Formaldehyde → HCID 22406883, compound

HRID 440481Notes

Reaction equation

HRID 440481 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1([CH:12]2[C:21]3[C:16](=[CH:17][C:18]([O:24][CH3:25])=[C:19]([O:22][CH3:23])[CH:20]=3)[CH2:15][CH2:14][NH:13]2)[CH2:11][CH2:10][CH2:9]1.[C:26]([C@@](C([O-])=O)(O)[C@@](C(=O)C1C=CC=CC=1)(O)C([O-])=O)(=O)C1C=CC=CC=1.C=O.C([BH3-])#N.[Na+]>C(O)(=O)C.C(#N)C>[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1([CH:12]2[C:21]3[C:16](=[CH:17][C:18]([O:24][CH3:25])=[C:19]([O:22][CH3:23])[CH:20]=3)[CH2:15][CH2:14][N:13]2[CH3:26])[CH2:9][CH2:10][CH2:11]1

Participants

7

Reactant 4

HCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 22406717HCID 22406717, compoundHCID 29414281HCID 29414281, compound

Product 1

HCID 22406883HCID 22406883, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6342AcetonitrileSolvent

Procedure

A mixture of (-)-1-[1-(2-bromophenyl)cyclobutyl]-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (1.85 g) [liberated from the dibenzoyl-(L)-tartrate salt (3.7 g)], acetonitrile (60 ml), 37-40% aqueous formaldehyde solution (1.8 ml) and sodium cyanoborohydride (0.46 g) was stirred for 15 minutes, then neutralised with glacial acetic acid and stirred for a further 45 minutes. The mixture was concentrated by evaporation and basified to pH 12 with dilute aqueous sodium hydroxide solution. The mixture was extracted with ethyl acetate, the extract yielding a gum which was purified via flash chromatography using a 1:2 mixture of ethyl acetate and petroleum ether as eluant to give (-)-1-[1-(2-bromophenyl)cyclobutyl]-6,7-dimethoxy-2-methyl-1,2,3,4-tetrahydroisoquinoline, which had a specific optical rotation αD of -33.6°. Yield 1.6 g.

Workup

  1. stirringstirred for a further 45 minutes
  2. concentrationThe mixture was concentrated by evaporation
  3. extractionThe mixture was extracted with ethyl acetate
  4. customthe extract yielding a gum which
  5. customwas purified via flash chromatography
  6. additiona 1:2 mixture of ethyl acetate and petroleum ether as eluant

Sources & evidence

ORD record
ord-abae21028cf24fe89de59bcb02177e28
Source dataset
uspto-grants-1996_05
Patent number
US05519034

Reaction notes

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