New Reactions of Nitro Compounds
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This dissertation has been 62-2176 microfilmed exactly as received KAPLAN, Ralph Benjamin, 1920- NEW REACTIONS OF NITRO COMPOUNDS. The Ohio State University, Ph.D., 1950 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan NEW REACTIONS OF NITRO COMPOUNDS DISSERTATION Presented In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of the Ohio State University By RALPH B. KAPLAN, B.A., The Ohio State University 1950 Approved by: Adviser TABLE OF CONTENTS Page INTRODUCTION Acknowledgments Statement of the Problem SECTION I REACTION OF SODIUM NITROALKANES WITH VARIOUS NITRATING AGENTS 1 I. Discussion 1 A. Introduction 1 B. Agents Investigated 2 1. Nltryl Chloride 2 a. Preparation 2 b. Review of thé Reactions of Nltryl Chloride With Organic Reagents U c. Reaction of Sodium 2-Nltropropane With Nltryl Chloride 6 d. Reaction of Sodium 2-Nltropropane with Nltryl Chloride and Aluminum Chloride 11 2. Mixed Nitric and Sulfuric Acid 12 a. Reaction of Sodium 2-Nltropropane With Mixed Nitric and Sulfuric Acid 12 3. Methyl Nitrate Ih a. Reaction of Sodium 2-Nltropropane and of Potassium Nltroethane l4 I. Alkyl Nitrates as Nitrating Agents 14 II. Discussion of Results 15 Page II. Experimental 21 A. Agents Investigated 21 1. Nltryl Chloride 21 a. Preparation 21 1. Intermediates; Chlorosulfonlc Acid and Nitric Acid, Anhydrous 11. Procedure for Making Nltryl-Chloride h. Reaction of Nltryl Chloride with a Secondary Nltroalkane 2k 1. 2-Nltropropane 11. Sodium 2-Nltropropane c. Reaction of Sodium 2-Nltropropane, Nltryl Chloride and Aluminum Chloride. 27 2. Reaction of Sodium 2-Nltropropane With Mixed Nitric and Sulfuric Acids 28 3. Methyl Nitrate 29 a. Reaction of Sodium 2-Nltropropane 29 h. Reaction of Nltroethane (Attempted Preparation of 1,1-Dlnltroethane). 52 III. Summary 35 SECTION II REACTION OF NITRIC OXIDE WITH SODIUM NITROALKANES 34 I. Discussion 34 A. Introduction 34 B. Agents Investigated 35 w Page II. Experimental hk A. The Agent th 1. Kitrlc Oxide a. Preparation kh b. Reaction With Sodium 2-Nitropropane (Formation of a Mixed Salt (l:l) of Sodium 2-Fitropropane and Sodium Nitrite). c. Reaction With Sodium 2-Nitrobutane (Formation of a Mixed Salt (l:l) of Sodium 2-Nitrobutane and Sodium Nitrite) d. Reaction With Sodium Nitrocyclohexane .(Formation of a Mixed Salt (l:l) of Sodium Nitrocyclohexane and Sodium Nitrate, Cyclohexanone, Cyclohexanone Oxime, and l,l-Dinitro-l,l-Dicyclohexyl B. Chemical Proof of Constitution of the Salts Derived frcrni Sodium Secondary Nitroalkanes and Nitric Oxide 4? 1. Acidification a. The Double Salt. Conversion to Pseudonitrole 4? b. Disodium l-Nitrosohydroxylamino-l-nitroethane and Disodium 1-Nitrosohydfoxylamino-1- nitropropane (Traube Products). 4° 2. Oxidation With Silver Ion 50 a. The Double Salt. Preparation of Secondary Gem-Dinitro Alkanes 50 1. 2,2-Dinitropropane ii. 2,2-Dinitrobutane iii. 1,1-Dlnitrocyclohexane b. Traube's Products. Degradation to Water Soluble Products. 55 lU Page 5 . Oxidations With Hydrogen Peroxide and With Salts of Persulfuric Acid 5U a. Coupling of Secondary Nltroalkane Anions to Dimeric Vicinal Dinitroalkanes 5^ i. 2,3-Dimethyl-2,5-dinitrobutane ii. 3,4-Dimethyl-3;4-dinitrohexane iii. 1,1'-Dinitrohicyclohexyl iv. l,l'-Dinltrobicyclohexyl 4. Action of Various Oxidizing Agents on the Doublt Salt of Sodium 2-Nitropropane and Sodium Nitrite 56 a. Oxidation with Mercuric Nitrate. Formation of 2,%-D methyl-2,3-dinitrobutane 56 b. Oxidation With Hypobrcmite. Formation of Water Soluble Products 56 c. Oxidation with Permanganate. Fonnation of Acetone 57 d. Oxidation With Ferric Chloride. Formation of Acetone. 57 III. Summary . 58 SECTION III PREPAEATION OF GEM-DINITEOCOMPOUNDS BY OXIDATIVE NITRATION 60 I. Discussion • 60 A . Introduction 60 B. Historical Review of Various Methods for the Preparation of Gem-Dinitro-Cr.mpounds 60 C. Discussion of Results 65 1. Reaction of Salts of Nitro Compounds With Sodium Nitrite and Silver Nitrate. Scope of the Reaction 63 a. General Procedure, Conditions for Reaction, Isolation of Products 65 \M Page b. Identification of Products 68 c. Side Reactions 75 2. The Preparation of Potassium Rinltromethane, Homologs and Related Compounds 7^ 5. The Effect of Various Oxidizing Agents in Oxidative Nitration 30 II. Experimental 02 A, Oxidative Nitration;,the Preparation of Gem-Dinitro Compounds 82 1. Preparation of 1,1-Dinitroethane 82 a. 1,1-Dinitroethane (as such) 82 h. Potassium 1,1-DJnltroethane 85 c. Silver 1,1-Dinitroethane 84 2. Preparation of 1,1-Dinitropropane 84 5 . Preparation o_ 2,2-Dinitropropane 85 4. Preparation of 2,2-Dinitrobutane 65 5 . Preparation of l,l-Dinitrodj'clohexane 66 6. Preparation of 9,9-Dinitrofluorene, 9,9'-Dinitro- 9,9'-difluorenyl and Fluorenone 87 7. Preparation of 2,2-Dimethyl-l,l,5-trinitropropane 89 a. Formation of the Intermediate, the Disodium Salt of 2,2-Dimethyl-l,5-dinitropropane 89 b. Nitration of the Intermediate Salt to Yield 2.2-Dimethyl-l,l,5-trinitropropane 89 8. Preparation of 2,2-Dinitro-l-ÿroÿanol 91 a. Sodium Salt of 2-Nitro-1-ÿropanol 9I b. Nitration of the Intermediate Salt to Yield 2.2-Dinltro-l-propanol 91 c. Preparation of Potassium 1,1-Dinitroethane 92 V v f Page 9. Preparationof 5,3-I>initro-2-butanol 92 a. Salt Product From 2-Nltro-2-butanol 92 b. Conversion of the Intermediate Salt Into 3#5-DJnitro-2-butanol.and 1,1-Dinitroethane 93 10. Preparation of 2,2-Dlnitro-l,3-propanediol 9^ a. Sodium 2-Nitro-l,3-propanediol 9^^ b. Conversion of the Intermediate Salt into 2,2-Dlnitro-l,3-propanediol 94 c. Preparation of Prtassium 2,2-Dlnitroethanol 95 11. Preparation of Potassium Dlnitromethane from l-Nitro-2-propanol 96 a. Sodium Derivative of l-Nitro-2-propanol 96 b. Conversion of the Intermediate Salt Into l,l-Dinitro-2-propanol (crude) 96 c. Cleavage of l,l-Dinitro-2-propanol 98 i. Potassium Dlnitromethane ii . Silver Dlnitromethane d. Cleavage of l,l-Dinitro-2-propanol to Acetaldehyde 100 12. Preparation of Dlnitromethane from Nitromethane 101 B. Attempted Preparation of Potassium Dlnitromethane from Potassium 2,2-Dinitroethanol 102 1. Preparationof Dipotassium 1,1,3,3-Tetranitropropane 102 a. Dipotassium 1,1,3,5-Tetranitropropane (as such) 102 b. Disilver 1,1,3,5-Tetranitropropane 103 C . Preparation of Dipotassium 1,1,3,5-Tetranitropane from Potassium Dlnitromethane and Potassium 2,2-Dinitroethanol I05 VI Page D. The Effect of Various Oxidizing Agents on the 2-Propanenltronate-Nltrlte Ion System 106 1. Oxidation With Mercuric Ion. Preparation of 2.2-Dlnitropropane 106 2. Oxidation With Persulfate Ion. Preparation of 2 .3-Dlmethyl-2,5-dlnltrohutane 107 3. Oxidation With Hydrogen Peroxide. Preparation of 2.3-Dimethyl-2,3-dinitrohutane 107 4. Oxidation With Cuprlc Ammonium Complex Ion. Preparation of 2,3-Dlmethyl-2,3-dinltrohutane 1C8 3. Oxidation With Cuprous Salts. Formation of Witer Soluble Products 1C9 III. Summary 109 SECTION IV OXIDATIVE COUPLING OF SALTS OF NITROALKANES TO YIELD VICINAL DINITRO COMPOUNDS 112 I. Discussion 112 A. Introduction 112 B. Historical Review of Coupling Reactions 115 C. Discussion of Results 115 1. Nitro Compounds and Oxidizing Agents Selected for Investigation 115 a. Oxidation of Salts of Nitroalkanes With Persulfates 115 h. Reaction of Sodium 2-Nitropropane With Hydrogen Peroxide ll8 c. Reaction of Sodium 2-Nitropropane With Potassium Ferricyanide ll8 d. Reaction of Sodium 2-Nitropropane With Other Oxidizing Agents IIQ 2. Correlation of Data 120 Mil Page 11 « Experimental 12k A. Oxidative Coupling (Dimerization) of Secondary Nitroalkanes 12U 1. Preparation of 2,3-Dimethyl-2,3-dinitrobutane Using Various Oxidizing Agents 12k a. Coupling by Persulfate Ion 12k 1. Formation of Acetone by a Side Reaction b. Coupling by Hydrogen Peroxide 126 c. Coupling by Potassium Ferricyanide 127 d. Coupling by Cupric Ammonium Complex Ion 127 2. Preparation of 3,k-Dimethyl-3,k-dinltrohexane 128 3 . Preparation of l,l_-Dinitro-l,l'-dicyclohexyl 128 k. Attempted Preparation of 2,2,3,3-Tetranitrobutane 129 3 . Attempted Preparation of Hexanitroethane 129 III. Summary 129 BIBLIOGRAPHY I3I AUTOBIOGRAPHY ViU ACKN0WLE3XÏMENTS The author wishes to express his appreciation for the encouragement and counsel of Professor Harold Shechter. The author is indebted to Mrs. Elizabeth Klotz and Mrs. Arlene Brooks and many others for their cooperation at various times during this research. To The Ohio State University Eesearch Foundation, the Aerojet Engineering Corporation, Azusa, California, and to the Office of Naval Eesearch the author expresses his sincere gratitude for the financial support that made this work possible. IX Statement of the Problem Advances in the chemistry of polynitronlkanes have been delayed for a long time by lack of adequate methods of synthesis. This is true because the compounds are sensitive and will not survive dras tic nitrations. It would be very desirable to have methods which would permit of adding nitro groups to the molecule under very mild conditions. An investigation of the reactions of salts of nitro compounds with various potential nitrating agents has therefore been initiated for the purpose of developing general methods for converting mono- nitro compounds into polynitro compounds. SECTION I REACTION OF SODIUli NITROALKANES WITH VARIOUS NITRATING AGENTS I « Discussion A, Introduction Primary and secondary nitroalkanes are pseudo acids; neutral- ization of these weak electrolytes (K = 10 ) yields the nitronate anion, R-NOg (l), a resonance hybrid of the following structures: y O - _ y) r C l o RR'-C=N(