SOME OBSERVATIONS ON THE FRIES REACTION¹

Abstract

hydrochloric and sulfuric acid solutions promoted furfural formation at distillation temperatures, the yield being dependent on the acid concentration, the temperature and on the duration of the distillation. This is a first order reaction.The behavior of mineral acids at distillation temperatures on furfural, arabinose, rhamnose, tetramethylene glycol, ketoxylose, xylonic acid, glycerol and erythritol was investigated. In the last four cases there was little or no reaction. The significance of these results on the mechanism of the pentose-to-furfural reaction has been discussed. Evanston, Illinois

Solvent Extraction of Gallium (III) from Basic Sodium Aluminate Solution by Alkanoyl Oxines

“…Route 1 was followed with the exception that CS2 was used instead of nitrobenzene (16). The intermediary product following AlCb reaction was heated on an oil bath to 85-110°C for 24 hours without the need of refluxing.…”

Synthesis of ethyl 6-substituted-chroman- and -chromone-2-carboxylates. Comparative structure-activity study employing the 6-phenyl and phenoxy analogs in the triton hyperlipidemic rat model

“…Ethyl 6-phenoxychromone-2-carboxylate (10) was prepared from diketo ester 20 (3.3 g, 0.01 mol) according to conditions identical with those employed in the synthesis of 9 from 19 affording 2.0 g (70%) of clear white needles: mp 108-109°; NMR (CDC13) I. 42 (t, 3, J = 7 Hz, ester methyl), 4.54 (q, 2, J = 7 Hz, ester methylene).…”

“…The Et20 extract was dried (MgS04), filtered, and concentrated under reduced pressure. The residue was crystallized from Et20benzene affording 1.8 g (32%) of white plates: mp 177-178°; NMR (Me2CO-de) 3.06 (d, 2, J = 6 Hz, acid methylene), 5.20 (t, 1 ,J = 6 Hz, acid methine), 7.40 (m, 9, aromatic protons), 10,34 2-Hydroxy-5-phenylacetophenone (16). A mixture of acetophenone 38 (3,0 g, 0.01 mol) and preequilibrated 10% Pd/C (0.5 g) in 40 ml of 95% EtOH was hydrogenated at room temperature under 35 psi for 2 hr.…”

“…4'-Acetyl-4-phenylphenol (28). A solution of 4-acetoxybiphenyl (27,10.5 g, 0.05 mol) in dry teirachloroethane (75 ml) was heated at 140°for 2 hr with finely powdered AICI3 (7.5 g, 0.05 mol) in a 250-ml round-bottom flask equipped with a condenser containing a drying tube. After cooling, 50 g of ice and 100 ml of 10% HC1 solution were added and the solvent was removed under reduced Wttiuk el al pressure.…”

“…The residue was recrystallized from AcOEt-petroleum ether to yield 21 g (90%) of white plates: mp 53-54°; NMR (CDCl.i) ó 1.42 ft. 3. J = 7 Hz, ester methyl), 4.44 (q, 2, J = 7 Hz, ester methylene), 6.90-7.70 (m, 8, aromatic protons), 10.44 (broad singlet, 1, phenolic proton); ir (Nujol) 1690 (ester), 3200 cm-1 (phenol). Anal.…”