DE2737032A1 - TRIORGANO TIN COMPOUNDS - Google Patents

Description

To you'

TUE! '- ^:. -iV- '
Π! Ί. '.: ·. ■ ■. ■

^{ϊ; ι}

8000 MUNICH 5

Case 1183

M&T CHEMICAIS INC.
Greenwich, Conn. / V.St. A.

Triorgano tin compounds

The invention relates to compositions to control fungi and pest insects, for example, mites, using a special class of organotin compounds check. The organisms against which the inventive Compounds that are effective are responsible for a significant portion of the annual damage to agricultural crops responsible. Although many trialkyl derivatives, especially tri-n-butyltin and tri-n-amyltin derivatives are effective control these organisms, but these compounds are not sufficiently selective over crops in which the fungi or insects are to be controlled, so that plants to which the organotin compounds are applied are caused to die off know.

The object of the invention is therefore to provide a new class of triorganotin compounds available that both Effectively control fungi as well as insects on living plants without significantly damaging the plants. Many Triorganotin compounds are active against either fungi or insects, but they are not active against either class of these organisms active, it has now surprisingly been found that triorganotin compounds beetimate in which the Hydrocarbon groups bonded to the tin contain a cyclopentyl structure, fulfill this task.

The invention therefore relates to new tricyclopentyl and tricyclopentylakyltin compounds of the general formula

SnX and

_J 3

I. > - -Sn lY > n- • - 2 - (CH ₂

where B stands for hydrogen or alkyl with 1 to 3 carbon atoms, η has the Vert O, 1 or 2, Σ for fluorine, nitrate, Cyanate, thiocyanate, carbamate, thiocarbamate, nitrate

-0-C

NH ₂ ,

Zip)

Alkoxy (-0R),

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Iithiocarbamovi

orRJ dialkyldithiophosphate »

Mercaptide (-SR)

where R ^{1 is} alkyl having 1 to 12 carbon atoms or

Phenyl

, where Z is hydrogen, Halo-

gen, C ₁ _, - alkyl, C ₁ alkoxy or nitro has (-NO _2), R 'represents alkyl having 1 to 12 carbon atoms, and Y is Sauer-0 0

Il It

substance, -OC (CH ₂ ) CO-, where m is an integer from 2 to 10,

-OC- (O

CO-

Sulfur, sulfate or carbonate.

These compounds are particularly effective as control agents for fungi and insects. However, they do not show the high phytotoxicity, those characteristic of tri-n-alkyltin compounds is.

The hydrocarbon groups of the triorganotin compounds according to the invention contain a cyclopentyl group that is either bonded directly to the tin atom, or from the tin atom through one or more methylene groups is separated. The cyclopentyl group can be substituted by an alkyl group having 1 to 3 carbon atoms to have.

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Tricyclopentyltin and tricyclopentylalkyltin halides, in which the halogen is chlorine, bromine or iodine, can in the Way to be produced that one'at least three KoI of the corresponding Cyclopentyl or cyclopentylakyl magnesium halide, CypMgZ or Cyp (CHp) Z, where Cyp is a cyclo-

pentyl ring, per mole of an alkyltin trihalide R ^ SnZi, where R * is lower alkyl, preferably having 1 to 4 carbon atoms stands, implements. The resulting tetraorganotin compound Cyp, SnR * is mixed with an equimolar amount of tin IV halide SnZ? implemented. During the reaction it never will drig-alkyl group R present in the tetraorganotin compound is replaced by a halogen atom of the tin IV halide. The reactions that take place in the formation of the inventive triorganotin compounds can be performed by the following two equations are presented, where Z, Z and Z independently selected from the group consisting of chlorine, bromine and iodine will.

3 CypMgZ + R SnZ ₃ ■ * ■ ■ CyP ₃ SnR * +

3 3 3

CypsSnR + SnZ, -> Cyp ₃ SnZ + R SnZ,

The alkyltin trihalide R ^ SnZi can in turn be prepared in such a way that the corresponding alkyl halide r'z ² with a tin (II) halide Snz | according to US Pat. No. 3,340. Reference is expressly made herein to the corresponding contents of this patent specification.

The reaction between the tin-IV halide and the tetraorganotin compound should be carried out under anhydrous conditions at temperatures of -25 to 80 ^° C., preferably -25 to 80 ^° C., in

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it

a hydrocarbon solvent. Preferred Examples of solvents are pentane, hexane and cyclohexane.

Preferably the tin IV halide is dissolved in an organic solvent and the resulting solution is added dropwise to a second solution containing the tetraorganotin compound in the same solvent. The temperature of the reaction mixture is preferably maintained below about 30 ° C. during the addition, which requires about an hour. Thereafter, the mixture to a temperature of 35 is heated to 80 ⁰ C. The reaction mixture is preferably carried out at the reflux temperature. Heating is continued for about 15 to 60 minutes to ensure complete conversion. The reaction mixture is then allowed to cool to ambient temperature and extracted with one or more portions of water or an aqueous mineral acid. The by-product of the reaction, a monoorganoζin trihalide, R ^ SnZi, is soluble in the aqueous phase of the reaction mixture. The desired product remains in the organic phase and is easily isolated by evaporating the hydrocarbon solvent. No further purification is usually required, but the product can be distilled if desired. The organic layer is preferably freed from any dissolved water after the extraction step. Any conventional chemical dehydrating agent is suitable provided that it does not react with either the triorganotin halide or the hydrocarbon solvent. Preferred desiccants are, for example, anhydrous magnesium sulfate, anhydrous sodium sulfate and anhydrous calcium sulfate.

Tricyclopentylalkyltin bromides can be made by gradually adding bromine to a solution containing the corresponding tetracyclopentylalkyltin compound contains, are obtained. The tetraorganotin compound is in turn prepared in such a way that

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a cyclopentylalkylmagnesium halide with a tin IV halide in a molar ratio of 4: 1.

The triorganotin halides of the invention are solids or liquids at ambient temperature. The halides can easily be converted into other derivatives, for example the oxide, acetate and sulfate, by known reactions. The desired anionic radical can be introduced in such a way that the corresponding triorganotin halide,
-hydroxide or -bistriorganotin oxide with the reagent indicated in the following table.

Organotin derivative

Chloride, bromide or iodide

It If M

η η

+ Reagent

Carboxylic acid + acid ac epto r, e.g. an amine

Alkali metal salt of a carboxylic acid

aqueous solution of an alkali metal hydroxide

Alkali metal alkoxide or alcohol + acid acceptor (e.g. an amine)

Alkali metal phenoxide or phenol + acid acceptor

Potassium fluoride or hydrofluoric acid

Alkali metal sulfide alkali metal sulfate

Mercaptan + acid acceptor

Alkali metal cyanate

Alkali metal thiocyanate

Alkali metal thiocarbamate
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desired product

Carboxylate, e.g., acetate

Oxide (or hydroxide)

Alkoxide

Phenoxide fluoride

Sulfide sulfate mercaptide

Cyanate thiocyanate

Thiocarbamate

Organotin derivative

Chloride, brcraid or iodide

Oxide or hydroxide

hydroxide

reagent

Alkali metal diethyl carbamate

Phosphoric acid or alkali metal phosphate

desired product

Dithiocarbamate

phosphate

Alkali metal dialkyl Dialkyldithio di thiopho sphat phosphate Carboxylic acid or Carboxylate -anhydride Alcohol (or phe Alkoxide (or nol) Phenoxide) Hydrogen fluoride Fluoride acid diluted (10-25 sulfate % by weight) aqueous sulfuric acid Hydrogen sulfide sulfide Alkyl or aryl Mercaptide mercaptan Carbon dioxide Carbonate Heating to remove oxide

tion of the water

The reaction conditions as well as the preferred solvents, Temperatures and reaction times for the preparation of the derivatives listed in the table above are known and therefore do not need to be described in detail at this point. A detailed overview can be found together with numerous references in the work of R.E. Ingham et al in the October 1960 issue of CHEMICAL REVIEWS (pages 4-59-539). The above derivatives can be liquids or solids at ambient temperature depending on the type of substituents X or T be.

The tricyclopentyltin and tricyclopentylalkyltin compounds of the invention effectively control many types of undesirable fungi and insects, especially puffs, though

plant them on level

be applied, which compared to a 8/0895

Are susceptible to infestation by these organisms. The combination of a fungicidal and miticidal activity is for a single one Organotin compound not common. A single application of these compounds to living plants or other substrates provides residual and extensive control of many varieties of fungi and insects over a significant period of time, the length of which depends to a certain extent on mechanical and biological influences, including the cousin. Preparations which contain the organotin compounds according to the invention can be applied directly to the organisms to be controlled be applied.

In making compositions for application to plants, the organotin compound is often used in the manner enhanced or modified by adding one or more commonly used pesticide additives or Auxiliaries such as organic solvents, water or others liquid carriers, surfactants to aid in dispersing or emulsifying the organotin compound, and mixed with finely divided solid carriers. Depending on the concentration of the triorganotin compound in them Compositions can these either without further diluents or as liquid concentrates, which are subsequently followed by a or with several inert liquids to the finishing compositions can be diluted. For compositions that are used as concentrates, the Triorganotin compound can be present in concentrations of from about 5 to about 98 weight percent. Other biologically active agents that are chemically compatible with the triorganotin compounds of the invention can also be added.

The optimal effective concentration of the tin compound used as a toxic agent in a composition, depends on whether the organism comes into contact with the agent or, as is the case with insects, the toxic agent records. The actual amount of compound that is the effective

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if

The same dose represents depends primarily on receptivity of the respective organism from the given triorganotin compound away. In the control of insects, good results are obtained with liquid or dusty compositions obtained containing, for example, only one ppm toxic agent. Compositions containing up to 90% by weight of the toxic Agent contained can be used to treat severely affected areas.

In the preparation of the powdery compositions can the organonin compound with many commonly used finely distributed, solid carriers are mixed, for example with Puller's earth, attapulgite, bentonite, pyrophyllite, vermiculite, Diatomaceous earth, talc, lime, gypsum and wood flour. The carrier, which is usually in finely divided form, is mixed with the grind or mix toxic agents or with a dispersion of the toxic agent moistened in a volatile liquid. Depending on the relative proportions of the toxic By means of and the carrier, these compositions can be used as concentrates, which can then be used with a further solid carrier are diluted, whereby the desired amount of the active ingredient is obtained. Alternatively, such concentrated dust compositions in combination with various known anionic, cationic and non-ionic wetting agents as Emulsifiers or dispersants can be used to form spray concentrates. Such concentrates are without further dispersible in liquid carriers, whereby spray compositions or liquid preparations are obtained, which contain the desired amount of the toxic agent. The choice and concentration of the surfactant are determined by the ability of the material to disperse the concentrate in the liquid carrier to obtain the desired liquid composition intended to facilitate. Suitable liquid carriers are, for example, water, methanol, ethanol, Isopropanol, methyl ethyl ketone, acetone, methylene chloride, chlorobenzene, toluene, X ^ aL #nd. Petroleum distillates. Under the loading

- yr-

vorzugten petroleum distillates fall those which boil at atmospheric pressure at a temperature below 204 ⁰ C and have a flash point of more than about 26.7 ⁰ C.

Liquid compositions can also be prepared in the manner be that one dissolves a triorganotin compound according to the invention in a mixture, the one immiscible with water organic liquid and a surfactant dispersant. The resulting emulsifiable concentrate is then further diluted with water and an oil to form spray mixtures in the form of oil-in-water emulsions. In such compositions the carrier is an aqueous emulsion, i.e. a mixture of the water-immiscible solvent, the emulsifier and water. Preferred dispersants for such compositions are oil soluble and include, for example, condensation products of alkylene oxides with phenols and organic and inorganic acids, polyoxyethylene derivatives of sorbitol esters, alkylarylsulfonates, complex ether alcohols, mahogany soaps, and the like. Suitable organic liquids for these compositions are, for example, petroleum distillates, hexanol, liquid halogenated hydrocarbons and synthetic organic oils. The surfactant dispersants are usually used in the liquid dispersions and aqueous emulsions in an amount of about 1 to 20% by weight based on the total weight of the dispersant and active toxic gown.

The organotin compound or a compound containing this The composition can be applied directly to the organism to be controlled or to the area to be protected, in particular plants and trees. The application to the foliage of plants is suitably carried out in such a way that power atomizers, tree sprays, and spray atomizers are used. When used in this manner, the compositions should not contain significant amounts of phytotoxic diluents. In the case of the large-sized company,

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NEN dusts or sprays with a small volume can be applied from an aircraft.

In the examples, preferred embodiments of the invention Compounds and their use as fungicides and insecticides are described. All parts and percentages are based on weight, unless otherwise stated.

Examples

Example 1 - Preparation of Tricyclopentyl Tin Chloride and Derivatives thereof

A - Manufacture of butyltricyclopentyltin

24.3 6 (1 gram atom) of magnesium chips, which had been heated under a nitrogen atmosphere at 40 ⁰ C, a 25 cm -Portion was added a solution containing 149 g (1 mol) of bromocyclopentane, dissolved in 750 cm * anhydrous tetrahydrofuran, contained. The reaction was initiated by a few drops of ethylene dibromide. The remainder of the bromocyclopentane solution was gradually added over 2 hours while the reaction mixture was heated to the boiling point. Heating was continued for an additional 1.5 hours. During this time were

15 cnr of a 3 standard solution of butyl magnesium bromide in tetrahydrofuran added so that a reaction with any impurities could take place, which would be able to prevent or inhibit the formation of cyclopentyl magnesium bromide. A small particle of iodine was also added as a reaction initiator. The reaction mixture was brought to ambient temperature left to cool and at this temperature about

Leave for 16 hours. During this period the mixture was continued to stir. At the end of this period, that seemed like it Having implemented all of the magnesium. A 100 cur serving of Tetrahydrofuran was added to make up for evaporation loss of the solvent. Then the reaction

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mix heated to boiling point for 2 hours. A 500 cubic centimeter portion of this solution containing 0.66 moles of cyclopentyl magnesium bromide was added dropwise to a stirred solution of dibutyltin trichloride (56.4 g, 0.2 mole) dissolved in 250 cubic centimeters of dry benzene. The encore took an hour. It was carried out under a nitrogen atmosphere. The temperature of the reaction mixture was kept below 45 ° C. during the addition. When the addition was complete, the reaction mixture was heated to boiling point for one hour, then allowed to cool to ambient temperature and stirred for 18 hours. A solution containing 200 cm * water and 35 U citric acid was added to the resulting mixture. The organic phase of the resulting two-phase liquid was separated and the water present therein was removed using a portion of anhydrous magnesium sulfate which had previously been removed by filtration. The solvent was evaporated under reduced pressure to give 72.25 g (94 % yield) of a liquid, namely butyltricyclopentyltin, having a refractive index (/ η jj ') of 1.5220. This liquid was extracted once with methanol. The vapor phase chromatographic analysis showed that the product had a purity of 96.7%. The product was found to contain 30.24-96 tin. The calculated value for butyltricyclopentyltin is 30.98%.

B - cleavage of butyltricyclopentyltin to tricyclopentyltin chloride

A 19.2 g (0.05 mole) portion of the butyltricyclopentyltin prepared in Part A above of this example was poured into 75 cm * heptane dissolved. A solution became to this solution given the 13.0 g (0.05 mol) of anhydrous tin IV chloride and contained 75 cnr of heptane. The addition took 20 minutes. Thereafter, the resulting mixture became boiling point for 30 minutes heated and then allowed to cool to ambient temperature. Then a solution was obtained by mixing

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of 4 cnr of 12 η aqueous hydrochloric acid and 96 cnr of water were added to the reaction mixture with vigorous stirring both during the addition and for 5 minutes thereafter. The organic layer of the resulting two-phase liquid was combined with an aqueous hydrochloric acid solution prepared as described above. The organic layer was isolated. The water therein was removed using an amount of anhydrous magnesium sulfate. The heptane was then evaporated under reduced pressure to obtain 17 »8 g pale yellow crystals nit a melting range of 4" -44 ⁰ C were obtained. The analysis of the product indicated by vapor phase chromatography that this had a purity of 97 "2%. After a recrystallization from pentane at -78 ⁰ C, the product had a melting point 44-45 ° C. the purity, as determined by vapor phase chromatography, was 99> 6%.

Tricyclopentyltin hydroxide was prepared by adding a solution of the appropriate chloride (18.1 g of the chloride in 40 cm * tetrahydrofuran) to a solution containing 3.0 g of sodium hydroxide, 12 cubic meters of water and 12 cubic meters of methanol. The addition was gradual and took 20 minutes. At this point 12 cubic meters of water were added. The resulting slurry was stirred for 0.5 hour. At this point 150 cubic meters of water was added to completely precipitate the product. The solid was isolated and washed with deionized water until there was no detectable amount of chloride ion in the water. The solid was then dried in a rotary oven kept at a temperature of 40 ° C. Analysis by potentiometric titration showed that the hydroxide had a purity of 98.6 to 99.1 % .

C - tricyclopentyl tin fluoride

Tricyclopentyl tin fluoride was made from the corresponding hydroxide manufactured. A solution containing 300 g of tricyclopentyltin

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hydroxide and 3600 cnr tetrahydrofuran, was clarified by filtration. A solution which had been obtained by mixing 50 g of a 48% strength aqueous hydrofluoric acid solution with 150 cnr water was gradually added to this solution. The resulting mixture, which contained a white precipitate, was ^{heated to boiling point (64 °} C.) for 0.25 hours and then cooled to ambient temperature. It was filtered and the precipitate was washed successively with 1 liter of a 0.1% strength aqueous hydrofluoric acid solution, 1 liter of deionized water and 500 cm * of methanol. After drying at reduced pressure and a temperature of 50 ^° C., the white solid (280 g) had a melting point of 275 to 280 ^° C. with signs of decomposition. The solid was found to contain 34.05% tin and 5-32% fluorine. The calculated values for tricyclopentyltin fluoride were 34.40 % tin and 5-51% fluorine.

D - Tricyclopenty1ζinnac etat

A solution of 3.15 g of acetic acid (glacial acetic acid) in 100 cm of diethyl ether was added dropwise over 0.25 hours to a suspension of 17.15 g of cyclopentyltin hydroxide in 100 cm of diethyl ether. The solids dissolved and the solution was stirred at 25 ° C for 0.25 hours. About 15 g of anhydrous magnesium sulfate was added to the solution, and the mixture was stirred for one hour to remove water generated during the reaction. The mixture was then filtered and the solvent removed on a rotary evaporator to give 20 g of a white solid. The solid was placed in a desiccator over sodium hydroxide pellets and held at reduced pressure for 48 hours to remove excess, unreacted acetic acid. The product, a white solid, had a weight of 18.7 g. The melting point was 52 to 54 ^° C.

Analysis: found: tin 30.65 #, acid number 160 Calc .: tin 30.82%, acid number 146

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E - tricyclopentyltin 2-ethylhexanoate

A 17.1 g serving of tricyclopentyltin hydroxide and 7.2 g of 2-ethylhexanoic acid in 200 cm? Benzene was heated to boiling point. The water formed as a by-product (0.84 cur) was with removed from a Dean-Stark trap. The benzene was reduced at Pressure evaporated, leaving 23.5 g of a yellow liquid

27
- T / ^ = 1.5058.

Analysis: found: Sn 25.14%, acid number 123.6 Calc .: Sn 25.29%, acid number 119.5

F - tricyclopentyl tin benzoate

The benzoate was prepared according to the procedure described for the 2-ethylhexanoate, using 17.1 g of tricyclopentyltin hydroxide and 6.1 g of benzoic acid. The product had after a single recrystallization from hexane-η g a weight of 19.6 at -70 ⁰ C. The melting point was from 37 to 38.5 ⁰ C.

Analysis: found: tin 26.42%, acid number 131 calc .: tin 26.54 ⁰ Zo ₁ acid number 125

G - Bis- ^ tricyclopentyltin 7-oxide

6 hours by heating a sample of the hydroxide at 100 ⁰ C and a pressure of 0.5 to 1.0 mmHg was a sample of the Bisoxids prepared which showed a strong absorption in the infrared spectrum at 785 cm, which on the Sn-O- Was due to Sn bonding. No absorption in terms of the Sn-OH bond was seen, indicating that the compound was completely dehydrated to the bisoxide.

809808/0895 H - Tricyclopentyl tin phenoxide

The phenoxide was prepared in such a way that one L6-

is

solution containing 17 * 15 g of tricyclopentyltin hydroxide, 4.71 g Phenol and 200 cm * benzene heated to boiling point. The water formed as a by-product (10.8 cnr) was released during the reaction removed.

Evaporation of the solvent gave 21.05 S of a yellow oil. η ² % - 1.5627.

Analysis: found: Sn 28.04, -OCgHc remainder 24.0% calc .: Sn 28.32, -OCgHc remainder 22.2 %

I - tricyclopentyl tin chloride (from the hydroxide)

To a suspension of 17.15 g of tricyclopentyltin hydroxide in 100 cm * pentane, 6 cnr of a 36% strength aqueous hydrochloric acid solution were added with stirring. The organic phase was separated off and, after adding 3 g of sodium sulphate and 100 cnr of ether in order to break up the emulsion, dried over magnesium sulphate. After filtration, the pentane phase was stripped of solvent to give 17 "05 g of white crystals having a melting point 39.5 to 42.5 C ^0.

Analysis: found: Sn 32.60, Cl 9.82%
calc .: Sn 32.83, Cl 9.81 %

Analysis by vapor phase chromatography showed the product to be greater than 95% pure.

J - tricyclopentyltin dimethyldithiocarbamate

To a solution containing sodium dimethyldithiocarbamate dihydrate (5.38 g) and 50 cur of water was added a solution which contained 10.84 g of tricyclopentyl tin chloride and 50 cm * acetone. The mixture was stirred for one hour and then poured into a separatory funnel. The lower phase became too 100 ei * acetone given. The aqueous phase was once with

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50 cnr hexane extracted. The hexane became the acetone solution and the mixture was dried with anhydrous magnesium sulfate for 1 1/2 hours. After filtering it was the solvent removed under reduced pressure, yielding 13.15 β of a beige pesticide with a melting point of 55 to 57 ° C were obtained.

Analysis: found: Sn 26.67, total sulfur 14.48 % calc .: Sn 26.60, total sulfur 14.30%

K - tricyclopentyltin - ^ - acetylaminobenzoate

A mixture containing 17-15 g of tricyclopentyltin hydroxide, 9.0 g of 4-acetylaminobenzoic acid and 250 cur of benzene was heated to the boiling point using a Dean-Stark palle to isolate the water formed. A 0.8 cm portion of water was collected over 1.5 hours. The hot solution was filtered and allowed to cool to room temperature. Crystals separated out. The crystals were filtered and dried in vacuo. Yield «21.49 g of white crystals with a melting point of 169 to ⁰

Analysis: found: Sn 23.87%, acid number II3 Calc .: Sn 23.54%, acid number 111

L - tricyclopentyltin 2-aminonicotinate

A mixture containing 17.2 grams of tricyclopentyl tin hydroxide, 6.90 grams 2-aminonicotinic acid and 250 cm * benzene was heated to the boiling point, using a Dean-Stark trap to prevent the as Collect by-product formed water (0.9 cm *). The hot one Solution was filtered and allowed to cool to tree temperature. During this time, 22.26 g of a yellow pest separated out with a melting point of 92 to 98 ° C. The crude product was recrystallized from 250 cm * heptane, leaving 11.48 g of white

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Crystals with a melting point of 101 to 1O3 ° C were obtained. Evaporation of the solution to 1/2 original volume under reduced pressure and cooling to ⁰ ° C separated from the heptane solution further 7.5 g of white crystals having a melting point of 99-101 ⁰ C from. Both quantities were combined and analyzed.

Analysis: found: Sn 26.29%, acid number 123 Calc .: Sn 25.63%, acid number 121

M - bis / ericyclopentyltin 7 sulfide

To an aqueous solution containing 12.1 g of disodium ethylenebis (dithiocarbamate) in 150 cubic meters of water was added dropwise over 1/4 hour a solution containing 25 g of tricyclopentyltin chloride and 150 cubic meters of acetone. In the beginning a plague developed. While stirring, however, £ _he solid to a yellow oil, which was suspended in a viscous fluid changed. The mixture was poured into a separatory funnel. 75 cnr of ither was added. The aqueous phase was removed and the organic phase was added to 100 cnr acetone. The organic phase was dried over anhydrous magnesium sulfate. Evaporation of the solvent gave 31.19 g of a mixture of a yellow viscous liquid and a solid. A 200 cm portion of benzene was added and the mixture was heated. The crude product was then ^{cooled to 25 °} C. and filtered. The filtrate was stripped of solvent to give 24-25 g of a yellow liquid plus solids. The mixture was filtered. The filtrate partially solidified over the course of 4 days. The resulting mixture was recrystallized from 100 cn isopropanol, whereby 6.6 g of yellow crystals having a melting point of 70 to 72 ° C were obtained.

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η '

Analysis: found: Sn 34.87, total sulfur 4.39 % calculated for: / XC , -Hq) ^ Sn / ₂ S

Sn 34.70, total sulfur 4.69 %

N - tricyclopentyltin 2-thiophene carboxylate

An 18.8 g portion of tricyclopentyltin hydroxide and 6.4 g of 2-thiophenecarboxylic acid were heated to the boiling point in 200 cur of benzene for two hours. During this time, 0.6 cm * of water was collected in a Dean-Stark trap. The hot reaction mixture was filtered and then the solvent was removed under reduced pressure. In this way were obtained 24.54 g of a white Peststoffes having a melting point 58 to 62 ⁰ C.

Analysis: found Sn 26.43%, acid number 118 Calc .: Sn 26.20%, acid number 124

0 - bis-tricyclopentyltin Z-adipate

The adipic acid derivative was prepared similarly as described above under N, with 18.8 g of tricyclopentyltin hydroxide and 3.65 g of adipic acid were used. A 0.85 cm portion of water was collected during the reaction. After removing the Benzene, 20.63 g of a white pesticide was isolated. The melting point was 61 to 65 ° C. The recrystallization from 100 cm * of methanol yielded 18.55 g of white crystals with a Melting point from 66 to 69 ° C.

Analysis: found: Sn 29.46%, acid number 142 calc .: Sn 29.81%, acid number 141

P - tricyclopentyl tin thiophene oxide

A mixture containing 18.8 g tricyclopentyl tin hydroxide, 5.5 g thiophenol and 200 cnr benzene was heated to the boiling point.

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A total of 0.84 cnr of water was added over the course of 1.5 hours collected. The resulting solution was filtered and the solvent was evaporated, leaving 22.9 g of a yellow

Oh.

liquid product were obtained. 7) _D «1.5385»

Analysis: found: Sn 29.25, S 6.68 %
ber .: Sn 25.29, S 6.82 %

Q - Tricyclopentyltin-1,2,4-triazole

A mixture containing 18.8 g of tricyclopentyltin hydroxide, 3 * 4-5 g 1,2,4-triazole and 200 cnr toluene were added for one hour Boiling point heated. During this time they were caught in a Dean-Stark trap 0.82 cnr of water collected. 100 cnr of toluene was then distilled off and the resulting solution was filtered. After cooling, crystals separated out and were isolated and dried. They weighed 19.1 g. A recrystallization from boiling toluene gave 17.9 g of a product with a melting point of 204-5 to 210 ° C.

Analysis: found: Sn 30.16, N 11.37%
calc .: Sn 30.12, N 10.66 %

Example 2 - Preparation of tri- (2-cyclopentylethyl) tin bromide and derivatives thereof

A - Tetra (2-cyclopentylethyl) tin

To a solution containing 0.5 mol of cyclopentylethylmagnesium bromide, prepared in a conventional manner from 0.5 mol of 2-cyclopentyl-1-bromoethane, 0.5 gram atom of magnesium chips and 250 cnr of tetrahydrofuran, a solution was added which contained 26.0 g (0 , 1 mole) tin-IV-chloride and 100 cnr benzene. The addition was gradual and took 0.5 hours to complete. At this point the reaction mixture was heated to boiling point for 2 hours. The ea was then allowed to cool to ambient temperature

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- & ■

calmly. The product was then hydrolyzed with a solution containing 15 g citric acid and 250 ml water. The organic portion of the resulting two-phase liquid was isolated. The water contained therein was removed with anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure to give 59 »3 g of a semi-solid which was mixed with 100 cubic centimeters of isopropanol and stirred for one hour. The resulting slurry was filtered, ^{washed with cold (0} ° C.) methanol and dried. In this way 49.15 g of a white solid with a melting point of 74 to 77 ° C were obtained.

Analysis: found: Sn 22.41%, Cl 0.13 %
calc .: Sn 23.40%, Cl 0.0 %

B - cleavage of tetra- (2-cyclopentylethyl) tin

To a solution containing AO, 6 g of tetra (2-cyclopentylethyl) tin, 90 cnr chloroform and 35 cnr methanol, which was maintained at ⁰ C O, a solution was added dropwise over 5 hours 12.8 g bromine mixed with 50 cm * methanol and 50 cnr chloroform. When the addition was complete, the mixture was allowed to warm to 25 ° C. The solvents were evaporated under reduced pressure to give 4-1.7 g of a white solid. The product was recrystallized from 150 cm 'of methanol by cooling to -20 ° C. The crystals were filtered, washed with methanol at a temperature of -60 ⁰ C and dried under reduced pressure. The first crop of crystals weighed 24.4 g. The melting point was 55 to 58 ° C. The mother liquor solution was evaporated to 1/3 of the original volume and then cooled to ^{0 ° C.} A second crop of crystals separated out, which were filtered and dried. This yield had a weight of 7.9 g. The melting point was 58 to 60 ^° C. The two yields were combined. The total weight was 32.3 g

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Analysis: found: Sn 23.90%, Br 15.22%

Calculated for tri ~ (cyclopentylethyl) tin bromide: Sn 24.22%, Br 16.31%

C - bis- / tri- (cyclopentylethyl) tin 7 oxide

A solution containing 9 »8 g of tri- (cyclopentylethyl) tin bromide, 100 cm * of methanol and 40 cm * of acetone. The addition was gradual and took 10 minutes. After the addition was complete, the reaction mixture was heated to boiling point (67 ° C.) for 2 hours and then cooled to ambient temperature. At this point 150 cubic centimeters of water and 100 cubic centimeters of diethyl ether were added and the resulting mixture was vigorously stirred for 5 minutes. The organic phase of the resulting biphasic liquid was isolated and dehydrated with anhydrous magnesium sulfate. The drying agent was removed after 2 hours and the solvent was evaporated under reduced pressure to give 8.2 g of a yellow oil containing 27> 33% tin. The tin content of pure bis / tri- (cyclopentylethyl) tin 7 oxide is 28.38. Analysis by vapor phase chromatography showed that the compound had a purity of 91.4 % .

Example 3 - Preparation of tri- (2-cyclopentylmethyl) tin bromide

Tetra (cyclopentylmethyl) tin was prepared according to the procedure of Example 2 from cyclopentylmethylmagnesium bromide and tin (IV) chloride. The product was a pest with a Melting point from 63 to 66 ° C. It contained 27.86% tin. The calculated tin content of tetra (cyclopentylmethyl) tin is 26.30%.

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j 3%

Tetra (cyclopentylmethyl) tin was cleaved by reacting the compound with bromine following the procedure of the previous example. After recrystallization from methanol, the product had a melting point of 32 to 3 ^ - ⁰ ° C. It contained 26.34 % tin and 17.84 % bromine. The calculated values for tri- (cyclopentylmethyl) tin bromide are 26.49% for tin and 17.84 % for bromine.

Example 4 - Preparation of tri- (cyclopentylmethyl) tin chloride and the corresponding oxide

Methyltri- (cyclopentylmethyl) tin was produced in the way that 0.425 mol of cyclopentylmethylmagnesium bromide were reacted with 30.5 g of methyltin trichloride in 150 cnr of benzene. The crude product emerged from the reaction mixture as a yellow oil (48.3 g) with an index of refraction of 1.5192 at 24 ° and in a purity of 85% isolated. After washing twice with methanol (75 cnr and 25 cnr) and distillation under reduced 33.8 g of a product were obtained under a

ο? 4

Pressure of 0.3 mmHg boiled at 140 ° C. Tj ^ »1.5230. Vapor phase chromatography showed the material to be 95.6% pure.

To a solution of methyltri- (cyclopentylmeth7l) tin (26.8 g) a solution of tin (IV) chloride was added dropwise in 100 cur pentane (18.2 g) in 100 cnr pentane over 20 minutes. The resulting yellow solution was 0.5 hours for Boiling point heated and then cooled to room temperature. The mixture was mixed with a solution containing 2 cnr 12 η hydrochloric acid and contained 98 cnr of water. Thereafter, the organic phase was separated off and a further portion of 2 cm 12 η Hydrochloric acid and 98 cnr water. The organic phase was separated again and the water was made with anhydrous magnesium sulfate removed. After filtering, the solvent was removed under reduced pressure to give 23.20 g of a white Obtained solid with a melting point of 88 to 90 ° C

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became.

Analysis: found: Sn 29.21, Cl 8.87%

calc .: for tri- (cyclopentylmethyl) tin chloride: Sn 29, M, Cl 8.80 %

Vapor phase chromatography showed the compound to be a Had purity of 98.3%.

Bis- / 6ri- (cyclopentylmethyl) tin 7-oxide

To a solution containing 1.8 g of sodium hydroxide, 10 cm of water and 10 cm of methanol was added dropwise over 15 minutes a solution containing 12.11 g of tris (cyclopentylmethyl) tin chloride and 25 cm of tetrahydrofuran. An initially formed oil dissolved again as the addition progressed. After the addition was complete, the solution was stirred at 25 ° C. for 0.5 hour. A 300 cubic meter portion of cold (10 ° C.) water was added and then 200 cubic centimeters of diethyl ether were added with vigorous stirring. The organic phase was isolated and the water contained therein was removed using anhydrous magnesium sulfate. After filtration, the solvent was removed under reduced pressure, whereby 11.28 g of a waxy solid having a melting point of 59 to 63 ° C were obtained. The crude product was purified by adding 60 cnr methanol and cooling to ⁰ ° C. A small amount of solid material precipitated on it. The solid was removed and the filtrate was evaporated under reduced pressure to give 11.35 g of a yellow liquid. 77 § 1.5296.

Analysis: found: Sn 30.16

Calculated for bis- / tri- (cyclopentylmethyl) tin / oxide: Sn 31.56.

Investigation by potentiometric titration ■ 92.6 % purity.

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Example 5 - Preparation of tri- (2-methylcyclopentyl) tin chloride and the corresponding oxide

A - methyltri- (2-methylcyclopentyl) tin

To a solution containing 0.31 moles of 2-methylcyclopentylmagnesium bromide in 150 cubic meters of tetrahydrofuran was added over one hour a solution containing 21.6 g of methyl tin trichloride in 150 cubic meters of dry toluene. When the addition was complete, the mixture was heated to the boiling point for two hours and then stirred at 25 ° C. for 16 hours. The reaction mixture was then hydrolyzed with a solution containing 25 grams of citric acid and 250 cubic meters of water. The organic phase was separated off and the water contained therein was removed with anhydrous magnesium sulfate. The liquid phase was then evaporated under reduced pressure, whereby 25.4-5 g of a crude product were obtained. Low-boiling impurities were distilled off at 25 to 75 ° C under a pressure of 0.1 mmHg. The residue containing the desired product had a weight of 33.85 g · He had a refractive index of 1.5192 at 24 ⁰ C.

Analysis: found: Sn 30.11

for methyltri- (2-methylcyclopentyl) tin: Sn 30.98

B - Tri- (2-methylcyclopentyl) tin chloride

To a solution containing 13.4 g of methyltri- (2-methylcyclopentyl) tin and 50 cubic meters of hexane, a solution containing 9 * 1 S tin (IV) chloride and 50 cubic meters of hexane was added in the course of 0.5 hours contained. When the addition was complete, the resulting mixture was heated to the boiling point for 15 minutes and then cooled to 25 ° C. The reaction mixture was then hydrolyzed with a solution containing 2 cnr concentrated (12N) hydrochloric acid and 100 cnr Contained water. The organic phase of the resulting two-

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phase liquid was isolated and combined with a second fortion of the aforementioned hydrochloric acid solution. The organic phase was isolated again and the water contained therein was removed with a portion of anhydrous magnesium sulfate. The liquid phase was then evaporated under reduced pressure, whereby 14 g of a yellow oil with a refractive index of {7) ^) 1.5333 were obtained. The product was found to contain 28.48% tin and 8.61% chlorine. The calculated values for the desired chloride are 29.4 % tin and 8.78% chlorine. ;

C- bis- / tri- (2-me-uiylcyclopentyl) -tin 7-03d.d

Bis- / tri- (2-methylcyclopentyl) tin 7-oxide was prepared by gradually adding a solution containing 8.1 g of the appropriate chloride (prepared as described in the previous section), 25 cn * methanol and 15 cn acetone Solution was added containing 1.2 g sodium hydroxide, 20 cm * water and 50 cnr methanol. The addition took a period of 0.5 hours. The resulting solution was then heated to the boiling point for 10 minutes and then cooled ^{to 15 ° C.} During this time 300 cubic meters of water was gradually added. The resulting mixture was stirred for one hour, the temperature being kept at 15 ^° C. A 50 cm portion of diethyl ether was then added while the mixture was being stirred at high speed. The organic phase of the resulting two-phase liquid was isolated. The water contained therein was removed with anhydrous magnesium sulfate. The liquid was then evaporated under reduced pressure to give 7.6 g of a yellow oil containing 30.54 % tin. The calculated tin content of bis / ri (2-methylcyclopentyl) tin 7 oxide is 31.56%. Potentiometric titration of the product showed it to be 98% pure.

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Biological activity of tricyclopentyltin and tri- ( cyclopentylalkyl) tin compounds

The following methods were used to control the effectiveness of the triorganotin compounds of the present invention to identify a number of representative fungi and insects.

Method 1 - Common spider mite (Tetranychus urticae), sugar beet owl (Spodoptera exigua) and cabbage worm (Trichoplusia ni) are used.

A cotton plant with two fully expanded leaves was immersed in an aqueous dispersion of the test compound. Another part was injected into the soil in the root zone. Lepidopterous insect larvae were in the Submerged in water dispersion and placed in petri dishes clipped around the treated foliage. at Using common spider mite as a test insect, the dipping step was not performed because the mites are on the leaf found before the plant was treated. A mortality count was made 6 days after treatment.

Method 2 - This was made using tobacco black stem mushroom (phytophtora parasitica var. nicotiane).

Tobacco plants were transplanted into soil containing the test organism was infected. Immediately after transplantation, the soil was watered with a solution of the test compound. The test was graded based on plant survival.

809-08 / 0895

Method 3 - This was made using pea powdery mildew (Erysiphe polygoni) carried out.

Bean seeds were planted in disinfected soil which was then watered with a solution of the test compound. After this the plants reached a suitable size, they were inoculated with the fungus. After 7 days the relative Number of healthy plants noted.

Method 4 · - This was made using powdery mildew of vine (Plasmopara viticola), rice brandy (Pericularia oryaze) and powdered apple powdery mildew (Podosphaera leucotricha) carried out.

The host plants (vines, rice plants or apple trees, depending on the fungus) were mixed with a water suspension of the test compound injected and then inoculated with the pathogen. After the symptoms of the disease are on the untreated control plants well, the test plants were examined and evaluated for disease control.

Method 5 - Secondary assessment of activity in the control of common spider mite (Tetranychus bimaculatis) and aphid.

Bean plants infected with the organisms were sprayed with a water dispersion containing the test compound. Percent mortality was observed three days after the injection.

Method 6 - This was made using codling moth larvae (Carpocapra pomonella).

Codling moth eggs were placed on a paraffin surface, which had previously been treated with an aqueous dispersion of the test compound. The paraffin was perforated and

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allowed the newly hatched larvae to feed on a putter pad. After 6 days there was one Mortality count.

Method 7 - This was done with owl butterfly larvae.

Five owl butterfly larvae in the third instar were placed on petri plates, one layer of a semi-synthetic one Putters included. These larvae were with 3 cnr one Solution or suspension of the chemical compound with 400 ppm sprayed at a distance of 33.1 cm, including a nozzle 40100-120 from Spraying Systems Company was used. After the injection, the lid of the Petri dish was replaced by a fiber lid, to allow air exchange. Mortality counts were performed after a hold period of up to 3 days.

Method 8 - This was done using apple scab (Venturia inaequalis).

Apple seedlings were infected with the fungus. The seedlings were then treated with an aqueous solution or suspension of the test compound injected. After an incubation period, the plants were examined for disease control and graded.

Method 9 - This method was performed on horn fly larvae.

The test compound was mixed with calf feces and horn fly eggs were introduced. After 2 days it was confirmed for the presence examined by fly larvae.

Method 10 - This method was performed using cabbage worm (Trichoplusia ni) to monitor system activity to determine.

An aqueous dispersion of the test compound was poured into the root

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zone of a bean plant that was infected with cabbage worm, injected. Porridge until six days after treatment were given Mortality counts carried out.

Method 11 - This was done using cabbage worm (Trichoplusia ni).

A bean plant was treated with an aqueous dispersion of the Test compound injected. A number of cabbage worms were placed on the treated foliage. After 3 days the Mortality determined.

Method 12 - This method was carried out with cabbage worm determine egg activity.

The test compound was dissolved in an appropriate water-miscible solvent and diluted with water to the desired concentration. Cabbage worm eggs taken from adult insects on a paper towel or other substrate were placed on the underside of the leaf of the test plant with Methocel or another suitable adhesive attached. Egg leaves with 25 to 50 eggs per plant were selected. There were cotton plants or some other suitable one Host plant used. The leaf of the plant to which eggs were attached was immersed in a solution containing the test compound contained. Ovicid observations were made 3 to 5 days after treatment. In the case of inactive materials, it was found that large areas of the foliage were occupied by newly hatched larvae.

Method 13 - This was done using western spotted cucumber beetle larvae.

75 g of air-dried earth were placed in 236 cm * round bottles and with a sufficient volume of a solution containing 400 ppm the test compound treated, the 25 ppm test compound, based on

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" ho '

on air-dried soil. The treated Soil was mixed by shaking and rolling after allowing to dry.

Western spotted cucumber beetle eggs (laid over a 3 or 4 day period) were collected. A measured amount of the eggs was suspended in water. The egg concentration was 70 to 80 eggs / 0.5 cm * solution. A part the suspension containing about 50 eggs was pipetted into the bottom of a clear, medical plastic vial. It was a sufficient amount of treated soil is added. One corn seed was brought to earth and treated with another Earth covered.

The mixture of soil, eggs and seeds was poured and more water was added in the required amount, that the growth of the corn seedling plant is maintained became. Care had to be taken not to add too much water to prevent the larvae from drowning. To The presence of larvae on both the top of the soil and at the roots of the seedling was determined over a period of 6 to 9 days.

Method 14 - This was done using codling moth larvae to increase ovicidal activity and determine the control of newly hatched larvae.

The test compound was dissolved in a small amount of a suitable water-miscible solvent and washed with water. water diluted to the desired concentration. The solution to the Test compound was applied to apples or pears, which were then covered with codling moth eggs. The fruit was then incubated in a greenhouse for 8 to 10 days. The number of living and dead larvae was then determined and a sample of an untreated fruit, which was used as

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Control sample used was compared.

Method 15 - This was done using Mo3kito larvae.

Aedes aegypti third instar or early fourth instar larvae were used as the test organism. 20 to 25 larvae were placed in distilled water containing the test compound . Activity was determined as the concentration (ppm) which was the lethal dose for 95 % of the population

Method 16 - This was done using powdered apple powdery mildew.

Aqueous solutions or suspensions of the test compounds were poured into vermiculite cups in which the plants grew. The aqueous system usually contained acetone and a humectant, both in non-toxic amounts. 2-4 days after application of the compound, the leaves were moistened with a spore suspension of powdered apple powdery mildew. The plants were then placed in a greenhouse. When the disease symptoms were clear , the plants were rated. TTn-treated plants were rated as a 0 % control. Plants free of the disease were rated as 100% control.

In the tables below, the values are compiled which were obtained by the aforementioned methods using representative compounds according to the invention .

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Table I.

Biological activity of tricyclopentyltin hydroxide against mushrooms

organism Method No. concentration
(■ DOa) valuation
the Kon
trolls (%) Tobacco black stem rorv) 25th
6.3 100
100 Bean powdery mildew 3 25th 100 Powdery mildew 4th
4th 100
6.2 100
95 Rice brandy 4th
4th 100
25th 93
67 Powdered apple mildew 4th
4th 100
25th 100
95 Table II

Biological activity of tricyclopentyltin hydroxide against insects

organism Method No. concentration
(υ-oa) valuation
the Kon
trolls (%) common spider mite 5
5
5 400
100
25th 100
100
86 Sugar roll 1 400 100 Cabbage worm 1 100 100 Codling moth larvae 6th 400 100 Owl butterfly larvae 7th 400 100 Aphids 5 400 100

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Table III

Biological activity of tricyclopentyl tin chloride as a fungicide

Valuation!'

Organism Method No. Concentration of the

(ppm) trolls (%)

Apple chorus 8 100 90

Rice brandy 4 100 95

4 100 70

Powdered apple mildew 16 100 70

Table IV

Biological activity of tricyclopentyl tin chloride as an insecticide

valuation

organism method No. concentration
(ppm) the Kon
trolls (ft) Cabbage worm
Codling moth larvae 1
14th 400
400 100
100 Tabel 7th

Biological activity of tricyclopentyltin acetate as a fungicide

valuation

Organism method ITr. Concentration of control (ppm) trolle (»)

Flour taxi 4 400 100

100 90

Powdered apple powdery mildew 4 100 90

809909/089

Table 71

Biological activity of tricyclopentyltin acetate as Insecticide

organism Method No. concentration
(ppm) valuation
the Eon
troll OO Cabbage worm 12th 400
100 90
90 Cucumber beetle larvae 13th 25th 100 Table VII

Biological activity of tricyclopentyltin fluoride as an insecticide and fungicide

Method No. concentration Table VIII concentration valuation organism (ppm) of tricyclopentyltin bromide (ppm) the Kon 1 400
100 Method No. 400 troll OO common spider mite 1 400 400 99
97 Cabbage worm 14th 400 1 25th 100 Ap fe Iw ic kl erl arven 4th 400 1 1 100 Powdery mildew 100 25th 100 50 15th 400 94 4th 400 2 100 80 Rice brandy 100 4th 96 4th 100 80 Powdered apple mildew 90 Biological activity valuation
the Kon organism troll OO 100 common spider mite 100 Cabbage worm 83 100 Mosquito larvae 100 Tobacco black stem 97 Powdery mildew 100

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Powdered apple mildew 4 400 90

100 97

6.3 75

Tabel IX Biological activity of tri-cyclopentylethyl tin hydroxide

Evaluation of the organism method Mr. Concentration of the

(ppa) trolls {%)

common spider mite 5 400
1ΩΩ 95
QP 400 83 l \ J \ J
25th 7 °
50 100 100 Powdery mildew 4th 400
100
25th 100
85
50 25th 100 Apple scab 8th 400 100 400 75 Table X Biological activity of tri- (cyclopentylethyl) tin broaid organism valuation
Method No. Concentration of the
(ppa) trolls (ff) Cabbage worm 1 Hora fly larvae 9 Tobacco black s te ng el 2 Powdered apple mildew 4th Table XI

Biological activity of tri- (2-methylcyclopentyl) tin chloride

valuation

Organism Method No. Concentration of control (ppsi) trolle (ff)

Cabbage worm 1,400 100

Powdery mildew 4 400 100

Apple scab 8 400 ICO

100 60

883868/0 8 9,

Claims (1)

Claims iJ triorganotin compounds of the general formula SnX or Sn J2 where X is fluorine, nitrate, cyanate, carbaate, thiocarbamate, Amide (NH ₂ ), amino (NE ₂ or NE ¹ H), nitrate, Alkoxy (-0R), DLthiocarbamoyl \ -SCN ^! S Λ! odeo Dialkyldithiophosphatt '(-SP ^ ι -0-C- (O) -NH ₂ , where E ^{1 is} alkyl with Λ to 12 carbon atoms or phenyl / τ \ * \ where Z is hydrogen, ₁ _, halogen, C - alkyl, C _1-5 -alkoxy or nitro has (-NO ₂₎ group, 809808/0895 is alkyl of 1 to 12 carbon atoms and Y is O O Tl ■ ' for oxygen, -OC (CH ,,) C-O-, where m is an integer O
is from 2 to 10, J _w " _Λ _ sulfur, sulfate or -OC- (O carbonate stands. 2. Triorganotin compounds according to claim 1, characterized in that that Y stands for oxygen. 3. triorganotin compounds according to claim 1, characterized S 0 0 ^) or -OC H ₂ N draws that X for _ _s _c _{N (C} k ₃ ) ₈ , -OC stands. 4. triorganotin compounds according to claim 1, characterized 0 0 ti Il indicates that Y is sulfur, _qc (CH) CO-0 0: / r \\ «« I stands. -OC / O) CO! 5 · Triorganotin compounds of the general formula (CH ₂ ) -13 SnX or (CH ₁ ) J Sn-4-Υ where m has the value 1 or 2, X stands for fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, 3 0 9 8 0 ^{8/0 ft ° - ς} Carbonate, nitrate, ~ ° ~ ^c "· Ff I, * j C-O- »^ N, phenoxy, alkoxy (-OR), dithiocarbanoylj ⁿ ^ »y» Mercaptidv (-SR) or Dlalkyldithiophosphate f "^ 0R ¹ -SP. where r ″ represents alkyl of 1 to 12 carbon atoms or V ^ / "^, where Z is hydrogen, halogen, C ^^^ alkyl, C _1-3 -AIkOXy or Nitro (-NO ₂ ), S ² for alkyl with 1 to Λ2 carbon atoms and T for acid 0 0 0 0 substance, ^lf "" / ^ \ "sulfur, sulfate or -OC (CH ₂ KC-O-, -OCVQVco- Hiosphate stands. 6. triorganotin compounds according to claim 5> characterized in that X is hydroxyl. 7. ^! Organotin compounds according to claim 5, characterized in that that Y stands for oxygen. 8. Organotin compounds of the general formula 809808/0895 - WS Sn X or --Y where R is alkyl having 1 to 3 carbon atoms, X for fluorine, hydroxyl, nitrate, cyanate, carbamate, thiocarbamate, phosphate, carbonate, nitrate, carboxylate, -6OCR), -O-C ν Ji, phenoxy, alkoxy (-0R), nithiocarbanoy: N ^ ι J , mercaptide / (-SR) or pialkyldlthlophosphatf where R is alkyl of 1 to 12 carbon atoms Z or \ XJ) ~~~ '■■ , in which Z is hydrogen, halogen, C ₁ , -alkyl, C _-1 , -alkoxy or nitro (-NO ₂ ), R ^{2 is} alkyl having 1 to 12 carbon atoms and Y for 809808/0895 O n Oxygen, OC (CHa) · CO, -OC- (Q or carbon · * is * ■ CO, sulfur, sulfate 9. Triorganozinnverbindungen according to claim 9 »characterized in that that Y is oxygen and R is methyl or ethyl. 10. Composition for killing felts and insects, thereby characterized in that it is an inert liquid or solid carrier and a fungicidally or insecticidally active one Amount of an organotin compound of the general formula SnX or Sn where X stands for fluorine, nitrate, cyanate, carbamate, thiocarbamate, amide (NH ₂ ), amino (NR ₂ or NR ¹ H), nitrate, 809808/0895 Xs, Alkoxy (-OR), dlithiocarbamoyl I -SCN _x ^ i 'S or dialkyl dithiophosphate · '-SP ι where fi ' ^{1 represents} alkyl having 1 to 12 carbon atoms or phenyl where Z is hydrogen, C ^^ - alkoxy or nitro (-NO ₂ ), stands, Halogen, C ₁ E ^{2 represents} alkyl having 1 to 12 carbon atoms and Y 0 0 Il Il for oxygen, -OC (CH ₂ ) CO-, where m is an integer of 2 to 10 is Carbonate stands -OC- '0 η Sulfur, sulfate or 11. Composition according to claim 10, characterized in that Y is oxygen. 12. Composition according to claim 10, characterized in that • S Il Il that Σ for -S-CN (CH ₃ ) _2> -OC- stands. 8 ^ 9808/0895 It -OC -NH ₂ or H _a N % ■ 13 · Composition according to claim 10, characterized in that that T stands for sulfur. 2 pp , CO- or -nc- -co- . Composition for killing felts and insects, thereby characterized in that it is an inert liquid or solid carrier and a fungicidally and insecticidally effective amount an organotin compound of the general formula SnX or (CH.) -) Sn - - Y where m has the value 1 or 2, X for fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate. Phosphate, It η
-OC- -NH ₂ , H ₂ N- Carbonate, nitrate, -o-c- Phenoxy, alkoxy (-OR), BLthiocarbamoy} Mercaptide (-SR *) or Hialkyldithiophosphat 809608 / 089B, where R1 is alkyl of 1 to 12 carbon atoms or - stands in which Z is hydrogen, halogen, C ₁ , -alkyl, C _1-5 -AIkOXy or nitro (-NO ₂ ) stands, E ^{2 stands} for alkyl with 1 to 12 carbon atoms and Y stands for acid It substance, -OC (CH ₂ ) »CO-, -OCH O. -CO-, sulfur, sulfate or phosphate. 15. Composition according to claim 14, characterized in that that X is hydroxyl. 16. Composition according to claim 14, characterized in that T is oxygen. 17. Composition for killing fungi and insects, thereby characterized in that it is an inert liquid or solid carrier and a fungicidally or insecticidally effective amount of one Organotin compound of the general formula Sn X or Sn where R is alkyl having 1 to 3 carbon atoms, X for fluorine, hydroxyl, nitrate, cyanate, carbamate, thiocarbamate phosphate, carbonate, nitrate, carboxylate, 809808/089 * _x χ J, mercaptide (-SR) or 'dialkyldithiophosphate It Il Il -fOCR), -O-C - < -OC- > -NH ₂ , ; xo. _N ^ .., phenoxy, alkoxy (-0R), dithiocarbamoyl where R is alkyl of 1 to 12 carbon atoms or -, where Z is hydrogen, halogen, > * - Ai. C _1-3 -AIkOXy or nitro (-NO ₂ ), R ^{d is} alkyl having 1 to 12 carbon atoms and Y is Il Il Oxygen, -OC (CH ₂ KC-O-, -OC- or carbonate) contains. Il -co- sulfur, SuIfal 18. Composition according to claim 17 »characterized in that that Y is oxygen and H is methyl or ethyl. 809808/0895 THING. H. FiMCH-, tv .-:., Ι r: ο. η. ηΟΗ M9U.IM0. S. StAtSLR. OK. let. n «U R. KNtISSl