CHEM 111 General Chemistry 26/03/2024
Combined spectroscopy problems
1
Index of hydrogen deficiency
Consider CmHnOqNr Xs Here X denotes Halogen
IHD or DBE = ½{(2m+2) –(n+s-r)}
For molecules containing only carbon, hydrogen,
monovalent halogens, nitrogen, and oxygen:
DBE = C + 1 – (X/2) – (H/2) + (N/2)
1H NMR CHEMICAL SHIFT RANGES
3
Important IR Stretching frequencies
Type of vibration Frequency (cm-1) Intensity
C-H Alkanes (stretch) 3000-2850 s
Alkenes (stretch) 3100-3000 m
Alkyne (stretch) 3300 s
Aldehyde 2900-2800 (2850) w
2800-2700 (2750) w
C≡N Nitriles 2260-2240 (2250) m
N=O Nitro (R-NO2) 1550 and 1350 s
C-O Alcohols, ethers, esters, acids, anhydrides 1300-1000 s
C=C Alkene 1680-1600 m-w
Aromatic 1600 -1475 m-w
C≡C Alkyne 2250-2100 (2150) m-w
C=O Aldehyde 1740-1720 (1725) s
Ketone 1725-1705 (1715) s
Carboxylic acid 1725-1700 (1710) s
Ester 1750-1730 (1735) s
Amide 1680-1630 (1690) s
Anhydride 1810 and 1760 s
Acid chloride 1800 s
O-H Alcohols, phenols
Free 3650-3600 m
H-bonded 3400-3200 m
Carboxylic acids 3400-2400 m
N-H Primary and secondary amines and amides (stretch)
Primary (2 peaks); secondary (1 peak); tertiary 3500-3100 m
(none)
Problem 1
An organic compound has molecular formula C3H5BrO2
(MW = 152). Deduce the structure of the compound from the
following spectral data. Assign the 1H NMR peaks to the
deduced structure.
IHD = ½ { (2x3 + 2) – 6 + 0} = 1; One double bond or a ring.
1717 cm-1 + 1 IHD C=O ; broad band at 3000 cm-1 OH
from COOH ?
Broad peak at 10 COOH; 2 sets of 2H’s (triplets) -CH2CH2-
The compound is BrCH2CH2COOH
Problem 2.
An organic compound has molecular formula C4H8O2.
Deduce the structure of the compound from the following
spectral data. Assign the proton NMR peaks and the
important IR peaks to the deduced structure.
IR (cm-1): 2986, 2955, 1743, 1437, 1203, 1086, 1022
1H NMR (δ): 1.15 (3H, triplet), 2.33 (2H, quartet), 3.67
(3H, singlet)
IHD = 1,
may be the presence of carbonyl group, probably an ester.
The structure of the compound is :
methyl propanoate
Problem 3.
Molecular formula of the compounds is C3H5O2Cl determine the
structures. IR spectrum of both the compounds give peak at ~1700 cm-1
and a broad peak between 2500- 3100 cm-1 .
CH3
CH
HOOC Cl
Cl CH2
CH2 COOH
Problem 4.
An organic compound has molecular formula C4H7BrO2. Deduce the
structure of the compound from the following spectral data. Assign
the 1H NMR peaks to the deduced structure.
IR (cm-1): 1714, 3400 (broad peak)
1H NMR (δ): 12 (1H, singlet), 4.3 (1H, triplet), 2.2 (2H,
quintet), 1.2 (3H, triplet)
Index of hydrogen deficiency IHD or double bond
equivalence = 1,
may be the presence of carboxylic acid group.
The structure of the compound is :
Problem 5: The molecular formula for an unknown compound
is C9H10O3 . Fig.1 and Fig.2 are the corresponding IR and
1H NMR spectra of the compound. Identify the compound and
deduce the structure.
2900
3400
3100
1490
3400 1720 1180 838
1040
Fig.1
AROMATIC
AROMATIC OUT OF PLANE (OOP) BENDING VIBRATIONS
690 & 750
750
690,780
880
800-850
11
Fig.2
CH2OH
COOCH 3
Problem 6: A compound is found to contain 21.3% carbon,
1.78% hydrogen and 62.8% chlorine. This compound
exhibited a doublet at 2842 cm-1 and 2745 cm-1 in its IR
spectrum. PMR spectrum of this compound is shown
below: (Atomic Weight of H = 1.008, C = 12; O =16; Cl =
35.5). Derive the structure of the compound.
doublet doublet
Cl
CHO
Cl H
9 8 7 6 5 4 3 2 1 0
PPM
Problem 7: An organic compound with molecular
formula C9H10O2 gave the following spectral data:
IR: Significant absorption bands at 3030 cm-1, 2940 cm-1,
1725 cm-1, 1605 cm-1, 1505 cm-1, 1060 cm-1 and 830 cm-1
PMR: δ 2.35 (3H, s), 3.82 (3H, s) and 7.20 -7.85
(unsymmetrical pattern, 4H).
Rationalising all the spectral data given, deduce the
structure of the compound.
CH3
COOCH 3
Problem 8: A compound of molecular formula C9H10O2
was found to have strong IR absorptions at 1745 cm-1,
1225 cm-1, 749 cm-1 and 697 cm-1. Its proton NMR
spectrum was found to have multiplet corresponding to 5
protons at δ 7.22, a singlet corresponding to 2 protons at
δ 5 and a singlet corresponding to 3 protons at δ 1.96.
Rationalising all the spectral data given deduce the
structure of the compound.
O
CH3
O
Problem 9: A compound with a molecular weight 120
gave a negative iodoform test. It shows significant IR
bands at 3042, 2941, 2862, 2740, 1722, 1605, 1575 and
1462 cm-1 in its IR spectrum. In the PMR spectrum, three
signals are present at δ 7.27 (multiplet), 2.8 (doublet) and
9.78 (triplet) in the intensity ratio 5:2:1, respectively.
Determine the structural formula of the compound. CHO
Problem 10: The proton NMR of an organic compound
C8H9Br showed a quartet at δ 5.5, a doublet at δ 2 and an
unsymmetrical multiplet at δ 7.4 in the intensity ratio
H C
1:3:5 respectively. Deduce the structure of the 3
Br
compound.
Problem 11: A compound of mass 136 containing Br
exhibited the following 1H NMR spectrum. Deduce the
structure of the compound giving proper justification.
Problem 12:
