2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 25-Hydroxycholesta-1,4,6-trien-3-one

HRID 1577074

Reaction equation

HRID 1577074 reaction equation
[OH:1][C:2]([CH2:5][CH2:6][CH2:7][C@H:8]([C@@H:10]1[C@:28]2([CH3:29])[C@H:13]([C@H:14]3[C@H:25]([CH2:26][CH2:27]2)[C@:23]2([CH3:24])[C:17]([CH2:18][C@H:19]([CH2:21][CH2:22]2)[OH:20])=[CH:16][CH2:15]3)[CH2:12][CH2:11]1)[CH3:9])([CH3:4])[CH3:3].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCOCC1>[OH:1][C:2]([CH2:5][CH2:6][CH2:7][C@H:8]([C@@H:10]1[C@:28]2([CH3:29])[C@H:13]([C@H:14]3[C@H:25]([CH2:26][CH2:27]2)[C@:23]2([CH3:24])[C:17](=[CH:18][C:19](=[O:20])[CH:21]=[CH:22]2)[CH:16]=[CH:15]3)[CH2:12][CH2:11]1)[CH3:9])([CH3:3])[CH3:4]

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 6509425-Hydroxycholesterol

Product 1

HCID 2279738725-Hydroxycholesta-1,4,6-trien-3-oneYield 149.5%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

25-Hydroxycholesterol (I) (10.0 gm, 0.0248 mol) was dissolved in 290 ml of dry dioxane. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (18.62 gm, 0.082 mol) was added and the reaction was refluxed 14 hours. The reaction mixture was allowed to cool and then filtered. The filtrate was concentrated, in vacuo, to give 14.7 gm red-brown solid. This solid was taken up in 40 ml ethyl acetate and chromatographed on 250 gm neutral alumina, eluting with ethyl acetate. Product-containing fractions were combined, concentrated and recrystallized from 50 ml ethyl acetate giving 5.80 g of the title compound (58%): m.p. 179.5°-181.5° C.; nmr (CDCl3): δ0.76 (s,3H,C19CH3), 1.20 (s,9H,C18 +C26 +C27CH3 's), 2.04 (s,1H,OH), 6.10 (m,4H,C2 +C4 +C6 +C7H's), 7.10 (d,J=12 Hz, 1H,C1H); UV (ethanol) λmax 225, 257, 299 nm.

Workup

  1. temperaturethe reaction was refluxed 14 hours
  2. temperatureto cool
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated, in vacuo

Sources & evidence

ORD record
ord-57b1180a1c3c4a3fb96826ff675ab9d0
Source dataset
uspto-grants-1981_09
Patent number
US04287129

Linked notes

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