Electrophilic halogenation

In organic chemistry, an electrophilic aromatic halogenation is a type of electrophilic aromatic substitution. This organic reaction is typical of aromatic compounds and a very useful method for adding substituents to an aromatic system.

A few types of aromatic compounds, such as phenol, will react without a catalyst, but for typical benzene derivatives with less reactive substrates, a Lewis acid catalyst is required. Typical Lewis acid catalysts include AlCl3, FeCl3, FeBr3, and ZnCl2. These work by forming a highly electrophilic complex which attacks the benzene ring.

Chlorination of Benzene
We will consider the production of chlorinated benzenes in a simple batch reactor. Initially the reactor contains only benzene (in the liquid phase) plus a catalyst. Then (a gas) is bubbled into the liquid continuously with HCl removed continuously out the top of the reactor. The system is approximately constant volume, with benzene consumed and the different chlorinated products produced over time. Chlorination takes place by first adding one chlorine atom to the benzene ring producing monochlorobenzene along with . Next an additional chlorine atom is added and dichlorobenzenes are produced as well.

There are 3 different isomeric dichlorobenzenes although only one is represented in the figure above (they differ by the relative positions of the chlorine atoms attached to the benzene ring). Each compound, except hexachlorobenzene, can be further chlorinated. Twelve chlorinated benzenes can be formed by replacing some or all of the hydrogen atoms of benzene with chlorine atoms. The product is always a mixture of chlorinated benzenes that can be separated by distillation and crystallization.

Chlorinated Benzene
The chlorinated benzenes have been products of commercial interest since the early 1900s. One of the main uses of chlorobenzene was in the production of DDT, a widely used insecticide. Due to environmental hazards, the use of DDT in the United States was later restricted by the EPA, greatly reducing the demand for chlorobenzene and shifting its main use to dye manufacturing and as a solvent. Some chlorobenzene producers stress production of dichlorobenzenes which have been in increasing demand in the manufacture of pesticides, space deodorants, moth control products, as solvents, in the production of dyes, and as other chemical intermediates. We will consider the production of chlorinated benzenes in a simple batch reactor. Initially the reactor contains only benzene (in the liquid phase) plus a catalyst. Then Cl (a gas) is bubbled into the liquid continuously with HCl removed continuously out the top of the reactor. The system is approximately constant volume, with benzene consumed and the different chlorinated products produced over time. The goal is: To determine how long to run the reactor in order to maximize the yield of one of the chlorinated benzenes.