Diethyl ether, reaction with copper nitrate

The efficient At-nitration of secondary amines has been achieved by transfer nitration with 4-chloro-5-methoxy-2-nitropyridazin-3-one, a reagent prepared from the nitration of the parent 4-chloro-5-methoxypyridazin-3-one with copper nitrate trihydrate in acetic anhydride. Reactions have been conducted in methylene chloride, ethyl acetate, acetonitrile and diethyl ether where yields of secondary nitramine are generally high. Homopiperazine is selectively nitrated to At-nitrohomopiperazine or At, At -dinitrohomopiperazine depending on the reaction stoichiometry. At-Nitration of primary amines or aromatic secondary amines is not achievable with this reagent. 

Reaction of Copper Nitrate with Dimethyl Ether. In sharp contrast to the behavior of diethyl ether, dimethyl ether shows little reactivity with copper nitrate. Dimethyl ether was condensed onto copper nitrate at —70° C. on warming to —20° C. ether evaporated to leave a pale blue solid which melted to a green oil at —12°. This oil was stable up to 50° C., and analysis showed it to be a molecular addition compound, Cu(N03)2.1.5 Me20 on treatment with water the dimethyl ether was evolved. Some decomposition of the addition compound does occur on long standing under vacuum (16),... 

The paper discusses two types of reaction involving metal complexes, and it is postulated that each proceeds by an initial free-radical step. In reactions between metal carbonyls and N2O4—NO2 mixtures, the nature of the product depends upon the phase in which the reaction is carried out. In the liquid phase, where the predominant equilibrium is N204 N0+ + NO3-, metal nitrates or carbonyl nitrates are formed in the gas phase, where the equilibrium is N2O4 2NO2/ nitrites or their derivatives are produced. Reactions of Mn2(CO) o Fe(CO)5, Co2(CO)3, and Ni(CO)4 are discussed. Anhydrous metal nitrates in which the nitrate group is covalently bonded to the metal have enhanced reactivity. This is believed to result from the dissociation M—O—N02 M—O + NO2 This can explain the solution properties of beryllium nitrates, and the vigorous (even explosive) reaction of anhydrous copper nitrate with diethyl ether. 

On the contrary, encapsulation of the larger K" " or NH4 ions should lead to the formation of metallacrown ether sandwich complexes (M+ MC= 1 2). Reaction of diethyl ketipinate H2L 13 with copper(ll) acetate in the presence of calcium nitrate affords green microcrystals 14 after crystallization from tetrahydro-furan/diethyl ether (Scheme 1). 

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