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Structure Problem Solving Using H and C NMR Spectral Data Tutorial Session

1. The document discusses solving problems involving the structural elucidation of organic compounds using 1H and 13C NMR spectral data. 2. Seven example problems are presented and solved step-by-step using clues from molecular formulas and peak assignments in NMR spectra. 3. Key structural features like functional groups and bonding patterns are identified that are consistent with the spectral data and molecular formulas. Likely structures are proposed for each compound.

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Saurav Paul
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74 views

Structure Problem Solving Using H and C NMR Spectral Data Tutorial Session

1. The document discusses solving problems involving the structural elucidation of organic compounds using 1H and 13C NMR spectral data. 2. Seven example problems are presented and solved step-by-step using clues from molecular formulas and peak assignments in NMR spectra. 3. Key structural features like functional groups and bonding patterns are identified that are consistent with the spectral data and molecular formulas. Likely structures are proposed for each compound.

Uploaded by

Saurav Paul
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Structure Problem solving using 1H and 13C NMR spectral data

Tutorial session

S. SANKARARAMAN
Department of Chemistry
Indian Institute of Technology Madras
Chennai 600036

[email protected]
Problem 1. C5H12O2 4.1 (s, 6H), 1.8 (s, 6H).

Molecular formula suggests that the compound is saturated


4.1 ppm (s, 6H) implies two methoxy groups - 2 x OCH3 group

1.8 ppm (s, 6H) implies two methyl groups attached to a carbon - CH3-C-CH3 group

Therefore the structure of the compound is


Problem 2.

C5H10O 5.95 (dd, 1H, J = 16, 7.6), 5.1 (dd, 1H, J = 16, 1.5), 4.95 (dd, 1H, J = 7.6, 1.5),

2.2 (s, 1H, D2O exchange), 1.2 (s, 6H).


From the formula, degree of unsaturation of this compound is ONE, DBE = 1

5.95 (dd, 1H, J = 16, 7.6), 5.1 (dd, 1H, J = 16, 1.5), 4.95 (dd, 1H, J = 7.6, 1.5)

The above data implies a monosubstituted double bond where the three olefinic
protons are mutually coupled
Hb Hc
Therefore the structural fragment corresponding to the above data is
Ha X
2.2 (s, 1H, D2O exchange) is a hydroxyl group – OH

1.2 (s, 6H) is a gem dimethyl group – C(CH3)2 group

All these fragments add up to the molecular formula


Therefore the structure of the compound is
Hb Hc
CH3
Ha
CH3
OH
Problem 3.
C6H12O2 3.85 (d, 2H, J = 7.2), 2.0 (s, 3H), 1.92 (9 line pattern with appropriate
intensities, 1H, J = 7.2), 0.9 (d, 6H, J = 7.2).
Degree of unsaturation for the above formula is ONE
1.92 (9 line pattern with appropriate intensities, 1H, J = 7.2)

9 line pattern is a nonet, this means that there are 8 equivalent adjacent protons
H3C
The only structural unit that satisfies the above data is CH2
H3C H
3.85 (d, 2H, J = 7.2) and 0.9 (d, 6H, J = 7.2) are the coupling parterns in the
above fragment. 3.85 ppm is due to CH2 group – OCH2CH(CH3)2
0.9 ppm is due to gem dimethyl groups
2.0 (s, 3H) is most likely due to COCH3 group, that takes care of DBE and another oxygen

The above fragments put together satisfies the


molecular formula and the given NMR data

Therefore the structure is


Problem 4.
C8H6O3 9.8 (s, 1H), 7.5 (dd, 1H, J = 8.0, 2.0), 7.4 (d, 1H, J = 2.0), 6.9 (d, 1H, J = 8.0),
6.0 (s, 2H).
Degree of unsaturation is SIX, DBE = 6
9.8 (s, 1H) is very characteristic of an aldehyde group – CHO group present
H
7.5 (dd, 1H, J = 8.0, 2.0), 7.4 (d, 1H, J = 2.0), 6.9 (d, 1H, J = 8.0) This data is X H
consistent with a aromatic ring with two hydrogens ortho (J = 8.0) and one
hydrogen meta (J = 2.0). The fragment corresponding to this data is Y Z
H
6.0 (s, 2H) is a CH2 group connected to two oxygens - O-CH2-O group
The molecular formula is satisfied with these fragments

By connecting the above fragment one gets the structure as


H
O H
H2C
O C=O
H H
Note: DBE for phenyl ring = 4
DBE for another ring = 1
DBE for aldehyde = 1, total DBE = 6
Problem 5. 1H NMR: 7.9 and 7.3
Molecular formula: C8H7OCl (AB pattern, 4H, J = 8 Hz),
2.6 (s, 3H).

13C NMR: 198 (s), 140 (s),


135 (s), 130, (d), 129 (d),
27 (q)
Problem 5.
Molecular formula: C8H7OCl
1H NMR: 7.9 and 7.3 (AB pattern, 4H, J = 8 Hz), 2.6 (s, 3H).
13C NMR: 198 (s), 140 (s), 135 (s), 130, (d), 129 (d), 27 (q)

Degree of unsaturation is FIVE, DBE = 5


X
7.9 and 7.3 (AB pattern, 4H, J = 8 Hz) implies para disubstituted derivative Ha Ha
Of which one of the substituent could be chlorine, say X = Cl
140 (s), 135 (s), 130, (d), 129 (d) in 13C NMR is also consistent with this. Hb Hb
Y
In proton NMR 2.6 (s, 3H) and in 13C
NMR 27 (q), 198 (s) are consistent
with acetyl group, -COCH3 might be present. Therefore the other substituent is
Acetyl group
The structure of the compound is 4-chloroacetophenone

7.9 and 7.3 (AB pattern, 4H, J = 8 Hz), 2.6 (s, 3H).
1H NMR: 9.5 (s, 1H),
Problem 6.
2.5 and 1.9
Molecular formula: C7H11NO
(AA’BB’ pattern, 4H),
1.2 (s, 6H).

13C NMR: 205 (d), 120 (s),


45 (s), 32, (t), 21 (q),
12 (t)
Problem 6.
Molecular formula: C7H11NO Degree of unsaturation is three, DBE = 3
1H NMR: 9.5 (s, 1H), 2.5 and 1.9 (AA’BB’ pattern, 4H), 1.2 (s, 6H).
13C NMR: 205 (d), 120 (s), 45 (s), 32, (t), 21 (q), 12 (t)

9.5 (s, 1H) in proton NMR and 205 (d) in carbon NMR implies CHO group
2.5 and 1.9 (AA’BB’) pattern could be only due to X-CH2-CH2-Y group
The two CH2 groups appear in carbon NMR at 32 and 12 ppm as triplet in the off resonance
1.2 (s, 6H) could be due to gem dimethyl group - -C(CH3)2
The balance from the molecular formula after subtracting all these fragments is CN group
The peak at 120 in carbon could be due to CN group.

The possible structures are

Structure 2 can be ruled out because CHO proton will not be singlet

Therefore structure 1 is most likely structure for this data.


Problem 7.
Molecular formula: C12H14O 1H NMR: 7.3 – 7.7 (m, 6H),
6.85 (d, 1H, J = 16),
2.95 (1H,
Septet (?), J = 7),
1.2 (d, 6H, J = 7)
13C NMR: 203.1, 142.1, 134.5,

130.2, 128.8, 128.2, 124.3,


39.1, 18.4
Problem 7.
Molecular formula: C12H14O Degree of unsaturation is six, DBE = 6
1H NMR: 7.3 – 7.7 (m, 6H), 6.85 (d, 1H, J = 16), 2.95 (1H, Septet (?), J = 7), 1.2 (d, 6H, J = 7)
13C NMR: 203.1, 142.1, 134.5, 130.2, 128.8, 128.2, 124.3, 39.1, 18.4

2.95 (1H, Septet (?), J = 7), 1.2 (d, 6H, J = 7) implies isopropyl group attached to CO
203 peak in carbon NMR supports the CO group along with 39.1 and 18.4 peaks
O
6.85 (d, 1H, J = 16) indicates trans alkene proton, CH3
but the coupling partner is missing. Is it merged with aromatic protons? H
CH3

7.3 – 7.7 (m, 6H) could be due to mono substituted phenyl ring and the missing alkene
Proton totaling 6 hydrogen intensity. Accidental merger of signals in aromatic region.

are present. These fragments satisfy the formula

Therefore the structure is


THANK YOU

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