Potassium Sodium Tartrate → 4-amino-8-bromo-N-cyclopropylcinnoline-3-carboxamide

HRID 2375590Notes

Reaction equation

HRID 2375590 reaction equation
[CH:1]1([NH:4][C:5](=[O:18])[C:6]([C:16]#[N:17])=[N:7][NH:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[Br:15])[CH2:3][CH2:2]1.[Cl-].[Al+3].[Cl-].[Cl-].[C@H](O)(C([O-])=O)[C@@H](O)C([O-])=O.[Na+].[K+]>C1(C)C=CC=CC=1.C(OCC)(=O)C>[NH2:17][C:16]1[C:14]2[C:9](=[C:10]([Br:15])[CH:11]=[CH:12][CH:13]=2)[N:8]=[N:7][C:6]=1[C:5]([NH:4][CH:1]1[CH2:3][CH2:2]1)=[O:18]

Participants

6

Reactant 3

HCID 9357Potassium Sodium TartrateHCID 6451240Aluminum(III) ChlorideHCID 86613100HCID 86613100, compound

Product 1

HCID 672292774-amino-8-bromo-N-cyclopropylcinnoline-3-carboxamideYield 54.1%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
72.5 °C

Procedure

A 500 mL, 3-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, reflux condenser, and addition funnel was charged with N-cyclopropyl-2-cyano-2-[(2-bromophenyl)hydrazono]acetamide (1.7 g, 5.6 mmol) in anhydrous toluene (0.2 L). The reaction mixture was cooled with stirring in an ice bath. Aluminum chloride (1.6 g, 12.0 mmol) was added in three portions. Removed ice bath and heated at 70-75° C. for 60 hours. The reaction mixture was allowed to cool to room temperature, diluted with ethyl acetate (200 mL), added saturated Rochelle's salt (100 mL), stirred vigorously for 1 hour (until purple color dissipated to orange/yellow). Decanted organic layer from thick white aqueous layer, washed with additional Rochelle's salt, brine, dried and concentrated to an orange residue. The residue was slurried in ether (20 mL) to give title compound (930 mg, 52% yield). MS APCI, m/z=307/309 (M+H).

Workup

  1. customA 500 mL, 3-necked flask equipped with a mechanical stirrer
  2. temperaturethermometer, nitrogen inlet, reflux
  3. additioncondenser, and addition funnel
  4. temperatureThe reaction mixture was cooled
  5. temperatureto cool to room temperature
  6. stirringstirred vigorously for 1 hour (until purple color dissipated to orange/yellow)
  7. washDecanted organic layer from thick white aqueous layer, washed with additional Rochelle's salt, brine
  8. customdried
  9. concentrationconcentrated to an orange residue

Sources & evidence

ORD record
ord-dda72be225cb4168992236d2ced5a86c
Source dataset
uspto-grants-2008_12
Patent number
US07465795B2

Reaction notes

Loading…