Sodium Carbonate → 4-(2-Aminopyridin-3-yl)phenol

HRID 1405742Notes

Reaction equation

HRID 1405742 reaction equation
Br[C:2]1[C:3]([NH2:8])=[N:4][CH:5]=[CH:6][CH:7]=1.[Si]([O:16][C:17]1[CH:22]=[CH:21][C:20](B(O)O)=[CH:19][CH:18]=1)(C(C)(C)C)(C)C.C(=O)([O-])[O-].[Na+].[Na+]>COCCOC.O.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>[NH2:8][C:3]1[C:2]([C:20]2[CH:21]=[CH:22][C:17]([OH:16])=[CH:18][CH:19]=2)=[CH:7][CH:6]=[CH:5][N:4]=1

Participants

7

Reactant 3

HCID 10340Sodium CarbonateHCID 8177002-Amino-3-bromopyridineHCID 111078154-(tert-Butyldimethylsilyloxy)phenylboronic Acid (contains varying amounts of Anhydride)

Product 1

HCID 667484774-(2-Aminopyridin-3-yl)phenolYield 35.6%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
100 °C

Procedure

Tetrakis(triphenylphosphine)palladium(0) (1.38 g) was added to a suspension of 3-bromopyridin-2-amine (20.6 g), 4-(tert-butyldimethylsilyloxy)phenylboronic acid (39.0 g) and sodium carbonate (25.2 g) in DME (650 mL) and water (130 mL) and the mixture was stirred at 100° C. under nitrogen 6 hr. Volatiles were removed in vacuo, water and EtOAc were added and the organic layer was separated, washed with brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was crystallized from EtOAc-hexane to give 4-(2-aminopyridin-3-yl)phenol (7.90 g) as yellow crystals. The filtrate of crystallization was purified by column chromatography (silica gel, eluted with EtOAc in hexane) to give 3-(4-{[tert-butyl(dimethyl)silyl]oxy}phenyl)pyridin-2-amine (23.4 g) as a white powder.

Workup

  1. customVolatiles were removed in vacuo, water and EtOAc
  2. additionwere added
  3. customthe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was crystallized from EtOAc-hexane

Sources & evidence

ORD record
ord-80b12234a61648788aa0affa3709fe65
Source dataset
uspto-grants-2014_12
Patent number
US08916551B2

Reaction notes

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