bluuebunny/crossref_metadata_2025 huggingface dataset:
THE ORIGIN OF CARBON ATOMS 4, 5, AND 6 OF RICININE
Authors: Essery J. M. , Juby P. F. , Marion Léo , Trumbull E.
Published: May 2006

Degradations to isolate the carbon atoms at positions 4,5, and 6 of the alkaloid ricinine from Ricinus communis L. are described. Tracer experiments with glycerol-1-14C and glycerol-2-14C suggest that glycerol or a closely related metabolic compound is a biosynthetic precursor of these carbon atoms.
THE MECHANISMS OF PERMANGANATE OXIDATION: VII. THE OXIDATION OF FLUORAL HYDRATE
Authors: Stewart Ross , Mocek Michael M.
Published: May 2006

The kinetics of the permanganate oxidation of fluoral hydrate have been examined over a very wide range of acidities. In the region between pH 2 and pH 8 the reaction is extremely slow but as the basicity is increased the reaction rate rises and can be correlated with the increasing concentration of the anions [Formula: see text] and CF3CHO2=. The latter is oxidized extremely rapidly. The mechanism is discussed in terms of hydride ion or hydrogen atom transfer from the anions to permanganate. Large isotope effects are observed in the oxidation of CF3CD(OH)2.In strong acid the oxidation rate rises again and this is interpreted in terms of a reaction between neutral fluoral hydrate and neutral permanganic acid. The acidity constant for the latter has been determined.
THE REACTIONS OF ELECTRONICALLY EXCITED NITRIC OXIDE MOLECULES WITH HYDROCARBONS
Authors: Strausz O. P. , Gunning H. E.
Published: May 2006

The reactions of NO(4II) molecules, generated by Hg 6(3P1) photosensitization, with methane, ethane, propane, neopentane, and benzene have been studied at room temperature in a circulatory system. In the case of ethane the following reaction products were identified: N2, N2O, H2O, NO2, CO, CO2, C2H4, acetaldehyde, nitroethane, ethyl nitrite, ethyl nitrate, nitroethylene, nitromethane, methyl nitrite, methyl nitrate, formaldehyde. For hydrocarbon consumption, under comparable conditions, the following quantum yield values were established: [Formula: see text]. The most probable primary process may be represented by the sequence[Formula: see text]

[Formula: see text]Alkyl free radicals catalyze the chain disproportionation of nitric oxide at room temperature according to the stoichiometric equation[Formula: see text]A minimal value of 12 was established for the average chain length.
METALLOCENE CHEMISTRY—A DECADE OF PROGRESS
Authors: Rausch M. D.
Published: May 2006

One of the most significant new frontiers in chemistry during the past decade has been the stabilization and study of π-organic derivatives of the transition metals. Over 60 elements are now known to form one or more cyclopentadienyl compounds. The aromatic-type reactions displayed by ferrocene and related complexes have also been extensively investigated. Ferrocene will undergo alkylation, acylation, sulphonation, metalation, arylation, formylation, aminomethylation, and other reactions characteristic of a highly reactive aromatic system. π-Cyclopentadienyl derivatives of vanadium, chromium, manganese, ruthenium, and osmium as well as certain π-arene complexes of chromium exhibit ring substitution reactions in varying degrees. Other metallocenes undergo ring addition reactions.The orientation effects of substituents on reactions of substituted ferrocenes have been studied. A variety of unique oxidation, reduction, dehydration, and rearrangement reactions are known in metallocene chemistry. Haloferrocenes and mercuriferrocenes are readily converted to biferrocenyl. Recent rate investigations have established that carbonium ions adjacent to metallocene nuclei possess unusual stabilization as a result of direct metal participation.
ELECTRONEGATIVITY: III. ORBITAL ELECTRONEGATIVITIES AND ELECTRON AFFINITIES OF TRANSITION METALS
Authors: Hinze Jürgen , Jaffé H. H.
Published: May 2006

The orbital electronegativities of the neutral transition metals of the first transition series have been calculated by the Mulliken formula for a wide variety of hybrid states. The electron affinities needed in the process have been calculated by isoelectronic and isoconfigurational extrapolation.
A KINETIC INVESTIGATION OF THE REACTION OF METHYLMAGNESIUM BROMIDE WITH BENZOPHENONE
Authors: Bikales Norbert M. , Becker Ernest I.
Published: May 2006

The reaction of methylmagnesium bromide with benzophenone in tetrahydrofuran was found to be homogeneous and essentially quantitative. The rates of this reaction were measured by following the decrease in absorbance of benzophenone in the ultraviolet as a function of time. Variables examined were concentrations of reactants, magnesium bromide, and temperature. Values were derived for the rate constants, and the energy and entropy of activation. The reaction was found to be initially first order in each reactant, but the rate decreased faster with time than would be predicted from the simple second-order rate equation. The implications of these findings are discussed.
OBSERVATIONS ON ALKYLBORANES
Authors: Lutz C. A. , Ritter D. M.
Published: May 2006

Some synthesis and exchange reactions of diborane and its alkyl derivatives and of the higher boron hydrides were reviewed as background for new work.In pursuit of an idea prompted by knowledge of the deuterium and B10 exchanges found for the reactive and unstable higher boron hydrides B4H10 and B5H11, mono- and di-methyldi-hydropentaborane and methyltetraborane have been prepared by direct reaction between the parent higher hydrides and 1,2-dimethyldiborane or monomethyldiborane. The identity and the reactions of each product have been delineated by gas chromatographic separation, gas density, and mass, infrared, and n.m.r. spectrometry. The H1 n.m.r. spectrum of dihydro-pentaborane has been reinterpreted and used to decide that monomethyldihydropentaborane is probably a BIII derivative which displays stereoisomerism.
SOME REACTIONS OF ORGANOALUMINUM COMPOUNDS WITH NITROGEN-CONTAINING BASES
Authors: Fetter Neil R. , Bartocha Bodo , Brinckman Jr. Frederick E. , Moore Donald W.
Published: May 2006

The reactions of Me3Al with Me2NNMe2 and Me2NCH2NMe2 have yielded complexes whose n.m.r. spectra suggest cyclic structures. They have the formulas Me3Al:Me2NNMe2 and Me3Al:Me2NCH2NMe2 respectively. Me3Al reacts with Me2NCH2CH2NMe2 to form a complex with a linear structure and the formula Me3Al:Me2NCH2CH2NMe2:AlMe3.The reactions of H3Al:NMe3 with several methyl hydrazines have yielded the following compounds: [—Al(HNNHMe)NHNMe—]n, [—HAlNNMe2—]n, H2Al—NHNEt2, [(—HAlNNEt2—):NMe3]n, and H2Al—NMe2. No reaction occurred between H3Al·(Et2O)n and tetramethylhydrazine and the reaction of 3 moles of H2NNMe2 with 1 mole of H3Al:NMe3 yielded a compound for which no structural formula could be assigned, but which had emperical formula C4H15N5Al.
CHARACTERIZATION OF THREE HEMICELLULOSES FROM THE WOOD OF AMABILIS FIR (ABIES AMABILIS)
Authors: Schwarz E. C. A. , Timell T. E.
Published: May 2006

An arabino-4-O-methylglucuronoxylan (10:14:76), a water-soluble galactoglucomannan (1:1:3), and an alkali-soluble galactoglucomannan (0.1:1:3) have been isolated in yields of 7, 4, and 8% from the wood of amabilis fir (Abies amabilis). The structure of the polysaccharides was established by methylation and periodate oxidation techniques. The xylan ([Formula: see text]) contained side chains of (1 → 2)-linked 4-O-methyl-α-D-glucuronic acid and (1 → 3)-linked α-L-arabinofuranose residues, both attached directly to a linear framework of (1 → 4)-linked β-D-xylose residues. The galactoglucomannans ([Formula: see text] 76 and 95) contained (1 → 6)-linked α-D-galactopyranosyl residues attached directly to a backbone of (1 → 4)-linked β-D-mannose and β-D-glucose residues. Partial hydrolysis of the two hexosans yielded 10 and 13 oligosaccharides, respectively, containing (1 → 4)-β-D-mannose, (1 → 4)-β-D-glucose, and (1 → 6)-α-D-galactopyranose residues. The molecular rotations of a series of mannooligosaccharides corresponded to a value of −54° for the specific rotation of an infinitely long mannan. It is concluded that the main hemicelluloses in amabilis fir wood are the same as those occurring in the wood of gymnosperms from other genera. The same three hemicelluloses are also present in the bark of this species.
CONSTITUTION OF THREE HEMICELLULOSES FROM THE WOOD OF ENGELMANN SPRUCE (PICEA ENGELMANNI)
Authors: Mills A. R. , Timell T. E.
Published: May 2006

An arabino-4-O-methylglucuronoxylan (10:70:12), a water-soluble galactoglucomannan (1:1:3), and an alkali-soluble galactoglucomannan (0.2:1:3) have been isolated in yields of 8.0, 1.0, and 8.1% from the wood of Engelmann spruce (Picea engelmanni). The xylan consisted of a linear framework of (1 → 4)-linked β-D-xylose residues to which were directly attached single side chains of (1 → 2)-linked 4-O-methyl-α-D-glucuronic acid and (1 → 3)-linked α-L-arabinofuranose residues. The galactoglucomannans were both composed of a backbone of (1 → 4)-linked β-D-mannose and β-D-glucose residues, some of which carried directly attached side chains of (1 → 6)-linked α-D-galactopyranose residues. Partial hydrolysis of the water-soluble galactoglucomannan yielded, among other oligosaccharides, a trisaccharide composed of galactose, glucose, and mannose residues. It is concluded that the main polysaccharides in the wood of Engelmann spruce are the same as those in most other gymnosperms. In the bark of this tree, the water-soluble galactoglucomannan is replaced by one or several polysaccharides of an entirely different composition.
THE X-RAY DIFFRACTION PATTERNS OF ALUMINUM CARBIDE Al4C3 AND ALUMINUM OXYCARBIDE Al4O4C
Authors: Cox J. H. , Pidgeon L. M.
Published: May 2006

An X-ray investigation of the compounds aluminum carbide, Al4C3, and aluminum oxycarbide Al4O4C yielded data which differed from that in the A.S.T.M. files. The aluminum carbide pattern was similar in many ways to that calculated by Stackelberg and Schnorrenberg (Z. Physik. Chem., Sect. B, 27, 37 (1934). Minor differences occurred in the Al4O4C pattern.
THE PREPARATION, PROPERTIES, AND STRUCTURE OF 2,6-BIS-(ALKYLAMINO)-2,5-HEPTADIEN-4-ONES
Authors: Cook Denys
Published: May 2006

2,6-Bis-(alkylamino)-2,5-heptadien-4-ones have been prepared by the action of aqueous amines on (1) 3-acetyl-4-hydroxy-6-methyl-2-pyrone (dehydroacetic acid), (2) 3-(1-alkylimino-ethyl)-4-hydroxy-6-methyl-2-pyrone, (3) 3-carboxy-2,6-dimethyl-4-pyrone, (4) 2,6-dimethyl-4-pyrone, (5) 2,6-dihydroxy-2,5-heptadien-4-one. The reactions are facile and proceed smoothly at temperatures near, or slightly above, room temperature. In (1) the first products are 3-(1-alkyliminoethyl)-4-hydroxy-6-methyl-2-pyrones, followed by the 2,6-bis-(alkylamino)-2,5-heptadien-4-one. The other reactions yield only the latter product, but in all cases it decomposes to the 4-pyridone at higher temperature, or on prolonged reaction or by the action of acid.The 2,6-bis-(alkylamino)-2,5-heptadien-4-ones are pale yellow compounds with a slight violet fluorescence. Infrared, n.m.r., and ultraviolet spectra are consistent with an open-chain, internally hydrogen-bonded structure.
THE EFFECT OF ELECTRIC FIELDS, AND A RELATED DEPENDENCE ON DOSE RATE, IN THE γ-RADIOLYSIS OF HYDROCARBON GASES
Authors: Woodward T. W. , Back R. A.
Published: May 2006

The effect of electric fields on the γ-radiolysis of ethane, propane, and the butanes has been investigated briefly at 800 mm pressure, with dose rates between 2 × 1010 and 400 × 1010 ev/cc sec. Yields of hydrogen were reduced when a saturation field was applied, except with ethane at low dose rate, where a slight increase in hydrogen yield was observed. With propane and n-butane, the yield of hydrogen in the presence of a saturation field was independent of dose rate, while with ethane, it decreased with decreasing dose rate. At the same time, a dose rate dependence was discovered in the simple radiolysis, in the absence of any field, of ethane, propane, and n-butane, a decrease in the yield of hydrogen at low dose rates being observed. An explanation of these observations is suggested in terms of a competition between neutralization of ions in the gas phase and diffusion of ions to the wall. High dose rates should favor the former process, and low dose rates the latter. At sufficiently high dose rates, all ions should be neutralized in the gas phase. At sufficiently low dose rates, all ions should diffuse to the wall before neutralization, and it is suggested that the radiolysis under these conditions should closely resemble that in the presence of a saturation field at higher dose rates.
THE INTERACTION OF SILICON TETRAFLUORIDE WITH METHANOL
Authors: Guertin J. P. , Onyszchuk M.
Published: May 2006

Silicon tetrafluoride reacts with methanol in a 1:4 mole ratio, forming the complex SiF4.4CH3OH, which freezes to a glass at about −20° and is completely dissociated in the gaseous phase at 25°. Conductivity measurements show clearly that it is a very weak electrolyte in methanol solution. Its infrared spectrum does not contain an Si—O bond stretching absorption band. Proton magnetic resonance measurements provide strong evidence of hydrogen bonding between silicon tetrafluoride and methanol. These results indicate that the structure of the complex requires tetracovalent rather than hexacovalent silicon and strong hydrogen bonds between methanol and each of the four fluorine atoms.
PSEUDACONITINE, AND THE STEREOCHEMICAL RELATIONSHIP OF THE HIGHLY OXYGENATED ACONITE ALKALOIDS
Authors: Tsuda Y. , Marion Léo
Published: May 2006

An alkaloid isolated from Aconitum spicatum Stapf has been found to be identical not only with the originally described pseudaconitine but also with 'α-pseudaconitine'. The product of the partial hydrolysis of the base, i.e., veratroylpseudaconine, is dextrorotatory, and not laevorotatory as recorded in the old literature. On heating, pseudaconitine undergoes pyrolysis, loses the elements of acetic acid, and gives rise to pyropseudaconitine. This substance, on treatment with lithium aluminum hydride, is converted to demethoxyisopyropseudaconine which is identical with the Wolff–Kishner reduction product of pyraconine. This correlation establishes that pseudaconitine and aconitine possess the same absolute configuration, which, in the light of previous knowledge, is extended also to indaconitine, delphinine, mesaconitine, and jesaconitine.
THE OXYMERCURATION OF 1,4-↑↑-METHYLENE-Δ5-CYCLOHEXENE-2-CARBOXYLIC ACIDS
Authors: Malaiyandi M. , Wright George F
Published: May 2006

The oxymercuration of 1,4-↑↑-methylene-Δ5-cyclohexene-2-↑-carboxylic acid yields two diastereomeric hydroxychloromercurials. Their configurations cannot be specified on the basis of information now available with certainty. The oxymercuration of 1,4-↑↑-methylene-Δ5-cyclohexene-2-↓-carboxylic acid also yields two diastereomers, which are designated as 6-↓-hydroxy-5-↓-chloromercuri-1,4-↑↑-methylenecyclohexane-2-↓-carboxylic acid, γ-lactone and 6-↓-hydroxy-5-↑-chloromercuri-1,4-↑↑-methylenecyclohexane-2-↓-dicarboxylic acid, γ-lactone because the former is more easily deoxymercurated than the latter and because their dipole moments match relatively the corresponding moments of the analogous dicarboxylic acid γ-lactones, the configurations of which have been proved chemically. This is the first instance where two diastereomers of opposite configuration have been shown to be formed in an oxymercuration.
COORDINATION POLYMERIZATION OF OLEFINS: CATALYST STUDIES. PART I. THE INFRARED SPECTROSCOPIC INVESTIGATION OF THE SYSTEMS (CH3)3Al–TiCl4AND (CH3)2Zn–TiCl4
Authors: Gray A. P. , Callear A. B. , Edgecombe F. H. C.
Published: May 2006

An infrared spectroscopic investigation of the reaction between titanium tetrachloride and trimethyl aluminum in the vapor phase was carried out at six different reactant ratios. The study defined the course of the initial reactions; demonstrated the importance of equilibria among the products in this system as contrasted with dimethyl zinc – titanium tetrachloride; indicated the relative alkylating power of trimethyl, dimethylchloro, and methyldichloro aluminum toward titanium tetrachloride and methyl titanium trichloride; and supported the view that the active catalyst site in such systems is the titanium–carbon bond in reduced titanium alkyls. A new mode of decomposition of methyl titanium trichloride leading to active catalyst was found which can account for reported variable catalyst activities at Al/Ti ratios less than 1. Individual infrared spectra in the range 1500 to 300 cm−1for trimethyl aluminum, dimethyl aluminum dichloride, methyl aluminum dichloride, methyl titanium trichloride, and dimethyl titanium dichloride as well as those of the initial reaction mixtures are presented.
OCCURRENCE OF D-GLUCURONIC ACID IN TAMARACK ARABINOGALACTAN
Authors: Urbas B. , Bishop C. T. , Adams G. A.
Published: May 2006

The aldobiouronic acid 6-O-(β-D-glucopyranosyluronic acid)-D-galactose and D-glucuronic acid have been isolated from a hydrolyzate of an arabinogalactan from tamarack (Larix laricina). The identity of the aldobiouronic acid and the evidence for homogeneity of the polysaccharide showed that these acidic components are almost certainly constituents of the arabinogalactan.
THE ALKALINE CLEAVAGE OF o-NITROBENZYLTRIMETHYLSILANE SOLVENT EFFECTS IN THE DIOXANE–WATER SYSTEM
Authors: Allcock H. R.
Published: May 2006

The kinetics of alkaline cleavage of o-nitrobenzyltrimethylsilane were examined in aqueous dioxane media. At high water concentrations, increases in solvent polarity retard the cleavage, as required by a mechanism involving charge dispersion in the transition state. At high dioxane concentrations, solvent polarity increases are accompanied by increases in the rate of reaction, a result which may reflect association between the solvent components.
A NEW ASPIDOSPERMA ALKALOID: O-DEMETHYLASPIDOCARPINE
Authors: Ferrari C. , McLean S. , Marion Léo , Palmer K.
Published: May 2006

From the stem bark of Aspidosperma album four alkaloids have been isolated. Two of these (aspidoalbine and its N-acetyl-N-depropionyl homologue) have been reported recently and their structures established by Djerassi and his co-workers. The other two consist of aspidocarpine, and a new alkaloid, the structure of which has been determined. It is O-demethylaspidocarpine.
THE SYNTHESIS AND PROPERTIES OF THE ANHYDROUS HEXACHLOROTITANATES OF RUBIDIUM AND CESIUM
Authors: Lister R. L. , Flengas S. N.
Published: May 2006

The hexachlorotitanates of rubidium and cesium have been produced in a closed system, following the reaction[Formula: see text]where M is respectively Rb and Cs. With the titanium tetrachloride vapor at 1 atm, the optimum temperature for both reactions is 410 ± 10 °C.
NICKEL–MAGNESIA CATALYST AS REVEALED BY ADSORPTION AND ELECTRON OPTICAL STUDIES
Authors: Ramasubramanian N. , Yeddanapalli L. M.
Published: May 2006

A combined electron diffraction and hydrogen adsorption study on a nickel–magnesia catalyst with 36% nickel is reported. A comparison of the adsorption results with those on the previously reported 79% and 18% catalysts indicates the possibility of the unreduced nickel in the catalysts taking part in high-temperature fast adsorption. The electron optical studies show that there are structural changes taking place during the reduction treatment the catalyst undergoes. However, diffraction study in situ appears to be necessary to show, beyond doubt, the presence of reduced and unreduced nickel on the catalyst's surface.
METHYL 3-NITRO- AND 3-AMINO-3-DEOXY-β-D-GALACTOPYRANOSIDE AND -MANNOPYRANOSIDE
Authors: Baer Hans Helmut , Kienzle Frank
Published: May 2006

The steric course of the nitromethane cyclization of L′-methoxy-D-hydroxymethyldiglycolic aldehyde was investigated. Methyl 3-nitro-3-deoxy-β-D-galactopyranoside was shown to arise as a second major reaction product in addition to the previously isolated principal stereoisomer, the gluco derivative. The corresponding manno stereoisomer is formed to a smaller extent. The configurations of the new methyl nitrodeoxyglycosides were established by conversion into the corresponding amino derivatives and hydrolysis of these latter to the known 3-amino-3-deoxy-D-galactose and -D-mannose hydrochlorides. All the products were obtained in a crystalline state. The reaction lends itself to a facile preparation of the nitrogenous galactose derivatives.
THE INFLUENCE OF A VEHICLE-IMMISCIBLE, ADSORBABLE, THIRD COMPONENT ON THE FLOCCULATION OF LARGE-DIAMETER PARTICLES
Authors: Chessick J. J. , Zettlemoyer A. C. , Christian John B.
Published: May 2006

not available
RELATIVE SIGNS OF PROTON COUPLING CONSTANTS IN 1-CHLORO-2,2-DIMETHYLCYCLOPROPANE
Authors: Hutton H. M. , Schaefer T.
Published: May 2006

not available
IONIZATION OF DEUTERATED ALCOHOLS IN ACID SOLUTION
Authors: Mocek Michael M. , Stewart Ross
Published: May 2006

not available
5-(DISUBSTITUTED)AMINO-1,2,3,4-THIATRIAZOLES
Authors: Lieber Eugene , Rao C. N. R. , Lawyer C. B. , Trivedi J. P.
Published: May 2006

not available
A SIMPLE METHOD FOR TRAPPING AND COLLECTING THE GASES NOT CONDENSABLE AT −196° IN A FAST-FLOWING, LOW-PRESSURE SYSTEM
Authors: Demchuk Nick , Gesser H.
Published: May 2006

not available
THE DECOMPOSITION OF 2-METHYL-Δ2-OXAZOLINE IN AQUEOUS SOLUTION
Authors: Greenhalgh R. , Heggie R. M. , Weinberger M. A.
Published: May 2006

Nuclear magnetic resonance has been used to follow the decomposition of aqueous solutions of 2-methyl-Δ2-oxazoline (0.29 M) at constant pH values in the range −1 to 14. The decomposition is first order with respect to total oxazoline at any specific pH, but deviates from the simple reaction of water with the protonated species above pH 5. At neutral pH values this is shown to be partially due to a second reaction involving 2-methyl-Δ2-oxazoline and O-acetylethanolamine which yields N-2-acetoxyethyl N′-2-hydroxyethyl acetamidate. The decrease in rate constant at pH < 2 is accounted for by variation in the water concentration, which is related to the acidity function. A kinetic expression is derived for the decomposition over the whole pH range studied. The decomposition of the amidate is also discussed.
SULPHONIUM SALT SOLVOLYSIS: PART IV. SOLVENT EFFECTS
Authors: Hyne J. B. , Jensen J. H.
Published: May 2006

The variation of rate of solvolysis of dimethyl-t-butyl sulphonium iodide as a function of solvent composition is reported for various binary mixtures of water with ethanol, N,N-dimethylformamide, N-methylformamide, dioxane, and ethylene glycol. The inadequacy of solvent bulk dielectric constant as a correlating parameter is demonstrated and solvent Y and Z parameters are compared in this respect. The importance of the specific microscopic role of the solvent in the activation process is demonstrated and a possible important nucleophilic role for the amides suggested. Deviations in dioxane and ethylene glycol systems are discussed.
QUELQUES METABOLITES POSSIBLES DE LA THALIDOMIDE
Authors: Ménard Marcel , Erichomovitch Lucien , Brooy Michael La , Chubb Francis L.
Published: May 2006

La synthèse de dérivés hydroxylés en positions 3 et 4 de 1′ α-phtalimidoglutarimide et de ses produits d'hydrolyse est décrite.
ISOTOPE EFFECT STUDIES ON ELIMINATION REACTIONS: III. NITROGEN ISOTOPE EFFECTS IN THE E2 REACTION OF ETHYLTRIMETHYL-AMMONIUM AND 2-PHENYLETHYLTRIMETHYLAMMONIUM IONS
Authors: Ayrey G. , Bourns A. N. , Vyas V. A.
Published: May 2006

Nitrogen isotope effects have been determined for the E2 reaction of two quaternary ammonium salts with ethoxide ion in ethanol. Ethyltrimethylammonium iodide gave k14/k15 values of 1.017 at 60° and 1.015 at 95°, while 2-phenylethyltrimethylammonium bromide gave 1.012 at 40° and 1.009 at 60°. These results and the β-deuterium isotope effects reported by others have been interpreted in terms of the relative extent of Cα—N+ and Cβ—H bond weakening in the transition states of the two reactions.
TWO-PHASE FLOW OF ADSORBED VAPORS
Authors: Barrer R. M.
Published: May 2006

Through a microporous medium, transport of a vapor may occur in an adsorbed film and in the gas phase. The formulation of this two-phase transport has been given in terms of forces and associated phenomenological coefficients, and the resultant expression for the total flux has then been related to the complex Darcy law and Fick law coefficients of flow and diffusion respectively. It is suggested how the various coefficients may be determined as functions of gas pressure or surface concentration of sorbate. The diffusive and hydrodynamic models of transport are considered as two limiting cases of the transport phenomenon, the former of increasing importance for decreasing sorption below monolayer coverage and the latter dominant above monolayer coverage. Steady state total concentration gradients are considered in presence and absence of blockage of gas phase flow by capillary condensate and multilayers, and when there is and is not interconversion between surface and gas phase fluxes along the direction of flow. Finally, the fluxes of each component in a two-phase two-component flow are derived. This problem is of major importance in the separation of mixtures by flow through microporous barriers.
THE THERMAL DECOMPOSITION OF PERACETIC ACID IN AROMATIC SOLVENTS
Authors: Evans F. W. , Sehon A. H.
Published: May 2006

The thermal decomposition of peracetic acid in toluene, benzene, and p-xylene was studied over the temperature range 75–95°C. The main products of decomposition were found to be CH4, CO2, CH3COOH; small amounts of methanol, phenols, and polymeric compounds were also detected.The rate of the overall decomposition was first order with respect to peracetic acid, and the results could be explained by postulating the participation of the two simultaneous reactions:[Formula: see text]

[Formula: see text]The rate constant of reaction (1) was independent of the solvent, whereas k2 was dependent on the solvent. The ratio k2/k1 was about 10.
SELF-CONDENSATION OF METHYL PROPIOLATE
Authors: Wenkert Ernest , Adams K. A. H. , Leicht Curtis L.
Published: May 2006

not available
THE KINETICS OF THE TRIBUTYLAMINE-CATALYZED REACTION OF PHENYL ISOCYANATE WITH 1-BUTANETHIOL IN VARIOUS SOLVENTS
Authors: Iwakura Yoshio , Okada Hisao
Published: May 2006

not available
PROTON RESONANCE SPECTRA OF VINYL-METALLIC COMPOUNDS: PART II. HEXAVINYLDIGERMANE
Authors: Cawley S. , Danyluk S. S.
Published: May 2006

not available
SYMMETRIZATION OF SPIN FUNCTIONS FOR THREE EQUIVALENT SPIN 1/2 NUCLEI BY MEANS OF THE POINT GROUP C3
Authors: Schaefer T. , Hruska F.
Published: May 2006

not available
THE INTERACTION OF HYDRAZINE WITH BORON AND ALUMINUM HALIDES
Authors: Paterson W. G. , Onyszchuk M.
Published: May 2006

The interaction of boron halides BX3 (where X is Cl or Br) or aluminum halides Al2X6 (where X is Cl, Br, or I) with hydrazine is characterized by the elimination of hydrogen halide and the formation of substances with boron– (or aluminium–) nitrogen linkages. The hydrogen halide appears in the products as hydrazine hydrohalide, which can be separated by a hydrazine washing technique, leaving a polymeric material with empirical formula MN4H5 (where M is Al or B). A reaction scheme is proposed and possible structures of this polymeric product are discussed.
THE SYNTHESIS OF 3-HEXULOSES: PART II. DERIVATIVES OF 1-DEOXY-L-arabo-3-HEXULOSE (SYN. 6-DEOXY-L-lyxo-4-HEXULOSE)
Authors: Bird J. W. , Jones J. K. N.
Published: May 2006

Oxidation of 1,3:2,5-di-O-methylene-L-rhamnitol yielded 2,5:4,6-di-O-methylene-1-deoxy-L-arabo-3-hexulose, which was characterized as its 2,5-dichlorophenylhydrazone and by reduction to derivatives of L-rhamnitol and of 6-deoxy-L-talitol. Oxidation of 2,5-O-methylene-L-rhamnitol 1-benzoate yielded a syrupy 3,4-diketose which was characterized as the crystalline quinoxaline derivative. Attempts to convert 1,2:4,5-di-O-isopropylidene-D-mannitol 6-benzoate to a ketose were unsuccessful.
THE Co60 γ-RADIOLYSIS OF AQUEOUS CYSTINE SOLUTIONS: I. THE EFFECT OF CHLORIDE ION ON THE AMMONIA YIELD
Authors: Armstrong W. A. , Grant D. W.
Published: May 2006

Sodium chloride has been found to increase the ammonia yield from Co60γ-irradiated cystine in 0.02 M H2SO4. The effect is attributed to the participation of chlorine atoms, which deaminate the amino acid to a greater extent than hydroxyl radicals. The ratio of the rate constants [Formula: see text] is determined to be 24 in 0.02 M H2SO4.
DETERMINATION OF α OR β SUBSTITUTION OF THE INDOLE NUCLEUS BY NUCLEAR MAGNETIC RESONANCE
Authors: Jardine R. V. , Brown R. K.
Published: May 2006

Marked differences in chemical shift of the signal for the α proton in indole and substituted indoles occur when spectra are obtained in non-polar and polar solvents. In contrast, using polar and non-polar solvents, only small differences are observed in the chemical shift of the signal for the β proton in indoles. The utility of the solvent effect on the chemical shift to distinguish between α and β substitution of the indole nucleus is pointed out.
GAS CHROMATOGRAPHIC SEPARATION OF DEUTERIUM-SUBSTITUTED OLEFINS BY UNSTABLE COMPLEX FORMATION
Authors: Cvetanović; R. J. , Duncan F. J. , Falconer W. E.
Published: May 2006

not available
1(7),4(8)-p-MENTHADIENE
Authors: Mitzner B. M. , Theimer E. T. , Lemberg S.
Published: May 2006

not available
PREPARATION OF ANTIDOTES FOR ANTICHOLINESTERASE POISONING: II. TERTIARY AND QUATERNARY SALTS OF PARPANIT AND PARPANIT ANALOGUES
Authors: Bannard R. A. B. , Parkkari J. H. , Coleman I. W.
Published: May 2006

not available
HIGH-YIELD SYNTHESES OF N-MONO- AND N,N-DI-SUBSTITUTED UREAS AND THIOUREAS FROM SILICON PSEUDOHALIDES
Authors: Neville Roy G. , McGee John J.
Published: May 2006

This study demonstrates that N-mono- and N,N-di-substituted ureas and thioureas may expediently be synthesized, in essentially theoretical yield, by reacting primary or secondary aliphatic, alicyclic, aralkyl, aromatic, and heterocyclic amines with silicon tetraisocyanate or tetraisothiocyanate, or the corresponding methyl-substituted analogues. The method fails with aromatic amines possessing bulky (e.g. phenyl, bromo), or strongly electronegative (e.g. trifluoromethyl), substituents in the 2-, or 2,6-positions of the aromatic nucleus. Data on several new substituted ureas and thioureas are reported, and improved preparative procedures for the silicon pseudohalides are described.
THERMAL DECOMPOSITION OF MOLECULAR COMPLEXES: III. UREA INCLUSION COMPOUNDS OF MONOSUBSTITUTED ALIPHATIC SERIES
Authors: McAdie H. G.
Published: May 2006

Examination of the thermal decomposition of urea inclusion compounds has been extended to complexes of the even-numbered members of the following aliphatic series: n-alcohols, n-alkylamines, n-alkyl bromides, and n-carboxylic acids. The decomposition has been studied primarily by differential thermal analysis and an attempt made to correlate the observed decomposition temperatures and heats of decomposition with the particular guest species. The decomposition mechanism appears to involve acquisition of sufficient energy by the guest molecule to permit its diffusion from the canal, the decomposition temperature being related to the activation energy required for this diffusion process.
THE CARBONYL-STRETCHING VIBRATION OF ARYLALIPHATIC ESTERS
Authors: Bowden Keith , Chapman N. B. , Shorter J.
Published: May 2006

The infrared spectra in the carbonyl-stretching region of certain arylaliphatic esters, RCOOMe, have been examined. The stretching frequencies and absorption intensities are presented and are discussed in terms of polar and α-mass effects and the occurrence of conformational isomers.
THE NEAR-ULTRAVIOLET SPECTRA OF SOME 9-ALKYLPHENANTHRENES
Authors: Anet F. A. L. , Bavin P. M. G.
Published: May 2006

The ultraviolet spectra are reported of a series of 9-alkylphenanthrenes. The bathochromic shifts relative to phenanthrene of the longest-wavelength (α) band are not explicable in terms of hyperconjugation. It is suggested that the band envelope is influenced by the rotameric forms of the alkyl substituents.
REACTIONS OF CARBOHYDRATE DERIVATIVES DURING GAS–LIQUID CHROMATOGRAPHY
Authors: Bishop C. T. , Cooper F. P. , Murray R. K.
Published: May 2006

The following reactions have been shown to occur during gas–liquid chromatography of carbohydrate derivatives: (a) deamidation, (b) change in size of the sugar ring, (c) rearrangement of acetal or ketal groups, (d) degradative rearrangement of acetylated amino sugars. The results emphasize that stability of a compound under conditions used in gas–liquid chromatography is a necessary prerequisite to the application of that technique; the precautions that should be followed to determine stability are indicated.
A REINVESTIGATION OF THE RANGE OF Na24 IONS OF KEV ENERGIES IN ALUMINUM
Authors: McCargo M. , Brown F. , Davies J. A.
Published: May 2006

The range of Na24 in aluminum has been reinvestigated in the energy region 1.0–100 kev, using an isotopically separated beam of Na24. Below 10 kev, the results differ significantly from our earlier data in which a much larger integrated flux of alkali metal ions (Na23 + Na24) was required. Above 10 kev the discrepancy between the two sets of data disappears. The recent theoretical treatment of Oen, Holmes, and Robinson is found to be in quite reasonable agreement with the median ranges [Formula: see text] obtained in the present work, particularly if an allowance for the electronic stopping contribution at the higher energies is included.
STERIC EFFECTS IN AROMATIC CARBONYL COMPOUNDS: I. BASICITIES AND ULTRAVIOLET SPECTRA
Authors: Yates Keith , Scott Brian F.
Published: May 2006

The basicities of eight o-methyl and o-dimethyl carbonyl compounds have been determined by spectrophotometric methods in aqueous sulphuric acid. The basicities of a further 19 compounds of the same class have been recalculated from literature data using a recently determined H0 scale of acidity. The effects of ortho substitution on the base strength have been found to increase with the steric requirements of the group attached to the carbonyl carbon.The ultraviolet intensities of 18 of the above compounds have either been freshly determined or carefully redetermined. The mean interplanar angle θ between carbonyl and phenyl groups has been obtained for both base and conjugate acid forms using the relationship ε/εplanar ≈ cos2θ.For the conjugate acids of the o-methyl derivatives a linear relation exists between ε/εplanar and the steric effect on basicity. This is discussed in terms of inhibition of resonance in the cations. No similar relation exists for the o-dimethyl derivatives. Steric effects on basicity in the latter are discussed in terms of steric inhibition of solvation of the cations.
DIBENZOYLSILANES AND SUBSTITUTED BENZOYLSILANES
Authors: Brook A. G. , Peddle G. J. D.
Published: May 2006

A number of silicon-substituted benzoylsilanes have been prepared. These all showed identical carbonyl infrared stretching wavelengths, and were all yellow, having essentially identical ultraviolet absorption spectra. Hence it is concluded that the spectral properties of benzoylsilanes are insensitive to the nature of the groups attached to silicon, even when these could provide dπ−pπ bonding.
EXTRACTIVES FROM POPULUS TREMULOIDES HEARTWOOD: THE TRITERPENE ALCOHOLS
Authors: Abramovitch R. A. , Micetich R. G.
Published: May 2006

The 'unsaturated alcohol fraction' from P. tremuloides heartwood (R. A. Abramovitch, R. G. Micetich, and S. J. Smith, Tappi, 46, 37 (1963)) has been found to contain α- and β-amyrin, butyrospermol, 24-methylenecycloartanol, lupeol, and α-amyrenonol. Some aspects of the infrared and n.m.r. spectra of these compounds are discussed and the suggestion is made that the tritisterols and orysterols may actually be C31H52O triterpenes containing a cyclopropane ring.
SYNTHESIS OF DEUTERIATED METHYL BENZOATES AND DIMETHYL PHTHALATES
Authors: Phillips R. , Leitch L. C.
Published: May 2006

not available
THE DIMER OF BROMOTRIFLUOROETHYLENE
Authors: Cullen W. R. , Singh Pritam
Published: May 2006

not available
BORATE COMPLEXING BY FIVE-MEMBERED-RING vic-DIOLS VAPOR PRESSURE EQUILIBRIUM AND N.M.R. SPECTRAL OBSERVATIONS
Authors: Mazurek M. , Perlin A. S.
Published: May 2006

Thermometric measurement of vapor pressure equilibria in reaction mixtures containing borate ion and cis-3,4-dihydroxytetrahydrofuran (I) or D-glucose 5,6-carbonate (II) indicate that complexing involves at least three different equilibria. Borate complexing by I is characterized by a gross change in n.m.r. spectral characteristics, most striking being a strong overall decoupling effect. Alterations in the spectrum of II and of 5-O-methyl D-glucose in the presence of borate, when compared with those of D-glucose, suggest that complex formation by the latter sugar proceeds with a pyranose-to-furanose interconversion. The O—C—C—O dihedral angle, within the range 0° to about 40°, does not appear to be a factor determining the stability of borate complexes. Crystalline spirane-type complexes of I, II, and of D-threose have been prepared, illustrating the usefulness of borate complexing for the isolation of some furanose sugars and derivatives.Solutions of alkali tetraborates are found by thermometric vapor pressure measurements to behave as equimolecular mixtures of alkali borate and boric acid.
THE THEORY OF CURRENT DISTRIBUTION AND POTENTIAL PROFILE AT AN ELECTRODE OF SIGNIFICANT OHMIC RESISTANCE
Authors: Conway B. E. , Gileadi E. , Oswin H. G.
Published: May 2006

The problem of current distribution at an electrode of linear geometry having a significant ohmic resistance is examined for conditions where the ohmic potential drop along the electrode material is of the same order of magnitude as the metal–solution potential difference. This problem is of practical significance in primary and secondary cells at high current drains and in certain types of fuel cell electrodes. The current distribution and metal–solution potential profiles are calculated as limiting cases of a general theory. The true and apparent current–potential relations are compared theoretically.
METHYLATION OF SUGAR DITHIOACETALS: V. D-MANNOSE DIETHYL DITHIOACETAL
Authors: Dutton G. G. S. , Tanaka Y.
Published: May 2006

Partial methylation of D-mannose diethyl dithioacetal in tetrahydrofuran with methyl iodide and silver oxide yielded 2-, 3-, and 6-O-methyl-D-mannose in the ratio of 12:1:1, respectively. The major component, 2-O-methyl-D-mannose, was characterized as the phenyl-hydrazone and the other isomers identified by electrophoresis. The Mg values of these mono-O-methyl ethers were recorded.
THE SPALLATION OF IRIDIUM WITH PROTONS OF ENERGIES 9–87 MEV
Authors: Grant G. R. , Yaffe L.
Published: May 2006

Iridium metal has been bombarded with protons varying in energy from 8 to 87 Mev. The spallation products were radiochemically separated and decay characteristics and formation cross sections were determined. It was confirmed that both Pt187 and Pt186 have half-lives of about 3 hr, and a half-life of 13.3 ± 0.2 days was found for Ir189. An isomeric state of Ir186 with half-life 2.0 ± 0.5 hr has been found. Fair agreement was obtained between excitation functions for (p,xn) reactions determined experimentally and those predicted by the Jackson model. The (p,pn) yield at 84 Mev has been compared with that calculated from Monte Carlo cascade data combined with evaporation theory and found to be too high by a factor of 4.
A MASS SPECTROMETRIC STUDY OF THE OXIDATION OF HYDROGEN SULPHIDE PART I. OBSERVATION AND IDENTIFICATION OF SOME INTERMEDIATES
Authors: Marsden D. G. H.
Published: May 2006

The oxidation of hydrogen sulphide has been followed mass-spectrometrically by direct sampling from a reaction vessel having a small leak. In the neighborhood of the third explosion limit, there is a period of 8–12 seconds of accelerating reaction before the explosion; during this time peaks are observed to grow, disappearing after explosion. By using D2S/16O2 and H2S/18O2 mixtures, it has been shown that these peaks arise from the ions H2+, S2O+, H2SO+, S2+, and H2S2+. It is evident that the first two ions represent the intermediate formation of hydrogen and disulphur monoxide; the parents of the last three ions are discussed, and it is concluded that the most likely possibilities are H2SO2, S2, and H2S2. Only during the explosion itself is there any evidence for SO radical.
NUCLEAR ISOMERS Hg197m,g, Hg195m,g AND Au196m,g FORMED BY BOMBARDMENT OF GOLD WITH PROTONS OF ENERGIES FROM 8 TO 60 MEV
Authors: Tilbury R. S. , Yaffe L.
Published: May 2006

Gold has been bombarded with protons of energies from 8 to 60 Mev to study excitation functions and isomer yield ratios for the formation of the isomeric pairs Hg197m,g, Hg195m,g, and Au196m,g. For Hg197m,g and Hg195m,g, the ratio of the yield of the metastable state to that of the ground state, σm/σg, was found to increase with increasing proton bombarding energy up to 20 and 35 Mev respectively, whilst that for Au196m,g showed a maximum at about 40 Mev.
SECONDARY PROCESSES IN THE PHOTOLYSIS OF CYCLOPENTANONE: THE PHOTOLYSIS OF 4-PENTENAL
Authors: Singh Pritam
Published: May 2006

not available
DETERMINATION OF RELATIVE SIGNS OF H—F COUPLING CONSTANTS IN FLUOROBENZENES BY NUCLEAR MAGNETIC DOUBLE RESONANCE
Authors: Paterson W. G. , Spedding H.
Published: May 2006

not available
THE OCCURRENCE OF D-glycero-D-manno-HEPTOSE IN THE EXTRACELLULAR POLYSACCHARIDE PRODUCED BY AZOTOBACTER INDICUM
Authors: Jones J. K. N. , Perry M. B. , Sowa W.
Published: May 2006

not available
THE OXIDATION OF SODIUM FORMATE BY SODIUM HYPOCHLORITE
Authors: Lister M. W. , Rosenblum P.
Published: May 2006

not available
LYCOPODIUM ALKALOIDS: XIV. FLABELLINE
Authors: Young J. C. F. , MacLean D. B.
Published: May 2006

A new alkaloid, C18H28ON2, designated flabelline, has been isolated by countercurrent distribution from the extract of Lycopodium flabelliforme. The structure and stereochemistry of flabelline have been established by its conversion to and preparation from lycopodine.
THE PROTON MAGNETIC RESONANCE SPECTRUM OF CYCLOPROPYLAMINE, THE A2A2′X CASE WITH STRONG CROSS-COUPLING: A PSEUDO FIRST-ORDER SPECTRUM WITH COMBINATION LINES
Authors: Hutton H. M. , Schaefer T.
Published: May 2006

By means of the anisotropic solvent effect of benzene on the ring protons of cyclopropylamine the proton spectrum is converted to A2A2′X. Since the cross-coupling from the A2 to the A2′ protons is large the spectrum does not approximate to a pseudo first-order AX4 spectrum. Instead, it is one which may be described as pseudo first-order with combination lines. The presence of the latter allows a fairly complete set of coupling constants to be derived in a simpler way than by a computer attack on the general A2B2X spectrum. Conversely, the approach developed here, when applicable, allows the derivation of reliable input parameters for a computer program. From the temperature dependence of the A2A2′X case the A2 and A2′ protons can be distinguished and it is found that the protons trans to the amino group are preferentially shifted to high field by the benzene molecules.
THE STRUCTURE OF THE EXTRACELLULAR POLYSACCHARIDE OF AZOTOBACTER INDICUM
Authors: Parikh V. M. , Jones J. K. N.
Published: May 2006

The extracellular polysaccharide of the Azotobacter indicum has been shown to be a mixture of two polymers of which the acidic polymer was a major fraction. The acidic polymer contained D-glycero-D-mannoheptose in the molar ratio of 1:1:1 plus traces of mannose. It consumed 1 mole of sodium metaperiodate per mole of an average anhydroaldose unit and released 0.95 moles of formaldehyde per anhydroheptose unit. Reduction of the oxidized polymer followed by hydrolysis yielded D-glucose, glycerose, glycolaldehyde, and glycerol. Complete fission of the methylated polymer yielded 2,3-di-O-methyl-D-glucuronic acid, 2,4,6,-tri-O-methyl α-D-glucose and 3,4,6,7-tetra-O-methyl D-glycero-D-mannoheptose. Partial hydrolysis of the methylated polymer produced a methylated aldotriouronic acid composed of 1 mole each of 2,3-di-O-methyl-D-glucuronic acid, 2,4,6-tri-O-methyl-D-glucose and 3,4,6,7-tetra-O-methyl D-glycero-D-mannoheptose. A methylated aldobiouronic acid was also produced and was shown to be composed of 2,3-di-O-methyl-D-glucuronic acid and 2,4,6-tri-O-methyl D-glucose.On the basis of these results it is proposed that the polysaccharide is a linear molecule composed of repeating units of D-glucuronic acid, D-glucose, and D-glycero-D-mannoheptose.
THE BARIEAU–LI CONTROVERSY AND ITS SIGNIFICANCE FOR GENERAL THERMODYNAMICS
Authors: Elliott G. A.
Published: May 2006

The Barieau–Li controversy shows the need for a general method of discussing conditions of validity of thermodynamic equations. Such a method is here developed and illustrations of its usefulness are given. It is shown how Barieau's principle can be applied in all cases.
GAS–LIQUID CHROMATOGRAPHY OF TERPENES: PART IX. THE VOLATILE OIL OF THE LEAVES OF JUNIPERUS SABINA L.
Authors: Rudloff E. Von
Published: May 2006

The chemical composition of the volatile oil of the leaves of local savin juniper and of commercial oil of savin was determined by an improved gas chromatographic technique. Both oils contain d-sabinyl acetate (38, 37.5%) and d-sabinene (30.5, 26%) as the major constituents. Smaller amounts of d,α-pinene, d-myrcene, d-limonene, γ-terpinene, p-cymene, d-isothujone, d-terpinen-4-ol, d-sabinol, d-citronellol, d-cadinene, and l-elemol were isolated. Trace amounts of α-thujene, camphene, α-terpinene, 1,8-cineole, terpinolene, thujone, geraniol, a cadinene isomer, and δ-cadinol were tentatively identified. A fraction having the typical pungent odor of juniper leaves was isolated, but it was found to consist mainly of the methyl ester of d-citronellic acid. Several unidentified oxygenated sesquiterpenes and a phenol ether were isolated in trace amounts.Some phylogenetic relationships with other thujone-bearing oils analyzed in this series are discussed.
SYNTHESIS OF DIKETOPIPERAZINES
Authors: Vining L. C.
Published: May 2006

not available
N.M.R. SOLVENT STUDIES: HYDRAZINE AS A SOLVENT
Authors: Agahigian H. , Gauthier H. , Hoberecht H. , Raphaelian L.
Published: May 2006

not available
A LINEAR RELATIONSHIP BETWEEN BOND ORDERS AND STRETCHING FORCE CONSTANTS
Authors: Robinson E. A. , Lister M. W.
Published: May 2006

A linear correlation between the bond orders and stretching force constants of bonds, which appears to have general application, is derived on the basis of a potential energy function previously used by Pauling in a correlation of C—C bond length with bond order. The relationship is shown to be consistent with predicted bond orders and experimentally determined force constants of C—C, C—O, N—N, and N—O bonds.The possible effects of anharmonicity and resonance energy on the force constant and equilibrium C—C bond distance are considered for the case of the benzene molecule, and it is concluded that the best agreement with experiment is obtained if we postulate a low degree of anharmonicity and allow for the change of resonance energy with bond distance.
RATES OF REACTION OF HYPOCHLORITE IONS WITH SULPHITE AND IODIDE IONS
Authors: Lister M. W. , Rosenblum P.
Published: May 2006

The rates of reaction of sodium hypochlorite with sodium iodide and sodium sulphite have been measured by means of a rapid-flow technique. The measurements were made over a range of temperature and hydroxide concentrations, and show that the actual slow steps of the reactions are [Formula: see text][Formula: see text]and[Formula: see text][Formula: see text]with time in seconds.The decomposition of hypoiodite ions was also measured.These results, and those for other reactions of hypochlorite ions, or hypochlorous acid, form a series similar to the reactions of peroxides. It is found that the regularities observed for peroxides apply to some extent to the present reactions, and other possible regularities are also examined.