Nitric oxide alkenes

Ozone ALkenes, aromatic compounds, bromine, diethyl ether, ethylene, HBr, HI, nitric oxide, nitrogen dioxide, rubber, stibine... 

A substantial portion of fhe gas and vapors emitted to the atmosphere in appreciable quantity from anthropogenic sources tends to be relatively simple in chemical structure carbon dioxide, carbon monoxide, sulfur dioxide, and nitric oxide from combustion processes hydrogen sulfide, ammonia, hydrogen chloride, and hydrogen fluoride from industrial processes. The solvents and gasoline fractions that evaporate are alkanes, alkenes, and aromatics with relatively simple structures. In addition, more complex... 

A convenient preparative method for conjugated nitroalkenes has been developed based on the reaction of nitrogen oxides. Nitric oxide (NO) is commercially available and used in the industry for the mass production of nitric acid. Nitric oxide is currently one of the most studied molecules in the fields of biochemistry, medicine, and environmental science.47 Thus, the reaction of NO with alkenes under aerobic conditions is of a renewed importance.48... 

Alkanes n-butene, isopentane, isooctane Cydoalkanes t dohezane, methylcyclopentane Olefins (sometimes called alkenes ) ethylene, propylene, butene Cydoolefins ( clohezene Alkynes acetylene Aromatics toluene, i ene CHLORINATED HYDROCARBONS ALDEHYDES, RCHO formaldehyde, acetaldehyde KETONES, RCX R " acetone, methylethylketone NITRIC OXIDE, NO ... 

Much evidence has been accumulated that the ozone-olefin reaction has a predominant role in aerosol formation from alkenes, cyclic olefins, diolefins, and other unsaturated compounds. Free radicals are formed in the reaction and can react further, along with nitric oxide and nitrogen dioxide, either with the various intermediates or with the olefin itself (see the recent review by Pitts and Finlayson ). 

In atmospheric chemistry, reactions between pure nitric oxide and a range of activated alkenes have been examined. However, no addition products were observed." Only in the presence of NO2 was addition to give jS-nitroalkyl radicals, followed by trapping to /3-nitronitroso compounds, observed. These final products can also trap other radicals to give aminoxyl radicals. 

A very remote secondary H/D isotope effect has been measured for the 2 + 2-cycloaddition of TCNE to 2,7-dimethylocta-2,fran -4,6-triene. The reaction of nitric oxide with iV-benzylidene-4-methoxyaniline to produce 4-methoxybenzenediazonium nitrate and benzaldehyde is thought to proceed via a 2 + 2-cycloaddition between nitric oxide and the imine double bond. A novel mechanism for the stepwise dimerization of the parent silaethylene to 1,3-disilacyclobutane involves a low-barrier [1,2]-sigmatropic shift. Density functional, correlated ab initio calculations, and frontier MO analysis support a concerted 2 + 2-pathway for the addition of SO3 to alkenes. " The enone cycloaddition reactions of dienones and quinones have been reviewed. The 2 + 2-photocycloadditions of homochiral 2(5H)-furanones to vinylene carbonate are highly diastereoisomeric. ... 

Park J. S. B., Walton J. C. Reactions of nitric oxide and nitrogen dioxide with functionalised alkenes and dienes. J. Chem. Soc., Perkin Trans. 2 1997 2579-83. 

There is one direct method of preparing primary diamines from alkoies, in which the alkene is treated with nitric oxide and a cobalt complex, and the intermediate worked up reductively. The two-stage reduction gives better stereoselectivity (Scheme 38). Typical yields from alkenes listed and cisurans se-lectivities (expected product first) are cyclopentene, 70%, 70 30 rr[Pg.484]

Preparation of nitronitroso dimers from a variety of straight chain alkenes has been patented. " The reactions of nitric oxide with alkenes are extremely complex (e.g. isobutylene) and are rarely usefiil. Perfluoroalkenes add nitric oxide at room temperature in the da tetraflucMoethylene gives ONCF2CF2NO (68%) the reaction with perfluoropropene is more complex. ... 

The reaction of alkenes with nitric oxide (NO), a mixture of nitric oxide and oxygen, or dinitrogen trioxide leads to /i-nitroso nitro compounds ( / -nitrosites or pseudo-nitrosites), which can convert to nitroso dimers79. Nitroalkenes are common byproducts in these reactions. The formation of /i-nitroso nitro compounds in the reaction between alkenes and nitric oxide is explained by the presence of nitrogen dioxide and dinitrogen trioxide in the nitric oxide. The reaction may be initiated by the attack of the N02 radical on the alkene to give a /i-nitroalkyl radical which then couples with nitric oxide. 

The reaction of alkenes with pure nitric oxide, however, occurs only at a pressure of 5 atmospheres or more, affording the /i-nitroso nitro compounds in rather low yields together with more complex unidentified materials80. Under these conditions it is presumed that initial disproportionation of nitric oxide occurs. 

Protonated A-nitroso amines undergo photolytic decomposition from the excited state generating transient aminium radicals and nitric oxide. Aminium radicals, which are electrophilic radicals, initiate the addition to alkenes to give //-amino nitroso compounds or oc-amino oximes (Section 7.2.5.2), however, under an oxygen atmosphere, //-nitryloxy amines (/i-amino nitrates) are produced through peroxynitrites intermediates97-99. 

The decomposition products include p-toluenesulfonic acid, amide and esters, nitric oxide and side chain alkene. 

Nitric oxide replaces ligands such as CO, tertiary phosphines, and alkenes as in the following reactions (20-22) ... 

The nitric oxide/peroxynitrite mechanism proposed for chemical sensitization illnesses 23,46 dictates that chemicals that lead to oxidative stress in the body would exacerbate the effects by increasing nitric oxide and peroxynitrite concentrations. Many of the chemicals listed in Table 26.4 as well as other heavy metals, polyaromatic hydrocarbons, haloalkanes, aromatic amines, phenols, alkenes, alcohols, and other compounds lead to increased nitric oxide and peroxynitrite concentrations. 77-81 Table 26.5 contains a partial list of these chemicals. 

Jennings and coworkers " were the first to report on a mass spectrometric method of locating double bonds by use of gas-phase ion/molecule reactions. Ionized alkyl vinyl ethers proved to be highly suitable reagent ions, and the principle of this gas-phase method for double-bond localization is illustrated for prototype dienes 76-78 in Scheme 22. At the same time. Hunt and coworkers introduced nitric oxide (NO) as a reagent gas in Cl mass spectrometry and studied the reactions of the NO+ and [NONO]+ ions with alkenes and also with several acyclic dienes and 1,3,5-cycloheptatriene. Thereafter, several groups have contributed to the development and only some classical work concerning simple alkenes may be mentioned here. 

The simplest alkene of this subgroup is propylene. Its first vacuum UV photochemistry study was published in 1965 (33) and was followed by several others (34-36). For example, at 147.0 nm, many products were identified. From partially deuterated material, as well as from the effect of added nitric oxide, the molecular formation of hydrogen and methane was observed as well as those of hydrogen... 

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