RESEARCH

in Brief, from the 130th National ACS Meeting • Mye -inositol's B-vitamin status is stSH in question. Many workers in the past have demonstrated the compound increases growth of such animals as mice, chickens, and turkeys. But in recent work, optimium growth has been obtained without inositol in the diet. Some feei more purified forms of myo-inositol will be needed before any significant results can be obtained.

G. M. Briggs, National Institutes of Health

Carbohydrate Division

• A new amino sugar found in uridine diphosphate amino sugar compounds formed in penicillin-treated phosphorus metabolism is the same as the uniden­tified amino sugar found in cell walls of certain gram positive bacteria. The Elson-Morgan test can be used to de­termine the sugar in the presence of glycosamine, and in the latter's pres­ence, can be separated on a cation ex­change resin. The effluent sugar is similar in properties to amino-uronic acid, but different from synthetic glu-cosamin-uronic acid.

J . T. Park, University of Pennsylvania Carbohydrate Division

ί Strong analgesic activity is shown by a series of compounds related to meperidine—ethyl l-aralkyl-4-phenyl-piperidine-4-carboxylates. Pharmaco­logical evaluation by a rat thermal stimulus method indicates that the most effective aralkyl groups are those hav­ing a three-carbon unsaturated chain. Bill Elpern, Lorraine N. Gardner, & Leonard Grumbach., Sterling-Winthrop Research Institute

Medicinal Division

• Compounds similar in structure t o serotonin (5-hydroxytryptamine) have been prepared by Hofmann rear­rangement of the amides obtained on addition of acrylamide or methacryl-amide to benzimidazoles. The com­pounds are l-(j8-aminoethyl)- and 1-( /^aininopropyl ) -benzimidazoles. Pre­liminary pharmacological study shows that some cause a rise in blood pressure and/or a contraction of smooth muscle, actions comparable to serotonin. Others, however, have the Opposite effects. These benzimidazoles thus ap­pear to have an effect on the central nervous system, and this pbase is being investigated. William B. Wheatley, Bristol Laboratories, & Gerald" F . Stiner, State University of New York

Medicinal Division

• A n e w series of ketones and methyl­pyrazine homologs have been prepared in high yield by treating pyrazylmethyl-sodium (prepared by reaction of methylpyrazine with sodium amide in liquid ammonia) with a variety of ali­

phatic, aromatic, and heterocyclic es­ters and alkyl halides. Pharmacologi­cal evaluation is under way. The com­pounds may have valuable drug activ­ity themselves or may serve as inter­mediates.

John D. Behun & Robert Levine, University of Pittsburgh

Medicinal Division

• Toxic effects of selenium include growth rate inhibition and various de­grees of liver damage. Growth rate is retarded more in female than in male rats. Addition of choline chloride re­verses grovvrth rate inhibition and in­creases duration of life. No protection against selenium-induced liver injury is furnished by choline.

Irene Rosenfeld & H . F. Eppson, University of Wyoming

Biological Division

• Human skeleton takes up calcium in preference to strontium, resulting in calcium enrichment of bone and stron­tium enrichment of soft tissue. Results were obtained with Sr85 and Ca45 ad­ministration. Biological fractionation of the two elements is important, since accumulation of radioactive strontium is a hazard stemming from fission fall­out debris. Subsequent strontium ex­cretion results in eventual calcium en­richment of soft tissue as well. Arthur Schulert, Martin Charles, E. A. Peets,

Walter^ Eckelmann, Daniel Laszlo, Columbia University and Montefiore Hospital

Biological Division

^Conditioning the body to resist a state of severe shock, such as occurs in accidents and war, may be in prospect. Resistance to injury was developed in rats by inflicting a series of small, non­fatal injuries, or by subjecting them to electric shocks. After conditioning, only 25% of group died after being exposed to injuries that normally kill as many as 75%.

R. L. Griswold & W. J. Decker, Walter Reed Army Medical Center

Biological Division

• Changing the pathways of cellulose synthesis experimentally may be pos­sible. Biosynthesis of C 1 4 specifically labeled cellulose shows that after D-glu-cose-C14 is added initially and again in one to two days after inoculation with Acetobacter xylinum, a 10 to 12% in­crease of C 1 4 is found in original posi­tion of D-glucose-C14 of cellulose when labeled sugar is added 4 8 hours after inoculation.

G. A. Greathouse, Orlando Research & University of Florida

Biological Division

ί Presence of free amino groups seems to be a common feature of most

protein antigen-antibody systems. In each of six unrelated systems observed, free amino groups are critically in­volved in reactive sites of antibody molecules. Antibody is completely in­activated by acetylation, while same treatment does not affect antigen activ­ity. Antigen excess protects homolo­gous antibody against acetylation inao tivation.

S . J. Singer, Yale University Biological Division

• New route €or synthesis of alkyl azides from hydrazine derivatives may be a means of making alkyl azides not conveniendy m a d e by displacement of halide by sodium azide. Since re­quired intermediates are aminoure-thanes and 2-alkylsemicarbazides (which can b e prepared from alkyl-amines or alkylhydrazines), this route makes it in principle possible to make azides from nitroalkane or fatty-aedd derivatives as raw materials. As nitro­gen atoms are introduced step-wise i n synthesis, method also can serve as means of preparing nitrogen-labeled compounds. Peter A. S. SmiUb, University of Michigan,. &

John M. Clegg, Hooker Electrochemical Organic Division

• A single-step route to certain sub­stituted phthalic anhydrides previously available only by roundabout proce­dures. This involves the reaction of bromo- or ehlorobenzene with sodium carbonate a n d carbon monoxide in presence of catalytic amounts of nickel carbonyl. Art apparent intermediate, benzoic anhydride, disproportionates smoothly to phthalic anhydride and benzene under reaction conditions (temperatures ranging from 250° to 375° C , and pressures of 100 to 6 0 0 atmospheres). The permissible sub­stituent groups include alkyl, aryl, arid alkoxyl. Disproportionation of ben­zoic anhydride has been extended to conversion of: N,2V-dibenzoylaniline to N-phenylpbtbalimide and benzene.

W . W. Prichard, Du Pont Organic Division

• Solid state reactions in formation of condensed phosphates indicate the pres­ence of an intermediate amorphous phase that provides a medium for trans­port of ions. In formation of sodium tripolyphospliate the high temperature, metastable form crystallizes first from the reaction mixture, then transforms to** the low temperature, stable modifica-«-* tion. Theory consistent with experi­mental data involves the diffusion of small cations and water through the

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RESEARCH

amorphous phase. A mobile equilib­rium between water and the condensed phosphate ions maintains a level of orthophosphate to support its reaction with pyrophosphate to give the tripoly-phosphate.

James W. Edwards & A m ο Κ. Monsanto Chemical

Physical & Inorganic Division

• Nonstoichiometry of uranium hy­dride appears to he due to hydrogen vacancies in the U H 3 lattice. Isotherms for hydrogen pressures as high as 65 atmospheres show that hydrogen can be removed from "fully" hydrided uranium hydride, creating vacancies and causing the pressure to drop sharply; then when saturation concen­tration of vacancies is reached, the lat­tice cannot accommodate any more vacancies and the hydride breaks down into a two-phase system consisting of uranium metal and hydride containing the maximum number of vacancies.

G. G. Libowitz and T . R. P . Gibb, Jr., Tufts University

Physical & Inorganic Division

• Ions, not free radicals, get the credit for the reactions that occur when meth­ane is subjected to high energy radia­tion, such as from a 2 m.e.v. Van de Graaff. This conclusion, largely ig­nored for almost 3 0 years, is drawn from the fact that the energy yields of the reaction are apparently independ­ent of pressure, temperature, and radia­tion intensity. This can be accounted for by the ion—molecule reaction CH4

+

+ CH4 — > CH5+ -f- CH 3 which has

been observed in the mass spectrometer.

F. W. Lampe, Humble Oil & Refining Physical & Inorganic Division

• Diatomic potassium molecules could account for the apparent association of dissolved metal in the potassium-potassium halide systems correspond­ing to positive deviation from Raoult's Law. Solubility of the solid halide in the metal near the monotectic tem­perature (about 20° C. below the melting point of the pure salt) is of the same order of magnitude as its solubility in water at room temperature. Complete miscibility of potassium metal and its halides in the liquid state occurs at 790° C. for the chloride, 727° C. for the bromide, and 717° C. for the iodide.

J. W . Johnson & M. A . Bredig, Oak Ridge National Laboratory

Physical & Inorganic Division

• Chronopotentiometric methods may b e more suitable than potentiometry and polarography for high-temperature analysis of molten systems such as occur in metallurgy, glass manufacture, or the fused salt systems found in some

atomic reactors. Several components can be determined simultaneously, analyses can be carried out under such conditions that virtually all mass trans­port is by linear diffusion, and the total electrolysis product formed in the process is too small to produce trouble­some deposits.

H. A. Laitinen & W. S. Ferguson, University of Illinois

Analytical Division

r C^one in concentrations of up to 35 p.p.h.m. have been found on days of heavy smog in Pasadena, Calif. The measurements, made with a long-path (approximately 300 feet) ultraviolet spectrometer in the band between 254 and 3 6 5 πιμ, were recorded automati­cally and continuously over 24-hour periods. Ozone concentration charac­teristically showed a sharp rise in the morning, reached a peak during the middle of the day, and gradually diminished in the afternoon.

X . A. Renzetti, Air Pollution Foundation * Analytical Division

r Detector crayons tha t leave marks which will turn various colors in the presence of small quantities of toxic gases have been prepared by combin­ing sensitive indicating chemicals with suitable fillers and binders. For ex­ample, as little as eight parts of phos­gene in a billion parts of air cause one type of crayon to turn vivid red within a minute. Other crayons can be used to indicate hydrogen cyanide, Lewisite, or cyanogen chloride in concentrations not considered harmful.

Benjamin Witten & Arnold Prostak, Army Chemical Center

Analytical Division

• Optimum a m o u n t of fluoride in drinking water to obtain the best bal­ance between caries reduction and pres­ence of tooth enamel mottling has been calculated to be 0.75 p.p.m.; the pres­ently accepted level is 1.0 to 1.2 p.p.m. This conclusion comes from applying graphical calculus to data of Dean et al. taken in 1941-1942 covering 12- to 14-year-old children in 21 cities. At the 0.75 p.p.m. level, caries are present in 86% of the 12 to 14 year old children and mottling shows in 9.5% of the same age group. A. A. Hirsch, Department of Water and Sew­

erage, Shreveport, La. Water, Sewage, & Sanitation Division

• Temperaure and duration of the final bake of epoxy coatings have sig­nificant effect on subsequent oxidiza­bility of the film. Above 400° ' F., some film degradation occurs and these bake temperatures can cause consider­able volatilization of the coating.

W . B . R. Park & Jesse Blount, Jr.. Case Institute of Technology

Paint, Plastics, & Printing Ink Division

• Urethane rubbers are formed by hydroxy-isocyanate reaction. This is confirmed by tests with liquid elasto­mers made from glycerol and diisocy-anate-modified polyesters. Stoichiomet­ric ratio of these reactants called for by this type reaction (3 :2 ) gives maximum modulus of resulting elastomer. G. T. E . Graham & R. A. Gregg, U. S . Rubber

Paint, Plastics, & Printing Ink Division

• fpsilon-caprolactones synthesized from low-cost mixed cresols and xylenols are attractive intermediates for urethane products. Substituted capro-lactones can be obtained in high yields and efficiencies by conversion of the phenol mixtures to cyclohexanones, fol­lowed by oxidation with peracetic acid. Use of the substituted caprolactones offers an extremely large number of building blocks for urethane polymers. D . M. Young, F. Hostettler, L.. C. Shriver &

R. W. MacLaughlin, Carbide & Carbon Paint, Plastics, & Printing Ink Division

• A significant improvement in cata­lytic cracking characteristics may be ob­tained under quite mild hydrotreating conditions at operating pressures down to 500 p.s.i.g. Cobalt molybdate on alumina or bauxite is a good catalyst for treating a variety of stocks, includ­ing wide-range high-sulfur gas oils, vis-breaker gas oils, and even wide-range virgin gas oils from low-sulfur crudes.

C. R. Eberline, R. T . Wilson, & L. G. Larson, Phillips Petroleum

Petroleum Division

• Tidewater Oi9 realizes substantial savings in gasoline production through reduced consumption of T E L and in­hibitors. Storage space, too, has been cut in half by reduction in inhibitor sweetening time. The trick: add a very small amount of lead (in the form of doctor solution) to caustic used for sweetening. Gasoline components, after sweetening in this manner, have a very low peroxide number and coppei dish gum, and a higher end point.

L. D . Rarapino & M. J. Gorham, Tidewater Oil Petroleum Division

• Conversion of petroleum residues into valuable lighter fractions may be­come economically attractive in the next decade. Houdry researchers have developed a catalytic hydrocracking process which uses a light hydrocarbon diluent and has reduced catalyst poison­ing. Their method produces high yields of gasoline and other distillates « with only occasional catalyst régénéra- * tion.

Heinz Heinemann & D . H. Stevenson, Houdry Process Corp.

Petroleum Division

4 8 9 0 C&EN OCT. 8, 1956