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    Spectroscopy - II (Du, 13C NMR, IR, MS) (L)

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    The document discusses determining the degrees of unsaturation (d.u.) in organic molecules. It provides formulas for calculating d.u. from molecular formulas and explains that multiple bonds and rings each contribute one d.u. Examples are given of calculating d.u. for various molecules. The rest of the document focuses on explaining 1H NMR, 13C NMR, IR spectroscopy, and mass spectrometry for analyzing organic compounds and determining their structures. Key features and interpretations of each technique are outlined.

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    Spectroscopy - II (Du, 13C NMR, IR, MS) (L)

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    imu4u_786
    119 views16 pages
    The document discusses determining the degrees of unsaturation (d.u.) in organic molecules. It provides formulas for calculating d.u. from molecular formulas and explains that multiple bonds and rings each contribute one d.u. Examples are given of calculating d.u. for various molecules. The rest of the document focuses on explaining 1H NMR, 13C NMR, IR spectroscopy, and mass spectrometry for analyzing organic compounds and determining their structures. Key features and interpretations of each technique are outlined.

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    The document discusses determining the degrees of unsaturation (d.u.) in organic molecules. It provides formulas for calculating d.u. from molecular formulas and explains that multiple bonds and rings each contribute one d.u. Examples are given of calculating d.u. for various molecules. The rest of the document focuses on explaining 1H NMR, 13C NMR, IR spectroscopy, and mass spectrometry for analyzing organic compounds and determining their structures. Key features and interpretations of each technique are outlined.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    119 views16 pages

    Spectroscopy - II (Du, 13C NMR, IR, MS) (L)

    Uploaded by

    imu4u_786
    The document discusses determining the degrees of unsaturation (d.u.) in organic molecules. It provides formulas for calculating d.u. from molecular formulas and explains that multiple bonds and rings each contribute one d.u. Examples are given of calculating d.u. for various molecules. The rest of the document focuses on explaining 1H NMR, 13C NMR, IR spectroscopy, and mass spectrometry for analyzing organic compounds and determining their structures. Key features and interpretations of each technique are outlined.

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    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
    1

    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
    3

    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

    Christopher B. Martin CHEM 3412

    1H

    &

    13C

    NMR of 1,3-dioxane

    Christopher B. Martin CHEM 3412

    1H

    &

    13C

    NMR of 2-butanol

    Christopher B. Martin CHEM 3412

    Comparing 1H &

    13C

    NMR of a diester

    Christopher B. Martin CHEM 3412

    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.
    Christopher B. Martin CHEM 3412
    9

    The Electromagnetic Spectrum - IR

    Christopher B. Martin CHEM 3412

    10

    Concept of IR - Masses on Springs

    Christopher B. Martin CHEM 3412

    11

    Concept of IR - Masses on Springs

    Christopher B. Martin CHEM 3412

    12

    IR Chart

    Christopher B. Martin CHEM 3412

    13

    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
    14

    H3C C C CH3

    Christopher B. Martin CHEM 3412

    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
    Christopher B. Martin CHEM 3412
    15

    (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)
    16

    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.

    Christopher B. Martin CHEM 3412

    17

    n-octane

    Christopher B. Martin CHEM 3412

    18

    n-hexane vs. 1-hexene

    Christopher B. Martin CHEM 3412

    19

    1-octyne vs. 4-octyne

    Christopher B. Martin CHEM 3412

    20

    10

    1-butanol vs. dipropylamine

    Christopher B. Martin CHEM 3412

    21

    Ketone vs. Aldehyde

    Christopher B. Martin CHEM 3412

    22

    11

    Nitrile (C=N)

    Christopher B. Martin CHEM 3412

    23

    Crude Summary of IR Regions

    Christopher B. Martin CHEM 3412

    24

    12

    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
    Christopher B. Martin CHEM 3412

    fragments
    25

    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?

    Christopher B. Martin CHEM 3412

    26

    13

    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
    27

    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

    28

    14

    IR and MS of 1,4-dioxane

    Christopher B. Martin CHEM 3412

    29

    IR and MS of 2-butanol

    Christopher B. Martin CHEM 3412

    30

    15

    IR and MS of a diester

    Christopher B. Martin CHEM 3412

    31

    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.

    Christopher B. Martin CHEM 3412

    32

    16

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