Trifluoroacetic acid → Ethyl 2-(4-bromo-2-fluorophenyl)-2-(4-ethyl-3-oxo-1-oxa-4,9-diazaspiro[5.5]undecan-9-yl)acetate

HRID 1525921ノート

反応式

HRID 1525921 の反応式
[CH2:1]([N:3]1[CH2:8][C:7]2([CH2:13][CH2:12][N:11](C(OC(C)(C)C)=O)[CH2:10][CH2:9]2)[O:6][CH2:5][C:4]1=[O:21])[CH3:2].C(O)(C(F)(F)[F:25])=O.C(=O)([O-])[O-].[K+].[K+].Br[CH:36]([C:42]1[CH:47]=[CH:46][C:45]([Br:48])=[CH:44][CH:43]=1)[C:37]([O:39][CH2:40][CH3:41])=[O:38]>ClCCl.O>[Br:48][C:45]1[CH:46]=[CH:47][C:42]([CH:36]([N:11]2[CH2:12][CH2:13][C:7]3([O:6][CH2:5][C:4](=[O:21])[N:3]([CH2:1][CH3:2])[CH2:8]3)[CH2:9][CH2:10]2)[C:37]([O:39][CH2:40][CH3:41])=[O:38])=[C:43]([F:25])[CH:44]=1

参加物

7

反応物 4

HCID 6422Trifluoroacetic acidHCID 11430Potassium CarbonateHCID 12754876Ethyl 2-bromo-(4-bromophenyl)acetateHCID 71270774Tert-butyl 4-ethyl-3-oxo-1-oxa-4,9-diazaspiro[5.5]undecane-9-carboxylate

生成物 1

HCID 71270877Ethyl 2-(4-bromo-2-fluorophenyl)-2-(4-ethyl-3-oxo-1-oxa-4,9-diazaspiro[5.5]undecan-9-yl)acetate

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒

実験手順

To a solution of tert-butyl 4-ethyl-3-oxo-1-oxa-4,9-diazaspiro[5.5]undecane-9-carboxylate (1 g, 3.35 mmol) in dichloromethane (10 mL) was added TFA (0.775 mL, 10.05 mmol). The reaction mixture was stirred at room temperature overnight, at which point the deprotection had proceeded to completion. The reaction mixture was concentrated in vacuo, dichloromethane was added, and the solution was concentrated in vacuo again. The residue was dissolved with N,N-dimethylformamide (12 mL). To this solution was added potassium carbonate (0.463 g, 3.35 mmol) and ethyl 2-bromo-2-(4-bromophenyl)acetate (1.079 g, 3.35 mmol). The reaction mixture was stirred at 40° C. for overnight, at which point the reaction had proceeded to completion. The reaction mixture was poured into water (120 mL) and was extracted with ethyl acetate (80 mL×3). The combined organic layers were dried and concentrated in vacuo. Crude ethyl 2-(4-bromo-2-fluorophenyl)-2-(4-ethyl-3-oxo-1-oxa-4,9-diazaspiro[5.5]undecan-9-yl)acetate was obtained (590 mg) and was used directly in the next step. MS(ES)+ m/e 457 [M+H]+.

後処理

  1. concentrationThe reaction mixture was concentrated in vacuo, dichloromethane
  2. additionwas added
  3. concentrationthe solution was concentrated in vacuo again
  4. dissolutionThe residue was dissolved with N,N-dimethylformamide (12 mL)
  5. stirringThe reaction mixture was stirred at 40° C. for overnight, at which
  6. extractionwas extracted with ethyl acetate (80 mL×3)
  7. customThe combined organic layers were dried
  8. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-71e0fda66ae04575bfc195f9d1444ff1
出典データセット
uspto-grants-2015_07
特許番号
US09084794B2

反応ノート

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