Ammonium Acetate → 3,4,5,6-Tetrahydro-3,10-diazabenzo[e]azulene-1-carboxylic acid ethyl ester

HRID 497393

反応式

HRID 497393 の反応式
[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:15](=O)[CH2:14][CH2:13][CH2:12][CH2:11][C:8]=2[NH:9][CH:10]=1)=[O:5])[CH3:2].[NH2:17][CH:18]=[CH:19][CH:20]=O.C([O-])(=O)C.[NH4+]>C(N(CC)CC)C.ClCCl.C([O-])(O)=O.[Na+]>[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:15]3[N:17]=[CH:18][CH:19]=[CH:20][C:14]=3[CH2:13][CH2:12][CH2:11][C:8]=2[NH:9][CH:10]=1)=[O:5])[CH3:2]

参加物

7

反応物 3

HCID 517165Ammonium AcetateHCID 18696565Ethyl 4-oxo-1,4,5,6,7,8-hexahydrocyclohepta[B]pyrrole-3-carboxylateHCID 539779123-Aminoacrolein

生成物 1

HCID 206056123,4,5,6-Tetrahydro-3,10-diazabenzo[e]azulene-1-carboxylic acid ethyl ester収率 20%

試薬・触媒・溶媒 3

HCID 6344Dichloromethane溶媒HCID 8471Triethylamine溶媒HCID 516892Sodium Bicarbonate溶媒

反応条件

温度
110 °C

実験手順

A mixture of 4-oxo-1,4,5,6,7,8-hexahydrocyclohepta(b)pyrrole-3-carboxylic acid ethyl ester (7.0 g, 31.67 mmol), 3-amino-prop-2-enal (3.37 g, 47.5 mmol) and ammonium acetate (365 mg, 4.75 mmol) in triethylamine (7 mL) is heated at 110° C. for 4 h. It is cooled to room temperature and the solid residue is dissolved in 100 mL dichloromethane and 100 mL sat. NaHCO3 solution. Layers are separated and the aqueous phase is extracted with 4:1 DCM/2-propanol (4×100 mL). Combined organic layers are dried (Na2SO4) and evaporated. Flash Chromatography on silica gel, eluting with EtOAc:triethylamine (20:1), provides 3,4,5,6-tetrahydro-3,10-diaza-benzo[e]azulene-1-carboxylic acid ethyl ester (1.6 g, 20%) as off-white solid. 1H NMR (400 MHz, CD3OD) δ 1.247 (3H, t), 2.227 (2H, m), 2.631 (4H, m), 4.197 (2H, q), 7.170 (1H, m), 7.405 (1H, s), 7.686 (1H, d), 8.375 (1H, d). MS (ES+) 257 (M+1).

後処理

  1. temperatureIt is cooled to room temperature
  2. customLayers are separated
  3. extractionthe aqueous phase is extracted with 4:1 DCM/2-propanol (4×100 mL)
  4. dry with materialCombined organic layers are dried (Na2SO4)
  5. customevaporated
  6. washFlash Chromatography on silica gel, eluting with EtOAc:triethylamine (20:1)

出典と根拠

ORDレコード
ord-22cf06cdd80b46439b9ac3a9b45263bd
出典データセット
uspto-grants-2005_09
特許番号
US06949562B2

関連ノート

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