TY - JOUR A1 - Zilch, H. A1 - Tacke, Reinhold T1 - Fluorid-induzierte Fragmentierung von Acetyldimethylphenylsilan N2 - Acetyldimethylphenylsilane (2) reacts with TBAF · 3H\(_2\)O in THF and with KF in DMSO/H\(_2\)0, respectively, to give [(CH\(_3\) )\(_2\)SiO]\(_x\) and 1-Phenylethanol (3) which can be isolated with a nearly quantitative yield. The way 2 reacts with F\(^-\) contrasts with that of some aroyl- and heteroaroyltrimethylsilanes, described in the literature. A reaction mechanism is discussed which involves among others a 1 ,2-phenyl shift and a Brook rearrangement. N2 - Acetyldimethylphenylsilan (2) reagiert bei Raumtemperatur mit TBAF · 3H\(_2\)O in THF bzw. mit KF in DMSO/H\(_2\)O zu [(CH\(_3\))\(_2\)SiO]\(_x\) und 1-Phenylethanol (3), welches mit praktisch quantitativer Ausbeute isoliert werden kann. Dieses Reaktionsverhalten von 2 gegenüber F\(^-\) weicht drastisch ab von dem in der Literatur beschriebenen Verhalten einiger Aroyl- und Heteroaroyltrimethylsilane. Ein Reaktionsmcchanismus, der u.a. eine 1,2-Phenylverschiebung und eine BrookUmlagerung beinhaltet, wird zur Diskussion gestellt. KW - Anorganische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63802 ER - TY - JOUR A1 - Wrobel, D. A1 - Tacke, Reinhold A1 - Wannagat, U. A1 - Harder, U. T1 - Sila-Analoga tertiärer Carbinole mit Duftwirkung T1 - Sila Analogues of Tertiary Carbinols as Perfumes N2 - Es wurden Silanale RR'R"SiOH 7 dargestellt, die Carbinolen RR'R"COH 1 (R = CH\(_3\) , R' = CH\(_3\) , CH = CH\(_2\) , C\(_2\)H\(_5\) , R" = CH\(_2\)C\(_6\)H\(_5\) , CH\(_2\)CH\(_2\)C\(_6\)H\(_5\)) mit starker Duftwirkung im Bereich blumiger Noten (Maiglöckchen-Hyazinthe-Rose) analog waren. Ihr Syntheseweg verläuft über die Reaktionsschritte (3) mit teilweise bisher unbekannten Zwischenstufen 6. Die Sila-Riechstoffe 7 sind in Intensität und Duftbereich den Carbinolen 1 ähnlich, doch ist allgemein eine Verschiebung der Duftnote von Maiglöckchen zu Hyazinthe zu beobachten. N2 - Silanals RR'R"SiOH 7 which areanalog to carbinols 1 with strong odour in the region of flowery notes (lily of the valley-hyacinth-rose) were prepared via reaction steps (3) and partially unknown intermediates 6. Sila perfumes 7 are similar in intensity and spectrum of odour to 1 but a shift from lily of the valley towards hyacinth notes is generally observed. KW - Anorganische Chemie Y1 - 1982 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63705 ER - TY - JOUR A1 - Wiese, D. A1 - Tacke, Reinhold A1 - Wannagat, U. T1 - 9,9-Dimethyl-10-(3-dimethylaminopropyl)-9-silaacridan, ein Sila-Analogon des Dimetacrins, und strukturverwandte Verbindungen T1 - 9,9-Dimethyl-10-(3-dimethylaminopropyl)-9-silaacridane,a Sila-Analogue of Dimetacrine, and Structurally Related Compounds N2 - Das Sila-Dimetacrin (3a), ein Sila-Analogon des Psychopharmakons Dimetacrin (2), und sein N,N-Diethylderivat 3 b sowie sein 3-Chlorderivat 3 c wurden, von den o-Halogenanilinen 4 a- c ausgehend, über die teilweise unbekannten Stufen 5 a- c bis 10a- d synthetisiert, in ihren Eigenschaften beschrieben und in ihrer Struktur über Elementaranalysen, \(^1\)H-NMR- und Massenspektren sichergestellt. Die Synthese des Zwischenproduktes Bis(2-bromphenyl)amin (9a) konnte optimiert werden. N2 - Sila-dimetacrine (Ja), a sila-analogue of the psychotropic drug dimetacrine (2), and its N,N-diethyl derivative 3 b as well as its 3-chloro derivative 3 c were synthesized from o-haloanilines 4 a- c via the - partially unknown - intermediates S a- c to 10 a- d. Their properties are described and their structure is confirmed by eiemental analysis, \(^1\)H-NMR, and mass spectroscopy. The preparation of the intermediate bis(2-bromophenyl)amine (9a) could be improved. KW - Anorganische Chemie Y1 - 1981 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63691 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Zimonyi-Hegedüs, E. A1 - Wannagat, U. T1 - Si-C-Spaltung in 2-Thienylsilanen durch sekundäre Amine N2 - Die Umsetzung von Diphenyl-vinylsilan mit zyklischen sekundären Aminen (z.B. Morpholin) in Gegenwart der entsprechenden Lithium-amide führt zu einer Substitution des an Silicium gebundenen H-Atoms durch eine Aminogruppe und zu einer Addition des Amins an die Vinylgruppe. 2-Thienylphenyl- vinylsilan reagiert jedoch zusätzlich unter Spaltung der Si-e-Bindung und Aminosubstitution der 2-Thienylgruppe. N2 - Treatment of diphenylvinylsilane with cyclic secondary amines (e.g. morpholine) in the presence of the corresponding Iithium amides leads to substitution of the SiH hydrogen atom by an amino group and to. addition of the amine to the vinyl group. A similar reaction observed in the case of 2-thienylphenylvinylsilane is accompanied by cleavage of the Si-e band and substitution of the 2-thienyl group by an amino group. KW - Anorganische Chemie Y1 - 1979 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63608 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Zimonyi-Hegedüs, E. A1 - Strecker, M. A1 - Heeg, E. A1 - Berndt, B. A1 - Langner, R. T1 - Sila-Analogon des Tiemoniumiodids T1 - Sila-Analogue of Tiemonium Iodide N2 - Sila-Tiemoniumiodid (16b), ein Sila-Analogon des Anticholinergicums Tiemoniumiodid (16a), und das Sila-Analogon 14b der entsprechenden Tiemonium-Base 14a wurden erstmalig synthetisiert.14b und 16b sowie die Vorstufen 10-13 und 15 wurden in ihren physikalischen und chemischen Eigenschaften charakterisiert und in ihrer Struktur durch Elementaranalysen sowie \(^1\)H-NMR- und Massenspektren sichergestellt. Die spasmolytischen Eigenschaften der Paare 14a/14b und 16a/16b wurden am isolierten Meerschweinchendarm vergleichend untersucht. N2 - Silatiemonium iodide (16b), a sila-analogue of the anticholinergic tiemonium iodide (16a), and the siJa-analogue 14b of the corresponding free base 14a were synthesized for the first time. Compounds 14b and 16b as weil as their precursors 10-13 and 15 were characterized by their physical and chemical properties. Their structures were confirmed by elementary analyses, (^1\)H NMRand massspectroscopy. The spasmolytic properties of the pairs 14a/14b and 16a/16b were compared on the isolated guinea pig ileum. KW - Anorganische Chemie Y1 - 1980 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63669 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wiesenberger, Frank A1 - Lopez-Mras, Angel A1 - Sperlich, Jörg A1 - Mattern, Günter T1 - Neuartige zwitterionische λ5-Spirosilicate: Synthese und Kristallstruktur von Bis[1,2-benzoldiolato(2-)][2-(dimethylammonio)phenyl]silicat sowie Synthese von Bis[2,3-naphthalindiolato(2-)][2-(dimethylammonio)phenyl]silicat-Hemiacetonitril-Solvat N2 - No abstract available. KW - Silicate KW - Bis[1,2-benzenediolato(2-)][2-(dimethylammonio)phenyl]silicate KW - Bis[2,3-naphthalenediolato(2-)][2-(dimethylammonio)phenyl]silicate KW - zwitterionic λ5-Spirosilicates Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-86916 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wiesenberger, Frank T1 - (Acetoxymethyl)methylphenylgerman: Synthese, thermisches Verhalten und olfaktorische Eigenschaften T1 - (Acetoxymethyl)methylphenylgermane: Synthesis, Thermal Behaviour and Olfactoric Properties N2 - No abstract available. KW - Chemische Synthese KW - Temperaturabhängigkeit KW - Olfaktorische Analyse KW - (Acetoxymethyl)methylphenylgermane KW - (Acetoxymethyl)methylphenylsilane KW - hydratropyl acetate KW - thermal stability KW - perfumes Y1 - 1991 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-86927 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wiesenberger, F. A1 - Becker, B. A1 - Rohr-Aehle, R. A1 - Schneider, P. B. A1 - Ulbrich, U. A1 - Sarge, S. M. A1 - Cammenga, H. K. A1 - Koslowski, T. A1 - Niessen, W. von T1 - Ester von (Hydroxymethyl)diorganylsilanen: Synthese und thermisch induzierte Umlagerung T1 - Esters of (Hydroxymethyl)diorganylsllanes: Synthesis and Thermally Induced Rearrangement N2 - Twenty silanes of the type R\(^1\)R\(^2\)Si(H)CH\(_2\)OR\(^3\) (A) were syn- and entropy of activation) of these reactions were studied by thesized {R\(^1\), R\(^2\) = Me, Ph, 1-naphthyl, PhCH\(_2\), Me\(_3\)SiCH\(_2\); OR\(^3\) means of düferential scanning calorimetry (DSC). In addition, = OC(O)Me, OC(O)Ph, OC(O)CF\(_3\) , OS(0)\(_2\)CF\(_3\), OP(O)Ph\(_2\), the kinetics of all reactions were investigated by 1H-NMR OC(O)Cl, and studied for their thermal behaviour. The silanes spectroscopy. The transition state of the rearrangement was A undergo a thermally induced rearrangement to give the investigated by an ab initio study based on the model comcorresponding silanes R\(^1\)R\(^2\)Si(OR\(^3\))Me (B). For compounds with pound H\(_3\)SiCH\(_2\)OC(O)H (-> MeH\(_2\)SiOC(O)H]. The theoretical OR3 = OC(O)Cl, an additional decarboxylation takes place to data and the experimentally obtained energetic and kinetic yield the chlorosilanes R1R2Si(Cl)Me. Except for the deriva- data are discussed in terms of mechanistic aspects of the retives with OR\(^3\) = OC(O)Cl, the energetic (reaction enthalpy) arrangement reaction A -> B. and kinetic data (reaction order, frequency factor, enthalpy ... KW - Anorganische Chemie Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64188 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wannagat, U. T1 - Sila-Analoga des Mephenhydramins T1 - Sila-Analogues of Mephenhydramine N2 - Sila-Analogues A 2, B 2 and C 2 of the drug mephenhydramine from the class of benzhydryl ethers were synthesized for the first time by the steps shown in scheme 1, and they and their precursors I-V characterized by their physical {table 1) and chemical properties, and their structures confirmed by NMR, n1ass and infrared spectroscopy (tables 3-5). Their physiological effects were investigated a.nd compared -with those of the parent carbon compounds (section 5). KW - Anorganische Chemie Y1 - 1975 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63525 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wannagat, U. T1 - Sila-Analoga des Chlorphenoxamins und des Clofenetamins T1 - Sila-Analogues of Ohlorphenoxamine and Clofenetamine N2 - Sila-ana.logues A 2 and B 2 of two drugs from the benzhydryl ether class, chlorphenoxamine and clofenetamine, were synthesized for the first time by the steps shown in scheme 1. They and their precursors I-VI v;rere characterized by their physical (Table 1) and chemical properties and their structures confirmed by n.m.r., mass and infrared spectroscopy (Tab]es 2-5). Their physiological effects were invest.igated and compared with those of the carbon analogues (Chapter 5). KW - Anorganische Chemie Y1 - 1976 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63531 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wannagat, U. T1 - Sila-Analoga des Mebrophenhydramins T1 - Sila-Analogues of Mebrophenhydramine N2 - Sila-analogues A 2, B 2 and C 2 of the drug mebrophenhydramine from the class of benzhydryl ethers -were synthesized for the first time by the steps shown in scheme 1, and they and their precurso:rs I-Ill were characterized by their physical (Table 1) and chemical properties, a.nd their structures confirmed by NMR, mass and infrared spectroscopy (Tables 3-5). The histaminolytic and anticholinergic effects of A 2 and C 2 were investigated and compared with some structure-activity relationships of analogue carbon compounds. KW - Anorganische Chemie Y1 - 1976 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63542 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wannagat, U. T1 - Sila-Analogon des Cicloniumbromids T1 - Sila-Analogue of Ciclonium Bromide N2 - Sila-Analogues B 2 and A 2 of the spasmolytic ciclonium bromide (B 1) respectively the corresponding free base A 1 were synthesized for the first time according to the reaction steps sho·wn in scheme 1, and they and their precursors I and II were characterized by ph;ysical (Table 1} and chemical properties and their structures confirmed by NMR, and mass spectroscopy (Tables 2 and 3}. The pharmacological effects of A 2 and B 2 were investigated and compared with those of the parent carbon compound B 1 (chapter 5). KW - Anorganische Chemie Y1 - 1976 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63556 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wannagat, U. T1 - Derivate des Sila-Mephenhydramins und Sila-Chlorphenoxamins T1 - Derivatives of Sila-Mephenhydramine and Sila-Ohlorphenoxamine N2 - Derivatives A and B of the two sila-antihistam.ines silamephenhydramine and sila-chlorphenoxamine were synthesized for the first time by the steps shown in scheme 1. They and their precursors III and IV were characterized by their physical (Table 1) and chemical properties and their structures confirmed by NMR and mass spectroscopy (Tables 2 and 3). Their pharmacological effects were investigated and compared with those of the corresponding sila-antihistamines. KW - Anorganische Chemie Y1 - 1976 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63562 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wannagat, U. T1 - Isoelektronische Derivate des Sila-Clofenetamins und des Sila-Mebrophenhydramins T1 - Isoelectronic Derivatives of Sila-Clofenetamine and Sila-Mebrophenhydramine N2 - Isoelectronic derivatives (A and B) and a homolog (C) of the two sila-antihistamines sila-clofenetamine and silamebrophenhydramine were synthesized for the first time by the steps shown in scheme 1. They and their unknown precursors II-IV were characterized by their physical (Table 1) and chemical properties and their structures confinned by lH-NMR and rnass spectroscopy (Tables 2 and 3). The pharrnacological effects of A and B were investigated and compared with those of the corresponding 0-isosteric sila-antihistarnines (Chapter 5). KW - Anorganische Chemie Y1 - 1976 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63574 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wannagat, U. T1 - N-Quaternäre Derivate basischer Sila-benzhydryläther T1 - N-Quaternary Derivatives of Basic Silabenzhydryl Ethers N2 - Die quartären Ammoniumsalze 1-10 einiger bioaktiver Sila-benzhydryläther wurden erstmalig durch Reaktion der entsprechenden freien Basen A-E mit CH\(_3\)J, CH\(_3\)Br bzw. CH\(_3\)Cl in CH\(_3\)CN dargestellt. Die Strukturen von 1-10 wurden durch Elementaranalysen und 1 H-NMR-Spektren bestätigt. Die pharmakologischen Effekte einiger Verbindungen wurden sowohl mit den Eigenschaft der entsprechenden freien Basen als auch mit einigen Struktur-Wirkungsbeziehungen analoger Kohlenstoffverbindungen verglichen. N2 - Quaternary ammonium salts 1-10 of some biologically active silabenzhydryl ethers were synthesized for the frrst time by the reaction of the corresponding free bases A-E with CH\(_3\)I, CH\(_3\)Br or CH\(_3\)Cl in CH\(_3\)CN. The structures of 1-10 were confirmed by elementary analysis and 1 HNMR spectroscopy. The pharmacological effects of some compounds were compared with those of the corresponding free bases and of analogaus carbon cornpounds. KW - Anorganische Chemie Y1 - 1977 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63583 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Wagner, S. A. A1 - Sperlich, J. T1 - Synthese von (-)-(Acetoxymethyl)(hydroxy-methyl)methyl(phenyl)german [(-)-MePhGe(CH\(_2\)OAc)(CH\(_2\)OH)] durch eine Esterase-katalysierte Umesterung: Die erste enzymatische Synthese eines optisch aktiven Germans N2 - No abstract available. KW - Anorganische Chemie KW - Germane KW - optically active KW - Biotransformation KW - stereoselective Transesterification KW - enzymatic KW - Porcine liver esterase Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64310 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Strecker, M. A1 - Sheldrick, W. S. A1 - Ernst, L. A1 - Heeg, E. A1 - Berndt, B. A1 - Knapstein, C.-M. A1 - Niedner, R. T1 - Sila-Pridinol und Pridinol: Darstellung und Eigenschaften sowie Strukturen im kristallinen und gelösten Zustand T1 - Sila-Pridinol and Pridinol: Preparation and Properties as weil as Structures ln the Solid Stateand in Solution N2 - Sila-Pridinol (2 b), ein Sila-Analogon des Anticholinergicums Pridinol (2a), wurde auf zwei verschiedenen Wegen dargestellt. Die Kristall- und Molekülstrukturen von 2 a und 2 b wurden röntgenstrukturanalytisch bestimmt. 2a bildet im festen Zustand intramolekulare Wasserstoffbrückenbindungen aus, während sich in kristallinem 2 b zentrosymmetrische, durch intermolekulare H-Brückenbindungen verknüpfte cyclische Dimere finden. IR- und \8^1\)H-NMR-spektroskopische sowie kryoskopische Untersuchungen ergaben Informationen über die Strukturen von 2a und 2 b in verschiedenen Lösungsmitteln. - Die pharmakologischen und toxikologischen Eigen" schaften von 2a und 2b wurden unter dem Gesichtspunkt bekannter Struktur-Wirkungs-Beziehungen vergleichend untersucht. 2 b erwies sich als ein etwa fünfmal so starkes Anticholincrgicum wie 2a. N2 - Sila"pridinol (2 b), a sila"analogue of the anticholinergic pridinol (2a). was prepared by two different routes. The crystal and molecular structures of 2 a and 2 b were determined by X-ray structural analyses. 2a forms intramolecular hydrogen bonds in the solid state, whereas centrosymrnetric cyclic dimers linked through intermolecular hydrogen bonds are observed for crystalline 2 b. IR- and \(^1\)H NMR spectroscopic as weil as cryoscopic studies yielded information ab out the structures of 2a and 2 bin different solvents. - The pharmacological and toxicological properties of2a and 2b were compared with one another on the basis ofknown structure-activity relationships. The anticholinergic properties of 2b were found tobe about five times as strong as those of 2a. KW - Anorganische Chemie Y1 - 1980 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63654 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Strecker, M. A1 - Niedner, R. T1 - Cholinesterase-hemmende Organophosphorsäureester und ihre Sila-Analoga T1 - Organophosphates with Anticholinesterase Activity and their Sila-Analogues N2 - Die Organophosphorsäureester la-4a und ihre Sila-Analoga lb-4b des Typs R\(^1\)R\(^2\)P(O)( p-OC\(_6\)H\(_4\)ElMe\(_3\)) (EI = C, Si) wurden synthetisiert. Die Kohlenstoff-Verbindungen 1 a- 4a zeigen hinsichtlich ihrer Anticholinesterase-Aktivität die gleichen Struktur-Wirkungs-Beziehungen wie die Silicium-Verbindungen 1 b- 4 b. Letztere sind jeweils wirksamer als die entsprechenden C-Analoga. N2 - The organophosphates la-4a and their sila-analogues lb-4b of the type R\(^1\)R\(^2\)P(O)( p-OC\(_6\)H\(_4\)ElMe\(_3\) (El = C, Si) were synthesized. With regard to their anticholinesterase activity, the carbon compounds ta- 4a exhibit the same structure-activity relationships as the silicon compounds 1 b- 4b. The latter are more activ than the corresponding C-analogues. KW - Anorganische Chemie Y1 - 1981 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63689 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Strecker, M. A1 - Lambrecht, G. A1 - Moser, U. A1 - Mutschler, E. T1 - (2-Aminoethyl)-cycloalkylphenylsilanole: Bioisosterer C/Si-Austausch bei Parasympatholytika vom Typ des Trihexyphenidyls, Cycrimins und Procyclidins T1 - (2-Aminoethyl)cycloalkylphenylsilanols: Bioisosteric C/Si Exchange in Parasympatholy1ics of lhe Trihexyphenidyl, Cycrimine, and Procyclidine Type N2 - Die Synthese der (2-Aminoethyl)cycloalkylphenylsilanole Sb (Sila-Trihexyphenidyl), 6b (SilaCycrimin), 7 b (Sila-Procyclidin) und Sb wird beschrieben. Sb- Sb wurden - ausgehend von Cl\(_2\)(C\(_6\)H\(_5\))SiCH = CH\(_2\) (9) - durch eine fünfstufige Reaktionsfolge mit einer Gesamtausbeute von 32- 40% erhalten. Am isolierten Ileum des Meerschweinchens wurden die C/Si-Paare Sa, b- 8a, b vergleichend auf ihre antimuskarinische Aktivität geprüft. Die durch die Sila-Substilution von Sa-8a erreichte Zunahme der Affinität zum Muskarinrezeptor ist deutlich weniger ausgeprägt als bei den strukturverwandten C/Si-Paaren I a, b- 4a, b. N2 - Thc synthesis of thc (2-aminoethyl)cycloalkylphenylsilanols Sb (sila-trihexyphenidyl), 6b (silacycrimine), 7b (sila-procyclidine), and Sb is described. Starting with Cl2(C6H5)SiCH = CH2 (9), Sb- 8 b were obtained by five reaction steps with a total yield of 32- 40%. The C/Si pairs Sa,b- 8a, b were tested for antimuscarinic activity on the isolated guinea-pig ileum. Thc increase of affinity for the muscarinic reccptor caused by sila-substitution of S a- 8a is less marked than in the case of the structurally related C/Si pairs la,b-4a,b. KW - Anorganische Chemie Y1 - 1983 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63741 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Strecker, M. A1 - Lambrecht, G. A1 - Moser, U. A1 - Mutschler, E. T1 - Bioisosterer C/Si-Austausch bei Parasympatholytika vom Typ des Pridinols T1 - Bioisosterie C/Si Exchange in Parasympatholytia of tbe Pridinol Type N2 - Die Synthese der (2·Aminoethyl)diphenylsilanole 3b und 4b wird beschrieben. Die parasympatholytischen Eigenschaften der CISi-Paare la/lb-4a/4b wurden am isolierten Ileum des Meerschweinchens untersucht. In allen Fällen führt der C/Si-Austausch zu einer Zunahme der Affinität zum Muskarin-Rezeptor. N2 - The synthesis of the (2·aminoethyl)diphenylsilanols 3b and 4b is described. The Q'Si pairs lallb-4a/4b were tested for atropine-like activity on the isolated guinea-pig ileum. In all cases the C/Si exchange Ieads to an increased affinity for the muscarine-sensitive acetylcholine receptor. KW - Anorganische Chemie Y1 - 1984 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63766 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Sperlich, Jörg A1 - Strohmann, Carsten A1 - Frank, Brigitta A1 - Mattern, Günter T1 - Bis[3,4,5,6-tetrabrom-1,2-benzoldiolato(2-)]-(pyrrolidiniomethyl)silicat-Acetonitril-Solvat [(C6Br4O2)2SiCH2(H)NC4H8 · CH3CN]: Synthese sowie Kristall- und Molekülstruktur eines zwitterionischen [lambda]5-Spirosilicats N2 - Single crystal X-ray studies on bis[3,4,5,6-tetrabromo-1 ,2-benzenediolato(2- )](pyrrolidiniomethyl)silicate acetonitrile solvate [(C6Br40 2hSiCH2(H)NC4H8 · CH3CN; monoclinic, P2t/c, a = 808.5(4), b = 1533.0(8), c = 2212.6(1) pm, ß = 97.67(2)0 , Z = 4] revealed a zwitterionic structure with a pentacoordinate, formally negatively charged silicon atom and a positively charged ammonium moiety. The silicon atom is surrounded by four oxygen atoms and one carbon atom in a trigonalbipyramidal fashion, with the carbon atom in an equatorial position. The structure is displaced by 7.0% from the trigonal bipyramid towards the square pyramid. The zwitterion and the CH3CN molecule form intermolecular N-H · · · N hydrogen bonds. KW - Kristallstruktur KW - Spirosilicate KW - crystal structure KW - zwitterionic spirosilicate Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-86884 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Rohr-Aehle, R. T1 - Ester des (Hydroxymethyl)[(trimethylsilyl)methyl]silans: Synthese und thermisch induzierte Umlagerung N2 - Die Synthese des (Hydroxymethyl)[(trimethylsilyl)methyl]silans (3) sowie des hiervon abzuleitenden Acetats 4 und Chlorformiats 6 wird beschrieben. 4 und 6 unterliegen einer thermisch induzierten Umwandlung zu den difunktionellen Silanen 5 bzw. 8. Die Umwandlungen 4 -> 5 und 6 -> 8 erfolgen gemäß einer Kinetik 1. Ordnung mit Halbwertszeiten von 10.0 bzw. 3.6 h (135 ° C, in C\(_6\)D\(_6\)). N2 - The synthesis of (hydroxymethyl)[(trimethylsilyl)methyl]silane (3) and that of the corresponding acetate 4 and chloroformiate 6 are described. 4 and 6 undergo a thermally induced rearrangement to give the difunctional silanes 5 and 8, respectively. The transformations 4 -> 5 and 6 -> 8 follow a first order rate law with half life times of 10.0 and 3.6 h, respectively (135 o C, in C\(_6\)D\(_6\) ). KW - Anorganische Chemie Y1 - 1988 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63889 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Pikies, J. A1 - Linoh, H. A1 - Rohr-Aehle, R. A1 - Gönne, S. T1 - Sila-Procyclidin: Eine neue Synthese sowie Untersuchungen zur peripheren und zentralen anticholinergen Wirkung N2 - Sila-Procyclidin (1 b) sowie dessen Derivate 2b (Sila-Tribexyphenidyl), 3b und 4b (Sila-Cycrimin) wurden - ausgehend von Cl\(_3\)SiCH\(_2\)Cl - durch eine neue, sechsstufige Synthese mit einer Gesamtausbeute von 16 (lb), t9 (2b), 8 (3b) bzw. 7% (4b) dar· gestellt. - Vergleichende in-vivo-Untcrsuchungen (Maus, per-osApplikation) hinsichtlich der peripheren und zentralen auticholincrgen Wirkung haben gezeigt, daß die Silicium-Verbindung 1 b dem Kohlenstoff-Analogon Ia (Procyclidin) überlegen ist. N2 - Starting with Cl\(_3\)SiCH\(_2\)Cl. sila-procycUdine (I b) as well as its derivatives 2b (sila-trihexyphenidyl), 3b, and 4b (sila-cycrimine) were prepared by a new six-step synthesis witb a total yield of 16 (lb), 19 (2b), 8 (31) aud 7% (4b), respectively. - Comparative in vivo investigations (mice per os administration) with respect to the peripheral and centrat anticholinergic activity bavc shown that the silicon compound 1 b is advantageous over the c:arbon aualogue t a (procyclidine). KW - Anorganische Chemie Y1 - 1987 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63815 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Niedner, R. A1 - Frohnecke, J. A1 - Ernst, L. A1 - Sheldrick, W. S. T1 - Darstellung und Eigenschaften potentiell curarewirksamer Silicium-Verbindungen, II T1 - Preparation and Properties of Silicon Compounds withPotential Curare-Like Activity, II N2 - Die potentiell curarewirksamen Silicium-Verbindungen Sa, Sc, Sd, Sg, Sh und 9a-9d wurden dargestellt. \(^1\)H-NMR-spektroskopische Untersuchungen ergaben Informationen über die Konformationen von 5 a- Sc in Lösung. Die Kristall- und Molekülstruktur von 5 c wurde röntgenstrukturanalytisch bestimmt. Die muskelrelaxierenden Eigenschaften von S a- 5 h und 9 a-9 d wurden vergleichend an der Maus (i.v., LD50-Werte) untersucht. Die ermittelten Struktur-WirkungsBeziehungen werden in Hinblick auf die unterschiedlichen kovalenten Radien des Kohlenstoffund Siliciumatoms und die hieraus resultierenden N ... N-Abstände diskutiert. N2 - 'The potential curare-like silicon compounds Sa, Sc, Sd, Sg, Sb, and 9a-9d were synthesized. \(^1\)H-NMR spectroscopic investigations provided information about the conformations of Sa-Sc in solution. The crystal and molecular structures 5 c were determined by X-ray structural analysis. The muscle relaxing properties of Sa-Sb and 9a-9d were investigated comparatively on mice (i. v., LD50 values). The observed structure-activity relationships are discussed with respect to the different covalent radii of the carbon and silicon atoms and the N ... N distances resulting therefrom. KW - Anorganische Chemie Y1 - 1980 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63670 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Niederer, Reinhold T1 - Sila-Pharmaka, 9. Mitt. [1] Darstellung und Eigenschaften potentiell curarewirksamer Silicium-Verbindungen, I T1 - Sila-Drugs, 9th Communication [1] Preparation and Properties of Silicon Compounds with Potential Curare-Like Activity, I JF - Zeitschrift für Naturforschung B N2 - Organosilicon compounds 8, 9 and 10 with potential curare-like action and their precursors 0, 6 and 7 were synthesized for the first time. 0-10 were characterized by their physical and chemical properties, and their structures were confirmed by analyses, IH NMR and mass spectroscopy (only for 0-7). The pharmacological and toxicological data of 8, 9 and 10 are reported. KW - curare-like activity KW - toxicological properties KW - pharmacological properties KW - silicon compounds Y1 - 1978 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-128277 VL - 33 IS - 4 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Mühleisen, M. A1 - Jones, P. G. T1 - Das erste zwitterionische, optisch aktive Disilicat mit pentakoordiniertem Silicium N2 - No abstract available KW - Anorganische Chemie Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64343 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Mühleisen, M. T1 - Hexakoordiniertes Silicium in einer molekularen Verbindung mit einer F\(_5\)SiC-Einheit N2 - No abstract available KW - Anorganische Chemie Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64365 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Lopez-Mras, A. A1 - Sperlich, J. A1 - Strohmann, C. A1 - Kuhs, W. F. A1 - Mattern, G. A1 - Sebald, A. T1 - Neue zwitterionische \(\lambda_5\)-Spirosilicate: Synthesen, Einkristall-Röntgenstrukturanalysen und Festkörper-NMR-Untersuchungen T1 - New Zwitterionic \(\lambda_5\)-Spirosilicates: Syntheses, Single-Crystal X-Ray Strudure Analyses, and Solid-State NMR Studies N2 - The zwitterionic spirocyclic \(\lambda_5\) -Silicates bis(3,4,5,6-tetrabromo- 1,2-benzenediolato(2- ))[2-(pyrrolidinio)ethyl]silicate (5; and its monohydrate 5 · H\(_2\)O) and bis[1,2-benzenediolato(2- )][( dimethylammonio)methyl]silicate (6) were synthesized by various methods including Si-C bond cleavage reactions. The crystal structures of 5, 5 · H\(_2\)O, and 6 were investigated by Xray düfraction. Furthermore, 5, 5 · H\(_2\)O, 6, and the related zwitterionic \(\lambda_5\)-spirosilicates 1 · 1/4 CH\(_3\)CN, 2 · CH\(_3\)CN, 3 · CH\(_3\)CN, and 4 were characterized by solid-state NMR spectroscopy (\(^{29}\)Si and \(^{15}\)N CP/MAS). The pentacoordinate silicon atoms of 5, 5 · H\(_2\)O (two crystallographically independent ZWitterions and two crystallographically independent water molecules), and 6 (two crystallographically independent zwitterions) are surrounded by four oxygen atoms and one carbon atom. The coordination polyhedrons around the silicon atoms of 5 and 6 can be described as distorted (5) or nearly ideal (6) trigonal bipyramids, the carbon atoms being in equatorial positions. 5 forms intramolecular and 6 intermolecular (--+ formation of dimeric units) N- H···O hydrogen bonds. The coordination polyhedrons around the two crystallographically independent silicon atoms of 5 · H\(_2\)O can be described as a nearly ideal and slightly distorted square pyramid, respectively, the carbon atoms being in the apical positions. In the crystal lattice of 5 · H\(_2\)O, intermolecular N-H···O and 0-H···O hydrogen bonds between the zwitterions and water molecules are observed. The results obtained by X-ray diffraction and solid-state NMR spectroscopy are consistent for each compound studied. KW - Anorganische Chemie KW - Spirosilicates KW - zwitterionic KW - Silicon KW - pentacoordinate KW - Bond cleavage KW - Si-C I Solid-state NMR KW - 29Si and 15N Y1 - 1993 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64251 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Lopez-Mras, A. A1 - Sheldrick, W. S. A1 - Sebald, A. T1 - Synthesen, Einkristall-Röntgenstrukturanalysen und \(^{29}\)Si-Festkörper-NMR-Untersuchungen eines zwitter- ionischen \(\lambda_5\)-Spirosilicats und eines käfigartigen Octa(silasesquioxans) : [Professor Hartmut Bärnighausen zum 60. Geburtstage gewidmet] T1 - Syntheses, Single-Crystal x ... Ray Analyses and Solid-State \(^{29}\)Si NMR Studies of a Zwitterionic \(\lambda_5\)-Spirosilicate and a Cage-like Octa(silasesquioxane) N2 - No abstract available KW - Anorganische Chemie Y1 - 1993 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64243 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Lopez-Mras, A. A1 - Becht, J. A1 - Sheldrick, W. S. T1 - Synthese sowie Kristall- und Molekülstruktur von Tetrafluoro[2-(pyrrolidinio)ethyl]silicat T1 - Synthesis and Crystal and Molecular Structure of Tetrafluoro[2-(pyrrolidinio)etbyl]silicate N2 - Das zwitterionische Tctratluoro[2-(pyrrolidinio) ethyl]silicat (4) wurde durch Reaktion von Trimethoxy( 2-pyrrolidinoethyl)silan (5) mit Fluorwasserstoff in einem Ethanol/Flußsäure-Gemisch bei 0 °C synthetisiert. Die Kristall- und Molekülstruktur von 4 wurde bei - 100 °C mittels einer Einkristall-Röntgenstrukturanalyse untersucht. Außerdem wurde 4 durch NMR-Untersuchungen in Lösung charakterisiert (CD\(_3\)CN: \(^1\)H, \(^{13}\)C). N2 - The zwitterionic tetrafluoro[2-(pyrrolidinio) ethyl]silicate (4) was synthesized by reaction of trimethoxy( 2-pyrrolidinoethyl)silane (5) with hydrogen fluoride in elhanollhydrofluoric acid at 0 °C. The crystal and mo1ecular structure of 4 was studied at - 100 °C by singlc-crystal X-ray diffraction. ln addition, 4 was characterized by solution-state NMR sturlies (CD\(_3\)CN: \(^1\)H, \(^{13}\)C). KW - Anorganische Chemie KW - Zwitterionic KW - Lambda5-organofluorosilicate KW - pentacoordinate silicon KW - crystal structure Y1 - 1993 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64269 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Linoh, Haryanto A1 - Stumpf, Burghard A1 - Abraham, Wolf-Rainer A1 - Kieslich, Klaus A1 - Ernst, Ludger T1 - Mikrobiologische Umwandlung von Silicium-Verbindungen: Enantioselektive Reduktion von Acetessigsäure-(trimethylsilylalkyl)estern und deren Carba-Analoga T1 - Microbiological Transformation of Silicon Compounds: Enantioselective Reduction of Trimethylsilylalkyl Acetoacetates and their Carba-Analogues JF - Zeitschrift für Naturforschung B N2 - The trimethylsilylalkyl acetoacetates 1 b and 2 b as well as their carba analogues 1 a and 2 a have been reduced microbiologically by Kloeckera corticis (ATCC 20109), leading to the corresponding ( + )-3(S)-hydroxybutanoates 3b, 4b, 3a, and 4a. The enantiomeric purity was found to be 80% (3a, 3b, 4b) and 65% (4a), respectively. The reduction of lb and 2b is - to our knowledge - the first example for a controlled microbiological transformation of organosilicon substrates. KW - enantioselective reduction KW - microbiological transformation KW - silicon compounds Y1 - 1983 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-128304 VL - 38 IS - 5 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Linoh, Haryanto A1 - Attar-Bashi, Moayad T. A1 - Sheldrick, William S. A1 - Ernst, Ludger A1 - Niedner, Roland A1 - Frohnecke, Joachim T1 - Sila-Pharmaka, 26. Mitt. [1] Darstellung und Eigenschaften potentiell curarewirksamer Silicium-Verbindungen, III T1 - Sila-Pharmaca, 26th Communication [1] Preparation and Properties of Silicon Compounds with Potential Curare-Like Activity, III JF - Zeitschrift für Naturforschung B N2 - The potentially curare-like silicon compounds 8a- 8f were synthesized and investigated with respect to their structure-activity relationships. The conformations of the compounds in the solid state and in solution were studied by X-ray diffraction analysis (8a- 8e) and IR NMR spectroscopy (8a- 8f), respectively. The muscle relaxing properties of 8a- 8f were investigated on the mouse. The observed structure-activity relationships are not in accordance with the classical "14 Å model" for neuromuscular blocking agents. KW - structure-activity relationships KW - X-ray KW - curare-lik activity KW - silicon compounds KW - conformational anaylses Y1 - 1982 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-128402 VL - 37 IS - 11 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Linoh, H. A1 - Zilch, H. A1 - Wess, J. A1 - Moser, U. A1 - Mutschler, E. A1 - Lambrecht, G. T1 - Synthese und Eigenschaften des selektiven Antimuskarinikums Cyclohexylphenyl(3-piperidinopropyl)silanol T1 - Syntbesis and Properries of the Selective Antimuscarinic Agent Cyclohexylphenyl(3-piperidinopropyl)silanol N2 - Die Synthese des selektiven Antimuskarinikums Cyclohexylpheny\{3-piperidinopropyl)sila· nol (1 b) wird beschrieben. 1 b wurde - ausgehend von (3·Chlorpropyl)trimethoxysilan - durch eine vierstufige Reaktionsfolge erhalten und als Hydrochlorid 2b mit einer Gesamtausbeute von etwa 45°/o isoliert. - 1 b ist aufgrund seiner großen pharmakologischen Se· lektivität zu einer Standardsubstanz in der experimentellen Pharmakologie bei der Differenzierung von Muskarinrezeptoren geworden. N2 - The synthesis of thc selective antimuscarinic agent cyclohexylphenyl(3-piperidinopropyl)silanol (1 b) is described. Starting with (3-chloropropyl)trimethoxysilane, I b was obtained by four reaction steps and isolated as hydrochloride 2b with a total yield of about 45°/o. - Because of its high pharmacological selectivity 1 b has become a reference drug in experimental pharmacology for the differentiation of muscarinic rcceptors. KW - Anorganische Chemie Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63798 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Linoh, H. A1 - Rafeiner, K. A1 - Lambrecht, G. A1 - Mutschler, E. T1 - Synthese und Eigenschaften des selektiven Antimuscarinikums Sila-Hexocyclium-methylsulfat N2 - Sila-Hexocyclium-methylsulfat (7b), ein Silicium-Analogon des therapeutisch eingesetzten Antimuscarinileums Hexocyclium-methylsulfat (7a), wurde durch eine sechsstufige Synthese - ausgehend von (CH\(_3\)0)\(_3\)SiCH\(_2\)Cl - dargestellt (Gesamtausbeute 16%). Außerdem wurden die hiervon abzuleitende freie Base 9b (fünfstufige Synthese, ausgehend von (CH\(_3\)0)\(_3\)SiCH\(_2\)O; Gesamtausbeute 29%) und das strukturverwandte (Aminomethyl)silanol 13 (dreistufige Synthese, ausgehend von cyclo-C\(_6\)H\(_{11}\)(C\(_6\)H\(_5\))Si(OCH\(_3\))CH\(_2\)Cl, Gesamtausbeute 46$) synthetisiert. 7b ist ein hochwirksames und selektives Antimuscarinikum, das in der experimentellen Pharmakologie aufgrund seines bemerkenswerten Selektivitätsprofils zur Klassifizierung von Subtypen muscarinischer Rezeptoren eingesetzt wird. N2 - Sila-hexocyclium methyl sulfate (7b), a silicon analogue of the antimuscarinic agent hexocyclium methyl sulfate (7a), has been prepared by a six-step synthesis (total yield 16%) starting from (CH\(_3\)O)\(_3\)SiCH\(_2\)Cl. In addition, the corresponding free base (a five-step synthesis, starting from (CH\(_3\)O)\(_3\)SiCH\(_2\)Cl; total yield 29%) and the structurally related (aminomethyl)silanol (a three-step synthesis, starting from cyclo-C\(_6\)H\(_{11}\)(C\(_6\)H\(_5\))Si(OCH\(_3\))CH\(_2\)Cl; total yield 46%) have been synthesized. 7b is a potent and highly selective antim.uscarinic agent. Because of its remarkable selectivity profile, it is used in experimental phannacology to classify the various subtypes of musearlnie receptors. KW - Anorganische Chemie Y1 - 1989 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63921 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Linoh, H. A1 - Ernst, L. A1 - Moser, U. A1 - Mutschler, E. A1 - Sarge, S. A1 - Cammenga, H. K. A1 - Lambrecht, G. T1 - Darstellung und Eigenschaften der Enantiomere der Antimuskarinika Sila-Procyclidin und Sila-Tricyclamol-iodid: Optisch aktive Silanole mit Silicium als Chiralitätszentrum N2 - Durch Racematspaltung mit L-( + )- bzw. o-(-}-Weinsäure wurden die Enantiomere des Sila-Procyclidins (R}-1 b und (S}-1 b erhalten (>97% ce (NMR), 99.7% ee {DSC)]. Daraus wurden die Hydrochloride (R}-2b und (S)-lb und durch Umsetzung mit CH31 die Enantiomerc des Sila-Tricyclamol-iodids (R)-3b und (S}-3b [>96% ee (NMR)] hergestelll Die optisch aktiven Silanoie sind in k:ristalliner Form und in inerten Lösungsmitteln konfigurationsstabil. während sie in wässeriger Lösung raoemisieren (3 b schneller als 111). In. Analogie zur Stereoselektivität der antimuskarin. iscben Wirkung der Enantiomere der Kohlenstoff-Analoga Procyclidin (la) und Tricyclamol-iodid (3a) besitzen die (R)Enantiomere von 1 b und 311 eine größere Affinität zu den ilealen M2&- und atrialen M2ar-Muskarinrezeptorcn des Meerschwein,;, cbens als die (S)-Antipoden. Alle Silicium-Verbindungen sind stärker antiinuskarinisch wirksam als ihre Kohlenstoff-Analoga, deren Stereoselektivität jedoch stärker ausgeprägt ist. Die Unterschiede in der A1Tmität von (R}-1 b und (S)-1 b zu den ilealen und atrialen Muskarinrezeptoren bestätigen das Konzept der Heterogenität musk:arinis.cher M 2-Rezeptoren (M 2\(_\alpha\): atrialer Typ; M2\(_\beta\): ilealer Typ). N2 - The enantiomers of sila-procyclidine (R}-1 band (S)-1 b [ > 97% ee (NMR~ 99.7% ee (DSC}] were obtained by resolution with L( + )· and o-(-)-tartaric acid. rcspectively. Starting from (R}-1 b and (S)-1 b. the hydrochlorides (R)-lla and (S)-lb wcre ptepared and thc enantiomcrs of sila-tricyclamol iodide {R)-311 and (S}-3b [>96% ee (NMR)] were syothesized by reaction witb CH31. Tbe optically active silanols show configurational stabiUty in the crystalline state and in inert solvents. whereas they racemizc in aqucous solution (3b faster tban 1 b). By analogy with the stereoselectivity of antimuscarinic action of the enantiomers of tbe carbon analogues procyclidine (la) and tricyclamol iodide (Ja), tbe t.R) enantiomers of 1b and 3b show a greater aftinity for the ileal M211 and atrial M2a _muscarinic reoeptors of the guinea pig than the corresponding (S) antipodes. AU silicon compounds e:xhibit a greater antimuscarinic potency than their carbon analogues, whercas the stereoselectivity of action is more pronounced for the carbon compounds. The difTerences in affmity for (R}-1 b and (S}l b for ileal and atrial muscarinic receptors confirm the present concept of heterogencity in muscarinic M2 rccepton (M 2\(_\alpha\): atrial type; M 2\(_beta\): ileal type). KW - Anorganische Chemie Y1 - 1987 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63822 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Link, Matthias A1 - Joppien, Hartmut A1 - Ernst, Ludger T1 - Sila-Substitution des Akarizids Fenbutatinoxid und einiger seiner Derivate: Synthese und Eigenschaften von Hexakis[(dimethylphenylsilyl)methyl]distannoxan und Tris[(dimethylphenylsilyl)methyl](1,2,4-triazol-1-yl)stannan T1 - Sila-substitution of the Acaricide Fenbutatinoxide and some of its derivatives: synthesis and properties of Hexakis[(dimethylphenylsilyl)methyl](1,2,4-triazol-1-yl)stannane N2 - No abstract available. KW - Chemische Synthese KW - Akarizid KW - sila-substitution KW - fenbutatinoxide KW - hexasila-fenbutatinoxide KW - acaricides KW - syntheses Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-86937 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Link, Matthias A1 - Bentlage-Felten, Anke A1 - Zilch, Harald T1 - Zum thermischen Verhalten einiger Kohlensäure[(methylphenylsilyl)methyl]ester-Derivate T1 - On the Thermal Behaviour of Some (Methylphenylsilyl)methyl Carbonate Derivatives JF - Zeitschrift für Naturforschung B N2 - The synthesis and the thermal behaviour of the (methylphenylsilyl)methyl carbonates \(CH_3(C_6H_5)Si(H)CH_2OC(O)X (6: X = OCH_3; 7: X = Cl; 8: X = N(CH_3)_2)\) is described. 8 rearranges in toluene solution at 100 °C quantitatively to give the carbam oyloxysilane \(C_6H_5(CH_3)_2SiOC(O)N(CH_3)_2\) (11), whereas neat 6 and 7 at 135 °C undergo quantitative formation of \(C_6H_5(CH_3)_2SiOCH_3\) (12) and \(C_6H_5(CH_3)_2SiCl\) (13), respectively. The formation of 12 and 13 is explained by a rearrangement reaction (by analogy to the rearrangement of 8), follow ed by a decarboxylation. The thermally induced transformations 6 →12, 7 →13, and 8 →11 were found to be first-order reactions with half-lifes of ~2.6 h (135 °C, neat), ~4.5 h (135 °C, neat), and ~3.7 h (100 °C, in toluene), respectively. KW - decarboxylation KW - (Methylphenylsilyl)methyl carbonates KW - rearrangement KW - dimethylphenylsilyl carbonates Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-128293 VL - 40 IS - 7 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Link, M. A1 - Zilch, H. T1 - Eine neue in situ-Darstellung von (Trimethyl-silyl)trifluormethansulfonat durch thermisch induzierte Umlagerung T1 - A New in situ Preparation of Trimethylsilyl Trifluoromethanesulfonateby Thermally Induced Rearrangement N2 - A new in situ preparation of trimethylsilyl trifluoromethanesulfonate (3) is described: 3 is generated by a thermally induced rearrangement of (dimethylsilyl)methyl trifluoromethanesulfonate (2), which can be prepared by reaction of (CH\(_3\))\(_2\)Si(H)CH\(_2\)OH (1) with (CF\(_3\)SO\(_2\))\(_2\)O. Starting with C\(_6\)H\(_5\)(CH\(_3\))Si(H)CH\(_2\)OH (5), the derivative (methylphenylsilyl)methyl trifluoromethanesulfonate (6) can be obtained by a similar method. Its thermally induced rearrangement Ieads to dimethylphenylsilyl trifluoromethanesulfonate (7). The rearrangements 2---> 3 and 6---> 7 were found to be first-order reactions with half-lifes at 80 oc of 0.75 and 1.7 h, respectively. KW - Anorganische Chemie Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63784 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Lange, Hartwig A1 - Sheldrick, William S. A1 - Lambrecht, Günter A1 - Moser, Ulrich A1 - Mutschler, Ernst T1 - Sila-Pharmaka, 31. Mitt. [1] Synthese, Struktur und pharmakologische Eigenschaften von Diphenyl(2-piperidinoethoxymethyl)silanol und seinem Kohlenstoff-Analogon T1 - Sila-Pharmaca, 31 th Communication [1] Synthesis, Structure, and Pharmacological Properties of Diphenyl(2-piperidinoethoxymethyl)silanol and its Carbon Analogue JF - Zeitschrift für Naturforschung B N2 - In the course of systematic investigations on sila-substituted parasympatholytics the diphenyl(2-aminoethoxymethyl)silanols 3b and 4b (and its carbon analogue 4a) were synthesized and characterized by their physical and chemical properties. In the solid state 4a and 4b form strong O-H---N hydrogen bonds, which are intramolecular (4a) and intermolecular (4b), respectively. 4a and 4b were found to be weak antimuscarinic agents (4b >4a) and strong papaverine-like spasmolytics (4a ≈4b). KW - antimuscarinic and papaverine-like activity KW - sila-substitution KW - crystal and molecular structure Y1 - 1983 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-128410 VL - 38 IS - 6 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Lange, Hartwig A1 - Bentlage, Anke A1 - Sheldrick, William S. A1 - Ernst, Ludger T1 - 2.2.5.5-Tetraorganyl-1.4-dioxa-2.5-disilacyclohexane/2,2,5,5-Tetraorganyl-1,4-dioxa-2,5-disilacyclohexanes JF - Zeitschrift für Naturforschung B N2 - The 2,2,5,5-tetraorganyl-1,4-dioxa-2,5-disilacyclohexanes 2a-2c were prepared by condensation of the corresponding (hydroxymethyl)diorganylsilanes 1 a-1 c. The constitution of the heterocycles was confirmed by elemental analyses, cryoscopic measurements, mass spectrometry, and NMR-spectroscopic \((^1H, ^{13}C)\) investigations. The molecular structure of 2 b was determined by X-ray diffraction analysis. KW - 1,4-Dioxa-2 KW - 5-disila-cyclohexane ring system KW - synthesis KW - structure Y1 - 1983 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-128423 VL - 38 IS - 2 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Lange, H. A1 - Bentlage, A. T1 - Synthese und Eigenschaften von (Hydroxy-methyl)diorganylsilanen T1 - Synthesis and Properties of (Hydroxymethyl)diorgaoylsilanes N2 - The synthesis of the (hydroxymethyl)diorganylsilanes R\(^1\)R\(^2\)Si(H)CH\(_2\)OH (4a: R\(^1\) = R\(^2\) = CH\(_3\), 2-silaisobutanol; 4b: R\(^1\) = CH\(_3\), R\(^2\) == C\(_6\)H\(_5\); 4c: R\(^1\) == R\(^2\) = C\(_6\)H\(_5\))is achieved bythereactionof R\(^1\)R\(^2\)Si(Cl)CH\(_2\)Cl (2a-c) with AcOH/NEt\(_3\) to R\(^1\)R\(^2\)Si(OAc)CH\(_2\)OAc (Ja-c), followed by treating with LiAlH\(_4\) and hydrolysis. KW - Anorganische Chemie Y1 - 1982 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63727 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Lange, H. A1 - Attar-Bashi, M. T. T1 - Baseninduzierte 1,2-Hydridverschiebungen vom Silicium zum Kohlenstoff: "Anomale" Substitutionsreaktionen an (Halogen-methyl)diorganylsilanen T1 - Base Induced l,2-Hydride Shifts from Silicon to Carbon: "Anomalous" Substitution Reactionswith (Halomethyl)diorganosilanes N2 - (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)X (1 a: X = Cl; 1 b: X = I) und C\(_6\)H\(_5\)(CH\(_3\))Si(H)CH\(_2\)CI (10) reagieren mit LiOCH\(_2\)CH\(_2\)N(CH\(_3\))\(_2\) (2b) zu den Alkoxysilanen (C\(_6\)H\(_5\))\(_2\)Si(CH\(_3\))OCH\(_2\)CH\(_2\)N(CH\(_3\))\(_2\) (5) bzw. C\(_6\)H\(_5\)(CH\(_3\))\(_2\)SiOCH\(_2\)CH\(_2\)N(CH\(_3\))\(_2\) (12). Die Bildung dieser unerwarteten Reaktionsprodukte wird durch einen nucleophilen Angriff des Alkoxids am Si-Atom gedeutet. dem sich eine intramolekulare 1 ,2-Hydridverschiebung vom Si zum C und Eliminierung von Cl e anschließt. Mit weichen Basen, wie z. B. I (-) und (-)SCH\(_2\)CH\(_2\)N(CH\(_3\))\(_2\), wurden dagegen "normale" Substitutionsreaktionen am C-Atom der SiCH\(_2\)Cl-Gruppe beobachtet N2 - (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)X (Ia: X = Cl; 1 b: X = I) and C\(_6\)H\(_5\)(CH\(_3\))Si(H)CH\(_2\)CI (10) react with LiOCH\(_2\)CH\(_2\)N(CH\(_3\))\(_2\) (2b) to give the alkoxysilanes (C\(_6\)H\(_5\))\(_2\)Si(CH\(_3\))OCH\(_2\)CH\(_2\)N(CH\(_3\))\(_2\) (5) and C\(_6\)H\(_5\)(CH\(_3\))\(_2\)SiOCH\(_2\)CH\(_2\)N(CH\(_3\))\(_2\) (12), respectively. The formation of these unexpected reaction products is interpreted by a nucleophilic attack of the alkoxide at the Si atom, followed by an intramolecular 1 ,2-hydride shift from Si to C and elimination of Cl 8. However, with soft bases [for example l e and (-)SCH\(_2\)CH\(_2\)N(CH\(_3\))\(_2\) "normal" substitution reactions at the C atom of the SiCH\(_2\)Cl group were observed. KW - Anorganische Chemie Y1 - 1982 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63734 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Lange, H. T1 - Thermisch induzierte Umlagerung von (Acyloxymethyl)- diorganylsilanen T1 - Thermally Induced Rearrangement of (Acyloxymethyl)diorganylsilanes N2 - Die (Acyloxymethyl)diorganylsilane R\(^1\)R\(^2\)Si(H)CH\(_2\)OC(O)R\(^3\) (2a- d) unterliegen einer thermisch induzierten Umlagerung zu den entsprechenden Acyloxy(methyl)diorganylsilanen R\(^1\)R\(^2\)Si(CH\(_3\))OC(O)R\(^3\) (3a- d). Diese Reaktion beinhaltet formal einen Austausch des am Silicium gebundenen Wasserstoffs mit dem am Kohlenstoff gebundenen Acyloxy-Rest. Bezüglich der 1,2- Wasserstoff-Verschiebung konnte experimentell ein intramolekularer Prozeß bewiesen werden. N2 - The (acyloxymethyl)diorganylsilanes R\(^1\)R\(^2\)Si(H)CH\(_2\)OC(O)R\(^3\) (2a-d) rearrange to the corresponding acyloxy(methyl)diorganylsilanes R\(^1\)R\(^2\)Si(CH\(_3\))OC(O)R\(^3\) (3a-d). This reaction is formally equivalent to an exchange of the hydrogen bound to silicon and the acyloxy group bound to carbon. The 1 ,2-hydrogen shift could be shown experimentally to be an intramolecular process. KW - Anorganische Chemie Y1 - 1983 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63752 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Kropfgans, Martin A1 - Tafel, Andrea A1 - Wiesenberger, Frank A1 - Sheldrick, William S. A1 - Mutschler, Ernst A1 - Egerer, Hansjörg A1 - Rettenmayr, Nikola A1 - Gross, Jan A1 - Waelbroeck, Magali A1 - Lambrecht, Günter T1 - (Hydroxymethyl)diphenyl(piperidinoalkyl)silane des Typs (HOCH2)(C6H5)2Si(CH2)nNC5H10 (n = 2,3) und deren Methoiodide: Synthese, Struktur und antimuscarinische Eigenschaften N2 - No abstract available. KW - (Hydroxymethyl)diphenyl(piperidinoalkyl)silanes KW - Sila-pridinol KW - Sila-difenidol KW - muscarinic antagonists KW - muscarinic receptors Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-86904 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Hengelsberg, H. A1 - Klingner, E. A1 - Henke, H. T1 - Synthese der Si-funktionellen Acetylsilane tBu(Me\(_3\)SiCH\(_2\))[MeC(O)]SiF und tBu(Me\(_3\)SiCH\(_2\))[MeC(O)]SiH sowie Synthese und Kristallstruktur des Acetylsilanols tBu(Me\(_3\)SiCH\(_2\))[MeC(O)]SiOH: Substrate für mikrobielle Reduktionen N2 - The racemic Si-functional acetylsilanes tBu(Me\(_3\)SiCH\(_2\))[ MeC(O)]SiF (1) and tBu(Me\(_3\)SiCH\(_2\))[MeC(O)]SiH (2) and the racemic acetylsilanol tBu(Me\(_3\)SiCH\(_2\))[MeC(O)]SiOH (3) were synthesized from Si(OMe)\(_4\) (4) as substrates for microbial reductions [4 -> tBuSi(OMe)\(_3\) (5) -> tBu(Me\(_3\)SiCH\(_2\))Si(OMe)\(_2\) (6) -> tBu(Me\(_3\)SiCH\(_2\))SiF\(_2\) (7)-> tBu(Me\(_3\)SiCH\(_2\))(CH\(_2\) = C(OMe))SiF (8) -> 1; 8 -> tBu(Me\(_3\)SiCH\(_2\))[CH\(_2\) = C(OMe)]SiH (9) -> 2; 6 -> tBu(Me\(_3\)SiCH\(_2\))[CH\(_2\) = C(OMe)]SiOMe (10) -> 3]. Compounds 1-3 were found to be reduced by cells of Trigonapsis variabilis (DSM 70714) ( = SiC(O)Me -> = SiCH(OH)Me}. The crystal and molecular structure of 3 was studied by singlecrystal X-ray diffraction. In the crystal, racemic 3 forms infinite chains built up by intermolecular 0-H .. ·O bonds between the hydroxyl and acetyl groups of molecules of the same absolute configuration. KW - Anorganische Chemie KW - Silanes KW - acetyl- KW - Si-functional KW - Silanol KW - crystal structure of KW - Microbial reduction Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64192 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Heeg, E. A1 - Berndt, B T1 - Sila-Analogon des Rythmols T1 - Sila Analogue of Rythmol N2 - Sila-Rythmol (llb), ein Sila-Analogon des Antiarrhythmieums Rythmol (lla), wurde erstmalig dargestellt. llb sowie die Vorstufen und Nebenprodukte 4, 5, 6, 7, 9b und lOb wurden in ihren physikalischen und chemischen Eigenschaften charakterisiert und in ihrer Struktur sichergestellt. Die pharmakologischen und toxikologischen Eigenschaften der Analoga lla und llb wurden vergleichend untersucht. N2 - Silarythmol (llb), a sila analogue of the antiarrhythmic rythmol (lla), was synthesized for the first time. llb as weil as the precursors and byproducts 4, 5, 6, 7, 9b, and lOb were characterized by their physical and chemical properties. The pharmacological and toxicological properties of the analogues lla and llb were also investigated. KW - Anorganische Chemie Y1 - 1980 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63642 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Haller, Ingo A1 - Zeiler, Hans-Joachim T1 - Sila-Analoga der Antiseptica Octafoniumchlorid und p-tert-Butylphenol N2 - No abstract available. KW - Silaanaloga KW - Antiseptikum Y1 - 1979 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-86893 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Frohnecke, J. A1 - Niedner, R. T1 - Darstellung und Eigenschaften potentiell curarewirksamer Silicium-Verbindungen, IV T1 - Preparation and Properties of Silicon Compounds with Potential Curare-Like Activity, IV N2 - Die Synthese der Organosilicium· Verbindungen 3 a- d wird erstmalig beschrieben. Sie wurden durch ihre physikalischen, chemischen und pharmakologischen Eigenschaften charakterisiert. Ja- d wirken als uKurzzeit-Muskelrelaxantien", deren Entgiftung durch Hydrolyse der Si- OeBindungen (Sollbruchstellen) erfolgt. N2 - The synthesis of the organosilicon compounds Ja-d is described for the first time. They were characterized by their physical, chemical, and pharmacological properties. 3 a- d are shortly acting muscle relaxants. Their detoxification is achieved by hydrolysis of the Si-OC bonds ("intended sites of cleavage"). KW - Anorganische Chemie Y1 - 1982 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63711 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Fritsche, K. A1 - Tafel, A. A1 - Wuttke, F. T1 - Synthese von racemischem Acetyl(t-butyl)methylphenylsilan und Acetylmethylphenyl[(trimethylsilyl)methyl]silan: Substrate für stereoselektive mikrobielle Reduktionen KW - Anorganische Chemie Y1 - 1990 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64055 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Bentlagem, A. A1 - Towart, R. A1 - Meyer, H. A1 - Bossert, F. A1 - Vater, W. A1 - Stoepe, K. T1 - Sila-Analoga von Nifedipin-ähnlichen 4-Aryl-2.6-dimethyl-1.4-dihydropyridin-3.5-dicarbonsäure-dialkylestern, I N2 - no abstract available KW - Chemie Y1 - 1980 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-82430 ER -