Cyanoethylene

As well as the cr-complexes discussed above, aromatic molecules combine with such compounds as quinones, polynitro-aromatics and tetra-cyanoethylene to give more loosely bound structures called charge-transfer complexes. Closely related to these, but usually known as Tt-complexes, are the associations formed by aromatic compounds and halogens, hydrogen halides, silver ions and other electrophiles. 

Malonic acid, amino-, diethyl ester, HYDROCHLORIDE, 40, 24 Malonic acid, bts(hydroxymethyl)-, DIETHYL ETHER, 40, 27 Malonitrile, condensation with tetra-cyanoethylene, 41, 99 2-Mercaptopyrimidine, 43, 6S hydrochloride of, 43, 68 Mercuric oxide in preparation of bromo-cyclopropane, 43, 9 Mesityl isocyanide, 41,103 5-Methallyl-l,2,3,4,5-pentachlorocyclo-pentadiene, 43, 92 Methane, dimesityl-, 43, 57 Methanesiileinyl chloride, 40, 62 Methanesulfonic acid, solvent for making peroxybenzoic acid from benzoic acid, 43, 93... 

Alternatively, acrylonitrile is metabolized to 2-cyanoethylene oxide by the microsomal enzyme system. 2-Cyanoethylene oxide can react directly with tissue macromolecules or it can be further metabolized to oxidation products that release cyanide. Cyanide is converted to thiocyanate and excreted in the urine. 2-Cyanoethylene oxide is also conjugated with glutathione and metabolized to 2- hydroxyethylmercapturic acid which is excreted in the urine. 

The increased metabolism of acrylonitrile to 2-cyanoethylene oxide has significant implications in acrylonitrile toxicity. 2-Cyanoethylene oxide has been shown to react with cell macromolecules (including nucleic acids) both in vivo and in vitro (Guengerich et al. 1981 Hogy and Guengerich 1986). This metabolite may be responsible for the carcinogenic effects of acrylonitrile. 

Comparative studies of the metabolism and pharmacokinetics of acrylonitrile and cyanoethylene oxide in mice and rats BP... 

Development of a physiologically-based dosimetry model for acrylonitrile and cyanoethylene oxide... 

Acrylonitrile Cyanoethylene 2-propenenitri1e vinyl Acritet, Caswell No. 01 Fumigrain, Ventox... 

Guengerich FP, Geiger LE, Hogy LL, et al. 1981. In vitro metabolism of acrylonitrile to 2-cyanoethylene oxide, reaction with glutathione, and irreversible binding to proteins and nucleic acids. Cancer Res 41 4925-4933. 

Hogy LL, Guengerich FP. 1986. In vivo interaction of acrylonitrile and 2-cyanoethylene oxide with DNA in rats. Cancer Res 46 3932-3938. 

Recio L, Skopek TR. 1988. Mutagenicity of acrylonitrile and its metabolite 2-cyanoethylene oxide in human lymphoblasts in vitro. Mutat Res 206 297-305. 

Roberts AE, Lacy SA, Pilon D, et al. 1989. Metabolism of acrylonitrile to 2-cyanoethylene oxide in F-344 rat liver microsomes, lung microsomes, and lung cells. Drug Metab Dipos 17 481-486. 

Venitt S, Bushell CT, Osborne M. 1977. Mutagenicity of acrylonitrile (cyanoethylene) in Escherichia coli. Mutat Res 45 283-288. 

Cupron, b50 Cyanoacetonitrile, m5 Cyanoanilines, al21, al22, al23 Cyanobenzene, b51 2-Cyanoethanol, hl73 Cyanoethylene, a63 Cyanomethane, a29... 

All of these compounds bear at least one strongly electron withdrawing substituent or a double or a triple bond. Thus tetra cyanoethylene is about 4.6 x 108 times as reactive as cyclopentadiene. As a result of sensual studies, the following conclusions have been obtained. 

Most of the data in Table 12 come from the work of Shvo et al. (78). Careful band-shape analysis and solvent-effect studies permitted evaluation of the rate constants and AG values at 298 K, which renders the discussion of substituent effects more meaningful than usual. The authors obtained reasonably linear Hammett plots when correlating log km with Or (79) for X and Y, holding one of these substituents constant. They also found that the dihydropyridine system may act as an unusually efficient donor, giving a AG of 17.6 kcal/mol with X, Y = H, CN, the only barrier below 25 kcal/mol reported for any donor-substituted cyanoethylene. However, with other acceptor combinations the dihydropyridine moiety is not so outstanding, and this illustrates the difficulty of measuring donor and/or acceptor effects by rotational barriers alone (vide infra). 

Synonyms Acritet Acrylon Acrylonitrile monomer AI3-00054 AN BRN 0605310 Carbacryl Caswell No. 010 CCRIS 8 Cyanoethene Cyanoethylene EINECS 203-466-5 ENT 54 EPA pesticide chemical code 000601 Fumigrain Miller s fumigrain NCI-C50215 Nitrile NSC 6362 Propenenitrile 2-Propenenitrile RCRA waste number U009 TL 314 UN 1093 VCN Ventox Vinyl cyanide. 

Chemical/Physical. Ozonolysis of acrylonitrile in the liquid phase yielded formaldehyde and the tentatively identified compound glyoxal, an epoxide of acrylonitrile and acetamide. The reported rate constant for the reaction of acrylonitrile and ozone in the gas phase is 1.38 x lO cm moFsec (Munshi et al., 1989). In the gas phase, cyanoethylene oxide was reported as an ozonolysis product... 

Cupric chloride, see Carbon tetrachloride Cyanazine amide, see Cvanazine Cyanoethylene, see Acrylonitrile Cyanogen chloride, see Aniline, Benzene. 

Unexpectedly, the analysis of the MOs of the cation-radical from (5-cyano vinylferrocene reveals the possibility for cis trans conversion if more than one-electron oxidation takes place. Namely, the cation-radical has an MO, which is four levels higher in energy than the one occupied by the single electron, that is centered on the cyanoethylene fragment (Todres et al. 1992). 

Reductive elimination on transition metal complexes seems to be enhanced by coordination of electron-withdrawing 71-acids such as cyanobenzene and cyanoethylene. For example, the reductive elimination reaction of NiR2(bpy) (R=alkyl or aryl group bpy =2,2 -bipyridyl) is enhanced by electron-withdrawing olefinic and aromatic compounds [12-16] (Scheme 1). 

Norbornadiene adds typical dienophiles in a homo-Diels-Alder reaction whereby, for example, the adduct 86 is obtained with tetra-cyanoethylene. Dimethyl acetylenedicarboxylate and dicyanoacetyl-ene add to barrelene (bicyclo[2.2.2]octa-2,5,7-triene) in a similar way. °... 

Synonyms ACN cyanoethylene propeneni-trile vinyl cyanide... 

Namely, when electron-transfer adsorbates such as the electron-acceptor tetra-cyanoethylene (TCNE) and electron-donor tetrathiafulvalene (TTF) molecules interact with the inorganic framework, the energy gap of the mesoporous NU-Ge-1 (1.87 eV) is red-shifted to 1.71 and 1.64 eV, respectively. Indeed, this change in electronic structure is reversible and the optical adsorption onsets going to 1.83 eV upon formation of the inactive TTF-TCNE complex inside the pores. Incorporation of molecules without electron-acceptor or electron-donor properties such as anthracene did not affect the electronic structure of NU-Ge-1. 

The formation of various 1 1 adducts from dehydrodithizone 413, R = R = Ph, and various 1,3-dipolarophiles has been reported. Thus, dimethyl acetylenedicarboxylate yields 419, X = COOMe, tetra-cyanoethylene yields 420, and e oxycarbonylmethylenetriphenylphos-phorane yields the betaine 421. These transformations have been considered as 1,3-dipolar cycloaddition reactions of a novel type. It seems to us rather unlikely that these transformations are concerted 1,3-dipolar cycloadditions the alternative that they are reactions involving dipolar intermediates (e.g., 422, 423, and 424) should also be considered. The... 

CN-stretching frequencies, 12 387 Cyanodifluorophosphine, 13 382, 383 Cyanoethylene complexes with group VIB metals, 12 223 Cyanogen... 

A good example for which experimental data are available, involves activation energies for Diels-Alder cycloadditions of different cyanoethylenes as dienophiles with cyclopentadiene, relative to the addition of acrylonitrile with cyclopentadiene as a standard. 

Potassium hydroxide-mediated elimination of cyanoethylene from the 4-cyanoethyltriazoloozadiazole 131 yielded the potassium salt 68 (Equation 6) <1996TL8577>. 

Since the energy of D+A- is governed by the magnitude of /D — Aa, D + A" will be stabilized when the diene is substituted by electron-releasing substituents (/ is lowered) and the ene by electron-withdrawing ones (Aa is increased). Indeed, cycloadditions proceed more rapidly in such cases. For example, 1,2-dicyanoethylene undergoes cycloaddition with cyclopentadiene c. 80 times faster than cyanoethylene (Sauer, 1967). In the former case / — Aa is 7.8 eV while in the latter case it is 8.6 eV. 

Cyanide of Calcium Cyanoacetic Acid Cyanobenzene 2-Cyanoethanol Cyanoethylene... 

The rate of solution depends upon the fineness of the tetra-cyanoethylene powder however, solution should occur soon after the temperature reaches 60-70°. 

---