7304-68-9

Upstream product

• 13464-19-2 phenyl chlorothioformate 
• 124-40-3 dimethyl amine 
• 108-98-5 thiophenol 
• 79-44-7 N,N-Dimethylcarbamoyl chloride 
• 16906-70-0 phenyl N,N-dimethyl dithiocarbamate 
• 16241-04-6 O-phenyl N,N-dimethylthiocarbamate 
• 201230-82-2 carbon monoxide 
• 24380-79-8 S-phenyl-N,N-dimethylsulfenamide 
• 13509-36-9 S,S’-diphenyl dithiocarbonate 
• 108-95-2 phenol 
• 1005-56-7 phenylcarbonochloridothioate 
• 68-12-2 N,N-dimethyl-formamide 
• 882-33-7 diphenyldisulfane 
• 139-02-6 sodium phenoxide 

Downstream Products

• 108-98-5 thiophenol 
• 670-98-4 methyl benzenesulfinate 
• 2297-65-6 benzenesulfonyl bromide 
• 20320-27-8 N,N-dimethylcarbamoyl-phenylsulfone 
• 16906-70-0 phenyl N,N-dimethyl dithiocarbamate 

Relevant academic research and scientific papers

Visible-light-promoted synthesis of secondary and tertiary thiocarbamates from thiosulfonates andN-substituted formamides

A general visible-light-promoted metal-free synthesis of secondary and tertiary thiocarbamates starting from thiosulfonates andN-substituted formamides is developed. By employing rhodamine B as a photocatalyst andtert-butyl hydroperoxide (TBHP) as an oxidant, a wide scope of thiocarbamates can be obtained through direct thiolation of acyl C-H bonds under irradiation of blue light at room temperature for 12 h.

Iron(II)/Persulfate Mediated Newman-Kwart Rearrangement

Herein, we report that iron(II)/ammonium persulfate in aqueous acetonitrile mediates the Newman-Kwart rearrangement of O-aryl carbamothioates. Electron-rich substrates react rapidly under moderate heating to afford the rearranged products in excellent yie

Electrochemically Catalyzed Newman-Kwart Rearrangement: Mechanism, Structure-Reactivity Relationship, and Parallels to Photoredox Catalysis

The facilitation of redox-neutral reactions by electrochemical injection of holes and electrons, also known as "electrochemical catalysis", is a little explored approach that has the potential to expand the scope of electrosynthesis immensely. To systematically improve existing protocols and to pave the way toward new developments, a better understanding of the underlying principles is crucial. In this context, we have studied the Newman-Kwart rearrangement of O-arylthiocarbamates to the corresponding S-aryl derivatives, the key step in the synthesis of thiophenols from the corresponding phenols. This transformation is a particularly useful example because the conventional method requires temperatures up to 300 °C, whereas electrochemical catalysis facilitates the reaction at room temperature. A combined experimental-quantum chemical approach revealed several reaction channels and rendered an explanation for the relationship between the structure and reactivity. Furthermore, it is shown how rapid cyclic voltammetry measurements can serve as a tool to predict the feasibility for specific substrates. The study also revealed distinct parallels to photoredox-catalyzed reactions, in which back-electron transfer and chain propagation are competing pathways.

Mechanistic Investigations into the Cation Radical Newman-Kwart Rearrangement

Efforts to elucidate the governing factors in the cation radical Newman-Kwart rearrangement are described. Through a combination of spectroscopic and kinetic analyses, it has been shown that the reactive intermediate is a thione cation radical that has si

AlCl3-promoted thiolation of acyl C-H bonds with arylsulfonyl hydrazides

AlCl3-promoted thiolation of acyl C-H bonds with arylsulfonyl hydrazides was developed, which represents an effective synthesis of S-aryl thiocarbamates via C-S bond formation reaction.

Palladium-catalyzed insertion reactions of isocyanides into thiocarbamates and selenocarbamates

The insertion reaction of isocyanides with thiocarbamates and selenocarbamates in the presence of a Pd(0) catalyst to selectively give 2-oxoethanimidothioates and -selenoates is reported. This is the first example of the insertion of an isocyanide into a

Ambient-Temperature Newman-Kwart Rearrangement Mediated by Organic Photoredox Catalysis

The Newman-Kwart rearrangement is perhaps the quintessential method for the synthesis of thiophenols from the corresponding phenol. However, the high thermal conditions required for the rearrangement of the requisite O-aryl carbamothioates often leads to decomposition. Herein, we present a general strategy for catalysis of O-aryl carbamothioates to S-aryl carbamothioates using catalytic quantities of a commercially available organic single-electron photooxidant. Importantly, this reaction is facilitated at ambient temperatures.

Palladium-catalyzed intramolecular oxidative C-H sulfuration of aryl thiocarbamates

A palladium-catalyzed intramolecular C-H bond sulfuration reaction of aryl thiocarbamates has been developed. This strategy provides a new route to benzo[d][1,3]oxathiol-2-ones with tolerance of a wide range of substituents. Mechanistic studies suggested

Cu(OAc)Catalyzed Thiolation of Acyl C-H bonds with thiols using TBHP as an oxidant

Cu(OAc)promoted TBHP oxidative coupling reaction of formamides with thiols successfully proceeded through direct C-H bond activation of formamides. The corresponding S-phenyl dialkyl thiocarbamate compounds were formed with high yield under solvent-free c

Metal-free oxidative C(sp3)-H bond thiolation of ethers with disulfides

A novel method for the preparation of alkyl aryl sulfides through direct oxidation thiolation of commercial ethers with diaryl disulfides using di-tert-butyl peroxide (DTBP) as the oxidant without a metal catalyst was established. The C(sp3)-H