Diethyl Ether → HCID 86663045, compound

HRID 2410798Notes

Reaction equation

HRID 2410798 reaction equation
[NH2:1][C:2]1[C:11]([C:12]2[CH:17]=[CH:16][C:15]([C:18]([O:20][CH:21]([CH3:23])[CH3:22])=[O:19])=[CH:14][CH:13]=2)=[N:10][C:9]([Br:24])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].N([O-])=O.[Na+].[N-:29]=[N+:30]=[N-].[Na+].CCOCC>C(O)(C(F)(F)F)=O>[N:1]([C:2]1[C:11]([C:12]2[CH:17]=[CH:16][C:15]([C:18]([O:20][CH:21]([CH3:22])[CH3:23])=[O:19])=[CH:14][CH:13]=2)=[N:10][C:9]([Br:24])=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5])=[N+:29]=[N-:30]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 86663044HCID 86663044, compound

Product 1

HCID 86663045HCID 86663045, compoundYield 92%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

Methyl 3-amino-6-bromo-2-(4-(isopropoxycarbonyl)phenyl)isonicotinate (1.0 g, 2.54 mmol) was dissolved in TFA (15 mL) and the yellow solution was cooled in an ice bath. Sodium nitrite (0.351 g, 5.09 mmol) was added with stirring to give a dark yellow mixture. After 30 min, sodium azide (1.65 g, 25.4 mmol) was added followed immediately by Et2O (15 mL). The light yellow mixture was stirred in the ice bath for 30 min. It was partitioned between EtOAc and sufficient sat. aq. NaHCO3 solution to neutralize the acid. The organic phase was washed with brine, dried with sodium sulfate, and the solvent removed to leave methyl 3-azido-6-bromo-2-(4-(isopropoxycarbonyl)phenyl)isonicotinate (1.0 gm, 2.3 mmole, 92% yield). 1H NMR (500 MHz, chloroform-d) δ ppm 8.13 (2H, d, J=8.24 Hz), 7.82 (2H, d, J=4.58 Hz), 7.80 (1H, s), 5.24-5.30 (1H, m), 4.01 (3H, s), 1.38 (6H, d, J=6.10 Hz).

Workup

  1. temperaturethe yellow solution was cooled in an ice bath
  2. customto give a dark yellow mixture
  3. customIt was partitioned between EtOAc and sufficient sat. aq. NaHCO3 solution
  4. washThe organic phase was washed with brine
  5. dry with materialdried with sodium sulfate
  6. customthe solvent removed

Sources & evidence

ORD record
ord-4b4933c02ea4492399fe3f95ee8683b3
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

Loading…