反应详情

温度

5 °C

A flask was equipped with a magnetic stirrer, a heating mantle, an addition funnel a condensor with N2 inlet and a glass stopper. A mixture of isopropylamine (8.87 g, 150.0 mmol) HCl (37%, 7.39 g, 75.0 mmol), glacial acetic acid (9.01 g, 150.0 mmol) and parformaldehyde (9.46 g, 315.0 mmol) in deoxygenated (N2 bubbled in for 2 h) methanol (125 ml) was stirred at reflux for 15 min under N2. A solution of N-isopropyl-4-piperidinone (101, 21.18 g, 150.0 mmol) and glacial acetic acid (9.01 g, 150.0 mmol) was added dropwise over a period of 1.5 h, which was followed by a period of boiling for an additional 23 h. After the initial 10 h of heating, paraformaldehyde (9.46 g, 315.0 mmol) was added in one portion to the mixture. Concentration of the solution (after 23 h) gave an orange oil which was redissolved in H2O (150 ml), and extracts (ether, 2×100 ml) thereof were discarded. The aqueous layer was chilled (5° C.) in an ice bath and made basic (pH~12) with NaOH pellets. Extraction (H2CCl2, 3×75 ml) gave a solution which was dried (Na2SO4), filtered, and concentrated to give a viscous, reddish-orange oil. Distillation of the oil under reduced pressure (110°-120° C./10-5 mm Hg) gave 22.53 g (67.3% of a light yellow oil 47. IR (film) 2975, 2910, 2830 (C-H), 1735 (C=O) cm-1. 1H NMR (DCCl3) δ1.02 (d, 12 H, CH3 isopropyl), 2.58 [m, 2 H, H(1,5)], 2.87 [m, 6 H, H(2,4,6,8)ax, C-H isopropyl], 3.04 [dd, 4 H, H(2,4,6,8)eq ]; 13C NMR (DCCl3) ppm 17.9, 18.2 (CH 3, isopropyl), 46.82 C(1.5), 53.17 (C-H isopropyl), 53.27, 53.36 C(2,4,6,8), 215 C(9). Anal. Calcd for C13H24N2O: C, 69.59; H, 10.78; N, 12.49. Found: C, 69.39; H, 10.61; N, 12.21.

1. customA flask was equipped with a magnetic stirrer
2. customin deoxygenated (N2 bubbled in for 2 h) methanol (125 ml)
3. temperatureat reflux for 15 min under N2
4. waitwhich was followed by a period
5. temperatureAfter the initial 10 h of heating
6. customConcentration of the solution (after 23 h) gave an orange oil which
7. extractionExtraction (H2CCl2, 3×75 ml)
8. customgave a solution which
9. dry with materialwas dried (Na2SO4)
10. filtrationfiltered
11. concentrationconcentrated
12. customto give a viscous, reddish-orange oil
13. distillationDistillation of the oil under reduced pressure (110°-120° C./10-5 mm Hg)