Thiazinephosphonic acid derivatives

Abstract

Novel thiazinephosphonic acid derivatives (I): ##STR1## wherein R.sup.1 and R.sup.2 each is lower alkoxy, lower alkynyloxy, lower alkylthio, arylthio (e.g., monocyclic aromatic group), or lower alkylamino; R.sup.3 and R.sup.4 each is hydrogen or lower alkyl; R.sup.5, R.sup.6, and R.sup.7 each is hydrogen, lower alyl, lower alkoxy, halogen, or trifluoromethyl; and X is oxygen or sulfur, are disclosed. A method for the production thereof, and pesticides comprising said compounds (I) are provided.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel thiazinephosphonic acid derivatives, production thereof, and pesticides comprising the thiazine phosphonic acid derivatives as an effective ingredient.

2. Prior Art

A lot of insecticides containing phosphorus atom are commercially available at present, while any insecticides having a thiazine ring are not known. A phosphonic acid diester bound to the nitrogen atom of a morphorinyl group is disclosed in JPN Unexamd. Pat Publn. No.49-101545, but no phosphorus compound having a thiazine ring is known.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a compound of the formula (I): ##STR2## wherein R.sup.1 and R.sup.2 each is lower alkoxy, lower alkynyloxy, lower alkylthio, arylthio, or lower alkylamino; R.sup.3 and R.sup.4 each is hydrogen or lower alkyl; R.sup.5, R.sup.6, and R.sup.7 each is hydrogen, lower alkyl, lower alkoxy, halogen, or trifluoromethyl; and X is oxygen or sulfur and production thereof; and it also relates to a pesticidal composition comprising one or more of said compounds and one or more carriers.

The compound (I) can be prepared by reacting a 2-phenylimino-3,4,5,6-tetrahydro-2H-1,3-thiazine (II) with a reactive phosphonic acid derivative (III). ##STR3## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and X each has the same meaning as defined above; and Y is a leaving group.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a compound of the formula (I): ##STR4## wherein R.sup.1 and R.sup.2 each is lower alkoxy, lower alkynyloxy, lower alkylthio, arylthio, or lower alkylamino; R.sup.3 and R.sup.4 each is hydrogen or lower alkyl; R.sup.5, R.sup.6, and R.sup.7 each is hydrogen, lower alkyl, lower alkoxy, halogen, or trifluoromethyl; and X is oxygen or sulfur and it also relates to a pesticidal composition comprising one or more of said compounds (I) and one or more carriers.

Furthermore, the present invention also relates to a process for preparing the compound of the formula (I): ##STR5## wherein R.sup.1 and R.sup.2 each is lower alkoxy, lower alkynyloxy, lower alkylthio, arylthio, or lower alkylamino; R.sup.3 and R.sup.4 each is hydrogen or lower alkyl; R.sup.5, R.sup.6, and R.sup.7 each is hydrogen, lower alkyl, lower alkoxy, halogen, or trifluoromethyl; and X is oxygen or sulfur, which comprises reacting a compound of the formula (II): ##STR6## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 each has the same meaning as defined above, with a compound of the formula (III): ##STR7## wherein R.sup.1, R.sup.2, and X each has the same meaning as defined above; and Y is a leaving group.

The present inventors have investigated various organic phosphorus pesticides and found that the 2-phenylimino-tetrahydro-1,3-thiazine-3-phosphonic acid esters (I) have potent pesticidal activities with low toxicities against human beings or animals. This invention is based on these findings.

The definitions in the above formulae will be explained in more detail as follows.

The group attached by the term "lower" in the definitions means a group having not more than 6 carbon atoms, especially not more than 5 carbon atoms, unless the term is particularly defined.

"The lower alkyl" means straight or branched chain saturated hydrocarbon residue, in particular C.sub.1 -C.sub.5 alkyl. Examples of the lower alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, neo-pentyl, 1-methylbutyl, 1,2-dimethylpropyl, hexyl, and the like.

"The lower alkoxy" means a group formed from the above lower alkyl and a bivalent oxygen. Representatives of the lower alkoxy are C.sub.1 -C.sub.6 alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, and the like.

"The alkynyloxy" includes C.sub.2 -C.sub.5 alkynyloxy, for example, ethynyloxy, 2-propynyloxy, 3-butynyloxy, 4-pentynyloxy, etc.

"The alkylthio" means a group formed from the lower alkyl and a bivalent sulfur, especially C.sub.1 -C.sub.6 alkylthio, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, pentylthio, hexylthio, etc.

"The alkylamino" includes a group formed from the lower alkyl and an imino. Examples of the lower alkylamino are C.sub.1 -C.sub.6 alkylamino such as methylamino, ethylamino, propylamino, isopropylamino, butylamino, pentylamino, hexylamino, and the like.

"The arylthio" is aryl, preferably a group formed from a monocyclic aryl or monocyclic aromatic group bound to a bivalent sulfur. The arylthio includes phenylthio, tolylthio, xylylthio, and the like.

"The halogen" includes fluorine, chlorine, bromine, iodine, and the like.

"The leaving group" means a group which can be easily eliminated during the reaction. Examples of the leaving group are acid residues such as chlorine, bromine iodine, and the like. The compound (I) can be prepared according to the following reaction sequence. ##STR8## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, and X each has the same meaning as defined above; and Y is a leaving group.

The reaction can be carried out even in the absence of a solvent, but preferably it proceeds in the presence of a solvent.

As the solvent, inert solvent such as aliphatic hydrocarbons (e.g., n-hexane, cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), ketones (e.g., acetone, methyl isobutyl ketone, etc.), ethers (e.g., diethyl ether, tetrahydrofurane, dioxane, etc.), halogenohydrocarbons (e.g., dichloromethane, chlorobenzene, etc.), and the like can be employed.

Preferably, this reaction is carried out in the presence of an acid-acceptor (a base).

The acid-acceptor includes organic base such as aliphatic tertiary amine (e.g., trimethylamine, triethylamine, tributylamine, etc.), aromatic amine (e.g., dimethylaniline, diethylaniline, etc.), and heterocyclic amine (e.g., pyridine, .alpha.-picoline, .gamma.-picoline, etc.); and inorganic base such as sodium carbonate, potassium carbonate, and the like.

The reaction may be carried out at a temperature of 0.degree..about.100.degree. C., preferably at a temperature of 20.degree..about.80.degree. C. and it terminates within a period of 1 to 12 hours, preferably 2 to 8 hours.

The product can be isolated in a conventional manner for purification such as extraction, recrystallization, column-chromatography, or the like.

The starting material (II) may be prepared according to the following reaction sequence. ##STR9## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 each has the same meaning as defined above.

The reaction of the compound (IV) with the compound (V) may be carried out in the absence or presence of a solvent with stirring at a temperature of 0.degree..about.60.degree. C. for 10.about.60 minutes. The solvent includes ether, benzene, and the like.

The compound (IV) is prepared from the corresponding amine in the same manner as described in, for example, J. Org. Chem. 29, 3098 (1964).

The compound (VI) can be converted into the compound (II) under reflux in the presence of an acid such as hydrochloric acid for 1 to 3 hours.

[Effect]

The compounds (I) have potent pesticidal activities against harmful plant-parasitic nematodes, insects belong to Orthoptera, Hemiptera, Lepidoptera, Diptera, Coleoptera (beetles), and mites. The compounds (I) can be employed by themselves or in a formulation such as powder, granules, wettable powder, emulsion, suspension, aerosol, flowable, and the like by mixing with appropriate solid or liquid carriers and adjuvants.

The formulations can be prepared in a conventional manner.

The solid carriers include vegetable powder (e.g., corn, soybean, wheat, wood), mineral powder (e.g., clay, bentonite, acid clay, vermiculite, talc, diatomaceous earth, pumice, active carbon), synthetic resin (e.g., vinyl chloride, polystyrene), and the like.

The liquid carriers include hydrocarbons (e.g., kerosene, solvent naphtha, toluene, xylene), alkanols (e.g., methanol, ethanol, ethylene glycol, polypropylene glycol), ethers (e.g., dioxane, cellosolve), ketones (e.g., methyl isobutyl ketone, cyclohexanone), halogenohydrocarbons (e.g., dichloroethane, trichloroethane), esters (e.g., dioctylphthalate), amides (e.g., dimethylformamide), nitriles (e.g., acetonitrile), fats and oils; and water.

As the adjuvant, surface active agents, wetting agents, sticking agents, thickeners, stabilizers, and the like may be employed. Examples of the adjuvants are anionic surface active agents (e.g., alkyl sulfonate, lignin sulfonate, alkylsulfate), nonionic surface active agents (e.g., alkylpolyoxyethylene ether, sorbitan ester, polyoxyethylene fatty acid ester, sucrose ester), water-soluble high-molecular compounds (e.g., casein, gelatin, CMC, PVA, gum arabic, alginic acid) can be used.

The compounds (I) are preferably used at a concentration of 0.1.about.99.9%, preferably 20.about.80% in the above formulation.

Furthermore, the compounds (I) can be used in combination with other insecticides, fungicides, herbicides, soil modifiers, fertilizers, and the like.

The application rate should be decided in consideration of the application method, application time, application place, objective insects, mites, or nematodes; or objective plants; generally the application rate is 1.about.500 g/10 are.

The present invention will be explained in more detail by the following Examples and the effect of the present invention will be confirmed by the following Experiments.

EXAMPLE 1

(Compound No. 25)

To a mixture of 5.64 g (25.6 mmol) of 2-phenylimino-5,5-dimethyl-3,4,5,6-tetrahydro-2H-1,3-thiazine, 2.85 g (28.2 mmol) of triethylamine, and 50 ml of benzene is dropwise added 5.29 g (25.6 mmol) of S-sec-butyl O-methyl monochlorothiolphosphonate with stirring at 10.degree..about.20.degree. C. The mixture is allowed to react at 25.degree..about.30.degree. C. for 6 hours; and the resulting triethylamine hydrochloride is removed by filtration. The benzene layer is washed with 3% hydrochloric acid, 3% aqueous sodium carbonate, and water; and then concentrated under reduced pressure to give 9.91 g of an oily material. The oily material is purified by silica-gel column chromatography (Wako gel C-300: registered trademark; solvent: n-hexane/acetone=10/1); and the fractions containing the objective compound are collected and the solvent is removed under reduced pressure to give 6.99 g (yield: 70.6%) of white crystalline S-sec-butyl O-methyl 2-phenylimino-5,5-dimethyl-3,4,5,6-tetrahydro-2H-1,3-thiazine-3-thiolphosphonate. m.p.: 41.0.degree..about. 42.5.degree. C.

EXAMPLE 2

(Compound No. 36)

To a mixture of 5.00 g (18.6 mmol) of 2-[(2-methyl-4-chlorophenyl)imino]-5,5-dimethyl-3,4,5,6-tetrahydro-2H-1,3-thiazine, 2.07 g (20.5 mmol) of triethylamine, and 50 ml of toluene is dropwise added 3.77 g (18.6 mmol) of S-sec-butyl O-methyl monochlorothiol-phosphonate at 10.degree..about.20.degree. C. The mixture is stirred at 30.degree..about.35.degree. C. for 4 hours. The resulting triethylamine hydrochloride is removed by filtration; the toluene layer is concentrated under reduced pressure to give 8.05 g of pale yellowish viscous oily material. The oily material is purified in the same manner as in Example 1 and the resultant transparent liquid is cooled to give 4.59 g (yield: 56.7%) of white crystalline S-sec-butyl O-methyl 2-[(2-methyl-4-chlorophenyl)imino]-5,5-dimethyl-3,4,5,6-tetrahydro-2H-1,3-thiazine-3-thiolphosphonate, m.p. 48.5.degree..about.49.5.degree. C.

EXAMPLE 3

(Compound No. 2)

To a mixture of 1.00 g (5.20 mmol) of 2-phenylimino-3,4,5,6-tetrahydro-2H-1,3-thiazine, 0.58 g (5.72 mmol) of triethylamine, and 10 ml of toluene is dropwise added 1.14 g (5.20 mmol) of O-ethyl S-n-propyl monochlorodithiophosphonate with stirring at 10.degree..about.20.degree. C. The mixture is stirred at 25.degree..about.30.degree. C. for 4 hours. The resulting triethylamine hydrochloride is removed by filtration, the toluene layer is concentrated under reduced pressure to give 1.56 g a pale yellowish viscous oily material. The oily material is purified in the same manner as in Example 1 to give 1.21 g (yield: 62.1%) of O-ethyl S-n-propyl 2-phenylimino-3,4,5,6-tetrahydro-2H-1,3-thiazine-3-dithiophosphonate as colorless transparent liquid. n.sub.D.sup.25 =1.5337.

The physical constants of the compounds provided in the above Examples and those of the compounds (I) prepared in the same manner as in Examples 1.about.3 are shown in the following Table 1.

TABLE 1__________________________________________________________________________Compd.No. R.sup.1, R.sup.2 R.sup.3, R.sup.4 R.sup.5 R.sup.6 R.sup.7 X mp (.degree.C.) (temp. .degree.C.) .sup.n D__________________________________________________________________________ 1 EtO EtO H H H H H S colorless liquid (25)1.5713 2 EtO n-PrS H H H H H S colorless liquid (25)1.5337 3 EtO i-PrNH H H H H H S white crystals 48.0.about.50.0 4 EtO EtO H H H H H O colorless liquid (25)1.5517 5 EtO n-PrS H H H H H O colorless liquid (20)1.5877 6 MeO MeO H H H H H O white crystals 74.0.about.75.5 7 n-PrO n-PrO H H H H H O colorless liquid 8 EtO MeNH H H H H H S colorless liquid (20)1.5532 9 EtO i-BuS H H H H H O colorless liquid (20)1.578610 MeO s-BuS H H H H H O colorless liquid (20)1.584511 EtO s-BuS H H H H H O colorless liquid (20)1.581112 EtO MeS H H H H H O colorless liquid13 EtO i-PrNH H H 2-Me 4-Cl H S white crystals 77.0.about.78.514 EtO n-PrS H H 2-Me 4-Cl H O colorless liquid (25)1.561015 EtO n-PrS H H 2-Me 4-Cl H S colorless liquid16 EtO i-BuS H H 2-Me 4-Cl H O colorless liquid (20)1.573617 EtO MeS H H 2-Me 4-Cl H O white crystals 86.5.about.87.518 MeO s-BuS H H 2-Me 4-Cl H O colorless liquid (20)1.585419 EtO s-BuS H H 2-Me 4-Cl H O colorless liquid (20)1.577520 EtO i-PrS H H 2-Me 4-Cl H O colorless liquid (20)1.577321 EtO i-PrNH H H 3-CF.sub.3 H H S colorless liquid (25)1.535022 EtO EtO Me Me H H H O white crystals 33.0.about.34.523 EtO n-PrS Me Me H H H O white crystals 37.5.about.39.024 EtO i-BuS Me Me H H H O white crystals 40.5.about.42.025 MeO s-BuS Me Me H H H O white crystals 41.0.about.42.526 EtO n-BuS Me Me H H H O pale yellowish liquid (20)1.563227 EtO C.sub.6 H.sub.5 S Me Me H H H O colorless liquid (20)1.600928 EtO EtO Me Me 2-MeO H H O pale brownish viscous liquid29 EtO n-PrS Me Me 2-MeO H H O pale yellowish liquid30 MeO s-BuS Me Me 2-MeO H H O pale yellowish liquid (20)1.557831 EtO s-BuS Me Me 2-MeO H H O pale brownish liquid (20)1.561932 EtO n-PrS H H 2-MeO H H O pale brownish viscous liquid33 MeO s-BuS H H 2-MeO H H O pale brownish liquid34 EtO s-Bus H H 2-MeO H H O white crystals 45.0.about.46.535 EtO n-PrS Me Me 2-Me 4-Cl H O white crystals 70.0.about.71.536 MeO s-BuS Me Me 2-Me 4-Cl H O white crystals 48.5.about.49.537 EtO n-BuS Me Me 2-Me 4-Cl H O colorless liquid (20)1.560438 EtO EtO Me Me 2-Me 4-Cl H O white crystals 45.0.about.46.539 MeO n-BuS Me Me 2-Me 4-Cl H O colorless liquid (20)1.557440 MeO i-BuS Me Me 2-Me 4-Cl H O yellow liquid (20)1.563141 EtO n-PrS H H H 4-n-Bu H O colorless liquid (20)1.563942 EtO n-PrS Me Me H 4-n-Bu H O colorless liquid (20)1.554943 MeO s-BuS Me Me H 4-n-Bu H O pale yellowish liquid (20)1.555244 EtO s-BuS Me Me H 4-n-Bu H O colorless liquid (20)1.551345 EtO n-BuS Me Me H 4-n-Bu H O colorless liquid (20)1.550346 EtO n-PrS H H 2-Me 6-Me H O white liquid (20)1.572847 MeO s-BuS H H 2-Me 6-Me H O white liquid (20)1.558248 EtO n-BuS H H 2-Me 6-Me H O white crystals 50.0.about.51.549 CH.tbd.CCH.sub.2 O EtS H H 2-Me 6-Me H O white crystals 77.5.about.78.550 MeO s-BuS H H 2-i-Pr H H O colorless liquid51 EtO s-BuS H H 2-i-Pr H H O colorless liquid (20)1.562652 CH.tbd.CCH.sub.2 O EtS H H 2-i-Pr H H O white crystals 83.0.about.84.053 EtO C.sub.6 H.sub.5 S H H 2-i-Pr H H O colorless liquid (20)1.600454 EtO n-PrS Me Me 2-i-Pr H H O white crystals 50.5.about.52.055 MeO s-BuS Me Me 2-i-Pr H H O colorless liquid (20)1.557956 EtO s-BuS Me Me 2-i-Pr H H O white crystals 54.0.about.55.557 EtO C.sub.6 H.sub.5 S Me Me 2-i-Pr H H O colorless liquid (20)1.588358 MeO s-BuS Me Me 2-Me 6-Me H O colorless viscous liquid (20)1.554259 MeO s-BuS Me Me 2-Et 6-Et H O colorless viscous liquid (20)1.550760 MeO s-BuS Me Me 2-i-Pr 6-i-Pr H O white crystals 78.5.about.80.061 MeO s-BuS Me Me 2-Me 4-Me H O white viscous liquid (20)1.560362 MeO s-Bus Me Me H 4-EtO H O pale yellowish viscous (20)1.573663 MeO s-BuS Me Me 2-F 4-F H O white crystals 77.0.about.79.064 EtO n-PrS Me Me 2-F 4-F H O white crystals 65.0.about.66.065 MeO s-BuS Me Me 2-Cl 4-Me H O colorless liquid (20)1.568066 EtO n-PrS Me Me 2-Cl 4-Me H O white crystals 51.5.about.53.567 EtO EtO Me Me 4-n-Bu H H O colorless transparent__________________________________________________________________________ liquid Note Me: methyl; Et: ethyl; Pr: propyl; Bu: butyl

EXAMPLE 4

______________________________________ (Percent by weight)______________________________________Effective ingredient (Compound No. 25) 2Clay 88Talc 10______________________________________

The above components are mixed to give a powder.

EXAMPLE 5

______________________________________ (Percent by weight)______________________________________Effective ingredient (Compound No. 36) 30Diatomaceous earth 45White carbon 20Sodium lauryl sulfate 3Sodium lignin sulfate 2______________________________________

The above components are mixed to give a wettable powder.

EXAMPLE 6

______________________________________ (Percent by weight)______________________________________Effective ingredient (Compound No. 2) 20Xylene 60Polyoxyethylene phenylphenol polymer 20emulsifier______________________________________

The above components are mixed to give an emulsion.

REFERENTIAL EXAMPLE

(Production of starting material)

A mixture of 18.0 g (0.068 mol) of N-4-n-butylphenyl-N'-3-hydroxypropylthiourea and 20 ml of 12N HCl is heated under reflux for 1 hour. After cooling, the mixture is basified with 100 ml of 4N NaOH and extracted with chloroform. The extract is dried and concentrated; and the resulting residue is recrystallized from hexane to give 14.7 g (yield: 88%) of 2-[(4-n-butylphenyl)imino]-3,4,5,6-tetrahydro-2H-1,3-thiazine, m.p. 77.degree..about.78.5.degree. C.

The compounds (II) provided in the same manner as in the above Referential Example are shown in Table 2.

TABLE 2______________________________________R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 mp (.degree.C.)______________________________________H H H H H 118-119Me Me H H H 157-158H H 4-n-Bu H H 77-78.5Me Me 4-n-Bu H H 126-127H H 2-Me 4-Cl H 133-134Me Me 2-Me 4-Cl H 155.5-157H H 2-MeO H H 126-129.5Me Me 2-MeO H H 97-99H H 2-i-Pr H H 151-152Me Me 2-i-Pr H H 155-157H H 2-Me 6-Me H 131-132Me Me 2-Me 6-Me H 158-160H H 4-EtO H H 128-130Me Me 2-Me 4-Me H 135-138Me Me 2-i-Pr 6-i-Pr H 199-200Me Me 2-Et 6-Et H 132-133Me Me 2-F 4-F H 169-171H H 3-CF.sub.3 H H 152-152.5Me Me 2-Cl 4-Me H 145-147______________________________________ (Note) Me: methyl; Et: ethyl; Pr: propyl; Bu: butyl

EXPERIMENT 1

[Preparation of a test solution]

A solution of the compound (I) in a small amount of DMF (dimethylformamide) is diluted with distilled water containing TWEEN 20 (registered trademark) at a concentration of 100 ppm to prepare a predetermined amount of the test solution.

[Test Method]

A. Insecticidal test on larvae of Spodoptera litura

Cabbage leaves (5.times.5 cm) were soaked in the test solution and dried in air. Ten larvae (2 instar) of Spodoptera litura were put on the 2 cabbage leaves in a Petri dish (9 cm in diameter) and allowed to feed at 25.degree. C. for 48 hours; and insecticidal rate was calculated.

B. Insecticidal test on larvae of Plutella xylostella

Cabbage leaves (5.times.5 cm) were soaked in the test solution and dried in air. Ten larvae (3 instar) of Plutella xylostella were put on the cabbage leaf in a Petri dish (9 cm in diameter) and allowed to feed at 25.degree. C. for 48 hours; and insecticidal rate was calculated.

C. Insecticidal test on larvae of Adoxophyes orana

Tea leaves (whole leaves) were soaked in the test solution and dried in air. The three tea leaves were placed on a polyethylene cup (6 cm in diameter, 4 cm in depth). Ten larvae (4 instar) of Adoxophyes orana were put on the leaf in the cup and kept at 25.degree. C. for 48 hours; and insecticidal rate was calculated.

D. Insecticidal test on susceptible adults of Nephotettix cincticeps

Stem of six to seven rice seedlings (1.5.about.2 leaves) were bundled up with a sponge tape, which was fixed in a polyethylene cup (6 cm in diameter, 4 cm in depth) containing a small amount of water.

Test solution (2 ml) was applied to the foliage of the plants in a rotary sprayer and the bunch was dried in air, and it was covered with a transparent plastic cylinder. Ten female adults to Nephotettix cincticeps were confined in the cylinder and allowed to feed at 25.degree. C. for 48 hours. Then, insecticidal rate was calculated.

I. Insecticical test on susceptible larvae of Myzus persicae

J. Insecticidal test on resistant larvae of Myzus persicae

A leaf (3.times.3 cm) of a chinese cabbage was placed on a polyethylene cup (6 cm in diameter, 4 cm in depth) filled with 0.3% agar-gel. One apterous adult of Myzus persicae was put on the leaf and allowed to keep at 25.degree. C. for 24 hours to make larviposition. After removal of the adult, 2 ml of the test solution was applied to the foliage under a rotary sprayer; and larvae of Myzus persicae were allowed to keep at 25.degree. C. for 48 hours. Then insecticidal rate was calculated.

K. Miticidal test on adults of Tetranychus cinnabarinus

N. Miticidal test on adults Tetranychus urticae

A leaf (2 cm in diameter) of kidney beans was placed on a polyethylene cup (6 cm in diameter, 4 cm in depth) filled with 0.3% agar-gel. Twelve female adults were put on the leaf and allowed to keep at 25.degree. C. for 24 hours. After removal of dead and unhealthy individuals, 2 ml of the test solution was applied to the leaf in a rotary sprayer. The adults were allowed to keep at 25.degree. C. for 48 hours. Then insecticidal rate was calculated.

L. Miticidal test on larvae of Tetranychus cinnabarinus

O. Miticidal test on larvae of Tetranychus urticae

A leaf (2 cm in diameter) of kidney beans was placed on a polyethylene cup (6 cm in diameter, 4 cm in depth) filled with 0.3% agar-gel. Seven female adults were put on the leaf and allowed to keep at 25.degree. C. for 24 hours to make them lay eggs.

After removal of the adults, 2 ml of the test solution was applied to the leaf in a rotary sprayer. The larvae was allowed to keep at 25.degree. C. for 7 days and the number of dead hatched larvae out of all of those were counted; and miticidal rate was calculated.

M. Miticidal test on eggs of Tetranychus cinnabarinus

P. Miticidal test on eggs of Tetranychus urticae

The test was carried out in the same manner as in Tests L and O, the cup was kept at 25.degree. C. for 7 days and the number of dead eggs were counted; and ovicidal rate was calculated.

Q. Insecticidal test on adults of Epilachna vigintioctopunctata

A leaf (6.times.6 cm) of an eggplant was soaked in the test solution and dried in air. Five imagos (per leaf) of Epilachna vigintioctopunctata was put on the leaf in a Petri dish (9 cm in diameter) and allowed to feed at 25.degree. C. for 48 hours. Then insecticidal rate was calculated.

R. Insecticidal test on larvae of Periplaneta americana

A filter paper (9 cm in diameter) was soaked in the test solution in a Petri dish. Five larvae (1.about.7 days after hatching) were confined in the Petri dish and allowed to keep at 25.degree. C. for 48 hours. Then insecticidal rate was calculated.

S. Insecticidal test on adults of Callosobruchus chinensis

Ten adults within 24 hours after adult eclosion was laid in a screw tube (1.8 cm in diameter, 5 cm in height) of which the top and the bottom were covered with stainless steel net. The adults in the screw tube were immersed in the test solution, dried in air, and allowed to keep at 25.degree. C. for 48 hours. Then insecticidal rate was caluculated.

The results were shown in the following Table 3.

TABLE 3__________________________________________________________________________Comp No. PPM A B C D I J K L M N O P Q R S__________________________________________________________________________ 6 2000 87 100 100 4 2000 100 100 100 93 1000 100 100 79 93 250 100 100 63 91 95 16 87 81 1 2000 100 100 100 1000 100 80 100 250 100 100 63 10022 2000 100 100 100 250 100 97 100 95 63 100 16 96 7 2000 100 100 100 250 9612 2000 7417 2000 71 2 2000 100 100 100 90 100 1000 100 100 250 100 100 63 70 5 2000 100 100 1000 7715 2000 100 100 100 83 100 250 94 97 100 63 10014 2000 100 100 100 100 83 100 1000 100 95 100 100 100 250 70 75 81 100 100 100 63 100 70 16 9523 2000 100 100 100 100 100 1000 100 250 100 100 100 97 70 63 100 100 70 16 8720 2000 100 100 100 250 70 100 100 63 100 9510 2000 100 10018 2000 100 100 100 90 100 250 100 63 100 16 9525 2000 100 100 100 100 100 1000 100 100 250 100 75 100 100 97 100 100 63 100 100 100 82 100 100 16 100 4 100 1 8911 2000 100 75 100 100 100 100 250 90 100 100 71 63 100 100 16 10019 2000 100 100 100 100 82 100 1000 100 250 85 100 100 90 100 100 63 100 100 90 100 16 100 9 2000 100 100 100 80 100 250 70 100 100 100 100 63 100 100 92 16 70 9516 2000 100 100 100 100 70 100 250 70 100 100 100 100 100 63 100 100 100 80 16 85 100 4 7124 2000 100 70 100 100 100 100 1000 100 250 100 100 100 100 100 63 100 100 90 86 70 16 100 8 2000 81 100 100 100 250 100 3 2000 100 100 1000 100 9713 2000 100 100 1000 10021 2000 10067 1000 100 86 250 9032 1000 100 76 250 7535 1000 100 100 100 100 100 100 250 75 85 100 100 100 100 100 100 73 91 63 100 100 94 100 80 96 16 100 100 74 98 1 10042 1000 100 100 100 100 100 100 250 70 100 82 100 74 84 63 100 100 100 16 94 7526 1000 75 95 100 95 100 100 250 100 100 97 97 63 73 100 100 16 8037 1000 95 73 100 90 73 70 100 250 80 100 100 100 63 100 90 90 16 10045 1000 100 100 100 100 250 85 100 100 63 76 8844 1000 100 100 100 100 81 100 100 250 80 100 97 63 100 100 16 89 9534 1000 100 100 100 100 91 250 100 94 63 100 8133 1000 70 100 100 100 100 90 250 100 100 97 86 63 95 100 76 16 9136 1000 100 100 100 100 100 100 100 250 85 95 90 100 100 100 100 100 100 88 63 90 100 100 100 100 100 100 87 16 100 100 79 100 100 86 1 10043 1000 100 100 100 100 83 100 100 250 100 100 83 100 100 92 63 100 100 100 85 93 16 100 92 1 7441 1000 95 100 100 100 100 250 100 100 100 63 100 100 16 94 9547 1000 100 100 100 100 94 100 100 250 100 70 100 72 100 100 100 100 100 100 63 75 100 100 100 100 80 100 100 100 16 100 100 91 92 8646 1000 95 71 100 100 100 100 250 85 100 100 91 100 80 100 63 70 100 100 85 100 95 16 100 8748 1000 100 100 100 100 100 250 85 100 100 63 100 16 8849 1000 7950 1000 100 82 97 100 98 100 100 250 75 100 100 99 100 100 100 100 63 100 100 83 100 80 90 94 16 100 90 88 4 8954 1000 100 100 100 100 80 100 250 78 100 85 100 96 63 81 97 90 86 16 70 8651 1000 100 100 100 100 92 100 100 250 100 79 100 100 100 100 63 100 100 100 80 100 100 16 100 100 10052 1000 92 250 100 63 8955 1000 100 100 100 100 86 100 100 250 85 70 100 100 100 100 100 63 100 100 100 72 87 100 100 100 16 97 10056 1000 95 100 100 100 100 100 250 100 100 100 100 63 100 100 100 16 85 10057 1000 100 9039 1000 100 100 100 90 100 250 80 100 100 100 100 100 63 100 100 91 100 16 8640 1000 100 100 100 100 89 100 100 250 70 100 100 100 87 100 100 100 63 100 100 100 100 100 16 100 100 100 100 4 100 1 8361 1000 100 97 100 100 100 100 250 95 90 63 80 100 95 16 10047 1000 100 100 100 100 77 100 100 250 100 100 95 100 70 80 63 75 100 100 100 16 70 10059 1000 100 100 100 100 98 100 100 250 100 100 97 90 63 100 100 100 70 16 100 95 4 10060 1000 100 86 100 100 96 100 100 250 100 100 100 63 70 100 100 100 16 100 100 4 10062 1000 100 100 100 100 100 100 250 80 79 63 100 16 9564 1000 100 100 100 97 100 100 250 100 80 100 100 100 100 100 90 63 75 100 100 91 100 80 16 100 72 4 10063 1000 75 100 100 100 100 250 100 100 100 100 100 100 63 88 100 100 99 100 100 90 100 16 100 100 100 70 4 10066 1000 100 100 100 90 250 100 100 100 63 100 8065 1000 100 92 100 100 100 100 250 75 95 80 100 100 100 70 70 63 80 100 100 78 16 100 100__________________________________________________________________________ (Note) A, B, C, D, I, J, K, L, M, N, O, P, Q, R, and S represent the effects on insects or mites as described below. A: Spodoptera litura (larvae) B: Plutella xylostella (larvae) C: Adoxophyes orana (larvae) D: Nephotettix cincticeps (adults) I: Myzus persicae (susceptible larvae) J: Myzus persicae (resistant larvae) K: Tetranychus cinnabarinus (adults) L: Tetranychus cinnabarinus (larvae) M: Tetranychus cinnabarinus (eggs) N: Tetranychus urticae (adults) O: Tetranychus urticae (larvae) P: Tetranychus urticae (eggs) Q: Epilachna vigintioctopunctata (adults) R: Periplaneta americana (larvae) S: Callosobruchus chinensis (adults) The number means lethal rate (%).

As the result of the tests, it is found that the compounds of the present invention show potent effects on various kinds of harmful insects and mites, in particular Tetranychus cinnabarinus and Myzus persicae injurious to crop plants.

Claims

1. A compound of the formula: ##STR10## wherein R.sup.1 and R.sup.2 each is lower alkoxy, lower alkynyloxy, lower alkylthio, lower alkylamino, or C.sub.6 -C.sub.8 arylthio selected from the group consisting of phenylthio, tolylthio and xylylthio; R.sup.3 and R.sup.4 each is hydrogen or lower alkyl; R.sup.5, R.sup.6, and R.sup.7 each is hydrogen, lower alkyl, lower alkoxy, halogen, or trifluoromethyl; and X is oxygen or sulfur.

2. The compound claimed in claim 1, wherein R.sup.1 and R.sup.2 each is C.sub.1 -C.sub.6 alkoxy, C.sub.2 -C.sub.5 alkynyloxy, C.sub.1 -C.sub.6 alkylthio, C.sub.1 -C.sub.6 alkylamino, or C.sub.6 -C.sub.8 arylthio selected from the group consisting of phenylthio, tolylthio and xylylthio; R.sup.3 and R.sup.4 each is hydrogen or C.sub.1 -C.sub.6 alkyl; R.sub.5 is C.sub.1 -C.sub.5 alkyl, C.sub.1 -C.sub.6 alkoxy, halogen, or trifluromethyl.

3. The compound claimed in claim 1, wherein X is oxygen.

4. The compound claimed in claim 1, wherein R.sup.1 and R.sup.2 each is C.sub.1 -C.sub.6 alkoxy or C.sub.1 -C.sub.5 alkylthio.

5. The compound claimed in claim 2, wherein X is oxygen.

6. The compound claimed in claim 2 wherein R.sup.1 and R.sup.2 each is C.sub.1 -C.sub.6 alkoxy or C.sub.1 -C.sub.6 alkylthio.

7. The compound claimed in claim 1, wherein the lower alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, neo-pentyl, 1-methylbutyl, 1,2-dimethylpropyl and hexyl; the C.sub.1 -C.sub.6 alkoxy is selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy and hexyloxy; and the C.sub.2 -C.sub.5 alkynyloxy is selected from the group consisting of ethynyloxy, 2-propynyloxy, 3-butynyloxy, and 4-pentynyloxy.

8. The compound according to claim 2, wherein the C.sub.1 -C.sub.6 alkylthio is selected from the group consisting of methylthio, ethylthio, propylthio, isopropylthio, butylthio, pentylthio and hexylthio and the C.sub.1 -C.sub.6 alkylamino is selected from the group consisting of methylamino, ethylamino, propylamino, isopropylamino, butylamino, pentylamino and hexylamino.

9. An insecticidal composition comprising an insecticidally effective amount of one or more of the compounds of the formula: ##STR11## wherein R.sup.1 and R.sup.2 each is lower alkoxy, lower alkynyloxy, lower alkylthio, lower alkylamino, or C.sub.6 -C.sub.8 arylthio selected from the group consisting of phenylthio, tolylthio and xylylthio; R.sup.3 and R.sup.4 each is hydrogen or lower alkyl; R.sup.5, R.sup.6, and R.sup.7 each is hydrogen, lower alkyl, lower alkoxy, halogen, or trifluoromethyl; and X is oxygen or sulfur and one or more carriers therefor.

10. The composition according to claim 8, wherein the lower alkyl is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, neo-pentyl, 1-methylbutyl, 1,2-dimethylpropyl and hexyl; the C.sub.1 -C.sub.6 alkoxy is selected from the group consisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy and hexyloxy, and; the C.sub.2 -C.sub.5 alkynyloxy is selected from the group consisting of ethynyloxy, 2-propynyloxy, 3-butynyloxy, and 4-pentynyloxy.

11. The composition according to claim 9, wherein the C.sub.1 -C.sub.6 alkylthio is selected, from the group consisting of methylthio, ethylthio, propylthio, isopropylthio, butylthio, pentylthio and hexylthio.

12. The composition according to claim 9, having an effective insecticidal activity against insects belonging to the group consisting of Orthoptera, Hemiptera, Lepidoptera, Diptera, Coleoptera and mites.

13. The composition according to claim 9, which is in the form of a powder, granules, wettable powder, emulsion, suspension or aerosol.

14. The composition according to claim 13, which contains a solid carrier selected from the group consisting of vegetable powder, mineral powder and synthetic resin.

15. The composition according to claim 13, which contains a liquid carrier selected from the group consisting of hydrocarbons, alkanols, ethers, ketones, halogenohydrocarbons, esters, amides, nitriles, fats, oils, and water.

16. The composition according to claim 13, which contains an adjuvant selected from the group consisting of surface active agents, wetting agents, sticking agents, thickeners and stabilizers.

17. The composition according to claim 16, which contains an adjuvant selected from the group consisting of anionic surface active agents, nonionic surface active agents and water-soluble high-molecular compounds.

18. The composition according to claim 9, wherein said compound is present at a concentration of 0.1 to 99.9%.

19. The composition according to claim 18, wherein said compound is present at a concentration of 20 to 80%.

20. A method for treating insects comprising applying an insecticidally effective amount of the composition of claim 9 to insects or to the habitats of insects.

21. The method according to claim 20, wherein the application rate is 1-500 g/10 are.