Note: Descriptions are shown in the official language in which they were submitted.
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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
--1--
,.~''~,, ~.
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
R4 R7
(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.
--2--
1 0
- 3 -
~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
-- 4 --
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 ~
-- 8 --
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.
-- 10 --
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.
-14-
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--17--
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