Acetic Acid → 2,5-Dimethoxy-4-cyanoaminopyrimidine
Reaction equation
[N:1]#[C:2][NH2:3].[Na].Cl[C:6]1[C:11]([O:12][CH3:13])=[CH:10][N:9]=[C:8]([O:14][CH3:15])[N:7]=1.C(O)(=O)C.[Cl-].[Na+]>CN1CCCC1=O>[CH3:15][O:14][C:8]1[N:7]=[C:6]([NH:3][C:2]#[N:1])[C:11]([O:12][CH3:13])=[CH:10][N:9]=1Participants
Procedure
To a 100 mL three-neck round bottom flask were added sequentially 7.8 g (121.53 mmol)) of sodium hydrogen cyanamide and then 34.2 g of N-methyl-2-pyrrolidinone (NMP) in one portion, and the slurry mixture was cooled in an ambient temperature water bath. To this mixture was added 10.0 g (54.99 mmol) of 96% 4-chloro-2,5-dimethoxypyrimidine (1; CDMP) in one portion. The mixture was allowed to stir at ambient temperature (<20° C.). After 48 hours (h), 3.78 g (62.95 mmol) of glacial acetic acid was added in one portion and the internal pot temperature rose from 19° C. to 23° C. This reaction slurry was poured over 85 g of crushed ice and the ice was allowed to melt. To this mixture was added 10 g of sodium chloride. The mixture was allowed to stand for 16 minutes (min). Once melted, the cold slurry was suction filtered and the filter cake was washed with two 20-mL portions of water and a final 10 mL water wash. The wet cake transferred to a drying dish and allowed to air dry for 48 h to give 6.78 g (98.8% pure by NMR assay using benzyl acetate) of 2,5-dimethoxy-4-cyanoaminopyrimidine (2) as a light yellow solid in 68% yield. 1H and 13C NMR spectra were identical to that reported in Example 1.
Workup
- customrose from 19° C. to 23° C
- filtrationfiltered
- washthe filter cake was washed with two 20-mL portions of water
- washa final 10 mL water wash
- customto air dry for 48 h
Sources & evidence
- ORD record
- ord-01b8fa00f0064f28bc0982af78963f8b
- Source dataset
- uspto-grants-2015_04
- Patent number
- US09000160B2
Reaction notes
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