Diazomethane → Diazomethane

HRID 1587611Notes

Reaction equation

HRID 1587611 reaction equation
[N:1]([N:3](C)[C:4](N)=O)=O.[OH-].[K+].[CH3:10][O:11][C:12]([O:14][C@@H:15]1[C@@:36]2([CH3:37])[C:19](=[CH:20][CH:21]=[C:22]3[C@@H:35]2[CH2:34][CH2:33][C@@:32]2([CH3:38])[C@H:23]3[CH2:24][CH2:25][C@@H:26]2[CH:27]([C:29]([OH:31])=[O:30])[CH3:28])[CH2:18][C@@H:17]([O:39][C:40]([O:42][CH3:43])=[O:41])[CH2:16]1)=[O:13].[N+](=[CH2:46])=[N-]>C(OCC)C.C(O)(=O)C>[N+:3](=[CH2:4])=[N-:1].[CH3:10][O:11][C:12]([O:14][C@@H:15]1[C@@:36]2([CH3:37])[C:19](=[CH:20][CH:21]=[C:22]3[C@@H:35]2[CH2:34][CH2:33][C@@:32]2([CH3:38])[C@H:23]3[CH2:24][CH2:25][C@@H:26]2[CH:27]([C:29]([O:31][CH3:46])=[O:30])[CH3:28])[CH2:18][C@@H:17]([O:39][C:40]([O:42][CH3:43])=[O:41])[CH2:16]1)=[O:13]

Participants

8

Reactant 4

HCID 9550Diazomethane2×HCID 12699N-Methyl-N-nitrosoureaHCID 14797Potassium HydroxideHCID 537642171alpha,3beta-Bis(methoxycarbonyloxy)pregna-5,7-diene-20-carboxylic acid

Product 2

HCID 9550DiazomethaneHCID 18652401Methyl 1alpha,3beta-bis(methoxycarbonyloxy)pregna-5,7-diene-20 carboxylate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 3283Diethyl EtherSolvent3×

Procedure

A solution of diazomethane in diethyl ether was prepared by adding N-nitroso-N-methylurea to a mixture of 50% aqueous potassium hydroxide solution and diethyl ether in accordance with the method described in Organic Syntheses Collective Volume 2, p. 165 (1943) and this solution was added to a solution of 85 mg of 1α,3β-bis(methoxycarbonyloxy)pregna-5,7-diene-20-carboxylic acid (prepared in Example 6 above) in 5 ml of diethyl ether until the yellow color of diazomethane would be persistent. After the excess diazomethane was decomposed by addition of acetic acid, the reaction mixture was washed with aqueous sodium hydrogen carbonate solution and aqueous sodium chloride solution, dried over sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography to give 79 mg of methyl 1α,3β-bis(methoxycarbonyloxy)pregna-5,7-diene-20-carboxylate.

Workup

  1. washthe reaction mixture was washed with aqueous sodium hydrogen carbonate solution and aqueous sodium chloride solution
  2. dry with materialdried over sodium sulfate
  3. concentrationconcentrated
  4. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-c42d566e63ad4428b3857bf8afb3479d
Source dataset
uspto-grants-1993_06
Patent number
US05218109

Reaction notes

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