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

HRID 980954Notes

Reaction equation

HRID 980954 reaction equation
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

Participants

11

Reactant 5

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

Product 1

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

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 241BenzeneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

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.

Workup

  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),

Sources & evidence

ORD record
ord-3ba27f16b164407c8ba237c304b9ecef
Source dataset
uspto-grants-1987_01
Patent number
US04639441

Reaction notes

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