Table Of ContentThe 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.
