Ammonia reactions with ozone

TS-1 is a material that perfectly fits the definition of single-site catalyst discussed in the previous Section. It is an active and selective catalyst in a number of low-temperature oxidation reactions with aqueous H2O2 as the oxidant. Such reactions include phenol hydroxylation [9,17], olefin epoxida-tion [9,10,14,17,40], alkane oxidation [11,17,20], oxidation of ammonia to hydroxylamine [14,17,18], cyclohexanone ammoximation [8,17,18,41], conversion of secondary amines to dialkylhydroxylamines [8,17], and conversion of secondary alcohols to ketones [9,17], (see Fig. 1). Few oxidation reactions with ozone and oxygen as oxidants have been investigated. 

Ozonides, MO3, containing the paramagnetic, bent [03] ion (see Section 15.4), are known for all the alkali metals. The salts KO3, Rb03 and CSO3 can be prepared from the peroxides or superoxides by reaction with ozone, but this method fails, or gives low yields, for LiOs and NaOs. These ozonides have recently been prepared in liquid ammonia by the interaction of CSO3 with an ion-exchange resin loaded with either Li or Na ions. The ozonides are violently explosive. 

Fig. 3. compares the ammonia conversion for nanostructured vanadia/TiOa catalysts pretreated with O2 and 100 ppm O3/O2 gases. The reactions were conducted at 348 K for 3 h. No N2O and NO byproducts were detected in the reactor outlet. It is clear from the figure that higher vanadium content is beneficial to the reaction and ozone pretreatment yields a more active catalyst. Unlike the current catalysts, which require a reaction temperature of at least 473 K, the new catalyst is able to perform at much lower temperature. Also, unlike these catalysts, complete conversion to nitrogen was achieved with the new catalysts. Table 2 shows that the reaction rate of the new catalysts compared favorably with the established catalysts. 

Chemical/Physical. The gas-phase reaction of ozone with pyridine in synthetic air at 23 °C yielded a nitrated salt having the formula [CeHsNHJ NOs (Atkinson et al., 1987). Ozonation of pyridine in aqueous solutions at 25 °C was studied with and without the addition of ferf-butyl alcohol (20 mM) as a radical scavenger. With tert-hniyX alcohol, ozonation of pyridine yielded mainly pyridine W-oxide (80% yield), which was very stable towards ozone. Without terf-butyl alcohol, the heterocyclic ring is rapidly cleaved forming ammonia, nitrate, and the amidic compound W-formyl oxamic acid (Andreozzi et al., 1991). 

The Ozonide Ion.—The red crystalline substance potassium ozonide, KO3, is obtained by recrystallizing from liquid ammonia the product of reaction of ozone and potassium hydroxide.47 The corresponding ozonides NaO and CsO hasre been shown48 to have magnetic susceptibility corresponding to the presence of the OjT ion with one odd electron. The electronic structure of the ozonide ion is... 

One approach to unnatural amino acids is to use a readily available amino acid, such as L-phenyl-alanine, as the starting material. The Birch reduction of L-phenylalanine (1) was carried out with lithium in ammonia, followed by acylation of the amino group to produce compound 2, which was further esterihed to produce the cyclohexa-l,4-dienyl-L-alanine derivative 3 (Scheme 11.1). The ozonolysis step of the reaction was carried out at -78°C in a dichloromethane solution presaturated with ozone to reduce the extent of oxidation of the diene 3 to produce 4. Cyclization was then carried out by the introduction of either hydroxylamine hydrochloride to produce the isoxazol-5-ylalanine derivative 5 or phenylhydrazine to give a 1 1 mixture of (l-phenylpyrazol-3-yl)alanine derivative 6 and the (l-phenylpyrazol-2-yl)alanine derivative 7.4,5... 

SAFETY PROFILE Poison by inhalation. Potentially explosive decomposition at 200°C. Flammable when exposed to heat or flame. Explosive reaction with ammonia + heat, chlorine, concentrated nitric acid, ozone. Incompatible with oxidants. The decomposition products are hydrogen and metallic antimony. When heated to decomposition it emits toxic fumes of Sb. Used as a fumigating agent. See also ANTIMONY COMPOUNDS and HYDRIDES. 

OLSZYNA AND HEicKLEN Reaction of Ozone with Ammonia... 

---