Diisopropylamine → 4,4,4-Trifluoro-3-hydroxy-3-methyl-1-(4-[2-pyridylcarbonyl]phenyl)but-1-yne

HRID 35894

反応式

HRID 35894 の反応式
C(NC(C)C)(C)C.C([Li])CCC.[N:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:19]([C:21]1[CH:26]=[CH:25][C:24]([C:27]#[CH:28])=[CH:23][CH:22]=1)=[O:20].[F:29][C:30]([F:35])([F:34])[C:31]([CH3:33])=[O:32].[NH4+].[Cl-]>O1CCCC1>[F:29][C:30]([F:35])([F:34])[C:31]([OH:32])([CH3:33])[C:28]#[C:27][C:24]1[CH:23]=[CH:22][C:21]([C:19]([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][N:13]=2)=[O:20])=[CH:26][CH:25]=1

参加物

7

反応物 5

HCID 7912DiisopropylamineHCID 9871Methyl trifluoromethyl ketoneHCID 25517Ammonium ChlorideHCID 541685884-(2-Pyridylcarbonyl) phenyl ethyneHCID 178418339Butyllithium

生成物 1

HCID 199393054,4,4-Trifluoro-3-hydroxy-3-methyl-1-(4-[2-pyridylcarbonyl]phenyl)but-1-yne収率 1.1%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To 150 mL tetrahydrofuran was added diisopropylamine (2.4 g), and the mixture was then cooled to -78° C. n-Butyl-lithium was added (8.1 mL, 2.5 molar solution in hexanes). To this mixture was added a solution which had been prepared by dissolving 4-(2-pyridylcarbonyl) phenyl ethyne (3.5 g) in a few mL tetrahydrofuran. The mixture was allowed to stir for 25 minutes. 1,1,1-trifluoroacetone (4.76 g) was added in one portion and the mixture was stirred for 15 minutes. The reaction mixture was then poured into 30 mL aqueous saturated NH4Cl. The ensuing mixture was extracted with 3×300 mL diethyl ether. The organic layers were combined, dried over MgSO4, filtered and evaporated to dryness. The oily residue was chromatographed on silica gel eluting with 80/20 hexane/ethyl acetate. The appropriate fractions were combined and evaporated to dryness. The remaining solid was recrystallized from diethyl ether-hexanes to yield 60 mg of the title compound; mp 116°-118° C.; (300 MHz, (CDCl3): 1.74 (s,3, methyl), 2.79 (s,1, OH), 7.49-7.53 (m,2, aromatic), 7.54-7.58 (d,2, aromatic), 7.89-7.95 (t,1, aromatic), 8.06-8.09 (d,2, aromatic), 8.71-8.73 (d,1, aromatic); Analysis for C17H12F3O2N: Calculated: C, 63.95; H, 3.79; N, 4.39; Found: C, 63.96; H, 3.97; N, 4.38.

後処理

  1. additionTo this mixture was added a solution which
  2. customhad been prepared
  3. stirringthe mixture was stirred for 15 minutes
  4. extractionThe ensuing mixture was extracted with 3×300 mL diethyl ether
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated to dryness
  8. customThe oily residue was chromatographed on silica gel eluting with 80/20 hexane/ethyl acetate
  9. customevaporated to dryness
  10. customThe remaining solid was recrystallized from diethyl ether-hexanes

出典と根拠

ORDレコード
ord-934bf027cd034ced9ceff08e87d00cfc
出典データセット
uspto-grants-1995_05
特許番号
US05411973

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