Potassium Bromide → HCID 68542914, compound

HRID 1441521Notes

Reaction equation

HRID 1441521 reaction equation
[O:1]1[C@@H:13]2[C@@:14]34[CH2:16][CH2:17][N:18]([CH3:19])[C@@H:8]([C@:9]3([O:21][CH2:22][CH2:23][CH2:24][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[CH2:10][CH2:11][C:12]2=[O:20])[CH2:7][C:6]2=[C:15]4[C:2]1=[C:3](OC1N(C3C=CC=CC=3)N=NN=1)[CH:4]=[CH:5]2.[K+].[Br-]>[Pd].C(O)(=O)C>[O:1]1[C@@H:13]2[C@@:14]34[CH2:16][CH2:17][N:18]([CH3:19])[C@@H:8]([C@:9]3([O:21][CH2:22][CH2:23][CH2:24][C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=3)[CH2:10][CH2:11][C:12]2=[O:20])[CH2:7][C:6]2=[C:15]4[C:2]1=[CH:3][CH:4]=[CH:5]2

Participants

5

Reactant 2

HCID 253877Potassium BromideHCID 68541542HCID 68541542, compound

Product 1

HCID 68542914HCID 68542914, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolvent

Procedure

A mixture of 4,5α-epoxy-17-methyl-14β-[(3-phenylpropyl)oxy]-3-[(1-phenyl-1H-tetrazol-5-yl)oxy]morphinan-6-one (6.20 g, 11.00 mmol), 10% Pd/C catalyst (2.48 g) and 100 ml glacial acetic acid was hydrogenated at 50 psi and 40° C. for 17 h. After filtering off the catalyst, the filtrate was reduced down to a volume of 30 ml, 150 ml of ice/water mixture was added to it and after alkalising with conc. NH4OH it was extracted with CH2Cl2 (1×100 ml, 3×75 ml). The combined organic phases were washed with saturated NaCl solution (4×200 ml), dried over Na2SO4 and evaporated down. The evaporation residue (4.15 g of yellowish oil, DC pure) was crystallised out of a little methanol and in this way 3.20 g (72%) of the compound 53 was obtained as colourless crystals. Fp. 105-109° C.; MS (CI): 404 (M++1); IR (KBr): 1721 (C═O) cm−1; 1H-NMR (DMSO-d6): δ 7.29-7.16 (m, 5 arom. H), 7.04 (t, J=8.0 Hz, 1 arom. H), 6.73 (d, J=8.0 Hz, 1 arom. H), 6.64 (d, J=8.0 Hz, 1 arom. H), 4.75 (s, 1H, C5-H), 2.28 (s, 3H, N17-CH3).

Workup

  1. filtrationAfter filtering off the catalyst
  2. additionwas added to it
  3. extractionwas extracted with CH2Cl2 (1×100 ml, 3×75 ml)
  4. washThe combined organic phases were washed with saturated NaCl solution (4×200 ml)
  5. dry with materialdried over Na2SO4
  6. customevaporated down
  7. customThe evaporation residue (4.15 g of yellowish oil, DC pure) was crystallised out of a little methanol and in this way 3.20 g (72%) of the compound 53
  8. customwas obtained as colourless crystals
  9. custom105-109° C.

Sources & evidence

ORD record
ord-4e2d86379a7b4c99a8296124faef4915
Source dataset
uspto-grants-2010_02
Patent number
US07655671B2

Reaction notes

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