bluuebunny/crossref_metadata_2025 huggingface dataset:
INTERFACE KINETICS: HYDROGEN PEROXIDE OXIDATION OF CUPROUS ION
Authors: Colcleugh D. W. , Graydon W. F.
Published: May 2006

It has been established (D. W. Colcleugh and W. F. Graydon. J. Phys. Chem. In press) that hydrogen peroxide is produced during the dissolution of polycrystalline copper in dilute aqueous solutions. The hydrogen peroxide formed during the dissolution further attacked the metal, producing additional cupric copper in solution. The kinetics of this heterogeneous reaction was investigated in aerated sulphuric acid solutions. Under these experimental conditions the ratio of the increase in concentration of cupric ion to the decrease in concentration of hydrogen peroxide was constant at the value of 2. In deaerated sulphuric acid this stoichiometric ratio was constant at the value of 1 under similar experimental conditions.Rate equations for the formation of cupric ion in solution and for the decomposition of hydrogen peroxide in the solution were determined as a function of sample area, corroding solution volume, temperature, hydronium ion concentration, cupric ion concentration, and hydrogen peroxide concentration.A reaction mechanism was suggested to describe the empirical rate equations and the stoichiometry obtained experimentally.
IONIZATION OF ORGANIC COMPOUNDS: IV. STUDIES OF ETHANOL AND ETHYL ETHER IN SULPHURIC ACID BY NUCLEAR MAGNETIC RESONANCE
Authors: Edward J. T. , Leane J. B. , Wang I. C.
Published: May 2006

The chemical shift of the methyl protons relative to the methylenic protons of an ethyl group attached to a basic center increases with the acidity of the medium. This increase may be attributed to two effects: over a relatively narrow range of acidity function (H0) values, to protonation of the basic center; over the complete H0 range investigated, to a general solvent effect, which may be due to changing strengths of hydrogen bonds between the basic center or its conjugate acid and solvent water molecules. Protonation constants [Formula: see text] of −1.1 for propionamide and −6.9 for propionic acid have been calculated, in good agreement with values obtained by the ultraviolet spectrophotometric method; the constants calculated for diethyl ether (−6.2) and ethanol (−4.8) are much less certain, because of the greater magnitude of the solvent effect with these compounds.
OXIMES: I. THE SYNTHESIS OF SOME SUBSTITUTED 2-OXIMINOACETOPHENONES
Authors: Norman J. J. , Heggie R. M. , Larose J. B.
Published: May 2006

The preparation of some p-(ω′-dimethylaminoalkyl)- and p-(ω′-dimethylaminoalkoxy)-2-oximinoacetophenones and their methiodides is described.No general method was found for synthesis of short-chain (C0, C1, C2) p-(ω′-dimethylaminoalkyl)-2-oximinoacetophenones. The longer-chain compounds (C3, C4) were prepared by a method which would appear to be general. ω-Phenyl-1-haloalkanes undergo Friedel–Crafts acylation to yield p-(ω′-haloalkyl)-acetophenones. These were converted to the dimethylamino compounds, which, subsequently, yielded 2-oximinoacetophenones. No method of preparation of p-(2′-dimethylaminoethyl)-2-oximinoacetophenone was found.Synthesis of p-(ω′-dimethylaminoalkoxy)-2-oximinoacetophenones was accomplished using mixed α,ω-dihaloalkanes and p-hydroxyacetophenone. The p-(ω′-haloalkoxy)-acetophenones from these reactants were first converted to oximes and then to the dimethylamino compounds. Syntheses of p-(ω′-dimethylamino-ethoxy, -propoxy, -butoxy, and -pentoxy)-2-oximinoacetophenones were achieved. That of p-(dimethylaminomethoxy)-2-oximinoacetophenone was unsuccessful.
AN APPARATUS FOR THE STUDY OF SHORT-LIVED FISSION PRODUCT RARE GASES
Authors: Ockenden D. W. , Tomlinson R. H.
Published: May 2006

A procedure is described for the isolation, separation, and study of short-lived krypton and xenon isotopes formed by thermal fission of uranium. The gases are swept out from a thin film of uranium-235 stearate, rapidly separated by gas chromatography, and examined by gamma-spectrometric techniques. Krypton isotopes have been studied within 10 seconds of their formation in the reactor and xenon isotopes within 25 seconds. Spectra are reported for krypton-89 and -90, xenon-137, -138, and -139.
SOME REACTIONS INVOLVED IN THE PHOTOBROMINATION OF SIMPLE ALCOHOLS AND KETONES IN THE VAPOR PHASE
Authors: Buckley E. , Whittle E.
Published: May 2006

The vapor phase brominations of methanol, ethanol, formaldehyde, and acetaldehyde are all photosensitive. The products have been identified and mechanisms postulated to explain their formation. The vapor phase reactions between formaldehyde and HBr, acetaldehyde and HBr, acetaldehyde and acetyl bromide, and ethanol and acetyl bromide have also been studied.
REACTIONS OF ALIPHATIC ARYLHYDRAZONES AND OF ANILINE WITH CARBON MONOXIDE TO YIELD UREAS
Authors: Rosenthal Alex
Published: May 2006

not available
THE PREPARATION AND RAMAN SPECTRUM OF DIPHOSPHORYL TETRAFLUORIDE: COMPARISON WITH THE SPECTRUM OF DIPHOSPHORYL TETRACHLORIDE
Authors: Robinson E. A.
Published: May 2006

Diphosphoryl tetrafluoride has been prepared by the dehydration of difluorophosphoric acid with phosphoric anhydride. The Raman and F19 n.m.r. spectra have been determined and are consistent with a symmetric structure F2P(O)—O—P(O)F2. The Raman spectrum is compared with that of diphosphoryl tetrachloride and partial assignments of the frequencies to normal modes of vibration are made by comparison with the spectra of POF3 and POCl3.
TRIMETHYL ORTHOBORATE – AMINE INCLUSION COMPOUNDS
Authors: Young D. M. , Anderson C. D.
Published: May 2006

A new class of non-stoichiometric crystalline inclusion compounds has been discovered, having the general formula[Formula: see text]where 0.5 < n < 1.0 and 0 < x < 3 depending on the method of preparation and on the nature of the amine and solvent. Such compounds have been prepared with ammonia and a variety of primary and secondary amines. Among the solvents which can be incorporated into the crystals are alcohols, ketones, ethers, esters, nitriles, nitroparaffins, and hydrocarbons. Such compounds are also formed by triphenyl orthoborate, with 1.7 < n < 2.4 and 1.2 < x < 1.6.The incorporated solvent has been shown to exert a definite vapor pressure. Furthermore, many of the compounds sublime at room temperature to form large transparent crystals which also contain incorporated solvent. The mechanism probably involves dissociation, followed by reassociation on the walls of the vessel. Preliminary X-ray diffraction measurements suggest that the trimethyl orthoborate – ammonia inclusion compounds have essentially the same crystal lattice as pure trimethyl orthoborate – ammonia.
THE KINETICS OF THE FORMATION OF THE MONOSULPHATO COMPLEX OF IRON (III) IN AQUEOUS SOLUTION
Authors: Davis G. G. , Smith W. MacF.
Published: May 2006

The kinetics of formation of the monosulphato complex of iron (III) has been examined spectrophotometrically using a continuous-flow technique over the range of temperatures 15.6 to 34.5 °C in an aqueous medium of ionic strength 0.5 and a range of concentrations of hydrogen ions 0.05 to 0.30 M. The experimental data may be interpreted on the assumption that the significant reactions are a bimolecular association opposed by a first-order dissociation [Formula: see text] For the forward reaction ΔH≠ is 18.0 kcal mole−1 and ΔS≠ is 19.4 cal mole−1 deg−1.
THE ELECTROLYSIS OF ω-BROMOCARBOXYLIC ACIDS
Authors: Woolford R.G.
Published: May 2006

The first successful preparation of ω,ω′-dibromides from the electrolyses of a series of ω-bromocarboxylic acids, Br(CH2)nCOOH (n = 5 to n = 11), is reported. Under conditions of fairly low temperature and current density, yields from 54 to 71% of these dibromides were obtained.The electrolysis of 11-bromoundecanoic acid is discussed as an example of how a small change in experimental conditions can produce a considerable change in the products of reaction. At 50°, the product was mainly 1,20-dibromoeicosane, whereas at 65° the products were mainly the esters methyl 11-bromoundecanoate and methyl 11-methoxyundecanoate.
NUCLEAR MAGNETIC RESONANCE SPECTRA OF SIX-MEMBERED ALCYCLIC RING COMPOUNDS AT LOW TEMPERATURE: IV. PARTIALLY DEUTERATED 1,2-trans-CHLOROIODOCYCLOHEXANE
Authors: Premuzic E. , Reeves L. W.
Published: May 2006

A 50/50 mole% mixture of 1-iodo-2-chloro-1,3,3-trideutero-, and 1-chloro-2-iodo-1,3,3-trideutero-cyclohexane has been synthesized. At −93 °C in a CS2 solution iodochlorocyclohexane shows resolution into diaxial and diequatorial halogen forms. Analysis of the adjacent proton resonance signal intensities shows that this compound exists 68±3 mole% in the diaxial halogan form. This is quite similar to 1,2-dibromocyclohexane, which has 70 mole% in the diaxial form, and is in contrast to 1,2-dichlorocyclohexane, which has a more stable diequatorial form.
SYNTHESIS AND PHYSIOLOGICAL PROPERTIES OF 9-HYDROXY-2-DECENOIC ACID
Authors: Brown Wm. H. , Felauer Ethel E. , Smith M. V.
Published: May 2006

not available
THE ELECTRON SPIN RESONANCE OF NON-ALTERNANT AROMATIC HYDROCARBON – IODINE COMPLEXES
Authors: Danyluk S. S. , Schneider W. G.
Published: May 2006

not available
NITRATION AND REDUCTION OF SUBSTITUTED AZOBENZENES AND AZOXYBENZENES
Authors: Singh Joginder , Singh Pritam , Boivin Jean L. , Gagnon Paul E.
Published: May 2006

The nitration of some symmetrically tetrasubstituted azo- and azoxy-benzenes in various nitrating media was found to yield the 4-nitro derivatives in some cases, while more drastic conditions gave the 4,4′-dinitro compounds. Some nitroazobenzenes were transformed to the 4-nitroazo and 4,4′-dinitroazoxy derivatives.Reduction of the mononitroazo-, dinitroazo-, and azoxy-benzenes gave the monoaminoazo, diaminoazo, and azoxy derivatives under mild conditions while strong reducing agents converted the whole molecule to 1,4-diaminobenzene. One exception was found with 2,2′,5,5′-tetramethyl-4,4′-dinitroazobenzene, which was reduced to 2,2′,5,5′-tetramethyl-4,4′-dinitrohydrazobenzene.
THE PRODUCTS OF THE PREVOST REACTION ON D-GLUCAL TRIACETATE
Authors: Lemieux R. U. , Levine S.
Published: May 2006

The compound reported by Stanek and Schwarz (Collection Czechoslov. Chem. Communs. 20, 42 (1955)) to be 1-O-benzoyl-2-iodo-2-deoxy-α-D-glucopyranose triacetate is actually an approximately equimolar mixture of 1-O-benzoyl-2-iodo-2-deoxy-β-D-glucopyranose triacetate and the stereoisomer with the α-D-manno configuration. Methanolysis of these compounds yielded methyl 2-iodo-2-deoxy-β-D-glucopyranoside and methyl 2-iodo-2-deoxy-α-D-manno-pyranoside, respectively. Hydrogenolysis of the latter iodoglycosides using a palladium catalyst gave near-quantitative yields of the corresponding methyl 2-deoxy-D-glucopyranosides. Several other properties of the iodides are reported.
ELECTROCHEMISTRY OF THE NICKEL OXIDE ELECTRODE: PART IV. ELECTROCHEMICAL KINETIC STUDIES OF REVERSIBLE POTENTIALS AS A FUNCTION OF DEGREE OF OXIDATION
Authors: Conway B. E. , Gileadi E.
Published: May 2006

Electrochemical kinetic studies have been carried out at the nickel oxide electrode showing that the reversible potential for the NiII–NiIII system is independent of the state of oxidation of the bulk oxide in the electrode over a wide range of degrees of oxidation. The properties of the electrode are shown to be determined by the state of a surface phase, which is completely charged when the bulk oxide material in the electrode has been charged to 10% of its total charge capacity. Experiments on sparingly charged electrodes have proved that charging of the bulk oxide does not commence significantly until the electrode is charged to about 1.5%. Consecutive electrochemical reactions possibly involved in the charging process are discussed.
MECHANISM OF ALKALINE HYDROLYSIS OF HINDERED AROMATIC ESTERS, THE BAL2 MECHANISM
Authors: Barclay L. R. C. , Hall N. D. , Cooke G. A.
Published: May 2006

Kinetic and isotopic exchange data employing H2O18 are presented to establish the bimolecular alkaline hydrolysis with alkyol–oxygen fission (BAL2) for the highly hindered ester methyl 2,4,6-tri-t-butylbenzoate. Methyl 2-methyl-4,6-di-t-butylbenzoate also cleaved predominately by alkyl–oxygen fission. Other hindered esters, methyl 2,4,6-trimethylbenzoate and methyl 2,5-di-t-butylbenzoate, hydrolyzed by the usual acyl–oxygen fission.
INFRARED SPECTRA OF CARBON MONOXIDE AND CARBON DIOXIDE ADSORBED ON CHROMIA–ALUMINA AND ON ALUMINA
Authors: Little L. H. , Amberg C. H.
Published: May 2006

Infrared spectra of CO and CO2 adsorbed on chromia–alumina and on alumina surfaces have been determined. A band near 2200 cm−1 formed by CO on both surfaces at room temperature was due to a weak, non-activated sorption, but also contained a contribution from a more strongly sorbed, activated species on the chromia–alumina. The assignment of this band was discussed in some detail. Bands in the region 1200–1800 cm−1 were considered in terms of surface CO2− species, although in certain instances the appearance of bands at 1750 and 1430 cm−1 may have indicated carbonate ion formation.
OXIMES: II. THE INFRARED SPECTRA OF SOME COMPLEX OXIMES
Authors: Norman J. J.
Published: May 2006

The infrared spectra of several ω′-substituted p-alkyl- and p-alkoxy-2-oximinoacetophenones were investigated. When the ω′-substituent was the dimethylamino group, the spectra were incompatible with a simple α-ketooxime structure. The spectra of these dimethylamino compounds showed a diffuse absorption with broad peaks at 2500 and 1850 cm−1. The hydroxyl band at 3150 cm−1 and the dimethylamino doublet at 2820 and 2770 cm−1 had nearly disappeared while the carbonyl and N—O frequencies had undergone large shifts. The spectra are best interpreted in terms of a zwitterion carrying a novel anion. The structure of this anion is considered.
3,4-DIHYDRO-β-CARBOLINES: II. THE EXHAUSTIVE METHYLATION OF 3,4-DIHYDRO-β-CARBOLINE
Authors: Gupta R. N. , Spenser Ian D.
Published: May 2006

The methiodide of 3,4-dihydro-β-carboline yields a dimeric anhydro base which, on heating, disproportionates to a β-carboline and a tetrahydro-β-carboline derivative, and on methylation is converted to 3-[2-formylindolyl]-β-ethyltrimethylamnionium iodide.
THE ULTRAVIOLET ABSORPTION SPECTRUM OF NITROUS ACID IN THE VAPOR STATE
Authors: King G. W. , Moule D.
Published: May 2006

The diffuse absorption bands of HON14O, HON16O, DON16O, and DON15O in the near ultraviolet have been examined. Transitions from both rotational isomers of nitrous acid contribute to the vibrational structure, with the excited state σ(N=O) stretching vibrations active in the most intense progressions. The cis–trans energy separation increases from 500 cal/mole in the ground state to 1200 cal/mole in the upper state. This is attributed to weakening of the internal hydrogen bond in the cis state upon an electronic promotion of primarily nO → π* type. The accompanying change in geometry is responsible for the appearance of the cis ground-state δ(ONO) bending mode in the spectrum.
EXOCELLULAR BACTERIAL POLYSACCHARIDE FROM XANTHOMONAS CAMPESTRIS NRRL B-1459: PART I. CONSTITUTION
Authors: Sloneker J. H. , Jeanes Allene
Published: May 2006

Polysaccharide B-1459 is the first bacterial polysaccharide reported to contain pyruvic acid as a constituent. The polysaccharide, isolated as the potassium salt, was shown to be composed of D-glucose, D-mannose, and D-glucuronic acid, acetic acid, and pyruvic acid in the ratio 2.8:3.0:2.0:1.7:0.51–0.63. One-third of the total mannose was released readily as free mannose by graded acid hydrolysis with only a slow loss of the high solution viscosity. The remainder of the mannose was isolated as the acid-stable aldobiouronic acid 2-O-(β-D-glucopyranosyluronic acid)-D-mannose. Partial acid hydrolysis and preparative paper chromatography afforded two higher oligosaccharides: an aldotriouronic acid composed of glucuronic acid β-linked 1,2 to mannose with glucose as the reducing end group, and what appears to be an aldotetraouronic acid composed of glucuronic acid, mannose, and glucose.
IDENTIFICATION OF CONJUGATED TRIENE FATTY ACIDS IN CERTAIN SEED OILS
Authors: Hopkins C. Y. , Chisholm Mary J.
Published: May 2006

Seed oils were hydrolyzed under mild conditions and the major conjugated fatty acid of each oil was isolated and identified. In two families, species which were closely related botanically contained different but isomeric acids. Thus, in the Bignoniaceae, Jacaranda chelonia had cis trans,cis-8,10,12-octadecatrienoic acid as a major acid while Catalpa speciosa had trans,trans,cis-9,11,13-octadecatrienoic acid. In the Cucurbitaceae, Momordica charantia had the ordinary cis,trans,trans-9,11,13-octadecatrienoic (α-eleostearic) acid while M. balsamina had cis,trans,cis-9,11,13-octadecatrienoic (punicic) acid. M. balsamina is a new and convenient source of punicic acid. α-Eleostearic acid was identified as a major acid in examples of Valerianaceae and Rosaceae. Further proof was obtained that the fatty acid of Calendula officinalis (Compositae) is trans,trans,cis-8,10,12-octadecatrienoic acid.
STUDIES ON THE INFRARED SPECTRA OF A MERCAPTOTRIAZOLE AND MERCAPTOTHIAZOLINE AND THEIR ADSORPTION ON SILVER IODIDE
Authors: Little L. H. , Ottewill R. H.
Published: May 2006

An investigation has been carried out on the infrared spectra of 3-mercapto-4-methyl-5-ethyl-1,2,4-triazole and 2-mercaptothiazoline, both in solution and in the crystalline form. The spectra of the deuterated compounds and the silver salts have also been examined. The results allow some assignment of bands to be made. The spectra of these compounds adsorbed on silver iodide were then examined. It would appear that in the concentration range examined physical adsorption occurs.
N-MUSTARD DERIVATIVES OF ESTROGENS
Authors: Nogrady Thomas , Vagi Kitty M. , Adamkiewicz Vincent W.
Published: May 2006

N-Mustard urethanes of estrone and stilbestrol, as well as an N-mustard-phosphoramidate of stilbestrol, were synthesized. Only the estrone derivative proved to be slightly active against an adenocarcinoma.
THE CONFORMATIONS OF THE 20-KETO SIDE CHAIN OF C21-STEROIDS
Authors: Rakhit S. , Engel Ch. R.
Published: May 2006

not available
THE SYNTHESIS OF LIGNIN MODEL SUBSTANCES: 5-HYDROXYVANILLIN AND 5-HYDROXYACETOGUAIACONE
Authors: Banerjee S. K. , Manolopoulo M. , Pepper J. M.
Published: May 2006

not available
THE p-BROMOPHENYLOSAZONES OF 3- AND 5-O-METHYL-D-XYLOSE AND AN APPLICATION OF THIN-LAYER CHROMATOGRAPHY
Authors: Applegarth D. A. , Dutton G. G. S. , Tanaka Y.
Published: May 2006

not available
SYNTHESIS AND PROPERTIES OF HOMOTAURINE
Authors: Sen N. P.
Published: May 2006

not available
THERMAL DECOMPOSITION OF MOLECULAR COMPLEXES: I. UREA-n-PARAFFIN INCLUSION COMPOUNDS
Authors: McAdie H. G.
Published: May 2006

The molecular complexes of urea and even-numbered n-paraffins up to C28 undergo thermal decomposition below the melting point of urea at temperatures which increase with the n-paraffin chain length. The decomposition is endothermal and is accompanied by changes in crystal structure, appearance, and by loss of the n-paraffin. Based on the enthalpy change a mechanism for the decomposition process is proposed.
THE CARBOHYDRATE–PROTEIN LINKAGE IN GLYCOPROTEINS: PART II. THE SYNTHESIS OF N-L-SERYL-D-GLUCOSAMINE AND N-L-THREONYL-D-GLUCOSAMINE
Authors: Jones J. K. N. , Millington J. P. , Perry M. B.
Published: May 2006

N-L-Seryl-D-glucosamine has been prepared by the condensation of N-carbobenzoxy-L-serine with D-glucosamine in the presence of dicyclohexyl carbodiimide followed by hydrogenolysis of the resulting N-(N-carbobenzoxy-L-seryl)-D-glucosamine to remove the N-carbobenzoxy protecting group.N-L-Threonyl-D-glucosamine has been prepared by (a) the condensation of 1,3,4,6-tetra-O-acetyl-α- (and β-) D-glucosamine and N-carbobenzoxy-O-tetrahydropyranyl-L-threonine in the presence of diisopropyl carbodiimide followed by the removal of the protecting groups from the resulting N-(N-carbobenzoxy-O-tetrahydropyranyl-L-threonyl)-1,3,4,6-tetra-O-acetyl-α- (and β-) D-glucosamine, and (b) by the condensation of N-carbobenzoxy-L-threonine with D-glucosamine in the presence of dicyclohexyl carbodiimide followed by removal of the N-carbobenzoxy group from the resulting N-(N-carbobenzoxy-L-threonyl-D-glucosamine by hydrogenolysis.
COORDINATION COMPLEXES OF TITANIUM (IV) HALIDES: IV. PREPARATION AND INFRARED SPECTRA OF THE COMPLEXES OF TITANIUM TETRACHLORIDE WITH CHLORINE-SUBSTITUTED ESTERS OF MONOBASIC ACIDS AS LIGANDS
Authors: Jain Sumer Chand , Rivest Roland
Published: May 2006

Coordination complexes between titanium tetrachloride and some chlorine-substituted monoesters have been prepared.Infrared spectra of these complexes and their melting points indicate that the strength of the coordination bonds decreases as the number of chlorines increases in the acid radical. When the substitution is in the alkyl radical, it is possible to prepare complexes of the formula TiCl4•2 ester, since the chlorine substitution decreases the basic properties of the oxygen of the ether group in the ligand.
STUDIES ON THE MECHANISM OF PERSULPHATE-INITIATED GRAFTING ONTO CELLULOSE
Authors: Sankalia S. M. , Chaudhuri D. K. Ray , Hermans J. J.
Published: May 2006

When the polymerization of vinyl acetate or acrylonitrile is initiated by persulphate in the presence of cellophane, grafting onto the cellulosic backbone occurs. This is proved by comparing the graft with a physical mixture of cellulose and homopolymer.Some aspects of the mechanism of this grafting are studied by means of model compounds, in particular pinacol. It is found that the rate of polymerization of acrylonitrile initiated by persulphate is increased by the addition of pinacol, but decreases on addition of more pinacol. This may be explained by assuming that the radicals formed from the pinacol can terminate each other and that this reaction competes with the reaction between these radicals and the monomer. The amount of acetone formed by the persulphate oxidation of pinacol at low pinacol concentrations is about 0.5 mole per mole persulphate and decreases with increasing pinacol concentration. This indicates complexities that do not exist in the ceric ion oxidation of pinacol.
THE VIBRATIONAL MECHANISM OF THE FUNDAMENTAL NH2 STRETCHING VIBRATIONS IN ANILINES
Authors: Krueger Peter J.
Published: May 2006

The integrated intensities, frequencies, and half-band widths of the fundamental symmetric and asymmetric NH2 stretching vibrations in 33 ortho-substituted anilines, measured in dilute carbon tetrachloride solution, have been examined in relation to the corresponding absorption band parameters for 31 meta- and para-substituted anilines, taking into consideration the electronic effects of the substituents. From an almost tetrahedral configuration in p-phenylenediamine, the calculated s-character of the nitrogen atom gradually increases as the substituent groups become more electron withdrawing, with a resultant increase in the apparent HNH angle and the NH force constant. Ortho substitution in general leads to enhanced HNH angle opening, probably because of intramolecular hydrogen bonding. The decrease in half-band width for both vibrational modes in ortho-substituted anilines with respect to corresponding values in meta and para compounds is ascribed to steric hindrance to solvation of the amino group.The asymmetric intensities in ortho-substituted anilines are generally increased over corresponding values in meta and para compounds, unlike the behavior of the symmetric mode. These results are consistent with a vibrational mechanism taking into account the following factors for each mode: (i) the direction of the transition moment, (ii) the extent of nitrogen lone pair and aromatic π-electron participation, and (iii) the direct field effect of the ortho substituent.
THE REDUCTION OF NITROBENZENE BY HYDROSULPHIDE ION IN AQUEOUS MEDIA
Authors: Cope O. J. , Brown R. K.
Published: May 2006

The reduction of nitrobenzene by sodium hydrosulphide and sodium hydrodisulphide in aqueous media at 50° has been examined. Goldschmidt's report of first-order dependence upon both nitrobenzene and hydrosulphide is corroborated. The action of hydrosulphide on nitrobenzene produces phenylhydroxylamine, which is reduced by hydrosulphide much more slowly than is nitrobenzene. As reaction progresses, nitrobenzene reduction produces yellow hydrodisulphide, which is responsible for the observed autocatalytic effect. Hydrodisulphide reduces phenylhydroxylamine more rapidly than it does the original nitrobenzene, and hence as reaction time is extended, phenylhydroxylamine disappears more rapidly than does nitrobenzene, yielding only aniline and some unreacted nitrobenzene towards the end of the reaction. Hydrosulphide reduction of phenylhydroxylamine to aniline produces thiosulphate but apparently no hydrodisulphide. Hydrodisulphide reduction of the phenylhydroxylamine leads only to conversion of the yellow hydrodisulphide to a colorless species, apparently thiosulphate. On the other hand hydrosulphide or hydrodisulphide reduction of nitrobenzene is accompanied by thiosulphate formation and some increase in hydrodisulphide. A comparison of the rate constants shows that under the conditions of the reaction, hydrodisulphide ion reduces nitrobenzene about seven times more rapidly than does hydrosulphide ion while phenylhydroxylamine is reduced two to three times more rapidly by hydrodisulphide than is nitrobenzene.
NUCLEAR MAGNETIC RESONANCE STUDIES: PART II. SOLVENT EFFECTS IN THE N.M.R. SPECTRA OF AROMATIC ALDEHYDES
Authors: Klinck R. E. , Stothers J. B.
Published: May 2006

The chemical shifts for the aromatic and formyl protons of a series of substituted benzaldehydes have been obtained in a number of solvents. Relative to the shifts observed in chloroform, pronounced effects are observed in acetone and benzene solutions. In general, the shielding of these nuclei is decreased in acetone and increased in benzene, while in benzene the magnitude of the solvent shift for a given proton depends markedly on the nature of the substituent group. These results can be rationalized in terms of a specific solute-solvent interaction in which the site of association is governed by the electron distribution in the solute molecule. The nature of the solvent interactions in this and related systems is discussed.
BIOGENETIC STUDIES ON VOLUCRISPORIN
Authors: Read G. , Vining L. C. , Haskins R. H.
Published: May 2006

In experiments with C14-labelled compounds, shikimic acid, phenylalanine, phenyllactic acid, and metatyrosine were found to be precursors of the terphenylquinone pigment volucrisporin. It is suggested that the pigment is biosynthesized by the self-condensation of two molecules of an unbranched phenylpropanoid intermediate, and that hydroxylation of the phenyl rings in the meta position occurs before the condensation step.
KINETICS OF THE REACTIONS OF ATOMIC HYDROGEN EFFECT OF DIFFUSION ON THE DETERMINATION OF H ATOM CONCENTRATION
Authors: Schulz W. R. , Roy D. J. Le
Published: May 2006

not available
METABOLITES OF PATHOGENIC FUNGI: III. THE STRUCTURE OF XANTHOMEGNIN
Authors: Just George , Day William C. , Blank Fritz
Published: May 2006

Xanthomegnin, a pigment isolated from Trichophyton megnini, was shown to be (−) 3,3′-bis-[2-methoxy-5-hydroxy-7-(2-hydroxypropyl)-8-carboxy-l,4-naphthoquinone lactone]. Application of the Hudson–Klyne lactone rule (C. S. Hudson, J. Am. Chem. Soc., 32, 338 (1910); W. Klyne, Chem. Ind. (London), 1198 (1954)) gave results which supported the proposed stereochemistry.
THE S32 (n,p) P32 REACTION AS A FAST-NEUTRON FLUX MONITOR
Authors: Santry D. C. , Butler J. P.
Published: May 2006

An extensive study is made of the use of sulphur as a monitor for neutrons with energies from 2 to 20 Mev. Irradiated disks of pressed sulphur are burnt before counting to increase the efficiency and reproducibility of determining the P32 activity. It was established that on burning irradiated sulphur 95.5 ± 0.5% of the P32 activity is retained with a reproducibility of ± 1.0%. Measurements of relative cross sections for the S32 (n,p) P32 reaction have been extended to 20.3 Mev using the T (d,n) He4 and D (d,n) He3 reactions to produce monoenergetic neutrons. Neutron production using Zr−T targets is examined as is the effect of extraneous neutrons from the D (d,np) D process on the S32 (n,p) reaction.
CONCURRENT ION–MOLECULE REACTIONS IN ETHYLENE AND PROPYLENE
Authors: Harrison A. G.
Published: May 2006

The ion–molecule reactions occurring in ethylene and in propylene at high pressures in the mass spectrometer ion source have been studied. It has been shown that two of the six secondary ions in ethylene and four of the nine secondary ions studied in propylene are products of more than one ion–molecule reaction. The cross sections for the separate reactions at 10 v/cm field strength are reported.
THERMOGRAVIMETRY OF THE DEHYDRATION OF Mg(OH)2
Authors: Turner R. C. , Hoffman I. , Chen D.
Published: May 2006

The DTG curves for the dehydration of a number of preparations of Mg(OH)2 were determined. Equations necessary to calculate energies of activation and rate constants from these curves were derived on the basis of a two-thirds-order process for dehydration. It was found that the energy of activation was about 5 kcal greater for naturally occurring than for precipitated Mg(OH)2. This was interpreted to mean that there was a difference in the energy levels of the two preparations, and therefore a difference in their apparent solubility products. Differences obtained in the DTG curves for four different preparations of Mg(OH)2 indicated the probability of a series of energy levels for Mg(OH)2.
APPLICATION OF QUASI-LATTICE THEORY TO ALCOHOL – CARBON TETRACHLORIDE SYSTEMS
Authors: Dacre B. , Benson G. C.
Published: May 2006

Values of heats of mixing are reported for methanol, n-butanol, and n-octanol with carbon tetrachloride at 25 °C. The experimental results are combined with data from other sources and an analysis of the excess thermodynamic functions for carbon tetrachloride solutions of methanol, ethanol, n-propanol, n-butanol, and n-octanol in terms of Barker's theory of solutions is described. The behavior of these systems can be reproduced fairly well by the Barker model.
THE DETECTION AND ESTIMATION OF BRANCHING IN DEXTRAN BY PROTON MAGNETIC RESONANCE SPECTROSCOPY
Authors: Pasika W. M. , Cragg L. H.
Published: May 2006

The proton magnetic resonance spectrum of branched dextran contains a peak, not found in the spectrum of linear dextran, which is assigned to C1 protons at non-1,6-linkages—linkages which in most branched dextrans form the branch points. A quantitative measure of the extent of branching—the ratio of 1,6-linkages to non-1,6-linkages—is obtained by taking the ratio of the areas of the peaks associated with these two types of linkages. The value so obtained agrees well with that obtained by periodate analysis.For polysaccharides in which the non-1,6-linkages are known to be at branch points, n.m.r. spectroscopy thus affords a means of detecting and estimating branching which is more convenient than methods currently in use.
THE MERCURY-SENSITIZED PRIMARY DECOMPOSITION OF DEUTERATED PROPANES: A MASS SPECTROMETRIC STUDY AT LOW PRESSURES: PART II
Authors: Avrahami M. , Kebarle P.
Published: May 2006

The primary decomposition of C3H8, CD3CH2CD3, CH3CD2CH3, and C3D8 was found equal to: 10, 8, 5.5, and 5%.The primary reactions were[Formula: see text]The ratio a/b was strongly affected by deuterium substitution. The numerical values of the ratio for the compounds in the order given above are: 1.2, 6.8, 0.2, 0.9. Elucidation of the underlying reasons for this surprisingly large isotope effect might throw new light on the excited mercury – paraffin interaction.
FORMATION OF DIASTEREOISOMERIC ORTHOACETATES OF D-MANNOSE: N.M.R. SPECTRAL EVIDENCE
Authors: Perlin A. S.
Published: May 2006

Diastereoisomeric 1,2-orthoacetates of D-mannose are formed under conditions of the Königs–Knorr synthesis. This is shown by the isolation of two crystalline isomers of β-D-mannose 1,2-(benzyl orthoacetate), and also by examination of the nuclear magnetic resonance (n.m.r.) spectra of several D-mannose orthoacetates. The diastereoisomers show notable differences in respective chemical shifts for the C-methyl and other protons and these variations, together with isomer-ratio data, suggest that the major isomer of a given pair possesses the configuration in which the C-methyl group is endo- and the OR group is exo-. On acid hydrolysis the orthoacetates yield mainly 2-O-acetyl-D-mannose, the structure of which is confirmed by n.m.r. spectral evidence.
THE SULPHURIC ACID SOLVENT SYSTEM: PART IV. SULPHATOCOMPOUNDS OF ARSENIC (III)
Authors: Gillespie R. J. , Robinson E. A.
Published: May 2006

The cryoscopic and conductimetric behavior of arsenic (III) oxide in 100% sulphuric acid and in dilute oleum have been investigated. It is concluded that in very dilute solutions in 100% sulphuric acid, arsenic (III) oxide forms arsonyl (III) hydrogen sulphate, AsO.HSO4, which is partly ionized to give the AsO+ cation. Both these species probably exist mainly in solvated forms, e.g., As(OH)(SO4H)2, and As(OH)(SO4H)+ respectively. At higher concentrations polymeric species such as HO.As(HSO4)OAs(HSO4)2 are present in increasing amounts and eventually the insoluble polymeric compound [(AsO)2SO4]n separates from solution. In oleum the more sulphated species As(HSO4)3, [(HSO4)2As]2O, and [(HSO4)2As]2SO4 are formed. Related structures are proposed for some previously prepared compounds of arsenic (III) oxide and sulphur trioxide.
STEREOCHEMISTRY OF ARSENIC: VIII. CYANODIMETHYLARSINE (CACODYL CYANIDE)
Authors: Camerman N. , Trotter J.
Published: May 2006

Crystals of cyanodimethylarsine, (CH3)2AsCN, are triclinic with two molecules in a unit cell of dimensions a = 6.31, b = 8.02, c = 6.27 Å, α = 110°00′, β = 119°45′, γ = 81°47′, space group [Formula: see text]. The structure has been determined from projections along the three crystallographic axes, and the mean values of the bond lengths and valency angles (with estimated standard deviations) are: As—C = 1.96±0.03 Å, C—N = 1.16 ± 0.07 Å, [Formula: see text], [Formula: see text], [Formula: see text]. There is an unusually short As … N intermolecular separation, which is indicative of charge-transfer bonding involving donation of nitrogen lone pair electrons to vacant arsenic 4d orbitals; the other intermolecular approaches correspond to normal van der Waals interactions.
INFRARED SPECTRA OF XANTHONE: LEWIS ACID COMPLEXES
Authors: Cook Denys
Published: May 2006

Xanthone, a member of the γ-pyrone species, which have basic carbonyl groups, forms an excellent series of solid complexes with Lewis acids. In these complexes the carbonyl oxygen atom is the donor site, and the carbonyl stretching vibration moves to progressively lower frequency as the Lewis acid strength increases. The carbonyl frequency in the BI3 complex, 1400 cm−1, is one of the lowest encountered in complexes of this type.The wide range of Lewis acids used to form these complexes has enabled a quantitative estimate of the Lewis acid strength to be made, which compares reasonably well with previous estimates.
EXCHANGE RATE AND ACTIVATION ENERGY OF EXCHANGE FOR N,N-DIMETHYLANILINE IN TRIFLUORACETIC ACID
Authors: Reynolds W. F. , Schaefer T.
Published: May 2006

not available
THE THERMAL DECOMPOSITION OF AZOMETHANE: I. EFFECT OF ADDED OLEFIN AND NITRIC OXIDE
Authors: Forst W. , Rice O. K.
Published: May 2006

The addition of ethylene and propylene reduces the rate of azomethane decomposition as measured by the rate of nitrogen production, and also reduces the ratio CH4/N2 in the products, but the reduction in the value of both quantities is different for each of the two olefins. In 100% decomposition, ethylene and propylene both increase somewhat the ratio (nitrogen recovered)/(azomethane decomposed). These results are interpreted to mean that there is in fact a short chain in the pyrolysis, but that ethylene and propylene are unsuitable inhibitors.The addition of a few millimeters of NO reduces the rate to a minimum which is lower than that with added propylene or ethylene (apparent chain length 2 to 3), but further addition of NO increases the rate again. Identical result is obtained in a packed vessel. The yield of methane, ethane, and ethylene is reduced to almost zero with a sufficient amount of NO. The ratio (NO consumed)/(nitrogen produced) reaches the value of two in the neighborhood of the rate minimum. It is concluded that the net inhibited rate, i.e. rate corrected for the stimulatory effect of NO, refers to the initial unimolecular process CH3N2CH3 → 2CH3 + N2. The rate as well as the activation energy of this process is found to be pressure dependent.It is shown by the use of the isotopic nitric oxide 15NO that about one-half of the rate increase at higher NO pressures is due to nitrogen produced from NO. The remainder of the rate increase is accounted for by a NO-induced decomposition of azomethane.
SYNTHESIS OF A SUGAR DERIVATIVE WITH NITROGEN IN THE RING
Authors: Jones J. K. N. , Szarek W. A.
Published: May 2006

l-Acetyl-D-gulo(ido)-2,3,4,5-tetrahydroxypiperidine, a sugar derivative with nitrogen in the ring, has been synthesized from D-xylose. The synthetic route and proof of structure are described.
LYCOPODIUM ALKALOIDS: V. THE BROMINATION OF LYCOPODINE AND THE STRUCTURE OF ALKALOID L.20
Authors: Ayer W. A. , Berezowsky J. A. , Law D. A.
Published: May 2006

Monobromination of lycopodine hydrobromide in chloroform yields 6α-bromolycopodine hydrobromide, which can be epimerized to 6β-bromolycopodine hydrobromide. Hydrolysis of 6α-bromolycopodine proceeds with overall retention of configuration to give 6 α-hydroxylycopodine, which is identical with the Lycopodium lucidulum alkaloid L.20. On the basis of some of the rotatory dispersion data presented it is suggested that positively charged nitrogen has a negative specific rotativity.
PROTON COUPLING CONSTANTS IN SUBSTITUTED CYCLOPROPANES
Authors: Hutton H. M. , Schaefer T.
Published: May 2006

Coupling constants between geminal protons are reported for a number of cyclopropane derivatives. They are compared with results from previous work and other values in the literature. It is suggested that the geminal couplings are of opposite sign to the vicinal couplings and therefore negative. Comparison of the H—C—H angles with the former are therefore no longer valid. It is also suggested that the geminal couplings are zero in ethylene sulphides and positive in epoxides and that there is a change in sign in going from carbon through sulphur to oxygen as the third atom in the ring. The vicinal coupling constants depend on the dihedral angle as predicted by theory but the substituent effects do not appear to follow a simple dependence on the electronegativity as they do in substituted ethanes.
THE CHEMILUMINESCENT REACTION OF ACTIVE NITROGEN WITH THALLOUS HALIDES
Authors: Phillips L. F.
Published: May 2006

Energy transfer from active nitrogen to gaseous thallous halides leads to dissociation of the halide molecules with simultaneous production of excited thallium atoms. Thallium emission lines have been observed to correspond to the transfer of up to 221 kcal/mole to the TlX molecule. The process is kinetically third order but the high overall efficiency of light emission and thallous halide destruction requires a mechanism which involves a bimolecular reaction of TlX with an excited N2 formed during N-atom recombination.
A STATISTICAL APPROACH TO THE ANALYSIS OF INFRARED BAND PROFILES
Authors: Jones R. Norman , Seshadri K. S. , Jonathan N. B. W. , Hopkins J. W.
Published: May 2006

A method is described for the quantitative description of the profile and asymmetry of an infrared absorption band, based on the computation of the second and third incomplete moments of the absorbance curve. Provision is included for differentiation between the intrinsic band asymmetry and that induced by instrumental factors dependent on the direction of scan. A program has been prepared for an I.B.M. 1620 computer to facilitate the calculation of the moments. This program also yields the incomplete fourth moments, the statistical kurtosis parameter ([Formula: see text]), and the Gauss–Cauchy index, though these quantities are not employed in the present investigation. Examples are given of the application of these computations to the analysis of the effect of the spectral slit width on the profiles of bands at 812.7 and 726.6 cm−1 respectively in the spectra of carbon disulphide solutions of perylene and anthracene, and of the effect of the amplifier time constant on the asymmetry of the band at 2234.4 cm−1 in the spectrum of p-chlorobenzonitrile in tetrachloroethylene solution.
TEMPERATURE CONTROL ATTACHMENTS FOR VARIABLE AND FIXED PATH LENGTH INFRARED CELLS
Authors: Smith M. S. , Maine P. A. D. De
Published: May 2006

not available
3-TRIFLUOROMETHYL AND 4-t-BUTYL DERIVATIVES OF TETRAPHENYLTIN
Authors: Neville Roy G.
Published: May 2006

not available
THE PHOTOLYSIS OF ISOCYANIC ACID VAPOR
Authors: Mui J. Y. P. , Back R. A.
Published: May 2006

The photolysis of isocyanic acid vapor has been studied at temperatures ranging from −31 to 200 °C, and pressures from about 2 to 200 mm. Products identified were CO and N2 in a ratio which varied from 2.5 to 5, together with much smaller amounts of hydrogen. The mechanism[Formula: see text]accounts approximately for the products of the photolysis at low HNCO pressures and low temperatures. Additional reactions of NCO radicals with HNCO are postulated to account for increased production of CO and N2 as the temperature and HNCO pressures were increased.The effects of adding ethylene and hydrogen to the system were briefly investigated. The results are explained in terms of reactions of NH and NCO radicals with hydrogen and ethylene.
KINETICS AND MECHANISMS OF THE PYROLYSIS OF n-BUTANE: PART II. THE REACTION INHIBITED BY NITRIC OXIDE
Authors: Sagert N. H. , Laidler K. J.
Published: May 2006

The kinetics of the pyrolysis of n-butane, when maximally inhibited by nitric oxide, were studied at temperatures from 540° to 610 °C, and at pressures from 30 to 550 mm Hg. The reaction has a short induction period and is accurately of the three-halves order; the activation energy was 65.9 kcal mole−1 and the frequency factor 5.3 × 1016 cc1/2 mole−1/2 sec−1. The reaction was somewhat less inhibited by surface than was the uninhibited reaction. Excess of carbon dioxide had no effect on the rate. The results are explained in terms of a free-radical mechanism for the maximally inhibited decomposition. It is proposed that the initiation step in the inhibited decomposition is mainly C4H10 + NO → C4H9 + HNO. This is followed by the ordinary chain-propagating reactions, and by processes such as C2H5 + NO → C2H5NO. The main chain-terminating step, of the type β + βNO, is concluded to be C2H5 + C2H5NO → C4H10 + NO or C2H6 + C2H4 + NO. This scheme leads to three-halves-order kinetics, and provides a satisfactory quantitative interpretation of the experimental behavior.
HYDROLYTIC REACTIONS OF DISULPHUR MONOXIDE IN A HOMOGENEOUS MEDIUM
Authors: Nair C. G. Ramachandran , Murthy A. R. Vasudeva
Published: May 2006

The hydrolytic reactions of disulphur monoxide are studied in a homogeneous medium. Alkaline hydrolysis gives a mixture of sulphide, sulphite, and thiosulphate. Hydrolysis in the presence of sulphite in neutral medium gives equimolar amounts of trithionate and thiosulphate. These reactions are closely similar to the reactions of derivatives of thiosulphurous acid. The production of trithionate is explained on the basis of the formation of thiosulphurous acid as the primary product during hydrolysis and therefore it is suggested that disulphur monoxide is the true anhydride of this acid.
A STUDY OF THE VAPOR PHASE REACTION OF OZONE WITH OLEFINS IN THE PRESENCE AND ABSENCE OF MOLECULAR OXYGEN
Authors: Wei Y. K. , Cvetanović; R. J.
Published: May 2006

Relative rates of reaction of ozone with a number of olefins in the vapor phase have been determined at room temperature in the presence and absence of molecular oxygen. In the absence of oxygen the rates appear to follow more closely an electrophilic trend, although some of the deviations observed previously in the presence of oxygen still persist to some extent. The ratio of olefin to ozone consumed is unity in the absence of oxygen and varies from about 1.4 to 2 in its presence. In the presence of molecular oxygen, therefore, a secondary attack on the olefins takes place as well. The yields of products are similarly affected.
CO-CATALYSIS IN FRIEDEL–CRAFTS REACTIONS: VI. POLYMERIZATION OF 2-BUTENE BY BORON FLUORIDE – METHANOL
Authors: Allcock H. R. , Eastham A. M.
Published: May 2006

2-Butene is polymerized by boron fluoride and methanol in ethylene dichloride solution at ordinary temperatures to give very low molecular weight polymers. The rate of polymerization shows exactly the same dependence on catalyst concentration as did the rate of isomerization of the cis- and trans-2-butenes, i.e. first order both in free boron fluoride and in the boron fluoride – methanol complex. The polymerization, however, shows a first-order dependence in olefin over a concentration range where the isomerization is, experimentally, virtually independent of the olefin concentration.
PROTON MAGNETIC RESONANCE SHIFTS AND THE ELECTRON DENSITY DISTRIBUTION IN AROMATIC SYSTEMS
Authors: Schaefer T. , Schneider W. G.
Published: May 2006

The quantitative nature of the empirical linear correlation between the proton resonance shifts in aromatic molecules and the local electron density on the carbon atom to which the proton is bonded has been investigated. The application of this relationship to the determination of the electron density distribution of a variety of aromatic molecules, as well as the main limitations inherent in this application, are discussed. Electron density distributions have been derived for aniline, anisole, azulene, acepleiadylene, pyridine, pyridinium ion, and for the aromatic ions pentalenyl, indenyl, fluorenyl, triphenylmethyl cation, and azulene dianion, and are compared with those calculated by molecular orbital methods. In general there is a fairly good correspondence between the experimental and calculated density values, although for the aromatic ions the excess charge tends to be somewhat more uniformly distributed over the molecule than would be indicated by simple MO calculations.
INFLUENCE OF A PULSED ELECTRIC FIELD ON LUMINESCENCE IN THE RARE GASES EXCITED BY IONIZING RADIATION
Authors: Szymanski Aleksander , Herman Jan A.
Published: May 2006

not available
PHTHALIDE FORMATION: IV. CONDENSATIONS WITH 5-METHOXY-3-METHYLBENZOIC ACID
Authors: Charlesworth E. H. , Levene Leon
Published: May 2006

The products of the condensation of 5-methoxy-3-methylbenzoic acid with aqueous formaldehyde and hydrochloric acid in the presence of glacial acetic acid are dependent on the length of the heating period. A very short period of heating (2 minutes) yields 6-methoxy-4-methylphthalide and the two chloromethylphthalides of m.p. 135° and 154 °C, related to the unisolated 4-methoxy-6-methylphthalide. If the period of heating is 20 minutes or longer, the above chloromethylphthalide melting at 135° is formed and in addition some of the 6-methoxy-4-methylphthalide is chloromethylated to 6-methoxy-7-chloromethyl-4-methylphthalide, melting at 179°. The orientation of all three chloromethylphthalides has been established.
THE STABILITY OF METALLIC COMPLEXES OF TWO DIMETHYLPHENANTHROLINES
Authors: Brisbin D. A. , Mcbryde W. A. E.
Published: May 2006

The stepwise formation constants for the complexes formed by 5,6-dimethyl- and 4,7-dimethyl-1,10-phenanthroline with bivalent iron, cobalt, nickel, copper, and zinc were determined by a partition method. The measurements were made at 25 °C and in aqueous solutions having an ionic strength maintained at 0.1. The enhanced basicity of the ligands compared to the parent phenanthroline is paralleled by increased stability of the metallic complexes. The abnormally high formation constants of the cobalt complexes suggest oxidation to cobalt (III).