Estimates place the amount of chloromethane (methyl chloride; CH₃Cl) that results from natural biological processes at more than five million tons (five billion kilograms) per year. Most of this is produced in the oceans by marine algae and kelp, but terrestrial organisms—especially fungi—also contribute. Smaller quantities (less than 250,000 tons per year) enter the atmosphere as a result of volcanic emissions, forest fires, and human activity. Ocean-living organisms are a source of bromomethane (CH₃Br) and iodomethane (CH₃I). More than 50 organohalogen compounds, including CHBr₃, CHBrClI, BrCH₂CH₂I, CH₂I₂, Br₂CHCH=O, I₂CHCO₂H, and (Cl₃C)₂C=O, have been identified as being present in the Hawaiian red seaweed Asparagopsis taxiformis. Virtually every marine plant that has been assayed has been found to produce organohalogen compounds, many of which have quite complicated structures.

Several naturally occurring halogen-containing substances have pharmaceutical applications. An example is the antibiotic chloramphenicol produced by Streptomyces venezuelae.

Fluorine-containing natural products are relatively rare, the most prominent examples being ω-fluoro fatty acids. (The prefix ω indicates that the substitution occurs at the end of a chain.) Fluoroacetic acid, FCH₂CO₂H, occurs in the South African plant Dichapetalum cymosum and is quite toxic. A related Dichapetalum species contains 16-fluorohexadecanoic acid, FCH₂(CH₂)₁₄CO₂H, which is also poisonous when ingested, because of its subsequent metabolic conversion to fluoroacetic acid.

Synthesis

Alkyl halides are prepared by three main methods.

The first is the reaction of an alcohol with a hydrogen halide, as in the following synthesis of 1-bromobutane.

The second method is addition of a hydrogen halide to an alkene; e.g.,

The third method is free-radical halogenation of an alkane; e.g.,

Each of these three methods suffers from certain features that limit its generality. Consequently, the particular method chosen depends on the structure of the desired alkyl halide.

Vicinal dihalides, compounds that have halogens on adjacent carbons, are prepared by the reaction between a halogen and an alkene. The simplest example is the reaction between ethylene and chlorine to give 1,2-dichloroethane (ethylene dichloride). 1,2-Dichloroethane leads all other organohalogen compounds in terms of its annual production, which averages nearly 20 million tons globally per year. Most of this material is converted to vinyl chloride and then to polyvinyl chloride, or PVC.

The methods described above are best suited for preparing alkyl chlorides and bromides. Alkyl fluorides and iodides are normally made from the corresponding chloride or bromide by nucleophilic substitution (see below Reactions).

Among one-carbon organohalogen compounds, chloromethane is important as the starting material for the preparation of dichlorodimethylsilane, (CH₃)₂SiCl₂, from which silicone polymers are produced. The main method for the synthesis of chloromethane is the reaction of methanol with hydrogen chloride:

A second method, the high-temperature gas-phase chlorination of methane, contributes about one-third of the annual chloromethane production.

Dichloromethane, used as a solvent, a paint remover, and aerosol propellant, is prepared by chlorination of chloromethane, and trichloromethane is prepared by chlorination of dichloromethane.

Production of a large number of other one- or two-carbon organohalogen compounds has either been curtailed or eliminated because of the hazards they present with regard to ozone depletion, global warming, carcinogenicity, or toxicity. One example is the group of compounds called chlorofluorocarbons, or CFCs. A typical CFC is dichlorodifluoromethane (CCl₂F₂; also known as CFC-12). Chlorofluorocarbons were introduced in the 1930s as safe, stable, nontoxic refrigerant gases and shortly thereafter became the standard materials for this purpose. In the 1970s, however, research by American chemists F. Sherwood Rowland and Mario Molina and by Dutch chemist Paul Crutzen, who shared the 1995 Nobel Prize for Chemistry, indicated that CFCs were involved in the thinning of the ozone layer in Antarctica. Being very stable gases, CFCs diffuse through the atmosphere and into the stratosphere (the atmospheric region that is approximately 10 to 50 km [6 to 30 miles] above the Earth’s surface), where ultraviolet radiation induces their dissociation by carbon-chlorine bond cleavage. The products of this cleavage are a chlorine atom and a chlorodifluoromethyl radical. (A free radical is a species that has one or more unpaired electrons.)

With respect to ozone depletion, the chlorine atom is the more important product of this dissociation. The chlorine atom reacts with atmospheric ozone, abstracting an oxygen atom to form chlorine monoxide:

At this point, one chlorine atom has reacted with one ozone molecule. However, a sequence of several steps follows in which chlorine monoxide reacts further to cleave a second molecule of ozone while regenerating a chlorine atom. This chlorine atom can then react with another ozone molecule to continue the process, eventually causing the destruction of thousands of ozone molecules.

Because ozone is an important absorber of ultraviolet radiation, any decrease in the stratospheric concentration of ozone carries with it an increased risk of skin cancer. In 1987 the United Nations Environment Programme drafted the Montreal Protocol on Substances That Deplete the Ozone Layer, under which most of the world’s industrialized nations agreed in 1990 to phase out all uses of CFCs by the year 2000. Later amendments to the Montreal Protocol have allowed developed countries to continue to produce and use certain CFCs, including chloromethane, but they are expected to phase out their dependence on these chemicals by 2030.

In addition to CFCs, which are sources of chlorine atoms, sources of bromine atoms are ozone depleters. Bromomethane (methyl bromide) is an example, and it was scheduled to be phased out by 2005; however, developed countries have been granted permission to negotiate annual exemptions. In 2006 the global production of bromomethane was capped at 13,000 metric tons—a 20 percent reduction from the previous year. Less-developed countries are expected to phase out their use of bromomethane by 2015. Most of the atmospheric bromomethane arises from biological processes that occur in the oceans, but about one-quarter results from the bromomethane used each year as a soil fumigant for agricultural purposes.