Triphenylphosphine → HCID 178502812, compound

Participants

Reaction Steps

340 mg (0.446 mmol) of p-methoxybenzyl 7β-[2-(2-tritylaminothiazol-4-yl) -(Z)-2-methoxyiminoacetamido]-3-hydroxy-3-cephem-4-carboxylate and 146 mg (0.557 mmol) of triphenylphosphine were dissolved in 7 ml of tetrahydrofuran, and a solution of tetrahydrofuran (3.5 ml) of 170 mg (0.446 mmol) of 4,5-bis(4-methoxybenzyloxy)-2-hydroxymethylpyridine was added thereto at -20° C. under nitrogen atmosphere. Then, a solution of 0.087 ml (0.55 mmol) of diethylazodicarboxylate in 3.5 ml of tetrahydrofuran was dropwise added to the solution at -20° C., and the mixture was stirred for 1 hour at the same temperature. 30 ml of ethylacetate was added thereto. The solution was washed sequentially with water, a 1N hydrochloric acid aqueous solution, a saturated sodium hydrogencarbonate aqueous solution and a saturated sodium chloride aqueous solution and dried over magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (Wakogel C-300, elution with 1-2% methanol-chloroform) to obtain 325 mg (yield: 64.8%) of p-methoxybenzyl 7β-[2-(2-tritylaminothiazol-4-yl)-(Z) -2-methoxyiminoacetamido]-[3,4-bis(4-methoxybenzyloxy) -6-pyridylmethoxy]-3-cephem-4-carboxylate as a powder. 325 mg (0.289 mmol) of this powder was dissolved in 28 ml of methylene chloride, and a solution of 0.067 ml (0.592 mmol) of methyltrilrate in 2 ml of methylene chloride was dropwise added thereto at -20° C. under nitrogen atmosphere. The mixture was stirred for 1 hour at room temperature. The solvent was distilled off, and the residue was triturated to obtain 355 mg (yield: 95.2%) of p-methoxybenzyl 7β-[2-(2-tritylaminothiazol-4-yl) -(Z)-2-methoxyiminoacetamido]-[3,4-bis(4-methoxybenzyloxy) -1-methyl-6-pyridiniomethoxy]-3-cephem-4-carboxylate trifluoromethanesulfonate as a powder. 355 mg (0.275 mmol) of this powder was dissolved in 429 mg (2.79 mmol) of 3-methyl-4-methylthiophenol, 2 ml of methylene chloride and 0.34 ml (2.5 mmol) of thioanisole, and 2 ml of trifluoroacetic acid was added thereto under cooling with ice. The mixture was stirred for 1 hour at room temperature. The solvent was distilled off, and ethyl ether was added to the residue to obtain the trifluoroacetate of the above-identified compound as a powder. This powder was dissolved in water and insolubles were filtered off. The filtrate was purified by reversed phase column chromatography (Chemco LC-SORB, SP-β-ODS, elution with 30% methanol aqueous solution) and freeze-dried to obtain 28.1 mg (yield: 19%) of the above-identified compound.

Provenance & Evidence