This ppt. is based on my research with benzene platform for its derivitization with various functionalities.

1. UNSYMMETRICAL DERIVATIZATION OF THE BENZENE
PLATFORM WITH 8-HYDROXYQUINOLINE or 2-
AMINOTHIOPHENOL
A
THESIS
SUBMITTED TO THE GURU NANAK DEV UNIVERSITY
AMRITSAR
FOR PARTIAL FULFILLMENT OF THE DEGREE
MASTER OF SCIENCE
IN
CHEMISTRY (HONOURS SCHOOL)
2013
Supervised By
Dr. Prabhpreet Singh
Submitted By
Ankit Grover
DEPARTMENT OF CHEMISTRY
GURU NANAK DEV UNIVERSITY
AMRITSAR-143005 (pb)

2. INTRODUCTION
The Benzene ring is useful as a small, rigid platform for receptor systems. However, in the easily
accessible 1,3,5-substituted benzene (A), mesitylene based host molecules (B), Durene based host
molecules (C) a conformational control of the binding groups is essentially non-existent. In 1976.
McNicol discover the preorganization of the functional groups in hexa-substituted benzene derivatives
(D) .In these systems, six identical substituents are disposed alternatingly above and below the
benzene plane. The major limitation for a wider use of these per- substituted benzene systems was
the difficulty to synthesize receptors with different functionalities on one phenyl ring that is the fact
that all six substituents had to be the same.

3. In this present research project, we have exploited the planer platform such as benzene for
multiple unsymmetrical functionalization. This could provide a platform for doing the sensing
R
RR
R
R
R
X
R
X
R
X
R
X
R
X
R
X
R
X
R
X
R
A B C D
X = S or CH2

4. Luigi Fabbrizzi et. al. described that molecular luminescent sensor for anions or cations can be built
through a modular approach, i.e. by covalently linking an appropriate photoactive fragment to the
receptor displaying a satisfactory affinity towards the desired substrate.
Perylene diimides (PDIs) are inexpensive, readily available compounds. Perylene diimides have
attracted great interest as a result of their unique optical and photo physical properties.
Benzene platform with 8-hydroxyquinoline on one and 2-aminothiophenol functionality on the other
arm could be utilized for functionalization of the perylene dianhydride. This could provide a
platform for doing the sensing on the perylene core.

5. EXPERIMENTAL SECTION
We started our project with the synthesis of these starting materials. We have carried out
bromomethylation of mesitylene and Durene core.
Br
potassiumphthalimide
90o
C,12h N
O
O
With these bromides in our hand, we carried out phthalation reaction with potassium phthalimide
by dissolving bromide in dimethylformamide (DMF) followed by addition of potassium phthalimide
slowly.
1-(Bromomethyl)-2, 3, 5, 6-tetramethylbenzene
2-(2,3,5,6-tetramethylbenzyl)isoindoline-1,3-dione
Br
HBr/Acetic acid
paraformaldehyde
40 °C, 8h
N
O
O
(HCHO)n,ZnBr2
HBr/Aceticacid(33%)
Aceticacid,100o
C,18h
N
O
O
Br
Now we are concern with doing the bromomethylation of these phthalimide derivatives allows
the complete conversion of the ArH into bromo-methylated derivatives

6. Next step in the way of next challenge is to synthesize benzene core either with 8-hydroxy
quinoline or 2-aminothiophenol functionality.
2-(2,4,6-trimethyl
-3,5-bis((quinolin-8-yloxy)methyl)benzyl)
isoindoline-1,3-dione
2-(4-(bromomethyl)
-2,3,5,6-tetramethylbenzyl)
isoindoline-1,3-dione
N
O
O
Br N
O
O
O
N
K2CO3, 8-hydroxyquinoline
DMF, 90o
C,10h
1H NMR (300 MHz, CDCl3, 25 ○C, TMS) δ (ppm): 2.33 (s, 6H, 2x CH3), δ 2.36 (s, 6H, 2x CH3), 5.00 (s,
2H, CH2O), 5.20 (s, 2H, CH2N), 7.29 (d, 1H), 7.39 (m, 1H), 7.43 (m, 1H), 7.41 (d, 1H), 7.61 (m,
2H), 7.70 (m, 2H), 8.13 (m, 1H), 8.91 (m, 1H).

7. 1H NMR (300 MHz, CDCl3, 25 ○C, TMS) δ (ppm): 2.2 (s, 6H), 2.3 (s, 6H), 4.0 (s, 2H), 4.91 (s, 2H), 6.58
(m, 1H), 6.71 (m, 1H), 7.09 (d, 1H), 7.16 (d, 1H), 7.69 (m, 2H), 7.79 (m, 2H).
N
O
O
B r N
O
O
S
N H 2
N a H , 2 - a m i n o t h i o p h e n o l
D M F , 9 0 o
C ,1 0 h
2-(4-((2-aminophenylthio)methyl)
-2,3,5,6-tetramethylbenzyl)
isoindoline-1,3-dione
2-(4-(bromomethyl)
-2,3,5,6-tetramethylbenzyl)
isoindoline-1,3-dione

8.  8-Hydroxyquinoline and its derivatives possess good photo-stability and strong ability to complex
metal ions and are used in organic light emitting diode devices in chromatography and in
electrochemi-luminescence etc. Recently, 8-hydroxyquinoline based fluoroionophores have been
developed for detecting Cd2+, Hg2+, Zn2+ ions and have proved to be effective in discriminating
Cd2+ over Zn2+.
 2-aminothiophenol is a sulphur and nitrogen containing compound and can be introduced around
the benzene platforms and this will leads to introduction of more than one thiol groups on
benzene platform and thus could leads to the enhanced bond strength to metal cations.
CONCLUSION

9. Thanks