Sodium hydride → 4-(5-Bromo-3-nitropyrid-2-yl)-4,4-bis(carbethoxy)butyronitrile

HRID 371405

Reaction equation

HRID 371405 reaction equation
[CH2:1]([O:3][C:4](=[O:15])[CH:5]([CH2:11][CH2:12][C:13]#[N:14])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH3:2].[H-].[Na+].Cl[C:19]1[C:24]([N+:25]([O-:27])=[O:26])=[CH:23][C:22]([Br:28])=[CH:21][N:20]=1>O1CCCC1>[Br:28][C:22]1[CH:23]=[C:24]([N+:25]([O-:27])=[O:26])[C:19]([C:5]([C:4]([O:3][CH2:1][CH3:2])=[O:15])([C:6]([O:8][CH2:9][CH3:10])=[O:7])[CH2:11][CH2:12][C:13]#[N:14])=[N:20][CH:21]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 87005Diethyl (2-cyanoethyl)malonateHCID 70194125-Bromo-2-chloro-3-nitropyridine

Product 1

HCID 145374574-(5-Bromo-3-nitropyrid-2-yl)-4,4-bis(carbethoxy)butyronitrileYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A solution of 2-(2-cyanoethyl)malonic acid diethyl ester (24.2 g) in tetrahydrofuran (15 ml) was added to a suspension of sodium hydride (2.45 g) in tetrahydrofuran (30 ml) at 20° C. under nitrogen. To this was added 2-chloro-3-nitro-5-bromopyridine (22 g) and the mixture so obtained was heated to 93°-95° C. A small amount of tetrahydrofuran was allowed to distil off. The mixture was heated under reflux for 2.5 hr. The reaction mixture was poured into water and neutralised to pH 7 with concentrated hydrochloric acid. The aqueous phase was extracted with chloroform, dried (MgSO4) decolourised with charcoal and filtered through a silica column. The chloroform eluant was evaporated to yield an oil which slowly crystallised. The crystals were washed in petroleum ether (40°-60° C.) and dried to yield 4-(5-bromo-3-nitropyrid-2-yl)-4,4-bis(carbethoxy)butyronitrile (28 g) m.p. 58°-62° C.

Workup

  1. customthe mixture so obtained
  2. temperaturewas heated to 93°-95° C
  3. customto distil off
  4. temperatureThe mixture was heated
  5. temperatureunder reflux for 2.5 hr
  6. additionThe reaction mixture was poured into water and neutralised to pH 7 with concentrated hydrochloric acid
  7. extractionThe aqueous phase was extracted with chloroform
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered through a silica column
  10. customThe chloroform eluant was evaporated
  11. customto yield an oil which
  12. customslowly crystallised
  13. washThe crystals were washed in petroleum ether (40°-60° C.)
  14. customdried

Sources & evidence

ORD record
ord-fe419116281541baab93d574c1bdf899
Source dataset
uspto-grants-1985_07
Patent number
US04532252

Linked notes

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