- Synthesis of the cyclohexadienyl ruthenium arene complexes [(η5-C6H3Me4)Ru(η6-arene)]+from the dimethyloctadienyl ruthenium chloride[(μ-η3:η3-C10H16)RuCl2]2
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Reaction of the readily accessible dimethyloctadienyl ruthenium chloride [(μ-η3:η3-C10H16)RuCl2]2(1) with 1,3,5,5-tetramethylcyclohexadiene and arenes in the presence of TlPF6gives cyclohexadienyl ruthenium arene complexes [(η5-C6H3Me4)Ru(η6-arene)]+in ca. 50% yield (arene = benzene, naphthalene, pyrene, thiophene, ethyl ester of N-acetyl-phenylalanine). In the absence of appropriate arene the major product is the mesitylene complex [(η5-C6H3Me4)Ru(η6-C6H3Me3)]+formed via splitting of the C-Me bond in the 1,3,5,5-tetramethylcyclohexadienyl ligand. The reaction of 1 with p-xylene and TlPF6in the absence of diene gives a methyl-isobutyl substituted pentadienyl complex [(η5-C5H5(iBu)Me)Ru(η6-C6H4Me2)]+(6) via isomerization of the dimethyloctadienyl ligand. The structures of [(η5-C6H3Me4)Ru(η6-naphthalene)]PF6and [6]BPh4were confirmed by X-ray diffraction.
- Trifonova, Evgeniya A.,Perekalin, Dmitry S.,Loskutova, Natalia L.,Nelyubina, Yulia V.,Kudinov, Alexander R.
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- Comprehensive kinetic and mechanistic considerations for the gas-phase behaviour of pinane-type compounds
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The thermal behaviour of selected pinane-type compounds, α-pinene (1), β-pinene (2), pinane (3) and nopinone (4), has been investigated. The conversion of the bicyclic starting materials to their acyclic and monocyclic isomers as well as the consecutive reactions of the acyclic main isomerisation products are discussed. The conversion of 1-4 in a reaction network is presented and the experimental evidence for the formation of pyrolysis products by a biradical pathway is discussed. In addition to these results a kinetic model describing the isomerisation of the bicyclic compounds to their acyclic and monocyclic isomers is presented. A good correlation between kinetic simulations and experimental data is revealed. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Stolle, Achim,Ondruschka, Bernd,Bonrath, Werner
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p. 2310 - 2317
(2008/02/08)
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- The reaction of cyclic allylic alcohols with aliphatic alcohols in the presence of cerium(III) chloride
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Cyclic secondary and tertiary allylic alcohols react with primary aliphatic alcohols in the presence of cerium(III) chloride heptahydrate to give alkyl allylic ethers. When secondary or tertiary aliphatic alcohols are used 1,3-dienes are obtained from allylic alcohols heaving the 3-methyl-2-en-1-ol moiety (3-8, 13-15).
- Uzarewicz,Dresler
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p. 181 - 195
(2007/10/03)
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- Cycloadditions of 1-(4-Methoxyphenyl)-2-methylvinyl Cation to Olefins. Stereochemistry and Structure of the Reaction Products
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(E)-1-Bromo-1-(4-methoxyphenyl)-1-propene (1a) reacts stereospecifically with (Z)-2-butene and silver tetrafluoroborate by cycloaddition of the intermediate vinyl cation 2a to give cis-1-(4-methoxyphenyl)-2,3,4-trimethyl-1-cyclobutene (3); with (E)-2-butene, 3 and trans-1-(4-methoxyphenyl)-2,3,4-trimethyl-1-cyclobutene (4) are formed in a ratio of 1:4.These results are in accord with a synchronous cycloaddition of the vinyl cation 2a to (Z)- and (E)-2-butene.Cyclohexene derivatives 14a, 14b, and 14c are obtained predominantly by the reaction of 1a and AgBF4 or AgSbF6 with vinylcyclopropane (11), ethyl vinyl ether (12), and isobutene (13), respectively.
- Bofinger, Klaus Rainer,Hanack, Michael
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p. 2993 - 3003
(2007/10/02)
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- Regioselectivity and Steric Course of Lewis Acid Promoted Ring Enlargement of Cyclohexadiene Complexes with Carbon Monoxide
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Treating the tricarbonyliron complexes 5 and 7 of substituted cyclohexadienes with AlCl3 yields complexes 6, 8, and 9 of seven-membered ring ketones, containing carbon monoxide inserted into one of the double bonds with high regioselectivity depending on the substitution pattern.The mechanism of this ring enlargement is discussed, and an X-ray analysis of 8e is carried out.
- Eilbracht, Peter,Jelitte, Ruediger,Walz, Leonhard
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p. 3473 - 3489
(2007/10/02)
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- 4-Butyl-3,4,5-trimethylcyclohexa-25-dienone
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Processes and compositions are described for use in foodstuff, chewing gum, toothpaste and medicinal product flavor and aroma; tobacco flavor and aroma; perfume and perfumed article aroma augmenting, enhancing and imparting compositions; and as foodstuff,
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