TY - JOUR A1 - Tacke, R. A1 - Strecker, M. A1 - Sheldrick, W. S. A1 - Heeg, E. A1 - Berndt, B. A1 - Knapstein, K. M. T1 - Sila-Pharmaka, 14. Mitt. Darstellung und Eigenschaften sowie Kristall-und Molekülstruktur von Sila-Difenidol JF - Zeitschrift für Naturforschung B N2 - Sila-difenidol (6b), a sila-analogue of the drug difenidol (6a), was synthesized according to Scheme 1. 6b and its new precursors 3 and 5 were characterized by their physical and chemical properties, and their structures confirmed by elementary analyses, 1H NMR and mass spectroscopy. 6 b crystallizes orthorhombic \(P2_12_12_1\) with a = 11.523(1), b = 14.366(4), c = 11.450(1) Å, Z = 4, \(D_{ber} = 1.14 gcm^{-3}\). The structure was refined to R = 0.050 for 1897 reflexions. A strong nearly linear intramolecular O-H···N hydrogen bond of 2.685 Å is observed. The anticholinergic, histaminolytic and musculotropic spasmolytic activities of 6 a and 6 b are reported. KW - sila-difenidol KW - syntheses KW - crystal structure KW - molecular structure KW - biological activity Y1 - 1979 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-128391 VL - 34 IS - 9 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 - 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 - 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 - 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 - Eltze, M. A1 - Ullrich, B. A1 - Mutschler, E. A1 - Moser, U. A1 - Bungardt, E. A1 - Friebe, T. A1 - Gubitz, C. A1 - Tacke, Reinhold A1 - Lambrecht, G. T1 - Characterization of muscarinic receptors mediating vasodilation in rat perfused kidney N2 - The muscarinic receptor mediating vasodilation of resistance vessels in the rat isolated, constant-pressure perfused kidney (preconstriction by w- 7 M cirazoline) was characterized by subtype-preferring agonists and se]ective antagonists. The agonists produced vasodi1ation with the fol1owing rank order of potency: arecaidine propargy] ester (APE) > 5-methylfurtrethonium = methacholine = oxotremorine > (S)-aceclidine > arecaidine 2-butyne-1,4-diyl bisester > 4-Cl-McN-A-343 = (R)-nipecotic acid ethyl ester = N-ethyl-guvacine propargyl ester- (R)-aceclidine = (S)-nipecotic acid ethyl ester > McN-A-343. Agonist-induced vasodilation disappeared after destruction of the endothelium with detergent. Highly significant correlations of agonist potencies for vasodilation were found between rat kidney and guinea-pig ileum submucosal arterioles as weH as agonist potencies at smooth muscle muscarinic M\(_3\) receptors of the guinea-pig ileum. The rank order of antagonist potencies (4-diphenylacetoxy-Nmethylpiperidine methiodide (4-DAMP) > (R)-hexahydro-difenidol - hexahydro-sila-difenidol > pirenzepine - p-fluorohexahydro- sila-difenidol- himbacine- AF-DX 384- AQ-RA 741 > (S)-hexahydro-difenidol) to attenuate vasodilation to APE in rat kidney, correlated significantly with affinities at M\(_3\) receptors in submucosal arterioles and in smooth muscle of the guinea-pig ileum, but differed from those at M\(_1\) and M\(_2\) receptors in rabbit vas deferens. The agonist and antagonist potencies suggest that vasodilation elicited by muscarinic stimuli in endothelium-intact rat renal vasculature is mediated by functional muscarinic M\(_3\) receptors. KW - Anorganische Chemie KW - Kidney (perfused KW - rat) KW - Muscarinic receptor agonists KW - Muscarinic receptor antagonists KW - Arterioles (submucosal) KW - Ileum; Atrium KW - Vas deferens Y1 - 1993 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64283 ER - TY - JOUR A1 - Mühleisen, M. A1 - Tacke, Reinhold T1 - Twofold deprotonated citric acid as a bidentate ligand of pentacoordinate silicon: synthesis and structural characterization of the zwitterionic \(\lambda_5\)Si-spirosilicate bis[citrato(2-)-O\(^3\),O\(^4\)][(dimethylammonio)methyl]silicate hydrate N2 - The zwitterionic \(\lambda_5\) Si-spirosilicate bis[ citrato(2-)-0\(^3\) ,0\(^4\) )[ ( dimethylammonio) methyl]silicate (4) was synthesized by reaction of (MeO)\(_3\)SiCH\(_2\)NMe\(_2\) (3) with citric acid (molar ratio 1 :2) in acetonitrile at room temperature and isolated, after crystallization from water, as the hydrate 4 · H\(_2\)O (yield 81 %). The crystal structure of 4 · H\(_2\)O was studied by single-crystal X-ray diffraction. The alcoxide oxygen atoms and central carboxylate oxygen atoms of two citrato(2-) ligands and one carbon atom coordinate to the silicon atom of 4 · H\(_2\)O. The coordination polyhedron around the pentacoordinate silicon atom (SiO\(_4\)C framework) can be described as a distorted trigonal bipyramid, the two carboxylate oxygen atoms occupying the axial sites. The \(\lambda_5\) Si~silicon(IV) complex 4 also exists in solution (DMSO, H\(_2\)O). KW - Anorganische Chemie KW - Silicon KW - pentacoordinate KW - Lambda5Si-Spirosilicate KW - zwitterionic KW - Citrato(2-)-03 KW - 04ligand Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64388 ER - TY - JOUR A1 - Mühleisen, M. A1 - Tacke, Reinhold T1 - meso-[1,4-Piperaziniumdiylbis(methylene)]bis{bis[2-methyllactato(2-)-O1,O2]silicate} octahydrate: synthesis and crystal structure analysis of a zwitterionic dispirocyclic \(\lambda^5\)Si,\(\lambda^5\)Si'-disilicate N2 - The zwitterionic dispirocyclic \(\lambda^5\)Si,\(\lambda^5\)Si'-disilicate meso-[1 ,4-piperaziniumdiylbis( methylene)]bis{ bis[ 2-methyllactato(2-)-O\(^1\),O\(^2\)]silicate} octahydrate (6-8H\(_2\)O) was synthesized by reaction of 1,4-bis[(trimethoxysilyl}methyl] piperazine (8) with 2-methyllactic acid (molar ratio 1:4) in water/acetone (yield 82%). The molecular dinuclear silicon(IV) complex 6 contains two pentacoordinate (formally negatively charged) silicon atoms and two tetracoordinate (formally positively charged) nitrogen atoms. The crystal structure of 6•8H20 was studied by X-ray diffraction. KW - Anorganische Chemie Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64396 ER - TY - JOUR A1 - Tacke, Reinhold A1 - Mühleisen, M. T1 - Bis[benzilato(2-)-O\(^1\),O\(^2\)][2-(dimethylammonio)ethoxy]silicate: synthesis and structural characterization of a zwitterionic \(\lambda^5\)Si-silicate with a SiO\(_5\) framework N2 - No abstract available KW - Anorganische Chemie Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64400 ER -