Sodium reaction with oxygen

The oxygen reaction with sodium erythorbate is catalyzed by traces of nickel, copper, or iron in solution, so stainless steel or plastic stor-... 

A calorimetric study of reaction with sodium or potassium hydroxides in ethanol or 2-propanol is given. At starting temperatures below 70°C the product is the appropriate nitrophenyl ether above that temperature, reduction of the nitro groups may come into play, to give much more energy and a variety of other products. This reaction is inhibited by oxygen. There is potential for runaway if such reactions are operated industrially with poor temperature control. The editor suspects that the stimulus for this study was an accident which sprayed the German environment with 2-nitroanisole. 

Metals react with nonmetals. These reactions are oxidation-reduction reactions. (See Chapters 4 and 18). Oxidation of the metal occurs in conjunction with reduction of the nonmetal. In most cases, only simple compounds will form. For example, oxygen, 02, reacts with nearly all metals to form oxides (compounds containing O2-). Exceptions are the reaction with sodium where sodium peroxide, Na202, forms and the reaction with potassium, rubidium, and cesium where the superoxides, K02, Rb02, and Cs02 form. 

The chlorohydrin reaction with sodium hydroxide is assumed to be a two-step process in which a rate-determining intramolecular displacement of chloride ion by negatively charged oxygen follows a prior equilibrium between the hydroxide ion and the hydroxyl group of the halohydrin (5). 

The bulk material may ignite or explode in storage. Traces of water may initiate the reaction. A rapid exothermic decomposition above 175°C releases oxygen and chlorine. Moderately explosive in its solid form when heated. Explosive reaction with acetic acid + potassium cyanide, amines, ammonium chloride, carbon or charcoal + heat, carbon tetrachloride + heat, N,N-dichloromethyl-amine + heat, ethanol, methanol, iron oxide, rust, 1-propanethiol, isobutanethiol, turpentine. Potentially explosive reaction with sodium hydrogen sulfate + starch + sodium carbonate. Reaction with acetylene or nitrogenous bases forms explosive products. 

In addition to the complexes of platinum(II), a number of olefin complexes of platinum(O) have been prepared. Chatt, Shaw, and Williams (103) have described the complex (olefin)bis(triphenylphosphine)-platinum(O) prepared by reaction of the olefin at 60°C with cis-dichloro-bis(triphenylphosphine)platinum(Il) in ethyl alcohol containing hydrazine hydrate. The complex was formed only with ethylene complex (C2H4)Pt[P(CgH5)3]2 has been prepared (121) by reduction of the corresponding oxygen complex with sodium borohydride in the presence of the olefin. 

I Shcherbakova, E. V. Kuznetsov, I. A. Yudilevich, O. E. Konpan, A. T. Balaban, A. H. Abolin, A. V. Polyakov, and Y. T. Struchkov, Oxygen analogs of Reissert compounds molecular structure and reactions with sodium hydroxide, Tetrahedron 44, 6217-6224 (1988). 

Pyridine is an aromatic 6n electron heterocycle, which is isoelectronic with benzene, but electron deficient. Nucleophiles thus add almost invariably to carbon C2 of the imine-like C=N double bond. Perhaps the best known nucleophilic addition is the Chichibabin reaction with sodium amide in liquid ammonia, giving 2-aminopyr-idine. Reactions of the quinoline moiety of cinchona alkaloids can be more complex. Although expected 2 -addition can be achieved easily with organolithium reagents to yield 13 (Scheme 12.6) [9], LiAlH4, for example, has been shown to attack C4 en route to quincorine and quincoridine (Schemes 12.4 and 12.5). C4 selectivity is due to chelation of aluminum by the C9 OH oxygen. 

The imino-chloride character of 3-chloro-l,5-diphenyl-U, 2,4-thiadiazine 1-oxide (139) has been exploited and displacements of the halogen by oxygen and sulfur nucleophiles, and by hydrazine, to give 3-alkoxy-, 3-alkyIthio-, and 3-hydrazino- (140) 12 ,2,4-thiadiazine 1-oxides have been carried out. On the basis of PMR spectroscopic evidence the product from the reaction with sodium hydrogen sulfide appears to be the 3(4 -thione (141) rather than the tautomeric 3-thiol (Scheme 17) <90JCS(P1)447>. 

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