Novel method for the oxidation of thiophenes
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 10, October, 2004
2247
Synthesis of thiophene dioxides 16—23 in trifluoroacetic acid
(general procedure). Trifluoroacetic anhydride (10.5 g, 50 mmol)
and one to two drops of trifluoroacetic acid as a catalyst were
added at –10 °C to a vigorously stirred 95—98% H2O2 (1.02 g,
30 mmol). The reaction mixture was stirred for 10 min in an ice
bath until it became transparent and homogeneous and then a
solution or suspension of a corresponding thiophene (10 mmol)
in 10 mL of trifluoroacetic acid was added. The reaction mixture
was vigorously stirred in the dark at ~20 °C for 48 to 120 h,
depending on the substituent in the thiophene ring (Table 4).
The course of the reaction was monitored by TLC. All highly
volatile products were removed in water aspirator vacuum. The
residue was separated from traces of trifluoroacetic acid in vacuo
(oil pump, 1—2 Torr) and recrystallized from CHCl3, CH3CN,
or their mixture.
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Received February 12, 2004;
in revised form July 7, 2004