Ammonia catalyzed reaction with ethylene

Eastham and Derwent474 have also studied the kinetics of the perchloric acid-catalyzed reaction of ethylene oxide with pyridine. In excess of pyridine the rate was found to be dependent on the Conor Titrations of ethylene oxide and perchloric add. Addition of stronger bases,. g. ammonia, triethylamine, or benzylamiae, depressed the vum of cleavage, presumably by competing with ethylene oxide for thr-available proton source, believed to be pyridinium perchlorate in this case. Other acids examined included nitric acid and hydroiodie irireaction rate depended to a certain extent... 

The use of ethylene adduct lb is particularly important when the species added to activate catalyst la is incompatible with one of the reaction components. Iridium-catalyzed monoallylation of ammonia requires high concentrations of ammonia, but these conditions are not compatible with the additive [Ir(COD)Cl]2 because this complex reacts with ammonia [102]. Thus, a reaction between ammonia and ethyl ciimamyl carbonate catalyzed by ethylene adduct lb produces the monoallylation product in higher yield than the same reaction catalyzed by la and [Ir(COD)Cl]2 (Scheme 27). Ammonia reacts with a range of allylic carbonates in the presence of lb to form branched primary allylic amines in good yield and high enantioselectivity (Scheme 28). Quenching these reactions with acyl chlorides or anhydrides leads to a one-pot synthesis of branched allylic amides that are not yet directly accessible by metal-catalyzed allylation of amides. 

The feasibility of acid-catalyzed direct hydroamination has been demonstrated. Acidic zeolites afford, at low conversions, highly selective formation of ethyla-mine,297,298 isopropylamine,298 and ferf-butylamine,298-301 in the reaction of ammonia with ethylene, propylene, and isobutylene, respectively. Amine formation is explained as a reaction of surface carbocation intermediates with adsorbed or... 

The first attempt to couple aryl halides with ammonia catalyzed by copper/ligand was reported by a Merck group (Scheme 9.1) [15]. In this case ethylene glycol may serve as both ligand and solvent, and the reaction proceded at 80 °C under elevated pressure. Mild conditions were discovered by Kim and Chang, in which L-proHne (LI) was employed as the ligand (Scheme 9.2) [16]. Both NH4CI and NH3-H20... 

Benzoguanamine is obtained by the reaction (heat and pressure) of ammonia dicyandiamide in the presence of aniline or by the sodium metal-catalyzed reaction of benzonitrile with dicyandiamide in ethylene glycol monomethyl ether. 

The intermolecular hydroamination of xmactivated alkenes with alkali metal catalysts has been known for a long time and a comprehensive review is available [7]. Reactions with ammonia or primary amines catalyzed by elemental lithium [140], sodium [141-144], potassium [141], alkali metal hydrides [141], and amides [145, 146] with ethylene typically require high reaction temperatures (250-500°C) and pressures (up to 1000 bar) and result in mixtures of mono-, di- and triethy-lamine in moderate yields. 

Ammonolysis of PET involves the reaction of PET and ammonia with heating and usually in die presence of ethylene glycol to form terephdialdiamide. The reaction is catalyzed by zinc acetate. 

In contrast, reactions catalyzed by la were typically conducted with added [Ir (C0D)C1]2 to trap the K -phosphoramidite ligand after dissociation, and thereby, to leave the unsaturated active catalyst. Under these conductions, as much as half of the iridium in the system is present in an inactive acyclic species. In contrast, when ethylene adduct lb is used as the catalyst, all of the iridium belongs to the active metalacyclic species. Hartwig and coworkers have recently taken advantage of the increased availability of the active catalyst generated from lb to develop new allylic substitution reactions. These new processes include the reactions of carbamates, nitrogen heterocycles, and ammonia. 

A number of zeolitic materials have been claimed to catalyze this reaction and reaction temperatures are on the order of 200-350 0 with pressures as high as 18000 kPa (2600 psi) reported. This is a low conversion process and recycle of the unconverted starting materials is necessary to proride an economical process. Amination of ethylene to produce ethylamines catalyzed by ammonium iodide is reported, but not believed to be practiced commercially (15,16). Alkyl Halide Amination (Method 7). The oldest technology for producing amines is the reaction of ammonia with an alkyl hahde. This... 

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