Hydrogen Bromide → 9-[[(o-carboethoxy)benzyl]oxy]-4-oxo-4H-pyrido[1,2-alpha]-pyrimidine-3-carboxylic Acid, Ethyl Ester, Hydrobromide

HRID 1657365Notes

Reaction equation

HRID 1657365 reaction equation
[Br:1][CH2:2][C:3]1[C:4]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:5][CH:6]=[CH:7][CH:8]=1.[OH:14][C:15]1[C:20]2=[N:21][CH:22]=[C:23]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:24](=[O:25])[N:19]2[CH:18]=[CH:17][CH:16]=1.P([O-])([O-])(O)=O.[K+].[K+].Br>C(O)(=O)C.CC(CC)=O>[BrH:1].[C:9]([C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[CH2:2][O:14][C:15]1[C:20]2=[N:21][CH:22]=[C:23]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:24](=[O:25])[N:19]2[CH:18]=[CH:17][CH:16]=1)([O:11][CH2:12][CH3:13])=[O:10]

Participants

7

Reactant 4

HCID 260Hydrogen BromideHCID 24450Potassium Phosphate, DibasicHCID 616445Ethyl 9-hydroxy-4-oxo-4H-pyrido[1,2-a]pyrimidine-3-carboxylateHCID 11032082Ethyl 2-(bromomethyl)benzoate

Product 1

HCID 1317102569-[[(o-carboethoxy)benzyl]oxy]-4-oxo-4H-pyrido[1,2-alpha]-pyrimidine-3-carboxylic Acid, Ethyl Ester, Hydrobromide

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 6569Methyl Ethyl KetoneSolvent

Procedure

To a solution of 5.0 g of ethyl α-bromo-o-toluate, 4.7 g of 9-hydroxy-4-oxo-4H-pyrido[1,2-α]pyrimidine-3-carboxylic acid, ethyl ester, and 200 ml of ethyl methyl ketone is added 3.9 g of anhydrous dipotassium hydrogen phosphate and the mixture stired and heated under reflux for 18 hours. The cooled mixture is filtered, and the filtrate is concentrated in vacuo to give a semi-solid product. To this product, 3.9 g, in 10 ml of acetic acid is added a solution of 0.81 g of hydrogen bromide in 4 ml of glacial acetic acid, dropwise, with agitation. The crystalline product that separates is filtered, washed with anhydrous ether, and recrystallized from acetonitrile to give the named product.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 18 hours
  3. filtrationThe cooled mixture is filtered
  4. concentrationthe filtrate is concentrated in vacuo
  5. customto give a semi-solid product
  6. filtrationThe crystalline product that separates is filtered
  7. washwashed with anhydrous ether
  8. customrecrystallized from acetonitrile
  9. customto give the named product

Sources & evidence

ORD record
ord-82e0ce18634b4c6cbd3c0b13d6fc42fe
Source dataset
uspto-grants-1976_06
Patent number
US03960847

Reaction notes

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