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NMR SPECTROSCOPY-Part II Coupling Constants The distance between the peaks of a multiplet (measured in Hertz) is called the coupling

constant. Coupling constants are represented by J, and the coupling constant between two protons Ha and Hb is represented by Jab. For protons Ha and Hb separated by 3-sigma bonds (ie on adjacent carbons), the coupling constant is represented by 3Jab.
3
1

Jab.

Ha Hb
3

R C C R'
2

The superscript "3" indicates coupling to a 3-bond neighbor

They are usually determined by measuring the distance between two peak signals in ppm multiplied by the spectrometer frequency. In general, 1. Protons bonded to the same carbon atom (germinal protons) can split each others signal only if they are non-equivalent. Equivalent protons do not split each other.
H
1

H C
2

2. Non-equivalent protons on adjacent carbon atoms (vicinal protons) (ie separated by 3-sigma bonds) split each others signal (Spin-spin coupling is observed).
H H
1

R C C R'
2

3. Protons separated by more than 3-sigma bonds do not produce observable spin-spin splitting. Occasionally, long range coupling does occur.
H
1

H
4

R C C C R'
2
3

The table below shows typical values of coupling constants.


___________________________________________________________ Aproximate J (Hz) Partial Structure ___________________________________________________________

C H

C H

Free rotation

7 (6 - 8)

C C H H C C H H C C H H

Cis

6 - 12

Trans

12 - 20

Geminal

H ortho H 8

H meta H 2

C C C H H 6

Coupling constants helps to distinguish among the possible stereoisomers of compounds. For example in the figure below;
H C C Cl COOCH3 Cl H H C C H
3

COOCH3

(Z)-methyl 3-chloroacrylate
3

(E)-methyl 3-chloroacrylate J = 15 Hz

J = 9 Hz

While the HNMR spectra of the above compounds will be similar, the coupling constants of the vinyl protons will unambiguously distinguish the Z-stereoisomer from that of the E-isomer. While the coupling constant of the vinyl protons of the Z-isomer is about 9 Hz, that of the Eisomer is about 15 Hz. A 1H-1H spin-spin coupling exists between any 2- and 3-bond neighboring Hs. However, the only couplings that can be observed in the spectrum are those between chemically non- equivalent Hs. Examples are shown below. a)
C

H C H O H

Singlet. Therse protons are chemically equivalent

b)
H H3C O H CH3

J coupling is not observed in the 1H NMR spectrum. These 2H's are chemically equivalent and appear as a quartet due to 3J coupling with the methyl H's (three 3-bond neighbors).

c)
O H C O H

Singlet. No 2J coupling can be observed in the 1HNMR spectrum. The two protons are chemically equivalent

However,

H3C H3C C H3C

O Ha C Hb O

These two protons Ha and Hb are chemically non-equivalent and therefore 2J coupling observed in the 1H NMR spectrum.

Jab Hb

A doublet for each of the 2 geminal protons (Ha and Hb)

________________________ Ha Hb

H3C H3C H3C

O O

Ha

For vinyl protons; a)


Ha C C X Hb Y trans vicinal coupling 3 Jab = 12 - 20 Hz Ha C C X Y Hb cis vicinal coupling 3 Jab = 6 - 12 Hz

Hence, 3Jtrans > 3Jcis

b) When a proton signal is split by adjacent protons of more than one type with different coupling constants, a complex splitting pattern results. For example, in the styrene structure below;
Ha C C Hb Hc

Styrene The chemical shift of Ha is 6.6 ppm, deshielded by both the vinyl and the aromatic ring. Ha is coupled to Hb with a typical coupling constant 3Jab = 17 Hz. It is also coupled to proton Hc with 3 Jac = 11 Hz. The Ha signal is split into a doublet of spacing 17 Hz, and each of those peaks is

further split into a doublet of spacing 11 Hz, for a total of four peaks. This kind of splitting is known as doublet of doublets.
For Ha 6.6 Chemical shift of Ha

Upon intereaction with Hb

Jab = 17 Hz

Then upon interaction with Hc. each of the doublets splits into a doublet Doublet of doublets
3

Jac = 11 Hz

Jac = 11 Hz

For Hb

5.65 Chemical shift of Hb

Upon intereaction with Ha

Jab = 17 Hz

Then upon interaction with Hc. each of the doublets splits into a doublet witha relatively smaller couplingconstants (geminal coupling) Doublet of doublets
3 3

Jbc = 1.4 Hz

Jbc = 1.4 Hz

Aromatic Hydrogens: Typically 3J ~ 8Hz (ortho); 4J ~ <1 Hz (meta); 5J ~ 0 Hz a) para-Disubstituted Benzene


R, (d) Ha (d) Hb R2 Ha (d) Hb (d) d = doublet

Two groups of chemically equivalent aromatic H's: each shows up as a doublet as a result of 3Jab ~ 8 Hz with a 2 H-intensity. b) Three isomers of nitroaniline

Chemical shifts of each of these aromatic H's are can be explained in terms of resonance contributions of the NH2 and NO2 groups
H H H H H high field shift (smaller ppm) some electron density increase H H H highest field shift (smaller ppm) most electron density increase

H N H

H H

c) Long-range couplings

doublet at 7.40 ppm CH3 Hc Hb NO2 doublet of doublets at 8.04 ppm Br Ha

singlet st 2.5 ppm


3

CH3 ~ 8.6 Hz J (ortho coupling) Hc Hb Br Ha NO2

~ 0 Hz J (para coupling)

doublet at 8.38 ppm

~ 2.2 Hz J (meta coupling)

Topicity
A. Nuclei can be categorized as :
1. Homotopic : Chemically equivalent in every respect and exhibit the same NMR properties

of the molecule, and exhibit the same NMR properties 3. Diastereotopic : Connectively equivalent , but chemically non-equivalent H's are distinguishable by NMR B. Topicity c a n b e d e t e r m i n e d using a deuterium subsititution test:

2. Enantiotopic : Chemically equivalent except for their contributions to the optical properties

e.g. these two H's are diastereotopic

H H Cl CH3 * chiral center Cl H Cl D H


S S

H D CH3 Cl
R S

CH3

Cl H

Cl H

Diastereomers

Question: Determine whether the pairs of protons below are homotopic, enantiotopic or diastereotopic.

13

C NMR SPECTROSCOPY

A. Splitting 1. 13C - 13C coupling is ignored (natural abundance 1.1 % )


2. 1 H - 13C coupling (natural abundance of 1 H is 99.9 %) 3. "Decoupled spectrum" - coupling due to 1 H is experimentally eliminated to keep things simple . B. No Integration C. Chemical Shift (range 0 to 220 ppm)

O H2 C H3C 4 O 3 CH3 2 1 Ethyl acetate 3 4 2

INTERPRETING 1HNMR SPECTRA When you first look at a 1HNMR spectrum, consider the major features before getting into the minor details. 1. If the molecular formula is known, use it to determine the degree of unsaturation in the compound. The degree of unsaturation will be indicative of the presence of a double bond, a triple bond or a ring. 2. Any broadened singlets in the spectrum might be due to OH or NH. If the singlet is deshielded past 10 ppm, an acid OH group is likely. (-COOH). 3. A signal around 3 and 4 suggests protons on a carbon bearing an electronegative element such as oxygen, nitrogen or a halogen.
O C H X C H X = F, Cl, Br, N

4. A proton signal around 7 to 8 suggests the presence of an aromatic ring.


R

5. Signals around 5 to 6 suggest vinyl protons. Coupling constants can differentiate cis from trans isomers.
H C C H H H around 5 to 6; 3 J = 15 Hz C C

around 5 to 6; 3 J = 10 Hz

6. Recognize ethyl groups (-CH2CH3 ) characteristic splitting patterns.

ethyl group

7. Signals around 2.1 to 2.5 may be indicative of protons adjacent to a carbonyl group or next to an aromatic ring. A signal at 2.1 is usually a methyl group next to a carbonyl group.
O C C H around 2.1 - O C CH 3 singlet at 2.1 CH3

singlet at 2.3

8. Signals around 9 to 10 suggest an aldehyde.


O R H

9. A signal around 2.5 suggests a terminal alkyne.


R C C H

Question: An unknown compound (C3H2NCl) shows moderately strong IR absorptions around 1650 cm-1 and 2200 cm-1. Its NMR spectrum consist of two doublets (J = 14 Hz) at 5.9 and 7.1. Propose a structure consistent with these data.