Construction of interstellar cumulenes and heterocumulenes: Mass Spectrometric Studies

Blanksby, Stephen J.; Bowie, John H.

doi:10.1002/(sici)1098-2787(1999)18:2<131::aid-mas3>3.0.co;2-h

Cited by 58 publications

(54 citation statements)

References 116 publications

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“…A gas-phase Fischer indole synthesis via acid-catalyzed elimination of NH 3 from protonated phenylhydrazones was reported from this laboratory [39]. This result exactly parallels the condensed-phase study of McClelland et al [41] in which they found that 4-biphenylnitrenium ion reacts with ethyl vinyl ether to yield 5-phenylindole using a laser flash photolysis (LFP) technique, providing another example [39,[42][43][44][45] of the fact that ion/molecule reactions can bridge the gas phase/condensed phase gap. Figure 4a shows the product ion mass spectrum of the ion/molecule reaction between phenylnitrenium ions PhNH ϩ (m/z 92) and ethyl vinyl ether.…”

Section: Synthesis Of N-heterocycles Using Arylnitrenium Ionssupporting

confidence: 75%

Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of N-Heterocycles

Chen

Cooks

et al. 2004

J. Am. Soc. Mass Spectrom.

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Nitro-reduction by the vinyl halide radical cation CH2 = CH-X+* (X = Cl or Br) converts nitroaromatics into arylnitrenium ions, significant intermediates in carcinogenesis, and the present study reports on the scope and regioselectivity of this versatile reaction. The reaction is general for different kinds of substituted nitroaromatics; para/meta substitutents have little effect on the reaction while ortho substitutents result in low yields of arylnitrenium ions. The phenylnitrenium ion PhNH+ can be generated by chemical ionization (CI) of nitrobenzene using 1,2-dichloroethane as the reagent gas or by atmospheric pressure chemical ionization (APCI) of 1,2-dichloroethane solution doped with nitrobenzene. The chemical reactivities of the arylnitrenium ions include one-step ion/molecule reactions with nucleophiles ethyl vinyl ether and 1,3-dioxolanes, respectively, involving the direct formation of new CN bonds and synthesis of indole and benzomorpholine derivatives. The indole formation reaction parallels known condensed phase chemistry, while the concise morpholine-forming reaction remains to be sought in solution. The combination of collision-induced dissociation (CID) with novel ion/molecule reactions should provide a selective method for the detection of explosives such as TNT, RDX and HMX in mixtures using mass spectrometry. In addition to the reduction of the nitro group, reduction of methyl phenyl sulfone PhS(O)2Me to the thioanisole radical cation PhSMe+* occurs using the same chemical ionization reagent 1,2-dichloroethane. This probably involves an analogous reduction reaction by the reagent ion CH2 = CH-Cl+*.

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Section: Synthesis Of N-heterocycles Using Arylnitrenium Ionssupporting

confidence: 75%

Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of N-Heterocycles

Chen

Cooks

et al. 2004

J. Am. Soc. Mass Spectrom.

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“…2). In mass spectrometry, in its many forms, charged carbenes, notably cumulene carbenes, are frequently generated in the gas phase [26]. Quantification of cis-EODA in human plasma by SRM of the product ions at m/z 155 and 156 was as accurate as that by SRM of the product ions at m/z 171 and 172.…”

Section: Discussionmentioning

confidence: 99%

Gas chromatography–mass spectrometry of cis-9,10-epoxyoctadecanoic acid (cis-EODA)

Tsikas

Mitschke

Gutzki

et al. 2004

Journal of Chromatography B

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“…They include nucleophilic substitution reactions [9,157,[160][161][162], the Friedel-Crafts acylation [163], the Diels-Alder cycloaddition [164,165], the Wittig reaction [166,167], the Reformatsky reaction [168], Michael addition [169,170], the Kolbe reaction [171], the Cannizzaro reaction [172], Claisen-Schmidt reactions [173], the Meerwein-Ponndorf-Verley reduction/Oppenauer oxidation [174,175], the Haber-Weiss reaction [176], the pinacol [177], Claisen [178,179], Hofmann [180,181], Cope [182,183], Lossen [184,185], and Wolff rearrangements [186], and the Fischer indole [177] and cumulene syntheses [187]. They include nucleophilic substitution reactions [9,157,[160][161][162], the Friedel-Crafts acylation [163], the Diels-Alder cycloaddition [164,165], the Wittig reaction [166,167], the Reformatsky reaction [168], Michael addition [169,170]...…”

Section: Mechanism Elucidation Of Classical Organic Reactionsmentioning

confidence: 99%

Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

Chen

2009

Reactive Intermediates

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Mass spectrometry (MS), originally developing from nineteenth-century physics, has a history dating back more than a hundred years. Since then, the technique has advanced enormously. The advent of new methods of ion production, novel mass analyzers, and new tools for data processing has made it possible to analyze almost all chemical entities, ranging from small organic compounds to large biological molecules and whole living cells/tissues. Today, mass spectrometry has become one of the most powerful and popular modern physical-chemical methods to study the details of elemental and molecular processes in nature. Because of its unparalleled capability of providing information on molecular weight, chemical structures, isotopic content, and even molecular dynamics, mass spectrometry is playing an increasingly significant role in the chemical and life sciences. As a traditional analytical tool and a booming technology for biomedicine, it has found extensive applications in nearly every discipline involving chemical analysis such as petroleum prospecting and refining, food processing, drug discovery, metablomics, genomics, proteomics and structural biology, as well as the environment, public safety, and industrial process monitoring. Along with the development of mass spectrometric technology, the chemistry of gaseous ions has been explored by the study of unimolecular and collision-induced dissociation (CID) [1][2][3][4] and by the study of ion/molecule reactions [2,[5][6][7][8][9][10][11][12][13][14][15][16][17] and ion/ion reactions [18][19][20][21][22][23][24][25][26] in the gas phase. The study of gas-phase ion chemistry has both fundamental and practical significance because it not only provides diverse information on ion reactivity, thermochemistry, and dynamics, but it also forms one basis for chemical analysis using mass spectrometry. In addition, the ion reactivity examined in the isolated gas-phase environment of mass spectrometers has a strong connection with reaction chemistry in solution, as well as contrasting with it. Many important ionic intermediates which are hard to probe in the condensed phase can be easily accessed in the gas phase. Therefore, mass spectrometry has also become an important and unique tool for the mechanistic investigation of organic reactions (particularly organometallic reactions), since soft electrospray ionization (ESI) technology [27, 28] became available. In this regard, there is a large body of work in the literature, which is reviewed in this book. j37This chapter will provide an overview of the history and the current state of the art of mass spectrometry-based study of ion chemistry, specifically of ion/molecule reactions. As this is a broad topic with an immense literature (over 15 000 papers), our emphasis will be placed on the applications of ESI-MS coupled with gas-phase ion/ molecule reactions and tandem mass spectrometry in organometallic chemistry, including probing key intermediates and reaction pathways of organometallic reactions in solution. We will start with...

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Construction of interstellar cumulenes and heterocumulenes: Mass Spectrometric Studies

Cited by 58 publications

References 116 publications

Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of N-Heterocycles

Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of N-Heterocycles

Gas chromatography–mass spectrometry of cis-9,10-epoxyoctadecanoic acid (cis-EODA)

Historical Perspectives in the Study of Ion Chemistry by Mass Spectrometry: From the Gas Phase to Solution

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