Acetylene → HCID 86745850, compound

HRID 1196835Notes

Reaction equation

HRID 1196835 reaction equation
[CH2:1]([Mg]Br)[CH3:2].C#C.[CH3:7][C@:8]12[CH2:24][CH2:23][C@H:22]3[C@@H:13]([CH2:14][CH2:15][C@@H:16]4[C@@H:21]3[CH2:20][CH:19]=[CH:18][CH2:17]4)[C@@H:12]1[CH2:11][CH2:10][C:9]2=[O:25].[Cl-].[NH4+]>O1CCCC1.CCOCC.O>[OH:25][C@@:9]1([C:1]#[CH:2])[CH2:10][CH2:11][C@H:12]2[C@H:13]3[C@H:22]([CH2:23][CH2:24][C@:8]12[CH3:7])[C@@H:21]1[C@H:16]([CH2:17][CH:18]=[CH:19][CH2:20]1)[CH2:15][CH2:14]3

Participants

8

Reactant 4

HCID 6326Acetylene2×HCID 25517Ammonium ChlorideHCID 54148456HCID 54148456, compound2×HCID 178418443HCID 178418443, compound3×

Product 1

HCID 86745850HCID 86745850, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To 20 ml of dry tetrahydrofuran at 0° C. is added 0.75 ml of ethylmagnesium bromide (3 molar in ethyl ether) and through this solution is passed a stream of acetylene gas. After 30 min, 0.50 of ethylmagnesium bromide was added, followed after 30 min by another 0.50 ml of ethylmagnesium bromide. Acetylene gas is passed through the mixture all the time, and is continued for another 2 hr after the last addition. To the Grignard reagent is added dropwise 0.160 g of 5α-estr-2-en-17-one, Compound 6, dissolved in 5 ml of dry tetrahydrofuran. The combined reaction mixture is stirred at 0° C. for 2 hr, and then at room temperature for 16 hr. To the reaction mixture is added dropwise saturated ammonium chloride solution, water (30 ml) and ether (30 ml). The organic phase is separated, and the water phase is extracted once more with 12 ml of ether. The combined organic phase is washed twice with sodium chloride solution and dried over sodium sulfate. Evaporation of the solvent gave a brownish oil, which was purified on a silica gel column to give 0.087 g of Compound Ia, mp 107.5°-109° C.

Workup

  1. waitis continued for another 2 hr
  2. additionafter the last addition
  3. customThe combined reaction mixture
  4. waitat room temperature for 16 hr
  5. customThe organic phase is separated
  6. extractionthe water phase is extracted once more with 12 ml of ether
  7. washThe combined organic phase is washed twice with sodium chloride solution
  8. dry with materialdried over sodium sulfate
  9. customEvaporation of the solvent
  10. customgave a brownish oil, which
  11. customwas purified on a silica gel column

Sources & evidence

ORD record
ord-e022dbc83e1a4df98d170e9a05e9791b
Source dataset
uspto-grants-1992_05
Patent number
US05116830

Reaction notes

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