| 85% |
With trichlorophosphate; at 0 - 20℃; |
To a chilled solution of α-tetralone (1) (5 g) in dry dimethylformamide(15 mL), POCl3 (7.5 mL), was added drop wise at 0-5 C for 0.5-1 h and the resulting reaction mixture was stirred at room temperature for 45 hrs.29 The reaction mixture was poured intoice-cold water (150 mL) containing sodium acetate (10 g). The contentswere extracted with ethyl acetate (3x 100 mL). The combined extract were pooled and washed with water (3x 50 mL), dried over anhydroussodium sulfate (Na2SO4) and concentrated on rotary vapour under reduced pressure to give crude product which was purified on silica gelcolumn using petroleum ether and ethyl acetate (99:1) as an eluent togive yellow oily liquid compound 1-chloro-3,4-dihydronaphthalene-2-carbaldehyde (2) with 85% yield. 1H NMR(400 MHz, CDCl3) δ 10.38 (s, 1H), 7.85 (d, J=8.0 Hz, 1H), 7.39-7.31(m, 2H), 7.22 (d, J=8.0 Hz, 1H), 2.84 (t, J=7.6 Hz, 2H), 2.63 (t,J=7.6 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.64, 145.90, 138.96,132.03, 131.93, 131.43, 127.74, 127.11, 126.31, 27.00, 21.58; HRMSm/z [M+H]+ calcd for C11H9ClO: 193.0415, found: 193.0405. |
| 57.1% |
With trichlorophosphate; at 0 - 80℃; for 2.5h; |
Phosphorus oxychloride (2.1 g, 13.7 mmol) was slowly added dropwise to a stirred solution of dry DMF (4.0 g, 54.8 mmol) at 0 C, maintaining the temperature not exceeding 5 C, slowly to the above mixture 1-tetralone (2 g, 13.7 mmol) was added dropwise. The reaction solution was stirred at 0 C for half an hour, raised to 80 C and stirred for another 2 hours. After the reaction was completed, it was poured into a cold aqueous solution of sodium acetate (25% w/v, 25 mL), and extracted with diethyl ether (2×50 mL). The organic phase was washed with saturated brine (3×50 mL) Dry over sodium sulfate, filter and concentrate. The crude product was separated and purified by silica gel column chromatography.Elution with ΡΕ/ΕΑ = 6/1 gave 1.5 g of a viscous liquid with a yield of 57.1%. |
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EXAMPLE 12A 1-chloro-3,4-dihydronaphthalene-2-carbaldehyde To N,N-dimethylformamide (2.3 mL) at 0 C. was added phosphorus oxychloride (2.33 mL) dropwise and the solution stirred at ambient temperature for 30 minutes. To this solution was added 3,4-dihydronaphthalen-1(2H)-one (1.46 g) and the mixture heated to 45 C. for 1 hour. The mixture was quenched with ice and extracted with diethyl ether. The combined organic layers were washed with water, saturated sodium bicarbonate, and water, dried over magnesium sulfate, filtered, and concentrated to provide 1.9 g of the title compound as a yellow oil, which was used without further purification. 1H NMR (DMSO-d6) δ 10.28 (s, 1H), 7.81-7.84 (m, 1H), 7.33-7.50 (m, 3H), 2.82-2.87 (m, 2H), 2.54-2.57 (m, 2H). |
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EXAMPLE 12A 1-chloro-3,4-dihydronaphthalene-2-carbaldehyde To N,N-dimethylformamide (2.3 mL) at 0 C. was added phosphorus oxychloride (2.33 mL) dropwise and the solution stirred at ambient temperature for 30 minutes. To this solution was added 3,4-dihydronaphthalen-1(2H)-one (1.46 g) and the mixture heated to 45 C. for 1 hour. The mixture was quenched with ice and extracted with diethyl ether. The combined organic layers were washed with water, saturated sodium bicarbonate, and water, dried over magnesium sulfate, filtered, and concentrated to provide 1.9 g of the title compound as a yellow oil, which was used without further purification. 1H NMR (DMSO-d6) δ 10.28 (s, 1H), 7.81-7.84 (m, 1H), 7.33-7.50 (m, 3H), 2.82-2.87 (m, 2H), 2.54-2.57 (m, 2H). |
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