Phosphorus oxychloride → 6-Chloropyrimidine-4-carbonyl chloride

HRID 1746648Notes

Reaction equation

HRID 1746648 reaction equation
O[C:2]1[N:7]=[CH:6][N:5]=C(C(O)=O)[CH:3]=1.P(Cl)(Cl)(Cl)(Cl)Cl.P(Cl)(Cl)([Cl:19])=O.[C:22](Cl)(=O)[C:23]([Cl:25])=[O:24]>ClCCl.CN(C=O)C>[Cl:19][C:2]1[N:7]=[CH:6][N:5]=[C:22]([C:23]([Cl:25])=[O:24])[CH:3]=1

Participants

7

Reactant 4

HCID 24813Phosphorus oxychlorideHCID 24819Phosphorus pentachlorideHCID 65578Oxalyl chlorideHCID 178524636HCID 178524636, compound

Product 1

HCID 184220986-Chloropyrimidine-4-carbonyl chloride

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A stirred mixture of 6-hydroxypyrimidine-4-carboxylic acid (10.0 g, 71.4 mmol, prepared according to the method described by Daves, G. C.; Baiocchi, F.; Robins, R. K.; Cheng, C. C. in J. Org. Chem. 1961, 26, 2755-2763) and phosphorus pentachloride (58.0 g, 0.27 mol) was treated with phosphorus oxychloride (100 mL, 1.07 mol) and the resultant mixture was refluxed for 16 hours under nitrogen. The excess phosphorus oxychloride was distilled off and the residue was azeotroped three times with toluene and dried in vacuo. The solid product obtained was suspended in dry dichloromethane (100 mL), cooled (0° C.) and treated with dry DMF (2 mL) and oxalyl chloride (7.9 mL, 91 mmol). The resultant mixture was stirred at room temperature for 15 hours and evaporated in vacuo to afford 6-chloropyrimidine-4-carbonyl chloride as a brown liquid, which was used for the next step.

Workup

  1. customprepared
  2. distillationThe excess phosphorus oxychloride was distilled off
  3. customthe residue was azeotroped three times with toluene
  4. customdried in vacuo
  5. customThe solid product obtained
  6. customevaporated in vacuo

Sources & evidence

ORD record
ord-057b1ce2171d4e14a308ccb0cf5f1ba2
Source dataset
uspto-grants-2015_10
Patent number
US09150519B2

Reaction notes

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