bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthèse et structure cristalline de la dihydro‐2, 3 (nitro‐5 pyridyl‐2)‐3 propyl‐6 thioxo‐2 1h pyrimidinone‐4
Authors: Dupont L. , Dideberg D. , Jamoulle J. C. , Lapière C. L. , Bourdais J.
Published: September 2010

Condensation of 2‐chloro‐5‐nitro pyridine with propyl‐thiouracil has been carried selectively on the S as well as on N(3) of propylthiouracil. The crystal structure of the latter compound (C12H12N4O3S) has been determined. Space group is P21, Z=8, a=12.476(4), b=22.625(5), c=9.878(4)Å, B=90.883(10)°. The four independent molecules have almost the same conformation with the nitro group rotated by 7° to 11° from the pyridine rings: the dihedral angles between the latter and the pyrimidine planes are included in the limits 80 to 84°.
Mechanistic Aspects of Reduction of Ditelluratocuprate (III) by α‐Hydroxy Acids in Alkaline Medium
Authors: Murthy C. P. , Sethuram B. , Rao T. Navaneeth
Published: September 2010

The kinetics and mechanism of oxidation of lactic acid, glycolic acid and mandelic acid by tellurate complex of trivalent copper in alkaline medium was studied. The kinetics were monitored by following the disappearance of Cu (III) spectrophotometrically at 405 nm. The reactions are first order in each [reactant] and fractional order in [ligand] and [OH−]. The results are discussed with reference to electron density on ‐OH− or ‐COO substrate sites and probable mechanism suggested.
Bepaling van Aantalgemiddeld Molecuulgewicht en Heterogeniteitsindex Via Diffusie‐Experimenten
Authors: Peeters F. A. H. , Soeteman A. A.
Published: September 2010

The determination of averages of diffusion coefficients and among others, from them, the number‐average molecular weight, becomes possible after reformulation of Sundelöf's method of processing of free diffusion data. An index of heterogeneity may be calculated too.
Characterization of Structural Isomers in Commercial 2‐Hydroxypropyl Methacrylate
Authors: Schacht Etienne , Bruyn André De , Simondsxs Ronald , Goethals Eric
Published: September 2010

Commercial 2‐hydroxypropylmethacrylate contains a structural isomer: 2‐hydroxy‐1‐methyl‐methacrylate. The mixture was analysed by GC‐MS and 360 MHz 1H NMR. The NMR parameters for both isomers are reported.
Reductive Couplings of Ketones by Low‐Valent Titanium, Prepared from TiCl4 and Reducing Agents
Authors: Dams R. , Malinowski M. , Geise H. J.
Published: September 2010

The reductive coupling of benzophenone to tetraphenylethene was studied. The coupling reagent, low‐valent titanium, was obtained after reduction of TiCl4. The results are compared with those of similar couplings using low‐valent titanium obtained after reduction of TiCl3.

E.s.r. measurements and chemical observations show that the TiCl4‐and the TiCl3‐system behave completely analoguous with respect to reduction to low‐valent titanium as well as with respect to reactivity towards ketones and alcohols.
Étude Structurale des Analogues de la Minaprine: 1. Structure Moléculaire du Dichlorhydrate de la Desméthylminaprine
Authors: Michel A. , Gustin R. , Evrard G. , Durant F.
Published: September 2010

This paper initiates a series of structural studies on analogs of minaprine, a psychotropic drug, in order to establish structure‐activity relationships. The results of the crystal structure analysis of the desmethylminaprine.2 HCl.H2O are related. In particular, we discuss the electronic delocalization in the aminopyridazlnium moiety.
Crystal Structure of Baurenyl Acetate from Tabernaemontana Longipes Donn. Smith
Authors: Tinant B. , Germain G. , Declercq J. P. , van Meerssche M. , Ciccio J. F. , Hoet P.
Published: September 2010

The structure of the title compound (D:C‐Friedours‐7‐en‐3‐ol acetate 3β) has been determined by single crystal X‐ray diffractometry. Crystal data are as follow: orthorhombic, P212121, a = 8.291(1), b = 11.084(3), c = 30.041 (8) Å, V =2761(1) Å3, Dx = 1.13 Mg m−3 for Z = 4.
Les Polymères Bioactifs XI. Insolubilisation de la β‐Amylase Sur les Dérivés de la Cellulose
Authors: Bouzaher Y. , Dumitriu S. , Simionescu Cr.
Published: September 2010

The immobilization of β‐amylase on acid chloride of carboxymethylcellulose (DS = 2.02) and BIOZAN R is presented. Kinetic studies established the following conditions for a optimum coupling: pH = 8.4, time = 2 h, temperature = 5°C. The immobilization on BIOZAN R was carried out by using the BIOZAN R acid chloride or by activation with dicyclocarbodiimide. The results showed that the nature of the carrier and the method of immobilization determine directly the quantity and the activity of the coupled β‐amylase.
The Crystal Structure of (3R,65)‐3‐Benzyl‐4‐Methyl‐1, 4‐Diaza‐Bicyclo [4.4.0] Decan‐2,5‐Dione
Authors: van Poucke M. , Lenstra A. T. H.
Published: September 2010

The piperidine ring in the title compound is in the chair conformation, whereas the diketopiperazine ring has a boat form. The benzyl group is axially positioned and folded above the diketopiperazine ring. No dimerisation is observed.
Isolement par Chromatographie Liquide a Haute Performance Préparative D'Appariement D'Ions et Identification des Constituants Majeurs du Jaune de Quinoléine (C.I. 47005)
Authors: Masiala‐Tsobo C. , Gelbcke M. , Dumont L. , Parmentier F. , Grimée R.
Published: September 2010

A qualitative and quantitative study of the constituents of quinoline yellow (C.I. 47005) in several samples is presented here. The isolation through preparative ion pairs HPLC of these constituents, followed by a spectroscopic examination (UV‐visible, IR, 1H ‐ NMR) and by a study which compares them to synthesized derivatives, shows that quinoline yellow commercial samples contain chiefly disodic salts of 2‐(2′‐quinolyl) 1, 3‐indandione sulfonic acids sulfonated respectively on 5,6′ and 5,8′ positions. Some samples contain also important quantities of the last mentioned compound methylated on 6′ position.
Étude en RMN du Carbone‐13 de Quelques Colorants (Quinoleinyl‐2′)‐2 Indanedione‐1, 3 Sulfones
Authors: Gelbcke M. , Masiala‐Tsobo C. , Dumont L. , Parmentier F. , Grimée R.
Published: September 2010

Carbon‐13 nuclear magnetic resonance spectra of some sulfonated 2‐(2′‐quinolyl)‐1, 3‐indanedione dyes have been reported and fully assigned.
Amino Steroids ‐ 12‐Oxygenated Heteroconanine Derivatives. Preparation and Properties
Authors: van De Woude G. , Biesemans M. , van Hove L.
Published: September 2010

Treatment of N‐methyl‐5α‐conaninium iodides, diversely oxygenated at position 12, with a boiling solution of potassium hydroxide in ethylene glycol most often appears to be a satisfactory method to obtain the title compounds. The latter are free bases of reversed configuration at C‐20 with regard to the starting compounds. The conversion is however never complete: the conanine base and an isomer of the normal Hofmann elimination product are always formed, occasionally together with minor degradation products.

Comparison of the properties of heteroconan‐3β‐ols carrying an oxygen function at C‐12 with those of the corresponding conan‐3β‐ols revealed differences which can be used as rules to distinguish the epimers of a pair. Deviations from the generally observed regularities seem to be dependent on the nature of the oxygen function located at C‐12.
Structural Studies of 2‐Aceto‐1‐naphthol‐Salicyl Hydrazone Complexes of Cu(II), Co(II), Ni(II), Mn(II), Ce(III) and UO
Authors: Khattab M. A. , Soliman M. S. , El‐Enany G.
Published: September 2010

Complexes of Cu(II), Co(II), Ni(II), Mn(II), Ce(III) and UO2+2 with 2‐aceto‐ 1 ‐naphthol‐N‐salicly hydrazone (AN.S.H) have been prepared and characterized on the basis of analytical, UV, visible, and IR spectroscopic, conductance and magnetic moment data. The measurements revealed the existence of mono‐ and bis‐ligand complexes. The electronic spectra of the complexes in dimethyl formamide solution indicate that the bis‐ligand complexes of Cu, Ni, Co and Mn have octahedral structure, and the mono‐ligand complexes of Cu and Ni are square planar. Spectrophotometric studies suggest the use of this ligand for the micro‐determination of metal ions in solution. The apparent formation constants of the complexes have been determind.
1H NMR study of 1, 6‐Anhydro‐β‐D‐Glucopyranose Tosylated at 2‐ and/or 4‐Position
Authors: van Rijsbergen Ronan , Anteunis Marc J. O. , De Bruyn André
Published: September 2010

The 1H nmr spectra of 1,6‐anhydro‐2‐0‐tosyl‐, 1,6‐anhydro‐4‐0‐tosyl‐ and 1,6‐anhydro‐2,4‐di‐O‐tosyl‐β‐D‐glucopyranose have been analyzed. The data allow to discriminate between the two monosubstituted levoglucosans.
Hydrogenation and Other Side‐Reactions During the Reductive Coupling of Ketones with Lowvalent Titanium (McMurry Synthesis)
Authors: Malinowski R. Dams , Geise H. J.
Published: September 2010

Active titanium slurries, effective in the McMurry coupling reaction of ketones to olefins, are also hydrogenation agents. Sometimes they also promote isomerisation of the originally formed olefin as well as aldol type and pinacol type condensations under special reaction conditions.

The most prominent factors promoting hydrogenation are the use of high ratios LiAlH4: TiCl3 and low temperatures in the formation of the low‐valent titanium species.
The Analysis of the Homogeneous Saponification Method Applied to High Pressure Ethylene Vinylacetate Copolymers. Part I: Kinetical Consideration
Authors: Koopmans R. J. , van Der Linden R. , Vansant E. F.
Published: September 2010

Three high pressure ethylene vinylacetate (EVA) copolymers having a mol % VA between 0 and 20 are transformed into ethylene vinylalcohol vinylacetate (EVALVA) terpolymers by an homogeneous saponification method. The acetoxy‐hydroxide conversion proved to be caused by two similtaneously occuring reactions, a saponification and a transesterification. The overall reaction, however, could be discribed by second order kinetics. The lower VA conversion rate of EVA types having 3.5 vs 12.0 and 18.8 mol % VA was explained a combined steric and neighbouring group effect. Finally a mechanism applicable to any EVA type copolymer was forwarded to comprehend the acetoxy‐hydroxide conversion.
π‐π Molecular Complexes of Nitrones with Tetracyanoethylene and 1, 4‐Benzoquinones
Authors: Nour‐el‐Din Ahmed M. , Mourad Aboul‐Fetouh E.
Published: September 2010

Charge‐transfer molecular complexes between some nitrones with different substituents and tetracyanoethylene, 2, 3‐dichloro‐5, 6‐dicyanobenzoquinone and chloranil have been studied in methylene chloride solution at 25° C. The maximum absorption wavelengths, stoichiometry, apparent formation constants and transition energies confirm the formation of the π ‐ π molecular complexes. The effect of solvent, the formation and stability of these complexes have been discussed.
Structure Cristalline des Complexes du Cuivre(I) Avec la Thiourée III. Complexes Contenant des Cations Cu4 (tu)4 +6 DE TYPE ADAMANTANE: A. LE BIS (BISULFATE) SULFATE D'HEXAKIS (THIOUREE)‐TETRACUIVRE(I) MONOHYDRATE Cu4 [SC(NH2) 2] 6 (HSO4) 2SO4.H2O B. LE SULFATE D'HEXAKIS (THIOUREE)‐TETRACUIVRE (I) DIHYDRATE Cu4 [SC(NH2) 2] 6 (SO4) 2 · 2H2O
Authors: van Meerssche M. , Kamara R. , Germain G. , Declercq J. P.
Published: September 2010

The two title compounds have been prepared from sulfuric (A) or acetic (B) acid solution of CuSO4 and thiourea. Their crystal structure were determined from X ray diffractometer measurements. The crystal data are as follows: A: triclinic, space group P1, a = 13.863 (5), b = 13.385 (5), c = 10.251 (3)Å, α = 68.56 (2), β = 70.11 (2), γ = 82.51 (2)°, V = 1664. 9 (1.0)Å3 and Z = 2 for Dx = 2.03 Mg m−3. B: orthorhombic, Pbca, a = 35.487(12), b = 9.970(3), c = 33.147(10)Å, V = 11727. 6(6.4)Å3 and Z = 16 for Dx = 2.13 Mg m−3. In both compounds the cationic fragment Cu4S6 exhibits an adamantane‐type structure. The anion H2(SO4)4 ‐3 of the A compound shows very short hydrogen bonds (2.43 Å).
Solvent Effect Upon the Polarity and Stability of Pentabromophenol‐Amine Adducts
Authors: Majerz I. , Malarski Z. , Sobczyk L.
Published: September 2010

Dipole moments and formation equilibrium constants of a series of pentabromophenol complexes with ternary amines in carbon tetrachloride, chloroform and 1,2‐dichloroethane were measured. The values of the hydrogen bond polarity, Δμ, were correlated with the ΔpKa parameter and the effect of the solvent activity on the charge distribution in hydrogen bonded complexes was discussed.
Multielement Determination of Trace Elements in Plant Samples by Inductively Coupled Plasma Emission Spectroscopy: Preconcentration and Elimination of Alkaline Earth Metal Interferences
Authors: Camerlynck R. , Martens R. , Verloo M.
Published: September 2010

Direct trace element determination with ICP‐spectrometry in plant samples is hampered by severe interferences of Ca and Mg.

A method is proposed to eliminate chemically the interfering concomitants while at the same time several trace elements are preconcentrated with the aid of a chelating ion exchange resin.
Structure and Reactivity of a Stable Oxirane Derived from 2,2,6,6‐Tetrachloro‐3,3,5‐Trimethylcyclohexanone and Methanolic Sodium Methoxide
Authors: De Buyck Laurent , Dewaele Marc , De Kimpe Norbert , Verhé Roland , Schamp Niceas
Published: September 2010

The title ketone 1 afforded > 95% of fairly stable t‐1,3,3‐trichloro‐t‐2‐methoxy‐4,6,6‐trimethyl‐1,2‐epoxycyclohexane (2) by reaction with cold methanolic sodium methoxide. Heating or contact with sulfuric acid or boron trifluoride caused stereospecific rearrangement of 2 into t‐2,3,3‐trichloro‐2‐methoxy‐4,6,6‐trimethylcyclohexanone (3). On the contrary, rearrangement into the epimeric ketone 4 was induced by trifluoroacetic or dichloroacetic acid in carbon tetrachloride. Epimer 4 was distinctly more reactive than 3 towards dehalogenation with zinc in acetic acid and towards sodium methoxide. Good yields of 3,3‐dichloro‐4, 6,6‐trimethyl‐1,2‐cyclohexanedione (7) were obtained from 2, 3 or 4 in hot solutions of zinc chloride in acetic acid.

The symmetric 2,2,6,6‐tetrachloro‐3,3,5,5‐tetramethylcyclohexanone (8) showed analogous reactions.
Catalytic Activity of Pt/AlPO4 and Related Systems. II.‐ Gas‐Phase Hydrogenation of Xylenes
Authors: Aramendia M. A. , Borau V. , Jimenez C. , Marinas J. M.
Published: September 2010

In the present paper data are reported on the gas‐phase hydrogenation of O‐, m‐, and p‐xylene and O‐, m‐, and p‐ethylmethylbenzene using a pulse reactor. New systems obtained by supporting Pt on AlPO4 ‐Al2O3 (75/25), pure AlPO4 and SiO2 ‐AlPO4 (80/20) have been used as catalysts. The effect of the reduction temperature of the catalysts and the hydrogen pressure on the selectivity to cis‐ and trans‐dimethylcyclohexanes and ethylmethylcyclohexanes has been investigated. The results obtained are interpreted by assuming a Horiuti‐Polanyi mechanism, with suprafacial addition of hydrogen.
Contribution a l'Étude Électrochimique de Derives de L'Acide Mercapto‐3 Pyridine Carboxylique‐2
Authors: Lejeune R. , Vandenbalck J. L. , Patriarche G. J. , Lapiere C. L.
Published: September 2010

2‐methoxycarbonyl‐1‐methyl‐3‐methylthio‐pyridinium iodide (Ia), 2‐carboxy‐1‐methyl‐3‐methylthio‐pyridinium iodide (Ib), 3‐mercapto‐2‐methoxycarbonyl‐1‐methyl‐pyridinium iodide (IIa) and 2‐carboxy‐3‐mercapto‐1‐methyl‐pyridinium iodide (IIb) have been studied by recent electrochemical techniques such as direct (DC), alternating current (AC), differential pulse polarography (DPP) and cyclic voltammetry.

The influence of the pH has been observed and put in connection with the structure of the compounds studied.

Cyclic voltammetry has permitted to differentiate Ia and Ib by the existence of reversible phenomena that become evident only for the carboxycompound.

The study of the influence of the concentration has permitted to set up the best conditions for the determination of these compounds by direct current (DC) and differential pulse polarography (DPP).
Contribution a L'étude Électrochimique de Derives de L'Acide Mercapto‐3 Pyridine Carboxylique‐2
Authors: Lejeune R. , Vandenbalck J. L. , Patriarche G. J. , Lapiere C. L.
Published: September 2010

3‐methylthiopyridine‐2‐carboxylic acid and its methylic ester have been investigated by recent electrochemical techniques such as direct (DC), alternating (AC) current, differential pulse polarography (DPP), controlled potential coulometry and cyclic voltammetry. The influence of polarographical parameters, pH and concentration on the electrochemical behaviour of these compounds permits to explore several of their chemical properties. On the other hand, the optimal conditions for the quantitative determination of traces have been established.
Diffusie‐, Visceus en GPC‐Gedrag van Dextranen in Water als Functie van Hun Molecuulgewicht
Authors: Soeteman A. A. , Peeters F. A. H.
Published: September 2010

For a number of dextrans (Pharmacia) with known molecular weight M, the viscous and GPC behaviour, in aqueous solutions at 30 °C, have been investigated. In spite of branching, well‐defined calibration curves based on M or the viscosity number [η], could be constructed, proving the homologous character of this dextrans. The dispersion‐corrected Mark‐Houwink relation is: [η] = 7.53. 10−2. M0. 523 (ml/g), for 104 ≤ M ≤ 105. At higher molecular weights the exponent decreases up to 0.34. Processing of classical diffusion experiments, following Sundelöf, enables determination of a number of averages of diffusion coefficients Dp, with p > ‐1/2, from the deviation function, and, moreover, of the reduced height‐area ratio DA. Using the chromatograms, the M‐based calibration curve and these D‐averages, we corrected the D, M‐relation for dispersion: D = 8.84. 10−5. M−0. 476 (cm2/s), for 104 ≤ M ≤ 105. With the number‐averaged M values at one's disposal, the use of GPC may be circumvented in the calculation of the relation. From this and the deviation function several averages of M resulted, being reasonably in accordance with the GPC values. The ratio of radii, rη/rf, calculated from M, [η] and D, equals the value one very closely, but diminishes somewhat with M.
Thermodynamic Properties of n‐Butanol‐Cyclohexanone and N‐Butanol‐Ethylacetate Systems
Authors: Shanmugasundaram V. , Mohan R.
Published: September 2010

The temperature dependence of the equilibrium constants of n‐butanol‐cyclohexanone and n‐butanol‐ethylacetate systems has been studied by the dielectric method. The excess thermodynamic quantities of these systems are calculated and are used to point out the nature of interactions in these systems.
Synthesis in the Field of Natural Products of Biological Relevance
Authors: Arcamone Federico
Published: September 2010

The chemical manipulation of the aminosugar, daunosamine, has resulted in the development of new interesting doxorubicin analogues, namely 4′‐epi‐ and 4′‐deoxydoxorubicin, whereas the total synthesis of new aglycones has provided new structural types of the anthracyclines. In the field of beta‐lactams, efforts aimed to the discovery of original anti‐infective compounds have led to the synthesis of novel “penem” derivatives starting from methyl penicillinate.
Theoretical studies of localization phenomena in excited states of polyene chains
Authors: Brédas J. L. , Thémans B. , André J. M. , Piela L.
Published: September 2010

We present π‐electrons RHF‐SCF and CI calculations of the evolution of the first singlet excited state transition energy as a function of chain length, in polyene oligomers ranging from C2H4 up to C42H44. The results indicate that in small oligomers, the excitation is delocalized over the whole molecule. Localization phenomena are present in the larger chains (larger than ∼ C14H16) thereby explaining the failure of the RHF‐SCF technique to properly describe the first singlet excited state energies in the extended oligomers. Consequences in the use of so‐called OAO techniques are pointed out.
Synthesis of heterocycles from 3‐phenyl‐4‐tosylimino‐1, 3‐thiazetidine‐2‐thione
Authors: L'abbé Gerrit , Vangheluwe Patricia , Toppet Suzanne
Published: September 2010

The title compound 3 is transformed into the heterocycles 4‐7 by treatment with the reagents given in Scheme I. In all cases, initial nucleophilic attack occurs at the CS function of 3. The facile ring‐expansion reaction 3‐7 has been successfully extended to other 1,3‐thiazetidin‐2‐thiones (2, RPh, Tol) to give the corresponding 1, 2, 4‐dithiazolidine‐3‐thiones (13 and 14) in high yield.
3α‐Hydroxy‐8β‐Trinervita‐1,11‐Diene: A Novel Diterpene From TwoTrinervitermesSpecies
Authors: Braekman J. C. , Daloze D. , Dupont A. , Arrieta J. M. , Piccinni‐Leopardi C. , Germain G. , van Meerssche M.
Published: September 2010

This paper describes the structure determination of a novel diterpene, 3α‐hydroxy‐8β‐trinervita‐1,11‐diene, isolated from the defensive secretion of two West‐African termites:Trinervitermes oeconomusandT. trinervius.
Organotin Compounds: New Organometallic Derivatives Exhibiting Anti‐Tumour Activity
Authors: Haiduc Ionel , Silvestru Cristian , Gielen Marcel
Published: September 2010

The activity of sixteen organotin compounds in vivo towards the P388 lymphocytic leukaemia tumour in mice is given and discussed.
On the Use of the Minimal STO‐3G Basis Set in Calculating The Geometries of Si Compounds
Authors: Roelandt F. F. , van De Vondel D. F. , van Der Kelen G. P.
Published: September 2010

The minimal STO‐3G basis set is applied to the ab initio calculation of the geometry of Si compounds. It is found that better results are obtained when scaling the ls H exponent scale factor to 1.06 instead of the usual value of 1.24. Changing the 3sp Si valence exponent seems to be less effective.
Large Ring Heterocycles: Template Synthesis and Structure
Authors: Shanzer Abraham
Published: September 2010

One of the major differences between synthetic and natural ion carriers is the abundance of amide and lactone groups in the natural compounds. In order to shed light on the role of the carbonyl groups in these molecules, several series of macrocyclic polycarbonyl compounds have been prepared, and their conformations compared with those of the naturally occurring ionophores. The synthesis of these compounds was achieved via the use of cyclic silicon and tin derivatives as templates. The conformation of the macrocyclic products was determined both in solution and in the solid state. This structural comparison led to recognize the effect of ring symmetry on conformation, and to realize that the presence of rotational symmetry is a prerequisite for a macrocyclic polycarbonyl compound to simulate the conformation of natural ionophores.
Spectres RMN‐1H et ‐13C de L'Acide Mercapto‐6 Pyridinecarboxylique‐2 et de Ses Dérivés Méthyles Correspondants
Authors: Gelbcke M. , Grimée R. , Lejeune R. , Thunus L. , Dejardin J. V.
Published: September 2010

Proton and carbon‐13 chemical shifts and coupling constants of 6‐mercapto‐2‐pyridinecarboxylic acid and its seven methylated derivatives are reported. Substituent effects are discussed
Separation, and characterization of the rotamers of hexakis (2‐methoxyphenyl) benzene and hexakis (2‐methylphenyl) benzene
Authors: Pepermans Henri , Gielen Marcel , Hoogzand Cornelis , Willem Rudolph
Published: September 2010

The HPLC separation and characterization of the rotamers of hexakis (2‐methoxy‐phenyl)benzene and hexakis (2‐methylphenyl) benzene are discussed. Preliminary results on the kinetics of the interconversion of the rotamers of hexakis (2‐methoxyphenyl) benzene are presented.
Triterpenoïdes de Harpullia Cupanioïdes
Authors: Dimbi Makoso Zeza , Warin Roger , Delaude Clément , Huls Robert , Mpuza Kapundu
Published: September 2010

Tree new triterpenoids have been isolated from acid hydrolyzate of the root bark saponin of Harpullia cupanioides Roxb.. Their structures have been established from spectral data as camelliagenin A 16‐tiglate, camelliagenin A l6‐β,β‐dimethylacrylate and camelliagenin A 22‐β, β‐dimethylacrylate.

Besides these, other polyhydroxy triterpenoids characterized as camelliagenin A 22‐angelate, A1‐barrigenol 22‐angelate and A1‐barrigenol 22‐β, β‐dimethylacrylate have also been isolated.
Influence of P:V Ratio on the Reducibility and Oxidizability of Vanadium Phosphorus Oxide Catalysts
Authors: Hodnett B. K. , Delmon B.
Published: September 2010

Preliminary results on reducibility and oxidizability of vanadium phosphorus oxide catalysts with differing P:V ratios are reported. Small amounts of phosphorus in excess of the stoichiometric amount strongly inhibit oxidation of the catalyst during calcination. No clear correlation seems to exist between the kinetics of reoxidation and the initial reactivity of the catalysts towards hydrogen.
Synthesis of alkylindoles in gas phase on an aluminium orthophosphate
Authors: Esteban S. , Marinas J. M. , Martinez‐Alcazar M. P. , Martinez M. , Agarrabeitia A. R.
Published: September 2010

The synthesis of alkylindoles in the gas phase over an aluminium orthophosphate Kearby type catalyst has been studied. As reactants different carbonyl compounds and phenylhydrazine or aniline have been employed. The conditions of temperature and molar ratio of carbonyl compound/nitrogenous compound have been changed. The best results were reached in the reactions between the lower aldehydes and aniline. Thus, 75% alkylindoles were obtained from propanaldehyde and 62% from butyraldehyde. Also remarkable is the reaction between cyclopentanone and phenylhydrazine because 45% 2,3‐trimethyleneindole was obtained.
Mass spectrometric study of (CH3)4‐nSi(SCH3)n (n=1‐4) and (CH3)2Si(‐SCH2‐)2
Authors: Naessens L. A. , Claeys E. G. , Hoste S. , van Der Kelen G. P.
Published: September 2010

The mass spectra of the series (CH3)4‐nSi(SCH3)n (n=1‐4) and of (CH3)2Si(‐SCH2‐)2 were studied and the fragmentation processes under electron impact are discussed. The main features of the mass spectra are: (i) the high abundance of the molecular ions, (ii) the competitive loss of methyl and thiomethyl radicals from the molecular ions with formation of the base peak ions, (iii) the elimination of a number of neutral fragments as the most likely fragmentation process of the base peak ions.
Approaches Towards the Synthesis of Allenyl Azides
Authors: L'abbé Gerrit , Mahy Michel , Bollyn Marcus , Germain Gabriel , Scheefer Guy
Published: September 2010

Methods which are known to produce allenes under mild conditions have failed to synthesize the yet unknown title compounds. These are (i) azide substitution of propargyl sulfonates, (ii) reactions of α‐azido acid chlorides with ynamines, and (iii) Wittig condensation of α‐azido acid chlorides with phosphorus ylides. The reaction products obtained are respectively azidoalkyl‐1, 2, 3‐triazoles (4), pyrrolinones (6) or pyridines (8), and a disubstituted ylide (11) or the fused triazole 12.
Synthèse, Par la Méthode de Hewett, Des Benzo [a]Naphto[2,1‐j]Anthracéne, Naphto[2,1‐c]Chrysene, Benzo[a]Picéne et 8,16‐Diméthoxycarbonylbenzo[c] Naphto [2,1‐1] Chrysene
Authors: Brison Jean , Martin Richard H.
Published: September 2010

Synthesis, by Hewett's method, of benzo[a] naphtho [2,1‐j]anthracene, naphtho[2,1‐c]chrysene, benzo[a]picene and 8,16‐dimethoxycarbonylbenzo[c] naphtho[2,1‐1]chrysene. The title compounds 8b, 9b and 10b were obtained by potash fusion of α‐(1‐bromo‐2‐naphthyl)‐β‐(2‐phenanthryl) acrylic acid (7) followed by decarboxylation. The dicarboxylic ester 13 was prepared a. by potash fusion of 12a and 12b followed by esterification b. by the double photocyclisation of the dimethyl esters 12b and 12c.
Synthèse Photochimique D'Hydrocarbures Polycycliques Aromatiques et Étude en RMN‐1H Des Protons de Baie. Effets de Solvant Specifiques et Effets Nucleaires Overhauser
Authors: Brison Jean , De Bakker Claude , Defay Nicole , Geerts‐Evrard France , Marchant Marie‐Jeanne , Martin Richard H.
Published: September 2010

“Photochemical synthesis of polycyclic aromatic hydrocarbons and NMR‐1H study of bay protons. Specific solvent effects and nuclear Overhauser effects”. Dinaphtho[1,2‐a 2′,1′‐j]anthracene (4a), 9‐bromo‐dinaphto [1,2‐a; 2′,1′‐j]anthracene (4b), 9‐methyldinaphtho[1,2‐a; 2′,1′‐j]anthracene (4c), benzo [c]naphtho [2,1‐1]chrysene (7), benzo [a]naphtho [2,1‐j]anthracene (3), naphtho [2,1‐c]chrysene (9) and dibenzo [c,1] chrysene (12) have been synthesized by the photocyclodehydrogenation of 1,2‐diarylethylenes (5,8) and bis (arylvinyl)arenes (6, 10). The NMR study has been mainly focused on the bay protons involved in specific solvent effects (Table 4) and nuclear Overhauser effects (Table 5).
Carbon‐13 Chemical Shifts of Three Oxo‐, Six Monohydroxy‐, and Four Dihydroxycyclohexyl Derivatives of Trihexyphenidyl
Authors: Paeme G. , Grimée R. , Vercruysse A.
Published: September 2010

A number of oxo‐, monohydroxy‐ and dihydroxycyclohexyl derivatives of trihexyphenidyl were synthetised as potential metabolites of this drug in the rat. They were identified by 13C‐NMR spectroscopy.
Preparative Investigations of Bromoarsenate (III) Complexes
Authors: Rizvi S. S. A.
Published: September 2010

The reaction of AsBr3 with different amine hydrobromides were studied in aqueous hydrobromic acid (48 %) medium. A few of these compounds were prepared by Popov (1) in chloroform medium. Two types of complexes like 1:1 and 2:3 were prepared. Arsenic, nitrogen, bromine, carbon and hydrogen have been estimated and chemical nomenclature suggested.
EnzymaticIn VitroReduction of Ketones. Part 111. The Unexpected Steric Course of the HLAD Catalyzed Reduction of 3‐Cyanocyclohexanone
Authors: Willaert Jan J. , Lemière Guy L. , Dommisse Roger A. , Lepoivre Joseph A. , Alderweireldt Frank C.
Published: September 2010

3‐Cyanocyclohexanone is a suitable substrate for preparative HLAD reduction, delivering enantiomerically pure (1S, 3S)‐transand (1R, 3S)‐cis‐alcohols. Details are given on the kinetics of the reduction and the absolute configuration of the products.

In contrast to recently developed reaction models an important amount of (1R,3S)‐cis‐alcohol is formed.

Some side reactions of the substrate with the TRIS‐buffered medium are described.
Une Nouvelle Methode De Bromation: Le Tribromure De Tetrabutylammonium
Authors: Fournier M. , Fournier F. , Berthelot J.
Published: September 2010

Tetrabutylammonium tribromide (TBA Br3) is used under mild conditions as bromating agent for the addition on double bonds of alkenes and for selective α‐substitution of acetals in high yields.
NMR Studies on Imidines. IV.H and 13C Nuclear Magnetic Resonance Study of Tautomerism in 2‐Aminopyrrolin‐5‐One
Authors: Spiessens Luc I. , Anteunis Marc J. O.
Published: September 2010

2‐Aminopyrrolin‐5‐one (2) is shown to be present in solution as the amino tautomer 2a by 13C NMR chemical shift comparison with model compounds: 2‐(dimethylamino) pyrrolin‐5‐one (5), 2,3,4‐trihydropyrrolidino [1,2‐a] pyrimidin‐6‐one (6) and (E)‐1‐methyl‐5‐methylimino‐2‐pyrrolidinone (7). Their syntheses are described and extensive 1H and 13C NMR data are given. The monomethyl derivative of 2, 2‐(methylamino) pyrrolidin‐5‐one (8), is similarly shown to be an amino tautomer and is present in solution as a mixture of Z and E isomers with respect to the hindered rotation around the exocyclic C‐N bond. It is suggested that succinimidine is best represented by the 2‐amino‐5‐iminopyrroline structure (1a).
NMR Studies on Imidines. V. 1H and 13C Nuclear Magnetic Resonance Study of the Tautomerism and Geometrical Isomerism of 1,3‐Bis(Arylimino)Isoindolines
Authors: Spiessens Luc I. , Anteunis Marc J. O.
Published: September 2010

Detailed 1H and 13C NMR data are given for a series of 1,3‐bis(arylimino) isoindolines [aryl = phenyl (2), p‐tolyl (3), p‐methoxyphenyl (4) and 2‐pyridyl (5)] and for two N‐methyl derivatives: 1,3‐bis(phenylimino)‐2‐methylisoindoline (6) and 3‐N,N‐methyl, p‐tolyamino‐1‐(p‐tolylimino)‐1H‐isoindole (7). The diimino form is shown to be the predominant tautomer in compounds 2 – 5 by 13C chemical shift comparison with model compounds 6 and 7. Geometrical isomerism about the exocyclic C=N (C‐N) bonds is discussed. The imino model 6 adopts the EE configuration exclusively. The amino model 7 is present in a 90:10 ZE:EE ratio with respect to the p‐tolylimino substituent at C‐1. Compounds 2 – 4 show a mixture of ZZ and ZE isomers in a ratio of about 70:30. The bis‐pyridyl derivative 5 is present exclusively as the ZZ geometrical isomer due to an intramolecular hydrogen bond bridging mechanism.
New Trinervitane Diterpenes from NEO ‐ GuineanNasutitermessp.(1)
Authors: Braekman J. C. , Daloze D. , Dupont A. , Pasteels J. M. , Ottinger R.
Published: September 2010

Four new 1 (15),8 (19)‐trinervitadiene derivatives have been isolated from nasute termite soldiers from Papua‐New Guinea and their structures determined on the basis of their spectral properties. They have been identified as 9β‐acetoxy‐2β,3α‐dihydroxy‐1 (15),8 (19)‐trinervitadiene (1), 2β,3α,9α, 13β‐tetraacetoxy‐1 (15),8 (19)‐trinervitadiene (2) and 2β,3α,9α,13β‐tetraacetoxy‐1 (15),8 (19)‐trinervitadienes (3 and 4). These last two derivatives are epimeric at C‐11. The configurations at C‐9 and C‐13 of 8, a previously isolated tetraacetate, are also assigned.
Structure du chlorotris (1,4,7‐trimethylindenyl) uranium
Authors: Meunier‐Piret J. , van Meerssche M.
Published: September 2010

The crystal structure of Chlorotris (1,4,7‐trimethylindenyl) uranium was determined from three‐dimensional X‐ray data. [U(C12H13)3Cl] crystallizes in space groupP21/c witha= 9.763(4),b= 16.480(11), c = 18.763(10)Å, β = 101.07(4)° andDx= 1.670 Mg cm−1forZ= 4. The structure was solved by the heavy‐atom method. The U‐atom is π‐bonded to C5‐ring of the indenyl ligand and has a distorted tetrahedral environment. The structures of [U(C12H13)3Cl] and [Th(C12H13)3Cl] are isomorphous.
Synthesis of Some Low Molecular Weight Derivatives of Procainamide
Authors: Ruys Luc , Schacht Etienne
Published: September 2010

Low molecular weight derivatives of procainamide, with a terminal functional group have been prepared. The synthesis and characterization of the succinic half‐amide respectively of N‐(ω‐amino alkanoyl)derivatives of the parent drug are reported.
Novel Synthetic Approaches to Monocyclic β‐Lactam Antibiotics
Authors: Hanessian Stephen , Sahoo Soumya P. , Couture Claude , Wyss Heinz
Published: September 2010

Access to optically active 3‐ and 3,4‐substituted azetidinones and to β‐substituted amino acids is reported with applications in the area of monobactam antibiotics.
Catalytic Functionalities of Supported Sulfides III. Correlation of activities at Elevated Pressure with Oxygen Chemisorption
Authors: Liu Y. , Massoth F. E. , Shabtai Joseph
Published: September 2010

A number of different supported CoMo catalysts, that had been characterized by O2chemisorption measurements, were evaluated for hydrodesulfurization of dibenzothiophene, hydrogenation of naphthalene, and C‐N‐bond hydrogenolysis of indole at elevated pressure. Only rough correlations between the different catalyst functionalities, and between the functionalities and O2chemisorption, were obtained. It is concluded that different active sites are involved for the different reactions, and that O2chemisorption is generally related to the dispersion of the active MoS2phase rather than to any specific reaction site.
Fast and Slow Steps of Hydrodesulfurization
Authors: Schulz Hans , Do Dac‐Vong
Published: September 2010

Two model mixtures (2‐methylthiophene, phenol, o‐toluidine, ethylbenzene and benzothiophene, o‐cresol, aniline, o‐xylene) were used to characterize activity and selectivity of different sulfur resistant catalysts for simultaneous HDS, HDO, HDN and hydrogenation of aromatics. 2‐methyltetrahydrothiophene and dihydrobenzothiophene were found as intermediates. A mechanism for the HDS‐reaction is discussed and compared to the HDN mechanism of quinoline.
Carbon‐Supported Iron Sulfide Catalysts
Authors: Groot C. K. , van Der Kraan A. M. , De Beer V. H. J. , Prins R.
Published: September 2010

Carbon‐supported iron sulfide catalysts were characterized by means of thiophene hydrodesulfurization and butene hydrogenation activity measurements in a flow micro reactor, operating at atmospheric pressure. The iron content was varied from 0.03–1.9 Fe atoms per nm2 support surface area (0.3–17.7 wt% Fe). Oxidic catalyst precursor systems were dried either at 293K, or at 293K and subsequently at 383K.

Dispersion of the oxidic iron phase present in the dried catalyst precursors and in the reoxidized sulfided catalysts was determined by Mössbauer spectroscopy, while X‐ray photoelectron spectroscopy was used for characterization of oxidic and sulfided catalysts.

Carbon‐supported iron sulfide catalysts had a much higher HDS activity than alumina‐supported ones. They were also more active and less sensitive to deactivation than carbon‐supported molybdenum sulfide catalysts, which were the better hydrogenation catalysts.

Drying of oxidic iron catalyst precursors at 383K caused a significant sintering and a lower catalytic activity. Sintering was also observed to occur during catalyst presulfiding. The extent of sintering appeared to increase with surface loading. The oxidic iron phase of the freshly prepared catalyst precursors dried at 293K consisted mainly of small iron(III) oxide particles (<40 A), which were, at least at low surface loadings, inhomogeneously distributed over the support surface.

Iron(II) sulfide was found to be the main active phase. It was also noticed that considerable amounts of elemental sulfur are formed during sulfiding.
Characterization of Sulfided Ni‐Mo/γ‐Al2O3 Catalysts by O2 and NO Chemisorption. Influence of the Method of Preparation
Authors: Agudo A. LÓPez , Gil Llambías F. J. , Tascón J. M. D. , Fierro J. L. G.
Published: September 2010

Two Ni‐Mo/γ‐Al2O3 catalyst series prepared by sequential or simultaneous impregnation with a Mo content of ca. 8 wt% MoO3 and NiO content ranging between 0 and 8.9 wt% were studied in their sulfided state. Quantitative determination of irreversible chemisorption of NO at room temperature and of O2 at ‐78°C indicated that NO uptake was much higher than that of O2 for both catalyst series. Besides, NO uptake increased with promoter content until Ni/Mo ca. 0.8 and then leveled off, whereas O2 uptake steadily increased with increasing Ni/Mo ratios. Absorbance of IR band of NO chemisorbed on Ni atoms at 1840–1845 cm−1 were always higher for the sequentially impregnated catalysts. The absorbance of NO in both series vs. Ni/Mo ratio followed volcano‐type curves, such as those found for hydrodesulfurization (HDS) activity. A possible correlation between HDS activity and both, NO‐ and O2‐ uptake and NO absorbance on Ni atoms is attempted.
A Geometrical Model of Hydrotreating Catalysts ‐ Prediction of Catalytic Activity Variations with Composition
Authors: Kasztelan S. , Toulhoat H. , Grimblot J. , Bonnelle J. P.
Published: September 2010

A geometrical model of the active phase of hydrotreating catalysts is proposed. The existence of MoS2 patches on a carrier and the reactivity of the edge sites of these patches are the two experimental observations used for the development of this model. The promotor effect is taken into account by an edge decoration of the patches. A partial loss of promotor ions into the Al2O3 carrier and formation of a promotor bulk sulphide are also considered. The specific activity for a given reaction, the amount of chemisorbed oxygen and promotor effect are predicted and can be compared to experimental results previously published in the literature by different authors. The good fitting obtained put in evidence that both HDS, hydrogenation and O2 chemisorption Involve the edge sites (unpromoted or promoted) of the patches. The model has a general character and may apply to MoS2 or WS2, promoted or unpromoted, supported and unsupported hydrotreating catalysts.
Carbon ‐ Supported Transition Metal Sulfides
Authors: Vissers J. P. R. , Groot C. K. , van Oers E. M. , Beer De , Prins R.
Published: September 2010

First, second and third row transition metal sulfides ranging from group VI to group VIII c, supported on activated carbon were evaluated for their ability to catalyze the hydrodesulfurization of thiophene at atmospheric pressure. X‐ray photoelectron spectroscopy was used to measure the chemical state and to obtain an indication of the dispersion of the supported sulfide particles. Second and third row elements display volcano curves with catalytic activity varying over more than an order of magnitude and maxima occuring at Rh in the second and Ir in the third row. First row elements show a twin‐shaped pattern with maximum activity located at Cr and Co. The resemblance of these experimental activity trends with those previously reported for unsupported transition metal sulfides demonstrate the advantage of carbon supports in studies on the intrinsic catalytic properties of small sulfide particles. A correlation between the catalytic activity of second and third row elements and the shift in XPS binding energies between metal and metal sulfide phases was found. Superior catalysts have low binding energy shifts and preserve a high degree of metal character under sulfiding conditions.
Quantum Chemical Studies of the Adsorption of Thiophene on MOS2 Hydroprocessing Sites
Authors: Joffre J. , Lerner D. A. , Geneste P.
Published: September 2010

The modelisation of an HDS site from the MoS2 structure is undertaken in order to understand the desulfurisation of thiophene. Depending on the number of coordinative unsaturation degrees (one, two and three anionic vacancies) and on their stoechiometry (Mo3S13H12”, MOS5H5”, MOS5H4”, MOS4H4 and MOS3H3+) these models may represent sites on basal planes, edges, or corners of the MOS2 crystal.

Different types of adsorption (vertical, horizontal, on S, on the hetero‐cycle and on one pi bond) of the thiophene molecule on the different model sites are computed using the EHT quantum chemical method. The comparison of the adsorption energy curves obtained by approaching thiophene near the site shows that the vertical one point adsorption of the S atom of thiophene is prefered over any. This adsorption step can be readily followed by a desulfurization process supposing C4H4 radical is an intermediate. These theoretical predictions agree with different conclusions of the literature. The MOS4H4 model seems to be the best choice for the site.
Practical Synthesis of 2,2,5,5‐Tetrachloro‐1,6‐Hexanedioic Acid, from Trans‐1,2‐Cyclohexanediol or Cyclohexanone, Involving Oxidation of 3,3,6,6‐Tetrachloro‐1,2‐Cyclohexanedione
Authors: Buyck Laurent De , Vanslembrouck Jan , Kimpe Norbert De , Verhé Roland , Schamp Niceas
Published: September 2010

Trans‐1,2‐cyclohexanediol was quantitatively converted into 3,3,6,6‐tetrachloro‐1,2‐cyclohexanedione (2) by treatment with chlorine in dimethylformamide. The hydrate of the dione was oxidized by aqueous potassium permanganate to afford the title acid 1 in 91% overall yield. An alternative low cost preparation was elaborated, providing 2 in 61–74% yield starting from cyclohexanone in a three step procedure without isolation of intermediates. The reaction sequence involves substitution of α‐dichloro‐ and trichlorocyclohexanones by sodium acetate in acetic acid and chlorination of the resulting 2‐hydroxy‐ and 2‐acetoxy‐2‐cyclohexenones in dimethylformamide.
Conformational Analysis of Trans and CIS Isomers of N‐Trifluoroacetyl‐2‐Methoxy‐4‐t. Butylpiperidine and N‐Trifluoroacetyl‐2‐Methoxy‐4‐Methyl Piperidine
Authors: Duquet Dirk , Callens Roland E. A. , Anteunis Marc J. O. , Borremans Frans A. M.
Published: September 2010

The solution conformation of both Z and E rotamers of trans and cis isomers of N‐trifluoroacetyl‐2‐methoxy‐4‐t.butylpiperidine and N‐trifluoroacetyl‐2‐methoxy‐4‐methylpiperidine is determined from a complete analysis and assignment of proton and carbon nuclear magnetic resonance data. The trans isomers have chair conformations and a Z/E amide bond rotation barrier of ca. 76 kJ.mol−1. The cis 4‐t.butyl analogue is a flexible D2 twist with the two‐fold symmetry axis through Cα,Cδ for the Z rotamer, but rather through Cβ,Cε for the E rotamer, with a lowered interconversion barrier of ca. 63 kJ.mol−1. The cis 4‐methyl compound is a greatly distorted chair with a Z/E activation barrier of ca. 65 kJ.mol−1. These results are relevant in relation to the potential importance of twist‐boat cyclic imino acids as β‐bend inducing entities in synthetic peptides.
Transition‐Metal‐Catalysed Reactions of Diazoesters. Insertion into C‐H Bonds of Paraffins Catalysed by Bulky Rhodium(II) Carboxylates: Enhanced Attack on Primary C‐H Bonds
Authors: Demonceau A. , Noels A. F. , Hubert A. J. , Teyssié P.
Published: September 2010

Rhodium(II) carboxylates associated with bulky ligands catalyse the insertion of carbalkoxycarbenes (generated from diszoesters) into C‐H bonds of normal and branched alkanes with selectivities differing substantially from those associated with non‐bulky carboxylates.
Effets de la Substitution Captodative XXX1. Addition Des Radicaux Dérivés de Cétones, D'Aldéhydes et de Formiates À L'α‐Tert‐Butylthioacrylonitrile2
Authors: Mignani S. , Merényi R. , Janousek Z. , Viehe H. G.
Published: September 2010

Oxydation of ketones, aldehydes and formiates in the presence of radicophilic olefin α‐tert‐butylthioacrylonitrile 3 with captodative (cd) substitution does not give the usual radical decay products: The radical adducts dimerize, thus building a four carbon‐bridge between the original radicals R°.
New Insight in the Synthesis and Reactivity of Selenenic Acids
Authors: Labar Daniel , Krief Alain
Published: September 2010

o‐nitrophenyl selenic acid has been observed during the reduction of the corresponding seleninic acid with hypophosphorous acid. An acid catalysis was found essential for the addition of at least o‐nitrophenyl selenic acid to olefins.
Iminoalkylation Des Ènamines Avec Des Nitriles Via Le Sel De Nitrilium: Une Nouvelle Méthode De Synthèse D'Ènaminocétones Et De β‐Dicétones.
Authors: Baudoux Dominique , Fuks Robert
Published: September 2010

The reaction of nitrilium salts with enamines leads to a mixture of enaminimines 4 and enaminoketones 5 by an iminoalkylation reaction. Partial hydrolysis of 4 with diluted acetic acid leads to the isolation of these new enaminoketones 5 in high yields. Refluxing them in HCl 6 N give β‐diketones, well described and usually obtained by acylation of enamines with acid chlorides. The nitrilium salt being easily prepared “in situ” from the corresponding nitrile this reaction constitutes a novel way to enaminoketones 5 and β‐diketones 6. A nitrilium salt being a much stronger electrophile than an acid chloride, the experimental conditions are milder and do not need the presence of triethylamine. The scope and limits of this novel reaction in relation to the nature of the starting nitrile are discussed.
Synthesis, Characterisation and Anti‐Tumour Activity of Bis(Polyfluoroalkyl)Tin Dihalides
Authors: Clercq Ludo De , Willem Rudolph , Gielen Marcel , Atassi Ghanem
Published: September 2010

The synthesis and characterisation of fifteen new organotin compounds containing at least two CF3(CF2)5CH2‐CH2 groups bound to tin are described. The activity of six of these compounds towards the murine P388 lymphocytic leukaemia tumour is given.
Redox Polymerization. Kinetics of the Reaction Initiated by Dimethyl Sulphoxide Ce(IV) System In HClO4 Medium
Authors: Nageswar Rao K. , Sethuram B. , Navaneeth Rao T.
Published: September 2010

The kinetics of polymerization of acrylonitrile (AN) initiated by ceric perchlorate‐dimethyl sulphoxide (DMSO) redox system has been found to be proportional to (a) square of [AN], (b) the [DMSO] and (c) independent of [Ce(IV)]. The rate of ceric disappearance is found to be proportional to the [Ce(IV)], fractional power of [DMSO]. A kinetic scheme has been proposed whereby both the ceric ion and the radicals produced from the oxidation of DMSO by ceric ion have been shown to initiate the polymerization while the termination occurs exclusively by the interaction of chain radicals with ceric ions.