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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
Authors

Foad Shaghayeghi Toosi

Submission Date August 5, 2015
Publication Date January 11, 2016
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.