3-tetrafluoropropylthio group or 2. ' 2, 3.3, 4.4.
A 4-hexafluorophthylthio group is preferred, and a trifluoromethylthio group is particularly preferred. When the 4-position substituent is a haloalkyl group, the halogen atom is preferably a bromine atom, a chlorine atom, or a fluorine atom, with a fluorine atom being particularly preferred. Examples of haloalkyl groups include trifluoromethyl group, pentafluoroethyl group, normal-
A heptafluoropropyl group or a 2,2,2-trifluoroethyl group is preferred, and a trifluoromethyl group or a pentafluoroethyl group is particularly preferred. When the 4-position substituent is a haloalkenyl group, the halogen atom is preferably a bromine atom, a chlorine atom, or a fluorine atom, particularly a chlorine atom or a fluorine atom. Examples of the haloalkenyl group include 2,2-difluorovinyl L2.
'2-dichlorovinyl group, 2,2-dibromovinyl group,
2-fluoro-33,3-)lifluoro-1-propenyl group, 2-chloro-3,3,3-)lifluoro-1-propenyl group, 2-bromo-3,'3.3-)lifluoro-1-propenyl group The group is preferred, especially 2-chloro-3,3
,3-)lifluoro-1-propenyl group is preferred.
Further, as a substituent for the 5-position phenyl group, which is a substituent of the thiadiazine ring, 4-position methoxy group substitution or 4-position ethoxy group substitution is preferable.

Examples of salts of the compound of the present invention represented by general formula (1) include hydrochloride, hydrobromide, hydroiodide, hydrofluoride, sulfate, hydrogen sulfate, nitrate, and chloric acid salt. salt, perchlorate, phosphate, hydrogen phosphate, dihydrogen phosphate,
Inorganic acid salts such as thiocyanate, tetrafluoroborate, formate, acetate, trichloroacetate, trifluoroacetate, citrate, lactate, oxalate, glycolate, malonate, succinate Examples include organic acid salts such as acid salts, malates, dodecylbenzenesulfonates, benzoates, salicylates, and nicotinates.

Next, typical examples of the compounds of the present invention represented by the general formula (1) are shown in Table 1, but the present invention is not limited thereto.

Table 1 CH3 C1(:l CH:l CH.

CH3 CH.

zHs C2H1 C2) 15 2H5 C(CH3), l 0CF.

CF3 CF3 2F5 C)l=cc1cF3 C(CH3)3 CF3 CF3 CH=CCICF+ The compound of the present invention represented by the general formula (1) can be produced by the following method.

1 2 (1) (In the formula, R1 and RZ have the above meanings.) That is,
-i It can be obtained by reacting the carbamoyl chloride derivative represented by formula (II) with the thiourea derivative represented by formula (I) in the absence or presence of a solvent, preferably in the presence of a solvent. Suitable solvents include acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl ether, benzene, toluene, acetonitrile, ethanol, propatool, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1.3 ~Dimethyl 2-imidazolidinone, water and other solvents that do not affect the reaction can be used.

The reaction is carried out with heat or in the presence of a base. When the reaction is carried out by heating, the reaction temperature can be varied over a wide range depending on the starting materials;
0°C1 Preferably 40-15 (1'C8 reaction time is
The time is 0.1 to 30 hours, preferably 0.5 to 24 hours. When carrying out the reaction using a base, suitable bases include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, triethylamine, pyridine, N,N-dimethylaniline, 1, 8-
Examples include diazabicyclo-[5,4,0]-7-undecene. The reaction temperature and reaction time can be varied within a wide range depending on the starting materials, but in terms of -i, the reaction temperature is between -10 and 200°C, preferably between room temperature and 150°C.
°C1 reaction time is 0.1-30 hours, preferably 0.5
~24 hours.

In carrying out the reaction according to the present invention, -Form (II)
A carbamoyl chloride derivative represented by the formula (I[[
The thiourea derivatives represented by ) may be used in equimolar amounts or in a slight excess of either one.

When performing a reaction using a base to obtain the compound represented by the general formula (1) in a free form, it is preferable to use the base in an amount of twice the molar amount or slightly in excess of the carbamoyl chloride derivative represented by the - format (■). .

In addition, in the above reaction formula, a carbamoyl chloride derivative, which is a starting compound represented by general formula (II), can be prepared by a known method (Journal of Organic Chemistry:
Journal of Organic Chemi
39, p. 2897 (1974)). Furthermore, thiourea represented by formula (I[l) can be synthesized according to known methods.

Salts of the compound of the present invention represented by general formula (I) can be produced according to known methods. That is, -11
The compound of the present invention represented by formula (1) can be treated with hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, nitric acid, chloric acid,
Inorganic acids such as perchloric acid, phosphoric acid, thiocyanic acid, and tetrafluoroboric acid; formic acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, citric acid, lactic acid, oxalic acid, glycolic acid, -? It can be produced by treatment with a desired acid such as organic acids such as roic acid, succinic acid, malic acid, and dodecylbenpentaenoic acid.

The compound of the present invention represented by general formula (I) can be used in agriculture, forestry,
It can be used to protect plants from a wide variety of harmful arthropods encountered in fields such as horticulture.

For example, brown planthopper, brown planthopper, brown planthopper, black leafhopper, white leafhopper, brown leafhopper, psyllid, whitefly, citrus whitefly, green peach aphid, cotton aphid, Japanese radish aphid, snowdrop aphid, dung beetle, red stink bug. , Honhari stink bug,
Spider-edge stink bug, white stink bug, southern green stink bug, green stink bug, San Jose scale bug,
Hemiptera (Hen + 1pter) such as the scrub insect
a) Pests, Japanese beetle moth, Knot beetle moth, Red beetle moth,
Lepidoptera (Lepidoptera), such as the black-and-white moth, the yellow-bellied moth, the common yellowtail moth, the black-and-white moth, the yellow-bellied moth, the six-spotted moth, the apple leaf moth, the Japanese peach moth, the citrus leafminer moth, the pear moth, the white moth, the gypsy moth, the white-winged moth, the yellowtail moth, the armyworm moth, the armyworm moth, the Japanese armyworm moth, and the yellow-legged leafminer moth.
optera) Pests, Pygmy spp., P. optera,
Coleoptera (Lep.
idoptera) pests, Diptera pests such as the yellowtail fly, soybean pod fly, melon fruit fly, citrus fruit fly, rice leafminer fly, green leafminer fly, eggplant leafminer fly, onion fly, and seed fly, and pickpockets such as tea thrips, southern yellow thrips, and black thrips. Lapus, Two-spotted spider mite, Kanzawa spider mite, false two-spotted spider mite, orange spider mite, apple spider mite,
It is effective against mites such as the American spider mite and the teal spider mite. In addition to the above-mentioned fields, there are also various pests that cause harm to humans and livestock by transmitting infectious diseases, sucking blood, biting, causing dermatitis, etc. House fly, Sentinic fly, Giant black fly, Black fruit fly, Yellow fruit fly, American cockroach, German cockroach, Black cockroach, Brown cockroach, Mountain cockroach, House dust mite, Body bug, Head lice, Bed bug, Human flea, Dog flea, Cat flea, Helicoptera moth, Chado moth, Blue-winged cockroach, Green-winged roach moth S , blue-eared beetle, etc.
In addition, pests that cause damage to food and grain storage, such as woolly mites, staghorn mites, stag beetle weevils, red bean weevils, white-spotted beetles, and cypress moths, as well as pests that damage furniture, building materials, books, clothing, etc. , for example, Japanese termites, Japanese termites, Japanese yellow beetles, white beetles, burrs,
It is also useful for preventing damage from a wide variety of harmful arthropods, such as so-called nuisance insect pests, such as the Japanese carp fly, the Japanese chironomid, the black-and-white stink bug, the black-spotted beetle, the yellow millipede, the pill bug, and the woodlice. In particular, the compounds of the present invention exhibited remarkable insecticidal activity against Lepidoptera pests compared to known compounds.

When the compound of the present invention is actually applied, it can be used alone without the addition of other ingredients, but in order to make it easier to use as a pesticidal agent, it is generally applied with a carrier added thereto. The compounds of the present invention can be formulated into emulsions, wettable powders, powders, granules, fine granules, oils, and aerosols by methods well known in the art in the same manner as -g pesticides, without requiring any special conditions. It can be adjusted to any dosage form, such as smoke, smoke, poison bait, etc., and can be used for various purposes depending on the purpose.

Carrier here means an inorganic or organic substance, synthetic or natural, which is incorporated to aid in the delivery of the active ingredient to the area to be treated and to facilitate storage, transport and handling of the active ingredient compound. .

Suitable solid carriers include clays such as montmorillonite and kaolinite; inorganic materials such as diatomaceous earth, clay clay, cruzi, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate; and vegetable organic materials such as soybean flour, sawdust, and wheat flour. Examples include substances and urea.

Suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene; paraffinic hydrocarbons such as kerosene and mineral oil; halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane; acetone and methyl ethyl ketone. Ketones, dioxane, ethers such as tetrahydrofuran 1 methanol, ethanol,
Examples include alcohols such as propatool and ethylene glycol; dimethylformamide, dimethyl sulfoxide; and water.

Furthermore, in order to enhance the efficacy of the compound of the present invention, the following adjuvants may be used individually or in combination depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

For purposes such as emulsification, dispersion, spreading, wetting, binding, and stabilization, lignin sulfonates, alkylbenzenesulfonates,
Anionic surfactants such as alkyl sulfates; polyoxyalkylene alkyl ethers, polyoxyalkylene alkylaryl ethers, polyoxyalkylene alkyl amines, polyoxyalkylene alkylamides, polyoxyalkylene alkyl thioethers, polyoxyalkylene fatty acid esters, Nonionic surfactants such as glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene turbicun fatty acid ester, polyoxypropylene polyoxyethylene block polymer; lubricants such as calcium stearate and wax; stabilizers such as isopropylhydrodiene phosphate; Other examples include methylcellulose, carboxymethylcellulose, casein, and gum arabic. However, these components are not limited to those mentioned above. Furthermore, two or more of these compounds of the present invention can be used in combination to exhibit even more excellent insecticidal power. Also, for example, fenthion, fenitrothion, diazinon, chlorpyrifos, chlorpyrifos methyl, methidathion, dichlorvos, thiometone,
Acephate, trichlorfone, isoxathion, pyridafenthione, salithion, prothiophos, propafos, EPN, sulprofos, NAC, MTMC, MI
'PC, BPMC, PH-C, MPMC, XMC, pirimicarb, carbosulfan, benfuracarb, methomyl, oxamyl, pyrethrin, tetramethrin, phthalthrin, Paper Swan, allethrin, resmethrin,
Fenvalerate, nisphenevalerate, vermethrin, cypermethrin, fluno\linate, etofenbrox, crudisulinate, dihalothrin, bifuenthrin, diflubenzuron, chlorofluazuron, tefluhenzuron, flufenoxuron, sibronzin,
Insecticides such as buprofezin, phenoxycarb, penzoepine, neraistoxin, bensultap, thiocyclam, avermectin, deicofol, amitraz, polynactin complex, fenbutastin oxide, tricyclohexyltin hydroxide, hexythiasolis, flubenzamine, trialacene, clofuentedine, milbemycin,
A multi-purpose composition that becomes more effective when mixed with acaricides and other insecticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers, machine oil, other agricultural chemicals, etc. can be created, and synergistic effects can also be expected. The compounds of the present invention are stable against light, heat, oxidation, etc., but if necessary, antioxidants or ultraviolet absorbers, such as BIT (2,6-di-t-butyl-4-methylphenol), BHA ( By adding appropriate amounts of phenol derivatives such as (butylhydroxyanisole), bisphenol derivatives, arylamines such as phenyl α-naphthylamine, phenyl-β-naphthylamine, condensates of phenetidine and acetone, or benzophenone compounds as stabilizers, A composition with more stable effects can be obtained.

The insecticide and acaricide according to the present invention contains the compound as an active ingredient in an amount of 0.1 to 95% by weight, preferably 0.3 to 50% by weight. To apply the insecticide and acaricide of the present invention,
Generally, it is desirable to use the active ingredient at a concentration of 0.01 to 5000 ppm, preferably 0.1 to 11000 ppm. Moreover, the application amount per 10a is generally 1 g to 300 g of the active ingredient.

[Example 1] Next, the method for synthesizing the compound of the present invention will be explained by giving Examples of the compound of the present invention represented by the general formula (I), but the present invention is not limited thereto.

Example 1. 2-(2,2,2-trifluoroethylimino)-3-(4-tert-butylhendyl)
-5-(4-methoxyphenyl)-tetrahydro-1,
3,5-thiadiazin-4-one (compound No. 1
) composition.

Dissolve 0.33 g of N-chloromethyl-N-(4-methoxyphenyl)carbamoyl chloride and 0.32 g of 1-(4-tertiarybutylbenzyl)-3-(2,22-trifluoroethyl)thiourea in 20 mH of toluene. The mixture was heated under reflux for 3 hours. After the reaction, benzene was distilled off under reduced pressure and the resulting oil was subjected to column chromatography (
Purify with silica gel, developing solvent: hexane-ethyl acetate (9:1)) and obtain the desired 2-(2,2,2-trifluoroethyliminol)-5-(4-methoxyphenyl)-tetrahydro-
1.3.5-Thiadiazin-4-one 0. 20g was obtained. Melting point. 83.0~87.0°CBr I R v (cm-'.) 1695, 167
5, 1660, 1610, 15151460, 1440
, 1395, 1290, 1270, 1250, 1210
, 1140.10901030, 830,760,75
0.

MS 3, 80 (3H, s), 3.81 (IH+Q, J=9H
z), 4.77 (2N, s>, 5, 27 (2H, s),
6.80-7.5'O (8H., m).

(100KHz) Example 2. 2-(2,2.2-)lifluoroethylimino)'-1-(4-')lifluoromethylbenzyl)-5. Synthesis of -(4-methoxyphenyl)-tetrahydro-1.3.5-thiadiazin-4-one (Compound No. 4).

N-chloromethyl-N-(4-methoxyphenyl)carbamoyl chloride 1. OOg and 1-(4trifluoromethylbenzyl)-3-(2,2.

1.00 g of 2-trifluoroethyl)thiourea was dissolved in 50 d of toluene and heated under reflux for 3 hours. After the reaction, toluene was distilled off under reduced pressure, and the resulting oil was purified by column chromatography (silica gel, developing solvent: hexane-ethyl acetate (9:1)) to obtain the desired 2-(2.2
, 2-)lifluoroethylimino)-3-(4-trifluoromethylbenzyl)-5-(4-methoxyphenyl)-tetrahydro 1,3.5-thiadiazin-4-one 0.72 g was obtained. Melting point. 98.0~100.0'
C1395, 1335, 1290, 1270, 1255
, 1130.1110, 1090, 1065840.

MS 3, 81 (3H s), 4.81 (2B, s), 5.2
'9 (2H.s), 6.93 (2H, d, J=9Hz)
, 7.21 (2■, d, J = 9.Hz), 7.54 (2
1(, d, J=8.61(z), 7.56(2Lcl,
J=8.6Hz).

(100MHz) Example 3. 2-(2,2,2-)lifluoroethylimino)-3-(4-)lifluoromethylbenzyl)-
5-(4-ethoxyphenyl)-tetrahydro-135
- Synthesis of thiadiazin-4-one (compound No. 9).

1.88 g of N-chloromethyl-N-(4-ethoxyphenyl)carbamoyl chloride 1.50 g of 1-(4-trifluoromethylbenzyl)-1-(2,2゜2-trifluoroethyl)thiourea and 50 ml of toluene The mixture was dissolved in water and heated under reflux for 7 hours. After the reaction, toluene was distilled off under reduced pressure, and the resulting oil was subjected to column chromatography (silica gel, developing solvent: hexane-ethyl acetate (9
:1) ) to obtain the desired 1-(2,2,1-)lifluoroethylimino)-3=(4-trifluoromethylbenzyl)5-(4-ethoxyphenyl)-tetrahydro 1.3.5 -0.77 g of thiadiazin-4-one was obtained. Refractive index n D”=1.5219 1265.1140.1060.1040.1010.
930.820.755°MS 3.79 (2H, q, J = 9.4Hz), 4.03 (2
H, q, J=7Hz), 4.81 (2H, s), 5.2
9 (2H, s), 6.92 (2B, d, J=9Hz),
1.19 (2H, d, J=9Hz>, 1.55C4H,
s) (270 MHz) Next, a production example of the starting material for the compound of the present invention will be shown below.

Reference=i[1-(4-trifluoromethylhensyl)-3
-Synthesis of (2,2,2-)lifluoroethyl)thiourea.

(1) 4-) Lifluoromethylbenzyl isothiocyanate 10g of 4-trifluoromethylbenzylamine and 11.78g of dicyclohexylcarbodiimide (occ),
The mixture was added dropwise to a mixed solution of 25 m2 of carbon disulfide and 50 m2 of ethyl ether at -10°C while stirring. The mixture was returned to room temperature and left for 12 hours. The reaction solution was filtered, the residual aroma was washed with ethyl ether, the mixture was combined with the filtrate, the solvent was distilled off under reduced pressure, and the resulting oil was subjected to column chromatography (silica gel, developing solvent: hexane-ethyl acetate (10:
1)) to obtain 11.15 g of the target 4-trifluoromethylhendylisothiocyanate. Refractive index n n
”=1.52.70eat I Rv (cm-'): 2930.2180.2
090.1690.1620aX 1420.1325.1165.1125.1065.
7.0 g of 1020.815° diisothiocyanate and 2.2. ．． 2-,) 3.83g of trifluoroethylamine
was dissolved in 50 d of ethyl acetate and left at room temperature for 24 hours. Ethyl acetate was distilled off under reduced pressure, and the obtained white crystals were recrystallized with hexane to obtain the desired product (1-(4-)lifluoromethylbenzyl)-3-(2,2,2-)lifluoroethyl).
8.79 g of thiourea was obtained. Melting point: 80.0-82.0
°C01190,1180,1145,1320,13
05, 1280, 1245, 1160, 1115, 11
05,1060°MS 7.47 (28, d, J=8Hz), 7.66 (2H,
d, J=8Hz), (100MHz)References Angewante Hemi-International Nission:
Angewandte Chemie Tntern
ational Edition: Volume 6, p. 174 (1967) (2) 4 obtained with 1-(4-)lifluoromethylhenzyl)3-(2,2,2-trifluoroethyl)thiourea (1) -Trifluoromethylben MS 4.76 (2H, d, J=6Hz), 6. ．． 02 (IH
, m), 6.56 (IH, m), 7.38 (2B, d
J=8Hz), 7.57 (2H, il, J=8Hz).

(100MI(z)) Next, the formulation containing the compound of the present invention represented by form (I) as an active ingredient and the formulation method of the insecticide according to the present invention will be specifically explained using formulation examples. is not limited to these.

Formulation example 1. Emulsion Compound of the present invention・・・・・・・・・・・・・・・・・・
・10 parts Tsurupol 355S・・・・・・・・・・・・
・・・・Part 1 (Toho Chemical registered trade name) Xylene・・・・・・・・・・・・・・・ Self・・・・
- Obtain an emulsion by dissolving and mixing 80 parts or more.

Formulation example 2. Wettable powder Compound of the present invention・・・・・・・・・・・・・・・・・・
20 parts Sodium ligninsulfonate 10 parts Sodium alkylnaphthalene sulfonate 5 parts White carbon 5 parts
Diatomaceous earth・・・・・・・・・・・・・・・・・・
...60 parts or more are uniformly mixed and pulverized to obtain a wettable powder.

Formulation example 3. Powder 3 parts of the compound of the present invention are dissolved in 710 parts of acetate, 87 parts of clay for powder are added, and the acetone is evaporated to obtain a powder.

Formulation example 4. Granules 3 parts of the compound of the present invention, 1 part of sodium lignosulfonate, 20 parts of talc, and 76 parts of bentonite are mixed, an appropriate amount of water is added, kneaded, granulated, and dried to obtain granules.

Formulation example 5. Poison bait: 1 part of the compound of the present invention, 5 parts of sugar, 50 parts of bran, 2 parts of rice bran
After mixing 0 parts and 24 parts of wheat flour, adding an appropriate amount of water and kneading, the mixture is granulated and dried to obtain a poison bait.

Next, in order to clarify that the compound of the present invention has excellent insecticidal activity, it will be specifically explained in the following test examples. Furthermore, all tests were conducted in triplicate, and the results are shown as the average value.

Test example 1. Effect on Spodoptera trifoliata The emulsion prepared according to Formulation Example 1 is diluted with water to a concentration of 500 ppm, and the leaves of Citrus orchid are immersed. After air-drying, transfer the treated leaves to a plastic cup and place the 2nd instar larva of Spodoptera japonica 1.
The mortality rate was investigated 5 days after feeding each animal. The results are shown in Table 2. In addition, the following compounds were used as comparative compounds.

2 Comparative Compound (a) Japanese Patent Publication 1986-140
Compounds described in No. 577.

Table 2: Effect on Spodoptera spp.) (CH, 0) 2-P-C1-CI-CC12 Comparative Compound (c) Compound described in Japanese Patent Publication No. 1983-3083 (-Ship name: Buprofezin).

CH3 100 2200 100 100 10100 Comparative compound (a) 0 Comparative compound (b) 100 Comparative compound (c) 0 No treatment 0 From Table 2, the compounds of the present invention have stronger insecticidal activity than known structurally similar comparative compounds. It turns out that it has.

Test example 2. Effect on diamondback moth The emulsion prepared according to Formulation Example 1 was diluted with water to a concentration of 500 ppm, and sprayed with a hand sprayer to the extent that the drug solution dripped lightly onto potted Orchid seedlings (5-6 leaf stage). The air-dried transplants were cut and placed in a plastic cup, and 10 second-instar diamondback moth larvae were fed, and the mortality rate was examined 5 days later. The results are shown in Table 3.

Table 3: Effect on diamondback moth"' 500 ppm 100 2 100 4 100 100 9 100 Comparative compound (a) 0 Comparative compound (b) 80 Comparative compound (c) 0 No treatment 0 From Table 3, it can be seen that the compounds of the present invention It is found that this compound has stronger insecticidal activity than comparative compounds with similar structure.

Therefore, the above test examples show that the compound of the present invention has a stronger insecticidal activity against Lepidoptera pests than a known structurally similar comparative compound.

[Effects of the Invention] As is clear from the above explanation, the tetrahydro-13,5-thiadiazin-4-ones represented by the general formula (1) or its salts according to the present invention have an extremely excellent pest control effect. It is a compound that shows Further, the agricultural chemicals containing the tetrahydro-1,3,5-thiadiazin-4-ones represented by the general formula (1) or salts thereof according to the present invention have excellent properties and are useful as insecticides.

Claims (3)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 represents an alkyl group having 1 to 4 carbon atoms,
R^2 is an alkyl group having 1 to 4 carbon atoms, a haloalkyloxy group having 1 to 4 carbon atoms, a haloalkylthio group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms;
4 shows a haloalkenyl group. ) Tetrahydro-1,3,5-thiadiazin-4-ones or salts thereof. (2) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 represents an alkyl group having 1 to 4 carbon atoms.)
The compound represented by the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R^2 is an alkyl group having 1 to 4 carbon atoms, or a haloalkyloxy group having 1 to 4 carbon atoms. , a haloalkylthio group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkenyl group having 1 to 4 carbon atoms. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) Tetrahydro-1,3,5-thiadiazin-4-one represented by (In the formula, R^1 and R^2 each have the above meanings.) or their salts. (3) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R^1 represents an alkyl group having 1 to 4 carbon atoms,
R^2 is an alkyl group having 1 to 4 carbon atoms, a haloalkyloxy group having 1 to 4 carbon atoms, a haloalkylthio group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms;
4 shows a haloalkenyl group. ) An insecticide or acaricide containing one or more of the following tetrahydro-1,3,5-thiadiazin-4-ones or their salts as an active ingredient.