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Orthoamide und Iminiumsalze, IC. Synthese und Reaktionen von N,N,N′,N′,N′′-Pentaalkyl-N′′-[2-(N,N,N′,N′,N′′-pentaalkylguanidinio)ethyl]-guanidiniumsalzen

  • Willi Kantlehner EMAIL logo , Ioannis Tiritiris , Wolfgang Frey and Ralf Kreß
Published/Copyright: July 16, 2020
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 75 Issue 6-7

Abstract

Bis[bis(dibutylamino)methylen]hydrazine 8 is prepared from N,N,N′,N′-tetrabutylchloroformamidinium chloride (4c) and hydrazine. Bromine transforms 8 to the heterocyclic guanidinium salt 15a which is isolated as tetraphenylborate. From N,N,N′,N′-tetraalkylchloroformamidiniumchlorides and ethylendiamine the diguanidines are prepared which are alkylated to give diguanidinium salts, From these salts guanidinium salts can be prepared by anion metathesis with tetraphenylborate-, iodide-, hexafluorphosphate-, trifluoromethansulfonat-, bis(trifluormethansulfonyl)imide and tricyanmethanide as counteranions. The structure of the compounds 15 and 17b is confirmed by crystal structure analyses.

Keywords: alkylation; anion metathesis; diguanidines; diguanidinium salts; N,N,N′,N′-tetraalkylchlorformamidinium chlorides; N,N′-bis[bis(dibutylamino)methylene]hydrazine
Corresponding author: Willi Kantlehner, Institut für Angewandte Forschung, Abteilung Technische Organische Synthesechemie und Katalyseforschung (TOSKA), Hochschule Aalen, Germany und Institut für Organische Chemie, Universität Stuttgart, Beethovenstr. 1, D-73430 Aalen, Pfaffenwaldring 55, 70569, Stuttgart, Germany, E-mail:

Orthoamide und Iminiumsalze, IIC see ref. [1].

  1. Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: State Foundation of Baden Württemberg.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

Literatur

1. Kantlehner, W., Tiritiris, I., Vettel, M., Frey, W. Z. Naturforsch. 2020, 75b, 665.10.1515/znb-2019-0229Search in Google Scholar

2. Lecher, H., Graf, F. Ber. Dtsch. Chem. Ges. 1923, 56, 1326.10.1002/cber.19230560614Search in Google Scholar

3. Lecher, H., Graf, F. Liebigs Ann. Chem. 1924, 438, 154.10.1002/jlac.19244380108Search in Google Scholar

4. Lecher, H., Graf, F. Liebigs Ann. Chem. 1925, 445, 61.10.1002/jlac.19254450104Search in Google Scholar

5. Lecher, H., Graf, F., Gnädiger, F., Bolz, K. Liebigs Ann. Chem. 1927, 455, 139.10.1002/jlac.19274550111Search in Google Scholar

6. Kantlehner, W., Mezger, J., Kreß, R., Hartmann, H., Moschny, T., Tiritiris, I., Iliev, B., Scherr, O., Ziegler, G., Souley, B., Frey, W., Ivanov, I. C., Bogdanov, M. G., U. Jäger U, Dospil, G., Viefhaus, T. Z. Naturforsch. 2010, 65b, 873.10.1515/znb-2010-0712Search in Google Scholar

7. Knobloch, G., Saur, S., Tussetschläger, S., Gentner, R., Stein, T., Hader, B., Kantlehner, W. Z. Naturforsch. 2016, 71b, 709.10.1515/znb-2015-0180Search in Google Scholar

8. Schlama, T., Gouverneur, V., Valleix, A., Greiner, A., Toupet, L., Mioskowski, C. J. Org. Chem. 1997, 62, 4200.10.1021/jo961573qSearch in Google Scholar

9. Mateus, N. M. M., Branco, L. C., Lourenço, N. M. T., Alfonso, C. A. M. Green Chemistry 2003, 5, 347.10.1039/B303408ASearch in Google Scholar

10. Kantlehner, W., Haug, E., Mergen, W. W., Speh, P., Maier, T., Kapassakalidis, J. J., Bräuner, H.-J. Synthesis 1983, 15, 904.10.1055/s-1983-30558Search in Google Scholar

11. Kantlehner, W., Haug, E., Mergen, W. W., Speh, P., Maier, T., Kapassakalidis, J. J., Bräuner, H.-J., Hagen, H. Liebigs Ann. Chem. 1984, 108.Search in Google Scholar

12. Bogdanov, M. G., Petkova, D., Hristeva, S, Swingarow, J., Kantlehner, W. Z. Naturforsch. 2010, 65b, 37.10.1515/znb-2010-0108Search in Google Scholar

13. Tiritiris, I., Lissner, F., Schleid, T., Kantlehner, W. Z. Naturforsch. 2010, 65b, 907.10.1515/znb-2010-0713Search in Google Scholar

14. Tiritiris, I., Mezger, J., Stoyanov, E. V., Kantlehner, W. Z. Naturforsch. 2011, 66b, 407.10.5560/ZNB.2011.66b0164Search in Google Scholar

15. Tiritiris, I., Kantlehner, W. Z. Naturforsch. 2012, 67b, 685.10.5560/znb.2012-0061Search in Google Scholar

16. Tiritiris, I., Kantlehner, W. Adv. Chem. Lett. 2013, 1, 1.10.1166/acl.2013.1044Search in Google Scholar

17. Brunelle, D. J., Haitko, D. H., Barren, J. P., Sing, S. (General Electric Co.), US Pat 5.123.423 (21.7.1997, Appl. 13.3.1991), Chem. Abstr. 1993, 118, 124192.Search in Google Scholar

18. Brunelle, D. J. (General Electric Co.), US Pat 5.229.482 (20.7.1993, Appl. 28.2.1991), Chem. Abstr. 1994, 120, 31523.Search in Google Scholar

19. Ikgumnov, S., Delyagina, N. I., Knunjants, I. L. Izv. Akad. Nauk SSSR, Ser. Khim. 1986, 1315; Bull. Acad. Sci. USSR 1986, 1191.Search in Google Scholar

20. Kantlehner, W., Kreß, R., Mezger, J., Ziegler, G. Z. Naturforsch. 2015, 70b, 9.10.1515/znb-2014-0102Search in Google Scholar

21. Kunkel, H., Maas, G. Eur. J. Org. Chem. 2007, 3746.10.1002/ejoc.200700303Search in Google Scholar

22. Xie, H., Zhang, S., Duan, H. Tetrahedron Lett. 2004, 45, 2013.10.1016/j.tetlet.2003.12.141Search in Google Scholar

23. Gao, Y., Arritt, S. W., Twamley, B., Shreeve, J. M. Inorg. Chem. 2005, 44, 1704.10.1021/ic048513kSearch in Google Scholar PubMed

24. Kessler, H., Leibfritz, D. Chem. Ber. 1971, 104, 2158.10.1002/cber.19711040716Search in Google Scholar

25. Wieland, G., Simchen, G. Liebigs Ann. Chem. 1985, 2178.10.1002/jlac.198519851108Search in Google Scholar

26. Ignatiev, N., Welz-Biermann, U., Willner, H., Bissky, G. (Merck Patent GmbH), DOS 10325051A1, 2. Juni 2003.Search in Google Scholar

27. Ignatiev, N., Welz-Biermann, U., Willner, H., Bissky, G. (Merck Patent GmbH), DOS 10325051, 23. Dezember 2004.Search in Google Scholar

28. Kantlehner, W., Edelmann, K., Gissel, A., Scherr, O., Vetter, J., Wezstein, M., Ziegler, G., Mezger, J., Iliev, B. Acta Chim. Slov. 2009, 56, 612.Search in Google Scholar

29. King, J. A. Jr.Phelps, P. D. US Pat. 5.726.85, 10. März 1998.Search in Google Scholar

30. Hobbs, C. F., Weingarten, H. J. Org. Chem. 1971, 36, 2885.10.1021/jo00818a035Search in Google Scholar

31. Ignat’ev, N. V., Welz-Biermann, U., Kucharyna, A., Bissky, G., Willner, H. J. Fluorine Chem. 2005, 126, 1150.10.1016/j.jfluchem.2005.04.017Search in Google Scholar

32. Weingarten, H., White, W. A. J. Am. Chem. Soc. 1968, 88, 2885.10.1021/ja00964a071Search in Google Scholar

33. Salchner, R., Kahlenberg, V., Gelbrich, T., Wurst, K., Rausch, M., Laus, G., Schottenberger, H. Crystals 2014, 4, 404.10.3390/cryst4030404Search in Google Scholar

34. Flossner, D. A., Olofson, R. A. Tetrahedron Lett. 2002, 43, 4275.10.1016/S0040-4039(02)00738-4Search in Google Scholar

35. Pentin, Yu., Makhon’kov, D. I., D’yachhova, L. A., Baburina, I. I., Zefirov, N. S. Zh. Obsh. Khim. 1978, 48, 1850; J. Gen. Chem. USSR (Engl. Transl.) 1979, 1688.Search in Google Scholar

36. Wang, P., Zaakeruddin, S. M., Grätzel, M., Kantlehner, W., Mezger, J., Stoyanov, E. V., Scherr, O. Appl. Phys. 2004, A79, 73.10.1007/s00339-003-2505-xSearch in Google Scholar

37. Petz, W., Krüger, C., Goddard, R. Chem. Ber. 1979, 117, 3413.10.1002/cber.19791121009Search in Google Scholar

38. Petz, W. J. Organomet. Chem. 1975, 90, 223.10.1016/S0022-328X(00)92115-6Search in Google Scholar

39. Petz, W. Z. Naturforsch. 1976, 31b, 1007.10.1515/znb-1976-0726Search in Google Scholar

40. Petz, W. J. Organomet. Chem. 1976, 105, C19.10.1016/S0022-328X(00)91985-5Search in Google Scholar

41. Mayr, A., Lin, Y. C., Boag, N. M., Kampe, C. E., Knobler, C. B., Kaesz, H. D. Inorg. Chem. 1984, 23, 4640.10.1021/ic00194a045Search in Google Scholar

42. Mayr, A., Lin, Y. C., Boag, N. M., Kaesz, H. D. Inorg. Chem. 1982, 21, 1704.10.1021/ic00134a098Search in Google Scholar

43. Jokisch, A., Schier, A., Schmidbaur, H. Chem. Ber. 1997, 130, 1739.10.1002/cber.19971301206Search in Google Scholar

44. Wittmann, H., Schorm, A., Sundermeyer, J. Z. Anorg. Allg. Chem. 2000, 626, 1583.10.1002/1521-3749(200007)626:7<1583::AID-ZAAC1583>3.0.CO;2-3Search in Google Scholar

45. Herres-Pawlis, E., Neuba, A., Seewald, O., Seshhadri, T., Egold, H., Flörke, U., Henkel, G. Eur. J. Org. Chem. 2005, 4879.10.1002/ejoc.200500340Search in Google Scholar

46. Weingarten, H., Wager, J. S. Tetrahedron Letters 1969, 3267.10.1016/S0040-4039(01)88405-7Search in Google Scholar

47. Kantlehner, W., Lehmann, H., Stahl, T., Kaim, W. Chemiker Ztg. 1991, 115, 183.Search in Google Scholar

48. Vettel, M. Dissertation, Universität Stuttgart, Stuttgart, 1995, S. 58.Search in Google Scholar

49. Stella, L., Janousek, Z., Marényi, R., Viehe, H. G. Angew. Chem., Int. Ed. Engl. 1978, 17, 691.10.1002/anie.197806911Search in Google Scholar

50. Tiritiris, I., Kantlehner, W. IUCrData 2016, 1, x160047.10.1107/S241431461600047XSearch in Google Scholar

51. Bock, H. Z. Anorg. All. Chem. 1957, 293, 264.10.1002/zaac.19582930505Search in Google Scholar

Erhalten: 2019-12-18
Angenommen: 2020-05-06
Online erschienen: 2020-07-16
Erschienen im Druck: 2020-08-27

© 2020 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Research articles
  4. Derivatives of the triaminoguanidinium ion, 7: unsymmetrically substituted N,N',N''-triaminoguanidinium salts via a cyclopentanone spiroaminal intermediate
  5. Diethyl (iodoethynyl)phosphonate and (iodoethynyl)diphenylphosphane oxide: crystal structures and some cycloaddition reactions
  6. Synthesis, molecular structure and BSA-binding properties of a new binuclear Cd(II) complex based on 2-(1H-tetrazol-1-methyl)-1H-imidazole-4,5-dicarboxylic acid
  7. Microwave synthesis of a blue luminescent silver(I) coordination polymer with a rigid tris-triazole ligand
  8. Single-crystal structure determination of LaNi5–xInx and LaNi9–xIn2+x
  9. The reaction of imidazo[1,5-a]pyridines with ninhydrin revisited
  10. The syntheses, structures, and magnetic properties of two mononuclear manganese(II) complexes involving in situ hydrothermal decarboxylation
  11. A cobalt(II) coordination polymer constructed with the 2-carboxy-phenoxyacetate linker showing a corrugated layer structure: synthesis, structure analysis and magnetic properties
  12. Hexaniobate anions connected by [Ni(cyclam)]2+ complexes yield two interpenetrating three-dimensional networks
  13. High-pressure synthesis and crystal structure of the samarium meta-oxoborate γ-Sm(BO2)3
  14. High-pressure synthesis and characterization of the non-centrosymmetric scandium borate ScB6O9(OH)3
  15. Al5B12O25(OH) and Ga4InB12O25(OH) – two additional triel borates with the structure type M5B12O25(OH) (M = Ga, In)
  16. Al/N-based active Lewis pairs: isocyanate insertion products as efficient nucleophiles employed for the facile generation of highly functional molecules
  17. New compounds of the Li2MSn3S8 type
  18. Synthesis and magnetic properties of the extended RE4Pd9Al24 series (RE = Sc, Y, Ce–Nd, Sm, Gd–Lu)
  19. Solid solutions EuAu4Cd2−xMgx with a remarkably stable ferromagnetic ground state
  20. Mechanistic investigations on C–H activated dealkylating cyclo-amination reactions of substituted triazenes, formamidines and amidines
  21. Orthoamide und Iminiumsalze, IIC. Darstellung von N-(ω-Ammonioalkyl)-N,N′,N′,N″,N″-peralkylierten Guanidiniumsalzen und N-(ω-Aminoalkyl)-N′,N′,N″,N″-tetramethylguanidinen
  22. Orthoamide und Iminiumsalze, IC. Synthese und Reaktionen von N,N,N′,N′,N′′-Pentaalkyl-N′′-[2-(N,N,N′,N′,N′′-pentaalkylguanidinio)ethyl]-guanidiniumsalzen
  23. Orthoamide und Iminiumsalze, C. Vinyloge Guanidiniumsalz-basierte ionische Flüssigkeiten sowie phenyloge Guanidiniumsalze und Orthoamide
  24. Notes
  25. La5Ir1.73In4.27 with Lu5Ni2In4-type structure
  26. The scandium-rich indide Sc50Pt13.47In2.53
https://doi.org/10.1515/znb-2019-0230
Keywords for this article
alkylation; anion metathesis; diguanidines; diguanidinium salts; N,N,N′,N′-tetraalkylchlorformamidinium chlorides; N,N′-bis[bis(dibutylamino)methylene]hydrazine

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Research articles
  4. Derivatives of the triaminoguanidinium ion, 7: unsymmetrically substituted N,N',N''-triaminoguanidinium salts via a cyclopentanone spiroaminal intermediate
  5. Diethyl (iodoethynyl)phosphonate and (iodoethynyl)diphenylphosphane oxide: crystal structures and some cycloaddition reactions
  6. Synthesis, molecular structure and BSA-binding properties of a new binuclear Cd(II) complex based on 2-(1H-tetrazol-1-methyl)-1H-imidazole-4,5-dicarboxylic acid
  7. Microwave synthesis of a blue luminescent silver(I) coordination polymer with a rigid tris-triazole ligand
  8. Single-crystal structure determination of LaNi5–xInx and LaNi9–xIn2+x
  9. The reaction of imidazo[1,5-a]pyridines with ninhydrin revisited
  10. The syntheses, structures, and magnetic properties of two mononuclear manganese(II) complexes involving in situ hydrothermal decarboxylation
  11. A cobalt(II) coordination polymer constructed with the 2-carboxy-phenoxyacetate linker showing a corrugated layer structure: synthesis, structure analysis and magnetic properties
  12. Hexaniobate anions connected by [Ni(cyclam)]2+ complexes yield two interpenetrating three-dimensional networks
  13. High-pressure synthesis and crystal structure of the samarium meta-oxoborate γ-Sm(BO2)3
  14. High-pressure synthesis and characterization of the non-centrosymmetric scandium borate ScB6O9(OH)3
  15. Al5B12O25(OH) and Ga4InB12O25(OH) – two additional triel borates with the structure type M5B12O25(OH) (M = Ga, In)
  16. Al/N-based active Lewis pairs: isocyanate insertion products as efficient nucleophiles employed for the facile generation of highly functional molecules
  17. New compounds of the Li2MSn3S8 type
  18. Synthesis and magnetic properties of the extended RE4Pd9Al24 series (RE = Sc, Y, Ce–Nd, Sm, Gd–Lu)
  19. Solid solutions EuAu4Cd2−xMgx with a remarkably stable ferromagnetic ground state
  20. Mechanistic investigations on C–H activated dealkylating cyclo-amination reactions of substituted triazenes, formamidines and amidines
  21. Orthoamide und Iminiumsalze, IIC. Darstellung von N-(ω-Ammonioalkyl)-N,N′,N′,N″,N″-peralkylierten Guanidiniumsalzen und N-(ω-Aminoalkyl)-N′,N′,N″,N″-tetramethylguanidinen
  22. Orthoamide und Iminiumsalze, IC. Synthese und Reaktionen von N,N,N′,N′,N′′-Pentaalkyl-N′′-[2-(N,N,N′,N′,N′′-pentaalkylguanidinio)ethyl]-guanidiniumsalzen
  23. Orthoamide und Iminiumsalze, C. Vinyloge Guanidiniumsalz-basierte ionische Flüssigkeiten sowie phenyloge Guanidiniumsalze und Orthoamide
  24. Notes
  25. La5Ir1.73In4.27 with Lu5Ni2In4-type structure
  26. The scandium-rich indide Sc50Pt13.47In2.53
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