Acetic Acid → 4,6-dichloro-2-(2-pyridinyl)pyrimidine

HRID 1822772Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][N:5]=[CH:4][CH:3]=1.[Cl:8][C:9]1[CH:14]=[C:13]([Cl:15])[N:12]=[CH:11][N:10]=1.O.C(O)(=O)C.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C(OCC)C>[N:5]1[CH:6]=[CH:7][CH:2]=[CH:3][C:4]=1[C:11]1[N:12]=[C:13]([Cl:15])[CH:14]=[C:9]([Cl:8])[N:10]=1

Participants

Conditions

Temperature: -30 °C

Procedure

nButyllithium (1.5 M in hexanes/1.53 mL, 2.3 mmol) was added dropwise to a solution of 4-bromopyridine (200 μL, 2.08 mmol) and in diethyl ether (20 mL)−78° C. After 30 minutes, the reaction mixture was warmed to −30° C. and 4,6-dichloropyrimidine (283 mg, 1.9 mmol) was added. The reaction mixture was allowed to warm to 0° C. over 60 min after which water (2 mmol) and acetic acid (4 mmol) were added followed by DDQ (431 mg, 1.9 mmol). After 30 minutes, the reaction mixture was diluted with diethyl ether (30 mL) and washed three times with aqueous 3M NaOH. the organic layer was dried over MgSO4. Filtration and removal of volatiles under reduced pressure yielded a brown gummy solid which was purified by flash chromatography to afford 2-pyridyl-4,6-dichloropyrimidine as a white solid (0.261 mg, 61%). 1H NMR: (CDCl3) δ 7.40, 1H, s; 8.23, 2H, d; 8.80, 2H, d.

Workup

additionwere added
waitAfter 30 minutes
washwashed three times with aqueous 3M NaOH
dry with materialthe organic layer was dried over MgSO4
filtrationFiltration and removal of volatiles under reduced pressure
customyielded a brown gummy solid which
customwas purified by flash chromatography

Sources & evidence

ORD record: ord-ed763e16b8e04ab893f60c74cece211f
Source dataset: uspto-grants-2006_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07037916B2

Reaction notes

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