DOCSLIB.ORG

I Preparation of N-Sulfonylsulfilimines Via

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
I Preparation of N-Sulfonylsulfilimines Via University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 1968 I PREPARATION OF N-SULFONYLSULFILIMINES VIA CYCLOADDITION REACTIONS OF N-SULFONYL ISOTHIOCYANATES AND N-SULFONYL PHOSPHINIMINES WITH SUFOXIDES II ATTEMPT AT PREPARING (METHYLSULFINYL)ALKYL ISOTHIOCYANATES VIA OPTICALLY ACTIVE METHANESULFINATE ESTERS JOHN BUTLER O'BRIEN University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation O'BRIEN, JOHN BUTLER, "I PREPARATION OF N-SULFONYLSULFILIMINES VIA CYCLOADDITION REACTIONS OF N-SULFONYL ISOTHIOCYANATES AND N-SULFONYL PHOSPHINIMINES WITH SUFOXIDES II ATTEMPT AT PREPARING (METHYLSULFINYL)ALKYL ISOTHIOCYANATES VIA OPTICALLY ACTIVE METHANESULFINATE ESTERS" (1968). Doctoral Dissertations. 2363. https://scholars.unh.edu/dissertation/2363 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. This dissertation has been microfilmed exactly as received 68-9768 O 'B R IEN , John B utler, 1941- I. PREPARATION OF N-SULFONYLSULFILIMINES VIA CYCLOADDITION REACTIONS OF N-SULFONYL- ISOTHIOCYANATES AND N-SULFONYLPHOSPHINI- MINES WITH SULFOXIDES. II. ATTEMPT AT PREPARE ING (METHYLSULFINYL)ALKYL ISOTHIOCYANAT ES VIA OPTICALLY ACTIVE METHANESULFINATE ESTERS. University of New Hampshire, Ph.D.91968 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. I. PREPARATION OF N-SULFONYLSULFILIMINES VIA CYCLOADDITION REACTIONS OF N-SULFONYLISOTHIOCYANATES AND N-SULFONYLPHOSPHINIMINES WITH SULFOXIDES. II. ATTEMPT AT PREPARING (METHYLSULFINYL)ALKYL ISOTHIOCYANATES VIA OPTICALLY ACTIVE METHANESULFINATE ESTERS By JOHN B^fc'BRIEN B. A., LAFAYETTE COLLEGE, 1963 A THESIS Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Graduate School Department of Chemistry January, 1968 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This thesis has been examined and approved. Qj u i a j j ]// A Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS The author wishes to extend his sincere gratitude to Dr. Kenneth K, Andersen, whose guidance and encouragement aided greatly in the completion of this work. The author would like to thank Dr. Paul R. Jones for reading the entire thesis and making many helpful suggestions. Thanks are also due the entire Organic Staff for their co­ operation and assistance. Financial support from the National Institutes of Health is gratefully acknowledged. The author wishes to dedicate this thesis to his wife, whose patience and understanding has made the completion of this work possible# H i Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS Page L i S t Of T &b l©S®o®®o®®«®eQaa9®«eee®®®o»®®«e»®®»B®®B®o.8a®®9a®«.3CH L i s t Of F ig\X2?@ Sase.a.aa.QOaB®®.®®®®®®.®®®®®®®®®®®®®®®®®®®®®®®® 3£lV PART I INTRODUCTION e®®.®®®®®®©®®.®.®®®®.®®®.®®®®®®®®®®®®®.®®®®®®®®®®©®®^ Early history of sulf ilimines« i •> m><i i d >i • ® > • • •®2 St rueture of sulf i1 imineSo®o®®®«8«®a®ofl®®®«a®«®«o®®®®®©®®®®®®®®®3 Mechanism of general sulf ilimine reaction.......... *......... ® ®^ Preparation of N-sulfonylsulfilimines... .................. ® ® ® • ®5 Preparation of N—acylsulfilimines. >•®•«■® ®•«•«®••■®««••® «■® < ® ®•i5 Cycloaddltlon Route to N-sulf onylsulf ilimines............ ©6 Cycloadditlon Route to N-acylsulfilimines. Preparation of an optically active N-sulf onylsulf ilimine. ...... 7 Mechanism of the N-sulf inylsulfonamide reaction. • ...... ® ..«••• 8 Purpose of this investigation.o®®®«ee®®e®®®®®o»«®®®®®a««ae®o®®®.8 RESULTS AND DISCUSSION o....oaQo.oflo.fi.8oe«88oa«Ba880o..®eao®o.oo9 Phosphinimine and phosphoramidate route • • • •. •. • ..... 9 Structure and Wittig reaction of phosphlnimines...... 10 Mechanism of phosphinimine reaction. ...... 11 Reaction of N-jo-toluenesulfonyltriphenylphosphlnlmine with d ime thy1 sulfoxid6 ^ « i « • s ■* * m m « a > < * >> i • 1 1 * »*•«i *•««»s12 iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Page Reaction of N-^-toluenesulfonyltriethoxyphosphinimine with dime thyX sulf ox id@« m i « « • • > i « ■ i * > « « * i • m * « i • • * •• < « ■ * *• *12 Reaction of dimethyl N-]D-toluenesulfonylphosphoramidate with d imethy1 sulfoxlde®*©©8ao®®e«®®aa®®oaaa®*o®®®©«©®®«®a®®®®13 Reaction of N-^-toluenesulfonyltrichlorophosphlnimine with dIme thy1 SUlfOX ide eo»>a««oao«o 9 e«flo9 i o o a » 0 o « o t o » « o » 4 >fte«i 1^4* Mechanism of the reaction® ® ®«©see«t®>«® 9 ®g®«®i®s<®®«s®®®®®«®<« ®13 Discussion of effect of substituents on reactivity of phosphinimines•••••••••••••••■•••••••••••••••••••••••••••13 Possibilities for future work®•••••••t®®®«®®®®®®®«®<®a®®*®®®®®#16 1,2-Cycloaddition route with N-sulfonyl- and N-acylisothiocyanatesee®®®®®®®®®^^®®®®®®®®®®®®®®®®®®®®®®®16 Reactivity of N-acyl- and sulfonyllsocyanates. •. ........ 17 Reaction of N-sulfonylisocyanates with sulfoxides®®18 Reactivity of isothiocyanate in terms of structure® ©. • ....... .18 Reaction of N-£-toluenesulfonylisothiocyanate with dimethyl sulf oxide ©.o®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®©.®®®©©® 19 New preparation for N-jd- toluene sulf onyl isothiocyanate...........19 Reaction of N-benzoylisothiocyanate with dibenzyl sulfoxide...♦20 Reaction of N-benzoylisothiocyanate with dimethyl sulfoxide.••.20 Possibilities for future work® ®«®®®®®o®®o®®®e®o®e®®®oo®®®®®®®® ®20 DESCRIPTION OF EXPERIMENTS e.®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®*®®®® 21 N-£-Toluenesulf onyltriphenylphosphinimlne •. *. ......... .22 Attempted reaction of N-jo-toluenesulf onyltriphenylphosphinimlne Wl th dIme thy1 sulf oxide ee««eaeea«««s«asea®®«®aaso«o®®®ae ® 2 2 V Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Page TristhyX phosphite©®©®#©©©©©©®©®©®©©©®®©©©®©®©®®©©©®®®©©®®®®®®®^^ N-jo-Toluenesulfonyltriethoxyphosphlnimine ....................... 22 Attempted Reaction of N-jo-toluenesulf onyltrlethoxyphosphinlmine with dimethyl sulf oxide ©©•©©©©©••©©©©©©©©©©©©©©©•©s©©©©®© 23 Diethyl N-jd-toluene sulf onylphosphoramldate® ...... 23 Dimethyl N-jo-toluene sulf onylphosphoramldate©.. © •.............. .23 Attempted reaction of dimethyl N-]D-toluenesulfonylphosphoramldate with d ime thy1 sulf oxide ©•©©©©•©•©©©■©•©••©©•••©©•oo©*«s©©23 N-g-Toluenesulf onyltrichlorophosphinimine © ©... ©.......... ...... 2^ Reaction of N-j>-toluenesulfonyltrichlorophosphinimine with d ime thy1 sulfoxlde9®®®©®®©©eo9©©©©o©oo©©t©©e®©®©©«®®®©©®©23 Reaction of N-jo-toluenesulfonyltrichlorophosphinimine with dipheny1 sulf OXlde»©9«e©o»©9o®»«©®o«9®9e»©90©©©®®»©8©®®8o23 N-Benzoy1 is o th1ocyanate ©a©©©©©®©©©©©©©©®©©©®©©©®®®©©©®©®®©®©®©© 26 Potassium N-^-toluene sulf onyl iminodithlocarbonate® ©•..•....©••• 26 N-j>-Toluenesulf onyllsothiocyanate .............. 26 Chlorination of Potassium N-j>-toluenesulfonylimino- d1th1ocarbonate ©«©©©«©»©©©•©©oo©©©©©©©©©©©©©©©©©©©©©©©©®® 27 Reaction of N-£-toluenesulfonyllsothiocyanate with dimethyl SUlfOXldeoo©e«©©©©«&oe©9«©©e©©«©o©©©®o«o®o©©Q©©®®o®©®®©®©2d Reaction of N-£-toluenesulfonylisothiocyanate with alkyl aryl SUlfOXldeS99©aoofie9©fle©a©o©«e©©©©©©®©«oe©9©©©©©o©©©®©®©©®23 Reaction of N-benzoylisothiocyanate with dlbenzyl sulfoxide.©«.29 Reaction of N-benzoylisothiocyanate with dimethyl sulfoxide..•.29 BIBLIOGRAPH Y ©o©9©«Q©©©©o0©«e©©©8O8Q©oo9®®®©©ae®©©oe©o9e©©®©®®©o3"^* Vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS PART II Page INTRODUCTION 36 Early hIs tory9©©©#®a®©®®®0®®®®®©®«®®®®09®©®®®®9®©©©©©®®®®®®©®®36 Structure of the isothiocyanate glucoside. ..........*37 Early Isolation. worlc© g®®®®®®®®®®®*©®®®©®®®®®®#©®®®*©®®®©®®®®© «3® Optical rotatory dispersion studies.............. ®>.®>®«39 Reaction of (-)-menthyl arenesulfinate ester with Grignard reagents 90®©®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®®© 40 Optical analog for isothiocyanate sulf oxides«. ............... 41 X-Ray study on isothiocyanate sulfoxides® •. ..... • ••*.. ®.......42 Purpose of this investigation® ©©o©®®©®©®®®®®®®®®®®®®®®®®®®®©© ©43 RESULTS AND DISCUSSION a®®®®®®®®®®®®®®®®®®®®®®®©®®©®*®®®©®®®©® ®44 (4") — Ethy 1 £-toly 1 sulf oxide 9®®®®®®®®®®®®®®®®®®®®®©®®®®®®®©®®®® 44 N-Methyl-N-^3-(methylsulfinyl)-propyl]-aniline.*..... .45 Assignment of absolute configuration. ©...... 46 Asymmetric Synthesis of jo-toluenesulfinate esters............. ®47 (-)-(JL)-Methyl phenyl sulfoxide via menthyl methanesulfinate..48 Purification1of (— )—isoborneol® e®®®®®®®®®®©®.®®®©©©®©©©©©©®©® ®48 ( + )-(R_)-Methyl £-tolyl sulfoxide via (-)-hornyl (db)—me thane sulf1nate9©©o99««ee©©e©o«oo«9e©««9oo©«o©e®®«©49 (+)-(Jj“Methyl phenyl sulfoxide via (-)-isobornyl (dc)—me thane sulf inate 0®©®®©©©..©®®®©®©.©®®®®®®®®©®©©©©©©® ^0 vii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Page ( + )-ii-Butyl methyl sulfoxide via (-)-cholesteryl (i )-methanesulf inate oaoooeoaaooeeeaao.eeaooooeeaaaaaoeooo
Load more

Recommended publications
  • Reactivity and Structural Diversity in the Reaction Of
    Reactivity and Structural Diversity in the Reaction of Guanidine 1,5,7-Triazabicyclo[4.4.0]dec-5-ene with CO 2 , CS 2 , and Other Heterocumulenes Niklas von Wolff, Claude Villiers, Pierre Thuéry, Guillaume Lefèvre, Michel Ephritikhine, Thibault Cantat To cite this version: Niklas von Wolff, Claude Villiers, Pierre Thuéry, Guillaume Lefèvre, Michel Ephritikhine, etal.. Reactivity and Structural Diversity in the Reaction of Guanidine 1,5,7-Triazabicyclo[4.4.0]dec-5-ene with CO 2 , CS 2 , and Other Heterocumulenes. European Journal of Organic Chemistry, Wiley-VCH Verlag, 2017, 2017, pp.676-686. 10.1002/ejoc.201601267. cea-01447886 HAL Id: cea-01447886 https://hal-cea.archives-ouvertes.fr/cea-01447886 Submitted on 27 Jan 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Reactivity and Structural Diversity in the Reaction of the TBD Guanidine with CO2, CS2 and Other Heterocumulenes Niklas von Wolff,[a] Claude Villiers,[a] Pierre Thuéry,[a] Guillaume Lefèvre,[a] Michel Ephritikhine*[a] and Thibault Cantat*[a] Abstract: The guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene
    [Show full text]
  • Carbenes, Heteroaryl(Trifluoromethyl)Carbenes and Phenylbis(Trifluoromethyl)Carbenes
    University of Nevada, Reno Matrix Isolation of Aryl(trifluoromethyl)carbenes, Heteroaryl(trifluoromethyl)carbenes and Phenylbis(trifluoromethyl)carbenes A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry by Pei Wang Dr. Robert S. Sheridan/Dissertation Advisor August, 2015 THE GRADUATE SCHOOL We recommend that the dissertation prepared under our supervision by PEI WANG Entitled Matrix Isolation Of Aryl(Trifluoromethyl)Carbenes, Heteroaryl(Trifluoromethyl)Carbenes And Phenylbis(Trifluoromethyl)Carbenes be accepted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Dr. Robert S. Sheridan, Advisor Dr. Kent M Ervin, Committee Member Dr. Chris Jeffrey, Committee Member Dr. Paula J Noble, Committee Member Dr. W. Patrick Arnott, Graduate School Representative David W. Zeh, Ph. D., Dean, Graduate School August, 2015 i Abstract We have isolated and studied 2-naphthyl(trifluoromethyl)carbene, 1- naphthyl(trifluoromethyl)carbene, 4-pyridyl (trifluoromethyl)carbene, 2-pyridyl (trifluoromethyl)carbene, 3-pyridyl (trifluoromethyl)carbene, 3-bromo-5-pyridyl (trifluoromethyl)carbene, meta-phenylbis(trifluoromethyl)carbene and para- phenylbis(trifluoromethyl)carbene in low temperature matrices for the first time. The naphthyl(trifluoromethyl)carbenes are photostable and have triplet ground states in matrices as most of the other studied ary(trifluoromethyl)carbenes. The 1- and 2- naphthyl(trifluoromethyl)diazirines, the precursors of 1- and 2- naphthyl(trifluoromethyl)carbenes, have dissimilar geometric structures leading to different UV/Vis absorptions. In the studied pyridyl(trifluoromethyl)carbenes, 4- pyridyl(trifluoromethyl)carbene was the most stable one in matrice: no photoproduct from 4- pyridyl(trifluoromethyl)carbene was observed. However, we obtained a small amount of photoproducts of 2 - pyridyl(trifluoromethyl)carbene, even though the result was not repeatable.
    [Show full text]
  • Gas Phase Synthesis of Interstellar Cumulenes. Mass Spectrometric and Theoretical Studies."
    rl ì 6. .B,1l thesis titled: "Gas Phase Synthesis of Interstellar Cumulenes. Mass Spectrometric and Theoretical studies." submitted for the Degree of Doctor of Philosophy (Ph.D') by Stephen J. Blanksby B.Sc.(Hons,) from the Department of ChemistrY The University of Adelaide Cì UCE April 1999 Preface Contents Title page (i) Contents (ii) Abstract (v) Statement of OriginalitY (vi) Acknowledgments (vii) List of Figures (ix) Phase" I Chapter 1. "The Generation and Characterisation of Ions in the Gas 1.I Abstract I 1.II Generating ions 2 t0 l.ru The Mass SPectrometer t2 1.IV Characterisation of Ions 1.V Fragmentation Behaviour 22 Chapter 2 "Theoretical Methods for the Determination of Structure and 26 Energetics" 26 2,7 Abstract 27 2.IT Molecular Orbital Theory JJ 2.TII Density Functional Theory 2.rv Calculation of Molecular Properties 34 2.V Unimolecular Reactions 35 Chapter 3 "Interstellar and Circumstellar Cumulenes. Mass Spectrometric and 38 Related Studies" 3.I Abstract 38 3.II Interstellar Cumulenes 39 3.III Generation of Interstellar Cumulenes by Mass Spectrometry 46 3.IV Summary 59 Preface Chapter 4 "Generation of Two Isomers of C5H from the Corresponding Anions' 61 ATheoreticallyMotivatedMassSpectrometricStudy.'. 6l 4.r Abstract 62 4.rl Introduction 66 4.III Results and Discussion 83 4.IV Conclusions 84 4.V Experimental Section 89 4.VI Appendices 92 Chapter 5 "Gas Phase Syntheses of Three Isomeric CSHZ Radical Anions and Their Elusive Neutrals. A Joint Experimental and Theoretical Study." 92 5.I Abstract 93 5.II Introduction 95 5.ru Results and Discussion t12 5.IV Conclusions 113 5.V Experimental Section ttl 5.VI Appendices t20 Chapter 6 "Gas Phase Syntheses of Three Isomeric ClHz Radical Anions and Their Elusive Neutrals.
    [Show full text]
  • Title of Thesis Or Dissertation, Worded
    DEVELOPMENT OF CHEMICAL TOOLS FOR STUDYING REACTIVE SULFUR SPECIES by MATTHEW MICHAEL CERDA A DISSERTATION Presented to the Department of Chemistry and Biochemistry and the Graduate School of the University of Oregon in partial fulfillment of the requirements for the degree of Doctor of Philosophy June 2020 DISSERTATION APPROVAL PAGE Student: Matthew Michael Cerda Title: Development of Chemical Tools for Studying Reactive Sulfur Species This dissertation has been accepted and approved in partial fulfillment of the requirements for the Doctor of Philosophy degree in the Department of Chemistry and Biochemistry by: Michael M. Haley Chairperson Michael D. Pluth Advisor Darren W. Johnson Core Member Raghuveer Parthasarathy Institutional Representative and Kate Mondloch Interim Vice Provost and Dean of the Graduate School Original approval signatures are on file with the University of Oregon Graduate School. Degree awarded June 2020 ii © 2020 Matthew Michael Cerda This work is licensed under a Creative Commons Attribution-NonCommerical-NoDerivs (United States) License. iii DISSERTATION ABSTRACT Matthew Michael Cerda Doctor of Philosophy Department of Chemistry and Biochemistry June 2020 Title: Development of Chemical Tools for Studying Reactive Sulfur Species Hydrogen sulfide (H2S) has recently emerged as an important biological signaling molecule involved in a number of key physiological processes. These observations have generated interest in harnessing H2S as a potential therapeutic agent to treat disease states and chronic conditions associated with H2S-based signaling. A mechanistic analysis of these physiological processes reveals the prevalence of H2S and other reactive sulfur species including sulfane sulfur and persulfides. To better understand the biological properties of these reactive sulfur species, chemical tools which provide methods of generating these fleeting species under controlled reaction conditions are needed.
    [Show full text]
  • AIM and NBO Analysis of Oxocarbon Heterocumulenes As Divalent Carbon(0) Species Final Paper
    Massachusetts Institute of Technology 5.05 Main Group Chemistry AIM and NBO Analysis of Oxocarbon Heterocumulenes as Divalent Carbon(0) Species Final Paper Author: Jonathan Melville Instructor: Christopher C. \Kit" Cummins December 13, 2016 Contents 1 Abstract 1 2 Introduction 1 3 Results and Discussion 1 3.1 Dicarbon Monoxide (C2O)..........................1 3.1.1 C2O..................................2 3.1.2 C2O·BH3 ...............................2 3.1.3 C2O·2 BH3 ..............................3 3.1.4 C2O·3 BH3 ..............................4 3.2 Carbon Suboxide (C3O2)...........................5 3.2.1 C3O2 ..................................6 3.2.2 C3O2·BH3 ...............................7 3.2.3 C3O2·2 BH3 ..............................8 4 Experimental 9 5 Conclusion 9 6 Acknowledgments 10 References 10 List of Figures 1 NRT-calculated C2O resonance structures . .2 2 C2O geometry . .2 3 C2O·BH3 geometry . .2 4 NRT-calculated C2O·BH3 resonance structures . .3 5 C2O·2 BH3 geometry . .3 6 NRT-calculated C2O·2 BH3 resonance structures . .4 7 NRT-calculated C2O·3 BH3 resonance structures . .5 8 C2O·3 BH3 geometry . .5 9 NRT-calculated C3O2 resonance structures . .6 10 C3O2 geometry . .6 11 C3O2·BH3 geometry . .7 12 NRT-calculated C3O2·BH3 resonance structures . .7 13 C3O2·2 BH3 geometry . .8 14 NRT-calculated C3O2·2 BH3 resonance structures . .9 List of Tables 1 NRT resonance state weightings of C2O. .2 2 Selected NRT resonance state weightings of C2O·BH3............3 3 Selected NRT resonance state weightings of C2O·2 BH3...........4 4 Selected
    [Show full text]
  • Aspects of Heterocyclisation Reactions Mediated by Nucleophilic Interaction of Aromatic Nitro Groups with Ortho Heterocumulene Side Chains
    Issue in Honor of Dr. Douglas Lloyd ARKIVOC 2002 (iii) 80-89 Aspects of heterocyclisation reactions mediated by nucleophilic interaction of aromatic nitro groups with ortho heterocumulene side chains Kevin J. Duffy,† a George Tennant,* a Christopher J. Wallis,b and George W. Weaver ‡ a a Department of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, UK b GlaxoSmithKline Medicines Research Centre, Gunnels Wood Road, Stevenage, SG1 2NY, UK E-mail: [email protected] Dedicated to Douglas Lloyd on the occasion of his 80th birthday Abstract Evidence is presented for the involvement of ketene intermediates in the thermal transformations of ethyl 4-nitro-1H-imidazol-5-ylethanoates into 4H-imidazo[4,5-c]isoxazole derivatives. Direct heterocyclisation of a 1-(4-nitro-1H-imidazol-5-yl)-3-phenylcarbodiimide intermediate is proposed to account for the reaction of a triphenyl N-(4-nitro-1H-imidazol-5-yl)phosphinimine with phenyl isocyanate exemplifying a new, flexible, and potentially general route to 2-aryl- 2H,4H-imidazo[4,5-d][1,2,3]triazoles. Keywords: Heterocyclisation, thermal transformations, ketene, ethyl 4-nitro-1H-imidazol-5- ylethanoates, 4H-imidazo[4,5-c]isoxazoles Introduction Direct interaction of the nitro substituent with electron-rich and electron-poor side-chains in ortho-substituted nitroaromatic and nitroheteroaromatic compounds is a well documented1-3 and fruitful source of novel heterocyclisation reactions. However, among such processes, heterocyclisations initiated by the nucleophilic interaction of aromatic/heteroaromatic nitro groups with ortho heterocumulene substituents are relatively rare. Seminal examples include (Scheme 1), the thermolysis4 of 2-nitrophenyl isocyanate 1 to benzofurazan 2, and the deep-seated thermal conversion5 of 1-(2-nitrophenyl)-3-phenylcarbodiimide 3 into 2-phenyl-2H- benzo-1,2,3-triazole 4.
    [Show full text]
  • Generation of Electron Deficient Carbodiimides and Their
    University of Vermont ScholarWorks @ UVM Graduate College Dissertations and Theses Dissertations and Theses 2017 Generation Of Electron Deficient Carbodiimides And Their Application In The uaG nidine Forming, Zwitterionic 1,3-Diaza-Claisen Rearrangement Joel Walker University of Vermont Follow this and additional works at: https://scholarworks.uvm.edu/graddis Part of the Organic Chemistry Commons Recommended Citation Walker, Joel, "Generation Of Electron Deficient Carbodiimides And Their Application In The uaG nidine Forming, Zwitterionic 1,3-Diaza-Claisen Rearrangement" (2017). Graduate College Dissertations and Theses. 674. https://scholarworks.uvm.edu/graddis/674 This Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks @ UVM. It has been accepted for inclusion in Graduate College Dissertations and Theses by an authorized administrator of ScholarWorks @ UVM. For more information, please contact [email protected]. GENERATION OF ELECTRON DEFICIENT CARBODIIMIDES AND THEIR APPLICATION IN THE GUANIDINE FORMING, ZWITTERIONIC 1,3-DIAZA- CLAISEN REARRANGEMENT A Dissertation Presented by Joel Walker to The Faculty of the Graduate College of The University of Vermont In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy Specializing in Chemistry January, 2017 Defense Date: October 18, 2016 Dissertation Examination Committee: José S. Madalengoitia, Ph.D., Advisor Adrian Del Maestro, Ph.D., Chairperson Adam Whalley, Ph.D. Matthew Liptak, Ph.D. Cynthia J. Forehand, Ph.D., Dean of the Graduate College ABSTRACT The 1,3-diaza Claisen rearrangement was initially discovered by the Madalengoitia group in the early 2000s. Tertiary, allylic, amines nucleophilically add to the carbon of a heterocumulene (isocyanate, isothiocyanate, or carbodiimide) to generate a zwitterion which then undergoes [3,3]-sigmatropic rearrangement.
    [Show full text]
  • Preparation of Benzoenyne -Allenes, Enyne
    Graduate Theses, Dissertations, and Problem Reports 2002 Preparation of benzoenyne -allenes, enyne -isocyanates and enyne -carbodiimides and their applications in the synthesis of polycyclic aromatic hydrocarbons and heterocycles Hongbin Li West Virginia University Follow this and additional works at: https://researchrepository.wvu.edu/etd Recommended Citation Li, Hongbin, "Preparation of benzoenyne -allenes, enyne -isocyanates and enyne -carbodiimides and their applications in the synthesis of polycyclic aromatic hydrocarbons and heterocycles" (2002). Graduate Theses, Dissertations, and Problem Reports. 1595. https://researchrepository.wvu.edu/etd/1595 This Dissertation is protected by copyright and/or related rights. It has been brought to you by the The Research Repository @ WVU with permission from the rights-holder(s). You are free to use this Dissertation in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you must obtain permission from the rights-holder(s) directly, unless additional rights are indicated by a Creative Commons license in the record and/ or on the work itself. This Dissertation has been accepted for inclusion in WVU Graduate Theses, Dissertations, and Problem Reports collection by an authorized administrator of The Research Repository @ WVU. For more information, please contact [email protected]. Preparation of Benzoenyne-Allenes, Enyne-Isocyanates and Enyne- Carbodiimides and Their Applications in the Synthesis of Polycyclic Aromatic Hydrocarbons and Heterocycles Hongbin Li A dissertation submitted to the Eberly College of Arts and Science at West Virginia University in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Organic Chemistry Kung K. Wang, Ph.D., Chair Harry O.
    [Show full text]
  • April 27-30, 2005
    Program and Abstracts Separations Program Heavy Element Chemistry Program Contractors’ Meeting Doubletree Hotel Rockville, Maryland April 27-30, 2005 Chemical Sciences, Geosciences, and Biosciences Division Office of Basic Energy Sciences Office of Science U.S. Department of Energy Cover graphics: Rigid and flexible calixarene-based ligands for selective metal ion separations (see abstract by BARTSCH et al.) Molecular structure of Pu(IV)-hyrdroxypyridonatye complex, a model for actinide decorporation agents (see abstract by GORDEN et al.) This document describes activities performed under contract number DE-AC05-00OR22750 between the U.S. Department of Energy and Oak Ridge Associated Universities. FOREWORD This abstract booklet provides a record of the sixth U.S. Department of Energy (DOE) contractors’ meeting in separations sciences and the third in heavy element chemistry. The Chemical Sciences, Geosciences and Biosciences Division of the Office of Basic Energy Sciences and its predecessors have sponsored research in heavy element chemistry and separations sciences for some sixty years. Although these are distinct disciplines, they have much in common for many reasons, in particular because novel separations research is needed to produce pure heavy-element samples and because heavy element chemistry provides the basis for many separations processes. In addition, separation processes are major industrial sources of energy consumption and waste generation. This is the second joint meeting of these programs. The objective of this meeting is to provide a fruitful environment in which researchers with common interests will present and exchange information about their activities, will build collaborations among research groups with mutually reinforcing strengths, will identify needs of the research community, and will focus on opportunities for future research directions.
    [Show full text]
  • Elucidation of Heterocumulene Activation by a Nucleophilic-At-Metal Iridium(I) Carbene Matthew T
    Subscriber access provided by Caltech Library Services Article Elucidation of Heterocumulene Activation by a Nucleophilic-at-Metal Iridium(I) Carbene Matthew T. Whited, and Robert H. Grubbs Organometallics, 2009, 28 (1), 161-166 • DOI: 10.1021/om8009766 • Publication Date (Web): 24 November 2008 Downloaded from http://pubs.acs.org on January 24, 2009 More About This Article Additional resources and features associated with this article are available within the HTML version: • Supporting Information • Access to high resolution figures • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Organometallics is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 provided by Caltech Authors View metadata, citation and similar papers at core.ac.uk CORE brought to you by Organometallics 2009, 28, 161–166 161 Elucidation of Heterocumulene Activation by a Nucleophilic-at-Metal Iridium(I) Carbene Matthew T. Whited and Robert H. Grubbs* Arnold and Mabel Beckman Laboratories of Chemical Synthesis, DiVision of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 ReceiVed October 9, 2008 A carbene complex supported by the (PNP)Ir framework is shown to facilitate sulfur-atom transfer from CS2 and PhNCS by an unusual multiple-bond metathesis pathway, and kinetically trapped intermediates are provided to support the proposed metal-initiated mechanism for heterocumulene activation. Experimental and theoretical studies on a series of (PNP)Ir-L complexes suggest that a high- lying, nucleophilic Ir(dz2) orbital mediates this unique reactivity. The combination of evidence indicates that square-planar Ir(I) carbenes of this type are best formulated as nucleophilic-at-metal carbenes, exhibiting reactivity initiated by a nucleophilic metal center rather than a nucleophilic or electrophilic carbene and providing products that are complementary to those typically observed for high-valent alkylidenes.
    [Show full text]
  • Zouchoune, B. ELECTRONIC STRUCTURE and RELATIVE STABILITIES of 10-AND 12-VERTEX
    NBO 2018 – 1969 references Updated by Ariel Andrea on 2019-04-05 Ababsa, S.; Zouchoune, B. ELECTRONIC STRUCTURE AND RELATIVE STABILITIES OF 10-AND 12-VERTEX. CLOSO- AND NIDO- HETEROBORANE CLUSTERS OF Ga, Ge, AND As ELEMENTS Journal of Structural Chemistry, (59): 276-289. 2018. 10.1134/s002247661802004x Abbasi, A.; Sardroodi, J. J. A highly sensitive chemical gas detecting device based on N-doped ZnO as a modified nanostructure media: A DFT plus NBO analysis Surface Science, (668): 150-163. 2018. 10.1016/j.susc.2017.10.029 Abbasi, A.; Sardroodi, J. J. Investigation of the adsorption of ozone molecules on TiO2/WSe2 nanocomposites by DFT computations: Applications to gas sensor devices Applied Surface Science, (436): 27-41. 2018. 10.1016/apsusc.2017.12.010 Abbenseth, J.; Bete, S. C.; Finger, M.; Volkmann, C.; Wurtele, C.; Schneider, S. Four- and Five-Coordinate Osmium(IV) Nitrides and Imides: Circumventing the "Nitrido Wall" Organometallics, (37): 802-811. 2018. 10.1021/acs.organomet.7b00707 Abdel-Latif, S. A.; Mohamed, A. A. Novel Zn(II) complexes of 1,3-diphenyl-4-(arylazo)pyrazol-5-one derivatives: Synthesis, spectroscopic properties, DFT calculations and first order nonlinear optical properties Journal of Molecular Structure, (1156): 712-725. 2018. 10.1016/j.molstruc.2017.12.028 Abdel-Latif, S. A.; Mohamed, A. A. Synthesis, spectroscopic characterization, first order nonlinear optical properties and DFT calculations of novel Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) complexes with 1,3-diphenyl-4-phenylazo-5- pyrazolone ligand Journal of Molecular Structure, (1153): 248-261. 2018. 10.1016/j.molstruc.2017.10.002 Abdel-Latif, S.
    [Show full text]
  • The Chemistry of Transition Metals with Three-Membered Ring Heterocycles Chung-Yang (Dennis) Huang and Abigail G
    Review pubs.acs.org/CR The Chemistry of Transition Metals with Three-Membered Ring Heterocycles Chung-Yang (Dennis) Huang and Abigail G. Doyle* Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States 11. Germiranes 8191 12. Conclusion 8192 Author Information 8192 Corresponding Author 8192 Notes 8192 Biography 8192 Acknowledgments 8192 Abbreviations 8192 CONTENTS References 8193 1. Introduction 8153 2. Epoxides 8154 2.1. Carbonylations 8154 1. INTRODUCTION 2.2. Carboxylations 8155 The chemistry of three-membered ring heterocycles has played 2.3. Deoxygenations 8156 a dominant role in the history of organic synthesis.1 Countless 2.4. Isomerizations 8156 classic and modern protocols exist for their preparation from 2.5. Hydrogenations 8158 simple starting materials. At the same time, the intrinsic ring 2.6. Cross-Coupling Reactions 8159 strain of these compounds primes them for facile ring-opening. 2.7. Miscellaneous Isolated Organometallic Com- As a result, much attention continues to be given to the plexes from Epoxides 8161 discovery of reactions that harness the reactivity of three- 3. Aziridines 8162 membered ring heterocycles as entry points to the synthesis of 3.1. Carbonylations 8162 complex heteroatom-containing products. 3.2. Cycloadditions 8164 Transition metal chemistry is another field that has seen a 3.3. Isomerizations 8165 long history of development. A detailed understanding of the 3.4. Hydrogenations 8166 properties of organometallic complexes and the mechanisms of 3.5. Cross-Coupling Reactions 8166 their reactions has facilitated the design of practical method- 3.6. Miscellaneous Isolated Organometallic Com- ologies that are widely utilized in synthetic chemistry. plexes from Aziridines 8168 Combining organometallic chemistry with reactions of three- 4.
    [Show full text]