16327-38-1Relevant articles and documents
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Hartmann et al.
, p. 853 (1972)
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Synthesis and radical polymerization of various 2-cyclopropylacrylates
De Meijere, Armin,Bagutski, Viktor,Zeuner, Frank,Fischer, Urs Karl,Rheinberger, Volker,Moszner, Norbert
, p. 3669 - 3678 (2007/10/03)
Fourteen new alkyl 2-cyclopropylacrylates 1a-n with various substituents R1-R5 were synthesized from readily available precursors by applying standard transformations such as cyanohydrin formation from an aldehyde, alcoholysis to an α-hydroxycarboxylic ester, oxidation and Wittig methylenation of an α-oxocarboxylic ester. Overall yields ranged from 33 to 54%. A new method for the hydrolysis of dimethyl cyclopropanedicarboxylates to the corresponding half-esters was developed. The α-oxocarboxylates 7g-n were prepared by dirhodium tetraacetate catalyzed cyclopropanation of alkenes 8g-n with methyl or ethyl diazopyruvate in 32-58% yield. The monomers 1a-n were characterized by 1H, 13C NMR spectroscopy, mass spectrometry and elemental analysis. The radical homopolymerizations of 1a-n were carried out with 2,2′- azabisisobutyronitrile (AIBN) as initiator in chlorobenzene at 65 °C. The highest polymer yields were obtained in the polymerizations of If and 1h or 1k and 11, i.e. from monomers with an annelated five- or six-membered ring. In the case of 1h and 1k, both the polymer yields (99 and 98%, respectively) and the glass transition temperatures (Tg) of 57 and 93 °C were significantly higher than those observed for the polymer from 1,1-bis(ethoxycarbonyl)-2-vinylcyclopropane (DECVCP), which was used as a benchmark for the monomer reactivities in the radical polymerizations of all the vinylcyclopropane derivatives 1a-n. The bicyclic monomers 1h and 1k also demonstrated drastically improved reactivities in the radical copolymerization with methyl methacrylate when compared to DECVCP. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
