13026-23-8Relevant articles and documents
Intramolecular Electron Transfer and SN2 Reactions in the Radical Anions of 1-(4-Biphenylyl)-ω-haloalkane Studied by Pulse Radiolysis
Kigawa, Hitoshi,Takamuku, Setsuo,Toki, Susumu,Kimura, Norio,Takeda, Seishi,et al.
, p. 5176 - 5179 (1981)
One-electron reduction of 1-(4-biphenylyl)-ω-haloalkane (BPX-n) by solvated electrons and the intramolecular reactions of the radical anion thus formed have been investigated using the pulse-radiolysis technique.The spectrum observed immediately after the pulse has an absorption maximum at 410 nm which is assigned to the corresponding biphenyl radical anion.The decay behavior of all these 410-nm bands follows first-order kinetics and the rates are dependent on the methylene chain length, n.With BPCl-0 and BPCl-2, which provide large rate constants (7.5E7 and 1.7E8 s-1, respectively) and large G values of 4-alkylbiphenyl formation, an intramolecular electron transfer from a biphenyl radical anion to a C-Cl bond is presumed.The rate constants of the radical anions decrease in the order BPCl-1 > BPCl-2 > BPCl-0 which is roughly parallel to the C-Cl bond energy of these compounds and does not correlate with the chain length n, which corresponds to the distance required for the electron transfer.On the other hand, in the case of BPCl-3 and BPCl-4, the decay of the 410-nm band decreased about two orders of magnitude (5.5E5 and 1.2E6 s-1, respectively) and was characterized by a simultanous formation of a 330-nm band which is assigned to a spirocyclic radical.The G values of the corresponding 4-alkylbiphenyl formation were low for these compounds.On the basis of these observations, an intramolecular carbanionic displacement of the biphenyl radical anion on the chlorine center, which is a novel type of intramolecular SN2 reaction, has been concluded.Intramolecular reactions of bromo and iodo derivatives were also investigated and compared with those of corresponding chlorides.
Dual Nickel/Ruthenium Strategy for Photoinduced Decarboxylative Cross-Coupling of α,β-Unsaturated Carboxylic Acids with Cycloketone Oxime Esters
Gao, Ang,Jiang, Run-Chuang,Liu, Chuang-Chuang,Liu, Qi-Le,Lu, Xiao-Yu,Xia, Ze-Jie
supporting information, p. 8829 - 8842 (2021/06/30)
Herein, a dual nickel/ruthenium strategy is developed for photoinduced decarboxylative cross-coupling between α,β-unsaturated carboxylic acids and cycloketone oxime esters. The reaction mechanism is distinct from previous photoinduced decarboxylation of α,β-unsaturated carboxylic acids. This reaction might proceed through a nickelacyclopropane intermediate. The C(sp2)-C(sp3) bond constructed by the aforementioned reaction provides an efficient approach to obtaining various cyanoalkyl alkenes, which are synthetically valuable organic skeletons in organic and medicinal chemistry, under mild reaction conditions. The protocol tolerates many critical functional groups and provides a route for the modification of complex organic molecules.
Method for preparing alpha, beta-unsaturated carboxylic acid compound
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Paragraph 0103-0104; 0479-0494, (2021/05/05)
The invention discloses a method for preparing an alpha, beta-unsaturated carboxylic acid compound, which comprises the following steps: 1) in an atmosphere containing carbon dioxide, heating and reacting a mixture containing hydrosilane and a copper catalyst to obtain a system I; and 2) adding a raw material containing alkyne and a nickel catalyst into the system I in the step 1), and heating to react. The method has the advantages of simple, easily available, cheap and stable raw materials, common, easily available and stable catalyst, mild reaction conditions, simple post-treatment, high yield and the like.