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Synthesis of Guanidines via Reaction of Amines with Carbodiimides in the Presence of Ionic Liquid

Year 2016, Volume: 3 Issue: 1, 19 - 26, 11.01.2016

Abstract

Different ionic liquids (ILs) were synthesized and evaluated for the preparation of substituted guanidines from the reaction of amines and carbodiimides. 1-methylimidazolium tetrafluoroborate [HMIm]BF4 was found to be the best ionic liquid for this reaction. This IL acted as a promoter for the addition of primary and secondary amines to carbodiimides. By this efficient approach, various guanidines were prepared in excellent yields.

References

  • Mori A, Cohen BD, Lowenthal A, Japan Guanidino Compounds Research Association, editors. Guanidines: historical, biological, biochemical, and clinical aspects of the naturally occurring guanidino compounds. New York: Plenum Press; 1985. 479 p. ISSN: 978-0-306-41920-1. .
  • a)Wu Y-Q, Hamilton SK, Wilkinson DE, Hamilton GS. Direct Synthesis of Guanidines Using Di(imidazole-1-yl)methanimine. The Journal of Organic Chemistry. 2002 Oct;67(21):7553–6. DOI: 10.1021/jo0202381. b) Evindar G, Batey RA. Copper- and Palladium-Catalyzed Intramolecular Aryl Guanidinylation: An Efficient Method for the Synthesis of 2-Aminobenzimidazoles †. Organic Letters. 2003 Jan;5(2):133–6. DOI: 10.1021/ol027061h. c) Powell DA, Ramsden PD, Batey RA. Phase-Transfer-Catalyzed Alkylation of Guanidines by Alkyl Halides under Biphasic Conditions: A Convenient Protocol for the Synthesis of Highly Functionalized Guanidines. The Journal of Organic Chemistry. 2003 Mar;68(6):2300–9. DOI: 10.1021/jo0265535.
  • Li J, Zhang Z, Fan E. Solid-phase synthesis of 1,5-substituted 2-(N-alkylamino)-imidazolidin-4-ones. Tetrahedron Letters. 2004 Feb;45(6):1267–9. DOI: 10.1016/j.tetlet.2003.11.127.
  • Vaidyanathan G, Zalutsky MR. A New Route to Guanidines from Bromoalkanes. The Journal of Organic Chemistry. 1997 Jul;62(14):4867–9. DOI: 10.1021/jo9704164.
  • Linton BR, Carr AJ, Orner BP, Hamilton AD. A Versatile One-Pot Synthesis of 1,3-Substituted Guanidines from Carbamoyl Isothiocyanates. The Journal of Organic Chemistry. 2000 Mar;65(5):1566–8. DOI: 10.1021/jo991458q.
  • Feichtinger K, Zapf C, Sings HL, Goodman M. Diprotected Triflylguanidines: A New Class of Guanidinylation Reagents. The Journal of Organic Chemistry. 1998 Jun;63(12):3804–5.
  • Tin MKT, Thirupathi N, Yap GPA, Richeson DS. Guanidinate anions and dianions. Reactions involving alkylguanidines, (RNH)2CNR (R = i-Pr or Cy), and metal amido complexes M(NMe2)5 (M = Ta or Nb). Journal of the Chemical Society, Dalton Transactions. 1999;(17):2947–51. DOI: 10.1039/a904072b.
  • a) Zhang W-X, Hou Z. Catalytic addition of alkyne C–H, amine N–H, and phosphine P–H bonds to carbodiimides: an efficient route to propiolamidines, guanidines, and phosphaguanidines. Organic & Biomolecular Chemistry. 2008;6(10):1720. DOI: 10.1039/b800135a. b) Zhang W-X, Nishiura M, Hou Z. Catalytic Addition of Amine NH Bonds to Carbodiimides by Half-Sandwich Rare-Earth Metal Complexes: Efficient Synthesis of Substituted Guanidines through Amine Protonolysis of Rare-Earth Metal Guanidinates. Chemistry - A European Journal. 2007 May 7;13(14):4037–51. DOI: 10.1002/chem.200601383. c) Zhang W-X, Nishiura M, Hou Z. Catalytic Addition of Secondary Amines to Carbodiimides by a Half-Sandwich Yttrium Complex: An Efficient Route to N,N′,N′′,N′′-Tetra¬substituted Guanidines. Synlett. 2006 May;2006(8):1213–6. DOI: 10.1055/s-2006-939081.
  • a) Ong T-G, Yap GPA, Richeson DS. Catalytic Construction and Reconstruction of Guanidines: Ti-Mediated Guanylation of Amines and Transamination of Guanidines. Journal of the American Chemical Society. 2003 Jul;125(27):8100–1. DOI: 10.1021/ja035716j. b) Montilla F, Pastor A, Galindo A. Guanylation of aromatic amines catalyzed by vanadium imido complexes. Journal of Organometallic Chemistry. 2004 Mar;689(6):993–6. DOI: 10.1016/j.jorganchem.2004.01.005. DOI: 10.1016/j.jorganchem.2004.01.005.
  • Zhu X, Du Z, Xu F, Shen Q. Ytterbium Triflate: A Highly Active Catalyst for Addition of Amines to Carbodiimides to N , N ′, N ′′-Trisubstituted Guanidines. The Journal of Organic Chemistry. 2009 Aug 21;74(16):6347–9. DOI: 10.1021/jo900903t.
  • Zhang W-X, Li D, Wang Z, Xi Z. Alkyl Aluminum-Catalyzed Addition of Amines to Carbodiimides: A Highly Efficient Route to Substituted Guanidines. Organometallics. 2009 Feb 9;28(3):882–7. DOI: 10.1021/om801035t.
  • Du Z, Li W, Zhu X, Xu F, Shen Q. Divalent Lanthanide Complexes: Highly Active Precatalysts for the Addition of N−H and C−H Bonds to Carbodiimides. The Journal of Organic Chemistry. 2008 Nov 21;73(22):8966–72. DOI: 10.1021/jo801693z.
  • Shen H, Chan H-S, Xie Z. Guanylation of Amines Catalyzed by a Half-Sandwich Titanacarborane Amide Complex. Organometallics. 2006 Nov;25(23):5515–7. DOI: 10.1021/om060811x.
  • Wasserscheid P, Welton T. Ionic liquids in synthesis [Internet]. Weinheim: Wiley-VCH; 2003 [cited 2016 Jan 16]. ISBN: 978-3-527-60544-6 978-3-527-60070-0.
  • Greaves TL, Drummond CJ. Protic Ionic Liquids: Properties and Applications. Chemical Reviews. 2008 Jan;108(1):206–37. DOI: 10.1021/cr068040u.
  • a) Holbrey JD, Seddon KR. The phase behaviour of 1-alkyl-3-methylimidazolium tetrafluoroborates; ionic liquids and ionic liquid crystals. Journal of the Chemical Society, Dalton Transactions. 1999;(13):2133–40. DOI: 10.1039/a902818h. b) Palimkar SS, Siddiqui SA, Daniel T, Lahoti RJ, Srinivasan KV. Ionic Liquid-Promoted Regiospecific Friedlander Annulation: Novel Synthesis of Quinolines and Fused Polycyclic Quinolines. The Journal of Organic Chemistry. 2003 Nov;68(24):9371–8. DOI: 10.1021/jo035153u. c) Zhu A, Jiang T, Han B, Huang J, Zhang J, Ma X. Study on guanidine-based task-specific ionic liquids as catalysts for direct aldol reactions without solvent. New Journal of Chemistry. 2006;30(5):736. DOI: 10.1039/b600277c. d) Cole AC, Jensen JL, Ntai I, Tran KLT, Weaver KJ, Forbes DC, et al. Novel Brønsted Acidic Ionic Liquids and Their Use as Dual Solvent−Catalysts. Journal of the American Chemical Society. 2002 May;124(21):5962–3. DOI: 10.1021/ja026290w. e) Leng Y, Wang J, Zhu D, Ren X, Ge H, Shen L. Heteropolyanion-Based Ionic Liquids: Reaction-Induced Self-Separation Catalysts for Esterification. Angewandte Chemie. 2009 Jan;121(1):174–7. DOI: 10.1002/ange.200803567.
Year 2016, Volume: 3 Issue: 1, 19 - 26, 11.01.2016

Abstract

References

  • Mori A, Cohen BD, Lowenthal A, Japan Guanidino Compounds Research Association, editors. Guanidines: historical, biological, biochemical, and clinical aspects of the naturally occurring guanidino compounds. New York: Plenum Press; 1985. 479 p. ISSN: 978-0-306-41920-1. .
  • a)Wu Y-Q, Hamilton SK, Wilkinson DE, Hamilton GS. Direct Synthesis of Guanidines Using Di(imidazole-1-yl)methanimine. The Journal of Organic Chemistry. 2002 Oct;67(21):7553–6. DOI: 10.1021/jo0202381. b) Evindar G, Batey RA. Copper- and Palladium-Catalyzed Intramolecular Aryl Guanidinylation: An Efficient Method for the Synthesis of 2-Aminobenzimidazoles †. Organic Letters. 2003 Jan;5(2):133–6. DOI: 10.1021/ol027061h. c) Powell DA, Ramsden PD, Batey RA. Phase-Transfer-Catalyzed Alkylation of Guanidines by Alkyl Halides under Biphasic Conditions: A Convenient Protocol for the Synthesis of Highly Functionalized Guanidines. The Journal of Organic Chemistry. 2003 Mar;68(6):2300–9. DOI: 10.1021/jo0265535.
  • Li J, Zhang Z, Fan E. Solid-phase synthesis of 1,5-substituted 2-(N-alkylamino)-imidazolidin-4-ones. Tetrahedron Letters. 2004 Feb;45(6):1267–9. DOI: 10.1016/j.tetlet.2003.11.127.
  • Vaidyanathan G, Zalutsky MR. A New Route to Guanidines from Bromoalkanes. The Journal of Organic Chemistry. 1997 Jul;62(14):4867–9. DOI: 10.1021/jo9704164.
  • Linton BR, Carr AJ, Orner BP, Hamilton AD. A Versatile One-Pot Synthesis of 1,3-Substituted Guanidines from Carbamoyl Isothiocyanates. The Journal of Organic Chemistry. 2000 Mar;65(5):1566–8. DOI: 10.1021/jo991458q.
  • Feichtinger K, Zapf C, Sings HL, Goodman M. Diprotected Triflylguanidines: A New Class of Guanidinylation Reagents. The Journal of Organic Chemistry. 1998 Jun;63(12):3804–5.
  • Tin MKT, Thirupathi N, Yap GPA, Richeson DS. Guanidinate anions and dianions. Reactions involving alkylguanidines, (RNH)2CNR (R = i-Pr or Cy), and metal amido complexes M(NMe2)5 (M = Ta or Nb). Journal of the Chemical Society, Dalton Transactions. 1999;(17):2947–51. DOI: 10.1039/a904072b.
  • a) Zhang W-X, Hou Z. Catalytic addition of alkyne C–H, amine N–H, and phosphine P–H bonds to carbodiimides: an efficient route to propiolamidines, guanidines, and phosphaguanidines. Organic & Biomolecular Chemistry. 2008;6(10):1720. DOI: 10.1039/b800135a. b) Zhang W-X, Nishiura M, Hou Z. Catalytic Addition of Amine NH Bonds to Carbodiimides by Half-Sandwich Rare-Earth Metal Complexes: Efficient Synthesis of Substituted Guanidines through Amine Protonolysis of Rare-Earth Metal Guanidinates. Chemistry - A European Journal. 2007 May 7;13(14):4037–51. DOI: 10.1002/chem.200601383. c) Zhang W-X, Nishiura M, Hou Z. Catalytic Addition of Secondary Amines to Carbodiimides by a Half-Sandwich Yttrium Complex: An Efficient Route to N,N′,N′′,N′′-Tetra¬substituted Guanidines. Synlett. 2006 May;2006(8):1213–6. DOI: 10.1055/s-2006-939081.
  • a) Ong T-G, Yap GPA, Richeson DS. Catalytic Construction and Reconstruction of Guanidines: Ti-Mediated Guanylation of Amines and Transamination of Guanidines. Journal of the American Chemical Society. 2003 Jul;125(27):8100–1. DOI: 10.1021/ja035716j. b) Montilla F, Pastor A, Galindo A. Guanylation of aromatic amines catalyzed by vanadium imido complexes. Journal of Organometallic Chemistry. 2004 Mar;689(6):993–6. DOI: 10.1016/j.jorganchem.2004.01.005. DOI: 10.1016/j.jorganchem.2004.01.005.
  • Zhu X, Du Z, Xu F, Shen Q. Ytterbium Triflate: A Highly Active Catalyst for Addition of Amines to Carbodiimides to N , N ′, N ′′-Trisubstituted Guanidines. The Journal of Organic Chemistry. 2009 Aug 21;74(16):6347–9. DOI: 10.1021/jo900903t.
  • Zhang W-X, Li D, Wang Z, Xi Z. Alkyl Aluminum-Catalyzed Addition of Amines to Carbodiimides: A Highly Efficient Route to Substituted Guanidines. Organometallics. 2009 Feb 9;28(3):882–7. DOI: 10.1021/om801035t.
  • Du Z, Li W, Zhu X, Xu F, Shen Q. Divalent Lanthanide Complexes: Highly Active Precatalysts for the Addition of N−H and C−H Bonds to Carbodiimides. The Journal of Organic Chemistry. 2008 Nov 21;73(22):8966–72. DOI: 10.1021/jo801693z.
  • Shen H, Chan H-S, Xie Z. Guanylation of Amines Catalyzed by a Half-Sandwich Titanacarborane Amide Complex. Organometallics. 2006 Nov;25(23):5515–7. DOI: 10.1021/om060811x.
  • Wasserscheid P, Welton T. Ionic liquids in synthesis [Internet]. Weinheim: Wiley-VCH; 2003 [cited 2016 Jan 16]. ISBN: 978-3-527-60544-6 978-3-527-60070-0.
  • Greaves TL, Drummond CJ. Protic Ionic Liquids: Properties and Applications. Chemical Reviews. 2008 Jan;108(1):206–37. DOI: 10.1021/cr068040u.
  • a) Holbrey JD, Seddon KR. The phase behaviour of 1-alkyl-3-methylimidazolium tetrafluoroborates; ionic liquids and ionic liquid crystals. Journal of the Chemical Society, Dalton Transactions. 1999;(13):2133–40. DOI: 10.1039/a902818h. b) Palimkar SS, Siddiqui SA, Daniel T, Lahoti RJ, Srinivasan KV. Ionic Liquid-Promoted Regiospecific Friedlander Annulation: Novel Synthesis of Quinolines and Fused Polycyclic Quinolines. The Journal of Organic Chemistry. 2003 Nov;68(24):9371–8. DOI: 10.1021/jo035153u. c) Zhu A, Jiang T, Han B, Huang J, Zhang J, Ma X. Study on guanidine-based task-specific ionic liquids as catalysts for direct aldol reactions without solvent. New Journal of Chemistry. 2006;30(5):736. DOI: 10.1039/b600277c. d) Cole AC, Jensen JL, Ntai I, Tran KLT, Weaver KJ, Forbes DC, et al. Novel Brønsted Acidic Ionic Liquids and Their Use as Dual Solvent−Catalysts. Journal of the American Chemical Society. 2002 May;124(21):5962–3. DOI: 10.1021/ja026290w. e) Leng Y, Wang J, Zhu D, Ren X, Ge H, Shen L. Heteropolyanion-Based Ionic Liquids: Reaction-Induced Self-Separation Catalysts for Esterification. Angewandte Chemie. 2009 Jan;121(1):174–7. DOI: 10.1002/ange.200803567.
There are 16 citations in total.

Details

Primary Language English
Journal Section Articles
Authors

Foad Shaghayeghi Toosi

Publication Date January 11, 2016
Submission Date August 5, 2015
Published in Issue Year 2016 Volume: 3 Issue: 1

Cite

Vancouver Shaghayeghi Toosi F. Synthesis of Guanidines via Reaction of Amines with Carbodiimides in the Presence of Ionic Liquid. JOTCSA. 2016;3(1):19-26.