IR – Spectroscopy

Part II

1
 Carbonyl - compounds
For simple aldehydes and ketones, the stretching vibration of the carbonyl group
has a strong infrared absorption between 1710 and 1740 cm-1.

Alkyl substituents are Electron Donating Groups

– inductive effect lower the bond strength of C=O
ketone carbonyls have slightly lower stretching frequencies, 1715 ± 7 cm-1,
compared with aldehydes, 1730 ± 7 cm-1.

2
Ketones and aldehydes

Gas phase

1727 cm-1

3
Ketones and aldehydes

1740 cm-1

1715 cm-1

4
 Ketones and aldehydes – conjugated systems

Conjugation of C=O bond with a double bond or phenyl ring lowers the stretching
frequency.
5
Ketones and aldehydes – conjugated systems

1685 cm-1

6
Ketones and aldehydes – influence of EDG and EWG

7
Ketones and aldehydes – influence of EDG and EWG

8
 Ketones and aldehydes – influence of EDG and EWG

Two above isomeric ketones has diffirent absorbtion of C=O group,

Please, draw appropiate mesomeric structures to explain observed facts.

9
 Ketones– ring size

Incorporation of the carbonyl group into a small ring, increase the stretching
frequency.

10
Carbonyl compounds

11
 Acid chlorides –aliphatic - butyryl chloride

Additional band in C=O region is a result of Fermi resonance of C-Cl and C=O
12
Acid chlorides –aromatic - benzoyl chloride

1775 cm-1 1733cm-1

13
 Carboxylic anhydrides

Anhydrides C=O stretch: 2 bands separated by 60 -30 cm-1)

Acyclic anhydrides, 1750 and 1820 cm-1;
6-membered ring, 1750 and 1820;
5-membered ring, 1785 and 1865
14
 Carboxylic acid – hydrogen bonds

Spectrum of carboxylic acid in gas phase – only monomeric molecules

15
 Carboxylic acid – hydrogen bonds

Spectrum of carboxylic acid in solution– dimeric and monomeric

16
 Carboxylic acid – hydrogen bonds

Spectrum of liquid carboxylic acid (pure substance) – only dimer is observed

17
 Primary Amides

Amide I band ν C=O stretching, Amide II band δ N-H bending in plane

Why the wavenumber of I amide band is usualy below 1700 cm-1 ?

18
 Amides bond properites

Conjugation of C=O bond with an EDG : (lone pair, double bond or phenyl ring)
lowers the stretching frequency.
19
 Secondary Amides

ω NH (out of plane)
711cm-1 645

ν NH ν C=O
3326 cm-1 ν C-N
1638 cm-1
1450 cm-1

δ NH (in plane)
1554cm-1
ω CH aromatic (out of plane)
711cm-1 645

One stretching band

20
 TertiaryAmides

Overtone C=O
3471 cm-1

ν C-N
None N-H ν C=O 1428 cm-1
stretching band 1640 cm-1

21
 Lactams

• 1° & 2°-amides, 1510 to 1700 cm-1 (2 bands)

non-cyclic amides
• 3°-amides, 1650± 15 (one band);

• 6-membered lactams, 1670 ± 10 (one band)

• 5-membered lactams, 1700 ± 15 ; cyclic amides
• 4-membered lactams, 1745 ± 15.

ν C=O ν C=O ν C=O ν C=O ν C=O

1640 cm-1 1671 cm-1 1666cm-1 1700cm-1 1745 cm-1

22
 Lactones
Esters, 1740 +/- 10 cm-1; non-cyclic esters

6 membered lactone, 1740 +/- 10 cm-1;

5 membered lactone, 1765 +/- 10 cm-1; cyclic esters
4 membered lactone, 1840 +/- 5 cm-1

ν C=O ν C=O ν C=O ν C=O

1749 cm-1 1740cm-1 1775cm-1 1818 cm-1

23
Alkohols – hydrogen bonds

24
 Alcoholic C-O Stretch
Alcohol Type Absorption Range
cm-1
1 Saturated tertiary 1205-1124
Secondary (highly symmetrical)

3 Secondary saturated, 1124-1087

α-unsaturated or cyclic tertiary

4 Secondary α-unsaturated, 1085-1050

Secondary alicyclic five or six- membered ring,
Saturated primary

5 Tertiary, highly α-unsaturated <1050

Secondary di-α-unsaturated
Secondary α-unsaturated
Secondary alicyclic seven or eight membered ring
Primary α-unsaturated

25
Alcoholic C-O Stretch

ν C-O
1205 cm-1

ν C-O
1160 cm-1 1130 cm-1

26
 Alkyls - Tert-butyl ver isopropyl

cm-1
1390 and 1370 cm-1 600 -650 cm-1
H) 1480 cm-1 and cm-1
CH3 and CH2  s CH3 C-O)
H)
as s out of plane
dublet

27
Tert-butyl ver isopropyl

s CH3 1395 and 1370 cm-1

s CH3 1385 and 1370 cm-1

28
Aromatic Ring Substitution orto- meta- para-
Substitution Structure Range cm-1 Intensity
1 mono 910-890 m*
770-730 s
710-680 s
2 1,2-di 780-735 s
Ortho-
3 1,3-di 900-835 m
meta- 810-750 s
725-670 m-s
4 1,4-di 860-800 s
para-
1,2,3,4-tetra 860-780 s
5 1,2,3-tri 800-750 s
780-760 m*
720-680 m
6 1,3,5-tri 900-840 m
865-800 s
730-675 m*
(1,2,3,5-tetra
1,2,4,5-tetra
penta-) 900-840 m
29
* Sometimes lack of band
Aromatic Ring Substitution- overtones of γ – out of plane vibration
2000 cm-1 1667 cm-1

30
 Mono substituted

2000 cm-1 1667cm-1 910-890 m*

770-730 s
710-680 s
31
 Ortho substituted

2000 cm-1 1667 cm-1

780-735 s

32
 meta substituted

840

2000 cm-1 1667 cm-1 900-835 m

810-750 s
725-670 m-s
33
 para substituted

840

2000 cm-1 1667 cm-1

860-800 s
34
 EWG substituted aromatic ring

935

794 682
νas NO2 852
νs NO2
703

para- ?
2000 cm-1 mono-
1667 cm-1
910-890 m*
770-730 s
710-680 s 860-800 s
35
 Alkenes substitution
Structure (γ) bending (ν) stretching (ν) stretching overtones
out of plane =C-H [cm-1] C=C [cm-1]
[cm-1]
1 1005-985 s 3095-3075 m 1660-1635 m 1860-1800 m
920-900 s 3040-3010 m
2 900-880 s 3095-3075 m 1660-1640 m 1800-1750 m

3 990-960 s 3040-3010 m 1690-1665 w -------------------

4 730-665 m 3040-3010 m 1690-1665 w -------------------

5 850-790 m 3040-3010 m 1690-1665 -------------------

w-m
(sometimes absent)

6 -------------- ---------------- 1690-1650 w -------------------

(sometimes absent)

36
 Alkenes substitution - terminal CH2

1643 cm-1
-1
3080 cm 1826 cm-1 C=C)
CH) C=CH2 CH) C=CH2 993 i 912 cm-1
overtone 1417 cm-1 CH) C=CH2
bendinging out of-plane
s CH) C=CH2
scissoring

1 1005-985 s 3095-3075 m 1660-1635 m 1860-1800 m

920-900 s 3040-3010 m
37
 Alkenes substitution - terminal CH2

3076 cm-1
CH) C=CH2 1650 cm-1
889 cm-1
1783cm-1 CH) C=CH2
2*CH) C=CH2
C=C) bendinging out of-plane
overtone

2 900-880 s 3095-3075 m 1660-1640 m 1800-1750 m

38
 Alkenes substitution

Structure (γ) bending (ν) stretching (ν) stretching overtones

out of plane [cm-1] =C-H [cm-1] C=C [cm-1]

6 -------------- ---------------- 1690-1650 w -------------------

(sometimes absent) 39
Alkenes substitution: Z and E

Z  (C–H) 730 – 665 cm-1

medium intensity

E  (C–H) 990 – 960 cm-1

Strong intensity

40