Sodium Thiosulfate → HCID 11810229, compound

HRID 1701797Notes

Reaction equation

HRID 1701797 reaction equation
[I-].[Li+].S([O-])([O-])(=O)=S.[Na+].[Na+].[C:10]([O:13][C@H:14]1[C@@H:19]([O:20][C:21](=[O:23])[CH3:22])[C@@H:18]([CH2:24][O:25][C:26](=[O:28])[CH3:27])[O:17][C@H:16](I)[C@@H:15]1[N:30]=[N+:31]=[N-:32])(=[O:12])[CH3:11].[Cl-:33].[Li+]>C(#N)C.[Cl-].C([N+](CC)(CC)CC)C.C(OCC)C>[C:10]([O:13][C@H:14]1[C@@H:19]([O:20][C:21](=[O:23])[CH3:22])[C@@H:18]([CH2:24][O:25][C:26](=[O:28])[CH3:27])[O:17][C@@H:16]([Cl:33])[C@@H:15]1[N:30]=[N+:31]=[N-:32])(=[O:12])[CH3:11]

Participants

8

Reactant 4

HCID 24477Sodium ThiosulfateHCID 66321Lithium iodideHCID 433294Lithium ChlorideHCID 10575138α-D-Galactopyranosyl iodide, 2-azido-2-deoxy-, 3,4,6-triacetate2×

Product 1

HCID 11810229HCID 11810229, compoundYield 50%

Reagents, catalysts & solvents 3

HCID 5946Tetraethylammonium ChlorideCatalystHCID 3283Diethyl EtherSolventHCID 6342AcetonitrileSolvent2×

Procedure

The mixture of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α- and β-D-galactopyranosyl nitrates (II and III) (0.781 g, 2.09 mmole) prepared as described in either Example I or Example II was added to a suspension of anhydrous lithium iodide (1.86 g, 14 mmole) in anhydrous acetonitrile (3 ml). This mixture was stirred in the dark at room temperature for 15-17 minutes and then poured into an ice cold 1% aqueous solution of sodium thiosulfate. A dichloromethane (10 ml) extract was dried over sodium sulfate, filtered and evaporated to give a white foam which discolored upon standing. The p.m.r. spectrum of this compound in CDCl3 showed no remaining starting material and contained a doublet with J=4.0 Hz at 6.93 p.p.m. which was assigned to the anomeric proton of 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyl iodide (XXIV). This α-D-iodide (XXIV) (2.09 mmole) was immediately treated with a molar equivalent of either tetraethylammonium chloride (0.344 g, 2.09 mmole) dissolved in anhydrous acetonitrile (2 ml) or lithium chloride (0.081 g, 2.0 mmole) at ambient temperature. After 1.5 minutes, the solution was poured into ice cold water (10 ml) and extracted with cold dichloromethane (10 ml). The organic solution was dried and evaporated to give a light yellow syrup which, on trituration with ethyl ether, afforded crystalline 3,4,6-tri-O-acetyl-2-azido-2-deoxy-β-D-galactopyranosyl chloride (XXIII) in 50-60% yield; m.p. 102°-104°, [α]D25 -16.5 (c 1, chloroform).

Workup

  1. customprepared
  2. extractionA dichloromethane (10 ml) extract
  3. dry with materialwas dried over sodium sulfate
  4. filtrationfiltered
  5. customevaporated
  6. customto give a white foam which
  7. customat ambient temperature
  8. waitAfter 1.5 minutes
  9. extractionextracted with cold dichloromethane (10 ml)
  10. customThe organic solution was dried
  11. customevaporated
  12. customto give a light yellow syrup which

Sources & evidence

ORD record
ord-e3200d51db3c436582c032d129dcb69d
Source dataset
uspto-grants-1980_03
Patent number
US04195174

Reaction notes

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