Azidotrimethylsilane → ethyl 2-(5-azido-7-bromo-3-chloro-5H-chromeno[2,3-c]pyridin-5-yl)acetate

HRID 455596Notes

Reaction equation

HRID 455596 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:14](=[CH:15][CH:16]=1)[O:13][C:7]1[CH:8]=[N:9][C:10]([Cl:12])=[CH:11][C:6]=1[C:5]2([CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])O.[N:24]([Si](C)(C)C)=[N+:25]=[N-:26].C([O+]([B-](F)(F)F)CC)C>C1(C)C=CC=CC=1>[N:24]([C:5]1([CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:6]2[CH:11]=[C:10]([Cl:12])[N:9]=[CH:8][C:7]=2[O:13][C:14]2[C:4]1=[CH:3][C:2]([Br:1])=[CH:16][CH:15]=2)=[N+:25]=[N-:26]

Participants

5

Reactant 3

HCID 78378AzidotrimethylsilaneHCID 86658372ethyl 2-(7-bromo-3-chloro-5-hydroxy-5H-chromeno[2,3-c]pyridin-5-yl)acetateHCID 178467671HCID 178467671, compound

Product 1

HCID 86658373ethyl 2-(5-azido-7-bromo-3-chloro-5H-chromeno[2,3-c]pyridin-5-yl)acetateYield 99.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of ethyl 2-(7-bromo-3-chloro-5-hydroxy-5H-chromeno[2,3-c]pyridin-5-yl)acetate (38.5 g, 97 mmol) in toluene (400 ml) was added azidotrimethylsilane (38.4 ml, 290 mmol) followed by (diethyloxonio)trifluoroborate (24.48 ml, 193 mmol) under an atmosphere of nitrogen. The reaction mixture was stirred at RT for 16 hours. The reaction mixture was quenched with MeOH (200 mL) and diluted with EtOAc. The organic phase was separated, washed with saturated aqueous sodium bicarbonate solution and brine. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to afford ethyl 2-(5-azido-7-bromo-3-chloro-5H-chromeno[2,3-c]pyridin-5-yl)acetate (40.82 g) which was used in the next step without further purification.

Workup

  1. customThe reaction mixture was quenched with MeOH (200 mL)
  2. additiondiluted with EtOAc
  3. customThe organic phase was separated
  4. washwashed with saturated aqueous sodium bicarbonate solution and brine
  5. dry with materialThe organic layer was dried over magnesium sulfate
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-1bf6fa0712d54467a28cec5671fe51a3
Source dataset
uspto-grants-2013_07
Patent number
US08497264B2

Reaction notes

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