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DISSERTATION Presented in Partial Eulfillment of the Requirements For ÎHTRATED AMD BENZYLATED .ALIXDÎHC ACIDS AMD IKEIR USE IN SYNTHESES DISSERTATION Presented in Partial Eulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State Universi ty B y ADEX ROSENTHAL, D.Sc., B.Ed. , M.Sc, The Ohio State University 19 52 Approved hy: Adviser 1 TABLE OF CONTENTS PART I Page I. OBJECTIVE..................................... 1 II. HISTORICAL.................................... 2 A . General.................................. 2 B. AldonicAcids and Their Lactones........ 3 C. Preparation of D-Gluconic and D- Galactonic Acids........................ 7 1, Commercial Preparation of D-Glu­ conic Acid by Fermentation Methods............. 7 2, Preparation of D-Galactonic Acid... 10 3, Chemical and Electrolytic Methods of Preparing Aldonic Acids........ 11 D . Preparation of Aldonamides.............. 14- E. Preparation of Sugar Nitrates 15 1. General............... 15 2. Nitration of Carbohydrates with Nitrogen Pentoxide.............. 18 (a) Nitrogen Pentoxide......,,..,, IS (b) Use of Nitrogen Pentoxide as a Nitrating Agent.......... 19 F . Fully 0—Esterifled Aldonic Acids....... 21 G. Reaction of Diazomethane with Sugar Acids....... 24. 1. Diazomethane..................... 24- 2. Action of Diazomethane on Aldonic Acids....................... 27 S81010 11 TABLE OF CONTENTS (cont.) Page H, Stabilizers of Nitrated Carbohydrates.. 27 I, Stability Tests of Nitrated Carbohydrates............................ 30 J. Double-Base Powders and Films........ 32 III. EXPERIMENTAL................................. 34 A. Synthesis of Methyl D-Galactonate Pentanitrate ....... 34 1. Preparation of D-Galactonamide 34 2. Attempted Nitration of D-Galac- tonamide with Nitric-Sulfuric Acids...... 35 3. Attempted Nitration of D-Galac— tonamide with Nitric-Acetic Acids,. 35 4. Preparation of Nitrogen Pentoxide,. 36 5. Synthesis of D—Galactonamide 0-Pentanitrate...... 3B 6. Synthesis of D-Galactonic Acid.,.., Pentanitrate... ................ 40 7. Preparation of Diazomethane........ 42 8. Synthesis of Methyl D-Galacton- ate Pentanitrate ..... 43 B. Synthesis of Methyl D-Gluconate Pentanitrate ...................... 45 1. Preparation of D-Gluconamide ...... 45 2. Synthesis of D—Gluconamide 0-Pentanitrate................... 46 3. Synthesis of D-Gluconic Acid Pentanitrate. ........ 47 4. Synthesis of Methyl D-Gluconate Pentanitrate ............ 48 Ill TABLE OF CONTENTS (cont.) Page 0. Stability and Sensitivity of Nitrates,, 49 1, Determination of Stability of Nitrates ........... 49 2, Determination of Sensitivity of Nitrates............................. 49 D . Compatibility of Nitrated Aldonic Acid Derivatives and Cellulose Nitrate 51 1, Preparation of Films of Cellulose Nitrate and Derivatives of Aldonic Acid Nitrates. ........ 51 2, Preparation of Films of Cellulose Nitrate, Aldonic Acid Nitrate Derivatives and Diphenylamine...... 52 3, Determination of Stability of Double-Base Films,......... 52 IV. DISCUSSION OF RESULTS....................... 55 A. General........ 55 B. Preparation of Starting Materials...... 55 1. Preparation of D-Galactonamide 55 2. Preparation of D-Gluconamide....... 56 3. Preparation of Nitrogen Pentoxide.. 56 C, Preparation of Aldonamide 0—Pentanitrates 1. Attempted Nitration of Aldonamides with Nitric Sulfuric Acids........ 57 2. Attempted Nitration of D—Galac— tonamide with Nitric-Acetic Acids., 57 3. Preparation of Aldonamide 0-Penta- nitrates Using Nitrogen Pentoxide,, 58 D, Preparation of Aldonic Acid Pentanitrates............................ 62 iv TABLE OF CONTENTS (cont,) Page E, Preparation of Methyl Aldonate Pentanitrates............... .......... 64 1. Diazomethane....................... 64 2, Preparation of Methyl D-Galactonate Pentanitrate and Methyl D-Gluconate Pentanitrate............ .... ...... 65 F, Stability and Sensitivity of Nitrated Aldonic Acids and Their Derivatives... 66 G, Compatibility and Stability of Films of Aldonic Acid Nitrate Derivatives and Cellulose Nitrate............... 69 H, Action of Diphenylamine on Double- Base Films................. .... ...... 70 V. ACKNOWLEDGMENTS............................. 71 VI. SUMMARY....................................... 72 V TABLE OF CONTENTS (cont.) TABLES Page Table I» Stability and Sensitivity of Nitrates,,,.......................... 50 Table II. Films of Aldonic Acid Penta­ nitrate Derivatives and Cellulose Nitrate, 53 Table III, Films of Aldonic Acid Penta­ nitrate Derivatives and Cellulose Nitrate with Di— phenylamine ..................... 54 vi TABLE OF CONTEKTS PART II Page I. OBJECTIVE.................................... 74 II. HISTORICAL ................................. 76 A, Polyesters.............................. 76 III. EXPERIMENTAL................................. 79 A. Preparation of D-Galactony1 Chloride Pentanitrate............ 79 1, Using Phosphorus Pentachloride,.., 79 2, Using Thionyl Chloride............ SO B. Attempted Preparation of Ethylene Glycol Di-D-Galactonate Penta­ nitrate ............................... SO 1. Using Pyridine as Catalyst........ SO 2. Using Excess Pyridine and Ether as a Diluent. SI 3. Using Excess Pyridine............. S2 4. Using n-Tributylamine as Catalyst.............. ........ S2 5. Using Kalcite HCR (Resin) as Catalyst. ........ S2 6. Using No Catalyst and Dioxane as Solvent,........................ S3 7. Using No Basic Catalyst and Glacial Acetic Acidas Solvent,.., S3 8. Using Silver Carbonate.......... 83 C. Attempted Direct Estérification of D-Galactonic Acid Pentanitrate with Methanol. ........... 84 vil TABLE OF CONTENTS (cont.) Page 1. Using Dowex 50 as Catalyst......... B4- 2, Using Sulfonic Acid as Catalyst......... ............... 85 IV. DISCUSSION................................... 86 A, Preparation of D-Galactony1 Chloride Pentanitrate........................... 86 B, Attempted Preparation of Ethylene Glycol Di-D-Galactonate Penta­ nitrate ........................ 86 C, Attempted Direct Estérification of D-Galactonic Acid Pentanitrate with Methanol................ ... 88 1. Using Dowex 50 (Resin) as Catalyst 88 2. Using 2,-Toluene Sulfonic Acid as Catalyst........................ 88 V. SUMMARY...................................... 89 viii TABLE OF CONTEHTS PART III Page I. OBJECTIVE............................ 90 II. HISTORICAL.................................. 94 A. Benzyl Ethers of Carbohydrates 94 B. Sugar Mercaptals............ 97 III, EXPERIMENTAL........... 100 A. Attempted Complete Benzylation of D—GluconannSe. 100 1. First Benzylation of 0-Potassium Alkoxide of D-Gluconamide with Benzyl Chloride in the Presence of Liquid Ammonia .......... 100 2. First Rebenzylation of Partially Benzylated D-Gluconamide with Benzyl Chloride in the Presence of Liquid Ammonia. ........ 101 3. Second Rebenzylation of Partially Benzylated D-Gluconamide with Benzyl Chloride 101 B. Attempted Benzylation of D-Gluconamide with Sodium Naphthalene Reagent and Benzyl B r o m i d e . 103 1. Preparation of Sodium Naphtha­ lene Reagent. 103 2. Attempted Benzylation of D- Gluconamide with Sodium Naphtha­ lene Reagent...... .......... 104 C. Preparation of D—Gluconic Acid Pentaacetate . ..... 103 D . Attempted Preparation of Penta-0- benzyl-D-Gluconic Acid. ...... 105 ix TABLE OF CONTENTS (cont.) Page 1, Using Benzyl Bromide as Be-nzylating Agent,...,,,,,,,,,..,, 105 2, Chromatography of Benzylated D-Gluconic Acid,,.................... 107 3, Using Benzyl Chloride as Benzy- lating Agent.,.,....... 109 E. Preparation of Pentabenzyl-D—Glucose Diethyl Mercaptal....... 110 1. Preparation of D-Glucose Diethyl Mercaptal. .............. 110 2. Attempted Benzylation of Alkoxide of D—Glucose Diethyl Mercaptal,.., 110 3. Synthesis of Pentabenzyl-D-Glucose Diethyl Mercaptal................ Ill (a) First Benzylation of D- Glucose Diethyl Mercaptal,.., Ill (b) Second Benzylation...... 113 (c) Third Benzylation............ 114 (d) Chromatography of 0—Penta— benzyl-D-Glucose Diethyl Mercaptal................... , 115 F . Preparation of Pentabenzyl-aldehvdo-D- Glucose ..... 116 G. Synthesis of Pentabenzyl-D-Gluconic Acid........................... 117 17. DISCUSSION...,.............................. 120 A, General. ....... 120 B, Attempted Complete Benzylation of D- Gluconamide ........ 121 1, Attempted Benzylation of (O- Potassium Alkoxide)of D-Glucon­ amide with Benzyl Chloride........ 121 X TABLE OF CONTENTS (cont.) Page 2, Attempted Benzylation of D-Glncon- amide with Sodium Naphthalene Reagent and Benzyl Bromide........ 122 C. Attempted Preparation of Pentabenzyl-D- Gluconic Acid.... ....... 123 1, Using Benzyl Bromide........... 123 2, Using Benzyl Chloride............. 125 D. Synthesis of Pentabenzyl-D-Glucose Diethyl Mercaptal................ 125 1. Preparation of D-Glucose Diethyl Mercaptal .»... 125 2. Attempted Benzylation of (O- Potassium Alkoxide)of D-Glucose Diethyl Mercaptal.............. 126 3. Synthesis of Pentabenzyl-D- Glucose Diethyl Mercaptal,, 126 E. Preparation of Pentabenzyl-aldehydo-D- Glucose............ 129 F . Synthesis of Pentabenzyl-^-Glucorfic Acid................................. 129 V. SUMMARY..................... .. 131 VI. CHRONOLOGICAL BIBLIOGRAPHY............ 133 VII. ACKNOWLEDGMENTS.......................... lAl VIII. AUTOBIOGRAPHY,.............. 14-2 - 1- NITRATED AND BENZYLATED ALDONIC ACIDS AND THEIR USE IN SYNTHESES PART I NITRATED ALDONIC ACIDS I. OBJECTIVE The only monosaccharide sugar nitrates formerly quite extensively investigated for their explosive properties have been those derived by nitrating aldoses or methyl aldosides
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