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'({JIXOAA* Laiuoaim ' ' SYNTHESIS AND REACTIONS OF INTERMEDIATES FOR STEROID ELABORATION DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Arlen B. Mekler, B.S., M.S. • • • o o The Ohio State University 1959 Approved by '({JIXOAA* lAiUOAim ' ' " Adviser Department of Chemistry DEDICATION TO LEV A. MEKLER ii ACKNOWLEDGMENT The author wishes to express his sincere appreciation to Dr. Melvin S. Newman for stimulating ideas and helpful advice, for interesting discussions and constructive criticisms, for invaluable laboratory techniques, for his personal friendship and his inspirational guidance throughout this research. The author is also grateful for the receipt of the following awards: Charles P. Kettering Founda­ tion Fellowship, 1956-1957; Melvin S. Newman Scholarship, 1957; U. S. Industrial Company Fellow­ ship, 1957-1958; Allied Chemical Company Fellowship, 1958-1959; and E. I. Du Pont Research Fellowship, 1959. iii TABLE OP CONTENTS Page ACKNOWLEDGMENT. ... .. ill OBJECTIVE 1 HISTORICAL BACKGROUND 4 DISCUSSION OP RESULTS 20 SUGGESTIONS FOR FURTHER WORK 39 EXPERIMENTAL «,.... 42 General Procedures, 42 2-Methyl-l, 3-cyclohexanedione 43 4-Diethylamino-3-butanone0 44 1,6-Dioxo-8a-methyl-l, 2, 3, 4, 6,7,8, 8a- oc tahydronaphthalene. ••• 44 K -(6-Methyl-3-keto-l-cyclohexene- 1-yl)-butyric acid 47 Methyl ^-(6-Methyl-3-keto-l-cyclo- hexene-1-yl) butyrate • 48 Methyl &"-(3-Acetoxy-6-methyl-l,3- cyclohexadien-1-yl) butyrate. 49 Methyl #-( 5-Hydroxy-2-methylphenyl) - butyrate 50 Action of Sodium Methoxide on Methyl ^-{ 5-Hydroxy-2-methylphenyl) butyrate 51 3- (4-Hydroxybutyl) - 4-me thylphenol 51 3- ( 4-Bromobutyl) - 4-me thylphenol • 52 Attempted Synthesis of 3-(4-bromobutyl)- 4-Methylphenol Employing Acetic Acid.. 52 iv Page Base-Induced Cyclization of 3-(4- Bromobutyl)-4-raethylphenol A) Action of Methanolic Sodium Me thoxi de 53 B) Action of Sodium Amide in Liquid Ammonia 54 r -(2-Hydroxy-5-methylbenzoyl)-propionic acid. 55 *^-(2-Hydroxy-5-methylphenol)-butyric acid.... 56 Methyl -(2-Hydroxy-5-methylphenyl) butyrate. 57 2- ( 4-Hydroxybutyl)-4-methylphenol 58 2- ( 4-Bromobutyl) - 4-me thylphenol 59 Attempted Synthesis of 2-(4-Bromobutyl)- 4-methylphenol Employing Acetic acid 59 Base-Induced Cyclizations of 2-(4- Bromobutyl)-4-methylphenol A) Action of Methanolic Sodium Methoxide 60 B) Action of Sodium Amide in Liquid Ammonia 61 C) Action of Lithium Amide in Liquid Ammonia 62 1,8-Dioxo-4-methyl-l, 2, 3,5,6, 7,8,8a- octahydronaphthalene 63 4-Methyl-8-oxo-5,6,7,8-tetrahydro-l-naphthol.• 65 Lithium Aluminum Hydride Reduction of 1,8-Cioxo-4-methyl-l,2, 3,5,6,7,8,8a- octahydronaphthalene 66 c<.-Methylnaphthalene 67 4-Methyl-5,6,7,8-tetrahydro-l-naphthol 67 v Page l-Oxo-4,8-dimethyl-8-hydroxy- 1,2, 3,4,6,7, 8,8a-oetahydronaphthalene 68 1, 4-Dime thylnaphthalene «... .....«*.. 69 SUMMARY.. • 70 APPENDIX 73 AUTOBIOGRAPHY 76 vl OBJECTIVE It was the purpose of this work to study the base-induced cyclization reactions of 2-(4-bromobutyl)- 4-methylphenol, I and 5-(4-bromobutyl)-4-methylphenol, II. Upon treatment with base the bromide, I, might be expected to cyclize by one of two paths (Figure I) to give the cyclic ether, Ilia, if the chain cyclizes at position a or the spiro decadienone, Illb, if the alkylation occurs at position b. Of particular interest to us was the path of base- induced cyclization of the bromide, II, since this might serve as an interesting path to 10-methyl-2-keto- 2,5,6,7,8,10-hexahydronaphthalene, V (path d), a possible intermediate for steroid synthesis. The cyclization could also proceed by an alternate route to yield 4-methyl-5,6,7,8-tetrahydro-l-naphthol, IV, (path c) (Figure I). The preparation of the bromide, I, from p-cresol via '8'-(2-hydroxy-5-methylphenyl) butyric acid, VI, was straightforward and offered no synthetic problem. 1 -x ,a, OH o0 ^ CH3 Q^(CH2)3-CH2Br (CH^ CH2Br Ilia base A CH. CH. III b OH OH ,o CH ban 3 (c) IV r (CH2)3 CH2Br 2^3^ ^2® CH, <& CH3 J Figur« I OH ,(tH2)j-C02H 0) For the synthesis of the bromide, II, it was necessary to prepare quantities of l-6-dioxo-8a~methyl-l, 2,3, 4,6V"7,8,8a-octahydronaphthalene, VII, which was then cleaved with sodium methoxide to produce the keto ester, VIII, which possessed the carbon skeleton necessary for the formation of II. The ester, VIII was aromatized and the ester grouping then reduced and treated with hydi?obromic acid to yield II. o Ha OC*3 j. CHjOH o VII " (2.) During the course of the preparation of the keto ester, VIII, it was noted that in the presence of excess methanolic sodium methoxide, the 1,6-dione, VII, under­ went a novel transacylatlon reaction to yield 1,8-dioxo- 4-methyl-2,3,5,6,7,8,8a-octahydronaphthalene, IX. ° firCHj o— CH3°H JO 0, The course of this reaction, as well as the properties of IX, was investigated. HISTORICAL BACKGROUND Because of the varied scope of the studies involved, the background material, pertinent to the investigations described herein, has been divided into the following convenient catagories: (A) Cycliza- tion of 4-p-hydroxyphenyl-l-butyl-p-bromobenzene- sulfonate; (B) Synthesis of X-(2-hydroxy-5-methyl- phenyl) butyric acid; (G) Synthesis of 1,6-diaxo- 8a-methyl-l,2,3,4,6,7,8,8a-octahydronaphthalene; (D) Synthesis of 1,8-decalindione; and (E) Alkylation of Hagemannfs ester and related °<. , (3 -unsaturated ketones. Only a limited amount of work related to the studies on the base-induced cyclization of the bromides I and II, has been reported by others. l H-oNy H-0'\x' *(ctf,iJCHlBr (CtiJ3CHz*r I )l 4 5 Cycllzation of 4-(p-Hydroxyphenyl) - 1-butyl p-bromobenzene Sulfonate X When 4-(p-hydroxyphenyl)-1-butyl p-bromobenzene sulfonate, X, was treated with a slight excess of potassium t-butoxide in anhydrous t-butyl alcohol, spiro-(4;5)-deca-l, 4-dien-3-one, II, was isolated 1 in 50% yield. The ketone, XI, has been subjected o to the dienone-phenol rearrangement to yield 5,6, 7,8-tetrahydro-2-naphthol, XII, in quantitative yield. i No work has been reported, however, on the analogous reactions with molecules in which the alkyl side chain is on a position meta or ortho to the phenolic hydroxyl group. Is. Winstein and R. Baird, J. Am. Chem. Soc, 79, 756 (1957). 2 A. L. Wilds and C. Djerassi, J. Am. Chem. Soc, 68, 1715 (1946). 6 The possibility that the base-catalyzed rearrangement of the bromide, II, might lead to the formation of the dienone V seemed most intriguing as V serves as an interesting model for synthesis of steroids. Compound V has been synthesized previously in low yield by the condensation of 2-methylcyclohexanone and methylethynyl ketone in the presence of sodium hydride. The ketone, V, has also been prepared in a little higher yield from 2-methyl-2-formylcyclo- hexanone by condensation with acetone in piperidine and acetic acid. o cw, o O + CH,-C-CHCH . MaH, ether Pi PeriJl'ine acetic *cij (s) 1 R. B. Woodward and T. Singh, J. Am. Chem. Soc, 72, 494 (1950). 7 The dienone, V, can be rearranged by treatment with acetic anhydride and sulfuric acid to yield 4-methyl-5-,6,7,8-tetrahydro-l-naphthol, IV. XX) -±~ §0 V Crt3 (6) Synthesis of >^-(2-Hydroxy-5 methylphenyl) butyric Acid, VI ^-( 2-Hydroxy-5 methylphenyl) butyric acid was an intermediate in the synthetic route chosen for the preparation of 2~(4-bromobutyl)-4-methylphenol, I, (Figure IV). The acid, VI, has been synthesized1* 2 by treatment of p-methylanisole, XIII, with succinic acid in the presence of aluminum chloride to give @>-(2~hydroxy- 5-methylbenzoyl) propionic acid, XIV. Compound XIV was then subjected to a Clemmensen reduction to produce VI in 54% yield. R. B. Woodward and T. Singh, J. Am. Chem. Soc, 72, 494 (1950). 2 R. D. Desai and M. A. Wali, Proc. Ind. Acad. Sc. (A) 6, 144 (1937) C. A. 32, 509 (1938). 8 OH O ort Nitrobenzene ru_ Toluene XII) Synthesis of l,6-Dioxo-8a-methyl- 1,2,5,4,6,7,8,8a-octahydronaphthalene, VII It was necessary to prepare l,6-dioxo-8a-methyl- 1,2, 5, 4, 6, 7, 8,8a-octahydronaphthalene, VII, in large quantity since it was a precursor in the chosen path for the synthesis of 4-(5-hydroxy-2-methyl-phenyl)- 1-bromobutane, II, (Figure III), A survey of the literature revealed that 2-methyl-l,3-cyclohexanedione, XVII, served as the starting material in all syntheses of VII. Compound 1 2 XVII has been prepared ' by high pressure hydro- genation of an alkaline solution of resorcinol, XV, to give dihydroresorclnol, XVI, in 90% yield, followed by methylation with methyl iodide employing sodium M. Klingenfuss, XL. S. Pat. 1965, 499 (1934). *R. R. Thompson, Org. Syntheses, Coll. Vol. 3, 278 (1955). 9 1 2 methoxlde In methanol ' potassium hydroxide in 9 4 aqueous methanol, potassium methoxlde in methanol, potassium hydroxide in aqueous acetone, potassium 6 carbonate in aqueous acetone, or sodium ethoxide in 7 ethanol, but the yield of pure X was never better than 42%'. ow o o X\/ xv» XVII (8) 2-Methyl-l,3-cyclohexanedione, XVII, has also been prepared by embolization of ethyl 5-oxoheptanoate and g methyl 5-oxoheptanoate with sodium ethoxide and XM. S. Newman and S. Swaminathan, Tetrahedron, 2, 88 (1958).
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