Tricyclopropylamine and its radical cation

Angewandte Chemie - International Edition

Volumn 38, Issue 16, 1999, Pages 2430-2433

  De Meijere, Armin ^a   Chaplinski, Vladimir ^a   Winsel, Harald ^a   Kusnetsov, Mikhael A ^a   Rademacher, Paul ^c   Boese, Roland ^c   Haumann, Thomas ^c   Traetteberg, Marit ^d   Schleyer, Paul Von R ^e   Zywietz, Tosja ^a   Jiao, Haijun ^e   Merstetter, Pascal ^b   Gerson, Fabian ^b  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

^b UNIVERSITY OF BASEL   (Switzerland)

^c UNIVERSITY OF DUISBURG ESSEN   (Germany)

^d NORWEGIAN UNIVERSITY OF SCIENCE AND TECHNOLOGY   (Norway)

^e UNIVERSITY OF GEORGIA   (United States)

Author keywords

Density functional calculations; Electron diffraction; EPR spectroscopy; Photoelectron spectroscopy; Structure elucidation

Indexed keywords

CATION; PROPYLAMINE;

ARTICLE; CHEMICAL BOND; CONFORMATIONAL TRANSITION; CRYSTAL STRUCTURE; STEREOSPECIFICITY; STRUCTURE ANALYSIS; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

EID: 0033549734     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19990816)38:16<2430::AID-ANIE2430>3.0.CO;2-V     Document Type: Article

References (31)

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3. f(R) = 0.00 (Me), 0.86 (Et), 2.29 (iPr), 3.82 (tBu), 1.33 (cPr), 1.81 (cPent).
4. f(R) = 0.00 (Me), 0.86 (Et), 2.29 (iPr), 3.82 (tBu), 1.33 (cPr), 1.81 (cPent).
5. See: A. de Meijere, Angew. Chem. 1979, 91, 867-884; Angew. Chem. Int. Ed. Engl. 1979, 18, 809-826, and references therein.
6. See: A. de Meijere, Angew. Chem. 1979, 91, 867-884; Angew. Chem. Int. Ed. Engl. 1979, 18, 809-826, and references therein.
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9. V. Chaplinski, A. de Meijere, Angew. Chem. 1996, 108, 491-492; Angew. Chem. Int. Ed. Engl. 1996, 35, 413-414.
10. Improved protocol: V. Chaplinski, H. Winsel, M. Kordes, A. de Meijere. Synlett, 1997, 111-114.
11. [8] to provide 3 (overall yield from benzylcydopropylformamide: 28%) along with dicyclopropylamine. Our synthesis of 3 was presented in a lecture at the Gordon Conference on Physical Organic Chemistry, July 2-7, 1995, in Plymouth, NH, USA. Four months later, an alternative synthesis of tricyclopropylamine 3 was reported: M. L. Gillaspy, B. A. Lefker, W. A. Hada, D. J. Hoover, Tetrahedron Lett. 1995, 36, 7399-7402.
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13. -3. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-101130. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
14. R. Boese, M. Nussbaumer in Organic Crystal Chemistry (Ed.: D. W. Jones), Oxford University Press, Oxford, England, 1994, p. 20.
15. [7] Thus, this analysis can be considered as confirming the overall geometry of the molecule, but it does not allow any deeper interpretation of bond lengths and angles.
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18. Details of this gas-phase electron diffraction structure analysis of 3 will be reported elsewhere.
19. R. Boese, D. Bläser, M. Yu. Antipin, V. Chaplinski, A. de Meijere, Chem. Commun. 1998, 781-782.
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21. The tertiary cyclopropylamines 4-6 were prepared by the same methodology as applied to produce 3, starting from diisopropylformamide, diethylformamide, and cyclopropylisopropylformamide, respectively. Dicyclopropylethylamine (7) was obtained by twofold cyclopropanation of ethyldiformylamine (see refs. [5,20]), V. Chaplinski, Dissertation, Universität Göttingen, 1996.
22. I-PE spectra were recorded on a Leybold-Heraeus UPG200 spectrometer. The calibration of the energy scale was performed with an argon/xenon mixture. The accuracy of ionization energies is ±0.03eV.
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24. Full details of this crystal structure analysis of 4 and the preparations of 4-7 will be published separately. R. Boese, D. Bläser, H. Winsel, A. de Meijere, unpublished results.
25. In mixed cyclopropyl-isopropyl-hexasubstituted benzenes, though, the cyclopropyl groups also do not join in the "tongue and grove" orientations of the isopropyl groups. See: W. Weissensteiner, A. Gutierrez, M. D. Radcliffe, J. Siegel, P. J. Tuohey, K. Mislow, J. Org. Chem. 1985, 5822-5827.
26. A. de Meijere, V. Chaplinski, F. Gerson, P. Merstetter, E. Haselbach, J. Org. Chem. in press.
27. In contrast, the EPR spectrum of the cyclopropylamine radical cation could not be observed, as it rapidly underwent ring-opening when formed by γ-irradiation of cyclopropylamine in several Freon matrices. See: X.-Z. Quin, F. Williams, J. Am. Chem. Soc. 1987, 109, 595-597.
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30. SOS-DFPT = sum-over-states density functional perturbation theory: V. G. Malkin, O. L. Malkin, L. A. Eriksson, D. R. Salahub, J. Am. Chem. Soc. 1994,116, 5898; V. G. Malkin, O. L. Malkin, D. R. Salahub, Chem. Phys. Lett. 1994, 221, 91.
31. For a review see: V. G. Malkin, O. L. Malkin, L. A. Eriksson, D. R. Salahub in Modern Density Functional Theory (Eds. : J. M. Seminario, P. Politzer), Elsevier, Amsterdam, 1995, p. 273, and references therein.