Formamidine acetate → 3,4,5,6-Tetrahydro-3,8,10-triaza-benzo[e]azulene-1-carboxylic acid ethyl ester

HRID 481079ノート

反応式

HRID 481079 の反応式
[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:15](=O)[C:14](=[CH:17][N:18]([CH3:20])C)[CH2:13][CH2:12][CH2:11][C:8]=2[NH:9][CH:10]=1)=[O:5])[CH3:2].C(O)(=O)C.C(N)=[NH:26]>CCO.C(Cl)Cl>[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:15]3[N:26]=[CH:20][N:18]=[CH:17][C:14]=3[CH2:13][CH2:12][CH2:11][C:8]=2[NH:9][CH:10]=1)=[O:5])[CH3:2]

参加物

5

反応物 2

HCID 160693Formamidine acetateHCID 590720525-Dimethylaminomethylene-4-oxo-1,4,5,6,7,8-hexahydro-cyclohepta[b]pyrrole-3-carboxylic acid ethyl ester

生成物 1

HCID 206056153,4,5,6-Tetrahydro-3,8,10-triaza-benzo[e]azulene-1-carboxylic acid ethyl ester収率 77.5%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
120 °C

実験手順

A mixture of 5-dimethylaminomethylene-4-oxo-1,4,5,6,7,8-hexahydro-cyclohepta [b]pyrrole-3-carboxylic acid ethyl ester (840 mg) and formamidine acetate (956 mg, 9.1 mmol) in EtOH (10 mL) is stirred at 120° C. for 4 h. After cooling, the reaction mixture is diluted with CH2Cl2 and washed with half saturated aq NaHCO3 (25 mL), H2O (25 mL), and brine (25 mL) The aqueous washes are reextracted once with CH2Cl2, and the combined extracts are dried over K2CO3 and concentrated. The crude material is purified by flash chromatography on silica gel. Elution with 30:1 CHCl3-MeOH followed by 20:1 CHCl3-MeOH and finally 15:1 CHCl3-MeOH afforded 606 mg (77%) of 3,4,5,6-tetrahydro-3,8,10-triaza-benzo[e]azulene-1-carboxylic acid ethyl ester as a light yellow solid. 1H NMR (CDCl3, 300 MHz) δ9.30 (br s, 1H), 9.02 (s, 1H), 8.43 (s, 1H), 7.24 (d, J=2.7 Hz, 1H), 4.26 (q, J=7.2 Hz, 2H), 2.78 (t, J=7.2 Hz, 2H) 2.70 (m, 2H), 2.12 (m, 2H), 1.26 (t, J=7.2 Hz, 3H).

後処理

  1. temperatureAfter cooling
  2. washwashed with half saturated aq NaHCO3 (25 mL), H2O (25 mL), and brine (25 mL) The aqueous washes
  3. dry with materialthe combined extracts are dried over K2CO3
  4. concentrationconcentrated
  5. customThe crude material is purified by flash chromatography on silica gel
  6. washElution with 30:1 CHCl3-MeOH

出典と根拠

ORDレコード
ord-bc6133f89dca4ebf9b634c87ad50af77
出典データセット
uspto-grants-2003_11
特許番号
US06653471B2

反応ノート

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