bluuebunny/crossref_metadata_2025 huggingface dataset:
Etude spectrographique des complexes formés par les halogénures d'aluminium et le trifluorure de bore. III – Spectre d'absorption infrarouge et pression de vapeur du composé d'addition des fluorures de bore et d'acétyle
Authors: Susz Bernard P. , Wuhrmann Jean‐Jacques
Published: December 2004

Le spectre d'absorption infrarouge du composé CH3COF, BF3, à −40° (état solide), donne les fréquences de l'ion (BF4)−. Les fréquences caractéristiques de l'ion (CH3CO)+ ont done pu être déterminées. La fréquence normale ω(CO) de CH3COF ayant disparu du spectre du fluoborate d'acétylium, les auteurs forment l'hypothèse que la fréquence nouvelle intense ω = 2299 em−1 représente cette vibration de valence dans l'ion acétylium. Ils proposent la formule de résonance
equation image
avec faible contribution de la structure non‐ionisée.
Etudes sur les matières végétales volatiles – CXLV. Sur l'iso‐α‐irone et sur les iso‐α‐irols et néo‐iso‐α‐irols
Authors: Naves Yves‐René
Published: December 2004

Theiso‐α‐irone (2,6)trans(21,22)cis‐α‐irone) was obtained by fractional distillation of the crude irone prepared by cyclisation of pseudo‐irones by means of boron trifluoride. This ketone and its ethylenic stereoisomer, theneo‐iso‐α‐irone (2,6)trans(21, 22)trans‐α‐irone were reduced to alcohols by means of lithium‐aluminium hydride without noticeable stereomutation.
Über die Alkaloide aus der Rinde von Strychnos melinoniana Baillon. 25. Mitteilung über Calebassen‐Alkaloide
Authors: Bächli E. , Vamvacas C. , Schmid H. , Karrer P.
Published: December 2004

Aus der Rinde von Strychnos melinoniana Baillon wurden ausser den von E. Schlittler & J. Hohl früher dargestellten Melinoninen A und B 12 weitere Alkaloide isoliert: Melinonine E, F, G, H, I, K, L, M, Mavacurin, Fluorocurin sowie l‐Narcotin und Thebaïn. Die beiden letzteren Pflanzenbasen stammen sehr wahrscheinlich nicht aus der Rinde, sondern sind während deren Aufarbeitung künstlich eingeschleppt worden.
Isolierung und Aufteilung der chloroformlöslichen Bestandteile der chinesischen Krötengiftdroge Ch'an Su. Über Krötengifte, 10. Mitteilung
Authors: Ruckstuhl Jean‐Pierre , Meyer Kuno
Published: December 2004

Mit Hilfe des chromatographischen Aufteilungsverfahrens an Al2O3 und durch Papierchromatographie liessen sich im Chloroformextrakt eines neuen Handelsmusters von Ch'an Su 11 Bufogenine nachweisen, wovon 10 in reiner Form präparativ herausgearbeitet werden konnten, während das elfte (Substanz B = Desacetyl‐bufotalin) nur auf indirektem Wege (durch Verseifung von Bufotalin) rein erhalten werden konnte. Die einzelnen Bufogenine waren im untersuchten Ch'an‐Su‐Muster in folgenden Mengen enthalten (bezogen auf die rohe Droge): Cinobufagin 4,2–4,5%, Resibufogenin ∥roh) 1,7–2 %, Bufalin 1,25–1,5 %, Cinobufotalin 1,0–1,2 %, Gamabufotalin 0,85 bis 1,0 %, Bufotalin 0,6–0,8 %, Telocinobufagin 0,5–0,6 %, Substanz A = Desacetyl‐cinobufagin 0,3–0,4 %, Substanz C = Hellebrigenin 0,17–0,2 %, Substanz D = Desacetyl‐cinobufotalin 0,12–0, 15 %, Substanz B = Desacetyl‐bufotalin 0,10–0,15 %.
Versuch zur Erklärung des papierchromatographischen Verhaltens von Zuckern
Authors: Jäger Herbert , Ramel A. , Scindler O.
Published: December 2004

Die Wanderungsgeschwindigkeit von Zuckern im Papierchromatogramm wird in Beziehung gebracht zu der Konstellation der Hydroxylgruppen in der pyranosiden Form.

Die Tatsache, dass Zucker im Papierchromatogramm als einheitliche Substanz wandern, obgleich sie in Lösung in verschiedenen im Gleichgewicht stehenden Formen existieren, wird theoretisch begründet.
Zur quantitativen Beschreibung des Einflusses von Substituenten auf das Absorptionsspektrum ebener Molekeln. Anwendung auf Anthrachinon
Authors: Labhart H.
Published: December 2004

Es wird gezeigt, wie man ein System von Parametern finden kann, mit dessen Hilfe es möglich ist, bei Kenntnis der Spektren einiger Derivate einer Grundsubstanz die Absorptionswellenlängen und Intensitäten anderer Derivate mit guter Genauigkeit zu extrapolieren. Bei der Anwendung auf disubstituierte Anthrachinonderivate ergab sich eine Genauigkeit zwischen experimentellem und berechnetem Wert von ± 8μ in der Wellenlänge des langwelligsten π‐Elektronenüberganges. Der Einfluss intramolekularer H‐Brücken auf die Absorption scheint gering. Die Polarisationsrichtung des behandelten Überganges liegt sehr wahrscheinlich parallel der Querachse der Anthrachinonmolekel.
Untersuchungen über den sterischen Verlauf säurekatalysierter Cyclisationen bei terpenoiden Polyenverbindungen. 3. Mitteilung. Zur Stereochemie der Bicyclofarnesylsäuren
Authors: Stadler P. A. , Eschenmoser A. , Schinz H. , Stork G.
Published: December 2004

Die Stereochemie der seinerzeit von A. Caliezi & H. Schinz sowie G. Stork & A. W. Burgstahler beschriebenen Bicyclofarnesylsäuren (Smp. bzw. 131°, 138° und 154°) wurde festgelegt. Es handelt sich in diesen Verbindungen um Derivate des trans‐Decalins.
Azeotropismus und Mischungswärme chemisch und physikalisch ähnlicher Verbindungen (Häufigkeit des Azeotropismus durch Kompensation von Beiträgen bei der Dampfdruckdifferenz und Summierung beim Energiebedarf der Vermischung)
Authors: Kuhn Werner , Kuhn H. J.
Published: December 2004

Die Siedepunktsdifferenz ΔT von Substanzen, welche einander physikalisch und chemisch ähnlich sind, wird darauf zurückgeführt, dass gewisse für die van der Waal'sche Anziehung der Molekeln wichtige Kenngrössen wie Molekelradien, Polarisierbarkeiten, Dipolmomente usw. für solche Substanzen nahezu, aber nicht ganz dieselben Werte besitzen. Die Unterschiede werden durch für die Unterschiede in den einzelnen Kenngrössen charakteristische Differenzparameter festgehalten.
Über Muscarin. 8. Mitteilung. Herstellung von racemischem Allomuscarin
Authors: Corrodi H. , Hardegger E. , Kögl F.
Published: December 2004

Die Nomenklatur für Stereoisomere des Muscarins wird festgelegt. Es werden Reaktionsbedingungen angegeben, die auf dem im Formelschema angedeuteten Weg aus einfachen Estern in guter Ausbeute zu racemischem Allomuscarin führen, obwohl als Zwischenprodukte Gemische diastereomerer Verbindungen auftreten.
Elektronenstruktur und physikalisch‐chemische Eigenschaften von Azo‐Verbindungen Teil V: Über den Einfluss von Substituenten auf das Absorptions‐Spektrum des Phenyl‐azo‐azulens, ein Beitrag zur Kenntnis der PLATTNER'schen Verschiebungsregel
Authors: Gerson F. , Heilbronner E.
Published: December 2004

It is shown that for phenyl‐azo‐azulenes substituted in the benzene nucleus

the position ṼB.Iof the band corresponding to the long‐wave transition depends linearly on the Hammett σxvalue of the substituent X

the shift ΔṼB.IIof the intense π→π* transition at 24 000 cm−1on protonation of the azo link depends linearly on σx, provided that σx‐ σ′xis negative.
Chemischer Beweis der 12β‐HO‐Gruppe in Diginatigenin
Authors: Linde Horst , Murphy James E. , Meyer Kuno
Published: December 2004

The 12β‐HO‐group in diginatigenin was unambiguously proved by chemical connexion of this aglycon with digoxigenin.
Synthese des Colchicins
Authors: Schreiber J. , Leimgruber W. , Pesaro M. , Schudel P. , Threlfall T. , Eschenmoser A.
Published: December 2004

Es wird eine von Purpurogallin, bzw. Pyrogallol ausgehende Totalsynthese des Colchicins, des Hauptalkaloids der Herbstzeitlose, beschrieben.
Etude préliminaire au dosage des éléments par activation aux neutrons, basé sur la formation d'isotopes à courte période: séparations rapides et détermination des pertes
Authors: Monnier D. , Haerdi W. , Vogel J.
Published: December 2004

The authors submit a method for the rapid separation of cobalt by toluene extraction of its β‐nitroso‐α‐naphthol complex, with estimation of the losses involved. Iron, the chief element causing disturbance in assay by gamma spectrometry (60Co) after activation, gives a complex with sodium fluoride‐acetate‐citrate in a medium at pH 5–6 and remains quantitatively in the aqueous phase. In this way it has been possible to separate 0,1 μg of cobalt in presence of 100 mg of iron. The estimation of losses is carried out by means of a radioactive tracer (58Co), isotope of the element being assayed (cobalt 60 or 60 m). The time necessary for separation and estimation is about 20 min and would thus permit a cobalt assay based on that of the cobalt 60 m (periode 10,5 min) wich is formed by activation. A chemical method for the control of losses has also been studied.
Strahlungschemie der Kohlenwasserstoffe. 2. Mitteilung. Benzol ‐ Cyclohexan
Authors: Gäumann Tino
Published: December 2004

The behaviour of benzene and its mixtures with cyclohexane and iodine under the influence of ionising radation is examined. All the more important dimers are identified and a kinetic way of their formation is proposed. This way explains also part of the polymer production. Iodine does not act as a pure radical scavenger. It is shown that energy transfer between cyclohexane and benzene is much less important than was formerly believed.
Über elektrophoretische Ionenfokussierung X. Die Analyse von Seltenen Erdgemischen
Authors: Friedli Walter , Schumacher Ernst
Published: December 2004

1) The method of Electrophoretic Focussing of Ions (EFI) (focussing ion exchange) has been applied to an analysis of rare earth mixtures. Using two systems of pH‐pL‐gradients, the groups La‐Tb and Eu‐Lu are separated in the course of 5 min. The identification, the purity control and the quantitative determination of the lines in the EFI‐spectrum are effected by radioactivation and several radiochemical measurements : radiogram, autoradiogram, isotope dilution, β‐absorption, γ‐spectrum, decay curves.
Réactivité des bromures de benzyle substitués envers le thiophénate et le méthylate de lithium
Authors: Klopman G. , Hudson R. F.
Published: December 2004

The rate of reaction of several p‐substituted benzyl bromides with lithium thiophenoxide (kphs) and lithium methoxide (KMeO) in methanol have been measured polarographically. In both series of reactions, the reactivity increases on introduction of electron releasing and electron attracting substituents. This is explained by a change in the transition state structure from an essentially ionic form, to a more covalent form stabilised by conjugation between the benzene ring and the pseudo‐π orbitals forming the reaction coordinates. The ratio kPhs/kMeo increases with the HAMMETT σ value for the substituent in the benzyl bromide, showing that the selectivity of the nucleophile increases with the extent of covalent bond formation in the transition state.
Thermodynamik der Färbevorgänge. I. Absorptionsmodelle
Authors: Milićcević B. , Kern F.
Published: December 2004

After a general introduction into the thermodynamics of dyeing, the sorption problem of dispersed dyes by hydrophobic fibers is treated by use of relations developed on the basis of different absorption models. The effects of additives (salts, organic solvents and dispersing agents) are discussed.
Stoffwechselprodukte von Actinomyceten. 32. Mitteilung. Über die Konstitution von Nonactin
Authors: Dominguez J. , Dunitz J. D. , Gerlach H. , Prelog V.
Published: December 2004

The neutral, colourless and optically inactive metabolite nonactin, C40H64O12, obtained from cultures of several Actinomyces strains, is a macrocyclic tetralactone (“macrotetrolide”) I of racemic nonactic acid, C10H18O4. The constitution II has been established for the latter by degradation. Crystallographic data for nonactin are reported.
Über die Dünnschichtchromatographie von Lipiden. 1. Mitteilung. Untersuchungen von Gehirngewebe Multiple‐Sklerose‐Kranker und Normaler
Authors: Honegger C. G.
Published: December 2004

1. Brain tissue (white and grey matter) of two multiple sclerosis patients and two normals has been extracted with 2:1 chloroform‐methanol.
Aromatische Substitution des Tyrosins bei der sauren Hydrolyse seiner Carbobenzoxyderivate
Authors: Iselin B.
Published: December 2004

The side reactions observed on acid hydrolysis (6 N HCl; 20 hrs at 115°C) of carbobenzoxy derivatives of tyrosine containing peptides were investigated by hydrolyzing carbobenzoxy‐L‐tyrosine or O‐benzyl‐L‐tyrosine under the same conditions or by reacting L‐tyrosine with benzylchloride in the presence of 6N HCl. In every instance the reaction mixture contained besides tyrosine 3 new products distinguishable by paper chromatography. The fractionation of the mixture yielded a mono‐benzylated tyrosine considered to be 3‐benzyl‐L‐tyrosine (I) and two different products which were shown to contain 2–3 benzyl residues in the aromatic ring. These results demonstrate that the benzyl cation formed in the course of the hydrolysis of carbobenzoxy derivatives of tyrosine containing peptides transforms L‐tyrosine into derivatives substituted in the aromatic nucleus.
Konstitution und Reaktionsfähigkeit von Trichlor‐pyrimidylamino‐Verbindungen
Authors: Ackermann H. , Dussy P.
Published: December 2004

2,4,5,6‐Tetrachlorpyrimidin wurde mit Ammoniak, aliphatischen und aromatischen Aminen umgesetzt und es konnte gezeigt werden, dass dabei fast ausschliesslich das Chlor in 4‐Stellung des Pyrimidinrings substituiert wird.
Reaktionen von Steroid‐Hypojoditen VI. Substitutionen tertiärer Wasserstoffatome. Über Steroide, 200. Mitteilung
Authors: Heusler K. , Kalvoda J.
Published: December 2004

The attack of an oxy radical (produced by the hypoiodite reaction) on a tertiary hydrogen atom, followed by base treatment, leads to an allylic ether: a 4α‐hydroxy‐5 βH‐steroid gives a Δ‐4α, 9α‐oxide as the main reaction product. It is postulated, that in cases where the initial 1,5‐hydrogen shift from carbon to oxygen leads to a sterically hindered carbon radical, the iodine atom does not combine with the radical. By transfer of an electron from carbon to iodine an ion pair is formed which decomposes by elimination of HI. The final allylic ether is produced by addition of a newly formed oxy radical to this double bond, followed by another oxidation and/or substitution elimination reaction.
Structure et réactions du composé d'addition: triphénylphosphine ‐ anhydride maléique
Authors: Hudson R. F. , Chopard P. A.
Published: December 2004

The structure of the adduct between maleic anhydride and triphenylphosphine has been determined by direct synthesis and spectral analysis. It is analogous to a phosphine methylene derivative (WITTIG reagent) stabilized by an u‐carbonyl group. With aldehydes, it gave none or very poor yields of the expected olefins; water (or alcohols) caused the anhydride ring to open, instead of forming triphenylphosphine oxide plus the corresponding hydrocarbon.
Pyridinderivate als Komplexbildner V. Die Metallkomplexe von 1,10‐Phenanthrolin und α, α′‐Dipyridyl
Authors: Anderegg G.
Published: December 2004

The complex formation of Mg2+, Ca2+, Pb2+, Mn2+, Fe2+, C02+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+ and Cu+ with l,l0‐Phenanthroline and K, α′‐Dipyridil have been investigated using potentiometric measurements (20°, μ = 0,l (NaNO3)). Since some of these complexes are formed in rather acid solution the usual procedure of pH titration would not be very suitable. For this season displacement reactions have been measured in many cases. The results of these measurements are in good agreement with those obtained using the pHg‐method or redox potential measurements.
Fluoreszenzmethoden zur histochemischen Sichtbarmachung von Monoaminen. 1. Identifizierung der fluoreszierenden Produkte aus Modellversuchen mit 6,7‐Dimethoxyisochinolinderivaten und Formaldehyd
Authors: Corrodi H. , Hillarp N. Å.
Published: December 2004

When primary or secondary catecholamines are treated with formaldehyde gas in a dried protein layer a strong fluorescence appears which is used for histochemical identification of these amines in central and peripheral adrenergic nerves.
Beiträge zur Chemie der Si‐N‐Bindung, XVIII [1]. Über lineare, cyclodisilazan‐modifizierte Oligosiloxane
Authors: Fink Walter
Published: December 2004

Linear oligosiloxanes with cyclodisilazane rings built into the siloxane chain were prepared by the reaction of hydroxysilyl substituted cyclodisilazanes in the form of their lithiumsilanolates with dimethyldichlorosilane, α,ω‐chlorosiloxanes or dimethylchlorosilyl substituted cyclodisilazanes.
Etudes sur les composés organométalliques. X [1]. Action d'organomagnésiens sur la benzophénone
Authors: Dubsky George Jon , Jacot‐Guillarmod André
Published: December 2004

Various Grignard reagents and their diorganomagnesium complexes with ether or pyridine have been reacted with benzophenone, using different mole ratios and orders of addition. Analysis of the reaction products has provided information as to probable reaction mechanisms of addition and reduction. A monomeric diorganomagnesium reagent, favoured either by addition of the reagent to the ketone or by complexation of the reagent with pyridine, enhances if possible the reduction reaction.
Structure of hygromycin B, an antibiotic from Streptomyces hygroscopicus; The use of CMR. spectra in structure determination, I
Authors: Neuss N. , Koch K. F. , Molloy B. B. , Day W. , Huckstep L. L. , Dorman D. E. , Roberts J. D.
Published: December 2004

Das Antibioticum Hygromycin B, eine Verbindung C20H37N3O13 aus Streptomyces hygroscopicus, wurde hydrolytisch gespalten und die Spaltprodukte charakterisiert und identifiziert. Die Kenntnis ihrer Struktur und die Interpretation von 13C‐NMR.– (CMR.)‐ Spektren führten zur Strukturaufklärung des Antibiotikums.
Vernetzung von Phenolcarbonsäureestern von Polysacchariden durch oxydative phenolische Kupplung
Authors: Geissmann T. , Neukom H.
Published: December 2004

Guaran, a watersoluble polysaccharide, was esterified with various phenolic acids. Solutions of these esters formed gels upon oxidation. In these gels the phenolic ester groups were crosslinked by oxidative phenolic coupling, the corresponding dimeric phenolic acids being liberated by saponification.
Biosynthesis of Betalaines. On the Cleavage of the Aromatic Ring during the Enzymatic Transformation of Dopa into Betalamic Acid
Authors: Fischer Nikolaus , Dreiding André S.
Published: December 2004

Bei der enzymatischen Umwandlung von 3′,4′‐Dihydroxyphenylalanin (Dopa) in Betalaminsäure, in Betalain‐haltigen Centrospermen, wird der aromatische Ring an der Bindung neben den beiden Hydroxylgruppen (C(4′)‐C(5′)) und nicht zwischen den Hydroxyl gruppen (C(3′)‐C(4′)) gespalten. Dies ergab sich aus dem Einbau von L‐Tyrosin‐[3′,5′‐3H] in Betanin mit Kaktusfruchtmiaterial. Das [3H]‐Betanin und das daraus durch Hydrolyse erhaltene Betanidin enthielten ∼90% des Tritiums am C(11), denn nach Behandlung des Betanins mit Prolin fanden sich ∼90% der Radioaktivität im Indicaxanthin und nur ∼10% im Cyclodopaderivat, und Behandlung des Betanidins mit CF3COOH bewirkte keine Radioaktivitätsverminderung durch 1H‐3H‐Austausch.
Thermochemische Untersuchungen an cyclischen Ketonen
Authors: Wolf G.
Published: December 2004

The enthalpies of formation of the nine cyclic ketones CnH2n−2O (n = 4–12) were determined by combustion calorimetry. The heats of vaporization were determined by measuring the vapor pressure as a function of temperature and the heats of fusion of the three compounds with n = 8, 9, 12 which are solids at room temperature, by DSC.
Isolierung von (2S, 4S)‐(+)‐γ‐Hydroxynorvalin und (2S, 4R)‐(−)‐γ‐Hydroxynorvalin aus Boletus satanas Lenz
Authors: Matzinger P. , Catalfomo Ph. , Eugster C. H.
Published: December 2004

We have isolated from the carpophores of Boletus satanas Lenz (Basidiomycetae) (2S,4S)‐(+)‐γ‐hydroxynorvaline (1) and (2S,4R)‐(−)‐γ‐hydroxynorvaline (2). The chirality of each diastereomer has been determined by chemical synthesis starting from optically active precursors and by application of different chiroptical methods. Gaschromatographic separation of the derived diastereomeric N‐[(S)‐α‐methoxypropionyl]‐lactones reveals that the optical purity of natural 2 is 88% whereas 1 exists as a partial racemate: (2S,4S): (2R,4R) = 3:2.

Muscarine could not be detected in the carpophores of B. satanas, contrary to some literature data but basic substances of unknown structure are present in low concentration.
Farbstoffsensibilisierte Photoreaktionen von vinylogen Epoxycarbonylverbindungen
Authors: Skorianetz Werner , Ohloff Günther
Published: December 2004

On irradiation in the presence of dye sensitizers, vinylogous epoxy carbonyl compounds undergo a novel photofragmentation reaction, to give furyl ketones in good yields. The fragmentation process is probably preceded by trans‐cis isomerization of the double bond; in one case the cis‐isomer could be isolated. In a side reaction epoxyenone 10 gives the cyclopentanone derivatives 13 and 14 by a [1, 2] shift of a methyl group.

Similar dye sensitized photolysis of the endo‐peroxide 2 also gives the corresponding furyl ketone 4, and the corresponding vinylogous epoxyketone C is probably an intermediate in this transformation.

The finding that dyes of relatively low triplet energies (∼ 30 kcal/mol) efficiently sensitize these reactions, and a certain wave length dependence suggest that the usual triplet mechanism cannot be involved.
Zur Kenntnis von Rifamycin‐S. Reaktionen des chinoiden Nucleus. Modifikationen von Antibiotica, 9. Mitteilung [1]
Authors: Kump Wilhelm , Bickel Hans
Published: December 2004

The reactivity of rifamycin‐S (1) with respect to nucleophilic reagents has been studied. Several new classes of derivatives, some of which show interesting biological activities, are described.
Organic Phosphorus Compounds. Part 64 synthesis of 4,6‐dimethylamino‐2‐cyclohexyl‐2H‐1,3,5,2‐Pv‐thiadiazaphosphorin‐2‐thione
Authors: Maier Ludwig
Published: December 2004

In the reaction of cyclohexylmonothiophosphonic anhydride, [C6H11P(S)O]3, with dimethylcyanamide not the expected 2H‐1,3,5,2‐Pv‐thiadiazaphosphorin‐2‐oxide derivative is formed, but the corresponding thione derivative, the title compound, is obtained.
Zur Kontrolle von Solid‐phase Peptidsynthesen durch Eluat‐Chloridbestimmung
Authors: Fankhauser Peter , Fries Peter , Brenner Max
Published: December 2004

The origin of chloride ion in chloroform and methylene chloride solutions of tertiary amines is studied. The applicability of such solutions in the analytical control of solid phase peptide synthesis must be seriously questioned. An alternative procedure, amenable to automation, is suggested.
Absolute Konfiguration der enantiomeren α‐CyclogeraniumsäUren, α‐Cyclogeraniale, α‐Jonone, γ‐Jonone, α‐und ϵ‐Carotine
Authors: Buchecker Richard , Egli Robert , Regel‐Wild Helen , Tscharner Christoph , Eugster Conrad Hans , Uhde Gerald , Ohloff Günther
Published: December 2004

By chemical correlation with manool and ambrein the absolute configurations of the enantiomeric α‐cyclogeranic acids, α‐cyclogeranials, α‐ionones and α‐ and ϵ‐carotenes have been elucidated.
Quinazolines et benzodiazépines‐1,4. LX Imidazo[5,1‐c]benzodiazépines‐1,4
Authors: Jaunin Roland , Arnold Wolf
Published: December 2004

Upon treatment with oxalyl chloride followed by reaction with the appropriate nucleophile, the 3‐carbamoyl‐benzodiazepines 6, 7 and 8 were converted stereospecifically to the tricyclic compounds 12, 13, 14, 16 and 19. Epimerization of 19 in presence of p‐toluenesulfonic acid led to 21. The stereochemistry of these tricyclic compounds and of some of their N(2)‐alkyl derivatives (22‐31) has been established by NMR. spectroscopy. Under proper reaction conditions, attack by bases on the tricyclic esters 13 and 26 was shown to cause an inversion of the chiral center C(11a) and to yield stereospecifically rearranged products, e.g. 23 from 26 and 33 from 13.
The Reaction of Singlet Oxygen with α‐ and β‐Pinenes
Authors: Jefford Charles W. , Boschung André F. , Moriarty Robert M. , Rimbault Christian G. , Laffer Mostyn H.
Published: December 2004

The reaction of photogenerated singlet oxygen with α‐ and β‐pinenes has been carefully re‐examined. α‐Pinene almost exclusively (99.3% yield) furnishes trans‐3‐hydroperoxy‐pin2(10)‐ene. However, detectable amounts of the three other possible products are also found, viz., cis‐3‐hydroperoxypin‐2 (10)‐ene (˜0.8%), and cis‐ and trans‐2‐hydroperoxypin‐3 (4)‐ene (˜0.04%). β‐Pinene gives 99.9% of 10‐hydroperoxypin‐2 (3)‐ene and a trace (˜0.01%) of norpinan‐2‐one. Rates of reaction and product composition are treated by modal analysis and reflect the operation of steric and stereoelectronic factors in a reactant‐like transition state.
Thermochemical Kinetics of Nitrogen Compounds. Part 4. The gas phase unimolecular thermal decomposition of triallylamine
Authors: Vitins Peter , Egger Kurt W.
Published: December 2004

The gas phase thermal decomposition of triallylamine was studied in the temperature range 531 to 620 K. The major products observed in the reaction were propylene and 3‐picoline. The first order rate constants for depletion of triallylamine, obtained using the internal standard technique, are found to be independent of pressure and conversion, and fit the Arrheniusrelationship

The reaction appears to be homogeneous, as a 15‐fold change in thc surface‐to‐volume ratio of the vessel left the rate constants unchanged. The Arrhenius parameters are consistent with a molecular elimination reaction involving a six‐center transition state, yielding propylene and N‐allyl‐prop‐2‐enaldimine. It is proposed that the latter product undergoes a 1,5‐hydrogen transfer, followed by a ring closure reaction to yield dihydropicoline, which in turn reacts forming 3‐picoline via a self‐initiated decomposition reaction.
Alkylierung der 3‐Acyl‐thio‐ und ‐dithio‐carbazinester‐Gruppierung CONHNHCSYR
Authors: Rüfenacht Kurt
Published: December 2004

3‐Benzoyl‐thiocarbazic acid O‐methyl ester 7a and 3‐benzoyl‐dithiocarbazic acid methyl ester 7b are methylated, in presence of alkali, at the SH group of 1a, the ene‐thiol tautomer of 1, to give the 3‐benzoyl‐isothiocarbazic acid O, S‐dimethyl ester 8a and the 3‐benzoyl‐isodithiocarbazic acid dimethyl ester 8b resp., which clearly differ from the N‐methylated compounds 11a and 12a or 11b and 12b prepared from the two N‐methyl benzohydrazides 9 and 10 resp. (melting points, thin‐layer chromatography and NMR. spectra).

The previously reported [1] ring closure of 3‐(ω‐chloroalkanoyl)‐thiocarbazic acid O‐alkyl esters and ‐dithiocarbazic acid alkyl esters can be interpretated as an intramolecular auto‐alkylation of CONHNHCSYR: the 3‐(chloroacetyl)‐compounds 2 are S‐alkylated (enethiol form) to the six‐membered thiadiazinones 4, but the 3‐(3‐chloropropionyl)‐compounds 3 are N‐alkylated to the pyrazolidinones 6, the five‐membered ring being preferred in the latter case to the seven‐membered ring 5 which would be formed by S‐alkylation. Hence the position of alkylating attack depends on the size of the ring to be formed.

As a consequence, starting from 3‐(4‐chlorobutyryl) compounds 13, an alternative between the two N‐alkylation products 14 (five‐membered ring) and 15 (six‐membered ring) would be expected. On the contrary however, a combination of 1,3,4‐thiadiazole ring closure and chlorine elimination predominates, giving the 5‐(3‐hydroxypropyl)‐1,3,4‐thiadiazoles 16. This reaction may proceed via the butyrolactone intermediates 18 and could therefore be interpreted as O‐alkylation followed by rearrangement.
Die Addition von Fluorcarbenen an Norbornadien: Eine Homo‐1,4‐addition
Authors: Jefford Charles W. , Kabengele Ntanda , Kovacs Josef , Burger Ulrich
Published: December 2004

It has been found that difluorocarbene undergoes extensive addition to the endo‐face of norbornadiene, yeilding the cheletropic adduct, 4.4‐difluorotetracyclo[3.3.0.02,8.03,6]‐octane. Similar behaviour has been observed for fluorochlorocarbene. Possible mechanisms to rationalize this novel behaviour of carbenes are discussed.
Haschisch‐Inhaltsstoffe. 7. Mitteilung. Synthese von (−)‐11‐Hydroxy‐Δ8‐6a, 10a‐trans‐Tetrahydrocannabinol
Authors: Petrzilka Theodor , Demuth Martin
Published: December 2004

When (−)‐Δ8‐6a, 10a‐trans‐THC (THC = Tetrahydrocannabinol), in the form of its diacetate, was irradiated in the presence of oxygen and a sensitizer, followed by reduction with NaBH4, three allylic alcohols were formed: (−)‐8α‐and (−)‐8β‐hydroxy‐Δ9,11‐THC (proportion 3:1) and (−)‐9α‐hydroxy‐Δ7,8‐THC. Acetylation of the epimeric 8‐hydroxy‐compounds with Ac2O/pyridine gave the corresponding diacetates.

When (−)‐Δ8‐6a, 10a‐trans‐THC, in the form of its tetrahydropyranyl derivative, was heated with m‐chloroperbenzoic acid, the two epimeric 8,9‐epoxides were formed in equal amounts. These compounds, on treatment with butyllithium, afforded (−)‐8α‐ and (−)‐8β‐hydroxy‐Δ9,11‐ 6a, 10a‐trans‐THC‐tetrahydropyranylether. After removing the protecting group and treatment with Ac2O/pyridine the same diacetates, as formed by photooxygenation of (−)‐Δ8‐THC‐acetate, were obtained as a 1:1‐mixture.

On heating these epimeric diacetates to 290° they underwent allylic rearrangement to (−)‐11‐acetoxy‐Δ8‐THC‐acetate. From this (−)‐11‐hydroxy‐Δ8‐6a, 10a‐trans‐THC was obtained by treatment with LiAlH4.
Stereoselective Effects in Reactions of Metal Complexes III. Asymmetric hydrogenation of 5, 7, 7, 12, 14, 14‐hexamethyl‐1, 4, 8, 11‐tetraazacyclotetradeca‐4, 11‐diene‐nickel (II)
Authors: Wermeille Maurice , Sledziewska Ewa , Bernauer Klaus
Published: December 2004

The catalytic hydrogenation in acidic solution (pH ∼ 2) of the title compound

In order to represent this and the related compounds by meaningful abbreviations, we shall adopt the numerotation system proposed in the literature [8] [12]. The complete abbreviation of the title compound is [Ni(5, 7, 7, 12, 14, 14‐Me6‐[14]‐4, 11‐diene‐1, 4, 8, 11‐N4)]2+. As in the present work the 14‐membered ring system with six methyl groups remains unchanged, we shall use [Ni(4, 11‐dieneN4)]2+ and [Ni(4, 11‐aneN4)]2+ and [Ni(4, 11‐aneN4)]2+ for the complex with the unsaturated and saturated ligand, respectively.

[Ni(4, 11‐dieneN4)]2+ (I) has been studied. The reaction yields only C‐meso‐ 5, 7, 7, 12, 14, 14‐hexa‐methyl‐1, 4, 8, 11‐tetraaza‐cyclotetradecane‐nickel (II) (C‐meso‐[Ni(4, 11‐aneN4)]2+), when meso‐[Ni(4, 11‐dieneN4)]2+ is the starting material. Rac‐[Ni(4, 11‐dieneN4)]2+ yields the unstable α‐C‐rac‐[Ni(4, 11‐aneN4)]2+. When optically active [Ni(4, 11‐dieneN4)]2+ is reduced, optically active α‐[Ni(4, 11‐aneN4)]2+ is obtained, which in neutral or basic solution shows mutarotation due to conversion into optically active β‐[Ni(4, 11‐aneN4)]2+ no racemization is observed. Reaction with cyanide ions yields the optically active free tetramine ligand.

The reaction mechanism of this asymmetric synthesis is discussed.
Edman‐Abbau als analytische methode in der ‘Solid phase’‐Peptidsynthese. Vorläufige Mitteilung
Authors: Fankhauser Peter , Fries Peter , Stahala Peter , Brenner Max
Published: December 2004

The systematic analysis of solid phase peptide synthesis by Edman degradation becomes possible by the development of a technique (high pressure liquid chromatography) for the determination of phenylthiohydantoins in trace amounts. By its qualitative beside the quantitative results the degradation method offers the possibility to follow formation and propagation of failure sequences over more than one synthetic cycle. Scope and limitations of the method are discussed.
Über Pterinchemie. 48. Mitteilung. Zur Herstellung und analytischen Charakterisierung reiner, hydrierter Pterine
Authors: Weber Rudolf , Frick Willi , Viscontini Max
Published: December 2004

Zur Abklärung von stereochemischen und rückoxydativen Problemen an vier verschiedenen methylsubstituierten 5,6,7,8‐Tetrahydropterinen wurden diese durch Umkristallisation gereinigt und die Reinheit der kristallinen Substanzen durch DC. in basischem Milieu unter Stickstoff, GC., NMR. und MS. festgestellt. Die reinen Substanzen wurden silyliert und wiesen je nach Reaktionsbedingungen verschiedene Silylierungsgrade auf. Die erhaltenen Derivate wurden durch kombinierte GC./MS. getrennt und identifiziert. Der Ort der Silylierung im hydrierten Pyrazinring wird vorwiegend von sterischen Faktoren bestimmt und erweist sich als unabhängig von der Basizität der reaktiven Zentren. Das Gemisch von vier Tetrahydro‐ und zwei Dihydropterinen konnte durch hochauflösende Glaskapillarchromatographie getrennt werden.
Formation and Properties of Losod, a New Sodium Zeolite
Authors: Sieber Werner , Meier Walter M.
Published: December 2004

Losod, a new type of crystalline hydrated sodium aluminosilicate, Na12Al12Si12O48 · q H2O, has been prepared from reaction mixtures containing bulky quaternary alkylammonium ions, particularly azonia‐spiro[4.4]nonane, besides sodium ions. Losod crystallizes from batches with a low sodium content (Na/Al ≤ 1 and Si/Al ≈︁ 1). The quaternary ammonium hydroxide primarily serves as a source of hydroxide ions and is not incorporated into the zeolite crystals. These bulky bases provide a useful means for controlling the alkalinity of the system independently of the concentration of the necessary cations built into the zeolite.

The crystals of Losod are hexagonal (a = 12.91 and c = 10.54 Å) and the proposed framework structure shows a polytypic relationship to sodalite and cancrinite. Losod has reversible sorption and ion exchange properties typical of a small‐pore zeolite and in essential agreement with the proposed structure.
Substituent Increments for the 1H‐NMR. Chemical Shifts of the 18‐ and 19‐Methyl Protons of Steroids. Part I: 9β, 10α(Retro)‐Steroids
Authors: Englert Gerhard , Arnold Wolf , Els Hans , Fürst Andor , Meier Arthur , Meister Walter
Published: December 2004

This paper reports 261 substituent increments for the 1HNMR. chemical shifts (solvent: CDCl3) of the 18‐ and 19‐methyl protons of 9β, 10α(retro)‐steroids relative to 5β,9β,10α,‐androstane. The increments were calculated by a least‐squares procedure from 1334 spectra of 759 different steroids.
Carotinoid‐Glycoside. 1. Mitteilung. Partialsynthese und Charakterisierung von Zeaxanthin Mono‐ und Diglucosid
Authors: Pfander Hanspeter , Hodler Martin
Published: December 2004

Peracetyliertes Zeaxanthin Mono‐ und Diglucosid sowie die entsprechenden freien Glucoside wurden partialsynthetisiert und mit Hilfe von UV./VIS.‐, IR.‐, Massen‐ und NMR.‐Spektren identifiziert. Mit den kristallinen freien Glucosiden wurden anschliessend Beständigkeitsversuche durchgeführt.

Die Partialsynthese erfolgte aus α‐Acetobromglucose und Zeaxanthin (3,3′‐Dihydroxy‐β,β‐carotin) nach der Methode von Koenigs & Knorr. Die freien Glucoside wurden durch Verseifen der peracetylierten Verbindungen in methanolischem Kaliumhydroxid erhalten.

Die kristallinen freien Glucoside liessen sich in Mengen von ungefähr 100 ppm (Monoglucosid) und 800 ppm (Diglucosid) in Wasser lösen. Die wässerigen Lösungen erwiesen sich als sehr beständig gegen Lichteinwirkung und Kontakt mit Luftsauerstoff. Das Diglucosid erwies sich sowohl gegenüber der sauren (pH 3) als auch gegenüber der basischen (pH 9) Hydrolyse als beständig.
Über Pterinchemie. 49. Mitteilung. Eine neue Synthese von 5‐Formyl‐6, 7‐dimethyl‐5,6,7,8‐tetrahydropterin und 5,6,7‐Trimethyl‐5,6,7,8‐tetrahydropterin
Authors: Bieri Jost H. , Viscontini Max
Published: December 2004

Starting with 5‐formyl‐6,7‐dimethyl‐5,6,7,8‐tetrahydropterine (II), a new synthesis of 5,6,7‐trimethyl‐5,6,7,8‐tetrahydropterine (III) is described. Thereby the chemical behaviour of the 5‐formyl group in II is investigated, in order to enable the unequivocal differentiation between formylation at position 5 and at position 10 in folic and tetrahydrofolic acid derivatives. 13C‐NMR. spectra of II and III are discussed.
Spezifisch π→π*‐induzierte Reaktionen von γ‐Dimethoxymethylcyclohexen‐2‐onen: 1,3‐Umlagerung und Wasserstoffabstraktion durch das α‐Kohlenstoffatom
Authors: Gloor Jean , Schaffner Kurt
Published: December 2004

When α,β‐unsaturated γ‐dimethoxymethyl cyclohexenones are excited to the S2(π,π*) state, certain unimolecular reactions can be observed to compete with S2 → S1 internal conversion. These reactions do not occur from the S1(n,π*) or the lowest T(π,π* and n,π*) states. They comprise the radical elimination of the formylacetal substituent (cf. 8, 9 → 32 + 33), γ → α formylacetal migration (cf. 6 → 27, 8 → 30, 9 → 34, 12 → 37), and a cyclization process involving the transfer of a methoxyl hydrogen to the α carbon and ring closure at the β position (cf. 6 → 28, 8 → 31, 12 → 38, 20 → 40 + 41).

The quantum yield of the ring closure 20a → 40a + 41a is 0.016 at ≤ 0.05M concentration. It is independent of the excitation wavelength within the π→π* absorption band (238–254 nm), but Φ (40a + 41a) decreases at higher concentrations. According to the experimental data the reactive species of these specifically π→π*‐induced transformations is placed energetically higher than the S1(n,π*) state, and it is either identical with the thermally equilibrated S2(n,π*) state, or reached via this latter state.

The linear dienone 14 undergoes a similar π→π*‐induced cyclization (→ 42) whereas the benzohomologue 26 proved unreactive, and the dienone 22 at both n → π and π→π* excitation only gives rise to rearrangements generally characteristic of cross‐conjugated cyclohexadienones.
Structure of a Tricyclic Photoproduct C15H24O3 by X‐Ray Analysis
Authors: Bernardinelli Gérald , Gerdil Raymond
Published: December 2004

The crystal structure of the photoproduct 1 (C15H24O3; monoclinic, a = 7.682, b = 14.448, c = 12.925 Å, β = 108.4°; space group P21/c, Z = 4) has been determined by X‐ray analysis. The structure was solved by direct methods and the positions of all hydrogen atoms were obtained from a difference synthesis. The final R factor is 0.049. The polycyclic skeleton of 1 consists of a trans‐decalone ring system axially fused to an oxolane ring in a conformation intermediate between the envelope and twist form. Strong intramolecular non‐bonded interactions are observed among the substituent atoms.
Synthesis and Structure of Tris (2′‐[2‐phenyl‐1,3‐dioxolano])‐chromium(III)
Authors: Daly John J. , Sanz Francisco , Sneeden Raymond P. A. , Zeiss Harold H.
Published: December 2004

Tris(2′‐[2‐phenyl‐1,3‐dioxolano])chromium(III) 3 has been synthesised and has been shown to have the cis (or fac) configuration 3a by X‐ray analysis: the CrC bond length is 2.037 (10) Å.
Automerisierung von 1,3,5,5‐Tetramethylcyclohexa‐1,3‐dien. Vorläufige Mitteilung
Authors: Baumann Bruno C. , Dreiding André S.
Published: December 2004

1,3,5,5‐Tetramethylcyclohexa‐1,3‐diene, specifically deuterated in all positions except the gem.‐dimethyl groups (11), was synthesized and found to undergo a rearrangement in the gas phase at 560°, which leads to a statistical distribution of the 6 hydrogen atoms to all 16 positions. This shows that the title compound (2) automerizes under these conditions and that the reaction proceeds via a series of ring openings (to 5) followed by degenerate [1,7]‐H‐shifts and rig closures (back to 2) rather than via [1,5]‐CH3‐shifts. It is suggested that the previously studied rearrangement of 5,5‐dimethylcyclohexa‐1,3‐diene (1) to 1,5‐dimethylcyclohexa‐1,3‐diene (3) takes its course by the same reaction pathway.
Vinca alkaloids XXXIV. Preparation of des‐Na‐methyl‐vindoline by microbiological conversion of vindoline, a major alkaloid from Vinca roseaL
Authors: Neuss Norbert , Fukuda D. S. , Brannon D. R. , Huckstep L. L.
Published: December 2004

The conversion of vindoline (II) using S. albogriseolus led to the isolation of several compounds including des‐Na‐methyl vindoline (III) in 8–10% yield.
Carotinoid‐Glykoside 2. Mitteilung Untersuchungen zur Carotinoid‐Zusammensetzung im Safran
Authors: Pfander Hanspeter , Wittwer Fritz
Published: December 2004

In der vorliegenden Arbeit wurde der Äthanolextrakt (70proz.) von Safran naturalis untersucht und die drei Hauptprodukte isoliert. Die kristallisierten Verbindungen wurden in natürlich vorkommender und in peracetylierter Form mit Hilfe von UV./VIS.‐, IR.‐, NMR.‐ und Massen‐Spektren charakterisiert. Der Zuckernachweis in den drei verseiften Komponenten erfolgte mittels Papier‐, Dünnschicht‐ und Gas‐Chromatographie. Bei den drei Verbindungen handelt es sich um Crocin = Crocetin‐di‐(β‐D‐gentiobiosyl)‐ester (I), Crocetin‐(β‐D‐gentiobiosyl)‐(β‐D‐glucosyl)‐ester (II) und Crocetin‐di‐(β‐D‐glucosyl)‐ester (III). Die Vergleichsspektren der partialsynthetisierten, peracetylierten Derivate Crocetin‐di‐(2,3,4,8,9,10,12‐hepta‐O‐acetyl‐β‐D‐gentiobiosyl)‐ester (IV) und Crocetin‐di‐(2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucosyl)‐ester (VI) bestätigen die Strukturen der gefundenen Verbindungen.
MO‐Calculation of the Optical Activity of Oligopeptides. II. Open‐chain conformations. Comparison with some cyclic systems
Authors: Iseli Max , Geiger Rudolf , Wagnière Georges
Published: December 2004

Using the Frozen Core (FC) MO procedure described in a previous communication, we have computed the long‐wavelength chiroptic properties of oligopeptides in the parallel‐chain (PC) pleated sheet conformation, in the poly (L‐proline) I and poly (L‐proline) II conformations. The main features of the computed results are: (a) In the PC pleated sheet conformation the π–π* transition with the highest positive rotatory strength appears at shorter wavelength than the π–π* transition with highest negative rotatory strength and is polarized mainly perpendicularly to the chain axis. There is an analogy between the computed PC pleated sheet spectrum and that calculated for a cyclohexapeptide of low symmetry, in a conformation which is probably stabilized by intra‐annular hydrogen bonds. (b) In the polyproline I conformation the computed π–π* transition with highest positive rotatory strength is also the longest‐wavelength π–π* transition and is polarized mainly along the helix axis. There is an analogy between this spectrum and that calculated for cyclo(tri‐L‐proline) of symmetry C3. (c) The poly‐proline II CD. spectrum may be qualitatively reproduced only by invoking very strong n – π interaction. The local n –π mixing parameter Λ must take on values ⪖3 eV, which is of the order of a nearest‐neighbor core resonance integral between atomic 2p orbitals of same spatial orientation. The question concerning the structural reasons for this situation is raised. As far as comparisons with experimental data are possible, qualitative agreement is obtained.
Nukleophile Alkylierung aromatischer Nitroverbindungen
Authors: Kienzle Frank
Published: December 2004

Nucleophilic alkylation of aromatic nitro compounds

Aromatic nitro compounds may be alkylated in o‐ or p‐position by treatment with alkyl lithium or alkyl Grignard reagents.
Fermentation of Fragrances: Biotransformation of β‐Ionone by Lasiodiplodia theobromae
Authors: Krasnobajew Victor , Helmlinger Daniel
Published: December 2004

Pre‐grown mycelia of Lasiodiplodia theobromae ATCC 28570 transform β‐ionone (1) into a large variety of metabolites, by mainly degrading the side‐chain of the β‐ionone molecule by a C2‐unity. The enzyme system responsible for this degradation is proposed to be an oxygenase, which gives rise to the formation of the main product β‐cyclo‐homogeraniol (8) in analogy to a Baeyer‐ Villiger oxidation. Further enzymic actions of Lasiodiplodia such as hydrogenations and hydroxylations lead to an accumulation of several not yet described β‐ionone metabolites.
Synthése totale d'α‐disaccharidyles de tridésoxy‐2,5,6‐streptamine apparentés aux aminosides à partir du maltose et du lactose
Authors: Rolland Nicole , Vass Georges , Cleophax Jeanine , Sepulchre Anne‐Marie , Gero Stephan D. , Cier André
Published: December 2004

Total synthesis of α‐disaccharidyl‐2,5,6‐trideoxy‐streptamines related to aminoglycoside antibiotics derived from maltose and lactose

The synthesis of the hitherto unknown 4‐O‐substituted α‐linked pseudo‐tri‐saccharides 1,2 and 3 is described. The key intermediates required in the reaction sequence are the glycals 12, 13 and 14, prepared from maltose, lactose and the chiral ditosyloxy‐cyclohexanol 15, readily accessible from quinic acid. The pivotal step in the reaction's scheme ‐ a stereospecific α‐glycosylution procedure ‐, is an acid‐catalyzed addition of the alcohol 15 to the glycals 12, 13 and 14 leading to the corresponding 2,3‐unsaturated trisaccharides. The latter compounds were transformed to the target α‐glycosides of 2,5,6‐trideoxystreptamine 1, 2 and 3 which were devoid of significant antibacterial activity. These results indicate that the presence of an ether linkage at the position 4′ is probably critical for antibacterial activity.
Makrocyclische Benzolactone durch Ringerweiterung von 2‐Nitrocycloalkanonen
Authors: Stach Hans , Hesse Manfred
Published: December 2004

Macrocyclic Benzolactones by Ring Enlargement of 2‐Nitrocycloalkanones

Reaction of 2‐nitroalkanones with 1,4‐benzoquinone in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐en gave (hydroxybenzo)nitrolactones of general formula 6 (Scheme 1). The transformation involves a Michael reaction, aromatization, and ring enlargement via a five‐membered intermediate. The (hydroxybenzo)nitrolactones were converted to the already known (acetoxybenzo)oxolactones 15–17. The characteristic mass spectral behavior of the ring‐enlarged products is discussed.
Analytic and preparative resolution of recemic γ‐ and δ‐lactones by chromatography on cellulose triacetate. Relationship between elution order and absolute configuration
Authors: Francotte Eric , Lohmann Dieter
Published: December 2004

Enantiomers of various chiral five‐ and six‐membered‐ring lactones, Which are important classes of compounds (flavour and Pheromone components, key intermediates in the synthesis of biologically active substances) have been separated chromatographically on the chiral phase cellulose triacetate, crystallographic form I (CTAI). For different series of five‐membered‐ring lactones, relationships have been found between the elution order of the enantiomers and their absolute configuration. Preparative resolutions of γ‐Phenyl‐γ‐butyrolactone (1) and of the Pheromone component 5b have been carried out to demonstrate the applicability of the method to g‐scale separations.