3-methoxy-4-(2,2,2-trifluoroethoxy)benzaldehyde

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Repeating Example 3, except that 4-difluoromethoxy-3-methoxybenzaldehyde was replaced with 70 grams (0.3 mol) of 4-trifluoroethoxy-3-methoxybenzaldehyde to give 4-trifluoroethoxy-3-hydroxybenzaldehyde (m.p. 133˜135° C.) in a yield of 81%. 1H-NMR (ppm) δ: 9.81 (1H, s; —CHO); 7.26 (1H, m; 6-ArH); 7.17 (1H, m; 2-ArH); 6.79 (1H, m; 5-ArH); 4.88 (1H, s; —OH); 4.45 (2H, q; J3H-F=7.2 Hz; —CH2CF3). 13C-NMR (ppm)) δ: 191.0 (CHO), 157.2 (4-ArC), 146.2 (3-ArC), 130.6 (1-ArC), 126 (q, CF3), 123.5 (6-ArC), 116.7 (2-ArC), 116.2 (5-ArC), 87 (m, CH2).

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Repeating Example 3, except that 4-difluoromethoxy-3-methoxybenzaldehyde was replaced with 70 grams (0.3 mol) of 4-trifluoroethoxy-3-methoxybenzaldehyde to give 4-trifluoroethoxy-3-hydroxybenzaldehyde (m.p. 133˜135° C.) in a yield of 81%. 1H-NMR (ppm) δ: 9.81 (1H, s; —CHO); 7.26 (1H, m; 6-ArH); 7.17 (1H, m; 2-ArH); 6.79 (1H, m; 5-ArH); 4.88 (1H, s; —OH); 4.45 (2H, q; J3H-F=7.2 Hz; —CH2CF3). 13C-NMR (ppm)) δ: 191.0 (CHO), 157.2 (4-ArC), 146.2 (3-ArC), 130.6 (1-ArC), 126 (q, CF3), 123.5 (6-ArC), 116.7 (2-ArC), 116.2 (5-ArC), 87 (m, CH2).

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 3.96 g of vaniline (e-1) (26.0 mmol) in 26 ml of dry DMF was added 1.04 g of 60% NaH (26.0 mmol) slowly, and the mixture was stirred for 30 min. in a stream of nitrogen. 2,2,2-Trifluoroethyl trifluoromethanesulfonate (6.64 g: 28.6 mmol) was added dropwise to the mixture and stirred overnight at room temperature. The reaction solution was poured into water and extracted with ether. The ether layer was washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography, eluting with benzene-AcOEt to give 5.98 g of the objective compound 3-methoxy-4-(2,2,2-trifluoroethoxy)benzaldehyde (f-1) (Yield: 98.2%). stirred overnight at room temperature extracted with ether The ether layer was washed with water dried over anhydrous sodium sulfate concentrated under reduced pressure eluting with benzene-AcOEt

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Repeating Example 3, except that 4-difluoromethoxy-3-methoxybenzaldehyde was replaced with 70 grams (0.3 mol) of 4-trifluoroethoxy-3-methoxybenzaldehyde to give 4-trifluoroethoxy-3-hydroxybenzaldehyde (m.p. 133˜135° C.) in a yield of 81%. 1H-NMR (ppm) δ: 9.81 (1H, s; —CHO); 7.26 (1H, m; 6-ArH); 7.17 (1H, m; 2-ArH); 6.79 (1H, m; 5-ArH); 4.88 (1H, s; —OH); 4.45 (2H, q; J3H-F=7.2 Hz; —CH2CF3). 13C-NMR (ppm)) δ: 191.0 (CHO), 157.2 (4-ArC), 146.2 (3-ArC), 130.6 (1-ArC), 126 (q, CF3), 123.5 (6-ArC), 116.7 (2-ArC), 116.2 (5-ArC), 87 (m, CH2).