Dimethyl Sulfide → 2-[4-(p-Toluenesulphonylthio)-3-(alpha-tert.butoxycarbonylamino-alpha-phenylacetylamino)-2-oxoazetidin-1-yl]-3-hydroxy-crotonic acid diphenylmethyl ester

HRID 26107Notes

Reaction equation

HRID 26107 reaction equation
O=[O+][O-].[O:4]=O.[C:6]1([CH:12]([O:19][C:20](=[O:59])[CH:21]([N:25]2[CH:28]([S:29][S:30]([C:33]3[CH:38]=[CH:37][C:36]([CH3:39])=[CH:35][CH:34]=3)(=[O:32])=[O:31])[CH:27]([NH:40][C:41](=[O:57])[CH:42]([NH:49][C:50]([O:52][C:53]([CH3:56])([CH3:55])[CH3:54])=[O:51])[C:43]3[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=3)[C:26]2=[O:58])[C:22](=[CH2:24])C)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.CSC>C(Cl)Cl>[C:6]1([CH:12]([O:19][C:20](=[O:59])/[C:21](/[N:25]2[CH:28]([S:29][S:30]([C:33]3[CH:34]=[CH:35][C:36]([CH3:39])=[CH:37][CH:38]=3)(=[O:31])=[O:32])[CH:27]([NH:40][C:41](=[O:57])[CH:42]([NH:49][C:50]([O:52][C:53]([CH3:55])([CH3:54])[CH3:56])=[O:51])[C:43]3[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=3)[C:26]2=[O:58])=[C:22](\[OH:4])/[CH3:24])[C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

5

Reactant 3

HCID 1068Dimethyl SulfideHCID 570698652-[4-(p-Toluenesulphonylthio)-3-(alpha-tert.butoxycarbonylamino-alpha-phenylacetylamino)-2-oxoazetidin-1-yl]-3-methylene-butyric acid diphenylmethyl esterHCID 131711318Oxygen ozone

Product 1

HCID 705588652-[4-(p-Toluenesulphonylthio)-3-(alpha-tert.butoxycarbonylamino-alpha-phenylacetylamino)-2-oxoazetidin-1-yl]-3-hydroxy-crotonic acid diphenylmethyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

An ozone/oxygen stream (0.5 mmol per minute) is passed for 7 minutes into a solution, cooled to -70° C., of 2.30 g (3.0 mmols) of 2-[4-(p-toluenesulphonylthio)-3-(α-tert.butoxycarbonylamino-α-phenylacetylamino)-2-oxoazetidin-1-yl]-3-methylene-butyric acid diphenylmethyl ester in 230 ml of methylene chloride. After adding 1 ml of dimethyl sulphide, the solution is stirred for a further hour without cooling and is then concentrated by evaporation in vacuo. The residue is recrystallised from methylene chloride/ether/hexane and gives 2-[4-(p-toluenesulphonylthio)-3-(α-tert.butoxycarbonylamino-α-phenylacetylamino)-2-oxoazetidin-1-yl]-3-hydroxy-crotonic acid diphenylmethyl ester of melting point 182°-184° C.; UV spectrum (ethanol): ~max = 259 mμ (ε =13,400); IR spectrum (methylene chloride): characteristic bands at 2.92, 5.59, 5.83, 5.92, 6.03 (shoulder), 6.18 and 6.68 μ; thin layer chromatogram: Rf value~ 0.55 (silica gel; toluene/ethyl acetate, 1:1).

Workup

  1. temperaturewithout cooling
  2. concentrationis then concentrated by evaporation in vacuo
  3. customThe residue is recrystallised from methylene chloride/ether/hexane

Sources & evidence

ORD record
ord-f21bf999d2d54739826d8e3aaf6f0398
Source dataset
uspto-grants-1979_04
Patent number
US04147864

Reaction notes

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