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

HRID 31092

反応式

HRID 31092 の反応式
[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]

参加物

6

反応物 4

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

生成物 1

HCID 672287024-Amino-8-bromo-N-butyl-cinnoline-3-carboxamide収率 26.1%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
90 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-62949ba2dcc5444088e93c3ccb8dc2a7
出典データセット
uspto-grants-2008_09
特許番号
US07425556B2

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