Carbon Disulfide → p-Nitrobenzyl 2-(4-methylthio-2-azetidinon-1-yl)-2-(4-oxo-1,3-dithietan-2-ylidene)acetat

HRID 980954ノート

反応式

HRID 980954 の反応式
C[Si](C)(C)N[Si](C)(C)C.C([Li])CCC.[CH3:15][S:16][CH:17]1[N:20]([CH2:21][C:22]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][C:29]([N+:32]([O-:34])=[O:33])=[CH:28][CH:27]=2)=[O:23])[C:19](=[O:35])[CH2:18]1.[C:36](Cl)(Cl)=[O:37].[C:40](=[S:42])=[S:41]>O1CCCC1.CCCCCC.C1C=CC=CC=1.C(OCC)(=O)C.C(O)(=O)C>[CH3:15][S:16][CH:17]1[N:20]([C:21](=[C:40]2[S:42][C:36](=[O:37])[S:41]2)[C:22]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][C:29]([N+:32]([O-:34])=[O:33])=[CH:28][CH:27]=2)=[O:23])[C:19](=[O:35])[CH2:18]1

参加物

11

反応物 5

HCID 6348Carbon DisulfideHCID 6371PhosgeneHCID 13838HexamethyldisilazaneHCID 20220761p-Nitrobenzyl (4-methylthio-2-azetidinon-1-yl)acetateHCID 178418339Butyllithium

生成物 1

HCID 20220704p-Nitrobenzyl 2-(4-methylthio-2-azetidinon-1-yl)-2-(4-oxo-1,3-dithietan-2-ylidene)acetat

試薬・触媒・溶媒 5

HCID 176Acetic Acid溶媒HCID 241Benzene溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of 740 μl hexamethyldisilazane in 12 ml of tetrahydrofuran was added a solution of butyllithium in hexane (2.4 ml, 163 mmoles/ml) at room temperature, and then the mixture was stirred for 30 minutes. A solution of 620 mg of p-nitrobenzyl 2-(4-methylthio-2-azetidinon-1-yl)acetate in 8 ml of tetrahydrofuran was then added, after cooling the mixture of -78° C., after which it was stirred for 5 minutes. To the resulting solution was added carbon disulphide (181.2 μl), and the mixture was stirred for 20 minutes. A solution of phosgene (198 mg) in benzene (468 μl) was added to the solution, and stirring was continued at -78° C. for 1 hour. Acetic acid (680 μl) was added to the reaction mixture. The resulting mixture was diluted with ethyl acetate, washed successively with water and an aqueous solution of sodium chloride, and dried over anhydrous sodium sulphate. The solvent was distilled off under reduced pressure and the resulting residue was purified by column chromatography (eluent: a 4:1 by volume mixture of benzene and ethyl acetate), to give 703 mg of the desired compound as a foamy substance.

後処理

  1. temperatureafter cooling
  2. additionthe mixture of -78° C.
  3. stirringafter which it was stirred for 5 minutes
  4. stirringthe mixture was stirred for 20 minutes
  5. stirringstirring
  6. waitwas continued at -78° C. for 1 hour
  7. washwashed successively with water
  8. dry with materialan aqueous solution of sodium chloride, and dried over anhydrous sodium sulphate
  9. distillationThe solvent was distilled off under reduced pressure
  10. customthe resulting residue was purified by column chromatography (eluent
  11. additiona 4:1 by volume mixture of benzene and ethyl acetate),

出典と根拠

ORDレコード
ord-3ba27f16b164407c8ba237c304b9ecef
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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