Methanol → 2-(4-Fluorophenyl)-6-methoxy-1,3-benzothiazole

Participants

Reaction Conditions

Reaction Steps

A solution of Kryptofix® 2.2.2 (23.4 mg, 0.062 mmol) in acetonitrile (2 mL) was added to a solution of KF (7.3 mg, 0.125 mmol) in water (0.5 mL). The solvents were evaporated at 120° C. and the residue was dried by azeotropic distillation with acetonitrile (3×1 mL). A solution of the iodyl precursor 2-(4-iodylphenyl)-6-methoxy-1,3-benzothiazole (7) (5.2 mg, 0.0125 mmol; dried over P2O5 under high vacuum for 2 hours before use) in hot DMSO (0.5 mL) was added to the dried KF-Kryptofix® complex. The reaction mixture was stirred at 120° C., 150° C. or 180° C. for 10 min. The reaction mixture was cooled and diluted with ice water (3 mL) and passed through a C-18 Sep-Pak® pre-activated with methanol (5 mL) followed by water (10 mL). The Sep-Pak was flushed with water (2×5 mL) and the crude product 9a retained on the Sep-Pak® was eluted off with CH2Cl2 (2×5 mL). The dichloromethane eluent was quantitatively analyzed by analytical HPLC (Waters Symmetry C18 column, 5μ particle size, 150×4.6 mm; eluent: MeCN/H2O 1:1; flow rate: 1 mL/min; UV 325 nm or 254 nm; RT=27 min) using an authentic sample of 2-(4-fluorophenyl)-6-methoxy-1,3-benzothiazole (9a) as a standard and the yield of the fluoro product 9a formed at 120° C., 150° C. and 180° C. was determined as 6.5%, 3.4% and 34.6%, respectively. The authentic sample of 9a was prepared in accordance with the nucleophilic displacement method for synthesis of non-rigid PBZ polymers described in U.S. Pat. No. 5,104,960.

Provenance & Evidence