N-methyl-2-pyrrolidone → 2-Nitro-5-((trimethylsilyl)ethynyl)pyridine

HRID 1927213Notes

Reaction equation

HRID 1927213 reaction equation
CN1C(=O)CCC1.Br[C:9]1[CH:10]=[CH:11][C:12]([N+:15]([O-:17])=[O:16])=[N:13][CH:14]=1.[CH3:18][Si:19]([C:22]#[CH:23])([CH3:21])[CH3:20].C(N(CC)C(C)C)(C)C>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.O>[N+:15]([C:12]1[CH:11]=[CH:10][C:9]([C:23]#[C:22][Si:19]([CH3:21])([CH3:20])[CH3:18])=[CH:14][N:13]=1)([O-:17])=[O:16]

Participants

8

Reactant 4

HCID 13387N-methyl-2-pyrrolidoneHCID 66111TrimethylsilylacetyleneHCID 81531DiisopropylethylamineHCID 8176205-Bromo-2-nitropyridine

Product 1

HCID 580762652-Nitro-5-((trimethylsilyl)ethynyl)pyridine

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
65 °C

Procedure

To a NMP solution (20 mL) of 5-bromo-2-nitropyridine (1.00 g, 4.93 mmol) were added trimethylsilyl acetylene (1.4 mL), tetrakis(triphenylphosphine)palladium(0) (110 mg), copper(I) iodide (38 mg), and N,N-diisopropylethylamine (1.7 mL) at room temperature, which was stirred under a nitrogen atmosphere for 4 hours at 65° C. Water was added at 0° C. to the reaction solution, which was then extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, after which the solvent was evaporated from the filtrate under a reduced pressure. The residue was purified by silica gel column chromatography (heptane:ethyl acetate=6:1) to obtain the titled compound (490 mg).

Workup

  1. extractionwas then extracted with ethyl acetate
  2. washThe organic layer was washed with water and saturated brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. filtrationfiltered
  5. customafter which the solvent was evaporated from the filtrate under a reduced pressure
  6. customThe residue was purified by silica gel column chromatography (heptane:ethyl acetate=6:1)

Sources & evidence

ORD record
ord-c313cc8c21d84bf7b5c9114ef199fce3
Source dataset
uspto-grants-2012_05
Patent number
US08183264B2

Reaction notes

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