The preparation of fluoranthene derivatives by a Diels-Alder reaction with acenaphthylene

114 Pages·04.765 MB·English

by  Mertel, Holly Edgar

THE PREPARATION OF FLUORANTHENE DERIVATIVES BY A
DIELS-ALDER REACTION WITH ACENAPHTHYLENE
A Dissertation
Presented to
the Faculty of the Chemistry Department
The University of Southern California
In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy
by
Holly Edgar Mertel
June 1950
UMI Number: DP21745
All rights reserved
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This dissertation, written by
HOLLY EDGAR MERTEL
under the guidance of h..-k®. Faculty Committee
on Studies, and approved by all its members, has
been presented to and accepted by the Council
on Graduate Study and Research, in partial ful­
fillment of requirements for the degree of
DOCTOR OF PHILOSOPHY
.........
/ Dean
....
Committee on Studies
°.A-
L O . K . 1a )
ill
ACKNOWLEDGMENTS
The author wishes to express his appreciation to
Dr. Milton C. Kloetzel for his careful direction of the
research and study programs.
Most of the microanalyses reported in this work were
done by Dr. Adalbert Elek.
iv
TABLE OF CONTENTS
CHAPTER PAGE
I. THE SCOPE AND PURPOSE OF THE INVESTIGATION . 1
The P r o b l e m ............................... 1
Statement of the Problem . . . . 1
Importance of the Investigation . . . 2
Organization of the Dissertation . . . 5
II. OCCURRENCE, STRUCTURE AND PHYSICAL PROPERTIES
OF FLUORANTHENE ........................... 7
Discovery and Occurrence of Fluoranthene . 7
Availability of Fluoranthene . . . . 7
Incorrect Early Structure of Fluoranthene . 8
Proof of Structure . . . . . . 9
Deductions from Correct Structure of
Fluoranthene.......................... 10
Physical Properties of Fluoranthene . . 11
III. THE CHEMISTRY OF FLUORANTHENE . . . . 12
Molecular Addition Compounds . . . . 13
Reduction of Fluoranthene.....................13
Reduction of Fluoranthene Derivatives . . 14
Oxidation of Fluoranthene.................. 15
Bromination of Fluoranthene . . . . 16
Reactions of the Bromofluoranthenes . . 17
Nitration of Fluoranthene . . . . . 17
Reaction of Fluoranthene with Sodium Amide 18
V
CHAPTER PAGE
Sulf©nation of Fluoranthene . . . . 18
Acetylation of Fluoranthene . . . . 19
Fluoranthenecarboxylic Acids . . . . 20
Aroylation of Fluoranthene . . . . 20
Friedel-Crafts Alkylation . . . . . 21
IV. DERIVATIVES OF FLUORANTHENE BY SYNTHESIS . 22
Diels-Alder Reactions with Substituted
Gyclopentadienones .................... 22
Fluoranthenes by the Michael Condensation . . 23
Fluoranthene Derivatives from 1,2-Dialkyl-
1,2-acenaphthenediols................ 24
Fluoranthene Derivatives from 9-Alkyl-9-
hydroxyfluorenes.........................24
V. THE PREPARATION OF ACENAPHTHYLENE . . . 27
Preparation of Acenaphthylene from 1-Acetoxy-
acenaphthene....................... 28
Treatment of 1-Acenaphthenol with Thionyl
Chloride .............................29
Treatment of 1-Acenaphthenol with Hydro-
bromic Acid........................... 29
A Probable Sequence for the Reaction . . 34
Attempted Preparation of Acenaphthylene
from 1-Acenaphthenylxanthogenate . . 36
Acenaphthylene by Thermal Dehydrogenation
of Acenaphthene....................... 36
Vi
CHAPTER PAGE
Acenaphthylene by Dehydrogenation of Ace-
naphthene with Chloranll . . . . 36
Reaction of Acenaphthene with N-Bromo-
suceinimide............................... 37
Experimental............................... 39
VI. THE DIELS-ALDER STUDIES....................... 50
Dienophillc Activity of Acenaphthylene . 50
Preparation of Adducts from Acenaphthylene 54
Dehydrogenation of the Adducts . . . 56
Verification of structure of the Fluoranthene
Derivatives.............................. 56
Reactions Leading to No Adduct Due to Pre­
dominating Side Reactions . . . . 61
Dienoid Character of Furan Derivatives . 62
Experimental............................... 65
VII. SUMMARY ........................... 93
BIBLIOGRAPHY...................................... 99
vii
LIST OF TABLES
TABLE PAGE
I. Preparation of Acenaphthylene from 1-Acetoxy-
acenaphthene.......................... 30
II. Formation of Acenaphthylene from 1-Acenaph-
thenol by Reaction with Thionyl Chloride
and P y r i d i n e .............................31
III. Formation of Acenaphthylene from 1-Acenaph-
thenol by Reaction with Hydrobromic Acid
and P y r i d i n e .......................... 33
CHAPTER I
THE SCOPE AND PURPOSE OP THE INVESTIGATION
The polycyclic hydrocarbon fluoranthene (I), which
Mb
is now available from coal tar, serves as a suitable star­
ting material for the preparation of a number of its deri­
vatives. Derivatives with substituents in certain positions,
however, are available only by synthesis of the fluoranthene
ring system. It has been the main purpose of this investi­
gation to demonstrate a method for the preparation of other­
wise .unavailable fluoranthene derivatives by synthesis from
materials other than the parent hydrocarbon.
I. THE PROBLEM
Statement of the Problem. There have been three
major purposes of this investigation: (a) To demonstrate
a general method for preparing otherwise unavailable deri­
vatives of fluoranthene. The method consisted of a Diels-
Alder diene synthesis with acenaphthylene (II) as a dieno-
phile as illustrated, (b) To determine the extent of reac-
tivity of acenaphthylene as a dienophile. (c) To develop
a convenient laboratory method for preparing acenaphthylene*
Importance of the Investigation. While fluoranthene
and certain of its derivatives have been found to be non-
carcinogenic (58), the structure of the fluoranthene mole­
cule does somewhat resemble certain of the known carcino­
genic materials. It Is of value, therefore, to be able to
prepare derivatives of fluoranthene of known structure,
since in certain other cases the carcinogenic activity of
polynuclear hydrocarbons and their derivatives has been
found to vary widely with only slight variation in struc­
ture. Such variation in carcinogenic activity is illustra­
ted by the following examples.
CARCINOGENIC COMPOUNDS
ch3 cm3 ch3
III IV V
NHCOCH3
CH,
VI VII VIII
III 7-Methylbenz [a] anthracene (107)
IV 6,7-Dimethylbenz[a]anthracene (107)