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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
Notes
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Reaction equation

HRID 1509648 reaction equation
[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]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 4

HCID 2734215
2-(Di-tert-butylphosphino)biphenyl
Catalyst
HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst
HCID 1140TolueneSolvent
HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-d94ce7bfbe574092b26604bc11147585
Source dataset
uspto-grants-2015_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09224963B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes