CA1092127A - Tricyclopentyltin compounds and pesticidal compositions containing same - Google Patents

Abstract

Abstract of the Disclosure - Trioirganotin compounds of the general formula or effectively control fungi an various types insects when incorporated into formulations that are applied directly to these organisms or to substrates, particularly plants, that are susceptible to infestation with these types of organisms.
The present compounds are particularly advantageous due to their considerably lower phytotoxicity relative to homologous triorfanotin compounds wherein the hydrocarbon radicals are linear and contain from 5 to 7 carbon atoms. In the foregoing formulae R is selected from the group consisting of hydrogen and alkyl containing from 1 to 3 carbon atoms, n is 0, 1 or 2, X is selected from the group consisting of chlorine, bromine, fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, nitrate, carboxylate , phenoxy, alkoxy (-OR2), dithiocarbamoyl , mercaptide (-SR1) and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R1 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen,, wherein m is an integer from 2 to 10, inclusive,

Description

I RS(1183 )MS
~ 9Z127' NOVEL TRICYCLOPENTYI,TIN COMPOUMDS AND
PESTICIDAL COMPOSITIONS CONTAINING SAME
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BACKGROUND
Thls invention relates to compositions for selectively controlling ~ungi and pestiferous insects, including mites using a specified class of triorganotin compounds. The organisms against which the present compounds are effective are responsible for a considerable portion of the annual damage to agricultural crops. Many tri- alkyl ~erivatives particularly tri-n butyltin and tri-n-amyltin derivatives may effectively control these organisms, however, these compound I are sufficiently non selective toward desirable plant crops in that while the fungus or insect attacking the plant may be controlled, any plant to which the organotin compound is applied may be killed or severely damaged.
It is therefore an objective of this invention to provide a class of triorganotin compounds that can effecti~ely I control both fungi and insects on living plants without ¦ significantly damaging the plant. Many triorganotin compounds ¦¦ are active against either fungi or insects but not both of these classes of organisms. Surprisingly it has been found ¦~ that certain triorganotin compounds wherein the hydrocarbon 1¦ groups bonded to the tin atom contain a cyclopentyl structure I satisfy this ob~ective.

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iO~21'~7 SUMMARY OF THR INVRNTION
This lnvention provides novel tricyclopentyl- and tricyclopentylalkyltin compounds of the general formulae ~ (CH~)n t 5nX and ¦ ~ (CH~)n ~ ~S ¦

wherein R is selected from the group consisting of hydrogen 5and alkyl containing from 1 to 3 carbon atoms, n is O, 1 or 2, : I X is selected from the group consisting of fluorine, nitrate, : cyanate, thiocycanate, carbamate, thiocarbamate, nitrate, -O-C ~ NH2~ ~ alkoxy (-OR ), " R~
~I dithiocarbamoyl ~SCN /~ ~ , mercaptide t-SR~ ) 10~ and dialkyldithiophosphate (SP~ ~ whereln R

-2-~z~z~ l represents alkyl containing from l to 12 carbon atom~ or phenyl Z
erein Z 1s nydrogen, ~a~oeen,_1,3 oarbon alkyl, 1-3 carbon alkoxy .or nitro (-NO2), R is alkyl containing ,0, 0 from l to 12 carbon atoms and Y is oxygen,-OC(CH2jmC-O- , O ' 5wherein m is an integer fr~m 2 to lO, inclusive, -OC

sulfur, sulfate or carbonate.
These compounds are particularly effective as control agents for fungi and insects yet do not exhibit the high level of phytotoxicity characteristic of tri-n-alkyltin compounds.
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2~27 The present invention provides a triorganotin compound exhibiting a formula selected from the group consisting of I ~ ~CII2) - r~ SnX and ~ (C~I2)n ~ Sn wherein R is hydrogen or alkyl of from 1 to 3 carbon atoms; N is O, 1 or 2;
X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, carbonate, amide (NH2), amino (NR2 or NRlH), -O-C ~_NH2, H2N ~ , ~3_ C O ~ ~
~ S /R ~
phenoxy, alkoxy (-OR ), dithiocarbamoyl, ~SCN J , mercaptide (SR ), dialkyldithiophosphate ~SP ~ provided that X is not hydroxyl when ~ \OR J
R is hydrogen and n is O; wherein Rl represents alkyl containing from 1 to 12 carbon atoms or ~ Z wherein Z is hydrogen, halogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 3 carbon atoms, or nitro (-NO2) J

R is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, O O
-OC(CH2)m C-O- wherein m is an integer from 2 to 10 inclusive, O O
-OC { >- CO -, sulfur, sulfate, phosphate or carbonate.

~B 3a -1, ~09ZlZ7 ¦; DRTAILED DESCRIPTION OF THE INVENTION
The hydrocarbon groups of the present triorganotin compounds contain a cyclopentyl group either bond:~d directly ¦~ to the tin atom or separated from the tin atom by one or two ! ~ethylene groups. The cyclopentyl group may have as a ~I substituent an alkyl group contain~ng from 1 to 3 carbon ~toms.
l Tri(cyclopentyl~tin and tri(cyclopentylalkyl)tin halides wherein the halogen is chlorine, bromine or iodine ` can be prepared by reacting at least three moles of the i corresponding cyclopentyl or cyclopentylalkyl magnesium halide, CypMgZ or Cyp(CH2)nZ ~ wherein Cyp represents a cyclopentyl i ring, for every mole of an alkyltin trihalide R SnZ 3 wherein !~ 3 R is lower alkyl and preferably contains from 1 to 4 carbon ¦~ atoms. The resultant tetraorgano~in compound, Cyp3SnR , is reacted witn an equimolar amount of a stannic halide 3 SnZ 4 . During the reaction the lower alkyl group R
present on the tetraorganotin compound is replaced by a halogen atom from the stannic halide. The reactions involved in the formation of the present triorganotin compound~ can be ~0 , represented by the following two equations where Z , Z and Z
,~ !
are individually selected from the group consisting of chlorine, bromine and iodine.
1~ , ~t ` . I
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1~ 1 ~L09ZlL7 1 ~) 2 3 ~ 2

3 CypMgZ ~ R Sn~3 -~ Cyp3SnR + 3MgZ Z
9 3 ~ 3 3 Cyp3SnR + SnZ~ ) Cyp3SnZ + R SnZ3 3 2 The aforementioned alkyltin trihalide R SnZ 3 can, in turn, be prepared by reacting the corresponding alkyl halide, R Z , with a stannous halide SnZz as described in ¦ United States Patent 3,340,283~ issued September 5, 1967 to ' Carl R. Glosk~y assigned to M ~ T Chemicals Inc.
The reaction between the stannic halide and tetra-1~ organotin compound should be performed under ar~ydrous ji conditions at temperatures from about -25 to 80C., preferably from +25 to 80C.~ in a hydrocarbon solvent. Prererred solvents include pentane, hexane and cyclohexane.
Preferably the stannic halide is dissolved in an I organic solvent and the resultant solution added dropwise to 1' a second solution containing the tetraorganotin compound in I~
the same solvent. The temperature of the reaction mixture ~s preferably maintained below about 30C. during the addition, which requires about one hour, after which the mixture is heated to a temperature from 35 to 80C. Preferably the temperature employed is the reflux temperature of the reaction mixture. Heating is continued for from about 15 to 60 minutes to ensure complete reaction. The reaction mixture is then allowed to cool to ambient temperature, and extracted with one or more portions of water or aqueous mineral acid. The by-il 3 3 product of the reaction, a monoorganotin trihalide, R SnZ3, i3 " soluble in the aqueous phase of the reaction mixture. Thedesired product remains in the organic phase, and is readily ,1 jl I

1~9Z~LZ7 lsolated by bolllng o~f the hydrocarbon solvent. No rurther puri~ication is usually requiréd, however the product can be distilled if desired. The organic layer is preferably freed of any dlssolved water following the extracting step.
Any of the conventional chemical dehydrating agents are suitable, provided that they wlll not react with either the triorganotin halide or the hydrocarbon solvent. Preferred drying agents include anhydrous magnesium sulfate, anhydrous I sodium sulfate and anhydrous calcium sulfate.
l Tri(cyclopentylalkyl)tin bromides can be prepared by ¦ the gradual addition of bromine to a solution containing the corresponding tetra(cyclopentylalkyl)tin compound. The tetraorganotin compound is, in turn, prepared by reacting a cyclopentylalkyl magnesium halide with a stannic halide in a ~1 molar ratio of 4:1, respectively.
¦ The present triorganotin halides are solids or liquidsl ll at ambient temperature. The halides can readily be converted to' ¦ other derivatives such as the oxide, acetate and sulfate 1i using known reactions. The desired anionic radical can be !! introduced by react~ng the corresponding triorganotin halide, hydroxide or bis(trior~anotin~ oxide Tith the reagent indioated ln tne following table.

109Z~'~7 OR~lANOTIN DERIVATIVE + REAGENT DESIRED PRODUCT
Chloride, Bromide Carboxylic acid + carboxylake, or Iodide acid acceptor, e.K. e.g. acetate an amine " alkali metal salt of "
a carboxylic acid " aqueous solution of oxide tor alkali metal hydroxide hydroxide) " alkali metal alkoxide alkoxlde or alcohol + acid acceptor (e.g. an amine) " alkali metal phenoxide phenoxide or phenol + acid acceptor " potassium fluoride or fluoride hydrofluoric acid " alkali metal sulfide sulfide " alkali metal sulfate sulfate " mercaptan + acid mercaptide acceptor " alkali metal cyanate cyanate " alkali metal khiocyanate thiocyanate " alkali metal thiocarbamate khiocarbamate " alkali metal dithiocarbamate dithiocarbamate 1~921%7 ORGANOTIN DERIVATIVE ~ REAGENT DESIRED PRODUCT
. . . _ _ _ Chloride, Bromide phosphoric acid phosphate or Iodide or alkali metal phosphate .~ alkali metal dialkyldithio-dialkyldithio- phosphate phosphate Oxide or ~ydroxide carboxylic acid or carboxylate anhydride " alcohol ~or phenol) alkoxide (or l - phenoxide) : " hydrofluoric acid fluoride " dilute (10-25 weight sulfate %) aqueous sulfuric " hydrogen sulfide sulfide alkyl or aryl mercaptide mercaptan " carbon dioxide carbonate Hydroxide heat to remove oxide water ;
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The reactlon condltion~ such as preferred solvents, temperatures and reaction tlmes for preparing the derivatives summarized in the preceding table are known ln the art and, I therefore, do not require a detailed description in the present I specification. A comprehensive treatment o~ this sub~ect matter together wlth numerous literature references is j contained in an article by R. K. Ingham et al. that appeared in the October, 1960 issue of CHEMICAL RE~-IEWS (pp. 459-539).
The aforementioned derivatives may be liquids or solids at ¦ ambient temperature, depending upon the type of substituents represented by X or Y.
The present tricyclopentyltin and tricyclopentyl-¦ alkyltin compounds effectively control many types of undesirable ll fungi and insects, particularly mites, when applied to living ¦1 plants that are susceptible to infestations of these organismsO
!~ The combination of fungicidal and miticidal activity is not i common for a single organotin compound. A single application !' f these compounds to living plants or other substrates provides ~I residual and extended control o~ many varieties of ~ungi and 1~ insects for a considerable period of time, the duration of which s dep_ndent to some extent upor mechanical and j biological influences, including weather. Formulations containing the present organotin compounds can be applied directly to the organism to be controlled.

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In preparing compositions ~or application to plants the organotin compound is often augmented or modified by combining it with one or more commonly employed pesticide additives or adjuvants includ:Lng organic solvents, water or other liquid carriers, surfactants to aid in dispersing or emulsi-fying the organotin compound and rinely comminuted solid carriers. Depending upon the concentration of triorganotin compound in these compositions, they can be employed either without additional diluents or as liquid concentrates which are subsequently diluted with one or more additional inert liquids to produce the ultimate treating compositions. In compositions employed as concen-trates, the triorganotin compound can be present at concentrations of from about 5 to about 98% by weight. Other biologically active agents that are chemically compatible with-the present triorganotin compounds can also be added.
The optimum effective concentration of tin compound . ; to be employed as toxicant in a composition is dependant upon whether the organism is contacted with or, as in the case Of insects~ ingests the toxicant. The actual weight of compound constituting an effecti~e dose is primarily dependent upon the susceptibility of the particular organism to a given triorganoti n compound. For control of insects, good results are obtai~ned with liquid or dust compositions containing as little as one part per million by weight of toxicant. Compositions contain-ing up to 90 percent by weight of toxicant can be employed to treat a heavily infested area.

~O~ZIZ7 In the preparatlon of dust composition~, the organo-tin compound can be blended with many commonly employed finely dlvlded solid carriers such as ~uller's earth, attapulgite, bentonite, pyrophyllite, vermiculite, diatomaceou3 earth, talc, chalkg gypsum a~d wood flour. The carrier, usually ln a ~inely divided form, is ground or mixed with the toxicant or wetted wlth a dispersion o~ the toxicant in a volatile liquid. Depending upon the relative proportions of toxicant and carrier, these compositions can be employed as concentrates that are subsequently diluted with additional solid carrier to obtain the desired amount of active ingredient.
Alternatively, such concentrate dust compositions can be employed in combination with various known anionic, cationlc or non-ionic surfactants as emulsifying or dispersing agents to lorm spray concentrates. Such concentrates are readily disper~lble ln liquid carriers to form spray composltions or llquld formulations contalning ~he toxicants in any desired amount. Th~ choice and concentration of surfactant are ; determlned by the abillty of the material to facilitate ~he dlspersi.ng o~ the concentrate in the liquld carrier to produce ~he desired liquid compositlon. Suitable liquid carriers include water, methanol, ethanol, isopropanol, methyl ethyl ketone, acetone, methylene chloride, chlorobenzene, toluene, xylene and petroleum distlllates. Among the pre~erred petrolleum distlllates are those boiling under 400F. at ~¦ atmospher1 pressure and hav~ng a flash po~nt abo~e aoou~ ôOF.

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~'.)!~21;',~ ~

Ll~uid compositions can also be prepared by dissolvlng one of the present triorganotin compounds in a mixture containing a water-immisci.ble organic llquid and a surface active dispersing agent. The resultant emulsifiable concentrate is then further diluted wikh water and an oil to form spray m~i~x~res in the form of oll-in-wa~er emulslons.
In such compo~ltion~l the carrier comprises an aqueous emulsion, i.e. a mixture of water-lmmiscible solvent, emulsifying agent and water. Preferred dispersing agents for these composltions are oil-soluble and include the condensation products of alkylene oxides with phenols and organic and inorganic acids, polyoxyethylene derivatives of sorbitan esters, alky~arylsulfonates~ complex ether alcohols, . . mahogany soaps and the like. Suitable organic liquids to be: 15 . employed in the compositions include petroleum distillates, hexanol, llquid halohydrocarbons.and synthetic organic olls.
The surface active dispersing agents .are usually employed in - the liquid dispersions and aqueous emulsions in the amount Or from about 1 to about 20 percent by weighk of the combined .
~3 ~r~ight o~ ~he dlspersing agent and the active toxicant.
When operating in accordance with the present .
. lnventio~? the organotin compound or a composition cont~.inin~
the co~pound can be applied directly onto the organism to be controlled or to the site to be protected, particularly plants and trees. Application to the follage of plants is convenlently carried out using power dusters, boom sprayers and spray dusters;`~~When employed in this manner the composltion : should ~ot contain any significant amounts o~ phytotoxlc dlluenks. In large scale operations, dusts or low volume sprays may be appl:Led from an aircraft.

1 09Zi.27 ¦¦ The following examples represent prererred embodiments of the present compounds anA their use as fungicides and insecticides, and are not intended to limit the ~I scope of the accompanying claims. All parts and percentages 1 are by weight unless otherwise specified.

EXAMPLES

EXAMPLE 1 - Preparation of Tricyclopentyltin Chloride , and Derivatives Thereof j~ A. Prepara~ tric~clopentyltin ,~
o ! To 24.3 g. (1 g. atom) of magnesium chips heated to a temperature of 40C. under a nitrogen atmosphere was added a 25 cc. portlon of a solution containing 149 g.
(1 mole) of bromocyclopentane dissolved in 750 cc. o~
anhydrous tetrahydrofuran. The reaction was initiated using .i , ~ a few drops of ethylene dibromide. The remaining portion of the bromocyclopentane solution was gradually added during a period of 2 hours while the reaction mixture was heated to the boiling point. Heating was continued for an addltional 1.5`
hours, during which time 15 cc. o~ a 3 normal solution o~
butylmagneslum bromide in tetrahydrofl-~ran was added to react wiih any impurities which could prevent or inhibit the formation of the cyclopentylmagnesium bro~ide. A small particle Or iodine was also added as an initiator for the ~ reaction. The reaction mixture was allowed to cool to ambient temperature and remain at this temperature for about 16 hours, during which time stirring of the mixture was continued. At the end of this period all of the magnesium appeared to have reacted. A 100 cc. portion of tetrahydrofuran !

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iu~32~ z7 ~I was added to compensate for solvent loss resulting from ,~ evaporation, after which the reaction mixture was heated to the bolllng point for two hours. A 500 cc. portion of this solution containing o.66 mole of cyclopentyl magnesium bromide ¦
, was added dropwlse to a stirred solution of butyltin trichlorld~
56.4 g.~ 0.2 mole) dissolved in 250 cc. of dry benzene. The addition required one hour and was conducted under a nitrogen atmosphere. During the addition the temperature of the 1, reaction mixture was maintained below 45OC. Following completion of the addition the reaction mixture was heated to ~ the boiling point for one hour, then allowed to cool to 'i ambien~ temperature and stirred for 18 hours. To the resultant mixture was added a solution containing 200 cc. water and 35 g.
of citric acid. The organic phase of the resultant two phase ~5 liquid was separated and the water ~resent therein removed " using a portion of anhydrous magnesium sulfate, which was subse~uently removed by filtration. The solvent was evaporated~
under reduced pressure to yield 72.25 g. (94% yield) of a l!iquid, butyltricyclopentyltin, exhibiting a refractive .' Z7 index (n D) of 1.5220. This liquid was extracted 1 time with methanol. Analysis by yapor phase chromatography indicated that ihe product was 96.7% pure. The product was ~ound to contain 30.24% tin. The calculated value for butyltricyclo-;! pentyltin is 30.98%.
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Il l Zl.~7 B. Cleavage of Butyltricyclopentyltin to ~! T icyclopentyltin Chloride 'i A 19.2 g. (0.05 mole) portion of the butyltricyclo- ¦
Il pentyltin prepared as described in part A of this example ~, was dlssolved ln 75 cc. of heptane. To this solution was added a solution containing 13.0 g. ~0.05 mole) of anhydrou~
stannic chloride and 75 cc. heptane. The addition required 20 minutes3 following whlch the resultant mixture was heated to the boiling point for 30 minutes and then allowed to - I
1~ cool to ambient temperature. A solution obtained by combining ¦

4 cc. of 12N aqueous hydrochloric acid and 96 cc. water was then added to the reaction .nixture with vigorous stirring Ij both durlng the addition and f'or five minutes thereafter.
il The organic layer of the resultant two-phase liquid was . .
~I combined with an aqueous hydrochloric acid solution prepared as described hereinabove. I'he organic layer was isolated and the water therein removed using a quantity of anhydrous ~ !' !
magnesium sulfate. The heptane was then evaporated under reduced pressure to yield 17.8 g. of pale yellow crystals l~ exhibiting a melting range of 41-44C. Upon analysis by vapor phase chromatography the product was found to be 97.2%
pure. Following a recrystalization from pentane at -7~C., the~
product melted between 44 and 45C. and was 99.6% pure, as `
determined by vapor phase chromatography.

~ Tricyclopentyltin hydroxide was prepared by adding I a solution of the corresponding chloride (18.1 g. of the chlorlde in 40 cc. of tetrahydro~uran) to a solution containing, 3.0 g. o~ sodium hydroxide, 12 cc. water and 12 cc. methanol. I

" The addition was gradual and required 20 minutes, at which time !
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, 12 cc. of water were added. The resultant slurry was stirred i:
for 0.5 hour, at which time 150 cc. of water were added to I completely precipitate the product. The solid was isolated I and washed with deionized water until no detectible amount 1, of chloride ion was present in the water. The solid was then 'l dried in a circulating air oven maintained at a temperature , i I
of 40 C. Analysis by potentiometric titration indicated that the hydroxide was between 98.6 and 99.1% pure.

¦, C. TricycloPentyltin Fluoride 10r~ Tricyclopentyltin fluoride was prepared from the corresponding hydroxide. A solution containing 300 g. of i - ~` tricyclopentyltin hydroxide and 3600 cc. of tetrahydrofuran wasi ; clarified by filtration. To this solution was gradually I added a solution obtained by combining 50 g. of a 48~ aqueous " hydrofluoric acid solution with 150 cc. of water. The resultant mixture, which contained a white precipitate, was heated to the boiling point (64C.) for 0.25 hour, then cooled to ambient temperature filtered, and washed sequentially with 1 liter of a 0.1% aqueous hydrofluoric acid solution, 2Q ~ lter deionized water and 500 cc. methanol. After being dried under reduced pressure at a temperature of 50~C. the white solid (280 g.) melted from 275 to 280C. with evidence of decom~osition. The solid was found to contain ~, 34.05% tin and 5.32% fluorine. The calculated values for ' tri(cyclopentyl)tin fluoride are 34.40% tin and 5.51% fluorine.
~i i , ll i !l - ,¦ D. Tricyclopentyltin Acetate To a suspension of 17.15 g. tricyclopentyltin hydroxide in 100 cc. o~ dlethyl ether was added dropwise over 0.25 hour, a solution of 3.15 g. acekic acid (glacial) in 'l 100 cc. diethyl ether. The solids dissolved and the solution was stirred for 0.25 hour at 25C. About 15 g. of anhydrous magnesium sulfate were added to the solution and the mixture stirred for 1 hour to remove water formed during reaction.
~ The mixture was then filtered and solvent removed on a rotary .~ 10 i! evaporator to yield 20 g. of a white solid. The solid was placed in a desiccator over sodium hydroxide pellets and held ~ under reduced pressure for 48 hours to remove excess unreacted ; ,; acetic acid. The product, a white solid, weighed 18.7 g~ and il melted from 52 to 54C.

l~ Analysis: Found: Tin, 30.65%; Acid No. 160 , Calculated: Tln, 30.82%; Acid No. 146 li ¦I E. Tricyclo~entyltin ?-Ethylhexanoate A 17.1 g. portion of tricyclopentyltin hydroxide !~ and 7.2 g. of 2-ethylhexanoic acid in 200 cc. benzene were heated to the boiling point and the ~y-product water (o.84 cc.) removed using a Dean-Stark trap. The benzene was evaporated ~i under reduced pressure to yield 23.5 g. of a yellow liquid, n D = 1.5068.

~Analysis: Found: Sn, 25.14%; Acid No. 123.6.

,iCalculated: Sn, 25.29%; Acid No. 119.5. ~

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¦l F. Tricyclopent;yltin Benzoate j The benzoate was prepared using the procedure , described for the 2-ethylhexanoate using 17.1 g. tricyclo- ¦
,' pentyltin hydroxide and 6.1 g. benzoic acid. The product, ~ recrystallized once from n-hexane at -70C., weighed 19.6 g.
and melted from 37 to 38.5C.
Analysis: Found: Tin, 26.42%; Acid No. 131.
,~ Calculated: Tin, 26.54%, Acid No. 125.

G. Bis[tricyclopentyltin] Oxide i, ¦¦ By heating a sample of the hydroxide for 6 hours at ~ 100C. under a pressure o O.5 to 1.0 mm. Hg., a sample of '~ the bls-oxide was prepared which showed a strong absorption in the infra-red spectrum at 785 cm. , attributable to the ~ Sn-O-Sn linkage. No absorption character stic of the Sn-OH
linkage was evident, indicating that the com~ound had been entirely dehydrated to the bis-oxide.
~5 H- Tricyclopentyltin Phenoxide i The phenoxide was prepared by heating to the boiling point a solution containing '7.15 g. t~~cyolopentyltin ~ hydroxide, 4.71 g. phenol and 200 cc. benzene. The by-product i~ I
water ~10.8 ccO) was removed during the reaction.
Evaporation o~ the solvent yielded 21.05 g. of a yellow oil, 1, 25 '' n D = 1.~627.
` Analysis: Found: Sn, 28.04; -OC6H~ residue, 2400%.
Calculated: Sn9 28.32; -OC6H5 residue, 22.2%.

~l -18-3Z~LZ7 I Tricyclope--nt~lt-l-n--c-hloride (from the h~droxlde) I
To a suspension of 17.15 g. tricyclopentyltin hydroxide in 100 cc. of pentane was added 6cc. of ¦¦ a 36% aqueous hydrochloric acid solution with stirring. The organic phase was separated and dried over magneslum sulfate after adding 3 g. sodium sulfate and 100 cc.
ether to break up the emulsion. After filterlng, the pentane ,' phase was stripped of solvent to yield 17.05 g. of white ~- crystals, melting from 39.5 to 42.5C.
1, Analysis: Found: Sn, 32.60; Cl, 9.82%.
Zli Calculated: Sn, 32083; Cl, 9.81%.
' Analysis by vapor phase chromatography indicated that ,~ the product was over 95% pure.
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Z,l J. Tricyclopentyltin Dimethy'l'dithioc'arb'ama'te . ,1 - 1, ~ To a solution containing sodium dimethyldithiocar-'' bamate dihydrate t5.38 g.) and 50 cc. water was added a ' solution containing 10.84 g. tricyclopentyltin chloride and ~! 50 cc. acetone. The mixture was stirred ~or 1 hour., then , .
~ poured into a separatory funnel. The lower phase was added to Z, - lG0 cc. of acetone. The aqueous phase was extracted once ~ with 50 cc. hexane, the hexane added to the acetone solution and the mixture dried using anhydrous magnesium sulfate for l l/2 hours. After filtering, the solvent was removed under reduced pressure to yield 13.15 g. of a beige solid, that Z
j melted from 55 to 57C.

Analysis: Found: Sn, 26.67; S total 14.48%.
il Calculated: Sn, 26.60; S total 14.30%. 3 - I, 109Z~ 7 , K. Tricyclopentyltin 4-Acetylaminobenzoate Il .
A mixture containing 17.15 g. tricyclopentyltln ' hydroxide, 9.0 g. 4-acetylaminobenzoic acid and 250 cc. benzene ,I were heated to the boiling point using a Dean-Stark trap to ,t isolate the water formed. A o.8 cc. portion of water was 5 I' collected over a 1.5 hour period. The hot solution was filtered and allowed to cool to room temperature as crystals were deposited. The crystals were filtered and dried under vacuum.
Yield=21.49 g. of white crystals melting from 169 to 174C.
j Analysis: Found: Sn, 23.87%; Acid No. 113.
' Calculated: Sn, 23.54%; Acid No. lll.

L. Tricyclopentyltin 2-Aminonicotinate ~) A mix~ure containing 17.2 g. tricyclopentYltin - hydroxide, 5.90 g. 2-aminonicotinic acid and 250 cc. benzene ``
was heated to the boiling point using a Dean-Stark trap to collect the water (0.9 cc.) ~ormed as a by-product~ The hot ' solution was filtered and allowed to cool to room temperature, during which time it deposited 22.26 g. of yellow solids melting from 92 to 98C. The crude product was recrystallized ~rom 250 cc. heptane to yield 11.48 g. of ~hite crystals melting t.i from lOl to 103C. When evaporated to 1/2 o~ the original volume under reduced pressure a~d cooled to 0C. the heptane ' solution deposited another 7.5 g. of white crystals melting from 99 to 101C. Both crops were combined and analyzed.
Analysis: Found: Sn, 26.29%; Acid No. 123.
~ Calculated: Sn, 25.63%; Acid No. 121.

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: I! M. Bis~tric,yclopent~ltin] Su~lr~de To an aqueous solution contalning 12.1 g. o~ disodium I ¦ ethylenebis(dithiocarbamate) in 150 cc. water was added dropwise over 1/4 hour a solution containing 25 g. tricyclo-1; pentyltin chloride and 150 cc. acetone. Sollds initially formed, however during l hour of stirring the solid changed to Il a yellow oil suspended in a viscous liquid. The mixture was poured lnto a separatory funnel and 75 cc. of ether were added.
~ The aqueous phase was removed and the organic phase added to lO0 cc. acetone. The organic phase was dried over anhydrous magnesium sulfate. Evaporation of the solvent yielded 31.19 g.
i of a mixture of yellow viscous liquid and solids. A 200 cc.
;
portion of benzene was added and the mixtur-e heated. The .
crude product was then cooled to 25C. and filtered. The - 15 filtrate was stripped of solvent to give 24.25 g. of a yellow liquid plus solids. This mixture was filtered and over a period of four days the filtrate partially solidified. The resultant mixture was recrystallized from 100 cc. isopropanol to yield ` 6.6 g. of yellow crystals melting from 70 to 72C.
Analysis: ~ound: -Sn, 34.87; S total3 4.39%~
Calculated for [~C,Hg)gSn]2 S
Sn, 34.70, S total, 4.69%.
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I~ N. Tricyclo~entyltin 2-ThioE~ e Carboxylate A 18.8 g. portion of tricyclopentyltin hydroxide and 6.4 g. 2-thiophene carboxylic acid were heated to the boiling ; , point for 2 hours in 200 cc. benzene, during which time 0.6 cc.
~ water collected in the Dean Stark trap. The hot reaction mixturè
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was filtered9 then freed of solvent under reduced pressure to ¦ yield 24.54 g. of a whlte solid meltlng ~rom 58 to 62C.

'~! Analysis: Found: Sn, 26.43%, Acld No. 118.
~i Calculated: Sng 26.20%; Acid No. 124.

I 0. Bis[tricyclopentyltln] Adi~ate The adlpic acid derivative was prepared ln a manner similar to the foregoing procedure N using 18.8 g. tricyclopentyl-tin hydroxide and 3.65 g. adiplc acid. A o.85 cc. portion ~ of water was collected during the reaction. On removing the benzene, 20.63 g. of a white solld were isolated and melted from 61 to 65C. Recrystallization from 100 cc. methanol ; ~ yielded 18.55 g. of white crystalæ that melted from 66 to 69C.

-~ Analysis: Found: Sn, 29.46%; Acid No. 142.
~; Calculated: Sn, 29.81%; Acid No. 141.
i, ..
~ P. Tricyclopentyltin Thiophenoxide ~t .
` A mixture containing 18.8 g. tricyclopentyltin hydroxide, 5.5 g. thiophenol and 200 cc. benzene was heated to the boiling point. A total of o.84 cc. of water was collected }
' over a 1.5 bour period. The resultant solution was flltered and solvQnt evaporated to yield 22.9 g. of yellow liquid ;: 2 ~
product~ ~ D = 1.5885.

Analysis: Found: Sn, 29.25; S~ 6.68%.
` Calculated: Sn, 25.29; S, 6.82%.

`ti~ !
,~ 1i il -22-,.~
;I t 1()~21~7 Q. Trlcyclopentyltin ]~2,4-Triazole A mixture containing 18.8 g. tricyclopentyltin hydroxide, 3.45 g. 1,2,4-triazole and 200 cc. toluene was ~I heated to the boiling point for 1 hour during which time 0.82 cc. of water was collected using a Dean-Stark trap.
A 100 cc~ of toluene was then distilled off and the hot solution filtered. On cooling, crystals were deposited which when isolated and dried, weighed 19.1 g. One recrystallization ij from boiling toluene yielded 17.9 g. of product melting from I, 204.5 to 210C.
¦¦ Analysis: Found: Sn, 30.16, N, 11.37%.
Calculated: Sn, 30.12; N, 10.66%.

EXAMPLE 2 - Preparation of Tri(2-cyclopentylethyl)tin Bromide l and Derivatives Thereof l A. Tetra(2-cyclopentylethyl)tin ¦¦ To a solution containing 0.5 mole of cyclopentylethyl magnesium bromide prepared in the conventional manner from 0.5 mole 2-cyclopentyl-1-bromoethanel 0.5 g.-atom magnesium chips and 250 cc. tetrahydrofuran was added a solution containing 26.0 g. (0.1 mole) stannic chloride and 100 cc.
benzene. The addition was gradual and required 0.5 hour to complete, at which time the reaction mixture was heated to the ¦
boiling point for 2 hours then allowed to cool to ambient Il temperature. The product was then hydrolyzed using a solution 1i containing 15 g. of citric acid and ?50 cc. of water. The organic portion of the resultant two-phase liquid was isolated ~ and the water therein removed usin~ anhydrous magnesium sulfate ¦I The solvent was evaporated under reduced pressure to yield ¦ 59.3 g. of a semi-solid material which was comblned with 100 cc~
of isopropanol and stirred for one hour. The resultant slurry ¦

li ~

~.~9z~z7 was flltered, washed wlth cold (0C.) methanol and dried 'co ! yield 49.15 g. of a whlte solld that melted from 74 to 77C.
I Analysis: Found: Sn, 22.41%; Cl, 0.13%.
!I Calculated: Sn, 23.40%; Cl, 0.0%.
i1 l, B. Cleavage of Tetra(?-cvclopentyleth~l)tin I
~ o a solution containing 40.6 g. tetra(2-cyclopentyl-j ethyl)tin, 90 cc. chloroform and 35 cc. methanol maintained at 0C. was added dropwise over 5 hours a solution containing "
I, 12.8 g. br~mine in a mixture of 50 cc. methanol and 50 cc.

chloroform. When the addition was complete, the mixture was !~ I
allowed to warm to 25C. then the solvents were evaporated under reduced pressure to yield 41.7 g. of white solids. These were ,'' t recrystalllzed from 150 cc. methanol by cooling to -20 C.
The crystals were filtered, washed wikh methanol at a temperature f -600C and dried under reduced pressure. The first crop i of crystals weighed 24.4 g. and melted from 55 to 58OC. The mother liquor solution was evaporated to 1/3 of the original volume then cooled to 0 C. whereupon it deposited a second crop of cr~stals which were filtered and dried. This crop ~0 weighed 7 9 g. and melted from 58 to 60. The two crops when combined weighed 32.3 g.

Analysis: Found: Sn, 23.90%; Br, 15.22%.
Calculated for tri(cyclopentylethyl)tin bromlde:
i Sn, 24.22%; Br, 16.31%.

`~ _z4_ %~

l C. BisCtri(cycloventylethyl)tin; Oxlde ll I To a solution contalning 1.6 g. (0.04 mole) of sodium ,i hydroxide, 50 cc. methanol and 50 cc. water was added a I~ solution containing 9.8 g. trl(cyclopentylethyl)tin bromide, 1 5 !. loo cc . methanol and 40 cc.~acetone. The additlon was gradual and required 10 minutes. Following completlon of the addition the reaction mixture was heated to the boiling point (670C.) for two hours, then cooled to ambient temperature, at whlch ,~ time 150 cc. of water and 100 cc. of diethyl ether were added and the resultant mixture stirred vigorously for five minutes. The organic phase of the resultant two-phase liquid was isolated and freed of water using anhydrous ; magnesium sulfate. The drying agent was removed after two hours and the solvent evaporated under reduced pressure to yield 8.2 g. of a yellow oil which was found to contain 27.33%
ii tin. The tin content of pure bis[tri(cyclopentylethyl)tin]
oxide is 28.38. Analysis by vapor phase chromatography demonstrated that the compound was 91.4% pure.
.. i;
EXAMPLE 3 - Preparation of tri(2-cyclopentylmethyl)tin Bromide lZ Tetra(cyclopentylmethyl)tin was prepared using the procedure described in Example 2 from cyclopentylmethyl- ¦
magnesium bromide and stannic chloride. The product was a ! ~
solid melting from 63 to 66~C. and contained 27.86% tin.
The calculated tin content Of tetra(cyclopentylmethyl)tin ' is 26.30%.
'I
i~1, , .

il -25-, .

lO~ .Z~
I

Tetra(cyclopentylmethyl)tin was cleaved by reactlng the compound with bromine uslng the procedure described in li the preceding example. Following one recrystallization ~rom ~ methanol the product melted from 32 to 340C. and was found !~ to contain 26.34% tin and 17.84% bromine. The calculated values for tritcyclopentylmethyl)tin bromide are 26.49% for tin and 17.84% ~or bromine.

EXAMPLE 4 - Preparation of Tri(cyclopentylmethyl)tin Chloride and the Corresponding Oxide i( I
l,~ Methyltri(cyclopentylmethyl)tin was prepared by reacting 0.425 mole of cyclopentylmethylmagnesium bromide with i 30.5 g. methyltin trichloride in 150 cc. of benzene. The , crude product was isolated from the reaction mixture as a ~`
yellow~oil (48.3 g.) of refractive index 1.5192 at 24 and in 85% purity. After washing twice with methanol (75 cc. and 25 cc ) and distillation under reduced pressure 33.8 g. of product boiling at 140QC. under 0.3 mm. Hg were obtained~ i j. 24 n D = 1.5230. Vapor phas~ chrom~tography showe~ ~he material to be 95.6% pure.

1l To a solution o~ methyltri(cyclopentylmethyl)tin (26.8 g.) in 100 cc. of pentane, was added dropwise a solution !, . ' - _. I
of stannic chloride (18.2 g.) in 100 cc. pentane over 20 minutes. The resultant yellow solution was heated to the ` boiling point for 0.5 hour then cooled to room temperature.
~ The mixture was combine_ with a solution containing 2 cc. 12N
hydrochloric acid and 98 cc. water, following which the organic phase was separated and washed with another portion of ,j 11 ~

1109ZlZ7 1~ ~
2 cc 12N hydrochloric acid and 98 cc water. The organic phase was again separated and the water therein removed using anhydrous magnesium sulfate. After filtration, the ,~ solvent was removed under reduced pressure to yield 28.20 g.
5 Il, of a white solid that melted from 88 to 90C-Analysis: Found: Sn, 29.21; Cl, 8.87%.
~t Calculated for tri(cyclopentylmethyl)tin chloride:
Sn, 29.41; Cl, 8.80%.
~j Vapor phase chromatography indicated the compound to be i 98.3% pure.
., ~
is[tri(cyclopentylmethyl)tin] Oxide To a solution containing 1.8 g. sodium hydroxide,10 cc. water and 10 cc. methanol was added dropwise a solution containine 12.11 g. tris(cyclopentylmethyl)tin chloride and , ' , 25 cc tetr2hydrofuran over 15 minutes. An oil formed initiall~
and dissol~ed as the addition proceeded. When the addition was complete, the solution was stirred at 25C. ~or 0.5 hour. ¦
A 300 cc. portion of cold (10C.) water was added followed by 200 cc. of diethyl ether with vigorous stirring. The organic ~ phase was isolated and the water therein removed using anhydrous ~agnesium sulfate. After filtratlon the solvent was removed under reduced pressure to yield 11.28 g. of a waxy solid melting from 59 to 630. The crude product was purified b~ adding 60 cc. methanol and cooling to 0~C.
whereupon a small amount of solid material precipitated. The '~ solid was removed and the ~iltrate evaporated under reduced pressure to yield 11.35 g. of yellow liquid, n D = 1.5296.

Analysis: Found: Sn, 30.16.
Caleulated for bis[tri(cyclopentylmethyl)tin] oxide:
ji Sn, 31.56. `
Assay by potentiornetric titration = 92.6% purity.

lO~Zl'~q I ~' EXAMPLE 5 - Preparation of Tr1(2-methylcyclopenkyl)tin Chlorlde and the Corresponding Oxide.
A. Methyltri(2-methylcyclopent~l)tin To a solution contalning 0.31 mole of 2-methyl-cyclopentylmagnesium bromide in 15C cc. of tetrahydrofuran was , added a solution containing 21.6 g. methyltin trichloride in 150 cc. dry toluene over a period of l hour. When the ~! addition was complete, the mixture was heated to the boiling l~ point ~or 2 hours and then stirred at 25C. for 16 hours. The I
reaction mixture was then hydrolyzed uslng a solution containing 25 g. cltric acid and 250 cc. water. The organic phase was `` separated and the water therein removed using anhydrous i/
' magnesium sulfate. The liquid phase was then evaporated under I
, .
reduced pressure to yield 25.45 g. of crude product. Low i boiling impurities were distilled off at from 25 to 75C. under¦
1~
IJ a pressure of 0.1 mm. Hg. The residue, which contained the i desired product, weighed 33.85 g. and exhibited a refractive index of 1.5192 at 24C.
Analysis: Found: Sn, 30.11.
,~ Calculated for methyl tri(2-methylcyclopentyl)tin: ,3 Sn9 30.98.
9. T~i(2-methylcyclcpentjl)tin Chloride To a solutlon containing 13.4 g. of methyl tri(2-methylcyclopentyl)tin and 50 cc. of hexane was added over a 0.5 hour period a solution containing 9.1 g. of stannic , chloride and 50 cc. of hexane. Following completion of the ;, addition the resultant mixture was heated to the boiling point ¦¦ for 15 minutes then cooled to 25C. The reaction mixture was 5,~' then hydrolyzed by addition of a solution containing 2 cc.
, il ~ 28-3' ~ I
., . I

i 1~3Z~Z7 1' concentrated (12N) hydrochlorlc acid and 100 cc. of water The organic phase of the resultant two-phase liquld was ''I isolated and combined wlth a second portion of the afore-ll mentioned hydrochloric acid solution. The organic phase was ', again isolated and the water therein removed using a portion of anhydrous magnesium sulfate. The liquid phase was then evaporated under reduced pressure to yield 14 g. of a yellow oil that exhibited a refractive index (~ D) of 1.5333 and 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.
! I
C. Bis~trit2-methylcyclopentyl)tin] Oxide ' Bis[tri(2-methylcyclopentyl)tin~ oxide was prepared by gradually adding a solution containing ~.l g. of the !~ corresponding chloride (prepared as described in the foregoing ., , ; paragraph) 25 cc. methanol and 15 cc. acetone to a solution containing l.2 g. of sodium hydroxide, 20 cc. water and 50 cc. I
methanol. The addition required 0.5 hourg following which the ¦
'I
~ 'I resultant solution was heated to the boiling point for 10 .. !
~ 20 ; minutes, then cooled to 15C., during which time 300 cc. of .. , ~
water were gradually added. The resultant mixture was stirred for l hour while the temperature was maintained at 15C. A
~I 50 cc. portion of diethyl ether was then added while the mixturè
; ~ was stirred at high speed. The organic phase of the resultant !
25 ~ `' two-phase liquid was isolated and the water therein removed using anhydrous magnesium sulfate. The liquid was then evaporated under reduced pressure to yield 7.6 g. of a pale j~ -29-i i i~ 1.

g~Q9~LZ7 yellow oil which was found to contain 30.54% tin. The calculated tln content of bis~tri(2-methylcyclopentyl)tin~
oxide is 31.56%. A potentiometric titration of the product indicated that it was 98% pure.

Biological Activity o~ Trlcyclopentyltin and Tri(cyclopentylalkyl)tin Compounds ; The following procedures were employed to evaluate the efficacy of the present triorganotin compounds in I controlling a number of representative fungi and insects.
~ Procedure 1 - Employed Using Two-spotted Spider Mite (Tetranychus urticae), Beet Army Worm (Spodoptera exigua) and Cabbage Looper (Trichoplusia ni).
A cotton plant with two fully expanded leaves is ¦l dipped into an aqueous dispersion of the tesk compound. An ¦~ additional portion is in~ected into the soil at the root zone.
Lepidopterous insect larvae are dipped into the water dispersion and placed in petri dish cages clamped around the ~treated foliage. When using the two-spot~ed spider mite as the test insect the dipping step is not performed since the ,~ mites are on the leaf before the plant is treated. A mortality count is taken six days after treatment.
Procedure 2 - Employed Using Tobacco Black Shank Fungus (phytophthora parasitica var.- nicotiane)O
¦I Tobacco plants are transplanted into soil infested ll wlth the test organism. Immediately after transplanting the soil is drenched with a solution o~ test chemical. The test ¦1 is graded on the basis of plant survival.

. I

lO~)Z1~7 Procedure 3 - Ernployed Using Bean Mildew (Erysiphe polygoni).
Bean seeds are planted in fumigated soil which is then drenched with a solution of the test compound. When the plants reach a suitable size they are inoculated with the fungus. After 7 days the relative number of healthy plants is noted.
Procedure 4 - Employed Using Grape Downy Mildew (Plasmopara viticola) Rice Blast (Pericularia oryzae) and ! Apple Powdery Mildew (Podosphaera leucotricha).
~ost plants, (grape, rice or apple, depending upon the fungus) are sprayed with a water suspension of the test compound and then inoculated with the pathogen. After disease ¦
symptoms are well developed on untreated control plants the 1i test plants are graded for disease control.
Procedure 5 - Secondary Evaluation of Activity In Combatting Two-spotted Spider Mite (Tetranychus bimaculatis) I l¦ and Aphid.
¦I Bean plants infested with the organism are sprayed ll with a water disperslon containing the test compound. The , percent mortality is observed three days after spraying ~¦ Procedure 6 - Employed Using Codling Moth ~arvae (Carpocapra pomonella).
I Codling moth eggs are placed on a paraffin surface ¦I that has previously been treated with a water dispersion of ~ the test compound. The paraffin is perforated, allowing the li newly hatched larva ~o feed on an underlay of food. After ¦~ six days a mortality count is made.

109Zl'7 Procedure 7 - Employed Using bollworm Larvae Five third instar bollworm larvae are placed in petri plates containing a layer of semi-synthetic diet. These ~ larvae are sprayed with 3 cc. of a 400 ppm solution or I suspension of the chemlcal from a distance Or 15 inches using a Spraying Systems Company nozzle 40100-120. After spraying, ~I the petri dish cover is replaced with a fiber brewer lid to il permit limited air exchange. Following a holding period of ll up to 3 days, mortality counts are made.
Ij Procedure 8 - Employed Using Apple Scab (Venturia inaequalis).
Apple seedlings are infected with the fungus. The seedlings are then sprayed with an aqueous solution or sus-pension of the test chemical. After a period of incubation ~, the plants are rated for disease control.
¦I Procedure 9 - Employed Using Hornfly Larvae The test compound is mixed with caIf feces and horn~ly eggs are introduced. After 2 days observation is made to determine the presence of fly larvae.
¦, Procedure 10 - Employed Using Cabbage Looper ,ll (Trichoplusia ni) To Determine Sllstems Activity.
A water dispersion of the test compound is injected into the root zone of a bean plant that is infested with the ~ cabbage looper. Mortality counts are made 3 to 6 days after I treatment.

ll -32-109Z~ 7 Procedure 11 - Employed Using Cabbage Looper (Trichoplusia ni).
A bean plant is sprayed with a water dispersion of ~est compound and a number of cabbage loopers are placed on the treated foliage. A check for mortality is made after 3 days.
Procedure 12 - Employed Using Cabbage Looper To ¦ Determine Ovicical Activity.
The test chemlcal is dissolved in a suitable water-ll miscible solvent and diluted with water to the desired concentration. Eggs of the cabbage looper, having been deposited by the adult insects on paper toweling or other 3 ~ ~ substrate~ are fastened to the underside of a test plant leaf ; I~ with methocel or other appropriate adhesive. Egg sheets are 1 selected having 25-50 eggs per plant. Cotton or other 3 ¦l appropriate host plants are used. The leaf of the plant to I~ which eggs are attached is dipped in the solution containing 5 ~¦ the test chemical. Ovicidal observations are recorded 3-5 Il days after treatment. Inactive materials show large areas of l foliage consumed by freshly emerged larvae.

[J9Z~

Procedure 13 - Employed Using Western Spotted j Cucumber Beetle Larvae.
¦ Seventy-five grams o~ air-dried soil are placed in 1 236 cc. capaciky round bottle and treated with sufficient ,' volume of a solution containing 400 ppm of the chemical to give 25 ppm of toxicant on an air-dried soil basis. The ~ treated soil after being allowed to air dry is mixed by j! shaking and rolllng.
1~ Eggs of the western spotted cucumber beetle (laid over a period Or 3 or 4 days) are collected and a measured , quantity of eggs are suspended in water. The egg concentration i is 70-80 eggs/0.5 cc. of solution. A portion of the suspension ' conkaining about 50 eggs is pipetted into the bottom of a clear ii , plastic medicinal vial. An amount of treated soil sufficient - 15 ` to cover the eggs is added, a corn seed is placed on the soil and covered with additional treated soil.
i' The soil3 eggs and seed mix is watered and additional water is added as necessary to maintain growth of the seedling I ~ corn plant. Care must be ~aken not to add too much water or ~ the larvae will drown. After a period of from 6-9 days an observation ls made to determine the presence of larvae both on top of the soil and at the roots of the seedling.

1, _34 !i ~

~11 ' ",, Il . .' ., . , . ~, lO~Z1~7 Procedure 14 - Employed Using Codling Moth Larvae To Determine Ovlcidal Activity And Control Of Newly Hatched Larvae The test chemical is dissolved in a small amount of a suitable water-miscible solvent and diluted with water to achieve the desired concentration. The chemical solution is I applied to apples or pears which are then covered with eggs ¦ of the codling moth. The fruit is then incubated for from ii eight to ten days ln a greenhouse. The number of living and ~i dead larvae are then counted and compared with a sample of untreated ~ru1t used as a control.
¦ Procedure 15 - Employed Using Mosquito Larvae ¦ Third or early fourth instar larvae of Aedes aegypti are used for the test organiem. Twenty to twenty-five larvae ~/ are placed in distilled water containing the candidate chemical.
Activity I8 recorded as the concentration (p.p.m.) constituting ¦ a lethal dose ~or 95 percent o~ the population (LDg~).
¦ Procedure 16 - Employed Using Apple Powdery Mildew I ~ ¦! Aqueous solutions or suspensions of the experimental 20~ chemical are poured into cups of vermiculite in which plants are gro~7ing.~ The aqueous system usua'ly contains acetone and a wettlng agent, both in non~toxic amounts. Two to four days after the compound is appl~ed the leaves are wet with a 1l spore suspension of apple powdery mildew. The plants are ' then put in a greenhouse. When disease symptoms are clear, ~I the plan~s are graded. Untreated plants are rated as "0%
!~ control" and the disease ~ree plants are rated as 100% control.
I . .. ..

Il .. , ..,':"' ', :' " ,,,' I

~19~ 7 The accompanying ~ables summarize the data obtalned uslng the aforementioned procedures with representative compounds encompassed by the accompanying claims.
I TABLE I
Biologlcal Activity of Tricyclopentyltin Hydroxide Again~t - Fungi Organism Proc.No. Concentration Control Rating : (p.p.m.) (%) - Tobacco Black Shank 2 25 100 l 2 6.3 100 j Bean Mildew 3 25 100 Grape Downy Milaew 4 100 100 4 6.2 95 Rice Blast 4 100 93 ~l ~ 4 25 67 , .l Apple Powdery Mildew 4 loo loo TABLE II
Biological Activity of Tricyclopentyltin Hydroxide Against Insects Organism Proc. No. Concentration Control Rating Spider Mite 5 400 100 i 5 100 100 :: ~25 1 5 25 86 ~ li Beet Army Worm 1 400 100 ;1 ~ Cabbage Looper 1 100 100 Codling Moth Larvae 6 400 loo Bollworm Larvae 7 4bo loo I Aphid 5 400 100 ! -11 ' lO~Z:1.27 TABLE III
Blological Activity Or Trlcyclopentyltin Chloride A~ A
Fungicide Or~anism Proc. No. Concentration Control Rating Apple Scab 8 100 90 I Rice Blast 4 400 95 I Apple Powdery Mildew 16 - 100 70 ¦ TABLE IV
¦ Biological Activity of Tricyclopentyltin Chloride As An Insectic~de Or~anismProc. No. Concentration Control Ratin~ ¦
! (p,p.m.) ¦I Cabbage Looper1 400 100 Codling Moth Larvae 14 400 100 TABLE V
,I Biological Activity of Tricyclopentyltin Acetate As A
Il Fungicide ', Or~ ismProc. No. Concentration Control Rating i (p.P.m.) Grape Downy Mildew 4 400 100 ~1 100 90 ¦, Apple Powdery Mildew 4 100 90 li , 1~ Biological Activity of Tricyclopentyltin Acetate As An jj Insecticide ; Organism Pro~ No. Con(centration Control Ratin~

ll Cabbage Looper 12 400 90 Cucumùer Beetle Larvae 13 25 100 11 .

lO~lZl'~7 iTABLE VII
. .. .
; Biological Activity of Tricyclopentyltin Fluoride As An Insecticide And Fungicide Organism Proc. No. Concentration Control Ratln (P~P.-m.-) Spider Mite 1 400 99 li Cabbage Looper 1 400 100 - !I Codling Moth Larvae 14 400 100 j, Grape Downy Mildew4 400 100 I , 100 94 ~ 50 80 Rice Blast 4 400 96 ' Apple Powdery Mildew 4 100 90 TABLE ~III !
Biological Activity of Tricyclopentyltin Bromide iI Pr~ No. Conc~ntration Controlr~R)ating l Spider Mite 1 400 100 Cabbage Looper 1 400 1803 Mosquito Larvae 15 1 100 , Tobacco Black Shank 2 25 100 25.... ', ~rape nowny~.r~ildew4 400 97 : !l loo loo '' Apple Powdery Mildew 4 400 90 i' 100 97 1 6.3 75 ; -38-I
l . l lZiZ'7 TABLE IX
Biological Activity of Tri(cYCloPentYlethYl)tin Hydroxide . Organism Proc. No. Concentration Control Ratin~

Spider Mite 5 400 95 . 100 98 Grape Downy Mildew 4 400 1~0 ~ . 100 55 Apple Scab 8 400 100 TABLE X
Biological Activity of Tri(cyclopentylethyl)tin Bromide 'I Or~anism Proc. No. Concentration Control Rating Cabbage Looper 1 400 83 Horn~ly Larva 9 100 100 : I Tobacco Black Shank 2 25 100 ~ Apple Powdery Mildew 4 400 75 Il , I
¦¦ TABLE XI
,j Biological Activity of Tri(2-methylcyclopentyl~tin Chloride Organism Proc~ No. Concentration ControL Ratin~ ¦

il Cabbage Looper 1 400 100 ¦i Grape Downy Mildew 4 400 100 !j Apple Scab 8 400 100 loo 60

Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A triorganotin compound exhibiting a formula selected from the group consisting of and wherein R is hydrogen or alkyl of from 1 to 3 carbon atoms;
N is O, 1 or 2;
X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, carbonate, amide (NH2), amino (NR? or NR1?), , , phenoxy, alkoxy (-OR2), dithiocarbamoyl, , mercaptide (SR1), dialkyldithiophosphate provided that X is not hydroxyl when R is hydrogen and n is 0;
wherein R1 represents alkyl containing from 1 to 12 carbon atoms or wherein Z is hydrogen, halogen, alkyl containing 1 to 3 carbon atoms, alkoxy containing 1 to 3 carbon atoms, or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen wherein m is an integer from 2 to 10 inclusive , sulfur, sulfate, phosphate or carbonate.

2. A triorganotin compound exhibiting a formula selected from the group consisting of and wherein R is hydrogen or alkyl of from 1 to 3 carbon atoms n is 0, 1 or 2 and X is selected from the group consisting of fluorine, nitrate, cyanate, carba-mate, thiocarbamate, amide (NH2), amino (NR? or NR1H), , , alkoxy (-OR2), and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms or phenyl wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, , wherein m is an integer from 2 to 10, inclusive, , sulfur, sulfate or carbonate.

3. A triorganotin compound exhibiting a formula selected from the group consisting of and wherein X is selected from the group consisting of fluorine, nitrate, cyanate, carbamate, thiocarbamate, amide (NH2), amino (NR? or NR1H), , , alkoxy (-OR2), dithiocarbamoyl and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms or phenyl wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, , wherein m is an integer from 2 to 10, inclusive, , sulfur, sulfate or carbonate.

4. A triorganotin compound according to claim 3 wherein Y is oxygen.

5. A triorganotin compound according to claim 3 wherein X is , or .

6. A triorganotin compound according to claim 3 wherein Y is sulfur, or .

7. A triorganotin compound of the formula or wherein m is 1 or 2, X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate, phosphate, carbonate, , , , , phenoxy, alkoxy (-OR2), dithiocarbamoyl , mercaptide (-SR1) and dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms or wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and Y is oxygen, , , sulfur, sulfate or phosphate.

8. A triorganotin compound according to claim 7 wherein X is hydroxyl.

9. A triorganotin compound according to claim 7 wherein Y is oxygen.

10. A triorganotin compound of the formula or wherein R is alkyl and contains from 1 to 3 carbon atoms, X is selected from the group consisting of fluorine, hydroxyl, nitrate, cyanate, carbamate, thiocarbamate, phosphate, carbonate, carboxylate , , , , , phenoxy, alkoxy (-OR2), dithiocarbamoyl mercaptide (-SR1) dialkyldithiophosphate wherein R1 represents alkyl containing from 1 to 12 carbon atoms or wherein Z is hydrogen, halogen, 1-3 carbon alkyl, 1-3 carbon alkoxy or nitro (-NO2), R2 is alkyl containing from 1 to 12 carbon atoms and .gamma. is oxygen, , , sulfur, sulfate or carbonate.

11. A triorganotin compound according to claim 10 wherein .gamma. is oxygen and R is methyl or ethyl.