Water → 6-Oximino-17-cyclopropylmethyl-4,5alpha-epoxy-3,14-dihydroxymorphinan

HRID 845825

Reaction equation

HRID 845825 reaction equation
[CH:1]1[C:6]2[CH2:7][C@H:8]3[N:13]([CH2:14][CH:15]4[CH2:17][CH2:16]4)[CH2:12][CH2:11][C@:10]45[C@H:18]([C:20]([CH2:22][CH2:23][C@@:9]34[OH:24])=O)[O:19][C:4]([C:5]=25)=[C:3]([OH:25])[CH:2]=1.Cl.Cl.[NH2:28][OH:29].[OH-].[Na+].O>CO>[N:28](=[C:20]1[CH2:22][CH2:23][C@:9]2([OH:24])[C@:10]34[CH2:11][CH2:12][N:13]([CH2:14][CH:15]5[CH2:17][CH2:16]5)[C@@H:8]2[CH2:7][C:6]2[CH:1]=[CH:2][C:3]([OH:25])=[C:4]([O:19][C@@H:18]13)[C:5]4=2)[OH:29]

Participants

6

Reactant 4

HCID 962WaterHCID 14798Sodium HydroxideHCID 443297Hydroxyamine hydrochlorideHCID 5485201Naltrexone Hydrochloride

Product 1

HCID 867422946-Oximino-17-cyclopropylmethyl-4,5alpha-epoxy-3,14-dihydroxymorphinan

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A mixture of naltrexone hydrochloride (1.34 g, 3 mmol) and hydroxylamine hydrochloride (0.28 g, 4 mmol) was dissolved in 20 mL of MeOH and 2.8 mL of aqueous NaOH added. The mixture was stirred for 15 h. Water was added (100 mL) and the mixture extracted with 150 mL CHCl3 (3×50 mL). The combined extracts were dried (MgSO4) and evaporated. The residue obtained was chromatographed on a column of silica gel (approx. size 40 microns) using ethyl acetate-ethanol-NH4OH (300:1.5:2) as eluent. The combined fractions were evaporated and the residue recrystallized from CH2Cl2 -petroleum ether. Yield: 0.54 g (50.5%) mp 235-236° C. IR (KBr): No C=O absorption at 1720 cm-1. 1H NMR (CDCl3) δ6.7 (2d, 2H, J=10 Hz) 5 (s,C5H); Rf: silica gel 60 in ethylacetate-EtOH-NH4OH (100:1:1) 0.22. Anal. Calcd for C20H24N2O4 : C, 67.40; H, 6.79; N, 7.86. Found: C, 67.12; H, 6.88; N, 7.63.

Workup

  1. extractionthe mixture extracted with 150 mL CHCl3 (3×50 mL)
  2. dry with materialThe combined extracts were dried (MgSO4)
  3. customevaporated
  4. customThe residue obtained
  5. customwas chromatographed on a column of silica gel (approx. size 40 microns)
  6. customThe combined fractions were evaporated
  7. customthe residue recrystallized from CH2Cl2 -petroleum ether
  8. customIR (KBr): No C=O absorption at 1720 cm-1

Sources & evidence

ORD record
ord-62ceef49c77447859b572a476de99f30
Source dataset
uspto-grants-1988_07
Patent number
US04760069

Linked notes

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