bluuebunny/crossref_metadata_2025 huggingface dataset:
THE CHEMICAL SHIFT OF AROMATIC ALKOXY GROUPS
Authors: Heathcock Clayton
Published: May 2006

The nuclear magnetic resonance (n.m.r.) spectra of 42 variously substituted anisoles and phenetoles have been obtained. The chemical shifts of the alkoxy hydrogens have been assembled in charts for ready use in interpreting the n.m.r. spectra of unknown compounds. For meta- and para-substituted anisoles, a reasonably good correlation has been shown to exist between the methyl resonance and the corresponding Hammett σ parameter. With anisole itself, a preferential solvent effect has been noticed which suggests a specific type of interaction between solute molecules.
STEREOCHEMISTRY OF ARSENIC: V. CRYSTAL DATA FOR TRIARYLARSINES
Authors: Trotter J.
Published: May 2006

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THE DE-O-ACETYLATION OF ACETYLATED AMINO SUGARS
Authors: Whitaker D. R. , Tate M. E. , Bishop C. T.
Published: May 2006

not available
METHYLATION OF SUGAR DITHIOACETALS: IV.D-XYLOSE DIETHYL DITHIOACETAL
Authors: Dutton G. G. S. , Tanaka Y.
Published: May 2006

Partial methylation of D-xylose diethyl dithioacetal in tetrahydrofuran with methyl iodide and silver oxide yielded 2-, 3-, and 5-O-methyl-D-xyloses in the ratio of 20:10:1. The poly-O-methylated components were not examined. The 2-O-methyl-D-xylose was identified as the crystalline sugar and the 3-O-methyl ether as the phenylosazone and p-bromophenylosazone. An alternative preparation of the dithioacetal in tetrahydrofuran solution is described.
ISOTOPE EFFECTS IN NEUTRAL H2O–D2O IRRADIATED SOLUTIONS AND THE NATURE OF THE REDUCING RADICAL
Authors: Lifshitz Chava
Published: May 2006

Neutral solutions of sodium formate in H2O–D2O mixtures were irradiated by 200-kv X rays. The atomic deuterium isotope effect (αA) and its dependence on deuterium concentration were determined. In a 1 × 10−1 M HCOONa, 96% D2O solution, G(hydrogen) = 1.14 and αA = 4.3. It is concluded that the hydrogen atom cannot be formed from a single water molecule. Possible mechanisms of hydrogen atom formation are discussed. The alternative possibilities for the atoms to react as H or H2O− are viewed in the light of the proposed mechanisms.
ORGANOPHOSPHORUS COMPOUNDS: IX. DIARYL PHOSPHOROFLUORIDATES AND DIARYL PHOSPHOROFLUORIDOTHIOATES
Authors: Olah George A. , Oswald Alexis A.
Published: May 2006

Diaryl phosphorofluoridates and diaryl phosphorofluoridothioates were prepared and their properties investigated.
A PROPOSED STRUCTURE FOR ANNEALED ANODIC OXIDE FILMS OF TANTALUM
Authors: Calvert L. D. , Draper P. H. G.
Published: May 2006

Anodic oxide films (~1500 Å thick) formed on tantalum in saturated H3BO3, saturated Na2SO4, 86% H3PO4, 1% H2SO4, and 100% H2SO4 have been examined by a simple but sensitive glancing angle X-ray technique. They are amorphous as formed but can be crystallized on annealing at various temperatures between 500 and 1000 °C. The times and temperatures required for crystallization depend on the electrolyte used. The crystallization process is competitive with the dissolution of oxygen in the substrate metal. The observed powder diffraction patterns show considerable variation from sample to sample. Similar variations have been reported in the literature for different samples of Ta2O5. A structural model is proposed for β-Ta2O5 based on the isostructural relationship with U2O5, whose structure is related to that of α-UO3. This proposed structure consists of linear chains of Ta—O—Ta—O— parallel to the c axis with varying disorder in the ab plane. This disorder accounts for the observed variations in the patterns. The proposed structure is a defect one and the ordering of these defects may account for some of the reports of irreversible transformations observed on heating Ta2O5.
ORGANOPHOSPHORUS COMPOUNDS: X. PHOSPHORISOCYANATIDIC DIFLUORIDE AND CHLORIDE FLUORIDE. PREPARATION OF ALKYL CARBAMATOPHOSPHORODIFLUORIDATES AND UREIDOPHOSPHORODIFLUORIDATES
Authors: Kuhn Stephen J. , Olah George A.
Published: May 2006

Phosphorisocyanatidic difluoride and phosphorisocyanatidic chloride fluoride were prepared. Addition reactions with alcohols (phenol) and amines were investigated, leading to carbamatophosphorodifluoridates and ureidophosphorodifluoridates.
OBSERVATIONS ON THE KARPLUS CURVE IN RELATION TO THE CONFORMATION OF THE 1,3-DIOXOLANE RING
Authors: Lemieux R. U. , Stevens J. D. , Fraser R. R.
Published: May 2006

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.
GAS–LIQUID CHROMATOGRAPHIC ANALYSIS OF LIGNIN OXIDATION PRODUCTS
Authors: Pepper J. M. , Manolopoulo M. , Burton R.
Published: May 2006

The gas–liquid chromatographic separation of vanillin, syringaldehyde, and p-hydroxybenzaldehyde has been effected using a 15% Apiezon N on Fluoropak column at 220 °C. Using standard solutions of the reference compounds and measuring peak areas, the percentage composition of mixtures of milligram amounts of these aldehydes may be determined quantitatively to within 5%.The method has been applied to the quantitative analysis of the phenolic aldehydes resulting from the alkaline nitrobenzene oxidation of aspen and spruce wood and wheat straw meals as well as the lignins isolated from these same plant materials. The results are reproducible and generally in good agreement with those reported earlier for similar lignified substances as determined using the spectrophotometer method of Stone and Blundell.
CONCURRENT ION–MOLECULE REACTIONS LEADING TO THE SAME PRODUCTION
Authors: Harrison A. G. , Tait J. M. S.
Published: May 2006

Seven of the major secondary ions in the high-pressure mass spectrum of cyclopropane have been studied. A method has been developed for studying concurrent ion–molecule reactions and it has been shown that four of the secondary ions are the products of more than one reaction. Cross sections for the separate reactions are reported. The appearance potentials of the major primary ions in the mass spectrum of cyclopropane have been measured.
REACTIONS OF METHYL RADICALS WITH NITRIC OXIDE
Authors: Hoare D. E.
Published: May 2006

Methyl radicals have been produced by the photolysis of acetone at 200 °C and their reaction with nitric oxide has been studied. The reaction CH3 + NO + M → CH3NO + M is shown to be third order with a rate constant of 8.8 × 10−31 cm6 molecule−2sec−1, with acetone as M. It is further shown that the nitrosomethane formed reacts with either methyl radicals or nitric oxide. The probability of reactions such as CH3CO + NO → CH3CO•NO taking place is shown.
EXTRACTIVES FROM POPULUS TREMULOÏDES HEARTWOOD: THE STRUCTURE AND SYNTHESIS OF TREMULONE
Authors: Abramovitch R. A. , Micetich R. G.
Published: May 2006

Tremulone, a dienone isolated from Populus tremuloïdes heartwood, has been shown to be stigmasta-3,5-diene-7-one. This has been confirmed by a partial synthesis from β-sitosterol. The possibility that tremulone might be an artifact arising from the isolation procedure is discussed.
THE PREPARATION AND INFRARED AND N.M.R. SPECTRA OF MONODEUTERATED PYRIDINE AND 3-PICOLINE
Authors: Abramovitch R. A. , Kroeger D. J. , Staskun B.
Published: May 2006

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THIOCARBONATES AS BLOCKING GROUPS FOR THE SYNTHESIS OF PARTIAL ESTERS OF CARBOHYDRATES
Authors: Willard J. J.
Published: May 2006

It has been found that the thiocarbonate, or (alkylthio)carbonyl derivative, serves as a versatile blocking group for the synthesis of partial ester derivatives of carbohydrates. The (alkylthio)carbonyl group is readily substituted in pyridine solution, is stable to mild acid conditions, but is decomposed by mild oxidation. Crystalline methyl 4,6-di-O-benzoyl-α-D-glucopyranoside has been synthesized and its structure proved by an independent synthesis of its 2,3-di-O-phenylcarbamate derivative. Methyl 4,6-di-O-benzoyl-β-D-glucopyranoside was also synthesized and its structure proved by acetylation to the known 2,3-di-O-acetyl derivative.
LYCOPODIUM ALKALOIDS: IV. THE CONSTITUTION AND STEREOCHEMISTRY OF LYCOCLAVINE, AN ALKALOID OF LYCOPODIUM CLAVATUM VAR. MEGASTACHYON
Authors: Ayer W. A. , Law D. A.
Published: May 2006

The alkaloids of Lycopodium clavatum var. megastachyon have been examined and two hitherto unreported alkaloids, lycoclavine and acetyllycoclavine, were isolated and their structures determined. The nuclear magnetic resonance spectra of these and related compounds are discussed in terms of the conformation of ring B in these alkaloids.
THE CONSTITUTION OF A SYNTHETIC XYLAN: II. CONTROLLED PERIODATE DEGRADATION
Authors: Dutton G. G. S. , Unrau A. M.
Published: May 2006

The controlled periodate degradation of the synthetic xylan resulted in the formation of ethylene glycol, glycerol, xylose, and at least eight non-reducing oligosaccharides. The composition, approximate D.P., periodate oxidation, and possible structure of these oligosaccharides are reported and discussed.
THE NUCLEAR MAGNETIC RESONANCE SPECTRA OF PARA-SUBSTITUTED PHENOLS
Authors: Paterson W. G. , Tipman N. R.
Published: May 2006

The nuclear magnetic resonance spectra of a number of para-substituted phenols have been examined. The —OH chemical shifts, extrapolated to infinite dilution in benzene and in carbon tetrachloride, were found to be almost independent of the nature of the ring substituent. Approximately linear relationships were observed between the internal chemical shift of the ring protons and other physical properties.
THE REACTION OF 4-PYRONES WITH HYDROXYLAMINE
Authors: Yates Peter , Jorgenson Margaret Jefraim , Roy Sunil Kumar
Published: May 2006

Treatment of 2,6-dimethyl-4-pyrone with hydroxylamine gives 4-hydroxyamino-2,6-lutidine 1-oxide. Under the influence of light or in weakly basic media this is converted in the presence of air to 4,4′-azoxydi-2,6-lutidine 1,1′-dioxide. In a strongly basic medium it is converted to 4,4′-azodi-2,6-lutidine 1,1′-dioxide. Similar results are obtained in the case of 2,6-diethyl-4-pyrone.
THE FRANCK–CONDON PRINCIPLE AND THE IONIZATION OF MOLECULES
Authors: Collin Jacques E.
Published: May 2006

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SOME EXAMPLES OF THE USE OF OXYGEN AS A DIAGNOSTIC TEST FOR THE TRIPLET STATE IN CHEMICAL REACTIONS
Authors: Setser D. W. , Placzek D. W. , Cvetanović R. J. , Rabinovitch B. S.
Published: May 2006

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EXOCELLULAR BACTERIAL POLYSACCHARIDE FROM XANTHOMONAS CAMPESTRIS NRRL B–1459: PART II. LINKAGE OF THE PYRUVIC ACID
Authors: Sloneker J. H. , Orentas Danute G.
Published: May 2006

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THERMAL DECOMPOSITION OF SODIUM AZIDE CRYSTALS
Authors: Secco E. A.
Published: May 2006

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SYNTHESIS OF DIPEPTIDES CONTAINING 1-AMINOCYCLOALKYLCARBOXYLIC ACIDS: PART II
Authors: Tailleur Patrice , Berlinguet Louis
Published: May 2006

Six new dipeptides containing either 1-aminocyclopentanecarboxylic acid or 1-aminocyclohexanecarboxylic acid placed at either the N-or the C-terminal of L-phenylalanine or L-leucine have been synthesized. Two molecules of 1-aminocyclopentanecarboxylic acid were also linked with a peptide bond. These seven dipeptides were cyclized into the corresponding substituted 2,5-piperazinediones.
COORDINATION COMPLEXES OF TITANIUM (IV) HALIDES: III. PREPARATION AND INFRARED SPECTRA OF THE COMPLEXES OF TITANIUM TETRACHLORIDE WITH UREA, THIOUREA, AND SOME OF THEIR DERIVATIVES
Authors: Rivest Roland
Published: May 2006

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.
PHYSICOCHEMICAL STUDIES OF WATER CHESTNUT STARCH (TRAPA BISPINOSA ROXB)
Authors: Murty V. L. N. , Choudhury D. , Bagchi P.
Published: May 2006

The starch present in the kernel of water chestnut (Trapa bispinosa Roxb) has been isolated and obtained free from protein. Potentiometric titration showed that the starch contained 15% amylose. The starch was resolved into amylose and amylopectin through complex formation. The components were characterized by chemical and enzymic techniques. The average length of unit chain has been shown to be 22 in the amylopectin and 360 in amylose by both methylation and periodate oxidation studies. Molecular weights of the two components by viscosity and light scattering are also described.
SPECTROSCOPIC STUDIES OF KETO–ENOL EQUILIBRIA: PART 2. ANOMALOUS ULTRAVIOLET ABSORPTION SPECTRA OF SATURATED 1,2-DICYANO ESTERS
Authors: Kasturi T. R. , Mylari B. N. , Balasubramanian A. , Rao C. N. R.
Published: May 2006

1,2-Dicyano esters show an absorption band around 245 mμ in alcoholic solutions which is not found in non-polar and other polar solvents. This anomalous behavior has been found to be due to the unusual solvent dependence of the equilibrium between the keto and enol forms. The intensity of the absorption band in alcoholic solutions decreases with increase in concentration of the 1,2-dicyano ester, indicating association of the enol form. The keto–enol equilibrium is also found to be sensitive to the substituent R of the alcohol ROH.
METAMECONINE AS A MODEL COMPOUND IN THE STUDY OF AROMATIC REACTIONS
Authors: Safe S. , Allen Marjorie , Moir R. Y.
Published: May 2006

Previous work had shown the somewhat unexpected course of nitration, bromination, and demethylation reactions of metameconine and its derivatives. The discovery that metameconine could easily be dinitrated enabled us to bring to light equally interesting results in the relative rates of reduction of the nitro groups, in the course of certain nucleophilic substitution reactions, in the activation of the methylene group, and in certain physical properties. Much of the work, past and present, now holds as its main interest the somewhat special character of a nitro group in the 7-position.
HYDROGEN ATOM RECOMBINATION IN THE FLOW SYSTEM ATTACHED TO A MASS SPECTROMETER AND USED FOR THE STUDY OF MERCURY-SENSITIZED REACTIONS
Authors: Kebarle P. , Avrahami M.
Published: May 2006

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THE STRUCTURE OF TUBEROSTEMONINE
Authors: Edwards O. E. , Feniak G.
Published: May 2006

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ON PAOLONI'S NOTE ENTITLED: THE STRUCTURE OF CARBOLINES AND RELATED COMPOUNDS
Authors: Abramovitch R. A.
Published: May 2006

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GAS–LIQUID CHROMATOGRAPHY OF TERPENES: PART VII. THE DEHYDRATION OF p-MENTHAN-8-OL
Authors: Rudloff E. von
Published: May 2006

Mixtures of cis- and trans-p-menthan-8-ol were prepared by hydrogenation of α-terpineol over platinum or palladium catalysts and the isomer ratios obtained were determined by gas–liquid chromatography. The dehydration of a 1:1 mixture, as well as of the pure stereoisomers, was studied with a number of reagents. Aqueous oxalic and acetic acids, fused potassium hydrogen sulphate, anhydrous oxalic, silicic, and boric acids, and "Florisil" promoted the typical acid-catalyzed dehydration, with p-menth-4(8)-ene and smaller amounts of isomeric p-menth-8-enes as the primary products, and p-menth-3-ene the final product owing to isomerization. With anhydrous silicic acid the latter was obtained in better than 80% yield. With non-acidic alumina, or thionyl chloride in excess pyridine, the main product was p-menth-8-ene (up to 90%); no isomerization to p-menth-3-ene was obtained. The possible reaction mechanisms are discussed.
ELECTRON SPIN RESONANCE OF AN X-RAY IRRADIATED SINGLE CRYSTAL OF DIKETOPIPERAZINE
Authors: Lin W. C. , McDowell C. A.
Published: May 2006

The electron spin resonance of an X-ray irradiated single crystal of diketopiperazine has been measured at 9 Gc/sec for various orientations of the crystal in the static magnetic field. From an analysis of the hyperfine structure observed we have been able to calculate the components of the hyperfine interaction tensor for the radical produced by the irradiation. The principal values for the hyperfine interaction tensor are similar to those found for the radical produced by the X-ray or γ-ray irradiation of glycylglycine and N-acetylglycine and is therefore attributed to a radical with a C—H fragment. The fine details of the spectrum indicate that the radical responsible for the electron resonance observed probably has the structure

[Formula: see text]which is formed from diketopiperazine by the loss of a hydrogen atom from one of the CH2 groups in that molecule.
SODIUM CHELATES OF ETHYLENEDIAMINETETRAACETIC ACID
Authors: Palaty Vladimir
Published: May 2006

The stability constant of the sodium chelate of EDTA was determined by means of a sodium-sensitive glass electrode. It appears that a hydrogen chelate of the formula NaHY2− is formed in the neutral solution of EDTA, but is very unstable. The stability constants, pKNaY = −2.61 and pKNaHY = 0.03, are comparable to the value obtained by Schwarzenbach and Ackermann under different experimental conditions by a less sensitive method.
NEW APPROACHES TO THE STUDY OF ELECTROCHEMICAL DECARBOXYLATION AND THE KOLBE REACTION: PART I. THE MODEL REACTION WITH FORMATE
Authors: Conway B. E. , Dzieciuch M.
Published: May 2006

The kinetics of electrochemical decarboxylation of formate ions has been studied in detail for the first time as a model reaction for examination of the decarboxylation and radical coupling that occurs with higher aliphatic acids. Current–potential curves have been obtained which show a sharp transition region, not diffusion controlled, which is characteristic of passivation phenomena. The behavior is observed with gold, palladium, platinum, and gold–palladium alloys. Tafel slopes and exchange currents have been evaluated for the reaction and possible reaction mechanisms are examined in relation to the experimental results.Galvanostatic charging, reverse pulse discharging, and open-circuit decay transients have been obtained which indicate formation of films of adsorbed intermediates on the surface. The transition regions in the current–potential curves are associated with formation of this ad-layer. The galvanostatic results enable distinctions to be made between some of the possible reaction mechanisms proposed and estimates to be made of the extent of film formation by adsorbed intermediates formed in the reaction.
NEW APPROACHES TO THE STUDY OF ELECTROCHEMICAL DECARBOXYLATION AND THE KOLBE REACTION: PART II. THE MODEL REACTION WITH TRIFLUOROACETATE AND COMPARISONS WITH AQUEOUS SOLUTION BEHAVIOR
Authors: Conway B. E. , Dzieciuch M.
Published: May 2006

Electrochemical kinetic studies on the Kolbe reaction have been carried out in the trifluoroacetate–100% trifluoroacetic acid system, where the reaction can be examined from an electrochemical viewpoint with minimum complication by oxidative side reactions. High yields of the Kolbe products C2F6 and CO2 are obtained and current–potential curves exhibiting transition behavior and linear Tafel regions are found. Tafel slopes are deduced for "Langmuir" and "Temkin" conditions of surface coverage by intermediates and compared with the experimental observations. Plausible reaction mechanisms are proposed, which are supported by galvanostatic discharge transients; the latter indicate that the coverage by adsorbed intermediates in the trifluoroacetate reaction approaches a monolayer. In the aqueous formate systems, multilayer formation is indicated, including deposition of layers of different species corresponding to different arrest regions in the galvanostatic discharge transients. It is suggested that these layers may consist of oxide and the discharged carboxylate and that the transition behavior and critical potentials in the Kolbe reaction correspond to conditions for passivation of the metal by oxide and carboxylate species.
THE ACIDITY FUNCTION, H0, IN AQUEOUS CONCENTRATED ACID AND SALT SOLUTIONS
Authors: Rosenthal Donald , Dwyer James S.
Published: May 2006

Some H0 measurements in concentrated LiCl solutions are reported. It is shown that the H0 values in 1–9 M LiCl, 1–9 M HClO4, and 1–11 M HCl solutions can be calculated using the equation[Formula: see text]where aw is the activity of water, C is either the molar or molal concentration, and n and B are least-squares constants. Values of n = 2 (molar equation) and n = 1 (molal equation) fit the experimental data better than does n = 4. With the molar equation a non-integral value of n for HClO4 is required to give reasonable H0 values. The adequacy and significance of integral and non-integral values of n are considered. The nature of the constant B is also discussed. A more general equation is developed which under certain conditions reduces to the simpler equation. The more general equation is based upon a model which assumes the existence of more than one hydrated form of the indicator base, its conjugate acid, and H3O+. Some of the implications of this more general equation are considered
PAPER CHROMATOGRAPHY OF ETHYLENEDIAMINE DIHYDROCHLORIDE AND DIACETATE IN ACIDIC SOLVENT SYSTEMS
Authors: Bannard R. A. B. , Casselman A. A.
Published: May 2006

Quantitative chromatography of ethylenediamine dihydrochloride on unwashed Whatman No. 17 paper in t-butanol:acetic acid:water (2:1:1) resulted in a 1% conversion to ethylenediamine diacetate (RF 0.51) and a 98% recovery of the dihydrochloride (RF 0.28). The cause of the multiple zoning, which was not observed on acid-washed papers, was traced to minor quantities of alkaline earth metals which are present as impurities in unwashed papers. Ion exchange mechanisms are suggested to account for the observed conversion. Quantitative chromatography of ethylenediamine diacetate on unwashed or acid-washed Whatman No. 17 paper in t-butanol:0.5% hydrochloric acid (3:1) resulted in quantitative recovery of the dihydrochloride due to displacement of the weak acid in the substrate by the strong acid in the solvent system.
PHOTOCHEMICAL SYNTHESES: SULPHENES AS PHOTOCHEMICAL INTERMEDIATES
Authors: King J. F. , Mayo P. De , Morkved E. , Sattar A. B. M. A. , Stoessl A.
Published: May 2006

The present status of sulphenes (R′R″C:SO2) as stable entities or chemical intermediates is discussed. The early report by Locher and Fierz (Helv. Chim. Acta, 10, 642 (1927)) of the preparation of a stable crystalline sulphene has been investigated; it is concluded that their claim is unfounded.The irradiation of unsaturated sultones in the presence of methanol is shown to give sulphonic esters: the corresponding thermal reaction of sultones is known to lead to sulphonic acid derivatives. It is proposed that the irradiation of unsaturated sultones yields sulphenes, which then react with the medium.
THE CHEMISTRY OF THE AMINOCHROMES: PART V. REARRANGEMENTS IN THE PRESENCE OF SODIUM HYDROXIDE AND ZINC ACETATE
Authors: Heacock R. A. , Mattok G. L.
Published: May 2006

The rates of rearrangement of several aminochromes have been measured in: (1) water, (2) aqueous sodium hydroxide, and (3) aqueous zinc acetate. The rates were found to be first order with respect to aminochrome concentration in each reaction medium, and to zinc acetate concentration. However, no simple kinetic relationship between the rate of rearrangement and alkali concentration was detected. The rate increased very rapidly with increasing alkali concentration.Mechanisms for these rearrangements are suggested, based on the influence of substituents in the 1-, 2-, and 3-positions of the aminochrome molecule on the kinetic and thermodynamic features of the reaction.
THE STRUCTURE OF PULCHERRIMINIC ACID
Authors: MacDonald J. C.
Published: May 2006

The red pigment pulcherrimin was isolated from three strains of Candida pulcherrima and converted to pulcherriminic acid. The properties of derivatives of this acid and the products obtained from its reduction indicate that it differs from pulcherriminic acid isolated by other workers. A probable structure for the new pulcherriminic acid is 2,5-diisobutyl-3,6-dihydroxy-pyrazine-1,4-dioxide. The structures of the compounds obtained from its reduction were also investigated.
PRESSURE-INDEPENDENT FLOW SYSTEM PYROLYSIS OF DIMETHYL MERCURY
Authors: Krech M. , Price S. J.
Published: May 2006

The pyrolysis of HgMe2 has been investigated in a benzene carrier system using temperatures from 693 °K to 800 °K and pressures from 0.36 cm to 26.0 cm. High-pressure limiting rate constants were obtained above approximately 10 cm pressure. The high-pressure activation energy, E0, of 53.7 ± 0.5 kcal/mole is identified with D(MeHg—Me) within the limits D < E0 < D + RT.
SYNTHESIS OF SOME PHENAZINE DERIVATIVES
Authors: Stammer Chaim , Taurins Alfred
Published: May 2006

Nitration of 2-amino-, 2-N-methylamino-, and 1-amino-phenazine resulted in the formation of 2-amino-1-nitro-, 2-N-methylamino-1-nitro-, and 1-amino-4-nitro-phenazine, respectively. Nitration of 2-aminophenazine was shown to proceed via the intermediate nitramine, which was isolated and identified. 2-Hydroxy-1-nitrophenazine was found to exist in the solid state exclusively in the hydroxy form, and 4-nitro-1(5H)-phenazinone was the only solid obtained on acidification of a 1-hydroxy-4-nitrophenazine salt solution.
HINDERED DIPHENYL ETHERS RELATED TO THE BISBENZYLISOQUINOLINE ALKALOIDS
Authors: Allen Marjorie , Moir R. Y.
Published: May 2006

Sixteen steps from vanillin led to syntheses of (a) dimethyl 3-(4′-carbomethoxyphenoxy)-4,5-dimethoxyphthalate (Ic), a known degradation product of isochondrodendrine, and (b) the more hindered dimethyl 3-(4′-carbomethoxy-2′-methoxyphenoxy)-4,5-dimethoxyphthalate (Ia), which has not been derived from any alkaloid, though the usual concepts of biosynthesis do not rule out the occurrence of alkaloids which could lead to it. Diphenyl ethers related to Ia would be expected to show the effects of steric hindrance, but even with the most hindered member of the group, 7-(4′-carboxy-2′-iodophenoxy)metameconine (VAe), no evidence for an appreciable half-life of rotational isomers could be obtained. Attempts to make diphenyl ethers through the condensation of phenols with dicyclohexylcarbodiimide led to other products.
FLUORESCENCE EFFICIENCY OF CYCLOPENTANONE VAPOR AND ITS RELATION TO PHOTOLYSIS
Authors: Paglia S. R. La , Roquitte B. C.
Published: May 2006

Cyclopentanone vapor, when excited by light of wavelength 3130 Å, gives rise to four different photoproducts and fluorescence. The photochemistry of the molecule has been investigated by Srinivasan (J. Am. Chem. Soc. 81, 1546 (1959); 83, 4344, 4348 (1961)). In the present work the fluorescence spectrum and fluorescence efficiency of cyclopentanone vapor are reported for the first time. The fluorescence spectrum is identical with that obtained from liquid solutions of cyclopentanone, with a maximum at 4100 Å. Time, temperature, oxygen, and inert gases do not affect the spectrum, which contains no component ascribable to phosphorescence, maximum 4450 Å. Beer's law is obeyed.The fluorescence efficiency is also found to be independent of the variables temperature and pressure of inert gas, cyclopentanone, and oxygen. This is in marked contrast with the behavior of the photochemical yields (see work by Srinivasan). The yields of cyclobutane and ethylene tend to increase at high vibrational energy content of the excited molecule (low pressure, high temperature, short exciting wavelengths), while the yield of pentenal increases under conditions of decreasing vibrational energy content (high pressures, etc.). The fact that fluorescence stabilization does not occur in cyclopentanone can be related to the results of photolysis.
THE ABSOLUTE CONFIGURATION OFdextro-1-DEUTERIOETHANOL
Authors: Lemieux R. U. , Howard J.
Published: May 2006

Reduction of 1,2-O-isopropylidene-3-O-benzyl-5-oxo-α-D-xylofuranose with lithium aluminum deuteride followed by removal of the isopropylidene and benzyl groups provided 5-deuterio-D-xylose. Nuclear magnetic resonance examination of the 5-deuterio-β-D-xylopyranose tetraacetate showed the isomer with the 5-carbon in the R-configuration (deuterium equatorial) to be present in 30% excess. The substance was degraded to 1-deuterioethanol, which possessed a dextrorotation of the magnitude expected and which necessarily possessed the R-configuration. This result confirmed the prediction made by Brewster (Tetrahedron Letters, 20, 23 (1959)).
PERFLUOROALKYL ARSENICALS: PART VI. SOME REACTIONS OF TRISTRIFLUOROMETHYLARSINE AND DICHLOROTRIFLUOROMETHYLARSINE
Authors: Cullen W. R.
Published: May 2006

Tristrifluoromethylarsine reacts with arsenic trichloride at 210° to give dichlorotrifluoromethylarsine. Attempts to prepare trifluoromethyl derivatives of mercury, boron, and aluminum by interaction of trifluoromethylarsine with halides of these elements have been unsuccessful. Tristrifluoromethylarsine is stable to phosphorus at 220° but reacts with nitric oxide at 70° to give nitrogen and low yields of trifluoronitroso- and trifluoronitro-methane. It probably forms a weak 1:2 complex with pyridine.Dichlorotrifluoromethylarsine is easily reduced, at 20°, to trifluoromethylarsine by shaking with hydrogen chloride in the presence of mercury. Pyridine reacts with the chloroarsine at 20°.
THE ZINC CHLORIDE CATALYZED MIGRATION OF HALOGEN IN THE CLAISEN REARRANGEMENT
Authors: Piers E. , Brown R. K.
Published: May 2006

The zinc chloride catalyzed rearrangement of allyl 2,6-dichlorophenyl ether in nitrobenzene solution gave a good yield of 2-allyl-4,6-dichlorophenol along with some 2,6-dichlorophenol and 2-methyl-5,7-dichlorocoumaran. The coumaran increased at the expense of the 2-allyl-4,6-dichlorophenol. This is in contrast to the thermal rearrangement of this ether, which gave mainly 4-allyl-2,6-dichlorophenol along with smaller amounts of 2-allyl-6-chlorophenol and 2-allyl-4,6-dichlorophenol.
PROTON MAGNETIC RESONANCE ABSORPTION IN ETHYL STEARATE
Authors: Grant R. F. , Williams D. Llewelyn
Published: May 2006

The proton magnetic resonance absorption in ethyl stearate has been investigated at −77, 0, and 24 °C in the solid β-phase and at 28 °C in the solid α-phase. Spin-lattice proton magnetic resonance relaxation times were measured in the liquid up to 75 °C and in the solid α-phase. The results suggest that the α-phase is composed partly of molecules in a liquid-like state and partly of molecules constrained to rotate about their longitudinal axes. The results also support the proposal that the dielectric dispersion observed in the β-phase is due to molecular motion in crystal defects.
THE PROTON RESONANCE SPECTRA OF BENZYL ACETONE
Authors: Danyluk Steven S.
Published: May 2006

The proton resonance spectra of benzyl acetone (4-phenyl-2-butanone) are reported in a variety of solvents at 23 °C. A marked solvent dependence is noted for the CH3 group and the methylene protons adjacent to the keto group. The shifts to high field in aromatic solvents are interpreted in terms of a specific dipole-induced interaction with solvent molecules.The signals for the two non-equivalent pairs of methylene protons show changes in coupling constant with temperature. From this it is concluded that rapid rotation occurs about the C—C bond in the temperature range investigated with an increase in population of the trans conformation at low temperature. Significant changes in relative chemical shifts are also noted with temperature change for the two pairs of methylene protons and are attributed to the formation of weak molecular complexes in aromatic solvents.
PHOTOCHEMICAL SYNTHESES: 6. THE FORMATION OF HEPTANDIONES FROM ACETYLACETONE AND ALKENES
Authors: Mayo P. De , Takeshita H.
Published: May 2006

The irradiation of acetylacetone in the presence of oct-1-ene, cyclopentene, cyclohexene, and 1-methylcyclohexene gives substituted heptandiones. These diketones may then be cyclized with acid or base. Irradiation of isopropenyl acetate and acetylacetone gives, after cyclization, m-5-xylenol. The mechanism of the reaction is discussed: it represents the first cycloaddition to an isolated ethylenic linkage.
THE QUENCHING OF MERCURY RESONANCE RADIATION BY HYDROCARBONS: THE EFFECT OF DEUTERIUM SUBSTITUTION
Authors: Rousseau Yves , Gunning Harry E.
Published: May 2006

The effect of deuteration on the quenching cross section (σQ2) has been determined for propane, cyclopropane, isobutane, and propylene. The results were as follows, with the σQ2 values, in Å2, in parentheses: C3H8 (1.2); CH3CD2CH3 (0.17); CD3CH2CD3 (1.0); C3D8 (0.09); cyclo-C3D6 (0.29); (CH3)3CH (4.8); (CH3)3CD (0.44); C3H6 (29.8); and C3D6 (28.7). The deuterium isotope effect is most pronounced in the secondary C—H bonds of propane, and the tertiary C—H bond of isobutane. In the latter case, the isotope effect is estimated to be 15–16. For propylene, perdeuteration has little, if any, effect on σQ2, indicating that C—H bonds are not involved in quenching. Further implications of the results with respect to the quenching process are discussed.
TOTAL SYNTHESIS OF STEROIDAL DERIVATIVES: II. SYNTHESIS OF HYDROCHRYSENE ANALOGUES AND RELATED COMPOUNDS
Authors: Kutney James P. , Winter John , McCrae Wm. , By Arnold
Published: May 2006

A synthetic sequence leading to the total synthesis of hydrochrysene derivatives possessing the trans–anti–trans backbone is described. The introduction of a ketonic function into ring C of these compounds is also given. It is noted that these substances allow entry into the synthesis of intermediates which have an open ring C.
THE PREPARATION OF SOME NEW 1-PHENYL-2-NITROETHANOL DERIVATIVES
Authors: Heacock R. A. , Hutzinger O.
Published: May 2006

not available
BIOSYNTHESIS OF PLANT CONSTITUENTS: I. THE COMPLETE DEGRADATION OF 2-DEOXY-D-RIBOSE AND SOME 2-DEOXY-D-HEXOSES
Authors: Unrau A. M. , Canvin D. T.
Published: May 2006

A simple procedure is described whereby the complete stepwise degradation of 2-deoxy-D-ribose was achieved. Yields as high as 90% or better of the available carbon was obtained. The 2-deoxy pentose was reduced (KBH4) to the corresponding polyol and the latter oxidatively cleaved with periodate. Formic acid (C4) was converted to CO2quantitatively by oxidation with HgO. Formaldehyde and β-hydroxypropionaldehyde were oxidized with bromine. Formic acid (C5) thus formed was converted to CO2in quantitative yields and the hydroxy acid decarboxylated with permanganate; thusly C3was obtained. The acetic acid (from C1and C2) was extracted with ether and subsequently degraded by the Schmidt–Phares procedure. The procedure was further used to degrade some 2-deoxy hexoses.
STEROIDS AND RELATED PRODUCTS: XXI. THE SYNTHESIS OF 17α-BROMO-6α -METHYLPROGESTERONE
Authors: Rakhit S. , Deghenghi R. , Engel Ch. R.
Published: May 2006

The synthesis fo 17α-bromo-6α-methylprogesterone, from pregnenolone acetate, is reported. The product is a potent luteoid with marked oral activity. In the course of this investigation, a useful variation of the synthesis of 6α-methylprogesterone, from pregnenolone, was devised. The rearrangement of a 5β,6β-epoxide to a 6-ketone, upon chromatography on aluminum oxide "Woelm", was observed.
EXCHANGE BROADENING OF SPIN–SPIN TRIPLETS IN NUCLEAR MAGNETIC RESONANCE SPECTRA. APPLICATION TO THE SYSTEM ETHANOL–WATER
Authors: Paterson W. G.
Published: May 2006

Using an extension of the method of McConnell (1), an expression is derived for the nuclear magnetic resonance spectrum of a hydroxyl proton in a —CH2OH group which is undergoing intermolecular exchange. A graphical method is presented which enables a rapid evaluation of τ, the average lifetime of a hydroxyl proton between exchange events. Measurements of line widths and multiplet spacings in the n.m.r. spectra of ethanol—water solutions are interpreted in terms of the proton exchange reaction[Formula: see text]for which a value of 2.7 1. mole−1 sec−1 at 42 ± 1 °C is suggested as an upper limit to the rate constant.
IONIZATION OF ORGANIC COMPOUNDS: V. THIOLACTAMS IN SULPHURIC ACID
Authors: Edward J. T. , Stollar H.
Published: May 2006

The ionization in aqueous sulphuric acid of thiolactams consisting of five-, six-, and seven-membered rings has been studied. With increasing concentration of acid the ionization ratio increases more rapidly than h0. A possible explanation involving the hydration of the thio-lactam is given. Changes in the basicity of thiolactams with ring size parallel changes previously found for lactams.
THE ALUMINUM REDUCTION OF MAGNESIUM COMPOUNDS: III. THE VAPOR PRESSURE OF MAGNESIUM OVER THE SYSTEM Al–Mg2SiO4 (OLIVINE)
Authors: Grjotheim K. , Herstad O. , Skarbö R. , Toguri J. M.
Published: May 2006

The equilibrium vapor pressure of magnesium over the reaction between olivine (Mg2SiO4) and aluminum was measured by means of the transportation method in the temperature range 943–1150 °C.It was concluded that olivine and aluminum form an unstable system which reacts completely according to the equation[Formula: see text]However, in the presence of excess aluminum, an Al–Si alloy results. This alloy in turn reacts with magnesium oxide according to the equilibrium[Formula: see text]The vapor pressure of magnesium over this equilibrium system was found to obey the equation[Formula: see text]The aluminum activity of the Al–Si alloy along the liquidus line of the silicon side of the phase diagram has been calculated. Within the temperature range 943–1150 °C this activity can be represented by the equation[Formula: see text]
PENTAERYTHRITOL DERIVATIVES: I.MECHANISM OF FORMATION OF DIPENTAERYTHRITOL
Authors: Trevoy L. W. , Myers M. E.
Published: May 2006

Dipentaerythritol, (CH2OH)3CCH2OCH2C(CH2OH)3, is a product of the base-catalyzed Tollens condensation of acetaldehyde with formaldehyde. The mechanism for formation of dipentaerythritol has not been hitherto established.Three types of experimental evidence support the conclusion that monopentaerythritol, C(CH2OH)4, is an intermediate in the sequence of reactions leading to dipentaerythritol: (1) the isolation of radioactive dipentaerythritol from a Tollens condensation in which mono-pentaerythritol-C14 was present, (2) comparison of the radioactivity levels of mono- and di-pentaerythritol prepared by reaction of formaldehyde-C14 with inactive monopentaery-thritol and inactive acetaldehyde, and (3) the observed dependence of the yield of dipentaerythritol on the concentration of monopentaerythritol present in the condensation reaction mixture.
THE BIOSYNTHESIS OF HYDRASTINE AND BERBERINE
Authors: Gear J. R. , Spenser Ian D.
Published: May 2006

The biosynthesis of hydrastine and of berberine was investigated by administering radioactive glucose, phenylalanine, tyrosine, and dopamine to Hydrastis canadensis L. Both hydrastine and berberine were found to be specifically derived from two molecules of tyrosine. The ratio of incorporation of the two molecules of radiotyrosine into hydrastine was not unity, and varied with time. Dopamine was also incorporated into hydrastine without randomization, but only one molecule was utilized. These results, which are consistent with the classical hypothesis and disprove the prephenic acid hypothesis of biogenesis, provide direct evidence for some of the steps in the biosynthetic pathway by which hydrastine and berberine are formed in the plant.
THE VINYLTRIFLUOROBORATE ANION
Authors: Stafford S. L.
Published: May 2006

not available
THE PHOTOLYSIS OF LIQUID O2–N2 SOLUTIONS
Authors: Demore W. B. , Raper Odell
Published: May 2006

not available
THE ALDOL CONDENSATION WITH 2,3-DIPHENYL-4-THIAZOLIDINONE
Authors: Brown Frances C. , Jones R. Sidney , Kent Mildred
Published: May 2006

The aldol condensation between 2,3-diphenyl-4-thiazolidinone and aromatic aldehydes, which cannot be effected by the usual catalysts used in the analogous reactions of 2-thiono-, 2-oxo-, and 2-imino-4-thiazolidinones, was achieved by the use of ethoxide ion. The structure of the 2,3-diphenyl-5-arylidene-4-thiazolidinone was confirmed by ultraviolet spectral data.
HYDROXYMETHYL PHOSPHORUS DERIVATIVES FROM TETRAKIS(HYDROXYMETHYL) PHOSPHONIUM CHLORIDE. REACTION WITH LEAD CARBONATE AND OXIDE
Authors: Filipescu N. , Kindley L. M. , Podall H. E. , Serafin F. A.
Published: May 2006

A novel and convenient method has been developed for the preparation of tris(hydroxy-methyl) phosphine oxide (THPO) from tetrakis (hydroxymethyl) phosphonium chloride (THPC). The method consists essentially of oxidative deformylation of THPC with lead carbonate in n-propyl alcohol. The reaction is facilitated by azeotropic distillation of di-n-propylformal and n -propyl alcohol.The reaction of THPC with lead carbonate as well as with lead oxide has been studied in detail in aqueous solution and in n-propyl alcohol. The reaction proceeds via the initial formation of tetrakis(hydroxymethyl) phosphonium hydroxide (THPOH) followed by deformylation to tris (hydroxymethyl) phosphine (THP). THP then undergoes oxidation by air as well as by lead carbonate or oxide to THPO. If air is bubbled through the mixture at elevated temperatures, atmospheric oxidation predominates with little or no oxidation by the lead compound.Depending upon the reaction conditions, a phosphonium hydroxide, a phosphine, or a phosphine oxide are products of the reaction of tetrakis(hydoxymethyl) phosphonium chloride with lead carbonate or oxide.
KINETICS AND MECHANISMS OF THE PYROLYSIS OF n-BUTANE: PART I. THE UNINHIBITED DECOMPOSITION
Authors: Sagert N. H. , Laidler K. J.
Published: May 2006

The kinetics of the pyrolysis of n-butane have been studied at temperatures from 520° to 590 °C, and at pressures from 30 to 600 mm Hg; the rate was followed from pressure changes and by gas chromatography. The reaction was accurately of the three-halves order; the activation energy was found to be 59.9 kcal mole−1, and the frequency factor 3.24 × 1015 cc1/2 mole−1/2 sec−1. The reaction is sensitive to surface; packing the vessel and 'conditioning' it usually led to a decrease in rate and an increase in activation energy. The reaction is concluded to be largely homogeneous, and to occur almost entirely by a free-radical mechanism; the initiation reaction is considered to be the dissociation of a butane molecule into two ethyl radicals, in its first-order region, and termination is believed to be the second-order combination of ethyl radicals. The mechanism proposed is shown to account satisfactorily for the observed behavior. The surface effect is attributed to a certain amount of initiation by abstraction, by a surface atom, of a hydrogen atom from butane, and to surface catalysis of the recombination of ethyl radicals.
COORDINATION COMPOUNDS OF HYDRAZINE: PART III. THE INTERACTION OF SILICON TETRAFLUORIDE WITH HYDRAZINE
Authors: Aggarwal R. C. , Onyszchuk M.
Published: May 2006

Silicon tetrafluoride and hydrazine react in a vacuum to produce a white, non-volatile, solid, 1:2 complex, SiF4.2N2H4. This compound sublimes with decomposition above 200° and is insoluble in common organic solvents. It reacts with (a) 55% hydrofluoric acid, (b) anhydrous hydrogen chloride, (c) ethylenediamine, (d) ammonia, and (e) boron trifluoride, producing: (a) (N2H5+)2SiF62−, (b) N2H5+Cl−, (c) SiF4.NH2(CH2)2NH2, (d) SiF4.2NH3, and (e) BF3.N2H4. A comparison of the infrared spectra of SiF4.2NH3, SiF4.2N2H4, and SiF4.NH2(CH2)2NH2 suggests that all three complexes have cis octahedral structure.
THE β-D -CONFIGURATION OF THE RIBOSYL NICOTINAMIDE PORTION OF DIPHOSPHOPYRIDINE NUCLEOTIDE
Authors: Lemieux R. U. , Lown J. W.
Published: May 2006

The configurations of the anomeric N-(tetra-O-acetyl-D-glucopyranosyl)-3-carboxamido-pyridium bromides were established by nuclear magnetic resonance (n.m.r.) spectroscopy. The β-D-anomer was found to undergo deacetylation without anomerization. This compound on oxidation with periodate has been shown (M. Viscontini and E. Hürzeler-Jucker. Helv. Chim. Acta, 39, 1620 (1956)) to yield a different product than did a synthetic N- (D-ribo-furanosyl)-3-carboxamidopyridinium chloride. Therefore, the anomeric configuration of the latter compound must be is α-D. Since its anomer was used (N. A. Hughes, G. W. Kenner, and A. Todd. J. Chem. Soc. 3733 (1957)) to synthesize diphosphopyridine nucleotide (DPN), the configuration of the anomeric center in this portion of the coenzyme must be β-D. Optical rotatory dispersion curves are reported for DPN, its component nucleotides, and the above-mentioned D-glucosides.
AZA STEROIDS: III. SYNTHESIS OF 11-AZA STEROIDS—A NOVEL CLASS OF STEROIDAL SAPOGENIN ANALOGUES
Authors: Kutney James P. , Vlattas I. , Rao Ganti Venkat
Published: May 2006

The cyclization of a 9,12-seco-11-nor keto acid in the hecogenin series in the presence of benzylamine and anhydrous ammonia is described. The benzylamine reaction follows an unusual course whereas the ammonia reaction proceeds normally to provide an enol lactam. The sequence represents the first synthesis of an 11-aza derivative in the steroidal sapogenin series.
THE HYDRATES OF FLUORAL
Authors: McGreer D. E. , Stewart R. , Mocek M. M.
Published: May 2006

not available
SOME 4-OXYGENATED CYCLOHEPTANONES
Authors: Yates Peter , Anderson Charles D.
Published: May 2006

not available
THE NUCLEAR MAGNETIC RESONANCE SPECTRA OF SOME 2-METHYL-Δ2-OXAZOLINES AND 2-METHYL-Δ2-THIAZOLINES
Authors: Weinberger M. A. , Greenhalgh R.
Published: May 2006

not available
PYRIDINES FROM BASE TREATMENT OF BENZALMALONONITRILE
Authors: Weir M. R. S. , Helmer K. E. , Hyne J. B.
Published: May 2006

not available
THE DECOMPOSITION OF HYDRAZINE VAPOR IN ELECTRICAL DISCHARGES
Authors: Jones R. A. , Barton S. S.
Published: May 2006

not available
ALKYLALUMINUM HYDRIDE TRIMETHYLAMINE COMPLEXES
Authors: Peters F. M. , Bartocha B. , Bilbo A. J.
Published: May 2006

Alkylaluminum hydride trimethylamine complexes have been obtained by several different methods: (a) reduction of an alkylaluminum halide trimethylamine complex with lithium hydride, (b) alkylation of aluminum hydride trimethylamine with dialkylmercury, (c) reaction of trialkylaluminum trimethylamine and aluminum hydride trimethylamine, and (d) reaction of dialkylaluminum chloride with lithium aluminum hydride and trimethylamine. Some physical properties of the compounds are reported, including the infrared and proton magnetic resonance spectra. Cryoscopic molecular weight determinations indicate that the compounds are associated in cyclohexane. Their possible structures are discussed.
REACTION OF CHROMYL CHLORIDE WITH SOME OLEFINS: PART I. THE PRODUCTS FROM CYCLOHEXENE, CYCLOPENTENE, 1-HEXENE, AND 2-METHYL-1-PENTENE
Authors: Stairs R.A. , Diaper D. G. M. , Gatzke A. L.
Published: May 2006

Chromyl chloride in carbon tetrachloride solution reacts in the cold with cyclohexene, cyclopentene, and 1-hexene to give the various isomeric chlorohydrins as the major products. The major product from 2-methyl-1-pentene was 2-methylpentanal. Significant amounts of α-chloro carbonyl compounds and some α,β-unsaturated carbonyl compounds were also produced. The significance of these results is discussed.
THE REACTION OF ACTIVE NITROGEN WITH METHANOL
Authors: Sole M. J. , Gartaganis P. A.
Published: May 2006

The reaction of active nitrogen with methanol has been investigated at several temperatures in the range 30 to 480 °C using a fast-flow system. The only condensable products found in appreciable amounts were water and hydrogen cyanide. The overall activation energy is 3.0 and 3.2 kcal/mole and the steric factors 1.3 × 10−3 and 2.1 × 10−3 for streamline and turbulent flow respectively.It is postulated that the mechanism consists of the initial formation of a collision complex, [NCH3OH], which breaks down to two fragments, NCH3 and OH, from which the two condensable products are formed,[Formula: see text]Attack of the methanol molecules by hydrogen atoms resulting from the main reaction occurs to a lesser extent and is responsible for the production of small quantities of methane, carbon monoxide, and additional water.