Allylic compounds 2- acrylonitrile

The activity of transition metal allyl compounds for the polymerization of vinyl monomers has been studied by Ballard, Janes, and Medinger (10) and their results are summarized in Table II. Monomers that polymerize readily with anionic initiators, such as sodium or lithium alkyls, polymerize vigorously with allyl compounds typical of these are acrylonitrile, methyl methacrylate, and the diene isoprene. Vinyl acetate, vinyl chloride, ethyl acrylate, and allylic monomers do not respond to these initiators under the conditions given in Table II. 

The free radical copolymerization of methyl methacrylate or acrylonitrile in the presence of zinc chloride with allylic compounds such as allyl alcohol, allyl acetate, and allyl chloride or butene isomers such as isobutylene, 1-butene, and 2-butene is characterized by the incorporation of greater amounts of comonomer than is noted in the absence of zinc chloride (35). Analogous to the radical homopolymerization of allylic monomers in the presence of zince chloride, the increase in the electron-accepting capability of the methyl methacrylate or acrylonitrile as a result of complexation results in the formation of a charge transfer complex which undergoes homopolymerization and/or copolymerization with a polar monomer-complexed polar monomer complex. 

Catalysts are now known that facilitate the metathesis of olefins containing all types of functional groups. Such reactions are described for acyclic olefins in Ch. 7, and for cyclic olefins in Ch. 12 and 13. Not only can allyl compounds be metathesized (Mol 1979), reaction (9), but even acrylonitrile will undergo crossmetathesis (Crowe 1995). 

Besides acrylonitrile and acrylates other functional olefins such as vinyl or allyl compounds can also be dimerized. An important example for vinyl compounds is styrene, which can be dimerized to 1,3-diphenyH-butene. Owing to its high tendency to poljmerize spontaneously, the reaction conditions must be chosen carefuUy. Thus the dimerization catalyzed by PdCl2 at 100 °C yielded only 33% of a dimer fraction with more than 60% of a dark polymeric residue [49]. Using Ni( 1/ -03115)2 as the catalyst, styrene is converted to l,3-diphenyl-/mn5-l-butene [58, 59]. With [PdCl r] -C,U,)] dimers and trimers are obtained (Equation 43) [60]. 

Class 6 Poisons such as acetone cyanohydrin, acetonitrile, acrylonitrile, allyl alcohol, allyl chloride, airiline, epiclilorohydrin, lead alkyls, organophosphorus compounds. 

Individually indexed compounds are f Acetonitrile, 0758 f Acrylonitrile, 1107 Allyl isothiocyanate, 1471... 

Oxidation of the allylic carbon of alkenes may lead to allylic alcohols and derivatives or a, 3-unsaturated carbonyl compounds. Selenium dioxide is the reagent of choice to carry out the former transformation. In the latter process, which is more difficult to accomplish, Cr(VI) compounds are usually applied. In certain cases, mixture of products of both types of oxidation, as well as isomeric compounds resulting from allylic rearrangement, may be formed. Oxidation of 2-alkenes to the corresponding cc,p-unsaturated carboxylic acids, particularly the oxidation of propylene to acrolein and acrylic acid, as well as ammoxidation to acrylonitrile, has commercial importance (see Sections 9.5.2 and 9.5.3). 

Reactivity studies of compounds of this class have received little attention. Aryl-substituted complexes (161) (Rsj, = Ar) are, under heat and photolysis, sources of radical coupling reactions with acrylonitrile to give predominantly (189). As the conditions for reaction are also sufficient for conversion of the corresponding (jj -allyl)Fp complexes (12) to (161), compounds of type (12) may also be used as reageuts. ... 

AH catalysts claimed are multi-functional systems. Indeed, the formation of acrylonitrile from propane occurs mainly via the intermediate formation of propene, which is then transformed to acrylonitrile via the allylic intermediate. It follows that the catalyst possesses different kinds of active site one site that is able to activate the paraffin and oxidehydrogenates it to the olefin, and one site that (amm)oxidizes the adsorbed olefinic intermediate. This second step must be very rapid to limit, as much as possible, the desorption of the olefin. In order to develop an effective cooperation between the two sites, it is necessary to have systems in which they are in close proximity. The muIti-functionaHty is achieved either through the combination of two different compounds (phase-cooperation), or through the presence of different elements inside a single crystaUine structure. In antimonate-based systems, the cooperation between the metal antimonate (having the rutile crystalline structure), responsible for propane oxidative dehydrogenation to propene and propene activation, and antimony oxide, active in allylic ammoxidation, is made more efficient through the dispersion of the latter compound over... 

Acrylates Acrylonitriles Allyl Esters Cellulose esters Epoxies Ethylenic (unsaturated) hydrocarbons Poly-hydroxy esters(eg Pentaerythritol tetramethacrylate,Ethylene Glycol diacrylate) Polyolefins Vinyl compound esters, acids)... 

The rate of conversion of propane is practically the same in the presence and in the absence of ammonia. The oxidation yields propylene and carbon oxides, which are the prevailing products. However, when ammonia is added to the feedstock, the yield to propylene remains unchanged, while the yield to carbon oxides is remarkably decreased in favour of the formation of acrylonitrile. This suggests that in the absence of ammonia the propylene is oxidized to a compound or to an intermediate which under these conditions is burnt to carbon oxides. The addition of ammonia allows this intermediate compound (which might be acrolein or an allyl radical species) to be quickly transformed to the stable... 

Ammoxidation refers to the formation of nitriles by oxidation of hydrocarbons with oxygen in the presence of ammonia (Figure 1) [1]. Ammoxidation is best conducted with olefins, or with aromatic or heteroaromatic compounds, containing a readily abstractable H atom (allylic or benzylic intermediates are formed), although the ammoxidation of alkanes (e. g. propane to acrylonitrile [e. g. 2-4] or ethane to acetonitrile [e. g. 5]) is also possible. An exceptional example is the ammoxidation of methane to hydrogen cyanide by the Andrussov reaction [6]. 

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