4-Toluenesulfonyl chloride → HCID 15231302, compound

HRID 1492099Notes

Reaction equation

HRID 1492099 reaction equation
[C:1]([O:4][C@H:5]1[CH2:27][CH2:26][C@@:25]2([CH3:28])[C@@H:7]([CH2:8][CH2:9][C:10]3[C@@H:24]2[CH2:23][CH2:22][C@@:21]2([CH3:29])[C:11]=3[C:12](=[O:30])[CH2:13][C@@H:14]2[C@H:15]([CH3:20])[CH2:16][CH2:17][CH2:18][OH:19])[CH2:6]1)(=[O:3])[CH3:2].[C:31]1([CH3:41])[CH:36]=[CH:35][C:34]([S:37](Cl)(=[O:39])=[O:38])=[CH:33][CH:32]=1>N1C=CC=CC=1>[C:1]([O:4][C@H:5]1[CH2:27][CH2:26][C@@:25]2([CH3:28])[C@@H:7]([CH2:8][CH2:9][C:10]3[C@@H:24]2[CH2:23][CH2:22][C@@:21]2([CH3:29])[C:11]=3[C:12](=[O:30])[CH2:13][C@@H:14]2[C@H:15]([CH3:20])[CH2:16][CH2:17][CH2:18][O:19][S:37]([C:34]2[CH:35]=[CH:36][C:31]([CH3:41])=[CH:32][CH:33]=2)(=[O:39])=[O:38])[CH2:6]1)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 73974-Toluenesulfonyl chlorideHCID 15125792HCID 15125792, compound

Product 1

HCID 15231302HCID 15231302, compoundYield 71.5%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent2×

Procedure

A solution of 3β-acetoxy-24-hydroxy-5α-chol-8(14)-en-15-one (400 mg) in dry pyridine (3 ml) and a solution of p-toluenesulfonyl chloride (300 mg) in dry pyridine (2 ml) were cooled in sealed vials in a freezer, combined, and kept at 5° C. in a sealed vial for 24 h. The reaction mixture was poured onto ice and the solid product was collected on a filter and washed with water. Reversed phase HPLC analysis on a Microsorb C18 column (solvent, methanol) indicated the following composition: 3β-acetoxy-24-tosyloxy-5α-chol-8(14)-en-15-one, 95%; unreacted 3β-acetoxy-24-hydroxy-5α-chol-8(14)-en-15-one , 3%; and 3β-acetoxy-24-chloro-5α-chol-8(14)-en-15-one, 2%. The crude tosylate (497 mg) was subjected to chromatography on a silica gel (70-230 mesh) column (250 mm×14 mm). Using 5% ethyl acetate in hexane, fractions 20 ml in volume were collected. At fractions 39 and 77, the eluting solvent was changed to 20% ethyl acetate in hexane and 50% ethyl acetate in hexane, respectively. The contents of fractions 41-74 contained 3β-acetoxy-24-tosyloxy-5α-chol-8(14)-en-15-one (392 mg, 66% yield) with a purity of 99% as judged by HPLC analysis. Additional material (62 mg) of 95% purity was recovered in fractions 75-83. The contents of fractions 41-44 (171 mg) were recrystallized from ether-hexane to give 3β-acetoxy-24-tosyloxy-5α-chol-8(14)-en-15-one (150 mg) melting at 158.0°-159.5° C. The structure was confirmed using I.R., N.M.R., and M.S. analyses.

Workup

  1. customkept at 5° C.
  2. customsealed vial for 24 h
  3. additionThe reaction mixture was poured onto ice
  4. customthe solid product was collected on
  5. filtrationa filter
  6. washwashed with water
  7. customwere collected

Sources & evidence

ORD record
ord-9668f40ba38047999443bbdb46e8059d
Source dataset
uspto-grants-1994_12
Patent number
US05371077

Reaction notes

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