Sodium Azide → Ethyl 4-azidobutanoate

HRID 2280971Notes

Reaction equation

HRID 2280971 reaction equation
Br[CH2:2][CH2:3][CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[N-:10]=[N+:11]=[N-:12].[Na+]>CN(C=O)C>[N:10]([CH2:2][CH2:3][CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6])=[N+:11]=[N-:12]

Participants

4

Reactant 2

HCID 33557Sodium AzideHCID 76300Ethyl 4-bromobutyrate

Product 1

HCID 12382175Ethyl 4-azidobutanoateYield 96.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Ethyl 4-bromobutanoate (17.11 g, 87.7 mmol) and NaN3 (28.50 g, 438.5 mmol) was dissolved in 70 mL DMF and reacted at 77° C. for 30 hours. 250 mL of 4:1 EtOAc/hexanes was added, and was washed twice with 250 mL saturated aqueous sodium bicarbonate, and once with 200 mL water. Organic layer was dried over sodium sulfate, filtered and concentrated in vacuo to give ethyl 4-azidobutanoate 6 (13.26 g, 96%). Ethyl 4-azidobutanoate 6 (6.18 g, 39.29 mmol) was then saponified using excess KOH in 12:10 methanol/water at 0° C. for 5 minutes and then ambient temperature for 11 hours, followed by acid workup to yield 4-Azidobutanoic acid 7 (4.69 g, 92%). 1H NMR (400 MHz, cdcl3) δ 1.71-1.98 (2H, m), 2.45 (2H, t, J=7.2 Hz), 3.35 (2H, t, J=6.7 Hz), 11.21 (1H, s) ppm.

Workup

  1. customreacted at 77° C. for 30 hours
  2. washwas washed twice with 250 mL saturated aqueous sodium bicarbonate
  3. dry with materialOrganic layer was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-70d09a27cf9743368a88d02edb85db7c
Source dataset
uspto-grants-2015_09
Patent number
US09139565B2

Reaction notes

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