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Diethyl Ether → Methyl 3-azido-6-bromo-6'-morpholino-2,3'-bipyridine-4-carboxylate

HRID 2410752
Notes
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Reaction equation

HRID 2410752 reaction equation
[NH2:1][C:2]1[C:3]([C:13]2[CH:14]=[N:15][C:16]([N:19]3[CH2:24][CH2:23][O:22][CH2:21][CH2:20]3)=[CH:17][CH:18]=2)=[N:4][C:5]([Br:12])=[CH:6][C:7]=1[C:8]([O:10][CH3:11])=[O:9].N([O-])=O.[Na+].[N-:29]=[N+:30]=[N-].[Na+].CCOCC>C(O)(C(F)(F)F)=O.O>[N:1]([C:2]1[C:3]([C:13]2[CH:14]=[N:15][C:16]([N:19]3[CH2:20][CH2:21][O:22][CH2:23][CH2:24]3)=[CH:17][CH:18]=2)=[N:4][C:5]([Br:12])=[CH:6][C:7]=1[C:8]([O:10][CH3:11])=[O:9])=[N+:29]=[N-:30]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 33557Sodium AzideHCID 23668193Sodium NitriteHCID 86663022Methyl 3-amino-6-bromo-6'-morpholino-2,3'-bipyridine-4-carboxylate

Product 1

HCID 86663023Methyl 3-azido-6-bromo-6'-morpholino-2,3'-bipyridine-4-carboxylateYield 98%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent
HCID 6422Trifluoroacetic acidSolvent

Procedure

Methyl 3-amino-6-bromo-6′-morpholino-2,3′-bipyridine-4-carboxylate (230 mg, 0.59 mmol) was dissolved in TFA (2.9 mL) and the solution was cooled in an ice bath. Solid sodium nitrite (89 mg, 1.29 mmol) was added slowly with stirring to give a red solution. After 30 min, powdered sodium azide (380 mg, 5.85 mmol) was added in portions with gas evolution. Et2O (29 mL) was added with stirring after 0.5 hr, water was added and the mixture was extracted with EtOAc. The combined organic extracts were washed with, water (3×), saturated Na2CO3 solution (until the aqueous phase was basic), and brine (1×). After drying the solvent with sodium sulfate, the solvent was removed. Flash chromatography (step gradient elution with DCM containing 0 to 20% EtOAc) afforded methyl 3-azido-6-bromo-6′-morpholino-2,3′-bipyridine-4-carboxylate (240 mg, 0.57 mmol, 98% yield) yellow solid. 1H NMR (500 MHz, chloroform-d) δ ppm 8.73 (1H, d, J=2.44 Hz), 7.99 (1H, dd, J=9.00, 2.59 Hz), 7.71 (1H, s), 6.68 (1H, d, J=8.85 Hz), 4.00 (3H, s), 3.79-3.86 (4H, m), 3.59-3.66 (4H, m).

Workup

  1. temperaturethe solution was cooled in an ice bath
  2. customto give a red solution
  3. stirringwith stirring after 0.5 hr
  4. extractionthe mixture was extracted with EtOAc
  5. washThe combined organic extracts were washed with, water (3×), saturated Na2CO3 solution (until the aqueous phase
  6. dry with materialAfter drying the solvent with sodium sulfate
  7. customthe solvent was removed
  8. washFlash chromatography (step gradient elution with DCM containing 0 to 20% EtOAc)

Sources & evidence

ORD record
ord-66317d6883524e70b31e53e571173fac
Source dataset
uspto-grants-2014_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08815840B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes