Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides

Witt M, Kreft D, Grützmacher H-F (2003)
EUROPEAN JOURNAL OF MASS SPECTROMETRY 9(1): 81-95.

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Autor*in
Witt, Matthias; Kreft, Dirk; Grützmacher, Hans-FriedrichUniBi
Abstract / Bemerkung
The proton affinity (PA) of cyclopentane carboxamide 1, cyclohexane carboxamide 2 and their secondary and tertiary amide derivatives S1, S2, T1 and T2, was determined by the thermokinetic method and the kinetic method [PA(1) = 888 +/- 5 kJ mol(-1); PA(2) = 892 +/- 5 kJ mol(-1); PA(S1) = 920 +/- 6 kJ mol(-1); PA(S2) = 920 +/- 6 kJ mol(-1); PA(T1) = 938 +/- 6 kJ mol(-1); PA(T2) = 938 +/- 6 kJ mol(-1)]. Special entropy effects are not observed. Additionally, the effects of protonation have been studied using an advanced kinetic method for all isomers 3-7 of cyclopentane dicarboxamides and cyclohexane dicarboxamides (with the exception of cis-cyclopentane-1,2-dicarboxamide) and their bis-tertiary derivatives T3-T7 by estimating the PA and the apparent entropy of protonation Delta(DeltaS(app)). Finally, the study was extended to bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxamide 8 and its bis-tertiary derivative T8, to all stereoisomers of bicyclo[2.2.1]heptane-2,3-dicarboxamide 9, their secondary and tertiary amide derivatives S9 and T9, and to endo-endo-bicyclo[2.2.1]heptane-2,5-dicarboxamide 10 and the corresponding secondary and tertiary derivatives S10 and T10. Compared with 1 and 2, all alicyclic diamides exhibit a significant increase of the PA (DeltaPA) and special entropy effects on protonation. For alicyclic diamides, which can not accommodate a conformation appropriate for building a proton bridge, the values of DeltaPA and Delta(DeltaS(app)) are small to moderate. This is explained by ion/dipole interactions between the protonated and neutral amide group which stabilize the protonated species but hinder the free rotation of the amide groups. If any of the conformations of the alicyclic diamide allows formation of a proton bridge, DeltaPA and Delta(DeltaS(app)) increase considerably. A spectacular case is cis-cyclohexane-1,4-dicarboxamide 7c which is the most basic monocyclic diamide, although generation of the proton bridge requires the unfavorable boat conformation with both amide substituents at a flagpole position. A pre-orientation of the two amide groups in such a 1,4-position in 10 results in a particularly large PA of < 1000 kJ mol(-1). The observation of comparable values for Delta(DeltaS(app)) for linear and monocyclic diamides indicates that a major part of the entropy effects originates from freezing the free rotation of the amide groups by formation of the proton bridge. This is corroborated by observing corresponding effects during the protonation of dicarboxamides containing the rigid bicyclo[2.2.1]heptane carbon skeleton, where the only internal movements of the molecules corresponds to rotation of the amide substituents.
Stichworte
amides; proton affinity; proton bound dimers; spectrometry; FT-ICR; alicyclic diamides; tandem mass spectrometry; thermokinetic method; method; entropy effect; kinetic
Erscheinungsjahr
2003
Zeitschriftentitel
EUROPEAN JOURNAL OF MASS SPECTROMETRY
Band
9
Ausgabe
1
Seite(n)
81-95
ISSN
1356-1049
Page URI
https://pub.uni-bielefeld.de/record/1611209

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Witt M, Kreft D, Grützmacher H-F. Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides. EUROPEAN JOURNAL OF MASS SPECTROMETRY. 2003;9(1):81-95.
Witt, M., Kreft, D., & Grützmacher, H. - F. (2003). Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides. EUROPEAN JOURNAL OF MASS SPECTROMETRY, 9(1), 81-95. https://doi.org/10.1255/ejms.535
Witt, Matthias, Kreft, Dirk, and Grützmacher, Hans-Friedrich. 2003. “Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides”. EUROPEAN JOURNAL OF MASS SPECTROMETRY 9 (1): 81-95.
Witt, M., Kreft, D., and Grützmacher, H. - F. (2003). Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides. EUROPEAN JOURNAL OF MASS SPECTROMETRY 9, 81-95.
Witt, M., Kreft, D., & Grützmacher, H.-F., 2003. Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides. EUROPEAN JOURNAL OF MASS SPECTROMETRY, 9(1), p 81-95.
M. Witt, D. Kreft, and H.-F. Grützmacher, “Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides”, EUROPEAN JOURNAL OF MASS SPECTROMETRY, vol. 9, 2003, pp. 81-95.
Witt, M., Kreft, D., Grützmacher, H.-F.: Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides. EUROPEAN JOURNAL OF MASS SPECTROMETRY. 9, 81-95 (2003).
Witt, Matthias, Kreft, Dirk, and Grützmacher, Hans-Friedrich. “Effects of internal hydrogen bonds between amide groups: protonation of alicyclic diamides”. EUROPEAN JOURNAL OF MASS SPECTROMETRY 9.1 (2003): 81-95.

3 Zitationen in Europe PMC

Daten bereitgestellt von Europe PubMed Central.

Current literature in mass spectrometry.
, J Mass Spectrom 38(9), 2003
PMID: 14505330

24 References

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Pimentel, 1960

Meot-Ner(Mautner), J. Am. Chem. Soc. 101(), 1979

Zhang, J. Am. Chem. Soc. 116(), 1994

Witt, Int. J. Mass Spectrom. 164(), 1997

Witt, 1998

Witt, Eur. Mass Spectrom. 5(), 2000

Cooks, J. Am. Chem. Soc. 99(), 1977

Caprioli, 1973

Anicich, J. Phys. Chem. Ref. Data 22(), 1993

Bartmess, Vacuum 33(), 1983

AUTHOR UNKNOWN, 1996

Su, J. Chem. Phys. 76(), 1982

Bouchoux, Int. J. Mass Spectrom. Ion Processes 153(), 1996

Bohme, J. Chem. Phys. 73(), 1980

Houriet, New J. Chem. 11(), 1987

Cooks, J. Mass Spectrom. 34(), 1999
Entropy measurements and the kinetic method: a statistically meaningful approach
Armentrout PB., J. Am. Soc. Mass Spectrom. 11(5), 2000
PMID: 10790840

Cao, Eur. Mass Spectrom. 5(), 1999

Witt, Int. J. Mass Spectrom. 222(), 2003

Eliel, 1962

Frisch, 1998

Dewar, J. Am. Chem. Soc. 108(), 2003
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