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Triethylamine → tert-Butyl {5-[(3-aminophenyl)ethynyl]pyridin-3-yl}carbamate

HRID 541866
Notes
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Reaction equation

HRID 541866 reaction equation
Br[C:2]1[CH:3]=[C:4]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[N:6][CH:7]=1.C(N(CC)CC)C.[C:23]([C:25]1[CH:26]=[C:27]([CH:29]=[CH:30][CH:31]=1)[NH2:28])#[CH:24]>[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCCC1>[NH2:28][C:27]1[CH:26]=[C:25]([C:23]#[C:24][C:2]2[CH:3]=[C:4]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:5]=[N:6][CH:7]=2)[CH:31]=[CH:30][CH:29]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 104682Benzenamine, 3-ethynyl-HCID 11403050tert-Butyl (5-bromopyridin-3-yl)carbamate

Product 1

HCID 57961935tert-Butyl {5-[(3-aminophenyl)ethynyl]pyridin-3-yl}carbamateYield 49%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)
Catalyst
HCID 178418476HCID 178418476, compoundCatalyst
HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
50 °C

Procedure

Into the reaction flask were added tert-butyl (5-bromopyridin-3-yl)carbamate (2.00 g, 7.32 mmol), copper(I) iodide (56 mg, 0.29 mmol), bis(triphenylphosphine)palladium(II) chloride (0.20 g, 0.29 mmol), tetrahydrofuran (20 mL) and triethylamine (1.1 mL, 8.0 mmol). The reaction mixture was stirred under N2 bubbling for 5 min. 3-Ethynylaniline (0.849 g, 7.3 mmol) was then added. The reaction mixture was heated at 50° C. overnight. After removal of the solvent, the residue was treated with EtOAc and water. The organic layer was dried over Na2SO4 and concentrated under vacuum. The crude was purified by silica gel column chromatography to give the desired product as a yellow gel (0.60 g, 49%). LCMS for C14H12N3O2 ([M-(tBu)+H]+H)+: m/z=254.0.

Workup

  1. customAfter removal of the solvent
  2. additionthe residue was treated with EtOAc and water
  3. dry with materialThe organic layer was dried over Na2SO4
  4. concentrationconcentrated under vacuum
  5. customThe crude was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-f89739a0ba204327ae8d388cc7d375f5
Source dataset
uspto-grants-2014_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08871753B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes