Ammonium Hydroxide → HCID 56607916, compound

HRID 904208Notes

Reaction equation

HRID 904208 reaction equation
Cl.[CH3:2][O:3][C:4]1[CH:5]=[CH:6][C:7]2[CH2:8][C@H:9]3[NH:20][CH2:19][CH2:18][C@@:15]4([C:16]=2[CH:17]=1)[C@H:10]3[C@@H:11]([CH3:22])[CH2:12][C:13](=[O:21])[CH2:14]4.C([O-])(O)=O.[Na+].[CH:28]1([CH2:31]Br)[CH2:30][CH2:29]1.[NH4+].[OH-]>CN(C=O)C.O>[CH:28]1([CH2:31][N:20]2[CH2:19][CH2:18][C@@:15]34[C:16]5[CH:17]=[C:4]([O:3][CH3:2])[CH:5]=[CH:6][C:7]=5[CH2:8][C@@H:9]2[C@@H:10]3[C@@H:11]([CH3:22])[CH2:12][C:13](=[O:21])[CH2:14]4)[CH2:30][CH2:29]1

Participants

7

Reactant 4

HCID 14923Ammonium HydroxideHCID 81503BromomethylcyclopropaneHCID 516892Sodium BicarbonateHCID 70586442HCID 70586442, compound

Product 1

HCID 56607916HCID 56607916, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a suspension of 3-methoxy-8β-methylmorphinan-6-one hydrochloride (prepared in Part C) in DMF (1 g/10 ml) was added NaHCO3 (2.2 equivalents [eq]) and cyclopropylmethyl bromide (1.5 eq). The mixture was heated under an argon atmosphere at 100° C. for 16 hours, then cooled. The mixture was filtered and the filtrate was evaporated in high vacuum to yield a residue. The residue was dissolved in water, adjusted to about pH 11 with concentrated NH4OH and extracted with three portions of benzene. The organic phase was dried, filtered and evaporated to a residue. The residue was chromatographed over silica Gel G using 15:1 (V/V) chloroform:methanol as the eluant. Pure chromatographic fractions were combined and the product crystallized as the free base, mp 114°-115° C., in 72% yield.

Workup

  1. temperaturecooled
  2. filtrationThe mixture was filtered
  3. customthe filtrate was evaporated in high vacuum
  4. customto yield a residue
  5. extractionextracted with three portions of benzene
  6. customThe organic phase was dried
  7. filtrationfiltered
  8. customevaporated to a residue
  9. customThe residue was chromatographed over silica Gel G
  10. customthe product crystallized as the free base, mp 114°-115° C., in 72% yield

Sources & evidence

ORD record
ord-b008fe37198640cfb472ee0723c68822
Source dataset
uspto-grants-1980_10
Patent number
US04230712

Reaction notes

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