Phosphorus pentachloride → cis-3-{2-(2-Chloroacetamido-4-thiazolyl)-2-[1-methyl-1-(2-trimethylsilylethoxycarbonyl)ethoxyimino]acetamido}-4-methoxycarbonyl-2-oxoazetidine

HRID 465264Notes

Reaction equation

HRID 465264 reaction equation
[Cl:1][CH2:2][C:3]([NH:5][C:6]1[S:7][CH:8]=[C:9]([C:11](=[N:15][O:16][C:17]([CH3:28])([C:19]([O:21][CH2:22][CH2:23][Si:24]([CH3:27])([CH3:26])[CH3:25])=[O:20])[CH3:18])[C:12](O)=[O:13])[N:10]=1)=[O:4].P(Cl)(Cl)(Cl)(Cl)Cl.[NH2:35][C@H:36]1[C@@H:39]([C:40]([O:42][CH3:43])=[O:41])[NH:38][C:37]1=[O:44].C(=O)([O-])O.[Na+]>C(Cl)Cl.O1CCCC1.O.C(N(CC)CC)C>[Cl:1][CH2:2][C:3]([NH:5][C:6]1[S:7][CH:8]=[C:9]([C:11](=[N:15][O:16][C:17]([CH3:28])([C:19]([O:21][CH2:22][CH2:23][Si:24]([CH3:25])([CH3:27])[CH3:26])=[O:20])[CH3:18])[C:12]([NH:35][C@H:36]2[C@@H:39]([C:40]([O:42][CH3:43])=[O:41])[NH:38][C:37]2=[O:44])=[O:13])[N:10]=1)=[O:4]

Participants

9

Reactant 4

HCID 24819Phosphorus pentachlorideHCID 516892Sodium BicarbonateHCID 536965212-(2-Chloroacetamido-4-thiazolyl)-2-[1-methyl-1-(2-trimethylsilylethoxycarbonyl)ethoxyimino]acetic acidHCID 53988551cis-3-Amino-4-methoxycarbonyl-2-oxoazetidine

Product 1

HCID 86740483cis-3-{2-(2-Chloroacetamido-4-thiazolyl)-2-[1-methyl-1-(2-trimethylsilylethoxycarbonyl)ethoxyimino]acetamido}-4-methoxycarbonyl-2-oxoazetidine

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Procedure

In 25 ml of methylene chloride is dissolved 820 mg of 2-(2-chloroacetamido-4-thiazolyl)-2-[1-methyl-1-(2-trimethylsilylethoxycarbonyl)ethoxyimino]acetic acid, and under ice-cooling 221 mg of triethylamine and then 380 mg of phosphorus pentachloride are added. The mixture is stirred under ice-cooling for 15 minutes and then at room temperature for 2 hours. The reaction mixture is concentrated under reduced pressure and the residue is dissolved in 5 ml of tetrahydrofuran to prepare a solution containing the acid chloride. On the other hand, 219 mg of cis-3-amino-4-methoxycarbonyl-2-oxoazetidine is dissolved in a mixture of 5 ml of tetrahydrofuran and 10 ml of water, followed by addition of 638 mg of sodium hydrogen carbonate under ice-cooling. To this solution is added dropwise the above acid chloride solution under stirring. The mixture is stirred under ice-cooling for 15 minutes and then at room temperature for one hour and extracted with ethyl acetate. The extract is dried over anhydrous magnesium sulfate and the solvent is distilled off to give cis-3-{2-(2-chloroacetamido-4-thiazolyl)-2-[1-methyl-1-(2-trimethylsilylethoxycarbonyl)ethoxyimino]acetamido}-4- methoxycarbonyl-2-oxoazetidine (syn-isomer).

Workup

  1. temperaturecooling for 15 minutes
  2. concentrationThe reaction mixture is concentrated under reduced pressure
  3. dissolutionthe residue is dissolved in 5 ml of tetrahydrofuran
  4. customto prepare a solution
  5. temperaturecooling
  6. stirringunder stirring
  7. stirringThe mixture is stirred under ice-
  8. temperaturecooling for 15 minutes
  9. waitat room temperature for one hour
  10. extractionextracted with ethyl acetate
  11. dry with materialThe extract is dried over anhydrous magnesium sulfate
  12. distillationthe solvent is distilled off

Sources & evidence

ORD record
ord-ef4aae84ded74ecca092a8d863a3137d
Source dataset
uspto-grants-1985_10
Patent number
US04550105

Reaction notes

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