CA1097373A - Algicidal and fungicidal sulfones - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Sulfones of the formulas

Description

~73~3 DESCRIPTION OF THE PRIOR ART
Chemical Abstracts 68 59110t (1968) and 67 108135v (1967) disclose the preparation of beta-substituted ethyl vinyl sulfones by the addition of alcohols and mercaptans to divinyl sulfone.
E.N. Prilezhaeva and Laba et al, Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2149-2156, October 1969, and No. 7, pp. 1602-1608, July 1970, disclose a multi-step synthesis of ethyl 2-ethylthiovinyl sulfone.
DESCRIPTION OF THE INVENTION
In its broadest aspect this invention provides a compound of formula RSCH - fH ~ S2Z
A B
wherein R represents an alkyl group of 1 to 6 carbon atoms, a phenyl group or a substituted phenyl group having 1 to 3 su~stitu-ents, which may be the same or different and are chosen from chloro, bromo, nitro, alkyl of 1 to 4 carbon atoms or fluoro;
A and B taken together are chosen from (i~ A represents hydrogen and B represents halogen, or (ii) A and B together represent a second (carbon-carbon) bond; Z represents (i) a group Rl when A
represents hydrogen and B represents halogen, or (ii) a group R2 when A and B together represent a second bond; Rl represents (i) a grouping -CH2 - CHX - SR, wherein X represents halogen, and R
is as defined above; or (ii) a group R as defined above; R2 represents (i) the group -CH - CH - SR, in which group R is as defined above, or (ii) a group - CH = CH2, an alkyl group of 1 to 6 carbon atoms, a phenyl group, or a phenyl group having 1 to 3 substituents which may be the same or different and are chosen from fluoro, chloro, bromo, nitro, or alkyl of 1 to 4 carbon atoms, provided that (a) when R is phenyl, R2 is substituted phenyl; (b) when either R or R~ is phenyl, the other is not p-

-2- ~
D,,~

737~

nitrophenyl; (c) R and R2 when the same do not contain a p-chloro, p-methyl, or p-nitro substituent; (d) when two groups R are pre-sent they may be the same or different, provided that both are not alkyl when A ~nd B together represent a second (carbon-carbon) bond.
In a first preferred aspect this invention provides a compound of the formula RSCH=CH SO2R

wherein R is alkyl of 1 to 6 carbon atoms, phenyl or phenyl sub-stituted with 1 to 3 of the same or different substituents selec-ted from fluoro, chloro; bromo, nitro or alkyl of 1 to 4 carbon atoms and R is -CH=CH2, -CH=CH-SR or R provided that (a) when R
is phenyl, R2 is substituted phenyl; (b) when either R or R2 is phenyl, the other is not p-nitrophenyl; (c) R and R2 when the same do not contain p-chloro, p-methyl, or p~nitro substituent;
and (d) when two groups R are present they may be the same or dif-ferent, provided that both are not alkyl.
In a second preferred aspect this invention provides a compound of the formula RSCE~21HS2R

wherein E~ is alkyl of 1 to 6 carbon atoms, phenyl or phenyl sub-stituted with 1 to 3 of the same or different substituents selec-ted from fluoro, chloro, bromo, nitro, or alkyl of 1 to 4 carbon atoms and R is alkyl of 1 to 6 carbon atoms, phenyl or phenyl substituted with 1 to 3 of the same or different substituents selected from fluoro, chloro, bromo, nitro or alkyl of 1 to 4 carbon atoms, and X is halogen.
Representative alkyl R, Rl and R2 groups are methyl, r~
- -2a-37:3 ethyl, propyl and hexyl. Representative aryl R, R , and R groups are 4-chlorophenyl, 2-fluorophenyl, 3,S-dibromophenyl, 2-nitro-4-methylphenyl, 4-tolyl, 2-chloro-4-methylphenyl and 2,4,6-trichloro-phenyl.
Preferably R is phenyl or phenyl substituted with 1 to 2 of the same or diEferent substituents selected from fluoro, chloro, bromo, nitro or alkyl of 1 to 4 carbon atoms. Most preferably, R is phenyl substituted with 1 to 2 chloro or bromo.

-2b-~7373 1 Representative compounds of ~he invention ~h~rein Rl or 2 R2 are alkyl or aryl ~i.e., 1-halo-2-substit.uted-thioethyl

3 sulfon~s or 2-substituted-thiovinyl sulfon~s) include:

4 m_thyl 1-chloro-2-methylthio~thyl sulrone, phanyl-1-bromo-2-hexylthioethyi sulfone, 6 p-tolyl 1-chloro-2-p-bromo-4-methylphanylthio~hyl sulfone, 7 hexyl 1 chl~ro-2-o-nitrophenylthioethyl sulfon~, 8 e'hyl 1-bromo-2-o-fluorophenylthiosthyl sulfons, 9 mathyl 2-methylthiovinyl sulfone, 2,4-dichlor~phenyl-2-o-chlorophenylthiovinyl sulfone, 11 hexyl 2-(2-~ethyl-4-chlorophenylthio)vinyl sul~one, ~n~
12 ethyl 2-(2-bromo-4-chlorophenylthio)vinyl sulfone.
13 ~he compounds of the inventi~n wherein R~ is -CH(%)C~2-14 SR are bis-(1~halo-2-substituted-thioe~hyl) sulfon~s and are represented by the formula 17 1 ~ (III) 19 and compounds of the invsntion wher~in R2 is -CH=CH-S~ are bis-20 ~2-substitutsd-thiovinyl) sulfones and are represented by the 21 formula 22 RSCH-CHS02CH=CHSR (IV~
2 3 wh~r~in R i~ as de~ined above.
24 Representative compounds of ~ormQlas ~III; and (Ilt) 25 include~
2~ bis~ chloro-2-methylthio) sulfo~e, ~7 bis~ brom~ 2-ethylthioethyl) sulfona, 28 bis~ bromo-2-o-fluorophenyl~hioethyl~ sulfone, 29 bis (1:-Chloro-2-o-chior~-p-bromophe~ylthio~thylJ sulfone, bis-~2-methylthiovin~l~ sll~o~e, ~1 bis- ~2-hexylthio~ inyl~ sul~one, 32 bis- (2-p-tolylthioYinyl) sul~one, 33 bis-(2-o-fluorophenylthiovinyl) sulone~ and ., 34 bis- (2-o-ni~ro-p-chlorophenylthiovi~lyL) sulfo~e! ~
: , The co~pounds of the invention wherein RZ ~S Yinyl are 36 ~ vinyl 2-substituted-thiovinyl sulfones and are repre6ented by the 37 for~ula (Y):
38 RSC8=CHSO2CH=cH2 (V~

39 Represe~tati~e co~pounds o~ formula (V) include:
vinyl 2-~2-chlorophenylthio)vi~yl sulfone, 41 , ~inyl 2-(2-chloro-4-bro~ophenylthio)vinyl sulfone, 4Z vinyl 2-(2-~thyl-4-~thylphe~ylthio)vinyl slllfone, ;

~97373 1 vinyl 2-(2-methyl-~-ethylphenylthio)vinyl sulfone, 2 vinyl 2-(2-methy1-4-nitrophenylthlolvinyl sulfone, 3 ~inyl 2-~sthylthlovinyl sulfone, 4 vinyl 2-isopropylthiovinyl sulfone, and vinyl 2-hexylthiovinyl sulfone.
6 The co~pounds of formula (I) wher2in R~ is alkyl ~r 7 aryl (1-halo-2-substituted-thioethyl sulfones) ar~ prepared by 8 adding ~ sulfenyl halide (VI) to an alkyl vinyl sul~one (vIr) and 9 the 2-substituted-thiovinyl sulfones (II) are prep~red by dehydrohalogenating the 1-halo-2-substituted-thio~thyl sul~ones 11 (I3 ~ith a b3se, as depicted in the ~ollowing reactions:

13 ~-SX CHz-CHSO2Rl -> RSC~zCHSO2~t 14 (VI~ (YII) X (I~ tl) !
RSCHzCHSO2R2 ~ B -> RSCH=C~S0z~2 ~ B~HX

17 X (I, Rl=RZ) (II) (2) 18 ~hereln ~ and X have the same significance as previously defined, 19 Rl and R2 individually are alkyl or arylt as preYi~usly defin~d, and B is a base.
21 Reaction (1) is conducted ~y r~acting substantially 22 equimolar amounts of the sulfenyl halide (YI) and the alkyl vinyl 23 sulfone (VII) in the liquid phase at a temperature of about 0~ to 24 100C. Generally~ an inort organic solvan , such as an alkan~, a haloalkane or an aro~atic compound, is employed in the reaction.
26 ReactLon p~essure is suitably atmospheric~ subatmospheric or 27 supsratmosphericO Por con~enience, ~he reactio~ pressure is 28 generally at~ospheric. The reaction is generally e~othermic and 29 is co~pleted ln about 1 to 24 hours. The 1-halo-2-s~bsti~tuted-thioethyl sulfone product (I) is isolated and purifi~d by conYen-i 31 ~ional procedures such as extraction, filtration, ch~omatography, 32 distillationt or alternatively, i~ us~d directly in Feaction ~2) 33 ~ithout pu~ification and/or isolation.
34 In ~saction (2), the ~-halo-2-suDstituted-thioethyl sul~one (I) is treat~d vith substantiaLly.~quimolar amounts o~ a i 1 base. The preferrsd base is an oryanic ~ase such as a pyridine 2 compound, e.g., pyridine or an alkylpyridine, or a trialkylamine, t 3 e.g., triethylamine. Reaction ~2~ is conducted in the liquid 4 phase at a temperature of 0 to 100C. Generally, ~n inert organic diluent such as a haloalkane, e.y., dichlorqmethane or aa 6 aromatic hydrocarbon, e.g., benzena, is employed in the reaction.
7 The reaction pressure is not critical, and, for convenience, the ô pressure is generally atmospheric. The reaction is generally 9 complete ~lthin about 1 to 24 hours. Th~ product ~II) is ~solated and puri~ied by conventional procedures such as filtra- !
~1 tion, eYtraction, dis~illation, chromatography, etc.
12 The bls-(1-halo-2-substituted-~hioethyl) sulfones (III~
13 are prepared by adding a sulfenyl halide (VI) to divinyl 14 sulfon~lVIII) and the bis-(2-subs~ituted-~hiovinyl~ sulfones (IV) are prepared by dehydrohalogenating the Dls(1-halo-2-substituted-16 thioethyl~ sulfones (III) ~ith a base, as depicted in the 17 followlng reactioas:
18 2RSX ~ CH2-CHS02CH=C~2 -> BSC~2CHS02CHCH2SR
~VI) (YIII) X X (III) (3) 21 RSC~2C~S0zCHCH2S~ ~ 2B--~RSC~-C~SO2CH=C~SR ~ 2B-HX

23 ~ X X (III) ~,IV) (4~ 1 24 wbereln B and X have the same si~gniricance as previously defined, ~S and B is a base.
26 Raaction (3) i5 ooDducted Dy reacting subs~antially 2 27 mols of the sulfenyl halide (VI) p~r mol of the di~ipyl sul~one 28 ~ ~VIII) in th~ liquid phas~ at a temperatura of about 0 to 100C.
29 Generally, an inert organic sol~ent, suc~ as an alkane, a .
30~ ~ baloalkane or a~ aromatic compound is employed in the reac~ion.
3~ Reaction pressure is suitably atmospheric, subatmosp~eric or 32 s~perato~spheric. ~or conynie~ce~ the reaction pressure is 33 g~2srally atmospheric~ The reaction is ~enerally exqthermic aad ~0~7373 1 is completed in a~out 1 to 24 hours. ~ha bis-(1-halo-2-2 substituted-thioethyl) ~ulfone pr~duct (lII) is isolat~d and 3 purified by conventio~al procedures suc~ as extraction, 4 filtration, chromato~raphy, distillation, or, alternatively, is used directly in reaction (4) without purification ~nd/or 6 isolation.
In reaction (4), th6 bis~ haio-2-substituted 8 thioethyl) sulfone ~III) is tr~ated ~i~h about 2 equivale~ts of a 9 base. The preferred base is an crganic Dase such as a pyridine compou~d, e.g., pyridine or an alkylpyiridine, or a 11 trialkylamine, e.gO, triethylamine~ ~eact~on ~4~ is conduct~d in 12 the liquid p~ase at a temperature o~ 0~ to 100C. Generally, an 13 inert organic dil~ent such as a haloalkane, e.g., dichloro-14 methane, or an aromatic hydrocarbon, a.g., benzene, is employed in ~he reac~ion. The reac~ion pressure 15 not critical, and, for 16 convenisnce, the pres~ure is generally atmospheric. The reac~ion 17 is generally co~plete withi~ about 1 to ~4 hours. The product 18 tIY) is isola'ced and purified by co~Yentional procedures~ such as 19 filtratio~ extraction, distlllation, ch~o~atography~ etc.
~he vinyl 2-substituted-thiovi~yl sul~on~ ~V3 are 21 prepared by adding a sulf~nyl halide (~I~ to divinyl sulfone ~IX) 22 a~d dehydrohalogenating the resulti~g 1~2~addition product (X) , 23 w~th a base to ob~ain the vinyl 2-su~stituted-~bio~inyl sulfone Z4 produc~ (V), as deFicted ~n the ~oliowi~g reaction6:
~SX + CH~-CHSO2CH=CH2--~~S~HzCHSO2CH=CH2 2fi 27 (VI) (IX) ~ (X) (S) 28 RSCH2C~SO2CH-CH2 ~ B -> RSC~=C~SO~CH=CH2 ~ BHX

X (X~ (V) ~6) 31 ~herei~ R has the ~ame significance as pr~Yiously de~ined, X is 32 chloro o~ bromo, and 2 i5 a base.

1 Reaction (S~ is conducte~ by raacting substantially 2 e~uimolar amou~ts of the sulfenyl halide (VI) and divinyl sulfone 3 (IX~ in the liquid phase at a temperature of about 0 to 100C, 4 as d~scribed for reaction (1). In reaction ~6), the 1,2-addition product (X) is treated with substansially equimolar amounts of a 6 base, as described in reaction (2).

8 The compounds of the invention are useful for 9 cantrolling fungi, particularly pla~t fu~al infections saused by Botrytis _ineEea, leaf blights caused by organisms such as 11 Pythrlum gltimum, Helmlnthos~_rum sa~lv_m, Yusarium mQnilifor~e, 12 Rh ~QCto~i_ s~lanl, Bonolinia fEuctlcola and Uromyces ~hasegli 13 typiSa. ~o~e~er9 some fungicidal compou~ds of the in~ention may 14 be more fungicidally active than others dgainst particular fungi.
~ ~hen used as fungicides, the compounds of the inYention 16 are applied in fungicidally ef~ective amounts to fungi a~d/or 17 :- their habitats, such as vegetati~e hosts and non-vegetative 18 hosts, e.g., ani~al prod~cts~ The amou~ used ~ill, of course, 19 depend on several factors such as the host, the type of fungus aDd the particular compound of the i~vention. As with ~os~
21 pa$ticidal compou~ds9 the ~unglc~des of ~h~ in~en~ion are ~ot 22 usually: appl~ed ~ull s~etlg~h,, but are ~en~rally i~corporat*d 23 with conventional biologicall~ inert e~tenders or carriers 2~4 normally employed for facilitating dlspersion of actiYe fungicldal co~pounds9 recogniziag that ~he formulation and mode 26 o~ ~pplication ~ay a~fect the actiYity oi the fungicide. Thus, 27 the ~ungicides of the inve~tion may be formulated and applied as .
28 yranules, as po~dery dusts, as uettable po~ders, as ~mulsifiable 29 o~oncentrates, as solutions, or as a~y ~f several other known types of ormulations, depending on the desired ~ode of 31 application.
t ~97373 1 Wettable po~ders are in the form of finely divided 2 particles vhich disperse readily in ~at~r or other dispersant.
3 These compositions normally contain from about 5-80% fungicide, 4 and the rest inert materlal, which includss dispersing agents, S emulsifying agents and wetting age~ts. The powder ~ay be applied 6 to the soil as a dry dust, or preferably as a suspe4sion in 7 water. Typical carriers include fuller's earth, kaolin clays, 8 silicas, and other h~ghly absorbent, readily ~ettable, inorganic 9 diluants. Typical wetting, dispersing or emulsify~ng agents include, for example: the aryl and alkylaryl sulfonates and 11 their sodium salts; alkylamide sulfo~ates, including fat y methyl 12 taurides; alkylaryl polyether alcohols, suLfated higher alcohols, 13 and polyvinyl alcohols; polyethylene oxldes, sulfonated animal 14 and vegetable oils; sulfonated petroleum oils, fatty acid esters of polyhydric alcohols and the ethy~ene o~ide addition products 16 of such esters; and the addition produc~s of long-chain 17 mercaptans and ethylene oxide. Many other types of useful ¦ -18 surface-active agents are available in c:o~erce. The sur~ace-19 activ8 agent, ~hen used" normally com~rises from 1~ to 15~ by veight of the fungicidal composition.
21 Dusks are freely flowiDg ad~i~tures of the actire 22 ~ungicide ~it~ finely divided solids SUCh as talc~ ~atural clays, 23 kleselguhr, pyrophyllitet ohalk, diatomaceous earths, calcium 24 phosphates, calcium and ~agnesiu~ carbo~ates, sulfurr li~e, flours, and other orga~ic and inorga~ic solids ~hich act as ~6 dispersants and carriers for the toxicant. These fipely divided 27 solids have an average particle size of less than abQut 50 28 micro~s. A typical dust i'ormulation useful herein contains 75 29 sllica and 25% of the toxicant. Use~ul liguid con~e~trates 30 ~ nclude the e~ulsifiable conce~trates ~hlch are homs~eneous 31 liquid Dr paste compssitions ~hich are r~adily dispeLtsed in water 1 or oth~r dispersant, and may consist entirely of the fungicide 2 ~ith a liquid or solid emulsifying ag~nt, or may also contain a 3 liquid carrier such as xylene, heavy aromatic napht~as, 4 isophorone, and other nonvolatile organic solvents. For application, these concentrates are dispersed in w~er or other 6 liquid carrier, and are normally ap~lied as a spray to the area 7 to be treated.
~ Other useful formulations for fungicidal applications 9 incl~d~ sl~ple solutions of the actire fungicide in a disper~ant in ~hich it ls completely soluble at the desired concentration, 11 such as ac~toner alkylated naphthalenes~ xylener or other organic 12 solvents. Granular formula~ions, ~herein the fungicide is 13 carried on relatively coarse particles, ar~ of particular utility 14 for aerial distribu~ion or for penetration of cover-crop canopy.
Pressu~izsd sprays, typically aerosols wnerein the active 16 ingredien~ is dispersed in finely divid~ form as a result of 17 Yaporization of a lo~-boiling dispersant sol~ent carrier, such as 13 ~h~ Preons~ may also be used. ~11 of those t:echniques for 19 formulating and appl~ng fungicides are well kno~n in the art.
The percentages by weight of the fungicide ma~ vary 21 according to the manner in which tha composition is to be applied ~22 and the particular type of formulatio~, DUt in general comprise 23 0.5% to 95% of the toxic~nt by ~eight of the fungicidal 24 compositionO
The fu~gicidal compositio~s may be formula~ed and 26 applied ~dith other active ingredients, i~cluding o~h~r 27 ~ungicides, insecticides, ne~atocides, ~actericides, plant gro~th -28 regulators, fertilizers, etc.
29 ~he compounds o~ the inYention are also useful for corltrolling microbiolo~ical organi3~s such as alga~, bacteria, 3~ ~lds, a~d occa~ionall7 aquat~c ~eeds which foul agu~ous ~7373 industrial effluents and cooling streams, such as those occurring in the paper and food-processing industries. They may also be used to control such organisms in other aqueous bodies such as lakes, streams, canals, pools, and the like. When so used, a biocidal quantity of one or more of the compounds of this invention is added to the aqueous growth environment of the organisms. Usually, this dosage will range between about 0.1 to 50 ppm. In any given ins-tance, the optimum dosage will depena -upon the particular organism and aqueous body involved. For instance, when used to control algae, these compounds will usually be employed at concentrations of about 0.1 to 10 ppm. In terms of pounds of compound per acre of water one foot deep, 0.1 to 10 ppm is equal to about 0.3 to 30 pounds per acre of water one foot deep. These compounds may be applied to the aqueous growth environments of such organisms as dispersible powders or in solution with water-miscible solvents.

Example 1 -- Preparation of eth~l 2-(4-chl~ ~ sulfone.
4-chlorophenylsulfenyl chloride, 7.5 g, was added to

5.0 g of ethyl vinyl sulfone in 20 ml of dichloromethane. There was no exotherm, and the system was refluxed for 3 hours. The dichloromethane was removed by stripping and the residue was dissolred in 50 ml of benzene. Triethylamine, 4.2 g, was added drop~ise with cooling, and after standing for 1 hour, the triethylamine hydrochloride was removed by filtration and the benzene stripped to give a crude product. Purification was carried out by chromatography on a silica gel column. The product, ethyl 2~(4-chlorophenylthio) vinyl sulfone, 4.2 g, was obtained as a clear oil showing one spot by thin-layer chroma-tography, calculated for CloHllC102S2: Cl, 13.4, S, 24.4; found:
C1, 12.7, S, 24.5.

~ 10 -~7~7~

1 ~xamination by infrared and N~ spectroscopy was in 2 complete accord with the proposed structure. The product is 3 tabulated in Table I as Compound No. 1.
4 Example 2 -- ereparatlon of ethYl_2~l4-nitro~henvlthio~vmnvl sulf_ge

6 Te~ grams of 4-ni~rophenylsulfenyl chlori~e was

7 combined with 6-4 g of ethyl vinyl suLfo~e in 30 ml of dichloro-

8 methane and refluxad for 6 hours. Strippi~g and reaction ~ith

9 triethylamine in benzene~ initially yave a crude red oil uhich crystalLized on standing, m . p. 55-58C.
11 The NNR spectrum fully supports the structure for ethyl 12 2-(4-nitrophenylthio)~inyl sulfone. ~e product and its 13 elem~ntal analy~is are tabulated in TabL~ I as Compound No. 2.
14 Compound laos. 3-8 of ~abl~ I ~er~ prepared by a 15 procedure similar to that of Examples 1 and 2.
16 Example 3 -- erepara io~ of 17 ethYl_1~chloro-2~2~chloroPhe~thioethyl__ulfQne 18 Five grams of 4-chlorophe~ylsulfenyl chloride ~as 19 refluxed with 3.3 9 ethyl vinyl sulfone ~or 3 hours in 20 ml of !
~20 dichloromethane. The stripped product sho~ed 3 spots by thin-21 layer chromatography and ~as puri~ied oy chro~a~ography over 22 ~ilica gel. The puri~iea produc~ was ~luted w~th d~chloromethane 23 a~d solidified af~er s~ripping to a whit~ solid, 6.~ g, ~.p. 60-:24 62C, calcuated for C~oHi2Cl20~52: :Cl, ~3~4~ S, 21.~; found:
Cl, 23.3, 8, 21.9~
26 Th~ product ana i~s elemental analysis are tabulated in 27 Ta~le I as Compound NO. 9 28 Example 4 -- Pre~aration of 29 bis~ 4 bEm~he~Xlthlo~lnYl sulf_ne f i Pifteen grams of 4-bromophenylsuLfenyl chl~ride vas 31 addsd slo~rly to a solution o~ 3.0 g divinyl sulfone in 30 ~l ¦

32 chlorofor~ so that thare was ~o exotherm. The reaction mixture 33 ~s heated under refl~x for 2-1/2 hours and then stripped. The i 73~

1 crude product vas treated with 5.2 g o~ tristhylamine in 40 ~l of 2 benzene overnight, then filSered and strlpped. The crude product 3 vas a red semisolid showing 3 spots on thi~-layer chromatography.
4 The crude product, 7.0 9, ~as chromatographed through silica gel (CH2Cl2 eluant) t~ give 3.2 g bis-2-(4-bromophenylt~io)~inyl 6 sulf one as a red liquid. Thin-layer chro~atography of the 7 product sho~ed a single spot. The ~roduct and its elemental 8 analysis are ta~lated in Table II as Compound No. 3.
9 The other compounds lexcept Nos. 9 or 10~ tabulated i~
Table II were prepared by a procedure si~ilar to that of Example 11 4. t 12 Example 5 -- Preparation of 13 bls-L1-Qhlo~o-2-~4-chlo o~heny~th _Leth~lLSul~n~
14 4-Chlorophenylsulfenyl chloride, 7. fi g, and 2.5 g of divinyl sulfone ~ere refluxed for 3 hours in 30 ml of methylene 16 chloride. Stripping ga~e a crude oil showing 4 spots by thin-17 layer chromatography. Purificatio~ ~as carried out by chroma-18 tography oYer silica gel. The product ~as eluted first with 19 m~thylene chloride and then with 3:1 ~et~ylene chloride-acetonQ ~, ZO to obtain a purified fraction, 3.4 9, calculated for 21 Cl~HI~Cl~02S3: S, 20.2, found 21.5. The product is tabulated in 22 Tabla II as Co~pouDd No, 9 23 ~xaople 6 -- Preparation of 24 yln Yl ~4 chlorQ~henxlthloLy Yl_SUlf_ne Pity grams ~f ~-chlorophenyl sul~enyl chloride Yas 26 added slo~rly to 33 . O g o di~inyl sulfona in 150 ~l of dichloro- !
27 methane ~i'ch cooling to remove the heat of reaction. After a fe~ ~
28 hours of standing at a~bient temFerature, the solvent ~as - j 29 stri:pped ~nd the crude adduc~ ~as dissolYed in 200 ml of benzene.
Thirty-one g of ~riethylamine ~as added slowly with ~¢ooling to 31 ma~ ntain aobient tQ~peratUre.. Afte~ sta~ding for ono hour, tha 32 triethylamine hydrochloride ~a~ removed by filtration. Aftar , 1 ~ashi~g ~ith tlater and drying ovPr magnesium sulfate, the solvent 2 was stripped to give 64 g of crude yroduct. This was purified by 3 chro~atography over silica gel to give 48 g of vinyl 2-(4-4 chlorophenylthio)vinyl sulfone, calculated for CloHgClO2S2 S, 24.6, found 24.4 6 The infrared aad NN8 spectra support the ~tructure.
7 Thin-layer chromatcgraphy on silica gel shows the presence f 8 cis- nd t~ansisomers as two adjace~ spots. The product is 9 tabulated in Table III as Compound ho. 1.
Example 7 -- Preparati~n of 11 vln~ t-bUtXlPhe~Xlth~L~Yl_sU~ e 12 In a manner analogous to EYample 6, 4-~-butylpehnyl- j 13 sulfenyl chloride ~as added in 1:1 propo~tlon to divinyl sulfone, 14 sub~t3cted to treatment with triethylamine in benzene~ and ~ purified by column chromatography. ~he ~roduct, vinyl 2-(4-t-16 buthylphqnrlthio)vinyl sulfone, uas obtai~ed as a brot~n oil ~hich 17 cyxstallized on s~anding, m.p. 62-64C: calcuated for 18 C~ 8~2S2: S~ 2~.7; ~ouna, S~ 22.00 Cl~ 0. t 19 Spectroscopic examination by infrared and N~R are i~
full accord ~ith tbe proposed s~ructure. The product is 21 tabulated ln ~able III a~ Compou~d ~o- 10.
22 The other co~po ~ds tabulated ln Table III were 23 prepared by procsdure~ similar to that described in Example 6.
24 ~3!!!~ Q~ xc lLaL,, Ia~_bit on A number of the compounds of the present i~ention ~ere 26 : evaluated for ~ungicidal efectiYe~ess by ~eans of a mycelial 27 i~hibition test. This test is desig~ed to measura t~e fungitoYic 2 8 activity of ~ungicidal che~icals in terms of their degree of ;
29 inhibition of ~celium gro~ Each compound to be ~ested was 30 dissol~ed in acetone ~o 500 ppm co~centration. Paper strips ~ere 31 inoculated ~i~h the pazticular mycelium gro~th by co~ering ~he 1 paper with a potato dextrose broth cul~ure of mycelial 2 suspension. The i~oculated papers were th~n placed on potato 3 dextrose agar plates and sprayed by ~eans of a ~icro-sprayer ~ith 4 the fungicidal soluti~n. The treated papar strips ~ere incubated at 25C and data were take~ after 24 hou~s. Fungicidal 6 activities ~ere measursd by a zone of i~hi~ited mycelial growth 7 fro~ the cent~r of the paper strip. The effectivaness of the 8 compounds tested for fungicidal activity is reported in Tables 9 IV-VI in terms Qf the micrograms/c~2 for 99~ control of the fu~gus.
11 E~3m~lQ9~ AlUa_cntrl !
12 Representatlve co~pounds o~ th~ invantion were tested 13 as algicide~ by the f ollowing ~etho~. Tha alqa ~est species ~ere 14 Lemna, Elodea and SD rQlina.
An acetone solution of tha test compound and a small 16 amount o a~ alkylarylpolyoxyethylene giycol-containing surfac-17 tant was prepared. This solution was mi~ed with a nutrient broth 18 i~ a quantity su~ficient to give a concentra~ion of 2 ppm. A
19 240-~l co~ainer was filled with this mi~ture. A sample of the test alga ~as added to ~ach container a~d the container was then 21 placed in a~ illuminated ~vlron~eJlt mal~tained at a temperatllre 22 Of about 2ûC ~or lncubation. The co~talrlers Yrera ~bserved 23 p~iodically for alga grow~h (as compara~ tO an unt~eat~3d check~ .
24 ~he algicidal effectiveness o~ the test compound Na s determinPd 2$ based on a final observation of alga groYth after 7 to 10 days.
26 The reslllts of the test, on a 0-to-100 basis -- 0 iD,dicating no 27 effectivenes~ a~d 100 inaica~ing complet~ effectiveness -- are 28 reported in 'rables VII-IX.

737~

TA8~,~E_~
2 Com ~ounds of the formula ~SCH-CHSOzR
3 Com~ _Ele m en t a l_A~lysis~
4 pound Physical Sulfur__ Haloaen No. ___R ___ R l_ ____State _ Calc. Four~d Calc. Yound 6 1 p-Cl-~ C2Hs Liquid 24.4 24.~13.512.7 7 2 p-NOz-0 C2 Hs ~. p. 55-58C23. 4 22. ~
8 3 3,4-C12-p' C2~s Oil 21.5 21.723.825.0 9 4 p-CH3-~ C2 HS Liguid 26 . 526. ~ __ _ p-Cl-p' C~13 Liguid 25. 8 25. 414 315 2 11 6 2,5-C~ CH3 m.p. 197~109C 22.622.425 0 25 6 12 7 p-~r-0 CH3 Liquid 21.9 21. 327.325.9 -:
~3 8 p-Br-p' CzHs Liquid 20.9 20.626.029.,3 14 9~ p-Cl-0 C2H5 m.p~ 60-62~C 21.4 21.923.723.2 0 ~ ph Qnyl 16 ~Compound is ethyl-1-chloro-2-p-cb~orophenylthioethyl sulfone 17 T~BL~
18 Compounds of the formula SO2(CH=CHSR)2 19 ____Elementa1_An alYs-s~
Compound Physical ___Sgl~r_ _ __Hal_~en___ t 21 No. _ R __State___ Calc Fo nd Calc. Found 22 1 p-C1-0 ~iqui.d 23.9 22.9 17.61602 23 2 m-Cl-~ Oil 23.8 23. 5 17.617.7 24 3 p-Br-0 Oil 19.5 18.6 32.,5 33.6 4 2~5-C1z-p Oil 20.4 19.0 30.030.3 26 S p-F-0 m.p. 85-89C 22.5 24.3 10.39.7 1 -27 6 p-NO2-0 Semlsolid 22 . 7 21. 4 28 7 3,4--C12 =p Oil 20.4 20. 2 30.,0 29.2 r 29 8 0 ûil 28.7 ~5. 3 3 0 9 (a) Oil 20 . 2 21~, 5 31 1 0 ~b) m . p. 143-5~ C 23 . 6 2 3 . 7 32 p = phenyl 33 (a) bis~ 1-chloro-2- ~4-chlorophenylthio) ethyl~ sulfone 34 ~ ~b) bis-2- (4-chlorophenylth~o) ethyl sulfone ' ; ' , i ~9~3~3 T A B L E~
2 Compounds of the ~ormula RSC~IsCHSO2CH=CHz 4 Compound Physical ___sulf ur___ __Haloqen___ O P~ St3te caic PoundCalc Pound 6 1 p-Cl-p Liquid 24.6 23.5 13.6 13 4 7 2 m-Cl-p' Oil 2 4 . 6 24 . 2 13 . 6 1 4 8 3 p-Br-0 Liquid 21.0 20.7 26.2 28.8 9 4 p-CH3-0 Oil 26. 6 24. 4 2, 5-Cl2 -p Oil ~ 20. 224. 0 2 5. 5 11 6 p-F-~d Oil 2~.3 24. 1 7.8 8.4 12 7 p-NOz ~0 Semisoli d ~3 . 621. 9 -- -_ 13 ~ 3,4-CL2-,o Oil ;~1.7 20. 924.0 26 2 14 9 g~ Oil 2~,.3 2~. 9 -- _ i p-(t-C~H9)-0 ~.,p. 62-64QC 22.7 22~2 -- -- i 16 11 CH3 Oil 39.0 40.5 -- --17 ,d represents phenyl 8 TA~E_IV
19 ~Yc~ Inb.~it.~o~ Crograms~!cm2-for-9g~ _ontrol .;
20Compound ~ Q ~ l3L _l4L_ ~sL_ 22 1 0.76 o~ 63 0.63 0.87 o. 34 ,-23 2 0.92 o.92 0~3 >1.7 o.76 24 3 1.6 0.65 1.5 1.5 o 54 2s 4 >1.7 0.92 1.2 >1.7 0 65 26 5 0.36 0.31 0.50 0.63 --27 6 0.8~ 0.~6 0~,580.56 -- ~
28 7 0,48 o. 41 0~59 0~76 - i 29 8- 0.7a 0.4 0.76 0.7 --

10~ >1.7 ,$.$ >1.7 >1.7 >1.7 32 11** >1.7 ~1.7 >1.7 >1.7 ~1 7 33 12*~* ~1.7 >1.7 >1.7 >1~7 ~1 7 34 *No. 10 is ~thyl 2 (p-chloro~henyl~hio)ethyl sulfone **No. 11 is ethyl ~ yl sulfo~e 36 *~*No. 12 is ethy~ methylthiovinyl su}fone 37 ~ 2t~ m ul~um:
38 (2) = ~izQ~to~ia s~ni 39 ~3~ z As~ill~S n eE
~4~ = Pu~o monI~orma 41 ~5~ = 80~L~i_ c~e~ `

:

.
:

TABLE V
2 ~ celia Inhibitio~_microqra~s~CmZ for_29~ contro 3 Compound 4 _No . ~ 2l_ _ (3L_ _ (4L_ _~5~_ S 1 0.22 0. 9 o.a6 > 1 7 --6 2 >1.7 1.5 1.1 >1 7 1.2 7 3 >1.7 1.4 0.73 >1.7 1.4 8 4 >1.7 1.2 >1.7 >1.7 Q 70 9 5 >1.7 ~1.7 ~1.7 >1.7 >1 7 6 0.7~ O.S0 0.34 >1.7 0 7

11 7 0.78 0.97 1.1 1.0 0 70

12 8 >1.7 0.88 0.50 >1.7 1.5

13 9 0.65 1. 5 1.3 1.3 1.1

14 10 >1.7 >1.7 >1.7 .>1.7 >1.7 ~ 2), (~), (4~ and (5) are as l~ Table IV.

T~BL E_yI
17 M~celi3_Inhibi'cioaL_mlCr Eams C~2 for 92% n~rl 18 1 0.24 0.8 0.6 1 5 0 98 19 2 >1.7 0.7 0.8 1 1 0 34 3 >1.7 0.85 1.10 78 0 69 21 4 0.67 >1.7 0.680 68 0 83 22 S >1.7 1.3 >1.7>1.7 0.67 23 6 1. 1 0.76 0.~71.5 1 .0 24 7 a.82 0.37: 1.5 1 6 0 80 25: 8 0.86 0.95 0.57>1 7 0 87 26 9 : 1.1 0.6 O.BI~>1.7 0,.56 27 10 >1.7 0.65~ 0.88 1.1 . >1.7 2~` ll 1.,6 >1:.7 >1.7~1.7 1.6 !, 29 ~1j, S2),~(3), (4~ a~d ~5) are as ill Table IV.
A~LE Yll:
~ 31 : ~9 ~ tlc_~Z C~a~
3 2: Co~pound ' ;-33: ~ ~Q~ mBa ~,odea S~,~lin~
34 ~ : 1 100 39 ~
: 35 2 ~ 0 9,0 36 3 . 60 39 90 37 ~ 4 o >o ao s gg ~ 60 sp 3~ 6 :99 :7v 80 4~ 7 99 78 75 41 ~ 8 99 50 8P
4 2 ~ _9 ______9 0 _~___7 ~ _ 9Q____ 44 - 11** o o 7 4s: ~ 12*~*100 o o , . : :
46 *, *~. and *** are aS in Table ~V.

::
~ : - 1 7 -'373 TA~ ~ V~I
Fercent Aquatic_Wet3d_Contro 3 Com po und 4 Nct- Lemna Elod~aS~lrollna 1 fi8 97 --7 3 94 9il 40 8 4 39 70 ao 9 5 ~0 70 ao 14~ 10 0 0 0 TABLE_IX
16 ~e~cen~_A~uat~ ead ContEol !
17 Com po un d 18 __No ___ Lemna Elo~ctaSPiroli~a 2 100 99 100 . .

23 5 90 7d 0 24 ~ 100 100 80 7 99 1~0 50 2~ ~ 94 70 40 28. 10 22 0 40 ,: :

:: ~
, i .

, .-' ~: ' }

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula RSCH=CH SO2R2 wherein R is alkyl of 1 to 6 carbon atoms, phenyl or phenyl substituted with 1 to 3 of the same or different substituents selected from fluoro, chloro, bromo, nitro or alkyl of 1 to 4 carbon atoms and R2 is -CH=CH2, -CH=CH-SR
or R provided that (a) when R is phenyl, R2 is substituted phenyl;
(b) when either R or R2 is phenyl, the other is not p-nitro-phenyl;
(c) R and R2 when the same do not contain a p-chloro, p-methyl, or p-nitro substituent; and (d) when two groups R are present they may be the same or dif-ferent, provided that both are not alkyl.

2. The compound of claim 1 wherein R is alkyl of l to 6 carbon atoms, phenyl or phenyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo, nitro or alkyl of 1 to 4 carbon atoms, and R2 is alkyl of 1 to 6 carbon atoms, phenyl or phenyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo nitro or alkyl of 1 to 4 carbon atoms, with the proviso that at least one R or R2 group is phenyl or substituted phenyl.

3. The compound of claim 1 wherein R is phenyl or phenyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro bromo, nitro or alkyl of 1 to 4 carbon atoms and R2 is alkyl of 1 to 6 carbon atoms.

4. The compound of claim 1 wherein R is p-chlorophenyl and R2 is ethyl.

5. The compound of claim 1 wherein R2 is -CH=CH-SR.

6. The compound of claim 5 wherein R is phenyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo, nitro or alkyl of 1 to 4 carbon atoms.

7. The compound of claim 5 wherein R is phenyl substituted with 1 to 2 chloro or bromo.

8. The compound of claim 1 wherein R2 is -CH=CH2.

9. The compound of claim 8 wherein R is alkyl.

10. The compound of claim 8 wherein R is phenyl or phenyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo, nitro or alkyl of 1 to 4 carbon atoms.

11. The compound of claim 8 wherein R is methyl or p-chloro-phenyl.

12. A compound of the formula wherein R is alkyl of 1 to 6 carbon atoms, phenyl or phenyl sub-stituted with 1 to 3 of the same or different substituents selec-ted from fluoro, chloro, bromo, nitro, or alkyl of 1 to 4 carbon atoms and R1 is alkyl of 1 to 6 carbon atoms, phenyl or phenyl substituted with 1 to 3 of the same or different substituents selected from fluoro, chloro, bromo, nitro or alkyl of 1 to 4 carbon atoms, and X is halogen.

13. A method for the control of fungi which comprises applying to said fungi or their habitat a compound of the formula defined in claims 1 or 12.

14. A method for the control of algae which comprises apply-ing to said algae or their habitat an algicidally effective amount of a compound of the formula defined in claims 1 or 12.

15. A compound of formula wherein R represents an alkyl group of 1 to 6 carbon atoms, a phenyl group or a substituted phenyl group having 1 to 3 substituents, which may be the same or different and are chosen from chloro, bromo, nitro, alkyl of 1 to 4 carbon atoms; or fluoro;
A and B taken together are chosen from (i) A represents hydrogen and B represents halogen, or (ii) A and B together represent a second (carbon-carbon) bond;
z represents (i) a group R1 when A represents hydrogen and B repre-sents halogen, or (ii) a group R2 when A and B together represent a second bond;
R1 represents (i) a grouping -CH2 - CHX - SR, wherein X represents halogen, and R is as defined above; or (ii) a group R as defined above;
R2 represents (i) the group -CH = CH - SR, in which group R is as de-fined above, or (ii) a group - CH = CH2, an alkyl group of 1 to 6 carbon atoms, a phenyl group, or a phenyl group having 1 to 3 substituents which may be the same or different and are chosen from fluoro, chloro, bromo, nitro, or alkyl of 1 to 4 carbon atoms, provided that (a) when R is phenyl, R2 is substituted phenyl;
(b) when either R or R2 is phenyl, the other is not p-nitrophenyl;
(c) R and R2 when the same do not contain a p-chloro, p-methyl, or p-nitro substituent;
(d) when two groups R are present they may be the same or different, provided that both are not alkyl when A and B together represent a second (carbon-carbon) bond.