Diethyl Ether → HCID 86663048, compound

HRID 2410806Notes

Reaction equation

HRID 2410806 reaction equation
[NH2:1][C:2]1[C:11]([C:12]2[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][CH:13]=2)=[N:10][C:9]([Br:21])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].N([O-])=O.[Na+].[N-:26]=[N+:27]=[N-].[Na+].CCOCC>C(O)(C(F)(F)F)=O.C(Cl)Cl.C1COCC1>[N:1]([C:2]1[C:11]([C:12]2[CH:13]=[CH:14][C:15]([N+:18]([O-:20])=[O:19])=[CH:16][CH:17]=2)=[N:10][C:9]([Br:21])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])=[N+:26]=[N-:27]

Participants

8

Reactant 4

HCID 3283Diethyl EtherHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 86663047HCID 86663047, compound

Product 1

HCID 86663048HCID 86663048, compoundYield 330%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 6422Trifluoroacetic acidSolventHCID 8028TetrahydrofuranSolvent

Procedure

Methyl 3-amino-6-bromo-2-(4-nitrophenyl)isonicotinate (7.2 g, 20 5 mmol) was dissolved in TFA (70 mL) and the yellow solution was cooled in an ice bath. Sodium nitrite (2.82 g, 40.9 mmol) was added in small portions with stirring to give a dark yellow mixture. After 30 min, sodium azide (13.29 g, 204 mmol) was added in small portions followed by Et2O (20 mL). The light yellow mixture was stirred in the ice-bath for 30 min and then partitioned between DCM and water. The organic phase washed with water (3×250 mL), sat. aq. Na2CO3 solution (3×250 mL), brine, dried with sodium sulfate, and the solvent removed. Silica gel chromatography (30% THF in DCM) afforded methyl 3-azido-6-bromo-2-(4-nitrophenyl)isonicotinate (6.8 g, 16.5 mmol, 81% yield). 1H NMR (500 MHz, DMSO-d6) δ ppm 8.37 (2H, d, J=8.85 Hz), 8.06 (1H, s), 8.02 (2H, d, J=9.16 Hz), 3.97 (3H, s).

Workup

  1. temperaturethe yellow solution was cooled in an ice bath
  2. customto give a dark yellow mixture
  3. custompartitioned between DCM and water
  4. washThe organic phase washed with water (3×250 mL), sat. aq. Na2CO3 solution (3×250 mL), brine
  5. dry with materialdried with sodium sulfate
  6. customthe solvent removed

Sources & evidence

ORD record
ord-13c2f44f810848c89a801e7c422c16b5
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

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