Publication Cover
Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 33, 2003 - Issue 18
176
Views
15
CrossRef citations to date
0
Altmetric
Original Articles

A Convenient “One-Pot” Reaction for Selective Monoalkylation of N,N′-Disubstituted Ethylenediamines

, &
Pages 3193-3204 | Received 18 Dec 2002, Published online: 17 Aug 2006

References

  • Lis , R. and Marisca , A.J. 1988 . A convenient synthesis of n-aryl-n′-benzyl-1,2-ethanediamines . Synthetic Commun. , 18 : 45 – 50 . Among others:
  • von Angerer , E. , Egginger , G. , Kranfelder , G. , Bernahauer , H. and Schoenenberger , H. 1982 . N,N′-Dialkyl-1,2-bis(hydroxyphenyl)ethylenediamines and N,N′-dialkyl-4,5-bis(4-hydroxyphenyl)imidazolidines. Synthesis and evaluation of their mammary tumor inhibiting activity . J. Med. Chem. , 25 : 832 – 837 .
  • von Angerer , E. 1982 . Effect of N,N′-diethyl-1,2-bis(2,6-dichloro-4-hydroxyphenyl)ethylenediamines on the 7,12-dimethylbenzyl(a)antracene-induced mammary carcinoma of the rat . J. Med. Chem. , 25 : 1374 – 1377 .
  • Kraml , M. , Humber , L.G. , Dubuc , J. and Gaudry , R.J. 1964 . Agents affecting lipid metabolism. viii. N,N′-dibenzylethylenediamine, the key to a novel class of cholesterol biosynthesis inhibitors . J. Med. Chem. , 7 : 499 – 502 .
  • Pallavicini , M. , Valoti , E. and Piccolo , O. 1995 . Synthesis of N,N′-dibenzylethylenediamine via palladium-carbon-catalyzed reductive alkylation . J. Chem. Res. Synop. , 11 : 472 – 473 .
  • Lehman , B. 1997 . Ger. DE 19,604,102. Process for the manufacture of high purity N,N-dibenzylethylenediamine diacetate from 1,2-diaminoethane and benzaldehyde . Chem. Abstr. , 127 : 135631t
  • Le Bihan , G. , Rondu , F. , Pele-Tounian , A. , Wang , X. , Lidy , S. , Touboul , E. , Lamouri , A. , Dive , G. , Huet , J. , Pfeiffer , B. , Renard , P. , Guardiola-Lemaitre , B. , Manechez , D. , Penicaud , L. , Ktorza , A. and Godfroid , J.-J. 1999 . Design and synthesis of imidazoline derivatives active on glucose homeostasis in a rat model of type II diabetes. 2. Synthesis and biological activities of 1,4-dialkyl, 1,4-dibenzyl, and 1-benzyl-4-alkyl-2-(4′,5′-dihydro-1′H-imidazol-2′-yl)piperazines and isosteric analogues of imidazoline . J. Med. Chem. , 42 : 1587 – 1603 .
  • Short , J.H. , Chan , W.L. , Freifelder , H. , Mikolasek , D.G. , Schmidt , J.L. , Schoepeke , H.G. , Shannon , C. and Stone , J.R.J. 1963 . The hypotensive activity of N-cyclohexyl and N-methyl derivatives of alkylenediamines . J. Med. Chem. , 6 : 596 – 598 .
  • Khan , N.H. , Siddique , A.K. and Lodh , L.B. 1966 . Chemoterapeutic agents. I. Synthesis and antimicrobial activities of N,N-diethyl-N′-phenylethylenediamines . Pakistan J. Biol. Agr. Sci. , 9 : 41 – 43 .
  • Werbel , L.M. , Capps , D.B. , Elslager , E.F. , Pearlman , W. , Short , F.W. , Weinstein , E.A. and Worth , D.F. 1963 . N-Mono- and N,N′-dialkyl-N′-1-naphthylalkylenediamines . J. Med. Chem. , 6 : 637 – 646 .
  • Wright , W.B. , Brabander , H.J. and Hardy , R.A. Jr. 1959 . N-(tert-aminoalkyl)propionanilides: a new series of potent analgesics . J. Am. Chem. Soc. , 81 : 1518 – 1519 .
  • Wright , W.B. Jr. , Brabander , H.J. and Hardy , R.A. Jr. 1961 . Synthetic analgesics. II. Basic anilides and carbanilates . J. Org. Chem. , 26 : 476 – 485 .
  • Orelli , L. , Salerno , A. , Hedrera , M. and Perillo , I. 1998 . A convenient synthesis of unsymmetrical N,N′-disubstituted α,ω-diaminoalkanes . Synth. Commun. , 28 : 1625 – 1639 . Among others:
  • Orelli , L. , Blanco , M.M. , García , M.B. , Hedrera , M. and Perillo , I. 2001 . A new synthetic aproach to N,N′-disubstituted 1,n-alkanediamines . Synth. Commun. , 31 : 685 – 695 .
  • Fazio , M.J. 1984 . Nucleophylic ring opening of 2-oxazolines with amines: a convenient synthesis for unsymmetrically substituted ethylenediamines . J. Org. Chem. , 49 : 4889 – 4893 .
  • Yamamoto , H. and Maruoka , K. 1981 . Regioselective carbonyl amination using diisobutyl-aluminum hydride . J. Am. Chem. Soc. , 103 : 4186 – 4194 .
  • Chapuis , C. , Gauvreau , A. , Klaebe , A. , Lattes , A and Perie , J. 1973 . Condensation de diamines-1,2- sur les composés carbonylés. Syntheses d′imidazolidines: mécanisme de la réaction . Bull. Soc. Chim. Fr. , : 977 – 985 . Among others:
  • Crank , G. , Harding , D.R.K. and Szinai , S.S. 1970 . Perfluoroalkyl carbonyl compounds. 1. Perfluoroaldehyde and perfluorocarboxylic acid derivatives . J. Med. Chem. , 13 : 1212 – 1217 .
  • Hine , J. and Narducy , K.W. 1973 . Imines, imidazolidines, and imidazolidinium ions from the reactions of ethylenediamine derivatives with isobutyraldehyde and acetone . J. Am. Chem. Soc. , 95 : 3362 – 3368 .
  • Billman , J.H. , Ho , J.Y.C. and Caswell , L.R. 1952 . The formation of solid derivatives of aldehydes. I. 2-substituted-1,3-bis(p-methoxybenzyl)tetrahydroimidazoles . J. Am. Chem. Soc. , 17 : 1375 – 1377 .
  • Wilson , E.M. 1965 . The identity of piptamine and ormosanine and the structures of ormojanine, ormosimine, and panamine . Tetrahedron , 21 : 2561 – 2571 .
  • Northrop , R.C. Jr. and Russ , P.L. 1975 . Reductive cleavage of imidazolidines by borane-tetrahydrofuran . J. Org. Chem. , 40 : 558 – 559 .
  • Salerno , A. , Ceriani , V. and Perillo , I. 1992 . Reduction of substituted 1H-4,5-dihydroimidazolium salts . J. Heterocyclic Chem. , 29 : 1725 – 1733 .
  • Performing solvent free reactions avoid any carcinogenic solvent effect .
  • Varma , R.S. 1997 . Microwave-Assisted Reactions under Solvent-Free“Dry” Conditions in Microwaves: Theory and Application in Material Processing IV Edited by: Clark , D.E. , Sutton , W.H. and Lewis , D.A. 357 – 365 . Westerville, , Ohio : American Ceramic Society .
  • van Alphen , J. 1935 . N,N′-Di(benzyl)ethylenediamine (alkylated ethylenediamine derivatives I) . Rec. Trav. Chim. , 54 : 885 – 888 .
  • Billman , J.H. , Chem Ho , J.J. and Caswell , L.R. 1957 . Solid derivatives of aldehydes. II. A specific reagent for aldehydes: 1,2-bis(p-chlorobenzylamino)ethane . J. Org. Chem. , 22 : 538 – 541 .
  • N-Benzylidene-N′-p-chlorophenylethylenediamine was obtained as an oil and extracted with chloroform. A analytical sample was obtained by column chromatography. It proved to exist in a ring chain tautomeric equilibrium with the corresponding imidazolidine. The 1H-NMR spectrum in deuteriochloroform shows characteristic signals a δ = 5.50 ppm (s, imidazolidine C2-H) and δ = 8.37 ppm (s, N = CH-Ar) (imine:imidazolidine, 35:65). Anal. calcd. for C15H15ClN2C 69.63, H 5.84, N 10.83; Found: C 69.52, H 5.76, N 10.70 .
  • In deuteriochloroform, this compound proved to be a tautomeric mixture of 1-p-nitrophenyl-2-phenylimidazolidine and the corresponding imine .
  • Göblyös , A. , Lázár , L. , Evanics , F. and Fulöp , F. 1999 . Substituent effects in the ring-chain tautomerism of 1,2-diarylimidazolidines . Heterocycles , 51 : 2431 – 2438 .
  • Perillo , I.A. and Lamdan , S. 1975 . Reaction of an asymmetric imidazolinium compound with nucleophiles . J. Chem. Soc. Perkin Trans. I , : 894 – 896 .
  • This method is also inapplicable to the N-alkylation of N,N′-diarylethylenediamines, so far 1,3-diarylimidazolidines had proved to be stable in the reductive reaction medium of sodium borohydride .
  • Salerno , A. , Caterina , C. and Perillo , I. 2000 . Synthesis of substituted 1H-4,5-dihydroimidazolium salts by dehydrogenation of imidazolidines . Synth. Commun. , 30 : 3369 – 3382 .
  • Wright , W.B. Jr. and Brabander , H.J. 1961 . Debenzylation of tertiary benzylamines with ethyl chloroformate . J. Org. Chem. , 26 : 4057 – 4059 .
  • Billman , J.H. and McDowell , M. 1961 . Reduction of schiff bases. III. Reduction with dimethylamine borane . J. Org. Chem. , 26 : 1437 – 1440 .
  • Salerno , A. , Hedrera , M. , D'Accorso , N. , Martins Alho , M. and Perillo , I. 2000 . Spectroscopic analyses of imidazolidines. part I: electron impact mass spectrometry . J. Heterocyclic Chem. , 37 : 57 – 62 .

Reprints and Corporate Permissions

Please note: Selecting permissions does not provide access to the full text of the article, please see our help page How do I view content?

To request a reprint or corporate permissions for this article, please click on the relevant link below:

Academic Permissions

Please note: Selecting permissions does not provide access to the full text of the article, please see our help page How do I view content?

Obtain permissions instantly via Rightslink by clicking on the button below:

If you are unable to obtain permissions via Rightslink, please complete and submit this Permissions form. For more information, please visit our Permissions help page.