Ozonides organic

BQDI 53 is the principal product of both sacrificial and depleting transformations of PD in model hydrocarbons, PO and rubbers and is formed via oxidation with ROO , oxygen, ozone, ozonides, organic peroxides or ions of transition metals. BQDI have therefore been found in PD doped polymers degraded under various conditions [3-5,58]. They are formed in high preparative yield by oxidation with femcyanide and also result in interactions of PD with some rubber chemicals, e.g, with benzothiazolyl-2-sulfenemorpholide. 

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. 

Organic peroxides are highly explosive, hence it is best to carry out the ozonisation in a solvent which dissolves both the original compound and the ozonide. 

AH of the commercial inorganic peroxo compounds except hydrogen peroxide are described herein, as are those commercial organic oxidation reactions that are beheved to proceed via inorganic peroxo intermediates. Ozonides and superoxides are also included, but not the dioxygen complexes of the transition metals. 

Organic peroxides can be classified according to peroxide stmcture. There are seven principal classes hydroperoxides dialkyl peroxides a-oxygen substitued alkyl hydroperoxides and dialkyl peroxides primary and secondary ozonides peroxyacids diacyl peroxides (acyl and organosulfonyl peroxides) and alkyl peroxyesters (peroxycarboxylates, peroxysulfonates, and peroxyphosphates). 

H. Ozonizalion of organic compounds. The ozonization of each unsaturated organic compound is more or less an individual problem, but some general comments may be made. Organic ozonides are highly explosive, and hence it is safest to carry out the ozonization in a solvent which dissolves both the original compound and the ozonide. In all cases, a shatterproof screen of laminated safety glass should be placed between the operator and the tubes H, I, and J. A second screen should be placed back of the tubes to protect other pieces of the apparatus. 

The principal organic reaction of ozone is its addition to the carbon-carbon double bond of an ethylenic compd. The resulting ozone-olefin addition compd is known as an ozonide. Decompn of the ozonide gives a mixt of oxygenated products containing carbonyl compds and acids. 

The reaction of ozone with an unsaturated organic compd was reported more than a century ago (Schonbein, JPraktChem 66, 282 (1855)), however, complete explanation of this reaction has not been made until recent times. In 1905, Harries (Ref 1) postulated that the addition of ozone to an olefin resulted in the formation of an ozonide according to the formula ... 

Urushioldimethylethertetraozonide (Tetra-ozonide des Urushiol-dunethylathers in Ger). C22H3402(03)4, yel, semi-solid substance explds violently when heated to about 60°, or when touched by a flame. Prepd by Majima (Ref 2) by passing 15% ozone thru a chloroform soln of dimethylurushiol, cooled in ice, for 10 hours, After removal of the chlf in vac, the residue was dissolved in ether and pptd by hexane Refs 1) Beil — not found 2) R. Majima, Ber 42,3667-72(1909) 3) P. Karrer, Organic... 

Also, see under Organic Hydroperoxides in Vol 7, H224-R to H227-R and under Ozonides in this Vol... 

O-O-H (hydroperoxide), ozonides, -C(0)-O-O-H peracids, -0-0- (peroxide), and -0-0-0-connected to inorganic or organic radicals ... 

Ozone is a useful oxidizing agent in organic reactions, especially when double bonds are involved. The product of such a reaction is known as an ozonide, and the general reaction can be shown as... 

The reducing properties of organic compounds of sulfur, such as methyl mercaptan, show up in partial reduction of trigeminal to geminal dihalides [243]. Dimethyl sulfide reduces hydroperoxides to alcohols and ozonides to aldehydes while being converted to dimethyl sulfoxide [244]. 

Significant advances in the chemistry of these ring systems over the past 10 years include the first unambiguous detection, and characterization by microwave spectroscopy as 1,2,3-trioxolane, of the primary ozonide from ethene and ozone (cf. Section 4.15.3.2), and the introduction of 1,3,2-dioxathiolane 2,2-dioxides as epoxide equivalents in organic synthesis (cf. Section 4.15.5.3). Advances have also been made in the synthesis and characterization of the chemistry of 1,2,3-trithiolanes and 1,2,3-trithioles. 

Ozone reacts with organics, attacking most kinds of double bonds. It reacts with ethylene forming ethylene ozonide, a cyclic compound containing three oxygen atoms ... 

O NMR spectroscopy of organic compounds containing the —0—0—group 175 TABLE 3. NMR data of ozonides 6-14"... 

Temperature-programmed thermal desorption particle beam MS of collected secondary aerosol particles shows that the major ozonization products of normal alkenes in an environmental chamber include organic hydroperoxides, peroxides, final ozonides and monocarboxylic acids. Attempts to analyze these compounds by GC result in their decomposition to simpler molecules". 

The structure of 113a was established by single-crystal X-ray analysis. The Ge—O, Ge—C and 0—0 bond distances are essentially within the range of normal valnes. The dihedral angle between the 0—0 bond and the plane containing the Ge(l), C(l) and Ge(2) atoms is 57.7°. These features are comparable to those of the well-known, structurally related organic ozonides. ... 

Gas electron diffraction (GED) acyl peroxides, 702 peroxynitrates, 743-4 see also Electron diffraction Gas-hqiud chromatography (GLC) hydroperoxide determination, 684-5 ozonide determination, 719 Gas-phase addition, hydroperoxides, 157 Gas-phase epoxidation, alkenes, 58 gauche arrangement, acyclic organic peroxides, 102, 104-5 GED (gas electron diffraction), 743-4 Geminal regioselectivity... 

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