Nitrogen → HCID 54321703, compound

HRID 2166740Notes

Reaction equation

HRID 2166740 reaction equation
[OH:1][C:2]1[CH:15]=[C:14]([OH:16])[C:13]2[C@:12]34[CH2:17][CH2:18][N:19]([CH:20]=[O:21])[C@@H:6]([C@@H:7]3[CH2:8][CH2:9][C:10](=[O:22])[CH2:11]4)[CH2:5][C:4]=2[CH:3]=1.Cl[C:24]1[N:28]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[N:27]=[N:26][N:25]=1.C([O-])([O-])=O.[K+].[K+].N#N>CN(C=O)C.[OH-].[Na+]>[OH:16][C:14]1[C:13]2[C@:12]34[CH2:17][CH2:18][N:19]([CH:20]=[O:21])[C@@H:6]([C@@H:7]3[CH2:8][CH2:9][C:10](=[O:22])[CH2:11]4)[CH2:5][C:4]=2[CH:3]=[C:2]([O:1][C:24]2[N:28]([C:29]3[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=3)[N:27]=[N:26][N:25]=2)[CH:15]=1

Participants

7

Reactant 4

HCID 947NitrogenHCID 11430Potassium CarbonateHCID 842621H-Tetrazole, 5-chloro-1-phenyl-HCID 22823463HCID 22823463, compound

Product 1

HCID 54321703HCID 54321703, compoundYield 117.9%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 14798Sodium HydroxideSolvent

Procedure

A mixture of 2,4-dihydroxy-N-formylmorphinan-6-one (3.6 g, 12 mmol), 5-chloro-1-phenyltetrazole (2.3 g, 12.7 mmol) and anhydrous K2CO3 (8.4 g, 60.8 mmol) in 150 ml DMF was stirred at 80+ 5° C. for 16 hrs uner N2. The K2CO3 was filtered off and washed with 10 ml DMF. The combined filtrates were evaporated under vacuum to afford a dark brown residue which was taken up in 200 ml 2 N NaOH and the aqueous solution washed with ether (2×100 ml). The basic solution was the acidified with conc. HCl and extracted with CHCl3 :i-PrOH=3:2. The combined organic extracts were washed with brine, dried over sodium sulfate and evaporated to give 6.3 g of a gum. The crude product was chromatographed over silica gel and eluted with CHCl3 /MeOH=40:1 to give 1.3 g of pure ketone which after crystallization from DMF-EtOAc had a m.p. of 254°-256°.

Workup

  1. filtrationThe K2CO3 was filtered off
  2. washwashed with 10 ml DMF
  3. customThe combined filtrates were evaporated under vacuum
  4. customto afford a dark brown residue which
  5. washthe aqueous solution washed with ether (2×100 ml)
  6. extractionextracted with CHCl3
  7. washThe combined organic extracts were washed with brine
  8. dry with materialdried over sodium sulfate
  9. customevaporated

Sources & evidence

ORD record
ord-167627e3b1d14c3382e21099ce9012ef
Source dataset
uspto-grants-1983_06
Patent number
US04388463

Reaction notes

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