Try it on paper first. A hint, the key idea and the worked solution are here when you need them.
2-Methylbutane, , gives four monohalo products. Replacing a hydrogen on carbon 1 or on the methyl branch gives 1-halo-2-methylbutane (6 hydrogen atoms in all). Carbon 2 gives 2-halo-2-methylbutane (1 hydrogen atom). Carbon 3 gives 2-halo-3-methylbutane (2 hydrogen atoms). Carbon 4 gives 1-halo-3-methylbutane (3 hydrogen atoms). At room temperature with chlorine, the reactivities of one primary, secondary and tertiary hydrogen are . With bromine at they are . Find the percentage of each chloro product, and the percentage of 2-bromo-2-methylbutane in the bromination.
In free radical halogenation the share of a product is proportional to the number of hydrogen atoms times their reactivity. Bond enthalpies give the energy change of a step: bonds broken minus bonds formed. Hydrogen halides add to alkenes by Markovnikov's rule, and an alcohol with NaBr and sulphuric acid gives a bromoalkane.
Have you tried it?
Work it out on paper first. It is fine to get stuck or make a mistake: that is how we learn. When you are ready, go through the solution one step at a time, and check each step against your own.
Plan. Weight each product, add the weights, then take shares.
Step 1. Chlorine weights. 1-Chloro-2-methylbutane: . 2-Chloro-2-methylbutane: . 2-Chloro-3-methylbutane: . 1-Chloro-3-methylbutane: . The sum is .
Step 2. Chlorine shares. , , and .
Step 3. Bromine weights. ; ; ; . The sum is .
Step 4. Bromine share. is the tertiary bromide.
Answer: chlorination gives , , and . Bromination gives of 2-bromo-2-methylbutane.
Check. The four chlorine shares add to . Bromine is much more selective, because the reaction with the tertiary hydrogen is much faster.
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