US3144383A

US3144383A - Nematocides

Info

Publication number: US3144383A
Application number: US73229A
Authority: US
Inventors: Paul C Aichenegg; Carl D Emerson
Original assignee: Chemagro Corp
Current assignee: Chemagro Corp
Priority date: 1960-12-02
Filing date: 1960-12-02
Publication date: 1964-08-11
Anticipated expiration: 1981-08-11

Description

United States Patent Oifice 3,144,383 Patented Aug. 11, 1964 3,144,383 NEMATOCHDES Paul C. Aichenegg, Prairie Village, lKans., and Carl D.

Emerson, Liberty, Mm, assignors to Chernagro Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Dec. 2, 1960, Ser. No. 73,229 7 Claims. (Cl. 167-22) The present invention relates to novel nematocides,

It is an object of the present invention to develop an improved process for killing nematodes.

Another object is to develop formulations for killing nematodes which are non-injurious to plants.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by applying to the soil containing nematodes a composition containing a di-u,,8-unsaturated sulfone having one of the formulae In the formulae R and R can be the same or different and are hydrogen or alkyl. R is aryl or substituted aryl, e.g., phenyl, naphthyl, halophenyl, nitrophenyl, alkyl phenyl, and alkoxyphenyl, or is cycloalkenyl, e.g., cyclohexenyl. In the case where R is cycloalkenyl the double bond should be on the carbons e t? to the sulfone group, The aromatic double bond in the phenyl or substituted phenyl compounds also meets this requirement.

The most preferred compound is divinyl sulfone.

Another especially preferred class of compounds is phenyl vinyl sulfone and ring substituted phenyl vinyl sulfones.

It has been found important for outstanding nematocidal action that both carbons which form C-S bonds with the sulfone group be themselves part of a C=C unsaturation and that at least one of these two groupings be an unsubstituted vinyl group. Otherwise the product has poorer nematocidal activity.

The compounds of the present invention have strongly toxic properties against both saprophytic and parasitic nematodes among such nematodes are Panagrellus, Rhabditis spp. and Meloidogyne spp. which are known to cause severe damage to the roots and lowering the weight yield of such crops, e.g., cucumbers, and tomatoes, tobacco sugar beets and other vegetables, citrus fruits, forage crops etc.

While it has previously been proposed to employ certain sulfones, including divinyl sulfone as herbicides, Fincke Patent 2,634,202, such is no indication that the sulfones would be highly effective as nematocides. In fact some of the sulfones preferred by Fincke as herbicides are relatively ineffective as nemotocides.

Nematocides are normally applied to the soil prior to sowing the crop. It is important therefore, that the nematocides not act as a pre-emergent herbicide. It has been found that the sulfones employed in the present invenvention can be used in concentrations which will not cause undesirable herbicidal activity.

In general it has been found desirable to employ the sulfones as nematocides in concentrations of 6 to 200 lbs/acre, preferably 20 to 80 lbs'./ acre.

As examples of sulfones which can be used as nematocides according to the invention there are divinyl sulfone, l-methylvinyl vinyl sulfone, Z-methylvinyl vinyl sulfone, 2-hexylvinyl vinyl sulfone (l-octenyl vinyl sulfone), l-hexylvinyl vinyl sulfone, l-cyclohexenyl vinyl sulfone, phenyl vinyl sulfone, ot-naphthyl vinyl sulfone, B-naphthyl vinyl sulfone, 2-chlorophenyl vinyl sulfone, 3-chlorophenyl vinyl sulfone, 4-chlorophenyl vinyl sulfone, 3,4-dichlorophenyl vinyl sulfone, 3-bromophenyl vinyl sulfone, 2-chloro-4-bromophenyl vinyl sulfone, 4-- iodophenyl vinyl sulfone, 3-fluorophenyl vinyl sulfone, Z-methylphenyl vinyl sulfone, 3-methylphenyl vinyl sulfone, 4-methylphenyl vinyl sulfone, 3,4-dimethylphenyl vinyl sulfone, 3-octylphenyl vinyl sulfone, 4-tertiary butylphenyl vinyl sulfone, 4-n-butylphenyl vinyl sulfone, 4-nitrophenyl vinyl sulfone, 3-nitrophenyl vinyl sulfone, Z-nitrophenyl vinyl sulfone, 2-chloro-4-nitrophenyl vinyl sulfone, 3-methoxyphenyl vinyl sulfone, 4-ethoxyphenyl vinyl sulfone and Z-butoxyphenyl vinyl sulfone.

Many of the above mentioned compounds are known. The others can be prepared by conventional procedures. For example, divinyl sulfone can be formed by dehydrating 2,2'-dihydroxy diethyl sulfone. Symmetric unsaturated sulfones can also be made by reacting olefins with sulfur dichloride and by dehydrochlorinating the formed B-chloro sulfides before or after their oxidation to the sulfones. Other vinyl sulfones can be prepared by reacting cycloalkenyl, arylor substituted aryl-sulfenyl chlorides with ethylene followed by dehydrochlorination of the formed ,B-chloroethyl-cycloalkenyl or aryl-sulfides before or after their oxidation to the desired sulfones.

While compounds of the above illustrated class are preferred, some nematocidal activity is observed by other sulfones having the general formula R SO R where R, is alkenyl, phenyl, alkylphenyl, halophenyl, nitrophenyl or aralkenyl and R is alkenyl, phenyl, alkylphenyl, halophenyl, nitrophenyl or aralkenyl.

Examples of such compounds having lesser nematocidal activity are diallyl sulfone, diphenyl sulfone, di-lpropenyl sulfone, di-2-butenyl sulfone-2, di-l-dodecenyl sulfone-1, di-l-octadecenyl sulfone-1, di-styryl sulfone-2, di-3-phenyl propenyl sulfone-1, di-2-chlorophenyl sulfone, di-3-chlorophenyl sulfone, di-4-chlorophenyl sulfone, di-3-bromophenyl sulfone, di-3-nitrophenyl sulfone, di-Z-methylphenyl sulfone, di-3-methylphenyl sulfone, di- 4-methylphenyl sulfone, di-3-fluorophenyl sulfone and di- 3-butylphenyl sulfone.

The compounds included as nematocides vary from highly viscous oils to solids and while they can be applied as such to the soil habitat of the nematodes, it has been found desirable to apply them together with inert solids, to form dusts, or more preferably suspended in a suitable liquid diluent, preferably water. There can also be added surface active agents and inert solids in such liquid formulations. Desirably, 0.05l% by weight of surface active agent is employed. The active ingredient can be from 0.011 to by weight of the entire composition in such cases.

In place of water there can be employed organic solvents as carriers, e.g., hydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil, fuel oil, and petroleum naphtha, ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and perchloroethylene, esters such as ethyl acetate, amyl acetate and butyl acetate, glycol ethers, e.g., monomethyl ether of ethylene glycol and monomethyl ether of diethylene glycol, alcohols, e.g., ethanol, isopropanol and amyl alcohol, etc.

The sulfones can also be applied along with inert solid fungicidal adjuvants or carriers such as talc, pyrophyllite, synthetic fine silica Attaclay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fullers earth, cotton-seed hulls, Wheat flour, soybean flour, etc.,

J pumice, tripoli, wood flour, walnut shell flour, redwood flour, and lignin.

It is frequently desirable to incorporate a surface active agent in the pesticidal compositions of this invention' Such surface active agents are advantageously employed in both the solid and liquid compositions. The surface active agent can be anionic, cationic or nonionic in character.

Typical classes of surface active agents include alkyl sulfonates, alkylaryl sulfonates, alkyl sulfates, alkylamide sulfonates, alkylaryl polyether alcohols, fatty acid esters of polyhydric alcohols, ethylene oxide addition products of such esters; addition products of long chain mercaptans and ethylene oxide; sodium alkyl benzene sulfonates having 14 to 18 carbon atoms, alkylphenolethylene oxides, for example, p-isooctyl phenol condensed with 10 ethylene oxide units; and soaps, for example, sodium stearate and sodium oleate. Typical surface active agents are: Aerosol OS (sodium salt of propylated naphthalenesulfonic acid); Aerosol OT [(di-2-ethylhexyl) ester of sodium sulfosuccinic acid]; Alkanol B (sodium alkylnaphthalene sulfonate); Alrosene 31 (sodium salt of modified alcohol sulfate from cocoanut fatty acids); Arctic Syntex M (sodium salt sulfonated monoglyceride of cocoanut fatty acids); Areslrap 100 t -H s icfiua' i n w man Areskap 300 [(C H (SO Na)C H C H Arlacel C (sorbitan sesquioleate); Arquad 12 (mainly lauryltrimethyl ammonium chloride); Arquad 18 (mainly octadecyltrimethyl ammonium chloride); Brij 35 (polyethylene glycol lauryl ether); Daxad No. 11 (sodium salt of polymerized alkylated arene sulfonic acid); Duponol LS (sodium oleyl sulfate); Duponol WA (sodium lauryl sulfate); Emulsept Ethofats (polyethylene esters of fatty acids or rosin acids, for example, Ethofat 3, 7, 11, 13, 15, 19, etc.); Ethomeens [C H; (CH1) nN (CHZCHZOMH for example, Ethomeen 8, 10, 12, 14, etc.: Ethomids CH CH OhH [OHKCHQHCON :l

2 zOH for example, Ethomid 8, 10, 12, 14, etc.: Igepal CA (alkylphenyl polyethylene glycol ether); Igepon T (sodium N-methyl-N-oleyltaurate); Igepon A (sodium oleyl isethionate); Intramine [(RCONHCH CH OSO Na) where RCOOH is commercial lauric acid containing myristic acid]; Invadine C (sodium alkylnaphthalene sulfonate); Leonil SA (sodium dibutyl naphthalene sulfonate); Marasperse C (sodium lignin sulfonate); Maypon 4C (protein-oleyl chloride condensation product); Miranols N Hz Cn 2a NCH; OH- I CH2CH2ONa CHzCOONa Myrj (polyethylene glycol stearate); Nacconal NR (sodium dodecyl benzene sulfonate); Nekal A (sodium salt of isopropylated naphthalenesulfonic acid); Nekal BX (sodium salt of butylated naphthalenesulfonic acid); Ninol 1281 (fatty acid ethanolamide); Nonic 218 (tertiary dodecyl polyethylene glycol thioether); Pluronics (condensation product of ethylene oxide and polypropylene glycol); Renex 25 (solidified urea complex of polyethylene glycol ester of mixed fatty and rosin acids); Santomerse No. 1 (sodium dodecyl benzensulfonate);

&

Santomerse D (sodium dodecyl benzensulfonate); Santomerse B [m-C H (COOC H )(50 N201; Sapamine KW [CH3(CHZ)7CHICH(CHZ)7 CONI-ICH CH N(CH (C H [CH OSO Span 20 (sorbitan monolaurate); Span 40 (sorbitan monopalmitate); Span 60 (sorbitan monostearate); Span (sorbitan monooleate); Sterox CD (polyethylene glycol ester of tall oil acids); Sulframin DR (sodium salt of sulfonated condensation product of ethanolamine with a fatty acid); Tergitol O8 where C H is diisobutyl]; Tween 20 [tris (polyoxyethylene) sorbitan monolaurate]; Tween 40 [tris (polyoxyethylene) sorbitan monopalmitate]; Tween 60 [tris (polyoxyethylene sorbitan monostearate]; Tween 80 [tris (polyoxyethylene) sorbitan monooleate]; Ultrawet SK (sodium alkylbenzene sulfonate); Ultravon K (sodium salt of sulfonated alkyl benzimidazole); Aerosol MA (sodium dihexyl sulfosuccinate); Nekal BV (sodium dibutyl naphthalenesulfonate); Dreft (an alkyl sulfate); and Turkey red oil.

The solid and liquid formulations can be prepared by any suitable method. Thus, the active ingredients, in finely divided form if a solid, may be tumbled together with finely divided solid carrier. Alternatively, the active ingredient in liquid form, including solutions, dispersions, emulsions and suspensions thereof, may be admixed with the solid carrier in finely divided form in amounts small enough to preserve the free-flowing property of the final dust composition.

In the following examples illustrating nematocidal activity the sulfones were formulated as wettable powders consisting of 50% sulfone (active material) (46% Hi-Sil 233 (ultra fine silica), 2% Marasperse N (sodium lignin sulfonate) and 2% Pluronic L61 (polyethylene oxidepolypropylene oxide, molecular weight about 1000).

These 50% by weight sulfone containing wettable powders were diluted with water to such an extent as to obtain final concentrations of the sulfones of 200, 100, 50, 25 and 12.5 ppm. during the actual tests.

The contact saprophytic nematode test was carried out in water as the medium with Panagrellus and Rhabditis spp. at room temperature. The results recorded in Table I were obtained at the end of a 48 hour period.

TABLE I Percent Kill 0t Nematodes at Rates of I).[).Il1. Compound Divinyl sulfone 100 100 100 95 Diallyl sulfone 60 40 20 20 20 Methyl vinyl sulfone 20 l0 10 Methyl allyl sulfone. 20 10 10 10 10 Phenyl vinyl sulfone 95 95 50 50 Diphenyl sulfone 60 40 .10 20 20 Di-l-propenyl sulfone 20 20 20 2t) 20 Di-Z-butenyl sulioue-2 80 40 20 20 20 Di-l-dodecenyl sulfone-1.. 60 60 -10 20 20 Di-l-ootadeccnyl sulfone-1... 80 60 40 20 '20 Di-styryl sulfone-2 60 40 20 20 20 Di-3-phenyl propenyl sulfone 30 20 20 20 20 4-chlorophenyl vinyl sulfone." 100 100 80 20 10 4-rnethylphenyl vinyl sulfone" 100 70 20 10 10 Z-methylphenyl vinyl sulfone 90 40 10 10 1O 3-methylphenyl vinyl sulfone 85 50 20 10 1D The parasitic nematocide test was carried out on agar as the medium with Meloidogyne spp. at room temperature at the same application rates. Infested roots of tomato plants were first treated in the presence of soil for 24 hours with the appropriate chemical at the desired rate of application, transferred onto a previously prepared agar plate and small quantities of water applied to form an aqueous film for the nematodes to disperse on the agar surface. The readings were taken after a period of seven days and the test results recorded in Table II.

TABLE II Percent Kill of Nematodes at; Rates of p.p.m. Compound Divinyl sulfone 100 100 95 95 9.) Diallyl sulfone 0 0 0 0 Phcnyl vinyl sulfone... 95 95 95 95 95 Diphenyl sulfone 50 30 30 10 0 Di-l-propenyl sulfone 100 100 90 40 Di-Q-butenyl sulfone- 50 20 20 10 0 Di-l-dodeoenyl sulfone-1 0 O 0 0 0 Di-Loctadecenyl su lfone-1 0 0 0 O 0 Di-styryl sulfone-2 (i0 50 20 20 Di-3-phenyl propenyl sulfone-1 95 70 70 50 30 i-chlorophenyl vinyl sulfone 100 100 50 1O 10 4-methylphenyl vinyl sulfone 100 100 30 10 10 DD (dichloropropylene mixed with dichloropropane), a standard nematocide, shows the following results in the same tests.

Thus, all of the sulfones employed in the present invention were equal to or better than DD at the rate of 12.5 p.p.m. in the saprophytic test and many of the sulfones were superior to DD in the parasitic test at 12.5 p.p.m. The two compounds divinyl sulfone and phenyl vinyl sulfone gave outstanding results at all concentrations.

Both divinyl sulfone and phenyl vinyl sulfone showed no phytotoxicity for broadleaf plants, e.g. cotton, and grass at rates of application as contact herbicides at rates of 50 p.p.m. or below.

The following examples show the preparation of the sulfones employed in the tests of Tables I and II.

EXAMPLE 1 Divinyl Sulfone 155 g. (12.1 M) thiodiglycol was mixed with 30 g. H PO and oxidized by adding 2,460 ml. (24.2 M) 29% H 0 directly under cooling and agitating at or below 70 C. Final heating ona steam cone for 4 to hours completed the reaction. The whole was then stripped in vacuum (20 mm. Hg, steam bath). The yield was 1,800 g. or 98% of thiodiglycol sulfone.

The dehydration was carried out in 2 molar runs. 1400 ml. 85% H PO was first dehydrated by heating at 300 C. (20 mm. Hg) until no more water appeared to distill over (approximately 1 hour). Cooling of the now dehydrated H PO to 280 C., adding 308 g. (2 M) of warm (55 C.) sulfone (as obtained above) at such a rate as to maintain an equal distillation rate, separating the obtained bottom layer formed in the receiver, drying over anhydrous Na SO and redistillation gave 210 g. (89% yield) of pure divinyl sulfone, B 9091 C., 11 1.4780.

IR-analysis shows strong SO -peaks at 1315 and 1130 cm. as well as typical peaks for the vinyl group at 625, 1390, and 975 cmf 6 EXAMPLE 2 Diallyl Sulfone 376 g. (3.33 M) diallyl sulfide was mixed with 200 ml. glacial acetic acid and oxidized by dropwise addition of 720 ml. 30% H 0 (3% excess) under stirring and cooling. The first one-half of the H 0 solution was added at or below room temperature (20-30 C.) and the second one-half of the H 0 solution at 7080 C. After standing overnight, heating two hours on the steam cone and cooling to room temperature, about one-haif of the expected quantity of the product settled out. The supernatant aqueous acetic solution was extracted 3 times with -200 ml. portions CHC13. These extracts were combined with the initially obtained bottom layer, washed with Water until free of acetic acid, dried over anhydrous Na SO and stripped free of solvent. Obtained were 454 g. (94% yield) of crude diallyl sulfone, faintly yellow oil n 1.4899. The product distills at 92 to 93 C./.35 mm. Hg, 11 1.4874.

IR-scan showed typical sO -absorption bands at 1315 and 1130 cm? and an expected number of terminal vinyl group absorptions at 1640, 1424, 1399, 990, 945, and 870 cmf EXAMPLE 3 Methyl Vinyl Sulfone (a) DEHYDROCHLORINATION PROCEDURE To 24 g. (0.174 M) methyl-Z-chloroethyl sulfone in ml. benzene, 17.6 g. (0.174 M) triethyl amine were added dropwise with stirring and the reaction was allowed to proceed at room temperature. After standing overnight 15 g. triethyl amine hydrochloride were removed by filtration, the benzene solution washed free of unreacted triethyl amine with dilute HCl, dried over anhydrous Na SO and stripped. 17.7 g. crude methyl vinyl sulfone (95% yield) were obtained.

IR-scan showed typical peaks for the SO -group (1305 and 1135 cm.- and for the vinyl group (1415, 1319, 958, 785 cmf (b) DEHYDRATION PROCEDURE 92 g. (1 M) methyl-Lhydroxyethyl sulfide were oxidized with 220 ml. (5% excess) of 30% H 0 in glacial acetic acid (100 ml.) in the usual way, heated on the steam cone for two hours and was allowed to stand overnight. All volatile material (H 0 and acetic acid) was removed in vacuum (20 mm. Hg) at 7080 C., the hot residue added dropwise to previously dehydrated 300 ml. H PO at 285 to 300 C./20 mm. Hg and the simultaneously distilling H O-vinyl methyl sulfone mixture collected in the receiver. Extraction into CHCl drying over anhydrous Na SO and stripping gave 61 g. (57.5% yield) of a yellow oil, n 1.4580. Distillation at 77 to 80 C./0.7 mm. Hg yielded 50 g. pure methyl vinyl sulfone 11 1.4589. IR-scan showed identical peaks as reported in Example 3a).

EXAMPLE 4 Methyl Allyl Sulfone 22 g. (0.25 M) methyl allyl sulfide were dissolved in 25 ml. acetic acid, 55.1 ml. (0.5 M, 5% excess) 30% H 0 added, the first half at or below 70 C. and the second half at 85-90 C., heated for two hours on the steam cone, cooled, extracted into CHCI Washed three times with H O to remove acetic acid, dried over anhydrous Na SO stripped and distilled. 29 g. (97% yield) crude material was obtained, 11 1.4730, most of which distilled at 141 C. at 23 mm. Hg, r1 1.4735. IR-absorptions at 1302 and 1135 cm? showed the presence of the SO -group and various peaks such as those at 1640, 1420, 995, and 880 cm.- characterized the terminal C=C double bond.

7 EXAMPLE 5 Plzelzyl Vinyl S ulfone 0.25 M diphenyl disulfide, made from 55 g. (0.5 M) PhSH and I were dissolved in 4-500 ml. CCl 17.7 g. (0.25 M) chlorine gas were introduced at to 5 C. during 30-40 minutes and the formed orange-red CCL; solution of the phenylsulfenyl chloride cooled to between C. to C. 14 to 16 g. of ethylene gas (slight excess) were then introduced during 40 to 60 minutes keeping the reaction temperature between 10 and 15 C. The color of the reaction mixture gradually changed from deep orange-red to faintly yellow at the end of the reaction and was allowed to warm to room temperature. Standing overnight and stripping yielded 84 g. (98% yield) of practically pure 2-chloroethylphenylsulfide, 11 1.5812. All of this was taken up in 200 ml. glacial acetic acid and oxidized by gradual addition of a total of 110 ml. 30% H 0 (about 5% excess) at 50 C. (first one-half of H 0 and at 70-80 C. (second one-half of H 0 and finally heated on a steam cone for four hours. Standing for 48 hours, heating for a further 2 hours on a steam cone, cooling and diluting with 1 vol. water gave 75 g. crude sulfone as heavy oil and an additional 25 g. product from CHCI extraction of the aqueous acetic acid solution. 99.5 g. (97.5% over-all yield) of crude 2- chloroethyl phenyl sulfone were obtained which was purified by recrystallization (after seeding) from small amounts of benzene, M.P. 50 C.

83.5 g. of this (0.41 M) were dissolved in 250300 ml. warm (-40 C.) benzene and 45 g. Et N (10% excess) added dropwise while allowing the reaction to proceed without cooling to attain a temperature of 5560 C. at the end of the Et N-addition. After keeping the reaction mixture under gentle reflux for /2 hour, cooling, removing the formed Et NHCl by filtration and the excess unreacted Et N by washing the benzene solution with dilute HCl and water, drying and stripping 59.8 g. (87% yield) of crude phenyl vinyl sulfone was obtained as a yellow oil. The latter solidified on stirring with a small quantity of petroleum ether and could be recrystallized from CCl Two such recrystallizations gave pure phenyl vinyl sulfone, M.P. 69-70" C.

IR reveals strong peaks at 1315 and 1145 emf for the sulfone group, peaks such as at 1000 and 975 cm.- for the vinyl group and peaks such as 700 and 685 cm.- for the phenyl group.

EXAMPLE 6 Diphenyl S ulfone g. (0.25 M) AlCl were suspended in 200 ml. benzene at room temperature and 44 g. (0.25 M) benzene sulfonyl chloride were gradually (1 drop/3-5 see.) added during a period of 2 hours at room temperature. The reaction proceeded smoothly under evolution of HCl and attained a temperature of between and 45 C. at the end of the addition of the reagent. Stirring was continued overnight and the mixture gently refluxed on a steam cone until no more HCl was evolved (about 2 hours). The cooled mixture was poured on ice 1 dilute HCl mixture and the formed solids taken up in CHCI The solution of the product in CHcl W21S washed with water, dried over Na SO and concentrated. While still hot, 1 vol. of ethyl alcohol was added and the solution allowed to crystallize on cooling. 52 g. (97% yield) of diphenylsulfone were obtained as white plates, MP. 127129 C.

IR showed typical absorption for the S0 group (1320 and 1155 CH1.1) and for the phenyl groups (760, 727 cmr etc).

EXAMPLE 7 Di-Propenyl Sulfone 1 liter CHCl was cooled to 10 to -15 C. and a total of 87 g. (2 M, 6% excess) of propylene gas were introduced. As soon as 41 g. of propylene gas were absorbed (after 1 to 2 hours), the dropwise addition of 103g. (1 M) SCI was started simultaneously while still further propylene gas was being absorbed. The outside cooling bath was kept at 20 to -25C. In order that the reaction proceeded at between 10 and 15 C. After a total reaction period of approximately 2 hours, the mixture was allowed to attain room temperature. After standing for 72 hours, the mixture was fractionated and a total of 121 g. (65% yield), B 86-88 C., B 7884 C., n 1.5032 of the 2-chloropropyl sulfide were obtained.

100 g. (0.66 M) of this were mixed with 200 ml. acetic acid and oxidized with a total of 145 ml. 30% H 0 (2 M, 5% excess) which was added dropwise at 30 C. with occasional cooling. After completed addition of the H 0 solution, the reaction mixture was then slowly heated to between and C. and kept at this temperature 40-50 minutes) until the temperature ceased to rise on its own accord. Standing overnight, heating on a steam cone three hours, cooling and diluting with 2 vols. of H 0 furnished 130 g. crude 2-chloropropyl sulfone, containing 9 g. acetic acid. Washing with water and drying gave 121 g. (quantitative yield) of 2-chloropropyl sulfone, H1325 1.4885.

100 g. (0.6 M) of this were mixed with 300 ml. benzene and treated with 121 g. Et N (1.2 M) gave, after removal of the formed amine salt and stripping off the solvent, 54.0 g. (82% yield) crude dipropenylsultone. 26 g. of the latter were distilled and a total of 21 g. (80% yield) of an isomeric mixture boiling at 98-107 C./O. 30.5 mm. Hg was obtained, 11, 1.4886-1.4917. VPC and IR indicated two predominant stero isomers present in about equal quantities. Typical IR-peaks were 1325 and 1125 cm.- for the sulfone group, 1645 and 668 cm.- for the cisand 835, 810 and 950 cmf respectively, for the trans C=C double bond.

EXAMPLE 8 Di-Z-ButenyL (2 -Sulf0ne (a) Cis butene-Z (56.1 g., 1.0 M) was dissolved in 750 ml. CHC13 at 20 to -15 C. and 51.4 g. (0.5 M) SC1 in 50 ml. CHCl were added to the butene-2-chloroform mixture at -20 to -15 C. The rate of the reaction could easily be observed by the rate of decoloration of the added SCl After completed addition of the reagent, allowing the mixture to warm to room temperature and stripping in vacuum of 20 mm. Hg and finally at 0.5 mm. Hg at room temperature, 120 g. yield) of crude 2-chloro-1-methyl propyl sulfide were obtained as a faintly yellow oil, 1.5005.

75.5 g. (0.35 M) of this bis-2-(3-chloro butyl)-sulfide were oxidized in 100 ml. acetic acid by dropwise addition of 75 ml. (0.7, M 2% excess) of 30% H 0 at 50 to 55 C. (first one-half of H 0 and 8590 C. (second one-half of H 0 Heating for one additional hour on the steam cone and cooling furnished a bottom layer. The latter was separated and combined with the CHCl solution obtained by extracting the remaining aqueous acetic acid solution, washed with NaI-ICO solution and H 0 to remove acetic acid, dried over Na SO and stripped in vacuum of 20 mm. Hg (79 C.). 74 g. of a faintly yellow oil, 11 1.4985, were obtained.

64 g (0.26 M) of this bis-2-(chloro butyl)-sulfone were dissolved in 100 ml. benzene, 52.1 g. (0.52 M) Et N were added and refluxed for 3 hours. After this period of time, 33 g Et NHCl were obtained, i.e., the dehydrochlorination proceeded to an extent of 46%. 54% unchanged Et N could be recovered from the henzene solution. The latter was dried and the solvent removed by vacuum distillation. The total quantity of raw material was 41 g. 81.5 g. of this was subjected to distillation and about 9 g. of material (48.5%) were obtained as mixed fractions boiling from -130 C. at 0.65 to 9 0.75 mm. Hg, a 1.4960 to 1.5000. The latter consisted of a mixture of stereo isomers.

IR-scan showed typical absorption bands for the S group (1305 and 1130 cm.- some sulfoxide which must have co-distilled according to the 1052 ern.- peak and peak for cis and trans C=C double bond such as 1660, 710 and 826 cmr respectively.

(b) Trans butene was reacted in exactly the same way with SC1 using 65 g. (1.16 M) of starting material and 59.7 g. (0.58 M) SCl as described under (a), the formed bis-2-(3-chlorobutyl)sulfide (obtained were 113.5 g., 92% yield, n 1.5020) oxidized to the sulfone (obtained were 72 g., 84% yield from 75.5 g. (.35 M) bis-2-(3-chlorolf5utyl)- sulfide) and the latter dehydrochlorinated as be ore.

From 62 g. (0.25 M) bis 2 (3 chlorobutyD-sulfonc were obtained 40 g. crude end-product, 15 g. of which were subjected to vacuum distillation. 7.5 g. (50% calcu* lated for crude product used) were obtained as mixed fractions boiling from 125 to 135 C. at 0.65 to 0.80 mm. Hg, 11 1.4984-1.5035. This stereo isomer mixture obtained in a yield of approximately 50% was not further resolved. A similar product was obtained as that formed when using cis butene.

IR-scan revealed similar peaks as described in Example 8a.

EXAMPLE 9 Di-Dodecenyl Sulfone-I 100 g. (0.6 M) of dodecene-l were dissolved in 250 ml. CHCl cooled to 15 to '20 C. and 30.5 g. (0.3 M) SC1 added dropwise at a rate to maintain a reaction temperature of 15 C. The addition of the reagent was completed within 30 minutes. Allowing the reaction mixture to warm to room temperature, standing for one hour and removing the solvent in vacuum yielded 132 g. (quantitative yield) of 2-chlorododecyl sulfide, 11 1.4741.

87.9 g. (0.195 M) of this material were dispersed (rapid stirring) in 150 ml. glacial acetic acid and oxidized by dropwise addition of 42 ml. 30% H 0 at 55-60 C. and at 8085 C. for the oxidation stages for sulfoxide and sulfone respectively. Heating for 2 hours at 95 C. cooling the mixture, taking up the formed top layer in CHCl removing the dissolved acetic acid by washing the CHCl solution with H 0 and drying over anhydrous Na SO yielded, after stripping, 74.5 g. (81% yield) of 2-chlorododecyl sulfone as a light yellow oil which solidified on standing. Crystallization from ethyl alcohol gave a white product, M.P. 4748 C.

62 g. (0.132 M) of this 2-chloro dodecyl sulfone were dissolved in 100 ml. benzene and treated with 26.6 g. (0.264 M) Et N. After refluxing for one hour, removing the formed Et NHCl and unreacted Et N by filtration and washing with dilute HCl, decolorizing the benzene solution with charcoal and drying over anhydrous Na SO and stripping, 42 g. (80% yield) of crude di-dodecenyl sulfone were obtained as a heavy, reddish oil.

IR-absorption, at 1318 and 1128 cm? shows S0 at 1045 cm? some SO and at 1640 and 995 cm." cis and trans C=C double bonds, respectively.

EXAMPLE Di-Octaa'ecenyl-I -Sulf0ne-1 115 g. (0.46 M) of octadecene-l were dissolved in 4-600 ml. CHCl the solution cooled to 20 to ---25 C. and 23.7 g. (0.23 M) SC1 added dropwise at a rate to maintain a reaction temperature of -10 to --15 C. After completed addition of the reagent (about 40 minutes) the reaction mixture was allowed to warm to room temperature and all solvent removed in vacuum. 141 g. (quantitative yield) of crude 2-chloro octadecyl sulfide was obtained which solidified after standing for a few hours, M.P. 3545 C.

70.5 g. (0.115 M) of this were dispersed (stirring) in 150 ml. warm (35 C.) glacial acetic acid and oxidized by adding 22 ml. 30% H 0 solution at 50 C. and .C., respectively, for the two oxidation stages (sulfoxide and sulfone). Three hours heating on the steam cone under vigorous stirring and standing overnight furnished a top layer which solidified. The whole was diluted with 1 vol. of H 0, extracted with CHCl (using NaCl to break emulsions formed), the CHCl extract freed from acetic acid by washing several times with 25% NaCl solution, dried over anhydrous Na SO stripped, and allowed to crystallize. 27 g. (37% yield) of pure (washed with cold acetone) 2-chloro-octadecyl sulfone were obtained, M.P. 71-2 C. Combined residues of mother liquors and acetone washing furnished after oxidation with 8 ml. 30% H 0 in acetic acid an additional 30 g. of the same product. The total yield obtained amounted to 78%.

22.5 g. (0.035 M) of this were dissolved in 200 ml. benzene and treated (stirring) with 7.5 g. Et N. After one hour on a steam bath, the formed Et N-HCl was removed by filtration and the benzene solution freed of unreacted Et N by Washing with dilute HCl and H 0. On removing the solvent after drying over anhydrous Na SO 20 g. of crude end-product were obtained, which, after recrystallization from acetone, gave 18 g. (90% yield) of l-octadecenyl sulfone, M.P. 68 C.

IR-absorptions at 1322 and 1118 cmr show S0 at 1650 CIILTI show cisand at 955 cm. trans C=C double bond groups.

EXAMPLE 11 Di-Z-Styryl Sulfone 208 g. (2 M) of styrene were dissolved in 750 ml. CHCI cooled to 15 to '20 C. and 102.9 g. (1 M) SC1 were added dropwise during a one hour period at a rate to maintain a reaction temperature of -15 C. After allowing the reaction mixture to warm to room temperature and standing for one-half hour, the'CHCl was completely removed in vacuum. Obtained were 304 g. (98% yield) of 2-chloro-2-phenyl ethyl sulfide as a pale yellow oil, 11 1.6010, which could not be distilled without decomposition at 0.5 mm. Hg.

100 g. (0.32 M) of this sulfide were dissolved in 250 ml. glacial acetic acid and oxidized with 66 ml. (0.64 M) 30% H 0 at 55 and 80 C., respectively (SO and S0 stages), allowed to stand overnight followed by heating on the steam cone for one hour. Extraction of the aqueous acetic acid solution with CHCI combining it with the formed bottom oil, washing the CHCl solution with H O, drying over anhydrous Na SO and removing the solvent in vacuum, yielded 97 g. (88% yield) of 2-chloro-2-phenyl ethyl sulfone as a light brown syrup.

80 g. (0.233 M) of the sulfone were dissolved in 300 ml. benzene and treated with 47 g. (0.466 M) Et N in the usual way. After removing the Et NHCl and unreacted Et N by filtration and washing the benzene solution with dilute HCl, dry (anhydrous Na SO and removing the solvent in vacuum, 45 g. (72% yield) of 2- styryl sulfone were obtained as brown syrup which did not solidify on standing.

IR-scan revealed typical absorptions for the S0 group at 1315 and 1125 cm. absorptions for the C=C double bonds at 970 and 830 cm. and for the phenyl groups at 695, 1500 and 1610 cm together with some sulfoxide at 1035 cmf EXAMPLE 12 3-Phenyl Propenyl S ulfone 23 g. (0.2 M) of allylbenzene were dissolved in ml. CI-lCl cooled to 20 to 25 C. and 10.5 g. SC1 were added dropwise in such a way as to maintain a reaction temperature of 10 to -15 C. After allowing the mixture to warm to room temperature and standing for one further hour, the solvent was removed in vacuum and a total of 33 g. (98% yield) of 2-chloro-3-phenyl 11 propyl sulfide were obtained as heavy oil which decomposes on distillation in a vacuum of 0.5 mm. Hg.

27.5 g. (0.9 M) of this were dissolved in 50 ml. glacial acetic acid and oxidized with 20 ml. (0.2 M, 5% excess) 30% H at 7080 C. Standing overnight (rapid stirring), heating on a steam cone for one hour, cooling, diluting with 1 vol. of H 0 and extracting with CHCl yielded 27.5 g. (92% yield) of sulfone as brown syrup after drying and removing the solvent.

22.8 g. (0.068 M) of this 2-chloro-3-phenyl propyl sulfone were dehydrochlorinated in the usual way with 15 g. Et N in 100 ml. of benzene as solvent. Removing the amine hydrochloride and excess unreacted amine by washing with H 0 and dilute HCl, drying (anhydrous Na SO of the benzene solution and removing the solvent in vacuum yielded 15.6 g. (88% yield) of 3-phenyl propenyl sulfone as a syrup which solidified after long standing.

IR-analysis reveals SO -peaks at 1295 and 1110 cmr' peaks for cis-(955 cm.- and trans-(815 cmf C=C double bonds and those for the phenyl group at 699, 1500, 1695 and 1750 cmr EXAMPLE 13 p-Chloro Phenyl Vinyl Sulfone 0.5 M of p-chloro phenyl disulfide, (M.P. 701 C. made in quantitative yield from p-chloro thiophenol by om'dation) on chlorination and reaction in the known way with ethylene gave p-chloro phenyl-2-chloro ethyl sulfide (11 1.5975, 98% yield) which on oxidation gave a 91% yield of the sulfone, M.P. 9890 C. The latter was dehydrochlorinated in the usual way to give the desired p-chloro phenyl vinyl sulfone (quantitative yield) as a colorless oil B. 105-6 C., n,;, 1.5675.

EXAMPLE 14 p-Tolyl Vinyl Sulfone 0.2 M of p-tolyl sulfide (M.P. 46 C., made in quantitative yield from p-thiocresol by oxidation) on chlorination and reaction in the known way with ethylene gave p-tolyl-Z-chloroethyl sulfide (n 1.5697, quantitative yield) which on oxidation gave a quantitative yield of the sulfone, M.P. 77-8" C. The latter was dehydrochlorinated in the usual way to give the desired p-tolyl vinyl sulfone (93% yield) as a white crystalline solid, M.P. 59-60" C.

EXAMPLE 15 o-Tolyl Vinyl Sulfone 0.142 M o-tolyl disulfide (made in quantitative yield from o-thiocresol by oxidation) on chlorination and reaction in the known way with ethylene gave o-tolyl-2- chloro ethyl sulfide (11 1.5840, crude yield 93.5%)

1 2 which on oxidation gave a yield of the sulfone n 1.5654, crude. The latter was dehydrochlorinated in the usual way to give the desired o-tolyl vinyl sulfone (quantitative yield) as a colorless oil B. 1091l0 C., n,;, 1.5616.

EXAMPLE 16 m-Tolyl Vinyl Sulfone 0.159 M m-tolyl disulfide (made in a 91% yield from m-thiocresol by oxidation) on chlorination and reaction of the formed sulfenyl chloride with ethylene gave mtolyl-2-chloroethyl-sulfide (11 1.5775, crude, quantitative yield) which on oxidation gave 94% yield of the crude sulfone n 1.5546. The latter was dehydrochlorinated in the usual way to give the desired m-tolyl vinyl sulfone (86.5% yield) as a colorless oil, B l05107 C., n 1.5520.

We claim:

1. A process of killing nematodes comprising applying to nematode infested soil in an amount sufiicient to exert nematocidal action a compound having the formula RSO R where R is vinyl and R is selected from the group consisting of alkenyl, aryl, haloaryl, nitroaryl, alkoxyaryl, cycloalkenyl and aralkenyl and R has between 2 and 18 carbon atoms.

2. A process of killing nematodes comprising applying to nematode infested soil in an amount sufficient to exert nematocidal action divinyl sulfone.

3. A process of killing nematodes comprising applying to nematode infested soil in an amount sufiicient to exert nematocidal action aryl vinyl sulfone wherein the aryl group has up to 14 carbon atoms.

4. A process according to claim 3 where the aryl vinyl sulfone is phenyl vinyl sulfone.

5. A process according to claim 3 where the aryl vinyl sulfone is methylphenyl vinyl sulfone.

6. A process of killing nematodes comprising applying to nematode infested soil in an amount sufiicient to exert nematocidal action halophenyl vinyl sulfone.

7. A process according to claim 6 wherein the halophenyl vinyl sulfone is chlorophenyl vinyl sulfone.

References Cited in the file of this patent UNITED STATES PATENTS 2,045,925 Remy June 30, 1936 2,623,838 Bender Dec. 30, 1952 2,812,281 Meltzer Nov. 5, 1957 2,954,319 Uhlenbroek Sept. 27, 1960 2,968,678 Oswald Jan. 17, 1961 OTHER REFERENCES King: US. Dept. Agr. Handbook No. 69, May 1954, pages 319, 320.

Claims

1. A PROCESS OF KILLING NEMATODES COMPRISING APPLYING TO NEMATODE INFESTED SOIL IN AN AMOUNT SUFFICIENT TO EXERT NEMATOCIDAL ACTION A COMPOUND HAVING THE FORMULA RSO2R1 WHERE R IS VINYL AND R1 IS SELECTED FROM THE GROUP CONSISTING OF ALKENYL, ARYL, HALOARYL, NITROARYL, ALKOXYARYL, CYCLOALKENYL AND ARALKENYL AND R1 HAS BETWEEN 2 AND 18 CARBON ATOMS.