Ammonium Hydroxide → HCID 11729014, compound

HRID 369004Notes

Reaction equation

HRID 369004 reaction equation
B(Br)(Br)Br.Cl.[CH:6]1([CH2:9][N:10]2[CH2:29][CH2:28][C@:17]34[C:18]5[C:19]6[O:27][C@@:16]3([CH3:30])[C:15](=[O:31])[CH2:14][CH2:13][C@@:12]4([O:32][CH2:33][CH2:34][CH3:35])[C@H:11]2[CH2:24][C:23]=5[CH:22]=[CH:21][C:20]=6[O:25]C)[CH2:8][CH2:7]1.[NH4+].[OH-]>C(Cl)Cl>[CH:6]1([CH2:9][N:10]2[CH2:29][CH2:28][C@:17]34[C:18]5[C:19]6[O:27][C@@:16]3([CH3:30])[C:15](=[O:31])[CH2:14][CH2:13][C@@:12]4([O:32][CH2:33][CH2:34][CH3:35])[C@H:11]2[CH2:24][C:23]=5[CH:22]=[CH:21][C:20]=6[OH:25])[CH2:7][CH2:8]1

Participants

5

Reactant 3

HCID 14923Ammonium HydroxideHCID 25134Boron tribromideHCID 69036841HCID 69036841, compound

Product 1

HCID 11729014HCID 11729014, compoundYield 70.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
2.5 °C

Procedure

A 1 M solution of boron tribrornide in CH2Cl2 (7.3 ml) was added at once to an ice-cooled solution of the compound 16 (480 mg, 0.97 inmol) in 50 ml of CH2Cl2. After 50 min stirring at 0-5° C., a mixture of 13 g ice and 3 ml conc. NH4OH was added. The resulting mixture was stirred at room temperature for 30 min and the extracted with CH2Cl2 (3×30 ml). The combined organic layers were washed with brine (45 ml), dried over Na2SO4 and evaporated. The residue (204 mg slightly brown foam) was treated with 0.5 ml hot MeOH to afford 302 mg (55%) of 17-(cyclopropylmethyl)-4,5α-epoxy-3-hydroxy-5-methyl-14-n-propyloxymorphinan-6-one (compound 17). M.p. 184-186° C. IR (KBr): 3390 (OH), 1720 (CO)cm-1. CI-MS: m/z 397 (M+ +1). 1H-NMR (CDCl3): δ 10.24 (broad s, OH), 6.73 (d, J=8.2 Hz, 1 arom. H), 6.65 (d, J=8.2 Hz, 1 arom. H)1.62 (s, CH3 --C(5)), 1.00 (t,J=7.3 Hz, CH3). Analysis calculated for C24H31NO4. 0.6 MeOH (416.74): C 70.90, H 8.08, N 3.36; found: C 70.76, H 7.73, N 3.52.

Workup

  1. additionwas added
  2. stirringThe resulting mixture was stirred at room temperature for 30 min
  3. extractionthe extracted with CH2Cl2 (3×30 ml)
  4. washThe combined organic layers were washed with brine (45 ml)
  5. dry with materialdried over Na2SO4
  6. customevaporated
  7. additionThe residue (204 mg slightly brown foam) was treated with 0.5 ml hot MeOH

Sources & evidence

ORD record
ord-531e6b3006f8476a88d3c6533dc5373d
Source dataset
uspto-grants-2000_10
Patent number
US06136817

Reaction notes

Loading…