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1.
Mono- and diprotonated carbocations and the two-electron oxidation dications derived from parent pyrene and its nonalternant isomers "azupyrene"(dicyclopenta[ef,kl]heptalene)(DCPH) and dicyclohepta[ed,gh]pentalene (DCHP) were studied by DFT at the B3LYP/6-31G(d) level. The most likely site(s) for mono- and diprotonation were determined based on relative arenium ion energies and the structures of the energetically most favored carbocations were determined by geometry optimization. The NMR chemical shifts for the protonated mono- and dications and the oxidation dications were computed by GIAO-NMR at the B3LYP/6-31G(d)//B3LYP/6-31G(d) level and their charge delocalization paths were deduced based on magnitude of the computed [capital Delta][small delta](13)C values and the NPA-derived changes in charges. Relative aromaticity/antiaromaticity in various rings in the energetically favored mono- and dications was estimated via NICS and [capital Delta]NICS. Calculated NMR chemical shift data for and were compared with the available experimental NMR values. The available data on chemical and physical properties of DCPH and DCHP are extremely limited and biological activity data are non-existent. The present study provides the first glance into their carbocations and oxidation dications, while augmenting and reinforcing the previous stable ion data on the pyrenium cations. 相似文献
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Lantsetti N. A. Ryabova S. Yu. Alekseeva L. M. Shashkov A. S. Granik V. G. 《Russian Chemical Bulletin》2002,51(3):506-512
1-Aryl-2-oxo-1,2,3,6-tetrahydro[1,4]diazepino[6,5-b]indole N-oxides were synthesized based on 3-(N"-aryl-N"-chloroacetyl)amino-2-formylindoles. Deoxidation of 2-oxo-1-phenyl-1,2,3,6-tetrahydro[1,4]diazepino[6,5-b]indole N-oxide afforded 1,2,3,6-tetrahydro- and 1,2,3,4,5,6-hexahydro[1,4]diazepino[6,5-b]indole derivatives. A new approach to the synthesis of pyrido[3,2-b]indole and pyrimido[5,4-b]indole derivatives was developed. 相似文献
4.
E. Yu. Kambulov V. K. Vasilin E. A. Kaigorodova L. D. Konyushkin G. D. Krapivin 《Chemistry of Heterocyclic Compounds》2003,39(2):255-266
Derivatives of a new heterocyclic system - benz[4,5]imidazo[1,2-c]pyrido[3',2';4,5]thieno[2,3-e]pyrimidine have been obtained by successive reactions in three stages - alkylation of 3-cyanopyridine-2(1H)-thiones with 2-chloromethylbenzylimidazole to give 2-benzimidazolylmethylthio-3-cyanopyridines, closing the thiophene ring in the latter to form 3-amino-2-(benzimidazolyl-2)thieno[2,3-b]pyridines, and cyclization of the pyrimidine ring by acylation with carboxylic acid anhydrides or chlorides. 相似文献
5.
V. M. Kisil L. M. Potikha A. V. Turov V. A. Kovtunenko 《Chemistry of Heterocyclic Compounds》2008,44(2):214-224
The reaction of 7,12-dihydro-5H-isoquino[2,3-a]quinazolin-5-ones with o-xylidene dibromide leads to 11-oxo-4bH,5H,10H,11H,16H-10a-aza-15b-azoniadibenzo[a,e]pleiadene
bromides, which are converted to 11-oxo-10H,11H,16H-10a-aza-15b-azoniadibenzo[a,e]pleiadene salts upon oxidation using nitrobenzene.
The reaction of these salts with benzylamine leads to 6-{2-[(benzylimino)methyl]phenyl}-7,12-dihydroisoquino[3,2-b][2]benzazepin-14(6H)-ones,
which recyclize to 11-oxo-5H,10H,11H-10a-aza-15b-azoniadibenzo[a,e]pleiadene perchlorates upon the action of perchloric acid.
The reactions of the 10a,15b-diazadibenzo[a,e]pleiadene salts obtained with NaBH4 were studied and the structures of the reduction products were determined by spectral methods.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 280–292, February, 2008. 相似文献
6.
L. M. Potikha N. V. Shkilna V. M. Kisil V. A. Kovtunenko 《Chemistry of Heterocyclic Compounds》2004,40(8):1052-1062
The alkylation of benzimidazo[1,2-b]isoquinolin-11(5H)-one has been studied. This occurs at N(5) or C(6) depending on the type of alkylating agent and the reaction conditions. It was shown that C(6) alkylation is effected in reactions with reactive alkyl halides. A repeat alkylation occurs preferentially at the same position. Interaction with o-xylylidene dibromide leads to spiro[benzimidazo[1,2-b]-isoquinolin-6,2'-indan]-11-one and 1,6-dihydro-11H-6a,11b-diazobenzo[b]benzo[5,6]cyclohepta[1,2,3-l,m]fluoren-11-one, which are derivatives of new heterocyclic systems. 相似文献
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L. M. Potikha N. V. Shkilna V. M. Kisil V. O. Kovtunenko 《Chemistry of Heterocyclic Compounds》2004,40(5):603-615
A study has shown that the acylation of benzo[4,5]imidazol[1,2-b]isoquinolin-11(5H)-one occurs at N(5) or at C(6) depending on the nature of the acylating reagent and the reaction conditions. It was found that principally C-acylation takes place in the absence of base. The reaction with -halo-substituted carboxylic acid chlorides leads to the formation of C-acylated products which are converted to derivatives of the novel heterocyclic system 7H-2a,6b-diazabenzo[b]cyclopenta[l,m]fluorene-1,7(2H)-dione in the presence of base. 相似文献
8.
S. A. Osadchii M. D. Stanescu V. I. Mamatyuk V. G. Shuhin 《Russian Chemical Bulletin》1996,45(2):381-383
The 1-hydroxy-2-(5H-dibenzo[a,d]cyclohepten-5-yl)-1-phenylethyl cation generated under long life conditions undergoes fragmentation to afford 5H-dibenzo[a,d]cycloheptenyl-and methylphenylhydroxycarbinyl canons but does not undergo carbocationic cyclization.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 397–399, February, 1996. 相似文献
9.
The acylation of benzo[b]furan-, benzo[b]thiophene, and indolyl-3-acetic acid arylamides using acetic anhydride in the presence of 70% perchloric acid occurs at the -position of the heterocycle to give 2-acetylbenzo[b]furan-, 2-acetylbenzo[b]thiophene, and 2-acetylindolyl-3-acetic acid arylamides. Depending on the amount of perchloric used in the reaction they undergo cyclodehydration to 3-arylamino-1-methylhetero[2,3-c]pyrilium salts and to N-aryl-1-methyl-3(2H)hetero[2,3-c]pyridones. 相似文献
10.
Summary 4- and 5-nitro-benzo[c]thiophenes react as heterocyclic dienes with N-substituted maleic imides. [4+2] cycloaddition gives rise to the formation ofendo, exo configuratedDiels-Alder adducts. This efficient transformation can be utilized for the synthesis of benzo-annelated 7-thiabicyclo[2.2.1]heptenes. Their spectroscopic data are reported and compared with those of the [4 + 2] adducts of isoelectronic 4-(5)-nitro-2-tert-butyl-2H-isoindoles. 相似文献
11.
V. I. Terenin E. A. Sumtsova S. Z. Vatsadze E. V. Kabanova I. F. Leshcheva A. P. Pleshkova N. V. Zyk 《Chemistry of Heterocyclic Compounds》2003,39(7):943-952
We have studied the behavior of asymmetrically substituted dipyrrolo[1,2-a;2',1'-c]pyrazines and their 5,6-dihydro analogs under phosphorylation reaction conditions. 相似文献
12.
Summary By condensation of 2,2-difluoro-4-methyl-benzo[d]-1,3,2-2H-dioxaborines (12) with cyano acetic acid derivatives in presence of weak bases, 3-cyano-4-methyl-benzo[b]pyran-2-ones (13) or their 3-cyano-4-methyl-benzo[b]pyran-2-imine precursors (14) are available in satisfactory yields.
Zur Kondensation von 2,2-Difluor-4-methyl-benzo[d]-1,3,2-2H-dioxaborinen mit Cyanessigsäure- Derivaten. Bildung und Umwandlung von 3-Cyano-4-methyl-benzo[b]pyran-2-onen und ihrer 2-Imino-Vorstufen
Zusammenfassung Durch Kondensation von 2,2-Difluor-4-methyl-benzo[d]-1,3,2-2H-dioxaborinen (12) mit Cyanessigsäure-Derivaten in Gegenwart von Hilfsbasen entstehen in befriedigenden Ausbeuten 3-Cyan-4-methyl-benzo[b]pyran-2-one (13) oder ihre 3-Cyan-4-methyl-benzo[b]pyran-2-imino-Vorstufen (14).相似文献
13.
V. I. Terenin E. A. Sumtsova E. V. Kabanova A. P. Pleshkova N. V. Zyk 《Chemistry of Heterocyclic Compounds》2004,40(4):436-445
Esters, nitriles, and amides of dipyrrolo[1,2-a:2',1'-c]pyrazines have been synthesized by the acylation of dipyrrolo[1,2-a:2',1'-c]pyrazines and 5,6-dihydrodipyrrolo[1,2-a:2',1'-c]pyrazines with trichloroacetic acid chloride, p-tosyl isocyanate, and isocyanatophosphoric acid dichloride (Kirsanov isocyanate). 相似文献
14.
N. N. Polygalova A. G. Mikhailovskii E. V. Vikhareva M. I. Vakhrin 《Chemistry of Heterocyclic Compounds》2007,43(7):900-905
It has been shown that the Chichibabin reaction of enamines of the 1,2,3,4-tetrahydroisoquinoline series and 1,2,3,4-tetrahydrobenzo[f]isoquinoline
series with p-bromophenacyl bromide leads to pyrrolo[2,1-a]isoquinoline derivatives. The same heterocyclic system is obtained
on interaction of 1-alkyl-3,4-dihydroisoquinolines or their benzo[f]-analogs with oxalyl chloride. The obtained dioxopyrrolines
form derivatives of benzo[g]quinoxalino[2,3-b]indolizine on condensation with o-phenylenediamine.
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Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1068–1074, July, 2007. 相似文献
15.
A series of polyfluoro-substituted dibenz[b,f]-1,4-oxazepines with morpholinyl-4 or 4-R-piperazinyl-1 groups in positions 3, 7, or 11 has been synthesized. 相似文献
16.
Heterogeneous catalytic synthesis and structure of 5,5a,10a,11-tetrahydro-10H-indeno[1,2-b]quinoline
Pleshakov V. G. Ambacheu K. D. Ryashentseva M. A. Sergeeva N. D. Vener M. V. Murugova L. A. Zvolinsky O. V. Prostakov N. S. 《Russian Chemical Bulletin》1994,43(6):1037-1040
Hydrogenation of 10H-indeno[1,2-b]quinoline in benzene in the presence of R2S7
gave 5,5a,10a,11-tetrahydro-10H-indeno[1,2-b]quinoline, the structure of which was established by mass-, IR, UV,13C, and1H NMR spectra. Thecis fusion of the indan and tetrahydroquinoline fragments, the axial orientation of the proton at C(5a), and the equatorial orientation of the proton at C(10a) were confirmed by molecular mechanics calculations using the PC MODEL program.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1098–1101, June, 1994. 相似文献
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L. G. Voskressensky T. N. Borisova I. V. Vorob’ev N. M. Postika E. A. Sorokina A. V. Varlamov 《Russian Chemical Bulletin》2008,57(7):1547-1558
A reaction of 10-R-substituted tetrahydrobenzo[b][1,6]naphthyridines (R = CN, CONH2, Me) with dimethyl acetylenedicarboxylate, methyl and ethyl propiolates, and acetylacetylene has been studied. It was found
that 1-acryloyl-10-cyanotetrahydrobenzo[b][1,6]naphthyridines are the major products of the reaction of alkyl propiolates with 10-cyano-substituted naphthyridines,
whereas the reaction with 10-carbamoyl-substituted naphthyridines gives a mixture of 1-acryloyl-substituted naphthyridines
and hexahydrobenzo[b]pyrido[3,4,5-d,e][1,6]naphthyridines. The latter are the only products in the reaction of 10-carbamoyl-substituted naphthyridines with acetylacetylene.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1516–1527, July, 2008. 相似文献
19.
L. M. Potikha N. V. Shkilna V. M. Kisil V. A. Kovtunenko 《Chemistry of Heterocyclic Compounds》2004,40(9):1179-1184
The reaction of benzimidazo[1,2-b]isoquinolin-11(5H)-one with activated olefins has been studied. The derivatives of 3,10-dioxo-3H,10H-benzimidazo[1,2,3-ij]benzo[c][1,8]naphthyridine formed are the result of an initial Michael reaction at C(6) followed by intramolecular heterocyclization. 相似文献
20.
The reactions of 6-methoxybenzo[b]furan-3(2H)-one with 2-aryl-1,1-dicyanoethylenes and malononitrile or with aromatic aldehyde and two moles of malononitrile afford 2-amino-4-aryl-1,3-dicyano-7-methoxydibenzo[b,d]furans. The reactions of benzo[b]thiophen-3(2H)-one with 2-aryl-1,1-dicyanoethylenes or with aromatic aldehyde and one mole of malononitrile produce 2-amino-4-aryl-3-cyano-4H-benzothieno[3,2-b]pyrans. 相似文献