The Preparation of Some Organophosphorus Compounds Possessing Anticholinesterase Activity¹

Abstract

1379taining group (i.e., the sulfonyl group), as in the change from hippurate ion to benzenesulfonylglycinate, causes a very large decrease in the strength of combination. This large effect may be entirely steric and due to the larger space requirement of two oxygens.In the absence of the carbonyl group, there seems to be some correlation between the combining power of the hapten and the distance between the benzene group and the carboxylate ion. Phenylbutyrate ion, in which the benzene and carboxylate have the same distance between them as in the homologous benzoylpropionate ion, is somewhat more effective in combining with anti-BzP antibodies than are the phenylvalerate and the phenylpropionate (hydrocinnamate) ions which contain one methylene group more or less than the butyrate.The importance of the van der Waals interaction of the benzene ring is emphasized by a comparison of the combination of anti-BzP antibody with valerate and with phenylbutyrate, AFre¡ for the combination with the aliphatic compound is at least 700 cal. greater. New York, N. Y.

Synthesis and Proton Dissociation Properties of Arylphosphonates: A Microwave‐Assisted Catalytic Arbuzov Reaction with Aryl Bromides

“…After complete hydrolysis, the mixture was concentrated in vacuum to afford the products ( 3a–l ) in yields of 71–93% in a purity of at least 98%. From among the arylphosphonic acids, 3a, 3c, 3f, 3g , and 3k have been described and partially characterized , 3b and 3h–j were described and characterized only by a melting point , whereas the remaining products 3d, 3e , and 3l are new. Spectral parameters of the known species were compared with those of authentic samples.…”

“…(2‐Fluorophenyl)Phosphonic Acid ( 3i ) . Yield: 81%; mp: 144–146°C, mp : 146–149°C; 31 P NMR (DMSO) δ : 7.4; 13 C NMR (DMSO) δ : 115.6 (dd, J 1 = 7.1, J 2 = 22.4, C 3 ), 121.2 (dd, J 1 = 178.7, J 2 = 19.1, C 1 ), 123.8 (dd, J 1 = 12.8, J 2 = 3.3, C 5 ), 133.2 (dd, J 1 = 5.3, J 2 = 5.0, C 4 ), 133.5 (dd, J 1 = 8.3, J 2 = 1.5, C 6 ), 162.4 (d, J = 247.4, C 2 ); 1 H NMR (DMSO) δ : 7.18–7.28 (m, 2H, ArH) 7.52–7.59 (m, 1H, ArH), 7.65–7.75 (m, 1H, ArH); (M + H) + found = 177.0123, C 6 H 7 FO 3 P requires 177.0117.…”

Non‐Tethered Organometallic Phosphonate Inhibitors for Lipase Inhibition: Positioning of the Metal Center in the Active Site of Cutinase

“…A possible explanation for the lack of inhibitory activity by 3 and 4 could be that these complexes exist in the basic buffer solution as ionic complexes, which probably interact with the hydrophobic surface of cutinase in a repelling manner, thereby preventing them from entering the active site. Related to this, Freedman et al reported the inhibitory activity of related phenylphosphonic and phenylphosphinic acids toward acetylcholine esterase, for which strong inhibition activities were found in some examples 15. The enzyme has an active site similar to that of cutinase (i.e.…”

“…However, they have never been tested for lipases, e.g. cutinase 15. From a synthetic point of view, pincer‐containing phosphonic acids 3 and 4 (Figure 2) are of interest, since the route to their synthesis appeared to be considerably shorter than the synthetic route to phosphonate compounds like 1 and 2 16.…”

On the rearrangement of N-aryl-N-Boc-phosphoramidates to N-Boc-protected o-aminoarylphosphonates

“…o -Aminophenylphosphonic acid was tested for its anticholesterinase activity [ 27 ] and 2-amino-4-methylphenylphosphonic acid for removing formaldehyde adducts [ 28 ] from RNA and DNA bases. The protected o -aminoarylphosphonates prepared by [1,3]-migration of phosphorus can be deprotected to give o -aminoarylphosphonic acids as shown for three examples (Scheme 8 ).…”