Organic perchlorates

The silver perchlorate [7783-93-9] salt, AgClO, is dehquescent and forms a light-sensitive monohydrate that can be dehydrated at 43°C and is soluble in a variety of organic solvents. Explosions of silver perchlorate have been reported (40—42). Gold forms organic perchlorate [42774-61-8] complexes as well as complexes with silver, eg, (CgH )2AgAu(CgF )2C104. 

Phenylacetylene reacts with anhydrous perchloric acid at -180°C and forms an organic perchlorate, which decomposes violently at a temperature starting at -78°C. The following reaction has been suggested ... 

Except with nitric acid, most dangerous reactions are those of alcohols with perchloric acid or its salts (that can form acid). All accidents reported are caused by the formation of highly unstable organic perchlorates. 

Reaction gives explosive volatile organic perchlorates, probably ethyl perchlorate. 

Traces of perchloric acid used as hydration catalyst for ring opening of nitrogenous epoxides caused precipitation of an organic perchlorate salt which was highly explosive. The concentration of acid was less than 1% by vol. 

The thermal stability, structures and physical properties of various non-metal perchlorates (nitrosyl, nitronium, hydrazinium, ammonium, etc.) have been reviewed [1], Many organic perchlorates were examined for sensitivity to impact. The salts of cations containing only C, H and S exploded quite consistently, while those with C, H, and N, or C, H, N, and S did not explode, except 1,2-bis(ethylammonio)ethane diperchlorate [2],... 

H. E. Roscoe s cupric salt is supposed to be cupric hexammino-diaquo-perchlorate, [Cu(NH3)4(H20)2](C104)2. Hydrated ferric perchlorate is likewise regarded as [Fe(H2O)0](ClO4.H2O)3. A number of organic perchlorates have been prepared by K. K. A. Hobold,27 R. Roth, and A. G. von Zedtwitz. 

For a review of the synthesis and reactions of organic perchlorates, sec Zefirov Zhdankin Koz min Russ. Chem. Rev 1988, 57. 1041-1053. 

Perchlorates and perchloric acid. At 160° perchloric acid is an exceedingly strong oxidising acid and a strong dehydrating agent. Organic perchlorates, such as methyl and ethyl perchlorates, are unstable and are violently... 

Group 14 (IVA) Perchlorates. Perchlorates containing organic carbon have been reported, as have diazomum perchlorates, oxonium perchlorates, and the perchlorate esters. Extreme caution must be used in working with organic perchlorates many decompose violently when healed, contacted with other reagents, or subjected to mechanical shock. 

This organic oxidant, initially claimed a safe reagent, later showed the treacherous explosibility normal to organic perchlorates. The far less hazardous tetrafluoroborate is an equally effective reagent. 

Mixtures of inorganic perchlorates with combustible materials are readily ignited mixtures with finely divided combustible materials frequently react explosively. Organic perchlorates are self-contained explosives.1... 

Synthesis of new inorganic or organic perchlorates should only be undertaken by an experienced, cautious, investigator who is familiar with the literature. 

The oxidation of tertiary amines other than trimethylamine with organic perchlorates, aimed at producing salts 35, has also been carried out. ... 

Avoid skin contact. Flammable by chemical reaction powerful oxidizers. All perchlorates are potentially hazardous when in contact with reducing materials. Moderate explosion hazard when shocked or exposed to heat or by chemical reaction. Perchlorates, when mixed with carbonaceous material, form explosive mixtures. Many perchlorates of nitrogenous bases (e.g., hydroxylamine, urea, methylamine, ethylamine, isopropylamine, 4-ethylpyridine, diaminoethane) and organic perchlorates are explosives. Diazonium perchlorates are very dangerous. All perchlorates are considered to be fire and explosive hazards when associated with carbonaceous materials or finely divided metals. This is also true in the presence of calcium hydride, sulfur,... 

Caution. In view of the well-known shock sensitivity of organic perchlorates, 1-ethyl-l-phenylphospholanium perchlorate should be handled with care. Attempts to detonate 1-6 mg samples with a hammer on a concrete surface failed to produce an explosion. It is quite probable that salts with the PFi ion can be produced by using KPFf, in place of NaClO, but this is not done in the present example. 

Among the strong oxidizing agents, perchloric acid is probably the most hazardous. It can form heavy metal and organic perchlorates that are explosive, and it can react explosively if it comes in contact with organic compounds. 

Caution must be exercised when handling perchlorates. Silver perchlorate is explosive grinding it in a mortar should be avoided. For use in reference electrodes, it may be prepared by anodic dissolution of silver in a perchlorate medium [202]. Evaporation of solutions of organic perchlorates is discouraged but, if necessary, must occur in vacuo and at moderate temperatures. Even sodium perchlorate, which can be dried at 100°C without undue risk, may cause explosions when heated with an organic solvent. 

---