Sulfuric Acid → 4-amino-N-(1,1-dimethylethyl)-3-oxoandrosta-4,6-diene-17beta-carboxamide

HRID 654352Notes

Reaction equation

HRID 654352 reaction equation
O1[C:3]23[C@:16]([CH3:21])([CH2:17][CH2:18][C:19](=[O:20])[CH:2]12)[C@@H:15]1[C@H:6]([C@H:7]2[C@@:11]([CH2:13][CH2:14]1)([CH3:12])[C@@H:10]([C:22]([NH:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:9][CH2:8]2)[CH2:5][CH2:4]3.[N-:29]=[N+]=[N-].[Na+].[N-]=[N+]=[N-].S(=O)(=O)(O)O>CS(C)=O>[NH2:29][C:2]1[C:19](=[O:20])[CH2:18][CH2:17][C@@:16]2([CH3:21])[C:3]=1[CH:4]=[CH:5][C@@H:6]1[C@@H:15]2[CH2:14][CH2:13][C@@:11]2([CH3:12])[C@H:7]1[CH2:8][CH2:9][C@@H:10]2[C:22]([NH:24][C:25]([CH3:27])([CH3:28])[CH3:26])=[O:23]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 33558AzideHCID 86745913N-(1,1-Dimethylethyl)-4,5-epoxy3-oxoandrostane-17beta-carboxamide

Product 1

HCID 677532974-amino-N-(1,1-dimethylethyl)-3-oxoandrosta-4,6-diene-17beta-carboxamide

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
60 °C

Procedure

A solution of 4,5-epoxy-N-(1,1-dimethylethyl)-3-oxoandrostane-17β-carboxamide (3.0 g, 7.7 mmole) in dimethyl sulfoxide (40 mL), under a nitrogen atmosphere, was placed in an oil bath heated at 60° C. The solution was stirred vigorously as sodium azide (8.11 g, 0.338 mole) was slowly added. After the addition of the azide was complete, concentrated sulfuric acid (0.54 mL) was added. The bath temperature was raised to 100° C. and the reaction was stirred at this temperature for 90 minutes. The reaction was removed from the oil bath and cooled to room temperature and the resulting solid mass was broken up and poured into cold water (550 mL). The mixture was stirred for 30 min and the solids were collected by filtration, washed with water and dried to a yellow solid. The crude product was purified by flash chromatography (hexane-30% ethyl acetate) to give 4-amino-N-(1,1-dimethylethyl)-3-oxoandrosta-4,6-diene-17β-carboxamide as a crystalline, yellow solid (0.90 g, 30%) (aq methanol). IR 3442, 3372, 1662, 1616, 1592, 1570, 1512 cm-1 ; MS (CI) m/z 385 (100%, M+ +1); (EI) m/z 384 (35%, M+), 150 (100%); 1H NMR (CDCl3) δ 0.77 (3H, s, C18 -Me), 1.06 (3H, s, C18 -Me), 1.37 (s, tBu-Me's), 2.44-2.54 (1H, pr dd), 2.58-2.72 (1H, pr dd), 3.70 (1.6H, br, NH2), 5.13 (1H, s, NH), 5.97 (1H, dd), 6.30 (1H, dd); 13C NMR (CDCl3) δ 132.27, 132.44, 135.90, 171.51, 194.27. This compound has the following structure: ##STR3##

Workup

  1. additionwas slowly added
  2. temperatureThe bath temperature was raised to 100° C.
  3. customThe reaction was removed from the oil bath
  4. temperaturecooled to room temperature
  5. additionpoured into cold water (550 mL)
  6. stirringThe mixture was stirred for 30 min
  7. filtrationthe solids were collected by filtration
  8. washwashed with water
  9. customdried to a yellow solid
  10. customThe crude product was purified by flash chromatography (hexane-30% ethyl acetate)

Sources & evidence

ORD record
ord-3e3e4d5180a5487d8f710cd1a8eb6b45
Source dataset
uspto-grants-1992_07
Patent number
US05130424

Reaction notes

Loading…