Ethanol → 4-cyanophenyl 2,3,4-tri-O-acetyl-5-thio-beta-D-xylopyranoside

HRID 6027

Reaction equation

HRID 6027 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[CH2:8][S:7][C@@H:6]1Br)(=[O:3])[CH3:2].[OH:20][C:21]1[CH:28]=[CH:27][C:24]([C:25]#[N:26])=[CH:23][CH:22]=1.C(O)C>C(Cl)Cl.[Cl-].[Zn+2].[Cl-].[N-]1C=CN=C1.[Ag+]>[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[CH2:8][S:7][C@H:6]1[O:20][C:21]1[CH:28]=[CH:27][C:24]([C:25]#[N:26])=[CH:23][CH:22]=1)(=[O:3])[CH3:2]

Participants

7

Reactant 3

HCID 702EthanolHCID 130194-CyanophenolHCID 109263142,3,4-tri-O-acetyl-5-thio-alpha-xylopyranosyl bromide3×

Product 1

HCID 150678464-cyanophenyl 2,3,4-tri-O-acetyl-5-thio-beta-D-xylopyranosideYield 112.5%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalyst2×HCID 10931941Silver imidazolateCatalyst2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

A suspension of 6.5 g (12.3.10-3 mol) of 2,3,4-tri-O-acetyl-5-thio-α-D-xylopyranosyl bromide, 6 g (50.4.10-3 mol) of 4-hydroxybenzonitrile, 6.9 g (50.5.10-3 mol) of zinc chloride and 4.4 g (25.1.10-3 mol) of silver imidazolate in 200 ml of anhydrous methylene chloride is stirred at 40° C., under an inert atmosphere, in the absence of light and in the presence of a molecular sieve (400 pm). After 7 h at this temperature, 6.9 g (50.5.10-3 mol) of zinc chloride, 4.4 g (25.1.10-3 mol) of silver imidazolate and 6.5 g (18.3.10-3 mol) of 2,3,4-tri-O-acetyl-5-thio-α-D-xylopyranosyl bromide are added. The reaction medium is left overnight under these conditions and 6.5 g (12.3.10-3 mol) of 2,3,4-tri-O-acetyl-5-thio-α-D-xylopyranosyl bromide are then added. After 24 h, the reaction mixture is filtered on Celite® , washed with a 1N aqueous solution of hydrochloric acid and then water and dried over magnesium sulfate. After evaporation under reduced pressure, the residue is purified by chromatography on silica gel using a hexane/ethyl acetate mixture (3/1 v/v) as the eluent. 8.1 g (yield:41%) of the expected product are obtained by crystallization from ethanol.

Workup

  1. additionare then added
  2. filtrationthe reaction mixture is filtered on Celite®
  3. washwashed with a 1N aqueous solution of hydrochloric acid
  4. dry with materialwater and dried over magnesium sulfate
  5. customAfter evaporation under reduced pressure
  6. customthe residue is purified by chromatography on silica gel using a hexane/ethyl acetate mixture (3/1 v/v) as the eluent

Sources & evidence

ORD record
ord-4b2ec04873ae4d519d8ca8b0c0b1965c
Source dataset
uspto-grants-1993_09
Patent number
US05246961

Linked notes

Loading…