ELUSIDASI STRUKTUR SENYAWA

ORGANIK
MATA DIKLAT : KIMIA ORGANIK

KELAS XIII
SEMESTER GASAL

DISUSUN OLEH :
GINA LIBRIA N., S.Si., M.T

KEMENTERIAN PERINDUSTRIAN R.I

PUSAT PENDIDIKAN DAN PELATIHAN INDUSTRI
SEKOLAH MENENGAH KEJURUAN – SMAK BOGOR
2017
1
PROCEDURE TO DETERMINE STRUCTURE OF ORGANIC
COMPOUND
Procedure:
1. Obtain the Mr and use it to look up the molecular formula.

2.Rule out functional groups that cannot belong to the molecular formula.

3. Examine the IR spectrum to determine the presence of suspected functional groups. This is
done by examining the peaks in the functional group region (4000 - 1100cm-1) for peaks in
positions that are characteristic of functional groups that can fit with the molecular formula.

4.List the (main) possible isomeric structures.

PROCEDURE TO DETERMINE STRUCTURE OF ORGANIC
COMPOUND (2)

5. Examine the NMR spectrum and note the number of peak groups and their integrals. This may indicate
the number of methyl (CH3), methylene (CH2) and methine (CH) groups.

6. Examine the NMR spectrum chemical shifts and attempt to determine the proximities of nearby
protons to the functional group. If a functional group proton is suspected, it may be possible to locate it
by consideration of the integral and chemical shift data.

7. Examine the NMR spectrum for peak multiplicity in order to determine the number of protons on
neighbouring groups. This will give the proton sequence that determines which isomer is the correct
structure.

8. Confirm the structure by checking the MS fragmentation pattern.

EXAMPLE

Example No. 1: Mr = 60.0977

Example No. 1: Mr = 60.0977

NMR SPECTRA
HOW TO INTERPRETE:

Working out:
Mr = 60.0977 means that the molecular formula is C3H8O.
The molecular formula rules out the possiblity of a carboxylic acid or amine.
(Also - must not contain a carbonyl group or multiple C-C bonds, to accommodate all eight Hs
in the structure)

IR Strong and fairly broad absorption from 2800 to 3300 cm-1

Hence, probably an alcohol (H-bonded in solution).
Sharp peak at about 1100 cm-1 would be the C-O absorption of the alcohol.
Alcohol isomers CH3CH2CH2OH CH3CH(OH)CH3 (CH3)2CHOH
• NMR Shows three peaks:
delta4.0 multiplet (5 or 6 peaks) integrates as 1.
delta3.4 broad single, peak integrates as 1.
delta1.2 sharp, doublet integrates as 6.
• There are six equivalent protons at delta1.2 suggesting two CH3 groups arranged symmetrically (same chemical
environment).
• The chemical shift agrees with CH3-C-OH.
• Since the absorption is a doublet, there must be -CH- next to each of the two methyl groups. i.e. it must be
between them.
• The structure so far would be: CH3-CH-CH3
• The multiplet at delta4.0 would belong to the -CH- since it integrates as 1 and would be extensively split by the
two adjacent methyl groups.
• The delta3.4 absorption would belong to -OH (integrates as 1) which is in the correct range (0.5 - 5.5) for a
hydroxyl proton. The hydroxyl group would be attached at C2.
• The final structure is CH3CH(OH)CH3 2-propanol
• The mass spectrum has the characteristic M - H2O (60 - 18 = 42) peak for an alcohol.
• The M - CH3 peak (at 45) appears as would be expected for this structure.
Example No. 2: Mr = 102.1360
Mr = 102.1360 means that the molecular formula is C5H10O2
The molecular formula rules out the possibility of an amine.
IR Strong absorption 1750 cm-1 Hence, carbonyl group of an ester.
Broad absorption below 1300 cm-1 for the C-O absorption of the ester.

Ester isomers:
CH3CH2CH2COOCH3 (CH3)2CHCOOCH3
CH3CH2COOCH2CH3
CH3COOCH2CH2CH3 CH3COOCH(CH3)2
NMR Four absorptions shown:

3.8 singlet integrates as 3.

2.2 triplet integrates as 2.

1.4 sextuplet integrates as 2.

0.9 triplet integrates as 3.

There are three protons at 3.8 so it is probably CH 3. The singlet shows that the protons are isolated: could be methyl ester. The chemical shift of 3.8 is in good agreement with
R-CO-O-CH3 (located at 3.7).
There are two protons at 2.2 suggesting a CH 2 group.
The chemical shift agrees with -C-CH2-CO-O-R'.

The triplet splitting further suggests that there is an additional CH 2 neighbour (see absorption at 1.4).
 The structure so far would be: -CH2-CH2-CO-O-CH3

The sextuplet at 1.4, integrating as two, would belong to -CH2 - and would
be split by CH2 and CH3 (see 0.9) groups on either side.
The chemical shift agrees well with -CH2-C-CO-O-R'.
The 0.9 absorption would belong to CH3 (integrates as 3). It is split into a
triplet by a neighbouring CH2.
The final structure is CH3CH2CH2COOCH3 methyl butyrate

The mass spectrum shows: 71 M - 31 for removal of OCH3 from

RCOOCH3
59 appearance of CO+OCH3 from RCOOCH3