Water → HCID 10427683, compound

HRID 1885331Notes

Reaction equation

HRID 1885331 reaction equation
[N:1]([C:4]1[C:24](=[O:25])[CH2:23][CH2:22][C@@:21]2([CH3:26])[C:5]=1[CH2:6][CH2:7][C@@H:8]1[C@@H:20]2[CH2:19][CH2:18][C@@:17]2([CH3:27])[C@H:9]1[CH2:10][CH2:11][C@@H:12]2[C@H:13]([CH3:16])[CH2:14][OH:15])=[N+]=[N-].O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1>[NH2:1][C:4]1[C:24](=[O:25])[CH2:23][CH2:22][C@@:21]2([CH3:26])[C:5]=1[CH2:6][CH2:7][C@@H:8]1[C@@H:20]2[CH2:19][CH2:18][C@@:17]2([CH3:27])[C@H:9]1[CH2:10][CH2:11][C@@H:12]2[C@H:13]([CH3:16])[CH2:14][OH:15]

Participants

5

Reactant 3

HCID 962WaterHCID 11776TriphenylphosphineHCID 57106076HCID 57106076, compound

Product 1

HCID 10427683HCID 10427683, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of (20S)-4-azido-21-hydroxy-20-methylpregn-4-en-3-one (3.15 mmole) in tetrahydrofuran (20 mL)-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 (20S)-4-amino-21-hydroxy-20-methylpregn-4-en-3-one. IR 3510, 3470, 3384, 1648, 1614, 1576 cm-1 ; MS (CI) 346 (100%, M+ +1) (EI) 345 (65%, M+), 302 (100%); 1H NMR δ (CDCl3) 0.73 (3H, s, C18 -Me), 1.04 (d, C21 -Me), 1.15 (s, C19 -Me), 2.42-2.56 (3H m) 3.73 (v br NH2) 3.36 (1H dd 1/2 C21 -CH2), 3.63 (1H, dd, 1/2 C21 -CH2); 13C NMR δ (CDCl3) 132.85, 139.15, 194.38. This compound has the following structure: ##STR4##

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-49b029e83b844881b2b46e2c37c9f8f9
Source dataset
uspto-grants-1992_09
Patent number
US05143909

Reaction notes

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