Triethylamine → 4-(4'-Cyano-biphenyl-4-yl)4-oxo-butyric acid, methyl ester

HRID 1979161ノート

反応式

HRID 1979161 の反応式
[C:1]([C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][CH:4]=1)#[N:2].Br[C:13]1[CH:18]=[CH:17][C:16]([C:19](=[O:26])[CH2:20][CH2:21][C:22]([O:24][CH3:25])=[O:23])=[CH:15][CH:14]=1.C(N(CC)CC)C>CN(C)C=O.C(OCC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:1]([C:3]1[CH:8]=[CH:7][C:6]([C:13]2[CH:14]=[CH:15][C:16]([C:19](=[O:26])[CH2:20][CH2:21][C:22]([O:24][CH3:25])=[O:23])=[CH:17][CH:18]=2)=[CH:5][CH:4]=1)#[N:2]

参加物

7

反応物 3

HCID 8471TriethylamineHCID 838865Methyl 4-(4-bromophenyl)-4-oxobutanoateHCID 27343264-Cyanophenylboronic acid

生成物 1

HCID 217517094-(4'-Cyano-biphenyl-4-yl)4-oxo-butyric acid, methyl ester収率 58.6%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 3283Diethyl Ether溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
105 °C

実験手順

A stirred mixture of (4-cyano-phenyl)boronic acid (0.220 g, 0.00150 mol), 4-(4-bromo-phenyl)-4-oxo-butyric acid, methyl ester (0.2715 g, 0.00100 mol), triethylamine (0.418 mL, 0.0030 mol), tri(O-toluyl)phosphine (0.0191 g, 0.0000628 mol) and palladium(II)acetate (0.0067 g, 0.000030 mol) in dry dimethylformamide (4.0 mL) was heated at 105° C. under nitrogen for 2 hours and allowed to cool. For convenience, allowed to stand overnight. The mixture was diluted with diethyl ether, and the resulting suspension was filtered through Celite. The Celite and filtercake were washed with additional diethyl ether then dichloromethane. The filtrate and washings were combined and washed with 0.5 M aqueous hydrochloric acid, water, 3% aqueous ammonium hydroxide, water, and brine. The organics were dried (Na2SO4) and rotary evaporated. The residue was dissolved (chloroform) and chromatographed on silica gel (35 g, 230-400 mesh), eluting with hexanes-acetone (4:1, 30×30 mL) to give 0.172 g of 4-(4′-cyano-biphenyl-4-yl)-4-oxo-butyric acid, methyl ester as a pale yellow solid; mp 149-151° C.

後処理

  1. temperatureto cool
  2. filtrationthe resulting suspension was filtered through Celite
  3. washThe Celite and filtercake were washed with additional diethyl ether
  4. washwashed with 0.5 M aqueous hydrochloric acid, water, 3% aqueous ammonium hydroxide, water, and brine
  5. dry with materialThe organics were dried (Na2SO4) and rotary evaporated
  6. dissolutionThe residue was dissolved (chloroform)
  7. customchromatographed on silica gel (35 g, 230-400 mesh)
  8. washeluting with hexanes-acetone (4:1, 30×30 mL)

出典と根拠

ORDレコード
ord-408e2ab2152e4154b7b2dd9d9d7f012f
出典データセット
uspto-grants-2001_05
特許番号
US06239288B1

反応ノート

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