- Liberation of acrylates from nickelalactones via Ni─O ring opening with alkyl iodides
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The utilization of carbon dioxide as a feedstock for the production of raw chemicals is of high current industrial interest. One attractive reaction is the transformation of carbon dioxide into acrylic acid or acrylates. The cleavage of the Ni─O bond of nickelalactones may result in the formation of acrylates. In this work, C2H5I, CF3CH2I and CF3I are studied as alkylation reagents for the Ni─O ring opening of nickelalactones. The results indicate that both C2H5I and CF3CH2I are able to release acrylates from nickelalactones. Based on the experimental evidence and literature precedents, a mechanism – proceeding via Ni─O ring opening of nickelalactone, β-H elimination to release the acrylate and reductive elimination for recovery of the Ni(0) species – is proposed.
- Zhang, Zhizhi,Guo, Fangjie,Kühn, Fritz E.,Sun, Jing,Zhou, Mingdong,Fang, Xiangchen
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- The 'Baylis - Hillman reaction' mechanism and applications revisited
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It is shown that reaction of aryl, benzyl, alkyl and functionalised alkyl acrylic esters with benzaldehyde, in the presence of 1,4-diazabicyclo[2.2.2] octane, strongly depends upon the electronic and steric effects of the ester part. This influence is also observed in condensation of furfuraldehyde. Moreover, for the first time, it is shown that the overall condensation is equilibrated.
- Fort, Yves,Berthe, Marie Christine,Caubere, Paul
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p. 6371 - 6384
(2007/10/02)
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Several fluorinated and chlorofluorinated acrylates and methacrylates were synthesized from the alcohols RFCH2OH with RF=CCl3, CHClCH2CCl3, (CF2CFCl)nCl, (C2F4)nH, CF3, C7F15 and C6F13CH2. The corresponding polymers were also studied for their application as transparent polymeric materials. For this purpose the refractive indices n20D of the monomers and the polymers were measured as were the Tg values of the polymers. A study of their infrared spectra shows to what extent these products could be utilized taking into consideration their absorption in the long wavelength range between 0.85 and 1.50 m. The refractive indices of these polymers, which are reduced when increasing the number of fluorine atoms in the molecule, and that of the Tg measured between 50 and 70° C for the fluorinated methacrylates, indicate a potential use of these polymers as sheathing materials for optical fibres.
- Boutevin,Rigal,Rousseau,Bosc
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