91525-56-3

Upstream product

• 64168-52-1 4'-nitrobenzenesulfenanilide 
• 75-05-8 acetonitrile 
• 110-83-8 cyclohexene 
• 100-47-0 benzonitrile 
• 14032-03-2 ((1R,2R)-2-chlorocyclohexyl)(phenyl)sulfane 
• 100-01-6 4-nitro-aniline 

Relevant academic research and scientific papers

Synthetic utility of 4'-nitrobenzenesulfenanilide in the functionalization of carbon-carbon double and triple bonds: Its use in the bromosulfenylation of alkenes and alkynes

The reaction of 4'-nitrobenzenesulfenanilide (NBSA) with hydrobromic acid, suitably carried out at room temperature in the presence of cyclohexene, trans-hex-3-ene, hex-1-ene and 3,3-dimethylbut-1-ene, results in quantitative isolation of corresponding 2-bromoalkyl phenyl sulfides which occur with trans-stereospecificity and anti-Markovnikov regiospecificity through electrophilic addition of initially-formed benzenesulfenyl bromide to the alkene double bond. Similar reaction in the presence of mono- and di- substituted alkyl- and phenyl-acetylenes generally affords (E)-2-bromovinyl phenyl sulfides in good yields, which become lower with decreasing nucleophilic power of the alkyne employed. However, in the presence of parent acetylene, no virtual formation of the corresponding sulfide adduct occurs, but almost exclusive formation of diphenyl disulfide essentially ascribable to preferred decomposition of the highly unstable benzenesulfenyl bromide intermediate. The present additions of benzenesulfenyl bromide to alkenes and alkynes are believed to involve the initial intermediacy of thiiranium- and thiirenium-like ions, respectively, by analogy with related Ad(E) reactions of sulfenyl chlorides.

Boron Trifluoride-Promoted Reaction of Benzenesulphenanilides with Alkenes in Acetonitrile and Benzonitrile: Amidino- and Amido-sulphenylation of Alkenes

Benzenesulphenanilides (1) react at room temperature with alkenes in acetonitrile or benzonitrile in the presence of boron trifluoride-diethyl ether to give amidino sulphides (5; R=Me, Ph) in fair to good yields together with varying amounts of amido sulphides (7; R=Me, Ph) and arylamino sulphides (4), whereas at 100 deg C and in the presence of water 4'-nitrobenzenesulphenanilide affords amido sulphides (7; R=Me, Ph) as the main products.With cyclohexene a high selectivity for trans-addition is observed.With terminal alkenes the terminal sulphides are produced with high regioselectivity.The findings are consistent with a mechanism involving intermediacy of episulphonium ions (3) which result from alkene attack at the sulphur atom of an anilide-BF3 complex.

THERMAL REACTIVITY OF 4'SUBSTITUTED- AND 4'-SUBSTITUTED-2-PHENYL-BENZENESUPHENANILIDES

The thermal decomposition of 4'-nitro, 4'-H, and 4'-methoxy-benzenesulphenanilides in benzene and/or furan, and of 4'-substituted-2-phenylbenzenesulphenanilides ( 1d-1f ) in benzene, was found to proceed by two distinct pathways: ( i ) nucleophilic displacement by furan and/or another sulphenanilide unit and ( ii ) homolytic S-N bond fission to give sulphenyl and anilino radicals.An increase in the electron-withdrawning capability of the 4'-substituted favours the ionic pathway, whwreas the radical pathway is favoured by an increase in the reaction temperature.

BORON TRIFLUORIDE PROMOTED REACTION OF BENZENESULPHENANILIDES WITH ALKENES

The boron trifluoride-promoted reaction of a series of 3'- and 4'-substituted benzenesulphenanilides (1) with various alkenes has been investigated as a potential synthetic route to arylaminosulphides.The benzenesulphenanilides (1) investigated generally afford arylaminosulphenylation adducts in fair to good yields except for the methoxy-substituted anilides (1e and f), which largely lead to decomposition products under comparable conditions.In all cases examined, the addition proceeds with trans-stereospecificity and, with terminal alkenes, leads regioselectively to the exclusive (or predominant) formation of the terminal sulphides.The findings are interpreted by assuming that boron trifluoride transforms the sluggish benzenesulphenanilides (1) into reactive electrophilic species, which can undergo nucleophilic attack at sulphur by an alkene, presumably affording episulphonium-borate ion-pair intermediates, in competition with attack by another sulphenanilide unit.

BORON TRIFLUORIDE PROMOTED REACTION OF BEZENESULPHENANILIDES WITH ALKENES-ARYLAMINOSULPHENYLATION OF ALKENES.

The addition of benzenesulphenanilides to alkenes in the presence of boron trifluoride provides a practicable synthetic procedure for the arylaminosulphenylation of alkenes.