Sulfuric Acid → Methyl 4-[7,12-dihydroxy-3-(2-hydroxyethoxy)-10,13-dimethylhexadecahydrocyclopenta[a]phenanthren-17-yl]pentanoate

HRID 1280863Notes

Reaction equation

HRID 1280863 reaction equation
[OH:1][CH:2]1[CH:18]2[CH:10]([CH2:11][CH:12]([OH:27])[C:13]3([CH3:26])[CH:17]2[CH2:16][CH2:15][CH:14]3[CH:19]([CH3:25])[CH2:20][CH2:21][C:22]([OH:24])=[O:23])[C:9]2([CH3:28])[CH:4]([CH2:5][CH:6]([O:29]S(C)(=O)=O)[CH2:7][CH2:8]2)[CH2:3]1.[CH2:34](N(CC)CC)C.OS(O)(=O)=O.[C:46](Cl)(=[O:48])[CH3:47]>O.CO>[OH:1][CH:2]1[CH:18]2[CH:10]([CH2:11][CH:12]([OH:27])[C:13]3([CH3:26])[CH:17]2[CH2:16][CH2:15][CH:14]3[CH:19]([CH3:25])[CH2:20][CH2:21][C:22]([O:24][CH3:34])=[O:23])[C:9]2([CH3:28])[CH:4]([CH2:5][CH:6]([O:29][CH2:47][CH2:46][OH:48])[CH2:7][CH2:8]2)[CH2:3]1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 6367Acetyl chlorideHCID 8471TriethylamineHCID 184251314-(7,12-Dihydroxy-3-methanesulfonyloxy-10,13-dimethylhexadecahydrocyclopenta[a]phenanthren-17-yl) pentanoic acid

Product 1

HCID 21873220Methyl 4-[7,12-dihydroxy-3-(2-hydroxyethoxy)-10,13-dimethylhexadecahydrocyclopenta[a]phenanthren-17-yl]pentanoate

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent2×

Conditions

Temperature
115 °C

Procedure

116 g of 4-(7,12-dihydroxy-3-methanesulfonyloxy-10,13-dimethylhexadecahydrocyclopenta[a]phenanthren-17-yl) pentanoic acid and 130 ml of triethylamine are dissolved in 650 ml of glycol and stirred at 100° C. for 3 hours and 115° C. for 7.5 hours. The reaction mixture is poured into a solution of 400 ml of H2SO4 in 3 l of water at 0° C. and extracted 7 times using 750 ml of EA each time. The extract is dried over Na2SO4 and the solvent is removed in vacuo. The intermediate product IP is obtained. 130 ml of acetyl chloride are added dropwise to 900 ml of methanol at 0° C. A solution of IP in 400 ml is then added and the mixture is stirred at RT for 6 hours. It is allowed to stand at RT for 60 hours, then poured into 2.6 l of water and extracted 8 times using 500 ml of diisopropyl ether (DIP) each time. The organic phase is then washed a further 6 times with 600 ml of a semisaturated aqueous NaHCO3 solution each time. It is dried over Na2SO4 and the solvent is removed in vacuo. Chromatography on silica gel using EA yields 32 g of a resinous solid.

Workup

  1. extractionextracted 7 times
  2. dry with materialThe extract is dried over Na2SO4
  3. customthe solvent is removed in vacuo
  4. customThe intermediate product IP is obtained
  5. additionA solution of IP in 400 ml is then added
  6. stirringthe mixture is stirred at RT for 6 hours
  7. waitto stand at RT for 60 hours
  8. extractionextracted 8 times
  9. washThe organic phase is then washed a further 6 times with 600 ml of a semisaturated aqueous NaHCO3 solution each time
  10. dry with materialIt is dried over Na2SO4
  11. customthe solvent is removed in vacuo

Sources & evidence

ORD record
ord-c72dc7b27a9b4468b4e6e2c373d648d5
Source dataset
uspto-grants-2002_09
Patent number
US06451781B1

Reaction notes

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