Preparation of mixed trialkyl alkylcarbonate derivatives of etidronic acid via an unusual route

• Petri A. Turhanen,
• Janne Weisell and
• Jouko J. Vepsäläinen

Beilstein J. Org. Chem. 2012, 8, 2019–2024, doi:10.3762/bjoc.8.228

• scientific literature [19], while phosphorous (approximately 600 compounds) and phosphonic acid carbonates (approximately 20 compounds) are well known molecules. Since BPs are very hydrophilic, their bioavailabilities are very poor [20]. It would be a clear advantage if one could prepare more lipophilic and

• -methoxycarbonyloxyphosphoryl)ethyl]phosphonic acid dimethyl ester (3a): Pair of diastereomers (ratio ca. 60:40). Yield: 88 mg, 67%. 1H NMR (500.1 MHz, CDCl3) δ 4.04–3.99 (m, 3H), 3.92–3.84 (m, 9H), 3.80–3.78 (m, 3H), 1.979 (dd, 3JHP = 16.0, 3JHP' = 17.0 Hz) and 1.973 (dd, 3JHP = 15.5, 3JHP' = 17.0 Hz, 3H); 13C NMR (125.8 MHz

• , 387.0264. [1-Ethoxycarbonyloxy-1-(ethoxy-ethoxycarbonyloxyphosphoryl)ethyl]phosphonic acid diethyl ester (3b): Pair of diastereomers (ratio ca. 50:50). Yield: 101 mg, 65%. 1H NMR (500.1 MHz, CDCl3) δ 4.50–4.43 (m, 2H), 4.36–4.19 (m, 8H), 2.02 (dd, 3JHP = 16.0, 3JHP' = 16.5 Hz, 3H), 1.42–1.30 (m, 15H); 13C

Liquid-crystalline nanoparticles: Hybrid design and mesophase structures

• Gareth L. Nealon,
• Romain Greget,
• Cristina Dominguez,
• Zsuzsanna T. Nagy,
• Daniel Guillon,
• Jean-Louis Gallani and
• Bertrand Donnio

Beilstein J. Org. Chem. 2012, 8, 349–370, doi:10.3762/bjoc.8.39

• , mesophase behaviour was reported for systems involving α-Fe2O3 NPs coated with mesogenic ligands containing a phosphonic acid anchoring group [59]. The NPs were prepared by using a sol–gel method, and grafting of the ligands was undertaken with 1:1 and 1:2 ligand/NP mass ratios. Mesogenic behaviour was

• (phenylene vinylene) derived ligands included phosphonic acid functional groups (17 and 18, Figure 19) for anchoring onto the surface of the NPs. The ferrite nanoparticles were prepared by using a coprecipitation method, followed by a hydrothermal growth process to give cuboidal NPs of 39 ± 5 nm width. These

• NPs were synthesised by the thermal decomposition of iron oleate complexes at high temperature in high-boiling-point solvent to give products of 3.3 ± 0.7 nm diameter. The cyanobiphenyl terminated ligands 20 and 21 (Figure 21) with carboxylic acid and phosphonic acid anchoring groups, respectively

Regioselective ester cleavage during the preparation of bisphosphonate methacrylate monomers

• Kamel Chougrani,
• Gilles Niel,
• Bernard Boutevin and
• Ghislain David

Beilstein J. Org. Chem. 2011, 7, 364–368, doi:10.3762/bjoc.7.46

• ester function without affecting the methacrylate ester. Keywords: bifunctional monomer; phosphonic acid; regioselective ester cleavage; Introduction The potential applications for polymer products containing phosphorus are numerous; dental adhesives, ion-exchange resins and adhesion promotors are

• many applications such as dental adhesives, ion-exchange resins and adhesion promotors. However, these polymers must be in the acidic form, i.e., with phosphonic acid groups, to function efficiently [26]. The intermediate bisphosphonates were then subjected to a two-step deprotection process to restore

• both the latter cases careful 1H NMR examination of the reaction mixture from the methanolysis step revealed that the phosphonic acid 4a, respectively 5a, was the sole compound until evaporation of the solvent. These results showed that the internal carboxylic ester was only cleaved after concentration

Novel 2-(ω-phosphonooxy-2-oxaalkyl)acrylate monomers for self-etching self-priming one part adhesive

• Joachim E. Klee and
• Uwe Lehmann

Beilstein J. Org. Chem. 2010, 6, 766–772, doi:10.3762/bjoc.6.95

• stable acidic monomers. Recently, some interesting approaches to acidic monomers were developed based on derivatives of α-hydroxymethylacrylate esters [1], with one [2][3][4] or two phosphonic acid moieties [5], or with phosphoric [4][6] or sulfonic acid groups [7] as well as with carboxylic acid groups

A novel and efficient method to prepare 2-aryltetrahydrofuran-2-ylphosphonic acids

• Vsevolod V. Komissarov,
• Anatoly M. Kritzyn and
• Jouko J. Vepsäläinen

Beilstein J. Org. Chem. 2010, 6, No. 63, doi:10.3762/bjoc.6.63

• result of anchimeric assistance of the phosphonic acid group. Keywords: 4-chloro-1-aryl-1-butanones; cyclization; furan; heterocycle; phosphonic acids; Introduction Our laboratory has conducted systematic evaluation of polymethylene derivatives of nucleic bases with various terminal functional groups

• . Previously, to obtain phenylvinylphosphonic acids 3, Conant [9] heated the reaction mixture under atmospheric pressure at high temperature (~280 °C). Initially, we also followed this procedure, but soon realized that the yield of phosphonic acid 2a was significantly higher under the milder conditions shown

N-alkyl-N-(phosphonoethyl) substituted (meth)acrylamides – new adhesive monomers for self-etching self-priming one part dental adhesive

• Joachim E. Klee and
• Uwe Lehmann

Beilstein J. Org. Chem. 2009, 5, No. 72, doi:10.3762/bjoc.5.72

• -methylacrylamidomethyl)benzylphosphonic acid [2] and a bis(meth)acrylamide comprising one phosphoric acid moiety [3] have been prepared and were investigated for a dental adhesive. Furthermore, (meth)acrylamides with one [4][5][6][7][8] or two [7][8][9] phosphonic acid groups were suggested as hydrolytically stable

• acidic monomers. The aim of the presented work was to synthesize novel (meth)acrylamides with phosphonic acid moieties and to investigate the influence of monomers bearing different aliphatic side chains and a different number of polymerizable and acidic groups on the adhesion of enamel and dentin

• acid ethyl ester with trimethylsilyl bromide (Scheme 1, Table 1). (Meth)acrylamides 3a and 3b were prepared by addition of vinylphosphonic acid ethyl ester to acrylamide and methacrylamide respectively and the same procedure for methanolysis of the phosphonic acid ethyl ester as that described above

Synthesis of novel (1-alkanoyloxy- 4-alkanoylaminobutylidene)-1,1-bisphosphonic acid derivatives

• Petri A. Turhanen and
• Jouko J. Vepsäläinen

Beilstein J. Org. Chem. 2006, 2, No. 2, doi:10.1186/1860-5397-2-2

• hydrophilic, highly anionic and their bioavailabilities are very poor. [12][13][14] It would be a clear advance to prepare more lipophilic and biodegradable derivatives of BPs. A rather straightforward method to improve the lipophilicity of amino BPs is to convert hydroxyl or/and amino group or the phosphonic

• acid groups with a biodegradable ester or amide functionality. Our group has designed, synthesized and studied in vitro several different clodronate (R1 = R2 = Cl, Figure 1) and etidronate (R1 = CH3 R2 = OH, Figure 1) ester and amide derivatives to act as biodegradable prodrugs. [15][16][17][18][19] We