2-Bromo-6-methylpyridine → 2-{4-[3-(6-Methylpyridin-2-yl)prop-2-ynylidene]piperidin-1-yl}-3-nitropyridine

HRID 1895951Notes

Reaction equation

HRID 1895951 reaction equation
[N+:1]([C:4]1[C:5]([N:10]2[CH2:15][CH2:14][C:13](=[CH:16][C:17]#[CH:18])[CH2:12][CH2:11]2)=[N:6][CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].Br[C:20]1[CH:25]=[CH:24][CH:23]=[C:22]([CH3:26])[N:21]=1>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.[Cu]I>[CH3:26][C:22]1[N:21]=[C:20]([C:18]#[C:17][CH:16]=[C:13]2[CH2:14][CH2:15][N:10]([C:5]3[C:4]([N+:1]([O-:3])=[O:2])=[CH:9][CH:8]=[CH:7][N:6]=3)[CH2:11][CH2:12]2)[CH:25]=[CH:24][CH:23]=1

Participants

5

Reactant 2

HCID 792052-Bromo-6-methylpyridineHCID 866273353-Nitro-2-(4-prop-2-ynylidenepiperidin-1-yl)pyridine

Product 1

HCID 251836682-{4-[3-(6-Methylpyridin-2-yl)prop-2-ynylidene]piperidin-1-yl}-3-nitropyridineYield 69.6%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
80 °C

Procedure

A mixture of Compound 1c (0.21 g, 0.86 mmol), 2-bromo-6-methylpyridine (0.11 mL, 0.95 mmol), tetrakis(triphenylphosphine)palladium(0) (70 mg, 0.06 mmol), CuI (16 mg, 0.09 mmol) in anhydrous and degassed triethylamine (10 mL) was heated at 80° C. under a nitrogen atmosphere for 2 h in sealed vessel. The reaction mixture was cooled, poured into water and extracted with EtOAc. The combined organic layers were washed with brine, dried on Na2SO4 and evaporated to dryness in vacuo to afford a residue, which was purified by flash chromatography (EtOAc—Petroleum Ether 3.5:6.5) affording the title product (0.20 g).

Workup

  1. customdegassed triethylamine (10 mL)
  2. temperatureThe reaction mixture was cooled
  3. additionpoured into water
  4. extractionextracted with EtOAc
  5. washThe combined organic layers were washed with brine
  6. customdried on Na2SO4
  7. customevaporated to dryness in vacuo
  8. customto afford a residue, which
  9. customwas purified by flash chromatography (EtOAc—Petroleum Ether 3.5:6.5)

Sources & evidence

ORD record
ord-364c87f6c7544ea3b84d53f2d13c04b3
Source dataset
uspto-grants-2013_08
Patent number
US08518916B2

Reaction notes

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