Pyridine → HCID 68134277, compound

HRID 1580513Notes

Reaction equation

HRID 1580513 reaction equation
[CH3:1][O:2][C:3]([C:5]1[O:32][C:8]([CH2:9][C:10]2[CH2:11][S:12][C@@H:13]3[C@H:20]([NH:21]C(=O)CC4C=CC=CC=4)[C:19](=[O:31])[N:14]3[C:15]=2[C:16]([OH:18])=[O:17])=[CH:7][CH:6]=1)=[O:4].N1C=CC=CC=1.C[Si](C)(C)Cl.P(Cl)(Cl)(Cl)(Cl)Cl>C(Cl)Cl.C(N(CC)CC)C.C(O)=O.CO>[NH2:21][C@@H:20]1[C:19](=[O:31])[N:14]2[C:15]([C:16]([OH:18])=[O:17])=[C:10]([CH2:9][C:8]3[O:32][C:5]([C:3]([O:2][CH3:1])=[O:4])=[CH:6][CH:7]=3)[CH2:11][S:12][C@H:13]12

Participants

9

Reactant 4

HCID 1049Pyridine2×HCID 6397ChlorotrimethylsilaneHCID 24819Phosphorus pentachlorideHCID 68134210HCID 68134210, compound

Product 1

HCID 68134277HCID 68134277, compound

Reagents, catalysts & solvents 4

HCID 284Formic AcidSolventHCID 887MethanolSolventHCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent2×

Procedure

A suspension of 0.456 g of 3-(5-methoxycarbonylfurfuryl)-7β-phenylacetylamino-ceph- 3-em-4-carboxylic acid in 30 ml of absolute methylene chloride is stirred for 30 minutes at 30° with 0.89 ml of absolute pyridine and 1.5 ml of trimethylchlorosilane. The resulting clear yellow solution is treated with 1.08 ml of pyridine and cooled to below -20°, then 8.9 ml of an 8% phosphorous pentachloride solution in methylene chloride is added dropwise and the solution is stirred for 40 minutes at a temperature of -12°. The brown solution is cooled again to below -20° and treated with 12.1 ml of absolute methanol. The mixture is allowed to react for 30 minutes at room temperature, whereupon the solution largely loses its colour. Upon addition of 2.5 ml of 25% aqueous formic acid, the pH of the solution is adjusted to 2.0 with 2.6 ml of triethylamine. The resulting suspension is further stirred for 30 minutes at room temperature. The pH is raised to 3.5 by the further addition of 9.6 ml of triethylamine. The suspension is left to stand for 1 hour at 0°; the fine, rather stimy precipitate is filtered off, washed with methanol, methylene chloride and diethyl ether and dried under a high vacuum. The 7β-amino-3-(5-methoxycarbonyl-furfuryl)-ceph-3-em-4-carboxylic acid is obtained in the form of a yellowish, microcrystalline powder. Additional, somewhat less pure material can be isolated by digesting the evaporated mother liquors and rinsing liquors with methylene chloride; ultraviolet absorption spectrum (in 0.1 N aqueous sodium hydrogen carbonate solution): λmax = 270 mμ (ε = 21400) and λmin = 234 mμ (ε = 8200); infrared absorption spectrum (in mineral oil): characteristic bands at 3,13μ, 3,83μ, 4,24μ, 5,54μ, 5,77μ, 6,17μ, 6,54μ, 6,58μ, (shoulder), 7.08μ, 7,39μ, 7,63μ, 7,72μ, 8,38μ, 8,84μ, 9,49μ, 9,78μ, 10,12μ, 12,62μ and 13,21μ.

Workup

  1. temperaturecooled to below -20°
  2. temperatureThe brown solution is cooled again to below -20°
  3. customto react for 30 minutes at room temperature, whereupon the solution
  4. stirringThe resulting suspension is further stirred for 30 minutes at room temperature
  5. waitThe suspension is left
  6. waitto stand for 1 hour at 0°
  7. filtrationthe fine, rather stimy precipitate is filtered off
  8. washwashed with methanol, methylene chloride and diethyl ether
  9. customdried under a high vacuum

Sources & evidence

ORD record
ord-a282a54a79da41668e63d7cb1137947d
Source dataset
uspto-grants-1976_01
Patent number
US03932465

Reaction notes

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