SPEKTROSKOPI NMR

Soerya Dewi M
Elusidasi Struktur Senyawa Organik 1
Referensi:
◼ Dasar-dasar penentuan struktur molekul berdasarkan data
spektrum 1H & 13C NMR, 2016, Yana M Syah, Lab. Spektroskopi
Massa dan NMR, ITB.
◼ NMR Spectroscopy, Basic Principles and Applications, by Roger
S. Macomber
◼ Organic Chemistry, 5th Edition, 2003, L. G. Wade Jr., Prentice
Hall.
◼ Some figures copy from the web page by Guillermo Moyna,
University of the Sciences in Philadelphia
◼ http//www.cis.rit.edu/htbooks/nmr/ by Joseph P. Hornak

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NMR 400 MHz

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Spektrum 1H NMR

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 Spektroskopi NMR
Dimana posisinya?

1nm 10 102 103 104 105 106 107

(the wave) X-ray UV/VIS Infrared Microwave Radio

Frequency
(the transition) electronic Vibration Rotation Nuclear
(spectrometer) X-ray UV/VIS Infrared/Raman NMR
Fluorescence

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NMR (Nuclear Magnetic Resonance)
◼ Pengukuran yang didasarkan pada absorpsi radiasi
gelombang elektromagnetik pada daerah frekuensi
gelombang radio (~4-900 MHz)
◼ Teknik analisis:

- sampel diletakkan dalam medan magnit kuat

(homogen dan konstan)
- diradiasi oleh sinar gelombang radio
- dideteksi sinyal magnetik yang dihasilkan
▪ Dua tipe :
- 1H NMR digunakan untuk menentukan tipe dan
jumlah atom H dari suatu molekul
- 13C NMR digunakan untuk menentukan tipe dan
jumlah atom C dari suatu molekul
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 DATA INSTRUMENT

UV-vis : lmax(nm)
IR : n (cm-1) (bil. gelombang)
1H NMR : d (ppm); m (s, d, t); J (Hz)
13C NMR : d (ppm)
MS : m/z

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 DATA YANG DIPEROLEH

UV-vis : Gugus kromofor, kerangka?

IR : Gugus fungsi
1H NMR : Jenis dan jumlah proton
13C NMR : Jenis & jumlah karbon, kerangka struktur
1D & 2D : Gugus fungsi, kromofor, stereokimia
MS : Massa relatif, unit struktur, rumus molekul

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Fenomena resonansi

Inti Atom
(bermuatan +)

berputar pada
sumbunya

Putaran inti (+) menghasilkan

momen magnet
Momen Magnet
()
Fenomena resonansi
Apakah semua inti dapat menghasilkan momen magnet ???
tergantung kepada bilangan kuantum spin (I)

I=0 I=½ I = 1, 3/2, 2, ...

12C, 18O 1H, 13C, 15N 2H, 11B, 14N

19F, 29Si, 31P 17O, 33S, 35Cl

tidak ada
momen
magnet ada momen magnet
Spin inti atom (I)
◼ Hanya inti atom yang mempunyai I  0 yang dapat
menyerap/memancarkan radiasi elektromagnetik.
-Inti atom dengan masa genap (A) dan muatan genap
(Z) → I = 0,
contoh: 12C, 16O, 32S → tdk ada sinyal NMR
- Inti atom dengan masa genap (A) dan muatan ganjil
(Z) → I  0,
contoh: 2H, 10B, 14N → ada sinyal NMR
- Inti atom dengan masa ganjil (A) → I  0,
contoh: 1H, 13C, 15N, 31P → ada sinyal NMR

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Fenomena resonansi

Tingkat energi spin

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Fenomena resonansi

kutub magnet

Bo Bo

kutub magnet
arah momen magnet
tidak beraturan arah momen magnet menjadi
searah () atau berlawanan ()
terhadap Bo
Bo = medan magnet luar
Fenomena resonansi
kutub magnet kutub magnet

hn
Bo Bo

kutub magnet kutub magnet

berlawanan arah
dengan arah Bo

searah dengan
arah Bo
Perpindahan dari keadaan energi  ke  = RESONANSI
Perpindahan dari keadaan energi  ke  = relaksasi
Fenomena resonansi
Analisis vektor memperlihatkan bahwa arah vektor magnet inti
dibawah pengaruh medan luar (Bo) tidak searah dengan arah
medan magnet tersebut melainkan membentuk putaran presesi
seperti giroskop (‘panggal’)
z
z


hn Bo



 
Frekuensi angular (frekuensi Larmor) gerakan presesi dinyatakan:
o =  Bo E =  (h/2)Bo
 =perbandingan giromagnetik (tergantung kepada jenis inti)
Spins Orientation in a Magnetic Field (Energy Levels)

• Transition from the low energy to high energy spin state

occurs through an absorption of a photon of radio-frequency
(RF) energy

RF

Frequency of absorption: n =  Bo / 2

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Fenomena resonansi

semakin besar 
semakin besar E

E =  (h/2)Bo E
 E = hn  E’ = hn’

Bo
Semakin besar Bo (Gauss atau
Tesla, 1T = 4G), semakin besar E

Menentukan perbandingan populasi inti pada

keadaan  dan  (distribusi Boltzmann):

n () E/kT Semakin besar E, semakin besar

= e populasi inti yang searah dengan Bo ()
n ()
Bo – external magnetic field
h – Planck’s constant
 – gyromagnetic ratio
 Table 1.1 Nuclei of Major Interest to NMR Spectroscopists

Abundance 2 -8b
Relativec ν0 at
Iostope Ζ Spin μ γ×10 At 7.04T
(%) sensitivity
1T(MHz)

1
H 99.9844 1 1/2 2.7927 2.6752 1.000 42.577 300

2
H 0.0156 1 1 0.8574 0.4107 0.00964 6.536 46

10
B 18.83 5 3 1.8006 0.2875 0.0199 4.575

11
B 81.17 5 3/2 2.6880 0.8583 0.165 13.660

13
C 1.108 6 1/2 0.7022 0.6726 0.0159 10.705 75.4

14
N 99.635 7 1 0.4036 0.1933 0.00101 3.076

15
N 0.365 7 1/2 -0.2830 -0.2711 0.00104 4.315 30.4

19
F 100 9 1/2 2.6273 2.5167 0.834 40.055 282.3

29
Si 4.70 14 1/2 -0.5548 -0.5316 0.0785 8.460

31
P 100 15 1/2 1.1305 1.0829 0.0664 17.235 121.4

a Magnetic moment in units of the nuclear magneton, eh/(ΔμMp c)

b Magnetogyric ratio in SI units 26
c For equal numbers of nuclei at constant field
KESIMPULAN

Pengukuran NMR adalah menempatkan

suatu sampel dalam suatu medan kuat Bo
sehingga terjadi frekuensi Larmor dari
setiap magnet inti aktif yang apabila diberi
radiasi sesuai dengan frekuensi Larmor
tersebut akan terjadi resonansi (absorbsi).

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Aplikasi NMR: O

1) Elusidasi struktur O

‚ Natural product chemistry

O NH O
OH

‚ Synthetic organic chemistry

OH

HO
O O

- analytical tool of choice of synthetic chemists

O
O

- used in conjunction with MS and IR

2.) Mempelajari proses dinamik:
Taxol (natural product)

‚ reaction kinetics
‚ study of equilibrium (chemical or structural)
3.) Mempelajari struktur tiga dimensi
‚ Proteins, Protein-ligand complexes
‚ DNA, RNA, Protein/DNA complexes
‚ Polysaccharides
4.) Metabolomics
5.) Drug Design
‚ Structure Activity Relationships by NMR NMR Structure of MMP-13
6.) Medicine -MRI
complexed to a ligand

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1H NMR—The Spectrum
• An NMR spectrum is a plot of the intensity of a peak against its chemical shift,
measured in parts per million (ppm).

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1H NMR—The Spectrum
• NMR absorptions generally appear as sharp peaks.
• Increasing chemical shift is plotted from right to left
• Most protons absorb between 0-12 ppm.
• The terms “upfield” and “downfield” describe the relative
location of peaks. Upfield means to the right. Downfield
means to the left.
• NMR absorptions are measured relative to the position of
a reference peak at 0 ppm on the d scale due to
tetramethylsilane (TMS). TMS is a volatile inert
compound that gives a single peak upfield from typical
NMR absorptions.

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1H NMR—The Spectrum

• Four different features of a 1H NMR spectrum

provide information about a compound’s
structure:
a. Number of signals (multiplisitas)
b. Position of signals (geseran kimia)
c. Intensity of signals (integrasi)
d. Spin-spin splitting of signals (kopling)

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1H NMR—The Spectrum of butanol (300 MHz, CD3Cl)

OH
CH3
H3C
Tetrametilsilan
2-Butanol (standar nol ppm)

J d
J J
J J OH H
H t
H
H C C
39 mm 60 mm 63 mm
C C H
20 mm H H TMS
H H qi
sext d

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1H NMR—Number of Signals
• The number of NMR signals equals the number of different types
of protons in a compound.
• Protons in different environments give different NMR signals.
• Equivalent protons give the same NMR signal.

• To determine equivalent protons in cycloalkanes and alkenes,

always draw all bonds to hydrogen.

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1H NMR—Number of Signals

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1H NMR—Number of Signals
• In comparing two H atoms on a ring or double bond, two
protons are equivalent only if they are cis (or trans) to
the same groups.

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1H NMR—Number of Signals

• Proton equivalency in cycloalkanes can be determined

similarly.

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1H NMR—Position of Signals
• In the vicinity of the nucleus, the magnetic field generated by the
circulating electron decreases the external magnetic field that
the proton “feels”.
• Since the electron experiences a lower magnetic field strength, it
needs a lower frequency to achieve resonance. Lower frequency is
to the right in an NMR spectrum, toward a lower chemical shift,
so shielding shifts the absorption upfield.

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1H NMR—Position of Signals

• The less shielded the nucleus becomes, the more of the

applied magnetic field (B0) it feels.
• This deshielded nucleus experiences a higher magnetic
field strength, to it needs a higher frequency to achieve
resonance.
• Higher frequency is to the left in an NMR spectrum,
toward higher chemical shift—so deshielding shifts an
absorption downfield.
• Protons near electronegative atoms are deshielded, so
they absorb downfield.

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1H NMR—Position of Signals

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1H NMR—Position of Signals

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1H NMR—Position of Signals

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1H NMR—Chemical Shift Values

• The chemical shift of a C—H bond increases with increasing alkyl

substitution.

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1H NMR—Chemical Shift Values
• In a magnetic field, the six  electrons in benzene circulate around the
ring creating a ring current.
• The magnetic field induced by these moving electrons reinforces the
applied magnetic field in the vicinity of the protons.
• The protons thus feel a stronger magnetic field and a higher
frequency is needed for resonance. Thus they are deshielded and
absorb downfield.

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1H NMR—Chemical Shift Values
• In a magnetic field, the loosely held  electrons of the double bond
create a magnetic field that reinforces the applied field in the vicinity
of the protons.
• The protons now feel a stronger magnetic field, and require a higher
frequency for resonance. Thus the protons are deshielded and the
absorption is downfield.

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1H NMR—Chemical Shift Values
• In a magnetic field, the  electrons of a carbon-carbon triple bond
are induced to circulate, but in this case the induced magnetic field
opposes the applied magnetic field (B0).
• Thus, the proton feels a weaker magnetic field, so a lower frequency
is needed for resonance. The nucleus is shielded and the
absorption is upfield.

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1H NMR—Chemical Shift Values

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1H NMR—Chemical Shift Values)

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1H NMR of Methyl Acetate

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2,3-Dimethyl-2-Butene

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1H NMR—Intensity of Signals
• The area under an NMR signal is proportional to the
number of absorbing protons.
• An NMR spectrometer automatically integrates the area
under the peaks, and prints out a stepped curve (integral)
on the spectrum.
• The height of each step is proportional to the area under
the peak, which in turn is proportional to the number of
absorbing protons.
• Modern NMR spectrometers automatically calculate and
plot the value of each integral in arbitrary units.
• The ratio of integrals to one another gives the ratio of
absorbing protons in a spectrum. Note that this gives a
ratio, and not the absolute number, of absorbing protons.
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1H NMR—Intensity of Signals

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Methyl ,-Dimethylpropionate

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How Many Hydrogens?
When the molecular formula is known,
each integral rise can be assigned to a
particular number of hydrogens.

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 1H NMR—Spin-Spin Splitting

• Consider the spectrum below:

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1,1,2-Tribromoethane
Nonequivalent protons on adjacent carbons.

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Ethyl Bromide

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 Spin-Spin Splitting in 1H NMR Spectra
• Peaks are often split into multiple peaks due to
magnetic interactions between nonequivalent
protons on adjacent carbons, The process is
called spin-spin splitting
• The splitting is into one more peak than the
number of H’s on the adjacent carbon(s), This is
the “n+1 rule”
• The relative intensities are in proportion of a
binomial distribution given by Pascal’s Triangle
• The set of peaks is a multiplet (2 = doublet, 3 =
triplet, 4 = quartet, 5=pentet, 6=hextet,
7=heptet…..)
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Rules for Spin-Spin Splitting
◼ Equivalent protons do not split each other

◼ Protons that are farther than two carbon atoms

apart do not split each other

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If Ha and Hb are not equivalent, splitting is observed when:

Splitting is not generally observed between protons

separated by more than three  bonds.

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Doublet: 1 Adjacent Proton

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 The Origin of 1H NMR—Spin-Spin Splitting
Let us now consider how a triplet arises:

• When placed in an applied magnetic field (B0), the

adjacent protons Ha and Hb can each be aligned with () or
against () B0.
• Thus, the absorbing proton feels three slightly different
magnetic fields—one slightly larger than B0(ab). one
slightly smaller than B0(ab) and one the same strength
as B0 (ab).

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Triplet: 2 Adjacent Protons

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The Origin of 1H NMR—Spin-Spin Splitting

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 The Origin of 1H NMR—Spin-Spin Splitting
• Because the absorbing proton feels three different
magnetic fields, it absorbs at three different frequencies in
the NMR spectrum, thus splitting a single absorption into a
triplet.
• Because there are two different ways to align one proton
with B0, and one proton against B0—that is, ab and ab—
the middle peak of the triplet is twice as intense as the
two outer peaks, making the ratio of the areas under the
three peaks 1:2:1.
• Two adjacent protons split an NMR signal into a triplet.
• When two protons split each other, they are said to be
coupled.
• The spacing between peaks in a split NMR signal, measured
by the J value, is equal for coupled protons.
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The Origin of 1H NMR—Spin-Spin Splitting

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Multiplisitas

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Splitting for Ethyl Groups

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Splitting for Isopropyl Groups

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Coupling Constants
◼ Distance between the peaks of multiplet
◼ Measured in Hz
◼ Not dependent on strength of the
external field
◼ Multiplets with the same coupling
constants may come from adjacent
groups of protons that split each other.

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Values for Coupling Constants

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 a c
H H
C C Complex Splitting
Hb

◼ Signals may be split by adjacent protons,

different from each other, with different
coupling constants.
◼ Example: Ha of styrene which is split by an
adjacent H trans to it (J = 17 Hz) and an
adjacent H cis to it (J = 11 Hz).

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H
a
H
c Splitting Tree
C C
Hb

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Spectrum for Styrene

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 Hydroxyl
Proton
◼ Ultrapure samples
of ethanol show
splitting.
◼ Ethanol with a
small amount of
acidic or basic
impurities will not
show splitting.

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N-H Proton
◼ Moderate rate of exchange.
◼ Peak may be broad.

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1H NMR—Structure Determination

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1H NMR—Structure Determination

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1H NMR—Structure Determination

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1H NMR—Structure Determination

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1H NMR (500 MHz, CDCl3)
OH O

O CH3
1H NMR (500 MHz, CDCl3)

O
H2
C O
O C
H2