Carbon Disulfide → Methyl 2-(4-hydroxy-4-methyl-1,3-dithiolan-2-ylidene)-2-(4-methylthio-2-azetidinon-1-yl)acetate

HRID 980965ノート

反応式

HRID 980965 の反応式
C([Li])CCC.C[Si](C)(C)N[Si](C)(C)C.[CH3:15][O:16][C:17](=[O:26])[CH2:18][N:19]1[CH:22]([S:23][CH3:24])[CH2:21][C:20]1=[O:25].Br[CH2:28][C:29](=[O:31])[CH3:30].[C:32](=[S:34])=[S:33]>CCCCCC.O1CCCC1.C(O)(=O)C.C(OCC)(=O)C>[OH:31][C:29]1([CH3:30])[CH2:28][S:34][C:32](=[C:18]([N:19]2[CH:22]([S:23][CH3:24])[CH2:21][C:20]2=[O:25])[C:17]([O:16][CH3:15])=[O:26])[S:33]1

参加物

10

反応物 5

HCID 6348Carbon DisulfideHCID 11715BromoacetoneHCID 13838HexamethyldisilazaneHCID 13556624Methyl (4-methylthio-2-oxoazetidin-1-yl)acetateHCID 178418339Butyllithium

生成物 1

HCID 86741251Methyl 2-(4-hydroxy-4-methyl-1,3-dithiolan-2-ylidene)-2-(4-methylthio-2-azetidinon-1-yl)acetate

試薬・触媒・溶媒 4

HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒3 回HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-78 °C

実験手順

A solution of butyllithium in hexane (1.35 ml, 1.63 mmoles/ml) was added to a solution of hexamethyldisilazane (387 μl) in tetrahydrofuran (5 ml) at room temperature, and the mixture was stirred for 30 minutes. The solution was cooled to -78° C. and a solution of methyl(4-methylthio-2-azetidinon-1-yl)acetate (189 mg) in tetrahydrofuran (3 ml) was added thereto, after which the mixture was stirred for 10 minutes. Carbon disulphide (84 μl) was added to the solution and the mixture was stirred for 1 hour. A solution of bromoacetone (153 mg) in tetrahydrofuran (2 ml) was added to the resulting mixture, which was then stirred at -78° C. for 2 hours. The reaction mixture was then diluted with acetic acid (100 μl) and ethyl acetate, washed successively with an aqueous solution of sodium chloride, an aqueous solution of sodium bicarbonate and again an aqueous solution of sodium chloride, after which it was dried over anhydrous sodium sulphate. The solvent was distilled off under reduced pressure and the resulting residue was purified by preparative thin layer chromatography (eluent: a 2:1 by volume mixture of benzene and ethyl acetate), to give 290 mg of the desired product as a foamy substance.

後処理

  1. stirringafter which the mixture was stirred for 10 minutes
  2. stirringthe mixture was stirred for 1 hour
  3. stirringwas then stirred at -78° C. for 2 hours
  4. washwashed successively with an aqueous solution of sodium chloride
  5. dry with materialan aqueous solution of sodium bicarbonate and again an aqueous solution of sodium chloride, after which it was dried over anhydrous sodium sulphate
  6. distillationThe solvent was distilled off under reduced pressure
  7. customthe resulting residue was purified by preparative thin layer chromatography (eluent
  8. additiona 2:1 by volume mixture of benzene and ethyl acetate),

出典と根拠

ORDレコード
ord-5c3479e8ab5d48148e3a06db83e01c3b
出典データセット
uspto-grants-1987_01
特許番号
US04639441

反応ノート

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