The Pennsylvania State College The Graduate School Department of Chemistry I. The Urea and Thiourea Adduction of C^ to C^ Hydrocarbons II, The Reaction of Dodecyllithium with 2,5>-Dicyclopentyli- denecyclopentanone and with 2,5-Dicyclopentylcyclo- pentanone III, The Reaction of Cyc1opentyllithium with Ethyl Acetate and with Methyl Palirdtate A thesis by David F litter Submitted in partial fulfillm ent of the requirements for the degree of Doctor of Philosophy ' January 1952 Approved: Chemistry Head of the/Department ACKNOWLEDGMENT To paraphrase Euclid, there is no royal road to a doctoral thesis* Generally it is the work of more persons than the author himself* It was so in this case, and the author acknowledges his gratitude to the people who helped him along the way* Sincere thanks to the director of the American Petroleum Institute Research Project lt2, Dr, Robert W. Schiessler, who gave so much of his time, experience, and guidance to the investigation. Special mention to the author* s wife, Jean D. F litter, without whose help and patience the work would have been impossible. Thanks also to E. Ann Graham for her excellent per­ formance in preparing the manuscript, and thanks to all the members of Project it2 whose contributions enabled the completion of the thesis* The author is happy to acknowledge the grant of funds from the American Petroleum Institute which supported the study. 366719 TABLE OF CONTENTS Page I, The Urea and Thiourea Adduction of to Cjn Hydrocarbons Introduction and H istorical • • 1 Experimental Reagents • ............................ 5 Procedure ...................................................................... 5 Detection of Crystalline Complex......................... 6 Discussion ................................ 8 Summary............................................ 17 II. The Reaction of Dodecyllithium with 2,5-Dicyclopentyl- idenecyclopentanone and with 2,5>-Dicyclopentylcyclo- pentanone Introduction ....................................................... 18 H istorical ......................... 20 Method of Preparation of PSC Hydrocarbons .......... 22 Table of Physical Properties ........................... 21; Discussion of R eaction .................................................. 27 Effect of Cyclopentyl Group on Physical Properties Viscosity .............................................................................. 29 Table of Comparative Properties ............................. 30 Slope ..................................................................... 31 Density and Refractive Index 32 Aniline and Furfural Points ................................................. 33 Molecular Volume and R efraction......................................... 33 Comparative Properties of PSC 199 Table of Properties ............................................................ Viscosity »............................................................................... Slope .......................................................................................... Density and Refractive Index ........................ Boiling Point at 1 mm. .................................................. Aniline and Furfural Points ........................................... Summary ........................................................................ Experimental 2.5-Dicyclopentylidenecyclopentanon e .................... 2.5-Dicyclopentylcyclopentanone .................................. Dodecyl Chloride ...................................................... Dodecyllithium ....................................................... Addition Reaction of C-^Li and Unsaturated Ketone Addition Reaction ............................................................ Separation of Products ..................................... Hydrogenation of Addition Product ............... Materials Balance ..................................................... Dehydration of Addition Product . . . . . . . . . . . . . . . Analysis with Standardized LiAlH^ . ..................... Addition Reaction of C-^Li and Saturated Ketone Dodecyllithium Preparation ........................ Addition Reaction ................................................... Separation of Products ............................................... Dehydration of Tertiary Alcohol .............................. Purification of Olefin Mixture .................... Characterization of Products............... Materials Balance ................................... Hydrogenation of Olefin M ixture....................................... 70 Purification of l,l-Dicyclopentyl-2-hexadecyl- cyclopentane, PSC 199 .................................................. 71 The Reaction of Cyclopentyllithium with Ethyl Acetate and with Methyl Palmitate Introduction ....................................................... 73 H istorical ............................................................................................ 75 Discussion of the Reaction ........................................................ 77 Method of Preparation of the Hydrocarbons.......................... 83 Effect of Cyclopentyl on Physical Properties A. 1,1-Dicyclopentylethane and Related Hydrocarbons Table of Physical Properties ................................. 85 V iscosity............................................................................. 86 Slope ............................................................................... 86 Density and Refractive Index .......... 87 Boiling P o in t.......................................... 87 Aniline and Furfural P o in ts...................................... 88 Molar Volume and R efraction....................................... 89 Bo 1,1-Dicyclopentylhexadecane and Related Hydrocarbons Table of Physical Properties ................................. 90 Viscosity ........................................................................... 91 S lope.................................................. 92 Density and Refractive Index ................................... 92 Boiling Point ..................... 93 Melting Point ............................................................... 93 Aniline and Furfui*al P o in ts.............. 9h Molar Volume and Refraction ................. 9h Page Summary ................................................................................................ 9$ Experimental A. 1,1-Dicyclopentylethane Intermediates Cyclopentanone...................................... 97 Cyclopentanol ................................................ 97 Cyclopentyl C hloride ..................................... 98 Cyclopentyllithium .......... 99 Addition of Ethyl Acetate to Cyclopentyllithium 101 Separation of High-Boiling Product ................ 103 Separation of Methyldicyclopentylcarbinol ..... 101; Dehydration with Oxalic Acid ...................... 101* Purification of Olefin fix tu re ............................. 10$ Hydrogenation to 1.1-Dicyclopentylethane ...... 10$ Purification of l^l-Dicyclopentylethane ....... 106 Characterization of Products 1. In Recovered Solvent .......... 107 2. In Low-Boiling Product .................................. 109 3. In High-Boiling Product.................................. 110 Saponifiable Product ...*•••.......... Ill Materials Balance ............ 112 B. 1,1-Dicyclopentylhexadecane Intermediates Methyl Palm itate......................... 11$ Cyclopentyllithium ...................................................... 11$ Addition of Methyl Palmitate to Cyclopentyl­ lithium ............................... 116 a Page Preliminary Separation of Products .......... 116 Dehydration of Crude Tertiary Alcohol .................. 117 Purification of Olefin Mixture ............................... 118 Hydrogenation to 1,1-Dicyclopentylhexadecane .• 119 Purification of 1,1-Dicyclopentylhexadecane ... 120 Appendix A, Determination of Physical Properties ..... 122 B. Apparatus.......................................................................... .»• 128 Bibliography................................................................................ 131 SECTION I* THE UREA AND THIOUREA ADDUCTION OF C^ TO C^ HYDROCARBONS * The material reported in this section was presented at the X lllth International Congress of Pure and Applied Chemistry, Sept­ ember 13, 195>1> New York City* INTRODUCTION AND HISTORICAL For some time it has been known that crystalline molecular combinations form between a parent substance and a variety of other molecules. As long ago as 181$ Wohler (l) found that hydroquinone and hydrogen sulfide formed crystals, from aqueous solution, diff­ erent in appearance from the crystals of hydroquinonej however, he did not investigate the matter thoroughly. Later, Mylius (2) found that hydroquinone formed crystals with hydrocyanic acid and with formic acid. This behavior led him to suggest that the hydroquinone molecules were somehow able to lock other molecules, even volatile ones, in position during crystallisation. Gomberg and Cone (3) ob­ served sim ilar behavior between phenols and hydrogen bromide. Other examples of this are the combinations, known as "picrates", between picric acid and certain aromatic hydrocarbons and the com­ binations, known as "choleic acids", between desoxycholic acid and alcohols, fatty acids or hydrocarbons. A recently discovered class of such combinations is one involving urea or thiourea and a wide variety of hydrocarbons, alcohols, ketones, and halogen derivatives. Since the discovery in 191*0 by Bengen (1*) that urea displayed this behavior the phen­ omenon has been the subject of widespread investigation with the purpose of revealing the basis of "adduction", as this phenomenon is now called (£), or else for the purpose of developing it into a separation process akin to extraction. In the case of urea, work of Schlenk (6, 7, 8) indicated that branched hydrocarbons did not associate with area and that a certain minimum length of chain was necessary* No simple whole number ratio existed between the moles of urea and hydrocarbon, but the longer the chain of carbon atoms the more urea was needed. The adduction process is exothermic, and Schlenk estimated the heat effects to be of the order of magnitude of those brought about by interaction of van der Waals forces. Zimmerschied and co-workers (5) confirmed and extended some of Schlenk1s results. As regards the molal ratio of the adduct com­ ponents, Zimmerschied found there was approximately 0*8 mole of urea per carbon atom. The heat effect was approximately 1*!? Kcal.Z-CHg Since x-ray powder patterns pointed out that a distortion of the urea lattice was required to allow entry of an n-alkyl chain, Zimmer­ schied1 s group suggested that the net heat effect was the resultant of the exothermic process of adduction and the endothermic one of distortion of the urea lattice* In addition to these findings it was also observed that the process of adduction could be promoted or inhibited by different types of compounds. Redlich and co­ workers (9) developed an empirical relationship for the composition of adducts of n-paraffins in the range n-C^ to n-CL^. This was m = 0.653n + 1.51 where n was the number of carbon atoms and m the molal ratio of urea/hydrocarbon. This was in good agreement with the results of x-ray analysis by Smith (10), who found: m = 0.6925>n -f 1.2$. X-ray studies by Smith showed that the channel in the urea lattice, into o which n-hexadecane just fitted , had a cross-section of lj*l x lj.8 A.