Methyl chloroacetate → 2-(Chloromethyl)-5,7-dimethyl-[1,2,4]triazolo[1,5-a]pyrimidine
Reaction equation
CC1C=C(C)C=C(C)C=1S([O-])(=O)=O.[NH2:14][N:15]1[C:20]([CH3:21])=[CH:19][C:18]([CH3:22])=[N:17][C:16]1=[NH2+:23].[OH-].[Na+].CO[C:28](=O)[CH2:29][Cl:30]>CCO>[Cl:30][CH2:29][C:28]1[N:23]=[C:16]2[N:17]=[C:18]([CH3:22])[CH:19]=[C:20]([CH3:21])[N:15]2[N:14]=1Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 55 °C
Procedure
A mixture of 1-Amino-4,6-dimethyl-1H-pyrimidin-2-ylidene-ammonium 2,4,6-Trimethyl-benzenesulfonate (40 g, 0.1 mol) and NaOH (10 g, 0.2 mol) in 500 mL of EtOH was stirred at 50-60° C. for 1 hour. After chloroacetic acid methyl ester (16.6 g, 0.15 mol) was added, the resultant mixture was stirred at reflux for 4 hours. After being concentrated under reduce pressure, the residue was diluted with water (1000 mL) and extracted with CH2Cl2 (300 mL×3). The combined organic layers were washed with brine (200 mL), dried over Na2SO4, filtered, and concentrated under vacuum. The residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=2/1) to give 2 g of 2-Chloromethyl-5,7-dimethyl-[1,2,4]triazolo[1,5-a]pyrimidine in 9% yield. 1H NMR (300 MHz, DMSO-d6): δ 8.55 (s, 1H), 6.25 (s, 2H), 4.05 (s, 3H), 3.95 (s, 3H); LC-MS (MH+): m/z=196.9, tR (minutes, method A)=0.52
Workup
- temperatureat reflux for 4 hours
- concentrationAfter being concentrated
- additionthe residue was diluted with water (1000 mL)
- extractionextracted with CH2Cl2 (300 mL×3)
- washThe combined organic layers were washed with brine (200 mL)
- dry with materialdried over Na2SO4
- filtrationfiltered
- concentrationconcentrated under vacuum
- customThe residue was purified by column chromatography on silica gel (petroleum ether/EtOAc=2/1)
Sources & evidence
- ORD record
- ord-102c86723ec145a887ce35c070b5711e
- Source dataset
- uspto-grants-2015_08
- Patent number
- US09096589B2
Reaction notes
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