GB1593589A – Triorganotin compounds for combating fungi and insects
– Google Patents
GB1593589A – Triorganotin compounds for combating fungi and insects
– Google Patents
Triorganotin compounds for combating fungi and insects
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Publication number
GB1593589A
GB1593589A
GB10749/78A
GB1074978A
GB1593589A
GB 1593589 A
GB1593589 A
GB 1593589A
GB 10749/78 A
GB10749/78 A
GB 10749/78A
GB 1074978 A
GB1074978 A
GB 1074978A
GB 1593589 A
GB1593589 A
GB 1593589A
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United Kingdom
Prior art keywords
tri
tin
triorganotin
compounds
dimethylbutyl
Prior art date
1977-03-18
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GB10749/78A
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M&T Chemicals Inc
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M&T Chemicals Inc
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1977-03-18
Filing date
1978-03-17
Publication date
1981-07-22
1978-03-17
Application filed by M&T Chemicals Inc
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M&T Chemicals Inc
1981-07-22
Publication of GB1593589A
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patent/GB1593589A/en
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Classifications
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
C07F7/22—Tin compounds
C07F7/226—Compounds with one or more Sn-S linkages
A—HUMAN NECESSITIES
A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
A01N55/04—Tin
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
C07F7/22—Tin compounds
C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
C07F7/22—Tin compounds
C07F7/2224—Compounds having one or more tin-oxygen linkages
Description
(54) NOVEL TRIORGANOTIN COMPOUNDS FOR
COMBATING FUNGI AND INSECTS
(71) We, M & T CHEMICALS INC., a corporation organized and existing under the laws of the State of Delaware, United States of America, with executive offices at 22 Gate
House Road, Stamford, Connecticut, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention is concerned with the selective control of fungi and insects, especially mites. The organisms against which the compounds are effective -are responsible for a considerable portion of the annual damage to agricultural crops. Many tri-n-alkyltin compounds, particularly tri-n-butyltin and tri-n-amyltin derivatives, effectively control these organisms but these compounds are relatively non-selective towards both agricultural and decorative plants in that while the – fungus or insect attacking the plant may be controlled, the plant to which the compound is applied is frequently killed or severely damaged.
The invention provides, as new compounds useful for the above purpose, organotin compounds of the formula
wherein Rl is methyl or ethyl, R2 is hydrogen, methyl or ethyl and n is 0, 1 or 2, with the proviso that each of the three hydrocarbon radicals bonded to the tin atom contains from 6 to 9 carbon, atoms, X is selected from chlorine, bromine, fluorine, hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate,
phenoxy, alkoxy (-OR4), dithiocarbamate
mercaptide (-SR3) and dialkyldithiophosphate
wherein R3 is an alkyl group containing 1 to 12 carbon atoms or
wherein Z is hydrogen, halogen, an alkyl or alkoxy group containing’ 1 to 3 carbon atoms or nitro (-NO2), R4 is an alkyl group containing 1 to 12 carbon atoms, Y is
wherein m is 2 to 10,
oxygen, sulphur, sulphate, phosphate or carbonate and a represents the valency’of Y and is 2 or 3.
These sterically hindered triorganotin compounds are considerably less phytotoxic than homologous triorganotin compounds wherein the hydrocarbon radicals are linear and contain 4 to 6 carbon atoms.
Examples of compounds of the above formulae are those wherein X is halogen, in particular chlorine or bromine, or hydroxyl; Y is oxygen; R1 and R2 are methyl and n is 1 and Rl is ethyl, R2 is hydrogen and n is 1.
The preferred hydrocarbon radicals bonded to the tin atom are 2,2-dimethylbutyl and 2-ethylbutyl.
Compounds of the foregoing formula wherein X represents chlorine,, bromine or iodine may conveniently be prepared by reacting a tetraorganotin compound of the general formula
wherein R1 and R2 are as previously defined and R5 represents an alkyl radical that preferably contains 1 to 4 carbon atoms, with an equimolar amount of a stannic halide.
During the reaction the alkyl radical R5 is replaced by a halogen atom from the stannic halide. The reactions involved can be represented by the following equations wherein A is
and Z1, Z2 and Z3 are chlorine, bromine or iodine.
3AMgZ1 + R5SnZ32 < A3SnRs + 3MgZ1Z2 A3SnRs + SnZ43 A3SnZ3 + R5SnZ3 The by-product of the second reaction, R5SnZ33, can be recycled to prepare a second portion of the tetra-organotin compound by reaction with the appropriate organomagnesium halide, AMgZ1. Specific procedures for preparing representative compounds are described in the accompanying examples.
The aforementioned alkyltin trihalide R5SnZ32 can, in turn be prepared by reacting the corresponding alkyl halide, R5Z2, with a stannous halide SnZ2 as described in United States
Patent 3,340,283.
The reaction between the stannic halide and the tetraorganotin compound should be performed under anhydrous conditions at temperatures from -25 to 800C., preferably from +25 to 800C., in a liquid hydrocarbon solvent. Preferred solvents include pentane, hexane and cyclohexane.
Preferably the stannic halide is dissolved in such a solvent and the resultant solution added dropwise to a second solution containing the tetraorganotin compound in the same solvent. The temperature of the reaction mixture is preferably maintained below 40"C.
during the addition, which requires about one hour, after which the mixture is heated to a temperature of 35 to 800C. Preferably the temperature employed is the reflux temperature of the reaction mixture. Heating is continued for 15 to 60 minutes to ensure complete reaction. The reacton mixture is then allowed to cool to ambient temperature, and extracted with one or more portions of water or a dilute aqueous mineral acid. The monoorganotin trihalide, R5SnZ33, is soluble in the aqueous phase of the reaction mixture while the desired product remains in the organic phase, and may readily be isolated by boiling off the hydrocarbon solvent. No further purification is usually required, but the product can be distilled or recrystallized if desired. The organic layer is preferably freed of any dissolved water following the extraction step. Any of the conventional chemical dehydrating agents are suitable, provided that they do not react with either' the triorganotin halide or the hydrocarbon solvent. Preferred drying agents include anhydrous magnesium sulphate, anhydrous sodium sulphate and anhydrous calcium sulphate.
Alternatively, the triorganotin bromides can be prepared by the gradual addition of bromine to a solution containing the corresponding tetraorganotin compound of the formula A4Sn, which has been prepared by reacting the corresponding organomagnesium halide, AMgZ, with a stannic halide in a molar ratio of 4:1, respectively.
The triorganotin halides are solids or liquids at ambient temperature. They can readily be converted to other derivatives such as the oxide, acetate and sulphate using known reactions. The desired anionic radical can be introduced by reacting the corresponding triorganotin halide, hydroxide or bis(triorganotin) oxide with the reagent indicated in the following table.
Organotin Derivative + Reagent Desired Product
Chloride, Bromide Carboxylic acid + carboxylate,
or Iodide acid acceptor, e.g. e.g. acetate
an amine alkali metal salt of
a carboxylic acid
aqueous solution of oxide (or
alkali metal hydroxide hydroxide) alkali metal alkoxide alkoxide
or alcohol + acid
acceptor (e.g. an
amine)
alkali metal phenoxide phenoxide
or phenol + acid
acceptor potassium fluoride or fluoride
hydrofluoric acid alkali metal sulphide sulphide alkali metal sulphate sulphate mercaptan + acid mercaptide
acceptor alkali metal cyanate
cyanate alkali metal thiocyanate
thiocyanate alkali metal thiocarbamate
thiocarbamate alkali metal dithiocarbamate
dithiocarbamate
Chloride, Bromide phosphoric acid phosphate
or Iodide or alkali metal
phosphate
alkali metal dialkyldithio
dialkyldithio- phosphate
phosphate
Oxide or Hydroxide carboxylic acid or carboxylate
anhydride alcohol (or phenol) alkoxide (or
phenoxide) hydrofluoric acid fluoride
dilute (10-25 weight sulphate
%) aqueous
sulphuric acid
hydrogen sulphide sulphide alkyl or aryl mercaptide
mercaptan
carbon dioxide carbonate
Hydroxide heat to remove oxide
water
The reaction conditions such as preferred solvents, temperatures and reaction times for preparing the derivatives summarized in the preceding table are known in the art and, therefore, do not require a detailed description in the present specification. A comprehensive treatment of this subject matter together with numerous literature references is contained in an article by R.K. Ingham et al. that appeared in the October, 1960 issue of
CHEMICAL REVIEWS (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 sterically hindered trialkyltin compounds according to the invention effectively control many types of undesirable fungi and insects, particularly mites, when applied to living plants that are susceptible to infestations of these organisms. The combination of fungicidal and miticidal activity is not common for a singl organotin compound. A single application of these compounds to living plants or other substrates provides residual and extended control of many varieties of fungi and insects for a considerable period of time, the duration of which is dependent to some extent upon mechanical and biological influences, including weather. Formulations containing these organotin compounds can be applied directly to the organism to be controlled or to environments that will subsequently be infested with the organism.
The invention accordingly includes a pesticidal composition for controlling fungi and insects, said composition comprising a liquid or solid carrier and a triorganotin compound according to either of the two foregoing formulae.
In preparing compositions for application to plants the organotin compound is often augmented or modified by combining it with one or more commonly employed pesticide additives or adjuvants including organic solvents, water or other liquid carriers, surfactants to aid in dispersing or emulsifying the organotin compound and finely comminuted solid carriers. Depending upon the concentration of triorganotin compound in these composi tions, 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 concentrates, the triorganotin compound can be present at concentrations of 5 to 98So by weight, based on the weight of a composition. Other biologically active agents that are chemically compatible with the triorganotin compounds can also be added.
The optimum effective concentration of triorganotin 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 effective dose is primarily dependent upon the susceptibility of the particular organism to a given triorganotin compound. For control of insects, good results are obtained with liquid or dust compositions containing as little as one part per million by weight of toxicant.
Compositions containing up to 90 percent by weight of toxicant can be employed to treat a heavily infested area.
In the preparation of dust compositions, the organotin compound can be blended with many commonly employed finely divided solid carriers such as fuller's earth, attapulgite, bentonite, pyrophyllite, vermiculite, diatomaceous earth, talc, chalk, gypsum and wood flour. The carrier, usually in a finely divided form, is ground or mixed with the toxicant or wetted with a dispersion of 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, cationic or non-ionic surfactants as emulsifying or dispersing agents to form spray concentrates. Such concentrates are readily dispersible in liquid carriers to form spray compositions or liquid formulations containing the toxicants in any desired amount. The choice and concentration of surfactant are determined by the ability of the material to facilitate the dispersing of the concentrate in the liquid carrier to produce the desired liquid composition. Suitable liquid carriers include water, methanol, ethanol, isopropanol, methyl ethyl ketone, acetone, methylene chloride, chlorobenzene, toluene, xylene and petroleum distillates. Among the preferred petrolleum distillates are those boiling below 400"F. at atmospheric pressure and having a flash point above 80"F.
Liquid compositions can also be prepared by dissolving one of the present triorganotin compounds in a mixture containing a water-immiscible organic liquid and a surface active dispersing agent. The resultant emulsifiable concentrate may then be further. dilute.d with water and an oil to form a spray mixture in the form of an oil-in-water emulsiont ffin such compositions, the carrier comprises an aqueous emulsion, i.e. a mixture of waterimmiscible solvent, emulsifying agent and water. Preferred dispersing agents fUr these compositions are oil-soluble and include the condensation products of alkylene oxides with phenols and organic or inorganic acids, polyoxyethylene derivatives of sorbitan esters, alkylarylsulfonates, complex ether alcohols and mahogany soaps. Suitable organic liquids to be employed in the compositions include petroleum distillates, hexanol, liquid halohydrocarbons and synthetic organic oils. The surface active dispersing agents--are usually employed in the liquid dispersions and aqueous emulsions in the amount of 1 to 20 percent by weight of the combined weight of the dispersing agent and the active toxicant.
When operating in accordance with the present invention, the organotin compound or a composition containing the compound can be applied directly onto the organism to be controlled or to the site to be protected, particularly plants and trees. Application to the foliage of plants is conveniently carried out using power dusters, boom sprayers and spray dusters. When employed in this manner the composition should not contain any significant amounts of phytotoxic diluents. In large scale operations, dusts or low volume sprays may be applied from an aircraft.
In the following examples all parts, percentages and ratios are by weight unless otherwise specified.
EXAMPLES
EXAMPLE 1
Preparation of Tri(2-ethylbutyl)tin Bromide and Derivatives Thereof
A. Preparation of Tetra(2-ethylbutyl)tin
25 cc. of a solution of 165 g. (1 mole) of 1-bromo-2-ethylbutane in 450 cc. of anhydrous tetrahydrofuran was added to 24.3 g. (1 g. atom) of magnesium chips heated to a temperature of 40"C. under a nitrogen atmosphere. The reaction was initiated by the addition of a few drops of ethylene dibromide. The remainder of the solution of 1-bromo-2-ethylbutane was gradually added during a period of 1.5 hours. The heat generated was sufficient to maintain the reaction mixture at the boiling point. External heat was applied for an additional hour, following completion of the addition. The reaction mixture was allowed to cool to ambient temperature and remain at this temperature for one hour, during which time stirring of the mixture was continued. At the end of this period all of the magnesium appeared to have reacted. 200 cc. of this solution containing 0.4 mole of 2-ethylbutyl magnesium bromide was placed in a reactor under a nitrogen atmosphere and a solution containing 26 g. (0.1 mole) of stannic chloride dissolved in 150 cc. of benzene was gradually added to this solution. The addition required 2 hours, during which time the temperature of the reaction mixture was maintained below 40"C. Following completion of the addition the reaction mixture was heated to the boiling point for 1.5 hours, then allowed to cool to ambient temperature. To the resultant mixture was added a solution containing 250 cc. water and 25 g. of citric acid. The organic phase of the resultant two phase liquid was separated and the water present therein removed using anhydrous magnesium sulphate, which was subsequently removed by filtration. The solvent was evaporated under reduced pressure to yield 43.1 g. (94% yield) of a liquid, tetra(2-ethylbutyl)tin. The product was found to contain 25.90% tin. The calculated value for tetra(2-ethylbutyl)tin is 25.86%.
B. Cleavage of Tetra (2-ethylbutyl) tin to Tri(2-ethylbutyl)tin Bromide
45.9 g. (0.1 mole) of tetra(2-ethylbutyl)tin prepared as described in part A of this example was dissolved in a mixture of 200 cc. chloroform and 200 cc. methanol and cooled to 0 C To this solution was added a solution containing 16.0 g. (0.2 g. atom) of bromine and 100 cc. of the aforementioned chloroform-methanol mixture. The addition required 3 hours, following which the resultant mixture was stirred for 0.25 hours while being cooled to 0 C. The solvent was then removed under reduced pressure to yield 46.6 g. of a yellow liquid. The product was found to contain 25.14% tin and 15.19% bromine. The calculated values for tri(2-ethylbutyl)tin bromide are 26.14% tin and 17.60% bromine.
Bis[tri(2-ethylbutyl)tin] oxide was prepared by adding a solution of the corresponding bromide (45.4 g. of the bromide in 100 cc. of methanol) to a solution containing 8 g. of sodium hydroxide, 50 cc. water and 50 cc. methanol. The addition was gradual and required 0.25 hour, after which the mixture was heated at the boiling point for 20 minutes, then allowed to cool to ambient temperature. 300 cc. of diethyl ether was then added, followed by 400 cc. of water. The organic phase of the resultant 2-phase liquid was isolated and
combined with anhydrous magnesium sulphate to remove traces of water. The aqueous phase was discarded. The ether present in the organic layer was removed to yield 36.5 g. of
a clear yellow liquid exhibiting a refractive index (n20) of 1.4915. The liquid was found to
contain 30.10% tin. The calculated tin content for bis[tri(2-ethylbutyl)tin oxide is 31.06%.
EXAMPLE 2
Preparation of Tri(2,2-dimethylbutyl)tin Chloride
A. Preparation of Methyl Tri(2,2-dimethylbutyl)tin To 12.2 g. (0.5 g. atom) of magnesium chips heated to a temperature of 40"C. under a
nitrogen atmosphere was added 25 cc. of a solution of 82.5 g. (0.5 mole) of
1-bromo-2,2-dimethylbutane in 250 cc. of anhydrous tetrahydrofuran. The reaction was
initiated using a few drops of ethylene dibromide. The remaining portion of the
1-bromo-2,2-dimethylbutane solution was gradually added during a period of one hour
while the reaction mixture was heated to the boiling point. Heating was continued for an
additional hour, during which time 6 cc. of a 3 normal solution of methylmagnesium
bromide in tetrahydrofuran was added to react with any impurities which could prevent or
inhibit the formation of 2,2-dimethylbutyl magnesium bromide. The reaction mixture was
then allowed to cool to ambient temperature. 250 cc. of this solution containing 0.18 mole
of 2,2-dimethylbutyl magnesium bromide was added dropwise to a stirred solution of
methyltin trichloride (14 g., 0.06 mole) dissolved in 100 cc. of dry cyclohexane. The
addition required 0.5 hour and was conducted under a nitrogen atmosphere. During the
addition the temperature of the reaction mixture was maintained below 40"C. Following
completion of the addition the reaction mixture was heated to the boiling point for one
hour, then allowed to cool to ambient temperature. To the resultant mixture was added a
solution containing 100 cc. water and 25 g. citric acid. The organic phase of the resultant
two phase liquid was separated and the water present therein removed using anhydrous
magnesium sulphate, which was subsequently removed by filtration. The solvent was
evaporated under reduced pressure to yield 43.4 g. of a liquid, crude methyl tri(2,2
dimethylbutyl)tin. This liquid was distilled and the portion boiling at 87 to 92"C. was
collected. Analysis by vapour phase chromatography indicated that the product was 90%
pure. The product was found to contain 30.17% tin. The calculated value for methyl
tri(2,2-dimethylbutyl)tin is 30.50%.
B. Cleavage of Methyl Tri(2,2-dimethylbutyl)tin to Tzi(2,2-dimethylbutyl)tin Chloride
11.7 g. (0.03 mole) of the methyl tri(2,2-dimethylbutyl)tin prepared as described in part
A of this example was dissolved in 50 cc. of dry pentane. To this solution was added a solution containing 7.8 g. (0.03 mole) of anhydrous stannic chloride and 50 cc. pentane. The addition required 0.5 hour, 'following which the resultant mixture was heated to the broiling.
point for 0.5 hour and then allowed to cool to ambient temperature. A solution obtained by combining 2 cc. of 12N aqueous hydrochloric acid and 100 cc. water was then added to the reaction mixture with vigorous stirring both during the addition and for five minutes thereafter. The organic layer of the resultant two-phase liquid was isolated and the water therein removed using anhydrous magnesium sulphate. The solvent phase was then separated and concentrated under reduced pressure to yield 12;2 g. of a solid. Following one recrystallization from methanol, the product weighed 8.6 g., was white in colour and melted between 44 and 45"C. Upon analysis the compound was found to contain 28.66% tin. The calculated tin content for tri(2,2-dirnethylbutyl)tin chloride is 28.98%.
EXAMPLE 3
Conversion of tri(2,2-dimethylbutyl)tin Chloride to the Corresponding Hydroxide and
Acetate
Tri(2,2-dimethylbutyl)tin hydroxide was prepared by dissolving 12.4 g. (0.03 mole) of the chloride, prepared as described in the preceding Example 2, in a mixture of 25 cc. of methanol and 15 cc. of acetone. The resultant solution was added over a 15 minute period to a stirred solution containing 1.8 g. (0.045 mole) of sodium hydroxide, 520 cc. deionized water and 25 cc. methanol. The temperature of the reaction mixture was maintained below 25"C. during the addition of the chloride. Following completion of the addition the mixture was heated to the boiling point for 10 minutes using a water-cooled condenser. The solid product was recovered from the reaction mixture by the addition of 500 cc. deionized water and cooling to OOC. The product was then isolated, washed with water until the wash water was free of detectable chloride, and then dried under reduced pressure. The weight of the final product was 11.0 g., equivalent to a yield of 94%. The product was found to contain 31.16% tin and no chlorine. The calculated tin content for tri(2,2-dimethylbutyl)tin hydroxide is 30.35%. Analysis by potentiometric titration indicated that the product was 97.9% pure. 4.05 g. (0.01 mole) of this material was converted to the corresponding acetate by dissolving it in 100 cc. of dichloromethane. To the resultant yellow solution was gradually added during a five minute period a solution containing 0.66 g. (0.011 mole) of glacial acetic acid and 50 cc. dichloromethane. After stirring for ten minutes the solvent was evaporated under reduced pressure to yield 4.2 g. (98% yield) of a solid that was found to contain 27.25% tin. The calculated tin content of tri(2,2-dimethylbutyl)tin acetate is 27.40%.
EXAMPLE 4
Pesticidal Activity of Sterically Hindered Triorganotin Compounds
Bis[tri(2-ethylbutyl)tin] oxide and tri(2,2-dimethylbutyl)tin chloride were evaluated to determine their efficacy as control agents for fungi and insects. The test procedures and results are summarized below.
Procedure 1
Bean plants infested with two-spotted spider mites (Tetranychus bimaculatis) are sprayed to the saturation point with an aqueous dispersion containing a specified concentration of the organotin compound in the form of a wettable powder consisting of equal parts by weight of organotin compound and a finely divided clay. The dispersions contained a small amount of a nonionic surfactant. The percent mortality is observed three days after the plants are sprayed.
Procedure 2
A bean plant is sprayed to the saturation point with an aqueous dispersion containing a specified concentration of the organotin compound. A number of cabbage loopers (Trichoplusia ni) are then placed on the leaves. The percent mortality is observed three days after the plants are sprayed.
Procedure 3
This procedure is identical to Procedure 2 with the exception that the aqueous dispersion of the organotin compound is injected into the soil at the root zone in addition to being sprayed onto the leaves of the plant, and the mortality count is taken six days after the plant r rax
Procedure 4
Grape plants are sprayed to the saturation point with an aqueous dispersion containing the desired concentration of organotin compound, after which the plants are innoculated with grape downy mildew spores and placed in a 100% humidity environment for three days and in a greenhouse for an additional three days. Seven days after being sprayed, the plants are rated for control of the fungus. If no symptoms appear after seven days, the percent control is presumed to be 100%.
Procedure 5
Tobacco plants are transplanted into soil infested with tobacco black shank (Phytophthora parasitica, var. nicotiane). The soil is immediately drenched with an aqueous dispersion containing the desired concentration of the organotin compound. The test is graded on the basis of transplant survival.
Procedure 6
Adult German roaches are confined in cages and sprayed with an aqueous dispersion containing the desired concentration of organotin compound. A mortality count is taken three days after the insects are sprayed.
Procedure 7
Tender green bean plants with fully expanded primary leaves were placed adjacent to plants infested with the powdery mildew fungus (Ersiphe polygoni) 48 hours prior to the application of the organotin compound. The compound was applied buy placing the plants on a revolving turntable and spraying them with a formulation containing the triorganotin compound. Once the spray had dried, the plants were placed in a greenhouse for between 7 and 10 days after which time the amount of mildew on the primary leaves was rated.
Untreated plants served as controls.
TABLE I
Efficacy of Bis[tri(2-ethylbutyl)tin] Oxide
As A Pesticide
Organism Test Concentration % Control
Procedure (parts per million)
Spider Mite 1 200 100
25 97
Cabbage Looper 2 25 100
Tobacco Black Shank 5 6.3 100
Powdery Mildew 7 25 100
TABLE II
Efficacy of Tri(2,2-dimethylbutyl)tin Chloride
As A Pesticide
Organism Test Concentration % Control
Procedure (parts per million)
Spider Mite 1 400 100
200 99
100 95
Cabbage Looper 3 400 100
German Roach 6 400 83
Tabacco Black Shank 5 25 100
Grape Downy Mildew 4 400 100
Two compounds within the scope of this invention-were evaluated as miticides concurrently with two control compounds, tri(3,3-dimethylbutyl)tin chloride and tricyclohexyltin hydroxide, using test procedure 1. The results of this evaluation appear in the following table.
Compound (p.p.m.) % Mortality Tri(2,2-dimethylbutyl tin chloride 400 100 Tri 2,2-dimethylbutyl tin chloride 25) 83 Tri 2,2-dimethylbutyl tin chloride 6.2) 40 Bisrtri(2-ethylbutyl)tin] oxide (400) 100
Bis tri 2-ethylbutyl tin oxide 25) 97 Bis tri(2-ethylbutyl)tin oxide 6.2) ' 58
Controls Tri(3,3-dimethylbutyl)tin chloride (400)
Tri(3,3-dimethylbutyl)tin chloride 25 25) Tricyclohexyltin hydroxide (400) 100
Tricyclohexyltin hydroxide 25) 83
Tricyclohexyltin hydroxide 6.2) 25
The compounds according to the invention effectively control mites at considerably lower use levels (6.2 parts per million) than prior art compounds such as tricyclohexyltin hydroxide. This is economically advantageous, since less of the present compounds would be required to achieve a desired level of pest control.
None of the plants tested using any of the foregoing test procedures were significantly damaged by the triorganotin compound according to the invention. By comparison, plants treated with the same amount of linear triorganotin compounds, such as bis(tri-n-butyl)tin oxide have been killed or severely damaged. The triorganotin compounds according to the invention are characterized by a low degree of phytotoxicity and a high level of efficacy as pesticides, 'particularly toward mites. This-desirable combination of properties is unusual for triorganotin compounds and is not characteristic of compounds containing linear alkyl or phenyl- groups bonded to the tin atom.
DB
Claims (14)
**WARNING** start of CLMS field may overlap end of DESC **. Two compounds within the scope of this invention-were evaluated as miticides concurrently with two control compounds, tri(3,3-dimethylbutyl)tin chloride and tricyclohexyltin hydroxide, using test procedure 1. The results of this evaluation appear in the following table. Compound (p.p.m.) % Mortality Tri(2,2-dimethylbutyl tin chloride 400 100 Tri 2,2-dimethylbutyl tin chloride 25) 83 Tri 2,2-dimethylbutyl tin chloride 6.2) 40 Bisrtri(2-ethylbutyl)tin] oxide (400) 100 Bis tri 2-ethylbutyl tin oxide 25) 97 Bis tri(2-ethylbutyl)tin oxide 6.2) ' 58 Controls Tri(3,3-dimethylbutyl)tin chloride (400) Tri(3,3-dimethylbutyl)tin chloride 25 25) Tricyclohexyltin hydroxide (400) 100 Tricyclohexyltin hydroxide 25) 83 Tricyclohexyltin hydroxide 6.2) 25 The compounds according to the invention effectively control mites at considerably lower use levels (6.2 parts per million) than prior art compounds such as tricyclohexyltin hydroxide. This is economically advantageous, since less of the present compounds would be required to achieve a desired level of pest control. None of the plants tested using any of the foregoing test procedures were significantly damaged by the triorganotin compound according to the invention. By comparison, plants treated with the same amount of linear triorganotin compounds, such as bis(tri-n-butyl)tin oxide have been killed or severely damaged. The triorganotin compounds according to the invention are characterized by a low degree of phytotoxicity and a high level of efficacy as pesticides, 'particularly toward mites. This-desirable combination of properties is unusual for triorganotin compounds and is not characteristic of compounds containing linear alkyl or phenyl- groups bonded to the tin atom. WHAT WE CLAIM IS:
1. A triorganotin compound of the formula
wherein Rl is methyl or ethyl, R2 is hydrogen, methyl or ethyl and n is 0, 1 or 2, with the proviso that each of the three hydrocarbon radicals bonded to the tin atom contains from 6to 9 carbon atoms, X is selected from chlorine, bromine, fluorine; hydroxyl, nitrate, cyanate, thiocyanate, carbamate, thiocarbamate,
phenoxy, alkoxy (-OR4), dithiocarbamate
mercaptide (-SR3) and dialkyldithiophosphate
wherein R3 is an alkyl group containing 1 to 12 carbon atoms or
wherein Z is hydrogen, halogen, an alkyl or alkoxy group containing 1 to 3 carbon atoms or nitro (-NO2), R4 is an alkyl group containing 1 to 12 carbon atoms, Y is
wherein m is 2 to 10,
oxygen, sulphur, sulphate, phosphate or carbonate and a represents the valency of Y and is 2 or 3.
2. A triorganotin compound according to Claim 1, wherein X is halogen or hydroxyl.
3. A triorganotin compound according to Claim 2, wherein X is chlorine or bromine.
4. A triorganotin compound according to Claim 1, wherein Y is oxygen.
5. A triorganotin compound according to Claim 1, wherein R1 and R2 are each methyl and n is 1.
6. A triorganotin compound according to Claim 1, wherein R1 is ethyl, R2 is hydrogen and n is 1.
7. Bis(tri(2-ethylbutyl)tin) oxide.
8. Tri(2 ,2-dimethylbutyl)tin chloride.
9. A pesticidal composition for controlling fungi and insects, said composition comprising a liquid or solid carrier and a triorganotin compound as claimed in any one of the preceding claims.
10. A pesticidal composition according to Claim 9, wherein the carrier is a liquid.
11. A pesticidal composition according to Claim 10, wherein the liquid is water.
12. A pesticidal composition according to Claim 9, wherein the concentration of the triorganotin compound is 1 to 900,000 parts per million, based on the weight of the composition.
13. A pesticidal composition according to Claim 9, which is in the form of a concentrate for subsequent dilution with additional carrier prior to use.
14. A pesticidal composition according to Claim 13, wherein the concentration of triorganotin compound is 5 to 98%, based on the weight of the composition.
GB10749/78A
1977-03-18
1978-03-17
Triorganotin compounds for combating fungi and insects
Expired
GB1593589A
(en)
Applications Claiming Priority (1)
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US77918777A
1977-03-18
1977-03-18
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GB1593589A
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GB1593589A
(en)
1981-07-22
Family
ID=25115611
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Priority Date
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GB1593589A
(en)
1977-03-18
1978-03-17
Triorganotin compounds for combating fungi and insects
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JP
(1)
JPS53121723A
(en)
AU
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AU514580B2
(en)
BE
(1)
BE864712A
(en)
BR
(1)
BR7801664A
(en)
CA
(1)
CA1097651A
(en)
DE
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DE2809593A1
(en)
DK
(1)
DK122478A
(en)
ES
(1)
ES467985A1
(en)
FR
(1)
FR2383954A1
(en)
GB
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GB1593589A
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IT
(1)
IT1103081B
(en)
NL
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Cited By (1)
* Cited by examiner, † Cited by third party
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Title
CN112771058A
(en)
*
2020-12-31
2021-05-07
安徽金禾实业股份有限公司
Monotin organic compound, preparation method and application thereof
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* Cited by examiner, † Cited by third party
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GB1163738A
(en)
*
1965-10-27
1969-09-10
Pfizer & Co C
Process for Suppressing the Growth of Microorganisms
ZA743999B
(en)
*
1973-08-30
1975-06-25
M & T Chem Ind
Method for combating fungi and mites using certain triorganotin compounds
1978
1978-02-22
AU
AU33511/78A
patent/AU514580B2/en
not_active
Expired
1978-03-06
DE
DE19782809593
patent/DE2809593A1/en
not_active
Withdrawn
1978-03-07
FR
FR7806416A
patent/FR2383954A1/en
active
Pending
1978-03-09
BE
BE185785A
patent/BE864712A/en
unknown
1978-03-13
SE
SE7802838A
patent/SE7802838L/en
unknown
1978-03-15
IT
IT09374/78A
patent/IT1103081B/en
active
1978-03-16
CA
CA299,117A
patent/CA1097651A/en
not_active
Expired
1978-03-17
GB
GB10749/78A
patent/GB1593589A/en
not_active
Expired
1978-03-17
BR
BR7801664A
patent/BR7801664A/en
unknown
1978-03-17
NL
NL7802913A
patent/NL7802913A/en
not_active
Application Discontinuation
1978-03-17
DK
DK122478A
patent/DK122478A/en
not_active
Application Discontinuation
1978-03-17
ES
ES467985A
patent/ES467985A1/en
not_active
Expired
1978-03-17
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Cited By (2)
* Cited by examiner, † Cited by third party
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CN112771058A
(en)
*
2020-12-31
2021-05-07
安徽金禾实业股份有限公司
Monotin organic compound, preparation method and application thereof
WO2022141457A1
(en)
*
2020-12-31
2022-07-07
安徽金禾实业股份有限公司
Mono-tin organic compound, preparation method therefor and use thereof
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DK122478A
(en)
1978-09-19
SE7802838L
(en)
1978-09-19
JPS53121723A
(en)
1978-10-24
DE2809593A1
(en)
1978-09-21
CA1097651A
(en)
1981-03-17
BR7801664A
(en)
1979-01-02
ES467985A1
(en)
1978-12-01
IT1103081B
(en)
1985-10-14
NL7802913A
(en)
1978-09-20
FR2383954A1
(en)
1978-10-13
AU3351178A
(en)
1979-08-30
AU514580B2
(en)
1981-02-19
IT7809374D0
(en)
1978-03-15
BE864712A
(en)
1978-07-03
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Legal Events
Date
Code
Title
Description
1981-10-07
PS
Patent sealed
1983-11-09
PCNP
Patent ceased through non-payment of renewal fee
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