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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 744 (1971), S. 81-87 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Pyrroles, Pyrazolines and Pyrazoles via Bis-en-hydrazinesSpecial cyclic and open-chain carbonyl compounds react with N.N′-dimethyl-hydrazine to bis-en-hydrazines 3 as intermediates which by thermolysis or acid catalysis give rise to the formation of N-methyl-pyrroles. Monomethylhydrazine gives in this reaction the same N-methyl-pyrroles, selectively. If the cyclization leads to pyrazolines, then the presence of a suitable leaving group effects the formation of the pyrazole or pyrazolium system by β-elimination.  -  The mechanisms of the reactions are discussed.
    Notes: Spezielle cyclische und offenkettige Carbonylverbindungen liefern bei der Umsetzung mit N.N′-Dimethyl-hydrazin über die entsprechenden Bis-en-hydrazine 3 als Zwischenstufen bei Säurekatalyse oder Thermolyse N-Methyl-pyrrole. Desgleichen führt die Umsetzung mit Monomethylhydrazin selektiv zu N-Methyl-pyrrolen. Infolge einer Konkurrenzreaktion werden gegebenenfalls Pyrazoline gebildet. Das Pyrazolin-System kann dabei, falls β-Eliminierung möglich ist, in das Pyrazol- bzw. Pyrazolium-System umgewandelt werden.  -  Die Mechanismen der Reaktionen werden diskutiert.
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  • 2
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Solvolysis of Spirocyclopropyl-Substituted 2-Benzonorbornenyl Tosylates. A Contribution to the Nature of the 2-Benzonorbornenyl CationThe 2-epimeric at C-7 and C-3 spirocyclopropyl-substituted 2-benzonorbornenols (4a/6a, 7a/9a) have been synthesized. The solvolysis of their tosylates is studied in 80% acetone. Substitution at C-7 shows no important effect, but a spirocyclopropyl group at C-3 has a strong influence on the reaction center at C-2 and a significant decrease of the kexo/kendo ratio is observed (table 1). It is shown that the kinetic results are consistent with the non-classical interpretation of the 2-benzonorbornenyl cation.
    Notes: Die epimeren Alkohole 4a und 6a sowie 7a und 9a werden synthetisiert. Die Solvolyse ihrer Tosylate wird in 80 proz. Aceton untersucht. Während die Spirocyclopropyl-Gruppe an C-7 bei 4a und 6a keinen Einfluß ausübt, zeigt sie an C-3 einen ausgeprägten Effekt, was sich in einer Erniedrigung des kexo/kendo-Verhältnisses ausdrückt (Tab. 1). Die kinetischen Befunde stehen mit der nicht-klassischen Formulierung des 2-Benzonorbornenyl-Kations in übereinstimmung.
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  • 3
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Joint Action of Elementary Sulfur and Gaseous Ammonia on Ketones, LXXVII. Reaction of α-Mercaptoketones with Epoxides and EpisulfidesIn the presence of basic catalysts α-mercaptoketones are added to epoxides to give β-[2-hydroxy-alkylmercapto]-ketones 1a-e (table 1) in an exothermic reaction at room temperature. These are converted to the crystalline 3.5-dinitrobenzoates (table 1) by 3.5-dinitrobenzoyl-chloride. In the presence of acid catalysts the compounds 1a-e condense to substituted 2.3-dihydro-p-oxathiins 2a-x (table 3), which are obtained in good yields also without prior isolation of 1a-e. Using selected examples it is shown that compounds 2a-x give the p-oxathiin-S-oxides 3a-c (table 4) at 0-20° with equimolar amounts of H2O2. With a three-fold molar excess of H2O2 at 70° the p-oxathiin-S-dioxides 4a-g (table 5) are obtained. - Episulfides (Thiiranes) react analogously with α-mercaptoketones to give β-[2-mercapto-alkylmercapto]-ketones (e. g. 5a, c); these condense even without prior isolation to give the substituted 2.3-dihydro-p-dithiins 6a-o (table 6). The p-dithiins 6p-s (table 7) derived from ethylene sulfide are better prepared from α-haloketones and the sodium salt of 1.2-dimercaptoethane to avoid the polymerisation of the ethylene sulfide. - These new syntheses of 2.3-dihydro-p-oxathiins and -p-dithiins may be applied on a broad scale by appropriate choice of the α-mercaptoketones and epoxides or thiiranes.
    Notes: α-Mercaptoketone addieren sich in Gegenwart basischer Katalysatoren bei Raumtemperatur in exothermer Reaktion an Epoxide zu β-[2-Hydroxy-alkylmercapto]-ketonen 1a-e, aus denen mit 3.5-Dinitro-benzoylchlorid die kristallinen Dinitrobenzoesäureester entstehen (Tab. 1). - Die Verbindungen 1a-e kondensieren in Gegenwart saurer Katalysatoren zu substituierten 2.3-Dihydro-p-oxathiinen 2a-x (Tab. 3), die auch ohne Isolierung von 1a-e direkt aus deren Ausgangssubstanzen in guten Ausbeuten erhalten werden. An ausgewählten Beispielen wird gezeigt, daß die Verbindungen 2a-x mit der äquimolaren Menge H2O2 bei 0-20° p-Oxathiin-S-oxide 3a-c (Tab. 4), mit der 3 fach molaren Menge H2O2 bei 70° p-Oxathiin-S-dioxide 4a-g (Tab. 5) bilden. - Analog reagieren Episulfide (Thiirane) mit α-Mercaptoketonen zu β-[2-Mercapto-alkylmercapto]-ketonen (z. B. 5a, c) die auch ohne vorhergehende Isolierung zu substituierten 2.3-Dihydro-p-dithiinen 6a-o (Tab. 6) Kondensieren. Die vom Äthylensulfid hergeleiteten p-Dithiine 6p-s (Tab. 7) lassen sich zur Vermeidung der Äthylensulfid-Polymerisation besser aus α-Halogenketonen und dem Mononatriumsalz des 1.2-Dimercapto-äthans darstellen. - Diese neuen Synthesen für 2.3-Dihydro-p-oxathiine bzw. -p-dithiine besitzen durch Wahlmöglichkeit der α-Mercaptoketone und der Epoxide bzw. Thiirane große Anwendungsbreite
    Additional Material: 13 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 759 (1972), S. 208-210 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation of Pure D-GlucosonePure D-arabino-2-hexosulose (D-glucosone, 5) can be prepared in a yield of 25% by the reaction of 1-amino-1-deoxy-D-fructose-hydrochloride (1) with 3,5-di-tert-butyl-1,2-benzoquinone (2).
    Notes: Durch Umsetzung von 1-Desoxy-1-amino-D-fructose-hydrochlorid (1) mit 3.5-Di-tert.-butyl-1.2-benzochinon (2) erhält man reine D-arabino-2-Hexosulose (D-Glucoson, 5) in einer Ausbeute von 25% d. Th.
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  • 5
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Raman Spectroscopy and Molecular Structure, VII1). - Infrared, Raman and Photoelectron Spectrum of Hexamethylcommat( Dewar Benzene) Normal Coordinate Calculations and Investigation of π-Electron Interaction α′The frequencies and modes of all vibrations of hexamethyl(Dewar benzene) have been calculated. The frequencies thus obtained agree within a mean deviation of 1.3 % with the values observed in the infrared and Raman spectra. The calculated force constants give no indication of ring-strain effects. However, some of the calculated force constants deviate from the expected values. The bond orders derived from force constants according to Siebert) are 0.87 for the central Cl—C4-bond and 1.64 for the C=C-bonds. Surprisingly. The bond orders of the neighbouring single bonds hardly deviate from unity. - The photoelectron spectrum shows a π-electron ionisation potential splitting of 0.41 eV; this is attributed to the competing direct through-space interaction of the π-orbitals as well as to coupling with the central 1,4-σ-orbital. The latter mechanism predominates, and leads to an “inverted” order of the π-orbital energies.
    Notes: Die Frequenzen und Formen sämtlicher Schwingungen des Hexamethyl-Dewarbenzols wurden berechnet. Diese Frequenzen stimmen, bei einer mittleren Abweichung von 1.3 %, mit den im Infrarot- und Ramanspektrum gemessenen überein. Die bei der Berechnung ermittelten Kraftkonstanten zeigen keine Auswirkung der “Ringspannung” des Moleküls. Einige Kraftkonstanten weichen jedoch von den erwarteten Werten ab. Die aus den Kraftkonstanten nach Siebert9) ermittelte Bindungsordnung der zentralen C1 —C4-Bindung beträgt 0.87 und die der C=C-Bindungen 1.64, ohne daß die Bindungsordnung der benachbarten Einfachbindungen wesentlich von 1 abweicht. - Das Photoelektronenspektrum des Hexamethyl-Dewarbenzols zeigt eine Aufspaltung der Ionisationspotentiale der π-Elektronen um 0.41 eV, diese ist auf die gleichzeitige direkte Wechselwirkung der n-Orbitale durch den Raum und durch Kopplung mit dem zentralen (C1 —C4)-σ-Orbital zurückzuführen. Wir sind der Meinung, daß der zuletzt genannte Mechanismus überwiegt und zu einer “invertierten” Ordnung der Energie der π-Orbitale führt.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1974 (1974), S. 809-820 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Elimination Reactions of S,S′-Dimethyl-1,4-dithianium SaltsOn heating a t 140°C with potassium bromide in dimethyl formamide, 2,5-bis(methoxycarbonyl)-S,S′-dimethyl-l,4-dithianium difluoroborate (6) yields methyl 2-(methylthio)acrylate (3a, formed by a normal Hofmann elimination reaction) and 20% of methyl 2,3-bis(methyl- thio)acrylate (4a) in addition to other products. Analogous elimination reactions are also observed with S,S′-dimethyl-1,4-dithianium difluoroborate (9), albeit to a far smaller extent; demethylation of 9 to yield 1,4-dithiane then predominates. Treatment of 9 with phenyllithium yields acetaldehyde dimethyl thioacetal (13) besides normal elimination products. The formation of the thioacetal 13 is explained in terms of a ring contraction of an ylid (formed as primary product of the reaction of 9 with phenyllithium) to yield 1,2,3-trimethyl-1,3-dithiolanium ion. This mechanism appears probable in the light of corresponding reactions of 1,2,3-trimethyl-l,3-dithiolanium difluoroborate (19).
    Notes: 2,5-Bis(methoxycarbonyl)-S,S′-dimethyl-l,4-dithianium-difluoroborat (6) liefert mit Kaliumbromid in Dimethylformamid bei ca. 140°C neben 2-(Methylthio)acrylsäure-methylester (3a, entstanden im Sinne einer normalen Hofmann-Eliminierungsreaktion) in 20proz. Ausbeute 2,3-Bis(methylthio)acrylsäure-methylester (4a) neben anderen Produkten. Analoge Eliminierungsreaktionen werden auch bei S,S′-Dimethyl-l,4-dithianium-difluoroborat (9) beobachtet, allerdings in erheblich geringerem Umfang; hier ist die Entmethylierung zu 1,4-Dithian die Hauptreaktion. Bei Einwirkung von Phenyllithium auf 9 entsteht außer normalen Eliminierungsprodukten auch Acetaldehyd-dimethylthioacetal (13), dessen Bildung durch eine Ringkontraktion des primär aus 9 entstehenden Ylids zu 1,2,3-Trimethyl-1,3-dithiolaniumion erklärt wird. Dieser Mechanismus wird durch entsprechende Umsetzungen von 1,2,3- Trimethyl-1,3-dithiolanium-difluoroborat (19) wahrscheinlich gemacht.
    Additional Material: 2 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1973 (1973), S. 727-729 
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Note on the Photochemical Cycloaddition of 2,3-Dihydro-2,2-dimethyl-4-pyranone to OlefinsPhotoaddition of the title compound 1 to various olefins 2 affords the trans- and cis-fused cyclobutanes 3 and 4. The product ratio 3 : 4 is temperature dependent. A mechanism for the formation of both products via a common intermediate is discussed.
    Notes: Photoaddition der im Titel genannten Verbindung 1 an verschiedene Olefine 2 führt zur Bildung je eines trans- und cis-verknüpften Cyclobutanderivates 3 bzw. 4. Das Produktverhältnis 3 : 4 ist abhängig von der Temperatur der bestrahlten Lösung. Ein Mechanismus für die Bildung beider Produkte über ein gemeinsames Zwischenprodukt wird diskutiert.
    Additional Material: 1 Ill.
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  • 8
    ISSN: 0075-4617
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Methylenecyclopropane, 1- and 3-Methylcyclopropenes from Methallyl Chlorides and Alkali AmidesThe reactions of the α-, β-, and γ-methallylchlorides with alkali amides (Li, Na, K) in various solvents (ethers) were investigated in the temperature range 65-150°C. Improved methods for the syntheses of pure 1-methylcyclopropene (1) and 3-methylcyclopropene (3) have been developed. A new method for the preparation of high purity methylenecyclopropane (2) on a kg-scale from β-methallyl chloride and sodium amide in boiling dibutylether has also been developed. - Ether decomposition, C4H6-Oligomerisations and the formation of β-methallyl- and isobutenyl-amines were found to be the principal side reactions in these C4H6-syntheses.
    Notes: Die Reaktionen der α-, β- und γ-Methallylchloride mit Alkalimetallamiden wurden unter Variation der Alkalimetalle (Li, Na, K), der Lösungsmittel (verschiedene Äther) sowie der Temperatur (65 bis 150°C) untersucht. Es konnten verbesserte Synthesen für reines 1-Methyl-cyclopropen (1) und 3-Methylcyclopropen (3) sowie eine neue Darstellungsmethode für Methylencyclopropan (2) ausgearbeitet werden. Verbindung 2 ist so in hoher Reinheit im kg-Maßstab aus β-Methallylchlorid und Natriumamid in siedendem Dibutyläther zugänglich. - Nebenreaktionen sind C4H6-Oligomerisationen, die Bildung von β-Methallyl- und Isobutenylaminen sowie Ätherspaltungen.
    Additional Material: 9 Tab.
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  • 9
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of oxidation of 4, 6-dimethyl-benzocyclobutenolThis nomenclature is preferred in the literature [1] [2] to the more systematic name (7-hydroxy-3, 5-dimethyl-bicyclo [4.2.0] octa-1,3,5-triene). (1) with chromium trioxide has been measured. After correction for the influence of the two methyl substituents the rate of oxidation of 1 is lower than that of 1-tetralol (9) and 1-indanol (10) by factors of 3 and 5 respectively. The lower oxidation rate of 1 as compared to 9 and 10 is interpreted in terms of a steric rate retardation arising from angle strain in the developing carbonyl function of 4, 6-dimethylbenzocyclobutenone (4).
    Additional Material: 1 Tab.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 55 (1972), S. 2400-2406 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of the reactions between bromide ion and methyl tosylate have been determined in 12 solvents and extrapolated to infinite dilution. The data are correlated with Parker's solvent activity coefficients by means of an empirical equation of the type: logks - logk0 = A log0γsi + B with the constants A = 0.788 and B = 0,108 and a correlation coefficient of 0.983.
    Additional Material: 2 Ill.
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