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

HRID 1429117ノート

反応式

HRID 1429117 の反応式
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

参加物

6

反応物 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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-b3ca65a7a349487093da0ba64a2014c5
出典データセット
uspto-grants-2015_01
特許番号
US08937303B2

反応ノート

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