bluuebunny/crossref_metadata_2025 huggingface dataset:
Untersuchungen über das Verhalten organischer Mischphasen. 4. Mitteilung. Dampfdrücke, thermodynamische Mischungsfunktionen und Brechungsindizes der binären Systeme Tetrahydrofuran‐Diäthyläther und Methanol‐Tetrahydrofuran bei 25°
Authors: Arm H. , Bánkay D. , Schaller R. , Wälti M.
Published: December 2004

The total vapor pressure and the heats of mixing of the system tetrahydrofurane‐diethyl ether, and methanol‐tetrahydrofurane were measured at 25°C. The index of refraction was used to determine concentrations for the total pressure measurements. The partial pressures, activity coefficients, excess free energies, and entropy functions were calculated.
Recherches sur la formation et la transformation des esters LXXI Sur la préparation des acides ω‐(phénylthiocarbamylamino)‐alcoylphosphoriques et sur leur scission à divers pH
Authors: Cherbuliez Emile , Baehler Br. , Espejo O. , Frankenfeld E. , Rabinowitz J.
Published: December 2004

Sodium ω‐phenylthiocarbamylaminoalkyl phosphates C6H5NHCSNH–(CH2)n–OPO3Na2 have been obtained by reacting phenylisothiocyanate with the corresponding aminoalkyl phosphoric monoester in the presence of 2 eq. of NaOH.
Photochemische Reaktionen. 40. Mitteilung. O‐Acetyl‐6,7‐methylen‐ und O‐Acetyl‐1‐dehydro‐6,7‐methylentestosterone: Stereochemie und Resultate der UV.‐Bestrahlung
Authors: Pfister J. , Wehrli H. , Schaffner K.
Published: December 2004

The stereochemistry of the isomeric 6, 7‐methylene steroids 2 and 3 was established by reduction to the known 7‐methyl compounds 6 and 8, respectively. These results revise previous steric assignments based on n.m.r. data [4].
Die Cardenolide der Samen von Strophanthus gratus (Wall. et Hook.) Franch. 2. Mitteilung. Glykoside und Aglykone, 284. Mitteilung
Authors: Geiger U. P. , Weiss Ek. , Teichstein T.
Published: December 2004

Extracts from the seeds of Strophanthus gratus showed the presence of 30 cardenolides after being subjected mainly to techniques of preparative separation and partly through acetylation of these concentrates. These 30 cardenolides have been differentiated from one another by paper chromatography in five solvent systems. Among the identified cardenolides were most of the compounds isolated earlier by Jäger et al. [1]. In accordance with the results of these authors, ouabain (ca. 7%) was by far the predominant constituent, followed by acolongifloroside K (ca. 0.4%) and strogoside (0.4%). These three compounds have been isolated in crystalline form. Strogoside (structure elucidation see following paper) is a new name for the compound K described by JÄGER et al. Of the compounds present in trace amounts, only sarmentoside E was isolated in crystalline form directly, and the new compound λ after acetylation, which yielded O‐acetyl‐λ. The compound λ seems to be a dilactone with a structure similar to that of strogoside but containing rhamnose as the sugar and an aglycone probably different from strogogenin.
Strogosid, Strukturbestimmung. Glykoside und Aglykone, 285. Mitteilung
Authors: Geiger U. P. , Weiss Ek. , Reichstein T.
Published: December 2004

Strogoside (from Strophanthus gratus (Wall. et Hook.) FRANCH.) is shown to be the 6‐deoxy‐L‐talopyranoside of 1β, 3β, 5β, 11α, 14β‐pentahydroxy‐19‐acid‐carda‐20:22‐en‐(19→11), (23→21)‐diolide (= acolongifloroside K‐19‐acid‐(19→11)‐lactone) 12 in two ways:

3, 11‐Di‐O‐acetylouabagenin 3 was selectively oxydized in the 19‐position. The crystalline acid 5 obtained was transformed into the crystalline 1, 3, 11‐tri‐O‐acetylouabagenin‐19‐acid‐methylester 11. The latter was also obtained‐although in poor yield‐from strogoside by mild alcaline hydrolysis of the (19→11)‐lactone ring, followed by methylation, acid hydrolysis, and acetylation.

Degradation of Di‐O‐acetylstrogogenin 18 yielded the etianic ester 16, which was also obtained from the ester 11 by degradation to its etianic acid, followed by complete saponification, methylation, and acetylation.

The sugar was isolated in crystals and shown to be 6‐deoxy‐L‐talose.
Zur Kenntnis der Neutrallipide aus Säuglingshirnen
Authors: Lesch Peter , Meier Sylvia , Bernhard Karl
Published: December 2004

Five brains of 6 weeks old children have been examined by previously published methods. Pure lipids from different brain regions have been separated into various fractions.
Zur Kenntnis der metastabilen Übergänge in Massenspektren organischer Verbindungen
Authors: Seibl J.
Published: December 2004

Observations in the mass spectra of several organic compounds indicate that metastable ions do not constitute conclusive evidence for one‐step decomposition processes or elimination of structural entities. Contrary to accepted views it appears that metastable ions may arise from two‐step or possibly even from multi‐step fragmentation reactions.
19‐nor‐Steroide V. Neue Synthese von 6‐Dehydro‐19‐nor‐Steroiden. Über Steroide, 208. Mitteilung
Authors: Kalvoda J. , Anner G.
Published: December 2004

A new efficient approach to the synthesis of Δ4,6‐3‐oxo‐19‐norsteroids is described. Starting from 3β, 17α‐diacyloxy‐20‐oxo‐Δ5‐pregnenes, the derivatives VIIIa and VIIIb of 6‐dehydro‐19‐norprogesterone have been synthesized, which exhibit high progestational activity. Modification of the procedure leads to the new group of steroidal Δ5(10),6‐dienes.
Etude des composés d'addition des acides de LEWIS XXIX. Composés d'addition entre acides aromatiques et SbCl5, AlCl3, TiCl4, SnCl4 ou ZnCl2
Authors: Petitpierre B. , Susz B. P.
Published: December 2004

The adducts of benzoic, p‐toluic, mesitoic and cinnamic acids with SbCl5, AlCl3, TiCl4, SnCl4 and ZnCl2 have been prepared, and the IR. absorption spectra of the compounds, in the solid state or in solution in CCl4, studied. The lowering of the carbonyl frequency shows that the acceptor is linked by a dative bond to the carbonyl oxygen atom acting as donor. A calculation, by the Wilson GF method, of force constants and their contributions in potential energy of vibration for monomeric benzoïc acid and its adduct with TiCl4 confirmed that the carbonyl stretching force constant, and therefore the CO bond order, is lowered by the formation of the adducts.
Die Cardenolide der Samen von Mansonia altissima A. CHEV. 2. Mitteilung Die Struktur von Mansonin und Strophothevosid Glykoside und Aglykone, 287. Mitteilung
Authors: Allgeier H. , Weiss Ek. , Reichstein T.
Published: December 2004

Mansonin is the 2,3‐di‐O‐methyl‐6‐deoxy‐β‐D‐glucopyranoside of strophanthidin, and strophothevoside the corresponding 3‐O‐methyl‐6‐deoxy‐β‐D‐glucopyranoside.
Gymnemagenin, vermutliche struktur Glykoside und Aglykone, 289. Mitteilung
Authors: Stöcklin W.
Published: December 2004

Gymnemagenin, the aglycone obtained from gymnemic acid by fermentative degradation and alkaline hydrolysis, is probably a new hexahydroxy‐triterpene. The proposed structures are derived mainly from data obtained by physical methods. Gymnemagenin is probably a 3β,15α(or 16β), 21β,22α,23,28‐ or 3β,15α,16β,21β(or 22α), 23,28‐hexahydroxy‐olean‐12‐ene. Further experimental information is necessary for decision concerning the correct structure.
Über Papaver bracteatum LINDL. IV. Mitteilung Zur Struktur des Alkaloids E
Authors: Guggisberg A. , Hesse M. , Schmid H. , Böhm H. , Rönsch H. , Mothes K.
Published: December 2004

From Papaver bracteatum LINDL. «Halle III» a new alkaloid representing the rhoeadine type has been isolated, the structure of which was elucidated by means of high resolution mass spectrometry and NMR. spectroscopy mainly.
Synthese von Exalton und racemischem Muscon aus Cyclododecanon Vorläufige Mitteilung
Authors: Ohloff G. , Becker J. , Schulte‐Elte K. H.
Published: December 2004

New lines for the preparation of cyclopentadecanone (exaltone) and racemic muscon starting from cyclododecanone via bicyclic intermediate steps are described.
Stoffwechselprodukte von Mikroorganismen 55. Mitteilung [1] über die Konstitution des Borrelidins
Authors: Keller‐Schierlein W.
Published: December 2004

By means of chemical degradation, N.M.R. and mass spectrometry structure II has been determined for the antibiotic borrelidin.
Das ESR.‐Spektrum der 1,2,3‐Trihydropyrenyls
Authors: Gerson F. , Heilbronner E. , Reddoch H. A. , Paskovich D. H. , Das N. C.
Published: December 2004

The two isomeric tetrahydropyrenes II and III have been prepared by Birch reduction of pyrene. Air oxidation of either compound yields 1,2,3‐trihydropyrenyl (1,9‐trimethylene‐phenalenyl; IV); its ESR. hyperfine structure is shown to be closely related to that of phenalenyl.
Les spectres de masse dans l' analyse 10e communication [1] les transferts d'hygrogène dans des cétones norbornyliques
Authors: Thomas Aaln F. , Waillhalm B.
Published: December 2004

Some simple rules for predicting the transfer of endo hydrogens in the mass spectra of norbornane carbonyl derivatives are proposed. Transfers from C‐6 to C‐2 generally occur, but are repressed if a methyl group is on C‐1. Transfers from C‐5 to C‐2 can occur, but are less favorable than 1‐3 transfers. Endo‐2‐acetylnorbornanes undergo a γ‐hydrogen transfer from C‐5 with ring fission.
Untersuchung reversibler Photoprozesse durch Blitzlichtphotolyse IV. Triplettzustände des 1, 3, 6′, 8′‐ tetramethyl‐dehydrodianthrons
Authors: Huber J. R. , Wild U. , Günthard Hs. H.
Published: December 2004

By means of the flash photolysis technique, transient absorption spectra attributed to tetramethyl‐dehydrodianthrone (TMD) in both the photochromic and triplet states have been investigated in polymethylmethacrylate matrices and in the solvent triacetin. In polymethylmethacrylate matrices and in rigid glasses of triacetin the triplet state of TMD is heavily populated. Triplet‐triplet absorption and phosphorescence measurements show that below 180°K the triplet decay follows first order kinetics with the decay constant k=11,3 ± 0,1 s−1. In incompletely solidified triacetin glass it is possible to monitor the transient absorption of the photochromic and the triplet state simultaneously. It is shown that the photochromic state 1A1* is not generated via the triplet state. Therefore the authors suggest a kinetic scheme characterised by a direct singlet state ‐ photochromic state transition.
Über die gas‐chromatographische Bestimmung von Amphetamin als (1‐phenyl‐isopropyl)‐isothiocyanat
Authors: Brandenberger H. , Hellbach Esther
Published: December 2004

Amphetamine (I) reacts spontaneously at room temperature with carbon disulfide to form (1‐phenyl‐isopropyl)‐isothiocyanate, which was identified by UV.‐, IR.‐ and mass spectrometry. This reaction is used for the analytical determination of I by gas chromatography. The characteristic peak shift which occurs after addition of carbon disulfide differentiates I from N‐methylamphetamine (II). The method is applied to urine analysis of I and II (which partially metabolizes to I) and might be useful in doping control.
Über pentacyclische Azofarbstoff‐ Chrom (III)‐und kobalt (III)‐komplexe vom «DREW‐PFITZNER»‐Typus
Authors: Schetty G.
Published: December 2004

For the first time pentacyclic azo dyestuff chromium(III) and cobalt(III) complexes with Drew‐Pfitzner configuration have been produced. Comparison of their electronic spectra with those of analogous 1:2 complexes enables novel conclusions as to the shape of the octahedron formed by the metal‐binding atoms.
Zur Struktur des γ‐MnO2
Authors: Giovanoli R. , Maurer R. , Feitknecht W.
Published: December 2004

By treating Mn3O4 of a specific surface of about 30 m2/g with hot diluted nitric acid, a relatively well crystallised γ‐MnO2 has been obtained. It consists of flat needles of approximately 40,000 × 2000 × 500 Å. Selected area electron diffraction patterns from such single crystals give the (b c) zone of Ramsdellite with c as needle axis. The reflections are broadened in the b‐direction, which is consistent with the shift and broadening of the X‐ray reflections of similar type. The X‐ray Guinier pattern is consistent with the postulated intergrowth structure, proposed by BYSTRÖM and later by de Wolff. Hence the present product consists of a Ramsdellite matrix with statistically distributed Pyrolusite microdomains. The domains are supposed to have the size of one cell only in the b‐direction and of a few cells in the a‐direction, and to be present in relatively small concentrations. From the absence of satellites in the electron diffraction pattern it follows that the domains are disordered and do not form a super‐lattice with giant periods as might be supposed. There is no need to distinguish between η‐ and γ‐MnO2 (GLEMSER [2]); the whole group of varieties, hitherto distinguished by Glemser as «η‐ and γ‐MnO2», have the same lattice and differ only by crystallite size and concentration of microdomains.
Die Lipide aus einjährigen Kinderhirnen
Authors: Lesch Peter , Bernhard Karl
Published: December 2004

Pure lipids from different parts of brains from 1 year old children have been isolated and separated into different fractions. Compared with previous results concerning brains of new‐born and 6 weeks old children clear differences are found, i.e. an increase of cerebrosides and a decrease of lecithines with advancing years and progressing myelinization.
Beiträge zur Chemie der Si‐N‐Bindung, XI [1] polymere 1, 3‐diaza‐2‐sila‐cyclopentane
Authors: Fink Walter
Published: December 2004

Linear polymers are built up by polycondensation of aminodimethylsilyl‐ or aminodiphenylsilyl‐terminated monomeric or oligomeric 1,3‐diaza‐2‐sila‐cyclo‐pentanes with bisphenols or disilanols. The thermal properties of the polymers are determined.
Die Protonierung von 1‐Formyl‐ und 1‐Acetyl‐azulenen
Authors: Meuche Doris , Dreyer D. , Hafner K. , Heilbronner E.
Published: December 2004

NMR. data show that protonation of 1‐formyl‐azulene yields essentially a one‐to‐one mixture of conjugate acids in which the hydroxyl group assumes the syn‐planar or anti‐planar configuration relative to the tropylium nucleus. The presence of a minute amount of protonation in position 3 is demonstrated by the rapid hydrogendeuterium exchange in this position. Steric interference in 1‐formyl‐azulenes with a methyl group in the peri position 8 favours the anti‐planar configuration. As shown by one example, the conjugate acids of 1‐acetyl‐azulenes without substituents in positions 2 or 8 assume the anti‐planar configuration. In 1‐acetyl‐azulenes carrying a methyl group in position 8, addition of a proton to the carbon centre 1 is the preferred route of protonation, as a consequence of the accompanying strain release.
Die Glykoside der Wurzeln von Gongronema taylorii (SCHLTR. & RENDLE) BULLOCK. Glykoside und Aglykone, 292. Mitteilung
Authors: Jaeggi K. A. , Weiss Ek. , Wehrli W. , Reichstein T.
Published: December 2004

The roots of Gongronema taylorii are rich in glycosides. These glycosides form a complex mixture of substances, of which some are closely related. From this mixture, six more or less pure but amorphous glycosides could be separated. Mild acid hydrolysis followed by alkaline hydrolysis led to the isolation of 5α‐dihydrosarcostin (1) and some tayloron (3), whose probable structures have been reported earlier. In the original mixture, these genins are esterified predominantly with benzoic and cinnamic acids, and are also bound through glycosidic linkages to a series of sugars of which the following four could be identified by paper and thin layer chromatography: cymarose, digitoxose, oleandrose and pachybiose. Pachybiose and its two anomeric methyl glycosides have been isolated for the first time in a cristalline state.
Die Glykoside der Blätter von Isoplexis isabelliana (WEBB) MASF.. 3. Mitteilung
Authors: Freitag Hellmut , Spengel Sigrid , Linde Horst H. A. , Meyer Kuno
Published: December 2004

The isolation, characterisation and chemical investigation of the cardiac glycosides of the dried leaves of Isoplexis isabelliana (WEBB) MASF. are described. 7 glucosides B, D, E, J (monoside), K, M, and 1 (monoside) could be obtained in homogenous form, 3 others were mixtures (“A” = A1 + A2, “C” = C1 + C2, and “G” = G + K). The substances B (gluco‐evatromonoside), D (cheiroside A), E (digitoxigenin‐glucosido‐6‐deoxyglucoside), J (digitoxigenin glucoside), and M (digitalinum verum) could be identified with known substances. The new glycosides are derived from 3 genins: digitoxigenin, uzarigenin, and xysmalogenin, which are directly bound to one of the following sugars: 6‐deoxyglucose, 2‐O‐acetyl‐6‐deoxy‐D‐glucose, 2,6‐dideoxy‐D‐arabinohexose (= D‐canarose), and 2,6‐dideoxy‐D‐ribohexose (= D‐digitoxose), terminated by a glucose unit. –Canarobiose, a new crystalline disaccharide of D‐glucose and D‐canarose, has also been obtained. –Apart from these cardiac glycosides 3 C21‐steroids have been isolated (in addition to the 2 known genins γ‐digiprogenin and purpnigenin), and their structures elucidated. The presence of 2 sapogenins has been detected.
Sur l'acylation des méthylfluorènes II [1]. Benzoylation et acétylation du méthyl‐2‐fluorène
Authors: Chardonnens Louis , Dousse Roland
Published: December 2004

Benzoylation and acetylation of 2‐methyl‐fluorene according of Friedel‐Crafts in carbon disulfide with aluminium chloride yielded the corresponding 7‐acylderivatives. By oxydation the benzoyl derivative gave 7‐benzoyl‐9‐oxo‐fluorene‐2‐carboxylic acid, which was decarboxylated to the known 2‐benzoyl‐9‐oxo‐fluorene. By reduction according to Clemmensen the acetyl derivative gave 2‐methyl‐7‐ethylfluorene.
Sur les spectres d'absorption infrarouge, entre 2,5 et 16 μ, de semicarbazones
Authors: Naves Yves‐René , Jacot‐Guillarmod André , Zanesco Cornélia Rodica
Published: December 2004

The spectra of 120 semicarbazones in the solide state have been studied between 2.5 and 16 microns in order to correlate absorptions and structures. We have considered most particularly the absorptions v(N‐H) and the so‐called amid‐I and amid‐II bands.
De la chimie des ptérines. 19e communication [1]. Essai d'interprétation des propriétés chimiques des ptérines au moyen de calcul d'orbitales moléculaires
Authors: Bobst A.
Published: December 2004

HMO and semi‐empirical SCF calculations on pterine systems of biochemical interest have been performed. The most basic center of each molecule has been determined by correlating the perturbation effect on the transition energy and the spectroscopic data. Additional calculations attempt to show why the redox‐system which interfers in hydroxylation reactions consists of 5,6,7,8‐tetrahydropterine and a quinoidic form. Finally the formation of radicals in the oxidation step of hydrogenated pterines is discussed.
Über Alkaloide aus Laurelia novae‐zelandiae A. CUNN. 5. Mitteilung über natürliche und synthetische Isochinolinderivate
Authors: Bernauer Karl
Published: December 2004

From an extract of Laurelia novae‐zelandiae A. CUNN. the aporphine alkaloids (−)‐pukateine (I), (−)‐pukateine methyl ether (II), (−)‐roemerine (IV), (−)‐mecambroline (V), (+)‐boldine (VII), (+)‐isoboldine (VIII), (+)‐laurolitsine (IX), and the proaporphine alkaloid (+)‐stepharine (X) were isolated. Compounds II and V were up to now not described as natural alkaloids. These and the alkaloids IV, VII, VIII, IX and X are new for L. novae‐zelandiae.
Die Cardenolide der Samen von Mallotus paniculatus MÜLL.‐ARG. (Euphorbiaceae). 2. Mitt.: Strukturbeweise. Glykoside und Aglykone, 295. Mitteilung
Authors: Roberts K. D. , Weiss Ek. , Reichstein T.
Published: December 2004

The structures of the following cardenolides, isolated from Mallotus paniculatus have been reported: Genin D = 11‐oxo‐uzarigenin (1), genin F = mallogenin = 11β‐hydroxy‐uzarigenin (3). Glycoside K = mallosid (5) is an L‐rhamnoside of mallogenin, and glycoside L (21) is an L‐rhamnoside of a new genine which we have called panogenin. Panogenin was isolated in crystalline form by the hydrolysis of panoside, and its structure was found to be that of 11β‐hydroxy‐coroglaucigenin (23). Glycoside N = glucopanoside (22), the predominant glycoside of the unfermented seeds, was found to contain one molecule of D‐glucose bound in glycosidic form; its position was not investigated.
Zur Nomenklatur einer neueren Klasse von Sesquiterpenen
Authors: Godtfredsen W. O. , Grove John Frederick , Tamm C. H.
Published: December 2004

The name «trichothecane» (I) with a particular numbering is proposed for the basic skeleton of a series of related sesquiterpenes, the corresponding rearranged skeleton (II) (its atoms with the numbers they had in I) is called «apo‐trichothecane».
Photoreaktionen von Iminiumsalzen mit Methanol und mit Formamid
Authors: Dörscheln W. , Tiefenthaler H. , Göth H. , Cerutti P. , Schmid H.
Published: December 2004

By irradiation in methanol at ∼250 nm of iminium salts, e.g. cyclohexylidene‐pyrrolidinium perchlorate (1), in the absence of oxygen and in the presence of benzophenone as sensitizer, good yields of methanol addition products to the C,N‐double bond (e.g. 8) could be obtained. These can be classed as β‐amino‐alcohol derivatives.
Die Reaktion von halogenierten s‐Triazinen mit Cyclopentadienylnatrium. 2. Mitteilung
Authors: Neuenschwander M. , Schaltegger H.
Published: December 2004

Aus den beim Umsatz von 2‐Chlor‐4,6‐dimethoxy‐s‐triazin und von 2,4‐Dichlor‐6‐methoxy‐s‐triazin mit Cyclopentadienylnatrium dargestellten dimeren Cyclopentadienyltriazinen wurden durch Erhitzen im Hochvakuum die monomeren 2‐Cyclopenta‐1′,3′‐dienyl‐s‐triazine II erhalten. Die durchlaufende Konjugation der überwiegenden Monomeren wird durch das NMR.‐Spektrum der unter schonenden Bedingungen dargestellten Maleinsäure‐Addukte bestätigt.
Stoffwechselprodukte von Mikroorganismen. 58. Mitteilung [1]. Neue Makrotetrolide aus Actinomyceten
Authors: Gerlach H. , Hütter R. , Keller‐Schierlein W. , Seibl J. , Zähner H.
Published: December 2004

Aus einem Stamm der Spezies Streptomyces flaveolus (WAKSMAN) WAKSMAN et HENRICI wurden neben Nonactin, Monactin, Dinactin und Trinactin vier neue Makrotetrolide isoliert, an deren Aufbau ausser den bekannten Hydroxysäuren Nonactin‐säure und Homononactinsäure auch die Bishomononactinsäure (VIII) beteiligt ist.
Zusatzgerät zu Spektropolarimetern für die Lösumgsmittelkompensierte Messung der magneto‐optischen Rotationsdispersion (MORD.)
Authors: Clerc J. T. , Wipf H.‐K. , Simon W.
Published: December 2004

A simple attachment to a spectropolarimeter for recording fully compensated magneto‐optical rotatory dispersion (MORD.) spectra is described.
Über die 1,2‐Verschiebung der Säureamidgruppe bei der Benzilsäureumlagerung von Chinisatin
Authors: Dahn H. , Donzel A.
Published: December 2004

Labelling with 14C shows that the benzilic acid type rearrangement of quinisatine (I) to isatine (III) proceeds essentially by a 1,2‐shift of the intact carbonamid group to the carbonyl group at C‐4. The reaction rate was determined by polarography.
[2.2. …] Metacyclophane
Authors: Burri K. , Jenny W.
Published: December 2004

The synthesis of [2.2.2] metacyclophane (yield 7,5%), [2.2.2.2]metacyclophane (yield 1,7%), [2.2.2.2.2]metacyclophane (yield 5,1%), [2.2.2.2.2.2]metacyclophane (yield 3,1%) and [2.2.2.2.2.2.2.2]metacyclophane (yield 0,5%) by a WURTZ reaction with α,α'‐dibromo‐m‐xylene is described. The structure of the new ring systems was confirmed by UV.‐, NMR.‐ and mass spectra analyses. In connection with the resulting melting points and NMR.‐spectra probable conformations of these higher ring systems are discussed.
Stoffwechselprodukte von Mikroorganismen. 60. Mitteilung [1]. Synthese der 8‐Desoxynonactinsäure
Authors: Gerlach H. , Huber E.
Published: December 2004

8‐Deoxynonactic acid, a degradation product of the antibiotic nonactin, has been synthesized.
Fragmentierung von α,β‐Epoxy‐ketoximen zu Acetylenketonen. Vorläufige Mitteilung
Authors: Wieland P. , Kaufmann H. , Eschenmoser A.
Published: December 2004

A new version of the oxidoketone‐alkynone fragmentation is described. Two steroidal α,β‐oxido‐oximes are shown to fragment to the corresponding alkynones when treated with hydroxylamine‐O‐sulfonic acid in alcaline solution at room temperature.
Recherches sur la formation et la transformation des esters LXXVII [1]. Etude à l'aide de H2[18O] de la scission de quelques monoesters phosphoreux et de l'acide propargyl‐benzènephosphonique
Authors: Cherbuliez Emile , Moll H. , Hunkeler F. , Prince R. , Rabinowitz J.
Published: December 2004

(1) Monopotassium phosphite KH2PO3 heated at 300°C with CO[18O] exchanges one atom of oxygen after 3 hours, one to two atoms after 6 hours, and its three O atoms after 12 hours; the probable mecanism of this exchange is discussed. When the same treatment is carried out in the presence of o‐phenylene diamine hydrochloride, the exchange is total (three O) after 3 hours at 300°C. Treated by this last procedure, benzenephosphonic acid C6H5PO(OH)2 undergoes equally a total exchange of its O atoms in 3 hours.
Apparatur zur Molekulargewichtsbestimmung an hochverdünnten (10−4M). Lösungen mittels Dampfdruckosmometrie
Authors: Dohner R. E. , Wachter A. H. , Simon W.
Published: December 2004

A vapour pressure osmometer for the determination of number‐average molecular weights is described. With this improved design 10−4M solutions can be measured with a standard deviation of 1.3% (carbon tetrachloride, 30°C). Molecular weight determinations up to 160000 (± 7.5%; polystyrene in carbon tetrachloride) are presented.
Etude du transfert d'énergie en milieu liquide à 1'aide du coupage de la scintillation
Authors: Cosandey Maurice , Lerch Pierre
Published: December 2004

The scintillation quenching effect in a liquid medium (toluene) has been studied for numerous compounds W. The quenching power ξ = d(I0/I)/d[W] of most aliphatic compounds is small, less than 1 1/mole, and may be interpreted by a collision theory. The ketones, and in general all compounds with a high extinction coefficient for toluene fluorescence, have such a high quenching effect that it appears to be due to a transfer by resonance. The experimental data fit the theory perfectly if, in the expression for collisional energy transfer, the average molecular radius is replaced by half the FÖRSTER critical resonance distance, and if a coefficient of migration of energy is added to the diffusion constant. The transfer is more or less reversible. For compounds which can only be deecxitated by a π‐π* transition, it is completely reversible, and quenching is null. When the excitation energy can be degraded by a n‐π* transition, the transfer is completely irreversible, and the quenching is maximum. For intermediate cases, the quenching effect is interpreted with the supplementary hypothesis of an intramolecular energy transfer.
Etude des composés d'addition des acides de Lewis XXX [1]. Note préliminaire sur les composés d'addition entre aldéhydes et TiCl4
Authors: Weber R. , Susz B. P.
Published: December 2004

The adducts of acetic, benzoic, cinnamic, and anisic aldehydes with TiCl4 have been prepared, and the IR. spectra of the compounds, in the solid state or in solution in CH2Cl2, studied. The lowering of the carbonyl frequency shows that the acceptor is linked by a dative bond to the carbonyl oxygen atom acting as donor.
Recherches sur les arǒmes. 16e communication [1]. Sur l'arǒme du cacao III
Authors: Flament I. , Willhalm B. , Stoll M.
Published: December 2004

The isolation and analysis of a cocoa concentrate is described: 62 constituents have been identified, 42 of which for the first time. Most identifications are based upon mass spectrometry combined in many cases with IR. spectrometry, and comparison with reference compounds. A number of minor constituents could not be identified.
Zur Synthese des Ecdysons IX. Mitteilung über Insektenhormone
Authors: Furlenmeier A. , Fürst A. , Langemann A. , Waldvogel G. , Hocks P. , Kerb U. , Wiechert R.
Published: December 2004

A synthesis of ecdysone is described by which the insect moulting hormone can be readily prepared. Oxidation of ergosterol gave the 6‐keto‐Δ7‐function, and preparation of the Δ2‐olefine followed by stereospecific hydroxylation led to the 2β,3β‐glycol system. Ozonization furnished (20 S)‐2β,3β‐diacetoxy‐20‐formyl‐5α‐pregn‐7‐en‐6‐one into which the side chain was introduced by a Grignard reaction with 2‐methyl‐3‐butyn‐2‐ol tetrahydropyran‐2‐yl ether and a subsequent reduction of the triple bond. Hydroxylation at C‐14 and isomerization at C‐5 gave ecdysone. By an interchange of the sequence of the reactions C‐22 isoecdysone was obtained stereospecifically.
Photochemische Umwandlungen. XV [1] Photochemische Isomerisierung des exo‐Tricyclo[4.2.1.02′5]nona‐3,7‐dien‐Systems. Vorläufige Mitteilung
Authors: Eberbach W. , Prinzbach H.
Published: December 2004

The acetone sensitized isomerization of two exo‐tricyclo[4.2.1.02,5]nonadiene derivatives, of the corresponding tricyclo[4.3.0.02,5]nonadienes, and the photoisomerization of two bicyclo[4.3.0]nonatrienes by direct excitation are described.
Das Elektronenspektrum eines vinylogen Tropons (Die photochemische darstellung des 2‐Hydroxy‐guaj‐azulens)
Authors: Hagen R. , Heilbronner E. , Straub P. A.
Published: December 2004

Irradiation of guaj‐azulene‐2‐sulfonic acid (VII) in 40 percent aqueous or methanolic sulfuric acid with light of 370 nm wave‐length yields 2‐hydroxy‐guaj‐azulene (V) or 2‐methoxy‐guaj‐azulene (X) respectively. The former compound (V) exhibits a keto‐enol tautomerism V ⇋ VI, the equilibrium constant of which is strongly dependent on solvent. The keto form VI contains the π‐electron system of a vinylogue tropone IV. The theoretical analysis of the electronic spectrum of VI, using a CI‐model of the PARISER‐PARR‐POPLE type, supports the previously proposed assignement of the electronic transitions observed in tropone (I), benzotropone (II) and naphthotropone (III).
Elektronenstruktur und physikalisch‐chemische Eigenschaften von Azo‐Verbindungen. Teil XIV: Die Konformation des Benzalanilins
Authors: Haselbach E. , Heilbronner E.
Published: December 2004

A re‐evaluation of the electronic spectra of benzalaniline (II), 3, 3‐dimethyl‐2‐phenyl‐indolenine (X), mono‐aryl substituted azomethines (XI, XIV, XV) and trimethylindolenine (XII) as well as of their conjugate acids strongly supports the hypothesis of ISMAILSKI& SMIRNOV[14] and of EBARA[15] that benzalaniline exists in a preferred peri‐perpendicular conformation. The same is true for N‐phenylazomethines. Then→ π* transition of a ‘planar benzalaniline’ has been located at 27 600 cm−1(ε ≈ 60).
Contribution à 1′étude des acides de CLEVE Le système quinaire Na+‐M++‐amino‐1‐naphtalène‐sulfonate‐6‐amino‐1‐naphtalène‐sulfonate‐7‐C1−‐H2O entre 0° et 75°
Authors: Rochat A. C. , Flatt R.
Published: December 2004

The solubility diagram of the quinary system Na+‐Mg++‐1‐anminonaphtalene‐6‐sulfonate‐1‐aminonaphtalene‐7‐sulfonate‐Cl−‐H2O has been partially investigated between 0° and 75°.

From this diagram a simple and effective procedure to separate the two CLEVE'S acids has been calculated, with yields in acid 1.7 (extracted as sodium salt) of 95.1% and in acid 1.6 (obtained as magnesium salt) of 70.0%.

This theoretical procedure was adapted to the fraction of a crude industrial mixture of CLEVE's acids.
Salzebullioskopie II Die Gültigkeit des salzebullioskopischen und salzkryoskopischen Grenzgesetzes in verschiedenen Inertsalz‐Fremdsalz‐Systemen
Authors: Magyar B.
Published: December 2004

The vapor pressure of a saturated salf solution (the salt acting as inert electrolyte) is lowered by foreign solutes by an amount which is proportional to the molal concentration of the foreign solute. Any ion not in common with the inert electrolyte is acting as a foreign solute. This effect is used in salt ebullioscopy, a new procedure for the determinaton of the relative weights of ions which has been described recently [2]: The number ν of foreign ions per formula unit of the solute is determined experimentally and permits the evaluation of relative ionic weights. It was found that the apparent number ν(m2) of foreign ions per mole of solute determined at different concentrations of the solute sows a linear dependence on concentration: v(m2) = νo + N · m2. The linearity has been tested on 31 systems differing in the pair foreign salt –inert salt. The largest deviation of νo from the true value of ν was 0,1. It is shown theoretically that the slope N is the sum of a stöichiometric term N*, and of a term caused by the change of the activity coefficient γ2 of the solute. Therefore, γ2 can be calculated from (N – N*). The nuclearity (n = 1/ν) of the antimony complex in the compound potassium antimony tartrate was found to be 2.
Totalsynthese des neuen Leguminosen‐Alkaloids Hystrin 16. Mitteilung über Leguminosen‐Alkaloide
Authors: Steinegger E. , Weber P.
Published: December 2004

A total synthesis of hystrine has been realised with good yield by the introduction of a double link into the piperidine nucleus of synthetic ammodendrine, followed by deacetylation, and purification with the aid of the nitroso derivative.

The identity of the synthetic product with authentic hystrine was established by its chromatographic behaviour, by UV.‐, IR.‐ and mass spectra as well as by the properties of its nitroso derivative. Thus the proposed structure of hystrine as 3‐(2, 3, 4, 5‐tetrahydropyrid‐6‐yl)‐1, 4, 5, 6‐tetrahydropyridine (V) is proved.
Chemie der Komplexe von Liganden mit schweren Donoratomen II. MÖSSBAUER‐Untersuchung der Eisenkomplexe von Di‐isopropyl‐dithiophosphat
Authors: Korecz L. , Burger K. , Jgrgensen C. K.
Published: December 2004

The MÖSSBAUER spectra of the new complexes Fe(dptp)3 and trans‐Fe(dptp)2py2 (dptp− = (C3H7O)2PS2−; py = C5H5N) are measured and discussed.
Thyrocalcitonin. I. Isolierung und Charakterisierung wirksamer Peptide aus Schweineschilddrüsen
Authors: Kahnt F. W. , Riniker B. , Macintyre I. , Neher R.
Published: December 2004

α‐ and β‐thyrocalcitonic isolated from pig thyroids were found to be single‐chain polypeptides with 32 amino acid residues containing a disulphide bridge. Tryptic digestion yielded inactive hepta‐, undeca‐and tetradecapeptides, the amino acid composition of which is given. β‐thyrocalcitonin proved to be the methionine sulphoxide derivative of the easily oxidizable methionine peptide α‐thyrocalcitonin; thus, the designation β can be eliminated. Both peptides have a potency of about 200 MRC units/mg dry weight. They can readily be differentiated by their electrophoretic and chromatographic properties, as well as by their tryptic undecapeptide, whereas the hepta‐ and tetradecapeptides, respectively, produced by trypsin are identical.
Photochemische Reaktionen. 43. Mitteilung [1]. UV.‐Bestrahlung von N‐Phenylurethan und N‐Phenylthiourethan
Authors: Belluš D. , Schaffner K.
Published: December 2004

Ultraviolet irradiation of N‐phenylurethane (I) solutions with wavelength 253,7 nm resulted in the formation o polymeric material, the characteristic pattern of monomeric products associated with Photo‐FRIES‐type rearrangements [→ ethyl anthranilate (II), ethyl p‐aminobenzoate (III)], and accompanying dissociation products [→ aniline (IV)].

N‐Phenylthiourethance (V) showed no tendency to undergo Photo‐FRIES‐type rearrangements. Formation of polymeric material and aniline (IV), and in the presence of molecular oxygen, cyclodehydrogenation to the 2‐ethoxy‐benzthiazol (VI) as well as a ready exchange of the sulfure atom in V by oxygen occurred instead.
Recherches sur la formation et la transformation des esters LXXIX [1]. Sur la réaction de l′isothiocyanate d′o‐méthoxycarbonyl‐phényle avec divers acides et l′acide sérinephosphorique
Authors: Cherbuliez Emile , Espejo O. , Willhalm B. , Rabinowitz J.
Published: December 2004

Amino acids devoid of «leaving groups» on their β carbon atom (neither OH: serine, nor SH: cysteine) react with o‐methoxycarbonyl‐phenyl isothiocyanate (I) in the presence of one equivalent of NaOH, in water‐dioxane or in ethanol, to yield the corresponding hydroquinazolinone derivatives II which were isolated as free acids.

When treated with CH3COOH + conc. HCl the hydroquinazolinone resulting from the reaction of L‐serine with I undergoes a nucleophilic attack of the carbon bearing the leaving group OH by a lone pair of electrons of S; this attack produces the formation of an additional thiazolidine ring, yielding the thiazoloquinazolinone derivative (−)‐III. In an analogous reaction DL‐serine phosphoric acid treated with I at pH 8–9 yields the corresponding substituted hydroquinazolinone which, boiled in 1N hydrochloric acid, undergoes ring closure to (±)‐III by the same mechanism as the serine derivative (leaving group: OPO3H2).

L‐Cysteine reacted with 2 equiv. of I and then treated with CH3COOH + conc. HCl gives two products: (−)‐III produced by the same mechanism as for serine (leaving group: SH), and the quinazolinone derivative IV where the SH group is also thiocarbamoylated.
Die Reaktion von halogenierten s‐Triazinen mit Cyclopentadienylnatrium 3. Mitteilung
Authors: Neuenschwander M. , Schaltegger H.
Published: December 2004

Bei der Reaktion von äquimolaren Mengen 2‐Chlor‐4, 6‐dimethoxy‐s‐triazin und Cyclopentadienylnatrium entsteht ein disubstituiertes Cyclopentadien, welches auf Grund der spektroskopischen Daten als 4, 6‐Dimethoxy‐2‐[2′‐(4″, 6″‐dimethoxy‐2″‐s‐triazinyl)‐cyclopentadienyliden]‐1, 2‐dihydro‐striazin (II) betrachtet wird.
Struktur der Pachybiose und Asclepobiose. Desoxyzucker, 44. Mitteilung
Authors: Allgeier H.
Published: December 2004

Pachybiose (1) is shown to be 4‐O‐(3‐O‐methyl‐6‐deoxy‐β‐D‐allopyranosyl)‐D‐oleandrose and asclepobiose (14) 4‐O‐(3‐O‐methyl‐6‐deoxy‐β‐D‐allopyranosyl)‐D‐cymarose.
Herstellung von 1,4‐Dichlornaphtalin aus 1,4‐Dichlor‐5‐nitro‐naphtalin
Authors: Kniel P.
Published: December 2004

Treatment of 1,4‐dichloro‐5‐nitro‐naphthalene with sodium borohydride in dimethylformamide yielded 1,4‐dichloronaphthalene (80–83%).
Über En‐Synthesen mit Singulett‐Sauerstoff Die Farbstoff‐sensibilisierte Photooxygenierung von (−)‐Caryophyllen und (−)‐iso‐Caryophyllen und die Stereochemie der dargestellten Caryophylladienole
Authors: Schulte‐Elte K. H. , Ohloff G.
Published: December 2004

The dye‐sensitized photooxygenation leads in the case of (−)‐caryophyllene (1) to 4 allylhydroperoxides, and with (−)‐iso‐caryophyllene (2) additionally to 2 tertiary compounds of this kind. The stereochemistry of the isolated 6 caryophylladienols derivatives 6–11 is elucidated. By that way an interpretation of the reaction mechanism is possible.
Sulfonylgruppenhaltige Liganden in Chromkomplexen von drei‐ und sechszähnigen Mono‐ bzw. Disazofarbstoffen aus 4,5‐Diphenylimidazol als Kupplungskomponente
Authors: Schetty G.
Published: December 2004

o‐Aminobenzenesulfonic acid → 4,5‐diphenylimidazole [DPI] forms an unstable 1:2‐chromium complex, accordingly the DREW‐PFITZNER arrangement is indicated. o‐Aminobenzenesulfonic acid ethylamide → DPI yields no chromium complex, whilst 1,3‐di‐(2‐aminobenzolsulfonamido)‐propane → DPI forms an unstable pentacyclic chromium complex.
Das Protonenresonanzspektrum von orientiertem Furan in nematisch‐kristallinflüssiger Lösung
Authors: Diehl P. , Khetrapal C. L. , Kellerhals H. P.
Published: December 2004

The proton spectrum of furan oriented in the nematic phase of anisoleazophenyl‐n‐capronate has been analysed. The ratios of the various interproton distances as well as the orientation parameters and the signs of the indirect coupling constants for furan are determined.
Zur Bestimmung von Aktivitäten und Konzentrationen mit natriumempfindlichen Glaselektroden
Authors: Schindler P. , Wälti E.
Published: December 2004

The e.m.f. of the cell Ag, AgCl/NaCl solution/sodium sensitive glass electrode was measured at 25°C. In pure water as a solvent, measured activity coefficients agree with tabulated osmotically determined values; hence, the ideality of the sodium response of the glass electrode is confirmed. Choosing a Tris – Tris. HCl buffer of the constant ionic strength 0,5M as a solvent, the applicability of HARNED'S rule was demonstrated. Conditions for measuring sodium ion concentrations with sodium sensitive glass electrodes are discussed.
Die Zustandsdiagramme von Quecksilber(II)‐Jodid mit den dreiwertigen Jodiden von drei Elementen der 5. Gruppe des Periodischen Systems
Authors: Gämann A.
Published: December 2004

The temperature/concentration diagrams of the binary systems of HgJ2 with AsJ3, SbJ3, and BiJ3 are determined by differential‐thermal analysis. In addition to the temperature of the several phase transitions the peak areas of the differential curves are evaluated as a new quantity of measurement. Eutectic systems are found in each case.
Darstellung von (−)‐iso‐Caryophyllen aus (−)‐Caryophyllen durch photochemisch erzeugte Thiylradikale
Authors: Schulte‐Elte K. H. , Ohloff G.
Published: December 2004

A simple method for preparing (−)‐iso‐caryophyllene (2) by irradiation of (−)‐caryophyllene (1) with a high‐pressure mercury lamp in the presence of small quantities of diphenyldisulphide is described.
ESR.‐Spektrum von Diphenylpicrylhydrazyl (DPPH)
Authors: Haniotis Z. , Günthard Hs. H.
Published: December 2004

The ESR. sprectra of DPPH in mixed organic solvents have been measured with a K‐band superheterodyne spectrometer and self‐locking magnetometer with high precision. Approximately 150 lines have been resolved in the spectra. Both the zero and first order derivative spectra were analyzed by a line shape analysis program for determination of the coupling constants. The smallest coupling constant was found to be 377 ± 5 mG, all other coupling parameter are multiples of this constant. A set of most probable coupling constants is given. The two nitrogen coupling constants are found to be equal within experimental error, and there exist several rotational relations and several possible assignments.
Über die Darstellung eines 1:2‐Chrom(III)‐Komplexes vom Sandwichtypus für FOURIER‐Analyse
Authors: Schetty G.
Published: December 2004

A 1:2‐Chromium(III)‐«sandwich»‐complex of the anthranilic acid → pyrazolone series has been prepared for FOURIER‐analysis.
Umsetzungen des Cyclohex‐3‐en‐carbaldehyd‐p‐toluolsulfonylhydrazons
Authors: Rey M. , Begrich R. , Kirmse W. , Dreiding André S.
Published: December 2004

The vacuum thermolysis (80–90°) of the sodium salt of cyclohex‐3‐ene‐carbaldehyde p‐toluenesulfonylhydrazone (1) in silicone oil gave diazomethyl‐cyclohex‐3‐ene (2). Pyrolytic and photolytic decomposition of this diazo compound 2 lead to methylenecyclohex‐3‐ene (5) and bicyclo [4.1.0]hept‐2‐ene (6) (about 3:1), while the CuCl catalyzed cleavage yielded only 5. The postulated carbene mechanism should also apply under the direct aprotic decomposition conditions of the sodium salt of 1 in diglyme, where methylenecyclohex‐3‐ene and bicyclo[4.1.0]hept‐2‐ene (about 3:1) were formed besides small amounts of 1‐methylcyclohexa‐1, 3‐diene (9) and bicyclo [4.1.0]hept‐3‐ene (8). Under protic conditions (in ethylene‐glycol) methylenecyclohex‐3‐ene, 1‐methylcyclohexa‐1, 3‐diene and 1‐methylcyclohexa‐1, 4‐diene (14) were produced in a ratio of 1:1:1.

The direct mild thermolysis of cyclohex‐3‐ene‐carbaldehyde p‐toluenesulfonylhydrazone (1) in benzene solution afforded N‐(p‐toluenesulfinyl)‐O‐(p‐toluenesulfinyl)‐cyclohex‐3‐en‐yl‐α‐methanolamine (15) and di‐(cyclohex‐3‐en‐yl‐methyl)‐ammonium p‐toluenesulfonate (16), the structures of which were supported by their nmr. spectra and by alkaline cleavage.
Magneto‐optische Rotationsdispersion von gesättigten aliphatischen Kohlenwasserstoffen
Authors: Wipf H.‐K. , Clerc J. T. , Simon W.
Published: December 2004

Magneto‐optical rotatory dispersion (MORD.) of saturated aliphatic hydrocarbons can be described very accurately by an equation of the DRUDE type. The two parameters, appearing in such an equation, have been determined from MOR. measurements in the region of 240 to 500 nm by the method of least squares. These parameters show a systematic dependence on the structure of the investigated hydrocarbons. An empirical rule for the approximation of the DRUDE parameters is given which in turn allow the calculation of the VERDET constant for a given structure at any wavelength between 240 and 500 nm.
Thermoanalytische und massenspektrometrische Untersuchung der Zersetzung von Zinkoxalat‐Dihydrat. Thermoanalytische Untersuchungen XII
Authors: Giovanoli R. , Wiedemann H. G.
Published: December 2004

The dehydration and pyrolysis of zinc oxalate dihydrate are re‐examined by thermo‐analytical methods at linearily increasing temperature in air, nitrogen, water vapour, and high vacuum. Simultaneous analysis of the gaseous decomposition products by means of mass spectrometry confirms previous authors' results obtained with other methods. The activation energy of the thermal decomposition of ZnC2O4 above 340° has been found to be 40,4 ± 2,6 kcal/mol.

The rehydration of ZnC2O4 has been investigated at various water vapour pressures. In an atmosphere virtually saturated with moisture, the rehydration leads to the dihydrate and is easily controlled on the thermobalance. The dihydrate itself takes up an ill‐defined fraction of surplus water. The thermal effects resulting from surface water on the dihydrate have been investigated by DTA (freezing and melting peaks). They disappear below 5% w/w of surplus water in the dihydrate.

The surface of cristallites of the decomposition products calculated from particle size (from X‐ray line broadening) is much larger than the surface determined by the BET‐method. However, for ZnO in its state immediately after decomposition of ZnC2O4, both methods give similar results. Thus, dihydration of ZnC2O4 · 2 H2O produces a considerable inner surface of ZnC2O4 not accessible to gas adsorption. This surface is considered to be covered by adsorbed water, which would explain the remarkable amount of water retained during dehydration. The final product, ZnO, sinters rapidly at temperatures higher than 500–600°.
Sur une nouvelle synthèse et les caractéristiques chimico‐physiques du picolylidène‐2‐bis‐(p‐phénylsulfate de sodium) (DCI: «Picosulfate de sodium»)
Authors: Pala G. , Crescenzi E. , Bietti G.
Published: December 2004

The synthesis of 2‐picolylidene‐bis‐(p‐phenylsulfuric acid) disodium salt (I, DCI: ‘sodium picosulfate’) has been realized by two routes. I has been characterized by the usual analytical data and UV., IR. and PMR. spectral properties.
Sigmatropische Umlagerungen von Aryl‐propargyläthern; Synthese von 1, 5‐Dimethyl‐6‐methylen‐tricyclo[3, 2, 1, 02,7]‐oct‐3‐en‐8‐on‐Derivaten. Vorläufige Mitteilung
Authors: Zsindely J. , Schmid H.
Published: December 2004

2, 6‐Dimethylphenyl propargyl ether (10) and its derivatives 12–15 rearrange thermally to 1, 5‐dimethyl‐6‐methylene‐tricyclo [3.2.1.02,7]oct‐3‐en‐8‐one (9) and related compounds 16–19. The ethers undergo first an aromatic [3, 3]‐sigmatropic rearrangement to ortho‐allenyldienones 11, which then undergo ring closure to the tricyclic products by an electrocyclic reaction.

Only in the case of the γ‐methylpropargyl ether 13, the ortho‐dienone 11 is further rearranged in low yield to the para‐butynylphenol 20, but the tricyclic ketone 17 is again the main product.

New data show that the known thermal cyclisation of aryl propargyl ethers to chromenes (e. g. 4 → 8) involves a preliminary [3, 3]‐sigmatropic rearrangement.
5,5′‐Disubstituierte Diphensäure‐Derivate
Authors: Weis C. D.
Published: December 2004

5,5′‐Dichloro‐2,2′‐biphenyldicarboxylic acid is readily accessible by oxidation of 3,6‐dichloro‐9, 10‐phenanthrenequinone, which in turn has been prepared earlier starting from DDT. Various substitutions and transformations of the 5, 5′‐dichloro‐2, 2′‐biphenyldicarboxylic acid and derivatives are reported.
Über die Wertigkeit des Kobalts in Azofarbstoffkomplexen
Authors: Wittwer C.
Published: December 2004

The CoII‐azocomplexes (1:2) have been prepared and the conditions for their existence are defined. The oxidation to the CoIII‐complex by either oxygen or by the dyestuff itself is described. In the case of dyestuff‐oxidation, the azo group is reduced to the respective amines. The formation of CoIII‐azocomplexes in a technical scale by metallizing with CoII‐salts is discussed.
Selektive Reduktion der 1,2‐Doppelbindung in Δ1,4‐3‐Oxo‐Steroiden. Über Steroide, 213. Mitteilung
Authors: Wieland P. , Anner G.
Published: December 2004

A new method for the selective reduction of the 1,2‐double bond in Δ1,4‐3‐oxo‐steroids is described.