Sulfuric Acid → Ethyl 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylate

HRID 907429Notes

Reaction equation

HRID 907429 reaction equation
S(=O)(=O)(O)O.[Cl:6][C:7]1[C:8]([NH2:23])=[N:9][C:10]([CH:20]2[CH2:22][CH2:21]2)=[N:11][C:12]=1[CH:13]([O:17]CC)[O:14][CH2:15][CH3:16].S(OOS([O-])(=O)=O)([O-])(=O)=O.[NH4+].[NH4+].C(=O)(O)[O-].[Na+]>C(#N)C>[NH2:23][C:8]1[N:9]=[C:10]([CH:20]2[CH2:22][CH2:21]2)[N:11]=[C:12]([C:13]([O:14][CH2:15][CH3:16])=[O:17])[C:7]=1[Cl:6]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 62648Ammonium PersulfateHCID 516892Sodium BicarbonateHCID 177478745-Chloro-2-cyclopropyl-6-(diethoxymethyl)-4-pyrimidinamine2×

Product 1

HCID 11989828Ethyl 6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylateYield 55%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Sulfuric acid (1.97 g, 20 mmol) was added dropwise to 5-chloro-2-cyclopropyl-6-(diethoxymethyl)-4-pyrimidinamine (i.e. the product of Example 6) (2.71 g, 10 mmol) in acetonitrile (27.5 mL) at room temperature. The temperature rose to 35° C. When the mixture had cooled to 29° C. ammonium persulfate (0.5 g, 2.21 mmol) was added in one portion. After stirring for 20 h at room temperature the mixture was poured into saturated aqueous sodium bicarbonate solution (100 mL). The mixture was extracted with ethyl acetate (2×70 mL). The combined extracts were dried and evaporated to leave the product as an off-white solid (1.32 g, 55% yield). Product purified by chromatography on silica gel (eluted with 40:60 ethyl acetate-hexanes) followed by washing with hydrochloric acid (1 N) melted at 93-95° C.

Workup

  1. customrose to 35° C
  2. additionwas added in one portion
  3. extractionThe mixture was extracted with ethyl acetate (2×70 mL)
  4. customThe combined extracts were dried
  5. customevaporated

Sources & evidence

ORD record
ord-055b547ba62b4cd3a062c6bcea57983c
Source dataset
uspto-grants-2011_09
Patent number
US08013155B2

Reaction notes

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