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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
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HRID 1509648 반응식
[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]
참가 물질반응 조건실험 절차후처리출처 및 근거반응 노트

참가 물질

8

반응물 3

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

생성물 1

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

시약·촉매·용매 4

HCID 27342152-(Di-tert-butylphosphino)biphenyl
촉매
HCID 9811564Bis(dibenzylideneacetone)palladium촉매
HCID 1140Toluene용매
HCID 312751,4-Dioxane용매

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온도
100 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-d94ce7bfbe574092b26604bc11147585
출처 데이터셋
uspto-grants-2015_12
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09224963B2

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