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JZ39
PA D.
DEGREE. _ PUBLICATION NO.
^ UNIVERSITY MICROFILMS
S”
ANN ARBOR • MICHIGAN
The Pennsylvania State College
The Graduate School
Department of Chemistry
THE SYNTHESIS AND PROPERTIES OF HIGHER HYDROCARBONS
I. TRICYCLOPENTYL HYDROCARBONS
II. DIDECALYLETHANES
III. FUSED MTJLTICYCLICS
A Dissertation
by
William Kerr Conn
Submitted in partial fulfillment of the
requirements for the degree of
DOCTOR OF PHILOSOPHY
August 1951
Approved S / j /
Assistant Professor dxChemistry
Approved AUG 3 1951
Head, Department of Chemistry
ACKN OVYLEDG EPEh T
The author expresses his sincere gratitude to Dr.
Robert W. Schiessler whose inspiration, encouragement and
direction were invaluable throughout the course of this work.
The Research Staff of Project I|.2 are appreciated for their
assistance, cooperation and suggestions. The writer is also
indebted to the American Petroleum Institute for the grants
which supported this work.
TABLE OF CONTENTS
Page
I Introduction ........... 1
II Historical...................................... h
III Discussion ....... . . . . . . 9
A. The Hydrocarbons and Their Properties . . . . . . 9
B. Effect of Structure on Properties............... 10
1. Tricyclopentyl Hydrocarbons ............... 10
2. Didecalylethanes ............... . . . . . 32
C. Calculated Properties ........... U8
D. Ring Analysis............................ 50
E. Methods of Synthesis........................ 53
1. Apparatus.................................. 53
2. Purity.................................. 55
3. General Methods of Preparation..............56
a. 1,1-Di (alpha-de calyl) ethane............. 56
b. l,2-Di(alpha-decalyl)ethane ........... 57
c. Tricyclopentylmethane................... 57
d. 1,5-Dicyclopentyl-3(2-cyclopentylethyl)2-
pentene...............................£8
e. 9,9,-Perhydrobiphenanthryl ........... 65
f. l,l;,5>8-Dimethanoanthracene Derivatives . 66
IV Experimental......... 68
A. Determination of Physical Properties ......... 68
XV
Page
B. Synthesis of Hydrocarbons and Their Intermediates . 71
1. l,l-Di(alpha-deealyl)ethane .............. 71
2. 1,2-Di(alpha-decalyl)ethane ...... 77
3* Tricyclopentylmethane.............. 82
1|. 1 ,5>-Dicyclopentyl-3 (2-cyclopentylethyl)2-
pentene ......................... 92
ljf3-Dicyclopentyl-3(2-cyclopentylethyl)pentane. 100
6. 9f91-Perhydrobiphenanthryl . . . . . . . . . . 102
7. ljUj^^S-Dimethanoanthracene Derivatives . . . . Ill
C. Attempted Preparations of 2-Cyclopentylethanol. . . 122
Appendix . . . . . . - .............. 136
Bibliography .............................................. lUl
INTRODUCTION
Because of the lack of valuable data on pure hydrocarbons in
the high molecular weight range, the late Dean Prank C. 'Whitmore
originated a project to investigate this field at The Pennsylvania
State College in 19l±0. The aims of the-program were (a) to develop
suitable methods for the preparation of pure, high molecular weight
hydrocarbons, (b) to synthesize a large number of hydrocarbons of
widely varying molecular structure (aliphatic, napthenic and aromatic),
(c) to determine some of their important liquid physical properties
and (d) to correlate their properties with structure. Since 19U3,
the program, known as American Petroleum Institute Research Project
U2, has continued under the leadership of Dr. Robert W. Schiessler,
its present director. The material presented herein represents a
portion of the research completed by Project ij.2.
The hydrocarbons studied have been carefully selected with
several prime considerations. First, series of hydrocarbons were
chosen so that, as much as possible, only one structural character
istic was changed in going from one member of a series to the next.
By so doing, the changes in physical properties can be assigned to
the effect of that particular characteristic. Second, the compounds
were of such a nature that there was no ambiguity concerning structure
as exists, for example, in the dimethylanthracenes.
Synthetic methods were chosen or developed wherein impurities
caused by side reactions had chemical or physical properties suffi
ciently different from the hydrocarbons to permit thorough purifica
tion readily. The author has prepared and determined the physical
2
properties of the following hydrocarbons:
PSG 552 l,5-Dicyclopentyl-3(2-cyclopentylethyl)2— pentene
PSC 553 1, 5-I»icyclopentyl-3 ( 2-cyclopentyletbyl )pentane
PSC 562 l,2-Di(alpha-decalyl)ethane
PSC 563 1,1-Di(alpha-decalyl)ethane
PSC 56U Tricyclopentylmetharie
The author also has prepared 9»9'-perhydrobiphenanthryl and
attempted the synthesis of 1,U,5j8-dimethanoperhydroanthracene deriva
tives.
It is noted that PSC 56^ PSC 5^3 and 9,9’-perhydrobiphenanthryl
consist of a mixture of a large number of cis-trans isomers. No
attempt has been made to isolate or identify the geometric isomers
as this would constitute an exceedingly difficult problem. Admittedly,
the physical property data do not represent those of a single compound;
however, data on the fused hydroarom^-tics are essential in the over-all
relationship of structure and properties.
To the present time only a fet*- pure high molecular weight
hydrocarbons have been prepared which contain the decalyl grouping.
Only two compounds containing two decalyl nuclei per molecule have
been synthesized previously by members of the project. The di-decalyl
ethanes were prepared to further the study of this type of molecule
and to compare the relative effect of the phenyl, cyclohexyl and decalyl
groups on physical properties.
The tri—cyclopentyl hydrocarbon series is a continuation of a
study of the effect of interpolation of methylene groups between the
3
tertiary carbon and the rings in the symmetrically tri-substitated
methanes. The first section of the work is given in the author's
Master’s thesis (l) in which the phenyl and cyclohexyl series are
discussed.
The fused multicyclic compounds have several interesting fea
tures. To date, no PSC hydrocarbon has been prepared consisting
entirely of fused hydroaromatic rings, while only one hydrocarbon
has been synthesized which contains a methylene bridge. Unfortunately,
the completely aromatic compound, 9,9'-biphenanthryl, is not suitable
for study because of its high melting point, 185j°C.
The following physical properties of each hydrocarbon are re
ported: densities at 32°, 68°, 100°, lU0° and 210°F; viscosities in
centipoises at 32°, 68°, 100°, lU0° and 210°F; slope; boiling points
at 0 .50, 1 .00, 2 .0, £.0 and 10.0 mm. pressure; melting point or pour
point; heat of fusion and mole per cent impurity when possible; re
fractive indices at 20.0°, 30.0°, and 1*0.0°C; specific and molecular
refractions and molar volume.
Correlations of physical properties are made with appropriate
compounds prepared by other members of the group.
HISTORICAL
The synthesis of pure hydrocarbons of high molecular weight
(C-jt; - C^q) for physical property study was really begun just eleven
years ago at Penn State. Previous researchers in synthetic hydrocarbons
in this range reported only the properties usually given for organic
compounds or were not concerned with specific structures but merely
attempted to identify hydrocarbon type.
It is logical that the first research in the field was stimulated
by interest in the lubricating oil range of petroleum. Since the ana
lytical approach, i.e., the separation and identification of components
of petroleum, proved prohibitive above the kerosene range, the promising
synthetic method was investigated.
Hugel (2) carried out the first research by preparing a series
of aliphatic, aromatic and hydroaromatic hydrocarbons, Landa and co
workers (3), Suida and Planckh (U) and Becker and Strating (5>) syn
thesized and studied isoparaffins of high molecular weight, Neyman-
Pilat and co-workers (6 ) have prepared seven C22 naphthenic and
aromatic hydrocarbons which were of definite structure and determined
their important physical properties. Suida and Gemassmer (7) and
Schmidt and Gemassmer (8 ) contributed the early information on
cyclopentyl derivatives with a discussion of the reactions by which
they may be made in the pure state. Viscosity-temperature correlations
of multicyclopentyls were studied by Goheen (9). Larsen, Thorpe and
Armfield (10) made 13 hydrocarbons above C22 i*1 connection with oxida
tion studies. The most important contribution was made by Mikeska (11)
5
■who prepared 5>2 hydrocarbons of different molecular type (phenyl,
tetralyl and decalyl derivatives), and determined their important
physical properties. Unfortunately, many of these compounds were of
questionable structure and purity.
Many attempts have been made to correlate various physical
properties of hydrocarbons with the constitution of their mixtures.
Mabery (12), using fractional solution, contributed the first important
paper on the constitution of lubrication oils. Bestuschew (13)
studied six Russian oils and drew certain conclusions as to the effect
of structure on physical properties. Some of these have been proven
wrong by subsequent synthetic work.
Davis and McAllister (lU) have proposed a function relating
molecular weight and molecular volume with number of carbon atoms in
rings per molecule. Using aniline point in conjunction with hydro
genation data, Vlugter, Waterman and Van Westen (l5) obtained rough
determinations of the fractions of aromatics, naphthenes and paraffin
side chains in a given oil. Lipkin, Martin and Kurtz (16) have pro
posed a method for naphthenic-paraffin and aromatic content based on
density and variation of density with temperature. Density coefficient
and refractive index correlation have been used by Lipkin and Martin
(17) to determine paraffin-naphthene mixtures. Recently Fenske and
co—workers (1 8 ) have developed an empirical procedure of ring analysis
based only on refractive index and molecular weight data.
In recent years, various methods have been proposed for cal
culating some important properties of pure hydrocarbons. Kurtz and
Lipkin (19) have given an equation which enables the molecular volume
