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THE BENZOCYCLOBUTENE SYSTEM DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosoph

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THE BENZOCYCLOBUTENE SYSTEM DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosoph THE BENZOCYCLOBUTENE SYSTEM DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By DONALD RAY NAPIER, B. S. a****** The Ohio State University 1957 Approved hy: •YU f I J. v f i . Adviser Department of Chemistry ACKNOWLEDGMENT The author wishes to express his deepest apprecia­ tion to Dr. Michael P. Cava, who suggested this problem and whose guidance and council were of inestimable value toward its completion. He also wishes to thank fellow graduate students and members of the staff for their co­ operation. ii TABLE OP CONTENTS PAGE I. INTRODUCTION .......................... 1 II. DISCUSSION AND INTERPRETATION OP RESULTS . 13 III. EXPERIMENTAL .......... ..................... 45 Reaction of a,a,a',a'-tetrabromo-o-xylene (XXXIII) with sodium iodide ........... 45 1.2-Dibromobenzocyclobutene (XXXIV) .... 46 Treatment with maleic anhydride.. ....... 47 Oxidation to phthalic acid ....... 47 Reaction with bromine ................... 48 Treatment with potassium acetate .... 49 1 .2-Diiodobenzocyclobutene (XXXVII) .... 49 Benzocyclobutadiene dimer (XLVI) ....... 50 Aromatization with N-bromosuccinimide . 52 Behavior with other aromatizing reagents 53 Dibromide of benzocyclobutadiene dimer . 55 Dehydrobromination to monobromide XLIX . 55 5-Bromobenzo-[a3-biphenylene (XLVII) . 56 Zinc dehalogenation of triiodide L . 57 Dehydrohalogenation of triiodide L . 53 Benzocyclobutene (I) 58 Thermal stability and acid sensitivity . 61 Attempted HI reduction of diiodide XXXVII . 62 Action of LiAlH^ on diiodide XXXVII .... 63 1-Bromobenzocyclobutene (LXI) ............. 63 iii iv PAGE Reaction with, potassium t-butoxide . 64 Reaction with sodium methoxide ........ 65 Reaction with magnesium ................. 65 1-Cyanobenzocyclobutene (LXIII) ........... 66 Oxidation to benzocyclobutene-l-carbox- amide (LXIV) ..... ................. 67 l=Aminomethyl-benzocyclobutene hydrochlor­ ide ..................... ............ 68 Benzocyclobutene-l-carboxylic acid (LXYI) . 68 1.2-Bis-(trifluoroacetoxy)-benzocyclobu- tene (LXIX) ............................ 69 Hydrolysis o f ............................ 70 Gis and trans esters of 1,2-benzocyclobu- tenediol (LXXIa and LXXIb) ............. 71 1.2-Diketobenzocyclobutene (LXXII) .... 72 Quinoxaline derivative ......... 73 2,4-Dinitrophenylhydrazone 73 Oxidation to phthalic a c i d ............. 79- Conversion to phthalaldehydic acid . 79- Reaction with potassium t-butoxide . 75 5-t-Butoxyphthalide (LXXXI) ............. 76 Hydrolysis to phthalaldehydic acid . 77 APPENDIX I: INFRARED ABSORPTION SPECTRA ......... 79 APPENDIX II: ULTRAVIOLET ABSORPTION SPECTRA . 87 AUTOBIOGRAPHY....................................... 96 LIST OP TABLES TABLE PAGE I. Ultraviolet Absorption Maxima for Benzocyclo­ butene, Indane, and Tetralin ............... 30 II. Influence of Reaction Variables in tbe Aroma- tization of Benzocyclobutadiene Dimer (XLVI) ..................................... 53 III. Fractional Distillation of Crude Benzocyclo­ butene ( I ) ........................ 59 LIST OF CHARTS CHART PAGE I. Proposed Mechanisms for the Formation of 1,2-Dibromobenzocyclobutene and 1,2- Diiodobenzocyclobutene . .................... 20 II. Proposed Mechanisms for the Formation of Triiodide (L) ..... ...................... 28 THE BENZOCYCLOBUTENE SYSTEM I. INTRODUCTION Until recently^" the simplest known alicylic-aroma- tic system was indane (II). Although the higher homologs of indane such as tetralin (III) are well known, no au­ thenticated synthesis of even a simple derivative of the 2 lower homolog, Benzocyclobutene (I) , has been previous- lL ly described. As early as 1888, W. H. Perkin, Jr. wrote of unsuccessful attempts to prepare benzocyclobutene der- I II III ivativas, however, no mention was made of the specific reactions employed. Since that time the problem has been attacked in principally two ways - by the attempted ring contraction of indane derivatives and ring closure of o~ xylene derivatives. ^A part of the work recorded in this dissertation has been published elsewhere. See reference 3« P For the nomenclature of these compounds see refer­ ence 3» ^M. Cava and D. Napier, J. Am. Chem. Soc., 500 (1956); ibid., Z2, 1701 (1957). \ . H. Perkin, Jr., J. Chem, Soc., 1 (1888). The lack of any success in these attempts can un- doubtably he attributed to the strain existing in a sys­ tem such as I. In the absence of any thermochemical data on unsubstituted cyclobutene only a crude approximation can be made as to the magnitude of the strain induced on passing from indane to benzocyclobutene. However, it must be considerably lower than that in the unknown benzo­ cyclobutadiene (IV) or the known biphenylene (V). Prom heats of combustion data it has been estimated that the latter is strained to the extent of 60 + 5 kcal. with re­ spect to biphenyl.^ It possesses however, a net stabil­ ization energy of some 22+5 kcal. On the assumption IV V that three of the bonds in I are aliphatic and comprable to those of cyclobutane (each with approximately 6 kcal. of strain)^ and the bond common to both rings is similar to the corresponding one in V, then the net strain is 18 + 15 or 33 kcal. ^From thermochemical data it is estimated that the strain in indane is no greater than in unsubstituted cy- clopentane (1.5-2 kcal.). See M. Dolliner, T. Gresham and G. Kistiakowsky, J. Am. Chem. Soc., ^9, 831 (1937)* 6R. Cass, H. Springall and P. Quincy, J. Chem. Soc., 1188, 1955. 7The experimental value for the strain in cyclobutane is 26.2 kcal. as determined by S. Kaarsemaker and J. Coops, Rec. trav. chim., 261, (1952). Although, the assumptions made are perhaps unjust­ ified, it is to be noted that value of 33 kcal. is less than that of the positive delocalization energy of benzene (36-40 kcal.), to which must be added a small but not in­ significant amount of hyperconjugation energy. Referring to biphenylene as an exception, doubts have been expressed concerning the stability of any other system containing a four membered ring fused to an aroma- 8 tic nucleus. These doubts were based on the nonexis­ tence of such systems at that time and on the expectation that the resonance stabilization of the aromatic ring would not fully compensate for the instability induced by straining the bond angles through 40 degrees. In regard to bond angles, it has been pointed out that the lines of maximum charge density for the orbitals forming the bonds do not necessarily coincide with the directions of the Q attached atoms. Also, it is to be noted that irrespec­ tive of the actual magnitude of the strain, unsubstituted cyclobutene is an isolable hydrocarbon."1'0 Referring next to benzocyclobutadiene (IY), the magnitude of the strain in this system - if comparable to that in biphenylene (60 ®W. baker, J. Chem. Soc., 258, 1945. ^Cf. C. Coulson and W. Moffitt, Phil. Mag., 40, 26 (1949). 10Por reconfirmations of Willstater and von Schmae- del's original synthesis, see J. Roberts and C. Sauer, J. Am. Chem. Soc., 5925 (1949). kcal.) - is significantly greater than that of its calcu- 11 lated resonance energy 2.38^ (42 kcal.). It might be expected, therefore, that this system would be consider­ ably less stable than that of benzocyclobutene. With the object of preparing the bridged tautomer 12 of napthalene, VI, Ingold and Challenor once attempted the synthesis of compounds Vila and Vllb which were to be used as intermediates. Treating the dibromides Villa or V U I b with a variety of different bases resulted in the isolation of only polymers of compositions approximating to those of the compounds Vila and Vllb. However, in the presence of ethyl sodiomalonate Vllb gave a small amount vr VIIa, R = VIII *,(?=C04EI V///, IX XI ^FromFrom simple M.OM.O. Calculations by J. Roberts and A Streitwieser, J. Am. Chem. Soc., 2fh» 9-579 (1954). 12C. Ingold and W. Challenor, J. Chem. Soc., 123, 2066 (1923). of an enolic material (subsequently converted to/^-Uap- " thol) which, was assigned the structure IX. Since the pro­ posed intermediate Vllb was never isolated, the possibil­ ity of the product being the ^- N a p thol derivative X(iso- meric with IX) cannot be excluded. It would then be un­ necessary to assume the existence of any four membered ring intermediates since, for example, X may arise by a Michael addition of ethyl malonate to an o-methylenequi- none intermediate XI; the subsequent formation of X in the basic medium would be unexceptional. More recently a claim to the effect that deriva­ tives of both the unknown systems I and IV are obtained in the same reaction has been made by the Russian chem- 13 ° ists Logidze and Petrov. Heating a mixture of 1,4-di­ ace toxybutyne -2 , benzene and aluminum chloride gave in addition to other products 20% of a liquid °12H14° 120°/2 mm.) which was assigned the structure XII and 12% of a solid GqqHqo (m.p. 103°) suggested to be XIII. The basis for the assignment of structure XII to the compound C12H14^ Was oxid-a'tiori 'fco hemimellitic acid. On re- o duction with Raney nickel the substance C^H-^q gave G-^^^ the Raman spectra of which indicated a very symmetrical molecule. Other reactions of XIII included its bromina- 1^R. Logidze and A. Petrov, Doklady Akad. Hauk S.S.S.R., 83, 235 (1952). tion to a monobromide, chromic oxide oxidation to Cn,,Ho0o m- o d and oxonolysis, resulting in the isolation of both formic and benzoic acids. The formation of benzoic acid on ozonolysis was cited as evidence that XIII had the pro-Q perties of a "chemical cliameleon". In the absence of more definited proof, it would appear that the structures of XII and XIII have been proposed without adequate ex­ perimental justification and must therefore be considered 14 untenable. Recent attempts have been made to prepare Ac ■X H XII XIII these compounds dn order to study them in more detail; o o however, in spite of extensive efforts no materials with physical or chemical properties resembling those ascrib­ ed to either XII or XIII could be isolated from reaction mixtures of benzene, aluminum chloride and 1,4-diacetoxy- butyne-2. Still another reference to a possible synthesis of a benzocyclobutene derivative is to be found in the clas­ sical work of E.
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