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WALKER, Charles Carey, 1936- PART I: the PREPARATION, PROPERTIES and CHEMISTRY of TRIPHENYLPHOSPHAZINES and N-BENZAMIDOTRIPHENYLPHOSPHINIMINE

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WALKER, Charles Carey, 1936- PART I: the PREPARATION, PROPERTIES and CHEMISTRY of TRIPHENYLPHOSPHAZINES and N-BENZAMIDOTRIPHENYLPHOSPHINIMINE This dissertation has been microiihned exactly as received 66—6309 WALKER, Charles Carey, 1936- PART I: THE PREPARATION, PROPERTIES AND CHEMISTRY OF TRIPHENYLPHOSPHAZINES AND N-BENZAMIDOTRIPHENYLPHOSPHINIMINE. PART II: THE REACTION OF GLYOXAL WITH P-TOLUENESULFONYL HYDRAZIDE AND 12-NAPHTHALENESULFONYL HYDRAZIDE: THE BASE CATALYZED DECOMPOSITION OF VICINAL- T :^ M ’0LUENESULF0NAMID0-1 ,2,3-TRIAZ OLES. PART IE: THE ATTEMPTED PREPARATION OF University Microfilms, Inc., Ann Arbor, Michigan This dissertation has been microiihned exactly as received 66-6309 WALKER, Charles Carey, 1936- BICYCLIC AMIDES. The Ohio State University, Ph.D., 1965 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan PART I TBE PREPARATION, PROPERTIES AND CHEMISTRY OF TRIPHENYL­ PHOSPHAZINES AND N-BENZAMDOTKEPHENYLPHOSPHINIMIHE PART II THE REACTION OF GLYOXAL WITH P-TOLUENESULFONYL HYDRAZIDE AND ÿ-NAPHTHALENESULFONYL HYDRAZIDE: THE BASE CATALYZED DECOMPOSITION OF VICINAL-BIS-P-TOLUENESULFONYLHYDRAZONES AND 1-P-TOLUENESULFONAMIDO-l, 2,3-TRIAZOLES PART III THE ATTEMPTED PREPARATCON OF BICYCUC AMIDIS DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Charles Carey Walker, B,Sc., M.Sc« The Ohio State University 1965 Approved by Adviser Department of Chemistry Dedicated to my wife, Diane, whose patience and understanding helped make this nossible. 11 ACKNOWLEDGMENTS I wish to thank Dr. Harold Shechter for his assistance and direction in the course of this work, and for his invaluable help in the preparation of this manuscript. Thanks also are given to fellow graduate students and professors for many helpful discussions and donations of time and materials. I also am grateful to the Chemistry Department, The Sinclair Corporation, Union Carbide and Carbon Corporation, E. I. du Pont de Nemours Company (inc.) and the National Science Foundation for finan­ cial assistance. Ill VITA September 30, 193o--------- Born, Pittsburgh, Pennsylvania 1 9 5 8 ---------------------B.Sc. - John Carroll University, Cleveland, Ohio i960--------------------- M. Sc. - John Carroll University, Cleveland., Ohio 1960-1961 ----------------- Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1961-196 2----------------- Union Carbide Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio 1962-196 3----------------- Sinclair Fellow, Department of Chemistry, Hie Ohio State University, Columbus, Ohio 1963-196 5----------------- Research Fellow, Department of Chemistry, The Ohio State University, Columbus, Ohio IV CONTENTS PART I THE PREPAR/iTION, PROPERTIES AND CHEffiSTRY OR TRIPHENYLPHOSPHAZINES AND N-BENZAMIDOTRIPHENYLPHOSPHINIMINE Page INTRODUCTION ............................................ 2 HISTORICAL.............................................. DISCUSSION.......... 6 EXPERBIENTAL............................................ 3O General Inforination ................................ 30 Reactions of II:7Rrazinotriphen3'’lphosphoniU]n Bromide with Aldehydes and Ketones. A New Synthesis of Triphenylphosphaziniuin Hydr obr oral des................. 3I Reaction with acetaldehyde ...................... 3I butyraldéhyde ..................... 3I bensaldehyde .................. ^3 £-methoxybenzaldehyde ............. 03 £-nitrobenzaldehyde .............. ?i, cinnamaldéhyde .................... 25 acetone .......................... 35 cyclohexanone....... 36 acetophenone ...................... 30 mesityl oxide ..................... oj benzophenone ................ 37 benzil........................... f luorenone........................ 3Q 9 ^10-phenanthrenequinone ........... 30 The Reaction of Triphenylphosphaziniura Hydrobromides with Base. A New Synthesis of Triphenylphosphazines... kO CONTENTS (Contd.) Pa.Ke Acetone triphenylphosphaziniuia hydrobranide........ ):0 Benzaldehyde triphenylphosphaziniuia hydrobromide ):l Acetophenone triphenylphosphaziniura hydrobromide .... k2 Fluorenone triphenylphosphazinium hydrobromide..... k-2 ^-Nitrobenzaldehyde triphenylphosphaziniuia hydrobromide.................................. 4] Isobutyraldéhyde triphenylphosphazinium hydrobromide ........................... 4] Cyclohexanone triphenylphosphaziniuia hydrobromide .......................... Lli Reactions of N-/\minotriphenylphosphinimine with Carbonyl Compounds .................... ......... Reaction with £-nitrobenzaldehyde.................. acetophenone.............. ........ .. benzophenone ................ 46 fluorenone ........... 4^ Atterapted Decomposition of Triphenylphosphazines ........ 48 Acetophenone triphenylphosphazine with methyl iodide ......... 48 Fluorenone triphenylphosphazine with methyl iodide .................................. 48 £-I'Iitrobenzaldehyde triphenylphosphazine with methyl iodide.............................. ll_8 Therraolysis of acetophenone triphenyl­ phosphazine in tetrahydrofuran........ 48 Pyrolysis of acetophenone triphenylphosphazine...... J1.9 Irradiation of acetophenone triphenylphosphazine ]|.c) Vacuuia pyrolysis of fluorenone triphenylphosphazine...... l|.o The Preparation, Properties and Reactions of N-Benzam.idotriphenylphosphinimine.................... 1|.q Preparation of IJ-benzamidotriphenylphosphinimine 51 Preparation of o(-hydroxybenzylidenetriphenyl- phosphininine .................................. 53 Reaction of o(-hydroxybenzylidenetriphenylphos- phazine with benzoyl chlorides .................. 56 VI CONÏEHTS (Contd.) PART II Page THE REi'vCTION OF GLYOXAL VŒTH P-TOLUEIIESULFOIIYL HYDRAZIDE AMD P-N/\PI'ITHi'\LSWESULFOÎJYL HYDRAZIDE; THE BASE CATALYZED DECOM­ POSITION OF VICIimL-BIS-TOSYU-IYDRALOKES AND l-p-TOLUENESUL- FOM/LUDO-I ,2,3 -TRIALOLES Page X INTRODUCTION .............................................. 65 EESTORIC.'L................................................ 69 DISCUSSION................................................ jh. EÎCPERIMSNT/L ....................................... 80 Genei’al Iniomation .................................. 80 Tlie Attempted Preparation of Glyoxal Mono-£- toluenesulfonylhydrazone and Glyoxal Mono-^-naphtlialenesulfonylhydrazone.............. BO Decompositions ....................................... 86 Glyoxal bis-p-tosylhydrazone ...................... 86 Biacetyl bis-p-tosylhydrazone......................... 88 Pyruvic aldehyde bis-p-tosylhydrazone ............. 91 Benzil bis-p-tosylhydrazone ....................... 09 4 ,4 '-Dinitrobenzil bis-p-tosylhydrazone ...... 93 4 ,4 '-Dimethoxybenzil bis-p-tosylhydrazone .......... 95 Methylphenylglyoxal bis-p-nitrobenzene- sulfonylhydrazone ..................... gy PART III TES ATTEMPTED PREPARATION OF BRIDGED AMIDES Page INTRODUCTION .............................................. 100 HISTORICAL................................................ 101 DISCUSSION.................................... 104 vii COMTEIWS ( Contd. ) Page EŒERII'IEMTAl ............................................. lOG The Pyrolysis of 4 ,5-Dietho%y-4 ,5-Diphenyl- 2-Iiiiidazolidine ................................... 108 The Attempted Preparation of 1 ,5-Diazobieyclo- 12) : 2 : g -6/f-diphenyl-6-octen-8-one ................ 108 The Attempted Preijaration of 4 ,^-Diphenyl-l-g^- Toluenesulfonyl-4 -l!nidazolin-2-one .................. 110 Vlll T/LBLES (Part l) Table Page 1 . Triphenylphosphaainimi Salts and. Triphenyl­ phosphazines from Hydrazinotriphenyl- phosphoniuin Bromides and Aldehydes or Ketones .......................................... 11 2 . Triphenylphosphazines from K-/toino-triphenyl- phosphinii.iine andAldehydes or Ketones .................. 15 3 . I,3 ,i4— Oxadiazoles from o<-Hydroxybenzylidene— triphenylphosphazine and Benzoyl Chlorides ............... 23 T-'lBLSS (PART II) 1 . Acetylenes formed from Vicinal-bis-tosylhydrazones ....... JJ 2. 1 ;2 ,3-Triazoles formed from Vdrcinal-bis- tosylhydrazones ............... JJ IX ILLUSm\TIOKS Figure Page Ini'rared Spectra of the '.Criphenylphosphaziniuia Kydrobroiaides of - 1. Butyraldéhyde ....................................... 59 2. Benzaldehyde .............................. 59 3. £-Nitrobenzaldehyde do U. Acetophenone .................................... 60 5. Fluorenone ........................................... 60 Infrared Spectra of the Triphenylphosphazines of 6. Acetophenone ......................................... 60 7. Fluorenone ........................................... 51 8. ]j-Nitrobensaldehyde ........................... 8l 9. Benzophenone ......................................... 6l Infrared Spectra of IT-Benzatnidotriphenylphosphiniiiiine ....... 9 " 12. 53 c^-Eydroxybenzylidenetriphenylphosphazine ............... 62 1:" - 63 X PART I THE PREPARATION, PROPERTIES AND CHEMISTRY OF TRIPHENYLPHOSPHAZINES AND N-BENZAMDOTRIPHENYL- PHOSPHINIMINE. INTRODUCTION Staudinger and Meyer (l) in attempts to prepare phosphoranes I (l) H. Staudinger and J. Meyer, Helv. Chim. Acta, 2 , 619 (19IO). (Equation l) by decomposition of diazo compounds in the presence of triphenylphosphine isolated instead simple adducts which were named phosphazines II (Equation 2 ). R'gP^CEg+Ng (1) R'oP + Eg CNg (I) > RA P=N-N=GRg (2) (II) This reaction of a diazo compound with triphenylphosphine subsequently was employed for synthesis of a variety of triphenylphosphazines (2). (2) a. H. Staudinger and G. Lus cher, Helv. Chim. Acta, 5,^75 (1922); b. F. Ramirez and S. Levy, J. Org. Chem., 23, 20]6 (1998)j c. H. J, Bestmann, H. Buckschewski, and H. Leube, Ber., 92, 13^5 (1959); d. W.
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