Nitrate esters anion

Nichols and co-workersstudied the formation of j8-hydroxy nitrate esters via the acid-catalyzed ring-opening of epoxides with nitrate anion. Reactions were conducted in aqueous media using solutions of ammonium nitrate is nitric acid and under nonaqueous conditions using solutions of pure nitric acid in chloroform. 2-Nitratoethanol (32) is formed in 58 % yield from ethylene oxide (30) using either of these methods. ... 

Unsymmetrical epoxides (39) can form two isomers, (40) and (41), on reaction with nitrate anion and so raise the issue of regioselectivity. Under acidic conditions terminal epoxides are found to predominantly yield the primary nitrate ester (41) although this is not clear cut and propylene oxide is reported to yield an ill defined mixture of isomers. A comprehensive study on the regioselectivity of epoxide opening with nitrate anion under acidic conditions was conducted on glycidol. ... 

Displacements with azido anion are tolerant of many pre-existing explosophoric groups but the nitrate ester group readily undergoes displacement as seen for the synthesis of bis(2-azidoethyl)nitramine (13) from Ai-nitrodiethanolamine dinitrate (12) (DINA). " ... 

We also were successful in applying the alkyl nitrate nitration to TT-deficient heterocyclic compounds such as 2- and 4-meth-ylpyridines, 4-methyl pyrimidine, and to ir-excessive heterocyclics such as 2-methylbenzoxazole and 2-methylbenzothiazole (15). Both sodium and potassium amides in liquid ammonia were found to be effective as bases. In the KNH2-JI.NH3 system optimum yields are obtained if the molar ratio of base to substrate to nitrate ester is 2.0 1.0 2.5. After allowing 2-3 minutes for anion formation the nitrate ester is added as rapidly as possible while maintaining the temperature below -33°. Next the ammonia is replaced with ether and the nitro salt filtered off and acidified with aqueous acetic acid. 

A remarkable special property of nitrate esters is the ability to catalyze some additional polymerization reactions [42]. In nitroglycerine, both styrene and methyl methacrylate can be self-polymerized. If the amount of nitroglycerine is up to 5-20 portion (weight fraction), equals to 10 % of polymers, the polymerization rate will be fastened. The molecular weight of polymers is less than that obtained through slowly polymerization or in situ anionic polymerization. 

Formation of vinyl acetate by the reaction of ethylene with Pd(OAc)2 can be understood by the acetoxypalladation and )3-H elimination (path a). No hydride shift occurs because the acetoxy group is electron-attracting. In addition, ethylene glycol monoacetate (9) is formed as a nucleophilic addition product in the presence of nitrate anion (path b) [13]. Formation of glycol monoacetate is explained by the displacement of Pd-OAc with a nitrate anion, followed by hydrolysis of the nitrate ester. 

Cationic, anionic, and amphoteric surfactants derive thek water solubiUty from thek ionic charge, whereas the nonionic hydrophile derives its water solubihty from highly polar terminal hydroxyl groups. Cationic surfactants perform well in polar substrates like styrenics and polyurethane. Examples of cationic surfactants ate quaternary ammonium chlorides, quaternary ammonium methosulfates, and quaternary ammonium nitrates (see QuARTERNARY AMMONIUM compounds). Anionic surfactants work well in PVC and styrenics. Examples of anionic surfactants ate fatty phosphate esters and alkyl sulfonates. 

Experimental observations and test calculations pointed out a special behaviour of the nitrate anion when faced with 6arbocations. Therefore a detailed investigation with the assistance of the MINDO/3 and the Huron-Claverie method was carried out122). It appeared that in addition to the ester formation and the proton transfer to the counterion, the formation of NO+ by oxygen transfer to the cation must be considered as well (see Fig. 11). 

Among cations, potassium, acetylcholine, some cationic surfactants (where the ion-exchanger ion is the / -chlorotetraphenylborate or tetra-phenylborate), calcium (long-chain alkyl esters of phosphoric acid as ion-exchanger ions), among anions, nitrate, perchlorate and tetrafluoro-borate (long-chain tetraalkylammonium cations in the membrane), etc., are determined with this type of ion-selective electrodes. 

Displacement of sulfonate esters with nitrate anion... 

Uranyl ions form complexes in solutions with most anions. Uranyl sulfate and carbonate complexes are especially strong and are used in extracting uranium from its ores. Of great practical importance are the complexes of the uranyl ions with nitrate that are soluble in organic liquids such as alcohols, ethers, ketones, and esters. One of the most important of these reactions is that involving the extraction of uranyl nitrate into TBP (the Purex process) ... 

The diols (97) from asymmetric dil droxylation are easily converted to cyclic sii e esters (98) and thence to cyclic sulfate esters (99).This two-step process, reaction of the diol (97) with thionyl chloride followed by ruthenium tetroxide catalyzed oxidation, can be done in one pot if desired and transforms the relatively unreactive diol into an epoxide mimic, ue. the 1,2-cyclic sulfate (99), which is an excellent electrophile. A survey of reactions shows that cyclic sulfates can be opened by hydride, azide, fluoride, thiocyanide, carboxylate and nitrate ions. Benzylmagnesium chloride and thie anion of dimethyl malonate can also be used to open the cyclic sulfates. Opening by a nucleophile leads to formation of an intermediate 3-sidfate aiuon (100) which is easily hydrolyzed to a -hydroxy compound (101). Conditions for cat ytic acid hydrolysis have been developed that allow for selective removal of the sulfate ester in the presence of other acid sensitive groups such as acetals, ketals and silyl ethers. 

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