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Cesium carbonate → Tert-butyl 2-(2-(benzyloxy)-5-(4-(dimethylamino)piperidin-1-yl)benzamido)-4-phenylbenzoate

HRID 454604
ノート
印刷プレビュー

反応式

HRID 454604 の反応式
Cl.Cl.[CH3:3][N:4]([CH3:11])[CH:5]1[CH2:10][CH2:9][NH:8][CH2:7][CH2:6]1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:18]([O:25][C:26]1[CH:53]=[CH:52][C:51](Br)=[CH:50][C:27]=1[C:28]([NH:30][C:31]1[CH:43]=[C:42]([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[CH:41]=[CH:40][C:32]=1[C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])=[O:29])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.C(Cl)(Cl)Cl.O.C1(C)C=CC=CC=1>[CH2:18]([O:25][C:26]1[CH:53]=[CH:52][C:51]([N:8]2[CH2:9][CH2:10][CH:5]([N:4]([CH3:11])[CH3:3])[CH2:6][CH2:7]2)=[CH:50][C:27]=1[C:28]([NH:30][C:31]1[CH:43]=[C:42]([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[CH:41]=[CH:40][C:32]=1[C:33]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])=[O:29])[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

11

反応物 4

HCID 10796Cesium carbonate2 回HCID 62657Potassium Phosphate, TribasicHCID 225914404-(Dimethylamino)piperidine dihydrochlorideHCID 66990333Tert-butyl 2-(2-(benzyloxy)-5-bromobenzamido)-4-phenylbenzoate

生成物 1

HCID 66989971Tert-butyl 2-(2-(benzyloxy)-5-(4-(dimethylamino)piperidin-1-yl)benzamido)-4-phenylbenzoate収率 79.9%

試薬・触媒・溶媒 6

HCID 167845palladium(II) acetate触媒3 回HCID 9811564Bis(dibenzylideneacetone)palladium触媒3 回HCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl触媒3 回HCID 962Water溶媒HCID 1140Toluene溶媒HCID 6212Chloroform溶媒

実験手順

4-(Dimethylamino)piperidine dihydrochloride (0.11 g), cesium carbonate (0.44 g), tris(dibenzylideneacetone)dipalladium(0) (2.5 mg), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (6.4 mg), and palladium(II) acetate (1.2 mg) were added to a toluene (2.3 mL) solution of tert-butyl 2-(2-(benzyloxy)-5-bromobenzamido)-4-phenylbenzoate (0.15 g), followed by heating to reflux under a nitrogen atmosphere for 3 hours. The reaction mixture was cooled to room temperature, and cesium carbonate (0.13 g), tris(dibenzylideneacetone)dipalladium(0) (2.5 mg), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (6.4 mg), and palladium(II) acetate (1.2 mg) were added to the reaction mixture, followed by heating to reflux under a nitrogen atmosphere for 7 hours. The reaction mixture was cooled to room temperature, and tripotassium phosphate (0.29 g), tris(dibenzylideneacetone)dipalladium(0) (2.5 mg), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (6.4 mg), and palladium(II) acetate (1.2 mg) were added to the reaction mixture, followed by heating to reflux under a nitrogen atmosphere for 2 hours and 30 minutes. The reaction mixture was cooled to room temperature, and water and chloroform were added thereto. The insoluble substance was removed by filtration. The organic layer was separated and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography [Kanto Chemical Co., Inc., silica gel 60 (spherical), eluent: 100-90% chloroform/methanol] to obtain 0.13 g of tert-butyl 2-(2-(benzyloxy)-5-(4-(dimethylamino)piperidin-1-yl)benzamido)-4-phenylbenzoate.

後処理

  1. temperatureby heating
  2. temperatureto reflux under a nitrogen atmosphere for 3 hours
  3. temperatureby heating
  4. temperatureto reflux under a nitrogen atmosphere for 7 hours
  5. temperatureThe reaction mixture was cooled to room temperature
  6. temperatureby heating
  7. temperatureto reflux under a nitrogen atmosphere for 2 hours and 30 minutes
  8. temperatureThe reaction mixture was cooled to room temperature
  9. customThe insoluble substance was removed by filtration
  10. customThe organic layer was separated
  11. dry with materialdried over anhydrous sodium sulfate
  12. customthe solvent was evaporated under reduced pressure
  13. customThe obtained residue was purified by silica gel column chromatography [Kanto Chemical Co., Inc., silica gel 60 (spherical), eluent: 100-90% chloroform/methanol]

出典と根拠

ORDレコード
ord-62e47d063d614d2489678a361990ba65
出典データセット
uspto-grants-2013_07
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08492582B2

反応ノート

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