Nitrogen → Androstenone

HRID 326978

Reaction equation

HRID 326978 reaction equation
C(=O)([O-])OC.COC(O[C@H:11]1[CH2:16][CH2:15][C@H:14]2[C@H:17]3[C@H:27]([CH2:28][CH2:29][C@:12]12[CH3:13])[C@:25]1([CH3:26])[C@H:20]([CH2:21][C:22](=[O:30])[CH2:23][CH2:24]1)[CH2:19][CH2:18]3)=O.N#N>C1(C)C=CC=CC=1>[CH3:13][C@:12]12[CH2:29][CH2:28][C@H:27]3[C@@H:17]([CH2:18][CH2:19][C@@H:20]4[C@:25]3([CH3:26])[CH2:24][CH2:23][C:22](=[O:30])[CH2:21]4)[C@@H:14]1[CH2:15][CH:16]=[CH:11]2

Participants

5

Reactant 3

HCID 947NitrogenHCID 4585885MethylcarbonateHCID 8674741617beta-Methoxycarbonyloxy-5alpha-androstan-3-one

Product 1

HCID 6852393AndrostenoneYield 87%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

This synthesis is depicted in FIG. 1. A solution of the methyl carbonate, 17β-methoxycarbonyloxy-5α-androstan-3-one (II) (9.6 g, 27.6 mmol) in toluene (200 ml) was pyrolyzed (b) in a Pyrex glass column (l=10 m, φ=9 mm) at 480° (N2 stream ca. 11 ml/min) at a rate of ca. 1 g/h. The crude product (collected in two liquid N2 -cooled traps) was washed with sat. aq. NaHCO3 - and NaCl-solution, dried (Na2SO4) and evaporated. The residue (7.24 g, 97%) was recrystallized from PE at 0° to give 6.42 g (87%) of 1. An analytical sample was recrystallized from acetonitrile at RT. M.p. 142°-144°, [a]D =+35.6° (c=1.15) ([2]: m.p. 140°-141°, [a]D17 =+38° (c=2.08)). - IR. (CDCl3): 1710s, 1595w. - 1H-NMR. (360 Mhz): 0.79 (s, 3 H); 1.05 (s, 3 H); 5.70 (m, 1 H); 5.84 (m, 1 H).

Workup

  1. customat 480°
  2. washThe crude product (collected in two liquid N2 -cooled traps) was washed with sat. aq. NaHCO3 - and NaCl-solution
  3. dry with materialdried (Na2SO4)
  4. customevaporated
  5. customThe residue (7.24 g, 97%) was recrystallized from PE at 0°

Sources & evidence

ORD record
ord-d0342f68a7d542b88fd1198266f47f4f
Source dataset
uspto-grants-1993_12
Patent number
US05272134

Linked notes

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