US3044926A - Sulfonyl ethylene fungicides - Google Patents

Description

United States Patent Office 3,044,926 SULFONYL ETHYLENE FUNGICDES James P. Flavin, Mission, and Joseph R. Riden, Jr., Overland Park, Kans., assignors to Chemagro Corporation, New York, N.Y., a corporation of New York No Drawing. Filed May 29, 1958, Ser. No. 738,659 Claims priority, application France May 21, 1958 19 Claims. (Cl. 167-22) The present invention relates to new ethenyl sulfones and to their use primarily as fungicides, but also as pesticides to control other pests, e.g., as bactericides, nematocides and even as insecticides and weedicides.

It is an object of the present invention to prepare novel ethenyl sulfones.

Another object is to provide compositions containing ethenyl sulfones which have outstanding utility in protecting a wide variety of materials from fungi.

An additional object is to provide compounds which afford protection against a wide range of pests.

A further object is to provide compositions containing ethenyl sulfones which have outstanding utility in protecting a wide variety of materials from bacteria.

Still another object is to provide ethenyl sulfone compositions which protect plants .against nematodes.

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 the preparation of ethenyl sulfones of the formula where R R and R are each alkyl groups and X is a halogen of atomic Weight not over 80, Le. fluorine, chlorine or bromine, or hydrogen. The preferred compounds are those where X is chlorine or hydrogen. Preferably R R and R are lower alkyl groups, generally of 1 to 8 carbon atoms and most desirably not over 4 carbon atoms.

Typical examples of compounds which can be made and used according to the present invention are tris- (methylsulfonyl) ethylene; tris(methylsulfonyl) chloroethylene; tris(methylsulfonyl) bromoethylene; tris(methylsulfonyl) fiuoroethylene; tris(ethylsulfonyl) ethylene; tris(ethylsulfonyl) chloroethylene; tris(n-propylsulfonyl) ethylene; tris(n-propylsulfonyl) ethylene; tris(n-propylsulfonyl) chloroethylene; tris(isopropylsulfonyl) ethylene; tris(isopropylsulfonyl) chloroethylene; tris(n-butylsulfonyl) ethylene; tris(n-butylsulfonyl) chloroethylene; tris(isobutylsulfonyl) ethylene; tris(isobutylsulfonyl) chloroethylene; tris(sec. butylsulfonyl) ethylene; tris- (sec. butylsulfonyl) chloroethylene; tris(tert. butylsulfonyl) ethylene; tris(tert. butylsulfonyl) chloroethylene; tris(n-amylsulfonyl) ethylene; tris(n-amylsulfonyl) chloroethylene; tris(n-hexylsulfonyl) ethylene; tris(n-hexylsulfonyl) chloroethylene; tris(n-octylsulfonyl) ethylene; tris(n-cctylsulfonyl) chloroethylene; tris(Z-ethylhexylsulfonyl) ethylene; tris(Z-ethylhexylsulfonyl) chloroethylene; tris(n decylsulfonyl) ethylene; tris(n-decylsulfonyl) chloroethylene; tris(dodecylsulfonyl) ethylene; tris(noctadecylsulfonyl) ethylene; tris(n-octadecylsulfonyl) chloroethylene; l,2-di(methyl sulfonyl) l-n-propylsulfonyl ethylene; and l-methyl sulfonyl-Z-ethyl sulfonyl-2- propylsulfonyl chloroethylene.

The compounds of the invention are effective as pesticides for controlling fungi, bacteria, smuts, mildew, nematodes and other organisms in the class of plant pests.

The compounds of the present invention are also uses ful for protectingcloth, leather, Wood and painted surfacesfrom attack by fungi and other organisms. While it is possible to apply the compounds of the present invention in undiluted form to the plant or other material to be protected, it is frequently desirable to apply the novel sulfones in admixture with either solid or liquid inert, pesticidal adjuvants. Thus, the sulfones can be applied to the plants for fungicidal purposes, for example,

by spraying them with aqueous or organic solvent dispersions of the sulfone. Similarly, wood surfaces canbe protected by applying a protective film of the sulfone by brushing, spraying or dipping, utilizing a liquid dispersion of the sulfone. The choice of an appropriate solvent is determined largely by the concentration of active ingredient which it is desired to employ, by the volatility required in a solvent, the cost of the solvent and the nature of the material being treated. Among the many suitable organic solvents which can be employed as carriers for the present pesticides, there may be mentioned hydrocarbons such as benzene, toluene, xylene, kerosene, diesel oil, fuel oil, petroleum, naphtha, ketones such as acetone, methyl ethyl ketone and cyclohexanone, chlorinated hydrocarbons, such as carbon tetrachloride, chloroform, trichloroethylene, perchloroethylene, esters such as ethyl acetate, amyl acetate and .butyl acetate,.,the monoalkyl ethers of ethylene glycol, e.g., the monomethyl ethers and the monoalkyl ethers of diethylene glycol, e.g., the monoethyl ether, alcohols such as ethanol, isopropanol and amyl alcohol, etc.

The sulfones can also be applied to plants and other materials along with inert solid fungicidal adjuvants or carriers such as talc,pyrophyllite, Attaclay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fullers earth, cottonseed hulls, wheat flour, soybean flour, etc., pumice, tripoli, wood flour, Walnut shell 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, e.g., p-isooctyl phenol condensed with 10 ethylene oxide units; and soaps, e.g., sodium stearate and sodium oleate. Typical surface active agents are: Aerosol OS (sodium salt of propylated naphthalenesulfonic acid); AerosolOT [(di-Z-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); Areskap [oHOC H C H (C H (SO;;=Na)]; Areskap 300 4 9) 's e s e sl ethylene glycol lauryl ether); Daxad No. 11 (sodium salt of polymerized alkylated arene sulfonic acid); Duponol Patented July 17, 1962 LS (sodium oleyl sulfate); Duponol WA (sodium lauryl sulfate); Emulsept N-OH2 011 23 N-CHz CHzCHzONa CHzC O 0N8 Myrj (polyethylene glycol stearate); Nacconol NR (sodium dodecyl benzene sulfonate); Wekal 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 (solidifiedurea complex of polyethylene glycol ester of mixed fatty and resin acids); Santomerse No. 1 (sodium dodecyl benzenesulfonate); Santomerse D (sodium decyl benzenesulfonate); Santomerse B Sapamine KW [CH CH 7CH:CH (CH C0 NHCH CH N 3) a s) 2] l s s] Span 20 (sorbitan monolaurate); Span 40 (sorbitan monopalmitate); Span 60 (sorbitan monostearate); Span 80 (sorbitan monooleate); Sterox CD (polyethylene glycol ester of tall oil acids); Snlframin DR (sodium salt of sulfonated condensation product of ethanolamine with a fatty acid); Tergitol 08 [C H CH(C H )CH OSO Na]; Tergitol4 [C H CH(C H CH CH CH (CH CH (CH OSO Na] Tergitol 7 Triton [p-C H 7C H4(OCH2CH2)2OSO3N3. where C H is diisobutyl]; Triton X-lOO Tween 20 [tris(polyoxyethylene) sorbitan monolaurate]; Tween 40 [tris(giolyoxyethylene) sorbitan monopalmitate]; Tween 60 [tris(polyoxyethylene) sorbitan monostearate]; Tween 80 [tris(polyethylene) sorbitan monooleate]; Ultrawet SK (sodium alkylbenzene sulfonate) Ultravon K (sodium salt of sulfonated alkyl be'nzimidazole); 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 in 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 prop erty of the final dust composition.

When solid compositions are employed, in order to obtain a high degree of coverage with a minimum dosage of the formulation, it is desirable that the formulation be in finely divided form. The dust containing active ingredient usually should be sutficiently fine that substantially all will pass through a 20 mesh Tyler sieve. A dust which passes through a 200 mesh Tyler sieve also is satisfactory.

For dusting purposes, preferably formulations are employed in which the active ingredient is present in an amount of S to 50% of the total by weight. However,. concentrations outside this range are operative and compositions containing from 1 to 99% of active ingredient by weight are contemplated, the remainder being carrier and/or any other additive or adjuvant material which may be desired. It is often advantageous to add small percentages of surface active agents, e.g., 0.5 to 1% of the total composition by weight, to dust formulations, such as the surface active agents previously set forth.

For spray application, the active ingredient may be dissolved or dispersed in a liquid carrier, such as water or other suitable liquid. The active ingredient can be in the form of a solution, suspension, dispersion or emulsion in aqueous or non-aqueous medium. Desirably, 0.5 to 1.0% of a surface active agent by weight is included in the liquid composition.

For adjuvant purposes, any desired quantity of surface active agent may be employed, such as up to 250% of the active ingredient by weight. If the surface active agent is used only to impart wetting qualities, for example, to the spray solution, as little as 0.05% by weight or less of the spray solution need be employed. The use of larger amounts of surface active agent is not based upon wetting properties but is a function of the physiological behavior of the surface active agent. These considerations are particularly applicable in the case of the treatment of plants. In liquid formulations the active ingredient often constitutes not over 30% by weight of the total and may be 10%, or even as low as 0.01%.

The novel sulfones of the present invention can be employed in compositions containing other pesticides, more especially fungicides, insecticides and bactericides, e.g., phenothiazine, pyrethrum, rotenone, DDT, etc.

The novel sulfones of the present invention can be prepared by reacting a mercaptan having the formula RSH where R is an alkyl group with a substituted ethylene having the formula where at least three substituents are halogen of atomic weight not over 80 and the remaining substituent is such a halogen or hydrogen to form an ethenyl type sulfide followed by oxidation of this sulfide to the corresponding sulfone. The oxidation of the sulfide is preferably carried out with hydrogen peroxide. However, other oxidizing agents can be used such as permanganates, e.g., potassium permanganate, chromic acid, nitric acid, bypochlorites, e.g., sodium hypochlorite, organic peroxides,

e.g., benzoyl peroxide, etc. The oxidation frequently is bonates, bicarbonates and organic bases.

carried out in an organic solvent.

The preliminary reaction of the mercaptan with the polyhalo substituted ethylene is carried out in the presence of an acid acceptor such as alkali hydroxides, car- Typical acid acceptors include sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, tetraethyl ammonium hydroxide, etc. Preferably, an organic solvent is also present, e.g., ethyl alcohol, methyl alcohol, n-butanol, etc.

The general scheme of the reaction is illustrated below.

In the specification and claims unless otherwise indicated all parts and percentages are by weight.

Unless otherwise indicated the hydrogen peroxide concentration in the examples is 30%.

EXAMPLE 1 Bis(n-Propylsulfonyl)-1-Chl0r0ethylene and Tris(n-Propylsulfonyl) Ethylene Trichloroethylene 260 g. (2 mol) n-Propylmercaptan 76 g. 1 mol) Sodium hydroxide :60 g. (1.5 mol) The trichloroethylene was mixed with 100 ml. of alcohol andthen a mixture of the n-propyl mercaptan and sodium hydroxide dissolved in 300 ml. of alcohol were added dropwise. The mixture was heated to 70 C. and after addition of all the material was refluxed for an hour. The sodium chloride was filtered olf and the alcohol removed under aspirator vacuum. Two volumes of Water were added and the mixture thenextracted with 3 volumes of benzene. The benzene was distilled off under aspirator vacuum.

The product was then distilled under aspirator vacuum to give 3 fractions. The first fraction distilled at 77- 120 C.; the second fraction distilled at l20-l44 C. and the third fraction was the high boiling residue.

There were then separately oxidized 20 g. of the first fraction, g. of the second fraction and g. of the third fraction, using in each case 30 ml. of glacial acetic acid and 30 ml. of 35% hydrogen peroxide at 70 C. for 2 hours.

The oxidized first fraction was primarily n-propylsulfonyl 1,2-dichloroethylene. The oxidized second fraction was primarily bis(n-propylsulfonyl) chloroethylene.

The oxidized third fraction was primarily tris(n-propy1- sulfonyl) ethylene. It was observed that the impure mixtures obtained as the fractions in this example could he successfully used as fungicides in the same manner as the pure compounds.

'6 EXAMPLE 2 Tris(n-Propylsulfonyl) Ethylene Trichloroethylene 1.30 g. (1 mol) n-Propyl mercaptan 228 g. (3 mol) Sodium hydroxide 120 g. (3 mol) The procedure of Example 1 was repeated to obtain substantially pure tris(n-pr0pylsulfonyl) ethylene.

EXAMPLE 3 Tris(n-Propylsulfonyl) Chloroethylene The trichloroethylene of Example 2 was replaced by 166 g. of tetrachloroethylene and the product obtained was tris(n-propylsulfonyl) chloroethylene.

EXAMPLE 4 Bis(Ethylsulfonyl) Chloroethylene and Tris(Eth-ylsulfonyl) Ethylene Trichloroethylene 260 g. (2 mol). Ethyl mercaptan .62 g. (1 mol) Sodium hydroxide 50 g. (1.25 mol) The trichloroethylene was mixed with 200 ml. of ethyl alcohol and there were added the sodium hydroxide in 200 ml. of ethyl alcohol followed by the mercaptan. Ethyl alcohol was added until all the materials were in solution. The addition of the mercaptan and sodium hydroxide was accomplished at reflux over a period of 1 hour. The mixture was further refluxed for 3 hours, cooled, the sodium chloride filtered off, 500 m1. of alcohol removed by distillation and the mixture taken up in 2 volumes of water and extracted with 4 volumes of benzene. The benzene was distilled off and the mixture fractionally distilled under aspirator vacuum to give the following products:

B.P., C. Ethyltbio 1,2-chloroethylene 78-83 Bis(ethylthio -dichloroethylene 92 Tris(ethylthio) ethylene 132 Ten grams of the bis(ethylthio) chloroethylene was oxidized with 0.5 mol of hydrogen peroxide in glacial acetic acid at C. to obtain bis(ethylsulfonyl) chloroethylene. f

In similar fashion 18 g. of the tris(ethylthio) ethylene was oxidized with 0.4 mol of hydrogen peroxide in of trichloroethylene to 200 ml. of ethyl alcohol and slowly adding 76 g. (1 mol) of isopropyl mercaptan and 50 g. (1.25 mols) of sodium hydroxide dissolved in 400 ml. of ethyl alcohol. The mercaptan'was added over 1 hour and the mixture was refluxed for 3 more hours. The sodium chloride was filtered off, the alcohol taken off and then water was added and the mixture extracted with benzene and washed with water. The benzene was removed at atmospheric pressure'and several cuts were distilled over at aspirator pressure. The cuts boiling below 129 C. were discarded and the cut boiling at l29'139 C.- recovered. This cut'was a mixture containing tris(isopropylthio) ethylene together wtih some bis(isopropylthio) chloroethylene. 12.5 g. of the cut was oxidized with 45 ml. of 35% hydrogen peroxide and 30ml; of acetic acid at 90 C. for 2 hours to obtain tris(isopropyl sulfonyl) ethylene asan oil.

EXAMPLE 6 Tris(Methylsulfonyl) Ethylene Example 5 was repeated using double The isopropyl mercaptan was replaced by 100 g. of methyl mercaptan. The tris(methylthio) ethylene had a BI. range of 1l5-l40 C. at the aspirator and contained some bis(methylthio) chloroethylene.

To 166 gms. of the tris(methylthio) ethylene were added 90 ml. of 35% hydrogen peroxide and 30 ml. of acetic acid. The mixture was held at 90-95" C. with stirring for 2 hours and the tris(methylsulfonyl) ethylene recovered as an oil.

Typical examples of suitable formulations are given below.

EXAMPLE 7 A wettable powder fungicide was made from 20% tris(n-propylsulfonyl) ethylene, 38% diatomaceous earth, 40% kaolin clay and 2% sodium N-methyl-N- oleoyl taurine (wetting agent). The mixture was ground so that over 90% passed through a 325 mesh U.S. standard sieve.

In place of the tris(n-propylsulfonyl) ethylene formulation of this example there were also made up three other formulations which were identical except that the tris- (n-propylsulfonyl) ethylene Was replaced by an equal weight of tris(n-propylsulfonyl) chloroethylene in the first case, by an equal weight of tris(n-butylsulfonyl) ethylene in the second case and t1is(methylsulfonyl) ethylene in the third case.

EXAMPLE 8 A granular fungicide comprising of tris(isopropylsulfonyl) ethylene as the active compound and 95% of calcined diatomaceons earth of 20 to 70 mesh size (U.S. standard sieve) as a granular absorbent diluent was prepared by spraying the sulfone in liquid state on the granules with mixing.

In place of the tris(isopropylsulfonyl) ethylene formulation of this example there were also made up two other formulations which were identical except that in one case the tris(isopropylsulfonyl) ethylene was replaced by an equal amount of tris (methylsulfonyl) ethylene and in the other case tris(ethylsulfonyl) ethylene was used as the replacement.

EXAMPLE 9 An emulsifiable spray concentrate fungicidepreparation comprising 48 grams of tris(methylsulfonyl) ethylene, 10 grams of polyoxyethylene sorbitan monolaurate (Tween 20), as an emulsifier and sufiicient xylene to make the mixture up to 100 ml. was prepared by stirring the ingredients together. Ln place of the tris(methylsulfony-l) ethylene concentrate of this example there were also made up two other concentrates which were identical except that in one case the tris(:rnethylsulfonyl) ethylene was replaced by an equal amount of tn's(ethylsulfonyl) ethylene while in the other case tris(isopropylsulfonyl) ethylene was used as a replacement.

EXAMPLE 10 The three spray concentrates of Example 9 were each diluted with 480 liters of water to give an aqueous emulsion containing 100 ppm. of active ingredient in each case.

Satisfactory results have also been obtained for example, by emulsifying the sulfones directly in water without the addition of an organic solvent. Thus one part of tris(n-butylsulfonyl) ethylene can be emulsified in 100 parts of water directly with the aid of 0.1 part of polyoxyethylene sorbitol (Atlox 1045).

The compounds of the present invention were tested as soil fungicides as shown in Table I. The chemical to be tested was mixed with soil naturally infested with Pythium spp. Pea seeds were planted and the efficiency of the chemicals noted as percent emergence.

TABLE I Lbs. of chemical/acre Chemical 200 100 50 25 12.5 6. 25

tris(methylsulfonyl) ethylene... 100 100 100 40 tris(ethylsulfonyl) ethylene. 100 100 60 tris(isopropylsultonyl) ethylene. 90 90 20 0 The compounds of the present invention also are good seed disinfectants, being in a class with the mercurials in this respect. Table II shows the results as a seed disinfectant using oat seeds naturally infested with Helminthosporium victoriae. The results are expressed as percent control of this fungus which causes Victoria blight.

TABLE II Ounces/bushel Chemicals tris(methylsull0nyl) ethylene, percent" 20 tris(ethylsulionyl) ethylene, pcrcent. 100 90 tris(isopropylsulfonyl) ethylene, per- 40 0 cent wherein R R and R are each alkyl groups and X is selected from the group consisting of a halogen of atomic weight not over 80 and hydrogen.

2. A compound according to claim 1 wherein R R and R are each alkyl groups having 1 to 18 carbon atoms. 3. A compound according to claim 1 wherein X is hydrogen.

4. A compound according to claim 1 wherein R R and R each have 1 to 4 carbon atoms and X is hydrogen. 5. A compound according to claim 1 wherein R R and R each have 1 to 8 carbon atoms.

6. A compound according to claim 5 wherein X is hydrogen.

7. A compound having the formula C: SO2Rz wherein R R and R are each alkyl groups and X is a halogen selected from the group consisting of fluorine, chlorine and bromine.

8. A pesticidal composition comprising a compound having the formula C=CSOaRa wherein R R and R are each alkyl groups and X is selected from the group consisting of a halogen of atomic weight not over 80 and hydrogen together with a surface active agent.

9. A composition according to claim 8 wherein X is hydrogen.

10. A composition according to claim 8 wherein R R and R each have 1 to 4 carbon atoms and X is hydrogen.

11. A composition according to claim 8 wherein R R and R each have 1 to 8 carbon atoms.

12. A composition according to claim 11 wherein X is hydrogen.

13. A process for killing fungi comprising applying to the fungi habitat an effective amount of a compound having the formula C=C-SOaRa R SOg wherein R R and R are each alkyl groups and X is selected from the group consisting of a halogen of atomic weight not over 80 and hydrogen.

-14. A process according to claim 13 wherein X is hydrogen.

15. A process according to claim 14 wherein R R and R each have 1 to 8 carbon atoms.

16. A process according to claim 14 wherein R R and R each have 1 to 4 carbon atoms.

17. A process for protecting material from attack by fungi comprising applying to said material an effective amount of tris(alkylsulfonyl) ethylene.

wherein R R R are each alkyl groups and X is a halo gen selected from the group consisting of fluorine, chlorine and bromine.

References Cited in the file of this patent UNITED STATES PATENTS Schoene Jan. 3, 1950 Raasch July 7, 1959 OTHER REFERENCES Schneider: Chemische Berichte, 84, 911-916 (esp. p. 916), 1951.

Frear: A Catalogue of Insecticides and Fungicides, vol. I, page 58, 1947, Chronica Botanica Co.

Claims (1)

13. A PROCESS FOR KILLING FUNGI COMPRISING APPLYING TO THE FUNGI HABITAT AN EFFECTIVE AMOUNT OF A COMPOUND HAVING THE FORMULA