4-Toluenesulfonyl chloride → 5-bromo-3-iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine

HRID 603015Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([I:11])=[CH:9][NH:8][C:5]2=[N:6][CH:7]=1.[C:12]1([CH3:22])[CH:17]=[CH:16][C:15]([S:18](Cl)(=[O:20])=[O:19])=[CH:14][CH:13]=1>C1COCC1>[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([I:11])=[CH:9][N:8]([S:18]([C:15]3[CH:16]=[CH:17][C:12]([CH3:22])=[CH:13][CH:14]=3)(=[O:20])=[O:19])[C:5]2=[N:6][CH:7]=1

Participants

Conditions

Temperature: 0 °C

Procedure

Into a 250 mL round bottomed flask, were added 5-bromo-3-iodo-1H-pyrrolo[2,3-b]pyridine (8.00 g, 40.6 mmol) and 120 mL dry THF. The solution was cooled in an ice bath, at 0° C. and Nail (2.40 g, 60.0 mmol) was added in three portions. After 20 min, p-toluenesulfonyl chloride (8.70 g, 45.63 mmol) was added, and die reaction mixture was allowed to warm to it over 30 min. The reaction mixture was concentrated and hexanes was added to obtain a precipitate, which was collected and washed with ice cold 2M NaOH. The crude product was recrystallized from EtOAc/hexanes to afford 17.8 g (92%) of the title compound as a light tan powder. 1H-NMR (500 MHz, d6-DMSO) δ 8.49 (d, J=2.5 Hz, 1H), 8.21 (s, 1H), 7.99 (d, J=2.0 Hz, 1H), 7.98 (d, j=8.5 Hz, 2H), 7.42 (d, J=8.5 Hz, 2H), 2.32 (s, 3H); MS: m/z 476.8/478.8 [MH+].

Workup

additionNail (2.40 g, 60.0 mmol) was added in three portions
customdie reaction mixture
temperatureto warm to it over 30 min
concentrationThe reaction mixture was concentrated
additionhexanes was added
customto obtain a precipitate, which
customwas collected
washwashed with ice cold 2M NaOH
customThe crude product was recrystallized from EtOAc/hexanes

Sources & evidence

ORD record: ord-ad59c8f1dd0d4ce6b76cceb49b5f42cc
Source dataset: uspto-grants-2011_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07906648B2

Reaction notes

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