Potassium Sodium Tartrate → 4-Amino-8-bromo-N-ethyl-cinnoline-3-carboxamide

HRID 31090

Reaction equation

HRID 31090 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][N:9]=[C:10]([C:16]#[N:17])[C:11]([NH:13][CH2:14][CH3:15])=[O:12].[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:4]2[C:3](=[C:2]([Br:1])[CH:7]=[CH:6][CH:5]=2)[N:8]=[N:9][C:10]=1[C:11]([NH:13][CH2:14][CH3:15])=[O:12]

Participants

6

Reactant 3

HCID 9357Potassium Sodium TartrateHCID 6451240Aluminum(III) ChlorideHCID 866130962-[(2-bromophenyl)-hydrazono]-N-ethyl-2-cyanoacetamide

Product 1

HCID 672286714-Amino-8-bromo-N-ethyl-cinnoline-3-carboxamideYield 69.3%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To a stirred solution of 2-[(2-bromophenyl)-hydrazono]-N-ethyl-2-cyanoacetamide (260 mg, 0.88 mmol) in anhydrous toluene (10 mL) was added aluminum chloride (370 mg, 2.78 mmol). The reaction was heated with vigorous stirring at 90° C. for 1.5 hours, cooled, diluted with ethyl acetate (40 mL), and treated with Rochelle's salt (saturated aqueous solution). After stirring for 30 minutes, the organic layer was decanted into a separator funnel. (The white precipitate was rinsed with ethyl acetate three times.) The organic layer was washed with 1:1 brine:Rochelle's salt solution, dried over sodium sulfate, and concentrated to a light brown solid. The solid was slurred in ether and filtered to afford the title compound as a brown solid (180 mg, 69%). 1H NMR (300.132 MHz, CDCl3) δ 8.52 (s, 1H), 8.13 (dd, J=7.4, 1.1 Hz, 1H), 7.82 (dd, J=8.4, 1.1 Hz, 1H), 7.51 (dd, J=8.4, 7.5 Hz, 1H), 3.56 (dq, J=5.8, 7.3 Hz, 2H), 1.31 (t, J=7.3 Hz, 3H). MS APCI, m/z=395/397 (M+H). HPLC 1.90 min.

Workup

  1. temperatureThe reaction was heated
  2. temperaturecooled
  3. stirringAfter stirring for 30 minutes
  4. customthe organic layer was decanted into a separator funnel
  5. wash(The white precipitate was rinsed with ethyl acetate three times
  6. wash) The organic layer was washed with 1:1 brine
  7. dry with materialRochelle's salt solution, dried over sodium sulfate
  8. concentrationconcentrated to a light brown solid
  9. filtrationfiltered

Sources & evidence

ORD record
ord-007e2dcc42ed49c4ba2ee43329806979
Source dataset
uspto-grants-2008_09
Patent number
US07425556B2

Linked notes

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