DE2705820A1 - SULPHONE DERIVATIVES AND MIXTURES CONTAINING THEM - Google Patents

Description

Our no. 20 878 Ka / La

Chevron Research Company San Francisco, CaI., V.St.A.

Sulfone derivatives and mixtures containing the same

The present invention relates to compounds of the general formulas

RSCH ₂ CHSO ₂ R ¹ and RSCH = CHSO ₂ R ² X

(I) (ID

wherein R is an alkyl radical having 1 to 6 carbon atoms, a Phenyl radical or a phenyl radical with 1 to 3 fluorine atoms, chlorine atoms, bromine atoms, nitro radicals or alkyl radicals with 1 to 4 carbon atoms, where the substituents can be identical or different, R is a

Radical of the formula -CH (X) CH ₉ SR or the radical R, where R is the

has the meaning given above, and R is a radical

of the formulas -CH = CH ₂ , -CH = CH-SR or the radical R, where R has the meaning given above and X is a chlorine atom or a bromine atom, with the proviso that both radicals

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-X-

ρ
R and R are not an alkyl radical, ie at least one

ρ
R or R radical denotes a radical of the formulas -CH = CH ₂ , -CH = CH-SR, a phenyl radical or a substituted phenyl radical, and mixtures containing the same.

Chemical Abstracts 68, 59HOt (1968) and 67, 108l35v (1967) describe the preparation of β-substituted ethyl vinyl sulfones by adding alcohols and mercaptans to divinyl sulfone.

E.N. Prilezhaeva and Laba et al, Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 21 * 19-2156, October I969 and No. 7, pp. 16O2-16O8, July 1970 describe one Multi-step synthesis of ethyl 2-ethylthiovinyl sulfone.

In the formulas given above, mean representative

1 2 Alkyl radical »R, R and R methyl radicals, ethyl radicals, propyl radicals

1 2

and hexyl radicals. Representative aryl radicals R, R and R are der! »- chlorophenyl-, 2-fluorophenyl-, 3» 5-dibromophenyl-, 2-nitro-4-methylphenyl-, ¹ -tolyl-, 2-chloro- ⁱ l-methylphenyl- and the 2, ¹ », 6-trichlorophenyl radical.

R preferably denotes a phenyl radical or a phenyl radical which has 1 to 2 fluorine atoms, chlorine atoms, bromine atoms, Is substituted by nitro radicals or alkyl radicals with 1 to M carbon atoms, it being possible for the substituents to be identical or different. In particular, R denotes a phenyl radical which is substituted by 1 to 2 chlorine atoms or bromine atoms.

Representative compounds of the present invention

1 2 where R or R are alkyl or aryl (i.e. 1-halogen-2-substituted-thioethylsulphones or 2-substituted-thiovinylsulphones) include:

709833/09 **

Methyl-l-chloro-2-methylthioethyl sulfone, Phenyl-l-bromo-2-hexylthioäthylaulfon,

p-Tolyl-1-chloro-2-p- ^bromo-1 »-methylphenylthioethylsulfone,

Hexyl-l-chloro-2-o-nitrophenylthioethylsulfone, Ethyl-l-bromo-2-o-fluorophenylthioethylsulfone, Methyl-2-methylthiovinylsulfone,

2, ⁱ l-dichlorophenyl-2-o-chlorophenylthiovinyl sulfone,

Hexyl 2- (2-methyl-4-chlorophenylthio) vinyl sulfone and Ethyl 2- (2-bromo-4-chlorophenylthio) vinyl sulfone.

The compounds according to the invention in which R is a radical of the formula -CH (X) CH ₃ -SR are bis- (1-halogen-2-substituted-thioethyl) sulfones, represented by the formula

X X

and compounds according to the invention

ο
where R is a radical of the formula -CH = CH-SR

Bis- (2-substituted-thiovinyl) sulfones, represented by the formula RSCH = CHSO ₂ CH = CHSr (IV)

wherein R has the meaning given above, are represented.

Representative compounds of Formulas III and IV include

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Bis (l-chloro-2-methylthio) sulfone, Bis- (l-bromo-2-ethylthioethyl) sulfone, bis- (l-bromo-2-o-fluorophenylthioethyl) sulfone,

Bis- (l-chloro-2-o-chloro-p-bromophenylthioethyl) sulfone,

Bis- (2-raethylthioviny1) sulfone, Bis (2-hexylthioviny1) sulfone, Bis (2-p-tolylthioviny1) sulfone, Bis- (2-o-fluorophenylthiovinyDsulfone and Bis- (2-o-nitro-p-chlorophenylthiovinyl) sulfone.

The compounds according to the invention in which R is a vinyl radical means are vinyl-2-substituted-thiovinylsulfones, the by the formula

RSCH = CHSo ₂ CH = CH ₂ (V)

being represented.

Representative compounds of Formula V include:

Vinyl 2- (2-chlorophenylthio) vinyl sulfone, Viny1-2- (2-chloro - ^ - bromophenylthio) vinyl sulfone,

Viny1-2- (2-methyl-4-ethylphenylthio) vinylsulfone, Viny 1-2- (2-methyl- ¹ »-äthylphenylthio) vinyl isulfone, Viny1-2- (2-methyl-4-nitrophenylthio) vinylsulfone,

Viny1-2-methylthiovinylsulfone, Viny1-2-isopropylthiovinylsulfone and Viny1-2-hexylthiovinyl sulfone.

The compounds of general formula I in which R is a Means an alkyl radical or an aryl radical, i.e. 1-halogen-2-substituted-thioethylsulfones, are converted into an alkyl vinyl sulfone by adding a sulfenyl halide of the formula VI Formula VII prepared, and the 2-substituted-thiovinylsulfones of the formula II are prepared by dehydrohalogenation of the 1-halogen-2-substituted-thioethylsulfones of the formula I with a base, as can be seen from the following reaction equations:

R-SX + CH ₂ = CHSO ₂ R ¹ > RSCHgCHSOgR ¹

(VI) (VII) X (I) (1)

RSCH ₂ CHSO ₂ R ² + B> RSCH = CHSO ₂ R ² ♦ B · HX

X (I, R ¹ = R ² ) (II) (2)

wherein R and X have the meaning given above,

1 2

R and R individually denote alkyl or aryl, as indicated above, and B denotes a base.

The reaction 1 is carried out by reacting in the liquid phase at a temperature of about 0 to 100 ⁰ C substantially equimolar amounts of the Sulfenylhalogenides of formula VI and the Alkylvinylsulfons of formula VII. In general, an inert organic solvent is used in the reaction; such as an alkane, a haloalkane or an aromatic compound. The reaction pressure is suitably atmospheric pressure, reduced pressure or elevated pressure. For convenience, the reaction pressure is generally atmospheric pressure. The reaction is generally exothermic and is complete in about 1 to 24 hours. The 1-halogen-2-substituted-thioethylsulfone of the formula I is _{isolated and purified by suitable processes a} such as extraction, filtration, chromatography, distillation or, alternatively, used directly in reaction 2 without purification and / or isolation.

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In reaction 2, the 1-halogen-2-substituted-thioethylsulfone of the formula I is treated with essentially equimolar amounts of a base. The preferred base is an organic base such as a pyridine compound, for example pyridine or an alkyl pyridine, or a trialkylamine, for example triethylamine. Reaction 2 is carried out in the liquid phase at a temperature from about 0 to about 100 ° C. In general, an organic diluent such as a haloalkane, for example dichloromethane, or an aromatic hydrocarbon, for example benzene, is used in the reaction. The reaction pressure is not critical and, for convenience, atmospheric pressure is generally used. The reaction is generally complete in about 1 to about 2k hours. The product of formula II is isolated and purified by suitable methods such as filtration, extraction, distillation, chromatography and the like.

The bis (l-halogen-2-substituted-thioethyl) sulfones of the general formula III are prepared .. by adding a Sulfenyl halides of the formula VI to a divinyl sulfone of the formula VIII and the bis (2-substituted-thiovinyl) sulfones of the formula IV are obtained by dehydrohalogenation of the bis (1-halogen-2-substituted-thioethyl) sulfones of formula III prepared with a base, as shown in the following reaction equations can be seen:

2RSX + CH ₂ = CHSO ₂ CH = CH ₂ > ₂₂₂

(VI) (VIII) X X (III) (3)

RSCH ₂ CHSO ₂ CHCh ₂ SR + 2B ► RSCHsCHSO ₂ CH = CHSR + 2Β · ΗΧ

X X (III) (IV)

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where R and X are as defined above and B is a base.

Reaction 3 is carried out by putting in liquid Phase at a temperature of about 0 to 100 ° C. essentially 2 moles of the sulfenyl halide of the formula VI per mole of the divinyl sulfone of the formula VIII. In general, an inert organic solvent is used in the reaction, such as an alkane, a haloalkane or an aromatic compound. The reaction pressure is suitable Atmospheric pressure, negative or positive pressure. For convenience, atmospheric pressure is generally used. the The reaction is generally exothermic and is complete in about 1 to 24 hours. The bis (l-halogen-2-substituted-thioethyl) sulfone of the formula III is by conventional methods such as Extraction, filtration, chromatography, distillation / isö- * lated and cleaned or alternatively without cleaning and / or Isolation used directly in reaction 4.

In reaction 4, the bis (1-halogen-2-substituted-thioethyl) sulfone of the formula III is treated with about 2 equivalents of a base. The preferred base is an organic base such as a pyridine compound, for example pyridine or an alkyl pyridine, or a trialkylamine, for example triethylamine. The reaction is carried out in liquid phase at a temperature of O to 100 ⁰ C. In general, an inert organic diluent, such as a haloalkane, for example dichloromethane, or an aromatic hydrocarbon, for example benzene, is used in the reaction. The reaction pressure is not critical and, for convenience, atmospheric pressure is generally used. The reaction is generally complete in 1 to 21 hours. The product of the formula IV is isolated and purified by conventional methods such as filtration, extraction, distillation, chromatography and the like.

709833/0907

The vinyl-2-substituted-thiovinylsulfones of the formula V are by adding a sulfenyl halide of the formula VI to a divinyl sulfone of the formula IX and dehydrohalogenation of the resulting 1,2-addition product of the formula X prepared with a base, as can be seen from the following reaction equations:

RSX + CH ₂ = CHSO ₂ CH = CH ₂ ν ₂₂₂

(VI) (IX) X (X) (5)

RSCH ₂ CHSO ₂ CH = Ch ₂ + B »- RSCH = CHSO ₂ Ch = CH ₂ + Β · ΗΧ

X (X) · (V) (6)

where R has the meaning given above, X is a chlorine or a bromine atom and B is a base.

The reaction 5 is performed by as described in liquid phase at a temperature of about O to 100 ⁰ C for the reaction 1, substantially equimolar amounts of the Sulfenylhalogenides of formula VI and of the formula IX is reacted Divinylsulfons. In reaction 6, the 1,2-addition product of formula X as described in reaction 2, with substantially equimolar quantities of a base treated.

The compounds according to the invention are for controlling fungi, in particular fungal infections of plants, which caused by Botrytis cinerea, powdery mildew caused by organisms such as Pythrium ultimum, Helminthosporum sfcivum, Fusarium moniliforme, Rhizoctonia solani, Monolinia fructicola and Uromyces phaseoli typica. However, some fungicidal compounds according to the invention may be more fungicidal than others against particular fungi,

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When the compounds according to the invention are used as fungicides, they are present in fungicidally effective amounts Fungi and or their habitats or sites, such as vegetative hosts and non-vegetative hosts, e.g. animal products applied. The amount used depends of course on various factors; such as the host, the type of fungus and the particular compound of the invention. As the most pesticidal compounds will be those of the invention Fungicides usually not used at full strength, but are generally used with conventional biologically inert diluents or carriers that are normally used for relief the dispersion of the active fungicidal compounds, taking into account the fact that the The formulation and method of application can affect the activity of the fungicides being applied, processed. Thus, the fungicides according to the invention can be used as granules, powdery dusts, wettable powders, as emulsifiable Concentrates, as solutions or in the form of any of the other various types of formulation known, depending of the desired type of application, formulated and applied.

Wettable powders or wettable powders are in the form of finely divided particles which are easily dispersed in water or other dispersants. These mixtures normally contain from about 5 to 80 percent fungicide and the balance inert material comprising dispersants, emulsifiers and wetting agents. The powders can be applied to the ground as dry dust or, preferably, as a suspension in water. Typical carriers include fuller's earth, kaolin clays, silicas and other highly absorbent, easily wettable inorganic diluents. Typical wetting, dispersing or emulsifying agents include, for example, the aryl and alkyl aryl sulfonates and their sodium salts, alkyl

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-ψ-

amide sulfonates, including fatty methyl taurides, alkylaryl polyether alcohols, sulfated higher alcohols and polyvinyl alcohols, polyethylene oxides, sulfonated animal and vegetable oils, sulfonated petroleum oils, fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters and the addition products of long chain mercaptans and ethylene oxide. Many other types of useful surfactants are commercially available. The surface-active Agent, when used, typically constitutes from 1 to 15% by weight of the fungicidal mixture.

Dusts are free-flowing mixtures of the effective fungicide with finely divided solids, such as TaIk ₁ natural clays, kieselguhr, pyrophyllite, chalk, diatomaceous earth, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours and other organic and inorganic solids, which are used as Dispersants and carriers for the toxic agent act. These finely divided solids have an average particle size of less than about 50 microns. A typical dust formulation useful in the present invention contains 75 % silica and 25 % of the toxic agent. Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquids or pasty mixtures that are readily dispersed in water or other dispersants

can consist entirely of the fungicide with a liquid or solid emulsifier or also a liquid Carriers ^ such as xylene, heavy aromatic naphthas (heavy aromatic naphthas), isophorone and other non-volatile

May contain organic solvents These concentrates are dispersed in water or other liquid carriers and are usually used as a spray on the too area to be treated or the area to be treated applied.

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near hand I.

Other useful formulations for fungicidal applications include simple solutions of the active fungicide all in one Dispersants in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Granular Formulations in which the fungicide is on relatively coarse particles are of particular usefulness for the distribution from the air by means of an airplane, e.g. by spraying, or for penetration by the plants created protective cover for fungi or for the habitat of the fungi. Pressurized sprays, typically aerosols, in which the active ingredient is the result of evaporation of a low-boiling, dispersant solvent carrier, such as the freons, dispersed in finely divided form can also be used. All of these techniques for formulating and applying fungicides are well known in the art.

The weight percentages of the fungicide may vary according to the manner in which the mixture is applied and the particular type of formulation, but generally comprise from 0.5 to 95 % of the toxic agent based on the weight of the fungicidal mixture.

The fungicidal mixtures can be used with other active ingredients, including other fungicides, insecticides, nematocides, Bactericidal, plant growth regulating agents, fertilizers and the like can be formulated and applied.

The compounds according to the invention are also used to combat microbiological organisms such as algae, bacteria, Molds and weeds that occasionally occur in fresh water or plants growing in undesired places, which, aqueous industrial outflows and cooling streams such as those used in the paper and food processing industries

709833 / 09S7

occur, contaminate or clog. They can also be used to combat such organisms in other aqueous ones Bodies such as those used in lakes, rivers, canals, ponds and the like. When used in this way thus, a biocidally effective amount of one or more compounds of the invention will become the aqueous growth environment added to the organisms. Usually this dose will range between about 0.1 to 50 ppm. In any given The optimal dose depends on the particular organism and the affected watery body or area away. For example, when these compounds are used to control algae, they are used in concentrations used from about 0.1 to 10 ppm. Expressed in g the

2
Compounds per m of water at a depth of 0.3 m mean 0.1 to 10

2
ppm 0.03363 g to 3.363 g per meter of water at a depth of 0.3048 meters These compounds can be applied to the aqueous wax environment of such microorganisms as dispersible powders or in solution with water-miscible solvents.

The following examples serve to illustrate the present Invention.

example 1

Manufacture of ethyl 2- ( ¹ 4-chlorophenylthio) vinyl sulfone.

7.5 g of chlorophenylsulfenyl chloride became 5.0 g of ethylvinylsulfone added in 20 ml of dichloromethane. The reaction was not exothermic. The system was refluxed for 3 hours heated. The dichloromethane was removed by stripping and the residue was dissolved in 50 ml of benzene. 1.2 g

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Triethylamine was added dropwise with cooling and after standing for 1 hour, the triethylamine hydrochloride was removed by filtration and the benzene was obtained to obtain stripped of a crude product. Purification was carried out by chromatography on a silica gel column. The product, Ί, 2 g of ethyl 2- (1-chlorophenylthio) vinyl sulfone was obtained as a clear oil, which in the thin layer chromatography showed a stain.

Analysis; (for

Cl % S % ber .: 13.1 21, 1 found: 12.7 21.5.

The check by IR and NMR spectroscopy showed a complete agreement with the proposed structure.

The product is referred to in Table I as Compound No. 1,

Example 2

Manufacture of ethyl 2- (1-nitrophenylthio) vinyl sulfone.

10 g of 1-nitrophenylsulfenyl chloride were mixed with 6.1 g of ethylvinylsulfone combined in 30 ml of dichloromethane and refluxed for 6 hours. The stripping and implementation with

crude triethylamine in benzene gave initially a rohes'Öl which crystallized on standing and had a melting point of 55-58 ⁰ C.

The NMR spectrum fully supported the structure for ethyl 2- (1-nitrophenylthio) vinyl sulfone. The product and its elemental analysis are given in Table I under compound no.

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The compounds identified in Table I with the numbers 3 to 8 were prepared by a procedure similar to that described in Examples 1 and 2.

Example 3

Manufacture of ethyl-1-chloro-2-p-chlorophenylthioethyl sulfone.

5 g '♦ -chlorophenylsulfenyl chloride were 3 hours in 20 ml Dichloromethane heated under reflux with 3.3 g of ethyl vinyl sulfone. The stripped product showed 3 spots on thin layer chromatography and was confirmed by chromatography cleaned over silica gel. The purified product was eluted with dichloromethane and solidified after stripping a white solid. 6.4 g of the product with a melting point of 60 to 62 ° C. were obtained.

Analysis ;

Cl % S. % ber .: 23.4 21 found: 23.3 , 9.

The product is identified as Compound No. 9 in Table I.

Example 4

Production of bis-2- ( ¹ »-bromophenylthio) vinyl sulfone.

15 g of 4-bromophenylsulfenyl chloride slowly became a solution of 3.0 g of divinyl sulfone in 30 ml of chloroform added so that no heat dissipation occurred. The reaction mixture was refluxed for 2.5 hours and then stripped.

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The crude product was treated overnight with 5.2 g of triethylamine in 1 »0 ml of benzene, then filtered and stripped. The crude product was a red semi-solid which showed 3 spots on thin layer chromatography. The crude product, 7.0 g, was _{chromatographed on silica gel eluting with CHpCl 2 to give} 3.2 g of bis-2- ( ¹ »-bromophenylthio) vinyl sulfone as a red liquid. Thin layer chromatography of this product showed a single spot. The product is identified as Compound No. 3 in Table II.

The other compounds shown in Table II (except No. 9 or 10) were prepared by a procedure similar to the procedure of Example 4.

Example 5

Production of bis-Zi-chloro-2- (4-chlorophenylthio) -ethyl7-sulfone.

7.6 g of iI-chlorophenylsulfenyl chloride and 2.5 g of divinyl sulfone were refluxed for 3 hours in 30 ml of methylene chloride. Stripping gave a crude which showed 4 spots on thin layer chromatography. The cleaning was done carried out by chromatography on silica gel. That Product was first treated with methylene chloride and then with a mixture of methylene chloride and acetone (3: 1) eluted, with 3, Ί g of a purified fraction obtained became.

Analysis ; (for C ₁₆ H ₁₄ Cl ₁₁ O ₂ S ₃ ) S %

calc .: 20.2 found: 21.5

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-y-

The product is identified as Compound No. 9 in Table II.

Example 6

Manufacture of vinyl 2- ( ¹ <-chlorophenylthio) vinyl sulfone.

50 g of 4-chlorophenylsulfenyl chloride slowly became 33.0 ε Divinyl sulfone in 150 ml dichloromethane with cooling for removal added to the heat of reaction. After the mixture had stood for a few hours at ambient temperature, the solvent was stripped off and the crude adduct was dissolved in 200 ml of benzene. 31 g of triethylamine were added slowly with cooling to maintain ambient temperature. After standing for one hour, the triethylamine hydrochloride was filtered off. After washing with water and drying over magnesium sulfate, the solvent was stripped to give 64 g of crude product. That The crude product was purified by chromatography over silica gel, yielding 48 g of vinyl 2- (4-chlorophenylthio) vinyl sulfone were obtained.

Analysis : (for C ₁₀ H ₉ ClO ₂ S ₂ ) S Jt

calc .: 24.6 found: 21.4

The IR and NMR spectra supported the structure. Thin layer chromatography on silica gel showed the presence of the cis and trans isomers as 2 adjacent spots- '. That Product is identified as Compound No. 1 in Table III.

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Example 7 Production of vinyl 2- (4-tert-butylphenylthio) vinyl sulfone.

In a manner analogous to that in Example 6, tert-butylphenylsulfenyl chloride was added in a ratio of 1: 1 to divinyl sulfone, and the mixture was treated with triethylamine in Ββηζοί and purified by column chromatography. The product, vinyl 2- ( ¹ »-tert-butylphenylthio) vinyl sulfone, was obtained as a brown oil which crystallized on standing and had a melting point of 62 to 64 ° C.

Analysis ; CfUrC ₁₁₁ H ₁₈ O ₂ S ₂ ) S % Cl %

calc .: 22.7

found: 22.0 0

The spectroscopic verification by means of IR and NMR spectra showed complete agreement with the proposed structure. The product is listed in Table III as Compound No. 10 designated.

The other compounds listed in Table III were prepared using procedures similar to that described in Example 6.

Example 8 Inhibition of the mycelium.

A number of the compounds according to the invention were subjected to a mycelial inhibition test to determine their fungicidal activity. According to this test, the

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fungitoxic efficacy of fungicidal agents, expressed as the degree of inhibition of mycelial growth, measured. Each compound to be examined was dissolved in acetone to a concentration of 500 ppm. Paper strips were inoculated with the particular mycelial growth by covering the paper with a potato dextrose broth culture of the mycelial suspension. The inoculated papers were then placed on potato dextrose agar plates and sprayed with the fungicidal solution using a microspray device. The treated paper strips were incubated at 25 ° C and the values were read after 2 ¹ »hours. The fungicidal activities were measured by a zone of inhibited mycelial growth from the center of the paper strip. The effectiveness of the compounds tested for fungicidal effectiveness

2 is in Tables IV through VI, expressed in ag / cm for

99 {ige control of the fungus, reproduced. Example 9 Control of Algae

Representative compounds of the invention were tested for algicidal activity by the following procedure. The species used in the test were Lemna, Elodea and Spirolina.

An acetone solution of the test compound and a small amount of an alkylaryl polyoxyethylene glycol-containing surfactant was prepared. This solution was mixed with a nutrient broth in an amount sufficient to give a concentration of 2 ppm. A 2 ¹ K) ml container was filled with this mixture. One

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Sample of the test algae was added to each container and the container was then placed in an illuminated environment which was kept at a temperature of about 20 ° C for incubation. The containers were periodically observed for algae growth (compared to an untreated sample). The algicidal activity of the test compound was determined based on a final observation of algae growth after 7 to 10 days. The results of the test on a basis of 0 to 100, where 0 means no activity and 100 means complete activity, are summarized in Tables VII to IX.

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Table I.

Compounds of the formula RSCH = CHSO ₂ R ¹

Elemental analysis

link R. R ¹ Physically. State sulfur 24.5 halogen 12.7 C. 1 p-Cl-0 C ₂ H ₅ fluid calculated found 22.6 —— 2 P ~ rIO ~ Φ C ₂ H ₅ Melting point 55 -
58 ° C 24.4 21.7 calculated found 25.0 70983 3 C ₂ H ₅ oil 23.4 26.0 13.5 - Approx 4th p-CH, -0 C ₂ H ₅ fluid 21.5 25.4 15.2 09! 5 p-Cl-0 CH ₃ fluid 26.5 22.4 23.8 25.6 VB 6th 2,5-Cl ₂ -0 CH ₃ Melting point 107 - 25.8 - Nj
-O
O
cn 109 ° C 22.6 21.3 14.3 25.9 co
IV) 7th p-Br-0 CH ₃ fluid 20.6 25.0 29.3 I ^ fc ^
CD 8th p-Br-0 C ₂ H ₅ fluid 21.9 21.9 23.2 9 * p-Cl-0 C ₂ H ₅ Melting point 60 -
62 ⁰ C 20.9 27.3 0 = phenyl 21.4 ; hylsulfon 26.0 * = The Ve binding is Ethyl-1-chloro-2-p-chloropheny 23.7 lthioate

Table II

Compounds of the formula SO ₂ (CH = CHSR) ₂

Elemental analysis

link R. Physically. State sulfur 22.9 halogen 16.2 1 p-Cl-0 fluid calculated found 23.5 calculated found 17.7 2 m-Cl-0 oil 23.9 18.6
19.0 17.6 33.6
30.3 σ 3
4th p-Br-0
2,5-Cl ₂ -0 oil
oil 23.8 24.3
21.4 17.6 9.7 9833 / 5
6th pF-0
p-NO ₂ -0 Melting point 85 -
89 ⁰ C
semi-solid 19.5
20.4 20.2 32.5
30.0 29.2 0987 7th 3,4-Cl ₂ -0 oil 22.5
22.7 25.3 10.3 - 8th 0 oil 20.4 21.5 30.0 9 (a) oil 28.7 23.7 - 10 (b) Melting point 143 -
145 ⁰ C 20.2 - 23.6

0 - phenyl

(a) = bis / T-chloro-2- (4-chlorophenylthio) ethyl sulfone

(b) 5 bis-2- (4-chlorophenylthio) ethyl sulfone

OO

Table III

Compounds of the formula RSCH = CHSO ₂ Ch = CH ₂

Elemental analysis

OO U) CO

sulfur

link R. Physically. State calculated found 1 p-Cl-0 fluid 24.6 23.5 2 m-Cl-0 oil 24.6 24.2 3 p-Br-0 fluid 21.0 20.7 4th p-CH, -0 oil 26.6 24.4 5 2,5-Cl ₂ -0 oil 21.7 20.2 6th p-F-0 oil 26.3 24.1 7th p-NO ₂ -0 semi-solid 23.6 21.9 8th 3,4-Cl ₂ -0 oil 21.7 20.9 9 0 oil 28.3 25.9 10
11 CH _ 0 melting point 62 -
64 ° C
oil 22.7
39.0 22.2
40.5

Halogen calculated found

13.6 13.4
13.6 14.7
26.2 28.8

24.0
7.8

24.0

25.5
8.4

26.2

means phenyl

ro -j O cn 00 ro

CD

σ co οο

Tabel IV (2) (3) ! active fight (5) Mycelium inhibition, micrograms / cm for 99 0.63 0.68 0.34 link 0.92 0.73 (4) 0.76 No (D 0.65 1.5 0.87 0.54 1 0.76 0.92 1.2 > 1.7 0.65 2 0.92 0.31 0.50 1.5 - 3 1.6 0.26 0.68 > 1.7 - 4th > 1.7 0.41 0.59 0.63 - 5 0.36 0.4 0.76 0.56 - 6th 0.85 0.17 0.6 0.76 - 7th 0.48 > 1.7 > 1 »7 0.7 > 1 »7 8th 0.78 > 1 »7 > 1.7 0.73 > 1.7 9 > 1.7 > 1.7 > 1.7 > according to 7 > 1.7 1O ⁺ > 1 »7 > 1 »7 : ^{11 ++} > 1.7 > 1.7 12 ⁺⁺⁺ > 1.7

+ No. 10 is ethyl-2- (p-chlorophenylthio) ethyl sulfone

++ No. 11 is ethyl vinyl sulfone ¹ ^

+++ No. 12 is ethyl methylthiovinyl sulfone CD

(1) = Pythium ultimum JJ

(2) = Rhizoctonia solani κ>

(3) ^s Asperqillus niger

(4) = Fusarium moniloforma, (5) = Botrytis cinerea

Table V

2 Mycelium inhibition, micrograms / cm for 99> days control

link

No. (1) (2) (3) ÜL ili

1 0.22 0.9 0.86> 1.7

^, 2> 1.7 1.5 1.1> 1.7 1.2

g 3> 1.7 1.4 0.73> 1.7 1.4

oo 4 5 * 1.7 1.2> 1.7> 1.7 0.70 co

5 6 0.73 0.50 0.34> 1.7 0.7

Jg 7 0.78 0.97 1.1 1.0 0.70

-J 8> 1.7 0.88 0.50> 1.7 1.3

9 0.65 1.5 1.3 1.3 1.1

(1), (2), (3), (4) and (5) have the same meaning as in Table IV.

cn co κ?

link Table VI (2) Micrograms / cm for 99 jige ill Combat No. Mycelium Inhibition ^ 0.8 1.5 1 0.7 (3) 1.1 (5) 2 (D 0.85 0.6 0.78 0.98 3 0.24 > 1.7 0.8 0.68 0.34 4th > 1.7 1.3 1.1 > 1.7 0.69 CD 5 > 1.7 0.76 0.68 1.5 0.83 CO 6th 0.67 0.37 > 1.7 1.6 0.67 ω 7th > 1.7 0.95 0.47 > 1.7 1.0 / - ^ 8th 1.1 0.6 1.5 > 1.7 0.80 Smmt
CO 9 0.82 0.65 0.57 1.1 0.87 al 10 0.86 > 1 »7 0.88 ■> 1.7 0.56 11 1.1 0.88 > 1.7 > 1.7 > 1 7 1.6 1.6

(1), (2), (3), ( ¹ O and (5) have the same meaning as in Table IV.

OO NJ O

Table VII Percentage control of undesired occurrences in freshwater

Plants connection

No. Lemna Elodea Spirolina

1 1Θ0 39 60

2 0 0 90 <i 3 60 39 90

S lJ 0> 0 80 ι

£ 5 99 60 90 ^

<*> 6 99 70 80

ö 7 99 78 75

% 8 99 50 80

** 9 90 78 90

1O ⁺ OO 0

11 ⁺⁺ 0 0 70

12 ⁺⁺⁺ 100 0 0

+, ++ and +++ have the same meaning as in Table IV.

Table VIII Percentage control of undesired occurrences in freshwater

Connection plants

No. Lemna Elodea Spirolina

1 68 97

2 100 94 0

3 9k 9k ko ο i »39 70 80 S 5 30 70 80 S 6 99 78 90 ^ 7 70 90 95 α» 8 0 39 30 3 9 22 22 90

10 0 0 0

O CD OO CJ CO

ο oo β »

Table IX Percentage control of undesired occurrences in freshwater

Plant Compound No. Lemna Elodea Spirolina

1 100 100 -_ 2 100 99 100 3 99 90 100 Ii 100 96 90 5 90 78 0 6th 100 100 80 7th 99 100 50 8th 90 90 0 9 9 * 70 i »o 10 22nd 0 Mon 11 100 70 70

cn oo ro

Claims (1)

Claims ; wherein R is an alkyl radical with 1 to 6 carbon atoms, a phenyl radical or a phenyl radical with 1 to fluorine atoms, chlorine atoms, bromine atoms, nitro radicals or Alkyl radicals having 1 to 4 carbon atoms is substituted, the substituents being identical or different 2
can, and R is a radical of the formulas -CH = CH ₀ , -CH = CH-SR 2 or R, where both radicals R and R are not one Mean alkyl radical. 2. A compound according to claim 1, characterized in that R of the formula is an alkyl radical with 1 to 6 carbon atoms, a phenyl radical or a phenyl radical which is substituted with 1 to 2 fluorine atoms, chlorine atoms, bromine atoms, nitro radicals or alkyl radicals with 1 to k carbon atoms, where the substituents can be the same or different, and R is an alkyl radical having 1 to 6 carbon atoms, a phenyl radical or a phenyl radical having 1 to 2 fluorine atoms, chlorine atoms, bromine en atoms, nitro radicals or alkyl radicals with 1 to M carbon atoms is substituted, where the substituents can be identical or different, mean, where 2 at least one of the radicals R or R is a phenylresi or represents a substituted phenyl radical. Compound according to claim 1, characterized in that R of the general formula is a phenyl radical or a Phenyl radical with 1 to 2 fluorine atoms, chlorine atoms, 709833/0987 - ORIGINAL INSPECTED Bromine atoms, nitro radicals or alkyl radicals with 1 to 4 Carbon atoms is substituted, the substituents 2 can be the same or different, and R is an alkyl mean rest with 1 to 6 carbon atoms. 4. A compound according to claim I _1, characterized in that in the general formula R is the p-chlorophenyl radical and R is the ethyl radical. 5. A compound according to claim 1, characterized in that in general] -CH = CH-SR means. 2 in the general formula R is a radical of the formula 6. A compound according to claim 5, characterized in that R denotes a phenyl radical with 1 to 2 fluorine atoms, chlorine atoms, bromine atoms, nitro radicals or alkyl radicals is substituted by 1 to 4 carbon atoms, the Substituents can be the same or different. 7. A compound according to claim 5 »characterized in that in the general formula R is a phenyl radical, which is substituted with 1 to 2 chlorine or bromine atoms. 8. A compound according to claim 1, characterized in that 2
in the general formula R is a radical of the formula -CH = CH ₂ means. 9. A compound according to claim 8, characterized in that in the general formula R is an alkyl radical. 10. A compound according to claim 8, characterized in that in the general formula R is a phenyl radical or a Phenyl radical with 1 to 2 fluorine atoms, chlorine atoms, bromine atoms, nitro radicals or alkyl radicals with 1 to 4 Carbon atoms is substituted, where the substituents can be identical or different, means. 709833/0987 11. A compound according to claim 8, characterized in that in the general formula R is the methyl radical or the means p-chlorophenyl radical. 12. Compound of the general formula RSCH ₀ CHSO ₅ R ¹ X wherein R is an alkyl radical having 1 to 6 carbon atoms, a phenyl radical or a phenyl radical having 1 to Fluorine atoms, chlorine atoms, bromine atoms, nitro radicals or alkyl radicals substituted with 1 to U carbon atoms is, where the substituents can be identical or different, and R is a radical of the formula -CH-CH ₀ SR X is substituted alkyl of 1 to 6 carbon atoms, a phenyl radical or a phenyl radical which barren with 1 to 3 fluorine atoms, chlorine atoms, bromine atoms, nitro groups alkyl of 1 to ¹ I carbon atoms wherein the substituents may be identical or different, represent. 13. Fungicidal agent, characterized in that it contains a compound according to claim 1 as an active ingredient. Ik. Algicidal agent, characterized in that it contains a compound according to Claim 1 as active ingredient. For: Chevron Research Company San Franciaco, / Äal., V.St.A, Dr.H.JkWolff Lawyer 709833/09 * 7