Sodium Carbonate → 5-Bromo-2-cyclohexenylpyridin-3-amine

HRID 1431361Notes

Reaction equation

HRID 1431361 reaction equation
Br[C:2]1[C:7]([NH2:8])=[CH:6][C:5]([Br:9])=[CH:4][N:3]=1.[C:10]1(B2OC(C)(C)C(C)(C)O2)[CH2:15][CH2:14][CH2:13][CH2:12][CH:11]=1.C(=O)([O-])[O-].[Na+].[Na+]>C1(C)C=CC=CC=1.C(O)C.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>[Br:9][C:5]1[CH:6]=[C:7]([NH2:8])[C:2]([C:10]2[CH2:15][CH2:14][CH2:13][CH2:12][CH:11]=2)=[N:3][CH:4]=1

Participants

8

Reactant 3

HCID 10340Sodium CarbonateHCID 109326752-(Cyclohex-1-en-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 193875322,5-Dibromopyridin-3-amine

Product 1

HCID 596312915-Bromo-2-cyclohexenylpyridin-3-amine

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

A stirred mixture of 2,5-dibromopyridin-3-amine (0.2135 g, 0.848 mmol), 1-cyclohexen-1-yl-boronic acid pinacol ester (0.30 mL, 1.40 mmol), tetrakis(triphenylphosphine)palladium (0.098 g, 0.084 mmol), and 2.0M sodium carbonate (2.0 mL, 4.00 mmol) in toluene (1.5 mL) and ethanol (0.5 mL) was heated to 90° C. After 2.5 h, the reaction was cooled to rt then diluted with water. After extraction with EtOAc, the organic extraction was dried over anhydrous sodium sulfate. After filtration and concentration, the residue was purified on silica gel (0-35% EtOAc in hexanes) to afford a white solid as 5-bromo-2-cyclohexenylpyridin-3-amine. 1H NMR (400 MHz, CDCl3) δ ppm 8.01 (1H, d, J=2.0 Hz), 7.10 (1H, d, J=2.3 Hz), 6.00 (1H, tt, J=3.7, 2.0 Hz), 3.96 (2H, br. s.), 2.45 (2H, m), 2.26 (2H, m), 1.87 (4H, m). 2,5-Dicyclohexenylpyridin-3-amine was also isolated. 1H NMR (400 MHz, CDCl3) δ ppm 8.07 (1H, d, J=2.0 Hz), 6.95 (1H, d, J=2.0 Hz), 6.16 (1H, m), 6.05 (1H, m), 3.81 (2H, br. s.), 2.48 (4H, m), 2.27 (4H, m), 1.87 (8H, m).

Workup

  1. temperaturethe reaction was cooled to rt
  2. extractionAfter extraction with EtOAc
  3. extractionthe organic extraction
  4. dry with materialwas dried over anhydrous sodium sulfate
  5. filtrationAfter filtration and concentration
  6. customthe residue was purified on silica gel (0-35% EtOAc in hexanes)

Sources & evidence

ORD record
ord-905c60bc0f3e49a39bd7ef71e4fde0bf
Source dataset
uspto-grants-2015_01
Patent number
US08940724B2

Reaction notes

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