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Norbornadiene

About: Norbornadiene is a research topic. Over the lifetime, 2389 publications have been published within this topic receiving 38603 citations.


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Journal ArticleDOI
TL;DR: In this article, the Fourier transform ion cyclotron resonance (FTICR) mass spectrometer was used to determine the reaction mechanisms and rate constants for the reactions of ions produced from a number of precursors.
Abstract: : The reactions of C5H3+ and C5H5+ ions with acetylene and diacetylene were investigated using a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. The ejection capabilities of FTICR were used to determine the reaction mechanisms and rate constants for the reactions of ions produced from a number of precursors. While different structures could be attributed to C5H3+ ions produced from different precursors on the basis of reactivity, this could not be done for C5H5+ ions, whose reactivity was similar regardless of precursor. Different percentages of reactive C5H5+ structure(s) were produced from various precursors using several charge transfer gases. Formation of C5H5+ from norbornadiene and cycloheptatriene was studied in more detail and existence of a second formation mechanism was shown to be possible. Results are discussed in relation to previous work involving C3H3+ and C5H5+ reactions and a proposed ionic route to soot formation.

18 citations

Journal ArticleDOI
TL;DR: Dipole 1 is cleaved by HCl, giving the corresponding (thioxophosphoranyl)diazomethane 15, while addition of HCl to 2a leads to hydrazonoyl chloride 16, in 70% isolated yield.
Abstract: N-[Bis(diisopropylamino)phosphino]-C-[bis(diisopropylamino)thioxophosphoranyl]nitrilimine (1) reacts with electron-poor dipolarophiles such as maleimide, methyl vinyl ketone, and 1,4-naphthoquinone via HOMO(dipole)-controlled [2+3] cycloadditions, while N-[bis(diisopropylamino)(methyl)phosphonio]-C-[bis(diisopropylamino)thioxophosphoranyl]nitrilimine (2a) reacts with electron-rich dipolarophiles such as norbornadiene and ethyl trans-pyrrolineacrylate via LUMO(dipole)-controlled [2+3] cycloadditions. Carbon disulfide reacts with 1 via a formal [4+2] cycloaddition leading to phosphazene containing heterocycle 11 in 75% yield. Dipole 1 is cleaved by HCl, giving the corresponding (thioxophosphoranyl)diazomethane 15, while addition of HCl to 2a leads to hydrazonoyl chloride 16, in 70% isolated yield. Hydrazone 17' (95%) and phosphazine 18(80%) are obtained by a 1,3-addition of BuLi to 1 and PhOLi to 2a, respectively. Trimethylphosphine reacts with 2a by a phosphine-carbene coupling reaction, giving the ylide 20 which is isolated in 75% yield.

18 citations

Journal ArticleDOI
TL;DR: The ring-opening polymerisation of ester group-substituted cycloolefines leads to linear polyalkenylenes with pendant ester groups in the presense of suitable metathesis-catalysts like WCl6/(CH3)4Sn as mentioned in this paper.
Abstract: Die ringoffnende Polymerisation von Estergruppen-substituierten Cycloolefinen in Gegenwart geeigneter Metathese-Katalysatoren wie WCl6/(CH3)4Sn fuhrt zu linearen Polyalkenylenen mit seitenstandigen Estergruppen. Die Ausgangsmonomeren 9-Athoxycarbonyl-bicyclo[6.1.0]non-cis-4-en (3), 13-Athoxycarbonyl-bicyclo[10.1.0]trideca-trans-4, trans-8-dien (5) und 3-Athoxycarbonyl-tricyclo[3.2.1.02,4]oct-6-en (7) werden uber eine Carbenreaktion mit Diazoessigsaureathylester aus den Cycloolefinen cis-1, cis-5-Cyclooctadien (2), cis-1, trans-5, trans-9-Cyclododecatrien (4) und Norbornadien (6) erhalten. Die entsprechenden Polyalkenylene (3a, 5a sowie 7a) besitzen relativ hohe Molekularge-wichte. Ihre Konstitution wird spektroskopisch und durch gaschromatographische Analyse der Abbauprodukte nach Olefin-Metathese mit einem niedermolekularen Olefin (4-Octen) bestimmt. The ring-opening polymerisation of ester group-substituted cycloolefines leads to linear polyalkenylenes with pendant ester groups in the presense of suitable metathesis-catalysts like WCl6/(CH3)4Sn. The monomers 9-ethoxycarbonyl-bicyclo[6.1.0]non-cis-4-ene (3), 13-ethoxycarbonyl-bicyclo[10.1.0]trideca-trans-4, trans-8-diene (5) and 3-ethoxycarbonyl-tricyclo[3.2.1.02,4]oct-6-ene (7) are obtained from the cycloolefines cis-1, cis-5-cyclooctadiene (2), cis-1, trans-5, trans-9-cyclododecatriene (4) and norbornadiene (6) via carbene reaction with ethyl diazoacetate. The corresponding polyalkenylenes (3a, 5a and 7a) show relatively high molecular weights. Their constitutions are determined spectroscopically and by gaschromatographic analysis of the degradation products after olefin-metathesis with a low molecular weight olefine (4-octene).

18 citations

Journal ArticleDOI
TL;DR: In acetonitrile, the cation from cyclooctadiene partitions between deprotonation and Ritter addition, while the one from norbornadiene is reduced; both cations undergo nucleophilic addition in trifluoroethanol and the relevance of these cationic reactions under unusually mild conditions is discussed.
Abstract: The irradiation of N,N-dimethyl-4-chloroaniline in the presence of open-chain dienes in acetonitrile leads to addition of the aminophenyl and chloro groups across one of the double bonds; transannular cyclization takes place with cyclic dienes, leading to an arylnortricyclene from norbornadiene and to 1-arylbicyclo[3.3.0]octanes from 1,5-cyclooctadiene. The reaction proceeds by photoheterolysis of the chloroaniline to yield the 4-aminophenyl cation and addition to a C=C double bond. The chemistry of the adduct cation depends on structure and medium, involving ion pairs in MeCN and solvated ions in CF 3 CH 2 OH. In the latter solvent, formation of ethers from open-chain alkenes is accompanied by Wagner-Meerwein hydride shift. In acetonitrile, the cation from cyclooctadiene partitions between deprotonation and Ritter addition, while the one from norbornadiene is reduced; both cations undergo nucleophilic addition in trifluoroethanol. The relevance of these cationic reactions under unusually mild conditions is discussed.

18 citations

Journal ArticleDOI
TL;DR: A series of poly(aryl ether) dendrimers with a norbornadiene (NBD) group attaching to the core (G n -NBD), generations 1-4, were synthesized and characterized, and their photophysical and photochemical properties were examined.
Abstract: A series of poly(aryl ether) dendrimers with a norbornadiene (NBD) group attaching to the core (G n -NBD), generations 1–4, were synthesized and characterized, and their photophysical and photochemical properties were examined. The fluorescence of the dendrimer backbone is quenched by the norbornadiene group as a result of the electron transfer and energy transfer from the dendrimer backbone to the norbornadiene group in G n -NBD. Selective excitation of the dendrimer backbone results in an isomerization of the norbornadiene group to the quadricyclane (QC) group. The intramolecular electron transfer and energy transfer efficiencies are ca. 0.93, 0.73, 0.54, 0.30 in dichloromethane, and ca. 0.90, 0.70, 0.55, 0.34 in tetrahydrofuran for generations 1–4, respectively, with the rate constant ca. 10 10 s −1 . The light-harvesting ability of these dendritic molecules is demonstrated by the enhanced valence isomerization rate of NBD to QC with increasing generation.

18 citations


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Performance
Metrics
No. of papers in the topic in previous years
YearPapers
202316
202240
202133
202040
201930
201829