반응 #59370

반응 방정식

Rochelle's salt

Water

2-[(2-bromophenyl)-hydrazono]-N-butyl-2-cyanoacetamide

aluminum chloride

→

title compound

수율 26.1%

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

수율 26.1%

용매

toluene

반응 조건

후처리

1. 1
   온도then cooled to ˜0° C
2. 2
   workup.STIRRINGThe reaction was stirred for 25 minutes
3. 3
   workup.ADDITIONpoured into a separator funnel
4. 4
   기타was quickly removed
5. 5
   세척The organic layer was washed with Rochelle's salt and brine
6. 6
   건조dried over magnesium sulfate
7. 7
   여과filtered
8. 8
   농축concentrated
9. 9
   기타to give 2.6 g slightly crude product which
10. 10
    기타was purified on silica gel using a gradient of 20 to 60% ethyl acetate in hexane
11. 11
    기타Recrystallization from ethyl acetate/hexanes (10 mL each, 0° C. overnight)

실험 절차

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.

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