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C NMR and 1H NMR

Background
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C NMR: Nuclear magnetic resonance (NMR) is one of the most important diagnostic tools available to an organic chemist. It provides information about the relative positions of spin active nuclei (protons, 1 H; carbons, 13C) in a compound and can be used to identify the structural features of a molecule. Nuclear looks at the nuclei of atoms Magnetic in the presence of a strong magnet Resonance at the energy levels which causes spins to flip Certain nuclei, like electrons, have spin associated with them. They behave like spinning tops. The spinning is associated with a magnetic field, so each nuclei acts like little magnets. Under normal conditions, these nuclei in a sample have a random orientation. In the presence of a strong magnet, they will all become parallel to the magnetic field, either aligned with the field, , or against the field, (higher in energy). There is an energy difference between the and states. When you put in the right amount of energy, you can cause the spins to flip to the spin state (this is called resonance). We detect a signal when the ratio of spins in the to states changes. Presence of electrons around a nucleus has an effect on the energy needed to flip the spins. So nuclei with a lot of electron density, such as alkane carbons, will require less energy than nuclei with electronegative groups attached. This leads to differences in the carbons position in the spectrum. What to look for in an NMR spectrum: 1. Chemical Shift - Position in the spectrum. Why does it matter where a peak is located in a spectrum? The shift gives information about the chemical environment around a 13C nucleus. a. Nuclei surrounded with a lot of electron density will be on the right side of the spectrum (upfield). b. Nuclei attached to electronegative groups do not have much electron density around them and they are found on the left side of the spectrum (downfield). Chemical Shift 0-30 15-55 20-60 30-65 40-80 75-95 105-145 115-125 110-160 Type of Carbon sp3 CH3 sp3 CH2 sp3 CH C-N C-O C C C=C C N Aromatic (benzene)

160-230

C=O

2. Number of signals Number of different types of carbon. Some carbon atoms in a molecule are in the same environment. These carbons will show the same signal in the NMR spectrum. 3. Splitting - In normal 13C spectra, hydrogens are coupled to the adjacent carbon. This causes the signal to be split into 2 or more peaks, obeying the n+1 rule. These spectra are called coupled. Decoupled spectra do not show splitting from adjacent atoms. In a coupled spectrum: If there are 0 hydrogens on a carbon, there will be one peak, called a singlet (s) If there is 1 hydrogen on a carbon, there will be two peaks, called a doublet (d) If there are 2 hydrogens on a carbon, there will be three peaks, called a triplet (t) If there are 3 hydrogens on a carbon, there will be four peaks, called a quartet (q)
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H NMR: In 13C NMR spectroscopy, we looked at where carbon atoms in a molecule showed up in the NMR spectrum. In another technique, 1H NMR spectroscopy, we will look at where the hydrogens (called protons) in a molecule show up in the spectrum. Protons show up in the NMR spectrum because, like carbon 13, protons can spin. When the spinning nuclei are irradiated with electromagnetic radiation of the proper frequency, energy is absorbed, resulting in a spin flip. When the energy difference between the states equals the frequency of radiation, this is called resonance and results in a spin flip. Absorption of energy is detected and is shown as a peak. In a molecule, the proton is not isolated but attached to another atom. Electron distribution in the molecule affects the environment of the proton. Electrons circulate creating a magnetic field that opposes the applied field. Therefore the proton experiences a magnetic field less than the actual field strength. So to reach resonance, the frequency of radiation is lowered and the proton is said to be shielded (from the full magnetic field). If there are electronegative atoms near the proton that draw away electron density, the proton will be less shielded, called deshielded, from the full magnetic field. The proton will have a different chemical shift than a proton in a molecule with no electron withdrawing groups. A chemical shift () is the change in the resonance position of a proton because of its molecular environment. Molecule: Chemical shift: CH3Cl 3.1 CH4 0.2

Environment affects the chemical shift () of a proton: INCREASED ELECTRONEGATIVITY CH3F 4.3 CH3F 4.3 CHCl3 7.3 CH3Cl 3.1 CH3OCH3 3.2 CH2Cl2 5.3 CH3Br 2.7 (CH3)3N 2.2 CH3Cl 3.1 CH3I 2.2 CH3CH3 0.9

Special Cases: Double bonds allow the electrons to circulate in other ways than single bonds, so instead of shielding the protons, it deshields them. Examples and their chemical shifts are below.

H H H

H H H

H H

H H
Cyclohexane, 1.4 Benzene, 7.3

Ethane, 0.9

Ethylene, 5.3

Each type of proton in a molecule will produce a signal in a 1H NMR spectrum. 2 types of protons will result in two signals. CH3CH2CH3 ClCH2OCH3 How many different types of protons are in this molecule? How many different types of protons are in this molecule?

Intensity of the signals (or area under the peak) tells you how many equivalent protons are represented by each signal. Called integration, because we use integrals to determine the area. Protons will couple with other protons that are three chemical bonds away, referred to as neighboring protons. Multiplicity (splitting) the n+1 rule 1 H NMR spectroscopy: n = # of protons three bonds away (protons on neighboring carbons) n+1 = # of peaks Splitting Singlet Doublet Triplet Quartet n= 0 1 2 3 not quadruplet what does this splitting look like

Pentet Sextet Septet Octet

4 5 6 7

not quintet

Only non-equivalent protons will split one another. Butane example CH3CH2CH2CH3 t q q t CH3CH2CH2CH3 not this: t sext. sext. t

Pre-lab questions: 1. Try to solve these unknowns: Molecular formula: C5H10O What is the SODAR? What are possible structures? A. Which of the possible structures would give these peaks in the 13C NMR? 212 (s) 36 (t) 8 (q) Assign the peaks to the carbons in the structure. B. Which of the possible structures would give these peaks in the 13C NMR? 151 (d) 88 (t) 72 (d) 22 (q) Assign the peaks to the carbons in the structure. 2. Analyze these compounds:
O O H3C H H H Br CH3

For each, how many hydrogens are there. How many different types of hydrogen are there in each molecule? Based on the table above, where will those hydrogens be in the NMR spectrum. During this lab period, you will practice analyzing IR and NMR spectra. You will be randomly assigned to four stations. At these stations you will be filling out the worksheets in this handout as you did in the last lab.

Procedure
There will not be a formal write-up for this experiment. We will only collect the IR/NMR worksheets. Do not write on any of the IR or NMR spectra. Completing the pre-lab questions is strongly advised. Obtain a list of four IR/NMR stations from your TA. You will solve the spectra at these stations. There are 3 types of in-class worksheets for you to complete found on p. 7-13. Turn all of these in to your TA at the end of the period. Go to your assigned stations around the lab. At each station there will be an NMR spectrum along with the IR spectrum and molecular formula for that compound. You will need to complete two 13C NMR stations by filling out the worksheets from the Lab Manual (p.7-8) for each unknown. You will also complete 1H NMR stations (p. 9-13). Turn all of these worksheets in to your TA at the end of the period. Steps for analyzing the IR and 13C NMR and 1H NMR of unknown compounds: 1. Analyze the molecular formula using the SODAR method. See which structural features are possible (and which cannot exist) based on the formula. Show the SODAR calculation on the worksheet and write the SODAR in the assigned space. Think about some of the isomers that may be possible. Make quick notes (e.g. ether, aldehyde, alcohol). 2. Analyze the IR spectrum noting any important stretching and bending vibrations. Look at the IR Correlation Chart and decide what functional group is present in the unknown. Record the functional group in the blank provided. Explain how you determined this functional group using the IR data. Think again about the possible isomers and eliminate the ones that do not correlate with the IR data. Make quick notes (e.g. no alcohol, possibly aldehyde). 3. Look at the 13C NMR spectrum. Fill out the table in the worksheet indicating the chemical shift and splitting of each signal. You may not need to fill in all the blanks. 4. Using the information in the splitting column, determine how many hydrogens are on each carbon (n+1 rule). Make notes about the type of carbon groups in your unknown (-CH3, -CH2-, -CH-). Do similar analysis for 1H NMR spectra. 5. Write out the Lewis structures (or line drawings) for the isomers that fit your data. Be sure to include information from all sources (formula, IR, NMR). If you are having trouble, include some structures that might fit even if you arent sure. You may have missed something that will be more obvious when you look at the structures. 6. Circle the compound that you think is the unknown. Explain how you came to this conclusion. You may be able to get full credit without the correct answer if we think your compound fits all the data and you have a good explanation. You will not get any credit if you only give a structure (even if it is correct) and you have not written down notes for steps 1-5. Post-lab questions: See lab syllabus or announcements for questions.

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C NMR Correlation Table

Chemical Shift, 8-30 15-55 20-60 25-65 35-80 30-65 40-80 Alkyne Carbon Alkene Carbon Aromatic Carbon Nitrile Carbon Carbonyl Carbon 65-85 100-150

Type of Carbon Written in Bold CH3 C H2 C H C Br C Cl C N C O C C C C C Primary Carbon Secondary Carbon Tertiary Carbon

110-160 110-120 170-210

N C C O

H NMR Correlation Table

Type of Hydrogen
RCH2Br RCH2Cl

Type of Hydrogen
CH3 C H2 H C

Chemical Shift 0.8-1.1 1.2-1.4

Chemical Shift 3.4-3.6 3.6-3.8 3.3-4.0 4.5-5.0

Primary Akyl Secondary Alkyl

Alkyl Bromide Alkyl Chloride Ether Vinylic

ROCH2R R H H R R H

Tertiary Alkyl Primary Allylic

1.4-1.7 1.6-1.9 2.1-2.6

Vinylic

5.0-6.5

CH3 O

Ketone
R CH3 CH3

Aromatic
O H

6.0-9.0 9.7-10 10-11

Benzylic Acetylenic Alkyl Iodide

2.2-2.7 2.5-3.0 3.1-3.3

Aldehydic Acidic
OH

R RCH2I

IR/13C NMR Spectroscopy Worksheet

Name: _______________________________ Chemical formula: ________________
Show the SODAR calculation:

Station #: ________ SODAR: ________

What functional groups are in this compound? _____________________________ Explain which stretches and bends you used to determine this:

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C NMR Signals: Chemical Shift

_____________ _____________ _____________ _____________ _____________ _____________ _____________ _____________

Signal #
1 2 3 4 5 6 7 8

Splitting
________ ________ ________ ________ ________ ________ ________ ________

How many hydrogens are on this carbon?

_________ _________ _________ _________ _________ _________ _________ _________

Write the Lewis structures of structural isomers that are consistent with the IR and NMR spectra. If you have more than one structure, circle the isomer which best accounts for the IR and NMR data. Explain your structure(s).

IR/13C NMR Spectroscopy Worksheet

Name: _______________________________ Chemical formula: ________________
Show the SODAR calculation:

Station #: ________ SODAR: ________

What functional groups are in this compound? _____________________________ Explain which stretches and bends you used to determine this:

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C NMR Signals: Chemical Shift

_____________ _____________ _____________ _____________ _____________ _____________ _____________ _____________

Signal #
1 2 3 4 5 6 7 8

Splitting
________ ________ ________ ________ ________ ________ ________ ________

How many hydrogens are on this carbon?

_________ _________ _________ _________ _________ _________ _________ _________

Write the Lewis structures of structural isomers that are consistent with the IR and NMR spectra. If you have more than one structure, circle the isomer which best accounts for the IR and NMR data. Explain your structure(s).

IR/1H NMR Spectroscopy Worksheet

Name: _______________________________ Chemical formula: ________________
Show the SODAR calculation:

Station #: ________ SODAR: ________

What functional groups are in this compound? _____________________________ Explain which stretches and bends you used to determine this:

H NMR Signals: Chemical Shift

_____________ _____________ _____________ _____________ _____________ _____________ _____________ _____________

Signal #
1 2 3 4 5 6 7 8

# Hydrogens
________ ________ ________ ________ ________ ________ ________ ________

Splitting
_________ _________ _________ _________ _________ _________ _________ _________

How many hydrogens are three bonds away (neighbors)?

_________ _________ _________ _________ _________ _________ _________ _________

Write the Lewis structures of structural isomers that are consistent with the IR and NMR spectra. If you have more than one structure, circle the isomer which best accounts for the IR and NMR data. Explain your structure(s).

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IR/1H NMR Spectroscopy Worksheet

Name: _______________________________ Chemical formula: ________________
Show the SODAR calculation:

Station #: ________ SODAR: ________

What functional groups are in this compound? _____________________________ Explain which stretches and bends you used to determine this:

H NMR Signals: Chemical Shift

_____________ _____________ _____________ _____________ _____________ _____________ _____________ _____________

Signal #
1 2 3 4 5 6 7 8

# Hydrogens
________ ________ ________ ________ ________ ________ ________ ________

Splitting
_________ _________ _________ _________ _________ _________ _________ _________

How many hydrogens are three bonds away (neighbors)?

_________ _________ _________ _________ _________ _________ _________ _________

Write the Lewis structures of structural isomers that are consistent with the IR and NMR spectra. If you have more than one structure, circle the isomer which best accounts for the IR and NMR data. Explain your structure(s).

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IR/1H NMR Spectroscopy Worksheet

Name: _______________________________ Chemical formula: ________________
Show the SODAR calculation:

Station #: ________ SODAR: ________

What functional groups are in this compound? _____________________________ Explain which stretches and bends you used to determine this:

H NMR Signals: Chemical Shift

_____________ _____________ _____________ _____________ _____________ _____________ _____________ _____________

Signal #
1 2 3 4 5 6 7 8

# Hydrogens
________ ________ ________ ________ ________ ________ ________ ________

Splitting
_________ _________ _________ _________ _________ _________ _________ _________

How many hydrogens are three bonds away (neighbors)?

_________ _________ _________ _________ _________ _________ _________ _________

Write the Lewis structures of structural isomers that are consistent with the IR and NMR spectra. If you have more than one structure, circle the isomer which best accounts for the IR and NMR data. Explain your structure(s).

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IR/1H NMR Spectroscopy Worksheet

Name: _______________________________ Chemical formula: ________________
Show the SODAR calculation:

Station #: ________ SODAR: ________

What functional groups are in this compound? _____________________________ Explain which stretches and bends you used to determine this:

H NMR Signals: Chemical Shift

_____________ _____________ _____________ _____________ _____________ _____________ _____________ _____________

Signal #
1 2 3 4 5 6 7 8

# Hydrogens
________ ________ ________ ________ ________ ________ ________ ________

Splitting
_________ _________ _________ _________ _________ _________ _________ _________

How many hydrogens are three bonds away (neighbors)?

_________ _________ _________ _________ _________ _________ _________ _________

Write the Lewis structures of structural isomers that are consistent with the IR and NMR spectra. If you have more than one structure, circle the isomer which best accounts for the IR and NMR data. Explain your structure(s).

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Name _______________________________
Predict the NMR of the following structure (draw the structure):

Station # ________

How many types of nonequivalent protons are there? Label (on the structure you wrote) each type with a letter, A, B, C, etc. On the line below, draw a scale and predict what the spectrum would look like (assign peaks (A, B, C, etc) and include splitting (s, t, d, etc) and the integration (1H, 3H, etc) ) :

_____________________________________________________________________________________

Station # ________
Predict the NMR of the following structure (draw the structure):

How many types of nonequivalent protons are there? Label (on the structure you wrote) each type with a letter, A, B, C, etc. On the line below, draw a scale and predict what the spectrum would look like (assign peaks (A, B, C, etc) and include splitting (s, t, d, etc) and the integration (1H, 3H, etc) ) :

_____________________________________________________________________________________