Trisubstituted Ethylenes Research Articles

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

ABSTRACT Condensation of isopropyl cyanoacetate and substituted benzoic aldehydes resulted in formation of novel isopropyl esters of 2-cyano-3-phenyl-2-propenoic acid, RPhCH = C(CN)CO2CH(CH3)2 (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). Copolymerization of the esters with vinyl benzene in solution with radical initiation (ABCN) at 70°C led to formation copolymers. The products were characterized by CHN elemental analysis, IR, 1 H- and 13 C-NMR, GPC, DSC, and TGA.

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

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 novel trisubstituted ethylenes: 11. Halogen ring-substituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C3H7 (where R is 4-chloro-3-fluoro, 2-fluoro-5-iodo, 2-fluoro-6-iodo, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-trifluoromethoxy, 3-trifluoromethoxy, and 4-trifluoromethoxy) were prepared and copolymerized with styrene. The ethylenes were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN analysis, FTIR, 1H and 13C 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 FTIR, 1H and 13C NMR. Decomposition of the copolymers in nitrogen (TGA) occurred in two steps, first in the 250–500 °C range with residue (0.5–3.1% wt.), which then decomposed in the 500–700 °C range.

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 1. Alkyl ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, alkyl ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2CH(CH3)2 (where R is H, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-propyl, 4-i-propyl, 4-butyl, 4-i-butyl, 4-t-butyl) were prepared and copolymerized with styrene. The ethylenes were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and isopropyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C NMR. All the ethylenes were copolymerized with styrene in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by FTIR, 1H and 13C NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 250–500°C range with residue (2-5% wt.), which then decomposed in the 500–800°C range.

Synthesis of Polyaryl-Substituted Olefins via a Rh(III)-Catalyzed One-Pot Reaction Using N-Phenoxyacetamides, Ketones, and Hydrazines.

A Rh(III)-catalyzed one-pot reaction of N-phenoxyacetamides, ketones, and hydrazines for a facile access to disubstituted and trisubstituted ethylenes is reported. In this method, various ketones are transformed into donor-donor diazo compounds, which engage in insertion with N-phenoxyacetamides, following β-H elimination under Rh(III) catalysis to generate (E)-polyaryl-substituted olefins. This chemistry features simple starting materials, mild reaction conditions, and good functional group tolerance.

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 3. Alkoxy ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, alkoxy ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2CH(CH3)2 (where R is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy, 3-ethoxy, 4-ethoxy, 4-propoxy, 4-butoxy, 4-hexyloxy) were prepared and copolymerized with styrene. The ethylenes were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and isopropyl cyanoacetate, and characterized by CHN analysis, FTIR, 1H and 13C NMR. All the ethylenes were copolymerized with styrene in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by FTIR, 1H and 13C NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 250-500ºC range with residue (2.6–3.9% wt.), which then decomposed in the 500-800ºC range.

Novel copolymers of styrene. 10. Bromo and chloro ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2C3H7 (where R is 2-bromo-4-methyl, 2-chloro-6-methyl, 3-chloro-4-methyl, 2,5-dibromo, 3,5-dibromo, 2,3-dichloro, and 2,4-dichloro) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, 1H and 13C-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, 1H and 13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (7-12% wt.), which then decomposed in the 500-800°C range.

Novel copolymers of styrene. 9. Chloro and fluoro ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2C3H7 (where R is 2,5-dichloro, 2,6-dichloro, 3,4-dichloro, 2,3-difluoro, 2,4-difluoro, 2,5-difluoro, 2,6-difluoro) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) 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, 1H and 13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.2–3.1% wt.), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 8. Fluoro, methoxy, and methyl ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO2C3H7 (where R is 2-fluoro-5-methoxy, 2-fluoro-6-methoxy, 3-fluoro-4-methoxy, 4-fluoro-3-methoxy, 5-fluoro-2-methoxy, 2-fluoro-6-methyl, 3-fluoro-2-methyl, 4-fluoro-2-methyl, 4-fluoro-3-methyl, 5-fluoro-2-methyl) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) 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, 1H and 13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.4–3.0% wt.), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 7. Some ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2C3H7 (where R is 2-bromo-5-methoxy, 3-bromo-4-methoxy, 5-bromo-2-methoxy, 2-chloro-3-methoxy, 3-chloro-4-methoxy, 2-fluoro-3-methoxy, 2-fluoro-4-methoxy, 3-fluoro-4-methyl, 4-fluoro-3-phenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) 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, 1H and 13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3–7% wt.), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 6. Some oxy ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, oxy ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2C3H7 (where R is 4-methoxy-2-methyl, 4-methoxy-3-methyl, 3-ethoxy-4-methoxy, 3,4-dibenzyloxy, 3-benzyloxy-4-methoxy, 4-benzyloxy-3-methoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) 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, 1H and 13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3–22% wt.), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 5. Alkyl and alkoxy ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, alkyl and alkoxy ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO2C3H7 (where R is 2,3-dimethyl, 2,5-dimethyl, 2,6-dimethyl, 3,4-dimethyl, 2,3-dimethoxy, 2,4-dimethoxy, 2,5-dimethoxy, 2,6-dimethoxy 3,4-dimethoxy, 3,5-dimethoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) 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, 1H and 13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (0.6–5.0% wt.), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 4. Halogen ring-substituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, halogen ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH ˭ C(CN)CO2C3H7 (where R is 2-Br, 3-Br, 4-Br, 2-Cl, 3-Cl, 4-Cl, 2-F, 3-F, 4-F were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (0.9–4.7% wt.), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 3. Some ring-substituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO2C3H7 (where R is 2-C6H5CH2O, 3-C6H5CH2O, 4-C6H5CH2O, 4-CH3COO, 3-CH3CO, 4-CH3CONH, 2-CN, 3-CN, 4-CN, 4-(CH3)2N, 4-(C2H5)2N) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (2.7–8.6% wt.), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 2. Oxy ring-substituted propyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, oxy ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO2C3H7 (where R is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy, 3-ethoxy, 4-ethoxy, 4-propoxy, 4-butoxy, 3-phenoxy, 4-phenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of oxy ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) 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, 1H and 13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.2–3.6% wt.), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 14. Halogen ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, halogen ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH ˭C(CN)CO2C4H9 (where R is 3-bromo-4,5-dimethoxy, 5-bromo-2,4-dimethoxy, 2-bromo-3-hydroxy-4-methoxy, 3-chloro-2,6-difluoro, 4-chloro-2,6-difluoro, 2,3,5-trichloro, 2,3,6-trichloro, 2,4,5-trifluoro) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3–5% wt.), which then decomposed in the 500–800°C range.

ChemInform Abstract: A Metal‐Free Addition/Dearomatization—Cyclization/Decarboxylation Cascade of Aryl 3‐Arylpropiolate Toward the Synthesis of 1,1‐Diaryl‐2‐alkyl‐substituted Ethylenes.

AbstractA facile protocol is developed for the cascade reaction of arylpropiolates with ethers or cyclohexane to give trisubstituted ethylenes.

Novel copolymers of styrene. 13. Methyl and methoxy ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel electrophilic trisubstituted ethylenes, methyl and methoxy ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C4H9 where R is 2,4,5-trimethyl, 2,4,6-trimethyl, 2,3-dimethyl-4-methoxy, 2,5-dimethyl-4-methoxy, 2,4-dimethoxy-3-methyl, 2,3,4-trimethoxy, 2,4,5-trimethoxy, 2,4,6-trimethoxy, 3,4,5-trimethoxy were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-trisubstituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (2–5% wt), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 12. Halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTElectrophilic trisubstituted ethylenes, halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO2C4H9 where R is 2-chloro-4-fluoro, 2-chloro-6-fluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro, 2-fluoro-5-iodo, 3-(3,4-dichlorophenoxy), 4-(2,4-dichlorophenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR.Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.7–6.8% wt), which then decomposed in the 500–800°C range.

Novel copolymers of styrene. 11. Fluoro ring-substituted butyl 2-cyano-3-phenyl-2-propenoates

ABSTRACTNovel trisubstituted ethylenes, fluorine ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCHC˭(CN)CO2C4H9 (where R is 2,3-diF, 2,4-diF, 2,5-diF, 2,6-diF, 3,4-diF, 3,5-diF, and 2,4,5-triF) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, 1H and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H and 13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (1.5–2.3% wt.), which then decomposed in the 500–800°C range.