Water → 4-Amino-8-bromo-N-butyl-cinnoline-3-carboxamide

HRID 31092

Reaktionsgleichung

Reaktionsgleichung von HRID 31092
[Br:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[NH:8][N:9]=[C:10]([C:18]#[N:19])[C:11]([NH:13][CH2:14][CH2:15][CH2:16][CH3:17])=[O:12].[Cl-].[Al+3].[Cl-].[Cl-].O.[C@H](O)(C([O-])=O)[C@@H](O)C([O-])=O.[Na+].[K+]>C1(C)C=CC=CC=1>[NH2:19][C:18]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][CH2:15][CH2:16][CH3:17])=[O:12]

Komponenten

6

Edukt 4

HCID 962WaterHCID 9357Potassium Sodium TartrateHCID 6451240Aluminum(III) ChlorideHCID 866130982-[(2-bromophenyl)-hydrazono]-N-butyl-2-cyanoacetamide

Produkt 1

HCID 672287024-Amino-8-bromo-N-butyl-cinnoline-3-carboxamideAusbeute 26,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
90 °C

Versuchsvorschrift

To a solution of 2-[(2-bromophenyl)-hydrazono]-N-butyl-2-cyanoacetamide (2.5 g, 7.7 mmol) in anhydrous toluene (Aldrich, 50 mL) under N2 was added portion-wise aluminum chloride (Aldrich, 3.1 g, 23.2 mmol) over 5 minutes. The mixture was heated to 90° C. with vigorous stirring for 1.5 hours then cooled to ˜0° C. Water (3 mL) was added drop wise followed by careful addition of Rochelle's salt (saturated aqueous potassium sodium tart rate, 50 mL). The reaction was stirred for 25 minutes and then poured into a separator funnel. The aqueous layer contained a thick white precipitate and was quickly removed. The organic layer was washed with Rochelle's salt and brine, dried over magnesium sulfate, filtered and concentrated to give 2.6 g slightly crude product which was purified on silica gel using a gradient of 20 to 60% ethyl acetate in hexane. Recrystallization from ethyl acetate/hexanes (10 mL each, 0° C. overnight) afforded the title compound as a white solid (650 mg, 26%). 1H NMR (300.132 MHz, CDCl3) δ 8.55 (bs, 1H), 8.13 (dd, J=7.4, 1.0 Hz, 1H), 7.82 (dd, J=8.5, 1.0 Hz, 1H), 7.50 (dd, J=8.5, 7.6 Hz, 1H), 3.52 (q, J=6.6 Hz, 2H), 1.65 (quintet, J=7.2 Hz, 2H), 1.47 (sextet, J=7.3 Hz, 2H), 0.97 (t, J=7.3 Hz, 3H). MS APCI, m/z=323/325 (M+H). HPLC 1.93 min.

Aufarbeitung

  1. temperaturethen cooled to ˜0° C
  2. stirringThe reaction was stirred for 25 minutes
  3. additionpoured into a separator funnel
  4. customwas quickly removed
  5. washThe organic layer was washed with Rochelle's salt and brine
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give 2.6 g slightly crude product which
  10. customwas purified on silica gel using a gradient of 20 to 60% ethyl acetate in hexane
  11. customRecrystallization from ethyl acetate/hexanes (10 mL each, 0° C. overnight)

Quellen und Nachweise

ORD-Eintrag
ord-62949ba2dcc5444088e93c3ccb8dc2a7
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07425556B2

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