共查询到20条相似文献,搜索用时 31 毫秒
1.
Rozenberg V. I. Sergeeva E. V. Kharitonov V. G. Vorontsova N. V. Vorontsov E. V. Mikul'shina V. V. 《Russian Chemical Bulletin》1994,43(6):1018-1023
The cross-coupling reactions of 4-bromo[2.2]paracyclophane withp-tolylmagnesium bromide in the presence of various palladium and nickel complexes have been studied. It was found that [1,1 -bis(diphenylphosphinoferrocene)]palladium dichloride (PdCl2 · dppf) shows the highest catalitic activity in this reaction. A series of new mono- and diaryl [2.2]paracyclophane derivatives with various substituents in the arene ring have been synthesized using this catalyst. It was shown that it is possible to cross-couple organozinc [2.2]paracyclophane derivatives with aromatic bromides. The composition and structure of the compounds obtained have been established on the basis of elemental analysis and spectral data. Some correlations between the structure and spectral parameters of mono- and diarylsubstituted [2.2]paracyclophanes have been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1081–1085, June, 1994.The present work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5246).The authors wish to express their gratitude to Prof. N. A. Bumagin for his scientific interest and helpful discussions. 相似文献
2.
K. P. Butin A. A. Moiseeva T. V. Magdesieva E. V. Sergeeva V. I. Rozenberg V. G. Kharitonov 《Russian Chemical Bulletin》1994,43(5):783-789
The potentials of electrochemical oxidation (
) and reduction (
) of monobromo- and isomeric di- and tribromo[2.2]paracyclophanes as well as
of mono-, di-, and tribromobenzenes were measured in acetonitrile. The similarity between the properties ofpseudo-para-disubstituted cyclophanes andmeta-disubstituted benzenes, on the one hand, andpseudo-meta-disubstituted cyclophanes andpara-disubstituted benzenes, on the other hand, was confirmed by the existence of a linear relationship between
of bromo-substituted [2.2]paracyclophanes and
of the corresponding bromo-substituted benzenes. The results were explained in terms of the qualitative theory of molecular orbitals, taking into account a through space interaction between the -systems of the benzene rings.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 839–845, May, 1994.The authors wish to express their gratitude to Professor R. Hoffmann (Cornell University, USA) for a useful discussion and criticisms of the text of this paper.This work was financially supported by the Russian Foundation for Basic Research (Project 93-03-5246). 相似文献
3.
Vorontsova N. V. Rozenberg V. I. Vorontsov E. V. Antonov D. Yu. Starikova Z. A. Bubnov Yu. N. 《Russian Chemical Bulletin》2002,51(8):1483-1490
The nucleophilic addition of butyllithium, phenyllithium, methyllithium, and triallylborane to [2.2]paracyclophane-4,7-quinone (1) proceeded regio- and stereospecifically to give the corresponding cis-4,7-disubstituted 4,7-dihydroxy-4,7-dihydro[2.2]paracyclophanes 2—5 with the endo orientation of the hydroxy groups. The structures of quinone 1 and diols 2, 4, and 5 were established by X-ray diffraction analysis. 相似文献
4.
Planar chiral hydroxy derivatives of [2.2]paracyclophane as auxiliaries for asymmetric allylboration
N. V. Vorontsova R. P. Zhuravsky E. V. Sergeeva E. V. Vorontsov Z. A. Starikova V. I. Rozenberg 《Russian Chemical Bulletin》2007,56(11):2225-2231
Allylboronic esters with various structures were synthesized for the first time based on [2.2]paracyclophane derivatives containing
one or two hydroxy groups. It was demonstrated that these esters can be used as chiral inductors in the asymmetric allylboration
of benzaldehyde. The highest enantiomeric excess of 1-phenylbut-3-en-1-ol (60%) was achieved in the reactions with acyclic
bis-O,O′-(paracyclophanyl) allylboronates based on (S)-4-hydroxy-and (S)-12-bromo-4-hydroxy[2.2]paracyclophanes. (S)-4-Hydroxy[2.2]paracyclophane was studied by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2149–2155, November, 2007. 相似文献
5.
DDQ treatment of the Diels-Alder products 1 unexpectedly led to chloroderivatives 2. Chlorination did not occur during DDQ treatment of the fully aromatised compounds 3. These results point out that DDQ acted as an oxidant and source of chlorine. 相似文献
6.
Ethynyl[2.2]paracyclophanes and 4-isocyano[2.2]paracyclophane as ligands in organometallic chemistry
Sébastien Clément Michael Knorr Stefan Dilsky Marta Arroyo 《Journal of organometallic chemistry》2007,692(4):839-850
An alternative synthesis of (±)-4-ethynyl[2.2]paracyclophane (PCPCCH) (5) and 4,16-diethynyl[2.2]paracyclophane (6) via the Corey-Fuchs reaction has been developed. The olefinic intermediate 4-dibromovinyl[2.2]paracyclophane (3) has been isolated and structurally characterized. The racemic terminal alkyne 5 was employed as starting material for assembling of a luminescent extended π-conjugated system containing a thiophene unit and for a catalytic bis-silylation reaction yielding the olefinic dithioether Z-PhSCH2Me2SiC(H)C(PCP)SiMe2CH2SPh (9). The dimetallatetrahedran [Co2(CO)6(μ-η2-PCP-CCH)] (10) has been prepared and its crystal structure determined by an X-ray diffraction analysis. Alkyne 5 has also been used for the preparation of the Pt(0) complex [Pt(PPh3)2(PCPCCH)] (11) and the heterodinuclear dimetallacyclopentenone [(OC)2Fe{μC(O)C(PCP)C(H)}(μ-dppm)Pt(PPh3)] (12). The synthesis and reactivity of 4-isocyano[2.2]paracyclophane (15) towards heterobimetallic iron-platinum and palladium-platinum complexes is also presented. Opening of the dative iron → platinum bond of [(OC)4Fe(μ-dppm)PtCl2] (16) occurred upon addition of 15 to a CH2Cl2 solution of 16 leading to [(OC)4Fe{μ-dppm}PtCl2(CNPCP)] (17). Treatment of [ClPd(μ-dppm)2PtCl] (18) with isocyanide 15 in a 1:1 ratio affords the A-frame compound [ClPd(μ-dppm)2(μ-CNPCP)PtCl] (19), resulting from formal insertion of 15 into the Pd-Pt bond. Addition of 2 equiv. of 15-18 leads to the ionic A-frame compound [ClPd(μ-dppm)2(μ-CNPCP)Pt(CNPCP)]Cl (20). 相似文献
7.
Charges on carbon atoms in the molecules of 4-aryl-substituted [2.2]paracyclophanes were estimated and the role of charge
control as a kinetic factor in regioselectivity of their complexation with (NH3)3Cr(CO)3 was investigated using electron density distribution analysis by the Bader, Weinhold-Reed (NPA), and Mulliken methods. The
most plausible picture of the electron density distribution in substituted [2.2]paracyclophanes was obtained by the Bader
method and compared with experimental data on the yields of reaction products. Topological analysis of the electron density
distribution in the [2.2]paracyclophane molecule by the Bader method confirmed the existence of a weak antibonding interaction
between the stacked benzene rings.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–444, March, 1999. 相似文献
8.
V. A. Nikanorov V. G. Kharitonov E. V. Yatsenko D. P. Krut'ko M. V. Galakhov S. O. Yakushin V. V. Mikul'shina V. I. Rozenberg V. N. Guryshev V. P. Yur'ev O. A. Reutov 《Russian Chemical Bulletin》1992,41(8):1430-1434
From the reaction mixtures in the uncatalyzed polybromination of [2.2]paracyclophane by the action of excess Br2 in CCl4, there have been found along with the known products — 4,15- and 4,16-dibromo[2.2]paracyclophanes — two new aromatic tribromides of this series, which have been isolated in pure form: 4,12,15- and 4,15,16-tribromo[2.2]paracyclophanes. Special experiments demonstrated that the mixtures of these tribromides are formed as a result of competitive monobromination of 4,15-dibromo[2.2]paracyclophane; the 4,15,16-tribromo[2.2]paracyclophane, together with still another newly isolated isomer of this series — 4,8,12-tribromo[2.2]paracyclophane — is formed as a result of competitive monobromination of 4,16-dibromo[2.2]paracyclophane. As an explanation of the features of the orienting effect of substituents in these competing reactions, a rule was proposed: On the conventional orientation (from the electronic point of view) of entry of the bromine atom into the substituted ring (para > ortho > meta), a steric limitation is imposed on its attack in the pseudo-gem-position, owing to the bulky bromine atom that is transannularly positioned above it in the neighboring aromatic ring. The structures of all of the tribromides were established on the basis of elemental analyses, mass spectrometry, and1H NMR spectrometry (including PMR using the homonuclear Overhauser effect). The data obtained in this work indicate that the 4,12,15-tribromo[2.2]paracyclophane and 4,15,16-tribromo[2.2]paracyclophane are predecessors of the two tetrabromides previously obtained by Cram — 4,7,12,15- and 4,5,15,16-tetrabromo[2.2]paracyclophanes; and the 4,8,12-tribromo[2.2]paracyclophane is a possible predecessor of 4,8,12,16-tetrabromo[2.2]paracyclophane, which is unknown up to the present time.A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1837–1843, August, 1992. 相似文献
9.
A comparative molecular orbital study of [2.2]paracyclophane and simple arenes as ligands toward a Cr(CO)3 group was performed with the aim of accounting for the observed coordination patterns. While the inter-ring repulsion is
an important factor in [2.2]paracyclophane activation, it is not the only one. The molecular orbitals of two arene rings stacked
parallel to each other were analyzed in some detail. The inward hybridization (toward the other ring) of the (arene)2 HOMO was shown to reduce the strength of consequent bonding with the Cr(CO)3 is fragment. The overall stabilization of [2.2]paracyclophane complex with Cr(CO)3 is enhanced by a reduction of the inter-ring repulsion and strengthening of the Ar−Cr bond, and reduced by weakening of the
intra-ring carbon-carbon bonds. The inter-ring repulsion increases with approach of the arenes to each other, as appears to
happen in the structure of [2.2]paracyclophane complex with Cr(CO)3. This explains the high donor ability of the free ring of the (arene)2Cr(CO)3 complex toward another Cr(CO)3 fragment. It was proposed that the stabilization of the [2.2]paracyclophane complex with Cr(CO)3 results ultimately from the relaxation of the strained framework of [2.2]paracyclophane. The kinetic factor in Cr(CO)3 complexation was also studied by analyzing the charges on competing arene rings in monoaryl-substituted derivatives of [2.2]paracyclophanes.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 151–157, January, 1998. 相似文献
10.
The novel [2.2]paracyclophanes 4-7 with an extended π-conjugation due to the presence of a linear arylethynyl chain have been synthesized by the Pd-catalyzed Sonogashira coupling reaction. 相似文献
11.
12.
The 5-nitro[2.2]paracyclophanepyran-6-one 2 has been synthesized. DBN treatment of the Diels-Alder cycloadducts of 2 followed by DDQ oxidation unexpectedly led to [2.2]paracyclophanes containing a condensed benzofuran subunit. 相似文献
13.
4,16-Dibromo[2.2]paracyclophane (4) is isomerised to 4,12-dibromo[2.2]paracyclophane (1) by the application of microwaves in DMF solution. 相似文献
14.
Lucian G. Bahrin Henning Hopf Peter G. Jones Mihail L. Birsa Laura G. Sarbu 《Molecules (Basel, Switzerland)》2020,25(22)
The synthesis of paracyclophane-based tetrathiafulvalene precursors is described in the context of the importance of these compounds in the field of material chemistry. Pseudo-geminal bis(1,3-dithia-2-thione) was synthesized via the corresponding 1,3-dithiol-2-ylium salt. The latter was obtained by a synthetic procedure that involves 4,15-bis(acetyl)[2.2]paracyclophane, a new compound of interest for many researchers. 相似文献
15.
Antoni K. Wisor Leszek Czuchajowski 《Monatshefte für Chemie / Chemical Monthly》1983,114(10):1023-1034
Ultraviolet spectra of 4-phenyl-[2.2]paracyclophane and of the 4,7- and 4,13-diphenyl derivatives were interpreted. MINDO/3 total molecular energy andPPP—CI-1 energies of singlet transitions were calculated for different values of the dihedral angle of the phenyl ring with respect to the benzene ring of paracyclophane. Although most of the theoretical transitions correspond to local excitation within thePCP fragment, some of them result in a transfer of electron charge to the phenyl substituents.
Elektronenspektren und Konformationen von Mono- und Diphenylderivaten des [2.2]Paracyclophans
Zusammenfassung Es werden die UV-Spektren von 4-Phenyl-[2.2]paracyclophan, 4,7- und 4,13-Diphenyl-[2.2]paracyclophan interpretiert. Für verschiedene Diederwinkel der Phenylringe relativ zu dem Benzolring des Paracyclophans wurden MINDO/3-Rechnungen für die Gesamtenergie undPPP—CI-1 Rechnungen für die Singlet-Übergänge durchgeführt. Die meisten der berechneten Übergänge gehören zu lokalen Anregungen innerhalb desPCP-Fragments, einige sind jedoch einem Elektronentransfer zu den Phenylsubstituenten zuzuschreiben.相似文献
16.
D. Yu. Antonov E. V. Sergeeva E. V. Vorontsov V. I. Rozenberg 《Russian Chemical Bulletin》1997,46(11):1897-1900
An efficient three-step synthesis of [2.2]paracyclophane-pseudo-ortho-dicarboxylic acid by dibromination of [2.2]paracyclophane, thermal isomerization of the resultingpseudopara-dibromide topseudo-ortho-isomer, followed by lithiation/carboxylation was developed. The possibility of preparation of two other novelpseudo-ortho-disubstituted carbonyl derivatives, 4-carboxy-12-(1-oxopenthyl)-[2.2]paracyclophane and di(4-carboxy[2.2]paracyclophanyl-12)ketone,
was demonstrated when an excess of lithiation reagent (4 or 10 eq.) was used in the final step.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2001–2004, November, 1997. 相似文献
17.
Yu. A. Ustynyuk O. I. Trifonova A. V. Yatsenko A. A. Borisenko H. -J. Hansen P. Uebelhart 《Russian Chemical Bulletin》1994,43(12):2100-2106
Reactions of 1,2,5,6,8,10-hexamethylheptalene (1) and its bond isomer, 1,4,5,6,8,10-hexamethylheptalene (2), with tricarbonylchromium complexes L{in3}Cr(CO){in3} (L=NH{in3} and Py) have been investigated. Thermodynamically less stable complex 1 exhibits higher reactivity with respect to Py{in3}Cr(CO){in3}/BF{in3} · Et{in2}O under the conditions of Öfele's reaction than complex2. At 10–30 °C, the Cr(CO){in3} group is coordinated to the asymmetrically substituted ring, which is accomplished by the shift of double bonds in the ligand, to afford tricarbonyl-[1,4,5,6,8,10-hexamethyl-{su6}-(10a, 1–5)heptalene]-chromium (6) as the only mononuclear complex. Under more drastic conditions (Raush's reaction, 80 °C),1 2 interconversion proceeds faster than the reaction of individual bond isomers with coordinatively unsaturated hot particles (solv){inn}Cr(CO){in3}. In this case, all of the four possible isomeric mononuclear complexes (6–9) and two binuclear complexes (10 and 11) are formed. The structures of complexes 6–11 have been studied by NMR and mass spectrometry, the structure of6 has been established by X-ray diffraction analysis. Heating a solution of6 in octane at 115 °C results in the isomerization of6 into complex7 through the intracycle 1,2-shift of the Cr(CO){in3} group and also in its conversion into complex8, which is the first example of interring {su6}{su6}-haptotropic rearrangement in nonplanar seven-membered -systems.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2220–2226, December, 1994.We would like to thank N. S. Kulikov for measuring mass spectra and L. A. Aslanov for helpful discussion of the results of X-ray diffraction analysis.The Research Group from the Moscow State University gratefully acknowledges the support of this work by the International Science Foundation (Grant No. MQ 5000) and the Russian Foundation for Basic Research (Project No. 94-03-08325). 相似文献
18.
Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives
Zahid Hassan Eduard Spuling Daniel M. Knoll Stefan Brse 《Angewandte Chemie (International ed. in English)》2020,59(6):2156-2170
[2.2]Paracyclophane (PCP) is a prevalent scaffold that is widely utilized in asymmetric synthesis, π‐stacked polymers, energy materials, and functional parylene coatings that finds broad applications in bio‐ and materials science. In the last few years, [2.2]paracyclophane chemistry has progressed tremendously, enabling the fine‐tuning of its structural and functional properties. This Minireview highlights the most important recent synthetic developments in the selective functionalization of PCP that govern distinct features of planar chirality as well as chiroptical and optoelectronic properties. Special focus is given to the function‐inspired design of [2.2]paracyclophane‐based π‐stacked conjugated materials by transition‐metal‐catalyzed cross‐coupling reactions. Current synthetic challenges, limitations, as well as future research directions and new avenues for advancing cyclophane chemistry are also summarized. 相似文献
19.
A. V. Vorogushin M. D. Reshetova N. G. Akhmedov Yu. A. Ustynyuk I. L. Eremenko S. E. Nefedov A. I. Zinin 《Russian Chemical Bulletin》1998,47(4):699-703
The reaction of Cr(CO)6 with 7,7-dichloro-3,4-benzobicyclo[4.1.0]heptane gave the correspondingexo- andendo-chromium tricarbonyl complexes in a ratio of 4.5:1. The structures of the resulting compounds were established by NMR spectroscopy,
mass spectrometry, and X-ray structural analysis. Reduction of dichlorobenzobicycloheptane and its chromium tricarbonyl complexes
with LiAlH4 affordedexo- andendo-7-chloro-3,4-benzobicyclo[4.1.0]heptanes in a 3.5:1 ratio.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 720–724, April, 1998. 相似文献
20.
The character of distortions of the paracyclophane skeleton in various substituted [2.2]paracyclophanes was analyzed based on X ray diffraction data. The rigidity of the skeleton is provided by ethylene bridges and flexibility of the benzene rings, which adopt a boat conformation. The flexibility of the skeleton is manifested in the displacement of the benzene rings with respect to each other and conformational changes of ethylene bridges. The changes in these characteristics are very sensitive to intra- and intermolecular steric factors and are indicative of the absence of strong specific stacking interactions between the be nzene rings. Precision X-ray diffraction study and quantum-chemical calculations for unsubstituted [2.2]paracyclophane and 4,7-benzoquinono[2.2]paracyclophane demonstrated that there are no attractive interactions between the benzene rings, and the electron density is localized predominantly on the outer surface of the rings. This fact can be considered as the cage molecular effect of the [2.2]paracyclophane skeleton.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1707–1732, September, 2004. 相似文献