bluuebunny/crossref_metadata_2025 huggingface dataset:
X‐ray investigation of d‐α‐Br, Cl and CN‐camphor . A direct determination of a molecular structure by comparison of isomorphous crystal structures
Authors: Wiebenga E. H. , Krom C. J.
Published: September 2010

The structure of the camphor molecule was determined by comparison of the X‐ray diagrams of the isomorphous α‐Br, Cl and CN derivatives. This rather general procedure, avoiding the usual difficulty of Fourier synthesis by a direct determination of the signs of the Fourier components, is described in the introduction of part I. The structure thus found has been checked in part II by comparison of calculated and observed intensities.
The determination of different sugars in aqueous extracts of rye milling products in connection with amylolysis. I. Pre‐existing reducing sugars
Authors: Hintzer H. M. R.
Published: September 2010

Exact knowledge of the carbohydrate system of the cereal grain is important with regard to the distinction between the kinds of cereals, and especially in the case of rye for the sake of information about its baking value.

A method by which the soluble carbohydrates of the cereal grain can be determined side by side with sufficient accuracy cannot be found in the literature up to the present moment. In the following paper a method is indicated by which the reducing sugars in rye flour may be determined biochemically.
The interaction of 1‐chloro‐2‐cyano‐4‐nitrobenzene and 1‐chloro‐4‐nitrobenzene with sodium glycolate and sodium glycerolate
Authors: Blanksma J. J. , Fohr P. G.
Published: September 2010

The chlorine atom in 1‐chloro‐2‐cyano‐4‐nitrobenzene can be replaced by the OCH2. CH2OH and the OCH2. CHOH. CH2OH groups, respectively, by treatment with sodium glycolate and sodium glycerolate. With an anhydrous solution of sodium glycolate in glycol at 150°, 1‐chloro‐4‐nitrobenzene gives 4‐nitrophenyl β‐hydroxy‐ethyl ether. No crystalline compound could be obtained by the interaction of sodium glycolerate and 1‐chloro‐4‐nitrobenzene.
Substitution of mobile halogen atoms in some halogenonitrobenzenes with glycol and glycerol
Authors: Blanksma J. J. , Fohr P. G.
Published: September 2010

The mobile halogen atom in 1‐chloro‐2:4‐dinitrobenzene and other halogenonitrobenzenes can be replaced, by interaction with sodium glycolate or sodium glycerolate, by the β‐hydroxyethyl‐, OCH2.CH2OH and βγ‐dihydroxypropyl, OCH2.CHOH.CH2OH group, respectively. Glycol and glycerol are sweet but 2: 4‐dinitrophenyl β‐hydroxy‐ethyl ether and 2: 4‐dinitrophenyl βγ‐dihydroxypropyl ether, obtained from them, are bitter and these compounds on partial reduction with sodium disulphide afford 2‐amino‐4‐nitrophenyl β‐hydroxyethyl ether, which is twenty times as sweet as cane sugar and 2‐amino‐4‐nitrophenyl‐βγ‐dihydroxypropyl ether, which is thirteen times as sweet as cane sugar. Since 2‐amino‐4‐nitrophenyl ethyl ether is 1,400 times and 2‐amino‐4‐nitro‐phenyl n‐propyl ether, 5.000 times as sweet as sugar, the replacement of the ethoxy group by a β‐hydroxy‐ethoxy group and the replacement of n‐propoxy‐by a dihydroxypropoxy group leads to a very considerable decrease in the intensity of the sweet taste. For the development of the sweet taste, in the compounds mentioned, a free amino group is necessary, since the corresponding acylated derivatives are tasteless, which is in agreement with the observations made previously with 1‐alkoxy‐2‐amino‐4‐nitrobenzenes

) J. J. Blanksma and P. W. M. van der Weyden, Rec. trav. chim. 59, 629 (1940).

.
The reaction between ethyl chlorocarbonate and pyridine compounds
Authors: Arens J. F. , van Dorp D. A.
Published: September 2010

By the action of ethyl chlorocarbonate upon 2‐ and 4‐alkyl pyridines high‐boiling substances are formed from 2 molecules of the pyridine compound and 1 molecule of the chloro‐ester minus hydrochloric acid. It is highly probable that these substances contain an unsaturated chain, formed by the opening of one pyridine ring, attached to the nitrogen atom of a 1,2‐dihydropyridine ring (formula V). By the action of acids and alkalies the substances decompose into the original pyridine compound and carbon dioxide.
Application de la theorie de l'hyperconjugaison a l'etude de la reactivite des molecules organiques
Authors: Buu‐Hoï Ng. Ph. , Daudel Raymond
Published: September 2010

Il est montré que la théorie de l'hyperconjugaison permet d'expliquer les règles de substitution expérimentalement trouvées, non seulement pour le noyau benzénique, mais également pour le noyau du naphtalène. La généralisation du concept de l'hyperconjugaison à des combinaisons non aromatiques permet de rendre compte de nombreuses propriétés physiques et chimiques importantes de ces corps.
Derivatives of hydrazine‐N. N′‐dicarboxylic acid
Authors: Vogelesang C.
Published: September 2010

Hydrazine‐N, N′‐dicarboxylic acid is not known in the free state, but the methyl and ethyl esters are of some importance because they form the starting materials for the preparation of the corresponding azo‐esters. Various other derivatives of hydrazine‐N,N′‐dicarboxylic acid are known, such as the amide, the azide and the hydrazide. These have been studied further.

In the hope of being able to prepare nitrohydrazines their behaviour towards absolute nitric acid was investigated; both the esters and the methylamides were completely oxidized. This occurred also with dimethyl methylhydrazine‐N,N′dicarboxylate and methylhydrazine‐ N,N′‐dicarbomethylamide, compounds in which three of the four hydrogen atoms in hydrazine are replaced by protecting groups; nevertheless the stability towards absolute nitric acid appears to be insufficient and these substances differ from compounds like acetanilide and methylaniline, which afford nitramines.

The dimethyl ester of (hydrazine‐N,N′‐dicarbohydrazide)‐ωω′‐dicarboxylic acid still gives a visible coloration with 1 part of copper in 4 × 106 parts of water.
Note on the preparation of fumaric nitrile
Authors: Gaade W.
Published: September 2010

An improved method for the preparation of fumaric nitrile is described, giving a considerably higher yield than the method known from the literature.
On the use of the rotating step sector in combination with intermittent light sources in spectrochemical analysis II
Authors: Schmidt R.
Published: September 2010

In a previous communication

) R. Schmidt, Rec. trav. chim. 62, 437 (1943).

) it was shown that it is possible to apply the combination of an interrupted are, as used by the author

) R. Schmidt, A. Schuringa, Rec. trav. chim. 64, 349 (1945). R. Schmidt, thesis Amsterdam 1942.

), and a slowly rotating step sector to the determination of a function of the relative intensities of two spectral lines, which may be used in quantitative spectrochemical analysis as a measure of concentration.

To this end the sector speed must be adjusted so that one flash ‐ or an integral multiple ‐ passes the smallest aperture of the sector during one revolution.

Arguments are now put forward toward the conclusion that true relative intensities may be measured in this way if the sector speed exceeds a certain critical value, which depends on the photographic emulsion and the illumination (energy/cm2‐sec).

Several photographic emulsions were tested with respect to this point.
The separation of long‐chain and compact molecules by adsorption
Authors: Nederbragt G. W. , de Jong J. J.
Published: September 2010

Binary mixtures of saturated hydrocarbons (paraffins and naphthenes), dissolved in pentane, were passed through large quantities of earth.

Extremely good separations were obtained, the long‐chain molecules being the most retained by the earth.
Untersuchungen über Indolderivate. IX . Die reaktion zwischen methyl‐α‐brompropylketon und primären und sekundären aromatischen aminen
Authors: Janetzky E. F. J. , Verkade P. E.
Published: September 2010

In Anschluss an früheren Untersuchungen wird die Reaktion zwischen Methyl‐α‐brompropylketon und Anilin bzw. Monomethylanilin untersucht.
Organic analysis of hevea latex. IX. Some details of the mainfractions
Authors: Altman R. F. A.
Published: September 2010

Some details of the preparation, properties and chemical composition of the main fractions separated from Hevea latex are outlined. The results, which relate exclusively to fresh unammoniated latex of Hevea clone “Tjirandji 1”, are summarized in the table on page 923.
The preparation of peroxides by the oxidation of propane
Authors: Kooijman P. L.
Published: September 2010

The following is a description of an investigation into the optimum conditions for the preparation of peroxides by incomplete oxidation of propane. Special attention has been paid to the optimum formation of hydrogen peroxide.

In connection with the removal of heat, it is probably only possible to use a 90/10 propane‐oxygen mixture in a technical apparatus. With this mixture the optimum production of hydrogen peroxide was found at an average reaction temperature of 465°C and a contact time of 4 sec.

Under these conditions 15 moles of peroxides (9 moles of which was free hydrogen peroxide) was formed per 100 moles of propane used. At the same time 83 moles of propene was formed, in addition to 87 moles of water, 34 moles of carbon oxides, 12 moles of aldehydes, 1 mole of alcohol and 1 mole of hydrogen.
The mechanism of uranium fission
Authors: Meijer Martin
Published: September 2010

A possible mechanisms of uranium fission is given, the endproducts being 13856Ba and 8436Kr.
Some properties of the ecgonines and their esters V: Conversion of 1‐ecgonine in aqueous solutions
Authors: de Jong A. W. K.
Published: September 2010

By heating l‐ecgonine in weakly acidified aqueous solution and also in strong hydrochloric acid solution, l‐ecgonine is converted to the extent of 10.5‐12.5% into d‐φ‐ecgonine, an equilibrium mixture of ecgonines being formed.

Both l‐ and d‐φ‐ecgonine give black crystals like l‐ecgonidine with hydriodic acid solution containing iodine; these crystals, when boiled with water, give solutions which show respectively leavo‐ and dextro‐gyratory rotations.

On boiling l‐ecgonine as an alkali‐salt in saturated alkali chloride solution, another equilibrium is reached between the ecgonines; the sodium salt gave a 86.9% conversion into d‐φ‐ecgonine, the potassium salt one of 69% and the calcium salt one of 78.5%.
Researches on heat of combustion I: Method and apparatus for the accurate determination of heats of combustion
Authors: Coops J. , van Nes K. , Kentie A. , Dienske J. W.
Published: September 2010

After a brief description of a new apparatus for the determination of heats of combustion, the theory of an isothermally jacketed calorimeter is discussed. Several factors which require attention in accurate determinations are dealt with, viz.: purity of reagents, completeness of the combustion reaction, determination of time, determination of weight and corrections of the second order. A description is then given of some details of the apparatus and method. The accuracy attained, 0.01‐0.02%, is demonstrated in a series of experiments. Finally, it is shown that the heat of combusiton of our sample of benzoic acid is in excellent agreement with that of preparation 39b of the National Bureau of Standards, Washington.
Researches on heat of combustion III: The use of the Beckmann thermometer as a very accurate instrument for use in isothermally jacketed calorimeters
Authors: Coops J. , van Nes K.
Published: September 2010

For measuring a rise in temperature the ordinary Beckmann thermometer is in no way inferior to the resistance thermometer if the measurements are carried out in a definite way and if at the same time a number of precautions (with regard to vibrator, manostat and water jacket around the scale) are taken, in order to obviate the effects of possible errors in the instrument. In an example it is shown that by taking these things into consideration it is possible to obtain a (relative) temperature reading, which is accurate to 5 × 10−5°. Thus it is possible, by using the Beckmann thermometer, to carry out heat measurements reproducible to 0.01%.
Researches on heat of combustion IV: Technique for the determination of the heats of combustion of volatile liquids
Authors: Coops J. , Mulder D. , Dienske J. W. , Smittenberg J.
Published: September 2010

A method is described for filling thin‐walled ampullae with volatile liquids with the total exclusion of air and water. In this way it is possible to weigh out accurately the amount of material used for a heat of combustion measurement before the experiment is made. To aid the combustion reaction in proceeding to completion a high platinum crucible is used covered with a platinum shield. In a normal heat of combustion reaction it is impossible to detect the presence of carbon monoxide in the combustion gases. The reproducibility obtained is 0.01‐0.02%.
The relation between the nature of the bond in copper salts used for intravenous injection, and the rate of absorption of copper by the liver
Authors: Havinga E. , Bykerk R.
Published: September 2010

Solutions of radioactively tagged Cu‐acetate, Cu‐glycinate and “Ebesal” were injected intravenously in calves. After about 3 1/2 h the animals were killed, their livers destructed and metallic copper isolated from the destruction liquid by precipitation with A1.

Measurement of the radioactivity showed increasing absorption with increasing strength of binding of the copper in the salts injected (acetate → glycinate → Ebesal). The suggestion is made that the liver might be able to destroy the Cu complex much better than other organs and so might collect the copper without serious competition by other organs.
Investigations concerning polymerization of propene and ethene induced by tetraethyl lead
Authors: Kooijman P. L. , Ghijsen W. L.
Published: September 2010

The following describes an investigation into the polymerization of propene and ethene induced by tetraethyl lead at temperatures of about 300°C and a maximum initial pressure of about 250 atm.

The experiments were made in an autoclave. The amount of olefine in g mol polymerizing under the inducing influence of tetraethyl lead was determined as a function of the reaction temperature and the initial pressure; further, the products of the thermal polymerization as well as those formed by the induced polymerization were examined.

A discussion is given regarding the possible procedure of the reaction based on the results obtained.
Researches on sulphanilamide, para‐amino‐benzoic acid and their derivatives. IV: The behaviour of sulphanilamide, p‐aminobenzoic acid and of their derivatives with respect to the mercury/solution interface (polarographic investigations) and to lecithin and protein monolayers
Authors: Veldstra H. , Havinga E.
Published: September 2010

Sulphanilamide, p‐aminobenzoic acid and a number of their derivatives are studied polarographically in order to ascertain whether or not it is probable that p‐aminobenzoic acid functions in a redox system, and to compare their affinities for the rather apolar mercury/solution boundary. The latter serves to a certain extent as a model for a lipophilic membrane of a type within which London‐van der Waals' forces predominantly determine the degree of interaction. In this way very typical differences come to the fore which generally parallel those obtained in the investigations of U.V. absorption spectra and electrochemical properties, as well as the activity of the compounds in vivo. For p‐aminobenzoic acid it may be concluded that a direct function in a redox system is very improbable. In addition mono‐layers of lipoid or protein character are used as models for membranes in which other types of forces than those considered above play a rōle.
Researches on the alkoxy‐amino‐nitrobenzenes. III: Nitration of 1‐alkoxy‐2‐aminobenzenes and 1‐alkoxy‐2‐acetylaminobenzenes
Authors: Verkade P. E. , Roelfzema H. , Meerburg W. , Bosma G. S. K.
Published: September 2010

Nitration of 1‐alkoxy‐2‐acetylaminobenzenes with an excess of nitric acid, sp. gr. 1.40, leads to a mixture of the 4‐nitro and the 5‐nitro derivative, in which the latter substance predominates.

Nitration of 1‐alkyloxy‐2‐aminobenzenes or 1‐alkyloxy‐2‐acetylaminobenzenes with the calculated amount of nitric acid in concentrated sulphuric acid gives the 4‐nitro derivative as the sole or practically sole nitration product.

The results obtained in the nitration are discussed from a theoretical point of view.
The bromination of 1‐aminonaphthalene in concentrated hydrochloric acid. (discrepancies in the literature I)
Authors: van Alphen J.
Published: September 2010

Upon bromination of 1‐aminonaphthalene in concentrated hydrochloric acid at 0° 2,4‐dibromo‐1‐aminonaphthalene is formed.
A qualitative demonstration of Gibbs surface tension equation
Authors: Nieuwenhuis K. J.
Published: September 2010

The exact quantitative derivation of the Gibbs formula, relating the adsorption of the solute at the interface of a solution with another phase to the change in interfacial tension (free energy of the interface) as the concentration of the solute varies, requires a thorough knowledge of thermodynamics.

For instructural purposes and for better understanding the foundations of the equation it seems worth while to look for a qualitative demonstration.

It appears, that it is impossible to prove the law expressed by the equation, in quite the same manner in the two cases of positive and negative adsorption. But a fictitious process to produce one cm2 of the actual surface can be devised which consists of two steps and is applicable to both cases, if only the order of the two steps is reversed.

This demonstration is based on the properties of the particles (molecules or ions) of the solute, which influence both the sign of the adsorption positive or negative) and the change of the surface tension.
L'hydrogénation de la 2,6‐Diméthylpyrone‐4
Authors: de Vrieze J. J.
Published: September 2010

L'hydrogénation de la diméthylpyrone à l'aide de nickel Raney donne le tétrahydropyranol et un diol acyclique. Le tétrahydropyranol est un mélange de deux isomères, qui ne diffèrent que par la position du groupe hydroxyle et de l'hydrogène liés à l'atome de carbone 4. Les deux groupes méthyle occupent la position cis. L'oxydation des deux tétrahydropyranols aboutit à la même cétone.
Studies of gas absorption: III. Gas phase resistance to gas absorption in scrubbers
Authors: van Krevelen D. W. , Hoftijzer P. J. , van Hooren C. J.
Published: September 2010

A modified Sherwood‐Gilliland equation for mass transfer in the gas phase is applied to gas absorption in scrubbers. The equation can be written in the following dimensionless form:

where the dimensionless groups have the following significance

The equation is checked on the available data in the literature and on experiments by the authors.

The “constant” c appears to depend on the ratio:

\documentclass{article}\pagestyle{empty}\begin{document}$\frac{{\rm d}}{{\rm h}}\, = \,\frac{{{\rm diameter}\,{\rm of}\,{\rm packings}}}{{{\rm height}\,{\rm op}\,{\rm packed}\,{\rm column}}}$\end{document} this function may be approximated by the relationship: \documentclass{article}\pagestyle{empty}\begin{document}${\rm c} = {\rm c}_0 \left( {\frac{{\rm d}}{{\rm h}}} \right)^{1/3} .$\end{document}

For wood grid packing the average value of co is 0.35; for rings and other packings there seems to be a trend to smaller co‐values at smaller packing sizes.
The extinctiometric determination of small quantities of histamine
Authors: Havinga E. , Seekles L. , Strengers Th.
Published: September 2010

The most sensitive chemical methods for the determination of histamine described in the literature are based on the so‐called diazo reaction. The reliability of these methods is however too low for them to have become generally accepted, while we found it impossible by these methods to determine smaller amounts than 5 γ of histamine.

When a number of conditions were observed we succeeded in determining quantitatively amounts of histamine down to 0.2 γ with great accuracy.

A method of procedure for the determination and the results of a number of determinations according to this procedure are given.
Carbonyl‐substituted naphthoquinones. Part I. Methyl ketones unsubstituted in the side chain
Authors: Spruit C. J. P.
Published: September 2010

The preparation of a number of compounds, derived from, or related to 1,4‐naphthoquinone, containing a carbonyl group in a side chain is described.
Transposition Intramoléculaire des Nitrophénylsulfonylguanidines
Authors: Backer H. J. , Moed H. D.
Published: September 2010

La décomposition des nitrophénylsulfonylguanidines, en présence de bases diluées, avec production d'anhydride sulfureux, repose sur une transposition intramoléculaire. Les auteurs se sont appliqués à étudier le mécanisme et les conditions de cette transposition. Elle constitue un procédé pratique pour la synthèse de nitrophénylguanidines et de nitrodiphénylamines.
The ozonization of pyridine and some of its homologues in connection with the bond structure of pyridine
Authors: Kooyman E. C. , Wibaut J. P.
Published: September 2010

The ozonization of pyridine, 4‐ethylpyridine, 2,6‐dimethylpyridine, 2,4,6‐trimethylpyridine, 2,3‐dimethylpyridine, 3,4‐dimethylpyridine and 2,3,4‐trimethylpyridine is described.

The products formed upon hydrolysis of the ozonized bases were found to consist of glyoxal derivatives, acids, ammonia and peroxides. Probably, acid amides are also present.

The glyoxal derivatives could be isolated and identified in the form of the corresponding bis‐(p‐nitrophenyl)‐hydrazones. The formation of glyoxal, methylglyoxal and diacetyl from 2,3‐dimethylpyridine, 3,4‐dimethylpyridine and 2,3,4‐trimethylpyridine proved these bases to react as if consisting of a mixture of their Körner‐Dewar forms.

This result, which is analogous to that which is found in the ozonolysis of benzene homologues, may be explained by assumptions based on the theory of resonance.

A tentative scheme is given for the primary reactions involved, which is in full agreement with experimental evidence but which has not been proved with certainty.

The conversion of the pyridine bases was found to proceed very slowly as compared with the corresponding reaction in the benzene series, the major part of the starting material being recovered.

Some of the main results of this investigation have already been described by us in a preliminary communication2).
Viscosities of cis‐ and trans‐ 1‐2‐dichloroethene, in connection with Eyring's theory of viscous flow
Authors: Ketelaar J. A. A. , de Vries L. , van Velden P. F. , Kooy J. S.
Published: September 2010

Using a modified form of the Ostwald viscosimeter, viscosity‐measurements have been carried out over a temperature‐range from the melting points up to about 20°C for the two isomers of 1,2‐dichloroethene. Densitymeasurements were made over the same range of temperature. Special care has been taken in purifying the samples used. From the data obtained, values of the free energy, the energy and the entropy of activation for viscous flow have been calculated, using the theory of Eyring. It appears that the experimental quantity Evis, defined by
equation image
, has a temperature‐independent value of about the same magnitude for both isomers, whereas Eyring's “energy of activation for viscous flow” is temperature‐dependent.

It is concluded that both isomers behave as normal unassociated substances, which conclusion is reached as well from consideration of the values of the “rheochor” and from the relation between the surface tension and Evis.
An integrating Weissenberg‐apparatus for X‐ray analysis
Authors: Wiebenga E. H.
Published: September 2010

A Weissenberg‐apparatus is described, giving accurate values of the integrated reflexion‐intensities without the use of an integrating photometer.
On α‐hydroxy‐β.β‐dioxymethylbutyrolactone
Authors: Rinkes I. J. , van Schelven Th.
Published: September 2010

This short communication contains an accurate statement on the melting point of the above‐mentioned compound.
Disintegration of silver halide crystals by irradiation with ultraviolet light
Authors: Kooy J. N. , Burgers W. G.
Published: September 2010

The disintegration of silver halide crystals by irradiation with ultraviolet light manifests itself in Debije‐Scherrer photographs of powdered preparations in various ways: by diminishing the discontinuous appearance of the interference lines of the non‐irradiated crystallites and by a broadening of the lines of the Kα1α2‐doublet, as shown by high‐order reflections. Also the formation of silver in a finely divided form is clearly visible.

On irradiation of single crystals of silver chloride, the X‐ray photographs show the presence of silver crystallites with preferential orientations, as evident from the appearance of Debije‐interference lines with intensity maxima. This points to a formation of individual small silver crystallites with partly coinciding orientations. The exact crystallographic character of the preferred orientation and its possible connection with that of the irradiated AgCl‐crystal, has not been investigated.
Cétones, phénols, et naphtols dérivés du chaulmoogra
Authors: Buu‐Hoï N. G. Ph. , Cagniant Paul
Published: September 2010

Dans ce travail, les auteurs décrivent la préparation et les propriétés d'une série de cétones provenant de réactions de Friedel‐Crafts entre les chlorures des acides hydrogénés de l'huile de chaulmoogra (acides hydnocarpique et chaulmoogrique hydrogénés) et une série d'éthers‐oxydes de monophénols, de polyphénols, et de naphtols. Certaines de ces cétones ont été réduites par la methode de Clemmensen, et les éthersoxydes à longue chaîne obtenus ainsi ont été transformés en phénols libres. Les substances ainsi préparées sont très peu toxiques, et inhibent très légèrement la croissance du bacille de Koch. Des observations intéressantes ont pu être faites sur la fission hydrolytique de certaines des cétones ainsi preparées, sous l'action des hydracides.
Des Cétones Dérivées du Thionaphtène
Authors: Buu‐Hoï N. G. Ph. , Cagniant Paul
Published: September 2010

Dans ce travail, les auteurs décrivent les réactions de Friedel‐Crafts entre une série de chlorures d'acides gras aliphatiques et le thionaphtène. De nombreuses cétones nouvelles ainsi que certains de leurs dérivés sont mentionnées à ce propos, et les analogies de comportement entre le thionaphtène et le naphtalène sont évoquées.
The action of hydrogen peroxide on α‐and β‐glycerophosphoric acids
Authors: Neumann H.
Published: September 2010

The following is a discussion of the oxidation of α‐ and β‐glycerophosphoric acids by hydrogen peroxide under various conditions. The above mentioned esters of phosphoric acid appear to be unsuitable as a substrate in phosphatase determinations, when the action of the peroxide on the phosphatase reaction is being examined; phosphoric acid is split off from these esters by hydrogen peroxide.
Studies of gas absorption. IV. Simultaneous gas absorption and chemical reaction
Authors: van Krevelen D. W. , Hoftijzer P. J. , van Hooren C. J.
Published: September 2010

Gas absorption with simultaneous chemical reaction can be divided into three characteristic groups.

For the very slow reactions the rate‐determining step is the diffusion of the solute gas through the liquid film.

Chemical reaction velocity is determinative for moderately rapid and slow reactions.

For the very fast reactions gas film resistance to the solute gas and liquid film resistance to the reactive liquid component are rate‐determining.

Rate equations for the last group in terms of the individual mass transfer coefficients have been derived and have been checked on absorption experiments.

The experimental results prove to be correlated satisfactorily.
A complete extraction of the bases and the acid esters of l‐nor‐ecgonine from coca leaves
Authors: de Jong A. W. K.
Published: September 2010

The leaves, 20 g. are mixed with finely pulverised quick lime, containing a quantity of calcium oxide corresponding exactly with the moisture content of the leaves. After remaining for 24 hours in a closed flask they are transferred to an extractor containing a mixture of 100 cm3 of anhydrous benzene and 5 cm3 of absolute methyl alcohol. A quantity of ammonia solution, containing exactly 1.938 g of water is added and the leaves mixed with the solvents. After 24 hours, finely pulverised quick lime possessing a quantity of calcium oxide corresponding with the quantity of water used in the ammonia solution is added and after mixing, the extractor closed until the following day. Percolation is then started in a slow rate. As soon as the solvent mixture is run down a quantity of the mixture of anhydrous benzene and absolute methyl alcohol boiling at 58° is added to the leaves. Percolation with this solvent mixture is finished when the percolate mesures 800 cm3. The mixture boiling at 58° is distilled from this percolate and the remaining benzene solution is filtered from the calcium salts insoluble in benzene. The residue from the benzene solution is shaken with 25 cm3 of n/5 HCl solution and 100 cm3 of ether. The quantity of bases, the cocaines and the methyl ester of ecgonine can be determined in the hydrochloric acid solution so obtained. The quantity of l‐nor‐ecgonine can be determined in the mixture of calcium salts.
The preparation of ozone by electrolysis
Authors: Boer H.
Published: September 2010

Instructions are given for the construction of an electrolytic ozonizer. The ozone percentage reached is 12.5% by weight with an ozone production of 13.5 mmol./hour and a gas flow of 3.5‐4 l per hour of oxygen.
La Réaction de L'Aniline sur L'Orthoformiate D'Éthyle
Authors: Backer H. J. , Wanmaker W. L.
Published: September 2010

Contrairement à l'opinion courante, la réaction de l'aniline sur l'orthoformiate d'éthyle ne donne pas le trianilinométhane, mais la diphénylformamidine.
On the solubilisation of aromatic amines by purines
Authors: Neish W. J. P.
Published: September 2010

The solubilities of the carcinogenic amines, 2‐naphthylamine, 2‐aminofluorene, 2‐anthramine, 4‐aminostilbene, 4‐aminoazobenzene and benzidine in water and in aqueous solutions of caffeine have been examined and it has been found that caffeine exerts a solubilising action on all these amines. Caffeine has quite a marked solubilising action on the simpler amine, 1‐methoxy‐2‐amino‐4‐nitrobenzene and it has been shown that sulphapyridine and sulphathiazole are more soluble in caffeine solutions than in water.

The solubility of 2‐aminofluorene has been examined in aqueous solutions of various purines and the results are of the same order as those obtained by Weil‐Malherbe for the solubility of benzpyrene in solutions of the same purines. The most efficient purines are those with the greatest degree of N‐methylation.

The influence of a mixture of caffeine and 1,3,7‐trimethyluric acid on the solubility of 2‐aminofluorene in water has been studied and it is shown that the solubilising power of the mixture is less than the sum of the separate effects of each purine on the solubility of the amine. This is taken to mean that the purines antagonise each other probably owing to forces acting between themselves of the same nature as those responsible for the aminofluorene‐purine solubility effects. This effect, which requires further study would probably be of importance in biological systems.

Some evidence is given that 2‐phenyl‐quinoline‐4‐carboxylic acid (cinchophen) is solubilised by aqueous solutions of caffeine.
Note on the synthesis of pyridine derivatives from glutarimide by W. W. Crouch and H. L. Lochte
Authors: den Hertog H. J. , Farenhorst E.
Published: September 2010

Crouch and Lochte have described a new synthesis of pyridine derivatives, in which they start from glutarimide or from its alkyl derivatives

W. W. Crouch and H. L. Lochte, J. Am. Chem. Soc. 65, 270 (1943).

). By the action of phosphorus pentachloride on glutarimide at a slightly raised temperature they obtained a trichloropyridine, m.p. 66‐67° and they have shown indirectly that this compound is the 2,3,6‐isomer.

We have now reacted glutarimide with phosphorus pentabromide and have confirmed the reasoning of Crouch and Lochte, because the tribromopyridine obtained has been identified with 2,3,6‐tribromopyridine, prepared by brominating 3‐bromopyridine at 500°

H. J. den Hertog and J. P. Wibaut, Rec. trav. chim. 51, 940 (1932).

. Moreover, 2,3,5,6‐tetra‐bromopyridine appeared to be formed, which was identified with a sample obtained by brominating 3,5‐dibromopyridine at 500°.

Glutarimide (1 g) was mixed with phosphorus pentabromide (12 g) and the mixture held at 80‐90° for 2 1/2 hours. The reaction product was then poured out into water and the crystals, which separated after a little time, were submitted to a steam distillation. The first fraction in the steam distillation (60 cm3) contained a colourless solid, which melted at 82.5‐83.5° after crystallisation from ethanol. (Mixed m.p. with a sample of 2,3,6‐tribromopyridine: 82‐83°.) After an intermediate fraction of 50 cm3 had passed over in the steam distillation, a further fraction was obtained (250 cm3), which contained a colourless substance melting at 103‐104° after crystallisation from ethanol. (Mixed m.p. with a sample of 2,3,5,6‐tetrabromopyridine: 103‐104°).
The reactivity of bromine atoms in brominated pyridines. The action of sodium phenate on 2,4,6‐tribromopyridine
Authors: den Hertog H. J. , de Jonge A. P.
Published: September 2010

The action of sodium phenate on 2,4,6‐tribromopyridine has been investigated. The order in which the bromine atoms are replaced appeared to be dependent on the solvent used. In phenol the bromine atoms in positions 2 and 6 reacted first and then that in position 4; in water the rate of replacement of the 4 bromine atom had relatively increased, becoming even greater than that of the atoms in positions 2 and 6.

The structure of the substances formed was proved by converting them into phenoxypyridines, the constitution of which was established by synthesis from mono‐ and dibromopyridines.
The system sulphur‐anthracene
Authors: Ketelaar J. A. A. , Jibben B.
Published: September 2010

The melting point diagram of the system sulphur‐anthracene has been determined. It is characterized by an inflection point in the anthracene branch with a rather small inclination. No liquid immiscibility in the metastable nor in the stable region was detected.
Investigations on glycidyl ethers, II. Oxidation of aromatic allyl ethers with perbenzoic acid
Authors: Werner E. G. G.
Published: September 2010

Phenyl allyl ether was oxidized with perbenzoic acid to form phenyl glycidyl ether. In a similar way the two carbon double bonds in cinnamyl allyl ether added on oxygen, with formation of two epoxy‐groups.

Hydroquinone diallyl ether reacted with formation of a mixture containing a small quantity of only one of the two diastereoisomeric hydroquinone bisglycidyl ethers (viz. the higher melting one), but consisting chiefly of 2,3‐ and 2,5‐bisglycidyl‐1,4‐benzoquinone. Apparently, hydroquinone diallyl ether undergoes a Claisen rearrangement during oxidation with perbenzoic acid, resulting in the formation of 2,3‐ and 2,5‐diallyl hydroquinone.
Investigations on glycidyl ethers, III. Reactions of hydroquinone bisglycidyl ether with water and with hydrochloric acid
Authors: Werner E. G. G.
Published: September 2010

The addition of water and of hydrochloric acid to the two diastereoisomeric hydroquinone bisglycidyl ethers was investigated. On hydration, the lowest‐melting isomer (I) yielded one bisglyceryl ether, the highest‐melting one (II) yielded two isomeric bisglyceryl ethers.

On addition of hydrochloric acid the two diastereoisomers showed an exactly opposite behaviour.

These results may be explained by assuming that the addition to a glycidyl group sometimes corresponds to an S (bimolecular nucleophilic substitution) and sometimes to an S mechanism.
Les propriétés du groupe sulfonyle: I. Sur la bromuration d'allylsulfones
Authors: Backer H. J. , Stevens W. , Dost N.
Published: September 2010

Les auteurs ont examiné l'influence du groupe sulfonyle sur l'activité de la fonction allylique vis‐à‐vis de la bromosuccinimide. L'introduction de brome ne réussit ni pour les sulfones cycliques de butadiène et d'isoprène, ni pour la sulfone isomère de butadiène. La benzylallylsulfone, la benzylméthallylsulfone et la diallylsulfone ne réagissent pas davantage. Le groupe sulfonyle supprime donc l'activité allylique, même si le, carbone allylique” se trouve à une certaine distance (β ou γ) du groupe sulfonyle, Cette influence à distance est discutée au point de vue de la théorie électronique.
The change in the composition of the cocaines in java coca leaves during their growth. The acids of the esters of l‐nor‐ecgonine from coca leaves
Authors: de Jong A. W. K.
Published: September 2010

The contradiction noted previously, that the quantity of the cocaines in the leaves on a branch remains almost constant for 8 successive leaves with the exception of that of the youngest leaf, while the composition of the cocaines in the leaves alters during their growth, ‐ young leaves contain more cinnamylcocaines than cocaine and old leaves more cocaine than cinnamylcocaines, ‐ is explained as being caused by the continuous formation of fresh cocaines in the leaves, and the continuous decomposition of an almost equal quantity of cocaines containing less cocaine and more cinnamylcocaines than the percentages in the fresh formed cocaines. Reasons for the quicker decomposition of the cinnamylcocaines in the leaves are indicated.

In agreement with this explanation it is noted, that the acids of the esters of l‐nor‐ecgonine consist for the main part of formic acid, benzoic acid being not present. The way in which l‐nor‐formylecgonine can be formed in the leaves from the cinnamylcocaines is indicated.
A new method for the synthesis of furan derivatives: I. Introduction
Authors: Morel Th. , Verkade P. E.
Published: September 2010

A new method for the synthesis of furan derivatives is outlined. By the action of a mixture of concentrated sulphuric acid and acetic anhydride in the molecular ratio of 1:2 on αβ‐ or β γ‐unsaturated ketones, having a branching of the carbon skeleton in the β‐position, δ‐sultones with two conjugated double bonds in the hetero‐ring are obtained. On pyrolysis these δ‐sultones yield sulphur dioxide and a furan derivative.
The‐rate of hydrolysis and composition of tetraethyl pyrophosphate (T.E.P.P.)
Authors: Ketelaar J. A. A. , Bloksma A. H.
Published: September 2010

Tetraethyl pyrophosphate hydrolyses in a first order reaction with a value of the rate constant of 0.093 h−1 at 25° C and an activation energy of 10.7 kcal/mol. Technical preparations with this substance as active ingredient contain also triethyl orthophosphate and probably polymeric ethyl metaphosphate. By extraction and molecular distillation the components can be separated and pure T.E.P.P. can be obtained. The polymeric ethyl metaphosphate apparently hydrolyses very rapidly probably to symmetric diethyl pyrophosphoric acid thus giving rise to the first rapid formation of acid on dissolving technical preparations in water. A third, very slow hydrolysis observed is probably due to the further hydrolysis of this pyrophosphoric acid ester to monoethyl orthophosphoric acid.
On the use of Evjen's method in calculating madelung potentials
Authors: de Boer F.
Published: September 2010

The complications, arising when Evjen's method is applied to lattices, where the finite part used in the calculation has surfaces which are not electrically neutral, are investigated for a simple lattice: the CsCl lattice bounded by cube faces. A correction is calculated and is applied to the spinel lattice.
The photometric determination of cobalt with nitroso‐R‐salt
Authors: Claassen A. , Westerveld W.
Published: September 2010

As the result of a discussion on the choice of the most suitable wavelength to be used in the photometric determination of cobalt with nitroso‐R‐salt, a wave‐length of 550 mμ is recommended, using absorption cells of 2 to 5 cm length.

The interference by copper and nickel is extensively dealt with. Some data are given on the interference by other elements.
The separation of tin (IV) and antimony according to F. W. Clarke. I. Basis of the method
Authors: Karsten P. , Kies H. L.
Published: September 2010

The stability of the oxalate complexes with respect to hydrogen sulphide was studied experimentally and theoretically as a function of the pH.
Relations between refraction, density and structure of series of homologous hydrocarbons. II. Refraction and density at 20° C of n. alkyl‐cyclopentanes, ‐cyclohexanes and ‐benzenes
Authors: Smittenberg J. , Mulder D.
Published: September 2010

In continuation of the first publication of this series mathematical relations were developed between refraction, density and number of carbon atoms per molecule for n‐alkyl‐cyclopentanes, ‐cyclohexanes and benzenes. The results are compared with those of the n‐alkanes and n‐alpha‐alkenes, presented in the first publication.
The crystal structure of glutaric and pimelic acid. Alternation of properties in the series of dicarboxylic acids
Authors: Macgillavry Caroline H. , Hoogschagen G. , Sixma F. L. J.
Published: September 2010

Glutaric acid and pimelic acid have analogous crystal structures. The CH2 chains are stretched along the c‐axis, the plane of the zigzag is nearly parallel to (100). Packing of the COOH groups is practically identical to that in adipic acid. This packing enforces a torsion in the molecules of the odd acids as a result of their axial symmetry. This torsion may well be the cause of the higher energy content of the odd dicarboxylic acids; an estimate of the torsion energy is made and is shown to be of the right order of magnitude.
Les Propriétés du Groupe Sulfonyle: III. Oxydation du tétrathioorthocarbonate tétraméthylique
Authors: Backer H. J.
Published: September 2010

Le tétrakis‐méthylthio‐méthane, en présence d'acide perbenzoïque en excès, consomme 7 à 8 atomes d'oxygéne. En lavant le produit d'oxydation à l'eau, on élimine de l'acide méthanesulfonique.

Le résidu est un mélange, dont on peut séparer, par des procédés variés, le tris‐méthylsulfonyl‐méthane CH(SO2Me)5 (acide fort). Le principal composant du mélange peut engendrer une sulfoxyde‐disulfone (MeSO)CH(SO2Me)2, dont il est peut‐étre un isomère; il se décompose à 110° en donnant l'acide méthanesulfonique, le dioxyde de diméthyldisulfure Me2S2O2 et d'autres produits encore. II n'est pas impossible qu'une tétrasulfone se soit formée parmi les produits primaires de l'oxydation, et, si c'est le cas, elle s'est décomposée rapidement.

En introduisant deux groupes thiométhyle dans le bis‐méthylsulfonyl‐méthane, on synthétise un dérivé du tétrathioéther avec deux groupes sulfonyle (MeS)2C(SO2Me)2, dérivé qui, soumis à l'oxydation, se comporte, dans les grand lignes, comme le tétrathioéther. On n'obtient pas de tétrasulfone.
Les Potentiels Electrocinetiques du Sulfate de Barium
Authors: Ruyssen R. , Loos R.
Published: September 2010

Le potentiel d'écoulement de cristaux de BaSO4 en milieu hydroalcoolique a été mesuré. Dans certains cas on observe une positivation des cristaux. Ce phénomène parait étre dû à une désorption des ions sulfuriques ou à l'adsorption des ions barium.
1,3,5‐Tri‐p‐methoxybenzylcyclohexane
Authors: van der Zanden J. M. , de Vries G.
Published: September 2010

Both stereo‐isomers of 1,3,5‐tri‐p‐methoxybenzylcyclohexane (CH3O. C6H4. CH2)3C6H9have been synthesized in connection with our investigation on polymerisation products from methylchavicol.
On some derivatives of diphenylamine
Authors: Blanksma J. J.
Published: September 2010

The coupling of 1‐chloro‐2,4‐dinitrobenzene with 3,5‐dichloroaniline gives 3,5‐dichloro‐2′,4′‐dinitrodiphenylamine. The nitration of this formerly unknown compound with anhydrous nitric acid gives 3,5‐dichloro‐2,4‐2′,4′‐tetranitrodiphenylamine, in which the chlorine atoms are mobile and can be replaced by amino groups.

The partial reduction of 2,4‐dinitrodiphenylamine and its derivatives can be accomplished better with Na2S2 than with Na2S. magnified image
The binary melting‐point diagram of the two isomeric ketones C5Cl6O
Authors: Engelsma J. W. , Gerding H.
Published: September 2010

The binary melting‐point diagram of the two isomeric ketones C5Cl6O was determined.
Steric effects on mesomerism. IV. Steric effects on mesomerism in derivatives of ortho‐nitro‐acetanilide
Authors: Wepster B. M. , Verkade P. E.
Published: September 2010

This paper contains data on the (pseudo) catalytic deacylation of a number of derivatives ofortho‐nitro‐acetanilide in which steric effects on mesomerism are to be expected. The rate of deacylation found for each compound is discussed in some detail on the basis of current electronic theory.

It is shown that the occurrence of steric inhibition of mesomerism can sometimes be used to advantage in the separation of mixtures of isomeric nitroaryl‐acylamines.
Halogen derivatives of isoprene
Authors: Ultée A. J.
Published: September 2010

Many halogen derivatives of isoprene were prepared and their structure studied, the starting materials being two addition products of hydrochloric acid and isoprene. This addition leads to 3‐chloro‐3‐methylbutene‐l, i.e. 1,2‐addition (II), which had not been isolated by previous workers. This tertiary chloride undergoes an allylic rearrangement to the primary chloride (I) under the catalytic influence of hydrochloric acid.

Chlorine on the other hand yields mainly the 1,4‐addition product of isoprene1) (VI), but the 3,4‐addition product (V) is also formed as a by‐product.

Sulphuryl chloride in the presence of peroxides reacts in the expected way, leading essentially to the additon of two chlorine atoms to the double bond. In the presence of an anti‐oxidant, however, substitution becomes predominant. This result is contrary to the previous experience of Kharash and Brown2) with olefines.

Vinyl halides with a chlorine atom in α‐position to the vinyl chloride do not add iodine chloride.

Only vinyl halides are non‐reactive with piperidine (in nitrobenzene solution) at 100°. This reaction can therefore be used for the identification of vinyl halide groups.
A complete extraction of the bases and the acid esters of l‐nor‐ecgonine from coca leaves. II
Authors: de Jong A. W. K.
Published: September 2010

The results of experiments have shown that 20 g of coca leaves manipulated as previously indicated should be extracted first with a mixture of 400 cm3 of benzene with 20 cm3 of methyl alcohol and thereafter with about 600 cm3 of the 58° boiling mixture, to obtain complete extraction of the bases.

It is argued, that after the addition of the ammonia solution to the leaves deprived of their moisture by powdered quick lime present in the mixture of benzene with about 5% by volume of methyl alcohol, an equilibrium is formed in the unbroken cells of the leaves between the base salts, the bases and ammonia in dilute methyl alcohol. The bases outside the cells will be set free by calcium hydroxide. The acid esters of l‐nor‐ecgonine in the unbroken cells will be in the free state after the action of ammonia and will be converted to calcium salts outside the cells. Therefore it will be an adventage to use coarse pulverised leaves for extraction.
Derivatives of bis(4‐aminophenyl)‐sulfone II. Condensation of bis(4‐aminophenyl)‐sulfone with some aromatic aldehydes
Authors: Sah Peter P. T. , Oneto John F. , Rohrmann Ewald , Kleiderer E. C.
Published: September 2010

For chemotherapeutic studies, five anils were prepared by the direct condensation of bis(4‐aminophenyl)‐sulfone (I) in absolute ethanol with aromatic aldehydes, i.e. bis (4‐o‐chlorobenzalaminophenyl)‐sulfone (II) from I and o‐chlorobenzaldehyde, bis (4‐p‐chlorobenzalaminophenyl)‐sulfone (III) from I and p‐chlorobenzaldehyde, bis (4‐o,p‐dichlorobenzalaminophenyl)‐sulfone (IV) from I and o,p‐dichlorobenzaldehyde, bis(4‐m,p‐dichlorobenzalaminophenyl)‐sulfone (V) from I and m,p‐dichlorobenzaldehyde, bis (4‐2′‐hydroxy‐1′‐naphthalaminophenyl)‐sulfone (VI), from I and 2‐hydroxy‐1‐naphthaldehyde.

Of this group of anils II is the most active biologically. Its antitubercular activity is comparable to salicylacetone. It is also slightly more effective than sulfanilamide in streptococci hemolyticus infected mice at 5 mg X 2 dosage.