Bromine → HCID 54045133, compound

HRID 280837Notes

Reaction equation

HRID 280837 reaction equation
[C:1]([O:4][CH2:5][C@@H:6]1[C@@:23]2([CH3:24])[C@@H:10]([CH2:11][CH2:12][C@@H:13]3[C@@H:22]2[CH2:21][CH2:20][C@@:18]2([CH3:19])[C@H:14]3[CH2:15][CH2:16][C@@H:17]2[O:25]C(=O)C)[CH2:9][C:8](=[O:29])[CH2:7]1)(=[O:3])[CH3:2].BrBr>C(O)(=O)C>[C:1]([O:4][CH2:5][C:6]1[C@@:23]2([CH3:24])[C:10]([CH2:11][CH2:12][C@@H:13]3[C@@H:22]2[CH2:21][CH2:20][C@@:18]2([CH3:19])[C@H:14]3[CH2:15][CH2:16][C:17]2=[O:25])=[CH:9][C:8](=[O:29])[CH:7]=1)(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 24408BromineHCID 13371263HCID 13371263, compound

Product 1

HCID 54045133HCID 54045133, compoundYield 28.7%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

9.1 g of 1α-acetoxymethyl-17β-acetoxy-5α-androstan-3-one (mp 193°-194° C.) [prepared from 3,3-ethylenedioxyl-1-methylene-5α-androstan-17β-ol ("Naturwissenschaften" [Natural Sciences 51: 86 (1963)) by hydroboration, acetylation, and ketal cleavage] is dissolved in 90 ml of glacial acetic acid. To this solution is added dropwise 3.2 ml of bromine in 25 ml of glacial acetic acid, and the mixture is agitated for 10 minutes. After precipitation in ice water which contains sodium sulfite, the product is suctioned off, washed with water, and dried. 16.5 g of crude dibromide is stirred in 100 ml of dimethylformamide with 10 g of lithium bromide and 20 g of calcium carbonate for 3.5 hours at a bath temperature of 120° C. After cooling, the inorganic salts are suctioned off and washed with 150 ml of methanol. The filtrate is combined with 6 g of potassium hydroxide in 20 ml of water and stirred for 16 hours at room temperature. The reaction solution is poured into ice water, the product is suctioned off and dried. The crude 1-hydroxymethyl-17β-hydroxyandrosta-1,4-dien-3-one (7.5 g) is dissolved in 100 ml of dimethylformamide, combined with 1 g of lead diacetate and 15 ml of acetic anhydride and stirred for 6.5 hours at room temperature. After precipitating in water and removal of the product by vacuum filtering, oxidation is carried out with chromic acid as described in Example 1. Recrystallization from acetone/hexane yields 2.3 g of 1-acetoxymethylandrosta-1,4-diene-3,17-dione, mp 121°-123° C.

Workup

  1. customAfter precipitation in ice water which
  2. washwashed with water
  3. customdried
  4. stirring16.5 g of crude dibromide is stirred in 100 ml of dimethylformamide with 10 g of lithium bromide and 20 g of calcium carbonate for 3.5 hours at a bath temperature of 120° C
  5. temperatureAfter cooling
  6. washwashed with 150 ml of methanol
  7. stirringstirred for 16 hours at room temperature
  8. additionThe reaction solution is poured into ice water
  9. customdried
  10. dissolutionThe crude 1-hydroxymethyl-17β-hydroxyandrosta-1,4-dien-3-one (7.5 g) is dissolved in 100 ml of dimethylformamide
  11. stirringstirred for 6.5 hours at room temperature
  12. customAfter precipitating in water
  13. customremoval of the product by vacuum
  14. filtrationfiltering
  15. customRecrystallization from acetone/hexane

Sources & evidence

ORD record
ord-055749741c67443ca7547ba6132acf7d
Source dataset
uspto-grants-1986_05
Patent number
US04591585

Reaction notes

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