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  - Waelbroeck, M.
A1  - Tastenoy, M.
A1  - Camus, J.
A1  - Christophe, J.
A1  - Strohmann, C.
A1  - Linoh, H.
A1  - Zilch, H.
A1  - Tacke, Reinhold
A1  - Mutschler, E.
A1  - Lambrecht, G.
T1  - Binding and functional properties of antimuscarinics of the hexocyclium/sila-hexocyclium and hexahydro-diphenidol/hexahydro-sila-diphenidol type to muscarinic receptor subtypes
N2  - l In an attempt to assess the structural requirements for the musearlnie receptor selectivity of hexahydro-diphenidol (hexahydro-difenidol) and hexahydro-sila-diphenidol (hexahydro-sila-difenidol), a serles of structurally related C/Si pairs were investigated, along with atropine, pirenzepine and methoctramine, for their binding affinities in NB-OK 1 cells as well as in rat heart and pancreas. 2 The action of these antagonists at musearlnie receptors mediating negative inotropic responses in guinea-pig atrla and ileal contractions has also been assessed. 3 Antagonist binding data indicated that NB-OK 1 cells (M\(_1\) type) as weil as rat heart (cardiac type) and pancreas (glandularjsmooth muscle type) possess different muscarinic receptor subtypes. 4 A highly significant correlation was found between the binding affinities of the antagonists to muscarinic receptors in rat heart and pancreas, respectively, and the affinities to muscarinic receptors in guinea-pig atria and ileum. This implies that the musearlnie binding sites in rat heart and the receptors in guinea-pig atrla are essentially similar, but different from those in pancreas and ileum. 5 The antimuscarinic potency of hexahydro-diphenidol and hexahydro-sila-diphenidol at the three subtypes was inftuenced differently by structural modifications (e.g. quaternization). Different selectivity profiles for the antagonists were obtained, which makes these compounds useful tools to investigate further muscarinic receptor heterogeneity. lndeed, the tertiary analogues hexahydrodiphenidol (HHD) and hexahydro-sila-diphenidol (HHSiD) bad an M\(_1\) = glandularjsmooth muscle > cardiac selectivity profile, whereas the quaternary analogues HHD methiodide and HHSiD methiodide were M\(_1\) preferring (M\(_1\) > glandularjsmooth muscle, cardiac).
KW  - Anorganische Chemie
Y1  - 1989
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63944
ER  - 
TY  - JOUR
A1  - Waelbroeck, M.
A1  - Camus, J.
A1  - Tastenoy, M.
A1  - Mutschler, E.
A1  - Strohmann, C.
A1  - Tacke, Reinhold
A1  - Schjelderup, L.
A1  - Aasen, A.
A1  - Lambrecht, G.
A1  - Christophe, J.
T1  - Stereoselective interaction of procyclidine, hexahydro-difenidol, hexbutinol and oxyphencyclimine, and of related antagonists, with four muscarinic receptors
N2  - Wc invcstigatcd thc binding properlies of thc (R)- and (Sl-cnantiomcrs of thc muscarinic antagonists trihcxyphcnidyl, procyclidinc, hcxahydro-difcnidol. p-fluoro-hcxahydro-difcnidol. hcxbutinol, p-fluoro-hcxbutinnl. and thcir corrcsponding methiodidcs at muscarinic M\(_1\), M\(_2\)• M\(_3\) and M\(_4\) receptor subtypes. In addition. binding properlies of thc (R)- and (S)-cnantiomcrs of oxyphcncycliminc wcrc studicd. The {R)- cnantiomcrs (cutomcrs} of all the compounds had a grcatcr affinity than the (S)-isomcrs for thc four muscarinic rcccptor subtypcs. Thc binding pattcrns of thc (R)- and (S)-enantiomers wcrc gcncrally different. We did not obscrvc any gcncral corrclation hctwccn thc potcncy of thc high-affinity enantiomer and Lhc affinity ratio (cudismic ratio) of the two cnantiomcrs. Thc rcsuhs arc discusscd in tcrms of a 'four suhsitcs' binding modcl.
KW  - Anorganische Chemie
KW  - Muscarinic receptors
KW  - Hexahydro-difenidol
KW  - Oxyphencyclimine
Y1  - 1992
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64237
ER  - 
TY  - JOUR
A1  - Waelbroeck, M.
A1  - Camus, J.
A1  - Tastenoy, M.
A1  - Mutschler, E.
A1  - Strohmann, C.
A1  - Tacke, Reinhold
A1  - Lambrecht, G.
A1  - Christophe, J.
T1  - Binding affinities of hexahydro-difenidol and hexahydro-sila-difenidol analogues at four muscarinic receptor subtypes: constitutional and stereochemical aspects
N2  - Hexahydro-sila-difenidoJ and eight analogues behaved as simple cumpetitive inhibitors of eHJN·methyl·scopoJamine binding to homogenates frorn human neuroblastoma NB-OK 1 cells (M\(_1\) sites), rat heart (M\(_2\) sites), rat pancreas (M\(_3\) sites), and rat striatum 'B' sites (M\(_4\) sites). Pyrrolidino- and hexamethyleneimino analogues showed the same sekctivity profile as the parent compound. Hexahydro-sila-difenidol methiodide and the methiodide of p-fluoro-hexahydro·sila-difenidol had a fügher affinity but a lower selectivity than the tertiary amines. Compounds containing a p·methoxy, p-chJoro or p-fluoro substituent in the phenyl ring of hexahydro-sila-difenidol showed a qualitative)y similar selectivity profile as the parent compound (i.e., M\(_1\)= M\(_3\) = M\(_4\) >M\(_2\) ), but up to 16-fold lower affinities. o-Methoxy-hexahydro-sila-difenidol has a lower affinity than hexahydro-sila-difeni.:!o! at the four binding sites. lts selectivity profile (M\(_4\) > M\(_1\), M\(_3\) > M\(_2\) ) was different from hexahydro-sila-difenidol. Replacement of the centrat silicon atom of hexahydro-sila-difenidol, p-fluoro-hexahydro-sila-difenidol and thdr quatemary (N-methylated) analogues by a carbon atom did not change their binding affinities significantly. The iour muscarinic receptors showed a higher affinity for the (R)- than for the (S)-enantiomers of hexahydro-difenidol, p-fluorohexahydro-difenidol and their methiodides. The stereoselectivity varied depending on the receptor subtype and drug considered.
KW  - Anorganische Chemie
KW  - Muscarinic receptor antagonists (selective)
KW  - Hexahydro-sila-difenidol analogues
KW  - p-Fluoro-hexahydro-sila-difenidol
KW  - Stereoselectivity
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64128
ER  - 
TY  - JOUR
A1  - Waelbroeck, M.
A1  - Camus, J.
A1  - Tastenoy, M.
A1  - Mutschler, E.
A1  - Strohmann, C.
A1  - Tacke, Reinhold
A1  - Lambrecht, G.
A1  - Christophe, J.
T1  - Stereoselectivity of (R)- and (S)-hexahydro-difenidol binding to neuroblastoma M\(_1\), cardiac M\(_2\), pancreatic M\(_3\), and striatum M\(_4\) muscarinic receptors
N2  - (R)-Hexahydro-difenidol has a higher affinity for M\(_1\) receptors in NB-OK 1 cells, pancreas M\(_3\) and striatum M\(_4\) receptors (pKi 7.9 to 8.3) than for cardiac M2 receptors (pKi 7 .0). (8)-Hexahydro-difenidol, by contrast, is nonselective (pKi 5.8 to 6.1). Our goal in the present study was to evaluate the importance ofthe hydrophobic phenyl, and cyclohexyl rings of hexahydro-difenidol for the stereoselectivity and reeeptor selectivity of hexahydro-difenidol binding to the four muscarinic receptors. Our results indieated that replacement of the phenyl ring of hexahydro-difenidol by a cyclohexyl group <~ dicyclidol) and ofthe cyclohexyl ring by a phenyl moiety <~ difenidol) indueed a !arge (4- to 80-fold) decrease in binding affinity for all musearlnie receptors. Difenidol had a signifieant preference for M\(_1\) , M\(_3\) , and M\(_4\) over M\(_2\) receptors; dicyclidol, by eontrast, had a greater affinity for M\(_1\) and M\(_4\) than for M\(_2\) and M\(_3\) receptors. The binding free energy deerease due to replacement ofthe phenyl and the cyelohexyl groups of(R)-hexahydro-difenidol by, respectively, a eyclohexyl and a phenyl moiety was almostadditive in the ease of M\(_4\) (striatum) binding sites. In the ease ofthe cardiac M\(_2\), pancreatic M\(_3\) , or NB-OK 1 M\(_1\) receptors the respective binding free energies were not eompletely additive. These results suggest that the four (R)-hexahydro-difenidol ''binding moieties" (phenyl, cyclohexyl, hydroxy, and protonated amino group) cannot simultaneously form optimal interaetions with the M\(_1\), M\(_2\), and M\(_3\) muscarinic receptors. When eaeh of the hydrophobic groups is modified, the position of the whole molecule, relative to the four subsites, was changed to allow an optimal overall interaction with the musearlnie receptor.
KW  - Anorganische Chemie
KW  - hexahydro-difenidol enantiomers
KW  - muscarinic receptor subtypes
KW  - stereoselective interaction
KW  - difenidol
KW  - dicyclidol
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64135
ER  - 
TY  - JOUR
A1  - Waelbroeck, M.
A1  - Camus, J.
A1  - Tastenoy, M.
A1  - Lambrecht, G.
A1  - Mutschler, E.
A1  - Tacke, Reinhold
A1  - Christophe, J.
T1  - Stereoselectivity of procyclidine binding to muscarinic receptor subtypes M\(_1\), M\(_2\) and M\(_4\)
N2  - The goals of the present study were: (1) to investigate thc binding properlies oi (R)- and (S)-procyclidine and two aehiral derivatives of muscarinic M\(_1\)• M\(_2\) and M\(_4\) receptor subtypes and (2) to identify the interaetions which allow these receptors to diseriminate between the two stereoisomers. (R)-Procyclidine showed a higher affinity for human neuroblastoma NB-OK 1 muscarinie M\(_1\) and rat striatum musearinie M\(_4\) receptors. a~ compared to rat cardiac M\(_2\) receptors. (S)-Procyclidine had a 130-iold lower affinity than (R)-procyclidine for M\(_1\) and M\(_4\) receptors. and a 40-fold lower affinity for M\(_2\) receptors. Pyrrinol. the aehiral diphenyl derivative with the eyclohexyl g.roup of (S}-procyclidine replaeed by a phenyl group, has an eight-fold lower affinity for M\(_1\) and M\(_4\) receptors. as eompared to (R)-procyclidine, and a three-fold lower affinity for M\(_2\) receptors. Hexahydro-procyclidine. the eorresponding achiral dicyclohexyl compound, had a 10- to 20-fold lower affinity than (R)-procyclidine for the three reeeptors. The inerease in binding free energy, which is observed when the phenyl and eyclohexyl groups of procyelidine are separately replaeed by cyclohexyJ and phenyl groups, respectively. was additive in the ease of M\(_1\)• M\(_2\) and M\(_4\) receptcrs. This indicates that the musearinic reeeptor s!ereoseleetivity was based on the eoexistence of two binding sites, one preferring a phenylrather than eyclohexyl group and the seeond preferring a cyclohexyl rather than a phenyl group. In addition. there were aiso binding sites for the hydroxy moiety and the protonated amino group of the ligands. The greater affinity and stereoselectivity of M\(_1\) and M\(_4\) muscarinic receptors for (R)-procyelidine reflected the better fit of the eyclohexyl group of (R)-procyclidine to the subsite of M\(_1\) and M\(_4\) as compared to M\(_2\) receptors.
KW  - Anorganische Chemie
KW  - Musearlnie M1
KW  - receptors
KW  - Muscarinie M2 receptors
KW  - Musearinic M4 receptors
KW  - Pyrrinol
KW  - Hexahydro-procyclidine
KW  - Muscarinic receptors
Y1  - 1990
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64034
ER  - 
TY  - JOUR
A1  - Verspohl, E. J.
A1  - Tacke, Reinhold
A1  - Mutschler, E.
A1  - Lambrecht, G.
T1  - Muscarinic receptor subtypes in rat pancreatic islets: binding and functional studies
N2  - Cholinergie agents arepotent modulators of insulin release that aet via musearinie reeeptors. We now investigated the muscarinic receptor subtype present in rat panereatic islets in binding and funetional studies. Binding of 5 nM [ \(^3\)H]N-methylscopolamine ([\(^3\)H]NMS) was half maximal at 30 min. At 60 min, the maximal total bindingwas 1.29% and the non-specifie binding (presence of 100 ,uM atropine) was 0.18% of the total radioaetivity per 10 f.'g islet protein. Unlabelled atropine inhibited [\(^3\)H]NMS binding with an IC50 of ca. 30 nM. The rank order of antagonist high-affinity binding was atropine > sila-hexocyelium methyl sulfate (SiHC; M\(_1\) > M\(_3\) > M\(_2\) ) > pirenzepine (M\(_1\)> M\(_2\) = M\(_3\) ) = methoctramine (M\(_2\) > M\(_1\) > M\(_3\) ). The high-affinity K\(_d\)s were 8.5, 56, 1300 and 1300 nM, respectively. The high affinity Kd of the muscarinie receptor agonist, arecaidine propargyl ester (APE), was 8.1 nM. The EC\(_{50}\) for the biologieal effects of APE on insulin and glucagon secretion was 3.2 and 2.3 nM. The rank order for the high-affinity biological effects of antagonists (inhibition of APE-mediated insulin/ glucagon release) was almost the same as for binding. The data indicate that rat pancreatie islets contain neither an M\(_1\) subtype (high-affinity for pirenzepine) nor an M\(_2\) subtype (high-affinity for methoctramine) receptor. However, the data evidence an M\(_3\) receptor subtype, since SiHC in the absence of the M\(_1\) receptor subtype shows a relatively high affinity to the receptors in rat panereatic islets.
KW  - Anorganische Chemie
KW  - Muscarinic receptor subtypes
KW  - Islets of Langerhans (rat)
KW  - Insulin
KW  - Glucagon
Y1  - 1990
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63993
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  - Wuttke, F.
A1  - Henke, H.
T1  - Zur Stereochemie der mikrobiellen Reduktion von rac-Acetyl( t-butyl)methylphenylsilan mit Trigonopsis variabilis (DSM 70714) und Corynebacterium dioxydans (ATCC 21766): Aufklärung der absoluten Konfiguration der Biotransformationsprodukte (SiR,CR)- und ( SiS ,CR)-t-Butyl( 1-hydroxyethyl)methylphenylsilan
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1992
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64176
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  - Wagner, S. A.
A1  - Brakmann, S.
A1  - Wuttke, F.
A1  - Eilert, U.
A1  - Fischer, L.
A1  - Syldatk, C.
T1  - Synthesis of acetyldimethyl(phenyl)silane and its enantioselective conversion into (R)-(1-hydroxyethyl)dimethyl(phenyl)silane by plant cell suspension culytures of Symphytum officinale L. and Ruta graveolens L.
N2  - Starting from chlorodimethyl(phenyl)silane (3), acetyldimethyl(phenyl)silane (l) was prepared by a two-step synthesis in a total yield of 90% [PhMe\(_2\)SiCl (3)-> PhMe\(_2\)SiCCOMe)=CH\(_2\) (4)-> PhMe\(_2\)SiC(O)Me (1)]. The prochiral acetylsilane 1 was transfonned enantioselectively into (R)-(1-hydroxyethyl)dimethyl(phenyl)silane [(R)-2] using plant cell Suspension cultures of Symphytum officinale L. or Ruta graveolens L. Under preparative conditions (300-mg scale, not optimized), (R)-2 was isolated in 15% (Symphytum) and 9% yield (Ruta), respectively. The enantiomeric purities of the products were 81% ee (Syrnphytum) and 60% ee (Ruta), respectively.
KW  - Anorganische Chemie
Y1  - 1993
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64299
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Strohmann, C.
A1  - Sarge, S.
A1  - Cammenga, H. K.
A1  - Schomburg, D.
A1  - Mutschler, E.
A1  - Lambrecht, G.
T1  - Darstellung und Eigenschaften der Enantiomere des selektiven Antimuscarinikums 1-Cyclohexyl-1-phenyl-4-piperidino-1-butanol (Hexahydro-Difenidol)
N2  - No abstract available
KW  - Anorganische Chemie
KW  - Difenidol
KW  - (R)- and (S)-hexahydro- / Antimuscarinic properties / Muscarinic receptor subtypes
Y1  - 1989
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63950
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  - Sperlich, J.
A1  - Becker, B.
T1  - Bis[2,3-naphthalenediolato(2-)](pyrrolidinio-methyl)germanate-tetartoacetonitrile, the first zwitterionic \(\lambda_5\)-germanate: synthesis and crystal structure analysis
N2  - The zwitterionic spirocyclic \(\lambda_5\)-germanate bis(2,3-naphthalenediolato( 2-)](pyrrolidiniomethyl)germanate (8) was synthesized and the crystal structure of its tetartoacetonitrile solvate 8 · 1/4 CH\(_3\)CN studied by single-crystal X-ray diffraction. Compound 8 was prepared by reaction of (MeO)\(_3\)GeCH\(_2\)NC\(_4\)H\(_8\) (11; NC\(_4\)H\(_8\) = pyrrolidino) with two equivalents of 2,3-naphthalenediol (isolated as 8 · 1/4 CH\(_3\)CN; yield 92%). The coordination polyhedron around the pentacoordi- naphthalenediolatonate germanium atom of 8 · 1/4 CH\(_3\)CN can be described as a strongly distorted trigonal bipyramid (the structure is displaced by 38.9% from the ideal trigonal bipyrarnid towards the ideal square pyramid), the carbon atom occupying an equatorial position. In the crystal lattice of 8 · 1/4 CH\(_3\)CN, the zwitterions form intermolecular N-H ... o hydrogen bonds leading to the formation of dimers. 1H- and \(^{13}\C-NMR studies revealed that 8 also exists in solution ([D\(_6\)]DMSO).
KW  - Anorganische Chemie
KW  - Lambda5-Germanate
KW  - zwitterionic
KW  - Germanium
KW  - pentacoordinate
Y1  - 1994
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64329
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Saad, S. M.
T1  - Silylation of cellulose
N2  - Ethane-l:2-diol and propane-l:3-diol reaet with 1: 1:3:3-tetramethyl-l:3-dichlorodisiloxane forming the corresponding rings. However, no ring compounds could be traced tbrough the reaction between butane-l :4-diol, glycerol and the dichlorodisiloxane respectively, where only polymeric compounds are formed. The silylation products of the di- and trihydroxy alcohols, as model compounds, has confirmed that the ring formation during silylation of cellulose with dichlorodisiloxane is uncertain.
KW  - Anorganische Chemie
Y1  - 1977
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-78368
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  - Rafeiner, K.
A1  - Strohmann, C.
A1  - Mutschler, E.
A1  - Lambrecht, G.
T1  - Synthesis of the selective antimuscarinic agent 4-{[cyclohexylhydroxy(2-methoxyphenyl)silyl]methyl}-1,1-dimethylpiperazinium methyl sulfate (o-methoxy-sila-hexocyclium methyl sulfate)
N2  - The synthesis of the potent and highly selective silicon-containing antimuscarinic agent o-methoxysila- hexocyclium methyl sulfate and its corresponding tertiary amine (isolated as the dihydrochloride) is described. The quarternary compound is an omethoxy derivative of sila-hexocyclium methyl sulfate, which represents one of the tools currently used in experimental pharmacology for the subclassification of muscarinic receptors. The omethoxy derivative, the pharmacological profile of which differs substantially from tbat of the nonmethoxy compound, is also recommended as a tool for the investigation of muscarinic receptor heterogeneity.
KW  - Anorganische Chemie
KW  - o-methoxy-sila-hexocyclium
KW  - silahexocyclium
KW  - sila-drugs
KW  - antimuscarinics
KW  - muscarinic receptor subtypes
Y1  - 1989
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63930
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Pikies, J.
A1  - Wiesenberger, F.
A1  - Ernst, L.
A1  - Schomburg, D.
A1  - Waelbroeck, M.
A1  - Christophe, J.
A1  - Lambrecht, G.
A1  - Gross, J.
A1  - Mutschler, E.
T1  - Sila-biperiden und endo-Sila-biperiden: Synthesen, Kristallstrukturen und antimuscarinische Eigenschaften
N2  - Starting from trichloro(vinyl)silane (Cl\(_3\)SiCH=CH\(_2\)), the musearinic antagonists sila-biperiden [rac-(SiRS,C2SR>-ao-2] and endosila- biperiden [rac-(SiRS,C2SR)-endo-2] were prepared by a seven-step synthesis. Both silanols are configurationally stableininert organic solvents but undergo slow epimerization in aqueous solution (pH 7.4, 32°C) by inversion of the configuration at the silicon atom. The relative configurations of sila-biperiden and endo-sila-biperiden were detennined by single-crystal X-ray diffraction. Both compounds form intennolecular 0-H · · · N hydrogen bonds in the crystal leading to the fonnation of centrosymmetric dimers (sila-biperiden) and infinite chains (endo-sila-biperiden), respectively. Sila-biperiden is a silicon analogue (C/Si exchange) of the antiparkinsonian drug biperiden [rac-(CRS/C2SR}-exo-1]. In functional phannacological experiments, as well as in radioligand competition studies, biperiden, sila-biperiden and endo-sila-biperiden behaved as simple competitive antagonists at muscarinic Ml-, M2-, M3- and M4-receptors. The three compounds displayed the highest affinity for Ml-receptors (pA\(_2\) values: 8.72-8.80; pK\(_i\) values: 8.8-9.1), intermediate affinity for M4- and M3-receptors, and lowest affinity for M2-receptors (pA\(_2\) values: 7.57-7.79; pK\(_i\) values: 7.7-7.8). The affinity profile (Ml >. M4 > M3 > M2) of biperiden, sila-biperiden and endo-sila-biperiden is qualitatively similar to that of the M1-selective muscarinic antagonist pirenzepine. The antimuscarinic properlies of the C/Si analogues biperiden and sila-biperiden are almost identical.
N2  - Die Antimuscarinica Sila-biperiden [rac-(SiRS,C2SR)-exo-2] und endo-Sila-biperiden [rac-(SiRS,C2SR)-endo-2] wurden ausgehend von Trichlor(vinyl)silan (Cl\(_3\)SiCH=CH\(_2\)) durch eine siebenstufige Synthese dargestellt. Die beiden Silanoie sind in inerten organischen Solvenzien konfigurationsstabil, unterliegen aber in wässeriger Lösung (pH 7.4, 3ZOC) einer Epimerisierung durch Inversion der Konfiguration am Silicium-Atom. Die relativen Konfigurationen von Sila-biperiden und endo-Sila-biperiden wurden durch Einkristall-Röntgenstrukturanalysen bestimmt. Beide Verbindungen bilden im Kristall intermolekulare 0-H · · · N-Wasserstoff- Brückenbindungen aus, die zum Aufbau von zentrosymmetrischen Dimeren (Sila-biperiden) bzw. unendlichen Ketten (endo-Sila-biperiden) führen. Sila-biperiden ist ein Silicium-Analogon (C/Si-Austausch) des Antiparkinsonmittels Biperiden [rac-(CRS,C2SR>-ao-1). Sowohl in funktionellen pharmakologischen Untersuchungen als auch in Radioligand-Kompetitionsexperimenten erwiesen sich Biperiden, Sila-biperiden und endo-Sila-biperiden als rein kompetitive Antagonisten an muscarinischen M1-, M2-, M3- und M4-Rezeptoren. Alle drei Verbindungen zeigten die höchste Affinität zu den Mt-Rezeptoren (pA\(_2\)-Werte: 8.72-8.80; pKrWerte: 8.8-9.1), eine deutlich geringere Affinität zu den M4- und M3-Rezeptoren und die niedrigste Affinität zu den kardialen M2-Rezeptoren (pA\(_2\)-Werte: 7.57-7.79; pKi-Werte: 7.7-7.8). Das Affinitätsprofil (Ml > M4 > M3 > M2) von Biperiden, Sila-biperiden und endo-Sila-biperiden ist dem des Mt-selektiven Antimuscarinicums Pirenzepin qualitativ sehr ähnlich. Die antimuscarinischen Eigenschaften der C/Si-Analoga Biperiden und Sila-biperiden sind nahezu identisch.
KW  - Anorganische Chemie
KW  - Silicon
KW  - Silanol
KW  - Sila-biperiden
KW  - Bioorganosilicon chemistry
KW  - Muscarinic antagonist
KW  - Muscarinic receptor subtype
Y1  - 1994
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64303
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.
A1  - Jones, P. G.
T1  - The first zwitterionic, optically active disilicate with pentacoordinate silicon
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1994
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64358
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  - 
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  - Mühleisen, M.
T1  - Hexacoordinate silicon in a compound with an F\(_5\)SiC unit
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1994
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64378
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Mahner, K.
A1  - Strohmann, C.
A1  - Forth, B.
A1  - Mutschler, E.
A1  - Friebe, T.
A1  - Lambrecht, G.
T1  - Cyclohexyl(4-fluorophenyl)(3-piperidinopropyl)silanol (p-fluoro-hexahydro-sila-difenidol, p-F-HHSiD) and derivatives: synthesis and antimuscarinic properties
N2  - Four different syntheses of the potent and selective muscanruc antagonist cyclohexyl( 4- fluorophenyl)(3-piperidinopropyl)silanol ( p-fluoro-hexahydro-sila-difenidol, p-F-HHSiD (2b); isolated as hydrochloride 2b· HCl) are described (starting materials: (CH\(_3\)O)\(_2\)SiCH\(_2\)CH\(_2\)CH\(_2\)Cl and Si(OCH\(_3\))\(_4\) ). In addition, the synthesis of the corresponding carbon analogue p-fluoro-hexahydro-difenidol ( p-F-HHD (2a); isolated as 2a· HCI) and the syntheses of three p-F-HHSiD derivatives (3-5), with a modified cyclic amino group, are reported (3: piperidinojpyrrolidino exchange, isolated as 3· HCI; 4: piperidinoj hexamethylenimino exchange, isolated as 4 · HCl; 5: quaternization of 2b with methyl iodide). The chiral compounds 2a, 2b, 3, 4 and 5 were prepared as racemates. In functional pharmacological studies, 3-5 behaved as simple competitive antagonists at musearlnie Ml receptors in rabbit vas deferens, M2 receptors in guinea-pig atria, and M3 receptors in guinea-pig ileal smooth rnuscle. The pyrrolidino (3) and hexamethylenimino (4) analogues of the parent drug p-F-HHSiD (2b) displayed the highest affinity for Ml and M3 receptors (pA\(_2\) values: 7.0-7.4) but exhibited lower affinity for cardiac M2 receptors (pA\(_2\) : 5.9 and 6.0). Their affinity profile (Ml- M3 > M2) is different from that of p-F-HHSiD (2b) (M3 > Ml > M2), but qualitatively very similar tothat of p-F-HHD (2a). The methiodide 5 exhibited the highest affinity for Ml receptors (pA\(_2\) : 8.5) but lower affinity for M2 and M3 receptors by factors of 5.6 and 3.6, respectively.
KW  - Anorganische Chemie
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64162
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  - Jones, P. G.
T1  - Syntheses, crystal structure analyses, and NMR studies of [2-(dimethylammonio)phenyl]bis[glycolato(2-)-O1,O2]silicate and related zwitterionic spirocyclic \(\lambda_5\)Si-silicates
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1994
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64339
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  - Zilch, H.
A1  - Stumpf, B.
T1  - Enantioselective microbial reduction of 1,1-dimethyl-1-sila-cyclohexan-2-one with growing cells of the yeast Kloeckera corticis (ATCC 20109)
N2  - (R)-1,1-Dimethyl-1-sila-cyclohexan-2-ol [(R)-2] was prepared by enantioselective microbial reduction of 1,1-dimethyl-1-sila-cyclohexan-2-one (1) with growing cells of the yeast Kloeckera corticis (ATCC 20109). At a substrate concentration of 0.5 g/1 (temperature 27° C, incubation time 16 h), (R}-2 was obtained on a preparative scale in 60% yield and with an enantiomeric purity of 92% ee. Repeated recrystallization of the biotransformation product from n-hexane raised the enantiomeric purity to 99% ee.
KW  - Anorganische Chemie
Y1  - 1989
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64010
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  - Brakmann, S.
A1  - Wuttke, F.
A1  - Fooladi, J.
A1  - Syldatk, C.
A1  - Schomburg, D.
T1  - Stereoselective microbial reduction of racemic acetyl(t-butyl)methylphenylsilane by Trigonopsis variabilis (DSM 70714) and Corynebacterium dioxydans (ATCC 21766)
N2  - (SiR,CR)- and (SiS,CR)-t-butyl(l-hydroxyethyl)methylphenylsilane [(SiR,CR)-2 and (SiS,CR)-3] have been prepared by (R)-selective microbial rcduction of racemic acetyl(t-butyl)methylphenylsilane (rac-1) using resting free cells of the yeast Trigonopsis variabilis (DSM 70714) or the bacterium Corynebacterium dioxydans (ATCC 21766). The biotransfonnations were carried out on a 10 g scale. Afterseparation by column chromatography on silica gel, the optically active diastereomers (SiR,CR)-2 and (SiS,CR)-3 produccd by T. variabilis were obtained in good yields [74% ((SiR,CR)-2). 78% ((SiS,CR)-3)]. The products obtained from the reduction with C. dioxydans were isolated in significantly lower yields [20% ((SiR,CR)-2), 20% ((SiS,CR)-3)]; reaction conditions not optimized). Both bioconversions gave products with high enantiomeric purities (T. variabilis: 91% ee ((SiR,CR)-2), 96% ee ((SiS,CR)-3); C. dioxydons: ~ 991 ee ((SiR,CR)-l), ~ 99% ee ((SiS,CR)-3)). To throw light on the stereochemical aspects of these biotransfonnations, an X-ray diffraction study was carried out on the 3,5-dinitrobenzoate of rac-(SiR,CS/SiS,CR)-3. In addition, 1H NMR spectroscopic stereochemical correlation studies were performed with the (S)-MTPA esters derived from (SiR,CR)-l, (SiS,CR)-3, rac-(SiR,CRjSiS,CS)-2 and rac-(SiR,CSjSiS,CR)-3 [rac-(SiR,CR/ SiS,CS)-2 and rac-(SiR,CS/SiS,CR)-3 were obtained by reduction of rac-1 with LiAIH\(_4\) in diethylether, followed by chromatographic separation of the diastereomers on silica gel]. These stereochemical studies allowed assignment of the absolute configurations and enantiomeric purities of the biotransformation products.
KW  - Anorganische Chemie
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64109
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  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Bentlage-Felten, Anke
A1  - Linoh, Haryanto
A1  - Magda, Stephen
T1  - Sila-Analoga des Triparanols und Ethamoxytriphetols: Synthese sowie pharmakologische und toxikologische Eigenschaften
T1  - Sila-analogues of Triparanol and Ethamoxytriphetol: synthesis as well as pharmacological and toxicological properties
N2  - No abstract available.
KW  - sila-subsitution
KW  - triparanol
KW  - ethamoxytriphetol
KW  - hypolipidemic activity
KW  - toxicological properties
Y1  - 1986
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-86940
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Bentlage, Anke
A1  - Towart, Robertson
A1  - Möller, Eike
T1  - Sila-pharmaca, XXV. Sila-analogues of nifedipine-like dialkyl 2,6-dimethyl-4-aryl-1,4 dihydropyridine-3,5-dicarboxylates, III
N2  - IS neue C/Si-Analogenpaare (C-Verbindungen und sila- bzw. disila-substituierte Derivate), die sich strukturell vom Nifedipin ableiten, wurden synthetisiert. Diese und einige weitere C/Si-Paare wurden hinsichtlich ihrer physikochemischen und pharmakologischen Eigenschaften vergleichend untersucht. Mittels reversed-phase-Dünnschichtchromatographie wurde gezeigt, daß die Sila- bzw. Disila-Analoga lipophiler sind als die entsprechenden C-Verbindungen. Bezüglich der spasmolytischen in vitra-Aktivitäten zeigen die Si-Verbindungen in erster Näherung ähnliche Struktur-Wirkungs-Beziehungen wie ihre Carba-Analoga. Dagegen konnten hinsichtlich der ill vlva-Effekte (cardiovasculäre und antihypertensive Aktivität) in einigen Fällen große Unterschiede nachgewiesen werden.
N2  - 15 new C/Si-analogue pairs (C-compounds and sila- or disila-substituted derivatives, respectively), which are structurally related to nifedipine, have been synthesized. These and some further C/Si-pairs have been investigated comparatively with respect to their physicochemical and pharmacological properties. Using reversed-phase thin-layer chromatography it was shown that both the sila- and disila-analogues are more Iipophilic than the corresponding C-compounds. With respect to the in vitra spasmolytic potencies the Si-compounds show approximately similar structure-activity relationships to their carba-analogues. However, in some cases marked differences in in vivo effects (cardiovascular and antihypertensive activity) could be demonstrated.
KW  - Anorganische Chemie
Y1  - 1983
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-78357
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Becker, B.
A1  - Lange, H.
T1  - (Thioacetoxy-S-methyl)diorganylsilane und (Mercaptomethyl)diorganylsilane: Synthese und Eigenschaften
N2  - Die erstmalige Synthese der (Thioacetoxy-S-methyl)diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (9) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (10) und der (Mercaptomethyl) diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)SH (11) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SH (12) wird beschrieben. Während sich die Silane 9 und 10 leicht handhaben lassen, neigen die strukturanalogen (Hydroxymethyl)diorganylsilane (CH\(_3\))\(_2\)Si(H)CH\(_2\)OH (1) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OH (2) zu einer basenkatalysierten Zersetzung (Bildung oligomerer (polymerer) Alkoxysilane und Wasserstoff). Im Gegensatz zu den thermisch labilen (Acetoxymethyl)diorganylsilanen (CH\(_3\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (3) und (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (4) (--+ Umlagerung zu den entsprechenden Acetoxy(methyl) diorganylsilanen (CH\(_3\)) \(_3\)SiOC(O)CH\(_3\) (5) und CH\(_3\)(C\(_6\)H\(_5\))\(_2\)SiOC(O)CH\(_3\) {6)) sind die Thio-Analoga 9 und 10 thermisch stabil (I-molare Lösungen in C\(_6\)D\(_6\), 30 h bei 180 o C).
N2  - The novel synthesis of the (thioacetoxy-S-methyl)diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (9) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SC(O)CH\(_3\) (10) and the (mercaptomethyl) diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)SH (11) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)SH (12) is described. The silanes 11 and 12 areeasy to handle, whereas the structurally analogous (hydroxymethyl)diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)OH (1) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OH (2) tend to undergo a base-catalyzed decomposition (formation of oligomeric (polymeric) alkoxysilanes and hydrogen). In cantrast to the thermally unstable (acetoxymethyl)diorganylsilanes (CH\(_3\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (3) and (C\(_6\)H\(_5\))\(_2\)Si(H)CH\(_2\)OC(O)CH\(_3\) (4) (--+ rearrangement to the corresponding acetoxy(methyl)diorganylsilanes (CH\(_3\)) \(_3\)SiOC(O)CH\(_3\) (5) and CH\(_3\)(C\(_6\)H\(_5\))\(_2\)SiOC(O)CH\(_3\) (6)), the thio-analogues 9 and 10 are thermally stable (1 molar solutions in C\(_6\)D\(_6\) , 30 h at 180°C).
KW  - Anorganische Chemie
Y1  - 1990
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64065
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Becker, B.
A1  - Berg, D.
A1  - Brandes, W.
A1  - Dutzmann, S.
A1  - Schaller, S.
T1  - Bis(4-fluorophenyl)methyl(1H-1,2,4-triazol-1-yl-methyl)germane, a germanium analogue of the agricultural fungicide flusilazole: synthesis and biological properties
N2  - Bis( 4-fluorophenyl)methyl(l H-1,2,4-triazol-1-yl-methyl)germane (2), a germanium analogue of the agricultural fungicide flusilazole (1), has been synthesized from Cl\(_3\)GeCH\(_2\)CI (3) by both a three-step and a four-step synthesis (3-> (p-F-C\(_6\)H\(_4\))\(_2\)Ge(CH\(_2\)Cl)Br (4)-> (p-F-C\(_6\)H\(_4\))\(_2\)Ge(CH\(_2\)CI)CH\(_3\) (S)-> 2; S ~ (p-F-C\(_6\)H\(_4\))\(_2\)Ge(CH\(_2\)I)CH\(_3\) (6)-> l). The fungicidal properties of l have been compared with those of the parent silicon compound 1 (studies on Si/Ge bioisosterism). In various test systems, the SijGe analogues 1 and 2 showed comparable fungicidal properlies (in activity against plant pathogenic fungi: in agar plate diffusion tests and greenhause evaluations; in activity against human pathogenic fungi: in serial dilution tests). In addition, 1 and 2 displayed comparable potencies in respect of sterol biosynthesis inhibition in Sacclulromycopsis üpolytica and Pyricularia oryzae, the mode of action being primarily an inhtbition of oxidative C14-demethylation.
KW  - Anorganische Chemie
Y1  - 1992
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64224
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Becker, B.
T1  - Synthese und Eigenschaften von (Hydroxymethyl)dimethylgerman und (Hydroxymethyl)diphenylgerman
N2  - Die (Hydroxymethyl)diorganylgermane (CH\(_3\))\(_2\)Ge(H)CH\(_2\)OH und (C\(_6\)H\(_5\))\(_2\)Ge(H)CH\(_2\)OH wurden - ausgehend von GeCl\(_4\) - durch eine jeweils vierstufige Synthese mit einer Gesamtausbeute von 15 bzw. 32% dargestellt (GeCl\(_4\) ---+ Cl\(_3\)GeCH\(_2\)Cl -> R \(_2\)Ge(Cl)CH \(_2\)Cl ->R \(_2\)Ge(OAc)CH\(_2\)OAc--) R \(_2\)Ge(H)CH\(_2\)OH; R = CH\(_3\) bzw. C\(_6\)H\(_5\) ). Die chemische Reaktivität der Germane (CH\(_3\))\(_2\)Ge(H)CH\(_2\)OH und (C\(_6\)H\(_5\))\(_2\)Ge(H)CH\(_2\)OH wird durch deren Ge-H- und 0-H-Bindung bestimmt.
N2  - Starting from GeCl\(_4\) , the (hydroxymethyl)diorganylgermanes (CH\(_3\)) \(_2\)Ge(H)CH\(_2\)- 0H and (C\(_6\)H\(_5\)) \(_2\)Ge(H)CH\(_2\)OH were prepared by a four-step synthesis in total yields of 15 and 32%, respectively (GeCl\(_4\) ---. Cl\(_3\)GeCH\(_2\)Cl -> R \(_2\)Ge(Cl)CH\(_2\)Cl -> R \(_2\)Ge(OAc)CH\(_2\)OAc--+ R \(_2\)Ge(H)CH\(_2\)OH; R = CH\(_3\) or C\(_6\)H\(_5\) ). The chemical reactivity of (CH\(_3\) ) \(_2\)Ge(H)CH\(_2\)OH and (C\(_6\)H\(_5\)) \(_2\)Ge(H)CH \(_2\)OH was found to be determined by their Ge-Hand 0-H bonds.
KW  - Anorganische Chemie
Y1  - 1988
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63895
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Becht, J.
A1  - Mattern, G.
A1  - Kuhs, W. F.
T1  - Zur Existenz zwitterionischer \(\lambda_5\)-(Ammonioorganyl)tetrafluorosilicate: Synthese sowie Kristall- und Molekülstruktur von Tetrafluoro(pyrrolidiniomethyl)silicat
T1  - On the Existence of Zwitterionic \(\lambda_5\)-(Ammonioorganyl)tetrafluorosillcates: Synthesis and Crystal and Molecular Structure of Tetrafluoro(pyrrolidiniomethyl)silicate
N2  - The zwitterionic tetrafluoro(pyrrolidiniomethyl)silicate (6) was synthesized by the reaction of trimethoxy(pyrrolidinomethyl) silane (7) with hydrogen fluoride in ethanol/hydrofluoric acid (yield 83%). 6 crystallizes in the space group P2\(_1\)fc with two crystallographically distinct molecules in the asymmetric unit. In both molecules the pentacoordinate silicon atom is surrounded by four fluorine atoms and one carbon atom, the latter being in an equatorial position. The coordination polyhedron of the silicon atoms can be described as a slightly distorted trigonal bipyramid. The zwitterionic structure was also proved for dissolved 6 (solution in CD\(_3\)CN, NMRspectroscopic studies).
KW  - Anorganische Chemie
KW  - Fluorosilicates
KW  - zwitterionic
KW  - Pentacoordinate silicon
Y1  - 1992
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64217
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
A1  - Becht, J.
A1  - Lopez-Mras, A.
A1  - Sheldrick, W. S.
A1  - Sebald, A.
T1  - Syntheses, X-ray crystal structure analyses, and solid-state NMR studies of some zwitterionic organofluorosilicates
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1993
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64272
ER  - 
TY  - JOUR
A1  - Tacke, Reinhold
T1  - Sila-Analoga des Meflophenhydramins
T1  - Sila-analogues of Meflophenhydramine
N2  - Die Sila-Analoga A, 8, C des Antihistaminikums Meflophenhydramin, sowie die Derivate D und E, das Hydrolyseprodukt 8 und die Vorstufen 3-7 wurden dargestellt. Die chemischen und physikalischen Eigenschaften aller Verbindungen und das pharmakologische Verhalten von A-D und 8 wurden untersucht.
N2  - Sila-analogues A, 8, C of the antihistamine meflophenhydramine as weil as the derivatives D and E, the product of hydrolysis 8 and the precursors 3-7 were synthesized. The chemical and physical properties and the pharmacological behaviour of A-D and 8 are described.
KW  - Anorganische Chemie
Y1  - 1977
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63594
ER  - 
TY  - JOUR
A1  - Syldatk, C.
A1  - Stoffregen, A.
A1  - Wuttke, F.
A1  - Tacke, Reinhold
T1  - Enantioselective reduction of acetyldimethylphenylsilane: a screening with thirty strains of microorganisms
N2  - Thirty strains of microorganisms (bacteria, yeasts, fungi and green algae) were tested as resting free cells for their ability to transform acetyldimethylphenylsilane (1) enantioselectively into (R)-(1-hydroxyethyl) dimethylphenylsilane [(R)-2]. The biotransformations were monitared by GC (packed OV-17 column), and the enantiomeric purities of the products isolated were determined by HPLC (cellulose triacetate column, UV detection). All microorganisms tested were found to reduce 1 enantioselectively to give (R)-2. Under the test conditions used, the yeast Trigonapsis variabilis (DSM 70714) was found to 1 exhibif the highest specific activity (1.5 mg product x g cell wet mass\(^{-1}\) x min\(^{-1}\) ), whereas the highest enantioselectivities were observed for the bacteria Acinetobacter ca lcoaceticus (ATCC 31012) (>95% ee), Brevfbacterium species (ATCC 21860) (90% ee) and Corynebacterium dioxydans (ATCC 21766) (>95% ee), the yeast Candida humico la (OSM 70067) (90% ee), the fungus Cunninghame lla e legans (ATCC 26269) (94% ee), as well as the cyanobacterium Synechococcus leopoliensis (94% ee).· From the green algae tested, Chlamydomonas reinhardii showed the highest.enantioselectivity (85% ee).
KW  - Anorganische Chemie
Y1  - 1988
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63906
ER  - 
TY  - JOUR
A1  - Syldatk, C.
A1  - Andree, H.
A1  - Stoffregen, A.
A1  - Wagner, F.
A1  - Stumpf, B.
A1  - Ernst, L.
A1  - Zilch, H.
A1  - Tacke, Reinhold
T1  - Enantioselective reduction of acetyldimethylphenylsilane by Trigonopsis variabilis (DSM 70714)
N2  - Growing and resting cells of the yeast Trigonapsis variabilis (DSM 70714) can be used for the enantioselective reduction of the organosilicon compound acetyldimethylphenylsilane (J) to give optically active (R)-(1-hydroxyethyl)dimethylphenylsilane [(R)-2] in good yields. The enantiomeric purity of the isolated product was determined tobe 62-86% ee depending on the substrate concentration used. Both substrate and product caused an inhibition of the reaction at concentrations higher than 0.35 and 0.5 g/1, respectively. Besides, higher substrate and product concentrations led to increased formation of the by-product 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane. Considering the limiting substrate and product concentrations, it was possible to use the same biomass at least 5 times without significant loss of enzyme activity. 3-Methyl-3-phenyl-2-butanone (5) and acetyldimethylphenylgermane (7), which represent carbon and germanium analogues of 1, were also found to be accepted as substrates by Trigonapsis variabilis (DSM 70714). The reduction rates of the silicon {1) and germanium compound {7) were much higher than the transformation rate of the corresponding carbon analogue 5.
KW  - Anorganische Chemie
Y1  - 1987
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63836
ER  - 
TY  - JOUR
A1  - Strohmann, C.
A1  - Tacke, Reinhold
A1  - Mattern, G.
A1  - Kuhs, W. F.
T1  - Bis(2,3-naphthalindiolato)[2-(pyrrolidinio)ethyl]silicat: Synthese und strukturelle Charakterisierung eines zwitterionischen \(\lambda_5\)-Spirosilicates
N2  - The zwi tterionic spirocyclic bis(2,3-naphthalenediolato )[2-(pyrrolidinio )ethyl]silicate [ ( C\(_{10}\)H\(_6\)O\(_2\)-SiCH\(_2\)CH\(_2\)(H)NC\(_4\)H\(_8\), 3 was synthesized and its structure characterized (single crystal X-ray structural analysis; \(^1\)H, \(^{13}\)C and \(^{29}\)Si NMR studies of solutions in DMSO). 3 was obtained by reaction of cyclohexylmethoxyphenyl(2-pyrrolidinoethyl)silane [C\(_6\)H\(_{11}\)(CH\(_3\)O)Si(C\(_6\)H\(_5\))CH\(_2\)CH\(_2\) NC\(_4\)H\(_8\), 4] with 2,3-dihydroxynaphthalene [C\(_{10}\)H\(_6\)(OH)\(_2\)] in acetonitrile at room temperature (isolated as 3·CH\(_3\)CN, yield 81 %). The formation of 3 involves two unusual Si-C cleavage reactions (cleavage of Si-C\(_6\)H\(_5\) and Si-C\(_6\)H\(_{11}\) under mild reaction conditions). In addition, 3 was prepared by reaction of 2,3-dihydroxynaphthalene with dimethoxyphenyl(2-pyrrolidinoethyl)silane [C\(_6\)H\(_5\) (CH\(_3\)O)\(_2\)SiCH\(_2\)CH\(_2\)NC\(_4\)H\(_8\) , 5] and trimethoxy( 2-pyrrolidinoethyl)silane [(CH\(_3\)O)\(_3\)SiCH\(_2\)CH\(_2\)NC\(_4\)H\(_8\), 6], respectively (isolated as 3·CH\(_3\)CN; yields 83 and 86%, respectively). 3·CH\(_3\)CN crystallizes in the space group Pbca with a = 8.877(2) A. b-= 22.823(4) Ä, c""" 24.597(4) A, and Z = 8 (R- 0.0592, Rw = 0.0529). The pentacoordinated Si atom of 3·CH\(_3\)CN is surrounded by its ligands in a nearly ideal square-pyramidal fashion (four basal 0 atoms and one apical C atom). The CH3CN molecule does not coordinate to the Si atom.
N2  - Das Zwitterionische spirocyclische Bis(2,3-naphthalindiolato )[2-(pyrrolidinio )ethyl)silicat [( C\(_{10}\)H\(_6\)O\(_2\)-SiCH\(_2\)CH\(_2\)(H)NC\(_4\)H\(_8\), 3) wurde synthetisiert und strukturell charakterisiert (Einkristallröntgenstrukturanalyse von 3·CH\(_3\)CN; \(^1\)H-, \(^{13}\)C- und \(^{29}\)Si-NMR-Untersuchungen von Lösungen in DMSO). 3 wurde durch Reaktion von Cyclohexylmethoxyphenyl(2·pyrrolidinoetbyl)silan [C\(_6\)H\(_{11}\)(CH\(_3\)O)Si(C\(_6\)H\(_5\))CH\(_2\)CH\(_2\) NC\(_4\)H\(_8\), 4] mit 2,3-Dihydroxynaphthalin [C\(_{10}\)H\(_6\)(OH)\(_2\)] in Acetonitril bei Raumtemperatur erhalten (isoliert als 3·CH\(_3\)CN, Ausbeute 81%). Der Bildung von 3 liegen zwei ungewöhnliche Si-eSpaltungen zugrunde (Spaltung von Si-C\(_6\)H\(_5\) und Si-C\(_6\)H\(_{11}\) unter milden Reaktionsbedingungen). 3 wurde auch durch Reaktion von 2,3-Dibydroxynaphthalin mit Dimethoxyphenyl(2-pyrrolidinoethyl)silan [C\(_6\)H\(_5\) (CH\(_3\)O)\(_2\)SiCH\(_2\)CH\(_2\)NC\(_4\)H\(_8\), 5) bzw. Trimethoxy(2-pyrrolidinoethyl)silan [(CH\(_3\)O)\(_3\)SiCH\(_2\)CH\(_2\)NC\(_4\)H\(_8\),6] dargestellt (isoliert als 3·CH\(_3\)CN, Ausbeute 83 bzw. 86%). 3·CH\(_3\)CN kristallisiert in der Raumgruppe Pbca mit a- 8.877(2) b = 22.823(4), c- 24.597(4) A und Z-8 (R == 0.0592,
KW  - Anorganische Chemie
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64095
ER  - 
TY  - JOUR
A1  - Strohmann, C.
A1  - Bauerecker, S.
A1  - Cammenga, H. K.
A1  - Jones, P. G.
A1  - Mutschler, E.
A1  - Lambrecht, G.
A1  - Tacke, Reinhold
T1  - Enantiomers of the muscarinic antagonist 1-cyclohexyl-1-(4-fluorophenyl)-4-piperidino-1-butanol (p-fluoro-hexahydro-difenidol): synthesis, absolute configuration, and enantiomeric purity
N2  - The enantiomers of the antimuscarinic agent 1-cyclohexyl-1- (4-fluorophenyl)-4-piperidino-1-butanol [(R)- and (S)-p-fluorohexahydro- difenidol] ((R)- and (S)-2a] and their methiodides (R)- 3 and (S)-3 were prepared with high enantiomeric purity. (R)- 2a and (S)-2a (isolated as hydrochlorides) were obtained by catalytic hydrogenation (Pd/C contact) of the corresponding enantiomers of 1-cyclohexyl-1-( 4-fl uorophen yl)-4-piperidino- 2-butyn-1-ol [(R)- and (S)-4]. Reaction of (R)-2a and (S)-2a with rnethyl iodide led to (R)-3 and (S)-3, respectively. The unsaturated precursors (R)- and (S}-4 (enantiorneric purity ~ 99.80 and ~99.94% e.e.; calorimetric analysis) were prepared by res-sepaolution of rac-4 [available from 4-FC\(_6\)H\(_4\)C(O)C\(_6\)H\(_{11}\) by reaction with LiC ~ CCH\(_2\)NC\(_5\)H\(_{10}\)] using (R)- and (S)-mandelic acid as resolving agents. The absolute configurations of the (R) and (S) enantiomers of 2a, 3, and 4 were determined by an X-ray crystal-structure analysis of (S)-5, the methiodide of (S)-4. (R)- 2a and (R)-3 exhibit a higher affinity for muscarinic M1, M2, M3, and M4 receptors (by up to two orders of magnitude) than their corresponding antipodes (S)-2a and (S)-3, the degree of stereoselectivity depending on the receptor subtype involved. (R)-2a represents a useful tool for rnuscarinic receptor research (affinity profile: M1 ~ M3 ~ M4 > M2).
KW  - Anorganische Chemie
KW  - Difenidol
KW  - p-fluoro-hexahydro-
KW  - enantiomers of / Muscarinic receptors
KW  - subtypes of
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64144
ER  - 
TY  - JOUR
A1  - Steiling, L.
A1  - Tacke, Reinhold
A1  - Wannagat, U.
T1  - Diphenyl(3-piperidinopropyl)silanol, ein Sila-Analogon des Difenidols
T1  - Dipbenyl(3-piperidinopropyl)silanol, a Sila-Analogue of Difenidol
N2  - Diphenyl(3-piperidinopropyl)silanol (6b), ein Sila-Analogon des Arzneimittels Difenidol (6a), und dessen Methoiodid 7 wurden erstmals gemäß Schema 1 synthetisiert. - Die pharmakologischen und toxikologischen Eigenschaften der Analoga 6a und 6b wurden vergleichend untersucht.
N2  - Diphenyl(3-piperidinopropyl)silanol (6b), a sila-analogue of the drug difenidol (6a), and its methoiodide 7 were synthesized for the firsttime according to scheme 1. - The pharmacological and toxicological properties of the analogues 6a and 6b were investigated comparatively.
KW  - Anorganische Chemie
Y1  - 1979
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63618
ER  - 
TY  - JOUR
A1  - Sperlich, Jörg
A1  - Becht, Joachim
A1  - Mühleisen, Mathias
A1  - Wagner, Stephan A.
A1  - Mattern, Günter
A1  - Tacke, Reinhold
T1  - Zwitterionische Bis[vic-arendiolato(2-)][(morpholinio)alkyl]silicate: Synthese sowie strukturelle Charakterisierung in Lösung und im Kristall
N2  - No abstract available.
KW  - Silicate
KW  - Bis[1,2-benzendiolato(2-)][(morpholinio)alkyl]silicates
KW  - Bis[2,3-naphthalenediolato(2-)][(morpholinio)alkyl]silicates
KW  - Zwitterionic [lambda]5-Spirosilicates
Y1  - 1993
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-73153
ER  - 
TY  - JOUR
A1  - Sheldrick, W. S.
A1  - Linoh, H.
A1  - Tacke, Reinhold
A1  - Lambrecht, G.
A1  - Moser, U.
A1  - Mutschler, E.
T1  - Crystal and molecular structures of the (R)-enantiomer and the racemate of the antimuscarinic agent (cyclohexyl)phenyl[2-(pyrrolidin-1-yl)ethyl]silanol (sila-procyclidine)
N2  - The crystal structures of the (R)-enantiomer (2b) and the racemate (1 b) of (cyclohexyl)phenyl[2- (pyrrolidin-1-yl)ethyl]silanol (sila--procyclidine) have been determined by X -ray structural analysis. The absolute configuration of (2b) was established. (2b) crystallizes in the orthorhombic space group P2\(_1\)2\(_1\)2\(_1\), with a = 15.221 (1 ), b = 17.967(1 ), c = 6.463(1) A, and Z = 4. (1 b) crystallizes in the monoclinic space group P2\(_1\)/c, with a = 6.441 (1 ), b = 17.1 82(7), c = 16.707(4) A, ß = 1 03.86(2r, and Z = 4. The structures were refined to respective R factors of 0.044 and 0.058. The molecular conformation of sila-procyclidine is identical in the two different structures. lntermolecular 0-H • • • N hydrogen bonding is observed in both crystallattices.ln (1 b) (R)- and (S)-configurated molecules form centrosymmetric dimers, in (2b) the (R)-configurated molecules are linked into infinite chains parallel to the c axis. The (R)-configurated sila--procyclidine (2b) has higher affinity for ileal and atrial muscarinic receptors of the guinea pig than the (S)-configurated enantiomer (3b).
KW  - Anorganische Chemie
Y1  - 1985
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63776
ER  - 
TY  - JOUR
A1  - Schomburg, D.
A1  - Link, M.
A1  - Linoh, H.
A1  - Tacke, Reinhold
T1  - Molekülstruktur der Akarizide Chlortrineophylstannan, Chlortris[(dimethylphenylsilyl)methyl]stannan und Trineophyl(1,2,4-triazol-1-yl)stannan-hemihydrat sowie des 2,5-Dimethyl-2,5-diphenylhexans (Bineophyl)
N2  - Die Kristall- und Molekülstrukturen der Akarizide Chlortrineophylstannan (Ia), Chlortris[ ( dimethylphenylsilyl)methyl]stannan (tb) und Trineophyl(1,2,4-triazol-1- yl)stannan-hemihydrat (2a · 0.5H\(_2\)0) wurden durch Einkristall-Röntgenstrukturanalysen bestimmt. Zu V ergleichszwecken wurde ausserdem die Struktur des 2,5-Dimethyl-2,5-diphenylhexans (Bineophyl, 4) untersucht. Die Knüpfung von drei sehr raumerfüllenden N eophyl-Resten an ein Zinnatom führt zu einer deutlichen Verzerrung der tetraedrischen Geometrie [ta: C-Sn-C 117.2°, C-Sn-Cl99.7°; 2a·0.5H20: C-Sn-C 116.9° (Mittelwert), C-Sn-N 100.2° (Mittelwert)]. Austausch der zentralen Kohlenstoffatome in den Neophyt-Substituenten von la durch Siliciumatome führt zu einer Verringerung des Raumbedarfs und dadurch zu einer erkennbaren Angleichung an die tetraedrische Geometrie [lb: C-Sn-C 113.3° (Mittelwert), C-Sn-Cl 105.3° (Mittelwert)].
N2  - The crystal and molecular structures of the acaricides chlorotrineophylstannane (ta), chlorotris[( dimethylphenylsilyl)methyl]stannane (tb ), and trineophyl(1,2,4-triazol- 1-yl)stannane hemihydrate (2a · 0.5H\(_2\)0), have been determined by single-crystal X-ray diffraction studies. The structure of 2,5-dimethyl-2,5-diphenylhexane (4) was also investigated for comparison. Binding of three very bulky neophyl ligands around tin causes serious distortion of the tetrahedral geometry [la: C-Sn-C 117.2°, C-Sn-Cl 99.7°; la · 0.5H20: C-Sn-C 116.9° (mean), C-Sn-N 100.2° (mean)]. Replacement of the central carbon atoms in the neophyl substituents of ta by silicon atoms Ieads to a decrease in steric strain and hence to a much smaller distortion of the tetrahedral geometry [lb: C-Sn-C 113.3° (mean), C-Sn-Cl105.3° (mean)].
KW  - Anorganische Chemie
Y1  - 1988
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63840
ER  - 
TY  - JOUR
A1  - Sarge, S.
A1  - Cammenga, H. K.
A1  - Becker, B.
A1  - Rohr-Aehle, R.
A1  - Tacke, Reinhold
T1  - Energetic and kinetic investigation of thermally induced molecular rearrangements of esters of (hydroxymethyl)hydridosilanes by DSC
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1988
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63850
ER  - 
TY  - JOUR
A1  - Saad, S. M.
A1  - Tacke, Reinhold
T1  - Zur Darstellung von 1,1,3,3-Tetramethyl-1,3-disila-2,4,7-trioxa-cycloheptan (1) und 1,1,3,3-Tetramethyl-1,3-disila-2,4,8-trioxa-cyclooctan (2)
N2  - No abstract available.
KW  - Anorganische Analyse
Y1  - 1977
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-86958
ER  - 
TY  - JOUR
A1  - Rettenmayr, N. M.
A1  - Rodrigues de Miranda, J. F.
A1  - Rijntjes, N. V. M.
A1  - Russel, F. G. M.
A1  - van Ginneken, C. A. M.
A1  - Strohmann, C.
A1  - Tacke, Reinhold
A1  - Lambrecht, G.
A1  - Mutschler, E.
T1  - Pharmacokinetic properties of the antimuscarinic drug [\(^3\)H]-hexahydro-sila-difenidol in the rat
N2  - The pharmacokinetics of tritiated hexahydrosila- difenidol ([\(^3\)H]-HHSiD) were examined in rats. Furthermore, the distribution of radioactivity was studied by means of whole body autoradiography. After i. v. administration of 2.9 mg/kg HHSiD plus [\(^3\)H]-HHSiD to anaesthetized rats bearing a catheter implanted in the ductus choledochus and receiving a mannitol infusion, HHSiD was rapidly distributed and metabolized. Only 5% ofthe radioactivity was recovered in blood after 23 s and 0.4% after 2.5 h. 64% of the plasma radioactivity could be extracted with hexane from the samples taken 23 s after administration. 52% of the radioactivity was eliminated within 2.5 h, 13% by urinary and 39% by biliary excretion. Following oral administration of 8.6 mg/kg HHSiD plus [\(^3\)H]-HHSiD there was an absorption of approximately one fourth of the administered radioactivity within 4 h. By means of whole body autoradiography (i. v. injection) as well as by tissue distribution measurement the highest Ievels of radioactivity were found in bile, urine, lung, kidney, adrenals, liver and .pancreas. Thus, after i. v. administration to rats HHSiD is rather quickly distributed, metabolized and excreted. This explains its low antimuscarinic potency in vivo.
KW  - Anorganische Chemie
KW  - Pharmacokinetics
KW  - [3H]-Hexahydro-siladifenidol
KW  - Sila-drug
KW  - Rat
KW  - Autoradiography
Y1  - 1990
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64022
ER  - 
TY  - JOUR
A1  - Polidori, C.
A1  - Massi, M.
A1  - Lambrecht, G.
A1  - Mutschler, E.
A1  - Tacke, Reinhold
A1  - Melchiorre, C.
T1  - Selective antagonists provide evidence that M\(_1\) muscarinic receptors may mediate carbachol-induced drinking in the rat
N2  - The present study served to investigate the ability of seven selective muscarinic antagonists to inhibit carbachol-induced drinking in the rat. The muscarinic antagonists were given by intracerebroventricular (i.c.v.) injection 1 min before the i.c.v. injection of carbachol (1 \(\mu\)g/rat). The M\(_2\) antagonist, methoctramine, was inactive up to 80.3 nmol/rat. The M\(_3\) antagonist, p-fluoro-hexahydro-sila-difenidol, elicited a modest (42%) but statistically significant inhibition of drinking only at 80 nmol/rat. On the other band, the selective M\(_1\) antagonists, (R)-trihexyphenidyl, o-methoxy-sila-hexocyclium and pirenzepine, produced a marked and dose-dependent inhibition of carbachol-induced drinking, their 1050 values being 0.51. 7.36 and 9.31 nmoljrat. Also the M\(_1\)/M\(_3\) antagonists, 4-diphenylacetoxy-Nmethylpiperidine methiodide and hexahydro-sila-difen.idol, were potent inhibitors of carbachol-induced drinking, their ID\(_50\) values (0.28 and 11.09 nmoljrat) being related to their pA\(_2\) values for M1 receptors in rabbi t vas deferens. These data suggest that carbachol-induced drinking may be mediated by activation of muscarinic M\(_1\) receptors.
KW  - Anorganische Chemie
KW  - Carbachol-induced drinking
KW  - Muscarinic receptor antagonists
KW  - Muscarinic receptor subtypes
KW  - Muscarinic M1 receptors; Muscarinic M2 receptors
Y1  - 1990
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64044
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  - Lambrecht, G.
A1  - Gmelin, G.
A1  - Rafeiner, K.
A1  - Strohmann, C.
A1  - Tacke, Reinhold
A1  - Mutschler, E.
T1  - o-Methoxy-sila-hexocyclium: a new quaternary M\(_1\)-selective muscarinic antagonist
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1988
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63862
ER  - 
TY  - JOUR
A1  - Lambrecht, G.
A1  - Feifel, R.
A1  - Wagner-Röder, M.
A1  - Strohmann, C.
A1  - Zilch, H.
A1  - Tacke, Reinhold
A1  - Waelbroeck, M.
A1  - Christophe, J.
A1  - Boddeke, H.
A1  - Mutschler, E.
T1  - Affinity profiles of hexahydro-sila-difenidol analogues at muscarinic receptor subtypes
N2  - In an attempt to assess the structural requirements of hexahydro-sila-difenidol for potency and selectivity, a series of analogues modified in the amino group and the phenyl ring were investigated for their affinity to muscarinic M1- (rabbit vas deferens), Mr (guinea-pig atria) and Mr (guinea-pig ileum) receptors. All compounds were competitive antagonists in the three tissues. Their affinities to the three muscarinic receptor subtypes differed by more than two orders of magnitude and the observed receptor selectivities were not associated with high affinity. The pyrrolidino and hexamethyleneimino analogues, compounds substituted in the phenylring with a methoxy group or a chlorine atom as weil as p-fluoro-hexahydro-difenidol displayed the same affinity profile as the parent compound, hexahydro-sila-difenidol: M1 = M3 > M2 • A different selectivity patternwas observed for p-fluoro-hexahydro-sila-difenidol: M3 > M1 > M2 • This compound exhibited its highest affinity for M3-receptors in guinea-pig ileum (pA 2 = 7.84), intermediate affinity for M1-receptors in rabbit vas deferens (pA 2 = 6.68) and lowest affinity for the Mrreceptors in guinea-pig atria (pA 2 = 6.01). This receptor selectivity profile of p-fluoro-hexahydro-sila-difenidol was confirmed in ganglia (M1), atria (M2 ) and ileum (M 3 ) of the rat. Furthermore, dose ratios obtained with either pirenzepine (Mt) or hexahydrosila- difenidol (M2 and M3) and the p-fluoro analogue used in combination suggested that the antagonism was additive, implying mutual competition with a single population of muscarinic receptor subtypes. These results indicate that p-fluoro-hexahydro-sila-difenidol represents a valuable tool for characterization of muscarinic receptor subtypes.
KW  - Anorganische Chemie
KW  - Muscarinic receptor subtypes
KW  - Muscarinic M3selective antagonists
KW  - Hexahydro-sila-difenidol analogues
Y1  - 1989
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63979
ER  - 
TY  - JOUR
A1  - Lambrecht, G.
A1  - Feifel, R.
A1  - Forth, B.
A1  - Strohmann, C.
A1  - Tacke, Reinhold
A1  - Mutschler, E.
T1  - p-Fluoro-hexahydro-sila-difenidol: the first M\(_{2\beta}\)-selective muscarinic antagonist
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1988
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63872
ER  - 
TY  - JOUR
A1  - Kopp, R.
A1  - Lambrecht, G.
A1  - Mutschler, E.
A1  - Moser, U.
A1  - Tacke, Reinhold
A1  - Pfeiffer, A.
T1  - Human HT-29 colon carcinoma cells contain mucarinic M\(_3\) receptors coupled to phosphoinositide metabolism
N2  - Five different musearlnie receptor subtypes ean be distinguished by the differenees in their amino aeid sequence, the eoupled signal transduetion system, pharmaeologieal binding properties and aetivation of ionie fluxes. The present study served to eharaeterize the binding profile of musearlnie receptors in human eolon eareinoma eells (HT-29) using seleetive musearlnie antagonists. The affinities of the compounds were eompared with their poteney to inhibit cholinergieally-aetivated phosphoinositide metabolism. Pirenzepine displaced [\(^3\)H]N-methyl-scopolamine binding and inhibited inositolphosphate (IP) release with potencies typieal of those of non-M\(_1\) receptors. The M\(_3\) subtype-selective antagonists sila-hexocyelium and hexahydro-sila-difenidol bad high affinity to the musearlnie reeeptors in HT-29 cells (K0 = 3.1 nM and 27 nM, respectively) and inhibited IP release at nanomolar concentrations. The M\(_2\) receptor antagonists, AF-DX 116 and methoctramine, had low antimusearinic poteneies. Our results demonstrate that HT-29 human colon earcinoma cells contain an apparently pure population of M\(_3\) receptors. These cells could serve as a model system for further investigations coneerning regulatory and signal transduction mechanisms associated with glandular muscarinic M\(_3\) receptors.
KW  - Anorganische Chemie
KW  - Muscarinic M3 receptor subtypes
KW  - HT-29 colon carcinoma cells
KW  - Phosphatidylinositol metabolism
KW  - AF-DX 116
Y1  - 1989
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63989
ER  - 
TY  - JOUR
A1  - Jaiswal, Neelam
A1  - Lambrecht, Günter
A1  - Mutschler, Ernst
A1  - Tacke, Reinhold
A1  - Malik, Kafait U.
T1  - Pharmacological characterization of the vascular muscarinic receptors mediating relaxation and contraction in rabbit aorta
JF  - Journal of Pharmacology and Experimental Therapeutics
N2  - Studies were performed in the rabbit aortic rings, precontracted with norepinephrine, to determine the subtype(s) of muscarinic receptors involved in endothelium-dependent relaxation and contraction in the absence of endothelium elicited by cholinergic stimuli. Acetylcholine (ACh) and arecaidine propargyl ester (APE), a M2 and M3 agonist, produced a dose-dependent relaxation and contraction in endothelium-intact and endothelium-denuded rabbit aortic rings, respectively. Both of these responses were blocked by the muscarinic receptor antagonist atropine. M1 selective agonist McN-A-343 [4-[N-(3-chlorophenyl)carbamoyloxy]-2-butinyltrimethylammonium+ ++ chloride] did not produce any effect on the tone of precontracted aortic rings. ACh- and APE-induced relaxation in aortic rings with intact endothelium was selectively blocked by M3 receptor antagonists hexahydrosila-difenidol and p-fluoro-hexahydro-sila-difenidol (pA2 of 7.84 and 7.18) but not by M1 antagonist pirenzepine or M2 receptor antagonists AF-DX 116 [11-(2-[(diethylamino)methyl]- 1-piperidinyl]acetyl)-5, 11-dihydro-6H-pyrido-[2,3-b][1,4]-benzo-diazepin-6-one] and methoctramine. ACh- and APE-induced contraction was inhibited by M2 receptor antagonists AF-DX 116 and methoctramine (pA2 of 7.11 and 6.71) but not by pirenzepine, hexahydro-sila-difenidol or p-fluoro-hexahydro-sila-difenidol. ACh- and APE-induced relaxation or contraction were not altered by nicotinic receptor antagonist hexamethonium or cyclooxygenase inhibitor indomethacin. These data suggest that relaxation elicited by cholinergic stimulin in endothelium-intact aortic rings is mediated via release of endothelium-derived relaxing factor consequent to activation of M3 receptors located on endothelial cells, whereas the contraction in aortic rings denuded of their endothelium is mediated via stimulation of M2 receptors located on smooth muscle cells.
KW  - (4-(m-Chlorophenylcarbamoyloxy)-2-butynyl)trimethylammonium chloride/pharmacology
KW  - acetylcholine
KW  - animals
KW  - antihypertensive agents / pharmacology
KW  - aorta, abdominal / drug effects
KW  - aorta, abdominal / physiology
KW  - aorta, abdominal / ultrastructure
KW  - arecoline/analogs & derivatives
KW  - arecoline
KW  - atropine
KW  - diamines
KW  - endothelium, vascular / drug effects
KW  - endothelium, vascular / physiology
KW  - hexamethonium
KW  - hexamethonium compounds
KW  - indomethacin
KW  - male
KW  - muscarinic antagonists
KW  - muscle contraction
KW  - muscle relaxation
KW  - norepinephrine
KW  - parasympatholytics
KW  - piperidines
KW  - pirenzepine
KW  - rabbits
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-128358
VL  - 258
IS  - 3
ER  - 
TY  - JOUR
A1  - Hengelsberg, H.
A1  - Tacke, Reinhold
A1  - Fritsche, K.
A1  - Syldatk, C.
A1  - Wagner, F.
T1  - Synthesis and enantioselective enzymatic hydrolysis of rac-dimethylphenyl[1-(phenylacetamido)- ethyl]silane
N2  - Racemic dimethylphenyl(l-(phenylacetamido)ethyl)silane [rac-5) has been made by a four-step synthesis starting from (chloromethyl)dimethylphenylsilane [PhMe\(_2\)SiCH2Cl (1) ~ PhMe\(_2\)SiCH(Cl)Me (rac-2) - PhMe\(_2\)SiCH(l)Me (rac-3) - PhMe2SiCH(NH2)Me (rac-4) ~ PhMe\(_2\)SiCH[N(H)C(O)CH\(_2\)Ph]Me ( rac-5); total yield 41% ). Enantioselective enzymatic hydrolysis of rac-5, catalyzed by immobilized penicillin G acylase (E.C. 3.5.1.11) from Escherichia coli 5K (pHM 12), gave (R)-(1- aminoethyl)dimethylphenylsilane [( R )-4] in 40% yield with an enantiomeric purity of 92% ee.
KW  - Anorganische Chemie
Y1  - 1991
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64153
ER  - 
TY  - JOUR
A1  - Fritsche, K.
A1  - Syldatk, C.
A1  - Wagner, F.
A1  - Hengelsberg, H.
A1  - Tacke, Reinhold
T1  - Enzymatic resolution of rac-1,1-dimethyl-1-sila-cyclohexan-2-ol by ester hydrolysis or transesterification using a crude lipase preparation of Candida cylindracea
N2  - No abstract available
KW  - Anorganische Chemie
Y1  - 1989
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-63967
ER  - 
TY  - JOUR
A1  - Feifel, R.
A1  - Wagner-Röder, M.
A1  - Strohmann, C.
A1  - Tacke, Reinhold
A1  - Waelbroeck, M.
A1  - Christophe, J.
A1  - Mutschler, E.
A1  - Lambrecht, G.
T1  - Stereoselective inhibition of muscarinic receptor subtypes by the enantiomers of hexahydro-difenidol and acetylenic analogues
N2  - 1 Tbc affinities of the (R)- and (S)-enantiomers of hexahydro-difenidol (1) and its acetylenie analogues hexbutinol (2), hexbutinol methiodide (3) and p-fluoro-hexbutinol (4) (stereochemieal purity > 99.8%) for musearlnie receptors in rabbit vas deferens (M1), guinea-pig atria (M2) and guinea-pig ileum (M3) were measured by dose-ratio experiments. 2 The (R)-enantiomers consistently showed higher aßinities than the (S)-isomers. The stereosclectivity ratios [(R)/(S)] wcrc greatest with thc enantiomers of 1 (vas deferens: 550; ilcum: 191; atria: 17) and least with thosc ofthc p-Fluoro-analogue 4 (vas defercns: 34; ileum: 8.5; atria: 1.7). 3 The enantiomerie potency ratios for compounds 1-4 were highest in rabbit vas deferens, intermediate in guinea-pig ileum and much less in guinea-pig atria. Thus, these ratios may serve as a predietor of muscarinic receptor subtype identity. 4 (S)-p-Fluoro-hexbutinol [(S)-4] showed a novel receptor selectivity profile with preference for M\(_3\) receptors: M\(_3\) > M\(_2\) \(\geq\) M\(_1\)• 5 These results do not conform to Pfeiffer's rule that aetivity differences between enantiomers are greater with more potent compounds.
KW  - Anorganische Chemie
Y1  - 1990
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-64002
ER  -