US3415883A

US3415883A - alpha-halosulfonium ylids and alpha-halosulfonium salts

Info

Publication number: US3415883A
Application number: US549162A
Authority: US
Inventors: Ratts Kenneth Wayne
Original assignee: Monsanto Co
Current assignee: Monsanto Co
Priority date: 1966-05-11
Filing date: 1966-05-11
Publication date: 1968-12-10
Anticipated expiration: 1985-12-10

Description

3,415,883 a-HALOSULFONIUM YLIDS AND a-HALOSULFONIUM SALTS Kenneth Wayne Ratts, Creve Coeur, M0., assignor to Monsanto Company, St. Louis, Missouri, a corporation of Delaware No Drawing. Filed May 11, 1966, Ser. No. 549,162

- 15 Claims. (Cl. 260-592) ABSTRACT OF THE DISCLOSURE The a-halosulfonium compounds of this invention are represented by a formula selected from the group consisting of (a) R e RCHz X Q RC Ra a. and

(h) Rh RCH; X 0

atHLQ R CH 2 R X- wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing 1, 2 or 3 halogen atoms, X is halogen (Cl, Br and I), R is selected from the group consisting of halogen (Cl, Br, F and I) and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R is phenyl, a is an integer from 0 to 5 inclusive, b is an integer from 0 to 2 inclusive and c is an integer from 0 to 1.

The u-halosulfoni-um compounds of this invention are represented by a formula selected 'from the group consisting of RClTz X O 1006 R R b and RCH: X 0

-c'ani'w R 0 r, R R b wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing 1, 2 or 3 halogen atoms, X is halogen (Cl, Br and I), R is selected from the group consisting of halogen (Cl, Br, F and I) and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R is phenyl, a is an integer :from 0 to 5 inclusive, b is an integer from 0 to 2 inclusive and c is an integer from 0 to 1.

This invention relates to whalosulfonium ylids and a-halosulfonium salts, and to processes of making them. This invention further relates to fungicidal compositions and methods for the control of fungal organisms.

United States Patent 0 3,415,883 Patented Dec. 10, 1968 In the above formula, R and R can be hydrogen, alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-'butyl, isobutyl, tert-butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and the various homologues and isomers of alkyl having from 1 to 12 carbon atoms and haloalkyl such as chloromethyl, iodornethyl, bromomethyl, fluoromethyl, chloroethyl, iodoethyl, lbromoethyl, fluoroethyl, trichloro methyl, diiodo-ethyl, tribromomethyl, trifluoromethyl, dichloroethyl, chloro-n-propyl, bromo-n-propyl, iodoisopropyl, bromo-n-butyl, bromotert-butyl, 1,3,3-trichlorobutyl, 1,3,3-tribromobutyl, chloropentyl, bromopentyl, 2,3-dichloropentyl 3,3-dibromopentyl, chlorohexyl, bromohexyl, 2,4-dichlorohexyl, 1,3- dibromohexyl, 1,3,4-trichlorohexyl, chloroheptyl bromoheptyl, fiuoroheptyl, 1,3-dichloroheptyl, 1,4,4-trichloroheptyl, 2,4-di(ch1oromethyl)heptyl, chlorooctyl, bromooctyl, iodooctyl, 2,4-di(chloromethyl)hexyl, 2,4-dichlorooctyl, 2,4,4-tri(chloromethyl)pentyl, 1,3,5-tribromooctyl and the halogenated straight and branched chain nonyl, decyl, undecyl and dodecyl. In the above formulae R and R are preferably hydrogen, lower alkyl (1 to 4 carbon atoms) or lower haloalkyl (1 to 4 carbon atoms).

In the above formulae R as alkyl can be the alkyl disclosed above for R and R of not more than 4 carbon atoms. As alkoxy, R can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy.

The u-halosulfonium salts of this invention are prepared by a process which comprises halogenation of a sulfonium ylid in accordance with the following representative synthesis R RCH: (H)

s=o1-Io% Q X2 RICH; R Rn,

wherein R, R R R R, X, a, b and c are as defined above.

Halogenation in accordance 'with this invention is carried out by admixing substantially equimolar amounts of reactants in the presence of an insert organic medium at room temperature, i.e. about 20 C. to 25 C. However, higher or lower temperatures can be employed, the tem perature not being critical.

Suitable insert organic media which can be used in the preparation of the a-halosulfonium salts of this invention include by way of example hydrocarbons such as benzene, toluene, xylene, cyclohexane, methylcyclohexane, n-heptane, n-hexane and the like; ethers such as isopropyl ether, n-butyl ether, 1,4-dioxane, isobutyl ether, diethyl ether and the like; aliphatic and cycloaliphatic ketones such as methyl isopropyl ketone, methyl .isobutyl ketone, methyl isoamyl ketone, diisopropyl 'ketone, cyclohexanone and the like; and organic halides such as carbon tetrachloride, n-butyl chloride, ethylene dichloride, and the like.

The a-halosulfonium ylids of the present invention are prepared by a process which comprises reacting an onhalosulfonium salt of the formula RC I R OHi wherein R, R R R R X, a, b and c are as defined above with a substantially equimolar amount of an alkali metal hydride such as sodium hydride under substantially anhydrous conditions in the presence of an inert organic media until a substantially equimolar amount of hydrogen has evolved. The process is suitably carried out at room temperature, i.e. about 20 C. to 25 C. However, higher or lower temperatures can be used, the temperature not being critical. Inert organic media for use in this invention include, for example, tetrahydrofuran, diglyme, diethylether and the like.

Pressure is not a critical factor in either of the above processes of this invention. Pressure both above and below atmospheric can be employed although atmospheric pressure is preferred for convenience.

The separation of the resulting tx-halosulfonium ylids or a-halosulfonium salts from the reaction mixture is readily accomplished. The a-halosulfonium salts are separated from the reaction mixtures by filtration or decantation. In some cases it may be necessary to remove the solvent from the resulting filtrate by stripping or distillation, preferably low temperature vacuum distillation, to recover all of the product salts. The a-halosulfoniurn ylids are separated from the reaction mixture by removing the alkali metal halide salt formed during the reaction by filtration and the solvent from the filtrate by stripping or distillation. The product ylids and salts can be purified by any of the conventional means well known in the art, e.g. selective extraction, recrystallization or a combination of these methods.

The a-halosulfonium ylids and ot-halosulfonium salts of this invention are crystalline solid materials 'which are insoluble in water but somewhat soluble in many organic solvents, for example, alcohols, ketones, hydrocarbons such as benzene, toluene, xylene and the like and chlorohydrocarbons such as chlorobenzene, carbon tetrachloride and the like.

The following examples illustrate the invention. Parts and percent are by weight unless otherwise indicated.

Example 1 To a suitable reaction vessel charged with about 4.5 parts of dimethylsulfonium phenacylide and 50 parts of trichloromethane is added 4.0 parts of bromine with stirring at room temperature (about 20 C.). At the end of the bromine addition, the reaction mixture is filtered and the solids (4.35 parts) are crystallized from methyl alcohol to give (a-bromophenacyl) dimethylsulfonium bromide, M.P. 124-125 C.

Calcd. for C H Br SO: C, 35.31; H, 3.56; Br, 47.00; S, 9.43. Found: C, 35.23; H, 3.38; Br, 47.05; S, 9.61.

Following substantially the same procedure as in the foregoing example the following a-halosulfonium salts of this invention are prepared.

Example 2 (oz-chlorophenacyl) dimethylsulfonium chloride 3 (a-iodophenacyl) dimethylsulfonium iodide 4 (a-chloro-4-chlorophenacyl) dimethylsulfonium chloride 5 (a-chloro-2,4-dichlorophenacyl) dimethylsulfonium chloride 6 (u-chloro-2,4,fi-trichlorophenacyl) dimethylsulfonium chloride 7 (a-c-hloro-4-methylphenacyl) dimethylsulfonium chloride 8 (ot-chloro-4-tert-butylphenacyl) dimethylsulfonium chloride 9 (a-chloro-2,4-dirnethylphenacyl) dimethylsulfonium chloride 10 (a-chloro-2,4,6-trimethylphenacyl) dimethylsulfonium chloride 11 (a-chloro-2,5-diethylphenacyl) dimethylsulfonium chloride 12 (u-chloro-2,6-di-tert-butylphenacyl) dimethylsulfonium chloride 13 (a-cholor-4-bromophenacyl dimethylsulfonium chloride 14 (a-ehloro-3,5-dibromophenacyl) chloride 15 (a-chloro-2-iodophenacyl) dimethylsulfonium chloride dimethylsulfonium 19 (ot-chloro-2,3,4,5,6-pentachlorophenacyl) dimethylsulfonium chloride 20 (a-chloro-4-nitrophenacyl) dimethylsulfonium chloride 21 (a-chloro-Z,4-dinitrofphenacyl) dimethylsulfonium chloride 22 (a-chloro-4-methoxyphenacyl) dimethylsulfonium chloride 23 (a-chloro-2,4-dimethoxyphenacyl) dimethylsulfonium chloride 24 (a-chloro-Z,S-dimethoxyphenacyl) dimethylsufonium chloride 25 (a-chloro4-n-butoxyphenacyl) dimethylsulfonium chloride 26 (a-chloro-4-phenylphenacyl) dimethylsulfonium chloride 27 (ot-ch1oro-2-methyl-4-nitrophenacyl) dimethylsulfonium chloride 28 (a-chloro-Z-methoxy-4-chlorophenacyl) dimethylsulfonium chloride 29 (a-fiuoro-2-methyl-4-methoxyphenacyl) dimethylsulfonium chloride 30 (u-bromophenacyl) diethylsulfonium bromide 31 (a-bromophenacyl) di(n-butyDsulfonium bromide 32 (a-bromophenacyl) di(n-octyl) sulfonium bromide 33 (a-bromophenacyl) di(2-chloroethyl)sulfonium bromide 34 (wiodophenacyl) di(3-chlorobutyl)sulfonium bromide 35 (ot-chlorophenacyl) di(n-dodecyDsulfonium chloride 36 (u-chloro-4-chlorophenacyl) di(4,4-dichloropentyl)- sulfonium chloride 37 (gt-chlorophenacyl) di(2,2,4-tribromobutyl)sulfonium chloride 38 (a-chlorophenacyl) di(Z-fluoropentyl)sulfonium chloride 39 (a-chlorophenacyl) di(2-iodoethyl)sulfonium chloride 40 (u-bro'mo-2,4-dimethylphenacyl) diethylsulfonium bromide Example 41 A suitable reaction vessel is charged with about 750 parts of tetrahydrofuran, 17.0 parts of (OL-bI'OII'lOPhCIlYl) dimethylsulfonium bromide and 2.3 parts of sodium hydride. The reaction mixture is stirred at room temperature until the evolution of hydrogen is substantially complete. The reaction mixture is filtered to remove the solids which are then extracted with methylene chloride. The methylene chloride extract is concentrated by evaporation to give 10.5 parts of dimethylsulfonium a-bromophenacylide, M.P. 129132 C. The filtrate from the reaction mixture is evaporated under vacuum to give an additional 1.6 parts of dimethylsufonium a-bromophenacylide.

Calcd. for C I-I BrOS: C, 46.34; H, 4.28; Br, 30.84; 0, 6.17; S, 12.37. Found: C, 46.12; H, 4.28; Br, 30.70; 0, 6. 89; S, 12.11.

Following substantially the same procedure as in Example 41 above the following a-halosulfonium ylids of this invention are prepared.

Example 42 dimethylsulfonium a-chlorophenacylide 43 dimethylsulfonium ot-iodophenacvlide 44 dimcthylsulfonium a-bromo-4-chlorophenacylide 4S dimethylsulfonium a-brom 2,4-dichlorophenacylide 46 dimethylsulfonium a-bromo-2,4-6'-trichlorophenacylide 47 dimethylsulfonium a-chloro-4-methylphenacylide 4'8 dimethylsulfonium a-chloro-4-tert-butylphenacylide 49 dimethylsulfonium a-chloro-ZA-dimethylphenacylide 0 dimethylsulfonium a-chloro-2,4, 6'-trimethylphenacylide 51 dimethylsulfonium a-chloro-2,5-diethylphenacylide 52 dimethylsulfonium a-chloro-2,6-di(tert-butyl)phenacylide 53 dimethylsulfonium a-bromo-4-bromophenacylide 54 dimethylsulfonium u-bromo-3,5-dibromophenacylide 55 dimethylsulfonium a-bromo-2-iodophenacylide 5 6 dimethylsulfonium a-bromo-2, 6-difiuorophenacylide 57 dimethylsulfonium a-chloro2,5-dimethy1phenacylide 5'8 dimethylsulfonium a-chloro-Il,S-dimethylphenacylide 59 dimethylsulfonium u-chloro-2,3,4,5,6-pentachlorophenacylide 60 dimethylsulfonium a-bromo- 4-nitrophenacylide 61 dimethylsulfonium a-bromo-2, 4-dinitrophenacylide 62 dimethylsulfonium a-bromo-4-methoxyphenacylide 63 dimethylsulfonium m-bromo-2,4-dimethoxyphenacylide 64 dimethylsulfonium u-bromo-2,5-dimethoxyphenacylide 65 dimethylsulfonium ot-chloro-4-n-butoxyphenacylide 66 dimethylsulfonium m-chloro-4-phenylphenacylide 67 dimethylsulfonium a-chloro-2-methyl-4-nitrophenacylide 68 dimethylsulfonium u-chloro-2-methoxy-4'chlorophenacylide 69 dimethylsulfonium a-chloro-2-methyl-4-methoxyphenacylide 70 diethylsulfonium ut-bromophenacylide 71 di(n-butyl)sulfonium u-bromophenacylide 72 di(n-octyl)sulfonium ot-bromophenacylide 73 di-(Z-chloroethyl)sulfonium ot-bromophenacylide 74 di(3-chlorobutyl)sulfonium u-bromophenacylide 75 di(n-dodecyl)sulfonium a-bromophenacylide 76 di(4,4-dichloropentyl)sulfonium a-chloro-4-chlorophenacylide 77 di(2,2,4-tribromobutyl)sulfonium a-chlorophenacylide 7 8 di(2-fluoropentyl)sulfonium a-chlorophenacylide 79 di(2-iodoethyl)sulfonium ot-chlorophenacylide 80 diethylsulfonium u-bromo-2,4-dimethylphenacylide The sulfonium ylids used as starting materials in the preparation of the a-halosulfonium salts of this invention and processes for making them are disclosed and claimed in application Ser. No. 549,166, now United States Patent No. 3,359,222, filed of even date herewith. Said process comprises reacting a sulfonium salt of the formula wherein R, R R R R X, a, b and c are as defined above with a substantially equimolar amount of an alkaline material such as sodium hydride or sodium hydroxide in the presence of an inert liquid medium such as an aqueous medium or organic medium. Temperature is not critical and room temperature is usually employed.

The a-halosulfonium ylids and a-halosulfonium salts of this invention are useful for various purposes such as fire retardants, rust inhibitors, rust removers, tanning agents and water-insoluble dispersion agents, and as chemical intermediates for petroleum additives and agricultural chemicals. For example, the a-halosulfonium ylids and a-halosulfonium salts of this invention are useful as pesticides, particularly fungicides. In practicing the fungicidal methods of this invention, one or more of the present rx-halosulfonium ylid or a-halosulfonium salts is applied to the fungal organisms or the material to be treated for the control of fungi in an amount sufiicient to exert fungicidal activity. The fungicidal sulfonium compounds of this invention are particularly effective when applied directly to the soil for control of soil borne fungal organisms. They are also effective in the treatment of plant life such as vegetables, ornamental plants and fruit-bearing trees; organic fibers and fabrics; leather; paints and lubricating oils and various cellulosic materials such as wood. In application to soil and plants, fungicidal control is obtained in most instances by the application of from about 0.01 pound to about 25 pounds of active ingredient per acre. The preferred amount is determined by and dependent upon the particular fungicidal compound selected, the method of application, and in the case of application to plant life, the state and condition of growth and the climatic conditions.

The fungicidal activity of the a-halosulfonium compounds of the invention is demonstrated as follows.

An intimate mixture of 2 volumes of yellow corn meal and 3 volumes of white sand is infested with a particular pathogen (below itemized) and incubated for two weeks at 20 C. Then one volume of this infested mixture is blended uniformly with 3 volumes of a good grade of top soil which had been sterilized. To accomplish complete blending the composite of soil and .infested mixture is passed through a No. 8 screen three times. A number of small cups are then tightly packed with 30 gram portions of the composite and the surface thereof leveled.

A sulficient amount of (a-iodophenacy)dimethylsulfonium iodide is dissolved in acetone to make a 1% by weight solution which is then diluted with water to provide a formulation having a concentration of 0.1% by Weight. To provide the desired concentration in the aforedescribed soil composite the following further dilutions with water are made:

Conc. desired in soil in ppm. 30 Ml. of 0.1% formulation 1 M1. of water added to formulation 3 1=no growth 2=growth from corn meal only 3=some growth in soil away from corn meal particles 4=surface covered but little aerial growth 5 growth equivalent to that on untreated soil.

The results obtained with (a-iodophenacyl) dimethylsulfonium iodide at a soil concentrationof 30 p.-p.m. are set forth below for each of the two identical fungal orgamsms:

Fungal organism: Rating Pythium ultimum 1 Rhizoctonia solani l The fungicidal compositions of this invention contain at least one active ingredient and a material referred to in the art as a fungicidal adjuvant in liquid or solid form. The fungicidal compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids, granules, pellets, solutions, aerosols and aqueous dispersions or emulsions. Thus the active: ingredient can be used with an adjuvant such as afinely-divided particulate solid, a liquid of organic, water, a wetting agent, dispersing agent, an emulsifying agent or any suitable combination of these.

Typical finely-divided solid carrier and extenders which can be used in the fungicidal compositions of this invention include, for example, the tales, clays, pumice, silica, diatomaceous earth, chancoal, quartz, Fullers earth salt, sulfur, powdered cork, powdered wood, Walnut flour, chalk, tobacco dust, volcanic ash, and the like. Typical liquid diluents include, for example, water, kerosene, Stoddard solvent, hexane, benzene, toluene, acetone, ethylene dichloride, xylene, alcohols, diesel oil, glycols and the like. Typical diluents for aerosols include, for example, Freons such as di chlorofiuoromethane, trichlorofluoromethane, and the like.

The fungicidal compositions of this invention, particularly liquids and Wettable particles, usually contain as a conditioning agent one or more surface-active agents in amounts sufiicient to render a given composition readily dispersible in water or in oil. By the term surface-active agent it is understood that wetting agents, dispersing agents, suspending agents, emulsifying agents and the like are included therein.

The surface-active agents employed can be of the anionic, cationic or nonionic type. They include, for example, sodium oleate, sulfonated petroleum oils, alkyl aryl sulfonates, sodium lauryl sulfate, polyethylene oxides, lignin sulfonates, and other surface-active agents.

The fungicidal compositions of this invention generally contain from about 0.005% to about 95% by weight of the active fungicidal ingredient.

The fungicidal compounds of the present invention can be employed in combination with other fungicides to give compositions that have broad spectrum fungicidal activity. In these mixtures, the auxiliary fungicidally active materials can be present in any desired amount, ordinarily from about 0.1 to about 20 parts by weight per 1 part by weight of a compound of the present invention. In some instances it may even be desirable to employ two or more auxiliary fungicides.

Typical of the auxiliary fungicides that can be employed in combination with the compounds of the present invention are the following:

N-trichloro-methylthio-4-cyclohexene-1,2-dicarboximide Tetramethylthiurarn disulfide Manganese ethylene-bis-dithiocarbamate Ferric dimethyl dithiocarbamate Zinc ethylene-bis-dithiocarbamate Zinc dimethyl dithiocarbamate Tetra copper calcium oxychloride Tetrachloro-p-benzoquinone 2,3-dichloro-1,4-naphthoquinone 2-dichloro-6- o-chloroanilino) triazine Ethylene thiuram monosulfide Z-heptadecyl glyxalidine acetate Ferric dimethyl dithiocarbamate plus Z-mercaptobenzothiazole Manganese dimethyl dithiocarbamate plus 2-mercaptobenzothiazole Copper dihydrazinium sulfate Copper-S-quinolinolate Cycloheximide Terramycin Streptomycin When operating in accordance with the present invention, the a-halosulfonium compounds or a composition containing them can be applied to the fungal organisms to be controlled, or to their habitats in any convenient fashion, e.g., by means of hand dusters or sprayers. Applications to the above-ground portions of plants conveniently can be carried out with powder dusters, boom sprayers and spray clusters. In foliar applications, the employed compositions should not contain any appreciable amount of phytotoxic diluents. In large scale operations, dusts or low volume sprays may be applied from airplanes.

The term fungicidal composition as used herein and in the appended claims is intended to mean not only compositions in a suitable form for application but also concentrated compositions which require dilution or extension with a suitable quantity of liquid or solid adjuvant prior to application.

The emodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Compound having a formula selected from the group consisting of rt /SZG C{\ 11 011, R R

and

rt s-ono R cHz R20 R 1,

wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing from 1 to 3 halogen atoms, X is selected from the group consisting of Cl, Br and I, R is selected from the group consisting of halogen and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R is phenyl, a is an integer from 0 to S inclusive, b is an integer from 0 to 2 inclusive and c is an integer from 0 to l inclusive.

2. Compound of claim 1 having the formula represented by (a).

3. Compound of claim 1 having the formula represented by (b).

4. Compound of claim 1 which is (u-bromophenacyl) dimethylsulfonium bromide.

5. Compound of claim 1 which is (a-chloro-2,4-dichlorophenacyl) dimethylsulfonium chloride.

6. Compound of claim 1 which is (a-chloro-2,4,6-trimethylphenacyl) dimethylsulfonium chloride.

7. Compound of claim 1 which is (a-chlorophenacyl) dimethylsulfonium chloride.

8. Compound of claim 1 which is (ot-chlorophenacyl) diethylsulfonium chloride.

9. Compound of claim 1 which is (a-iodophenacyl) dimethylsulfonium iodide.

10- Compound of claim 1 which is dimethylsulfonium a-chlorophenacylide.

11. Compound of claim 1 which is dimethylusulfoniurn a-bromophenacylide.

12. Compound of claim 1 which is dimethylsulfonium a-iodophenacylide.

13. Process for the preparation of a compound of the formula RCH;

wherein R and R are each selected from the group consisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing from 1 to 3 halogen atoms, X is selected from the group consisting of Cl, Br and I, R is selected from the group consisting of halogen and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R is phenyl, a is an integer from 0 to 5 inclusive, b is an integer from 0 to 2 inclusive and c is an integer from to 1, which comprises reacting a sulfonium ylid of the formula R CH:

with a substantially equimolar amount of a halogen selected from the group consisting of chlorine, bromine and iodine, wherein R, R R R R a, b and c are as defined above.

14. Process for the preparation of a compound of the formula wherein R and R are each selected from the group con sisting of hydrogen, alkyl of not more than 12 carbon atoms and haloalkyl of not more than 12 carbon atoms containing from 1 to 3 halogen atoms, X is selected from the group consisting of Cl, Br and I, R is selected from the group consisting of halogen and alkyl of not more than 4 carbon atoms, R is selected from the group consisting of N0 and alkoxy of not more than 4 carbon atoms, R; is phenyl, a is an integer from 0 to inclusive, b is an integer from '0 to 2 inclusive and c is an integer from 0 to 1, which comprises reacting an ot-halosulfonium salt of the formula References Cited UNITED STATES PATENTS 3,359,322 12/1967 Ratts.

OTHER REFERENCES Speziale et al., J. Am. Chem. Soc. 87, 3460-3462 (1965).

DANIEL D. HORWIT Z, Primary Examiner.

US. Cl. X.R. 16730