Hydrochloric Acid → 6-(3,3,3-Triphenylpropoxy)-2-naphthonitrile

HRID 363702Notes

Reaction equation

HRID 363702 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8](O)[CH:7]=[CH:6]2)#N.C1CCN(C(N=NC([N:26]2[CH2:31][CH2:30][CH2:29][CH2:28][CH2:27]2)=O)=O)CC1.P([CH2:41][CH2:42][CH2:43][CH3:44])(CCCC)CCCC.[BH4-].[CH2:46]([N+](CCCC)(CCCC)CCCC)[CH2:47]CC.Cl.[CH3:64][CH2:65][O:66][CH2:67][CH3:68].[CH3:69][CH2:70][CH2:71][CH2:72][CH2:73][CH3:74]>ClCCl.O>[C:71]1([C:4]([C:3]2[CH:1]=[CH:47][CH:46]=[CH:11][CH:12]=2)([C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH2:64][CH2:65][O:66][C:67]2[CH:41]=[C:42]3[C:28](=[CH:27][CH:68]=2)[CH:29]=[C:30]([C:31]#[N:26])[CH:44]=[CH:43]3)[CH:70]=[CH:69][CH:74]=[CH:73][CH:72]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 13831TributylphosphineHCID 730421,1'-(Azodicarbonyl)dipiperidineHCID 169536Tetrabutylammonium borohydrideHCID 45894766-Hydroxy-2-naphthonitrileHCID 21584099Diethylether hexane

Product 1

HCID 544498336-(3,3,3-Triphenylpropoxy)-2-naphthonitrileYield 50%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-b501fe33fcbb4de6b85457a40a672a86
Source dataset
uspto-grants-1999_02
Patent number
US05874436

Reaction notes

Loading…