Synthesis and Styrene Copolymerization of Novel Chloro and Fluoro Ring-Trisubstituted Propyl Cyanophenylpropenoates

Abstract

Novel trisubstituted ethylenes, ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C3H7 (where R is 2,3,6-trichloro, 2,3,4-trifluoro, 2,3,5-trifluoro, 2,4,5-trifluoro, 2,4,6-trifluoro, 3,4,5-trifluoro) were prepared by the piperidine catalyzed Knoevenagel condensation of ring-trisubstituted benzaldehydes and propyl cyanoacetate.
 
 The ethylenes when copolymerized with styrene in solution with radical initiation (ABCN) at 70°C resulted in formation of copolymers. The composition of the copolymers was calculated from nitrogen analysis. The structures and properties were characterized by IR, 1H and 13C-NMR, GPC, DSC, and TGA.

Synthesis and Styrene Copolymerization of New Halogen and Methoxy Ring-Trisubstituted Propyl Cyanophenylpropenoates

“…Our purposes in exploration of novel propyl cyanophenylpropenoates were twofold: (1) to utilize aldol condensation for synthesis of alkenes with a variety of potentially reactive functional groups; (2) to employ conventional radical copolymerization of novel functional comonomers with a commercial monomer styrene. Thus, in continuation of our investigation of new of propyl cyanophenylpropenoates (Bates et al, 2019, Humanski et al, 2018, Kharas et al, 2017 we have prepared halogen and methoxy ring-trisubstituted propyl cyanophenylpropenoates (PCPP), RPhCH=C(CN)CO 2 C 3 H 7 , where R is 2-bromo-3-hydroxy-4-methoxy, 5-bromo-2,3-dimethoxy, 5-bromo-2,4-dimethoxy, 6-bromo-3,4-dimethoxy, 2-chloro-3,4-dimetoxy, 5-chloro-2,3-dimetoxy, 4-bromo-2,6-difluoro, 3-chloro-2,6-difluoro, 4-chloro-2,6-difluoro, and explore the feasibility of their copolymerization with styrene. To the best of our knowledge, there have been no reports on either synthesis of these propyl cyanophenylpropenoates, nor their copolymerization with styrene.…”

Synthesis and vinyl benzene copolymerization of novel trisubstituted ethylenes: 15. Halogen and methoxy ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates

“…We continue to explore synthesis and copolymerization of CPP compounds; thus, we have prepared and copolymerized with vinyl benzene ring-trisubstituted methyl [15], ethyl [16], propyl [17,18], and butyl [19,20] esters of 2-cyano-3-phenyl-2-propenoic acid. Recently we have reported synthesis and vinyl benzene copolymerization of a number of novel chloro and methoxy [21] and dimethoxy [22] ring-disubstituted isopropyl esters of 2-cyano-3-phenyl-2-propenoic acid.…”