bluuebunny/crossref_metadata_2025 huggingface dataset:
Reactions of Bisamides. X. Condensations of N,N′‐(arylmethylene)bisamides with phenols and naphthols
Authors: Stefanović G. J. , Bojanović J. , Vandjel V. , Maksimović Z. , Mihailović M. Lj.
Published: September 2010

N,N′‐(Arylmethylene)bisamides react with phenols by substitution of one amide residue, affording α‐acylaminobenzylcresols. Ortho‐derivatives are usually obtained, but when both ortho‐positions are occupied the reaction takes place at the para‐position, although in the latter case the yields are lower. The same compounds are obtained by condensing aldehydes, acid amides and phenols. β‐Naphthol reacts with bisamides or with aldehydes and acid amides in the same way as phenols. With α‐naphthol, however, the reaction takes a different course; both amide residues in the bisamide molecule are eliminated and benzylidenedi‐α‐naphthol, a compound of the triphenylmethane type, is obtained.
The reactivity of the bromine atom of some nitro‐bromonaphthalenes towards piperidine
Authors: van Berk P. , Verkade P. E. , Wepster B. M.
Published: September 2010

Reaction rate constants are determined for the piperidino‐debromination of a number of nitro‐bromonaphthalenes. The results are discussed and compared with those obtained in the catalytic deacetylation of the corresponding nitro‐acetylaminonaphthalenes in an alkaline medium.
The electrolysis of some 3‐arylpropionic acids isomerization of free radicals
Authors: Breederveld H. , Kooyman E. C.
Published: September 2010

The electrolysis of some substituted 3‐arylpropionic acids has been investigated with a view to a possible rearrangement of free radicals formed through discharge of anions.

With 3‐phenylisovaleric acid in methanol containing an excess of sodium acetate the main product isolated was t‐amylbenzene, no rearrangement having occurred.

3,3,3‐Triphenylpropionic acid in methanol containing sodium ions gave mainly the phenyl ester of 3,3‐diphenyl‐3‐methoxypropionic acid. The analogous tri‐p‐t‐butylphenylpropionic acid yielded the p‐t‐butylphenyl ester of 3,3‐di‐p‐t‐butylphenyl‐3‐methoxypropionic acid. The latter results are interpreted as involving a novel type of rearrangement of acyloxy radicals, an oxygen atom attacking an aromatic ring at its point of attachment to the C‐3 atom:

magnified image

In a discussion on the mechanism of isomerizations occurring in electrolysis, it is suggested that acyloxy radicals may also play a part rather than alkyl radicals only.
Hydrocarbures polycycliques aromatiques. IV. Sur la chimie du dibenzo[a, h] pyrène
Authors: Buu‐Hoï N. P. , Lavit Denise
Published: September 2010

Quelques réactions de substitution du dibenzo [a,h] pyrène, hydrocarbure fortement cancériqène, ont été examinées: l'action du chlorure de sulfuryle a conduit au dérivé 7,14‐dichloré, et celle de la N‐méthylformanilide, au dérivé 7‐formylé; le 7‐méthyl‐dibenzo [a,h] pyrène, préparé à partir de ce dernier par réduction, peut être converti en 14‐formyl‐7‐méthyl‐dibenzo [a,h] pyrène, lequel, à son tour, est réductible en 7, 14‐diméthyl‐dibenzo [a,h] pyrène.
Mollisin, a dichloronaphthoquinone derivative produced by the fungus: Mollisia caesia
Authors: van der Kerk G. J. M. , Overeem J. C.
Published: September 2010

The isolation and characterisation of mollisin, the yellow pigment from the fungus Mollisia caesia, are described.

Mollisin must be regarded as 2,3‐dichloro‐5‐hydroxy‐7‐(or 6‐) methyl‐8‐acetonylnaphthoquinone‐1,4.
The Raman and infra‐red spectra of methane‐, ethane‐ and isopropane‐phosphoryl dichloride
Authors: Gerding H. , Maarsen J. W.
Published: September 2010

The Raman and infrared spectra of H3CPOCl2, H5C2POCl2, and iso‐H7C3POCl2 have been investigated. Assuming the symmetry C8 for the skeletal structure CPOCl2 in these compounds, the frequencies found can be assigned fully for H3CPOCl2 and H5C2POCl2, and in the lower region in iso‐H7C3POCl2 only in part. The doubling of the P  O stretching in H5C2‐ and iso‐H7C3POCl2 can be explained from Fermi interaction with a CH deformation vibration. Of the two possible P‐Cl stretching frequencies only the symmetrical one is of high intensity.
On the theory of chromatography II
Authors: van den Hoek A. , Smit W. M.
Published: September 2010

Experimental part.

A careful experimental check carried out on the theory presented in part I, shows fair agreement between theory and experimental results. A simple chromatographic method for separating aromatic and paraffinic hydrocarbons is demonstrated.

Experimental evidence is given that apparent deviations from the equilibrium theory may be due mainly to channeling and to a far less extent to diffusion or lack of equilibrium.
Isolation of dehydroepiandrosterone sulphate from the urine of a male patient with adrenal neoplasm
Authors: Huis in 'T Veld Leonora G.
Published: September 2010

1) A compound with the empirical formula C19H27O5SNa. 2 H2O was isolated from the butanol extract of the urine of a male patient suffering from an adrenal‐cortical tumour with liver metastasis.

2) It has been identified by m.p., mixed m.p., optical rotation and infrared spectrum as sodium dehydroepiandrosterone sulphate.

3) Hydrolysis of this compound in a neutral medium produced i‐androstan‐6‐ol‐17‐one.
The action of p‐toluenesulphonyl chloride on pyridine‐N‐oxide (II) : The reaction of pyridine‐N‐oxide with 2‐, 3‐ and 4‐pyridyl p‐toluenesulphonate
Authors: de Villiers P. A. , den Hertog H. J.
Published: September 2010

2‐ and 3‐Pyridyl p‐toluenesulphonate behave differently when heated with pyridine‐N‐oxide. Whilst 3‐pyridyl p‐toluenesulphonate remains practically unchanged, the 2‐pyridyl compound yields a complicated reaction mixture, from which N‐(2′‐pyridyl)‐pyridone‐2 as chief product and further N‐(4′‐pyridyl)‐pyridone‐2 and 2,3′‐dipyridyl ether have been isolated. In order to elucidate the mechanism of this reaction, we also reacted 2‐pyridyl p‐toluenesulphonate with 3‐bromopyridine‐N‐oxide; this process yielded chiefly N‐[2′‐(3′‐bromopyridyl)]‐pyridone‐2. In an orienting experiment we isolated N‐(4′‐pyridyl)‐pyridone‐4 from the mixture obtained by heating 4‐pyridyl p‐toluenesulphonate and pyridine‐N‐oxide. The picrates and mercuric chloride compounds of the reaction products and some related substances are described, and their UV absorption spectra have been measured.
Investigations on agricultural fungicides. II. Compounds structurally related to trichloromethyl thiolsulphonates
Authors: Uhlenbroek J. H. , Koopmans M. J.
Published: September 2010

The preparation and the fungitoxic properties of some thiolsulphonic esters (type p‐CH3C6H4SO2SR′) and of some reaction products of trichloromethanesulphenyl chloride with thiosulphonic acid salts and with thiophenols are described in this paper.
A chemical routine determination of vitamin‐D; correlation with the biological determination. (Analysis of fat soluble vitamins II))
Authors: Mulder F. J. , Roborgh J. R. , de Man Th. J. , Keuning K. J. , Hanewald K. H.
Published: September 2010

A chemical routine method for the determination of vitamins‐D2 and ‐D3 in a number of preparations is presented. The results obtained agree very well with those obtained with the rat and chick assays respectively.

A procedure for the routine determination of vitamin‐D especially for synthetic ergo‐ and chole‐calciferol is described in detail.

It is a combination of a maleic anhydride addition extrapolated to zero time, and a colorimetric determination with antimony trichloride. Solutions of crystalline calciferols, irradiation products (resins and solutions in oil or volatile solvents), emulsions, solubilized solutions and dry products are covered by this method.

The concentration limit after removal of volatile solvents from the products or from an extract is about 50,000 I.U./g.

Interferences by fatty oils, unsaturated acids, by‐products from the irradiation, especially tachysterols, are allowed for. Interference by vitamin‐A could not be eliminated however.

A determination takes about 200,000 I.U. A number of representative analyses is presented.

The coefficient of variation is about 2 %.

The curative test (rat assay) for vitamin‐D2 and the prophylactic test (chick assay) for vitamin‐D3 give essentially the same results (94.4 ± 16.7 % and 106.8 ± 15.8 %) as the chemical determination.

It is possible to substitute the determination presented here for the bio‐assay as an analytical routine method.
Electronic spectra of mono‐ and di‐negative aromatic ions
Authors: Balk P. , Hoijtink G. J. , Schreurs J. W. H.
Published: September 2010

The electronic spectra in the 32‐4 kK region of the mononegative ions of naphthalene, anthracene, tetracene, phenanthrene, diphenyl, terphenyl, quaterphenyl, pyrene, perylene, triphenylene and coronene are given. The spectra of the dinegative ions of anthracene, tetracene, terphenyl, quaterphenyl and perylene have also been investigated.
The stability constants of metal complexes of some N‐dialkyldithiocarbamic acids: Part II. Copper complexes in ethanol/water mixtures of various compositions
Authors: Janssen M. J.
Published: September 2010

The stability constants of copper complexes of N‐dimethyl‐, N‐di‐n‐propyl‐, cyclotetramethylene‐ and 3‐carboxy‐cyclo‐pentamethylene‐dithiocarbamic acids were measured in 51.7, 75.0 and 89.0% (v/v) ethanol/water; that of the last‐mentioned compound also in water. With the aid of these results a fairly good estimate could be made of the stability constants of copper complexes of the three first‐mentioned acids in water.
Chemistry of acetylenic ethers XXVI. Ethyl orthothioacetate and 1,1‐bis‐ethylthioethene (ketene diethyl mercaptal)
Authors: Volger H. C. , Arens J. F.
Published: September 2010

The preparation of ethyl orthothioacetate (VII) from acetyl chloride and excess of ethanethiol in the presence of zinc chloride has been studied. The substance can easily be converted into 1,1‐bis‐ethylthioethene (VI), which can also be obtained directly from acetyl chloride (or ethyl acetate) and two moles of ethanethiol under the influence of zinc chloride. 1,1‐bis‐Ethylthioethene (VI) is produced also by the action of potassium tert.butoxide on ethylthioacetaldehyde diethylmercaptal (X).
Electronic spectra of alternant hydrocarbon mononegative ions
Authors: Balk P. , de Bruijn S. , Hoijtink G. J.
Published: September 2010

The electronic spectra of the mononegative ions of naphthalene, anthracene, tetracene, phenanthrene, pyrene, perylene, biphenyl, terphenyl and quater‐phenyl have been qualitatively interpreted with the aid of L.C.A.O.‐M.O. calculations including configuration interaction. The calculated dipole strengths are on the average about twice to three times as high as the experimental values. In a relative sense, however, the agreement between observed and calculated dipole strengths is satisfactory.
A kinetical investigation of the reaction between amides and formaldehyde
Authors: Ugelstad J. , de Jonge J.
Published: September 2010

This paper deals with the kinetic measurement of the reaction between formaldehyde and the amides of carboxylic acids and urea.

It is shown that the formation of a methylol amide proceeds by a bimolecular reaction, while its decomposition is a monomolecular reaction. The reactions are catalysed by H3O+ and OH− ions and show general acid catalysis. General base catalysis was found in the urea‐formaldehyde system, but could not be detected in reactions of formaldehyde with amides of carboxylic acids. A mechanism for the reactions of formaldehyde with amides in general (including urea) is proposed.

In strongly alkaline solution the rates of decomposition of methylol amides were found to be independent of the hydroxyl ion concentration. The acid dissociation constant of some methylol amides have values of about 10−14 moles 1−1 at 0° C.
Chemistry of acetylenic ethers XXVII: Reactions of 1,1‐diazido‐1‐ethoxyethane with nucleophilic reagents
Authors: Sinnema Y. A. , Arens J. F.
Published: September 2010

The reactions of 1,1‐diazido‐1‐ethoxyethane with several nucleophilic reagents have been studied. Strong nucleophilic reagents rapidly substitute both azido groups. Weak nucleophiles require a reaction temperature of about 70° C. At this temperature nitrogen splits off from the diazide, so that side reactions may occur. One of these is the reduction of an azido group by a thiol. Another is the “reductive” removal of an azido group by the action of hydrazoic acid. The latter reaction can be applied for the conversion of ethoxyethynylcarbinols into α, β‐unsaturated aldehydes.
Hydrocarbures Polycycliques Aromatiques: VII. Synthèse du 2‐phényl‐ et du 2‐p‐biphénylanthracène par la réaction d'Elbs
Authors: Buu‐HoÏ N. P. , Lavit Denise , Jacquignon Pierre
Published: September 2010

On décrit une nouvelle synthèse du 2‐phenylanthracène, par pyrolyse du 4‐o‐toluoylbiphényle; le 2‐p‐biphénylanthracène, non encore décrit jusqu'à présent, a été synthétisé de façon analogue par pyrolyse du 4′‐o‐toluoyl p‐terphényle. Cette dernière cétone est préparée, en méme temps que le 4′,4″‐bis(o‐toluoyl)‐p‐terphényle, dans la réaction de Friedel‐Crafts entre le chlorure d'o‐toluoyle et le p‐terphényle. Les spectres d'absorption et de fluorescence du 2‐phényl‐ et du 2‐p‐biphénylanthracène ont été déterminés.
Thermodynamic properties of mixtures of alkanes differing in chain length, IV: Volumes of mixing
Authors: Desmyter A. , van der Waals J. H.
Published: September 2010

The change in volume on mixing two alkanes of different molecular weight has been studied in order to provide further experimental data for testing current theories of solutions. A description is given of a dilatometer which permits a determination of the volume of mixing as a function of composition over a wide range of concentrations in a single experiment.

Binary mixtures of n‐alkanes (C5 + C16, C6 + C16, C7 + C16, C8 + C16, C10 + C16 and C6 + C12) and the system iso‐octane‐n‐hexadecane were investigated in the temperature range of 20‐50° C. In all cases a contraction is observed which increases with temperature and with the difference in chain length of the two components. It ranges from 0.03% for the system n‐decane/n‐hexadecane to about 0.5% for a mixture of n‐pentane and n‐hexadecane at room temperature.

It appears that the excess volumes of binary mixtures of n‐alkanes can be predicted from the molal volumes of the pure n‐alkanes on the basis of Brønsted's principle of congruence.
Foam stability. Part I. Structure and stability of foams
Authors: de Vries A. J.
Published: September 2010

A critical survey is given of the various factors governing the stability of foams. Special attention is paid to the role of surface tension and to the importance of Gibbs' effect of surface elasticity of thin liquid films: The contribution of the last factor to the free energy of deformation of foam lamellae is estimated.

The two different forms of foam structure which may occur, foams with spherical bubbles and foams containing polyhedral cells, are described and their differences are explained in particular with respect to both processes responsible for the spontaneous destabilization of foams: transfer of gas between the bubbles and collapse of the lamellae.
Untersuchungen ueber Nitroderivate des Pyridins
Authors: Czuba Wladyslaw , Plaźek Edwin
Published: September 2010

2,6‐Dinitro‐3‐hydroxypyridin bildet sich bei der Nitrierung des 2‐Nitro‐3‐hydroxypyridins in Gegenwart von Essigsäureanhydrid. Mit PCl5 entsteht daraus 2,6‐Dinitro‐3‐chlorpyridin. Diese Verbindung tauscht bei der Einwirkung von NH2‐NH2, NH3, KOH nicht das Chloratom, sondern ausschliesslich die NO2 Gruppe in 2‐Stellung aus.
Investigations on organic insecticides. I. Preparation and insecticidal properties of some substituted polyenamides
Authors: Huisman H. O. , Smit A. , Meltzer J.
Published: September 2010

The preparation and insecticidal properties of a number of substituted polyenamides are described in connection with the occurrence of this type of compound in nature.
The preparation of pyridine derivatives from halogenopyridines by means of the Grignard Reaction VI: Preparation of 2‐allylpyridine from 2‐bromopyridine and of 2,6‐diallylpyridine from 2,6‐dibromopyridine
Authors: Wibaut J. P. , Bloemendal H.
Published: September 2010

The synthesis of 2‐allylpyridine and 2,6‐diallylpyridine by the reaction of allyl bromide with 2‐pyridylmagnesium bromide and pyridenyl‐2,6‐bis‐magnesium bromide, respectively, is described.
On the sensitivity to light of polyene fungicides
Authors: Hendriks B. , Berends W.
Published: September 2010

During recent years various fungicides having a polyene structure have been isolated from streptomycetes. During the study of the action mechanism of a new representative of this group, pimaricin, it was established that the suppression of respiration of yeast by this substance was completely neutralised, if at the same time riboflavin and light were present. The cause of this phenomenon appears to be traceable back to a photodynamic destruction of pimiracin under the influence of riboflavin.

The effect is not restricted to riboflavin; some other colouring matters also possess this property. Ascorbic acid and hydroquinone repress the photodynamic reaction greatly. Arguments are presented for supposing that hydroxyl radicals are responsible for the annulment of the polyene group of the fungicide. So far hydrogen peroxide has been regarded as the substance bringing about the photo‐dynamic reactions.
Ionylamines II: Synthesis of tetra‐ and hexa‐hydro‐ψ‐ionylamines and their spasmolytic action
Authors: Moed H. D. , Kralt T. , van Dijk J.
Published: September 2010

The synthesis and properties of amines with the C‐skeleton of ψ‐ionone are described. The spasmolytic activities of the compounds have been determined. The results are discussed and the conclusions are reached that the ψ‐ionylamines form a series of compounds with high musculotropic spasmolytic activity and that in this series there exists a fairly clear and regular relationship between chemical structure and spasmolytic activity.
The reaction between ethyl diazoacetate and 1‐butoxybutane
Authors: de Graaff G. B. R. , van de Kolk G.
Published: September 2010

In continuation of a previously published investigation on the reaction between ethyl diazoacetate and ethers of different types

G. B. R. de Graaff, Mrs. J. H. van Dijck‐Rothuis and G. van de Kolk, Rec. trav. chim. 74, 143 (1955).

, the reaction mentioned in the title has been examined more completely.

It has been found that several esters of butoxy derivatives of normal and branched caproic acids are formed together with ethyl butoxyacetate and butene‐1.

Thus, two reactions appear to occur simultaneously viz.:

an addition reaction of the radical, formed from the reagent, to the oxygen atom of the ether;

direct attack by the radical of the various carbon atoms of the alkyl groups.

The structure of the reaction products has been proved and a discussion on the results obtained is given.
Investigations on sterols. X: The conversion of ergosterol and pre‐ergocalciferol by U.V. light of 254 mμ
Authors: Rappoldt M. P. , Westerhof P. , Hanewald K. H. , Buisman J. A. Keverling
Published: September 2010

A study is presented of the conversion of ergosterol and pre‐ergocalciferol by U.V. light of 254 mμ From the experiments certain conclusions are drawn regarding the formation of tachysterol2 from ergosterol and on the quantum‐efficiency of the interconversion of pre‐ergocalciferol and tachysterol2.
A simple recording balance
Authors: Scholten P. C. , Smit W. M. , Wijnen M. D.
Published: September 2010

A recording balance, consisting of a simple analytical balance, an electronic part and a recorder, is described.

In a normal balance any deflection causes a compensating force due to gravity.

The present balance has been made mechanically indifferent and an electrical zero‐point has been introduced, which may be shifted at will. The compensating force (which is free from any gravity component at any deflection) is directed by the deflection of the balance with the aid of a simple electro‐optical system. The electrical system, which contains no servo‐motor, also provides damping. Equilibrium is attained without restoring the balance to an initial position.

The sensivity of the balance may be changed easily from 25 mg to 200 mg full scale deflection of the recorder.

The accuracy, which is mainly determined by the accuracy of the recorder, amounts to 0.3% of full scale deflection.

The use of the present balance as a thermobalance is described.

But for the recorder the apparatus is simple and inexpensive.
The mercuration of pyridine‐N‐oxide
Authors: van Ammers M. , den Hertog H. J.
Published: September 2010

By heating pyridine‐N‐oxide with mercuric acetate in acetic acid solution at 130°, a reaction product was obtained, which afforded, after reacting successively with sodium chloride solution and bromine, a mixture containing 2‐bromo‐ and 2,6‐dibromopyridine‐N‐oxide. The structure of the dibromo‐compound was proved by converting it via 2,6‐dibromo‐4‐nitro‐pyridine‐N‐oxide into the known 4‐amino‐2,6‐dibromopyridine. Our result differs from that obtained by Ukai, Yamamoto and Hirano who record the 4‐monosubstituted derivative as the sole product of reaction under the same conditions 2).

2,6‐Dibromopyridine‐N‐oxide is an excellent intermediate for the preparation of derivatives of pyridine and its N‐oxide, especially for those substituted in positions 2, 4 and 6.
Selective reduction by calcium hexammine: Part I. Aromatic hydrocarbons
Authors: Boer H. , Duinker P. M.
Published: September 2010

Following up an investigation by Kazanskii

B. A. Kazanskii and N. V. Smirnova, Bull. Acad. Sci. U.S.S.R., class. Sci. math. nat. 1937, 547; B. A. Kazanskii and N. F. Glushnev, J. Gen. Chem. U.S.S.R. 8, 642 (1937).

), the authors have investigated fne use of calcium hexammine, Ca(NH3)6. as an agent for laboratory‐scale selective reductions of aromatic hydrocarbons.

Under carefully adjusted reaction conditions it proved to be possible to reduce polynuclear aromatic hydrocarbons to compounds containing only one isolated benzene ring. Under somewhat different conditions alkyl‐benzenes could be reduced to the corresponding cycloalkadienes or cyclo‐alkenes. It is assumed that reduction by metalammonia reagents requires a conjugated system of double bonds.

The method described opens up possibilities for the preparation of compounds which are difficult to synthesize in other ways. Thus, cyclohexadiene‐1,4, as‐octahydrophenanthrene and some alkyltetralins were synthesized in fair yields.

Some remarks are made on the mechanism of the reaction.

A convenient method for the preparation of calcium hexammine is described.
Thermodynamic properties of quinol clathrates II. Vapour pressures of argon clathrates
Authors: Platteeuw J. C.
Published: September 2010

The equilibrium clathrate‐gas has been studied for the quinol‐argon compound at 60° C. It was found that the argon pressure is related to the composition of the clathrate according to a Langmuir isotherm, as predicted on theoretical grounds.
Foam stability: Part V. Mechanism of film rupture
Authors: de Vries A. J.
Published: September 2010

Lamellae of pure liquid and low‐molecular solutions are unstable because of the absence of a limiting thickness. Rapid collapse of these lamellae may start at relatively large thickness (∼ 500 Å) under influence of the London‐van der Waals attractive forces. Small quantities of surface active ions will prevent this collapse mechanism to occur in aqueous lamellae. A sufficient amount of activation energy for rupturing a “stable” lamella may be supplied by a local depression of surface tension in a small volume element of the film. The minimum surface area of such an element is calculated as a function of the film thickness, and its dependence on the rheological properties of the superficial layers of liquid (plasticity, viscosity and elasticity) is explained.

Some results are given of an experimental investigation of the influence of a local rise in temperature on the lifetime of isolated lamellae of a Tee‐pol solution. The destabilizing effect of local heating is interpreted as a result of the decrease of surface tension in the warmer portion of the film. The importance of local temperature variations for the instability of foams is discussed. A calculation is given of the magnitude, frequency and average lifetime of spontaneous temperature fluctuations in liquid lamellae under adiabatic conditions. It is shown that these fluctuations are able to affect the stability of very thin lamellae only (thickness of the order of some tens of Å).

A general explanation of the action of anti‐foaming agents is given, based on the occurrence of local depressions in surface tension. Finally the effect of mechanical disturbances on the probability of film rupture is considered.
Hydrocarbures Polycycliques Aromatiques. VIII. Sur deux homologues monométhylés du naphto[2,3‐a]pyrène
Authors: Buu‐Hoï N. P. , Lavit Denise , Jacquignon Pierre , Chalvet Odilon
Published: September 2010

On décrit la synthèse de deux homologues monométhylés du naphto [2,3‐a] pyrène. Le 10‐méthylnaphto[ 2,3‐a] pyrène a été préparé par la réaction d'Elbs à partir du 3‐(2,5‐diméthylbenzoyl)pyrène; d'autre part, la formylation du naphto [2,3‐a] pyrène conduit principalement à un aldéhyde qui, d'après le calcul des indices de valence libre effectué selon la méthode des combinaisons linéaires d'orbitales atomiques, doit étre le 6‐formylnaphto‐[2,3‐a] pyrène; comme sous‐produit de la réaction, on obtient un peu de 7‐formylnaphto[2,3‐a]pyrène. La réduction du dérivé 6‐formylé fournit le 6‐méthylnaphto[2,3‐a]pyrène, lequel peut être formylé à son tour pour donner le 7‐formyl‐6‐méthylnaphto[2,3‐a]pyrène.
Hydrocarbures Polycycliques Aromatiques. IX. Synthèse des 1,2‐ et 2,3‐cyclopenténoanthracènes, du 1,2‐benzanthracène et du naphtacène par la réaction d'Elbs
Authors: Buu‐Hoï N. P. , Lavit Denise
Published: September 2010

Il est montré que la réaction d'Elbs, pratiquée sur le 5‐o‐toluoylindane, conduit principalement au 2,3‐cyclopenténoanthracène, le 1,2‐cyclopenténoanthracène étant obtenu en petites quantités comme sous‐produit de la réaction; la pyrolyse de la 2‐o‐toluoyltétraline, suivie de la déshydrogénation du produit de la réaction, conduit au 1,2‐benzanthracène et au naphtacène. Le 2,3‐cyclopenténoanthracène peut être formylé en position méso pour donner le 9‐formyl‐2,3‐cyclopenténoanthracène, lequel est réduit par la méthode de Kishner‐Wolff en 9‐méthyl‐2,3‐cyclopenténoanthracène.
Steric effects on mesomerism. XVII. Some properties of aromatic nitro‐, amino‐, and acylamino compounds with bulky ortho‐substituents
Authors: Burgers J. , Hoefnagel M. A. , Verkade P. E. , Visser H. , Wepster B. M.
Published: September 2010

Following up earlier work, this paper discusses the influence of 2‐methyl‐6‐tert.butyl substitution and/or 2,6‐di‐tert.butyl substitution on certain properties of compounds such as nitrobenzene, aniline, N‐methylaniline, N,N‐dimethylaniline, acetanilide, 4‐nitro‐aniline, and 4‐nitro‐acetanilide.

For the derivatives of nitrobenzene, N,N‐dimethylaniline, and acetanilide the electronic absorption spectra indicate a complete or almost complete elimination of the mesomeric interaction. In contrast with this it has to be concluded for all the primary amines investigated that the mesomerism is fully developed; in the relevant discussion the vectorial treatment of absorption Intensities has been of decisive importance. The secondary amines take up an intermediate position; in these cases, owing to the pyramidal configuration of the nitrogen atom, the angle of twist cannot be forced to values exceeding about 60°.

The basic strength of 2,6‐di‐tert.butyl‐substituted primary amines is lower by a factor of about 108 than might be expected on the basis of the electrical effects of the alkyl groups; the basic strength of 2‐methyl‐6‐tert.butyl‐substituted N,N‐dimethylanilines is lower by a factor of about 106 than might be expected on the basis of the electrical effects of the alkyl groups and the steric inhibition of the mesomerism present in these compounds. These reductions of the basic strength have been ascribed to steric hindrance to solvation.

The basic strength of 3,5‐di‐tert.butyl‐4‐nitroaniline confirms previously obtained information on the quantitative significance of the inductive and the mesomeric effect of the nitro group in 4‐nitroaniline as well as on the meta/para ratio of the inductive effect.
A new factor involved in amino acid incorporation and nucleic aced synthesis
Authors: Gale E. F.
Published: September 2010

Table II summarises the present situation concerning the activities of the incorporation factor preparation. If disrupted staphylococcal cells are treated so that the greater part of their nucleic acid is removed, then the incorporation of a single amino acid such as glycine or glutamic acid can be promoted by the IF preparation to the same extent as by nucleic acid. The synthesis of RNA, as measured by the incorporation of adenine into the RNA fraction, requires the presence of a complete mixture of amino acids, the natural purines and pyrimidines, DNA and the IF preparation. The synthesis of protein, as judged by the development of catalase and β‐galactosidase, requires a complete mixture of amino acids, DNA and, in the case of catalase, RNA or in the case of β‐galactosidase, the synthesis of RNA; in neither case does IF have any effect over and above that involved in the nucleic acid or its synthesis. This may mean that the factor is concerned in the synthesis of ribonucleic acid and the role of amino acids in that synthesis rather than in the formation of protein per se.
Steric effects in the electronic spectra of substituted benzophenones III: Duryl ketones
Authors: Rekker R. F. , Nauta W. Th.
Published: September 2010

The U.V.‐absorption spectra of diduryl ketone, diisoduryl ketone and durylisoduryl ketone have been measured and mutually compared.

A ketone previously described by Coops et al. as diduryl ketone was definitely established as durylisoduryl ketone.
Hydrocarbures Polycycliques Aromatiques. X: La formylation de l'acénaphtylène et du fluoranthène
Authors: Buu‐Hoï N. P. , Lavit Denise
Published: September 2010

Dans le cadre d'une étude sur le comportement des hydrocarbures polycycliques péri‐condensés dans la réaction de formylation par les formiamides N,N‐disubstitués, il est montré que l'acénaphtylène conduit au 1‐formylacénaphtylène, alors que, dans les mêmes conditions, le fluoranthène ne réagit pas. On discute également de la corrélation entre la facilité de formylation et les valeurs des indices de valence libre chez les hydrocarbures polycycliques péri‐condensés.
Chemistry of acetylenic ethers XXXII. Formation of 1,3‐dialkyl‐2‐ethoxy‐cyclobut‐2‐ene‐4‐ones from ethyl 1‐alkynyl ethers
Authors: Nieuwenhuis J. , Arens J. F.
Published: September 2010

On heating, ethylene is eliminated from an ethyl 1‐alkynyl ether; the product formed in good yield is a 1,3‐dialkyl‐2‐ethoxy‐cyclobut‐2‐ene‐4‐one. The ethoxy group can easily be saponified and the resulting product is a dimer of an alkyl ketene. Other reactions are summarised in scheme B.
1,3,5‐Triacetylbenzene as a base material for the preparation of symmetrical trialkylbenzenes
Authors: Wibaut J. P. , Paulis B.
Published: September 2010

The Grignard reaction of 1,3,5‐triacetylbenzene with CH3MgX has been studied; the synthesis is described and physical constants are given of four symmetrical trialkylbenzenes:

1,3,5‐triisopropylbenzene,

1,3‐diisopropyl‐5‐ethylbenzene,

1‐isopropyl‐3,5‐diethylbenzene and

1,3,5‐triethylbenzene.
Synthesis and some physical constants of three 5‐alkylindanes and two 6‐alkyltetralins
Authors: Wibaut J. P. , Paulis B.
Published: September 2010

The synthesis is described and physical constants are given of some 5‐alkylindanes and 6‐alkyltetralins, all containing fifteen carbon atoms: 5‐n‐hexylindane, 5‐(2‐methylpentyl)indane. 5‐(2‐ethylbutyl)indane. 6‐n‐pentyltetralin and 6‐(1‐ethylpropyl)tetralin.
The temperature variation of orthobaric density difference in liquid‐vapour systems. IV. Fatty acids
Authors: Costello J. M. , Bowden S. T.
Published: September 2010

The density of a series of fatty acids has been determined over ranges of temperature below and above the boiling point. It is shown that the variation of orthobaric density difference with temperature is well represented by the Verschaffelt equation. In general the exponent does not depart greatly from the standard value for non‐associated systems and its variability with temperature is not so marked as that found for water and the aliphatic alcohols. The equation applies with considerable precision to acetic acid from 0° to 280°C. The mean deviation between observed and calculated values of the orthobaric density difference for the higher acids generally does not exceed 0.3%.
Structure and musk odour: I. Indane derivatives
Authors: Beets M. G. J. , van Essen H. , Meerburg W.
Published: September 2010

A series of new indane derivatives with musk odour is described).
The application of ion‐exchangers in detergent analysis
Authors: Voogt P.
Published: September 2010

A method is described for the separation of mixtures of the sodium salts of some alkylsulphuric or sulphonic acids, fatty acids and non‐ionic material into three fractions containing strong acid, weak acid, and non‐ionic constituents respectively. To this end, the mixtures are successively passed over the ion‐exchangers Dowex‐50, X8, [H+], Dowex‐1, X2, [Ac−], and Dowex‐2, X8, [OH−]. The individual acids can be titrated potentiometrically. From the amount of titrant used and the weight of the salts formed as a result of the titration, both the contents and the molecular weights of the acids can be calculated. The content of non‐ionic constituents can be determined gravimetrically.
Assignment of the vibrational frequencies of S2X2 molecules
Authors: Hooge F. N. , Ketelaar J. A. A.
Published: September 2010

A survey is given of the spectra of H2S2, S2(CH3)2, S2F2, S2Cl2 and S2Br2. The vibrational frequencies are calculated for a simplified planar cis model. This calculation leads to an assignment of the observed frequencies, which differs at some points from assignments given previously by other authors.
The assignment of the vibrational frequency of the P = S group
Authors: Hooge F. N. , Christen P. J.
Published: September 2010

The infrared spectra are given of (C2H5)3P, (C2H5),PO, (C2H5)3PS. (CH3)3PS and (C2H5)PSCl2.

From these spectra and spectra of other P = S compounds published previously a useful correlation was found between the position of the P = S band and the different groups attached to the phosphorus atom in XYZP=S molecules. This correlation is supported by model calculations. A survey is given in fig. 10.
Some reactions of 1,1,1,3‐tetrachlorobutane
Authors: Kooyman E. C. , Wagner W. M.
Published: September 2010

1,1,1,3‐Tetrachlorobutane reacts with an excess of many nucleophilic reagents to give good yields of products Cl2C = CH‐CHX‐CH3, in which X may be an OH, O‐alkyl, O‐aryl, aryl‐OH, NH2, alkylamino or dialkylamino group. Trichlorobutenes are probably intermediates, a mixture of 1,1,3‐trichlorobutene‐1 and 1,1,1‐trichlorobutene‐2 being formed when using a molecular proportion of alkali.

The results are compared with those recently reported by Nesmeyanov et al.

A. N. Nesmeyanov, R. Kh. Freidlina, L. I. Zakharkin and A. B. Belyavsky, Zhur. Obshchei. Khim. 26, 1070 (1956): Chem. Abstr. 50, 16658 (1956). Compare also A. N. Nesmeyanov et al., Quart. Revs. 10, 330 (1956).

.
Etude Polarographique des Bishydroperoxydes Stéroïdes
Authors: Legrand Maurice , Delaroff Vladimir , Bimbad Madeleine
Published: September 2010

En milieu hydro‐alcoolique contenant du p‐toluéne sulfonate de sodium, les bishydroperoxydes stéroïdes fournissent, entre pH 5 et 8, des polarogrammes présentant en général quatre vagues. Les deux dernières permettent d'effectuer des dosages.

La troisième vague correspondrait à la réduction du bishydroperoxyde qui redonnerait la cétone de départ et de l'eau oxygénée ensuite réduite au niveau de la dernière vague.
Researches on plant growth regulators, XXIV. Structure/activity, IX. Tetrazole derivatives
Authors: van de Westeringh C. , Veldstra H.
Published: September 2010

Tetrazole analogues of different types of carboxylic acids active as growth substances, were synthesized and analyzed as to their activity in the pea test and in the avena straight growth test.

A large difference between the activities of indole and naphthalene derivatives, not normally found with growth substances, was observed.
Synthesis of β‐phenylethylamine derivatives VI Stereoisomers of 1‐(4′‐hydroxyphenyl)‐2‐(1″‐methyl‐2″‐phenoxyethylamino) propanol‐1
Authors: van Dijk J. , Moed H. D.
Published: September 2010

The synthesis is described of the four pairs of enantiomeric modifications of magnified image

The stereochemical structures have been correlated with those of erythro‐ and threo‐ephedrine.

Conformation analysis has been used to explain the configuration of the amino‐alcohols formed.
Studies on sedum alkaloids V. Synthesis and optical resolution of sedamine and sedridine
Authors: Beyerman H. C. , Eenshuistra J. , Eveleens W. , Zweistra A.
Published: September 2010

The synthesis of the racemates of the alkaloids sedamine and sedridine, the separation of the racemates, and their resolution into optical antipodes are described, with the exception of the resolution of (±)‐allosedridine and so far as no earlier information about these subjects has been given by us.

The results are compared with data about the natural products obtained from Sedum acre and Lobelia inflata.
Hydrogenation of 2,6‐dimethyl‐4‐pyrone II
Authors: de Vrieze J. J.
Published: September 2010

Hydrogenation of 2,6‐dimethyl‐4‐pyrone affords pure 2,6‐dimethyltetrahydropyran‐4‐ol with a modified Raney‐nickel catalyst whereas with a palladium catalyst 2,6‐dimethyltetrahydro‐4‐pyrone is eventually obtained. Partial hydrogenation with a palladium catalyst affords a mixture of 2,6‐dimethyldihydro‐4‐pyrone and 2,6‐dimethyltetrahydro‐4‐pyrone. The latter is hydrogenated to 2,6‐dimethyltetrahydropyran‐4‐ol in presence of platinum.
Thermodynamic properties of gas hydrates II: Phase equilibria in the system H2S‐C3H3‐H2O AT −3°C
Authors: Platteeuw J. C. , van der Waals J. H.
Published: September 2010

The system H2S‐C3H8‐H2O was investigated at −3°C. It was found that the H2S/C3H8 ratio in the hydrate phase depends on the composition of the coexisting gas phase. In this respect it is similar to the system CH4‐C3H8‐H2O studied previously. Unlike the latter, the present system exhibits a minimum pressure (“azeotrope”). It is shown that the solution theory of clathrates can account for this phenomenon.

Our investigation of hydrates in ternary systems leads us to the conclusion that von Stackelberg's distinction between double hydrates and mixed hydrates is not an essential one: both types of hydrates are solid solutions of two volatile solutes in a hydrate lattice.
The reaction of alkylmagnesium halides with thiophosphoryl chloride. I. Formation of bi(dialkylphosphinothioyl) compounds
Authors: Christen P. J. , van der Linde L. M. , Hooge F. N.
Published: September 2010

The reaction of PSCl3, with alkylmagnesium halides has been studied. In the case of methyl‐, ethyl‐, propyl‐, butyl‐ and isobutyl‐magnesium halides compounds with formula (R2PS)2, were formed. Their infrared spectra were recorded from 400 cm−1 to 3000 cm−1. From these spectra it was concluded that bi(dialkylphosphinothioyl) compounds were formed.

In most cases a number of by‐products were isolated and some of these were identified.
An improved synthesis of vitamin B6 (pyridoxol)
Authors: Wuest H. M. , Bigot J. A. , de Boer Th. J. , Wal B. V. D. , Wibaut J. P.
Published: September 2010

The known synthesis of “Ichiba acid”, 2‐methyl‐3‐hydroxypyridine 4,5‐dicarboxylic acid (VII), starting from ethyl acetylpyruvate and cyanoacetamide, has been reinvestigated and simplified to a five step process.

Several derivatives of Ichiba acid have been prepared including the tribenzyl derivative (XIV), with easily accessible dimethylphenylbenzylammonium hydroxide, and the 3‐acetoxy‐anhydride (XVI) with acetic anhydride.

These derivatives are reduced with LiAlH4 to vitamin B6 (VIII) in yields of 72 and 53% respectively.

Results have been compared with the reduction of related pyridine 4,5‐ dicarboxylic acid derivatives with LiAlH4.
Reaction products of primary β‐hydroxyamines with carbonyl compounds. XIII. Condensation of Primary β‐Mercaptoamines with Carbonyl Compounds
Authors: Bergmann Ernst D. , Kaluszyner A.
Published: September 2010

2‐Mercaptoethylamine and 2‐amino‐3‐mercaptobutane have been condensed with various carbonyl compounds. The structure of 14 of these condensation products has been studied by physical methods (molecular refraction, infrared spectrum, ultraviolet spectrum). In all cases, the products formed were thiazolidines and not Schiff bases; in this respect, the 2‐mercaptoamines behave differently from their oxygen isologs.

For comparison, the condensations of N‐substituted 2‐mercaptoethylamines with various carbonyl compounds have also been studied (22 examples). The thiazolidine ring causes a depression of the molecular refraction and is characterized by a series of infrared bands in the 1000–1380 cm−1 region. Contrary to the experience with N‐phenylethanolamine, N‐phenyl‐2‐mercaptoethylamine is capable of condensing not only with aldehydes, but also with ketones.
Synthesis and reactions of diphenyl (β‐pyridyl) chloromethane; Formation of a diphenyl‐(β‐pyridyl)methyl radical
Authors: Otto P. Ph. H. L. , Wibaut J. P.
Published: September 2010

The synthesis and properties of some new compounds connected with diphenyl (β‐pyridyl) carbinol, viz. diphenyl (β‐pyridyl) carbinol hydrochloride, diphenyl (β‐pyridyl) chloromethane and its hydrochloride, bis[diphenyl‐ (β‐pyridyl) methyl] peroxide and a compound C36H28N2, are described. The peroxide is very probably produced from the diphenyl (β‐pyridyl)‐methyl radical formed initially.
The condensation of rhodanine and derivatives with trialdehydes containing a 1,3,5‐triazine ring
Authors: Allan F. J. , Allan G. G.
Published: September 2010

The condensation products of rhodanine, 3‐ethylrhodanine and 3‐phenylrhodanine with various trialdehydes containing a 1,3,5‐triazine ring have been prepared for bacterial and fungicidal evaluation. The condensation of rhodanine and its derivatives with aldehydes, previously described for mono and dialdehydes, has thus been extended to the trialdehydes. The 1,3,5‐triazine ring is itself the basis of compounds of known fungicidal properties and may therefore enhance the already known fungicidal character of the substituted rhodanines. The trialdehydes are novel compounds which were prepared by the interaction of the hydroxybenzaldehydes and 2,4,6‐trichloro‐1,3,5‐triazine. Condensations between the rhodanines and the trialdehydes were carried out in acid medium and crystalline coloured condensation products were obtained in good yield.
Investigations on nematicides: II. Structure of a second nematicidal principle isolated from Tagetes roots
Authors: Uhlenbroek J. H. , Bijloo J. D.
Published: September 2010

A second nematicidal principle isolated from Tagetes roots has been identified as 5‐(3‐buten‐1‐ynyl)‐2.2′‐bithienyl. Upon catalytic hydrogenation 5‐butyl‐2.2′‐bithienyl was obtained which by comparison of infrared spectra proved to be identical with a synthetically prepared sample. The 5‐(3‐buten‐1‐ynyl)‐2,2′‐bithienyl was further characterized by its infrared absorption.
The sodium potassium‐selectivity of complexes of bovine serum albumin with positively or negatively charged detergents, measured by ultrafiltration
Authors: van Oss C. J. , Simonnet H. , Annicolas D.
Published: September 2010

Pure bovine serum albumin, which has no Na•/K•‐selectivity, may become strongly selective for Na• or for K• if it is associated with positive or negative detergents.

A strong influence of the salt anion is observed: if Br′ is used instead of Cl′, the negative charge of the albumin grows considerably in most cases. The Na•/K•‐selectivity is highest when the negative charge of the albumin is low.
Osmotic pressures of aqueous poly‐(acrylic acid) solutions
Authors: Orofino T. A.
Published: September 2010

Osmotic pressure measurements over a range of polymer concentration are reported for a high molecular weight sodium polyacrylate fraction of one‐third and full neutralization in 0.1 M‐sodium chloride solutions. From data on solutions sufficiently concentrated in polymer to justify representation as uniform dispersions of segments in solvent, values of an effective charge parameter are calculated. These are compared with charge parameters deduced indirectly, although in an equivalent manner, from previous dilute solution studies on related systems.
Preparation of diphenylpyridylmethanes and phenyldipyridylmethanes from the corresponding trisubstituted methanols by reduction
Authors: Otto P. Ph. H. L. , Wibaut J. P. , Groenendaal G. W. J. M.
Published: September 2010

The corresponding diphenylpyridylmethanes and phenyldipyridylmethanes are produced from diphenylpyridylcarbinols and phenyldipyridyl carbinols, respectively, by reduction with hydriodic acid in glacial acetic acid or with phosphorus triiodide and hydriodic acid. Tripyridylcarbinols are not reduced under these conditions.

Diphenyl(β‐pyridyl) acetic acid is obtained from diphenyl(β‐pyridyl) methane by the action of phenyllithium‐phenylsodium and subsequent carboxylation.
The reaction of alkylmagnesium halides with thiophosphoryl chloride: II. Formation of dialkylphosphinic chlorides
Authors: Christen P. J. , van der Linde L. M.
Published: September 2010

The preparation of dimethyl‐, diethyl‐, dipropyl‐, dibutyl‐, and di‐isobutylphosphinic chlorides from bi(dialkylphosphinothioyl) compounds, mentioned in the first part of this paper1, is described (Table I).

In the reactions of alkylmagnesium halides with PSCl3, where several phosphinic acidic reaction products are formed [for instance (R2PS)2, R2PSCl, and R2P(S)SH], the combined reaction products from each Grignard reaction are oxidized and the crude phosphinic acids converted into the phosphinic chlorides. In this way dipropyl‐, di‐isopropyl‐, dibutyl‐, di‐isobutyl, di‐s‐butyl‐, and dipentylphosphinic chlorides are obtained in good yield (Table II).
The reaction of N,N‐dimethyl‐ and N,N‐diethylaniline with silicon tetrabromide
Authors: Breederveld H.
Published: September 2010

N‐methylanilino‐tribromosilane, N‐ethylanilino‐tribromosilane, and di(N‐ethylanilino)‐dibromosilane have been prepared from the corresponding N,N‐dialkylaniline and silicon tetrabromide at about 180°.
Micro‐determination of the iodine‐value
Authors: Smits P.
Published: September 2010

The development of a method, enabling the iodine‐values of micro amounts of fatty acids or their esters to be easily determined, is described. An excess of iodine is added to the sample and the amount of bound iodine determined spectrophotometrically.
The halochromism of benzophenone oximes.
Authors: Rekker R. F. , Veenland J. U.
Published: September 2010

A comparison of spectral data on benzophenone oximes in concentrated sulphuric acid and those of benzophenones in ethanol or iso‐octane suggests phenyl‐phenyl interaction as absorption mechanism for benzophenone oximes in concentrated sulphuric acid.
The reaction of phenol with formaldehyde: II. The ratio of ortho‐ and para‐hydroxymethylphenol in the base‐catalyzed hydroxymethylation of phenol.
Authors: Peer H. G.
Published: September 2010

A kinetic study of the first step in the reaction of phenol and formaldehyde, the formation of ortho‐ and para‐hydroxymethylphenol, is described.

It is found that when using NaOH or KOH as a catalyst under weakly alkaline conditions (pH = 8.5‐10.5) at 30° C, the para‐position in the phenolic nucleus is nearly twice as reactive as the ortho‐position (the ortho/para ratio being 1.10). Interesting effects are observed in more strongly alkaline media (pH = 10.5‐13.5), inter alia a sharp decrease in the ortho/para ratio with increasing value of pH.

When other hydroxides are used, an increasing value of the ortho/para ratio is found with the hydroxides of K, Na, Li, Ba, Sr, Ca and Mg, respectively. Probably chelate formation occurs in the transition state for ortho substitution.