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NMR

Netti Herawati Halik


nuclear magnetic resonance/ nmr
Nuclear Magnetic Resonance (nmr)
-Inti beberapa atom yang memiliki spin : 1H, 13C, 19F, …
-Inti beberapa atom yang tidak memiliki spin : 2H, 12C, 16O, …
- Partikel bermuatan yang bergerak menimbulkan medan magnet ()

-Jika ditempatkan diantara kutub medan magnet yang kuat, spinning inti
akan sejajar atau berlawanan dengan medan terapan dengan energi yang
berbeda. Jika menggunakan frekuensi radio yang tepat/tertentu, medan
magnet diubah hingga ΔE = EEM. Jika energi cocok, maka inti akan
mengubah keadaan spin (resonansi) dan memberikan signal magnetik.

ΔE
Medan magnet = 14,092 gauss
for 1H v = 60,000,000 Hz (60 MHz)

Spektrum nmr

Medan magnet 

10 9 8 7 6 5 4 3 2 1 0

Pergeseran kimia (ppm)


Inti 1H di lindungi ( shielded) medan magnet yang dihasilkan oleh
elektron disekelilingnya. Semakin tinggi kepadatan elektron disekeliling
inti, semakin tinggi medan magnet yang dibutuhkan untuk menyebabkan
resonansi

CH3Cl versus CH4

Densitas elektron Densitas elektron


rendah, beresonansi tinggi, beresonansi
pada medan terapan pada medan terapan
lebih rendah lebih tinggi

CHCCl3 ??
Informasi dari spektrum 1H-nmr :

1. Jumlah signal: berapa banyak tipe hidrogen yang


berbeda dalam molekul.
2. Posisi signal (pergeseran kimia): menyatakan tipe
dari hidrogen.
3. Luas relatif daerah di bawah signal (integrasi):
berapa banyak hidrogen tiap tipe/jenis.
4. pemisahan: Berapa banyak hidrogen tetangga.
Signal Splitting; Aturan (n + 1)

• Peak/puncak: unit di mana sebuah signal NMR


terpisah; doublet, triplet, quartet, multiplet, etc.
• Signal splitting/pemisahan signal:
pemisahan/Splitting suatu signalNMR menjadi
sebuah set peak karena pengaruh hidrogen tetangga
yang non ekuivalen
• Aturan (n + 1) : Jika sebuah hidrogen memiliki n
hidrogen tetangga yang non ekuivalen dengan dirinya
tetapi ekuivalen dengan sesamanya pada atom yang
sama atau berdekatan, signal 1H-NMR akan terpisah
menjadi (n + 1) puncak/peaks.
Signal Splitting (n + 1)

– 1H-NMR spectrum of 1,1-dichloroethane.

For these hydrogens, n = 1; For this hydrogen, n = 3;


their signal is split into CH3 - CH- Cl its signal is split into
(1 + 1) = 2 peaks; a doublet Cl (3 + 1) = 4 peaks; a quartet
Signal Splitting (n + 1)
Soal: Prediksi jumlah signal 1H-NMR dan pola
pemisahan tiap hidrogen

O
(a) CH3 CCH2 CH3

O
(b) CH3 CH2 CCH2 CH3

O
(c) CH3 CCH( CH3 ) 2
Origins of Signal Splitting
• Signal coupling: An interaction in which the nuclear
spins of adjacent atoms influence each other and
lead to the splitting of NMR signals.
• Coupling constant (J): The separation on an NMR
spectrum (in hertz) between adjacent peaks in a
multiplet.
– A quantitative measure of the spin-spin coupling
with adjacent nuclei.
Origins of Signal Splitting
• Illustration of spin-spin coupling that gives rise to
signal splitting in 1H-NMR spectra.
Origins of Signal Splitting
– The quartet-triplet 1H-NMR signals of 3-pentanone
with the original trace and an expansion to show the
signal splitting clearly.
Coupling Constants
• Coupling constant (J): The distance between peaks in a
split signal, expressed in hertz.
– The value is a quantitative measure of the magnetic
interaction of nuclei with coupled spins.
Ha Ha
Ha Hb
H
C C Hb Hb a

Hb
6-8 Hz 8-14 Hz 0-5 Hz 0-5 Hz

Ha Ha Hb Ha Ha
C C C C C C
Hb Hb Hb
11-18 Hz 5-10 Hz 0-5 Hz 8-11 Hz
Origins of Signal Splitting
• The origins of signal splitting patterns. Each arrow
represents an Hb nuclear spin orientation.
Signal Splitting
• Pascal’s triangle.
– As illustrated by the
highlighted entries, each
entry is the sum of the
values immediately above
it to the left and the right.
Physical Basis for (n + 1) Rule
• Coupling of nuclear spins is mediated through
intervening bonds.
– H atoms with more than three bonds between them
generally do not exhibit coupling.
– For H atoms three bonds apart, the coupling is called
vicinal coupling.
Physical Basis for (n + 1) Rule

• Coupling that arises when Hb is split by two


different nonequivalent H atoms, Ha and Hc.
More Complex Splitting Patterns

– Complex coupling that arises when Hb is split by Ha


and two equivalent atoms Hc.
More Complex Splitting Patterns
– Since the angle between C-H bond determines the extent of
coupling, bond rotation is a key parameter.
– In molecules with free rotation about C-C sigma bonds, H
atoms bonded to the same carbon in CH3 and CH2 groups are
equivalent.
– If there is restricted rotation, as in alkenes and cyclic
structures, H atoms bonded to the same carbon may not be
equivalent.
– Nonequivalent H on the same carbon will couple and cause
signal splitting.
– This type of coupling is called geminal coupling.
More Complex Splitting Patterns
– In ethyl propenoate, an unsymmetrical terminal
alkene, the three vinylic hydrogens are
nonequivalent.
More Complex Splitting Patterns
– Tree diagram for the complex coupling seen for the
three alkenyl H atoms in ethyl propenoate.
More Complex Splitting Patterns
– Cyclic structures often have restricted rotation about
their C-C bonds and have constrained conformations.
– As a result, two H atoms on a CH2 group can be
nonequivalent, leading to complex splitting.
More Complex Splitting Patterns
– A tree diagram for the complex coupling seen for
the vinyl group and the oxirane ring H atoms of 2-
methyl-2-vinyloxirane.
More Complex Splitting Patterns
• Complex coupling in flexible molecules.
– Coupling in molecules with unrestricted bond rotation
often gives only m + n + I peaks.
– That is, the number of peaks for a signal is the number of
adjacent hydrogens + 1, no matter how many different
sets of equivalent H atoms that represents.
– The explanation is that bond rotation averages the
coupling constants throughout molecules with freely
rotation bonds and tends to make them similar; for
example in the 6- to 8-Hz range for H atoms on freely
rotating sp3 hybridized C atoms.
More Complex Splitting Patterns
– Simplification of signal splitting occurs when
coupling constants are the same.
1. Jumlah signal: berapa banyak tipe hidrogen yang
berbeda dalam molekul.

Hidrogen yang memiliki medan magnet yang sama


(equivalent) beresonansi pada medan terapan yang
sama

Hidrogen yang ekuivalen secara magnetik juga ekuivalen


secara kimiawi

# berapa signal ? CH4 CH3CH3


Berapa banyak signal
yang muncul?

H3C CH3
C
C
H3C CH3
one
one

CH3

CH3
one
two
CH3
H3C C CH3 CH3CH2-Br
Br
two
one

CH3CH2CH2-Br CH3CHCH3
Cl
three
two
CH3CHCH2CH3 Cl-CH2CH2CH2-Cl
Br

four two

CH3
CH2Cl

three
2. Posisi signal (pergeseran kimia): menyatakan tipe
dari hidrogen.
combinations may greatly
primary 0.9 ppm influence chemical shifts.
secondary 1.3 For example, the benzyl
tertiary 1.5 hydrogens in benzyl chloride
aromatic 6-8.5 are shifted to lower field by
allyl 1.7 the chlorine and resonate at
benzyl 2.2-3 4.5 ppm.
chlorides 3-4 H-C-Cl
bromides 2.5-4 H-C-Br
iodides 2-4 H-C-I
alcohols 3.4-4 H-C-O
alcohols 1-5.5 H-O- (variable)
Senyawa referensi = tetramethylsilane (CH3)4Si @ 0.0 ppm

ingat: medan magnet 


 pergeseran kimia

convention: let most upfield signal = a, next most upfield = b, etc.


… c b a tms
toluene

CH3

b a

b a
chemical shifts

H3C CH3
C
a C a
H3C CH3

CH3 a

a b

CH3
a
a a b
CH3
H3C C CH3 CH3CH2-Br
a Br a

a b c a b a
CH3CH2CH2-Br CH3CHCH3
Cl
b d c a b a b
CH3CHCH2CH3 Cl-CH2CH2CH2-Cl
Br

a
CH3
CH2Cl
b

c
3. Luas relatif daerah di bawah signal (integrasi): berapa banyak hidrogen
tiap tipe/jenis.

a b c
CH3CH2CH2Br a 3H a:b:c=3:2:2
b 2H
c 2H

a b a
CH3CHCH3 a 6H a:b=6:1
Cl b 1H
integration

H3C CH3
C
a C a
H3C CH3

a 12 H a 12 H

CH3 a

a b

CH3
a 6H a
a 6H
b 4H
a a b
CH3
H3C C CH3 CH3CH2-Br
a Br a
a 3H
a 9H b 2H

a b c a b a
CH3CH2CH2-Br CH3CHCH3
Cl
a 3H
b 2H a 6H
c 2H b 1H
b d c a b a b
CH3CHCH2CH3 Cl-CH2CH2CH2-Cl
Br
a 3H a 2H
b 3H b 4H
c 2H a
d 1H CH3
CH2Cl
b
a 3H
c b 2H
c 4H
c b a

Integrasi: I tiap tahap ukuran tinggi dalam tiap integrasi dan dihitung
sebagai perbandingan terendah: a:b:c = 24 mm : 16 mm : 32 mm = 1.5 :
1.0 : 2.0  3H : 2H : 4H
If the formula is known ( C8H9OF ), add up all of the “steps” and divide by
the number of hydrogens = (24 + 16 + 32 mm) / 9H = 8.0 mm / Hydrogen.
a = 24 mm / 8.0 mm/H  3 H; b = 16 mm/8.0 mm/H  2H; c
= 32 mm/8.0 mm/H  4H.
4. pemisahan: Berapa banyak hidrogen tetangga.
Secara umum, n-hidrogen tetangga ekuivalen akan terpisah dalam sebuah
signal 1H dengan pola pascal ( n + 1 ) .
“tetangga /neighboring” – tidak lebih dari 3 ikatan
n n+1 Pascal pattern:
0 1 1 singlet
1 2 1 1 doublet
2 3 1 2 1 triplet
3 4 1 3 3 1 quartet
4 5 1 4 6 4 1 quintet
note: n harus hidrogen tetangga yang ekuivalen must
be equivalent neighboring hydrogens untuk
menghasilkan pemisahan dengan pola pascall. Jika
tetangga tersebut tidak ekuivalen, maka akan nampak
sebagai pola yang kompleks (aka complex multiplet).

note: hidrogen alkohol –OH biasanya tidak memisahkan


(split) signal hidrogen tetangga dan juga signalnya tidak
terpisah. Normalnya integrasi sebuah singlet 1 – 5.5
ppm (variable).
Bagaimana pola
pemisahannya?

H3C CH3
C
a C a
H3C CH3

a 12 H singlet a 12 H singlet

CH3 a

a b

CH3
a 6 H singlet a
a 6 H singlet
b 4 H singlet
a a b
CH3
H3C C CH3 CH3CH2-Br
a Br a
a 3 H triplet
a 9 H singlet b 2 H quartet

a b c a b a
CH3CH2CH2-Br CH3CHCH3
Cl
a 3 H triplet
b 2 H complex a 6 H doublet
c 2 H triplet b 1 H septet
b d c a b a b
CH3CHCH2CH3 Cl-CH2CH2CH2-Cl
Br
a 3H triplet a 2 H quintet
b 3H doublet b 4 H triplet
c 2H complex
d 1H complex

a
CH3 a b c
CH2Cl CH3CH2-OH
b
a 3 H triplet
c a 3 H singlet b 2 H quartet
b 2 H singlet c 1 H singlet
c 4 H ~singlet
cyclohexane

a singlet 12H
2,3-dimethyl-2-butene

H3C CH3
C C a singlet 12H
H3C CH3
benzene

a singlet 6H
p-xylene
H3C CH3
a a
b

a singlet 6H
b singlet 4H
tert-butyl bromide

CH3 a singlet 9H
H3C C CH3
Br
Etil bromida

a b
CH3CH2-Br

a triplet 3H
b quartet 2H
1-bromopropane

a b c
CH3CH2CH2-Br

a triplet 3H
b complex 2H
c triplet 3H
isopropyl chloride

a b a
CH3CHCH3
Cl

a doublet 6H
b septet 1H
2-bromobutane
b d c a
CH3CHCH2CH3
Br

a triplet 3H
b doublet 3H
c complex 2H
d complex 1H
o-methylbenzyl chloride

a
CH3 b
CH2Cl

c a singlet 3H
b singlet 2H
c ~ singlet 4H
ethanol

a c b
CH3CH2-OH

a triplet 3H
b singlet 1H
c quartet 2H
c
ethylbenzene b a
CH2CH3

a triplet 3H
b quartet 2H
c ~singlet 5H
p-diethylbenzene
a b c b a
CH3CH2 CH2CH3

a triplet 6H
b quartet 4H
c singlet 4H
m-diethylbenzene
o-diethylbenzene
2-bromo-2-methylbutane

b
CH3
b CH3CCH2CH3 a
Br c

a triplet 3H
b singlet 6H
c quartet 2H b & c overlap
di-n-propylether

a b c c b a
CH3CH2CH2-O-CH2CH2CH3

a triplet 6H
b complex 4H
c triplet 4H
1-propanol

a b d c
CH3CH2CH2-OH

a triplet 3H
b complex 2H
c singlet 1H
d triplet 2H
C11H16

a 9H = 3CH3, no neighbors
9H
c 5H = monosubstituted benzene
b 2H, no neighbors
c b a
CH3
CH2 C CH3
CH3

neopentylbenzene
2H
5H
C4H8Br2

a = 6H, two CH3 with no neighbors


(CH3)2C— 6H

b = CH2, no neighbors & shifted downfield due


to Br

CH3
2H
H3C C CH2
Br Br
C7H8O

c = monosubst. benzene
b = CH2
5H
c = OH
OH
H2 C

2H

1H
C4H9Br
a doublet 1.04 ppm 6H
b complex 1.95 ppm 1H
c doublet 3.33 ppm 2H

a = two equivalent CH3’s with one neighboring H (b?)


c = CH2 with one neighbor H (also b)

a
CH3 a 6H doublet
CH3CHCH2Br b 1H complex
a b c c 2H doublet
C10H13Cl
a singlet 1.57 ppm 6H
b singlet 3.07 ppm 2H
c singlet 7.27 ppm 5H

a = two-equilalent CH3’s with no neighbors


c = monosubstituted benzene ring
b = CH2

a singlet 6H
a
b CH3 b singlet 2H
c
c singlet 5H
CH2 C CH3
Cl

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