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Nuclear Substitution Reactions of Dibenzo-P-Dioxin Joseph Jacob Dietrich Iowa State College

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Nuclear Substitution Reactions of Dibenzo-P-Dioxin Joseph Jacob Dietrich Iowa State College Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1957 Nuclear substitution reactions of dibenzo-p-dioxin Joseph Jacob Dietrich Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation Dietrich, Joseph Jacob, "Nuclear substitution reactions of dibenzo-p-dioxin " (1957). Retrospective Theses and Dissertations. 1336. https://lib.dr.iastate.edu/rtd/1336 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]. NUCLEAR SUBSTITUTION REACTIONS OF DI3ENZC-£-BIOXIN by- Joseph Jacob Dietrich A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of 'DOCTOR OF PHILOSOPHY Major Subject : Organic Chemistry Approved: Signature was redacted for privacy. in Charge of I-'*ajor *.7ork Signature was redacted for privacy. Head of Ma nartment Signature was redacted for privacy. Dean of Graduate College Io?;a State College 1957 11 TABLE OF CONTENTS Page INTRODUCTION 1 -ISTJRICAL 5 Dibenzo-n-dioxin 5 Alkyl Derivatives Ô Carbonyl Derivatives 8 Carbozyl Derivatives 9 Dithiocarboxylate Derivatives 10 Halogen Derivatives 10 Hydroxy Derivatives 12 Methoxy Derivatives 12 Nitrogen Derivatives 13 Metallic Derivatives 14 Reduction of Dibenzo-^-dioxin 15 Kiscellaneous Derivatives of Dibenzo-jD-dioxin 15 Chemical Correlations 16 Derivatives of Dibenzo-n-dioxin 16 EXPERBSNTAL 2? Derivatives 2? 1-Iododibenzo-jD-dioxin 27 1,5(9 )-Bliododibenzo-;o-dioxin 28 2-lododibenzo-D-O-ioxin via diazotization 28 2-Iododibenzo-o-dioxin emgloying iodine monochloride 29 2-Iododibenzo-jo-dioxin ( attempted) 10 A diiodoclbenzo-jD-dioxin mixture 30 2, 3,7 « 8- T e i; r a chl or o d 1 b e n z o-;o- d io x in 31 2-Cyanodibenzo-;o-dicxin (attempted). Run I 32 Run II ' 32 2- Br o mo- 7- n i tr o d ib e n z o - x>- d io xin. Run I 33 Run II 33 2-Amino-7-bromodibenzo-p-dioxin 34 2, ?-Dibromodicenzo-_o-dioxin. Run I 35 Run II 36 2,8-Dibromo-3,7-dinitrodibenzo-^-dioxin 36 2-Bro:no-7, X-dinitrodibenzo-D-dioxin 37 2, X- Dib r oir.o- 7- ni t r o d i c e n z o-_o- d ioxi n 37 2- A M i no - X- br OHÎO d i be n z o - D- d i o x in 38 2,7-Diacet anidodibenzo-io-dioxin. Run I 39 Run II 39 ill Page 2- N1 tr odibe n zo-jD- diox in 40 2-Aminodibenzo-;o-dioxin 40 2-Acetamidodibenzo-p-dioxin 4l 2, f-Dinltrodibenzo-jD-dioxln 4l 2,?-DlL 3minodibenzG-_D-d.ioxin 42 2,3,?-Trinitrodibenzo-n-dioxln 43 2, 3J7,S-Tetranitrodibenzo-p.-dioxin. Run I 43 Run II 44 1,1 '-Bis( dicenzo-jD-dioxin) 44 2,2'-3is( dibenzo-jo-dioxin) 4< 2-Phenyldibenzo-n-dioxin 46 1-( 2-3ibenzo-t>-dioxinyl )-l, 2-diphenylethan.ol 4? 1-( 2-Di cenzo-n-dioxinyl )-1, 2-dipher.yle the ne 47 2-Acetyldibenzo-jO-dioxin 48 2-Acetyldibenzo-jo-dioxin oxime 48 2,7-3iacetyldlbenzo-j2-'^ioxin 49 2, 7-Diacetyldlbenzo-j3-dioxin dioxlme 50 2-Benzoylcibenzo-^-dioxin. Run I $0 Run II 51 2-3enzoyldlbenzc-jo-ô.ioxin oxime 2,7-I'ibenz.oyldlbenzo-j2-dloxin 52 2, 7-Bibenzoyldibenzo-T>-dioxin dioxime 52 Dibenzo-o-dioxin-l-carboxyllc acid 53 Bibenzo-o-dioxin-1,X-dicarboxylic acid 5^ Bibenzo-£-dioxin-2-carboxylic acid 55 Blbenzo-jD-^loxin-l-borcnic acid 55 Bibenzo-D-dioxin-1,X-diboronic acid 56 Halogen-metal interconversion of 2-brorr.odibenzo- jD-cioxin ( e.ttennted). Run I 57 Run II 57 Run III 57 Kercuration of dicenzo-_o-dioxin (attempted). Run I 58 Run II 58 Run III 58 Run IV 59 2, 2'-Azodibenzo-jo-dioxin 59 Dibenzo-jD-dioxin-X,Y-disulfonyl chloride 60 Coupling of jD-nitrobenzeneciazonium chloride vit h dibenzo-jD-dioxin (attempted) 61 Coupling of 2,4-dinitrobenzenediazcnium chloride with dibenzo-jo-dioxin ( attempted) 62 Cleavage of dibenzo-^o-dioxin vit h hydriodic acid (attempted). Run I 62 Run II 63 iv -age DISCUSSION 64 General Elucidation of Structure 54 By intermolecular ring closure 54 By intramolecular ring closure o4 By ring cleavage * 65 By direct nuclear substitution S5 By indirect nuclear substitution 56 By physical means 66 Structural Assignments of the Experimental Section 67 1 Position 67 2 Position 58 2,3 Positions 68 2,7 Positions 59 1,5(9) Positions 70 2,3,7 Positions 71 2,3,7,8 Positions 71 Melting Point Discrepancies 72 Directive Influence of Substltuents 72 Attempted Reactions 74 Kercuration 74 Diazo coupling 74 Hydriodic acid cleavage 75 Liquid Solution Scintillators 75 Suggested Studies 78 SUKKARY 80 ACKNOWLEDGMENT 82 1 INTRODUCTION Three numbering systems have been employed in the litera­ ture to describe derivatives of dibenzo-g-dioxin. The one adopted by Chemical Abstracts and also to be used in this dis­ sertation is shown by I. The other two systems are illustrated by II and III. Even though the use of I is most common, a certain amount of confusion still exists due to the usage by some abstractors of II, which, because of the symmetry of the molecule, is not too ambiguous. Diphenylene dioxide is the common neme for dibenzo-n- dioxin and appears frequently in the literature. The Japanese workers still favor this name and have used it in recent publications. Other names now rarely used are dibenzo—1,4- dioxin, p-dibensodioxin, and phendloxin. The planarity or non-planar 1 t.y of c.ibenzo-p-dioxin is still undecided. It does not form a solid solution with phenoxathiin"*", a non-planar molecule, and was found to have a zero or nearly zero dipole moment when measured in carbon 2 tetrachloride $ cyclohexane, or benzene solutions. The re­ sults obtained from x-ray studies ere consistent with a planar q molecule, but the other possibility cannot be excluded.- •4* ^ Eigasi and Uyeo ' reported dipole moments of 0.64 and 0.57 Debye units when dibenzo-jD-dioxin vas measured in benzene and cyclohexane, respectively. This was interpreted as showing the molecule to be folded about the 0-0 axis with the benzene o rings lying at an angle of ISO . The oxygen valence angle is 117°. using the same method, they also found 2,7-dimethyldi­ ce nzo-t>-diox in and 2,7-dichlorodibenzo-x>-dioxin to have dipole moments of 0.61 and 0.62 Debye units, respectively. From the """N. Cull inane and F.ees, Trans. Faradav 5oc. , 35, 50? (1940). ' ^ p _ G-. Bennett, D. ^ar-c>, and S. Glas s ton, Chem. Soc. , 1179 (193^). -^H. Wood and G-. v.*illiams, Phil. M^g. , 31. 115 ( 19^-1 ) [G. èjL.* 11» 2766 (1941Q . 4 1C. Eigasi, Sci_. Pa-cers Inst. Phys. Chem. Ke search, (Tokyo), JS7 331 Tï^oTCçrX, 25, 3496 (194l)J . ^K. Eigasi and £. Uyeo, J. Chem. Soc. J a r>a.n, 62, 396 (1941)[Ç, , Jl, 6103 (19391%. 3 evidence presented, it may be concluded that dibenzo-n-dioxin deviates only slightly, if at all, from a planar configuration. It forms crystals of the monoclinic holohedral class and con­ tains four molecules per unit cell with a strong tendency for twinning.^ The substituted dibenzo-£-dioxin nucleus has been isolated from the degradation of some naturally occurring materials such g 7 as trilobine, isotrilobine , and micranthine. Neither these nor dibenzo-jD-dioxin itself has any pharmacological value at the present time. Of the many dibenzo-B-dioxin derivatives tested for anti­ bacterial activity, only 2, ?-di( ^ -chloropropionyl)dibenzo-x>- dloxin and its ^ substituted derivatives were effective (at a dilution of 1:160,000) for Mycobacterium tuberculosis. Sta-ohvlococcus aureas. and 5s. coll.® Subcutaneous injections of dibenzo-p-dioxin and the hydrochloric acid salt of 2- aminodibenzo-j>-dioxin were tried on mice, rabbits, and frogs. Both proved to be depressants and death was due to respiratory failure when a dosage of 50-100 mg. per kg. was used.^ ®M. To mit a and C. Tanl, J. Phsrm. Soc. Ja-pan. 62, 468 (19^2) [Ct 4£, 4728 (I95llj. ?1. Bick and A. Todd, J. Chem. Soc., 1602 (1950). g M. Tomita and W. Watanabe, J. Pharm. Soc. Japan, 71. 1198 (1951) Qk A-, 46, 7617 (19525]. ^M. Okada and S. Frese, Japan J. Med. Sci. IV, Pharmacol. Trans., £, 9 (1936) [JL At. 8021 (1937 )J . 4 The present study was undertaken to elucidate the basic chemistry of dibenzo-jD-dioxin. This necessarily led to the preparation of many derivatives and proof of their structures by both chemical and physical means. Direct nuclear substitu­ tion is especially attractive since the molecule contains two oxygen atoms capable of delivering their activating influence to eight positions, four of which are known to be susceptible to eleetrophilic attack. In addition to elucidating the basic chemistry of dibenzo- n-dioxin, some of the dibenzo-jo-dioxin derivatives are being tested for possible use in brain tumor therapy by Dr. Otho D. Easterday of the Brookhaven National Laboratory. Others have been evaluated as organic liquid solution scintillators by Drs. Wright H. Langham, F. Newton Hayes, and Donald G. Ott of the Los Alamos Laboratories. 5 HISTORICAL The literature has been surveyed up to March, 1957, and will cover only derivatives that can conceivably be made by direct nuclear substitution and are pertinent to the elucida­ tion and prediction of new nuclearly substituted products.
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