2-Nitrochlorobenzene Explained

2-Nitrochlorobenzene is an organic compound with the formula ClC6H4NO2. It is one of three isomeric nitrochlorobenzenes.[1] It is a yellow crystalline solid that is important as a precursor to other compounds due to its two functional groups.

Synthesis

Nitrochlorobenzene is typically synthesized by nitration of chlorobenzene in the presence of sulfuric acid:

C6H5Cl + HNO3 → O2NC6H4Cl + H2O

This reaction affords a mixture of isomers. Using an acid ratio of 30% nitric acid, 56% sulfuric acid and 14% water, the product mix is typically 34-36% 2-nitrochlorobenzene and 63-65% 4-nitrochlorobenzene, with only about 1% 3-nitrochlorobenzene.[1]

Reactions

2-Nitrochlorobenzene can be reduced to the 2-chloroaniline with Fe/HCl mixture, the Bechamp reduction.[1]

2-Nitrochlorobenzene, like its isomers, is reactive toward nucleophiles, resulting in chloride substitution. With polysulfide, it reacts to give di-orthonitrophenyl disulfide:[2]

Similarly, it reacts with sodium methoxide to give 2-nitroanisole.

Substitution of chloride by fluoride is also practiced commercially to convert 2-nitrochlorobenzene to 2-fluoronitrobenzene. The Halex process uses potassium fluoride in polar solvents like sulfolane :

Applications

2-Nitrochlorobenzene is useful because both of its reactive sites can be utilized to create further compounds that are mutually ortho. Its derivative 2-chloroaniline is a precursor to 3,3’-dichlorobenzidine, a precursor to dyes and pesticides.

References

  1. Book: 10.1002/14356007.a17_411 . Nitro Compounds, Aromatic . Ullmann's Encyclopedia of Industrial Chemistry . 2000 . Booth . Gerald . 978-3-527-30385-4. Wiley-VCH. Weinheim.
  2. 10.15227/orgsyn.008.0064 . Di-o-Nitrophenyl Disulfide . Organic Syntheses . 1928 . 8 . 64. Marston T. . Bogert. Arthur. Stull .