bluuebunny/crossref_metadata_2025 huggingface dataset:
The properties of the electrical double layer III: The capacity of the double layer on Hg and on AgI
Authors: Mackor E. L.
Published: September 2010

A model of the double layer on the basis of the Gouy‐Stern theory is given assuming the absence of chemisorption of counterions. The capacity K of the Stern layer is taken to be constant, but the χ potential located in the first water layer at the phase boundary is assumed to be a function of the surface charge. This theory is discussed using as an example the capacities of the Hg electrode in NaF solutions.

The adsorption of silver and iodide ions on AgI at different concentrations of NaClO4 in water, 25% vol. and 100% vol. acetone were determined. The capacities of the double layer on AgI calculated from these adsorption curves are in many respects similar to the usual capacity curves of Hg. There are, however, some qualitative differences.

The theory of Grimley and Mott about the double diffuse layer is discussed. Comparison with experiment shows the influence of the diffuse layer in solid AgI on the total capacity to be small.
Composition and properties of bromine hydrate and potassium polybromide
Authors: Zernike J. , Nawab Md. Ali , Aziz Md. Abdul
Published: September 2010

Phase theoretical study of the system KBr‐Br2‐H2O at 0° leads to Br2.7 H2O and KBr6.1½H2O as solid compounds with incongruent melting points of 5.85 and 25.85° respectively. Potassium polybromide is diamagnetic; the aqueous phase with which it is in equilibrium at its melting point has the composition 21.4% KBr, 70.4% Br2 and 8.2% H2O by weight.
The structure of 2,4‐dihydroxypyridines
Authors: Woodburn Henry M. , Hellmann Max
Published: September 2010

Chemical experiments designed to give information regarding the structure of 2,4‐dihydroxypyridines indicated that one rather active hydroxy group was present, but failed to detect a keto group. Acetylation produced only monoacetates but benzoylation in two cases gave dibenzoates also. Only monoethers resulted from diazomethane reaction.

Comparison of the absorption of selected compounds between the wavelengths 220 and 340 mμ indicated that this region of the spectrum is unsatisfactory as a source of structural data.
Réactions de Friedel‐Crafts avec les 4‐alkylbiphényles et le 4‐benzylbiphényle
Authors: Buu‐Hoï Ng. Ph. , Royer René
Published: September 2010

Comme suite à des recherches antérieures, on étudie dans le présent travail le comportement du 4‐éthyl‐, du 4‐n‐propyl‐, et du 4‐benzylbiphényle dans les réactions de Friedel‐Crafts avec les chlorures d'acides. Il est montré que les radicaux alkyles et benzyle orientent en position 4'. Au cours de ces recherches, de nombreux nouveaux dérivés du biphényle ont pu être synthétisés, certains en vue d'études biologiques.
Synthetic oxytocics. I: 3‐(piperidyl‐(N)‐methyl‐)indoles and related compounds
Authors: Akkerman A. M. , de Jongh D. K. , Veldstra H.
Published: September 2010

3‐(piperydyl‐(N)‐methyl‐)indole and a number of derivatives with substituents in the piperidine‐nucleus, together with some related compounds, were synthesized as simplified analogues of the ergot alkaloïds. Some of them proved to be highly active on the rabbit uterus in situ (sensitized with estrone), the highest active 3‐(2′,6′‐dimethyl‐piperidyl‐(N)‐methyl)‐indole being half as effective as ergometrine. On the isolated uterus of the guinea pig in some cases the activity of the natural drug is surpassed. Structure/activity relationships are indicated, to be followed by a more extensive discussion after 3‐(piperidyl (2) methyl‐) indoles have been evaluated pharmacologically.
Investigations on organic fungicides: IV. Chemical constitution and fungistatic activity of dithiocarbamates, thiuram sulphides and structurally related compounds
Authors: Klöpping H. L. , van der Kerk G. J. M.
Published: September 2010

The work reported below forms a part of current investigations on the mode of antifungal action of tetramethylthiuram disulphide and other notorious sulphur fungicides. The relations between chemical constitution and fungistatic activity, and the structural conditions for optimum activity in the group of dithiocarbamates and thiuram disulphides are dealt with. In this group the dimethyldithiocarbamate ion contains all structural elements required for optimum antifungal activity.
The preparation of ozone by electrolysis II
Authors: Boer H.
Published: September 2010

Some improvements in the design of the previously described electrolytic ozone generator are described. These make the apparatus easier to construct and to handle; in addition, the ozone percentage and production are increased, amounting to 15½ % by weight and 14½ mmols/hr at 15 A, and to 15% by weight and 17 mmols/hr., respectively, at 18 A.

By stabilization of the electrolyzing current the apparatus has been shown to be highly satisfactory for quantitative purposes. A stabilizer is described by which the composition of the ozone‐oxygen mixture can be kept constant within a few units per mille for several hours.

An apparatus capable of producing smaller amounts of high‐percentage ozone, for use at low current strength, without the need of internally cooling the anode, is also described.
Thermal quantities of some cycloparaffins: Part I syntheses
Authors: Kaarsemaker Sj. , Coops J.
Published: September 2010

The following substances were prepared with a view to the accurate determination of their heats of combustion: cyclobutane (from cyclobutanone, originating from the reaction between ketene and diazomethane), cycloheptane, cyclooctane and cyclononane (from the cyclanones, which were made by ringenlargement from cyclohexanone).
On the structure of andrographolide
Authors: Kleipool R. J. C. , Kostermans D. G. F. R.
Published: September 2010

The infrared spectrum of andrographolide shows the presence of a five‐membered unsaturated lactone‐ring and a terminal methylene group in the molecule. On catalytic hydrogenation more than four atoms of hydrogen are taken up. A new diacetyl‐anhydro‐andrographolide is described.
The raman effect of an equimolecular liquid mixture of nitric acid and sulphur trioxide
Authors: Gerding H. , Steeman J. W. M.
Published: September 2010

The Raman spectrum of an equimolecular liquid mixture of one mole of HNO3 with one mole of SO3 has been determined. From the frequency shifts and the polarization of the Raman lines it is inferred, that the reaction HNO3 + SO3 → NO2+ + HSO4− takes place in a strong, although not in a practically quantitative way.
Gradual separation and economy: 6th Communication, separation by distillation in batches
Authors: Treub J. P.
Published: September 2010

In this communication a diagram is developed for fixing the number of distillation elements necessary in the fractionating column for various purities of distillate and residue and for various types of binary systems in distilling with total reflux and with central introduction of intermediates, similar to the diagram given in the 5th communication1) but now in a more general manner. An example of the use of the diagram is also given.
Sur l'alkylation de la phtalylhydrazine (phtalaz‐1,4‐dione)
Authors: Buu‐Hoï Ng. Ph. , le Bihan H. , Binon F.
Published: September 2010

On montre dans ce travail que la dialkylation de la phtalylhydrazine au moyen de divers halogénures d'alkyles conduit toujours à des 1‐alkyloxy‐3‐alkyl‐4‐phtalazones. Ces derniers composés, traités par le chlorhydrate de pyridine, sont sélectivement déalkylés en position 1, et conduisent à des 3‐alkylphtalaz‐1,4‐diones.
Deacylation of aromatic acetylamino compounds in acid alcoholic medium
Authors: van Roon J. P. , Verkade P. E. , Wepster B. M.
Published: September 2010

Aromatic acetylamino compounds are converted into the corresponding amino compounds by heating with absolute alcoholic hydrogen chloride; the acetyl group is split off in the form of an ester. This acid deacylation has been studied more closely and compared with the (pseudo) catalytic deacylation in alkaline medium.

Contrary to what was found in the latter process, the mesomeric effect (‐M‐effect) of substituents present in the nucleus plays no significant role; acid deacylation is not, like alkaline deacylation, dominated by quinonoid structures. Consequently steric inhibition of the mesomerism in this case has no appreciable influence on the rate of deacylation.

Derivatives of acetanilide with two ortho‐substituents are deacylated strikingly slowly. There is no doubt that here we are dealing with cases of classical steric hindrance; on the contrary, this phenomenon does not occur in alkaline deacylation.

Acid deacylation is frequently very useful for preparative purposes, particularly in the presence of alkoxycarbonyl groups, carbonamido groups, cyano groups and the like. These substituents remain Intact during the reaction, which is not the case in the classical methods for hydrolysing acetylamino compounds.
Non‐newtonian flow of dilute polymer solutions: III. Sodium carboxy methyl cellulose in solutions of sodium chloride)
Authors: Akkerman F. , Pals D. T. F. , Hermans J. J.
Published: September 2010

A direct and straightforward method is used to derive the influence? of the shearing stress on the intrinsic viscosity from the experimental data without introducing empirical or semi‐empirical relations. It can be shown that the method of plotting (t – t0)/t0c where t is the flow time and c the concentration. is in error.

The application to carboxy methyl cellulose in dilute salt solutions reveals a pronounced effect of small shear rates on the intrinsic viscosity. On comparing with existing hydrodynamic theories it is found that even the fully extended length of the polymer molecule would be too small to explain the results.
Mass spectrometric determination of deuterium in organic compounds
Authors: den Boer D. H. W. , Borg W. A. J.
Published: September 2010

A method is described suitable for the determination of deuterium in organic compounds by means of a mass spectrometer.
Vaccenic acid
Authors: van Loon J. , van der Linden D.
Published: September 2010

A short review of earlier work on vaccenic acid is given and a new synthesis is described.
The spectrophotometric determination of molybdenum in molybdenum steels
Authors: Karsten P. , van Mourik J. H. C.
Published: September 2010

The existing Mo determination with thiocyanate has been put on a firmer basis, the recommended procedure has been adapted to it and applied to Mo steels.
A new synthesis of aryl‐aliphatic alcohols. IV. Application of the method to bicyclic hydrocarbons
Authors: Beets M. G. J. , van Essen H.
Published: September 2010

The method described in the preceding papers of this series3) is applied to 1,2‐dihydronaphthalene and indene. The products of the reaction of indene with formaldehyde are investigated.
An unexpected rearrangement of a benzhydrylammonium compound
Authors: Harms A. F. , Nauta W. Th.
Published: September 2010

Heating of benzhydryl‐dimethyl‐2‐hydroxyethyl‐ammoniumchloride gives rise to a rearrangement in which the benzhydrylgroup migrates from the nitrogen atom to the oxygen, with the formation of benzhydryl‐dimethyl‐aminoethyl‐ether hydrochloride.
The mechanism of the reaction between ozone and aromatic bonds. A reply to G. M. Badger
Authors: Sixma F. L. J. , Wibaut J. P.
Published: September 2010

A summary is given of experiments which lead to the conclusion that the addition of ozone is an electrophilic reaction. The points of difference and agreement in mechanism between the addition of ozone and electrophilic substitution are discussed. The suggested mechanism is not in opposition to the interpretation of Kooyman and Ketelaar.
The carboxylation of m‐Amino‐Phenol
Authors: Stelt C. V. D. , Suurmond B. G. , Nauta W. Th.
Published: September 2010

Although 2‐amino‐4‐hydroxy‐benzoic acid is one of the compounds to be expected as a result of the reaction of carbon dioxide with m.amino‐phenol and potassium bicarbonate in the presence of water, the only monobasic reaction product that could be identified by several authors was 4‐amino‐2‐hydroxy‐benzoic acid. The presence of small quantities of 2‐amino‐4‐hydroxy‐benzoic acid could, however, be demonstrated by the present authors.
Steric effects on mesomerism. VI. Preparation and dipole moment of nitrodurene
Authors: Kofod H. , Sutton L. E. , de Jong W. A. , Verkade P. E. , Wepster B. M.
Published: September 2010

The substance supposed to be nitrodurene, prepared by Birtles and Hampson1), has been found to be impure nitroethoxydurene. Pure nitrodurene could be obtained by two independent methods; its dipole moment has been measured for the first time.
Contribution a la connaissance des diazomethyl‐cetones
Authors: Ultée A. J. , Soons J. B. J.
Published: September 2010

Au cours de recherches synthétiques dans le domaine de l'auxine‐a, les auteurs ont eu l'occasion d'étudier de plus près les propriétés de quelques diazocétones aliphatiques; ils ont constaté que la transposition de Wolff ne s'effectue pas toujours aisément.
Course of the reaction between orthophthalaldehyde and hydroxylamine
Authors: Kampschmidt L. W. F. , Wibaut J. P.
Published: September 2010

The formation of the mono‐oxime of phthalimide (IV) by the reaction of ortho‐phthalaldehyde with hydroxylamine is found to take place via several intermediate steps. In this reaction some dioxime of phthalimide is formed. A simple method for preparing the mono‐oxime of phthalimide is described.
The influence of cations on the gelatin gel. III. The influence on the elasticity
Authors: Nobel P. C.
Published: September 2010

The influence of the chlorides of a number of monovalent and divalent metals on the elasticity of gelatin gels was studied. Upon the elasticity values being plotted against the equivalent conductances of the cations, the curve found for the divalent metals was analogous to the curve found in the swelling experiments. The monovalent cations have the same influence on the elasticity, except for the lithium ion, which causes a greater elasticity value. The change of the elasticity during the ageing of the gel was investigated.
The formation and decomposition of dimethylolurea
Authors: de Jong J. I. , de Jonge J.
Published: September 2010

The formation and decomposition of dimethylolurea shows a close resemblance to that of monomethylolurea previously studied

J. I. de Jong and J. de Jonge, Rec. trav. chim. 71, 643 (1952).

a) The reaction between formaldehyde and monomethylurea giving dimethylolurea leads to an equilibrium which can be reached from both sides. The equilibrium is independent of the pH of the solution.

b) The formation of dimethylolurea from formaldehyde and monomethylolurea appeared to be a bimolecular reaction. The decomposition of dimethylolurea is monomolecular.

c) Both reactions are catalyzed to the same extent by hydrogen ions and by hydroxyl ions and there is an influence of the buffer concentration on the velocity. The reaction rates are found to be directly proportional to the hydrogen and hydroxyl—ion concentrations.

d) The activation energies have been determined. Within experimental error these energies were found to be about the same as the activation energies of the monomethylolurea formation and decomposition, viz. 14 and 19 kcal/mole.

The reaction mechanism is briefly discussed.

The formation of trimethylolurea could not be observed.
La thermomécanique des phenomenes de transport
Authors: Verschaffelt J. E.
Published: September 2010

Je montre comment la théorie thermomécanique des phénomènes de transport, en particulier de ceux qui se produisent à travers une membrane, peut être développée d'une manière tout à fait indépendante du principe d'Onsager.
La thermomécanique des phenomenes de transport. Quelques remarques à propos de l'article de m. j. e. Verschaffelt
Authors: Overbeek J. Th. G. , Mazur P.
Published: September 2010

Les auteurs montrent comment la théorie thermomécanique des phénomènes de transport conduit dans le cas des phénomènes electrocinétiques à un résultat qui est contraire à l'expérience.
Determination of radioactive cobalt in biological material
Authors: de Wael J.
Published: September 2010

A rapid method for the determination of 60Co in biological material is proposed. After wet ashing of the organic substances with nitric acid and hydrogen peroxide 60Co is precipitated in the presence of a large excess of 59Co as potassium cobaltinitrite. The latter is collected on a filter paper. The amount of 60Co present in the precipitate is measured with the help of a Geiger‐Müller tube, comparing the counts registered by the scaler with the counts obtained using a precipitate of potassium cobaltinitrite containing a known amount of 60Co.
The raman effect of N2O4. 3 SO3 and N2O5. 3 SO3
Authors: Gerding H. , Eriks K.
Published: September 2010

The preparation of a compound corresponding to the formula N2O5. 3 SO3 is given. Neither in the manner of preparation described by Pictet and Karl, nor in other way was a stable compound of composition N2O5. 4 SO3 obtained. The Raman spectrum of solid N2O5. 3 SO3 and of a solid preparation of the average composition N2O4. 3 SO3 are determined. Herefrom it may be concluded that N2O5. 3 SO3 has to be considered as (NO2+)2. S3O10−−, whereas the product of formula N2O4. 3 SO3 contains NO2+ and NO+ ions besides the same negative ions S3O10−−.
Untersuchungen über Derivate von 2,3‐Dihydropyran‐2,4‐dion. (1. Mitteilung) )
Authors: Kögl F. , Salemink C. A.
Published: September 2010

Die vorliegende Arbeit beschäftigt sich mit der Darstellung von bisher nicht beschriebenen höheren Homologen der Dehydracetsäure und des Triacetsäure‐lactons. Diese Verbindungen zeigen antibakterielle Wirkungen, welche ein näheres Studium wünschenswert erscheinen liessen.
Mechanisms of reactions for introducing sulphonic acid groups into fatty acids
Authors: de Boer J. H.
Published: September 2010

Aliphatic sulpho carbonic acids are mostly prepared by one of three methods, viz.

the direct sulphonation of fatty acids

the addition of bisulphite to an unsaturated fatty acid

the substitution of halogen by the sulphonic acid group.

All three methods have been thoroughly studied by H. J. Backer and his collaborators. All experimental evidence of method a) indicates the mechanism to be a consecutive series of ionic reactions, the real sulphonation agent being the (SO3H) + ion.

It may be that in method b) the negatively charged (SO3H)− ion is the acting agent. Experiments of the author, executed in 1922 in Backer's lab. and only published in his doctor's thesis, indicate that method c) may be governed by a radical mechanism. Such a mechanism is not entirely excluded for method b).
Compounds related to provitamin D3 (IV) ): 3‐Methylcholesterol and the corresponding provitamin (3‐methylprovitamin D3)
Authors: Strating J.
Published: September 2010

3‐Methylcholesterol (II), obtained by the action of Δ5‐cholestenone‐3 (I) with methylmagnesium iodide, probably has the same steric configuration (3β) at carbon atom 3 as cholesterol itself, because it gives, like cholesterol, a digitonide.

Bromination of the benzoate (IIIb) by means of bromosuccinimide, followed by elimination of HBr, leads to the benzoate of 3‐methyl‐provitamin D3 (IVb). This difficultly saponifiable ester is easily converted into the corresponding 3‐methylprovitamin D3 (7‐dehydro‐3‐methylcholesterol) (V) by action with LiAlH4.

The anti‐rachitic activity of the irradiated compound is about 1/80 of that of vitamin D3.
Reactions of thiophene dioxides
Authors: Melles J. L.
Published: September 2010

The substituted thiophene‐1.1‐dioxides are stable substances; they react with maleic anhydride, with nucleophilic reagents, and with reducing agents.

Phenylated and methylated thiophene‐1,1‐dioxides and maleic anhydrides give—with one exception—endovinylene‐cyclohexane‐tetracarboxylic anhydrides; the intermediate endosulphonyl compounds could not be isolated.

Most of the sulphones are not stable towards alkalis and amines. Definite reaction products were isolated in a few cases, e.g. from 3,4‐dimethylthiophene‐1,1‐dioxide and piperidine. Another synthesis of this sulphone is the dehydrohalogenation of 3,4‐dibromo‐3,4‐dimethyl‐thiacyclopentane‐1,1‐dioxide.

Many of these sulphones can be reduced to real thiophene derivatives. In one case both the reduction and the hydrogenation product are identified.
magnified image
The preparation of 1‐methyl‐2‐hydroxy‐3‐diazobenzene‐5‐sulphonic acid
Authors: Klaassens K. H. , Schoot C. J.
Published: September 2010

The preparation of 1‐methyl‐2‐hydroxy‐3‐diazobenzene‐5‐sulphonic acid, starting from o‐cresol, is described. With a small quantity of a strong acid a suspension of 1‐methyl‐2‐hydroxy‐3‐aminobenzene‐5‐sulphonic acid in a solution of sodium nitrite gives the sodium salt of the diazonium compound.
Synthesis of β‐phenyl‐ethylamine derivatives II condensation of phenols with amino‐acetonitriles
Authors: Moed H. D. , Asscher M. , van Draanen P. J. A. , Niewind H.
Published: September 2010

A description is given of the condensation of amino‐acetonitriles with phenols according to the method of Houben‐Hoesch. The condensations have led to the preparation of a number of compounds of the type:
magnified image
A number of s̀‐amino‐acetophenones have been converted into compounds with sympathomimetic activity. An investigation has been made into the conditions and the mechanism of the synthesis, and the influence of substituents in the benzene nucleus on the reactivity of the phenol component. A discussion is devoted to the electronic interpretation of the synthesis according to Houben‐Hoesch.
Preparation of aldehydes by the oxidation of alcohols with lead tetra‐acetate. Part I. Pyridylaldehydes
Authors: Mićović V. M. , Mihailović M. Lj.
Published: September 2010

A method is described for the preparation of pyridylaldehydes (pyridylmethanals), as well as of several derivatives of these compounds, some of which have not hitherto been mentioned in the literature. The aldehydes were obtained from the corresponding pyridinecarboxylic acids, which were esterified, the ethyl esters reduced with lithium aluminium hydride to the pyridylmethanols and the latter in turn oxidized with lead tetra‐acetate in benzene solution.
Sur le Dosage de Traces de Cobalt
Authors: Gallego R. , Deijs W. B. , Feldmeijer J. H.
Published: September 2010

Nous avons étudié les facteurs principaux pouvant modifier la formation du complexe du cobalt avec le sel du nitrosodérivé de l'acide R et aussi ceux qui peuvent intervenir dans la décomposition de ce complexe. Ensuite nous avons étudié les moyens qui permettent d'éliminer les complexes des autres métaux et l'excès du sel du nitrosodérivé de l'acide R.

La méthode à l'acide nitrique cause une destruction incomplète du réactif libre, tandis que l'acide chlorhydrique décompose seulement les complexes des autres métaux et protège le complexe de cobalt pendant la bromuration, donnant ainsi des résultats très reproductibles. Le brome est un réactif excellent pour détruire l'excès du sel du nitrosodérivé de l'acide R, mais il faut employer du sulfite pour réduire les restes de brome libre.
Kinetical experiments on ozonization reactions. IV. Pyridine and some of its derivatives
Authors: Sixma F. L. J.
Published: September 2010

The addition of ozone to 3‐methylpyridine, 2,6‐dimethylpyridine, and 2,4,6‐trimethylpyridine was studied quantitatively. After hydrolysis of the reaction products, the quantity of ammonia formed was measured. The results show that in all the cases investigated the action of ozone leads to the formation of a diozonide; no indication of the addition of ozone to the CN bond was found with any of these compounds.

Further the velocity was measured of the ozone addition to the abovementioned compounds, and also to pyridine, 2‐ and 4‐methylpyridine, and 4‐ethylpyridine. The reaction velocity is smaller than that of the corresponding benzene derivatives. Introduction of methyl groups into the pyridine nucleus enhances the reactivity with regard to ozone.
Reactivity of 4‐nitropyridine‐N‐oxide (III): Reduction in alkaline medium
Authors: den Hertog H. J. , Henkens C. H. , van Roon J. H.
Published: September 2010

It is shown that by reduction of 4‐nitropyridine‐N‐oxide in alkaline medium there are formed i.a. 4,4′‐azopyridine, 4,4′‐azopyridine‐N‐oxide, and 4,4′‐azopyridine‐N,N′‐dioxide.

Syntheses of 4,4′‐azoxypyridine, one of its monoxides, and its dioxide from 4‐nitropyridine are described.

The structure of the above‐mentioned substances is discussed in connection with their ultraviolet absorption spectra.
Investigations on organic fungicides. VII. Further considerations regarding the relations between chemical structure and antifungal action of dithiocarbamate and bisdithiocarbamate derivatives
Authors: van der Kerk G. J. M. , Klöpping H. L.
Published: September 2010

The present paper is a continuation of current work on dithiocarbamic acid derivatives.

By using four test organisms a limited antifungal spectrum is obtained for each compound investigated. These antifungal spectra can be subdivided into four different specificity types, each type comprising compounds or groups of compounds which may be related as to their general mode of antifungal action. This subdivision is supported by the results of respiration measurements. Theoretical considerations allow a more profound specification of the relations between constitution and antifungal activity in the dithiocarbamic acid series.
Studies in azo‐dyestuffs from 6‐amino‐2,3‐dihydro‐3‐ketobenzo‐1,4‐thiazine, with special reference to their possible anthelmintic effects and dyeing properties
Authors: Mackie Alexander , Cutler A. Anthony
Published: September 2010

Azo‐dyestuffs have been prepared from 6‐amino‐2,3‐dihydro‐3‐ketobenzo‐1,4‐thiazine by coupling with various hydroxy‐compounds and with anthranilic acid. Some of them have shown depressant effects on Ascaris lumbricoides and liver fluke (Fasciola hepatica) in vitro, and gave good shades and wool. All the colours were fast to light.
Evaporation of mercury from a solution of a mercurous salt at room temperature
Authors: de Jonge J.
Published: September 2010

A solution of mercurous nitrate gives off mercury vapour at room temperature due to the occurence of the equilibrium magnified image.
Nouvelle Synthèse de Sulfonamides: Réaction de L'anhydride sulfureux sur le Diphényl‐Diazométhane en Présence D'amines. Propriétés du groupe sulfonyle XXIX
Authors: Kloosterziel H. , Deinema M. H. , Backer H. J.
Published: September 2010

La réaction de SO2 sur le diphényldiazométhane en présence d'amines aliphatiques primaires et secondaires conduit aux amides substitués de l'acide diphénylméthanesulfonique. On peut admettre que les amines se fixent sur la double liaison d'un sulfène intermédiaire.
Thermodynamic study on the influence of the carbon chain length of homologous compounds on physical and chemical equilibria in systems consisting of one or more phases
Authors: Eerbeek C. D. F.
Published: September 2010

It is to be expected that for the higher members of a homologous series the heat of formation at a given temperature and state of aggregation is a linear function of the number of C atoms in the normal alkyl group; the increment of the heat of formation per C atom is independent of the nature of the series.

Assuming that this law remains true for infinitely diluted solutions, corollaries are derived for various thermodynamic equilibria in which a member of a homologous series occurs.

It is found that the relations derived for the distribution equilibrium for two liquid phases at infinite dilution, the equilibrium constant for chemical reactions at infinite dilution, the vapour pressure of a homologous series at a given temperature, etc. contain either

quantities independent of n (i.e. the number of C atoms in the normal alkyl group)

quantities linearly related to n, or

quantities whose logarithms are linearly related to n.
The Raman spectra of the compounds NaCl. ALCL3 and NOCl. ALCL3
Authors: Gerding H. , Houtgraaf H.
Published: September 2010

The Raman frequency shifts and the depolarization ratio of the Raman lines have been determined for the compounds NaCl. AlCl3 and NOCl. AlCl3 (in the last case with qualitative polarization measurements only). The preparation of pure NOCl. AlCl3 is described in extenso. The properties of the compound finally obtained are different from those given in the literature. NaCl. AlCl3, has to be considered as Na+AlCl4−, and NOCl. AlCl3 as NO+AlCl4−. There is a perceptible interaction between nitrosyl and the chlorines of AlCl4− in the last compound. The properties of NOCl. AlCl3 are intermediate between those for a pure heteropolar compound (NO+AlCl4−) and a pure molecular compound NOCl. AlCl3, being more alike those of the heteropolar form.

Force constants have been calculated for AlCl4;−, making use of the Lechner formulae and of those for a Urey‐Bradley field and also of those for the orbital valence force field of Heath and Linnett.
Derivatives of p‐diethoxybenzene: I. 1,4‐diethoxy‐2‐chlorobenzene‐5‐diazoniumborofluoride
Authors: Klaassens K. H. , Schoot C. J.
Published: September 2010

The preparation of 1,4‐diethoxy‐2‐chlorobenzene‐5‐diazoniumborofluoride is described and the structure is proved.
Tracer studies on the exchange reactions of some oxygen acids of sulfur: (Short Communication)
Authors: van der Heijde Herman B.
Published: September 2010

Orientating experiments were carried out on the exchange of S35 between labeled sulfurous acid and dithionous acid or their ions at different pH‐levels.
Influence of the solvent on the reactivity of halogeno‐ and alkoxy‐derivatives of nitropyridines towards ammonia
Authors: den Hertog H. J. , Jouwersma C.
Published: September 2010

The reactivity of 2‐bromo‐3‐ethoxy‐6‐nitropyridine, 2‐bromo‐6‐ethoxy‐3‐nitropyridine, 5‐bromo‐2‐nitropyridine, and 3‐ethoxy‐2‐nitropyridine towards solutions of ammonia in water and ethanol has been investigated.

It was shown that in these reactions higher polarity of the solvent accelerates all the substitution processes observed. This effect influences the replacement of substituents occupying the para or ortho position towards the nitro‐group rather than that of the other substituents.

Applying the effect of the solvent, methods were developed for the synthesis of several derivatives of 2‐ and 3‐aminopyridine, inter alia 2‐amino‐3‐ethoxy‐6‐nitropyridine (an analogon of the 1‐alkoxy‐2‐amino‐4‐nitrobenzenes, the group of sweeting substances studied by Blanksma and Verkade) and two mononitro‐derivatives of 3‐aminopyridine.
Chemical investigation of “Karaffs” (english equivalent, celery, apium graveolens, linn.) seed oil
Authors: Farooq M. O. , Kiamuddin M. , Osman S. M.
Published: September 2010

The fixed oil from the seeds of ‘Karaffs’ has been analysed and its fatty acid composition determined by ester fractionation method. Petroselinic (Δ‐6,7‐octadecenoic) acid has been isolated in colourless shining crystals m.p. 29‐30° and found to be the major component of the fatty acids. The total acids of the oil are composed of resin acids 7% and fatty acids 93% (consisting of palmitic 11.7%, petroselinic 41.1%, oleic 30.5% and linoleic 9.7%).
Kinetics of the formation of methylene linkages in solutions of urea and formaldehyde
Authors: de Jong J. I. , de Jonge J.
Published: September 2010

A kinetic investigation is made of the reactions between monomethylol urea, dimethylol urea and urea in acid aqueous solution.

Strong indications are obtained that these reactions are all of one type viz. bimolecular hydrogen ion catalyzed reactions between an amidomethylol group and an amide group, leading to the formation of methylene linkages between urea fragments:

magnified image

The rate constant of this reaction appeared to depend on the type of amide group or amidomethylol group that are reacting. The activation energy is about 15 kcal/mole.

The reaction between two molecules of dimethylol urea was found to be very slow if occurring at all.

The formation of cyclic structures by trimerisation of monomeric methylene urea and the formation of dimethylene ether linkages between urea fragments may be excluded.
Viscous flow through an elastic tube
Authors: Prins W. , Hermans J. J.
Published: September 2010

An approximate theory of viscous flow in elastic capillaries was developed in earlier work2). Because of its biological interest, this theory is compared with the results of model experiments. The wall of the capillary is of rubber; the liquid investigated is a 2.5% Na‐CMC solution in water. Since this liquid is not Newtonian, the theory is extended to non‐Newtonian flow (Sect. 2).

It is found that the agreement between theory and experiment is quite satisfactory. The experimental errors are discussed, and an estimate is made of the error involved in the theoretical treatment.
Kinetical experiments on ozonization reactions: V. The ozonization of some norcaradiene derivatives
Authors: Sixma F. L. J. , Detilleux E.
Published: September 2010

The addition of ozone to some norcaradiene derivatives has been studied quantitatively. The reaction of ozone with methyl and ethyl norcaradiene‐7‐carboxylate (I) results in the formation of a diozonide. Ethyl benzonorcaradiene carboxylate (II) forms a monozonide, which subsequently reacts at a much lower reaction rate, probably producing a tetraozonide.

These results are in opposition to the hypothesis of Badger, stating that the reactivity of the double bond reagents in norcaradiene derivatives towards “double bond reagents” is greatly reduced by conjugation with the cyclopropane ring.

Pure methyl norcaradiene‐7‐carboxylate has been prepared via its dibromo‐derivative.
Derivatives of p‐Diethoxybenzene: II. 1,4‐diethoxy‐2‐aminobenzene‐5‐diazoniumborofluoride
Authors: Klaassens K. H. , Schoot C. J.
Published: September 2010

The preparation of 1,4‐diethoxy‐2‐aminobenzene‐5‐diazoniumborofluoride is described and the structure is proved.
Chloramphenicol analogues I: DL‐2‐dichloroacetamido‐1‐(4‐pyridyl)‐1,3‐propanediol
Authors: van der Meer S. , Kofman H. , Veldstra H.
Published: September 2010

The synthesis of one of the stereoisomeric forms (probably the threo‐form) of DL‐2‐dichloroacetamido‐1‐(4‐pyridyl)‐1,3‐propanediol, the pyridine analogue of chloramphenicol, is described.

Its activity against Salm. typhimurium and Ebert. typhi is 1‐3 per cent of that of chloramphenicol only.
On the reaction of Cyclopentadiene with formaldehyde
Authors: Beets M. G. J. , Drukker E. A.
Published: September 2010

When cyclopentadiene reacts with formaldehyde in the presence of an acid catalyst, an unsaturated m ‐dioxan‐derivative or, under different reaction conditions, an unsaturated diol is formed. Both have been hydrogenated and the properties of the unsaturated and the saturated compounds are described.

Some experiments with other unsaturated compounds are reported.
Polarography of some tropolones
Authors: Neish William J. P. , Müller Otto H.
Published: September 2010

The polarographic behaviour of β,γ‐benzotropolone, tropolone, β‐methyltropolone, and β‐methyltropolone methyl ether is described. Certain correlations between these compounds and the naturally occurring tropolones, colchicine and colchiceine, are pointed out. An explanation is offered for discrepancies between the present results for tropolone and data given by James and Speakman 10) for this substance.
The magnetic susceptibilities of pure and slightly oxidized ferrous hydroxide
Authors: Zernike J.
Published: September 2010

Preparation of pure white ferrous hydroxide; determination of its magnetic susceptibility (χ = 11 200 × 10−6 at 28.4°); also of the more or less oxidized product.
Sesquioxydes obtenus par oxydation de thiophenes: (Propriétés du groupe sulfonyle XXXVI
Authors: Melles J. L. , Backer H. J.
Published: September 2010

L'oxydation de quelques dérivés simples de thiophène rappelle celle du thiophène lui‐même, en conduisant à des produits ayant la composition de sesquioxydes. Ces produits présentent la formule moléculaire de dimères qui se sont formés par addition diénique entre des sulfones et des sulfoxydes.
Kinetics of the hydroxymethylation of phenols in dilute aqueous solution
Authors: de Jong J. I. , de Jonge J.
Published: September 2010

The hydroxymethylation of phenols has been investigated in the pH range 1‐11 and between 70‐130° C in dilute aqueous solution.

The reaction appeared to be bimolecular. Below about pH = 4 the rates were found to be proportional to the concentration of the hydrogen ions, while a proportionality to the concentration of the hydroxyl ions was observed in more alcaline solutions. An influence of the concentration of buffers on the rates has not been observed. The presence of small amounts of triethanolamine does not influence the rate of the reaction. The mechanism of the reaction is discussed.
On the theory of aromatic substitution: II. The orienting effect in some β‐substituted styrene derivatives
Authors: Sixma F. L. J.
Published: September 2010

A theoretical discussion is given of the orienting effect of electrophilic substitution in cinnamic acid, cinnamic aldehyde, β‐nitrostyrene, and similar styrene derivatives. The principal formation of ortho‐ and para‐substitution products is in accordance with the theory.
On the theory of aromatic substitution: III. Reactivity in electrophilic and nucleophilic substitution reactions
Authors: Sixma F. L. J.
Published: September 2010

The effect exercised by substituents on the velocity of electrophilic and nucleophilic substitution reactions of benzene derivatives is discussed in the light of a theoretical treatment of the inductive effect2). The theory is checked against the bromination of substituted phenols and the reaction velocity of piperidine with 2‐nitrobromobenzenes substituted in the 4‐position. A linear relationship exists between the logarithm of the reaction velocity and the effect of the substituent on the activation energy of the reaction (as calculated from the theory).
Reaction of hydrogen atoms with elaidic acid
Authors: Boelhouwer C. , van Steenis J. , Waterman H. I.
Published: September 2010

The reaction of elaidic acid with atomic hydrogen at low temperatures (50° C) was investigated. Besides polymerization, a considerable hydrogenation took place; in contrast with catalytic hydrogenation processes no cis‐trans isomerism could be detected, and displacement of the double bond occurred to a small extent only.
Ueber eine synthese des 3,5‐dinitropyridins
Authors: Plažek Edwin
Published: September 2010

Das 3,5‐Dinitropyridin wurde auf synthetischem Wege dargestelt, seine Eigenschaften wurden untersucht und einige neue, bisher unbekannte Pyridinderivate als Zwischenprodukte erhalten.
The effect of certain biologically active substances upon photosynthesis and dark CO2 fixation
Authors: Havinga E. , Lynch V. , Norris L. , Calvin M.
Published: September 2010

The influence of certain antibiotics and other biochemically active substances on CO2 fixation in the dark and in the light was studied by C14 tracer techniques. Dinitrophenol stopped both processes, whereas antifolics did not show any influence on the rate or the pattern in CO2 fixation by Scenedesmus obliquus under the conditions of our experiments. Chloromycetin did not alter the velocity of CO2 uptake in the dark or in the light.

Penicillin did not alter the total uptake of CO2 but apparently altered the metabolic pattern in dark fixation, e.g. the decrease in the amount of radioactive malic acid formed. In control experiments it was confirmed that malic acid becomes strongly labeled during dark CO2 fixation. Pyrithiamine had no significant influence on total dark fixation, although it lowered the activity of the malic acid spot.

Aureomycin hydrochloride had an inhibiting effect on dark fixation in concentrations of about 10−3 M. It accelerated photosynthesis about two times in 3 × 10−5 M concentration and six times in 1.5 × 10−4 M and higher concentrations. Terramycin hydrochloride showed a similar behaviour. Probably part of this effect is due to shifts in pH and another part to increased buffering capacity. While it was possible to eliminate the direct pH effect, it is difficult to estimate the influence of the buffer capacity. Analysis of the chromatograms of the products formed revealed that the activity in most of the products found in short period photosynthesis was increased proportionally. However, addition of aureomycin produced an abnormally high increase in sucrose. Phosphate increased the amount of alanine produced. A short discussion of these phenomena has been given.
The polarographic reduction of conjugated hydrocarbons: II. The reduction of 1,n‐diphenylpolyenes
Authors: Hoijtink G. J. , van Schooten J.
Published: September 2010

The current‐voltage curves of some 1,n‐diphenylpolyenes were measured in a 0.175 molar solution of tetrabutylammoniumiodide in 96% dioxanewater at 25° and 75° C. The experimental half‐wave potentials and the roots a of the M.O. secular equation, corresponding to the lowest non‐occupied π‐electronic level of the conjugated systems, fit the linear equation: ϵ1/2 = a · γ − 1.05 Volts, discussed in part I, giving a mean value of y¯ = − 2.18 ± 0.04 ev (stand, dev.).

The theoretical discussion of the course of the reduction of conjugated hydrocarbons has been extended, taking into account the effect of the methylene group on the π‐electronic distribution in the intermediately formed radical ions. From a comparison between the results of these theoretical approximations and the experimental data some reasonable suppositions have been made about the behaviour of these polyenes and their partial reduction products at the dropping mercury electrode during electrolysis.
The preparation of some 1,2,3‐tri(trialkylsiloxy) propanes
Authors: Breederveld H. , Steuns C. H. , Waterman H. I.
Published: September 2010

Some 1,2,3‐tri(trialkylsiloxy)propanes have been prepared from the respective trialkylchlorosilanes and glycerol in the presence of pyridine. The specific refractions of these compounds deviate from the theoretical values, as may be expected on the ground of the English theory.
Synthesis of tetrahydroquinoline‐3‐alkyl‐carboxylic acids: Part I. Synthesis of 2‐carboxy‐4‐hydroxy‐3‐quinoline‐alkylcarboxylic acids
Authors: Stefanovic Gjorgje , Čelap Milenko B.
Published: September 2010

The synthesis of 2‐carboxy‐4‐hydroxy‐3‐quinoline‐alkylcarboxylic acids is described, these acids being prepared by the condensation of the triethyl esters of α‐oxalyldicarboxylic acids with aniline. By heating the anils thus obtained, esters are formed which, upon saponification, yield the free acids.
Vinylogie chez les composés de sulfonyle II: (Propriétés du groupe sulfonyle XL)
Authors: Backer H. J. , Strating J. , Hazenberg J. F. A.
Published: September 2010

Poursuivant leurs recherches sur les composes sulfones vinylogues, les auteurs ont fait réagir le 1,2‐dichloro‐1‐tertiobutylsulfonyl‐éthène (I) avec l'ammoniac, plusieurs amines primaires et secondaires; quelques composés à méthylène actif et avec des magnésiens.

Enfin on a soumis le sulfochlorure vinylogue (I) à une réduction, qui conduit à plusieurs produits.
Die Absorptionsgeschwindigkeit von Ammoniak in Wasser bei vorhandensein von Kohlendioxyd: Ein Beitrag zur Berechnung von Ammoniakwäschern in Gaswerken
Authors: Bramslev E.
Published: September 2010

Die für Gaswerke so wichtige gleichzeitige Auswaschung von Ammoniak und Kohlendioxyd wird als ein Diffusionsprozess in Verbindung mit einer chemischen Reaktion behandelt.

Die aufgestellten Differentialgleichungen werden unter Vernachlässigung von Gliedern weniger Bedeutung integriert und, es wird gezeigt, wie das Resultat für einen Satz gegebener Werte mit einer numerischen Integration in guter Übereinstimmung ist.

Die Absorption von Kohlendioxyd in Ammoniakwasser wird nach derselben Methode behandelt und die Resultate stimmen hier mit van Krevelen5) überein.

In einem mit 5 mm Raschigringen gefüllten Glasturm werden Absorptions‐versuche mit Gas mit wechselndem Ammoniak‐ und Kohlendioxydgehalt ausgeführt, und die Resultate sind mit den entwickelten Formeln in guter Übereinstimmung.
Migration of halogen atoms in halogeno‐derivatives of 2,4‐dihydroxypyridine (II)
Authors: Kolder C. R. , den Hertog H. J.
Published: September 2010

When 3‐bromo‐2,4‐dihydroxypyridine is heated with an aqueous solution of nitric acid, 5‐bromo‐2,4‐dihydroxy‐3‐nitropyridine is formed. This reaction product was also obtained by nitrating 5‐bromo‐2,4‐dihydroxypyridine and by brominating 2,4‐dihydroxy‐3‐nitropyridine; its structure was established by converting it into the known 5‐bromo‐2,3,4‐trichloropyridine.

The mechanism of the nitration of 3‐bromo‐2,4‐dihydroxypyridine is discussed in comparison with that of its chlorination.
The dependence of potential difference on limiting current in mixed electrolytes
Authors: Macgillavry D.
Published: September 2010

The steady states of ionic motions and the steady distributions of concentrations are developed for mixed electrolytes when only one kind of ions is reducible at the cathode. The resulting potential difference in solution is derived. The analysis is given for the limiting case that maximum current is reached.
The determination of organic acids in plant material by means of paper chromatography
Authors: van Duuren A. J.
Published: September 2010

An improved procedure for the determination of organic acids in plant products by paper chromatography is described.
The polarographic reduction of conjugated hydrocarbons: III. Comparison of various M.O. approximations with experimental half‐wave potentials of alternant hydrocarbons
Authors: Hoijtink G. J. , van Schooten J.
Published: September 2010

The linear relation ϵ = a. γ −1.05 Volts1a) has been discussed, using for the computation a the following M.O. approximations:

a) the original method of Hückel;

b) the approximation used by Wheland (overlap integral 1/4);

c) the non‐bonding M.O. method of Longuet‐Higgins.

Substituting in the linear equation the half‐wave potentials of twenty alternant hydrocarbons and the computed roots a, the following mean values of the resonance parameter γ were obtained:

magnified image

Some conclusions have been drawn about the applicability of these semiempirical methods.
Thorium ‐ its estimation and separation from cerite earths: Use of 7‐hydroxy coumarin‐4‐acetic acid
Authors: Eswaranarayana N.
Published: September 2010

7‐Hydroxy coumarin‐4‐acetic acid precipitates thorium completely in the pH range 2.5 to 3.2. The precipitate is crystalline and may be filtered easily. Thorium in monazite is estimated after a single precipitation. As little as 1 mg of thorium is accurately estimated. The metal is further separated from twice its amount of uranium in a single precipitation. Most of the common elements do not interfere.
The chemical composition of some condensates of urea and formaldehyde
Authors: de Jong J. I. , de Jonge J.
Published: September 2010

Some condensates of urea and formaldehyde were prepared from solutions of pH 2‐7 at temperatures of 20‐76° C. These products have been analysed with respect to their content of methylene groups, methylol groups and urea groups. The average molecular weights could be estimated. The analytical data are in harmony with the occurrence of methylene bridges between the urea fragments. The condensates will be formed by a stepwise condensation reaction.

“Methylene urea” may be a mixture of condensates with an average molecular weight of 300‐500.
Steric hindrance in the para‐nitroanilides of 2,3‐ and 2,5‐dimethylbenzoic acid
Authors: Soei Ng Tet , Verkade P. E. , Wepster B. M.
Published: September 2010

The deacylation rate constants of the compounds mentioned in the title provide corroborative evidence for the existence of the “ortho‐xylene effect”.