ABSTRACT The synthesis and characterization of five new linear diazaphenoxazine compounds is reported. The key intermediate, 3-chloro-1-9-diazaphenoxazine, was prepared via a base catalyzed reaction of 2-amino-3-hydroxypyridine with 2,3,5-trichloropyridine in aqueous 1, 4-dioxane. Five 3-amino derivatives of the key intermediate were prepared via Buchwald – Hartwigamination coupling reaction between 3-chloro-1,9-diazaphenoxazine and various heterocyclic amines, under the catalytic influence of palladium acetate. The assignment of structures to the synthesized compounds was done by the use of combined information from Uv-vis, IR, and NMR spectra.
TABLE OF CONTENTS
Title page...................................................................................................................i
Approval page………………………………………………………………………………………………………ii
Certification…………………………………………………………………………………………………………iii
Dedication……………………………………………………………………………………………………………iv
Acknowledgement………………………………………………………………………………………………..v
Abstract……………………………………………………………………………………………………………….vi
Table of contents………………………………………………………………………………………………..vii
CHPTER ONE…………………………………………………………………………………………………………1
1.0 Introduction…………………………………………………………………………………………….…….1
1.1 Background of study………………………………………………………………………………….……3
1.2 Statement of the problem………………………………………………………………………….…..5
1.3 Objectives of the study……………………………………………………………………………….....6
1.4 Justification of the study………………………………………………………………………………..6
CHAPTER TWO…………………………………………………………………………………………………….7
2.0 LiteratureReview…………………………………………………………………………………..........7
2.1 TandemAmination and Amidation………………………………………………………………..7
2.2 LinearPhenoxazines……………………………………………………………………………….……19
2.2.1 Non-azaanalogues of phenoxazines…..……………………………………………….…..20
2.2.1.1Benzo[b]phenoxazine……………………………………………………………………………..20
2.2.1.2 2-Amino-4,4α-dihydro-4α,7-dimethyl-3H-Phenoxazine-3-one………………22
2.2.2 Aza analogues of phenoxazines………………………………………………………......23
2.2.2.1 1-Azaphenoxazine……………………………………………………………………………24
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2.2.2.2 2-Azaphenoxazine……………………………………………………………………………27
2.2.2.3 3–Azaphenoxazine……………………………………………………………………………28
2.2.2.4 4–Azaphenoxazine……………………………………………………………………………33
2.2.2.5 3,4-Diazaphenoxazine……………………………………………………………………….34
2.2.2.6 1,4-Diazaphenoxazine…………..…………………………………………………………..35
2.2.2.7 1,9-Diazaphenoxazine ………………………………………………………………………37
2.2.3 Nitro, Amino, N-Acetyl and N-Alkyl Phenoxazines…………………………….38
CHAPTER THREE………………………………………………………………………………………………..42
3.0 Experimental……………………………………………………………………………….………...42
3.1 General Information……………………………………………………………………………....42
3.2 3-Chloro-1,9-diazphenoxazine………………………………………………………………..43
3.3 Preparations of Single Crystals of 3-Chloro-1,9-diazaphenoxazine ………..43
3. 4 1,4-Bis(2-hydroxy–3,5–ditert–butylbenzyl)piperazine…………………..………..44
3. 5 General Procedure for the Synthesis of 3-AminoDerivativesof 1,9-
Diazaphenoxazine……………………………………………………………………………………..……….44
3. 5. 1 3-(2-Amino-3–nitropyridino)-1,9-diazaphenoxazine……………………………..45
3. 5. 2 3-(2–Aminopyrazino)–1,9–diazaphenoxazine……………………………………..45
3. 5. 3 3-(2-Aminopyridino)–1,9–diazaphenoxazine……………………………………….46
3. 5. 4 3–(2–Aminophenyl)–1,9–diazaphenoxazine………………………………………..46
3. 5. 5 3–Anilino-1,9–diazaphenoxazine………………………………………………………..46
CHAPTER FOUR …………………………………………………………………………………………………47
4.0 Results and Discussion ……………………………………………………………………………47
4.1 3–Chloro–1,9-diazaphenoxazine ……………………………………………………………47
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4.2 1,4–Bis(2–hydroxy–3,5-ditert–butylbenzyl)piperazine …………………………..49
4.3 Catalyst Preactivation …………………………………………………………………………….49
4.4 3–(2–Amino-3–nitropyridino)-1,9-diazaphenoxazine ……………………………...49
4.5 3–(2–Aminopyrazino)-1,9–diazaphenoxazine…………………...........................50
4.6 3–(2–Aminopyridino)-1,9–diazaphenoxazine………………………………….………..51
4.7 3–(2–Aminophenyl)–1,9–diazaphenoxazine………………………………….…………52
4.8 3–Anilino–1,9–diazaphenoxazine………………………………………………..…………52
CHAPTER FIVE ……………………………………………………………………………………………………54
5.0 Conclusion …………………………………………………………………………………………….……54
REFERENCES…………………………………………………………………………………….…..55
IFEYINWA, E (2022). Tandem Amination Catalysis in the Synthesis of Diazaphenoxazine Compounds of Pharmaceutical Interest. Afribary. Retrieved from https://afribary.com/works/tandem-amination-catalysis-in-the-synthesis-of-diazaphenoxazine-compounds-of-pharmaceutical-interest
IFEYINWA, EGBO "Tandem Amination Catalysis in the Synthesis of Diazaphenoxazine Compounds of Pharmaceutical Interest" Afribary. Afribary, 18 Oct. 2022, https://afribary.com/works/tandem-amination-catalysis-in-the-synthesis-of-diazaphenoxazine-compounds-of-pharmaceutical-interest. Accessed 19 Apr. 2024.
IFEYINWA, EGBO . "Tandem Amination Catalysis in the Synthesis of Diazaphenoxazine Compounds of Pharmaceutical Interest". Afribary, Afribary, 18 Oct. 2022. Web. 19 Apr. 2024. < https://afribary.com/works/tandem-amination-catalysis-in-the-synthesis-of-diazaphenoxazine-compounds-of-pharmaceutical-interest >.
IFEYINWA, EGBO . "Tandem Amination Catalysis in the Synthesis of Diazaphenoxazine Compounds of Pharmaceutical Interest" Afribary (2022). Accessed April 19, 2024. https://afribary.com/works/tandem-amination-catalysis-in-the-synthesis-of-diazaphenoxazine-compounds-of-pharmaceutical-interest