The Use of Liquid Phase Oxidation for the Preparation of Nuclearly Substituted Styrenes. I. Methyl p-Vinylbenzoate<sup>1</sup>

Emerson, William S.; Heyd, J.W.; Lucas, Victor E.; Chapin, Earl C.; Owens, Grafton R.; Shortridge, Robert W.

doi:10.1021/ja01208a045

Cited by 11 publications

(4 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Materials. 4-(Ethyl) methyl benzoate ( 7) was synthesized as described previously . Tetrahydrofuran (THF) was distilled from sodium benzophenone dianion.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Living/Controlled Radical Polymerization of Ethyl and n-Butyl Acrylates at 90 °C Mediated by β-Sulfinyl Nitroxides: Influence of the Persistent Radical Stereochemistry

2004

View full text Add to dashboard Cite

Herein we report the living/controlled radical polymerization of ethyl and n-butyl acrylates mediated by β-sulfinyl nitroxides at temperatures below 90 °C. This study examined the effect of the persistent radical stereochemistry on the polymerization kinetics of ethyl acrylate. Experiments were carried out in the presence of alkoxyamines based on 1-phenylethyl transient radicals bearing a 4-hydrogen or a 4-(methyl carboxylate) group, and two enantiomerically pure mixtures of N-tert-butyl-N-(1-tert-butyl-2-ethylsulfinyl)propyl nitroxide (BESN); i.e., a 1:1 S S R β R α/R S S β S α and a 1:1 R S R β R α/S S S β S α racemic mixtures. The dissociation rate constants (k d) of the alkoxyamines and poly(ethyl acrylate) chains capped by both nitroxide racemic mixtures were determined by ESR spectroscopy measurements. Kinetic and ESR studies of ethyl acrylate polymerization experiments allowed the determination of the equilibrium constants (K 90) and the rate constants of combination (k c 90) for each system. The rate constants of combination were found to be slightly dependent on the nitroxide stereochemistry whereas an order of magnitude difference was observed for the rate constants of dissociation. Then, well-defined poly(ethyl acrylate) and poly(n-butyl acrylate) were prepared, at 90 °C, from alkoxyamines based on the R S R β R α/S S S β S α nitroxide diastereomers.

show abstract

“…Materials. 4-(Ethyl) methyl benzoate ( 7) was synthesized as described previously . Tetrahydrofuran (THF) was distilled from sodium benzophenone dianion.…”

Section: Methodsmentioning

confidence: 99%

“…4-(Ethyl) methyl benzoate (7) was synthesized as described previously. 51 Tetrahydrofuran (THF) was distilled from sodium benzophenone dianion. Benzene (Aldrich, 99%) was distilled from 1,1-diphenylethylene/n-BuLi and stored under argon.…”

Section: Methodsmentioning

confidence: 99%

Living/Controlled Radical Polymerization of Ethyl and n-Butyl Acrylates at 90 °C Mediated by β-Sulfinyl Nitroxides: Influence of the Persistent Radical Stereochemistry

2004

View full text Add to dashboard Cite

show abstract

“…When alumina on pumice was used for the preparation of p-ethylstyrene at 300°C., some alcohol was recovered and some p-ethyl-a-phenethyl ether was obtained (80). When the vapors of p-carbethoxy-a-phenethyl alcohol together with steam were passed over activated alumina at 300-350°C., 8 per cent of p-vinylbenzoic acid was isolated along with 35 per cent of its polymer (44).…”

Section: Archohch3 Gpo^c! Arch2ch3 + Arcoch3mentioning

confidence: 99%

The Preparation of Substituted Styrenes by Methods Not Involving Hydrocarbon Cracking.

Emerson¹

1949

Chem. Rev.

Self Cite

View full text Add to dashboard Cite

“…8-Methyl-14-benzoxathian (8).-A solution of 50 ml of benzene, 1.56 g of (0.02 mole) of /3-mercaptoethanol, and 5.10 g (0.019 mole) of bromo ketone, 6, was heated under reflux for 1.5 hr. Very little water was collected in the Dean-Stark trap and no hydrogen bromide could be detected.…”

mentioning

confidence: 99%

Deuterium isotope effect in a nonaqueous acid-base system

Welch¹,

Abell²

1968

J. Org. Chem.

View full text Add to dashboard Cite

The Use of Liquid Phase Oxidation for the Preparation of Nuclearly Substituted Styrenes. I. Methyl p-Vinylbenzoate¹

Cited by 11 publications

References 0 publications

Living/Controlled Radical Polymerization of Ethyl and n-Butyl Acrylates at 90 °C Mediated by β-Sulfinyl Nitroxides: Influence of the Persistent Radical Stereochemistry

Living/Controlled Radical Polymerization of Ethyl and n-Butyl Acrylates at 90 °C Mediated by β-Sulfinyl Nitroxides: Influence of the Persistent Radical Stereochemistry

The Preparation of Substituted Styrenes by Methods Not Involving Hydrocarbon Cracking.

Deuterium isotope effect in a nonaqueous acid-base system

Contact Info

Product

Resources

About

The Use of Liquid Phase Oxidation for the Preparation of Nuclearly Substituted Styrenes. I. Methyl p-Vinylbenzoate1

Cited by 11 publications

References 0 publications

Living/Controlled Radical Polymerization of Ethyl and n-Butyl Acrylates at 90 °C Mediated by β-Sulfinyl Nitroxides: Influence of the Persistent Radical Stereochemistry

Living/Controlled Radical Polymerization of Ethyl and n-Butyl Acrylates at 90 °C Mediated by β-Sulfinyl Nitroxides: Influence of the Persistent Radical Stereochemistry

The Preparation of Substituted Styrenes by Methods Not Involving Hydrocarbon Cracking.

Deuterium isotope effect in a nonaqueous acid-base system

Contact Info

Product

Resources

About

The Use of Liquid Phase Oxidation for the Preparation of Nuclearly Substituted Styrenes. I. Methyl p-Vinylbenzoate¹