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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

  • Willi Kantlehner EMAIL logo , Ioannis Tiritiris , Markus Vettel and Wolfgang Frey
Published/Copyright: July 13, 2020
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 75 Issue 6-7

Abstract

N,N,N′,N′-Tetraalkylchlorformamidiniumchlorides 1a, b react with ω-dimethylaminoalkylamines 19, 20 to give mixtures of N-(ω-dimethylammonioalkyl)-guanidinium salts 12, 13 and N-(ω-dimethylaminoalkyl)-guanidinium salts 21, 22. These mixtures are transformed to mixtures of the ureas 15, 17 and N-(ω-dimethylaminoalkyl)-guanidines 23, 25 on treatment with aqueous sodium hydroxide. The reaction of N-(3-dimethylammoniopropyl)-guanidin 25a with dimethylsulfate in a molar ratio of 1:1 delivers a mixture of the N-(3-dimethylaminopropyl)-N,N,N′,N′,N″,N″-pentamethyl-guanidinium salt 29a and the N-(3-dimethylammoniopropyl)-N,N′,N′,N″,N″-pentamethyl-guanidinium-bis (methylsulfate) 33a. The action of dimethylsulfate on the guanidines 23a, 25a in a molar ratio of 2:1 affords the bisquarternary salts 32a, 33a. Alkylating reagents as methyliodide, benzylbromide, allylbromide and chloroacetonitrile attack N-(2-dimethylaminoethyl)-N′,N′,N″,N″-tetraethylguanidine (23b) in a molar ratio of 1:1 cleanly at the dimethylaminoethylgroup to give the ammonium salts 30a–d. As a strong base the guanidine 23b dehydrochlorinates β-Chlorpropionitrile and chloroacetone under formation of the guanidinium salt 21c. In contrast to this the reaction of ethyl bromoacetate with the N-(2-dimethylaminoethyl)guanidine 23b occurs at the guanidinogroup giving the guanidinium salt 28c. The methylation of the guanidinium chlorides 21a, 22a with dimethyl sulfate affords the bis-quaternary salts 35b, 36b with mixed anions. From the heterocyclic guanidines 14, 16 and the alkylating reagents benzylbromide and ethyl bromoacetate the heterocyclic guanidinium salts 37a, b, 39a, b can be obtained. The reactions with ethyl chloroformiate proceed in an analogous way giving the guanidinium salts 37c, 39c. The N-alkyl-N,N,N′,N′-tetramethyl-(3-ureidopropyl)guanidinium salts 41a, b can be prepared from the N′,N′,N″,N″-tetramethyl-N′′-(3-ureidopropyl) guanidine 17a and the alkylating compounds dimethyl sulfate and benzyl bromide. Several compounds obtained that way were transformed to the corresponding tetraphenyloborates and bis(tetraphenylborates), respectively.

Keywords: alkylation; heterocyclic guanidinium salts; N-alkyl-N′,N′,N″,N″-tetramethyl-N-(3-ureidopropyl) guanidinium salts; N-(ω-alkyldimethylammonioalkyl)-N,N′,N′,N″,N″-pentaalkyl-guanidinium salts; N-(ω-dimethylaminoalkyl)-N′,N′,N″,N″-tetraalkylguanidines

Widmung: Herrn Professor Dr. Franz X. Effenberger zum 90. Geburts-tag.

Corresponding author: Willi Kantlehner, Institut für Angewandte Forschung, Abteilung Technische Organische Synthesechemie und Katalyseforschung (TOSKA), Hochschule Aalen, Beethovenstr. 1, D-73430 Aalen, Germany; Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany, E-mail:

Orthoamide und Iminiumsalze, IIIC 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: Die vorliegende Arbeit wurde im Rahmen des BMBF-Projekts „Schmelzelektrolyte und photosensibilisierende Lösungsmittel für photoelektro-chemische Solarzellen“ (FKZ 1705598) und des Projekts „Kohlendioxid als Baustein für Energieträger – Ein Beitrag zur Reduzierung des Treibhauseffektes“ der Landesstiftung des Landes Baden Württemberg durchgeführt.

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

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Received: 2019-12-18
Accepted: 2020-04-30
Published Online: 2020-07-13
Published in Print: 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-2019-0229
Keywords for this article
alkylation; heterocyclic guanidinium salts; N-alkyl-N′,N′,N″,N″-tetramethyl-N-(3-ureidopropyl) guanidinium salts; N-(ω-alkyldimethylammonioalkyl)-N,N′,N′,N″,N″-pentaalkyl-guanidinium salts; N-(ω-dimethylaminoalkyl)-N′,N′,N″,N″-tetraalkylguanidines

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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