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Transcript of Page 1 hv (UV) hv (Vis.). Synthesis of spironaphthoxazine derivative having potential applications...
Synthesis of spironaphthoxazine derivativehaving potential applications in Smart Polymers.
Presented by : Sampath Weerasinghe
Supervised by: Dr. Thilini Gunasekara
Department of Chemistry,
University of Sri Jayewardenepura
18/02/2014
Page 3
What are Smart Polymers?
Learn and self-correct over time
Respond to external stimuli
Chen,M.; Wang,X.; Cheng,F. Light-driven mobile robot based on light-induced bending polymer film,
J. of Mech. Engineering Research, 2011,03,114
Smart polymerResponseExternal stimuli
pHHeatLight Stress
Chemicals
ShapeColour
SolubilitySol-to-gel transition
physical or chemical changes
Introduction
Page 4
Introduction
Photochromic polymer
Yu, Y.; Ikedaa, T., Alignment modulation of azobenzene-containing liquid crystal systems by
photochemical reactions. J. Photochem. and Photobiol. 2004, 5, 247–265.
hv
Photoresponsive chromophore Polymer system
Synthesis Incorporate
Page 5
Introduction
Spironaphthoxazine
Photoresponsive chromophore
Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in
metal ion-containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, 236-240.
CH3
N
CH3
CH3
N
O O
CH3CH3
N
CH3
N hv(UV)
hv(Vis)
CH3
N
CH3
CH3
N
O
1,3,3-Trimethylspiroindolinenaphthoxazine
O-
CH3CH3
C+
N
CH3
Nhv (UV)
hv (Vis.)hv (Vis)
hv (UV)
Page 6
Synthesise 1,3,3-Trimethyl-9’-
hydroxyspiroindolinenaphthoxazine pendant group which
could be used in future to develop novel smart polymers.
Research objectives
I.Develop and optimize simple synthesis pathway to produce
1,3,3-Trimethyl-9’-hydroxyspiroindolinenaphthoxazine.
II.Identify suitable purification methods.
III.Analyse and characterize the products.
Objectives
Page 7
Proposed synthesis pathway
Experimental methodology
OHOHOHOH
NO
CH3 CH3
N
N
O
CH3
OH
Step 1 Step 2
2,7-Dihydroxynaphthalene 2,7-Dihydroxy-1-nitrosonaphthalene
1,3,3-Trimethyl-9’-hydroxyspiroindolinenaphthoxazine
Page 8
Synthesis of 2,7-Dihydroxy-1-nitrosonaphthalene
Experimental methodology (step 1)
OHOH
1.00 g, 6.25 mmol
0.6M NaOH
15 ml
0 0C
0 0C
0 0C
NaNO0.43 g, 6.25 mmol
Conc. H2SO4
1.4 ml
Stir 1hlow temperature
Page 9
Analysis of the crude product 1
S – starting material R – reaction mixture
Mobile phase - 6 : 1, v/v mixture of Chloroform : Methanol
Results and Discussion (step 1)
R S
Stir for 1 hour
Page 10
Characterization of product 1 by GC-MS
Results and Discussion (step 1)
Gas chromatogram
4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.0012.00 13.0014.00 15.0016.00 17.00
50000
100000
150000
200000
250000
300000
350000
400000
450000
500000
550000
600000
650000
700000
750000
800000
850000
900000
950000
1000000
1050000
1100000
1150000
1200000
1250000
1300000
1350000
1400000
1450000
T ime-->
Abundance
T IC: SJ P .GCMS_09.10.2013_CHEM_SAMPATH_P1H.D\ data.ms 3.939
Stir for 1 hour
Page 11
. +
. +
Results and Discussion (step 1)
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 2100
1000
2000
3000
4000
5000
6000
7000
8000
9000
m/ z-->
Abundance
Scan 150 (3.945 min): S J P .GCMS_09.10.2013_CHEM_SAMPATH_P1H.D\ data.ms (-136) (-)160.0
131.0
77.0 103.051.0
191.0145.9 207.8
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 2100
1000
2000
3000
4000
5000
6000
7000
8000
9000
m/ z-->
Abundance
#30166: 2,7-Naphthalenediol160.0
131.0
77.0 103.051.0
29.0
131.0
OH OH
160.0
Mass Spectrum Stir for 1 hour
C+
Page 12
Analysis of the crude product 2
Results and Discussion (step 1)
S R
S – starting material R – reaction mixture
Mobile phase - 6 : 1, v/v mixture of Chloroform : Methanol
Stir for 2 hours
Page 13
Characterization of product 2 by GC-MS
Results and Discussion (step 1)
Gas chromatogram
4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.000
50000
100000
150000
200000
250000
300000
350000
T ime-->
Abundance
[_GCMS_SMT]*T IC: SJ P .GCMS_09.10.2013_CHEM_SAMPATH_P2H.D\ data.
3.259
3.882
3.974
4.500
5.553
6.543
8.139
Stir for 2 hours
Page 14
. +
. +
Results and Discussion (step 1)
Mass Spectrum
60 80 100 120 140 160 180 200 220 240 260 2800
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
26000
28000
30000
m/ z-->
Abundance
Scan 602 (6.531 min): S J P .GCMS_09.10.2013_CHEM_SAMPATH_P2H.D\ data.ms (-596) (-)189.0
172.0
143.9
77.0
102.1
51.0
119.0209.0 263.1 281.0
OHOH
NOOH
C+
NO
OHOH C+
OH189.0
172.0
159.0
144.0
Stir for 2 hours
Page 15
Characterization of product 2 by IR spectrum
Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in metal
ion-containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, 236-240.
Results and Discussion (step 1)
1301
.98
3143
.54
-30
-20
-10
0
10
20
30
40
50
60
70
80
90
%T
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
OH
NOOHOH
NO
Page 16
Experimental methodology (step 2)
Synthesis of 1,3,3-Trimethyl-9’-hydroxyspiroindolinenaphthoxazine
1.6 ml (drop vice)
1,3,3,-trimethyl-2-methyleneindoline
2,7-dihydroxy-1-nitrosonaphthalene
1.88 g, 6.210mmol
CH3 CH3
N
CH3
CH2
OHOH
NO
anhydrous CH3OH
50 ml
OHOH
NO
CH3 CH3
N
N
O
CH3
OH
Step 2
Page 17
Experimental methodology (step 2)
1,3,3,-trimethyl-2-methyleneindoline
2,7-dihydroxy-1-nitrosonaphthalene in anhydrous methanol
Anhydrous Silica N2 gas
Page 18
Purification of crude product by column chromatography
Determination of solvents/ solvent system for column chromatography
Results and Discussion (step 2)
Solvent systems
Ratio of volume
used in the solvent system
1 Methanol 1
2 Ethanol 1
3 Ethyl acetate : Hexane 3 :1
4 Ethyl acetate : Hexane 1 : 1
5 Ethyl acetate : Hexane 1 : 2
6 Ethyl acetate : Hexane 1 : 4
5 6
Rf–0.90
Rf–0.83
Rf–0.91
Rf–0.40
Page 19
Characterization of the purified product
Results and Discussion (step 2)
Gas chromatogram
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00
500000
1000000
1500000
2000000
2500000
3000000
3500000
T ime-->
Abundance
T IC: SJ P .GCMS_27.11.2013_CHEM_SAMPATH_PR 131107.D\ data.ms11.836
20.224
Page 20
Characterization of the purified product
Results and Discussion (step 2)
Mass Spectrum
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 3800
1000
2000
3000
4000
5000
6000
7000
8000
9000
m/ z-->
Abundance
Scan 1530 (11.842 min): SJ P .GCMS_27.11.2013_CHEM_SAMPATH_PR131107.D\ data.ms (-1506) (-)149.0
57.0279.1
113.183.1
180.0 221.0 390.4249.1 361.4333.1
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 3800
1000
2000
3000
4000
5000
6000
7000
8000
9000
m/ z-->
Abundance
#119596: 1,2-Benzenedicarboxylic acid, mono(2-ethylhexyl) ester149.0
57.0
113.0279.083.029.0
180.0
1,2-Benzenedicarboxylic acid
O
OHOHO
Page 21
Characterization of the purified product
Results and Discussion (step 2)
Gas chromatogram
4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00
500000
1000000
1500000
2000000
2500000
3000000
3500000
T ime-->
Abundance
T IC: SJ P .GCMS_27.11.2013_CHEM_SAMPATH_PR 131107.D\ data.ms11.836
20.224
Page 22
. +
Results and Discussion (step 2)
Mass Spectrum
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 3600
1000
2000
3000
4000
5000
6000
7000
8000
9000
m/ z-->
Abundance
Scan 2994 (20.219 min): S J P .GCMS_27.11.2013_CHEM_SAMPATH_PR 131107.D\ data.ms (-2870) (-)159.1
344.1
115.1 185.1314.177.0
286.1256.151.1 228.1 368.4
40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 3600
1000
2000
3000
4000
5000
6000
7000
8000
9000
m/ z-->
Abundance
#29912: 1H-Indole, 5,6,7-trimethyl-144.0
39.0115.065.0
91.0
CH3 CH3
N
N
O
CH3
OH
344.1CH3
C+
N
N
O
CH3
OH
329.2
CH+
N
N
O
CH3
OH
314.1
CH3 CH3
CH+
N
CH3
159.1
CH3
CH+
N
CH3
144.1
Page 23
Characterization of the purified product
Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in metal ion-
containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, 236-240.
Results and Discussion (step 2)
IR spectroscopy
743.
46
829.
44
1356
.19
1627
.25
3064
.25
3313
.51
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
%T
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
OH
C-O
C=N
=C-H
CH3 CH3
N
N
O
CH3
OH
Page 24
Results and Discussion (step 2)
Characterization of the purified product
Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in
metal ion-containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, 236-240.
UV-Vis spectrophotometry
Page 26
Optimized the 1st synthesis step and successfully able to
synthesize 2,7-Dihydroxy-1-nitrosonaphthalene.
Peaks at 189.0, 172.0, 159.0 and 144.0 in the GC-MS
spectrum, we can conclude that the targeted product 2,7-
Dihydroxy-1-nitrosonaphthalene was successfully
synthesized.
IR spectroscopy, UV-Vis spectroscopy and Gas
Chromatography- Mass Spectrometry the final product was
characterized and identified.
Conclusion
Page 27
From the peaks at 344.1, 329.2, 314.1, 299.1, 172.1, 159.1,
144.1 in the GC-MS spectrum, we can conclude that the
targeted product 1,3,3-Trimethyl-9’-
hydroxyspiroindolinenaphthoxazine was successfully
synthesized.
Finally, we can confirm that we have successfully able to
synthesised a photo and electro sensitive chromophore.
Conclusion
Page 28
NMR spectrum analysis, can confirm the structure of 1,3,3-
Trimethyl-9’-hydroxyspiroindolinenaphthoxazine.
Carry out photochromic studies of 1,3,3-Trimethyl-9’-
hydroxyspiroindolinenaphthoxazine.
Incorporate into a polymer matrix to develop a novel smart
polymer material.
Future work
Page 31
Dr. Thilini Gunasekara, Lecturer, Department of Chemistry
Prof. P. M. Jayaweera, Head - Department of Chemistry
Dr. S. D. M. Chinthaka, Coordinator of Central Instrumentation Facility
Mr. J. G. R. P. S. Ubesena, Central Instrumentation Facility
Dr. U. Weerasuriya and Dr. Sujeewa at University of Texas at Austin,
USA for their precious support of this research.
Dr. M. N. Kaumal and Dr. Ashani Thilakarathne Department of Chemistry,
University of Colombo.
Mr. W. Senadeera and other non academic staff.
My parents, colleagues and to my friends.
Acknowledgement
Page 33
Appendix
IR spectrum of 2,7-Naphthalenediol
796.
79
829.
22
882.
13
1149
.17
1180
.48
1183
.31
1368
.46
1465
.88
1518
.90
1615
.8930
51.9
9
3181
.63
3284
.90
40
45
50
55
60
65
70
75
80
85
90
%T
500 1000 1500 2000 2500 3000 3500 4000
Wavenumbers (cm-1)
Page 34
Appendix
UV-Vis spectrum of literature reported 1,3,3-Trimethyl-9’
hydroxyspiroindolinenaphthoxazine
Nishikiori, H.; Takamura, T.; Shimamura, S.; Fujii, T., Photochromic behavior of spironaphthoxazine in
metal ion-containing solutions, J. Photo.chem. Photo.biol. Chem. 2001, 222, 236-240.
Page 35
The oven temperature was initially programmed at 200 0C and hold for
5minutes. Then the temperature was increased at the rate of 100Cmin-1 to
2800C and hold for 20minutes.