2,4-Dimethyl-6-hydroxypyrimidine

Chemical Properties

white crystalline needles

Uses

2,4-DIMETHYL-6-HYDROXYPYRIMIDINE (abbreviated as DMHP) can act as a chelating oxygen-containing pyrimidine ligand, undergoing a substitution reaction with alkyl groups of Group 4 metals to form O,N-chelated complexes of monometallic titanium or zirconium [4].

Synthesis

General procedure for the synthesis of 2,4-dimethyl-6-hydroxypyrimidines from acetamidine hydrochloride and ethyl acetoacetate: to a solution of sodium ethanolate (10.5 g, 154 mmol) in ethanol (200 mL) was added ethyl 3-oxobutanoate (10.0 g, 77 mmol) and acetamidine hydrochloride (7.23 g, 77 mmol) sequentially. The reaction mixture was heated to reflux for 20 hours. After completion of the reaction, water (10 mL) was added to the mixture. The reaction mixture was concentrated under reduced pressure to give the crude product. The crude product was purified by column chromatography (silica gel as stationary phase, dichloromethane/methanol=15:1 as mobile phase) to afford 2,6-dimethylpyrimidin-4-ol as a yellow solid (3.43 g, 36% yield).LRMS (M+H+) m/z: Calculated value 124.06; measured value 124.

References

[1] Patent: WO2013/75083,  2013,  A1. Location in patent: Paragraph 00374; 00375
[2] Synthesis (Germany),  2016,  vol. 48,  # 23,  p. 4246 - 4252
[3] Patent: US2012/95031,  2012,  A1. Location in patent: Page/Page column 159-160
[4] Antiñolo, A., Carrillo-Hermosilla, F., Corrochano, A. E., Fandos, R., Fernández-Baeza, J., Rodríguez, A. M., Ruiz, M. J., & Otero, A. (1999). New Monocyclopentadienyl Complexes of Titanium(IV) and Zirconium(IV) with Chelating Pyrimidinethiolate, Oxypyrimidine, and Oxypyridine Ligands. Molecular Structure of [Zr(η⁵-C₅Me₅)(η²-O,N-ON₂C₆H₇)₃]. Organometallics, 18(25), 5219–5224. https://doi.org/10.1021/om990335t