AROMATIC AMINO COMPOUNDS

The aromatic amino compounds are a class of chemicals derived from aromatic hydrocarbons, such as benzene, toluene, naphthalene, anthracene and diphenyl by the replacement of at least one hydrogen atom by an amino group. A compound with a free amino group is described as a primary amine. When one of the hydrogen atoms of the group is replaced by an alkyl or aryl group, the resultant compound is a secondary amine; when both hydrogen atoms are replaced, a tertiary amine results. The hydrocarbon may have one amino group or two, more rarely three. It is thus possible to produce a considerable range of compounds and, in effect, the aromatic amines constitute a large class of chemicals of great technical and commercial value.

Aniline is the simplest aromatic amino compound, consisting of one group attached to a benzene ring and its derivatives are most widely used in industry. Other common single-ring compounds include dimethylaniline and diethylaniline, the chloroanilines, nitroanilines, toluidines, the chlorotoluidines, the phenylenediamines and acetanilide. Benzidine, o-tolidine, o-dianisidine, 3,3-dichlorobenzidine and 4aminodiphenyl are the most important conjoined ring compounds from the point of view of occupational health. Of compounds with ring structures, the naphthylamines and aminoanthracenes have attracted much attention because of problems of carcinogenicity. Strict precautions necessary for handling carcinogens apply to many members of this family.

Azo and diazo dyes Azo dye is a comprehensive term applied to a group of dyestuffs that carry the azo (N=N-) group in the molecular structure. The group may be divided into subgroups of monoazo, diazo and triazo dye and further in accordance with the number of the azo group in the molecule. From a toxicological perspective, it is important to take into account that the commercial grade dyestuffs usually contain impurities up to 20% or even higher. The composition and quantity of the impurities are variable depending on several factors such as the purity of the starting materials for the synthesis, the process of synthesis employed and the requirements of the users.

Production Azos dyes are synthesized by diazotization or tetrazotization of aromatic monoamine or aromatic diamine compounds with sodium nitrite in the HCl medium, followed by coupling with dye intermediates such as various aromatic compounds or heterocyclic

compounds. When the coupling component carries an amino group, it is possible to produce long-chained polyazo dye by the repetition of diazotization and coupling. The generalized structural formulae for the first three members of the family are:

R-N=N-R R-N=N-R-N=N-R" R-N=N-R-N=N-R"-N=NR

monoazo dye diazo dye triazo dye

Tetrazotization of benzidine and coupling with naphthionic acid yields the very popular dye Congo Red.

Uses Aromatic amino compounds are primarily used as intermediates in the manufacture of dyes and pigments. The largest class of dyestuffs is that of the azo colours, which are made by diazotization, a process by which a primary aromatic amine reacts with nitrous acid in the presence of excess mineral acid to produce a diazo (-N=N-) compound; this compound is subsequently coupled with a phenol or an amine. Another important class of dyestuffs, the triphenylmethane colours, is also manufactured from aromatic amines. In addition to serving as chemical intermediates in the dyestuffs industry, several compounds are employed as dyes or intermediates in the pharmaceutical, fur, hairdressing, textile and photography industries.

o-Aminophenol is used for dyeing furs and hair. It is also a developer in the photography industry and an intermediate for pharmaceuticals. p-Aminophenol is used in dyeing textiles, hair, furs and feathers. It finds use in photographic developers, pharmaceuticals, antioxidants and oil additives. 2,4-Diaminoanisole provides an oxidation base for dyeing fur. o-Toluidine, p-phenylenediamine, diphenylamine and Nphenyl-2-naphthylamine find additional uses as antioxidants in the rubber industry.

Diphenylamine is also employed in the pharmaceutical and explosives industries and as a pesticide. N-Phenyl-2-naphthylamine serves as a vulcanization accelerator, a stabilizer for silicone enamels and a lubricant. It is a component of rocket fuels, surgical plaster, tin-electroplating baths and dyes. 2,4-Diaminotoluene and 4,4diaminodiphenylmethane are useful intermediates in the manufacture of isocyanates, basic raw materials for the production of polyurethanes.

The major use of benzidine is in the manufacture of dyestuffs. It is tetrazotized and coupled with other intermediates to form colours. Its use in the rubber industry has been abandoned. Auramine is used in printing inks and as an antiseptic and a fungicide.

o-Phenylenediamine is a photographic developing agent and a hair dye component while p-phenylenediamine is used as a photographic chemical and a dyeing agent for fur and hair. However, p-phenylenediamine has been banned for use as an oxidation dye for hair in some countries. p-Phenylenediamine is also a vulcanization accelerator, a component of gasoline antioxidants. m-Phenylenediamine has numerous functions in the dyestuffs, rubber, textile, hairdressing and photography industries. It finds use in rubber curing agents, ion exchange and decolorizing resins, urethanes, textile fibers, petroleum additives, corrosion inhibitors and hair dyes. It is used as an promoter for adhering tire cords to rubber.

Xylidine serves as a gasoline additive as well as raw material in the manufacture of dyes and pharmaceuticals. Melamine is used in moulding compounds, textile and paper treating resins, and in adhesive resins for gluing lumber, plywood and flooring. In addition, it is useful in organic synthesis and in leather tanning. o-Tolidine is a reagent for the detection of gold.

Anilines The anilines are primarily used as intermediates for dyes and pigments. Several compounds are intermediates for pharmaceuticals, herbicides, insecticides and rubber processing chemicals, as well. Aniline itself is widely used in the manufacture of synthetic dyestuffs. It is also used in printing and cloth marking inks and in the manufacture of resins, varnishes, perfumes, shoe blacks, photographic chemicals, explosives, herbicides and fungicides. Aniline is useful in the manufacture of rubber as a vulcanizing agent, as an antioxidant, and as an antiozone agent. A further important function of aniline is in the manufacture of

p,p-methylenebisphenyldiisocyanate (MDI), which is then used to prepare polyurethane resin and spandex fibers and to bond rubber to rayon and nylon.

Chloroaniline exists in three isomeric forms: ortho, meta and para, of these only the first and the last are important for manufacturing dyes, drugs and pesticides. pNitroaniline is a chemical intermediate for antioxidants, dyes, pigments, gasoline gum inhibitors and pharmaceuticals. It is used in diazotized form to retain fastness of dyes after washing. 4,4-Methylene-bis(2-chloroaniline), MbOCA, is used as a curing agent with isocyanate-containing polymers for the manufacture of solid abrasion-resistant

urethane rubbers and moulded semi-rigid polyurethane foam articles with a hardened skin. These materials are used in an extensive range of products, including wheels, rollers, conveyor pulleys, cable connectors and seals, shoe soles, antivibration mounts and acoustic components. p-Nitroso-N,N,-dimethylaniline and 5-chloro-o-toluidine are used as intermediates in the dyestuffs industry. N,N-Diethylaniline and N,Ndimethylaniline are used in the synthesis of dyestuffs and other intermediates. N,NDimethylaniline also serves as a catalytic hardener in certain fibreglass resins.

Azo compounds Azo compounds are among the most popular groups of various dyes including direct dyes, acid dyes, basic dyes, naphthol dyes, acid mordant dyes, disperse dyes, etc., and are extensively used in textiles, fabrics, leather goods, paper products, plastics and many other items.

Hazards The manufacture and use in industry of certain aromatic amines may constitute a grave and sometimes unexpected hazard. However, since these hazards have become better known, there has, over recent years, been a tendency to substitute other substances or to take precautions which have reduced the hazard. Discussion has also taken place concerning the possibility of aromatic amines having health effects either when they exist as impurities in a finished product, or when they may be restored as the result of a chemical reaction taking place during the use of a derivative, or-and this is a totally different case-as the result of metabolic degradation within the organism of persons who may be absorbing more complex derivatives.

Absorption pathways Generally speaking, the principal risk of absorption lies in skin contact: the aromatic amines are nearly all lipid-soluble. This particular hazard is all the more important because in industrial practice it is one often not sufficiently appreciated. In addition to skin adsorption, there is also a considerable risk of absorption by inhalation. This may be the result of inhaling the vapours, even though most of these amines are of low volatility at normal temperatures; or it may result from breathing in dust from the solid products. This applies particularly in the case of the amine salts such as sulphates and chlorohydrates, which have a very low volatility and lipid solubility: the occupational hazard from the practical point of view is less but their over-all toxicity is about the same as the corresponding amine, and thus the inhalation of their dust and even skin contact must be considered dangerous.

Absorption by way of the digestive tract does represent a potential danger if inadequate eating and sanitary facilities are provided or if workers do not exercise excellent person hygiene practices. Contamination of food and cigarette smoking with dirty hands are two examples of possible ingestion routes.

Many of the aromatic amines are flammable and represent a moderate fire hazard. Combustion products can often be highly toxic. The primary health danger of industrial exposure to aniline arises from the ease with which it can be absorbed, either by inhalation or from skin absorption. Because of these absorptive properties, prevention of aniline poisoning requires high standards of industrial and personal hygiene. The most important specific measure for the prevention of spillage or contamination of the work atmosphere with aniline vapour is proper plant design. Ventilation control of the contaminant should be designed as close to the point of generation as possible. Work clothing should be changed daily and facilities for an obligatory bath or shower at the end of the working period should be provided. Any contamination of skin or clothing should be washed off immediately and the individual kept under medical supervision. Both workers and supervisors should be educated to be aware of the nature and extent of the hazard and to carry out the work in a clean, safe manner. Maintenance work should be preceded with sufficient attention to removal of possible sources of contact with the offending chemicals.

Since many cases of aniline poisoning result from contamination of the skin or clothing that leads to absorption through the skin, contaminated clothing should be removed and laundered. Even when intoxication results from inhalation, the clothing is likely to be contaminated and should be removed. The entire body surface, including hair and fingernails, should be carefully washed with soap and tepid water. Where methaemoglobinemia is present, appropriate emergency precautions should be taken and the occupational health service must be fully equipped and trained to handle such emergencies. Laundry workers should be provided with adequate precautions to avoid contamination from the aniline compounds.