O-Phenylenediamine

Preparation

Commonly, 2-nitrochlorobenzene is treated with ammonia to generate 2-nitroaniline, whose nitro group is then reduced: :ClC6H4NO2 + 2 NH3 → H2NC6H4NO2 + NH4Cl

:H2NC6H4NO2 + 3 H2 → H2NC6H4NH2 + 2 H2O

In the laboratory, the reduction of the nitroaniline is effected with zinc powder in ethanol, followed by purification of the diamine as the hydrochloride salt. Darkened impure samples can be purified by treatment of its aqueous solution with sodium dithionite and activated carbon.

Reactions and uses

o-Phenylenediamine condenses with ketones and aldehydes to give rise to various valuable products. Its reactions with formic acids to produce benzimidazole. Other carboxylic acids give 2-substituted benzimidazoles. The herbicides benomyl and fuberidazole are made in this manner. Thiophanate-methyl is another herbicide produced from o-phenylenediamine. With nitrous acid, o-phenylenediamine condenses to give benzotriazole, a corrosion inhibitor.

Quinoxalinedione may be prepared by condensation of o-phenylenediamine with dimethyl oxalate. Mercaptoimidazole are commonly used as antioxidants in rubber production, obtained by condensing xanthate esters. Condensation of substituted o-phenylenediamine with diketones yields various pharmaceuticals.

OPD is a ligand in coordination chemistry. Oxidation of metal-phenylenediamine complexes affords the diimine derivatives. OPD condenses with salicylaldehyde to give chelating Schiff base ligands.

It reacts with thionyl chloride to give 2,1,3-benzothiadiazole:

Safety

With an LD50 of 44 mg/L (in water), o-phenylenediamine is about 1000 times less toxic than the para-isomer. Anilines are typically handled as if they are carcinogenic. For many applications, OPD has been replaced by safer alternatives such as 3,3',5,5'-tetramethylbenzidine.

References

References

1. "DuPont Specialty Intermediates: o-Phenylenediamine (OPD)".
2. (2016). "CRC Handbook of Chemistry and Physics". [[CRC Press]].
3. "Hazardous Substances Data Bank (HSDB) : 2893 - PubChem". PubChem.
4. (2000). "Phenylene- and Toluenediamines".
5. E. L. Martin. (1939). "''o''-Phenylenediamine". Organic Syntheses.
6. (1939). "Benzimidazole". Organic Syntheses.
7. (1950). "2-Mercaptobenzimidazole". Organic Syntheses.
8. (1940). "1,2,3-Benzotriazole". Organic Syntheses.
9. Renault, J.. (1981). "Heterocyclic quinones. Quinoxaline-5,6 and 5,8 diones, potential antitumoral agents". Eur. J. Med. Chem..
10. (2015). "New Avenues for Ligand-Mediated Processes – Expanding Metal Reactivity by the Use of Redox-Active Catechol, o-Aminophenol and o-Phenylenediamine Ligands". Chemical Society Reviews.
11. Deshpande SS. (1996). "Enzyme Immunoassays: From Concept to Product Development". Chapman & Hall.