Synthesis and Styrene Copolymerization of Novel Chloro and Fluoro Ring-Disubstituted Isopropyl Cyanophenylacrylates

Abstract

<p>Novel chloro and fluoro ring-disubstituted isopropyl 3-phenyl-2-cyanoacrylates, RPhCH=C(CN)CO<sub>2</sub>CH(CH<sub>3</sub>)<sub>2 </sub>(where R is 2-chloro-4-fluoro, 2-chloro-6-fluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro) were prepared and copolymerized with styrene. The acrylates were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and isopropyl cyanoacetate and characterized by CHN elemental analysis, IR, <sup>1</sup>H- and <sup>13</sup>C-NMR. All the acrylates 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.</p>

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 8. Dichloro and difluoro ring-substituted octyl phenylcyanoacrylates

“…The conversion of the copolymers was kept between 10 and 20% to minimize compositional drift (Table 1). Nitrogen elemental analysis showed that between 19.4 and 40.1 mol% of OPCA is present in the copolymers prepared at ST/ OPCA = 3 (mol), which is indicative of relatively high reactivity of the OPCA monomers towards ST radical which is typical of ring-substituted OPCA [18][19][20][21][22][23][24][25][26]. Since OPCA monomers do not homopolymerize, the most likely structure of the copolymers would be isolated OPCA monomer units alternating with short ST sequences (Scheme 2).…”

“…Thus, copolymerization of electrophylic TSE monomers having double bonds substituted with halo, cyano, and carbonyl groups and electron-rich monosubstituted ethylenes such as styrene, N-vinylcarbazole, and vinyl acetate [16][17][18] show a tendency toward the formation of alternating copolymers -thus suggesting a way of functionalization of commercial polymers via introduction of isolated monomer units in copolymers. Earlier we have reported synthesis and styrene copolymerization of a number of dichloro and difluoro ringsubstituted methyl [19][20][21], ethyl [22], propyl [23][24][25], isopropyl [26,27], butyl [28,29], isobutyl [30,31], and 2-methoxyethyl [32] PCAs.…”

Synthesis and styrene copolymerization of novel ring-substituted tert-butyl phenylcyanoacrylates

“…3-Chloro-2-fluorophenyl propyl [1], isopropyl [2], isobutyl [3], and butyl [4] phenylcyanoacrylates (PCA) are synthesized and copolymerized with ethynyl benzene.…”

“…4-(trifluoromethyl)phenyl ethyl PCA is reported in C(sp 3 )-H functionalizations of light hydrocarbons using decatungstate photocatalysis [9]; in a study of kinetic isotope effects for various hydride transfer reactions [10]; in conjugate hydrocyanation of αcyanoacrylates using potassium hexacyanoferrate(II) as cyanating reagent [11]; in study of solid superbase derived from lanthanum-magnesium composite oxide and its catalytic performance in the Knoevenagel condensation under solvent-free condition [12]; in novel multicomponent reaction involving isoquinoline, allenoate and cyanoacrylates [13]; in construction of heterocycles via 1,4-dipolar cycloaddition of quinoline-DMAD zwitterion with various dipolarophiles [14]; in a novel three-component reaction of triphenylphosphine, DMAD, and electron-deficient styrenes: synthesis of cyclopentenyl phosphoranes [15], and in the multicomponent reaction of dimethoxycarbene, dimethyl butynedioate and electrophilic styrenes leading to synthesis of highly substituted cyclopentenone acetals [16]. 2,4, as well as its butyl PCA [18] were prepared and copolymerized with styrene, in addition to being involved in catalyst study of the Knoevenagel condensation [19]. 4-Hydroxy-3,5dimethoxyphenyl ethyl PCA is mentioned in synthesis of biologically potent heterocycles [20]; in study of main-chain and guest-host NLO polymers [21], whereas its isopropyl PCA was synthesized and copolymerized with ethenyl benzene [22].…”