Methanesulfonyl chloride → HCID 70614858, compound

HRID 2420236Notes

Reaction equation

HRID 2420236 reaction equation
[OH:1][C@:2]12[CH2:19][CH:18]=[CH:17][CH2:16][C@:15]1([CH3:20])[C@@H:14]1[C@H:5]([C@H:6]3[C@@:10]([CH2:12][CH2:13]1)([CH3:11])[C:9]([Br:21])=[CH:8][CH2:7]3)[CH2:4][C@H:3]2O.CS([Cl:27])(=O)=O>N1C=CC=CC=1>[OH:1][C@:2]12[CH2:19][CH:18]=[CH:17][CH2:16][C@:15]1([CH3:20])[C@@H:14]1[C@H:5]([C@H:6]3[C@@:10]([CH2:12][CH2:13]1)([CH3:11])[C:9]([Br:21])=[CH:8][CH2:7]3)[CH2:4][C@H:3]2[Cl:27]

Participants

4

Reactant 2

HCID 31297Methanesulfonyl chlorideHCID 54276311HCID 54276311, compound

Product 1

HCID 70614858HCID 70614858, compound

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

95 g (0.258 mole) of 5α,6β-dihydroxy-17-bromo-androsta-2,16-diene are dissolved in 950 ml of anhydrous pyridine, and 21 ml (0.276 mole) of methanesulfonic acid chloride are added under stirring at room temperature to the solution. The reaction mixture is allowed to stand for 16 hours and then poured under vigorous stirring into 9 liters of ice water. The precipitating difficulty separable substance is extracted with 1600 ml of dichloro methane. The dichloro methane extract is washed with aqueous 10% hydrochloric acid solution to remove the pyridine and then with water until neutral, dried over sodium sulfate and evaporated to dryness. The evaporation residue, which is a mixture of 5α-hydroxy-6β-chloro-17-bromo-androsta-2,16-diene and 5α,6β-epoxy-17-bromo-androsta-2,16-diene, is dissolved in diethyl ether and etheral hydrochloric acid solution is added thereto until pH = 2 to 3. The so obtained 5α-hydroxy-6β-chloro-17-bromo-androsta-2,16-diene is separated and purified by mixing it with 10-fold amount of petroleum ether. 79.0 g of 5α-hydroxy-6β-chloro-17 -bromo-androsta-2,16-diene (79.0%) are obtained; m.p. 125°-126° C; [α]D25 = + 3.8° (c = 1 in chloroform).

Workup

  1. additionpoured
  2. extractionThe precipitating difficulty separable substance is extracted with 1600 ml of dichloro methane
  3. extractionThe dichloro methane extract
  4. washis washed with aqueous 10% hydrochloric acid solution
  5. customto remove the pyridine
  6. dry with materialwith water until neutral, dried over sodium sulfate
  7. customevaporated to dryness
  8. additiona mixture of 5α-hydroxy-6β-chloro-17-bromo-androsta-2,16-diene and 5α,6β-epoxy-17-bromo-androsta-2,16-diene
  9. dissolutionis dissolved in diethyl ether
  10. additionetheral hydrochloric acid solution is added

Sources & evidence

ORD record
ord-ca499502b9d84c2ca8b2c3f3e749358e
Source dataset
uspto-grants-1978_08
Patent number
US04110326

Reaction notes

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