Hydrochloric Acid → HCID 13374363, compound

HRID 1632765Notes

Reaction equation

HRID 1632765 reaction equation
[CH3:1][O:2][C:3]1[C:8]2[O:9][CH:10]3[CH:19]4[CH2:20][CH2:21][C:16]5([CH2:17][CH2:18]4)[C:11]3([CH2:12][CH2:13][N:14]([CH3:23])[C:15]5=O)[C:7]=2[CH:6]=[CH:5][CH:4]=1.B.CSC.Cl>O1CCCC1>[CH3:1][O:2][C:3]1[C:8]2[O:9][CH:10]3[CH:19]4[CH2:20][CH2:21][C:16]5([CH2:17][CH2:18]4)[C:11]3([CH2:12][CH2:13][N:14]([CH3:23])[CH2:15]5)[C:7]=2[CH:6]=[CH:5][CH:4]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 12423031(Dimethyl sulfide)trihydroboronHCID 86739697HCID 86739697, compound

Product 1

HCID 13374363HCID 13374363, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The 9-methoxy-3-methyl-1,2,5,6,7,7a-hexahydro-4a,7-ethanobenzofuro[3,2-e]isoquinolin-4(3H)-one (V; R1 =Me, R2 =OMe, R3 =H) so obtained was heated under reflux with 0.7 mL of borane-methyl sulfide in tetrahydrofuran overnight. Conc. hydrochloric acid was added, the tetrahydrofuran was removed, and the residue was heated under reflux with 7 mL of acetic acid and 3 mL of conc. hydrochloric acid for two hours. The solvents were removed, water and toluene were added, and the aqueous layer was made basic and extracted with methylene chloride. Removal of the solvent and short-path distillation of the residue [150° bath, 0.5 μm (0.07 Pa)] gave 0.52 g of 9-methoxy-3-methyl-1,2,3,4,5,6,7,7a-octahydro-4a,7-ethanobenzofuro[3,2-e]isoquinoline as a viscous oil that slowly solidified. NMR spectrum (220 MHz in CDCl3): τ3.1 (d/d, J=6.5/2.5 Hz, 1); 3.5 (m, 2); 5.7 (narrow m, 1); 6.2 (s, 3); 8.0 (s, 3); and 7.5-9.3 (m, 15).

Workup

  1. temperaturewas heated
  2. customthe tetrahydrofuran was removed
  3. temperaturethe residue was heated
  4. temperatureunder reflux with 7 mL of acetic acid and 3 mL of conc. hydrochloric acid for two hours
  5. customThe solvents were removed
  6. additionwater and toluene were added
  7. extractionextracted with methylene chloride
  8. customRemoval of the solvent and short-path distillation of the residue [150° bath, 0.5 μm (0.07 Pa)]

Sources & evidence

ORD record
ord-448b62c74f254c6985cd19e1c8afdc9f
Source dataset
uspto-grants-1984_10
Patent number
US04477456

Reaction notes

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