Potassium Carbonate → 4-Cyano-2'-nitro-biphenyl-2-carboxylic acid methyl ester

HRID 1519254ノート

反応式

HRID 1519254 の反応式
[CH3:1][O:2][C:3](=[O:13])[C:4]1[CH:9]=[C:8]([C:10]#[N:11])[CH:7]=[CH:6][C:5]=1Br.[N+:14]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1B(O)O)([O-:16])=[O:15].C([O-])([O-])=O.[K+].[K+]>O.O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:1][O:2][C:3]([C:4]1[C:5]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=2[N+:14]([O-:16])=[O:15])=[CH:6][CH:7]=[C:8]([C:10]#[N:11])[CH:9]=1)=[O:13]

参加物

7

反応物 3

HCID 11430Potassium CarbonateHCID 2773548(2-Nitrophenyl)boronic acidHCID 26370474Methyl 2-bromo-5-cyanobenzoate2 回

生成物 1

HCID 866798314-Cyano-2'-nitro-biphenyl-2-carboxylic acid methyl ester収率 51%

試薬・触媒・溶媒 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

実験手順

A mixture of 2-bromo-5-cyano-benzoic acid methyl ester (which may be prepared as described for Intermediate 2; 17.4 g, 72.6 mmol), 2-nitrophenylboronic acid (available from Aldrich Chemical Company, Inc.; 13.2 g, 79.9 mmol), Pd(dppf)Cl2 (available from Aldrich Chemical Company, Inc.; 7 g, 8.7 mmol) and K2CO3 (29.9 g, 218 mmol) in a mixture of water (26.5 mL) and dioxane (530 mL) was heated at reflux for 3.5 h. The reaction mixture was cooled and evaporated to dryness. The residue was co-evaporated with toluene, and then purified by silica gel chromatography, using 20-33% ethyl acetate/petroleum ether as eluent, to give 4-cyano-2′-nitro-biphenyl-2-carboxylic acid methyl ester (10.4 g, 51%). 1H NMR (300 MHz, CDCl3) δ 8.38 (d, J=1.7 Hz, 1H), 8.20 (d, J=8.0 Hz, 1H), 7.88-7.83 (m, 1H), 7.71-7.57 (m, 2H), 7.37 (d, J=7.9 Hz, 1H), 7.30-7.22 (m, 1H), 3.71 (s, 3H).

後処理

  1. temperaturewas heated
  2. temperatureat reflux for 3.5 h
  3. temperatureThe reaction mixture was cooled
  4. customevaporated to dryness
  5. custompurified by silica gel chromatography

出典と根拠

ORDレコード
ord-58c1854cbd53422abbf539a16b464d2a
出典データセット
uspto-grants-2015_07
特許番号
US09073881B2

反応ノート

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