Synlett 2003(2): 0247-0249
DOI: 10.1055/s-2003-36806
LETTER
© Georg Thieme Verlag Stuttgart · New York

Phase-Vanishing Method: Friedel-Crafts Acylation of Thiophene with Tin Tetrachloride and its Application to Convenient Parallel Synthesis

Hiroshi Matsubara, Shinji Yasuda, Ilhyong Ryu*
Department of Chemistry, Faculty of Arts and Sciences, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan
Fax: +81(72)2549695; e-Mail: ryu@ms.cias.osakafu-u.ac.jp;
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Publikationsverlauf

Received 19 November 2002
Publikationsdatum:
22. Januar 2003 (online)

Abstract

Phase-vanishing (PV) method was applied to Friedel-Crafts acylations of aromatic compounds with tin tetrachloride as a Lewis acid. The reaction proceeded smoothly and acylation products were obtained in good yield. Parallel, four different Friedel-Crafts acylation reactions were carried out successfully based on the present PV method.

    References

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7

A typical experimental procedure: Tin tetrachloride (2.2 mmol, 573 mg) was added slowly to FC-72 (3 mL) in a test tube (14.4 mmφ × 130 mm) with a septum by using a glass pipette and then thiophene (2.0 mmol, 168 mg) and propionyl chloride (2.2 mmol, 204 mg) in benzene (3 mL) was added slowly, forming three layers. The bottom layer was stirred gently at 30 °C for 3 h, taking care not to mix the three layers. The dark purple benzene layer was taken up with a pipette. Additional benzene (2 mL × 4) was then placed on the residual FC-72 layer, followed by decanting off. The combined benzene layer was washed with 1 M HCl (20 mL × 2) and water (20 mL × 2), and dried over MgSO4, and concentrated. Purification by a short column chromatography on silica gel with benzene gave 2-propionylthiophene (1.43 mmol, 201 mg) in 72% yield.

8

We confirmed that no contamination among products was observed in this parallel experiment under the conditions specified in Scheme [2] .