Structure of the C2H5O+ ion in the mass spectra of 2-alkanols

Harrison, Alex G.; Keyes, B. G.

doi:10.1021/ja01020a062

Cited by 25 publications

(8 citation statements)

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“…Therefore, we conclude that the production of H (3Àn) D n O þ is a stepwise process through the intermediate C 2 H (5Àm) D m O þ ions, similar to the process of excitation by electron ionization. [6][7][8][9] The result of a curve-fitting deconvolution of the H 3 O þ profile from 2-propanol is shown in Fig. 5.…”

Section: Time Constant Of the Metastable Decompositionmentioning

confidence: 99%

“…The process of H 3 O þ formation from organic molecular ions proceeds through metastable-ion decomposition of the intermediate C 2 H 5 O þ ion produced by electron ionization. [6][7][8][9] Raalte and Harrison 6 performed an electron ionization experiment using partially deuterated samples and showed that H/D scrambling of four hydrogen atoms originally belonging to the CÀC site of C 2 H (4Àm) D m -OH þ or C 2 H (4Àm) D m -OD þ (m ¼ 0-4) precedes H (3Àn) D n O þ (n ¼ 0-3) elimination based on the relative yields of H (3Àn) D n O þ . Keyes and Harrison 9 demonstrated that the H (3Àn) D n O þ branching ratios were reproduced by assuming a partial exchange ($30%) of the hydrogen atom in the OH group with four hydrogen atoms at the CÀC site.…”

mentioning

confidence: 99%

“…They also performed an experiment using 13 C-labeled samples and demonstrated that two carbon atoms in the CCO skeletal structure of CH 3 CHOH þ are exchanged with each other through the protonated ethylene oxide structure, which should contribute to the hydrogen exchange. 8 Therefore, isomerization of the metastable C 2 H 5 O þ ion is an interesting subject for research. In recent experiments using intense laser fields, Hoshina et al reported that 2-propanol undergoes efficient H 3 O þ formation.…”

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confidence: 99%

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Formation of H₃O⁺ from alcohols and ethers induced by intense laser fields

Shirota

Mano

Tsuge

et al. 2010

Rapid Comm Mass Spectrometry

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The processes of H(3)O(+) production from alcohols (ethanol, 2-propanol, 1-propanol, 2-butanol) and ethers (diethyl ether and ethyl methyl ether), and their deuterium-substituted species, by intense laser fields (800 nm, 100 fs, approximately 1 x 10(14) W/cm) were investigated through time-of-flight (TOF) mass spectrometry. H(3)O(+) formation was observed for all these compounds except for ethyl methyl ether. From the analysis of TOF signals of H((3-n))D(n)O(+) (n = 0, 1, 2, and 3) that have expanding tails with increasing flight time, it has been confirmed that the reaction proceeds through metastable dissociation from the intermediate species C(2)H((5-m))D(m)O(+)(m = 0-5). The common shape of the H((3-n))D(n)O(+) signal profiles contains two major distributions in the time constant, i.e., fast and slow components of <50 ns and approximately 500 ns, respectively. The H((3-n))D(n)O(+) branching ratio is interpreted to be the result of complete scrambling of four hydrogen atoms at the C-C site in C(2)H(4)-OH(+), and partial exchange (18-38%) of a hydrogen atom in the OH group with four other hydrogen atoms within 1 ns prior to H((3-n))D(n)O(+) production. Ab initio calculations for the isomers and transition states of C(2)H(5)O(+) were also performed, and the observed H((3-n))D(n)O(+) production mechanism has been discussed. In addition, a stable isomer having a complex structure and two isomerization pathways were discovered to contribute to the H(3)O(+) formation process.

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Section: Time Constant Of the Metastable Decompositionmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Formation of H₃O⁺ from alcohols and ethers induced by intense laser fields

Shirota

Mano

Tsuge

et al. 2010

Rapid Comm Mass Spectrometry

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“…Molecules with specific functional groups undergo typical fragmentation patterns, which can be used to obtain structural information. [6][7][8][9][10][11][12][13][14][15] The typical example is the formation of prominent ions of general formula, C n H 2n O +• , observed in the mass spectra of alcohols and ethers. 9,10 The relative abundances of fragment ions and their fragmentation patterns depend on the functional groups of ionized molecule.…”

Section: Introductionmentioning

confidence: 99%

“…[6][7][8][9][10][11][12][13][14][15] The typical example is the formation of prominent ions of general formula, C n H 2n O +• , observed in the mass spectra of alcohols and ethers. 9,10 The relative abundances of fragment ions and their fragmentation patterns depend on the functional groups of ionized molecule. [13][14][15] In the precedent work 14 analyzing the chemical ionization of geometrical isomers of ROOCCR'=CHCOOR (R and R'=H, CH 3 , C 2 H 5 ), the relative abundances of typical ions such as [M+H] + and [M+H-ROH] + were different depending on the functional groups.…”

Section: Introductionmentioning

confidence: 99%

Substituent Effect on Fragmentations and Ion-Molecule Reactions of Ionized Alkyn Alcohols

Choi

So²,

Kim³

2005

Bulletin of the Korean Chemical Society

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The fragmentation patterns and ion-molecule reactions of two alkyn alcohols, 2-propyn-1-ol (HC ≡ CCH 2 OH) and 2-methyl-3-butyn-2-ol (HC ≡ CC(CH 3 ) 2 OH), were investigated using Fourier transform mass spectrometry (FTMS). The most abundant fragment ions formed from the molecular ions were [M-H] + for 2-propyn- + from 2-methyl-3-butyn-2-ol were more favorable than those from 2-propyn-1-ol due to stabilization by two methyl groups at α-carbon. Ion-neutral complexes formed at long ion trapping time gave dehydrated and/or deacetylenylated ion products by further dissociation.

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