City University of New York (CUNY) CUNY Academic Works Dissertations, Theses, and Capstone Projects CUNY Graduate Center 1983 The Theory and Synthesis of [2.2.2] Propellane Theodore Mark Prociv The Graduate Center, City University of New York How does access to this work benefit ou?y Let us know! More information about this work at: https://academicworks.cuny.edu/gc_etds/4125 Discover additional works at: https://academicworks.cuny.edu This work is made publicly available by the City University of New York (CUNY). Contact: [email protected] INFORMATION TO USERS This reproduction was made from a copy of a document sent to us for microfilming. While the most advanced technology has been used to photograph and reproduce this document, the quality of the reproduction is heavily dependent upon the quality of the material submitted. The following explanation of techniques is provided to help clarify markings or notations which may appear on this reproduction. 1. 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Zeeb Road, Ann Arbor, MI 48106 Copyright 1982 by Prociv, Theodore Mark All Rights Reserved 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 num bered ___________, Text follows. 14. Curling and wrinkled pages ______ 15. Other_______________________________________________________________ University Microfilms International THE THEORY AND SYNTHESIS OF [2.2.2] PROPELLANE BY THEODORE M. PROCIV A dissertation submitted to the Graduate Faculty in Chemistry in partial fulfillment of the require­ ments for the degree of Doctor of Philosophy, The City University of New York. 1982 9 COPYRIGHT BY THEODORE M. PROCIV 1982 ii This manuscript has been read and accepted for the Graduate Faculty in Chemistry in satisfaction of the dissertation requirement for the degree of Doctor of Philosophy. [Signature] so P^/rs-2- date Chaimapr of Examining Committe [Signature] date Executive Officer [Signature] [Signature] Supervisory Committee The City University of New York iii Abstract THE THEORY AND SYNTHESIS OF [2.2.2] PROPELLANE by Theodore M. Prociv Advisor: Professor Joseph J. Dannenberg INDO calculations indicated that the triplet state of dimethylene cyclohexane could rearrange to gometrically relaxed triplets which should collapse pref­ erentially to the ground state [2.2.2] Propellane. A mercury sensitized photolysis of the dimethylene cyclohexane did in fact result in detectable quantities of the propellane, trapped as 1,4 dibromobioyolo octane. Synthesis of 1,4 dibromobioyolo ootane and 1,1,6,6 tetradeuterodimethylene-cyclohexane are presented in the dissertation. Included in the dissertation are the results of INDO calculations of various propellane isomers having nitrogens and borons in the bridgehead positions. iv TABLE OP CONTENTS Page CHAPTER I. THEORETICAL APPROACH TO THE SYNTHESIS OF [2.2.2] PROPELLANE ................................................ 1 Introduction .............................. 1 Description of Project .................................. 3 Experimental History Related to the Propellanes ........... 5 Theoretioal History Related to Propellanes ................. 12 EH Calculation ..................................... 12 Ab-Initio SCF/CI ....................................... 16 Geometrical Strain Consideration .................... 16 Competition With the Cope Rearrangement ................. 16 Summary and Justification .................................. 22 II. MOLECULAR ORBITAL TREATMENT OF [2.2.2] PROPELLANE ENERGY SURFACE .............................................. 24 Method of Calculation of this Thesis ................. 24 Selection of Method ............................... 24 INDO Method ............................................ 25 Theoretioal Approach .................................. 26 Results: Optimization of Geometries ......................... 28 Disoussion of Calculations ....................... 32 Singlet State Isomers ...................................... 32 The Triplet State .......................... 35 Suggested Experimental Approaoh ................... 35 III. SYNTHESIS OF [2.2.2] PROPELLANE ............................ 40 An Approaoh to the Synthesis of 2 40 Choice of Starting Material .................. 41 Dibromo Derivative of 2 42 v TABLE OF CONTENTS (Continued) Page Experimental Approaches .................. 44 A. Photolysis of 1,4-Dimethyleneoyolohexane Cuprous Chloride Complex .......................... 44 B. Triplet Sensitization ......................... 46 C. Meroury Sensitization ............................ 47 Results of Syntheses ....... 47 A. Results of CuCl Complex Irradiation ............... 47 B. Results of Aoetone Sensitization Experiments ...... 50 C. Results of Meroury Sensitization Experiments ...... 50 Discussion ..................................... 62 Conclusion ............................................ 64 Experimental ....................................... 65 Apparatus ........ 65 A. Irradiation of 24 66 B. Aoetone Sensitization ............................ 68 C. Meroury Sensitized Photolysis of 4 68 D. Preparation of 1,4-Dibromoblcyclooctane, 22 70 1.4-Dicarbethoxy-2.5 Diketobicyolo[2.2.2]octane, 2J ............................................... 70 Bis-(trimethylene)meroaptol of Dioarbethoxy- 2.5 Dike to Bioyolo[2.2.2]ootane, 28 72 Diethyl Bicyolo[2.2.2]octane-1,4-Dioarboxylate, 29 72 Bicyclo[2.2.2]octane-l,4-Dicarboxylic Acid, _30 ....... 73 1.4-Dibromobioyolo[2.2.2] ootane, 22 73 IV. SYNTHESIS AND REACTION OF 2,2,3,3-TETRADEUTERO [2.2.2] PROPELLANE ........................................ 75 Experimental Design ................... 75 Descriptions of Experiments ............................. 77 Synthesis of £2 by Wittig Reaction .................... 77 Reverse Deuteration of 4, ............................. 77 An Alternative Synthesis of 32 79 Irradiation of 32 79 vi TABLE OF CONTENTS (Continued) Page Results ............................................. 79 Synthesis of 22 79 Irradiation of 32 31 Experimental .................................... 84 di| 1,4-Diemthylene Cyclohexane, £2 84 A. Triphenylmethylphosphonium Iodide ......... 84 B. 1,4-Dimethylene Cyclohexane 32 in DMSO/NaH .... 84 C. £2 in KtBuO/KtBuOH ............................ 85 Alternative Synthesis for 32 86 1.4-Dimethanol Cyolohexane (dij), 38 86 1.4-Cyelohexane Dimethanol Tosyl Ester (djj), 40 87 1.4-Cyolohexane Dimethyl Iodide (di|), 4J[ ......... 87 1.4-Dimethylene Cyolohexane (dij), £2 88 Irradiation of £2, Meroury Sensitized ................. 88 CHAPTER V. THEORETICAL TREATMENT OF ISOSTRUCTURAL ISOMERS ............. 90 Introduction ............... 90 Theoretioal Approach ...................... 92 Results ....................... 94 Discussion ........................... 124 The rj | Bond Distance ................................. 124 C+2 Dictation .............................. 126 DABCO and Isomers ........................... 129 BO isomers ..................................... 132 44 Eleotron System ....................... 135 VI. CONCLUSIONS ..............................................