TY - JOUR
A1 - Irngartinger, H.
A1 - Reimann, W.
A1 - Lang, R.
A1 - Christl, Manfred
T1 - Electron Density Distribution in a Bicyclo[l.l.0]butane
N2 - No abstract available
Y1 - 1990
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-31576
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Brunn, E.
A1 - Kraft, A.
A1 - Irngartinger, H.
A1 - Huber-Patz, U.
T1 - Nichtbindende Wechselwirkungen in zwei 7-Spirotetracyclo[4.1.0.0\(^{2,4}\).0\(^{3,5}\)]heptanen
T1 - Nonbonded Interactions in two 7-Spirotetracyclo[4.1.0.0\(^{2,4}\).0\(^{3,5}\)]beptanes
N2 - Die Reaktion von Tetrachlordiazocyclopentadien mit Be.nzvalen (2) ergab das Fulven-Derivat 3. Dagegen führten die Umsetzungen von Diazoßuoren und 5-Diazo-10,1 1-dihydro-SH-dibenzo[ a.d]cyclohepten mit 2 zu den erwarteten Spiro-1-pyrazolinen 4 bzw. 5. Die photolytische Abspaltung von Stickstoff aus 4 und 5 lieferte die Spirotetracycloheptane 6 bzw. 7. Die Röntgenstrukturanalyse von 6 beweist einen engen Kontakt zwischen je eineßl Wasserstoffatom der Tetracycloheptan- und der Fluoren-Einheit. Dieser kurze Abstand (2.15 A) ruft Winkelaufweitungen hervor und wird auch als Grund für starke Entschirmungen der betreffenden Protonen und eine formal über sieben Bindungen reichende 0.6-Hz-Kopplung zwischen ihnen angesehen. 7 ist das erste chiralc Tetracyclohcptan. Ursache dafür ist eine nichtebene Konformation des Siebenrings, der bei Raumtemperatur nicht invertiert. Auf der Basis von NOE-Messungen gelang die Zuordnung der tH-NMR-Signale von 6 und 7.
N2 - The reaction or tctrachlorodiazocyclopentadiene with benzvalene (2) gavc, the fulvene derivative 3. In contrast, treatment of diazoßuorene and 5-diazo-1 0,1 1-dihydro·SH -dibenzo[ a,d]cycloheptene with l:afl'orded the expected spiro-1-pyrazolines 4 and 5, respectively. Photolytic extrusion of nitrogen from 4 and S led to the corresponding spirotetracyclobeptanes 6 and 7. The X-ray structure analysis of 6 revealed a close contact between one hydrogen atom cach of the tetracycloheptane and the ßuorene subunits. This short distance (2.15 A) causes an increase in bond angles and is believed to produce strong deshielding of the respective protons and a 0.6-Hz coupling between them, which is formally a long-range coupling across seven bonds. Compound 7 is the first chirat tetracycloheptane. This is due to a nonplanar confonnation of the seven-membered ring, which does not invert at room temperature. On tbe basis of NOE measurements the 1H-NMR signals of 6 and 7 are assigned.
KW - Organische Chemie
KW - 5H-Dibenzo[a
KW - d]cycloheptene
KW - 10
KW - 11-dihydro- / 1-Pyrazoline
KW - Nonbonded Interactions
KW - Spirotetracyclo[4.1.0.02
KW - 4.03
KW - 5]beptanes
KW - Long-range coupling constants
KW - mtrogen extruston
Y1 - 1989
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58489
ER -
TY - JOUR
A1 - Christl, Manfred
A1 - Freund, S.
A1 - Henneberger, H.
A1 - Kraft, A.
A1 - Hauck, J.
A1 - Irngartinger, H.
T1 - Several Polycyclic Valence Isomers of Dimethyl [14]Annulene-1,8-dicarboxylate. Reactivity of a "Nonconjugated" Bis(bicyclo[1.1.0]butane)
N2 - Diels-Alder reaction of dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate (5) with benzvalene (4), norbornene, and norbornadiene afforded the azo compounds 7 and 8. Theseare derivatives of 2,3-diazabicyclo[2.2.2]oct-2-ene as is azo compound 3, which had been obtained previously from 5 and 2 equiv of benzvalene (4). The photochemical extrusion of nitrogen from 3, 7, and 8 has been studied. Whereas 7 and 8 on direct irradiation in benzene gave rise exclusively to the bicyclo[2.2.0]hexane derivatives 9 and 10, respectively, from 3 in addition to the bicyclo[2.2.0]hexane 11, the diolefin 1l was formed. Diolefin 12 has cisdouble bonds in the nine-membered ring and is fixed in a boat conformation in a manner so that the two bicyclobutane systems approach each other very closely. This geometry suggests the unusual ring opening of the intermediate 1,4-cyclohexanediyl diradical from a boat conformation, which arises by inversion of the primarily generated boat conformation. Sensitized photolysis of 3 as weilasthat of ll produced the saturated isomer 13 of 11 and 12. The proximity of the bicyclobutane systems in 1l causes unprecedented reactions leading to cage compounds. When ll was heated at 90 °C, a rearrangement to the pentacyclic product 10 took place. Utilization of tetradeuteriated substrate ll-d4 supported a pathway with two diradical intermediates. Behaving in a convcntional manncr, bicyclobutane 9 and bis(bicyclobutane) 11 took up 1 and 2 equiv of thiophenol most probably in a radical-chain addition to give the thioethers 28 and 19, respectively. In contrast, bis(bicyclobutane) ll was converted by 1 equiv of thiophenol into cagc compound 30 in a process involving both the strained a systems. Heating at 80 °C subjected 30 to a reversible Copc rearrangement, resulting in a 6:1 mixture of 31 and 30. When it was treated with bromine, 11 was transformed to cage compound 38. This addition is believed to proceed via a cationic intermediate. The structure of cage compound 10 was established by a singlc-crystal X-ray analysis of dialcohol 11 prepared from 20 and methyllithium.
KW - Organische Chemie
Y1 - 1988
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58413
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 - Lang, R.
A1 - Reimann, W.
A1 - Irngartinger, H.
T1 - Darstellung und Röntgenstrukturanalyse des Diels-Alder-Addukts von 4-Phenyl-4H-1,2,4-triazol-3,5-dion an Octavalen
N2 - No abstract available
KW - Organische Chemie
Y1 - 1984
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-58162
ER -