3-Chloro-2,2-dimethylpropanoyl chloride → p-Nitrobenzyl 2-(4-tert-butylthio-2-oxo-1-azetidinyl)-5-chloro-4,4-dimethyl-3-oxopentanoate

HRID 2371895ノート

反応式

HRID 2371895 の反応式
C[Si]([NH-])(C)C.C[Si]([NH-])(C)C.[Li+].[Li+].[C:13]([S:17][CH:18]1[N:21]([CH2:22][C:23]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=2)=[O:24])[C:20](=[O:36])[CH2:19]1)([CH3:16])([CH3:15])[CH3:14].[Cl:37][CH2:38][C:39]([CH3:44])([CH3:43])[C:40](Cl)=[O:41]>C1COCC1.C1(C)C=CC=CC=1.Cl.[Na+].[Cl-]>[C:13]([S:17][CH:18]1[N:21]([CH:22]([C:40](=[O:41])[C:39]([CH3:44])([CH3:43])[CH2:38][Cl:37])[C:23]([O:25][CH2:26][C:27]2[CH:28]=[CH:29][C:30]([N+:33]([O-:35])=[O:34])=[CH:31][CH:32]=2)=[O:24])[C:20](=[O:36])[CH2:19]1)([CH3:16])([CH3:14])[CH3:15]

参加物

8

反応物 3

HCID 613453-Chloro-2,2-dimethylpropanoyl chlorideHCID 14460289p-Nitrobenzyl (4-tert-butylthio-2-oxo-1-azetidinyl)acetateHCID 86588160Lithim bis(trimethylsilylamide)

生成物 1

HCID 14460305p-Nitrobenzyl 2-(4-tert-butylthio-2-oxo-1-azetidinyl)-5-chloro-4,4-dimethyl-3-oxopentanoate収率 69.4%

試薬・触媒・溶媒 4

HCID 313Hydrochloric Acid溶媒HCID 1140Toluene溶媒HCID 5234Sodium Chloride溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-70 °C

実験手順

6 ml of a 1M solution of lithium bis(trimethylsilylamide) in THF is slowly added dropwise to a stirred mixture, at 70° C., of 1.06 g (3 mmol) of p-nitrobenzyl 2-(4-tertbutylthio-2-oxo-1-azetidinyl)acetate and 410 μl (3.17 mmol) of chloropivaloyl chloride in 38 ml of absolute tetrahydrofuran, and the mixture is stirred for a further 30 minutes at -70° C. The reaction mixture is diluted with 250 ml of toluene, and 10 ml of 2N aqueous HCl and 100 ml of saturated NaCl solution are added. After separation, the organic phase is again washed with 100 ml of saturated NaCl solution then dried over MgSO4, and filtered, and the solvent is removed in vacuo on a rotary evaporator. The non-crystalline residue is chromatographed over 46 g of silica gel using toluene:ethyl acetate (19:1), to give 980 mg of non-crystalline title compound. IR in CH2Cl2 : 2930, 1770, 1760, 1725, 1615, 1530, 1465, 1370, 1250, 1215, 1190, 1110, 1040, 1000, 847 cm-1.

後処理

  1. additionare added
  2. customAfter separation
  3. washthe organic phase is again washed with 100 ml of saturated NaCl solution
  4. dry with materialthen dried over MgSO4
  5. filtrationfiltered
  6. customthe solvent is removed in vacuo on a rotary evaporator
  7. customThe non-crystalline residue is chromatographed over 46 g of silica gel

出典と根拠

ORDレコード
ord-279b1b53757941a48299cb50d5acb403
出典データセット
uspto-grants-1992_03
特許番号
US05096899

反応ノート

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