Table Of ContentI
UNIVERSITY OF CINCINNATI
M A ^ 2 iq So
I hereby recommend that the thesis prepared under my
supervision by A- O ehlrch a abl&.a ________
entitled S oM e AFt-h ek s___<? f ig -zA r yj. tlHllAXA hok
be accepted as fulfilling this part of the requirements for the
degree of_____ Docrotz of Piuasop^y_____________
Approved by:
Form 668—G.S. and Ed.—500-3-42
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SOME ETKEBS OP lO-ARYLTHIAXANTHENOL
A dissertation submitted to the
Graduate School of Arts and Sciences
of the University of Cincinnati
in partial fulfillment of the
requirements for the degree of
DOCTOR OP PHILOSOPHY
1950
) ■
by
H. Fred Oehlschlaeger
B.S. University of Cincinnati 1947
M.S. University of Cincinnati 1948
AUG 28 1950
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UMI Number: DP15965
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TABLE OP CONTENTS
Acknowledgement......................... vi
Dedication........................ vii
Part I. Introduction ........ 1
J
Part II. History of tMaxanthene and derivatives..2
Thiaxanthone............ ........2
TMaxanthene. ........... 6
TMaxanthene- 5-dioxide.................. 8
Thlaxanthone-5-dioxide ...... 8
TMaxanthenol-5-dioxide.............. 10
^ Thiaxanthene-5-oxide......... ....12
an
TMaxanthenol or 10-hydroxythiaxanthene. 13
10-Alkyl or aryl derivatives of thiaxan-
thenol ........... 17
Phenyl thiaxanthenol...... 18
10-Phenyl-10-cMorothiaxanthene.........19
lO-Phemyl-10-aminothiaxanthene......... 20
10-Benzylthiaxanthenol............ 21
10-Benzylidenethiaxanthene or 10-benzal-
thiaxanthene........................... 21
10-Methylthiaxanthenol................. 22
10-Methylene tMaxanthene............. ..23
10-lethyltMaxanthene............. .23
10-Benzhydryl thiaxanthenol ...... 23
10-Benzhydrylldenethiaxanthene 24
10-Phenylthiaxantheno1-dioxide..........24
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10-Phenylthiaxanthene-dioxide. ....... 24
lO-Phenyl-10-chlorothlaxanthene-dioxide.... 25
Part:III. Procedure and Discussion. ......... 26
Statement of the Problem.............. ....26
Thiaxanthene Derivatives as Medicinals..... 27
$ -Diethylaminoethyl-thiaxanthene-10-car-
boxylate....... ....................... 27
10-Alkaminoalkyl thiaxanthene........ ..29
Miracil................................ 30
Compounds having Structures Similar to Alka-
mine ethers of Thiaxanthenol.......... ....32
Alkamine Ethers ........ 37
Part IV. Suggestions For Future Thesis Problems.....47
Part V. Experimental Details. 51
A. Preparation of Dithiosalicylie Acid....51
B. Preparation of Thiosalieyllc Acid. 52
C. Preparation of Thiaxanthone............54
(1) From Dithiosalicylie Acid......... 54
(2) From Thiosalieyllc Acid............ 55
D. 10-Phenyl thiaxanthenol............ 56
E. The Ferrichloride Addition Compound of
10-Phenyl thiaxanthenol ..... 57
(1) From Aqueous Solution......... ....57
(2) From Ethereal Solution.............57
F. §>' -Diethylamlnoethyl-10-phenylthiaxanthyl
Ether Methiodide....... 58
Method 1................... 53
Method 2.......... .59
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G. (2> -Morpholinoethyl-10-phenylthiaxanthyl
Ether Methiodide.................. 61
H. ^ -Piperidinoethyl-10-phenylthiaxanthyl
Ether Methiodide.............. . .62
I. ft -Dimethyl amino ethyl - 10-pheny lthiaxan-
thyl Ether Methiodide........ 63
J. P-Bromoohlorobenzene...... 64
K. 10-(4-Chlorophenyl)-thiaxanthenol......65
L. ^-Morpholinoethyl-10-(4-chlorophenyl)-
thiaxanthyl Ether Methiodide. ..... 66
M. ^-Dimethylaminoethyl-10- (4-chlorophenyl) -
thiaxanthyl Ether Methiodide....... 67
N. ^-Piperidinoethyl-10-(4-chlorophenyl)-
thiaxanthyl Ether Methiodide.......... .68
0. 10-Phenylthiaxanthenol-dioxide.........68
P. 10-Pheayl-10-chlorothiaxanthene-dioxide.69
Q. $ -Diethylaminoethyl-10-phenylthiaxanthyl-
dioxide Ether Hydrochloride............ 69
R. p-Morpholinoethyl-10-phenylthiaxanthyl-
dioxide Ether Hydrochloride.............70
S. Thiaxanthenol...... .71
Fart VI. Stammary..... * .......... .73
Bibliography ...... 75
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Acknowledgement
The author wishes to express his gratitude to Dr. Ian
R* MacGregor for his helpful suggestions and sincere Interest
during the progress of this work.
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To
Betty D. Qehlsehlaeger
for her ■unfailing encouragement, this
work is affectionately dedicated.
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I IlfHOmCTIOM
la fcli® proposed work the heterocyclic molecule
thiaxanthene will he utilized as a nucleus to prepare a
number of compounds which might reasonably he expected
to he of some value as chemotherapeutic agents* A corre
lation between structure and physiological activity will
be attempted in so far as allowed by the rather meager
information furnished in the literature.
It is beyond the scope of this work to attempt to
report and classify all of the derivatives of thiaxanthene
and related compounds that have been reported. However,
some knowledge of the chemistry of thiaxanthene and its
corresponding ketone, thiaxanthone, is desirable in order
to understand the nature of the problem and the difficulties
encountered in its solution. No attempt will be made by
the author to include any ring substituted compounds, most
of whieh are prepared by ring closure. Only two eases of
substitution on any thiaxanthene type structure have been
reported. We will, however, attempt to discuss the chemis
try of thiaxanthene which contains both an oxidlzable methy
lene group and a sulfur atom as bridges between two aromatic
rings. It will also be necessary to present a partial re
view of the 10-substituted thiaxanthenes since these relate
directly to the problem.
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