Trifluoroacetic acid → HCID 70528331, compound

HRID 329238Notes

Reaction equation

HRID 329238 reaction equation
[OH:1][CH:2]([C:19]1[S:20][CH:21]=[CH:22][CH:23]=1)[C:3]([NH:5][CH:6]1[C:17](=[O:18])[N:8]2[C:9]([C:14]([O-:16])=[O:15])=[C:10]([CH3:13])[CH2:11][S:12][C@H:7]12)=[O:4].FC(F)(F)C(O)=O>C1(OC)C=CC=CC=1>[OH:1][CH:2]([C:19]1[S:20][CH:21]=[CH:22][CH:23]=1)[C:3]([NH:5][CH:6]1[C:17](=[O:18])[N:8]2[C:9]([C:14]([OH:16])=[O:15])=[C:10]([CH3:13])[CH2:11][S:12][C@H:7]12)=[O:4]

Participants

4

Reactant 2

HCID 6422Trifluoroacetic acidHCID 131710426HCID 131710426, compound

Product 1

HCID 70528331HCID 70528331, compoundYield 91%

Reagents, catalysts & solvents 1

HCID 7519AnisoleSolvent

Procedure

Diphenylmethyl (6R,7R,2'R and S)-7-(2' -hydroxy-2'-[thien-2-yl]-acetamido)-3-methylceph-3-em-4-carboxylate (543mg, 1.05mmole) was dissolved in anisole (4ml) and stirred with trifluoroacetic acid (4 ml) at +20 to +25° for 7 mins. The anisole and trifluoroacetic acid were evaporated and the residue partitioned between 3%-aqueous sodium bicarbonate solution (ca 50ml) and ethyl acetate (ca 50ml). The aqueous layer was washed with ethyl acetate (3×ca 50ml), layered with ethyl acetate and adjusted to pH 2.5. The ethyl layer was combined with the ethyl acetate backwash of the aqueous layer, dried, and evaporated to give (6R,7R,2'R and S)-7-(2' -hydroxy-2'-[thien-2-yl]-acetamido)-3-methylceph-3-em-4-carboxylic acid as a foam (337mg, 91%). This foam was dissolved in acetone (3ml) and stirred with a solution of sodium 2-ethylhexanoate (186mg, 1.05 mmole) in acetone (2ml) and ether (2ml). The precipitated material was filtered off, washed with ether, and dried to give the title compound containing 2mole-equivalents of water (i.r., microanalysis and 1/6 mole-equivalents of ether (n.m.r., microanalysis) as a pale-brown solid (183mg, 0.486 mmole, 46.4%); λmax (pH6-buffer) 237.5nm, inflexion at 255nm (ε12,640 and 9,250 respectively); νmax (nujol) 3380 (NH,H2O), 1760 (azetidin-2-one), 1680 and 1528 (CONH), and 1600 cm-1 (CO2 -); τ (Me2SO-D6) 1.48 and 1.63 (total 1H, 2d,J9Hz,NH), 2.54 to 3.10 (3H, m, thiophene protons), 4.46 (ca 1H, m, C7 -H), 4.60 and 4.62 (total ca 1H, 2S, CHOH), 5.00 (1H,d,J4.5Hz, C7 -H), 6.49 and 6.87 (2H, ABq, J18Hz, C2 -H2), 8.01 (3H,s, C3 -CH3). A signal at τ 8.89 revealed the presence of 1/6 mole-equivalent of diethyl ether. (Found: C,41.1, 41.4; H,3.6, 3.8;N,6.6, 7.0; S,14.5. C14H13N2NaO5S2. 1/6 C2H5OC2H5. 2H2O (424.7) requires C,41.5; H,4.4; N,6.5; S,15.1%).

Workup

  1. customThe anisole and trifluoroacetic acid were evaporated
  2. customthe residue partitioned between 3%-aqueous sodium bicarbonate solution (ca 50ml) and ethyl acetate (ca 50ml)
  3. washThe aqueous layer was washed with ethyl acetate (3×ca 50ml)
  4. customdried
  5. customevaporated

Sources & evidence

ORD record
ord-e58b61ca225547c2885eed803746d6bd
Source dataset
uspto-grants-1977_04
Patent number
US04020077

Reaction notes

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