Butadiene reaction with ammonia

Direct addition of ammonia to olefmic bonds would be an attractive method for amine synthesis, if it could be carried out smoothly. Like water, ammonia reacts with butadiene only under particular reaction conditions. Almost no reaction takes place with pure ammonia in organic solvents. The presence of water accelerates the reaction considerably. The reaction of aqueous ammonia (28%) with butadiene in MeCN in the presence orPd(OAc)i and PhjP at 80 C for 10 h gives tri-2,7-octadienylamine (47) as the main product, accompanied by a small amount of di-2,7-octadienylamine (46)[46,47], Isomeric branched... 

Reaction of aqueous ammonia (28%) with butadiene in MeCN in the presence of Pd(OAc)2 and PI13P at 80 °C gives tri-2,7-octadienylamine (141) as the main product [66,67], The reaction proceeds stepwise, but the primary amine 142 is more reactive than ammonia, and the secondary amine is more reactive than the primary amine. Thus the main product is the trioctadienylamine (141), even when the reaction is stopped before completion. 

The most characteristic reaction of butadiene catalyzed by palladium catalysts is the dimerization with incorporation of various nucleophiles [Eq. (11)]. The main product of this telomerization reaction is the 8-substituted 1,6-octadiene, 17. Also, 3-substituted 1,7-octadiene, 18, is formed as a minor product. So far, the following nucleophiles are known to react with butadiene to form corresponding telomers water, carboxylic acids, primary and secondary alcohols, phenols, ammonia, primary and secondary amines, enamines, active methylene compounds activated by two electron-attracting groups, and nitroalkanes. Some of these nucleophiles are known to react oxidatively with simple olefins in the presence of Pd2+ salts. Carbon monoxide and hydrosilanes also take part in the telomerization. The telomerization reactions are surveyed based on the classification by the nucleophiles. 

SYN NITROGEN CHLORIDE DOT CLASSIFICATION Forbidden SAFETY PROFILE Strong irritant by inhalation. An extremely unstable explosive. Reacts with liquid ammonia to form an explosive liquid. Explosive reaction with 1,3-butadiene, C2H6, C2H4, CH4, CsHs, phopshorus, silver azide, sodium. Reacts with water or steam to produce toxic and corrosive fumes of HCl. Has been used as an initiator in chemical gas lasers. When heated to decomposition it emits toxic fumes of Cr and NOx- See also CHLORINE and AZIDES. 

Explosive reaction with acetylene, antimony powder, hafnium powder + heat, tetraamine copper(II) sulfate + ethanol, trioxygen difluoride (possibly ignition), polyacetylene (at 113°C). Forms sensitive, explosive mixtures with potassium (impact-and heat-sensitive), sodium (shock-sensitive), oxygen difluoride (heat-sensitive). Reacts to form explosive products with ammonia, ammonia + Uthium 1-heptynide, ammonia + potassium, butadiene + ethanol + mercuric oxide, silver azide. 

Telomerizations have been among the first reactions tested under biphasic conditions [45, 190], starting with butadiene and methanol on Pd/TPPMS catalysts and yielding l-methoxy-2,7-octadiene. The telomerization in the presence of water as reactant (hydrodimerization cf Scheme 1) has been commercialized [15, 31, 42-44]. These biphasic developments of the Kuraray Corporation yield 1-octanol or 1,9-nonanediol, respectively (cf [15, 31, 42 4, 86, 133, 137, 244 e] and Section 2.3.5). Similar developments (but without technical realization) have been described by BASF [134], Mitsubishi [135], and Shell [136], and others [215 d, 242, 268]. The telomerization of butadiene and ammonia may also be biphasic [243]. 

Derivation (1) Reaction of adipic acid and ammonia (catalytic vapor phase) to yield adiponitrile, followed by liquid-phase catalytic hydrogenation. (2) Chlorination of butadiene followed by reaction with sodium cyanide (cuprous chloride catalyst) to 1,4-dicyanobutylene and hydrogenation. 

By analogy with butadiene, we might expect an aptitude kinetically for reaction in the s-cis conformation. This has barely been looked at lithium in ammonia reduction of various a,/3-unsaturated ketones gives mixtures of the E- and Z-enolates possibly reflecting the proportions of the s-trans and s-cis conformers, respectively, in the starting material as well as their relative reactivity with respect to accepting an electron. There is, however, some evidence that the proportion of Z-enolate is a little higher than the proportion of s-cis conformer.169... 

SULFUROUS OXIDE (7446-09-5) SO, Noncombustible liquefied gas under pressure or liquid. Contact with air forms hydrogen chloride fumes. Violent reaction with water or steam, forming sulfurous acid, a medium-strong acid and corrosion hazard. Reacts violently with acetylene, acrolein, alcohols, aluminum powder alkali metals (i.e., potassium, sodium) amines, ammonia, bromine pentafluoride butadiene caustics, cesium acetylene carbide chlorates, chlorine trifluoride chromium powder copper or copper alloy powders chlorine, diethylzinc, fluorine, ethylene oxide lead dioxide lithium acetylene carbide diamino-, metal powders monolithium acetylide-ammonia nitryl chloride potassium acetylene carbide potassium acetylide, potassium chlorate rubidium carbide silver azide sodium acetylide staimous oxide. Decon oses in... 

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