19207-89-7

Upstream product

• 75-18-3 dimethylsulfide 
• 43084-97-5 tert-butyl perester of 4-methoxybenzoic acid 
• 72818-30-5 Anisoyl-4-tolylsulfon 
• 67-68-5 dimethyl sulfoxide 
• 100-07-2 4-methoxy-benzoyl chloride 
• 100-09-4 4-methoxybenzoic acid 

Relevant academic research and scientific papers

On the development of a nucleophilic methylthiolation methodology

Methylthiolation reactions are usually explored to access organosulfur compounds using methanethiol, an extremely flammable and toxic compound. Herein, methylthiomethyl esters were successfully applied as novel methylthiolation reagents in a low cost, transition-metal-free methodology. These reagents allowed the methylthiolation of a wide scope of chalcones, acyl ester derivatives and Morita-Baylis-Hillman acetates with good group tolerance, affording the methylthiolated products in moderate to excellent yields. The reaction mechanism was investigated through several control experiments, as well as by theoretical calculations employing Density Functional Theory. The results strongly support that a sulfurane and a sulfonium ylide appear as key intermediates and that a Pummerer type rearrangement is also crucial for the formation of this novel reagent. Furthermore, the methylthiolation mechanism is likely to proceed through the nucleophilic attack of the reagent, followed by an entropically favoured step involving the acetate attack to the positively charged species, then releasing the product. This journal is

Synthetic method of methylthiomethyl

The invention provides a synthetic method of methylthiomethyl. The synthetic method comprises the step of carrying out crossed dehydrogenation on a carboxylic acid compound and dimethylsulfoxide in the presence of nitrogen and organic amine, so as to gene

Facile synthesis of methylthiomethyl esters through Pummerer-type rearrangement of carboxylic acids and DMSO under metal-free conditions

A green and cost-effective Pummerer-type rearrangement between readily accessible carboxylic acids and DMSO has been achieved under metal-free conditions in satisfactory to excellent yields. The transformation for the synthesis of valuable methylthiomethy

Fe2O3-catalyzed Pummerer rearrangement of acyl chlorides and sulfoxides: Facile synthesis of alkylthiomethyl ester

A simple, effective approach for the Pummerer rearrangement of acyl chlorides with sulfoxides by using a low-cost and more abundant Fe catalyst has been described. The alkylthiomethyl ester products were prepared in good to excellent yields for a range of different substrates including asymmetrical sulfoxides and acyl chlorides with a variety of functional groups under mild reaction conditions. The reaction features short reaction time, simple manipulation, cheap reagents and a broad substrate scope. Single crystal X-ray analysis of a representative methylthiomethyl (MTM) group containing product was also reported.

Electron transfer reactions (ETR) of tert-butyl perbenzoates with dimethyl sulfide: The rates controlled by translational entropy

Various tert-butyl perbenzoates were prepared according to the known methods. The mixtures of tert-butyl perbenzoate and dimethyl sulfide underwent thermolysis at several temperatures (T°C: 80, 90, 100, and 110). The rates of consumption of the peresters (kobs) were obtained from In C 0/Ct = kobs × t where Co and Ct are the concentration of the perester at time 0 and t, respectively. For example: The decrease of the perester satisfied pseudo first order kinetics, and kobs were determined. kHom. and k ET were obtained from kobs = kHom. + k ET[CH3SCH3] where [CH3SCH 3]/[perester] > 10. kET and its relative rates are produced from plot of kobs against [CH3SCH3]. Hammett correlation are plotted against σ and σ+ in which σ is better correlated than σ+. Hammett ρ could be considered selectivity which stays constant irrespective of temperature. The phenomenon is not consistent with reactivity/selectivity principle. The differential activation entropies linearly increase with substituent constant σ to give slope of 2.63 while the similar slope for differential enthalpies shows much lower value of 0.892. The dominance of differential entropic terms clearly indicates the entropy control of the rates. Copyright

REACTION OF NUCLEOPHILES WITH ELECTRON ACCEPTORS BY SN2 OR ELECTRON TRANSFER (ET) MECHANISMS: TERT-BUTYL PEROXYBENZOATE/DIMETHYL SULFIDE AND BENZOYL PEROXIDE/N,N-DIMETHYLANILINE SYSTEMS.

This study is one of a series that probes the reactions of nucleophiles with peroxides, reactions that can occur either by an initial S//N2 reaction or by an electron-transfer (ET) reaction. The products and kinetics are reported for the reaction of dimethyl sulfide and a series of ring-substituted aryl methyl sulfides with tert-butyl peroxybenzoate (TBP) and four ring-substituted TPB's. Kinetic analysis allows the separation of the rate constants for unimolecular homolysis (k//1) and those for the decomposition of the TBP by the sulfide (k//2). The bimolecular reaction is accelerated by electron-withdrawing substituents in the TBP; for example, when 3,5-(NO//2)//2-TBP is used, k//2/k//1 is 12,000. The products that are formed are consistent with a radical process; however, this evidence is not regarded as conclusive.

α-Oxosulfones, 3. - Reactions of Acyclic α-Oxosulfones

The course of reactions of acyclic α-oxosulfones with protic and aprotic nucleophiles is described.A far-reaching analogy to reactions of acyl halides is noticed.