Potassium sodium tartarate → HCID 12851151, compound

HRID 1105845Notes

Reaction equation

HRID 1105845 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].C([O:10][C@@H:11]1[C@@:41]2([CH3:42])[C:15](=[CH:16][CH2:17][C@@H:18]3[C@@H:40]2[CH2:39][CH2:38][C@@:37]2([CH3:43])[C@H:19]3[CH2:20][CH2:21][C@@H:22]2[C@H:23]([CH3:36])[CH2:24][O:25][S:26]([C:29]2[CH:34]=[CH:33][C:32]([CH3:35])=[CH:31][CH:30]=2)(=[O:28])=[O:27])[CH2:14][C@@H:13]([O:44]C(=O)C)[CH2:12]1)(=O)C.O1CCCC1.C(OCC)(=O)C.C(C(C(C([O-])=O)O)O)([O-])=O.[Na+].[K+]>O1CCCC1>[OH:10][C@@H:11]1[C@@:41]2([CH3:42])[C:15](=[CH:16][CH2:17][C@@H:18]3[C@@H:40]2[CH2:39][CH2:38][C@@:37]2([CH3:43])[C@H:19]3[CH2:20][CH2:21][C@@H:22]2[C@H:23]([CH3:36])[CH2:24][O:25][S:26]([C:29]2[CH:34]=[CH:33][C:32]([CH3:35])=[CH:31][CH:30]=2)(=[O:28])=[O:27])[CH2:14][C@@H:13]([OH:44])[CH2:12]1

Participants

6

Reactant 4

HCID 9855836Potassium sodium tartarateHCID 12790113HCID 12790113, compoundHCID 21226445Aluminium lithium hydrideHCID 21939870Tetrahydrofuran ethyl acetate

Product 1

HCID 12851151HCID 12851151, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

In a 2.5 l 4-neck flask equipped with a stirrer, 500 ml dropping funnel with pressure equilizer, thermometer and argon inlet, 800 ml of tetrahydrofuran (product from freshly-opened bottle was stored for 16 hr. over molecular sieves) at room temperature was added in one portion with stirring to 10.84 g (0.28 mol) of lithium aluminum hydride. The suspension was cooled to -20°, and, during cooling and stirring for 30 min., a solution of 26.5 g crude (20S)-1α,3β-diacetyloxy-20-methyl-21-p-toluenesulfonyloxypregn-5-ene in 450 ml tetrahydrofuran under an argon atmosphere was dripped into the flask in such a way that the temperature did not surpass -18°. After stirring for 1.5 hr. under argon at -20°, 1.2 l of tetrahydrofuran--ethyl acetate (1:1) was added to the suspension over a period of 30 min. in such a way that the temperature did not surpass -18°. The cold reaction mixture was poured into a stirred solution, precooled to 0°, of 0.8 l of 2 M potassium sodium tartrate solution. The organic solvent was removed under vacuum at 40°, and the aqueous residue was extracted first with 500 ml and then twice with 300 ml (total of 1.1 l) of ether. The ether extracts were washed successively 2 times with 250 ml of water and 2 times with 250 ml of sat. NaCl solution, combined and dried over sodium sulfate. After removal of the solvent under reduced pressure at 40°, the residue amounted to 24.1 g of crude (20S)-1α,3β-dihydroxy-20-methyl-21-p-toluenesulfonyloxypregn-5-ene (the crude product still contained some unreacted triol because of incomplete tosylation).

Workup

  1. customIn a 2.5 l 4-neck flask equipped with a stirrer
  2. additionover molecular sieves) at room temperature was added in one portion
  3. temperatureThe suspension was cooled to -20°
  4. temperatureduring cooling
  5. customdid not surpass -18°
  6. stirringAfter stirring for 1.5 hr
  7. customdid not surpass -18°
  8. customThe cold reaction mixture
  9. additionwas poured into a stirred solution
  10. customThe organic solvent was removed under vacuum at 40°
  11. extractionthe aqueous residue was extracted first with 500 ml
  12. washThe ether extracts were washed successively 2 times with 250 ml of water and 2 times with 250 ml of sat. NaCl solution
  13. dry with materialdried over sodium sulfate
  14. customAfter removal of the solvent under reduced pressure at 40°

Sources & evidence

ORD record
ord-30ad5809a0444c8498edc107b20f5948
Source dataset
uspto-grants-1982_01
Patent number
US04310467

Reaction notes

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