Acetic Anhydride → Tert-butyl 5-amino-1-(4-methoxycarbonylphenyl)pyrazole-4-carboxylate

HRID 1160522ノート

反応式

HRID 1160522 の反応式
[C:1]([CH2:3][C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])#[N:2].[CH:11](OCC)(OCC)OCC.C(OC(=O)C)(=O)C.Cl.[NH:29]([C:31]1[CH:40]=[CH:39][C:34]([C:35]([O:37][CH3:38])=[O:36])=[CH:33][CH:32]=1)[NH2:30].CCN(C(C)C)C(C)C>C(OCC)(=O)C>[NH2:2][C:1]1[N:29]([C:31]2[CH:32]=[CH:33][C:34]([C:35]([O:37][CH3:38])=[O:36])=[CH:39][CH:40]=2)[N:30]=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5]

参加物

7

反応物 5

HCID 7918Acetic AnhydrideHCID 31214Ethyl orthoformateHCID 70693tert-Butyl cyanoacetateHCID 81531DiisopropylethylamineHCID 2788448Methyl 4-hydrazinobenzoate hydrochloride

生成物 1

HCID 57437895Tert-butyl 5-amino-1-(4-methoxycarbonylphenyl)pyrazole-4-carboxylate

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

反応条件

温度
125 °C

実験手順

t-Butyl cyanoacetate (14.1 g, 100 mmol) was dissolved in triethyl orthoformate (24.8 mL, 150 mmol). Acetic anhydride (9.625 mL, 100 mL) was added and the mixture heated to 125° C. for 3 h and then volatiles were removed by evaporation under reduced pressure. The residue was dissolved in ethanol (100 mL) and methyl 4-hydrazinylbenzoate hydrochloride (Intermediate#123) (6.06 g, 30 mmol) and DIPEA (5.23 mL, 30 mmol) was added. The mixture was heated to reflux for 5 h and then evaporated under reduced pressure to leave a brown oil which was dissolved in ethyl acetate (300 mL) and washed with water (2×100 mL) and brine (100 mL), dried (MgSO4) and evaporated. The residue was purified by chromatography on silica gel (120 g silica, EtOAc/Hexane 0-50%) to give the title compound as a yellow solid. (7.1 g)

後処理

  1. customvolatiles were removed by evaporation under reduced pressure
  2. dissolutionThe residue was dissolved in ethanol (100 mL)
  3. temperatureThe mixture was heated
  4. temperatureto reflux for 5 h
  5. customevaporated under reduced pressure
  6. customto leave a brown oil which
  7. washwashed with water (2×100 mL) and brine (100 mL)
  8. dry with materialdried (MgSO4)
  9. customevaporated
  10. customThe residue was purified by chromatography on silica gel (120 g silica, EtOAc/Hexane 0-50%)

出典と根拠

ORDレコード
ord-3fe0d4e9adda44ee97e4cc1ca45be55b
出典データセット
uspto-grants-2010_10
特許番号
US07816391B2

反応ノート

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