79597-54-9

Upstream product

• 108-98-5 thiophenol 
• 513-81-5 2,3-dimethyl-buta-1,3-diene 
• 79597-63-0 2-Chlor-2,3-dimethyl-1-(phenylthio)butan 
• 79597-70-9 (1-Chloromethyl-1,2-dimethyl-propylsulfanyl)-benzene 
• 563-78-0 2,3-Dimethyl-1-butene 
• 931-59-9 benzenesulfenyl chloride 
• 101384-19-4 2-Chloro-2,3-dimethyl-1-phenylthiobut-3-ene 
• 666833-85-8 1-Chloro-2,3-dimethyl-4-phenylthiobut-2-ene 
• 180078-61-9 2,3-Dimethyl-1-phenylsulfanyl-butan-2-ol 
• 4985-62-0 phenylthiyl 
• 563-80-4 3-methyl-butan-2-one 
• 100-68-5 methyl-phenyl-thioether 
• 563-79-1 2,3-Dimethyl-2-butene 
• 882-33-7 diphenyldisulfane 

Downstream Products

• 101384-22-9 1-(phenylsulfinyl)-2,3-dimethyl-2-butene 
• 84602-85-7 1-(phenylsulfonyl)-2,3-dimethyl-2-butene 
• 114597-56-7 2-Methyl-3-phenylsulfanylmethyl-but-3-en-2-yl-hydroperoxide 
• 114597-57-8 (S)-2,3-Dimethyl-1-phenylsulfanyl-but-3-en-2-yl-hydroperoxide 
• 267668-32-6 N-tert-butyloxycarbonyl-N-(1,1,2-trimethyl-2-propenyl)benzenesulfenamide 
• 563-79-1 2,3-Dimethyl-2-butene 

Relevant academic research and scientific papers

Reactions of benzeneselenyl and benzenesulfenyl chlorides with syn-and anti-9-9′-bibenzonorbornenylidenes

Reaction of syn-9,9′-bibenzonorbornenylidene (1a) with benzeneselenyl chloride produced vic-dichloride (4) exclusively, which corresponds to the cis-addition product of 1a with molecular chlorine, with retention of the original alkene configuration. Moreo

Direct Allylic C(sp3)-H Thiolation with Disulfides via Visible Light Photoredox Catalysis

In spite of the wide utility of allyl thioethers, the direct catalytic allylic C(sp3)-H thiolation remains elusive. Herein, we report the direct allylic C(sp3)-H thiolation mediated by visible light photoredox catalysis. The use of in situ-generated thiyl radical from disulfide as a hydrogen atom transfer (HAT) reagent and a coupling partner enabled selective cleavage of the allylic C(sp3)-H bond followed by C(sp3)-S bond formation. The undesired hydrothiolation, a prevalent reaction from facile thiyl radical addition to olefins, was prevented by the immediate deprotonation of thiol under basic conditions. A wide range of diaryl disulfides and olefins participated in the reaction, producing allyl thioethers with high efficiency. Mechanistic investigations revealed the participation of the photocatalyst as a redox mediator, which was crucial for the transformation of the allyl radical into the allyl cation and further ionic coupling process. Based on the proposed mechanism, a limitation in the synthesis of alkyl allyl sulfide was solved with a rationally designed more reducible unsymmetrical disulfide, which makes the desired catalytic cycle operative.

Novel photoinduced reduction of conjugate dienes by the combination of benzenethiol and diphenyl diselenide

By using a binary system that consisted of benzenethiol and diphenyl diselenide under photoirradiation through a Pyrex vessel with a xenon lamp (λ > 300 nm), a variety of conjugate dienes could be reduced to the corresponding internal alkenes under mild conditions.

Photochemical reactions of thiols with organic nitrates - Oxygen atom transfer via a thionitrate

Nitroglycerin is an organic nitrate that has been used in the clinical treatment of angina for 130 years, yet important details of its mechanism of action remain unanswered. The biological activity of nitrates suggests that they are bioactivated to NO via a three-electron reduction. The involvement of free or bound protein thiols in this reduction has often been proposed. To examine the involvement of thiyl radicals in such a process, the photochemical generation of benzenethiyl radical from thiol and disulfide precursors was studied in the presence of isopropyl nitrate. Analysis of reaction products and kinetics led to the conclusion that photolysis of the nitrate to NO2 dominated the observed photochemistry. Formation of sulfonothioate and NO as products, and trapping of NO2 by 4-chlorophenol, indicated a mechanism involving oxygen atom transfer from N to S via a thionitrate intermediate. The results of the study did not indicate a rapid reaction between thiyl radical and organic nitrate. Despite weak nitrate absorption of light >300 nm and a relatively high BDE for homolysis to give NO2, the photochemistry under thiyl-generating conditions was driven by nitrate photolysis to NO2. A novel nitrate, containing a phenyl disulfanyl group linked to nitrate groups, did not undergo photolysis to NO2 or generate sulfonothioate, but did yield NO. These observations suggest that reaction between thiyl radicals and nitrates leading to NO release is a viable pathway, but it is subservient to other competing reactions, such as photolysis, in the case of IPN, and reaction with thiolate, in the case of the novel nitrate.

Fe(II)-catalyzed imidation of allyl sulfides and subsequent [2,3]- sigmatropic rearrangement. Preparation of α-branched N-tert-butyloxycarbonyl (Boc)-protected N-allylamines

Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]- sigmatropic rearrangement reaction upon treatment with N-tert- butyloxycarbonyl azide (BocN3) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples). Whereas the reaction is well suited for the transformation of α-unbranched sulfides to α-branched sulfenamides, the enantiomerically pure α-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% ee). A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of α- branched amines that bear a secondary allyl substituent (five examples, 71- 93% yield). This method failed for the α-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)3/NEt3 in CH2Cl2 (three examples, 43-62% yield).

Selective Functionalisation of 1,3-Dienes via Organosulphur Intermediates

The 1,2-adducts from 1,3-dienes and sulphenyl chlorides are shown to be useful intermediates by their conversions into a variety of functionalised alkenes.

Synthesis of Allyl Thioethers

Addition of C6H5SCl to alkenes 8, 10, and 14 yields allyl thioethers 9, 11, and 15 + 16 after thermolysis at 120 - 200 deg C.Vinyl thioethers are not observed.The influence of substituents R1 and R2 on the regioselectivity (Table 1) and the rate of the elimination (Table 2) is examined.