Phosphoric Acid → HCID 86734926, compound

HRID 258779Notes

Reaction equation

HRID 258779 reaction equation
C(O[CH2:5][C:6]1[CH2:13][S:12][CH:11]2[N:8]([C:9](=[O:24])[CH:10]2[NH:14][C:15](=[O:23])[CH2:16][C:17]2[S:18][C:19](=[O:22])[S:20][CH:21]=2)[C:7]=1[C:25]([OH:27])=[O:26])(=O)C.C(=O)(O)[O-].[Na+].[S-][C:34]#[N:35].[K+].P(=O)(O)(O)O>O.C(C(C)=O)C(C)C.N1C=CC=CC=1>[C:25]([C:7]1[N:8]2[CH:11]([S:12][CH2:13][C:6]=1[CH2:5][N+:35]1[CH:34]=[CH:25][CH:7]=[CH:6][CH:5]=1)[CH:10]([NH:14][C:15](=[O:23])[CH2:16][C:17]1[S:18][C:19](=[O:22])[S:20][CH:21]=1)[C:9]2=[O:24])([O-:27])=[O:26]

Participants

8

Reactant 4

HCID 1004Phosphoric AcidHCID 516872Potassium thiocyanateHCID 516892Sodium BicarbonateHCID 21426457HCID 21426457, compound

Product 1

HCID 86734926HCID 86734926, compoundYield 101.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent3×HCID 1049PyridineSolventHCID 7909Methyl Isobutyl KetoneSolvent

Conditions

Temperature
60 °C

Procedure

Water (50 cc.) and pyridine (8.3 cc.) are added to 3-acetoxymethyl-2-carboxy-8-oxo-7-[(1,3-dithiol-2-on-4-yl)-acetamido]-5-thia-1-aza-bicyclo[4.2.0]-oct-2-ene (22 g.), sodium bicarbonate (4.35 g.) and potassium thiocyanate (99.5 g.). After stirring, a syrupy homogeneous medium is obtained, the pH of which is adjusted to 6.5 by adding concentrated phosphoric acid. The mixture is heated to 60° C. for 5 hours. After cooling, it is diluted with distilled water (350 cc.) and washed three times with chloroform (a total of 300 cc.). The last traces of chloroform are removed from the aqueous phase under reduced pressure (20 mm Hg), and this phase is then treated with decolourising charcoal, filtered over "Supercel" and cooled with an ice-water bath. It is acidified to pH= 2 by adding 4 N hydrochloric acid whilst maintaining the temperature below 5° C. After precipitation, the mixture is stirred for 1 hour whilst continuing to cool it with an ice-water bath, and is then washed twice by decanting, using iced water (one liter). The precipitate is isolated by filtration and washed three times with iced water (a total of 300 cc.). The moist solid obtained is suspended in water (100 cc.) and a 25% solution of Amberlite LA 2 in methyl isobutyl ketone (100 cc.) is added. The mixture is stirred until the solid has completely dissolved and the organic phase is then decanted and discarded. The aqueous phase is extracted twice with a 25% Amberlite LA 2 solution in methylisobutyl ketone (a total of 150 cc.), then with ethyl acetate (100 cc.) and finally 3 times with ethyl ether (a total of 300 cc.). The water is evaporated under reduced pressure (20 mm Hg) at 40° C. An oil is obtained which, when triturated in acetone (150 cc.), gives a white solid which is filtered off. The compound obtained is washed three times with acetone (a total of 150 cc.) and then dried under reduced pressure (0.5 mm Hg) to give 2-carboxylato-8-oxo-7-[(1,3-dithiol-2-on-4-yl)-acetamido]-3-(1-pyridinio-methyl)-5-thia-1-aza-bicyclo[4.2.0]oct-2-ene (11.7 g.).

Workup

  1. customa syrupy homogeneous medium is obtained
  2. temperatureAfter cooling
  3. washwashed three times with chloroform (a total of 300 cc
  4. customThe last traces of chloroform are removed from the aqueous phase under reduced pressure (20 mm Hg)
  5. additionthis phase is then treated with decolourising charcoal
  6. filtrationfiltered over "Supercel"
  7. temperaturecooled with an ice-water bath
  8. additionby adding 4 N hydrochloric acid
  9. temperaturewhilst maintaining the temperature below 5° C
  10. customAfter precipitation
  11. stirringthe mixture is stirred for 1 hour
  12. temperatureto cool it with an ice-water bath
  13. washis then washed twice
  14. customby decanting
  15. customThe precipitate is isolated by filtration
  16. washwashed three times with iced water (a total of 300 cc
  17. customThe moist solid obtained
  18. stirringThe mixture is stirred until the solid
  19. dissolutionhas completely dissolved
  20. customthe organic phase is then decanted
  21. extractionThe aqueous phase is extracted twice with a 25% Amberlite LA 2 solution in methylisobutyl ketone (a total of 150 cc
  22. customThe water is evaporated under reduced pressure (20 mm Hg) at 40° C
  23. customAn oil is obtained which, when
  24. customtriturated in acetone (150 cc.)
  25. customgives a white solid which
  26. filtrationis filtered off
  27. customThe compound obtained
  28. washis washed three times with acetone (a total of 150 cc
  29. custom) and then dried under reduced pressure (0.5 mm Hg)

Sources & evidence

ORD record
ord-d307b251489b47f2a4cdbe9d0553ff58
Source dataset
uspto-grants-1977_07
Patent number
US04034090

Reaction notes

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