bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kallidin, Synthese und Eigenschaften. (Vorläufige Mitteilung)
Authors: Pless J. , Stürmer E. , Guttman St. , Boissonnas R. A. 
Published: December 2004

AbstractKallidin, a homologue of bradykinin (H‐Lys‐Arg‐Pro‐Pro‐Gly‐Phe‐Ser‐Pro‐Phe‐Arg‐OH) has been synthetized and shown to have the chemical and–so far investigated‐biological properties of natural pure kallidin which differ from those of bradykinin.
Selbstintegrierende Methode zur raschen Bestimmung von Kohlenstoff und Wasserstoff in organischen Verbindungen an Milligramm‐ und Submilligramm‐Mengen unter Verwendung von Katharometern. Vorläufige Mitteilung
Authors: Sommer P. F. , Sauter W. , Clerc J. T. , Simon W. 
Published: December 2004

AbstractA very simple apparatus for the simultaneous determination of carbon and hydrogen on milligram and submilligram samples is described. The sample combustion products, carbon dioxide and water, are trapped in an evacuated system of two thermal conductivity cells with simultaneous removal of water and carbon dioxide, respectively, so that the signals of the first and second cell are proportional to the amount of hydrogen and carbon burned in the sample, respectively. A single determination, including the weighing of the sample, is performed within 7 minutes.
Auf das Zentralnervensystem wirkende Substanzen XXIX. Über neuartige schwefelhaltige Heterocyclen: 4,4‐Dialkyl‐1,2‐thioazetidin‐3‐on‐1,1‐dioxide und 2,4,4‐Trialkyl‐1,2‐thioazetidin‐3‐on‐1,1‐dioxide
Authors: Nicolaus Bruno J. R. , Bellasio Elvio , Testa Emilio 
Published: December 2004

AbstractEs wird der Aufbau von 4,4‐Dialkyl‐1, 2‐thioazetidin‐3‐on‐1,1‐dioxiden beschrieben, die Derivate eines bisher praktisch unbekannten viergliedrigen Heterocyclus mit zwei benachbarten Heteroatomen sind. Diese Substanzen werden aus den α,α‐Dialkylsulfonylessigsäure‐dinatriumsalzen über die entsprechenden Säuredichloride mit Ammoniak erhalten. Neben der Synthese wird über chemische und physikalische Eigenschaften dieser neuen Imide und ihrer noch nicht beschriebenen Zwischen‐produkte, sowie über einige ihrer Umsetzungen berichtet.
Über Steroide und Sexualhormone. 225. Mitteilung. UV.‐Bestrahlung von 11‐Oxo‐Steroiden II Die Darstellung von Δ4‐ und Delta;5‐11β, 19‐Cyclo‐pregnen‐ sowie 5β‐11β, 19‐Cyclo‐ und 5, 19‐Cyclo‐pregnan‐Verbindungen
Authors: Heller M. S. , Wehrli H. , Schaffner K. , Jeger O. 
Published: December 2004

Abstract
In analogy to the previously described photochemical isomerisation of 3,20‐diethylenedioxy‐11‐oxo‐5 α‐pregnane (I → II) the UV.‐irradiation of the Δ5‐ and 5β‐11‐oxo‐steroids III and XXII gives rise to the 11 α‐hydroxy‐11, 19‐cyclo derivatives IV and XXIII, respectively. The observed yields of these tertiary cyclobutanol products decrease in the order II > IV > XXIII. The possible significance of these structure‐dependent rate differences is discussed.
Cerebrosid‐Gehalte verschiedener Bezirke alter menschlicher Gehirne Ein Beitrag zur quantitativen Isolierung reiner Cerebroside
Authors: Bernhard K. , Hany A. , Hausheer L. , Pedersen W. 
Published: December 2004

AbstractAn approximately quantitative method for the isolation of pure brain cerebrosides is reported. Crude cerebrosides are obtained out of total lipids by chromatography on an alumina column, pure cerebrosides are subsequently eluted with chloroform‐methanol from a silicagel column. Those are free of phosphatides, sphingomyelines, gangliosides and sulfatides.
Metallkomplexe mit Polyaminen XI: Mit 2‐Aminomethyl‐1, 3‐diamino‐propan
Authors: Anderegg G. 
Published: December 2004

AbstractThe tendency of 2‐aminomethyl‐1, 3‐diamino‐propane to form complexes with Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Cd2+, Zn2+ and Ag+ was studied using the method of Schwarzenbach.
Die Alkaloide von Ammocharis coranica (KER.‐GAWL.) HERB. emend. M.‐REDH. 3. Mitteilung über Amaryllidaceen‐Alkaloide
Authors: Hauth H. , Stauffacher D. 
Published: December 2004

AbstractA 1,23% alkaloid content was found in fresh Ammocharis coranica (Ker.‐Gawl.) Herb. emend. M.‐Redh. (Amaryllidacee) bulbs. Of this, 14,2% consisted of phenolic bases. Eleven alkaloids have been isolated from the non‐phenolic bases. Four of these (lycorine, crinamine, coranine and acetylcaranine) had already been obtained from this drug, whilst five other known alkaloids (6‐hydroxycrinamine, (+)‐epicrinine, buphanisine, buphanidrine and ambelline) have been isolated for the first time from A. coranica. In addition, small amounts of two new alkaloids ((+)‐epi‐buphanisine and coranicine) have been found.
Über die Reaktion zwischen Epichlorhydrin und Cyclopentadienyl‐natrium
Authors: Schaltegger H. 
Published: December 2004

AbstractBei der Reaktion von Epichlorhydrin mit Cyclopentadienylnatrium wird in etwa 70% Ausbeute ein Produkt erhalten, für welches die Struktur eines 2‐Cyclopentadienyl‐allylalkohols vorgeschlagen wird.
Heilmittelchemische Studien in der heterocyclischen Reihe. 33. Mitteilung. Pyridazine XII. Über 1‐Aryl‐2‐alkyl‐3,6‐dioxo‐1,2,3,6‐tetrahydro‐pyridazine
Authors: Druey J. , Meier Kd. , Staehelin A. 
Published: December 2004

AbstractSeveral 1,2‐disubstituted 3,6‐dioxo‐1,2,3,6‐tetrahydro‐pyridazines have been prepared. Direct alkylation of 1‐aryl‐3‐hydroxy‐6‐oxo‐1,6‐dihydro‐pyridazines with dialkyl sulfates is shown to give either 1‐aryl‐2‐alkyl‐3,6‐dioxo‐1,2,3,6‐tetrahydro‐pyridazines or a mixture of these with 1‐aryl‐3‐alkoxy‐6‐oxo‐1,6‐dihydro‐pyridazines.
Stoffwechselprodukte von Mikroorganismen. 44. Mitteilung. Zur Konstitution von Ferrichrysin und Ferricrocin
Authors: Keller‐Schierlein W. , Deér A. 
Published: December 2004

AbstractThe structures of the fungal sideramines ferrichrysine and ferricrocine have been determined with the exception of their amino‐acid sequence. They are iron complexes of cyclic hexapeptides composed of 3 mols. δ‐N‐acetyl‐δ‐N‐hydroxy‐ornithine, 2 mols serine and 1 mol. glycine (ferrichrysine), resp. 3 mols. δ‐N‐acetyl‐δ‐N‐hydroxy‐ornithine, 1 mol. serine and 2 mols. glycine (ferricrocine).
Die Kristallstruktur des Kaliummethylats
Authors: Weiss E. 
Published: December 2004

AbstractThe crystal structure of potassium methoxide has been determined from X‐ray powder data. KOCH3 is tetragonal (space group P4/nmmD) with a = 3,95 å, c = 8,77 å Z = 2. It has a double‐layer structure with KOCH3‐units arranged perpendicularly to the plane, having their methyl groups alternately on either side of the layer. The arrangement of the oxygen atoms and potassium ions is very similar to that previously reported for potassium acetylenediolate, with K‐O: 2,66 and 2,80 å K‐K: 3,68 å O–O: 4,03 å OCH3: 1,40 Å.
Desoxypodophyllinsäure‐1 β‐D‐glucopyranosyl‐ester, ein neues. Lignanderivat aus Podophyllum peltatum L. und P. emodi WALL. 13. Mitteilung über mitosehemmende Naturstoffe
Authors: Kuhn Max , von Wartburg A. 
Published: December 2004

AbstractThe isolation of lignan J, C28H34O13, a new compound from the roots and rhizomes of American Podophyllum peltatum L. and Indian P. emodi Wall. is described. Lignan J is easily cleaved to desoxypodphyllotoxin and D‐glucose. By degradation of its penta‐phenylurethane, the structure of lignan J has been deduced as the 1β‐D‐glucopyranosylester of desoxypodophyllinic acid. It is suggested that glucose esters of this type may act as intermediates in the biogenesis of lignans.
Etude de structures peptidiques à l'aide de phénylisothiocyanate V. Sur la formation des phénylthiohydantoïnes‐[35S] et sur leur chromatographie
Authors: Cherbuliez Emile , Baehler B. R. , Marszalek J. , Sussmann A. R. , Rabinowitz J. 
Published: December 2004

AbstractUsing a solution of [35S]‐phenylisothiocyanate in pentane with a specific activity of 30 to 8O mC/mmole, the authors have determined the sequence of di‐, tri‐peptides and a pentapeptide on the following quantities: 1 to 2 nmole of peptide when the [35S]‐phenylthiohydantoines obtained in each step of EDMAN'S degradation are identified by classical paper chromatography; 0,l to 0,2 nmole of peptide when these [35S]‐phenylthiohydantoines are identified by silica thin layer chromatography.
Der 1: 2‐Kobalt (III)‐Komplex aus einem o‐Hydroxy‐o′‐alkylamino‐azofarbstoff im Vergleich mit dem durch Verbrückung erhaltenen analogen pentacyclischen Komplex
Authors: Schetty G. 
Published: December 2004

AbstractA pentacyclic CoIII complex is described which is comparable with the tetracyclic 1:2 CoIII complex from 2‐aminophenol‐4‐methyl‐sulphone → N‐ethyl‐2‐naphtylamine. Formally, the two ethyl groups of this latter dyestuff are eliminated in the new compound and replaced by a propylene group joining the two amine‐nitrogen atoms together. The pentacycle occurs in two forms: one with a single positive charge and one with a single negative charge. Both amine‐nitrogen atoms are protonated in the cation and deprotonated in the anion. The tetracyclic 1:2 complex cannot form a corresponding cation; it decomposes in acid medium. The stability of the cationoid pentacycle results from a positive chelate effect due to the additional ring. From the comparison of the electron spectra of the pentacyclic and the tetracyclic 1:2 complexes the author concludes that in the pentacyclic complex the azo dyestoff halves have merely undergone a displacement of position but no torsion.
Synthese von Benzazepinen und ihre Umlagerung in Chinoline und Pyrrolo [2,3‐b]chinoline
Authors: Vogel A. , Troxler F. , Lindenmann A. 
Published: December 2004

AbstractBECKMANN or SCHMIDT rearrangement of ethyl trans‐4‐oxo‐1‐phenyl‐2‐tetralincarboxylate (2) affords ethyl trans‐2,3,4,5‐tetrahydro‐2‐oxo‐5‐phenyl‐1H‐benzo [b] azepine‐4‐carboxylate (4). Mild treatment of trans‐2,3,4,5‐tetrahydro‐1‐methyl‐2‐oxo‐5‐phenyl‐1 H‐benzo‐[b] azepine‐4‐carboxylic acid (7) with thionyl chloride and pyridine in dimethylformamide and subsequent reaction with an amine yields the corresponding benzazepine‐4‐carboxamide. If he it is applied during the preparation of the acid chloride, rearrangement occurs yielding cis and trans derivatives of hydrocarbostyril.2,3,4,5‐Tetrahydro‐1,4‐methano‐1‐methyl‐5‐phenyl‐1 H‐benzo‐[b] azepinium chloride (25) reacts with primary or secondary amines to cis‐tetrahydroquinoline derivatives.When heated above its melting point, trans‐4,5‐dihydro‐2‐methylamino‐5‐phenyl‐3H‐benzo‐[b] azepine‐4‐carboxylic acid (29) rearranges with elimination of water to a mixture of cis‐and trans‐2,3,3a,4‐tetrahydro‐1‐methyl‐2‐oxo‐4‐phenyl‐1H‐pyrrolo [2,3‐b] quinoline (32 and 31). The reduction of 31 was investigated.The mechanisms of the rearrangements are discussed.
Bifunktionelle Katalyse und Mechanismus der Monomethylol‐Bildung aus Harnstoff und Formaldehyd in Wasser
Authors: Eugster P. , Zollinger H. 
Published: December 2004

Abstract
The third‐order catalytic rate constants of the reaction of formaldehyde with urea with 5 general acid‐base catalysts in aqueous solution were measured polarographically in the temperature range 30–45°.
The catalytic constants obtained with hydrogencarbonate, primary and secondary phosphate are higher than expected on the basis of the BRÖNSTED relationship. The activation entropies for the reactions with these catalysts are 15 to 20 entropy units lower than those with the water molecule and the hydroxyl ion as catalysts.
These observations indicate a bifunctional catalysis with a cyclic rate‐determining transition state by the three firstmentioned catalysts. It is postulated that with mono‐ and bifunctional catalysts no termolecular collison step takes place, but first a hydrogen‐bonded complex of the general acid catalyst with formaldehyde or the general base with urea is formed.
Abwandlungen von 18‐Cyanopregnanen II. Synthese von Derivaten des 18‐Homoconanins. 18‐Homoconessin. Über Steroide, 218. Mitteilung
Authors: Kalvoda J. , Anner G. 
Published: December 2004

Abstract18‐Cyano‐pregnenolone, easily available by the ‘oxidative cyanohydrine‐cyanoketone rearrangement’ [3] from pregnenolone cyanohydrine [1], was used as starting material for the synthesis of several representatives of the new group of 18‐homoconanine derivatives, such as 18‐homoconessine (XVIII) and 18‐homolatifoline (XIII).
Über Pyromellitsäure‐ und Cumidinsäure‐Derivate. XIV. Teil [1]. Imidazole aus Pyromellitsäure‐dianhydrid
Authors: Manukian B. K. 
Published: December 2004

AbstractFarbstoffe aus der Reihe der Terephtaloylen‐bis‐benzimidazole stellen für Polyvinylchlorid migrierechte Pigmente dar. Dichlor‐terephtaloylen‐bis‐benzimidazol zeigte in Färbungen von Weich‐PVC eine gute Licht‐ und Migrationsechtheit.
Untersuchungen über Steroide XLII. Umwandlung des 17α‐Pseudostrophanthidins in 19‐Hydroxy‐8, 19‐epoxy‐14β, 17α‐cortexon und 8‐Hydroxy‐19‐nor‐14β, 17α‐cortexon
Authors: Merkel Wolfgang , Ehrenstein Maximilian 
Published: December 2004

AbstractThe synthesis of a structural isomer of aldosterone, viz. 19‐hydroxy‐8, 19‐epoxy‐(11‐) de(s)oxycorticosterone (= 19‐hydroxy‐8, 19‐epoxy‐cortexone), and a number of related compounds was reported earlier from this laboratory [1]. It appeared desirable to prepare the corresponding compounds of the 17α‐series also, such as 19‐hydroxy‐8, 19‐epoxy‐14 β, 17 (βH)‐deoxycorticosterone (28). 17 α‐Pseudostrophanthidin (2), which has not yet been described in the literature, was considered as starting material for the synthesis of 28. 2 has now been prepared by heating a solution of pseudostrophanthidin (1) in dimethylformamide in the presence of sodium p‐toluenesulfonate and anhydrous sodium acetate. 2 was characterized as the 3, 19‐diacetate (7), the 19‐methylal (8) and the 3‐monoacetat (9). 9 was also obtained by acetylating the methylal 8 and demethylating the resulting reaction product 10. To support the structures assigned to 9 and, by implication, to 2, a series of further reactions were carried out.
Effets stéréosélectifs dans les réactions des complexes métalliques. I. Stéréosélectivité de la réaction de l'anion D‐N‐(hydroxy‐2‐éthyl)‐propylènediaminetriacétatoferrate (III) avec quelques dérivés d'acides aminés
Authors: Humbel F. , Vonderschmitt D. , Bernauer K. 
Published: December 2004

AbstractA chromatographic method for studying small effects of ligand stereoselectivity in the formation of labile metal complexes has been developed.It is shown that unidentate ligands can react stereospecifically with labile optically active metal complexes. An anion‐exchanger charged with an optically active form of FeIII‐N‐(2‐hydroxy‐ethyl)‐propylenediamine triacetate is used as a support in chromatography of N‐acylated amino acids, and differences in retentions have been measured by elution and by frontal analysis.
Endocyclische SN‐Reaktionen am gesättigten Kohlenstoff? Vorläufige Mitteilung
Authors: Tenud L. , Farooq S. , Seibl J. , Eschenmoser A. 
Published: December 2004

AbstractFig. 1 illustrates a definition of the terms endocyclic and exocyclic SN‐reactions, referring to intramolecular nucleophilic substitution processes that occur by an SN2‐analogous mechanism.Crossing experiments show that the methyl transfer I → II (see scheme 1) does not follow the formally appealing mechanism of the endocyclic SN‐process III; the reaction proceeds intermolecularly under all conditions investigated. Kinetic measurements indicate that the methyl transfer XI → XII (see scheme 3) occurs in a similar fashion. This behaviour is believed to follow from the preference of tetrahedral carbon for backside attack by the nucleophile in SN2‐reactions.The general experience, according to which intramolecular reaction paths over cyclic transition states with ring sizes of 5 or 6 are preferred to their intermolecular counterparts, is not to be extrapolated to SN2‐reactions at tetrahedral carbon.
Darstellung und Eigenschaften von Tris‐(β‐chloräthyl) phosphinoxid und Bis‐(β‐chloräthyl)‐(chlormethyl)‐phosphinoxid. 43. Mitteilung über organische Phosphorverbindungen [1]
Authors: Maier Ludwig 
Published: December 2004

AbstractThe oxidative degradation of [(HOCH2CH2)3PCH2OH]+Cl− (1) with Cl2 yields, dependent on the pH used, either (HOCH2CH2)3PO (2) or (HOCH2CH2)2 (HOCH2) PO (3). Chlorination of 2 and 3 with PCl5 produces the corresponding chlorides (ClCH2CH2)3PO (4) and (ClCH2CH2)2 (ClCH2)PO (5), respectively. Acetylation of 2 and 3 gives the corresponding esters (CH3CO2CH2CH2)3PO (6), and (CH3CO2CH2CH2)2 (CH3CO2CH2)PO (7), respectively. Reaction of 7 with HBr results in the formation of (BrCH2CH2)2 (BrCH2)PO. Nucleophilic substitution of the chlorine atoms in 4 and 5 with alkoxide or mercaptide gives e.g., 9, 10, 11 or 11a, while treatment with tertiary amines yields the vinyl compounds (CH2CH)3PO (12) and (CH2CH)2 (CH2Cl)PO (13). 4 and 5 also undergo an Arbuzov type reaction with tertiary phosphites to give 14 and 15, respectively, which on hydrolysis with conc. HCl give the corresponding acids 16 and 17, respectively.
Etude de composés d'addition des acides de Lewis ‐ XXXI [1]. Composés d'addition de divers aldéhydes aliphatiques et aromatiques
Authors: Susz B.‐P. , Weber Roberto 
Published: December 2004

AbstractDouze composés d'addition d'aldéhydes avec divers acides de Lewis, possédant une stoechiométrie bien définie, ont été préparés à l'état solide.La fréquence de vibration ω (CO) ≃ 1700 cm−1 de l'aldéhyde subit lors de la synthèse un très fort abaissement, de l'ordre de Δω ≃ −100 cm−1, ce qui prouve que la formation de ces composés est due à une liaison de coordination entre l'oxygène carbonylique et le métal de l'accepteur. Alors qu'en solution dans CH2Cl2 les pics de RMN. des protons non aldéhydiques sont déplacés dans les composés d'addition vers les champs faibles, le pic du proton aldéhydique (τ ∼ 0 ppm) ne change presque pas de position. Δτ du proton aldéhydique peut même être très légèrement positif pour les composés d'aldéhydes benzoïques substitués en para par un groupe électro‐attracteur.Il existe une bonne corrélation linéaire entre Δω et les constantes σp de Hammett. En se basant sur les résultats expérimentaux les auteurs ont calculé pour un modèle de CH3CHO → A à 8 points que la constante de force ƒCO = 10,5 md/Å de l'aldéhyde est abaissée à ƒCO→A = 8,50 md/Å pour le complexe. La contribution de la vibration de valence du carbonyle est d'environ 63% pour 1′Cner‐ gie potentielle de ω(CO) = 1747 cm−1 de l'aldéhyde acétique etd'environ 41% pour ω(CO → A) = 1657 cm−1 du composé d'addition.
Menschliches Calcitonin. VI. Die Synthese von Calcitonin M
Authors: Sieber P. , Riniker B. , Brugger M. , Kamber B. , Rittel W. 
Published: December 2004

AbstractA detailed account is given of the total synthesis of human calcitonin M, the hypocalcaemic hormone possessing the dotriacontapeptide sequence I. In the build up of I, the protected sequences 1–10 and 11–32 served as intermediates for the preparation of the protected precursor dotriacontapeptide 1–32 (II). While the synthesis of the fragment 1–10 has been reported previously [1], the present account includes a detailed description of the build up of the intermediate 11–32. Racemisation encountered in the synthesis of this fragment is discussed and conditions indicated in which it is minimized.From the final coupling step using dicyclohexylcarbodiimide‐N‐hydroxysuccinimide [3], the protected dotriacontapeptide II was obtained pure in a yield of 65% after counter‐current distribution.In the removal by acidolysis of the protecting groups from II even under optimal conditions two side reactions occur: alkylation of the 8‐methionine side chain and N to O acyl migration at the serine or threonine residues. By‐products from these reactions were removed by counter‐current distribution giving very pure I free of diastereoisomers and possessing the biological activity of highly purified natural calcitonin M. In the routine assay [4] after repeated testing its activity was evaluated at 100 ± 5 U/mg (calculated on content of free peptide).
Steroide und Sexualhormone. 237. Mitteilung [1]. Die Synthese von 5βO,19N‐Ep (oxyäthanoimino)‐Steroiden
Authors: Berner H. , Berner‐Fenz Frau L. , Binder R. , Graf W. , Grütter Frl. T. , Pascual C. , Wehrli H. 
Published: December 2004

AbstractThe synthesis of the novel bridged title compounds 13–16 and 21–23 is described.
Recherches dans la série des cyclitols, XL. Préparation de cyclopentane‐triols et de cyclopentène‐triols et ‐diols
Authors: Wolczunowicz G. , Cocu F. G. , Posternak Th. 
Published: December 2004

AbstractTwo as yet unknown cyclopentene‐triols have been prepared. The replacement of the halogen of cyclopentene derivatives brominated in the allylic position has been investigated. In the presence of dimethyl sulfoxide and sodium hydrogen carbonate, the bromine of some of the above mentioned allylic derivatives or the tosyloxy group of a dibenzoyloxy‐monotosyloxy‐cyclopentane derivative is replaced by a hydroxyl group without formation of any keto compound. The mechanism of action of the substitution agents is discussed.
3‐Hydroxyhydantoine: Eine neue Klasse cyclisch diacylierter Hydroxylamine
Authors: Fankhauser P. , Brenner M. 
Published: December 2004

Abstract3‐Hydroxyhydantoins, representing a new class of compounds, are easily accessible from esters of α‐isocyanato fatty acids and hydroxylamine via esters of α‐hydroxyureido fatty acids. Structural assignment is based on Exner correlations of infrared spectra and other physical data. Chemical properties are as expected from those of hydantoins.
Eine neue Synthese von substituierten Arylchinonen mittels elektrophiler Substitution von Phenolen, Phenoläthern, ar. Aminen una ar. Kohlenwasserstoffen durch negativ substituierte 1, 4‐Benzochinone
Authors: Kuser P. , Inderbitzin M. , Brauchli J. , Eugster C. H. 
Published: December 2004

AbstractAcetylbenzochinon und Methoxycarbonylbenzochinon lassen sich in säurekatalysierter Reaktion und unter milden Bedingungen mit Phenolen, Phenoläthern, Dimethylanilin, Alkylbenzolen, Methoxybenzoesäureestern und Hydroxybenzoesäureestern zu Biphenylhydrochinonen und ‐chinonen kondensieren, deren Strukturen durch Spektren und, wenn nötig, durch oxydativen Abbau gesichert wurden. Die Substitutionsorte entsprechen weitgehend denjenigen einer Friedel‐Crafts'schen Acylierungsreaktion.
Synthese und Chiralität der stereoisomeren Achillene, Achillenole und Hymentherene
Authors: Schulte‐Elte K. H. , Gadola M. 
Published: December 2004

Abstract(+)‐cis‐Achillene (10) and (−)‐trans‐achillenol (7), two monoterpenes recently isolated [1] from the essential oil of Achilleafilipendulina, were synthesized, together with their stereoisomers (−)‐(9) and (+)‐(8), starting from (S)‐(+)‐2,6‐trans‐dimethylocta‐1,3, 7‐triene (1).The isomeric ß‐hymen thereties ((−)‐3 and (+)‐4), often quoted [2] [3] [4] but never isolated, were obtained as intermediates. The mode of synthesis chosen establishesis (R)‐chirality for naturally occurring (−)‐trans‐achillenol (7) and (+)‐cis‐achillene (10) as well as for the purely synthetic 4, 7‐diene derivatives described in this paper.
Nuclear Magnetic Resonance Studies of Tertiary Phosphines Adducts with Titanium Tetrachloride, using 1H and 31P
Authors: Calderazzo F. , Losi S. A. , Susz B. P. 
Published: December 2004

AbstractProton and 31P NMR. spectra in solution of several TiCl4PR3 systems have been measured at variable temperatures. The results suggest the presence of fast equilibria in solution involving 1:1 and 1:2 adducts, and free tertiary phosphine. In addition there is evidence for the probable existence, at low temperature, of binuclear species of the type Ti2Cl8(PR3). Correlations are found between the 31P chemical shifts for the 1:1 adducts on the one hand, and Taft's constants and half‐neutralisation potentials on the other. Some new 1:1 and 1:2 TiCl4PR3 adducts have been isolated and have been characterised by analysis and infrared spectroscopy.