Methanol → p-Toluenesulfonic acid

HRID 1759219Notes

Reaction equation

HRID 1759219 reaction equation
O(CC([NH:11][CH:12]1[C:19](=[O:20])[N:18]2[CH:13]1[S:14][CH2:15][N:16]([S:31]([C:34]([F:37])([F:36])[F:35])(=[O:33])=[O:32])[CH:17]2[C:21]([O:23][CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)=[O:22])=O)C1C=CC=CC=1.CN(C)[C:40]1C=[CH:44][CH:43]=[CH:42][CH:41]=1.P(Cl)(Cl)(Cl)(Cl)Cl.C[OH:54].C(O[CH2:58][CH3:59])C>C(Cl)Cl.O>[C:58]1([CH3:59])[CH:44]=[CH:43][C:42]([S:31]([OH:33])(=[O:54])=[O:32])=[CH:41][CH:40]=1.[NH2:11][CH:12]1[C:19](=[O:20])[N:18]2[CH:13]1[S:14][CH2:15][N:16]([S:31]([C:34]([F:35])([F:37])[F:36])(=[O:33])=[O:32])[CH:17]2[C:21]([O:23][CH2:24][C:25]1[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=1)=[O:22]

Participants

9

Reactant 5

HCID 887MethanolHCID 949N,N-DimethylanilineHCID 3283Diethyl EtherHCID 24819Phosphorus pentachlorideHCID 14230826HCID 14230826, compound

Product 2

HCID 6101p-Toluenesulfonic acidHCID 20429062HCID 20429062, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
-55 °C

Procedure

To a solution of benzyl 7-phenoxyacetamido-8-oxo-3-trifluoromethanesulfonyl-5-thia-1,3-diazabicyclo[4,2,0]octane-2-carboxylate (1.50 g.) and N,N-dimethylaniline (0.41 ml.) in methylene chloride (30 ml.) was added phosphorus pentachloride (1.115 g.) at -35° C. under nitrogen atmosphere, and the mixture was stirred at -30° to -25° C. for 2.3 hours. The reaction mixture was cooled to -55° C., and thereto was added methanol (2.4 ml.). This mixture was allowed to warm to 0° C. over a period of 2 hours. Thereto was added water (2.4 ml.), and after stirring at 0° C. for an hour, the reaction mixture was poured into ice-water and extracted twice with ethyl acetate (120 ml. and 50 ml.). The combined extracts were washed with a small amount of water, a dilute aqueous solution of potassium dihydrogenphosphate, a phosphate buffer solution (pH 7, ×2) and an aqueous solution of sodium chloride, successively. After drying over magnesium sulfate and filtration, to the filtrate was added p-toluenesulfonic acid monohydrate (509 mg.) and concentrated to give a crystalline residue, to which diethyl ether was added. The crystals were collected by filtration and washed with diethyl ether to afford p-toluenesulfonic acid salt of benzyl 7-amino-8-oxo-3-trifluoromethanesulfonyl-5-thia-1,3-diazabicyclo[4,2,0]octane-2-carboxylate (1.365 g.), mp 155°-158° C. (dec.).

Workup

  1. temperatureto warm to 0° C. over a period of 2 hours
  2. stirringafter stirring at 0° C. for an hour
  3. extractionextracted twice with ethyl acetate (120 ml. and 50 ml.)
  4. washThe combined extracts were washed with a small amount of water
  5. dry with materialAfter drying over magnesium sulfate and filtration, to the filtrate
  6. additionwas added p-toluenesulfonic acid monohydrate (509 mg.)
  7. concentrationconcentrated
  8. customto give a crystalline residue
  9. filtrationThe crystals were collected by filtration
  10. washwashed with diethyl ether

Sources & evidence

ORD record
ord-52b01e2787a449a09daad9100e4102ea
Source dataset
uspto-grants-1982_07
Patent number
US04339449

Reaction notes

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