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I. Gas-Phase Intramolecular Diels-Alder Reactions of 2,3-Dimethylene-2,3-Dihydrofurans; II

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I. Gas-Phase Intramolecular Diels-Alder Reactions of 2,3-Dimethylene-2,3-Dihydrofurans; II Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1987 I. Gas-phase intramolecular Diels-Alder reactions of 2,3-dimethylene-2,3-dihydrofurans; II. Formation of anthracene and other polycyclic aromatic compounds in the pyrolysis of 1,5-dibenzocyclooctadienes and related compounds; III. Formation of 9-methylanthracene and anthracene in the pyrolysis of 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene and other related compounds; IV. Preparation of cyclopentadienones by flash vacuum pyrolysis and their dimerization and intramolecular reactions Suk Kyu Lee Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Lee, Suk Kyu, "I. Gas-phase intramolecular Diels-Alder reactions of 2,3-dimethylene-2,3-dihydrofurans; II. Formation of anthracene and other polycyclic aromatic compounds in the pyrolysis of 1,5-dibenzocyclooctadienes and related compounds; III. Formation of 9-methylanthracene and anthracene in the pyrolysis of 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene and other related compounds; IV. Preparation of cyclopentadienones by flash vacuum pyrolysis and their dimerization and intramolecular reactions" (1987). Retrospective Theses and Dissertations. 8557. https://lib.dr.iastate.edu/rtd/8557 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]. INFORMATION TO USERS While the most advanced technology has been used to photograph and reproduce this manuscript, the quality of the reproduction is heavily dependent upon the quality of the material submitted. For example: • Manuscript pages may have indistinct print. In such cases, the best available copy has been filmed. • Manuscripts may not always be complete. In such cases, a note will indicate that it is not possible to obtain missing pages. • Copyrighted material may have been removed from the manuscript. In such cases, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, and charts) are photographed by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each oversize page is also filmed as one exposure and is available, for an additional charge, as a standard 35mm slide or as a 17"x 23" black and white photographic print. Most photographs reproduce acceptably on positive microfilm or microfiche but lack the clarity on xerographic copies made from the microfilm. For an additional charge, 35mm slides of 6"x 9" black and white photographic prints are available for any photographs or illustrations that cannot be reproduced satisfactorily by xerography. 8716787 Lee, Suk Kyu I. GAS-PHASE INTRAMOLECULAR DIELS-ALDER REACTIONS OF 2,3- DIMETHYLENE-2,3-DIHYDROFURANS. II. FORMATION OF ANTHRACENE AND OTHER POLYCYCLIC AROMATIC COMPOUNDS iN THE PYROLYSIS OF 1,5-DIBENZOCYCLOOCTADIENES AND RELATED COMPOUNDS. III. FORMATION OF 9-METHYLANTHRACENE AND ANTHRACENE IN THE PYROLYSIS OF 5,6,11,12-TETRAHYDRODIBENZO(A,E)CYCLOOCTENE AND OTHER RELATED COMPOUNDS. IV. PREPARATION OF CYCLOPENTADIENONES BY FLASH VACUUM PYROLYSIS AND THEIR DIMERiZATION AND INTRAMOLECULAR REACTIONS Iowa State University PH.D. 1987 University Microfilms IntGrn&tiOnSi 300N.ZeebRoad, Arbor, Ml 48106 PLEASE NOTE: In all cases this material has been filmed in the best possible way from the available copy. {Problems encountered with this document have been identified here with a check mark V . 1. Glossy photographs or pages 2. Colored illustrations, paper or print 3. Photographs with dark background 4. Illustrations are poor copy 5. Pages with black marks, not original copy 6. Print shows through as there is text on both sides of page 7. Indistinct, broken or small print on several pages 8. Print exceeds margin requirements 9. Tightly bound copy with print lost in spine 10. Computer printout pages with indistinct print 11. Page(s) lacking when material received, and not available from school or author. 12. Page(s) seem to be missing in numbering only as text follows. 13. Two pages numbered . Text follows. 14. Curling and wrinkled pages 15. Dissertation contains pages with print at a slant, filmed as received 16. Other University Microfilms International I, Gas-phase intramolecular Diels-Alder reactions of 2,3-dimethylene-2,3-dihydrofurans. II. Formation of anthracene and other polycyclic aromatic compounds in the pyrolysis of 1,5-dibenzocyclooctadienes and related compounds. III. Formation of 9-methylanthracene and anthracene in the pyrolysis of 5,6,11»12-tetrahydrodibenzo[a,e]cyclooctene and other related compounds. IV. Preparation of cyclopentadienones by flash vacuum pyrolysis and their dimerization and intramolecular reactions by Suk Kyu Lee A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Chemistry Major; Organic Chemistry Approved Signature was redacted for privacy. In Charge of Major Wo: Signature was redacted for privacy. For the Major Department Signature was redacted for privacy. For the Gr^hate Colleg Iowa State University Ames, Iowa 1987 ii TABLE OF CONTENTS Page GENERAL INTRODUCTION 1 Explanation of Dissertation Format 2 PART I. GAS-PHASE INTRAMOLECULAR DIELS-ALDER REACTIONS OF 2,3-DIMETHYLENE-2,3-DIHYDROFURANS 3 INTRODUCTION 4 RESULTS 7 DISCUSSION 22 EXPERIMENTAL 26 Methods and Materials 26 4,4-Dimethyl-2-(3-furyl)-2-oxazoline (25) 27 7-Broino-l-heptene (43) 27 4,4-Dimethyl-2-[2-(5-hexenyl)-3-furyl]- 2-oxazoline (26) 28 4,4-Dimethyl-2-[2-(6-heptenyl)-3-furyl]- 2-oxazoline (27) 29 4,4-Dimethyl-2-[2-(7-octenyl)-3-furyl]-2- oxazoline (28) 29 ~~ 2-(5-Hexenyl)-3-furoic acid (29) 30 2-(6-Heptenyl)-3-furoic acid (30) 30 2-(7-Octenyl)-3-furoic acid (31) 31 2-(5-Hexenyl)-3-furyImethanol (44) 31 2-(6-Heptenyl)-3-furylmethanol (45) 31 2-(7-Octenyl)-3-furylmethanol (46) 32 2-Methyl-3-furoic acid (47) 32 N,N-Dimethyl-2-methyl-3-furamide (33) 32 iii N,N-Dimethyl-2-(6-heptenyl)-3-furamide (34) 33 2-(6-Heptenyl)-3-furoic acid (30) 34 2-(5-Hexenyl)-3-furylmekhyl benzoate (21) 35 2-(6-Heptenyl)-3-furylmethyl benzoate (22) 36 2-(7-Octenyl)-3-furylmethyl benzoate (23) 36 2-(5-Hexenyl)-3-furylmethyl-obenzoate (Zl-Ég) 37 General pyrolysis procedure 37 Pyrolysis of 2-(5-hexenyl)-3-furylmethyl benzoate (21) 38 Pyrolysis of 2-(5-hexenyl)-3-furylmethyl- a,a-à^ benzoate (21-d«) 39 ' —2 'w —2 Pyrolysis of 2-(6-heptenyl)-3-furylmethyl benzoate (22) 39 Pyrolysis of 2-(7-octenyl)-3-furylmethyl benzoate (23) 41 REFERENCES 43 PART II. FORMATION OF ANTHRACENE AND OTHER POLYCYCLIC AROMATIC COMPOUNDS IN THE PYROLYSIS OF 1,5-DIBENZOCYCLOOCTADIENES AND RELATED COMPOUNDS 46 INTRODUCTION 47 RESULTS 51 DISCUSSION 60 EXPERIMENTAL 64 Methods and Materials 64 4H,5H,9H,lOH-Cycloocta[If2-b:6,5-b']difuran (15) 64 5f6fllf12-Tetrahydrodibenzo[bff]azocine (16) 65 6H,llH-Dibenzo[bff][If4]-dioxocin (17) 65 iv 5-Methyl-lO,ll-dihydro-5H-dibenzo[a,d]- cycloheptene (22) 5-Ethylidene-lO,ll-dihydro-5H-dibenzo[a,d]- cycloheptene (54) 5-Ethyl-lO,ll-dihydro-5H-dibenzo[a,d]- cycloheptene (23) General FVP procedure FVP of 4H,5H,9H,10H-cycloocta[l,2-b:6,5-b']- difuran (15) FVP of 5,6,11,12-tetrahydrodibenzo[b,f]- azocine (16) FVP of 6H,llH-dibenzo[b,f][1,4]-dioxocin (17) FVP of 10,ll-dihydro-5H-dibenzo[a,d]- cycloheptene (21) FVP of 5-methyl-lO,ll-dihydro-5H-dibenzo[a,d] cycloheptene (22) FVP of 5-ethyl-lO,ll-dihydro-5H-dibenzo[a,d]- cycloheptene (23) REFERENCES PART III. FORMATION OF 9-M ETH YLANTHRACENE AND ANTHRACENE IN THE PYROLYSIS OF 5,6,11,12- TETRAHYDRODIB ENZ0[a,e]C YC LOOCTENE AND RELATED COMPOUNDS INTRODUCTION RESULTS DISCUSSION EXPERIMENTAL Methods and Materials Di-o-tolyl sulfone (86) trans-2,2'-DimethylStilbene (14) V 5r 6,11,12-Tetrahydrodibenzo[a,e]cyclooctene- 5-ol (87) 113 5,6,11,12-Tetrahydrodibenzo[a,e]cyclooctenyl acetate (24) 114 5,6-Dihydrodibenzo[a,e]cyclooctene (12) 115 Dibenzosuberyl acetate (34) 115 1,2-Di-o-tolylethane (15) 116 2-Methyl-a,a-dideuterobenzyl alcohol (88) 116 a,a-Dideutero-a-bromo-o-xylene (89) 116 1,2-Di-o-tolyltetradeuteroethane (15-d^) 116 5-Methyl-lO,ll-dihydro-5H-dibenzo[a,d]- cycloheptene (16) 117 5-Ethyl-lO,ll-dihydro-5H-dibenzo[a,d]- cycloheptene (18) 117 2,2',5-Trimethylstilbene (91) 117 2, 2',5-Triinethylbibenzyl (25) 118 2,2*,5,5'-Tetramethylbibenzyl (26) 118 General FVP procedure 118 FVP of 5,6-dihydrodibenzo[a,e]cyclooctene (12) 118 F VP of trans-2,2'-dimethylstilbene (14) 119 FVP of 5,6,11,12-tetrahydrodibenzo[a,e]- cyclooctenyl acetate (24) 119 FVP of 2,2',5-trimethylbibenzyl (25) 119 FVP of dibenzosuberyl acetate (34) 120 General sealed tube pyrolysis procedure 121 Sealed tube pyrolysis of 5,6,11,12-tetrahydro- dibenzo[a,e]cyclooctene (1) 121 vi Sealed tube pyrolysis of 2,8-dimethyl- 5,6,11,12-tetrahydrodibenzo[a,e]cyclooctene (3) 121 Sealed tube pyrolysis of 2,9-dimethyl-5,6,11,12- tetrahydrodibenzo[a,e]cyclooctene (4) 122 Sealed tube pyrolysis of dibenzo[c,g]thiapin- dioxide (13) 122 Sealed tube pyrolysis of 5,6-dihydrodibenzo- [a,e]cyclooctene (12) 123 Sealed tube pyrolysis of trans-2,2'-dimethy1- stilbene (14) 123 Sealed tube pyrolysis of 1,2-di-o-tolylethane (15) 124 Sealed tube pyrolysis of 2,2',5-trimethyl- bibenzyl (25) 124 Sealed tube pyrolysis of 2,2',5,5'-tetramethyl- bibenzyl (26) 124 Sealed tube pyrolysis of p-tolyl-a,a,g,6-d.- ethane (15-d.) 125 Sealed tube pyrolysis of dibenzosuberane (17) 125 Sealed tube pyrolysis of methyldibenzosuberane (16) 126 /v/v Sealed tube pyrolysis of ethyldibenzosuberane (18) 126 Sealed tube pyrolysis of dibenzosuberone (19) 126 Sealed tube pyrolysis of 2,9-dimethyIdibenzo- suberone (20) 127 REFERENCES 128 PART IV.
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