TY - JOUR A1 - Christl, Manfred A1 - Brüntrup, Gisela T1 - Diimine Reduction and Ozonolysis of Benzvalene N2 - Via reduction of benzvalene (1) with diirnine tricyclo[3.1.0.02•6]hexane is obtained in good yield. The procedure renders 3, which has already been synthesized by Lemal and Shim, accessible much easier and in larger quantities. IH and 13C n.m.r. spectroscopic data are discussed. Both the thermal and the AgBF4-catalyzed rearrangernent of 3 yield 1,3-cyclohexadiene (8). - The ozonolysis of 1 with subsequent LiAIH4-reduction results in cis-I,3- bis(hydroxyrnethyl)cyclobutane (13a). N2 - Durch Reduktion von Benzvalen (1) mit Diimin wird das Tricyc1o[3.1.0.02•6]hexan (3) in guter Ausbeute erhalten. Das Verfahren macht das bereits von Lemal und Shim dargestellte 3 erheblich leichter und in größeren Mengen zugänglich. IH- und 13C-NMR-spektroskopische Daten werden diskutiert. Sowohl die thermische als auch die AgBF4-katalysierte Umlagerung von 3 führt zu 1,3-Cyclohexadien (8). - Die Ozonolyse von 1 mit anschließender LiAlH4-Reduktion ergibt das cis-l,3-Bis(hydroxymethyl)cyclobutan (13a). KW - Organische Chemie Y1 - 1974 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-57953 ER - TY - JOUR A1 - Bentley, T. W. A1 - Christl, Manfred A1 - Kemmer, R. A1 - Llewellyn, G. A1 - Oakley, J. E. T1 - Kinetic and Spectroscopic Characterisation of Highly Reactive Methanesulfonates. Leaving Group Effects for Solvolyses and Comments on Geminal Electronic Effects Influencing S\(_N\)1 Reactivity N2 - Highly reactive methanesulfonates (mesylates, ROMs) have been prepared from 1-phenylethanol. cyclohex-2-en-1-ol, diphenylmethanol and p-methoxybenzyl alcohol by treatment with methanesulfonyl chloride and triethylamine in dichloro- or trichloro-methane at - 20 to 0 °C. The mesylates. characterised in solution by \(^1\)H and \(^{13}\)C NMR at -20 °C, were obtained in satisfactory purity (ca. 95%) in cold solutions but they decomposed by reaction with chloride, triethylamine or the parent alcohol. Rate constants for solvolyses in aqueous acetone and aqueous ethanol have been determined by a fast response conductimetric method. Product selectivities for solvolyses of pmethoxybenzyl mesylate in aqueous ethanol and methanol at 0 °C have been determined by HPLC. From additional new or Iiterature kinetic data for solvolyses of corresponding bromides. chlorides and p-nitrobenzoates (OPNB). Br/CI. OMs/Br and OMs/OPNB rate ratios were calculated; the results are consistent with electronic effects stabilising the carbocationic transition states and increasing OMs/Br rate ratios for these SN 1 solvolyses; none of the evidence supports a geminal electronic effect on Br/CI rate ratios (e.g. caused by stabilisation of the initial state in pmethoxybenzyl chloride). Steric effects on ester /halide rate ratios for solvolyses of tertiary substrates are confirmed. Relative rates over a 10\(^{16}\) range for ester and halide leaving groups are evaluated for solvolyses of 1-phenylethyl substrates in 80% ethanol-water. updating previous work by Noyce et al. (1972). KW - Organische Chemie Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58748 ER - TY - JOUR A1 - Christl, Manfred A1 - Türk, M. A1 - Peters, K. A1 - Peters, E.-M. A1 - Schnering, H. G. von T1 - Octahydro-1,2,3:4,5,6-dimethenopentalene-2-carbonitrile, the First Derivative of a Yet-Unknown (CH)\(_{10}\)-Hydrocarbon N2 - No abstract available KW - Organische Chemie Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58731 ER - TY - JOUR A1 - Bentley, T. W. A1 - Norman, S. J. A1 - Gerstner, E. A1 - Kemmer, R. A1 - Christl, Manfred T1 - Solvolysis of Tricyclo[3.1.0.0\(^{2,6}\)]hex-3-yl and Bicyclo[2.1.1]hex-2-yl Sulfonates N2 - No abstract available KW - Organische Chemie KW - Bicyclo[1.1.0]butylcarbinyl sulfonates KW - solvolysis of KW - Cyclobutylcarbinyl sulfonates KW - Anchimeric assistance in solvolysis KW - Rearrangement of carbocations KW - Electron demand in ditosylates Y1 - 1993 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58689 ER - TY - JOUR A1 - Christl, Manfred A1 - Braun, Martin A1 - Müller, Germar T1 - 1,2,4-Cyclohexatriene, an Isobenzene, and Bicyclo[4.4.0)deca-1,3,5,7,8-pentaene, an Isonaphthalene: Generation and Trapping Reactions N2 - No abstract available KW - Organische Chemie Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58639 ER - TY - JOUR A1 - Bentley, T. W. A1 - Christl, Manfred A1 - Norman, S. J. T1 - Methanesulfonate/p-Nitrobenzoate and p-Toluenesulfonate/p-Nitrobenzoate Rate Ratios. Solvolyses of 1-Adamantyl and Benzhydryl Substrates N2 - No abstract available KW - Organische Chemie Y1 - 1991 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58599 ER - TY - JOUR A1 - Markgraf, J. H. A1 - Cort, J. R. A1 - Davis, H. A. A1 - Lindeman, N. I. A1 - Myers, C. R. A1 - Kraft, A. A1 - Christl, Manfred T1 - Strained Heterocyclic Systems. 20. Basicities of Bicyclic Quinoxalines N2 - No abstract available KW - Organische Chemie Y1 - 1991 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58584 ER - TY - JOUR A1 - Christl, Manfred A1 - Reuchlein, H. T1 - Synthesis and NMR Spectra of 2,3-Dihydro-1,3-methanoindene Derivatives and 1,2,3,5-Tetrahydro-1,3-methanopentalene N2 - No abstract available KW - Organische Chemie Y1 - 1990 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58557 ER - TY - JOUR A1 - Kim, E. A1 - Christl, Manfred A1 - Kochl, J. K. T1 - Charge-Transfer Cycloaddition of Homobenzvalene with Tetracyanoethylene N2 - The transient yellow color observed in the cycloaddition of homobenzvalene (HB) with tetracyanoethylene (TCNE) is associated with the charge-transfer complex [HB, TCNE). The deliberate photoexcitation of [HB,TCNE) affords a mixture of charge-transfer cycloadducts (1, 2, and 3) that differs from that obtained in thermal cycloaddition. The relationship of {HB t TCNE•) radical-ion pair (as the critical reactive intermediate in charge-transfer cycloaddition) to the activation process for thermal cycloaddition is discussed. KW - Organische Chemie KW - Electron transfer KW - photochemical KW - Radical-ion pair KW - Photochemistry Y1 - 1990 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58537 ER - TY - JOUR A1 - Christl, Manfred A1 - Braun, Max T1 - Photocycloadditions of Benzvalene N2 - No abstract available KW - Organische Chemie Y1 - 1989 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58506 ER -