Pyridine → HCID 70561141, compound

HRID 1413131Notes

Reaction equation

HRID 1413131 reaction equation
N1C=CC=CC=1.P(Cl)(Cl)(Cl)(Cl)Cl.[CH3:13][O:14][C:15]([CH2:17][C:18]1[CH2:19][S:20][C@@H:21]2[C@H:41]([NH:42]C(=O)COC3C=CC=CC=3)[C:40](=[O:53])[N:22]2[C:23]=1[C:24]([O:26][CH:27]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:25])=[O:16].P([O-])(O)(O)=O.[K+]>C(Cl)Cl.CO>[CH3:13][O:14][C:15]([CH2:17][C:18]1[CH2:19][S:20][C@@H:21]2[C@H:41]([NH2:42])[C:40](=[O:53])[N:22]2[C:23]=1[C:24]([O:26][CH:27]([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)=[O:25])=[O:16]

Participants

7

Reactant 4

HCID 1049PyridineHCID 24819Phosphorus pentachlorideHCID 516951Monobasic potassium phosphateHCID 70560519HCID 70560519, compound

Product 1

HCID 70561141HCID 70561141, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

4.4 ml of pyridine and 44 ml of an 8% strength suspension of phosphorus pentachloride in methylene chloride are added to a solution, which has been cooled to -17°, of 3.10 g (5.42 mmols) of diphenylmethyl 3-methoxycarbonylmethyl-7β-phenoxyacetylamino-3-cephem-4-carboxylate in 110 ml of methylene chloride and the mixture is then stirred for 3 hours in an ice bath. After cooling to -30°, 27 ml of absolute methanol are added and the residue mixture is stirred for 1 hour at -10°, for 1 hour at 0° and for 1 hour at room temperature. The pH is adjusted to 2.5 by adding a 0.5 M solution of potassium dihydrogen phosphate, the mixture is stirred for a further 0.5 hour and, for working up, the organic phase is separated off, the aqueous phase is subsequently extracted with twice 50 ml of methylene chloride and the combined methylene chloride phases are extracted by shaking with a saturated solution of sodium chloride, dried over sodium sulphate and evaporated. Chromatography of the crude product over 100 g of silica gel and elution with toluene and 20-30% of ethyl acetate gives amorphous diphenylmethyl 3-methoxycarbonylmethyl-7β-amino-3-cephem-4-carboxylate, which according to thin layer chromatography is a single compound and which is characterised in the form of the crystalline toluenesulphonate; melting point 157°- 158° (decomposition); Rf 0.45 (on silica gel, with ethyl acetate); UV spectrum (in ethanol): λmax =257 nm; IR spectrum (in Nujol): bands at 2.87, 5.57, 5.72, 5.79 and 6.12μ.

Workup

  1. additionare added to a solution, which
  2. temperatureAfter cooling to -30°
  3. stirringthe residue mixture is stirred for 1 hour at -10°, for 1 hour at 0° and for 1 hour at room temperature
  4. stirringthe mixture is stirred for a further 0.5 hour
  5. customthe organic phase is separated off
  6. extractionthe aqueous phase is subsequently extracted with twice 50 ml of methylene chloride
  7. extractionthe combined methylene chloride phases are extracted
  8. stirringby shaking with a saturated solution of sodium chloride
  9. dry with materialdried over sodium sulphate
  10. customevaporated
  11. washChromatography of the crude product over 100 g of silica gel and elution with toluene and 20-30% of ethyl acetate

Sources & evidence

ORD record
ord-21691c3701d1457d80f4e871b5dbd280
Source dataset
uspto-grants-1981_02
Patent number
US04248868

Reaction notes

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