p-Toluenesulfonic acid → 13-Ethinyl-3-ethoxy-10-methyl-gona-3,5-dien-17-one

HRID 972274Notes

Reaction equation

HRID 972274 reaction equation
[C:1]([C@:3]12[CH2:11][CH2:10][C@@H:9]3[C@:12]4([CH3:21])[C:17]([CH2:18][CH2:19][C@H:8]3[C@@H:7]1[CH2:6][CH2:5][C:4]2=[O:22])=[CH:16][C:15](=[O:20])[CH2:14][CH2:13]4)#[CH:2].O1CCO[CH2:25][CH2:24]1.C(OC(O)O)C.C1(C)C=CC(S(O)(=O)=O)=CC=1>O.N1C=CC=CC=1>[C:1]([C@:3]12[CH2:11][CH2:10][C@@H:9]3[C@:12]4([CH3:21])[C:17](=[CH:18][CH2:19][C@H:8]3[C@@H:7]1[CH2:6][CH2:5][C:4]2=[O:22])[CH:16]=[C:15]([O:20][CH2:24][CH3:25])[CH2:14][CH2:13]4)#[CH:2]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 312751,4-DioxaneHCID 5231668OrthoameisensaureathylesterHCID 1570448413-Ethinyl-10-methyl-gon-4-ene-3,17-dione

Product 1

HCID 13171092513-Ethinyl-3-ethoxy-10-methyl-gona-3,5-dien-17-one

Reagents, catalysts & solvents 2

HCID 962WaterCatalystHCID 1049PyridineSolvent

Procedure

A mixture of 1.2 g of 13-ethinyl-10-methyl-gon-4-ene-3,17-dione, 20 ml of dioxane, 2 ml of orthoformic acid ethyl ester and 60 mg of p-toluenesulphonic acid is stirred at room temperature for 3 3/4 hours with exclusion of light. The reaction mixture is poured into 150 ml of water containing 5 drops of pyridine and extracted twice with ethyl acetate and the organic layer is washed with water and saturated sodium chloride solution until neutral, dried and evaporated in a water pump vacuum. The crystalline crude 13-ethinyl-3-ethoxy-10-methyl-gona-3,5-dien-17-one, which is obtained, is then dissolved in 20 ml of dioxane and the solution is added dropwise, in the course of 30 minutes, to a solution, which is saturated with acetylene, of 6 g of a lithium acetylide/ethylenediamine complex in 60 ml of dioxane, whilst passing acetylene through the mixture at the same time. The reaction mixtue is then stirred for a further 15 minutes at room temperature and treated, whilst cooling, with saturated ammonium chloride solution and with ethyl acetate and the organic phase is washed successively with 1 N hydrochloric acid and saturated sodium chloride solution, dried and evaporated in a water pump vacuum.

Workup

  1. extractionextracted twice with ethyl acetate
  2. washthe organic layer is washed with water and saturated sodium chloride solution until neutral,
  3. customdried
  4. customevaporated in a water pump vacuum

Sources & evidence

ORD record
ord-00b4025d0be9440eaa6ff3a3db55ef66
Source dataset
uspto-grants-1977_10
Patent number
US04052421

Reaction notes

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