bluuebunny/crossref_metadata_2025 huggingface dataset:
THE FRIES REARRANGEMENT OF PHENYL ISOBUTYRATE
Authors: Briggs T. I. , Dutton G. G. S. , Merler E.
Published: May 2006

Phenyl isobutyrate has been found to undergo a normal Fries rearrangement with anhydrous aluminum chloride at 140 °C. to give a mixture of 2-hydroxy-(40%) and 4-hydroxy-isobutyrophenone (11%). When the reaction was carried out in nitrobenzene solution at room temperature the 4-isomer was formed in 86% yield. Methylation of these compounds furnished 2- and 4-methoxy-isobutyrophenone, identical with the compounds obtained by direct acylation of anisole. Reduction of the hydroxy-isobutyrophenones, which were also prepared by direct acylation of phenol, afforded an alternative route to the isobutylphenols. The orientation of each methoxy ketone was verified by oxidation to the corresponding acid.
ORGANIC NITRATES AS SYNTHETIC INTERMEDIATES: PREPARATIONS OF NITRATES AND SOME REPRESENTATIVE REACTIONS
Authors: Pattison F. L. M. , Brown G. M.
Published: May 2006

It has been shown that the carbon–oxygen bond of nitrate esters is susceptible to cleavage by certain representative nucleophilic reagents, of which sodium iodide, sodium cyanide, and potassium thiocyanate have received particular attention. Allyl, 3-hydroxypropyl, 4-fluorobutyl, hexyl, and benzyl nitrate were examined in order to determine the effect if any of functional groups on the ease and efficiency of cleavage.
THE REACTION OF ACTIVE NITROGEN WITH MERCURY DIETHYL
Authors: Armstrong D. A. , Winkler C. A.
Published: May 2006

The main organic product of the reaction was hydrogen cyanide, the maximum yield of which was practically independent of temperature in the range 130 ° to 330 °C, and appeared to correspond to about one-half the active nitrogen concentration present. Presumably the reactant or products, or both, caused deactivation of about one-half the active nitrogen. Small amounts of butane, propane, ethane, methane, propylene, ethylene, acetylene, and cyanogen were also found in the products.
A NEW SYNTHESIS OF DL-γ-HYDROXY-ORNITHINE
Authors: Talbot Guy , Gaudry Roger , Berlinguet Louis
Published: May 2006

A convenient synthesis of DL-hydroxy-ornithine is described. Starting from diethyl allylmalonate, it involves treatment with sulphuryl chloride followed by hydrolysis and distillation to give a 90% yield of 2,5-dichloro-4-valerolactone. Condensation of this with two equivalents of potassium phthalimide in dimethyl-formamide gives a quantitative yield of crude 2,5-diphthalimido-4-valerolactone. This lactone is converted quantitatively by acid hydrolysis to DL-γ-hydroxyornithine, isolated as the dihydrochloride of the corresponding 2,5-diamino-4-valerolactone. The over-all yield calculated from allyl chloride is 80%.
α-ARYL-β-AROYLPROPIONIC ACIDS AND THEIR CONDENSATION PRODUCTS WITH AROMATIC ALDEHYDES
Authors: Allen C. F. H. , Davis T. J. , Stewart D. W. , VanAllan J. A.
Published: May 2006

It has been shown, by means of spectral analysis, that α-aryl-β-aroylpropionic acids exist in an open-chain configuration while the condensation products of these latter acids with aromatic aldehydes are lactols. The mesityl derivatives constitute exceptions in both series. These findings necessitate a revision of some of the earlier literature.
REACTIONS OF ARYLSULPHONIC ESTERS: V. AN INTERPRETATION OF ACTIVATION ENERGIES OF SOLVOLYSIS OF METHYL BENZENESULPHONATE IN MIXED HYDROXYLIC SOLVENTS
Authors: Hyne J. B. , Robertson R. E.
Published: May 2006

The rates of solvolysis of methyl benzenesulphonate at 50 ° and 75 °C. in several binary aliphatic alcohol–water mixtures have been determined over the composition ranges. The derived activation energies are compared with those calculated from an extended form of the equation employed in accounting for solvolytic activation energies in pure hydroxylic solvents. The physical significance of the equation is discussed in terms of a spectrum of solvolytic mechanisms covering the range between SN1 and SN2 mechanisms. The equation predicts activation energy values well within the experimental uncertainty. Product ratio and activation entropy data are shown to be in keeping with the reaction mechanism proposed.
A METHOD OF RECORDING a-c. POLAROGRAMS ON A CONVENTIONAL d-c. POLAROGRAPH
Authors: Miller D. M.
Published: May 2006

An increase in the usefulness of the recording polarograph is obtained by a modification which allows either a-c. or d-c. polarograms to be obtained from it. A description of such a modification performed on the Sargent Model XXI is given in detail. A comparison of a-c. and d-c. polarography is made and illustrated by polarograms obtained from this instrument.
GRAFT COPOLYMERS OF STYRENE AND METHYL METHACRYLATE: PART II: VISCOSITY BEHAVIOR
Authors: Jones M. H.
Published: May 2006

A study of the viscosity behavior of the graft copolymers described in Part I has been made with dilute solutions in benzene at 25 °C. Although the slope constants of the Huggins equation increase with the frequency of branching when measurements are made in a capillary viscometer under 'free fall' conditions, this is shown to be attributable to the dependence of viscosity on shear gradient. At a constant shear rate, the Huggins k′ values approximate to those of linear polymers. It is suggested that the marked increase in viscosity observed with decreasing shear rate for the graft copolymers is due to molecular entanglement.
THE ADSORPTION OF NITROGEN BY BROMINATED GRAPHITE AND CARBON BLACK
Authors: McDermot H. L. , Arnell J. C.
Published: May 2006

The adsorption of nitrogen has been measured at 78 °K. for three artificial graphites and one carbon black, which have been brominated to saturation and then debrominated by heat-treatment under vacuum or in the presence of an inert gas over a range of temperatures. During the bromine removal, the graphites were heated to a maximum temperature of 1000 °C. and the carbon black to a maximum of 1200 °C. When the graphite of smallest area was brominated it did not return to its original area even after heat-treatment at 1000 °C, whereas the graphite of largest area exceeded its original area when it was brominated and heated at 1000 °C. The surface area of the brominated carbon black was restored to the original value when it was evacuated at 400 °C. After evacuation at 600 °C, the surface area was greater than that of the original carbon black, but fell to a value less than the original area when the sample was evacuated at 1200 °C. These observations are believed to be in accord with the known structures of the graphites and the carbon black.
THE INFRARED AND RAMAN SPECTRA OF ALLENE-1,1-d2
Authors: Evans J. C. , Wilmshurst J. K. , Bernstein H. J.
Published: May 2006

not available
THE OXIDATION OF HYDRAZOBENZENE BY AMMONIUM PERSULPHATE IN ACETONITRILE–WATER SOLUTION
Authors: Whalley B. J. P. , Evans H. G. V. , Winkler C. A.
Published: May 2006

In a given experiment, second order kinetics were displayed during the greater part of the reaction over a considerable range of initial concentrations of reactants. In general, the second order behavior was maintained to greater extent of reaction when hydrazobenzene was in excess. The calculated second order rate constant, k, decreased with increase in initial hydrazobenzene concentration and increased with increase in initial concentration of ammonium persulphate. For different equimolar concentrations of reactants, k was virtually independent of initial concentrations. The value of k was proportional to the square root of the ratio of the initial concentrations of persulphate and hydrazobenzene. The activation energy of the over-all reaction was 16 kcal. per mole. A free radical mechanism appears to account reasonably well for the major experimental observations.
L-SERYLGLYCYLGLYCINE
Authors: Baer Erich , Maurukas Jonas , Clarke Donald D.
Published: May 2006

A synthesis of the hitherto unreported L-serylglycylglycine by two different methods is described. N-carbobenzoxy L-serylglycylglycine benzyl ester, an intermediate in the preparation of the tripeptide, was found to be a suitable derivative in the synthesis of L-α-phosphatidyl L-serylglycylglycine.
LYCOPODIUM ALKALOIDS: III. FUNCTIONAL GROUPS OF SOME MINOR ALKALOIDS OF L. ANNOTINUM
Authors: Perry G. S. , MacLean David B.
Published: May 2006

Four minor alkaloids of L. annotinum have been examined by chemical methods and infrared spectroscopy for their functional groups. Acrifoline (L.27) C16H23O2N has a double bond, a carbonyl group, and an hydroxyl function. Annotine (L.11) C16H21O3N has a double bond, a carbonyl group, an hydroxyl function, and an inert oxygen probably present in an ether linkage. Alkaloid L.12 (C18H25O3N) is O-acetylacrifoline. Alkaloid L.8 (C16H25O2N) has only been studied by infrared spectroscopy where it shows carbonyl and hydroxyl absorption. All four alkaloids therefore contain a basic tetracyclic ring system as do the majority of other lycopodium alkaloids. Annotoxine, a molecular compound of acrifoline and annotine, has been isolated from extracts of Canadian plant material.
DEUTERIUM MIGRATION DURING THE IONIZATION OF 1-BUTENE-4-d3 BY ELECTRON IMPACT
Authors: Bryce W. A. , Kebarle Paul
Published: May 2006

The mass spectrum of CD3—CH2—CH=CH2 has been measured in a 90° Nier-type mass spectrometer using 50-volt electrons. High resolution nuclear magnetic resonance measurements showed that the methyl group was fully deuterated and that there were no D-atoms located elsewhere in the molecule. This result was supported by infrared analysis. A comparison of the mass spectrum with that of CH3—CH2—CH=CH2 shows that the total intensities of each group of C4, C3, C2, and C1 fragments are the same for both compounds. This indicates equal probabilities of C—C bond rupture in the dissociation of the corresponding parent ions. The distribution of fragments within the groups in the deuterated compound shows, however, that extensive migration of the D-atoms has occurred during ionization. Migration is also evident at much lower electron energies (approximately 15 ev.). The thermal cracking patterns of the two compounds, as determined by gas chromatographic analyses, are very similar.
THIAZOLES: II. PREPARATION OF ALKYL-2-NITRAMINOTHIAZOLES
Authors: Kasman Sidney , Taurins Alfred
Published: May 2006

1-Chloro-3-methyl-2-butanone and 2-amino-4-isopropylthiazole have been synthesized. The mononitration of 2-aminothiazole and five alkyl-2-aminothiazoles in the 2-amino group has been carried out with absolute nitric acid in concentrated sulphuric acid at low temperatures ranging from 0° to −10°. 2-Nitramino- and alkyl-2-nitramino-thiazoles are crystalline, stable compounds. The dinitration of some alkyl-2-aminothiazoles under the same conditions lead to the formation of alkyl-2-nitramino-5-nitrothiazoles. The rearrangement of 2-nitraminothiazole to 2-amino-5-nitrothiazole was studied in the presence of mesitylene for the first time.
THE REACTIONS OF ACTIVE NITROGEN WITH ORGANIC MOLECULES
Authors: Evans H. G. V. , Freeman G. R. , Winkler C. A.
Published: May 2006

The main features of the reactions of active nitrogen with various organic molecules are reviewed, and a unified mechanism outlined to account for at least the more significant experimental observations.
LIGHT ABSORPTION STUDIES: PART III. STRUCTURE AND LIGHT ABSORPTION OF TRISUBSTITUTED BENZENE DERIVATIVES
Authors: Forbes W. F. , Mueller W. A.
Published: May 2006

The spectra of a number of trisubstituted benzene derivatives which have recently been described by Doub and Vandenbelt are discussed in terms of the electronic and steric effects. The assumption of Doub and Vandenbelt, that the steric effects are usually small in absorption spectra, is criticized.
LIGHT ABSORPTION STUDIES: PART IV. THE EFFECTS OF STERICALLY HINDERED CONFORMATIONS ON THE ELECTRONIC SPECTRA (B-BANDS) OF CONJUGATED SYSTEMS
Authors: Forbes W. F. , Mueller W. A.
Published: May 2006

The equation ε/ε0 = cos2(θ1 − θ2) recently proposed by Braude and co-workers is developed to account more rigorously for the spectra of unsymmetrical molecules. The results obtained from the revised equation, [Formula: see text] support the interference value of hydrogen obtained independently from spectral data, and suggest a re-examination of the reported theories accounting for the spectra of alicyclic enones and dienones, and for steric effects of type I.
THE SYNTHESIS OF INDOLE-3-ACETYL-D,L-ASPARTIC ACID AND RELATED COMPOUNDS
Authors: Good Norman E.
Published: May 2006

not available
PREPARATIVE PARTITION CHROMATOGRAPHY OF CARBOHYDRATES ON CELITE COLUMNS
Authors: Lemieux R. U. , Bishop C. T. , Pelletier G. E.
Published: May 2006

Partition on Celite columns, using both elution and extrusion techniques, was found to be a convenient and satisfactory chromatographic method for preparative or analytical work involving carbohydrates and their derivatives. The method is superior to other chromatographic procedures for carbohydrates in resolution of mixtures; cost, ease, and speed of operation; yield and purity of products; and range of applicability. To illustrate these advantages a number of specific examples are given involving partially methylated derivatives of D-glucose and D-xylose and isolation of products from reaction mixtures.
EFFECTS OF COMPLEXING ON THE HOMOGENEOUS REDUCTION OF MERCURIC SALTS IN AQUEOUS SOLUTION BY MOLECULAR HYDROGEN
Authors: Korinek G. J. , Halpern J.
Published: May 2006

The effects of various complexing agents on the homogeneous reduction of mercuric salts by molecular hydrogen in aqueous solution were determined. In all cases the kinetics suggest that the rate-determining step is a bimolecular reaction between a mercuric ion or complex and a hydrogen molecule, probably leading to the formation of an intermediate mercury atom. The reactivity of various mercuric complexes was found to decrease in the following order: HgSO4 > Hg++ > HgAc2, HgPr2 > HgCl2 > HgBr2 > Hg(EDA)2++. Addition of anions such as OH−, CO3=, Ac−, Pr−, and Cl−, in excess of the amounts required to form stable mercuric complexes, was found to increase the rate. An interpretation of these effects is given.
PERIODATE–PERMANGANATE OXIDATIONS: V. OXIDATION OF LIPIDS IN MEDIA CONTAINING ORGANIC SOLVENTS
Authors: Rudloff E. Von
Published: May 2006

The periodate–permanganate reaction with methyl oleate and triolein has been studied in media containing a variety of organic solvents. The oxidation proceeded favorably in media containing tertiary butanol or pyridine and conditions have been found which permit the quantitative analysis of unsaturated lipids.
A CONVENIENT SYNTHESIS OF DL-GLUTAMIC ACID FROM β-PROPIOLACTONE
Authors: Talbot Guy , Gaudry Roger , Berlinguet Louis
Published: May 2006

A new synthesis of DL-glutamic acid was carried out in an over-all yield of 87% from condensation between β-propiolactone and the sodium salt of diethyl acetamidomalonate, followed by acid hydrolysis. When desired, the intermediate product, the diethyl ester of N-acetyl-2-carbethoxyglutamic acid, could be isolated in a 68% yield and hydrolyzed to glutamic acid via the hydrochloride in a 95% yield.
THE REACTIONS OF ACTIVE NITROGEN WITH METHANE AND ETHANE
Authors: Gartaganis P. A. , Winkler C. A.
Published: May 2006

Reinvestigation of the active nitrogen – methane reaction in the temperature range 45° to 500 °C. has confirmed hydrogen cyanide as the only product, other than hydrogen, formed in measurable amounts. An “induction” effect in the hydrogen cyanide production was observed with increase of methane flow rate. This induction decreased with increase of temperature and was shown to be due to concomitant hydrogen atom reactions, since it could be eliminated by addition of hydrogen atoms to the reaction mixture. Reinvestigation of the active nitrogen – ethane reaction over the temperature range −100° to 475 °C. also confirmed hydrogen cyanide to be the only measurable product, other than hydrogen, of that reaction. There was some indication that an induction effect was present with ethane, as with methane, and it may be concluded tentatively that both reactions are carried substantially by hydrogen atom reactions.
THERMODYNAMIC PROPERTIES OF BENZOIC ACID
Authors: Goton R. , Whalley E.
Published: May 2006

not available
THE RELATION BETWEEN ACTIVATION ENERGY OF THE VISCOSITY AND HEAT OF VAPORIZATION FOR MOLTEN SALTS
Authors: Zeggeren F. Van
Published: May 2006

not available
TOXIC FLUORINE COMPOUNDS: XII. ESTERS OF ω-FLUOROALCOHOLS
Authors: Millington J. E. , Pattison F. L. M.
Published: May 2006

Representative members of the series of ω-fluoroalkyl methanesulphonates, p-toluenesulphonates, acetates, and benzoates have been prepared, and some of their chemical, physical, and toxicological properties determined.
AN EXPERIMENTAL DETERMINATION OF THE SURFACE ENTHALPY OF SODIUM CHLORIDE
Authors: Benson G. C. , Schreiber H. P. , Zeggeren F. Van
Published: May 2006

The surface enthalpy of NaCl has been redetermined from heats of solution of salt samples of different specific surface areas. Special care was taken in the preparation of these samples to avoid contamination by nitrate and excess sodium. The value obtained, 276 ergs/cm.2, differs from that reported by Benson and Benson, viz. 305 ergs/cm.2, for samples containing some nitrate impurity.
AN IMPROVED SYNTHESIS OF ACETOSYRINGONE
Authors: Crawford L. W. , Eaton E. O. , Pepper J. M.
Published: May 2006

Acetosyringone has been synthesized from acetovanillone, in better than a 50% yield, through conversion to 5-iodoacetovanillone followed by its interaction with sodium methoxide in the presence of copper catalyst. The previously unreported intermediate, 5-iodoacetovanillone, was characterized by methylation to 5-iodoacetoveratrone and subsequent oxidation to the known 5-iodoveratric acid.
THE REACTION OF TETRAMETHYLTHIURAMDISULPHIDE WITH ACETONE: II. THE EFFECTS OF ADDITIVES
Authors: Craig David , Robinson J. R. , Fowler Ray B.
Published: May 2006

A discussion of the effects of additives upon the reaction of tetramethylthiuramdisulphide with acetone leads to the suggestion that the process is autocatalytic, that dimethylamine is the natural catalyst, and that the time required for its formation describes the induction period. The formation of the various products of the reaction is explained in terms of a free-radical mechanism.
THE SYSTEM LITHIUM CHLORATE – LITHIUM CHLORIDE – WATER AT VARIOUS TEMPERATURES
Authors: Campbell A. N. , Griffiths J. E.
Published: May 2006

The equilibrium diagram of the system lithium chlorate – water has been determined at all temperatures and that of the system lithium chlorate – lithium chloride – water at the temperatures 3.0°, 6.0°, 8.5°, and 25.0 °C.Lithium chlorate forms three hydrates having the formulae:(i) (LiClO3)4.H2O—stable in contact with solution from 20.5° to 42.0 °C.(ii) LiClO3.H2O—stable in contact with solution from −0.1° to 20.5 °C.(iii) LiClO3.3 H2O—melts congruently at 8.4 °C.Hydrate (i) was discovered by Berg but he gave to it the formula (LiClO3)3.H2O.Lithium chlorate and lithium chloride form no double salts at the temperatures of investigation.Lithium chlorate exists in two enantiotropic forms, namely the α and the β forms. The transition, α ↔ β, takes place at 99.8 °C. and the α form has the lower density. The γ form, proposed by Kraus and Burgess, does not exist either stably or metastably. The X-ray diffraction pattern of β-LiClO3 has been obtained.
THE HEAT OF NEUTRALIZATION OF STRONG ACIDS AND BASES IN HIGHLY DILUTE AQUEOUS SOLUTIONS
Authors: Papee H. M. , Canady W. J. , Laidler K. J.
Published: May 2006

Heats of neutralization of sulphuric and hydrochloric acids by sodium hydroxide have been determined, using a microcalorimeter of the Tian–Calvet type. The range of concentrations employed was 5 × 10−4 N to 3 × 10−2 N, which is sufficiently low to permit an accurate extrapolation to be made down to zero concentration. The extrapolated values obtained were: for H2SO4–NaOH, 13.48 ± 0.05 kcal. per gm-equiv. and for HCl–NaOH, 13.52 ± 0.05 kcal. per gm-equiv. These values, which correspond to the process H3O+ + OH− → 2H2O, are significantly higher than the values of 13.32–13.37 kcal. obtained on the basis of previous calorimetric studies in a much higher concentration range. The present values, however, agree well with those calculated by Harned and co-workers and by Everett and Wynne-Jones from electrochemical data.
MEASUREMENT OF PRESSURES IN THE TITANIUM IODINE SYSTEM USING THE EFFUSION METHOD
Authors: Herczog A. , Pidgeon L. M.
Published: May 2006

The equilibrium vapor pressures of TiI4 and TiI2, obtained by the simultaneous decomposition and evaporation of TiI2 in the presence of excess Ti, have been measured over the temperature range 750–902 °K. using the effusion method. Thermodynamic data have been calculated for the equilibrium systems:[Formula: see text]
THE ADSORPTION OF NITROGEN BY BROMINATED CHARCOAL
Authors: McDermot H. L.
Published: May 2006

The adsorption of nitrogen has been measured at 78 °K, for two charcoals which have been brominated and heat-treated at a variety of temperatures. In no instance did removal of the sorbed bromine by heat-treatment bring about activation of the charcoal. The "densities" of bromine sorbed by charcoal have been calculated from the volumes of nitrogen sorbed by charcoal containing varying amounts of residual bromine. In all cases, the "density" of sorbed bromine was found to be less than that of solid bromine.
ON THE STRUCTURE OF AGAR FROM GELIDIUM CARTILAGINIUM
Authors: O'Neill A. N. , Stewart D. K. R.
Published: May 2006

Agar from Gelidium cartilaginium has been analyzed for D-galactose, 3,6-anhydro-L-galactose, and sulphate. From these analyses and a study of the products of mercaptolysis it is suggested that agar from this source be represented as a chain of alternating D-galactose and 3,6-anhydro-L-galactose residues with a half-ester sulphate on about every 10th galactose unit.
SOLVOLYSIS IN DEUTERIUM AND HYDROGEN OXIDE
Authors: Laughton P. M. , Robertson R. E.
Published: May 2006

Rate data for a series of benzenesulphonates, halides, and methyl methanesulphonate were determined in light and heavy water. The rate ratio [Formula: see text] varied with the nature of the anion being formed from 0.94. for the hydrolysis of methyl methanesulphonate to 0.78 for methyl chloride. This difference in ratio was attributed to differences in the nature of the solvation of the initial states. No appreciable differences arose, however, through the alkyl series methyl, ethyl, isopropyl benzenesulphonates, and the difference for the ratio [Formula: see text] between MeCl and t-butyl chloride was small, contrary to recently published work.
THE OXIDATION OF CARBON MONOXIDE BY SOLID SILVER PERMANGANATE REAGENTS: VI. REACTION KINETICS AND ADSORPTION OF WATER VAPOR
Authors: Katz Morris , Riberdy R. , Grant G. A.
Published: May 2006

The temperature dependence of the rate constant, k, in the heterogeneous oxidation of carbon monoxide on the surface of silver permanganate – zinc oxide, indicates that in the temperature range of about 11° to 40 °C, the process is subject to diffusion or transport control and the experimental activation energy is 1.4 to 1.9 kcal. per mole. In the range of 11° to −3 °C. the rate of the surface chemical reaction decreases with a corresponding increase in activation energy to 15 kcal. in this transition stage. At lower temperatures the system is subject to chemical control and E rises to about 27 kcal.Four adsorption isotherms for water vapor on this reagent have been obtained in the range of −10° to 20 °C. The isotherms are sigmoid and indicative of Type II adsorption.The mechanism of this heterogeneous reaction is discussed on the basis of several possibilities for providing oxygen ions in the electron–ion exchange step of the over-all reaction.
L'OXYDATION STOÏCHIOMÉTRIQUE DE L'OXYDE D'AZOTE PAR L'OZONE ÉTABLIE PAR PHOTOMÉTRIE DU BIOXYDE D'AZOTE
Authors: Goyer Guy G.
Published: May 2006

not available
THE POLAROGRAPHY OF THE METHYL DERIVATIVES OF MALEIC HYDRAZIDE AND EXPLANATION OF THE MALEIC HYDRAZIDE WAVES
Authors: Miller D. M.
Published: May 2006

Maleic hydrazide was previously reported to have two sets of pH dependent double waves, one at low pH for which existing theories provide adequate explanation and one at higher pH for which no explanation has been offered to date. The present work is an attempt to discover the reasons for the existence of the second set of waves. An investigation of several methyl derivatives of maleic hydrazide failed to provide the desired explanation; however, a mechanism which gives a good qualitative and approximately quantitative expression for the dependence of diffusion currents and half wave potentials on pH is offered. This theory is based on the fact that succinic hydrazide, a probable product of the reduction of maleic hydrazide, has been found to have a pKa of 8.10 and thus to be present in both ionized and unionized forms over the pH range for which the double waves occur.
THE SYNTHESIS OF THE UROPORPHYRINS II AND IV
Authors: MacDonald S. F. , Michl K. H.
Published: May 2006

Uroporphyrin II and uroporphyrin IV have been synthesized by rational methods. The former has also been separated from a mixture of uroporphyrins previously synthesized.
THE INFRARED SPECTRA OF SECONDARY AMINES AND THEIR SALTS
Authors: Heacock R. A. , Marion Léo
Published: May 2006

The infrared spectra of a number of secondary bases and of their salts have been examined. The spectra of the salts differ from those of the corresponding bases in containing several absorption bands that are absent from the latter. Those of the new bands occurring in the region 1620 to 1560 cm.−1, which are due to NH2+ deformation vibrations, are characteristic of secondary amine salts, and can be used to detect the presence of a secondary amino group in the original molecule. With aromatic bases the spectra are complicated because the ring absorption occurs in the same region, but in many cases the assignment can still be made, although with less certainty. In zwitterionic substances such as the secondary aliphatic amino acids, the function is more difficult to detect.
A MANNAN PRODUCED BY SACCHAROMYCES ROUXII
Authors: Gorin P. A. J. , Perlin A. S.
Published: May 2006

The main slime polysaccharide produced by Saccharomyccs rouxii during the fermentation of D-glucose to D-arabitol is a mannan. Acetolysis of the polymer has afforded di- and tri-saccharides in good yield, but no higher oligosaccharides were produced. The disaccharide is shown by methylation and lead tetraacetate oxidation to be 2-O-α-D-mannopyranosyl-D-mannose, establishing the presence of a 1,2-α-linkage in the polysaccharide. On acid hydrolysis the methylated mannan gives mainly 2,3,4,6-tetra-O-methyl-D-mannose, 3,4,6-tri-O-methyl-D-mannose, and 3,4-di-O-methyl-D-mannose; lesser components found are 2,4,6-tri-O-methyl-D-mannose and 3-O-methyl-D-mannose. The methylation and acetolysis data together suggest an average structural unit consisting of a main chain of D-mannopyranose units containing alternate 1,2- and 1,6-linkages, to which single D-mannopyranose units are attached by 1,2-linkages as side chains; alternatively, 1,2-disaccharide units are attached as side chains by 1,2-linkages to a 1,6-linked main chain.
INFRARED SPECTRUM OF SOLID SULPHUR DIOXIDE
Authors: Giguère Paul A. , Falk M.
Published: May 2006

not available
A NEW SYNTHESIS OF 1-SUBSTITUTED-2,3,5,6-TETRAHYDRO-1-IMIDAZ(1,2-a)IMIDAZOLES
Authors: McKay A. F. , Garmaise D. L.
Published: May 2006

A number of 1-(β-hydroxyethyl)-2-(substituted amino)-2-imidazolines have been prepared by the reaction of amines with 1-(β-hydroxyethyl)-2-methylmercapto-2-imidazoline. These intermediates on chlorination and dehydrochlorination give the corresponding 1-substituted-2,3,5,6-tetrahydro-1-imidaz (1,2-a) imidazoles.
THE STRUCTURE OF ARTIFICIAL GRAPHITES AS REVEALED BY X-RAY, ELECTRON MICROSCOPE, AND ADSORPTION STUDIES
Authors: Wilson L. G. , McDermot H. L.
Published: May 2006

Three artificial graphites have been studied by X-ray, electron microscope, and adsorption techniques. Surface areas were calculated from the adsorption isotherms and from the X-ray spectra. The two sets of areas were of the same order of magnitude and varied from 18 m.2/g. for the graphite of smallest surface area to 385 m.2/g. for the graphite of largest surface area. The appearance of the graphites under the electron microscope was in qualitative agreement with the adsorption and X-ray data.
PYRROLE CHEMISTRY: I. SUBSTITUTION REACTIONS OF 1-METHYLPYRROLE
Authors: Anderson Hugh J.
Published: May 2006

An investigation of some substitution reactions of 1-methylpyrrole has indicated that the α-directing effect of the hetero nitrogen during nitration is even less than it is in pyrrole. 3-Nitro-1-methylpyrrole has been prepared together with the 2-isomer by direct nitration of 1-methylpyrrole as well as indirectly. These two compounds have been found to undergo Friedel-Crafts acylation, a reaction not previously reported among simple nitro compounds of the 5-membered heterocycles. It has been found, contrary to the results of previous workers, that direct nitration of pyrrole itself yields a mononitro product containing about 7% of the 3-isomer.
SELECTIVE SUBSTITUTION IN SUCROSE: I. THE SYNTHESIS OF 1′,4,6′-TRI-O-METHYL SUCROSE
Authors: McKeown G. G. , Serenius R. S. E. , Hayward L. D.
Published: May 2006

Sucrose was tritylated and acetylated to give a crystalline tri-O-trityl-penta-O-acetyl sucrose derivative, and detritylation of this product by graded hydrolysis with acetic acid followed by methylation and deacetylation yielded 1′,4,6′-tri-O-methyl sucrose. The structure of the tri-O-methyl sucrose was established by periodate oxidation and by hydrolysis to the corresponding O-methyl ethers of glucose and fructose. Acetyl group migration from C4 to C6 in the glucose moiety of sucrose probably occurred during the methylation reaction.Some aspects of syntheses involving sucrose are discussed.
THE PAPILIONACEOUS ALKALOIDS: XXIII. THE STRUCTURE OF BAPTIFOLINE
Authors: Martin-Smith M. , Marion Léo
Published: May 2006

Baptifoline (C15H20O2N2) has been found on spectroscopic evidence to contain a hydroxyl group and an α-pyridone ring. On catalytic hydrogenation it gives rise to tetrahydrobaptifoline, which has been identified as l-hydroxylupanine. Baptifoline is, therefore, l-13-hydroxyanagyrine.
TRIARYLMETHANE COMPOUNDS AS REDOX INDICATORS IN THE SCHOENEMANN REACTION: I. MECHANISM OF THE SCHOENEMANN REACTION
Authors: Grant G. A. , Blanchfield R. , Smith D. Morison
Published: May 2006

A method is outlined for the detection of anticholinesterase agents similar to sarin (isopropyl methylphosphonofluoridate) in aqueous solution at concentrations as low as 0.1 p.p.m. in 10 ml. of solution by the use of the Schoenemann reaction. A new series of indicators, 4,4′-(2-thenylidene)bis[N,N-dimethylaniline] variously substituted in the thiophene ring, was used in the investigation. The dependence of color formation on pH, chloride ion concentration, and other factors led to an explanation of the mechanism of the reaction involved. Chloride ion is necessary for the reaction and, in the absence of the indicator, free chlorine can be detected in acid solution. Presumably, then, during acidification perphosphonate ion reacts with chloride ion to give hypochlorous acid, which oxidizes the mono ion of the leuco compound to a dye.Ions such as cyanide ion, with a lower oxidation–reduction potential than the leuco compounds, interfere with the test. Oxidation of the leuco compound by hypochlorous acid is bypassed in the method described for the detection of sarin in the presence of hypochlorous acid.
SYNTHESIS OF 3,5-DI-O-METHYL-D-GLUCOSE
Authors: Bishop C. T.
Published: May 2006

3,5-Di-O-methyl-D-glucose has been synthesized by methylation of 1,2-O-isopropylidene-6-O-trityl-D-glucofuranose and removal of the blocking groups by acid hydrolysis. The di-O-methyl glucose furnished a crystalline osazone without loss of a methoxyl group and yielded a monobasic and dibasic acid when oxidized by bromine and nitric acid respectively. Both acids formed gamma lactones and crystalline amides by which the parent compound is characterized. The foregoing reactions proved the structure of 3,5-di-O-methyl-D-glucose predicted by its method of synthesis.
RADIATION-INDUCED EXCHANGE OF DEUTERIUM BETWEEN HEAVY WATER AND DISSOLVED HYDROGEN
Authors: Bardwell J. , Dyne P. J.
Published: May 2006

Exchange of deuterium between deuterium oxide and molecular hydrogen is induced by gamma rays from Co60. The reaction was studied by irradiating heavy water solutions saturated with hydrogen gas, and then analyzing the gas with a mass spectrometer. The reaction rate conforms to the exponential exchange law. The exchange yield is independent of dose rate and of hydrogen concentration over a moderate range. Prolonged irradiation leads to a steady state where the isotopic composition of the gas is close to that of the solution. This state differs greatly from that for thermodynamic equilibrium at room temperature.
MASS SPECTROMETRIC STUDY OF THE SPECIES CS, SO, AND CCl2 PRODUCED IN PRIMARY HETEROGENEOUS REACTIONS
Authors: Blanchard L. P. , Goff P. Le
Published: May 2006

In a flow system and at very low pressures, the reactions of CS2, H2S, SO2, and CCl4, on pure and carburized tungsten ribbons, were studied at 1300–2000° K.In the decomposition of CS2, on pure tungsten, CS and S2 are found—in that of H2S, H2 and S2—in that of SO2, O2 and SO or S2, according to the temperature—CCl4 gives CCl2, Cl2, and Cl. H2, S2, and Cl2 molecules are probably formed by recombination on the walls of atoms produced on the ribbon. With carburized tungsten the formation of S2 and O2 is replaced by that of CS and CO. On the contrary, no decarburization occurs with chlorine.Ionization potentials of the different species are measured and the deduced bond dissociation energies are discussed.
ULTRAVIOLET IRRADIATION OF PYRIMIDINE DERIVATIVES: I. 1,3-DIMETHYLURACIL
Authors: Moore A. M. , Thomson C. H.
Published: May 2006

The isolation, analysis, and synthesis of the principal product of the ultraviolet (2537 Å) irradiation of aqueous 1,3-dimethyluracil has made it possible to establish that the irradiation results in hydration of the 5:6 double bond of the uracil ring to form 1,3-dimethyl-6-oxy-hydrouracil. This hydration is spontaneously reversible, the dehydration being catalyzed by either acid or base. Kinetic studies of the catalyzed regeneration reactions are reported
A QUANTITATIVE INFRARED SPECTROMETRIC STUDY OF MOLECULAR ASSOCIATION IN ALCOHOLS
Authors: Ens Adolf , Murray F. E.
Published: May 2006

The absorption spectra of methanol, ethanol, isobutanol, tert-amyl alcohol, and octanol-2 were studied in the wavelength region of the first harmonic of the O—H vibration. The data obtained were used in each case to calculate the number of monomers combined to form an association polymer and the equilibrium constant for the association reaction in carbon tetrachloride solution. It was found for all alcohols studied that the association number was between three and four.
ANOMALOUS APPARENT DIELECTRIC CONSTANTS OF GASES ON SEVERAL POROUS ADSORBENTS
Authors: Petrie S. E. , McIntosh R.
Published: May 2006

Changes in the capacity of a test cell which contained porous Vycor glass have been measured following the adsorption of butane and ethyl chloride. The results are similar to those obtained by Snelgrove and McIntosh using silica gel and these adsorbates. That is, a sudden drop in the apparent polarization is observed at a well defined quantity of adsorbed gas. This observation thus appears characteristic of porous adsorbents. To explain the phenomenon one may postulate a low density for the material of low apparent polarizability, or its location in a different electrical field in the heterogeneous dielectric. The former is ruled out with Vycor glass because of insufficient pore volume. The latter approach has been examined using the "cluster" treatment of Channen and McIntosh with the data for silica gel systems as well as porous glass. The attempt has proved only partially successful.
THE PARTIAL MOLAL VOLUMES OF IONS IN AQUEOUS SOLUTION: II. AN EMPIRICAL EQUATION FOR OXY-ANIONS
Authors: Couture A. M. , Laidler K. J.
Published: May 2006

The partial molal volumes of oxy-anions, obtained from density data, have been correlated with the radius, the charge, and the number of ligands of the ions. The volumes relative to a value of −6.0 ml. for the proton are represented by the equation:[Formula: see text]where r and z_ have the same significance as in the preceding paper on entropies. The equation is compared with the one for monatomic ions, and the significance of the effective radius r is discussed.
THE SYNTHESES AND REACTIONS OF ALKYLATED FURANS
Authors: Brown Wm. H. , Wright George F
Published: May 2006

The reaction of 2-chloromercurifuran with t-butyl bromide does not yield 2-t-butylfuran. Instead 2,5-di-t-butylfuran, 2,2,7,7-tetramethyloctane-3,6-dione, and 2-t-butyl-5-[2,4,4-trimethyl-2-pentyl]furan are produced. Air-oxidation of di-t-butylfuran yields trans-2,2,7,7-tetramethyl-4-octene-3,6-dione (converted to the cis isomer photochemically) which forms a dibromide identical with the dibromo substitution product from tetramethyloctanedione. Cold nitric acid oxidation of di-t-butylfuran or tetramethyloctanedione yields 4-hydroxy-5-isonitroso-2,2,7,7-tetramethyloctane-3,6-dione, but hot nitric acid oxidation of the tetramethyloctanedione yields the expected 2-trimethylacetyl-5-t-butylisoxazole. The corresponding oxidation product of t-butyltrimethylpentylfuran has not been identified, although it yields 2,2,4,4-tetramethylpentanoic acid, indicative of the isoöctyl substituent, upon hydrolysis. The same acid is obtained by permanganate oxidation of Friedel–Crafts-synthesized 2,5-di-[2,4,4-trimethyl-2-pentyl]furan, a compound which yields trans-2,2,4,4,9,9,11,11-octamethyl-6-dodecene-5,8-dione.
NUCLEAR MAGNETIC RESONANCE MEASUREMENTS OF COMPLEXES OF CHLOROFORM WITH AROMATIC MOLECULES AND OLEFINS
Authors: Reeves L. W. , Schneider W. G.
Published: May 2006

In order to study the effect of association with π-donors, the proton resonance signal of chloroform in the aromatic solvents benzene, toluene, mesitylene, chlorobenzene, o-dichlorobenzene, bromobenzene, nitrobenzene and in the olefinic solvents 1-hexene, cyclohexene, and cyclohexadiene was measured as a function of concentration. The observed shifts of the resonance signal are indicative of specific complex formation. In the aromatic solvents benzene, toluene, and mesitylene, complex formation results in an anomalous shift of the chloroform resonance to high field, which can be attributed to a large induced diamagnetism resulting from the circulation of π-electrons in the aromatic ring. An approximate calculation indicates that the chloroform molecule in the complex is oriented with the hydrogen atom near the six-fold axis above the plane of the aromatic ring and the chlorines directed away from the ring. In nitrobenzene this type of association with chloroform gives way to n-donor association with the oxygen atom of the nitro group. This type of association also occurs to some extent in the halogenated benzenes. A small shift of the chloroform signal to low field is observed with the olefinic solvents, which is attributable to weak π-donor association. Analysis of the freezing-point diagrams of the binary systems with chloroform provide further evidence of complex formation.
THE CONFIGURATION OF GLYCOSIDIC LINKAGES IN OLIGOSACCHARIDES: III. O-α-D-MANNOPYRANOSYL-(1 → 2)-O-α-D-MANNOPYRANOSYL-(1 → 2)-D-MANNOSE
Authors: Gorin P. A. J. , Perlin A. S.
Published: May 2006

A trisaccharide obtained after acetolysis of Saccharomycesrouxii mannan is shown to be O-α-D-mannopyranosyl-(1 → 2)-O-α-D-mannopyranosyl-(1 → 2)-D-mannose. Methylation and lead tetraacetate Oxidation techniques define the positions of the glycosidic linkages. The configurations of the two linkages are determined through use of two novel degradative methods which yield 2-O-α-D-mannopyranosyl-D-mannose and 2-O-α-D-mannopyranosyl-glycerol, each containing one of the glycosidic linkages of the parent trisaccharide.
DÉRIVÉS DU TRIMÉTHYL-1,8,8 BICYCLO[3,2,1]OCTANE: II. SUR LES ÉTHERS CÉTOÉNOLIQUES MÉTHYLIQUES ET ÉTHYLIQUES DE LA TRIMÉTHYL-1,8,8 BICYCLO[3,2,1]OCTANEDIONE-2,4
Authors: Favre H. , Marinier B.
Published: May 2006

not available
2-(β-DIALKYLAMINOETHYLMERCAPTO)-2-IMIDAZOLINES
Authors: Winthrop Stanley O. , Grant Gordon A.
Published: May 2006

not available
SURFACE STUDIES USING ION EXCHANGE AUTOCHROMATOGRAPHY
Authors: Krehbiel Ruth E. , Spinks J. W. T.
Published: May 2006

In order to investigate surface exchange phenomena in detail, a new method, the method of ion exchange autochromatography, has been developed. Its application to the study of finely divided precipitates of strontium sulphate is described.
ORGANIC DEUTERIUM COMPOUNDS: XVII. A SYNTHESIS OF DEUTERATED METHYL CHLOROFORM
Authors: Francis J. E. , Leitch L. C.
Published: May 2006

1,1,1-Trichloroethane-d3 has been synthesized from trichloroethylene in four steps via trichloroethylene-d, 1,1,1,2-tetrachloroethane-d2, and 1,1-dichloroethylene-d2.
SOME ACENAPHTHENE COMPOUNDS
Authors: Charlesworth E. H. , Campbell H. , Conn J. J. , Elston C. T. , Stachiw D. L.
Published: May 2006

A new geometric isomer of 1,2-dichloroacenaphthene has been isolated among the reaction products of acenaphthylene and hypochlorous acid. Some new derivatives of acenaphthenone and acenaphthenol are reported.
A RECORDING VACUUM THERMOBALANCE
Authors: Hooley J. G.
Published: May 2006

A recording quartz spring balance is described, with which weight changes up to 1000 mg. can be followed linearly on a millivolt recorder for samples weighing up to 10 g. During the recording operation the sample may be under vacuum or pressure and may be heated or cooled. The maximum practical sensitivity is about 20 millivolts per milligram and the over-all error in reading the record is about 1 millivolt. The temperature coefficient of fused quartz springs is reported to be − (1.25 ± 0.02) × 10−4 per degree centigrade in the range 20° to 35 °C.The device could be readily adapted for heavier loads and greater weight changes by using less sensitive springs and could be used for measuring dimensional changes of solids with a maximum sensitivity of at least 2000 mv. per millimeter.
VISCOSITY OF NATURAL RUBBER SOLUTIONS AT VERY LOW RATES OF SHEAR
Authors: Golub Morton A.
Published: May 2006

The shear dependence of viscosity of benzene solutions of natural rubber was studied at rates of shear from about 500 down to less than 1 sec.−1. Measurements involved following the change of pressure head with time of the various solutions flowing in a capillary, U-tube viscometer. Curvature in the plots of the logarithm of pressure head versus time indicated non-Newtonian flow. From such curves, reduced viscosity data over the above-mentioned shear range were readily derived. As a check, data over the range 100–500 sec.−1 were also obtained with a five-bulb viscometer of the Krigbaum–Flory type, and these data overlapped those obtained with the U tube. The reduced viscosity increased very sharply with decrease in gradient, making extrapolation to the viscosity axis quite unreliable. However, a theoretical relation proposed by Bueche fitted the composite data rather well. This work furnished a nice technique for determining the zero shear reduced viscosity (ηap/c)0 without the necessity of performing an uncertain extrapolation: evaluate the parameters of the Bueche formula which best satisfies the experimental data over a fairly wide range of shear rates, and then calculate (ηap/c)0 directly.
STRUCTURE OF A HEMICELLULOSE FROM MAPLE WOOD PREVIOUSLY EXTRACTED BY LIQUID AMMONIA
Authors: Neubauer L. G. , Purves C. B.
Published: May 2006

The extraction of maple wood meal with anhydrous liquid ammonia under pressure near 20° altered the wood in such a way that an additional small amount of lignin could be extracted with ethanol, and 1.9% of crude hemicelluloses with hot water. An additional 0.25% of nitrogen was retained, apparently as insoluble amides, by the residual wood. After elimination of pectic material by acetylation, the three subtractions of the hemicellulose acetate had identical specific rotations of −61 ± 1° in chloroform; all three corresponded in composition to a combination of one methylglucuronic anhydride to six anhydroxylose units. A conventional study by the methylation method suggested that the hemicellulose was a branched-chain structure averaging four anhydroxylose units linked 1—4, with one also substituted in the second position, and another linked 1—3.
OXIDATION OF THE ANALYTICAL REAGENT "TIRON" (DISODIUM-4,5-DIHYDROXYBENZENE-1,3-DISULPHONATE)
Authors: Atkinson G. F. , McBryde W. A. E.
Published: May 2006

The analytical reagent "tiron" undergoes oxidation in alkaline solution by the oxygen of the atmosphere to a yellow-colored substance, which is assumed to be the corresponding quinone. In certain circumstances the reagent may be oxidized with production of a green substance believed to be a semiquinone. Interference in the colorimetric determination of iron by means of this reagent may occur in alkaline solution owing to the overlap of the iron III derivative and of the oxidation product. Alkaline solutions of tiron react with iron II salts even in the rigorous absence of oxygen to form the iron III tironate FeR3−9. Oxygenated solutions of tiron in alkali fail to produce this compound with iron III salts, but do so with iron II salts.
THE PREPARATION OF METHYL BISNORCHOLANATE
Authors: Whittingham D. J. , Jones R. Norman
Published: May 2006

not available
ADDITION OF ETHYL RADICALS TO ETHYLENE
Authors: Pinder J. A. , Roy D. J. Le
Published: May 2006

The addition of ethyl radicals to ethylene has been studied in the temperature range 58° to 123 °C. The radicals were produced by the mercury photosensitized decomposition of hydrogen in the presence of ethylene, and the rate of the addition reaction was measured in terms of the rate of formation of n-hexane by the combination of ethyl and butyl radicals. Corrections were made for the non-uniformity of radical concentrations in the reaction zone. Assuming a negligible activation energy for the combination of two ethyl radicals, the activation energy for the addition reaction is 5.5 kcal. per mole; the steric factor, relative to the square root of the steric factor for ethyl radical combination, is 5.0 × 10−5.
PREPARATION OF SOME PURE POLYOXYETHYLENEGLYCOL ETHERS. PART I
Authors: Gingras B. A. , Bayley C. H.
Published: May 2006

The Williamson ether synthesis has been applied to the preparation of polyoxyethyleneglycol mono- and di-ethers. These were obtained by reacting the mixed potassium salts of hexaoxyethyleneglycol with alkyl or aryl halides. Hexaoxyethyleneglycol monoethers of the type R•O(CH2CH2•O)6H, (R = n-C10H21, n-C12H25, n-C14H29, and p-iso-C8•H17•C6H4•O•CH2CH2) and diethers of the type R•O(CH2•CH2•O)6•R, (R = n-C10H21, n-C12H25, and n-C14H29) have been prepared in pure state and some of their properties determined.
POLAROGRAPHIC BEHAVIOR OF THE VIOLOGEN INDICATORS
Authors: Elofson R. M. , Edsberg R. L.
Published: May 2006

The polarographic behavior of 1,1′-dimethyl- and 1,1′-dibenzyl-4,4′-bipyridinium dichloride has been investigated over the pH range of 1 to 13. Reversible reduction waves are obtained for the first single-electron step for both compounds. The second step is electrochemically irreversible but evidence is presented to indicate that the second step is fleetingly reversible at the dropping mercury electrode for methyl viologen but not benzyl viologen. Minor waves due to adsorption of the reduced viologen on the surface of the mercury have been observed.