Oximes chemical reactivities

Machiguchi, Nozoe and coworkers have very recently observed that in contrast to chemical reactivity of tropones, the tosylate of tropone oxime undergoes a facile ring-opening to 6-substituted (Z,Z,Z)-1,3,5-hexatriene nitriles on reaction with various nucleophiles305. For example, reaction of phenyl lithium results in the corresponding hexatriene carbonitrile (equation 183). 

Reactive oximes and their salts, such as potassium 2,3-butanedione monoximate found in commercially available Reactive Skin Decontaminant Lotion (RSDL), are extremely effective at rapidly detoxifying sulfur vesicants. Some chloroisocyanurates, similar to those found in the Canadian Aqueous System for Chemical-Biological Agent Decontamination (CAS-CAD), are effective at detoxifying sulfur vesicants, and so is oxone, a peroxymonosulfate triple salt. 

Inverting the orientation of the C4-N3 imine unit of a 2,3,1-diheterabotine gives a boron heterocycle with a markedly different chemical reactivity. In effect, the weakly basic oxime- or hydrazone-type imine nitrogen in the 2,3,1-diheteraborine is replaced by a much more basic imidate- or amidine-type imine nitrogen in the 2,4,1-diheteraborine. Likely, the Lewis acid tendency of the boron is enhanced by the ready protonation of this basic N4, and the formation of a stable borate-based zwitterion becomes thermodynamically favored. 

Similar studies by Fukuto et al. have correlated chemical reactivity, anti-ChE activity, and toxicity to insects of a series of oximes of substituted acetophenones and benzalde-hydes with the free-energy parameters, F, ° R, ir, and Excellent correlation was obtained between these... 

Metabolic activation of a,/ -unsaturated oximes, such as 46, leads to the conclusion that this class of unsaturated oximes are pro-haptens. They can undergo epoxidation that eventually produces reactive nitroso intermediates which act as strong contact sensitizers . Here, the oxime function plays a major role in the chemical activation that results in the reactive nitrosoaUcenes. It was further pointed by the authors that oximes can be hydrolyzed in vivo to the corresponding carbonyl compounds which are potential allergens. 

After completion of Volume 1, three new panels were established to Identify and assess evidence on the possible long-term health effects or delayed sequelae of the three chemical classes tested. This was done over a period of a year, during which each panel met three times. Pertinent material was examined to evaluate the possibility that experimental exposure of soldiers may have resulted in untoward health effects. The three panels were separately concerned with four cholinesterase reactivator chemicals (oximes) two types of psychochemicals (phencyclidine and dlmethylheptylpyran and congeners), administered In pure form, as opposed to street drugs and mustard gas and several lacrlmatory and respiratory irritants (such as CN, CS, CR, and CA). 

Complexes involving oxime ligands display a variety of reactivity modes that lead to unusual types of chemical compounds. As far as the oxime chemistry of platinum is concerned, these complexes are involved in facile deprotonation of the OH group with formation of oximato complexes, reduction of Pt(IV) species, Pt(II)-assisted reactions with coordinated allene," alkylation by ketones, oxime-ligand-supported stabilization of Pt(III)—Pt(III) compounds, oxidative conversion into rare nitrosoalkane platinum(II) species, and coupling with organocyanamides. ... 

The magnitude of general-acid-base catalysis by oxygen and nitrogen bases depends only on their pATa s, and is independent of their chemical natures (apart from an enhanced activity of oximes in general-acid catalysis). Nucleophilic reactivity depends markedly on the nature of the reagents. These reactions may be divided into two broad classes nucleophilic attack on soft and on hard electrophilic centers.47... 

Steric and electronic effects on the photochemical reactivity of oxime acetates of p/y-unsaturated aldehydes. Journal of the Chemical Society, Perkin Transactions 1, 163-169 (b) Armesto, D., Horspool, W.M., Mancheno, M.J., and Ortiz, M.J. (1990) The aza-di-jt-methane rearrangement of stable derivatives of 2,2-dimethyl-4,4-diphenylbut-3-enal. Journal of the Chemical Society, Perkin Transactions... 

---