Spectroscopy in Organic - II

Degrees of Unsaturation Unsaturation means places where hydrogens could be added. Points of unsaturation include multiple bonds or rings. Every multiple bond and ring each counts as one d.u. Once you have a molecular formula, you can easily calculate the number of d.u. in a molecule. When you know how many multiple bonds and/or rings are in a molecule, you can more easily determine the pieces and how to put them together. You can either determine the d.u. by using a formula, or alternatively, a little trial and error. d.u.= (2C+N+2-H-X) ignore O and S Dont underestimate thisits easy to determineand it can be very useful. Lets try a few on the next page
Christopher B. Martin CHEM 3412
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Examples Determining d.u.

O Cl N

C6H12

C4H9Cl

C4H9NO

d.u.=1

d.u.=0
H N Br Br

d.u.=1

C7H8

C 3H7Br2N

C11H20

d.u.=4

d.u.=0
NH2

d.u.=2

N N

d.u.=6 d.u.=9
O N N H

C14H12O

C5H5N5

Christopher B. Martin CHEM 3412

13C

- Not as much information

Carbon-13 NMR Spectra Chemical Shift (ppm, ) -where in the spectrum is the signal found -chemical environment of the carbon In general, you CANNOT integrate a 13C spectrum Usually, 13C NMRs are decoupled, therefore there is NOT ANY splitting 13C NMRs are used to tell you how many different kinds of carbons you have. Although they are on different scales, regions of a proton and carbon NMR are generally in the same area. A very crude approximation is to multiply the proton NMR chemical shift by 20 to get the carbon chemical shift.
Christopher B. Martin CHEM 3412
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Why is

13C

so Limited compared to 1H?

About 99.9% of hydrogen occurring in nature is 1H and NMR active. Only 0.1% of carbon occurring in nature is 13C and NMR active. Just in the nature of carbon, it takes longer to obtain a set of data than compared to hydrogen (30 sec. vs. 7 sec.). With 1H NMR, you dont have to wait long, so its easy to get an integratable 1H NMR spectrum. When you add on the fact that the NMR active nucleus is abundant in only 0.1% of the atoms, there arent many atoms that give signals. In order to get a 13C NMR that can be integrated, you need to wait a long time between data collections. Usually, this is not done. In actuality, you can get 13C NMR spectra that can be integrated, you only need to let the samples run a long time (relaxation time). The statistical chance of getting NMR active carbon atoms beside each other (for C-C splitting) is nearly zero. Thats why theres no splitting.

Christopher B. Martin CHEM 3412

1H

&

13C

NMR of 1,4-dioxane

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1H

&

13C

NMR of 1,3-dioxane

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1H

&

13C

NMR of 2-butanol

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Comparing 1H &

13C

NMR of a diester

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Fancy 13C NMR Spectra

DEPT You can tell how many hydrogens are attached to a carbon atom in a DEPT by looking at the way that the peaks point in a DEPT. In a standard 13C NMR, all peaks point . In a DEPT, CH and CH3 point , CH2 point , and carbons with no hydrogens dont show up at all in the DEPT. Proton Coupled Proton coupled 13C spectra look at the 13C-1H coupling. Carbon peaks are split once for every hydrogen that is directly attached to that carbon. Therefore carbons that have no attached hydrogens stay as singlets, with one hydrogen becomes doubltes, with two hydrogens becomes triplets, and methyl groups show up as a quartet.
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The Electromagnetic Spectrum - IR

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Concept of IR - Masses on Springs

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Concept of IR - Masses on Springs

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IR Chart

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When can I expect IR bands?

Vibrations and other transitions are IR active when they have a net change in the dipole moment. (Yes, electronegativity IS important.) If these transitions are symmetrical, then there is no change in dipole, and therefore these transitions would not be seen on the IR. Consider the different bonds in the molecules below and discuss what may (or may not) be IR active.

H C C H

H H H3C

O C CH3
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H3C C C CH3

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Some Typical IR Bond Stretches

C-C C=C C=C C=C C=C (sp3)C-H (sp2)C-H (sp)C-H ~1200 cm-1 ~1660 cm-1 ~1620-1640 cm-1 ~1600 cm-1 ~2200 cm-1 ~2800-3000 cm-1 ~3000-3100 cm-1 ~3300 cm-1
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(isolated) (conj.) (aromatic) (weak)

Some Typical IR Bond Stretches

O-H N-H C=O C(=O)-H N-C=O C=O C-N C=N C=N ~3300 cm-1 ~3300 cm-1 ~1710 cm-1 ~1620-1680 cm-1 ~1685-1690 cm-1 ~1200 cm-1 ~1600 cm-1 ~>2200 cm-1 (alcohol & C.A., broad) (amine, broad w/spikes) (ketone, aldehyde, & C.A.)

~2700-2800 cm-1 (aldehyde C-H) (carbonyl conj. w/lone pairs) (carbonyl conj. w/alkene) (strong) (strong) (strong)
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Christopher B. Martin CHEM 3412

Lets try to analyze some IR spectra

1. Realize that you cannot use IR alone to determine the complete structure. Think of it as the distinguishing characteristics of a person in a police line-up. Look for some of the obvious functional groups. -carbonyls, alcohols, C-H stretches 3. Try to narrow down anything you can (like the specific carbonyl stretch) to reduce the possibilities.

2.

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n-octane

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n-hexane vs. 1-hexene

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1-octyne vs. 4-octyne

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1-butanol vs. dipropylamine

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Ketone vs. Aldehyde

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Nitrile (C=N)

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Crude Summary of IR Regions

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Mass Spectrometry (MS)

Lets assume that you have about a million molecules of a compound. If you shatter them, you could take a look at the pieces and try to determine how they would fit together again. In mass spectrometry (MS), thats exactly what is done. Since we know a little about which bonds are weaker and which fragments are more stable, information about the sizes of these fragments provide clues as the the structure of the initial molecule. First, lets examine exactly how each molecule is fragmented.

2e
M
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fragments
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MS Fragments Stable Ions

OKwe have a molecule that has had an electron knocked out and now its a radical cation. This isnt stable, and the molecule will break apart. Since you start with a radical cation, you can either produce a neutral molecule and a radical cation as products, or a radical and then a cation. Either way, youre looking at cation stability. The more stable the cation, the more likely that fragment will form. Look at the molecule belowwhich arrow is at the best fragmentation?

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MS
CH3

CH3

As you can see, one fragmentation produces a very highly substituted cation where the others do not. This will result in a lot of molecules fragmenting to produce a fragment with the mass of this more stable piece.
Christopher B. Martin CHEM 3412
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MS Fragmentations
Molecules will fragment at places where a resulting carbocation (or radical) will be most stable. Common places for bond fragmentation is at branch points, adjacent to carbonyls, and adjacent to N or O (because of the lone pairs that can stabilize cations). Lets take a look at the molecules we examined earlier for the proton and carbon NMR and see if the IR or MS helps out at all.

Christopher B. Martin CHEM 3412

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IR and MS of 1,4-dioxane

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IR and MS of 2-butanol

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IR and MS of a diester

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Summary
Understand, be able to explain, and be able to use 1H NMR, 13C NMR, IR, and MS. Know what each one can tell youand what it cannot. Examine all of the spectra given to you in the packet and interpret each type of spectra and identify what the molecule is. You will be responsible for knowing and using this not only on this first exam, but also in lab, and on any exam through the rest of the semester.

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