bluuebunny/crossref_metadata_2025 huggingface dataset:
SYNTHESIS OF CYCLIC PHOSPHOROUS ACID ESTERS BY TRANSESTERIFICATION
Authors: Oswald Alexis A.
Published: May 2006

Five- and six-membered cyclic phosphorous acid esters were synthesized by transesterification of phosphites with 1,2- and 1,3-glycols: Diethyl hydrogen phosphite was transesterified to give cyclic hydrogen phosphites. Partial transesterification of tris-2-chloroethyl phosphite resulted in cyclic 2-chloroethyl phosphites.
SYNTHESIS OF 2,4-THIAZOLIDINEDIONE-2-AZINES AND 2,4-THIAZOLIDINEDIONE-2-DIMETHYLHYDRAZONES FROM THIOCYANOESTERS AND HYDRAZINES
Authors: Gagnon Paul E. , Boivin Jean-L. , Brown Gordon M.
Published: May 2006

Thiocyanoesters were prepared from 2-bromoesters and potassium thiocyanate, and a series of substituted thiazolidinedione-2-azines was obtained from these thiocyanoesters using hydrazine hydrate. The structure of the thiazolidinedione-2-azines was determined by hydrolysis using hydrochloric acid in ethanol. The reaction of thiocyanoesters with dimethylhydrazine, generally speaking, was analogous to their reaction with hydrazine, but there were many differences. Only 1 mole of alcohol was eliminated rather than 2, and there was no apparent reaction for the ethyl 2-thiocyanononanoate and the methyl phenylthiocyanoacetate. Furthermore, the reaction of methyl 2-thiocyanoisobutyrate with dimethylhydrazine did not give a 2,4-thiazolidinedione-2-dimethylhydrazone but rather an addition product, N-dimethylamino-S-(1-methyl-1-carbomethoxy) ethylisothiourea. To illustrate the reactivity of the thiocyano group, benzyl thiocyanate was treated with hydrazine and the product was found to be dibenzyldisulphide, and ammonia was evolved. Similarly, trimethylene dithiocyanate gave the dimer of trimethylene disulphide. Finally, benzyl thiocyanate formed an addition product with dimethylhydrazine which was N-dimethylamino-S-benzylthiourea.
THE REACTION OF OXYGEN ATOMS WITH NO
Authors: Ogryzlo E. A. , Schiff H. I.
Published: May 2006

In the reaction between NO and O-atoms, the concentration of NO remains essentially unaltered. The reaction can therefore be considered as a NO-catalyzed recombination of O-atoms. Its rate can be conveniently studied by following the disappearance of O-atoms by an isothermal calorimetric technique. The reaction was found to be third order, first order in the concentrations of O, NO, and M, where M is some third body. The third-order rate constant was found to be 1.85 × 1016 cc2 mole−2 sec−1 when M = O2, A, or He and 2.0 × 1016 cc2 mole−2 sec−1 when M = CO2 The rate constant was found to have a slight negative temperature coefficient which corresponded to a negative Arrhenius activation energy of about 0.2 kcal/mole. A detailed mechanism for the reaction has been proposed.
THE MERCURY-PHOTOSENSITIZED DECOMPOSITION OF BENZALDEHYDE, ACROLEIN, AND CROTONALDEHYDE
Authors: Harrison A. G. , Lossing F. P.
Published: May 2006

The Hg3P1-photosensitized decomposition of benzaldehyde at low pressure and high radiation intensity forms predominantly a polymeric material. In the fraction of the reaction which forms the identifiable final products benzene and carbon monoxide, both a direct molecular rearrangement and a free radical split to phenyl and formyl radicals occur. The decomposition reactions of acrolein and crotonaldehyde involve the three primary processes:[Formula: see text]
THE PHOTOLYSIS OF TRIFLUOROMETHYL CYANIDE
Authors: King A. Bruce , Steacie E. W. R.
Published: May 2006

The photolysis of CF3CN at 1849 Å has been studied. The major products are hexafluoroethane, cyanogen, and perfluoro-3-methyl-2-aza-2-butene. The experimental value for [Formula: see text]is:[Formula: see text]where:[Formula: see text]Another product was isolated in smaller amounts and has been tentatively identified as perfluorotrimethyl-aza-2-pentene.
A RAPID DETERMINATION OF SOME SURFACE PROPERTIES OF SOLIDS
Authors: Schreiber H. P. , Waldman M. H.
Published: May 2006

not available
SYNTHESIS, REACTIONS, AND PROPERTIES OF SOME HIGHLY HINDERED DIPHENYL ETHERS
Authors: Allen Marjorie , Moir R. Y.
Published: May 2006

In the Hems synthesis of diphenyl ethers, an ortho-carbonyl offered less obstruction when held in a lactone ring than when present as an ester. Side reactions interfered with the Hems synthesis of highly hindered diphenyl ethers, and the highly hindered, highly activated ethers produced in the synthesis were easily cleaved by nucleophilic reagents, often in a few minutes at room temperature. The latter fact added a lively interest to the transformation of the ethers into other derivatives. Three of these were of special interest: (a) methyl 2-(6′-amino-4′-carbomethoxy-2′-nitrophenoxy)benzoate (VIc) which existed in remarkably stable dimorphic forms, (b) the dibenzoxazepine VIII, and (c) the quadruply orthosubstituted, asymmetrical 7-(4′-carbomethoxy -6′-laevo-menthoxyacetamino- 2′-nitrophenoxy)metameconine (IX). Attempts to isolate diastereoisomeric substances having the diphenyl ether link as an element of asymmetry failed, the classical explanation of the low configurational stability (due to bending and twisting of bonds) being superior to the quantum mechanical explanation of a tunnelling oscillation of oxygen.This paper describes the synthesis of diphenyl ethers bearing three or four groups ortho to the ethereal linkage, their conversion into asymmetrical derivatives, and our tentative conclusion that the unsymmetrical derivatives cannot be resolved into optical isomers at room temperature. The most interesting part of the paper describes the synthetic methods that must be used in the face of the very great ease of disruption of the ethereal linkage.
OXIDATION OFD-GALACTURONIC ACID WITH SOME DELIGNIFYING AND BLEACHING AGENTS
Authors: Zienius R. H. , Purves C. B.
Published: May 2006

D-Galacturonic acid was oxidized with decreasing ease, and in the approximate order shown, by excess of the following agents: sodium chlorite near pH 2.8 and 75°; sodium hypochlorite at pH 10–11 and 25°; chlorine dioxide, pH 1.3 or 5 at 75°; chlorine near 0° and pH 5 (slight); and hydrogen peroxide at pH 10–11 and 25° (negligible). Some uronic acid was always recovered unchanged, even from conditions that would have oxidized glucose quantitatively to gluconic acid. The only other products were mucic acid, together with DL-tartaric acid and tartronic acid presumably derived therefrom. Chlorine dioxide, however, never produced tartronic acid. Methyl-α-D-galacturonoside methyl ester yielded some galacturonic acid when exposed to alkaline hypochlorite or peroxide, and this cleavage of the glycosidic group was tentatively attributed to the oxidants rather than to the alkalinity of the systems.Anhydrous bromine degraded the silver salt of methyl-α-D-galacturonoside in poor yield to a syrup which was probably L-arabotrihydroxyglutaric dialdehyde.
1′,2;3,6;3′,6′-TRIANHYDROSUCROSE
Authors: Lemieux R. U. , Barrette J. P.
Published: May 2006

The "trianhydrosucrose" obtained on treatment of amorphous "sucrose tritosylate" with sodium methoxide was found to be 1′,2;3,6;3′,6′-trianhydrosucrose.
LIGHT ABSORPTION STUDIES: PART XVI. THE ULTRAVIOLET ABSORPTION SPECTRA OF FLUOROBENZENES
Authors: Forbes W. F.
Published: May 2006

The ultraviolet absorption spectra of a series of fluorobenzenes are determined. It is found that as a first approximation a fluoro substituent does not appreciably affect the benzenoid absorption. The spectra are discussed on the assumption that the mesomeric effect of the fluorine atom is small.
TERNARY COMPOUNDS IN THE SYSTEM NH3–H2O2–H2O
Authors: Giguère Paul A. , Chin David
Published: May 2006

A thermal analysis of the three-component system ammonia–hydrogen peroxide –water was carried out by adding anhydrous ammonia to the hydrate H2O2•2H2O. A first compound was found, with formula NH3•3H2O2•6H2O, melting at −23.9 °C; another compound melting around 15° appears to be a hydrate of ammonium peroxide, (NH4)2O2•2H2O. The eutectics are at −54.5°, 0.7% NH3, and −33.4°, 12.5% NH3. Careful redeterminations have confirmed that the melting point of the hydrate H2O2•2H2O is −52°, not −50° as was sometimes claimed. The latent heat of fusion of that compound is estimated to be 3.9 kcal and the degree of dissociation on melting, about one-third.
THE PROTON MAGNETIC RESONANCE SPECTRUM OF THIOPHENE
Authors: Abraham R. J. , Bernstein H. J.
Published: May 2006

not available
OOSPOREIN FROM AN ACREMONIUM SP.
Authors: Divekar P. V. , Haskins R. H. , Vining L. C.
Published: May 2006

not available
THE MECHANISM OF ORGANOMERCURIAL OXIDATION BY MERCURIC SALTS
Authors: Robson J. H. , Wright George F
Published: May 2006

It has been shown that the oxidation of organomercuric salts by inorganic mercuric salts is inhibited by oxygen, accelerated to some extent by acids, and will form esters as products even in the presence of much water. Moreover, the system will polymerize acrylonitrile. These evidences of free radical participation are substantiated by the formation of the same products when pernitrous acid replaces inorganic mercuric salt in the system. Kinetic studies show that radicals are involved in a self-regenerating chain in which active monomeric mercurous salt seems to be the carrier.
CYCLIALKYLATIONS OF ALKYL BENZENES WITH OLEFINS AND ALKYL HALIDES
Authors: Barclay L. Ross C. , Hilchie J. W. , Gray A. H. , Hall N. D.
Published: May 2006

A revised mechanism is given for the formation of octamethyloctahydroanthracene from 1,3,5-tri-t-butylbenzene and t-butyl chloride. 1,3,5-Tri-t-butylbenzene reacts with isopropyl chloride to yield an octamethylhydrindacene which also forms when 1,3,5-triisopropylbenzene is cyclialkylated with isobutene. 1,3,5-Triisopropylbenzene is cyclialkylated with 2-methyl-2-butene to yield a decamethylhydrindacene. Treatment of 1,3,5-triisopropylbenzene with 2-chloro-2,4,4-trimethylpentane yields a hydrocarbon, C23H38, most probably 1,1,3-trimethyl-5,6-diisopropyl-3-neopentylindan. Structures assigned to the cyclialkylation products are based on ultraviolet, infrared, and mass spectroscopic data, and in some instances classical syntheses. Mechanisms are suggested to account for these reactions.
CHEMISTRY OF THE TRIFLUOROMETHYL GROUP: PART I. COMPLEX FORMATION BY PHOSPHINES CONTAINING THE TRIFLUOROMETHYL GROUP
Authors: Beg M. A. A. , Clark H. C.
Published: May 2006

The formation of co-ordination compounds of (CH3)3P, (CH3)2PCF3, CH3P(CF3)2, and P(CF3)3, with boron trifluoride and platinum (II) chloride has been studied. The properties of the new compounds (CH3)2PCF3.BF3, [(CH3)2PCF3]2PtCl2, [CH3P(CF3)2]2PtCl2 are described, and it is hence concluded that the stabilities of the boron trifluoride compounds decrease in the order.[Formula: see text]while for the platinum (II) complexes the order of stability is[Formula: see text]These two orders are related to the electronegativity of the trifluoromethyl group and its influence on the bonding properties of the phosphorus atoms.
THE PREFERENTIAL TOSYLATION OF THE ENDO-5-HYDROXYL GROUP OF 1,4;3,6-DIANHYDRO-D-GLUCITOL
Authors: Lemieux R. U. , McInnes A. G.
Published: May 2006

Reaction of 1,4;3,6-dianhydro-D-glucitol (isosorbide) with an equimolar amount of tosyl chloride in pyridine gave a fourfold greater yield of the endo-5-tosylate (IV) than of the exo-2-tosylate (III). Compound III reacted about 1.4 times more rapidly with tosyl chloride than did IV. The structures of III and IV were established by infrared spectroscopy and by their reaction with sodium methoxide. The exo-tosyloxy group of the monoacetate of III resists replacement by iodide ion.
ADSORPTION EQUILIBRIA OF HYDROGEN, DEUTERIUM, AND THEIR MIXTURES. PART II
Authors: Basmadjian D.
Published: May 2006

An investigation has been made of the fundamental factors which determine isotope separation factors on adsorbents, based on hydrogen and deuterium isotherms reported in Part I. Through the use of a semiempirical thermodynamic approach, the binary separation factors α have been related to the single component isotherms (p = f(v)), and these in turn broken down into a number of terms involving the isosteric heat of adsorption q, temperature T, and surface coverage. If the less important contributions are neglected, the treatment leads to the following sequence of approximate relations:[Formula: see text]where ε0 = total vibrational zero-point energy of adsorbed molecules.The rigorous form of equation [I] agrees well with the experimental results, and semi-quantitative agreement with the data is shown by equation [II]. A qualitative discussion of [III] is given. It is suggested that the horizontal zero-point vibrations of the adsorbed species in some cases constitute an important contributing factor in addition to the vertical vibrations previously thought to be solely responsible for differences in isotope behavior.
CALCULATION OF HEATS OF SOLUTION IN SATURATED MIXED ELECTROLYTES
Authors: Iyengar Y.
Published: May 2006

Theoretical equations have been derived for calculating heats of solutions of an electrolyte in its saturated system comprising one or more electrolytes. These expressions involve the application of "Harned's rule" concerning activity coefficients in mixed electrolytic solutions to an extension of van't Hoff's equation dealing with the temperature coefficient of solubility product in non-ideal systems. The commonly occurring case of mixed electrolytic pairs has been considered in detail. Application of theoretical equations to calculate the heats of solutions KCl, NaCl, and KNO3 in the saturated systems KCl–NaCl–H2O and KCl–KNO3–H2O is briefly discussed.
6-O-ETHYL-D-GALACTOSE
Authors: McKeown G. G. , Hayward L. D.
Published: May 2006

not available
THE CHEMICAL COMPOSITION OF THE HEARTWOOD EXTRACTIVES OF LARIX LYALLII PARL.
Authors: Nair G. V. , Rudloff E. von
Published: May 2006

The heartwood of Canadian Alpine larch was found to contain 4.8% acetone-soluble material. From this extract taxifolin and aromadendrin were isolated in 26% and 17% yield, as well as conidendrin in a small amount. About one-quarter of the extract was composed of esters of phthalic, ferulic, and fatty acids. After saponification β-sitosterol, nonan-2-ol, phthalic acid, and a mixture of fatty acids were isolated. Gas-liquid chromatography indicated the presence of palmitic, an unidentified C16, stearic, oleic, linoleic, linolenic, an unidentified C20 acid, and two unidentified alcohols.
THE ACTIVATION ENERGY FOR THE RECOMBINATION OF TRIFLUOROMETHYL RADICALS
Authors: Pritchard G. O. , Dacey J. R.
Published: May 2006

By photolyzing mixtures of acetone and hexafluoroacetone, and measuring the rates of formation of the three ethanes, we have found [Formula: see text] which means that the activation energy for the recombination of CF3 radicals is 2140 ± 200 cal, assuming zero activation energies for the other two radical recombinations, and that none of the ethanes is formed except by radical recombination.
SOME DEUTERIUM ISOTOPE EFFECTS: I. WATER SOLVOLYSIS OF METHYL-d3 ESTERS
Authors: Llewellyn J. A. , Robertson R. E. , Scott J. M. W.
Published: May 2006

The α-deuterium isotope effect has been examined for the solvolysis of a series of esters containing a fully deuterated methyl group. The possible sources of the effect have been divided into "thermodynamic" effects which appear to favor more rapid reaction of the protium compound and "zero point" effects where stiffening of out-of-plane vibrations may account for the direction of the observed isotope effects. It appears that the inverse isotope effect may be a measure of the spatial restrictions placed on the hydrogen atoms on the carbon atom in the activated complex.
THE LUMINESCENCE OF COMPLEX MOLECULES IN RELATION TO THE INTERNAL CONVERSION OF EXCITATION ENERGY: PART II. N-HETEROAROMATICS
Authors: Hochstrasser Robin M.
Published: May 2006

The relative fluorescence and/or phosphorescence yields of a number of methyl- and halogeno-quinolines, isoquinolines, and acridines have been measured as a function of the wavelength of the exciting light. In all cases the solvent was absolute ethanol. The results show that the efficiency of internal conversion processes between excited singlet states is extremely high in comparison to other intramolecular steps. The effect of substituted heavy atoms is discussed, as well as the fluorescence of the conjugate acids of the bases.
STRUCTURE OF AN ARABOGALACTAN FROM TAMARACK (LARIX LARICINA)
Authors: Adams G. A.
Published: May 2006

A water-soluble polysaccharide containing L-arabinose and D-galactose in a molar ratio 1:3.8 was isolated from tamarack. Fractionation with ethanol from aqueous solution yielded one main component which was judged to be homogeneous on the basis of electrophoresis and sedimentation data. Hydrolysis of the fully methylated polysaccharide yielded, 2,3,5-tri-O-methyl-L-arabinose (2 moles); 2,3,4,6-tetra-O-methyl-D-galactose (16 moles); 2,5-di-O-methyl-L-arabinose (5 moles); 2,3,4-tri-O-methyl-L-arabinose (5.5 moles); 2,3,4-tri-O-methyl-D-galactose (11 moles); 2,4,6-tri-O-methyl-D-galactose (3 moles); 2,6-di-O-methyl-D-galactose (1 mole); 2,4-di-O-methyl-D-galactose (20 moles); 2-O-methyl-D-galactose (3 moles).Possible structures for the arabogalactan are proposed and discussed on the basis of these results.
KINETICS OF THE THERMAL DECOMPOSITION OF TETRAMETHYLTETRAZEN
Authors: Watson J. S. , Waring A. J.
Published: May 2006

The kinetics of the thermal decomposition of tetramethyltetrazen (T.M.T.) have been studied in a static system at pressures up to 1.8 × 10−2 mm and temperatures between 125.5 and 147.5 °C by measuring the rate of production of nitrogen. The results show that the decomposition is first order in T.M.T. at the pressures used and give approximate values for the Arrhenius parameters.
A CHEMICAL SYNTHESIS OF 4-O-METHYL-D-GLUCURONIC ACID
Authors: Bowering W. D. S. , Timell T. E.
Published: May 2006

not available
THE PENTITOL PENTANITRATES
Authors: Wright I. G. , Hayward L. D.
Published: May 2006

not available
MAGNETIC PROPERTIES OF MESONAPHTHODIANTHRENE
Authors: Matsunaga Yoshio
Published: May 2006

Electron spin resonance absorption was detected in mesonaphthodianthrene and mesonaphthodianthrone. The spectra of both of these compounds consist of, at least, seven lines with a separation of 4.4 oersteds and the central line has a g-value of 2.0024 ± 0.0002. The growth of the central line by admission of air was observed in the case of the hydrocarbon. Some suggestions are presented as to the nature of the unpaired electrons in these compounds. The magnitude of the molar diamagnetic susceptibility of mesonaphthodianthrene, after correction for the paramagnetic contribution from the unpaired electrons, is discussed in relation to the molecular structure.
THE REACTIONS OF ACTIVE NITROGEN WITH CYANOGEN AND CN RADICALS
Authors: Haggart Catherine , Winkler C. A.
Published: May 2006

Cyanogen is destroyed by active nitrogen at temperatures of 80° to 400 °C, and nitrogen pressures of 0.34 to 3.1 mm, with the formation of polymer. At 400 °C and sufficiently high flow rates of cyanogen, a constant amount is destroyed, which apparently corresponds to practically complete consumption of the available nitrogen atoms.The formation of CN radicals in the reaction of cyanogen with active nitrogen was established by the production of HCN and CH3CN when hydrogen or methane was added to the reaction mixture. The rate of destruction of cyanide radicals, when they were transported through a reaction vessel, was determined by introducing hydrogen below the site of reaction, and found to follow first order kinetics.
THE BIOGENESIS OF ALKALOIDS: XXV. THE ROLE OF HYGRIC ACID IN THE BIOGENESIS OF STACHYDRINE
Authors: Robertson A. V. , Marion Léo
Published: May 2006

In alfalfa 2–3 weeks old neither labelled ornithine nor labelled proline act as precursors of stachydrine. It has been shown, however, that the methyl group of methionine becomes incorporated into the alkaloid so that the biogenesis appears to occur at that time of growth. It is now shown that hygric acid (N-methylproline) is a precursor of stachydrine. The implications of the results obtained are discussed.
THE PRIMARY PROCESS IN THE MERCURY-6(3P1)-PHOTOSENSITIZED POLYMERIZATION OF ACETYLENE
Authors: Sherwood Alden G. , Gunning Harry E.
Published: May 2006

not available
SENSITIVE FREQUENCIES. V. THE SENSITIVE AMMINE FREQUENCIES AND ELECTRONEGATIVITIES OF COMPLEX TRANSITION METAL ION RADICALS
Authors: Wilmshurst J. K.
Published: May 2006

not available
REMOVAL OF OXYGEN FROM METHANE AND THE USE OF NUCLEAR SPIN RELAXATION TO MEASURE OXYGEN CONCENTRATION
Authors: Sandhu H. S. , Lees J. , Bloom M.
Published: May 2006

Nuclear spin relaxation measurements are used to measure quantitatively the amount of oxygen present in methane. An upper limit of 2.5 × 10−4% is placed on the amount of oxygen present in methane after treatment with a getter made of misch metal.
THE CHEMISTRY OF THE "AMINOCHROMES": PART III. ON THE STRUCTURES OF "IODOÖXOADRENOCHROME" AND IODOEPINOCHROME
Authors: Heacock R. A. , Scott B. D.
Published: May 2006

A substance prepared by the oxidation of adrenaline with iodic acid and described in the literature as 2-idoöxoadrenochrome appears, after consideration of a number of its physical and chemical properties to be identical with 2-iodoadrenochrome. The iodine atom in iodoepinochrome, obtained by the oxidation of epinine with potassium iodate, has been shown to be in the 2-position of the heterocyclic ring in the molecule.
LYCOPODIUM ALKALOIDS: IX. CYCLIZED PRODUCTS FROM α- AND β-CYANOBROMOLYCOPODINE
Authors: MacLean D. B. , Song Won-Ryul , Harrison W. A.
Published: May 2006

A study has been made of the products formed on treatment of α- and β-cyanobromolycopodine with potassium hydroxide in methanol and potassium acetate in ethanol, respectively. The product derived from the α-isomer is apparently formed in a cyclization reaction taking place alpha to the carbonyl group while that formed from the β-isomer may be an enol ether. The olefin expected from a normal dehydrobromination of α-cyanobromolycopodine has been prepared by an indirect method. Attempts to prepare the analogous olefin in the β-series led to the formation of a saturated cyclic ether. The hydrogenolysis product of β-cyanobromolycopodine has been prepared.
FREE RADICALS BY MASS SPECTROMETRY: XIX. PRIMARY STEPS IN THE MERCURY-PHOTOSENSITIZED DECOMPOSITION OF FORMALDEHYDE
Authors: Harrison A. G. , Lossing F. P.
Published: May 2006

In the Hg3P, photosensitized decomposition of formaldehyde, evidence from deuterium labelling shows that 40% of the primary dissociation proceeds by way of an intramolecular elimination of H2. The remainder dissociates by formation of H and HCO, or of 2H and CO. A clear distinction between these latter two processes cannot be made under the reaction conditions employed.
TRYPTAMINES, CARBOLINES, AND RELATED COMPOUNDS: PART V. 3-(α-ALKYL-β-AMINOETHYL)INDOLES
Authors: Abramovitch R. A. , Muchowski J. M.
Published: May 2006

The scope of the tryptamine synthesis via 1-oxo-1,2,3,4-tetrahydro-β-carbolines has been extended to tryptamines bearing a side-chain α-alkyl group. The preparation of 3-(2-amino-1-methylethyl)indole by this procedure is described.
RATES OF ADSORPTION OF HYDROGEN ON PALLADIUM AND ON RHODIUM
Authors: Low Manfred J. D.
Published: May 2006

A study of the effects of temperature and initial gas pressure on the kinetics of chemisorption of hydrogen on alumina-supported palladium and rhodium catalysts revealed, for both gas–solid systems, that the adsorption proceeded via three distinct and consecutive kinetic stages. Each stage could be described by the Elovich equation. The temporal range of existence of each kinetic stage was temperature- and pressure-sensitive, low initial pressures and high temperatures favoring early appearance of each stage. On increasing the temperatures from 0° to 400 °C, the amounts of hydrogen adsorbed on both solids decrease. Over that temperature range the rates of adsorption on Pd decrease, while those on Rh increase, with increasing temperature. The general effect of increasing the initial gas pressure over the range 10–60°mm Hg is to increase both rates and extents of adsorption.
DECOMPOSITION OF ZING OXIDE
Authors: Secco E. A.
Published: May 2006

Experimental results on the loss in weight of zinc oxide in a closed vessel under varying conditions of temperature, initial zinc pressure, oxygen pressure, and vacuum are reported. The data show more consistency interpreted in terms of dissociation rather than sublimation of the oxide. Plots of log10Kp versus 1/T and log10PZnO versus 1/T yield slopes corresponding to 24.0 ± 2.0 kcal and 43.0 ± 5.0 kcal, respectively. These results cannot be explained on the basis of available thermodynamic data. Interpretations of these results in terms of an unstable suboxide and non-equilibrium are discussed.
THE ACIDITY FUNCTIONS H0 AND J0(HR) FOR THE SYSTEM FORMIC ACID–WATER
Authors: Stewart Ross , Mathews Trevor
Published: May 2006

The acidity functions H0 and J0(HR) have been measured for the whole range of the formic acid – water system. The large negative J0 values for the more concentrated solutions fail to correlate with the functions derived by Gold on the basis of certain assumptions regarding the activity coefficients of the species involved. The cause of this deviation is discussed. The term log [R+]/[ROH] for the ionization of triphenylcarbinols in formic acid has been found to vary linearly with 1/T.
MAGNETIC MOMENT OF Ni2+ ION IN (Ph3P)2NiBr2(PhBr)2
Authors: Matsunaga Yoshio
Published: May 2006

not available
HYDROGENOLYSIS OF CARBOHYDRATES: VIII. COMPARATIVE STUDIES ON METHYL GLYCOPYRANOSIDES
Authors: Gorin P. A. J.
Published: May 2006

Several methyl glycopyranosides have been hydrogenated under pressure at 180 °C with copper chromite catalyst in dioxane. Many glycosides underwent hydroxyl group inversion and another reaction observed consisted of hydrogenolytic removal of the methoxyl group coupled with reduction of a hydroxyl group to a methylene group. Other glycosides were stable under these conditions, and these included methyl β- and methyl α-D-glucopyranosides and unexpectedly methyl β-D-mannopyranoside and methyl α-D-talopyranoside. The data indicated that generally β-glycosides are more stable than their α-anomers in the hexopyranoside series and that the methyl hexopyranosides are more stable than the methyl pentopyranosides. Explanations have been made in the theoretical section in order to cover these observations. At 240 °C, however, methyl α-D-glucopyranoside is hydrogenolyzed giving 11% of 1,5-anhydro-4-deoxy-hexitols. These polyols have been fractionated and the mixture shown to contain lyxo- and arabo-1,5-anhydro-4-deoxy-D-hexitols.
MOLECULAR AREAS OF SOAPS AT THE SURFACE OF LATEX PARTICLES
Authors: Orr R. J. , Breitman L.
Published: May 2006

The molecular area (i.e., the area occupied by a molecule of soap adsorbed on a surface) has been determined for a number of anionic, cationic, and non-ionic emulsifiers, adsorbed on latex particles. Measurements were made by surface tension and electron microscopic techniques. The composition of the polymer did not affect the molecular area of either anionic or cationic soaps. When a mixture of non-ionic and anionic soaps was used, interaction between the soaps prevented application of the conventional methods for measuring molecular area. The interaction is manifested by a decrease in the area occupied by an anionic soap molecule which can be explained in terms of reduction in electrostatic repulsive forces between ionic soap molecules. The configuration of the polyethylene oxide chain of the non-ionic on the surface of the latex particle is deduced to be that of caterpillarlike folds.
ELECTRON SPIN RESONANCE ABSORPTION OF DIPHENYLPICRYLHYDRAZYL–ZINC OXIDE MIXTURES
Authors: Matsunaga Y. , McDowell C. A.
Published: May 2006

Electron spin resonance measurements on mixtures of αα-diphenyl-β-picrylhydrazyl (DPPH) and zinc oxide when compared with corresponding determinations on DPPH itself, and with DPPH–potassium chloride mixtures, indicate that there is a transfer of electrons between the DPPH and the zinc oxide. These observations support earlier published views of Harrison and McDowell, who found that the above mixture was able to enhance the catalysis of the ortho–para hydrogen conversion, and the hydrogen–deuterium exchange reaction.
HEAT OF MIXING OF CARBON TETRACHLORIDE WITH FURFURAL
Authors: Jeun S. K. , Lu Benjamin C.-Y.
Published: May 2006

not available
THE PYROLYSIS OF DIALLYL (1,5-HEXADIENE)
Authors: Ruzicka D. J. , Bryce W. A.
Published: May 2006

The mechanism of decomposition of diallyl has been studied in a static system in the temperature range 460–520 °C. The principal gaseous products (room temperature) were propylene, methane, ethylene, and 1-butene, and the liquid products were cyclopentene, cyclopentadiene, 1-hexene, and benzene. The over-all activation energy of decomposition was 31.3 ± 1.0 kcal/mole for an A factor of 107 sec−1. A mechanism of decomposition based on hydrogen abstraction by allyl and the addition of allyl to olefinic double bonds is proposed. Some decomposition by a non-radical mechanism may also occur.
THE DIFFERENTIAL THERMAL ANALYSIS OF NATURAL AND SYNTHETIC HYDRATES OF CALCIUM SULPHATE
Authors: Fleck W. E. P. , Jones M. H. , Kuntze R. A. , McAdie H. G.
Published: May 2006

A variety of naturally occurring forms of calcium sulphate dihydrate produce substantially identical differential thermograms under conditions of uniform heating rate and particle size. These thermograms closely resemble those for synthetic dihydrate and β-hemihydrate, showing four endothermic effects and one exothermic effect below 500 °C. Two of these endothermic effects, at about 170° and 300 °C, respectively, which have not been reported previously, were found to be easily masked by changes in heating rate or sample concentration. Resolution of the several effects was improved by using different heating rates at different stages of the thermogram. Thermograms of the α-hemihydrate were similar, except that the endothermic effect at 300 °C was not evident and the exothermic effect occurred at a much lower temperature than for the dihydrate. No conspicuous differences were found in the temperatures corresponding to the various endothermic and exothermic effects which might be correlated with the general dehydration behavior of the particular material. The endothermic effect at about 170 °C appears to be associated with part of the hemihydrate to soluble anhydrite transition, possibly arising during the removal of the last traces of water.
MOLECULAR COMPLEXES DERIVED FROM 1,3,6,8-TETRANITROPYRENE
Authors: Bavin P. M. G.
Published: May 2006

not available
HEATS OF MIXING OF POLYISOBUTYLENE WITH SOME ORGANIC SOLVENTS
Authors: Watters Claude , Daoust Hubert , Rinfret Marcel
Published: May 2006

The heats of mixing of four fractions of polyisobutylene with five organic solvents have been measured at 25 °C with the use of a Tian–Calvet microcalorimeter. The maximum concentrations attained were of the order of 3% in polymer. It has been found that the enthalpy parameter k0 is independent of the molecular weight of the polymer sample in the investigated molecular weight range. All the values for k0 calculated from the Van Laar–Scatchard equation for the different polymer–solvent pairs are different from the values estimated from the partial molal quantities. This is explained with the use of new theories on the thermodynamics of high polymer solutions by Orofino and Flory and by Huggins.
LIGHT ABSORPTION STUDIES: PART XVII. THE ULTRAVIOLET ABSORPTION SPECTRA OF CHLOROBENZENES
Authors: Forbes W. F.
Published: May 2006

The ultraviolet absorption spectra of a series of chlorobenzenes are determined. The spectral data suggest that the apparent mesomeric effect of the chlorine atom is greater than that of the fluorine atom, that solvent–solute interactions are generally less important in chlorobenzenes than in fluorobenzenes, and that, as expected, the effective interference radius of the chlorine atom is large. Moreover, spectral changes in o-substituted chlorobenzenes are consistent with the assumption that maximum electronic interaction requires the chlorine atom to be in the same plane as the benzene ring. The conformations of o-chloroacetophenone and o-chlorophenol are briefly discussed.
THE REACTION OF SULPHURYL CHLORIDE WITH GLYCOSIDES AND SUGAR ALCOHOLS: PART II
Authors: Jones J. K. N. , Perry M. B. , Turner J. C.
Published: May 2006

The structures of methyl 4,6-dichloro-4,6-dideoxy-α-D-hexoside and methyl "4-chloro-4-deoxy-β-pentoside" (I) have been investigated. The desulphation reaction leading to the formation of the latter compound is described. Replacement of the hydroxyl group at C(4) by a chlorine atom in both compounds is shown to have occurred with inversion of configuration.
STEROIDS AND RELATED PRODUCTS: XIV. THE SYNTHESIS OF 17α-HALOGENATED 20,21-KETOLS OF THE CORTICOID TYPE
Authors: Engel Ch. R. , Hoegerle R.-M. , Deghenghi R.
Published: May 2006

In continuation of previous work, the hindering effect of 17α-substituents on replacement reactions in position 21 of the steroid molecule was further studied. It is shown that the impossibility of replacing a 21-halogen substituent by an acetoxy group in the presence of a bromine atom in position 17α is due both to a steric effect of the bulky 17-substituent and to its facile elimination. It is further shown that the replacement reaction in 21 may be carried out in the presence of the smaller and less readily eliminated 17α-chlorine substituent. In connection with these investigations, 17α-chloro-11-dehydrocorticosterone, the 17-chloro analogue of cortisone, was synthesized. The introduction of a chlorine atom into position 17 lowers the glucocorticoid activity.
SOLID–LIQUID REACTIONS: PART II. SOLID–LIQUID REACTIONS AMONGST THE CALCIUM ALUMINATES AND SULPHOALUMINATES
Authors: Kelly Roger
Published: May 2006

When 3CaO.Al2O3.6H2O (i.e. C3AH6) was placed in contact with a solution of Ca(OH)2 labeled with Ca45 and maintained at 25 °C, there was very little change in either the activity or composition of the liquid. These observations, when taken together, indicate that the compound is probably stable in the system used. On the other hand, when either C3AH6 or 3CaO.Al2O3.CaSO4.12H2O (i.e. C3AΣH12) was added to a mixed Ca(OH)2–CaSO4 solution, the composition of the liquid varied in a manner consistent with the formation of 3CaO.Al2O3. 3CaSO4.31H2O (i.e. C3AΣ3H31). The activity also changed markedly, and a detailed consideration of the relations between activity and composition enabled the reaction mechanisms to be determined. In further experiments, the reactions of C3AH6 and C3AΣH12 to form C3AΣ3H31 were shown to proceed also at 70° and 90 °C. The consistently greater ultimate stability of C3AΣ3H31 over C3AΣH12 between 25° and 90 °C is to be contrasted with the fact, observed in the course of preparing the C3AΣH12, that when solutions of A12(SO4)3, CaSO4, and Ca(OH)2 are mixed the immediate precipitate is C3AΣ3H31 at room temperature, but C3AΣH12 at boiling temperature.
A MECHANISM FOR THE INDUCTIVE EFFECT
Authors: Bent Henry A.
Published: May 2006

not available
THIAZOLES. IV. PROTON MAGNETIC RESONANCE SPECTRA OF THIAZOLE AND ITS METHYL DERIVATIVES
Authors: Taurins A. , Schneider W. G.
Published: May 2006

not available
CLAM POISON:I. THE PAPER CHROMATOGRAPHIC PURIFICATION OF CLAM POISON DIHYDROCHLORIDE
Authors: Casselman A. A. , Greenhalgh R. , Brownell H. H. , Bannard R. A. B.
Published: May 2006

A semimicro (10–25 mg) paper chromatographic method for purification of clam poison has been developed. This procedure when applied to a partially purified (toxicity 4150 MU/mg) sample of the toxin gave a 74% recovery of clam poison dihydrochloride of purity identical with that of the best material obtained by Schantz etal. (2) via the alumina chromatographic method. The upper limit of purity of toxin resulting from paper chromatography is estimated to be 98% because of traces of impurity introduced by the paper. The paper chromatographic procedure has been found capable of enriching low-grade toxic residues (35%) from the alumina process to a purity of 75% with an over-all recovery of 70%.
THE ABSTRACTION OF HYDROGEN ATOMS FROM AMINES AND RELATED COMPOUNDS
Authors: Brinton R. K.
Published: May 2006

The reaction of methyl radicals with a group of amines and amine-like compounds has been investigated in the temperature range 125° to 157 °C. The abstraction activation energies of hydrogen atoms from these compounds, the corresponding pre-exponential factors, and the actual reaction rates indicate that the N—H hydrogen atoms are more labile than the C—H atoms in these compounds.
THE SULPHURIC ACID SOLVENT SYSTEM: PART I. ACID-BASE REACTIONS
Authors: Flowers R. H. , Gillespie R. J. , Robinson E. A.
Published: May 2006

Acid–base reactions in the solvent sulphuric acid are discussed. Such reactions are conveniently studied by electrical conductivity measurements. A relation between the composition at which the conductivity has a minimum value and the strengths of the acid and base is derived. Values of the dissociation constants of acids and bases obtained in this way are shown to be in good agreement with values obtained by other methods.
KINETICS OF THE THERMAL DECOMPOSITION OF ETHYL PROPIONATE
Authors: Blades Arthur T. , Gilderson P. W.
Published: May 2006

The pyrolysis of ethyl propionate has been studied in the temperature range 505–602 °C, yielding the Arrhenius equation[Formula: see text]By the copyrolysis of this compound with ethyl-d5 acetate at 384 and 488 °C, and comparison of this temperature coefficient with that for the isotopic ethyl acetates, an activation energy difference between ethyl acetate and propionate of 20 ± 65 cal/mole was found, rather than 500 cal/mole as indicated in the individual studies. Since other evidence exists for an inductive effect in the decomposition due to the acid alkyl group, the lack of difference in activation energies is attributed to the change in effect being small and obscured by other effects.
ABSORPTION SPECTRA OF 2,5-DIMERCAPTO-1,3,4-THIADIAZOLE AND ITS METHYL DERIVATIVES
Authors: Thorn G. D.
Published: May 2006

The absorption spectra of the three tautomeric forms of 2,5-dimercapto-1,3,4-thiadiazole have been determined by using the N- and S-methyl derivatives. In the ultraviolet region, a hypsochromic shift in absorption maxima is shown in the change from the dithionic to the thionic–thiolic and to the dithiolic forms. Strong bands in the infrared at 1508–1475 cm−1 and 1435–1415 cm−1 have been assigned to [Formula: see text]respectively.
THE POLYSACCHARIDES OFCRYPTOCOCCUS LAURENTII(NRRL Y-1401): PART I
Authors: Abercrombie M. J. , Jones J. K. N. , Lock M. V. , Perry M. B. , Stoodley R. J.
Published: May 2006

The extracellular polysaccharides produced by Cryptococcuslaurentii have been isolated and shown to consist of (A) an acidic polysaccharide containing D-mannose, D-xylose, and D-glucuronic acid; (B) a neutral polysaccharide containing D-glucose only.Preliminary structural studies on the acidic material suggest that it consists of a mannose-containing backbone with xylose and glucuronic acid as end groups, while the glucan contains 1 → 3, 1 → 4, 1 → 2, and (or) 1 → 6 linked residues.
PRESSURE DEPENDENCE OF ROTATIONALLY PERTURBED LINES IN THE ULTRAVIOLET BAND SPECTRUM OF CN
Authors: Broida H. P. , Golden Sidney
Published: May 2006

Intensity measurements of the components of rotationally perturbed lines (K' = 4, 7, 11, and 15) in the 0,0 transition of the violet system (B2Σ+ − X2Σ+) of the CN formed in an "active" nitrogen flame have been made at pressures from 0.1 to 100 mm Hg. A simple kinetic model considering competition between formation, radiation, and collisional interchange of states gives a reasonable fit to the data over the entire range of measured pressures. At high pressures the intensity ratios of the components of rotationally perturbed lines depend only upon the radiative transition probabilities and at low pressures, only upon the relative rates at which they are populated. At intermediate pressures, the intensity ratios depend upon the collision frequency for the interchange of the rotationally perturbed states. The collision frequency determined in this manner is of the same order of magnitude as the gas kinetic collision frequency.
HOT ATOM REACTIONS AND RADIATION-INDUCED EFFECTS IN THE REACTIONS OF RECOIL TRITIUM WITH CYCLOPROPANE
Authors: Lee J. K. , Musgrave Burdon , Rowland F. S.
Published: May 2006

Recoil He3 (n, p) tritium atoms have been reacted with cyclopropane in the gas phase under a variety of experimental conditions. The labeled hydrocarbon and molecular hydrogen products have been separated by gas chromatography and assayed by gas proportional counting.The observed products show a strong dependence upon irradiation dose—cyclopropane is very inert toward reactions with hydrogen atoms and organic radicals, and the labeled olefinic products react preferentially, in effect as scavengers, with the reactive species from radiolysis of the parent molecule.Energetic tritium atoms are able to react with cyclopropane to give labeled cyclopropane as a product without causing isomerization or decomposition of the molecule. The relative yields of cyclopropane and propylene are dependent upon the average collisional de-excitation times, indicating that a fraction of the labeled cyclopropane molecules are decomposing in times of approximately 10−9 seconds. Cyclopropane, propylene, ethylene, hydrogen, and small amounts of allene and methylacetylene are observed as "hot" products in the presence of gaseous free radical scavengers. Many additional compounds are found as the result of free radical and/or radiolysis reactions in the absence of scavengers.The "hot" reactions are explained in terms of the single-step interactions of high kinetic energy tritium atoms with the cyclopropane molecules—the energy for endothermic and high activation energy processes is obtained from the recoil energy. The kinetic energy of the recoil atom at reaction is estimated to be of the order of 130 kcal/mole for some of the observed labeled compounds.
VIBRATIONAL DISEQUILIBRIUM IN REACTIONS BETWEEN ATOMS AND MOLECULES
Authors: Basco N. , Norrish R. G. W.
Published: May 2006

Observations on the production of vibrationally excited oxygen molecules in the flash photolysis of nitrogen peroxide and of ozone have extended previous work on these systems. In the case of nitrogen peroxide it has been shown that oxygen molecules possessing the entire exothermicity of the reaction in the form of vibrational energy are produced. A new class of reactions is reported in which vibrationally excited hydroxyl radicals are produced under isothermal conditions by the reaction O(1D) + RH → OH* + R, in which the energy for excitation is contributed by the electronic energy of the oxygen atom.These and other cases of non-equilibrated energy distributions in reaction products and theories accounting for this phenomenon are reviewed.
SEVEN MECHANISMS IN THE PHOTOLYSIS OF NO2 BETWEEN 3100 AND 3700 Å
Authors: Ford Hadley
Published: May 2006

Nitrogen dioxide has been photolyzed by various investigators under seven different limiting conditions, all at wavelengths between 3100 and 3700 Å. The results are reviewed and discussed in terms of two general mechanisms, both of which quantitatively relate the experimental data. The mechanisms differ in that one postulates that atomic oxygen attacks NO2 in two ways, yielding NO and O2 in one case and excited NO3 in the other. The excited NO3 can decompose to form atomic oxygen and NO2; it can be deactivated, or it can react with NO2. The second mechanism postulates a single mode of attack on NO2 by atomic oxygen, again yielding excited NO3. The NO3 can decompose to form NO and O2; it can be deactivated, or it can react with NO2. Of the two mechanisms the first seems more consistent with the thermal reactions of NO2 and NO3. It is believed that both the linear and the triangular NO3 play important roles in the photolysis.
NITRATION OF BICYCLIC GUANIDINES
Authors: McKay A. F. , Kreling M.-E.
Published: May 2006

The course of the nitration of a bicyclic guanidine system has been shown to depend on substitution at an adjacent carbon atom. The pyrimidine ring in 5-keto-2,3,6,7-tetrahydro-5(H)-thiazolo(3,2-α)pyrimidine is opened more rapidly by benzylamine and ethanolic hydrogen chloride than the pyrimidine ring in 5-keto-2,3,6,7-tetrahydro-1(H),5(H)-imidazo(1,2-α) pyrimidine. These effects are interpreted in terms of the resonance ion structure at the ring junctions.
THE SEPARATION OF SOME INORGANIC IONS BY HIGH-VOLTAGE ELECTROMIGRATION IN PAPER
Authors: Bailey R. A. , Yaffe L.
Published: May 2006

A number of inorganic ions have been separated by high-voltage electromigration in paper. The systems considered include some of particular radiochemical interest, such as Sr–Y, Ba–La, Mo–Tc, Pb–Bi–Po, as well as the alkali metals, some elements of the first long period, and other metals. Background electrolytes were usually solutions of complex-forming organic acids.
RELAXATION OF SURFACE PRESSURE AND COLLAPSE OF UNIMOLECULAR FILMS OF STEARIC ACID
Authors: Rabinovitch W. , Robertson R. F. , Mason S. G.
Published: May 2006

A study has been made of the time variations of π–A isotherms of stearic acid films at air/water interfaces using an automatic recording surface balance of the vertical pull type. The existence of coherent films below molecular areas of 22 sq. Å/molecule has been found to be dependent on the temperature, rate of compression, and the history of compression of a given film. The behavior at or near collapse, the decrease in π with time after sudden compression (relaxation), and the increase in π with time after sudden expansion (recovery) have been studied.The results have been interpreted on the basis of structural changes in the monolayer.
THE POLYSACGHARIDES OF CRYPTOCOCCUS LAURENTII (Y1401): PART II. BIOSYNTHESIS OF THE CARBOHYDRATES FOUND IN THE ACIDIC POLYSACCHARIDE
Authors: Abercrombie M. J. , Jones J. K. N. , Perry M. B.
Published: May 2006

Cryptococcuslaurentii was grown on media which contained D-glucose-1-C14, D-glucose-6-C14, D-mannose-1-C14D-galactose-1-C14, D-xylose-1-C14, and L-arabinose-1-C14. The radioactive polysaccharides were isolated and hydrolyzed. The distribution of the radioactivity in D-mannose, D-xylose, and D-glucuronic acid isolated from the polysaccharides was determined.The results show that (A) D-mannose and D-glucuronic acids are formed from the hexoses without any appreciable breakdown of the hexose skeleton; (B) D-xylose is formed from the hexoses mainly by a process involving loss of carbon-6; (C) D-xylose and L-arabinose are both converted to D-mannose, D-xylose, and D-glucuronic acid with rearrangement of the pentose skeleton that may involve the action of transaldolase and transketolase.
ÉTARD REACTION: III. NATURE OF THE COMPLEX
Authors: Wheeler Owen H.
Published: May 2006

Magnetic susceptibility measurements have shown that the chromium atoms in the toluene–chromyl chloride complex are tetravalent. The structure of the complex and the reaction mechanism are discussed. Spectroscopic evidence has been found of the initial formation of a π-complex. The products of reaction of chromyl chloride and ethylbenzene, isopropylbenzene, tetralin, and indane have been determined.
THE SOLID–LIQUID EQUILIBRIUM BETWEEN ANHYDROUS MAGNESIUM CHLORIDE AND N,N-DIMETHYLFORMAMIDE
Authors: Cook Denys
Published: May 2006

The solid–liquid equilibrium between anhydrous magnesium chloride and N,N-dimethylformamide has been investigated between −58° and +97 °C, and up to 25 mole% in magnesium chloride by the techniques of thermal analysis. The following compounds and their melting points have been noted: MgCl2.12DMF, 8.7°; MgCl2.6DMF, 35.0° (incongruent); MgCl2.5DiMF, 51.0°; MgCl.4DMF, 69.0 °C. Infrared examination of some of the compounds suggests that co-ordination is through the carbonyl group.