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

HRID 970314

반응식

HRID 970314 반응식
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

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 1140Toluene용매HCID 3283Diethyl Ether용매

반응 조건

온도
100 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-0bf03931b142489ebaac81ba47c01ea0
출처 데이터셋
uspto-grants-2007_12
특허 번호
US07312209B2

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