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BEA-Ha,5,7,9Nfentaenve PART 11 the REARRANGEMENTS of Monosuefitwuted CYCLOOCTATETRAEHEB

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BEA-Ha,5,7,9Nfentaenve PART 11 the REARRANGEMENTS of Monosuefitwuted CYCLOOCTATETRAEHEB PART 1 SWQIES CONCERNED WETH THE EYfoéxESES CF QCTALEEQE ANfl BICYCLE [@3‘0]BEA-ha,5,7,9nFENTAENVE PART 11 THE REARRANGEMENTS OF MONOSUEfiTWUTED CYCLOOCTATETRAEHEB Thesis 5o;- Nac Dogma of DE. D. MiCHlGAN STATE UNIVERSITY Greg A. Bullock 1968 g is r' ,_ p, Viv-f L i u .- .4 4< 1 ' ‘lichigan Sm é University This is to certify that the thesis entitled Part I: STUDIES CONCERNED WITH THE SYNTHESIS OF OCTALENE .,AND BICYCLO[6.2.0]DECA-l,3,5,7,9-PENTAENE Part II: THE REARRANGEMENTS 0F MDNOSUBSTITUTED CYCLOOCTATETRAENES presented by Greg A. Bullock ._ _.._I-_ 4 has been accepted towards fulfillment of the requirements for .-—*<7-» -.. Ph.D. degree in Chemistry Major pro sor _ Datuéymililfé? .-_ ._ 0-169 .I.‘—..._._.,._._-_.—_ -a_..-_.-__.IV.._._~_ .I ABSTRACT PART I STUDIES CONCERNED WITH THE SYNTHESIS OF OCTALENE AND BICYCLO[6.2.0]DECA-1,3,5,7,9-PENTAENE PART II THE REARRANGEMENTS OF MONOSUBSTITUTED CYCLOCCTATETRAENES by Greg A. Bullock The initial goal of this investigation concerned the synthesis of bicyclo[6.6.0]tetradeca-1,3,5,7,9,11,13-heptaene (octalene). Several synthetic approaches leading to the preparation of octalene were attempted. None of these ap- proaches, however, was successful. During the course of this investigation a new synthetic route to [2.2]paracyclo- phanes was discovered. 4.5.12,13—Tetracarbomethoxy[2.2]para— cyclophane was synthesized from dimethyl 3,6-bis(hydroxy— methyl)-1,4-cyclohexadiene-1,2-dicarboxylate diepftoluene- sulfonate by solvolysis in buffered acetic acid. The bis- (hydroxymethyl)cyclohexadiene was prepared from a Diels- Alder reaction between trans,trans—2,4-hexadiene-1,6-diol and dimethyl acetylenedicarboxylate. The synthesis of bicyclo[6.2.0]deca-1,3,5,7,9-pentaene was also attempted. Synthetic approaches to the bicyclic decapentaene involved the attempted condensation of both dehydrocyclooctatetraene and N{N-diethylaminocyclobctatetra- ene with substituted acetylenes. The condensation of N,N,diethylaminocyclobctatetraene with dimethyl Greg A. Bullock acetylenedicarboxylate yields dimethYLJSZ-naphthalenedicar- boxylate as the only isolable product. A logical proposal for the formation of this product is that the condensation product, dimethyl l-N,N-diethylaminobicyclo[6.2.0]deca— 2,4,6,9—tetraene-9,10-dicarboxylate, ring opens to produce dimethyl l-N,N—diethylaminocyclodecapentaene-2,3-dicarboxyl- ate. The [10]annulene could then cyclize accompanied by the loss of diethyl amine to yield the observed product. The preparation of bicyclo[6.2.0]decapentaene was attempted also from tetramethyltricyclo[6.2.0.03I6]decane-2,7-dione-4,5,9,10- ‘tetracarboxylate without success. The stereochemical con- figuration of tetramethyl bicyclo[6.2.0.0316]decane-2,7- dione-4,5,9,10-tetracarboxylate was established from its nmr spectrum and from the configuration of tetramethyl 11—oxa- tetracyclo[4.4.1.02t5.07:1°]undecane-3,4,8,9-tetracarboxylate, one of its reaction products. The cyclohexadione ring of the tetramethyl dione exists in a boat form with the two cyclobutane rings gig fused to the pseudoequatorial posi- tions. The carbomethoxy groups are believed to be gig to each other and trans to the cyclohexadione—cyclobutane ring junction. Chloro- and bromocyclobctatetraene thermally rearrange to trans—fi-chloro- and Eganng-bromostyrene, respectively. The solvolysis of chlorocyclodctatetraene in methanolic solu— tions containing various nucleophiles is also discussed. Methanolysis of chlorocyclooctatetraene yields a mixture of Greg A. Bullock trans—B-chlorostyrene, trans-B-methoxystyrene, and phenyl- acetaldehyde dimethyl acetal. If methanolfi§_is used as the solvent, the phenyacetaldehyde dimethyl acetal is labeled in the benzylic position. *Methanolysis of chlorocyclobcta- tetraene in the presence of sodium methoxide produces, along with trans-B-chlorostyrene and trans-B-methoxystyrene, meth- oxycyclooctatetraene whereas methanolysis in the presence of lithium bromide yields trans-B-chlorostyrene, trans-B— methoxystyrene, and trans—fi-bromostyrene. These results are compatible with the View that the valence tautomer of chlorocyclooctatetraene, 1-chlorobicyclo[4.2.0]octa—2,4,7- triene, ionizes to the corresponding bicyclic octatrienyl carbonium ion. A mechanism for the formation of the pro- ducts in these reactions is discussed. The rearrangement takes a different pathway when diethylamino- or Efbutoxy- cyclooctatetraene are heated. In both of these cases the a-substituted styrenes are produced. A mechanism for the latter rearrangement is proposed. PART I STUDIES CONCERNED WITH THE SYNTHESIS OF OCTALENE AND BICYCLO[6.2.0]DECA-1,3,5,7,9-PENTAENE PART II THE REARRANGEMENTS OF MONOSUBSTITUTED CYCLOOCTATETRAENES BY ‘09 Greg A. Bullock A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1968 ACKNOWLEDGMENT The author wishes to express his sincere gratitude to Professor Eugene LeGoff for encouragement, guidance and en— thusiasm throughout the course of this investigation and also for arranging financial support from September, 1967 to August, 1968. Appreciation is extended to Michigan State University for a teaching assistantship from September, 1965 to August. 1966, t0 Lubrizol Corporation for a research fellowship from September, 1966 to August, 1967 and to Petroleum Research Foundation for a research fellowship from September, 1967 to August, 1968. ii To Lisa iii TABLE OF CONTENTS Page PART I HISTORICAL AND INTRODUCTION . Previous Approaches to Octalene . 10 Previous Approaches to Bicyclo[6.2.0]deca- 1,3,5,7,9-pentaene . 11 RESULTS AND DISCUSSION . 15 Octalene . 15 Bicyclo[6.2.0]deca-1,3,5,7,9-pentene . 27 EXPERIMENTAL . 45 General Procedures . 45 Diels—Alder Adduct of 1,4—Dipheny1-2-styryl- 1,3-butadiene and Maleic Anhydride . 45 1,4,5,8-Tetrahydro-1,4,5,8-naphthalenetetracar- boxylic Acid . 46 Dimethyl 3,6—Bis(hydroxymethyl)-l,4-cyclo- hexadiene—l,2-dicarboxylate . 47 Dimethyl 3,6—Bis(hydroxymethyl)-1,4—cyclohexa— diene-1,2-dicarboxylate Di-pftoluenesulfonate 48 Attempted Ring Expansion of Dimethyl 3,6-Bis- (hydroxymethyl)-1,4-cyclohexadiene-1,2-di— carboxylate Di-pftoluenesulfonate . 48 9,10-Diethylbicyclo[6.2.0]deca-l,3,5,7,9- pentaene (Attempted) . 50 9-Ethyl-10-methoxybic clo[6.2.0]deca-1,3,5,7,9- pentaene (Attempted ; Preparation of EjAmyl- oxycyclofictatetraene . 51 N.N-Diethylaminocycloactatetraene . 52 iv TABLE or CONTENTS (cont.) PART I ' Page Dimethyl l-N,N-Diethylaminobicyclo[6.2.0]deca- 2,4,6,9-tetraene—9,lO-dicarboxylate (Attempted); Preparation of Dimethyl 1,2-Naphthalenedi- carboxylate . 53 Tetramethyl Tricycld[6.2.0.03:5]decane-2,7- dione-4,5,9,10-tetracarboxylate . 54 Tetramethyl Tricyclo[6.2.0.03I6]decane—2,7-di- one-2,7—bisoxime-4,5,9,10-tetracarboxylate . 54 Tetramethyl Tricyclo[6.2.0.03:6]decane-2,7-dione— 2,7-bistosylhydrazone-4,5,9,10-tetracarboxylate 56 Tetramethyl 2,7-Dihydroxytricyclo[6.2.0.03'6]- decane-4,5,9,10-tetracarboxylate . 56 Tetramethyl 2,7-Dibromotricyclo[6.2.0.03:5]- decane-4,5,9,10-tetracarboxylate (Attempted) 57 Tetramethyl 2,7-Dihydroxytricyclo[6.2.O.03'6]- decane-4,5,9,10-tetracarboxylate DifEf toluenesulfonate . 58 Tetramethyl 11-0xatetracyclo[4.4.1.02[5.07:101- undecane-3,4,8,9-tetracarboxylate . 59 ll-Oxatetracyclo[4.4.1.02I5.07:1°]undecane- 3,4,8,9-tetracarboxylic Acid Monohydrate . 60 PART II HISTORICAL AND INTRODUCTION . 62 RESULTS AND DISCUSSION . 64 EXPERIMENTAL . 80 Thermal Rearrangement of Chlorocyclobctatetraene to trans-B—Chlorostyrene . 80 Rearrangement of Chlorocyclobctatetraene in Refluxing Methanol . 80 TABLE OF CONTENTS (cont.) PART II Page Rearrangement of Chlorocyclobctatetraene in Methanolic Sodium Methoxide . 81 Rearrangement of Chlorocyclobctatetraene in Methanolic Lithium Bromide . 82 Tetracyanoethylene Dials-Alder Adduct of Chloro- cyclobctatetraene . 83 Thermal Rearrangement of N,N-Diethylaminocyclo— octatetraene . 83 Thermal Rearrangement of EfButoxycyc108cta- tetraene . 84 Tetracyanoethylene Dials-Alder Adduct of E- Butoxycyclobctatetraene . 85 The Diels-Alder Reaction of E-Butoxycycloocta- tetraene with Dimethyl Acetylenedicarboxylate 85 LITERATURE CITED . 95 vi LIST OF SCHEMES SCHEME Page A Proposed Synthetic Route to Triphenyl- octalene . 16 II. A Proposed Synthetic Route to Octalene 18 III. The Synthesis of 3,6-Bis(hydroxymethyl)-1,4- cyclohexadiene-l,2-dicarboxylate Difipf toluenesulfonate 24 IV. The Chemical Reactions of Dehydrocyclobcta- tetraene . 29 V. The Chemical Reactions of Benzyne 3O VI. A Proposed Synthetic Route to Bicyclo[6.2.0]— deca-1,3,5,7,9-pentaene 34 VII. A Proposed Synthetic Route to Tricyclo- [6.2.0.03I6]decane-2,7—dione-4,5,9,10— tetracarboxylic Acid 36 VIII. Proposed Synthetic Routes to Tetramethyl Tri— cyclo[6.2.0.03I6]deca-1,7—diene-4,5,9,10— tetracarboxylate 38 IX. A Mechanism for the Rearrangement of Chloro— cyclooctatetraene in Methanol-d 69 Mechanism for the Rearrangement of Chloro- cycloocatetraene in Methanolic Sodium Methoxide . 7O XI. A Mechanism for the Rearrangement of Chloro- cyclobctatetraene in Methanolic Lithium Bromide . 71 XII. A Mechanism for the Thermal Rearrangement of N.N—Diethylamino- and EfButoxycyclobcta— tetraene . 77 vii LIST OF FIGURES FIGURE Page 1. Infrared Spectrum of 1,4,5,8-Tetrahydro- 1,4,5,8-naphthalenetetracarboxylic Acid . 87 2. Infrared Spectrum of 4,5,12,13-Tetracarbo- methoxy[2.2]paracyclophane . 87 3. Infrared.Spectrum of EfAmyloxycyclobctatetraene 87 4. Infrared Spectrum of N,N-Diethylaminocyclo— Octatetraene . 88 5. Infrared Spectrum of Tetramethyl Tricyclo— [6.2.0.03I5]decane-Z,7-dione—2,7—bisoxime- 4,5,9,10-tetracarboxylate . 88 6. Infrared Spectrum of the Diacetate of Tetra— methyl Tricyclo[6.2.0.03'6]decane-2,7—dione-2,7- bisoxime-4,5,9,10-tetracarboxylate . 88 7. Infrared Spectrum of Tetramethyl Tricyclo- [6.2.0.03I6]decane-2,7-dione-2,7-bistosyl— hydrazone-4,5,9,10—tetracarboxylate . 89 8. Infrared Spectrum of Tetramethyl 2,7-Dihydroxy- tricyclo[6.2.0.03t6]decane-4,5,9,10-tetracare boxylate .
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