24165-91-1Relevant academic research and scientific papers
A fast and selective decarboxylative difunctionalization and cyclization for easy access to gem-dihalo alcohol, ether, ester and bromo-1,4-dioxane
Khamarui, Saikat,Sarkar, Deblina,Pandit, Palash,Maiti, Dilip K.
supporting information; experimental part, p. 12667 - 12669 (2012/01/03)
A general strategy for fast decarboxylative difunctionalization to gem-dihalohydrin, gem-dihaloether, gem-dibromoester and cyclized bromo-1,4-dioxane synthons with outstanding regio- and stereoselectivity is demonstrated. The Royal Society of Chemistry 20
Methoxide-induced fragmentation of 2,2,3-trihalogeno- and 2,2-dihalogeno-3-methoxy-1,3-diphenylpropanones
Montani, Rosana S.,Garay, Raul O.,Cabaleiro, Mercedes C.
, p. 1125 - 1130 (2007/10/02)
The reaction of 2,2,3-trihalogeno-1,3-diphenylpropanones with sodium methoxide in methanol occurs with exclusive formation of fragmentation products.Kinetic and stereochemical evidence is interpreted in terms of a concerted intramolecular process promoted by initial attack of methoxide anion at the carbonyl carbon.In the case of 2,2-dihalogeno-3-methoxy-1,3-diphenylpropanones the reaction gives fragmentation, rearrangement, and elimination products.The former products are believed to be formed through competing reactions involving an intermediate formed on addition of methoxide to the substrate.For the fragmentation pathway the results are consistent with a carbanionic-intermediate mechanism.
Oxyanionic Substituent Effect on the C-H Insertion of Carbenes. Reaction of Alkoxides with Dichlorocarbene and Chlorophenylcarbene
Harada, Toshiro,Akiba, Eiji,Oku, Akira
, p. 2771 - 2776 (2007/10/02)
The lithium alkoxides of benzylic, allylic, and simple alkyl alcohols were allowed to react with chloroform in the presence of t-BuOLi in THF-hexane to give, in 32-91percent yields, dichloromethylcarbinols, which were produced by the insertion of dichlorocarbene into the α C-H bond of alkoxides but not by the Wittig rearrangement of carbanions of alkyl dichloromethyl ethers.The enhanced reactivity toward dichlorocarbene of the α C-H bond of alkoxides was clearly demonstrated by the high selectivity of the insertion.The potassium alkoxides of a series of analogous alcohols reacted analogously with benzal chloride in the presence of t-BuOK in THF to give the corresponding substituted oxiranes (16-79percent); e.g., the reaction of potassium benzyl oxide gave 2,3-diphenyloxirane (79percent) as a mixture of stereoisomers (trans:cis = 1.0).With 2-phenethoxide, n-octyl oxide, or 2-methoxyethoxide, the corresponding dialkyl acetals of benzaldehyde were also formed in 9, 6, and 6percent yield, respectively, and their formation is explained in terms of nucleophilic attack of alkoxide on chlorophenylcarbene.With trans-crotyl oxide or 2-phenetoxide, 1,3-diphenylpropan-1-one(33percent) and 1-phenylpent-3-en-1-one (6percent) were produced, respectively, as byproducts through the isomerization of the primary product oxiranes.Oxiranes were produced by the insertion of chlorophenylcarbene into the α C-H bond of alkoxides followed by the cyclization of the intermediate 1-substituted 2-chloro-2-phenethyl alkoxide.These reactions provide us with new preparative methods of synthetically useful dichloromethyl carbinols and oxiranes.
NOVEL SELECTIVE SYNTHESIS OF α-CHLOROMETHYL, α,α-DICHLOROMETHYL, AND α,α,α-TRICHLOROMETHYL KETONES FROM ALDEHYDE UTILIZING ELECTROREDUCTION AS KEY REACTIONS
Shono, Tatsuya,Kise, Naoki,Yamazaki, Akira,Ohmizu, Hiroshi
, p. 1609 - 1612 (2007/10/02)
A variety of α-chloromethyl, α,α-dichloromethyl, and α,α,α-trichloromethyl ketones were synthesized from aldehyde utilizing cathodic reduction as key reactions.
