Oxalyl chloride → HCID 6475156, compound

HRID 1939863Notes

Reaction equation

HRID 1939863 reaction equation
[Cl:1][C:2]1[CH:13]=[C:12]([Cl:14])[C:11]([O:15][CH3:16])=[CH:10][C:3]=1[O:4][C@@H:5]([CH3:9])[C:6]([OH:8])=O.C(Cl)(=O)C(Cl)=O.[NH2:23][CH2:24][C@H:25]1[O:29][C@@H:28]([N:30]2[CH:37]=[C:36]([CH2:38][CH3:39])[C:34](=[O:35])[NH:33][C:31]2=[O:32])[C@@H:27]([F:40])[C@@H:26]1[OH:41]>C1(C)C=CC=CC=1.CN(C)C=O.[OH-].[Na+]>[Cl:1][C:2]1[CH:13]=[C:12]([Cl:14])[C:11]([O:15][CH3:16])=[CH:10][C:3]=1[O:4][C@@H:5]([CH3:9])[C:6]([NH:23][CH2:24][C@H:25]1[O:29][C@@H:28]([N:30]2[CH:37]=[C:36]([CH2:38][CH3:39])[C:34](=[O:35])[NH:33][C:31]2=[O:32])[C@@H:27]([F:40])[C@@H:26]1[OH:41])=[O:8]

Participants

7

Reactant 3

HCID 65578Oxalyl chlorideHCID 15460476HCID 15460476, compoundHCID 54253886HCID 54253886, compound

Product 1

HCID 6475156HCID 6475156, compoundYield 70.7%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 6228DimethylformamideSolventHCID 14798Sodium HydroxideSolvent

Procedure

24.2 g (0.091 mol) of (S)-2-(2,4-dichloro-5-methoxyphenoxy)-propionic acid were suspended in a mixture of 150 ml of toluene and 0.5 ml of dimethylformamide and the suspension was stirred under nitrogen. 15.0 ml (0.17 mol) of oxalyl chloride were added, with vigorous evolution of gas occurring. The mixture was stirred for 1 hour to give a homogeneous solution. The solvents were removed by evaporation, the residue was taken up in 100 ml of diethyl ether and the solution was added to a solution of 24.6 g (0.090 mol) of 1-(5-amino-2,5-dideoxy-2-fluoro-β-D-arabinofuranosyl)-5-ethyluracil in 290 ml of 0.31M sodium hydroxide solution. The heterogeneous mixture was shaken vigorously for 10 minutes to give a white precipitate which was filtered off and washed firstly with water and then with diethyl ether. The crude product was recrystallized from hot methanol to give 33.1 g (69.7%) of 1-[5-[2(S)-(2,4-dichloro-5-methoxyphenoxy)propionamido]-2,5-dideoxy-2-fluoro-β-D-arabinofuranosyl]-5-ethyluracil as a white crystalline solid, m.p. 195°-196° C.

Workup

  1. stirringThe mixture was stirred for 1 hour
  2. customto give a homogeneous solution
  3. customThe solvents were removed by evaporation
  4. stirringThe heterogeneous mixture was shaken vigorously for 10 minutes
  5. customto give a white precipitate which
  6. filtrationwas filtered off
  7. washwashed firstly with water
  8. customThe crude product was recrystallized from hot methanol

Sources & evidence

ORD record
ord-0a7cbab9d9784085930b52325b986db8
Source dataset
uspto-grants-1997_12
Patent number
US05698532

Reaction notes

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