Compare stability of 1 and 2:

1: 5‐methylcyclohexa‐1,3‐diene; 2: 3‐methylenecyclohexene


1 is more stable than 2.

My approach

  • Both have the same number of π-bonds.
  • Both have one resonance structure.
  • Both are non-aromatic.
  • In 1 there are three α-hydrogens, whereas in 2 there are four α-hydrogens.

As extent of hyper-conjugation is more in 2 than in 1, making 2 more stable, which contradicts the answer.

  • $\begingroup$ A factor you haven't considered is ring strain. I'm not sure which of the two structures would have more ring strain, though. $\endgroup$ – zwol Apr 15 at 17:53
  • $\begingroup$ AFAIK, given that short of running an (expensive) numerical simulation, we only got some heuristics to work with, it'd be worth knowing to what extent do those really differ in terms of stability. If it's a small difference (say <1%), then I'd imagine that the heuristics may not be accurate enough to be trustworthy. It'd really help to know whether the authors of the textbook that posed this question have actually made any measurements or used published data, otherwise any answers you get may be misleading (garbage in = garbage out). $\endgroup$ – Kuba hasn't forgotten Monica Apr 15 at 19:05
  • $\begingroup$ question was asked in NSEC 2011, an Olympiad exam, tho they haven't given any explanation for their answer. $\endgroup$ – Vega Apr 16 at 4:03

As far as I have read, in general, exocyclic double bonds (which are outside the ring) are stable for 3 or 4 numbered rings while endocyclic double bonds (which are inside the ring) are stable in 5 or 6 numbered rings.

As you note all the factors, more or less all factors are same in both cases, so it becomes a little handwavy thing.

Additional Reading:

  1. Goumans, T.; Ehlers, A.; Lammertsma, K.; Würthwein, E. endo/exo Preferences for Double Bonds in Three-Membered Rings Including Phosphorus Compounds. Eur. J. Org. Chem. 2003, 2003 (15), 2941–2946. DOI: 10.1002/ejoc.200300120.

  2. Fleck, B. Notes - Stability and Ease of Formation of Endo and Exo Double Bonds in 5- and 6- Ring Systems. J. Org. Chem. 1957, 22 (4), 439–439. DOI: 10.1021/jo01355a023.

  3. Exocyclic vs. endocyclic double bonds in E1 elimination (although this one is not much relevant here).


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