Acetic Acid → 4-amino-3-(6-chloro-8-oxo-8,9-dihydro-7H-purin-2-ylamino)benzonitrile

HRID 2074190Notes

Reaction equation

[Cl:1][C:2]1[N:10]=[C:9]([NH:11][C:12]2[CH:13]=[C:14]([CH:17]=[CH:18][C:19]=2[N+:20]([O-])=O)[C:15]#[N:16])[N:8]=[C:7]2[C:3]=1[NH:4][C:5](=[O:23])[NH:6]2.C(O)(=O)C.O.[NH4+].[OH-]>[Fe].C(O)C>[NH2:20][C:19]1[CH:18]=[CH:17][C:14]([C:15]#[N:16])=[CH:13][C:12]=1[NH:11][C:9]1[N:8]=[C:7]2[C:3]([NH:4][C:5](=[O:23])[NH:6]2)=[C:2]([Cl:1])[N:10]=1

Participants

Conditions

Temperature: 90 °C

Procedure

To 3-(6-chloro-8-oxo-8,9-dihydro-7H-purin-2-ylamino)-4-nitrobenzonitrile (0.41 g, 1.23 mmol) was added glacial acetic acid (30 mL), water (75 mL) and ethanol (150 mL), followed by iron powder (Aldrich, 0.69 g, 12.3 mmol, 10 equiv.) and the reaction mixture was stirred at 90° C. for 15 min (LC-MS monitoring), when it became a clear dark orange solution. It was cooled to r.t., then concentrated NH4OH (50 mL) was added to bring the pH to 11. The reaction mixture was stirred at r.t. for 30 min. Repeated extractions into ethyl acetate, then into 25% isopropanol in CH2Cl2 (total volume 2 L), drying of the combined organic extracts, and in vacuo evaporation of the solvent provided the desired product as a brown solid, which was used in the next step without further purification. MS (EI) m/z 302.1 (MH)+.

Workup

temperatureIt was cooled to r.t.
stirringThe reaction mixture was stirred at r.t. for 30 min
extractionextractions into ethyl acetate
dry with materialinto 25% isopropanol in CH2Cl2 (total volume 2 L), drying of the combined organic extracts
customin vacuo evaporation of the solvent

Sources & evidence

ORD record: ord-48fd233c01fc48b4aafee724c3e47d86
Source dataset: uspto-grants-2011_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07919490B2

Reaction notes

Loading…