Abstract:
Novel thiazinephosphonic acid derivatives (I): ##STR1## wherein R 1  and R 2  each is lower alkoxy, lower alkynyloxy, lower alkylthio, arylthio (e.g., monocyclic aromatic group), or lower alkylamino; R 3  and R 4  each is hydrogen or lower alkyl; R 5 , R 6 , and R 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 1  and R 2  each is lower alkoxy, lower alkynyloxy, lower alkylthio, arylthio, or lower alkylamino; R 3  and R 4  each is hydrogen or lower alkyl; R 5 , R 6 , and R 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 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 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 1  and R 2  each is lower alkoxy, lower alkynyloxy, lower alkylthio, arylthio, or lower alkylamino; R 3  and R 4  each is hydrogen or lower alkyl; R 5 , R 6 , and R 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 1  and R 2  each is lower alkoxy, lower alkynyloxy, lower alkylthio, arylthio, or lower alkylamino; R 3  and R 4  each is hydrogen or lower alkyl; R 5 , R 6 , and R 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 3 , R 4 , R 5 , R 6 , and R 7  each has the same meaning as defined above, with a compound of the formula (III): ##STR7## wherein R 1 , R 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 &#34;lower&#34; 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. 
     &#34;The lower alkyl&#34; means straight or branched chain saturated hydrocarbon residue, in particular C 1  -C 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. 
     &#34;The lower alkoxy&#34; means a group formed from the above lower alkyl and a bivalent oxygen. Representatives of the lower alkoxy are C 1  -C 6  alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, and the like. 
     &#34;The alkynyloxy&#34; includes C 2  -C 5  alkynyloxy, for example, ethynyloxy, 2-propynyloxy, 3-butynyloxy, 4-pentynyloxy, etc. 
     &#34;The alkylthio&#34; means a group formed from the lower alkyl and a bivalent sulfur, especially C 1  -C 6  alkylthio, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, pentylthio, hexylthio, etc. 
     &#34;The alkylamino&#34; includes a group formed from the lower alkyl and an imino. Examples of the lower alkylamino are C 1  -C 6  alkylamino such as methylamino, ethylamino, propylamino, isopropylamino, butylamino, pentylamino, hexylamino, and the like. 
     &#34;The arylthio&#34; 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. 
     &#34;The halogen&#34; includes fluorine, chlorine, bromine, iodine, and the like. 
     &#34;The leaving group&#34; 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 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 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, α-picoline, γ-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°˜100° C., preferably at a temperature of 20°˜80° 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 3 , R 4 , R 5 , R 6 , and R 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°˜60° C. for 10˜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˜99.9%, preferably 20˜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˜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°˜20° C. The mixture is allowed to react at 25°˜30° 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°˜ 42.5° 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°˜20° C. The mixture is stirred at 30°˜35° 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°˜49.5° 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°˜20° C. The mixture is stirred at 25°˜30° 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 D   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˜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 (°C.)                                                 (temp. °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˜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˜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˜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˜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˜34.523   EtO    n-PrS           Me Me H   H   H O white crystals                                           37.5˜39.024   EtO    i-BuS           Me Me H   H   H O white crystals                                           40.5˜42.025   MeO    s-BuS           Me Me H   H   H O white crystals                                           41.0˜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˜46.535   EtO    n-PrS           Me Me 2-Me                     4-Cl                         H O white crystals                                           70.0˜71.536   MeO    s-BuS           Me Me 2-Me                     4-Cl                         H O white crystals                                           48.5˜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˜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˜51.549   CH.tbd.CCH.sub.2 O       EtS H  H  2-Me                     6-Me                         H O white crystals                                           77.5˜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˜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˜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˜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˜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˜79.064   EtO    n-PrS           Me Me 2-F 4-F H O white crystals                                           65.0˜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˜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&#39;-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°˜78.5° 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 (°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 (5×5 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° C. for 48 hours; and insecticidal rate was calculated. 
     B. Insecticidal test on larvae of Plutella xylostella 
     Cabbage leaves (5×5 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° 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° 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˜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° 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 (3×3 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° 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° 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° 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° 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° 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° 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° 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 (6×6 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° 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˜7 days after hatching) were confined in the Petri dish and allowed to keep at 25° 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° 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.