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Some Organometallic Reactions with Heterocyclic Compounds Justin Ward Diehl Iowa State University

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Some Organometallic Reactions with Heterocyclic Compounds Justin Ward Diehl Iowa State University Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1959 Some organometallic reactions with heterocyclic compounds Justin Ward Diehl Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Diehl, Justin Ward, "Some organometallic reactions with heterocyclic compounds " (1959). Retrospective Theses and Dissertations. 2574. https://lib.dr.iastate.edu/rtd/2574 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. SOME ORGANOMETALLIC REACTIONS WITH HETEROCYCLIC COMPOUNDS Justin Ward Diehl A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subject: Organic Chemistry Approved: Signature was redacted for privacy. Signature was redacted for privacy. Signature was redacted for privacy. D ! College Iowa State University Of Science and Technology Ames, Iowa 1959 11 TABLE OF CONTENTS Page I. INTRODUCTION 1 II. HISTORICAL 4 A. Thlaxanthene Chemistry 4 1. Introduction 4 2. Thlaxanthene 6 3. 10-Thiaxanthenol 8 4. 10-Thlaxanthenone 9 B. Reactions of Organosllylmetalllc Reagents. 13 1. With carbonyls 13 2. In metalation reactions 15 3. With organic halldes 17 C. Aromatic Heterocyclic Silicon Systems. ... 23 1. Organosilanes containing heterocyclic groups 23 a. Furan. 23 b. Thiophene 24 c. Benzothiophene 26 d. Dibenzothiophene 26 e. Dibenzofuran 27 f. Benzothiazole 27 g. Carbazole 28 h. Qulnoline 28 1. Pyridine 29 j. Xanthene 30 k. Phenothiazine 30 1. Acrldine 31 m. Miscellaneous 32 2. Cyclic organosllicon compounds 32 D. Sl-H Bond and Related Types as Reducing Agents 37 III. EXPERIMENTAL 44 ill Page A. Chemistry of Thiaxanthene and Related Compounds 44 1. Thiaxanthene 44 2. Reaction of thiaxanthene-5-oxide with hydrobromlc acid 45 3. 10-Thlaxanthenecarboxyllc acid from thiaxanthene and trlphenyl- silylllthium 46 4. 10-Trlphenylsllylthiaxanthene 47 5. 10-Thiaxanthenone 49 6. 2-Amino-10- thl axanthenone 49 a. By reduction of 2-nitro-10- thlaxanthenone 49 b. Hydroxylamlne with 10-thlaxan­ thenone ( attempted) 50 7. 2-Bromo-10-thl axanthenone 50 a. Cyclization 50 b. Dlazotization of 2-amlno-10- thi axanthenone 51 8. 2-Chloro-10-thiaxanthenone 52 9. 2-Me thy 1-10-thi axanthenone 53 10. Reaction of triphenylsllyllithlum with 10-thiaxanthenone 54 11. 10-Thlaxanthenone-5-oxide ( attempted). 55 12. 2-Bromo-10-thlaxanthenone-5,5-dloxlde. 56 a. Oxidation of 2-bromo-10- thi axan then one 56 b. Cyclization of 4-bromo-2- carboxydiphenyl sulfone 56 13. 2-Chloro-10-thiaxanthenone-5,5-dloxide . 57 14. 2-Me thy1-10-thi axanthenon e-5,5-dloxide . 57 B. Reactions of Triphenylsllyllithlum with Heterocycles 58 1. 9 «-E thy le arb az o le and dlbenzofur-an derivatives 58 a. 9-Ethyl-3-csrbazolyltrlphenylsilane. 58 iv Page b. Reaction of triphenylsllyllithlum with halogenated heterocycles. 59 2. 10-Ethylphenothiazine derivatives. ... 59 a. 10-Ethylpheno thiazine 59 b. 10-Ethylphenothlazin e- 5- oxl d e. ... 61 e. 10-Ethylphenothiazine-5,5-dioxide. 62 3. Preparation of 10-ethylphenothiazine derivatives 63 a. 3-Bromo-10-e thylpheno thi a zine- 5-oxide 63 b. 3-Bromo-10-ethylphenothiazine- 5,5-dloxlde 64 c. Some 10-ethylphenothiazine-5,5- dioxides 64 d. 2-Chloro-10-ethylphenothiazine ... 66 e. 2-Chloro-10-ethylphenothi azlne- 5-oxide 67 f. 3-Bromo-7-nltro-10-ethyl­ pheno thiazine 68 g. 3-Bromo-?-nltro-10-ethyl­ phenothlazlne- 5-oxide 68 h. 3-Bromo-7-amino-10-ethyl­ pheno thiazine-5, 5-dioxide 69 1. 3,7-Dlbromo-10-ethylpheno­ thiazine- 5, 5-dioxide 70 1. By reductive bromination of 3-bromo-10-ethylpheno- thlazlne-5-oxide followed by oxidation 70 il. Dlazotization of 3-bromo-7- ami no-10-e thylphenothiazine- 5,5-dioxide 70 J . 3, 7-Dichloro-10-ethylpheno­ thiazine-5-oxide 72 4. Incorporation of the triphenylsllyl group Into the 10-ethylphenothiazine molecule 73 a. 10-Triphenylsilylphenothiazine ( attempted) 73 V Page b. N-Triphenylsilyldicyclohexylamlne ( attempted) 73 c. 1-Trlphenylsilylphenothiazine ( attempted) 74 d. 2-Triphenylsilyl-10-ethyl­ phenothiazine - 75 e. 10-(2-Triphenyleilyle thyl)pheno- thiazine 75 f. 3-Triphenylsilyl-10-ethyl­ pheno thiazine 76 g. 3,7-Bis(triphenylsllyl)-10-ethyl- phenothiazine-5,5-dloxide 78 h. 4-Triphenylsilyl-10-ethyl­ phenothiazine . 79 i. Reactions of triphenylsllyllithlum with halogenated 10-ethylpheno- thiazlnes 80 C. Preparation of Cyclic-silicon Compounds. 80 1. o-(MethyldiphenyIsilyl)benzoic acid. 80 2. o-(Triphenylsilyl)benzolc acid ( attempted) 82 a. Oxidation of trlphenyl- ( o-tolyl)silane 82 b. Reaction of the lithium salt of o-lithiobenzoic acid with tripheny lchloro silane 83 c. Reaction of triphenylsllyllithlum with o-bromobenzoic acid 84 3. Reactions of dlphenyIs1lane with thiaxanthene 85 D. Reactions of Sl-H Compounds with Carbonyl Containing Compounds 87 1. Reaction of dlphenylsilane with 10- thiaxan thenone 87 a. At 230° 87 b. At reflux 88 c. At reflux for various lengths of time 88 vi Page 2. Reaction of diphenylsilane with benzophenone 89 a. At 220-230° 89 b. At 230-235° 89 c. At reflux 89 3. Reaction of diphenylsilane 90 a. With 9-fluorenone 90 b. With 9-xanthenone 90 c. With anthraquinone 91 d. With phenanthraquinone 91 e• With benzhydrol 92 f. With acetophenone 92 g. With 4-chlorobenzophenone 92 h. With 4-me thy lbenzophe no ne 93 i. With quinoline 94 j. With phenanthridine 94 4. Heating of benzhydryloxydiphenylsilane . 94 5. Reaction of phenylsilsne with 10-thi axanthenone 95 6. Reaction of trlphenylsilane 95 a. With benzophenone 95 b. With bromobenzene 96 c. With anthraquinone 96 IV. DISCUSSION 97 A. Chemistry of the Thiaxanthene System .... 97 B. Triphenylsllyllithlum as a Metalating Agent. 107 C. Reactions of Triphenylsilylithium with Heterocycles 109 D. Preparation of Cyclic-silicon Compounds. 113 E. Si-H Bond and Related Types as Reducing Agents 115 F. Suggestions for Further Research 119 V. SUMMARY 123 VI. ACKNOWLEDGMENT 125 1 I. INTRODUCTION The advent of accelerated silylmetallic research began with the development of tetrahydrofuran as a solvent for the lithium cleavage of hexaphenyldisilane."1" Tetrahydrofuran had been previously recognized for its catalytic effect in the P cleavage of silicon-silicon bonds and for its favorable in- •Z A flueace exerted on various organometallic reactions. ' Thus a silylmetallic in tetrahydrofuran is a powerful tool in the synthesis of new organosllicon compounds. Monomerle organo­ sllicon compounds usually possess admirable thermal stabil­ ities and therefore offer promise for use as high temperature lubricants or in related applications. Despite the ample publications on certain aspects of 5 6 7 organosllicon chemistry, ' * the first comprehensive review ^H. Gilman and G. D. Llchtenwalter, J. Am. Chem. Soc.. gO, 608 (1958). Gilman, R. K. Ingham and A. G. Smith, J. Org. Chem.. 18, 1743 (1953). 3H. Gilman and B. J. GaJ, Ibid.. 22, 447 (1957). 4H. Gilman and T. S. Soddy, ibid.. 22, 1121 (1957). 5H. W. Post. Silicones and other organic silicon com­ pounds. New York, N.Y., Reinhold Publishing Corp. 1949. ®E. G. Rochow. An introduction to the chemistry of sili­ cones. 2nd ed. New York, N.Y., John Wiley and Sons, Inc. 1951. 7P. D. George, M. Prober and J. R. Elliot, Chem. Revs., 56, 1065 (1956). 2 of organoBllylmetaille compounds has Just recently appeared.® As a continuation of the research in determining the scope of silylmetallic chemistry, this investigation pursues the reactivity of organosilylmetallies, specifically, triphenyl­ sllyllithlum, with heterocycles. Initially, thiaxanthene was selected for study because, in spite of the considerable work done, the chemical knowledge of this system is fragmentary. Later, another heterocycle, namely, phenothiazine, was in­ vestigated and the preparation of some of its silicon deriva­ tives was undertaken. The purpose of this Investigation has been: (1) to col­ lect, systematize and extend the knowledge of the syntheses and orientation in thiaxanthene and related compounds ; (2) to compare the effect of the solvent and the halogen on the re­ activity of triphenylsllyllithlum with mono-halogenated heterocycles; (3) to prepare several halogenated derivatives of 10-ethylphenothiazine and study their reaction with tri- phenylsilyllithium in the hope that some of these coupled compounds might manifest favorable thermal stabilities; (4) to ascertain the possible utilization of silicon hydrides as selective reagents for hydrogénations and hydrogenolyses. The historical section has been developed so as to ®D. Wittenberg and H. Gilman, Quart. Revs. (London), June (1959). 3 present information which will be pertinent to the investiga­ tion described in the later parts of this dissertation. 4 II. HISTORICAL A. Thiaxanthene Chemistry 1. Introduction Although thiaxanthene has been known for nearly seventy- five years there has been relatively little work reported dur­ ing that period. Only one review on thiaxanthene and related compounds has appeared in the literature.9 Several names have been applied to the parent hetero­ cyclic compound. Thiaxanthene is given as the preferred name by Patterson and Cape11^ and will be employed in this dis­ cussion. Other names often encountered In the literature
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