Arenesulfenyl Chlorides Research Articles

N-arylsulfinyl-1,4-benzoquinonimines

Stable N-arylsulfinyl-1,4-benzoquinonimines were synthesized by acylation of the corresponding 1,4-benzoquinone monooximes with arenesulfenyl chlorides. The process involves transformation of sulfur(II) into sulfur(IV).

The role of nonbonded sulfur-oxygen interaction in the dissociative electron transfer to nitro-substituted arenesulfenyl chlorides.

The electrochemical reduction of p-nitrophenyl sulfenyl chloride, o-nitrophenyl sulfenyl chloride as well as bis(4-nitrophenyl) disulfide and bis(2-dinitrophenyl) disulfide was investigated in acetonitrile at an inert electrode. Reduction standard potentials as well standard heterogeneous electron-transfer rate constants have been determined using convolution analysis. An unexpected big difference in the thermodynamics and kinetics of the initial electron-transfer process as well as a striking change in the reductive cleavage mechanism of the S-Cl bond as a function of the nitro group position on the aryl ring of the aryl sulfenyl chloride is observed. A computational study at the B3LYP level shows that this difference in behavior is due to the through-space nonbonded S...O interaction in the o-nitrophenyl sulfenyl chloride.

Novel Approach Toward the Preparation of 1,6‐Enynes — Substrates for the Intramolecular Pauson—Khand Cyclization.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Novel approach toward the preparation of 1,6-enynes — substrates for the intramolecular Pauson-Khand cyclization

A novel approach to the synthesis of polysubstituted 1,6-enynes is elaborated based on the protocol of the three-component coupling of arenesulfenyl chlorides, dicobalthexacarbonyl complexes of conjugated enynes, and nucleophiles of the π-donor type and a possibility to employ the 1,6-enyne derivatives thus prepared as the substrates for the intramolecular Pauson—Khand cyclization is demonstrated.

Recent Progress in the Chemistry of Sulfur‐Containing Indoles

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Reactions of Tris(2‐pyridyl)phosphine Oxides with Electrophiles: Formation of 5‐Substituted 2,2′‐Bipyridyls.

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Reactions of tris(2‐pyridyl)phosphine oxides with electrophiles: Formation of 5‐substituted 2,2′‐bipyridyls

AbstractThe reaction of tris(2‐pyridyl)phosphine oxides with benzeneselenenyl chloride in methanol gave the corresponding 5‐phenylseleno‐2,2′‐bipyridyls together with a small amount of 2,2′‐bipyridyls. Similarly, the reaction with arenesulfenyl chlorides in aqueous acetonitrile afforded two kinds of coupling products, 5‐phenylthio‐2,2′‐bipyridyls and 2,2′‐bipyridyls. While in the reaction with arenesulfinyl chlorides in aqueous acetonitrile, four corresponding bipyridyl derivatives, 2,2′‐bipyridyls, 5‐arylthio‐2,2′‐bipyridyls, 5‐arylsulfinyl‐2,2′‐bipyridyls, and 5‐arylsulfonyl‐2,2′‐bipyridyls, were formed. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:72–81, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10085

ChemInform Abstract: Reactions of Dichlorocarbene and Arenesulfenyl Chlorides with 3,4‐Epoxy‐1‐butene and Vinylethylene Carbonate.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reactions of Dichlorocarbene and Arenesulfenyl Chlorides with 3,4-Epoxy-1-butene and Vinylethylene Carbonate

Reaction of 3,4-epoxy-1-butene with dichlorocarbene is accompanied by deoxygenation and yields a mixture of 1,1-dichloro-2-vinylcyclopropane, 2,2,2',2'-tetrachlorobicyclopropyl, and 2,2-dichlorocyclopropyloxirane. Arenesulfenyl chlorides react with 3,4-epoxy-1-butene to afford both Markownikoff and anti-Markownikoff addition products, whereas vinylethylene carbonate gives rise exclusively to the anti-Markownikoff adducts.

S-ArylN,N-dialkylamidothiosulfates, a novel class of sulfenic acid derivatives

A method for the synthesis ofS-arylN,N-dialkylamidothiosulfates, a novel class of sulfenic acid derivatives, was proposed. The method is based on the reaction of arenesulfenyl chlorides withN,N-dialkylamidosulfinic acids or with secondary amines in liquid SO2 in the presence of triethylamine. In the presence of halogen-containing Lewis acids,S-arylN,N-dialkyl-amidothiosulfates add to the C=C bonds to give aryl β-haloalkyl sulfides.

Neighboring Group Participation by Heteroaromatic Rings: The Wagner–Meerwein Type Skeletal Rearrangement in the Electrophilic Addition Reactions of Norbornadiene-Fused Furans, Pyrroles, and Thiophenes

Abstract The electrophilic addition reactions of norbornadiene-fused furans, pyrroles, and thiophenes with bromine, arenesulfenyl chlorides, or a triazoledione generally afforded skeletally rearranged adducts except for a dibenzoyl-substituted thiophene. The formations of the adducts are attributable to the neighboring group participation by five-membered heteroaromatic rings, accompanied by the formations of bridged heteroarenium ions and the subsequent Wagner–Meewein type skeletal rearrangement.

CoC bond cleavage in the reactions of alkyl, benzyl and heteroaromaticmethyl cobaloximes with arene sulfenyl chloride: Homolytic and heterolytic pathways

The reactions of arene sulfenyl chlorides, ArSCl, (Ar=Ph, C 6Cl 5, 2,4 (NO 2) 2C 6H 3) with organocobaloximes, RCo(dmgH) 2Py, (R=alkyl, benzyl and heteroaromaticmethyl) were carried out under thermal and photochemical conditions. A variety of organic and organometallic products are formed depending upon the substrate cobaloxime. For 3-methoxybenzyl and heteroaromaticmethyl cobaloximes the results suggest that they represent a unique class of cobaloximes whereby both the aromatic ring as well as the CoC bond are highly activated towards attack by the arene sulfenyl chloride. Both homolytic as well as heterolytic pathways are operative.

ChemInform Abstract: Four‐Components Coupling Based on the Sequence of AdE Reactions Involving Arenesulfenyl Chloride, Two Alkyl Vinyl Ethers and Silicon‐Containing π‐Donors as a Method for the Preparation of Polyfunctional Compounds.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Four-component couplingvia a sequence of threeAd E reactions involving arenesulfenyl chloride, two alkyl vinyl ether units, and silicon-containing π-donors as a method for the synthesis of polyfunctional compounds

A protocol for the synthesis of polyfunctional compounds by a Lewis acid initiated tandem sequence of threeAd E reactions of sulfur-containing electrophiles with two alkyl vinyl ether units and silicon containing π-donors is proposed.

Synthesis of organocobaloximes: Modification of the organic group in organocobaloximes

5-Substituted heteroaromaticmethyl cobaloximes are synthesized by a very simple reaction of arenesulfenyl chloride, ArSCI (Ar = Ph, C 6Cl 5 and 2,4-(NO 2) 2C 6H 3) with heteroaromaticmethyl cobaloximes, RCo III(dmgH) 2Py [R = 2- and 3-thienylmethyl, furfuryl] in the dark at 0°C. As organocobaloximes are susceptible to CoC bond cleavage by the electrophiles and free radicals, the ring substitution is quite remarkable.

Studies on isocyanides and related compounds. An unusual synthesis of imidazolyloxazolones

AbstractThe reaction between ethyl (Z)‐3‐dimethylamino‐2‐isocyanoacrylate (1) and arenesulfenyl chlorides 6a‐c afforded the unexpected imidazolyloxazolones 7a‐c. The structure of compounds 7a‐c was in agreement with their 1H nmr, ir and ms data and was confirmed by X‐ray analysis of 7a.

Application of the Michaelis–Arbusov reaction to the synthesis of internucleoside 3′-S-phosphorothiolate inkages

The 5′-O-monomethoxytrityl-3′-S-(aryldisulfanyl)-3′-deoxythymidines 7 and 8 have been prepared by the reaction of 5′-O-monomethoxytrityl-3′-thiothymidine with the appropriate arenesulfenyl chloride. These disulfides undergo a Michaelis–Arbusov reaction with simple trialkyl phosphites to yield 5′-O-monomethoxytrityl-3′-thiothymidin-3′-yl O,O-dialkyl phosphorothiolates. More interestingly, 3′-deoxy-3′-S-(2, 4-dinitrophenylsulfanyl)-5′-O-monomethoxytritylthymidine 8 reacts with a variety of thymidin-5′-yl dialkyl phosphites to give dithymidine phosphorothiolate triesters with the phosphorothiolate group protected with either a methyl or a 2-cyanoethyl group.

Reactions of diphenyl[bis(trimethylsilyl)amido](trimethylsilylimido)phosphorane with organochalcogen halides: preparation, x-ray structure, and reactions of Ph2PN2(SiMe3)2(SPh) with E2Cl2 (E = S, Se) and PhSeCl

The reactions of Ph 2 PN 2 (SiMe 3 ), with arenesulfenyl chlorides in a 1:1 or 1:3 molar ratio in methylene dichloride produces the metathetical products Ph 2 PN 2 (SiMe 3 ) 2 (SAr) [1a, Ar=Ph; 1b, Ar=2,4-(NO 2 ) 2 C 6 H 3 ] or Ph 2 PN 2 (SAr) 3 (2d, Ar=2,4-(NO 2 ) 2 C 6 H 3 ), respectively

Triorganogermanium Selenocarboxylates: Synthesis and Reactions

A series of triphenylgermanium selenocarboxylates 3 were synthesized and characterized. The esters 3 are thermally stable, but labile towards moisture and oxygen. They react with arenesulfenyl chlorides and areneselenenyl bromides at room temperature to afford the corresponding acyl arenesulfenyl selenides and acyl aryl diselenides in moderate yields.

ChemInform Abstract: Alkylation of π‐Donor Compounds with Methoxyallene ‐ Arenesulfenyl Chloride Adducts.

ChemInform Abstract: Alkylation of π‐Donor Compounds with Methoxyallene ‐ Arenesulfenyl Chloride Adducts.