p-Toluenesulfonic acid monohydrate → 1-Acetoxy-3-methoxy-17-propionyloxyestra-1,3,5(10),16-tetraene

HRID 839757Notes

Reaction equation

HRID 839757 reaction equation
[C:1]([O:4][C:5]1[C:22]2[C@@H:21]3[C@H:12]([C@H:13]4[C@@:17]([CH2:19][CH2:20]3)([CH3:18])[C:16](=[O:23])[CH2:15][CH2:14]4)[CH2:11][CH2:10][C:9]=2[CH:8]=[C:7]([O:24][CH3:25])[CH:6]=1)(=[O:3])[CH3:2].[C:26](OC(C)=C)(=[O:29])[CH2:27][CH3:28].O.C1(C)C=CC(S(O)(=O)=O)=CC=1>CCOCC>[C:1]([O:4][C:5]1[C:22]2[C@@H:21]3[C@H:12]([C@H:13]4[C@@:17]([CH2:19][CH2:20]3)([CH3:18])[C:16]([O:23][C:26](=[O:29])[CH2:27][CH3:28])=[CH:15][CH2:14]4)[CH2:11][CH2:10][C:9]=2[CH:8]=[C:7]([O:24][CH3:25])[CH:6]=1)(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 521998p-Toluenesulfonic acid monohydrateHCID 156854901-Propen-2-ol, 2-propanoateHCID 544622991-Acetoxy-3-methoxyestra-1,3,5(10)-trien-17-one

Product 1

HCID 537894971-Acetoxy-3-methoxy-17-propionyloxyestra-1,3,5(10),16-tetraene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A solution of 1-acetoxy-3-methoxyestra-1,3,5(10)-trien-17-one (0.884 g, 26 mM), isopropenyl propionate (15.1 g, 123 mM) and p-toluenesulfonic acid monohydrate (0.134 g, 0.7 mM) is heated at 120° on a set-up employing a Vigreaux column as described in Example 9. After heating at 120° for 12 hrs, the temperature is raised to 150° for 1 hr. The pot residue is poured into ether. The ethereal solution is extracted with saturated sodium bicarbonate solution, cold H2O and dried over MgSO4. Evaporation of the solvent gives a residue which upon chromatography on neutral silica gel affords 1-acetoxy-3-methoxy-17-propionyloxyestra-1,3,5(10),16-tetraene.

Workup

  1. temperatureAfter heating at 120° for 12 hrs
  2. temperaturethe temperature is raised to 150° for 1 hr
  3. extractionThe ethereal solution is extracted with saturated sodium bicarbonate solution, cold H2O
  4. dry with materialdried over MgSO4
  5. customEvaporation of the solvent
  6. customgives a residue which upon chromatography on neutral silica gel

Sources & evidence

ORD record
ord-fa13c917f4a941329c50efaf6569d03d
Source dataset
uspto-grants-1978_06
Patent number
US04096253

Reaction notes

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