bluuebunny/crossref_metadata_2025 huggingface dataset:
CONTRIBUTION TO THE STUDY OF 4-MONOSUBSTITUTED-3-AMINO-5-PYRAZOLONES
Authors: Gagnon Paul E. , Boivin Jean L. , Giguere Jacques
Published: May 2006

The condensation of monosubstituted cyanoacetic esters with hydrazine gave rise to 4-R-3-amino-5-pyrazolones. The pyrazolones prepared were those in which R = o-chlorobenzyl, β-p-methylphenoxyethyl, γ-p-methylphenoxypropyl, β-p-ethylphenoxyethyl, β-p-chlorophenoxyethyl, γ-p-chlorophenoxypropyl, γ-p-bromophenoxypropyl, or n-dodecyl.The ultraviolet absorption spectra of these pyrazolones were determined in neutral, acid, and alkaline medium.
EXCHANGE REACTIONS OF ALICYCLIC IODIDES WITH SODIUM IODIDE
Authors: Van Straten Sylvia F. , Nicholls R. V. V. , Winkler C. A.
Published: May 2006

The activation energies for the exchange reactions between sodium iodide and cyclopentyl, cycloheptyl, cycloöctyl, cyclopentadecyl, and 2-heptyl iodides were all in the range 21 ± 1 kcal. per mole. For cyclohexyl iodide the value was 25.6 kcal. per mole. This difference seems to be explained from a consideration of the initial potential energies of the various rings. An inverse relation appears to exist between log PZ and [Formula: see text], the reciprocal of the number of carbon atoms in the iodides investigated, for all the iodides except cyclopentyl iodide. This might be due to a change in the number of equivalent constellations in the activated state.
THE ULTRAVIOLET ABSORPTION SPECTRA OF SEVERAL DEHYDRATION AND OXIDATION DERIVATIVES OF CHOLESTEROL
Authors: Cox R. H. , Spencer E. Y.
Published: May 2006

Certain dehydration and oxidation products of cholesterol were prepared for subsequent animal experimentation. The ultraviolet absorption spectra of those derivatives possessing two or more conjugate chromophores were determined spectrophotometrically over the wave length range of 220 mμ to 350 mμ. The relative coincidence of the experimental λmaxand εmaxvalues of cholestadiene-3, 5 and of the enol acetate of cholesten–4–one–3 is offered as support for a 3, 5-diene structure for the latter steroid in particular and for enol esters of 4,5-unsaturated 3-ketosteroids in general.
BIOCHEMISTRY OF THE USTILAGINALES: II. ISOLATION AND PARTIAL CHARACTERIZATION OF USTILAGIC ACID
Authors: Lemieux R. U. , Thorn J. A. , Brice Carol , Haskins R. H.
Published: May 2006

The needlelike crystals which form in aerated submerged cultures of the corn smut Ustilago zeae (PRL-119) were found to be a D-glucolipid, m.p. 146-7°C, [Formula: see text] (pyridine), which contained one carboxyl group, two ester groups, at least two terminal methyl groups, and two D-glucose residues per mole. On the basis of elementary analyses, neutralization equivalent, and molecular weight estimations, the molecular formula of the material isolated was approximately C37H62−6O17. The substance was not shown to be chemically homogeneous. Conditions used in culturing the fungus in stirred fermentors to produce the crystalline metabolic product, which was termed "ustilagic acid", are described, and a procedure for the isolation of the material is given.
THE BIOCHEMISTRY OF THE USTILAGINALES: III. THE DEGRADATION PRODUCTS AND PROOF OF THE CHEMICAL HETEROGENEITY OF USTILAGIC ACID
Authors: Lemieux R. U.
Published: May 2006

The D-glucolipid designated as ustilagic acid was shown to be a mixture of partially acylated derivatives of a di-D-glucosyl-dihydroxyhexadecanoic acid. The dihydroxyhexadecanoic acid was named "ustilic acid" and its di-D-glucosyl derivative was termed "glucoustilic acid". Alkaline hydrolysis of ustilagic acid yielded glucoustilic acid, acetic acid, dextro-β-hydroxy-n-caproic acid, dextro-β-hydroxy-n-caprylic acid and a small amount of n-caproic acid. The β-hydroxy-acids were characterized as dextro-β-hydroxy-n-caprohydrazide, m.p. 131–132°C., [α]D + 15.9° (water), and dextro-β-hydroxy-n-caprylhydrazide, m.p. 127–128°C., [α]D + 12° (water). Ustilic acid, m.p. 114–115°C., [α]D − 6.3° (methanol), yielded a methyl ester, m.p. 80−81.8°C, [α]D − 0.2 (chloroform). The methyl ustilate formed a di-phenylurethane derivative, m.p. 76–77°C. The infrared spectra of crystalline and amorphous samples of ustilagic acid are given. The specific rotation of glucoustilic acid, [α]D − 11° (methanol) was that expected of β-D-glucosides and the infrared spectrum of this substance showed a marked resemblance to that of methyl-β-D-glucopyranoside.
CONDUCTANCE OF AMMONIUM NITRATE IN WATER – NITRIC ACID – NITROGEN PENTOXIDE MIXTURES AT VARIOUS TEMPERATURES
Authors: Taylor Edward G. , Baker Charles A. N. , Lyne L. Murray
Published: May 2006

Conductance measurements have been made with ammonium nitrate in water – nitric acid – nitrogen pentoxide mixtures at various temperatures and over a wide range of concentrations. For all solutions except those rich in nitrogen pentoxide the variation of the specific conductance with the concentration of ammonium nitrate is similar to that observed for many electrolytes in a variety of solvents. With nitrogen-pentoxide-rich solvents however the specific conductance of ammonium nitrate is observed to decrease with increasing salt concentration. This is regarded as indicative of an interaction between the salt and one or more of the components of the nitric acid – nitrogen pentoxide system. The variation of conductance with temperature is normal in all cases. It is shown that ammonium nitrate confers a considerable degree of thermal stability on anhydrous nitric acid.
DROPPING AMALGAM ELECTRODES
Authors: Turner R. C. , Winkler C. A.
Published: May 2006

The anodic limiting current at a lead amalgam dropping electrode is shown to be proportional to the concentration of the lead in the amalgam, at constant flow rate. The original Ilkovic equation does not apply to the anodic limiting current from dropping amalgam electrodes.The anodic limiting currents with lead and cadmium amalgams have been found to agree with the 2nd approximation of the Ilkovic equation, as derived by Strehlow and Stackelberg for this process, for flow rates in the region below approximately 1.2 mgm. per sec. With flow rates greater than this, the lead amalgams gave a linear relation between the anodic limiting current divided by concentration and the mass flow rate. With cadmium amalgams no such linear relation was evident and the magnitude of the limiting current depended on the size of the drops as well as on the mass flow rates. The half wave potentials of lead and cadmium were found to depend on the flow rate of the dropping electrode.
ANALYSIS OF MIXTURES OF SIMPLE ALIPHATIC ALCOHOLS BY PARTITION CHROMATOGRAPHY
Authors: Neish A. C.
Published: May 2006

Mixtures of methanol, ethanol, isopropanol, n-butanol, and isoamyl alcohol were resolved by partition chromatography on Celite–water columns, using carbon tetrachloride and chloroform as developing solvents, each alcohol being determined quantitatively by dichromate oxidation of the fractions thus obtained. Only 0.5 ml. of an aqueous solution containing 1–5 mgm. of each alcohol was required for an analysis. The method was used successfully in the analysis of a mixture of volatile fermentation products containing n-butanol, isopropanol, ethanol, acetoin, diacetyl, and acetone.
THE DISTILLATION, EXTRACTION, AND CHROMATOGRAPHIC SEPARATION OF THE C2–C8FATTY ACIDS
Authors: Fairbairn D. , Harpur R. P.
Published: May 2006

Thirty-five milliliters of an aqueous solution containing 5 to 70 micromoles of volatile C2to C8acids was distilled to constant volume without refluxing. The distillate was titrated, made alkaline, and evaporated to dryness at 110°C. The free acids were regenerated by the addition of 0.03 ml. of 10 N sulphuric acid, absorbed on filter paper, and extracted quantitatively with 3 ml. of chloroform–butanol (99: 1). Acids present in the extract were separated by chromatography on a composite silica-gel column employing two internal indicators, and after elution were determined by titration, the details for which are given. The preparation of a reproducible silica is described.
A DILUTION EFFECT IN REACTIONS BETWEEN DIPOLAR MOLECULES IN SOLUTION
Authors: Bain Osias , Ouellet Cyrias
Published: May 2006

A study has been made of the variation of the reaction rate constant with increasing dilution in the case of three reactions between pairs of dipolar substances in ethanol solution. The reactions examined were those between aniline and 2,4-dinitrochlorobenzene, p-toluidine and 2,4-dinitrochlorobenzene, and p-toluidine and 2,4-dinitrobromobenzene. As the concentrations of the reactants in the first two cases are increased 50-fold, the bimolecular velocity coefficient decreases by approximately 12% in the case of the first reaction, and by 7% in the case of the second one. The rates decrease sharply as the solubility limits of the products in ethanol are approached, while they become relatively constant as high dilutions are attained.
CHEMICAL EFFECTS OF THE Cl35(γ, n)Cl34 REACTION IN SODIUM CHLORATE
Authors: McCallum K. J. , Holmes O. G.
Published: May 2006

The distribution of Cl34 among different valence states following the Cl35 (γ, n) Cl34 reaction in solid sodium chlorate has been investigated, using a betatron as the source of gamma rays. The percentage of the activity in the hypochlorite and perchlorate fractions differed from zero by less than the experimental error; the small activity separated with the chlorite fraction could be accounted for by an exchange reaction between chloride and chlorite ions. The major part of the activity, 91 ± 2%, was present in the chloride fraction, the remainder of the activity being present as chlorate ion. One-quarter of the activity in the chlorate fraction could be accounted for by an exchange reaction between chloride and chlorate ions. The results were not affected by an alteration in the peak energy of the gamma rays or by a change in the amount of radiation. The results are compared with those following the Cl37 (n, γ) Cl38 reaction in the same compound.
A Semimicro Filtration Apparatus
Authors: Cockburn W. F.
Published: May 2006

not available
STUDIES ON RDX AND RELATED COMPOUNDS: VI. THE HOMOGENEOUS HYDROLYSIS OF CYCLOTRIMETHYLENETRINITRAMINE (RDX) AND CYCLOTETRAMETHYLENETETRANITRAMINE (HMX) IN AQUEOUS ACETONE, AND ITS APPLICATION TO ANALYSIS OF HMX IN RDX(B)
Authors: Epstein S. , Winkler C. A.
Published: May 2006

Measurements of the rates of alkaline hydrolysis of cyclotrimethylenetrinitramine (RDX) and cyclotetramethylenetetranitramine (HMX) in aqueous acetone show these two reactions to involve consecutive steps, the first of which is second order and rate controlling. Activation energies were estimated as 14 and 25 kcal. respectively. By establishing calibration curves, and controlling temperature, alkali concentration relative to concentration of explosive, and reaction time, the differential hydrolysis permits analysis of the HMX content of RDX(B) with an error of approximately ±0.2% HMX.
THE FORMATION OF LIGNIN IN WHEAT PLANTS
Authors: Stone J. E. , Blundell M. J. , Tanner K. G.
Published: May 2006

Wheat plants were harvested approximately every two weeks after emergence from the soil. Determination of the lignin content by the 72% sulphuric acid method showed a rapid increase between the period 45–70 days from seeding, and there was a corresponding increase in the yield of vanillin and syringaldehyde, obtained by alkaline nitrobenzene oxidation. The p-hydroxybenzaldehyde yield remained low at all times and seemed to be derived from a different system. It is suggested that the source of this aldehyde is not the lignin, but the tyrosine associated with the protein. The ratios of vanillin to syringaldehyde did not remain constant from plants of different ages, the percentage of syringaldehyde being lower than vanillin in the young plants and higher in those which were more mature. This is qualitatively in agreement with an increase in the methoxyl content of the lignin.When the yield of aldehydes from mature plants is taken as the criterion for the amount of lignin present, the youngest plants have a lignin content of about 0.13%, a value much lower than other bases for calculation would indicate.Oxidation of the whole plant and of the plant which had been extracted with alcohol–benzene, water, and 1% hydrochloric acid, gave similar percentages of aldehydes, owing partly to the removal of aldehyde-producing substances and partly to the degradation of the lignin during the extraction process. Oxidation of the extracts gave no trace of aldehyde in the hydrochloric acid extract, a trace in the water extract, and appreciable percentages in the alcohol–benzene extract. This latter extract consisted of two portions, a red water soluble, alcohol–benzene insoluble fraction and the main alcohol–benzene soluble fraction. The former gave rise to vanillin and p-hydroxybenzaldehyde on oxidation, the amount being a maximum at the first harvest and decreasing to zero after lignification had occurred. The latter, that is, the alcohol–benzene soluble extract, gave rise to syringaldehyde as well as the others, the amounts being low at first and increasing during lignification in the same way as the main body of the plant. It is believed that the alcohol–benzene removes a soluble portion of the lignin since the relative proportions of the aldehydes are very similar to those obtained from lignin itself.
BIOCHEMISTRY OF THE USTILAGINALES: VI: THE ACYL GROUPS OF USTILAGIC ACID
Authors: Lemieux R. U. , Charanduk R.
Published: May 2006

A partition chromatographic technique was established for the estimation of the acetic, n-caproic, L-β-hydroxy-n-caproic, and L-β-hydroxy-n-caprylic acids which are liberated on the hydrolysis of ustilagic acid. The free carboxyl group of ustilagic acid was shown to be derived from the ustilic acid residue. Since fractional precipitation of ustilagic acid did not alter the original composition, it was concluded that ustilagic acid consists of 65–70% of a monoacetyl-mono-L-β-hydroxy-n-caproylglucoustilic acid and 25–30% of a monoacetyl-mono-L-β-hydroxy-n-caprylylglucoustilic acid.
IONIC SPECIES IN CERIC PERCHLORATE SOLUTIONS
Authors: Hardwick T. J. , Robertson E.
Published: May 2006

Ceric ion has been shown to exist in perchloric acid solution as a mixture of Ce4+, CeOH3+, and a dimer, probably (Ce-O-Ce)6+. From a spectral study between 395 and 430 mμ, the values of the equilibrium ratios have been determined, along with the molar extinction coefficients of each ion over this region of wave length. The thermodynamic quantities ΔH, ΔF°, and ΔS° have been determined for each reaction.
SYNTHESIS AND ULTRAVIOLET ABSORPTION OF SOME PYRAZOLONES
Authors: Gagnon P. E. , Nolin B. , Jones R. N.
Published: May 2006

Thirteen 3-amino-5-pyrazolones substituted only in position 4 have been synthesized from the corresponding mono- or disubstituted cyanoacethydrazides or cyanoacetic esters in alkaline medium. Their ultraviolet light absorption spectra have been determined in neutral and acid solutions.
HYDROGEN PEROXIDE AND ITS ANALOGUES: IV. SOME THERMAL PROPERTIES OF HYDROGEN PEROXIDE
Authors: Foley William T. , Giguère Paul A.
Published: May 2006

Using a Bunsen ice calorimeter the following thermal data were obtained for pure hydrogen peroxide:Specific heat of liquid between0°and25°C …................... 0.632 ± 0. 003 cal. per.gm. per degreeSpecific heat of solid between−20°and −10°C.................. 0.41 ± 0.02 cal. per gm. per degreeLatent heat of fusion at meltingpoint, −0.46°C................... 85.83 ± 0.18 cal. per gm.Latent heat of vaporization at 0°C...... 370.17 ± 0.18 cal. per gm.The freezing points of very concentrated solutions of hydrogen peroxide calculated from these data agree closely with the experimental ones. Preliminary measurements of the heat of decomposition of hydrogen peroxide catalyzed by platinum black were also made at 0° and at various concentrations. The results point to 23.54 ± 0.04 kcal. per mole for the heat of the reaction[Formula: see text]a value slightly higher than those found by previous experimenters.
AN IMPROVED SYNTHESIS OF CIS-CIS-TRANS-CYCLOHEXANE-1,2,3-TRIOL
Authors: Gogek C. J. , Moir R. Y. , McRae J. A. , Purves C. B.
Published: May 2006

Cyclohexene-3-ol acetate was readily made from cyclohexene and when oxidized, preferably with performic acid, gave 20 to 25% yields of partly acylated cis-cis-trans-cyclohexane-1,2,3-triol, but only 1 to 2% of the cis-trans-cis isomer. The structures of the three cyclohexane-1,2,3-triols were deduced from the theory of the Walden Inversion.
THE BENZOATE AND THE METHYL ETHER OF 4-HYDROXYCYCLOHEXENE
Authors: Gogek C. J. , Moir R. Y. , Purves C. B.
Published: May 2006

Satisfactory preparations, from hydroquinone and its monomethyl ether respectively, were devised for the above compounds which were thought to be new. The methyl ether of 4-hydroxycyclohexene was an oil, [Formula: see text] boiling at 136 °C.; the uncrystallized benzoate had nD, 1.5360 and b.p. 149 °C. at 12 mm. pressure.
THE BIOGENESIS OF ALKALOIDS: III. A STUDY OF HYOSCYAMINE BIOSYNTHESIS USING ISOTOPIC PUTRESCINE
Authors: Diaper D. G. M. , Kirkwood Sam , Marion Léo
Published: May 2006

Putrescine-1: 4-C14 was fed to mature Daturastramonium in an investigation of the biosynthesis of l-hyoscyamine. Although C14 was metabolized by the plant, no radioactivity was found in the isolated alkaloid; the mechanism of biosynthesis of the tropane nucleus is discussed in the light of published work and of this observation.
HYDROLYSIS AND POLYMERIZATION OF CYCLIC DIMETHYLETHYLENE OXALATES
Authors: Ripley L. G. , Watson R. W.
Published: May 2006

Macrocrystalline cyclic oxalates (2,3-dimethyl-5-6-p-dioxanediones) were prepared by vacuum distillation of the polymeric mixture formed on heating ethyl oxalate, and 1, 2-dimethylethylene glycol with an ester-interchange catalyst. Monomeric dimethylethylene oxalate polymerizes less readily than propylene oxalate, and only at an elevated temperature in the presence of a catalyst. Dimethyl substitution therefore confers marked stability on the six-membered ring. Hydrolysis reaches 50% completion almost instantaneously, followed by a slow first order reaction resulting in complete cleavage of the monobasic acid in about one month at room temperature. Hydrolysis constants for the levo- and meso- oxalates are 0.069 and 0.076 days−1 respectively. The crystalline monomers do not possess sharp melting points and represent stereoisomeric mixtures which display optical activity in solution.
THE REACTION OF NITROGEN ATOMS WITH METHANE AND ETHANE
Authors: Blades H. , Winkler C. A.
Published: May 2006

Methane reacted with nitrogen atoms at temperatures above 300°C. to produce hydrogen cyanide. An activation energy of 11 kcal. and a steric factor of 5 × 10−3 were obtained. The reaction of ethane with nitrogen atoms was studied up to 295°C., with hydrogen cyanide the only product found in measurable amounts. At high temperatures, nitrogen atom consumption was complete in excess ethane, and the hydrogen cyanide production under these conditions, compared with the atom concentration determined by a Wrede gauge, indicated the active species in the nitrogen stream to be only atomic nitrogen. The ethane – nitrogen atom reaction was second order, with an activation energy of 7 ± 1 kcal. and a steric factor between 10−1 and 10−3.
Synthesis of cis- and trans-1,2-Dichlorethylene-d
Authors: Leitch L. C. , Morse A. T.
Published: May 2006

not available
THE BIOGENESIS OF ALKALOIDS: V. RADIOAUTOGRAPHS OF BARLEY LEAVES FED WITH TRYPT0PHAN-β-C14
Authors: Bowden K. , Marion Léo
Published: May 2006

Radioautographs of leaves of barley fed with C14-tryptophan have been taken at intervals. In the early stages of development a radioactive area appeared at the bottom of the leaves, which was due mainly to free tryptophan. Later an area, consisting mainly of gramine, developed at the top of the leaves.
THE OXIDATION OF CARBON MONOXIDE BY SOLID SILVER PERMANGANATE REAGENTS: IV. CHEMICAL COMPOSITION IN RELATION TO ACTIVITY
Authors: Katz Morris , Wilson L. G. , Riberdy R.
Published: May 2006

The activity after progressive aging and thermal treatment of silver permanganate supported on zinc oxide and beryllium oxide was found to be closely related to the extent of decomposition of the crystalline silver permanganate. The silver salt decomposed, with loss of active oxygen, to a relatively insoluble, amorphous product resembling a manganito-manganate of the composition, Ag2O Mn2O5 or [AgMnO3]2. From a mass balance of solid–gas reactants in a reacting column, it was demonstrated that in the most active stage, during which the efficiency of oxidation did not fall below 90%, the course of the reaction was about evenly divided between stoichiometric and catalytic processes.
DIPHENYLCYANAMIDE DERIVATIVES
Authors: Robinson J. R. , Brown W. H.
Published: May 2006

Diphenylcyanamide is conveniently prepared by the action of cyanogen chloride on diphenylamine. When it is hydrolyzed in the presence of hydroxylated solvents, of the type ROH, stable isoureas are formed. These are readily hydrolyzed in aqueous alkaline medium to the corresponding urea derivative. Chlorination of diphenylcyanamide occurs in the para positions yielding a nitrogen analogue of DDT. This chlorinated derivative is only 1/80th as toxic as DDT to Sitophilusgranarius (L).
THE ADDITION COMPOUNDS OF SILICON TETRACHLORIDE WITH ALIPHATIC AMINES
Authors: Trost W. R.
Published: May 2006

Some diaminate and tetraminate addition compounds of silicon tetrachloride with butylamine, diethylamine, piperidine, triethylamine, and tributylamine have been prepared and analyzed. The tetraminates begin to decompose at temperatures above and below 200°C. The thermal stabilities and the products of the decompositions of these compounds indicate that coordinate bonds, and hydrogen bonds when possible, are involved in the formation of the tetraminates of silicon tetrachloride.
THE MERCAPTOLYSIS OF GLUCOSE AND GALACTOSE PENTAACETATES
Authors: Lemieux R. U.
Published: May 2006

The mercaptolysis of the α-and β-pentaacetyl derivatives of glucopyranose and galactopyranose at 0 °C. with zinc chloride catalyst was studied. The β-pentaacetates were rapidly transformed to the corresponding ethyl tetraacetyl-1-thio-β-D-glycosides in excellent yields; however, the α-anomers were highly resistant to the mercaptolytic conditions. The results are interpreted on the basis of a participation by the C2-acetoxy group in the replacements at the lactol carbon atom of the β-pentaacetates with the intermediate formation of a resonance stabilized cyclic carbonium ion.
AN EVALUATION OF OSMOTIC PRESSURE MEASUREMENTS USING POLYVINYL ACETATE SYSTEMS
Authors: McLeod L. A. , McIntosh R.
Published: May 2006

Measurements of osmotic pressures of polyvinyl acetate solutions in various solvents have been made. These pressures are precise to ±0.005 cm. of solvent and can be repeated on successive samples to 0.02 cm. In five solvents, plots of reduced osmotic pressure (π/C2) against concentration show distinct upward curvature which differs significantly from theoretical equations derived by Flory and by Huggins. The evidence suggests that further refinement of these theoretical equations is required to bring them into exact agreement with experimental data.
INVESTIGATION OF THE FORMS OF PHOSPHORUS IN NEUTRON-BOMBARDED PHOSPHATES: NATURE OF THE PHOSPHORUS-32
Authors: Fiskell J. G. A. , DeLong W. A. , Oliver W. F.
Published: May 2006

Evidence concerning the forms of phosphorus-32 occurring in neutron-bombarded calcium phosphates has been obtained using carrier ions for the different forms, and estimations of the proportional amounts present in these forms have been made. Ortho-, hypo-, pyro-, and metaphosphate forms of phosphorus-32 have been found as activity in the precipitation of the respective carriers; hypophosphate appeared to be an invariable and major component.
THE OXIDATION OF FERROUS SULPHATE SOLUTIONS BY γ-RAYS—THE ABSOLUTE YIELD
Authors: Hardwick T. J.
Published: May 2006

The absolute value of the yield of ferric ion on the irradiation of ferrous sulphate in 0.80  N sulphuric acid by γ-rays has been determined using the Bragg–Gray cavity principle. Sources of error in the measurements were reduced as much as possible. The yield obtained, 20.8 ± 0.3 ferric ions per 100 ev. absorbed, agrees well with Miller's value of 20.7 molecules per 100 ev.
STUDY OF 4-MONO- AND 4,4-DISUBSTITUTED-3-IMINO-2-BENZOYL-5-PYRAZOLONES
Authors: Gagnon Paul E. , Boivin Jean L. , Boivin Paul A. , Craig Hugh M.
Published: May 2006

4-Mono- and 4,4-disubstituted-3-imino-2-benzoyl-5-pyrazolones have been prepared from the corresponding ethyl mono- or disubstituted cyanoacetates and N-benzoylhydrazine. The presence of the imino group in 4,4-disubstituted-3-imino-2-benzoyl-5-pyrazolones was ascertained by the hydrolysis of 4,4-dibenzyl-3-imino-2-benzoyl-5-pyrazolone into 4,4-dibenzyl-3-oxo-2-benzoyl-5-pyrazolone. In order to prove that the benzoyl group in these pyrazolones was not in Position 1, the synthesis of 4-benzyl-3-amino-1-benzoyl-5-pyrazolone was attempted from 4-benzyl-3-carbethoxy-1-benzoyl-5-pyrazolone through a Curtius degradation of the 3-carbethoxy substituent into a 3-amino group. It was found that the 1-benzoyl group was hydrolyzed at the same time as the 3-carbethoxyamino substituent. The ultraviolet absorption spectra of all these compounds are reported and discussed briefly.
The Isotopic Constitution of Igneous Sulphur and the Primordial Abundance of the Terrestrial Sulphur Isotopes
Authors: Macnamara J. , Fleming W. , Szabo A. , Thode H. G.
Published: May 2006

not available
SYNTHESIS OF ORGANIC DEUTERIUM COMPOUNDS: II. PROPYNE-3-d3 AND PROPYNE-d4
Authors: Leitch L. C. , Renaud R.
Published: May 2006

A procedure for preparing magnesium carbide, Mg2C3; in 300 gm. lots is described. Propyne-d4 was prepared in good yields by the action of deuterium oxide on this carbide. The acetylenic deuterium in propyne-d4 was replaced by hydrogen via the mercury derivative giving propyne-3-d3 The vapor pressures of propyne-3-d3,and propyne-d4 were determined between −25 °C. and −60 °C.
2,2,5,5-TETRAMETHYLOLCYCLOPENTANOL PENTANITRATE
Authors: Downing D. C.
Published: May 2006

Tetramethylolcyclopentanone was hydrogenated (70% purified yield) and nitrated (74% purified yield) to give 2,2,5,5-tetramethylolcyclopentanol pentanitrate, m.p. 91°, a powerful explosive only slightly weaker than RDX. A number of its properties were determined.
Note On The Preparation Of Hydrazine By Arc Electrolysis In Liquid Ammonia
Authors: Ingraham Thomas R.
Published: May 2006

not available
INVESTIGATION OF THE FORMS OF PHOSPHORUS IN NEUTRON-BOMBARDED PHOSPHATES: III. SUPERPHOSPHATE AND CALCIUM SULPHATE HEMIHYDRATE
Authors: Fiskell J. G. A. , Delong W. A. , Oliver W. F.
Published: May 2006

Carrier-precipitation and serial molybdate precipitation procedures for the identification and estimation of chemical forms of phosphorus are presented in some detail. Application of these methods to the investigation of the forms of phosphorus-32 in superphosphate and calcium sulphate after neutron bombardment is described. The results obtained indicated that about 40% of the phosphorus-32 in the superphosphate was in the orthophosphate form and that the greater part of the remainder was present as metaphosphate and phosphite. Approximately 90% of the radioactive phosphorus present in the calcium sulphate was estimated to be in the orthophosphate form. The amount of phosphorus-32 in the superphosphate originating from the calcium sulphate component was estimated to be less than 0.2%.
THE MERCURY PHOTOSENSITIZED REACTIONS OF NITRIC OXIDE
Authors: Mcgilvery J. D. , Winkler C. A.
Published: May 2006

The photochemical decomposition of nitric oxide has been studied over a pressure range 60 to 500 mm., using a low pressure mercury arc source and a circulating system. Stoichiometrically, the reaction was found to be represented by 6NO → N2 + 2N2O3. Addition of nitrogen decreased the rate, as did also a decrease in the mercury vapor pressure. Using appropriate light filters at 1.7 × 10−3 mm. mercury pressure the decomposition was shown to be photosensitized by Hg (61P1) atoms. The primary process is probably dissociation of nitric oxide into nitrogen and oxygen atoms.
DICUMAROL-2-C14: SYNTHESIS AND METABOLISM STUDIES
Authors: Eisenhauer H. R. , Pepper J. M. , Jaques L. B. , Spinks J. W. T.
Published: May 2006

Dicumarol (3,3′-methylene bis(4-hydroxycoumarin)) has been synthesized labeled with C14 in the 2-position. Starting with active barium carbonate of specific activity 1.6 µc.per mgm., the intermediate compounds diethyl carbonate-1-C14 and 4-hydroxycoumarin-2-C14 were prepared. Subsequent reaction of the latter compound with aqueous formaldehyde yielded dicumarol-2-C14. The specific activity of the final product, once recrystallized from cyclohexanone, was 4.3 × 105 counts per min. per mgm. corrected for geometry and absorption. The expired carbon dioxide from a mouse injected with this C14-labeled product was collected and found to contain no radioactivity. This indicated that, in this animal, the 2-carbon of dicumarol does not enter into a metabolic process whereby it is expired as carbon dioxide.
REACTION OF OXYMERCURIALS WITH HYDRAZINE
Authors: Wright George F
Published: May 2006

The reduction of 2-methoxyalkylmercuric halides by hydrazine hydrate is thought to proceed through mercuri-bis-2-methoxyalkane, which decomposes to give 2-methoxyalkarie radicals. These radicals may lose or gain a hydrogen atom to form 2-methoxyalkene or alkane. The reaction seems to be definitive for structure proof. The bis-mercurial from the (α) 2-methoxycyclohexylmercuric chloride which is formed directly from cyclohexene is less stable than the diastereomeric (β) bis-mercurial, which can be purified by distillation. Conversion of this (β) bis-mercurial to pure β-2-methoxycyclohexylmercuric chloride shows that this reaction occurs by direct replacement. The hydrazine reduction may be used to convert β-1-chloromercuri-2-methoxy-1,2-diphenylethane (from trans-stilbene) to the α-diastereomer. Since the β-isomer in this case is more readily hydrolyzable than the α isomer, and each isomer may be converted cleanly back to its parent alkene, the series of reactions provides a method of converting trans- into cis-stilbene.
THE FLOW OF FLUIDS THROUGH ACTIVATED CARBON RODS.
Authors: Flood E. A. , Tomlinson R. H. , Leger A. E.
Published: May 2006

The flow rates of the vapors of benzene, ethyl chloride, diethyl ether, methanol, and water through activated carbon rods have been found to exceed, considerably, flow rates calculated by classical equations. The excess flow rates show maxima in widely different relative pressure regions and are ascribed to flow of adsorbed material. An empirical equation is presented which correlates the observed flow rates with relevant adsorption isotherms. Classical equations of flow through elliptical and rectangular pipes are discussed with reference to flow through fine-grained porous materials. It is shown that equations of the Adzumi type are roughly valid as applied to fine-grained porous bodies, but that without a knowledge of the frequency distributions of pore sizes and shapes, flow data cannot be related to pore dimensions in any literal sense. End effects are discussed.
THE FLOW OF FLUIDS THROUGH ACTIVATED CARBON RODS: II. THE PORE STRUCTURE OF ACTIVATED CARBON
Authors: Flood E. A. , Tomlinson R. H. , Leger A. E.
Published: May 2006

The flow rates of adsorbable gases through zinc chloride activated carbon rods are considerably greater than might be expected from classical considerations. From data independent of flow measurements, the pore-size frequency distributions of the activated carbon are deduced and a model macropore system presented. It is shown that flow rates of nonadsorbable gases are consistent with a mean macropore diameter of about 3 × 10−5 cm., as well as being consistent with what can be inferred concerning such structures. The macropore system is regarded as an interstitial structure and is described as a random assembly of "bottle necks" joining relatively large void spaces. The assembly is described by means of two constant parameters and one stochastic variable. The mean micro-pore diameter of zinc chloride activated carbons is generally regarded as being of the order of 2 × 10−7 cm. or less. It is shown that no ordinary type of effusive or diffusive flow through pores of the order of 2 × 10−7 cm. can be appreciable compared with the flow through the macropore system, unless surface forces increase flow rates by large factors. In the case of strongly adsorbed gases the anomalous flow rates are ascribed to a flow through the micropore system and hence it is inferred that surface forces introduce large factors tending to increase flow rates in these very small pores.
The Papilionaceous Alkaloids. XVI. Trilupine and Dilupine
Authors: Marion Léo
Published: May 2006

not available
THE PREPARATION OF SODIUM CHLORIDE OF LARGE SPECIFIC SURFACE
Authors: Craig A. , McIntosh R.
Published: May 2006

A procedure is outlined by which sodium chloride particles of specific surface up to 50 m2 per gm. may be prepared. The particles form in chains and are found to lose area rapidly in moist air. The fundamental units of the chain do not appear cubic. Single cubic particles or chains of cubic particles also have been prepared. The one sample identified as this type had a specific surface of 18 m2 per gm. The sintering in moist air appears to occur by a process of solution and recrystallization. A value of the interfacial free energy solid–liquid is calculated from the data.
A NEW SYNTHESIS OF C14 LABELED CYANIDE
Authors: Spyker J. W. , Neish A. C.
Published: May 2006

Sodium formate was converted to sodium cyanide in high yields, usually better than 85%, by heating with two molecular proportions of sodium amide at 620 °C. for 12 min. in a stainless steel bomb. A modified synthesis of sodium formate, from the carbon-14 sodium carbonate solution supplied commercially, is described, yield 95–97%.
The Reduction of Some Chlorinated Azobenzenes with Titanous Sulphate
Authors: Fainer Percy , Myers J. L. , Keirstead K. F.
Published: May 2006

not available
LYCOCTONINE AND ITS OXIDATION PRODUCTS
Authors: Edwards O. E. , Marion Léo
Published: May 2006

The ultraviolet spectra, basic strengths, and N-alkyl groups of the aconite alkaloids are discussed. Pyropseudaconine has been shown to contain a conjugated system. The formulation C19H19–2,(OH)3,(OCH3)4NC2H5has been confirmed for lycoctonine. Study of its oxidation products has shown that lycoctonine has a methylene group adjacent to the nitrogen and a primary hydroxyl group. The two remaining hydroxyls have been shown to be vicinal, with one probably secondary and the other tertiary. A carbinolamine structure is suggested for hydroxylycoctonine. The new bases, isolycoctonine, desoxylycoctonine, and des-(oxymethylene)-lycoctonine are described.
PAPER CHROMATOGRAPHIC SEPARATION OF SOME: BIOLOGICALLY IMPORTANT PHOSPHATE ESTERS
Authors: Mortimer D. C.
Published: May 2006

Any pair of the group of 11 phosphate esters studied may be separated on a paper chromatogram with one of three solvent mixtures: ethyl acetate – acetic acid – water, methyl Cellosolve – methyl ethyl ketone – ammonia water, ethyl acetate – formamide – pyridine. Separation of the components of more complex mixtures usually requires the use of two-dimensional paper chromatography. Position constants for the individual esters with each of the three solvents are listed, and diagrams showing the type of separation pattern obtained by two-dimensional chromatography of mixtures are presented.
THE SYNTHESIS OF PYRIDOCARBAZOLES
Authors: Kulka Marshall , Manske R. H. F.
Published: May 2006

7H-Pyrido(2,3-c)- (IX, R=H) and 7H-pyrido(3,2-c)carbazole (V, R=H) have been synthesized by unambiguous routes and shown to be identical with the products resulting from the Fischer-indole ring closure followed by dehydro-genation of 6- and 7-quinolylhydrazone of cyclohexanone respectively. The cyclization of N-substituted-1,2,3,4-tetrahydro-6- and -7-quinolylhydrazone of cyclohexanone followed by hydrolysis and dehydrogenation resulted in the linear polycyclic systems, 6H-pyrido(3,2-b)- (VIII) and 10H-pyrido(2,3-b)carbazole (IV) respectively. The 12 possible pyridocarbazoles have now been prepared.The structure of the Skraup reaction product of 1-phenyl-5-amino-1-benzo-triazole (X) has been established.
THE NITRATION OF SOME QUINOLINE DERIVATIVES
Authors: Kulka Marshall , Manske R. H. F.
Published: May 2006

Three compounds, namely 1,2,3,4-tetrahydroquinoline, N-acetyl-1,2,3,4-tetra-hydroquinoline, and 5,8-dichloroquinoline, have been nitrated and the nitration products orientated through reduction studies.
STUDIES OF RDX AND RELATED COMPOUNDS: VIII. THERMOCHEMISTRY OF RDX REACTIONS
Authors: Gilpin V. , Winkler C. A.
Published: May 2006

The following heats of reaction have been determined, where the subscripts "c" and "s" refer to solid and solution respectively:Hexamine(c) + HNO3 (97.5%) = RDX(s); ΔH = −88.0 kcal. per mole.Hexamine mononitrate(c) + HNO3 (97.5%) = RDX(s); ΔH = −69.2 kcal. per mole.Hexamine dinitrate(c) + HNO3 (97.5%) = RDX(s); ΔH = −41.7 kcal. permole.Hexamine(s) + Bachmann reagents = RDX(s); ΔH = −140 kcal. per mole.Hexamine mononitrate(s) + Bachmann reagents = RDX(s); ΔH = −126 kcal. per mole.Hexamine dinitrate(c) + Bachmann reagents = RDX(s); ΔH = −118 kcal. per mole.These measurements, together with some on heats of solution of the reagents, indicate that hexamine dinitrate is an intermediate in the direct nitrolysis of hexamine to RDX, but that hexamine mononitrate is a probable intermediate in the Bachmann conversion of hexamine to RDX.
THE BIOGENESIS OF ALKALOIDS: VI. THE FORMATION OF HORDENINE AND N-METHYLTYRAMINE FROM TYRAMINE IN BARLEY
Authors: Leete Edward , Kirkwood Sam , Marion Léo
Published: May 2006

Tyramine-α-C14, synthesized from C14-barium carbonate, was administered to sprouting barley and radioactive hordenine and N-methyltyramine isolated from the roots. Separation of these alkaloids by chromatography followed by degradation showed that all the activity was located in the α -carbon atom. The specific activity of the N-methyltyramine was about 10 times that of hordenine. From the results it is concluded that tyramine undergoes methylation in the barley root to N-methyltyramine and thence to hordenine.
MOLTEN SALTS. ELECTRICAL TRANSPORT IN THE SYSTEM SILVER NITRATE–SODIUM NITRATE
Authors: Aziz P. M. , Wetmore F. E. W.
Published: May 2006

Relative transport fractions have been measured in the molten system silver nitrate - sodium nitrate at 330° over the range 5 to 25 mole% silver nitrate. The individual fractions for silver, sodium, and nitrate ion have been assessed within limits. The results indicate that transport by silver ion is greater than that by sodium ion at the same concentration, although the latter has the smaller radius. The usual assumption that the largest ion (nitrate) does not transport charge is within the interpretation of the results.
On the Liquid–Vapor Coexistence Curve of Xenon in the Region of the Critical Temperature. II
Authors: Weinberger M. A. , Habgood H. W. , Schneider W. G.
Published: May 2006

not available
THE DECOMPOSITION OF HYPOCHLOROUS ACID
Authors: Lister M. W.
Published: May 2006

The rate of decomposition of hypochlorous acid has been measured in aqueous solution in the presence of much sodium hypochlorite. The rate is nearly independent of the hypochlorite concentration, and proportional to the square of the hypochlorous acid concentration. Hence the mechanism proposed is[Formula: see text][Formula: see text]The first step is the slower. The reaction[Formula: see text]also occurs, but is much slower. Oxygen is also evolved, by a first order reaction. Values for the rate constants at different temperatures of all these reactions are given. Measurements are also reported on certain equilibria present in these solutions: the ionization of hypochlorous and chlorous acids, and the reaction [Formula: see text].Details of modified analytical methods for hypochlorite and chlorate in the presence of chlorite are given.
THE REACTION OF ACTIVE NITROGEN WITH PROPYLENE
Authors: Trick G. S. , Winkler C. A.
Published: May 2006

The reaction of nitrogen atoms with propylene has been found to produce hydrogen cyanide and ethylene as the main products, together with smaller amounts of ethane and propane and traces of acetylene and of a C4 fraction. With excess propylene, the nitrogen atoms were completely consumed and for the reaction at 242 °C., 0.77 mole of ethylene was produced for each mole of excess propylene added. For reactions at lower temperatures, less ethylene was produced. The proposed mechanism involves formation of a complex between the nitrogen atom and the double bond of propylene, followed by decomposition to ethylene, hydrogen cyanide, and atomic hydrogen. The ethylene would then react with atomic nitrogen in a similar manner.
MOLTEN SALTS ELECTRICAL CONDUCTIVITY IN THE SYSTEM SILVER NITRATE–SODIUM NITRATE
Authors: Byrne June , Fleming Helen , Wetmore F. E. W.
Published: May 2006

Conductivity and density data have been obtained for the system silver nitrate – sodium nitrate. The Arrhenius energy of activation for electrical migration in sodium nitrate and in the binary melts decreases with rising temperature above the melting point, as was shown previously for silver nitrate. The equivalent conductivity isotherms for the binary melts are almost linear in the mole fraction.
STEROIDS. I. A CASE OF WALDEN INVERSION WITH NUCLEOPHILIC SUBSTITUTION AT POSITION 3 OF Δ5–STEROIDS
Authors: Vavasour G. R. , Bolker H. I. , McKay A. F.
Published: May 2006

When 3(β)-chlorocholest-5-ene is heated with benzylamine, inversion with partial racemization occurs to give a mixture of N-benzyl-3(α)-aminocholest-5-ene and N-benzyl-3(β)-aminocholest-5-ene. The configurations of the N-benzyland N-acetyl-3-aminocholest-5-enes have been determined.The preparation of N,N-bis.-(2-chloroethyl)-3(ξ)-aminocholest-5-ene hydrochloride is described.
INFRARED SPECTRUM, MOLECULAR STRUCTURE, AND THERMODYNAMIC FUNCTIONS OF HYDROXYLAMINE
Authors: Giguère Paul A. , Liu I. D.
Published: May 2006

The absorption spectrum of pure hydroxylamine in the vapor and solid states was measured with a prism instrument in the range 1.5–25 µ. Except in one case the fundamental vibrations were clearly outlined and in some instances, particularly the 1115 cm−1 band, the fine structure was resolved well enough for a significant calculation of the rotational constants. From the latter it was possible to confirm, within fairly close limits, the probable structure of the hydroxylamine molecule, a nearly symmetric top of point group Cs. At least two of the bands appeared to be doubled owing, presumably, to existence of a mixture of cis-and trans-forms of the molecule. The O—H and N—H distances have nearly the same value as in water and ammonia respectively and the N—O distance is 1.46 Å.The thermodynamic functions of gaseous hydroxylamine were calculated using the observed fundamental frequencies; some uncertainty accrues from the torsional oscillation. The infrared spectrum of crystalline hydroxylamine hydrochloride was also studied.
CYANOACETIC ESTERS, AMINO ACIDS, AND PYRAZOLONES
Authors: Boivin Paul A. , Gagnon Paul E. , Renaud Ernest , Bridgeo William A.
Published: May 2006

Ethyl α-substituted cyanoacetates were used to prepare hydrazides, azides, urethanes, and dl-α-amino-β-phenylbutyricacid, dl-α-amino-δ-o-bromophenoxyvaleric acid, and dl-α-amino-δ-o, p-dichlorophenoxyvaleric acid. Ethyl mono- and disubstituted cyanoacetates with hydrazine gave hydrazides which were transformed by treatment with sodium hydroxide into 4-α-phenylethyl-, 4-m-ethylphenoxyethyl-, 4-o-bromophenoxypropyl-, 4-o,p-dichlorophenoxypropyl-, 4,4-m-ethylphenoxy-ethyl-, and 4,4-m-methylphenoxypropyl-3-amino-5-pyrazolones. The ultraviolet absorption spectra of the pyrazolones were determined in neutral, acid, and alkaline solutions and their structures established.
A STUDY OF ADSORPTION HYSTERESIS BY MEANS OF LENGTH CHANGES OF A ROD OF POROUS GLASS
Authors: Amberg C. H. , McIntosh R.
Published: May 2006

From adsorption data and measurements of length changes of a porous glass rod, a qualitative description of the processes involved in the adsorption of water vapor is developed. Particular attention is devoted to the causes of the hysteresis loop. The qualitative theory appears to be useful in understanding the adsorption of water on charcoal, and may therefore be of value in interpreting the phenomenon of limited hysteresis on any porous adsorbent.Three attempts to test the theory quantitatively are presented. These involve the computation of surface areas, of Young's moduli, and of isosteric heats of adsorption. The quantitative treatment also leads to an estimate of the total number of pores and the mean length of the pores, in addition to the pore radius. Such an assessment of a porous structure has apparently not been possible earlier.
THE MOBILITY OF OIL DROPLETS, INTERFACIAL TENSION MEASUREMENTS, AND GEGEN ION ADSORPTION IN SOAP SOLUTIONS
Authors: Powell B. D. , Alexander A. E.
Published: May 2006

The electrophoretic mobility of oil droplets, in oil in water emulsions stabilized with paraffin chain salts, have been determined, together with interfacial tension measurements on the same systems, and the observations are explained. Electrokinetic theory is discussed and an estimate made of the fraction of the gegen ions which are bound to the droplet; the value of this fraction is similar to that found by others for the spherical soap micelle.
THE REACTION OF ACTIVE NITROGEN WITH ETHYLENE
Authors: Versteeg J. , Winkler C. A.
Published: May 2006

Reinvestigation of the active nitrogen–ethylene reaction has confirmed hydrogen cyanide as the principal product. Smaller quantities of ethane, cyanogen, acetylene, and methane have also been found and the variations in amounts of these products with ethylene flow rate have been established. No significant amount of polymeric material was found.
THE FISSION YIELD OF Te134
Authors: Yaffe L. , Day Alison E. , Greer Betsy A.
Published: May 2006

The fission yield of Te134 has been found to be 6.48% ± 0.47%. This makes the cumulative yield of I134 7.71% using Glendenin's value of 0.19 as the independent fractional chain yield of I134. This value, since it is very close to that found by Thode for Xe134, offers additional confirmation of the 54 min. iodine assignment to mass 134.
PHTHALIDE FORMATION: II. CONDENSATIONS WITH 3-HYDROXY-4-METHYLBENZOIC ACID
Authors: Charlesworth E. H. , Anderson H. J. , Thompson N. S.
Published: May 2006

The condensation of 3-hydroxy-4-methylbenzoic acid with aqueous formaldehyde and hydrochloric acid yields the lactone of 6-hydroxymethyl-1,3-benzodioxane-8-methyl-5-carboxylic acid. This dioxanylphthalide has also been produced in a similar type of condensation from 5-hydroxy-4-methylphthalide which can be obtained by demethylation with aluminum chloride of 5-methoxy-4-methylphthalide.Proof of the presence of the m-dioxane and phthalide rings in the condensation product has been obtained by opening these rings in succession. The action of alkaline permanganate opens the phthalide ring to yield a substituted phthalic acid. Acid hydrolysis then opens the m-dioxane ring with loss of formaldehyde and the formation of a new phthalide ring. Successive steps of decarboxylation, methylation, and oxidation of the new phthalide yield the known 3-methyl-4-methylphthalic acid.
THE PYROLYSIS OF CALCIUM SALTS OF CARBOXYLIC ACIDS
Authors: Lee C. C. , Spinks J. W. T.
Published: May 2006

not available
THE BIOGENESIS OF ALKALOIDS: VII. THE FORMATION OF HORDENINE AND N-METHYLTYRAMINE FROM TYROSINE IN BARLEY
Authors: Leete Edward , Marion Léo
Published: May 2006

Feeding dl-tyrosine-2-C14 to sprouting barley resulted in the formation of radioactive hordenine and N-methyltyramine in the roots. Isolation and degradation of these alkaloids showed that all the activity was located in the α-carbon atom of the side chain, thus indicating that tyrosine is a precursor of N-methyltyramine and hordenine.