Diethyl Ether → HCID 86663041, compound

HRID 2410788Notes

Reaction equation

HRID 2410788 reaction equation
[NH2:1][C:2]1[C:11]([C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=2)=[N:10][C:9]([Br:19])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].N([O-])=O.[Na+].[N-:24]=[N+:25]=[N-].[Na+].CCOCC>C(O)(C(F)(F)F)=O.O>[N:1]([C:2]1[C:11]([C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=2)=[N:10][C:9]([Br:19])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])=[N+:24]=[N-:25]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 86663040HCID 86663040, compound

Product 1

HCID 86663041HCID 86663041, compoundYield 218.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

Methyl 3-amino-6-bromo-2-(4-chlorophenyl)isonicotinate (3.86g, 11 3 mmol) was dissolved in TFA (57 mL) and the solution was cooled in an ice bath. Solid sodium nitrite (1.72 g, 24 9 mmol) was added slowly with stirring to give a brown solution with gas evolution. After 30 min solid sodium azide (7.35 g, 113 mmol) was added in portions over 5 min with gas evolution. Et2O (57 mL) was slowly added and a precipitate formed. After stirring for 0.5 h, water was added and the mixture was extracted with EtOAc. The combined organic phases were washed with water (3×) and brine (1×) and then saturated aqueous Na2CO3 solution (so that the aqueous phase was basic) and brine (1×). After drying with sodium sulfate, the solvent was removed to leave methyl 3-azido-6-bromo-2-(4-chlorophenyl)isonicotinate (2.41 g, 6.56 mmol, 58.0% yield) as a fluffy yellow solid. 1 H NMR (400 MHz, chloroform-d) δ ppm 7.79 (1H, s), 7.68-7.73 (2H, m), 7.42-7.47 (2H, m), 4.00 (3H, s).

Workup

  1. temperaturethe solution was cooled in an ice bath
  2. customto give a brown solution with gas evolution
  3. customa precipitate formed
  4. stirringAfter stirring for 0.5 h
  5. extractionthe mixture was extracted with EtOAc
  6. washThe combined organic phases were washed with water (3×) and brine (1×)
  7. dry with materialAfter drying with sodium sulfate
  8. customthe solvent was removed

Sources & evidence

ORD record
ord-fb82c737ab3a4cafb916301c1c698d9f
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

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