Cycloalkanes – Dashes And Wedges

by James

in Alkanes, Nomenclature, Organic Chemistry 1, Stereochemistry

In the last post, we mentioned that one of the consequences of the fact that carbon can form rings is that small rings (less than 8 carbons) are so rigid that they can’t be turned inside out [video]. One of the important consequences of this, as we’ll see today, is that it leads to the formation of new types of isomers we haven’t seen before. 

Remember isomers? If you’ve gone through the first few chapters covering alkanes, no doubt you have. The most familiar kind of isomer to us right now are constitutional isomers. These are molecules that have the same molecular formula, but different structural formula. In other words, different connectivity. A simple example is for C4H10, where we have n-butane (a straight chain of 4 carbons) and 2-methyl propane (with a longest chain of 3 carbons, and a methyl group attached to the middle carbon). 

Of course an easy way to remember constitutional isomers is to tie them back to cats. 

Constitutional

Constitutional Isocats! Same components, different connectivity

OK, let’s get back to the topic at hand. What do we understand so far about constitutional isomers and cyclic molecules? 
Let’s take the example of “dimethylcyclopropane”. This is a cyclopropane with two methyl groups (CH3) attached. Can you draw two constitutional isomers for dimethylcyclopropane? You should: here they are

1-constitutional

Here, both molecules have the same molecular formula but different connectivities. That’s why specifying “1,1” or “1,2” is important – it avoids ambiguity. An unambiguous name for a molecule is necessary in order to draw the structure perfectly from the name – just like an unambiguous address for your house is necessary to allow the postal service to deliver a letter to your door. Anything less and you get, “Return To Sender”. 

Funny thing about that. If you try to make a model of 1,2-dimethylcyclopropane, you might notice something. There are actually two of them!  In one version, the two methyl groups are on the same face of the three-membered ring. In the other, they are on the opposite face. Since the three membered ring is rigid, we can’t interconvert the two without bustimicating the three membered ring.  

2-12dimethylcyclopropaneThese molecules can’t be converted into each other without breaking the ring apart. The ring is too rigid. 
[Just like you can’t touch your left elbow with your left hand without breaking your forearm : – {   ] 

This means that the orientation of the groups on C-1 and C-2 are locked in place. Therefore they are two different molecules
In other words, they are isomers! That is, they have the same molecular formula (C5H10) but different structural formulae. (this is true for any two non-H substituents on C-1 and C-2 – not just methyl). 

They will have different physical properties (e.g. boiling and melting points): 

3-phys prop
What kind of isomers are they exactly? They can’t be constitutional isomers, since they have the same connectivity. We’ll need a different name. Since these two isomers of 1,2-dimethylcyclopropane differ only in their orientation in space, we call them stereoisomers.
Let’s highlight this with a cat example : – ) . Look at the white legs in each case.

cis trans

Stereoisocats

Now: there’s actually a much more convenient way to draw stereoisomers than by using these 3-D perspective drawings. Except in certain cases (mostly bridged rings – we’ll get there a few posts from now) in organic chem it’s usually much more convenient for us to draw the flat versions of molecules. 

This presents a little problem. How do we give the illusion of showing three dimensions on a two-dimensional page? 

We’re going to do two things. First of all, we’re going to draw these molecules from the perspective of looking straight on at them, rather than from the side. In other words, look at them such that the plane of the ring will be in the plane of the page. 

Some groups will be pointing towards us, while others will point away. 

So we’re going to take some inspiration from everyday life to give the effect of distance. 

In this lovely picture of the Austrian alps, notice how the mountains close to us have well defined outlines and sharp contrast, whereas the mountains farther away are more faint.

austrian-mountains-seen-in-the-distance

Foreground: high contrast, background: low contrast

We’re going to use a similar visual trick. With the ring in the plane of the page, groups that point towards us are going to have a dark solid line (“wedge”) whereas groups that point away from us will be denoted with a dashed line (“dash”). 

This is what it will look like:
4-wedge dashHere’s what the other one will look like: 
5-wedge dash Molecules are just like any other 3-D object.  Their structure is INDEPENDENT of the perspective you draw them from. Whether you choose to draw them from the top, the bottom, the side – they all represent the same three-dimensional object. By the way – we could also have chosen to look at it from the bottom instead. In that case the drawings would look like this 

6-wedge-dash

 

Regardless of whether we look at the molecule on the left from the top or the bottom, we’d get the same thing. Just like whether you photograph a propane tank from the top, the side, or the bottom, you’re still photographing the propane tank. One last illustration. 
7-wedge-dash

One last point remains. How do we name these molecules so that it’s clear which version of 1,2-dimethylcyclopropane we’re referring to? In a pinch, a good scientist retreats to Latin for naming duties. For the case where the two groups are on the same side of the ring, we refer to it as ‘cis‘ (from the Latin, meaning, “same side of”. For the case where the two groups are on the opposite side of the ring, we refer to it as “trans” (meaning “opposite side of'”). That gives us the following names (usually we italicize the cis and trans) 
8-cistrans

We can apply this to other groups (and rings) beside methyls and cyclopropane, of course. Note that in the absence of dashes/wedges, the structures drawn would be ambiguous. 
9-cistransmoreexamples
In the next post, we’ll talk about another interesting consequence of ring size: a phenomenon known as strain. 

 

P.S. Some of these structures (not all) are not even fully made unambiguous by the terms “cis” and “trans”. There’s an even deeper level of nomenclature we’ll need to describe, for example, trans-1,2-dimethylcyelopropane. If you’re really keen, you might be able to find it. If not, we’ll talk about it in future posts. 

 

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{ 2 comments… read them below or add one }

Anthony Hoffman

Just wanted to point out the word is not bustimicating but busticating.

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James

I’m Canadian, we use the longer version of words up here.

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