bluuebunny/crossref_metadata_2025_split huggingface dataset:
Die Komplexe der Hexamine «penten» und «ptetraen» Thermodynamik ihrer Bildung in wässeriger Lösung
Authors: Paoletti P. , Walser R. , Vacca A. , Schwarzenbach G. 
Published: December 2004

AbstractThe two hexamines (H2NCH2CH2)2N(CH2)nN(CH2CH2NH2)2, «penten» (n = 2) and «ptetraen» (n=3) have been investigated as chelating agents for COIII (preparative Study) and some of the divalent metal ions (potentiometric and calorimetric studies). Both amines function as sexadentate ligands for CoIII, CoII and NiII, but one of the terminal aminogroups is much easier detached from the metal in case of M (penten)v+ than in case of M(ptetraen)v+, thus revealing more strain in the fivemembered chelate rings of the girdle plane of the «penten» complexes. On the other hand, the sixmembered chelate ring in M(ptetraen)v+ is more strained than the five‐membered ring comprising the tertiary nitrogen atoms of M(penten)v+ CuII and ZnII coordinate with both ligands only 5 of the 6 basic nitrogen atoms present. Both hexaamines function as sexadentates again with MnII, but the metal is coordinated with a molecule of water in addition to the 6 nitrogen atoms in the «penten» complex in contrast to the «ptetraen» complex. The thermodynamic functions for the protonation of the hexamines and for the addition of metal ions in aqueous solution are understood in almost every detail. The dielectric shielding of the charges of the reactants exerted by the solvent has to be taken into account; it is reduced by electrostriction as well as by an increase in temperature. It is shown that the approach of charges of equal sign often is an exothermic process.
Höhere, kondensierte Ringsysteme. 6. Mitteilung [1]. NBS‐Dehydrierungen an 9,10‐Dihydrophenanthrensystemen Synthese von [23] (2,7) Phenanthrenophan‐trien
Authors: Baumgartner P. , Paioni R. , Jenny W. 
Published: December 2004

AbstractThe usefulness of the low temperature dehydrogenation by N‐bromosuccinimide is illustrated in the 9, 10‐dihydrophenantheren serie. The syntheses of 2, 7‐di‐chloromethyl‐phenanthrene, 2, 7‐di‐bromomethyl‐phenanthrene and hexabromo‐[23] (2,7) phenanthrenophane by NBS‐dehydrogenation are described. Debromination of hexabromo‐[23] (2,7) phenanthrenophane led to [23] (2,7) phenanthrenophane‐triene. The structure of these new compounds was confirmed by NMR.‐, UV.‐ and mass spectroscopy.
Pyrolysis of N‐Sulfinylaniline Microwave Detection of the SO Molecule. Preliminary communication
Authors: Saito Shuji , Wentrup Curt 
Published: December 2004

AbstractGas‐phase pyrolysis of N‐sulfinylaniline at 650–980°C produces SO (3Σ−), identified by its rotational line, J, K = 2,1 → 1,0 in the microwave spectrum, increasing in intensity with the temperature. SO2 was observed with a parallel absorption intensity in the same temperature interval; its partial pressure was determined as ca. 8% at 980°. The results confirm the dissociation of N‐sulfinylaniline into phenylnitrene and sulfur monoxide.
Die molekulare und kristalline Struktur von 9,10‐Dihydro‐4‐(3‐dimethylamino‐propyliden)‐4H‐benzo[4,5] cyclohepta[1,2‐b]thiophen‐hydrochlorid. Untersuchungen über synthetishe Arzneimittel, 19. Mitteilung [1]
Authors: Bastian J. M. , Weber H. P. 
Published: December 2004

AbstractThe α‐isomer of 9,10‐dihydro‐4‐(3‐dimethylamino‐propylidene)‐4 H‐benzo[4,5] cyclohepta [1, 2‐b] thiophen is shown to have the trans configuration by means of an X‐ray analysis of its hydrochloride.
Über den Verteilungssatz der Auxochrome bei Azokörpern, II Dihydroxy‐azobenzole
Authors: Kokkinos K. , Wizinger R. 
Published: December 2004

AbstractThe validity of the rule of repartition of the auxochromes is examined for dihydroxy‐azo and dihydroxy‐4′‐nitro‐azo compounds with hydroxy groups in 2,4‐, 3,4‐ and 2,5‐position. In conformity with the rule the absorption maximum of the 2, 5‐dihydroxy‐azobenzene is situated at a considerably longer wave length than the maximum of 2,4‐dihydroxy‐azobenzene. The 3, 4‐isomer with its absorption maximum at a relatively short wave‐length seems to contradict the rule. On the other hand all alkali salts of both series conform to the rule of repartition in an impressive way.
Zur Photochemie des Caryophyllens und des iso‐Caryophyllens Umlagerungen ihrer 1,5‐Diensysteme nach direkter π,π*‐Anregung in flüssiger Phase
Authors: Schulte‐Elte K. H. , Ohloff G. 
Published: December 2004

AbstractWhen caryophyllene (1) and isocaryophyllene (2) are irradiated at their π,π*‐ transitions (λ ≤ 253.7 nm) they rearrange relatively rapidly and in high yield to mixtures of isomeric sesquiterpene hydrocarbons. Compounds 3–11, the structural determinations of which are described, represent 90% of the photoisomers. All the rearrangements involve the 1, 5‐diene systems, and, with the exception of cis‐trans isomerizations, fragmentation of the doubly allylic σ‐bond and disappearance of the trisubstituted double bond always occur. The cyclopropane, acetylene, allene, and 1, 5‐diene compounds resulting are the first examples of this type of photo‐isomerization products obtained from unconjugated monomeric 1, 5‐dienes by direct excitation with light. Their formation appears to be stereospecific, and is dependent on the stereochemistry of the double bond system in 1 and 2. In addition to the cis‐isomer 2 caryophyllene yields only compounds 3, 4, and 5, while from isocaryophyllene, compounds 8, 9, 10 and 11 are formed in addition to 1. The only isomerization products common to both caryophyllenes (1 and 2) are 6 and 7. This behaviour and the lack of positive identification of a biradical (triplet) intermediate lead to the probable conclusion that the greater part of the photoisomerization occurs directly from the excited singlet states. Possible mechanisms for the formation of the photoisomerization products are discussed.
Die Synthese von Insulinfragmenten mit intakter interchenarer Disulfidbrücke A20‐B19
Authors: Kamber B. 
Published: December 2004

AbstractThe synthesis of six insulin fragments is described, in which various sequences of the two chains are linked by the disulfide bridge between A20 and B19. The fragments in question are: A20–21–B19–21, A20–21–B18–21, A20–21–B17–21, A19–21–B19–21, A16–21–B18–21 and A20–21–B12–21.In order to build up the simpler fragments the disulfide bridge was established by oxidation with iodine of two S‐trityl cysteine peptides in which the carboxyl and amino groups were protected by the t‐butyl and t‐butyloxycarbonyl residue. From the mixture obtained the unsymmetrical cystine peptide was separated in all cases from the two symmetrical ones by counter‐current distribution.In the synthesis of the more complex fragments advantageous use was made of smaller unsymmetrical fragments prepared as above but having one amino group protected by the N‐trityl residue. After selective elimination of this group it was possible to lengthen the peptide chain at this position.The free peptides were obtained by removal of the protecting groups with strong acids, in particular concentrated hydrochloric acid. While in this deprotecting step the disulfide bond was stable, conditions are discussed under which disproportionation was observed.None of the six synthetic insulin fragments showed activity in stimulating rat adipose tissue to convert 14C‐labelled glucose to CO2 in vitro.
Berechnung von freien Hydratationsenthalpien und Koordinationszahlen für Kationen aus leicht zugänglichen Parametern
Authors: Morf W. E. , Simon W. 
Published: December 2004

AbstractA model for the computation of free energies of hydration and coordination numbers of cations using easily available parameters is described. For 27 mono‐, di‐ and trivalent cations the mean deviation of the calculated from the experimental ΔG°H values is 3.9%. All the computed coordination numbers agree with experimental ones.
Gentisinacetal und Chlorgentisinalkohol, zwei neue Metabolite einer Phoma species
Authors: Séquin‐Frey M. , Tamm Ch. 
Published: December 2004

AbstractFrom cultures of a Phoma species (strain S729) (Fungi imperfecti) gentisylalcohol (1), toluhydroquinone (3), and two new metabolites, gentisylacetal (2) and chlorogentisylalcohol (4), have been isolated. The structure of 2 was proven by cleavage to gentisylalcohol (1) and acetaldehyde, and by resynthesis from these moieties. The synthesis of chlorogentisylalcohol (2,5‐dihydroxy‐3‐chloro‐benzyl alcohol) (4) and its two isomers 5 and 6 from chlorohydroquinone (10) via the aldehydes 7,8, and 9 respectively established the structure of this metabolite.
Photochemical Reactions. Part 63 [1]. The photodecarbonylation of α‐aryl aldehydes
Authors: Küntzel H. , Wolf H. , Schaffner K. 
Published: December 2004

AbstractUltraviolet irradiation of the aldehydes 6–11 in degassed solutions results exclusively in decarbonylation to the major products 34, 35 and 37–40, and to small amounts of 2, 3‐diphenyl‐2, 3‐dimethyl‐butanes 36 from the phenyl aldehydes 6 and 7. In the presence of tri‐n‐butylstannane, incorporation of stannane hydrogen competes, to substrate‐specific limits, with the intramolecular deuterium transfer in 7 → 35 and 11 → 40. The quantum yields for decarbonylation are Φ ∼ 0.4–1.0 for the phenyl aldehydes 6 and 9, and 0.02 for 8. Hammett correlations of Φ with resonance constants (R) for 6 (X = H, p‐CH3, OCH3) and (CF3) and with ωm+ values for the meta‐substituted isomers are in agreement with the proposed α‐cleavage to an associated radical pair with only moderate free radical character as the primary photochemical step.Φ for 10 (X = H) is 0.11, and for 10 (X = OCH3) 0.065. It is noteworthy that decarbonylation of 10 (X = OCH3) occurs also at 3340 Å (ΦCO = 0.11) i.e., upon excitation in an absorption band which is presumably lower in energy than the n → π* transition and corresponds to the aromatic Lb transition of 2‐methoxynaphthalene.Singlet multiplicity of the reactive excited states is probable on the basis of the fact that the decarbonylation of 6 (X = H) and 10 (X = H and OCH3) could be sensitised neither by acetone nor acetophenone, and could be quenched neither by naphthalene nor by cis‐1, 3‐pentadiene and nor by 1, 3‐cyclohexadiene.
Stabilité des carboxylates de terres rares, IV N‐acétylglycinates
Authors: Roulet R. , Chenaux R. , Vu Duc T. 
Published: December 2004

AbstractThe stability constants of N‐acetylgycinates of some rare earths in aqueous solution have been determined by a potentiometric method, and by a solvent extraction technique. The ligand forms 1:1 complexes which are stabilized by relatively large positive entropies of formation, the corresponding enthalpies being endothermic. This backs up the assumption that a conjugate base of an amino acid forms innersphere complexes and acts as a unidentate ligand towards a rare earth cation, like a simple carboxylate.
Chiroptische Eigenschaften und Äquilibrierungen stereoisomerer Yohimbane und ihrer 17‐Ketoderivate
Authors: Bartlett L. , Klyne W. , Dastoor N. J. , Schmid H. , Hrbek J. , Snatzkec G. 
Published: December 2004

AbstractThe chiroptical properties (CD. and ORD.) of four stereoisomeric yohimbanes (1–4) and the corresponding 17‐keto derivatives 5–8 have been studied. The aromatic and the ketonic Cotton effects have been considered in terms of the appropriate Sector and Octant Rules, respectively. Positively charged nitrogen makes an ‘anti‐octant’ contribution to the ketonic Cotton effect.The chiroptical properties, the NMR. spectra and dehydrogenation reactions with mercuric acetate together indicate the presence of a C/D‐trans‐quinolizidine system in all the compounds studied, except those of the pseudo series (3 and 7), in which a C/D‐cis‐quinolizidine system is present. An explanation of the unexpectedly slow dehydrogenation of the 3‐epi‐allo compounds 4 and 8 is suggested.Conformational analysis of the results of equilibration experiments on pairs of 3‐epimeric compounds (in both glacial acetic acid at 145° and in K‐t‐butylate at 211°) leads independently to conclusions which agree with those drawn from the physical methods. The great differences between the equilibrium positions of the free bases and the protonated forms are due to the presence in the latter cases of oriented ion pairs R3N+H…︁−O2CCH3.
Molecular Conformation of Benzylideneanilines
Authors: Bürgi H. B. , Dunitz J. D. 
Published: December 2004

AbstractThe non‐planar conformations of benzylideneanilines and the almost planar conformations of stilbene and azobenzene are consistently reproduced by a simple model, which takes into account the dependence of π‐electron energy and non‐bonded interactions on molecular conformation. Other aspects of the molecular geometry of benzylideneanilines.(bond angles influence of p‐substituents) are also discussed.
Synthese und Auftrennung von racemischen, isomeren Desoxo‐demethylcassain‐Derivaten. 1. Mitteilung über Cassain‐Analoga
Authors: Hauth H. , Stauffacher D. 
Published: December 2004

AbstractFor the synthesis of analogues of Erythrophleum alkaloids the tricyclic ketones 3 (trans‐anti‐trans) and 5 (trans‐anti‐cis) were prepared. Reaction of 3 and 5 with triethyl phosphonoacetate led to a mixture of cis/trans compounds, which could be separated in a preparative scale into the uniform racemic isomers 8 and 9, 22 and 23, respectively. Transesterification of these compounds gave the corresponding 2‐dimethylamino‐ethyl esters.
Zur Konfiguration racemischer 14‐Demethyl‐cassensäure‐und ‐isocassensäure‐Derivate. 2. Mitteilung über Cassain‐Analoga [1]
Authors: Hauth H. , Niklaus P. , Stauffacher D. 
Published: December 2004

AbstractThe structures of four synthetic isomeric analogues of cassaine were confirmed by detailed interpretation of their NMR. spectra.
Nachweis von (+)‐epi‐Muscarin in Inocybe geophylla. 36. Mitteilung über Muscarin und verwandte Stoffe
Authors: Bollinger H. , Eugster C. H. 
Published: December 2004

AbstractDie enantiomeren epi‐Normuscarine lassen sich in Form der diastereomeren α‐Methoxypropionsäureester gas‐chromatographisch trennen. Bei Verwendung von (S)‐α‐Methoxypropionsäure als Veresterungskomponente konnte gezeigt werden, dass das in Inocybe geophylla (Sow. ex Fr.) Quél. (Basidiomycetes) vorkommende epi‐Muscarin das (+)‐Enantionmere darstellt.
Contribution à l'étude du système quaternaire KClRbClCsClH2O: II. L'isotherme de 25°C
Authors: Merbach A. , Gonella J. 
Published: December 2004

AbstractThe experimental study at 25°C of the system KClRbClCsClH2O has shown the existence of a new type of quaternary system with formation of mixed crystals. — The solubility diagram is characterized by the presence of one univariant line and one binary miscibility gap. Two types of solid solutions are present: (K, Rb, Cs) Cl and (K, Rb, Cs) Cl; the incorporation in the latter is small.
Catalytic Aminomethylation of Alkenoic Compounds: I. Reaction of monoolefins with secondary amines, carbon monoxide, and water in the presence of rhodium and iron catalysts
Authors: Iqbal Abul F. M. 
Published: December 2004

AbstractReactions, in the presence of rhodium oxide and/or iron pentacarbonyl, of cyclic or acyclic higher olefins with carbon monoxide, water, and secondary amines to give the corresponding aminomethyl‐cycloalkanes or ‐alkanes (equ. 1) are described. As catalyst rhodium oxide is by far superior to iron carbonyl; however, optimum results are obtained with combinations of the two. The method can be applied to synthesis of long‐chain alkylamines, which are valuable as intermediates for synthetic detergents.
n→π*‐Übergänge in Dicarbonylverbindungen Der Einfluss der n, n‐ und π*, π*‐Wechselwirkung
Authors: Hug W. , Kuhn J. , Seibold K. J. , Labhart H. , Wagnière G. 
Published: December 2004

AbstractBy CNDO‐CI calculations we have found that dicarbonyl compounds exhibit only two n → π* transitions in the visible or near UV. region, instead of four as expected from simpler MO‐models. The dominant features of the long‐wavelength electronic spectra may be characterized by the relative energy of the two n and the two lowest π* orbitals. In general we distinguish between three cases:

Large splitting (about 2 eV) both between the n and the π* orbitals. The longest‐wavelength n → π* transition is shifted to the red. The higher transition remains roughly where it would appear in the monocarbonyl compound.
No or very small splitting between either the two n, or the two π* orbitals, or both. Both n → π* transitions merge, roughly, in the wavelength region of the corresponding monocarbonyl compound.
Intermediate (0.5–1.0 eV) splitting between the two n orbitals on one hand, the two π* orbitals on the other. Spectral properties between A. and B.
The splitting between the two n orbitals and the two π* orbitals depends not only on the distance between the two carbonyl groups, but also very strongly on their mutual position and on the nature of the molecular fragment connecting them. As one would expect, in α‐dicarbonyl compounds the splitting between the n orbitals is large, namely 1.8 eV. In some γ‐diketones such as P‐quinone, one still finds, however, a value of 0.7 eV. The splitting between the n orbitals gets significantly lowered if the two carbonyl groups are coaxial, but their 2pπ nodal planes are perpendicular to each other. In planar β‐diketones the splitting between the π* orbitals is small, but may increase to an effective value of 0.4 eV when they are skewed.Our calculations agree well with measured electronic spectra and CD. data. An electrochromism experiment on camphorquinone convincingly supports our conclusions on α‐dicarbonyl compounds.
Chimie et pharmacologie de l'apiose. IV. (Hydroxyméthyl‐3‐β‐D‐érythrofurannosyl)‐9‐adénine: Synthèse, conformation en solution et essais biologiques préliminaires
Authors: Tronchet J. M. J. , Tronchet Mme J. 
Published: December 2004

AbstractThe title compound, an apionucleoside, has been synthesized and is shown by NMR. to exist mainly in the conformation E3′. The reasons why this branched‐chain nucleoside is not a substrate for adenosine deaminase are discussed. The compound inhibits the growth of Escherichia coli and Staphylococcus aureus in synthetic liquid media.
Reaction of Bicyclo[3.2.1]octenols with Thionyl Chloride. Preliminary paper
Authors: Jefford C. W. , Gunsher J. A. 
Published: December 2004

AbstractThe allylic 1‐methyl‐3‐bromobicyclo[3.2.1]octenyl exo‐2 and exo‐4 alcohols were treated with thionyl chloride in ether or pentane solution at 0°. In each case, a 50/50 mixture of exo allylic chlorides was obtained. No evidence for a predominant SN l′ reaction was detected; reported cases of such SN l′ processes using these conditions should therefore be treated with reserve.
Die Jodierung von desaktivierten aromatischen Aminen in wässeriger Phase
Authors: Toth I. 
Published: December 2004

AbstractBy treatment of deactivated aromatic amines such as 4‐nitroaniline, 4‐aminobenzonitrile or 2‐bromo‐4‐nitro‐aniline with iodine in water at 90–93° for 30–35 hours, in the presence of hydrogen peroxide, monoiodinated products with over 99% purity are obtained in 88–98% yield.
Reaktivität von Koordinationsverbindungen, XXIII [1]. Bildung und Zerfall des Sauerstoffadduktes mit N,N′‐Bis‐(4‐(5)‐imidazolylmethyl)‐äthylendiamin‐kobalt (II)‐Ionen
Authors: Zuberbühler A. , Kaden Th. , Koechlin F. 
Published: December 2004

AbstractIn aqueous solution N, N′‐bis‐(4‐(5)‐imidazolylmethyl)‐ethylenediamine‐cobalt (II) (CoIMEN2+) takes up molecular oxygen giving μ‐dioxygen‐μ‐hydroxo‐bis‐[N, N′‐bis‐(4‐(5)‐imidazolylmethyl)‐ethylenediamine]‐dicobalt (II). (Co IMEN)2 O2 (OH)3+ is exceptionally stable against irreversible autoxydation to CoIII species. Its absorption spectrum is very similar to that of the known analogous complex (CoTRIEN)2 O2 (OH)3+.The kinetics of formation and dissociation of (CoIMEN)2O2(OH)3+ are studied by spectrophotometry and with an oxygen specific electrode. The rate of the forward reaction is described by vf = [CoIMEN2+]2 · [O2] · (k1 + k2 · [OH−]) with k1 = 9 · 104 M−2 s−1 and k2 = 1 · 1012M−3 S−1, at 25° and I = 0,2. A mechanism including hydroxylated as well as nonhydroxylated intermediates is proposed. Dissociation is preceeded by protonation of the oxygen adduct. At pH 1–2 the rate of dissociation is independent of [H+] and follows first order kinetics: vD = k3 · [(CoIMEN)2O2(OH)3+] with k3 = 2.15 · 10−2 S−1.
Über Sapogenine. 1. Mitteilung. Über die Konstitution eines neuen Sapogenins aus Helleborus odorus Waldtst. et Kit. und Helleborus niger L.
Authors: Linde Hermann F. G. , Isaac Otto , Linde Horst H. A. , Živanov Dobrila 
Published: December 2004

AbstractA new sapogenin, 1, isolated from Helleborus odorus Waldst. et Kit. and Helleborus niger L. (Ranunculaceae) is shown to be spirost‐5,25 (27)‐dien‐1b̃, 3b̃, 11α‐triol.
Das organoleptische Prinzip von Cassis‐Flavor im Buccublätteröl
Authors: Sundt E. , Willhalm B. , Chappaz R. , Ohloff G. 
Published: December 2004

AbstractThe diastereoisomeres of p‐menthone‐8‐thiol, derived from (+)‐menthol, are the first ketothiols of the terpene series to have been found in nature. Stereochemistry, methods of preparation and olfactory properties of the new compounds are described.
Synthesen der stereoisomeren (±)‐γ‐Damascone
Authors: Schulte‐Elte K. H. , Rautenstrauch V. , Ohloff G. 
Published: December 2004

AbstractUnder the conditions of the Wharton reaction, the (±)‐epoxy‐γ‐dihydroionones 2 and 3 are transformed into the allylic alcohols 4–10. γ‐Damascols 4, 5 and 8 were oxidised to cis‐ and trans‐γ‐damascone 12 and 13. Alternatively, dehydro‐γ‐damascol 18 was obtained by Wittig rearrangement of butinyl ether 17, and converted into damascones 12 and 13.
Spectres de masse des composés organiques. 5e communication. Perte de méthane et d'éthylène à partir des ions butyle
Authors: Liardon Réamy , Gäann Tino 
Published: December 2004

AbstractThe loss of methane and ethylene in the mass‐spectrometric fragmentation of different isomeric butyl ions which originate from butyl halides has been studied. The different carbon atoms in n‐butyl are already equivalent after 10−7 s, whereas the statistical distribution of the hydrogen atoms within the molecule can only be observed for the metastable peaks. A protonated cyclobutane structure is proposed as an intermediate product in the fragmentation of the n‐butyl ion. The fragmentation of this model has been simulated by a computer. This allows prediction as to the time‐scale of fragmentation. The comparison of this model fragmentation with that of isomeric butyl ions shows that, even in the decay of the tertiary butyl ion, the formation of the proposed rearranged cyclic structure competes favorably with the direct fragmentation.
Indolo[3,3a,4‐gh]chinoline und 10a, 6a‐Iminopropano‐indolo‐[3,3a,4‐gh]chinoline. Stereospezifische Synthesen und Umlagerungen. Teil II. 9. Mitteilung über synthetische Indolverbindungen
Authors: Stoll André P. , Niklaus P. , Troxler F. 
Published: December 2004

AbstractAlkaline hydrolysis of 1‐benzyl‐4, 4‐dicyanoethyl‐5‐oxo‐1,3,4,5‐tetrahydro‐benzo‐[cd]indole under controlled conditions leads to 4‐benzyl‐4,6,7,8‐tetrahydro‐10a, 6a‐iminopropanoindolo[3,3a,4‐gh]quinoline‐9(10H),12‐dione (2a), the first representative of such a ring system. Alkylation of this di‐lactam affords the N‐monoalkyl (2b), the N, N'‐dialkyl (3), and the N, O‐dialkyl (4) derivatives according to the conditions employed. Treatment of compounds such as 2 with sodium in liquid ammonia results in the opening of one of the lactam rings by a stereoelectronically controlled reductive cleavage of the benzylamine bond; subsequent protonation proceeds stereospecifically to give trans‐octahydroindolo[3,3a, 4‐gh]quinolines (viz. 5). The NMR. spectra and the mechanism of the reductive ring opening are discussed.
Synthese von 2‐Thioaldosen über α,β‐ungesättigte Nitrokörper
Authors: Wirz P. , Hardegger E. 
Published: December 2004

AbstractDie basenkatalysierte Reaktion von Thiocarbonsäuren oder Benzylmercaptan mit dem aus D‐Arabinose leicht zugänglichen α,β‐ungesättigten Nitrokörper III verläuft kinetisch kontrolliert bevorzugt zu Verbindungen der Reihe V mit D‐manno‐Konfiguration. Am Beispiel des Benzylthioäthers Vb wurde ein präparativ gangbarer Weg zur Synthese von 2‐Thio‐D‐mannose (XIV) und 2‐Thio‐D‐glucose (XVIII) gewiesen.