Methanol → 3-(1,1-Dimethoxy-methyl)-6-[2-methoxy4-(2-trimethylsilanyl-ethoxymethoxy)-phenyl]-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazole

HRID 1861105노트

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HRID 1861105 반응식
[CH3:1][O:2][CH:3]([C:6]1[C:14]2[C:9](=[CH:10][C:11](I)=[CH:12][CH:13]=2)[N:8]([CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])[N:7]=1)[O:4][CH3:5].[CH3:24][O:25][C:26]1[CH:31]=[C:30]([O:32][CH:33]([Si](C)(C)C)[O:34][CH2:35][CH3:36])[CH:29]=[CH:28][C:27]=1B(O)O.C(=O)([O-])[O-].[Na+].[Na+].CO>C1C=CC=CC=1.CCOCC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[CH3:1][O:2][CH:3]([C:6]1[C:14]2[C:9](=[CH:10][C:11]([C:27]3[CH:28]=[CH:29][C:30]([O:32][CH2:33][O:34][CH2:35][CH2:36][Si:20]([CH3:22])([CH3:21])[CH3:19])=[CH:31][C:26]=3[O:25][CH3:24])=[CH:12][CH:13]=2)[N:8]([CH2:16][O:17][CH2:18][CH2:19][Si:20]([CH3:23])([CH3:22])[CH3:21])[N:7]=1)[O:4][CH3:5]

참가 물질

9

반응물 4

HCID 887MethanolHCID 10340Sodium CarbonateHCID 218772983-(1,1-dimethoxy-methyl)-6-iodo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazoleHCID 218774492-Methoxy4-(trimethylsilanyl-ethoxymethoxy)-phenylboronic acid

생성물 1

HCID 218774213-(1,1-Dimethoxy-methyl)-6-[2-methoxy4-(2-trimethylsilanyl-ethoxymethoxy)-phenyl]-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazole수율 164.4%

시약·촉매·용매 4

HCID 178418397HCID 178418397, 화합물촉매HCID 241Benzene용매HCID 962Water용매HCID 3283Diethyl Ether용매

실험 절차

3-(1,1-Dimethoxy-methyl)-6-iodo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazole (1.06 g, 2.37 mmol), 2-methoxy-4-(trimethylsilanyl-ethoxymethoxy)-phenylboronic acid (0.99 g, 3.32 mmol), and sodium carbonate (352 mg, 1.4 mmol) were stirred in a mixture of benzene (15 mL), MeOH (3 mL), and water (1 mL) in a flask purged with argon. Tetrakis(triphenylphosphine)palladium(0) (220 mg, 0.19 mmol) was added, and the reaction stirred at reflux for 16 h. The reaction was allowed to cool and was diluted with ether (70 mL). Organics were washed with H2O and brine (30 mL each), dried (Na2SO4), and concentrated in vacuo. Purification by silica gel chromatography (15% EtOAc/hexanes) gave 1.12 g (82%) of 3-(1,1-dimethoxy-methyl)-6-[2-methoxy-4-(2-trimethylsilanyl-ethoxymethoxy)-phenyl]-1-(2-trimethylsilanyl-ethoxymethyl)-1H-indazole as a faintly yellow oil. 1H NMR (300 MHz, CDCl3) δ 7.91 (d, 1H, J=8.4 Hz), 7.64 (s, 1H), 7.37 (dd, 1H, J=8.4, 1.2 Hz), 7.29 (d, 1H, J=8.4 Hz), 6.71-6.77 (m, 2H), 5.82 (s, 1H), 5.75 (s, 2H), 5.28 (s, 2H), 3.77-3.83 (m, 5H), 3.57 (t, 2H, J=8.4 Hz), 3.46 (s, 6H), 1.00 (t, 2H, J=8.4 Hz), 0.88 (t, 2H, J=8.4 Hz), 0.03 (s, 9H), −0.05 (s, 9H).

후처리

  1. custompurged with argon
  2. temperatureat reflux for 16 h
  3. temperatureto cool
  4. washOrganics were washed with H2O and brine (30 mL each)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. customPurification by silica gel chromatography (15% EtOAc/hexanes)

출처 및 근거

ORD 기록
ord-418daf5089224e1ab590578fed90a5e1
출처 데이터셋
uspto-grants-2003_03
특허 번호
US06531491B1

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