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

HRID 1822772ノート

反応式

HRID 1822772 の反応式
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

参加物

7

反応物 5

HCID 176Acetic AcidHCID 962WaterHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 142684-BromopyridineHCID 709434,6-Dichloropyrimidine

生成物 1

HCID 120574654,6-dichloro-2-(2-pyridinyl)pyrimidine収率 61%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
-30 °C

実験手順

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.

後処理

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

出典と根拠

ORDレコード
ord-ed763e16b8e04ab893f60c74cece211f
出典データセット
uspto-grants-2006_05
特許番号
US07037916B2

反応ノート

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