Tetraalkyl Hydroxymethylene-bisphosphonate and Dialkyl 1-Diphenylphosphinoyl-1-hydroxy-ethylphosphonate Derivatives by the Pudovik Reaction and Their Rearranged Products (original) (raw)
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New hydroxy-methylenebisphosphonic derivatives were prepared with different P-functions. The outcome of the reaction of α-oxophosphonates (YC(O)P(O)(OR)2) and dialkyl phosphites or diarylphosphine oxides depended on the Y substituent of the oxo-compound, the nature of the P-reagent and the amount of the diethylamine catalyst. Starting from dimethyl α-oxoethylphosphonate, in the presence of 5% of diethylamine, the corresponding Pudovik adduct was the single product. While using 40% of the catalyst, the rearranged species with the >P(O)–O–CH–P(O)< skeleton was the exclusive component. A similar reaction of α-oxobenzylphosphonate followed the rearrangement protocol. X-ray crystallography revealed not only the spatial structures of the three products, but also an intricate pattern evolving from the interplay of slight chemical differences, solvent inclusion and disorder as well as H-bridge patterns, which invite further investigation. In vitro activity of the compounds was assesse...
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Recently, we established a highly efficient, 2-oxo driven catalyst free method for the synthesis of α-hydroxy-βoxophosphonates (HOP) and also described its applications to α-oxoesters and acids. 4 This prompted us to extend our reaction towards the development of a unique one-pot method for the direct coupling of 2-oxoaldehydes (2OA) Scheme 1. Summary of work and H-phosphonates/ diphenylphosphine oxide in basic environment for the generation of rearranged structures that are well known for their chemical and biological importance
Beilstein journal of organic chemistry, 2017
A family of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides was synthesized by the microwave-assisted solvent-free addition of dialkyl phosphites and diphenylphosphine oxide, respectively, to imines formed from benzaldehyde derivatives and primary amines. After optimization, the reactivity was mapped, and the fine mechanism was evaluated by DFT calculations. Two α-aminophosphonates were subjected to an X-ray study revealing a racemic dimer formation made through a N-H···O=P intermolecular hydrogen bridges pair.
The Pudovik reaction: the synthesis of bioactive α-aminophosphonates with long alkyl chains
Phosphorus, Sulfur, and Silicon and the Related Elements, 2019
In this research we investigated the reactions of substituted naphthaldehyde with amines. The condensation of do-, tetra-, hexa-, octadecan-1-amines with 2-hydroxy-1-naphthaldehyde yielded a series of azomethines in good yields. Subsequent reaction of these compounds with didodecylphosphine oxide yielded a-aminophosphonates. The in vitro microbiological activity of the synthesized phosphorus compounds against gram-positive, gram-negative bacteria and the yeast Candida albicans was determined in comparison to standard agents. The synthesized compounds showed a high antibacterial and antimycotic activity against human and animal pathogenic microflora. Every newly synthesized compound was characterized by elemental analyses, IR, 1 H NMR, 31 P NMR spectral studies. The thermal stability was studied by synchronous thermogravimetry and differential scanning calorimetry (TG/DSC).
NMR studies of the bishydroxy bisphosphonate synthesis fromo-phthalic aldehyde and diethyl phosphite
Heteroatom Chemistry, 2002
The reaction of the o-phthalic aldehyde with diethyl phosphite leading to the bishydroxy bisphosphonate has been studied. It was found that the reaction is complex and a cyclic acetal formed from the monohydroxyphosphonate is the first relatively stable product. It slowly transforms to the bishydroxy bisphosphonate. The latter compound undergoes intramolecular nucleophilic substitution of the phosphorus atom by the hydroxy group which results in a cyclic structure, a phosphonate-hydroxyphosphate compound. C 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:157-164, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). NMR spectra were recorded on an AMX 300 MHz Bruker instrument operating at 300.13 MHz ( 1 H) and 121.499 ( 31 P). Measurements were made in CDCl 3 (chloroform-d, isotopic purity 99.8 atom %, Dr. Glaser AG Basel).