Aniline production using

The major uses of aniline are in the manufacture of polymers, mbber, agricultural chemicals, dyes and pigments, pharmaceuticals, and photographic chemicals. Approximately 67% of the wodd production of aniline is used in the manufacture of rigid polyurethanes and reaction-injection-molded (RIM) parts for the constmction, automotive, and durable goods industries. 

Aniline is an aromatic amine (CgHjNHj). When used as a solvent, it is selective to aromatic molecules at low temperatures, and paraffins and naphthenes at higher temperature. Aniline is used to determine aromaticity of oil products, including FCC feedstocks. Aniline point (AP) is the minimum temperature for complete solubility of an oii sample in aniline. 

Meerwein reactions can conveniently be used for syntheses of intermediates which can be cyclized to heterocyclic compounds, if an appropriate heteroatom substituent is present in the 2-position of the aniline derivative used for diazotization. For instance, Raucher and Koolpe (1983) described an elegant method for the synthesis of a variety of substituted indoles via the Meerwein arylation of vinyl acetate, vinyl bromide, or 2-acetoxy-l-alkenes with arenediazonium salts derived from 2-nitroani-line (Scheme 10-46). In the Meerwein reaction one obtains a mixture of the usual arylation/HCl-addition product (10.9) and the carbonyl compound 10.10, i. e., the product of hydrolysis of 10.9. For the subsequent reductive cyclization to the indole (10.11) the mixture of 10.9 and 10.10 can be treated with any of a variety of reducing agents, preferably Fe/HOAc. 

Tu found that when aniline was used instead of the secondary amine under otherwise identical conditions 2,4-diphenyl-substituted quinoline was formed in 56% yield. Phenylacetylene and aniline were initially used as model substrates for exploring the aldehyde scope. With aromatic aldehydes the reactions proceeded smoothly to give the corresponding quinolines in moderate to good yields. A heteroaromatic aldehyde is also compatible with this transformation and the expected product was afforded in 83% yield. However, when ahphatic aldehydes were subjected to the reaction, the desired product was obtained in low yield (Scheme 19) [34]. 

The reduction of nitrobenzene to aniline is a major industrial process at the heart of the production of polyurethanes, and it is also often used as a marker reaction to compare activities of catalysts [1,2], It can be performed over a variety of catalysts and in a variety of solvents. As well as its main use in polymethanes, aniline is used in a wide range of industries such as dyes, agrochemicals, by further reaction and functionalisation. Reductive alkylation is one such way of functionalising aromatic amines [3, 4], The reaction usually takes place between an amine and a ketone, aldehyde or alcohol. However it is possible to reductively alkylate direct from the nitro precursor to the amine and in this way remove a processing step. In this study we examined the reductive alkylation of nitrobenzene and aniline by 1-hexanol. 

N-Nitroso compounds occur in many operations in the rubber industry. Some nitrosamines (nitrosodiphenylamine, N-N-dinitrosopentamethylenetetramine, polymerized N-nitroso 2,2,4-trimethyl-l,2-dihydroquinoline and N-methyl-N-4-dinitroso aniline) are used as organic accelerators and antioxidants in the production of rubber and often the products are found to be contaminated with such compounds [19]. 

The catalytic reduction of nitro groups is usually achieved using heterogeneous catalysts, although the iridium complex 28 has been shown to be effective for the reduction of p-nitroanisole 29 to the corresponding aniline 30 using isopropanol as the hydrogen donor (Scheme 8) [30]. In the reduction of some nitroarenes, azo compounds (Ar-N=N-Ar) could be formed as by-products or as the major product by variation of the reaction conditions. 

X 10mol/L). Both experiments were conducted at 25 °C. The decomposition rate of 4-nitro-aniline was very high by the photo-Fenton reaction in comparison to titanium dioxide-UV light (k = 365 nm). Decomposition products identified in both reactions were nitrobenzene, p-benzoquinone, hydroquinone, oxalic acid, and resorcinol. Oxalic acid, hydroquinone, and p-benzoquinone were identified as intermediate products using HPLC. 

Loxapine Loxapine, 2-chloro-11-(4-methyl-l-piperazinyl)dibenz [b,f][l,4]exazepine (6.5.3), which is synthesized from 2-(4-chlorophenoxy)anyline. Acylation of the resulting product using ethylchloroformate forms A-ethoxycarbonyl-2-(4-chlorophenoxy)aniline (6.5.2). Treatment of this product with a mixture of phosphorous oxychloride and phosphorous anhydride gives loxapine (6.5.3) [53-55]. 

CH3(CH3N=)CCH2COCH3 + (CH3(CH2)3NH2. A solution of the ligand (0.05 mole) in 10 ml. of n-butylamine was refluxed for one-half hour and distilled under reduced pressure (2 mm.). The product distilled at 77-80° at 2 mm., as did the pure ligand (recovery =95%). Similarly, only starting material was obtained (95% recovery) when aniline was used instead of n-butylamine. 

Nitrobenzene and nitrotoluenes that are manufactured are converted to aniline, isocyanates, and other products used in the production of dyes and pharmaceuticals. 

The use of certain vanadium compounds as catalysts has been increasing. Vanadium oxy trichloride is a catalyst in making ediylene-propylene rubber. Ammonium metavanadate and vanadium pentoxide aie used as oxidation catalysts, particularly in the production of polyamides, such as nylon, in the manufacture of H>S04 by the contact process, in the production of phdialic and maleic anhydrides, and in numerous other oxidation reactions, such as alcohol to acetaldehyde, anthracene to anthraquinone, sugar to oxalic acid, and diphenylamine to carbazole. Vanadium compounds have been used for many years 111 die ceramics field for enamels and glazes. Colors are produced by various combinations of vanadium oxide and silica, zirconia, zinc, lead, tin, selenium, and cadmium. Vanadium intermediate compounds also are used in the making of aniline Mack used by the dye industry... 

An enantioselective one-pot, three-component imino-Reformatsky reaction has been reported.20 Combining a benzaldehyde, an aniline, and an alkyl bromoacetate ester, (g) ees of up to 92% have been achieved in the /i-amino ester product, using a recyclable A-methylcphedrinc as auxiliary. A nickel(II) salt and dimethylzinc are employed the latter serves as dehydrating agent, reductant, and coordinating metal. 

The reaction of ammonia and phenol is also being used for aniline production. 

Aniline is used in the rubber industry for the manufacture of various vulcanization accelerators and age resistors. Aniline is also used in the production of herbicides, dyes and pigments, and specialty fibers. 

Nitrobenzene Nitrobenzene is made by the direct nitration of benzene with nitric/sulfuric acid mixtures primarily for aniline production. And aniline is a raw material for the manufacture of methylene diphenyl diisocyanate (MDI) that is used to make rigid foams. 

The primary aniline production process in the world is the hydrogenation of nitrobenzene. BASF, DuPont, ChemFirst (purchased by DuPont in 2002) and Rubicon use this process in the United States. This technology is also used by all Western European aniline producers and all but one Japanese aniline producer. 

Benzophenone imine is commercially available and serves as an ammonia surrogate that reacts with aryl halides in high yields under standard palladium-catalyzed conditions. Catalysts based on both DPPF- and BINAP-ligated palladium gave essentially quantitative yields for reactions of aryl bromides. These reactions can be conducted with either Cs2C03 or NaO-/-Bu as base [137,138]. The products are readily isolated by chromatographic techniques or by crystallization. They can be cleaved to the parent aniline by using hydroxylamine, acid, or Pd/C [138]. 

The high reactivity of aniline can actually be a problem. Suppose we wanted to put just one bromine atom on to the ring. With phenol, this is possible (p. 557)—if bromine is added slowly to a solution of phenol in carbon disulfide and the temperature is kept below 5 °C, the main product is para-bro-mophenol. Not so if aniline is used—the main product is the triply substituted product. 

In 2000, the aniline production in the United States was about 1.9 billion lb. Almost 98 percent of nitrobenzene is used for the production of aniline. Consequently many nitrobenzene plants are integrated with facilities for aniline production. The hydrogenation of nitrobenzene can be done in either the vapor over a copper-silica catalyst or in liquid phase over platinum-palladium catalyst. One of the smaller uses for nitrobenzene is the production of the pain reliever, acetaminophen. 

Aniline can also be made by two other methods. In the first, nitrobenzene is reduced by reaction with scrap iron in the presence of a hydrochloric acid catalyst. The iron is oxidized to the ferrous state, and the coproduct aniline is separated. This route accounts for less than 5 percent of the current aniline production. The other process avoids nitrobenzene entirely and involves the vapor-phase ammonolysis of phenol, using an alumina catalyst. Aniline is formed with dipheny-lamine as a by-product. About 20 percent of the aniline is produced by this route. 

Other aniline uses and the percent of worldwide aniline production that goes into these uses are rubber-processing chemicals (9%), dyes and pigments (2%), agricultural chemicals (3%), specialty fibers (1%), and miscellaneous, such as explosives, epoxy curing agents, and pharmaceuticals (1%).138,255... 

The amount of aniline used in the manufacture of blue is of great importance. In presence of a large excess of aniline the phenylation is more complete and rapid than when a small quantity is used. For production of pure triphenylrosaniline (green shade of blue) a large excess of aniline is used (ten times the theoretical amount) along with a correspondingly large amount of... 

In the laboratory of R. Bihovsky, a series of peptide mimetic aldehyde inhibitors of calpain I was prepared in which the P2 and P3 amino acids were replaced with substituted 3,4-dihydro-1,2-benzothiazine-3-carboxylate-1,1-dioxides. The synthesis began with the diazotization of the substituted aniline substrate using sodium nitrite and hydrochloric acid. The aqueous solution of the corresponding diazonium chloride product was added dropwise to the solution of acrylonitrile in a water-acetone mixture, which contained catalytic amounts of copper(ll) chloride. This Meerwein arylation step afforded the chloronitrile derivative, which was subjected to sulfonation with chlorosulfonic acid, and the resulting sulfonyl chloride was treated with the solution of ammonia in dioxane to give the desired 3,4-dihydro-1,2-benzothiazine-2-carboxamide. 

Spandex stretch fiber, based on polyurethanes, was developed by DuPont and appeared in 1962. From this time, polyurethanes would account for the greater part of demand for anilines. Aniline production alone had more than doubled, to over 100 million lbs. per year, between 1939 and 1957, in part to satisfy demand in products other than dyes. Half the US output was consumed in the production of rubber additives, mainly diphenylamine and cyclohexylamine, the latter used as a chain stopper in manufacture of polyurethanes (also as a boiler water additive and, in the US until banned in 1970, in the manufacture of cyclamate sweeteners). Other polymers, such as epoxy resins, relied on the bulk availability of various aromatic amines (Chapter 14). 

Over half of the remaining market for products used in the processing of rubber is made up of antioxidants, antiozonants and stabilizers, either amino compounds or phenols. Aniline is used to manufacture vulcanization accelerators, antioxidants and antidegradants. Of the latter, several are A-substituted derivatives of p-phenylenediamine and octyl dipheny-lamine. Diphenylamines terminate free-radical reactions by donating the amino hydrogen, and are used to protect a wide range of polymers and elastomers. Many synthetic rubbers incorporate alkylated diphenylamine antioxidants. Other antioxidants include aryl amine resinous products from, e.g. condensation of aniline and acetone in the presence of... 

The system was first applied for development of chemosensors for gaseous hydrogen chloride. Polyaniline, and its copolymers with different derivates of aniline were used. Then a similar approach was tested in the author s group for optimization of amperometric biosensors for glucose based on electrocatalytical detection of hydrogen peroxide. A pigment Prussian blue was used as an electrocatalyst for decomposition of this product of enzymatic oxidation of... 

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