Ethanolamine → Dihydrothebaine

HRID 1948839Notes

Reaction equation

HRID 1948839 reaction equation
[CH3:1][N:2]1[C@@H:18]2[CH2:19][C:7]3[CH:8]=[CH:9][C:10]([O:22][CH3:23])=[C:11]4[O:12][C@H:13]5[C:14]([O:20][CH3:21])=[CH:15][CH:16]=[C:17]2[C@:5]5([C:6]=34)[CH2:4][CH2:3]1.C(O)C.C(CN)O>O>[CH3:1][N:2]1[C@@H:18]2[CH2:19][C:7]3[CH:8]=[CH:9][C:10]([O:22][CH3:23])=[C:11]4[O:12][C@H:13]5[C:14]([O:20][CH3:21])=[CH:15][CH2:16][C@@H:17]2[C@:5]5([C:6]=34)[CH2:4][CH2:3]1

Participants

5

Reactant 3

HCID 700EthanolamineHCID 702EthanolHCID 5324289Thebaine

Product 1

HCID 5486617DihydrothebaineYield 91.3%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
70 °C

Procedure

Thebaine (142.86 g of 70 wt % material containing 30 wt % water, 100.00 g, 0.321 mol), p-toluene sulfonyl hydrazide (131.58 g, 0.706 mop and ethanol (400 ml) were stirred and heated to 70° C. Ethanol amine (43.16 g, 0.706 mol) was added to this solution over a 1 h period. The reaction was heated for a further 10 h at this temperature and then allowed to cool to room temperature. The reaction was diluted with water (400 ml) and the pH adjusted to >9.30 with concentrated (28.0-30.0%) ammonium hydroxide (30 ml) and cooled to <5° C. The product was isolated by filtration and washed with 1% v/v ammonium hydroxide in water (400 ml) to give 8,14-dihydro-thebaine as a white amorphous solid (91.94 g, 91.3% yield, 99.29 wt % by assay, with 0.16 wt % of the 6-β-parzone methyl ether impurity).

Workup

  1. temperatureThe reaction was heated for a further 10 h at this temperature
  2. temperatureto cool to room temperature
  3. concentrationwith concentrated (28.0-30.0%) ammonium hydroxide (30 ml)
  4. temperaturecooled to <5° C
  5. customThe product was isolated by filtration
  6. washwashed with 1% v/v ammonium hydroxide in water (400 ml)

Sources & evidence

ORD record
ord-4b6c07ed657e479697158a764be2cfae
Source dataset
uspto-grants-2013_03
Patent number
US08399671B2

Reaction notes

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