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2-Bromo-4-tert-butylpyridine → 2-(3-(3,5-dimethyl-1H-pyrazol-1-yl)phenoxy)-9-(4-tert-butylpyridin-2-yl)-9H-carbazole

HRID 1509648
ノート
印刷プレビュー

反応式

HRID 1509648 の反応式
[CH3:1][C:2]1[CH:6]=[C:5]([CH3:7])[N:4]([C:8]2[CH:9]=[C:10]([CH:25]=[CH:26][CH:27]=2)[O:11][C:12]2[CH:24]=[CH:23][C:22]3[C:21]4[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=4)[NH:15][C:14]=3[CH:13]=2)[N:3]=1.Br[C:29]1[CH:34]=[C:33]([C:35]([CH3:38])([CH3:37])[CH3:36])[CH:32]=[CH:31][N:30]=1.CC([O-])(C)C.[Na+]>C1(C)C=CC=CC=1.O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC(P(C(C)(C)C)C1C(C2C=CC=CC=2)=CC=CC=1)(C)C>[C:35]([C:33]1[CH:32]=[CH:31][N:30]=[C:29]([N:15]2[C:14]3[CH:13]=[C:12]([O:11][C:10]4[CH:25]=[CH:26][CH:27]=[C:8]([N:4]5[C:5]([CH3:7])=[CH:6][C:2]([CH3:1])=[N:3]5)[CH:9]=4)[CH:24]=[CH:23][C:22]=3[C:21]3[C:16]2=[CH:17][CH:18]=[CH:19][CH:20]=3)[CH:34]=1)([CH3:38])([CH3:37])[CH3:36]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 3

HCID 131833052-Bromo-4-tert-butylpyridineHCID 23676156Sodium t-butoxideHCID 681812542-[3-(3,5-Dimethylpyrazol-1-yl)-phenoxy]-carbazole

生成物 1

HCID 863439762-(3-(3,5-dimethyl-1H-pyrazol-1-yl)phenoxy)-9-(4-tert-butylpyridin-2-yl)-9H-carbazole収率 94%

試薬・触媒・溶媒 4

HCID 27342152-(Di-tert-butylphosphino)biphenyl
触媒
HCID 9811564Bis(dibenzylideneacetone)palladium触媒
HCID 1140Toluene溶媒
HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

A mixture of 2-(3-(3,5-dimethyl-1H-pyrazol-1-yl)phenoxy)-9H-carbazole 4 (530 mg, 1.5 mmol, 1.0 eq), 2-bromo-4-tert-butylpyridine (642 mg, 3.0 mmol, 2.0 eq), Pd2(dba)3 (55 mg, 0.06 mmol, 0.04 eq), JohnPhos (36 mg, 0.12 mmol, 0.08 eq) and tBuONa (231 mg, 2.4 mmol, 1.6 eq) in toluene (6 m) and dioxane (6 mL) was stirred at a temperature of 95-105° C. for 2 days under a nitrogen atmosphere. Then the mixture was cooled to ambient temperature. The solvent was removed under reduced pressure and the residue was purified through column chromatography on silica gel using hexane/ethyl acetate (10:1-5:1) as an eluent to obtain the desired product as a brown solid (685 mg in 94% yield). 1H NMR (DMSO-d6, 400 MHz): δ1.26 (s, 9H), 2.11 (s, 3H), 2.23 (s, 3H), 6.00 (s, 1H), 7.06-7.08 (m, 1H), 7.10 (dd, J=8.0, 2.4 Hz, 1H), 7.14 (t, J=2.4 Hz, 1H), 7.24-7.26 (m, 1H), 7.31 (t, J=7.2 Hz, 1H), 7.38 (d, J=2.0 Hz, 1H), 7.41-7.48 (m, 3H), 7.61 (d, J=1.6, 1H), 7.74 (d, J=8.4 Hz, 1H), 8.20 (d, J=8.0 Hz, 1H), 8.26 (d, J=8.8 Hz, 1H), 8.55 (d, J=4.8 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz): δ12.21, 13.22, 30.01, 34.81, 101.37, 107.50, 111.11, 113.01, 113.81, 115.78, 116.80, 118.49, 119.27, 119.72, 120.13, 121.11, 121.83, 123.20, 125.90, 130.45, 139.19, 139.43, 139.94, 141.01, 148.07, 149.37, 150.60, 155.32, 157.50, 163.03.

後処理

  1. temperatureThen the mixture was cooled to ambient temperature
  2. customThe solvent was removed under reduced pressure
  3. customthe residue was purified through column chromatography on silica gel

出典と根拠

ORDレコード
ord-d94ce7bfbe574092b26604bc11147585
出典データセット
uspto-grants-2015_12
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09224963B2

反応ノート

読み込み中…

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