M.S.

This investigation was undertaken to further the work of Wagner who isolated coniferyl aldehyde by the treatment of wood with stannous chloride. An attempt has been made to determine whether or not coniferyl aldehyde can be obtained by the action of stannous chloride on two different lignin preparations, and thus answer the question as to whether Wagner’s coniferyl aldehyde came from the lignin of the wood or existed free in the wood. 1. It is unlikely that white pine lignin will yield coniferyl aldehyde when isolated and treated with stannous chloride according to the methods described in this investigation. 2. It is probable that Wagner’s coniferyl aldehyde existed free in the wood. / M.S.

From the results obtained in this investigation, the following conclusions can be drawn: 1. A substance inhibits corrosion only under certain conditions, and under other conditions it may not be an inhibitor, but may be inert or an accelerator. 2. No compounds tested in concentrations of 0.01 and 0.10 percent nitrogen, were found to inhibit the corrosion of steel in 5 percent phosphoric acid at 25°C. and under the conditions of aeration and agitation used. 3. Sodium chromate is an inhibitor in concentrations of 1 percent for the corrosion of steel by a 5 percent, aerated, agitated, phosphoric acid solution at 25°C. 4. The mechanism of the corrosion of copper proposed by Whaley is not substantiated. Chelation probably is not the mechanism by which 2-nitro-l-butanol inhibits the corrosion of copper in a 5 percent phosphoric acid solution. 5. Inhibitors that are used and are efficient for one acid under certain conditions cannot always be said to work for other acids under other conditions. / M.S.

M.S.

The purpose of this study was to investigate the supported catalyst of the type CuO-Al₂O₃ which has been described by Lockwood and Frazer (13). This type of catalyst is unique in that it has a high activity at low temperatures, is suitable for use at high temperatures and has been reported to be truly catalytic in the oxidation of carbon monoxide. Lockwood and Frazer (15) have described the preparation of a catalyst of this type. Their description of the method of preparation and of the quantities of materials used is rather inadequate for an exact duplication of the catalyst which they prepared and studied. The method of procedure used in the study of this catalyst has been to vary both the composition and heat treatment of the catalysts and to observe the subsequent change in catalytic activity. 1. Increasing the copper oxide content of the copper oxide-aluminum catalysts increases the activity of the catalysts at least over the composition range studied. 2. Increasing the temperature to which the copper oxide-aluminum oxide catalysts are heated increases the activity. 3. The temperatures required for the catalysts to exhibit 100% activity are all above 270°C. 4. It was found impossible to reproduce the copper oxide-aluminum catalyst which was prepared by Lockwood and Frazer. 5. A catalyst prepared from pure copper oxide was more active than any of the catalysts which were studied. / M.S.

1. A systematic study of the reduction of organic sulfur compounds by different metals in liquid ammonia is reported for the first time. 2. A metal with a high half-cell potential favors a greater extent of reduction than a lower potential metal. 3. The greater the concentration of ammonium ion as a proton donor, the greater will be the evolution of hydrogen, and the lower will be the extent of reduction. 4. A mechanism for the reduction of organic sulfur compounds by metals in ammonia is presented. 5. A new procedure for the quantitative removal and determination of hydrogen sulfide in mercaptans was developed. 6. A new synthesis for allyl mercaptan was found. 7. The formation of a resin believed to be a thiophene polymer of the formula (C₄H₄S)_x is reported. / M.S.

Stopped-flow kinetics is a method in which two reactants are forced into a mixing chamber and their flow abruptly stopped. The progress of the reaction is monitored at an observation window, a short distance from the chamber along the flow path. Traditionally, data from the stopped-flow has been collected on film from a storage oscilloscope. Points were then measured from the photograph and results tabulated by hand. With the computer now available at a reasonable cost, this method of data acquisition is unacceptable. Presented in this work is an 8085-based, single board microcomputer system to acquire and store data from the stopped-flow apparatus. The system is user friendly, allowing the operator to set parameters such as rate, point total, and window of transmittance. The data once acquired, can be displayed at the work station or transmitted to a host computer for later manipulation. Data from a Beer's law investigation and from the well-documented FeCl3- KSCN reaction will be presented as a system evaluation. / M.S.

M.S.

N,N'-Dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones were successfully prepared from the respective primary amines via alkylation of their methanesulfonamide derivatives. Initially N,N'-diaminodiphenylmethanes and N,N'-diaminobenzophenones were treated 0 with 2.2 equivalents of methanesulfonyl chloride in pyridine at 80° to afford the corresponding bis methanesulfonamide derivatives in 79-91% yields. Alkylation was accomplished by reacting the sulfonamides with 2.2 equivalents of dry potassium hydroxide in hexamethylphosphoramide at 75°, followed by addition of 2.2 equivalents of alkylating agent (methyl iodide, ethyl iodide, and benzyl chloride) to afford 70-84% of the alkylated sulfonamides. Subsequently the N,N'-dialkylsulfonamides were cleanly cleaved using a mixture of concentrated sulfuric/acetic acids (40-60%, vol/vol) to afford N,N'-dimethyldiaminodiphenylmethanes and N,N'-dialkyldiaminobenzophenones in 68-87% and 64-85% yields, respectively. β-Hydroxy sulfonamides were prepared by treating N-methyl methanesulfonanilide with a 10% excess of n-butyllithium in tetrahydrofuran at -78°, followed by addition of benzophenone or acetone to afford the corresponding β-hydroxy sulfonanilides in 76% yield. Upon heating the sulfonanilide-benzophenone adduct in refluxing toluene, water was eliminated to form the corresponding unsaturated sulfonanilide in 89% yield. The attempted preparation of β-hydroxy sulfinamides involved initially the synthesis of N-methanesulfin-p-toluidide following the procedure of Corey and Durst. This compound was subsequently alkylated with sodium hydride and methyl iodide in 1.2-dimethoxyethane in 76% yield. Treatment of the resulting methylated sulfinamide with lithium 0 diisopropylamide at - 78° followed by addition of water, resulted in elimination of the methanesulfine group to afford N-methyl-p-toluidine as the major product. / M.S.

Three samples of flour were quantitatively analyzed for histidine, arginine, and lysine. The three diamino acids were separated from each other and from the non-basic amino acids by precipitating histidine silver at pH 7 .4, arginine silver between pH 8.5 and 14, and lysine with phosphotungstic acid. The histidine was isolated as the nitranilate, arginine as the flavianate, and lysine as the picrate. Analyses were also carried out for moisture, ash, fat, protein nitrogen, and total protein; the probable ash in the whole wheat was also calculated. It was concluded that the method was not too accurate due to the many possibilities for error and the exactness of technique necessary, and also the procedure was too long for the accuracy obtainable. Improvements in the method and further work were suggested for the future. / M.S.