Alcohols, reaction with acrylonitrile

N-Benzylacetamide, 43,18 n-Benzylacrylauide, 42,16 Benzyl alcohol, reaction with acrylonitrile, 42, 16... 

Benzophenone, conversion to ethyl /S-hydroxy-0,0-diphenylpro-pionate, 44, 57 Benzophenone oxime, 44, 52 Benzopyrazole, 42, 69 3-Benzoylpropionic add, condensation with benzaldehyde to give a-benzylidene-y-phenyl-A y -bu-tenolide, 43, 3 N-Benzylacetamide, 42,18 n-Benzyiacrylamide, 42,16 Benzyl alcohol, reaction with acrylonitrile, 42,16... 

This work comments on the slow induction period of the H2SO4 reaction with acrylonitrile and alcohol, and on possible safety issues. 

Methylenecyclobutanes are readily obtained by the condensation of an olefin with an allene. Thus, reaction of (221) with acrylonitrile gives (222) and the cyclohexenes (223), the latter resulting from prior rearrangement of (221) to 2-chlorobuta-1,3-diene followed by Diels-Alder reaction with acrylonitrile. Compound (222) cyclizes on dehydrochlorination to the unstable 3-methylenebicyclo[2,l,0]pentane (224). A second route to a 3-cyanomethylenecyclobutane involves vinyl Grignard addition to the ketones (225) and chlorination of the resulting alcohol (226 X = OH), which affords a mixture of (226 X = Cl) and (227). ... 

The sulfuric acid hydrolysis may be performed as a batch or continuous operation. Acrylonitrile is converted to acrylamide sulfate by treatment with a small excess of 85% sulfuric acid at 80—100°C. A hold-time of about 1 h provides complete conversion of the acrylonitrile. The reaction mixture may be hydrolyzed and the aqueous acryhc acid recovered by extraction and purified as described under the propylene oxidation process prior to esterification. Alternatively, after reaction with excess alcohol, a mixture of acryhc ester and alcohol is distilled and excess alcohol is recovered by aqueous extractive distillation. The ester in both cases is purified by distillation. 

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... 

Co-adsorption experiments show a complex role of the nature and concentration of chemisorbed ammonia species. Ammonia is not only one of the reactants for the synthesis of acrylonitrile, but also reaction with Br()>nsted sites inhibits their reactivity. In particular, IR experiments show that two pathways of reaction are possible from chemisorbed propylene (i) to acetone via isopropoxylate intermediate or (ii) to acrolein via allyl alcoholate intermediate. The first reaction occurs preferentially at lower temperatures and in the presence of hydroxyl groups. When their reactivity is blocked by the faster reaction with ammonia, the second pathway of reaction becomes preferential. The first pathway of reaction is responsible for a degradative pathway, because acetone further transform to an acetate species with carbon chain breakage. Ammonia as NH4 reacts faster with acrylate species (formed by transformation of the acrolein intermediate) to give an acrylamide intermediate. At higher temperatures the amide may be transformed to acrylonitrile, but when Brreform ammonia and free, weakly bonded, acrylic acid. The latter easily decarboxylate forming carbon oxides. 

We can, however, form alkoxide ions that are monosolvated by a single alcohol group, via the Riveros reaction [Equation (7)]. When the monosolvated methoxide is reacted with acrylonitrile, the addition process reaction (8a), is the major pathway, because there is a molecule of solvent available to carry off the excess energy. The proton transfer pathway, reaction (8b), becomes endothermic, because the methoxide-methanol hydrogen bond, at about 29 kcal/mol, must be broken in order to yield the products. Thus, one can observe either the unique gas phase mechanism in the gas phase, reaction (6b), or the solution phase mechanism in the gas phase, reaction (8a), and the only difference is in the presence of the first molecule of solvent. 

The reaction is usually performed with homogeneous basic catalysts such as alkali hydroxides, alkoxides, and tetraalkyl ammonium hydroxide (161,162). The mechanism accepted for this transformation starts with the abstraction by the base catalyst of a proton from the hydroxyl group of the alcohol to generate the alkoxide anion, which reacts with acrylonitrile to form the 3-alkoxypropanenitrile anion. The 3-alkoxypropanenitrile anion abstracts a proton from the catalyst to yield 3-alkoxypropane nitrile. 

Manufacturing processes and equipment are similar to those employed for alcohol ethoxylate preparation. In the absence of steric hindrance, ethylene oxide reacts with both hydrogens of primary amines at relatively low temperatures (90—120°C) without added catalysts (105). When the nitrogen atom is hindered, as it is in the Triton RW products, only one of the amino hydrogens reacts with ethylene oxide. Once this reaction is complete, a basic catalyst is added and ethoxylation proceeds in the manner of the alcohol-based nonionics. In IV-alkyl-l,3-propanediamine, all three amino hydrogens are available for reaction with ethylene oxide. N-Alkyl-1,3-propanediamines are prepared from fatty monoamines and acrylonitrile, followed by reduction of the resulting 3-cyanoethylalkyl amine. 

REPPE PROCESS. Any of several processes involving reaction of acetylene (1) with formaldehyde to produce 2-butync-l,4-diol which can be converted to butadiene (2) with formaldehyde under different conditions to produce propargyl alcohol and, form this, allyl alcohol (3) with hydrogen cyanide to yield acrylonitrile (4) with alcohols to give vinyl ethers (5) with amines or phenols to give vinyl derivatives (6) with carbon monoxide and alcohols to give esters of acrylic acid (7) by polymerization to produce cyclooctatetraene and (8) with phenols to make resins. The use of catalysis, pressures up to 30 atm, and special techniques to avoid or contain explosions are important factors in these processes. 

The high electron density in the double bond system of ethylenes makes nucleophilic attack unfavorable unless the system is substituted with one or more electron withdrawing groups such as -N02, -CN, -COR. When these substituents are present, attack by alcohols or alkoxide ions occurs at the beta-carbon predominantly. For example, researchers have found (12) that sodium methoxide or sodium ethoxide added rapidly at room temperature to beta-nitrostyrene leads to the alkoxide formation of the derivative (Reaction VIII). This reaction is generally not only for arylnitroalkenes (13) but also for other activated double bonds (14). Another example of alcohol addition to an activated double bond includes the reaction of alcohols with acrylonitrile to produce a cyano-ethylated ether (14A). 

Pyridylethyl derivatives of 2 are formed by reaction of a- or y-vinyl-pyridine with 2.107 Treatment of 1 or 2, as well as the 5-arylidene derivatives, with acrylonitrile in the presence of pyridine results in formation of 84 by cyanoethylation on the ring nitrogen (Scheme 2) however, cyanoethyla-tion of 5-aryl-2-iminothiazolidinones involves the exocyclic nitrogen.108 Aminoalkylation (Mannich reaction) of 2 or 2-aryl-4-thiazolidinones with formaldehyde and amines in warm alcoholic solvents affords the desired 3-alkylated product 85 (Scheme 2),109,110 whereas 3-aryl-2-iminothiazoli-dinones react with substituted anilines and aliphatic amines and formaldehyde to give the 2-arylaminomethyl derivatives 86 [Eq. (25)].111... 

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