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«STUDIES IN HETEROCYCLIC SYNTHESIS By LONGCHUAN HUANG A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL ...»

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STUDIES IN HETEROCYCLIC SYNTHESIS

By

LONGCHUAN HUANG

A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL

OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT

OF THE REQUIREMENTS FOR THE DEGREE OF

DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

© 2010 Longchuan Huang To my parents Fayun Huang and Miaorong Zhu, to my brother Jiajia Huang, and to my dear friends for their unconditional love and support

ACKNOWLEDGMENTS

I would like to express my gratitude to my advisor, Professor Alan R. Katritzky, for his consistant support and guidance, which were essential for me to complete my studies. His overall knowledge of science, not just chemistry, and his strong devotions to science and education is extremely impressive. His mentorship has guided me through many challenges as a graduate student, and I will always remain appreciative and thankful for the opportunity working with him. I would especially like to thank Dr. C.

Dennis Hall for his constructive and helpful suggestions for my research and for his kindness and patience with reading and correcting my writing over and over again. Also, I want to thank Dr. John Reynolds, Dr. Ion Ghiviriga, Dr. Weihong Tan and Dr. Fazil Najafi for their time as members of my committee. Their knowledge, advice, and support have been a valuable and cherished resource during my graduate career.

This work would not have been possible without the hard work of my coworkers with whom I have interacted: Dr. Rajeev Sakhuja for his expertise in both chemistry and as a group leader; Dr. Prahbu Mohapatra for the teamwork on the synthesis of 1,3,4oxadiazoles in Chapter 3. My thanks must go to Dr. Yuming Song, Ms. Reena Gyanda and Ms. Ling Wang who all have contributed to the triazole-polymer project described in Appendix. I would like to thank all of the present and past members of the Katritzky research group. I have made some great friends and enjoyed their company during the past four years. Their friendship and support have made this period of my life more pleasant and memorable.

TABLE OF CONTENTS

page ACKNOWLEDGMENTS

TABLE OF CONTENTS

LIST OF TABLES

LIST OF FIGURES

LIST OFSCHEMES

LIST OF ABBREVIATIONS

Abstract

CHAPTER 1 INTRODUCTION TO BENZOTRIAZOLE CHEMISTRY

1.1 Benzotriazole

1.1.1 Structure and Isomerization

1.1.2 Synthesis of Benzotriazoles

1.2 Activation Ability of the Benzotriazole Ring

1.2.1 As a Proton Activator or an Anion Stabilizer

1.2.2 As a Leaving Group

1.2.3 As an Ambient Anion-Directing Group

1.2.4 As a Radical Stabilizer or a Radical Precursor

1.2.5 As an Anion Precursor

1.3 N-Acylbenzotriazoles in Heterocyclic Synthesis

1.3.1 Preparation of N-Acylbenzotriazoles

1.3.2 N-Acylbenzotriazoles for N-, S-, C- and O- Acylation

1.3.2.1 Selective synthesis of S-acyl and N-acylcysteines

1.3.2.2 Selective synthesis of S-acylglutathiones and Nacylglutathiones

1.3.2.3 Synthesis of N-Cbz-protected (α-aminoacyl)methylenepyridines and -quinolines

1.3.2.4 Synthesis of S-acylisotripeptides

1.3.2.5 Synthesis of azo-dye labeled amino acids and amines.................. 31 1.3.2.6 Synthesis of chiral O-(α-protected-aminoacyl)steroids

1.3.2.7 Synthesis of pyridin-2-ylmethyl ketones

1.3.2.8 Synthesis of 1-(benzotriazol-1-yl)alkyl- ethers and esters.............. 33 1.3.2.9 Bt-mediated C-acylation

1.3.3 Expansion of the Scope for N-Acylbenzotriazole Applications in Heterocyclic Synthesis

2 EFFICIENT SYNTHESES OF NAPHTHOQUINONE DIPEPTIDES

2.1 Introduction

2.1.1 Background

2.1.2 Interaction of Quinones and Amino Acids in Nature

2.1.3 Application of Quinone-Amino Acid Conjugates

2.1.4 Literature Preparative Methods for Quinone-Amino Acid Conjugates..... 40

2.2 Results and Discussion

2.2.1 Reaction of Naphthoquinone-Amino Acid Conjugates

2.2.2 Reaction of Thio-substituted Benzoquinone with Amino Acids................ 47 2.2.3 Preparation of Benzotriazole Activated Benzoquinone-Amino Acid Conjugates

2.3 Conclusion

2.4 Experimental Section

3 1,3,4-OXADIAZOLES FROM FUCTIONALIZED N-ACYLBENZOTRIAZOLES AND ACYLHYDRAZIDES

3.1 Introduction

3.1.1 Oxadiazoles

3.1.2 Biologically Active 1,3,4-Oxadiazoles

3.1.3 Polymeric 1,3,4-Oxadiazoles

3.1.4 Luminescent Compounds, Dyes and Photosensitive Materials............... 68 3.1.5 Other Miscellaneous Applications

3.1.6 Literature Preparative Methods for 1,3,4-Oxadiazoles

3.2 Results and Discussion

3.3 Conclusion

3.4 Experimental Section

3.4.1 General Procedure for the Preparation of 1,3,4-Oxadiazole

4 OVERVIEW OF N-HYDROXYAMIDOXIMES, N-AMINOAMIDOXIMES AND HYDRAZIDINES

4.1 Introduction





4.2 Structure and Configuration

4.2.1 N-Hydroxyamidoximes

4.2.2 N-Aminoamidoxime

4.2.3 Hydrazidines

4.3 Preparative Methods

4.3.1 N-Hydroxyamidoximes and Their Derivatives

4.3.1.1 From oximidoyl chlorides and hydroxyamines

4.3.1.2 From amidoximes and hydroxyamine

4.3.1.3 From nitrile oxides and hydroxyamines

4.3.1.4 Miscellaneous preparative methods for di-O-alkyl derivatives of N-hydroxyamidoximes

4.3.2 N-Aminoamidoximes and Their Derivatives

4.3.2.1 From oxime chlorides or amidoximes

4.3.2.2 From oximebenzotriazoles and hydrazines

4.3.2.3 From N-hydroxyimidates and hydrazides

4.3.2.4 From oxyimidoylchlorides and hydrazines

4.3.2.5 From hydrazide imidate and hydroxyamine

4.3.3 Hydrazidines

4.3.3.1 From imidate salts and hydrazines

4.3.3.2 From amidoximes and hydrazines

4.3.3.3 From amidrazones and hydrazines

4.3.3.4 From diethoxy-N,N-dimethylethanamine and hydrazides............... 93 4.3.3.5 From hydrazonyl bromides and hydrazines

4.3.3.6 From triazines

4.4 Chemistry and Reactions

4.4.1 N-Hydroxyamidoximes

4.4.1.1 Reduction of N-hydroxyamidoximes

4.4.1.2 Oxidation of N-hydroxyamidoximes

4.4.1.3 Reaction with aldehydes

4.4.1.4 Reaction with ketones

4.4.2 N-Aminoamidoximes

4.4.2.1 Reaction with aldehydes

4.4.2.2 Cyclization in basic media to hydroxytriazoles

4.4.3 Hydrazidines

4.4.3.1 Reaction with aldehydes

4.4.3.2 Reaction with anhydrides

4.4.3.3 Reaction with diketones

4.3.3.4 Reaction with alpha-keto- acids or esters

4.4.3.5 Reaction with acylnitriles

4.4.3.6 Reaction with cyclopentadiene derivatives

4.4.3.7 Reaction with diketoesters

4.4.3.8 Reaction with formic acid

4.3.3.9 Reaction with thioesters

4.3.3.10 Reaction with hydrazine

4.4.3.11 Reduction of hydrazidines

4.4.3.12 Condensation with α-halo ketones

4.4.3.13 Miscellaneous reactions

4.5 Applications

4.5.1 N-Aminoamidoximes

4.5.1.1 As a prodrug model

4.5.1.2 Applications in inorganic chemistry

4.5.2 N-Aminoamidoximes

4.5.2.1 As metal ligands for important coordination compounds.............. 112 4.5.3 Hydrazidines

4.5.3.1 As new fibrous adsorbents

4.5.3.2 As anti-tuberculosis agents

4.5.3.3 As environmentally friendly dyes

4.6 Conclusions

5 SUMMARY OF ACHIEVEMENTS

APPENDIX

A HIGHLY FILLED CROSSLINKED 1,2,3-TRIAZOLE POLYMERS AS NOVEL

ROCKET PROPELLANT BINDERS

A-1 Introduction

A-1-1 Rocket Propellant Binders

A-1-2 Triazole Polymers as Novel Rocket Propellant Binders

A-2 Results and Discussion

A-2-1 Selection of Model Polymer System

A-2-2 Preparation of Monomers

A-2-3 Preparation of Dogbone Samples

A-2-4 Filler Loading Effect

A-3 Conclusions

A-4 Experimental Section

LIST OF REFERENCES

BIOGRAPHICAL SKETCH

–  –  –

2-1 Naphthoquinone-amino acid/ester conjugates

2-2 Naphthoquinone-aminoacylbenzotriazoles

2-3 Synthesis of Naphthoquinone-dipeptides

2-4 Thiol-substituted benzoquinone-amino acid congjugates

3-1 Reaction of N-acylbenzotriazoles with benzoic acid hydrazide

A-1 Strain and modulus of unfilled and filled crosslinked triazole polymers............ 127 A-2 Effect of filler loading (Al: 10-14 micron) on strain and modulus of crosslinked triazole polymers

A-3 Effect of filler loading (Al: 75 micron) on strain and modulus of crosslinked triazole polymers

A-4 Effect of filler loading (NaCl: 45-50 micron) on strain and modulus of mechanical properties of crosslinked triazole polymers

A-5 Effect of filler loading (NaCl: 83-105 micron) on strain and modulus of crosslinked triazole polymers

A-6 Effect of mixed filler loading (mixture of two different particle sized Aluminum) on strain and modulus of crosslinked triazole polymers

A-7 Effect of mixed filler loading (mixture of Aluminum and NaCl) on strain and modulus of crosslinked triazole polymers

A-8 Effect of mixed filler loading (mixture of Aluminum and NaCl) on strain and modulus of crosslinked triazole polymers

–  –  –

1-1 Isomerization of Benzotriazoles

1-2 1H-Benzotriazole functions as an excellent synthetic auxiliary

1-3 Compounds with the Bt-C-O functionality

2-1 Important drugs containing quinone moities

2-2 Doxorubicin molecules intercalating DNA

2-3 Naturally occurring quinones

2-4 Classes of quinones participating in biological redox processes

3-1 Four types of oxadiazoles

3-2 Biologically important oxadiazoles

3-3 Polymers containing 1,3,4-oxadiazoles

3-4 1,3,4-Oxdiazoles with interesting optical properties

3-5 Other applications of 1,3,4-oxidazoles

4-1 Structure of N-hydroxyamidoximes, N-aminoamidoxime & hydrazidine............. 82 4-2 N-Hydroxyamidoximes and their derivatives in the literature

4-3 Known N-aminoamidoximes and their derivatives

4-4 Hydrazidines and their derivatives

4-5 Tautomerization, conformation and configuration of N-hydroxyamidoxime........ 85 4-6 Configuration of N-aminoamidoximes

4-7 Configuration of hydrazidines

4-8 N-Hydroxybenzamidoxime derivatives

4-9 Acetohydroximic oxime and ethylnitrosolic acid

4-10 N-Aminobenzamidxoime cobalt(II) perchlorate complex

4-11 Environmental friendly dye ligands

A-1 Common rocket propellant binders

A-2 Dogbone mold containing filled and unfilled triazole polymers

A-3. nstron universal tensile testing machine

A-4 Effect of filler loading on modulus of crosslinked triazole polymers.................. 130 A-5 Effect of filler loading on strain of crosslinked triazole polymers

A-6 Effect of mixed filler loading on modulus of crosslinked triazole polymers....... 134 A-7 Effect of mixed filler loading on strain of crosslinked triazole polymers............ 135 A-8 Dimensions of dogbone mold and dogbone sample

–  –  –

1-1 Alkylation of 1H-benzotriazole

1-2 Synthesis of benzotriazole

1-3 Synthesis of 5,7-dinitro-1-phenylbenzotriazole

1-4 Reactions of benzotriazolyl-stabilized carbanions with electrophiles.................. 25 1-5 Reaction with Grignard reagent

1-6 Benzotriazole acts as an anion-directing group

1-7 Benzotriazole acts as an radical stabilizer or precursor

1-8 Reductive elimination of benzotriazole

1-9 Methods for preparation of N-acylbenzotriazoles

1-10 Selective synthesis of S-acyl and N-acylcysteines

1-11 Selective synthesis of S-acylglutathiones and N-acylglutathiones

Synthesis of N-Cbz-protected (α-aminoacyl)methylenepyridines and quinolines

1-13 Preparation of S-acylisotripeptides

1-14 Synthesis of azo-dye labeled amino acids and amines

1-15 Microwave assisted synthesis of chiral O-(α-protected-aminoacl)steroids and O-(α-protected-dipeptidoyl)steroids

1-16 Synthesis of pyridin-2-ylmethyl ketones mediated via N-acylbenzotriazoles...... 32 1-17 Synthesis of 1-(benzotriazol-1-yl)alkyl esters by N-acylbenzotriazoles.............. 33 1-18 Enaminones via C-acylation of ketimines with N-acylbenzotriazoles.................. 34 2-1 Quinone-amino acid conjugates linked via a vinylic spacer

2-2 Synthesis of quinone-amino acid hybrids via Cross-Enyne Metathesis and Diels-Alder reactions

2-3 N-Quinonyl amino acids obtained with chloro-substituted quinones

2-4 Synthesis of N-quinonyl amino acids by addition to S-substituted benzoquinone

2-5 Preparation of naphthoquinone-dipeptides

2-6 Synthesis of naphthoquinone-amino acid/ester conjugates

2-7 Synthesis of naphthoquinone-aminoacylbenzotriazole conjugates

2-8 Preparation of naphthoquinone dipeptide conjugates

2-9 Synthesis of thiol-substituted benzoquinone-amino acid conjugates.................. 48 2-10 Synthesis of benzoquinone-amino acid benzotriazole derivative

3-1 Cycloaddition reactions of 1,3,4-oxadiazoles in total synthesis of natural product

3-2 Preparation of 2,5-disubstituted 1,3,4-oxadiazoles from 1,2-diacylhydrazines... 70 3-3 Preparation of 2,5-disubstituted 1,3,4-oxadiazoles from hydrazones................. 71 3-4 Preparation of 1,3,4-oxadiazolinones

3-5 1,3,4-Oxadiazole ring synthesis from acyclic precursors

3-6 Preparation of 2-amino-1,3,4-oxadiazoles

3-7 One-pot syntheses of unsymmetrical 2,5-disubstituted 1,3,4-oxadiazoles......... 73 3-8 1,3,4-Oxadiazoles from N-acylbenzotriazoles

4-1 Preparation of N-hydroxybenzamidoxime

4-2 Preparation of N-hydroxypyridylamidoximes

4-3 Preparation of 2,6-dichloro-N-hydroxybenzaldoxime hydrochloride salt............. 87 4-4 Preparation of formic hydroxyamidoxime hydrochloride salt

4-5 Synthesis of N-hydroxyamidoximes from nitrile oxides



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