Acetic Acid → HCID 18640897, compound

HRID 1031421Notes

Reaction equation

HRID 1031421 reaction equation
[CH:1]([N:4]([CH:26]([CH3:28])[CH3:27])[C:5]([C@H:7]1[CH2:12][CH2:11][C@H:10]2[C@H:13]3[C@H:22]([CH2:23][CH2:24][C@:8]12[CH3:9])[C:21]1[CH:20]=[CH:19][C:18]([OH:25])=[CH:17][C:16]=1[CH2:15][CH2:14]3)=[O:6])([CH3:3])[CH3:2].C(O)(=O)C.[N+:33]([O-])([OH:35])=[O:34].[N:37]([O-:39])=[O:38].[Na+]>O>[CH:26]([N:4]([CH:1]([CH3:2])[CH3:3])[C:5]([C@H:7]1[CH2:12][CH2:11][C@H:10]2[C@H:13]3[C@H:22]([CH2:23][CH2:24][C@:8]12[CH3:9])[C:21]1[CH:20]=[C:19]([N+:33]([O-:35])=[O:34])[C:18]([OH:25])=[CH:17][C:16]=1[CH2:15][CH2:14]3)=[O:6])([CH3:28])[CH3:27].[CH:26]([N:4]([CH:1]([CH3:2])[CH3:3])[C:5]([C@H:7]1[CH2:12][CH2:11][C@H:10]2[C@H:13]3[C@H:22]([CH2:23][CH2:24][C@:8]12[CH3:9])[C:21]1[CH:20]=[CH:19][C:18]([OH:25])=[C:17]([N+:37]([O-:39])=[O:38])[C:16]=1[CH2:15][CH2:14]3)=[O:6])([CH3:28])[CH3:27]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 944Nitric AcidHCID 18640900HCID 18640900, compoundHCID 23668193Sodium Nitrite

Product 2

HCID 18640897HCID 18640897, compoundYield 35%HCID 18640899HCID 18640899, compoundYield 20%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
75 °C

Procedure

A solution of N,N-diisopropyl-estr-1,3,5(10)-triene-3-ol-17β-carboxamide (141 mg, 0.368 mmol) in boiling acetic acid (7 mL) was slowly cooled to 75° C. and treated with a solution of concentrated nitric acid (24.8 μL) in water (1.4 mL) containing a catalytic unit of sodium nitrite. The reaction mixture was allowed to slowly cool to room temperature, then was diluted with water and extracted with ethyl acetate. The extract was washed thoroughly with water, dried, concentrated and purified by chromatography (silica gel, dichloromethane containing 5 to 10% ether) affording 55.2 mg (35%, mp 143.5°-144.5° C.) of N,N-diisopropyl-2-nitro-estr-1,3,5(10)-triene-3-ol-17β-carboxamide and 32.2 mg (20%, mp 239°-241° C.) of N,N-diisopropyl-4-nitro-estr-1,3,5(10)-triene-3-ol-17β-carboxamide.

Workup

  1. temperatureto slowly cool to room temperature
  2. extractionextracted with ethyl acetate
  3. washThe extract was washed thoroughly with water
  4. customdried
  5. concentrationconcentrated
  6. custompurified by chromatography (silica gel, dichloromethane containing 5 to 10% ether)

Sources & evidence

ORD record
ord-9f5036176f264fcc9e75420796d26d78
Source dataset
uspto-grants-1990_09
Patent number
US04954446

Reaction notes

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