Hydrochloric Acid → 3-Bromo-9H-dipyrido[2,3-b;4',3'-d]pyrrole-6-carboxylic acid azide

HRID 1506030Notes

Reaction equation

Cl.[Br:2][C:3]1[CH:19]=[N:18][C:6]2[NH:7][C:8]3[CH:13]=[N:12][C:11]([C:14]([NH:16][NH2:17])=[O:15])=[CH:10][C:9]=3[C:5]=2[CH:4]=1.[N:20]([O-])=O.[Na+].C(=O)(O)[O-].[Na+]>O>[Br:2][C:3]1[CH:19]=[N:18][C:6]2[NH:7][C:8]3[CH:13]=[N:12][C:11]([C:14]([N:16]=[N+:17]=[N-:20])=[O:15])=[CH:10][C:9]=3[C:5]=2[CH:4]=1

Participants

Conditions

Temperature: 0 °C

Procedure

Hydrogen chloride (3.0 mL, 90 mmol) was added dropwise to a suspension of 3-bromo-9H-dipyrido[2,3-b;4′,3′-d]pyrrole-6-carboxylic acid hydrazide (530 mg, 1.73 mmol) in water (12.4 mL). Once homogeneous, the solution was cooled to 0° C. and a solution of 3N sodium nitrite in water (0.60 mL, 2.0 mmol) was added to the mixture. After 1 h, added another 1.03 eq. of 3N sodium nitrite in water (0.60 mL, 2.0 mmol) and allowed the reaction to warm to ambient temperature over night. After 17 h at room temperature, the reaction was cooled to 0° C. and a solution of 3N sodium nitrite in water (0.60 mL, 2.0 mmol) was added and then warmed to room temperature. The reaction was made basic with a solution of saturated sodium bicarbonate, and the solid precipitate was collected by filtration, washed with water, and dried in a dessicator under vacuum to provide a solid material that was 70% pure by LCMS analysis.

Workup

customthe reaction
temperatureto warm to ambient temperature over night
waitAfter 17 h at room temperature
temperaturethe reaction was cooled to 0° C.
temperaturewarmed to room temperature
filtrationthe solid precipitate was collected by filtration
washwashed with water
customdried in a dessicator under vacuum
customto provide a solid material that

Sources & evidence

ORD record: ord-31743c1242fb44dda117d05e25e4c380
Source dataset: uspto-grants-2015_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09216980B2

Reaction notes

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