THE CONTROLLED THERMAL DECOMPOSITION OF CELLULOSE NITRATE: CARBONYL 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 GUY PIERRE ARSENAULT, B.A.Sc. The Ohio State University 1958 Approved by: Adviser Department of Chemistry ACKNOWLEDGMENT The author wishea to extend his sincere apprecia­ tion and thanks to professor M. L. Wolfrom for his Interest In this work and for his guidance in technical matters. The spirit of sacrifice and unfailing assistance of the writer’s wife, Anne, who made valiant efforts to understand the field of chemistry, made this work possible. The writer wishes to thank Messrs. H. R. Menapace and V. G-. Wiley for the loan of their gas chromatographic equipment and calibration charts, and for their spirit of cooperation. Mr. A. Chaney and Dr. F. Shafiaadeh of The Ohio State University Research Foundation have given freely of their time at the writer’s request for aid. For this he is very thankful. Appreciation is expressed to the Monsanto Chemical Co. (1956-1957) and the Standard Oil Foundation inc. (Indiana) (1957-1958) for fellowships provided by them. This work was supported in part by the united States Army Ordnance Department under contracts (unclassified; DA3>0l9-ord-727, DA33-019-ord-14-76 and DA33-019-ord-2o42; supervising agency, The Ballistic Research Laboratories, Aberdeen Proving Ground, Maryland) with The Ohio State ii ill University Research Foundation (Projects 496, 591 and 679). TABLE OF CONTENTS Page INTRODUCTION .......... ...................... 1 STATEMENT OF THE PROBLEM.................... 3 HISTORICAL ................................... 5 Decomposition of Cellulose Nitrate ..... 5 Preparation of 2 ,4-Dinitrophenyl- hydrazine Derivatives .................. 26 Chromatography of 2,4-Dinitrophenyl- hydrazine Derivatives .................. 37 Characterization and identification of 2,4-Dinltrophenylhydrazine Derivatives .................... ........ 45 A. ultraviolet and visible spectrum 45 B. Infrared spectrum ....... '..... 50 C. Melting point ................. 52 D. Miscellaneous methods ......... 55 DISCUSSION OF RESULTS ....................... 57 Thermal Decomposition of Cellulose Nitrate ................................. 57 Fractionation, by Repeated Sublimation, of Some of the Major Organic Components of the Aqueous Solution of the Liquid Mixture of Cellulose Nitrate ignition Products .............. 61 preparation of 2,4-Dinitrophenyl- hydrazine Derivatives of Known Carbonyl Compounds ............ 69 A. Preparation of triose 2,4- dinitrophenylosazone .............. 7^ iv TABLE OF CONTENTS. Cont. Page B. Preparation of the 2,4- dinitrophenylhydrazflmes of short carbon chain sugars ........ 77 0. Preparation of mesoxaldehyde tris(2,4-dinitrophenylhydrazone)... 79 D. Reaction of £>-glucose with 2 ,4-dinitrophenyThydrazlne ....... 81 E. Preparation of mesoxaldehyde l,2-bis{2 1 ^ ’-dinitrophenyl- hydrazone) ........................ 83 F. Attempted preparation of mesoxaldehyde l,3-bis(2 ' ,4 '- dinitrophenylhydrazone) .......... 87 G-. Reaction of 2,4-dinitro- phenylhydrazine with triose- reductone ......................... 91 H. Miscellaneous data concerning 2 ,4-dinitrophenylhydrazine derivatives ....................... 93 Chromatography of 2,4-Dinitrophenyl­ hydraz ine Derivatives of Known Carbonyl Compounds ..................... 105 Fractionation, by Extraction with Alcohol (95?0, of the 2,4-Dinitro- phenylhydrazine Derivative of the Residue of the Repeatedly sublimed Condensate Aqueous Solution ........... 110 Investigation of the Alcohol-Soluble Fracti on ............................... 114 investigation of the Alcohol- Insoluble Residue....................... 12o Attempted Isolation of Triose 2,4- Dinitrophenylhydrazone from the Condensate Aqueous Solution ........... 121 v TABLE OF CONTENTS. Pont. .rase Gas Absorption Chromatography of the Liquid. Mixture of Cellulose Nitrate ignition products ............. 124 Origin of Compounds Isolated from the Liquid Mixture of Cellulose Nitrate Ignition Products .... 135 EXPERIMENTAL........................... 141 General Statements ..................... 141 Chromatography of Derivatives of 2,4-Dinltrophenylhydrazine ............ 144 Reaction of Some Carbonyl Compounds with 2,4-Dinltrophenylhydrazine ....... 148 A. Preparation of the 2,4- dinitrophenylhydrazones of some oi -hydroxy carbonyl compounds .... 148 B. Preparation of D,L-glyceral- dehyde 2,4-dlnItropTaefiylhydra- zone in the presence of a large excess of reagent .......... 151 C. Preparation of D,L-glyceral- dehyde 2 ,4-dinitropMenylhydra- zone in the presence of an acid catalyst .......................... 152 D. Preparation of triose 2,4- dlnitrophenylosazone ............. 152 E. Preparation of mesoxaldehyde tris(2,4-dinitrophenylhydrazone) .. 155 F. Reaction of D-glucose with 2 ,4-dinitrophenyTnydrazine 159 G. Preparation of mesoxaldehyde l,2-bist21,4'-dinitrophenyl­ hydrazone) ......... .............. 16 0 vi TABLE OF CONTENTS, Pont. Page H. Conversion of mesoxaldehyde I ,2 -bis(2 ’,41-dlnitrophenyl- hydrazone) into mesoxaldehyde tris(2 ,4-dinitrophenylhydrazone).... 163 I. Attempted preparation of mesoxaldehyde l,3-bis(2 1,41 - dinitrophenylhydrazone) ........... 164 J. Reaction of 2,4-dinitro- phenylhydrazine with triose- reductone .......................... 165 Miscellaneous Data Concerning 2,4- Dinitrophenylhydrazine Derivatives ...... 170 A. Infrared spectra of 2,4- dinitrophenylhydrazine derivatives., I70 B. Sublimation of 2,4-dlnitro- phenylhydrazine, 2,4-dinitro- aniline and 2 ,4-dinitrophenyl- hydrazine derivatives ............. 170 C. Solubility of 2,4-dinitro- phenylhydrazine derivatives in hot water ....................... 172 D. Light absorption spectrum of mesoxaldehyde l,2 -bis(2 1,41 - dinitrophenylhydrazone) - Solvent effect ..................... 172 Fractionation, by Repeated Sublimation, of Some of the Major Organic Components of the Aqueous Solution of the Liquid Mixture of Cellulose Nitrate Ignition products ....................... 174- Fractionation, by Extraction with Alcohol (95$)* of the 2,4-Dinitro- phenylhydrazine Derivative of the Residue of the Repeatedly Sublimed Condensate Aqueous Solution........... 178 vil TABLE OF' CONTENTS, Cont. Pap;e Investigation of the Alcohol- Soluble Fraction ....................... 179 A. Chromatographic separation ... 179 B. Zone 1 ......................... 179 C. Zone 2 ........................ 182 D. Zone 3 ........................ 184 E. Zone 4 ........................ 185 F. Zone 5 ........................ 186 G-, Zone 6 ........................ 187 Investigation of the Alcohol- Insoluhle Residue ...................... 189 Attempted Isolation of Trlose 2,4- Dinltrophenylhydrazone from the Condensate Aqueous Solution ............ 190 A, Reaction of the condensate aqueous solution with 2,4-dinitro- phenylhydrazine in boiling ethanol.. 190 B. Reaction of the condensate aqueous solution with a super­ saturated solution of 2,4-di- nitrophenylhydrazine in 2 ^ hydrochloric acid ................. 190 G-as Absorption Chromatography of the Liquid Mixture of Cellulose Nitrate Ignition Products ...................... 193 SUMMARY ..................................... 199 BIBLIOGRAPHY ................................ 203 AUTOBIOGRAPHY .... I.......................... 216 viii LIST OF TABLES Table Page I* Fractionation, by Repeated Sublimation, of Some of the Major Organic Components of the Aqueous Solution of the Liquid Mixture of Cellulose Nitrate Ignition products ................... 64 II. Melting Points of Some 2,4-Dinitro- phenylhydrazlne Derivatives .......... 70 III. Light Absorption Characteristics of Some Derivatives of 2,4- Dlnitrophenylhydrazine .............. 112 IV. Compounds Isolated, in Our Work, from the Liquid Mixture of Cellulose Nitrate ignition Products ............... 136 ix LIST OF FIG-URES Figure Page 1. Product Relationships ................ 62 2. Light Absorption Spectrum of Mesoxaldehyde 1,2-Bis(2',4'-dinitro­ phenylhydrazone J j in Ethyl Acetate; - - - -, in Ethanol (95%) •••* 86 3- Infrared Absorption Spectrum of G-lycolaldehyde 2,4-Dinitrophenyl- hydrazone ............................. 96 4. Infrared Absorption Spectrum of G-lyox- ylic Acid 2,4-Dinltrophenylhydrazone .. 97 5. Infrared Absorption Spectrum of Acetol 2,4-Dinitrophenylhydrazone ........... 98 6. Infrared Absorption Spectrum of Mesox- alic Acid 2 ,4-Dinitrophenylhydrazone .. 99 7. Infrared Absorption Spectrum of D,L- G-lyceraldehyde 2 ,4-Dinitrophenyl- “ hydrazone ............................. 100 8. Infrared Absorption Spectrum of Di- hydroxyacetone 2,4-Dinitrophenyl- hydrazone ............................. 101 9. Infrared Absorption Spectrum of Triose 2 ,4-Dinitrophenylosazone ...... 102 10. Infrared Absorption Spectrum of Mesox­ aldehyde Tris(2,4-dinitrophenylhydra- zone) ............................... 103 11. Infrared Absorption Spectrum of Mesoxaldehyde 1,2-Bis(2 1,4'-di­ nitrophenylhydrazone) .................. 104 12. Diagrammatic Representation of the Chromatogram of Extract I on Silicic Acid-Celite (5:1} 8% water) .......... 115 x LIST OF FIGURES. Qont. Figure Page 13. Diagrammatic Representation of the Chromatographic Separation on Silicic Acid-Celite (2:1; 0% water) of the Residue of Evaporation of the Mother Liquors from the Recrystallizations of the Sublimate of the Material in Zone 1 117 14. Schematic Diagram of the Gas Absorp­ tion Chromatography Apparatus ........ 125 15. Recorded Gas Chromatogram of the