Phosphorus oxychloride → 6-chloro-3-cyclopropyl-1-(3-nitrophenyl)-1H-pyrimidine-2,4-dione

HRID 75628Notes

Reaction equation

[CH:1]1([N:4]2[C:9](=[O:10])[CH2:8][C:7](=O)[N:6]([C:12]3[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[CH:13]=3)[C:5]2=[O:21])[CH2:3][CH2:2]1.P(Cl)(Cl)([Cl:24])=O>O>[Cl:24][C:7]1[N:6]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[CH:13]=2)[C:5](=[O:21])[N:4]([CH:1]2[CH2:3][CH2:2]2)[C:9](=[O:10])[CH:8]=1

Participants

Conditions

Temperature: 110 °C

Procedure

To 1-cyclopropyl-3-(3-nitrophenyl)pyrimidine-2,4,6-trione 5 (28 g) obtained in Step 2 was added water (3 ml), phosphorus oxychloride (72 ml) was added dropwise by small portions with stirring, and the mixture was stirred with heating at 110° C. for 1 hr. The reaction mixture was poured into ice water by small portions, and the precipitated solid was filtered by suction. The filtrate was dissolved in chloroform (300 ml), washed with water (30 ml) and brine (30 ml), and the organic layer was dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (chloroform:acetone=9:1) to give a 2:1 mixture (10 g, 34%) of 6-chloro-3-cyclopropyl-1-(3-nitrophenyl)-1H-pyrimidine-2,4-dione 6 and 4-chloro-3-cyclopropyl-1-(3-nitrophenyl)-1H-pyrimidine-2,6-dione 7 as a white solid.

Workup

additionwas added dropwise by small portions
stirringthe mixture was stirred
filtrationthe precipitated solid was filtered by suction
dissolutionThe filtrate was dissolved in chloroform (300 ml)
washwashed with water (30 ml) and brine (30 ml)
dry with materialthe organic layer was dried over anhydrous magnesium sulfate
concentrationconcentrated under reduced pressure
customThe residue was purified by column chromatography (chloroform:acetone=9:1)

Sources & evidence

ORD record: ord-7116f989d6ea45e5b97d99d2cd15708b
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08835443B2

Reaction notes

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