Sodium Carbonate → 4-(4'-Tert-butyl-biphenyl-4-yl)-4-oxo-butyric acid, methyl ester

HRID 381854

反応式

HRID 381854 の反応式
[C:1]([C:5]1[CH:10]=[CH:9][C:8](B(O)O)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].Br[C:15]1[CH:20]=[CH:19][C:18]([C:21](=[O:28])[CH2:22][CH2:23][C:24]([O:26][CH3:27])=[O:25])=[CH:17][CH:16]=1.C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:1]([C:5]1[CH:10]=[CH:9][C:8]([C:15]2[CH:16]=[CH:17][C:18]([C:21](=[O:28])[CH2:22][CH2:23][C:24]([O:26][CH3:27])=[O:25])=[CH:19][CH:20]=2)=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2]

参加物

6

反応物 3

HCID 10340Sodium CarbonateHCID 838865Methyl 4-(4-bromophenyl)-4-oxobutanoateHCID 27343204-tert-Butylphenylboronic acid

生成物 1

HCID 702122584-(4'-Tert-butyl-biphenyl-4-yl)-4-oxo-butyric acid, methyl ester収率 69.4%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 1140Toluene溶媒

実験手順

To a stirred solution of 4-tert-butyl-bromobenzene (21.3 g, 0.0999 mol) in THF (30 mL) at −78° C. under nitrogen was added dropwise a 2.1 M solution of n-butyl lithium in hexanes (45 mL, 0.095 mol), and the mixture was stirred for 1.5 hours. To the mixture was added dropwise neat trimethylborate (10.2 mL, 0.090 mol), and the mixture was allowed to slowly warm to room temperature. The mixture was stirred overnight, then quenched by dropwise addition of 1.0 M aqueous hydrochloric acid. Brine was added, and the organic layer was dried (Na2SO4) and rotary evaporated. The residue was crystallized from n-heptane to give 4.65 g of crude 4-tert-butyl-phenyl-boronic acid as white needles. This material was used directly in the next reaction without further characterization. Thus, in a manner similar to Example 12, Step (b), 4-tert-butyl-phenyl-boronic acid (0.4287 g, 0.00241 mol) was allowed to react with 4-(4-bromo-phenyl)-4-oxo-butyric acid, methyl ester (0.5443 g, 0.00200 mol) in the presence of tetrakis(triphenylphosphine)palladium(0) (0.0472 g, 0.0000408 mol) and 2.0 M aqueous sodium carbonate (2.4 mL, 0.0048 mol) in toluene (5 mL) to give, after chromatography on silica gel (270 g, 230-400 mesh), eluting with toluene then chloroform, 0.50 g. The material was dissolved in diethyl ether, washed with 0.10 M aqueous sodium hydroxide, water and brine. The organics were dried (K2CO3), and rotary evaporated to give 0.45 g of 4-(4′-tert-butyl-biphenyl-4-yl)-4-oxo-butyric acid, methyl ester as a white solid; mp 58-62° C.

後処理

  1. customThis material was used directly in the next reaction without further characterization
  2. customto give
  3. washafter chromatography on silica gel (270 g, 230-400 mesh), eluting with toluene
  4. dissolutionThe material was dissolved in diethyl ether
  5. washwashed with 0.10 M aqueous sodium hydroxide, water and brine
  6. dry with materialThe organics were dried (K2CO3)
  7. customrotary evaporated

出典と根拠

ORDレコード
ord-9b45f373d1a7446b99feb724d71c088b
出典データセット
uspto-grants-2001_10
特許番号
US06307089B2

関連ノート

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