Diethyl Ether → 5-Bromo-7-hydroxy-1H-pyrrolo[2,3-b]pyridin-7-ium 3-chlorobenzoate

HRID 1693690Notes

Reaction equation

HRID 1693690 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[CH:10]=[CH:9][NH:8][C:5]2=[N:6][CH:7]=1.[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[C:14]([C:18]([O:20]O)=[O:19])[CH:13]=1.CC[O:24]CC>CN1C(=O)CCC1>[Cl:11][C:12]1[CH:13]=[C:14]([CH:15]=[CH:16][CH:17]=1)[C:18]([O-:20])=[O:19].[Br:1][C:2]1[CH:3]=[C:4]2[CH:10]=[CH:9][NH:8][C:5]2=[N+:6]([OH:24])[CH:7]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 70297m-Chloroperbenzoic acidHCID 103079325-bromo-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 672805145-Bromo-7-hydroxy-1H-pyrrolo[2,3-b]pyridin-7-ium 3-chlorobenzoate

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent2×

Procedure

5-Bromo-1H-pyrrolo[2,3-b]pyridine (20 g, 0.1 mol) was suspended in 300 mL of NMP. A solution of 3-Chloroperbenzoic acid (40 g, 0.16 mol) in 100 mL NMP was added dropwise over 30 min. The solution was stirred at 23° C. for 1 h after which 600 mL of ether were added. The grey precipitate was filtered off and washed with ether to yield 18 g of 5-Bromo-7-hydroxy-1H-pyrrolo[2,3-b]pyridin-7-ium 3-chlorobenzoate. The filtrate was stirred with 250 mL saturated sodium bicarbonate solution and 250 mL water to give 5-Bromo-1H-pyrrolo[2,3-b]pyridine 7-oxide (4.3 g, 20.2 mmol). The filtered 5-Bromo-7-hydroxy-1H-pyrrolo[2,3-b]pyridin-7-ium 3-chlorobenzoate was suspended in 200 mL of water and 200 mL of saturated sodium bicarbonate solution and was vigorously stirred for 1 h. The grey solids were filtered and washed with water to give a second crop of 5-Bromo-1H-pyrrolo[2,3-b]pyridine 7-oxide (11.15 g, 52.3 mmol, 71% combined yield). 1H NMR (500 MHz, DMSO-d6) δ 12.68 (s, 1H), 8.39 (d, J=1.5 Hz, 1H), 7.9 (d, J=1.5 Hz, 1H), 7.5 (d, J=3.5 Hz, 1H), 6.54 (d, J=3.5 Hz, 1H). MS: m/z 212.9 (M+H+).

Workup

  1. additionwere added
  2. filtrationThe grey precipitate was filtered off
  3. washwashed with ether

Sources & evidence

ORD record
ord-eaee341749ca48b6af3677deabeb853c
Source dataset
uspto-grants-2012_04
Patent number
US08158647B2

Reaction notes

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