368. cycloHexane-1 : 3-diones. Part IV. The synthesis of further terphenyl derivatives

Ames, G. R.; Davey, Wheeler P.

doi:10.1039/jr9580001794

Cited by 17 publications

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“…6 Methyl C(-phenylacrylate was obtained by the reaction of formaldehyde and dimethyl oxalyl phenylacetate, which was prepared from methyl phenylacetate, dimethyl oxalate, and sodium methoxide. 7 Methyl C<'.-(p-bromophenyl)acrylate was prepared by the dehydration of the corresponding hydroxycarboxylic acid 8 4.20%; Cl, 13.54%. The NMR spectrum (10% CCl4 solution) showed peaks at 5.94 and 6.49 ppm (two doublets, 1.9 H) assigned to the /3-protons of vinyl group and at 7.0-7.5ppm (multiplet, 9.0 H) assigned to the phenyl protons.…”

Section: Methodsmentioning

confidence: 99%

Heterotactic Polymers of α-Substituted Acrylic Acid Esters

Hatäda

Sugino

Ise

et al. 1980

Polym J

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ABSTRACT:Polymerizations of various methacrylates and 0(-(p-substituted phenyl)acrylates were studied in toluene and tetrahydrofuran by several anionic initiators. The polymerization with octylpotassium in tetrahydrofuran was found to be the most suitable for the formation of the heterotactic polymer, defined as the polymer containing more than 50% heterotactic triads. Methacrylic acid esters of the primary alcohol gave the heterotactic polymers, whose heterotactic contents increased with an increase in the bulkiness of the ester group. Methacrylic esters of secondary alcohol generally gave heterotactic polymers with octylpotassium in tetrahydrofuran. In the polymerizations of methacrylic acid esters of tertiary alcohol, the heterotactic contents decreased with an increase in the bulkiness of the ester group. A perfectly atactic polymer was obtained in the polymerization of methyl 0(-phenylacrylate with butyllithium in tetrahydrofuran, but it gave the heterotactic polymer when initiated with octylpotassium in tetrahydrofuran. Methyl 0(-pchlorophenylacrylate produced the heterotactic polymer in tetrahydrofuran with butyllithium as well as with octylpotassium. In the case of methyl 0(-p-bromophenylacrylate, the heterotactic polymer was obtained even in the polymerization in toluene with butyllithium. These results indicate that the acrylic acid ester having the bulkier substituent tends to give the.heterotactic polymer more easily by anionic initiator. KEY WORDSHeterotactic Polymer / Alkyl Methacrylate / ()(-Substituted Acrylate / Methyl Methacrylate / Methyl 0(-Phenylacrylate / Cyclohexyl Methacrylate / Octylpotassium / Fluorenylcesium/ 13 C-NMR Spectrum / Glass Transition Temperature/ Many papers have been published on polymerization in which highly isotactic or syndiotactic polymers were obtained. However, there have been few publications concerning the formation of heterotactic polymers. Heterotactic poly(vinyl alcohol) was reported by Nozakura et al. 1 • 2 and heterotactic poly(acetaldehyde) by Brame and Vogl,3 and Goodman and Brandrup. 4 A polymer having more than 50% portion ofheterotactic triads should be defined as a heterotactic polymer since the heterotactic contents can attain at most 50% even when the regulation in the polymerization is sterically random. The formation ofheterotactic polymer appears to be very interesting since a higher order of stereoregulation would be required for the heterotactic polymerization than for the isotactic or syndiotactic one.In our previous paper 5 the formation ofheterotactic polymers of methyl a-(p-bromophenyl)acrylate and methyl a-(p-chlorophenyl)acrylate was briefly reported. In this work, we have studied the anionic polymerizations of various methacrylates and aphenylacrylates under various conditions, and found that the bulkiness of a-substituent was one of the important factor necessary for the heterotactic growth in the polymerization and that the polymerization in tetrahydrofuran initiated with octylpotassium was suitable for the formation of the heterotactic ...

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Section: Methodsmentioning

confidence: 99%

Heterotactic Polymers of α-Substituted Acrylic Acid Esters

Hatäda

Sugino

Ise

et al. 1980

Polym J

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“…4 The crude product was fractionally distilled under reduced nitrogen pressure: bp 59.5-60.5 (2 mm); nt 5 1.5380. The NMR spectrum (5.0-% CC14 solution) showed peaks at 3.…”

Section: Methodsmentioning

confidence: 99%

Stereospecific Polymerization of Methyl α-Phenylacrylate

Yuki

Hatäda

Niinomi

et al. 1971

Polym J

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ABSTRACT:The polymerization of methyl a-phenylacrylate was carried out in toluene by n-BuLi at -78~30°C. The yield of the polymer was highest at -45°C and then decreased with increasing the temperature. No polymer was obtained above 0°C. The polymer obtained at -78°C was rich in isotacticity. By increasing the polymerization temperature the fraction of isotactic triads decreased in association with the increases in the fracrions of heterotactic and syndiotactic triads. Above -45°C, the proportion, I: H: S of the polymer obtained was close to I : 2: 1, suggesting the random stereoregulation in the propagating step. The random polymer was also obtained by n-BuLi in polar solvent such as THF at low temperature as well as by AIBN. The addition of a small amount of methanol to the polymerization system by n-BuLi in toluene increased the yield, isotacticity, and molecular weight of the polymer, and the maximum values were obtained at CH3OH/n-BuLi=0.83. The polymerization by (iso-Bu)2AlNPh2 in toluene at -78°C gave a syndiotactic polymer in low yield. The reactivity of methyl a-phenylacrylate in anionic polymerization is briefly discussed in comparison with those of some other methyl a-alkylacrylates.KEY WORDS Stereospecific Polymerization / Poly(methyl a-phenylacrylate) / n-Butyllithium / Diisobutylaluminum Diphenylamide / Random Polymer / 13 C NMR Spectrum / DSC Analysis / Stereospecific polymerizations of methyl and other alkyl methacrylates have been reported by many authors. However, little attention has been paid to stereoregulation in the polymerization of a-alkylacrylate other than methacrylate

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“…mp (7) 145-147°C; (8) 149°C; (9) 146-148°C; mixture mp with an authentic sample, 148°C). 'H NMR (CD,OD), 6 (TMS): 3.73 and 4.26 (AB quartet), 7.24-7.66 (multiplet), and comparison with an authentic sample prepared by the literature route (4)(5)(6). 'H NMR spectra in D20 (Na salt) or CD,OD were identical for both samples.…”

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confidence: 98%

“…Acidification and extraction gave a product mixture shown by NMR analysis to contain small amounts of benzoic, mandelic, and atrolactic acids, but to be principally 2-phenylglyceric acid. This identification is based on comparison of NMR spectra with those of an authentic sample prepared by the literature route (4)(5)(6). 'H NMR spectra in D,O (Na salt) or CD,OD were identical for both samples.…”

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Dihydroxyacids from the chlorination of ketones: an unexpected process

Guthrie¹,

Cossar²,

Lu³

1991

Can. J. Chem.

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. Can. J. Chem. 69, 1904Chem. 69, (1991. Chlorination of propiophenone in aqueous alkali at room temperature, with low concentrations of hypochlorite, leads to 2-phenylglyceric acid as the major product. This acid is formed by further oxidation of 1-phenyl-1,2-propanedione, which is an intermediate in the oxidation of propiophenone. Formation of this acid is reasonable in the light of other halogenation chemistry. Analogous reactions are observed for butyrophenone, which yields 2,3-dihydroxy-2-phenylbutanoic acid, and for cycloheptanone, which yields 1,2-dihydroxycyclohexanecarboxylic acid.

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368. cycloHexane-1 : 3-diones. Part IV. The synthesis of further terphenyl derivatives

Cited by 17 publications

References 0 publications

Heterotactic Polymers of α-Substituted Acrylic Acid Esters

Heterotactic Polymers of α-Substituted Acrylic Acid Esters

Stereospecific Polymerization of Methyl α-Phenylacrylate

Dihydroxyacids from the chlorination of ketones: an unexpected process

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