反应详情

6-(3,3,3-Triphenylpropoxy)-2-naphthonitrile was prepared by the method of example 27 utilizing 6-cyano-2-naphthol, ADDP, and nBu3P. Colorless solid, mp=207°-208° C. (Et2O/hexane), 50% yield. 1H NMR (CDCl3) δ 8.09 (s, 1H), 7.72 (d, J=9.0, 1H), 7.63 (s, 1H), 7.50 (dd, J=1.4 and 8.5Hz, 1H), 7.20-7.37 (m, 16H), 6.76 (d, J=2.1, 1H), 3.90 (m, 2H), 3.20 (m, 2H). IR 2220, 1621, 1602, 1493, 1472, 1396 cm-1. MS 440 (MH+). Anal. calcd. for C32H25NO: C, 87.44; H, 5.73; N, 3.19. Found: C, 86.93; H, 5.78; N, 3.09. A mixture of the nitrile (0.440 g, 1 mmol) and tetra-n-butylammonium borohydride (0.775 g, 3 mmol) in dichloromethane was heated to reflux under an atmosphere of nitrogen for 18 h. The solvent was removed in vacuo and the residue treated with 10% HCl and refluxed for 3 h. The reaction mixture was then basified with solid NaOH and the liberated amine was extracted in dichloromethane/benzene. The organic extracts were washed with water, dried (Na2SO4), filtered and evaporated to dryness to obtain a solid residue which was converted to the hydrochloride salt by passing dry HCl gas into a dichloromethane solution and recrystallizing from dichloromethane/Et2O to obtain 0.210 g (44%), mp=137-140. 1H NMR (CDCl3) δ 8.44 (s, 2H, exchangeable), 7.10-7.47 (m, 19 H), 6.49 (dd, J=2.1 and 8.9 Hz, 1H), 6.44 (d, J=1.7, 1H), 3.72 (s, 2H), 3.66 (m, 2H), 3.05 (m, 2H). IR 3422-2600, 1634, 1607, 1490, 1475 cm-1. MS 444 (MH+). Anal. calcd. for: C32H29NO·HCl·0.2 H2O: C, 79.32; H, 6.34; N, 2.89. Found: C, 79.28; H, 6.41; N, 2.92.

1. temperaturewas heated
2. temperatureto reflux under an atmosphere of nitrogen for 18 h
3. customThe solvent was removed in vacuo
4. additionthe residue treated with 10% HCl
5. temperaturerefluxed for 3 h
6. extractionthe liberated amine was extracted in dichloromethane/benzene
7. washThe organic extracts were washed with water
8. dry with materialdried (Na2SO4)
9. filtrationfiltered
10. customevaporated to dryness
11. customto obtain a solid residue which
12. customrecrystallizing from dichloromethane/Et2O
13. customto obtain 0.210 g (44%), mp=137-140