Ethyl vinyl sulfones

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]. 

Masri, M.S., and Friedman, M. (1988) Protein reactions with methyl and ethyl vinyl sulfones./. Protein Chem. 7, 49-54. 

Figure 20. Sulfur 2p spectrum from casein modified with ethyl vinyl sulfone. (Reproduced, with permission, from Ref. 48. Copyright 1976, North-Holland...

In the presence of peroxide, the same type of addition-elimination reaction with alkyl iodide (71) and ethyl vinyl sulfone can be carried out as shown in eq. 4.29 [79]. However, the reaction pathway is rather complicated. 

The reaction of a,/ -unsaturated sulfones with chloroform, carried out under base/phase-trans-fer catalyst conditions, depends on the type of substituent on the sulfonyl group. Thus, phenyl vinyl sulfone underwent the Michael reaction with trichloromethyl anion to give 1, while ethyl vinyl sulfone underwent addition of dichlorocarbene to give cyclopropane 2. °... 

A limited number of examples restricts the evaluation of dibromocyclopropanation of unsaturated sulfones from a preparative point of view. Ethyl vinyl sulfone furnished the expected product 1 in a good yield. ... 

Pudovik, A.N., and Sitdikova, F.N., Addition of partial esters of phosphorus acids to nitroisoamylene and ethyl vinyl sulfone, Dokl. Akad. Nauk SSSR, 125, 826, 1959 Chem. Abstr, 53, 19850c, 1959. 

An interesting reaction between ethylene and SO2 occurs with palladium chloride as catalyst forming mainly crotyl ethyl sulfone and, to a minor extent, ethyl vinyl sulfone. The mechanism probably involves a hydridochloropaUadation complex as the true catalyst (Scheme 31). 

Vinylsulfonyl)ethanol, SCI. 2-Hydroxy ethyl vinyl sulfone [4271-48-1]... 

Ethyl vanillin, in D-00519 Ethyl vinyl sulfone, see E-00114 Ethyl violet, E-00122... 

The aziridine aldehyde 56 undergoes a facile Baylis-Hillman reaction with methyl or ethyl acrylate, acrylonitrile, methyl vinyl ketone, and vinyl sulfone [60]. The adducts 57 were obtained as mixtures of syn- and anfz-diastereomers. The synthetic utility of the Baylis-Hillman adducts was also investigated. With acetic anhydride in pyridine an SN2 -type substitution of the initially formed allylic acetate by an acetoxy group takes place to give product 58. Nucleophilic reactions of this product with, e. g., morpholine, thiol/Et3N, or sodium azide in DMSO resulted in an apparent displacement of the acetoxy group. Tentatively, this result may be explained by invoking the initial formation of an ionic intermediate 59, which is then followed by the reaction with the nucleophile as shown in Scheme 43. 

Carbanion 239 derived from vinyl sulfone 238 was shown to be alkylated regiospecifi-cally at the a-carbon atom The carbanions 240 and 241 derived from <5-ketosulfones were shown to be alkylated at both a- and y-carbons . Alkylation of 240 gave a-alkylated products predominantly, while the a/y ratio varied markedly by change of the alkylating agent in the reaction with 241. For example, methylation with methyl iodide gave the products in the a/y ratio of 72 28, while the a/y ratio was 27 73 in the ethylation with ethyl bromide ... 

A polymeric composition for reducing fluid loss in drilling muds and well cement compositions is obtained by the free radical-initiated polymerization of a water-soluble vinyl monomer in an aqueous suspension of lignin, modified lignins, lignite, brown coal, and modified brown coal [705,1847]. The vinyl monomers can be methacrylic acid, methacrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, vinylacetate, methyl vinyl ether, ethyl vinyl ether, N-methylmethacrylamide, N,N-dimethylmethacrylamide, vinyl sulfonate, and additional AMPS. In this process a grafting process to the coals by chain transfer may occur. 

The nonionic monomer can be acrylamide, N,N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-vinyl acetamide, or dimethylamino ethyl methacrylate. Ionic monomers are AMPS, sodium vinyl sulfonate, and vinylbenzene sulfonate. The terpolymer should have a molecular weight between 200,000 to 1,000,000 Dalton. 

N-vinyl acetamide, or dimethylamino ethyl methacrylate, 2-acrylamido-2-methylpropane sulfonic acid, sodium vinyl sulfonate, and vinylbenzene sulfonate... 

Vinyl ethers can also be generated by thermal elimination reactions. For example, base-catalyzed conjugate addition of allyl alcohols to phenyl vinyl sulfone generates 2-(phenylsulfinyl)ethyl ethers that can undergo elimination at 200° C.223 The sigmatropic... 

For the addition of ethylene, EtOAc as solvent was particularly advantageous and gave 418 in 60% yield (Scheme 6.86). The monosubstituted ethylenes 1-hexene, vinylcyclohexane, allyltrimethylsilane, allyl alcohol, ethyl vinyl ether, vinyl acetate and N-vinyl-2-pyrrolidone furnished [2 + 2]-cycloadducts of the type 419 in yields of 54—100%. Mixtures of [2 + 2]-cycloadducts of the types 419 and 420 were formed with vinylcyclopropane, styrene and derivatives substituted at the phenyl group, acrylonitrile, methyl acrylate and phenyl vinyl thioether (yields of 56-76%), in which the diastereomers 419 predominated up to a ratio of 2.5 1 except in the case of the styrenes, where this ratio was 1 1. The Hammett p value for the addition of the styrenes to 417 turned out to be -0.54, suggesting that there is little charge separation in the transition state [155]. In the case of 6, the p value was determined as +0.79 (see Section 6.3.1) and indicates a slight polarization in the opposite direction. This astounding variety of substrates for 417 is contrasted by only a few monosubstituted ethylenes whose addition products with 417 could not be observed or were formed in only small amounts phenyl vinyl ether, vinyl bromide, (perfluorobutyl)-ethylene, phenyl vinyl sulfoxide and sulfone, methyl vinyl ketone and the vinylpyri-dines. 

M. Shi and Y.-L. Shi reported the synthesis and application of new bifunctional axially chiral (thio) urea-phosphine organocatalysts in the asymmetric aza-Morita-Baylis-Hillman (MBH) reaction [176, 177] of N-sulfonated imines with methyl vinyl ketone (MVK), phenyl vinyl ketone (PVK), ethyl vinyl ketone (EVK) or acrolein [316]. The design of the catalyst structure is based on axially chiral BINOL-derived phosphines [317, 318] that have already been successfully utilized as bifunctional catalysts in asymmetric aza-MBH reactions. The formal replacement of the hydrogen-bonding phenol group with a (thio)urea functionality led to catalysts 166-168 (Figure 6.51). 

A solution of phenyl(3-pyridyl) vinyl sulfone (2.50 g) in toluene (5 ml) was added to the stirred polyleucine-hydrogen peroxide gel suspension in toluene. The mixture was stirred at room temperature for six hours and the reaction followed by TLC (eluent 60% ethyl acetate in hexane, vis. CAN). The product was isolated by hltration through Celite washing with ethyl acetate, drying over magnesium sulfate and concentration in vacuo. 

Free-radical-mediated four-component coupling reactions are rare. However, when an allyltin-mediated radical carbonylation is conducted in the presence of electron-deficient alkenes, four-component coupling reactions take place efficiently to give good yields of p-functionalized <5,fi-unsaturated ketones [40]. The wide scope of this four-component coupling reaction is noteworthy Primary, secondary, and tertiary alkyl bromides and iodides can be used as well as aromatic and vinylic halides. A variety of electron-deficient alkenes, such as methyl vinyl ketone, ethyl acrylate, acrolein, acrylonitrile, and vinyl sulfone, can be used as the acyl radical trap (Scheme 6.23). Fluorous allyltin compounds can also be used in four-component coupling reactions [41]. 

SAFETY PROFILE Poison by ingestion and intraperitoneal routes. May be corrosive to skin, eyes, and mucous membranes. Explosive reaction with ethyl vinyl ether. Incompatible with hydrogen fluoride. When heated to decomposition it emits toxic fumes of SOx. See also SULFONATES. 

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