Olefinic compounds

Rea.ctlons, Vinyl ethers undergo all of the expected reactions of olefinic compounds plus a number of reactions that are both usehil and... 

The reaction mechanisms by which the VOCs are oxidized are analogous to, but much more complex than, the CH oxidation mechanism. The fastest reacting species are the natural VOCs emitted from vegetation. However, natural VOCs also react rapidly with O, and whether they are a net source or sink is determined by the natural VOC to NO ratio and the sunlight intensity. At high VOC/NO ratios, there is insufficient NO2 formed to offset the O loss. However, when O reacts with the internally bonded olefinic compounds, carbonyls are formed and, the greater the sunshine, the better the chance the carbonyls will photolyze and produce OH which initiates the O.-forming chain reactions. 

At high enough concentrations, PAN is a potent eye irritant and phytotoxin. On a smoggy day in the Los Angeles area, PAN concentrations are typically 5 to 10 ppb in the rest of the United States PAN concentrations are generally a fraction of a ppb. An important formation route for formaldehyde [50-00-0] HCHO, is reaction 9. However, o2onolysis of olefinic compounds and some other reactions of VOCs can produce HCHO and other aldehydes. 

The other important direct alkylation processes involve reaction of electron-rich olefinic compounds with either tin metal or stannous chloride (tin(II) chloride) in the presence of stoichiometric amounts of hydrogen chloride (22). Butyl acrylate (R = C Hg) was used commercially in this process to prepare the estertin or P-carboalkoxyethyltin chlorides as iHustrated in the foUowing. 

A number of activated olefinic compounds react very weU in this scheme including methacrylates, crotonates, acrylonitrile, and vinyl ketones. These reactions are typicaHy mn in an etherial solvent and can be mn without the complications of undesirable side reactions leading to trialkylated tin species. 

Solvents. Petroleum naphtha is a generic term appHed to refined, pardy refined, or unrefined petroleum products. Naphthas are prepared by any of several methods, including fractionation of distillates or even cmde petroleum, solvent extraction, hydrocracking of distillates, polymerization of unsaturated (olefinic) compounds, and alkylation processes. Naphtha can also be a combination of product streams from more than one of these processes. 

The reactive species that iaitiate free-radical oxidatioa are preseat ia trace amouats. Exteasive studies (11) of the autoxidatioa mechanism have clearly estabUshed that the most reactive materials are thiols and disulfides, heterocycHc nitrogen compounds, diolefins, furans, and certain aromatic-olefin compounds. Because free-radical formation is accelerated by metal ions of copper, cobalt, and even iron (12), the presence of metals further compHcates the control of oxidation. It is difficult to avoid some metals, particularly iron, ia fuel systems. 

P. S. Bailey, Ozonation in Organic Chemistry, Vol. 1, Olefinic Compounds, Academic Press, New York, 1978, 272 pp. Vol. 2, Nonolefinic Compounds, 1982, 496 pp. S. D. Razumovski and G. E. Zaikov, Ozone and Its Reactions with Organic Compounds, Elsevier, Amsterdam, 1984, 404 pp. 

Naphtha from atmospheric distillation is characterized by an absence of olefinic compounds. Its main constituents are straight and branched-chain paraffins, cycloparaffms (naphthenes), and aromatics, and the ratios of these components are mainly a function of the crude origin. 

Products from coking processes vary considerably with feed type and process conditions. These products are hydrocarbon gases, cracked naphtha, middle distillates, and coke. The gas and liquid products are characterized by a high percentage of unsaturation. Hydrotreatment is usually required to saturate olefinic compounds and to desulfurize products from coking units. 

Aromatization of paraffins can occur through a dehydrocyclization reaction. Olefinic compounds formed by the beta scission can form a carbocation intermediate with the configuration conducive to cyclization. For example, if a carbocation such as that shown below is formed (by any of the methods mentioned earlier), cyclization is likely to occur. 

Addition polymerization requires a chain reaction in which one monomer molecule adds to a second, then a third and so on to form a macromolecule. Addition polymerization monomers are mainly low molecular-weight olefinic compounds (e.g., ethylene or styrene) or conjugated diolefins (e.g., hutadiene or isoprene). 

In contrast to the 1,4-dithiocin system, 1,4-dioxocin (1) is well-known and has been characterized as an olefinic compound by its spectra as well as its chemical behavior.5-6 The reason why 1,4-dioxocin in contrast to 1.4-dihydro-1.4-diazocine (see Section 1.4.) and 4//-l,4-oxazocinc (sec Section 1.12.), does not qualify as a 107r-aromatic species, is the less pronounced tendency of oxygen atoms for 7t-electron delocalization. An X-ray analysis of the 6-substituted 1,4-dioxocin 2 confirms the presumed nonplanar conformation of the 1,4-dioxocin structural element.9 The eight-membered ring exhibits a twisted boat-chair confirmation. 

Oxonin (1, X = O) has polyenic character, is heavily buckled and is thermally rather unstable. Azonines 1 (X = NR) incorporating electron-withdrawing groups R on nitrogen are also uniformly characterized as olefinic compounds They are thermally labile and are decidedly atropic according to their spectroscopic data. 

This procedure gives a product free of acetylenic groups. It illustrates the synthesis of an olefinic compound by cracking a cyclobutane into two fragments. 

Employing this phosphorylating technique, Jungermann and coworkers used long-chain olefinic compounds to prepare a series of phosphinic acids. Start-... 

Although the actual reaction mechanism of hydrosilation is not very clear, it is very well established that the important variables include the catalyst type and concentration, structure of the olefinic compound, reaction temperature and the solvent. used 1,4, J). Chloroplatinic acid (H2PtCl6 6 H20) is the most frequently used catalyst, usually in the form of a solution in isopropyl alcohol mixed with a polar solvent, such as diglyme or tetrahydrofuran S2). Other catalysts include rhodium, palladium, ruthenium, nickel and cobalt complexes as well as various organic peroxides, UV and y radiation. The efficiency of the catalyst used usually depends on many factors, including ligands on the platinum, the type and nature of the silane (or siloxane) and the olefinic compound used. For example in the chloroplatinic acid catalyzed hydrosilation of olefinic compounds, the reactivity is often observed to be proportional to the electron density on the alkene. Steric hindrance usually decreases the rate of... 

Deformation of symmetrical orbital extension of carbonyl or olefin compounds was proposed to be the origin of the facial selectivities. We illustrate the unsymmetrical orbital phase environment of % orbitals of carbonyl and olefin groups and facial selectivities in Fig. 1 [3, 4]. There are in-phase and out-of-phase combinations of... 

This reviews contends that, throughout the known examples of facial selections, from classical to recently discovered ones, a key role is played by the unsymmetri-zation of the orbital phase environments of n reaction centers arising from first-order perturbation, that is, the unsymmetrization of the orbital phase environment of the relevant n orbitals. This asymmetry of the n orbitals, if it occurs along the trajectory of addition, is proposed to be generally involved in facial selection in sterically unbiased systems. Experimentally, carbonyl and related olefin compounds, which bear a similar structural motif, exhibit the same facial preference in most cases, particularly in the cases of adamantanes. This feature seems to be compatible with the Cieplak model. However, this is not always the case for other types of molecules, or in reactions such as Diels-Alder cycloaddition. In contrast, unsymmetrization of orbital phase environment, including SOI in Diels-Alder reactions, is a general concept as a contributor to facial selectivity. Other interpretations of facial selectivities have also been reviewed [174-180]. 

E. Reactions of Carbon-Carbon Double Bonds Among the most important reactions of olefinic compounds are those involving the carbon-carbon double bond. It is convenient to divide phenomena occurring... 

The reaction of ozone with olefinic compounds is very rapid. Substiments on the double bond, which donate electrons, increase the rate of reaction, while electron-withdrawing substituents slow the reaction down. Thus, the rate of reaction with ozone decreases as follows polyisoprene > polybutadiene > polychloroprene [48]. The effect of substiments on the double bond is clearly demonstrated in Tables 15.2 and 15.3. Rubbers that contain only pendant double bonds such as EPDM do not cleave since the double bond is not in the polymer backbone. 

G. Lefebvre and Y. Chauvin Dimerisation and codimerisation of olefinic compounds by coordination catalysis, pp. 108-203. 

Additional adsorption sites are provided on open metal sites, when available. [Cu3(BTC)2] is performant in the selective adsorption and separation of olefinic compounds. The highly relevant separations of propene from propane and of isobutene from isobutane have been accomplished with separation factors of 2.0 and 2.1, respectively [101, 102]. [Cu3(BTC)2] also selectively takes up pentene isomers from aliphatic solvent in liquid phase, and even discriminates between a series of cis- and trans-olefin isomer mixtures with varying chain length, always preferring a double bond in cis-position. This behavior is ascribed to tt -complexation with the open Cu sites [100]. 

At present, based on the topochemical rule, the configuration of photoproducts, as well as photoreactivity, can be precisely predicted from the crystal structure of the starting olefin compounds, with certain exceptions. 

Several pairs of isomorphous diolefin compounds have been reported to form photoreactive mixed crystals, whereas formation of the mixed crystal, comprising two olefin compounds which are not isomorphous to each other, is rare. 

All these oxidants form t-complexes by accepting electrons from olefinic bonds, a property which has been widely discussed Oxidations by these species are not, however, restricted to olefinic compounds and there is considerable evidence that they are not totally restricted to two-equivalent action. Kinetic data on their oxidations, once rare, has become profuse in the last decade both for aqueous and non-aqueous media. 

Chloro- and A TV-dichloro-phosphoramidate esters (20) and (21) are readily prepared from the parent phosphoramidate by direct chlorination in mildly acidic solution but when R = Ph, the use of t-butyl hypochlorite is preferable, to avoid chlorination of the aromatic nucleus. These compounds behave as pseudohalogens, (21) reacting with olefinic compounds such as styrene to give (22), which is also formed by chlorination of the N-phosphorylaziridine (23). ... 

A. Synthetic Methods.—Electrophilic addition of P compounds to olefinic compounds is a well-established route to phosphonic acids, although yields are often disappointing. With phosphorus pentachloride it has been found that yields are greatly improved when phosphorus trichloride is added to the reaction mixture. Since the orientation of the addition implies that electrophilic addition to phosphorus rather than chlorine is the initial step, it seems likely that the trihalide participates by decreasing the free concentration of chlorine rather than by a more active role. This... 

Esters of a-diazoalkylphosphonic acids (95) show considerable thermal stability but react with acids, dienophiles, and triphenylphosphine to give the expected products. With olefinic compounds in the presence of copper they give cyclopropane derivatives (96), but with no such compounds present vinylphosphonic esters are formed by 1,2-hydrogen shift, or, when this route is not available, products such as (97) or (98) are formed, resulting from insertion of a carbenoid intermediate into C—C or C—H bonds. The related phosphonyl (and phosphoryl) azides (99) add to electron-rich alkynes to give 1,2,3-triazoles, from which the phosphoryl group is readily removed by hydrolysis. 

The seven-membered exocyclic phosphorane (111) with the fluorene-aldehyde (112) gave triphenylphosphine and the aldehyde (114) instead of the expected olefin. Compound (114) could have been formed as shown, the phosphorane functioning as a base to generate the anion (113). 

Arene and olefin compounds, pure or in admixture, are efficient ligands in promoting the aggregation of platinum atoms from mononuclear species to ligand-stabilized soluble clusters and solid-supported nanoparticles (Scheme 14). 

New interesting applications have been in the epoxidation of difficult olefin compounds (including hexafluoropropene) with NaOCl, side-chain chlorination of substituted toluenes, diazotization of pentafluoroaniline, polymerization with free radicals, etc. 

Synthesis of optically pure compounds via transition metal mediated chiral catalysis is very useful from an industrial point of view. We can produce large amounts of chiral compounds with the use of very small quantities of a chiral source. The advantage of transition metal catalysed asymmetric transformation is that there is a possibility of improving the catalyst by modification of the ligands. Recently, olefinic compounds have been transformed into the corresponding optically active alcohols (ee 94-97%) by a catalytic hydroxylation-oxidation procedure. 

It is important for oxygen to be absent in the feed to avoid oxidation of cuprous to cupric ions rendering adsorption with reaction unworkable. This strategy can be extended to the removal/recovery of olefinic compounds, for which cuprous-exchanged zeolites may also be useful. 

An enantioselective variant of the diene cydization reaction has been developed by application of chiral zirconocene derivatives, such as Brintzinger s catalyst (12) [10]. Mori and co-workers demonstrated that substituted dial-lylbenzylamine 25 could be cyclized to pyrrolidines 26 and 27 in a 2 1 ratio using chiral complex 12 in up to 79% yield with up to 95% ee (Eq. 4) [ 17,18]. This reaction was similarly applied to 2-substituted 1,6-dienes, which provided the analogous cyclopentane derivatives in up to 99% ee with similar diastereoselectivities [19]. When cyclic, internal olefins were used, spirocyclic compounds were isolated. The enantioselection in these reactions is thought to derive from either the ate or the transmetallation step. The stereoselectivity of this reaction has been extended to the selective reaction of enantiotopic olefin compounds to form bicyclic products such as 28, in 24% yield and 59% ee after deprotection (Eq. 5) [20]. 

For the conversion of a vicinal diol into an olefinic compound via a bisimidazo-lylsulfonate or a bisiodide see Chapter 21. 

The hydrostannation of olefinic compounds in the presence of azobisisobutyronitrile AIBN is quite a well known reaction in organotin chemistry. Its mechanism is given below... 

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