Hydrochloric Acid → HCID 67617838, compound

HRID 962627Notes

Reaction equation

HRID 962627 reaction equation
[H-].[Na+].O=[C:4]1[CH2:9][CH2:8][C@H:7]2[C@H:10]3[C@H:20]([CH2:21][CH2:22][C@:5]12[CH3:6])[C@:18]1([CH3:19])[C@H:13]([CH:14]([CH3:24])[C:15](=[O:23])[CH2:16][CH2:17]1)[CH2:12][CH2:11]3.[Cl:25][C:26]1[CH:40]=[CH:39][CH:38]=[CH:37][C:27]=1[CH2:28]P(=O)(OCC)OCC.Cl>CN(C=O)C.C(Cl)Cl.CC(C)=O>[Cl:25][C:26]1[CH:40]=[CH:39][CH:38]=[CH:37][C:27]=1[CH:28]=[C:4]1[CH2:9][CH2:8][C@H:7]2[C@H:10]3[C@H:20]([CH2:21][CH2:22][C@:5]12[CH3:6])[C@:18]1([CH3:19])[C@H:13]([CH:14]([CH3:24])[C:15](=[O:23])[CH2:16][CH2:17]1)[CH2:12][CH2:11]3

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 12520073Diethyl ((2-chlorophenyl)methyl)phosphonateHCID 54231630HCID 54231630, compound

Product 1

HCID 67617838HCID 67617838, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 21584124Propan-2-one--dichloromethane (1/1)Solvent

Conditions

Temperature
70 °C

Procedure

Sodium hydride (60%, 26 mg, 0.66 mmole) was added to a solution of 101 mg. (0.33 mol) of 17-keto-4-methyl-5α-androstan-3-one (F) and 173 mg (0.66 mol) of diethyl 2-chlorobenzylphosphonate in 1.0 ml of dry DMF at room temperature. The mixture was heated at 70° C. in a nitrogen atmosphere with stirring for 110 minutes, cooled, poured into 0.5N HCl (20 ml) and extracted with methylene chloride (3×). The organic phases were combined, washed with water (3×), saturated NaCl solution and dried over magnesium sulfate. The organic phase was concentrated under reduced pressure to yield a tan, gummy solid. Flash chromatography of the crude solid was conducted on a silica gel 60×20 mm column, and eluted with 4:1 methylene chloride/acetone in 6 ml. fractions. Fractions 18-24 contained the product which were combined and evaporated to yield a white solid, mp 205°-208° C., yielding one spot on silica gel TLC using 4:1 methylene chloride/acetone. The proton NMR confirmed the assigned structure for 39.

Workup

  1. customat room temperature
  2. temperaturecooled
  3. extractionextracted with methylene chloride (3×)
  4. washwashed with water (3×), saturated NaCl solution
  5. dry with materialdried over magnesium sulfate
  6. concentrationThe organic phase was concentrated under reduced pressure
  7. customto yield a tan, gummy solid
  8. washeluted with 4:1 methylene chloride/acetone in 6 ml
  9. customevaporated
  10. customto yield a white solid, mp 205°-208° C.
  11. customyielding one spot on silica gel TLC

Sources & evidence

ORD record
ord-29203157d64b4629aaf39fb9ff734350
Source dataset
uspto-grants-1998_06
Patent number
US05760045

Reaction notes

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