Pyridine → HCID 131709944, compound

HRID 1580505Notes

Reaction equation

HRID 1580505 reaction equation
[C:1]1([CH:7]([O:14][C:15]([CH:17]2[N:22]3[C:23](=[O:34])[C@@H:24]([C:25](=[O:33])[CH2:26][C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[C@H:21]3[S:20][C:19]([NH2:35])=[C:18]2[CH2:36][C:37]2[S:41][CH:40]=[CH:39][CH:38]=2)=[O:16])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.N1C=CC=CC=1>C(N(CC)CC)C>[C:1]1([CH:7]([O:14][C:15]([C:17]2[N:22]3[C:23](=[O:34])[C@@H:24]([C:25](=[O:33])[CH2:26][C:27]4[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=4)[C@H:21]3[S:20][CH:19]([NH2:35])[C:18]=2[CH2:36][C:37]2[S:41][CH:40]=[CH:39][CH:38]=2)=[O:16])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

4

Reactant 2

HCID 1049PyridineHCID 131709945HCID 131709945, compound

Product 1

HCID 131709944HCID 131709944, compound

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Procedure

A solution of 10.2 g of 7β-phenylacetyl-amino-3-(2-thenyl)-ceph-2-em-4ξ-carboxylic acid diphenylmethyl ester in 130 ml of a 9:1-mixture of pyridine and triethylamine is left to stand in the dark and under nitrogen for 31/2 days at room temperature, then evaporated under reduced pressure. The residue is evaporated several times to dryness with toluene and then triturated with ethyl acetate. The solid residue is recrystallised from ethyl acetate and yields the somewhat impure 7β-phenylacetyl-amino-3-(2-thenyl)-ceph-3-em-4-carboxylic acid diphenylmethyl ester. The mother liquors of trituration and crystallisation are evaporated to dryness and yield on evaporation a mixture of the 7β-phenylacetylamino-3-(2-thenyl)-ceph-2-em-4ξ-carboxylic acid diphenylmethyl ester and the 7β-phenylacetyl-amino-3-(2-thenyl)-ceph-3-em-4-carboxylic acid diphenylmethyl ester which is chromatographed on 160 g of silica gel. Elution is performed with methylene chloride containing 2% of ethyl acetate, fractions of 200 ml (of 100 ml from fraction 9) being taken. Fractions 5-8 yield some impure 7β-phenylacetyl-amino-3-(2-thenyl)-ceph-3-em-4-carboxylic acid diphenylmethyl ester and fractions 9-11 some impure 7β-phenylacetyl-amino-3-(2-thenyl)ceph-2-em-4ξ-carboxylic acid diphenylmethyl ester. The product of fractions 5-8 is crystallised from ethyl acetate and combined with the first crystalline product and chromatographed on 60 g of silica gel. Elution is performed with methylene chloride containing 0.5% of ethyl acetate, fractions of 60 ml being taken. Fractions 7-9 yields the pure 7β-phenylacetyl-amino-3-(2-thenyl)-ceph-3-em-4-carboxylic acid diphenylmethyl ester, which after crystallisation from ethyl acetate melts at 184°C; [α]D20 = -65° ± 1° (c = 0.968 in chloroform): thin-layer chromatogram (silica gel): Rf = 0.46 (system: toluene/ethyl acetate 4:1) and Rf = 0.57 (system: toluene/acetone 9:1); ultraviolet absorption spectrum (in 95% ethanol): λmax = 264μ (ε = 9600); infrared spectrum (in mineral oil); characteristic bands at 2,99μ, 5,59μ, 5,77μ, 5,98μ, 6,10μ and 6,50μ.

Workup

  1. custom2 days
  2. customat room temperature
  3. customevaporated under reduced pressure
  4. customThe residue is evaporated several times to dryness with toluene
  5. customtriturated with ethyl acetate
  6. customThe solid residue is recrystallised from ethyl acetate

Sources & evidence

ORD record
ord-0e38229d1c86444eb713db6610537bd5
Source dataset
uspto-grants-1976_01
Patent number
US03932465

Reaction notes

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