NMR Spectroscopy Differ From" Ir" Spectros

NMR SPECTROSCOPY DIFFER FROM” PART
IR” SPECTROSCOPY: TWO
1. The energy needed for NMR is much smaller than

that required for IR Spectroscopy.
2. Time scales of the two techniques are quite different.
(NMR about 10-3 second, while IR about 10-13 second)
1δ = 1 ppm
ppm (part of the million) of the operating frequency of the
instrument. e.g. if we use spectrometer operating at
Thus there is a considerable accidental overlap
of non equivalent signal will occur.
The advantages of using an instrument with higher
• It means that shielding and deshielding depend on the
orientation of the molecule with respect to applied
magnetic field. For example:
1. The NMR peak of the proton of acetylene is found
further to the right than electronegativity would
predict, (peak = 1.8 δ) more shielded than ethylene
protons (peak = 5.25 δ).
• Note: electron with drawing effect = SP > SP2 > SP3

2. Unexpected deshielding position of the aldehydic proton.
(9.7- 10)
3. Large deshielding of alkene protons.

4. Large deshielding of benzene ring protons, which is called
"ring current effect" (6.5_ 8).
Note: a proton held directly above or

below the aromatic ring is shielded.
RATIONALIZATION AND PREDICTION OF APPROXIMATE
CHEMICAL SHIFT DEPENDING ON INDUCTIVE EFFECT &
DIAMAGNETIC ANISOTROPY
SOLVENT SELECTION:
• Characteristic of the ideal solvent:
• 1. should contain no protons
• 2. inert
• 3. low boiling
• 4. inexpensive
• 5. Deuterated solvents are necessary for modern instruments
because they depend on a deuterium signal to lock or
stabilize the B° field of the magnet.
• Solvent used in NMR spectroscopy:
• 1. CCl4: because a/ it is contain no hydrogen.
• b/ good solvent for many organic compounds.
• c/ cheap and readily available.
• 2. CDCl3
INFORMATION OBTAINED FROM NMR SPECTRA:
• 1. Number of signal: → number of sets of chemically
equivalent protons.
• The equivalence or non-equivalence of two protons can
be determined by seeing whether the same or different
structures would result, if some group X were substituted
for one of protons.
• If the protons are chemically equivalent → same
product will be formed regardless of which protons is
replaced, if the protons are chemically non equivalent
→ different product.
• e.g. 2,3- dimethyl butene →
• all 12 protons are equivalent (CH3)2C = C(CH3)2 → 4
methyl are equivalent
e.g. 2- methyl ,2-butene → are not equivalent
Nuclear Magnetic Resonance Spectroscopy
1H NMR—Number of Signals
• The number of NMR signals equals the number of different types of
protons in a compound.
• Protons in different environments give different NMR signals.
• Equivalent protons give the same NMR signal.
• To determine equivalent protons in cycloalkanes and alkenes,

always draw all bonds to hydrogen.
13
Figure 14.2
The number of 1H NMR signals
of some representative
organic compounds
14
• In comparing two H atoms on a ring or double bond, two
protons are equivalent only if they are cis (or trans) to
the same groups.
15
• To predict the number of signals, must determine
how many sets of protons are in unique
environments:
• 2. Homotopic Hydrogens (equivalent)
• Hydrogens are chemically equivalent or homotopic if
replacing each in turn by the same group would lead to an
identical compound.
• 3. EnantiotopicHydrogens
If replacement of each of two hydrogens by some group leads to
enantiomers, those hydrogens are enantiotopic
• 4. Diastereotopic Hydrogens
• If replacement of each of two hydrogens by some group leads to

diastereomers, the hydrogens are diastereotopic
• H Diastereotopic hydrogens have different chemical shifts and will
give different signals
• The protons on a CH2 group are usually
diastereotopic if:
• On an unsymmetrical double bond
• t On opposite sides of a substituted ring
• t There is a chiral center in the molecule
• 2. the position of the signals (chemical shift in H-NMR
Spectroscopy)
FACTORS EFFECTING CHEMICAL SHIFT:
1. inductive effect:
2. anisotropic effect
3. vanderwaals deshielding: proton (a) is not effected by proton (b),
but if we substituted proton (b) by CH3 → repulsive because of steric
effect with the proton (a) → deshielding → down field.
• 4. Hydrogen bonding:
They cause decrease the density around the hydrogen →
deshielded by inductive effect.
•
The intensity of intermolecular hydrogen bonding depending
on:
• The concentration: increase concentration → increase
H-bonding → increase deshielding.
 The temperature: increase temperature → breakdown the H-
bonding → high field.
 The purity.
 Polarity of the solvent: the solvent should be deuterated
(CDCl3) and also should not polar.
• Intramolecular H - bonds are less affected by their
environment than are intermolecular H - bonds.

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NMR SPECTROSCOPY DIFFER FROM” PART

IR” SPECTROSCOPY: TWO

1. The energy needed for NMR is much smaller than

• Note: electron with drawing effect = SP > SP2 > SP3

3. Large deshielding of alkene protons.

Note: a proton held directly above or

• To determine equivalent protons in cycloalkanes and alkenes,

• If replacement of each of two hydrogens by some group leads to

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