# Halogenation of Alkanes

### Chlorination of Methane by Substitution

Halogenation is the replacement of one or more hydrogen atoms in an organic compound by a halogen (fluorine, chlorine, bromine or iodine). Unlike the complex transformations of combustion, the halogenation of an alkane appears to be a simple substitution reaction in which a C-H bond is broken and a new C-X bond is formed. The chlorination of methane, shown below, provides a simple example of this reaction.

CH4   +   Cl2   +   energy   →  CH3Cl   +   HCl

Since only two covalent bonds are broken (C-H & Cl-Cl) and two covalent bonds are formed (C-Cl & H-Cl), this reaction seems to be an ideal case for mechanistic investigation and speculation. However, one complication is that all the hydrogen atoms of an alkane may undergo substitution, resulting in a mixture of products, as shown in the following unbalanced equation. The relative amounts of the various products depend on the proportion of the two reactants used. In the case of methane, a large excess of the hydrocarbon favors formation of methyl chloride as the chief product; whereas, an excess of chlorine favors formation of chloroform and carbon tetrachloride.

CH4   +   Cl2   +   energy   →  CH3Cl   +   CH2Cl2   +   CHCl3   +   CCl4   +   HCl

### Empirical Considerations

The following facts must be accomodated by any reasonable mechanism for the halogenation reaction.

1. The reactivity of the halogens decreases in the following order: F2 > Cl2 > Br2 > I2.
2. We shall confine our attention to chlorine and bromine, since fluorine is so explosively reactive it is difficult to control, and iodine is generally unreactive.
3. Chlorinations and brominations are normally exothermic.
4. Energy input in the form of heat or light is necessary to initiate these halogenations.
5. If light is used to initiate halogenation, thousands of molecules react for each photon of light absorbed.
6. Halogenation reactions may be conducted in either the gaseous or liquid phase.
7. In gas phase chlorinations the presence of oxygen (a radical trap) inhibits the reaction.
8. In liquid phase halogenations radical initiators such as peroxides facilitate the reaction.

The most plausible mechanism for halogenation is a chain reaction involving neutral intermediates such as free radicals or atoms. The weakest covalent bond in the reactants is the halogen-halogen bond (Cl-Cl = 58 kcal/mole; Br-Br = 46 kcal/mole) so the initiating step is the homolytic cleavage of this bond by heat or light, note that chlorine and bromine both absorb visible light (they are colored). A chain reaction mechanism for the chlorination of methane has been described. Bromination of alkanes occurs by a similar mechanism, but is slower and more selective because a bromine atom is a less reactive hydrogen abstraction agent than a chlorine atom, as reflected by the higher bond energy of H-Cl than H-Br.

### Selectivity

When alkanes larger than ethane are halogenated, isomeric products are formed. Thus chlorination of propane gives both 1-chloropropane and 2-chloropropane as mono-chlorinated products. Four constitutionally isomeric dichlorinated products are possible, and five constitutional isomers exist for the trichlorinated propanes. Can you write structural formulas for the four dichlorinated isomers?

$CH_3CH_2CH_3 + 2Cl_2 \rightarrow \text{Four} \; C_3H_6Cl_2 \; \text{isomers} + 2 HCl$

The halogenation of propane discloses an interesting feature of these reactions. All the hydrogens in a complex alkane do not exhibit equal reactivity. For example, propane has eight hydrogens, six of them being structurally equivalent primary, and the other two being secondary. If all these hydrogen atoms were equally reactive, halogenation should give a 3:1 ratio of 1-halopropane to 2-halopropane mono-halogenated products, reflecting the primary/secondary numbers. This is not what we observe. Light-induced gas phase chlorination at 25 ºC gives 45% 1-chloropropane and 55% 2-chloropropane.

CH3-CH2-CH3   +   Cl2   →  45% CH3-CH2-CH2Cl   +   55% CH3-CHCl-CH3

The results of bromination ( light-induced at 25 ºC ) are even more suprising, with 2-bromopropane accounting for 97% of the mono-bromo product.

CH3-CH2-CH3   +   Br2  →  3% CH3-CH2-CH2Br   +   97% CH3-CHBr-CH3

These results suggest strongly that 2º-hydrogens are inherently more reactive than 1º-hydrogens, by a factor of about 3:1. Further experiments showed that 3º-hydrogens are even more reactive toward halogen atoms. Thus, light-induced chlorination of 2-methylpropane gave predominantly (65%) 2-chloro-2-methylpropane, the substitution product of the sole 3º-hydrogen, despite the presence of nine 1º-hydrogens in the molecule.

(CH3)3CH   +   Cl2   →  65% (CH3)3CCl   +   35% (CH3)2CHCH2Cl

It should be clear from a review of the two steps that make up the free radical chain reaction for halogenation that the first step (hydrogen abstraction) is the product determining step. Once a carbon radical is formed, subsequent bonding to a halogen atom (in the second step) can only occur at the radical site. Consequently, an understanding of the preference for substitution at 2º and 3º-carbon atoms must come from an analysis of this first step.

First Step:       R3CH   +   X·   →  R3C·   +   H-X

Second Step:     R3C·   +   X2   →  R3CX   +   X·

Since the H-X product is common to all possible reactions, differences in reactivity can only be attributed to differences in C-H bond dissociation energies. In our previous discussion of bond energy we assumed average values for all bonds of a given kind, but now we see that this is not strictly true. In the case of carbon-hydrogen bonds, there are significant differences, and the specific dissociation energies (energy required to break a bond homolytically) for various kinds of C-H bonds have been measured. These values are given in the following table.

R   (in R–H) methyl ethyl i-propyl t-butyl phenyl benzyl allyl vinyl
Bond Dissociation Energy
(kcal/mole)
103 98 95 93 110 85 88 112

The difference in C-H bond dissociation energy reported for primary (1º), secondary (2º) and tertiary (3º) sites agrees with the halogenation observations reported above, in that we would expect weaker bonds to be broken more easily than are strong bonds. By this reasoning we would expect benzylic and allylic sites to be exceptionally reactive in free radical halogenation, as experiments have shown. The methyl group of toluene, C6H5CH3, is readily chlorinated or brominated in the presence of free radical initiators (usually peroxides), and ethylbenzene is similarly chlorinated at the benzylic location exclusively. The hydrogens bonded to the aromatic ring (referred to as phenyl hydrogens above) have relatively high bond dissociation energies and are not substituted.

C6H5CH2CH3 + Cl2   →  C6H5CHClCH3   +   HCl

Since carbon-carbon double bonds add chlorine and bromine rapidly in liquid phase solutions, free radical substitution reactions of alkenes by these halogens must be carried out in the gas phase, or by other halogenating reagents. One such reagent is N-bromosuccinimide (NBS), shown in the second equation below. By using NBS as a brominating agent, allylic brominations are readily achieved in the liquid phase.

The covalent bond homolyses that define the bond dissociation energies listed above may are described by the general equation:

R3C-H   +   energy   →  R3C·   +   H·

C-H bond dissociation energies are commonly interpreted in terms of radical stability. However, this interpretation has been questioned by Gronert. Most importantly, in terms of the selectivity of free radical reactions, it is the energies of the bonds that matter, and not why they are what they are.