Sodium Carbonate → 3-(2,4-bis(5-methylthiophen-2-yl)-1H-imidazol-1-yl)-9-methyl-9H-carbazole

HRID 1429117노트

반응식

HRID 1429117 반응식
I[C:2]1[N:3]([C:13]2[CH:14]=[CH:15][C:16]3[N:17]([CH3:26])[C:18]4[C:23]([C:24]=3[CH:25]=2)=[CH:22][CH:21]=[CH:20][CH:19]=4)[CH:4]=[C:5]([C:7]2[S:8][C:9]([CH3:12])=[CH:10][CH:11]=2)[N:6]=1.[CH3:27][C:28]1[S:32][C:31](B2OC(C)(C)C(C)(C)O2)=[CH:30][CH:29]=1.C([O-])([O-])=O.[Na+].[Na+]>O.CN(C=O)C>[CH3:27][C:28]1[S:32][C:31]([C:2]2[N:3]([C:13]3[CH:14]=[CH:15][C:16]4[N:17]([CH3:26])[C:18]5[C:23]([C:24]=4[CH:25]=3)=[CH:22][CH:21]=[CH:20][CH:19]=5)[CH:4]=[C:5]([C:7]3[S:8][C:9]([CH3:12])=[CH:10][CH:11]=3)[N:6]=2)=[CH:30][CH:29]=1

참가 물질

6

반응물 3

HCID 10340Sodium CarbonateHCID 118169404,4,5,5-Tetramethyl-2-(5-methylthiophen-2-yl)-1,3,2-dioxaborolaneHCID 675115193-(2-iodo-4-(5-methylthiophen-2-yl)-1H-imidazol-1-yl)-9-methyl-9H-carbazole

생성물 1

HCID 675104043-(2,4-bis(5-methylthiophen-2-yl)-1H-imidazol-1-yl)-9-methyl-9H-carbazole수율 135.4%

시약·촉매·용매 2

HCID 962Water용매HCID 6228Dimethylformamide용매

실험 절차

A mixture of 3-(2-iodo-4-(5-methylthiophen-2-yl)-1H-imidazol-1-yl)-9-methyl-9H-carbazole 10 (920 g, 2.0 mmol), 5-methylthiophene-2-boronic acid pinacol ester (880 mg, 3.9 mmol), Na2CO3 (1.03 g, 9.81 mmol) in H2O (5 mL) and DMF (20 mL) was degassed (N2 bubbling). Pd(PPh3)4 (60 mg) was added and the mixture was heated to reflux for 8 h. The mixture was allowed to cool to room temperature and concentrated. The residue was washed with H2O (3 times) and EtOAc (1 time). The solid material was transferred to a soxlet apparatus and the material extracted with EtOAc. The organic extract was concentrated to ˜10 mL and the solid material was collected and recrystallised (EtOAc) to give 3-(2,4-bis(5-methylthiophen-2-yl)-1H-imidazol-1-yl)-9-methyl-9H-carbazole 11 (1.19 g, 76%) as colourless crystals. A portion of this material was further purified by sublimation (220° C., 10−6 mBar): m.p. 248-255° C. (DSC)1H NMR (CDCl3, 400 MHz) δ 2.33 (s, 3H), 2.51 (d, J=0.6 Hz, 3H), 3.94 (s, 3H), 6.48 (br s, 1H), 6.72 (d, J=2.5 Hz, 1H), 7.22 (s, 1H), 7.30 (t, 7.6 Hz, 1H), 7.43 (dd, J 2.0, 8.6 Hz, 1H), 7.49 (d, 8.5 Hz, 2H), 7.57 (dt, J 1.0, 7.6 Hz, 1H), 8.08 (d, 7.7 Hz, 1H), 8.10 (d, J=1.8 Hz, 1H); 13C NMR (CDCl3, 100 MHz) δ 15.1, 15.4, 109.0, 109.2, 117.9, 119.2, 119.8, 120.8, 122.2, 123.3, 124.5, 125.9, 126.1, 126.9, 141.1, 141.8, 142.6; HRMS (EI) m/z 439.1163 C24H22N2S [M]+. requires 439.1171.

후처리

  1. customwas degassed (N2 bubbling)
  2. additionPd(PPh3)4 (60 mg) was added
  3. temperaturethe mixture was heated
  4. temperatureto reflux for 8 h
  5. concentrationconcentrated
  6. washThe residue was washed with H2O (3 times) and EtOAc (1 time)
  7. extractionthe material extracted with EtOAc
  8. extractionThe organic extract
  9. concentrationwas concentrated to ˜10 mL
  10. customthe solid material was collected
  11. customrecrystallised (EtOAc)

출처 및 근거

ORD 기록
ord-b3ca65a7a349487093da0ba64a2014c5
출처 데이터셋
uspto-grants-2015_01
특허 번호
US08937303B2

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