Preparation of Some 4- diazo (hetero aryl)phenyl pyrazole and 2-diazo(hetero

Abstract

In the present work fifty six a new α, β - unsaturated carbonyl compounds and their cyclization reactions with varieties reagent (hydrazine derivatives, hydroxylamine and thio urea) pyrazole, isoxazole and thiopyrimidine derivatives were prepared. A process of the preparation of α, β – unsaturated carbonyl compounds by coupling to diazotized a p-aminoacetophenone with 1.3 di carbonyl compounds (ethyl acetoacetate, acetyl acetone, bezoylacetone and dimedone) in presence sodium acetate and ethanol (C-N) bond was formed. Some of the resultant compounds reacted with hydrazine derivatives lead to cyclized to the pyrazole derivatives and condensed with aromatic aldehyde give the synthesis α, β – unsaturated carbonyl. Later were prepared directly from some resultant of the coupling with dimedone in presence basic media sodium hydroxide at room temperature . The reaction progress for all synthesized compounds was checked by (TLC) technique , meting point, and yield percentage. The structure of synthesized compounds were confirmed by spectroscopic instruments IR, some of synthesized compound were confirmed by UV, IH-NMR, 13C-NMR, MS. 

Table of contents

 Dedication I

Acknowledgment II

Abstracts III

Arabic abstracts IV

Table of contents

List of table 42-92

List of schemes 26-40

List of fingers 1-14

List of Abbreviations

Chapter one 1

Introduction 1.

1.1 α, β - Unsaturated carbonyl compounds 1

1.1.1. Synthesis of α, β unsaturated carbonyl compounds 1

1.1.1. 1. Aldol condensation : 2

1.1.1.2.Claisen-Schmidt reaction 2

1.1.1.2. Claisen-Schmidt reaction 2

1.1.1.3.Fierde l-Carft Acylation 3

1.1.1.4.Suzuki coupling reaction 3

1.1.1.5. Boron trifluorid -etherate reaction. 4

1.1.1.6. Microwave Irradiation reaction 5

1.1.1.7. Von-Konstanecki reaction 5

1.1.2.reaction of α, β unsaturated carbonyl compounds 6

1.1.2.1. Reduction of olefinic group 6

1.1.2.2. Cyclization reaction 6

1.2. Pyrimidine 7

1.2.1Synthesis of pyrimidine derivatives 8

1.2.2. Biological activities of pyrimidine derivatives 9

1.3. Payrazoles 9

1.3.1.Synthesis of pyrazole derivatives 10

1.3.2Biological activities of pyrazole derivatives 13

1.4.Isoxazoles 14

1.4.1. Synthesis of isoxazole derivatives 14

1.4.2.Bioactivities of Isoxazole derivatives 17

Aims and objectives 17

Chapter Two

2.1.Materials and Methods 20

2.1.1 Chemicals 20

2.1.2 Solvent 20

2.1.3. Reagents 21

2.1.4. Thin layer chromatography (TLC) 21

2.1.5 Spectroscopic Instruments 21

2.1.5.1 Infra-red spectroscopy 21

2.1.5.2. Ultraviolet–visible spectrophotometer (UV) 21

2.1.5.3. Nuclear Magnetic Resonance(NMR) 21

2.1.5.4. Mass spectroscopy 21

2.1.6.General Instruments 21

2.2. Synthetic Methods 22

2.2.1. 3- di azo-(p-acetyl phenyl) -phenyl butane -1, 3-ones(I- IV) 22

2.2.2. 4- di azo-(p-acetyl phenyl)– substituted pyrazole(V- XII) 23

2.2.3. α, β unsaturated carbonyl compounds (XIII-LXVII) 23

2.2.4. 4-diazo-(aryl)-pyrazole-3-yl)-substitutedpyrazole 24

2.2.5. 4-diazo-(aryl)- isoxazol-5-yl)-substituted pyrazole(LXIX-CX) 24

2.2.6.4-diazo-(p-(5-(aryl)-2-thiopyrimidine-6-yl)-phenyl- substituted pyrazole(LXVII-CIX)

Chapter Three 94

RESULTS AND DISCUSSION 94

3. discussion 94

3.1 Organic Synthesis 94

3.2. Retrosynthetic of synthesis compounds 94

3.3. Reaction mechanism 96

3.3.1. α, β unsaturated carbonyl derivatives 96

3.3.2. pyrazole derivatives 96

3.3.3. isoxazole derivatives 97

3.3.4. pyrimidine thiol derivatives 98

3.4. Spectroscopic analysis 99

Conclusion and recommendation 107

Chapter four 109

References 109