Diethyl Ether → HCID 12836872, compound

HRID 848779Notes

Reaction equation

HRID 848779 reaction equation
[CH3:1][C@@:2]12[C@@H:10]([OH:11])[CH2:9][CH2:8][C@H:7]1[C@@H:6]1[CH2:12][CH2:13][C:14]3[C@@:20]([CH3:21])([C@H:5]1[CH2:4][CH2:3]2)CC[C:16](=[O:17])[CH:15]=3.C(N(CC)[CH:26]([CH3:28])[CH3:27])(C)C.CI.[CH2:33](OCC)C>CN(C=O)C.[Ag]=O>[CH3:33][O:11][C@H:10]1[CH2:9][CH2:8][C@H:7]2[C@H:6]3[C@H:5]([CH2:4][CH2:3][C@:2]12[CH3:1])[C@:20]1([CH3:21])[C:14](=[CH:15][C:16](=[O:17])[C@H:26]([CH3:27])[CH2:28]1)[CH2:13][CH2:12]3

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 6013TestosteroneHCID 6328Methyl iodideHCID 81531Diisopropylethylamine

Product 1

HCID 12836872HCID 12836872, compound

Reagents, catalysts & solvents 2

HCID 92152Silver(II) oxideCatalystHCID 6228DimethylformamideSolvent

Procedure

Testosterone (50 g.) in DMF (500 ml.) is cooled to 5° in an ice bath and silver oxide (58 g.) and N,N-diisopropylethylamine (85 ml.) are added. The mixture is stirred and methyl iodide (142 g., 62 ml.) is added in a slow stream. The temperature remains about 5° initially, the stirring is continued without further addition of ice to the bath and the mixture comes to 20°-25°. After 18 hours, diethyl ether (2 l.) is added and the mixture is filtered thru a bed of celite. The filtrate is washed successively with water, dilute hydrochloric acid, again with water, dried over sodium sulfate, filtered and concentrated. The concentrate is column chromatographed over silica gel (1 kg.) eluting by a gradient between SSB (5 l.) and SSB-ethyl acetate (80:20, 5 l.). The appropriate fractions (TLC) are pooled and concentrated to give the title compound; m.p. 130°-145°; UV (ethanol) λ=240 nm (ε=15,000); IR (mull) 1670 cm-1 ; NMR (CDCl3) 0.8, 1.1, 1.21, 3.26, 3.32, and 5.71 δ; MS (m/e) 316.

Workup

  1. customremains about 5°
  2. additionthe stirring is continued without further addition of ice to the bath
  3. customcomes to 20°-25°
  4. filtrationthe mixture is filtered thru a bed of celite
  5. washThe filtrate is washed successively with water, dilute hydrochloric acid, again with water
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customchromatographed over silica gel (1 kg.)
  10. washeluting by a gradient between SSB (5 l.) and SSB-ethyl acetate (80:20, 5 l.)
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-3b77f767499a490eab1f06a1b4f7625c
Source dataset
uspto-grants-1981_10
Patent number
US04297350

Reaction notes

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