bluuebunny/crossref_metadata_2025 huggingface dataset:
ELECTRON CORRELATION AND MOLECULAR SHAPE
Authors: Gillespie R. J.
Published: May 2006

It is proposed that the arrangements of the electron pairs in the valency shell of a central atom of a polyatomic molecule can be predicted by considering the equilibrium arrangements of similar particles on the surface of a sphere with an appropriate law of force between the particles. The arrangements resulting from an inverse square law of force, corresponding to electrostatic repulsions, and a force which is proportional to 1/rn where n is large, corresponding to Pauli forces, are considered specifically. It is shown that the arrangements predicted agree with those found experimentally for molecules containing only non-transitional elements. The possible arrangements for seven, eight, and nine pairs of electrons in a valency shell are discussed in detail. A method is suggested for predicting the arrangements of electron pairs in valency shells containing lone pairs which can occupy alternative non-equivalent positions. The effect of the interactions of electron pairs on bond lengths in certain molecules is discussed. The extension of the same principles to molecules containing transitional elements is briefly outlined.
REACTIONS OF ALLYL RADICALS WITH OLEFINS
Authors: Bryce W. A. , Ruzicka D. J.
Published: May 2006

A study has been made of the mechanisms of the reactions of allyl radicals, produced thermally from diallyl, with various hydrocarbons in the temperature range 460–506 °C. The allyl radical is capable of abstracting hydrogen from certain hydrocarbons and of adding to olefinic double bonds at these temperatures. The rates of formation of the principal products in the reactions between allyl and 1-butene, propylene, and ethylene are linearly related to the square root of the diallyl concentration. Mechanisms are proposed to account for the reaction products formed. In addition to reacting readily with olefins the allyl radical is observed to sensitize the decomposition of n-butane at 506 °C. The implications of the present results with respect to inhibition in pyrolysis of hydrocarbons are discussed briefly.
THE DECOMPOSITION OF METHANE BY LOW-ENERGY ELECTRONS
Authors: Manton J. E. , Tickner A. W.
Published: May 2006

The decomposition of methane by a beam of electrons having energies between 15 and 100 ev has been studied using methane pressures between 10−2and 10−3 mm of mercury. The products were frozen out on a surface cooled to about −220 °C and situated approximately 5 millimeters from the electron beam.Ethane, ethylene, and acetylene were found to be the main products along with smaller amounts of saturated and unsaturated higher hydrocarbons. The results provide some evidence that under these experimental conditions ions do not play a major part in the decomposition and a free radical mechanism has been proposed to explain the formation of the main products.
THE CELL WALL POLYSACCHARIDES OF CANDIDA ALBICANS: GLUCAN, MANNAN, AND CHITIN
Authors: Bishop C. T. , Blank F. , Gardner P. E.
Published: May 2006

Cells of Candida albicans, a pathogenic yeast, have been shown to contain, in addition to chitin, a glucan ([α]D − 30°) and a mannan ([α]D + 78°) in the approximate ratio of 1.00:0.64. The two polysaccharides were easily distinguishable by moving boundary electrophoresis in borate buffer and were separated from each other by fractionation of their copper complexes. Methylation and hydrolysis of the glucan yielded the following O-methyl ethers of D-glucose: 2,3,4,6-tetra-O-methyl (7 moles); 2,3,4-tri-O-methyl (13 moles); 2,4,6-tri-O-methyl (trace); 2,4-di-O-methyl (6 moles); and 2-O-methyl (1 mole). It was concluded that the glucan was a highly branched polysaccharide containing β 1 → 6 and β 1 → 3 linked residues. Periodate oxidation of the glucan supported this conclusion.Methylation and hydrolysis of the mannan yielded the following O-methyl ethers of D-mannose: 2,3,4,6-tetra-O-methyl (1.65 moles); 3,4,6-tri-O-methyl (1.00 mole); 2,3,6-tri-O-methyl (0.18 mole); 3,4-di-O-methyl (1.90 moles). The mannan was therefore a highly branched polysaccharide with short chains of α 1 → 2 linked mannose residues joined together by α 1 → 6 linkages. Results of periodate oxidation agreed with this structure.The differences between these two polysaccharides and glucans and mannans found in other yeasts are discussed.
ALIPHATIC CHEMISTRY OF FLUORENE: PART II. AN UNUSUAL GRIGNARD REACTION
Authors: Bavin P. M. G.
Published: May 2006

The reaction between methyl 9-methylfluorene-9-carboxylate and phenyl magnesium iodide gave 9,9′-dimethyl-9,9′-difluorenyl in almost quantitative yield. Evidence is presented which shows that 9-methylfluorene anion is an intermediate. The probable intervention of elemental iodine is discussed.9-Methyl-9,9′-difluorenyl and 9,9′-dimethyl-9,9′-difluorenyl have been synthesized. A convenient preparation of 9,9′-difluorenylidene is described.
ALIPHATIC CHEMISTRY OF FLUORENE: PART III. SOME DERIVATIVES OF FLUORENE AND PHENANTHRENE
Authors: Bavin P. M. G.
Published: May 2006

Methyl fluorene-9-carboxylate and 9-methyl-9-acetylfluorene have been nitrated and the products converted to 2-nitrophenanthrene and 2-nitro-9,10-dimethylphenanthrene, respectively.Acetylation of 9,10-dimethylphenanthrene has given only one ketone, probably the 3-isomer. 4-Nitrofluorenone has been synthesized by a convenient route.
ALIPHATIC CHEMISTRY OF FLUORENE:PART IV. PREPARATION AND ALKYLATION OF SOME SULPHIDES AND SULPHONES
Authors: Bavin P. M. G.
Published: May 2006

The preparations are described of some 9-fluorenyl sulphides which have been oxidized with peracetic acid to the corresponding sulphones.9-Fluorenyl p-tolyl sulphone has been alkylated with a range of alkyl halides; other sulphones, including 2-nitro-9-fluorenyl p-tolyl sulphone, have been methylated.Methyl fluorene-9-carboxylate anion was reduced by p-toluenesulphonyl chloride to dimethyl 9,9′-difluorenyl-9,9′-dicarboxylate.
GRISEOVIRIDIN: THE C6 FRAGMENT
Authors: Mayo P. De , Stoessl A.
Published: May 2006

The structure of a hydrolytic degradation product from griseoviridin, isolated as the 2,4-dinitrophenylhydrazone, has been shown, by synthesis, to be IV. A by-product of the synthesis was the stereoisomeric 2,4-dinitrophenylhydrazone. This establishes IX as a part structure of griseoviridin. Evidence is provided that the previously proposed structural environment of the sulphur atom is incorrect, and that the sulphur may, in fact, be attached to the C6 fragment.
STEROIDS: PART II. 6-AMINO STEROIDS
Authors: Ketcheson Barbara G. , Taurins Alfred
Published: May 2006

Reduction of methyl 3β-acetoxy-6-oximinodinorcholanate using sodium in n-propyl alcohol, and acetylation, gave 6α-acetamido-3β-acetoxydinorcholanic acid; treatment with lithium aluminum hydride in tetrahydrofuran provided 3β,22ξ-dihydroxydinorcholan-6-one. High-pressure hydrogenation of methyl 3β-acetoxy-6-nitro-5-dinorcholenate, using palladium black as catalyst in acetic acid medium, afforded methyl 6ξ-acetamido-3β-acetoxy-5α-dinorcholanate. Under identical conditions, catalytic hydrogenation of 3β-acetoxy-6-nitro-5-cholestene resulted in the formation of 6β-acetamido-3β-acetoxy-5α-cholestane and 6ξ-acetamido-3β-acetoxy-5β-cholestane.
STEROIDS: PART III. REDUCTION OF OXIMINOCHOLANIC ACIDS
Authors: Waid Ted H. , Taurins Alfred
Published: May 2006

The reduction of 12-oximino-, 3,12-dioximino-, and 7,12-dioximino-cholanic acids using sodium in alcohol resulted in the formation of 12β-amino-, 3α,12β-diamino-, and 7β,12β-diamino-cholanic acids respectively. The reaction of 3,12-dioximinocholanic acid with lithium aluminum hydride provided cholane-3ξ,12ξ,24-triol, while similar treatment of 7,12-dioximinocholanic acid afforded 7ξ-amino-12-oximinocholan-24-ol.
THEORETICAL STUDIES ON SOLVATION: PART II. NEW THEORY FOR EVALUATION OF IONIC SOLVATION NUMBER FOR DIVALENT IONS AT 25 °C
Authors: Azzam A. M.
Published: May 2006

The concepts of ionic solvation are discussed and the definition of four types are suggested. Utilizing Webb's theory, values of the dielectric constant of water in terms of distance from a divalent ion are evaluated. The statistical mechanics of the distribution of solvent molecules round a divalent ion in aqueous solution has been worked out.The present theory shows that all divalent ions with radius less than 1.6 Å can have a saturated envelope of eight water molecules in excess of the Goldschmidt co-ordination number have to be accounted for as inner primary solvation number. The concept of catonium is suggested for such a stable aquo-complex entity. The catonium entity is further hydrated electrostatically in the normal way by primary and secondary solvation types. The conditions governing all types of solvation and their possible termination boundaries are discussed and evaluated.The theoretically calculated values of the ionic solvation numbers are in good agreement with the experimental results.
ACID ACTIVATION OF MONTMORILLONITE
Authors: Heyding R. D. , Ironside R. , Norris A. R. , Prysiazniuk R. Y.
Published: May 2006

A Pembina montmorillonite clay has been activated with sulphuric acid at various dosages by the conventional wet process and by the new "dry" process. The products are compared with respect to the fractions of the metal ion components remaining after leaching, the hydrated silica content, the bleaching capacity, and the B.E.T. nitrogen and water surface areas which they exhibit. Surface areas were also determined after calcining the products invacuo. The surface areas are discussed with reference to the removal of metal ions occupying octahedral lattice sites in a model clay particle.
THE STRUCTURE AND STEREOISOMERISM OF THREE MITRAGYNA ALKALOIDS
Authors: Seaton J. C. , Nair M. D. , Edwards O. E. , Marion Léo
Published: May 2006

Isorhyncophylline, the isomer into which rhyncophylline is convertible, has been found to occur in nature. Both bases are interconvertible. Isorhyncophylline on hydrolysis with dilute hydrochloric acid is converted to an aldehyde reducible to isorhyncophyllol. When the aldehyde is reduced in the Wolff–Kishner reaction, it is also isomerized and the product is isorhyncophyllane. This reduction product is oxidized by mercuric acetate to a neutral dilactam which still contains the oxindole carbonyl and further contains a new lactam carbonyl present in a six-membered ring. Reduction of the dilactam with lithium aluminum hydride gave a product having the spectroscopic properties of an indole. This confirms the assumption previously made that in rhyncophylline, ring C is five-membered. The isomerization of rhyncophylline, mitraphylline, and formosanine is described. Formosanine has been shown to be identical with uncarine-B and thus uncarine-A is the iso base derivable from formosanine.
THE THERMAL DECOMPOSITION OF PHENYL METHYL SULPHIDE
Authors: Back Margaret H. , Sehon A. H.
Published: May 2006

The thermal decomposition of phenyl methyl sulphide was investigated in a flow system in an excess of toluene. The main products were methane, thiophenol, and dibenzyl. The primary mode of decomposition was ascribed to the reaction[Formula: see text]The rate constant for this process was given by the expression[Formula: see text]
THE SYNTHESIS OF SOME BASIC ESTERS OF 3,4,5-TRIMETHOXYBENZOIC ACID
Authors: Frangatos Gerassimos , Kohan Geza , Chubb Francis L.
Published: May 2006

A series of basic esters of 3,4,5-trimethoxybenzoic acid was obtained from the reaction of 2-chloroethyl and 3-chloropropyl 3,4,5-trimethoxybenzoate with secondary amines including 1,2,3,4-tetrahydro-β-carboline. The latter compound was prepared by the lithium aluminum hydride reduction of 1,2,3,4-tetrahydro-1-oxo-β-carboline.
THE INFRARED FREQUENCIES AND INTENSITIES OF THE HYDROXYL GROUP IN 2,6-DI-tert-BUTYL-4-SUBSTITUTED PHENOLS
Authors: Ingold K. U.
Published: May 2006

The infrared frequencies, intensities, and apparent half band widths of the O—H stretching band of a series of 2,6-di-tert-butyl-4-substituted phenols have been measured in carbon tetrachloride solution and compared with the corresponding 4-substituted phenols. The frequencies of the former are 36 cm−1 higher than the latter and the intensities are also slightly higher. Both the frequency and intensity follow a Hammett ρσ relation. It is shown that the O—H bond lies in the plane of the benzene ring, the increase in frequency and intensity being ascribed to a steric repulsion of the phenolic hydrogen by the adjacent tert-butyl group.
ALIPHATIC CHEMISTRY OF FLUORENE: PART V. SPIRO-KETONES
Authors: Bavin P. M. G.
Published: May 2006

A novel synthesis is described of 1,2;3,4-dibenzophenanthrene, based on the spiro-ketone (IIIb), which was cleaved by strong base to the acid (VIIb).An example is described of acylation of aliphatic carbon.
DISINTEGRATION-RATE DETERMINATION BY 4π-COUNTING: PART V. FURTHER STUDIES ON ABSORPTION AND SCATTERING OF β-RADIATION
Authors: Yaffe L. , Fishman J. B.
Published: May 2006

The work of Pate and Yaffe on the study of absorption and scattering of β-radiation in a 4π-counter has been extended to greater source-mount thickness. As the thickness is increased, the backscattering curves assume the juxtaposition obtained in <2π geometrical systems. The saturation backscattering value S is attained at a mass approximately one-fifth that of the range of the β-radiation. The relationship S = 0.070 log10Emax + 0.142, where Emax is the maximum energy of the β-radiation, is obeyed over the range studied. The phenomenon of coincident discharges, while adequately explained by Pate and Yaffe as caused by wall- and gas-scattering if thin film source mounts are used, cannot completely account for the results with thicker films. Other phenomena, such as bremsstrahlung and secondary electron production, begin to play a role.
THE ELECTRON SPIN RESONANCE ABSORPTION SPECTRA OF SEMIQUINONE IONS: PART II. THE HYPERFINE SPLITTING DUE TO AMINO GROUPS
Authors: Matsunaga Y. , McDowell C. A.
Published: May 2006

The electron spin resonance absorption spectra of amino-substituted p-benzosemiquinone ions have been examined. The hyperfine splittings due to the amino protons and the amino nitrogen atom have been demonstrated. It has been found that the magnitude of the hyper fine splitting constants due to these two kinds of nuclei depends very much on the nature of the free radical.
THE ELECTRIC MOMENTS OF SUPPOSEDLY SYMMETRICAL CYCLIC SUBSTANCES
Authors: Meredith C. C. , Wright George F
Published: May 2006

The distortion polarizations of polysubstituted benzenes and cyclobutanes which have been examined by the randomly oriented solid pellet technique seem to be lower but never higher than the electronic polarization values derived from bond refractions, and are considered to be more reliable than the latter. In almost all of the supposedly symmetrical substances which have been examined the total solute polarization always exceeds the measured distortion polarization and usually exceeds the calculated MRD. These substances must then be polarized, although the moments which have been determined are not numerically reliable because of solvent effects. Whenever possible the temperature coefficients of these apparent moments have been determined and are usually but not always positive. From these temperature coefficients it is presumed that some substances, like naphthalene, are rigidly dipolar whereas others, like hexachlorobenzene, have activation states which are unsymmetrical and therefore contributory to the moment which actually is measured.
SOLID–LIQUID REACTIONS: PART I. THE DETERMINATION OF SOLID–LIQUID REACTION MECHANISMS
Authors: Kelly Roger
Published: May 2006

A tracer method has been described by Graham, Spinks, and Thorvaldson for investigating the mechanisms of solid–liquid reactions. The present work represents an attempt to develop the theory of this method in detail and thereby allow for a greater variety of experimental conditions. Thus, no restrictions are placed on the compositions of the reacting and product solids, nor on the initial location of the tracer. The effect of exchange between the liquid and both solids is taken into account. Furthermore, two different systems of mechanisms are considered. In the one, which is shown to be the more realistic when rapid, multidirectional "external" exchange is present, mechanisms are classified according to whether or not the reaction proceeds at the surfaces of the solids; in the other, applicable in the absence of "external" exchange or when the exchange is slow, mechanisms are classified according to the degree of mixing with the liquid of successively reacting portions of the reacting solid.
THE THERMAL DECOMPOSITION OF PHENYLACETIC ACID
Authors: Back Margaret H. , Sehon A. H.
Published: May 2006

The thermal decomposition of phenylacetic acid was investigated by the toluene-carrier technique over the temperature range 587 to 722 °C. The products of the pyrolysis were carbon dioxide, carbon monoxide, hydrogen, methane, dibenzyl, and phenylketene. From the kinetics of the decomposition it was concluded that the reaction[Formula: see text]was a homogeneous, first-order process and that the rate constant of this dissociation step was represented by the expression k = 8 × 1012.e−55,000/RT sec−1. The activation energy of this reaction may be identified with D(C6H5CH2—COOH). The possible reactions of carboxyl radicals are discussed.
THE THERMAL DECOMPOSITION OF DIPHENYLACETIC ACID
Authors: Back Margaret H. , Sehon A. H.
Published: May 2006

The pyrolysis of diphenylacetic acid was investigated over the temperature range 515-636° C using the toluene-carrier technique. The main products of this system were similar to those formed in the thermal decomposition of phenylacetic acid. The rate constant for the reaction[Formula: see text]was calculated as k′ = 8 × 1012.exp(−52,000/RT) sec−1.The over-all decomposition reaction was found to be partly heterogeneous and, therefore, the activation energy for reaction [1] may be only tentatively identified with D[(C6H5CH)2—COOH].
COMPLEX MANGANESE PERIODATES
Authors: Lister M. W. , Yoshino Y.
Published: May 2006

The preparation of complex periodatomanganates, from manganous salts reacting with sodium (or potassium) hypochlorite and periodate, is described. The products were Na7H4Mn(IO6)3.17H2O and K7H4Mn(IO6)3.8H2O. The manganese was shown to be tetravalent from its redox equivalent in its reaction with iodide and with ferrous ions, and from its magnetic moment, which was 3.87 Bohr magnetons, corresponding to three unpaired electron spins. The ion has an absorption maximum at 483 mμ. Rather complicated pH curves were found for this compound in acid-base titrations. The complex ion decomposes slowly to permanganate and iodate; the kinetics of this reaction have been measured, and a possible mechanism has been suggested. The reaction proceeds in several steps by way of simpler complex ions. The same applies to the reaction between iodide ions and the complex ions when the pH is about 9.
SOME OBSERVATIONS ON THE THEORY OF π-BONDING IN INORGANIC COMPOUNDS
Authors: Westland A. D.
Published: May 2006

Evidence for the existence of multiple bonding due to d-electron donation by non-inert gas type ions is discussed briefly. A quantitative relation between the heats of formation of binary halides and chalcides containing non-inert gas type cations, on the one hand, and inert gas type cations, on the other, reveals an enhanced lattice energy in the former class of compounds. It is shown that this may be accounted for in the case of iron group elements without recourse to the postulate of participation of d-electrons in the bonding, as satisfactory estimates of the lattice energies of halides and sulphides may be made on the basis of values for group IIa compounds.
THE SYNTHESIS OF 3-O-β-D-XYLOPYRANOSYL-D-XYLOSE AND THE RECHARACTERIZATION OF SOME BENZYLIDENE DERIVATIVES OF D-XYLOSE
Authors: Curtis E. J. C. , Jones J. K. N.
Published: May 2006

The benzylidene groups of the di-O,O-benzylidene derivative of D-xylose diethyl dithioacetal have been located at the 2,4:3,5 positions, and not at the 2,3:4,5 positions suggested by Zinner, Rembarz, Linke, Ulbricht. Partial hydrolysis yielded the 2,4-O-benzylidene compound, from which 3-O-β-D-xylopyranosyl-D-xylose (rhodymenabiose) was prepared.
STEREOCHEMICAL STUDIES:I. CONFIGURATIONS OF SOME 4-AZACHOLESTANES
Authors: Edward J. T. , Morand Peter F.
Published: May 2006

The Beckmann rearrangement of the oxime of A-nor-5β-cholestan-3-one gave 4-aza-5β-cholestan-3-one; the isomeric lactam obtained by the reduction of the oxime of 5-oxo-3,5-seco-A-norcholestan-3-oic acid with sodium in alcohol must consequently be 4-aza-5α-cholestan-3-one. Other methods of reducing the oximino acid afforded hydroxamic acids. 4-Aza-5α- and 4-aza-5β-cholestane were obtained by reduction of the appropriate lactam or hydroxamic acid.
STEREOCHEMICAL STUDIES: II. CONFIGURATIONS OF SOME 4-OXACHOLESTANES
Authors: Edward J. T. , Morand Peter F.
Published: May 2006

The oxidation of A-nor-5β-cholestan-3-one with peracids gave 4-oxa-5β-cholestan-3-one. This was identical with one of the two lactones produced by the reduction of Windaus' keto acid; the other lactone must be 4-oxa-5α-cholestan-3-one. The two lactones were reduced by lithium aluminum hydride to diols, which were cyclized to 4-oxa-5α- and -5β-cholestane.
PROTON MAGNETIC RESONANCE SHIFTS FOR THE H2O–SO3SYSTEM AND SOME ELECTROLYTE SOLUTIONS IN SULPHURIC ACID
Authors: Gillespie R. J. , White R. F. M.
Published: May 2006

Proton magnetic resonance shifts have been measured for the H2O–SO3system. The results have been used to calculate the degree of ionization of water in solutions containing excess sulphuric acid. The shifts produced by a number of electrolytes in sulphuric acid have also been measured. The results are interpreted in terms of solute–solvent interactions, particularly polarization and hydrogen bonding, and are compared with the results of similar previous measurements on aqueous solutions.
THE PRESENCE OF MONOTHIOCARBONATE SUBSTITUENTS IN CELLULOSE XANTHATES
Authors: Andrews D. A. , Hurtubise F. G. , Krässig H.
Published: May 2006

The presence of monothiocarbonate substituents in viscose has been demonstrated by the infrared spectra of the gases evolved during the acid hydrolysis of cellulose xanthate salts and viscose. A comparison of the results of various methods of sulphur determination and the results obtained by ultraviolet spectroscopy has been made. The results of investigations on sodium cellulose monothiocarbonate preparations support the concept of monothiocarbonate substitution.
THE IDENTITY OF BAYERITE-a AND BAYERITE-b
Authors: Yamaguchi G. , Sakamoto K.
Published: May 2006

not available
THE SECONDARY HYDROGEN ISOTOPE EFFECTS IN THE PYROLYSIS OF ETHYL-d5 ACETATE AND ETHYL ACETATE-d3
Authors: Blades Arthur T. , Gilderson P. W.
Published: May 2006

Rate constant expressions have been obtained for ethyl acetate and ethyl-d5 acetate in the temperature ranges 500–603 °C and 501–614 °C.[Formula: see text]By measuring the relative rate of production of C2H4 and C2D4 from identical mixtures of the two esters at the temperatures 387 and 490 °C, it has been possible to determine the temperature coefficient of the relative rate constant more accurately. This, coupled with the relative rate constants at 500 °C derived from the above equations, gives the relative rate constant expression.[Formula: see text]These data are compared with the intramolecular isotope effect in the decomposition of ethyl-1,1,2,2-d4 acetate, and the differences attributed to secondary isotope effects.The rate of decomposition of ethyl acetate-d3 was found to be identical within experimental error with that of the normal acetate.
ORGANO ARSENIC COMPOUNDS: II. N,N-DIALKYL AMIDODIFLUOROARSENITES AND N-ALKYL IMIDOFLUOROARSENITES
Authors: Olah George A. , Oswald Alexis A.
Published: May 2006

The reaction of arsenic fluoride with aliphatic amines was studied. Secondary amines gave N,N-dialkyl amidodifluoroarsenites. Primary amines while reacting similarly lose HF subsequently and yield N-alkyl imidofluoroarsenites.
THE SYNTHESIS OF SOME INDOLYLALKYLAMINOALCOHOLS
Authors: Frangatos Gerassimos , Kohan Geza , Chubb Francis L.
Published: May 2006

A series of 3-indolylalkylaminoalcohols have been obtained from the lithium aluminum hydride reduction of the amides prepared by the reaction of 3-indoleglyoxylyl chloride and 2-methyl-3-indoleglyoxylyl chloride with primary aminoalcohols. When acetone was used as solvent in the reaction of 3-indoleglyoxylyis chloride and either 2-aminoethanol or 3-aminopropanol, the solvent participated in the reaction resulting in the formation of 2,2-dimethyl-3-(3-indoleglyoxyl)oxazolidine and 2,2-dimethyl-3-(3-indoleglyoxyl)tetrahydro-1,3-oxazine respectively. When the latter two compounds were reduced by lithium aluminum hydride, both carbonyl groups were completely reduced and reductive cleavage of the oxazolidine and tetrahydro-1,3-oxazine rings occurred to form the corresponding open-chain alcohols.
SOME DEUTERIUM KINETIC ISOTOPE EFFECTS: II. α-DEUTERIUM EFFECTS IN THE WATER SOLVOLYSIS OF SOME ALKYL COMPOUNDS
Authors: Leffek K. T. , Llewellyn J. A. , Robertson R. E.
Published: May 2006

As an extension of previous work on methyl compounds, α-deuterium kinetic effects have been measured for ethyl, n-propyl, and isopropyl compounds. The effects can be accounted for in terms of current theory but a modification involving intramolecular van der Waals forces seems to provide a more satisfactory description of some of the processes involved in the production of the rate changes.
THE RANGE OF ALKALI METAL IONS OF KILOELECTRON VOLT ENERGIES IN ALUMINUM
Authors: Davies J. A. , McIntyre J. D. , Cushing R. L. , Lounsbury M.
Published: May 2006

A simple electrostatic accelerator capable of producing a monoenergetic beam of alkali metal ions at energies up to 100 kev has been used to study the range of Cs137 ions in aluminum as a function of energy. The median range (RM) increases linearly with energy as predicted from the Bohr–Nielsen equation, but has a value about twice that predicted by this equation. Furthermore, the observed straggling about the mean value is not Gaussian in shape, but consists of an asymmetric peak with a pronounced exponential "tail". The possible significance of these results is discussed. Preliminary results are given for the range of 30-kev Rb86 and Na21 ions in aluminum.
ISOLATION AND STRUCTURE OF A NEW ALKALOID: ASPIDOCARPINE
Authors: McLean Stewart , Palmer K. , Marion Léo
Published: May 2006

From the root bark of Aspidospermmegalocarpon Muell. Arg. a new alkaloid, aspidocarpine, has been isolated. It has the empirical formula C22H30O3N2 and contains an N-acetyl, one methoxyl group, and one active hydrogen. The alkaloid, a phenolic monoacidic tertiary base, has been shown by its properties, those of its derivatives, and the spectroscopic data, to contain an N-acetyl-6-methoxy-7-hydroxydihydroindole moiety. Oxidation of aspidocarpine with chromic acid gave rise to a product identical in all respects with apoaspidospermine obtained from the similar oxidation of aspidospermine. Since the structure of aspidospermine is known, the foregoing results establish the structure of the alkaloid aspidocarpine.
THE ELECTROCHEMICAL BEHAVIOR OF THE NICKEL OXIDE ELECTRODE: PART II. QUASI-EQUILIBRIUM BEHAVIOR
Authors: Bourgault P. L. , Conway B. E.
Published: May 2006

The electrode potential of the nickel oxide electrode has been determined as a function of water and solute activity in aqueous solutions of potassium hydroxide. The electrode, which was charged to a mean state of oxidation corresponding to 50% Ni II and 50% Ni III, was examined after long periods of time and by cathodic and anodic e.m.f. decay measurements after polarization in order to establish the quasi-reversible potentials by two methods. The results are discussed in terms of the stoichiometry of the potential-determining reaction, and distinction between mixed and true reversible potentials is made.
THE PREPARATION OF CYCLIC PEROXIDES AND THEIR DECOMPOSITION IN SOLUTION
Authors: Russell K. E.
Published: May 2006

The cyclic dimers of sebacyl, dodecanedioyl, and tetradecanedioyl peroxide have been prepared, together with high yields of the corresponding high molecular weight polymeric peroxides. The decomposition of these peroxides in styrene and benzene solution has been studied. The results show that if diradicals are formed in the breakdown of the cyclic peroxides, they undergo self-termination before reacting with a significant number of styrene molecules. In the presence of low concentrations of 1,1-diphenyl-2-picrylhydrazyl (DPPH) in benzene solution, self-termination of diradicals is preferred to reaction with the hydrazyl.
INDOLYL-3-PYRUVIC ACID OXIME AS THE PRECURSOR OF INDOLYL-3-ACETONITRILE
Authors: Ahmad A. , Spenser Ian D.
Published: May 2006

Chemical and chromatographic evidence is presented compatible with the hypothesis that the auxin indolyl-3-acetonitrile is derived in plants from indolyl-3-pyruvic acid oxime (antiHO—COOH) by a concerted reaction.
A PROPOSED CRYOSCOPIC METHOD FOR DETERMINING THE HEAT OF COMPLEX FORMATION FOR A REACTION,
Authors: Maine P. A. D. de
Published: May 2006

not available
AMINONITRILES. II. SOME DERIVATIVES OF 2-AMINO-3-CYANOINDENE
Authors: Garmaise D. L. , Gelblum S.
Published: May 2006

not available
THE TRANSFER REACTIONS OF HALOGEN ATOMS
Authors: Fettis G. C. , Knox J. H. , Trotman-Dickenson A. F.
Published: May 2006

Extensive results on the reactions of fluorine, chlorine, and bromine atoms with alkanes and with some other molecules have been obtained from the study of competitive halogenations. The comparison of the A factors of the reactions provides an excellent test of the transition state theory. The activation energies of the bromine atom reactions can be combined with measurements of the activation energies for the reactions of alkyl radicals with hydrogen bromide to yield unusually reliable values of bond strengths. Information on the influence of polar effects on the activation energies of atomic reactions can be obtained from results on the reactions of fluorine and chlorine atoms with methyl halides.
ON THE EXCITATION OF THE EMISSION SPECTRUM OF NCO IN SOLID MATRICES CONDENSED AT 4 °K
Authors: Nicholls R. W. , Krishnamachari S. L. N. G.
Published: May 2006

Seventeen broad (∼50 Å wide) spectral features have been excited in emission between 3000 Å and 4600 Å in the products of a microwave discharge through N2 deposited on a cold (4 °K) surface on which the discharge products of CO + N2 had been previously condensed. The features which lie between 3650 Å and 4470 Å show close agreement with those observed in absorption by Dixon during the flash photolysis of NCO and assigned to the A2Σ − X2Πi transition. It therefore seems likely that the emission features arise from NCO also as a result of the reaction N(2P) + CO(X 1Σ+) → NCO[Formula: see text]at the solid surface.
THREE-BODY RECOMBINATION OF GASEOUS IONS
Authors: Fueno Takayuki , Eyring Henry , Ree Taikyue
Published: May 2006

The recombination of gaseous ions in the presence of third bodies is assumed to follow a sequence of two bimolecular steps: M + X+ [Formula: see text] MX+ and MX+ + Y− [Formula: see text] XY + M. The termolecular rate constants of the over-all processes are calculated for several ionized gases at various temperatures. For the calculation, the equilibrium internuclear separation and the corresponding binding energy of a complex ion, MX+, are obtained by minimizing the interaction energy between M and X+, which is approximated to the sum of the Lennard-Jones potential for the M–X interaction and the polarization energy between M and X+. The recombination coefficients of some ionized gases at 288 °K and various pressures are calculated and compared with the observed data. The agreement is found to be satisfactory. The limitations of this theoretical approach are discussed.
THE ROLE OF Hg 63P0 ATOMS IN MERCURY PHOTOSENSITIZATION. I. REACTIONS IN THE PRESENCE OF NITROGEN
Authors: Kimbell G. H. , Roy D. J. Le
Published: May 2006

A quantitative investigation has been made of the factors affecting the concentration of mercury 63P0 atoms formed by collisions of the second kind between mercury 63P1 atoms and nitrogen. The absorption of 4047 Å (63P0 − 73S1) and the emission of 2656 Å (63P0 − 61S0) were studied in the pressure range 0.06 mm to 140 mm. Both types of measurement indicate that the forbidden line arises from spontaneous as well as collision-induced emission. The lifetime for spontaneous emission is estimated to be 4.2 × 10−4 sec.
AN IMPROVED TECHNIQUE FOR THE OBSERVATION OF INFRARED CHEMILUMINESCENCE: RESOLVED INFRARED EMISSION OF OH ARISING FROM THE SYSTEM H + O2
Authors: Charters P. E. , Polanyi J. C.
Published: May 2006

A multiple reflection apparatus for the observation of infrared chemiluminescence is described. By means of this apparatus infrared emission from the system H + O2 has been identified as being due to vibrationally excited OH radicals in levels v = 1, 2, and 3 of the ground electronic state. The resolved infrared spectrum of the OH fundamental has been observed for the first time without interference from other emission. The most likely source of excited OH is the reaction H + HO2 → OH† + OH. The vibrational 'temperature' of OH† (vibrationally excited OH in its ground electronic state) in our system is in the region of TV = 2240 °K. These findings are discussed in relation to Krassovsky's suggestion that reaction between H and O2 could account for the Meinel hydroxyl bands in the night sky.
SOME OBSERVATIONS ON THE RADIATIVE COMBINATION OF ATOMIC HYDROGEN WITH ATOMIC HALOGENS IN BURNER FLAMES
Authors: Phillips L. F. , Sugden T. M.
Published: May 2006

When small quantities of gaseous molecular halogens chlorine, bromine, and iodine are introduced into the supply to premixed hydrogen–oxygen–nitrogen flames one of the most important spectroscopic features appearing is an apparently continuous emission in the visible, sometimes extending into the near ultraviolet. The intensity of this continuous emission has been studied as a function of amount of halogen, and of temperature, composition, and position with respect to the reaction zone in a wide variety of flames. In oxygen-rich flames it has been attributed to an over-all process,[Formula: see text]where X denotes an atom of halogen; one of the atoms may be in an excited state. Most of the work concerns hydrogen-rich flames, where a very strong correlation between the intensity and the product [H][X] is obtained. The over-all process may be written as[Formula: see text]The efficiency of this over-all process is measured as 1 quantum emitted for about 1010 ordinary kinetic collisions of the atoms. The mechanism is discussed from the aspects of direct radiative recombination and of stabilization by collision of an intermediate excited HX* before radiation.
RADICAL TERMINATION MECHANISMS IN BULK POLYMERIZATION
Authors: Funt B. L. , Pasika W.
Published: May 2006

The termination mechanism in the bulk polymerization of styrene and vinyl acetate initiated by α,α′-azobisisobutyronitrile has been investigated. C14-Labelled initiators were employed and activities of samples were determined by internal liquid scintillation counting. Measurements of fractionated and unfractionated polystyrene showed an average of 1.94 and 2.04 tagged fragments per molecule, respectively, and indicated termination by combination at 60 °C. For polyvinyl acetate 1.06 fragments were found per molecule, indicating termination by disproportionation at 60 °C.
CONDUCTANCES OF AQUEOUS SOLUTIONS OF SODIUM HEXANOATE (SODIUM CAPROATE) AND THE LIMITING CONDUCTANCES OF THE HEXANOATE ION, AT 25 °C AND 35 °C
Authors: Campbell A. N. , Friesen J.I.
Published: May 2006

The equivalent conductances, densities, and viscosities of aqueous solutions of sodium hexanoate have been determined at 25 °C and 35 °C at concentrations ranging from 0.0003 M to saturation.The limiting equivalent conductances of the hexanoate ion have been determined as 27.37 ± 0.04 mhos at 25 °C and 34.69 ± 0.05 mhos at 35 °C.The Robinson–Stokes and the Falkenhagen–Leist equations have been applied to the data. The Robinson–Stokes equation reproduces the data within 0.7 mho up to 0.5 M at 25 °C when å = 13 Å. At 35 °C the data are reproduced within 0.5 mho up to 0.05 M with å = 10 Å. The Falkenhagen–Leist equation reproduces the data at 25 °C within 0.4 mho up to 0.1 M with å = 5.5 Å. An å = 4.0 Å reproduces the 35 °C data within 0.5 mho up to 0.05 M.From the form of the conductance curves and from an estimation of the apparent molecular weight it was concluded that the hexanoate ion does not form ionic micelles.
THE PREPARATION OFL-ARGINYL DIPEPTIDES OF ASPARAGINE, GLUTAMINE, AND SOME BASIC AMINO ACIDS
Authors: Berse Casimir , Piché Lucien , Uchiyama Akira
Published: May 2006

The synthesis of the following dipeptides is described: L-arginyl-L-asparagine acetate, L-arginyl-L-glutamine acetate, L-arginyl-L-lysine diacetate, and L-arginyl-L-ornithine diacetate. The two former were prepared by coupling a mixed anhydride of α-carbobenzoxy-ω-nitro- L-arginine directly with L-asparagine or with L-glutamiae; catalytic hydrogenolysis of the resulting intermediates gave the dipeptides. The two others were obtained by combining α-carbobenzoxy-L-arginine with ω-carbobenzoxy- L-lysine methyl ester hydrochloride or with ω-carbobenzoxy-L-ornithine methyl ester hydrochloride in the presence of N,N′-dicyclohexyl-carbodiimide; saponification and hydrogenation was necessary to uncover the resulting dipeptides.
CATIONIC POLYMERIZATION OF ETHYLENE OXIDE: IV. THE PROPAGATION REACTIONS
Authors: Merrall G. T. , Latrémouille G. A. , Eastham A. M.
Published: May 2006

Studies of the boron-fluoride-catalyzed reaction of ethylene oxide with simple alcohols and low molecular weight polyglycols indicate three ways in which chain growth could occur, but only one of these is considered to be important after the initial stages of polymerization. The rate of disappearance of monomer reaches a maximum at a molecular weight of about 400. A mechanism is proposed to account for both polymerization and depolymerization and it is shown how equilibrium between these two reactions could result.
STEROIDS: PART IV. CONDENSATION OF CHOLESTAN-3-ONE AND CHOLESTANE-3,6-DIONE WITH FORMALDEHYDE
Authors: Waid Ted H. , Taurins Alfred
Published: May 2006

Cholestan-3-one and cholestane-3,6-dione were allowed to react under the conditions of the Mannich reaction with paraformaldehyde and amine hydrochlorides. The products obtained proved to be methylene-bis-ketones, and were formulated as di(2,2′-3-oxocholestanyl)methane and di(4,4′-3,6-dioxocholestanyl)methane respectively.
ORGANOPHOSPHORUS COMPOUNDS: VIII. O-ALKYL, O′-ARYL PHOSPHOROFLUORIDOTHIOATES AND O-ARYL N-ALKYL PHOSPHORAMIDOFLUORIDOTHIOATES
Authors: Olah G. A. , Oswald A. A.
Published: May 2006

O-Alkyl, O′-aryl phosphorofluoridothioates and O-aryl N-alkyl phosphoramidofluoridothioates were prepared from the corresponding aryl phosphorochlorofluoridothioates and aryl phosphorodifluoridothioates.
THE DETERMINATION OF THE AREAS OF RESOLVED AND PARTIALLY RESOLVED CHROMATOGRAPHY PEAKS
Authors: Bartlet John C. , Smith D. Morison
Published: May 2006

Gas chromatographic peaks were demonstrated to have the form of normal distribution curves. A mathematical treatment has been developed which permits the calculation of the areas of these curves from the statistical parameters, height of the mode (peak height), and standard deviation σ. The standard deviation equals the width of the peak at 0.882 of peak height. Methods given for the evaluation of the mutual effects of overlapping peaks have made it possible to obtain corrected peak heights. The standard deviation of the gas chromatography peak has been found to vary linearly with the retention time, thus permitting the graphical estimation of σ for use with corrected peak heights in the calculation of true areas for overlapping peaks. The method has also been extended to the treatment of skewed, overlapping peaks. The variation of σ with retention time, its constancy, and its relationship to the number of theoretical plates are discussed.
SOME FACTORS AFFECTING THE ZONE MOBILITY OF INORGANIC IONS DURING ELECTROMIGRATION IN PAPER
Authors: Bailey R. A. , Yaffe L.
Published: May 2006

A number of factors which affect the zone mobilities of inorganic ions were investigated. The influence of temperature was that expected from its effect on the conductance in free solution. The zone mobility tends to decrease, and the zone size to increase, with increasing migrant concentration. Excess foreign ions in the initial migrant zone can have a similar result. Experiments in the presence of the swelling agent thiourea indicate that swelling has at least a constant and perhaps a negligible influence on the obstructive factor. Finally, variation of the zone mobility with paper type was considered in relation to the ion-exchange capacity. Of the ions studied, only copper showed any correlation. Some observations were made using ion-exchange papers.
SELECTIVE ENZYMOLYSIS OF POLY-β-D-GLUCANS, AND THE STRUCTURE OF THE POLYMERS
Authors: Parrish F. W. , Perlin A. S. , Reese E. T.
Published: May 2006

The soluble poly-β-D-glucan from oats has been subjected to degradation by two different types of enzymes. "Cellulase" converts the polysaccharide to a trisaccharide, 4-O-β-D-lamina-ribiosyl-D-glucose, and two tetrasaccharides, 3′-O-β-D-cellobiosyl-D-cellobiose and 4′-O-β-D-laminaribiosyl-D-cellobiose. Degradation by the second enzyme, "laminarinase", produces a trisaccharide, 3-O-β-D-cellobiosyl-D-glucose, and a tetrasaccharide, 3-O-β-D-cellotriosyl-D-glucose. These products, which account for 75-85% of the polymer in each experiment, have been characterized by chemical methods. The data show that the glucan is composed almost entirely of two types of structural sequences: one is a tetrameric unit in which a single β-(1 → 3) linkage alternates with two β-(1 → 4) linkages, and the other, a pentameric unit in which a single β-(1 → 3) linkage alternates with three consecutive β-(1 → 4) linkages.The soluble poly-β-D-glucan from barley has been shown by enzymolysis with the "cellulase" to be closely related in detailed structure to the oat polymer.Steric aspects of the enzymic degradations are discussed.
STRUCTURE OF BRIDGMAN'S BLACK CARBON DISULPHIDE
Authors: Whalley E.
Published: May 2006

The infrared spectrum of black carbon disulphide dispersed in a potassium bromide disk has been examined. The blackness and the infrared spectrum are consistent with its being a linear polymer, —(C==S.S)n.
SEARCH FOR INDEPENDENT FORMATION OF Cs134m IN FISSION
Authors: Baerg A. P. , Bartholomew R. M. , Betts R. H.
Published: May 2006

The independent yield of Cs14m in thermal neutron fission of U235 is less than 1.7 × 10−6 of the mass 134 chain yield and that of Cs136 was found to be (0.94 ± 0.04) × 10−3 of the mass 136 chain yield. The half-life for Cs134m was measured as 2.91 ± 0.01 hours.
TRYPTAMINES, CARBOLINES, AND RELATED COMPOUNDS: PART VIII. δ-CARBOLINE
Authors: Abramovitch R. A. , Adams K. A. H. , Notation A. D.
Published: May 2006

The first unambiguous synthesis of δ-carboline has been achieved starting with 3-amino-2-phenylpyridine. This was converted to the azide which was thermally cyclized to δ-carboline. The carboline gave a py-N-methiodide which was converted to the anhydronium base. The pKa of the anhydronium base was determined and its significance is discussed. The anhydronium base formed a methiodide which, on dry distillation, gave ind-N-methyl-δ-carboline. The spectral properties of the various derivatives of δ-carboline were examined and the bond structures of the anhydronium base and the methiodides are discussed.
2,3-O-ISOPROPYLIDENE-L-ERYTHROTETRURONIC ACID AND -L-ERYTHROSE, AND THE METHYLD-ERYTHRO- ANDD-THREO-TETROFURANOSIDES
Authors: Baxter J. N. , Perlin A. S.
Published: May 2006

Oxidation of 2,3-O-isopropylidene-β-L-rhamnose (I) with hypoiodite, followed by periodate cleavage of the derived aldonic acid, affords 2,3-O-isopropylidene-L-erythrotetruronic acid. Reduction of I with sodium borohydride and periodate oxidation of the resulting glycitol gives 2,3-O-isopropylidene-L-erythrose. Both products have been obtained in high yield, and are readily hydrolyzed to L-erythrotetruronic acid and L-erythrose, respectively.Methyl α- and β-D-erythro- and D-threo-tetrofuranosides have been prepared by the Fischer glycoside synthesis from D-erythrose- and D-threose-formates, respectively. A notable anomeric difference in the lead tetraacetate oxidation behavior of the methyl D-threosides has been observed, the β-anomer being more reactive than the α-anomer.
ON THE EXISTENCE OF TERNARY COMPOUNDS IN THE SYSTEM NH3–H2O2–H2O
Authors: Mironov K. E.
Published: May 2006

not available
APPLICATION OF THE HAMMETT EQUATION TO THE HYDROLYSIS OF SUBSTITUTED BENZAMIDES
Authors: Edward J. T. , Chang H. S. , Yates K. , Stewart Ross
Published: May 2006

not available
TRYPTAMINES, CARBOLINES, AND RELATED COMPOUNDS: PART VII. INTERNUCLEAR CYCLIZATION ONTO A PYRIDINE RING
Authors: Abramovitch R. A.
Published: May 2006

not available
THE CONDENSATION OF GLYOXAL WITH p-CRESOL
Authors: Rosenthal Alex , Zaionchkovsky Alec
Published: May 2006

not available
NUCLEAR MAGNETIC RESONANCE SPECTRA OF SOME MODEL INDOLINE DERIVATIVES
Authors: McLean Stewart
Published: May 2006

not available
SCISSION OF STERICAIXY HINDERED vic-DIOLS
Authors: Goldschmid H. R. , Perlin A. S.
Published: May 2006

not available
ELECTRONIC STATES OF HYDRATED VANADIUM (II) ION
Authors: Bennett Ruth M. , Holmes O. G.
Published: May 2006

The optical absorption of a single crystal of VSO4.7H2O was measured in the range 9000–35,000 cm−1. The three observed bands were assigned to transitions between the four orbital levels resulting from cubic electrostatic perturbation of the spherical terms of configuration 3d3. Values of Dq = 1200 cm−1 and E = 10,000 cm−1 were derived from the spectral analysis.
THE OXIDATION OF MANGANATE BY PERIODATE
Authors: Lister M. W. , Yoshino Y.
Published: May 2006

The reaction between periodate and manganate ions in alkaline solution has been examined, and at 35 °C the rate is given by the equation, time being measured in minutes,[Formula: see text]It is proposed that the main reaction mechanism is[Formula: see text][Formula: see text]Hence k1 = 107 (g-molecule/l.)−1 min−1 at 35 °C, and it was found that the activation energy is about 13.9 kcal/g-molecule. Data of Carrington and Symonds (2), combined with the value for k1, make k2 = 2.8 × 106 (g-molecule/l.)−1 min−1. Added permanganate ions slow up the reaction; this is ascribed to the reverse of reaction (i) competing with reaction (ii). This gives a value for k3 of 2 × 107 (g-molecule/l.)−1 min−1; this is so large a rate constant as to make it probable that the hypomanganate ions are hydrolyzed. The effect of hydroxide concentration on the rate is ascribed to partial hydrolysis of manganate ions. The observed results would require the ionization constant of HMnO4− to be 7 × 10−11.
A SYSTEM OF MOLECULAR THERMOCHEMISTRY FOR ORGANIC GASES AND LIQUIDS: PART II. EXTENSION TO COMPOUNDS CONTAINING SULPHUR AND OXYGEN
Authors: Lovering Edward G. , Laidler Keith J.
Published: May 2006

The system of bond and group energies described in Part I has been extended and applied to certain compounds containing sulphur and oxygen. The substances treated are the alkanethiols, the thiaalkanes, and the dithiaalkanes. The bond additivity scheme enables reliable values for heats of formation, combustion, atomization, and vaporization to be calculated for these compounds.A similar treatment has been applied to the data for alcohols, ethers, and alkyl peroxides.
ABOUT THE PRIMARY ACT OF PHOTOCHEMICAL DECOMPOSITION REACTIONS OF MONOSUBSTITUTED COBALTIHEXAMINE IONS
Authors: Simon Z.
Published: May 2006

We will discuss the primary act of photochemical decomposition of Co(NH3)5Xn+ ions in aqueous solution. The potential energy surfaces are plotted correlating the complex ion's energy levels with those of the decomposition products. For this purpose spectral and kinetic data are used, as well as Wigner–Witmer correlation rules. The potential energy surfaces and certain rules regarding the radiationless transitions between them permit us to draw certain qualitative conclusions concerning these decompositions. Our conclusions seem to be confirmed by available experimental data.