p. 1034 — “Small amounts of radicals are formed in many reactions in which the products are actually formed by simple ionic processes.” Interesting — how ‘small’ is small?
p. 1036 — A very improbable mechanism (but true) given in the last reaction involving breaking benzene aromaticity and forming a cyclopropene ring to boot.
p. 1043 — Americans should note that gradient (as in Hammett’s rho constant) means slope (or derivative if the plot of substituents vs. sigma for a particular reaction isn’t a straight line). However we are talking log vs. log plots, and you can fit an elephant onto a log log plot. It’s worth remembering why logarithms are necessary iin the first place. Much of interest to chemists (equilibrium constants, reaction rates) are exponential in free energy (of products vs. reactants in the first case, of transition state vs. reactions in the second).
p. 1044 — Optimally I shouldn’t have to remember that a positve rho (for reaction value) means electrons flow toward the aromatic ring in the rate determining step), but should gut it out from the electron withdrawing or pushing effects on the transition state, and how this affects sigma, by remembering what equilibrium constant is over what for sigma, and rho), but this implies a very high working memory capacity (which I don’t have unfortunately). I think mathematicians do, which is why I’m so slow at it. They have to keep all sorts of definitions in working memory at once to come up with proofs (and I do to follow them).
Here are a few literature references
[ Science vol. 323 pp. 800 – 802 ’09 ] Intensive training on working memory tasks can improve working memory capacity, and reduce cognitively related clinical symptoms. The improvements have been associated with an increase in brain activity in parietal and frontal regions.
I think there are some websites which will train working memory (and claim to improve it). I may give them a shot.
p. 1050 — The unspoken assumption about the kinetic isotope effect is that the C-D and C-H bonds have the same strength (since the curve of potential energy vs. atomic separation is the same for both — this is probably true — but why? Also, there is no explanation of why the maximum kinetic isotope effect is 7.1. So I thought I’d look and see what the current Bible of physical organic chemistry had to say about it.
kH/kD = exp [ hc (vbarH – vbarD)/2KT }, and then in problem #2 plug in a stretching frequency for C-H of 3000 cm^-1 to calculate the isotope effect at 298 Kelvin coming up with 6.5
Far from satisfying. I doubt that the average organic chemist reading Anslyn and Dougherty could solve it. Perhaps I could have done it back in ’61 when I had the incredible experience of auditing E. B. Wilson’s course on Statistical Mechanics while waiting to go to med school (yes he’s the Wilson of Pauling and Wilson). More about him when I start reading Molecular Driving Forces.
p. 1052 — Entropy is a subtle concept (particularly in bulk thermodynamics), but easy enough to measure there. Organic chemists have a very intuitive concept of it as shown here.
p. 1054 — Very slick explanation of the inverse isotope effect.
p. 1061 — The trapping of the benzyne intermediate by a Diels Alder is clever and exactly what I was trying to do years ago in a failed PhD project — see https://luysii.wordpress.com/2012/10/04/carbenes-and-a-defense-of-pre-meds-and-docs/