Polymerization by Oxidative Coupling. The Function of Copper in the Oxidation of 2,6-Dimethylphenol

Finkbeiner, Herman; Hay, Allan S.; Blanchard, H. S.; Endres, G. F.

doi:10.1021/jo01340a048

Cited by 144 publications

(21 citation statements)

References 5 publications

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“…In general, an excess of amine ligand to CuCl is required to prevent the unfavorable CC coupling reaction during the polymerization . Tables and summarize the results of the effects of the reaction time and the amount of amine ligands on the oxidative coupling polymerization of o ‐cresol with 2‐phenylpyridine/CuCl or 2‐( p ‐tolyl)pyridine/CuCl catalyst.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of poly(o‐cresol) by oxidative coupling polymerization of o‐cresol

Aiba

Sun

Shibasaki

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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The oxidative coupling polymerization of o‐cresol was investigated using various 2‐substituted pyridine/CuCl catalysts under an oxygen atmosphere, in which 2‐phenylpyridine/CuCl and 2‐(p‐tolyl)pyridine/CuCl catalysts yielded poly(o‐cresol)s with higher regioselectivity for 1,4‐coupling. These polymerizations produced branched and crosslinked polymers in the later stages of polymerization. These polymers showed good thermal properties, such as 5% weight loss temperatures of up to 406 °C and glass transition temperatures of up to 151 °C. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 878–884

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Section: Resultsmentioning

confidence: 99%

Synthesis of poly(o‐cresol) by oxidative coupling polymerization of o‐cresol

Aiba

Sun

Shibasaki

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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“…The use of such compounds had been reported by Rogic and Demmin 41,42 and Tsuji and Takayanagi. 35,43 We used 3,5-di-tert-butylcatechol, the most recalcitrant substrate, 44 with pyridine copper methoxy chloride (PyCuClOMe) using various solvent combinations, but no ring-cleavage was observed and the product obtained in all reactions was 3,5-di-tertbutyl-o-benzoquinone. 31 Using the Speier and Tyeklar cupric methoxy chloride procedure 37 we found that the predominant product isolated in 57% yield was not the diester as previously reported 37 but the lactone, 3,5-ditert-butyl-5-methylcarboxymethyl-2-furanone, also observed in Scheme 7.…”

Section: Methodsmentioning

confidence: 99%

Simple Syntheses of Seven-Membered Rings via an Entropy/Strain Reduction Strategy

Byrne¹,

Gilheany²

2004

Synlett

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The straightforward four-step synthesis of unsaturated seven-membered carbocycles and heterocycles via a route starting from catechols and quinones is described. The route is based on the Perkin ring-closure reaction and was designed to alleviate the usual problems associated with the formation of medium rings. This is achieved through the presence of unsaturation in the starting material, which alleviates ring strain problems, reduces the entropy of activation and ensures that the chain ends are suitably orientated to encourage ring closure.

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“…Its formula was proposed by FINEBEINER et al 9) on the basic of preparation, chemical analysis and spectroscopic observations. A particular catalyst is highly selective to establish C-C or C -0 linkages and very efficient at room temperature and atmospheric pressure3).…”

Section: Introductionmentioning

confidence: 99%

The coordination complexes (CuCl, pyridine, methanol) used for oxidative coupling – study by high resolution NMR determination of the structure of the catalyst

1973

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A structure of the solid catalyst used for oxidative coupling of phenols is proposed from an NMR study in various solvents. The stoichiometry of the solid prepared via oxidation of Cu2Clz by 0 2 in a pyridine/methanol mixture is discussed in view of the coordination of the ligands. The catalytic activity could be due to the /O\ -cu-cugroup and the exchangeability of the pyridine ligands. ZUSAMMENFASSUNG:Aus NMR-spektroskopischen Untersuchungen in verschiedenen Losungsmitteln wird eine Struktur des Katalysators fur die oxidative Kupplung von Phenolen vorgestellt. Die Stochiometrie des durch 02-Oxidation von CuzCl2 in einem Pyridin/Methanol-Gemisch dargesteuten Festkorpers und die Ligandenkoordination werden diskutiert. Die Ursache der katalytischen Aktivitiit scheint in der Gegenwart der Gruppe /O\ -cu-cuund in der Austauschfahigkeit der Liganden am Pyridin zu bestehen.

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Polymerization by Oxidative Coupling. The Function of Copper in the Oxidation of 2,6-Dimethylphenol

Cited by 144 publications

References 5 publications

Synthesis of poly(o‐cresol) by oxidative coupling polymerization of o‐cresol

Synthesis of poly(o‐cresol) by oxidative coupling polymerization of o‐cresol

Simple Syntheses of Seven-Membered Rings via an Entropy/Strain Reduction Strategy

The coordination complexes (CuCl, pyridine, methanol) used for oxidative coupling – study by high resolution NMR determination of the structure of the catalyst

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