Acetic Acid → 6-Methyl-3-(6-(methylsulfinyl)pyrimidin-4-yl)pyrazolo[1,5-a]pyrimidin-2-amine

HRID 490116Notes

Reaction equation

[CH3:1][S:2][C:3]1[N:8]=[CH:7][N:6]=[C:5]([C:9]2[C:10]([NH2:15])=[N:11][NH:12][C:13]=2[NH2:14])[CH:4]=1.C(O[CH:19]=[C:20]([CH3:23])[CH:21]=O)C.C(O)(=[O:26])C.ClC1C=CC=C(C(OO)=O)C=1>C(O)(C)C.C(OCC)(=O)C.[OH-].[Na+]>[CH3:23][C:20]1[CH:19]=[N:14][C:13]2[N:12]([N:11]=[C:10]([NH2:15])[C:9]=2[C:5]2[CH:4]=[C:3]([S:2]([CH3:1])=[O:26])[N:8]=[CH:7][N:6]=2)[CH:21]=1

Participants

Conditions

Temperature: 160 °C

Procedure

4-(6-(methylthio)pyrimidin-4-yl)-1H-pyrazole-3,5-diamine (1.0 g, 4.5 mmol) was combined with 3-ethoxy-2-methylacrylaldehyde (0.63 g, 5.3 mmol) in isopropanol (12 mL). Acetic acid (0.1 mL) was added to the reaction mixture which was then sealed in a microwave vessel and heated to 160° C. for 15 min. The reaction mixture was diluted with ethyl acetate (200 mL) and 1N NaOH (60 mL), the layers separated and the organic layer concentrated to 60 mL. This solution was cooled to 0° C. and 77% m-chloroperbenzoic acid (1.9 g, 8.5 mmol) was added. After 1 hr. a yellow precipitate formed which was filter off, washed with ethyl acetate and dried to give the product, 0.39 g, 30% yield. LCMS MH+289.29. H NMR (500 MHz, DMSO-d6) 9.02 (s, 1H) 8.91 (s, 1H), 8.88 (s, 1H), 8.54 (s, 1H), 7.14 (s, 2H), 2.91 (s, 3H), 2.34 (s, 3H).

Workup

customwas then sealed in a microwave vessel
customthe layers separated
concentrationthe organic layer concentrated to 60 mL
temperatureThis solution was cooled to 0° C.
customa yellow precipitate formed which
filtrationwas filter off
washwashed with ethyl acetate
customdried
customto give the product, 0.39 g, 30% yield

Sources & evidence

ORD record: ord-5c8de0bb817b4576a1026089a29adc09
Source dataset: uspto-grants-2009_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07528138B2

Reaction notes

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