Water → HCID 15281055, compound

HRID 1587555Notes

Reaction equation

HRID 1587555 reaction equation
[CH3:1][C:2]([NH:5][C:6]([C@H:8]1[CH2:13][CH2:12][C@H:11]2[C@H:14]3[C@H:24]([CH2:25][CH2:26][C@:9]12[CH3:10])[C@:22]1([CH3:23])[C:17](=[C:18]([N:28]=[N+]=[N-])[C:19](=[O:27])[CH2:20][CH2:21]1)[CH2:16][CH2:15]3)=[O:7])([CH3:4])[CH3:3].O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1>[NH2:28][C:18]1[C:19](=[O:27])[CH2:20][CH2:21][C@@:22]2([CH3:23])[C:17]=1[CH2:16][CH2:15][C@@H:14]1[C@@H:24]2[CH2:25][CH2:26][C@@:9]2([CH3:10])[C@H:11]1[CH2:12][CH2:13][C@@H:8]2[C:6]([NH:5][C:2]([CH3:4])([CH3:3])[CH3:1])=[O:7]

Participants

5

Reactant 3

HCID 962WaterHCID 11776TriphenylphosphineHCID 15281054HCID 15281054, compound

Product 1

HCID 15281055HCID 15281055, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of N-(1,1-dimethylethyl)-4-azido-3-oxoandrost-4-ene-17β-carboxamide (1.3 g, 3.15 mmole) in tetrahydrofuran (20mL)-water (7 mL) was added triphenylphosphine (1.41 g, 5.38 mmole). The reaction was heated at reflux temperature for 16 hours. Most of the tetrahydrofuran was removed under vacuum. Dichloromethane was added to the mixture and the organic solution was placed atop a column of silica gel and flash chromatographed (hexane-30% ethyl acetate). The fractions containing the product were combined and concentrated to a white solid which was crystallized from diethyl ether to give the 4-amino-N-(1,1-dimethylethyl)-3-oxoandrost-4-ene-17β-carboxamide (0.67 g, 54.9%). IR 3476, 3442, 3382, 1672, 1659, 1620(m), 1580(m) cm-1 ; MS (CI) m/z 387 (100%, M+ +1); (EI) m/z 386 (10%, M+), 343 (100%); 1H NMR (CDCl3) δ 0.72 (3H, s, C18 -Me), 1.16 (s, C19 -Me), 1.34 (s, tBu-Me's), 3.49 (2H, br s, NH2 ), 5.08 (1H, s, NHCO); 13C NMR (CDCl3) δ 132.97, 138.39, 171.69, 194.22. This compound has the following structure: ##STR5##

Workup

  1. temperatureThe reaction was heated
  2. temperatureat reflux temperature for 16 hours
  3. customMost of the tetrahydrofuran was removed under vacuum
  4. additionDichloromethane was added to the mixture
  5. customchromatographed (hexane-30% ethyl acetate)
  6. additionThe fractions containing the product
  7. concentrationconcentrated to a white solid which
  8. customwas crystallized from diethyl ether

Sources & evidence

ORD record
ord-86dfd0bad38c4065ae40af3b4c1a063d
Source dataset
uspto-grants-1993_06
Patent number
US05218110

Reaction notes

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