100716-85-6

Upstream product

• 10486-08-5 sodium p-thiocresolate 
• 104-83-6 1-Chloro-4-(chloromethyl)benzene 
• 106-45-6 para-thiocresol 
• 873-76-7 para-Chlorobenzyl alcohol 
• 19350-69-7 4-chlorobenzaldehyde p-toluenesulfonylhydrazone 
• 622-95-7 4-chlorobenzyl bromide 
• 74-11-3 para-chlorobenzoic acid 
• 17530-79-9 1-chloro-4-((p-tolylsulfinyl)methyl)benzene 
• 1126-46-1 Methyl 4-chlorobenzoate 
• 624-31-7 4-tolyl iodide 
• 6258-66-8 (4-chlorophenyl)methanethiol 
• 874-72-6 4-chlorobenzylmagnesium chloride 
• 2943-42-2 di(4-methyl)phenylthiosulfonate 
• 51044-12-3 (4-chlorobenzyl)triphenylphosphonium bromide 

Downstream Products

• 1372784-01-4 (E)-methyl 3-{5-chloro-2-(p-tolylthiomethyl)phenyl}acrylate 
• 1372784-03-6 (E)-butyl 3-{5-chloro-2-(p-tolylthiomethyl)phenyl}acrylate 
• 20025-45-0 1--1--2-phenyl-aethan 
• 17530-79-9 1-chloro-4-((p-tolylsulfinyl)methyl)benzene 
• 20025-49-4 4-chlorobenzyl 4'-methylphenyl sulfone 

Relevant academic research and scientific papers

ZrCl4 dispersed on dry silica gel provides a useful reagent for S-alkylation of thiols with alcohols under solvent-free conditions

ZrCl4 which is commercially available and not a costly compound, is a relatively safe chemical [LD50 [ZrCl4, oral rat] = 1688 mg Kg]. In this report we describe the use of ZrCl4 dispersed on dry silica gel as an efficient reagent for the efficient preparation of thioethers from thiols with alcohols under solvent-free conditions.

Unusual Application for Phosphonium Salts and Phosphoranes: Synthesis of Chalcogenides

A novel strategy for the synthesis of sulfides and selenides from phosphonium salts and thio- or selenesulfonates, commercially available compounds, is described. When phosphoranes were used in the reaction, different products were obtained. The methodology does not require the use of metals, reactive species, or anhydrous conditions to be performed.

Synthesis of benzyl sulfidesviasubstitution reaction at the sulfur of phosphinic acid thioesters

An ambident electrophilicity of phosphinic acid thioesters is disclosed. Unexpected carbon-sulfur bond formation took place in the reaction between phosphinic acid thioesters and benzyl Grignard reagents. The developed method for benzyl sulfides has a wide substrate scope and was applicable for the synthesis of a drug analog.

Efficient dehydrative alkylation of thiols with alcohols catalyzed by alkyl halides

Alcohols can be efficiently converted into the useful thioethers by a transition metal- and base-free dehydrative S-alkylation reaction with thiols or disulfides by employing alkyl halides as the effective catalyst. This simple and efficient method is a green and practical way for the preparation of thioethers, as it tolerates a wide range of substrates such as aryl and alkyl thiols, as well as benzylic, allylic, secondary, tertiary, and even the less reactive aliphatic alcohols.

Photoredox Mediated Nickel Catalyzed Cross-Coupling of Thiols with Aryl and Heteroaryl Iodides via Thiyl Radicals

Ni-catalyzed cross-couplings of aryl, benzyl, and alkyl thiols with aryl and heteroaryl iodides were accomplished in the presence of an Ir-photoredox catalyst. Highly chemoselective C-S cross-coupling was achieved versus competitive C-O and C-N cross-couplings. This C-S cross-coupling method exhibits remarkable functional group tolerance, and the reactions can be carried out in the presence of molecular oxygen. Mechanistic investigations indicated that the reaction proceeded through transient Ni(I)-species and thiyl radicals. Distinct from nickel-catalyzed cross-coupling reactions involving carbon-centered radicals, control experiments and spectroscopic studies suggest that this C-S cross-coupling reaction does not involve a Ni(0)-species.

Indium-Catalyzed Reductive Sulfidation of Esters by Using Thiols: An Approach to the Diverse Synthesis of Sulfides

A new reductive preparation of unsymmetrical sulfides from esters and thiols in the presence of InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 as the reductant was developed. This protocol was applied to not only benzoic acid esters that have a methoxy, methyl, chloro, bromo, iodo, or trifluoromethyl group on the aromatic ring but also aliphatic acid esters with either aromatic or aliphatic thiols. A reaction mechanism is proposed by using Hammett plot results and several control experiments. The reductive preparation of unsymmetrical sulfides from esters and thiols by using InI3 and either 1,1,3,3-tetramethyldisiloxane (TMDS) or PhSiH3 was developed. Several mechanistic studies support that the present transformation proceeds through O,S-and S,S-acetals as the reaction intermediates. TMDS = 1,1,3,3-tetramethyldisiloxane, R = aliphatic group.

A novel method for the reduction of sulfoxides with the N, N, N g, N g-tetrabromobenzene-1,3-disulfonamide (TBBDA)/PPh3 system

A new method is described for the reduction of sulfoxides to sulfides using N,N,N',N'-tetrabromobenzene-1,3-disulfonamide [TBBDA] in combination with triphenylphosphine. Good to excellent yields, short reaction times, high efficiency and facile isolation of the desired products are the advantages of this method.

Synthesis of sulfur-bridged polycycles via Pd-catalyzed dehydrogenative cyclization

A general approach to sulfur-bridged polycycles by palladium-catalyzed double C(sp2)-H bond oxidative cyclization is presented. This protocol afforded diverse sulfur-bridged five-, six-, and seven-membered polycycles in moderate to good yields with a tolerance for a wide variety of functional groups. A sulfide-bridged six-membered pyrene-thienoacene compound was synthesized readily using this method, and excellent performance for photoluminescence quantum yield was observed.

Single-step thioetherification by indium-catalyzed reductive coupling of carboxylic acids with thiols

Direct thioetherification from a variety of aromatic carboxylic acids and thiols using a reducing system combined with InBr3 and 1,1,3,3-teramethyldisiloxane (TMDS) in a one-pot procedure is demonstrated. It was also found that a system combine

Palladium-catalyzed C-H alkenylation of arenes using thioethers as directing groups

Thioethers have been proven to be reliable directing groups for palladium catalyzed alkenylation of arenes via C-H activation. Mechanistic investigation reveals that the C-H cleavage of arenes is the turnover-limiting step, and an acetate-bridged dinuclear cyclopalladation intermediate is involved. The alkenylated thioethers can be easily removed and transformed into a variety of useful groups.