Indirect electrooxidation (an ex-cell method) of alkylbenzenes by recycle use of (NH4)2Ce(NO3)6 in various solvent systems

Sigeru Torii, Hideo Tanaka, Tsutomu Inokuchi, Shoji Nakane, Mitsuo Akada, Norio Saito, Tosifumi Sirakawa

Research output: Contribution to journalArticle

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Abstract

Indirect electrooxidation (an ex-cell method) of the side chain of alkylbenzenes has been performed by recycle use of (NH4)2Ce(NO3)6 (CAN) in various solvent systems. The side-chain oxidation of p-methoxytoluene (1) with CAN in methanol proceeds smoothly, yielding anisaldehyde (3, 94%), while use of aqueous methanol or acetic acid resulted in a mixture of 3 and the dimeric product 4 (19-35%) along with complex products (28-47%). Electrooxidation of the recovered cerium(III) salts was performed smoothly in methanol by passing 1.1-1.2 F/mol of electricity to give a reddish methanol solution of CAN, which can be used for the next oxidation of 1. The repeated use of CAN over 10 times produced the desired 3 in over 90% yields. Similarly, the oxidation of alkylbenzenes, bearing a p-methoxy group, gave the corresponding side-chain-oxidized products. In contrast, p-tert-butyltoluene (9e) could be oxidized by heating with CAN in aqueous 50% acetic acid at 85-90°C to give p-tert-butylbenzaldehyde in over 90% yield. The regeneration of CAN after the oxidation of 9e was also accomplished by electrolysis in the aqueous 50% acetic acid system. The reaction mechanisms in connection with the nature of CAN in various solvent systems are discussed.

Original languageEnglish
Pages (from-to)1647-1652
Number of pages6
JournalJournal of Organic Chemistry
Volume47
Issue number9
Publication statusPublished - 1982

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Electrooxidation
Methanol
Acetic Acid
Oxidation
Bearings (structural)
Cerium
Electrolysis
Electricity
Salts
Heating

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Torii, S., Tanaka, H., Inokuchi, T., Nakane, S., Akada, M., Saito, N., & Sirakawa, T. (1982). Indirect electrooxidation (an ex-cell method) of alkylbenzenes by recycle use of (NH4)2Ce(NO3)6 in various solvent systems. Journal of Organic Chemistry, 47(9), 1647-1652.

Indirect electrooxidation (an ex-cell method) of alkylbenzenes by recycle use of (NH4)2Ce(NO3)6 in various solvent systems. / Torii, Sigeru; Tanaka, Hideo; Inokuchi, Tsutomu; Nakane, Shoji; Akada, Mitsuo; Saito, Norio; Sirakawa, Tosifumi.

In: Journal of Organic Chemistry, Vol. 47, No. 9, 1982, p. 1647-1652.

Research output: Contribution to journalArticle

Torii, S, Tanaka, H, Inokuchi, T, Nakane, S, Akada, M, Saito, N & Sirakawa, T 1982, 'Indirect electrooxidation (an ex-cell method) of alkylbenzenes by recycle use of (NH4)2Ce(NO3)6 in various solvent systems', Journal of Organic Chemistry, vol. 47, no. 9, pp. 1647-1652.
Torii, Sigeru ; Tanaka, Hideo ; Inokuchi, Tsutomu ; Nakane, Shoji ; Akada, Mitsuo ; Saito, Norio ; Sirakawa, Tosifumi. / Indirect electrooxidation (an ex-cell method) of alkylbenzenes by recycle use of (NH4)2Ce(NO3)6 in various solvent systems. In: Journal of Organic Chemistry. 1982 ; Vol. 47, No. 9. pp. 1647-1652.
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abstract = "Indirect electrooxidation (an ex-cell method) of the side chain of alkylbenzenes has been performed by recycle use of (NH4)2Ce(NO3)6 (CAN) in various solvent systems. The side-chain oxidation of p-methoxytoluene (1) with CAN in methanol proceeds smoothly, yielding anisaldehyde (3, 94{\%}), while use of aqueous methanol or acetic acid resulted in a mixture of 3 and the dimeric product 4 (19-35{\%}) along with complex products (28-47{\%}). Electrooxidation of the recovered cerium(III) salts was performed smoothly in methanol by passing 1.1-1.2 F/mol of electricity to give a reddish methanol solution of CAN, which can be used for the next oxidation of 1. The repeated use of CAN over 10 times produced the desired 3 in over 90{\%} yields. Similarly, the oxidation of alkylbenzenes, bearing a p-methoxy group, gave the corresponding side-chain-oxidized products. In contrast, p-tert-butyltoluene (9e) could be oxidized by heating with CAN in aqueous 50{\%} acetic acid at 85-90°C to give p-tert-butylbenzaldehyde in over 90{\%} yield. The regeneration of CAN after the oxidation of 9e was also accomplished by electrolysis in the aqueous 50{\%} acetic acid system. The reaction mechanisms in connection with the nature of CAN in various solvent systems are discussed.",
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