p-Toluenesulfonic acid → HCID 18595306, compound

HRID 1580574Notes

Reaction equation

HRID 1580574 reaction equation
[Cl:1][C@H:2]1[CH2:22][C@@:21]2([CH3:23])[C@@H:13]([CH2:14][C@H:15]([CH3:25])[C@:16]2([OH:24])[C:17](=[O:20])[CH2:18][OH:19])[C@H:12]2[C@H:3]1[C@:4]1([CH3:27])[C:9]([CH2:10][CH2:11]2)=[CH:8][C:7](=[O:26])[CH:6]=[CH:5]1.[C:28](OC)(OC)([O:32]C)[CH:29]([CH3:31])[CH3:30].C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)(O)[O-].[Na+]>O1CCOCC1.CC(C)=O.O>[Cl:1][C@H:2]1[CH2:22][C@@:21]2([CH3:23])[C@@H:13]([CH2:14][C@H:15]([CH3:25])[C@:16]2([O:24][C:28](=[O:32])[CH:29]([CH3:31])[CH3:30])[C:17](=[O:20])[CH2:18][OH:19])[C@H:12]2[C@H:3]1[C@:4]1([CH3:27])[C:9]([CH2:10][CH2:11]2)=[CH:8][C:7](=[O:26])[CH:6]=[CH:5]1

Participants

8

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 404951,1,1-Trimethoxy-2-methylpropaneHCID 516892Sodium Bicarbonate2×HCID 18595305(11β,16β)-11-Chloro-17,21-dihydroxy-16-methylpregna-1,4-diene-3,20-dione

Product 1

HCID 18595306HCID 18595306, compound

Reagents, catalysts & solvents 3

HCID 180AcetoneSolventHCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of 11β-chloro-17,21-dihydroxy-16β-methylpregna-1,4-diene-3,20-dione (214 mg.) in dioxan (7 ml.) was treated with trimethyl orthoisobutyrate (0.22 ml.) and toluene p-sulphonic acid (23 mg.) at room temperature. After 45 minutes a little sodium bicarbonate was added and the mixture was then poured into a dilute solution of sodium bicarbonate. The oily product was extracted into ethyl acetate and washed with water. Evaporation of the organic solent gave an oil which was dissolved in acetone (10 ml.) and treated with 0.08 N-sulphuric acid (2.4 ml.). After keeping at room temperature for 30 minutes, the solution was diluted with water and the precipitated oil was extracted with ethyl acetate and washed with water. Evaporation of the organic solvent afforded the crude product which, on crystallization from ether-petroleum ether, gave the title compound, m.p. 163°-164° (K), [α]D + 108.5 (c 0.6 chloroform) λmax 240 nm (ε 15,460) (Found: C, 67.7; H, 7.7; Cl, 7.4. C26H35Cl O5 requires C, 67.45; H, 7.6; Cl, 7.65%).

Workup

  1. extractionThe oily product was extracted into ethyl acetate
  2. washwashed with water
  3. customEvaporation of the organic solent
  4. customgave an oil which
  5. extractionthe precipitated oil was extracted with ethyl acetate
  6. washwashed with water
  7. customEvaporation of the organic solvent
  8. customafforded the crude product which
  9. customon crystallization from ether-petroleum ether

Sources & evidence

ORD record
ord-8234be8e7c69430f95f2821e3c553ecb
Source dataset
uspto-grants-1976_01
Patent number
US03933799

Reaction notes

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