Ethene sulfonates

An intramolecular cycloaddition reaction of the ethene sulfonate (57) occurs at high pressure and leads predominantly to the cis fused sultone (58). The minor product is the trans fused diasteieoisomer <96JCS(P1)2297>. 

Scheme 8.38. Intramolecular Diels-Alder reaction of ethene sulfonates.

Sodium ethene sulfonate. See Sodium vinyl sulfonate... 

Sodium vanadate. See Sodium metavanadate Sodium vinyl sulfonate CAS 3039-83-6 EINECS/ELINCS 221-242-5 Synonyms Ethenesulfonic acid sodium salt Ethylenesulfonic acid sodium salt Sodium ethene sulfonate SVS Vinylsulfonic acid sodium salt... 

Rhodococcus sp. Strain WU-K2R A Rhodococcus strain capable of sulfur-specific desulfurization of benzothiophene, naphthothiophene (NT), and some of their alkyl derivatives was reported [35]. The metabolites of BT desulfurization were BT sulfone, benzo[c][l,2]oxanthiin S-oxide, benzo[c][l,2]oxanthiin S,S-dioxide, o-hydroxystyrene, 2,(2 -hydroxyphenyl)ethan-l-al, and benzofuran. The NT metabolites were NT sulfone, 2 -hydroxynaphthyl ethene, and naphtho[2,l-b]furan [35], The exact biochemical pathway was not determined, however, part of the pathway for BT desulfurization was speculated to be similar to Paenibacillus All-2. 

It should be noted that addition of the tributyltin radical to 1-fluoro-1-(phenylsulfonyl)ethene provides phenyl vinyl sulfone as the only isolated product. However, 2-trimethylsilyl-1-fluoro-1-(phenylsulfonyl)ethene reacts with tributyltin hydride in the presence of AIBN to provide (E)-2-trimethylsilyl-1-fluoro-1-tributylvinylstannane. The vinylstannane is an equivalent for the synthon "H2C=CF " providing a convenient route to 2-fluoro-1-alkenes.8 The trimethylsilyl group can be removed with potassium fluoride in dimethyl sulfoxide-water or oxalic acid-methanol at the end of the reaction sequence. 

The water-soluble palladium complex prepared from [Pd(MeCN)4](Bp4)2 and tetrasulfonated DPPP (34, n=3, m=0) catalyzed the copolymerization of CO and ethene in neutral aqueous solutions with much lower activity [21 g copolymer (g Pd) h ] [53] than the organosoluble analogue in methanol. Addition of strong Brpnsted acids with weakly coordinating anions substantially accelerated the reaction, and with a catalyst obtained from the same ligand and from [Pd(OTs)2(MeCN)2] but in the presence of p-toluenesulfonic acid (TsOH) 4 kg copolymer was produced per g Pd in one hour [54-56] (Scheme 7.16). Other tetrasulfonated diphosphines (34, n=2, 4 or 5, m=0) were also tried in place of the DPPP derivative, but only the sulfonated DPPB (n=4) gave a catalyst with considerably higher activity [56], Albeit with lower productivity, these Pd-complexes also catalyze the CO/ethene/propene terpolymerization. 

Water-soluble l,3-bis(di(hydroxyalkyl)phosphino)propane derivatives were thoroughly studied as components of Pd-catalysts for CO/ethene (or other a-olefins) copolymerization and for the terpolymerization of CO and ethene with various a-olefins in aqueous solution (Scheme 7.17) [59], The ligands with long hydroxyalkyl chains consistently gave catalysts with higher activity than sulfonated DPPP and this was even more expressed in copolymerization of CO with a-olefins other than ethene (e.g. propene or 1-hexene). Addition of anionic surfactants, such as dodecyl sulfate (potassium salt) resulted in about doubling the productivity of the CO/ethene copolymerization in a water/methanol (30/2) solvent (1.7 kg vs. 0.9 kg copolymer (g Pd)" h" under conditions of [59]) probably due to the concentration of the cationic Pd-catalyst at the interphase region or around the micelles which solubilize the reactants and products. Unfortunately under such conditions stable emulsions are formed which prevent the re-use... 

With olefins other than ethene two isomeric chlorohydrins can be obtained, one of them being chiral. When pyridine was replaced by monodentate chiral amines in [PdCl3(pyridine)], the enantioselectivities were low (8-12%) (Scheme 8.3) [14]. The mononuclear [PdCl2(L2)] complexes (L2 = sulfonated p-tolyl-BINAP) performed better providing the chird chlorohydrin in 46-76% e.e. Even better activities and... 

The major advantages of this procedure over the enol sulfonate procedure lie in the availability of diethyl 2-chloro-2-cycl opropyl ethene-1,1-dicarboxylate from the corresponding acylmalonate and phosphorus oxychloride, and the fast, homogeneous, decarboxyl at 1ve elimination reaction of the triethylamine salt of the half-ester in dry organic solvents. The conditions described here, with slight modifications (overnight treatment), have been used for a variety of g-chloro alkyl idene/aryl idene malonates as shown in Table I. 

Exercise 21-24 a. Sulfur dioxide is an angular molecule that can be represented as having a nonbonding electron pair in an sp2 hybrid orbital and one vacant p orbital on sulfur. Use this formulation to derive a thermally allowed transition state for the reversible 1,4-cycloaddition of S02 to 1,3-butadiene (Section 13-3C). b. The three-membered ring sulfone, shown below, is very unstable and rapidly dissociates to S02 and ethene. This process is used for the synthesis of alkenes by the dissociation of cyclic sulfones (Ramberg-Backlund reaction). Determine whether the transition state for the thermally favorable reaction is conrotatory or disrotatory. 

Dimethyl-1-cyclohexyl-1-trimethylsiloxy-ethene (191) gives by means of methyllithium/ethylbromide in dimethoxyethane (DME) 1-cyclohexyl-2,2-dimethyl-1-butanone (297)133 Dimerizations occur when substances such as 1-trimethylsiloxy-styrene (192) or 1-trimethylsiloxy-l-cyclopentene (195) are treated with silver oxide/ DMSO to afford l,5-diphenyl-2,5-butadione (198) and 2,2 -dicyclopentanonyl (199)l34 respectively. Under the catalytic influence of Cu2+ ions, 192 plus ben-zenesulfonyl chloride yield phenyl-(l-phenyl-l-ethanone-2-yl)sulfone (200)l3 ... 

Figure 3.19 Schematic illustration of the synthetic pathway to benzene sulfonic acid PMOs the first step involves a Diels-Alder reaction of the ethene bridges with benzocyclobutene in the second step the benzene moieties were sulfonated.

Methyl />-tolyl sulfone has been prepared by oxidation of methyl 7>-tolyl sulfide with hydrogen peroxide 4 r or ruthenium tetroxide,6 by alkylation of sodium -toluenesullinate with methyl iodide 7,8 or with methyl potassium sulfate,9 by decarboxylation of -tolylsulfonylacetic acid,7 by thermal decomposition of tetramethylammonium -toluenesulfinate,10 by reaction of cw-bis-(%tolylsulfonvl)-ethene with sodium hydroxide (low yield),11 by the reaction of methanesulfonyl chloride with toluene in the presence of aluminum chloride (mixture of isomers),12 by... 

The Ramberg-Backlund reaction involves a thiirane-1,1-dioxide intermediate 58 as shown in Scheme 8. J ng etal. determined the mechanisms of reaction of thiirane-1,1-dioxide 59 with hydroxide ion in water <1996PAC825>. Two pathways were identified, the one first order and the other second order in hydroxide. The first step is formation of a trigonal bipyramidal mono-anion 60 formed by attack of OH at S of the sulfone. That anion then reacts with water to afford ethane sulfonate anion 61 or with a second OH to afford ethene and sulfite anion via 62 or 63 (Scheme 9). Some rate constants and equilibrium constants were determined. 

Obtained from active methylene compounds, such as malonic esters, -0x0 esters and jS-oxo sulfones, iodonium ylides serve as precursors of the corresponding carbenes. Their decomposition by a catalytic amount of a copper salt in the presence of a C-C double bond has been used for inter- and intramolecular cyclopropanation reactions. Thus, reaction of cyclohexene with bis(methoxycarbonyl)methylene(phenyl)iodine(III) under the catalytic action of bis(acetylacetonato)copper(II) yielded dimethyl bicyclo[4.1.0]heptane-7,7-dicarboxylate (1) (38%, mp 91-93°C) in addition to tetrakis(methoxycarbonyl)ethene (41%). ... 

Various alkylcyclopropanes have been converted to (l-alkenyl)cyclopropanes by dehydrogenation with trimethylsilyl triflate, selenium dioxide,tetrachloro-1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-l,4-benzoquinone, di-/er/-butyl dicarbonate and potassium tert-butoxide/dimethyl sulfoxide. A related transformation is the Ramberg-Back-lund reaction of bis(l-trimethylsilylcyclopropylmethyl) sulfone which gave ( )-l,2-bis(l-trimethylsilylcyclopropyl)ethene in fair yield. ... 

Vinyl sulfoxide sulfone Divinyl sulfoxide 1,1-Sulfinylbis ethene c4h6os 1115-15-7 Dehydrochlorination of mustard... 

Substantial attention has been directed (Section 2.5) to the occurrence of sulfonated sulfur-containing metabolites including sulfones and sulfonates. These include both methylsulfonyl derivatives of PCBs and of 2,2 -bis(4-chlorophenyl)-l,l-dichloro-ethene (DDE) (Janak et al. 1998). These are noted further in Section 7.5.2 in the context of the metabolism of PCBs by seals and polar bears. 

Vinyl sulfones are useful dienophiles. The sulfonyl group can be removed reduc-tively with sodium amalgam. In this two-step reaction sequence, the vinyl sulfone functions as an ethene equivalent. The sulfonyl group also allows for alkylation of the... 

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