Carbon Disulfide → (3S, 4R)3-[(R)-1-t-Butyldimethylsilyloxyethyl]-4-[1-methyl-2-p-nitrobenzyloxycarbonylaminoethylthio(thiocarbonyl)]thioazetidin-2-one

HRID 1075218Notes

Reaction equation

HRID 1075218 reaction equation
[CH3:1][CH:2]([SH:18])[CH2:3][NH:4][C:5]([O:7][CH2:8][C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][CH:10]=1)=[O:6].[Na].[C:20](=[S:22])=[S:21].C(O[C@H:27]1[NH:30][C:29](=[O:31])[C@@H:28]1[C@H:32]([O:34][Si:35]([C:38]([CH3:41])([CH3:40])[CH3:39])([CH3:37])[CH3:36])[CH3:33])(=O)C>CO.C(OCC)(=O)C.C(O)(=O)C>[Si:35]([O:34][C@@H:32]([C@@H:28]1[C@@H:27]([S:21][C:20]([S:18][CH:2]([CH3:1])[CH2:3][NH:4][C:5]([O:7][CH2:8][C:9]2[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][CH:10]=2)=[O:6])=[S:22])[NH:30][C:29]1=[O:31])[CH3:33])([C:38]([CH3:41])([CH3:39])[CH3:40])([CH3:37])[CH3:36]

Participants

8

Reactant 4

HCID 6348Carbon DisulfideHCID 5360545SodiumHCID 10935078AzetidonHCID 13175758N-(p-nitrobenzyloxycarbonyl)-1-amino-2-propanethiol

Product 1

HCID 13175762(3S, 4R)3-[(R)-1-t-Butyldimethylsilyloxyethyl]-4-[1-methyl-2-p-nitrobenzyloxycarbonylaminoethylthio(thiocarbonyl)]thioazetidin-2-oneYield 77%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

168 mg (0.59 mmole) of 1-methyl-2-(p-nitrobenzyloxycarbonylamino)ethanethiol were added to a solution of 12.5 mg (0.57 mmole) of metallic sodium in 4 ml of methanol at -10° C., and then the mixture was stirred for 5 minutes. 45 mg (0.59 mmole) of carbon disulphide were added to the resulting solution at the same temperature, followed by stirring for 10 minutes. Then 154 mg (0.54 mmole) of (3R, 4R)-4-acetoxy-3-[(R)-1-t-butyldimethylsilyloxyethyl]azetidin-2-one were added to the solution at the same temperature. The bath temperature was slowly elevated to 0° C. over a period of about 1 hour. After completion of the reaction, the reaction solution was made slightly acidic by the addition of a drop of acetic acid, diluted with ethyl acetate, washed with a saturated aqueous solution of sodium chloride and dried. After evaporation of the solvent, the resulting residue was subjected to column chromatography through 10 g of silica gel eluted with a 10-15% v/v solution of ethyl acetate in benzene, to give 237 mg (yield 77%) of the desired product as a yellow oil.

Workup

  1. stirringby stirring for 10 minutes
  2. waitThe bath temperature was slowly elevated to 0° C. over a period of about 1 hour
  3. customAfter completion of the reaction
  4. washwashed with a saturated aqueous solution of sodium chloride
  5. customdried
  6. customAfter evaporation of the solvent
  7. washeluted with a 10-15% v/v solution of ethyl acetate in benzene

Sources & evidence

ORD record
ord-0d3ea99e4f8c4a0a9220d2e8d5a59a77
Source dataset
uspto-grants-1983_07
Patent number
US04395418

Reaction notes

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