DIAZONIUM PERCHLORATES

Another redox reaction leading to arenediazonium salts was described by Morkov-nik et al. (1988). They showed that the perchlorates of the cation-radicals of 4-A,A-dimethylamino- and 4-morpholinoaniline (2.63) react with gaseous nitric oxide in acetone in a closed vessel. The characteristic red coloration of these cation-radical salts (Michaelis and Granick, 1943) disappears within 20 min., and after addition of ether the diazonium perchlorate is obtained in 84% and 92% yields, respectively. This reaction (Scheme 2-39) is important in the context of the mechanism of diazotization by the classical method (see Sec. 3.1). 

Morkovnik et al. (1989) found experimentally that the addition of an equimolar amount of 4-morpholino- or 4-dimethylaminoaniline to a suspension of nitrosyl perchlorate in 100 % acetic acid, dioxan, or acetonitrile yields a mixture of the diazonium perchlorate and the perchlorate salt of the amine radical cation, with liberation of gaseous nitric oxide. Analogous results in benzene, including evidence for radicals by ESR spectroscopy and by spin trapping experiments, were obtained by Reszka et al. (1990). 

Explosive, very sensitive to heat or shock. See Other DIAZONIUM PERCHLORATES... 

Biphenylenebis(diazonium) perchlorate (1,1 -Biphenyl-4,4 -bisd iazon i u m perchlorate)... 

The three diazonium perchlorate isomers, and their 2-methyl-4,6-diphenyl analogues, all exploded on heating. 

As the anhydride of nitrous and perchloric acids, it is a very powerful oxidant. Pinene explodes sharply acetone and ethanol ignite, then explode ether evolves gas, then explodes after a few s delay. Small amounts of primary aromatic amines-aniline, toluidines, xylidines, mesidine-ignite on contact, while larger amounts exploded dangerously, probably owing to rapid formation of diazonium perchlorates. Urea ignites on stirring with the perchlorate, (probably for a similar reason). 

The diazonium perchlorates are extremely explosive, shock-sensitive materials when dry, some even when damp [1,2], The salt derived from diazotised p-phenylendiamine was considered to be more explosive than any other substance known in 1910 [3], Individually indexed compounds are 4-Aminobenzenediazonium perchlorate, 2304 Benzene-l,4-bis(diazonium perchlorate), 2160 Benzenediazonium perchlorate, 2232 4,4/-Biphenylenebis(diazonium) perchlorate, 3457... 

ARENEDIAZONIUM OXIDES, DIAZONIUM CARBOXYLATES DIAZONIUM PERCHLORATES, DIAZONIUM SULFATES DIAZONIUM SULFIDES AND DERIVATIVES DIAZONIUM TETRAHALOBORATES, DIAZONIUM TRIIODIDES... 

Existing knowledge on perchloric acid and its salts was reviewed extensively in 1960 in a monograph including the chapters Perchloric Acid Alkali Metal, Ammonium and Alkaline Earth Perchlorates Miscellaneous Perchlorates Manufacture of Perchloric Acid and Perchlorates Analytical Chemistry of Perchlorates Perchlorates in Explosives and Propellants Miscellaneous Uses of Perchlorates Safety Considerations in Handling Perchlorates [1], There is a shorter earlier review, with a detailed treatment of the potentially catastrophic acetic anhydride-acetic acid-perchloric acid system. The violently explosive properties of methyl, ethyl and lower alkyl perchlorate esters, and the likelihood of their formation in alcohol-perchloric acid systems, are stressed. The instability of diazonium perchlorates, some when damp, is discussed [2],... 

ALKYL PERCHLORATES, AMMINEMETAL OXOSALTS AMINIUM PERCHLORATES, DIAZONIUM PERCHLORATES METAL PERCHLORATES, NON-METAL PERCHLORATES PERCHLORATE SALTS OF NITROGENOUS BASES... 

Many of the salts of nitrogenous bases (particularly of high nitrogen content) with oxoacids are imstable or explosive. There are separate group entries for AMINIUM lODATES AND PERIODATES, AMINIUM PERCHLORATES DIAZONIUM PERCHLORATES, DICHROMATE SALTS OE NITROGENOUS BASES I-(I,3-DISELENONYLIDENE)PIPERIDINIUM PERCHLORATES HYDRAZINIUM SALTS, HYDROXYLAMINIUM SALTS... 

Diazobiphenyl Perchlorate. See Biphenyl-diazonium Perchlorate in Vol 1, p A191-L, under Aminobiphenyls... 

Di methyl -a inob l zcn9a4 diozc iiir f Per chlorate. Same as N,N-DimethyI-aniline-diazonium Perchlorate... 

Davis Huntress (Ref) patented the following method of prepn of diazonium perchlorates of general formula R.N2-C104, in which R is an organic radical, such as diphenyl-, nitrodiphenyl-, etc... 

The diazonium perchlorate, CaH5 N.O.Cl, mw 316.63, N 26.54%, was obtained by diazotizing nitroaminopyridylpyrazole in 4N hydrochloric acid soln, filtering the lukewarm soln and adding 70% perchloric acid. The separated crysts of the perchlorate were dried and ground in a mortar without producing an expln. The substance, however, expl with great violence when struck with a hammer or when heated to 160°... 

Preparation of m-Nitrobenzene.diazonium Perchlorate. Half a gram of m-nitroaniline is suspended in 5 ec. of water in a wide test tube, and 0.5 cc. of concentrated hydrochloric acid and 2.2 cc. of 20% perchloric acid solution are added. After the nitraniline has dissolved, 15 cc. of water is added and the solution is cooled by immersing the test tube in a beaker filled with a slurry of cracked ice. One-quarter of a gram of sodium nitrite dissolved in 1 or 2 cc. of water is added in 3 or 4 portions, the mixture being shaken after each addition or stirred with a stirring rod the end of which is covered with a short piece of rubber tubing. After standing in the cold for 5 minutes, the material is transferred to a filter, and the feltlike mass of pale yellow needles is washed with cold water, with alcohol, and with ether. The product is dried in several small portions on pieces of filter paper. 

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