Diisopropylamine → HCID 57722998、化合物

HRID 1987034ノート

反応式

HRID 1987034 の反応式
C([Li])CCC.C(NC(C)C)(C)C.[C:13]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])(=[O:15])[CH3:14].Br[CH2:22][C:23]1[C:24]([Cl:37])=[N:25][C:26]([Cl:36])=[CH:27][C:28]=1[C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=1[Cl:35]>C1COCC1.[Cl-].[Na+].O.C(OCC)(=O)C.C(O)(=O)C>[Cl:37][C:24]1[C:23]([CH2:22][CH2:14][C:13]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])=[C:28]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][C:30]=2[Cl:35])[CH:27]=[C:26]([Cl:36])[N:25]=1

参加物

9

反応物 4

HCID 7912DiisopropylamineHCID 10908tert-Butyl acetateHCID 57722989HCID 57722989、化合物HCID 178418339Butyllithium

生成物 1

HCID 57722998HCID 57722998、化合物収率 91%

試薬・触媒・溶媒 4

HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

n-Butyllithium in hexanes (1.6M, 18 ml, 28.8 mmol) was added to di-isopropylamine (4.1 ml, 29.25 mmol) in dry THF (200 ml) at −10° under nitrogen. After 5 min. the solution was cooled to −70° and tert-butyl acetate (3.9 ml, 28.93 mmol) added dropwise. After stirring at −70° for 15 min. under nitrogen, 3-(bromomethyl)-2,6-dichloro-4-(2-chlorophenyl)pyridine (2.44 g, 6.942 mmol) in dry THF (18 ml) was added dropwise over 10 min., and the mixture stirred at −70° for 1 h. Glacial acetic acid (2.3 ml) was added, the temperature allowed to rise to 22° and brine (200 ml) and ethyl acetate (100 ml) added. The phases were separated and the aqueous further extracted with ethyl acetate (150 ml). The extracts were dried (Na2SO4), evaporated in vacuo and the residue purified by flash chromatography over silica eluting with cyclohexane-ethyl acetate (100:0-50:50) to give the title compound as a viscous gum (2.44 g, 91%).

後処理

  1. temperatureAfter 5 min. the solution was cooled to −70°
  2. stirringthe mixture stirred at −70° for 1 h
  3. customto rise to 22°
  4. customThe phases were separated
  5. extractionthe aqueous further extracted with ethyl acetate (150 ml)
  6. dry with materialThe extracts were dried (Na2SO4)
  7. customevaporated in vacuo
  8. customthe residue purified by flash chromatography over silica eluting with cyclohexane-ethyl acetate (100:0-50:50)

出典と根拠

ORDレコード
ord-01837af03117470189c77db87251c528
出典データセット
uspto-grants-2009_06
特許番号
US07550480B2

反応ノート

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