5909-75-1Relevant academic research and scientific papers
Zirconium Catalyzed or Mediated Regioselective C-C Bond Formation Reactions of α,β-Unsaturated Acetals
Takahashi, Tamotsu,Kondakov, Denis Y.,Suzuki, Noriyuki
, p. 259 - 262 (1994)
Zirconium-alkyne complexes or zirconacyclopentenes, which are easily prepared in situ from alkynes, reacted with acrolein diethylacetal to afford vinyl ether derivatives.The C-C bond formation proceeded exclusively at β-position of the α,β-unsaturated acetal.Zirconium catalyzed C-C bond formation reactions of α,β-unsaturated acetals with EtMgBr also proceeded at β-position exclusively.
Living and Alternating Cationic Copolymerization of o-Phthalaldehyde and Various Bulky Enol Ethers: Elucidation of the "Limit" of Polymerizable Monomers
Hayashi, Keisuke,Kanazawa, Arihiro,Aoshima, Sadahito
, p. 1365 - 1375 (2022/02/23)
Cationic copolymerization of various bulky enol ethers, which have been difficult to homopolymerize and/or copolymerize, was shown to proceed when o-phthalaldehyde (OPA) was used as a comonomer. A series of enol ethers with various substituents on the β-carbon was synthesized from aliphatic aldehydes and alcohols. The relationships between the structures of the enol ethers and the copolymerization behavior were systematically investigated. As a result, monomers with one or two methyl and/or primary alkyl groups on the β-carbon were found to undergo alternating copolymerization with OPA. Moreover, living cationic copolymerization of enol ethers and OPA yielded alternating copolymers under appropriate polymerization conditions. To elucidate the limit of polymerizable monomers, the copolymerization of very bulky enol ethers such as β-t-butyl- or norbornenylidene-type monomers with OPA was also examined. OPA was found to be copolymerizable even with such very bulky monomers, indicating that the unique reactivity of the OPA-derived propagating carbocation with small steric hindrance is the key factor for successful copolymerization.
1H and 13C NMR Spectra of 2-Halo-2-alkenals and Their Acetals
Rulev, A. Yu.,Mokov, A. S.,Krivdin, L. B.,Keiko, N. A.,Voronkov, M. G.
, p. 1465 - 1469 (2007/10/03)
The electronic structure of a series of 2-halo-2-alkenals R2(R1)C=CXCHO and their acetals R2(R1)C=CXCH(OR3)2 is studied by 1H and 13C NMR spectroscopy.In the molecules of 2-fluoro-2-alkenals the electron density of the double bond is shifted toward the β-carbon atom.In contrast, in isostructural 2-chloro- and 2-bromo-2-alkenals the most probable centers of a nucleophilic attack are the β-carbon atom of the double bond and the carbonyl carbon atom.Owing to the lower acceptor power of the acetal group as compared to the aldehyde group, the reactivity of the double bond in acetals is decreased, and the direction of its polarization is the same as in haloalkenes.
