Azo dyes are organic compounds bearing the functional group R−N=N−R′, in which R and R′ are usually aryl. They are a commercially important family of azo compounds, i.e. compounds containing the linkage C-N=N-C. Azo dyes are pervasively used to treat textiles, leather articles, and some foods. Chemically related to azo dyes are azo pigments, which are insoluble in water and other solvents.
Many kinds of azo dyes are known, and several classification systems exist. Some classes include disperse Dyes, metal-complex dyes, reactive dyes and substantive dyes. Also called direct dyes, substantive dyes are employed for cellulose-based textiles, which includes cotton. The dyes bind to the textile by non-electrostatic forces. In another classification, azo dyes can be classified according to the number of azo groups.
Physical properties, structure, and bondingEdit
As a consequence of п-delocalization, aryl azo compounds have vivid colors, especially reds, oranges, and yellows. An example is Disperse Orange 1. Some azo compounds, e.g., methyl orange, are used as acid-base indicators. Most DVD-R/+R and some CD-R discs use blue azo dye as the recording layer.
Azo dyes are solids. Most are salts, the colored component being the anion usually, although some cationic azo dyes are known. The anionic character of most dyes arises from the presence 1-3 sulfonic acid groups, which are fully ionized at the pH of the dyed article:
- RSO3H → RSO3− + H+
Most proteins are cationic, thus dying of leather and wool corresponds to an ion exchange reaction. The anionic dye adheres to these articles through electrostatic forces. Cationic azo dyes typically contain quaternary ammonium centers.
Most azo dyes are prepared by azo coupling, which entails an electrophilic substitution reaction of an aryl diazonium cation with another compound, the coupling partner. Classically coupling partners are other aromatic compounds with electron-donating groups:
2 + Ar′H → ArN=NAr′ + H+
In practice, acetoacetic amide are widely used as coupling partners:
2 + Ar′NHC(O)CH2C(O)Me → ArN=NCH(C(O)Me)(C(O)NHAr′) + H+
Azo dyes are also prepared by the condensation of nitroaromatics with anilines followed by reduction of the resulting azoxy intermediate:
- ArNO2 + Ar′NH2 → ArN(O)=NAr′ + H2O
- ArN(O)=NAr′ + C6H12O6 → ArN=NAr′ + C6H10O6 + H2O
For textile dying, a typical nitro coupling partner would be disodium 4,4′-dinitrostilbene-2,2′-disulfonate. Typical aniline partners are shown below. Since anilines are prepared from nitro compounds, some azo dyes are produced by partial reduction of aromatic nitro compounds.
Many azo dyes are produced by reactions from pre-existing azo compounds. Typical reactions include metal complexation and acylation.
Basic Red 18, a cationic azo dye
Azo pigments are similar in chemical structure to azo dyes, but they lack solubilizing groups. Because they are insoluble in virtually all media, they are not readily purified, and thus require highly purified precursors.
Azo pigments are important in a variety of plastics, rubbers, and paints (including artist's paints). They have excellent coloring properties, mainly in the yellow to red range, as well as good lightfastness. The lightfastness depends not only on the properties of the organic azo compound, but also on the way they have been absorbed on the pigment carrier.
The waste stream from dye factories can be intensely colored as well as potentially toxic. Great interest has been shown in the degradation of aza dyes to deliver a nontoxic, colorless effluent. Methods include adsorption, precipitation, chemical and photo-oxidation. Biological routes, which involve oxidase and hydroxylase enzymes, show promise.
Mutagenic compounds isolated from water samples, taken at sites below the sewage plants of the Nishitakase River in Kyoto, Japan show, that the azo dye (AZO DYE-1), used as an industrial material, is converted to the corresponding 2-phenylbenzotriazole derivative with a reducing reagent and subsequently to PBTA-1 by chlorination. PBTA-1 showed potent mutagenic activities in Salmonella typhimurium TA98 and YG1024, inducing 88 000 and 3 000 000 revertants, respectively, per μg, with S9 mix. The observations suggested that PBTA-1 is produced from AZO DYE-1 through deClPBTA-1, during industrial processes at dyeing factories and the treatment of wastewater at sewage plants.
Safety and regulationEdit
Azo dyes derived from benzidine are carcinogens; exposure to them has classically been associated with bladder cancer. Accordingly, the production of benzidine azo dyes was discontinued in the 1980s "in the most important western industrialized countries".
Certain azo dyes degrade under reductive conditions to release any of a group of defined aromatic amines. Consumer goods which contain listed aromatic amines originating from azo dyes were prohibited from manufacture and sale in European Union countries in September 2003. As only a small number of dyes contained an equally small number of amines, relatively few products were affected.
- IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2009) "azo compounds".
- European Ban on Certain Azo Dyes Archived 2012-08-13 at the Wayback Machine., Dr. A. Püntener and Dr. C. Page, Quality and Environment, TFL
- Klaus Hunger, Peter Mischke, Wolfgang Rieper, et al.: "Azo Dyes" in Ullmann’s Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim.doi:10.1002/14356007.a03_245.
- Paola Gilli; Valerio Bertolasi; Loretta Pretto; et al. (2002). "The Nature of Solid-State N−H···O/O−H···N Tautomeric Competition in Resonant Systems. Intramolecular Proton Transfer in Low-Barrier Hydrogen Bonds Formed by the ···OC−CN−NH··· ⇄ ···HO−CC−NN··· Ketohydrazone−Azoenol System. A Variable-Temperature X-ray Crystallographic and DFT Computational Study". J. Am. Chem. Soc. 124: 13554–13567. doi:10.1021/ja020589x.
- H. T. Clarke; W. R. Kirner (1941). "Methyl Red". Organic Syntheses.; Collective Volume, 1, p. 374
- A. Stolz (2001). "Basic and applied aspects in the microbial degradation of azo dyes". Applied Microbiology and Biotechnology. 56: 69–80. doi:10.1007/s002530100686.
- Shiozawa, Tatsushi; Muraoka, Koichi; Nukaya, Haruo; Ohe, Takeshi; Sawanishi, Hiroyuki; Oguri, Atsuko; Wakabayashi, Keiji; Sugimura, Takashi; Terao, Yoshiyasu (1998-04-01). "Chemical Synthesis of a Novel Aromatic Amine Mutagen Isolated from Water of the Nishitakase River in Kyoto and a Possible Route of Its Formation". Chemical Research in Toxicology. 11 (4): 375–380. doi:10.1021/tx970222j. ISSN 0893-228X.
- Tucson University. "Health & Safety in the Arts, A Searchable Database of Health & Safety Information for Artists". Tucson University Studies. Archived from the original on 2009-05-10.
- Eva Engel; Heidi Ulrich; Rudolf Vasold; et al. (2008). "Azo Pigments and a Basal Cell Carcinoma at the Thumb". Dermatology. 216 (1): 76–80. doi:10.1159/000109363. PMID 18032904.
- Golka, K.; Kopps, S.; Myslak, Z. W. (June 2004). "Carcinogenicity of azo colorants: influence of solubility and bioavailability". Toxicology Letters. 151 (1): 203–10. doi:10.1016/j.toxlet.2003.11.016. PMID 15177655. Review.