Aniline → Dimethyl 2-anilinobenzene-1,4-dicarboxylate

HRID 970314

反応式

HRID 970314 の反応式
Br[C:2]1[CH:11]=[C:10]([C:12]([O:14][CH3:15])=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].[NH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.C1C=CC(P(C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>C(OCC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1>[CH3:15][O:14][C:12](=[O:13])[C:10]1[CH:11]=[C:2]([NH:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:3]([C:4]([O:6][CH3:7])=[O:5])=[CH:8][CH:9]=1

参加物

8

反応物 4

HCID 6115AnilineHCID 10796Cesium carbonateHCID 87741Dimethyl 2-bromoterephthalateHCID 634876Binap, (A+-)-

生成物 1

HCID 16748523Dimethyl 2-anilinobenzene-1,4-dicarboxylate

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 1140Toluene溶媒HCID 3283Diethyl Ether溶媒

反応条件

温度
100 °C

実験手順

To a mixture of dimethyl bromoterephthalate (4.5 g, 16.0 mmol), aniline (2.2 mL, 24.0 mmol), (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (922 mg, 1.48 mmol), and toluene (50 mL) was added cesium carbonate (7.53 g, 23.1 mmol), followed by palladium(II) acetate (0.22 g, 1.0 mmol). The mixture was heated to 100° C. for 24 h. HPLC indicated that the reaction was complete. The reaction mixture was cooled to room temperature, diluted with diethyl ether and filtered under reduced pressure through a pad of Celite. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography using a 1:10 mixture of EtOAc and hexane to give 4.58 (97%) of 1A as a bright yellow solid. HPLC retention time=3.74 min. (Condition A) and LC/MS M++1=286+. 1H-NMR (400 MHz, CDCl3): δ 9.50 (bs, 1H), 8.01 (d, J=8.30, 1H), 7.91 (d, J=1.50, 1H), 7.32-7.40 (m, 4H), 7.25 (m, 1H), 7.13 (m, 1H), 3.93 (s, 3H), 3.88 (s, 3H).

後処理

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationfiltered under reduced pressure through a pad of Celite
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. custompurified by silica gel chromatography
  5. additiona 1:10 mixture of EtOAc and hexane

出典と根拠

ORDレコード
ord-0bf03931b142489ebaac81ba47c01ea0
出典データセット
uspto-grants-2007_12
特許番号
US07312209B2

関連ノート

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