CARBON-13 NMR SPECTROSCOPY

Viju Kumar V G Assistant Professor Department of Chemistry University college, Thiruvananthapuram

CARBON-13 NMR SPECTROSCOPY

After hydrogen, the most useful atom providing information is carbon-13. Natural carbon contains about 1% of this isotope so the instruments for its detection need to be sensitive and spectra will take longer to record.

Only the chemical shift is important as each spectrum gives only single lines for each chemically equivalent carbon.

Environment C - C (alkanes) C - C=O C - Cl or C - Br C - N (amines) C - OH C = C (alkenes) aromatic Cs (benzene rings) C=O (esters, acids, amides) C=O (aldehydes, ketones)

Chemical shift / d 10 - 35 10 - 35 30 - 70 35 - 65 50 - 65 115 - 140 125 - 150 160 - 185 190 220

Carbon-13 nmr has wide applications in the study of natural products, biological molecules and polymers

Comparison of HYDROGEN-1 and CARBON-13

natural abundance 99.9844 % relative sensitivity 1 chemical shift range 10 ppm 1H-1H-spin-spin coupling chemical environment chemical structure, regiochemistry, stereochemistry, conformation
1H:

natural abundance 1.108% relative sensitivity 1.5910-2 Chemical shift range 250 ppm long relaxation times sensitive to subtle changes in the near electronic environment but insensitive for long-range interactions (solvent effects, diamagnetic anisotropy of neighbouring groups) no homonuclear coupling Separate resonance for every C in a molecule

13C:

CARBON-13 NMR SPECTRA

Isomers of C3H7Br

H H H

H Br H HCCCH H H H
2 peaks the two outer carbons are similar

HCCCBr
H H H
3 peaks all three carbons are different

CARBON-13 NMR SPECTRA

Isomers of C3H7Br

H H H

H Br H HCCCH H H H
2 peaks the two outer carbons are similar

HCCCBr
H H H
3 peaks all three carbons are different

Ethanol C2H5OH

H
HC

COH
H

H C C OH

This is where the proton nmr spectrum of ethanol would be on the same scale.

CARBON-13 NMR SPECTRA The carbon-13 spectrum of 2-methylbutane (CH3)2CHCH2CH3

chemically equivalent carbon atoms

H CH3 H

HCCCCH H H H H

There are four chemically different carbon atoms in the molecule so there are four peaks in the C-13 nmr spectrum.

NO SPLITTING WITH C-13 ONLY ONE PEAK FOR EACH CARBON

Other isomers of C5H12 pentane 2,3-dimethylpropane CH3CH2CH2CH2CH3 (CH3)4C 3 peaks 2 peaks

CARBON-13 NMR SPECTRA - QUESTIONS

How many peaks would you expect there to be in the carbon-13 spectrum of butane 2-methylpropane butanal butanone pentan-2-one pentan-3-one CH3CH2CH2CH3 CH3CH(CH3)CH3 CH3CH2CH2CHO CH3COCH2CH3 CH3COCH2CH2CH3 CH3CH2COCH2CH3

cyclohexane

C6H12

CARBON-13 NMR SPECTRA - QUESTIONS

How many peaks would you expect there to be in the carbon-13 spectrum of butane 2-methylpropane butanal butanone pentan-2-one pentan-3-one CH3CH2CH2CH3 CH3CH(CH3)CH3 CH3CH2CH2CHO CH3COCH2CH3 CH3COCH2CH2CH3 CH3CH2COCH2CH3 2 2 4 4 5 3

cyclohexane

C6H12

19

CARBON-13 NMR SPECTRA - QUESTIONS

Identify the isomers of C4H8O

CARBON-13 NMR SPECTRA - QUESTIONS

Identify the isomers of C4H8O

A butanal
B butanone C 2-methylpropanal

CARBON-13 NMR SPECTRA - QUESTIONS

Identify the isomers of C6H12

CARBON-13 NMR SPECTRA - QUESTIONS

Identify the isomers of C6H12

X hex-1-ene or hex-2-ene 2-methylpent-1-ene 3-methylpent-1-ene 2-methylpent-2-ene 3-methylpent-2-ene Y cyclohexane

Z 2,3-dimethylbut-2-ene

or or or or or

CARBON-13 NMR SPECTROSCOPY

The proton (lower) and carbon (upper) spectra have full width of the proton spectrum is 10 ppm, while the width of the 13C spectrum is 200 ppm (20 times as large). For example, the peak for the aldehyde proton is at 9.5 in the proton spectrum, so we expect the peak for the aldehyde carbon to appear at a chemical shift between 15 and 20 times as large (between 144 and 192) in the carbon spectrum. The actual position is at 180.

CARBON-13 NMR SPECTROSCOPY

The triplet at 77 in the l3C NMR spectrum is the carbon signal for deuterated chloroform (CDCI3), split into three equal-sized peaks by coupling with the deuterium atom. Chloroform-d (CDCI3) is a common solvent for I3C NMR because the spectrometer can "lock" onto the signal from deuterium at a different frequency from carbon. The CDCl3 solvent signal is a common feature of carbon NMR spectra.

CARBON-13 NMR SPECTROSCOPY

1

H NMR and 13C NMR spectra of 1,2,2-trichloropropane.

chemical shift effects are larger in 13C NMR, an electron-withdrawing group has a substantial effect on the chemical shift of a carbon atom beta (one carbon removed) to the group. The methyl (CH3) carbon absorbs at 33 ppm downfield from TMS because the two chlorine atoms on the adjacent - CCl2- carbon have a substantial effect on the methyl carbon. The chemical shift of this methyl carbon is about 15 times that of its attached protons ( 2.1 ).

CARBON-13 NMR SPECTROSCOPY

Differences between Proton and Carbon techniques

CARBON-13 NMR SPECTROSCOPY Spin-spin Splitting

Only 1 % of the carbon atoms in the 13C NMR sample are magnetic, so there is only a small probability that an observed 13C nucleus is adjacent to another 13C nucleus. Therefore, C-C splitting can be ignored. But Carbon-Hydrogen coupling is common. Extensive C-H coupling produces complicated splitting patterns. Proton Spin Decoupling : To simplify 13C NMR spectra, they are commonly recorded using proton spin decoupling, where the protons are continuously irradiated with a broadband ("noise") proton transmitter. As a result, all the protons are continuously in resonance, and they rapidly flip their spins. The carbon nuclei see an average of the possible combinations of proton spin states. Each carbon signal appears as a single, unsplit peak because any carbon-hydrogen splitting has been eliminated. Off- Resonance Decoupling : Proton spin decoupling produces spectra that are very simple, but some valuable information is lost in the process. Off-resonance decoupling simplifies the spectrum but allows some of the splitting information to be retained. With off-resonance decoupling, the 13C nuclei are split only by the protons directly bonded to them. The N + 1 rule applies, so a carbon atom with one proton appears as a doublet, a carbon with two attached protons gives a triplet, and a methyl carbon gives quartet. Off resonance decoupled spectra are recognized by the appearance of TMS as a quartet at 0 ppm, split by the three protons of each methyl group.

CARBON-13 NMR SPECTROSCOPY

The best procedure for obtaining a 13C NMR spectrum is to run the spectrum twice: The singlets in the broadband-decoupled spectrum indicate the number of nonequivalent types of carbon atoms and their chemical shifts. The multiplicities of the signals in the offresonance-decoupled spectrum indicate the number of hydrogen atoms bonded to each carbon atom. 13C spectra are often given with two traces, one broadband decoupled and the other off-resonance decoupled. If just one trace is given, it is usually broadband decoupled.

Try this

Decoupling of heteronuclear spin coupling causes the NUCLEAR OVERHAUSER EFFECT (NOE) Decoupling 1H-13C saturates 1H and changes the 13C-spin population excess 13C in the lower level compared with the equilibrium distribution more energy is absorbed DE = 1 + (gH/2gC) better S/N

NOE depends on the specific resonance

makes quantification difficult

The NOE is sensitive to the distance NOESY experiment

DEPT

DEPT
DEPT: Distortionless Enhancement by Polarisation Transfer Differentiation between CH, CH2 and CH3 by positive (CH, CH3) or negative (CH2) signal amplitudes, using improved sensitivity of polarisation transfer.

DEPT
DEPT and APT (Attached Proton Test) experiments gives us information on

the "multiplicity of the carbon atom (quaternary, methine, methylene,

methyl) which can be carried out very quickly. DEPT find its origin in the spin-echo sequence, devised by Hahn in 1952

and used for the determination of relaxation times.

The important feature of the experiment is that the carbon signals appear to have been simply broad-band decoupled, but that according to the

multiplicity they appear either in positive (normal) phase or in negative

phase.

DEPT
Each 13C nucleus is magnetically coupled to the protons bonded to it. Under the right circumstances, this magnetic coupling allows the transfer of polarization from the protons to the carbon nucleus. The number of protons bonded to the
13C

nucleus determines how this polarization transfer occurs. A DEPT

experiment usually includes three spectral scans:

1. The normal decoupled scan, in which each type of 13C nucleus appears as a
singlet. 2. The DEPT-90 scan, in which only the CH (methine) carbons bonded to exactly one proton appear. 3. The DEPT- 135 scan, in which the CH3 (methyl) groups and CH (methine) groups appear normally, and the CH2 groups give negative peaks. Carbons that are bonded to no protons do not appear.

DEPT

DEPT
The carbonyl carbon (Cb, no protons) appears only in the regular spectrum. Cc, with 1 proton, appears normally in all the spectra. Cd, with two protons, appears as a negative peak in the DEPT- 135 spectrum. Ca, the methyl carbon with three protons, vanishes in the DEPT-90 spectrum but appears as a normal peak in the DEPT- 135 spectrum.

DEPT
Now Your turn

DEPT
The spectrum in detail.

DEPT

DEPT

DEPT
The J-modulated spin-echo and the more frequently used DEPT

experiment are pulse sequences, which transform the information

of the CH signal multiplicity and of spin-spin coupling into phase relationships (positive and negative amplitudes) of the 13C signals in

the proton decoupled

13C

NMR spectra. The DEPT experiment

benefits from a 1H - 13C polarisation transfer which increases the sensitivity by up to a factor of 4. For this reason, this technique

provides the quickest way of determining the 13C 1H multiplicities.

DEPT

DEPT
A&B

DEPT

(A) Pulse sequence for the DEPT experiment.

DEPT

(B) Effect of the pulse sequence on 1H and 13C magnetization vectors. 13C magnetization can be recorded either as multiplets or, if broad-band decoupling is applied during the acquisition period, as singlets.