Oxygen → p-Toluenesulfonate

HRID 1632876Notes

Reaction equation

HRID 1632876 reaction equation
O=O.[O:3]=[O+][O-].[CH3:6][C:7]1[CH:12]=[CH:11][C:10]([S:13]([O-:16])(=[O:15])=[O:14])=[CH:9][CH:8]=1.[C:17]1([CH:23]([O:30][C:31]([C@@H:33]2[N:38]3[C:39](=[O:42])[C@@H:40]([NH2:41])[C@H:37]3[S:36][CH2:35][C:34]2=C)=[O:32])[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.CSC>CO>[CH3:6][C:7]1[CH:8]=[CH:9][C:10]([S:13]([O-:16])(=[O:15])=[O:14])=[CH:11][CH:12]=1.[C:24]1([CH:23]([O:30][C:31]([C@@H:33]2[N:38]3[C:39](=[O:42])[C@@H:40]([NH2:41])[C@H:37]3[S:36][CH2:35][C:34]2=[O:3])=[O:32])[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1

Participants

8

Reactant 5

HCID 977OxygenHCID 1068Dimethyl SulfideHCID 24823Ozone2×HCID 85570p-ToluenesulfonateHCID 13055583HCID 13055583, compound

Product 2

HCID 85570p-ToluenesulfonateHCID 131710694HCID 131710694, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
-12 °C

Procedure

A stream of oxygen and ozone (containing 0.35 mmol) of ozone per minute) is passed for 4 minutes through a solution, cooled to -60° C., of 0.553 g of the 4-methylphenylsulphonate of 7β-amino-3-methylene-cepham-4α-carboxylic acid diphenylmethyl ester in 50 ml of methanol. After a further 5 minutes, the pale blue-coloured solution is treated with 0.3 ml of dimethyl sulphide. The mixture is stirred for 15 minutes at -70° C., for one hour at -12° C. and for one hour in an ice bath and is then evaporated. The residue is taken up in a small amount of methylene chloride, diethyl ether is then added until the mixture turns cloudy, and the mixture is left to stand. The microcrystalline, reddish-coloured pulverulent precipitate is filtered off and yields the 4-methylphenylsulphonate of 7β-amino-cepham-3-one-4α-carboxylic acid diphenylmethyl ester which is mainly present in the enol form as the 4-methylphenylsulphonate of 7β-amino-3-cephem-3-ol-4-carboxylic acid diphenylmethyl ester, melting point=143°-145° C. (with decomposition); thin layer chromatogram (silica gel) Rf~0.28 (system: ethyl acetate/pyridine/water, 85:10:5); ultraviolet absorption spectrum (in ethanol): λmax =262 mμ (ε=3,050) and 282 mμ (ε=3,020); infrared absorption spectrum (in methylene chloride): characteristic bands at 5.58μ, 5.77μ (shoulder), 6.02μ and 6.22μ.

Workup

  1. customis then evaporated
  2. additionis then added until the mixture
  3. waitthe mixture is left
  4. filtrationThe microcrystalline, reddish-coloured pulverulent precipitate is filtered off

Sources & evidence

ORD record
ord-9adad79b59a943ef9c4df73a72436571
Source dataset
uspto-grants-1984_10
Patent number
US04477658

Reaction notes

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