Azo compound

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General chemical formula of azo compounds

Azo compounds are compounds bearing the functional group R-N=N-R', in which R and R' can be either aryl or alkyl. IUPAC defines azo compounds as: "Derivatives of diazene (diimide), HN=NH, wherein both hydrogens are substituted by hydrocarbyl groups, e.g. PhN=NPh azobenzene or diphenyldiazene."[1] The more stable derivatives contain two aryl groups. The N=N group is called an azo group. The name azo comes from azote, the French name for nitrogen that is derived from the Greek a (not) + zoe (to live).

Most colored textile and leather articles are treated with azo dyes and pigments.[2]

As dyes and pigments[edit]

A yellow azo dye

As a consequence of п-delocalization, aryl azo compounds have vivid colors, especially reds, oranges, and yellows. Therefore, they are used as dyes, and are commonly known as azo dyes, an example of which is Disperse Orange 1. Some azo compounds, e.g., methyl orange, are used as acid-base indicators due to the different colors of their acid and salt forms. Most DVD-R/+R and some CD-R discs use blue azo dye as the recording layer. The development of azo dyes was an important step in the development of the chemical industry.

Azo pigments consist of colorless particles (typically earths or clays) colored using an azo compound. Azo pigments are important in a variety of paints including artist's paints. They have excellent coloring properties, again 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.

Organic chemistry[edit]

Aryl azo compounds[edit]

Aryl azo compounds are usually stable, crystalline species. Azobenzene is the prototypical aromatic azo compound. It exists mainly as the trans isomer, but upon photolysis, converts to the cis isomer.

Preparation[edit]

Aromatic azo compounds can be synthesized by azo coupling, which entails an electrophilic substitution reaction where an aryl diazonium cation is attacked by another aryl ring, especially those substituted with electron-donating groups:[3]

ArN2+ + Ar'H → ArN=NAr' + H+

Since diazonium salts are often unstable near room temperature, the azo coupling reactions are typically conducted near ice temperatures. The oxidation of hydrazines (R-NH-NH-R') also gives azo compounds.[4] 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 the diazo anilines shown below.[5]

Alkyl azo compounds[edit]

Aliphatic azo compounds (R and/or R' = aliphatic) are less commonly encountered than the aryl azo compounds. A commercially important alkyl azo compound is azobisisobutyronitrile (AIBN), which is widely used as an initiator in free radical polymerizations and other radical-induced reactions It achieves this initiation by decomposition, eliminating a molecule of nitrogen gas to form two 2-cyanoprop-2-yl radicals:

Formation of Radicals from AIBN.png

For instance a mixture of styrene and maleic anhydride in toluene will react if heated, forming the copolymer upon addition of AIBN.

A simple dialkyl diazo compound is diethyldiazene, EtN=NEt.[6] Because of their instability, aliphatic azo compounds pose the risk of explosion.

Preparation[edit]

AIBN is produced by converting acetone cyanohydrin to the hydrazine derivative followed by oxidation:[7]

2 (CH3)2C(CN)OH + N2H4 → [(CH3)2C(CN)]2N2H2 + 2 H2O
[(CH3)2C(CN)]2N2H2 + Cl2 → [(CH3)2C(CN)]2N2 + 2 HCl

Safety and regulation[edit]

Many azo pigments are non-toxic, although some, such as dinitroaniline orange, ortho-nitroaniline orange, or pigment orange 1, 2, and 5 have been found to be mutagenic.[8] Likewise, several case studies have linked azo pigments with basal cell carcinoma.[9]

Azo dyes derived from benzidine are carcinogens; exposure to them has classically been associated with bladder cancer.[10] Accordingly, the production of benzidine azo dyes was discontinued in the 1980s "in the most important western industrialized countries".[5]

European regulation[edit]

Certain azo dyes can break down 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.[2]

See also[edit]

References[edit]

  1. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2009) "azo compounds".
  2. ^ a b European Ban on Certain Azo Dyes, Dr. A. Püntener and Dr. C. Page, Quality and Environment, TFL
  3. ^ H. T. Clarke and W. R. Kirner (1941), Methyl Red, Org. Synth. ; Coll. Vol. 1: 374 
  4. ^ March, J. “Advanced Organic Chemistry” 5th Ed. J. Wiley and Sons, 1992: New York. ISBN 0-471-60180-2.
  5. ^ a b Klaus Hunger, Peter Mischke, Wolfgang Rieper, Roderich Raue, Klaus Kunde, Aloys Engel "Azo Dyes” in Ullmann’s Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim.doi:10.1002/14356007.a03_245.
  6. ^ Ohme, R.; Preuschhof, H.; Heyne, H.-U. (1988), Azoethane, Org. Synth. ; Coll. Vol. 6: 78 
  7. ^ Jean-Pierre Schirmann, Paul Bourdauducq "Hydrazine" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002. doi:10.1002/14356007.a13_177.
  8. ^ Tucson University. "Health & Safety in the Arts, A Searchable Database of Health & Safety Information for Artists". Tucson University Studies. 
  9. ^ Eva Engel, Heidi Ulrich, Rudolf Vasold, Burkhard König, Michael Landthaler, Rudolf Süttinger, Wolfgang Bäumler (2008). "Azo Pigments and a Basal Cell Carcinoma at the Thumb". Dermatology 216 (1): 76–80. doi:10.1159/000109363. PMID 18032904. 
  10. ^ Golka K, Kopps S, Myslak ZW (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.