BE543377A - - Google Patents

Description

       

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   The present invention relates to a new class of fungicidal compounds and more particularly to bis (organosulfonyl) ethylenes having special utility as seed protection agents.



   The main object of the present invention is a new class of fungicidal compositions. She threw a means to fight the fungi and especially also a means to protect the seeds against the ravages of the fungi. A further subject of the invention is a new class of organic compounds.



   It has now been discovered that compounds of the class of compounds known by the name of bis (organosulfonyl) ethylenes possess remarkable fungicidal activity. Among the compounds in question, there may be mentioned, in particular, the bis (alkylsulfonyl) ethylenes of formula RSO2CH-CHSOZR 'in which R is an alkyl group comprising 3 to 12 carbon atoms. When applying bis (organosulfonyl) ethyl. nes to the habitat of fungi, in particular to seeds. before planting, a very effective control of the fungi activity is obtained.



   The bis (organosulfonyl) ethylenes which constitute the active ingredients according to the present invention can be represented by the general formula R1SO2CR2-CH3SO2R4 in which R1 and R4 are organic groups, usually hydrocarbon radicals of the alkyl type, aryl-substituted aryl and alkyl, and R2 as well as R3 are organic radicals or hydrogen (usually hydrogen).



   Several structural variants are included in the formula given in the previous paragraph and all such structural variants are encompassed in

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 the present invention.



   The preferred and most common variant of
 EMI2.1
 structure RlSOZCRZ = CR3soZR4 is that in which R1 and R4 are alkyl aryl hydrocarbon radicals, while R2 and R3 denote hydrogen. As examples of this type of compounds in the aliphatic series,
 EMI2.2
 the following may be mentioned: 1,2 iais (methylsulfenyl) ethylene; 12-bis (ethylsulfonyl) -ethylene; 1,2-bis (n-propylaulfonyl) -ethylene; 1,2-bis (isopropylsulfonyl) -ethylene; 1,2-bis (n-butylsulfonyl) -ethylene; 1,2-bis (isobutylsulfonyl) ethylene; 1,2 bis (-butylsulfonyl) ethylene; 1 * 2bis (amylsulfonyl) -ethylene; 1,2-bis (hexyosulfonyl) -ethylene; 1,2-bis (heptylsulfonyl) -ethylene; lu bis (octylsulfonyl) ethylene; 1 * 2 bis (nonylsulfonyl) ethylene; 1,2-bis (decylsulfonyl) -ethylene;

   1,2-bis (undecylsulfonyl) -ethylene, and 1,2.bis (dodecylsulfonyl) ethylene or 1,2-bis (laurylsulfonyl) ethylene. An example of this type of compounds in the class of compounds comprising an alkyl radical substituted by an aryl group is
 EMI2.3
 consisting of 1,2-bis (benzylsulfonyl) -ethylenel In the aromatic series, as examples of compounds according to the present invention, in which the aromatic component is an aryl hydrocarbon radical, mention may be made of
 EMI2.4
 the following: 1,2-bis (phenylsulfonyl) -ethylene; 1,2- bis (totylsulfonyl) -ethylene, especially 1,2-.bis (- 'tolylsulfonyl) .- ethylene, 1,2-bis (m tolylsulfonyl) - ethylene * and 1,2-bis (B-tolylsulfonyl )-ethylene; 2-bis (biphenylsulfonyl) -ethylene, and the like.

   As compounds in which the aryl group is substituted, mention may be made of
 EMI2.5
 the following: 12.bis (nitrophenylsulfonyljeth.t¯ene, especially 1 * 2-bis (o-nitrophenylsulfanyl) .ethyl: ne, 1,2- bis (m-nitrophenyleulfonyl) -ethylene, and 1,2.-bis ( , -nitro-phenylsulfonyl) -ethylene; 1,2-bis (halophenylsulfonyl) - ethylene, in particular 1 2-bis (zhlorophenylsulfonyl) -ethy.

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 EMI3.1
 lene and 1,2-bis (bromosulfonyl) ethylene; 1,2-bis (halonitrophenylsulfonyl) -ethylene; 1,2rbis (aminaphenylsulfa nyl) -ethylene, and the like.



   The present invention also encompasses bis (organosulfonyl) -ethylenes, in which R1 and R4 differ from each other. In this case, it may be two alkyl groups, two aryl hydrocarbon groups, one alkyl group and one aryl group, etc.



  As examples of this type of compound, mention may be made of
 EMI3.2
 . following: 1-phenylsulfonyl-2-2-tolylsulfonyl-ethylene; 1-phenylsulfonyl-2-2-nitrophenylsulfonyl-ethylene; 1-methylsulfonyl-2-phenylsulfonyl-ethylene; 1-hoxylaulfonyl-2-m-tolylsulfonyl-ethylene, and the like.



   Finally, the invention encompasses bis (organosulfonyl) -ethylenes, in which R2 and R3 are organic groups rather than hydrogen. As examples of these compounds, the following may be mentioned:
 EMI3.3
 23 bis (methylsulfonyl) butenes 2; 1,2-bis (tolylsuZfo nyl) -butene-1; and the like.



   It will be recalled that an ois-trans isomerism exists in this series of compounds and that the preparation-. Ordinary version gives mixtures of these isomers. However, it is possible to separate the cis isomer from the trans isomer by the usual methods used for such separation. The invention encompasses the use of not only pure cis and trans isomers, but also mixtures of cis-trans isomers, since such mixtures as well as pure isomers possess fungicidal activity.

   A particularly preferred embodiment of the present invention involves the use of trans isomers, since, as will be shown later, these particular isomers in many cases possess surprisingly greater fungicidal activity.

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 higher than that of the cis isomer or the mixture of cis and trans isomers. The expression "trans't isomer, as used in the present specification, designates the isomer whose melting point is the highest, this isomer generally having a lower solubility than that of the isomer whose melting point is the lowest.

   Although, as far as the applicant is aware, the higher melting point isomer and the trans isomer, it does not wish to be bound by this design and, when discussed herein In memory of the trans isomer, it is the one of the two geometric isomers of a given bis (organosulfonyl) -ethylene, which has the highest melting point.



   In accordance with the present invention, the applicant has also discovered a new class of chemical compounds possessing extremely high efficacy as seed protection agents.



  This new class of compounds includes bis (alkylsulfonyl) ethylenes of the formula RSO2CH = CHSO2R, in which R is an alkyl group comprising 3 to 12 carbon atoms. As examples of compounds belonging to this new class, the following may be mentioned:
 EMI4.1
 1,2-bis (n-propylsulfonyl) -ethylene -trans; 1,2-bis (isopropylsulfonyl) -ethylene-cisj 1,2-bis (n-butylsulfonyl) - ethylene-trans; 1,2-bis (isobutylsulfonyl) -ethylene-cis; 1,2-bis (t-butylsulfonyl) -ethylene-trans; 1,2-bis (amylsulfonyl) -ethylene-cis; 1,2-bis (hexylsu? ¯fonyl) -ethylene trans; 1,2-bis (heptylsulfonyl) -ethylene-cis; 1,2-bis (octylsulfonyl) -ethylenetransj 1,2-bis (nonylsulfonyl) -ethylene-cis; 112-bis (deeylsulfonyl) -ethylene-.trans; 1,2- bis (undecy1sulfony1) -ethy1ene cis; 1,2-bis (laurylsulfonyl) -ethylene trans;

   and 1,2-bis (laurylsulfonyl) -ethylè-ybzer

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 cis. As will be demonstrated later, this new class of compounds possesses a fungicidal activity and a seed protection function, which are even higher than those of the other sulfonylethylenes according to the present invention.



   The compounds according to the present invention can advantageously be prepared by reaction of an olefin, comprising halogen atoms on adjacent olefinically unsaturated carbon atoms, with a mercaptan or mixtures of mercaptans, followed by oxidation of the bis ( corresponding organomercaptyl) -ethylene to form the sulfone. When the desired product is one in which R2 and R3 denote hydrogen, the most suitable starting olefin is 1,2-dichlorethylene or, in general, 1,2-dihaloethylene, in which the halogen is, more commonly chlorine or bromine or one of these. When the desired product is a product, in which R2 and / or R3 is not hydrogen, other olefins should be used as starting materials.

   Thus, 'the use of 1,2-dichlorobutene-1 and / 2,3-dichlorobutene-2 gives rise to the production of products in which R2 and / or R3 denote alkyl radicals. When R1 and R4 are to be the same in the desired product, two moles of a mercaptan are reacted with one mole of the halogenated olefin, while when R1 and R4 are to be different, one reacts. one mole of a mercaptan corresponding to R1 with the olefin and the resulting product is reacted with a mercaptan corresponding to R4.



   As an example of a preferred typical process according to the invention, the reaction of 1,2-dichloroethylene with ethyl mercaptan gives 1,2-bis (ethylmercapto) -ethylene, which on treatment with peroxide

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 EMI6.1
 of hydrogen gives bis- (ethylsulfonyl) -ethylene according to the following equations:
 EMI6.2
 In addition to hydrogen peroxide, other oxidizing agents, such as potassium permanganate, sodium hypochlorite, chromic oxide and dilute nitric acid can be used, while the one can even operate an electrolytic reduction.

   In particular, in the aromatic series, the halogenated olefin can be reacted directly with a salt of a sulfinic acid, so as to directly produce bis (organosulfonyl) -ethylene.



   The following examples illustrate typical processes for the preparation of numerous compounds according to the invention.



   EXAMPLE I
 EMI6.3
 1,2-bis (ethylmercapto) - ethylene. 86 parts of potassium hydroxide were dissolved in 790 parts of 95% ethanol and 40 parts of ethyl mercaptan were added at once to the resulting solution. A solution of 48.5 parts of cis 1,2-dichlorethylene in 62 parts of ethanol was then added with stirring for 1 1/4 h while heating the mixture to reflux.



  During this addition and subsequently, the reaction system was only brought into contact with the atmosphere by means of two lead acetate traps and a column of charcoal impregnated with copper sulphate, these traps and this column being mounted in series. Stirring and heating to reflux were continued for a further 4 hours, after which the mixture was allowed to stand overnight. The precipitated salt was then filtered off and the solvent was

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 EMI7.1
 "..¯, ... 5. ... ï a'v.: J.c; ..;, '" ,,; ','. l.'1, ue until the volume is reduced by 60%. By dilution with several volumes of water, an oil was obtained, which was taken up in benzene and washed with water until the washings were neutral (4 times).

   After drying over calcium chloride, the distillation gave 45.3 parts (61%) of a 1,2 bis (ethylmercapto) -ethylene as a substantially colorless oil boiling at 91-94 C under pressure. of 5 mm. A top fraction boiling at 84-91 C under 5 mm pressure. was rejected.
 EMI7.2
 



  1.2b1séhlsulfonylethylene. 45.3 Game. 1,2-bis (ethylmercapto) -ethylene were added with stirring, over the course of one hour, to a mixture of 170 parts of 30% hydrogen peroxide and 262 parts of acetic acid, maintaining the temperature at 20-30 C by external cooling. Stirring at this temperature then continued for three hours, after which the mixture was allowed to stand overnight. The solvent was then removed by distillation under reduced pressure at 80 ° C. The residual acetic acid was then removed by drying under vacuum at room temperature, so that a residue of colorless crystals was obtained. , 64 parts (100%), PF: 82-87 C.

   The extended melting point appears to be due to the presence of a mixture of the cis and trans isomers. Fromm and Landmann, Ber. 56, 2290 (1923), indicate a M.P. of 88 C.



   EXAMPLE II
 EMI7.3
 1.2-bis (n-propylmercapto) -ethylene. A solution of 80 parts of n-propyl mercaptan, 52 parts of
 EMI7.4
 1.2 cis dichlorethylene, and 75 parts of potassium hydroxide in 800 parts of ethanol was heated under

 <Desc / Clms Page number 8>

 
 EMI8.1
 .......... - ",,, .¯ .... ¯¯.¯.- ¯¯, 1¯¯¯¯ <.... m¯ was filtered to separate the chloride of potassium precipitated and the volume of the filtrate was reduced by distillation.



  The residue was diluted with several volumes of water, the oily layer separated and the aqueous phase was extracted twice with benzene. The combined extracts were washed with water, dried over calcium chloride and freed from benzene by distillation.



  The residue was distilled under pressure, so that
 EMI8.2
 60.4 parts (65pela) of 1,2 = bis (propylmer.- capto) -ethylene were obtained in the form of a light amber liquid, slightly odorous, boiling at 134-142 C under pressure. of 18 mm. A fraction boiling at a constant temperature of 141 under 18 mm. had the following analytical composition: Calculated for C8H18S2; 0 = 54.5%; H, 9.09%; S 36.4%. Found C, 54.6%; H = 9.23%; S- 36.7%.



   EXAMPLE III
 EMI8.3
 1,2-bis (n-Dropylsulfonyl) -ethylene cis and tran, 63 parts of 30% hydrogen peroxide and 52 parts of glacial acetic acid were heated to 50 C and
 EMI8.4
 21.8 parts of 1,2-bis (n-propylmefcapto) -µthylene were added dropwise. The temperature was allowed to rise to 90 ° C. and was maintained at this last temperature by external cooling. After the addition in question, the solution was heated to 80-90 C for one hour and left to stand overnight. The reaction mixture was diluted with an equivalent volume of water and cooled for several hours in an ice salt bath.

   The product obtained was filtered, washed with ice water and dried in vacuo over potassium hydroxide, so that it was obtained.
 EMI8.5
 obtained 11.7 parts (49ù) of, '. 2-bis (n-propylsulfonyl) r

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 EMI9.1
 1 1 -n- us forms this v¯¯.s;: - .. x colorless. This product consisted of a mixture of cis and trans isomers melting over a wide range of temperatures. (45-135) Analysis: Calculated for C8H16S2O4: S = 26.6%. Found: S, 26.9%. On crystallization from a water-ethanol mixture gave 3.4 parts (11%) of the trans isomer, leaf: colorless, m.p. 153-154 C. Analysis: Calculated: C = 40.0%; H = 6.57%; S, 26.6%.

   Found C = 40.1%; H = 6.79%; S, 27.2%. The cis isomer was separated from the mother liquors by cooling in a cooler overnight. Rende. ment 7.0 parts (23%), colorless leaves, m.p. 42-44 C, Analysis: Found C = 39.5%; H = 6.79%; S, 27.0%.



   EXAMPLE IV
 EMI9.2
 1,2-bis (2-propylsulfonyl) -ethylene. 35 parts of 1,2-bis (2-propylmercaptokethene, prepared in a manner similar to that in which the mercaptoethylenes of the preceding examples are prepared, were added dropwise to a stirred solution of 102 parts of hydrogen peroxide at 30% in 95 parts of glacial acetic acid. External cooling was found necessary to keep the temperature from exceeding 80 to 90 C. When the heat of reaction developed, the solution was heated to boil for 30 minutes and then let stand until the next day.

   By adding water and cooling in ice, the product precipitated and was filtered and washed with ice water, whereby 38 parts (80%) of 1,2-bis (isopropylsulfonyl) were obtained. ) -ethylene in the form of white flakes melting after crystallization from a water-ethanol mixture at 132.5-133 C. Analysis: Calculated for C8H10O4S2: C = 40.0%; H = 5.67%; S - 26.6%.



  Found C- 39.9%; H = 6.75%; s, 26.9%.



     EXAMPLE V
 EMI9.3
 1,2-bis (p-tolylsulfonyl) '- ethylene. In a re-

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 actor equipped with a stirrer and a reflux condenser, 130 parts of glacial acetic acid were placed
 EMI10.1
 and 28.3 parts of 1,2-bis (E-tolylmercapto) -é% pylene. The mixture was heated at reflux until the solution was clear, after which 93.8 parts of 30% hydrogen peroxide was added. The mixture was heated at reflux for 2 hours and cooled.
 EMI10.2
 Duct, 1,2-bis (p-tolylsulfonyl) -ethylene, was collected by filtration. Yield: 33.4 parts (71%); P.F.



    139-144 C. (Truce and McManimic, J. Am. Chem. Soc. 75, 1672. (1953) indicate 147-153 C.)
EXAMPLE VI
 EMI10.3
 1,2-bis (methylsulfonyl) -ethylene. 38.5 parts of 1,2-bis (methylmercapt- ethene were / were added with stirring to a mixture of 170 parts of 30% aqueous hydrogen peroxide and 260 parts of acetic acid, maintaining the mixture. temperature to 20-30 ° C. by external cooling, as necessary The addition took half an hour, after which the mixture was allowed to stand overnight The solvent was then distilled off under pressure. reduced by heating the mixture to a temperature not exceeding 60 ° C.

   The residual oil was allowed to crystallize by treatment with diethyl ether. The gross product then consisted of
 EMI10.4
 55 parts (93%) of 12-bis (methylsulfonyl) ethyZenes which appeared as a tan-colored solid melting at 60-75 C. This product was recrystallized from 240 parts of ethanol. At this point, it was necessary to filter while hot, to separate small amounts of insoluble material. 34 parts (37%) of the product were obtained as colorless crystals melting at 74-80 ° C. The wide range of melting temperatures and the presence of a clearly soluble fraction made it impossible.

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 indicate the absence of cis and trans isomers in the product.

   Two parts of the product were recrystallized again from ethanol so that part of a more soluble fraction which is believed to be the cis isomer was obtained. Analysis: Calculated for C4H8O4S2; C, 26.1%; H - 4.35%; S - 34.8%. Found C - 25.9%; H - 4.63%; S, 34.9%.



   EXAMPLE VII
 EMI11.1
 1,2bis (laurylsulfonyl L, ethglen. This compound was prepared from 1,2-bis (laurylmercapto) -ethene and hydrogen peroxide as in the previous examples. Yield: 71.3f; mp: 80-83C Analysis: Calculated for C23H32O4S2; S - 13.0% Found: S - 12.3%.



   EXAMPLE VIII
 EMI11.2
 1.2. bis (n-octylsulfonyl) ethylene. This compound was prepared from 1,2-bis (n-ootylmercapto) -ethene and hydrogen peroxide, as in the previous examples. Yield: 89%; Mp: 83.8 C. Analysis: Calculated for C18H36O4S2; C - 56, $%; H - 9.43%.



  Found: C - 56.6%; H - 9.53%.



   EXAMPLE IX
In a reactor equipped with means for introducing a liquid, a mechanical stirring device and a reflux condenser, a solution was placed.
 EMI11.3
 of 20 parts of 1,2-bis- (p-tolylsulfonyl) -ethylene vis in 150 parts of chloroform. To this solution was slowly added about 3 parts of bromine. The bromine color was maintained by allowing the solution to stand. When the addition of bromine was complete, the mixture was irradiated with a sunlamp, so that the bromine color quickly dissipated with formation of a precipitate. The precipitate was cooled and washed with chloroform so that

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 EMI12.1
 obtained 12.5 parts of 1.2b.sR-, oiyisuîfc; 1.4ethyler, e in the form of colorless crystals, M.P .: 225-227 G.



  (value given in the literature: 228 C.). Analysis:
 EMI12.2
 Calculated for C10H36S20J 'S = 19.1%. Found: S = 19.1.



  Evaporation of the filtrate gave an additional 6.2 parts of the trans product melting at 210-212 ° C.



    EXAMPLE X
 EMI12.3
 1,2-bis (n-butylsulfonyl) -ethylene. In a reactor were placed 17.0 parts of 12bis (nbutylmercapto) -ethene dissolved in 75 parts of a 1: 1 mixture of glacial acetic acid and acetic anhydride. The solution was cooled externally and 54.9 parts of 30% hydrogen peroxide was added over 2 hours, maintaining the temperature between 20 and 40 C.



  After this addition, the solution was allowed to stand at room temperature for 4 days.



   At the end of this period, the solution had separated into two layers. These were poured into ice water with stirring. The product was collected by filtration, washed with water and dried in vacuo at room temperature over KOH. By recrystallization from a mixture of water and methyl alcohol, we obtained
 EMI12.4
 15.0 parts (79.7%) 1,2-bis (n..butylsulfonyl) ethylene, m.p .: 6l-63G. Analysis: Calculated for C10H0 :,20: C = 44.8%; H, 7.45%. Found: C = 44.7%; H, 7.34%.



   EXAMPLE XI
 EMI12.5
 1,2-bis (n-amylsulfonyl) -eth.ylene. 3 parts of 1,2-bis (n-amylmercapto% ethylene dissolved in 7 parts of a 1: 1 mixture of acetic acid and acetic anhydride were placed in a reactor. The solution was cooled. externally and 52.0 parts of 30% hydrogen peroxide were added over 2 hours, keeping the temperature between 20 and 40 C. After this ad-

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 Finally, the solution was allowed to stand at room temperature for 4 days. Yield (after recrystallization first from a mixture of acetic acid and water, then from a mixture of methyl alcohol and
 EMI13.1
 water), 16.9 parts (72.7%) of 1,2-bis (n. amylsulfonyl) - ethylene; M.P .: 51-53 C. Analysis: Calculated for
 EMI13.2
 CIH0S2; S 21.6%.

   Found: S = 218%.
EXAMPLE XII 1,2-bis (2-nitrophenylsulfonyl) -ethylene-dibenzene.
 EMI13.3
 p. (QN) C6HSCHCHSC6H (N0) P + 4HZOZ C6H6 p- {OZN) C6H4S02CH = CHSC2G4H4 (NOz) P tc6Hb) z To a stirred solution of 53 parts of 30% hydrogen peroxide in 210 parts of acetic acid ice cold heated to 90 ° C., 35 parts of
 EMI13.4
 1,2-Bis-n-n3.trophenylmercapto) ethylene powder at a rate such that the temperature does not exceed 96 C. This addition took 10 minutes and no external heating or cooling was necessary. . The mixture was then heated under reflux for 10 minutes. then cooled and filtered.

   The filtrate was poured into 500 parts of ice and 1000 parts of water containing about 2 parts of sodium chloride. The yellow precipitate was filtered, washed with ice water and dried in vacuo at room temperature. The crude product was extracted for several hours with 800 parts of benzene in a continuous liquid-solid extractor. The benzene extract was boiled with charcoal and filtered, after which 480 parts of benzene was distilled off. The product,
 EMI13.5
 Consisting of 1,2-bis- (2-nitrophenylsulfonyl) -ethylene containing 2 molecules of crystallizing benzene, was crystallized from cooled benzene solution.

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  Yield: 22 parts (38%); yellow platelets; M.P .: 148-153 C (rapid decomposition above about 1000 C). By crystallization from benzene, the melting point rose to 150153 C. Analysis:
 EMI14.1
 Calculated for 0z6HZZN20 $ S: N = 5s05;. 5 = 11.6%. Find! N, 5.11%; S, 11.7%.



   In order to exhibit maximum efficacy, the compounds of the present invention are ordinarily mixed in an amount effective from the viewpoint of their fungicidal action with a conditioning agent of the type commonly referred to as a modifier or adjuvant for control or control. pests. These conditioning agents are also known as surface active agents, dispersants and sometimes as surface active dispersants. In order to obtain compositions particularly suitable for effective application to pests with conventional devices or apparatus, these compositions include those of the liquid type as well as those of the solid type.

   These adjuvants have the effect of requiring only minimal quantities of the compounds defined above in certain compositions, in order to obtain effective protection. Another advantage of the dilution of the compounds in question resides in the fact that can apply the compositions on fields by easily usable methods, while allowing to completely cover the material to be protected.



   The compositions according to the present invention therefore contain a pesticidal ingredient of the type defined above as well as a material suitable as a dispersing or conditioning agent for this ingredient. The present invention should not be construed as being limited to specific proportions.

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 any active ingredient and adjuvant. The important characteristic of the invention is to provide a conditioning agent such that, during the preparation of a composition having the desired concentration of the application, the conditioning agent is present therein so as to ensure the appropriate type of contact with the material to be protected.

   Thus, in one embodiment, the conditioning agent may include a dispersing agent or a surface active agent, such as a detergent, soap or other substance which tends to lower the surface tension of the material. water. Such a composition can then comprise the active ingredient in combination with a minor proportion of the agent with perficial activity. Such a concentrated composition is useful in practice because of its concentrated form and its ease of transportation, storage and the like. On the other hand, such a concentrated composition is suitable directly for further dilution with any vehicle, without the need for complicated mixing and kneading treatments.

   Thus, such a composition can be suspended directly in water or be diluted with the aid of an oil forming, on mixing with water, an oil-in-water emulsion containing. the active ingredient. Another example of the utility) of such a composition is constituted by the preparation by dilution using a solid vehicle of a wettable powder, which by mixing with water before application forms a dispersion of the powder. active ingredient and solid vehicle in water. In the concentrated compositions in question, the amount of active ingredient varies between 5 and 99.9% of the whole.

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   The expression. "conditioning agent" also includes solid carriers of the type talc, pyrophyllite, "Attaclay", kieselguhr, chalk, diatomaceous earth and the like, as well as various mineral powders, such as as calcium carbonate and the like, which act as a dispersing agent, as a vehicle, while in some cases fulfilling the function of a surface active agent.



   One mode of application of these fungicides is by using them in the form of an aqueous suspension. To obtain a fungicidal aqueous suspension, it is preferred to use a surface active agent to disperse and suspend the pesticidal agent.

   As examples of surface active agents which can be used to form dispersions, there may be mentioned the metal salts of alkyl- and alkylarylsulfonates, such as sodium salt; alkyl sulfates; alkylmide sulfonates, in particular fatty methyltaurides; alkyl arylpolyetheric alcohols; fatty acid esters of polyhydric alcohols; the ethylene oxide adducts of these esters, such as, for example, hexitol product; and the adducts of long chain mercaptans and ethylene oxide. Other surface active agents may still be employed, the only agents mentioned above forming only a representative list of the most common materials.



   In the following examples, all parts are parts by weight.



   EXAMPLE XIII
A composition based on trans bis (n-propylsulfonyl) -ethylene is prepared by adding, while thoroughly stirring, 10 parts of this material to

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 1000 parts of water containing one part of an adduct of hexitol and ethylene oxide. This concentrated dispersion is then diluted a thousand times by adding water, so as to obtain a composition of concentration suitable for its application. Thus, the resulting dispersion contains 10 p.p.m. of fungicide in the aqueous dispersion.



     . The solubility of the active ingredients according to the present invention in organic solvents is, moreover, such that these ingredients can advantageously be applied in the form of a solution in this type of solvent and, for certain uses, this mode of application. application is preferred. Thus for the treatment of fabrics, leather or other fibrous articles, it is sometimes preferable to apply the fungicides in solution in a volatile solvent. After application, the volatile solvent evaporates, so that the fungicidal agent remains impregnated over the entire surface of the article and in the dispersed form, which has proved to be the most advantageous.



  Similarly, when applying the fungicide to smooth surfaces, especially when treating wood or other surfaces, a solution may be the most convenient way to apply a protective film by brushing, spraying or dipping. The choice of an appropriate solvent is determined to a large extent by the concentration of active ingredient desired to be employed, the required volatility of the solvent, its spread or flow characteristics, and the nature of the solvent. the material to be processed.

   Among the many organic solvents which can be used as a vehicle for the fungicide include its hydrocarbons, such as benzene, xylene or toluene; ketones, such as acetone, methyl ethyl ketone and cyclohexanone;

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 chlorinated solvents, such as carbon tetrachloride, trichlorethylene and perchlorethylene; esters, such as ethyl, butyl and amyl acetates; and alcohols, such as ethanol, isopropanol and amyl alcohols. Other solvents which can be used are carbitols and cellosolves, the former generally being constituted by the monoalkyl ethers of diethylene glycol and the latter by the monoalkyl ethers of ethylene glycol.

   In addition, combinations of these various typical solvents can be used, so that special volatility and viscosity characteristics can be imparted to the compositions.



   EXAMPLE XIV
A solution comprising 5 parts of bis- (p-nitrophenylsulfonyl) -ethylene in 250 parts of cyclohexanone is prepared by stirring the two components for 2 minutes at a temperature of about 25 ° C.



  This concentrated solution, suitable for storage and transport, is then diluted with kerosene to form a final product containing 50 p.p.m. of fungicidal ingredient, which is a suitable concentration for application.



   A preferred composition of the active fungicidal ingredient according to the invention is a wettable powder. Various methods can be used to prepare wettable powders. Thus, in accordance with the invention, compositions can be prepared comprising the active ingredient defined herein in combination with a small amount of a surface active agent. This surface active agent can be chosen, for example, from those mentioned above with regard to aqueous dispersions.

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  Other agents with surface activity can also be used, those mentioned above constituting only a representative list of the most common materials. These compositions can be readily mixed with a powdered vehicle. The compositions thus formed then comprise the active ingredient according to the present invention, a surface active agent and an inert vehicle. Among the inert vehicles which can be used for the preparation of wettable powders, there may be mentioned, for example, soybean flour, tobacco flour, nutshell flour, wood flour, sulfur, etc. tripolith, diatomaceous earth, calcium lime, magnetic lime, calcite, dalomite, gypsum, mica, talc, pyrophyllite, montmorillonite, kaolinite, attapulgite, apalite and stone pumice.

   For the preparation of concentrated wettable powders, it is preferred to use between 0.1 and 93% surface active agent, based on the total amount of surface active agent and active ingredient, and up to 85%. of inert vehicle, based on the total quality of the composition. These compositions have the advantage of allowing the storage and transport of the fungicide and of allowing subsequent dilution by simple mixing with water at the time of application. The invention also encompasses finished compositions suitable for direct application and comprising the fungicides defined herein, surface active agents as illustrated above and inert solid carriers also as illustrated above, all of these. ingredients being suspended in water.

   Depending on the intended application, these finished compositions may contain between 0.1 and 10,000 p.p.m. approximately of fungicide,

 <Desc / Clms Page number 20>

 A preferred concentration for agricultural applications is between 0.1 and 2,000 ppm. Typical compositions of such wettable powders according to the invention are illustrated in the following examples, in which an active ingredient according to the invention is used. - read as a fungicide.



   EXAMPLE XV
A mixture of 100 parts of bis (laurylsulfonyl) -ethylene, 1000 parts of pyrophyllite and 0.1 part of sodium kerylsulphonate is thoroughly kneaded in an L-shaped mixer. The 10% wettable powder thus prepared gives a satisfactory aqueous suspension when 11 parts are stirred in a sufficient quantity of water to produce a suspension containing 100 ppm of active ingredient.



   In addition to the above described methods of wet application of the active ingredient according to the invention, compositions can also be prepared in which the material is coated in talc, clay or other substances. - very inert diluents. These vehicles perform the function of conditioning agents as contact agents. Other specific examples of such typical inert solid carriers which can be employed as diluents in powder include fuller's earth, pyrophyllite, attaclay and the like.



   EXAMPLE XVI
A powder composition of the fungicide is prepared as follows: 1 part of bis (methylsulfonyl) -ethylene is placed in a ball mill with 100 parts of fuller's earth. This mixture is ground for one hour and sieved so as to collect a fraction passing through a 100 mesh sieve. This composition containing 1% by weight of fungicide can be applied directly or further diluted. A new diluted

 <Desc / Clms Page number 21>

 tion is obtained by repeating the process described above with an additional 100 parts of fuller's earth per part of the mixture obtained in the first place.



   For some applications it is preferable to use the fungicide in the form of oil-in-water emulsions. Thus, a concentrate of the fungicidal agent in a water insoluble solvent is prepared and the solution is then dispersed or emulsified in water containing a surface active agent. As typical examples of such solvents, there may be mentioned hydrocarbons, such as kerosene, benzene and naphtha; higher alcohols, such as butanol, oleyl alcohol, or their ethers and esters; chlorinated solvents, such as perchlorethylene and trichlorethylene.



   EXAMPLE XVII
An oil-in-water emulsion is prepared by dissolving 10 parts of bis (phenylsulfonyl) -ethylene in 1000 parts of kerosene. This solution is dispersed with vigorous stirring in water containing 1 part of fatty methyltauride; so as to get. a dispersion containing 10 p.p.m. 'of active agent.



   In addition, it has been found that an adhesive or tackifier, such as vegetable oils, natural gums or other adhesives, can be incorporated into the fungicidal compositions according to the invention. Likewise, humectants can be used in the compositions. In addition, these compositions can be used in admixture with other pesticidal or other biocidal materials, such as insecticides, larvicides, bactericides, vermicides, miticides, other fungicides, or with other materials which it is desired to apply in the same time as the fungicides according to the invention, y

 <Desc / Clms Page number 22>

 including mixtures of the active ingredients according to the invention.



   The fungicidal efficacy of the new compounds according to the invention is illustrated by the following results, which reveal that the active ingredients are effective as fungicides against the organisms Alternaria oleracea and Sclerotinia fructicola. For this purpose, a suspension of 100 parts of bis (organosulfonyl) -ethylene in 1000 parts of distilled water containing a small amount of a commercial dispersing agent (hexitol-oxide adduct). ethylene) was prepared. This suspension was tested and diluted with distilled water until the concentration of the active ingredient capable of preventing half of the aforementioned fungi from sporulating was determined; this observation was made in a drop of water under the microscope.
 EMI22.1
 
<tb>



  Compound <SEP> Concentration, <SEP> p.p.m.
<tb>
<tb> for <SEP> LD50 <SEP> screw <SEP> of the <SEP> fungi.
<tb>
 
 EMI22.2
 ¯¯¯¯¯¯¯¯¯¯¯¯¯¯ --------- .. ¯ .----
 EMI22.3
 
<tb> Alter.oler. <SEP> Scler.fruct.
<tb>
<tb>
<tb>
<tb>
<tb> bis <SEP> (n-propylsulfonyl) -éthy- <SEP>
<tb>
<tb> lene <SEP> trans <SEP> 0.5 <SEP> 5
<tb>
<tb>
<tb> bis (n-propylsulfonyl) -ethy-
<tb>
<tb> lène <SEP> cis <SEP> 5 <SEP> 5
<tb>
 
 EMI22.4
 bis (n-butylsulfonyl) -é thylene 5 "bis (p-aylsulfonyl) -éthy3ène 0,5 0,5 bis (, p-tolylsulfonyl) -ethylè-
 EMI22.5
 
<tb> ne <SEP> cis <SEP> 5 <SEP> 0.5
<tb>
<tb> bis (-tolylsulfonyl) -ethylene <SEP> 0.5 <SEP> 0.5
<tb>
 
 EMI22.6
 bis (p-nitrophenylsulfonyl-6-
 EMI22.7
 
<tb> thylene <SEP> 5 <SEP> 0,

  5
<tb>
 
The fungicidal activity of the compounds is also demonstrated by their efficacy against the leaf disease of tomato plants. The relative test

 <Desc / Clms Page number 23>

 the disease in question measures the percentage of destruction of the fungus of the late niola called Phytophthora infestans. In the primary sieve, chemicals are tested at concentrations of 2000 and 400 p, .p.m. The tomato plants are sprayed with the composition to be tested, allowed to dry and sprayed, at the same time as untreated test plants, with a suspension of sporangia. of Phytophthora infestans.

   The plants are kept in an atmosphere for 24 hours at 70 F for early: niello / - and at 60 F for late niello to allow spore germination and infection before greenhouse. After 2 to 4 days, lesion counts are made on the three upper fully developed leaves. Compounds giving 85% or more plant immunity to one or both infectious organisms at 400 p.p.m are further tested at dosages of 400, 80, 16 and 3.2 p.p.m. For advanced evaluation, dosages are adjusted according to the efficacy of the compound tested. This test method is a variation of that described by McCallan and Wellman (Contrib.

   Boyce Thompson, 13 (3); 93-134- July-September 1943). The ED95 of typical compounds according to the present invention against late niola fungus is 50 for bis (n-tutylsulfo).
 EMI23.1
 nyl) -ethylene, 80 for bis (n-amylsulfanyl) -ethylene and less than 16 for bis (-, o.y7.sulfonyl) -éthy-. lene (mixture of cis and trans isomers).



   As mentioned above, particularly remarkable results in the protection of seeds are obtained when the bis (organosulfonyl) -ethylene used is a compound of formula RSO2CH = CHSO2R, in which R is an alkyl group containing 3 to the

 <Desc / Clms Page number 24>

 carbon atoms. In fact, this new class of compounds represents the most potent group of organic seed protection agents known to date. This is especially revealed by the following test, by which the effectiveness of these materials as pitch seed protection agents was determined.

   In this test, pitch seeds of the so-called "Perfection" variety were uniformly coated with bis (organosulfonyl) -ethylene, by rolling mixtures of seed and fungicide in screw-top bottles on rollers rotating at great speed. The dosages were varied using (1) the undiluted chemical compound and (2) uniform mixtures of the chemical compound and Homer clay. The treated pitch seeds, along with untreated control seeds and a reference standard, were planted in contaminated soil using fungi. Untreated seeds were also planted in sterile soil as a control. After 14 days, the percentage of emergence. has been registered. The results obtained were as follows.

   With bis (ethylsulfonyl) -ethyl-
 EMI24.1
 lene and bis (methylsulfony1} -ethylene, which do not contain 3-12 carbon alkyl groups, the percent protection obtained at a concentration of the active ingredient of 0.48% was only 52 and 2 respectively.

   On the other hand, with bis (alkylsulphonyl) -ethylenes, the alkyl groups of which contain 3 to 12 carbon atoms, the percent protection obtained at an active ingredient concentration of 0.8 was 96 for bis (n-propylsulfonyl) -ethylene trans, 92 for bis (n-butylsulfonyl) -ethylene and 90 for bis (n-propylsulfonyl) -ethylene cis.

 <Desc / Clms Page number 25>

      
 EMI25.1
 elsewhere, the activity of bis (alkylsulfonyl) - 'r', 6ylenea whose alkyl groups have 3 to 12 carbon atoms, as seed protection agents, remains high when the concentration of the active ingredient is greatly reduced. .

   Thus, at a concentration of only 0.03% of active ingredient, the percentage of protection
 EMI25.2
 tion given by bie (n-butyleulfonyl) -éthy3, was still 75 and concentrations of only 0.009% of bis (a-propylsulfonyl) -ethylene gave 90% protection, while the same concentration of bis (isopropylsulfonyl) -ethylene gave 58% protection. Even at the extremely low concentration of 0.001%, the
 EMI25.3
 bis (n-propylsulfony1) -ethylene trans gave bzz of protection in this test.



   Good seed protection results
 EMI25.4
 are obtained with b3s (n-octylsulfonyl) -ethyl $ ne and bis (laurylsulfo: nyl) -ethylene, as well as with other bis (alkylsulfonyl) -ethylenes, the alkyl group of which contains 5 to 12 carbon atoms.



   CLAIMS 1. Process for the preparation of bis (organosulfonyl) - ethylenes, in which a 1,2-bis (alkyl, mercapto) -ethylene is reacted, the alkyl radical of which contains 3 to 12 carbon atoms, with an oxidizing agent, such as hydrogen peroxide, to form 1,2-bis
 EMI25.5
 (alkylsulfonyl) -ethylene corresponding.


    

Claims (1)

2. A method according to claim 1, in which - which is reacted 1,2-bis (n-propylmercapto) -ethylene with hydrogen peroxide, so as to form EMI25.6 a mixture of cis and trans 1,2-bis (n-propylsulfonyl) -ethylene. 3. The method of claim 2, in the- <Desc / Clms Page number 26> which the trans isomer is crystallized from a mixture of water and alcohol. 4. Process for the preparation of bis (organosulfonyl) ethylenes, in substance, as described above. 5. As a new compound, a bis (alkylsulfonyl) -ethylene of the formula RSO2CH = CHSO2R, in which R is an alkyl group having 3 to 12 carbon atoms. 6. A compound according to claim 2, wherein the compound is in the trans configuration. 7. Bis (n-propylsulfonyl) -ethylene trans. 8. A fungicidal composition comprising a bis (organosulfonyl) -ethylene as well as a conditioning agent. 9. Method of controlling fungi, in which the habitat of fungi is treated with a bis (organosulfonyl) -ethylene. 10. A method of protecting seeds against the ravages of fungi, in which the seeds are treated with a bis (organosulfonyl) -ethylene.