Phosphorus oxychloride → Ethyl 4-chloro-2-phenylpyrimidine-5-carboxylate

HRID 1584857Notes

Reaction equation

[C:1]1([C:7]2[N:12]=[C:11](O)[C:10]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:9][N:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.O=P(Cl)(Cl)[Cl:21]>>[C:1]1([C:7]2[N:12]=[C:11]([Cl:21])[C:10]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:9][N:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

Reactant 2

HCID 24813Phosphorus oxychloride

HCID 657593Ethyl 4-hydroxy-2-phenylpyrimidine-5-carboxylate

Product 1

HCID 239537Ethyl 4-chloro-2-phenylpyrimidine-5-carboxylateYield 81%

Procedure

The title compound was prepared by (a) reaction of diethylethoxymethylenemalonate (31 g, 144 mmol) with benzamidine (22 g, 144 mmol) under basic conditions to afford ethyl 2-phenyl-4-hydroxypyrimidine-5-carboxylate in 64% yield in analogy to Example 15, (b) reaction of ethyl 2-phenyl-4-hydroxypyrimidine-5-carboxylate (1.5 g, 6 mmol) and POCl3 (9.4 g, 62 mmol) to afford 81% of ethyl 2-phenyl-4-chloropyrimidine-5-carboxylate in analogy to Example 7, (c) reaction of ethyl 2-phenyl-4-chloropyrimidine-5-carboxylate (12 g, 46 mmol) with hydrazine (4.4 g, 137 mmol) to afford 99% of ethyl 4-hydrazino-2-phenylpyrimidine-5-carboxylate in analogy to Example 18, (d) reaction of ethyl 4-hydrazino-2-phenylpyrimidine-5-carboxylate (12 g, 46 mmol) with citraconic anhydride (10 g, 92 mmol) to afford 75% (12 g) of the title compound (m.p. 155-156° C.) in analogy to Example 21.

Sources & evidence

ORD record: ord-ef36711fdd4e40e18a9808c108dbad7b
Source dataset: uspto-grants-1999_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05935966

Reaction notes

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