Acrylonitrile 2-chloro

Synonyms Acrylonitrile, 2-chloro- Chloroacrylonitrile a-Chloroacrylonitrile 2-Chloro-2-propenenitrile 2-Propenenitrile, 2-chloro-... 

Many synthetic latices exist (16-18). They contain butadiene and styrene copolymers (elastomeric), styrene-butadiene copolymers (resinous), butadiene and acrylonitrile copolymers, butadiene with styrene and acrylonitrile, chloro-prene copolymers, methacrylate and acrylate ester copolymers, vinyl acetate copolymers, vinyl and vinylidene chloride copolymers, ethylene copolymers, fluori-nated copolymers, acrylamide copolymers, styrene-acrolein copolymers, and pyrrole and pyrrole copolymers. Many of these latices also have carboxylated versions. 

Copolymers of an acrylate and a small amount of other monomer which provides vulcanizability Copolymers fan acrylate and acrylonitrile Chloro-polyethylene Polychloro-trifluoro-ethylene Chloro-sulfonly-polyethylene Terpolymers of ethylene, propylene and a nonconjugated diene which results in pendant unsaturation (not in the main chain)... 

The synthesis of 2-chloro-2,3,3-trifluorocyclobutyl acetate illustrates a general method of preparing cyclobutanes by heating chlorotrifluoroethylene, tetrafluoroethylene, and other highly fluorinated ethylenes with alkenes. The reaction has recently been reviewed.11 Chlorotrifluoroethylene has been shown to form cyclobutanes in this way with acrylonitrile,6 vinylidene chloride,3 phenylacetylene,7 and methyl propiolate.3 A far greater number of cyclobutanes have been prepared from tetrafluoroethylene and alkenes 4,11 when tetrafluoroethylene is used, care must be exercised because of the danger of explosion. The fluorinated cyclobutanes can be converted to a variety of cyclobutanes, cyclobutenes, and butadienes. 

Acetyloxindole, 40, 1 Aud chlorides, from acids and chloro vmylamuies, 41, 23 from cyanoacetic acid, 41, 5 from pentaacetylglucomc acid, 41, 80 Acrylamide, N benzyl, 42,16 Acrylonitrile, reaction with benzyl alcohol, 42, 16... 

Pandey et al. have used ultrasonic velocity measurement to study compatibility of EPDM and acrylonitrile-butadiene rubber (NBR) blends at various blend ratios and in the presence of compa-tibilizers, namely chloro-sulfonated polyethylene (CSM) and chlorinated polyethylene (CM) [22]. They used an ultrasonic interferometer to measure sound velocity in solutions of the mbbers and then-blends. A plot of ultrasonic velocity versus composition of the blends is given in Eigure 11.1. Whereas the solution of the neat blends exhibits a wavy curve (with rise and fall), the curves for blends with compatibihzers (CSM and CM) are hnear. They resemble the curves for free energy change versus composition, where sinusoidal curves in the middle represent immiscibility and upper and lower curves stand for miscibihty. Similar curves are obtained for solutions containing 2 and 5 wt% of the blends. These results were confirmed by measurements with atomic force microscopy (AEM) and dynamic mechanical analysis as shown in Eigures 11.2 and 11.3. Substantial earher work on binary and ternary blends, particularly using EPDM and nitrile mbber, has been reported. 

FIGURE 11,1 Ultrasonic velocity versus acrylonitrile-butadiene mbber/ethylene-propylene-diene monomer (NBR-EPDM) blend composition (a) no compatibiUzer, (b) with chloro-sulfonated polyethylene (CSM), and (c) with chlorinated polyethylene (CM). (From Pandey, K.N., Setua, D.K., and Mathur, G.N., Polym. Eng. Set, 45, 1265, 2005.)... 

JME538, 1997CH739>. The main thiadiazole product 185, however, suffered chlorination in the a-position. The isolation of 2-amino acrylonitrile 184 from the reaction mixture supported decomposition of the 2-oximino acetonitrile 183 furthermore, treatment of the pure acrylonitrile under typical reaction conditions gave exclusively ot-chloro-3-chloro-l,2,5-thiadiazole 185 (Scheme 27 Table 11). Mechanisms explaining the formation of both thiadiazoles were proposed <1998H(48)2111>. 

The results of the olefin oxidation catalyzed by 19, 57, and 59-62 are summarized in Tables VI-VIII. Table VI shows that linear terminal olefins are selectively oxidized to 2-ketones, whereas cyclic olefins (cyclohexene and norbomene) are selectively oxidized to epoxides. Cyclopentene shows exceptional behavior, it is oxidized exclusively to cyclopentanone without any production of epoxypentane. This exception would be brought about by the more restrained and planar pen-tene ring, compared with other larger cyclic nonplanar olefins in Table VI, but the exact reason is not yet known. Linear inner olefin, 2-octene, is oxidized to both 2- and 3-octanones. 2-Methyl-2-butene is oxidized to 3-methyl-2-butanone, while ethyl vinyl ether is oxidized to acetaldehyde and ethyl alcohol. These products were identified by NMR, but could not be quantitatively determined because of the existence of overlapping small peaks in the GC chart. The last reaction corresponds to oxidative hydrolysis of ethyl vinyl ether. Those olefins having bulky (a-methylstyrene, j8-methylstyrene, and allylbenzene) or electon-withdrawing substituents (1-bromo-l-propene, 1-chloro-l-pro-pene, fumalonitrile, acrylonitrile, and methylacrylate) are not oxidized. 

Watts, Reddy and Goldstein found exactly the opposite effect for a-chloro-acrylonitrile (Table 18). A rough correlation is noted between the apparent increase and the reaction field term (e-l)/(2e+2.5). 

When 3-chloro-3-phenyl acrylonitrile was involved in this reaction, a bi-cyclic product, 6,6 -diphenyl-4,4 -bis(l,2,3-dithiazine) was formed in good yield [262]. Five-membered cyclic disulfides were obtained in this reaction when ethylenic esters or ketones were taken as an unsaturated substrate (Scheme 61) [263]. 

In a systematic study of the addition of cyclohexyl radicals to a-substi-tuted methyl acrylates, Giese (1983) has shown that the captodative-substituted example fits the linear correlation line of log with o-values as perfectly as the other cases studied. Thus, no special character of the captodative-substituted olefin is displayed. More recently, arylthiyl radicals have been added to disubstituted olefins in order to uncover a captodative effect in the rate data (Ito et aL, 1988). Even though a-A, A -dimethyl-aminoacrylonitrile reacts fastest in these additions, this observation cannot per se be interpreted as the manifestation of a captodative effect. Owing to the lack of rate data for the corresponding dicaptor- and didonor-substituted olefins, it is not possible to postulate a special captodative effect. The result confirms only that the A, A -dimethylamino-group, as expected from its a, -value, enhances the addition rate. In the sequence a-alkoxy-, a-chloro-, a-acetoxy- and a-methyl-substituted acrylonitriles, it reacts fastest. 

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

Acetamido-4-amino-6-chloro-s-triazine, see Atrazine Acetanilide, see Aniline, Chlorobenzene, Vinclozolin Acetic acid, see Acenaphthene, Acetaldehyde, Acetic anhydride. Acetone, Acetonitrile, Acrolein, Acrylonitrile, Aldicarb. Amyl acetate, sec-Amyl acetate, Bis(2-ethylhexyl) phthalate. Butyl acetate, sec-Butyl acetate, ferf-Butyl acetate, 2-Chlorophenol, Diazinon. 2,4-Dimethylphenol, 2,4-Dinitrophenol, 2,4-Dinitrotoluene, 1,4-Dioxane, 1,2-Diphenylhydrazine, Esfenvalerate. Ethyl acetate, Flucvthrinate. Formic acid, sec-Hexyl acetate. Isopropyl acetate, Isoamyl acetate. Isobutyl acetate, Methanol. Methyl acetate. 2-Methvl-2-butene. Methyl ferf-butvl ether. Methyl cellosolve acetate. 2-Methvlphenol. Methomvl. 4-Nitrophenol, Pentachlorophenol, Phenol. Propyl acetate. 1,1,1-Trichloroethane, Vinyl acetate. Vinyl chloride Acetoacetic acid, see Mevinphos Acetone, see Acrolein. Acrylonitrile. Atrazine. Butane. 

Monomers which can add to their own radicals are capable of copolymerizing with SO2 to give products of variable composition. These include styrene and ring-substituted styrenes (but not a-methylstyrene), vinyl acetate, vinyl bromide, vinyl chloride, and vinyl floride, acrylamide (but not N-substituted acrylamides) and allyl esters. Methyl methacrylate, acrylic acid, acrylates, and acrylonitrile do not copolymerize and in fact can be homopolymer-ized in SO2 as solvent. Dienes such as butadiene and 2-chloro-butadiene do copolymerize, and we will be concerned with the latter cortpound in this discussion. 

Chromium metal may be oxidized by Cl2, Br2 or I2 in ethanenitrile solution to give the octahedral complexes [CrCl3(MeCN)3]-MeCN, CrBr3(MeCN)3 and [CrI2(MeCN)4]I although the nitrile content of the bromo complex is somewhat variable.658 The chloro complex loses the uncoordinated nitrile when heated at 80 °C under vacuum. Some properties of these complexes are listed in Table 72. Reaction of CrCl3 with propanenitrile and acrylonitrile affords the dark purple complexes CrCl3(nitrile)3.6M... 

Of the lower members of this reactive group of compounds, the more lightly substituted are of high flammability and many are classed as peroxidisable and as polymerisable compounds. Individually indexed compounds are f Acrylonitrile, 1104 f 4-Bromo-l-butene, 1544 f 3-Bromo-l-propene, 1149 f l-Bromo-2-butene, 1543 4-Bromocyclopentene, 1878 f Bromoethylene, 0723 f Bromotrifluoroethylene, 0576 f 2-Chloro-1,3-butadiene, 1447 f 3-Chloro-l-butene, 1547... 

The intermediate adduct is generally stable enough so that spontaneous dehydrohalogenation does not take place. For example, the 3-(arylthio)-2-halonitriles which are obtained from thiols and a-chloro-acrylonitrile, form rearranged products only in the presence of dehydro-halogenating base (Birum and Heininger, 1957 Heininger and Birum, 1965). 

Sensitized addition of cyclic dienes with chlorinated alkenes, employing an excess of the latter, yields mixtures of [4+2] and [2+2] adducts (Sch. 10). A substantial proportion of [4+2] adduct 46a is formed when cyclopentadiene 32 is the diene, but cyclohexadiene 36 yields almost entirely the [2+2] adduct 46b. Use of acyclic 1,3-dienes leads only to [2+2] products. The regioselectivity of the cycloadditions is consistent with a biradical intermediate 48 [47]. Sensitized irradiation of cyclopentadiene with 1-acetoxy acrylonitrile 49 also gives a [4+2] and [2+2] mixture, but with a higher proportion of the [4+2] adduct than the reactions using chloro-alkenes 45 [33-35]. 

Alternatively, Michael reaction of the nonaol with acrylonitrile yields a nonanitrile, which can be reduced to the nonaamine. This nonaamine was allowed to react with chloro-carbonylmetallocenes and other chlorocarbonyl sandwich complexes to yield nonaamido-metallocenes [61-63] and nonaamido-sandwich compounds [63] (Scheme 20). These metallodendrimers also give rise to only one cyclic voltammetry wave, the intensity of which corresponds to approximately nine electrons using the technique indicated above (the solvent was CH2CI2 for the nonaamidoferrocene and MeCN for the polycationic dendrimers). Chemical reversibility was observed at room temperature, although some adsorption was noted. 

Indium-mediated Barbier-type reaction of glyoxal monoacetal with bromomethyl acrylonitrile or bromomethyl-acrylate gives a masked a-hydroxy aldehyde (Equation (48)).91 The reaction of 3-bromo-2-chloro-l-propene, an aldehyde, and indium in water gives the corresponding homoallyl alcohol, which upon ozonolysis in methanol furnishes a / -hydroxy ester. The overall reaction is equivalent to the Reformatsky reaction, which cannot be realized by a direct indium-mediated reaction of an ct-halo ester with an aldehyde in water (Scheme 59).235... 

FIG. 18.3 Activation energy of diffusion as a function of Tg for 21 different polymers from low to high temperatures, ( ) odd numbers (O) even numbers 1. Silicone rubber 2. Butadiene rubber 3. Hydropol (hydrogenated polybutadiene = amorphous polyethylene) 4. Styrene/butadiene rubber 5. Natural rubber 6. Butadiene/acrylonitrile rubber (80/20) 7. Butyl rubber 8. Ethylene/propylene rubber 9. Chloro-prene rubber (neoprene) 10. Poly(oxy methylene) 11. Butadiene/acrylonitrile rubber (60/40) 12. Polypropylene 13. Methyl rubber 14. Poly(viny[ acetate) 15. Nylon-11 16. Poly(ethyl methacrylate) 17. Polyethylene terephthalate) 18. Poly(vinyl chloride) 19. Polystyrene 20. Poly (bisphenol A carbonate) 21. Poly(2,6 dimethyl-p.phenylene oxide). 

Figure 4.1-4 Vibrational spectra of A acrylonitrile, B isoprene, and C 2-chloro-l,3-btitadiene, from Schrader (1989) C3-05, C2-01, and C2-14.

Certain olefinic nitriles ate readily available from a-chloro-/S ylpro-pionitriles obtained by the addition of diazonium salts to acrylonitrile. Dehydrohalogenation is effected by boiling with diethylaniline. ... 

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