JPS5828879B2 - Novel organic compounds, their production methods and invertebrate pest control formulations - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel organic compounds, processes for their preparation and formulations containing the compounds suitable for use as insecticides.

More particularly, the present invention relates to phosphinic acid derivatives of methyl aminothiocarbamate.

Insecticides consisting of substituted thio derivatives of carbamic acid methyl esters are known.

For example, US Pat. No. 3,781,331 (1973
(published on December 25, 1974) and Specification No. 3794733 (published on February 26, 1974) can be referred to as conventional related technical documents.

US Pat. No. 3,781,331 discloses insecticides consisting of acylaminothio derivatives of methyl carbamates.

Belgian Patent No. 86 issued on May 15, 1978
No. 0844 discloses N-[(phoshynyl)aminocothio-methyl carbamate.

However, to the present knowledge no one has produced an aminothiomethyl carbamate phosphinic acid derivative insecticide.

It is an object of the present invention to provide a methyl carbamate insecticide that is as effective or more effective against pests than the parent compound.

The methyl carbamate insecticide of the present invention has low toxicity to animals and plants, and high residual efficacy.

The objects of the invention are therefore achieved by the novel compounds of the invention.

Other valuable objects of the invention will be recognized by those skilled in the art.

The N1(phoshynyl)aminocothio-methylcarbamate and N-4(phoshythioyl)aminocothiomethylcarbamate of the present invention used as said insecticides are represented by the following general formula: (wherein R1 is lower alkyl and cycloalkyl; Q is (-〇C2H5,

) In the above definitions of substituents, ``lower alkyl'' refers to methyl, ethyl, propyl, butyl, pentyl, and isomers thereof.

On the other hand, +1 cycloalkyl +1 is cyclopropyl, cyclophthyl, cyclopentyl, cyclohexyl, etc., and methyl,
Indicates optional substitution by ethyl and propyl.

The novel N-[(phoshynyl)aminocothio-methylcarbamate and N-((phoshythioyl)aminocothio-methylcarbamate insecticidal compounds of the present invention of the formula ■) are selected from the following:
It is produced according to the process of the invention which consists of reacting the lK form with N-(halothio)phosphinic acid amide.

The chemical formula for this reaction is as follows: (In the formula, R4 and Q have the same meanings as above.

) The reaction is carried out at low temperatures, preferably in the range -20 DEG C. to +25 DEG C., in the presence of a suitable acid acceptor and an inert organic solvent.

Examples of suitable acid acceptors include trialkylamines (eg triethylamine), pyridine and lutidine.

Examples of organic solvents used in the reaction include dimethylformamide, diethyl ether, hexane, tetrahydrofuran, and acetonitrile.

When using non-polar and polar solvents, cuprous chloride and aluminum chloride can be used as reaction catalysts.

The desired compound represented by formula (1) is recovered and purified by conventional methods.

Techniques such as filtration, solvent evaporation, chromatography, and crystallization are used.

Some of the compounds are obtained in crystalline form, while others are purified as oils.

The phosphinic acid N-chlorothioamides of formula
is produced by reaction in the presence of a suitable acid acceptor and an inert organic solvent at a temperature of .

Phosphinic acid amides are commercially available or can otherwise be produced by methods disclosed in the known literature.

For example, "Methoden der Organi"
Shen Chemie (Houben-Weyl
)”, Vol, 12, Part 2.413 page, and Vol, 12.1 page, Georg Thiem
e Verlag (Pu too), S tuutgar
t.

Germany, 1963.

The compound of formula (■) exhibits an unprecedented degree of crystallinity.

For example, N-[[[[[(5,5-dimethyl-2-thioxoto-3,2-dioxaphospholinan-2yl)t-butylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate is extremely It is crystalline.

The physical properties associated with crystallinity make it easy to isolate the product from the reaction mixture.

Additionally, highly crystalline compounds can be prepared into aquariums.

Irrigation agents have advantageous advantages such as compressibility, flowability and high concentration of active ingredients.

The production of the novel compound represented by formula (1) will be explained below.

These are illustrative of the scope of the invention and are not intended to limit the scope of the invention.

It will be readily appreciated by those skilled in the art that the procedures with respect to methyl carbamate precursors, reaction conditions, and reaction techniques may be varied as appropriate.

The following examples represent the best mode currently known to the inventors.

In the description of the following Preparation Examples and Examples, "Florisil" refers to activated magnesium silicate.

Furthermore, "Skerisolve B I+" is a solvent mainly composed of n-hexane and having a boiling point of 60 to 68°C.

Production Example 1 Reactant, 0-O-diethyl N-(chlorothio)N-(
n-propyl)-phosphoramidothioate hexane 101 rLl and triethylamine 2 mhp
While stirring a solution of 2.981 (0.014 mol) of 0.0-diethyl n-propylphosphoramide thioate in 1 OTL of hexane, slowly dissolve 1 sulfur dichloride in 1 OTL of hexane.
．． Added to a cold (0° C.) solution of 0 ml (0,016 mol).

A violent reaction occurred and a heavy precipitate of triethylamine hydrochloride formed.

Added 20ml hexane.

The reaction mixture was maintained at 0-5°C and stirred for 30 minutes before being sipped.

The oral fluid was concentrated by evaporating the hexane under reduced pressure to give a pale yellow oil.

This oily substance is the target 0.〇-diethyl N'-(
chlorothio)-n-7''ropyl phosphoramide thioate.

This compound can be used later to react with N-methyl carbamate.

Production Example 2 Reactant, 0-O-diethyl N-(chlorothio)N-infropylphosphoramidothioate 0-O-diethylisofurohirphosphoramidothioate 9.95? (0
,0471 mol) and 6.5 rnl of triethylamine was slowly added with stirring to a cold solution of 3.0 ml (0.047 mol) of sulfur dichloride and 150 ml of hexane.

During the addition, the temperature was maintained at 0-5°C and stirring continued for 30 minutes.

The reaction mixture was sieved and the precipitated salts collected on the sieve were washed with hexane.

The oral fluid and hexane wash were combined and evaporated under reduced pressure to remove hexane.

Thus, the desired reactant 0.0-
Diethyl isopropyl phosphoramide thioate was obtained.

Example 1 Compound, 4-(dimethylamino)-3,5-xylyl [
Production of [(jetoxyphosthioyl)n-furopylamino]thio]methylcarbamate The crude 0-O-diethyl N-(chlorothio)-n-7”ropyruphosphoramidothioate produced in Production Example 1 was heated in a water bath. Cool in a tank and add 20 ml of dimethylformamide (
2 rul of triethylamine are added.

2.79 f (0,013 mol) of 4-(dimethylamino)3,5-xylylmethylcarbame) dissolved in ) were mixed at once.

The reaction mixture was stirred at 25° C. for 4 hours and then diluted with hexane.

The organic solution was washed with water, dried over anhydrous sodium sulfate, and the organic solvent was removed by evaporation under reduced pressure.

The residue thus obtained was treated with 0 Florisil.
il)” column.

First diethyl ether (10%) and petroleum ether (9%)
0%) and finally with a mixed solvent consisting of diethyl ether (30%) and petroleum ether (70%).

After collecting the latter eluate and removing the solvent by evaporation under reduced pressure, the desired 4-(dimethylamino)-3,5-xylyl [[(jetoxyphosphorus oil)] was obtained as a yellow oil. -npropylamino]thio]methyl carbamate was obtained.

Elemental analysis: Theoretical value as C19H34N304PS2 (
%): C, 49, 22; H, 7° 39: N, 9.
06° Analysis value (%): C, 49,84; Hl 7.89; N
, 8.52゜Example 2 Production of methyl N-((C[(dimethoxyphosphothioyyl)methylamino]thio]methylamino]carbonyl]oxy]ethanimidothiony).Methyl N-CC( Starting with methylamino)carbonyl]oxy]ethanimidothioate and the appropriate phosphoramidothioate, the following novel N-[(phoshynyl)
Aminocothiocarbamate and N-4(phoshitthioyl)aminocothiocarbamate were produced: (1) Methyl N-(C(CC(dimethoxyphosphotioyl)methylamino]thio[methylamino]carbonyl]oxy]ethane imidothioate m, p, 57°~5
8°C0 Elemental analysis: Theoretical value (%) as C3H18N3S304P
): C127,66; H, 5,22; N112.10 Analysis value (%): C127,88; N1527; N, 11
．． 95 (2) Methyl N-[[[[(dimethoxyphoshitthioyl)isopropylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p, 8
8 to 89°C0 Elemental analysis: Theoretical value (%) as Cl0H22N304PS3: C131,99; H, 5,91; N, 11.
19 Analysis value (%): C, 31,99; N15.86; N, 1
0.93 (3) Methyl N-C((((dimethoxyphosthioyl)n-butylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p, 60
°~6FC8 Elemental analysis: Theoretical value as C11H24N304PS3 (
%): C133,92; H, 6,21; N, 10.79 Analysis value (%): C, 33,84; H, 6,26; N11
0.44 (4) Methyl N-[([(jetoxyphosthioyl)methylamino"thio]methylamino]carbonyl]oxy]ethanimidothioate.

Elemental analysis: Theoretical value as Cl0H22N304PS3 (
%): C131,99; N15.91; N, 11.19 Analysis value (%): C, 32,00; N15.96; N, 1
0.58 (5) Methyl N- [
2-73℃.

Elemental analysis: Theoretical value as C1□H26N304PS3 (
%): C135,71; H, 6,50; N, 10.41 Analysis value (%): C135,77; N16.74; N, 1
0.09 (6) Methyl N-
Carbonyl]oxy]ethanimidothioate elemental analysis: Theoretical value (%) as Cl2H26N304PS3: C135,71; N16.50; N, 10.4
1 Analysis value (%): C135.48; N16.46; N,
9.82 Example 3 Methyl N-C(C(5,5-dimethyl-2-thioxoto3,2-dioxaphosphorinan-2-yl)infropylamino]thio]methylamino]carbonyl]oxy ] 5,5-dimethyl 2 to 2 omjl of ethanimidothionite) and lahydrofuran
A solution prepared by dissolving 3.001 (13.4 mmol) of -isopropylamino-2-thioxo-1,3,2-dioxaphosphorinane and 1.9 ml (13.5 mmol) of triethylamine was added to 20 ml of tetrahydrofuran.
! The mixture was added dropwise to a solution prepared by dissolving 1.00 ml (15.7 mmol) of sulfur dichloride in the solution under stirring at room temperature for 20 minutes.

After the addition, the reaction mixture was stirred at room temperature for 1 hour.

Add 0.25 P of cuprous chloride to the reaction mixture, followed by
Methyl N-[[(methylamino)carbonyl]oxy]ethanimidothioate 2.17'? in 20 Tnl of tetrahydrofuran? (13.4 mmol) and 1.90 ml (13.5 mmol) of triethylamine were added dropwise.

The reaction mixture was stirred at room temperature for 2 hours, then diluted with water and extracted with ethyl acetate.

The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure.

The resulting oil was chromatographed on silica gel eluting with a mixture of ethyl acetate and Kelisolve B (2:3).

The product obtained by chromatography was recrystallized from ethyl acetate to give methyl N-[[[(s·5-dimethyl-2-thioxoto3·2-dioxaphosphorinan-2-yl)isofuropylamino] Thio]methylamino]carbonyl]oxy]ethanimidothioate (white solid) was obtained.

m, p, 114-115°C, NMR and IR analysis results were consistent with the structure of the desired compound.

Elemental analysis value: Theoretical value (%) as C13H26N304PS3: C, 37,58; H, 6,31; N110.
11 Analysis value (%): C, 37,63; H, 6,25; N, 1
0.11 Example 4 Methyl N-C[(C(5,5-dimethyl-2-thioxoto3,2-dioxaphosphorinan-2-yl)t~butylamino)thio]methylamino]carbonyl'oxy] 2-t-butylamino- ethanimidothioate tetrahydrofuran 50ml
5,5-dimethyl-2-thioxo-1,3,2-dioxaphosphorinane7,4? A solution prepared by dissolving 2.0 ml (31 mmol) of sulfur dichloride in 20 ml of tetrahydrofuran was cooled to 0°C. 2 drops at a time while stirring into the solution.
Added over 0 minutes.

After the addition, the reaction mixture was stirred at 0° C. for 30 minutes.

0.31 of cuprous chloride is added to the reaction mixture followed by 5.1? (31 mmol) and triethylamine 4
．． A solution prepared by dissolving 4 ml (31 mmol) was added dropwise over 20 minutes.

After the addition, the reaction mixture was stirred for 2 hours and allowed to warm to room temperature.

The reaction mixture was diluted with ethyl acetate and washed with water.

The organic layer was dried over magnesium sulfate and concentrated under reduced pressure.

The resulting residue was treated once or twice with an ether-hexane mixture to precipitate the crude product.

Recrystallization from methanol twice gave pure product.

m,'p, 1.67-168.5°C, NMR and IR spectra were consistent with the structure of the desired compound.

Elemental analysis value: Theoretical value (%) as Cl4H28N304PS3: C, 39,14; H, 6,57; N,
9.78 Analysis value (%): C, 39,45; H, 6,73; N,
9.87 Example 5 Methyl N-CC([cyclohexyl(5,5-dimethyl-2-thioxoto 3,2-dioxaphosphorinane-2
-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate in 50 TLl of tetrahydrofuran and 2-cyclohexylamino-5,5-dimethyl-2-thioquine-1,3,2-
A solution prepared by dissolving 12.4 P of dioxaphospholinane and 6.55 ml of triethylamine was added to 50 ml of tetrahydrofuran and 3.0 ml of sulfur dichloride. 1 while stirring into a solution prepared by dissolving Qml and cooled to -5℃ to 0℃.
Addition was allowed over 5 minutes.

When 0.2 P of cuprous chloride was added, the reaction mixture was stirred at 0° C. for 45 minutes after the addition.

7,67 ml of methyl N-([:(methylamino)carbonyl]oxy]ethanimidothioate and 6.55 ml of l-IJ ethylamine in 50 ml of tetrahydrofuran.
A solution prepared by dissolving 1 was added after cooling for 15 minutes.

After the addition, the reaction mixture was stirred and allowed to warm to room temperature over 75 minutes.

The reaction mixture was washed with water, dried over magnesium sulfate and concentrated under reduced pressure.

The obtained semi-solid residue was recrystallized from a mixture of ethyl acetate and hexane to give methyl N-(C[:((cyclohexyl(5
・5-dimethyl-2-thioxo-1,3,2dioxaphosphorinan-2-yl)amino]thio]methylamino]
9.3 C1 of carbonyl]oxy]ethanimidothioate (white solid) was obtained.

m, p, 138-140'''c. Elemental analysis value: C15H
Theoretical value (%) as 3ON304PS3: C142,1
8; N16.64; N, 9.22 Analysis value (%): C, 42,39; H, 6,71; N19
The .32 NMR and IR spectra were consistent with the structure of the desired compound.

Example 6 Methyl N-[[[[[[isopropyl (5.5 diethyl-
2-thioxoto 3,2-dioxaphosphorinane-2-
yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioatetetrahydrofuran 2-isopropylaminonote 3,2-phospholinane5.
A solution prepared by dissolving 51 and triethylamine 6,05+711 was added dropwise over 15 minutes to a solution prepared by dissolving 2.72 rnl of sulfur dichloride in 50 ml of tetrahydrofuran and cooled to -5°C to 0°C. .

After the addition, the reaction mixture was stirred for 1 hour at 0° C. and 0.1 (l) of cuprous chloride was added.

Methyl N-C ((methylamino)carbonyl]oxy]ethanimidothiony) in 50 ml of tetrahydrofuran
A solution of 7.06P and 6.05 ml of triethylamine was added dropwise over 15 minutes.

The reaction mixture was stirred and allowed to warm to room temperature over 1 hour.

It was diluted with water and extracted with ethyl acetate.

The extracts were washed with water, dried over magnesium sulfate and concentrated under reduced pressure.

The resulting residue was chromatographed on silica gel using a mixture of ethyl acetate and hexane (1:1) to obtain the product.

Recrystallized from a mixture of ethyl acetate and hexane to give methyl N-[
[[[[isopropyl(5.5diethyl-2-thioxoto-3,2-phosphorinan-2-yl)amino]thio]
Methylamino]carbonyl]oxy]ethanimidothioate (white solid) was obtained.

m. p. 123-124.5°C.

Elemental analysis value: Theoretical value (%) as C15H3ON304PS3: C, 40.61; H, 6.82; N, 9
．． 48 Analysis value (%): C140.83; N16.91; N
19.6O NMR and IR spectra were consistent with the structure of the desired compound.

Example 7 The following compounds were produced in a manner similar to that described in Example 4, using the appropriate methyl carbamates and phosphoramidothioates as starting materials.

(1) Methyl N-(CC[isopropyl(2-thioxoto3-2-phosphoran-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p, 120-122°C.

Elemental analysis value: Theoretical value (%) as C1oH2oN304PS3: C132,16; N15.40; N111.2
5 Analysis value (%): C132.17; N15.31; N,
1.1.49 (2) Methyl N-(([cyclohexyl(5,5-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl [oxy]ethanimidothioate, m, p, 15
5-157°C.

Elemental analysis value: Theoretical value (%) as Cl8H34N304PS3: C144,70; H, 7,09; N, 8.
69 Analysis value (%): C144.96; N17.11; N,
8.81 (3) Methyl N-CC((Cisopropyl(2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m , p, 153-154°C.

Elemental analysis value: C1] Theoretical value (%) as H2□N304PS3: C, 43,10; H, 5,72; N, 10.8
4 Analysis value (%): C, 44,21; H, 5,87; N, 1
1.13 (4) Methyl N-
-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p, 111-1
126C elemental analysis value: C1□H24N304PS3 theoretical value (%): C135,90; Hl・6.03; N
110.47 Analysis value (%): C, 36,13; H, 6,22; N, 1
0.26 (5) Methyl N-[[[[[[isopropyl (4.4.6
-Dolimethyl-2-thioxo-1,3,2dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p,
123-127°G elemental analysis value: Cl4H27N304
Theoretical value (%) as PSs: C, 39,24; H, 6
, 35; N, 9.80 Analysis value (%): C139,76; H, 6,94; N,
9.76 (6) Methyl N-(((((methyl(2-thiokit3)
-2-dioxaphospholinan-2-yl)amino]thio]methylamino"carbonyl]oxy]ethanimidothioate, m, p.

94-96℃ Compounds of general formula (2) are effective as insecticides.

Therefore, this compound can be used for the control of vertebrae pests in agricultural, industrial and domestic areas.

Compounds of the invention were compared to the precursor methyl carbamate.

Examples of typical insect pests used in this comparative test are as follows: Lepidoptera, especially the southern snail fly (hereinafter abbreviated as SAW).

) (English name, 5outhern armyworm; Scientific name, Prodenia eridania Crame
r) ; Tobacco moth (hereinafter abbreviated as TB).

) (English name, tobacco budworm: scientific name,
Heliothis virescens): and Kumanaginuwaba (hereinafter abbreviated as CL).

) (English name, Cabbage 1ooper: scientific name,
Trichoplusia ni) Order Acarina, especially the two-spotted spider mite (hereinafter abbreviated as TSSM).

) (English name, two -5potted 5pider
m1te: Scientific name, Tetranychus urt'
1cae Koch): Diptera (0rder Dep.
tera), especially the house fly (hereinafter abbreviated as HF).

) (English name, housefly: Scientific name, Musca d
omes 1caI, 1nnaeus): or neck isima force (hereinafter abbreviated as YFM).

) (English name, yellow -fever mosqui
to: Scientific name, Aedes aegypti): Order Orthoptera, especially the house cricket (hereinafter abbreviated as HC).

) (English name, house cricket: scientific name, Ac
hetadomestious Linnaeus)
; or German cockroach (hereinafter abbreviated as GC).

) (English name, German cockroach; scientific name, Blatella germanica Linna
eus): Coleoptera
a) Especially Menkyu weevil (hereinafter abbreviated as BW).

) (English name, cotton boll weevil:
Scientific name, Anthonomus grandis Boh
Although the effectiveness against vertebrae pests depends on the specific pest used, it was tested at concentrations as low as 0.5 ppm.

Certain vertebrate pests are more sensitive to the compounds of the invention than others.

Therefore, other substances may be resistant.

Generally, the compound of formula (II) is used at a concentration within the range of about 30 to about 6000 ppm.

In general, the compounds of the invention have the lethal effects of the parent methyl carbamates, but also exhibit low toxicity and low phytotoxic effects.

Mammalian toxicity is described below.

4-(dimethylamino)-3,5-xylyl[[(jetoxyphosphothiol]-n-propylamino]thio]methylcarbamate (Example 1) Methyl N-C(([:C(jetoxyphosphothiol) oil) isopropylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate (Example 2 (5)
) Methyl N-(((CCcyclohexyl(5dimethyl-2
-thioquine-1,3,2-dioxaphosphorinane-2-
yl)amine]thio]methylamino]carbonyl]oxy]ethanimidothioate (Example 5) Mammalian toxicity; oral LD5o, rat>soo.

■/ky Methyl N-[[[[[[Isopropyl (5.5 diethyl-
2-thioxoto 3,2-dioxaphosphorinane-2-
yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate (Example 6) Mammalian toxicity: Oral LD5o, rat>2000■/k
y Methyl N-(C(M-inpropyl(2-thioxo-1.
3,2-phosphoran-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p, 120-122°C (Example 7 (1)) Methyl N-[[[[[ Cyclohexyl (5,5 diethyl-2-thioxote 3,2-dioxaphosphorinane-2
-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p, 155-15
7°C (Example 7 (2)) Mammalian toxicity: Oral LD5o
, rat > so o.

m/kg Methyl N-((C((isopropyl(2-thioxo-1)
・3,2-dioxaphospholinan-2yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p, 153-154 °C (Example 7
(3) ) Mammalian toxicity: oral LD5o, rat >2000yn9
/kg Methyl N-C(((Cethyl(5,5-dimethyl-2-
Thioxoto 3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy
Ethanimidothioate, m, p, 11.1-112°C
(Example 7 (4)) Methyl N-(C((Cisopropyl(4,4,6-drimethyl-2-thioxo-1,3)
・2-dioxaphospholinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate, m, p, 123-127°C (Example 7 (5)
) The details of carrying out the mortality test were as follows: Preparation of test compound - The test sample was dissolved in acetone.

These acetone solutions were applied neat or portions were diluted with Tween 20 wej water or 10% Zatucarose wej water.

The wetting water itself contained 0.132% v/v of Tween 20 (polyoxyethylene sorbitan monolaurate).

The insects, SAW (SAW) and SAW (CL), were tested on Henderson thatch, which features two primary leaves per replicate.

The leaves were soaked in a wet water emulsion of the test compound, allowed to dry, and then placed on a humidified filter disc in a 9 CrrL Petri dish.

Five larvae of the test insects were placed on the leaves and covered with the lid of a Petri dish, which was saved for later investigation.

The test was repeated three times for each treatment concentration.

House crickets (HC) were tested by pipetting 5 ml of the above acetone solution into a 9 crrL Petri dish and allowing the acetone to evaporate.

Place 10 house cricket pupae into the treated Petri dish.
I put the lid on.

The test was repeated three times for each treatment concentration.

For house flies (HF) and menkyu weevils (BW), golf ball dog claw cotton was added to 10% of the test compound.
The test was performed by saturating with a % wet sugar water formulation.

A potion cup (p.
(ortioncup).

An adult housefly or menkyu weevil was placed in a 5 oz cup and covered with a plastic lid for later examination.

The test was repeated twice for each treatment concentration.

For neck force (YFM), add the appropriate amount of wetting water and an acetone solution of the test compound to 100 mA of distilled water in a 5 oz. volume waxed paper cup! It was tested by adding it to.

Ten young mosquitoes were added.

After 24 hours, dry yeast was added.

The test was repeated twice for each treatment concentration.

Southern gore maggot fly (SAW), house fly = ¥
(HC), Menkyu weevil (BW), house fly (H
F) and Kumanaginuwaba (CL) tests were conducted at 22°C.

The YFM test was conducted at 27°C.

The test was conducted by evaluating the number of insects dying (including moribund and non-reviving) after 24 hours, 48 hours, and sometimes 72 hours.

In subsequent tests, for example, methyl N-[[[[
The phytotoxicity, residual effects, and zootoxicity of [(jetoxyphosthioyl)isopropylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate were investigated using the parent compound methyl N-[[(methylamino)carbonyl]. compared with oxy]ethanimidothioate.

Using a scale from 0, which is harmless, to 10, which indicates complete death of the plant, the new derivatives of the present invention are generally less phytotoxic than the parent compound, especially to sensitive plants, e.g., eggplant. It was significantly lower.

When the new derivatives were used at concentrations of 300 ppm and 600 ppm, the average phytotoxicity index after 8 days was 1.0 and 1.5, respectively.

The average phytotoxicity of the parent compounds was 4.25 and 5.25, respectively.
It was 0.

In addition, the residual effect of the novel derivatives of the present invention on leaves was measured on broad bean seedlings using the southern bean fly.

The compound of the present invention, methyl N- give.

In contrast, the activity of the parent compound at the same concentration is 14
By today, it had fallen to 20%.

In a comparative study for oral toxicity in male rats, the compound of the invention, methyl N- It was shown to have less than 1/4 of the toxicity of methyl carbamate.

Acute toxicity and LD50 (oral) are each 10.
5■/kg (body weight) and 17-24■/ky (body weight)
Met.

The above test results demonstrate that the objectives of the present invention have been fully achieved and that it has made a valuable contribution to the field of insecticides.

In addition, the above results further demonstrate that the N-[(phoshynyl)aminocothio-methyl carbamate and N-((
The phoshitthioyl) aminocothiomethyl carbamate can be used as a pure compound as described in the examples above, as a technical grade compound from commercial production, or as a mixture of each pure compound.

On the other hand, from practical considerations, diluents may be used with or without adjuvants, which facilitate the application of the active ingredient to the area where pest control is required and thus increase its effectiveness and economy. It is desirable to supply formulations containing the same to those skilled in the pesticide field.

There are many different types of diluent bulking agents suitable for the methods and formulation examples of the invention.

Dispersion carriers are commonly used in the art.

The carriers may contain adjuvants such as wetting agents, emulsifiers, tackifiers and other ingredients that indirectly enhance efficacy.

However, it may not be included.

The novel carbamates of general formula 1 can be used, for example, in dusts, wettable powders, etc., for application to sites, soil, plants, and leaves, seeds and other parts of plants.
e powder), emulsion (emulsif 1ab)
reconcentrate), aqueous dispersant (aqu
eous dispersion), solution (5olut
ion) and flowable Cree A (flowable
It is useful against insects, nematodes, and wall lice in dosage forms such as cream).

It can also be made into granules and applied to the soil or soil surface.

Furthermore, the novel compound of general formula (1) of the present invention can be present as the main ingredient in the formulation, or it can also contain other insecticide, nematicide or wallkill ingredients.

The novel solid compounds of general formula (1) can be easily formulated into powders by grinding a mixture of the compound and a finely divided carrier in the presence of each.

Grinding is conveniently carried out in a ball mill, a powder mill, or by means of an air blast micronizer.

A preferred minimum particle size is less than 60 microns.

Preferably, 95% of the particles are smaller than 50 microns;
and approximately 75% are between 5 and 20 microns.

Dusts of the above-mentioned degree of grinding are advantageously free-flowing and can therefore be effectively applied to animals, inanimate objects, fruit trees, cultivated plants, and soil by spreading and covering.

When applied from an airplane, dusts are particularly suitable for effectively controlling insects and wall lice over large areas.

Powders are also used to apply to unwanted plant foliage.

Representative suitable fine powder carriers include natural clays such as clay, Josiah clay, Baden clay, attapulgus clay, kaolin clay, and bentonite clay: minerals in their natural form, such as those obtained from the earth; For example, mica, pyrophyllite, quartz, diatomaceous earth, fuller's earth, chalk, sulfur, silicon, silicates; chemically altered minerals, such as
Washed bentonite, and colloidal silicon; and organic powders such as wood flour, walnut shell powder, soybean flour,
cotton seed powder, and tobacco powder and free-flowing;
There are hydrophobic starches.

Powders can also be prepared by dissolving an aminothiocarbamate phosphinic acid derivative insecticide of the general formula (1) in a volatile solvent such as methylene chloride and mixing this solution with a fine powder carrier;
It can then be manufactured by evaporating the solvent.

The proportions of the fine powder carrier and the active compound (general formula I) can vary over a wide range depending on the application, the pests and nematodes to be controlled and the treatment conditions.

Generally, powder formulations can contain up to about 90 wt% of active ingredient.

The aquarium of the present invention is produced by mixing a surfactant into the powder preparation prepared as described above.

When about 0.1% to about 12% surfactant is incorporated into the powder, the resulting irrigation agent can be later mixed with water for spraying on inanimate objects, products, fruit trees, soil crops, soil and livestock. It is particularly suitable for

Irrigation agents can be mixed with water to achieve the desired concentration of active ingredient, so that the mixture can be applied in amounts sufficient to provide a rate application as well as uniform distribution.

With this flexibility in mind, the aquariums of the present invention may preferably contain from about 5% to about 80% active ingredient.

Representative examples of surfactants useful in preparing the irrigation agents of the present invention include alkyl sulf/ates, alkyl sulfonates, alkylaryl sulfonates, sulfosuccinate esters, polyoxyethylene sulfates, oxyethylene sorbitan monolaurates,
Alkylaryl polyether sulfates, alkylaryl polyether alcohols, alkylnaphthalene sulfonates, alkyl quaternary ammonium salts,
Examples include sulfated fatty acids, sulfated fatty acid esters, sulfated fatty acid amides, glycerol mannicone laurate, polyalkyl ether condensates of fatty acids, and lignin sulfonates.

A preferred type of surfactant is a blend of sulfonated oils and polyalcohol carboxylic acid esters (Emcol H7
7), a blend of polyethoxyethanols (Trito
ns X-151, X=161, and a blend of modified vegetable oils (Agrimul N4 S).

Of course, the sulfate and sulfonate surfactants exemplified above preferably include their soluble salts,
For example, it is used in the form of its sodium salt.

All of these surfactants are capable of lowering the surface tension of water at concentrations of about 1% or less.

Wettable powders can be prepared if desired using mixtures of surfactants of the type exemplified.

A preferred irrigation agent is 327 pounds of Josiah Clay, 4.5 pounds of Inoctylphenoxy Polyethoxy Ethanol/L/L/(Triton 9 pounds of Daxad 27) and 113 pounds of the active ingredient, such as the compound of Example 2, and milling.

The resulting formulation has the following composition: (Unless otherwise specified, percentages are by weight.

) When this formulation is dispersed in water at a rate of 10 pounds per 100 gallons of water, it contains approximately 0.3% active ingredient (300
Apply a fume agent containing 0 ppm).

This fog can be applied to plants, fruit trees or other locations against insects or wall lice.

Alternatively, it can be used by spraying on soil against nematodes.

If desired, dispersants such as methylcellulose, polyvinyl alcohol, sodium lignin sulfonates, and the like can be included in the water preparations of the present invention.

Vegetable oil, natural gum, casein, Zona
rez) B, a series of polymerized terpenes, Unicera (
Adhesives or pressure-sensitive adhesives such as Unicez 709, maleic acid derivative resins, Polypole partially trimerized resin acids, and Dymerex, dimer resin acids, etc., can also be included.

Corrosion inhibitors such as epichlorohydrin and antifoam agents such as stearic acid can be included as well.

Methods of incorporating these ingredients into insecticides are well known to those skilled in the art and can be applied to the present invention.

The novel compounds of general formula I according to the invention can be applied to insects, lice, objects or plant organs as aqueous sprays without solid carriers.

However, since the compounds themselves are relatively insoluble in water, the compounds are preferably dissolved in a suitable inert organic solvent carrier.

Preferably, the solvent carrier is immiscible with water in order to be able to form an emulsifier of the solvent carrier in water.

For example, if a water-miscible solvent carrier such as ethanol is used, the solvent carrier will dissolve in the water so that excess compound of formula (I) will be driven out of solution.

In oil-in-water emulsions, a solvent phase is dispersed in an aqueous phase, and the dispersed phase contains the active ingredient.

In this way, homogeneous dispersion of water-insoluble active ingredients can be achieved in aqueous propellants.

In order to obtain relatively high concentrations of active ingredient, solvent carriers with high solubility of the novel compounds of general formula (1) are desirable.

To obtain a casting solution of the active ingredient, one or more solvent carriers, sometimes with or without auxiliaries, can be used.

The primary consideration is the use of water-immiscible solvents for the active ingredient that will retain the active ingredient in solution above the concentration range useful for insect and lice applications. .

The emulsions of the invention therefore contain active ingredients and surfactants such as cyclohexanone, methylpropyl ketone, forage oil, ethylene dichloride, and aromatic hydrocarbons such as benzene, toluene, xylene, and kerosene, diesel oil, etc. A substantially water-immiscible solvent carrier such as high boiling petroleum hydrocarbons such as
A solvent carrier that dissolves no more than 2.5% by volume in water at temperatures in the range of .

).

If desired, cosolvents such as methyl ethyl ketone, acetone, impropatol, and the like can be included in the solvent carrier to increase the solubility of the active ingredient.

An aqueous emulsifier with the desired concentration of active ingredient is then produced by mixing with water.

Surfactants that can be used in the aqueous emulsifier of the present invention are of the types exemplified above.

Mixtures of surfactants can be used if desired.

Conveniently, the concentration of active ingredient in the emulsion is from about 5 wt% to about 5
0 wt%, preferably about 10 wt% to about 4.0 wt%
wt% range.

An emulsion consisting of 20 wt. A mixture containing 700 parts can be used.

Similarly, one quart of 20% emulsion mixed with 40 gallons of water provides a concentration of active ingredient of about 1200 ppm.

Similarly, solutions containing higher concentrations of active ingredient can be prepared.

Emulsions of the invention contemplated for use in the form of aqueous dispersion emulsions may also contain humectants, ie, agents which retard the drying of the formulation of the invention on contact with the object to which it is applied.

Examples of suitable humectants are glycerol, diethylene glycol, solubilized lignins, such as calcium lignin sulfonate.

Granules of the present invention Cqranular formlat
ion) are convenient for application to soil when specific efficacy is desired.

Granules are easily applied over the entire surface or locally, for example by spreading in a line.

The size of the individual granules may be any desired size ranging from 10 to 60 mesh, preferably from 20 to 40 mesh.

Granules are produced by dissolving the active ingredient in a solvent such as methylene chloride, xylene or acetone and spreading the solution onto a bulk granular adsorbent carrier.

Examples of typical particulate sorbent carriers are ground corn cobs, ground walnut shells, ground peanut shells, and the like.

If desired, the impregnated granular adsorbent carrier is coated with a coating which preserves the active ingredient in the granules until the formulation is applied to an object or location convenient for the release of the active ingredient. be able to.

The amount of agent applied to insects, wall lice, soil, or other sites depends on the type of pest to be controlled, the presence or absence of the desired organism, the temperature of the treatment conditions, and the method and effectiveness of the application.

Generally from about 5 to about 2000 ppm, preferably from about 30 to about
When the compound is applied at a concentration of about 11000 pp, insecticidal and phyticidal activity is obtained.

For nematodes, 10 to 50 pounds/kneeker of active ingredient is required.

The preparation containing the novel thiocarbamate represented by the general formula (2) of the present invention can be applied to insects, wall lice, nematodes, soil or other sites by conventional methods.

For example, soil surfaces, buildings or plants can be treated with the irrigation agent by spraying with a sprayer or by spraying from a manual backpack sprayer.

Creams and ointments can be applied to the skin or objects for long-term protection from insects or wall lice.

The active ingredients of the invention can also be formulated at relatively low concentrations in an hydric insecticide carrier for household application.

For example, the active ingredient can be formulated into a powder containing about 0.1% to 5.0% active ingredient with deodorized kerosene for aerosol application.

Of course, the conditions under which the methods and formulations of the invention are applied can vary widely.

Variables that can be interpreted include the extent of the pest infestation, the specific pest to be controlled, the specific area being treated, the type of plant, and general weather conditions such as temperature, relative humidity, and rainfall. , dew, etc.

Claims (1)

[Scope of Claims] N-[(phoshynyl)aminocothio-methylcarbamate or N-[(phoshythioyl)aminocothio-methylcarbamate] represented by the following formula: (wherein R7 is selected from the group consisting of lower alkyl and cycloalkyl; Q is (-QC2H,, -0C2
H3), 2 The compound according to claim 1, wherein R1 is lower alkyl. 3. The compound according to claim 1, wherein R1 is cycloalkyl. 4 Methyl N-
The compound according to claim 1, which is oxy]ethanimidothioate. 5 Patent for methyl N-([[(5,5-dimethyl 2-thioquinoto 3,2-dioxaphosphorinan-2-yl)t-butylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate Compound according to claim 1. 6 Methyl N-
2-yl)amino[thio]methylamino]carbonyl]
The compound according to claim 1, which is oxy]ethanimidothioate. 7 Methyl N-1m[[[(ethyl (5,5-dimethyl-2-thioxoto3,2-dioxaphosphorinane-2
The compound according to claim 1, which is -yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate. 8 Methyl N-CCCCCisopropyl(2-thioxo-1,3,2-phosphoran-2-yl)amino]thio]
The compound according to claim 1, which is methylamino]carbonyl]oxy]ethanimidothioate. 9 Methyl N-[[[[isopropyl (2-thioxo-
1,3,2-dioxaphosphorinan-2yl)amino]
The compound according to claim 1, which is thio]methylamino]carbonyl]oxy]ethanimidothioate. 10 Methyl N-[(([[isopropyl(4.4.
The compound according to claim 1, which is 6-drimethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate. 11 Methyl N-[[[[[cyclohexyl (5.5
-diethyl-2-thioxo-1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate. 12 Methyl N-CC (([Cyclohexyl (5.5
-dimethyl-2-thioquinto 3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate. 13 Methyl N-[[[[[Methyl (2-thioxo-
The compound according to claim 1, which is 1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]etha/imidothioate. 14 Contains one or more types of N-C (phosphinyl)aminocothio-methyl carbamates or N-1: (phosphinyl)aminocothio-methyl carbamates represented by the following formula as an auxiliary carrier and an active ingredient in a biologically effective amount. A pest control preparation characterized by: (wherein R1 is selected from the group consisting of lower alkyl and cycloalkyl; Q is (-0C2H5). 15. Claim 14, wherein R1 is lower alkyl. A formulation according to claim 14, wherein R1 is cycloalkyl. 16 The formulation according to claim 14, wherein R1 is cycloalkyl. -dioxaphospholinan 2-yl)inpropylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N- phospholinan-2-yl)t-butylamino]thio]methylamino]carbonyl]oxy
Ethanimidothioate; Methyl N-(((Cisopropyl(5.5diethyl-
2-thioxoto 3,2-dioxaphosphorinane-2-
yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N-CC[Cethyl(5,5-dimethyl-2-thioxoto 3,2-dioxaphosphorinan-2-yl)
Amino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N-C1:4[(isopropyl(2-thioxo-1,3,2-phosphorane-2-
yl)amino]thio]methylamino]carbonyl]oquine]ethanimidothioate; Methyl N-[[[[[isopropyl(2-thioquine-1
・3,2-dioxaphospholinan-2yl)amine]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N-CC[C isopropyl(4,4,6-drimethyl-2-thioxoto 3,2) -dioxaphospholinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Linan-2
-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate; and methyl N-([C(cyclohexyl(5,5 diethyl-
2-thioxoto 3,2-dioxaphosphorinane-2-
15. The formulation of claim 14, wherein the formulation is selected from the group consisting of yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate. 18. The formulation according to claim 14.15.16 or 17, wherein the auxiliary carrier is a readily dispersible carrier. 19. The formulation according to claim 8, wherein the easily dispersible carrier is water. 20. The formulation according to claim 19, further comprising a surfactant and a fine powder. 21. The formulation according to claim 18, wherein the concentration of the active ingredient is between 0.5% and 75%. 22 N-[(phoshynyl)aminocothio or N-(((
Method for producing aminocothio-methyl carbamate (phoshitthioyl). (wherein R1 is selected from the group consisting of lower alkyl and cycloalkyl; 2-Dioxaphospholinan 2-yl)isopropylamino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N-C(C(((5,5-dimethyl-2thioxoto 3,2-dioxa phospholinan-2-yl)t-butylamino]thio]methylamino]carbonyl]oxy
Ethanimidothioate; Methyl N-
-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N-[[[[[ethyl(5,5-dimethyl-2-
Thioxoto 3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy
Ethanimidothioate: Methyl N-(C(((isopropyl(2-thioxo-1,3,2-phosphorane-2-
yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N-C(CCCisopropyl(2-thioxo-1
・3,2-dioxaphospholinan-2yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate: Methyl N-C(((isopropyl(4,4,6-drimethyl-2-thioxo- 1,3,2-dioxaphosphorinan-2-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N-・2-dioxaphosphorinane-2
-yl)amino]thio]methylamino]carbonyl]oxy]ethanimidothioate; Methyl N-([C[methyl(2-thioquinto3,2-dioxaphospholinan-2-yl)amino]thio]methylamino [carbonyl]oxy]ethanimidothioate; and methyl N-
23. The method of claim 22, wherein the compound is selected from the group consisting of -yl)amino]thio]methylamino]carbonyl]okyne]ethanimidothioate. 24 The product compound is methyl N-CC (CC cyclohexyl (5,5-dimethyl-2-thioxo-1,3,2-
23. The method of claim 22, wherein dioxaphospholinan-2-yl)aminocothio"methylamino]carbonyl]oxy]ethanimidothioate.