4th EucheMs chemistry congress

Poster Session 1
s1046
chem. Listy 106, s587–s1425 (2012)
Poster session 1 - organic chemistry
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ConverSionS of PhoSPhonoMethionine And
reLAted CoMPoundS
M. Kudzin 1 , z. Kudzin 2 , P. urBAniAK 2 ,
J. drABowiCz 3
1 Textile Research Institute, Laboratory of Chemical Testing and
Instrumental Analyses, Lodz, Poland
2 University of Lodz, Faculty of Chemistry, Lodz, Poland
3 Jan Dlugosz University in Czestochowa, Department of
Chemistry Enviromental Protection and Biotechnology,
Czestochowa, Poland
1-Aminoalkylphosphonic acids are structural analogs of
natural amino acids, obtained by an isosteric substitution of the
planar carboxylic group [C(O)OH] by the tetrahedral phosphonic
function [P(O)(OH) ]. In this class of amino acids the group
2
of special interest present so called, the proteinogenic
1-aminoalkylphosphonic acids, in this phosphonomethionine
(MetP ) and related compounds [1].
Phosphonomethionine – originally synthesized in 1980 [2],
and its analogs - phosphonohomocysteine (HcysP ) [2, 4] and
phosphonocysteine (CysP ) [3, 4], present the interesting subject
for chemical [5–8] and biological [9] explorations.
In this communication, we present our results on the further
sulfur functionalisation of this type of aminophosphonic acids,
especially their N-methyl, and N,N-dimethyl derivatives.
references:
1. Kudzin Z.H., Kudzin M.H., Drabowicz J., Stevens Ch.:
Aminophosphonic Acids - Phosphorus Analogues of Natural
Amino Acids. Part 1: Syntheses of α-Aminophosphonic
Acids. Curr. Org. Chem. 15 [2011] 2015-2071.
2. Kudzin Z.H., Stec W.J.: Phosphohomocysteine
derivatives. Synthesis 1980, 1032-1034.
3. Kudzin Z.H. Phosphocysteine derivatives.
Thioureidoalkanephos-phonates via acetals.
Synthesis 1981, 643-645.
4. Kudzin Z.H., Stec W.J.: Phosphocysteine and
phosphohomocysteine. Synthesis and isolation.
Synthesis: 1983, 812-814.
5. Kudzin Z.H., Andrijewski G., Drabowicz J.:
1-Aminothiaalkane-phosphonic acids – sulphinyl and
sulphonyl derivatives. Synthesis and acidic properties.
Heteroatom Chem. 5 [1994] 1-6.
6. Kudzin Z.H., Mokrzan J., Skowronski R.: Long chain
aminothiaalkane-phosphonates, their sulphinyl and
sulphonyl derivatives. A new class of complexane type
surfactants. Phosphorus & Sulfur 42[1982] 41-46.
7. Kudzin Z.H., Saganiak M., Andrijewski G., Drabowicz J.:
Oxidation of phosphonocysteine and
phosphono-homocysteine. Synthesis of phosphonocysteic
and phosphonohomocysteic acids. Pol. J. Chem. 79 [2005]
529-539.
8. Tam C.C., Mattocks K., Tishler M.: Synthesis of
phosphono-methionine and related compounds. Synthesis
1982, 188-191.
9. Kudzin M.H., Kudzin Z.H., Drabowicz J.: Derivatives of
aminoalkylphosphonic acids and glycylaminoalkylphosphonic
acids as antibacterial additives in biopolymers. European
Polymer Congress EPF-2011; Grenada 26.06-1.07.2011.
Keywords: Aminoalkylphosphonic acids;
Phosphonomethionine; Amino acids;
4 th EucheMs chemistry congress
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CritiCAL ASSeSSMent of the effiCienCy of
ChitoSAn-BASed MAteriALS AS PotentiAL
orGAnoCAtALyStS for C-C Bond forMAtion
d. KuehBeCK 1 , G. SAiduLu 2 , K. r. reddy 2 ,
d. diAz diAz 3
1Institute of Organic Chemistry, University of Regensburg,
Regensburg, Germany
2 Indian Institute of Chemical Technology, Inorganic and
Physical Chemistry Division, Hyderabad, India
3 ISQHC, Universidad de Zaragoza-CSIC, Zaragoza, Spain
Since petrochemical-based feedstocks will be limited in
future and are getting therefore much more expensive, cheap
alternative sustainable resources like polysaccharides (e.g.
chitosan, alginates, hyoluronic acid, carrageenan, cellulose, etc.)
already play and will play a more important role in high-tech
applications and industrial processes. [1] Beside such key
advantages like biodegradability, biocompatibility and
antibacterial activity, these materials are wide abundant on earth,
offer a variety of functional groups and own in most cases chiral
backbones. [2] Latter benefits qualify these compounds as potential
organocatalysts in different organic transformations.
In this study the effectiveness of commercial available
chitosan powder (CSP), air-dried chitosan hydrogel beads
(ADCSHB) and neutral pH chitosan hydrogel beads (CSHB) as a
green organocatalyst for different C-C bond forming reactions
(i.e. aldol reaction, Knoevenagel condensation, nitroaldol (Henry)
reaction and Michael addition) has been comprehensively
evaluated. Reaction rates, conversions and selectivities were
investigated in dependence of different input variables including
size, pH and reactive surface of the beads, catalyst loading,
temperature, molecular weight of the biopolymer, concentration,
solvent system and molar ratio of reactants. Moreover, the
chitosan-based materials were characterized by a variety of
techniques including, among others, SEM, FT-IR, TGA and
DSC. [3]
references:
1. R. Höfer and J. Bigorra, Green Chem., 2007, 9, 203-212.
2. M. Elnashar (Ed.), Biopolymers, InTech, 2010.
3. D. Kühbeck, G. Saidulu, K. R. Reddy, D. D. Díaz, Green
Chem., 2012, 14, 378-392.
Keywords: chitosan; hydrogel; C-C bond formation;
organocatalysis;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc