Acrylonitrile s. Cyanoethylation

X0 compounds 21, 304 Aeridizinium salts 21, 937 Acrylic acids s. a,j -Ethylene-carboxylic acids Acrylonitrile s. Cyanoethylation Activation s a. Functionalization... 

The addition of ammonia to acrylonitrile gives /S-aminopropionitrile and fczs-(/S-cyanoethyl)-amine. The former is hydrolyzed directly to /S-amino-propionic acid (90%) by barium hydroxide, " and the latter may also be converted through the intermediate phthalimide to the same amino acid (6S)%). A variation of this procedure involves condensation of phthalimide and acrylonitrile to /S-phthalimidopropionitrile, Both amino and carboxyl groups are formed during the subsequent hydrolysis by hydrochloric acid. The free /S-alanine (75%) is liberated from the hydrochloride by lithium hydroxide. ... 

Ghloropyrrolo [2,3-d] pyrimidine and ethyl acrylate added to a soln. of Na in abs. ethanol, and refluxed 3 hrs. under anhydrous conditions ethyl 4-chloro-pyrrolo[2,3-d]pyrimidine-7-propionate. Y 92%. F. e., also N-cyanoethylation with acrylonitrile, s. R. A. West, J. Org. Ghem. 28, 1991 (1963). 

Kamel, S., Hassan, E. M., and El-Sakhawy, M. 2006. Preparation and application of acrylonitrile-grafted cyanoethyl cellulose for the removal of copper (II) ions. /. Appl. Polym. Sci. 100 329-334. 

Acrylonitrile reacts with the sodium salt of 4.5-dimethvl-A-4-thiazoline-2-thione (73J (R4 = R5 = Me) to yield 3-(2-cyanoethyl)-4.5-dimethyl-A-4-thiazoline-2-thione (74) (R4 = R, = Me) (Scheme 35 (160). Humphlett s studies of this reaction showed that the size of the R4 substituent is a determinant factor for the S versus N ratio (161. 162). If R4 == H, 100% of the N-substituted product (74) is obtained this drops to 50% when R4 = methyl, and only the S-substituted product (75) is obtained when R4 = phenyl. The same trend is observed with various CH2 = CH-X (X = C00CH3. COCH3) reagents (149). The S/N ratio also depends on the electrophilic center for CH2 = CH-X systems thus S-reaction occurs predominantly with acrylonitrile, whereas N-substitution predominates with methvlvinvlketone (149). 

The side-chain cyanoethylation of alkyl thienyl ketones with acrylonitrile has been studied " and used for the preparation of 8-oxonitriles and S-oxoacids. Aminomethylation (Mannich reaction) of 2-acetylthiophene followed by steam distillation yielded 50% of 2-thienyl vinyl ketone, and has also been used for the synthesis of compounds of biological interest. ... 

Urinary metabolites of acrylonitrile include 5 -(2-cyanoethyl)mercapturic acid, N-acet T-3-carboxy-5-cyanotctrahydro-I,4-3//-thiazine and thiocyanate (Kopecky et al., 1979 Langvardt et al., 1980 Gut c/ al., 1981 Sapota, 1982). The proportion excreted as thiocyanate by rats is far higher (23% of dose) after oral dosing than after intraperitoneal, intravenous or subcutaneous administration (1-4% of dose Gut et al., 1981). Other metabolites derived from the mercapturic acid pathway include. S -carboxymethylcys-teine,. S -hydroxyethylmercapturic acid [jV-acetyl-5 -(2-hydroxyethyl)cysteine] and thiodi-glycolic acid (Muller et al., 1987). 

Alanine has been prepared by the catalytic reduction of cyanoacetic esters 1 or salts 2 by heating acrylonitrile,3 /3-amino-propionitrile,4 iw-(/3-cyanoethyl)-amine,5 /3-hydroxypropionitrile, /3-alkoxypropionitriles,7 u.s-(/3-cyanocthyl) ether,8 or bis-(fi-cyano-ethyl) sulfide 8 with aqueous ammonia at 150-225° by the hydrolysis of /3-aminopropionitrile with concentrated hydrochloric acid and subsequent removal of the acid with anion exchange resins.9 The method as described above has been published.10 Additional references to methods of preparation are given in connection with a procedure for the making of /3-alanine from suc-cinimide through the action of potassium hypobromite.11... 

A Monomer solution 32% acrylonitrile in 80% aqueous ZnCh B Cyanoethylated cellulose (D.S. 0.7) monomer solution same... 

A dramatic example of prevalence of y-alkylation over a-alkylation is provided by cyanoethylation of 3)S-acetoxy-5a-pregn-17-en-21-al (186) with acrylonitrile in benzene (see Part II, Chapter 1, refs. 213—216). The signs of the Cotton effects exhibited by the isomeric homoannular dienes (187) produced in this reaction violate the helicity rule for skewed dienes. ... 

Acrylonitrile CH2=CHCN is one of the best Michael acceptors for enol(ate)s. The reaction is known as cyanoethylation as it adds a -CH2CH2CN group to the enol(ate). 

There are four major pathways of metabolism for acrylonitrile formation of glucuronides, direct reaction with glutathione to form cyanoethyl mercapturic acid, direct reaction with the thiol groups of proteins, and epoxidation to 2-cyanoethylene oxide. N-AcetyT S-(2-cyanoethyl)-L-cysteine is a major urinary metabolite in human volunteers exposed to 5-10 mg. 

A mixture of acrylonitrile and trichlorosilane added dropwise to a little CU2O and TMEDA at 0°, and refluxed for 10 min (P-cyanoethyl)trichlorosilane. Y 98%. High yields were also obtained under ultrasonication at room temp. (80% after 2 h). Also hydrosilylation of acrylates s. A.B. Rajkumar, P. Boudjouk, Organometallics 8, 549-50 (1989). 

Michael addition of acrylonitrile to cellulose represents a second class of typical derivation procedures. Lower caustic concentrations are used to activate the cellulose and the reaction occurs a lower temperatures. The effect of various caustic concentrations on the rate and extent of substitution was studied in pure acrylonitrile and in acetone. Addition of TMAC to the pretreatment step has no discernable effect upon the initial rate of cyanoethylation. Upon addition of a twenty-fold excess of acrylonitrile to activated cellulose, a small endothermic heat of mixing is observed followed by a gradual increase in temperature produced by the exothermic Michael addition. The temperature was held at 27° to prevent a comcommitant anionic polymerization of acrylonitrile. The influence of the TMAC becomes evident as the reaction proceeds. Cyanoethylated cellulose imbibes the remaining reagent when the D.S. approachs 2 and an extremely viscous mass forms. Uncatalysed reactions stop at this point catalysed systems appear to autoaccelerate to degrees of substitution... 

Fig.3. Cyanoethylation of Wood Cellulose Cl, 5.0 g cellulose, 0-3 g TMAC 100 ml acrylonitrile stirred 3.S hr at 27 O, control (same conditions, TMAC omitted), No catalyst at 35 .

A major problem in cellulose cyanoethylation is control of the concommitant anionic polymerization of acrylonitrile. At base concentrations greater than 12%, exothermic polymerization occurs rapidly if the temperature is raised to 40 . In the presence of TMAC, the polymerization is suppressed, until a significant increase in the extent of substitution as evidenced by gelation occurs. However, at this point hydroxide ions must be released and a rapid polymerization ensues. Derivatives with apparent M.S. of 6.5 are isolated, but it is difficult to separate homopolyacrylonitrile from cyanoethyl cellulose to confirm if grafting has occurred. However, the initial suppression of base catalysed polymerization is a convincing demonstration of hydroxide transfer and binding in the cellulose phase. 

Cyanoethyl Cellulose. A. Neat Reaction. Wood cellulose, 5.0 g was treated with 0.15 g of tetramethylammonium chloride dissolved in 2 mL of water. The cellulose was slurried in 120 mL of acrylonitrile and 5 mL of 12% sodium hydroxide was added. The slurry was stirred at 25° for 4 hours during which time the mixture became very doughy. The reaction mixture was washed with isopropanol until a free flowing slurry formed. The product was recovered by filtration, 9.4 g, D.S. = 3.0, based upon a nitrogen content of 13.02%. 

B. Solvent Diluted Process. An activated substrate was prepared by dry-blending 5 g of cellulose, 0.3 g TMAC, and 5 ml of 10% sodium hydroxide at 25° for 15 min. A solution of acrylonitrile (100 ml) in 100 ml acetone was added and the reactor was immersed in a 40° oil bath. After 3.5 hr the mixture was a viscous yellow solution containing some unreated fibers. The product was precipitated in water, the acrylonitrile and acetone were removed by steam distillation, and the aqueous suspension of polymer neutralized with 5 % HCl. After isolating and drying in vacuo, 8.46 g of cyanoethyl cellulose, D.S.=2.14, was obtained. 

Acrolein heated with anthracene in toluene for 2.5 hrs. in an autoclave 9,10-dihydro-ll-formyl-9,10-ethanoanthracene (Y 79.5%) suspended in di-oxane, added during 20 min. at 20-25° to a soln. of acrylonitrile and 10%-KOH in dioxane, stirred 5 hrs. at 35°, then most of the solvent removed by distillation 9,10-dihydro-11-(2-cyanoethyl)-11-formyl-9,10-ethanoanthracene (Y 81%) heated with mineral oil at 220-225°/140-90 mm for 3 hrs. with distillation of the product 4-formyl-4-pentenonitrile (Y 68%). F. e. s. F. Weiss and R. Rusch, Bl. 19U, 550. 

A stoichiometric amount of 30%-H2O2 added slowly at ca. 0° under N2 to a soln. of n-octylphosphine in methanol, to the soln. of the resulting n-octyl-phosphine oxide Na-methoxide and acrylonitrile added, allowed to stand 3 days, then evaporated to dryness bis-(2-cyanoethyl)-n-octylphosphine oxide. Y 54%. F. e. s. S. A. Buckler and M. Epstein, Tetrahedron 18, 1221 (1962). 

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