Alkyl perchlorates

Chlorine heptoxide is more stable than either chlorine monoxide or chlorine dioxide however, the CX C) detonates when heated or subjected to shock. It melts at —91.5°C, bods at 80°C, has a molecular weight of 182.914, a heat of vapori2ation of 34.7 kj/mol (8.29 kcal/mol), and, at 0°C, a vapor pressure of 3.2 kPa (23.7 mm Hg) and a density of 1.86 g/mL (14,15). The infrared spectmm is consistent with the stmcture O CIOCIO (16). Cl O decomposes to chlorine and oxygen at low (0.2—10.7 kPa (1.5—80 mm Hg)) pressures and in a temperature range of 100—120°C (17). It is soluble in ben2ene, slowly attacking the solvent with water to form perchloric acid it also reacts with iodine to form iodine pentoxide and explodes on contact with a flame or by percussion. Reaction with olefins yields the impact-sensitive alkyl perchlorates (18). 

Acyl or alkyl nitrates Alkyl perchlorates Aminemetal oxosalts Arenediazo aryl sulfides Arenediazoniiimolates Azo compounds... 

O-X Alkyl perchlorates. Chlorite salts. Halogen oxides, Hypohalites, Perchloric acid, Perchloryl Compounds... 

The mechanism of these reactions is usually Sn2 with inversion taking place at a chiral RX, though there is strong evidence that an SET mechanism is involved in certain cases, ° especially where the nucleophile is an a-nitro carbanion and/or the substrate contains a nitro or cyano group. Tertiary alkyl groups can be introduced by an SnI mechanism if the ZCH2Z compound (not the enolate ion) is treated with a tertiary carbocation generated in situ from an alcohol or alkyl halide and BF3 or AlCla, or with a tertiary alkyl perchlorate. ... 

Distillation of mixtures with Ci -C3 alcohols gives the highly explosive alkyl perchlorates. Extreme shock-sensitivity is still shown by n-octyl perchlorate. 

The high explosive instability is due in part to the covalent character of the alkyl perchlorates, and also to the excess of oxygen in the molecule over that required to combust completely the other elements present (i.e. a positive oxygen balance). 

Propyl perchlorate [22755-14-2] Pr0C103 See entry alkyl perchlorates c3h7cio4... 

Propyl perchlorate [52936-53-1] Me2CH0C103 See entry alkyl perchlorates (reference 6) c3h7cio4... 

See related alkyl perchlorates, perchlorate salts of nitrogenous bases,... 

See Glycols and their ethers and Methanol, Triglycerides both below See ALKYL PERCHLORATES... 

See Other ALKYL PERCHLORATES, halogenation incidents Chloromethane... 

The anhydrous salt which had been used for drying unsaturated hydrocarbons exploded on heating to 220° C for reactivation. The need to avoid contact with acidic materials is stressed. (Traces of an alkyl perchlorate may conceivably have been formed from free perchloric acid). 

See related alkyl perchlorates See other metal perchlorates... 

Methyl, ethyl and propyl perchlorates, readily formed from the alcohol and anhydrous perchloric acid, are highly explosive oils, sensitive to shock, heat and friction [1], Many of the explosions which have occurred on contact of hydrox-ylic compounds with cone, perchloric acid or anhydrous metal perchlorates are attributable to the formation and decomposition of perchlorate esters [2,3,4], Safe procedures for preparation of solutions of 14 sec-alkyl perchlorates are described. Heated evaporation of solvent caused explosions in all cases [5], l-Chloro-2-propyl, iram-2-chlorocyclohexyl, l-chloro-2-propyl, 1,6-hexanediyl, hexyl, and 2-propyl perchlorates, prepared by a new method, are all explosive oils [6],... 

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... 

The need for great care to avoid the possibility of detonation of perchloryl compounds by exposure to shock, overheating or sparks is stressed. The compounds are generally more sensitive to impact than mercury fulminate and are of comparable sensitivity to lead azide [1], A range of highly explosive alkyl perchlorates [2] and perchlorylamines [3] have been prepared by interaction of dichlorine heptaoxide with alcohols or amines in carbon tetrachloride solution. The solutions of the products were not sensitive to mechanical shock and could... 

ALKYL PERCHLORATES AMINIUM PERCHLORATES CHLORITE SALTS HALOGEN OXIDES HYPOHALITES PERCHLORYL COMPOUNDS... 

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