2-Propene nitrile

In Figure 1.6.1 the conceptual differences between atom, bond, and function-oriented GCMs are demonstrated for propene nitrile. The symbols -, =, and denote a single, double, and triple bond, respectively. Note, for example, the different representations of the Csp atom in propene nitrile. (See chemistry texts for sp notation.) In the atom contribution approach, Csp is identified as -C. spn indicates... 

Figure 1.6.1 Various group contribution types for propene nitrile. The SMILES rotation is used to indicate the groups. The Csp hybridize carbon atom is in bold.

Acrylonitrile (2-propenonitrile, propene nitrile, vinyl cyanide, CH2=CHCN freezing point -83.5°C, boiling point 77.3°C, density 0.806) used to be manufactured completely from acetylene by reaction with hydrogen cyanide. 

Lignin has been grafted with ethenylbenzene [43,44] (styrene), 4-methyl-2-oxy-3-oxopent-4-ene [45,46] (methylmethacrylate), 2-propenamide (acrylamide), 2-propene nitrile [47] (acrylonitrile), cationic monomers, anionic monomers, and propenoic acid ethoxylates. An index of compounds listing structure, product name, and trivial name is given in Table 3. Two types of... 

SYNS 2-ACRYLONITRILE, 1-HYDROXYETHYL- 2-(l-HYDROXYETHYL)ACRYLONITRILE 2-PROPENE-NITRILE, (2-HYDROXYETHYL)-... 

The Diels-Alder cycloaddition reaction occurs most rapidly and in highest yield if the alkene component, or dienophile ( diene lover ), has an electron-withdrawing substituent group. Thus, ethylene itself reacts sluggishly, but propenal, ethyl propenoate, maleic anhydride, benzoquinone, propene-nitrile, and others are highly reactive. Note also that alkynes, such a.s methyl propynoate, can act as Diels-Alder dienophiles. 

First number = weight of 2-propene nitrile added and second number = weight of 2-propenamide added. 

An important nitrile is acrylonitrile H2C=CHCN It is prepared industrially from propene ammonia and oxygen m the presence of a special catalyst Polymers of acryl omtrile have many applications the most prominent being their use m the preparation of acrylic fibers... 

At higher temperatures, propene and NH, react over basic catalysts to afford a mixture of nitriles (Eq. 4.2) [42]. 

Otera et al. extended the tin-mediated allylation to 2-substituted allyl bromides.80 When 2-bromo and 2-acetoxy-3-bromo-l-propene were used, the allylation with tin produced the corresponding functionalized coupling products (Eqs. 8.36 and 8.37). In the case of 2,3-dibromopropene, the reaction occurred exclusively through allylation in the presence of the vinyl bromo group. The presence of other electrophiles such as a nitrile (-CN) or an ester (-COOR) did not interfere with the reaction. 

It is believed that SCR by hydrocarbons is an important way for elimination of nitrogen oxide emissions from diesel and lean-burn engines. Gerlach etal. [115] studied by infrared in batch condition the mechanism of the reaction between nitrogen dioxide and propene over acidic mordenites. The aim of their work was to elucidate the relevance of adsorbed N-containing species for the F>cNOx reaction to propose a mechanism. Infrared experiments showed that nitrosonium ions (NO+) are formed upon reaction between NO, NOz and the Brpnsted acid sites of H—MOR and that this species is highly reactive towards propene, forming propenal oxime at 120°C. At temperatures above 170°C, the propenal oxime is dehydrated to acrylonitrile. A mechanism is proposed to explain the acrylonitrile formation. The nitrile can further be hydrolysed to yield... 

In the direct ammoxidation of propane over Fe-zeolite catalysts the product mixture consisted of propene, acrylonitrile (AN), acetonitrile (AcN), and carbon oxides. Traces of methane, ethane, ethene and HCN were also detected with selectivity not exceeding 3%. The catalytic performances of the investigated catalysts are summarized in the Table 1. It must be noted that catalytic activity of MTW and silicalite matrix without iron (Fe concentration is lower than 50 ppm) was negligible. The propane conversion was below 1.5 % and no nitriles were detected. It is clearly seen from the Table 1 that the activity and selectivity of catalysts are influenced not only by the content of iron, but also by the zeolite framework structure. Typically, the Fe-MTW zeolites exhibit higher selectivity to propene (even at higher propane conversion than in the case of Fe-silicalite) and substantially lower selectivity to nitriles (both acrylonitrile and acetonitrile). The Fe-silicalite catalyst exhibits acrylonitrile selectivity 31.5 %, whereas the Fe-MTW catalysts with Fe concentration 1400 and 18900 ppm exhibit, at similar propane conversion, the AN selectivity 19.2 and 15.2 %, respectively. On the other hand, Fe-MTW zeolites exhibit higher AN/AcN ratio in comparison with Fe-silicalite catalyst (see Table 1). Fe-MTW-11500 catalyst reveals rather rare behavior. The concentration of Fe ions in the sample is comparable to Fe-sil-12900 catalyst, as well as... 

Propen-l-ol. See Allyl alcohol 2-Propenal. See Acrolein 2-Propenamide. See Acrylamide Propene, copolymerizations of, 16 111 Propene homopolymerization, 16 104-110 Propene polymerization, 16 94, 99 2-Propenenitrile. See Acrylonitrile (AN) Propenoic acid, physical properties, 5 31t Propenoic acid nitrile. See Acrylonitrile (AN)... 

Symmetrically substituted dienophiles such as p-bcnzoquinone and IV-phenylmaleimide reacted with 4 to give the expected [4 + 2] cycloadducts. No cycloaddition took place, however, in the reaction of l,l-difluoro-2-triphenylsilyloxy-l-propene with 2-chloroacrylo-nitrile, which showed the importance of an additional vinyl group for the reactivity of 4 in... 

A study of the regioselectivity of the 1,3-dipolar cycloaddition of aliphatic nitrile oxides with cinnamic acid esters has been published. AMI MO studies on the gas-phase 1,3-dipolar cycloaddition of 1,2,4-triazepine and formonitrile oxide show that the mechanism leading to the most stable adduct is concerted. An ab initio study of the regiochemistry of 1,3-dipolar cycloadditions of diazomethane and formonitrile oxide with ethene, propene, and methyl vinyl ether has been presented. The 1,3-dipolar cycloaddition of mesitonitrile oxide with 4,7-phenanthroline yields both mono-and bis-adducts. Alkynyl(phenyl)iodonium triflates undergo 2 - - 3-cycloaddition with ethyl diazoacetate, Ai-f-butyl-a-phenyl nitrone and f-butyl nitrile oxide to produce substituted pyrroles, dihydroisoxazoles, and isoxazoles respectively." 2/3-Vinyl-franwoctahydro-l,3-benzoxazine (43) undergoes 1,3-dipolar cycloaddition with nitrile oxides with high diastereoselectivity (90% de) (Scheme IS)." " ... 

Another cycloaddition to an a,(3-unsaturated compound involves the reaction of nitrile oxides with 3-methoxy- or 3-methylthio-1 -phenyl-2-propene-1 -one (Scheme 6.18) (133,134). The isoxazoles that are isolated are considered to arise from the respective intermediate isoxazolines by subsequent elimination of methanol or methanethiol. The regioselectivity observed was attributed to the presence of substituents with strong electron-donating ability, and this was accommodated in terms of the FMO theory (133,134). 

Ammoxidation can be successfully applied to methyl aromatics (e.g. toluene and xylene) as it can to propene. However, the subject has not received much attention in the literature, mainly due to the fact that there are no important applications for aromatic nitriles at present. 

Methyl side chains of aromatic hydrocarbons can be selectively ammox-idized to nitrile groups. The process is very similar to the ammoxidation of propene and the same catalysts are found to be effective. Identical mechanisms have been proposed, and will not be discussed here. 

Vinylpyrroles and vinylindoles are extremely sensitive to acid-catalyzed dimerization and polymerization and it is significant that much of the early research was conducted on systems which were produced in situ. Even by this approach, the dimerization of, for example, 2-(3-indolyl)propene and l-(3-indolyl)-l-phenylethylene was difficult to prevent (see the formation of 110 and 120, Section 3.05.1.2.8). Similarly, although it is possible to isolate ethyl 2-(2- and 3-indolyl)propenoates, they appear to be extremely unstable at room temperature even in the absence of acid (81UP30500) to give [ 4 + 2] cycloadducts of the type (348) (cf. 77JCS(P1)1204>. For many years simple vinylpyrroles also eluded isolation, on account of their facile acid-catalyzed polymerization. Application of the Wittig reaction, however, permits the synthesis of vinyl-pyrroles and -indoles under relatively mild and neutral conditions (see Section 3.05.2.5). In contrast, heteroarylvinyl ketones, esters, nitriles and nitro compounds, obtained by condensation of the appropriate activated methylene compound with the heteroaryl aldehydes (see Section 3.05.2.5), are thermally stable and... 

---