CA1238647A - S-aralkyltrithiophosphonate insecticides - Google Patents

Abstract

S-ARALKYLTRITHIOPHOSPHONATE INSECTICIDES

Abstract of the Disclosure Compounds having the formula in which R1 is C1-C3 alkyl; R2 is C3-C6 alkyl; R3 is hydrogen, halo, tri-fluoromethyl, C1-C4 alkyl, C1-C4 alkoxy, phenoxy, cyano, nitro or C2-C5 carboalkoxy; n is an integer from 1 to 5; -A- is

Description

~3~'7 S-A~ALRYLTRITHIOP~OSP ONATE INSECTICIDES

m is invention relates to a series of trithiophosphonate insec-ticides having the formula \ P-S-A ~ ~ (R3)n in which R1 is Cl-C3 alkylt R2 is C3-C6 alkyl; R3 i5 hydrogen, halo, tri-fluoromethyl, C1 C4 alkyl, C1-C4 alkoxy, phenoxyl cyano, nitro or C2-Cs carboalkoxy; n is an int0ger from 1 to 5; -A- is ~ E~-(CH2)m~;
R4 is hydrogen, C1-C4 alkyl or -CH2Y; m is 0 or 1; and Y is halo; together with insecticidal ccTFositicns containing such compounds, and methods for their use in controlling insects.

The teLm "halo" includes chloro, brcmo, fluoro and iodo, with chloro, bromo and fluoro being preferred. R1 is pre~erably meth~l or ethyl. R2 is preferably a branched alh~l group, and most preferably one at which the branching occurs at the alpha- or beta- carbon atom, such as sec-butyl or tertiary butyl. m e substituents on the phenyl ring may be located at one or more of the five possible positions. Preferably n is 1,

2 or 3. The group A is, for instan oe , methylene, 1,2-ethylene, 1,1-ethylene or 2-halo~ ethylene. Mbst preferably, A is a methylene group and the oompounds are S-(substituted) benzyl trithiophosphonates.

The term "insects" as used herein refers to the broad and com-monly understood usage rather ~han to those creatures which in the strict biological sense are classified as insects, and includes, in addition to those belonging to the class Insecta, some classes of acarids such as spiders, mites, ticks, and t~ like, particularly mites.

The oompo~ds of this invention have demonstrated activity against a number of insect species, and shcw particularly good activity against mites and aE~hids, and in some cases lepidoptera and Diabrotica.

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~3~ 7 m e c3mpo~nds of the present invention may be prepared by a two-step process.

In the first step the appropriate alkyl thionophosphine sulfide is reacted with tw~ equ.ivalents of a desir.ed mercaptan in the presence of a ~ase to produce a thioic acid salt, according to the equation:
S~S S S
(1 ) R1-P~ ~P-R1 + 2R2SH --~ 2Rl-P~H-base S base SR2 In the second step, the thioic acid salt is reacted with the appropriate aralkyl halide: ~

(2) Rl-P-SH-base ~ X~ ~ R1-P S-A ~ R3)n A, R1, R2, R3 an~ n are as defined above and X stands for halogen.

The starting material sulfides for Reaction 1 may be obtained for instance by the procedure descriked in P.E. Nbwalli5 et al~, Journal of O~l nic Chemistr~, 1962, Vol. 27, p. 3829.

~ eaction 1 is advantageously carried out at a temperature of from akout -40C to about 150C, preferably from about 0 to about 70C, in an organic solvent in the presen oe of a base, preferably a tertiary amine.
Suitable solvents include arcmatic hydrocarkcns such as benzene or tolu-ene, ethers such as diethyl ether or tetrahydrofuran, and ketones such as acetone. Suitable tertiary amines include triethylamine, dimethylaniline, diethylaniline, and pyridine. Inorganic bases such as sodium hydroxide oould be used in this step, but are less desirable as the resulting salts are less soluble in tha solvents utilized. As the reaction is exothermic, the base is preferc~bly added dropwiæ when operatin~ on the lc~boratory scale. Ihe produ t may be reo~vered by e~aporating or distilling off the solvent.

Reaction 2 is oonducted in c~n organic solvent such as that utilized in the first reaction, at a temperature of frcm about 20C to about 130C, prefercibly from c~b~ut 20 to cibout 70Co The aralkyl halide :

~3~ 7 may be either a chloride or bromide. The product may be recovered by remo~i~g ~he precipitated salt, followed by e~aporating or distilling off the solvent, and purification by either chrcmatography or distillation.
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The following represent examples of the preparation of oompounds of this invention.

,EXA~IE 1 _n of S-s-Butyl S-(2-Bromoben~2yl) Ethylphosphonotrithioate (ComFound 13 herein) (a.~ Tb a slurry of 30 grams (g) (0.121 mole) of ethylthiono-phosphine sulfide in 175 milliliters (ml) of tetrahydrofuran, maintained under nitrogen and at room temperature, was added 27.6 ml (22.9 g, 0.254 le) of 1-methyl-1-propanethiol. T~ the resultant solution was 2dded 35.4 ml (35.7 g, 0.254 mole) of triethylamine dropwise and the reaction mixture was refluxed for 4 hours. After cooling, the nuxture was evap-orated tG give 62.8 g (83%) of a viso~us oil, the triethylamine salt of S-s-butyl ethylphosphonotrithioc acid~

~b.) Tb a solution of 3.0 g (0.0095 mole) of the triethylamine salt [o~tained in step (a)] in 15 ml of tetrahydrofuran, maintained urder nitrogen and at room temFerature, was added dropw~se a solution of 2.86 g (0.0114 mol~) o-~ramobenzyl bromide in 10 ml of tetrah~drofuran. The resultant mixture was refluxed for 3 hours. After cooling, 10 ml of water was added and the mixture was extracted three times with 10 ml portions of ether. The ethereal layers were oombined and ~ashed wi~h 20 ml of water and 20 ml of brine, and dried with magnesium sulfate. Evaporation afforded a light yellow oil. Bulb-to-bulb distillation ~cven temperature 135-145C (0.005 torr)] yielded 2.88 9 (79~ of theoretical yield) of the title oomFound, a colorless oil. The structure was oonfirmed by nuclear magnetic resonance, infrared and mass spectroscopy~

Preparation of S-s (Compound 6 herein) ~ ollowing the procedure as shown in Zxample lj step (b), 1.25 g (35% of theoretical yield) of the title compound was prepared frcm 3.0 g ,.

~Z3~ t7 (0.0095 mole) of the triethylamine salt of S-s-butyl ethylphosphonotri-thioic acid (Example 1, step (a~) and 2.05 g (0.0105 mole) of 3,4-di-chlorobenzyl chloride. Purification was effected by a preparative, centrifugally acclerated, thin-layer (4 mm, silica gel) chromatograph, with 98:2 hexane-acetone as eluent. The structure was oonfinmed by spec-troscopy as in Example 1.

EXAMæLE 3 Preparation of S- -B
(ComFound 22 herein) Following the procedure as shown in Example 1, step (b), 3.0 g (0.01 mole) of the triethylamine salt of S-t-butyl methylphosphonotri-thioic acid (prepared from methylthionophosphine sulfide, t-butyl mercap-tan and triethylamine by the procedure shown in Example 1, step (a)) and 2.30 g (0.012 mole) of 2,4-dichlorobenzyl chloride afforded 1.36 g (44% of theQretical yield) of the title compound. Purification was effected by a preparative, centrifugally accelerated, thin-layer (4 mm, s~ ica gel) chromatograph, with 98:2 hexane-acetone as eluent. The structure was oon-firmed by spectrosoopic analy æ s as abcve.

Ihe followqng Table I depict~ representative oo~pounds of this invention, which may be prepared by the process previously describ~d.
Structures of these compounds were confirmed by analysis as above.

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;4L`7 s TABLE I
R1 \ S ~ (R3)n Compoun~ A ~ 30 Number Rl ~ ~
1 C2H5 t-C4H9 4-Cl CH2 1.5923 2 CH3 t-C4Hg 2,4-C1 CH2 1.6180

3 C2HS t-C4Hg 2,4-Cl CH2 1.6080

4 C2H5 sec-C4Hg 4-Cl CH2 1.6050 C2~15 sec-C4Hg 4-F CH2 oil 6 C2H5 sec-C4Hg 3,4-Cl C~2 1.6183 7 C2H5 sec-C4H9 4-CF3 ~CH2 oil 8 C2HS sec-C4Hg 2,3,4,5,6-F CH2 oil 9 C2H5 sec-C4Hg 2-Cl CH2 oil C2H5 sec-C4Hg H CH2 1.6065 11 C2H5 sec-C4Hg 2,4-C~13 CH2 oil 12 C2H5 sec-C4Hg 3-Cl CH2 oil 13 C2H5 sec-C4Hg 2-F CH2 1.5944 14 C2H5 sec-C4Hg 2-Br CH2 1.6228 C2H5 ~ec-C4Hg 2-CH3 CH2 oil 16 C2H5 sec-C4Hg 4-CH3 C~2 oil 17 C2H5 s~C-c4H9 2-OCH3 C~2 oil 18 C2H5 sec-C4Hg 2-CN CH2 thick oil 19 C2H5 sec-C4Hg 2-COCCH3 CH2 thick oil C2H5 sec~-C4Hg 2,6-Cl C~2 thick oil 21 C2H5 t-C4H9 H CH2 oil 22 ~H3 sec-C4Hg 2,4-C1 CH2 1.6247 23 C2H5 sec-C4Hg 2,4-C1 CH~ oil 24 i-C3H7 sec-C4Hg H CH2 oil nrC3H7 sec-C4Hg 2,4-C1 CH~ oil 26 CH3 sec-C4Hg 3,4-C1 CH2 106213 27 C2H5 sec-C4Hg 2,5-C1 CH2 1~6150 28 C2H5 sec-C4Hg 3~~ CH2 oil 29 C2H5 sec-C4Hg 3-CF3 CH2 oil C2H5 sec-C4Hg 4-N02 C~2 oil .

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il~3~ 7 TABLE I
(Continued) Compound 30 Number R1 - R2 ____~ _____ A n~
31 C2H5 sec-C4Hg 3-N02 CH2 1.6198 32 C2H5 sec-C4Hg 2-N02 CH2 oil 33 n-C3H7 seo-C~Hg H CH2 oil 34 C2H5 sec-C4Eg 2-CF3 CH2 1.5642 i-C3H7 sec-C4Hg 2,4-Cl C~2 oil 36 C2H5 nrC3H7 2,4-Cl CH2 1.6268 37 C2H5 n-C3H7 3,4-Cl CH2 oil 38 C2H5 n-C3H7 H CH2 oil 39 C2Hs n-C3H7 2-Br CH2 1.6353 C2H5 i-C3H7 2-Br CH2 oil 41 C2H5 i-C3H7 3,4-Cl C~2 oil 42 C2H5 i-C3H7 2,4-Cl CH2 oil 43 C2H5 sec-C4Hg 3-Br CH2 oil - 44 C2~5 sec~C4H9 4-Br CH2 oil C2E5 sec-C4Hg 3-CN CH2 oil 46 C2~5 sec-C~Hg 4-CN CH2 1~6154 47 ~2H5 sec-C4Hg 3-CH3 CH2 oil 48 C2H5 sec-C4Hg H -CH2CH~- oil c~3 49 C2H5 sec-C4-Hg H -CH- oil CH2Br C2H5 sec-C4Hg H -CH- thick oil 51 C2~5 t-C4Hg 3-Gc6H5 CH2 thick oil 52 C2H5 sec-C4Hg 3,5-C1 CH2 1~6150 53 C2~5 sec-C4Hg 2,3,4 cl C~2 1.6220 54 CH3 t-C4Hg H CH2 oil ~e The compounds in Table I a~ove were tested for insecticidal act-ivity using the following testin3 procedures. LD-50 values, based on the results of ~hese tests, and/or calculated according b~ dosage-mortality curves, are expressed in Table II~

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~38~

]Musca domestica]:
Test c~mpounds were diluted in acetone and aliquots pipetted onto the botton of aluminum dishes. Tb insure even spreadiny of ~he chem-ical on the bottom of the dishes, 1 ml of acetone containing 0.01% peanut oil was also added to each dish. After all solvents had evaporated, the dishes were placed in circular cardboard cages oontaining 25 female house-flies, 1-2 days old~ The cages were covered on the bottam with cellophane and on the top with tulle netting, and each contained a sugar-water saturated o~tton plug for maintenance of the flies. ~crtality was recorded after 48 hours. Test levels ranged from 100 ~g/~S female house~
flies downward. The LD-50 values are expressed below in Table II under the heading "HF-C", in terms of ~g of ~he test oompound per 25 female flies.

Black Bean Aphid ~A~ fabae (Scop.)]:
Nasturtium plants (Tropaeolum sp.) approximately 5 cm tall, were transplanted into sandy loam soil in small cups and infested with 25-50 black bean aphids of mixed ages Twenty-four hours later they were sprayed to the point of runoff with 50-50 acetone-water solutions of the test conpounds. Treated plants were held in the greenhouse and mortality was recorded after 4~ hours. Test ooncentratians ranged from 0.05% down-ward. The LD-50 values are expressed below in Table II under the heading "BA-CI- in terms of percent of the test compound in the sprayed solution.

Tobacco Budworm [Heliothis virescens tFabricius)]:
(a) Contact: Test compounds ~ere diluted in a 50-50 acetone-water solution. Cbtton ( ~ ~ ) cotyledons were immersed in the test solutions for 2-3 seoonds and placed on a wire screen to dry. The dried leaves were placed in petri dishes oontaining a moistened piece of filter paper and infested with 5 seoond-instar tobacco budworm larvae.
m e dishes were placed in a high humidity chamker for S days, and percent mortality of the larvae recorded. Test concentrations ranged from 0.1%
downward. Ihe LD~50 values are expressed below in Table II under the heading "TBW-C" in terms of percent of the t~st compound in the solu~ion.

(b). ~s: Paper towel patches of 2-day old eggs of the tobacoo budworm weYe dipped in acetone solutions of ~he test comFounds and placed in petri dishes containing a portion of larval rearing medium.

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Treat^d eggs ~-ere maintained at 78F. and mortality was recorded after all control eggs had hatched and the y3ung larvae were feeding on the media.
Test concentrations ranged from 0.1~ downward. The LD-50 values are expressed below in Table II under the heading "TBW-E" in terms oE percent of the test oompound in ~he solution.

Beet Army~ (Spodoptera exi~ua?:
Test compounds were diluted in a 50-50 acetone-water solution.
Young leaves of sugar beets (Beta ~ ) were immersed in the test solutions for 2-3 seconds and placed on a wire screen to dry. m e dried leaves were placed in petri dishes containing a moistened filter paper and infested t~th five second-instar beet anmyworm larvae. m e dishes were placed in a high humidity chamberO Mkrtality of the larvae was recorded five days later. Test concentrations ranged from 0.1% downward. The LD-50 values are expressed below in Table II under the heading "B~W" in terms of percent of the test oompound in solution.

Cabbage Lo per [ ~ nl (Hubner)~:
Test oompounds were diluted in a 50-50 acetone-water solution.
Cbtyledons of hyzini squash (Calabacita _obrinha), approxlmately 1 x .5 inches~ were immersed in the test ~olutions for 2-3 seconds and placed on a wire screen ~o dry. The dried leaves were placed in petri dishes con-tainin~ a moistened piece o filter paper and infested with 5 second-2D instar cabbage looper larvae. The dishes ~ere placed in a high humidity chamber. Mortality of the larvae was recorded 5 days later. Test concen-trations ranged from 0.1% downw2rd. The LD-50 values are expressed below in Table II under the heading "CL" in terms of percent of the test cDm~
FUnd in this solution.

W~ Fotted ~ucumber Beetle Larvae [Diabrotica ~ (Mannherheim)]:
Ten grams of m~ist potting soil was placed in a plastic cup.
Test oompounds were dissolved in acetone or an other appropriate solvent.
A 0.05 ml aliquot of the test sample, diluted to the desir~d ooncentra-tion, was added to the soil. The cup was capped and the soil was mixed on a vortex mixer for aproxima~ely 15 sec~nds, An indentation was m~de on the surface o the ~oil and approximately 50 Diabrotica eggs ~ere added~

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~3~ '7 The eggs were covered with soil and maintained at room tempera~ure (approximately 70F. or 21C.). Four days later a section of ~omaine lettuce (Latuca sativa) leaf was placed in the treated cups. One week later the cups were examined for live larvae. Test conoe ntrations range~
from 25 ppm downward. m e LD-50 values are expressed below in Table II
under the heading "Diabrotica" in terms of ppm of the test c~mpound in the SOil.

German Cockroach [Blatella germanica (Linn.)]
Test ccmpounds were diluted in a 50-50 acetone-water solution.
Two ml of the solution was sprayed through a hand spray gun into circular cardkoard cages containing 10 one~month old German cockroa,c,h nymphs. m e test cages were covered on the bottom with cellophane and on the top with tulle netting. Percent mortality was reoorded 4 days later. Test concentrations ranged from 0.1% downward. m e LD-50 vcalues are expressed below in Table II un~er the heading GR" in terms of percent of the test compound in the sprayed solution.

Lygus hesperus ~Knight)]:
Test compounds were diluted in a 50-50 acetone-water solution.
T~o ml of the solution was sprayed through a hand-spray gun into circular cardboard cages containiny 1 green bean pod and 10 c~dult lygus bugs. The test cages were covered on the bottom with cellophane and on the top with tulle netting. Percent mortality was recorded 48 hours later. Test con-centrations ranged from 0.05% downward. The LD-50 values are Yxpressed below in Table II under the heading "LB" in terms of percent of the test compound in the sprayed solution.

Acaricidal Evalua~ion Test The twc-s~otted mite (2SM) ~etran~chus urticae (Koch)] was employed in tests for miticides. m e test procedure was as follows:

Pinto bean plants (Phaseolus ~) approximately 10 om tall, were transplanted into sandy loam soil in small cups and thoroughly infested with two-spotted mites of mlxed ages and sexes. Twenty-four hours later the infested plants were inverted and dipped for 2-3 seconds in 50-50 acetone-water solutions of the test compounds. Treated plants were held ~;Z3~

in the greenhouse, and 7 days later mortality was determined for both adult mutes and the nymphs hatching frcm eg~s which were on the plants at the time of treatment. Test concentrations ranged from 0.05% downward.
The LD-50 values are ex~ressed below in Table II under the headings "2SM-A" (i.e., adults) and "2SM-E" (ile. eggs) in terms of percent concentration of the test oompound in the solution.

Systemic Assay on Black B _ n A~d [Aphis fabae ( c p.)]
Nasturtium plants (Tropaeolum s~.), approximately 5 cm tall, were transplanted into 400 grams of sandy loam soil in one pint con-tainers. Test chemicals were dissolved in acetone and aliquots diluted in 50-60 ml of water. The treated water was poured onto the surface of the soil and allowed to thoroughly soak in. The treated plants were infested with 25-5Q black bean aphids of mixed a3es and held in the greenhouse.
Mortality was recorded after three days. Test concentrations ranged from 10 ppm down to that at ~hich 50% mortality occurs. The LD-50 values are t5 expressed in Table II under the heading "BA(S)" in terms of ppm of the test ccmpound in the soil.

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However, in general, the campounds are first formulated with one or more inert (i.e. non-chemically reactive, plant ccmpatible or herbicidally inert) carriers or diluents suitable for insecticidal use, before being applied.

Ihe compositions or fonmulations, including a compound as described herein, may take any one of a number of solid cr liquid fon~s.
Examples of solid forms are dusts, granules, tablets, pow~ers and the like. Examples of liquid forms are emulsions, solutions, suspensicns, flowables, emulsifiable concentrates and E~astes. Such oompositions may contain, in addition to the active compour~ or campounds, various carriers or diluents; surface-active agents (wetting agents, dispersing agents and/
or emulsifying agents); solvents (water, or organic solvents such as aro-matic solvents or chlorinated aliphatic solvents); adhesives; thic~eners;
binders; anti-foaming agents; and other substances as mentioned herein Solid carriers or diluents included in such oompositions or formulations may include, for example, ground natural minerals such as kaolins, alum~
ina, calcium carbonate/ silica, kieselguhr, clavs, etc.; ground synthetic minerals such as v æ ious silicates and aluminosilicates and ground vege-~0 table products such as bark, cornmeal, sawdust, cellulose powder and thelike.

To manufacture solid compositions, the aotive substances are mixed with solid carriers or diluents such as those mentioned above and the mixture is ground to the appropriate size. Granules can be manufac-tured by dissolving an active compound in an organic solvent and applyin~the mixture, ~or example, by atomization, onto an absorptive granulated inert ma~erial, such as silica. Adhesives may be utilized to assist in the incorporation of the compound onto the solid particles.

Wettable powders a~d pastes are obtained by mixing and grinding an active oompound with one or more dispersing agents and/or olid car-riers or diluents. Also included may be wetting agents and/or dis~ersing agents, for example~ lignins, methyl cellulose, naphthalenesul~onic acid derivatives, fatty alcohol sulfa~es and various types of akali and alka-line earth metal salts of fatty acids.

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Emulsifiable concentrates are generally obtained by dissolving the active oompound in an organic solvent, for example, butanol, cyclo-hexanone, xylenes, or higher boiling aromatic hydrocarbons. To obtain suspensions or emulsions in water, wetting agents may also be added.

Flowables are prepared by mixiny an active comFound with one or more dispersing agents and/or solid additives, and a liquid (which may be water or an organic solvent) in which the active compoun~ is relatively insoluble, and grinding the mixture.

Both liquid and solid comFositions ~ay be in microcapsule or encapsulated form, to permit release of the enclosed active compound at a controlled rate over a period of time. Liquid ccmpositions of this type contain encapsulated droplets of approximately 1-50 microns in diameter, including the active oompound and optionally a solvent. The encapsulating material is an inert porous menbrane of a polymeric material.

Solid encapsulated comFositions generally take the form of gran-ules, in which the liquid containing the active component is trapped in the pores of the granular support by a porous polymeric membrane through whicb the active ingredient may migrate at a contr~lled rate, or which membrane breaks down at a controlled rate to permit escape of the active ingredient.

Typical encapsulating materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylo-nitriles, polyacrylates, polyamides, polyisocyanates, polyurethanes, mixed o~polymers of the foregoing and starcb xanthates.

It is ~ossible to use highly o~ncentrated liquid comp~sitions containing up to about 95% by weight of the active comFound, or even the 100% active compound alone, when applying the ocmpound in the form o~ a finely divided liquid by use of various atomizing equipment, for example by airplane spraying techniques. Fbr other purFoses, however, the various types of oompositions which can be utilized for ~hese compounds will con-tain varying amount~, of the compound accordin~ to the type of co~position and the intended use.

~llZ38~'7 In general, insecticidal oanpositions may contain from 5 to 95~
of the active canpound, more preEerably from 10 to ~5~. Scme typical co~r positions will contain an active compound as follows: wettable powders:
25 to 80% active canpound; oil suspensions, emulsions, solutions, flow-ables, and emulsifiable concentrates: 5 to 85~ active canpound; aqueoussuspensions: 20 to 50% active canFound; dusts and powders: 5 to 20%
active compound; granules and pellets: 5 to 20~ active oompound.

In addition to the active ocmpo~md and the various agents utilized i.n preparing ccmpositions and formulations ~entioned, such oompo-sitions may also contain one or more other. active ccmpounds of the typementioned herein as well as other active pesticidal agents~ such as herbi-cides, fungicides, insecticides, acaricides, nematocides, bactericides, and plant growth regulators. Such compounds may also contain soil disin-fectants or fumigants and may further conkain fertilizers, thus makiny it possible to provide multi-purFose oompositions containing one or more of the active ocmpounds described herein as well as, opkionally, other pesti-cides and also fertilizers, all intended and formulated for use at the same locu5.

C~ntrol o insect pests is accomplished by aF~lying a oomposi-tion containing an insecticidally effective amount of an active c~mpoundas described herein to the insect, to a locus at wh.ich insecticidal con=
trol is desired, or to food sour oe s (inclu~ing seeds~ on ~hich the insects fe~d. Fbr use in the last mentioned manner it is preferable to utilize a oomFound which is not volatileO Thus~ control ~ay be achieved by direct application of ~he ac~ive co.mFounds to the insects and indirectly by application of the oompounds to a locus to be protected (such as crop lands, grass ranges and forests), to a source of food for insects or to other insect habitats (for example, br~eding or swanming areas). The rates of application of the active ccmFound, and the con oe ntration applied, will vary according to whether the compound or oomposition is being directly applied to the insect or indirectly, to a locus, food or habi~at. In the latter case the rate of the application, depending on the nature o the insect or insects to be controlled, and the plant environ-ment, will generally vary from about 0.01 to about 100 pounds per acre (about 0.012 to about 111 kg/ha).

.

:~;23~7 It should be noted that the active c3mpound need not be insec-ticidally active Fer se to effect insect control. The purposes of this invention are fully served if such compounds are rendered active by exter-nal influences, such as light or heat, or by some physiological action ~hich occurs when the comound is ingested into the body of the insect.

Cbmpositions containing one or more of the active ccmpounds described, in an insecticidally effective amount, may be applied to the plant, locus or insect habitat in any conventional manner.

When used in connection with crop or other plant protection, application may be made in a preventive (i.e. before infestation) or eradicative manner (i.e~, after infestation). ~hus, powders and various liquid oompositions ccntaining the active oompound can be applied by the use of power dusters, boom and hand sprayers and spray dusters, or applied from airplan~s as dusts or sprays. ~hen applied in the la~ter method they may be effective in vexy low dosages.

Compositions including active compounds may al50 be applied by addition to irrigation waters supplied to the field to be treated. mis method of application permits penetration of the compounds into the soil as the water is absorbed therein.

Cbmpositions including active comFounds may additionally be used to protect plant seeds from being attacked by soil-borne insect pests after planting and during germination, by applying the composition to the seeds as a seed dressing. Ihis is performed generally by mixin~ the seeds with an astive oomposition in either liquid or solid form ~preferably 25 liquid) in a suitable mixing appQratus. Liquid oomposi~ions for this pur-pose may contain an adhesi~e or sticking agent, such as methyl cellulose, ethyl cellulose, etc.~ to assist the canp~sition in adhering to the seed.
. If a solid composition is utilized for this purpose, an ~hesive agent may be spray~d cn the seeds during or after mixin~.

Ebr use as a soil insecticide, the active ccmpound, or canposi-tions containing it, may be mixed :with the soil in any conventional man-ner, before, during or after planting of the plant seeds. Liquid ~2~ 7 compositions may be applied by spraying onto the surface or by inoorpora-tion in irrigation or spray~d water. Solid or liquid compositions con-taining an active compound may be incorporated into the soil prior to or during planting by discing, plowing or other mixing ~perations, in order to locate the active ingredien~ below the surface o the soil so as to be st effective in oontrolling undesirable larvae.

Some examples of ccmpositions containing the active compounds of this invention are:

Composition A: Granular Solid _ Wei~ht %
Compound 1 10 attapulgite clay ~ranules 90_ Ibtal 100%

Comp;sition B: Wettable Po~der Component Weight %
-Compound 3 80 wetting agent (sodium dialkyl- I
naphthalene sulfonate) dispersing agent (sodium 4 lignosulfonate) diluent ~aluminum magnesium 15 silicate) Tbtal 100 Composition C. 1~
~ W~
Compound 6 5 solvent (xylen~) 95 Tbtal 100%

~;Z ;3~

C~ Weight %
Comeound 9 50 Emulsifier (blend of metal sulfonates and polyoxy- 10 ethylenR ethers) solvent (xylene) 40 Total 100%

ComFosition E: Concentrated Solution ComEonent Weight %
Gcmpound 15 90 solvent (xylene) 10 Tbtal 100%

Claims (11)

WHAT IS CLAIMED IS:

1. A compound having the formula in which R1 is C1-C3 alkyl; R2 is C3-C6 alkyl; R3 is hydrogen, halo, tri-fluoromethyl, C1-C4 alkyl, C1-C4 alkoxy, phenoxy, cyano, nitro or C2-C5 carboalkoxy; n is an integer from 1 to 5; -A- is R4 is hydrogen, C1-C4 alkyl, or -CH2Y; m is O or 1; and Y is halo.

2. A compound according to Claim 1 in which R1 is methyl or ethyl.

3. A compound according to Claims 1 or 2 in which R2 is an alpha- or beta-branched alkyl group.

4. A compound according to Claims 1 or 2 in which R2 is n-propyl.

5. A compound according to Claim 1 in which A is methylene.

6. A compound according to Claim 1 in which R3 is halo and n is an integer from 1 to 3.

7. A compound according to Claim 5 in which R1 is ethyl, R2 is secondary butyl, A is methylene, and (R3)n is 3,4-dichloro.

8. An insecticidal composition comprising an insecticidally effective amount of a compound according to Claim 1 and an insecticidally suitable inert diluent or carrier.

9. A method for controlling insects comprising applying to said insect or to a locus at which control is desired an insecticidally effect-ive amount of a compound or composition according to Claim 1.

10. A method according to Claim 9 in which the insects to be controlled are mites.

11. A process for producing a compound according to Claim 1 comprising (a) reacting an alkyl thionophosphine sulfide having the formula with two equivalents of a mercaptan having the formula R2SH in the presence of a base to produce a thioic acid salt; and (b) reacting the thioic acid salt of step (a) with an aralkyl halide having the formula in which X stands for halogen.