Ozone, preparation

Aldaz, L. Flux measurement of atmospheric OGEone over land and water, Sectioa HI. In V. H. Regener and L. Aldaz. Eds. Studies of Atmospheric Ozone. Prepared for Air Force Cambridge Research l4iboratories. AFCRL-69-0138. Albuquerque Uni versity of New Mexico, Department of Physics and Astronomy, 1%9. 12 pp. 

Oxybutynin, 93 Oxycodone, 290 Oxymercuration, 224 Oxymestrone, 173 Oxymetazoline, 242 Oxymetholone, 173 Oxymorphone, 290, 291 Oxypendyl, 430 Oxyphenbutazone, 236 Oxyprenolol, 117 Oxypurinol, 426 Oxytetracycline, 212 Ozonization, preparative, 158... 

The sensitivity of the analyzer was determined by circulating synthetic mixtures of air and ozone prepared from 100% ozone with successive dilutions with air these mixtures were prepared by members of the Ozone Technology Group. 

Effect of Concentration and Time. A study was made in mice to determine whether ozone obeyed the toxicologic rule that the product of the concentration and time of exposure produced a constant, toxicologic response, CT = K, over a concentration range of from 1 to 50 p.p.m. If a positive correlation is found, such information permits interpolation and extrapolation of the variables of exposure without the labor of experimental determination. A plot of the values in Table II from 2.5 to 50 p.p.m. of ozone shows reasonably good linearity, with the exception of the single response to 4 p.p.m. of ozone prepared from air. When the entire experience of the other three tests at this level was used, however, close agreement to linearity was found. No fatal... 

Pure ozone, prepared from pure tank oxygen and mixed with air purified by careful scrubbing, is of itself highly toxic. 

Addition compounds called ozonides are produced when alkenes react with ozone and reductive cleavage of these compounds is used extensively in preparative and diagnostic organic chemistry. 

How would you obtain a sample of pure ozone Account for the conditions used in your method of preparation. What is the arrangement of oxygen atoms in an ozonide and what evidence would you cite in support of the structure you suggest ... 

The superacid-catalyzed electrophile oxygenation of saturated hydrocarbons, including methane with hydrogen peroxide (via H302 ) or ozone (via HOs ), allowed the efficient preparation of oxygenated derivatives. 

One of the chief uses of chloromethane is as a starting material from which sili cone polymers are made Dichloromethane is widely used as a paint stripper Trichloromethane was once used as an inhalation anesthetic but its toxicity caused it to be replaced by safer materials many years ago Tetrachloromethane is the starting mate rial for the preparation of several chlorofluorocarbons (CFCs) at one time widely used as refrigerant gases Most of the world s industrialized nations have agreed to phase out all uses of CFCs because these compounds have been implicated m atmospheric processes that degrade the Earth s ozone layer... 

Phosphoms oxyfluoride is a colorless gas which is susceptible to hydrolysis. It can be formed by the reaction of PF with water, and it can undergo further hydrolysis to form a mixture of fluorophosphoric acids. It reacts with HF to form PF. It can be prepared by fluorination of phosphoms oxytrichloride using HF, AsF, or SbF. It can also be prepared by the reaction of calcium phosphate and ammonium fluoride (40), by the oxidization of PF with NO2CI (41) and NOCl (42) in the presence of ozone (43) by the thermal decomposition of strontium fluorophosphate hydrate (44) by thermal decomposition of CaPO F 2H20 (45) and reaction of SiF and P2O5 (46). 

Tetrafluoroethylene Oxide TFEO has only been prepared by a process employing oxygen or ozone because of its extreme reactivity with ionic reagents. This reactivity may best be illustrated by its low temperature reaction with the weak nucleophile, dimethyl ether, to give either of two products (47) (eq. 10). 

Many of the chemical reactions used to modify lignosulfonates are also used to modify kraft lignins. These include ozonation, alkaline—air oxidation, condensation with formaldehyde and carboxylation with chloroacetic acid (100), and epoxysuccinate (101). In addition, cationic kraft lignins can be prepared by reaction with glycidjiamine (102). 

Ttinitroparaffins can be prepared from 1,1-dinitroparaffins by electrolytic nitration, ie, electrolysis in aqueous caustic sodium nitrate solution (57). Secondary nitroparaffins dimerize on electrolytic oxidation (58) for example, 2-nitropropane yields 2,3-dimethyl-2,3-dinitrobutane, as well as some 2,2-dinitropropane. Addition of sodium nitrate to the anolyte favors formation of the former. The oxidation of salts of i7k-2-nitropropane with either cationic or anionic oxidants generally gives both 2,2-dinitropropane and acetone (59) with ammonium peroxysulfate, for example, these products are formed in 53 and 14% yields, respectively. Ozone oxidation of nitroso groups gives nitro compounds 2-nitroso-2-nitropropane [5275-46-7] (propylpseudonitrole), for example, yields 2,2-dinitropropane (60). 

The relevant properties of peroxide and superoxide salts are given in Table 4 (see Peroxides and peroxide compounds, inorganic). Potassium peroxide is difficult to prepare and lithium superoxide is very unstable. The ozonides, MO3, of the alkah metals contain a very high percentage of oxygen, but are only stable below room temperature (see Ozone). 

The unstable ammonium ozonide [12161 -20-5] NH O, prepared at low temperatures by reaction of ozone withHquid ammonia, decomposes rapidly at room temperature to NH NO, oxygen, and water (51). Tetrametbylammonium ozonide [78657-29-1] also has been prepared. 

Commercial production and utilization of ozone by silent electric discharge consists of five basic unit operations gas preparation, electrical power supply, ozone generation, contacting (ie, ozone dissolution in water), and destmction of ozone in contactor off-gases (Fig. 1). 

The pharmaceutical industry employs ozone in organic reactions to produce peroxides as germicides in skin lotions, for the oxidation of intermediates for bacteriostats, and in the synthesis of steroids (qv) such as cortisone (see Disinfectants and antiseptics). Vitamin E can be prepared by ozonation of trimethyUiydroquinone. 

The ozonides are characterized by the presence of the ozonide ion, O - They are generally produced by the reaction of the inorganic oxide and ozone (qv). Two reviews of ozonide chemistry are available (1,117). Sodium ozonide [12058-54-7] NaO potassium ozonide [12030-89-6] 35 rubidium ozonide [12060-04-7] RbO and cesium ozonide [12053-67-7] CsO, have all been reported (1). Ammonium ozonide [12161 -20-5] NH O, and tetramethylammonium ozonide [78657-29-1/, (CH ) NO, have been prepared at low temperatures (118). 

Thermally unstable cycHc trioxides, 1,2,3-trioxolanes or primary o2onides are prepared by reaction of olefins with o2one (64) (see Ozone). Dialkyl trioxides, ROOOR, have been obtained by coupling of alkoxy radicals, RO , with alkylperoxy radicals, ROO , at low temperatures. DiaLkyl trioxides are unstable above —30° C (63). Dialkyl tetraoxides, ROOOOR, have been similarly produced by coupling of two alkylperoxy radicals, ROO , at low temperatures. Dialkyl tetraoxides are unstable above —80°C (63). 

Alkoxyall l Hydroperoxides. These compounds (1, X = OR , R = H) have been prepared by the ozonization of certain unsaturated compounds in alcohol solvents (10,125,126). 2-Methoxy-2-hydroperoxypropane [10027-74 ] (1, X = OR , R" = methyl), has been generated in methanol solution and spectral data obtained (127). A rapid exothermic decomposition upon concentration of this peroxide in a methylene chloride—methanol solution at 0°C has been reported (128). 2-Bromo-l-methoxy-l-methylethylhydroperoxide [98821-14-8]has been distilled (bp 60°C (bath temp.), 0.013 kPa) (129). Two cycHc alkoxyaLkyl hydroperoxides from cyclodecanone have been reported (1, where X = OR R, R = 5-oxo-l, 9-nonanediyl) with mp 94—95°C (R" = methyl) and mp 66—68°C (R" = ethyl) (130). Like other hydroperoxides, alkoxyaLkyl hydroperoxides can be acylated or alkylated (130,131). 

Titanium oxide dichloride [13780-39-8] TiOCl2, is a yellow hygroscopic soHd that may be prepared by bubbling ozone or chlorine monoxide through titanium tetrachloride. It is insoluble in nonpolar solvents but forms a large number of adducts with oxygen donors, eg, ether. It decomposes to titanium tetrachloride and titanium dioxide at temperatures of ca 180°C (136). 

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