Ammonia → HCID 67674265, compound

HRID 2399558Notes

Reaction equation

HRID 2399558 reaction equation
C([O:8][C@H:9]1[C@H:14]([O:15][CH3:16])[C@@H:13]([O:17]CC2C=CC=CC=2)[C@H:12]([CH2:25][OH:26])[O:11][CH2:10]1)C1C=CC=CC=1.N>CCOCC>[CH3:16][O:15][C@@H:14]1[C@@H:13]([OH:17])[C@H:12]([CH2:25][OH:26])[O:11][CH2:10][C@H:9]1[OH:8]

Participants

4

Reactant 2

HCID 222Ammonia2×HCID 67673453HCID 67673453, compound

Product 1

HCID 67674265HCID 67674265, compoundYield 78.6%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A solution of 2,4-di-O-benzyl-3-O-methyl-1,5-anhydro-L-glucitol (41.18 g, 115 mmole) in dry ether (80 ml) was added to a vigorously stirred solution of Na (15.8 g, 3.0 eq) in liquid ammonia under nitrogen atmosphere at -78° C. After 4 hr at the liquid ammonia boiling point (-33° C), the blue reaction mixture was carefully quenched by the slow addition of MeOH until the blue color disappeared. After evaporation of the liquid ammonia, water-MeOH (1:1) mixture (500 ml) was added and the resulting solution was neutralized by passing through Dowex 50W×8 (ca. 500 ml) column. The column was washed thoroughly with water-MeOH (1:1) mixture (500 ml) and the combined water-MeOH solution was evaporated under reduced pressure to give a crude product (38 g) as a brown oil. The brown oil was purified by silica gel column chromatography [SiO2 : ca. 1 kg] with CHCl3 /MeOH (4:1) as an eluent to give 3-O-methyl-1,5-anhydro-L-glucitol (16.09 g, 90.4 mmole) as a yellow viscous oil in 78.6% yield; FAB-MS: m/z 179 (MH+); 1H-NMR (CDCl3)d: 1.95 (1H,t,J=6 Hz), 2.10 (1H,d, J=4 Hz), 2.45 (1H,d,J=4 Hz), 3.13 (1H,t,J=9 Hz), 3.28(1H,t,J=10 Hz), 3.31 (1H,ddd,J=4, 5 & 9 Hz), 3.54 (1H,dt,J=4 & 9 Hz), 3.69 (3H, s), 3.66~3.80 (2H,m), 3.90 (1H,m), 4.0 (1H,dd,J=5.5 & 10 Hz).

Workup

  1. customthe blue reaction mixture
  2. customwas carefully quenched by the slow addition of MeOH until the blue color
  3. customAfter evaporation of the liquid ammonia, water-MeOH (1:1) mixture (500 ml)
  4. additionwas added
  5. washThe column was washed thoroughly with water-MeOH (1:1) mixture (500 ml)
  6. customthe combined water-MeOH solution was evaporated under reduced pressure
  7. customto give a crude product (38 g) as a brown oil
  8. customThe brown oil was purified by silica gel column chromatography [SiO2 : ca. 1 kg] with CHCl3 /MeOH (4:1) as an eluent

Sources & evidence

ORD record
ord-f2b95d2320204977a6885c6be18ce68a
Source dataset
uspto-grants-1995_09
Patent number
US05449785

Reaction notes

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