Benzaldehyde → HCID 67685756, compound

HRID 274050Notes

Reaction equation

HRID 274050 reaction equation
[CH3:1][O:2][C:3]1[CH:14]=[CH:13][C:6]2[CH2:7][CH2:8][CH2:9][C@H:10]([NH2:12])[CH2:11][C:5]=2[CH:4]=1.[CH:15](=O)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.[H][H].[ClH:25]>[Pd].C(OCC)(=O)C.C(O)C.C(O)(=O)C>[ClH:25].[CH2:15]([NH:12][C@H:10]1[CH2:9][CH2:8][CH2:7][C:6]2[CH:13]=[CH:14][C:3]([O:2][CH3:1])=[CH:4][C:5]=2[CH2:11]1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

9

Reactant 4

HCID 240BenzaldehydeHCID 313Hydrochloric AcidHCID 53750904HCID 53750904, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 67685756HCID 67685756, compound

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

(S)-3-Methoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-amine hydrochloride (35.5 g) was neutralized with cold 2N sodium hydroxide (155 ml) and the mixture was extracted once with ethyl acetate (310 ml). The extract was washed once with brine (155 ml), dried over anhydrous sodium sulfate, and concentrated in vacuo to afford (S)-3-methoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-amine (30.1 g). A mixture of (S)-3-methoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-amine (30.1 g), 10% palladium on carbon (50% wet; 5.96 g), acetic acid (0.89 ml), benzaldehyde (31.6 ml), and ethanol (300 ml) was stirred at ambient temperature for 3 hours. Then, hydrogen was introduced to the mixture and stirring was continued for an additional 1.5 hours. The catalyst was filtered off and washed with ethanol. Removal of the solvent in vacuo gave the residue, which was dissolved in ethyl acetate (423 ml). To this solution was added, with mechanically stirring in an ice-bath, 4N hydrogen chloride in ethyl acetate (77 ml). After stirring at ambient temperature for 1.5 hours, the mixture was filtered and the cake was washed with ethyl acetate (50 ml). The product was dried in vacuo to give (S)-N-benzyl-3-methoxy-6,7,8,9-tetrahydro-5H-benzocyclohepten-6-amine hydrochloride (47.3 g) as a white solid.

Workup

  1. stirringstirring
  2. waitwas continued for an additional 1.5 hours
  3. filtrationThe catalyst was filtered off
  4. washwashed with ethanol
  5. customRemoval of the solvent in vacuo
  6. customgave the residue, which
  7. additionTo this solution was added
  8. stirringwith mechanically stirring in an ice-bath
  9. stirringAfter stirring at ambient temperature for 1.5 hours
  10. filtrationthe mixture was filtered
  11. washthe cake was washed with ethyl acetate (50 ml)
  12. customThe product was dried in vacuo

Sources & evidence

ORD record
ord-527c8933cead491480c3f222b0ee1ddd
Source dataset
uspto-grants-1995_02
Patent number
US05387710

Reaction notes

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