Vinyl sulfone

Ethyl /m s -2-butenyl sulfone (86) together with some ethyl vinyl sulfone are obtained by the reaction of ethylene and. SO2 in wet benzene using PdCl2. SO2 behaves mechanistically similarly to CO in this reaction[66]. Hydrosulfination of alkenes with SO2 and H2 is catalyzed by the Pd(dppp) complex. The sulfinic acid 87 is a primary product, which reacts further to give the. S-alkyl alkanethiosulfonates 88 as the major product, and 89 and the sulfonic acid 90 as minor products[67]. 

Phenyl vinyl sulfoxide is chiral Phenyl vinyl sulfone is achiral... 

Reaction conditions depend on the reactants and usually involve acid or base catalysis. Examples of X include sulfate, acid sulfate, alkane- or arenesulfonate, chloride, bromide, hydroxyl, alkoxide, perchlorate, etc. RX can also be an alkyl orthoformate or alkyl carboxylate. The reaction of cycHc alkylating agents, eg, epoxides and a2iridines, with sodium or potassium salts of alkyl hydroperoxides also promotes formation of dialkyl peroxides (44,66). Olefinic alkylating agents include acycHc and cycHc olefinic hydrocarbons, vinyl and isopropenyl ethers, enamines, A[-vinylamides, vinyl sulfonates, divinyl sulfone, and a, P-unsaturated compounds, eg, methyl acrylate, mesityl oxide, acrylamide, and acrylonitrile (44,66). 

A number of synthetic polymers having the abHity to control filtration rates at high temperature and in the presence of calcium and magnesium have also been developed (88). Such materials include vinyl sulfonate—vinyl amide copolymers (89,90), a copolymer of AMPS and A/,A/-dialkyl (meth) acrylamide (91) and a sulfonated hydroxylated polymer (92). AppHcation levels for these materials range from 5 to 18 kg/m (2—6 lb /bbl). Sulfonated asphalt is also used for high temperature filtration control. 

The reactive dyes approved by the FDA are either dichloro-j -tria2ines or sulfatoethyl sulfones, termed vinyl sulfones. Both groups react with pendent hydroxyl groups on the polymer matrix. 

Fiber-Reactive Dyes. These dyes can enter iato chemical reaction with the fiber and form a covalent bond to become an iategral part of the fiber polymer. They therefore have exceptional wetfastness. Thein main use is on ceUulosic fibers where they are appHed neutral and then chemical reaction is initiated by the addition of alkaH. Reaction with the ceUulose can be by either nucleophilic substitution, using, for example, dyes containing activated halogen substituents, or by addition to the double bond in, for example, vinyl sulfone, —S02CH=CH2, groups. 

These constraints cause different reactive groups to be developed for dyeing wool. They fall into two groups novel reactive groups with more than one type of group in each molecule in order to increase the amount of dye fixed and minimise the wash-off problem, eg, Lanasol Dyes by CIBA-GEIGY, and those based on ceUulosic reactive dyes, but where the dye is appHed to the wool in a nonreactive form. On boiling, this form slowly converts to the reactive form that fixes rapidly in situ eg, the Hostalan Dyes by Hoechst, introduced in 1971 were precursors of vinyl sulfone dyes. 

For Reactive Blue 19 [2580-78-1] (Cl 61200 its reactive form, the vinyl sulfone (5), was found in the effluents of a textile mill and a wastewater treatment plant. The hydrolysis product of the vinyl sulfone was detected only in the effluent of the textile mill (257). 

In 1958, Hoechst introduced the vinyl sulfone reactive dyes, offered as the sulfatoester from which the reactive vinyl sulfone group was generated in the alkaline dye bath. 

There is a large variety of chloro or fluoro substituted heterocyclic rings which undergo X displacement by cell-0. Vinyl sulfones are usually generated under alkaline conditions from P-sulfatoethjisulfones,... 

An interesting concept is that of generating vinyl sulfones from P-(P-sulfatoethyl)sulfonylpropionamides (4) ... 

Tria2inyl reactive dyes show less tendency toward hydrolysis during washing than do the vinyl sulfone type. 

To overcome hydrolysis of vinyl sulfone dyes during appHcation under neutral dyeing of wool, Hoechst introduced dyes with the /V-methyl taurine... 

Benzo[h]thiophene sulfone (229) reacts as a vinyl sulfone and forms adducts (228) and (230) when treated with mercury(II) acetate in methanol and with cyclopentadiene, respectively. 

Methyl vinyl sulfone [3680-02-2] M 106.1, b 116-118 /20mm, d 1.215, n 1.461. Passed through a column of alumina, then degassed and distd on a vacuum line and stored at -190° until required. 

Verify, by making molecular models, that the bonds to sulfur are arranged in a trigonal pyramidal geometry in sulfoxides and in a tetrahedral geometry in sulfones. Is phenyl vinyl sulfoxide chiral What about phenyl vinyl sulfone ... 

However, when the bulky substituent is no longer present at the electrophilic carbon atom, the addition of the olefin to the morpholine enamine of cyclohexanone leads largely to the tetrasubstituted isomer. For instance the reaction of this enamine with phenyl vinyl sulfone gave a 1 3 mixture of... 

Reaction of the pyrrolidine enamine of cyclohexanone with phenyl vinyl sulfone afforded a 9 1 mixture of the tri- and tetrasubstituted isomers (2(5). The preference of the less substituted isomer in this case is in keeping with the greater overlap requirement between the n electrons of the double bond and the electron pair on the nitrogen atom, since the double bond exo to the five-membered ring is much more favored than the double bond exo to the six-membered ring. It is, however, hard to explain the formation of largely the trisubstituted isomer with the piperidine enamine of cyclohexanone, where both of the rings involved are six-membered. 

Similar cycloaddition reactions were observed with methyl vinyl sulfone (48) and )3-nitrostyrene (48,51). Methyl vinyl ketone, on the other hand, is reported to give dihydropyrans as the initial products (50,52,53). Thus (16) on reaction with methyl vinyl ketone at room temperature for 12 hr gave a 60% yield of 2-dimethylamino-3,3,6-trimethyl-3,4-dihydro-2H-pyran (59). 

The enamines derived from cyclic ketones give the normal alkylated products, although there is some evidence that unstable cycloadducts are initially formed (55b). Thus the enamine (28) derived from cyclohexanone and pyrrolidine on reaction with acrylonitrile, acrylate esters, or phenyl vinyl sulfone gave the 2-alkylated cyclohexanones (63) on hydrolysis of the intermediates (31,32,55,56). These additions are sensitive to the polarity of the solvent. Thus (28) in benzene or dioxane gave an 80% yield of the... 

Methyl vinyl sulfone forms 1,2-cycloaddition adducts with aldehydic enamines, both with and without 3 hydrogens (37). Simple alkylation was reported to take place when phenyl vinyl sulfone was allowed to react with cyclohexanone enamines (58,60), but it has recently been shown that phenyl vinyl sulfone also forms cyclobutane adducts (60a). 

When the Dnseoc group is used in nucleoside synthesis, the coupling yields are determined by measuring the absorbance at 350 nm of each eluate from the Dnseoc-deprotection steps containing the 5-(dimethylamino)naphthalene-l-yl-vinyl sulfone or by measuring the fluorescence at 530 nm. ... 

Perhydroindans (46) and (47) could be obtained in 73% yield from the carbonate (48) with only minor amounts of elimination product. The use of BSA and the triisopropyl phosphite-palladium acetate catalytic system provides further improvement. The low cisitrans selectivity in the formation of the first ring, and rapid subsequent cyclization account for the fact that the ratio of (46) to (47) is only 2 1 (Scheme 2.14). Even the presence of a bulky trialkylsiloxyl substituent adjacent to the vinyl sulfone moiety has only a minor influence on the cisitrans selectivity [24]. 

The formed vinyl sulfones are powerful Michael acceptors, which by treatment of the y-emti-product with base, undergo ring closure to diastereomerically pure 4-sulfonyltetrahydrofurans39. 

Addition of methyllithium to an enantiomerically pure vinyl sulfone to give the yv -adduct was a key step in the total synthesis of (-)-maytansinol14. 

The addition reactions of alkyllithium-lithium bromide complexes to a-trimethylsilyl vinyl sulfones that have as a chiral auxiliary a y-mono-thioacetal moiety derived from ( + )-camphor are highly diastereoselective. A transition state that involves chelation of the organolithium reagent to the oxygen of the thioacetal moiety has been invoked. The adducts are readily converted via hydrolysis, to chiral a-substituted aldehydes22. 

C8H802S, Phenyl vinyl sulfone [(Ethenylsulfonyl)benzene]... 

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