Organophosphorus compounds. XIX. Synthesis of 2,3-Dihydro-1 H-1,2-benzazaphosphole 2-oxides, variously substituted on nitrogen and phosphorus, by N-P cyclization of zwitterionic intermediates

1983 ◽  
Vol 36 (12) ◽  
pp. 2517 ◽  
Author(s):  
DJ Collins ◽  
PF Drygala ◽  
JM Swan
Keyword(s):  
Ethyl Ester ◽  
Organophosphorus Compounds ◽  
Phosphinic Acid ◽  
Nitrogen And Phosphorus ◽  
Hydrochloride Salt ◽  
Analogous Manner ◽  
Conventional Methods ◽  
Hydrolysis Of

2-Phenyl-2,3-dihydro-1H-1,2-benzazaphosphole 2-oxide (7a) was prepared by thermolysis of the corresponding zwitterionic amino phosphinic acid (4), or its hydrochloride salt (1). Thermolysis of methyl (2-aminobenzy1)phenylphosphinate (5a) was accompanied by intermolecular O→N transmethylation to give, after cyclization, l-methyl-2-phenyl-2,3-dihydro-1H-1,2-benzazaphosphole 2-oxide (9a); similarly, the ethyl ester (5b) gave the N-ethyl heterocycle (9b). Reaction of 2-phthalimidobenzyl bromide (13a) with diethyl methylphosphonite (14b) gave ethyl (2-phthalimidobenzy1)methylphosphinate (15a). Hydrolysis of (15a) afforded (2-aminobenzyl)- methylphosphinic acid (16), and thermolysis of this produced 2-methyl-2,3-dihydro-lH-1,2-benzaza- phosphole 2-oxide (18a). 1-Methyi-2-methoxy-2,3-dihydro-1H-l,2-benzazaphosphole 2-oxide (24) was synthesized in an analogous manner. Base catalysed N-alkylation of the benzazaphosphole derivatives (7a) and (18a) was readily achieved, and the interconversion of 2-oxides and 2-sulfides was accomplished by conventional methods.

Organophosphorus compounds. P-Arylated perhydro-1,2-azaphosphorines

1977 ◽  
Vol 30 (3) ◽  
pp. 579 ◽  
Author(s):  
DG Hewitt ◽  
GL Newland
Keyword(s):  
Thionyl Chloride ◽  
Good Yield ◽  
Aqueous Ammonia ◽  
Organophosphorus Compounds ◽  
Phosphinic Acid ◽  
Sodium Hydride ◽  
Hydrolysis Of ◽  
Phenylmagnesium Bromide

Treatment of ethyl 4-bromobutylphosphonochloridate with phenylmagnesium bromide, followed by acid-catalysed hydrolysis of the product, gave 4- bromobutyl(phenyl)phosphinic acid. This was converted into the corresponding phosphinamide by treatment with thionyl chloride and then with aqueous ammonia. Cyclodehydrobromination with sodium hydride in warm xylene then gave a good yield of 2-phenylperhydro-1,2- azaphosphorine 2-oxide. Some other routes to this compound were investigated.

Synthesis of Normuramic Acid Carba Analog and Its Glycopeptide Derivative Resistant to β-Elimination Splitting of the Side Chain

2000 ◽  
Vol 65 (11) ◽  
pp. 1726-1736 ◽  
Author(s):  
Miroslav Ledvina ◽  
Radka Pavelová ◽  
Anna Rohlenová ◽  
Jan Ježek ◽  
David Šaman
Keyword(s):  
Ethyl Ester ◽  
Alkaline Hydrolysis ◽  
Benzyl Ester ◽  
Side Chain ◽  
Propanoic Acid ◽  
Hydrolysis Of

Carba analogs of normuramic acid, i.e., 3-(benzyl 2-acetamido-2,3-dideoxy-4,6-O-isopropylidene-α-D-glucopyranosid-3-yl)propanoic acid derivatives (nitrile or esters) 3a-3c were prepared by addition of radicals generated from benzyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-3-O-[(methylsulfanyl)thiocarbonyl]- (2a) or -3-O-(phenoxythiocarbonyl)-α-D-glucopyranoside (2b) with Bu3SnH to acrylonitrile or acryl esters. Alkaline hydrolysis of ethyl ester 3c afforded 3-(benzyl 2-acetamido-2,3-dideoxy-4,6-O-isopropylidene-α-D-glucopyranosid-3-yl)propanoic acid (5). Coupling of acid 5 with L-2-aminobutanoyl-D-isoglutamine benzyl ester trifluoroacetate and subsequent deprotection of the intermediate 6 furnished N-[3-(2-acetamido-2,3-dideoxy-α-D-glucopyranosid-3-yl)propanoyl]-L-2-aminobutanoyl-D-isoglutamine (7).

scholarly journals MW irradiation and ionic liquids as green tools in hydrolyses and alcoholyses

2020 ◽  
Vol 10 (1) ◽  
pp. 001-010 ◽  
Author(s):  
Nikoletta Harsági ◽  
Betti Szőllősi ◽  
Nóra Zsuzsa Kiss ◽  
György Keglevich
Keyword(s):  
Ionic Liquids ◽  
Alkaline Hydrolysis ◽  
Alkyl Group ◽  
Phosphinic Acid ◽  
Reaction Times ◽  
Alternative Possibility ◽  
First Order ◽  
Pseudo First Order ◽  
Mw Irradiation ◽  
Hydrolysis Of

Abstract The optimized HCl-catalyzed hydrolysis of alkyl diphenylphosphinates is described. The reaction times and pseudo-first-order rate constants suggested the iPr > Me > Et ∼ Pr ∼ Bu order of reactivity in respect of the alkyl group of the phosphinates. The MW-assisted p-toluenesulfonic acid (PTSA)-catalyzed variation means a better alternative possibility due to the shorter reaction times, and the alkaline hydrolysis is another option. The transesterification of alkyl diphenylphosphinates took place only in the presence of suitable ionic liquids, such as butyl-methylimidazolium hexafluorophosphorate ([bmim][PF6]) and butyl-methylimidazolium tetrafluoroborate ([bmim][BF4]). The application of ethyl-methylimidazolium hydrosulfate ([emim][HSO4]) and butyl-methylimidazolium chloride ([bmim][Cl]) was not too efficient, as the formation of the ester was accompanied by the fission of the O–C bond resulting in the formation of Ph2P(O)OH. This surprising transformation may be utilized in the phosphinate → phosphinic acid conversion.

scholarly journals Simultaneous Hydrolysis and Detection of Organophosphate by Benzimidazole Containing Ligand-Based Zinc(II) Complexes

Crystals ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 714
Author(s):  
Gaber A. M. Mersal ◽  
Hamdy S. El-Sheshtawy ◽  
Mohammed A. Amin ◽  
Nasser Y. Mostafa ◽  
Amine Mezni ◽  
...  
Keyword(s):  
Square Wave Voltammetry ◽  
Limit Of Detection ◽  
Organophosphorus Compounds ◽  
Organophosphorus Pesticides ◽  
Carbon Paste ◽  
Square Wave ◽  
Wave Voltammetry ◽  
Carbon Past Electrode ◽  
Hydrolysis Of ◽  
Biomimetic Sensor

The agricultural use of organophosphorus pesticides is a widespread practice with significant advantages in crop health and product yield. An undesirable consequence is the contamination of soil and groundwater by these neurotoxins resulting from over application and run-off. Here, we design and synthesize the mononuclear zinc(II) complexes, namely, [Zn(AMB)2Cl](ClO4) 1 and [Zn(AMB)2(OH)](ClO4) 2 (AMB = 2-aminomethylbenzimidazole), as artificial catalysts inspired by phosphotriesterase (PTE) for the hydrolysis of organophosphorus compounds (OPs) and simultaneously detect the organophosphate pesticides such as fenitrothion and parathion. Spectral and DFT (B3LYP/Lanl2DZ) calculations revealed that complexes 1 and 2 have a square-pyramidal environment around zinc(II) centers with coordination chromophores of ZnN4Cl and ZnN4O, respectively. Both 1 and 2 were used as a modifier in the construction of a biomimetic sensor for the determination of toxic OPs, fenitrothion and parathion, in phosphate buffer by square wave voltammetry. The hydrolysis of OPs using 1 or 2 generates p-nitrophenol, which is subsequently oxidized at the surface of the modified carbon past electrode. The catalytic activity of 2 was higher than 1, which is attributed to the higher electronegativity of the former. The oxidation peak potentials of p-nitrophenol were obtained at +0.97 V (vs. Ag/AgCl) using cyclic voltammetry (CV) and +0.88 V (vs. Ag/AgCl) using square wave voltammetry. Several parameters were investigated to evaluate the performance of the biomimetic sensor obtained after the incorporation of zinc(II) complex 1 and 2 on a carbon paste electrode (CPE). The calibration curve showed a linear response ranging between 1.0 μM (0.29 ppm) and 5.5 μM (1.6 ppm) for fenitrothion and 1.0 μM (0.28 ppm) and 0.1 μM (0.028 ppm) for parathion with a limit of detection (LOD) of 0.08 μM (0.022 ppm) and 0.51 μM (0.149 ppm) for fenitrothion and parathion, respectively. The obtained results clearly demonstrated that the CPE modified by 1 and 2 has a remarkable electrocatalytic activity towards the hydrolysis of OPs under optimal conditions.

Study and modeling of mechanisms of cholinesterasis reactions in order to improve their catalytic properties in the neutralization reactions of organophosphorous compounds

2020 ◽  
pp. 134-174
Author(s):  
Sergey Varfolomeev ◽  
Bella Grigorenko ◽  
Sofya Lushchekina ◽  
Patrick Masson ◽  
Galina Mahaeva ◽  
...  
Keyword(s):  
First Generation ◽  
Organophosphorus Compounds ◽  
Protein Molecule ◽  
Catalytic Antibodies ◽  
High Rate ◽  
Biological Targets ◽  
Organophosphorous Compounds ◽  
Rate Of Hydrolysis ◽  
The Stability ◽  
Hydrolysis Of

“Biocleaners” or “bioscavengers” are biological objects (enzymes, catalytic antibodies) that are capable of binding and/or hydrolyzing organophosphorus compounds (OPC). Their use seems to be the most effective alternative to traditional antidotes to neutralize or detoxify OPC. The introduction of bioscavengers allows neutralizing toxicant molecules in the bloodstream before they reach their biological targets, thereby providing protection against poisoning. Bioscavengers of the first-generation neutralized OPC molecules by stoichiometrically binding to them. The safety and efficacy of human butyrylcholinesterase (BChE) for protecting against OPC poisoning has been shown. However, the stoichiometric neutralization of OPC requires the introduction of a huge amount of expensive biopharmaceuticals. Catalytic bioscavengers that hydrolytically neutralize OPC were introduced at a much lower dose to achieve the same degree of effectiveness. The most effective catalytic bioscavengers are enzymes. The most promising enzymes are artificial mammalian paraoxonase mutants and bacterial phosphotriesterases. However, studies of other enzymes, such as prolidases, oxidases, artificial mutants of cholinesterases and carboxyl esterases and catalytic antibodies are actively ongoing. Since OPC are pseudosubstrates of cholinesterases (ChEs), a detailed description of the mechanisms of inhibition, dealkylation, and spontaneous reactivation of phosphorylated ChEs is critical for the development of ChEs mutants with a high rate of hydrolysis of OPC. The review presents an analysis of different views on the mechanisms of interaction of ChEs with OPC, discusses the possible directions of creating effective catalytic biological traps based on BChE and changes in their mechanism of action as compared to the native enzyme. A separate section is devoted to the effect of mutations, both polymorphic and artificial, on the stability of the protein molecule of BChE.

Thermodynamics of the Hydrolysis of N-Acetyl-L-phenylalanine Ethyl Ester in Water and in Organic Solvents

1995 ◽  
Vol 99 (5) ◽  
pp. 1594-1601 ◽  
Author(s):  
Y. B. Tewari ◽  
M. M. Schantz ◽  
P. C. Pandey ◽  
M. V. Rekharsky ◽  
R. N. Goldberg
Keyword(s):  
Ethyl Ester ◽  
Organic Solvents ◽  
Hydrolysis Of
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