Walter T. Smith

The pyrolytic behavior of ethylenetetracarboxylic acid

Abstract The controlled pyrolysis of ethylenetetracarboxyclic acid at 220°C followed by methylation of the pyrolyzate results in the formation of methyl propiolate as the major product along with lesser amounts of methyl fumarate. Evidence is presented which indicates that the methyl fumarate probably arises from some precursor in the pyrolyzate during the methylation reaction. Extended heating of the tetra acid at its melting point produces, in addition to the substances cited above, ethylenetetracarboxylic dianhydride and dicarboxymaleic anhydride. The high-temperature (300–400°C) pyrolysis of the tetraacid gives l0–20% yields of dimethylmaleic anhydride.

Substituent effects in 2-pyridone-catalyzed mutarotation

Abstract Since 2-pysidone may be considered as a model of an active center of an enzyme, a series of substituted 2-pyridones has been used as catalysts for the mutarotation of 2,3,4,6-tetramethyl-α- d -glucose. The effect of position of the substituent on the rate has been studied by using 3-, 4-, 5-, and 6-methyl-2-pyridones. The effect of varying the electron density at a specific atom of 2-pyridone was studied by using 5-chloro-, 5-methyl-, and 5-nitro-2-pyridones. A methyl group in the 4 or 5 position enhances the catalysis; a 3-methyl group slows the rate; and a 6-methyl group has little net effect. A comparison of different substituents in the 5 position on the velocity of mutarotation gives the following order: methyl > hydrogen > chloro > nitro.

Use of 3,5-Dinitrosalicylate Reagent for Glucose Determination in Mixed Solvents

Abstract The reduction of 3,5-dinitrosalicylic acid to 3-amino-5-nitrosalicylic acid by glucose is the basis for a common method of glucose determination. We have demonstrated that the method can be used in mixed solvents consisting of water and any of several organic solvents. In some cases a calibration curve other than the curve for water alone must be used.

The Reaction of M-Chloroperbenzoic Acid with 1,2-Glycols

Abstract The use of m-chLoroperbenzoic acid for the determination of unsaturation can give high results if the sample contains a 1,2-glycol structure. An explanation for the high results is presented.