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Surviving Chair Structures. Surviving Chair Structures. A “How-to” Review. Step 1: Cyclohexane in 2-D. 2 groups on the ring can be Cis (on the same side) or Trans (on opposite sides). Step 1: Cyclohexane in 2-D. 2 groups on the ring can be Cis or Trans: Cis = Same Sides.

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surviving chair structures2

Surviving Chair Structures

A “How-to” Review

step 1 cyclohexane in 2 d
Step 1: Cyclohexane in 2-D
  • 2 groups on the ring can be Cis (on the same side) or Trans (on opposite sides)
step 1 cyclohexane in 2 d4
Step 1: Cyclohexane in 2-D
  • 2 groups on the ring can be Cis or Trans:
    • Cis = Same Sides
step 1 cyclohexane in 2 d5
Step 1: Cyclohexane in 2-D
  • 2 groups on the ring can be Cis or Trans:
    • Trans = Opposite Sides
step 1 cyclohexane in 2 d6
Step 1: Cyclohexane in 2-D
  • Which is it? Cis or Trans?
step 1 cyclohexane in 2 d7
Step 1: Cyclohexane in 2-D
  • Answer: One Up… One Down… Trans…
step 1 cyclohexane in 2 d8
Step 1: Cyclohexane in 2-D
  • Which are they? Cis or Trans?
step 2 draw cis 1 3 dimethylcyclohexane12
Step 2: Draw cis-1, 3-dimethylcyclohexane

… then pick a position to be #1 (and ANY position can be #1)…

step 2 draw cis 1 3 dimethylcyclohexane13
Step 2: Draw cis-1, 3-dimethylcyclohexane

… then number around the ring (CW or CCW) to find #3(since you are drawing a 1,3-disubstituted ring)

step 2 draw cis 1 3 dimethylcyclohexane14
Step 2: Draw cis-1, 3-dimethylcyclohexane

… then attach the necessary groups (two methyl groups, in this case) to the #1 and #3 positions you’ve decided to use…

step 2 draw cis 1 3 dimethylcyclohexane15
Step 2: Draw cis-1, 3-dimethylcyclohexane

…then add stereochemistry to show the relative positions (cis = same side, trans = opposite sides). Since the compound is cis-1,3-dimethylcyclohexane, either of the answers below will be correct answers…

step 2 draw cis 1 3 dimethylcyclohexane16
Step 2: Draw cis-1, 3-dimethylcyclohexane

… as would these, depending on where you placed your #1 and #3 positions…

step 3 converting to a chair structure18
Step 3: Converting to a Chair structure

Chair structures are the 3-D representation of the cyclohexane ring… Remember that this view is from the side of the ring, not from above or below…

step 3 converting to a chair structure19
Step 3: Converting to a Chair structure

First – let’s remind ourselves about the different positions on a chair structure…

step 3 converting to a chair structure20
Step 3: Converting to a Chair structure

Every cyclohexane chair has six carbons, three that zig-zag up and three that zig-zag down… make sure you can identify them…

step 3 converting to a chair structure21
Step 3: Converting to a Chair structure

On the positions that zig-zag UP, you will find the vertical UP AXIAL positions… on the positions that zig-zag DOWN, you will find the vertical DOWN AXIAL positions…

step 3 converting to a chair structure22
Step 3: Converting to a Chair structure

On the positions that zig-zag UP, you will find the (semi-horizontal) DOWN EQUATORIAL positions… on the positions that zig-zag DOWN, you will find the (semi-horizontal) UP EQUATORIAL positions…

step 3 converting to a chair structure23
Step 3: Converting to a Chair structure

All of the positions are shown below in one structure:

step 3 converting to a chair structure24
Step 3: Converting to a Chair structure

All positions, together on the ring… make sure you can find them to draw them… Fill them in on the template shown… (answer on previous slide!)

step 3 converting to a chair structure25
Step 3: Converting to a Chair structure

Translation required: wedges (or bold lines) in 2-D are the “UP” positions and dashes in 2-D are the “DOWN” positions… Up is Up and Down is Down, regardless of axial or equatorial…

step 3 converting to a chair structure26
Step 3: Converting to a Chair structure

Recall that any position on the cyclohexane can be #1…

step 3 convert to a chair structure
Step 3: Convert to a Chair structure

…and any position on the chair form can be #1…

step 3 convert to a chair structure28
Step 3: Convert to a Chair structure

…for practice and repetition’s sake (so you are less likely to make errors), choose your #1 on both and always stay in the same positions…

step 3 convert to a chair structure29
Step 3: Convert to a Chair structure

…for the purpose of this example, we will use the #1 position on the hexagon shown below…

step 3 convert to a chair structure30
Step 3: Convert to a Chair structure

…and this will correlate to the #1 position chosen here on this chair form… Remember that YOU can chose whichever #1 YOU want to use…

step 3 converting to a chair structure31
Step 3: Converting to a Chair structure

If this is #1 on the hexagon, number the ring accordingly… CW or CCW…

step 3 converting to a chair structure32
Step 3: Converting to a Chair structure

…then do likewise on the chair structure… again, CW versus CCW does not matter (its all RELATIVE to each other…)

step 3 converting to a chair structure33
Step 3: Converting to a Chair structure

…now you can see what carbons on the hexagon form of cyclohexane correlate to the chair form of cyclohexane…

step 3 converting to a chair structure34
Step 3: Converting to a Chair structure

Now let’s consider stereochemistry on the 2-dimensional version of cyclohexane…

step 3 converting to a chair structure35
Step 3: Converting to a Chair structure

Try This: Draw trans-1,4-dichlorocyclohexane in 2-dimensions… I numbered this one CW, just for fun…

step 3 converting to a chair structure36
Step 3: Converting to a Chair structure

How did you do? Your answer may not look exactly the same as the one below, but remember – its all RELATIVE… trans = one UP and one DOWN…

step 3 converting to a chair structure37
Step 3: Converting to a Chair structure

Now you have to convert this into a chair structure… Watch your UP’s and DOWN’s…

step 3 converting to a chair structure38
Step 3: Converting to a Chair structure

Position #1 has in this 2-D drawing an UP chloro group and position #4 has a DOWN chloro group…

step 3 converting to a chair structure39
Step 3: Converting to a Chair structure

Label position 1 and 4 on the chair structure you are using and then transfer the information. Position 1 has an UP chloro group and position 4 has a DOWN chloro group…

step 3 converting to a chair structure40
Step 3: Converting to a Chair structure

You need to fill in the groups on their positions (recall Axial and Equatorial positions). Position #1 has an UP chloro group and “up” on Position #1 will be AXIAL UP. Position #4 has a DOWN chloro group and “down” on Position #4 will be AXIAL DOWN.

step 3 converting to a chair structure41
Step 3: Converting to a Chair structure

Try it again: Draw cis-1-bromo-3-methylcyclohexane as a chair structure… Start in 2-D… Go ahead – before you move to the next slide… Note that this time I numbered CW…

step 3 converting to a chair structure42
Step 3: Converting to a Chair structure

Cis-1-bromo-3-methylcyclohexane, in 2-dimensions…

step 3 converting to a chair structure43
Step 3: Converting to a Chair structure

Draw cis-1-bromo-3-methylcyclohexane as a chair structure. Convert to 3-dimensions – find the positions you need… then determine axial versus equatorial… Down on #1… Down on #3…

step 3 converting to a chair structure44
Step 3: Converting to a Chair structure

Based on MY numbering, you should have had “cis” drawn as two substituents in the DOWN positions, as shown below. The chair structure would look like:

step 3 converting to a chair structure45
Step 3: Converting to a Chair structure

But if you picked a different #1 on the chair, it might look like:

step 3 converting to a chair structure46
Step 3: Converting to a Chair structure

And again: Draw trans-1-chloro-2-ethylcyclohexane as a chair structure. Start in 2-D…. Pick a #1 and number CW or CCW… Add your groups… Give them stereochemistry (wedges/dashes) to show “trans”…

step 3 converting to a chair structure47
Step 3: Converting to a Chair structure

Trans-1-chloro-2-ethylcyclohexane in 2-D….

step 3 converting to a chair structure48
Step 3: Converting to a Chair structure

Keep Going: Draw trans-1-chloro-2-ethylcyclohexane as a chair structure. Remember, there are lots of alternatives, depending on where you placed YOUR #1 and if you went CW or CCW to find #2…

step 3 converting to a chair structure49
Step 3: Converting to a Chair structure

How did you do? Remember that when drawing trans-1-chloro-2-ethylcyclohexane as a chair structure, there are lots of alternatives, depending on where you placed YOUR #1 and if you went CW or CCW to find #2…

step 4 drawing a chair flip structure51
Step 4: Drawing a Chair Flip Structure

When the chair structure of a cyclohexane ring does a “flip”, all of the axial substituents become equatorial and vice versa. Lock onto an “up” carbon (see #1 labeled below) and find its corresponding “down” carbon in the second conformation.

step 4 drawing a chair flip structure52
Step 4: Drawing a Chair Flip Structure

Notice how Axial substituents swapped places with Equatorial substituents, but those that were “up” stayed “up” and “down” stayed “down”…

step 4 drawing a chair flip structure53
Step 4: Drawing a Chair Flip Structure

Now try to transfer the information from one chair to its “flipped” conformation… Start with cis-1,3-dimethylcyclohexane… In this form, you see the two methyl groups are both UP… axial on #1, axial on #3…

step 4 drawing a chair flip structure54
Step 4: Drawing a Chair Flip Structure

Draw the “flipped” conformation of cis-1,3-dimethyl-cyclohexane… Remember the #1 carbon in the first form is an “up” carbon and must therefore be a “down” carbon in the flipped chair form… Number accordingly…

step 4 drawing a chair flip structure55
Step 4: Drawing a Chair Flip Structure

Then add the groups to the positions they belong on… #1 and #3, in this case… Remember the methyl groups are both “up” and must stay “up”… the axial methyls become equatorial… What will that look like?

step 4 drawing a chair flip structure56
Step 4: Drawing a Chair Flip Structure

The diaxial UP positions become diequatorial UP positions:

step 4 drawing a chair flip structure57
Step 4: Drawing a Chair Flip Structure

Now: Do it Again… Draw the following chair in its flipped form:

step 4 drawing a chair flip structure58
Step 4: Drawing a Chair Flip Structure

Like before – lock onto the #1 position and flip the chair…

step 4 drawing a chair flip structure59
Step 4: Drawing a Chair Flip Structure

There is a “down” chloro on MY #2 and an “up” alcohol group on MY #6… they must stay DOWN and UP, respectively… Axial becomes Equatorial and vice versa…

step 4 drawing a chair flip structure60
Step 4: Drawing a Chair Flip Structure

One more time… Practice makes Perfect…

Draw the chair flipped conformation for the compound shown below:

step 4 drawing a chair flip structure61
Step 4: Drawing a Chair Flip Structure

Find the positions, as always… note the “up” groups (#2, #3 and #4)… none of the groups are “down”…two are equatorial, one is axial.. Now flip the axials and equatorials…

step 4 drawing a chair flip structure62
Step 4: Drawing a Chair Flip Structure

And your answer should look like…

step 5 evaluating chair conformations and their relative energies
Step 5: Evaluating Chair Conformations and their Relative Energies

If the two chair conformations are exactly the same, they will be the same energy. See the two examples below. Both sets are equal in energy…

step 5 evaluating chair conformations and their relative energies64
Step 5: Evaluating Chair Conformations and their Relative Energies

Make sure you can see that in this example you have two of the same groups, both up, with one axial while the other one is equatorial. They will have the same energy value.

step 5 evaluating chair conformations and their relative energies65
Step 5: Evaluating Chair Conformations and their Relative Energies

If the two chairs are not the same, they will have different energies, caused by different interactions (e.g. sterics). Note how in the first chair form, the bromo group is axial. In the second it is equatorial. They are different, and therefore different in energy values.

step 5 evaluating chair conformations and their relative energies66
Step 5: Evaluating Chair Conformations and their Relative Energies

So – why are they different in energy? The equatorial groups are a lower energy state because they point out and away from the molecule. The axial groups, however, have a higher energy steric interaction…

step 5 evaluating chair conformations and their relative energies67
Step 5: Evaluating Chair Conformations and their Relative Energies

The steric interaction that needs to be considered is called the A1,3 interaction. It occurs for any axial group (top or bottom of ring) with the other axial groups on the same side (even H’s).

step 5 evaluating chair conformations and their relative energies68
Step 5: Evaluating Chair Conformations and their Relative Energies

The larger the group, the larger the energy value for the A1,3 interaction.

step 5 evaluating chair conformations and their relative energies69
Step 5: Evaluating Chair Conformations and their Relative Energies

Molecules have been studied for their energy values. The A1,3 interactions are quantified on tables that you can look up. As long as you know what X is, you can determine the energy of the system. For example, if X is a CH3, the A1,3 interaction is 0.9 kcal/mol for EACH CH3-H interaction…

step 5 evaluating chair conformations and their relative energies70
Step 5: Evaluating Chair Conformations and their Relative Energies

If the X group is a CH3, the A1,3 interactions occur with EACH H on the same side of the ring – thus the TOTAL energy is 0.9 kcal x 2… The total energy, for X = CH3 would be 1.8 kcal/mol.

step 5 evaluating chair conformations and their relative energies71
Step 5: Evaluating Chair Conformations and their Relative Energies

If the X group is a CH2CH3, the A1,3 interactions occur with EACH H on the same side of the ring – thus the TOTAL energy is 0.95 kcal x 2… The total energy, for X = CH2CH3 would be 1.9 kcal/mol.

step 5 evaluating chair conformations and their relative energies72
Step 5: Evaluating Chair Conformations and their Relative Energies

As the groups get larger, so does the energy of the conformation. If X group is a t-butyl group (-C(CH3)3], the A1,3 interactions with the H’s are EACH 4.8 kcal/mol. The total energy, for X = C(CH3)3 would be 9.6 kcal/mol.

step 5 evaluating chair conformations and their relative energies73
Step 5: Evaluating Chair Conformations and their Relative Energies

If X is an isopropyl group, the A1,3 interaction with one H would be 2.2 kcal/mol. What would be the total energy of the system shown below?

step 5 evaluating chair conformations and their relative energies74
Step 5: Evaluating Chair Conformations and their Relative Energies

With two isopropyl-H interactions, the total strain energy would be twice the value of one, or 4.4 kcal/mol.

step 5 evaluating chair conformations and their relative energies75
Step 5: Evaluating Chair Conformations and their Relative Energies

What about this one? Watch both the top AND the bottom of this ring. Remember the A1,3 value for methyl-H is 0.9 kcal and for ethyl-H is 0.95 kcal/mol.

step 5 evaluating chair conformations and their relative energies76
Step 5: Evaluating Chair Conformations and their Relative Energies

With two methyl-H interactions on top and two ethyl-H interactions on the bottom, the total would be (2 x 0.9) + (2 x 0.95) = 3.7 kcal/mol total energy.

step 5 evaluating chair conformations and their relative energies77
Step 5: Evaluating Chair Conformations and their Relative Energies

Now compare the two chair conformations and determine which one is more stable?

step 5 evaluating chair conformations and their relative energies78
Step 5: Evaluating Chair Conformations and their Relative Energies

The ring with the most and largest groups in axial positions will be the most UNSTABLE and HIGHEST energy conformation. Which one is that, here?

step 5 evaluating chair conformations and their relative energies79
Step 5: Evaluating Chair Conformations and their Relative Energies

Yes, the first conformation is definitely more unstable. The isopropyl group has two A1,3 interactions with H’s adding to 4.4 kcal/mol. The other has two methyl-H A1,3 interactions that add to 1.8 kcal/mol. The first is higher energy! By 2.6 kcal/mol…

surviving chair structures in conclusion
Surviving Chair Structures… In Conclusion…

Cyclohexane and what you should be able to do:

  • Draw in 2-D, showing stereochem
  • Transfer to a chair conformation
  • Draw the chair flipped conformation
  • Identify the high or low energy conformation (or calculate the values, if I give you the table of values)
surviving chair structures in conclusion81
Surviving Chair Structures… In Conclusion…

If you read through this IMMENSELY LONG slide show and found that it was helpful in learning about chair structures, drop me a note at jdiscord@towson.edu and let me know…

Thanks,

Dr. Discordia