Vinyl acetonitrile

Allyl cyanide (vinyl acetonitrile, allyl nitrile,... 

The production of three isomers is initiated by a C C bond breaking adjacent to the carbon connected to the functional group, channel 1 (Figure 6.2). The three isomers in channel 1 are cis-crotonitrile, /raMi-crotonitrile, and vinyl acetonitrile. The fourth isomer, methacrylonitrile, is obtained via channel 2. The production of the last is initiated by the C C bond breaking opposite to the C R bond, channel 2 (Figure 6.3). 

FIGURE 6.2 Reaction schemes for cyclopropane carbonitrile isomerizations to cis-, trans-crotonitrile, and vinyl acetonitrile (channel 1). All the energy values are calculated relative to the reactant. 

By condensing carbon oxysulfide with o-aminOnitriles the corresponding 2-hydroxy-5-aminothiazoles can be obtained. In the presence of benzaldehyde or its substituted derivatives the reaction leads to 5-benzy-lideneaminothiazole derivatives (218) in good yields (Scheme 114 and Table 11.35) (393, 442). However, the reaction fails with or-amino acetonitrile (206), R = H (317). The 2-alkoxy analogs (220), R = Me, Et, Pr, Bu, vinyl, were similarly obtained from 219 and benzylideneamino acetonitrile (Scheme 115a) (393). 

Copolymerization can be carried out with styrene, acetonitrile, vinyl chloride, methyl acrylate, vinylpyridines, 2-vinylfurans, and so forth. The addition of 2-substituted thiazoles to different dienes or mixtures of dienes with other vinyl compounds often increases the rate of polymeriza tion and improves the tensile strength and the rate of cure of the final polymers. This allows vulcanization at lower temperature, or with reduced amounts of accelerators and vulcanizing agents. 

Block copolymers of vinyl acetate with methyl methacrylate, acryflc acid, acrylonitrile, and vinyl pyrrohdinone have been prepared by copolymeriza tion in viscous conditions, with solvents that are poor solvents for the vinyl acetate macroradical (123). Similarly, the copolymeriza tion of vinyl acetate with methyl methacrylate is enhanced by the solvents acetonitrile and acetone and is decreased by propanol (124). Copolymers of vinyl acetate containing cycHc functional groups in the polymer chain have been prepared by copolymeriza tion of vinyl acetate with A/,A/-diaIlylcyanamide and W,W-diaIl5lamine (125,126). 

NOTE - Petrochemical plants also generate significant amounts of solid wastes and sludges, some of which may be considered hazardous because of the presence of toxic organics and heavy metals. Spent caustic and other hazardous wastes may be generated in significant quantities examples are distillation residues associated with units handling acetaldehyde, acetonitrile, benzyl chloride, carbon tetrachloride, cumene, phthallic anhydride, nitrobenzene, methyl ethyl pyridine, toluene diisocyanate, trichloroethane, trichloroethylene, perchloro-ethylene, aniline, chlorobenzenes, dimethyl hydrazine, ethylene dibromide, toluenediamine, epichlorohydrin, ethyl chloride, ethylene dichloride, and vinyl chloride. 

The principal components of the cut are butene-1, butene-2, isobutylene and butadiene-1,3. Methyl, ethyl, and vinyl acetylenes, butane and butadiene-1,2 are present in small quantities. Butadiene is recovered from the C4 fraction by extraction with cuprous ammonium acetate (CAA) solution, or by extractive distillation with aqueous acetonitrile (ACN). The former process is a liquid-liquid separation, and the latter a vapor-liquid separation. Both take advantage of differences in structure and reactivity of the various C4 components to bring about the desired separation. 

Dehydrochlorination of bis(tnfluoromethylthio)acetyl chloride with calcium oxide gives bis(trifluoromethylthio)ketene [5] (equation 6) Elimination of hydrogen chloride or hydrogen bromide by means of tetrabutylammonium or potassium fluoride from vinylic chlorides or bromides leads to acetylenes or allenes [6 (equation 7) Addition of dicyclohexyl-18-crown-6 ether raises the yields of potassium fluoride-promoted elimination of hydrogen bromide from (Z)-P-bromo-p-ni-trostyrene in acetonitrile from 0 to 53-71 % In dimethyl formamide, yields increase from 28-35% to 58-68%... 

Thermal cyclization of 2-vinyl-N,N-dialkylanilines 138 afforded 139 with creation of a new chiral center in 98% purity (89JOC199). In case of pyrrolidine with methyl or methoxymethyl substituent, cyclization with ZnCl2 occurs via an irreversible 1,5-hydrogen shift in boiling acetonitrile (87JA3136) or BuOH (91RTC115) to afford the diastereoisomers 140 (33%), 141 (35%) and 142 (6%) (87JA3136) (Scheme 27). 

Vinyl chloride is an important monomer for polyvinyl chloride (PVC). The main route for obtaining this monomer, however, is via ethylene (Chapter 7). A new approach to utilize ethane as an inexpensive chemical intermediate is to ammoxidize it to acetonitrile. The reaction takes place in presence of a cobalt-B-zeolite. 

A bicyclo[3.3.0]octane ring system 164 can be conveniently prepared by refluxing an acetonitrile solution of the azo compound 163 in the presence of excess of phenyl vinyl... 

Acetic acid, nitro-, methyl ester, 55, 77, 78 Acetic acid, trifluoro-, 55 70 Acetonitrile, diphenyl-, 55, 94, 102 Acetonitrile, diphenyl-2-(l-ethoxyethenyl)-[ Acetonitrile, diphenyl-2-(l-ethoxy-vinyl)-, 55, 102... 

Es kann ferner von Phenyl-acetonitril, Cyanessigsaure-athylester und Acrylsaure-nitril ausgegangen werden. lm letzteren Fall wird die Homologisierung durch Michael-Addition eincr C—H-aciden Verbindung an das erhal-tene 4,4,6-Trimethyl-2-vinyl-5,6-dihydro-4H-l,3-oxazin durchgefiihrt1. 

A strong acceptor TCNE undergoes [2+2] rather than [4+2] cycloaddition reactions even with dienes. 1,1-Diphenylbutadiene [20] and 2,5-dimethyl-2,4-hexadiene (Scheme 5) [21] afford mainly and exclusively vinyl cyclobutane derivatives, respectively. In the reactions of 2,5-dimethyl-2,4-hexadiene (1) the observed rate constant, is greater for chloroform solvent than for a more polar solvent, acetonitrile (2) the trapping of a zwitterion intermediate by either methanol or p-toluenethiol was unsuccessful (3) radical initiators such as benzyl peroxide, or radical inhibitors like hydroquinone, have no effect on the rate (4) the entropies of activation are of... 

The reaction between benzylidenetriphenylphosphorane and benzonitrile has been reinvestigated and the primary product (82) isolated. Stable ylides react similarly with activated nitriles, e.g. cyanogen and trifluoro-acetonitrile, but cyanomethylenetriphenylphosphorane with methyl cyano-formate gave largely the vinyl ether (83), the product of a normal olefin synthesis on the carbonyl of the ester group. 

The coupled fragments were then converted to a vinyl iodide. The key steps were a Z-selective Lindlar reduction and iodinolysis of the vinyl silane, which was done using NIS in acetonitrile (sequence F-l to F-ll). 

Petasis reported an efficient addition of vinyl boronic acid to iminium salts.92 While no reaction was observed when acetonitrile was used as solvent, the reaction went smoothly in water to give allyl amines (Eq. 11.54). The reaction of the boron reagent with iminium ions generated from glyoxylic acid and amines affords novel a-amino acids (Eq. 11.55). Carboalumination of alkynes in the presence of catalytic Cp2ZrCl2 and H2O affords vinylalane intermediates, which serve as nucleophiles in the subsequent addition to enantiomerically enriched... 

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