Addition, of ammonia to acrylonitrile

Addition of ammonia to acrylonitrile has been carried out in modest yield (31-33%). Hydrolysis of the nitrile group can be accomplished in the presence of either acids or bases. Hydrolysis in the presence of Ba(OH)2 has been reported in the literature to give /3-alanine in 85-90% yield. 

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. ... 

Derivation Addition of ammonia to (3-propiolac-tone, other processes based on the reaction of ammonia with acrylonitrile, etc. 

When mixed with bromine, acrylonitrile can explode. Dropwise addition of bromine to acrylonitrile without cooling the flask can also be violent. Reactions with strong oxidizers, strong bases, strong acids, ammonia, amines, and copper and its alloys can be violent. Lithium reacts exothermically with acrylonitrile. 

Although a wide variety of metals were claimed as active catalysts for formaldehyde hydrophosphination, platinum salts were preferred. Similarly, Group 10 metal salts were used to catalyze acrylonitrile hydrophosphination. Russian workers showed that Ni(II) or Co(II) salts in the presence of ammonia or amines would also catalyze the addition of phosphine to formaldehyde [6]. More recently, academic and industrial interest in these reactions was sparked by a series of papers by Pringle, who investigated late metal phosphine complexes as hydrophosphination catalysts. These and related studies are arranged below by substrate. 

Aminopropionitrile and bis-(fi-cyanoethyl)-amine have been made by the addition of anhydrous 2-3 or aqueous4 ammonia to acrylonitrile. 

Various p-aminonitriles, which are best prepared by the addition of ammonia, primary amines, or secondary amines to acrylonitrile,101 were successfully hydrogenated with Raney Ni at temperatures of 90-130°C and 6.7-27 MPa H2.102 A typical hydrogenation is shown in eq. 7.50 for P-morpholinopropionitrile. Hydrogenation of the nitrile at 190°C decreased the yield of y-morpholinopropylamine to 45%. The decrease in the yield may be explained by a reversal of the morpholine-acrylonitrile-... 

Other Addition Reactions - The photochemical addition in the gas phase of ammonia to a,P-unsaturated nitriles has been studied. The reactions are carried under conditions where all, or most, of the light is absorbed by the ammonia and this results in N-H bond fission and the production of NH2 radicals. These radicals add to the a-position of the substrate to yield 2-amino-propionitrile from acrylonitrile and analogous products are formed from crotononitrile, methacrylonitrile and 1-cyclohexenecarbonitrile. Additions also occur to but-2-yne nitrile which yields the Z, -isomers of 3-amino-crotononitrile with the E -isomer being predominant. The SET-induced amina-tion (using 1,4-dicyanobenzene as the sensitiser) of alkenylnaphthalene derivatives affords products of addition to both the alkene and the naphthalene skeleton. Suau et al. have examined the irradiation of phthalimide in the presence of low concentrations of hydroxide ion and alkenes. ° The result of this treatment is addition of the phthalimide moiety to the alkene. A SET... 

The rate of conversion of propane is practically the same in the presence and in the absence of ammonia. The oxidation yields propylene and carbon oxides, which are the prevailing products. However, when ammonia is added to the feedstock, the yield to propylene remains unchanged, while the yield to carbon oxides is remarkably decreased in favour of the formation of acrylonitrile. This suggests that in the absence of ammonia the propylene is oxidized to a compound or to an intermediate which under these conditions is burnt to carbon oxides. The addition of ammonia allows this intermediate compound (which might be acrolein or an allyl radical species) to be quickly transformed to the stable... 

Natural gas has become an important starting material for the manufacture of hydrogen, acetylene, and synthesis gas for producing methanol, Fischer-Tropsch hydrocarbons, ammonia, etc. The early processes for producing HCN from CH4, NH3, and air have been greatly improved, so that HCN can be added to the growing list of products derived from natural gas. An example of an important end product is Orion, the du Pont polyacrylonitrile synthetic fiber. The addition of HCN to acetylene yields the required acrylonitrile. 

In addition to these general comments, it may be adequate to mention here an example of potential practical interest, but possibly corresponding of a very particular case, actually a narrow alley. Oxynitrides were first studied as catalysts by Grange. One member of the family studied in his laboratory is extremely active and selective in the ammoxidation of propane to acrylonitrile (37-39). Even with the nonmodified, nondoped catalysts, a selectivity of 60% is easily achieved at 500°C with a productivity (e.g., per kilogram per hour) over 10 times higher than with the catalysts mentioned in literature. The catalyst is obtained by the action of ammonia on amorphous AlVi. Oy. This mixed oxide remains amorphous below 400°C, allowing... 

MAA and MMA may also be prepared via the ammoxidation of isobutylene to give meth acrylonitrile as the key intermediate. A mixture of isobutjiene, ammonia, and air are passed over a complex mixed metal oxide catalyst at elevated temperatures to give a 70—80% yield of methacrylonitrile. Suitable catalysts often include mixtures of molybdenum, bismuth, iron, and antimony, in addition to a noble metal (131—133). The meth acrylonitrile formed may then be hydrolyzed to methacrjiamide by treatment with one equivalent of sulfuric acid. The methacrjiamide can be esterified to MMA or hydrolyzed to MAA under conditions similar to those employed in the ACH process. The relatively modest yields obtainable in the ammoxidation reaction and the generation of a considerable acid waste stream combine to make this process economically less desirable than the ACH or C-4 oxidation to methacrolein processes. 

Acrylonitrile. Acrylonitrile is produced by reacting propylene, ammonia, and owgeu (air) in a single flmdized bed of a complex catalyst. Known as the SOHIO process, this process was first operated commercially in 1960. In addition to acrylonitrile, significant quantities of HCN and acetonitrile are also produced. This process is also exothermic. Temperature control is achieved by raising steam inside vertical tubes immersed in the bed [Veatch, Hydrocarbon Proce.ss. Pet. Refiner, 41, 18 (November 1962)]. 

Lengthening the side chain produces the antidepressant maprotiline (73), which has a topological relationship to the clinically useful tricyclic antidepressants. The requisite acid is constructed by conjugate addition of the carbanion of anthrone (64) to acrylonitrile, followed by hydrolysis to give 70. Reduction of the carbonyl group with zinc and ammonia gives anthracene 71 by dehydration of the intermediate... 

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