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University Microfilms, Inc., Ann Arbor, Michigan ADDITION of ELECTRON-DEFICIENT CARBON-CARBON This dissertation has been mlcrolUmed exactly as received 6 9-15,953 RICHMOND, Gary Donald, 1942- ADDITION OF ELECTRON-DEFICIENT CARBON- CARBON MULTIPLE BONDS TO STRAINED POLYCYCLIC HYDROCARBONS; THE CHEMICAL AND PHYSICAL PROPERTIES OF fi -KETO SULFOXIDES. The Ohio State University, Ph.D., 1969 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan ADDITION OF ELECTRON-DEFICIENT CARBON-CARBON MULTIPLE BONDS TO STRAINED POLYCYCLIC HYDROCARBONS; THE CHEMICAL AND PHYSICAL PROPERTIES OF P-KETO SULFOXIDES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Gary Donald Richmond, B.A. ■JHHBHHJ- The Olio State University 1968 Approved by Adviser Department of Chemistry ACKNOWLEDGMENTS The author wishes to express his appreciation to Professor Paul G. Gassman for his guidance, assisteince, and personal influence throughout the course of this work. 11 VITA April 6, 19^2 Washington, Pennsylvania 1964 B.A. Washington and Jefferson College, Washington, Pennsylvania September, 1964 Entered the Graduate School of The Ohio State University 1965-1968 National Institutes of Health Predoctoral Fellow PUBLICATIONS The Alkylation of P-Keto Sulfoxides. A General Route to Ketones, J. Org. Chem., 2555 (1966). Backside Attack on Bent Sigma Bonds, J. Am. Chem. Soc., go, 5657 (1968). FIELD OF STUDY Major Field: Organic Chemistry iii COiraEKTS Page ACKNOWIEDGÏŒNTS..................................... il VITA ................................................ iii TABLES............................... ix PART OME. ADDITION OF ELECTRON-DEFICIENT CARBON- CARBON MULTIPLE BONDS TO STRAINED POLY­ CYCLIC HYDROCARBONS ....................... 1 I. Introduction and Historical Review ........... 1 II. Results.................................... 13 A. Tricyclo[U.1.0.0^’^heptane .............. 13 1. Preparation......................... 13 2. Reactions ...... ................ 13 a. Dimethyl Acetylenedicarboxylate . I3 b. Dicyanoacetylene ................ lU c. Benzyne .............. ...... I6 B. Tricyclo[4.1.0.0^'^]heptane .............. 20 1. Preparation............ 20 2. Reactions................... 21 a. Benzyne......................... 21 b. Dicyanoacetylene ................ 22 III. Mechanism and Stereochemistry............ 25 iv CONTENTS (continued) Page PART TWO. CHEMICAL AND PHYSICAL PROPERTIES OP p- KETO SULFOXIDES.......................... 57 I. Introduction and Historical Review .......... 57 II. Experimental Results ....................... 45 A. Ketone Synthesis - Alkylation and Cleavage of P-Keto Sulfoxides............ 4-5 B. Acidity of p-Keto Sulfoxides............ 48 C. Radical Anion Formation .................. 52 EXPERIMENTAL - PART ONE.............................. 62 Instrumental Techniques ......................... 62 Solvents....................................... 65 R e a g e n t s ..................... 65 7.7-Dibromonorcarane ( ^ ) ....................... 65 Tricyclo[4.1.0.0^ heptane jl ^ ) ................ 65 Reaction of Dimethyl Acetylenedicarboxylate (5.) with 1^ ....................................... 64 Acetylenedicarboxamide ......................... 65 Dicyanoacetylene (6 ) 66 Reaction of Dicyanoacetylene with ^ ............ 66 Addition of Benzyne (^) to ^ .................. 68 Hydrogenation of endo-2-phenyl-tricyclo[4.1.0.0^'^]- heptane (50) 69 1.7-DideuteriotricycloC4.1.0.0^ heptane (4^) . 70 Reaction of 1,7-Dide uteri otri cyclo[4.1.0.0^'^]- heptane with Benzene ................... 71 CONTENTS (continued) Page 7-t-Butoxynorbornadiene ( ^ ) ..................... 71 7-Acetoxynorbornadiene (5^) and anti-7- Norbornenol (^6)................................ 71 Tricyclo[U.1.0.0 ’ ]heptane {2Q) ................ 72 Attempted Reaction of ^ with Benzyne............ 75 Addition of Dicyanoacetylene (^) to 1 0 .......... 75 Conversion of endo-tricyclo[4.1.0.0^ ^]heptyl- 5-maleonitrile to endo-5-carbomethoxy- tricyclo[1^.1.0. O^T^Jheptane (h p ) ................. 75 Hydrogenation of endo-$-carbomethoxytricyclo- [U. 1.0.0® heptane (4^) to endo-2-carbomethoxy- norbornane (jjjjO................................. j6 Authentic endo-2-carbomethoxynorbornane ............ 77 . Attempted Reaction of Bicyclo[2.1.0]pentane (2) with Benzyne....................... 77 EXPERIMENTAL - PART T W O .............................. 79 A. AlRylation and Reduction of p-Keto Sulfoxides................................. 79 S o l v e n t s ................................... 79 o)-(Methylsulfinyl)acetcphenone and Methyl- sulfinylmethyl-n-Pentyl Ketone ................ 79 Méthylation of m-(Methylsulfinyl)acetophenone in D M E ..................................... 79 Méthylation of w-(Methylsulfinyl)acetophenone in D M S O ..................................... 80 Priophenone.......................... • . 8l General Procedure for Combined Alkylation and Cleavage Steps ................. 8l vi COKTENTS (continued) Page Dialkylation - The Preparation of Iso- butyrophenone - A. Two-Step Process .......... 82 Dialkylation - The Preparation of Iso- butyrophenone - B. One-Step Process .......... 82 Propiophenone .............................. 8j Butyrophenone .............................. 83 Valerophenone .............................. 83 Oct an one................................... 84 2-Methyl-3-0ctancne 84 4-Nonanone........ 84 4-Nonanone................................. 84 B. Acidity of p-Keto Sulfoxides................ 85 C. Radical Dianion Formation................... 89 u)-(Methylsulfinyl) acetophenone (79) .......... 89 u)-(Phenylsulfinyl)acetophenone (84) .......... 89 U)-(Phenylsulfinyl)benzylphenyl Ketone (83). 90 u)-(Methylsulfonyl) acetophenone { 0 0 .......... 90 u)-(Phenylsulfonyl)acetophenone (87) .......... 91 Deuteration of ui-(Phenylsulfonyl)acetophenone (81)....................................... 91 Solvents.................................. 92 Radical Dianion Generation .................. 92 Reductions in THF, DME, and Diglyme ....... 92 vii COMTENTS (continued) Page Reductions in HMPA.......................... 95 Recovery Attempts.......................... 9^ Calculation of g~Values .... .............. 95 viii t a b l e s Table Page 1. Alkylation of OgHsCOCHsSOCH^ and Cleavage of CeHsCOGRR'SOCIfe.................. k6 2. Alkylation of C % (CHg)^COCHaSOCH^ and Cleavage of CHg ( CHg) 4COCBE ' 8OCH3.............. 4? 5. pKa Values for Various S-Disubstituted Carbonyl, Sulfinyl, and Sulfonyl Compounds.................................. 50 4. pKa Measurements of p-Keto Sulfoxides........... 87 5. pKa Measurements of p-Keto Sulfoxides ......... 88 ix FART OME ADDITION OF ELECTRON-DEFICIENT CARBON-CARBON MULTIPLE BONDS TO STRAINED POLYCYCLIC HYDROCARBONS I. Introduction and Historical Review The unique chemical and physical properties of cyclopropane, the 1 simplest cyclic hydrocarbon, are well documented. As discussed in most elementary organic textbooks, ring cleavage resulting from the addition of hydrogen or electrophilic reagents is typical of cyclo­ propane s. This chemj.cal reactivity has been attributed to an in- 2,3 herent strain of 27*15 kcal/mole in cyclopropane, and to the struc­ tural requirements of bond deviations from normal spf orbital hy­ bridization. This initial interest in cyclopropane has led to a study of strain energy and bonding characteristics as a basis for chemical reactivity in a variety of small polycyclic hydrocarbons. Two such ring systems are bicyclo[l. 1.0]butane (].) and bicyclo[2.1.0]pentane (2). ' 1. For a review of cyclopropane chemistry see: M. Y. Kukina, Russ. Chem. Rev., U19 (1962). 2. R. B. Turner and P. Goebel, Tetrahedron Letters, 997 (19^5)' 3 . J. W. Khowlton and F. D. Rossini, J. Research Natl. Bur. Standards, II3 (19^9). 2 0 â The most recent determination of strain energy from heats of 4 hydrogenation assigned a total strain of 68.2 kcal/mole (17 kcal per carbon) to l,3-dimethylbicyclo[l.1.0]butane. This high degree of strain energy is probably not localized in the ring fusion bond, but is distributed over several bonds. The hydrogenation of the 1,3- bond produces a cyclobutane derivative and releases U3.6 kcal/mole. The cleavage of a 1,2-bond relieves k2.2 kcal/mole of the total strain energy. The measured strain energy of ]. itself is 63.9 kcal/ 4 mole. A previous value of 6?.^ kcal/mole was calculated from heats 5 of formation obtained from an SCF MO theoretical treatment. From a consideration of heats of hydrogenation and heats of formation, the total strain energy of 2 was found to be $4.1 kcal/ mole. Since hydrogenation of the 1,4-bond forms cyclopentane with a strain energy of 6.0 kcal/mole, the strain energy of this ring fusion bond must be 48.1 kcal/mole. This value is greater than that for .1 ,3 -bond cleavage of by approximately 10 kcal/mole, con- 4. R. B. Turner, P. Goebel, B. J. Mallon, W. von E. Doering, J. p. Coburn, Jr., and M. Pomerantz, J. Am. Chem. Soc., 90, 4315 (1968). See also W. von E. Doering and J. F. Coburn, Jr., Tetra- \ hedron Letters, 991 (1965). 5. N. Baird and M. J. S. Dewar, ibid., 8 9 , 5966 (1967). 6 sidering the strain energy of cyclobutane to be 25-8 kcal/mole. The 1,4-bond dissociation energy is ^O.J kcal/mole compared with 54.4 7 kcal/mole for cyclopropane. The strain energy of a related struc­ ture, quadricyclane, was found to be 95-1 kcal/mole (l$.6 kcal per carbofi). It will become apparent that much of the chemistry of these small ring hydrocarbons is explicable on the basis of bonding char­ acteristics in addition to strain energy. For example, the chemical reactivity
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