Structure Elucidation

Pengantar Elusidasi Struktur

Infrared Spectroscopy

Dwi koko P., M. Sc., Apt.

Fakultas Farmasi
Universitas Jember
Pustaka
 Pavia, D., Lampman, G., Kriz, G., dan Vyvyan, J., 2014.
Introduction to Spectroscopy. Cengage Learning.
 Williams, D.H. dan Fleming, I., 2008. Spectroscopic Methods in
Organic Chemistry. McGraw-Hill.
 Panji, T., 2012. Teknik Spektroskopi untuk Elusidasi Struktur
Molekul. Graha Ilmu
Elusidasi struktur
 Identifikasi / Penentuan struktur senyawa
organik
 Cara Klasik : td, tl, indeks bias, rotasi optic,
uji kelarutan, uji gugus fungsi, analisis
elementer dll
 Spektroskopi : UV-Vis, IR, NMR dan MS
 Keunggulan :
 Jumlah sampel
 Struktur
 Waktu analisis
 Kehandalan
Elusidasi struktur
 Degree of unsaturation
(Unsaturation Number)
 Double-bond equivalents/DBE (William & Fleming,
2008)
 Index of hydrogen deficiency/IHD (Pavia, et. Al., 2014)
 Setelah diketahui BM maka dapat diketahui berapa banyak
ikatan rangkap (phi bond) atau system lingkar yang
mungkin ada dengan menghitung UN / DBE / IHD
Steps in calculating the degree of
unsaturation
1. take the molecular formula and replace all halogens by
hydrogens
2. omit all of the sulfur or oxygen atoms
3. for each nitrogen, omit the nitrogen and omit one hydrogen
4. After these 3 steps, the molecular formula is reduced to
CnHm and the degree of unsaturation is given by:
Latihan……

 C4H9N
O2
 C3H5O
Cl
 C10H14
N2
 Spektroskopi Inframerah

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 THE ELECTROMAGNETIC SPECTRUM

high Frequency (n) low

high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long

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 Types of Energy Transitions in Each Region
of the Electromagnetic Spectrum
REGION ENERGY TRANSITIONS

X-ray Bond-breaking
UV/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radio Frequency Nuclear and
(NMR) Electronic Spin
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 ❖Infrared Spectroscopy: Metode instrumental untuk
mendeteksi gugus fungsi
➢Radiasi EM pada rentang frekuensi IR diabsorbsi oleh
molekul pada frekuensi tertentu yang khas
 Energy diabsorbsi oleh ikatan pada molekul dan ikatannya
akan bergetar (ber”vibrasi”) semakin cepat
 Ikatan dapat menyerap energi dan bergetar lebih cepat hanya
ketika ditambahkan energi dengan frekuensi resonansi
tertentu
 Frekuensi absorpsi sangat khas pada tipe ikatan yang
terkandung dalam suatu molekul
 Tipe ikatan tsb terkait dengan gugus fungsi yang ada

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Infrared Radiation
 Frequencies - 12800 to 10 cm-1
 (cm-1 = wavenumbers)
 Divided into three Regions
 Near : 12800 to 4000 cm-1
 Middle: 4000 to 400 cm-1
 Far: 400 to 10 cm-1

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 Penggunaan Infra merah

Analisis kualitatif (elusidasi struktur)

Analisis kuantitatif

Quality Control

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 Jenis vibrasi
 The simplest types, or modes, of
vibrational motion in a molecule
that are infrared active—those that
give rise to absorptions—are the
stretching and bending modes.

 Stretching → Change in bond length

 Bending → Change in bond angle

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15
 Jenis-jenis vibrasi

Sym. stretch Scissoring

Rocking

Antisym. Stretch.
Wagging Twisting
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  Triple bonds (lebih kaku & kuat) vibrate at higher frequencies than double
bonds

 The IR spectrum of a molecule usually contains many peaks

 These peaks are due to the various types of vibrations available to each
of the different bonds
 The IR is a “fingerprint” region (700-1500 cm-1) dihasilkan dari
gabungan regangan (stretching) dan bengkokan (bending) dari atom
yang ada, khas untuk setiap senyawa

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 Spektrum IR

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19
 Typical Infrared Absorption
Regions
WAVELENGTH (mm)
2.5 4 5 5.5 6.1 6.5 15.4
O-H C-H C N C=O C=N C-Cl
Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

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 BASE VALUES These are
the minimum
(+/- 10 cm-1) number of
values to
memorize.
O-H 3600
N-H 3400
C-H 3000

C N 2250
C C 2150
C=O 1715
C=C 1650
21 C O ~1100 large range
 C-H STRETCH

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 The C-H stretching region
BASE VALUE = 3000 cm-1

•C-H sp stretch ~ 3300 cm-1

UNSATURATED
•C-H sp2 stretch > 3000 cm-1
3000 divides

•C-H sp3 stretch < 3000 cm-1 SATURATED

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 STRONGER BONDS HAVE LARGER FORCE CONSTANTS
AND ABSORB AT HIGHER FREQUENCIES
increasing frequency (cm-1)

3300 3100 3000 2900

=
=C-H =C-H -C-H

sp-1s sp2-1s sp3-1s

increasing CH Bond Strength

increasing force constant K
24 CH BASE VALUE = 3000 cm-1
METHYLENE GROUP STRETCHING VIBRATIONS
Two C-H bonds share a central carbon
(hydrogens attached to the same carbon)

H H H
Symmetric Stretch
C C
~2853 cm -1
H H

H H H
Asymmetric Stretch
C ~2926 cm-1C
H H
Any time you have two or more of the same kind of bond sharing
25 a central atom you will have symmetric and asymmetric modes.
 METHYL GROUP STRETCHING VIBRATIONS
Three C-H bonds share a central carbon
(hydrogens attached to the same carbon)

H
C H Symmetric Stretch
H ~2872 cm-1

H
C H Asymmetric Stretch
~2962 cm-1
H
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 ALKANE
Hexane

CH bending vibrations

CH includes
stretching CH3 sym and asym
vibrations CH2 sym and asym
CH3 CH2 CH2 CH2 CH2 CH3

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 C-H BENDING

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 THE C-H BENDING REGION

 CH2 bending ~ 1465 cm-1

 CH3 bending (asym) appears near

the CH2 value ~ 1460 cm-1

 CH3 bending (sym) ~ 1375 cm-1

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 METHYLENE GROUP BENDING VIBRATIONS
Scissoring Wagging

H ~1465 cm-1 H H H ~1250 cm-1

C C C
H H

H ~720 cm-1 H H H ~1250 cm-1

C C C
H H

Rocking Twisting

Bending
30 Vibrations
 ALKANE
Hexane

CH2
rocking
CH3
CH2 bend
bend
CH
stretch

CH3 CH2 CH2 CH2 CH2 CH3

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 ALKENE

1-Hexene

=CH
C=C CH2
CH3
bend

CH CH bend oop
CH2 CH CH2 CH2 CH2 CH3

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 AROMATIC

Toluene

Ar-H CH3

CH3 C=C
benzene

Ar-H oops

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 ALKYNE

1-Hexyne

=
C=C

CH2, CH3

= C-H HC C CH2 CH2 CH2 CH3

=C-H

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 O-H STRETCH

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 Typical Infrared Absorption
Regions
O-H WAVELENGTH (mm)
2.5 4 5 5.5 6.1 6.5 15.4
O-H C-H C N C=O C=N C-Cl
Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

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 The O-H stretching region
 O-H 3600 cm-1 (alcohol, free)
 O-H 3300 cm-1 (alcohols & acids,
H-bonding)

broadens
shifts
FREE H-BONDED

3600
3300
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 Effect of Hydrogen-Bonding
on O-H Stretching

Free
OH
Free C-H
OH

H-bonded H-bonded
OH C-H OH C-H

4000 3600 3200 2800 4000 3600 3200 2800 4000 3600 3200 2800

(a) Pure Liquid (b) Dilute Solution (c) Very Dilute Solution
“neat”
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1-Butanol
 HYDROGEN-BONDED HYDROXYL

Many kinds of OH
R R bonds of different
lengths and
O H O strengths
H H This leads to a
broad

R O R O O absorption.
H R
“Neat” solution.
H
O
R H Longer bonds are
weaker and lead to
lower frequency.

Hydrogen bonding occurs in concentrated solutions

39 ( for instance, undiluted alcohol ).
 “FREE” HYDROXYL
The “free” hydroxyl vibrates without interference from any
other molecule.

Distinct bond has a

CCl4 well-defined length
CCl4 and strength.
R O CCl4
H
CCl4
CCl4
Solvent molecules
surround but do not
hydrogen bond.

Occurs in dilute solutions of alcohol in an “inert” solvent like CCl4.

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 ALCOHOL

Cyclohexanol
neat solution

O-H OH CH2
H-bond
C-O

C-H

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 CARBOXYLIC ACID

Butanoic Acid
neat solution

O-H
H-bond

C-O
CH2 O

C-H C=O CH3 CH2 CH2 C OH

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 CARBOXYLIC ACID DIMER

O H O
C R
R C
O H O

Strong hydrogen bonding in the dimer weakens the OH

bond and leads to a broad peak at lower frequency.
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 N-H STRETCH

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 Typical Infrared Absorption
Regions
N-H WAVELENGTH (mm)
2.5 4 5 5.5 6.1 6.5 15.4
O-H C-H C N C=O C=N C-Cl
Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)

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 The N-H stretching region
N-H 3300 - 3400 cm-1

 Primary amines give two peaks

H H
N N
H H
symmetric asymmetric
 Secondary amines give one peak
 Tertiary amines give no peak

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 PRIMARY AMINE
aliphatic

1-Butanamine

NH2
scissor
CH3
CH2
NH2

CH3 CH2 CH2 CH2 NH2

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 PRIMARY AMINE
aromatic

3-Methylbenzenamine

-CH3

Ar-H NH2

NH2

benzene
CH3 Ar-H
oops

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 SECONDARY AMINE

N -Ethylbenzenamine

NH

NH CH2 CH3
CH3

Ar-H
benzene
oops

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 TERTIARY AMINE

N,N -Dimethylaniline
Ar-H

-CH3

CH3
no N-H
N
CH3
CH3
benzene Ar-H
oops

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 Pendekatan Analisis Spektra IR
1. Is a carbonyl group present?
The C=0 group gives rise to a strong absorption in the region 1820−1660 cm−1. The peak is often the
strongest in the spectrum and of medium width.You can’t miss it.
2. If the C=O is present, check the following types (if it is absent, go to 3).
ACIDS Is O−H also present?
• Broad absorption near 3400−2400 cm−1 (usually overlaps C−H).
AMIDES Is N−H also present?
• Medium absorption near 3400 cm−1; sometimes a double peak with
equivalent halves.
ESTERS Is C−O also present?
• Strong intensity absorption near 1300−1000 cm−1 .
ANHYDRIDES Two C=O absorption near 1810 and 1760 cm−1.
ALDEHYDES Is aldehyde C−H present?
• Two weak absorption near 2850 and 2750 cm−1 on right side of the
aliphatic C−H absorption.
KETONES The preceding five choices have been eliminated.
3. If the C=O is absent:
ALCOHOLS, PHENOLS Check for O−H.
• Broad absorption near 3400−3300 cm−1.
• Confirm this by finding C−O near 1300−1000 cm−1.
AMINES Check for N−H.
• Medium absorption(s) near 3400 cm−1.
ETHERS Check for C−O near 1300−1000 cm−1 (and absence of O−H near
3400 cm−1).

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 Pendekatan Analisis Spektra IR
4. Double bonds and/or aromatic rings
• C=C is a weak absorption near 1650 cm−1.
• Medium to strong absorption in the region 1600−1450 cm−1; this
often imply an aromatic ring.
• Confirm the double bond or aromatic ring by consulting the C−H
region; aromatic and vinyl C–H occurs to the left of 3000
cm−1 (aliphatic C−H occurs to the right this value).
5. Triple bonds • C≡N is a medium, sharp absorption near 2250 cm−1.
• C≡C is a weak, sharp absorption near 2150 cm−1.
• Check also for acetylenic C-H near 3300 cm−1.
6. Nitro groups • Two strong absorption at 1600−1530 cm−1 and 1390−1300 cm−1 .

7. Hydrocarbons • None of the preceding is found.

• Major absorptions are in C-H region near 3000 cm−1.
• Very simple spectrum; the only other absorptions appear near 1460
cm−1 and 1375 cm−1.

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 Contoh spektra molekul obat

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