Organophosphorus compounds, use

Krikorian SE, Chom TA, King JW. 1987. Determination of octanol/water partition coefficients of certain organophosphorus compounds using high-performance liquid chromatography. Quant Struct-Act Relat 6(2) 65-69. 

General catalytic hydrophosphinylation reaction of alkenes and alkynes with hypophosphorous compounds (385) to give H-phosphinic acid derivatives (386) has been described. Compounds (386) are important biologically active compounds as well as being synthetic intermediates which can be converted into a variety of other organophosphorus compounds using well-established procedures. ... 

Organophosphorus compounds Phosphites are the main organophosphorus compounds used to control oxidative degradation of lubricants. They eliminate hydroperoxides, peroxy and alkoxy radicals, retard the darkening of lubricants over time and also limit photodegradation. These performance characteristics may be of importance for polyalphaolefins, hydrocracked or severely hydrotreated base stocks and white oils. 

Oxohalides EOX3 form tetrahedral molecules with E=P, but polymeric structures with As and Sb. POCl3 is an important intermediate in the manufacture of organophosphorus compounds, used, for example, as insecticides. 

Organophosphorus compounds used as insecticides contain the pentavalent phosphorus atom. In the fundamental state the phosphorus atom has a 3s 3p external configuration however, 3d orbitals also contribute to the formation of its compounds. Transition to the 3s 3p 3d state, corresponding to the trigonal bipyramide, requires a high activation energy of about 800 KJ/mole (Hudson,... 

Other types of inhibitors may not be so tolerable. Organophosphorus compounds, used in nerve gases and weed killers (e.g., parathion), form a covalent irreversible bond with the active serine and permanently inactivate acetylcholinesterase. This is a type of suicide inhibition because the inhibitor reacts with the enzyme much like a substrate, but becomes blocked in the intermediate state where the enzyme-phosphoryl bond is stable, in contrast to the hydrolyzable enzyme-acetyl bond. These compounds are life-threatening. 

Table 23.4 shows recoveries of organophosphorus compounds using C18 octadecyl silica and different polymeric sorbents. Recoveries of 63 to 120% on 68 to 72% on XAD-2, ... 

Table 23.5 shows recoveries of organophosphorus compounds using C18 octadecyl silica and different polymeric sorbent disks. Recoveries of 53 to 164% onC18 except for dimethoate (0%) and 64 to 99% on polymers have been reported. Some metabolites have been determined with recoveries of 97 to 100%. " The chromatographic methods used in combination with SPE were LC-UV/DAD GC-NPD, and GC-MS. Detection limits using SPE with disks range from 0.02 to 4.3 /rg/1 depending of the sample volumes used for the extraction and of the analytical methods. 

The clean-up procedure recommended by EPA 3620 for organophosphorus compounds uses Florisil. It involves reducing the sample extract volume in hexane, transferring this concentrated extract onto the Horisil column and eluting the organophosphorus compounds in diethyl ether/hexane (30 70, v/v). 

Metrifonate (trichloifon bearcil) is an organophosphorus compound used as an insecticide and then as an anthelmintic, especially for S. haematobium. Metrifonate is a prodrug that is converted nonen-zymatically to dichlorvos (2,2-dichlorovinyl dimethyl phosphate, DDVP), a potent cholinesterase... 

The first organophosphorus compounds used as insecticides were very toxic to humans and they inclnded TFPP (12.96a), HFTP (mainly TFPP), parathion (12.96b) and paraoxon (12.96c). 

Tomilov and collaborators were the first to obtain trialkylphosphates by electrolysis of suspensions of phosphorus in alcohol + HCl [92]. This direct electrosynthesis of organophosphorus compounds using elementary phosphorus was further developed by the electrochemists in Kazan (joint pubUcatirMi [93]). It is worth mentioning that although Tomilov worked in a closed institute, he participated in many joint activities with electrochemists from open institutions... 

Vallet, V, Cruz, C., Josse, D., et al, 2007. In vitro percutaneous penetration of organophosphorus compounds using full-thickness and split-thickness pig and human skin. Toxicol. In Vitro 21 (6), 1182-1190. 

Gladilovich, V.D., Krasnov, I.A., Podolskaya, E.P., et al., 2010. Identification of serum albumin peptides, modified by organophosphorus compounds, using methods of chromatography and mass spectrometry. Nauchnoe Priborostroenie (Scientific Instrumentation) 20 (4), 84-92. 

T. C. Marrs, P. Edwards, Human adverse reactions to organophosphorus compounds used in veterinary medicines in Veterinary Pharmacovigilance. Adverse Reactions to Veterinary Medicinal Products, ed. K. N. Woodward, Wiley-Blackwell, Chichester, 2009, pp. 517 528. 

Sahin A, Dooley K, Cropek DM, West AC, Banta S (2011) A dual enzyme electrochemical assay for the detection of organophosphorus compounds using organophosphorus hydrolase and horseradish peroxidase. Sensor Actual B Chem 158(l) 353-360. doi 10.1016/j.snb.2011. 06.034... 

When saccharin is treated with diethyl phosphorothiolothionate, the 3-ethylmercapto compound is obtained, rather than the expected organophosphorus compound (77 ACS(B)460). Treatment of saccharin with phosphorus pentoxide and amines gives 3-(substituted-amino)-1,2-benzisothiazole 1,1-dioxides, via an intermediate phosphate (81ZN(B)1640). Reduction of saccharin with zinc and hydrochloric acid gives 2,3-dihydro-l,2-benzisothiazole 1,1-dioxide, the method being used to estimate saccharin in foodstuffs (75MI41701). 

Chiral phosphoryl and sulfinyl groups are known as efficient auxiliaries in asymmetric synthesis. As reported below, their asymmetric induction in the a-posi-tion has been used to prepare chiral non-racemic organophosphorus compounds a-substituted by a sulfur function. Such compounds can also be obtained from their a-hydroxy analogues by OH-4 SR stereoselective transformation. 

Among /1-thiosubstituted organophosphorus compounds bearing chiral groups, phosphono methyl thiazolines (Sect. 2.2.1, Scheme 8) and o-sulfanyl aryl phos-phonamides or phosphinoxides (Sect. 3.3, schemes 20 and 21) have already been mentioned. As a complement to this, some recent synthesis of non racemic /1-sulfinyl phosphines and phosphonates and thiazolidinyl phosphonates are reported below. Moreover, some chiral )8-thio-substituted phosphines have been used as metal ligands in asymmetric catalysis and are listed in Sect. 5.3. 

Tervalent organophosphorus compounds containing one single P-N bond with the valency of each atom saturated by protons or carbons (but no other heteroatoms) have been known since their discovery by MichaeUs more than one century ago [ 1 ] and named indistinctly as aminophosphanes, phosphanamines, phosphazanes, or phosphinous amides. This last chemical nomenclature is the one used by the Chemical Abstracts Service (CAS) for indexing these compounds and is also the one that best delimits the scope of this review those species derived from the parent H2P-NH2 (phosphinous amide in CAS nomenclature) by partial or total substitution of protons by hydrocarbon radicals (Table 1). 

The use of t.l.c. for separating organophosphorus compounds has been reviewed. In a study of phosphoryl compounds it was shown that / m values i.e. log [(1 - Rv)lRy on silica gel using hexane-acetone as eluant, depend upon the polarity of the P=0 group.The migration order found was... 

Absorbance detectors are also commonly used in combination with postcolumn reactors. Here, most issues of detector linearity and detection limit have to do with optimization of the performance of the reactor. In a typical application, organophosphorus compounds with weak optical absorbances have been separated, photolyzed to orthophosphate, and reacted with molybdic acid, with measurement being performed by optical absorbance.58... 

Other chemicals evaluated but not yet adopted commercially include organophosphorus compounds, triphenyltin compounds, quaternary ammonium salts, imidazoles, benzimidazoles, carbamates and the precocene anti-juvenile hormones [517]. Although none of the above has found use as an insect-resist agent, several have been used as antimicrobial agents for textiles. 

Anderson, R. L. et al., Clin. Chim. Acta, 1982, 121, 111-116 The standard method for assaying organophosphorus compounds can be modified to use sulfuric acid to digest the samples and hydrogen peroxide as oxidant in place of perchloric acid. 

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