Quinolinium Cations Research Articles

Preparation and Properties of AzaTCNQ− Anion Salts and Mixed AzaTCNQ−/TCNQ\ewdot Salts of N-Alkylpyridinium and Related Cations

Abstract The [Cation]+ATCNQ− type salts were prepared, where ATCNQ− is (4-dicyanomethyl-1-pyridinio)dicyanomethanide anion, so-called AzaTCNQ− anion, and [Cation]+ are N-alkylpyridinium, 4-cyano-N-alkylpyridinium, (4-methyl-1-pyrazinio)dicyanomethanide, N-alkylquinolinium (alkyl=Me and Et), N-methylacridinium, and N-methylphenazinium. Electrical resistivities of these salts as compacted samples fall in the range 106–109 Ωcm at 25 °C. The mixed ATCNQ−/TCNQ\ewdot salts (TCNQ\ewdot=7,7,8,8-tetracyano-p-quinodimethan radical anion) of N-alkylpyridinium and -quinolinium cations also were prepared; [Cation]+ (ATCNQ−)0.1(TCNQ\ewdot)0.9([Cation]+=N-methylpyridinium, N-ethylpyridinium, and N-ethylquinolinium) and [N-methylquinolinium]+(ATCNQ−)0.17(TCNQ\ewdot)0.83 whose electrical resistivities (104–106 Ωcm at 25 °C) are somewhat smaller than those of the corresponding TCNQ\ewdot salts. Stackings of ATCNQ− and TCNQ\ewdot anions are discussed on the basis of electronic reflectance and ESR spectra. The [Cation]+ATCNQ− salts react with iodine in hexane to give [Cation]+ATCNQ−·Ix ([Cation]+=N-methyl- and N-ethylpyridinium and -quinolinium; x=3.2–3.9). They exhibit electrical resistivities of 104–106 Ωcm at 25°C, which are lower by the 102–103 order than the resistivities of the undoped [Cation]+ATCNQ− salts.

Simultaneous formation of 2- and 4-quinolones from quinolinium cations catalysed by aldehyde oxidase.

Quinolinium salts were incubated with partially purified aldehyde oxidase, and the products were separated by high-pressure liquid chromatography and fully characterized by u.v. spectroscopy, i.r. spectroscopy and mass spectrometry. Oxidation of N-methylquinolinium salts with either rabbit or guinea-pig liver aldehyde oxidase in vitro gave two isomeric products, N-methyl-4-quinolone and N-methyl-2-quinolone. Incubation of N-phenylquinolinium perchlorate similarly yielded two oxidation products, N-phenyl-4-quinolone and N-phenyl-2-quinolone. The ratio of 2- to 4-quinolone production was species-dependent, the proportion of 4-quinolone with the guinea-pig enzyme being greater than that obtained with the rabbit liver enzyme. Kinetic constants were determined spectrophotometrically for both the quinolinium salts and a number of related quaternary compounds. In general, quaternization facilitated oxidation of a substrate, but a number of exceptions were noted, e.g. N-methylisoquinolinium and N-methylphen-anthridinium. Km values varied with the nature of electron acceptor employed, and this difference was more marked for quaternary substrates than the unquaternized counterparts. The product ratio obtained from N-methylquinolinium salts was found to be constant under various conditions, including purification of the enzyme and the use of either induced or inhibited aldehyde oxidase, but a change in the ratio was found at high pH values and in the presence of a competing substrate, N-methylphenanthridinium. This may indicate that a quaternary substrate binds to aldehyde oxidase in two alternative positions.

The c-alkylation of nitroalkame anions by l-substituted-2- [formula omitted]-butyl-4-phenyl- and -2,4-diphenyl-5,6-dihydrobenzo(ulbarh]quinolinium cations

- The N-substituents are transferred from the title cations to the C-atom of nitroalkane anions in high yield at 25-80°C in DMSO solution. The title cations are readily available from the appropriate pyrylium cations and primary amines of types RCH 2,NH 2, and RR'CHNH 2, allowing a general 2-step method for the preparation of higher nitro- alkanes. Spectral properties of a variety of nitroalkanes are discussed.

Kinetics and mechanisms of nucleophilic displacements with heterocycles as leaving groups. Part 11. ρ* plots for the solvolysis of 1-s-alkyl-5,6-dihydro-2,4-diphenylbenzo[h]quinolinium cations

The ρ* values for (1c–h) for (i) solvolysis in trifluoroacetic acid (–5.7), (ii) for solvolysis in pentanol (–1.2), and (iii) for unimolecular reaction with piperidine in chlorobenzene (–3.1) are discussed with respect to (a) the hypothesis that ρ* is a measure of the cation character of the transition state and (b) the SN2 (intermediate) mechanism. The results are explained for (i) in terms of determining ion-molecule pair dissociation, for (ii) as rate determining SN2 type solvent attack, and for (iii) as rate-determining ion-molecule pair formation.

Photochemical synthesis of 7H-indolo[1,2-a]quinolinium salts - a new ring system

Abstract Photodehydrocyclization of 1-phenyl-2-/2-arylethenyl/-3,3-dialkyl-3H-indolium cations leads in very good yield to 7H-indolo[1,2-a]quinolinium cations.

New method for allowance for the activity of the nucleophile in calculations of the reactivities of heteroaromatic compounds

A new method for allowance for the activity of the nucleophile in calculations of the reactivities of heteroaromatic compounds that is based on the special application of the valence molecular orbital (VMO) theory in the form of Dewar reactivity numbers is proposed. It is shown that there is a correspondence between the proposed method and the general VMO theory. The 5-azacinnoline molecule was calculated by both methods. According to the calculations, the 6-C atom should be the most active in reactions with hard bases, whereas the 4-C atom should be the most active in reactions with soft bases. A qualitative correspondence between the proposed method and the DMTS (delocalization model of the transition state) method is also demonstrated in the case of the quinolinium cation.

Excited state adduct formation between excited substituted quinolinium cations and specific inorganic anions

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTExcited state adduct formation between excited substituted quinolinium cations and specific inorganic anionsS. C. Chao, J. Tretzel, and F. W. SchneiderCite this: J. Am. Chem. Soc. 1979, 101, 1, 134–139Publication Date (Print):January 1, 1979Publication History Published online1 May 2002Published inissue 1 January 1979https://doi.org/10.1021/ja00495a022RIGHTS & PERMISSIONSArticle Views95Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (664 KB) Get e-Alerts Get e-Alerts

ChemInform Abstract: PSEUDOBASE FORMATION FROM QUATERNARY PYRIDINIUM, QUINOLINIUM AND ISOQUINOLINIUM CATIONS

Chemischer InformationsdienstVolume 8, Issue 34 Heterocyclic Compounds ChemInform Abstract: PSEUDOBASE FORMATION FROM QUATERNARY PYRIDINIUM, QUINOLINIUM AND ISOQUINOLINIUM CATIONS V. SIMANEK, V. SIMANEKSearch for more papers by this authorV. PREININGER, V. PREININGERSearch for more papers by this author V. SIMANEK, V. SIMANEKSearch for more papers by this authorV. PREININGER, V. PREININGERSearch for more papers by this author First published: August 23, 1977 https://doi.org/10.1002/chin.197734214Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume8, Issue34August 23, 1977 RelatedInformation

Monotropic Phase Transition of the Complex Anion-Radical Salts of TCNQ with the N-(Methyl)quinolinium Cation

Phase transitions were observed in various types of the complex salts of N-(methyl)quinolinium-7, 7, 8, 8-tetracyanoquinodimethan(MeQ-TCNQ). The specific resistivity increased irreversibly by a factor as high as 100 for crystals which included solvent molecules of crystallization and for those which were crystallized in a metastable form without any inclusion. Change in infrared spectra and powder X-ray patterns suggested that the latter crystal was monotropically transformed from a structure which is nearly isomorphous with that of quinolinium(TCNQ) 2 into a stable one which has distortions in linear chains of the stacks of the TCNQ molecules. The resistivity change of the inclusion compounds was caused by escape of the guest molecules which were thought to be originally situated in the channels between the TCNQ columns.

Dual fluorescence of the quinolinium cation

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDual fluorescence of the quinolinium cationStephen G. Schulman and Anthony C. CapomacchiaCite this: J. Am. Chem. Soc. 1973, 95, 9, 2763–2766Publication Date (Print):May 1, 1973Publication History Published online1 May 2002Published inissue 1 May 1973https://doi.org/10.1021/ja00790a002RIGHTS & PERMISSIONSArticle Views369Altmetric-Citations28LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (492 KB) Get e-Alerts Get e-Alerts

Electron localization in one-dimensional disordered systems: K 2Pt(CN) 4Br 0.3·xH 2O and quinolinium (TCNQ) 2⨪ and ⨥

Experimental evidence is presented to show that the one-dimensional chains of Pt ions in K 2Pt(CN) 4Br 0.3·xH 2O and the one-dimensional columns of TCNQ molecules in quinolinium (TCNQ) 2⨪ contain localized electronic states created by a random potential along the chains which originates at the cationic sites. The random potential in K 2Pt(CN) 4Br 0.3·xH 2O is most likely created by partial site occupancy of K + and Br − sites whereas in quinolinium (TCNQ) 2⨪ and ⨥ the random potential is caused by orientational disorder of the quinolinium cation. The electrical conductivity for both materials follows an exp-( T o T ) l n law at low temperatures with n = 2 for a one-dimensional system. T O = 5.9 × 10 4∘K for the Pt chain and 5.0 × 10 3∘K for the TCNQ columns. At intermediate temperatures σ α exp- Δ E kt with ΔE = 0.085 ev for the Pt chain and 0.023 ev for the TCNQ system. At still higher temperatures a semiconductor to “metal” transition occurs in the TCNQ system at T ≈ Δ E k . For the Pt chains decomposition occurs before the transition. It is suggested that the “metallic” region is not due to extended states but to correlated electron hopping. It is suggested that the transition temperature of the TCNQ system may be lowered by using more polarizable cations.

N-oxides and related compounds—XXXV : Reactions of N-alkoxy-pyridinium and -quinolinium cations with nucleophiles

Numerous new examples of reactions of N-alkoxy and N-acyloxy heterocycles with nucleophiles are classified into four types. The dependence of the reaction path on the hard/soft nature and other characteristics of the nucleophiles is discussed, and a rationalisation provided for the varied products produced under different conditions.

Adsorption of cationic surfactants to silver halide—Gelatin dispersions

In homodisperse and crystallographically defined AgBr-gelatin systems of known surface areas, reversible adsorption of organic cations increased with length of their alkyl chain. In neutral or alkaline 0.001 M KBr, the silver halide surface could be saturated by singly charged alkyl pyridinium or quinolinium cations at equilibrium concentrations below about 10 −3 M, provided the alkyl chains contained at least 12 methylene groups. Longer alkyl chains enhanced adsorbability without influencing the saturation coverage. Doubly charged α,ω-alkyl quaternaries gave similar adsorption characteristics but, compared with their singly charged long-chain analogs, the amounts adsorbed at saturation coverage were low. At equilibrium concentrations between 10 −4 and 10 −3 M, adsorption of both types of cations fitted the Langmuir equation for which adsorption coefficients were evaluated; these yielded free energies of adsorption ranging between 6 and 11 kcal./mole, depending on structure and substrate variables. The highest apparent free-energy values were obtained with a cationic cyanine dye in an iodide-containing substrate. It was demonstrated that the limiting area occupied by this dye or other quaternary salts was the same for cubic and octahedral substrates.