Basic isotopic hydrogen exchange of heteroaromatic compounds (review)

Zatsepina, N. N.; Tupitsyn, I. F.

doi:10.1007/bf00474317

Cited by 4 publications

(2 citation statements)

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“…The ion intensities at 178 to 180 amu were larger than expected, indicating that the sample contains more than two equivalents of deuterium and these must be in the indole moiety. Base-catalyzed ring deuteration of IAA, although not unexpected (38), has not been previously reported. Attempts to minimize this reaction, with maximal side chain labeling, by varying the ratios and concentrations of IAA and potassium deuteroxide, during the exchange procedure, were not successful.…”

Section: Resultsmentioning

confidence: 79%

Synthesis of 4,5,6,7 and 2,4,5,6,7 Deuterium-labeled Indole-3-Acetic Acid for Use in Mass Spectrometric Assays

Magnus

Bandurski²,

Schulze³

1980

Plant Physiol.

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Syntheses are described for tetra and pentadeutero indole-3-acetic acid (IAA) labeled in positions 4, 5, 6, 7 or 2, 4, 5, 6, 7 of the indole moiety. Polydeuterated IAA is proposed as an internal standard for gas chromatographic-mass spectrometric analysis of IAA by selected ion monitoring. Nanogram amounts of IAA may be assayed by monitoring the base peak of IAA at m/z = 130 (134 for d4-IAA) and the molecular ion of the methyl ester of IAA at 189 (193 for d4-IAA). Deuterium in positions 4,5,6,and 7 and, to only a slightly lesser extent, that in position 2 of IAA is retained during alkali treatment, thus permitting use of these compounds as internal standards for assay of IAA released by alkaline hydrolysis of ester and amide conjugates. The use of polydeutero internal standards separates the standards from the "isotope cluster" caused by the normal abundance of heavy isotopes and also permits use of reduced mass resolution, thus leading to a 10-fold increase in sensitivity.Tetradeutero IAA was used as an internal standard for determining free plus ester IAA in alkaline hydrolysates of Zea mays, and showed exact agreement between estimates based on the molecular ion of the methyl ester and those based upon base peak. Application of the method to measuring free IAA in the upper and lower halves of geotropically stimulated Zea shoots showed 61 ± 4% of the free IAA to be on the lower side.Indolylic compounds, other than tryptophan, occur in plant (cf. 3, 4) and in animal tissue (cf. 23) in ylM amounts. Low tissue concentrations of the indoles and their lability (16,22,24) make assay by GC-SIM-MS4, with deuterated IAA as an internal standard, an attractive procedure. A number of procedures have been described using side chain d2-indoles as standards for assay of IAA and 5-hydroxy-IAA in plants and animals (1, 6, 10, 26). However, plants contain most of their IAA as ester or amide conjugates, conveniently assayed as free IAA, following hydrolysis of the esters by 1 N NaOH and the amide conjugates in 7 N NaOH (4). Alkaline hydrolysis precludes use of d2-IAA with deuterium in the side chain, since these deuterium are lost during base treatment. Deuterium in positions 4, 5, 6, and 7 is not exchanged with hydrogen during alkaline hydrolysis. Even deuterium in the 2 position is only slightly exchanged. ' To whom reprint requests should be directed.4Abbreviations: GC-SIM-MS, gas chromatography-selected ion monitoring-mass spectrometry; mp, melting point; NMR, nuclear magnetic resonance. synthesis for 4,5,6,7-d4-IAA and 2,4,5,6,7-d5-IAA and use of these compounds as internal standards.In addition to alkali stability, polydeuterated compounds provide additional advantages as internal standards for GC-SIM-MS. The ions generated by d4-and d5-IAA during MS are remote from the ions of IAA and, thus, the background caused by the normal abundances of heavy ions at I and 2 mass units above the IAA is eliminated. Further, providing sample purity is adequate, mass resolution may be broadened to ±+ amu (fat peak monitoring) y...

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Section: Resultsmentioning

confidence: 79%

Synthesis of 4,5,6,7 and 2,4,5,6,7 Deuterium-labeled Indole-3-Acetic Acid for Use in Mass Spectrometric Assays

Magnus

Bandurski²,

Schulze³

1980

Plant Physiol.

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“…The methods for the preparation of heterocyclic and heteroaromatic compounds containing hydrogen isotopes have been reviewed. 59,60 The nucleic acid components exchange most readily the proton bound to the C(8) atom of the purine bases. The hydrogen bound to the C(2) atom is exchanged with a much greater difficulty.…”

Section: Reactions With Tritium-containing Solventsmentioning

confidence: 99%

Synthesis of tritium-labelled biologically important diazines

Sidorov¹,

Myasoedov²

1999

Russ. Chem. Rev.

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In a series of publications we presented a solution of the time-dependent Schrodinger equation for collisions between one-electron ions and atoms by an expansion in terms of two-centre wavefunctions of the Hylleraas type. In this contribution we present differential cross sections for direct and electron exchange processes in proton-hydrogen collisions at 1 and 2 keV. The scattering angle dependence as well as the energy dependence of the related charge exchange probability is studied and compared with competing theoretical approaches and experiment.

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Five-Membered Hetarynes

Reinecke

1982

Reactive Intermediates

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Basic isotopic hydrogen exchange of heteroaromatic compounds (review)

Cited by 4 publications

References 67 publications

Synthesis of 4,5,6,7 and 2,4,5,6,7 Deuterium-labeled Indole-3-Acetic Acid for Use in Mass Spectrometric Assays

Synthesis of 4,5,6,7 and 2,4,5,6,7 Deuterium-labeled Indole-3-Acetic Acid for Use in Mass Spectrometric Assays

Synthesis of tritium-labelled biologically important diazines

Five-Membered Hetarynes

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