Pyridine → HCID 53640968, compound

Participants

Reaction Steps

Titanium tetrachloride (28.8 mL, 1.0 M in CH2Cl2) is added dropwise to a stirred solution of pyridine (12.0 mL) in CH2Cl2 (100 mL) at 0° C. The resulting suspension is added to a solution of methyl anthranilate (6.8 g, 45.4 mmol) and 2,6-bis(1,1-dimethylethyl)-p-benzoquinone (10.0 g, 45.4 mol) in dry THF (200 mL). The reaction mixture is warmed to reflux under an argon atmosphere for four hours. At this time, another TiCl4 /pyridine suspension (prepared as above) is added. The reaction mixture is warmed at reflux for an additional 12 hours. It is cooled and filtered through Celite to remove the suspended solid. The solid is washed with ethyl acetate (100 mL) and the combined filtrates are evaporated. The residue is taken up in 200 mL of THF and stirred vigorously with a solution of sodium dithionite (100 g) in water (100 mL) for 30 minutes. The layers are separated and the aqueous layer is extracted with ethyl acetate (3×100 mL). The organic layers are combined, washed with brine (2×100 mL), dried over magnesium sulfate, and evaporated to give 2-[[(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)]amino]benzoic acid methyl ester; mp 155°-158° C.

Provenance & Evidence