2,6-Epoxy-3-benzazocine: Zentral wirksame N/O-Acetale durch Ringschluß von Amino- und Amidoacetalen

2,6-Epoxy-3-benzazocines: Centrally Active N/O-Acetals by Cyclization of Amino- and Amidoacetals Under acidic conditions the secondary amines 10a and 10b , the primary amine 15 , the amide 17a , and the urethane 17b were cyclized to yield the 2,6-epoxy-3-benzazocines 11a, 11b, 16, 18a and 18b , respectively. Ring closure of the inverse amide 5a , however, failed to give the tricyclic N/O-acetal 6 . With LiAlH₄ the epoxy bridge of the urethane 18b was opened to afford the bicyclic 3-benzazocine 20 . - While the N-(2-methoxyethyl) derivative 11b did not influence the behaviour of mice, the N-methyl derivative 11a showed strong central effects.     

Zur GC Analyse und zu chemischen Typen von Kamillenöl

GLC Analysis and Chemical Types of Chamomile Essential Oil Using the silicone phase QF-1 the best separation so far of the chamomile essential oil components, especially α-bisabolol and α-bisabolone oxide A, was carried out. Bisabolone oxide A¹ occurs in the majority of chamomile essential oils and it represents the dominant substance in the essential oil of Bulgarian origin. A high content of α-bisabolol was also found in the essential oil of Spanish origin.     

Über Abkömmlinge des Isothiochroman-S-dioxids Mitt. über Untersuchungen in der Isochroman- und Isothiochroman-Reihe

The aminoethylation of isothiochroman-S-dioxide (Ia) and 1-phenyl-isothiochroman-S-dioxide (Ib) is reported. The cyanoethylation of Ia yields the dinitrile IV, which can be transformed to the dicarboxylic acid Va, to the esters Vb and Vc, and also to the diamide Ve.     

Zur Reaktion von Quadratsäuredimethylester mit N,N-disubstituierten Hydrazin-Derivaten

The Reaction of Squaric Acid Dimethyl Ester with N,N-Disubstituted Hydrazines Reaction of 3,4-dimethoxy-3-cyclobutene-1,2-dione (2) with N,N-disubstituted hydrazines yields 3,4-bishydrazino-3-cyclobutene-1,2-diones 3 , which are converted into 3-amino-4-hydrazino-3-cyclobutene-1,2-diones 6 with N-N splitting by refluxing in ethanol.     

Über Mannichbasen, 17. Mitt. Amino- und Amidoalkylierung von 2-Methylnaphthol bzw. 1-Naphthol

Mannich Bases, XVII: Amino- and Amidoalkylation of 2-Methylnaphthol and 1-Naphthol Under the usual conditions of aminoalkylation 2-methylnaphthol yields the Mannich bases or the methylene biscompound 4 depending on the basicity of the amine. With iminium salts, however, the hydrochlorides of the aminoalkyl derivatives are obtained. The amidoalkylation of 1-naphthol yields mono- or disubstituted products depending on the starting components.     

Zur Objektivierung der Kühlwirkung von Kühlsalben, -gelen und Lotionen

On the Objective Measuring of the Cooling Effects of Cooling Topics An apparatus is described for measuring the cooling effect of topic preparations in cal or J and its registration in terms of temperature-time-cooling profiles. Ten dermathetics had cooling effects between 0 and 1900J/ml. The results of the 6 effective ones agreed with those obtained through sensoric analysis, but were more exact and could be better reproduced; in particular the duration of the cooling-effect is only measurable with the instrument and not sensorically. Results of the sensoric analysis were influenced by the colours of the preparations, but not by their smells. It is reported how the nature of gel formers as well as the consistency and the alcohol concentration of cooling gels influence the cooling effect.     

Thion- und Dithioester, 52. Mitt.: Zur Reaktion von Dithionmalonestern mit N,N-Dimethylformamidacetalen

Thiono and Dithio Esters, LII¹⁾: Reaction of Dithiono Malonates with N,N-Dimethylformamide Acetals The reaction of the dithiono malonates 1 with the formamide acetals 2 leads to the 2-dialkylaminomethylene dithionomalonates 4 and the thiono acrylates 6 . The condensation of 4 with hydrazines gives rise to the pyrazoles 7 and 8 , with hydroxylamine sulfonic acid to the isothiazoles 10 , and with amidines to the pyrimidines 11 - 13 .     

Zur Acetylierung von Spironolacton,Canrenon und 2-Methylencanrenon

Acetylation of Spironolactone, Canrenone, and 2-Methylene Canrenone Reaction of the title compounds with acetic anhydride and acetyl chloride yields the 3,5-dien-3-yl acetate 2 the isomeric 2,4,6- and 3,5,7-trien-3-yl acetates 3 and 4 as well as the 2,4,6,8(14)-tetraen-3-yl acetate 7 . The 2α-methyl-8,14-didehydro-canrenone ( 9 ) is obtained by hydrolysis of 7 . Binding affinities of 7 and 9 to hormone receptors as well as serum proteins (SHBG, CBG) are investigated. The compounds are inactive.     

Zur biologischen Bildung von N,N-Dimethylanilin-N-Oxyd und N,N-Dimethylaminoazobenzol-N4-Oxyd aus den Aminen sowie ihre Reaktionen mit Hämoglobin und mit Lebermikrosomen

Zusammenfassung An Meerschweinchen wurden die Wirkungen einiger Veratrum-Alkaloide auf die Impulsaktivität der Lungendehnungsreceptoren und auf die Atemtätigkeit untersucht. Bei intravenöser Verabreichung zeigten das Alkaloidgemisch Veratrin und die Einzelalkaloide Veratridin, Cevadin, Germin, Desacetylgermitetrin und Germitetrin, sowie Protoveratrin A und Protoveratrin B eine erregende Wirkung auf die Lungendehnungsreceptoren mit erheblichen Unterschieden bezüglich der Wirkungsdauer und der Dosimetrie. Es ließ sich ein rasch eintretender, kurzwirkender Veratrin-Typ bei Veratrin, Veratridin, Cevadin, Germin und Desacetylgermitetrin von einem langsam einsetzenden, langdauernden Protoveratrin-Typ bei Protoveratrin A, Protoveratrin B und Germitetrin unterscheiden.Bei beiden Typen folgte dem Maximum der Receptorenerregung eine Phase der Desensibilisierung. Am Beispiel von Veratrin wurde mit der von uns verwendeten Methode für die Erregungswirkung eine vollständige Dosis-Effekt-Kurve aufgestellt.Innerhalb der niedrigen Dosenbereiche kam es bei Veratrinsulfat und Protoveratrin A zu einer Tachypnoe, die durch Bivagotomie und Endoanaesthetica verhindert werden konnte. Bei höherer Dosierung trat die bekannte vagal-reflektorische Apnoe auf.

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Summary In guinea-pigs, various veratrum-alcaloids have been investigated on lung-stretch-receptors and on respiratory behaviour.Intravenous administration of veratrine, veratridine, cevadine, germine, desacetylgermitetrine, germitetrine as well as protoveratrine A and protoveratrine B brought about receptor stimulation of different degree and duration. Two types of stimulation could be distinguished: (1) the veratrine-type with immediate begin and short-lasting action as seen after veratrine, veratridine, cevadine, germine and desacetylgermitetrine and (2) the protoveratrine-type with delayed onset and long-lasting action as seen after protoveratrine A, protoveratrine B and germitetrine. The maximum of stimulation was followed by a phase of desensitization. By help of our method it became possible to set up a dose-effect-curve for the stimulative action of veratrine.Small doses of veratrine and of protoveratrine A caused tachypnea which could be prevented by endoanaesthesia. High doses brought about the well known vagus-induced reflex-apnea.

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Herrn Professor Dr. O. Schaumann zum 75. Geburtstag gewidmet.     

Zur Mannich-Reaktion von Hydrocodon und Oxycodon

Mannich-Reaction of Hydrocodone and Oxycodone The reaction of hydrocodone and oxycodone with N,N-dimethylmethylene iminium salts yields the Diels-Alder dimers of the 7-methylene ketones, exclusively. The structure of the spiro compounds 2 is proved by ms and nmr spectroscopy. Problems of the nomenclature are discussed.     

Zur Entgiftung von Schlafmitteln und Basisnarkotica

Ohne Zusammenfassung     

Zur Reinigung und Wirkungsweise von Kallikreinen

Ohne Zusammenfassung     

Zur Polymorphie von Arzneistoffen: Medrogeston,Phensuximid und Protionamid

On the Polymorphism of Drugs: Medrogestone, Phensuximide and Protionamide Medrogestone forms a metastable modification II, which occurs in the commercial product that was investigated. In addition, there exists an unstable modification III. From Phensuximide two modifications were prepared in addition to the stable crystalline one. They were characterized by their melting points and infrared spectra. Protionamide shows enantiotropy between modification I and II; the commercial product is modification II. Modifications III and IV are rather unstable.     

Zur N- und C-Silylierung von β-Lactamen

N- and C-Silylation of β-Lactams Silylation of 1,4-disubstituted β-lactams 1 yields 3-silyl compounds 2 , which isomerize to yield 3 . By an analogous reaction 5 and/or 6 were prepared from 4-phenyl-2-azetidinone ( 4 ). The N-silyl intermediates 7 and 8 were isolated and fully characterized. Reactions of silylated β-lactams with aldehydes or acetyl chloride are reported.     

Zur Struktur von Kondensationsprodukten aus Acetondicarbonsäureestern und Aldehyden

Structure of the Condensation Products of Dialkyl Acetone Dicarboxylates and Aldehydes Studies of ¹H-NMR-spectra have shown that the condensation products of dialkyl acetone dicarboxylates and aldehydes are substituted cyclohexanone-oles and that alkylidene-bis-structure for these compounds is not correct.