Sodium Iodide → Propanedioic acid, (4-azidobutyl)[3-(3-pyridinyl)propyl]-, diethyl ester

HRID 1494063Notes

Reaction equation

HRID 1494063 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH2:7][CH2:8][CH2:9][CH:10]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH:2]=1.[H-].[Na+].Br[CH2:24][CH2:25][CH2:26][CH2:27]Cl.[I-].[Na+].[N-:31]=[N+:32]=[N-:33].[Na+]>CN(C)C=O>[N:31]([CH2:24][CH2:25][CH2:26][CH2:27][C:10]([CH2:9][CH2:8][CH2:7][C:3]1[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=1)([C:16]([O:18][CH2:19][CH3:20])=[O:17])[C:11]([O:13][CH2:14][CH3:15])=[O:12])=[N+:32]=[N-:33]

Participants

7

Reactant 5

HCID 5238Sodium IodideHCID 24758Sodium hydrideHCID 33557Sodium AzideHCID 813641-Bromo-4-chlorobutaneHCID 10468827Diethyl [3-(3-pyridyl)-propyl]malonate

Product 1

HCID 10068124Propanedioic acid, (4-azidobutyl)[3-(3-pyridinyl)propyl]-, diethyl ester

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 63.34g (0.23 mole) of diethyl [3-(3-pyridyl)-propyl]malonate in 1.1L dimethylformamide is in small portions 9.91 g (0.25 mole) of sodium hydride as a 60% dispension in oil. After stirring at room temperature for 0.5 hours, 28 mL (0.23 mole) of 1-bromo-4-chlorobutane is added and then heated to 60° for 10 hours. Then 68.26 g (0.46 mole) sodium iodide is added followed by 44.44 g (0.68 mole) sodium azide and 9.0 g crown ether 18-Crown-6. The reaction mixture is heated for 15 hours at 60°, is then cooled and poured on ice. The mixture is then extracted with ether (4×500 mL). Combined organic extracts are extracted with 1N aqueous hydrochloric acid (1×200, 2×100 mL). Combined aqueous extract is adjusted to pH 8 by addition of solid sodium bicarbonate and then extracted with ether (3×300 mL). Combined organic extracts are washed with water (3×100 mL), brine (1×300 mL), dried (MgSO4), filtered and then evaporated to dryness to give diethyl [4-azidobutyl][3-(3-pyridyl)-propyl]-malonate as an oil.

Workup

  1. temperatureheated to 60° for 10 hours
  2. temperatureThe reaction mixture is heated for 15 hours at 60°
  3. temperatureis then cooled
  4. additionpoured on ice
  5. extractionThe mixture is then extracted with ether (4×500 mL)
  6. extractionCombined organic extracts are extracted with 1N aqueous hydrochloric acid (1×200, 2×100 mL)
  7. extractionCombined aqueous extract
  8. additionis adjusted to pH 8 by addition of solid sodium bicarbonate
  9. extractionextracted with ether (3×300 mL)
  10. washCombined organic extracts are washed with water (3×100 mL), brine (1×300 mL)
  11. dry with materialdried (MgSO4)
  12. filtrationfiltered
  13. customevaporated to dryness

Sources & evidence

ORD record
ord-2856ff07e56d47148332808877fdaa07
Source dataset
uspto-grants-1991_06
Patent number
US05025025

Reaction notes

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