Dimethylformamide → 2-Amino-4-chloro-6-cyano-pyrimidylacetate-t-butyl ester

HRID 230983

Reaction equation

HRID 230983 reaction equation
[H-].[Na+].[C:3]([CH2:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])#N.[NH2:13][C:14]1[N:19]=[C:18]([Cl:20])[CH:17]=[C:16](Cl)[N:15]=1.C[N:23](C)C=O>>[C:9]([O:8][C:6](=[O:7])[CH2:5][C:3]1[C:18]([Cl:20])=[N:19][C:14]([NH2:13])=[N:15][C:16]=1[C:17]#[N:23])([CH3:12])([CH3:11])[CH3:10]

Participants

5

Reactant 4

HCID 6228DimethylformamideHCID 24758Sodium hydrideHCID 655222-Amino-4,6-dichloropyrimidineHCID 70693tert-Butyl cyanoacetate

Product 1

HCID 539121792-Amino-4-chloro-6-cyano-pyrimidylacetate-t-butyl ester

Conditions

Temperature
0 °C

Procedure

To a suspension of sodium hydride (17.6 g, 733 mmol) in dry N,N-dimethylformamide (DMF) at 0° C. was added dropwise t-butyl cyanoacetate (96 g, 680 mmol). The tan suspension was stirred at 0° C. for 0.5 hours then 2-amino-4,6-dichloropyrimidine (58.7 g, 358 mmol) was added batchwise. The mixture was heated slowly to 90° C. and the reaction was held at 90° C. for 18 hours. The reaction mixture was poured onto water (1 l) and the mixture was filtered. The filtrate was acidified with con HCl to pH 6 and the resultant solid was filtered and washed with water and hexanes and dried to furnish 99.64 g of the desired subject as a green powder, m.p. 107°-109° C. NMR (200 mHz) D6-acetone δ 12.8 (bs, 1 H), 8.0 (bs, 1 H), 7.8 (bs, 1 H), 6.3 (s, 1 H), 1.5 (s, 9 H).

Workup

  1. temperatureThe mixture was heated slowly to 90° C.
  2. waitthe reaction was held at 90° C. for 18 hours
  3. additionThe reaction mixture was poured onto water (1 l)
  4. filtrationthe mixture was filtered
  5. filtrationthe resultant solid was filtered
  6. washwashed with water and hexanes
  7. customdried
  8. customto furnish 99.64 g of the

Sources & evidence

ORD record
ord-e99eef0083ba482a875cd85532f049a4
Source dataset
uspto-grants-1989_07
Patent number
US04844727

Linked notes

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