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

HRID 481074

반응식

HRID 481074 반응식
[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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 6344Dichloromethane용매HCID 8471Triethylamine용매HCID 516892Sodium Bicarbonate용매

반응 조건

온도
110 °C

실험 절차

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)

후처리

  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)

출처 및 근거

ORD 기록
ord-a2d273c7fe884f7ab25a83f859d90c45
출처 데이터셋
uspto-grants-2003_11
특허 번호
US06653471B2

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