Methanol → HCID 53993440, compound

HRID 2052412Notes

Reaction equation

HRID 2052412 reaction equation
[CH3:1][O:2][C:3](=[O:28])[CH2:4][CH2:5][C@H:6]([C@@H:8]1[C@:25]2([CH3:26])[C@H:11]([C@H:12]3[C@H:22]([CH2:23][CH2:24]2)[C@:20]2([CH3:21])[C:15]([CH2:16][C@@H:17]([OH:27])[CH2:18][CH2:19]2)=[CH:14][CH2:13]3)[CH2:10][CH2:9]1)[CH3:7].C1(C)C=CC(S(O)(=O)=O)=CC=1.[O:40]1[CH:45]=[CH:44][CH2:43][CH2:42][CH2:41]1.CO>O1CCOCC1>[CH3:1][O:2][C:3](=[O:28])[CH2:4][CH2:5][C@H:6]([C@@H:8]1[C@:25]2([CH3:26])[C@H:11]([C@H:12]3[C@H:22]([CH2:23][CH2:24]2)[C@:20]2([CH3:21])[C:15]([CH2:16][C@@H:17]([O:27][CH:41]4[CH2:42][CH2:43][CH2:44][CH2:45][O:40]4)[CH2:18][CH2:19]2)=[CH:14][CH2:13]3)[CH2:10][CH2:9]1)[CH3:7]

Participants

6

Reactant 4

HCID 887MethanolHCID 6101p-Toluenesulfonic acidHCID 80803,4-dihydro-2H-pyranHCID 11153463CHOL-5-EN-24-oic acid, 3-hydroxy-, methyl ester, (3beta)-

Product 1

HCID 53993440HCID 53993440, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

36.1 g (0.093 mole) of 3β-hydroxy-5-cholenic acid methyl ester was dissolved in 722 ml of dioxane at room temperature, and 1.81 g (0.05 mole of p-toluenesulfonic acid was added. Then, 26.83 ml (0.294 mole) of dihydropyrane was added dropwise over a period of 10 minutes. The temperature rose to 23°-27° C. The solution was stirred for two more hours at room temperature and then adjusted to pH 8 with 3.4 ml of a mixture of 1:1 methanol 29% ammonium hydroxide. An oily precipitate began forming. A semi-solid residue was obtained after the solvent was evaporated. The residue was dissolved in 1.1 liters of chloroform, washed with a 15% sodium bicarbonate solution, then with water. The chloroform solution was dried, decolorized with charcoal and evaporated. The solid residue was dissolved in 1.5 liters of boiling methanol, allowed to cool to room temperature and then filtered. The dried product weighed 34.5 g, mp 114°-115° C. (989-161-A). From the filtrate an additional amount of 8.0 g was isolated, which was recrystallized again from methanol and then from n-heptane. The second crop was 4.1 g, making a total of 38.6 g of 3β-(2-tetrahydropyranyloxy)-5-cholenic acid methyl ester, yield 84%. Anal. Calcd for C30H48O4, M. W. 472.715: C, 76.22; H, 10.24; O, 13.54. Found: C, 76.37; H, 10.21; O, 13.28 (989-161-A). NMR (989-157-A) (CDCl3): δ5.22-5.43 (m,1H, vinyl), ##STR17## 3.20-4.10 (br m, 3H, adjacent to oxygen), 3.63 (s, 3H, --OCH3), 1.00 (s, 3H, C-19 --CH3), 0.66 (s, 3H, C-18 --CH3). IR (989-157-A) (CHCl3) 2940, 2860, 1730, 1440, 1170, 1135, 1110, 1075, 1030, 1020 cm-1.

Workup

  1. customrose to 23°-27° C
  2. customAn oily precipitate began forming
  3. customA semi-solid residue was obtained after the solvent
  4. customwas evaporated
  5. dissolutionThe residue was dissolved in 1.1 liters of chloroform
  6. washwashed with a 15% sodium bicarbonate solution
  7. dry with materialThe chloroform solution was dried
  8. customevaporated
  9. dissolutionThe solid residue was dissolved in 1.5 liters of boiling methanol
  10. temperatureto cool to room temperature
  11. filtrationfiltered
  12. customFrom the filtrate an additional amount of 8.0 g was isolated
  13. customwhich was recrystallized again from methanol

Sources & evidence

ORD record
ord-70e0dbf209ae4c2fae405d3c8484f05f
Source dataset
uspto-grants-1980_01
Patent number
US04183852

Reaction notes

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