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both give us information about the number of

chemically nonequivalent nuclei
(nonequivalent hydrogens or nonequivalent
carbons)
both give us information about the
environment of the nuclei (hybridization state,
attached atoms, etc.)
 the signal for the NMR of a 13 C nucleus is
10-4 times weaker than the signal for a
hydrogen nucleus
a signal for a 13C nucleus is only about 1% as
intense as that for 1H because of the
magnetic properties of the nuclei, and
at the "natural abundance" level only 1.1% of
all the C atoms in a sample are 13C (most are
12C)
13Csignals are spread over a much wider
range than 1H signals making it easier to
identify and count individual nuclei
Check the spectra on the next slides: Figure
(A) shows the 1H NMR spectrum of 1-
chloropentane; Figure (B) shows the 13C
spectrum. It is much easier to identify the
compound as 1-chloropentane by its 13C
spectrum than by its 1H spectrum.
 1H

ClCH2 CH3
ClCH2CH2CH2CH2CH3

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (d, ppm)

 13C

ClCH2CH2CH2CH2CH3

a separate,
distinct peak
appears for each
of the 5 carbons CDCl3

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (d, ppm)

are measured in ppm (d)
from the carbons of TMS
 hybridizationstate of carbon
 electronegativity of groups attached to
carbon
 23

138

sp3 hybridized carbon is more shielded than sp2

 OH

61

202

sp3 hybridized carbon is more shielded than sp2

 OH

23 61

an electronegative atom deshields the carbon

to which it is attached
 O

138 202

an electronegative atom deshields the carbon

to which it is attached
Type of carbon Chemical shift (d), Type of carbon Chemical shift (d),
ppm ppm

RCH3 0-35 RC CR 65-90

R2CH2 15-40 R2C CR2 100-150

R3CH 25-50

110-175
R4C 30-40
 Chemical shift Chemical shift
Type of carbon (d),ppm Type of carbon (d),ppm

RCH2Br 20-40 O

RCH2Cl 25-50 RCOR 160-185

RCH2NH2 35-50 O

RCH2OH 50-65 RCR 190-220

RCH2OR 50-65
 Resonance frequency is ~ one-fourth, 15.1 MHz
instead of 60 MHz.
 Peak areas are not proportional to number of
carbons.

16
 Itis unlikely that a 13C would be adjacent to
another 13C, so splitting by carbon is
negligible.
 13C will magnetically couple with attached
protons and adjacent protons.
 These complex splitting patterns are difficult
to interpret.
=>

17
 To simplify the spectrum, protons are
continuously irradiated with “noise,” so they
are rapidly flipping.
 The carbon nuclei see an average of all the
possible proton spin states.
 Thus, each different kind of carbon gives a
single, unsplit peak.
=>

18
 13C nuclei are split only by the protons attached
directly to them.
 The N + 1 rule applies: a carbon with N number
of protons gives a signal with
N + 1 peaks.
=>

19
proton-
coupled

proton-
decoupled
proton-decoupled
HO-CH2-CH2-CH3

off-resonance-decoupled
Proton-Coupled 13C NMR of 2-Butanol
Proton-Decoupled 13C NMR of
2-Butanol
 The number of different signals indicates the
number of different kinds of carbon.
 The location (chemical shift) indicates the type
of functional group.
 The splitting pattern of off-resonance
decoupled spectrum indicates the number of
protons attached to the carbon.

25
 =>

26
 Nuclear Magnetic Resonance Spectroscopy
13C NMR
13C Spectra are easier to analyze than 1H spectra because the
signals are not split. Each type of carbon atom appears as a
single peak.

27
 Nuclear Magnetic Resonance Spectroscopy
13C NMR—Number of Signals
• The number of signals in a 13C spectrum gives the number of
different types of carbon atoms in a molecule.
• Because 13C NMR signals are not split, the number of signals
equals the number of lines in the 13C spectrum.
• In contrast to the 1H NMR situation, peak intensity is not
proportional to the number of absorbing carbons, so 13C NMR
signals are not integrated.

28
 Nuclear Magnetic Resonance Spectroscopy

13C NMR—Number of Signals

29
 Nuclear Magnetic Resonance Spectroscopy

13C NMR—Number of Signals

30
 Nuclear Magnetic Resonance Spectroscopy
13C NMR—Position of Signals
• In contrast to the small range of chemical shifts in 1H NMR (1-
10 ppm usually), 13C NMR absorptions occur over a much
broader range (0-220 ppm).
• The chemical shifts of carbon atoms in 13C NMR depend on
the same effects as the chemical shifts of protons in 1H NMR.

31
 =>

Chapter 13 35
The HETCOR spectrum of 2-methyl-3-pentanone
indicates coupling between protons and the carbon to
which they are attached
The COSY spectrum identifies protons that are coupled

Cross peaks indicate pairs of protons that are coupled

ChemNMR 13C Estimation

7.6
208.8
36.8 29.5
2-butanone

Estimation quality is indicated by color: good, medium, rough

220 200 180 160 140 120 100 80 60 40 20 0

PPM
ChemNMR 13C Estimation

16.9 16.9
210.8
13.6 44.8 44.8 13.6
4-heptanone

Estimation quality is indicated by color: good, medium, rough

220 200 180 160 140 120 100 80 60 40 20 0

PPM
ChemNMR 13C Estimation

18.3

18.3 31.3

81.8
OH

18.3 31.3

18.3
2,4-dimethyl-3-pentanol

Estimation quality is indicated by color: good, medium, rough

90 80 70 60 50 40 30 20 10 0
PPM
ChemNMR 13C Estimation

18.4
13.5 O
21.9
10.3
36.1 173.1

O
66.2
propyl butanoate

Estimation quality is indicated by color: good, medium, rough

180 160 140 120 100 80 60 40 20 0

PPM
ChemNMR 13C Estimation

22.9
O

24.3 62.1
170.2
22.9 O 20.7
38.7
isoamyl acetate

Estimation quality is indicated by color: good, medium, rough

180 160 140 120 100 80 60 40 20 0

PPM
ChemNMR 13C Estimation

202.2 24.3 13.8

O 43.2 22.2
1 pentanal

Estimation quality is indicated by color: good, medium, rough

220 200 180 160 140 120 100 80 60 40 20 0

PPM
ChemNMR 13C Estimation

129.5 129.8

191.0
21.3
144.2 133.9

O
129.5 129.8
4-methylbenzaldehyde

Estimation quality is indicated by color: good, medium, rough

200 180 160 140 120 100 80 60 40 20 0

PPM
ChemNMR 13C Estimation

18.1
178.4
13.5 OH
36.2
butanoic acid

Estimation quality is indicated by color: good, medium, rough

180 160 140 120 100 80 60 40 20 0

PPM