Diisopropylamine → 1-Methyl-3-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-4-phenyl-2-azetidinone

HRID 1199183

反応式

HRID 1199183 の反応式
C([Li])CCC.[CH:6]([NH:9][CH:10]([CH3:12])C)(C)C.C(O[C:16](=[O:27])[CH2:17][N:18]1[Si:22]([CH3:24])([CH3:23])[CH2:21][CH2:20][Si:19]1([CH3:26])[CH3:25])C.[Li+].[Cl-].[CH:30](=[CH:37]N)[C:31]1C=CC=[CH:33][CH:32]=1>CCCCCC.C(OCC)C.[Cl-].[Cl-].[Zn+2]>[CH3:6][N:9]1[CH:10]([C:12]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:37]=2)[CH:17]([N:18]2[Si:19]([CH3:25])([CH3:26])[CH2:20][CH2:21][Si:22]2([CH3:23])[CH3:24])[C:16]1=[O:27]

参加物

9

反応物 5

HCID 7912DiisopropylamineHCID 155076Ethenamine, 2-phenyl-HCID 433294Lithium ChlorideHCID 4305702Ethyl 2,2,5,5-tetramethyl-1,2,5-azadisilolidin-1-acetateHCID 178418339Butyllithium

生成物 1

HCID 140842721-Methyl-3-(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentyl)-4-phenyl-2-azetidinone収率 96%

試薬・触媒・溶媒 3

HCID 3007855Zincchloride触媒HCID 3283Diethyl Ether溶媒2 回HCID 8058Hexane溶媒

実験手順

10 mmoles of n-butyllithium (6.67 ml of a 1.5 molar solution in hexane) was added to a stirred solution containing diisopropylamine (1.40 ml; 10 mmoles) and 25 ml of diethyl ether at -70° C. This reaction mixture was stirred for 10 min and then 2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane-1-acetic acid ethyl ester (2.45 g; 10 mmoles) was added. The solution was stirred for another 15 min at -70° C. and then 10 mmoles of zinc dichloride (6.76 ml of a 1.48 molar solution in diethylether) was added. After 5 min at -70° C., a white solid (LiCl) began to precipitate. Then N-(benzylidene)methylamine (1.19 g; 10 mmoles) was added. The reaction mixture was stirred for another 15 min at -70° C. and, after being warmed up to room temperature, quenched with 20 ml of a saturated aqueous ammonium chloride solution. The water layer was extracted with diethyl ether. The diethyl ether extract was washed with water, dried with sodium sulfate and concentrated in vacuo to give 3.05 g (96%) of the pure 2-azetidinone product as a pale yellow solid. The 1H NMR spectrum revealed that the product was a mixture of cis and trans isomers (cis/trans ratio 8:92).

後処理

  1. stirringThe solution was stirred for another 15 min at -70° C.
  2. waitAfter 5 min at -70° C.
  3. customto precipitate
  4. stirringThe reaction mixture was stirred for another 15 min at -70° C.
  5. customquenched with 20 ml of a saturated aqueous ammonium chloride solution
  6. extractionThe water layer was extracted with diethyl ether
  7. extractionThe diethyl ether extract
  8. washwas washed with water
  9. dry with materialdried with sodium sulfate
  10. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-23674b60fe894e91a5962cbc60c29121
出典データセット
uspto-grants-1990_02
特許番号
US04898955

関連ノート

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