anthracene i i. friedel-crafts reaction applied to aromatic ethers and crotonic acid f

69 Pages·2014·1.89 MB·English

I. SYNTHESIS AND PURIFICATION OF
BENZ[!!_]ANTHRACENE
I I. FRIEDEL-CRAFTS REACTION APPLIED TO
AROMATIC ETHERS AND CROTONIC ACID
By
FAH1M UD-DIN
~HMED
Bachelor of Science
Dacca University
Dacca, Bangladesh
1968
Master of Science
Dacca University
Dacca, Bangladesh
1970
Submitted to the Faculty of the Graduate College
of the Oklahoma State University:' .
in partial fulfillment of the requirements
for the Degree of
MASTER OF SCIENCE
July, 1975
OKLAHOMA
STATE UNIVERSITY
LJBRARY
OCT 23 1975
' ·-~·· • ·-;:;;a1
I. SYNTHESIS AND PURIFICATION OF
BENZ[!!_]ANTHRACENE
II. FRIEDEL-CRAFTS REACTION APPLIED TO
AROMATIC ETHERS AND CROTONIC ACID
Thesis Approved:
Dean of the Graduate College
923451
i i
TO
My departed Father
i i i
ACKNOWLEDGEMENTS
I express my deep sense of gratitude to Dr. E. J. Eisenbraun for
his guidance, encouragement, and counsel throughout the course of my
graduate studies and this investigation. I am also grateful to
Dr. 0. C. Dermer for advice and for having read and made many helpful
suggestions during the preparation of this thesis. I thank Dr. T. E.
Moore for serving on my advisory committee. I thank also Mrs. Carol
Taylor for typing my thesis.
am grateful to the Chemistry Department of Oklahoma State
University (Teaching Assistantship), the American Petroleum Institute
(Research Assistantship), the Environmental Protection Agency (Research
Assistantship), and the Dow Chemical Company (Summer Fellowship) for
partial financial support during my graduate work.
thank my fellow graduate students and friends for their sugges-
tions, comments during my graduate work, and for having made this
study pleasurable.
Finally, I thank my Mother who did everything for me since my
!
Father died.
iv
TABLE OF CONTENTS
Chapter· Page
PART I. SYNTHESIS AND PURIFICATION
OF BENZ[~]ANTHRACENE
I. INTRODUCTION AND HISTORICAL 2
I I. RESULTS AND DISCUSSION 9
I I I. EXPERIMENTAL 13
Preparation of 2-(1-Naphthoyl)benzoic acid (2) 13
Cyclization of 2-(1-Naphthoyl)benzoio acid (2) 14
Reduction of 1,2-Benzathhraquinone (l) 15
Purification of Benz[~]anthracene (!_}'. 16
PART I I. FRIEDEL-CRAFTS REACTION APPLIED TO
AROMATIC ETHERS AND CROTONIC ACID
IV. INTRODUCTION AND HISTORICAL 19
V. RESULTS AND DISCUSSION 30
vI . EXPERIMENTAL 38
Preparation of E_-cresyl methyl ether (37) . 38
Preparation of 3 ,4-d i methoxyto 1u ene (4~ . . 38
Preparation of E_-methoxycrotonophenone 49) ..... 39
Preparation of 2-methoxy-5-methylcrotonophenone (51) 39
Preparation of 3,4-dimethoxy-6-methylcrotono- -
phenone (53) . . . . . . · · · · · · · · · · · · 40
Hydrogenation- of 3,4-dimethoxy-6-methylcrotono-
phenone (53) . . . . . · · · · · · · · · · · · 41
Wolf-Kishnei="""'"Reduction of 3,4-dimethoxybutyro-
phenone (55) . . . . . · · · · · · · · · · · · · · · 41
Oxidation of"""3,4•dimethoxy-6-methylcrotonophenone (53) 42
Cyclization of 3,4-dimethoxy-6-methylcrotono- -
phenone (2.J) 43
BIBLIOGRAPHY AND NOTES .. 44
v
Chapter Page
APPENDIX - SPECTRA OF SELECTED COMPOUNDS 53
Spectra of 2-(1-Naphthoyl)benzoic acid (2) 54
...
Spectra of 1,2-Benzanthraquinone (3) - · 55
Spectra of Benz[a]anthracene (1).-:- ..... 56
Spectra of 3,4-dTmethoxy-6-methycrotonophenone (53) 57
Spectra of 3,4-dimethoxy-6-methylbutyrophenone (55) 58
Spectra of 4-hydroxy-5-methoxy-3,7-dimethyl- ~
1-indanone (58a), or 4-methoxy-5-hydroxy-3,7-
dimethyl-1-indanone (58b) ........ . 59
Spectrum of 2-butyl-4,5-dimethoxytoluene (56) 60
Spectra of 4,5-dimethoxy-2-methylbenzoic ~
acid (57) ................ . 60
vi
LIST OF TABLES
Table Page
PART I
I. Proton Magnetic Resonance Spectral Data of .!_, ~'
and l . . . . _ . . . . . . 1 l
PART 11
I I. Selected Friedel-Crafts Reactions of Unsaturated Acids
and Acid Chlorides ..... 24
I I I. Proton Magnetic Resonance Spectral Data 34
vi i
LI ST OF FI GU RES
Figure Page
1. Syntheses of (!_). 3
.
2. Syntheses of (!_). 4
.
3. Syntheses of (!_). 5
~
4. Syntheses of (J_). 6
.
5. Syntheses of (!). 7
viii
PART I
SYNTHESIS AND PURIFICATION
OF BENZ[,!]ANTHRACENE
CHAPTER I
INTRODUCTION AND HISTORICAL
Ben:z[~.Janthracene (.!) is a known carcinogen1 and its carcinogeni-
ci. ty was d eterm1•n.e d t h roug h use o f a vari. ety o f m.i ce 2 an d rats. 3 It
was found that .!_produced skin tumors and lung tumors. Benz[~]anthra­
cene (.!) has been detected in cigarette smoke condensate,4 polluted
air and airborne partlculates5 found in industrial areas and large
cities, automobile exhaust condensate,6 coal tar,7 smoked and broiled
meat, fish, sausage, etc.,8 sewage,9 mineral oil, lO roasted coffee
an d t ea, 11. resi. ns, 12 o 1.1 ve 01· 1 , 13 d ust 1. n go ld m.i nes, 14 r. oasted
peanuts, 15 stack gases from pulp mi 1ls,16 carbon t,lack,17 wood smoke
f rom saw d ust, 18 commerc1• a 1 soaps, 19 wh .1 s ke y, 20 coconut 01. 1 , 21 an d
. . 22 23
chemical and petrochemical waste water, as well as petroleum.
Because of its widespread occurrence, a pure sample of.!_ for use as
a reference material was sought by the Environmental Protection
24
Agency.
Numerous syntheses of.!_ have been described; some of these are
ci·ted below. It was first obtained by reduction with zinc dust and
ammonia of 1,2-benzanthraquinone c1>25which in turn is prepared from
phthalic anhydride and naphthalene, as shown in Figur·e 1. This route
remains a reliable procedure for the preparation of.!. and it was used
in our work. Benz[~]anthracene (!)was also prepared by distillation
o f 2 w•i t h zi•n c d ust. 26
2