4-Thiobenzonitrile → 4-cyanophenyl 2,3,4-tri-O-acetyl-1,5-dithio-beta-D-xylopyranoside

HRID 5992

Reaction equation

HRID 5992 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][CH:6]1Br)(=[O:3])[CH3:2].[SH:20][C:21]1[CH:28]=[CH:27][C:24]([C:25]#[N:26])=[CH:23][CH:22]=1>C(#N)C.[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[S:20][C:21]1[CH:28]=[CH:27][C:24]([C:25]#[N:26])=[CH:23][CH:22]=1)(=[O:3])[CH3:2]

Participants

6

Reactant 2

HCID 5850584-ThiobenzonitrileHCID 113826832,3,4-Tri-o-acetyl-5-thioxylopyranosyl bromide

Product 1

HCID 147953324-cyanophenyl 2,3,4-tri-O-acetyl-1,5-dithio-beta-D-xylopyranosideYield 17%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 10931941Silver imidazolateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
50 °C

Procedure

A suspension of 625 mg (1.76.10-3 mol) of 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl bromide, 200 mg (1.48.10-3 mol) of 4-mercaptobenzonitrile and a 400 pm molecular sieve in 10 ml of acetonitrile is stirred in the presence of 605 mg (4.4.10-3 mol) of zinc chloride and 310 mg (1.8.10-3 mol) of silver imidazolate, in the absence of light, under an inert atmosphere. After heating at 50° C. for 3 h, the reaction mixture is filtered on Celite® in ethyl acetate. The filtrate is washed with a 1N solution of hydrochloric acid, water, a 1N solution of sodium hydroxide, water and finally a saturated solution of sodium chloride, dried over magnesium sulfate and evaporated under reduced pressure. After purification by chromatography on silica gel using a hexane/ethyl acetate mixture (3/1 v/v) as the eluent, and precipitation in ether, 100 mg (yield: 17%) of the expected product are obtained.

Workup

  1. filtrationthe reaction mixture is filtered on Celite® in ethyl acetate
  2. washThe filtrate is washed with a 1N solution of hydrochloric acid, water
  3. dry with materiala 1N solution of sodium hydroxide, water and finally a saturated solution of sodium chloride, dried over magnesium sulfate
  4. customevaporated under reduced pressure
  5. customAfter purification by chromatography on silica gel using a hexane/ethyl acetate mixture (3/1 v/v)
  6. customas the eluent, and precipitation in ether

Sources & evidence

ORD record
ord-6382314ae13e449e8e31eb63b6d50308
Source dataset
uspto-grants-1993_09
Patent number
US05246961

Linked notes

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