37434-59-6Relevant articles and documents
Reactions of dimethoxycarbene with carbon-sulfur double bonds
Dawid, Malgorzata,Reid, Darren L.,Warkentin, John,Mloston, Grzegorz
, p. 86 - 89 (2005)
Unlike electrophilic carbenes, which react at sulfur to produce thiocarbonyl ylide intermediates, dimethoxycarbene (DMC), generated by thermolysis of an oxadiazoline at 110°C in benzene in a sealed tube, reacts at carbon, possibly to generate a zwitterionic intermediate, or at both carbon and sulfur in a concerted process that generates a thiirane. In case of the strained 2,2,4,4-tetramethylcyclobutane-1,3-dithione (2), an assumed zwitterion undergoes ring expansion. In analogous reactions, unstrained thiones afford thiiranes, possibly by ring closure of the postulated intermediates or by concerted addition. Desulfurization of thiiranes, which occurs spontaneously in some instances, results in the formation of ketene acetals, many of which hydrolyze during workup. O-Alkyl thioesters and xanthates react to afford products via insertion of the DMC into Csp2-O or Csp2-S bonds, respectively. Copyright
Preparation method of penta-deuterium atom substituted 2-thiophenobarbital
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Paragraph 0021-0022, (2021/07/08)
The invention discloses a preparation method of penta-deuterium atom substituted 2-thiophenobarbital, and belongs to the field of organic synthesis and analysis detection. The preparation method comprises the steps that the penta-deuterium atom substituted 2-thiophenobarbital is prepared from methyl malonate as a raw material through Friedel-Crafts alkylation reaction, cyclization reaction and nucleophilic substitution reaction, separation and purification. The prepared deuterated 2-thiophenobarbital has the advantages of high chemical purity, stable deuterium atoms and the like. The method disclosed by the invention is simple to operate, high in yield and low in cost. The invention not only provides a synthesis method of penta-deuterium atom substituted 2-thiophenobarbital with independent intellectual property rights, but also provides a deuterated internal standard substance for analysis and detection.
Radical Addition Enables 1,2-Aryl Migration from a Vinyl-Substituted All-Carbon Quaternary Center
Li, Zexian,Shi, Zhuangzhi,Wang, Minyan
supporting information, p. 186 - 190 (2020/11/02)
An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed. The rearrangement reactions use fac-Ir(ppy)3, visible light and commercially available fluoroalkyl halides and can generate valuable multisubstituted perfluoroalkylated compounds in a single step that would be challenging to prepare by other methods. Mechanistically, the photoinduced alkyl radical addition to an alkene leads to the migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center with the concomitant generation of a C-radical bearing two electron-withdrawing groups that is further reduced by a hydrogen donor to complete the domino sequence.
UV-mediated decomposition of diazomalonates in benzene: Unexpected access to functionalized bicyclo[3.2.0]heptane skeleton
Chiang, Yi-Jung,Zhu, Jia-Liang
supporting information, p. 3081 - 3084 (2017/07/17)
Upon irradiation with 300-nm UV light, the photolysis of diazomalonates in benzene unexpectedly affords 2,6-dicarboxylate bicyclo[3.2.0]hepta-2,6-dienes in low yields. These products are proven to be derived from cyclohepta-1,3,5-triene intermediates presumably via a tandem 1,5-carboxylate migration/[2+2] cycloaddition sequence.
