Ministry of Higher Education
and Scientific Research
University of Baghdad
College of Science
Department of Chemistry
Synthesis and Characterization of new d i rivativ es of
9H- Carbazole
A thesis
Submitted to the College of Science University of Baghdad in Partial Fulfillment of the Requirements for t he
Degree of Master of Science in Organic Chemistry
By
Nahed Mahmood Ahmed
B.Sc . 2008/ Baghdad University
Supervised by
Prof. Suad M.Al-Araji
Prof. Assis. Dr.Ahmed W. Naser
1434 ‫ م‬2013
‫ھـ‬
‫ﻟﺧﯾر اﻟﺧﻠق و ل ﻣن طﺎﺑت اﻻﻧﻔس واﻻﻓواه ﺑﺎﻟﺻﻼة واﻟﺳﻼم ﻋﻠﯾﮫ اﻟﮭﺎدي اﻟﺑﺷﯾر)ﺻﻠﻰ‬
‫)ﷲ ﻋﻠﯾﮫ وﺳﻠم‬
‫ﻷﺑﻲ وأﻣﻲ‬
‫ﻟوﻻ دﻋﺎﺋﻛم ‪ ،‬ﺻﺑرﻛم ‪،‬ورﺿﺎﻛم ﻋﻧﻲ‬
‫‪ .‬ﻣﺎ وﻓﻘت ﻻﻣري‬
‫)ﻷﺧوﺗﻲ وأﺧواﺗﻲ وﺣﺑﯾﺑﺎﺗﻲ )ﻣرﯾم وﻣرام‬
‫واﻟﻰ ﻛل ﻣن وﻗف اﻟﻰ ﺟﺎﻧﺑﻲ ﺧﻼل ﻓﺗرة دراﺳﺗﻲ‬
‫اھدي اﻟﯾﻛم ﺟﮭدﻛم ﻣﻌﻲ‬
‫ﺷﻛرا ﻟﻛم‬
‫ﻧﺎھد ﻣﺣﻣود اﺣﻣد‬
‫ﺷﻛر وﺗﻘدﯾر‬
‫اﻟﺣﻣد واﻟﺷﻛر ﻣﺟﯾب اﻟدﻋﺎء ‪ ،‬اﻻﺻدق وﻋدا وﻋﻔوا ووﻓﺎء ﺑﻣﺎ ﯾﻛﺎﻓﺄ ﻋطﺎﯾﺎه وأﺗم اﻟﺻﻼة واﻟﺳﻼم ﻋﻠﻰ اﻟﺣﺑﯾب اﻟﻣﺻطﻔﻰ اﻟﻣﺧﺗﺎر‪ ،‬ﺳﯾدﻧﺎ‬
‫اﺑﺎ اﻟﻘﺎﺳم ﻣﺣﻣد ‪ ،‬اﻟراﺟﯾن ﺷﻔﺎﻋﺗﮫ ‪ ،‬ﺧﯾر اﻟﺧﻠق ‪ ،‬ﺧﺎﺗم اﻟرﺳل وﻣن ﻻ ﻧﺑﻲ ﻣن ﺑﻌده وﻋﻠﻰ آﻟﮫ وأﺻﺣﺎﺑﮫ اﻟطﯾﺑﯾن اﻟطﺎھرﯾن ﺑﻌدد ﻧﻌم ﷲ ظﺎھرة‬
‫‪ .‬وﺑﺎطﻧﺔ وﺑﻣﺎ ﺷﺎء وزاد‬
‫ﻟﻘد وﻓﻘﻧﻲ ﺳﺑﺣﺎﻧﮫ وﺗﻌﺎﻟﻰ إﻟﻰ أن أﺿﻊ ﺟﮭدي ﺑﯾن أﯾدﯾﻛم ذاﻛرًة ﻓﻲ أوﻟﮫ ﻓﺿل ﷲ رب اﻟﻌزة ان أﺗﻣﮫ ﻋﻠﻰ ﺧﯾر وﻟﯾﻛون اﻟﺣق ﺑﻌد اﻟﺣق ﺑﺎﻟذﻛر‬
‫ﺷﺎﻛرة ﺟﮭد وﺻﺑر أﺳﺗﺎذة واﻻم اﻟﺣﻧوﻧﺔ أ‪ .‬ﺳﻌﺎد ﻣﺻطﻔﻰ اﻻﻋرﺟﻲ ﻣﺗﻣﻧﯾﺔ ﻣن ﷲ ﻟﮭﺎ وﻟﻌﺎﺋﻠﺗﮭﺎ اﻟﺻﺣﺔ واﻟﻌﻣر اﻟﻣدﯾد‪ .‬وﺟﮭد اﻻﺳﺗﺎذ اﻟدﻛﺗور‬
‫‪.‬اﺣﻣد وﺣﯾد ﻧﺎﺻر واﺗﻣﻧﻰ ﻟﮫ اﻟﺻﺣﺔ واﻟﻌﻣر اﻟﻣدﯾد‬
‫واﻗدم اﻟﺷﻛر واﻷﻣﺗﻧﺎن اﻟﺟزﯾﻠﯾن اﻟﻰ ﻋﻣﺎدة ﻛﻠﯾﺔ اﻟﻌﻠوم‪/‬ﺟﺎﻣﻌﺔ ﺑﻐداد واﻟﻰ رﺋﺎﺳﺔ ﻗﺳم اﻟﻛﯾﻣﯾﺎء وﺳﻛرﺗﺎرﯾﺔ اﻟﻘﺳم وادارة اﻟﻣﺧزن‪ .‬ﻛﻣﺎ اﻗدم ﺷﻛري‬
‫‪.‬واﺣﺗراﻣﻲ اﻟﻰ ﺟﻣﯾﻊ اﺳﺗﺎذﺗﻲ اﻷﻓﺎﺿل ﻓﻲ ﻗﺳم اﻟﻛﯾﻣﯾﺎء ﻟﺗﻌﺎوﻧﮭم وﺗﺷﺟﯾﻌﮭم‬
‫‪.‬ﻛﻣﺎ اﺗﻘدم ﺑﺎﻟﺷﻛر اﻟﺟزﯾل ﻟﻠﺳت ﻣﻧﯾرة ﻓﻲ اﻟﻣﺧﺗﺑر اﻟﺧدﻣﻲ ﻟﺟﮭودھﺎ ﻓﻲ اﻧﺟﺎز اﻟﺗﺣﺎﻟﯾل اﻟطﯾﻔﯾﺔ‬
‫وأﺧﯾرا ﺷﻛرا ﻟﻌﺎﺋﻠﺗﻲ ‪ ،‬وﺟﻣﯾﻊ ﻣن ذﻛرﺗﮭم وﻣن ﻏﻔل اﻟﺑﺎل ﻋﻧﮭم ﻓﻌذرا ﻟﮭم‪ ،‬اﻧﺗم ﺟﻣﯾﻌﺎ ﺳﻧدي وذﺧري ﺣﻣﺎﻛم ﷲ ورزﻗﻛم ﻣن اﻟطﯾﺑﺎت ﺑﺎﻟدﻧﯾﺎ‬
‫‪.‬واﻻﺧرة ‪ ،‬وأدﻋوه أن ﯾوﻓﻘﻧﻲ ﻷرد وﻟو ﺟزءا ﻣن ﻓﺿﻠﻛم ﻋﻠﻲ‬
‫وﷲ وﻟﻲ اﻟﺗوﻓﯾق ‪ .....‬ﻧﺎھد ﻣﺣﻣود اﺣﻣد‬
CONTENTS
Subject
Page
List of content
I
List of Tables
IV
V,VI,
List of Figures
VII
List of Abbreviation
VIII
a bstract
IX
List of Contents
CHAPTER : INTRODUCTION
Page
1.1 Hetero cyclic compounds
1
1. 2 . Carbazole
1
1.3 Synthesis of 9H- carbazole
2
1.4 Reactions of carbazole
5
1.4.1:Nitratio n
5
1.4.2 : Acetylation
7
1.4.3 :Estrification
9
1.4.4 : Alkylation
12
1.4.5 : Schiff bases 12
1. 5. Biological activity of carbazole compounds
13
1.6. The Aim of this work
15
1.7. Future work 1 6
CHAPTER TWO: EXPERIMENTAL
2.1. Apparatus and Materials
17
2.1.1. Apparatus
17
2.1.2. Materials
18
2.2. Synthesis of 9- ethyl carbazole and its derivatives . 18
2.2.1 9-Ethyl carbazole( 1 )
18
2.2.2 3-Acetyl-9H-carbazole ( 2 )
18
2.2.3 Synthesis of 3-(1-oxopropen -1-yl)9-ethyl carbazole derivatives 3(a-h)
19
2.2.4. Synthesis of 3-(1-acetyl -5-aryl pyrazolin-3-yl) 9-ethyl carbazole derivatives 4(a-h)
20
2.2.5. Synthesis of 3-(1-phenyl-5-aryl pyrozoline-3-yl)9-ethyl carbazole derivatives 5 (a-h)
22
2.2.6. Synthesis of 3-(2-amino-6-aryl-4-pyrimidinyl)9-ethyl carbazole derivatives
23
6 (a-h)
2.2.7. Synthesis of 9-nirtosyl carbazole compound (7 )
24
2.2.8.The reduction of 9-nitrosyl carbazoleto give 9-amino carbazole compound (8 )
24
2.2.9. Synthesis of 9-amide carbazolederivatives 9 (a,b)
25
2.2.10 Synthesis of Schiff bases derivitives 10 (a-e)
25
CHAPTER THREE : R ESULTS AND DISCUSSION
3.1. 9-ethyl carbazole [1] 2 7
3.2. 3- acetyl - 9 – ethyl carbazole [2] 27
3.3. 3 – (3 – phenyl – 1 – ox o propen – 1 – y1) 9 – ethyl carbazole derivatives 3(a –h) 3 3
3.3.1. 3 – (3 – phenyl – 1 – ox o propen -1 – y1) 9 – ethyl carbazole(3a) 3 5
3.3. 2 3- (3 – o – methoxy phenyl – 1 – ox o propen – 1 – y1)(3b). 3 5
3.3.3 3- (3- o - nitro phenyl -1 - oxo propen-1-y1)9- ethylcarbazole(3c) 3 6
3.3.4 3-[3-( p – chlorophenyl ) – 1 – ox o propen] 9 – ethyl carbazole(3d) 3 6
3.3.5 3-[ 3 – ( p – bromo phenyl ) – 1 – ox o propen– 1 – y1 ] 9 – ethyl carbazole(3e) 37
3.3.6 3 – [ 3 – ( p- N,N – dimethyl amino phenyl ) – 1 – ox o propen – 1 – y1] 9 – ethyl carbazole(3f) 37
3.3.7 3 – [3 – (2,4 – dihydroxy phenyl ) – 1 – ox o propen – 1 – y1] 9 – ethyl carbazole (3 g) 3 8
3.3.8 3 – [ 3-(5 – phenyl ) – 1 – ox o pentadiene – 1 – y1) 9 – ethyl carbazole(3h) 3 8
3.4. 3-( 1 -acetyl -5-aryl pyrazolin-3-yl) 9-ethyl carbazole derivatives 4(a-h) 51
3.4.1. 3-( 1 - a cetyl-5-phenyl pyrozolin-3-yl)9-ethyl carbazole[4a] 53
3.4.2. 3-( 1 -acetyl-5-( o -methoxy phenyl) pyrozolin-3-yl)9-ethyl carbazole [4b] 53
3.4.3 . 3-( 1 -acetyl-5-( o -nitro phenyl) pyrozolin-3-yl)9-ethyl carbazole[4c] 5 4
3.4.4. 3-( 1 -acetyl-5-( p -chloro phenyl) pyrozolin-3-yl)9-ethyl carbazole[4d] 5 4
3.4.5. 3-( 1 -acetyl-5-( p -bromophenyl) pyrozolin-3-yl)9-ethyl carbazole [4e] 5 5
3.4.6. 3-( 1 -acetyl-5-( p- N,N-dimethylamino phenyl) pyrozolin-3-yl)9-ethyl carbazole [4f] 5 5
3.4.7. 3-( 1 -acetyl-5-(2,4-dihydroxy phenyl) pyrozolin-3-yl)9-ethyl carbazole [4g]
56
3.4.8. 3-( 1 -acetyl-5-styryl pyrozolin-3-yl)9-ethyl carbazole [4h]. 5 6
3.5. 3-(1-phenyl-5-Aryl pyrozoline-3-yl)9-Ethyl carbazole derivatives 5(a-h)
72
3.5.1 . 3- (1,5- diphenyl pyrazolin-3-yl )9-ethyl carbazole [5a] 74
3.5.2. 3-(1-phenyl-5-( o -methoxy phenyl) pyrozoline-3-yl)9-ethyl carbazole [ 5b ]
74
3.5.3. 3-(1-phenyl-5-( o -nitrophenyl) pyrozolin-3-yl)9-ethyl carbazole [5c] 7 5
3.5.4. 3-(1-phenyl-5-( p -chlorophenyl) pyrozolin-3-yl)9-ethyl carbazole [5d] 7 5
3.5.5. 3-(1-phenyl-5-( p -bromophenyl) pyrozolin-3-yl)
76
9-ethyl carbazole [5e] .
3.5.6. 3-(1-phenyl-5-( p- N,N-dimethyl amino phenyl) pyrozolin-3-yl)9-ethyl carbazole [5f] 7 6
3.5.7. 3-(1-phenyl -5-(2,4-dihydroxy phenyl) pyrozolin-3-yl)9-ethyl carbazole [5g] 7 7
3.5.8. 3-(1-phenyl-5-styrenyl pyrozolin-3-yl)9-ethyl carbazole [5h]
77
3.6. Synthesis of 3-(2-Amino-6-Aryl-4-Pyrimidinyl)9-Ethyl carbazole derivatives 6(a-h)
95
3.6.1 3-(2-amino-6-phenyl-4-pyrimidinyl)9-ethyl carbazole [6a] 9 7
3.6.2. 3-(2-amino-6-2-methoxy phenyl-4-pyrimid inyl)9-ethyl carbazole [6b] 9 7
3.6.3. 3-(2-amino-6-2-nitro phenyl-4-pyrimidinyl)9-ethyl carbazole[6c] 9 8
3.6.4. 3-(2-amino-6-4-chloro phenyl-4-pyrimidinyl)9-ethyl carbazole[6d] 9 8
3.6.5. 3-(2-amino-6-4-bromo phenyl -4-pyrimidinyl)9-ethyl carbazole [6e] 9 9
3.6.6. 3-(2-amino-6-N,N-dimethyl amino phenyl-4-pyrimidinyl)9-ethyl carbazole[6f] 9 9
3.6.7. 3-(2-amino-6-2,4-dihydroxy phenyl-4-pyrimidinyl)9-ethyl carbazole [6g] 100
3.6.8. 3-(2-amino-6-styrenyl-4-pyrimidinyl)9-ethyl carbazole[6h] 100
3.7. Synthesis of 9- nitrosyl carbazole compound ( 7 ) 11 8
3.8. Synthesis of 9- amino carbazole compound ( 8 ) 1 20
3. 9 . Synthesis of 9-amide carbazole derivatives 9 (a ,b ) 122
3.10. Synthesis of the Schiff-bases derivatives 10 (a-e) 127
List of Scheme
Subject
Page
Scheme 1: Reaction mechanism for the formation of compounds 3(a-h) 3 4
Scheme 2 : Reaction mechanism for the formation of compounds 4(a-h)
52
Scheme 3: Reaction mechanism for the formation of compounds 5(a-h) 73
Scheme 4 : Reaction mechanism for the formation of compounds 6 (a-h) 96
Scheme 5:Reaction mechanism for the reduction of 9- nitrosyl carbazole 1 20
Scheme 6 : Reaction mechanism for the formation of 9-amide carbazole derivatives 9 (a,b) 1 22
Scheme 7 : Reaction mechanism for the formation o f the Schiff-bases derivatives 10 (a-e) 12 7
List of Table
Table
Title
Page
3-1 Scientific name and chemical structure 3(a-h)
39
3-2 Physical properties of compounds 3(a-h)
40
3-3 Infrared absorption data of compounds 3(a-h)
41
3-4 Scientific name and chemical structure 4(a-h)
57
3-5 Physical properties of compounds 4(a-h)
58
3-6 Infrared absorption data of compounds 4(a-h)
59
3-7 UV absorption data of compounds (4a,4b,4d,4e,4g,4h)
68
3-8 Scientific name and chemical structure 5(a-h)
78
3-9 Physical properties of compounds 5(a-h)
79
3-10 Infrared absorption data of compounds 5(a-h)
80
3-11 UV absorption data of compounds 5(a-h)
90
3-12 Scientific name and chemical structure 6(a-h)
101
3-13 Physical properties of compounds 6(a-h)
102
3-14 Infrared absorption data of compounds 6(a-h)
103
3-15 UV absorption data of compounds 6(a-h)
113
3-16 Scientific name and chemical structure of 9-amide carbazole
derivatives 9 (a,b)
1 23
3-17
physical properties of 9-amide carbazole derivatives 9 (a,b) 1 24
3-18 Infrared absorption data 9-amide carbazole derivatives 9 (a,b)
1 24
3-19 Scientific name and chemical structur e of Schiff-bases derivatives
10 (a-e)
12 9
3-20 Physical properties o f Schiff-bases derivatives 10 (a-e)
1 30
3-21 Infrared absorption data for Schiff-beses derivatives 10 (a-e)
1 31
List of Figures
Figure
Title
Page
1
FTIR spectrum of compound [1]
29
2
FTIR spectrum of compound [ 2 ]
30
3
H-NMR spectrum of compound [2]
31
4
UV spectrum of compound [ 1 ]
32
5
UV spectrum of compound [2]
32
6
FTIR spectrum of compound [ 3 a ]
42
7
FTIR spectrum of compound [ 3 b ]
43
8
H-NMR spectrum of compound [3b]
44
9
FTIR spectrum of compound [ 3 c ]
45
LIST OF ABBREVIATIONS
Abbreviation
Phrase
IUPAC
International Union of pure and
Applied Chemistry
FT-IR
Fourier transform infra-red
NMR
Nuclear magnetic resonance
UV
Ultra violet
TLC
Thin layer chromatography
Ar
Aryl
%
Percentage
0C
Centigrade
m.p.
Melting point
s(in FT-IR) Strong
m (in FT-IR) Medium
str.
Stratching
g
Gram
l
Liter
M.Wt.
Molecular weight
λ max
Wave length maximum
ml.
Militer
hr.
Hour
Abstract
Carbazole and 9-ethyl carbazole derivatives are an important type of nitrogen containing aromatic heterocyclic
compounds which have attracted considerable of medicinal chemists due to their antimicrobial activities. For
this purpose new carbazole derivatives were synthesized . These heterocyclic compounds were synthesized
in two parts .The first part was started from 3-(ox o alken-1-yl)9-ethyl carbazole derivatives 3(a-h) which
obtained from the re a ction of 3-acetyl-9-ethyl carbazole with different aromatic aldehyde in presence of 1%
sodium hydroxide . React ion one of 3(a-h) with hydrazine hydrate in acetic acid gave 3-( 1 -acetyl -5-aryl
pyrazolin-3-yl) 9-ethyl carbazole derivatives 4(a-h). Treating p henyl hydrazine in presence of piperidine with
3(a-h) yield ing 3-(1-phenyl-5-aryl pyrozoline-3-yl)9-ethyl carbazole derivatives 5(a-h) .The reaction 3(a-h) with
guinidine carbonate afford 3-(2-amino-6-aryl-4-pyrimidinyl)9-ethyl carbazole derivatives 6(a-h). The first part i n
order to obtain N-NH 2 in carbazole instead of NH 2 , carbazole were reacted with NaNO 2 , conc. HCl gave
nitrosyl compound (7) which was treated with zinc powder and acetic acid at 0 0 C to give 9-amino carbazole
(8) . N-(9H-Carbazole -9-yl ) acet amide derivitives (9a) and (9b) were prepared by reaction 9-amino carbazole
with acetyl chloride and benzoyl chloride respectively . which was treated with some aromatic aldehydes to
give Schiff - bases 10(a-e) [N-Benzylidine-9H- carbazole-9-amine derivitives]
All steps of the prepared compounds were summarized in scheme below , a ll the synthesized comp ounds
were characterized by spectroscopic methods namely FT-IR, U.V and 1 H-NMR (for some of them ) and with
thin layer, and m.p.
1.1 Hetero cyclic compounds
Hetero cyclic compounds are cyclic compounds in which the ring atoms are of carbon and some
other element , containing nitrogen oxygen and sulfer are by far the most common , but other atoms
such as boron phosphorous , or silicon compound also be members of heterocyclic ring . some non
- aromatic heterocyclic and some aromatic heterocyclic (1-4)
1 . 2 Carbazole
Carbazole is an aromatic heterocyclic organic compound . It has tricyclic structure , consisting of
two six – membered benzene rings fused on either side of a fi ve - membered nitrogen - containing
ring . The compound structure is based on the indole structure but in which a second benzene ring
is fused into the five- membered ring at the 2-3 position of indo le (equivalent to the 9 a-4a double b
ond in carbazole respectively) ( 5 )
Carbazole is one of organic hetero cyclic compounds containing adibenzopyrrole, also known as 9azo fluorine (6) .
1.3 Synthesis of 9H- carbazole :
C lassic laboratory organic synthesis for carbazole is the Borsche- Drechsel cyclicization ( 7,8 )
Borsche-Drechsel method
Phenyl hydrazine is condense d with cyclohexanone to the corresponding imine , then the used of
hy drochloric acid as catalist . Rearregment reaction and ring- closing reaction to
tetrahydrocarbazole . In one modification, both steps are rolled into one by carrying out the
reaction in acetic acid ( 9 ) . In the third step this compound is oxidized by red lead to carbazole
itself .
A second classic laboratory chemical reaction used to synthesize carbazole from naphthols and
aryl hydrazines using sodium bisulfite.
The reaction is named after Hans T heoder Bucherer (1869-1949 ) w as a German chemist ( 10 )
German chemist method
The third method for the synthesis of carbazole is the Graebe - Ullmann reactio n .
In the first step, an N - phenyl-1-2-diamino benzene (N-phenyl-o-phenylenediamine) is converted
into adiazonium salt which in s pontan eously froms a 1,2,3-triazole . The triazole is unstable and at
elevated temperatures nitrogen is set free and the carbazole is formed ( 11,12 )
Graebe - Ullmann reaction
Modified methods for the synthesis of carbazole from phenothiazine . An efficient method for the
ring contraction of phenothiazine(1) to make carbazole (2) would prove useful because most region
chemically controlled synthesis routes to phenothiazine derivatives could then be directly applied to
the corresponding carbazoles. Although many examples of the hydride sulfurization of phenothiazine
to make diphenylamine have been reported, such less effort has focused on this contraction (13 )
Modified method for the synthesis of carbazole from phenothiazine
1.4 Reactions of carbazole
1 . 4. 1:Nitration
In this reaction the carbazole was react with alkyle halide [RBr] to give 9- alkyl carbazole (3 ) and
then, compound (3 ) was reacted with Cu(NO 3 ) 2 to give 3,6 - dinitro - 9 - alkyl carbazole (4 ) (1 4 )
Scheme(1)
Nit ration in acetic acid and acetic anhydri de provided the dinitro compound ( 5 ) Finally, palladium
catalyzed hydro genation of compound (1) led to diamine( 6 ).
Scheme ( 2 ):- Synthesis of 1,8-diamino-3,6-di n- butyl carbazole
1 . 4.2 : Acetylation
In this reaction the carbazole reacted with acetyl chloride in the presence of AlCl 3 and dichloro
ethane to produce 3-acetyl-9H-carbazole (1 5 )
The acetylation reaction of carbazole
While the diacetylation of carbazole using butyryl chloride in dichloro ethane afforded 3,6- dibutryl
carbazole ( 7 ) in 42% yield. Subsequent C leminson reduction yielded dibutylcarbazole ( 8 ) in yield
50% . The reaction shown in Scheme ( 3 ) as following:- (1 6 )
Scheme( 3 ): Diacelytion reaction.
According to the mechanism of Friedel-C rafts acylation ( 17 ) The complex comprised of catalyst
aluminum chloride and the acylation product must be broken down by the addition of water after the
reaction . The aluminum chloride in the formed complex could not longer catalyze acylation. So, in
acylation reactions, theoretically , the dosage of aluminum chloride should be at least equimolar to
the raw material, actually , it was 10-50% in excess of the equimolar dosage in many cases (18,19
)
Scheme ( 4 ): Synthesis of 3-acetyl -6- (O-methyl benzoyl )-N-ethyl carbazole
In scheme ( 5 ) synthesis of new compounds 9-ethyl-9-carbazole -3- carbaldehyde ( 11 ) was
obtained starting from ethylation of carbazole followed by treating the resu l ting 9- ethyl-9Hcarbazole with POCl 3 in DMF v ia V ilsmeier- Haack reaction ( 2 0 ) in 65% yield . compound ( 11 )
was further treated with NBS (N- bromo succini m ide ) to give 6-bromo -9-ethyl – 9H- carbazole –
3- carbaldehyde ( 12 ) .
Scheme ( 5 ): Synthesis of 6-bromo -9- ethyl -9H- carbazole -3- carbaldehyde from ethyl carbazole
1 . 4.3 : Estrification
In this reaction treatment of carbazole with ethyl chloro acetate gave ethyl- 9H- carbazole -9-yl
acetate ( 13 ). The acetate ester derivative was transformed into the 2-(9H-carbazole -9-y l )
acetohydrazide ( 14 ) through trea tment with hydrazine hydrate (2 1 ) as the following in Scheme ( 6
) :-
Scheme( 6 ): Synthetic protocol to synthesis compounds ( 1 3 , 1 4 )
A new carbazole - containing polymer has been synthesized for further photophysical studies .
Efficient synthesis of the substituted methyl methacrylate (18) has been accomplished via
microwave assisted synthesis of 1-chloro-4-carboxy-5,6,7,8-tetrahydro carbazole (15) followed by
further steps , such as reduction of the 4-substituted methyl carboxylate (16) , dechlorination of the
ring . T he reaction of the 4-hydroxymethyl-9-ethyl (17) with methylacryloylchloride ( 2 2 )
Scheme ( 7 ):- Estrification reaction of 9-ethyl carbazole
1 .4 .4 –Alkylation :In this reaction the carbazole was reacted with bromoethane in the presence of potassium
hydroxide in DMF as a solvent to give -9-ethyl carbazole (2 3 ) .
Ethyl carbazole will be interest for preparation of different derivatives . N-Ethyl carbazole is
used in the synthesis of useful dyes and pigment . It is used as one of the main constituents in the
synthesis of pigment , violet and its demand in printing ink ( 2 4 )
1.4.5- Schiff bases
In 1864 the German chemist Hugo Schiff described the formation of N- substituted imines so they
are called (Schiff base) ( 25 ) .Azomethine group (C= N) containing compounds, typically known as
Schiff , s bases, have been synthesized via condensation of primary amines with active carbonyls
(2 6 ) . Schiff bases are the important compound owing to their wide range of biological activities
and industrial application (2 7 ) . They have been found to possess the pharmacological activities
such as antimalarial ( 2 8 ) , anticancer ( 2 9 ) ,antibacterial ( 30 ) and antiviral ( 31 ) .
1.5. Biological activity of carbazole compounds
Carbazole , and especially heterocycl ic - containing carbazole derivatives, are embodied in many
nat urally occurring products ( 3 2 -3 4 ) and display abroad spectrum of useful biological activities
such as antitumor , anti b itotic , and antioxida nt activities ( 3 5 - 3 7 ) . They are also widely used as
building blocks for new organic materials ( 3 9 - 4 1 ) , and play avery important role in e lectroactive
and photoactive devices ( 4 2 - 4 5 ) .Therefore , a number of methodologies for the constraction of
heterocycle - containing carbazoles have been reported in recent years ( 4 6 - 50 ) most
heterocycle - containing carbazoles reported in the literature comprise a common heterocyclic ring
moiety fused with a carbazole ring, such as pyridocarbazoles ( 5 1 ,5 2 ) , thienocarbazoles ( 5 3 ,5 4 )
, pyranocarbazoles , pyrrolocarbazoles ( 5 5 , 5 6 ) , indolocarbazoles ( 5 7 - 5 9 ) and synthetic
analogues there of . However , there are very few reports in which the heterocyclic moiety is
substituted with a carbazole unit . Hence the synthesis of such compounds in desirable ( 60 , 6 1 )
on the other hand.The benzofuran derivatives are an important class of heterocyclic compounds
that are known to possess important biological properties ( 6 2 ,6 3 ) . Especially , recent studies
have shown that some benzofuroyl- based compounds display important biological properties as
antimicrobial ( 6 4 ) , anticonvulsant , anti - in flommatory ( 6 5 ) , anti- tumor ( 6 6 ) and antifungal ( 6
7- 6 9 ) activities. On account of these findings , extensive synthetic efforts have been devoted to
the development of more noval and interesting benzofuroyl - based compounds ( 70 -7 5 ) Nitrogen containing heterocycles are avery important group of organic compounds because of their mide
application in medicine, agriculture , and technology . ( 76 )
1.6. The Aim of this work
1. Synthesis
of some new derivatives of 9-ethyl carbazole at position three such as
b. 3-( 1 - A cetyl -5-aryl pyrazolin-3-yl)
9-ethyl carbazole derivatives 4(a-h).
c. 3-(1- P henyl-5- a ryl-4-py rozoline-3-yl)9-ethyl carbazole derivatives 5(a-h).
(c) 3-(2- A mino-6- a ryl-4-Pyrimidinyl)9 -ethylcarbazole
derivatives 6(a-h) . .
2- Synthesis of some new derivatives of carbazole substituted at position nine such as
(a) N-benzylidene -9H- carbazole -9-amine derivitives compounds 9(a-e) .
(b) N-(9H-carbazole -9-yl) acetamide derivatives compounds 10(a,b) .
1.7. Future work
1-Synthesis of some derivatives of 9-ethyl carbazole via cyclization the ox o propen compo unds
with urea and thioure.
2-Reaction of the ox o propen compound with active methylene group.
3-Synthesis of some β -lactam , oxaze p ine and imidazolidine derivatives by the cyclization of
Schiff-bases with chloro acetyl chloride , acid anhydride and α-amino acids respectively.
2.1 Apparatus and Materials :
2.1.1. Apparatus
1. FT-IR
Spectrophotometer :
IR spectra were recorded on a [SHIMADZU] FT-IR 8400 s spectrophotometer ; Solid sa mples were
run in KBr disk in Baghdad university.
1. Nuclear
Magnetic Resonance Spectrophotometer :
1 H-NMR spectra were recorded on ultra shield 300 MHz with tetramethylsilane as internal
standard , company : Bruker, origin : Switzerland . In Iran.
1. Ultraviolet
Spectrophotometer :
UV spectra were recorded on UV-Visible Spectrophotometer [SHIMADZU] UV-160A were
preformed by Baghdad University College of Science , Chemistry Department.
1. Melting point
apparatus :
Melting point were determined in a [ Gallen Kamp ] melting point apparatus with sample contained
in open capillary glass tube in an electrically heated metal block apparatus , and were uncorrected
.
1. Thin Layer
chromatography :
TLC were performed on pre-coate d plastic sheet with 0.25mm layer of silica-gel F254 . Spots
were detected with iodine vapour .
2.1.2 Material s :
All chemicals used were supplied from BDH company , Merck , Fluka and were used without further
purification .
2.1 . Synthesis of 9- ethyl carbazole and its derivatives .
2.2.1 9-E thyl carbazole ( 1 ) ( 77 )
Carbazole (20 g, 119.6 mmol), potassium hydroxide (20.13 g, 358.8 mmol) and bromoethane (39.1
g,358.8mmol) were dissolved in DMF (200 ml). The mixture was stirred overnight at 60 0 C.After
pouring into brine, and washing, th e mixture was extracted by methylene c hloride. The organic
extracts were dried with MgSO4 and concentrated by rotary evaporation. Purification of solid
residue by recrystallization from ethanol gave a white solid ( 85.6% , m.p=6 0 -6 2 0 C ).
2.2.2 3-A cetyl-9H-carbazole ( 2 ) ( 78 )
A mixture of ethyl carbazole (2 gm,0.05mol) , dichloro ethane (7 ml) , aluminium chloride
(4.6gm,0.035 mol ) was st irred in (0-5 0 C ) mean while and and the other solution of acetyl
chloride (6.5 ml,0.05mol) and dichloroethane (6ml) was added a dropwise over 0.5 hr.Upon
completion of the addition, the mixture was kept at (0-5 0 C ) for an additional 0.5hr. The reaction
mixture was then allowed to warm to room temperature and stirred for 0.5 hr.. T he mixture was
poured into water. After the phase separation, the organic layer was successively washed with
saturated sodium carbonate solution and water to neutralization and dried over Na 2 SO 4 . T he
solvent was completely evaporated under reduced pressure and the residue was extracted with
acetone (3x20ml).The combined acetone solution was cooled in the refrigerator to maintain a
tempreture of 0 0 C and kept for 12hr . The completion of the raction was checked by TLC
(benzene). The precipitate obtained was filtered and recrystallized from ethanol to give compound
(2) [52.5% , m.p.= 114 - 116 0 C]
2.2.3 Synthesis of 3-( 1- O x o propen -1-yl)9- e thyl carbazole derivatives 3 ( a-h ) ( 79 )
General procedure :A mixture of 3-acetyl-9-ethyl carbazole (3gm,0.013m ol) and ( 0.014mol) of appropriate aromatic
aldehyde namely (benzaldehyde,o-methox y benzaldehyde, o-nitrobenzaldehyde, pchlorobenzaldehyde, p - bromobenzaldehyde , cinnamyl aldehyde , pN,Ndimethylaminobenzaldehyde,2,4-dihydroxybenzaldehyde ) in (80 ml) of (95%) ethanol and (1.5
ml) of (1% NaOH) was refluxed for (5hr.) .The completion of reaction was checked by TLC
(benzene : chloroform) (3:2). The mixture was poured in to icewater . T he precipitate obtained
filtered and r ecrystallized from [ethanol-water] (3:1) to give compounds 3(a-h) respectively .
Table(3-1) shows the name of chemical structure compounds 3(a-h). T he following compounds
were prepared as described above . The physical properties are lis ted in [Table (3-2)].
3-(3- P henyl-1-ox o propen-1-yl)9-Ethyl carbazole ( 3a ) .
Yield 43%, m.p. 110-112 0 C
3-(3- ( o - M ethoxy phenyl ) -1-o xo propen-1-yl)9-ethyl carbazole ( 3b ) .
Y ield 51 % ,m.p. 97-99 0 C
3-(3- ( o - N itro phenyl ) -1-ox o propen-1-yl)9-ethyl carbazole ( 3c ) .
Yield 39 %, m.p. 175 - 177 0 C
3-(3- ( p - C hloro phenyl ) -1-ox o propen-1-yl)9-ethyl carbazole ( 3d ) .
Yield 37% , m.p. < 240 0 C
3-(3- ( p - B romo phenyl ) -1-ox o propen -1-yl)9-ethyl carbazole ( 3e ) .
Yield 39% ,m.p. 190-192 0 C
3-(3- ( p - N,N- D imethyl amino phenyl ) -1-ox o propen -1-yl)9-ethyl carbazole
( 3f ) .
Yield 34% , m.p. 180-182 0 C
3-(3- ( 2,4- D ihydroxy phenyl ) -1-ox o propen -1-yl)9-ethyl carbazole ( 3g ) .
Yield 44% , m.p. 250-252 0 C
3-( 3 - (5- P henyl ) -1-oxo-2,4- pentadiene-1-yl)9-ethyl carbazole (3h ) .
Yield 50% , m.p. 210-215 0 C
2.2.4. Synthesis of 3-( 1 - A cetyl -5-aryl pyrazolin-3-yl) 9-ethyl carbazole derivatives 4 (a-h) ( 80 )
G eneral procedure :To a solution of ox o alkene derivatives 3 (a -h ) ( 0.001mol) in ethanol (20ml), hydrazine hyd rate
(50%)(0.4ml) was added , the reaction mixt ure was refluxed for (5hr.).The completion of the
reaction was checked by TLC using ethyl acetate as eluent .A fter cooling the reaction mixture was
acidified with (2ml) glacial acetic acid . The formed precipitate was filtered and recrystallized from
ethanol to give compounds 4 ( a -h ) respectively . Table(3-4) shows the name of chemical structure
compounds 4(a-h) . The physical properties are listed in [Table (3- 5 )].
3-( 1 - A cetyl-5-phenyl pyrozolin-3-yl)9-ethyl carbazole (4a ) .
Yield 60% , m.p. 190 0 C
3-( 1 - A cetyl-5-( o -methoxy phenyl) pyrozolin-3-yl)9-ethyl carbazole (4b)
Yield 70% , m.p. 115 0 C
3-( 1 - A cetyl-5-( o -nitro phenyl) pyrozolin-3-yl)9-ethyl carbazole (4c) .
Yield 40%, m.p. 183 0 C
3-( 1 -A cetyl-5-( p -chloro phenyl) pyrozolin-3-yl)9-ethyl carbazole (4d) .
Yield 70% , m.p. 264 0 C
3-( 1 - A cetyl-5-( p -bromophenyl) pyrozolin-3-yl)9-ethyl carbazole (4e) .
Y ield 50% , m.p. 170 0 C
3-( 1 - A cetyl-5-( p - N,N -dimethylamino phenyl) pyrozolin-3-yl)9-ethyl carbazole (4f) .
Yield 50% , m.p. 195-197 0 C
3-( 1 - A cetyl-5-(2,4-dihydroxy phenyl) pyrozolin-3-yl)9-ethyl carbazole (4g) .
Yield 85%, m.p. 260 0 C
3-( 1 - A cetyl-5- styryl pyrozolin-3-yl)9-ethyl carbazole (4h) .
Yield 80 % , m.p. 240 0 C
2.2. 5 . Synthesis of 3-(1- P henyl-5- a ryl p yrozoline-3-yl)9- e thyl carbazole derivatives 5 (a-h) ( 81 )
General procedure:To a solution of ox o alkene3 (a -h ) ( 0.005mol),phenyl hydrazine ( 0.007mol) in ethanol (80ml) and
few drops of piperidine was added, then refluxed for (3hr.),after cooling the precipitate was formed
filtered , dried and the purity of product was checked by TLC with chloroform as eluent,
recrystallized from (ethano l-water ) (3:1) to give compound s 5 (a -h ) . Table(3-8) shows the name
of chemical structure compounds 5(a-h) T he following compounds were prepared as described
above . The physical properties are listed in [Table (3- 9 )].
3- [ 1 ,5 - Di phenyl-5-aryl pyrozoline-3-yl ] 9-ethyl carbazole (5a) .
Yield 28% ,m.p. 160-162 0 C
3- [ 1- P henyl-5- ( o -methoxy phenyl ) pyrozoline-3-yl ] 9-ethyl carbazole (5b) .
Yield 42% , m.p. 130 - 132 0 C
3- [ 1- P henyl-5- ( o -nitro phenyl ) pyrozolin-3-yl ] 9-ethyl carbazole (5c)
Yield 33 % , m.p. 196-198 0 C
3- [ 1- P henyl-5- ( p -chloro phenyl ) pyrozoline-3-yl ] 9-ethyl carbazole (5d)
Yield 25 % , m.p. 272 0 C
3- [ 1- P henyl-5- ( p -bromo phenyl) pyrozolin-3-yl] 9-ethyl carbazole (5e)
Yield 67 % , m.p. 195 0 C
3-[ 1- P henyl-5- ( p - N,N -dimethyl amino phenyl ) pyrozolin-3-yl] 9-ethyl carbazole (5f)
Yield 25 % , m.p. 210-212 0 C
3- [1- P henyl -5- (2,4-dihydroxy phenyl ) pyrozolin-3-yl ] 9-ethyl carbazole (5g)
Yield 58 % ,m.p. 150 0 C
3- [ 1- P henyl-5-styrenyl pyrozolin-3-yl ] 9-ethyl carbazole (5h)
Yield 75 % , m.p. 260 0 C
2.2.6. Synthesis of 3-(2- A mino-6- a ryl-4- p yrimidinyl)9- e thyl carbazole derivatives 6 (a-h): ( 82 )
General procedure :To a refluxed mixture of 3(a-h) ( 0.005mol) and guanidine carbonate (0.54gm,0.005mol) in ethanol (
50 ml), NaOH 40% (2.5ml) was added through 3hr. Then continued for 6hr. The completion of the
reaction was checked by TLC (ethylacetate).The precipitate was formed after colling , filtered and
wash with cold ethanol , dried and r ecrystallized from DMF- w ater (3:1) to give the compounds 6 (a
-h) . Table(3-12) shows the name of chemical structure compounds 6(a-h)T he following compounds
were prepared as described above . The physical properties are listed in [Table (3- 13 )]
3- [ 2- A mino-6-phenyl-4-pyrimidinyl ] 9-ethyl carbazole (6a)
Yield 80 % ,m.p. 250-252 0 C
3- [ 2- A mino-6- ( o -methoxy phenyl ) -4-pyrimidinyl ] 9-ethyl carbazole (6b)
Yield 75 % , m.p. 230 0 C
3- [ 2- A mino-6- ( o -nitro phenyl ) -4-pyrimidinyl ] 9-ethyl carbazole (6c)
Yield 50 % , m.p. 234-236 0 C
3- [ 2- A mino-6- ( p -chloro phenyl ) -4-pyrimidinyl ] 9-ethyl carbazole (6d)
Yield 45 %, m.p. 258-260 0 C
3- [ 2- A mino-6- ( p -bromo phenyl ) -4-pyrimidinyl ] 9-ethyl carbazole (6e)
Yield 60 % , m.p. 220 0 C
3- [ 2- A mino-6- ( p - N,N -dimethyl amino phenyl ) -4-pyrimidinyl ] 9-ethyl carbazole (6f)
Yield 55 % , m.p. 280 0 C
3- [ 2- A mino-6- ( 2,4-dihydroxy phenyl ) -4-pyrimidinyl ] 9-ethyl carbazole (6g)
Yield 40 % , m.p. 266-268 0 C
3- [ 2- A mino-6-styrenyl-4-pyrimidinyl ] 9-ethyl carbazole (6h)
Yield 50 % , m.p. 275 0 C
2.2.7. Synthesis of 9- N irtosyl carbazole compound ( 7 ) ( 83 )
A mixture of c arbazole (10g , 0.05 mole) and sodium nitrite (4.2 g ) in (150 ml) of ethanol was reflux
ed for 2 hr.. After co o ling (12ml) of concentrated (HCl) drop-wise was added. The yellow precipitate
obtained was filtered ,dried and recrystallized from ethyl acetate to give compound (3) (yield 90 % ,
m.p= 190 0 C ) .
2.2.8. The reduction of 9- N itrosyl carbazole to give 9-amino carbazole compound ( 8 )
A mixture of 9 - nitrosyl carbazole (9.0 g, 0.05mole) and zinc powder (5.0 g) in (25ml) acetic acid
was stirred for 2 hr. at 0 0 C . The filt ered and poured into about ( 500ml) water. The gray precipitate
obtained was filtrated , dried, recrystallized from ethanol to give compound ( 8 ) (yield 78%,m.p=
151-152 0 C )
2.2.9. Synthesis of 9-Amide carbazole derivatives 9 (a,b) ( 8 4 )
A mixture of 9-amino carbazole (0.5g,0.0027mole ),(0.1mole) of a appropriate acid chloride namely
acetyl chloride ,benzoyl chloride respectively and (0.2ml) of triethylamine in (10ml) of THF was
stirred for (2hr.) at room temperature .The reaction mixture was left overnight and the precipitate
formed was filtered ,dried and recrystallized from ethanol to give compounds 10(a,b) respectively
9- A cetamide carbazole (9 a ) : y ield 50 % ,m.p. 200 0 C
9- B enzamide carbazole (9 b ): y ield 70 % ,m.p. 230 0 C
2.2. 10 Synthesis of Schiff bases derivitives 10 (a-e) ( 85 )
A mixture of 9-amino carbazole (1.8g , 0.01 mole),and appropriate aromatic aldehyde namely [ p chlorobenzaldehyde , p -bromobenzaldehyde , 2,4-dihydroxy benzaldehyde, o methoxybenzaldehyde , p -nitro benzaldehyde] in 40ml ethanol and few drops of glacial acetic acid
was refluxed for (15-20 hr.).The mixture was poured into ice water .The precipitate obtained was
filtered and recrystallized from the appropriate solvent ethanol or ethanol-water to give compounds
8 (a-e) respectively.
9-( o - M ethoxybenzylidene) carbazole ( 10 a)
y ield 44 % , m.p. 182 0 C
9-( p - C hlorobenzylidene) carbazole ( 10 b )
y ield 70 % , m.p. (162-164) 0 C
9-( p - B romobenzylidene) carbazole ( 10 c )
y ield 40 % , m.p. 200 0 C
9-(2,4- D ihydroxy benzylidene)carbazole ( 10 d )
y ield 53 % , m.p. 153de. 0 C
9-( p - N itro benzylidene) carbazole ( 10 e )
y ield 65 % , m.p. 170 0 C
3.1. 9 - ethyl carbazole [1]:
For preparation of 9 - ethyl carbazole have been used . First method as the most widely encountered is the
reaction between 9H - carbazole and ethyl bromide in the presence of KOH (pot as s ium hydroxide ) at (60 0
c) give more than (90%) yields as a white crystalline compomd [1] .
FT- IR spe c trum of 9- ethyl carbazole ( F ig.1) showed the disapperence of stretching band at 3410 cm -1
(N– H) , strong band at 30 51 cm -1 aromatic (C – H) str., 1600 and 1620 cm -1 a ssigned to the aromatic
stretching system (C = C) str. UV spectrum in ( F ig .4 ) exhibited λ max at 340 nm due to (n-π * ) and 229 nm ,
246 nm due to (π-π * ) electronic transition.
3.2. 3- ace tyl - 9 – ethyl carbazole [2]
3 – acetyl – 9 – ethyl carbazole was obta ined when acetyl chloride in di c hloro ethane in presence of
anhydrous aluminum chloride as acatalyst was rea cted with 9 - ethyl carbazole (1).
FT IR spectrum of compound (2) ( F ig.2) , showed weak bands at 3043 cm for aromatic (C – H) str., 2873 cm
-1 , 2931 cm -1 and 2970 cm -1 aliphatic (C – H) str. o f (CH 3 ) acetyl group , strong and clear str. b ands at
1662 cm -1 (C = O) str., two bands at 1558 cm -1 and 1465 cm -1 aromatic system (C = C) str., and 756 cm -1
aromatic ring (= C – H) . UV spectrum in ( F ig .5 ) show e d λ max at 330 nm due to (n-π * ) and 242 nm due to
(π-π * ) electronic transition. 1 H-NMR spectrum in (Fig.3) , (t, 1.40-1.47, CH 3 ), (q, 4.34-4.2, CH 2 ), (m, 8.088.12, Ar -H) and (s, 2.0-2.5, CH 3 )
Fig. 1 : FT-IR spectrum of compound (1)
Fig.2: FT-IR spectrum of compound (2)
Fig.3 : H-NMR spectrum of compound (2)
Fig. 4 : UV spectrum of compound (1)
Fig. 5 : UV spectrum of compound ( 2 )
3.3 . 3 – (3 – P henyl – 1 – ox o propen – 1 – y1) 9 – ethyl carbazole derivatives 3( a –h )
3 ( a –h )
(2)
Where ( Ar ) is:-
a. b) c) d)
e) f) g) h)
Through nucleophilic addition reaction as the typi cal reaction of aldeh ydes , compound n o . (2) undergoes
the characteristic condensation reaction with different kinds of aromatic aldehydes in ethanol instead of 1%
NaoH solution as a catalyst to afford 3 ( a –h) there yields between ( 34 – 51%). T he FT IR spectra (8 6 -8 8 )
of compounds 3 ( a – h) showed absorption bands at (1647 – 1670) cm -1 (C = O) str., and (1477 – 1593) cm
-1 (C = C) str . The reaction mechanism of compounds 3 (a – h) may obtained mainly through two steps .T he
first step involves the abstraction of proton by the base , and the second step is a nucleophilic attack of the
aldehyde car b onyl group by the inolate ion . this may be simplified as in (scheme1) below ( 89 ) :Scheme (1) : Reaction mechanism for the formation of compounds 3(a-h)
3.3.1. 3 – [ 3 – P henyl – 1 – o x o propen -1 – y1 ] 9 – ethyl carbazole (3a)
B enzaldehyde and 3 – acetyl 9 – ethyl carbazole were dissolved in 80 ml of ethanol and (1.5 ml of 1% NaoH )
. this comound was obtained as yellow precipitate in 43% yield , m.p . (110 – 112) 0 C , which was
characterized by FT IR spectral data . FT IR spectrum as illustrated in ( F ig . 6 ) showed weak band at 3059
cm -1 for aromatic (C – H) str., 3028 cm -1 ole finic (C – H) str., 1675 cm -1 (C = O) str., 1608 cm -1 ole finic
(C = C) str ., 1597 cm -1 aromatic (C = C) str., and 756 cm -1 aromatic ring as shown in [ Table (3 – 3) ]
3.3. 3- [ 3 – ( o – M ethoxy phenyl ) – 1 – ox o propen – 1 – y1 ] 9-ethyl carbazole (3b) .
This compound was obtained as described in the previous section using o – methoxybansaldehyde , the
produet was characterized by m.p . , FT IR spectral data . FT IR spectrum (Fig . 7 ) showed medium strength
band at 3059 cm aromatic (C – H) str., 3012 cm -1 olefinic (C – H) str., stro ng band at 1662 cm -1 (C = O) str.,
1589 cm -1 (C =C) str., 1565 cm -1 , 1465 cm -1 aromatic (C = C) str. a nd weak band at 1246 cm -1 ( – O –
CH) s tr. As shown in [Table (3-3)]. The 1 H-NMR spectrum showed in (Fig.8) (t, 1.40-1.47, CH 3 ), (q, 4.34-
4.2, CH 2 ), (m, 8.08-8.12, Ar -H) and (s, 1.7-2.3, -CH=CH-) .
3.3. 3- [ 3- ( o - N itro phenyl ) - 1 – oxo propen-1-y1 ] 9- ethylcarbazole (3c)
This co mpound was prepared as described above by using (3- ac e tyl – 9 – ethyl carbazole ) and ( o - nitro
benzaldehyde ) , the product was characterized using m.p . , FT IR spectra l data . FT IR spectrum (Fig . 9 )
showed medium bands at 3047 cm -1 aromatic (C – H) str. 2931 cm -1 olefinic (C – H) str., strong bands at
1766 cm -1 (C = O) str., 1477 cm -1 (C = C) str., 1535 cm -1 and 1334 cm -1 asym. a nd sym . (NO 2 ) str.
1465 cm -1 aromatic(C = C) str., 841 cm -1 aromatic (C – N) str. a nd 756 cm -1 aromatic ring ɣ (= C – H) as
shown in [Table (3 – 3)]
3.3.4 3-[3-( p - C hlorophenyl ) – 1 – ox o propen ] 9 – ethyl carbazole (3d)
This compound was prepared as above using (3 – acetyl – 9 – ethyl carbazole ) and (p – chlorobenzeldehyde
the reaction product was characterized by m.p ., FT IR spectra l data . FT IR spectrum (Fig . 10 ) showed
medium bands at 3097 cm -1 aromatic (C – H) str., 3051 cm -1 olefinic (C –H) str., at 1651 cm -1 (C = O) str.,
1527 cm -1 (C = C) str., 1566 cm -1 and 1465 cm -1 aromatic (C = C) str., 748 cm -1 (C – C l ) and 756 cm -1
aromatic ɣ ( = C – H) as shown in [Table (3 – 3)] .
3.3.5 3-[ 3 – ( p - B romo phenyl ) – 1 – ox o propen – 1 – y1 ] 9 – ethyl carbazole (3e)
This compound was prep ared as above using (3 – acetyl – 9 – ethyl carbazole ) and (p –
bromobenzaldehyde ). The product was characterized by m.p . , FT- IR spectra l data . FT-IR spectrum (Fig .
11 ) showed medium bands at 3051 cm -1 aromatic (C – H) str., 2974 cm - 1 olefinic (C – H) str., strong bands
at 1647 cm -1 (C = O) str., 1539 cm -1 (C = C) str., 632 cm -1 (C – Br), 756 cm -1 aromatic ɣ (= C – H) as
shown in [Table(3 – 3)] .
3.3.6 3 – [ 3 – ( p - N,N – D imethyl amino phenyl ) – 1 – ox o propen – 1 – y1] 9 – ethyl carbazole (3f)
This compound was prepared as above using (3 – acetyl – 9 – ethyl carbazole ) and ( p -N,N- Dimethyl amino
benzaldehyde ) . the reaction product was characterized by m.p ., FT IR spectra l data ( F ig. 12 ) showed
medium bands at 3051 cm -1 aromatic (C – H) str., 2974 cm -1 o lefinic (C – H) str., strong bands at 1658 cm 1 (C = O) str., 1597 cm -1 (C = C) str., strong bands at1550 cm -1 (C – H) str., 756 cm -1 aromatic ɣ (= C – H)
as shown in [Table (3 – 3)]
3.3 .7 3 – [3 – (2,4 – D ihydroxy phenyl ) – 1 – ox o propen – 1 – y1] 9 – ethyl carbazole (3 g)
This compound was prepared as above using (3 – acetyl – 9 – ethyl carbazole ) and ( 2,4 – dihydroxy
benzaledhyde ). The reaction product was characterized by m.p ., FT-IR spectra l data . FT-IR spectrum ( F ig.
13 ) showed medium bands at 3126 cm -1 aromatic (C – H) str., 2968 cm -1 olefinic (C – H) str., strong bands
at 1660 cm -1 (C = O) str., 1573 cm -1 (C = C)str., 3402 cm -1 (O – H) str., 756 cm -1 aromatic ɣ ( = C – H) as
shown in [ Table (3 – 3)]
3.3.8 3 – [ 3 - (5 – P henyl ) – 1 – ox o -2,4- pentadie n e – 1 – y1) 9 – ethyl carbazole (3h)
This compound was prepared as above usin g (3 – acetyl – 9 – ethyl carbazole ) and ( cinnamylaldehyde ).
The reaction product was characterized by m.p . FT-IR spectrum (Fig . 14 ) showed medium bands at 3051
cm -1 aromatic (C – H) str., 2966 cm -1 olefinic (C – H) str., strong bands at 1670 cm -1 (C = O) str., 1593 cm 1 (C = C) str., 756 cm -1 aromatic ( = C – H) as shown in [Table(3 -3 )].
Table (3-1): Scientific name and chemical structure of3-(3-phenyl-1- o xy propen-1-yl)9- e thyl carbazole derivatives 3 (a-h)
Compd.
Scientific name
chemical structure
No.
3a
3- [ 3-Phenyl-1- o x o propen-1-yl ] 9-ethyl carbazole
3b
3- [ 3- ( O - M ethoxy phenyl ) -1-ox o propen-1-yl ] 9-ethyl carbazole
3c
3- [ 3- ( O - N itro phenyl ) -1-ox o propen-1-yl ] 9-ethyl carbazole
3d
3- [ 3- ( P - C hloro phenyl ) -1-ox o propen-1-yl ] 9-ethyl carbazole
3e
3- [ 3- ( P - B romo phenyl ) -1-ox o propen -1-yl ] 9-ethyl carbazole
3f
3- [ 3- ( P - N,N- D imethyl amino phenyl ) -1-ox o propen -1-yl)9-ethyl carbazole
3g
3- [ 3- ( 2,4- D ihydroxy phenyl ) -1-ox o propen -1-yl ] 9-ethyl carbazole
3h
3- [ 5- P henyl-1-ox o-2,4- pentadiene-1-yl ] 9-ethyl carbazole
T able(3-2) physical properties of compounds 3 (a-h)
M.Wt .
Compd.
Molecular
Ar -
No.
g/mol m.p . 0 C % yield Color of crystal
Formula
(theoretical)
3a
C 2 2 H 19 NO
313 .0
110-112
43
Yellow
3b
C 2 3 H 21 NO 2
3 43 .0
97-99
51
Yellow
3c
C 2 2 H 18 O 3 N 2
3 58 .0
175-177
39
Orange
3d
C 2 2 H 18 ONCl
3 47 .5
>
37
Yellowis h-orange
3e
C 2 2 H 18 ONBr
3 82 .0
190-192
39
Brown
3f
C 2 4 H 24 ON 2
369 .0
180-182
34
Brown
3g
C 2 2 H 20 O 3 N
346 .0
250-252
44
B rown
3h
C 2 4 H 21 ON
3 39 .0
210-215
50
Dark- brown
T able (3-3) : Infrared absorpti on data for compounds 3(a-h)
ᶹ
ᶹ
ᶹ
(C-H)
(C-H)
ᶹ (C=C)
Other
cm -1
cm -1
cm -1
Bands
aromatic
olefinic
3059
3028
ᶹ
Compd.
Structure (C=O)
No.
cm -1
3a
1675
cm -1
1597
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‫اﻟﺧﻼﺻﺔ‬
‫ﻣﺷﺗﻘﺎت اﻟﻛﺎرﺑﺎزول واﻻﺛﯾل ﻛﺎرﺑﺎزول ﺗﻌﺗﺑر ﻧوع ﻣن اﻟﻣرﻛﺑﺎت اﻟﺣﻠﻘﯾﺔ ﻏﯾر اﻟﻣﺗﺟﺎﻧﺳﺔ اﻟﻣﺣﺗوﯾﺔ ﻋﻠﻰ اﻟﻧﺗروﺟﯾن وھﻲ ﻣﺷﺗﻘﺎت ﻣﮭﻣﺔ ﻓﻲ‬
‫اﻟﻣﺟﺎل اﻟطﺑﻲ ‪ ,‬ﻟذﻟك اﻟﺑﺣث ﯾﺗﺿﻣن ﺗﺣﺿﯾر ﻣﺷﺗﻘﺎت ﺟدﯾدة ﻟﻠﻛﺎرﺑﺎزول ﺣﯾث ﺗم ﺗﺣﺿﯾر ھذه اﻟﻣرﻛﺑﺎت ﻋﻠﻰ ﺟزﺋﯾن‪ -:‬اﻟﺟزء اﻻول ﯾﺑدأ‬
‫ﺑﻣرﻛب ‪-3‬أﺳﺗﯾل ‪-9‬أﺛﯾل ﻛﺎرﺑﺎزول واﻟذي ﯾدﺧل ﻓﻲ ﺗﻔﺎﻋل ﻣﻊ اﻟدﯾﮭﺎﯾدات اروﻣﺎﺗﯾﺔ ﻣﺧﺗﻠﻔﺔ ﺑوﺟود ھﯾدروﻛﺳﯾد اﻟﺻودﯾوم ‪ %1‬ﻟﺗﻛوﯾن ﻣرﻛﺑﺎت‬
‫اﻟﺗﻲ ﻋﻧد ﻣﻔﺎﻋﻠﺗﮭﺎ ﻣﻊ اﻟﮭﯾدرازﯾن ھﯾدرﯾت ﺑوﺟود ﺣﺎﻣض اﻟﺧﻠﯾك أﻋطت ﻣﺷﺗﻘﺎت ‪)-3(a-h) -3‬أوﻛﺳوﺑروﺑﯾن‪-1-‬ﯾل(‪-9‬أﺛﯾل ﻛﺎرﺑﺎزول ‪3‬‬
‫ﻣﻊ اﻟﻔﻧﯾل ھﯾدرازﯾن ﺑوﺟود اﻟﺑﯾﺑرﯾدﯾن واﻟذي ‪ ( ( a-h 3‬وﺑﻌدھﺎ ﺗﻌﺎﻣل ﻣرﻛﺑﺎت ال )‪)(a-h‬أﺳﺗﯾل‪-5-‬أرﯾل ﺑﺎﯾروزوﻟﯾن (‪-9‬أﺛﯾل ك ارﺑﺎزو ل ‪4‬‬
‫ﻣﻊ اﻟﻛواﻧدﯾن ﻛﺎرﺑوﻧﯾت ‪ (a-h) 3‬وﺑﻌدھﺎ ﺗﻌﺎﻣل ﻣرﻛﺑﺎت ‪ (a-h) 5‬ﯾﻧﺗﺞ ﻣﺷﺗﻘﺎت ‪-1)-3‬ﻓﻧﯾل‪-5-‬أرﯾل ﺑﺎﯾروزوﻟﯾن‪-3-‬ﯾل(‪-9‬أﺛﯾل ﻛﺎرﺑﺎزول‬
‫)‪(a-h‬ﻟﺗﻧﺗﺞ ﻣﺷﺗﻘﺎت ‪-2)-3‬اﻣﯾﻧو‪-6-‬أرﯾل‪-4-‬ﺑرﯾﻣﯾدﯾﻧﯾل(‪-9‬أﺛﯾل ﻛﺎرﺑﺎزول ‪6.‬‬
‫ﻟﯾﻌطﻲ ) ‪ (N-NH 2‬اﻟﻰ )‪ (N-H‬اﻟﻣرﻛز ﺣﯾث ﺗم ﺗﺣوﯾل ال ‪ HCl‬ﯾﺗﺿﻣن اﻟﺟزء اﻟﺛﺎﻧﻲ ﺗﻔﺎﻋل اﻟﻛﺎرﺑﺎزول ﻣﻊ ﻧﺗرﯾت اﻟﺻودﯾوم وﺣﺎﻣض ال‬
‫‪-9‬ﻧﺗروﺳﯾل ﻛﺎرﺑﺎزول )‪ (7‬وﻋﻧد ﻣﻌﺎﻣﻠﺗﮫ ﻣﻊ ﺑﺎودر اﻟﺧﺎرﺻﯾن وﺣﺎﻣض اﻟﺧﻠﯾك ﻋﻧد درﺟﺔ اﻟﺻﻔر اﻟﻣﺋوي أﻋطﻰ ﻣرﻛب ‪-9‬أﻣﯾﻧو ﻛﺎرﺑﺎزول‬
‫ﻛﺎرﺑﺎزول(ﺑﻧز أﻣﺎﯾد ﺑﻣﻌﺎﻣﻠﺔ ﻣرﻛب ‪-9‬اﻣﯾﻧو ﻛﺎرﺑﺎزول )‪ (8‬ﻣﻊ‪ N -(9-‬ﻛﺎرﺑﺎزول‪-9-‬ﯾل(اﺳﯾت أﻣﺎﯾد و‪ . (8) N -(9-‬ﻛﻣﺎ ﺣﺿرت اﻟﻣرﻛﺑﺎت‬
‫ﻛﻠورﯾد اﻻﺳﺗﯾل وﻛﻠورﯾد اﻟﺑﻧزوﯾل ﻋﻠﻰ اﻟﺗواﻟﻲ‪ .‬وﻋﻧد ﻣﻌﺎﻣﻠﺔ اﻟﻣرﻛب )‪ (8‬ﻣﻊ ﺑﻌض اﻻﻟدﯾﮭﺎﯾدات اﻻروﻣﺎﺗﯾﺔ اﻟﻣﺧﺗﻠﻔﺔ أﻋطت ﻗواﻋد ﺷف واﻟﺗﻲ‬
‫‪ (a-e) .‬ﻛﺎرﺑﺎزول‪-9-‬أﻣﯾن ‪ H – 10‬ﺑﻧزﻟﯾدﯾن ‪ N – 9‬ھﻲ ﻣﺷﺗﻘﺎت‬
‫‪ U.V , FT-IR .‬وﺟﻣﯾﻌﮭﺎ ﺑﺎﻟطرق اﻟﻔﯾزﯾﺎوﯾﺔ واﻟطﯾﻔﯾﺔ ‪ H 1 -NMR‬ﺗم ﺗﺷﺧﯾص ﺑﻌض اﻟﻣرﻛﺑﺎت اﻟﻣﺣﺿرة ﺑﺎل‬
‫ﺟﻣﮭورﯾﺔ اﻟﻌراق‬
‫وزارة اﻟﺗﻌﻠﯾم اﻟﻌﺎﻟﻲ واﻟﺑﺣث اﻟﻌﻠﻣﻲ‬
‫ﺟﺎﻣﻌﺔ ﺑﻐداد ‪ -‬ﻛﻠﯾﺔ اﻟﻌﻠوم‬
‫ﻗﺳم اﻟﻛﯾﻣﯾﺎء‬
‫ك رﺑﺎزول ‪ H 9‬ﺗﺣﺿﯾر وﺗﺷﺧﯾص ﻣﺷﺗﻘﺎت ﺟدﯾدة ﻟـ‬
‫رﺳﺎﻟﺔ ﻣﻘدﻣﺔ إﻟﻰ ﻛﻠﯾﺔ اﻟﻌﻠوم ‪ /‬ﺟﺎﻣﻌﺔ ﺑﻐداد‬
‫وھﻲ ﺟزء ﻣن ﻣﺗطﻠﺑﺎت ﻧﯾل درﺟﺔ اﻟﻣﺎﺟﺳﺗﯾر ﻓﻲ ع ﻟوم اﻟﻛﯾﻣﯾﺎء‬
‫ﺗﻘدم ت ﺑﮭﺎ‬
‫ﻧﺎھد ﻣﺣﻣود اﺣﻣد‬
‫ﺑﻛﺎﻟورﯾوس ﻋﻠوم ﻛﯾﻣﯾﺎء ‪ /‬ﺟﺎﻣﻌﺔ ﺑﻐداد ‪2008‬‬
‫ﺑﺈﺷراف‬
‫أ‪.‬ﺳﻌﺎد ﻣﺻطﻔﻰ اﻻﻋرﺟﻲ‬
‫أ‪.‬م‪ .‬د‪ .‬اﺣﻣد وﺣﯾد ﻧﺎﺻر‬
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