bluuebunny/crossref_metadata_2025 huggingface dataset:
MOLECULAR INTERACTIONS: I. INFRARED SPECTRA OF SOME CARBOXYLIC ACIDS IN CARBON TETRACHLORIDE AND BENZENE SOLUTIONS
Authors: Murray F. E. , Sundaram S.
Published: May 2006

Infrared spectra of benzoic, o-chlorobenzoic, and salicylic acids in the range 700 to 3800 cm−1 have been studied. Measurements have been made on the three acids in carbon tetrachloride and benzene solutions, at a number of concentrations in each case. The results are interpreted in terms of the molecular species present in each solution and the effect of the solvents on these species. Assignments have been made of the observed bands to the various vibrational modes characteristic of the COOH group.
THE CRYSTAL AND MOLECULAR STRUCTURES OF m-DINITROBENZENE AND p-DINITROBENZENE
Authors: Trotter J.
Published: May 2006

The structures of m-dinitrobenzene and p-dinitrobenzene have been refined by three-dimensional (Fo—Fc) syntheses. The results indicate that both nitro groups in each molecule are twisted 11° out of the aromatic plane, about the C—N bonds, in contrast to nitrobenzene, where the whole molecule is completely planar. These molecular configurations are shown to be in accord with those which might be expected from intramolecular steric effects. The dimensions of the three molecules have also been compared.
THE ELECTRONIC STATES OF LINEAR METHYLENE
Authors: King G. W. , Malli G. L.
Published: May 2006

The electronic energy levels of the linear methylene radical, with r(C—H) = 1.0295 Å, have been calculated by the LCAO/MO/CI procedure. The state of lowest energy has 3∑g− symmetry, and is accompanied by low-lying 1Δg and 1∑g+ states. Allowed intravalence shell transitions from the ground state (3Πu−3∑g−,−3∑u−−3∑g−) are too high in energy to account for the observed transition at 8.6 ev, indicating that the latter is of Rydberg type if it is between linear combining states.
THE PROTON RESONANCE SPECTRA OF THE 2,5-DIMETHYL-2,5-DIMETHOXY-3,4-DIPHENYLHEXANES
Authors: Brownstein S.
Published: May 2006

The relative free energies of the various conformations for the diastereomeric 2,5-dimethyl-2,5-dimethoxy-3,4-diphenylhexanes have been determined. Hindered and free rotation about the various bonds has been observed and assignments of the proton resonance signals to specific conformations have been made.
APPLICATION OF THE VARRENTRAPP REACTION TO THE PREPARATION OF LONG-CHAIN DICARBOXYLIC ACIDS
Authors: Ackman R. G. , Bannerman M. A. , Retson M. E. , Vandenheuvel F. A.
Published: May 2006

not available
INFRARED SPECTRA OF XANTHATE COMPOUNDS: III. ORGANIC SOLVENT EFFECT ON THE C=S FREQUENCY
Authors: Little L. H. , Poling G. W. , Leja J.
Published: May 2006

The previously made absorption-band assignment (1) for the C=S stretching mode in xanthate-type compounds, 1020–1070 cm−1, has been confirmed by the characteristic behavior of the C=S dipole in a range of different solvents (Bellamy and Rogasch (2)).
METHYLATION OF SUGAR MERCAPTALS: II. L-ARABINOSE DIETHYL MERCAPTAL
Authors: Dutton G. G. S. , Tanaka Y.
Published: May 2006

Methylation of L-arabinose diethyl mercaptal in tetrahydrofuran with methyl iodide and silver oxide yielded mainly 2-O-methyl-L-arabinose and a trace of 5-O-methyl-L-arabinose. The identity of the major component was inferred by its behavior on electrophoresis and confirmed by the preparation of the crystalline amide. The polymethylated components were not examined. 2-O-Methyl-L-arabono-γ-lactone, previously known as a sirup, has now been obtained crystalline.
THE RADIOLYSIS OF ETHANOL: II. BINARY VAPOR MIXTURES
Authors: Ramaradhya J. M. , Freeman G. R.
Published: May 2006

Benzene and cyclohexene cause a marked decrease in the hydrogen yield from the vapor phase radiolysis of ethanol.The experimental data were tested against the two reaction mechanisms that gave straight-line plots for the corresponding cyclohexane–protector systems. Both of these mechanisms also gave straight-line plots for the ethanol–protector systems.One mechanism involved scavenging of hydrogen atoms. The values of the kinetic parameters derived from this mechanism are quite similar in the cyclohexane and ethanol systems.The second mechanism involved the transfer of energy (excitation or ionization) from ethanol to the protector. The values of the kinetic parameters derived from this mechanism showed some differences between the ethanol and cyclohexane systems.One possible reason for the lack of resolution between the two reaction mechanisms might be that they both occur to comparable extents. Two mechanisms appear to occur to comparable extents in the liquid cyclohexane system.
β,β,β-TRIFLUOROLACTIC ACID
Authors: Burstein Sumner H. , Ringold H. J.
Published: May 2006

not available
THE POLARIZATION OF THE FLUORESCENCE OF 1- AND 2-NAPHTHOIC ACID
Authors: Hochstrasser Robin M.
Published: May 2006

not available
IMPROVED PREPARATION OF BISTRIFLUOROMETHYLARSINE
Authors: Cullen W. R.
Published: May 2006

not available
INTEGRAL HEATS OF MIXING OF C6-ALKANES IN PERFLUOROTRIBUTYLAMINE AND IN PERFLUOROCYCLIC OXIDE (C8F16O) AT 60 °C
Authors: Nicholson Dan E.
Published: May 2006

not available
SOLVENT EFFECTS ON THE RING PROTON MAGNETIC RESONANCE SPECTRA OF SOME SUBSTITUTED QUINOLINES
Authors: Schaefer T.
Published: May 2006

not available
CLAM POISON: II. PURIFICATION OF CLAM POISON RESIDUES OF LOW TOXICITY BY A HEAVY-PAPER TECHNIQUE
Authors: Bannard R. A. B. , Casselman A. A.
Published: May 2006

The usefulness of Whatman seed-test and No. 17 papers has been examined for purification and recovery on a preparative scale of the toxin present in residues of low toxicity from the Schantz alumina chromatographic method for purification of clam poison. A method was developed to minimize introduction of impurities from the papers into fractions recovered after chromatography when t-butanol: acetic acid: water (2:1:1) was used as developer. Seed-test paper gave better separation of the toxin from other components of the residues than did No. 17 paper. Residues of bio-assay as low as 300 MU/mg were found to be capable of enrichment by the method. On a scale of 500 mg per 18 × 22-in. sheet of pretreated seed-test paper, using residues of toxicity 1400 MU/mg, a 67% recovery of toxin enriched fourfold to 5800 MU/mg was achieved in four passes. Increased loading of the paper led to a decrease in both enrichment per pass and over-all recovery of toxin. The paper chromatographic properties, toxicity, and infrared spectrum of the recovered poison agree with those reported by Schantz and co-workers for pure clam poison dihydrochloride, but the specific rotation is lower by 25%. Four possible alternative explanations for the observed anomalous rotation are discussed.
THE FRACTIONATION OF POLYTHENE
Authors: Blackmore W. R. , Alexander W.
Published: May 2006

An apparatus is described for fractionating large quantities (400 g) of polythene into five roughly equal fractions using a fractional precipitation technique. Application of this method of fractionation to a linear polythene has shown that the width of the molecular-weight distribution of the successive fractions decreases as the fractionation proceeds. Consequently, the initial high-molecular-weight fractions require refractionation to produce equally narrow distributions in them as are found in later fractions. Good agreement is obtained with the experimentally determined values of the number-average and weight-average molecular weight for the parent polymer when the measured values of Mn and Mw for each fraction are used to calculate the values for the parent. The differential molecular-weight distribution function of the parent polymer was calculated on a Bendix G-15 computer from the data for the fractions by using the weight, number-average and weight-average molecular weight, measured for each fraction in conjunction with an assumed log-normal or negative binomial molecular-weight distribution function in each fraction.
THE REACTION BETWEEN METHYL RADICALS AND ISOBUTANE
Authors: Blake A. R. , Henderson J. F. , Kutschke K. O.
Published: May 2006

It has been confirmed that the apparent rate constant for the reaction between methyl radicals, produced by the photolysis of deuterated acetone, and isobutane increases with decreasing isobutane pressure. An explanation is proposed to account for this observation suggesting that the production of methane by disproportionation between methyl and t-butyl radicals was not negligible as has been assumed previously.
THE CRYSTAL STRUCTURE OF 1,3-DICHLORONAPHTHALENE
Authors: Trotter J.
Published: May 2006

Crystals of 1,3-dichloronaphthalene are monoclinic with four molecules in a unit cell of dimensions a = 15.11, b = 3.92, c = 14.86 Å; β = 96.0°; space group P21/n. The x and z parameters of the chlorine and carbon atoms have been determined from Patterson and Fourier projections along the b-axis. The bond distances in the molecule, determined from the lengths projected on (010) together with estimated orientation angles, are very similar to the corresponding distances in naphthalene.
THE CONSTITUTION OF THE HEMICELLULOSE OF APPLE WOOD (MALUS PUMILA L. VAR. GOLDEN TRANSPARENT)
Authors: Dutton G. G. S. , Murata T. G.
Published: May 2006

The hemicellulose isolated by direct alkaline extraction of the wood has been shown to be a 4-O-methylglucuronoxylan. Methylation data indicate a backbone of approximately 120 D-xylopyranose units linked by β, 1—4 bonds with single units of 4-O-methyl-D-glucuronic acid linked by α, 1—2 bonds. The proportion of acid units to xylose is approximately 1:6. Two artifacts were isolated from the hydrolysis products of the methylated polysaccharide: 4-O-(2,3-di-O-methyl-α-D-xylopyranosyl)-2,3-di-O-methyl-D-xylose and 2,3-di-O-methyl-D-lyxose.
SOME FACTORS AFFECTING THE KÖNIGS–KNORR SYNTHESIS OF GLYCOSIDES
Authors: Goldschmid H. R. , Perlin A. S.
Published: May 2006

Glycosyl halides decompose readily in the presence of silver oxide under conditions generally used for the Königs–Knorr synthesis of glycosides. This "side reaction" probably accounts for the low yields commonly obtained in the synthesis of oligosaccharides, particularly those involving the formation of a glycosidic union through an unreactive secondary position. The rate of the side reaction, as well as that of the normal condensation reaction, is dependent on the condition of the silver oxide, and is retarded markedly by elemental iodine. This latter effect appears to be related to the improved yield obtained in Königs–Knorr syntheses when iodine is used. Among the products formed in the decomposition of 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl bromide are 2,3,4,6-tetra-O-acetyl-D-mannose, a heptaacetyl 1,2,1′-linked dimeric orthoacetate, and a second high-molecular-weight compound that also shows ortho ester properties.
PYRROLES RELATED TO PORPHOBILINOGEN
Authors: Arsenault G. P. , MacDonald S. F.
Published: May 2006

A study of the decarboxylation of pyrroles related to 5-carboxyporphobilinogen has led to an improved synthesis of porphobilinogen, to isoporphobilinogen, and to other pyrroles required for the preparation of possible intermediates in the biosynthesis of porphyrins.
PHOTOLYSIS OF POLYACRYLONITRILE
Authors: Jellinek H. H. G. , Bastien I. J.
Published: May 2006

The photolysis of polyacrylonitrile has been investigated in solution (80:20 by weight of ethylene carbonate to propylene carbonate), in powder form, and as a film. Experiments have been carried out in vacuum and in the presence of oxygen. All polymer samples were exposed to ultraviolet light of wavelength 2537 Å. In solution a random chain-scission reaction with a small quantum yield (ca. 10−4 main chain bonds broken/quantum absorbed) takes place; at the same time, photochemical reactions occur involving side groups of the polymer chains, as evidenced by the change in the ultraviolet spectra of the polymer solutions. It seems likely that double-bond formation, both conjugated and isolated, and cyclization are responsible for the change in spectra. Infrared spectra do not show any change. Exposed polymer films become cross-linked and exposed powder also cross-links and evolves small molecules, such as nitriles, particularly HCN. Degradation in oxygen suppresses what is believed to be double-bond formation as evidenced by ultraviolet absorption spectra. The photolysis of glutaronitrile as a model substance has also been studied.
STEREOCHEMICAL STUDIES: III. REACTIONS OF 4-OXA-5α-CHOLESTAN-3α-OL, A CARBOHYDRATE MODEL
Authors: Edward J. T. , Morand P. F. , Puskas I.
Published: May 2006

4-Oxa-5α-cholestan-3α-ol was prepared by reduction of 4-oxa-5α-cholestan-3-one with lithium aluminum hydride. It showed several typical carbohydrate reactions, such as mutarotation in aqueous tetrahydrofuran and condensation with alcohols in the presence of hydrogen chloride to give 3-alkoxy-4-oxa-5α-cholestanes. These compounds were also prepared by the reaction of alcohols with 3α-chloro-4-oxa-5α-cholestane in the presence of base. Factors governing the proportions of 3α and 3β isomers formed in these reactions are discussed.
LYCOPODIUM ALKALOIDS: XI. THE STRUCTURE AND REACTIONS OF ACRIFOLINE
Authors: French W. N. , MacLean D. B.
Published: May 2006

Structure A for acrifoline is proposed from a study of the products formed in the Hofmann degradation, von Braun degradation, and several oxidative degradations of the alkaloid. Structure C is proposed for a compound formed on treatment of dihydroacrifoline with copper sulphate in pyridine or with peroxytrifluoroacetic acid.
THE MOLECULAR STRUCTURE OF (−)-N-METHYL-GELSEMICINE HYDRIODIDE, C21H29O4N2I
Authors: Przybylska Maria , Marion Léo
Published: May 2006

not available
THE DECOMPOSITION OF HYDROGEN PEROXIDE IN THE PRESENCE OF HYDROGEN
Authors: Baldwin R. R. , Booth D. , Brattan D.
Published: May 2006

not available
CRYSTALLOGRAPHIC DATA FOR ETHYL 3,5-DINITROBENZOATE
Authors: Camerman N. , Trotter J.
Published: May 2006

not available
RADIATION CHEMISTRY OF CYCLOHEXANE: III. EFFECT OF BENZENE AND IODINE ON THE ISOTOPIC COMPOSITION OF RADIOLYTIC HYDROGEN FROM C6D12–C6H12 MIXTURES
Authors: Dyne P. J. , Jenkinson W. M.
Published: May 2006

The isotopic composition of hydrogen evolved in the radiolysis of C6D12–C6H12 mixtures has been measured in the presence of various amounts of benzene and iodine. The yield of the unimolecular decomposition and the specific yield of the bimolecular reaction are reduced in approximately the same proportion as the yield of total hydrogen. It is concluded that (i) iodine and benzene interact to a comparable extent with both unimolecular and bimolecular decomposition modes, (ii) it is probable that neither of these additives act by scavenging, and (iii) it is probable that they act by quenching a common precursor of the two decomposition modes.
CONFORMATIONAL EQUILIBRIA IN DIETHYL KETONE
Authors: Jones R. Norman , Noack K.
Published: May 2006

A variable-thickness, variable-temperature absorption cell, modified from the design of Holden, Taylor, and Johnston, has been used to compare the infrared spectrum of diethyl ketone at −75° and +25 °C. The Raman spectrum of diethyl ketone has also been measured at +6°, +25°, and +85 °C, and the proton magnetic resonance spectrum over the range −61° to 104 °C.Both the infrared and Raman spectra exhibit pronounced temperature sensitivity, which is attributed to the presence of at least two conformational isomers in the liquid phase. Possible structures for these isomers are considered. Small but significant chemical shifts are noted in the proton magnetic resonance spectrum.
CONFORMATIONAL EQUILIBRIA IN OPEN-CHAIN α,β-UNSATURATED KETONES
Authors: Noack K. , Jones R. Norman
Published: May 2006

The infrared and Raman spectra of trans-Δ3-penten-2-one have been measured over the temperature range +30° to −75° and +85° to +5° respectively. The temperature-dependent changes observed in the spectra indicate that this ketone exists as an equilibrium mixture of s-cis and s-trans conformational isomers in the liquid state. The s-trans form is the more stable and is present exclusively in the crystalline solid.Similar measurements have been carried out on Δ3-buten-2-one. The infrared and Raman spectra of this ketone also exhibit temperature effects that can be explained by a similar equilibrium, though the evidence is not as conclusive as for trans-Δ3-penten-2-one.The influence of alkyl substitution at the α- and β-carbon atoms on the relative stability of the s-cis and s-trans forms of α,β-unsaturated ketones is discussed.
THE DECOMPOSITION OF CARBON DIOXIDE BY Hg 6(3P1) AND Hg 6(3P0) ATOMS
Authors: Strausz Otto P. , Gunning Harry E.
Published: May 2006

Carbon dioxide has been shown to decompose into carbon monoxide and oxygen atoms, when exposed to radiation at 2537 Å, in the presence of mercury vapor. The rate rises steeply with decreasing substrate pressure, and varies directly with the 1.8 ± 0.1 power of the light intensity. The proposed mechanism attributes reaction to the collision of electronically excited CO2 molecules with Hg 6(3P1) atoms. The suppression of reaction at higher substrate pressures is readily explained in terms of collisional deactivation of the excited CO2 species. Nitrogen was found to increase the rate of CO formation; the maximum effect was obtained for a mixture of 7.4 mm nitrogen and 3.74 mm carbon dioxide, in which case the rate was 1.58 times that for pure substrate. It is shown that nitrogen serves to generate metastable Hg 6(3P0) atoms, which can sensitize the decomposition. The reaction might serve as a chemical method for monitoring Hg 6(3P0) atoms. For CO2–N2 mixtures, the rate was found to rise when the reacting system was exposed to radiation at 4047 Å. This is taken as direct evidence of sensitization by higher states of mercury, generated by stepwise excitation, since radiation at 4047 Å converts Hg 6(3P0) to Hg 7(3S1).
SOME ASPECTS OF THE NUCLEAR MAGNETIC RESONANCE SPECTRA OF COMPOUNDS CONTAINING C-METHYL GROUPS
Authors: Anet F. A. L.
Published: May 2006

The N.M.R. spectra of compounds containing various types of C-methyl groups are discussed with special reference to the effects of spin coupling. Particular attention is given to compounds containing the CHCH3 group in saturated systems. It is pointed out that the observed splitting of the methyl band is not always equal to the coupling constant between the methyl protons and the adjacent proton, even when the chemical shift between the two groups of protons is large.
STRUCTURAL RELATIONSHIPS OF EXTRACELLULAR POLYSACCHARIDES FROM PHYTOPATHOGENIC XANTHOMONAS SPP.: PART I. STRUCTURE OF THE EXTRACELLULAR POLYSACCHARIDE FROM XANTHOMONAS STEWARTII
Authors: Gorin P. A. J. , Spencer J. F. T.
Published: May 2006

Xanthomonasslewartii produces an extracellular polysaccharide which is markedly different from those formed by other Xanthomonas spp. examined in that it gave glucose, galactose, and an aldobiouronic acid on hydrolysis. Methylation followed by hydrolysis yielded 2,3,4,6-tetra-O-methyl-D-glucose (4 parts), 2,3,4-tri-O-methyl-D-glucose (2 parts), 2,4,6-tri-O-methyl-D-galactose (1 part), 2,3,4-tri-O-methyl-D-galactose (2 parts), and 2-O-methyl-D-galactose (1.8 parts). Partial acid hydrolysis yielded 6-O-β-D-glucopyranosyl-D-galactose, 3-O-β-D-glucopyranosyl-D-galactose, 3-0-β-D-galactopyranosyl-D-galactose, and 4-O-β-D-glucuronopyranosyl-D-galactose.
LIGHT ABSORPTION STUDIES: PART XIX. THE ULTRAVIOLET ABSORPTION SPECTRA OF IODOBENZENES
Authors: Forbes W. F.
Published: May 2006

As a sequel to previous studies on the ultraviolet absorption spectra of halogen-substituted benzenes the spectra of iodobenzene in various solvents, and the spectra of a series of substituted iodobenzenes in cyclohexane solution, are reported. It is shown that these spectra can be rationalized qualitatively in terms of simple resonance theory, if the apparent mesomeric effect of the iodine atom is assumed to be greater for iodine than for the other halogen atoms.
CHEMICAL CONSTITUENTS OF CHICOZAPOTE
Authors: Azpeitia E. , Bowers A. , Crabbé P. , Mancera O. , Matthews J. S. , Reynoso J. , Salazar J.
Published: May 2006

not available
CO-ORDINATION COMPOUNDS OF HYDRAZINE: PART II. THE INTERACTION OF TRIMETHYLBORANE AND TRIMETHYLALUMINUM WITH HYDRAZINE
Authors: Paterson W. G. , Onyszchuk M.
Published: May 2006

Trimethylborane and anhydrous hydrazine react at 25° in vacuum, yielding a 2:1 adduct, 2(CH3)3B•N2H4, which is stable at or below −78° and evolves trimethylborane slowly at higher temperatures, leaving a stable 1:1 adduct, (CH3)3B•N2H4 (m.p. 42–43°). The thermal decomposition of the latter at 150–160° is complex, producing nitrogen, methane, ammonia, a mixture of butane and the isomeric butenes, and a heterogeneous solid. At 25° diborane displaces trimethylborane from the 1:1 adduct and reacts with it to form 1,1-dimethyldiborane, in addition to hydrogen, methane, and a heterogeneous solid.Trimethylaluminum and hydrazine give a complex reaction in vacuum at 25°, but in diethyl ether solution the product was thought to be (CH3)2AlNHNHAl(CH3)2, which decomposes on being touched.
THE STEREOCHEMISTRY OF EIGHT-CO-ORDINATION: THE NATURE OF THE BONDING IN THE Mo6Cl84+, Nb6Cl122+, AND RELATED IONS
Authors: Gillespie R. J.
Published: May 2006

It is pointed out that the square-antiprism arrangement of eight ligands which is expected for an atom which has eight bonding electron pairs in its valency shell occurs in the polynuclear complex ions found in several basic salts of zirconium(IV), thorium(IV), cerium(IV), and uranium(IV). The nature of the bonding in Mo6Cl84+, Nb6Cl122+, and related ions is discussed, and it is shown that it may be described in a manner which is consistent with a square-antiprism arrangement of eight electron pairs around each metal atom.
THE SYNTHESIS OF ACETAMIDO-DEOXY KETOSES BY ACETOBACTER SUBOXYDANS: PART II
Authors: Jones J. K. N. , Perry M. B. , Turner J. C.
Published: May 2006

The microbiological oxidation of 1-deoxy-1-N-methylacetamido-D-glucitol and 2-acetamido-1,2-dideoxy-D-glucitol yielded a syrupy ketose and a crystalline ketose respectively. Crystalline derivatives of each were prepared and structural investigations of the ketoses showed the former to be 6-deoxy-6-N-methylacetamido-L-xylohexulose and the latter to be 5-acetamido-5,6-dideoxy-L-xylohexulose.
LIGHT ABSORPTION STUDIES: PART XX. THE ULTRAVIOLET ABSORPTION SPECTRA AND INFRARED CARBONYL BANDS OF BENZOYL CHLORIDES
Authors: Forbes W. F. , Myron J. J. J.
Published: May 2006

The ultraviolet absorption spectra and infrared carbonyl bands of a number of substituted benzoyl chlorides are determined. It is found that as a first approximation the B-bands of the ultraviolet spectra are similar for benzoyl chlorides and for the corresponding benzaldehydes and acetophenones. The spectra are discussed in terms of previously stated hypotheses. In this way the order of the apparent negative mesomeric effect is deduced to be —NO2 > — COCl > —CHO > —COCH3, and the effective size of these substituents is confirmed to be in the order —NO2 > —COCH3 > —COCl > —CHO.The infrared carbonyl band occurs as a well-defined doublet in most of the ring-substituted benzoyl chlorides. The most probable explanation is that these doublets occur because of an intramolecular vibration.
THE REACTION OF ETHANOL VAPOR WITH Hg 6(3P1) ATOMS
Authors: Knight Arthur R. , Gunning Harry E.
Published: May 2006

The reaction of ethanol vapor with Hg 6(3P1) atoms has been investigated under static conditions at 25 °C. To determine the nature and efficiency of the primary process, the reaction has been studied in the presence of nitric oxide, and also under conditions of inter mittent illumination. For the pure substrate the volatile products were H2 (0.53), CH3CHO (0.08), CO (0.025), C2H6 (0.006), and CH4 (0.002), with the bracketed numbers representing the quantum yields at zero exposure time. The heavy product was a mixture of butanediols containing 90% 2,3-, 8% 1,3-, and 2% 1,4-butanediol. With 20% added NO, the products were EtONO (0.25), N2O (0.14), H2O, and H2 (0.017). Under intermittent illumination, the quantum yield (Φ) of H2 formation for pure substrate was measured as a function of the light period (tL) and the dark period (tD). For maximum values of Φ(H2), it was found that tD had to exceed ca. 120 msec. Under these conditions, Φ(H2) rose linearly with decreasing log tL, to a maximum value of 0.96 at tL less than 0.4 msec.From the study it is concluded that ethanol reacts with Hg 6(3P1) atoms to form ethoxy radicals and H atoms with at least 96% efficiency. The primary ethoxy radicals disappear by hydrogen abstraction from the substrate to form mainly CH3CHOH radicals. Under continuous illumination the low value (0.53) for Φ(H2) is caused principally by the addition of H atoms to the CH3CHOH radicals.
STEADY-STATE DEPARTURE IN ENZYME REACTIONS
Authors: Shin Hyung Kyu , Giddings J. Calvin
Published: May 2006

A method is described for calculating the departure from steady-state conditions in enzyme reactions. This provides an immediate and simple criterion for the validity of the steady-state approximation. Several variations of the general method, differing in the degree of simplicity and in the treatment of initial transients, are formulated and discussed. These methods are applied to the general case of an enzyme reaction following the Michaelis–Menten mechanism. Specific applications are made using the data of Chance and Gutfreund. While in these specific cases the steady-state concentration of intermediate is reasonably accurate, the extent of reaction may easily vary from that calculated by means of the steady state.
TRYPTAMINES, CARBOLINES, AND RELATED COMPOUNDS: PART IX. THE CYCLIZATION OF SOME NITRO- AND AZIDO-PHENYLPYRIDINES. PYRIDO[1,2-b]INDAZOLE
Authors: Abramovitch R. A. , Adams K. A. H.
Published: May 2006

Heating 2-o-nitrophenylpyridine with ferrous oxalate gives rise to pyrido[1,2-b]indazole (III). The evidence for the structure of this compound is discussed. Similarly, heating 2-o-nitrophenylpyridine methiodide and N-oxide with ferrous oxalate gives (III), in each case, demethylation and deoxygenation preceding the cyclization. In the latter case a minute amount of δ-carboline is also formed. Heating pyridine-N-oxides with ferrous oxalate is a potentially general method of effecting deoxygenations of these compounds. Contrary to the results of Smith and Boyer (11), it is found that heating 2-o-azidophenylpyridine also gives rise to (III). On the other hand, the action of heat on 2-o-azidophenyIpyridine-N-oxide gives a mixture of δ-carboline and δ-carboline-py-N-oxide in low yield. The mechanism of the cyclization of the azides and of the reaction taking place on heating nitro-compounds with ferrous oxalate is discussed briefly; the formation of a nitrene intermediate is favored.The catalytic reduction of 2-o-nitrophenylpyridine-N-oxide giving rise to the azoxy-, azo-, and hydrazo-derivatives is described and the ultraviolet absorption spectra of these compounds are discussed. It is concluded the steric inhibition of coplanarity exists in the azoxy- and azo-compounds leading to the lack of effective conjugation across the N=N bond.
THE Hg 6(3P1)-PHOTOSENSITIZED DECOMPOSITION OF NITRIC OXIDE
Authors: Strausz Otto P. , Gunning Harry E.
Published: May 2006

The reaction of NO with Hg 6(3P1) atoms has been studied under static conditions at 30°, over the pressure range 1–286 mm. The products were found to be N2, N2O, and higher oxides of nitrogen. At NO pressures exceeding 4 mm, the total rate of formation of N2+N2O was constant, while the ratio N2O/N2 increased linearly with the substrate pressure. The rate was found to vary directly with the first power of the intensity at 2537 Å, and a value of 1.9 × 10−3 moles/einstein was established for the quantum yield of N2 + N2O production. In the proposed mechanism, reaction is attributed to the decomposition of an energy-rich dimer, (NO)2*, which is formed by the collision of electronically excited (4II) NO molecules with those in the ground state. The (NO)2* species is assumed to decompose by the steps: (NO)2* → N2 + O2 and (NO)2* + NO → N2O + NO2. The mechanism satisfactorily explains the observed behavior of the system.
STABILITY OF CoBr+ AND NiBr+
Authors: Lister M. W. , Wilson D. W.
Published: May 2006

not available
INVERSE INTERMOLECULAR KINETIC ISOTOPE EFFECTS IN UNIMOLECULAR REACTIONS. DIFFERENTIAL QUANTAL EFFECTS IN THE NON-EQUILIBRIUM BEHAVIOR
Authors: Rabinovitch B. S. , Setser D. W. , Schneider F. W.
Published: May 2006

not available
THE RATE OF REACTION OF ACTIVE NITROGEN WITH AMMONIA AND ETHYLENE
Authors: Wright A. N. , Winkler C. A.
Published: May 2006

The rate constants for the reactions of C2H4 and NH3 are determined by termination of the reactions in the gas phase after different times of reaction. The average value for the rate constant of the N atom–C2H4 reaction at 150 °C is 1.8 × 1010 cc mole−1 sec−1, when the initial N-atom concentration is determined from the maximum production of HCN. The average value for the rate constant for the over-all reaction of NH3 with excited nitrogen molecules, at 104 °C in the "poisoned" system, and 83 °C in the "unpoisoned" system, for low initial flow rates of NH3, or short reaction time, is 2.2 × 1010 cc mole−1 sec−1. The decrease in value of this rate constant at higher initial flow rates of NH3 and longer reaction times in the "poisoned" system indicates that the species responsible for NH3 decomposition is generated during the decay of N atoms in the presence of NH3. The value for the NH3 reaction is discussed in terms of energy transfer.
KINETIC STUDIES OF SOME ALCOHOL–ISOCYANATE REACTIONS
Authors: Lovering Edward G. , Laidler Keith J.
Published: May 2006

The kinetics of 12 alcohol–isocyanate reactions have been studied at a series of temperatures. The reactions were studied by a calorimetric technique, as well as the usual analytical method. The results are shown to be in agreement with a mechanism previously proposed by Baker. Certain objections to Baker's mechanism are discussed.
THE SYSTEM SILVER–INDIUM–GALLIUM
Authors: Campbell A. N. , Reynolds W. F.
Published: May 2006

The system silver–indium–gallium has been investigated by the standard techniques of thermal analysis, photomicrography, X-ray photography, and hardness testing. The smallness of the heat effects made the determination of the liquid surface indefinite, at least in the low-temperature region where the pronounced tendency for metastable liquid phase to persist rendered all measurements indefinite, but the room-temperature isotherm was determined with more certainty. Owing to the complexity of the diagram there is still some uncertainty about some areas.A one-phase area (α phase) exists in the silver-rich region of the ternary isotherm, representing the solid solubility of indium and gallium in silver. The silver-rich intermediate phase in the system silver–indium, δ, is shown to have a close-packed hexagonal structure and its lattice constants have been determined. The structure of γ, the corresponding phase in the system silver–gallium is more complex and was not determined. δ and γ phases do not form a continuous one-phase region.Ternary peritectics exist at 623 °C and 600 °C (approximately). It is possible that two peritectics exist at the latter temperature, in close proximity.The ternary eutectic lies at 14.5 °C and has an approximate composition of 2% silver, 24% indium, and 74% gallium.
REACTION OF IODOMETHANE WITH TERTIARY ARSINE MERCURIC IODIDE COMPLEXES
Authors: Baig M. M. , Cullen W. R. , Dawson D. S.
Published: May 2006

The reaction of 1:1 tertiary arsine mercuric iodide complexes with iodomethane gives arsonium derivatives of triiodomercury (II).
THE STRUCTURE OF LICHENIN: SELECTIVE ENZYMOLYSIS STUDIES
Authors: Perlin A. S. , Suzuki S.
Published: May 2006

Lichenin, the poly-β-D-glucan of Cetraria islandica (Iceland moss), is found by enzymic degradation to differ in fine structure from the poly-β-D-glucans of cereal grains. Enzymolysis has been carried out with a cellulase and a laminarinase preparation, the former yielding mainly O-β-D-glucopyranosyl-(1 → 3)-O-β-D-glucopyranosyl-(1 → 4)-α-D-glucose, and the latter mainly O-β-D-glucopyranosyl-(1 → 4)-O-β-D-glucopyranosyl-(1 → 3)-α-D-glucose. Di-and tetra-saccharides are produced in small proportions. Steric aspects of these enzymic degradations are discussed. The basis constitution of lichenin is represented by a tetrameric unit in which two adjacent (1 → 4) linkages alternate with an isolated (1 → 3) linkage; occasionally four consecutive monomers are linked by (1 → 4) bonds. The glucans of cereal origin differ mainly in possessing a higher proportion of the latter structural sequence. Despite their close chemical similarity to cellulose, all of these glucans are soluble, a property that appears to be related to the even distribution of β-(1 → 3) bonds along the chains, with a resulting disruption of linear orientation effects.
PHOTOCHEMICAL SYNTHESES: 2. THE IRRADIATION OF ACENAPHTHENE WITH BENZIL
Authors: Mayo P. De , Stoessl A.
Published: May 2006

The irradiation product of acenaphthene and benzil described by Oliveri-Mandalà, Giacalone, and Deleo has been shown to have the structure (III) and not that of the cyclobutane derivative (II, R = H) originally proposed. The main product obtained by the action of acetic anhydride and sulphuric acid on (III) is not the result of an acetylation process, but is the sultone (IV).
THE ESTABLISHMENT OF CONFIGURATION IN DIELS–ALDER ADDUCTS BY N.M.R. SPECTROSCOPY
Authors: Fraser Robert R.
Published: May 2006

It has been shown that the magnetically anisotropic double bond in bicyclic Diels–Alder adducts exerts a paramagnetic effect on protons in an exo configuration and a diamagnetic effect on protons in an endo configuration. Thus the configuration of a proton or proton-bearing substituent can be ascertained by observing the change in its chemical shift when the double bond is removed by hydrogenation. However, caution must be used in applying the method to compounds in which the double bond bears a magnetically anisotropic substituent.
INFRARED ABSORPTION OF FORMALDEHYDE AT LOW TEMPERATURES: EVIDENCE FOR MULTIPLE TRAPPING SITES IN AN ARGON MATRIX
Authors: Harvey K. B. , Ogilvie J. F.
Published: May 2006

The infrared absorption of formaldehyde in both the polycrystalline and the monomeric form has been measured at 4 °K. In the latter case the molecules were suspended in an inert matrix of Ar or N2. The fine structure of the matrix spectra is discussed from the point of view of rotation of the monomers but this interpretation is ruled out in favor of one based on multiple trapping sites in the matrix.
STUDIES ON THE STRUCTURE OF CATALPOSIDE
Authors: Lunn W. H. , Edward Deirdre Waldron , Edward J. T.
Published: May 2006

Catalposide extracted from the unripe fruit of Catalpa ovata affords bisdesoxyaucubin on reduction with lithium in liquid ammonia. The reduction is accompanied by the shift of a double bond. From this and other evidence, two possible structures are proposed for the compound.
SYNTHESIS OF POTENTIALLY PHYSIOLOGICALLY ACTIVE β-PHENYLETHYLAMINES: PART I. 3,4,5-TRIMETHOXY-α-AMINOMETHYLBENZYL ALCOHOL AND 4-ACETOXY-3,5-DIMETHOXY-α-AMINOMETHYLBENZYL ALCOHOL DERIVATIVES
Authors: Heacock R. A. , Hutzinger O.
Published: May 2006

The preparation of several 3,4,5-trisubstituted-β-hydroxy-β-phenylethylamines related to mescaline, by the reduction or reductive alkylation of the corresponding nitroalcohols, is described.
PREPARATION OF SYNTHETIC GELS FOR CHROMATOGRAPHY OF MACROMOLECULES
Authors: Lea D. J. , Sehon A. H.
Published: May 2006

not available
REACTION OF GROUP V IODIDES WITH IODOMETHANE AND TRIFLUOROIODOMETHANE IN THE PRESENCE OF MERCURY
Authors: Baig M. M. , Cullen W. R.
Published: May 2006

not available
IMPROVED SYNTHESIS OF N-ALKYL-ASPARTIC ACIDS
Authors: Laliberté R. , Berlinguet L.
Published: May 2006

not available
THE SYNTHESIS OF SOME BASIC DIPHENYL ETHERS
Authors: Frangatos Gerassimos , Dodsworth J. M. , Kohan Geza , Chubb Francis L.
Published: May 2006

not available
STUDIES IN THE PYRROLINE SERIES: I. THE PROTON MAGNETIC RESONANCE SPECTRA OF SOME PYRROLINES
Authors: Bonnett R. , McGreer D. E.
Published: May 2006

The proton magnetic resonance spectra of some pyrrolines and pyrroline oxides have been determined. The spectra accord with the Δ1 formulation of the bases.
STUDIES IN THE PYRROLINE SERIES: II. OXYGEN TRANSFER FROM CYCLIC NITRONES TO TRIPHENYLPHOSPHINE
Authors: Agolini Franco , Bonnett R.
Published: May 2006

Triphenylphosphine, triphenylarsine, triphenylstibine, and triphenylbismuthine have been evaluated as acceptors in oxygen transfer reactions involving 1-pyrroline-1-oxides. The first reagent especially offers a useful route from the nitrones to the corresponding pyrrolines.
AROMATIC SUBSTITUTION: PART I. THE REACTION OF PHENYLLITHIUM WITH 3-ALKYLPYRIDINES. STERIC EFFECT AND QUANTITATIVE ANALYSIS OF ISOMER RATIOS
Authors: Abramovitch R. A. , Giam Choo-Seng
Published: May 2006

No 4-phenylpyridine is formed in the reaction of phenyllithium with pyridine. When phenyllithium reacts with a 3-alkylpyridine the main product is the 3-alkyl-2-phenylpyridine if the alkyl group is methyl, ethyl, or isopropyl, but it is the 5-alkyl-2-phenylpyridine when the substituent is t-butyl. Methods are described for the separation and quantitative analysis of mixtures of 3-alkyl- and 5-alkyl-2-phenylpyridines using vapor phase chromatography. The results are discussed briefly and possible explanations of the observed orientations are mentioned.
ALIPHATIC CHEMISTRY OF FLUORENE: PART VIII. BENZYL 9-FLUORENYL SULPHOXIDE AND SOME 9-FLUORENYL SULPHIDES
Authors: Bavin P. M. G.
Published: May 2006

Allyl 9-fluorenyl sulphide, benzyl 9-fluorenyl sulphide, and di-9-fluorenyl sulphide are stable to boiling ethereal phenyl lithium, in marked contrast to the corresponding ethers. Benzyl 9-fluorenyl sulphoxide has been prepared and shown to be more weakly acidic than 9-fluorenyl sulphones.
GLYCOSIDATION OF SUGARS: I. FORMATION OF METHYL-D-XYLOSIDES
Authors: Bishop C. T. , Cooper F. P.
Published: May 2006

The reactions of D-xylose, methyl α-D-xylofuranoside, and methyl β-D-xylopyranoside with methanolic hydrogen chloride under controlled conditions have been followed by gas–liquid partition chromatographic analysis of the products. Rate curves were established for each of the four methyl-D-xylosides and the results showed that the following sequence of reactions occurs in the formation of methyl xylosides: (1) xylose → furanosides, (2) anomerization of furanosides, (3) furanosides → pyranosides, (4) anomerization of pyranosides. The relative rates of these four reactions in order of decreasing velocity are 2, 1, 3, 4. Reaction 3 appears to proceed with retention of configuration at the anomeric center. Possible intermediates in these reactions are discussed. Substitution of positions 2 and 3 in the D-xylose molecule by O-methyl groups resulted in an increase in the furanoside content of the methanolysis products at equilibrium.
SYNTHESIS OF 4-O-METHYL-L-ARABINOSE
Authors: Siddiqui I. R. , Bishop C. T.
Published: May 2006

4-O-Methyl-L-arabinose has been synthesized from ethyl 2,3-di-O-benzyl-α-L-arabinofuranoside by successive methanolysis, methylation, debenzylation, and hydrolysis; a proof of structure is presented. Ethyl 2,3-di-O-benzyl-α-L-arabinofuranoside yielded 57% furanoside and 43% pyranoside at equilibrium in methanolic hydrogen chloride.
THE REACTION OF NITROGEN ATOMS WITH HYDROGEN ATOMS
Authors: Mavroyannis C. , Winkler C. A.
Published: May 2006

The reaction has been studied in a fast-flow system by the addition of atomic hydrogen to active nitrogen. Hydrogen atom concentrations were estimated from the maximum destruction of hydrogen bromide in the atomic hydrogen stream. The nitrogen atom consumption, in the reaction mixture, was determined by addition of nitric oxide at different positions along the reaction tube. A lower limit of 4.87 ± 0.8 × 1014 cc2mole−2sec−1 was derived for the rate constant of the reaction of nitrogen atoms with hydrogen atoms, over the pressure range 2.5 to 4.5 mm, in an unheated reaction tube, poisoned with phosphoric acid. No reaction between nitrogen atoms and molecular hydrogen was observed, even at 350 °C.
ADSORPTION OF LIGNOSULPHONATES ON SOLIDS
Authors: Beeckmans J.
Published: May 2006

The adsorption of various fractionated lignosulphonates on kaolin and on titanium dioxide was studied as a function of acidity and ionic strength. The quantity adsorbed at surface saturation was found to be remarkably dependent on the pH, and to some extent on ionic strength. The adsorption was irreversible with respect to dilution for all but the lowest molecular weight fractions, but desorption could be induced by changes in the pH. This fact was employed to fractionate some lignosulphonates and may be of general utility as a method for fractionating polyelectrolytes. The data are interpreted in terms of the contributions of the electrostatic and hydrogen-bonding forces to the adsorption energy.
A SIMPLE METHOD OF SOLVING ILKOVIC'S DIFFERENTIAL EQUATION FOR THE TRANSFER OF DEPOLARIZER TO THE DROPPING MERCURY ELECTRODE
Authors: Subrahmanya R. S.
Published: May 2006

The method developed by Ilkovic for solving the differential equation[Formula: see text]which governs the diffusion of the depolarizer to the surface of the dropping mercury electrode is very difficult. In the present work a simple method is presented. The above equation is transformed into ∂C/∂T = ∂2C/∂s2 by introducing the two new variables s = xt2/3/2. √((3/7)D) and T = (1/4)t/7/3. The boundary conditions for the transformed differential equation are formulated and the equation is solved by the Laplace transform method.
THE INFRARED ABSORPTION SPECTRA OF DEUTERATED ESTERS: III. METHYL LAURATE
Authors: Jones R. Norman
Published: May 2006

The infrared absorption spectrum of methyl laurate in carbon tetrachloride and carbon disulphide solutions has been compared with the spectra of seven derivatives deuterated in the ω-methyl group, the α-methylene groups, the carbomethoxy group, and in binary and ternary combinations of these positions. The spectra of n-dodecanes deuterated in the terminal methyl groups and of methyl laurates chlorinated in the ω-methyl and α-methylene groups have also been measured.From an analysis of these spectra, all the bands and inflections between 3100 and 700 cm−1 in the spectrum of methyl laurate can be assigned to localized group vibrations. The spectra of some related acid chlorides, alcohols, and bromides are also briefly noted.
THE CHEMISTRY OF ALUMINUM–NITROGEN COMPOUNDS: II. REACTIONS OF TETRAMETHYLTETRAZENE WITH ALUMINUM HYDRIDE AND TRIALKYLALUMINUM COMPLEXES
Authors: Fetter Neil R. , Bartocha Bodo
Published: May 2006

The reaction of tetramethyltetrazene with Me3Al:NMe3, Et3Al, and H3Al:NMe3 has led to a new method for the preparation of (Me2Al—NMe2)2, (Et2Al—NMe2)2, and H2Al—NMe2, respectively. The reaction of tetramethyltetrazene with Me3Al has produced Al(NMe2)3, MeAl(NMe2)2, and Me2Al—NMe2, and with Et3Al:NMe3 has produced Et3Al:Me2NN=NNMe2, Et2Al—NMe2, and the polymer (—AlEtNEt—)n. In all but one case, the complexes are formed by the interaction of a dimethylamine radical, which results from the cleavage of Me2NN=NNMe2, with the aluminum moiety and the subsequent elimination of an alkane or hydrogen.
THE STRUCTURAL ANALYSIS OF SOME ACIDIC XYLANS BY PERIODATE OXIDATION
Authors: Dutton G. G. S. , Unrau A. M.
Published: May 2006

By determining the amount of formaldehyde produced on periodate oxidation of borohydride-reduced apple- and cherry-wood xylans the degree of polymerization was shown to be 155 and 100 respectively. Acid hydrolysis of the polyols obtained by periodate oxidation and borohydride reduction gave ethylene glycol in amounts indicating that these xylans have a small degree of branching. Mild acid hydrolysis of the polyols demonstrated that in these xylans D-glucuronic acid as well as 4-O-methyl-D-glucuronic acid was present and that some of the former occupied non-terminal positions.
SYNTHÈSES D'ACIDES AMINÉS CYCLIQUES À PARTIR DE DÉRIVÉS DE L'ACIDE ADIPIQUE
Authors: Nicole Lise , Berlinguet Louis
Published: May 2006

The Dieckmann reaction has been reinvestigated in view of obtaining alkyl-substituted cyclopentanones. Control of the reaction during alkylation now permits either the opening of the cyclopentane ring to give, without the isolation of intermediates, substituted adipic esters in excellent yields or normal substitution on the ring.Methyl- and allyl-substituted cyclopentanones were obtained from the corresponding Dieckmann esters or from the substituted adipic acids. These ketones were transformed by the Strecker method into their corresponding spirohydantoins. In both cases, two diastereo-isomers were isolated and studied.1-Amino-2-methyl-cyclopentanecarboxylic acid and 1-amino-2-allyl-cyclopentanecarboxylic acid were prepared in good yields from the spirohydantoins and characterized.
DI-(4-OXA-5α-CHOLESTAN-3α-YL) ETHER
Authors: Edward J. T. , Puskas I.
Published: May 2006

not available
ON ELECTRODEPOSITED THALLIC OXIDE
Authors: Foley William T.
Published: May 2006

Thallium oxide, electrolytically deposited at the anode, has a defective oxide structure and the thallium (I) content is about 1% by weight. The conductivity of the oxide is (1.54 ± 0.04) × 103 ohm−1 cm−1 and the conductivity is of the n-type. The oxide contains variable amounts of water, which it retains very tenaciously.
PERFLUOROALKYL ARSENICALS: PART IV. SOME REACTIONS OF TRIFLUOROIODOMETHANE WITH ALKYL ARSINES
Authors: Cullen W. R.
Published: May 2006

Trifluoroiodomethane reacts with triethyl- and tri-n-butylarsine, and tri-n-butylphosphine to give products of the type R2MCF3. Heptafluoroiodopropane reacts similarly with trimethylarsine. Trifluoroiodomethane also reacts with the compounds (CH3)2AsX (X = C6H5, Cl, I) and CH3AsI2 to give CH3As(CF3)2; and in most of these reactions the compound CH3As(CF3)I is also formed, which is converted to the compound CH3As(CF3)Cl by reaction with silver chloride.
THE INTERACTION OF FRIEDEL–CRAFTS CATALYSTS WITH ORGANIC MOLECULES: II. BORON TRIFLUORIDE WITH BENZOIC ANHYDRIDE
Authors: Cook Denys
Published: May 2006

The complex of boron trifluoride with benzoic anhydride has been prepared. One molecule of anhydride coordinates three molecules of boron trifluoride. The infrared spectrum shows that coordination takes place at the carbonyl groups, whose frequency is lowered some 200 cm−1. There is no trace of the benzoylium cation, C6H5O+. Although the spectra are complex, tentative assignments are made.
THE INTERACTION OF FRIEDEL–CRAFTS CATALYSTS WITH ORGANIC MOLECULES: III. THE CH3COCl:GaCl3 SYSTEM
Authors: Cook Denys
Published: May 2006

The equimolar complex of acetyl chloride and gallium trichloride has been prepared and its infrared spectrum, both in the pure state and in nitrobenzene solution, has been recorded. In the pure complex a strong band at 2300 cm−1, hitherto attributed to the acetylium ion, has been observed. In solution in nitrobenzene, the 2300 cm−1 band is almost completely replaced by one at 2200 cm−1, while undissociated CH3COCl is present. Certain bands in this spectrum are consistent with the presence of the nitrobenzene – gallium chloride complex. A re-evaluation of the assignments of the acetylium ion suggests that a more complicated ionic species may be present in the solid state, possibly [CH3CO … GaCl3]+Cl−.