viii
TABLE OF CONTENTS
CHAPTER
TITLE
DECLARATION
ii
DEDICATION
iii
ACKNOWLEDGMENTS
iv
PREFACE
v
ABSTRACT
vi
ABSTRAK
vii
TABLE OF CONTENTS
viii
LIST OF TABLES
xiii
LIST OF SCHEMES
xiv
LIST OF FIGURES
xvii
LIST OF ABBREVIATIONS
xx
LIST OF SYMBOLS
1
2
PAGE
INTRODUCTION
xxiii
1
1.1
General Introduction
1
1.2
Flavones in Nutrition and Health
2
1.3
Problems Statements
3
1.4
Objectives of Study
3
1.5
Scope of Study
4
LITERATURE REVIEW
5
2.1
Flavonoids
5
2.2
Naturally Occuring and Biological Activities of
6
Flavonoids
2.3
Classical Synthetic Pathway to Flavonoids
13
ix
2.4
2.3.1
Claisen-Schmidt Condensation
13
2.3.2
Baker Venkataraman Rearrangement
14
2.3.3
Algar-Flynn-Oyamada Reaction
15
Recent Developement in Synthetic Route to Flavonoids
15
2.4.1
15
Boron-Trifluoride Etherate (BF3-Et2O) as the
Catalyst
2.4.2
Suzuki Coupling Reaction
17
2.4.3
Sonogashira Coupling
18
2.4.4
Synthesis of Flavonoids via Microwave (MW)
19
Irradiation
2.5
Synthesis Route to Prenylated Flavonoids
20
2.5.1
Potassium Hydroxide (KOH) as the Catalyst
20
2.5.2
Potassium Carbonate (K2CO3) as the Catalyst
21
2.5.3
Boron-Trifluoride Etherate (BF3-Et2O) as the
23
Catalyst
2.5.4
1,8-diazobicyclo [5.4.0] undec-7-ene (DBU) as
23
the Catalyst
2.5.5
Mitsunobu Reaction
24
2.5.6
Tetrabutylammonium Hydroxide (TBAOH) as
25
the Catalyst
2.5.7
Dimethyl Sulfide Complex-Copper Bromide
25
(CuBr.DMS) as the Catalyst
3
RESULTS AND DISCUSSION
27
3.1
Synthesis of Precursors
27
3.1.1
27
Protecting the Hydroxyl Groups of Starting
Materials
3.1.2
Methylation of Starting Materials
30
3.1.3
Methylenedioxy Substitution of 3,4-
33
dihydroxybenzaldehyde (93)
3.1.4
3.2
Prenylation of Starting Materials
Retrosynthetic Analysis of 2ʹ,3,4-trihydroxy-4ʹ,6ʹdimethoxychalcone (110)
33
51
x
3.3
Synthesis of 2ʹ,4ʹ,6ʹ-trihydroxy-4,6-dimethoxychalcone
63
(120)
3.4
Synthesis of 4ʹ,5,7-trimethoxy-3ʹ-O-prenylflavanone
65
(123)
3.5
Synthesis of 4ʹ,5,7-trimethoxy-3ʹ-O-6-C-
75
diprenylflavanone (126)
3.6
Synthesis of 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4-
79
methylenedioxy-3ʹ-C-prenylchalcone (127)
3.7
Synthesis of 5,6-dichroman-7-methoxy-3ʹ,4ʹ-
84
methylenedioxyflavone (130)
3.8
Synthesis of 5,6,7,8-dichroman-3ʹ,4ʹ-
86
methylenedioxyflavone (132)
3.9
Synthesis of 5ʹ,6ʹ-chroman-2ʹ,3,4-trihydroxy-4ʹ-
96
methoxychalcone (134)
3.10 Retrosynthetic Analysis for the Synthesis of 3ʹ,4ʹ,5ʹ,6ʹ-
104
dichroman-2ʹ,3,4-trihydroxychalcone (137)
3.11 Synthesis of 3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4-dimethoxy-2ʹ-
107
hydroxychalcone (138)
3.12 Synthesis of 5ʹ,6ʹ-chroman-2ʹ-hydroxy-4ʹ-methoxy-3,4-
109
O-diprenylchalcone (139)
4
BIOACTIVITIES OF THE SYNTHETIC FLAVONOIDS
116
4.1
116
Antioxidant Studies of the Selected Synthesized
Compounds
4.1.1
4.2
4.3
5
DPPH Free radical Scavenging Assay
117
Anti-Inflammatory Studies
120
4.2.1
13-Lipoxygenase Assay
121
4.2.2
Xanthine Oxidase
122
Antibacterial Assay
124
EXPERIMENTAL
126
5.1
General Procedures
126
5.2
Synthesis of Precursors
127
xi
5.2.1
Protection of the Hydroxyl Groups
127
5.2.2
Methylation of 2,4,6-trihydroxyacetophenone
128
5.2.3
3,4-Methylenedioxybenzaldehyde (98)
129
5.2.4
Synthesis of Prenylated Precursors Using
130
Potassium Carbonate (K2CO3) as the Catalyst
5.2.5
Synthesis of Prenylated Precursors Using 1,8-
132
diazobicyclo [5.4.0] undec-7-ene (DBU) as the
Catalyst
5.3
Synthesis of 2ʹ,3,4-trihydroxy-4ʹ,6ʹ-dimethoxychalcone
133
(110) [107]
5.4
Synthesis of 2ʹ,4ʹ,6ʹ-trihydroxy-4,6-dimethoxychalcone
134
(120)
5.5
Synthesis of 4ʹ,5,7-trimethoxy-3ʹ-O-prenylflavanone
136
(123)
5.6
Synthesis of 4ʹ,5,7-trimethoxy-3ʹ-O-6-C-
138
diprenylflavanone (126)
5.7
Synthesis of 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4-
140
methylenedioxy-3ʹ-C-prenylchalcone (127)
5.8
Synthesis of 5,6-dichroman-7-methoxy-3ʹ,4ʹ-
141
methylenedioxyflavone (130)
5.9
Synthesis of 5,6,7,8-dichroman-3ʹ,4ʹ-
143
methylenedioxyflavone (132)
5.10 Synthesis of 5ʹ,6ʹ-chroman-2ʹ,3,4-trihydroxy-4ʹ-
144
methoxychalcone (134)
5.11 Synthesis of 3ʹ,4ʹ,5ʹ,6ʹ-dichroman-2ʹ,3,4-
146
trihydroxychalcone (137)
5.12 Sythesis of 3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4-dimethoxy-2ʹ-
147
hydroxychalcone (138)
5.13 Synthesis of 5ʹ,6ʹ-chroman-2ʹ-hydroxy-4ʹ-methoxy-3,4-
148
O-diprenylchalcone (139)
5.14 Bioactivity Procedures
5.14.1
149
Antioxidant Assay
149
5.14.1.1
149
Chemicals and Instrumentation
xii
5.14.1.2
DPPH Free Radical Scavenging
149
Assay
5.14.2
5.14.3
Anti-Inflammatory Assay
150
5.14.2.1
Chemicals and Instrumentation
150
5.14.2.2
13-Lipooxygenase Assay (13-LOX)
151
5.14.2.3
Xanthine Oxidase Assay (XO)
152
Antibacterial Activtiy
153
5.14.3.1
Chemicals and Microorganisms
153
5.14.3.2
Disc Diffusion Method Assay
153
5.14.3.3
Minimum Inhibition Concentration
154
(MIC)
5.14.3.4
Minimum Bactericidal Concentration
155
(MBC)
6
CONCLUSION AND RECOMMENDATIONS
156
6.1
Conclusion
156
6.2
Recommendations for Future Works
158
REFERENCES
159
APPENDICES
173
PUBLICATIONS
216
xiii
LIST OF TABLES
TABLE NO.
TITLE
PAGE
3.1
1
H NMR, 13C NMR and DEPT Data of Compound (104)
43
3.2
1
H, 13C and DEPT of Acetophenone (105)
44
3.3
1
H, 13C and DEPT for Chalcone (119)
64
3.4
1
H, 13C NMR and DEPT for Chalcone (122)
67
3.5
1
H, 13C and DEPT Data for Flavanone (123)
68
3.6
1
3.7
1
3.8
13
77
13
H, C NMR and DEPT Data of Flavone (132)
88
1
H NMR and 13C NMR Data of Compound (133)
97
3.9
1
H, 13C NMR and DEPT Data of Chalcone (136)
105
3.10
1
H NMR data for Chalcone (137)
106
3.11
1
H, 13C NMR and DEPT Data of Chalcone (138)
108
3.12
1
H, C NMR and DEPT for Flavanone (126)
13
H, C NMR and DEPT Data of Chalcone (139)
110
4.1
Antioxidant Activity of the Chalcones
117
4.2
13-Lipooxygnase Assay of the Chalcones
121
4.3
XO Activity of the Chalcones
123
4.4
MIC and MBC of the Tested Compounds
124
xiv
LIST OF SCHEMES
SCHEMES
TITLE
PAGE
2.1
Synthesis of Chalcones (31) via Claisen-Schmidt
Condensation
13
2.2
Synthesis of 3-acyl-γ-pyrones (32)
14
2.3
Synthesis of Morusin (33) via Baker-Venkataraman
Condensation
14
2.4
Algar-Flynn-Oyamada Reaction
15
2.5
Synthetic Pathway of Oroxylin A (41), Baicelin (42) and
Wogonin (44) by Using BF3-Et2O Method.
16
2.6
Synthetic Route of (55) by Suzuki Coupling Reaction
2.7
Synthesis of Alkynyl Ketones (58) by Using Sonogashira
Coupling
18
2.8
Synthesis of Compounds (62) and (63) via Sonogashira
Coupling
19
2.9
Microwave Irradiation to Synthesis 2-aryl-4-quinolone (65)
20
2.10
Synthetic Approach to Prenylated Precursor Using
Aqueous KOH
21
2.11
Synthesis of C-prenylated Precursors by Using Aqueous
KOH
21
2.12
Synthesis of Geranylated Acetophenone Using Anhydrous
K2CO3
22
2.13
Synthetic Pathway of C-prenylated Acetophenone
22
2.14
Synthesis of Prenylated Acetophenone by Using BF3Et2O
23
17-18
xv
2.15
Synthesis of C-prenylated Acetophenone (84) by Using
DBU
24
2.16
Synthesis of 5-O-prenylflavanone (86) by Mitsunobu
Reaction
24
2.17
Synthesis of C-prenylated Flavone (88) by Using TBAOH
25
2.18
Synthesis of C-prenylated Precursor (90) by Using
CuBr•DMS
26
3.1
Mechanism for the Formation of 2-hydroxy-4,6bis(methoxymethyloxy)acetophenone (92)
28
3.2
Mechanism for the Formation of Compound (95)
29
3.3
Mechanism for the Formation of 2-hydroxy-4,6dimethoxyacetophenone (97)
32
3.4
Methylenedioxy Substitution of 3,4dihydroxybenzaldehyde (93)
33
3.5
Prenylation on 2,4,6-trihydroxyacetophenone (72)
34
3.6
Prenylation on 3,4-dihydroxybenzaldehyde (93) Using
Freshly Ignited K2CO3 in Dry Acetone.
37
3.7
Possible Mechanism for prenylation of 3,4dihydroxybenzaldehyde (93)
38
3.8
Prenylation of (72) by Using DBU as the Catalyst in Dry
THF
41
3.9
Proposed Mechanism of Compound (104) and (105)
42
3.10
Retrosynthetic route to 2ʹ,3,4-trihydroxy-4ʹ,6ʹdimethoxychalcone (110)
52
3.11
Mechanism for the Formation of Compound (109)
53
3.12
Complexes of Compound (110) in the Presence of AlCl3
and AlCl3/HCl
55
3.13
Attempted Oxidative Cyclization of Chalcone (109) to
Flavone (117)
56
3.14
Synthesis of 2ʹ,4ʹ, 6ʹ-trihydroxy-4, 6-dimethoxychalcone
(120)
63
xvi
3.15
Synthetic Route of 4ʹ,5,7-trimethoxyflavanone-3ʹ-Oprenylflavanone (123)
65
3.16
Synthetic Route of 4ʹ,5,7-trimethoxy-3ʹ-O-6-Cdiprenylflavanone (126)
75
3.17
Fragmentation Pattern of Compound (126)
78
3.18
Formation of Compound (127)
79
3.19
Synthetic Route to 5,6-chroman-7-methoxy-3ʹ,4ʹmethylenedioxyflavone (130)
84
3.20
Synthetic Route to 5,6,7,8-dichroman-3ʹ,4ʹmethylenedioxyflavone (132)
87
3.21
Synthesis of 5ʹ,6ʹ-chroman-2ʹ,3,4-trihydroxy-4ʹmethoxychalcone (134)
96
3.22
Retrosynthetic Analysis of Chalcone (137)
104
3.23
Formation of 3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4-dimethoxy-2ʹhydroxy-chalcone (138)
107
3.24
Formation of 5ʹ,6ʹ-chroman-2ʹ-hydroxy-4ʹ-methoxy-3,4-Odiprenylchalcone (139)
109
4.1
Reaction of DPPH free radical mechanism with radical
(RH)
117
4.2
Mechanism of oxidation involving compounds attached as
ortho-, meta- and para- dihydroxyl substitution
119
4.3
The Mechanism of DPPH free radical onto chalcone (110)
120
4.4
Reactions of Xanthine with Xanthine Oxidase
123
xvii
LIST OF FIGURES
FIGURES
TITLE
PAGE
2.1
Prenylation Patterns Encountered in Flavonoids
3.1
1
H NMR Spectra of Three Different Prenyl-substituted of
Acetophenones (99), (100) and (101)
36
3.2
1
H NMR Spectra in Comparison Between Prenylsubstituted Benzaldehyde of (102) and (103)
39
3.3
13
C NMR and DEPT Spectra of 3-O-prenylbenzaldehyde
(102)
40
3.4
IR Spectrum of 2,4-dihydroxy-5,6-chromanacetophenone
(104)
45
3.5
1
H NMR Spectrum of 2,4-dihydroxy-5,6chromanacetophenone (104)
46
3.6
13
C NMR and DEPT Spectra of 2,4-dihydroxy-5,6chromanacetophenone (104)
47
3.7
IR Spectrum of 2-hydroxy-3,4,5,6-dichromanacetophenone
(105)
48
3.8
1
H NMR Spectra of 2-hydroxy-3,4,5,6dichromanacetophenone (105)
49
3.9
DEPT Spectrum of 2-hydroxy-3,4,5,6dichromanacetophenone (105)
50
3.10
IR Spectrum of 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4bis(methoxymethyloxy)chalcone (109)
57
3.11
1
H NMR Spectrum of 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4bis(methoxymethyloxy)chalcone (109)
58
3.12
13
59
C NMR Spectrum of 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4bis(methoxymethyloxy)chalcone (109)
8
xviii
3.13
DEPT Spectra of 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4bis(methoxymethyloxy)chalcone (109)
60
3.14
1
H NMR Spectrum of 2ʹ,3,4-trihydroxy-4ʹ,6ʹdimethoxychalcone (110)
61
3.15
UV-Vis Spectrum of 2ʹ,3,4-trihydroxy-4ʹ,6ʹdimethoxychalcone (110)
62
3.16
1
H NMR Spectrum of 3ʹ,5,7-trimethoxy-3ʹ-Oprenylflavanone (123)
70
3.17
COSY NMR Spectrum of 3ʹ,5,7-trimethoxy-3ʹ-Oprenylflavanone (123)
71
3.18
13
C NMR Spectrum of 3ʹ,5,7-trimethoxy-3ʹ-Oprenylflavanone (123)
72
3.19
HMQC NMR of 3ʹ,5,7-trimethoxy-3ʹ-O-prenylflavanone
(123)
73
3.20
DEPT Spectra of 3ʹ,5,7-trimethoxy-3ʹ-O-prenylflavanone
(123)
74
3.21
1
H NMR Spectrum of 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4methylenedioxy-3ʹ-prenylchalcone (127)
81
3.22
13
C NMR Spectrum of 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4methylenedioxy-3ʹ-prenylchalcone (127)
82
3.23
DEPT Spectra for 2ʹ-hydroxy-4ʹ,6ʹ-dimethoxy-3,4methylenedioxy-3ʹ-prenylchalcone (127)
83
3.24
1
90
3.25
13
91
3.26
1
H NMR Spectrum of 5,6,7,8-dichroman-3ʹ,4ʹmethylenedioxyflavone (132)
92
3.27
13
C NMR Spectrum of 5,6,7,8-dichroman-3ʹ,4ʹmethylenedioxyflavone (132)
93
3.28
HMQC Spectrum of 5,6,7,8-dichroman-3ʹ,4ʹmethylenedioxyflavone (132)
94
3.29
MS Spectrum of 5,6,7,8-dichroman-3ʹ,4ʹmethylenedioxyflavone (132)
95
H NMR Spectrum of Dichromanchalcone (131)
C and DEPT NMR spectra of dichromanochalcone (131)
xix
3.30
IR Spectrum of 2ʹ-hydroxy-5,6-chromane-4ʹ-methoxy-3,4bis(methoxymethyloxy)chalcone (133)
3.31
1
H NMR Spectrum of 2ʹ-hydroxy-5,6-chromane-4ʹmethoxy-3,4-bis(methoxymethyloxy)chalcone (133)
100
3.32
DEPT Spectra of 2ʹ-hydroxy-5,6-chromane-4ʹ-methoxy3,4-bis(methoxymethyloxy)chalcone (133)
101
3.33
1
H NMR Spectrum of 2ʹ,3,4-trihydroxy-5,6-chroman-4ʹmethoxychalcone (134)
102
3.34
UV Spectrum of 2ʹ,3,4-trihydroxy-5,6-chroman-4ʹmethoxychalcone (134)
103
3.35
1
H NMR of 5ʹ,6ʹ-chroman-2ʹ-hydroxy-4ʹ-methoxy-3,4-Odiprenylchalcone (139)
111
3.36
13
C NMR of 5ʹ,6ʹ-chroman-2ʹ-hydroxy-4ʹ-methoxy-3,4-Odiprenylchalcone (139)
112
3.37
DEPT Spectra of 5ʹ,6ʹ-chroman-2ʹ-hydroxy-4ʹ-methoxy3,4-O-diprenylchalcone (139)
113
3.38
COSY Spectrum of 5ʹ,6ʹ-chroman-2ʹ-hydroxy-4ʹ-methoxy3,4-O-diprenylchalcone (139)
114
3.39
HMQC Spectrum of 5ʹ,6ʹ-chroman-2ʹ-hydroxy-4ʹmethoxy-3,4-O-diprenylchalcone (139)
115
5.1
The Arrangement of the Samples and Control Discs in
Petri Dish
154
99
xx
LIST OF ABBREVIATIONS
BF3-Et2O
boron trifluoride etherate
BHT
butylated hydroxytoluene
br
broad
13
carbon-13
C
CD3COCD3
deuterated acetone
CDCl3
deuterated chloroform
COSY
correlation spectroscopy
CuBr.DMS
dimethyl sulphide complex-copper bromide
d
doublet
DBU
1,8-diazobicyclo [5.4.0] undec-7-ene
DCM
dichloromethane
dd
doublet of doublets
DDQ
2,3-dichloro-5,6-dicyano-1,4-benzoquinone
DEAD
diethyl azidocarboxylate
DEPT
Distortionless Enhancement by Polarization Transfer
DIAD
diisopropyl azidocarboxylate
DMAP
4-dimethylaminopyridine
DMSO
dimethylsulfoxide
DPPH
2,2-diphenyl-1-picrylhydrazyl
EIMS
Electron Impact Mass Spectrometry
Et2O
diethyl ether
EtOAc
ethyl acetate
EtOH
ethanol
hr
hour
1
proton
H
HMBC
heteronuclear multiple bond correlation
HMQC
heteronuclear multiple quantum coherence
xxi
Hz
hertz
IC50
inhibition concentration at 50%
IR
infrared
J
coupling constant
lit.
Literature
LOX
Lipooxygenase
m/z
mass to charge ratio
m
multiplet
M
molar
MBC
minimum bactericidal concentration
Me2SO4
dimethyl sulphate
MeI
iodomethane
MeOH
methanol
MgSO4
magnesium sulphate
MHz
megahertz
MIC
minimum inhibition concentration
MOM
methoxymethyloxy
MOMCl
methoxymethyl chloride
m.p
melting point
MS
mass spectrometry
NaOAc
sodium acetate
NaOMe
sodium methoxide
NDGA
nordihydroguaiaretic acid
NMR
nuclear magnetic resonance
nm
nanometer
Ph
phenyl
Pet
petroleum ether
ppm
parts per million
Rf
retention factor
SD
standard deviation
s
singlet
t
triplet
TBAOH
tetrabutylammonium hydroxide
TBATB
tetrabutylammonium tribromide
xxii
TLC
thin layer chromatography
UV
ultraviolet
XO
xanthine oxidase
δ
chemical shift
λ
lambda
xxiii
LIST OF APPENDICES
APPENDIX
TITLE
PAGE
1
1
H NMR spectrum of 2ʹ-hydroxy-3,4-dimethoxy-4ʹ,6ʹbis(methoxymethyloxy)chalcone (119)
174
2
13
C NMR spectrum of 2ʹ-hydroxy-3,4-dimethoxy-4ʹ,6ʹbis(methoxymethyloxy)chalcone (119)
175
3
DEPT spectra of 2ʹ-hydroxy-3,4-dimethoxy-4ʹ,6ʹbis(methoxymethyloxy)chalcone (119)
176
4
IR spectrum of 2ʹ,4ʹ,6ʹ-trihydroxy-3,4-dimethoxychalcone (120)
177
5
1
H NMR spectrum of 2ʹ,4ʹ,6ʹ-trihydroxy-3,4-dimethoxychalcone
(120)
178
6
UV spectrum of 2ʹ,4ʹ,6ʹ-trihydroxy-3,4-dimethoxychalcone (120)
179
7
IR spectrum of 4-methoxy-3-O-prenylbenzaldehyde (121)
180
8
1
181
9
IR spectrum of 3,4ʹ,6ʹ-trimethoxy-3-O-prenylchalcone (122)
182
10
1
H NMR spectrumof 3,4ʹ,6ʹ-trimethoxy-3-O-prenylchalcone
(122)
183
11
13
C NMR spectrumof 3,4ʹ,6ʹ-trimethoxy-3-O-prenylchalcone
(122)
184
12
1
H NMR spectrumof 3,4ʹ,6ʹ-trimethoxy-3-O-prenylchalcone
(122)
185
13
1
H NMR spectrum of 2-hydroxy-4,6-dimethoxy-5prenylacetophenone (124)
186
14
1
187
H NMR spectrum of 4-methoxy-3-O-prenylbenzaldehyde (121)
H NMR spectrum of 2-hydroxy-4,6-dimethoxy-5prenylacetophenone (124)
xxiv
15
IR spectrum of 3,4ʹ,6ʹ-trimethoxy-3-O-5-C-diprenylchalcone
(125)
188
16
1
H NMR spectrum of 3,4ʹ,6ʹ-trimethoxy-3-O-5-Cdiprenylchalcone (125)
189
17
13
C NMR spectrum of 3,4ʹ,6ʹ-trimethoxy-3-O-5-Cdiprenylchalcone (125)
190
18
DEPT spectra of 3,4ʹ,6ʹ-trimethoxy-3-O-5-C-diprenylchalcone
(125)
191
19
1
H NMR spectrum of 4’,5,7-trimethoxy-3’-O-6-Cdiprenylflavanone (126)
192
20
13
C NMR spectrum of 4',5,7-trimethoxy-3'-O-6-Cdiprenylflavanone (126)
193
21
DEPT spectra of 4ʹ,5,7-trimethoxy-3ʹ-O-6-C-diprenylflavanone
(126)
194
22
MS spectrum of 4ʹ,5,7-trimethoxy-3ʹ-O-6-C-diprenylflavanone
(126)
195
23
1
H NMR spectrum of 2-hydroxy-4-methoxy-5,6chromanacetophenone (128)
196
24
IR spectrum of 2ʹ-hydroxy-5ʹ,6ʹ-chroman-4ʹ-methoxy-3,4methylenedioxychalcone (129)
197
25
1
H NMR spectrum of 2ʹ-hydroxy-5ʹ,6ʹ-chroman-4ʹ-methoxy-3,4methylenedioxychalcone (129)
198
26
13
C NMR spectrum of 2ʹ-hydroxy-5ʹ,6ʹ-chromane-4ʹ-methoxy3,4-methylenedioxychalcone (129)
199
27
DEPT spectra of 2ʹ-hydroxy-5ʹ,6ʹ-chroman-4ʹ-methoxy-3,4methylenedioxychalcone (129)
200
28
MS spectrum of 2ʹ-hydroxy-5ʹ,6ʹ-chroman-4ʹ-methoxy-3,4methylenedioxychalcone (129)
201
29
1
H NMR spectrum of 5,6-chroman-7-methoxy-3ʹ,4ʹmethylenedioxyflavone (130)
202
30
13
C NMR spectrum of 5,6-chroman-7-methoxy-3ʹ,4ʹmethylenedioxyflavone (130)
203
31
DEPT NMR spectra of 5,6-chroman-7-methoxy-3ʹ,4ʹmethylenedioxyflavone (130)
204
xxv
32
HMQC spectrum of 5,6-chroman-7-methoxy-3ʹ,4ʹmethylenedioxyflavone (130)
205
33
MS spectrum of 5,6-chroman-7-methoxy-3ʹ,4ʹmethylenedioxyflavone (130)
206
34
IR spectrum of 2ʹ-hydroxy-3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4bis(methoxymethyloxy)chalcone (136)
207
35
1
H NMR spectrum of 2ʹ-hydroxy-3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4bis(methoxymethyloxy)chalcone (136)
208
36
13
C NMR spectrum of 2ʹ-hydroxy-3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4bis(methoxymethyloxy)chalcone (136)
209
37
DEPT spectra of 2ʹ-hydroxy-3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4bis(methoxymethyloxy)chalcone (136)
210
38
IR spectrum analysis of 2ʹ,3,4-trihydroxy-3ʹ,4ʹ,5ʹ,6ʹdichromanchalcone (137)
211
39
1
H NMR spectrum of 2ʹ,3,4-trihydroxy-3ʹ,4ʹ,5ʹ,6ʹdichromanchalcone (137)
212
40
UV spectrum of 2ʹ,3,4-trihydroxy-3ʹ,4ʹ,5ʹ,6ʹ-dichromanchalcone
(137)
213
41
1
H NMR spectrum of 3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4-dimethoxy-2ʹhydroxychalcone (138)
214
42
13
215
C and DEPT NMR spectrum of 3ʹ,4ʹ,5ʹ,6ʹ-dichroman-3,4dimethoxy-2ʹ-hydroxychalcone (138)