Showing papers in "Canadian Journal of Chemistry in 1962"
TL;DR: In this article, second-order perturbation theory is used to determine the manner in which the electron density present in a molecule is changed during a nuclear vibration, which is useful in determining the manner of electron density change.
Abstract: It is demonstrated that second-order perturbation theory is useful in determining the manner in which the electron density present in a molecule is changed during a nuclear vibration. Furthermore, ...
320 citations
TL;DR: The yield of extracellular glycolipid produced by Torulopsis magnoliae is increased three to fivefold by the addition of suitable compounds to the growing culture as mentioned in this paper.
Abstract: The yield of extracellular glycolipid produced by Torulopsis magnoliae is increased three-to five-fold by the addition of suitable compounds to the growing culture. The supplement, which can be a l...
143 citations
TL;DR: In this article, the Raman spectra of sulphuric acid, deuterosulphuric acids, chlorosulphyllophonic acid, and methanesulphonic acid were determined for the first time.
Abstract: The Raman spectra of sulphuric acid, deuterosulphuric acid, chlorosulphuric acid, and methanesulphonic acid have been redetermined, and the spectrum of fluorosulphuric acid measured for the first time. The spectra of fluorosulphuric acid – sulphuric acid, chlorosulphuric acid – sulphuric acid, and fluorosulphuric acid – arsenic trifluoride mixtures have also been measured. The spectra of the hydrogen sulphate, deutero sulphate, fluorosulphate, chlorosulphate, and methanesulphonate anions have been obtained in various solvents. Frequencies are assigned to the normal modes of vibration of all these acids and their anions and the assignments are compared with those of previous workers.
119 citations
TL;DR: A sensitive spray reagent has been developed for the analytical detection of acetates on the chromatographic plates and is based on the formation of the ferric hydroxamate of acetic acid.
Abstract: Thin layer chromatography on silica gel G with benzene–methanol mixtures is a rapid method for the analytical or semimicro preparative separation of low molecular weight carbohydrate acetates. Some...
113 citations
TL;DR: In this paper, the Stern-Grahame-Devanathan theory of the electrical double layer in aqueous systems is modified to include the so-called discreteness-of-charge effect of Esin and Shikov and Ershler.
Abstract: The Stern–Grahame–Devanathan theory of the electrical double layer in aqueous systems is modified to include the so-called discreteness-of-charge effect of Esin and Shikov and Ershler. This provide...
102 citations
TL;DR: The propagation step in the butyllithium-initiated polymerization of styrene in benzene solution is thought to be due to a small concentration of highly active free ion-pairs in equilibrium with un...
Abstract: The propagation step in the butyllithiuminitiated polymerization of styrene in benzene solution is thought to be due to a small concentration of highly active free ion-pairs in equilibrium with un...
98 citations
TL;DR: In this article, the thermal decomposition of TaX5 (X = NMe2, NEt2, NPr2N, NBu2n, NMeBun, and NC5H10) was shown to produce substantially the pentaderivatives TaCl5 and LiX.
Abstract: Reactions involving TaCl5 and LiX (where X = NMe2, NEt2, NPr2n, NBu2n, NMeBun, and NC5H10) were shown to produce substantially the pentaderivatives TaX5. The thermal decomposition of TaX5 (X = NMe2...
90 citations
TL;DR: In this paper, a strong correlation was found between the electronegativity, Ex, and the three proton coupling constant of the vinyl group in over a hundred compounds of the type CH2
Abstract: A strong correlation is found between the electronegativity, Ex, and the three proton coupling constant of the vinyl group in over a hundred compounds of the type CH2 = CHX. This correlation extends over the range Ex = 4 to 1 and over the range Jgem + Jcis + Jtrans = 14 to 50 c.p.s. Simple implications and some useful applications of this correlation are discussed.
88 citations
TL;DR: Three related diterpenoid quinones, royleanone, 9-acetoxyroyleanones, and 9-dehydroroyleanone, have been isolated from the roots of Inula royleana D. C..
Abstract: Three related diterpenoid quinones, royleanone, 9-acetoxyroyleanone, and 9-dehydroroyleanone, have been isolated from the roots of Inula royleana D. C. These have been assigned structures on the ba...
86 citations
TL;DR: In this article, the poly-β-D-glucan of Cetraria islandica (Iceland moss) was found by enzymic degradation to differ in fine structure from the polyβ-βDglucans of cereal grains.
Abstract: 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 carr
85 citations
TL;DR: From the analysis of the concentration dependence of the relaxation times, it was concluded that each system could be represented by the reactions where P refers to BSA or Ab, and D to N-R′ or NS—R′.
Abstract: The kinetics of protein–dye and antibody–hapten reactions were studied with the temperature-jump method. The systems used consisted of (i) bovine serum albumin (BSA) and the dye 1-naphthol-4-[4-(4′-azobenzene azo)phenyl arsonic acid], referred to as N—R′, (ii) BSA and the dye 1-naphthol-2-sulphonic acid-4-[4-(4′-azobenzene azo)phenyl arsonic acid], referred to as NS—R′, and (iii) rabbit antibodies to phenyl arsonic acid [Ab] and the hapten N—R′.Each of the systems exhibited a single relaxation time. From the analysis of the concentration dependence of the relaxation times, it was concluded that each system could be represented by the reactionswhere P refers to BSA or Ab, and D to N—R′ or NS—R′. The following rate constants were calculated for the three systems at 25 °C:The effects of temperature and pH on the rate constants of the system BSA – N—R′ are discussed.
TL;DR: In this article, the infrared spectra of CO and CO2 adsorbed on chromia-alumina and on alumina surfaces were determined, and a band near 2200 cm−1 formed by CO on both surfaces at room temperature was due to a weak, n...
Abstract: Infrared spectra of CO and CO2 adsorbed on chromia–alumina and on alumina surfaces have been determined. A band near 2200 cm−1 formed by CO on both surfaces at room temperature was due to a weak, n...
TL;DR: In this article, the authors measured the NH2 stretching vibrations in 33 ortho-substituted anilines, measured in dilute carbon tetrahedron, and integrated the integrated intensities, frequencies, and half-band widths of the fundamental symmetric and asymmetric NH 2 stretching vibrations.
Abstract: The integrated intensities, frequencies, and half-band widths of the fundamental symmetric and asymmetric NH2 stretching vibrations in 33 ortho-substituted anilines, measured in dilute carbon tetra...
TL;DR: In this article, the authors used styrene as the substrate, 2,6-di-tert-butyl-4-methyl-phenol as the inhibitor, and azo-bis-isobutyronitrile as the initiator.
Abstract: Most previous work on the inhibition of autoxidation by phenols has indicated that the reaction involves abstraction of the phenolic hydrogen. However, the apparent absence of any appreciable deuterium isotope effect made it difficult to believe that abstraction could be rate controlling. The present work using styrene as the substrate, 2,6-di-tert-butyl-4-methyl-phenol as the inhibitor, and azo-bis-isobutyronitrile as the initiator has shown that this reaction has an unexpectedly large isotope effect, e.g. ~10.6 at 65 °C. Previous failures to detect an isotope effect are attributed to the rapid exchange of deuterium which takes place between deuterated phenols and traces of moisture or other hydroxyl-containing compounds present in the substrate. Rate constants and activation energies for some of the elementary reactions in the inhibited and uninhibited oxidation of styrene have been measured. It is suggested that a compound which functions in the same way as a weak phenolic inhibitor is formed in the ap...
TL;DR: The first bacterial polysaccharide reported to contain pyruvic acid as a constituent was Polysaccharides B-1459, isolated as the potassium salt, was shown to be composed of D-gluc... as mentioned in this paper.
Abstract: Polysaccharide B-1459 is the first bacterial polysaccharide reported to contain pyruvic acid as a constituent. The polysaccharide, isolated as the potassium salt, was shown to be composed of D-gluc...
TL;DR: The photodimer of coumarin is shown to have the head-to-head cis cyclobutane structure I as mentioned in this paper, and an isomer, obtained by the lactonization of o-hydroxy-trans-cinnamic acid, is also shown to possess the headto-tai
Abstract: The photodimer of coumarin is shown to have the head-to-head cis cyclobutane structure I. An isomer, obtained by the lactonization of o-hydroxy-trans-cinnamic acid, is shown to have the head-to-tai...
TL;DR: In this article, it was 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 in a dihedral configuration.
Abstract: 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 i...
TL;DR: In this paper, the effects of structure on the shielding of formyl protons of aliphatic aldehydes have been examined and the potential use of these results as an aid for structural elucidations is discussed.
Abstract: The effects of structure on the shielding of formyl protons of aliphatic aldehydes have been examined. The survey included examples of acyclic, alicyclic, and α, β-unsaturated aldehydes. The potential use of these results as an aid for structural elucidations is discussed, and the limitations are noted.
TL;DR: The diffuse absorption bands of HON14O, HON16O, DON16O and DON15O in the near ultraviolet have been examined in this article, where the authors attributed the weakening of the internal hydrogen bond in the cis state upon an electronic promotion of primarily nO→π* type.
Abstract: The diffuse absorption bands of HON14O, HON16O, DON16O, and DON15O in the near ultraviolet have been examined. Transitions from both rotational isomers of nitrous acid contribute to the vibrational structure, with the excited state σ(N=O) stretching vibrations active in the most intense progressions. The cis–trans energy separation increases from 500 cal/mole in the ground state to 1200 cal/mole in the upper state. This is attributed to weakening of the internal hydrogen bond in the cis state upon an electronic promotion of primarily nO → π* type. The accompanying change in geometry is responsible for the appearance of the cis ground-state δ(ONO) bending mode in the spectrum.
TL;DR: In this paper, the reactions of D-xylose, methyl α-D-Xylofuranoside, and methyl β-Dxylopyranoside with methanolic hydrogen chloride under controlled conditions have been followed by gas-liquid partition chromato...
Abstract: 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 chromato...
TL;DR: In this article, the rate-controlling process in self-discharge of the nickel oxide electrode is the anodic partial reaction of oxygen evolution, based on a comparison of the two processes.
Abstract: Further evidence that the rate-controlling process in self-discharge of the nickel oxide electrode is the anodic partial reaction of oxygen evolution is reported and is based on: (a) comparison of ...
TL;DR: In this paper, the thermal decomposition of diazomethane (DM) into singlet methylene radicals and nitrogen has been studied from 225° to 450° in 10:1 olefin-diazomethsane mixtures.
Abstract: The thermal decomposition of diazomethane (DM) into singlet methylene radicals and nitrogen has been studied from 225° to 450° in 10:1 olefin–diazomethane mixtures. At 2.5 cm pressure, k = 1.2 × 1012 exp (−34,000/RT) sec−1. The methylene radicals have similar reactivity to methylene generated from photolytic decomposition of DM, as judged by the follow-up reactions with ethylene and cis-butene-2. The structural isomerization reactions of energized cyclopropane and the structural and geometric isomerization of 1,2-dimethyl-cyclopropane (DMC), formed from the addition of the thermally generated methylene to the olefins, were measured from 250° to 450° over a wide range of pressures. For comparison, cyclopropane formed from photolysis at 4358 A and 25° of DM and ethylene was studied. As judged from comparison of the experimental isomerization rate constants, the energy of the cyclopropanes formed at 350° in the thermal DM system is about the same as for cyclopropanes formed by photolysis at 4358 A of DM at 2...
TL;DR: The experimental evidence indicates that the Karplus curve, which relates the coupling constant between hydrogens on vicinal carbons and the dihedral angle defined by the hydrogens, is subject to displacement as discussed by the authors.
Abstract: The experimental evidence indicates that the Karplus curve, which relates the coupling constant between hydrogens on vicinal carbons and the dihedral angle defined by the hydrogens, is subject to displacement. An upward displacement of 2.2 c.p.s. is required to account for the coupling constants found for the neighboring hydrogens in both 1,3-dioxolane and its 2,2-dimethyl derivative. On this basis, the compounds exist in conformations wherein the cis neighboring hydrogens define dihedral angles of 35° and 41°, respectively.
TL;DR: In this article, the atisine family of diterpenoid acids with la-and ID-carbosyl groups were shown to have a stereochelnistic property, which was used to convert podocarpic acid to the enantiomer of the phenol I11.
Abstract: Irradiation of azides of diterpenoid acids with la- and ID-carbosyl groups gave the corresponding isocyanates and ca. 25% yields of lactams. The azide of hexanoic acid under cornparable conditions gave 8yo of hesanamide. The reaction has been used to convert podocarpic acid to the enantiomer of the phenol I11 derived from atisine. This colnpletes the structure proof of the atisine family of alkaloids, the Garrya alkaloids, and related diterpenes, and proves the absolute stereochelnistry of these substances.
TL;DR: This paper showed that Niobium pentachloride and lithium dialkylamides (LiNR2) led to considerable reduction of niobium to Nb(IV) as the length of the alkyl chains increase.
Abstract: Reactions involving niobium pentachloride and lithium dialkylamides (LiNR2, where R = Me, Et, Prn, Bun) led to considerable reduction of niobium to Nb(IV) as the length of the alkyl chains increase...
TL;DR: In this article, the isotopic vibrational frequencies and partition function ratios for various Se76- and Se82-containing compounds have been calculated using "normal vibration equations" and statistical mechanics.
Abstract: Using "normal vibration equations" and statistical mechanics, the isotopic vibrational frequencies and the partition function ratios for various Se76- and Se82-containing compounds have been calculated. The equilibrium constants for selenium isotope exchange reactions derived from these partition function ratios indicate that noticeable fractionation of selenium isotopes can be expected in the laboratory and in naturally occurring processes.The Se82/Se76 ratios for 16 natural samples have been compared mass spectrometrically. Variations of up to 1.5% found in this ratio are discussed.A kinetic isotope effect of 1.5% found in a chemical reduction of selenite ion to elemental selenium is also discussed.
TL;DR: In this paper, an experimental investigation of the univariant pressure-temperature stability lines for the complexes has been made and the thermodynamic functions calculated: the heat content change for complex dissociation is between 9 and 13kcal/mole of olefin liberated.
Abstract: Interaction of solid silver fluoborate with the gaseous olefins ethylene, propylene, and the four butenes has been observed to provide 12 new stoichiometric solid coordination compounds (silver fluoborate – olefin complexes) of high stability. Experimental investigation of the univariant pressure–temperature stability lines for the complexes has been made and the thermodynamic functions calculated: the heat content change for complex dissociation is between 9 and 13 kcal/mole of olefin liberated. Infrared spectra of the complexed olefins indicate that the strength of the silver–olefin bond is primarily dependent upon the basicity of the olefin and a comparison of the thermodynamics of dissociation shows anomalous behavior on the part of isobutylene and trans-2-butene as compared with the regularity displayed by the other four olefins.
TL;DR: In this paper, structure activity relationships in the muscarine and the quaternary 1,3-dioxolane (Fourneau series) series are briefly discussed, and the most active member of the latter series (2-methyl-4-dimethylaminomethyl-1,3dioxoline methiodide, F2268) was shown to consist of a mixture of 60% cis and 40% trans isomers.
Abstract: Structure activity relationships in the muscarine and the quaternary 1,3-dioxolane (Fourneau series) series are briefly discussed. The most active member of the latter series (2-methyl-4-dimethylaminomethyl-1,3-dioxolane methiodide, (IX), F2268) was shown to consist of a mixture of 60% cis and 40% trans isomers. The same was found to apply to all synthetic intermediates in that series. Unequivocal assignments of configuration were made by relating various intermediates leading to (IX) and its analogs to D-cis-1,3-dimethyl-1,3-dioxolane itself, obtained by degradation of 1,6-anhydrogalactose. Attempted separation of cis–trans isomers in the 1,3-dioxolane series was not successful. However, a mixture of cis, trans-2-trichloromethyl-4-hydroxymethyl-1,3-dioxolane (XVI) could be fractionated by crystallization of the corresponding tosylates. Catalytic hydrogenolysis converted the pure cis- and trans-trichloromethyl derivatives (XVII) and (XVIII) to pure cis- and trans-2-methyl-4-hydroxymethyl-1,3-dioxolane tos...
TL;DR: The following coordination complexes of titanium (IV) have been prepared: TiCl4•2CO(NH2)2, TiCl 4•CO(NHC6H5)2 and 2TiCl4-CSN(C6H 5)2; their infrared spectra have been measured and their molecular weight determined.
Abstract: The following coordination complexes of titanium (IV) have been prepared: TiCl4•2CO(NH2)2, TiCl4•CO(NHCH3)2, TiCl4•2CO(NHCH3)2, 2TiCl4•2NH2CON(C6H5)2, 2TiCl4•2CO(NHC6H5)2 TiCl4•2CS(NH2)2, 2TiCl4•CS(NHC2H5)2, 2TiCl4•NH2CSN(C6H5)2, and 2TiCl4•CS(NHC6H5)2; their infrared spectra have been measured and their molecular weight determined. For urea and its derivatives the coordination to titanium (IV) is always through the oxygen atom. The phenyl derivatives of urea led to dinuclear complexes which were best explained by assuming halogen bridging between the titanium atoms. Thiourea and its derivatives gave complexes in which coordination occurred through one of the nitrogens in the case of thiourea and through both nitrogens in the case of the derivatives. Halogen bridging was again assumed to explain the formation of the dinuclear complexes.
TL;DR: The molecular complexes of urea and even-numbered n-paraffins up to C28 undergo thermal decomposition below the melting point of Urea at temperatures which increase with the nparaffin chain length.
Abstract: The molecular complexes of urea and even-numbered n-paraffins up to C28 undergo thermal decomposition below the melting point of urea at temperatures which increase with the n-paraffin chain length...