Trifluoroacetic acid → HCID 131709930, compound

HRID 1580496Notes

Reaction equation

HRID 1580496 reaction equation
C(O[CH2:5][C:6]1[CH2:7][S:8][C@@H:9]2[C@H:16]([NH:17][CH:18]=[O:19])[C:15](=[O:20])[N:10]2[C:11]=1[C:12]([OH:14])=[O:13])(=O)C.C(OCC1C(C(O)=O)N2[C:35](=O)[C@@H:36](NC=O)[C@H:29]2[S:28][CH:27]=1)(=O)C.S1C=CC=C1.FC(F)(F)C(O)=O>>[CH:18]([NH:17][C@@H:16]1[C:15](=[O:20])[N:10]2[CH:11]([C:12]([OH:14])=[O:13])[C:6]([CH2:5][C:27]3[S:28][CH:29]=[CH:36][CH:35]=3)=[CH:7][S:8][C@H:9]12)=[O:19]

Participants

5

Reactant 4

HCID 6422Trifluoroacetic acidHCID 8030ThiopheneHCID 12764266HCID 12764266, compoundHCID 131709931HCID 131709931, compound

Product 1

HCID 131709930HCID 131709930, compound

Procedure

A mixture of 4.6 g of an approximately 1:3-mixture of 3-acetyloxymethyl-7β-formylamino-ceph-3-em-4-carboxylic acid and 3-acetyloxymethyl-7β-formylamino-ceph-2-em-4ξ-carboxylic acid (prepared as described below), 7 ml of thiophene and 28 ml of trifluoroacetic acid is allowed to stand for 20 minutes at room temperature and then evaporated to dryness while repeatedly adding toluene. The semi-crystalline residue is dissolved in hot methyl acetate and the solution diluted with methylene chloride and cyclohexane, whereupon a slightly yellow, coarsely crystalline precipitate forms, which is filtered off and dried, to yield the 7β-formylamino-3-(2-thenyl)-ceph-2-em-4ξ-carboxylic acid, m.p. 164°-166° (decomposition starts at 160°); thinlayer chromatogram (silica gel); Rf = 0.60 (system: n-butanol/acetic acid/water 75:7.5:21), Rf = 0.47 (system: n-butanol/ethanol/water 40:10:50), Rf = 0.66 (system: n-butanol/acetic acid/water 40:10:40) and Rf = 0.55 (system: ethyl acetate/pyridine/acetic acid/water 62:21:6:11); ultraviolet absorption spectrum (in 95% ethanol):λmax = 234 mμ (ε = 13900) and λmax = 216 mμ (ε =10900); infrared absorption spectrum (in mineral oil): characteristic bands at 3,08μ, 3,87μ, 5,68μ, 5,80μ, 6,04μ, 6,52μ 7,07μ, 8,06μ, 8,23μ, 8,53μ, 8,69μ, 9,65μ, 9,74μ, 11,79μ and 14,24μ. A further quantity of the desired product is obtained if the mother liquor is chromatographed on 50 times its weight of silica gel; the 7β-formulamino-3-(2-thenyl)-ceph-2-em-4ξ-carboxylic acid is eluted with a 3:1-mixture of methylene chloride and ethyl acetate.

Workup

  1. additionA mixture of 4.6 g of an approximately 1
  2. customevaporated to dryness while repeatedly adding toluene
  3. dissolutionThe semi-crystalline residue is dissolved in hot methyl acetate
  4. additionthe solution diluted with methylene chloride and cyclohexane
  5. filtrationwhereupon a slightly yellow, coarsely crystalline precipitate forms, which is filtered off
  6. customdried

Sources & evidence

ORD record
ord-38cd635e0b99437bb205d697ea680fbb
Source dataset
uspto-grants-1976_01
Patent number
US03932465

Reaction notes

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