Methanol → HCID 18637753, compound

HRID 1199273Notes

Reaction equation

HRID 1199273 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[O:7]1[CH2:12][CH2:11][CH2:10][CH2:9][CH:8]1[O:13][C@@H:14]1[C@@H:20]([O:21][CH:22]2[CH2:27][CH2:26][CH2:25][CH2:24][O:23]2)[C@H:19]([O:28][CH:29]2[CH2:34][CH2:33][CH2:32][CH2:31][O:30]2)[C@@H:18]([CH2:35][O:36][CH:37]2[CH2:42][CH2:41][CH2:40][CH2:39][O:38]2)[O:17][C:15]1([CH:43]1[S:48][CH2:47][CH2:46][CH2:45][S:44]1)[OH:16].CO>O1CCCC1.C(OCC)C>[O:7]1[CH2:12][CH2:11][CH2:10][CH2:9][CH:8]1[O:13][C@H:14]([C@H:20]([C@@H:19]([C@@H:18]([CH2:35][O:36][CH:37]1[CH2:42][CH2:41][CH2:40][CH2:39][O:38]1)[OH:17])[O:28][CH:29]1[CH2:34][CH2:33][CH2:32][CH2:31][O:30]1)[O:21][CH:22]1[CH2:27][CH2:26][CH2:25][CH2:24][O:23]1)[CH:15]([CH:43]1[S:44][CH2:45][CH2:46][CH2:47][S:48]1)[OH:16]

Participants

5

Reactant 3

HCID 887MethanolHCID 18637754HCID 18637754, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 18637753HCID 18637753, compoundYield 49.8%

Reagents, catalysts & solvents 1

HCID 21868444Ether tetrahydrofuranSolvent

Procedure

Lithium aluminum hydride (1.74 g) was added in small portions under ice-cooling to a solution of 2,3,4,6-tetra-O-(tetrahydropyranyl)-1-C-(1,3-dithian-2-yl)-D-glucopyranose (6.9 g) in tetrahydrofuran-ethyl ether (3:1, 100 mL), and stirred at the same temperature for 5 hours. Methanol (10 mL) was added to the mixture to work up the reaction, and then evaporated under reduced pressure. To the residue were added ethyl acetate (100 mL) and 2N hydrochloric acid (80 mL), the insoluble substances were filtrated off. The organic layer was separated, washed with water and saturated sodium hydrogencarbonate solution, dried over anhydrous sodium sulfate, and evaporated under reduced pressure. The residue was chromatographed on a column of silica gel (400 mL). The column was washed with toluene (500 mL) and eluted with toluene-ethyl acetate (3:2) and then with toluene-ethyl acetate (1:2). The compounds supposed to be the two stereoisomers ((1R)- and (1S)-isomers) of 2,3,4,6-tetra-O-(tetrahydropyranyl)-1-C-(1,3-dithian-2-yl)-D-glucitol were eluted separately. The fraction eluted with toluene-ethyl acetate (3:2) was evaporated to dryness under reduced pressure to give a colorless syrup (3.45 g), and the fraction eluted with toluene-ethyl acetate (1:2) was evaporated to dryness under reduced pressure to give a colorless syrup (1.52 g). The isomer eluted with toluene-ethyl acetate (3:2): Elemental analysis for C30H52O10S2 : Calc.(%): C, 56.58; H, 8.23; S, 10.07. Found(%): C, 56.60; H, 8.25; S, 10.23. The isomer eluted with toluene-ethyl acetate (1:2): Elemental analysis for C30H52O10S2 : Calc.(%): C, 56.58; H, 8.23; S, 10.07. Found(%): C, 56.93; H, 8.02; S, 9.73.

Workup

  1. customthe reaction
  2. customevaporated under reduced pressure
  3. additionTo the residue were added ethyl acetate (100 mL) and 2N hydrochloric acid (80 mL)
  4. filtrationthe insoluble substances were filtrated off
  5. customThe organic layer was separated
  6. washwashed with water and saturated sodium hydrogencarbonate solution
  7. dry with materialdried over anhydrous sodium sulfate
  8. customevaporated under reduced pressure
  9. customThe residue was chromatographed on a column of silica gel (400 mL)
  10. washThe column was washed with toluene (500 mL)
  11. washeluted with toluene-ethyl acetate (3:2)
  12. washwere eluted separately
  13. washThe fraction eluted with toluene-ethyl acetate (3:2)
  14. customwas evaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-3887db368b4d405598ea7d0df0fdf982
Source dataset
uspto-grants-1990_02
Patent number
US04898986

Reaction notes

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