75280-06-7

Upstream product

• 82751-11-9 diethyl (methylsthio)phenylmalonate 
• 4455-14-5 ethyl 2-(methylsulfinyl)acetate 
• 71-43-2 benzene 
• 32368-19-7 1,2-diphenyl-2-methylthio-1-ethanone 
• 101-97-3 Ethyl 2-phenylethanoate 
• 74-93-1 methylthiol 
• 2882-19-1 ethyl 2-phenyl-2-bromoacetate 
• 145628-18-8 ethyl 2-chloro-2-methylthio-acetate 
• 5188-07-8 sodium thiomethoxide 

Downstream Products

• 35809-43-9 Phenyl-(α-methylthio)acetaldehyd 
• 97611-71-7 ethyl α-phenyl-3,4-dimethoxyphenylacetate 
• 97611-73-9 2-(3,4-dimethoxyphenyl)-2-phenylpropionic acid 
• 97611-77-3 2-(3,4-Dimethoxy-phenyl)-N-methyl-2-phenyl-propionamide 
• 97611-72-8 2-(3,4-Dimethoxy-phenyl)-2-phenyl-propionic acid ethyl ester 
• 97611-54-6 1,2,3,4-terahydro-6,7-dimethoxy-2,4-dimethyl-4-phenylisoquinoline 
• 97611-85-3 6,7-Dimethoxy-2,4-dimethyl-4-phenyl-1,4-dihydro-2H-isoquinolin-3-one 
• 97611-70-6 ethyl α-methylthio-α-phenyl-3,4-dimethoxyphenylacetate 
• 1603-79-8 phenylglyoxylic acid ethyl ester 
• 141869-55-8 ethyl α,α-bis(methylthio)phenylacetate 
• 774-40-3 hydroxy-phenyl-acetic acid ethyl ester 
• 1521187-12-1 ethyl methylsulfinylphenylacetate 
• 2248-46-6 ethyl 2,2-difluoro-2-phenylacetate 
• 101-97-3 Ethyl 2-phenylethanoate 

Relevant academic research and scientific papers

On the thermal Pummerer rearrangement of substituted sulfoxides

Sulfoxides bearing thioester and ester groups at the position under heating at ca. 140C undergo Pummerer thermal rearrangement. However, for sulfonyl sulfoxide, a complex mixture of products is formed. Plausible mechanism is advanced(equation presented. 2013

Rhodium-catalyzed α-methylthiolation reaction of unactivated ketones using 1,2-diphenyl-2-methylthio-1-ethanone for the methylthio transfer reagent

In the presence of catalytic amounts of RhH(PPh3)4, 1,2-bis(diphenylphosphino)ethane (dppe), and dimethyl disulfide, ketones without α-activating groups were α-methylthiolated with 1,2-diphenyl-2-methylthio-1-ethanone giving α-methylthio ketones. The reaction of unsymmetrical ketones proceeded at the more substituted carbons. The initial formation of kinetic α-methylthiolated products followed by their rearrangement to thermodynamic products was observed in the reaction of α-phenyl ketones. Aldehydes, phenylacetate, and phenylacetonitrile were also α-methylthiolated under these conditions.

SYNTHESIS OF SUBSTITUTED TRANS-1,6-DIMETHYLBICYCLONON-2-ENES USING A CLAISEN REARRANGEMENT OF α-(THIOALKOXY)ESTERS

The Claisen rearrangement of α-(thioalkoxy)esters provided access to substituted trans-1,6-dimethylbicyclonon-2-enes characteristic of the CD rings of the cucurbitanes.

MILD REACTION OF PUMMERER REARRANGEMENT PRODUCTS WITH AROMATIC COMPOUNDS IN THE PRESENCE OF LEWIS ACIDS. APPLICATION TO THE PREPARATION OF ARYLMETHYLENE KETONES, ARYLACETOESTERS, AND ARYLACETONITRILES.

Pummerer intermediates generated from precursors (3), (4) and (5) reacted mildly with aromatic compounds in the presence of Lewis acids to give the corresponding sulfides which in turn desulfurized to arylmethylene ketones, arylacetoesters, and arylaceton

A Convenient Method for Preparation of 2-(Methylthio)alkanoic Acids and Their Related Compounds Using the Carbanions of Substituted Malonic Esters

Starting from alkyl- or aryl-substituted malonic esters prepared by various methods, 2-(methylthio)alkanoic acids are synthesized by successive treatment with sodium ethoxide and with S-methyl methanethiosulfonate, followed by alkaline hydrolysis which causes concurrent decarboxylation.Production of 2-(phenylthio)alkanoic acids is also achieved in a similar manner.

Synthesis of Ethyl Arylacetates by Means of Friedel-Crafts Reaction of Aromatic Compounds with Ethyl α-Chloro-α-(methylthio)acetate

Friedel-Crafts reaction of aromatic compounds with ethyl α-chloro-α-(methylthio)acetate (1) gave ethyl α-(methylthio)arylacetates (2), which were readily converted into ethyl arylacetates (3) by reductive desulfurization with Raney nickel or zinc dust-acetic acid.The reactions were applied to the syntheses of ibufenac (5) and alclofenac (6), which are anti-inflammatory agents.

ELECTROPHILIC AROMATIC SUBSTITUTION BY PUMMERER REACTION OF α-SULFINYLACETATE

Treatment of a mixture of aromatic compound and ethyl α-(methylsulfinyl)acetate (5) with p-toluenesulfonic acid under continuous removal of separated water brought about an intermolecular aromatic substitution to give ethyl α-(methylthio)arylacetate (6).S

Introduction of α-(acyl) methylthiomethyl group into the aromatic ring by Friedel-Crafts reaction

Friedel-Crafts α-(acyl)methylthiomethylations of aromatic compounds with α-ethoxycarbonyl, -acetyl, -benzoyl, and -cyano-α-(methylthio)methyl chlorides are described. The resulted products are easily converted to acylmethylated aromatics such as phenylacetate and phenylacetone by reductive desulfurization.