bluuebunny/crossref_metadata_2025 huggingface dataset:
THE ACETYL GROUP MIGRATIONS IN D-GLUCOSE DIETHYL THIOACETYL TETRAÁCETATE
Authors: Lemieux R.U. , Bauer H. F.
Published: May 2006

The D-glucose diethyl thioacetal tetraacetate prepared by Wolfrom and associates both by detritylation of 6-O-trityl-D-glucose diethyl thioacetal tetraacetate and mercaptalation of 2,3,4,6-tetra-O-acetyl-β-D-glucose was obtained by direct acetylation of D-glucose diethyl thioacetal with acetic anhydride and sodium acetate. Methylation of the tetraacetate followed by deacetylation and demercaptalation gave only 2-O-methyl glucose and methyl β-D-glucopyranoside.
THE KINETICS OF THE PYROLYSIS OF ETHYL AND ISOPROPYL FORMATES AND ACETATES
Authors: Blades Arthur T.
Published: May 2006

The pyrolysis of ethyl formate, isopropyl formate, ethyl acetate, and isopropyl acetate has been carried out under conditions which favor the decomposition of these esters into the corresponding acid and alkene to the exclusion of side reactions. The rate expressions found were: ethyl formate, k = 2.13 × 1011e−44,140 ± 200/RT sec−1; isopropyl formate, k = 3.8 × 1012e−44,000 ± 100/RT sec−1; ethyl acetate, k = 3.06 × 1012e−47,750 ± 100/RT sec−1; isopropyl acetate, k = 1.00 × 1013 e−45,000 ± 100/RTsec−1. The nature of the transition state is discussed and compared with that for similar decompositions.
THE SILVER CATALYZED OXIDATION OF ETHYLENE: III. KINETICS OF ETHYLENE OXIDE OXIDATION
Authors: Orzechowski A. , MacCormack K. E.
Published: May 2006

A flow type apparatus was used for kinetic studies of the silver catalyzed oxidation of ethylene oxide (EtO) by oxygen at 274 °C. Using N2 as diluent the concentrations of O2 and ethylene oxide were varied independently from 9.9 to 79% and 2.35 to 9.4% respectively while a total pressure of 1 atmosphere was maintained. Flow rates were varied to give a range of contact times varying from 0.06 to 0.25 sec. It was shown that EtO is oxidized without previous dissociation into C2H4 and O2. The dependence of the initial rate of oxidation of EtO on reactant concentrations excludes isomerization of EtO (to acetalde hyde) as a main step in its oxidation, and a direct oxidation mechanism is suggested. The results of a few experiments to determine the extent of isomerization of EtO to acetaldehyde in the absence of oxygen are presented. No steady state could be achieved but the results may be used semiquantitatively to support the belief that isomerization is not the rate determining step in the oxidation of ethylene oxide.
THE SILVER CATALYZED OXIDATION OF ETHYLENE: IV. REACTION MECHANISM
Authors: Orzechowski A. , MacCormack K. E.
Published: May 2006

A reaction mechanism for the silver catalyzed oxidation of C2H4 by oxygen has been formulated which is consistent with kinetic data for this system. It is suggested that both ethylene oxide and CO2 formation involve interaction of single gaseous C2H4 molecules with single oxygen adatoms. This may be a system of two parallel reactions of different activation energy requirements or a common initiation step to form adsorbed ethylene oxide which may then desorb immediately or isomerize to acetaldehyde followed by rapid oxidation to CO2 and H2O. Account is taken of the known adsorption characteristics of O2 on silver to deduce expressions for initial rates of ethylene oxide and CO2 formation as a function of reactant partial pressures. The generalized form of the equation is r = k(1 + a/pE + b/pO)−1, where k, a, and b are temperature dependent constants and pE and pO are partial pressures of ethylene and of oxygen respectively.A mechanism is also suggested for the heterogeneous oxidation of ethylene oxide which involves interaction between a gas phase ethylene oxide molecule and a single oxygen adatom to form an intermediate (probably formaldehyde) which is rapidly oxidized to CO2 and H2O. A similar expression to that above for the initial oxidation rate is deduced. These expressions have been fitted successfully to experimental data.
ATISINE: THE HETEROCYCLIC RING AND FUNCTIONAL GROUPS
Authors: Edwards O. E. , Singh Tara
Published: May 2006

Evidence is presented which confirms the presence in atisine and isoatisine of vinylamine double bonds, an N-(β-hydroxyethyl) group, an exocyclic methylene group, and a secondary hydroxyl in an allylic relation to the latter. The size and substitution of the heterocyclic ring is discussed. The pyrolysis of atisine and isoatisine hydrochlorides to give a C20H29ON base is described.
ORGANIC DEUTERIUM COMPOUNDS: XI. SYNTHESIS OF 1-CHLORO-1-ALKYNES AND 1-CHLORO-1-PROPYNE-d3
Authors: Morse A. T. , Leitch L. C.
Published: May 2006

Dehydrohalogenation of cis-1,2-dichloro-1-alkenes, RCCl═CHCl, with potassium hydroxide in butanol has been used to prepare a number of new 1-chloro-1-alkynes, viz. 1-chloro-1-propyne-d3, 1-chloro-1-propyne, 1-chloro-1-butyne, and 1-chloro-1-pentyne in good yields. The last three compounds were also prepared by chlorination of 1-propyne, 1-butyne, and 1-pentyne with sodium hypochlorite.
SOME OBSERVATIONS ON DETERMINING DENSITY OF FLUIDS BY THE FALLING DROP METHOD
Authors: Sims R. P. A.
Published: May 2006

The shape of the calibration curve obtained with a commercial Falling Drop apparatus has been investigated for drops varying in viscosity and surface tension and in media of varying solvent power. Drop velocity affects drop shape when the viscosity of the drop substance is low, and drop volume when the medium exerts solvent action on the drop. "End effect" appears to be significant even when "wall effect" is large.
ANALOGUES OF 2,2′-BIPYRIDYL WITH ISOQUINOLINE AND THIAZOLE RINGS. PART I
Authors: Knott R. F. , Breckenridge J. G.
Published: May 2006

Several analogues of 2,2′-bipyridyl, with isoquinoline, thiazole, and pyridine rings in various combinations, have been synthesized, and the effect of substituent groups in certain positions in the molecules studied with respect to their ability to react with cuprous and ferrous ion (the "cuproin" and "ferroin" reactions). The results agree with earlier work, and emphasize the desirability of two substituent groups "ortho" to the nitrogen atoms if a stable and sensitive cuprous ion reagent is wanted. The presence of one ortho substituent makes the reagent ineffective toward reaction with ferrous ion. Two of the compounds synthesized had groups in positions which did not allow a coplanar cis configuration of the molecule, and only in these cases were dipicrates formed; this situation is explained by assuming that hydrogen bond formation between the nitrogen atoms is not possible.
SPECTRES D'ABSORPTION INFRAROUGES DES URÉES SUBSTITUÉES
Authors: Boivin Jean L. , Boivin Paul A.
Published: May 2006

not available
A NOTE ON THE USE OF INDIUM FOR REMOVAL OF MERCURY VAPOR IN VACUUM SYSTEMS
Authors: Heyding R. D. , Flood E. A.
Published: May 2006

It is shown that metallic indium adsorbs mercury vapor quite rapidly after a short induction period. It is suggested that indium may be found useful in removing traces of mercury vapor from vacuum systems.
DERIVATIVES OF CHLOROBENZENE-2,4-DISULPHONIC ACID
Authors: Kulka Marshall
Published: May 2006

Chlorobenzene-2,4-disulphonates (II), -disulphones (IV), and -disulphonamides (V) have been prepared from chlorobenzene-2,4-disulphonyl chloride (I). The properties and reactions of I–V have been compared with those of related derivatives of p-chlorobenzenesulphonic acid and phenoxybenzene-4,4′-disulphonic acid.
DIHYDRO-N-norGELSEMINE AND SOME OF ITS DERIVATIVES
Authors: Habgood Thelma , Marion Léo
Published: May 2006

Treatment of gelsemine with cyanogen bromide produced N-cyano-norgelsemine which on catalytic hydrogenation gave rise to N-cyanodihydro-N-norgelsemine, identical with the product of the reaction of cyanogen bromide with dihydrogelsemine. N-Cyanodihydro-N-norgelsemine was hydrolyzed with hydrochloric acid to dihydro-N-norgelsemine which readily formed a mono- or a dibenzoyl derivative according to the conditions, and a p-toluenesulphonamide. The action of phosphorus pentachloride on the monobenzoyl derivative gave rise to N-benzoylchlorodihydro-N-norgelsemine, hydrolyzable by hydrochloric acid to chlorodihydro-N-norgelsemine. This chloro compound was converted by the action of formaldehyde and formic acid to chlorodihydrogelsemine, identical with the product of the action of phosphorus pentachloride on dihydrogelsemine. Chlorination of dihydrogelsemine with chlorine produced dichlorogelsemine.
TWO SYNTHESES OF 1,5:3,6-DIANHYDRO-2,4-O-METHYLENE-D-GLUCITOL: STABILITY OF THE METHYLENE ACETAL BRIDGE TOWARD AQUEOUS ACID
Authors: Baker Samuel B.
Published: May 2006

1,5:3,6-Dianhydro-2,4-O-methylene-D-glucitol has been synthesized by two wholly independent routes. The methylene acetal bridge was found to be stable in hot water and dilute aqueous acid and thus differs from the methylene bridges in 1,4:3,6-dianhydro-2,5-O-methylene-D-mannitol and in the D-iditol analogue of the latter compound. It is suggested that this difference may be due to the ease of folding of the glucitol derivative as compared to the rigidity of the mannitol and iditol structures.
THE BIOGENESIS OF ALKALOIDS: X. THE ORIGIN OF THE N-METHYL GROUPS OF THE ALKALOIDS OF BARLEY
Authors: Leete Edward , Marion Léo
Published: May 2006

Sodium formate-C14and C14-methyl-D- and L-methionine were each fed to sprouting barley under identical conditions and radioactive alkaloids were isolated from the leaves and roots. Degradation of these alkaloids showed that the D- and L-methionines were an equally efficient source of.the methyl groups of N-methyltyramine and hordenine, the root alkaloids; but D-methionine was a less efficient source than L-methionine of the methyl groups of gramine, from the leaves. The formate was a source of the methyl groups of all the alkaloids, however, less efficient than the methionines, and a very poor source for the methyl groups of gramine. The significance of these results is discussed.
ROTAMERISM DURING DEMETHYLATION OF THE 2,5-DIMETHOXY-2,5-DIMETHYL-3,4-DIPHENYLHEXANES
Authors: Smith J. G. , Wright George F
Published: May 2006

The fission of methanol from the diastereomeric 2,5-dimethoxy-2,5-dimethyl-3,4-diphenylhexanes leads to products which are best explained in terms of restriction about the central carbon-carbon bond. As would be expected from its stable conformation the dd,ll diastereomer easily forms the 2,2,5,5-tetramethyl-3,4-diphenyltetrahydrofuran, but the meso diastereomer forms a tetrahydrofuran with difficulty. On the other hand the meso diastereomer readily undergoes Friedel-Crafts types of condensation leading in different media to either 3,3-dimethyl-1-isopropenyl-2-phenylindane, 3,3-dimethyl-1-isopropyl-2-phenylindene or 5,5,10,10-tetramethyl-4b,5,9b, 10-tetrahydroindeno[2,1-α]-indene. These indenes are the expected products from a consideration of the conformation of the meso-dimethoxydimethyldiphenylhexane which is most free from steric restriction.
DIELECTRIC RELAXATION IN CELLULOSE CONTAINING SORBED VAPORS
Authors: Seidman R. , Mason S. G.
Published: May 2006

The dielectric constant and dielectric loss factor were measured in a dispersion region for a paper of high cellulose content. The complex arrangement of the paper in the measuring condenser did not effectively alter the position of the dispersion region of the paper itself, as shown by electrical analysis. From this analysis equations were derived from which the dielectric constant and maximum dielectric loss factor of the cellulose fiber were evaluated for varying amounts of sorbed water, methanol, and ethanol. The effect of each of these vapors on the position of the dispersion region was studied, measurements being performed over a range of frequency of 10 to 1000 kc.p.s., and a range of temperature of −58 to 26 °C. A typical plasticizing action was observed in all three cases. This was confirmed from an analysis of the data using the theory of absolute reaction rates.
THE THERMAL DECOMPOSITION OF DIMETHYL DISULPHIDE
Authors: Coope John A. R. , Bryce W. A.
Published: May 2006

The thermal decomposition of dimethyl disulphide has been studied in the gaseous state by a static method. The primary reaction, which follows a reproducible induction period, produces one mole of methyl mercaptan per mole of disulphide, together with a product of low volatility believed to be a thioformaldehyde polymer:[Formula: see text]There is also a competing reaction producing a large quantity of hydrogen sulphide. The remaining volatile products, hydrocarbons of two or more carbon atoms (believed to be chiefly ethylene), free sulphur, polysulphides, and carbon disulphide are formed either by the latter reaction or by the extensive decomposition of products. The decomposition is catalyzed by hydrogen sulphide, and more strongly by the complete reaction mixture. A mechanism is proposed for the main reaction.
THE CHARACTERIZATION OF DELCOSINE AND SOME OF ITS DERIVATIVES
Authors: Taylor W. I. , Walles W. E. , Marion Léo
Published: May 2006

Reanalysis of delcosine and several of its derivatives shows that the most likely empirical formula is C24H39O7N. Delcosine has been shown to be identical with Goodson's base C. Acetylation produces monoacetyldelcosine, identical with Goodson's naturally occurring base B. It has been possible to prepare two isomeric diacetyl derivatives, one of which has been reported previously, and a further acetylated compound also reported previously which seems to have lost the elements of water. A dipropionyldelcosine is also described. The base contains three methoxyls and four hydroxyls, only two of which are acetylated readily.
ORGANIC DEUTERIUM COMPOUNDS: XII. BENZENE-d6
Authors: Leitch L. C.
Published: May 2006

not available
SYNTHESES AND ABSORPTION SPECTRA OF 2-SUBSTITUTED-3-HYDROXY-5-PYRAZOLONES: 4-n-HEXYL-5-PYRAZOLONES-4-C14
Authors: Gagnon Paul E. , Boivin Jean L. , MacDonald Roderick , Yaffe Leo
Published: May 2006

2-Monosubstituted-3-hydroxy-5-pyrazolones were prepared from diethyl malonate itself and diethyl malonates monosubstituted with methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, and benzyl groups by condensation of the esters with o-, m-, and p-chlorophenylhydrazines, and n-hexylhydrazine. By using diethyl n-hexyl malonate-2-C14 and o-, m-, and p-chlorophenylhydrazines, and n-hexylhydrazine as starting materials the corresponding pyrazolones labelled with C14 were obtained. Their specific activities were 7.0, 8.8, 9.0, and 8.8 µc./gm. respectively. Ultraviolet absorption spectra were determined in neutral and alkaline solution and the infrared spectra were also obtained. From the data it was possible to ascribe the tautomeric structures best suited for the compounds.
MOLTEN SALTS: VISCOSITY OF SILVER NITRATE
Authors: Pugsley F. A. , Wetmore F. E. W.
Published: May 2006

Precise values for the viscosity of silver nitrate show that Frenkel's relation for comparison of the temperature dependence of viscosity and conductivity is valid for this system and that the energy of activation for viscous flow is proportional to that for electrical transport over a range of temperature.
SOME THERMODYNAMIC PROPERTIES OF HYDROCARBONS ADSORBED ON RUTILE
Authors: Schreiber H. P. , McIntosh R.
Published: May 2006

Differential thermodynamic properties of methane, ethane, propane, and n-butane adsorbed on rutile have been determined from isotherms over appreciable temperature ranges. Ordinary experimental techniques failed to yield reliable data in low temperature and surface coverage regions, but essentially simple modifications of these resulted in accurate thermodynamic values. For methane, the results compared well with similar ones computed by Pace, Heric, and Dennis from data obtained by means of calorimetry. Maximum error in isosteric heats of adsorption was 60 cal. mole−1; in differential molar entropies 0.8 cal. mole−1 degree−1. The thermodynamic properties of methane and ethane are similar but there is a departure in the set pattern for propane. A large change was observed in the heat of adsorption of propane, near 185° K. and surface coverages lower than 0.6 of the monolayer. A phase transition is suggested to account for this occurrence.
THE STRUCTURE OF THE THIURAM OXIDES
Authors: White Robert W.
Published: May 2006

The compounds identified by previous investigators as thiocarbamyl oxides (commonly known as "thiuram oxides") are shown to be, instead, the isomeric thiocarbamyl carbamyl sulphides.
THE SYNTHESIS OF UROPORPHYRIN I
Authors: MacDonald S. F. , Stedman R. J.
Published: May 2006

The analytical proof of H. Fischer's structure for uroporphyrin I has been completed, and the structure confirmed by synthesis.
DIPHENYLCYANAMIDE DERIVATIVES: II. 4,4′-DIMETHOXYDIPHENYLCYANAMIDE
Authors: Robinson J. R.
Published: May 2006

The synthesis of 4,4′-dimethoxydiphenylcyanamide has been accomplished by treatment of 4,4′-dimethoxydiphenylamine with cyanogen chloride or alternatively by removal of the elements of water from N,N-bis(4-methoxyphenyl)urea. These reactions may be reversed by hydrolysis of the cyanamide with alcoholic or aqueous alkali, respectively. This nitrogen analogue of methoxychlor exhibits a very slight toxic effect on mosquito larvae (Aedes aegypti (L.)).
FREE RADICAL MECHANISMS IN THE MERCURY PHOTOSENSITIZED REACTION OF HYDROGEN WITH ACETYLENE
Authors: Cashion J. K. , Roy D. J. Le
Published: May 2006

The Hg(3P1) photosensitized reaction of hydrogen with acetylene has been investigated with particular emphasis being placed on the identification of products and their dependence on hydrogen pressure. The results have been interpreted in terms of a number of elementary reactions in which vinyl and ethyl radicals play an important part.
AROMATIC HYDROXYLAMINES AS ORGANO-ANALYTICAL REAGENTS
Authors: Lutwick G. D. , Ryan D. E.
Published: May 2006

The investigation of the use, as analytical precipitants, of a number of aromatic phenylhydroxylamines is described. In general they react similarly, increasing in selectivity with an increase in acidity of the oxime group. In acid solutions (1% or more) only vanadium, tin, titanium, and zirconium are precipitated. Their variation in reaction with copper and the nature of their reaction with tin are described. All compounds can act as oxidants or rėductants with an oxidation potential of approximately −1.2 volts.
UNIT CELL, SPACE GROUP, AND INDEXED X-RAY DIFFRACTION POWDER DATA FOR CERTAIN NARCOTICS: I. CODEINE MONOHYDRATE, CODEINE (ANHYDROUS), DIHYDROCODEINONE
Authors: Barnes W. H. , Forsyth W. J.
Published: May 2006

not available
UNIT CELL, SPACE GROUP, AND INDEXED X-RAY DIFFRACTION DATA FOR CERTAIN NARCOTICS: III. dl-ALPHAPRODINE HYDROCHLORIDE, dl-BETAPRODINE HYDROCHLORIDE
Authors: Barnes W. H. , Forsyth W. J.
Published: May 2006

not available
UNIT CELL, SPACE GROUP, AND INDEXED X-RAY DIFFRACTION POWDER DATA FOR CERTAIN NARCOTICS: V. PAPAVERINE, PAPAVERINE HYDROCHLORIDE
Authors: Barnes W. H.
Published: May 2006

not available
REARRANGEMENT STUDIES WITH C14: II. THE PREPARATION OF 2-PHENYLETHYL HALIDES
Authors: Lee C. C. , Spinks J. W. T.
Published: May 2006

The 2-phenylethyl halides were prepared from the treatment of 2-phenylethanol-1-C14 with thionyl chloride alone, thionyl chloride in pyridine, 48% hydrobromic acid, 55% hydroiodic acid, or phosphorus and iodine. Except for the reaction with thionyl chloride in pyridine, these reactions gave rise to some rearrangement of the C14 activity from the C-1 to the C-2 position. It appears probable that these rearrangements resulted from reactions having the SN1 type of mechanism with the phenylethyl cation as reaction intermediate. The fact that the thionyl chloride in pyridine treatment leads to a product without rearrangement is of interest in that this method may have further applications in synthetic tracer chemistry.
THE POLAROGRAPHIC REDUCTION OF AMARANTH
Authors: McKeown G. G. , Thomson J. L.
Published: May 2006

Amaranth, a food color, has been studied polarographically over a pH range of 2.0 to 10.0 in aqueous solution and was found to give a well-defined wave, diffusion controlled and suitable for quantitative work. Irreversibility was indicated by the behavior of the half-wave potential to changes in pH and concentration. With pH, a direct relationship of −0.080 v. per pH unit held between pH 2.0 and 7.0, while with concentration, the half-wave potential was found to apparently vary directly with the logarithm of concentration. Using a coefficient of diffusion value obtained by conductance measurements the value of n for the reaction was calculated to be 4, which corresponds to a rupture of the azo group to yield the corresponding amines.
ON THE DRYING OF DIALYZED LIGNINSULPHONIC ACID
Authors: Newcombe Alan G.
Published: May 2006

To evaluate the effect of drying temperature on the composition of high molecular weight ligninsulphonic acids, samples of a dialyzed ligninsulphonic acid solution were dried in several ways. Analyses showed that heating the solution to 70 °C for 16 hr. did not give an anhydrous material. When this material was heated for an additional period of 22 hr. at 90 °C, it became anhydrous and also lost part of its sulphur content. Air drying of either the free acid or the calcium salt, followed by grinding and drying in vacuo to constant weight, produced materials with essentially the same elemental composition after allowance was made for the calcium content, and because of this it is concluded that no decomposition of the free acid occurred during this drying process. Elementary analyses were in good agreement with those reported by other workers. The hydroxyl content found for the free acid was lower, and the oxygen content was higher, than the corresponding values reported by Erdtman, Lindgren, and Pettersson or those reported by Freudenberg, Lautsch, and Piazolo.
THE ELECTRICAL CONDUCTANCES OF AQUEOUS SOLUTIONS OF SILVER NITRATE AND OF AMMONIUM NITRATE AT THE TEMPERATURES 221.7 °C. AND 180.0 °C, RESPECTIVELY
Authors: Campbell A. N. , Kartzmark E. M. , Bednas M. E. , Herron J. T.
Published: May 2006

The specific and equivalent conductances (which also involve the densities) of aqueous solutions of silver nitrate and of ammonium nitrate, ranging in concentration from 0.1 M to that of the pure molten salt, have been determined at temperatures of 221.7 °C and 180.0 °C, respectively. It has been found that when the equivalent conductance is plotted against logarithm of the concentration, a straight line is obtained in the region of concentrations greater than about 6 M or less. Hence the equivalent conductance can be calculated from the relation[Formula: see text]where D = the slope and Λa = equivalent conductance at the limiting experimental concentration, Ca (in the molten state).
THE OXIDATION OF CARBON MONOXIDE BY SOLID PERMANGANATE REAGENTS: VII. THERMAL DECOMPOSITION OF SILVER PERMANGANATE
Authors: Grant G. A. , Katz Morris
Published: May 2006

The thermal decomposition in a vacuum at 100 °C of both whole and ground crystals of pure dry silver permanganate was followed by the measurements of increase in pressure and of loss in weight. The decomposition products were determined by analysis and calculations to be silver oxide, silver, manganese dioxide, silver permanganite, and oxygen. On the basis of chemical analysis the following mechanism of decomposition is proposed:(1)[Formula: see text](2)[Formula: see text](3)[Formula: see text]The reaction proposed in equation (1) goes to completion, while the reaction proposed in equation (2) goes to approximately 37.7% completion, and that in equation (3) goes to approximately 6.6% completion.
LIGHT-SCATTERING AND SEDIMENTATION STUDIES OF BOVINE SERUM ALBUMIN AT LOW pH
Authors: Reichmann M. E. , Charlwood P. A.
Published: May 2006

Light-scattering measurements of bovine serum albumin made at pH 1.9 in 0.1 M-0.45 M potassium chloride show that the molecule is not dissociated, but has the same molecular weight as in neutral solution. At pH 1.9 in the absence of salt aggregation occurs, the extent increasing with time. The sedimentation constant at pH 1.9 increases from 3.2S in 0.1 M potassium chloride to 3.6 in the 0.5 M salt, compared with 4.3 in neutral solution. These differences are ascribed to changes of molecular shape.
THE BIOGENESIS OF ALKALOIDS: XII. THE MODE OF FORMATION OF THE TROPINE BASE OF HYOSCYAMINE
Authors: Leete Edward , Marion Léo , Spenser Ian D.
Published: May 2006

Ornithine-2-C14was fed to mature Datura stramonium plants and radioactive hyoscyamine was isolated from the whole plant, while the hyoscine obtained from the plant was inactive. Systematic degradation of the radioactive alkaloid indicated that all the activity was present in the 1 or 5, or both, positions of the tropine half of the alkaloid indicating that ornithine is a precursor of the ring system in tropine, but not of scopine, the base present in hyoscine.
A NEW CONCEPT ON THE MECHANISM OF AUTOXIDATION OF METHYL OLEATE, LINOLEATE, AND LINOLENATE
Authors: Khan N. A.
Published: May 2006

not available
ANTITUBERCULOUS ISONICOTINYLHYDRAZONES OF LOW TOXICITY
Authors: Zubrys A. , Siebenmann C. O.
Published: May 2006

In a search for antituberculous compounds of low toxicity, the isonicotinylhydrazones of monohydroxybenzaldehydes and of the corresponding aldehydophenoxyacetic acids were prepared. When tested inνiνo, the isonicotinylhydrazones of 2-formyl-phenoxyacetic acid and of 6-methoxy-2-formyl-phenoxyacetic acid showed the most marked antituberculous activity combined with low toxicity. The preparation of 6-methoxy-2-formyl-phenoxyacetic acid and of the isonicotinylhydrazone of 2-formyl-phenoxyacetic acid are described as representative examples. The results of microanalysis include data which define the antituberculous isonicotinylhydrazones of 2-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and 2-hydroxy-3-methoxybenzaldehyde (o-vanillin).
THE ALKALINE NITROBENZENE OXIDATION OF ASPEN WOOD AND LIGNIN MODEL SUBSTANCES
Authors: Kavanagh K. R. , Pepper J. M.
Published: May 2006

The yields of vanillin and syringaldehyde obtained by the alkaline nitrobenzene oxidation of aspen wood meal have been determined at various temperatures for various times. The maximum yield of each of these aldehydes, ca. 15 and 36% respectively, was obtained under the same conditions. Similar maximum yields result at 130 ± 5 °C. as at 170 ± 5 °C. if the reaction time is markedly increased. Treatment of the wood meal with sodium hydroxide at 160 °C. for two and one half hours prior to the addition of nitrobenzene and subsequent heating under the same conditions decreases, by over 30%, the yields of aldehydes. Samples of 3,4,5-trimethoxybenzaldehyde, β-D-glucovanillin, and β-D-glucosyringaldehyde were oxidized by alkaline nitrobenzene at 160 °C. for two and one half hours and yields of the corresponding phenolic aldehydes of 10.7, 69.6, and 71.9% respectively were obtained. These results are discussed with respect to the chemistry of aspen lignin.
SOME COMPLICATING FACTORS IN THE PHOTOLYSIS OF ACETONE
Authors: Ausloos P. , Steacie E. W. R.
Published: May 2006

The photolysis of acetone has been investigated at room temperature using low pressures and high intensities. In addition an investigation was made of the photolysis of azomethane–acetone mixtures. The results indicate that the curvature at low temperatures of Arrhenius plots of[Formula: see text][Acetone] is due to two causes (a) a reaction between methyl radicals and adsorbed acetone and (b) to the occurrence of the disproportionation reaction

[Formula: see text]Confirmatory evidence for wall effects was obtained from experiments at low pressures and higher temperatures.
STUDIES IN THE POLYOXYPHENOL SERIES: VII. THE OXIDATION OF VANILLIN WITH SODIUM CHLORITE AND CHLORINE DIOXIDE
Authors: Husband R. M. , Logan C. D. , Purves C. B.
Published: May 2006

Vanillin almost instantly reduced 1.2 to 1.5 moles of aqueous chlorine dioxide at 20 °C. or 5 °C. and any pH between 1.2 and 6.5, and a white crystalline substance with the composition of a dihydroxyvanillin, C7H5O4(OCH3), was isolated in roughly 25% yield independently of the pH. When oxidized with aqueous sodium chlorite at 20 °C. and pH 0.5, these crystals gave another crystalline substance with the composition of a dihydroxyvanillic acid, C7H5O5(OCH3). Although both these substances decomposed readily to red oils and then to brown powders free of methoxyl groups, seven well characterized derivatives were prepared. The results showed that the substances were unsaturated, monohydroxy, diketone tautomers of a dihydroxyvanillin and the corresponding dihydroxyvanillic acid, but precise structures could not be assigned. Parallel oxidations of vanillin with aqueous sodium chlorite at 20 °C. and pH 6 proceeded at a negligible rate, but near pH 5 a reaction that often seemed autocatalytic produced about 19% of 5-chlorovanillin. At pH 4 the aldehyde C7H5O4(OCH3) was isolated in 19% yield; at pH 1 this aldehyde (15%) was mixed with 7.7% of the corresponding acid C7H5O5(OCH3), but at pH 0.5 the latter alone was produced (28%). Chlorine dioxide and sodium chlorite therefore differed markedly in their oxidizing action and in the effect of pH upon it. When acting on vanillin, both oxidants also produced deep red, unstable oils with quinone-like properties and often containing chlorine.
A COMPARISON OF THE PROPERTIES OF PENTAACETATES AND METHYL 1,2-ORTHOACETATES OF GLUCOSE AND MANNOSE
Authors: Lemieux R. U. , Brice Carol
Published: May 2006

The rates of exchange of acetate—concurrent with anomerization—between the C1-acetoxy groups of the pentaacetates (0.05 M) of D-glucose and D-mannose and stannic trichloride acetate (0.05 M) in chloroform containing stannic chloride (0.05 M) were determined at 40 °C. using isotopically labelled acetate. 1,2-trans-α-D-Mannose pentaacetate underwent exchange seven times more rapidly than the β-1,2-cis-anomer but eight times less rapidly than 1,2-trans-β-D-glucose pentaacetate. The latter compound was 450 times more reactive than the α-1,2-cis-anomer. In accordance with these results, the D-mannose pentaacetate underwent mercaptolysis in ethyl mercaptan containing zinc chloride at rates intermediate to those found for the D-glucose pentaacetates. The main product from the mannose pentaacetates was in each case ethyl 1,2-trans-α-D-1-thiomannopyranoside tetraacetate (60–70% yield). Tetra-O-acetyl-β-D-glucopyranosyl chloride with silver acetate gave β-D-glucose pentaacetate when the reaction was carried out in dry acetic acid but gave 2,3,4,6-tetra-O-acetyl-α-D-glucose in 90% aqueous acetic acid. Tetra-O-acetyl-β-D-glucopyranosyl chloride with methanol and silver carbonate gave a sirupy product with the properties expected for methyl 1,2-ortho-O-acetyl-α-D-glucopyranose triacetate. The substance was hydrolyzed by 0.005 N hydrochloric acid in 95% dioxane 18 times more rapidly than the corresponding derivative of β-D-mannose. The significance of these observations toward an understanding of the effect of configuration on reactivity is discussed.
THE ACETOLYSES OF THEALPHAANDBETAMETHYLD-GLUCOPYRANOSIDE TETRAACETATES
Authors: Lemieux R. U. , Shyluk W. P. , Huber G.
Published: May 2006

The acetolyses of the alpha and beta methyl D-glucopyranoside tetraacetates in 1:1 acetic acid – acetic anhydride 0.5 M with respect to sulphuric acid were followed at 25 °C. by isotopic dilution analysis of products isolated after various intervals of time. The reaction of the α-glucoside was found to proceed mainly with inversion of the anomeric center. On the other hand, the β-glucoside was found to undergo acetolysis with retention of configuration concurrent with anomerization. It was shown that the polarimetric changes observed in the course of the reactions could be satisfactorily accounted for on the basis of these reaction routes. Reaction mechanisms are suggested.
SUBUNITS IN THE MOLECULE OF BOVINE PLASMA ALBUMIN
Authors: Reichmann Manfred E. , Colvin J. Ross
Published: May 2006

not available
SOME PROBLEMS IN SURFACE CHEMISTRY
Authors: Rideal Sir Eric
Published: May 2006

not available
THE GROWTH OF CRYSTALLINE LAYERS ON FOREIGN SURFACES
Authors: Singleton J. H. , Halsey Jr. G. D.
Published: May 2006

When the bulk phase of an adsorbent is solid, it has been shown that adsorption often proceeds only to a finite limit as the pressure reaches saturation. A theory is developed for this finite limit, in terms of the excess forces at the surface and the incompatibility of the crystal lattices of the adsorbent and adsorbate. It is applied to the stepwise adsorption of krypton on graphitized carbon black. An extrapolation formula applicable to smooth isotherms at high coverages is developed and shown to be analogous to the Harkins–Jura equation. It is applied to argon adsorbed on carbon black, on xenon preadsorbed on carbon black, on silver iodide, and on anatase. The energies obtained are compared with a theoretical estimate based on the Kirkwood–Müller equation. A theory for calculating isotherms on preadsorbed layers is developed and compared with the data for argon on xenon.
INTERACTION ENERGIES OF ORGANIC MOLECULES WITH RUTILE AND GRAPHON SURFACES FROM HEATS OF IMMERSION
Authors: Chessick J. J. , Zettlemoyer A. C. , Healey F. H. , Young G. J.
Published: May 2006

The heats of immersion of rutile in a series of short chain organic liquids are found experimentally to be an approximate linear function of the dipole moment of the wetting liquid. The significance of the relation is discussed in terms of the polar van der Waals force contribution which is primarily dependent on dipole moment. The average distance of approach of a dipole to the rutile surface and the effective surface force field extending from the rutile surface are calculated.The net adsorption energy, which is calculated directly from heat of immersion data, is related to the energy contributions resulting from the various polar and nonpolar van der Waals forces active in the adsorption process: These energy contributions which make up the total adsorption energy are calculated for the interaction of an alcohol and a hydrocarbon with both a heteropolar (rutile) and a homopolar (Graphon) surface. On the basis of the results obtained, the effects of chain length and functionality of the liquids on the heat of immersion are discussed.
THERMODYNAMIC PROPERTIES OF HYDROCARBONS ADSORBED ON RUTILE II
Authors: Schreiber H. P. , McIntosh R.
Published: May 2006

Integral molar heats and entropies of adsorbed methane and propane on rutile have been computed from data of isotherms at 103.2 ° and 110.2°K. for methane and 166.3° and 224.6°K. for propane. Some resemblance has been found between these functions and those for argon, nitrogen, and oxygen adsorbed on rutile, reported by Drain and Morrison. The integral molar entropy of adsorption made possible a test of the model of a localized film without interactions on a heterogeneous substrate. The model was found to be a reasonable representation of the state of adsorbed methane up to about 0.5 of the monolayer and of propane up to about 0.3 of the monolayer. A unique heat of adsorption curve for the adsorption of methane, ethane, propane, and n-butane has been derived and its significance is briefly discussed. The curve has been employed to derive functions for the distribution of energies among the adsorption sites of the substrate.
THE FORMATION OF THIN FILMS OF IRON OXIDE
Authors: Caule E. J. , Cohen M.
Published: May 2006

It is assumed that the free energy of a thin film of iron oxide is a function of its thickness. The effect on the dissociation pressure is calculated and the condition for stability of thickness is stated. A possible method for measuring the free energy change involved in oxide film formation on metal surfaces is presented which is based on measurements of the e.m.f. of the dry cell metal | oxide | oxygen.
CHARCOAL SORPTION STUDIES: III. THE ADSORPTION OF ETHYLENE AND PERFLUOROETHYLENE BY AN ACTIVATED CHARCOAL
Authors: McDermot H. L. , Arnell J. C. , Lawton B. E.
Published: May 2006

The adsorption of ethylene and perfluoroethylene by an activated charcoal has been measured over a range of temperatures. Integral and differential heats have been calculated and compared for the two gases. The heats of adsorption of perfluoroethylene are consistently higher than those of ethylene, but only by an amount to be expected from the difference in molecular weights. The absolute entropy of adsorbed ethylene has been calculated and found to be in agreement with a model in which the adsorbed molecules are mobile and possess at least two degrees of rotational freedom.
THE RATE OF ADSORPTION OF SOME LOW BOILING GASES ON A MODIFIED SARAN CHARCOAL
Authors: Dacey J. R. , Thomas D. G.
Published: May 2006

The pyrolysis at 300 °C. of vinylidene chloride monomer adsorbed on Saran charcoal alters the pore structure of the charcoal so that low boiling gases such as nitrogen are adsorbed slowly. The rates of adsorption of nitrogen, argon, and methane have been measured. They were found to vary with pressure and temperature, and from the temperature variation an activation energy may be calculated. A new method of determining this energy is described which involves changing the temperature during only one adsorption experiment.
THE PHOTOLYSIS OF MIXTURES OF ACETONE AND SOME HALOGENATED HYDROCARBONS
Authors: Ridge M. J. , Steacie E. W. R.
Published: May 2006

The composition of the products of photolysis of acetone in the presence of methyl chloride, methyl bromide, methylene chloride, and methylene bromide has been determined. These reactions are attended by complications not found with the photolysis of acetone–hydrocarbon mixtures. Failure to take into account reactions resulting from the formation of halogen hydrides and to allow for the presence of ethylene invalidates the values obtained by Raal and Steacie for the activation energy for hydrogen abstraction by methyl radicals from some halogenated hydrocarbons.
ATISINE: THE FUNCTIONAL GROUPS
Authors: Edwards O. E. , Singh Tara
Published: May 2006

not available
SIMPLE PYRROLES AS BASES
Authors: Stedman R.J. , MacDonald S. F.
Published: May 2006

Some simple pyrroles form stable hydrobromides. Their formation may interfere with some reactions, but offers analytical possibilities.
A COMPARATIVE STUDY OF THE DEHYDRATION KINETICS OF SEVERAL HYDRATED SALTS
Authors: Wheeler R. C. , Frost G. B.
Published: May 2006

Rates of dehydration under full vacuum, and also as the pressure of water vapor due to the dehydration process was allowed to increase, have been determined for a number of hydrated salts. The dehydration of manganous sulphate tetrahydrate, zinc sulphate heptahydrate, nickel sulphate hexahydrate, and magnesium sulphate heptahydrate has been found to proceed through the formation of amorphous intermediates, the last two of these being very stable. The dehydration of nickel nitrate hexahydrate, magnesium nitrate hexahydrate, and probably of ferrous sulphate heptahydrate and cobalt chloride hexahydrate at very low pressures takes place with the formation of crystalline intermediates. The results obtained are discussed in relation to the dependence of rate of dehydration on water vapor pressure previously reported for copper sulphate pentahydrate and for manganous oxalate dihydrate.
THE SYNTHESIS OF OPSOPYRROLE-DICARBOXYLIC ACID
Authors: MacDonald D. M. , MacDonald S. F.
Published: May 2006

The methyl groups of the pyrroles Ia and IIa react with sulphuryl chloride to give dichloromethyl derivatives which hydrolyze to aldehydes. The pyrrole Ia also forms a trichloromethyl derivative which hydrolyzes to the corresponding acid. Alkaline decarboxylation of the latter gives opsopyrrole-dicarboxylic acid, IVa.
THE MERCURY PHOTOSENSITIZED HYDROGENATION OF PROPYLENE AND THE ACTIVATION ENERGY OF THE REACTION C3H7+H2 = C3H8+H
Authors: Hoey G. R. , Roy D. J. Le
Published: May 2006

The reactions initiated in hydrogen–propylene mixtures by Hg(3P1) atoms were studied over the temperature range from room temperature to 320 °C. At 260° and above, the rate of formation of propane and the rate of pressure decrease are linear functions of the hydrogen pressure. This effect is attributed to the reaction C3H7+H2 = C3H8+H and its activation energy is estimated to be equal to or slightly greater than 12.5 kcal. per mole. This is 1.2 kcal. per mole greater than the corrected value for the activation energy of the analogous reaction C2H5+H2 = C2H6+H. The ratio kcombination/kdispropotionation is estimated to be approximately 2.0 at room temperature in the case of isopropyl radicals.
THE DEGRADATION OF CARRAGEENIN: I. KINETICS IN AQUEOUS SOLUTION AT pH 7
Authors: Masson C. R.
Published: May 2006

The degradation of carrageenin in buffered aqueous solution at pH 7.0 has been studied over the temperature range 60° to 101 °C. by following the change in viscosity and reducing properties. Kinetic analysis indicates the occurrence of two reactions: (a) an initial rapid degradation representing only about 0.3% of the complete hydrolysis, followed by (b) a first-order random degradation having k = 2.75 × 1013 e−29,200,/RT hr−1. The latter reaction becomes important at temperatures above 60 °C. The results indicate that carrageenin is more unstable than would be expected of a simple 1–3 galactan, and that two types of weak linkage are involved in the structure of the polysaccharide.
THE REACTION OF DIETHYL AZODICARBOXYLATE WITH DIHYDROGELSEMINE
Authors: Habgood Thelma , Marion Léo
Published: May 2006

Dihydrogelsemine reacts with diethyl azodicarboxylate yielding a carbinolamine which forms a methyl ether. Both this ether and the carbinolamine base can be oxidized by chromic acid to the same neutral lactam. That there has been no rearrangement of the carbon skeleton during these reactions is shown by reduction of the methyl ether of the carbinolamine with sodium borohydride to dihydrogelsemine and by reduction of the lactam with lithium aluminum hydride to tetrahydrodesoxygelsemine. It is concluded that both dihydrogelsemine and gelsemine contain a methylene group adjacent to N(b), and from the infrared spectrum of the lactam of dihydrogelsemine, N(b) appears to be part of a five-membered ring.
A 27 °C. ISOTHERMAL CALORIMETER
Authors: Giguère Paul A. , Morissette B. G. , Olmos A. W.
Published: May 2006

The need for a Bunsen-type isothermal calorimeter operating as close as possible to the standard thermochemical reference temperature, 25 °C., was fulfilled by means of diphenyl ether (m.p. 26.9 °C.) as the working substance. The instrument was calibrated electrically by comparison with the ice calorimeter and the constant was found to be 19.01 ± 0.02 cal. per gm. of mercury. From this and other known properties of diphenyl ether the density of the solid at the melting point was estimated at 1.188 gm. per ml. Check determinations based on the heat of vaporization of water showed that for such measurements the mantle of solid ether must first be melted inside by an amount equivalent to the heat to be measured. The calorimeter was operated in a large water-thermostat kept constant to within 0.001 °C. With highly purified diphenyl ether there was no noticeable temperature drift during the measurements. Quantities of heat up to 600 cal. could be measured with a reproducibility of the order of 0.2%. The new calorimeter is simpler to operate than the ice calorimeter and its sensitivity is more than three times as great.
THE SYNTHESIS OF C14-CARBOXYL-LABELLED ω-THIOETHYL FATTY ACIDS
Authors: Almond Anne E. , Burditt Anna Mary , Douglas D. E. , Eccles Jean
Published: May 2006

Syntheses on a semimicro scale of thioethyl acetic, ω-thioethyl propionic, and ω-thioethyl butyric acids labelled with carbon-14 in the carboxyl group are described. The compounds were chromatographed on filter paper with butanol–water–ammonia as the developing solvent, and the RF values determined.
THE REACTION OF ACTIVE NITROGEN WITH HYDRAZINE
Authors: Freeman G. R. , Winkler C. A.
Published: May 2006

Hydrazine was completely destroyed by active nitrogen, at both 150 °C. and 480 °C., up to a hydrazine flow rate of about 22 × 10−6 mole per sec., whereas ammonia production was small at hydrazine flow rates below about 12 × 10−6 mole per sec. Thus it appears that ammonia is formed in secondary reactions only. The results indicate that NH2 radicals rather than hydrogen atoms may be prominent in secondary reactions. Comparison of the rate of hydrazine destruction with the rate of production of hydrogen cyanide from ethylene indicates that excited nitrogen molecules do not make a large contribution to the chemical reactivity of active nitrogen.
IDENTIFICATION OF DIHYDROCONIFERYL ALCOHOL
Authors: Kvasnicka E. A. , McLaughlin R. R. , Reid S.
Published: May 2006

not available
ON THE INTERMOLECULAR FORCE FIELD OF NITRILES
Authors: Murray F. E. , Schneider W. G.
Published: May 2006

The nature of the intermolecular force field of the nitriles is considered on the basis of the electron orbital structure and charge distribution of the nitrile group. The directional nature of the force field is due to a well-directed lone pair orbital on the N atom, which may be expected to exhibit strong donor properties, and two π-orbitals which may exhibit weak donor properties. Accordingly with good acceptor molecules such as chloroform and hydrogen chloride, simple 1:1 molecular addition compounds should occur. The existence of molecular complexes of this type was confirmed with the aid of binary freezing-point diagrams which were determined for aceto-, propio-, butyro-, and benzo-nitrile with chloroform and hydrogen chloride. The 1:1 association complex was absent, however, in the system acetonitrile–chloroform. This is accounted for by the stronger association occurring in acetonitrile itself, the nature of which is discussed. The structure of the 1:1 molecular complexes is considered. Additional molecular complexes with lower nitrile mole ratios are indicated in the freezing-point diagrams. Of particular interest are the well-defined compounds appearing in the nitrile – hydrogen chloride systems with the composition RCN•5HCl. The possibility that the π-orbitals of the nitrile group may function as donors in these compounds is discussed, and a tentative structure is suggested.
THE RELATIVE ABUNDANCES OF NEODYMIUM AND SAMARIUM ISOTOPES IN THE THERMAL NEUTRON FISSION OF U235 AND U233
Authors: Melaika E. A. , Parker M. J. , Petruska J. A. , Tomlinson R. H.
Published: May 2006

The relative fission yields of neodymium and samarium isotopes have been measured with a mass spectrometer for samples of natural uranium and U233 that had been irradiated with moderated neutrons. The cross sections for neutron capture by Sm149 and Sm151 have been determined to be 66,200 ± 2500 barns and 12,000 barns respectively, relative to the cross section of a B10 monitor. The half-lives of Pm147 and Sm151 have been evaluated to be 2.52 ± 0.08 yr. and ~93 yr., respectively, from samarium fission yield data for samples differing in age by seven years.
FREE RADICALS BY MASS SPECTROMETRY: VII. THE IONIZATION POTENTIALS OF ETHYL, ISOPROPYL, AND PROPARGYL RADICALS AND THE APPEARANCE POTENTIALS OF THE RADICAL IONS IN SOME DERIVATIVES
Authors: Farmer J. B. , Lossing F. P.
Published: May 2006

The ionization potentials of ethyl, isopropyl, and propargyl radicals have been measured by electron impact on radicals produced by thermal decomposition of appropriate compounds. The values are:ethyl 8.78±0.05 ev., isopropyl 7.90±0.05 ev., and propargyl 8.25±0.08 ev. From the appearance potentials of these ions in various compounds, the following values of bond dissociation energies were obtained:[Formula: see text][Formula: see text] assuming no kinetic energy of the products.
THE HYDRATION OF PLASTER OF PARIS
Authors: Birss Fraser W. , Thorvaldson T.
Published: May 2006

The hemihydrate of calcium sulphate labelled with calcium-45 or sulphur-35 was hydrated in a supersaturated solution of calcium sulphate at 21 °C. The distribution of the radioactive isotope between the solution and the solid phases and the concentration of the solution throughout the period of hydration were measured. The exchange of calcium ions between crystalline gypsum and its solution was also studied. The experimental results are discussed from the viewpoint of the mechanism involved. They are found to be in agreement with a mechanism which postulates a single passage of the structural units of the solid hemihydrate through the solution and not consistent with one of direct hydration without temporary independent existence of the products in the liquid phase.