Synthesis and Styrene Copolymerization of Novel Halogen, Alkoxy, and Alkyl Ring-Disubstituted Isopropyl 2-Cyano-3-Phenyl-2-Propenoates

Abstract

<p>Novel trisubstituted ethylenes, ring-disubstituted isopropyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO<sub>2</sub>CH(CH<sub>3</sub>)<sub>2 </sub>(where R is 2-bromo-5-methoxy, 3-bromo-4-methoxy, 5-bromo-2-methoxy, 2-chloro-3-methoxy, 3-chloro-4-methoxy, 2-chloro-6-methyl, 2-fluoro-6-methyl, 3-fluoro-2-methyl, 3-fluoro-4-methyl, 4-fluoro-2-methyl, 4-fluoro-3-methyl) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and isopropyl cyanoacetate and characterized by CHN elemental analysis, IR, <sup>1</sup>H- and <sup>13</sup>C-NMR. All the ethylenes were copolymerized with styrene in solution with radical initiation (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, <sup>1</sup>H and <sup>13</sup>C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500ºC range with residue (1-8% wt.), which then decomposed in the 500-800ºC range.</p>

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. In this study we have prepared and copolymerized novel ring-substituted isopropyl esters of 2-cyano-3-phenyl-2-propenoic acid, RPhCH = C(CN)CO 2 CH(CH 3 ) 2 , ICPP, where R is 2,3,4-trimethoxy, 2,4,5-trimethoxy, 2,4,6-trimethoxy, 3-bromo-4,5-dimethoxy, 5-bromo-2,3-dimethoxy, 5-bromo-2,4-dimethoxy, 6-bromo-3,4-dimethoxy, 2-bromo-3-hydroxy-4-methoxy, 4-bromo-2,6-difluoro, 2-chloro-3,4-dimethoxy, 3-chloro-4,5-dimethoxy, 5-chloro-2,3-dimethoxy, 2,3,6-trichloro, 3-chloro-2,6-difluoro, 2,3,4-trifluoro, 2,4,5-trifluoro, 2,4,6-trifluoro, 3,4,5-trifluoro, 2,3,5,6-tetrafluoro, 2,3,4,5,6-pentafluoro.…”