Amines aromatic, nitration

Nevertheless, such reactions catalyzed by zeolites have been discussed in the review of 2001 (1) isomerization (double-bond shift, isomerization of tricyclic molecules, like synthesis of adamantane, isomerization of terpenes, diverse rearrangements, conversion of aldehydes into ketones), (2) electrophilic substitution in arenes (alkylation of aromatics, including the synthesis of linear alkylbenzenes, alkylation and acylation of phenols, heteroarenes and amines, aromatics nitration and halogenation), (3) cyclization, including the formation of heterocycles, Diels-Alder reaction, (4) nucleophilic substitution and addition,... 

The y -phenylenediamiaes are easily obtained by dinitrating, followed by catalyticaHy hydrogenating, an aromatic hydrocarbon. Thus, the toluenediamiaes are manufactured by nitrating toluene with a mixture of sulfuric acid, nitric acid, and 23% water at 330°C which first produces a mixture (60 40) of the ortho and para mononitrotoluenes. Further nitration produces the 80 20 mixture of 2,4- and 2,6-dinitrotoluene. Catalytic hydrogenation produces the commercial mixture of diamiaes which, when converted to diisocyanates, are widely used ia the production of polyurethanes (see Amines, aromatic, DIAMINOTOLUENES) (22). 

Since many dyes contain aromatic amines one of the most important reactions carried out in the synthesis of dye intermediates is aromatic nitration, involving use of stoichiometric amounts of nitric and sulfuric acid as discussed previously. Many cleaner nitration processes have been proposed, but here discussion will be limited to the use of lanthanide... 

The nitration of aromatic hydrocarbons is one of the most widely studied and well-documented reactions in organic chemistry. Aromatic nitro compounds are of huge industrial importance in the synthesis of pharmaceutical drugs, agrochemicals, polymers, solvents and perfumes, and for the synthesis of other industrially important chemicals containing amine and isocyanate functionality. However, early research into aromatic nitration was fuelled exclusively by their use as explosives and intermediates in the synthesis of dyestuffs. The former is the subject of this chapter. 

Show how you would prepare the following aromatic amines by aromatic nitration, followed by reduction. You may use benzene and toluene as your aromatic starting materials. 

Ketone, aromatic nitrate, tertiary amine, pyridine, sulfone, trialkyl phosphate or phosphine oxide + 0 + + 0 + +... 

The most widely used method for preparing aromatic amines involves nitration of the ring and subsequent reduction of the nitro group to an amino group ... 

The best route to aromatic primary amines is by reduction of the corresponding nitro compounds, which are in turn prepared by electrophilic aromatic nitration. The nitro group is easily reduced, either catalytically with hydrogen or by chemical-reducing agents. 

Aromatic nitriles are now available from the previously discussed (see Section 1, Primary Amines) ipso nitration products. Thus, the cyclohexadienyl chloride (17) reacts with sodium cyanide under phase-transfer conditions to produce the corresponding aromatic nitrile. ... 

Keywords Aromatic aldehydes, p-keto esters, amines, bismuth nitrate, ethanol, room temperature, homogeneous catalysis, tandem reaction, one-pot synthesis, multicomponent reaction (MCR), Mannich reaction, functionalized piperidines... 

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