Phenylacetylene → 5-Nitro-3-(phenylethynyl)pyridin-2-amine

HRID 2196670Notes

Reaction equation

HRID 2196670 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.[C:12]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)#[CH:13]>[Cu]I.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>[N+:8]([C:6]1[CH:7]=[C:2]([C:13]#[C:12][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:3]([NH2:11])=[N:4][CH:5]=1)([O-:10])=[O:9]

Participants

5

Reactant 2

HCID 10821PhenylacetyleneHCID 27344122-Amino-3-bromo-5-nitropyridine

Product 1

HCID 593229015-Nitro-3-(phenylethynyl)pyridin-2-amineYield 50%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Procedure

A solution of 3-bromo-5-nitropyridin-2-amine (655 mg, 3.0 mmol, 1.0 eq.) in 1:1 TEA/DMF (40 mL) was degassed with argon for 10 minutes, and ethynylbenzene (1.5 eq.), CuI (0.04 eq.), and PdCl2(PPh3)2 (0.04 eq.) were sequentially added. The mixture was degassed with argon for 10 minutes, and then stirred at room temperature for 16 hours. The volatiles were removed under reduced pressure, and CH2Cl2 (25 mL) was added. The mixture was sonicated for 15 minutes, cooled to 0° C., and collected by vacuum filtration to afford 5-nitro-3-(phenylethynyl)pyridin-2-amine (356 mg, 50%).

Workup

  1. customThe mixture was degassed with argon for 10 minutes
  2. customThe volatiles were removed under reduced pressure, and CH2Cl2 (25 mL)
  3. additionwas added
  4. customThe mixture was sonicated for 15 minutes
  5. temperaturecooled to 0° C.
  6. filtrationcollected by vacuum filtration

Sources & evidence

ORD record
ord-59cf437319694310ba6ab629fde7002c
Source dataset
uspto-grants-2012_12
Patent number
US08338452B2

Reaction notes

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