Synthesis, Chemistry and Applications of 5-Hydroxymethyl-furfural And Its Derivatives

The prospect of exciting research activity in the chemistry of furfural derived compounds such as 5-hydroxymethylfurfural (HMF), 2,5-furandicarbaldehyde and 2,5-furan-dicarboxylic acid prompted the writing of this article. As the field of application of these compounds is really enormous, it is no wonder that research in this area, starting at the end of 19th century, is still being developed. Numerous important scientific groups are carrying out studies on the synthesis, and applications of HMF and its derivatives. Notable among these are, Gaset (Toulouse), Descotes (Lyon), Lichtenthaler (Darmstadt), and Gelas (Clermont-Ferrand). Not only academic scientists are interested in this subject, the chemical industry, is represented by sugar companies such as Beghin-Say, and Süddeutsche Zucker. Despite this interest, there are not many comprehensive monographs or reviews covering the chemistry of HMF. Two classic reviews, by Newth and by Feather and Harris, appeared in 1951 and 1973 respectively. Reviews by Gaset et al.,3 Faury et al. and by Kuster are more recent, but they are not detailed. An important review review by Cottier and Descotes6 appeared in 1991. This review is written to update those above, to summarize the contributions of the last 100 years; and to emphasize recent developments especially in electrochemistry, and on dialdehyde and diacid chemistry.HMF is a good starting material for the synthesis of precursors of various pharmaceuticals, thermo-resistant polymers and complex macrocycles. Among these precursors, one can find 2,5- furandicarbaldehyde and 2,5-furandicarboxylic acid; these two compounds are described in detail in this article. The field of their applications is enormous – the dialdehyde offers itself to be the precursor for the synthesis of complexing macrocycles, oxo-porphirines, oxo-annulenes as well as mono- and bis alkenyl and alkynyl furans. The diacid is a building block for numerous polyesters and polyamides; its derivatives were found to be useful in pharmacology. No wonder then, that numerous methods for their preparation have been worked out and published.N/

THE REACTION OF TETRAMETHYLSILANE WITH BORON TRIBROMIDE

The reaction of tetramethylsilane with boron tribromide in deuterochloroform in ambient temperature or at 40°C led to bromotrimethylsilane (3) and to dibromomethylborane (4). Identity of products was confirmed by NMR spectroscopy. Analogical reaction carried out in 1,3-dichloropropane allowed to separate products of the reaction and to obtain them in 68% and 59% yields respectively.CNRS Franc

Addition of Di(trimethylsilyl) Phosphite to Schiff Bases of 2,5-Diformylfuran

A series of 2,5-Furanyl-bis-(aminomethylphosphonic Acids) has been synthesized by the addition of di(trimethylsilyl) phosphite to azomethine bond of achiral Schiff bases derved from 2,5-diformylfuran. The stereochemical aspect of this reaction has been studied and compared with the behaviour of achiral terephthalic Schiff bases in similar reaction. Whereas, addition to achiral terephthalic Schiff bases was found to be highly stereoselective, the analogous reaction with achiral 2,5-diformylfuran Schiff bases was stereoselective exclusively in the case when the substituent is benzyl.N/

The formation of dimethyl amino(pyrene-1-yl)methylphosphonates in the Kabachnik-Fields reaction with dibenzyl phosphite, pyrene-1-carboxaldehyde and a non-aromatic amine in methanol

<p></p> <p>The Kabachnik-Fields reaction of pyrene-1-carboxaldehyde with dibenzyl phosphite and aliphatic amines in methanol led to the formation of dimethyl amino(pyren-1-yl)methyl-phosphonates, in some cases accompanied by dimethyl hydroxy(pyren-1-yl)methyl-phosphonate. These results are exclusive for the above compounds, in all other studied cases (aromatic aldehydes, aromatic amines) the mixtures of several aminophosphonates were obtained.</p

Antagonistic Effects of CAPE (a Component of Propolis) on the Cytotoxicity and Genotoxicity of Irinotecan and SN38 in Human Gastrointestinal Cancer Cells In Vitro

The incidence of gastrointestinal cancers is increasing every year. Irinotecan (CPT-11), a drug used in the treatment of colorectal cancer and gastric cancer, is metabolized by carboxylesterases to an active metabolite, SN-38, which is more cytotoxic. CAPE (caffeic acid phenethyl ester) is an active component of propolis, which has a high antibacterial, antiviral, and antineoplastic potential. This study analyses the impact of CAPE on the cytotoxic (MTT assay), genotoxic (comet assay) and proapoptotic (caspase-3/7 activity) potential of irinotecan and its metabolite SN-38 in cultures of gastrointestinal neoplastic cells (HCT116, HT29, AGS). Cytotoxicity and genotoxicity activities of these compounds were carried out in comparison with human peripheral blood lymphocytes (PBLs) in vitro. The antioxidant potential of CAPE was investigated in relation H2O2-induced oxidative stress in the both neoplastic cells and PBLs. CAPE expressed cytotoxic, genotoxic, and pro-apoptotic activity against AGS, HCT116, and HT29 tumor cells. CAPE, in the presence of different concentrations of irinotecan or SN38, decreased the cytotoxicity, genotoxicity, and pro-apoptotic activity in these cell lines, but it has no such action on normal human peripheral blood lymphocytes