bluuebunny/crossref_metadata_2025 huggingface dataset:
ALKALOIDS OF LYCOPODIUM ANNOTINUM: PART II. ISOLATION OF FOUR NEW ALKALOIDS
Authors: Anet F. A. L. , Khan N. H.
Published: May 2006

Countercurrent distribution of the alkaloids of Lycopodiumannotinum gave four new bases: annofoline, lycofoline, and α- and β-lofoline. Annofoline, C16H25O2N, contained a keto and a hydroxyl group. Lycofoline, C16H25O2N, possessed at least one hydroxyl group and possibly a double bond, α- and β-Lofoline each had the formula C18H29O3N and contained a hydroxyl and an O-acetyl group.
THE REACTION BETWEEN DIPHENYLAMINE AND NITRATES IN ULTRAVIOLET LIGHT
Authors: Coldwell B. B. , McLean S. R.
Published: May 2006

Under the activating influence of short-wave ultraviolet light, diphenylamine and nitrate ions in solution or on filter paper react to yield a yellow-colored product. Between pH 4 and 10 this consists mainly of 2-nitrodiphenylamine and 4-nitrodiphenylamine. Over this range of pH, the absorption maxima at 405 mμ did not shift; however, the intensity of absorption appeared to reach a minimum at or near neutrality and then increase rapidly as the solution was made more alkaline. The reaction rate was not affected by lowering the concentration of diphenylamine from 0.38% to 0.038%. A similar change in nitrate concentration decreased the rate 5.4 times. No evidence of nitroso compounds was found. Possible mechanisms are suggested.
A STUDY ON THE STRUCTURE OF THE CYCLOPENTADIENYL ANION WITH C14 AS TRACER
Authors: Tkachuk R. , Lee C. C.
Published: May 2006

Starting with formaldehyde-C14, 1,2-dibromocyclopentane-4-C14 (XI) was synthesized in eight steps. Conversion of XI to cyclopentadiene was accomplished in three different ways, namely: the dehydrobromination of XI with quinoline at 195–198 °C, the preparation of 1,2-bis-(trimethylammonium)-cyclopentane-4-C14 hydroxide from XI followed by thermal decomposition, and the conversion of XI to 3,5-dibromocyclopentene followed by reaction of the latter with magnesium in dry ether. Degradations of the samples of cyclopentadiene obtained by these three synthetic routes showed a completely randomized distribution of the C14 activity, with 20% of the total activity on each of the five carbon positions. These results led to the conclusion that these preparations of cyclopentadiene very likely involved ionization to the cyclopentadienyl anion. The randomized distribution of C14 in the resulting products thus furnishes a strong indication that all five carbon positions in the cyclopentadienyl anion are equivalent.
THE MECHANISM OF THE PHOTOOXIDATION OF ACETALDEHYDE AT ROOM TEMPERATURE
Authors: Calvert Jack G. , Hanst Philip L.
Published: May 2006

The initial rates of product formation in the photooxidation of acetaldehyde at room temperature have been determined through the use of infrared spectrometry. The rates of formation of the products peroxyacetic acid, carbon monoxide, carbon dioxide, methanol, formic acid, and acetic acid were determined in experiments with various pressures of acetaldehyde, oxygen, and added gases. The amounts of methylhydroperoxide and acetylperoxide formed in all of the experiments were below the detection limit of the analytical methods. The results require that some modification and corrections be made to the mechanism suggested by McDowell and Sharples.
THE STUDY OF ELECTRICALLY DISCHARGED O2 BY MEANS OF AN ISOTHERMAL CALORIMETRIC DETECTOR
Authors: Elias L. , Ogryzlo E. A. , Schiff H. I.
Published: May 2006

Molecular oxygen was subjected to an electrodeless discharge in the pressure range 0.1–3 mm Hg. The oxygen atom concentration was measured as a function of time in a flow system by means of a movable atom detector which consisted of a platinum wire coated with a suitable catalyst for atom recombination. The atom concentration was calculated from the heat liberated when the detector was operated under isothermal conditions. The surface recombination was found to be first order in the atom concentration. A value of 7.7 × 10−5 was obtained for the recombination coefficient (γ) on Pyrex. No temperature dependence for γ was observed. The gas phase recombination of oxygen atoms was found to be consistent with the mechanism[Formula: see text]The rate constant for the third-order reaction was found to have a value of 1.0 × 1014 cc2 mole−2 sec−1, and a small negative temperature dependence.Evidence was also obtained for the presence of considerable amounts of excited molecular oxygen in electrically activated O2.
THE POLYOXYPHENOLS OF WESTERN RED CEDAR (THUJA PLICATA DONN.): I. ISOLATION AND PRELIMINARY CHARACTERIZATION OF PLICATIC ACID
Authors: Gardner J. A. F. , Barton G. M. , Maclean Harold
Published: May 2006

An amorphous, optically active, heat and light sensitive, polyoxyphenolic acid (pKa = 3) has been isolated from the mixture of polyoxyphenols present in the aqueous extractive of western red cedar. Analyses of crystalline derivatives are consistent with a molecular formula of C20H22O10. Color tests, spectra, methylation, and alkaline nitrobenzene oxidation results indicate it to be a propylphenol dimer, a lignan acid, in which one aromatic ring is 3-methoxy-4-hydroxyphenyl and the other is 3,4-dihydroxy-5-methoxyphenyl. Acetylation results and lactone formation require the presence of three alcoholic hydroxyls, one of which is in the γ position to the carboxyl.
INFRARED SPECTRA AND STRUCTURE OF POLYALDEHYDES: III. POLYACETALDEHYDE AND POLYPROPIONALDEHYDE
Authors: Novak A. , Whalley E.
Published: May 2006

Acetaldehyde and propionaldehyde have been polymerized at room temperature and pressures of about 10 kb. The infrared spectra of the polymers have been investigated and it is shown that the polymers have the formula HO(CHR•O)nH. The spectra are too complicated to be understood if there is only one monomer unit in the repeating unit of the chain; there are at least two units.
THE INFRARED SPECTRA AND STRUCTURE OF POLYALDEHYDES: IV. THE HIGHER POLYALDEHYDES
Authors: Novak A. , Whalley E.
Published: May 2006

The polymers of n- and iso-butyraldehyde and n-valeraldehyde, which were made by subjecting the aldehydes to pressures of about 8 kb, have been examined by infrared spectroscopy. They are homologues of polyformaldehyde, having the formula HO(CHR•O)nH.
INFRARED SPECTRA AND STRUCTURE OF POLYALDEHYDES: V. POLYMONOCHLOROACETALDEHYDE AND POLYDICHLOROACETALDEHYDE
Authors: Novak A. , Whalley E.
Published: May 2006

The polymers of monochloroacetaldehyde and dichloroacetaldehyde have been examined by infrared spectroscopy. They are homologues of polyformaldehyde, having the formula HO(CHR•O)nH. X-ray-diffraction powder photographs show that they are fairly crystalline.
INTERACTION BETWEEN KETONE AND TERTIARY AMINE GROUPS
Authors: Wheeler Owen H. , Levy Eric M.
Published: May 2006

Vapor pressure studies of trimethylamine and ketones in heptane solution have shown that unstable complexes are formed with cyclohexanone at 0° and with cyclohexanone and cyclopentanone at −40°. No complex formation was observed with methylethyl ketone, diethyl ketone, or cyclopentanone at 0°.
A SHORTER SYNTHESIS OF GLUTATHIONE
Authors: Berse Casimir , Boucher Roger , Piché Lucien
Published: May 2006

A preparation of glutathione is proposed, in which the cystinyl residue is at one stage only partially reduced, to uncover the basic groups necessary for ensuing condensation, but without cleavage of the disulphide linkage. This affords an economy of intermediate steps but it does not provide a substantial increase in over-all yield of the hormone.
AN ASYMMETRIC SYNTHESIS OFD- ANDL-MANNOSAMINE
Authors: O'Neill A. N.
Published: May 2006

The addition of ammonia to the ethylenic bond of D-arabo-tetraacetoxy-1-nitrohexene-1 was stereospecific and formed a crystalline product, 1-nitro-1-deoxy-N-acetyl-D-mannosaminol. Application of the Nef reaction to this compound gave 2-amino-2-deoxy-D-mannose, which was isolated as the crystalline pentaacetate and further characterized as the hydrochloride by deacetylation with hydrochloric acid. In the deacetylation of the pentaacetate with barium methoxide, however, an abnormal epimerization occurred to yield N-acetyl-D-glucosamine.L-Mannosamine pentaacetate was synthesized in a similar manner from L-arabo-tetra-acetoxy-1-nitrohexene-1.
SYNTHESIS OF SUGARS FROM SMALLER FRAGMENTS: PART XI. SYNTHESIS OF L-GALACTOHEPTULOSE
Authors: Jones J. K. N. , Matheson N. K.
Published: May 2006

1,3-Dihydroxy-2-propanone phosphate condenses with L-threose in the presence of the enzyme aldolase to yield L-galactoheptulose phosphate, from which the heptose was prepared.
LYCOPODIUM ALKALOIDS: VIII. LYCOPODINE
Authors: MacLean D. B. , Harrison W. A.
Published: May 2006

Information pertaining to the position of the carbonyl group relative to the nitrogen atom and to the size of one of the nitrogen rings in lycopodine has been obtained through a study of the reactions of α- and β-cyanobromolycopodine.
THE CONSTITUTION OF THE SODIUM–ACID PHOSPHATE GLASSES
Authors: Westman A. E. R. , Smith M. Joyce , Gartaganis P. A.
Published: May 2006

The preparation of phosphate glasses containing sodium and hydrogen is described. The over-all composition was calculated from the Na/P ratio of the starting mixture and the hydrogen content determined by a zinc oxide ignition. The chemical constitution was determined paper-chromatographically employing recent improvements in technique.Close resemblance between the molecular weight distributions of the sodium–acid glasses and the strong phosphoric acids is shown by the results, but it is also shown that there is no sharp transition to the molecular weight distribution shown by the sodium, potassium, and lithium glasses.The importance of stoichiometry on the constitution of glass is discussed, together with the statistical models from which several theories are derived to predict the distribution of the polymers in a glass. The theories of Van Wazer and Parks, which show the most satisfactory agreement with the experimental results, receive detailed consideration.
THE PREPARATION OF D-RIBOSE-1-C14, D-ARABINOSE-1-C14, AND D-2-DEOXYRIBOSE-1-C14
Authors: Murray D. H. , Butler G. C.
Published: May 2006

D-Ribose-1-C14 and D-arabinose-1-C14 have been synthesized by a modified Sowden–Fischer procedure in which the mixed sodium nitropentitols resulting from the condensation of erythrose and C14H3NO2 have been submitted to a Nef reaction. The epimeric labelled pentoses were isolated by cellulose column chromatography in an over-all radiochemical yield of 19%.Mixed nitropentitols-1-C14 have been acetylated, partially deacetylated with sodium bicarbonate in a non-polar solvent, and hydrogenated to yield triacetoxy-1-nitropentane-1-C14. The mixture of this material and the accompanying undeacetylated nitropentitols gave rise, via a Nef reaction, to D-2-deoxyribose-1-C14 (6.3%), D-ribose-1-C14 (3.1%), and D-arabinose-1-C14 (2.9%).
THE MERCURY-DISCHARGE REDUCTION OF PHOSPHORUS TRICHLORIDE
Authors: Finch Arthur
Published: May 2006

not available
INFRARED SPECTRUM OF AMMONIUM HYDROPEROXIDE
Authors: Knop Osvald , Glguère Paul A.
Published: May 2006

not available
THE EXCHANGE OF OXYGEN-18 BETWEEN CELLULOSE, ADSORBED WATER, AND WATER VAPOR
Authors: Lang A. R. G. , Mason S. G.
Published: May 2006

The adsorption on regenerated cellulose of water at vapor pressures of 0 to 40 μ Hg has been measured by an oxygen-18 dilution technique. The results showed that cellulose may be dried to less than 0.04% moisture by evacuation at 70 °C. The adsorption isotherm was compared with that of Taylor for viscose rayon.It was also shown that oxygen-18 does not exchange between cellulose and water.
THE ABSOLUTE CONFIGURATION OF (+)-DES-(OXYMETHYLENE)-LYCOCTONINE HYDRIODIDE MONOHYDRATE AND (+)-DEMETHANOLACONINONE HYDRIODIDE TRIHYDRATE
Authors: Przybylska Maria , Marion Léo
Published: May 2006

By X-ray analyses it has been possible to derive the absolute configuration of (+)-des-(oxymethylene)-lycoctonine and that of (+)-demethanolaconinone. These are shown in Figs. 2 and 3.
SYNTHESES IN THE TERPENE SERIES: VIII. SYNTHESIS OF THE CIS- AND TRANS-ISOMERS OF 7,7,10-TRIMETHYLDECAL-1-ONE. A CONVENIENT MODIFICATION OF THE BROWN HYDRATION REACTION
Authors: Sondheimer Franz , Wolfe Saul
Published: May 2006

7,7,10-Trimethyl-Δ1(9)-octal-2-one (VII) was converted to the cycloethylenedithioketal (VIII), which on Raney nickel reduction yielded 7,7,10-trimethyl-Δ1(9)-octalin (IX). Oxidation with perbenzoic acid led to the corresponding oxide (X), which could be rearranged in low yield to an equilibrium mixture of 7,7,10-trimethyldecal-1-one consisting essentially of the trans-isomer (XI).A convenient modification of the Brown hydration reaction is described, whereby the necessity of generating diborane or of using diglyme is avoided. 7,7,10-Trimethyl-Δ1(9)-octalin (IX) on Brown hydration using this modification stereospecifically furnished 7,7,10β-tri-methyl-cis-decal-1β-ol (XII), which was oxidized to 7,7,10-trimethyl-cis-decal-1-one (XIII). Isomerization resulted in the above-described equilibrium mixture containing at least 90% of the trans-isomer (XI). Similarly, the previously described 10-methyl-Δ1(9)-octalin (XVI) yielded a mixture of the cis- and trans-isomers of 10-methyldecal-1-one (XIX). Syntheses of 2-methylene-7,7,10-trimethyl-Δ1(9)-octalin (XIV) and of 7,7,10-trimethyl-cis-decal-2,3-dione 3-dithiotrimethylene ketal (XXII) are also described.
MYCOCHRYSONE: II. CARBON SKELETON, PRINCIPAL CHROMOPHORE, AND OXYGEN FUNCTIONS
Authors: Read G. , Vining L. C.
Published: May 2006

A mono-and di-methyl ether and two diacetates of mycochrysone have been prepared. Elemental analyses of these derivatives and of the purified pigment itself are consistent with a revised C20H12O7 formula for mycochrysone.The formation of a leucohexaacetate suggests that the molecule contains two hydroxyl or potential hydroxyl oxygen functions in addition to the quinonoid and phenolic (or enolic) groups already shown to be present. The infrared spectra of mycochrysone and derivatives provide evidence that the remaining oxygen atom is ketonic. The principal chromophore of mycochrysone is related to 8-hydroxy-1,2-naphthoquinone. Hydrogenation experiments indicate that the pigment has a perylene carbon skeleton.
CONDUCTANCES OF DILUTE SOLUTIONS OF POTASSIUM IODATE IN WATER AND WATER–DIOXANE MIXTURES AT 25 °C
Authors: Bock E.
Published: May 2006

Conductances of dilute solutions of potassium iodate in water and water–dioxane solutions, extending over the dielectric constant range from D = 78.54 to D = 29.71, have been measured over the concentration range from zero up to Ka < 0.2 at 25.00 °C. By applying the Fuoss–Onsager treatment to the data obtained, the association constants for the electrolyte in the various solvents, as well as å, the distance of closest approach of the ions, have been determined.
SENSITIVE VIBRATIONAL FREQUENCIES: IV. MASS EFFECTS
Authors: Wilmshurst J. K.
Published: May 2006

The correlation of vibrational frequencies with atomic properties of substituent atoms in the molecular system is critically examined for reality in the light of possible mass effects. The general rule is formulated that only frequencies continuously characteristic of a grouping in the mass–frequency plot can be used in such correlations. Calculated mass–frequency plots are presented for the systems XC≡N, XC≡CX, XC≡CY, X2C=CX2, X2C=O, X2P=O, XCH3, X2CH2, X3CH.
CATALYSIS OF THE CIS-TRANS ISOMERIZATION OF AZOBENZENE BY ACIDS AND CUPRIC SALTS
Authors: Ciccone Stefania , Halpern J.
Published: May 2006

The catalytic effects of various acids and metal salts on the cis-trans isomerization of azobenzene in aqueous ethanol were examined kinetically. The effect of perchloric acid is apparently due to H+ ions and is interpreted in terms of a catalytic mechanism involving the conjugate acid of azobenzene. The much greater catalytic effect found for hydrochloric acid is attributed to an additional path involving catalysis by the undissociated acid. Acetic acid was found to be inactive. Of the metal salts examined only those of Cu++ showed pronounced activity which was attributed to co-ordination with the azo group. Kinetic evidence was obtained for a catalytic path involving Cu++ and H+ simultaneously.
THE THIRD LAW ENTROPY AND STRUCTURE OF IRON PENTACARBONYL
Authors: Leadbetter A. J. , Spice J. E.
Published: May 2006

The heat capacity of solid and liquid iron pentacarbonyl has been measured from 20° to 290°K. The heat of fusion was also measured and found to be 3161 ± 3 cal/mole. From an investigation of the change of temperature of the sample during melting the triple point of iron pentacarbonyl was estimated to be 253.15°K and the purity of the sample 99.9 mole%. An anomalous absorption of energy amounting to 4.8 cal/mole was observed at about 230°K; this is shown to be due to an unknown impurity in the sample. The vapor pressure of the liquid was measured in the vicinity of room temperature and from these results the heat of vaporization at 25 °C was estimated to be 9.1 ± 0.1 kcal/mole.The entropy of iron pentacarbonyl as an ideal gas at 1 atm pressure and 25 °C computed from the thermal measurements is 106.4 ± 0.8 cal/mole deg. Comparison of this quantity with values calculated from spectroscopic data indicates that the iron pentacarbonyl molecule has the form of a trigonal bipyramid rather than that of a square pyramid.
THE SYNTHESIS OF 5-O-METHYL-L-ARABINOSE
Authors: Dutton G. G. S. , Tanaka Y. , Yates K.
Published: May 2006

5-O-Methyl-L-arabinose is thought to occur in the hydrolysis products of methylated wheat bran hemicellulose. This sugar has now been synthesized from ethyl 2,3-di-O-acetyl-5-O-trityl-α-L-arabinoside by detritylation, methylation, and hydrolysis. The free sugar was obtained as a sirup and was characterized by periodate oxidation together with the preparation of a crystalline osazone and a crystalline lactone.
TRANSFERENCE NUMBERS AND CONDUCTANCES IN CONCENTRATED SOLUTIONS: SILVER NITRATE AND SILVER PERCHLORATE AT 25.00 °C
Authors: Campbell A. N. , Singh K. P.
Published: May 2006

The transference numbers, equivalent conductances, densities, and viscosities of aqueous solutions of silver nitrate and of silver perchlorate have been determined from a concentration of 0.1 M up to 7.6 M, for silver nitrate, and up to 5.6 M for silver perchlorate. In both cases the cation transference number increases considerably with increasing concentration. Certain anomalies in the results for silver perchlorate raise the possibility of complex ion formation here. Similar anomalies appear in the behavior of equivalent conductance with respect to concentration.The results of the conductance measurements have been compared with the values calculated from the equations of Wishaw and Stokes and of Falkenhagen and Leist.
VOLUCRISPORIN: ISOLATION, STRUCTURE, AND SYNTHESIS OF THE METHYL ETHER
Authors: Divekar P. V. , Read G. , Vining L. C. , Haskins R. H.
Published: May 2006

A new pigment, volucrisporin, has been isolated from shaken cultures of the Hyphomycete Volucrisporaaurantiaca Haskins, and characterized as 2,5-(m-hydroxyphenyl)-1,4-benzoquinone. The structure has been confirmed by synthesis of the dimethyl ether.
THE NATURE OF THE SPECIFICITY OF ADSORPTION OF ALKYL ORANGE DYES ON SILICA GEL
Authors: Morrison John L. , Worsley M. , Shaw D. R. , Hodgson G. W.
Published: May 2006

The properties of silica gels sensitized by methyl orange and its homologues were critically examined in order to decide between the alternative hypotheses of a lock and key mechanism and an association mechanism to explain the enhancement of adsorption. Evidence appears to favor an association mechanism in which the unextractable dye particles act as centers to attract their own kind more strongly than one of their homologues. Nitrogen area measurements show that less than 0.5% of the gel surface area is used in adsorbing dye molecules. The dye series from methyl to butyl orange have a very sharp increase in solubility from ethyl to propyl when dissolved in 5% aqueous acetic acid solution (pH = 2.3).
THE DECAY OF ACTIVE NITROGEN AT HIGH TEMPERATURES
Authors: Back R. A. , Dutton W. , Winkler C. A.
Published: May 2006

Previous studies of the decay of active nitrogen have been extended to higher temperatures. A more detailed treatment of the results suggests that surface recombination of nitrogen atoms may be either first or zero order. Rate constants for both the surface and the homogeneous recombination of nitrogen atoms are reported. The latter shows a slight positive temperature coefficient.
L'ARYLATION DES QUINONES PAR LES SELS DE DIAZONIUM: VI. SUR L'IDENTIFICATION DE L'ISOMÈRE OBTENU PAR L'ARYLATION DE LA TOLUQUINONE
Authors: Hoegerle K. , L'écuyer P.
Published: May 2006

not available
ON THE COUPLING BETWEEN H1 AND F19 NUCLEI IN p-FLUOROTOLUENE. II
Authors: Schaefer T. , Schneider W. G.
Published: May 2006

By making use of specific solvent interaction effects it has been found possible to vary the relative chemical shift between ortho and meta protons in p-fluorotoluene continuously from about 0.2 p.p.m. to zero. The values of the HF coupling constants were found to be [Formula: see text] and [Formula: see text]. As the internal chemical shift goes to zero the ring proton spectrum collapses to two lines with a separation of 7.3 c/s. This splitting is interpreted as equal to [Formula: see text]. Corresponding changes observed in the CH3 proton spectrum are consistent with this interpretation.
SOLUBILIZATION IN AQUEOUS BUTYRIC ACID SOLUTIONS
Authors: Moule D. , Benson G. C.
Published: May 2006

not available
THE PREPARATION OF Δαβ-BUTENOLIDE
Authors: Smith R. J. D. , Jones R. N.
Published: May 2006

not available
SYNTHESIS OF POLYMETHYLENEBISISOTHIOCYANATES
Authors: Thorn G. D. , Huston B.
Published: May 2006

not available
SOME PROPERTIES OF SILICA DISPERSIONS
Authors: Sirianni A. F. , Meadus F. W. , Puddington I. E.
Published: May 2006

When silicic acid sols are formed from solutions of sodium silicate by acid neutralization, a pronounced minimum in the time required for the sol–gel transformation is observed if the titration is stopped near pH 8. If the sol is prepared by electrodialysis, a similar minimum is obtained when the operation is stopped at about pH 5.5. Intermediate values for the minimum are found if the original silicate solution is partially dialyzed followed by neutralization with acid. When the water content of the gels is replaced by liquid hydrocarbons, maximum interaction between the silica particles occurs when the aqua gel has been formed or conditioned at pH 5.5 regardless of the method of preparation of the sol. A minimum in electrophoretic mobility and a maximum in sedimentation rate of the particles are observed at a similar pH value. These properties are modified considerably if the system is thoroughly dehydrated.
THE RELATIVE ENTHALPIES OF CONCENTRATED POTASSIUM HYDROXIDE SOLUTIONS
Authors: Biermann Wendell J.
Published: May 2006

Measurements were made of the heats of neutralization of concentrated solutions of potassium hydroxide with hydrochloric acid, with an estimated accuracy better than one part per thousand. From this information it was possible to calculate relative enthalpy data for potassium hydroxide solutions up to 16 molal.
HYDROGEN BONDING IN DIASTEREOISOMERIC α-β AMINOALCOHOLS: A REINVESTIGATION OF THE EPHEDRINES BY N.M.R
Authors: Hyne James B.
Published: May 2006

The results of an n.m.r. study of the diastereoisomeric ephedrine and ψ-ephedrine molecules in non-polar solvents are interpreted and discussed in terms of the relative stabilities of the intramolecularly hydrogen-bonded conformers.
THE STRUCTURE OF 2-p-DIMETHYLAMINOBENZYLIDENEINDOXYL AND ITS SALTS
Authors: Abramovitch R. A. , Marko A. M.
Published: May 2006

2-p-Dimethylaminobenzylideneindoxyl has been shown to have mainly the dipolar quinonoid structure (II), though quaternization takes place at the dimethylamino nitrogen atom in the unperturbed structure (I). This has been established by a study of its infrared and ultraviolet absorption spectra and by a comparison of these with those of its monohydrochloride, its methiodide, and of 2-benzylideneindoxyl.
ADSORPTION EQUILIBRIA OF HYDROGEN, DEUTERIUM, AND THEIR MIXTURES. PART I
Authors: Basmadjian D.
Published: May 2006

Adsorption isotherms of hydrogen and deuterium have been measured at temperatures of 75–90 °K and pressures up to 760 mm Hg on the following six adsorbents: charcoal (2), silica gel, and Linde molecular sieves type 4A, 5A, and 13X.Deuterium was found to be adsorbed to a greater extent than hydrogen in all cases investigated, its isosteric heat of adsorption exceeding that of hydrogen by 50 to 300 cal/mole.Binary adsorption isotherms were determined on the same adsorbents in the range 10–90% D2 at temperatures of 75 and 90 °K and a total pressure π of 750 and 200 mm Hg. The analyses were performed by the thermal conductivity method using thermistor sensing elements in a static system at atmospheric pressure. The device proved of exceptional stability, requiring no recalibrations and yielding an analytical accuracy of better than 0.02% deuterium content. The binary separation factors α were found to be constant over the concentration range investigated, with values for α varying from about 1.25 on charcoal to 2.54 on type 4A molecular sieves at 75 °K and 750 mm Hg. The results suggest that the variations in α are due mainly to differences in chemical composition of the adsorbents rather than pore size, surface area, or origin of the materials.
HALF-LIVES OF THE NUCLIDES Au195, Pt195m, AND Pt197
Authors: Bresesti M. , Roy J. C.
Published: May 2006

The half-lives of Au195, Pt195m, and Pt197 have been measured. The radionuclides were produced by neutron irradiation in the NRX reactor at Chalk River and were radiochemically purified after the irradiation. The decay of the X rays and γ-radiations from Au195 and Pt195m was observed with a NaI (Tl) detector, and the β-decay of Pt197 was observed with an anthracene detector. The half-lives are:[Formula: see text]The errors quoted are the estimated reliability of the measurement and include the statistical counting error plus an estimated systematic error.
A METHOD OF INTEGRATION OF THE GIBBS–DUHEM EQUATION WHEN ACTIVITIES OF A SOLUTE ARE REQUIRED FROM THOSE OF THE SOLVENT
Authors: Lakhanpal M. L. , Conway B. E.
Published: May 2006

A new graphical method has been developed for integrating the Gibbs–Duhem equation for the case where activities of the solute are required from experimentally determined values of the activity of the solvent in a binary solution. This method has been applied to the determination of the activities of fractions of polyoxypropylene glycols in methanolic solutions. The accuracy of the procedure is discussed.
THE GAS HYDRATE OF BROMOCHLORODIFLUOROMETHANE
Authors: Glew D. N.
Published: May 2006

An experimental study has been made of the saturation pressure – temperature lines of liquid bromochlorodifluoromethane, liquid bromochlorodiflucromethane – water, bromochlorodifluoromethane hydrate – water, and bromochlorodifluoromethane hydrate – ice systems, for which the characteristic equations are given. Two quadruple points for the hydrate systems have been located and solubilities of water in bromochlorodifluoromethane and bromochlorodifluoromethane in water determined. A systematic treatment of gas hydrate saturation pressure data to yield thermodynamic equations is indicated, and the thermodynamic functions for bromochlorodifluoromethane hydrate and its phase reactions are tabulated. Bromochlorodifluoromethane hydrate is shown to be a stoichiometric compound, and its thermodynamic functions are considered in relation to those of other gas hydrates.
STUDIES IN THE WAGNER–MEERWEIN REARRANGEMENT: PART IV. DERIVATIVES OF BENZ[b]FLUORENE
Authors: Anet F. A. L. , Bavin P. M. G.
Published: May 2006

10-Methyl-10-benz[b]fluorenylmethyl tosylate gave mainly 5-methylbenz[a]anthracene on formolysis, but the related alcohol gave a mixture of the 5- and 6-methyl isomers by reaction with phosphorus pentoxide. Reaction of benz[b]fluorenone with excess diazomethane gave 5-methoxybenz[a]anthracene as the only isolable product. The alkylation of methyl benz[b]fluorene-10-carboxylate was studied.
PHYSICOCHEMICAL STUDIES OF ALKALI LIGNINS: III. SIZE AND SHAPE OF THE MACROMOLECULE
Authors: Gupta P. R. , Goring D. A. I.
Published: May 2006

Light-scattering measurements were made on the alkali lignin fractions described in a previous paper. The range of molecular weights found was from 50,000 to 48 × 106. The usual logarithmic graph of intrinsic viscosity and molecular weight was linear and gave a value of 0.32 for the exponent. From the logarithmic sedimentation coefficient – molecular weight relationship, the exponent was found as 0.52. Flory's hydrodynamic parameter [Formula: see text] was 2.3 × 106. These results suggested that the configuration of the alkali lignin macromolecule conformed to a structure between that of a random coil and an Einstein's sphere impenetrable to solvent. The branching parameter, g, introduced by Zimm and Stockmayer, decreased with an increase in molecular weight as expected. Most of the values of Huggins' constant, k′,were between 1 and 2 which indicated a compact particle. A marked increase in k′ was noted for fractions of low or very high molecular weight. The significance of the data is discussed and a model tentatively suggested for the macromolecule.
CHEMICAL SHIFTS IN THE NUCLEAR MAGNETIC RESONANCE SPECTRA OF MOLECULES CONTAINING POLAR GROUPS
Authors: Buckingham A. D.
Published: May 2006

It is shown that the electric field at a particular nucleus arising from polar groups in other parts of a molecule can lead to chemical shifts proportional to the first power of the field strength. The change Δσ in the proton screening constant of an X—H bond when it is subjected to an electric field E is approximately given by[Formula: see text]where Ez is the component of E in the bond direction. A field along the X—H bond draws the electrons in the enriched region between the nuclei away from the proton, thereby causing its resonance to occur at lower magnetic field strengths, while a field in the H—X direction leads to resonance at higher fields. The electric field produced by the polarization of neighboring solvent molecules may also be important and lead to a solvent shift related to the dielectric constant of the solvent. The direction of the internal field, and that due to the solvent, can easily be estimated when the molecule is rigid, so that the model can be useful in assigning spectra. It gives a simple and reasonably accurate account of the observed spectra of substituted benzenes and of some solvent effects on the proton resonances of cis- and trans-1,2-dichloroethene.
THE REACTION OF SODIUM METAPERIODATE WITH SOME NITROGEN DERIVATIVES OF CARBOHYDRATES
Authors: Abercrombie M. J. , Jones J. K. N.
Published: May 2006

not available
ELECTRON SPIN RESONANCE ABSORPTION OF BORO-ULTRAMARINE
Authors: Matsunaga Yoshio
Published: May 2006

not available
THE REACTIONS OF ACTIVE NITROGEN WITH HYDROGEN SULPHIDE AND CARBON DISULPHIDE
Authors: Westbury R. A. , Winkler C. A.
Published: May 2006

The destruction of either hydrogen sulphide or carbon disulphide by active nitrogen appears to be minimal at some temperature in the range 200–250 °C. Both reactions yield large amounts of polymer.It is postulated that the main reactions involve destruction of the reactant as it acts as a third body for recombination of nitrogen atoms. As the temperature is increased, dissociation of the nitrogen atom – reactant complex apparently increases. To account for the observed temperature effects, it is assumed that reactions also occur to regenerate reactant.
BACTERIOSTATS: III. OXYAMINES AND THEIR DERIVATIVES
Authors: McKay A. F. , Garmaise D. L. , Paris G. Y. , Gelblum S.
Published: May 2006

A number of benzyloxyamines were prepared for conversion into urea and thiourea derivatives. The benzyloxyamine hydrochlorides on treatment with phosgene gave a mixture of the corresponding benzyl 4-(benzyloxy)-allophanate and benzyloxycarbamyl chloride. Triethylamine converted the benzyloxycarbamyl chlorides into the corresponding 1,3,5-tri-(benzyloxy)-isocyanuric acids. The reactions of the allophanates with amines and sodium hydroxide are described.
PROTON MAGNETIC RESONANCE ABSORPTION IN THE C-FORM OF STEARIC ACID
Authors: Grant R. F. , Dunell B. A.
Published: May 2006

The proton magnetic resonance absorption in the C-form of stearic acid has been measured over a temperature range from −78 °C to the melting point. The results suggest that the methyl end groups may be free to rotate about their triad axes throughout this temperature range, and that premelting becomes significant above 40 °C.
ELECTRONIC POTENTIAL SURFACES OF ACETYLENE IN LCAO/MO APPROXIMATION
Authors: King G. W.
Published: May 2006

A digital computer has been programmed to carry out 6-electron LCAO/ASMO calculations for linear and trans-bent acetylene, with the following input variables; coefficients of the LCAO/MOs, carbon–carbon bond length, and effective nuclear charge on the carbon atoms. The effect of varying these parameters upon the calculated electronic energy levels is discussed, and approximations to "best" MOs are obtained for various states of the molecule, leading to values of hybridization parameters for the carbon atoms. Certain assumptions enable the electronic energies to be related to the C—C—H bending angle; from this it is concluded the ground state is linear and the lowest Au excited state is bent, in accordance with experiment. Values are given for electronic transition energies and hydrogen-bending force constants.
THE ACIDITY OF SOME AROMATIC FLUORO ALCOHOLS AND KETONES
Authors: Stewart Ross , Linden R. Van der
Published: May 2006

A series of five trifluoroacetophenones and five phenyl trifluoromethyl carbinols have been synthesized and their ionization constants in water measured. They are the unsubstituted, p-methoxy, p-methyl, m-bromo, and m-nitro compounds. The ketones exist as hydrates in aqueous solution and each is about two pK units stronger than the corresponding alcohol. The acidities of both series are correlated by the Hammett relation with ρ values of 1.11 and 1.01 for the ketone hydrates and alcohols respectively. The acid strengths vary from a pKa of 9.18 for m-nitro-α,α,α-trifluoroacetophenone to 12.24 for p-methoxyphenyl trifluoromethyl carbinol.
THE IONIZATION AND DISSOCIATION OF SOME HALOGEN MOLECULES BY ELECTRON IMPACT
Authors: Frost D. C. , McDowell C. A.
Published: May 2006

The ionization and dissociation of chlorine, bromine, iodine, iodine monochloride, and iodine monobromide by electron impact have been studied in a mass spectrometer which uses a monoenergetic electron source. Many ionization potentials have been observed for these molecules which, of course, refer to the formation of the parent molecular ions in different excited states. These experimental results are discussed in terms of simple molecular orbital theories of the electronic structures of the different halogen molecules.Electron-induced dissociative ionization processes for the different substances have also been studied. Where possible, appearance potentials of both the positive and negative ions have been determined. These results have been used to construct potential energy diagrams illustrating the origin of some of the negative ion and dissociation processes observed.
PERFLUOROALKYL ARSENICALS: PART I. THE PREPARATION OF ALKYL PERFLUOROALKYL ARSENICALS
Authors: Cullen W. R.
Published: May 2006

The reaction of tetramethyldiarsine with trifluoroiodomethane gives dimethyltrifluoromethylarsine. Trifluoroiodomethane and iodomethane similarly react with the compounds (CF3)2M—M(CF3)2 to give the compounds (CF3)3M and (CF3)2MCH3 respectively (M = As or P). Trifluoroiodomethane reacts with iododimethylarsine and diiodomethylarsine in the presence of mercury to give dimethyltrifluoromethylarsine and methylbistrifluoromethylarsine respectively. Heptafluoropropyldimethylarsine can be isolated from a similar reaction using heptafluoroiodopropane.
REACTION OF syn-BENZALDOXIME WITH CARBON MONOXIDE AND HYDROGEN TO YIELD SUBSTITUTED UREAS
Authors: Rosenthal A. , O'donnell J. P.
Published: May 2006

not available
THE YIELD OF Ba140 IN THE THERMAL NEUTRON FISSION OF U235
Authors: Santry D. C. , Yaffe L.
Published: May 2006

not available
AMINO ACID DISTRIBUTION IN BIOLOGICALLY ACTIVE PEPTIDES
Authors: Needleman Saul B. , Blackwell R. Quentin , Fosdick Leonard S.
Published: May 2006

A group of biologically active peptides were examined for possible favored chain positions exhibited by some of the 21 constituent amino acids as well as for the unusual occurrence of specific peptide linkages. High levels of significance were revealed for certain amino acid couplets when they were subjected to chi-square analyses.
THE CHEMISTRY OF THE "AMINOCHROMES": PART IV. SOME NEW AMINOCHROMES AND THEIR DERIVATIVES
Authors: Heacock R. A. , Scott B. D.
Published: May 2006

N-Ethylnoradrenochrome, N-isopropylnoradrenochrome, adrenochrome methyl ether, adrenochrome ethyl ether, and their 2-iodo derivatives have been prepared in crystalline form. The action of acetic anhydride in pyridine on these aminochromes has been studied; acetylated rearrangement products were obtained in each case. N-Ethylnoradrenochrome monosemicarbazone, N-ethylnoradrenolutin, 5,6-diacetoxy-N-ethyl-2-iodoindole, and 5,6-diacetoxy-2-iodo-N-isopropylindole have been prepared. The ultraviolet and visible absorption spectra of the aminochromes described above and several 5,6-diacetoxy- and 3,5,6-triacetoxy-N-alkylindoles have been measured and the paper chromatographic behavior of the unhalogenated aminochromes studied.
RADIATION CHEMISTRY OF CYCLOHEXANE: I. ISOTOPIC COMPOSITION OF HYDROGEN EVOLVED FROM MIXTURES OF C6D12 AND C6H12
Authors: Dyne P. J. , Jenkinson W. M.
Published: May 2006

The yield of D2 formed by a unimolecular process in the γ-ray irradiation of cyclohexane-d12 has been deduced from the isotopic composition of hydrogen evolved from C6H12–C6D12 mixtures. A value of 0.25 molecule/100 ev is found for this "molecular" yield. This yield is only slightly reduced by iodine but is considerably reduced in the presence of biphenyl.
SOLVENT EXTRACTION OF MINERAL ACIDS: PART III. SOLUTE–SOLVENT INTERACTION IN THE SYSTEM HYDROBROMIC ACID – WATER – TRI-n-BUTYL PHOSPHATE
Authors: Kertes A. S. , Kertes V.
Published: May 2006

Evidence, based on physical–chemical measurements of the organic layers, has been presented to show that tributyl phosphate extracts hydrobromic acid as its disolvate in medium acid concentrations, and probably as monosolvate in high concentrations. The determination of water in the tributyl phosphate phases indicates that at low and medium acid concentrations the acid is extracted as its tetrahydrate, and at high concentrations as an unhydrated species. From these results, the formation of [(TBP)2.HBr.(H2O)6] and [TBP.HBr. (H2O)3] could be deduced.
DIFFERENTIATION BETWEEN SOME 2,3- AND 2,5-DISUBSTITUTED PYRIDINE DERIVATIVES BY INFRARED SPECTROSCOPY
Authors: Abramovitch R. A. , Seng Giam Choo , Notation A. D.
Published: May 2006

not available
AN N.M.R. STUDY OF ELECTRON RELEASE BY ALKYL AND ALKOXY GROUPS IN VARIOUS SOLVENTS
Authors: Moodie R. B. , Connor T. M. , Stewart Ross
Published: May 2006

not available
THE SEPARATION OF SOME TERPENOID COMPOUNDS BY GAS–LIQUID CHROMATOGRAPHY
Authors: Rudloff E. von
Published: May 2006

A study has been made of the degree of separation of mixtures of some terpene hydrocarbons, some of their oxygenated derivatives, two sesquiterpene alcohols, and three monophenols on a variety of columns. Temperature and sample size affected the degree of separation and the solid support Chromosorb W, a calcined diatomaceous earth, was found to combine the advantages of Celite and C-22 firebrick without causing decomposition of the sample at higher temperatures. When Craig polyesters were used as liquid phases, separations equal to those obtained on polyethylene glycol were realized with the added advantage that these produced columns which are stable at 190 to 220 °C. Consequently, sesquiterpene alcohols and monophenols were also separated successfully. Another useful liquid phase for both low and high temperatures was found in a meta-linked polyphenyl ether. Squalene was found to be an efficient liquid phase for the separation of terpene hydrocarbons at 130 °C and lower. The possible application of the present findings for preparative work is discussed.
THE STRUCTURE OF SANDARACOPIMARIC ACID
Authors: Edwards O. E. , Nicolson A. , Rodger M. N.
Published: May 2006

Sandaracopimaric acid has been shown to be 7-epipimara-8(14), 18-dienoic acid (II), and Ukita's acid to be 7-epi-13β-pimara-9(14),18-dienoic acid (VI). A hydroxyl-containing acid from Sandarac resin is described.
PROTON MAGNETIC RESONANCE MEASUREMENTS OF FORMAMIDE
Authors: Sunners B. , Piette L. H. , Schneider W. G.
Published: May 2006

The high-resolution proton resonance spectrum of formamide has been measured and analyzed. Quadrupole broadening of the resonance signals due to the N14 nucleus was eliminated by substitution of the isotopic nucleus N15. Twenty-four lines were resolved in the spectrum, which is consistent with restricted rotation about the C—N bond. The non-equivalence of the two protons in the N15H2 group is characterized by a smaller screening constant and a greater spin–spin interaction of the proton which is in the trans position relative to the carbonyl group. It is suggested this difference in the spin coupling of the two protons may be associated with different N—H bond lengths. Pronounced changes in the chemical shifts and spin-coupling constants result when formamide is dissolved in dilute solution in water and acetone. In water solution the relative magnitudes of the spin coupling of the two protons in the NH2 group is reversed from that observed in pure formamide and the coupling of the aldehyde proton to N15 varies by nearly 50%. Heating of formamide above room temperature causes rotation of the NH2 group as well as proton exchange between neighboring molecules. The two effects could be separated. From the observed changes in the proton spectra as a function of temperature the barrier hindering rotation (measured in a 10 mole% solution of formamide in acetone) was found to be 18 ± 3 kcal/mole. The activation energy for proton exchange in pure liquid formamide was found to be 10 ± 3 kcal/mole.
POTASSIUM DERIVATIVES OF FLUORENE AS INTERMEDIATES IN THE PREPARATION OF C9-SUBSTITUTED FLUORENES: I. THE PREPARATION OF 9-FLUORENYL POTASSIUM AND THE INFRARED SPECTRA OF FLUORENE AND SOME C9-SUBSTITUTED FLUORENES
Authors: Scherf G. W. H. , Brown R. K.
Published: May 2006

9-Fluorenylpotassium and 9,9-fluorenyldipotassium have been prepared from the reaction of potassium metal with fluorene in dioxane. These organometallic compounds upon reaction with alkyl and aralkyl halides gave 9-substituted fluorenes.Six different absorption bands in the spectrum of fluorene could be associated with the methylene group: 2930, 1400, 1298, 952, and 692 cm−1. Evidence for this assignment was obtained from deuteration of the organometallic compounds of fluorene and from 9-substituted fluorenes.
THE PREPARATION OF SOME THIOSEMICARBAZONES AND THEIR COPPER COMPLEXES. PART I
Authors: Gingras B. A. , Hornal R. W. , Bayley C. H.
Published: May 2006

A number of thiosemicarbazones and their 1:1 copper complexes are described and the possible structures of the latter are discussed. Formation of copper complexes from aromatic aldehyde and ketone thiosemicarbazones results in a loss of one H atom as indicated by infrared spectra. In the aliphatic series, no loss of H atom is apparent upon complex formation. It is reasonable to assume that different processes are involved resulting in two possible structures for the aromatic and the aliphatic copper complexes. Some chemical evidence supports this view.
DISTRIBUTION OF SUBSTITUENTS IN A PARTIALLY METHYLATED 4-O-METHYLGLUCURONOXYLAN
Authors: Croon Ingemar , Timell T. E.
Published: May 2006

A 4-O-methylglucuronoxylan has been partially methylated and the distribution of the substituents has been established. The hydroxyl group at C3 was less reactive than that at C2 in both the main xylan chain and in the acid side chains. Caution should be exercised in attributing structural significance to the presence of small amounts of sugars containing C3 hydroxyl groups in hydrolyzates from methylated xylans.
THE STUDY OF HYDROGEN BONDING AND RELATED PHENOMENA BY ULTRAVIOLET LIGHT ABSORPTION: PART III. THE STRENGTH OF THE DIMERIC HYDROGEN BOND IN SUBSTITUTED BENZOIC ACIDS AS A MEASURE OF ELECTRONIC AND STERIC INTERACTIONS
Authors: Forbes W. F. , Knight A. R. , Coffen D. L.
Published: May 2006

The strength of the intermolecular (dimeric) hydrogen bond in substituted benzoic acids, as estimated from the observed concentration dependence of the ultraviolet absorption spectra, is found to vary with the nature and the position of the substituent. The effects of a number of substituents on the strength of the dimeric hydrogen bond can be rationalized in terms of the usual electronic and steric interactions. The data indicate that o-methoxybenzoic acid forms a stronger intramolecular hydrogen bond than o-fluorobenzoic acid.
A STUDY OF THE DIMER OF ETHYLENE PLATINOUS CHLORIDE BY PROTON MAGNETIC RESONANCE
Authors: Reeves Leonard W.
Published: May 2006

The proton magnetic resonance line of the powdered ethylene platinous chloride dimer complex has a second moment of 13.68 ± 1 gauss2 at 77 °K and an over-all line width of 11.15 ± 0.4 gauss. Measurements at various temperatures between 77° and 329 °K show that both second moment and line width decrease slightly with temperature. The mean separation of the doublet observed at 77 °K is found to be 4.80 ± 0.3 g.The results are interpreted in terms of a distorted ethylene molecule whose interproton distances correspond to an intermediate structure between ethylene and an ethane in a cis configuration but with two of the cis protons removed. This is consistent with earlier studies of the Raman spectrum. The π-type bond formed between a metal d orbital and an ethylene π* orbital is also consistent with the lack of rotation of ethylene at elevated temperatures.Available results from high-resolution proton resonance studies of ethylene complexed to metal atoms in solutions is discussed.
3-BENZYL-2-METHYL-3,4-DIHYDRO-4-KETOQUINAZOLINE
Authors: Anet Ragini , Somasekhara S.
Published: May 2006

not available
REARRANGEMENT STUDIES WITH C14: IX. THE FORMOLYSIS OF METHYL-C14-ISOPROPYLCARBINYL p-TOLUENESULPHONATE
Authors: Finlayson A. J. , Lee C. C.
Published: May 2006

Formolysis of methyl-C14-isopropylcarbinyl p-toluenesulphonate (I) at reflux temperature gave a mixture of 2-methyl-2-butene (II), 2-methyl-1-butene (III), and 3-methyl-l-butene (IV). The relative amounts of olefins II, III, IV were measured by gas-liquid chromatography to be 88%, 11%, and 1%, respectively. When the formolysis was carried out at 50 °C, besides olefins II, III, and IV, some t-amyl formate was obtained indicating a substitution reaction with neighboring hydrogen participation. Degradation of the mixture of olefins from formolysis gave, among other compounds, radioactive acetone, indicating an isotope position rearrangement in the chief product, 2-methyl-2-butene (II). This rearrangement may be attributed to a 1,2-methyl shift in one of the processes that gave rise to olefin II. A comparison of the data from the acetolysis and the formolysis of I showed that in the E1 reactions, neighboring hydrogen participation is predominant in either solvent. For a change of solvent from acetic acid to the more ionizing formic acid, it was demonstrated that there is a greater degree of neighboring methyl participation while the process involving no neighboring group participation assumes less importance.