Ethyl cyanoacetate → N-[(E)-3-[tert-butyl(diphenyl)silyl]oxypropylideneamino]-3-chloroaniline

HRID 1508323

反応式

HRID 1508323 の反応式
NC1[N:6]([C:7]2[CH:12]=[CH:11][CH:10]=[C:9]([Cl:13])[CH:8]=2)[N:5]=[C:4]([CH2:14][CH2:15][O:16][Si:17]([C:30]([CH3:33])([CH3:32])[CH3:31])([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)C=1C(OCC)=O.[Si](OCCC=O)(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.C1C(=O)N(Cl)C(=O)C1.C(OC(=O)CC#N)C.CC[O-].[Na+].N(Cl)Cl>CN(C=O)C.CCO>[Si:17]([O:16][CH2:15][CH2:14]/[CH:4]=[N:5]/[NH:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([Cl:13])[CH:8]=1)([C:30]([CH3:33])([CH3:32])[CH3:31])([C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1)[C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1

参加物

9

反応物 6

HCID 7764Ethyl cyanoacetateHCID 31398ChlorosuccinimideHCID 76939ChlorimideHCID 2723922Sodium ethoxideHCID 9995679Propanal, 3-[[(1,1-dimethylethyl)diphenylsilyl]oxy]-HCID 71255698Ethyl 5-amino-3-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-1-(3-chlorophenyl)-1H-pyrazole-4-carboxylate

生成物 1

HCID 89405959N-[(E)-3-[tert-butyl(diphenyl)silyl]oxypropylideneamino]-3-chloroaniline

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 6228Dimethylformamide溶媒

実験手順

Ethyl 5-amino-3-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-1-(3-chlorophenyl)-1H-pyrazole-4-carboxylate: To a solution of Intermediate 9A (1.34 g, 3.1 mmol) in DMF (5 mL) was added NCS (0.455, 3.41 mmol) and stirred at rt. After 4 h, the reaction mixture was quenched with H2O (100 mL) and extracted with EtOAc (2×). The organic layers were dried (MgSO4) and evaporated to a reddish oil. Separately ethylcyanoacetate (0.351 g, 3.10 mmol) was dissolved in EtOH (5 mL) and to this solution was added NaOEt (21%) (1.16 mL, 3.10 mmol) and the reaction was stirred at rt for 0.5 h followed by the introduction of the iminochloride crude mixture. The above mixture was then stirred at rt. After 2 h, the reaction was quenched with H2O and extracted with EtOAc (2×). The organic layers were dried (MgSO4) and evaporated to yield orange-red oil. The crude product was then purified using silica gel chromatography. Two peaks were isolated—one is the desired product and the other is the chlorinated pyrazoline compound and the two products were taken to the next step as a crude mixture. MS(ESI) m/z: 548.1 (M+H)+.

後処理

  1. customthe reaction mixture was quenched with H2O (100 mL)
  2. extractionextracted with EtOAc (2×)
  3. dry with materialThe organic layers were dried (MgSO4)
  4. customevaporated to a reddish oil
  5. stirringthe reaction was stirred at rt for 0.5 h
  6. stirringThe above mixture was then stirred at rt
  7. waitAfter 2 h
  8. customthe reaction was quenched with H2O
  9. extractionextracted with EtOAc (2×)
  10. dry with materialThe organic layers were dried (MgSO4)
  11. customevaporated
  12. customto yield orange-red oil
  13. customThe crude product was then purified
  14. customTwo peaks were isolated—one

出典と根拠

ORDレコード
ord-20b48038ad794213bf9a155f5cd0605c
出典データセット
uspto-grants-2015_12
特許番号
US09221818B2

関連ノート

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