You are on page 1of 6

Chapter 13: Spectroscopy – Nuclear Introduction

Magnetic Resonance (13C NMR) Three main areas of organic chemistry:


• Separation/ purification
OH – Chromatography, distillation, extraction,
recrystallization, natural products isolation, etc.
2-phenylethanol • Synthesis
– Reactions, mechanisms, chemoselectivity,
regioselectivity, etc.
• Identification
– Qualitative analysis, spectroscopy

Spectroscopy deals with the identification of


organic compounds based on their interactions
with electromagnetic radiation
1 2

Electromagnetic Radiation Electromagnetic Spectrum


• Electromagnetic radiation (ER) has both the properties of
particles and waves • Nuclear magnetic resonance spectroscopy: measurement
of amount of radiation absorbed by compounds within RF
• Particles of ER are called photons and they each possess an region:
amount of energy referred to as a quantum
– This energy is proportional to frequency: E = hν, where h =
Planck’s constant and ν is frequency
• Photons travel at the speed of light, c = 3.00×108 m/s (λν = c)
• The range of photon energies is described by the
electromagnetic spectrum
– Frequency and wavelength (λ) are inversely proportional
– E is directly proportional to frequency
– Molecules are very selective for the frequencies they absorb;
thus, measuring the energy of photons absorbed by a molecule
with a spectrometer gives us important clues about the 3 4
structure of the molecule

Electromagnetic Radiation Nuclear Magnetic Resonance (NMR)


• Why are molecules selective for absorbing photons of a Most widely used: proton NMR (1H NMR) and
certain energy? carbon-13 NMR (13C NMR)
– For a molecule to absorb a photon, the energy of the
NMR spectrum: provides information about the chemical
photon must exactly match the energy difference between
environment of nuclei, and thus can be used to deduce the atomic
two energetic states of the molecule (resonance)
bonding patterns (i.e., connectivity, structure ) in the molecule.
– All photons of incorrect energy simply pass through the
molecule unchanged NMR has developed to such a level of sophistication that it can be
– These energy gaps ∆E: used to determine the 3-D structures of huge protein molecules in
• Are quantized solution.
• Correspond to different Recently, NMR spectroscopy has found
molecular processes medical applications, known as
magnetic resonance imaging (MRI).
MRI utilizes the spinning motions of
atomic nuclei to provide a map of the
5 internal structure of human body tissue. 6
Background Nuclear Spin States - Carbon Nucleus
NMR spectroscopy looks at how particles with spin behave in a magnetic
field. Just like electrons, protons in the nucleus of a carbon
What is spin? Spin is a fundamental property of nature, like electrical atom have a spin number
charge or mass. Spin comes in multiples of 1/2 and can be + or -.
Protons, electrons, and neutrons possess spin. Individual unpaired
electrons, protons, and neutrons each possesses a spin of 1/2.
Recall: spin quantum number of electron can have a value of +1/2
or -1/2
Examples of nuclei with spin of +1/2 : 1H, 13C, 15N, 19F, 31P
+ 1 : 2H, 14N
+3/2 : 11B, 23Na, 35Cl The two states
+5/2 : 17O are equivalent
To be NMR active, i.e., able to generate NMR signals, spin has to be non- in energy in the
zero. absence of a
Some nuclei not detectable in NMR, e.g., 12C and 16O magnetic or an
Fortunately, spin = ½ for 1H and 13C, i.e., it allows NMR use of these + 1/2 - 1/2 electric field.8
7
most abundant nuclei for structure determination of organic compounds.

Carbon nuclei have two options in the presence of external magnetic field (B0):
Energy difference (∆E) depends on
i) type of nucleus (1H, 13C, 19F, etc.)

∆E
ii) molecular environment around nucleus
B0 iii) strength of B0 ∆E ∆E
Carbon spins aligned with B0 Carbon spins aligned against B0
α state β state
(a lower energy state) (a higher energy state)

A small energy difference between α and β states: ∆E= Eβ - Eα


Use matching energy (radio frequency “rf” photon) to promote spin from After rf radiation turned off, excited nucleus (promoted spin) will return to lower
α to β state (also called: α β transition, “spin flip”, spin resonance) energy state by releasing energy in the form of rf radiation.
Emitted rf signal (rf energy, rf frequency) is detected by receiver coils; NMR signal
is generated (stored and plotted).
β state β state
Different types of carbons release different amounts of rf energy depending on their
∆E = hν chemical environment, i.e. chemical structure. Thus, chemically different types of
B0 carbons absorb and then release different energies.

α state α state Release of energy is called: relaxation


9 10

Chemical shift (δ )
As noted earlier, resonance frequency of ∆E ∆E ∆E
spin flip depends on strength of applied
outside magnetic field (B0). INSTRUMENTATION
Since different magnetic field strength NMR magnets are used in labs,
comparison of spin flip in Hertz from these different magnetic field
strengths magnets would be cumbersome (e.g., the methyl carbon in
CH3Br measures 1475 Hz in one field strength magnet versus 738.6 Hz in
another).
PULSED FOURIER TRANSFORM
However, if frequencies of each spin flip are divided by the operating TECHNOLOGY
frequency of the instrument, a number that is independent of the strength
of magnet used is obtained. That number is called chemical shift.
FT-NMR
frequency of carbons from reference cpd (in Hz)
δ = = parts per million
operating frequency of NMR spectrometer (in MHz) requires a computer
11 12
(or ppm in short)
H2
PULSED EXCITATION Let’s consider ethyl bromide C
N H3C Br
Number of chemically different set of carbons: 2
Each carbon releases a different amount of energy
ν2 (frequency) as it relaxes (free-induction decay or FID)
ν1
Carbon next to bromine atom Carbon beta to bromine atom
O
BROADBAND
RF PULSE
O
contains a range
of frequencies
ν3

S The sum of FIDs are obtained and treated by Fourier-


All types of carbon are excited transform (FT) to obtain NMR spectrum.
13 14
simultaneously with the single RF pulse.

Sum of FIDs Fourier-transform NMR spectrum

FT
13C NMR SPECTROSCOPY
Fortunately for organic chemists, both carbon and
hydrogen nuclei are “NMR active”!

two different frequency signals


obtained from two chemically
different sets of carbons

15 16

TYPES OF INFORMATION 13C NMR spectrum of methyl acetate


FROM 13C NMR SPECTRA
1. Splitting patterns in 13C NMR are not important; all
peaks are singlets; the total number of peaks, however, is Lower frequency signal
important SHIELDED
2. 13C NMR signals cannot be integrated reliably; thus, no DESHIELDED
information can be obtained on the relative numbers of Higher frequency
carbons in a group. signals

3. The chemical shift (δ, in ppm) gives a clue as to the type of


carbon generating the peak (alkane, alkene, benzene,
aldehyde, etc.). The chemical shift range is very large for 13C
NMR, approx. 220 ppm. B0 increases
chemical shift scale
4. A separate experiment can be done to determine the # of low-field signals high-field signals
H’s directly attached to a carbon; this info is often indicated
Old designation:
on the spectrum (q = 3H’s, t = 2H’s, d = 1H, s = 0H’s) 17
downfield upfield 18
Cl
CH 2 O
# of chemically different sets of Cs = # of different signals H3C CH 3 H3C O CH 3
H3C

# of signals: 3 3

# of signals: 1 1 1 O
H3C O CH 3

CH3 CH2 CH2 CH3


HC
Br C O
N
Cl H2C O CH3 CH3CH2OH O CH 3 CH 2 O CH 3

2 2 H3 C CH 3 # of 4
# of signals: signals: 4
H3C CH3
O O

H3C CH3 H3C CH 3 CH 3 CH 2 O CH 3

2 2 4
19 20

For each of the following compounds predict the expected


number of signals in its 13C NMR spectrum. 13C Chemical shifts are most affected by:
1) CH 3
Si
H3C CH 3
H3C
• electronegativity of groups attached to carbon
a b c d e f g
• hybridization state of carbon
2) (CH3)3C-O-CH3 Br-CH2CH2-Br Br-CH2CH2CH2-Br (CH3)2CH-O-CH3
a b c d

O O O Cl
3)
a b c d

CH 3CH 2O
4) (CH 3)3C O CH 2CH 3 CH 3O CH 2 N(CH 3)2 CHCH 3
CH 3CH 2O
a b c
21 22

Types of Carbons Electronegativity effects on CH3


Classification 13C Chemical shift, δ 13C Chemical shift, δ

CH4 -2 CH4 -2
CH3CH3 primary 8 CH3NH2 27
CH3CH2CH3 secondary 16 CH3OH 50
(CH3)3CH tertiary 25 CH3F 75
(CH3)4C quaternary 28
Replacing H by C (more electronegative) deshields
C to which it is attached. 23 24
Electronegativity effects and chain length 13C Chemical shifts are most affected by:

Cl CH2 CH2 CH2 CH2 CH3 • electronegativity of groups attached to carbon


• hybridization state of carbon
Chemical 45 33 29 22 14
shift, δ

Deshielding effect of Cl decreases as


number of bonds between Cl and C increases.

25 26

Hybridization effects Carbonyl carbons are especially


deshielded
sp3 hybridized carbon is
more shielded than sp2 O
114 36
CH2 C O CH2 CH3
138 36 126-142
sp hybridized 41 171 61 14
carbon is more 127-134
shielded than sp2,
but less shielded H C C CH2 CH2 CH3
than sp3
68 84 22 20 13

27 28

Table 13.3 Table 13.3


Type of Chemical shift (δ), Type of Chemical shift (δ), Type of Chemical shift (δ), Type of Chemical shift (δ),
carbon [ppm] carbon [ppm] carbon [ppm] carbon [ppm]

RCH3 0-35 RC CR 65-90 RCH2Br 20-40 RC N 110-125


O
R2CH2 15-40 R2C CR2 100-150 RCH2Cl 25-50
RCOR 160-185
R3CH 25-50 RCH2NH2 35-50
110-175
R4C 30-40 RCH2OH 50-65 O

RCH2OR 50-65 RCR 190-220


29 30
Which trichloropropane isomer gives the following 13C NMR spectrum? Of the two structures on the right, which gives the 13C NMR spectrum
depicted below?
O
CH 3CH 2C OH

O
CH 3C O CH 3

A ketone with molecular formula C7H14O was given out as an unknown.


A cyclobutane derivative with molecular formula C6H12 provides the Its 13C NMR spectrum is shown below. Draw the structure of the ketone.
13C NMR spectrum as shown below. Draw the structure of the

derivative.

2 peaks

31 32

• Assign each structure to its 13C NMR spectrum. Briefly justify Match each of the following compounds with its 13C NMR spectrum.
your answers. O O H O Hint: how many 13C
OH
H signals expected
Hint: how many 13C O
OH P Q R S T for each cpd?
O O signals expected
X Y Z for each cpd? a b
a

c 2 peaks d
b 1 peak

1 peak

e
c
1 peak

33 34