NMR Lecture 5

Factors affecting 13C NMR spectra

How do you know 3 microsec = 22

Proton decoupler always on, no pulse delay

Pulse delay 400 s; gated decoupler-on

only when acquiring signal

Effects of the pulse delay between pulses, 400 s

Proton decoupler always on (NOE)

Information obtained by examining nmr spectra

1. Chemical shift (identifies nature of nucleus
2. Area (identifies relative number of nuclei)
3. Multiplicity ( (NOE)
2D NMR basically provides information about connectivity and
proximity

Applications of 1H and 13C NMR

Molecular
formula C9H10O

IR: 1720 cm-1

CH2

CH3
O

area: 5: 2: 3

O
C
CH3

CH3

C
CH2

CH3
CH3

H NMR

Molecular formula C7H14O2

IR 1720 cm-1

3:2:3:6

F NMR of F3

CF24

CF25H

=CF3-

NH2
F

F
H

Returning to Dynamic Nuclear Magnetic Resonance

For a simple exchange process coalescence /21/2
Most chemical shift differences are of the order of a few
hundred Hz or less. Rate constants are of the order of few
hundred sec-1. Large in comparison to k 10-4 10-5 sec-1,
measured by conventional kinetics but small relative to many
dynamic processes occurring in molecular systems such as
rotations about bonds.

Assign the spectrum and

explain the coupling observed

Lets do a thought experiment

What would the NMR spectrum of the methyl resonances of 4dimethyl-3-hydroxycyclobutenone look like if all the methine
hydrogens of this molecule had the same spin?
O

CH3

CH3
HO

CH3

CH3
HO

J13 J15 are of

opposite
sign

J13, J15 are the

same sign

CH3

CH3
HO

J13, J15 are of

opposite
sign

J13, J15 are the

same sign

What are some mechanisms by which the two methyl groups can
become identical?

CH3

CH3

H2O

CH3
HO

CH3
O

H
CH3

OH

CH3

CH3

CH3
HO

CH3
CH3
O

CH3

OH

CH3

CH3

H2O

OH

CH3

CH3
HO

HO

CH3

CH3

OH

CH3

CH3

CH3
HO

OH

CH3

HO

CH3

CH3

OH

CH3

CH3

1,3-hydrogen shift

OH

H3C

CH3
HO

CH3

CH3

1,3-hydrogen shift

OH

H3C

CH3
HO

CH3

CH3

CH3
HO

OH

H3C

CH3

J is of
opposite
sign

J is the same
sign

CH3

CH3

CH3

OH

OH

H
CH3
HO

HO

CH3

CH3

CH3

CH3
H

OH

CH3

HO

CH3

CH3
O

CH3

CH3

CH3

1,3-hydrogen shift; JAX

CH3
HO

and JAM of the same sign

OH

CH3

CH3
HO

CH3

CH3

1,3-hydrogen shift; JAX

and JAM of the opposite signs

OH

CH3

Problem Set DNMR

By line shape analysis, determine the activation energy for
rotation about a carbon nitrogen bond in an amide.

Go to my gateway and down load the Excel file.

A plot of ln k vs 1/T should result in a straight line and the

slope of the line should be - Ea/R. Your problem will be to fit
the lineshapes as best you can and evaluate k for a series of
temperatures. Remember that the most accurate k values will
be when the line shapes change the most.
k = rate constant