Introduction to Cycloalkanes (1)

by James

in Alkanes, Conformations

In the first few weeks of an organic chemistry class, we learn that:

  • Carbon can form up to four single bonds 
  • Carbon with four single bonds adopts a tetrahedral geometry (ideal bond angle: 109.5°)
  • Compared to other atoms on the periodic table, [O, N, S, Si for example] carbon forms very strong bonds with itself and can therefore form stable chains
  • Carbon-carbon single bonds can rotate freely, and the three-dimensional shapes that arise (“conformations”) can vary significantly in energy. 

Nothing particularly strange about that so far. How about this:

  • in addition to forming chains, carbon atoms can also form rings

Not strange either… right? Makes sense? 

 Take a second and see if you can imagine some consequences of that simple fact. How might it affect any of those bullet points we made above? 

It’s very difficult to imagine situations that may arise if you haven’t at least seen a glimpse of them yourself. 

I’m going to use this opportunity to make a gratuitous chess analogy. One important rule in chess is that if a pawn makes its way to the end of the board, it can be promoted to a piece of the players choice. 99% of the time, the best choice is a Queen, but there are (very rare) situations where it is optimal to promote to a different piece – a knight, for example (see below). [link]

Screen Shot 2014-02-17 at 4.11.48 PM

black to play

Cool, huh? An example like this one flows logically from the rules of the game, but you can’t really imagine situations like this one until you have a lot of board time under your belt.

Similarly, there are consequences of the fact that carbon can form rings that are not yet readily apparent. We’re going to start by exploring two of them today in this first post of a new series on cycloalkanes. 

220px-Serpiente_alquimica

Cycloalkanes

One of the first consequences of the fact that carbon can form rings can be found by comparing the condensed molecular formulae of linear alkanes with cyclic alkanes. Notice how the formula of linear alkanes follows the pattern   H = 2n + 2  (where “n” is the number of carbons) whereas the formula for cycloalkanes follows the pattern H = 2n. Just by forming a ring, the number of hydrogens decreases by two.’

cycloalkanes - 1

By the way, every successive ring decreases the hydrogen content by two – the bicyclic molecules below follow each follow the pattern #H = 2n –2. And the tricyclic molecule follows the pattern #H = 2n –4 . [Bonus Q – how many hydrogens would be in a tetracyclic molecule with 20 carbons (and no multiple bonds)? ]

bicyclic

Why does this matter? As you’ll see later, we’ll be able to use the fact that each ring decreases the hydrogen count of the molecule by 2 to help us deduce the structures of unknown compounds in some cases. It can be a small clue, but an important one nonetheless. 

There’s a second interesting observation with cycloalkanes that we’ll talk about in much greater detail next time, but is important to get out of the way because it’s often overlooked. See how there’s that empty space in the middle of a cycloalkane ring? Many everyday household objects – belts, elastics, wristbands – can be easily turned inside out. Can we do the same with cycloalkanes? What happens when we try to turn them inside out? 

 Because it’s much easier to show this rather than tell it, I made a quick video. 

The bottom line is that cycloalkanes of less than 8 carbons cannot be turned inside out without breaking carbon-carbon bonds.  >99% of the rings that you’ll see in Org 1 / Org 2 will fall into this category. 

This has far-ranging consequences that we’ll talk about in the next post in this series. 

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{ 1 comment… read it below or add one }

Diana

Hi James!!!
Turns out I’m back again.
In terms of priority, do bigger rings take priority or functional groups.
If you were to for example have an alcohol group on the smaller ring of a bicyclic compound versus a methyl group on the larger ring, how would the numbering work?

Thanks so much!

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