Computer generation and theoretical study of alicyclic caged structures without small-size cycles

Evtushenko, A. V.; Molchanova, Marina S.; Smirnov, B. B.; Shlyapochnikov, V. A.

doi:10.1007/bf01435372

Cited by 4 publications

(3 citation statements)

References 10 publications

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“…Unfortunately, out of all the above isomers, only ethanoadamantane 10 has ever been synthesized. Isomer 11 , which is the second most stable, is the only additional one to have been mentioned in a computational chemistry paper . All other isomers ( 12 – 17 ) have never been mentioned in the literature and do not have a CAS registry number.…”

Section: Results and Discussionmentioning

confidence: 99%

Technical Synthesis of 1,5,9-Cyclododecatriene Revisited: Surprising Byproducts from a Venerable Industrial Process

et al. 2019

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The synthesis of 1,5,9-cyclododecatriene by selective trimerization of butadiene catalyzed by TiCl4 and ethylaluminum sesquichloride has been commercially used since 1965. Although thoroughly investigated, not all details of the mechanism are completely understood. The recent development of a new process to produce cyclododecanone involving oxidation of 1,5,9-cyclododecatriene with N2O has led to the serendipitous discovery of an array of hitherto unknown byproducts, formed in the trimerization of butadiene: eleven tricyclic C12H20 and one tetracyclic C12H18 hydrocarbons, three of which had never been described before. The identification of these byproducts became possible by using a combination of chemical enrichment, high-resolution distillation, 13C-2D-INADEQUATE NMR, and comparison with ab initio calculated spectra, thus demonstrating the power of these combined techniques. The identification of these byproducts contributes to a better understanding of the mechanism of this centrally important reaction.

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Section: Results and Discussionmentioning

confidence: 99%

Technical Synthesis of 1,5,9-Cyclododecatriene Revisited: Surprising Byproducts from a Venerable Industrial Process

et al. 2019

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“…On exposure to 254-nm light, they afforded cage molecules 27 and 28 in 7 and 4.5% yield, respectively (Scheme 8). 56 Photoproducts 27 and 28 have a common pentacyclo[6.3.0.1 4,11 .0 2,6 .0 5,10 ]dodecane framework, which is known as one of the members of the C 12 H 16 hydrocarbon family 57 and was first constructed in one step by photoreactions. 56…”

Section: General Remarks On the Photoreactions Of Cyclophanes Containing Two Benzene Ringsmentioning

confidence: 99%

Photochemistry of Nitrogen-Bridged Cyclophanes: 2,11-Diaza[3₂]anthracenoparacyclophane and 2,11-Diaza[3₂]paracyclophane Systems

Okamoto¹,

Yamaji

Satake³

2008

Synlett

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This account provides an overview of the photochemical properties of cyclophanes possessing nitrogen atoms in the bridge chains, namely 2,11-diaza[3 2 ]anthracenoparacyclophane and 2,11-diaza[3 2 ]paracyclophane systems. Although the photoreactions of aromatic molecules that are bound by a linker or fixed in a cyclophane structure have been widely investigated, much less attention has been paid to the photochemistry of aromatic rings incorporated in a nitrogen-bridged cyclophane. During the course of our work on the photoreactions of cyclophanes possessing nitrogen atoms in their bridge chains, the nitrogen-bridged cyclophanes were found to display photoproperties significantly different from those of the nonbridged aromatic chromophores or the corresponding carbonbridged cyclophane analogues. The 2,11-diaza[3 2 ]anthracenoparacyclophane system displayed an efficient photochemical cycloaddition-adiabatic cycloreversion cycle in the excited singlet state, while in the triplet state, the photoisomer underwent a novel rearrangement and adiabatic cycloreversion. Upon photolysis of the 2,11-diaza[3 2 ]paracyclophane system, an octahedrane cage was formed. This is the first reported octahedrane formation to occur by the photochemical dimerization of benzene. Thus, the title cyclophane systems display a variety of photoprocesses involving cycloaddition, adiabatic cycloreversion accompanied by photoinduced chemiluminescence, novel rearrangements, and previously unknown benzene dimerization.

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“…Vier stammen aus den ursprünglich vorhandenen Trimethylenbrücken, zwei wurden aus den Benzolringen gebildet (Abbildung 1). Nach unserer Kenntnis wurde das Pentacyclo Familie entworfen, [11] aber bislang noch nicht synthetisiert. Es ähnelt Diamantan 7 (Pentacyclo[7.3.1.1 4,12 .0 2,7 .0 6,11 ]tetradecan), das 1965 erstmals von Schleyer et al synthetisiert worden war und ¹Congressanª genannt wurde.…”

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Bildung einer neuartigen Käfigverbindung mit einem Pentacyclo[6.3.0.14,11.02,6.05,10]dodecan-Skelett durch Photolyse von [34](1,2,4,5)Cyclophan

Lim

Yasutake

Shinmyozu³

2000

Angewandte Chemie

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Prismane bilden eine faszinierende Familie von (CH) n -Polyedern, [1] aus der einige Mitglieder ± Prisman, [2] Cuban [3] und Pentaprisman [4, 5] ± erfolgreich synthetisiert worden sind. Seit kurzem konzentriert man sich auf das herausfordernde Ziel, höhere Prismane und besonders die Hexaprismane 1 zu synthetisieren. Trotz vieler Versuche haben sich diese der Synthese bisher entzogen, hauptsächlich mangels geeigneter Synthesewege und wegen der gegenüber den niedereren Prismanen zu erwartenden höheren Spannung. Bei unserem Versuch zum Aufbau des Hexaprismanskeletts durch Photolyse mehrfach verbrückter [3 n ]Cyclophane (n 3 ± 6) optimierten wir zunächst die Reaktionsbedingungen unter Verwendung des kleinsten Homologen, [3 3 ](1,3,5)Cyclophan 2.Dabei stellten wir fest, dass 2 bei Bestrahlung mit einer Niederdruck-Hg-Lampe in H 2 O-gesättigtem CH 2 Cl 2 in das Bishomopentaprisman 3 überführt wird. [6] Um die Hexaprisman-Derivate zu synthetisieren und weitere Informationen über den Reaktionsmechanismus zu erhalten, wurde die Photolyse des nächsthöheren Homologen von 2, [3 4 ](1,2,4,5)Cyclophan 4, untersucht, [7] das kürzlich durch eine verbesserte und praktikable Synthesemethode leicht zugänglich geworden ist. [8] Eine Lösung von 4 in H 2 O-gesättigtem CH 2 Cl 2 (6.9 Â 10 À4 mol L À1 ) wurde mit einer Niederdruck-Hg-Lampe 1.5 h bei Raumtemperatur unter Ar bestrahlt. Der Verlauf der Reaktion wurde dabei mittels HPLC und DC verfolgt. Die säulenchromatographische Trennung des Rohprodukts (Kieselgel; AcOEt/Hexan, 1/2) lieferte die Ausgangsverbindung 4 (45 %) und die neue Käfigverbindung 5 in Form farbloser Kristalle (7 %; Schema 1). [9] Das Massenspektrum deutete auf die Summenformel C 24 H 32 O 2 (m/z 352.2). Das Fragemtion des bezweifelt werden, dass dieses unter den physiologischen Bedingungen geöffnet wird. Eher scheint der Epoxidring als solcher chemisch unverändert an den Rezeptor zu gelangen oder ist an einer intramolekularen Wasserstoffbrückenbindung zur 3-OH-Funktion beteiligt, so dass eine günstige Konformation resultiert. [9]

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Computer generation and theoretical study of alicyclic caged structures without small-size cycles

Cited by 4 publications

References 10 publications

Technical Synthesis of 1,5,9-Cyclododecatriene Revisited: Surprising Byproducts from a Venerable Industrial Process

Technical Synthesis of 1,5,9-Cyclododecatriene Revisited: Surprising Byproducts from a Venerable Industrial Process

Photochemistry of Nitrogen-Bridged Cyclophanes: 2,11-Diaza[3₂]anthracenoparacyclophane and 2,11-Diaza[3₂]paracyclophane Systems

Bildung einer neuartigen Käfigverbindung mit einem Pentacyclo[6.3.0.14,11.02,6.05,10]dodecan-Skelett durch Photolyse von [34](1,2,4,5)Cyclophan

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Computer generation and theoretical study of alicyclic caged structures without small-size cycles

Cited by 4 publications

References 10 publications

Technical Synthesis of 1,5,9-Cyclododecatriene Revisited: Surprising Byproducts from a Venerable Industrial Process

Technical Synthesis of 1,5,9-Cyclododecatriene Revisited: Surprising Byproducts from a Venerable Industrial Process

Photochemistry of Nitrogen-Bridged Cyclophanes: 2,11-Diaza[32]anthracenoparacyclophane and 2,11-Diaza[32]paracyclophane Systems

Bildung einer neuartigen Käfigverbindung mit einem Pentacyclo[6.3.0.14,11.02,6.05,10]dodecan-Skelett durch Photolyse von [34](1,2,4,5)Cyclophan

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Photochemistry of Nitrogen-Bridged Cyclophanes: 2,11-Diaza[3₂]anthracenoparacyclophane and 2,11-Diaza[3₂]paracyclophane Systems