bluuebunny/crossref_metadata_2025 huggingface dataset:
11-OCTADECENOIC ACID AND OTHER FATTY ACIDS OF ASCLEPIAS SYRIACA SEED OIL
Authors: Chisholm Mary J. , Hopkins C. Y.
Published: May 2006

The seed oil of Asclepiassyriaca L., family Asclepidaceae, was examined by gas chromatography and distillation of the methyl esters. The fatty acids were found to include a considerable proportion of cis-11-octadecenoic acid, which has not been observed previously in seed oils. It was obtained as a concentrate [Formula: see text] by low-temperature crystallization of the C18 acids and identified as 11,12-dihydroxystearic acid. The amount of 11-octadecenoic acid in the oil was determined by oxidative splitting of the total fatty acids and estimation of the resulting azelaic and undecanedioic acids by gas chromatography.The C16 acids included 9,12-hexadecadienoic acid, which is rare in seed oils,and an unusually large proportion of 9-hexadecenoic acid. The percentage composition of the fatty acids was estimated from the data as follows: palmitic 4,9-hexadecenoic 10, 9,12-hexadecadienoic 2, stearic < 1, oleic 15, 11-octadecenoic 15, linoleic 53, linolenic < 1. The unsaturated acids have the cis configuration.
EQUILIBRIUM DECOMPOSITION PRESSURES OF K2TiCl6
Authors: Flengas S. N. , Ingraham T. R.
Published: May 2006

The equilibrium decomposition pressures of K2TiCl6 were measured at temperatures between 370° and 530 °C, using a glass-bellows mercury manometer.The pressure–temperature relationship was found to obey the equation[Formula: see text]and the heat of the reaction[Formula: see text]was found to be[Formula: see text]
THE AQUEOUS BENZOATE SYSTEM AS A SENSITIVE DOSIMETER FOR IONIZING RADIATIONS
Authors: Armstrong W. A. , Grant D. W.
Published: May 2006

The aqueous benzoate system, as typified by 6 × 10−4 M calcium benzoate, meets many of the requirements for a sensitive chemical dosimeter. The concentration of salicylic acid, determined spectrophotofluorometrically, increases linearly with radiation dose in the range 5 to 5000 rads and is independent of temperature from 15 to 45 °C, of energy from 160 kev to 3 Mev, and of dose rate from 4 to about 1000 rads/minute. The decrease in sensitivity with increasing dose rate from 1000 to 85,000 rads/minute is reported.
SOME OPEN-CHAIN DERIVATIVES OF GLUCOSE AND MANNOSE
Authors: Curtis E. J. C. , Jones J. K. N.
Published: May 2006

The dimethyl thioacetals of D-glucose and D-mannose have been condensed with acetone. Mannose dimethyl thioacetal forms a crystalline 3,4:5,6-di-O-isopropylidene derivative while glucose forms a mixture of the crystalline 3,4:5,6-di-O-isopropylidene and syrupy 2,3:5,6-di-O-isopropylidene isomers. These three di-O-isopropylidene dimethyl thioacetals have been converted via crystalline intermediates into the corresponding di-O-isopropylidene dimethyl acetals. These derivatives are suitable open-chain compounds for use in Koenigs–Knorr syntheses and provide (a) mannose with the C2 hydroxyl free, (b) glucose with the C2 hydroxyl free, and (c) glucose with the C4 hydroxyl free.
THE STUDY OF HYDROGEN BONDING AND RELATED PHENOMENA BY ULTRAVIOLET LIGHT ABSORPTION: PART IV. INTERMOLECULAR HYDROGEN BONDING IN ANILINES AND PHENOLS
Authors: Dearden J. C. , Forbes W. F.
Published: May 2006

Intermolecular hydrogen bonding in anilines and phenols can be subdivided into bonding involving solute molecules only, and into bonding involving both solute and solvent molecules. Interactions which do not involve hydrogen bonding are also possible between solute and solvent molecules. Spectral effects which may be associated with each of these interactions are described and discussed for anilines and phenols. By noting the effects of substituents on the various interactions, tentative conclusions can be deduced concerning the nature of these interactions.
CARBON-13 KINETIC ISOTOPE EFFECTS IN THE SOLVOLYSIS OF 1-BROMO-1-PHENYLETHANE
Authors: Stothers J. B. , Bourns A. N.
Published: May 2006

Carbon-13 kinetic isotope effects have been measured for the solvolysis in methanol and ethanol of 1-bromo-1-phenylethane of natural isotopic abundance. Methanolysis of the bromide at 25 °C gave a kinetic isotope effect (k12/k13) of 1.0065 ± 0.0006, and ethanolysis at 45 °C gave 1.0064 ± 0.0010. These surprisingly low effects for a bond-rupture process have been interpreted in terms of a model for the transition state in which the bonding of the isotopic. carbon is strengthened by conjugation of the electron deficient center with the ring. The results are considered to provide support for the mass fragment model for evaluation of the effective mass term of the Bigeleisen expression for the theoretical calculation of kinetic isotope effects.
THE SYNTHESIS OF 2-O-β-D-GLUCOPYRANOSYL-D-XYLOSE
Authors: Jones J. K. N. , Reid P. E.
Published: May 2006

A synthesis of the disaccharide named in the title is described. Some aspects of the periodate oxidation of this sugar and of analogous sugar derivatives have been examined.
THE FREEZING OF WATER AND BENZENE IN POROUS VYCOR GLASS
Authors: Hodgson C. , McIntosh R.
Published: May 2006

Freezing has been detected in the adsorbed water and benzene of porous Vycor glass at temperatures below that at which the bulk phases freeze. The evidence presented by equilibrium pressure measurements and dimensional changes of the systems is considered in terms of theories of capillary condensation and freezing in cements and soil. Although not all the results can be explained, it is concluded that the freezing process is a gradual one for both adsorbate–adsorbent systems. The evidence further suggests that hysteresis is absent in isotherms if the solid phase has formed.
STEROIDS: PART I. THE SYNTHESIS OF SOME HETEROCYCLIC STEROID DERIVATIVES
Authors: Ketcheson Barbara G. , Taurins Alfred
Published: May 2006

Cyanoacetamide reacted with 3β-hydroxy-16-hydroxymethylene-5-androsten-17-one to form 1-cyano-2-hydroxy-2(16′-3′β-hydroxy-17′-oxo-5′-androstenyl) propionamide or 3-cyano-4,5-dehydro-6-hydroxy-5,6(16′,17′-3′β-hydroxy-5′-androstenyl)-2-piperidone depending on whether a catalytic or a molecular amount of piperidine was used as the basic condensing agent. Carboxamidoacetamidine, and acetamidine hydrochlorides, were condensed with the sodium salt of 3β-hydroxy-16-hydroxymethylene-5-androsten-17-one, and 3β-chloro-16-chloromethylene-5-androsten-17-one yielding 2-amino-3-carboxamido-5,6(16′, 17′-3′β-hydroxy-5′-androstenyl) pyridine and 2-methyl-5,6(16′,17′-3′β-chloro-5′-androstenyl) pyrimidine respectively.
THE SYNTHESIS OF 10-SUBSTITUTED PHENOXAZINES
Authors: Frangatos Gerassimos , Kohan Geza , Chubb Francis L.
Published: May 2006

not available
FREE RADICAL MECHANISMS FOR INHIBITED ORGANIC DECOMPOSITIONS
Authors: Wojciechowski B. W. , Laidler K. J.
Published: May 2006

It is suggested that organic decompositions that are fully inhibited by substances such as nitric oxide and propylene proceed not by molecular mechanisms, but by special types of free radical mechanisms in which the inhibitor is involved in both initiation and termination. In the case of nitric oxide inhibition, initiation is considered to be by the abstraction of a hydrogen atom by NO, while termination involves reaction between the most plentiful chain carrier and either HNO or NO, depending upon whether or not H is a chain carrier. Specific mechanisms are proposed for the decompositions of paraffins, ethers, and aldehydes, when inhibited by nitric oxide, and the resulting rate equations are shown to be consistent with the behavior observed experimentally. It is shown for the ethane decomposition that the same limiting rate is obtained for any inhibitor that can become involved in the same type of mechanism.
THE RADIOLYSIS OF CYCLOHEXANE: II. CYCLOHEXANE–CYCLOHEXENE SOLUTIONS AND PURE CYCLOHEXENE
Authors: Freeman G. R.
Published: May 2006

The γ-radiolysis of cyclohexane–cyclohexene solutions and of pure cyclohexene has been investigated. The previously determined yields of the two activated species in irradiated cyclohexane have been confirmed. G(c-C6H12′′) = 3.0 ± 0.3 and G(c-C6H12′) = 2.4 ± 0.3.The yields of the main products of cyclohexene radiolysis are G(H2) = 1.2, G(c-C6H12) = 1.0, G[(c-C6H9)2] = 1.4, and G(c-C6H10 → higher polymer) ≈ 4. There were smaller amounts of ethylene, acetylene, a C4 hydrocarbon (probably butadiene), cyclohexylcyclohexene, and dicyclohexyl.For the reactions[Formula: see text]and[Formula: see text]the value k7a/(k8ak6a)1/2 = 0.45 ± 0.08 was determined.The reaction mechanism that occurs during the radiolysis of cyclohexane–cyclohexene solutions is similar to that which occurs during the radiolysis of cyclohexane–benzene solutions (Part I of this series) with the additional consideration that cyclohexene itself is considerably decomposed during the radiolysis.
RELATIVE RATES OF REACTION OF OZONE WITH OLEFINS IN THE VAPOR PHASE
Authors: Vrbaski T. , Cvetanović R. J.
Published: May 2006

Relative rates of reaction of ozone with a number of olefins in the vapor phase have been determined by the use of the competitive method and GLC analysis of the reaction products. The results indicate a basic electrophilic trend onto which is superimposed a trend due to a partially inhibiting effect of the substituent groups, in particular of those on the more substituted carbon atom of the olefinic double bond. The results are discussed particularly in terms of a two-step addition process, involving an initial formation of an ozone–olefin π-complex and a slower rearrangement of the π-complex into the cyclic "initial ozonide".
A STUDY OF THE PRODUCTS OF THE REACTIONS OF OZONE WITH OLEFINS IN THE VAPOR PHASE AS DETERMINED BY GAS–LIQUID CHROMATOGRAPHY
Authors: Vrbaski T. , Cvetanović R. J.
Published: May 2006

A broad comparative survey has been made of the products of the vapor phase reactions of ozone with ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, isobutene, 2-methyl-1-butene, cis-2-butene, trans-2-butene, cis-2-pentene, trans-2-pentene, trimethyl ethylene, tetramethyl ethylene, cyclohexene, and 1,3-butadiene as determined by gas–liquid chromatography and, to a smaller extent, by other analytical methods.
CIS AND TRANS 1-ACETOXY-1,3-BUTADIENE: PHYSICAL AND CHEMICAL PROPERTIES, INFRARED AND ULTRAVIOLET SPECTRA
Authors: Georgieff K. K. , Dupré A.
Published: May 2006

1-Acetoxy-1,3-butadiene was prepared by the reaction of crotonaldehyde with acetic anhydride in the presence of potassium or sodium acetate. The product was found to consist of two forms which, from their physical properties and infrared spectra, appear to be cis and trans. Mass and ultraviolet spectra, and methods of analysis are also reported. The cis form was found to be a substantially stronger inhibitor than the trans in the bulk polymerization of vinyl acetate using benzoyl peroxide as catalyst.
BILE ACID DERIVATIVES
Authors: Amos A. A. , Ziegler P.
Published: May 2006

The potassium permanganate oxidation of 3α, 12α-diacetoxy-24,24-diphenyl-Δ23-cholene yielded a new compound which was identified as 3α,12α-diacetoxy-23-keto-24-hydroxy-24,24-diphenylcholane. The latter steroid, on reduction with sodium borohydride, produced two isomeric glycols which were subsequently dehydrated to provide the corresponding 23-keto-24,24-diphenyl derivative.
N-DICHLOROACETYL DERIVATIVES OF SERINE AND THREONINE AND OF THEIR ESTERS AND SODIUM SALTS
Authors: Levi I. , Koller A. E. , Laflamme G. , Weed J. W. R.
Published: May 2006

The N-dichloroacetyl derivatives of DL-serine and DL-threonine were prepared by the Schotten–Baumann reaction from the amino acids and dichloroacetyl chloride. Negative ninhydrin tests coupled with elementary analyses indicated that only the amino group was acylated. The ester derivatives of these compounds were prepared either by esterification of the N-dichloroacetyl-DL-amino acid with diazomethane or by the reaction of the amino acid ester with dichloroacetyl chloride in the presence of triethylamine. The sodium salts and the esters were tested for antitumor activity against sarcoma 37 in mice and Walker carcinoma 256 in rats. In both cases regression of the tumors was obtained.
ANODIC OXIDE FILMS ON NIOBIUM: THICKNESS, DIELECTRIC CONSTANT, DISPERSION, REFLECTION MINIMA, FORMATION FIELD STRENGTH, AND SURFACE AREA
Authors: Young L.
Published: May 2006

The wavelengths of minimum specular reflectivity (at 11° incidence) due to interference were determined using a spectrophotometer for a series of films formed on chemically polished niobium. With a value of the refractive index n = 2.46 ± 1% at 4358 Å wavelength by the Abelès method (reported elsewhere), the spectrophotometric data give the refractive index as a function of the wavelength λ, n = 2.26 + 0.398/(λ/103 Å − 2.56)1.2. To analyze the spectrophotometric results, an auxiliary measure of thickness was required (though, with the chart given below, the thickness of a film may be determined directly from spectrophotometric measurements alone). A combination of measurements of the a-c. capacity and of the charge required to form the films gives a suitable measure of thickness (in terms of ρ/ε, where ε = dielectric constant and ρ = density) which is not dependent on a knowledge of the true surface area. The spectrophotometric data provide a calibration of this measure of thickness and thus give ε/ρ. With ρ = 4.36 g cm−3 (reported for the bulk amorphous oxide) this gives ε about 41 (compared with about 27.6 for Ta2O5). The effective surface area of the chemically polished metal was then found to be about 7% greater than the apparent area. At the ionic current density used to form the films (10 ma cm−2), the field strength in the oxide was estimated as 4.96 × 106 v cm−1 within a few per cent uncertainty. Because the field to produce a given ionic current is lower than with Ta2O5 films, the capacity of films formed to a given voltage at a given current density and temperature is not so much greater for niobium than for tantalum as the dielectric constants might lead one to expect. It is suggested that there may be a correlation between dielectric constant and ionic conductivity. The Nb2O5 films recrystallize like Ta2O5 films under an applied field but more readily, at least with the purity of metal now available.
ALIPHATIC CHEMISTRY OF FLUORENE: PART VI. 3,4-BENZOFLUORENE-9-SPIRO-CYCLOHEXANE
Authors: Bavin P. M. G.
Published: May 2006

The quinoxaline (VI) has been prepared from 3,4-benzofluorene, establishing the structure of the cyclization product of I as 3,4-benzo-5,6,7,8-tetrahydrofluorene-9-spiro-cyclohexane. 3,4-Benzo-9,9-dimethylfluorene has been prepared and oxidized to the quinone (VIII) which formed the quinoxaline (IX), structurally related to VI.1,2:7,8-Dibenzo-9-methylfluorene has been synthesized from 1,2:7,8-dibenzofluorenone which, contrary to an earlier report (13), forms an oxime.
THE REACTION OF 2-CYANO-2-PROPYL FREE RADICALS WITH OXYGEN: 2-CYANO-2-PROPYL HYDROPEROXIDE
Authors: Talât-Erben M. , Önol Nevzat
Published: May 2006

The reaction with oxygen of cyanisopropyl free radicals generated by the polymerization catalyst 2,2′-azobisisobutyronitrile has been investigated. In xylene, or benzene, as solvent at 55° the products identified are: (1) a new compound, 2-cyano-2-propyl hydroperoxide; (2) acetone cyanohydrin; (3) hydrogen cyanide; (4) cyanogen; (5) acetone; (6) p-methyl benzaldehyde (in xylene only); and (7) tetramethylsuccinodinitrile. The hydroperoxide is surprisingly stable; its physical constants are: b.p. 37 °C at 1 mm Hg; m.p. −9 to −8°; [Formula: see text] 1.4138; d20 1.013 g/ml. In benzene under the same experimental conditions, only a very small amount of the hydroperoxide is obtained, the principal product being acetone cyanohydrin. A free-radical mechanism is proposed. The induced decomposition of the hydroperoxide, which is important in benzene, is almost completely inhibited in the presence of xylene. The new hydroperoxide can be used as a polymerization catalyst at moderately elevated temperatures.
THE ELECTRON SPIN RESONANCE ABSORPTION SPECTRA OF SEMIQUINONE IONS: PART III. FREE RADICAL SALTS OF QUINHYDRONES
Authors: Matsunaga Yoshio
Published: May 2006

Electron spin resonance absorption was observed in alkali salts of tetrachloro-p-benzoquin-hydrone, p-biphenoquinhydrone, and its tetrachloro and tetrabromo derivatives. The magnitude of g-value was found to be in the order of unsubstituted < chloro derivative < bromo derivative, and benzoquinhydrone salt < the corresponding p-biphenoquinhydrone salt. The frequency of C—O stretching vibration was observed in the range 1525 to 1550 cm−1. Based on these frequencies the estimation of the parameters which are necessary for the molecular orbital treatment of semiquinone ions was attempted. A set of αO = α + (l/3−l/2)β and βCO = β were derived. Independently values of αO = α + 2/3β and βCO = β were estimated using the hyperfine structure of the electron spin resonance spectrum of the α-naphthosemiquinone ion.
A NOTE ON THE CYCLIZATION OF 3-(2′-NAPHTHYL)-BUTYRIC ACID
Authors: Bavin P. M. G.
Published: May 2006

not available
A COLOR TEST FOR CERTAIN PIPERIDINE AND PYRROLIDINE ALKALOIDS
Authors: McCaldin D. J.
Published: May 2006

not available
SOME NEW BENZILIC ACID DERIVATIVES
Authors: Chubb Francis L. , Frangatos Gerassimos , Nissenbaum Jacqueline
Published: May 2006

not available
EFFECT OF NITRIC OXIDE IN THE γ-RADIOLYSIS OF ETHANE AT VERY LOW CONVERSIONS
Authors: Yang Kang
Published: May 2006

not available
STUDIES OF RATES OF CONVERSION AND POPULATIONS OF VARIOUS CONFORMATIONS OF SATURATED RING COMPOUNDS BY N.M.R.: I. CHLOROCYCLOHEXANE AND BROMOCYCLOHEXANE
Authors: Reeves L. W. , Strømme K. O.
Published: May 2006

The populations of equatorial and axial halogen forms of chloro- and bromo-cyclohexane have been studied by proton magnetic resonance between 25° and −104 °C in carbon disulphide solution. From the equilibrium constants obtained the free energy change between the two conformations is obtained. The bromo compound has 82% of the equatorial halogen form and the chloro compound 77%. Estimates of the populations are also available for room temperature from the chemical shift measurements. The energy barrier for conversion between the two forms is approximately 10,850 calories. A simple Lennard-Jones potential with the available estimates of van der Waals radii is used to calculate the differences in energy of the two forms.
NUCLEAR SHIELDING PARAMETERS FOR PROTONS IN HYDROGEN BONDS: II. CORRELATION OF CHEMICAL SHIFTS IN INTRAMOLECULAR HYDROGEN BONDS WITH INFRARED STRETCHING FREQUENCIES
Authors: Reeves L. W. , Allan E. A. , Strømme K. O.
Published: May 2006

Nuclear shielding parameters have been obtained for 24 intramolecularly hydrogen-bonded phenols and naphthols. The shielding parameters are corrected for large diamagnetic anisotropies and a value ΔσOH obtained which represents the change in shielding parameter in parts per million with reference to the infinite dilution chemical shift of phenol, α-naphthol, or β-naphthol. These values of ΔσOH are approximately proportional to the change ΔvOH in the OH stretching frequency on formation of the hydrogen bond.
OROTIC ACID AND ITS ANALOGUES: PART II. ON THE ALKALINE REARRANGEMENT OF 5-CARBOXYMETHYLIDENEHYDANTOIN
Authors: Deghenghi R. , Daneault G.
Published: May 2006

The in vitro conversion of 5-carboxymethylidenehydantoin to orotic acid is not likely to occur in vivo since the two substances have antagonistic effects (2). A sulphur analogue of the above hydantoin has been prepared and shown not to undergo alkaline rearrangement to the corresponding metathiazine structure. The mechanism of orotic acid formation is discussed.
CO-ORDINATION COMPLEXES OF TITANIUM (IV) HALIDES: 1. PREPARATION AND INFRARED SPECTRA OF THE COMPLEXES OF TITANIUM (IV) HALIDES WITH N,N-DIMETHYL AND N,N-DIPHENYL FORMAMIDE
Authors: Archambault Jacques , Rivest Roland
Published: May 2006

Co-ordination complexes of titanium (IV) halides with N,N-dimethyl formamide and N,N-diphenyl formamide have been prepared and their infrared spectra have been measured. In all these complexes, there is a metal-to-oxygen bond as evidenced in the infrared spectra by a negative shift of the carbonyl stretching frequency and a positive shift of the CN stretching frequency. The relative values of these shifts and the ease of decomposition observed for these complexes indicate that their stability decreases with decreasing the electronegativity of the halide bonded to titanium (IV).In the complexes of N,N-diphenyl formamide, the effect of the conjugated phenyl groups has been observed. In these complexes the decrease of double-bond character of the carbonyl group and the increase of double-bond character of the CN group, resulting from the metal-to-oxygen co-ordination bond, are quite larger than in the complexes of N,N-dimethyl formamide.
DIPHENYLCYANAMIDE DERIVATIVES. IV. 1,1-bis(4-CHLOROPHENYL)-UREA
Authors: Robinson J. R.
Published: May 2006

not available
ORGANO ARSENIC COMPOUNDS: I. N,N-DIALKYL AMIDODICHLOROARSENITES AND N-ALKYL IMIDOCHLOROARSENITES
Authors: Olah G. A. , Oswald A. A.
Published: May 2006

N,N-Dialkyl amidodichloroarsenites were prepared by the reaction of arsenic trichloride with aliphatic secondary amines. Arsenic trichloride and primary amines react similarly, but the N-alkyl amidodichloroarsenites formed usually lose HCl and give N-alkyl imidoarsenites on distillation.
ARYLPYRIDINES: PART II. REACTION OF PHENYLLITHIUM WITH 3-METHOXY- AND 3-AMINO-PYRIDINE
Authors: Abramovitch R. A. , Notation A. D.
Published: May 2006

Phenyllithium has been shown to react with 3-methoxy- and 3-amino-pyridine to give exclusively 3-methoxy-2-phenylpyridine and 3-amino-2-phenylpyridine respectively. The orientation of the products has been established unambiguously. None of the 2,5-isomer was detected in either case. An explanation for this unique orientation is suggested.
THE ATTACK OF CHROMITE BY SULPHURIC ACID
Authors: Biermann W. J. , Heinrichs Menno
Published: May 2006

A study was made of the attack of a "low grade" chromite concentrate by sulphuric acid of various concentrations with a view toward formulating a more adequate description, or mechanism, of the process. Consideration of available evidence eliminates the possibility of hydrolysis playing an important role in the process. A qualitative mechanism consistent with the available facts is based on an initial protonic attack, followed by formation of various sulphate complexes of chromium.
SYNTHESES OF POLYURETHANES FROM HYDROXY-TERMINATED POLYESTERS
Authors: Gagnon Paul E. , Boivin Jean-L. , House George W.
Published: May 2006

Hydroxy-terminated polyesters were synthesized by treating diols with the diethyl esters of dicarboxylic acids. Ethylene, diethylene, and triethylene glycols, four polyoxyethylene glycols ranging in molecular weight from 200 to 600, 1,2-propanediol, dipropylene glycol, five polyoxypropylene glycols ranging in molecular weight from 150 to 2025, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,2′-(methylimino)diethanol, 2,2′-(ethylimino)diethanol, 2,2′-(butylimino)diethanol, and 2,2′-thiodiethanol were condensed with diethyl succinate in the absence and presence of a catalyst, and with diethyl cyanomalonate, cyanosuccinate, and α-cyanoglutarate.Polyurethanes were obtained from the various polyesters prepared by treatment with different quantities of 2,4-tolylene diiocyanate. In general, non-elastomeric products were obtained from polyesters of monomeric glycols, while elastomeric polyurethanes with the lowest brittle points were formed from polyoxyethylene glycol 400 and 600, and polyoxypropylene glycol 750, 1025, and 2025 polyesters. Also the succinate polyurethanes, which did not contain nitrile groups, had the greatest tendency to be elastomeric and had the lowest brittle points. For the nitrile containing polyurethanes, the cyanomalonates had the lowest tendency to be elastomeric and had the highest brittle points. The cyanosuccinate and α-cyanoglutarates had about the same properties.
DETERMINATION OF TRACE AMOUNTS OF SILVER IN GALENA ORES
Authors: Bounsall E. J. , McBryde W. A. E.
Published: May 2006

An analytical method is described for the determination of microgram amounts of silver in galena ores, based on the "reversion" of silver dithizonate. Silver is separated from relatively large amounts of lead by extraction as dithizonate into chloroform from an aqueous 1:99 nitric acid solution. Separation from mercury, which is also extracted under these conditions and would, if present, interfere in the analysis, is achieved by reverting the dithizonate solution with a 5% aqueous sodium chloride solution which is also 0.015 molar in hydrochloric acid. Following dilution of this aqueous solution and adjustment of pH, silver is again extracted into chloroform as the dithizonate, and determined absorptiometrically. Analyses of a number of galena ore samples showed a precision of within 3% for a silver content ranging from 0.03 to 0.4%.Some other methods for isolating silver from these samples, which were tried but found unsatisfactory, are discussed.
17α-HALOGENATED PROGESTERONES: ORALLY-ACTIVE PROGESTINS
Authors: Marshall David J. , Gaudry Roger
Published: May 2006

17α-Chloroprogesterone, 6α-fluoro-17α-bromoprogesterone, 1-dehydro-6α-fluoro-17α-bromoprogesterone, and 6α-chloro-17α-bromoprogesterone have been synthesized. These compounds have been found to be orally-active progestins without androgenic properties.
PROTONATION OF THE AMIDE GROUP: I. THE BASICITIES OF SUBSTITUTED BENZAMIDES
Authors: Edward J. T. , Chang H. S. , Yates K. , Stewart Ross
Published: May 2006

The basicities of benzamide and of 11 meta- and para-substituted benzamides in sulphuric acid media have been determined by a spectrophotometric method. The [Formula: see text] values of the protonated benzamides were found to be proportional to the Hammett σ constants for the substituents, unlike the [Formula: see text] values of the protonated benzaldehydes, acetophenones, and benzoic acids, which are approximately proportional to σ+ constants. The lack of conjugation between the protonated amide group and the ring, which is indicated by these results, is most easily interpreted in terms of N-protonation although O-protonation cannot be completely excluded. Various other aspects of the problem of N- versus O-protonation are also discussed.
HYDROGEN ATOM ABSTRACTION BY ETHYL-d5 RADICALS. PART I
Authors: Boddy P. J. , Steacie E. W. R.
Published: May 2006

The photolysis of 3-pentanone-d10 has been used as a source of deuterated ethyl radicals and some of their hydrogen abstraction reactions studied over the temperature range 50–300 °C.The compounds neopentane, n-butane, and isobutane were chosen as representative of the basic structural features in the alkane series. The activation energies for abstraction [Formula: see text] are respectively 12.60 ± 0.7, 10.4 ± 0.75, and 8.9 ± 0.6 kcal/mole and the pre-exponential factors (log10(A8/A4)) are 0.300 ± 0.09, 0.082 ± 0.09, and −0.334 ± 0.066 where[Formula: see text]For abstraction of a deuterium atom from the ketone the values obtained are [Formula: see text] in agreement with previous investigations (1, 2).The value of the disproportionation to combination ratio for C2D5 radicals is 0.0985 ± 0.008 independent of temperature.
THE EFFECT OF SOLVENTS UPON EQUILIBRIA, SPECTRA, AND REACTION RATES
Authors: Brownstein S.
Published: May 2006

It is shown that the effect of solvent upon a wide variety of equilibria, reaction rates, and spectral shifts may be described by the equation log (ksolvent/kethanol) = SR. S is a constant related to the polarity of the solvent and R is a measure of the sensitivity of the system to change in solvent polarity. Tables of S and R are included.
DETERMINATION OF DIELECTRIC CONSTANT IN BINARY ORGANIC SYSTEMS
Authors: Miller C. G. , Maass O.
Published: May 2006

Measurements of the dielectric constants of binary systems have been made; hexane, benzene, toluene, acetone, isopropyl alcohol, and nitrobenzene have been used two at a time. It was the purpose to obtain accurate data for the dielectric constants for the 15 systems over the whole range of concentrations from 0 to 100%, with the absolute accuracy of 0.1%. It is claimed that the relative accuracy is of this order. From the data obtained regularities have been found which are expressed in the form of empirical equations which summarize the data. Tentative suggestions regarding theoretical conclusions are made in a number of cases.
CRYSTALLINE O-METHYL ETHERS OF D-GALACTITOL
Authors: Bishop C. T.
Published: May 2006

not available
SPIROHEXANE
Authors: McGreer Donald E.
Published: May 2006

not available
ABSOLUTE RATE MEASUREMENTS OF O-ATOM REACTIONS WITH ETHYLENE AND WITH BUTANE
Authors: Elias L. , Schiff H. I.
Published: May 2006

The absolute rate constants for the primary reactions of O-atoms with ethylene and with butane have been determined in a fast-flow system. The O-atoms were produced by electrodeless discharge of O2 and allowed to react with the hydrocarbon introduced downstream. Addition of a small amount of NO to the gas stream enabled a photometric monitoring of the O-atoms in the reaction zone. The initial atom concentration was determined by NO2 titration. The reaction could be stopped at any point in the reaction zone by means of a movable surface of cobalt oxide. The hydrocarbon concentration at any point could then be determined by condensation downstream and analysis of the products.Rate measurements were carried out over the temperature range −50° to 200 °C. The rates were found to be consistent with a two-body mechanism. For O-atoms with ethylene, k = 1.8(±0.6) × 10−11e−1600/RT cm3 molecule−1 sec−1 and for O-atoms with butane, k = 5.0(±1.6) × 10−11e−4200/RT cm3 molecule−1 sec−1.
ATOMIC REACTIONS IN THE UPPER ATMOSPHERE
Authors: Kaplan Joseph , Schade William J. , Barth Charles A. , Hildebrandt Alvin F.
Published: May 2006

The reaction rates of nine upper atmosphere chemical reactions have been analyzed with a digital computer. The dependence of the loss rates of atomic nitrogen and atomic oxygen as well as the relative concentrations of nitric oxide and nitrogen dioxide in the upper atmosphere are given. Using a flow system, nitrogen atoms were produced and then titrated by the addition of NO. The resulting nitrogen and oxygen atom densities were measured with an e.p.r. spectrometer. The dependence of the intensities of the nitrogen afterglow and the NO afterglow were related to the atom densities. An excitation mechanism for OI 5577 has been determined from the relation of the intensity of λ 5577 to the atom densities.
HIGH ENERGY REACTIONS OF ATOMIC HYDROGEN
Authors: Henchman Michael , Urch David , Wolfgang Richard
Published: May 2006

The chemistry of hot hydrogen atoms has been studied using tritium of high kinetic energy as produced by nuclear recoil. The possibilities and limitations of this technique are discussed using a collision theory for reactions of atoms having a very high initial energy. Using this theory and certain experimental data, it is concluded that hot hydrogen atoms react to combine with organic molecules at very high collision efficiency (of the order of approximately 0.2 to 0.4) in the energy range 3–10 ev. There is no indication that collisions at much higher energies lead to combination. With most systems, e.g. alkanes, a wide variety of reactions is observed. The systematics of these hot reactions is discussed and evidence on their detailed mechanism is presented. It appears that most products are formed by a fast displacement of an atom or group by the hot hydrogen. There is no evidence for the formation of a common, internally equilibrated, collision complex which decays on a statistically determined basis to the various products. Instead, the course of the reactions seems largely governed by the direction and point of impact of the hot atom. Thus, stereochemical evidence indicates that axial approach of the hot hydrogen atom along the C—H bond axis leads to abstraction while approach at large angles to this axis results in displacement without Walden inversion. In some cases sufficient excitation energy is introduced in the hot displacement process to cause further decomposition of the primary product. This model of high-energy reactions is compared with that of thermal reactions and its general implications are briefly discussed.
THE REACTIONS OF HYDROGEN ATOMS WITH SOME ORGANIC LIQUIDS
Authors: Ingalls R. B. , Hardy J. R.
Published: May 2006

Measurements have been made of isotopic exchange and deuterium pressure change during deuterium atom bombardment of o-terphenyl, toluene, and eicosane just above their melting points. The number of molecules of HD formed was larger than the number of molecules lost or gained by the gas phase. A mechanism of reaction of deuterium atoms with aromatic liquids is proposed.
THE STRUCTURE OF LYCODINE
Authors: Ayer W. A. , Iverach G. G.
Published: May 2006

The molecular formula of the Lycopodium alkaloid lycodine has been revised to C16H22N2. Transformation of β-obscurine (I) into N-methyl lycodine has shown that lycodine is the pyridine analogue of des-N-methyl-β-obscurine and is represented by structure II (R=H). The transformation of β-obscurine into α-obscurine is also described.
SOME EQUILIBRIUM CONSTANTS OF TRANSITION METAL HALIDES
Authors: Lister M. W. , Rosenblum P.
Published: May 2006

Measurements are reported on the formation of complex ions in solutions containing cupric and chloride or bromide ions, and solutions of nickel or cobalt with chloride. In each case the halide was present in very low amount. With copper a spectrophotometric method was used, and a cell voltage method with nickel and cobalt. The ionic strength was kept constant, but the temperature was varied. The data show difficulties of interpretation if it is assumed that only MX+ ions (M is the metal, X is the halogen) are formed, the difficulties arising from the anomalous variation of the equilibrium constant with temperature, and from the general drift of the calculated constants from the e.m.f. measurements. Various explanations are considered and it is shown that postulation of M2X+3 ions is at least a possible explanation.
THE STUDY OF HYDROGEN BONDING AND RELATED PHENOMENA BY ULTRAVIOLET LIGHT ABSORPTION: PART V. INTRAMOLECULAR HYDROGEN BONDING IN ANILINES AND PHENOLS
Authors: Dearden J. C. , Forbes W. F.
Published: May 2006

Information concerning intramolecular hydrogen bonding in phenols and anilines can be obtained from ultraviolet spectra by a variety of methods. One method is to note the spectral changes observed between the corresponding o-substituted phenols and anisoles. A second method is to compare the spectral changes between o-substituted phenols or anilines and the corresponding meta isomers. A third method is to note the absence of an appreciable spectral change, on altering the solvent conditions, which may also indicate the formation of an intramolecular hydrogen bond. The conclusions deduced from the three methods confirm previously stated generalizations concerning the nature of the hydrogen bond. One notable exception is that the spectral changes ascribed to the intramolecular hydrogen bond in o-nitrophenol can be explained in terms of an electrostatic model of the hydrogen bond.
THE STUDY OF HYDROGEN BONDING AND RELATED PHENOMENA BY ULTRAVIOLET LIGHT ABSORPTION: PART VI. THE EFFECT OF STERIC INTERACTIONS ON THE INTRAMOLECULAR HYDROGEN BOND IN o-NITROPHENOL
Authors: Dearden J. C. , Forbes W. F.
Published: May 2006

Intramolecular hydrogen bonding occurring in o-nitrophenol is discussed with special reference to the effects of the steric interactions on the absorption bands and on the bonding. An alkyl substituent vicinal to the OH group, or a methyl group vicinal to the NO2 group appears to strengthen the intramolecular hydrogen bond in o-nitrophenol. The O—H vibrational stretching frequency in o-nitrophenol appears to be more susceptible to steric than to mesomeric interactions, and a methyl substituent vicinal to the nitro group in o-nitrophenols is found to give rise to a characteristic O—H stretching vibration band. For 6-t-butyl-2-nitrophenol, a special, "protected" hydrogen bond is postulated. In some of the o-nitrophenols, intermolecular hydrogen bonding gives rise to appreciable ultraviolet intensity decreases presumably because of increased steric interactions.
ANIONIC POLYMERIZATION OF STYRENE
Authors: Worsfold D. J. , Bywater S.
Published: May 2006

A study of the kinetics of the initiation and propagation reactions in the polymerization of styrene by butyllithium in benzene solution has been made. The initiation has been shown to be first order in styrene and 0.155 order in butyllithium, the propagation to be first order in styrene and half order with respect to active chain ends. The apparent activation energies of the two reactions have been shown to be 18,000 calories and 14,300 calories respectively. The ultraviolet absorption spectra of colored species produced has been measured and compared with others found in similar systems.
A NEW SYNTHESIS OF METHYL β-D-GULOPYRANOSIDE
Authors: Antia N. J. , Perry M. B.
Published: May 2006

The oxidation of 1 mole of β-D-glycero-D-gulo-heptopyranoside with 1 mole of sodium metaperiodate, followed by reduction with sodium borohydride, gave rise to crystalline methyl β-D-gulopyranoside. The method provides a new synthetic route to the D-guloside and, thence, to D-gulose. The possibility of utilizing this reaction scheme as a general convenient method for preparing the relatively rare aldohexoses as well as for "labelling" carbon atom 1 of these compounds is discussed.
EXPERIMENTAL STUDIES OF SOLUTION PROCESSES: VI. EFFECT OF SOLVENT ON INFRARED ABSORPTION SPECTRA
Authors: Maine P. A. D. De , Daly L. H. , Maine M. M. De
Published: May 2006

Here are reported infrared absorption data between 4000 cm−1 and 700 cm−1 near 19 °C for methanol, n-propanol, isopropanol, cyclohexanol, benzyl alcohol, diethyl ether, anisole, 1,4-dioxane, diisopropyl ether, nitromethane, acetone, p-xylene, benzene, and hexane as pure substances and in carbon tetrachloride solution. Band frequencies accurate to within 1 cm−1 are reported. Except for the 3340 cm−1 band in dilute MeOH solutions no frequency shifts were observed even with gross changes of the electrical properties of the solutions. Molar extinction coefficients at absorption maxima are discussed briefly.
SYNTHÈSES D'ACIDES AMINOBUTYRIQUES. 1. ACIDES ALKYLAMINO-2 AMINO-4 BUTYRIQUES
Authors: Laliberté Réal , Berlinguet Louis
Published: May 2006

The syntheses of eight 2-alkylamino-4-aminobutyric acids are described. The starting material is 4-butyrolactone, which is opened with potassium phthalimide to give 4-phthalimidobutyric acid. After bromination the 2-bromo-4-phthalimidobutyric acid, obtained in excellent yield, is treated with aliphatic amines in alcoholic medium to give the desired substituted 2,4-diaminobutyric acids, which were characterized as the monohydrochlorides and the di(phenylcarbamates). Three of them cyclized easily to give the corresponding hydantoins. In the course of the reaction, substituted diamides of phthalic acid were isolated and characterized.
CONSTITUTION OF A GLUCOMANNAN FROM THE WOOD OF EASTERN WHITE PINE (PINUS STROBUS L.)
Authors: Gyaw M. O. , Timell T. E.
Published: May 2006

Glucomannans have been isolated from the wood of eastern white pine (Pinusstrobus L.) by two different methods, the ratios of mannose to glucose being 3.8:1 and 2.7:1, respectively. The yields, based on the mannose content of the wood, were 70 and 50%. Partial acid hydrolysis gave 4-O-β-D-mannopyranosyl-D-mannose, 4-O-β-D-mannopyranosyl-D-glucose, 4-O-β-D-glucopyranosyl-D-mannose, 4-O-β-D-glucopyranosyl-D-glucose, O-β-D-mannopyranosyl-(1 → 4)-O-β-D-mannopyranosyl-(l → 4)-D-mannose, and O-β-D-mannopyranosyl-(l → 4)-O-β-D-mannopyranosyl-(l → 4)-O-β-D-mannopyranosyl-(l → 4)-D-mannose. The fully methylated polysaccharide on hydrolysis gave a mixture of di-O-methylhexoses, 2,3,6-tri-O-methyl-D-mannose, 2,3,6-tri-O-methyl-D-glucose, and 2,3,4,6-tetra-O-methylhexose (mostly mannose) in a mole ratio of 4:61:21:1. The number-average degrees of polymerization of the methylated and the nitrated glucomannans were 96 and 93. On the basis of this and other evidence it is concluded that the glucomannan contains at least 90 mannose and glucose residues linked together by (1 → 4)-β-glycosidic bonds to linear macromolecules. The nature and relative composition of the oligosaccharides obtained on partial hydrolysis indicate that very few of the glucose residues are contiguous. The glucomannan is compared with similar polysaccharides from the wood of other gymnosperms.
CATALYTIC OXIDATION OF CARBON MONOXIDE PRESENT IN LOW CONCENTRATIONS
Authors: Sourirajan S. , Accomazzo Mauro A.
Published: May 2006

The oxidation of carbon monoxide present in low concentrations has been studied in the presence of the CuO–Al2O3 (1:1) catalyst using 1,000–10,000 p.p.m. of CO in air in the temperature range 120°–322 °C, and gas space velocities ranging from 8,000–16,000 hr−1. It was found that for the entire concentration range studied, the percentage of oxidation of CO at a given temperature was independent of its initial concentration and at temperatures above 200 °C, more than 95% of CO was removed by oxidation at all gas space velocities up to 16,000 hr−1. A simple first-order rate equation was found to fit the experimental data well. The presence of water vapor in the reactant gas was found to have no effect on the efficiency of the catalyst at temperatures above 225 °C. The possible practical utility of the above catalyst for the removal of carbon monoxide present in auto exhaust gases was tested using a six-cylinder Chevrolet engine run on leaded gasoline fuel. It was found that under all conditions of engine operation, more than 99% of carbon monoxide present in the exhaust gases was removed by catalytic oxidation when the initial temperature of the catalyst bed was kept at or above 220 °C.
A CHEMICAL PROCEDURE FOR DETERMINATION OF THE C14DISTRIBUTION IN SOME LABELLED CARBOHYDRATES
Authors: Abercrombie M. J. , Jones J. K. N.
Published: May 2006

A chemical procedure for the determination of the labelling in the terminal carbon atoms of some unsubstituted carbohydrates using 20 mg of material is described. The procedure has been tested on D-glucose-1-C11, D-glucose-6-C14, D-glucose-2-C14, and D-glucuronolactone-6-C14with satisfactory results.A procedure based on the work of Smith etal. for the degradation of hexoses via the methyl glucopyranosides is described and has been applied to D-glucose-1-C14and D-glucose-6-C14with satisfactory results. These procedures have been designed to give barium carbonate as the final product in each determination.
PHASE EQUILIBRIUM RELATIONSHIPS IN THE BINARY SYSTEM METHYL ETHYL KETONE–WATER
Authors: Siegelman Irwin , Sorum C. H.
Published: May 2006

A complete investigation of the phase equilibrium relationships in the binary system of the partially miscible liquid pair methyl ethyl ketone–water is presented. The system shows a minimum azeotrope at 73.35 ± 0.05 °C with a composition of 88.45 ± 0.15 wt.% ketone. The azeotrope falls outside of the miscibility gap for this system. The liquid–vapor curves intersect the miscibility gap at the temperature of 73.60 ± 0.05 °C at which two conjugate solutions of compositions 18.10 ± 0.10 and 87.78 ± 0.15 wt.% ketone, respectively, are in equilibrium with a vapor phase of composition 88.00 ± 0.15 wt.% ketone. The partially miscible liquid pair shows an upper consolute temperature of 139 ± 0.5 °C at a composition of 44.9 ± 0.2 wt.% ketone. The liquid–liquid curves intersect the solid–liquid curves at a temperature of −6.0 ± 0.5° C at which two conjugate solutions of composition 40.0 ± 0.2 and 78.0 ± 0.2 wt.% ketone, respectively, are in equilibrium with ice. A binary eutectic exists at a temperature of −89.0 ± 0.5 °C with composition of the eutectic solid equal to 99.4 ± 0.4 wt.% ketone. The freezing point of pure, dry methyl ethyl ketone is determined to be −83.5 ± 0.5 °C.
VAPOR/LIQUID PARTITION OF TRITIUM IN TRITIATED WATER
Authors: Sepall O. , Mason S. G.
Published: May 2006

not available
THE REACTION OF THE O- AND N-METHYL DERIVATIVES OF AROMATIC KETOXIMES WITH CARBON MONOXIDE AND HYDROGEN
Authors: Rosenthal Alex
Published: May 2006

not available
STOICHIOMETRY OF THE REACTION OF CHROMYL CHLORIDE WITH CYCLOHEXENE
Authors: Stairs R. A.
Published: May 2006

not available
3,5-DI-O-METHYL-D-GALACTOSE, A NEW METHYLATED SUGAR FROM A FULLY METHYLATED POLYSACCHARIDE OF GIBBERELLA FUJIKUROI (FUSARIUM MONILIFORME)
Authors: Siddiqui I. R. , Adams G. A.
Published: May 2006

not available
THE CHEMISTRY OF ETHYLENE OXIDE: VI. THE ACID-CATALYZED REACTION OF ETHYLENE OXIDE WITH ETHANOL–WATER MIXTURES
Authors: Brown R. K. , Eastham A. M.
Published: May 2006

The rate of reaction of ethylene oxide with alcohol–water mixtures at 25 °C has been determined. The ratio of glycol to ethoxyethanol in the product was determined for each mixture and found to be approximately equal to the molecular ratio of water to ethanol in the solvent.
THE PREPARATION OF SUBSTITUTED THIONOCARBAMATES
Authors: McKay A. F. , Garmaise D. L. , Paris G. Y. , Gelblum S. , Ranz R. J.
Published: May 2006

The preparations and properties of a number of substituted thionocarbamates are described.
LA RÉACTION DE REFORMATSKY APPLIQUÉE À L'OXO-2 CYCLOHEXANE-PROPIONITRILE ET À DES CÉTO-NITRILES ANALOGUES
Authors: Bruderlein F. , Bruderlein Hélène , Favre H. , Lapierre R. , Lefebvre Y.
Published: May 2006

not available
IONIZATION OF ORGANIC COMPOUNDS IN ACID I. ALIPHATIC KETONES
Authors: Campbell H. J. , Edward J. T.
Published: May 2006

The changes in the ultraviolet absorption spectra of aliphatic ketones in aqueous sulphuric acid have been followed as the acid strength is increased from 0 to 98%. With increase in strength up to 65% the weak peak at about 270 mμ is shifted to shorter wavelengths by a medium effect. However, with further increase in acid strength the peak disappears altogether because of protonation of the carbonyl group. The pKBH+ values of several ketones have been calculated from the spectrophotometric results to be about −7. The pKBH+ values of cyclic ketones vary systematically with ring size. The significance of the present work to recent studies on the rate of enolization of acetone is discussed.
THE USE OF THE HELLMANN–FEYNMAN THEOREM TO CALCULATE MOLECULAR ENERGIES
Authors: Bader Richard F. W.
Published: May 2006

The Hellmann–Feynman theorem has been employed to calculate the repulsion between two helium atoms and the molecular energies of H2 and H3. The method of molecular orbitals was used to determine the necessary expressions for the electron densities. The screening constants of the atomic orbitals comprising the molecular orbitals were treated as functions of the internuclear separation according to an empirical expression which duplicates very closely the "best" values for these parameters as determined by the variational method. The results of the calculations indicate that the present method is capable of yielding estimates of molecular energies which are comparable to those obtained by the more elaborate and time-consuming variational methods.
THE REACTIONS OF PERFLUOROETHYL RADICALS WITH HYDROGEN AND METHANE
Authors: Price S. J. W. , Kutschke K. O.
Published: May 2006

The reactions of C2F5 radicals, produced by the photolysis of (C2F5)2CO, with methane and hydrogen have been studied. Assuming zero activation energy for 2C2F5 → C4F10 the activation energies for C2F5 + CH4 → C2F5H + CH3 and C2F5 + H2 → C2F5H + H are 10.6 kcal/mole and 11.9 kcal/mole respectively. The present results have been correlated with data on the reactions of CF3, C3F7, and CH3 radicals with H2, D2, CH4, and C2H6. Taking Erecombination ≈ 0 in all cases and assuming the frequency factor for the recombination reaction varies little from radical to radical, the order of ease of hydrogen abstraction from a given substrate is CF3 > C2F5 > C3F7 > CH3. Similarly the ease of hydrogen abstraction from a substrate by a given fluorinated radical is C2H6 > H2 > CH4 > D2. A calculation based on very limited data indicates the reaction CH3 + C2F5COC2F5 → CH3COC2F5 + C2F5 may occur with an activation energy of approximately 7 kcal/mole.