4-Bromobutyronitrile → HCID 68131083, compound

HRID 1282904Notes

Reaction equation

HRID 1282904 reaction equation
[Na].[CH:2]1[C:18]2[CH2:17][C@H:16]3[N:19]([CH2:21][CH2:22][C@@:8]45[C@H:15]3[CH:14]=[CH:13][C@H:11]([OH:12])[C@@H:9]4[O:10][C:6]([C:7]=25)=[C:4]([OH:5])[CH:3]=1)[CH3:20].Br[CH2:24][CH2:25][CH2:26][C:27]#[N:28]>C(O)C>[C:27]([CH2:26][CH2:25][CH2:24][O:5][C:4]1[CH:3]=[CH:2][C:18]2[CH2:17][C@H:16]3[N:19]([CH3:20])[CH2:21][CH2:22][C@:8]45[C:7]=2[C:6]=1[O:10][C@H:9]4[C@@H:11]([OH:12])[CH:13]=[CH:14][C@@H:15]35)#[N:28]

Participants

5

Reactant 3

HCID 214124-BromobutyronitrileHCID 5288826MorphineHCID 5360545Sodium

Product 1

HCID 68131083HCID 68131083, compoundYield 94.6%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 0.973 g of sodium dissolved in 100 ml of abs. ethanol was added 12.1 g (0.042 mol) of morphine. After heating at reflux for 1 hr, the reaction mixture was cooled to room temperature and 6.3 g of 4-bromobutyronitrile was added; then heating under reflux was resumed for 16 hr. After removal of the ethanol, the residue was dissolved in chloroform (150 ml). The chloroform solution was washed with 2 N sodium hydroxide (2 × 50 ml) and with water (50 ml). After drying, the solvent was removed in vacuo to give 14.0 g of crude 3-(3-cyanopropoxy)-7,8-didehydro-4,5 α-epoxy-17-methylmorphinan-6 α-ol. A sample of this compound was distilled, b.p. 260°-265°/0.25 mm; [α]D25 -104.09°(c 1.06, MeOH).

Workup

  1. temperatureAfter heating
  2. temperatureat reflux for 1 hr
  3. temperaturethen heating
  4. temperatureunder reflux
  5. customAfter removal of the ethanol
  6. dissolutionthe residue was dissolved in chloroform (150 ml)
  7. washThe chloroform solution was washed with 2 N sodium hydroxide (2 × 50 ml) and with water (50 ml)
  8. customAfter drying
  9. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-2f5b9407c04a4024a0814ebc2faa0721
Source dataset
uspto-grants-1976_08
Patent number
US03972992

Reaction notes

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