Nitrogen → HCID 57908197, compound

HRID 1044005Notes

Reaction equation

HRID 1044005 reaction equation
Br[C:2]1[C:3]([NH2:11])=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1.CCN(CC)CC.[CH3:19][C:20]([CH3:24])([CH3:23])[C:21]#[CH:22].N#N>C1(C)C=CC=CC=1.O.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.[Cu]I>[CH3:19][C:20]([CH3:24])([CH3:23])[C:21]#[C:22][C:2]1[C:3]([NH2:11])=[N:4][CH:5]=[C:6]([N+:8]([O-:10])=[O:9])[CH:7]=1

Participants

8

Reactant 4

HCID 947NitrogenHCID 8471TriethylamineHCID 135123,3-Dimethyl-1-butyneHCID 27344122-Amino-3-bromo-5-nitropyridine

Product 1

HCID 57908197HCID 57908197, compoundYield 90%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 22272177Toluene waterSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 3-bromo-5-nitropyridin-2-amine (1.0 g, 4.6 mmol) in toluene/water (5 mL/2.5 mL), was added Et3N (1.2 mL, 9.2 mmol), Pd(PPh3)2Cl2 (0.3 g, 0.46 mmol), CuI (35 mg, 0.18 mmol) and 3,3-dimethyl-but-1-yne (0.75 g, 9.2 mmol) successively under N2 protection. The mixture was heated at 70° C. for 2.5 h. The solid was filtered and the organic layer was separated. The aqueous layer was exacted with ethyl acetate (10 mL×3). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated under vacuum to afford 3-(3,3-dimethylbut-1-ynyl)-5-nitropyridin-2-amine (0.9 g, 90%). 1H-NMR (CDCl3, 400 MHz) δ 8.87 (d, J=3.2 Hz, 1H), 8.25 (d, J=3.2 Hz, 1H), 5.80 (brs, 2H), 1.36 (s, 9H).

Workup

  1. filtrationThe solid was filtered
  2. customthe organic layer was separated
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-ec9ff3316d6b4c78b779d272b1e80663
Source dataset
uspto-grants-2013_10
Patent number
US08563573B2

Reaction notes

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