TY - JOUR A1 - Christl, Manfred A1 - Mattauch, B. T1 - Versuche zur Synthese eines formalen Nitriloxid-Addukts des Benzols. 1,3-Dipolare Cycloadditionen an Bicyclo[2.2.0]hex-5-en-2,3-dicarbonsäureanhydrid, Dewarbenzol und 1,4-Cyclohexadien N2 - No abstract available KW - Organische Chemie Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58216 ER - TY - JOUR A1 - Christl, Manfred A1 - Lanzendörfer, U. A1 - Grötsch, M. M. A1 - Hegmann, J. T1 - Primäraddukt, γ-Ketoketen und einige Folgeprodukte der Reaktion von 6-Oxo-5-phenyl-1,3,4-oxadiazin-2-carbonsäure-methylester mit Norbornen N2 - No abstract available KW - Organische Chemie Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58220 ER - TY - JOUR A1 - Christl, Manfred A1 - Lang, Reinhard A1 - Herzog, Clemens A1 - Stangl, Roland A1 - Peters, Karl A1 - Peters, Eva-Maria A1 - Schnering, Hans Georg von T1 - Reaktion von Homobenzvalen mit Tetracyanethylen : Bildung eines Tetracyandihydrobarbaralan- und eines Tetracyancyclopropan-Derivats N2 - In den Reaktionen von Tetracyanethylen (TCNE) und 5,6-Dichlor-2,3-dicyan-p-benzochinon mit Benzvalen haben wir kürzlich die ersten Beispiele für die lange gesuchte einstufige 1,4-Cycloaddition eines Alkens an ein Vinylcyclopropan gcfunden(I~J. Sie ist als [(.,2.+.2s)+ 112J-Prozeß der Dicls-Alder-Addition nahe verwandtllbl. Allerdings entsteht das betreffende TCNE-Addukt, ein Dihydrosemibullvalen-Derivat, nur in einer Ausbeute von wenigen Prozent. Die Hauptprodukte gehen aus einer Zwitterionischen Zwischenstufe hervor, die durch Anlagerung von TCNE an die Benzvalen-n-Bindung resultiert. Professor Rolf Huisgen zum 65. Geburtstag gewidmet KW - Chemie KW - Homobenzvalene Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-31839 ER - TY - JOUR A1 - Gleiter, Rolf A1 - Bischof, Peter A1 - Gubernator, Klaus A1 - Christl, Manfred A1 - Schwager, Luis A1 - Vogel, Pierre T1 - 2,3-Bis(methylene)bicyclo[2.1.1]hexane and 3,4-Bis(methylene)tricyclo[3.1.0.0\(^{2,6}\)]hexane : Interaction between a π System and a Cyclobutane or Bicyclobutane Moiety N2 - The He (I) photoelectron spectra of 2-bicyclo[2.1.l]hexene (1), 2,3-bis(methylene)bicyclo[2.1.l]hexane (3), and 3,4-bis(methylene)tricyclo[3.l.O.0\(^{2.6}\)]hexane (4) have been investigated. The assignment given is based on a ZDO model and semiempirical calculations. Tagether with the PE data of benzvalene (2), the reported data allow a comparison between 1-2 and 3-4. This yields a measure of the interactions between 8 cyclobutane or 8 bicyclobutane moiety and a double bond system within a ZDO model. The resonance integral found in the case of 1 and 3 amounts to -1.9 eV, that for 2 and 4, to -2.3 eV. The investigations furthermore reveal that the electronic factors which contribute to the higher reactivity of the bicyclobutane compounds amount to 5 kcal/mol. KW - Chemie Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-31845 ER - TY - JOUR A1 - Christl, Manfred A1 - Lanzendörfer, F. A1 - Hegmann, J. A1 - Peters, K. A1 - Peters, E.-M. A1 - Schnering, H. G. von T1 - Cycloadditionen von 6-0xo-l,3,4-oxadiazinen (4,5-Diaza-α-pyronen), 3 : Reaktionen von 6-Oxo-2,5-diaryl-1,3,4-oxadiazinen mit Alkenen T1 - Cycloadditions of 6-0xo-l,3,4-oxadiazines (4,5-Diaza-α-pyrones), 3 : Reactions of 6-0xo-2,5--diaryl-l,3,4-oxadiazines with Alkenes N2 - Das bekannte 6-0xo-2,5-diphenyl-6H-l,3,4-oxadiazin (1 a) und die neuen 2,5-Diarylderivate 1 b - g lagern Alkene an, und es entstehen stickstofIfreie Produkte. Im Falle von Cyclopropenen und Cyclobuten bilden sich die a,p-ungesättigten Siebenring-Enollactone 42 -45 bzw. das a,ß-ungesättigte Achtring-Enollacton 47. 42a und d erleiden an basischem Aluminiumoxid die H-Verschiebung zu den ß,y-ungesättigten Siebenring-Enollactonen 46a bzw. d. Bei weiteren Olefinen wurden die 'Y-Ketoketene des Typs 33 als Zwischenprodukte nachgewiesen oder sind aufgrund der Konstitution der Endprodukte wahrscheinlich. Aus 1 a werden mit Norbomen, Norbornadien, Cyc1openten, trans-Cycloocten und Styrol die Sechsring-Enollactone 10, 13, 15, 19 bzw. 21 und 22 erhalten. 10 isomerisiert mit Kalium-tert-butoxid zu 34, und die Methanolyse dieser Enollactone erbringt die diastereomeren Methy]ester 12 bzw. 35. Das y-Ketoketen 16 aus trans-Cycloocten nimmt schneller Wasser und Methanol zu 17 bzw. 18 auf als es zum Enollacton 19 cyclisiert. cis,trans-l,5-Cyc1ooctadien erbringt über die Stufe des nachgewiesenen y-Ketoketens 40 in einer intramolekularen [2 + 2J-Cyc1oaddition den Tricyclus 41. Tetracyclische Verbindungen des Typs 4 gehen aus der Umsetzung von Benzvalen (2) mit 1 hervor. Durch Röntgenstrukturanalysen wurden Konstitution und Konfiguration von 10, 19 und 41 aufgeklärt N2 - Cycloaddition of the known 6-oxo-2,5-diphenyl-6H-1,3,4-oxadiazine (1 a) and the new 2,5- diaryl derivatives 1 b - g with various alkenes yield nitrogen free products. Using cyclopropenes and cyclobutene, a,~-unsaturated seven-membered enollactones 42-45 and the C't,ßunsaturated eight-membered enollactone 47 are formed, respectively. In the presenee of basic aluminium oxide 42a and d undergo a hydrogen migration to form the ß.y-unsaturated enollactones 46a and d, respectively. With other alkenes, y-ketoketenes 33 have been observed, or are assumed to be intennediates, based on the structure of the isolated products. Tbe six-mernbered enollactones 10, 13, 15, 19, and 21 and 22 have been obtained with norbomene, norbornadiene, cyclopentene, trans-cyclooctene, and styrene. Cornpound 10 isomerizes to 34 on treatment with potassium tert-butoxide. The rnethanolyses of these enollactones result in the formation of the diastereomeric methyl esters 12 and 35. The yketoketene 16 forrned from trans-cyc1ooctene gives acid 17 and ester 18 with water and methanol, respectively. These reactions are faster than the cyc1ization to enollactone 19. From cis,trans-l,5-cyclooctadiene the more short-lived y-ketoketene 40 is formed. which undergoes intramolecular [2 + 2] cycloaddition, giving rise to the tricyclic cyclobutanone derivative 41. Tetracyclic products of type 4 are generated from benzvalene (2) and 1. The structures and configurations of compounds 10, 19, and 41 have been determined by means of X -ray analyses. KW - Organische Chemie Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58191 ER - TY - JOUR A1 - Christl, Manfred A1 - Herzog, C. A1 - Brückner, D. A1 - Lang, R. T1 - Neue Homobenzvalen-Derivate (Tricylo[4.1.0.0\(^{2,7}\)]hept-3-ene) N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58241 ER - TY - JOUR A1 - Christl, Manfred A1 - Lang, R. A1 - Herzog, C. T1 - The Synthesis of Octavalene (Tricyclo[5.1.0.0\(^{2,8}\)]octa-3,5-diene) and Several Substituted Octavalenes N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58254 ER - TY - JOUR A1 - Christl, Manfred A1 - Mattauch, B. A1 - Irngartinger, H. A1 - Goldmann, A. T1 - Additionen von Benzvalen an Nitriloxide. Eine Synthese für Benzvalen-3-carbonitril N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58269 ER - TY - JOUR A1 - Christl, Manfred A1 - Kemmer, P. A1 - Mattauch, B. T1 - 1-Methylbenzvalen. Synthese und einige Reaktionen N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58270 ER - TY - JOUR A1 - Engels, Bernd A1 - Peyerimhoff, S. D. T1 - Theoretical study of the bridging in β-Halo Ethyl N2 - Large-acale multi-reference configuration interaction (MRD-CI) calculations in a quite flexible AO basis are employed to study the energy hypersurface for the reaction intermediates XC\(_3\)H\(_4\) with X = Cl, Br and F. Particular emphasis is therby placed on determining the equilibrium conformations, the CH\(_2\) rotation barrier and the energy surface for a possible bridging (shuttling motion (1a] of X between the two carbon centers). The absolute minimum in the potential energy surface is found in all three cases for the asymmetric ß-halo radical in general agreement with ESR data at an XCC angle of ca. 110°, a c-c separation somewhat shorter than a single bond and an approximate sp3 type hybridization (\(\alpha _2 \approx \) 135-140°). In FC\(_2\)H\(_4\) the energy difference between the minimum in the symmetric conformation and the absolute minimum is found to be more than 30 kcal so that shuttling seems impossible in agreement with experimental findings. In BrC\(_2\)H\(_4\) the difference between these two potential minima is only between 1-2 kcal, i.e., smaller than the barrier to CH\(_2\), rotation, so that· shuttling is favored, while ClC\(_2\)H\(_4\) takes an intermediate position between these extremes. The use of correlated wavefunctions is found to be quite important for such a study; the results are related to various kinetic studies of these radicals. KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58779 ER - TY - JOUR A1 - Gleiter, Rolf A1 - Bischof, Peter A1 - Christl, Manfred T1 - Electronic Structure of Octavalene : Photoelectron Spectroscopic Investigations N2 - The He I photoelectron (PE) spectra of octavalene (5) as weil as its hydrogenated products 6-8 have been investigated. The assignment given is based on an empirical comparison of 5-8 with related compounds, a ZDO model, and semiempirical and ab initio calculations. Within the ZDO model the interaction between the buta.diene moiety and the bicyclobutane fragment of 5 is described by a resonance integral of -2.3 eV. The orbitalsequence of 5 is found tobe 2a\(_2\) (\(\pi\)-\(\sigma\)), 9a\(_1\) (\(\sigma\)), 3b1 (\(\pi\) - \(\sigma\)), 1a\(_2\) (\(\sigma\) + \(\pi\)), 2b\(_1\) (\(\sigma\) + \(\pi\)). KW - Chemie KW - Octavalen KW - Photoelektron Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-31588 ER - TY - JOUR A1 - Christl, Manfred A1 - Brückner, D. T1 - Der Einfluß von Phenylgruppen auf die Homokonjugation im Bicyclo[3.2.1]octa-3,6-dien-2-yl-Anion. Eine \(^{13}\)C-NMR-Studie N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58288 ER - TY - JOUR A1 - Herzog, C. A1 - Lang, R. A1 - Brückner, D. A1 - Kemmer, P. A1 - Christl, Manfred T1 - Norpinene (Bicyclo[3.1.1]hept-2-ene) aus Homobenzvalenen (Tricyclo[4.1.0.0\(^{2,7}\)]hept-3-enen) N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58302 ER - TY - JOUR A1 - Christl, Manfred A1 - Herzog, C. A1 - Kemmer, P. T1 - Tricyclo[5.1.0.0\(^{2,8}\)]oct-3-en, -oct-4-en und -octan: Darstellung und Thermolyse der Hydroderivate des Octavalens N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58310 ER - TY - JOUR A1 - Christl, Manfred A1 - Herzog, C. A1 - Nusser, R. T1 - Bicyclo[4.1.1]octa-2,4-dien, -oct-2-en, -oct-3-en und -octan aus Norpinen N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58326 ER - TY - JOUR A1 - Christl, Manfred A1 - Herzog, C. T1 - \(^{13}\)C-NMR-Spektroskopie: Besondere Hochfeldeffekte in Bicyclo[4.1.1]- und Tricyclo[5.1.0.0\(^{2,8}\)]octan-Systemen (1,3-Cycloheptadien-Effekt) und besondere Tieffeldeffekte in Dihalogenbicyclo[2.1.1]hex-2-enen (Cyclopenten-Effekt) N2 - No abstract available KW - Organische Chemie Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58334 ER - TY - RPRT A1 - Christl, Manfred T1 - Cycloadditions of 1,3,4-Oxadiazin-6-ones N2 - No abstract available Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-41677 ER - TY - JOUR A1 - Engels, Bernd A1 - Peyerimhoff, S.D. A1 - Davidson, E.R. T1 - Calculation of hyperfine coupling constants : An ab initio MRD-CI study for nitrogen to analyse the effects of the basis sets and CI parameter N2 - The hyperfine coupling constant for the nitrogen atom is evaluated by large-scale MRD-CI calculations. A detailed analysis of the charge density at the nucleus and the spin polarization in the ls and 2s shell as a function of various technical parameters is undertaken. Various (s, p) AO basis sets and the inftuence of correlation orbitals is investigated as weil as selection threshold and other properlies in CI calculations. The best value, obtained for the isotropic hyperfine coupling constant in an s, p, d basis, based on theoretical judgment of' best' quantities, is 9·9 MHz compared to 10·4509 MHz. KW - Organische Chemie Y1 - 1987 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58784 ER - TY - JOUR A1 - Schreck, Michael A1 - Christl, Manfred T1 - Generation and Interception of 1-Oxa-3,4-cyclohexadiene N2 - No abstract available KW - Chemie Y1 - 1987 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-31601 ER - TY - JOUR A1 - Christl, Manfred A1 - Schreck, Michael T1 - 1,2,3,5,8,8a-Hexahydronaphthalin aus 1,2-Cyclohexadien N2 - Reaktionen von 1,3-Butadien und einigen seiner Methylderivate mit 1a und 1- Methyl-1,2-cyclohexadien 1b sowie den Übergang der [2 + 2]-Cycloaddukte 2 und 3 in das bisher unbekannte 1,2,3,5,8,8a-HexahydronaphthaJin 4a und einige seiner Methylderivate KW - Chemie KW - Butadien Y1 - 1987 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-31656 ER -