JPH04217992A - Production of organic phosphorus compound and insecticide/miticide/nematicide containing the same - Google Patents

Abstract

PURPOSE:To obtain the title low toxic compound virtually free from offensive or irritating odor, having effective controlling activity on noxious insects, mite and nematode by reaction in the presence of a deoxidizer between a specific heterocyclic compound and a phosphoric acid compound. CONSTITUTION:The objective respective compounds of formulas IV-V can be obtained by reaction in the presence of a deoxidizer between (A) a compound of formula I (Z is CHNO2, N-NO2 or N-CN; A is ethylene or trimethylene, which may be substituted with 1-3C alkyl) and (B) compounds of formulas II-III (R<2> is 1-4C alkyl; Hal is halogen). The present compounds have markedly higher activity than those of conventional ones as insecticides/miticides/ nematicides, being also highly safe.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention applies to harmful insects, mites,
A method for producing an organophosphorus compound that exhibits an effective control action against nematodes, and an insecticide containing the compound as an active ingredient;
This relates to acaricides and nematicides.

0002

[Prior Art] JP-A No. 63-156786 discloses that in the production of insecticidal nitroimino or cyanoimino compounds, compounds used in the insecticide, acaricide, and nematocide of the present invention are included in the production intermediate compounds. Some are listed. However, these intermediate compounds are only used as intermediate raw materials in producing the above-mentioned insecticidal nitroimino or cyanoimino compounds, and their biological activity and use as insecticides, acaricides, and nematicides are not described at all.

0003

SUMMARY OF THE INVENTION An object of the present invention is to provide a drug that is far more effective and highly safe than conventional insecticides, acaricides, and nematicides.

0004

[Means for Solving the Problems] In order to develop effective insecticidal, acaricidal, and nematocidal agents, the present inventors synthesized various compounds and investigated their insecticidal, acaricidal, and nematicidal activities. As a result, general formula (I)

[0005]

[Chemical formula 8]

[0006] (In the formula, R1 and R2 are each C1 to
Represents a C4 alkyl group, Z is CHNO2, N-N
O2 or N-CN, A is an ethylene group optionally substituted with a C1 to C3 alkyl group or C1
The present inventors have discovered that compounds represented by the following formula (representing a trimethylene group optionally substituted with a C3 alkyl group) exhibit excellent effects, and have completed the present invention.

Furthermore, many conventional organic phosphorus compounds exhibit strong toxicity to warm-blooded animals, but the compound represented by the above general formula (I) has low toxicity and is extremely useful in terms of safety. big. The organic phosphorus compound represented by the above general formula (I) includes stereoisomers such as optical isomers. Also, the following general formula (I')

[0008]

[Chemical formula 9]

The active ingredient of the insecticide, acaricide and nematicide of the present invention can exist as a tautomer such as (wherein R1, R2, Z and A are as defined above). It can be used as The organic phosphorus compound represented by the above general formula (I) is, for example, the following (i) or (i)
i) It can be manufactured by the following method.

0010

[Chemical formula 10]

[0011]

[Chemical formula 11]

(In the formula, R1, R2, Z and A are as described above, and Hal is a halogen atom) The above reactions are usually carried out at -100 to +60°C, preferably -80 to +
It is carried out in a temperature range of 30°C. In addition, these reactions are carried out in the presence of a deoxidizing agent, and examples of the deoxidizing agent include organic lithium compounds such as n-butyllithium, t-butyllithium, and phenyllithium; sodium hydride, potassium hydride, metallic sodium, Examples include inorganic bases such as sodium hydroxide and potassium hydroxide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; and organic bases such as triethylamine and pyridine. In addition, these reactions are preferably carried out in the presence of a solvent, such as aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; cyclic or acyclic aliphatic hydrocarbons such as hexane and cyclohexane; diethyl Examples include ethers such as ether, methyl ethyl ether, dioxane, and tetrahydrofuran; nitriles such as acetonitrile, propionitrile, and acrylonitrile; aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, sulfolane, and hexamethylphosphoric acid triamide; .

Next, representative compounds represented by the general formula (I) are illustrated in Table 1. Compound numbers are referred to in the following description.

[0014]

[Chemical formula 12]

[0015] In Table 1, "←" in the column "←A-"
As shown in the above formula, represents a bond between a hydrogen atom and an N atom.

[0016]

[Chemical formula 13]

IR and NMR of the compounds in Table 1 are shown in Table 2.
As shown in the table.

[0018]

[Chemical formula 14]

[0019]

[Chemical formula 15]

[0020]

[Chemical formula 16]

The compound represented by the general formula (I) exhibits excellent activity as an active ingredient of insecticides, acaricides and nematicides. For example, Coleoptera such as scarab beetles, potato beetles, ladybird beetles, and rice weevils, Lepidoptera such as armyworms, cabbage butterflies, diamondback moths, silver beetles, leaf beetles, and beetles, planthoppers, leafhoppers, whiteflies, and aphids. , Hemiptera such as scale insects,
Agricultural and horticultural pests such as Thripsidae such as green tea thrips and southern yellow thrips, sanitary pests such as mosquitoes, flies, cockroaches, fleas, and lice, grain storage pests, clothing, house pests, and cat nematodes. , plant parasitic nematodes such as Negusarenematodes, two-spotted spider mites,
It is effective against plant-parasitic mites such as false red spider mite, Kanzawa spider mite, and orange spider mite. It is also effective against soil pests. Soil pests mentioned here include slugs, gastropods like snails, pill bugs,
Examples include isopods such as woodlice. Furthermore, it is effective against pests such as dicofol and organophosphate-resistant plant parasitic mites, organophosphate-resistant aphids, and house flies.

When using the compound represented by the general formula (I) as an active ingredient in insecticidal, acaricidal, nematicidal, or soil pesticidal compositions, it can be applied as is, but generally conventional methods are used. As in the case of agrochemical formulations, they can be formulated together with agrochemical auxiliaries into various forms such as emulsions, powders, wettable powders, liquids, aerosols, and pastes. The mixing ratio of these ingredients is usually 0.5 to 90 parts by weight of the active ingredient and 10 to 99.5 parts by weight of the pesticide auxiliary. When these preparations are actually used, they can be used as they are, or they can be diluted to a predetermined concentration with a diluent such as water. The pesticide adjuvants mentioned here include carriers, emulsifiers, suspending agents,
Examples include dispersants, spreading agents, penetrants, wetting agents, thickeners, stabilizers, etc., and they may be added as appropriate.

[0023] Carriers can be divided into solid carriers and liquid carriers. Solid carriers include animal and vegetable powders such as starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal, and milk powder; talc, kaolin, bentonite, calcium carbonate, zeolite,
Examples include mineral powders such as diatomaceous earth, white carbon, clay, alumina, and sulfur powder. Liquid carriers include water; alcohols such as methyl alcohol and ethylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran; aliphatic hydrocarbons such as kerosene and kerosene; Aromatic hydrocarbons such as methylbenzene, cyclohexane, and solvent naphtha; Halogenated hydrocarbons such as chloroform and chlorobenzene; Amides such as dimethylformamide; Esters such as ethyl acetate and glycerin esters of fatty acids;
Examples include nitriles such as acetonitrile; sulfur-containing compounds such as dimethyl sulfoxide.

[0024] Also, if necessary, it may be mixed or used in combination with other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, plant growth regulators, etc. can be used, and may show even better effects in this case. For example, as insecticides, acaricides, or nematicides, organic phosphate compounds such as DDVP, diazinon, malathion, fenitrothion, prothiophos, dioxabenzophos, acephate; carbaryl, propoxur, oxamyl, carbofuran, methomyl, etc. carbamate compounds; organochlorine compounds such as dicofol and tetradifone; organometallic compounds such as cyhexatin and fenbutatin oxide; pyrethroid compounds such as fenvalerate, permethrin, deltamethrin, and bifenthrin; diflubenzuron,
Urea compounds such as teflubenzuron and chlorfluazuron; heterocyclic compounds such as buprofezin and hexythiazox; other compounds include dinitro compounds, organic sulfur compounds, urea compounds, amidine compounds, and triazine compounds. It will be done. Furthermore, B.T.
It can also be used in combination or in combination with microbial pesticides such as insect pathogens and insect pathogen virus agents.

For example, as a disinfectant, organic phosphorus compounds such as iprobenfos, edifenphos, and focetil; organic copper compounds such as copper oxyquinoline and copper terephthalate; organic chlorine compounds such as phthalide and chlorothalonil; maneb, zineb, Dithiocarbamate compounds such as propineb; dicarboximide compounds such as iprodione, vinclozolin, and procymidone; azole compounds such as triadimefon, bitertanol, etaconazole, propiconazole, and penconazole;
Benzimidazole compounds such as thiophanate methyl and benomyl; carbinol compounds such as fenarimol and flutriafor; benzanilide compounds such as mepronil and flutolanil; phenylamide compounds such as metalaxyl and oxadixyl; and other compounds such as piperazine compounds and quinoxaline compounds. compounds, morpholine compounds, anthraquinone compounds, sulfenic acid compounds, crotonic acid compounds, urea compounds,
Examples include antibiotics.

As mentioned above, insecticides, acaricides, and nematicides containing the compound represented by the general formula (I) as an active ingredient are effective against various harmful insects, harmful mites, harmful nematodes, and harmful soil. It is effective in controlling pests, and the application is generally 1 to 20,000
000ppm, preferably 20-2,000ppm
The active ingredient concentration is The concentration of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, pest outbreak status, etc. For example, in the case of harmful aquatic insects, the concentration range of the active ingredient in water is below the above range, since it is possible to control aquatic pests by spraying a chemical solution with the above concentration range to the place of occurrence. The application amount per unit area is approximately 0.1 to 5,000 g as the active ingredient compound per 10 a.
Preferably 10 to 1,000 g are used. but,
In special cases it is also possible to depart from these ranges.

Various preparations containing the compound represented by the general formula (I) or their diluents can be applied by commonly used application methods, ie, spraying (e.g., scattering, spraying, misting, atomizing). , powder application, water surface application, etc.) soil application (mixing, irrigation, etc.), surface application (spraying, powder coating,
This can be done by using poison bait, etc.). It is also possible to feed livestock with the above-mentioned active ingredients mixed with their feed to control the growth and development of harmful insects, particularly harmful insects, in their excrement. It can also be applied by a so-called ultra-high concentration small amount spraying method. In this way, 100% active ingredient content is possible.

[0028]

EXAMPLES Next, the method for producing the compound represented by the general formula (I) will be explained in more detail with reference to synthetic examples. Synthesis Example 1 O-ethyl-S-n-propyl (2-nitroimino-1
-imidazolidinyl)phosphonothiolate (Compound No. 1) 3.52 g of 60% sodium hydride and N,N-
10.41 g of 2-nitroiminoimidazolidine was gradually added to a mixture of 50 ml of dimethylformamide. After a while, 29.7 g of a 59.2% toluene solution of O-ethyl-Sn-propylphosphorochloride thiolate was added.
was gradually added dropwise. After the dropwise addition was completed, the reaction solution was stirred at room temperature for 12 hours to complete the reaction. After the reaction was completed, the reaction solution was poured into ice water and extracted with chloroform. After washing the chloroform layer with water, it was dried over anhydrous magnesium sulfate, the chloroform was distilled off under reduced pressure, and then subjected to silica gel column chromatography (
Purification was performed using chloroform:methanol (solvent = 97:3) to obtain 11.8 g of the title compound as an oil. IR (neat): 3360 (NH), 1255 (p=0) cm-
1NMR (CDCl3) δ (ppm): 0.8-2
．． 1 (m, 8H, OCH2 CH3, SCH2 CH
2 CH3), 2.8-3.4 (m, 2H, SCH2
), 3.8-4.8 (m, 6H, OCH2, NCH
2 CH2 N), 8.8 (bs, 1H, NH) Synthesis Example 2 O-ethyl-S-n-propyl (2-nitroiminohexahydropyrimidin-1-yl)phosphonothiolate (
Compound No. 2) 2 in a mixture of 0.67 g of 60% sodium hydride and 10 ml of N,N-dimethylformamide.
- 2.00 g of nitroiminohexahydropyrimidine were added slowly. After a while, 5.70 g of a 59.2% toluene solution of O-ethyl-Sn-propylphosphorochloride thiolate was gradually added dropwise. After the dropwise addition was completed, the reaction solution was stirred at room temperature for 12 hours to complete the reaction. After the reaction was completed, the reaction solution was poured into ice water and extracted with dichloromethane. The dichloromethane layer was washed with water, dried over anhydrous magnesium sulfate, dichloromethane was distilled off under reduced pressure, and purified using silica gel column chromatography (solvent = chloroform: methanol = 97:3) to obtain a crystalline product with a melting point of 75-77°C. 1.63 g of the title compound was obtained. Synthesis Example 3 O-ethyl-S-n-propyl (2-dianoimino-1
-imidazolidinyl) phosphonothiolate (compound number 3) 1.1 g of 2-cyanoiminoimidazoline was added to N,N-
After dissolving in 15 ml of dimethylformamide, the solution was cooled to 0°C and 0.84 ml of 60% sodium hydride was added.
g was gradually added. The liquid temperature was maintained at 0°C and stirred for 1 hour. After a while, 2.4 g of an 88.2% toluene solution of O-ethyl-Sn-propylphosphorochloride thiolate was gradually added dropwise. After the dropwise addition was completed, the temperature was slowly returned to room temperature, and the reaction was further stirred for 12 hours to complete the reaction. After the reaction was completed, the reaction solution was poured into ice water and neutralized with 10% hydrochloric acid solution.
Extracted with chloroform. The chloroform layer was washed with water, dried over anhydrous magnesium sulfate, chloroform was distilled off under reduced pressure, and purified using silica gel chromatography (solvent = chloroform:methanol = 97:3) to give a melting point of 75.
1.50 g of the title compound was obtained in crystalline form at ~78°C. Synthesis Example 4 O-ethyl-S-n-propyl (5,5-dimethyl-2
-cyanoiminohexahydropyrimidin-1-yl)phosphonothiolate (compound number 7) 5,5-dimethyl-
1.5 g of 2-cyanoiminohexahydropyrimidine was added to N
, after dissolving in 20 ml of N-dimethylformamide,
The solution was cooled to 0°C and 60% sodium hydride 0°C.
．． 88g was added gradually. Thereafter, the liquid temperature was kept at 0° C. and stirred for 1 hour. After a while, 2.4 g of an 88.2% toluene solution of O-ethyl-Sn-propylphosphorochloride thiolate was gradually added dropwise. After the dropwise addition was completed, the temperature was slowly returned to room temperature, and the reaction was further stirred for 12 hours to complete the reaction. After the reaction was completed, the reaction solution was poured into ice water, neutralized with 10% hydrochloric acid solution, and then extracted with chloroform. The chloroform layer was washed with water, dried over anhydrous magnesium sulfate, chloroform was distilled off under reduced pressure, and purified using silica gel chromatography (solvent = chloroform:methanol = 97:3) to obtain 1.70 g of the title compound as an oil. Ta.

Next, specific formulation examples will be shown, but the carriers, surfactants, etc. to be added are not limited to those listed in these examples. Note that "parts" below means "parts by weight." Formulation example 1 (hydrating powder) 20 parts of compound No. 3, 56 parts of acid clay, 15 parts of white carbon, 4 parts of calcium lignin sulfonate, and 5 parts of polyoxyethylene alkylphenyl ether
A wettable powder was obtained by uniformly mixing and pulverizing the mixture. Formulation example 2 (emulsion) Add 75 parts of xylene to 20 parts of compound number 1,
To this was added 5 parts of New Calgen ST-20 (manufactured by Takemoto Yushi) as an emulsifier, and the mixture was mixed and dissolved to obtain an emulsion. Formulation example 3 (granules) 5 parts of compound No. 6, 3 parts of calcium lignosulfonate, 1 part of sodium dodecylbenzenesulfonate, 30 parts of bentonite, and 61 parts of clay were thoroughly ground and mixed, and water was added and kneaded well. After that, the mixture was granulated and dried to obtain granules.

Next, the insecticidal, acaricidal, and nematocidal effects of the compound represented by the general formula (I) will be shown by test examples. Test Example 1 The emulsion obtained in Formulation Example 2 was diluted with water to 500 ppm and 50 ppm and sprayed on Chinese cabbage leaves. After air-drying, it was placed in a plastic container measuring 21 cm long x 13 cm wide x 3 cm thick, and 10 3rd instar larvae of Spodoptera were released, placed in a thermostatic chamber at 26°C, and after 2 days, the larvae were checked to see if they were alive or dead.
The insect mortality rate was determined (two replicates). The results are shown in Table 3.
Table 3 Compounds
Active ingredient concentration
Mortality rate number
(ppm)
(%) 1
500
100
50
80 2
500 10
0
50
90 3
500 10
0
50
100 4
500 10
0
50
80 5
500
100
50
100 7
500 10
0
50
0 8
500 10
0
50
80 No treatment
−
0 Test Example 2 The emulsion obtained in Formulation Example 2 was diluted with water to 500 ppm, rice seedlings were immersed in it for 10 seconds, air-dried, the roots were wrapped with moist absorbent cotton, and placed in a test tube.
Release 10 instar larvae, cover the tube opening with gauze, and heat at 26°C.
The larvae were placed in a constant temperature chamber, and 2 days later, the survival of the larvae was examined to determine the mortality rate (2 repetitions). The results are shown in Table 4.
Table 4 Compound number
Active ingredient concentration (ppm)
Mortality rate (%) 1
500
100 2
5
00 100
3
500 10
0 4
500
100 5
500
100 6
500
100 7
5
00 100
8
500 10
0 No treatment
−
0 Test Example 3 A piece of green bean leaf cut into 3 cm (3 x 5) cm pieces was placed with the backside facing up on a filter paper moistened with water to prevent the leaf from drying out, and 20 female adult Kanzawa spider mites were placed on each leaf piece. Inoculated. 24 hours after inoculation, a chemical solution prepared by diluting the emulsion obtained in Formulation Example 2 with water to 500 ppm and 50 ppm was sprayed. After air-drying, it was allowed to stand in a constant temperature chamber at 26°C, and the number of live and dead insects was investigated after 24 hours to calculate the mortality rate (2 repetitions). The results are shown in Table 5.
Table 5 Compounds
Active ingredient concentration
Mortality rate number
(ppm)
(%) 1
500
100
50
90 2
500 10
0
50
80 3
500 10
0
50
100 4
500 10
0
50
80 5
500 10
0
50
100 6
500 10
0
50
40 7
500 10
0
50
30 8
500 10
0
50
60 No treatment
−
0 Test Example 4 A 1/5000 are pot was filled with soil contaminated with Nematode nematode, and the granules obtained in Formulation Example 3 were mixed with 250 g and 25 g of the active ingredient per 1 are. Two days later, tomato seedlings at the 3- to 4-leaf stage were transplanted, and 25 days later, the degree of adhesion of cat knots was investigated (two repetitions).

[0031] The degree of colonization was determined according to the following evaluation criteria. 0 No catfish growth 1
Nekobu epiphyte small 2
Nekobu epiphyte 3
Nekobu epiphyte 4
Table 6 shows the results of Nekobu settlement.
Table 6 Compounds
Active ingredient amount
Nekobu epiphyte number
(g/are)
Degree 1
250
0
25
0 2
250
0
25
0 3
250
0
25
0 5
250
0
25
0 6
250
0
25
0 7
250
0
25
2 8
250
0
25
0 Comparative compound
250 0

25
1 No treatment
−
4 The comparative compounds in Table 6 are compounds represented by the following formula.

[0032]

[Chemical formula 17]

[0033]

Effects of the Invention The organic phosphorus compound represented by the general formula (I) has an effective control effect against harmful insects, mites, and nematodes, has almost no bad odor or irritating odor, and has a warm temperature. It is used as a new insecticide, acaricide, and nematocide with low toxicity to animals.

Claims (3)

[Claims] Claim 1: General formula (II) [Formula 1] (wherein Z is CHNO2, N-NO2 or N-CN
and A represents an ethylene group optionally substituted with a C1-C3 alkyl group or a trimethylene group optionally substituted with a C1-C3 alkyl group), and a general React with a phosphoric acid compound represented by formula (III) [Chemical formula 2] (wherein R1 and R2 each represent a C1 to C4 alkyl group, and Hal represents a halogen atom) in the presence of a deoxidizing agent. A method for producing an organic phosphorus compound represented by the general formula (I): wherein R1, R2, Z and A are as described above. Claim 2: General formula (II) [Chemical formula 4] (wherein Z is CHNO2, N-NO2 or N-CN
and A represents an ethylene group optionally substituted with a C1-C3 alkyl group or a trimethylene group optionally substituted with a C1-C3 alkyl group), and a general Formula (IV) [Image Omitted] (In the formula, R2 represents a C1 to C4 alkyl group, and H
al represents a halogen atom) in the presence of a deoxidizing agent to obtain the general formula (V) [Chemical formula 6] (where Z, R2, Hal and A are as described above). A general method characterized by obtaining a compound represented by the formula (VI) and further reacting this compound with a compound represented by the general formula (VI) R1 OH (wherein R1 represents a C1 to C4 alkyl group). A method for producing an organic phosphorus compound represented by formula (I): (wherein R1, R2, Z and A are as described above). 3. An insecticide, acaricide, or nematocide comprising an organic phosphorus compound represented by the general formula (I) according to claim 1 as an active ingredient.