CA1181410A

CA1181410A - Tin compounds

Info

Publication number: CA1181410A
Application number: CA000386278A
Authority: CA
Inventors: Wolfgang Wehner; Saleem Farooq; Hans-Gunter Kostler
Original assignee: Ciba Geigy Investments Ltd
Current assignee: Novartis AG
Priority date: 1980-09-23
Filing date: 1981-09-21
Publication date: 1985-01-22
Also published as: IL63900A0; BR8106049A; EP0048696A3; NZ198439A; AR231298A1; ES505680A0; AU7556881A; EP0048696A2; ES8206539A1

Abstract

ABSTRACT OF THE DISCLOSURE
The invention relates to organo-tin ammonium salts or the formula (I) wherein each of R1, R2 and R3 is hydrogen or the same or different alkyl of up to 20 carbon atoms;
R4 is epoxyalkyl, haloalkyl or halohydroxyalkyl, each containing up to 6 carbon atoms;
R5 is alkyl of up to 6 carbon atoms, cyclohexyl or phenyl;
each of R6 and R7, independently of the other is either the same as R5 or the same as X1 as hereinafter defined;
X1 is chloro or bromo; and X2, X3 and X4 are either all chloro or all bromo. A process for the production of these compounds and their use in pest control are also described.

Description

-4 1 ~
The present invention relates to organo-tin ammonium salts, to the production thereof and to the use thereof in pest control.
The organo-tin ammonium salts have the formulae R2 1 ~9 ~3 R I / Xl ¦ ~ R12 - ~3 R5 Xl _ 2 ~

'1~14R3~ R7 2~ and Rl-R4R3, 2 R6 X4 ~ (I) wherein each of Rl, R2 and R3 is hydrogen or the same or different alkyl o:~ up to 20 carbon atoms;
Rll is epoxyalkyl, haloalkyl or halohydroxyalkyl, each containing up to 6 carbon atoms;
R5 is alkyl of up to 6 carbon atoms, cyclohexyl or phenyl;
each of R6 and R7, independently of the o-ther is either the same as R5 or the same as Xl as hereinafter defined;
Xl is chloro or bromo; and X2, X3 and XLI are either all chloro or bromo.
Halogen within the scope of the above definitions denotes .~luorine, chlorine, bromine or icdine, with chlorine or bromine being preferred.
The alkyl, haloalkyl, halohydroxyalkyl, or epoxyalkyl g:roups within the definitions of Rl to R7 can be straight-chain or branched, and those groups defined by Rl to R3 contain preferably 1 -to 6 carbon atoms in the chain. Representative examples o:~ such groups are: methyl, ethyl, ethyl chloride, ethyl bromide, propyl, isopropyl, n-butyl, isobutyl, sec- and tert-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-nonadecyl, n-eicosyl, and the isomers thereof, e.g. 2-ethylhexyl, -CH-CH-CH2Cl or -CH2-CH~ ,CH2.
OH

,.~''~,, ~.

Preferred compounds of the formula I are -those wherein each of Rl, R2 and R3 is methyl; R4 is chloroethyl, bromoethyl, 3-chloro-2-hydroxypropyl, or 2-hydroxyethyl; R5 is methyl, cyclohexyl or phenyl; each of R6 and R7 is chlorine, cyclohexyl or phenyl; Xl is chlorine and X2 is chlorine or bromine.
The most preferred compounds of the formula I, however, are those wherein each of R1, R2 and R3 is methyl, R4 is chloro-ethyl, bromoethyl, 3-chloro-2-hydroxypropyl, or 2-hydroxyethyl, each of R5, R6 and R7 is cyclohexyl, Xl is chlorine, and X2 is :L0 chlorine or bromine.
The organo-tin ammonium salts of the formula I can be obtained by methods which are known per se, e.g. as follows:

-N-R ¦ X2~3 + Rs-Sn-X

(II) (III) In the formulae II and III above, R1 to R7 and X1 and X2 are as defined for formula I.
The process is conveniently carried out in the temperature range from -10 to +180C, preferably from ~0 to 150(~C, under normal or slightly elevated temperature, and preferably ln the pr-esence of a solvent or diluent which is inert to the reactants.
Examples of suitable solvents or diluents are: alcohols such as methanol, ethanol or isopropanol; ethers and ethereal compounds such as diethyl ether, dioxane and tetrahydrofurane; and ketones such as acetone, cyclohexanone or methyl ethyl ketone.

~le starting materlals of the formulae II and III are known and can be prepared by known methods.

The compounds of ormula I are suitable for controlling a variety of pests of animals and plants and they also have a fungicidal and plant regulating action. Accordingly, they can be used for controlling insects, for example of the orders Lepidoptera, Coleoptera,~~lomoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura~ Isoptera, Psocoptera and Hymenoptera, and for controlling phy~opathogenic mites and ticks of the order AcarinaO

Of especial importance is the fact that the compounds of the formula I
have a surprisingly potent and specific action against plant-destruc-tive mites and mites which are parasites of animals. Thus the com-pounds of the formula I can be employed for controlling phytophagous mites e.g. of the families Tetranychidae and Phytoptipalpidae (spider ~ites), Tarsonemidae (soft-bodied mites) and Eriophyidae (gall mites).
The compounds of formula I are suitable in particular for controlling the following species of mites which infest crops of fruit and vegetables: Tetranychus urticae, Tetranychus cinnabarinus, Panonychus ulmi, Bryobia rubrioculus, Panonychus citri, Eriophyes pyri, Eriophyes ribis, Eriophyes vitis, Tarsomemus pallidus, Phyllocoptes vitis and Phyllocoptura oleivora. ~ith the aid of compounds of formula I it i9 also possible to control parasitic mites e.g. of the families Sarcoptidae~ Psoroptidae, Dermanyssidae and Demodicidae, in particular ~cab mites of the species Sarcoptes scabiei and Notoedres cati, which penetrate deep into the epider~is as ~ar as the nerve ends of domestic animals and productive livestock infested by them and cause severe irritation and damage9 and also mites of the species Derma~yssus gallinae and Psoroptes ovis.

4 ~ 0 The co~pounds of ~he formula I are used in unmodified for~ or, prefer-ably, together with the adiuvants conventionally ~m~loyed in the art of formulation~ and are therefore formulated in known manner to emul-sifiable concentrates, direccly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. The methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectiv2s and the prevailing circumstances, just l.ike the nature of the compositions.

The formulations, i.e. the co~positions or preparations containing the compound (active ;ngredient) of the formula I and, where appropriate, a solid or liquid adJuvant, are prepared in known man~er, e.g. by homo-geneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, ~here appropriate, surface-active compounds (surfactan~s).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms9 e.g. xylene mixtures or substi~uted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or parafi~s 9 alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, e~hylene glycol monomethyl or monoethyl ether~ ketones ~uch as cyclo-hexanone~ strongly polar solvents such as N~methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamlde, as well as epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

_ 5 ~
.

The solid carriers used e.g. for dus~s and dispersible powde-s, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve ~he physical pro-perties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable ~ranulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bento~ite; a~d suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the co~pound of the formula I to be for~u-lated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants havin~ good emulslfying, dispersing and wetting properties. The term "surfactants" will also be understood as compris-in~ m~xtures of surfactants.

Suitable a~ionic surfactants can be both water-soluble soaps and w~ter-soluble synthetic surface-active compounds.

Sui~able soaps are the alkali metal salts, alkaline earth ~etal salts or unsubsthtuted or substituted ammonium salts of higher fat~y acids (C10-C22), e.g. the sodi~ or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g.
rom coconut oil or tallow oil. ~ntion may also be made of fatty acid methyl-taurin salts~

More frequently~ however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substi~u~ed ~ ~ 8 ~
~ 6 --a~monium salts ant contain a C8-C~2alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. ~he sodium or calcium sal~ of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtai~ed from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohoL/ethylene oxide adducts. Th~ sulfonated benzimidazole deriva-tivss preferably contain 2 sulfonic acid groups ~nd one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylben~ene-sulfonic acid, dibutylnaphthalenesulfonic acid, or of a naphthalene-sul~onic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts o the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloalipha~ic alcohol~, or saturated or unsaturated fatty acids and alkylphenols, said deri~atives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkyl-phenols.

Further suitable ~on-ionic surfactan~s are the water-soluble adducts of polyethylene sxide with polypropylene glycol, ethylene diamino-propylene glycol and alkylpolypropylene glycol containi~g 1 to ~0 carbon atoms i~ the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples o~ non-ionic surfactanes are nonylphenol-polyethoxyetha~ols, castor oil polyglycol ethers, polypropylene/poly-oxyethylene adducts, t~ibutylphenoxypolyethoxyethanol, polye~hyle~e glycol a~d octylphenoxypolyethoxyethacol. Fatty acid esters of poly-oxyethyle~e sorbitan and polyoxyethylene sorbi~an ~rioleate are also suitable non-ionic surfactants.

~ ~14~0 Cationic surfactants are preferably quaternary æmmonium salts which contain, as N-substituent~ at least one C8-C22alkyl radical and~ as further substituents, lower unsubstituted or halogenated alkyl, ben~yl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl~rimethyl-ammonium chloride or benæyldi(~-chloroethyl)e~hyla~monium bromide.

The surfactants cus~omarily employed in the art of formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood, New Jersey~ 1979.

The pesticidal formulations usually contain 0.1 to 99%, preferably 0.1 to 95%, of a compound of the for~ula I, 1 to 99.9% of a solid or liquid adjuvant, and O to 25%, prefPrably 0.1 to 2~%, of a surfactant.

Whereas commercial protucts are preferably formulated as concentrates, the end user will normally employ dilute formulations.

The formulations can also contain further additi~es such as stabilisers, antifoams, viscosity regulators, binders, adhesives, as well as fertilisers, in order to produce spe~ial effects.

~ 3 ~

Formulation Exa~æ~

Formulation ~ les for _iquid active_ingredients of the for ula I
(throughout, percentages are by ~eight) 1) Emulsifiable ~oncentrates a) b) c~
active ingredient 20% 40% 50%
calcium dodecylbenzenesulfonate 5% 8% 5.8%
castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5% - -tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4.22 cyclohexanone - 15% 20%
xylene mixture 70% 25% 20%

Emulsions of any required concentration can be produced from such concentrates by dilution with water.

2) Solutions a) b) c) d) .
activ~ ingredient 80% 10% 52 95 ethylene glycol monomethyl ether 20%
polyethylene glycol 400 - 70% - -N-methyl-2-pyrrolidone - 20% - -epoxidised coconut oil - - 1% 5%
petroleum distillate(boiling range 160-190) - - 94%

~hese solutions are suitable for applica~ion in the form of microdrops.

3) Granulates a) b) active ingredient 5~ 10%
kaolin 94%
highly dispersed silicic acid 12 attapulgite . -- 90 - ~

The active ingredient i5 dissolved in methylene chloride, the solution is sprayed cnto the carrier, and the solvent is subsequently ~vaporated off in vacuo.

4) Dusts a) b) __ active i~gredient 2% 5%
highly dispersed silicic acid 1% 5%
talcum 97%
kaolin - 90Z

Ready-for-use dusts a~e obtained by intimately mixing the carriers ~ith the active ingredient.

Formulation examples for solid active ~redients of the formul_ I
(throughout, percentages are by weight)

5) Wettable ~ ers a) b) active ingredient 20% 60%
sodium lignosulfonate ` 5% 5%
sodium laurylsulfa~e 3%
sodium diisobutylnaphthalenesulfonate - 6%
octylphenol polyethylene glycol ether t7-8 moles of ethylene oxide) - 22 highly dispersed silicic acid 5% 27 kaolin 67%

The active ingredient is ehoroughly mi~ed ~ith the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable poweders ~hich can be diluted with ~ater to give suspensions of the desired concen~ration.

6) Emulsifiable concentrate active ingredient 10%
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3~
calcium d~decylbenzenesulfonate 3%
castor oil polyglycol ether (36 moles of ethylene oxide) 4%
cyclohexanone 33%
xylene mixture 50%

Emulsions of any required concentration can be obtained from this concentrate by dilution with water.

7) Du a) b) active ingredien~ 5% 8%
talcum 95%
kaolin - 92%

Dusts which are ready for use are obtained by mixing the active ingredient with the carriers 9 and grinding the mixture in a suitabla mill.

8) Extrucler ~ranulate active ingredient 10%
sodium lignosulfonate 2%
carboxymethylcellulose 1%
kaolin 87%

The active ingredien~ is mixed and ground with ~h~ adjuvants, and ehe mix~ure is subsequen~ly moistened ~ith water. The mixture is extruded and then dried in a s~ream of air.

' -1 4 1 ~

9~ Coated granulate -active ingredient 3%
polyethylene glycol 200 3%
kaolin 94%

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin ~oistened with polyethylene glycol~ No~-dusty coated granulates are obtained in this manner.

10) Suspension concentrate active ingredient 40%
ethylene glycol 10%
nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6%
~odium lignosulfonate 10%
carboxymethylcellulose 1%
37% aqueous for~aldehyds solution 0.2%
silicone oil in the form of a 75%
aqueous emulsion 0.8%
water 32%

The finely ground active ingredient is inti~ately mixed with ~he adjuvants, giving a euspension concentrate from ~hich suspensions of any desired concentration can be obtained by dilution with water.

- 12 - ~ 8 ~ 4 ~ O

Example 1: Preparation of the salt of the formula [( 3)3 ~ 2 ~ [ ( ~ / ~ S

80.7 g of the compound of ~he formula t~ H \ ~ Sn Cl .~. 3 and 49.4 g of the salt of the formula (C~3)3N - CB2CH2Br ~ ~ are dissolved in a mix~ure of 300 ml of methanol and 550 ml of ace~one.
The solution is heated under reflux for 1 hour and concentrated.
Precipitation with diethyl ether yields the compound of the formula [( 3)3 2 ' ~ i ( H /

with a melting point of 205-210~C.

l'he following compounds are also prepared in analogous msnner:

L 3~3 ~2CH2Cl~ [CH3- 5~\ ~ m.p.: 98-99C

~( 3)3N CB2C~2Cl ~ [ (~ ~ ~ Sn\ ~ m.p.: 132-133C

~ ~14~
~(CH3)3N-CH2CH2C1 ~ s n \ ] m . p . 194-196 C
~CH3)3N-CH2-8H-CH2-C1 ~ >~ s n \ ] m . p . 126-128C
¦EI3NC2H4C1 ] ~ >~ sn\ ~ m.p. 132-134C
[(C2~I5)2HNC2H4C1 ] ~ t~t~ - sn\ ] m.p. 126-128C
[C~I ) NC~ C~ C~I] ~3[(~ 3~ - - sn/ ] m.p. 112-114C
[~13NC2H4B~ [ (~ -- Br ] m.p. 135-137C
~CH3)3NC2H4OH ] [ (~ - sn ¦
m.p . 128-130C

4 ~ ~
Example 2: ~ction against plant-destructive acarids: Tetranychus urticae _(OP-sensitive) and Tetranychus cinnabarinus (OP-tolerant) 16 hours before the test for acaricidal action, the primary leaves of Phaseolus vulgaris plants are infected with an infested piece of leaf from a mass culutre of Tetranychus urticae (OP-sensitive) or Tetranychus cinnabarinus (OP-tolerant). (The tolerance refers to the tolerance to diazinone). The trea-ted, infested plants are sprayed dripping we-t with a test solution containing 25, 50, 100 or 200 ppm of the compound to be tes-ted.
L0 ~ count of the number of living and dead imagines and larvae (all mobile stages) is made under a stereoscopic microscope after 24 hours and again after 7 days. One plant is used for each test substance and test species. During the test run, the plants are kept in greenhouse compartments at 25C.
Within the above indicated concentration limits, the compounds of the preparatory Examples are effective against larvae o~ the species Tetranychus urticae and Tetranychus cinnabarinus (vide the following table).
Biological test results The results of the test carried out in the foregoing F.xample are reported in the table, using the following rating to :lndicate the percentage kill of the pests:
A: 100% klll at a concentration of 25 ppm B: 100% kil] at a concentration of 50 ppm C: 100% kill at a concentration of 100 ppm D: 100% kill at a concentration of 200 ppm.

~ o o~ ~

~ ~ ~ .¢

,c ~ ~ u`if~

r ~

1,, i 1 ~ IJ

,. ~

~n ~
~, r!
C~ ~
~ ~ ~ I ~ I I

(L) rl E~

tq O V ~ V
rl ~
E~ ~ ~

rl r-l r rl (3 ~

I V
O--V ~ I / O
O l~u V~
V Z ~ Z

o ~Yl V V V
o , ~ ~ L . ~

~81~1~

U~
,r r~
C) ,r l P, td ,r~, p (L) r~
(L) rt E~ C) rn rr r~ V V
,r,l ~rl rt_~

r t J

rrl t ~
V V
r-t ~ I\ /
V l~

~ (~I
~q V

r~ ~ ~Y) O
~z ~v o , ~ I ,, , ~
~ ~y .~. .^

Claims

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

1. An organo-tin substituted ammonium salt of the formula or of the formula wherein each of R1, R2 and R3 is hydrogen or the same or different alkyl of up to 20 carbon atoms;
R4 is epoxyalkyl, haloalkyl or halohydroxyalkyl, each containing up to 6 carbon atoms;
R5 is alkyl of up to 6 carbon atoms, cyclohexyl or phenyl;
each of R6 and R7, independently of the other is either the same as R5 or the same as X1 as hereinafter defined;
X1 is chloro or bromo; and X2, X3 and X4 are either all chloro or all bromo.

2. A compound according to claim 1 wherein said organo-tin substituted ammonium salt is of the formula:

wherein R4 is chloroethyl, bromoethyl or 3-chloro-2-hydroxypropyl;
R5 is methyl, cyclohexyl or phenyl;
each of R6 and R7, independently of the other, is chloro, cyclohexyl or phenyl; and X2 is chloro or bromo.

3. A compound according to claim 2 wherein said organo-tin substituted ammonium salt is of the formula:

wherein R4 is chloroethyl, bromoethyl or 3-chloro-2-hydroxypropyl.

4. The compound according to claim 3 of the formula

5. The compound according to claim 2 of the formula

6. The compound according to claim 2 of the formula

7. The compound according to claim 3 of the formula

8. The compound according to claim 3 of the formula

9. The compound according to claim 1 of the formula

10. The compound according to claim 1 of the formula

11. A process for the production of a compound according to claim 1, which process comprises reacting a compound of the formula with a compound of the formula in which formulae R1 to R6 and X1 and X2 are as defined for claim 1.

12. A method of controlling a variety of pests of animals and plants and of regulating plant growth, which comprises the use of a compound according to claim 1.

13. A method according to claim 12, wherein the pests to be controlled are insects and representatives of the order Acarina.

14. A method according to claim 12, wherein the pests to be controlled are phytopathogenic mites.