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Carbenic and Cationic Reactions of 3-Diazo-2, 5-Diphenylpyrrole

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Carbenic and Cationic Reactions of 3-Diazo-2, 5-Diphenylpyrrole INFORMATION TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Pagafsj". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image on the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image. You will find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It is customary to begin photoing at the upper left hand corner of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row and continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. 5. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. University Microfilms International 300 North Zeeb Road Ann Arbor. Michigan 48106 USA St. John's Road, Tyler's Careen High Wycombe, Bucks, England HP10 8HR I\ 78-12,372 NAGARAJAN, Madhavarao, 1951- CARBENIC AND CATICNIC REACTIONS OF 3-DIAZO-2, 5-DIPHENYLFVRROLE. The Ohio State University, Ph.D., 1978 Chemistry, organic University Microfilms International, Ann Arbor, Michigan 48ioe CARBENIC AND CATIONIC REACTIONS OF 3-DIAZO-2,5-DIPHENYLPYRROLE Dissertation Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By M. Nagarajan, B.Sc., M.Sc, * * * * * The Ohio State University 1978 Reading Committee: Approved by Dr. H. Shechter Dr. L. A. Paquette Dr. J. A. Secrist III Adviser Department of Chemistry To my family ACKNOWLEDGMENT I wish to express my thanks to Dr. Harold Shechter for his help and advice during the course of this research and his expert guidance in preparing this dissertation. To my colleagues, especially Drs. P.J. Card, T.V. Rajan Babu, K.T. Chang, Ms. Mridula Nair and Mr. P.R. Menard, I express my appreciation for their help and encouragement. Financial support from The National Institute of Health, The National Science Foundation, The Stauffer Chemical Company, and The Ohio State University is gratefully acknowledged. iii VITA June 17, 1951 ................. Born, Madras, India 197 ......................... B.Sc., University of Madras, Madras, India 1973 . M.Sc., Indian Institute of Technology, Madras, India 1 9 7 3 - 1 9 7 5 ................... Teaching Associate, The Ohio State University, Columbus, Ohio 1975 - 1976 ...................Research Associate, 19//1977 - oresentpresent Columbus,The Ohio stateOhio University, 1976 - 1977 ................... Stauffer Chemical Company Fellow, The Ohio State University, Columbus, Ohio FIELD OF STUDY Organic Chemistry TABLE OF CONTENTS Page ACKNOWLEDGMENTS................................... iii VITA .............................................. iv Chapter STATEMENT OF THE PROBLEM .................... 1 I. HISTORICAL................................ 2 II. RESULTS AND DISCUSSION ................... 19 III. EXPERIMENTAL.............................. 95 REFERENCES ................... 149 V STATEMENT OF PROBLEM The present study is an investigation of the chemistry of 3-diazo-2,5-diphenylpyrrole (1), 2,5-diphenyl-3H- pyrrolylidene (2), and 2, 5-diphenylpyrrole-3-diazonium salts <3)* ©v0^ ^ - a . C6H5j N s C6H5 S V " C6H5 C6H5 X N ^ C6H5 . The principal objectives of this research were (a) to determine the products of thermal and photolytic reactions of 1, 2, and 3 with various substrates; (b) to characterize the behaviour of 2 in its singlet (2s) and triplet (2t) iv 11 65 C -.H65 p . 65 65 2s 2t states and (c) to explore the possibility of using the above reactions for advantageous purposes in synthetic organic chemistry. 1 CHAPTER I. HISTORICAL In 1953, Doering and DePuy^ reported synthesis of diazocyclopentadiene (4). Unlike many other diazo compounds, 4 proved to be unusually stable. A principal reason for the stability of 4 is attributed to resonance in which the cyclopentadiene ring develops negative charge and an aromatic sextet as in 5. One of the logical 4 5 developments of 4 is its conversion to cyclopenta- dienylidene (6), a carbene of intense theoretical interest. Like 4, 6 also has a canonical form 7 in which a cyclic 611 electron system can be attained. Calculations indicate2 6 7 1W. von E. Doering and C.H. DePuy, J. Am. Chem. Soc., 75, 5955 (1953). 2 R. Gleiter and R. Hoffmann, J. Am. Chem. Soc., 90, 5457 (1968). 2 3 that 6**7 is indeed stabilized and as such will have electrophilic properties. ESR studies# however, have conclusively established the ground state of 6 to be a 3 triplet. The chemistry of 6 indicates that its reactions proceed through its singlet state. Thus, 6 adds to 4 5 olefins with retention of stereochemistry * (Eq. 1). (1) 6 100% Addition to p-substituted styrenes as in Eq. 2 results in a kinetic p value of -0.76 with a constants or p = -0.46 withct+ constants, thus revealing that 6 behaves as an 6 electrophile. 3 E. Wasserman, L. Barash, A.M. Trozzolo, R.W. Murray, and W.A. Yager, J. Am. Chem. Soc., 86, 2304 (1964). *R.A. Moss, J. Ora. Chem., 31, 3296 (1966). 5 R.A. Moss, and J.R. Przybyla, J. Orq. Chem., 33, 3816 (1968). g H. Durr and F. Werndorff, Anqew. Chem. Intemat. Edn. 13, 483 (1974). 4 6 + X - ^ O y ~ CH=CH2 --- > (2) Photolysis of 4 in benzene produces, presumably via 6, spironorcaradiene 8; 8, however, rearranges readily to Q bicyclo[6.3.0]undeca-[l , 2, 4,6, 9]-pentaene (11) via 7 spiro[6.4]undecapentaene 9 and thence 1£ (Eq. 3). O hv 4 + @ 8 9 (3) 10 11 Di-, tri-, and tetraphenyldiazocyclopentadienes show Q Q behavior similar to 4. ' A likely explanation for the singlet character of 6 and its phenyl derivatives is that the carbenes are so reactive as generated that their D. Schoenleber, Chem. Ber., 102, 1789 (1969). 8H. Durr and G. Scheppers, Chem. Ber.,103, 380 (1970). *H. Durr and L. Schrader, Chem. Ber., 102, 2026 (L969) . 5 intermolecular reactions occur faster than intersystem crossing to their triplet states. Although 4 and its derivatives have been intensively researched, little is known of the chemistry of their heterocyclic analogs even though some of them have been known for a long time. Angelico synthesized 3-diazo-2,5- diphenylpyrrole (!L) and 3-diazo-2, 4,5-triphenylpyrrole (lj2) by diazotizing their corresponding amines with nitrous acid and subsequent neutralization (Eq. 4).^° (4) C,H ' c ^-h : Ca H- 6 5 jj 65 o 5 6 5 R = H 1 R = C,Hc 12 6 5 ~~~ Fischer and co-workers, in their investigation of porphyrins, prepared 2-carbethoxy-3,5-dimethylpyrrole-4- diazonium salts by diazotization of 4-amino-2-carbethoxy- 3,5-dimethylpyrrole.^ ^ F . Angelico, Atti. Acad. Naz. Lincei., 14, II, 167 (1905) . ^ H . Fischer and A. Stern, Ann. Chem., 446, 229 (1926). 6 Synthesis of diazocyclopentadiene by routes which do not involve precursor amines prompted a search for related methods applicable to 5-membered heterocyclic systems. In 1960, 3-diazo-2,4,5-triphenylpyrrole (12) was prepared by reaction of 2,3,5-triphenylpyrrole and nitrous acid. 12 Application of this method to 2,5-diphenylpyrrole gave, however, 3-diazo-2,5-diphenylpyrrole (1) and 3-diazo-4- nitro-2,5-diphenylpyrrole, with the latter predominating. This problem was overcome by the simple expedient of bubbling nitric oxide through a solution of 3-nitroso-2,5- diphenylpyrrole (Eq. 5). Major Minor (5) 1 12 J.M. Tedder and B. Webster, J. Chem. Soc., 3270 (1960). 7 About the same time# the procedure for preparing 3-amino-2,5-diphenylpyrrole was improved and then preparation of 3-diazo-2, 5-diphenylpyrrole (1_) by 13 diazotization and neutralization became practical. 14 Subsequently, Tedder and Webster showed that their method for introduction of a diazo group could be employed for synthesis of 2-diazopyrroles (Eq. 6) which cannot be prepared by diazotization because of the instability of the precursor amines. C H C,H r t no 3 j = c (6 ) The only attempts to extend the Doering-DePuy synthesis of diazocyclopentadiene to the pyrrole area are by Yoshida, 15 Hashimoto and Yoneda. These workers reacted pyrrole- magnesium bromide with p-toluenesulfonyl azide and obtained 2,21-azopyrrole. A possible mechanism for formation of the azopyrrole involves generation of 2-diazopyrrole in situ 13A. Kreutzberger and P. Kalter, J. Orq. Chem., 26, 3790 (1961) . 14 J.M. Tedder and B. Webster, J. Chem. Soc., 1638 (1962). 15 Z. Yoshida, H. Hashimoto, and S. Yoneda, Chem. Comm., 1344 (1971) . 8 which reacts further with the Grignard reagent to give the observed product (Eq. 7). O + CH, S02n : ( MgBr (7) ON l MgBr O-—-ON N* H H Very little is known about the chemistry of diazo- pyrroles. It is mentioned that 3-diazo-2,5-diphenylpyrrole (.1) and 3-diazo-2, 4,5-triphenylpyrrole (1_2) are light sensitive, but no attempts were made to study the 16 products.
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