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TABLE OF CONTENTS
INTRODUCTION
CHAPTER 1. LITERATURE OVERVIEWS
CHAPTER 2. EXPERIMENTALS
CHAPTER 3. RESULTS AND DISCUSSIONS
CONCLUSIONS
TABLE OF CONTENTS
Pages
INTRODUCTION ...............................................................................................2
CHAPTER 1 LITERATURE OVERVIEWS ................................................3
1.1 Introduction of quinazoline compounds ..............................................3
1.2 Introduction of quinoxaline compounds..............................................5
1.3 Introduction of N-arylindole compounds.............................................7
1.4 Introduction of thiocromenone compounds.........................................9
1.5 Aims of this work ..............................................................................11
CHAPTER 2 EXPERIMENTALS...............................................................14
2.1 Materials and Instrumentations..........................................................14
2.2 Experimental procedures ...................................................................15
CHAPTER 3 RESULTS AND DISCUSSIONS..........................................16
3.1 Synthesis of quinazoline derivatives via peroxide-mediated direct
oxidative amination of C(sp3)-H bonds.........................................................16
3.2 Condensation of 1,2-phenylenediamines and dicarbonyl compounds in
ethyl acetate toward quinoxalines .................................................................17
3.3 Oxidative nucleophilic functionalization of nitrobenzene with N-H
bond to the synthesis of 1-(4-nitrophenyl)-1H-indoles.................................19
3.4 Elemental sulfur for the synthesis of 2-arylthiochromenones ...........20
CONCLUSIONS ...............................................................................................222
INTRODUCTION
Heterocyclic compounds are important compounds that exhibit an extensive
range of physical, chemical, and biological properties. Heterocyclic compounds
have been presented in numerous pharmacological areas, such as anti-cancer,
antibiotics, anti-inflammatory, anti-inflammatory and depression, anti-malarial,
anti-HIV, antibacterial, antifungal, antiviral, antidiabetic, herbicides, fungicides,
and insecticides. In addition, they have been considered in pharmaceutical
chemistry and agriculture. Accordingly, heterocyclic frameworks such as
quinazolines, quinoxalines, thiocromenones, and N-arylindoles have become the
interesting topics in organic synthesis.
Due to a wide range of applications of heterocyclic compounds in
pharmaceutical, cosmetic, and agricultural chemical industries, developing
effective processes to synthesize 5- and 6-membered heterocyclic compounds
such as quinazoline, quinoxaline, thiocromenone, and N-arylindole derivatives
have been highly demanding. However, the currently available reactions often
require transition metal catalysts and under extreme conditions. Therefore,
proposing new methods for the synthesis of heterocyclic compounds without the
use of any transition metal catalyst would be considered.
In the progression of studying documents, and investigating many reactions to
create heterocyclic compounds, the possible protocols for the synthesis of
4-phenylquinazoline, 2-phenylquinoxaline, 2-arylthiocromenone, and
N-arylindole derivatives without using transition metal catalysts were detected.
On that basis, the reaction conditions for each reaction were screened to
maximize yield, conducted survey products to develop plausible reaction
mechanisms, and extended the application scope of each response. As a result,
the thesis provided effective procedures to synthesize 4-phehylquinazolines,
2-phenylquinoxalines, N-arylindoles, and 2-arylthiocromenones, these methods
did not overlap with previous publications.
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CHAPTER 1 LITERATURE OVERVIEWS
1.1 Introduction of quinazoline compounds
1.1.1 Biological activity of the quinazoline compounds
Quinazoline derivatives are the organic compounds, based on the quinazoline
framework, which is an aromatic heterocyclic structure containing nitrogen.
They were commonly present in nature and also could be synthesized. Most of
the quinazoline derivatives were yellow solids and poorly soluble in water. Most
of them demonstrated a wide range of biological activities, and quinazoline
derivatives have attracted more and more attention from researchers.
The pharmacological studies of quinazoline compounds dated back to 1940s.
Researchers have identified many biological activities, including anti-cancer,
anti-viral, anti-convulsant, anti-inflammatory, analgesic, and anti-oxidation.
Several applications of quinazoline derivatives are shown in Figure1.1.
Figure 1.1 Pharmacological significance of quinazolines4
1.1.2 Synthetic approaches to quinazoline derivatives
There were many methods to synthesize quinazoline compounds. In this, five
main methods were epitomized. First, 2-phenylquinazolines were synthesized via
a tandem reaction following sp3 C-H functionalization between benzylamines
and substituted 2-aminobenzophenones (Scheme 1.1). The second one was
dehydrocyclization between benzonitrile and 2-amino aryl ketone in the presence
of a transition metal catalyst (Scheme 1.2). The third one was
copper-catalyzed N-arylation-cyclization via Ullmann-type coupling reactions
(Scheme 1.3). Fourth, quinazolines would be synthesized via mediated oxidative
C(sp3)-C(sp2) bond formation (Scheme 1.4). The last one was the direct oxidative
amination of C(sp3)–H bonds (Scheme 1.5).
Scheme 1.1 Synthesis of 2-phenylquinazolines via a tandem reaction following
sp3 C-H functionalization
Scheme 1.2 Synthesis of quinazoline derivatives catalyzed by commercial
Ru3(CO)12/Xantphos/t-BuOK catalyst
Scheme 1.3 Synthesis of quinazoline derivatives via Ullmann-type coupling
reactions
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Scheme 1.4 Synthesis of quinazoline derivatives via I2/KI-promoted oxidative
C(sp3)-C(sp2) bond formation
Scheme 1.5 Synthesis of 4-phenylquinazoline via direct oxidative amination of
C(sp3)–H bonds
Because of the fascinating various biological and pharmacological properties of
nitrogen-containing molecules, the formation of crucial C-N bond has been
required. Therefore, the synthesis of quinazoline compounds would be always
considered an essential research topic.
1.2 Introduction of quinoxaline compounds
1.2.1 Biological activity of quinoxaline compounds
Among many nitrogen heterocycles, quinoxaline compounds have been
well-recognized as the essential substances, possessing a wide range of
applications in pharmaceutical, agricultural, and material industries. Over the last
two decades, quinoxalines have been known to play an important role in
medicinal science. Quinoxaline derivatives showed highly significant biological
activities such as anti-cancer, anti-HIV, antimicrobial, anti-inflammatory,
anti-tumor, anti-tuberculosis, antioxidant, and anti-Alzheimer's. In addition, they
CONCLUSIONS
This thesis has successfully developed the synthesis of 4-substituted quinazoline
derivatives via direct oxidative amination of C(sp3)-H bonds. The transformation
proceeded readily in the presence of an organic peroxide without any added
catalyst. The nature of the oxidant significantly affected the reaction, in which
tert-butyl hydroperoxide in decane emerged as the peroxide of choice. Several
nitrogen sources were explored, and ammonium acetate exhibited the best
performance. A plausible reaction mechanism was proposed, in which acetic acid
originating from ammonium acetate was essential for the formation of the
4-substituted quinazoline product. A variety of sp3 carbon sources could be
utilized for the reaction, including N,N-dimethylaniline, N-methylaniline,
N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone,
dimethyl sulfoxide, and N,N-dimethyl-1-phenylmethanamine. Several
4-substituted quinazoline derivatives were synthesized via this approach in good
yields. The fact that 4-substituted quinazolines derivatives were achieved via
peroxide-mediated direct oxidative amination of C(sp3)-H bonds without any
added catalyst would offer a complementary synthetic pathway to previous
protocols.
For the synthesis of 2-phenylquinoxalines, this thesis has reported a new
pathway, in which 2-phenylquinoxalines were obtained via the condensations
between o-phenylenediamines and phenylglyoxals in ethyl acetate without any
added catalyst. The relevant conditions of the reaction were exposed and a
possible mechanism has been composed. A wide range of substituents could be
utilized for the reaction. All quinoxaline derivatives were synthesized via this
pathway in good and excellent yields. The significant points of this protocol were
(1) metal-free, (2) green solvent, (3) short duration, (4) in room temperature, (5)
excellent yields, and (6) a wide range of applications. With these advantages, the
procedure of synthesizing 2-phenylquinoxaline derivatives of the thesis would
be applied in the field of organic synthesis and pharmaceuticals.
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TABLE OF CONTENTS
INTRODUCTION
CHAPTER 1. LITERATURE OVERVIEWS
CHAPTER 2. EXPERIMENTALS
CHAPTER 3. RESULTS AND DISCUSSIONS
CONCLUSIONS
TABLE OF CONTENTS
Pages
INTRODUCTION ...............................................................................................2
CHAPTER 1 LITERATURE OVERVIEWS ................................................3
1.1 Introduction of quinazoline compounds ..............................................3
1.2 Introduction of quinoxaline compounds..............................................5
1.3 Introduction of N-arylindole compounds.............................................7
1.4 Introduction of thiocromenone compounds.........................................9
1.5 Aims of this work ..............................................................................11
CHAPTER 2 EXPERIMENTALS...............................................................14
2.1 Materials and Instrumentations..........................................................14
2.2 Experimental procedures ...................................................................15
CHAPTER 3 RESULTS AND DISCUSSIONS..........................................16
3.1 Synthesis of quinazoline derivatives via peroxide-mediated direct
oxidative amination of C(sp3)-H bonds.........................................................16
3.2 Condensation of 1,2-phenylenediamines and dicarbonyl compounds in
ethyl acetate toward quinoxalines .................................................................17
3.3 Oxidative nucleophilic functionalization of nitrobenzene with N-H
bond to the synthesis of 1-(4-nitrophenyl)-1H-indoles.................................19
3.4 Elemental sulfur for the synthesis of 2-arylthiochromenones ...........20
CONCLUSIONS ...............................................................................................222
INTRODUCTION
Heterocyclic compounds are important compounds that exhibit an extensive
range of physical, chemical, and biological properties. Heterocyclic compounds
have been presented in numerous pharmacological areas, such as anti-cancer,
antibiotics, anti-inflammatory, anti-inflammatory and depression, anti-malarial,
anti-HIV, antibacterial, antifungal, antiviral, antidiabetic, herbicides, fungicides,
and insecticides. In addition, they have been considered in pharmaceutical
chemistry and agriculture. Accordingly, heterocyclic frameworks such as
quinazolines, quinoxalines, thiocromenones, and N-arylindoles have become the
interesting topics in organic synthesis.
Due to a wide range of applications of heterocyclic compounds in
pharmaceutical, cosmetic, and agricultural chemical industries, developing
effective processes to synthesize 5- and 6-membered heterocyclic compounds
such as quinazoline, quinoxaline, thiocromenone, and N-arylindole derivatives
have been highly demanding. However, the currently available reactions often
require transition metal catalysts and under extreme conditions. Therefore,
proposing new methods for the synthesis of heterocyclic compounds without the
use of any transition metal catalyst would be considered.
In the progression of studying documents, and investigating many reactions to
create heterocyclic compounds, the possible protocols for the synthesis of
4-phenylquinazoline, 2-phenylquinoxaline, 2-arylthiocromenone, and
N-arylindole derivatives without using transition metal catalysts were detected.
On that basis, the reaction conditions for each reaction were screened to
maximize yield, conducted survey products to develop plausible reaction
mechanisms, and extended the application scope of each response. As a result,
the thesis provided effective procedures to synthesize 4-phehylquinazolines,
2-phenylquinoxalines, N-arylindoles, and 2-arylthiocromenones, these methods
did not overlap with previous publications.
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CHAPTER 1 LITERATURE OVERVIEWS
1.1 Introduction of quinazoline compounds
1.1.1 Biological activity of the quinazoline compounds
Quinazoline derivatives are the organic compounds, based on the quinazoline
framework, which is an aromatic heterocyclic structure containing nitrogen.
They were commonly present in nature and also could be synthesized. Most of
the quinazoline derivatives were yellow solids and poorly soluble in water. Most
of them demonstrated a wide range of biological activities, and quinazoline
derivatives have attracted more and more attention from researchers.
The pharmacological studies of quinazoline compounds dated back to 1940s.
Researchers have identified many biological activities, including anti-cancer,
anti-viral, anti-convulsant, anti-inflammatory, analgesic, and anti-oxidation.
Several applications of quinazoline derivatives are shown in Figure1.1.
Figure 1.1 Pharmacological significance of quinazolines4
1.1.2 Synthetic approaches to quinazoline derivatives
There were many methods to synthesize quinazoline compounds. In this, five
main methods were epitomized. First, 2-phenylquinazolines were synthesized via
a tandem reaction following sp3 C-H functionalization between benzylamines
and substituted 2-aminobenzophenones (Scheme 1.1). The second one was
dehydrocyclization between benzonitrile and 2-amino aryl ketone in the presence
of a transition metal catalyst (Scheme 1.2). The third one was
copper-catalyzed N-arylation-cyclization via Ullmann-type coupling reactions
(Scheme 1.3). Fourth, quinazolines would be synthesized via mediated oxidative
C(sp3)-C(sp2) bond formation (Scheme 1.4). The last one was the direct oxidative
amination of C(sp3)–H bonds (Scheme 1.5).
Scheme 1.1 Synthesis of 2-phenylquinazolines via a tandem reaction following
sp3 C-H functionalization
Scheme 1.2 Synthesis of quinazoline derivatives catalyzed by commercial
Ru3(CO)12/Xantphos/t-BuOK catalyst
Scheme 1.3 Synthesis of quinazoline derivatives via Ullmann-type coupling
reactions
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Scheme 1.4 Synthesis of quinazoline derivatives via I2/KI-promoted oxidative
C(sp3)-C(sp2) bond formation
Scheme 1.5 Synthesis of 4-phenylquinazoline via direct oxidative amination of
C(sp3)–H bonds
Because of the fascinating various biological and pharmacological properties of
nitrogen-containing molecules, the formation of crucial C-N bond has been
required. Therefore, the synthesis of quinazoline compounds would be always
considered an essential research topic.
1.2 Introduction of quinoxaline compounds
1.2.1 Biological activity of quinoxaline compounds
Among many nitrogen heterocycles, quinoxaline compounds have been
well-recognized as the essential substances, possessing a wide range of
applications in pharmaceutical, agricultural, and material industries. Over the last
two decades, quinoxalines have been known to play an important role in
medicinal science. Quinoxaline derivatives showed highly significant biological
activities such as anti-cancer, anti-HIV, antimicrobial, anti-inflammatory,
anti-tumor, anti-tuberculosis, antioxidant, and anti-Alzheimer's. In addition, they
CONCLUSIONS
This thesis has successfully developed the synthesis of 4-substituted quinazoline
derivatives via direct oxidative amination of C(sp3)-H bonds. The transformation
proceeded readily in the presence of an organic peroxide without any added
catalyst. The nature of the oxidant significantly affected the reaction, in which
tert-butyl hydroperoxide in decane emerged as the peroxide of choice. Several
nitrogen sources were explored, and ammonium acetate exhibited the best
performance. A plausible reaction mechanism was proposed, in which acetic acid
originating from ammonium acetate was essential for the formation of the
4-substituted quinazoline product. A variety of sp3 carbon sources could be
utilized for the reaction, including N,N-dimethylaniline, N-methylaniline,
N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone,
dimethyl sulfoxide, and N,N-dimethyl-1-phenylmethanamine. Several
4-substituted quinazoline derivatives were synthesized via this approach in good
yields. The fact that 4-substituted quinazolines derivatives were achieved via
peroxide-mediated direct oxidative amination of C(sp3)-H bonds without any
added catalyst would offer a complementary synthetic pathway to previous
protocols.
For the synthesis of 2-phenylquinoxalines, this thesis has reported a new
pathway, in which 2-phenylquinoxalines were obtained via the condensations
between o-phenylenediamines and phenylglyoxals in ethyl acetate without any
added catalyst. The relevant conditions of the reaction were exposed and a
possible mechanism has been composed. A wide range of substituents could be
utilized for the reaction. All quinoxaline derivatives were synthesized via this
pathway in good and excellent yields. The significant points of this protocol were
(1) metal-free, (2) green solvent, (3) short duration, (4) in room temperature, (5)
excellent yields, and (6) a wide range of applications. With these advantages, the
procedure of synthesizing 2-phenylquinoxaline derivatives of the thesis would
be applied in the field of organic synthesis and pharmaceuticals.
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