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Synlett 2002(3): 0522-0524
DOI: 10.1055/s-2002-20485
LETTER
© Georg Thieme Verlag Stuttgart · New York

Oxidative Cleavage of the Double Bonds of Styrenes with a Combination of Mesoporous Silica FSM-16 and I2 under Photoirradiation

Akichika Itoh*a, Tomohiro Kodamaa, Yukio Masakia, Shinji Inagakib
a Gifu Pharmaceutical University, 5-6-1 Mitahora-higashi, Gifu 502-8585, Japan
b Toyota Central R & D labs., Inc., Aichi, 480-1192, Japan
Fax: +81(58)2375979; e-Mail: itoha@gifu-pu.ac.jp;
Further Information

Publication History

Received 29 December 2001
Publication Date:
05 February 2007 (online)

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Abstract

A mesoporous silica FSM-16 was found to be a recyclable promoter for the oxidative cleavage of double bonds, which are conjugated with an aromatic nucleus, to afford the corresponding carboxylic acid in the presence of catalytic iodine under photoirradiation conditions.

Key words

oxidative cleavage - mesoporous silica - FSM-16 - iodine - photochemistry

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5

A typical procedure follows: In a pyrex tube, a suspension of 4-tert-butylstyrene (1, 50 mg), iodine and silica (100 mg) in dry i-Pr2O (5 mL) was stirred, and irradiated externally at room temperature with a 400-W high-pressure mercury lamp under aerobic atmosphere for 36 h. FSM-16 was then filtered off and washed with ethyl acetate, and the filtrate was washed with aq. sodium thiosulfate solution and brine. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. Pure 4-tert-butylbenzoic acid (2) (46 mg, 82%) was obtained after purification by preparative TLC.

7

The unit cell dimension of FSM-16 was 45.3 nm. The pore diameter was 2.8 nm, and the specific surface area was 948 m2/g.