JPS6176451A - Carboxyamidine derivative, its preparation and insecticide - Google Patents

Abstract

NEW MATERIAL:To compound of formula I [X is halogen or methyl; Y is H or halogen; A is lower alkyl, (halogen-substituted) benzimidazolyl, triazolyl, etc.; R1 is lower alkyl, lower alkoxy, etc.; R2 is H, halogen, nitro, etc.; R3 is H, halogen or lower alkyl]. EXAMPLE:N-( 2,6-difluorobenzoyl )-N'-[3-methyl-4-( 1,1,2,2-tetraflu-oroethoxy)phe nyl]-1-imidazolecarboxyamidine. USE:Insecticide having broad insecticidal spectrum and exhibiting excellent activity against lepidopterous, coleopterous or dipterous vermin, etc. PREPARATION:The compound of formula I can be prepared by reacting the thiourea derivative of formula II with the compound of formula A'-SO-A' [A' is lower alkyl or (halogen-substituted) benzimidazolyl, triazolyl, etc.] in a solvent such as methylene chloride, at 0-50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel azolecarboxamidine derivative, a metal salt thereof, a method for producing the same, and an insecticide containing the compound as an active ingredient.

1 (Prior Art) It has been widely known that the penzoyl ure derivative represented by the following general formula has insecticidal activity.
-6550, 51-101950, 52-1023
No. 9, etc.) JP-A-46-65 as commercialized
No. 50 (2 disclosed di f Lubenzur
on (-ship name) is a typical example.

(Means for Solving the Problems - Compounds and Manufacturing Methods) The present invention is based on the general formula [wherein, X is a halogen atom or a methyl group, Y is a hydrogen atom or a halogen atom, and A is a lower alkyl group or a halogen Benzimidazolyl group, benztriazolyl group, triazolyl group, birazolyl group or imidazolyl group t1 or formula 88-r (r is substituted with a lower alkyl group, a halogen atom or a methyl group) which may be substituted with an atom (10) (, OCH,
O- group, melon has hydrogen atom, halogen atom, nitro group, lower alkyl group, halogeno lower alkoxy group, halogeno lower alkenyloxy group.

(2) represents a hydrogen atom, a halogen atom 4, a lower alkyl group, or a lower alkoxy group. ] A compound represented by the above, a metal lump thereof, a method for producing the same, and an insecticide containing the compound as an active ingredient.

The compound of the present invention has a wide insecticidal spectrum and has excellent efficacy against various insect pests such as Lepidoptera, Coleoptera, and Diptera. It also has the effect of killing the eggs that are being laid.

The compound of the present invention is produced (in the second case, the general formula (in the formula,
X, Y, R, , R, and bird have the same meanings as above. ) Thiourea derivatives represented by the general formula % formula % () (wherein A' is a lower alkyl group or a benzimidazolyl group optionally substituted with a herogen atom, a benztriazolyl group, a triazolyl group, a pyrazolyl group) or imidazolyl group) in an organic solvent.

The compound represented by the general formula (III) is produced by reacting the corresponding azole with thionyl chloride in an organic solvent, and is usually reacted with the thiourea derivative without isolation. As the organic solvent, common inert solvents such as methylene chloride, chloroform, and acetonitrile can be used. The reaction temperature is 0° to 50°C, preferably 0° to room temperature,
Allow to react for ~10 hours. Among the compounds of the present invention, the compound in which A is a group represented by the formula S8r is a compound represented by the following reaction formula (as shown in 2, C2, a thiourea derivative represented by the above formula (2), and a lower alkylthiohalide or N-lower It can be produced by reacting with alkylthiosuccinoimide.

The reaction involves benzene, toluene, dimethoxyethane, acetone, tetrahydrofuran, and dichloromethane.

In a common inert solvent such as chloroform or acetonitrile, in the presence of an organic or inorganic base such as sodium alcolade, sodium carbonate, triethylamine, imidazole, etc., at 0°C to 50°C, preferably 0°C to room temperature, for 5 to 10 hours. be exposed.

Production of the metal salt of the compound of the present invention (secondly, the compound represented by the general formula (I) produced as described above is mixed in water or an organic solvent such as acetone, methanol, ethanol, dimethylformamide, etc.) A sodium salt or a potassium salt is obtained by mixing with a caustic alkali such as caustic soda or caustic potash, or with metallic sodium in an alcoholic solvent, and reacting with heating if necessary.

Next, the sodium salt or potassium salt is reacted with a salt of the desired metal in the same manner (2) to obtain the desired metal salt.In many cases, the metal salt is
It separates out as a precipitate or crystals in the above-mentioned solvents.

Examples of metal salts that form metal salts with the compound represented by the general formula +I) include Ca, Mg, Ba, Ni, Mn
, Co %Zn %re 1Ag , salts of monovalent, divalent or trivalent metals such as Na, K, e.g. chlorides,
Hydroxides, sulfates, nitrates, acetates, and other water or organic solvent (-soluble metal salts) are used.

The nanostructure was determined from the results of spectral analysis such as IR and MA88% Rare.

The compound of the present invention has two types of tautomeric structures shown below, each of which contains E and O isomers.

The present invention includes both isomers.
(Example) The following two examples will be given, and the compounds of the present invention will be further explained in detail.

Example 1 A solution of 1.11i of imidazole in 20ml of methylene chloride was cooled with ice water (while stirring twice, 0.5ml of thionyl chloride was
A solution of N in 5fnl of methylene chloride was added dropwise. After stirring for 10 minutes, N-(2,6-difluorobenzoyl)-N
'-[3-Methyl-4-(1,1,2,2,-tetrafluoroethoxy)phenyl]teoclea 1.5II was added and stirred at room temperature for 7 hours. The reaction solution was filtered, and insoluble materials were washed with methylene chloride. The P solution and the washing solution were combined, washed with water, dried over magnesium sulfate, and then methylene chloride was distilled off under reduced pressure. The residue was washed with diethyl ether to give a white powder of N-(2,6-difluorobenzoyl)-N.
'-[3-Methyl-4-(1,1°2.2-tetrafluoroethoxy)phenyl]-1-imidazolecarboxamidine 1. Obtained Og.

mp 139-141°, yield 61.6%.

Example 2 (Compound No. 11): 20 fijl of methylene chloride=1.19 imidazole was added, and while stirring at C2 while cooling with ice water, 0.0 ml of thionyl chloride was added.
A 5N methylene chloride 5frLl solution was added dropwise. After stirring for 10 minutes, N-(4-chloroA-3-trifluoromethoquinphenyl)-N'-(2,6-difluorobenzoyl)thiourea 1. ! 10 at room temperature after adding M+.
Stir for hours. The reaction solution was filtered, and insoluble matter was washed with methylene chloride. The solution F and the washing solution were then poured together and the methylene chloride was distilled off under reduced pressure. The residue was washed with diethyl ether to obtain a white powder of N-(4-chloro-3-trifluoromethoxyphenyl)-N'-(2,6-difluorobenzoyl)-1-imidazolecal, poquinamidine 1.2I.
I got it.

mp139-141°, yield 74.0%.

Example 3 (Compound No. 16): N-[3-chloro-5-methyl-4-(1,1,2゜2
-tetrafluoroethoxy)phenyl)-N'-(2,
6-difluorobenzoyl)teoclea 1.0 g N-isopropylsulfenylsuccinimide 0.45 I and imidazole 0.1 N were stirred in methylene chloride 10 f FIl at room temperature for 4 days. The reaction solution was washed with water, treated with activated carbon, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, mixed solvent (ether: n-hexane = 1:1)
N-[3-chloro-5-methyl-4-(1,
1,2,2-tetrafluoroethoxyle)phenyl)-N
'-(2,6-difluorobenzoyl)-s'-isopropylsulfenylisothiourea o,sg was obtained.

m, p, 82-86° Example 4 (Compound No. 20): Dissolve methanol 15fij+=sodium 0.11 II, stir at room temperature, and then dissolve N-(3-chloro-5-methyl-4-(1 , 1,2,2,-tetrafluoroethoxyV)phenyl)-N'-(2,6-difluorobenzoyl)-1-imidazole After adding and dissolving 2.5 g of carboxamidine, methanol was distilled off. After washing the residue with a mixed solvent (ether: n-hexane = 1:5),
Dry in a vacuum desiccator to obtain N-(3-chloro-5-
1.81 of methyl-4-(1,1,2,2-tetrafluoroethoxy)phenyl)-N'-(2,6-difluorobenzoyl)-1-4 mitasole carboxamidine sodium salt was obtained.

mp 145-149゜Example 5 (Compound No. 22): N-(3-'chloro-5-methyl-4-(1,1,2゜2-tetrafluoroethoxy)phenyl)-N'-(2
,6-difluorobenzoyl)-1-imidazolecarboxamidine sodium salt 0.7ON in water 10fret
(- □5t of dissolved calcium chloride 0.15g
nll aqueous solution was added, and the mixture was allowed to stand at room temperature for one day. The precipitated crystals were separated, washed with water, and then dried in a vacuum desiccator to obtain 0.55 g of calcium salt. mp 162-167
Representative examples of the compounds of the present invention are shown in Table 1.

Table 1 (Means for solving the problem - Insecticide) The insecticide of the present invention contains a compound represented by the general formula (I) as an active ingredient, and is a pure product of the active ingredient compound. Although it can be used as is, it is usually used in the form of common agricultural chemicals, such as wettable powders, powders, emulsions, and flowables. As additives and carriers, when the purpose is to use as a solidifying agent, vegetable powders such as soybean flour and wheat flour, diatomaceous earth,
Fine mineral powders such as apatite, gypsum, talc, pyrophyllite, and clay are used.

For liquid formulation purposes, use kerosene, mineral oil, petroleum,
Solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, water, etc. are used as the solvent. If necessary, a surfactant may be added to these preparations (=) in order to obtain a uniform and stable form.The wettable powders, emulsions, flowables, etc. obtained in this way can be mixed with water to a specified level. It is diluted to a concentration of C to make a suspension or emulsion, and powders and granules are used as they are by spraying them on plants.

(Example - Insecticide) The following (=Example of the formulation is shown, but the carrier, surfactant, etc. to be added are not limited to these examples.

Example 6 Emulsion Compound of the present invention 10 parts Acylphenylpolyoxyethylene 5
〃Dimethylformamide 3
5 parts xylene 50〃 Mix and dissolve, use (: l!li''; t, dilute with water and spray as an emulsion.

Example 7 Hydrating agent Compound of the present invention 20 parts Higher alcohol sulfate ester 5 parts
I
74 #White carbon
Mix 1 # or more of the mixture and grind it into a fine powder (C), then dilute it with water and spray it as a suspension.

Example 8 Powder Compound of the present invention 5 parts
Ruri
91 #silica
3 Alkylphenylpolyoxyethylene 1
〃Crush and mix the above ingredients and use (spread as is for the second time).

It goes without saying that the compound of the present invention is sufficiently effective alone, but since it has a slow-acting effect on larvae (=20), it may be used in combination with one or more fast-acting insecticides. The compound of the present invention can also be used in combination with one or more types of fungicides and acaricides other than fast-acting insecticides.

Representative examples of insecticides that can be used in combination with the compounds of the present invention are shown below.

Organophosphorus insecticide, carbamate insecticide fenthion,
fenitrothion, diazinon, chlorpyrifos,
ESF, vamidothion, phenthoate, dimethoate, formothion, marathon, dibuterex, thiometone, dichlorpol, isoxathion, pyridafenthione, chlorpyrifos, DMTP, prothiofos, sulprofos, profenofos, CVMP, saliteoi, E
PN%CYP.

Aldicarb, propoxur, virimicarp, methomyl, cartap, carbaryl, thiocyania
, Carbosulfen, Carbosulfen, Nicotine 221-pyrethroid insecticides permethrin, cypermethrin, decamerin, fenvalerate, fenpropathrin, rhinoconvex surin,
fluparinate, phencyflate, tralomethrin,
Cyfluthrin, Fluparinate, Pyrethrin, Allethrin, Tetramethrin, Resmethrin, Parsulin, Dimethrin, Propasurin, Prosulin (Effects of the Invention) Next, test examples will be given to demonstrate the insecticidal activity of the compounds of the present invention.

Test Example 1 Efficacy against fall armyworm (2) The compound of the present invention was diluted with water according to the formulation of the emulsion shown in Example 6 (=compound concentration: 500, 1251) to a concentration of 1 m (= water). 3
After immersion for 0 seconds and air drying, the leaves were placed in a chalet containing five 3rd instar armyworm larvae. Cover with a glass lid and place in a thermostatic chamber with a temperature of 25°C and humidity of 65%. After 5 days, the insect killing rate was determined. The results are shown in Table 2 (two bottles).

Table 2 Test Example 2 Efficacy against Spodoptera trifoliata (2) The compound of the present invention was prepared in Example 7 (=formulation of the indicated hydrating agent (: Therefore, the compound concentration was 125, 31.3 ppm +=C:
Diluted with water. Soak the sweet potato leaves in the chemical solution for 30 seconds, and after air-drying, put the leaves in a 9cIIL diameter chasselle containing five 3rd instar Spodoptera larvae and cover with a glass lid.The petri dish has a temperature of 25℃ and a humidity of 65℃. % in a constant temperature room (every two hours), and examined the insect killing rate after 5 days.The results are shown in Table 3 (two bottles).

Table 3 Rice Test Example 11=Same Test Example 3 Efficacy against Spodoptera spp. Egg 1'' The compound of the present invention was tested in Example 6 (according to the formula E of the double emulsion, compound concentration was 500 and 1251) I)m+: , diluted with 1 water.
After immersing the dish in the air and drying it, put it in a petri dish (with a glass lid) and place it in a constant temperature room at a temperature of 25°C and a humidity of 65%.
The results are shown in Table 4 (Same applicant as in Nihonmai Test Example 1: Nippon Soda Co., Ltd.)

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, X is substituted with a halogen atom or a methyl group, Y is a hydrogen atom or a halogen atom, and A is substituted with a lower alkyl group or a halogen atom. benzimidazolyl group, benztriazolyl group, triazolyl group, pyrazolyl group or imidazolyl group, or represented by the formula SS-r (r represents a lower alkyl group, a phenyl group substituted with a halogen atom or a methyl group); R_1 is a lower alkyl group, a lower alkoxy group, a halogeno lower alkoxy group, or together with R_2, -CH_2
OCH_2O- group, R_2 represents a hydrogen atom, halogen atom, nitro group, lower alkyl group, halogeno lower alkoxy group, or halogeno lower alkenyloxy group, R_3 represents a hydrogen atom, halogen atom, lower alkyl group, or lower alkoxy group . ] A compound represented by and its metal salt. (2) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, X is a halogen atom or a lower alkyl group, Y is a hydrogen atom or a halogen atom, R_1 is a lower alkyl group, a lower alkoxy group, a lower halide -CH_2 together with an alkoxy group or R_2
OCH_2O- group, R_2 represents a hydrogen atom, halogen atom, nitro group, lower alkyl group, halogeno lower alkoxy group, or halogeno lower alkenyloxy group, R_3 represents a hydrogen atom, halogen atom, lower alkyl group, or lower alkoxy group . ) and a compound represented by the general formula A'-SO-A' (wherein A' is a lower alkyl group or a benzimidazolyl group optionally substituted with a halogen atom, a benztriazolyl group, a triazolyl group, (In the formula, R_3 has the same meaning as above.) A method for producing a compound represented by: (3) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X is substituted with a halogen atom or a methyl group, Y is a hydrogen atom or a halogen atom, and A is substituted with a lower alkyl group or a halogen atom. benzimidazolyl group, benztriazolyl group, triazolyl group, pyrazolyl group or imidazolyl group, or represented by the formula SS-r (r represents a lower alkyl group, a phenyl group substituted with a halogen atom or a methyl group); R_1 is a lower alkyl group, a lower alkoxy group, a halogeno lower alkoxy group, or together with R_2, -CH_2
OCH_2O- group, R_2 represents a hydrogen atom, halogen atom, nitro group, lower alkyl group, halogeno lower alkoxy group, or halogeno lower alkenyloxy group, R_3 represents a hydrogen atom, halogen atom, lower alkyl group, or lower alkoxy group . ] An insecticide characterized by containing the compound represented by these or its metal salt as an active ingredient.