Oximes phosphorus compounds

As previously reported, oximes react with electrophilic tervalent phosphorus compounds to give the rearranged product (62). Hudson and his co-workers have... 

Caranto, G.R. et al. Amplification of the effectiveness of acetylcholinesterase for detoxification of organo-phosphorus compounds by bis-quatemary oximes, Biochem. Pharmacol, 47, 347, 1994. 

Childs AF, Davies DR, Green AL et al. (1955). The reactivation by oximes and hydroxamic acids of cholinesterase inhibited by organo-phosphorus compounds. Brit J Pharmacol, 10, 462-465. 

Laevo-menthone is converted into its oxime by means of hydroxylamine.. This is treated with strong sulphuric acid, and so inverted to isomenthone oxime. This is treated with phosphorus trichloride in chloroform solution, when hydrochloric acid is given off, and menthonitrile is formed. The last named is reduced by sodium into menthonylamine, and the oxalic acid compound of this is warmed with sodium niteite solution when, menthonyl alcohol is formed. This body has the following characters —... 

Replacement of the carbonyl oxygen atom by sulfur may be effected by heating with phosphorus pentasulfide (49JCS2142), boron sulfide or silicon disulfide which gives high yields under mild conditions, as, for example, in the synthesis of 7-methoxy-2-methylchromene-4-thione (438) (69JCS(C)2192). Such compounds are more easily converted into their oximes or hydrazones than the oxygen compounds. 

By treating o-chloromethylaniline hydrochloride with cu-benzyloxy-butyro- and -valeronitriles in refluxing o-dichlorobenzene in the presence of stannic chloride, Mufloz and Madroilero obtained the tricyclic compounds 124 and 202, respectively. The pyrido[2,l- )]quinazolines 289 were prepared by refluxing o-chloromethylaniline hydrochloride in dichlorobenzene with 2-chloropyridine and its tetrahydro derivative. The latter was obtained in situhy Beckmann rearrangement of cyclopentanone oxime with phosphorus pentachloride. 

This so-called Beckmann transformation has been of great significance for the explanation of the constitution of the isomeric oximes. If- eg., phosphorus pentachloride is allowed to act on both of the above formulated stereoisomeric oximes of the brombenzophenone, the same compounds are not obtained from both, but two different ones, which, as follows from their saponification products, correspond on the one hand to the benzoyl derivative of bromaniline, and, on the other, to the brombenzoyl derivative of aniline ... 

Tetrahedral phosphorus in a five-membered ring is highly strained. To relieve this strain, such compounds tend to expand the coordination of the phosphorus to five. It was reasoned that if indeed the thermal fragmentation should proceed by the four-centred mechanism outlined above, it would proceed much more readily in a five-membered cyclic a-hydroxyiminophosphonate. To test this, a five-membered cyclic benzoylphosphonate was reacted with hydroxylamine . This reaction yielded only the (E )-oxime along with a considerable amount of benzonitrile (equation 123). This result is consistent with the... 

There arc exceptions to the typical pesticidal OP structures described previously, and in the case of AChEs inhibited by these pesticides, less is known about reactivation rates, both spontaneous and oxime induced. These pesticides include EPN, leptophos, and cyanophenfos, which have one ethoxy and one phenyl group, and methamidophos, which is a methoxy. Wmethyl compound, Trichloronat, a phosphonate, has one ethoxy substituent and an ethyl group attached directly to the phosphorus atom. For some pesticides, it is not clear which group is... 

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