Name. (think carefully about the stereochemistry for this one) 2 Do you think this type of problem might show up on the final exam?

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1 Name 1 Chlorination of alkanes gives mixtures of products where chlorine has replaced H at every possible position. For example, chlorination of isobutane (CH 3 ) 3 CH produces a mixture of t- butyl chloride and isobutyl chloride. (Although any one of the 10 Hs can be replaced by Cl, only two products can be formed.) With this in mind, draw the monochlorination products of the following alkanes, including stereochemistry. Be careful not to draw the same product twice! (Experimentally, this reaction is difficult to control, and products with more than one Cl are often produced. But for this problem we're only looking for the monochloro products.) (think carefully about the stereochemistry for this one) 2 Do you think this type of problem might show up on the final exam?

2 Lecture outline For example, omine atom is much more selective than chlorine atom in which H(s) it abstracts. Cl + Cl vs 2 vs 3 Hs for for Cl To simplify this, the relative reactivities mean that: (1) is very finicky and will abstract H to give the most stable radical only; (2) Cl just grabs whatever random H it happens to run into, with (almost) no regard for radical stability. The key to understanding the difference in behavior of these two halogen atoms lies in the energetics of the first chain propagation step. For + H R, ΔH +7 (3 H) to +13 (1 H) kcal/mol For Cl + H R, ΔH 8 (3 H) to 2 (1 H) kcal/mol

3 This, combined with the observation that exothermic free radical abstractions generally have extremely low activation barriers, suggests the following rxn coordinate diagrams... Chlorination 1st prop step is exothermic transition states resemble reactants Cl H R Cl + alkane 1 R + HCl 3 R + HCl At the transition state, neither abstraction has gone very far, so the energy and structure of the transition state still look like the reactants (Cl + R H) (Hammond postulate). The big difference in energy of the final radicals, R, doesn't matter much because there's not much radical character on "R" at the transition state. Thus, the E a s are not very different, and the two pathways go at similar rates. omination 1st prop step is endothermic transition states resemble products H R 1 R + H 3 R + H + alkane At the transition state, both abstractions have gone almost all the way to completion, so the energy and structure of the transition state look like the products ( H + R) (Hammond postulate). This time the big difference in energy of the final radicals matters a lot because the radical character on "R" is almost fully developed at the transition state. Thus, the E a s are very different, and the two pathways go at very different rates.

4 Free radical halogenation at allylic positions is especially facile Allylic and benzylic C H bonds have relatively low BDEs H H How do these values compare with a 1 C H BDE of an alkane? In practice, we can't brominate alkenes just by tossing in 2 and turning on a light the 2 would add to the double bond much faster than the desired radical rxn ever got going. (Note that a light-initiated reaction won't go in the dark, but a thermal reaction one that doesn't require light can go whether there's light or not. Stated another way, dark is the absence of light, but light is not the absence of dark. There's still plenty of "dark" there, even if a few photons go whizzing by once in a while. If there's enough thermal energy the "dark rxn" can always go.) We can get around this problem by using N-bromosuccinimide (NBS) instead of 2. The rxn works by the same free radical chain that we've already learned for alkane + 2. NBS reacts with the H formed in the rxn to generate 2 O only as fast as the rxn proceeds. (The key is that the 2 addition is more complicated than you were led to believe it's very dependent on the 2 concentration; at very low concentration of bromine, the reaction is extremely slow. In the NBS reaction the concentration of 2 stays extremely low, which slows the competing addition to the π-bond, so the FR chain rxn wins.) O N N-bromosuccinimide (NBS)

5 An important practical difference between NBS brominations and simple brominations with 2 is that, like many free-radical rxns, the NBS rxn needs a separate initiator to get it going. In the 2 promination, 2 serves as the initiator as well as the reactant. NBS can't initiate the reaction because it doesn't absorb light and create radicals. Peroxides are good initiators because the weak O O bond breaks easily upon heating or when it absorbs UV light. Azoisobutyronitrile (AIBN) is another popular initiator (see text section 21.4) NBS (or!) and "RO OR" (a peroxide) or other f.r. initiator Although it's unclear exactly how this gets started, the propagation sequence has been established to be (complete the rxns)... + H + NBS 2 + "NHS" (i.e. just plain succinimide) + 2 Now, predict the products of the rxn below. To do this, you'll need to draw the allylic radical intermediate. partial mech NBS peroxide

6 What products would be produced here? NBS peroxide (Here, 2 different radical intermediates are formed, and each leads to 2 bromo-alkene products, so there are 4 products in all.) In general, formation of delocalized radicals is much faster than formation of localized radicals expect abstraction from all allylic positions (regardless of 1 vs 2 vs 3 is not very picky when it comes to small variations in the stability of delocalized radicals that are formed when it abstracts H. expect addition of bromine to every C with some radical character (i.e. every position with a δ ) don't try to predict relative amounts of the products from allylic radicals there are too many factors involved, and not enough info to figure it out.