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THE SYNTHESIS of STABLE Naphthoibjcyclobutadienes

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This dissertation has been microfilmed exactly as received 66—1792 HWANG, Bruce You—Huei, 1936— THE SYNTHESIS OF STABLE NAPHTHOIbjCYCLOBUTADIENES. The Ohio State University, Ph.D., 1965 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan THE SYNTHESIS OF STABLE NAPHTHOCb]GYCLOBUTADIENES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Bruce You-Huei Hwang, B. S., K, A. ********** The Ohio State University 196? Approved by in -1 Adviser Department of Chemistry ACKNOWLEDGMENTS The author wishes to express his deepest appreciation to Dr. Michael P. Cava, for his advice, guidance and encour­ agement throughout this research. Thanlcs are due to Dr. M. J . Mitchell for his help and to the author's colleagues for their cooperation and for bearing the brunt of his chemical dialectic while this work was in progress. The author also owes a debt of gratitude to Dr. and Mrs. P. Y. Yeh, who kindly furnished him with a home-like enviroment at a time of need. Lastly the author wishes to thank his parents, who contributed greatly to the completion of this work. 11 i VITA January 6, 193& .... Born - TaiwanCFormosa) July, 1958 ........ B. S., The National Taiv/an University Taipei, TaiwanCFormesa) August, 1961 ...... H. A., East Tennessee State University Johnson City, Tennessee Major Field of Study: Organic Chemistry iii CONTENTS Page I INTRODUCTION ................................ 1 II STATEMENT OF PR0BLEI4 ......................... 10 III DISCUSSION AND INTERPRETATION OF RESULTS ... I3 IV EXPERIMENTAL ................................ ^5 a 5 a’-Bis(phenylethynyl)-o-xylene-a,a '- diol (3*+) • • ^5 1.2-Dimethoxy-1,2-diphenylnaphtho[bi­ cycle butene (2 8) ........................ 46 1.2-Dichloro-1,2-diphenylnaphtho[b]- cyclobutene (2 9 ) ........ 4-7 Hethanolysis of 1,2-Dichloro-1,2-di- phenylnaphtho[b]cyclobutene C 2 9 ) to 1 ,2-Dimethoxy-1 ,2-diphenylnaphtho- [b] cyclobutene (2 8) ...................... 4-7 Oxidation of 1,2-Dimetlioxy-1,2-diphenyl­ naphtho [b] cyclobutene (2 8) to 2,3- Dibenzoylnaphthalene (4-7) ............... 4-8 Catalytic Reduction of 1 ,2-Dicliloro-1,2- diphenylnaphtho [b] cyclobutene (2 9 ) to cis-1,2-DiphenylnaphthoCb]cyclo­ butene (49a) ........ 4-8 Pyrolysis of 1,2-Dimethoxy-1,2-di­ phenylnaphtho [b]cyclobutene (28) to 5-Methoxy-12-phenylnaphthacene (53) ..... 4-9 IV CONTENTS (Conta.) Page Pyrolysis of 1,2-Dic}iloro-'l ,2-diphenyl­ naphtho [b] cyclobutene (2 9 ) to 5“ Chloro-12-phenylnaphthacene (55) .......... 50 Thermal Rearrangement of cis-1 ^2-Diphenyl- naphtho[b]cyclobutene (49a) to 5-phenyl- 5,12-dihydronaphthacene (56) .............. 50 Isomerization of cis-1,2-Diphenylnaphtho- [b]cyclobutene (49a) to tran^-1,2-Di- phenylnaphthoCb] cyclobutene (49b) ......... 50 N,1,4-Triphenyl-1,2,3,4-tetrahydro-2,3- antliracene-dicarboximide (59); cis- 1,2-Diphenylnaphtho[b]cyclo­ butene (49a) and N-Phenyl- maleimide Adduct ......................... 51 1,3-Diphenyl-1,3-dihydronaphtho[2,3~c] thiophene 2,2-dioxide (5#) ................ 52 Photolysis of 1,3-Diphenyl-1,3-aihydro- naphtho[2,3-c]thiophene 2,2-dioxide (58) .... 52 to trans-1,2-Diphenylnaphtho[b]- cyclobutene (49b) ............... 52 Aromatization of 5-Phenyl-5,12-dihydro- naphthacene (56) to 5-Phenyl- naphthacene (60) .................. 53 V . CONTENTS (Contdo) Page Synthesis of 5-Phenylnaphthacene (60) ....... 53 T,2-Diphenylnaphtho[b]cyclebutadiene (30) .... 5^ 1.2-Diphenylnaphtho[b]cyclebutadiene (30) and 2,^-,7-Trinitrefluorenene Complex...... 55 1.2-Dibreme-1,2-diphenylnaphtho[bi­ cycle butene (65) .................. 5& Oxidation of 1,2-Diphenylnaphtho[b]cyclo- butadiene (3 0 ) to 2,3-Dibenzoyl- naphthalene (4?) ......................... 56 Hydrogenation of 1,2-Diphenylnaphtho[bi­ cycle butadiene (30) to cis-1,2-Di- phenylnaphtho[blcyclobutene (49a) ......... 57 5j 5a,11b,12-Tetrahydro-5,5a, 11b,12-tetraphenyl- 5,12-epoxydibenzo[b,hlbiphenylene (66); Adduct of 1,2-Diphenylnaphtho[bicycle- butadiene (30) and 1,4-Diphenyl-2,3- benzofuran (14) .......................... 57 Preparation of 3,8-Diphenylnaphtho[bl- cyclobutene (21) ......................... 58 1 -Bromo-3,8-diphenylnaphtho[blcyclo­ butene (71) .............................. 59 trans-1,2-Dibromo-3,8-diphenylnaphtho[bl- cyclobutene (22b) .................... 60 VI CONTENTS (Contd.) Page 1,1-Dibromo-3,8-diphenylnaphtho[b]- cyclobutene (7 2) .......................... 60 1,1,2,2-Tetrabromo-3,8-diphonyl- naphtho [b] cyclobutene (3 1) ................ 61 Hydrolysis of 1-Bromo-3,8-diphenylnaphtho- [b]cyclobutene (71) to 1-Hydroxy-3?8-di- phenylnaphtho [b] cyclobutene (73) .......... 62 Hydrolysis of 1,1-Dibromo-3>8-diphenyl­ naphtho [b] cyclobutene (72) to 3,8-Di- phenylnaphtho[b]cyclobuten-1-one (7^) ...... 62 Oxidation of 1-Hydroxy-3,8-diphenyInaphtho- [b]cyclobutene (73) to 3,8-Diphenyl- naphthoLb]cyclobuten-1-one (743 ........... 63 Hydrolysis of 1,2-Dibromo-3)8-diphenyl­ naphtho [b] cyclobutene (22) to 1,2-Di- hydroxy-3,8-diphenylnaphtho[b]cyclo­ butene (75) .............................. 64 Hydrolysis of 1,1,2,2-Tetrabromo-3?8- diphenylnaphthoCb]cyclobutene (3 1) to 3,8-Diphenylnaphtho[b]cyclo­ butene 1 ,2-dione ( 76) .................... 64 Reduction of 3,8-Diphenylnaphtho[b]cyclo­ butene 1,2-dione (76) with Sodium Boro- hydride to 1,2-Dihydroxy-3,8-dlphenyl- naphtho[b]cyclobutene (75) ......... 65 vii CONTENTS (Gontd.) Page Attempted Synthesi's of 3,8-Diphenyl- naphthoCb]cyclebutadiene (17) ............. 66 Trapping of 3,8-Diphenylnaphtho[b]cyclo- butadiene (17) with 1,^-Diphenyl-2,3- benzofuran (140 ........................ 66 Attempted Synthesis of 1-Bromo-3,8-diphenyl­ naphtho Cb] cyclobutadiene (77) ............. 67 Trapping of 1-Bromo-3,8-diphenylnaphtho[b]- 4' cyclobutadiene (77) with 1,4-Diphenyl- 2,3-benzofuran (14) ...................... 67 1.2-Dibromo-3,8-diphenylnaphtho[b]- cyclobutadiene (3 2) ...................... 68 Addition of Bromine to 1,2-Dibromo-3,8-di- phenylnaphtho[b] cyclobutene (3 2) .... 69 1.2-Dibromo-3,8-diphenylnaphtho[b]cyclo­ butadiene (3 2) and 1,4-Diphenyl-2,3- benzofuran Adduct; 5a,1 lb-Dibromo- 5,6,11 ,12-tetraphenyl-5,5 a, 11b, 12- tetrahydro-5 ,12-epoxydibenzo[b,h]- biphenylene (7 9) .................... 70 Reaction of 1,2-Dibromo-3,8-diphenyl­ naphtho [b] cyclobutadiene (3 2) with Sodium Methoxide ........... 70 viii CONTENTS (Gontd.) Page 2-Bromo-3,8-diphenylnaphtho[b]- cyclobuten-1-one (80) .................... 70 2-Hydroxy-3)8-diphenylnaphtho[b]- cyclobuten-1-one (8l) .................... 71 APPENDIX I ULTRAVIOLET ABSORPTION SPECTRA ....... 72 APPENDIX II NUCLEAR MAG^IETIC RESONANCE SPECTRA 8l APPENDIX III INFRARED ABSORPTION SPECTRA .......... 90 IX I. INTRODUCTION For years, the chemistry of cyclobutadiene, benzocyclo- butadione, naphthocyclobutadiene and their derivatives has held the interest of many organic chemists. Until the start of this work, all isolable compounds containing a cyclo­ butadiene nucleus have been either stabilized as their tran­ sition metal complexes or fused on both side as in biphenyl­ ene, to aromatic systems. Among those cyclobutadiene derivatives, which are stabilized by fusion on both sides to aromatic rings, are biphenylene (1) and dibenzobiphenylenes. Biphenylene (1) •1 was first synthesized by Lothrop and 2,3,6,7-dibenzobi- p 3 1-1 phenylene (2) by Curtis and Viswanath.Cava and 8tucker ^ W. C. Lothrop, J. Am. Chem. Soc., 6^ 1l8? (19^1). p R. F. Curtis and G. Viswanath, Chem. and Ind., 117^ (19540. R. F. Curtis and G. Viswanath, J. Chem. Soc., 1670 (1959). ^ M. P. Cava and J. F. Stacker, J. Am. Chem. Soc., 22 6022 (1955). synthesized 1 ,2-benzobiphenylene (3) and 1,2,7,8-dibenzobi- phenylene (4), and pointed out that 2,3,6,7-dibenzobiphenyl- ene (2) is thermally more stable than 1,2,7,8-dibenzobi- phenylene (4). The stability of these compounds has also been discussed from the theoretical point of view by Ali and Coulson;^ from molecular orbital calculation of their pi- electron energies and bond orders, it was found that the resonance energy of ■2,3,6,7-dibenzobiphenylene (2) exceeds that of 1 ,2,758~dibenzcbiphenylene (4-) by ^.3 kcal/mol.. (1) (3) (W M. A. Ali and C. A. Coulson, Tetrahedron, 1_0 U-1 (I960). Another group of stabilized cyclobutadiene derivatives are the cyclobutadiene transition metal complexes; examples of the latter include 1,2,3,^--tetramethylcyclobutadiene 6 7 nickel bromide complex,’ 1,2,3,^-tetraphenylcyclobutadiene nickel bromide complex,8 1,2,3,4-tetraphenylcyclobutadiene ^ R. Criegee and D. Schroeder, Ann., 623 1 (1959)* ^ R. Criegee, Angew. Chem., 2h. 703 (1962). ^ H. H. Freedman, J. Am. Chem. Soc., 82 219^ (1961). Q -IQ iron carbonyl complex or palladium chloride complex, and the recently discovered benzocyclobutadiene iron tricarbonyl / "j 4 complex (5) etc. These complexes form a group of compounds in which the bonding between the metal and the carbocycle has considerable pi-character. 0 JJ--Fe(C0)3 (5) (6) (7) ^ W, Huebel, et al., J . Inorg. Nucl. Chem., 2 20*+ (1959). T. Blomquist and P. M. Maitlis, J. Am. Chem. Soc., ^ 2329 (1962). 1 1G. F. Emerson, L. Watts and R. Pettit, J. An. Chem. Soc., ^ 131 (1965). A group of stable compounds which may be considered to be closely related to cyclobutadiene are the cyclobutadieno- 12 quinones, such as phenylcyclobutadienoquinone (6 ) and 1 3 benzocyclobutadienoquinone (7), in which all four-membered ring carbons are sp^-hybridized. 12 E. J. Smutny, M. C. Caserio and J. D. Roberts, J. Am. Chem. Soc., ^ 1793 (I960). 1 3 M. P. Cava
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    US007968215B2 (12) United States Patent (10) Patent No.: US 7,968,215 B2 Begley et al. (45) Date of Patent: Jun. 28, 2011 (54) OLED DEVICE WITH CYCLOBUTENE 4,539,507 A 9/1985 Vanslyke et al. ELECTRON INUECTION MATERALS 4,720,432 A 1/1988 Vanslyke et al. 4,768,292 A 9, 1988 Manzei et al. 4,769,292 A 9/1988 Tang et al. (75) Inventors: William J. Begley, Webster, NY (US); 4.885,211 A 12/1989 Tang et al. Natasha Andrievsky, Webster, NY (US) 4.885,221 A 12/1989 TSuneeda et al. 5,059,861 A 10, 1991 Littman et al. (73) Assignee: Global OLED Technology LLC, 5,059,862 A 10/1991 VanSlyke et al. Wilmington, DE (US) 5,061,569 A 10/1991 VanSlyke et al. 5,077,142 A 12/1991 Sakon et al. 5,121,029 A 6/1992 Hosokawa et al. (*) Notice: Subject to any disclaimer, the term of this 5,141,671 A 8/1992 Bryan et al. patent is extended or adjusted under 35 U.S.C. 154(b) by 287 days. (Continued) (21) Appl. No.: 12/330,547 FOREIGN PATENT DOCUMENTS EP 681019 11, 1995 (22) Filed: Dec. 9, 2008 (Continued) (65) Prior Publication Data OTHER PUBLICATIONS US 2010/01.41122 A1 Jun. 10, 2010 “Double Injection Electroluminescence in Anthracene”. RCA Review, 30, 322, (1969). (51) Int. C. HOIL 5/54 (2006.01) (Continued) CO7D 40/02 (2006.01) CO7D 47L/04 (2006.01) Primary Examiner —Dawn L. Garrett CO7D 403/02 (2006.01) (74) Attorney, Agent, or Firm — McKenna Long & Aldridge CO7D 213/6 (2006.01) LLP CO7D 40/4 (2006.01) CO7D 409/4 (2006.01) (57) ABSTRACT (52) U.S.
  • Problems Discussed in the Videos

    Problems Discussed in the Videos

    Problems discussed in the videos: Video (2) 44. The isolation of a new form of molecular carbon, C60, was reported in 1990. The substance has the shape of a soccer ball of carbon atoms and possesses the nickname “buckyball” (you don’t want to know the IUPAC name). Hydrogenation produces a hydrocarbon with the molecular formula C60H36. How many degrees of unsaturation are present in C60? In C60H36? Does the hydrogenation result place limits on the numbers of π bonds and rings in “buckyball”? Videos (2) – (3) 46. Write the structures of as many simple alkenes as you can that, upon catalytic hydrogenation with H2 over Pt, will give as the product (a) 2-methylbutane; (b) 2,3- dimethylbutane; (c) 3,3-dimethylpentane; (d) 1,1,4-trimethylcyclohexane. In each case in which you have identified more than one alkane as an answer, rank the alkenes in order of stability. Video (3) 64. What is the empirical formula? (Compound drawn on blackboard in video.) 65. What is the degree of unsaturation in cyclobutane? Video (4) 66. What is the IUPAC name? (Compound drawn on blackboard in video.) 28. The bicyclic alkene car-3-ene (drawn on blackboard in video), a constituent of turpentine, undergoes catalytic hydrogenation to give only one of the two possible stereoisomeric products, with the methyl group and the cyclopropane ring on the same face of the cyclohexane ring. Suggest an explanation for this stereochemical outcome. Videos (4) – (5) 29. Give the expected major product of catalytic hydrogenation of each of the following alkenes (drawn on blackboard in videos).
  • Characterization and Catalytic Cracking of Tar Obtained in Coal

    Characterization and Catalytic Cracking of Tar Obtained in Coal

    University of North Dakota UND Scholarly Commons Theses and Dissertations Theses, Dissertations, and Senior Projects January 2015 Characterization And Catalytic Cracking Of Tar Obtained In Coal / Biomass / Municipal Solid Waste Gasification: The seU Of Basic Mineral Catalysts And Miscibility, Properties, And Corrosivity Of Petroleum-Biofuel Oils And Blends For Application In Oil-Fired Power Stations Stacy Joan Bjorgaard Follow this and additional works at: https://commons.und.edu/theses Recommended Citation Bjorgaard, Stacy Joan, "Characterization And Catalytic Cracking Of Tar Obtained In Coal / Biomass / Municipal Solid Waste Gasification: The sU e Of Basic Mineral Catalysts And Miscibility, Properties, And Corrosivity Of Petroleum-Biofuel Oils And Blends For Application In Oil-Fired Power Stations" (2015). Theses and Dissertations. 1744. https://commons.und.edu/theses/1744 This Dissertation is brought to you for free and open access by the Theses, Dissertations, and Senior Projects at UND Scholarly Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of UND Scholarly Commons. For more information, please contact [email protected]. CHARACTERIZATION AND CATALYTIC CRACKING OF TAR OBTAINED IN COAL / BIOMASS / MUNICIPAL SOLID WASTE GASIFICATION: THE USE OF BASIC MINERAL CATALYSTS AND MISCIBILITY, PROPERTIES, AND CORROSIVITY OF PETROLEUM-BIOFUEL OILS AND BLENDS FOR APPLICATION IN OIL-FIRED POWER STATIONS by Stacy Joan Bjorgaard Bachelor of Science, University of North Dakota, 2010