Organotin compounds and pesticides containing them

This invention relates to novel asymmetric triorganotin compounds, to their preparation and to pesticidal compositions containing the novel compounds.
There exist a wide variety of pests which are parasitic on plants. Among them, mites (Acarina) do considerable damage to a wide range of crops and garden plants, which causes a serious problem in agricultural management. Since such phytophagous mites rapidly acquire a tolerance to pesticides, novel and efficient pesticides have continuously been sought.
Organic compounds which are known to be useful for controlling such mites include, for example, cyhexatin (Plictran.RTM., U.S. Pat. No. 3,264,177) and fenbutatin oxide (Osadan.RTM., U.S. Pat. No. 3,657,451). However, such known compounds have drawbacks that their pesticidal activities varies depending on species of pests, and that they do not inhibit a certain species of spider mites because of the acquired tolerance.
In view of the above, the present inventors have made extensive study on organotin compounds in order to find effective compounds exhibiting pesticidal activity, in particular, those effective to the spider mites which have already acquired a tolerance against the existing pesticides. As a result of the study, it has been found that the asymmetric triorganotin compounds of the formula (I) below exhibit an excellent pesticidal activity, in particular, to the spider mites exhibiting tolerance against the known organotin compounds.
Thus, the present invention provides assymmetric triorganotin compounds having pesticidal activity of the formula (I): ##STR6## in which R.sup.1 represents alkyl, cycloalkyl or aralkyl, R* represents fluorophenyl or trifluoromethylphenyl when R.sup.1 is alkyl; R* represents dichlorophenyl, neopentyl, trimethylsilylmethyl, dimethylphenylsilylmethyl or a group of the formula: ##STR7## wherein R.sup.2 represents halogen, trifluoromethyl, lower alkyl or lower alkoxy when R.sup.1 is cycloalkyl; or R* represents 2-thienyl, 3-thienyl, neopentyl, trimethylsilylmethyl, dimethylphenylsilylmethyl or a group of the formula: ##STR8## wherein R.sup.3, R.sup.4 and R.sup.5 independently represent hydrogen, halogen, trifluoromethyl, lower alkyl or lower alkoxy when R.sup.1 is aralkyl, m represents 1 or 2, and X represents halogen, imidazolyl, triazolyl, phenylthio or a radical selected from the group consisting of: ##STR9## wherein R.sup.6 represents alkyl, R.sup.7 and R.sup.8 independently represent lower alkyl and R.sup.9 and R.sup.10 independently represent hydrogen or lower alkyl when m is 1; or they independently represent oxygen, sulfur or a radical selected from: ##STR10##
For purposes of the present invention, as disclosed and claimed herein, the following terms are as defined below.
The term "alkyl" refers to a straight or branched saturated hydrocarbon radical having one to twelve carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, neopentyl, 1-methylbutyl, 1,2-dimethylbutyl, hexyl, heptyl, octyl, nonyl, decyl, and the like.
The term "lower alkyl" refers to an alkyl radical having less than six carbons, of the above defined alkyl.
The term "aralkyl" refers to an alkyl substituted by an aryl radical and includes benzyl, phenylethyl, phenylpropyl, methylbenzyl, neophyl, and the like.
The term "cycloalkyl" refers to a saturated hydrocarbon ring having three to ten carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like.
The term "halogen" means chloro, bromo, iodo and fluoro.
The term "pests" herein used should be considered to mean both insects and mites harmful to plants, especially phytophagous ones, and, the term "pesticides" or "pesticidal composition" to include insecticides and acaricides.
The process for the preparation of the compounds of the formula (I) will be detailed below.
The compounds (I) wherein X is halogen, which will hereinafter be referred to as compound (Ia), can be prepared according to the following Reaction Scheme I, whereas the other compounds (I) wherein X is other than halogen can be prepared from the compounds (Ia) according to the Reaction Schemes II to IV hereinafter described. ##STR11## In the above scheme, R* and R.sup.1 are as previously defined, Hal, Y.sup.1 and Y.sup.2 are each chlorine, bromine or iodine, and n is 1 or 2, with the proviso that when n is 1, R* is a silicon-containing group and when n is 2, R* is an aryl or neopentyl group. The reactions are detailed below.
1st step
A compound (II) is reacted with an organotin halide (III) at a temperature from about 5.degree. C. to 100.degree. C. in a suitable solvent to yield an asymmetric tetraorganotin compound of the general formula (IV). Preferred solvents are ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and the like.
The starting compound (II) may be conventionally prepared under the conditions usually employed for the preparation of a Grignard reagent.
The starting organotin halide of the general formula (III) wherein n is 2 can be represented by the formula:
(R.sup.1).sub.2 Sn(Y.sup.2).sub.2
and may be prepared by redistribution reaction between a corresponding symmetric tetraorganotin compound of the formula:
(R.sup.1).sub.4 Sn
wherein R.sup.1 is as defined above, and a stannic halide according to known procedures. The asymmetric phenyldiorganotin halide, which corresponds to the starting compound of the formula (III) wherein n equals to 1 and has the formula:
(R.sup.1).sub.2 Sn(Phe)Y.sup.2
is itself an objective compound of the present invention and, therefore, may be prepared from the aforementioned starting compound (III) wherein n is 2, in accordance with the Reaction Scheme I.
2nd step
Halogenation of the asymmetric tetraorganotin compound of the formula (IV) is convertionally carried out by direct addition of a gaseous halogen, or by addition of halogen dissolved in a suitable solvent, to a solution of the asymmetric tetraorganotin compound dissolved in the same solvent, while maintaining the reaction temperature at -50.degree. C. to 30.degree. C. Suitable solvents employed in the reaction include chloroform, carbon tetrachloride, benzene, toluene, heptane, hexane, and the like. Chloroform and carbon tetrachloride are especially preferred.
A preferred molar ratio of the asymmetric tetraorganotin compound (IV) and halogen is about 1:1. The reaction temperature is preferably maintained in the range of -10.degree. C. to 10.degree. C.
The reaction terminates when the addition of halogen or a halogen solution is complete. The reaction mixture is concentrated, and the desired compound is separated and purified by recrystallization, vacuum distillation or column chromatography, if necessary. The asymmetric triorganotin halides (Ia) thus prepared are liquid or solid at room temperature.
These halides (Ia) are easily converted to other objective compounds (I) of the invention, such as hydroxides, bis(asymmetric triorganotin)oxides and other various derivatives as shown in the following Reaction Schemes, by known procedures. ##STR12##
In the above schemes, R*, R.sup.1, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and Hal are as defined previously, Az is 1,3-imidazol-1-yl or 1,2,4-triazol-1-yl. Desirable conditions for the reactions shown in the above schemes are known in the art, and disclosed, for example, by R. Inhan, Chemical Reviews, 459-539, 1960(October).
The compounds of formula (I) of the present invention exhibit an excellent pesticidal activity against phytophagous pests of various orders, such as Acarina, Lepidoptera, Hemiptera, Coleoptera, Orthoptera and Diptera. In particular, the compounds (I) exhibit an excellent inhibiting activity against a wide variety of acarina such as citrus red mite (Panonychus citri), European red mite (Panonychus ulmi), hawthorn spider mite (Tetranychus viennensis), Kanzawa spider mite (Tetranychus kanzawai), citrus flat mite (Brevipalpus lewisi), privet mite (Brevipalpus obovatus) and pink citrus rust mite (Aculops pelekassi). Moreover, the compounds (I) exert no harm, or only minor harm which is easily repaired, on crops and garden plants.
A certain class of spider mites, for example the kanzawa spider mite, shows resistance to known acaricides, cyhezatin (Plictran.RTM., Dow Chemical Co., see U.S. Pat. No. 3,264,177), and fenbutatin oxide (Osadan.RTM., Shell Oil Co., see U.S. Pat. No. 3,657,451). The compounds (I) of the invention, as stated before, show an excellent inhibiting activity even to the mites having resistance against such known acaricides.
Therefore, the present invention also provides a pesticidal composition which comprises as an active ingredient a compound of formula (I) together with a suitable carrier and/or adjuvant.
The pesticidal composition of the invention can be in any desirable form, such as wettable powders, emulsifiable concentrates, dusts or flowables, and prepared by mixing a compound (I) with one or more of non-phytotoxic carriers or adjuvants in accordance with conventional methods in the art. Such carriers and adjuvants include various liquid substances such as organic solvents and water, surfactants, granular or fine solid substances, and the like.
Wettable powders may be obtained by mixing a compound (I) with a solid carrier, such as clay, talc, white carbon, diatomaceous earth or bentonite, an ionic or nonionic emulsifier or dispersing agent, such as higher alkoxysulfonate, polyoxyehthylenesorbitan, alkylphenoxypolyethoxyethanol or lignosulfonate, and if required, wetting agents, protective colloid and the like. Emulsifiable concentrates may be obtained by dissolving a compound (I) in a suitable organic solvent and then adding thereto an appropriate surfactant. The emulsifiable concentrates can exist as water-in-oil concentrates or as oil-in-water concentrates having a high concentration comparable to a condensed mayonnaise.
The pesticidal compositions of the invention may be employed alone or after mixing with other acaricidal, insecticidal, or fungicidal compositions, plant growth regulator, fertillizer or the like.
The content of the compound (I) in the pesticidal composition in the form of wettable powder or emulsifiable concentrate is generally from 7 to 70 percent by weight, preferably from 20 to 50 percent by weight. The amount of the composition to be applied to loci of pests will vary depending on a number of factors, such as a method, season or locus of application, species of pests and crops, and the like. However, the composition is usually applied at the application rate of 200 to 600 liter per 10 are, after diluted to 500 to 10,000 fold, preferably 1,000 to 5,000 fold.
Dust compositions usually contain from 0.5 to 10 percent, preferably from 2 to 5 percent by weight of the compound (I), and are applied at application rate of from 3 to 5 kg per 10 are. Fine dust compositions contain the compounds (I) in the range of from 0.5 to 10 percent, preferably 1 to 5 percent by weight, and are applied at the rate in the range of from 1.5 to 5 kg per 10 are.
The following detailed Examples, Formulations and Experiments are presented by way of illustration of certain specific embodiments of the invention.

EXAMPLE 1
Dineophyl-metatrifluoromethylphenyltin fluoride (compound 1)
(1) Dineophyl-di(metatrifluoromethylphenyl)tin
A 1,000 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser was charged with magnesium (12.5 g, 0.51 mol) and flushed with nitrogen. Each 3 ml of a mixture of metatrifluoromethylphenyl bromide (113.4 g, 0.504 mol) and tetrahydrofuran (220 g) was portionwise added from the dropping funnel. The reaction occurred with fuming when the mixture was heated to 60.degree.-70.degree. C. While the temperature of the solution was maintained at 60.degree. C., the solution of metatrifluoromethylphenyl bromide dissolved in tetrahydrofuran was added dropwise over about 2 hours.
After completion of the addition, the mixture was refluxed for 5 hours and then cooled to room temperature. Next, a solution of dineophyltin dichloride (85.6 g, 0.188 mol) dissolved in tetrahydrofuran (200 g) was dropwise added from a dropping funnel over 30 minutes, while maintaining the temperature at 10.degree. to 20.degree. C. After the addition, the mixture was kept at the reflux temperature for 7 hours. The mixture was then cooled to room temperature and hydrolyzed by the addition of a saturated aqueous ammonium chloride solution. The organic layer was separated, washed with water, filtered and concentrated under reduced pressure to yield brown viscous liquid. To this substance was added n-hexane (300 g) and activated clay (50 g) for decolorization. The mixture was filtered and concentrated under reduced pressure to obtain 118 g of dineophyl-di(metatrifluoromethylphenyl)tin as a colorless, clear and viscous liquid. Analysis by gas chromatography of the viscous liquid showed 95% purity. Tin content was 17.2% (theoretical: 17.6%).
(2) Dineophyl-metatrifluoromethylphenyltin fluoride
A 500 ml four-necked flask with a stirrer, a thermometer, a dropping funnel and a condenser was charged with dineophyl-dl(metatrifluoromethylphenyl)tin (80 g, 0.118 mol) obtained in Example 1-(1) and chloroform (200 g). A mixture of bromine (19 g, 0.216 gram atom) and chloroform (100 ml) was dropwise added from the dropping funnel over about 2.5 hours with stirring, while maintaining the temperature of the reaction mixture at -5.degree. to 0.degree. C. After completion of the addition, the mixture was allowed to warm to room temperature, filtered and concentrated under reduced pressure to give 72.2 g of dineophyl-metatrifluoromethylphenyltin bromide as a viscous liquid. The purity of the liquid was 93% based on a gas chromatography analysis. Crude dineophyl-metatrifluoromethylphenyltin bromide (72.2 g) thus prepared, benzen (120 g), potassium fluoride (14 g) and water (56 g) were charged into a 500 ml three-necked flask, and the mixture was refluxed for 2 hours. After completion of the reaction, the aqueous layer was separated off and the organic layer was washed with water, filtered and concentrated under reduced pressure. The resulting residue was crystallized from n-hexane at the temperature of -20.degree. C. to obtain 33.8 g of dineophyl-metatrifluoromethylphenyltin bromide. This substance was a liquid at room temperature and has a refractive index of n.sup.30 =1.5555. Tin content was 21.1% (theoretical: 21.6%).
EXAMPLE 2
Bis(dineophyl-metatrifluoromethylphenyltin)oxide (Compound 3)
Dineophyl-metatrifluoromethylphenyltin fluoride (13 g, 23.7 mmol) obtained in Example 1 was dissolved in benzene (60 g). To the resultant solution was added a 20% aqueous sodium hydroxide solution (7.2 g), and the mixture was allowed to react for one hour at a temperature between 75.degree. C. and 80.degree. C. After completion of the reaction, the aqueous layer was removed and the organic layer was washed with water and filtered. The benzene was distilled of from the organic layer under reduced pressure to yield 11.8 g of bis(dineophyl-metatrifluoromethylphenyltin)oxide as a pale-yellow viscous liquid. Refractive index: n.sup.30 =1.5651; Tin content: 21.9% (theoretical: 22.1%).
EXAMPLE 3
Dineophyl-metatrifluoromethylphenyltin acetate (compound 5)
Bis(dineophyl-metatrifluoromethylphenyltin)oxide (6 g, 5.57 mmol) prepared in Example 2 was dissolved in n-hexane (30 g). To this solution was added glacial acetic acid (0.67 g, 11.16 mmol), and the mixture was heated at temperature of 70.degree. to 75.degree. C. for one hour to effect an azeotropic dehydration. After completion of the reaction, the mixture was filtered, and n-hexane was distilled off from the filtrate to obtain 6.4 g of dineophyl-metatrifluoromethylphenyltin acetate as a pale-yellow viscous liquid. Refractive index: n.sup.30 =1.5465. Tin content: 20.1% (theoretical: 20.1%).
EXAMPLE 4
Dineophyl-metatrifluoromethylphenyltindimethyldithiocarbamate (compound 6)
Dineophyl-metatrifluoromethylphenyltin fluoride (10 g, 18.2 mmol) prepared in Example 1 was dissolved in benzene (50 g), and the resulting solution was added with a solution of sodium dimethyldithiocarbamate dihydrate (3.9 g, 21.8 mmol) dissolved in water (15.6 g). The mixture was heated at a temperature of from 75.degree. to 80.degree. C. for one hour. The aqueous layer was removed and the organic layer was washed with water and filtered. The filtrate was distilled to remove the benzene under reduced pressure and the resultant residue was recrystallized from petroleum ether to give 11.4 g of dineophyl-metatrifluoromethylphenyltindimethyldithiocarbamate as a white solid.
Mp: 96.degree.-97.degree. C. Tin content: 18.1% (theoretical: 18.2%).
EXAMPLE 5
Dineophyl-orthotrifluoromethylphenyltin chloride (compound 25)
Dineophyl-diorthotrifluoromethylphenyltin (113 g), a pale-yellow viscous liquid, was prepared in accordance with the teaching of Example 1 except that orthotrifluoromethylphenyl bromide (113.4 g, 0.502 mol), rather than metatrifluoromethylphenyl bromide, was used. Analysis of the resulting liquid by gas chromatography showed 96.3% purity. Tin content was 17.3%(theoretical: 17.6%).
Dineophyl-diorthotrifluoromethylphenyltin (80 g, 0.108 mol) obtained above was dissolved in chloroform (200 g). Chlorine gas (7.6 g, 0.216 gram atom) was then introduced into the resultant solution while keeping the temperature of the solution at between 0.degree. C. and 5.degree. C. The reaction mixture was then concentrated under reduced pressure and the resulting residue was recrystallized from methanol to yield 61.1 g of dineophyl-orthotrifluoromethylphenyltin chloride as a white solid. Analysis by gas chromatography of the solid indicated
97.3% purity.
Mp: 49.degree.-50.degree. C. Tin content: 21.0% (theoretical: 21.0%).
EXAMPLE 6
Bis(dineophyl-orthotrifluoromethylphenyltin)oxide (compound 16)
Dineophyl-orthotrifluoromethylphenyltin chloride (13.4 g, 23.7 mmol) obtained in Example 5 was hydrolyzed in accordance with the procedure described in Example 2 and the resultant product was recrystallized from n-hexane to give 12.1 g of bis(dineophyl-orthotrifluoromethylphenyltin)oxide.
Mp: 42.degree.-44.degree. C. Tin content: 21.8% (theoretical: 22.1%).
EXAMPLE 7
Dineophyl(orthotrifluoromethylphenyl)(1,2,4-triazole-1-yl)tin (compound 7)
Bis(dineophyl-orthotrifluoromethylphenyltin)oxide (6 g, 5.57 mmol) prepared in Example 6 and 1,2,4-triazole (0.77 g, 11.1 mmol) were dissolved in toluene (30 g), and the mixture was heated at 110.degree.-112.degree. C. for one hour to perform an azeotropic dehydration. The reaction mixture was filtered and distilled to remove the benzene, which gave 6.5 g of (dineophyl)(orthotrifluoromethylphenyl)(1,2,4-triazol-1-yl)tin as a pale-yellow viscous liquid.
Refractive index: n.sup.30 =1.5690. Tin content: 20.7% (theoretical: 19.8%).
EXAMPLE 8
Bis(dineophyl-orthotrifluoromethylphenyltin)sulfate (compound 55)
Bis(dineophyl-orthotrifluoromethylphenyltin)oxide (2.7 g, 2.51 mmol) prepared in Example 6 was dissolved in benzene (30 ml). To the resultant solution was added a 50% aqueous sulfuric acid solution (5 ml) and the mixture was stirred at room temperature for 15 minutes. The aqueous layer was separated and removed, and the organic layer washed with water, filtered and concentrated under reduced pressure to give 2.8 g of bis(dineophyl-orthotrifluoromethylphenyltin)sulfate as a pale-yellow viscous liquid.
Refractive index: n.sup.30 =1.5700. Tin content: 21.0% (theoretical: 20.5%).
EXAMPLE 9
Dineophyl-p-fluorophenyltin fluoride (compound 9)
Dineophyl-diparafluorophenyltin (100.9 g) was obtained as a colorless viscous liquid, in accordance with the teaching of Example 1-(1) except that parafluorophenyl bromide (89.3 g, 0.51 mol), rather than metatrifluoromethylphenyl bromide, was employed.
Gas chromatography analysis of this liquid showed 96.9% purity of the desired compound. Tin content was 20.6% (theoretical: 20.6%).
Dineophyl-di(parafluorophenyl)tin (62.1 g, 0.108 mol) prepared above was dissolved in chloroform (200 g). While the resulting solution was maintained at -15.degree. to -20.degree. C., chlorine gas (7.6 g, 0.216 gram atom,) was introduced. The mixture was then concentrated under reduced pressure to give 56 g of dineophyl-parafluorophenyltin chloride as a pale-yellow liquid. Gas chromatography analysis indicated 87.5% purity of the desired product.
A mixture consisting of the crude dineophyl-parafluorophenyltin chloride (50 g) and potassium fluoride (5.8 g, 0.1 mol) was heated for 2 hours in the presence of benzene (120 g) and water (23 g). The aqueous layer of the reaction mixture was removed, and the organic layer was washed with water, filtered and concentrated under reduced pressure. The residue thus obtained was crystallized from petroleum ether to give 38.5 g of dineophyl-parafluorophenyltin fluoride as a white solid.
Mp: 59.degree.-62.degree. C. Tin content: 23.2% (theoretical: 23.8%).
EXAMPLE 10
Bis(dineophyl-parafluorophenyltin)sulfide (compound 58)
Dineophyl-parafluorophenyltin fluoride (6 g, 12 mmol) obtained above was dissolved in benzene (30 ml). To this solution was added potassium sulfide (1 g, 17.7 mmol) dissolved in water (4 g) and the mixture was refluxed for 2 hours.
After the aqueous layer was separated and removed from the mixture, the organic layer washed with water and filtered. Evaporation of the benzene under reduced pressure yielded 6.4 g of bis(dineophyl-parafluorophenyltin)sulfide as a pale-yellow viscous liquid.
Refractive index: n.sup.30 =1.6155. Tin content: 23.1% (theoretical: 23.9%).
EXAMPLE 11
Bis(dineophyl-parafluorophenyltin)oxide (compound 17)
Using dineophyl-parafluorophenyltin fluoride (15 g, 30 mmol) prepared in Example 9 and a 20% aqueous sodium hydroxide solution (9 g), bis(dineophyl-parafluorophenyltin)oxide was prepared in accordance with the procedure as described in Example 2, as a white solid.
Mp: 84.degree.-86.degree. C. Tin content: 24.5% (theoretical: 24.3%).
EXAMPLE 12
Dineophyl(parafluorophenyl)(1,3-imidazol-1-yl)tin (compound 54)
Bis(dineophyl-parafluorophenyltin)oxide (6 g, 6.14 mmol) prepared in Example 11 and 1,3-imidazole (0.83 g, 12.3 mmol) were dissolved in toluene (30 g) and the mixture was heated at 110.degree.-112.degree. C. for one hour to effect an azeotropic dehydration. Filteration of the reaction mixture and evaporation of the benzene gave a solid residue, which was crystallized from n-hexane to yield 5.1 g of dineophyl(parafluorophenyl)(1,3-imidazol-1-yl)tin.
Mp: 123.degree.-127.degree. C. Tin content: 21.2% (theoretical: 21.7%).
EXAMPLE 13
Dicyclohexyl-parafluorophenyltin fluoride (compound 14)
Dicyclohexyl-diparafluorophenyltin (85.2 g) was prepared in accordance with the procedure as described in Example 1(1) except that parafluorophenyl bromide (89.3 g, 0.51 mol) and dicyclohexyltin dichloride (76.9 g, 0.216 mol), rather than metatrifluoromethylphenyl bromide and dineophenyltin dichloride, were employed. Gas chromatography of the recrystallized product from isopropanol showed 98.6% purity.
Mp: 88.degree.-90.degree. C. Tin content: 25.1% (theoretical: 25.0%).
In accordance with the procedure as described in Example 1(2), the above product (20 g, 0.042 mol) was first reacted with bromine to produce crude dicyclohexyl-parafluorophenyltin bromide, which was then treated with sodium fluoride to yield 11.7 g of dicyclohexyl-parafluorophenyltin flouride as a white solid.
Mp: 234.degree.-240.degree. C. (dec.). Tin content: 29.9% (theoretical: 29.7%).
EXAMPLE 14
Dineophy-orthotrifluoromethylphenyltin isocyanate (compound 60)
Dineophyl-orthotrifluoromethylphenyltin chloride (6 g, 10.6 mmol) prepared in Example 5, sodium cyanate (1.1 g, 15.9 mmol) and acetone (40 g) were charged into a flask and the mixture was refluxed for 3 hours. The mixture was then added with benzene (50 g) and water (30 g). The aqueous layer was removed, and the organic layer was washed with water and filtered.
Evaporation of the benzene under reduced pressure gave 5.6 g of dineophyl-orthotritluoromethylphenyltin isocyanate as a colorless viscous liquid.
Refractive index: n.sup.30 =1.5609. Tin content: 21.0% (theoretical: 20.7%).
EXAMPLE 15
Dineophyl-orthotrifluoromethylphenyltin isothiocyanate (compound 59)
Dineophyl-orthotrifluoromethylphenyltin chloride (6 g, 10.6 mmol) prepared in Example 5, potassium thiocyanate (1.5 g, 15.9 mmol), benzene (40 g) and water (10 g) were charged into a flask and the mixture was refluxed for 2 hours. The aqueous layer was removed and the organic layer was washed with water and filtered. Evaporation of the benzene under reduced pressure gave 6.0 g of dineophyl-orthotrifluoromethylphenyltin isothiocyanate as a colorless viscous liquid.
Refractive index: n.sup.30 =1.5787. Tin content: 20.5% (theoretical: 20.2%).
EXAMPLE 16
Dineophyl-orthotrifluoromethylphenyltin methylsulfide (compound 67)
Dineophyl-orthotrifluoromethylphenyltin chloride (6 g, 10.6 mmol) prepared in Example 5, a 15% aqueous sodium methylsulfide solution (7.4 g, 15.9 mmol) and benzene (40 g) were charged into a flask and the mixture was refluxed for 2 hours. The aqueous layer was removed and the organic layer was washed with water and filtered. Evaporation of the benzene under reduced pressure yielded 4.6 g of dineophylorthotrifluoromethylphenyltin methylsulfide as a colorless viscous liquid.
Refractive index: n.sup.30 =1.5804. Tin content: 20.9% (theoretical: 20.6%).
EXAMPLE 17
Dineophyl-orthotrifluoromethylphenyltin phenoxide (compound 68)
Bis(dineophyl-orthotrifluoromethylphenyltin)oxide (6 g, 5.6 mmol) prepared in Example 6, phenol (1.0 g, 11.2 mmol) and toluene (40 g) were charged into a flask and the mixture was allowed to react substantially in accordance with the procedure described in Example 7. Evaporation of the toluene followed by recrystallization of the resulting residue from petroleum ether yielded 4.4 g of dineophyl-orthotrifluoromethylphenyltin phenoxide as a white solid.
Mp: 69.degree.-71.degree. C. Tin content: 19.1% (theoretical: 19.0%).
EXAMPLE 18
Dineophyl-orthotrifluoromethylphenyltin phenylsulfide (compound 69)
A mixture of bis(dineophyl-orthotrifluoromethylphenyltin)oxide (6.0 g, 5.6 mmol) prepared in Example 6, thiophenol (1.2 g, 11.2 mmol) and toluene (40 g) was treated with the procedure described in Example 7. The product was recrystallized from n-hexane to obtain 5.2 g of dineophylorthotrifluoromethylphenyltin phenylsulfide as a white solid.
Mp: 81.degree.-82.degree. C. Tin content: 18.7% (theoretical: 18.6%).
EXAMPLE 19
S-(Dineophyl-orthotrifluoromethylphenyltin)O,O-diethyldithiophosphate (compound 71)
In substantial accordance with the procedure described in Example 7, a mixture of bis(dineophyl-orthotrifluoromethylphenyltin)oxide (6.8 g, 6.4 mmol) prepared in Example 6, O,O-diethyldithiophosphate (2.2 g, 12.8 mmol) and toluene (40 g) was reacted to provide 8.0 g of S-(dineophylorthotrifluoromethylphenyltin)O,O-diethyldithiophosphate as a colorless viscous liquid.
Refractive index: n.sup.30 =1.5759.
EXAMPLE 20
Dineophyl(4-chloro-3-trifluoromethylphenyl)tin bromide (compound 74)
Dineophyl-di(4-chloro-3-trifluoromethylphenyl)tin (125.8 g), a pale-yellow viscous liquid, was prepared in substantial accordance with the procedure described in Example 1-(1) except that 4-chloro-3-trifluoromethylphenyl bromide (131.0 g, 0.504 mol), rather than metatrifluoromethylphenyl bromide, was employed. Gas chromatography analysis of this liquid showed 98.5% purity. Tin content was 15.6% (theoretical: 15.9%).
Following the procedure described in Example 1-(2), dineophyl-di(4-chloro-3-trifluoromethylphenyl)tin (87.8 g, 0.118 mol) obtained above was then reacted with bromine to obtain a pale-yellow solid (79.2 g). This solid was recrystallized from methanol (200 g) to give 65.7 g of dineophyl-4-chloro-3-trifluoromethylphenyltin bromide as a white solid. Gas chromatography analysis of this solid showed 99.0% purity. Mp: 72.degree.-74.degree. C. Tin content: 18.3% (theoretical: 18.4%).
EXAMPLE 21
Dineophyl-2,4-difluorophenyltin fluoride (compound 79)
Dineophyl-di(2,4-difluorophenyl)tin (107.9 g), a colorless viscous liquid, was prepared according to the procedure described in Example 1-(1) except that 2,4-difluorophenyl bromide (98.4 g, 0.51 mol), rather than metatrifluoromethylphenyl bromide, was used. Gas chromatography analysis of this liquid showed 95.5% purity. Tin content was 19.0% (theoretical: 19.4%).
Next, following the procedure described in Example 1(2), the above product (72.1 g, 0.118 mol) was reacted with bromine to obtain crude dineophyl-2,4-difluorophenyltin bromide, which was then treated with sodium fluoride. Recrystallization of the resultant product from n-hexane gave 30.6 g of dineophyl-2,4-difluorophenyltn fluoride as a white solid.
Mp: 60.degree.-65.degree. C. Tin content: 22.6% (theoretical: 22.9%).
EXAMPLE 22
Dineophyl-2,4,5-trifluorophenyltin chloride (compound 92)
Dineophyl-di(2,4,5-trifluorophenyl)tin (113.1 g), a pale-yellow viscous liquid, was prepared in substantial accordance with the procedure described in Example 1 (1) except that 2,4,5-trifluorophenyl bromide (105.9 g, 0.502 mol), rather than metatrifluoromethylphenyl bromide, was employed. Gas chromatography analysis of this liquid showed 96.0% purity. Tin content was 17.8% (theoretical: 18.3%).
The above product (76.4 g, 0.118 mol) was then reacted with chlorine and the reaction mixture was worked up in substantial accordance with the procedure described in Example 5. Recrystallization of the product from n-hexane gave 39.3 g of dineophyl-2,4,5-trifluorophenyltin chloride as a white solid. Gas chromatography analysis of this solid showed 99.9% purity.
Mp: 65.degree.-67.degree. C. Tin content: 21.7% (theoretical: 21.5%).
EXAMPLE 23
Dineophyl-parachlorophenyltin fluoride (compound 108)
Dineophyl-di(parachlorophenyl)tin (107.5 g), a colorless viscous liquid, was prepared in substantial accordance with the procedure described in Example 1 except that metachlorophenyl bromide (97.4 g, 0.51 mol), rather than metatrifluoromethylphenyl bromide, was employed. Gas chromatography analysis of this liquid indicated 97.5% purity. Tin content was 19.1% (theoretical: 19.5%).
In substantial accordance with the procedure described in Example 1(2), the above product (71.8 g, 0.118 mol) was reacted with bromine to obtain crude dineophyl-metachlorophenyltin bromide, which was then reacted with sodium fluoride. The resulting product was recrystallized from n-hexane to provide 32.7 g of dineophyl-metachlorophenyltin fluoride as a white solid.
Mp: 104.degree.-105.degree. C. Tin content: 23.0% (theoretical: 23.0%).
EXAMPLE 24
Dineophyl-phenyltin fluoride (compound 144)
Dineophyl-diphenyltin (108.9 g), a colorless viscous liquid, was prepared in substantial accordance with the procedure described in Example 1-(1) except that phenyl bromide (78.8 g, 0.502 mol), rather than metatrifluoromethylphenyl bromide, was employed. Gas chromatography analysis of this liquid showed 97.8% purity. Tin content was 21.7% (theoretical: 22.0%).
Dineophyl-phenyltin fluoride (39.6 g), a white solid, was prepared using the above product (80 g, 0.128 mol) as described in Example 1(2).
Mp: 37.degree.-40.degree. C. Tin content: 24.9% (theoretical: 24.7%).
EXAMPLE 25
Dineophyl-orthomethoxyphenyltin chloride (compound 133)
Dineophyl-di(orthomethoxyphenyl)tin (105.9 g), a colorless viscous liquid, was prepared in substantial accordance with the procedure described in Example 1(1) except that orthoanisyl bromide (93.8 g, 0.502 mol), rather than metatrifluoromethylphenyl bromide, was employed. Gas chromatography analysis of this liquid showed 96.5% purity. Tin content was 19.5% (theoretical: 19%).
Dineophyl-orthomethoxyphenyltin chloride (30.1 g), a white solid, was prepared using the above product (70.7 g, 0.118 mol) and chlorine in the manner as described in Example 5. Gas chromatography analysis of this solid showed 99.5% purity.
Mp: 69.degree.-72.degree. C. Tin content: 22.7% (theoretical: 22.5%).
EXAMPLE 26
Dineophyl-3-thienyltin fluoride (compound 215)
(1) Dineophyl-di(3-thienyl)tin
A 1,000 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser was charged with 3-thienyl bromide (75 g, 0.0461 mol) and absolute ether (200 g). n-Butyl lithium (185.3 g) (15% solution in n-hexane) was added in dropwise fashion from the dropping funnel while maintaining the temperature of the reaction mixture at below -50.degree. C. After completion of the addition, the reaction mixture was stirred for about 10 minutes at below -50.degree. C. and then added with a solution of dineophyltin chloride (73.5 g, 0.161 mol) dissolved in tetrahydrofuran (140 g) through the dropping funnel at -50.degree. to -60.degree. C. over about 30 minutes. After completion of the addition, the mixture was stirred for about 2 hours at that temperature, allowed to warm to room temperature and stirred for about additional one hour. The reaction mixture was then hydrolyzed by the addition of water (120 ml). The organic layer was separated, added with hexane (200 g), washed with water, filtered and concentrated under reduced pressure to yield a brown viscous liquid. To this liquid were added n-hexane (300 g) and activated clay (50 g) for discolorization. The mixture was filtered and concentrated under reduced pressure to obtain 81.7 g of dineophyl-di(3-thienyl)tin as a colorless, transparent and viscous liquid. Gas chromatography analysis of this liquid showed 95.0% purity. Tin content was 21.0% (theoretical: 21.6%).
(2) Dineophyl-3-thienyltin fluoride
In substantial accordance with the procedure described in Example 1(2), dineophyl-di(3-thienyl)tin (80 g, 0.145 mol) obtained above was reacted with bromine to give crude dineophyl-3-thienyltin bromide, which was then reacted with sodium fluoride. The resulting product was recrystallized from n-hexane to provide 21.5 g of dineophyl-3-thienyltin fluoride as a white solid.
Mp: 85.degree.-90.degree. C. Tin content: 24.7% (theoretical: 24.4%).
EXAMPLE 27
Dicyclohexyl-paratrifluoromethylphenyltin chloride (compound 164)
Crude dicyclohexyl-di(paratrifluoromethylphenyl)tin (101.7 g), a white solid, was prepared in accordance with the procedure described in Example 1(1) except that paratrifluoromethylphenyl bromide (113.4 g, 0.504 mol) and dicyclohexyltin dichloride (66.9 g, 0.188 mol), rather than metatrifluoromethylphenyl bromide and dineophyltin dichloride, were employed. Gas chromatography analysis of this solid indicated 93.3% purity.
In substantial accordance with the procedure described in Example 5, the above product (60 g, 0.105 mol) was then reacted with chlorine and the resulting mixture was worked up to yield 31.5 g of dicyclohexyl-paratrifluoromethylphenyltin chloride as a white solid. Gas chromatography analysis of this solid indicated 99.0% purity.
Mp: 74.degree.-75.degree. C. Tin content: 25.8% (theoretical: 25.5%).
EXAMPLE 28
Bis(dicyclohexyl-paratrifluoromethylphenyltin)oxide (compound 165)
Dicyclohexyl-paratrifluoromethylphenyltin chloride (15.0 g, 32.2 mmol) prepared in Example 27 was treated in the manner as described in Example 6 to provide 11.3 g of bis(dicyclohexyl-paratrifluoromethylphenyltin)oxide as a white solid.
Mp: 86.degree.-89.degree. C. Tin content: 26.8% (theoretical: 27.1%).
EXAMPLE 29
Dicyclohexyl-paratrifluoromethylphenyltin-n-butylthioglycolate (compound 167)
Bis(dicyclohexyl-paratrifluoromethylphenyltin)oxide (6 g, 16.8 mmol) prepared in Example 28 and n-butyl thioglycolate (2.0 g, 13.6 mmol) were dissolved in toluene (30 g) and the mixture was heated at 110.degree.-112.degree. C. for one hour to effect an azeotropic dehydration. Evaporation of the toluene under reduced pressure gave 7.8 g of pale-yellow liquid.
Refractive index: n.sup.30 =1.5337. Tin content: 20.4% (theoretical: 20.6%).
EXAMPLE 30
Dicyclohexyl-3,4-dichlorophenyltin fluoride (compound 190)
Dicyclohexyl-di(3,4-dichlorophenyl)tin (101.9 g), a colorless viscous liquid, was prepared in substantial accordance with the procedure described in Example 1(1) except that 3,4-dichlorophenyl bromide (113.8 g, 0.504 mol) and dicyclohexyltin dichloride (66.9 g, 0.188 mol), rather than metatrifluoromethylphenyl bromide and dineophyltin dichloride, were employed. Gas chromatography analysis of this liquid showed 95.9% purity. Tin content was 20.2% (theoretical: 20.6%).
Dicyclohexyl-di(3,4-dichlorophenyl)tin (86.5 g, 0.150 mol) prepared above was allowed to react and the resulting mixture was worked up, as described in Example 1-(2), to obtain 35.5 g of dicyclohexyl-3,4-dichlorophenyltin fluoride as a white solid.
Mp: 193.degree. C. Tin content: 26.0% (theoretical: 26.4%).
EXAMPLE 31
Dicyclohexyl-paratolyltin chloride (compound 197)
Dicyclohexyl-di(paratolyl)tin (82.5 g), a pale-yellow viscous liquid, was prepared in substantial accordance with the procedure described in Example 1(1) except that paratolyl bromide (86.2 g, 0.504 mol) and dicyclohexyltin dichloride (66.9 g, 0.188 mol), rather than metatrifluoromethylphenyl bromide and dineophyltin dichloride, were employed. Gas chromatography analysis of this liquid showed 94.5% purity. Tin content was 24.7% (theoretical: 25.4%).
The above product (70 g, 0.150 mol) was then allowed to react with chlorine and the resulting mixture was worked up, as described in Example 5, to obtain 34.5 g of dicyclohexyl-paratolyltin chloride as a colorless viscous liquid. Gas chromatography analysis of this liquid showed 98.4% purity.
Refractive index: n.sup.30 =1.5705. Tin content: 28.6% (theoretical: 28.8%).
EXAMPLE 32
Dicyclohexyl-trimethylsilylmethyltin chloride (compound 232)
(1) Dicyclohexyl-phenyltin chloride
Dicyclohexyl-di(phenyl)tin (155.2 g), a white solid, was prepared in substantial accordance with the procedure described in Example 1(1) except that phenyl bromide (156.2 g, 1.008 mol) and dicyclohexyltin dichloride (133.8 g, 0.376 mol), rather than metatrifluoromethylphenyl bromide and dineophyltin dichloride, were employed. Gas chromatography analysis of this solid showed 94.9% purity.
The above product (150.8 g, 0.343 mol) was then allowed to react with chlorine and the resultant mixture was worked up as described in Example 5. Recrystallization of the product from n-hexane gave 86.0 g of dicyclohexyl-phenyltin chloride as a white solid. Gas chromatography analysis of this solid showed 98.8% purity.
Mp: 50.degree.-52.degree. C. Tin content: 30.2% (theoretical: 29.9%).
(2) Dicyclohexyl-trimethylsilylmethyltin chloride
Dicyclohexyl-phenyl-trimethylsilylmethyltin (79.4 g), a colorless viscous liquid, was prepared as described in Example 1(1). Using dicyclohexyl-phenyltin chloride (74.7 g, 0.188 mol) obtained above and trimethylsilylmethyl chloride (30.8 g, 0.251 mol) instead of dineophyltin dichloride and metatrifluoromethylphenyl bromide respectively. In this example, 6.1 g (0.251 mol) of magnesium and 110 g of tetrahydrofuran were employed. Gas chromatography analysis of this liquid showed 97.5% purity.
In the manner as taught in Example 5, the above product (48.5 g, 0.108 mol) was reacted with chlorine, and the resultant mixture was concentrated. The residue was recrystallized from n-hexane to yield 35.2 g of dineophyl-trimethylsilylmethyltin chloride as a white solid. Gas chromatography analysis of this solid showed 99.0% purity.
Mp: 74.degree. C.
EXAMPLE 33
Bis(dicyclohexyl-trimethylsilylmethyltin)oxide (compound 233)
Dicyclohexyl-trimethylsilylmethyltin chloride (25.3 g, 0.062 mol) prepared in Example 32 was allowed to react and the resultant mixture was worked up, as described in Example 2, to provide 21.2 g of bis(dicyclohexyl-trimethylsilylmethyltin)oxide as a white solid. Mp: 151.degree.-153.degree. C.
EXAMPLE 34
o-(Dicyclohexyl-trimethylsilylmethyltin) o,o-dibutylphosphate (compound 237)
Bis(dicyclohexyl-trimethylsilylmethyltin)oxide (6.8 g, 8.9 mmol), o,o-dibutylphosphate (3.7 g, 17.8 mmol) and toluene (40 g) were allowed to react as described in Example 7. Evaporation of the toluene from the mixture and recrystallization of the residue from methanol/acetonitrile gave 8.3 g of o-(dicyclohexyl-trimethylsilylmethyltin) o,o-dibutylphosphate as a white solid. Mp: 130.degree.-132.degree. C.
In substantial accordance with the procedures as taught in the above examples, a variety of organotin compounds (I) of the invention were prepared. Physicochemical properties of the compounds are listed in Table 1.
In Table 1, the following abbreviations were employed:
Me: methyl
Et: ethyl
Bu: butyl
Oct: octyl
Phe: phenyl
Ac: acetyl
Tin content in parenthesis represents theoretical amount.
TABLE 1-1__________________________________________________________________________ ##STR13## Physical propertyCom- Tin GLCpound m.p. or content purityNo. R.sup.2 R.sup.1 m X Appearance b.p. n.sup.30 (%) (%)__________________________________________________________________________1 m-CF.sub.3 Neophyl 1 F Viscous liquid 1.5555 21.1 (21.6)2 p-F n-Butyl 1 F White solid 205-210.degree. C. 34.2 (34.4)3 m-CF.sub.3 Neophyl 2 O Viscous liquid 1.5651 21.9 (22.1)4 m-CF.sub.3 Neophyl 1 Cl Colorless liquid 1.5591 21.2 99.3 (21.0)5 m-CF.sub.3 Neophyl 1 OCOMe Viscous liquid 1.5465 20.1 (20.1)6 m-CF.sub.3 Neophyl 1 SSCN(Me).sub.2 White solid 96-97.degree. C. 18.1 (18.2)7 o-CF.sub.3 Neophyl 1 Triazolyl Viscous liquid 1.5690 20.7 (19.8)8 o-CF.sub.3 Neophyl 1 F White solid 38-40.degree. C. 21.0 (21.6)9 p-F Neophyl 1 F White solid 59-62.degree. C. 23.2 (23.8)10 m-F Neophyl 1 F White solid 35-38.degree. C. 23.3 (23.8)11 o-CF.sub.3 n-Butyl 1 F White solid 105-111.degree. C. 29.2 (decomp.) (29.9)12 m-CF.sub.3 n-Butyl 1 F White solid 142.degree. C. 29.2 (decomp.) (29.9)13 p-F n-Octyl 1 F White solid 57-60.degree. C. 26.0 (25.8)14 p-F Cyclohexyl 1 F White solid 235-240.degree. C. 29.9 (decomp.) (29.7)15 m-CF.sub.3 Cyclohexyl 1 F White solid 280.degree. C. 26.8 (decomp.) (26.4)16 o-CF.sub.3 Neophyl 2 O White solid 42-44.degree. C. 21.8 (22.1)17 p-F Neophyl 2 O White solid 84-86.degree. C. 24.5 (24.3)18 m-F Neophyl 2 O White solid 37-39.degree. C. 24.6 (24.3)19 o-CF.sub.3 n-Butyl 2 O Colorless liquid 1.5031 31.3 (32.2)20 m-CF.sub.3 n-Butyl 2 O Colorless liquid 1.4939 30.8 (30.7)21 p-F n-Butyl 2 O Colorless liquid 1.5285 35.3 (35.3)22 p-F n-Octyl 2 O Colorless liquid 1.5084 26.5 (26.5)23 p-F Cyclohexyl 2 O White solid 69-72.degree. C. 30.4 (30.6)24 m-CF.sub.3 n-Butyl 1 Br Colorless liquid 170-172.degree. C./ 1.5109 25.5 96.3 7 mmHg (25.9)25 o-CF.sub.3 Neophyl 1 Cl White solid 49-50.degree. C. 21.0 97.3 (21.0)26 p-F Neophyl 1 Cl Colorless liquid 1.5824 23.0 99.3 (23.0)27 m-F Neophyl 1 Cl Colorless liquid 1.5829 23.1 97.1 (23.0)28 o-CF.sub.3 n-Butyl 1 Cl Colorless liquid 1.5005 28.1 95.0 (28.7)29 p-F n-Butyl 1 Cl Colorless liquid 160-165.degree. C./ 1.5249 32.2 96.2 4-6 mmHg (32.7)30 p-F n-Octyl 1 Cl Colorless liquid 1.5041 25.1 96.2 (25.0)31 p-F Cyclohexyl 1 Cl White solid 52-55.degree. C. 28.6 98.7 (28.6)32 m-CF.sub.3 Cyclohexyl 1 Cl Pale yellow liquid 1.5352 24.5 98.4 (25.5)33 o-CF.sub.3 Neophyl 1 OCOMe Viscous liquid 1.5535 20.0 (25.1)34 p-F Neophyl 1 OCOMe Viscous liquid 1.5669 22.5 (22.0)35 m-F Neophyl 1 OCOMe Viscous liquid 1.5675 22.4 (22.0)36 o-CF.sub.3 n-Butyl 1 OCOMe Viscous liquid 1.4851 26.5 (27.2)37 m-CF.sub.3 n-Butyl 1 OCOMe Colorless solid 75-78.degree. C. 27.3 (27.2)38 p-F n-Butyl 1 OCOMe Colorless solid 83-85.degree. C. 31.1 (30.7)39 p-F n-Octyl 1 OCOMe Colorless solid 27-30.degree. C. 24.0 (23.8)40 p-F Cyclohexyl 1 OCOMe Colorless solid 48-50.degree. C. 27.5 (27.0)41 o-CF.sub.3 Neophyl 1 SSCN(Me).sub. 2 Colorless solid 102-105.degree. C. 18.5 (18.3)42 p-F Neophyl 1 SSCN(Me).sub.2 Colorless solid 74-76.degree. C. 19.6 (20.2)43 m-F Neophyl 1 SSCN(Me).sub.2 Solid 20.3 (20.2)44 o-CF.sub.3 n-Butyl 1 SSCN(Me).sub.2 Colorless solid 28-30.degree. C. 23.9 (23.8)45 m-CF.sub.3 n-Butyl 1 SSCN(Me).sub.2 Yellow liquid 1.5611 23.8 (23.8)46 p-F n-Butyl 1 SSCN(Me).sub.2 Pale yellow liquid 1.5880 26.5 (26.5)47 p-F n-Octyl 1 SSCN(Me).sub.2 Pale yellow liquid 1.5510 21.2 (21.2)44 p-F Cyclohexyl 1 SSCN(Me).sub.2 Colorless solid 101-105.degree. C. 24.2 (23.7)49 p-F Neophyl 1 1,2,4-Triazol-1-yl Colorless solid 134-137.degree. C. 21.0 (21.6)50 m-F Neophyl 1 1,2,4-Triazol-1-yl Colorless solid 154-157.degree. C. 21.6 (21.6)51 p-F n-Butyl 1 1,2,4-Triazol-1-yl Colorless solid 68-72.degree. C. 28.7 (30.0)52 m-CF.sub.3 n-Butyl 1 1,2,4-Triazol-1-yl Viscous liquid 1.5205 26.0 (26.6)53 p-F n-Octyl 1 1,2,4-Triazol-1-yl Viscous liquid 1.5220 22.8 (23.4)54 p-F Neophyl 1 1,3-Imidazol-1-yl Colorless solid 123-127.degree. C. 21.2 (21.7)55 o-CF.sub.3 Neophyl 2 OSO.sub.2 O Viscous liquid 1.5700 21.0 (20.5)56 p-F Neophyl 2 OSO.sub.2 O Viscous liquid 1.5961 23.0 (22.5)57 o-CF.sub.3 Neophyl 2 S Viscous liquid 1.6029 20.9 (21.7)58 p-F Neophyl 2 S Viscous liquid 1.6155 23.1 (23.9)59 o-CF.sub.3 Neophyl 1 NCO Liquid 1.5787 20.5 (20.2)60 p-F Neophyl 1 NCS Liquid 1.5609 21.0 (20.7)61 o-CF.sub.3 Neophyl 1 ##STR14## Liquid 1.5279 (16.3)16.562 o-CF.sub.3 Neophyl 1 ##STR15## Liquid 1.5414 (18.8)18.663 o-CF.sub.3 Neophyl 2 ##STR16## Solid 128-131.degree. C. (17.6)17.564 o-CF.sub.3 Neophyl 1 SCH.sub.2 COOn-Bu Liquid 1.563265 o-CF.sub.3 Neophyl 1 SCH.sub.2 COOn-Oct Liquid 1.549966 o-CF.sub.3 Neophyl 1 1,3-Imidazol-1-yl Viscous liquid 1.5686 19.7 (19.9)67 o-CF.sub.3 Neophyl 1 SMe Viscous liquid 1.5804 20.9 (20.6)68 o-CF.sub.3 Neophyl 1 Phenoxy Solid 69-71.degree. C. 19.1 (19.0)69 o-CF.sub. 3 Neophyl 1 Phenylthio Solid 81-82.degree. C. 18.7 (18.6)70 o-CF.sub.3 Neophyl 1 ##STR17## Solid 63-69.degree. C.71 o-CF.sub.3 Neophyl 1 ##STR18## Viscous liquid 1.575972 3-CF.sub.3 Neophyl 1 F Solid 50-56.degree. C. 20.6 4-Cl (20.3)73 3-CF.sub.3 Neophyl 1 Cl Solid 69-71.degree. C. 20.9 99.0 4-Cl (19.8)74 3-CF.sub.3 Neophyl 1 Br Solid 72-74.degree. C. 18.3 97.0 4-Cl (18.4)75 3-CF.sub.3 Neophyl 2 O Solid 58-61.degree. C. 20.4 4-Cl (20.7)76 3-CF.sub.3 Neophyl 1 OAc Solid 60-62.degree. C. 19.2 4-Cl (19.0)77 3-CF.sub.3 Neophyl 1 SSCN(Me).sub.2 Solid 86-88.degree. C. 17.6 4-Cl (17.3)78 3-CF.sub.3 Neophyl 1 1,2,4-Triazol-1-yl Solid 159-161.degree. C. 18.7 4-Cl (18.8)79 2,4-Difluoro Neophyl 1 F Solid 60-63.degree. C. 22.6 (22.9)80 2,4-Difluoro Neophyl 1 Cl Liquid 1.5730 21.9 98.1 (22.2)81 2,4-Difluoro Neophyl 2 O Viscous liquid 1.5821 23.1 (23.4)82 2,4-Difluoro Neophyl 1 OAc Viscous liquid 1.5598 21.3 (21.3)83 2,4-Difluoro Neophyl 1 SSCN(Me).sub.2 Viscous liquid 1.6156 19.1 (19.2)84 2,4-Difluoro Neophyl 1 1,2,4-Triazol-1-yl Solid 131-134.degree. C. 20.9 (21.0)85 3,4-Difluoro Neophyl 1 F Liquid 1.5793 23.2 (22.9)86 3,4-Difluoro Neophyl 1 Cl Liquid 1.5745 22.1 96.9 (22.2)87 3,4-Difluoro Neophyl 2 O Viscous liquid 1.5820 23.3 (23.4)88 3,4-Difluoro Neophyl 1 OAc Solid 33-35.degree. C. 21.3 (21.3)89 3,4-Difluoro Neophyl 1 SSCN(Me).sub.2 Solid 92-94.degree. C. 19.5 (19.2)90 3,4-Difluoro Neophyl 1 1,2,4-Triazol-1-yl Solid 50-53.degree. C. 20.8 (21.0)91 2,4,5-Trifluoro Neophyl 1 F Liquid 1.5644 22.0 (22.2)92 2,4,5-Trifluoro Neophyl 1 Cl Solid 65-67.degree. C. 21.7 99.9 (21.5)93 2,4,5-Trifluoro Neophyl 2 O Viscous liquid 1.5729 22.4 (22.6)94 2,4,5-Trifluoro Neophyl 1 OAc Solid 59-61.degree. C. 20.8 (20.6)95 2,4,5-Trifluoro Neophyl 1 SSCN(Me).sub.2 Solid 81-83.degree. C. 18.7 (18.7)96 2,4,5-Trifluoro Neophyl 1 1,2,4-Triazol-1-yl Solid 125-130.degree. C. 20.2 (20.3)97 o-Cl Neophyl 1 F Solid 72-74.degree. 23.2 (23.0)98 o-Cl Neophyl 1 Cl Viscous liquid 1.5981 22.2 (22.3)99 o-Cl Neophyl 2 O Viscous liquid 1.6070 23.4 (23.5)100 o-Cl Neophyl 1 OAc Viscous liquid 1.5800 21.2 (21.4)101 o-Cl Neophyl 1 SSCN(Me).sub.2 Solid 100-103.degree. C. 19.1 (18.7)102 m-Cl Neophyl 1 F Solid 58-62.degree. C. 23.1 (23.0)103 m-Cl Neophyl 1 Cl Solid 41-43.degree. C. 22.3 96.3 (22.3)104 m-Cl Neophyl 2 O Viscous liquid 1.6048 23.6 (23.5)105 m-Cl Neophyl 1 OAc Viscous liquid 1.5801 21.5 (21.4)106 m-Cl Neophyl 1 SSCN(Me).sub.2 Viscous liquid 1.6326 19.0 (19.2)107 m-Cl Neophyl 1 1,2,4-Triazol-1-yl Solid 165-169.degree. C. 21.1 (21.0)108 p-Cl Neophyl 1 F Solid 104-105.degree. C. 23.0 (23.0)109 p-Cl Neophyl 1 Cl Solid 70-72.degree. C. 22.6 99.0 (22.3)110 p-Cl Neophyl 2 O Viscous liquid 1.6045 23.4 (23.5)111 p-Cl Neophyl 1 OAc Viscous liquid 1.5808 21.5 (21.4)112 p-Cl Neophyl 1 SSCN(Me).sub.2 Solid 89-92.degree. C. 19.3 (19.2)113 p-Cl Neophyl 1 1,2,4-Triazol-1-yl Solid 70-73.degree. C. 20.8 (21.0)114 p-Me Neophyl 1 F Viscous liquid 1.5925 24.2 (24.0)115 p-Me Neophyl 1 Cl Solid 34.5-35.5.degree. C. 23.5 96.7 (23.2)116 p-Me Neophyl 2 O Viscous liquid 1.6013 24.4 (24.5)117 p-Me Neophyl 1 OAc Viscous liquid 1:5780 22.4 (22.2)118 p-Me Neophyl 1 SSCN(Me).sub.2 Solid 126-128.degree. C. 20.1 (19.9)119 p-Me Neophyl 1 1,2,4-Triazol-1-yl Solid 103-108.degree. C. 21.5 (21.8)120 m-Me Neophyl 1 F Solid 58-59.degree. C. 24.0 (24.0)121 m-Me Neophyl 1 Cl Viscous liquid 1.5893 23.5 98.2 (23.2)122 m-Me Neophyl 2 O Viscous liquid 1.5969 24.8 (24.5)123 m-Me Neophyl 1 OAc Viscous liquid 1.5748 22.5 (22.2)124 m-Me Neophyl 1 SSCN(Me).sub.2 Solid 51-54.degree. C. 20.1 (19.9)125 m-Me Neophyl 1 1,2,4-Triazol-1-yl Solid 130-135.degree. C. 21.5 (21.8)126 p-Me Neophyl 1 F Solid 95-98.degree. C. 24.1 (24.0)127 p-Me Neophyl 1 Cl Solid 51-53.degree. C. 23.3 99.3 (23.2)128 p-Me Neophyl 2 O Viscous liquid 1.5982 24.7 (24.5)129 p-Me Neophyl 1 OAc Viscous liquid 1.5755 22.4 (22.2)130 p-Me Neophyl 1 SSCN(Me).sub.2 Solid 92-94.degree. C. 20.2 (19.9)131 p-Me Neophyl 1 1,2,4-Triazol-1-yl Solid 146-148.degree. C. 21.5 (21.8)132 o-OMe Neophyl 1 F Viscous liquid 1.5885 23.0 (23.2)133 o-OMe Neophyl 1 Cl Solid 69-72.degree. C. 22.7 99.5 (22.5)134 o-OMe Neophyl 2 O Viscous liquid 1.6013 24.1 (23.7)135 o-OMe Neophyl 1 OAc Viscous liquid 93-96.degree. 1.5756 21.8 (21.5)136 o-OMe Neophyl 1 SSCN(Me).sub.2 Solid 93-96.degree. C. 19.6 (19.4)137 o-OMe Neophyl 1 1,2,4-Triazol-1-yl Solid 107-113.degree. C. 21.3 (21.2)138 p-OMe Neophyl 1 F Viscous liquid 1.5943 23.4 (23.2)139 p-OMe Neophyl 1 Cl Viscous liquid 1.5918 22.7 96.2 (22.5)140 p-OMe Neophyl 2 O Viscous liquid 1.6004 23.5 (23.7)141 p-OMe Neophyl 1 OAc Viscous liquid 1.5777 21.9 (21.5)142 p-OMe Neophyl 1 SSCN(Me).sub.2 Viscous liquid 1.6281 19.0 (19.4)143 p-OMe Neophyl 1 1,2,4-Triazol-1-yl Solid 134-140.degree. C. 21.4 (21.2)144 H Neophyl 1 F Solid 37-40.degree. C. 24.9 (24.7)145 H Neophyl 1 Cl Viscous liquid 1.5937 24.3 97.1 (23.9)146 H Neophyl 2 O Viscous liquid 1.6021 24.8 (25.2)147 H Neophyl 1 OAc Viscous liquid 1.5769 23.1 (22.8)148 H Neophyl 1 SSCN(Me).sub.2 Viscous liquid 1.6343 20.6 (20.4)149 H Neophyl 1 1,2,4-Triazol-1-yl Solid 130-135.degree. C. 22.5 (22.4)150 o-CF.sub.3 Cyclohexyl 1 F Solid 98-102.degree. C. 25.9 (26.4)151 o-CF.sub.3 Cyclohexyl 1 Cl Solid 51-52.degree. C. 25.4 98.6 (25.5)152 o-CF.sub.3 Cyclohexyl 2 O Solid 125-128.degree. C. 26.2 (27.1)153 o-CF.sub.3 Cyclohexyl 1 OAc Liquid 1.5250 23.8 (24.3)154 o-CF.sub.3 Cyclohexyl 1 ##STR19## Liquid 1.5111 21.8 (22.3)155 o-CF.sub.3 Cyclohexyl 1 SCH.sub.2 COOn-Bu Liquid 1.5400156 o-CF.sub.3 Cyclohexyl 1 SCH.sub.2 COOn-Oct Liquid 1.5312157 o-CF.sub.3 Cyclohexyl 1 SSCN(Me).sub.2 Solid 154-156.degree. C. 21.7 (21.7)158 o-CF.sub.3 Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 176-180.degree. C. 23.5 (23.8)159 m-CF.sub.3 Cyclohexyl 2 O Solid 84-86.degree. C. 26.9 (27.1)160 m-CF.sub.3 Cyclohexyl 1 OAc Solid 59-61.degree. C. 25.0 (24.3)161 m-CF.sub.3 Cyclohexyl 1 SSCN(Me).sub.2 Solid 124-126.degree. C. 21.6 (21.6)162 m-CF.sub.3 Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 191-184.degree. C. 22.9 (23.8)163 p-CF.sub.3 Cyclohexyl 1 F Solid 240.degree. C. 26.4 99.0 (decomp.) (26.4)164 p-CF.sub.3 Cyclohexyl 1 Cl Solid 74-75.degree. C. 25.8 (25.5)165 p-CF.sub.3 Cyclohexyl 2 O Solid 86-89.degree. C. 26.8 (27.1)166 p-CF.sub.3 Cyclohexyl 1 OAc Solid 68-71.degree. C. 23.9 (24.3)167 p-CF.sub.3 Cyclohexyl 1 SCH.sub.2 COOn-Bu Liquid 1.5337 20.4 (20.6)168 p-CF.sub.3 Cyclohexyl 1 SSCN(Me).sub.2 Solid 85-87.degree. C. 21.7 (21.6)169 p-CF.sub.3 Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 215-225.degree. C. 23.4 (23.8)170 m-F Cyclohexyl 1 F Solid 225.degree. C. 29.6 (decomp.) (29.7)171 m-F Cyclohexyl 1 Cl Solid 52-53.degree. C. 28.7 (28.6)172 m-F Cyclohexyl 2 O Solid 44-46.degree. C. 31.0 (30.6)173 m-F Cyclohexyl 1 OAc Solid 52-54.degree. C. 27.1 (27.0)174 m-F Cyclohexyl 1 SCH.sub.2 COOn-Bu Liquid 1.5555 22.9 (22.5)175 m-F Cyclohexyl 1 SSCN(Me).sub.2 Solid 110-112.degree. C. 24.0 (23.7)176 m-F Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 208.degree. C. 26.7 (decomp.) (26.5)177 o-CF.sub.3 Neophyl 1 SSCN(Et).sub.2 Liquid 1.5931 17.2 (17.5)178 o-CF.sub.3 Neophyl 1 o-t-Butylphenoxy Solid 75-76.degree. C. 17.5 (17.5)179 o-CF.sub.3 Neophyl 1 2,6-Diisopropylphenoxy Liquid 1.5619 16.7 (16.8)180 o-CF.sub.3 Cyclohexyl 1 SSCN(Et).sub.2 Solid 105-107.degree. C. 20.6 (20.5)181 o-CF.sub.3 Cyclohexyl 1 o-t-Butylphenoxy Liquid 1.5519 19.9 (20.5)182 o-CF.sub.3 Cyclohexyl 1 2,6-Diisopropylphenoxy Solid 53-57.degree. C. 19.3 (19.5)183 p-Cl Cyclohexyl 1 F Solid 256-258.degree. C. 28.2 (28.6)184 p-Cl Cyclohexyl 1 Cl Solid 49-50.degree. C. 27.1 (27.5)185 p-Cl Cyclohexyl 2 O Solid 111-113.degree. C. 29.4 (29.3)186 p-Cl Cyclohexyl 1 OAc Solid 97-99.degree. C. 26.4 (26.1)187 p-Cl Cyclohexyl 1 SCH.sub.2 COOn-Bu Liquid 1.5645 21.9 (21.8)188 p-Cl Cyclohexyl 1 SSCN(Me).sub.2 Solid 70-73.degree. C. 22.5 (23.0)189 p-Cl Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 217-223.degree. C. 25.5 (25.5)190 3,4-Dichloro Cyclohexyl 1 F Solid 193.degree. C. 26.0 (decomp.) (26.4)191 3,4-Dichloro Cyclohexyl 1 Cl Liquid 1.5903 25.1 97.2 (25.4)192 3,4-Dichloro Cyclohexyl 2 O Solid 129-130.degree. C. 27.4 (27.0)193 3,4-Dichloro Cyclohexyl 1 OAc Solid 99-101.degree. C. 24.4 (24.2)194 3,4-Dichloro Cyclohexyl 1 SSCN(Me).sub.2 Solid 138-140.degree. C. 21.5 (21.5)195 3,4-Dichloro Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 207-213.degree. C. 24.0 (23.8)196 p-Me Cyclohexyl 1 F Solid 245-247.degree. C. 29.7 (30.0)197 p-Me Cyclohexyl 1 Cl Liquid 1.5705 28.6 (28.8)198 p-Me Cyclohexyl 2 O Solid 71-73.degree. C. 31.0 (30.9)199 p-Me Cyclohexyl 1 OAc Solid 83-85.degree. C. 27.6 (27.3)200 p-Me Cyclohexyl 1 SCH.sub.2 COOn-Bu Liquid 1.5605 22.9 (22.7)201 p-Me Cyclohexyl 1 SSCN(Me).sub.2 Solid 92-94.degree. C. 23.8 (23.9)202 p-Me Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 205-210.degree. C. 26.5 (26.7)203 p-Methoxy Cyclohexyl 1 F Solid 234-236.degree. C. 29.4 (28.9)204 p-Methoxy Cyclohexyl 1 Cl Liquid 1.5749 27.6 96.9 (27.8)205 p-Methoxy Cyclohexyl 2 O Solid 65-69.degree. C. 29.6 (29.7)206 p-Methoxy Cyclohexyl 1 OAc Solid 82-84.degree. C. 26.7 (26.3)207 p-Methoxy Cyclohexyl 1 SCH.sub.2 COOn-Bu Liquid 1.5630 22.5 (22.0)208 p-Methoxy Cyclohexyl 1 SSCN(Me).sub.2 Solid 78-80.degree. C. 23.1 (23.2)209 p-Methoxy Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 202-207.degree. C. 25.4 (25.8)__________________________________________________________________________
TABLE 1-2__________________________________________________________________________ ##STR20## Physical property Tin GLCCompound m.p. or content purityNo. R* R.sup.1 m X Appearance b.p. n.sup.30 (%) (%)__________________________________________________________________________210 2-Thienyl Neophyl 1 Cl Viscous liquid 1.5987 23.5 (23.6)211 2-Thienyl Neophyl 2 O Solid 90-99.degree. C. 24.7 (24.9)212 2-Thienyl Neophyl 1 OAc Viscous liquid 1.5798 22.5 (22.6)213 2-Thienyl Neophyl 1 SSCN(Me).sub.2 Solid 77-79.degree. C. 20.4 (20.2)214 2-Thienyl Neophyl 1 1,2,4-Triazol-1-yl Solid 147-157.degree. C. 21.8 (22.1)215 3-Thienyl Neophyl 1 F Solid 85-90.degree. C. 24.7 (24.4)216 3-Thienyl Neophyl 1 Cl Viscous liquid 1.5988 23.9 97.8 (23.6)217 3-Thienyl Neophyl 2 O Solid 78-81.degree. C. 25.0 (24.9)218 3-Thienyl Neophyl 1 OAc Solid 46-48.degree. C. 22.7 (22.5)219 3-Thienyl Neophyl 1 SSCN(Me).sub.2 Solid 87-89.degree. C. 20.6 (20.2)220 3-Thienyl Neophyl 1 1,2,4-Triazol-1-yl Solid 140-144.degree. C. 21.9 (22.1)221 Trimethylsilylmethyl Neophyl 1 F Liquid 1.5412222 Trimethylsilylmethyl Neophyl 1 Cl Solid 42.5-43.5.degree. C. 99.0223 Trimethylsilymethyl Neophyl 2 O Solid 90.5-91.0.degree. C.224 Trimethylsilylmethyl Neophyl 1 OAc Liquid 1.5372225 Trimethylsilylmethyl Neophyl 1 SSCN(Me).sub.2 Solid 62-63.degree. C.226 Trimethylsilylmethyl Neophyl 1 1,2,4-Triazol-1-yl Solid 78-85.degree. C.227 Dimethylphenylsilylmethyl Neophyl 1 Cl Solid 30.degree. C. 99.0228 Dimethylphenylsilylmethyl Neophyl 2 O Solid 87-89.degree. C.229 Dimethylphenylsilylmethyl Neophyl 1 OAc Liquid 1.5617230 Dimethylphenylsilylmethyl Neophyl 1 SSCN(Me).sub.2 Liquid 1.6141231 Trimethylsilylmethyl Cyclohexyl 1 F Solid 167-170.degree. C.232 Trimethylsilylmethyl Cyclohexyl 1 Cl Solid 74.degree. C. 99.0233 Trimethylsilylmethyl Cyclohexyl 2 O Solid 151-153.degree. C.234 Trimethylsilylmethyl Cyclohexyl 1 OAc Solid 52-53.degree. C.235 Trimethylsilylmethyl Cyclohexyl 1 SSCN(Me).sub.2 Solid 101-102.degree. C.236 Trimethylsilylmethyl Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 197-201.degree. C. (decomp.)237 Trimethylsilylmethyl Cyclohexyl 1 ##STR21## Solid 130-132.degree. C.238 Neopentyl Neophyl 1 Cl Solid 65-66.degree. C. 23.6 99.9 (24.1)239 Neopentyl Neophyl 2 O Solid 100-101.degree. C. 25.7 (25.6)240 Neopentyl Cyclohexyl 1 Cl Solid 106-107.degree. C. 29.5 (30.3)241 Neopentyl Cyclohexyl 2 O Solid 202-203.degree. C. 32.5 (32.6)242 Dimethylphenylsilylmethyl Neophyl 1 F Solid 47-48.degree. C.243 Dimethylphenylsilylmethyl Neophyl 1 1,2,4-Triazol-1-yl Solid 66-71.degree. C.244 Dimethylphenylsilylmethyl Neophyl 1 ##STR22## Liquid 1.5484245 Dimethylphenylsilylmethyl Cyclohexyl 1 F Solid 107-110.degree. C.246 Dimethylphenylsilylmethyl Cyclohexyl 1 Cl Liquid 1.5593247 Dimethylphenylsilylmethyl Cyclohexyl 2 O Solid 48-51.degree. C.248 Dimethylphenylsilylmethyl Cyclohexyl 1 OAc Liquid 1.5421249 Dimethylphenylsilylmethyl Cyclohexyl 1 SSCN(Me).sub.2 Liquid 1.6054250 Dimethylphenylsilylmethyl Cyclohexyl 1 1,2,4-Triazol-1-yl Solid 118-124.degree. C.251 Dimethylphenylsilylmethyl Cyclohexyl 1 ##STR23## Solid 125-126.degree. C.__________________________________________________________________________
Various compounds to be employed in accordance with the present invention were formulated as wettable powders, emulsifiable concentrates, fine dusts, etc., as shown below.
______________________________________Ingredient Part by weight______________________________________Formulation 1 Wettable powderCompound No. 28 50.0Clay 40.5White carbon 5.0Polyoxyalkylenealkyl- 3.0allylethersulfateAlkylbenzensulfonate 1.5Formulation 2 Emulsifiable concentrateCompound No. 25 25.0Alkylallylsulfonate 3.0Polyoxyalkylenealkylallyl 10.0etherXylene 42.0Dimethylformamide 20.0______________________________________
Compound No. 25, alkylallylsulfonate and polyoxyalkylenealkylallyl ether are uniformly dissolved in xylene and dimethylformamide to obtain emulsifiable concentrate. The preparation is diluted with water when use.
______________________________________Formulation 3 Fine dust______________________________________Compound No. 33 15.0White carbon 20.0Isopropylazidophosphate 0.3Fine clay 64.7______________________________________
The above ingredients are mixed and ground. The mixture is finely ground by Jetmizer grinder to obtain fine dust. The preparation is used as it is.
______________________________________Formulation 4 Dust______________________________________Compound No. 49 5.0Clay 91.7White carbon 3.0Tall oil 0.3______________________________________
The above ingredients are mixed and ground to obtain dust preparation. The dust is used as it is.
Experiment 1
Sample
Compounds of the invention to be tested are dissolved in a minimum of DMF. Distilled water containing Tween 20 at the concentration of 100 ppm is thereto added to prepare a series of samples of the desired concentrations.
Test Procedure
A. Suppression of Spodoptera litura (common cutworm) larvae
Cabbage leaves (5.times.5 cm) were immersed in the sample solution as prepared above and air dried. Two leaves were placed in a petri dish (9 cm diameter) and 10 third-instar larvae of Spodoptera litura were placed in the dish. The dish was held at 25.degree. C. and the mortality of the larvae was measured after 48 hours.
C. Suppression of Plutella xylostella (diamond backmoth) larvae
Cabbage leaf (7.times.7 cm) was immersed in the sample solution and air dried. The leaf was placed in a petri dish (9 cm diameter) and 10 third-instar larvae of Plutella xylostella were placed in the dish. The dish was held at 25.degree. C. and the mortality of the larvae was measured after 48 hours.
D. Suppression of Adoxophyes sp. larvae
Whole tea leaves were immersed in the sample solution and air dried. Three leaves were placed in a polyethylene petri dish (6 cm diameter, 4 cm depth) and 10 forth-instar larvae of Adoxophyes sp. were placed in the dish. The dish was held at 25.degree. C. and the mortality of the larvae was measured after 48 hours.
E. Suppression of Nephotettix cincticeps (green rice leaf hopper) (sensitive)
Six or seven rice seedlings of 1.5 to 2 plant age in leaf number were bundled and the roots were wrapped in sponge.The seedlings were placed in a polyethylene cup (diameter 6 cm, depth 4 cm) and the cup is placed in a rotary application tower, whereby the leaves and sheaths of the seedlings were sprayed with 2 ml of the sample solution and air dried. The treated seedlings were covered with a transparent plastic cylinder and ten female larvae were placed in the cylinder. The atmosphere in the cylinder was ketp at 25.degree. C., and the mortality after 48 hours was measured.
I. and J. Suppression of Myzus persicae (green peach aphid) larvae (I: sensitive, J: resistant)
A polyethylene cup (diameter 6 cm, depth 4 cm) was filled with 0.3% agar gel and a piece of Chinese cabbage leaf (3.times.3 cm) was placed on the gel. An apterous adult of Myzus persicae was placed on the cabbage and allowed to egg-deposit while keeping the surrounding atmosphere at 25.degree. C. for 24 hours. After removing the adult, 2 ml of the sample was sprayed on the leaf under a rotary application tower. The test system was kept at 25.degree. C. for 48 hours and the mortality of born larvae was measured.
M. Suppression of Tetranychus cinnabrinus (carmine spider mite)
A polyethylene cup (diameter 6 cm, depth 4 cm) was filled with 0.3% agar gel and a piece of bush bean leaf (diameter 2 cm) was placed on the gel. About twelve adults of Tetranychus cinnabrinus were placed on the leaf. After 24 hours at 25.degree. C., dead and feeble adults were removed and 2 ml of the sample solution was sprayed on the leaf and audlts under a rotary application tower. Following such treatment the test system was kept at 25.degree. C. and the mortality was measured after 48 hours.
O. Suppression of Tetranychus urticae (Two-spotted spider mite)
The same test procedure as above was repeated on Tetranychus urticae.
X. Suppression of Tetranychus cinnabrinus larvae
A polyethylene cup (diameter 6 cm, depth 4 cm) was filled with 0.3% agar gel and a piece of bush bean leaf (diameter 2 cm) was placed on the gel. Seven adults of Tetranychus cinnabrinus were placed on the leaf and allowed to egg-deposit while keeping the surrounding atmosphere at 25.degree. C. for 24 hours. After removing the adult, 2 ml of the sample was sprayed on the leaf under a rotary application tower. The test system was kept at 25.degree. C. for 7 days and the mortality of born larvae was measured.
Y. Suppression of Tetranychus urticae larvae
The same test procedure as above was repeated on Tetranychus urticae larvae.
N. Suppression of Tetranychus cinnabrinus eggs
P. Suppression of Tetranychus urticae eggs
The test procedure as described in X and Y were repeated on Tetranychus cinnabrinus and urticae eggs. The test system was kept at 25.degree. C. for 7 days and the mortality of eggs was measured by counting the number of eggs which did not hatch.
T. Suppression of Henosepilachna vigintioctopunctata (twenty-eight-spotted beetle) adults
Japanese eggplant leaf (6.times.6 cm) was immersed in the sample solution and air dired. The leaf was placed in a petri dish (9 cm diameter) and 5 adults of Henosepilachna vigintioctopunctata were placed in the dish. The dish was held at 25.degree. C. and the mortality was measured after 48 hours.
R. Suppression of Periplaneta americana (American cockroach) larvae
A filter paper soaked with the sample solution was placed in a petri dish (diameter 9 cm). Five Periplaneta americana larvae within 7 days after hatching were placed in the dish hold at 25.degree. C. and the mortality after 48 hours was measured.
W. Suppression of Callosobruchus chinensis (adzuki bean weevil)
Ten Callosobruchus chinensis adults within 24 hours after hatching were placed in a screw cylinder (diameter 1.8 cm, height 5 cm) with stainless nets at the up-and-down openings. The cylinder was submerged in the sample solution, and the adults exposed to the solution were air dried. The mortality was measured after 48 hours at 25.degree. C.
K. Suppression of Panonychus citri (citrus red mite)
The same test procedure as M and O was repeated on Panonychus citri except that lemon leaf, rather than bush bean leaf, was employed.
Q. Suppression of Tetranychus kanzawai (kanzawa spider mite) (resistant adults)
The same test procedure as M and O was repreated on resistant adults of Teranychus kanzawai.
Test Results
Table 2 below shows the mortality (%) of various pests exposed to the indicated compounds (I) at several concentrations, wherein the following codes are employed for pests.
A: Spodoptera litura (larvae)
C: Plutella xylostella (larvae)
D: Adoxophyes sp. (larvae)
E: Nephotettix cincticeps (sensitive adults)
I: Myzus persicae (sensitive larvae)
J: Myzus persicae (resistant larvae)
K: Panonychus citri (adults)
L: Panonychus citri (eggs)
M: Tetranychus cinnabrinus (adults)
N: Tetranychus cinnabrinus (eggs)
O: Tetranychus urticae (adults)
P: Tetranychus urticae (eggs)
Q: Tetranychus kanzawai (resistant adults)
R: Periplaneta americana (larvae)
T: Henosepilachna vigintioctopunctata (adults)
W: Callosobruchus chinensis (adults)
X: Tetranychus cinnabrinus (eggs-larvae)
Y: Tetranychus urticae (eggs-larvae)
Table 2 also lists the test results on commercially available Osadan.RTM. and Plictran.RTM. employed as a control.
Resistant adults of Tetranychus kanzawai used in Test Q were those which acquired resistance against Osadan.RTM. and Plictran.RTM. and were gathered at Yaguchihara and Okadahara, Shizuoka, Japan. Test results on the adults from Yaguchihara and Okadahara are shown on the left and right, respectively, of column "Q" in Table 2.
TABLE 2__________________________________________________________________________ Con- cen-Com- tra-pound tionNo. (ppm) A C D E G H I J K L M N O P Q R T W X Y__________________________________________________________________________Osadan 1000 100 93 47 52 100 250 100 95 37 36 100 100 63 90 27 16 80Plic- 1000 100 100 51 69 100tran 250 100 100 100 23 36 100 100 63 100 100 93 10 24 40 50 15 88 1 31 1000 100 70 97 100 250 100 90 90 63 97 100 16 772 1000 100 100 250 100 100 100 63 70 100 973 1000 100 100 250 100 100 63 87 100 70 16 794 1000 100 100 70 100 250 100 97 70 100 63 91 100 80 16 765 1000 100 100 250 100 71 76 100 63 97 100 80 16 89 806 1000 100 100 250 100 100 63 90 100 80 16 86 727 1000 100 100 81 96 100 250 92 100 100 80 89 90 63 95 100 74 16 788 1000 100 100 95 100 100 250 95 100 100 83 79 93 100 63 94 1009 1000 100 100 100 250 100 70 100 79 85 96 100 100 63 97 100 100 84 95 90 16 74 8810 1000 100 96 100 250 100 95 96 100 63 84 100 70 16 9311 1000 100 72 100 100 90 80 100 100 100 250 100 95 100 92 100 75 100 100 100 63 70 87 81 100 9512 1000 100 93 100 100 250 90 90 95 80 6316 1000 100 100 87 100 100 250 86 100 100 88 76 93 100 63 100 100 79 16 74 9217 1000 100 97 100 250 100 80 86 81 89 100 100 63 97 100 100 100 98 16 73 75 8518 1000 100 100 250 100 87 78 92 100 63 94 100 70 70 100 16 91 8019 1000 100 100 100 100 95 80 100 100 100 250 80 80 84 100 100 92 100 100 100 63 81 86 100 98 16 9120 1000 70 100 100 100 100 250 97 97 70 80 63 8023 1000 100 94 98 250 90 100 6325 1000 100 100 85 100 100 100 250 94 100 100 86 89 100 63 97 97 8021 1000 100 100 100 83 80 100 250 80 100 100 93 100 100 63 100 100 1624 1000 75 100 100 100 80 100 250 90 100 100 100 70 100 63 73 92 9726 1000 100 100 100 250 100 100 78 83 93 100 100 63 97 91 97 100 95 16 85 7027 1000 100 100 100 250 100 88 97 100 63 100 95 16 82 7028 1000 100 100 96 100 100 100 100 250 100 100 100 100 71 100 100 63 95 100 10029 1000 100 100 100 85 100 100 250 75 100 100 100 63 77 97 10030 1000 100 250 6331 1000 100 93 95 250 95 85 63 1632 1000 100 100 100 100 80 250 80 80 83 100 9433 1000 100 100 100 100 250 93 100 100 70 86 92 100 63 92 100 16 72 7734 1000 100 100 100 250 100 84 100 83 96 100 100 63 97 100 100 79 80 98 16 78 79 8035 1000 100 100 250 100 74 100 63 94 100 90 16 9336 1000 100 84 100 100 98 100 100 100 100 250 70 75 100 100 85 100 100 100 63 74 100 10037 1000 85 100 100 100 250 100 100 100 74 100 75 100 100 63 93 8838 1000 100 100 100 95 250 95 75 100 100 100 100 100 63 100 100 10039 1000 84 92 100 250 10040 1000 100 100 100 91 100 100 250 87 100 9041 1000 100 100 73 85 100 250 100 73 90 63 97 9242 1000 100 72 100 100 250 100 84 100 96 100 100 63 97 100 100 71 70 98 16 91 84 7043 1000 100 100 250 100 92 89 100 63 90 97 71 80 16 8444 1000 100 100 100 100 250 70 100 90 100 92 100 100 100 63 80 9445 1000 100 100 100 100 250 80 84 100 100 85 100 63 93 7046 1000 100 100 100 82 100 100 250 100 100 100 100 80 100 63 100 69 97 10047 1000 85 100 90 250 100 9348 1000 100 100 100 250 85 88 100 100 63 90 71 9549 1000 100 100 250 100 84 100 100 100 63 91 94 100 70 7050 1000 100 250 100 82 95 63 82 97 16 8251 1000 100 100 100 75 100 100 250 85 75 100 100 100 100 63 70 100 9752 1000 100 100 100 100 250 80 80 75 100 100 100 100 63 94 8954 1000 100 250 100 100 63 97 9259 1000 250 100 100 63 10060 1000 250 75 100 100 63 10061 1000 250 100 100 63 9762 1000 250 89 100 6363 1000 250 97 100 63 10064 1000 250 63 100 90 16 92 8065 1000 250 63 100 7066 1000 250 72 100 90 63 10067 1000 250 83 9068 1000 250 90 100 100 63 100 16 7169 1000 250 100 100 63 9470 1000 250 100 100 63 8171 1000 250 100 100 63 9772 1000 250 100 100 63 8473 1000 250 100 100 63 8274 1000 250 100 100 63 8875 1000 250 100 100 63 9376 1000 250 100 100 63 9477 1000 250 100 10078 1000 250 100 100 63 7979 1000 250 100 100 100 98 63 79 97 9580 1000 250 100 100 100 98 63 83 70 89 7081 1000 250 100 100 100 100 63 87 80 10082 1000 250 100 100 100 100 63 90 92 8083 1000 250 96 100 100 100 63 93 8084 1000 250 100 100 95 100 63 9685 1000 250 90 100 63 100 16 9086 1000 250 100 100 100 100 63 84 70 84 7087 1000 250 97 94 95 100 63 73 76 7088 1000 250 100 100 100 100 63 90 9089 1000 250 100 93 100 100 63 77 95 16 8090 1000 250 94 100 100 100 63 80 8091 1000 250 97 98 63 7492 1000 250 83 100 82 97 80 63 84 93 16 7493 1000 250 100 100 63 9794 1000 250 100 100 63 9595 1000 250 100 100 63 9196 1000 250 100 100 63 10097 1000 250 74 100 100 63 100 16 7298 1000 250 94 100 78 100 63 9799 1000 250 100 100 63 100100 1000 250 100 100 63 95101 1000 250 100 70 63 94102 1000 250 100 100 63 94103 1000 250 100 100 63 93104 1000 250 100 100 63 100105 1000 250 100 100 63 97106 1000 250 72 100 63 89107 1000 86 250 63 93 90108 1000 250 100 100 63 96109 1000 250 100 100 63 100110 1000 250 100 100 63 100111 1000 250 100 63 92112 1000 250 100 100 63 91113 1000 250 100 100 63 90114 1000 250 63 94 90 16 80115 1000 250 63 98 80 16 79116 1000 250 63 92 98117 1000 250 63 90118 1000 250 63 93 75 16 75119 1000 250 63 100 85 16 88120 1000 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100 63 100 16 84225 1000 250 83 100 63 100 16 93226 1000 250 86 79 100 63 100 16 97227 1000 250 100 100 63 100 16 76228 1000 250 100 100 63 92229 1000 250 100 100 63 93230 1000 250 100 63 100231 1000 250 100 100 100 63 100 16 93232 1000 250 100 100 100 63 100 16 96233 1000 250 100 98 100 63 100 16 96234 1000 250 100 100 63 100 16 96235 1000 250 100 92 100 63 100 16 96236 1000 250 90 100 100 63 100 91 16 86237 1000 250 90 100 100 63 100 16 90__________________________________________________________________________

Number	Name	Date
3448131	Chan et al.	Jun 1969
3471539	Suzuki et al.	Oct 1969
3475472	Suzuki et al.	Oct 1969
3634479	Ridenour et al.	Jan 1972
3657451	Horne	Apr 1972
3677738	Minieri	Jul 1972
3789057	Reifenberg et al.	Jan 1974
3892863	Gitlitz et al.	Jul 1975
3906103	Kushlefsky et al.	Sep 1975
3923998	Gitlitz	Dec 1975
3969386	Ballard et al.	Jul 1976
4010276	Gitlitz	Mar 1977
4058545	Gitlitz	Nov 1977
4324798	Gitlitz et al.	Apr 1982
4343815	Gitlitz	Aug 1982

Organotin compounds and pesticides containing them

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