Projects Financial support from U.E.F.I.S.C.D.I Romania
PN-II-ID-PCE-2011-3-0128.
CONTRACT No. 260 / 05.11.2011
Iterative synthesis.
New dendritic melamines incorporating serinolic units.
Design, preparation, structural analysis and potential applications.





TEAM

Prof. Dr. Eng. Mircea DARABANTU, H.D.R. permanent position
Dr. Carmen SACALIS permanent position
Dr. Eng. Flavia Adina POPA (married MARTIN) (01.11.2011 – 28.02.2012)
Dr. Eng. Oana Salomia MOLDOVAN (married GRAD) (01.03.2012 - 30.04.2015)
Eng. Maria Cristina MORAR (married HADAREAN) (01.11.2011 - 30.09.2016)
Eng. NAGY Emöke Iulia (01.11.2011 - 31.12.2014)
Eng. Ana-Maria TICALA (married MÂRZA) 01.10.2012 – 30.09.2014)
Eng. Ioan BODEA (01.05.2015 – 30.09.2016)

Dara Carmen
Flavia Oana Crys Iulika Ani Ionica

ABSTRACT

The Project deals with design, iterative synthesis, structural characterization and applications of new N-substituted melamines of type G-2-D dendrimers and dimeric G-2-Dendrons (G-2-D)2, having the general formulae CR{LT[LT(PG1,PG2)]2}2 and CL{T{LT[LT(PG1,PG2)]2}2}2 respectively [CR: CoRe; CL: Central Linker; L: Linker; T: 1,3,5-triazine-2,4,6-triyl unit (Branch Cell)]. PG1 and PG2 stand for two types of Peripheral Groups : C-2-(Me, Et, CH2OH)-substituted-2-aminopropane-1,3-diols ("Serinols") as "Open Chain Units", PG1) in tandem with "Closed Chain Units" (PG2): (O-masked)-4-piperidone derivatives or enantiopure cyclic acetals (4S,5S)-5-amino-4-aryl-1,3-dioxanes based on C-1-(p-nitrophenyl, optionally phenyl)-substituted-2-aminopropane-1,3-diols "Phenylserinols").

OBJECTIFS

  1. Contributions to iterative synthesis of highly elaborated melamines by repetitive amination of cyanuric chloride with different as versatile amino-nucleophiles are envisaged.
  2. Contributions to the use of rotational restricted interactions about Csp2(s-triazine)-N(exocyclic) partial double bonds in dendritic melamines, directed to their Host-Guest aptitude as supramolecular status, are both targeted in solution and in solid state.
  3. Potential applications in medicinal chemistry (new delivery drug systems) and organic nanomaterials are under consideration.
  4. First use of C-2-substituted-2-amino-3-mercaptopropanols ("cysteinols", available via our improved "serinolic" synthetic approach) in the above chemistry is also explored.

RESULTS 2011 - 2012

1. Papers

  1. "Amino-s-triazines. Synthesis and Stereochemistry of Restricted Rotational Phenomena (I). First Use of a C-2-Substituted Serinol in Tandem with Masked 4-Piperidone for Selective Amination of Cyanuric Chloride"
    F. Popa, P. Lameiras, E. Hénon, O. Moldovan, A. Martinez, C. Bâtiu, Y. Ramondenc and M. Darabantu*
    Can. J. Chem. 2011, 89(10), 1207-1221; http://www.nrcresearchpress.com/doi/abs/10.1139/v11-075#;
  2. "New Serinolic Amino-s-triazines by Chemoselective Amination of Cyanuric Chloride and their (Pro)diastereomerism in Restricted Rotational Phenomena"
    O. Moldovan, P. Lameiras, E. Hénon, F. Popa, A. Martinez, D. Harakat, C. Sacalis, Y. Ramondenc and M. Darabantu*
    Centr. Eur. J. Chem., 2012, 10(4), 1119-1136; http://link.springer.com/article/10.2478/s11532-012-0015-4
  3. "Design, Synthesis and Structure of New Dendritic Melamines. First Use of a Tandem C-2-Substituted Serinol – O,O-Masked 4-Piperidone as a Peripheral Unit in Iterative Synthesis"
    F. Popa, P. Lameiras, O. Moldovan, M. Tomoaia-Cotisel, E. Hénon, A. Martinez, C. Sacalis, A. Mocanu, Y. Ramondenc and M. Darabantu*
    Tetrahedron, 2012, 68(43), 8945–8967; http://dx.doi.org/10.1016/j.tet.2012.07.096
  4. "Novel 1,3-Thiazolidines. Synthesis of 2-Aryl-4,4-bis(hydroxymethyl)-1,3-Thiazolidines by Direct Thioaminalisation"
    C. Morar, C. Sacalis*, P. Lameiras, I.Bratu, O. Moldovan, Y. Ramondenc and M. Darabantu*
    Stud. U. Babes-Bol. Che., 2012, LVII, 4, 145-156; http://www.chem.ubbcluj.ro/~studiachemia/docs/Chemia42012.pdf

2. People

  1. We congratulate Flavia for the Final Defence of her Ph. D. Thesis (Magna cum laude) in Co-Directorship between Prof. Dr. Eng. Mircea DARABANTU (University BABES – BOLYAI, Romania) and Prof. Dr. Yvan RAMONDENC (University of Rouen, France), March 29, 2012

    Title of the Ph. D. Manuscript

    "Systèmes py-déficitaires dendritiques à unités périphériques sérinoliques ou diaziniques: synthèse, stéréochimie et propriétés supramoléculaires"

    Jury

    Prof. Dr. Cristian SILVESTRU (University BABES - BOLYAI, Romania, President)
    Prof. Dr. Isabelle GILLAIZEAU (University of Orléans, France, Reviewer)
    Prof. Dr. Ionel MANGALAGIU ((University A. I. CUZA, Romania, Reviewer)
    Prof. Dr. Mircea DIUDEA (University BABES - BOLYAI, Romania, Reviewer)
    Prof. Dr. Nelly PLÉ (University of Rouen, France, Reviewer)
    Dr. Christine BAUDEQUIN (University of Rouen, France, Reviewer)


  2. We say farewell to Flavia, starting from 01.03.2012 wishing her all the best in the future career. We thank Flavia for her enthusiastic work. We are still missing her.
    We welcome Oana, starting from 01.03.2012.
    We welcome Ani, starting from 01.10.2012.


  3. We congratulate Oana for the Final Defence of her Ph. D. Thesis (Magna cum laude) in Co-Directorship between Prof. Dr. Eng. Mircea DARABANTU (University BABES – BOLYAI, Romania) and Prof. Dr. Yvan RAMONDENC (University of Rouen, France), November 22, 2012

    Title of the Ph. D. Manuscript

    "Ingénierie de systèmes conjugués A-π-D diaziniques et évaluation de leurs propriétés opto-électroniques. Mélamines spirodendritiques à partir des amino-1,3-dioxanes sérinoliques enantiopures. Design, synthèse et analyse structurale"

    Jury

    Prof. Dr. Cristian SILVESTRU (University BABES - BOLYAI, Romania, President)
    Prof. Dr. Vincent SOL (University of Limoges, France, Reviewer)
    Prof. Dr. Ionel MANGALAGIU ((University A. I. CUZA, Romania, Reviewer)
    Prof. Dr. Ion GROSU (University BABES - BOLYAI, Romania, Reviewer)
    Prof. Dr. Nelly PLÉ (University of Rouen, France, Reviewer)
    Dr. Christine BAUDEQUIN (University of Rouen, France, Reviewer)


3. Developments

Progress of our Laboratory new extension: L-18

RESULTS 2013

1. Papers

  1. "Stereochemistry of Six-membered Spiranes Arising From the First Use of a Diaza-trispiro-heneicosane Motif in the Synthesis of a G-1 Dendritic Melamine"
    O. Moldovan, P. Lameiras, I. Nagy, T. Opruta, F. Popa, C. Antheaume, Y. Ramondenc and M. Darabantu*
    Tetrahedron, 2013, 69(4), 2199–2213; http://dx.doi.org/10.1016/j.tet.2012.12.059
  2. "Synthesis and Photophysical Properties of Push-pull Structures Incorporating Diazines as Attracting Part and Fluorene Core"
    C. Denneval, O. Moldovan, C. Baudequin, S. Achelle, P. Baldeck, N. Plé, M. Darabantu and Y. Ramondenc
    Eur. J. Org. Chem. , 2013, 25, 5591-5602; DOI: 10.1002/ejoc.201300458;
  3. "Synthesis and Stereochemistry of New 1,3-Thiazolidine Systems Based on 2-Amino-2-(mercaptomethyl)propane-1,3-diol: 4,4-Bis(hydroxymethyl)-1,3-thiazolidines and c-5-Hydroxymethyl-3-oxa-7-thia-r-1-azabicyclo[3.3.0]octanes"
    C. Morar, C. Sacalis, P. Lameiras, A. Soran, H. Khartabil, C. Antheaume, I. Bratu, O. Moldovan and M. Darabantu*
    Tetrahedron 2013, 69(47), 9966-9985, DOI: 10.1016/j.tet.2013.09.070

2. People

Starting from 01.01.2013 Oana is promoted as Deputy Team Leader.

We congratulate Crys for the obtention of her M.S. degree in Engineering of Organic and Biochemical Processes

Title of the Dissertation Manuscript

"Synthesis and Stereochemistry of New 1,3-Thiazolidine Systems Based on 2-Amino-2-(mercaptomethyl)propane-1,3-diol: 4,4-Bis(hydroxymethyl)-1,3-thiazolidines and c-5-Hydroxymethyl-3-oxa-7-thia-r-1-azabicyclo[3.3.0]octanes" July 2 2013

RESULTS 2014

1. People

1.1. We congratulate Iulika for the obtention of her M.S. degree in Engineering of Organic and Biochemical Processes
Title of the Dissertation Manuscript
"Design, Iterative Synthesis and Structure of Novel Trispiro-dendritic Melamines Incorporating "Open-chain" vs. "Closed-chain" Serinolic Peripheral Units" February 2 2014

1.2. We say farewell to Ani, starting from 01.10.2014 wishing her all the best in the future career. We thank Ani for her enthusiastic work. We are still missing her.

2. Developments

Our Laboratory L-18 is now functional

RESULTS 2015

1. Papers

  1. "Synthesis of Some Selectively N-protected (1S,2S)-p-nitrophenylserinol Based Diamino-1,3-dioxanes and Tripodands"
    I. Nagy, O. Moldovan, F. Popa, P. Lameiras, C. Morar, C. Sacalis and M. Darabantu*
    Synthetic Commun. 2015, 45(20), 2319-2330, DOI: 10.1080/00397911.2015.1078360
  2. "Convergent versus Divergent Three Steps Synthesis of the First (4-Aminophenoxy)alkanoic Acids Based Tripodal Melamines"
    C. Morar, L. Cost, P. Lameiras, C. Antheaume and M. Darabantu*
    Synthetic Commun. 2015, 45(14), 1688-1695, DOI: 10.1080/00397911.2015.1041048
  3. "Design, Iterative Synthesis and Structure of Novel Trispiro-dendritic Melamines Incorporating "Open-chain" vs. "Closed-chain" Serinolic Peripheral Units"
    O. Moldovan, I. Nagy, P. Lameiras, C. Antheaume, C. Sacalis and M. Darabantu*
    Tetrahedron: Asymmetry 2015, 26(14), 683–701, DOI: 10.1016/j.tetasy.2015.05.003
  4. "Concise Synthesis of Some (4-Aminophenoxy)alkanoic Acids Based on Paracetamol"
    C. Morar, L. Cost and M. Darabantu* http://www.chem.ubbcluj.ro/~studiachemia/docs/Chemia22015T1.pdf
    Stud. U. Babes-Bol. Che. 2015, LX, 2, Tom I, 7-14

2. People

2.1. We congratulate Ani for the obtention of her M.S. degree in Engineering of Organic and Biochemical Processes
Title of the Dissertation Manuscript
"Iterative syntheses of some optically active G-1 melamine-serinolic dendrons and dendrimers containing saturated and anancomeric heterocyclic units" July 4, 2015

2.2. We say farewell to Iulika, starting from 01.01.2015 wishing her all the best in the future career. We thank Iulika for her enthusiastic work. We are still missing her.
We welcome Ionica starting from 01.05.2015
We say farewell to Oana, starting from 01.05.2015 wishing her all the best in the future career. We thank Oana for her enthusiastic work. We are still missing her.

RESULTS 2016

Papers

  1. 'Novel N-modified Gycines Based on a (1S,2S)-2-Amino-1-(4-nitrophenyl)propane-1,3-diol Skeleton: 1,3-Dioxanes and Tripodands"
    O Moldovan, K. Albert, I. Nagy, C. Morar, C. Sacalis and M. Darabantu*
    Tetrahedron Lett. 2016, submitted
  2. "New p-Aminophenol Based Dendritic Melamines. Iterative Synthesis, Structure and Electrochemical Characterisation"
    C. Morar, G. Turdean, A. Bende, P. Lameiras, C. Antheaume, L. M. Muresan* and M. Darabantu*
    C. R. Chim. 2016, http://dx.doi.org/10.1016/j.crci.2016.07.002
  3. "Glassy Carbon Electrode Modified with Hemin and New Melamine Compounds for H2O2 Amperometric Detection"
    A. R. Deac, C. Morar, G. L. Turdean, M. Darabantu, E. Gál, A. Bende and L. M. Muresan
    J. Solid State Electr. 2016, http://link.springer.com/article/10.1007/s10008-016-3298-0?view=classic
  4. "4-Aminopiperidine Based New Amino-s-Triazines as Potential Dendritic Building-Blocks"
    A. –M. Ticala, D. Porumb, C. Sacalis* and Mircea Darabantu* Stud. U. Babes-Bol. Che. 2016, submitted