Hydrogen Bromide → HCID 22406909, compound

HRID 440473Notes

Reaction equation

HRID 440473 reaction equation
C[O:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[O:13]C)[CH:9]([C:15]1([C:19]3[CH:28]=[CH:27][C:26]4[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=4)[CH:20]=3)[CH2:18][CH2:17][CH2:16]1)[NH:8][CH2:7][CH2:6]2.C=O.[C:31]([BH3-])#N.[Na+].Br>C(O)(=O)C.C(#N)C>[OH:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][C:12]=1[OH:13])[CH:9]([C:15]1([C:19]3[CH:28]=[CH:27][C:26]4[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=4)[CH:20]=3)[CH2:16][CH2:17][CH2:18]1)[N:8]([CH3:31])[CH2:7][CH2:6]2

Participants

7

Reactant 4

HCID 260Hydrogen BromideHCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 22406714HCID 22406714, compound

Product 1

HCID 22406909HCID 22406909, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 6342AcetonitrileSolvent

Procedure

A mixture of 6,7-dimethoxy-1-[1-(2-naphthyl)cyclobutyl]-1,2,3,4-tetrahydroisoquinoline (4.74 g prepared as described in Example RB20), 37-40% aqueous formaldehyde solution (5.1 ml), acetonitrile (120 ml) and sodium cyanoborohydride (1.3 g) was stirred at ambient temperature for 15 minutes. The mixture was neutralised by addition of glacial acetic acid and stirred for 45 minutes. The mixture was concentrated by evaporation and basified with 2N aqueous potassium hydroxide solution. The resulting mixture was extracted with ether. The extracts were washed with aqueous potassium hydroxide solution and extracted with aqueous hydrochloric acid. The acid extract was basified and extracted with ether. The ether extract yielded a residue, a portion (3.86 g) of which was mixed with 48% aqueous hydrobromic acid (40 ml) and glacial acetic acid (40 ml) and heated at 100° C. for two days. The solvent was removed by evaporation and the residue dried by azeotropic distillation with propan-2-ol. The residue was washed with ether and decolourised with charcoal in propan-2-ol. The mixture was filtered and yielded 6,7-dihydroxy-2-methyl-1-[1-(2-naphthyl)cyclobutyl]-1,2,3,4-tetrahydroisoquinoline 1.1 hydrobromide (m.p. 150°-153° C.) which was dried in vacuo.

Workup

  1. stirringstirred for 45 minutes
  2. concentrationThe mixture was concentrated by evaporation
  3. extractionThe resulting mixture was extracted with ether
  4. washThe extracts were washed with aqueous potassium hydroxide solution
  5. extractionextracted with aqueous hydrochloric acid
  6. extractionThe acid extract
  7. extractionextracted with ether
  8. extractionThe ether extract
  9. customyielded a residue
  10. temperatureheated at 100° C. for two days
  11. customThe solvent was removed by evaporation
  12. dry with materialthe residue dried by azeotropic distillation with propan-2-ol
  13. washThe residue was washed with ether
  14. filtrationThe mixture was filtered

Sources & evidence

ORD record
ord-cbefef94dc0b49788cf611ac9c13b788
Source dataset
uspto-grants-1996_05
Patent number
US05519034

Reaction notes

Loading…