51738-09-1Relevant articles and documents
Synthesis of Unsymmetrical 1,4-Dicarbonyl Compounds by Photocatalytic Oxidative Radical Additions
Dong, Ya,Li, Ruining,Zhou, Junliang,Sun, Zhankui
supporting information, p. 6387 - 6390 (2021/08/23)
Herein we report a photocatalytic oxidative radical addition reaction for the synthesis of unsymmetrical 1,4-dicarbonyl compounds. This reaction utilizes a desulfurization process to generate electrophilic radicals, which add to α-halogenated alkenes and undergo further oxidation to deliver 1,4-dicarbonyl compounds. This mild and highly efficient method provides a valuable alternative to known strategies.
Reaction of phenylenedioxytrihalogenophosphoranes with arylacetylenes. Synthesis and spatial structure of the derivatives of 2-oxo-4-aryl-5,6-benzo-1,2-oxaphosphorin-2-enes
Mironov, Vladimir F.,Gubaidullin, Aidar T.,Petrov, Ravil R.,Litvinov, Igor A.,Shtyrlina, Alfiya A.,Zyablikova, Tatyana A.,Azancheev, Nail M.,Konovalov, Alexander I.,Musin, Rashid Z.
, p. 377 - 380 (2007/10/03)
New method of synthesis of six-membered heterocycles - 2-R-2-oxo-4-aryl-2H-benzo[e][1,2]-oxaphosphorin-3-enes has been developed. It includes the interaction of arylenedioxy trihalogenophosphoranes with arylacetylenes. The formation of phosphoryl group and P-C bond, ipso-substitution of the aromatic oxygen and halogenation of the benzene ring take place in this unusual reaction. The influence of the phosphorane structure on synthetic result is discussed. If both para positions at benzene ring of the phosphorane are occupated by halogens, the evolving of halogen molecule occurs. The structures of 2-R-2-oxo-4-aryl-2H-benzo[e][1,2]-oxaphosphorin-3-enes are determined by X-ray analysis.
Vinylcations, 39. Zinc Chloride Catalysed Addition of Hydrogen Chloride to Cyclopropylalkynes
Hanack, Michael,Weber, Erhard
, p. 777 - 797 (2007/10/02)
Zinc chloride catalysed addition of hydrogen chloride to 1-cyclopropylalkynes 5a-e (R = CH3, c-C3H5, phenyl, p-tolyl, 4-methoxyphenyl) is studied and the results are compared with those of the addition of HCl/ZnCl2 to several substituted arylalkynes 10a-h.Thus, the alkynes are reacted with HCl/ZnCl2 in dichloromethane and the reaction products are investigated also with respect to their stereochemistry.All alkynes yield predominantly the direkt hydrogen chloride addition products.The 1-cyclopropylalkynes 5a-d give (E)-1-chloro-1-cyclopropyl-1-alkenes 15, and (E)-1-chloro-2-cyclopropyl-1-(4-methoxyphenyl)ethene (16e) is obtained as the major product from 5e (R = 4-CH3OC6H4).Moreover, ring opening to homoallenyl chlorides 19 and, as a side reaction, formation of the ketones 17 and 18 by the addition of water are observed.In a secondary addition reaction, the dichlorides 20 are also obtained by homoallyl rearrangement.The arylalkynes 10a-g react preferentially with formation of (E)-1-aryl-1-chloroalkenes 21.Relative rates are obtained by inter- and intramolecular competition reactions of the alkynes 23 and 5b-e with HCl/ZnCl2 showing the order of stabilization by substituents of the intermediate vinyl cation 2 to be 4-ClC6H4 E2 mechanism.The preferential formation of the addition products E-15, E-16, and E-21 is attributed to a syn-vinyl cation ion pair and to steric approach control of the β-substituents in the vinyl cation intermediate 2.
