2-Chloro-3-nitropyridine → HCID 23659336, compound

HRID 522511Notes

Reaction equation

HRID 522511 reaction equation
[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=[CH:4][N:3]=1.[Li+].[Cl-].Br[CH:14]1[CH2:19][CH2:18][CH2:17][CH:16]=[CH:15]1.C([Cu])#N>C1COCC1>[Cl:1][C:2]1[C:7]([N+:8]([O-:10])=[O:9])=[C:6]([CH:19]2[CH2:18][CH2:17][CH2:16][CH:15]=[CH:14]2)[CH:5]=[CH:4][N:3]=1

Participants

6

Reactant 4

HCID 796132-Chloro-3-nitropyridineHCID 1370573-BromocyclohexeneHCID 433294Lithium ChlorideHCID 178418546HCID 178418546, compound

Product 1

HCID 23659336HCID 23659336, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-50 °C

Procedure

2-Chloro-3-nitropyridine (18) (159 mg, 1.0 mmol) in THF (2 mL) was added to a solution of TMPZnCl.LiCl (2) (1.3 M in THF, 0.85 mL, 1.1 mmol) at 25° C. and the reaction mixture was then stirred at this temperature for 30 min according to TP 2. After cooling down to −50° C., 3-bromo-cyclohexene (192 mg, 1.2 mmol) and CuCN.2LiCl (1.0 M solution in THF, 0.05 mL, 0.05 mmol) were added and the reaction mixture was stirred for 1 h at the same temperature. The reaction mixture was quenched with a sat. aq. NH4Cl solution (20 mL), extracted with diethyl ether (3×50 mL) and dried over anhydrous Na2SO4. After filtration, the solvent was evaporated in vacuo. Purification by flash-chromatography (CH2Cl2/n-pentane, 1:1) furnished 2-chloro-4-cyclohex-2-enyl-3-nitro-pyridine (20) (173 mg, 73%) as a colourless solid.

Workup

  1. customThe reaction mixture was quenched with a sat. aq. NH4Cl solution (20 mL)
  2. extractionextracted with diethyl ether (3×50 mL)
  3. dry with materialdried over anhydrous Na2SO4
  4. filtrationAfter filtration
  5. customthe solvent was evaporated in vacuo
  6. customPurification by flash-chromatography (CH2Cl2/n-pentane, 1:1)

Sources & evidence

ORD record
ord-784bf049066d478395e69a260f31e6b3
Source dataset
uspto-grants-2016_05
Patent number
US09334237B2

Reaction notes

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