bluuebunny/crossref_metadata_2025 huggingface dataset:
N‐Acylamino acids and peptides V Improved synthesis of N‐Ferulylglycyl‐L‐Phenylalanine
Authors: van Rompaey L. , De Pooter H. , van Sumere C. F.
Published: September 2010

As a result of difficulties with the synthesis of pure O‐(m)ethoxycarbonylferulyl chloride, N‐ferulylglycyl‐L‐phenylalanine (XVI) was previously prepared by a mixed anhydride method. However, due to the fact that analogous N‐acyl‐dipeptides were easily obtained by the acid chloride method, the synthesis of XVI was reinvestigated.

After abortive tries to use the condensation of O‐p. bromophenacyl‐ferulyl chloride with N‐glycyl‐L‐phenylalanine t‐butyl ester, a method for the reproducible synthesis of pure 0‐ethoxycarbonylferulyl chloride was developed. Reaction of the latter substance with N‐glycyl‐L‐phenylalanine t‐butyl ester, followed by removal of the protecting groups from the condensation products, afforded N‐ferulylglycyl‐L‐phenylalanine in 51% yield. This last recovery compares favourably with the earlier published yield of 30%.
Studies of rhodium‐103 nuclear shielding by heteronuclear magnetic double resonance
Authors: McFarlane H. C. E. , McFarlane W. , Wood R. J.
Published: September 2010

Rhodium‐103 chemical shifts have been measured by 1H‐{103Rh} heteronuclear double resonance in a series of octahedral rhodium (III) complexes with phosphine/chalcogen ligands, including some mixed species. The shifts are significantly temperature dependent, and are also sensitive to fine details of molecular conformation and configuration.
Optically active transition metal complexes, XLIV. The nature of the chiral intermediates involved in the racemization and ligand exchange reactions of optically active manganese compounds
Authors: Brunner H. , Steger W.
Published: September 2010

The syntheses and spectra of new compounds of the type (RC5H4)Mn(NO)(COR')‐P(C6H5)3, (RC5H4)Mn(NO)(COR')CO, and (RC5H4)Mn(NO)(CO)R' with R=H, CH3; R=C6H5, CH3 are described.

The reaction of P(C6H5)3 with the σ‐methyl and σ‐phenyl complexes (RC5H4)‐Mn(NO)(CO)R' with formation of (RC5H4)Mn(NO)(COR')P(C6H5)3 is so slow that σ‐alkyl and σ‐aryl compounds cannot be the chiral intermediates involved in the racemization and ligand exchange reactions of (+)‐ and (‐)‐(RC5H4)‐Mn(NO)(COR')P(C6H5)3.
Calculs Extended Hückel sur Molécules et Réactions Organiques
Authors: Simonetta M. , Gavezzotti A.
Published: September 2010

Dans cette mémoire, les caractéristiques principales de la méthode Extended Hückel sont brièvement exposées. Des exemples d'application de cette méthode à l'étude de problèmes de structure et réactivité sont examinés et discutés.
Mass Spectrometry of o‐Ethyl‐o‐Aryl‐Phenylphosphonothioates
Authors: Steurbaut W. , Dejonckheere W. , De Kimpe N. , Schreyen L.
Published: September 2010

The mass spectra of O‐ethyl‐O‐aryl‐phenylphosphonothioates are investigated and discussed. Besides direct classical fragmentation (α‐fissions), migration of both an aryl group and a double bond occurs between sulphur and oxygen prior to fragmentation, resulting in some unexpected m/e valvues. The most abundant ion was m/e 157, which could be reasonably explained in terms of loss of a phenoxy moiety followed by ethylene expulsion.
The Dielectric Behaviour of the Propyleneglycol‐Water System from 15 to50°C
Authors: Verbeeck R. M. H. , Thun H. P. , Verbeek F.
Published: September 2010

Dielectric constants at 1.8 MHz of the propyleneglycol‐water system are determined from 15 to 50°C at 5° intervals. The dielectric behaviour of the system is discussed in terms of a deviation from a linear function of the volume fraction of the components. Comparison with the monohydric alcohols and ethyleneglycol reveals the importance of the apolar/polar group ratio in the intermolecular interactions.
Hétérocycles Organiques De L'Arsenic; VI Synthèse, Structure Et Stéréochimie D'Arsatranes Hexacoordinés
Authors: Maroni P. , Holeman M. , Wolf J. G.
Published: September 2010

From tetracoordinated “arsatranes” and orthochinons new arsenic derivatives were synthesised according a “Kukhtin‐Ramirez” reaction. PMR and X‐ray studies showed in these compounds the same N → As bond as in the starting products, thus revealing the existance of a new series of hexacoordinated “arsatranes”.
Une Synthèse Aisée De Diméthyl‐6",6" Pyrannoisoflavones Angulaires
Authors: Vilain C. , Jadot J.
Published: September 2010

3‐hydroxyisovaleraldehyde dimethyl acetal(I) is condensed in the presence of pyridine with 2,4‐dihydroxy phenyl benzyl ketones (IIa, b, c, d) to give 2,2‐dimethyl‐6‐phenylacetyl‐5‐hydroxychromenes (IIIa, b, c, d); these intermediates are directly converted into the corresponding angular 6", 6"‐dimethylpyranoisoflavones (IVa, b, c, d) by condensation with ethylorthoformate in the presence of pyridine and piperidine. Compounds IV b and IV d are respectively identical with the natural products Calopogonium Isoflavone A and B wich we have described earlier.
Intensity Study of the νOH Stretching Vibration in Some Complexes of Phenols With N, N‐Dimethyl‐2‐Amino‐3‐Dimethyl‐1‐Azirine
Authors: Vaes J. , Zeegers‐Huyskens Th.
Published: September 2010

The intensity of the νOH stretching vibration has been measured for hydrogen bonded complexes formed by phenol derivatives and N, N‐dimethyl‐2‐amino‐3‐dimethyl‐1‐azirine. In these closely related complexes, the square root of the intensity increment is linearly related with the pKa of the substituted phenol and with the complexation enthalpy.
Chemical Shifts of Aldohexopyranoses Revisited and Application to Gulosylglucose
Authors: De Bruyn André , Anteunis Marc , van Beeumen Jozef
Published: September 2010

The 1H‐nmr data of D‐gulopyranose and D‐altropyranose allowed to suggest new increment rules that can be used to predict the chemical shifts of D‐aldohexapyranoses within a range of ±0.09 ppm. The 1H‐nmr parameters of gulosylglucose are also determined. They suggest the structure of this disaccharide to be β‐D‐gulopyranosyl(1→4)‐D‐glucopyranose.
A Resonance‐Window Effect in the γOH Vibration of Some Hydrogen‐Bonded Complexes
Authors: Zeegers‐Huyskens Th.
Published: September 2010

The broad γOH bands of some substituted phenols (4‐CH3, 4‐F, 4‐Br, 4‐1) complexed with tetramethylurea are characterized by a transmission window at about 690 cm−1. This window is produced by a resonance interaction of the γOH and the ν4 vibrational levels of the same symmetry species.
Solution Conformation of the Ionophore A204A Na+‐Salt
Authors: Anteunis Marc J. O. , Verhegge Georges
Published: September 2010

Most of the parameters of the Na+‐salt of A204A could be extracted from its 300 MHz H‐nmr spectrum in CDCl3, by consecutive double irradiation and INDOR experiments. A comparison of the so‐obtained solution conformation (Figure 4) with that reported2 for the solid state disclose their striking analogy. The backbone forms a pseudocyclic structure, closed by head‐to‐tail hydrogen bond between OH‐15 and COOθ (1). The cation is fixed in the center by at least six ligands, forming an irregular octahedron. Rather OH‐3 or 0‐4 (instead of the second oxygen atom of the carboxylic function as proposed2 for the crystaline state) seems to be involved as one of the ligands. Also, the rotameric states of some side chains (methoxy groupings and ring G) behave presumably different in solution. The outside periphery of the pseudo cycle is not entirely hydrophobic and four methoxy groups, OH‐15 and at least three ether/acetal oxygen atoms point away from the central cavity into the surroundings. Most of these ambident functions are concentrate around one region, e. g. the dangling sugar‐like ring G. This is a chemically mobile entity and attached via an acetal function to the remaining architecture, the latter thus being the sole skeleton responsible for chelation.
Chemical Applications of Arc Plasma Techniques. The Thermal Decomposition of Molybdenite
Authors: De Vynck I. A.
Published: September 2010

Two different arc plasma techniques are used for the thermal dissociation at high temperatures of molybdenumdisulfide into metallic molybdenum and elemental sulfur. One plasma technique allows the generation of a plasma flame characterised by a large section, a small directed velocity and a less steep radial temperature profile as compared to a plasma jet generated by a classical plasmatorch. The other plasma technique make use of the so called transferred arc procedure.

Both methods allow the production of a high purity grade molybdenum metal but as far as the energy is concerned a combination of the two techniques in a two step procedure seems to be preferable.
Benzo‐ and Indoloquinolizines XIV The Conformational Equilibrium in the Rel‐(4bα, 8aα, 15bα)‐ 4b, 5, 6, 7, 8, 8a, 10, 11‐Octahydro‐15bH‐Isoquino [2, 1‐f] Phenanthridine Isomer
Authors: Tourwé D. , Vandersteen L. , van Binst G.
Published: September 2010

The observation of all the signals of the two conformers in the low temperature 13C NMR spectrum of the rel‐(4bα, 8aα, 15bα)‐ 4b, 5, 6, 7, 8, 8a, 10, 11‐octahydro‐15bH‐isoquino [2, 1‐f] phenanthridine isomer, allowed a reassignment of the conformational equilibrium. The two conformers have either a boat conformation of the B ring, or of the C ring.
Enethiols X. About 2‐Mercapto‐Cinnamic Acids
Authors: Jensen L. , Thomsen I. , Lawesson S.‐O.
Published: September 2010

Reaction of 5‐arylidene‐3‐methyl‐rhodanine and 4‐benzylidene‐1, 3‐oxathiolan‐ 5‐on with alcoholates yields esters of 2‐mercapto‐cinnamic acids. Reaction of 4‐benzylidene‐1, 3‐oxathiolan‐5‐on with primary amines gives 5‐benzylidene‐3‐alkyl‐4‐thiazolones except for methylamine which yields N‐methyl 2‐mercapto‐cinnamamide. Some derivatives (amides, ester, thioester) of 2‐methylthiocinnamic acid have been prepared.
Étude De La Structure Moléculaire De L'oxacilline Et De L‚Acide Penicilloique Correspondant
Authors: Blanpain P. , Laurent G. , Durant F.
Published: September 2010

The crystal structures of (5‐methyl‐3‐phenyl‐4‐isoxazolyl) penicillin monohydrate (I) and of the methyl diester of the corresponding penicilloic acid (II) were solved from X‐Ray diffraction by direct methods and refined to R = 0.043 and 0.087 respectively. Bond distances and angles of I agree with those of other penicillin derivatives. The side‐chains of molecules I and II have the same conformation.
Tri‐ and Tetrasubstituted Alkenes: Synthesis and Assignment of 3,4‐Diethylhexene‐2
Authors: De Valck Anny , Geise H. J. , Dommisse R. A. , Luyten Y.
Published: September 2010

Dehydration of 3, 4‐diethylhexanol‐3 by means of oxalic acid yields mainly a mixture of Z and E‐isomers of 3, 4‐diethylhexene‐2. After separation by preparative GLC the identification and configurational assignment was made by 13C and 1H n.m.r.
Correlation Between the Vibrational Properties and the Energy of the Hydrogen Bonds ‐ OH…N and OH…O=C Systems
Authors: Zeegers‐Huyskens Th.
Published: September 2010

The frequency shift and the intensity enhancement of the νOH stretching vibration have been compared for OH…N and for OH…O=C hydrogen bonded systems. It is suggested that the contribution of the charge transfer to the total intensity is higher for OH…N bonds but that the contribution of the induced moment to the intensity is higher for OH…O=C bonds.
New Derivatives of the Alloisohumulones
Authors: De Taeye Leo , De Keukeleire Denis , Verzele Maurice
Published: September 2010

Four new compounds, derivatives of the alloisohumulones, have been isolated and identified as: cis‐ and trans‐2‐(3‐methylbutanoyl)‐5‐(3‐methyl‐2‐butenyl)‐3, 4‐dihydroxy‐4‐(Δ2, 3‐epoxy‐4‐hydroxy‐4‐methylpentanoyl)‐2‐cyclopentenone (5 and 6, respectively); 2‐(3‐methylbutanoyl)‐5‐(3‐methyl‐2‐butenyl)‐3, 4‐dihydroxy‐4‐(3‐hydroxy‐4‐methyl‐2‐pentenoyl)‐2‐cyclopentenone (7) and 3′‐(3‐methylbutanoyl)‐5′‐(3‐methyl‐2‐butenyl)‐2′‐hydroxy‐3, 3‐dimethyl‐spiro [5.4]‐2‐oxa‐deca‐2′, 4‐diene‐4′, 5‐dione (8).
Synthesis of Benzoxazepine Derivatives III. Isoindolinones
Authors: Pecher Jacques , Waefelaer Adolphe , Poultier Paul
Published: September 2010

The condensation of 2‐aryloxyalkylamines (1) with 2‐formylbenzoic acid gives substituted aminophthalides (8) which can be isolated in some cases and which cyclize to benzo [a] 1,4‐oxazepino [5,4‐a]isoindoles (11) 2‐(3, 4‐Dimethoxyphenoxy) alkylamines and 2‐formylbenzoic acid give further a second type of cyclization.
Acetoxyéthylation Aromatique Homolytique
Authors: El Zein M. , Gardrat C. , Maillard B.
Published: September 2010

Acetoxyethyl radicals, generated by decomposition of di‐t‐butyl peroxide in the presence of 2‐methyl‐1,3‐dioxolane, react with aromatic compounds to give substitution products. From the orientation and relative reactivity data resulting from attack of acetoxyethyl radicals on several monosubstituted benzenes, it is concluded that the radical has a nucleophilic character. Partial rate factors for meta and para positions have been correlated with HAMMETT parameters to give a ρ value of + 0.24.
Regiospecificity in the diels‐alder reaction of 1,2,4‐trichloro‐3,5,5‐trimethoxycyclopentadiene.
Authors: van Bree Jan , Anteunis Marc J.O.
Published: September 2010

Some Diels‐Alder adducts of 1,2,4‐trichloro‐3,5,5‐trimethoxycyclopentadiene were prepared and their structure elaborated by chemical transformations. By this it was established that a preferred formation of the 5‐endo‐substituted adducts is found for allyl bromide and allyl acetate, while acrolein yields an excess of the 6‐endo‐isomer.
Synthese de 1‐methyl‐3‐hydroxypyrazolo [3,4‐b] pyridines.
Authors: van Haverbeke Y. , Maquestiau A. , Vanden Eynde J.‐J.
Published: September 2010

A number of 1‐R‐3‐hydroxypyrazolo [3,4‐b] pyridines are obtained by cyclocondensation of a 1‐R‐5‐aminopyrazolin‐3‐one with β‐dicarbonyl compounds.

The first step of this synthesis involves the most reactive carbonyl group exclusively and, competitively, the 4‐position and the amino function of the pyrazolone.

The orientation of the reaction is dependent on the nature of the β‐dicarbonyl precursor.
Les Nitrates Basiques Mixtes de Cuivre et de Cobalt
Authors: Glibert J. , Claes P.
Published: September 2010

The precipitate‐solution equilibrium obtained by the addition soda to 8 mixed solution of Cu(NO3)2Co(NO3)2 ( 0.165 M/1 ) leads by aging 20 or 75°C to the formation of the same solid solutions Cu4−xCOx(OH)6(NO3)2(monoclinic) (xmax.=2) for the high [Cu2+]/[Cu2+] ratios and CoI‐YCUy(OH)2 (hexagonal) (ymax.=O,2) for the low values. A zone of demixtion separates these two compounds. The distribution factor indicates a continuous preferential precipitation of copper but that one is strongly reinforced in the hydroxide phase.
Induction Asymétrique Dans L'Addition Conjuguée D'Organocuprates de Lithium a la Cyclohexenone (1)
Authors: Ghozland Freddy , Luche Jean‐Louis , Crabbé Pierre
Published: September 2010

A series of heterocuprates CH3 (RY)CuLi, prepared from mono‐ or bi‐functional chiral inductors, were reacted with cyclohexen‐2 one. Whereas no asymmetric induction was observed in the presence of chiral alcohols, enantiomeric excesses varying from −6 to +15.5% result from the use of amines or aminoalcohols.
Urey‐Bradley Force Field of CF3O−
Authors: So S. P.
Published: September 2010

The normal coordinate analysis of the trifluoromethoxide anion CF3O− in the Urey‐Bradley force field was performed using published vibrational frequencies. The analysis was carried out within Wilson's FG formalism and the force constants were evaluated by a computer program based on the least‐squares fit method. Results show that the bonding of CF3O− is similar to that of NF3O.
High‐Resolution 1H‐NMR Study of Carriomycin Free‐Acid and Its Sodium Salt
Authors: Rodios Nestor A. , Anteunis Marc J. O.
Published: September 2010

The spectroscopic data extracted from the 300 MHz 1H‐nmr of carriomycin (1) and its sodium salt (1) show that in solution both the free acid and Na+‐complex possess solute‐conformations that must be almost identical to the spatial structure previously found in the solid state of the thallium salt1. The backbone in both states, free and salt, forms a pseudocyclic structure closed by hydrogen bonding between the carboxylate fragment and OH‐13. The extra sugar‐like ring G does not participate in the ion trapping. No water molecule participates in the cyclization of carriomycin free acid nor in its salt.

The present member of the polyether antibiotics therefore is highly similar to others having a dangling sugar moiety (e.g. A204A4 and septamycin13), in contrast with lenoremycin10 where this sugar fragment does participate in complexation.
Use of shift reagent with mtpa derivatives in 19F NMR spectroscopy: III. Determination of absolute configuration and enantiomeric purity of secondary alcohols
Authors: Van Wal A. J. De , Merckx E. M. , Lemière G. L. , van Osselaer T. A. , Lepoivre J. A. , Alderweireldt F. C.
Published: September 2010

The LIS values produced by Eu(fod)3 for the CF3‐19F NMR signals of the MTPA esters of different stereoisomeric secondary alcohols have been measured. The applicability of these values for assigning the absolute configuration of the alcohols has been studied. The advantages of this method over the corresponding 1H NMR method of Yamaguchi and the limits of both have been investigated. A new model of the Eu(fod)3/MTPA ester complex is given.
Pseudoguaianolides. The total synthesis of (±)‐neoambrosin (±)‐parthenin and (±)‐hymenin
Authors: Kok Pierre , De Clercq Pierre , Vandewalle Maurits
Published: September 2010

Starting from an easily obtainable and already described intermediate 2, the total synthesis of three pseudoguaianolides is described. The transformation involves functionalization of the cyclopentane ring.
Synthesis of benzoxazepine derivatives. IV. Anthracenooxazepines
Authors: Pecher Jacques , Waefelaer Adolphe
Published: September 2010

The 3‐(3,4‐dimethoxyphenoxyalkylamino) phthalides (4) cyclize in PPA solution to demethylated and demethoxylated 2,3‐dihydro‐8‐oxo‐anthraceno [9, 9a, 1‐ef] 1,4‐oxazepines (7) as well as to 6,7,9,13b‐tetrahydro‐9‐oxo‐benzo [a] 1,4‐oxazepino [5,4‐a] isoindoles (6).
Nitration de la Vincamine et de la Vincamone ‐ Hemisynthèse de la Vincinone
Authors: Sarlet P. , Hannart J.
Published: September 2010

Nitration of vincamine (1) and vincamone (9) in acetic acid introduced only one NO2 group at the C(11) (major compound) vs C(9) (minor compound) position of the eburnane skeleton.

Starting from 11‐nitro vincamone (12), vincinone (17) was obtained by suitable transformations of the NO2 group, thus affording a chemical proof of the structure of the 11‐nitro derivatives.
Recherche Documentaires Automatiques Dans le Domaine des Prostaglandines à L'Aide du Système DARC
Authors: Berte M. , De Laet F.
Published: September 2010

The DARC system, created by professor E. DUBOIS, permits the representation of chemical structures by means of linear and biunivocal topologic descriptors (DEL). The system combines the advantages of a topologic code and those of a fragmentory one. The codification and retrieval is made directly on the basis of the structure and requires no knowledge of the system.

A pilot project has been started for novelty and inventivity search purposes; to this end a data bank of approximately 15.000 very similar structures has been utilised.
A General Method for the Interpretation of Second Order Properties in Terms of Localised Orbitals
Authors: Alsenoy Christian Van , Geerlings Paul , Figeys Hubert P.
Published: September 2010

A general method is presented for the interpretation of second order properties in terms of localised orbitals. The method leads to a set of linear equations which is to be solved but whose dimension rapidly becomes a prohibitive factor for routine work. Three approximation schemes are proposed. The first one uses the maximalisation of intraorbital electronic repulsion integrals, which is the basic idea in localisation procedures; the cither two are based on the well known NDO‐principle.
Structure de la Dichloro‐4,6 Cyano‐5 N‐Méthyl N‐β‐Chloroéthyl Amino‐2 Pyrimidine
Authors: Tinant B. , Germain G. , Declercq J. P. , van Meerssche M.
Published: September 2010

The structure of the title compound has been investigated using X‐ray diffractometer intensities. Crystal data are as follow: triclinic, P1; a = 12.019(4), b = 9.353(4), c = 5.062(1)Å, α = 94.31(2), β = 87.92(2), γ = 99.64(3)°; Z = 2; Dx = 1.57 Mg m−3.
Heterocycles from Acyl Isothiocyanates and Alkyl Azides
Authors: L'abbé Gerrit , Komatsu Mitsuo , Martens Catherina , Toppet Suzanne , Declercq Jean‐Paul , Germain Gabriel , Meerssche Maurice Van
Published: September 2010

Alkyl azides react with aroyl isothiocyanates at ca 50° to yield 1,2,4‐dithiazolidines (2) and 1,2,4‐thiadiazoles (4). The latter were isolated as the major products in all cases except that of p‐nitrobenzoyl isothiocyanate. Their structure attribution was based on elemental and spectral analyses, and, in the case of 4d, on an X‐ray diffraction study. Compound 4d exhibits a nearly linear NS…O arrangement with a S…O distance of 2.52 Å, indicating no‐bond resonance.
Synthèse de Thienylthieno [2,3‐b] Thiophènes, Bithieno [2,3‐b] Thiophènes et des Sulfures Correspondants
Authors: Meunier P.
Published: September 2010

Most of the compounds containing a thieno[2, 3‐b] thiophen ring connected directly or through a sulfur atom to a thiophen ring, or even to a second thieno [2, 3‐b] thiophen ring, are accessible from a thieno [2, 3‐b] thienyllithium. Derivatives which carry a halogen atom on each cycle in the “ortho” position to the junction can be prepared from a halogenothieno [2, 3‐b] thienyllithium, or by halogenation of the heterocycles. The structure of the compounds was established by NMR analysis.
A New Synthesis of (S) ‐ ( + ) ‐1,5‐Cyclotrimethylene‐3‐Phenyl‐2‐Thiohydantoin
Authors: Poupaert Jacques H. , Lhoëst Georges
Published: September 2010

(S)‐(‐)‐1,5‐Cyclotrimethylene‐3‐phenyl‐2‐thiohydantoin is synthesized by thermal cyclodehydration of corresponding phenylthiohydantoic acid. This method yields nearly quantitatively a product of molecular rotation higher than that obtained by acid catalysed cyclisation of the phenylthiohydantoic acid. Spectral data (mainly MS and IR) supporting the structure assignment are presented and the synthetic scope of the method is discussed.
Influence of the dispersion of platinum and effect of poisons on its activity and selectivity for various test reactions
Authors: Barbier J. , Morales A. , Marecot P. , Maurel R.
Published: September 2010

A series of Pt/Al2O3, catalysts was prepared, the metal dispersion ranging from 5 to 80% as the metal loading varies. Their activities in respect to the hydrogenation of benzene (I) epimerisation of cis 1‐2 dimethyl cyclohexane (II), hydrogenolysis of cyclopentane (III), exchange of benzene (IV), monoexchange of cyclopentane (V) and multiple exchange of cyclopentane yielding d product (VI) were measured.

It is shown that reactions (I) and (II) are structure insensitive. On the other hand, reactions (III), (IV), (V) and (VI) are structure sensitive but reactions (III) and (VI) point out the same sensitivity to the structure when the sensitivities of reactions (IV) and (V) are exactly the same.

The effect of adsorption of different compounds has been studied. It was found that many of those poisons are “non selective” i.e. they affect all reactions in the same ratios. In the other hand “selective” poisons display different toxicities for reactions which point out different structure sensitivity.

Some possible explanations are discussed but finally the surface presumably displays a variety of catalytic sites and the selective poisoning may be a consequence of non uniform adsorption of the poisons.
Force field study op some hexahalide ions
Authors: Namasivayam R. , Kannan K.
Published: September 2010

The force field study of some hexahalide ions (Mm6−n) is attempted by the method of Redington and Aljibury. The angle parameter has been fixed for all the ions to obtain the symmetrised force constants. Mean amplitudes of vibration and Coriolis coupling constants have also been evaluated. The results are discussed in detail.
Complexes of lanthanide nitrates with 2‐n‐acetylaminopyrimidine
Authors: Rajasekar N. , Soundararajan S.
Published: September 2010

New complexes of lanthanide nitrates with 2‐N‐acetylaminopyrimidine (ApymH) of the composition Ln(ApymH)2 (NO3)3 where Ln = La‐Yb and Y have been synthesised and characterised by conductance, infrared, 13C and 1H NMR (for La3+ and Y3+ complexes only) and electronic spectra. The molar conductance and infrared spectral data show that all nitrate groups are coordinated to the metals. IR and NMR evidence point to the bidentate chelation of the ligand through the pyrimidine nitrogen and oxygen of the acetylamino group. A probable coordination number of ten has been assigned for all the complexes.
The conformation of 1‐formyl‐ and 1‐acetylhexahelicene
Authors: Lindner Hans Jörg , Kitschke Brigitte
Published: September 2010

The structures of 1‐formylhexahelicene (1) and 1‐acetylhexahelicene (2) were determined by X‐ray structure analyses. In the crystalline state, both compounds have conformations with the smaller group of the substituents (H in 1, 0 in 2) directed to the centre of the helicene system. πhyphen;SCF‐ force field calculations predict that these conformations are the most stable ones of the isolated molecule as well.
Propellanes. LIV. Reactions of [4.4.1], [4.3.1] and [4.2.1] Propella‐2,4‐Dienes with 4‐Substituted‐1,2,4‐Triazoline‐3, 5‐Diones
Authors: Ashkenazi P. , Kaftory M. , Ginsburg D. , Grimme W. , Heger K. , Vogel E.
Published: September 2010

As expected, the title dienophile always undergoes Diels‐Alder reactions with the title dienes by attacking anti‐ to the cyclopropane ring.
The polarized luminescence and vibrational optical activity of calycanthine
Authors: Barnett Christopher J. , Drake Alexander F. , Mason Stephen F.
Published: September 2010

Measurements of the circular intensity differential in the fluorescence of calycanthine, and of the linearly‐polarized excitation and emission spectrum, are found to support the exciton analysis of the electronic CD spectrum, upon which the determination of the absolute stereochemical configuration of the molecule is based. The observed vibrational IRCD of the N‐H stretching mode of calycanthine is shown to originate principally from chromophore‐substituent coupling, and not from the degenerate interchromophore coupling particular to chiral dimers. The general chromophore‐substituent coupling mechanism provides a procedure for the determination of absolute configuration from the IRCD associated with a localised characteristic vibrational mode.
Addition of dihalocarbenes to quadricyclane
Authors: Jefford Charles W. , Gehret Jean‐Claude E. , de los Heros Viktor
Published: September 2010

Quadricyclane (1) was allowed to react with dichloro and difluorocarbene. Cheletropic reaction occurred in both cases affording cyclopropane and cyclobutane adducts. Dichlorocarbene, being more electrophilic, underwent predominantly 1,2 cheletropic reaction with 1 yielding the cyclobutane adduct. Difluorocarbene gave mostly the exo cyclopropane adduct via 1,4 cheletropic reaction. The results are discussed in terms of the frontier orbitals and compared to the results obtained with norbornadiene.
Cristallisation Hydrothermale de Gels Alumino‐Silicates et Magnesio‐Silicates en Présence D'Hydroxyde De Calcium
Authors: De Vynck Ivan A.
Published: September 2010

The hydrothermal transformations of different compositions belonging to the systems CaO‐Al2O3‐SiO2, X2O‐CaO‐AL2O3‐SiO2 (X = alcali), CaO‐MgO‐SiO2 and CaO‐MgO‐Al2O3‐SiO2 are studied in the temperature range 300 to 650°C.

The treatment of some mixtures containing CaO, Al2O3 and SiO2 some times gives pure phases such as margarite, hibschite and anorthite. More currently a mixture of different compounds is obtained, especially at the lower temperatures examinated. Although calcium hydroxide enhances the reactivity of the silicate phase, this action is not as pronounced as for alcali metal hydroxides. In order to obtain well crystallized products the temperature of the treatment must exceed 450 °C.

Calcium hydroxide also exhibits a positive action on the crystallization of chrysotile and talc from MgO‐SiO2 mixtures. Diopsite can be obtained as a pure and well crystallized phase at temperatures equal or exceeding 500°C.
The Ce(III), Th(IV), U(VI), La(III) and Y(III) chelates with arylidene salicylichydrazide. The micro‐analytical determination of these metals
Authors: Temerk Y. M. , Ahmed Z. A.
Published: September 2010

The complexes formed between arylidene salicylichydrazide and Ce(III), Th(IV), U(VI), La(III) and Y(III) have been investigated using spectrophotometric and conductometric method. The study revealed the formation of complexes having the metal: ligand ratios 1:1 and 1:2. The values of log β for the different complexes are determined. The mode of bonding of the ligands in the solid chelates were studied by IR spectrophotometry which showed that chelate formation takes place through the CO and CH groups. The high stability constants and absorptivity coefficients of metal complexes indicate that micro amounts of the metal ions investigated can be determined spectrophotometrically with fair accuracy.
Facile synthesis of dihydrobenzo[a]xanthone derivatives
Authors: Verhé R. , De Buyck L. , De Kirape N. , De Wispelaere W. , Schamp N.
Published: September 2010

A series of dihydrobenzo [a] xanthone derivatives has been prepared by thermal condensation of 2‐ethoxycarbonyl‐3,4‐dihydro‐[1H]‐naphtalene‐1‐one and 1‐ethoxycarbonyl‐3, 4‐dihydro‐[2H]‐naphtalene‐2‐one with phenolic substrates.
Structure de l'acide N‐Acetyl‐L‐Thiazolidinecarboxylique‐4 C6H9NO3S
Authors: Tinant B. , Declercq J. P.
Published: September 2010

Fran X‐ray analysis, conformation and molecular structure of N‐acetyl‐L‐thiazolidine‐4 ‐carboxylic acid has been determined. The conformation of the thiazolidine ring is that of an envelope β−. Crystal data are as follow: monoclinic, P21; a = 6.402(5), b = 10.382(7), c = 6.234 (5)Å, β = 105.56(7)°, V = 399.2 Å3, Z = 2, Dx = 1.46 Mg m−3.
Hydroxamic Acids in Gravimetric Analysis
Authors: Agrawal Y. K. , Roshania R. D.
Published: September 2010

The analytical potentialities of hydroxamic acids as reagents for gravimetric determination of aluminium, antimony, barium, beryllium, bismuth, cadmium, cerium, cobalt, copper, dysprosium, erbium, gadolinium, gallium, indium, iron, lanthanum, magnesium, mercury, molybdenum, neodymium, nickel, niobium, praseodymium, samarium, scandium, tantalum, thorium, tin, titanium, tungsten, terbium, uranium, vanadium, yttrium, zinc and zirconium are reviewed.
The thermal decomposition of cu(II) complex of 3,5‐dinitrosalicylic acid
Authors: Heda B. D. , Khadikar P. V.
Published: September 2010

The thermal decomposition of Cu(II) complex of 3,5‐dinitrosalicylic acid is studied by the TG, DTG, and DTA. The complex decomposes in the temperature range 100‐560°C with explosion at 280°C giving a low CuO content.
Use Of Calculated Carbon Chemical Shift Tables Of Saturated C‐7 To C‐Ll Sterol Side Chains For Structure Elucidation
Authors: Kelecom A.
Published: September 2010

The 13C NMR chemical shifts of C‐7 to C‐11 saturated sterol side chains have been calculated both by the LINDEMAN & ADAMS and by the GRANT & PAUL equations. The results have been compared with published data. Attributions of the literature have been revised. Calculated data presented allow convenient characterization of C‐7 to C‐ll saturated sterol side chains.
Charge Transfer Complexes of Crown Ethers with 2, 3, 5, 6 ‐ Tetracyano Pyrazine
Authors: Malini R. , Krishnan V.
Published: September 2010

The interaction of five crown ethers, 15‐crown‐5, 18‐crown‐6, benzo‐15‐crown‐5, dibenzo‐l8‐crown‐6, and dibenzo‐24‐crown‐8 with 2, 3, 5, 6 ‐ tetracyano pyrazine has been studied by spectroscopic methods. The association constants and thermodynamic parameters of the 1:1 complexes formed by donor ethers with the acceptor have been evaluated. There is an indication that oxygens of the ethers and aryl part of the ether act cooperatively in binding of the acceptor.
Structure de deux dérivés hydantoïniques de la proline: La l‐proline hydantoïne C6H8N2O2 et la d‐allohydroxyproline hydantoïne C6H8N2O3
Authors: Arte E. , Tinant B. , Decleroq J. P. , Germain G. , van Meerssche M.
Published: September 2010

The structure of L‐proline hydantoin(I) and D‐allohydroxyproline hydantoin(II) have been investigated using X‐ray diffractometer intensities. The conformation of proline ring is β+ for (I) and γ+ for (II). The deviations from planearity in the two hydantoins rings are not negligeable.

Crystal data are as follow (I) orthorhombic, P212121; a = 11.379(5), b = 8.009(3), c = 7.131(3) Å; V = 649.9 Å3; Z = 4; Dx = 1.43 Mg m–3.
Enzymatic “In Vitro” Reduction of Ketones VII.(1) Reduction rates and stereochemistry of the HLAD catalyzed reduction of 2‐alkyl cyclohexanones, dimethyl cyclohexanones, cycloalkanones and bicycloalkanones
Authors: van Osselaer T. A. , Lemière G. L. , Lepoivre J. A. , Alderweireldt F. C.
Published: September 2010

Values for the rate constants of the catalytic step HLAD‐NADH + ketone → HLAD‐NAD+ alcohol in the HLAD catalyzed reduction of some 2‐alkyl cyclohexanones, geminal dimethyl cyclohexanones, cycloalkanones and bicyclic ketones are presented. Also the thermodynamic parameters of activation are given and they are compared with the activation parameters of the NaBH4 reduction leading to a better understanding of some forces at work in enzymatic catalysis. The results are rationalized in the same way as was previously done for the 3‐alkyl and 4‐alkyl cyclohexanones. A reaction model is obtained in which steric hindrances and hydrophobic zones are responsible for rate decreasing, respectively increasing interactions between enzyme and substrates.
The breaking of molecular point group symmetry
Authors: Bunker P. R.
Published: September 2010

In this review paper the definition of the elements of the molecular point group are carefully considered. It is shown that certain terms in the molecular Hamiltonian are not invariant to these operations and, hence, these terms can break the point group symmetry. The symmetry labelling of the energy levels of H2, H2O and CH4 are studied in detail in order to demonstrate this point. It is shown that the rotational energy levels of molecules can be satisfactorily labelled using the Complete Nuclear Permutation Inversion Group or the Molecular Symmetry Group as appropriate.
Specific interactions between pyridines and tetrachloromethane or benzene
Authors: Huyskens P. , Mahillon PH.
Published: September 2010

The integral enthalpies of solution ΔHsol of pyridines were determined at a mole fraction xB of 0.03 in cyclohexane, tetrachloromethane and benzene. The dipole moments of these bases were also determined. The differences ΔHsol (C6H12) ‐ ΔHsol (CCl4) and ΔHsol (C6H12) ‐ ΔHsol (C6H6) increase with the pKa of the pyridines in water. This is also the case for the difference μB (CCl4) ‐ μB (C6H12). However there is no marked difference between the moments in C6H6 and C6H12. These results confirm the theory of Dumas and Gomel concerning the acceptor character of CCl4. They show further that, near (δ, σ) interactions between the π‐electrons of pyridine and CCl4, interactions of the n‐σ type involving the n‐electrons of the pyridine nitrogen atom play also an important role. However the intervention of n‐electrons in the specific interactions between pyridine and benzene remains negligible, these interactions being chiefly of the π‐π type.
Structure de deux dérivés hydantoïnes: La L‐hydantoïno [c] perhydrothiazine‐1, 4 C6H8N2O2S et la L‐N‐méthylhydantoino [c] perhydrothiazine‐1, 4 C7H10N2O2S
Authors: Tinant Bernard , Declercq Jean‐Paul , Germain Gabriel , Meerssche Maurice Van
Published: September 2010

The structure of L‐hydantoïno [c]‐1, 4‐perhydrothiazine (I) and L‐N‐methyl‐hydantoïno [c]‐1, 4‐perhydrothiazine (II) have been investigated using X‐ray diffractometer intensities.

Crystal data are as follow (I) orthorhombic, P212121, a = 6.106 (6), b = 5.217 (4), c = 22.725 (19) Å, V = 723.9 Å3, Z = 4. (II) orthorhombic, P212121, a = 5.616 (2), b = 9.414 (2), c = 16.444 (6) Å, V = 869.4 Å3, Z = 4.
Organometallic chemistry of metal surfaces ‐ ultra high vacuum studies
Authors: Muetterties E. L. , Tsai Min‐Chi
Published: September 2010

The effect of one type of molecule on another for chemisorption states on a platinum (111) surface is described. This effect was assayed from chemical displacement and thermal desorption experiments. Molecules studied in this fashion included CH3CN, CH3NC, C5H5N, P(CH3)3, CO, PF3, C6H6, and C2H4. The chemistry of Pt(111) is generally distinct from that of Ni(111) in both a qualitative and quantitative fashion.
Electron spin resonance and kinetic studies on tin centered radicals r3sn. with bulky substituents
Authors: Lehnig M. , Buschhaus H.‐U. , Neumann W. P. , Apoussidis TH.
Published: September 2010

ESR data of stannyl radicals R3Sn. with residues R of considerable bulkiness in solution are presented. With R = neophyl (PhMe2C‐CH2), (g = 2.0150) an alternating linewidth effect indicating hindered rotation around the Sn‐C bonds is found. The radical is non‐planar by 14.0° and configurationally stable. The radicals (2, 4, 6‐alkyl3Ph) Sn., alkyl = H, Me, Et, i‐Pr show singlets (g = 2.0023 ‐ 2.0078) broadened by unresolved hyperfine interactions with ring and alkyl protons, aH ≤ 0.05 mT. They are non‐planar by 15.1 – 16.1°, (i‐Pr3Ph)3Sn. being less pyramidal than Ph3Sn because of steric repulsions between the substituents, and are in recombination‐dissociation equilibria with the corresponding distannanes. The Sn‐Sn bond energies drop from 205 kj (alkyl = Me) to 36 kJ (alkyl = i‐Pr). For (Et3Ph)3Sn., the activation energy of recombination is 38 kJ/mol.
Stabilization by hydrogen bonds of ketones in water
Authors: Huyskens P. , Nauwelaerts F.
Published: September 2010

The distribution coefficients PB of 2‐propanone, 2‐butanone, 2‐ and 3‐pentanone and 2‐ and 3‐hexanone, between cyclohexane and water were determined at 298.16 K using U. V.‐spectrometry. These coefficients are related to the molar volume VB of the pure ketones by the relation: log PB = 0.87 + 0.029 VB ‐ b, the last parameter describing the effect of the hydrogen bonds between the dissolved ketones and the water molecules of the aqueous phase. For the ketones studied here b is approximately constant and equals 3.44±0.20. The effect is of the same order of magnitude as that observed for pyridine but is smaller than that given by triethylamine, and markedly larger than that observed for N, N disubstituted anilines. From these results it can be concluded that at room temperature the great majority of the ketone molecules dissolved in water from hydrogen bonds with the surroundings, the fraction of non hydrogen bonded molecules being only 3.6×10−4. The results also suggest that only one electron pair of the carbonyl group forms hydrogen bonds with the surrounding water molecules.
Polarography of aldoximes in buffer solutions
Authors: Damle M. V. , Kaushal R. , Tiwari M. , Malshe P. T.
Published: September 2010

The polarographic reduction of both isomers of benzaldoxime and furfurald‐oxime and the syn‐oximes of vanillin, O‐vanillin, p‐dimethylaminobenzaldehyde and salicylaldehyde have been studied in various buffers. It is observed that wave heights decrease upto pH 8.0, and the half‐wave potential shifts to more negative values. The reduction of the oxime possibly proceeds via the conjugate acid of the oxime(R‐CH: N‐OH) H+ at the electrode interface. The waves dis‐appear at pH>8, owing probably to the decreasing concentrations of H+ ions with increasing pH values. The mechanism of the reduction has been discussed.
An infrared study of the dimerization of trichloro‐ and tribromoacetic acid and their complexes with benzophenone
Authors: Synhaeve K. , Thijs C. , Zeegers‐Huyskens TH.
Published: September 2010

The dimerization of trichloroacetic (TCA) and tribromoacetic (TBA) acids and their interaction with benzophenone (BZ) are studied by infrared spectrometry in the 1800–1600 cm−1 range. In carbontetrachloride, at the temperature of 30°C, the dimerization constants of TCA and TBA are 210 and 295 dm3 mol−1. The equilibrium constants for the reaction TCA + BZ → TCA. BZ and TCA. BZ + TCA → (TCA)2. BZ are 150 and 21 dm3mol−1. For the interaction between TBA and BZ, these equilibrium constants are 123 and 60 dm3 mol−1. The influence of the concentration on the carbonyl bands of the acid and of the base, indicates that in the 1:2 complex, the two acid molecules are probably hydrogen bonded.
Triterpenoides de napoleonaea vogelii
Authors: Kapundu Mpuza , Warin R. , Delaude C. , Huls R.
Published: September 2010

Perchloric hydrolysis of the seed saponin of Napoleonaea vogelii allowed the isolation of two prosapogenins. One of these was identified as napoleogenin. The structure of the second component has been established as 21β–|6 deoxy‐3, 4 diangelate‐β‐galactopyranosyl|oxy 3β, 16α, 22α, 24, 28 pentahydroxy‐olean‐12‐ene. The name “Napoleogenin B” is proposed for this new prosapogenin. On further hydrolysis this saponin yields protoaescigenin, isoaescigenin and aescigenin. The structure of napoleogenol previously obtained by hydrolysis of the saponin of Napoleonaea imperialis is revised and shown to be identical to aescigenin.
Polarographic behaviour of aldoximes in tetraalkyl halides
Authors: Damle M. V. , Tiwari M. , Malphe P. T. , Kaushal R.
Published: September 2010

The polarography of a few aromatic aldoximes has been studied in unbuffered 8% ethanolic medium using tetramethyl ammonium halides and tetraethyl ammonium iodide as supporting electrolytes (vs. S. C. E.). Some syn‐forms gave two step waves and the anti‐forms only one wave. On the basis of diffusion controlled waves of the two forms, we have concluded that the diffusion current constant “I” of the syn‐forms is 3 ± 0.3 and that of the anti‐forms 5 ± 0.5. In general if only one form of the oxime is available, one can find out its configuration by calculating the diffusion current constant.
Addition de l'acétone à des alcynes vrais fonctionnels ou non
Authors: Gardrat C. , Montaudon E. , Lalande R.
Published: September 2010

Acetonyl radicals created by action of di‐t‐butylperoxide on acetone (molar ratios acetone/acetylenic compound/DTBP = 20/1/0.2; 150°C; 3h) add to acetylenic compounds and lead to the formation of 1/1 adducts in low to moderate yields. 2/1 adducts are not observed in these experimental conditions.
Assignment of 2, 3, 4 Acetylated Glycosides by the Lanthanide Induced “Cross‐Over” Phenomenon‐a Preliminary Investigation
Authors: Poncini L.
Published: September 2010

The “cross‐over” phenomenon induced by lanthanide shift reagents is investigated as a means for accurately assigning the 2, 3 and 4 ring O‐acetyl proton signals in the nuclear magnetic resonance spectrum of acetylated carbohydrates.
Chemical Composition of Airborne Particulate Matter in Belgium as Determined by Instrumental Neutron Activation Analysis
Authors: Demuynck M. , Dams R.
Published: September 2010

During one year atmospheric aerosols have been collected daily at 14 stations in Belgium. Total suspended particulate levels, determined from all samples, indicated a high particulate pollution level for the major part of the country. Instrumental neutron activation analysis of 280 samples yielded significant concentration data for 29 elements and 10 additional components were determined in a limited number of samples only. Comparison to background levels and to concentrations in other polluted areas showed strong enrichments and an overwhelming anthropogenic contribution for most elements. On the basis of the time‐variability and the geometric distributions of the concentrations some intense sources could be localized and the elements could be divided in 5 groups with different sources, namely sea spray, coal combustion and steel production, liquid fuel combustion, siderurgical plants and non‐ferrous plants.
Secondary Ion Emission by Anionic Surfactants
Authors: Nelen A. , Tavernier S. , Saelens R. , Gijbels R.
Published: September 2010

Positive secondary ion emission from anionic surfactant films on a gold substrate was mass spectrometrically studied under O2+bombardment. Signals from organic origin appear to be very sensitive to small variations in experimental parameters. The production of secondary metal ions (Na+, Mg+, K+, Ca+) is, however, quite reproducible. Their relative intensities drop exponentially with the first ionisation potential of the corresponding elements, yielding a so‐called plasma temperature in the range of 6500 to 8000 K. This suggests that the mechanism of secondary ion emission from adsorbed surfactants is essentially the same as for entirely different matrices. SIMS easily allows the detection of 10−14 g of adsorbed anionic surfactant via the metal counter ion.
Voltammetric Behaviour of the Ti(IV)/Ti(III) Couple at Glassy Carbon in H2SO4 Solutions
Authors: Kiekens P. , Vandenbruwaene J. , Temmerman E.
Published: September 2010

The voltammetric behaviour of the Ti(IV)/Ti(III) couple has been investigated at a glassy carbon electrode in sulphuric acid solutions. Only in highly concentrated acid solutions (CH2SO4 > 5 M) a reduction wave can be obtained that is separated from the hydrogen reduction wave. The Ti(III) oxidation produces a well‐defined irreversible wave from which some kinetic parameters were evaluated. However, the logarithmic analysis plot is curved. In all cases the apparent transfer coefficient and rate constant are found to be potential dependent. The oxidation reaction is calculated to be a first‐order one.
The Automatic Kinetic Determination of Iron (III) and Vitamine C
Authors: van Den Winkel P. , Mertens J.
Published: September 2010

Prompt mixing of acetate buffered Iron(III) and ascorbic acid solutions results in the formation of a short‐lived colored [Fe3Ac6O] Asc complex showing a maximum absorbance at 550 nm. Mathematical analysis of the kinetics curves allows the elaboration of analytical procedures for the manual and automated determination of Iron(III) and vitamine C in a concentration range 0,1‐100 ppm and 1‐2000 ppm respectively.
Heteroaromatic Photosubstitutions
Authors: Párkányi Cyril
Published: September 2010

Photosubstitution reactions of π‐electron heterocycles are reviewed and discussed. The reactions are divided into four major types: a) free‐radical photosubstitutions, b) electrophilic photosubstitutions, c) nucleophilic photosubstitutions, and d) electron‐transfer assisted photoreductions and photodehalogenations. Examples are given for each of the four types. Photodehalogenations and electron‐transfer assisted photodehalogenations are then treated in detail.
Quantum Mechanical Studies of Atomic, Bond, and Molecular Polarizabilities: Application to Some Metal Hexacarbonyls of Octahedral Symmetry
Authors: Nagarajan G.
Published: September 2010

A brief survey on the vibrational and structural studies has been made for the hexacarbonyls of chromium, molybdenum, and tungsten possessing an octahedral symmetry. The delta‐function potential model is developed and shown to be valuable in evaluating important quantities through the use of the vibrational method and the delta‐function electronic wave functions. It is then applied to the calculations of atomic polarizabilities, bond polarizabilities, contribution by the nonbonding electrons, bond perpendicular components of the polarisability, and the average molecular polarisability of both diatomic and polyatomic molecules. The delta‐function strengths, the values of the parameter c, and the atomic polaricabilities of all the atoms in the hexacarbonyls of chromium, molybdenum, and tungsten were calculated. The bond polaricabilities, contribution by the nonbonding electrons, bond perpendicular components, and average molecular polarisabilities were also calculated for these molecules. The results have been briefly discussed.
Search and Complete Listing of the Valence Structures of the Closo Boron Hydrides B9H and B10H
Authors: Gielen Marcel
Published: September 2010

A systematic search has allowed to find 196 valence structures (VS) 2‐2‐for B9H and 728 for B10H instead of the 16 and 72 respectively described by Lipscomb(1).

With these numbers of valence structures, (NVS), valence structure indexes (VSI) 2‐2‐ equal to 0.1637 and 0.1789 can be calculated for B9H and B10H resp. which are different from those determined by Aihara(4) (0.0860 and 0.1161 respectively).