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

HRID 481074

反応式

HRID 481074 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-hexahydro-cyclohepta(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) δ1.247 (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-a2d273c7fe884f7ab25a83f859d90c45
出典データセット
uspto-grants-2003_11
特許番号
US06653471B2

関連ノート

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