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A STUDY of Bls-Diels-ALDER ADDUCTS of DIMETHYL ACETYLENEDECARBOXYLATE and CERWN FURANS

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A STUDY of Bls-Diels-ALDER ADDUCTS of DIMETHYL ACETYLENEDECARBOXYLATE and CERWN FURANS PART I SYRTHETIC APPROACHES TO 8b, 86- DIMETHYLPYRASYCLENE PART I! A STUDY OF BlS-DiELS-ALDER ADDUCTS OF DIMETHYL ACETYLENEDECARBOXYLATE AND CERWN FURANS Thesis for the Degree of Ph. D. MICHIGAN STATE UNIVERSITY JAMES DUANE S‘LEE 1 96 9 in“ LIBRARY 1 Michigan State University This is to certify that the thesis entitled PART I: SYNTHETIC APPROACHES TO 8b, 8c-DIMETHYLPYRACYCLENE PART II: A STUDY OF BIS-DIELS-ALDER ADDUCTS OF DIMETHYL ACETYLENEDICARBOXYLATE AND CERTAIN FURMS presented by JAMES DUANE SLEE has been accepted towards fulfillment of the requirements for Ph. D. degree in Chemistry Major profe sor Date September 3, 1969 0-169 . w J '7 ML- ‘. , Income av ' ‘5 ‘. 5i ‘HOAG & SONS' ' . tayxtmqrmnt a '- n---'- 'n- . "riot-'— Q ABSTRACT PART I SYNTHETIC APPROACHES TO 3b.BC-DIMETHYLPYRACYCLENE PART II A STUDY OF BIS-DIEL59ALDER ADDUCTS OP DIMETHYL ACETYLENEDICARBOXYLATE AND CERTAIN FURANS BY James Duane Slee Synthetic methods for preparing 8b.8c-dimethylpyracy- clene (4) were investigated. A useful precursor to g'ap- peared to be dimethyl 2a,4a:6a,8a-diepoxy-l,2,5,6-tetrahydro- cyclopent[£,g]acenaphthalene-Bb,8c-dicarboxy1ate (z) (1). CH, /’ \\ \\ 1’ CH, i Reduction of Z'with lithium aluminum hydride in tetra- hydrofuran gave 2a,4az6a,8a-diepoxy-8b,8c-di(hydroxymcLhyl)- 1,2,5,6-tetrahydrocyclopent[f,g]acenaphthalcnc (ya). James Duane Slee Treatment of diol lg’with‘p-toluenesulfonyl chloride in pyridine led to 2a,4a:6a,8a-diepoxy-8b,8c-di(hydroxymethyl pftoluenesulfonate)-1,2,5,6-tetrahydrocyclopent[f,g]acenaph- thalene (1E). Reduction of 12 with lithium aluminum hydride gave rise to diol 123 Displacement of the tosylate groups of lg with sodium iodide under various conditions failed. Conditions necessary for the preparation of the di(meth- anesulfonate) of diol 12 were not found. Treatment of 5% with one equivalent of methanesulfonyl chloride in pyridine gave rise to 2a,4a:6a,8a:9,10—triepoxy-8b,8c-di(methylene)- 1,2,5,6-tetrahydrocyclopent[f,g]acenaphthalene (1Q). Experiments designed to convert the hydroxyl groups of diol lg’to a halide were unsuccessful. When 12 was treated with thionyl chloride cyclic sulfite 12 was obtained. Saponification of Z was accomplished with suspension of sodium hydroxide in dimethyl sulfoxide. The resulting di- acid lg'was then converted to its anhydride 1;. Another pyracyclene precursor, 2a,4a:6a,8a-diepoxy-8b,8c- bis(trif1uoromethy1)-1,2,5,6-tetrahydrocyclopent[f,g]acenaph- thalene (21) was prepared by allowing hexafluorobutyne-Z to react with [2.5](2,5)-furophane. Catalytic hydrogenation gave the corresponding octahydro derivative 22; Attempts to cleave the ether bridges in compounds 1. gl'and 22 were unsuccessful. James Duane Slee PART II Dimethyl acetylenedicarboxylate reacts with furan at room temperature to give 7-oxabicyclo[2.2.1]hept-2,5-diene- 2,3-dicarboxylate (£1) (2). A second mole of furan reacts with 21 at room temperature resulting in the formation of dimethyl (gxg:gg§g)l,4:5,8-diepoxy-1,4,5,8-tetrahydro- naphthalene-4a,8a-dicarboxylate (g2). When the same reac— tion is run at 100° dimethyl (gnggxgjl,4:5,8-diepoxy-1,4, 4a,5,8,8a-hexahydronaphthalene-2,3-dicarboxy1ate (Q1); dimethyl (gnggggg)1,4:5,8-diepoxy-l,4,4a,5,8,8a-hexahydro- naphthalene—2,3-dicarboxylate (gg) and dimethyl 1,4:5,10:6,9- triepoxy-l,4,4a,5,5a,6,9,9a,10,10a-decahydroanthacene-2,3- dicarboxylate (2}). ‘While the DielseAlder adduct of dimethyl acetylene- dicarboxylate and 2,5-dimethy1furan does not react with a second mole of 2,5-dimethyl furan at room temperature at 1000 dimethyl (exo-endo)1,4:5,8-diepoxy-1,4,5,8-tetramethyl- 1,4,4a,5,8,8a-hexahydronaphthalene-2,3-dicarboxylate (fig) is formed. Exhaustive catalytic hydrogenation of 22 gave the gigfdecahydro ester 22, Saponification of 22 led to its Eggngfdiacid QQ, Oxidative bisdecarboxylation gave (egg: gagg)1,4:5.8-diepoxy-1,4,5,8-tetramethyl-1,4,4a,5,6,7,8,8a- octahydro naphthalene (gl). Catalytic reduction let to the parent compound of this system, (exo-endo)1,4:5,8-diepoxy- 1.4,5.8-tetramethyldecahydronaphthalene (§Z). James Duane Slee Controlled catalytic hydrogenation of gg gave rise to dimethyl (exo-endo)1,4:5,8-diepoxy-1,4,4a,5,6,7,8,8a-octa- hydronaphthalene-2,3-dicarboxy1ate (QQ). Pyrolysis of fig led to dimethyl 2,5-dimethylfuran-3,4-dicarboxylate, 2,5- dimethylfuran and ethylene. Dimethyl 2,5-dimethylfuran-2,3- dicarboxylate and pfxylene were obtained when Qg'was treated with trifluoroacetic acid. Two additional bis—DielSaAlder adducts were synthesized. Dimethyl (exo-endo)1,4:5,8-diepoxy-1,4,5-trimethyl-1,4,4a, 5,8,8a—hexahydronaphthalene-2,3-dicarboxylate (gg) was pre— pared by allowing 2-methylfuran to react with 7-oxa-1,4- dimethylbicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate at 100°. Dimethyl (exo-endo)1,4:5,8-diepoxy-1,5,8-trimethyl- 1,4,4a,5,8,8a-hexahydronaphthalene-2,3-dicarboxylate g1 was synthesized in a similar manner from 2.5-dimethylfuran and 7-oxa-l-methylbicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylate. The saturated derivatives of these two compounds were also prepared. References 1. D. J. Cram and G. R. Knox, J. Am. Chem. Soc., §§, 2204 (1961). 2. 0. Diels and K. Alder, Ann., 410, 243 (1931). PART I SYNTHETIC APPROACHES TO 8b.8c-DIMETHYLPYRACYCLENE PART II A STUDY OF BIS-DIELS-ALDER ADDUCTS OF DIMETHYL ACETYLENEDICARBOXYLATE AND CERTAIN FURANS BY James Duane Slee A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1969 fl / / 4.),17- 79 To My Parents ii ACKNOWLEDGMENTS The author wishes to express his sincere appreciation to Dr. Eugene LeGoff for his enthusiastic guidance through- out the course of this investigation, and also for arranging financial support from the National Science Foundation. The author is also grateful to Dr. William Reusch for his suggestions concerning the preparation of this thesis. Appreciation is also extended to Mrs. Mary K. Conner for proofreading this and other manuscripts. iii TABLE OF CONTENTS Page INTRODUCTION . 2 RESULTS AND DISCUSSION . 10 EXPERIMENTAL . 25 General Procedures . 25 2a,4a:6a,8a-Diepoxy-1,2,5,6-tetrahydro- cyclopent[f,g]acenaphthalene-8b,8c-dicar- boxylic acid (12) . 26 2a,4a:6a,8a-Diepoxy—1,2,5,6-tetrahydro- cyclopent[f,g]acenaphthalene-8b,8c-dicar- boxylic anhydride (ll) . 27 2a,4a:6a,8a—Diepoxy—8b,8c-di(hydroxy- methy1)-1,2,5,6-tetrahydrocyclopent[f,g]- acenaphthalene (£2) . , . 27 2a,4a:63,8a-Diepoxy-8b,8c-dimethy1ene- 1,2,5,6-tetrahydrocyclopent[f,g]acenaph- thalene-9,10-sulfite (12). 28 2a,4a:6a,8a:9,10-Triepoxy-8b,8c-dimethylene- 1,2,5,6-tetrahydrocyclopent[f,g]acenaph- alene (1Q) . 28 2a,4a:6a,8a-Diepo -8b-8c-di(methylene pftoluenesulfonate -1,2,5,6-tetrahydrocyclo- pent[f,g]acenaphthalene (lg) . 29 2a,4a:6a,8a-Diepoxy-8b,8c—bis(trifluoromethyl)- 1,2,5,6-tetrahydrocylcopent[f,g]acenaph- thalene (21) . 3O 2a,4a:6a,8a-Diepoxy-8b,8c-(trifluoromethyl)- 1,2,5,6,7,8-octahydrocyclopent[f,g]- acenaphthalene (gg) . 31 iv TABLE OF CONTENTS (Cont.) Page PART II INTRODUCTION . 33 RESULTS AND DISCUSSION . 37 EXPERIMENTAL . 65 Dimethyl 7-Oxa-1-methylbicyclo[2.2.1]- hepta-2,3-dicarboxylate (2g) . 65 Dimethyl 7—Oxa—1,4-dimethylbicyclo 2.2.1]- hepta-2,5-diene-2,3-dicarboxylate 22) . 65 Dimethyl (exo-endo)1,4:5,8-Diepoxy-1,4,4a,5,8, 8a-hexahydronaphthalene—4a,8a-dicarboxylate (3A) 0 O O O O O O O O O O O O O O O O O O O O 66 Analysis of the Furan-Dimethyl Acetylene Reaction (2 weeks) . 66 Diels-Alder Adducts from Dimethyl Acetylene- dicarboxylate and Excess of Furan: (GXOfSEQ) Bis-adduct 37. (egg-endo) Bis-adduct ggfhnd Tris-adductfiTgl) . 67 Dimethyl 7-0xa-1,4-dimethylbicyclo[2.2.1]- heptane-2,3-dicarboxylate (23) . 69 Dimethyl (exo-endo)1,4:5,8-Diepoxy-1,4,5,8- tetramethyl-1,4,4a,5,8,8a-hexahydronaph- thalene-2,3-dicarboxylate ($6) . 7O cis-Dimethyl (exo-endo)1,4:5,8-Diepoxy-1,4,5,8- tetramethyldecahydronaphthalene-2,3-dicarboxy— late (4"2) 0 O O O O O O O O O O O O O O O O O 71 trans-(exo-endo)1,4:5,8-Diepoxy-1,4,5,8—tetra- methyldecahydronaphthalene-Z,3-dicarboxylic Acid (Q2) . 72 (endo-exo)1,4:5,8-Diepoxy-1,4,5,8-tetramethyl- 1,4,4a,5.6,7,8,8a-octahydronaphthalene (S1) . 73 V TABLE OF CONTENTS (Cont.) Page (exo-endo)1,4:5,8-Diepo -1,4,5,8-tetramethyl- decahydronaphthalene (Q23 . 74 Dimethyl (exo-endo)1 ,4 : 5 , 8-Diepoxy-l , 4 , 5-tri- methyl-1,4,4a,5,8,8a-hexahydronaphthalene- 2,3-dicarboxylate (Q8) . 75 Dimethyl (exo-endo)1,4:5.8-Diepoxy-1,5,6-tri- methyl-1,4,4a,5,8,8a-hexahydronaphthalene (61) 76 Dimethyl (exo-endofi,4:5,8-Diepoxy-1,4,5,8- tetramethyl-l,4,4a,5,6,7,8,8a-octahydro- naphthalene-2,3—dicarboxylate (62) . 77 Pyrolysis of Mono-olefin 63' Procedure A . 78 Procedure B . 78 Acid Catalyzed Degradation of Mono-olefin fig . 79 cis-gndo-Dimethyl (exo-endo)1,4:5,8-Diepoxy- 1,4.5-trimethyldecahydronaphthalene-2,3- dicarboxylate (1;) . 80 cis-endo-Dimethyl (exo-endo)1,4:5,8-Diepoxy- 5.5,8-trimethyldecahydronaphthalene (22’ .
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