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AN ABSTRACT OF THE THESIS OF
YILIN QIAO
in
for the
Chemistry
Title:
Master of Science
presented on
September 1st, 1994.
Synthesis of substituted Planar Triarylmethane.
Abstract approved:
Two protective groups, benzyl and butyl, were utilized to
protect the central carbon of sesquixanthene in electrophilic
sUbstitution reactions. Attempts were also made to perform
sUbstitution on unprotected sesquixanthene.
Nitration was carried out on sesquixanthene where the
central carbon was protected and where the central carbon was
unprotected. After bromination and nitration, cleavage of the
protective group by oxidation was successful. Reduction of the
nitro
groups
to
amino
groups
by
tin
metal
and
stannous
chloride was also attempted, but because of inavailability of
necessary analytical methods, the results were inconclusive.
_ ------1
~
SYNTHESIS OF SUBSTITUTED
PLANAR TRIARYLMETHANES
A Thesis
Presented to
the Department of Chemistry
EMPORIA STATE UNIVERSITY
In Partial Fulfillment
of the Requirements for the Degree
Master of Science
by
Yilin Qiao
~
September 1994
1
,<
ACKNOWLEDGEMENT
I would like to express my deepest thanks to my thesis
advisor and committee chair, Dr. Eric Trump, for the guidance
of my research project and my graduate study. He was always
willing to answer any questions that I might have about the
SUbject matter of this thesis. without his encouragement, this
thesis would never have been completed.
I would also like to express my sincere gratitude to my
academic advisor, Dr. Charles Greenlief, for his suggestions
and for his devoting time and tolerance to give all kinds of
help.
I would like to voice my appreciations to Dr. Robert
Jones for devoting his valuable time to give advice and to
review my thesis.
I
would like to express my sincere gratitude to Dr.
Arthur Landis and Dr. Kenneth Johnson for instructions in
using certain instrumentation.
i
CONTENTS
INTRODUCTION ••••••••••••••••••••••••••••••••••••••••••••••••• 1
EXPERIMENTAL SECTION ••••••••••••••••••••••••••••••••••••••••• 6
2,6,2',6',2.. ,6..-hexamethoxytriphenylcarbinol •••••••••••••• 6
9-(2,6-dimethoxyphenyl)-1,8-dimethoXYXanthydrol ••••••••••• 7
sesquixanthydrol
8
a. From 2,6,2',6',2.. ,6..-hexamethoxytriphenylcarbinol. •••• 8
b. From 9-(2,6-dimethoxyphenyl)-1,8-dimethoxyxanthydrol •• 8
Benzyl sesquixanthene and butyl sesquixanthene ••••••••••• 10
a. Reaction with fluoroboric acid ••••••••••••••••••••••• 10
b. Reaction with benzyl magnesium chloride •••••••••••••• 10
c. Reaction with butyl magnesium bromide •••••••••••••••• 11
Benzyl tribromosesquixanthene •••••••••••••••••••••••••••• 12
Butyl tribromosesquixanthene ••••••••••••••••••••••••••••• 12
cleavageofprotectinggroup ••••••••••••••••••••
. •.• .. 13
Fluoroboric trinitrosesquixanthene ••••••••••••••••••••••• 14
Reductionoffluoroborictrinitrosesquixanthene ••
• .15
Butyl trinitrosesquixanthene ••••••••••••••••••••
• .15
Reductionofbutyltrinitrosesquixanthene ••••••••••
• •• 15
DISCUSSION OF RESULTS ••••••••••••••••••••••••••••••••••••••• 17
CONCLUSION •••••••••••••••••••••••••••••••••••••••••••••••••• 23
REFERENCES. • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 2 4
IR SPECTRA •••••••••
• .26
NMR. SPECTRA ••••••••••••••••••••••••••••••••••••••••••••••••• 41
ii
LIST OF IR SPECTRA
1
1.
IR spectrum of 2,6,2',6',2",6"­
hexamethoxytriphenylcarbinol ••••••••••••••••••••••••••. 26
2.
IR spectrum of 9-(2,6-dimethoxyphenyl)­
1,8-dimethoXYXanthydrol •••••••••••••••••••••••••••••••• 27
3.
IRspectrumofsesquixanthydrol •••••••••••••••••••••••• 28
4.
IR spectrum of fluroboric sesquixanthene ••••••••••••••• 29
5.
IR spectrum of benzyl sesquixanthene ••••••••••••••••••• 30
6.
IR spectrum of butyl sesquixanthene •••••••••••••••••••• 31
7.
IR spectrum of the product obtained from bromination
of benzyl sesquixanthene ••••••••••••••••••••••••••••••• 32
8.
IR spectrum of product obtained from bromination
of butyl sesquixanthene •••••••••••••••••••••••••••••••• 33
9.
IR spectrum of the product obtained from oxidation
of benzyl trinitrosesquixanthene ••••••••••••••••••••••. 34
10.
IR spectrum of the product obtained from nitration
of fluoroboric sesquixanthene •••••••••••••••••••••••••. 35
11.
IR spectrum of the product obtained from reduction
of fluoroboric trinitrosesquixanthene •••••••••••••••.•. 36
12.
IR spectrum of the product obtained from nitration
of butyl sesquixanthene •••••••••••••••••••••••••••••••• 37
13.
IR spectrum of the product obtained from reduction
reactionofbutyltribromosesquixanthene ••••••••••••••• 38
14.
IR spectrum of the product obtained from nitration
reactionofbenzylsesquixanthene •••••••••••••••••••••. 39
15.
IR spectrum of the product obtained from bromination
of fluoroboric sesquixanthene •••••••••••••••••••••••••. 40
........
iii
LIST OF NMR SPECTRA
16. NMR spectrum of the solvent deuterated chloroform •••••• 41
17. NMR spectrum of the solvent deuterated acetone ••••••••• 42
18. NMR spectrum of 9-(2,6-dimethoxyphenyl)­
1,8-dimethoxyxanthydrol •••••••••••••••••••••••••••••••• 43
19. NMR spectrum of sesquixanthydrol ••••••••••••••••••••••• 44
20.
NMR spectrum of benzyl sesquixanthene •••••••••••••••••• 45
21.
NMR spectrum of butyl sesquixanthene ••••••••••••••••••• 46
22.
NMR spectrum of the product obtained from bromination
of benzyl sesquixanthene ••••••••••••••••••••••••••••••• 47
23.
NMR spectrum of the product obtained from nitration
of fluroboric sesquixanthene ••••••••••••••••••••••••••• 48
1
INTRODUCTION
Triarylmethane dyes have been used
chemistry.
They
are
useful
in many areas of
reagents
for
indicators, 1
dichromatic titration and redox indicators, determining the
presence
of
traces
of
halide
irons,2
and
the
spectrophotometric determination of Sb(III),3 Ta(V)," Ga(III),s
In,6 to list just a few. They are used in ball point pen inks'
and as corrosion inhibitors.' Several triarylmethane dyes are
good indicators of the titration for Fe(II), Ti(III), Cr(II),
Cu(I) with Ce(IV), and for the titration of Fe(II), Fe(CN):,
U(IV), Mo(V) and hydroquinone with dichromate.
Except for the azodyes,
dyes
are
the
most
triphenylmethane and xanthene
commonly
used
reagents
in
the
spectrophotometric determination of metals. Reports on the
most
common
phenylfluorone,
and
well
known
malachite green,
sUbstances--aluminon,
brilliant green,
crystal
violet, and rhodamine--were published over a half century ago.
In the phenol red group, for example, phenolsulfonphthalein
has been used for the kinetic determination of copper,' the
decomposition
of
the
dye
being
recorded
spectrophotometrically.
Two
problems
with
these
indicators
are
that
their
reactions are not all reversible and they are often not stable
in oxidizing solutions. In spite of these disadvantages, they
have been commonly used. 10,11
2
The unique properties of the central carbon atom have
aroused much chemical interest in triarylmethane dyes. A free
radical,
a
cation,
or
an
anion
can
occupy
the
central
position, with resonance delocalization on the aromatic rings.
The stabilization of triarylmethane dyes is dependent on the
degree of twist of three phenyl rings. The dye has maximum
stability when the rings are coplanar, but this is normally
impossible, so a propeller-shaped molecule results. 12,13
The stability of triarylmethanes is also dependent on the
ring
substituents.
Ortho-substitution
decreases
the
stabilization because of large steric effect. The cation of
this para-methyl substituted triarylmethane is five times as
stable
as
the
cation
of
tris
ortho-methyl
substituted
triarylmethane. 14 It may be seen that the effect of ortho
substitution
is
large
and
the
effect
is
most
readily
attributed to steric factors. Increasing the degree of ring
twist will decrease the degree of ring resonance and thus
decrease stabilization.
The
use
of
oxygen
bridges
to
force
planarity
of
triarylmethane or triaryl radicals has been investigated and
numerous 9-substituted xanthyl (I)
free radicals have been
reported by conant. IS stability increased because of the oxygen
bridges. The two oxygen bridged molecule (II) in the xanthyl
series has also been reported. 16 This radical was reported to
be 100% dissociated
in benzene at room temperature since
dilute solutions of the radical were found to obey Beer's law
3
and no darkening of the solution occurred on warming.
The
authors have interpreted this high degree of dissociation as
being due to high resonance stabilization in the free radical
due to planarity of the system. When compound (II) is compared
with compound (I),
it is observed that compound
(II)
shows
greater stabilization due to second oxygen bridge.
o
(II )
(I)
sesquixanthydrol (III) was of considerable synthetic and
chemical interest to us.
It has an unusually high basicity
caused by resonance distribution of the positive charge to the
oxygen bridge as shown in structure (IV).
0+
o
o
o
(III )
(IV)
4
In a sUfficiently acidic solution, sesquixanthydryl is
protonated and loses water. This type of compound is called a
"secondary base" and the equilibrium constant is expressed in
terms of KR + .18 Triphenylcarbinol, has a pKR + of -6.63. 19 Based
on
the
differences
between
the
resonance
structure
of
triarylmethane and sesquixanthene, the pKR + for sesquixanthene
is expected to be much larger than -6.63. Generally, electron
donating
groups
should
stabilize
the
carbonium
ion
and
increase pKR+. Three para dimethylamino groups increase the
pKR+ to 9.63 and three para methoxy groups change the pKR + to
0.82.
The planar sesquixanthydryl cation (IV) is noted for its
exceptional stability. Propeller-shaped crystal violet (V),
which contains electron-donating dialkylamino groups, is noted
for
its
intense
color,
but
it
is
not
fluorescent.
In
fluorescent Rhodamine B(VI),2° which contains dialkylamino
groups, two of the three rings are locked into the same plane
by
an
oxygen
bridge.
Combining
the
planarity
of
the
sesquixanthydryl cation with electron donating group such as
crystal
violet
(V)
produces
compound
such
as
triamino­
sesquixanthene (VII) is the objective of our research. Such a
series of compounds would be expected to be intensely colored
and strongly fluorescent.
A known synthetic route 21 for the preparation of amino
substituted sesquixanthene dyes is to start with a substituted
benzene which has a good leaving group, such as 3,5-dimethoxy
5
fluorobenzene.
This
route
avoids
protecting
the
central
carbonium ion. Our primary purpose was to create a different
synthetic
route
which
would
allow
us
to
synthesize
the
sesquixanthene base first and then add protecting group to
form a sesquixanthene dye as an intermediate, then to replace
a hydrogen on the aromatic ring with an amino group, forming
a basic amino dye. When this synthesis was carried out, we had
the opportunity to investigate the activity of the central
carbon,
the
protective
ability
of
different
substituted
groups, and the relationship between fluorescence and color.
~H3)2
a
(CH 3 )2 N
.//
N(CH 3 )2
( V)
H N
2
~
o
NH
2
(VII)
~
o
1/
:.J---C -OH
(CH 3 CH 2 ) 2 N
+
o
(VI)
N(CH 2 CH 3 )2
6
EXPERIMENT SECTION
synthesis of 2,6,2',6',2",6"-hexamethoxytriphenylcarbinol
6
+
I
H 3 c 6 i CH3
I
Li)
~
H3CO~OCH3
~
H3CDCH3
I
-t
~
H3 CO
CH30-~-OCH3
OCH3
cx:::H3
~
~./'1
H3 m
~
cx:::H3
A solution of phenyl lithium was prepared by the addition
of
bromobenzene (19.5 g,0.125 mole) to 65 mL of ether with
lithium wire (2.0 9 0.290 mole) and 30 mL of diethyl ether.
1,3-dimethyl benzene (15.0 g, 0.109 mole) was added and the
reaction mixture was allowed to stand at room temperature
under an atmosphere of nitrogen for sixty hours. 2, 6-dimethoxy
phenyl
lithium
was
formed
as
white
crystals. 29
Dimethyl
carbonate (3.24 g, 0.036 mole) in 200 mL of benzene was added
and the reaction mixture was refluxed for three days under a
protective nitrogen atmosphere. A white solid formed in the
reaction mixture during this time. After cooling, the reaction
mixture was poured into 300 mL of water to produce an aqueous
7
layer and an organic layer. The organic layer was separated
from the aqueous layer, washed twice with water, dried over
sodium sulfate and concentrated to yield a grey residue. The
residue was recrystallized once from ether to yield 14.98 g
of 2,6,2',6',2", 6"-hexamethoxytriphenyl carbinol with
(47%)
melting
point
163-164°C.
The
product
was
verified
by
IR
spectrum Figure 1.
Synthesis of 9-(2,6-dimethoxyphenyll-1,8-dimethoxyxanthydrol
OCH3
OCH3
CH3
A
solution
HCl
of
~
CH3
2,6,2',6',2",6"­
hexamethoxytriphenylcarbinol (4.0 g, 0.0508 mole) in 1,000 mL
of water and 10 mL of concentrated hydrochloric acid was
heated for two hours on a sand bath. The initial deep purple
solution became deep red during the reaction and a
white
precipitate formed. The precipitate was collected by suction
filtration and dried under vacuum to yield 3.48 g (96%) of 9­
(2,6-dimethoxyphenyl)-1,8-dimethoxyxanthydrol.
The product
was purified by one recrystallization from benzene-acetone to
give 2.58g of material with melting point 295-298°C.
This
8
was identified by infrared spectrum Figure 2. and NMR
spectrum Figure 18.
synthesis of sesquixanthydrol:
A. from 2,6,2',6',2 1 ,6"-hexamethoxytriphenylcarbinol
o
o
H -N+
Cl
~/i
~
H CO
3
OCH 3
pyridine
hydrochloride
(50.0
0.435
q,
2,6,2' ,6' ,2 1 ,6"-hexamethoxytriphenylcarbinol
mole)
mole)
(10.0 q,
and
0.023
were mixed and heated with stirrinq at 195°C for one
hour. The initial purple mass qradually became liquid under
these conditions and took on a red color. The reaction mixture
was washed into one litter of water to produce a red solid and
a yellow aqueous solution. The solution was filtered to remove
the red solid and was then basified with potassium hydroxide
to
produce
a
white
solid.
This
product
was
purified
by
recrystallization from a solution of diethyl ether, benzene,
and
ethanol
to
yield
0.9
q
of
pure
material
which
was
identified as sesquixanthydrol.
B. from 9-(2,6-dimethoxyphenyl)-1,8-dimethoxyxanthydrol
.....
9
CH
3
OCH
3
0I
.;.:-.....
0'
>
~
'0
+N
I
H U­
9-(2,6-dimethoxyphenyl)-1,8-dimethoxyxanthydrol (2.5 g,
0.006 mole) and pyridine hydrochloride (7.0 g, 0.061 mole)
were mixed and heated at maximum reflux on a sand bath for one
hour. The initial solid became a deep red liquid. At the end
of this time, the red liquid reaction product was poured into
water and the solids remaining in the reaction flask were
washed out with water. A red solid remained undissolved in the
water while the solution was a reddish yellow color. The
solution was filtered to remove the red material and was then
basified with potassium hydroxide Which discharged the yellow
color of the solution and produced a light brown precipitate.
The precipitate was collected and dried under vacuum to yield
1.75
g
(89%)
of
sesquixanthydrol.
The
product
was
recrystallized once from ether, purified by passing it through
aluminum absorption column to yield 1.17 g (65%) of white pure
sesquixanthydrol with melting point 303°C. The product was
verified by Infrared spectrum Figure 3,
and NMR spectrum
10
Figure 19.
synthesis of benzyl sesquixanthene and butyl sesquixanthene.
a. Reaction with fluoroboric acid.
7
+ HBF 4
Sesquixanthydrol (2.0 g, 0.007 mole) was dissolved in 200
ml ether and fluoroboric acid (1.75 ml, 0.014 mole) was added
in the presence of acetic anhydride. The reaction mixture was
stirred at room temperature for one hour. A yellow colored
solid gradually formed. The solution was separated by suction
filtration,
and the solid was washed with 20 Xl benzene to
yield 2.3 g (94%) of fluoboric sesquixanthydrol with melting
point above 350°C. verified by infrared spectrum Figure 4.
b. Reaction with benzyl magnesium chloride.
(rH Cl.
2
)
Mg
~
0
d
9C'
OCH:>"9Cl
OCE
...
11
Fluroboric sesquixanthene (1.7 g, 0.0046 mole) was added
to 100 mL of diethyl ether. Freshly prepared benzyl magnesium
chloride was added dropwise under nitrogen while stirring. The
yellow solid disappeared gradually. The solution was allowed
to stand for 30 minutes after all solid had disappeared. The
solution was washed using 40% concentrated HCl. The organic
layer was separated from the aqueous layer, washed once with
water, dried over sodium sulfate and concentrated to yield a
light brown solid. The brown solid was recrystallized once
from
hexane
to
yield
1.45
g
(84%)
of
pure
benzyl
sesquixanthydrol with melting point 173-175°C. The product was
analyzed
spectroscopically
using
IR
and
NMR,
giving
the
infrared spectrum Figure 5, and NMR spectrum Figure 20.
c. Reaction with butyl magnesium bromide.
CIl CH CH cH m:
2
2
2
3
+
Br
~
CH CH CH CH Br
2
2
2
3
CH CH CH cH Br
2
2
2
3
+
Mg
?
CH CH CH cH MgBr
2
2
2
3
CI-l CH CH CH
3
2
2
3
o
o
CH CH CH cH MgBr
3
2
2
2
~
o
Fluoboric sesquixanthene (0.8 g, 0.002 mole) was added in
70 mL of ethyl ether. Freshly prepared butyl magnesium bromide
was added dropwise under nitrogen with stirring. The yellow
12
solid disappeared gradually. The solution was allowed to stand
for 30 minutes after all the solid disappeared. The solution
was washed with 10% hydrochloric acid. The organic layer was
separated from aqueous layer, washed once with water, dried
over sodium sUlfate and concentrated to yield a light brown
solid. The brown solid was recrystallized once from hexane to
yield 0.7 g
melting
(95%) of white, pure butyl sesquixanthene with
point
161-161. 5°C.
spectroscopically
using
IR
The
and
product
NMR,
giving
was
analyzed
the
infrared
spectrum Figure 6 and NMR spectrum Figure 21.
synthesis of 1,1' ,1"-tribromo-benzyl sesquixanthene I 1,1' ,1"­
tribromo butyl sesquixanthene:
>
CH 2 {
+
Br2
>
CH 2 {
~
Br
Br
Finely
powdered
benzyl
sesquixanthene
or
butyl
sesquixanthene was placed in a weighing bottle cover, and then
the bottle cover was placed in a large neck Erlenmeyer flask
(the ideal vessel is a desiccator). Another weighing bottle
cover containing chemical quantitative bromine liquid (neat)
was
,
set
side
by
side
with weighing
bottle
cover
in
the
13
Erlenmeyer
flask.
flask.
In
the
sesquixanthene
A rubber
flask,
was
in
stopper
benzyl
contact
sealed
the
erlenmeyer
sesquixanthene
with
bromine
I
butyl
vapor.
The
Erlenmeyer flask and its contents was allowed to stand 8 hours
or overnight. During this period, a needle was inserted, at
two hour intervals,
to provide a means of escape for
the
hydrogen bromide. The orange solid was then removed from the
Erlenmeyer flask and allowed to stand in the air under the
hood for four hours to allow the evaporation of bromine. The
crude 2,2',2"-tribromo benzyl sesquixanthene was dissolved in
30 JIlL of benzene,
filtered and cooled in an ice-bath. The
resulting crystals were filtered and air dried. Both of the
products
were
sesquixanthene,
light
pink
color.
For
tribromo
benzyl
the melting point was 261°C and for butyl
tribromosesquixanthene,
the
melting
point
was
220°C.
The
products were analyzed by IR spectrum, Figures 7 and 8, and
NMR spectrum Figure 22.
Cleavage of protective group.
B;H 2
-O~
_
o
Br
o
KMno~
H+
Br
A solution was prepared by adding 1,1' ,1"-tribromo benzyl
14
sesquixanthene
(0 .1S
g,
0.0003
mole)
in so mL of diethyl
ether, potassium permanganate (0.14 g, 0.0009 mole) in 20 mL
of water, and 2 mL of sulfuric acid. The mixture was allowed
to reflux overnight. At the end of the reaction, a white solid
product was formed between the ether and aqueous layers. The
solid mixture was collected by suction filtration and then
poured into ethyl ether with stirring for ten minutes. The
ether insoluble portion was separated by suction filtration.
The ether layer was dried over sodium sulfate and concentrated
to yield a white solid with melting point at 30SoC.
This
product was analyzed by IR spectrum and this spectrum is shown
in Figure 9.
synthesis of Fluroboric trinitrosesquixanthene.
HNO
J
~
N0
2
Fluroboric sesquixanthene 0.6 g, 0.0016 mole) was placed
in an Erlenmeyer flask, and 30 mL of concentrated nitric acid
was added. The Erlenmeyer flask was heated and maintained in
a
SO°C
water bath for
two hours.
After cooling,
a
small
portion was dried in air. A needle-shaped product was formed.
The rest was poured into 100 mL of crushed ice. At this time,
15
a golden orange colored solid was formed.
The product was
collected by suction filtration, dried in 80 0 e oven to yield
0.39 g, 0.0009 mole (59%) of the product, which was platelet
shaped with a
melting point above 350 oe.
The product was
analyzed by IR in Figure 10 and NMR in Figure 23. A test by
iron (II) hydroxide was positive.
Reduction reaction of fluoroboric trinitrosesquixanthene.
The
procedure
of
reducing
the
fluoroboric
trinitrosesquixanthene was the same as the procedure for the
reduction reaction of butyl trinitrosesquixanthene, but the
color of the product was different.
The melting point was
above 360 oe. The IR spectrum is presented in Figure 11.
synthesis of Butyl trinitrosesquixanthene.
The nitration procedure with butyl sesquixanthene was
almost the same as the procedure for the
nitration reaction
of fluoroboric sesquixanthene. The only difference was that a
little sUlfuric acid was added. The melting point was 292­
296°e. The product was analyzed by IR spectrum, Figure 12.
Reduction of butyl trinitrosesquixanthene.
Butyl
trini trosesquixanthene
(1.32
gO. 003
mole)
was
placed in round-bottomed flask which was fitted with a reflux
condenser. 100 mL of concentrated hydrochloric acid was added.
The mixture was heated with vigorous stirring in order to
dissolve the fluoroboric trinitrosesquixanthene.
solid dissolved
After the
(it was difficult to dissolve all of the
solid), granulated tin metal (2.5 g, 0.02 mole) was added in
16
very small portions during a 6 hours period. After adding tin
metal,
orange.
the color of the solution changed from yellow to
When the reaction was
complete,
an orange
solid
precipitated. As the reaction mixture cooled, the product was
separated by suction filtration. The solid portion was washed
with 20 mL of water and dried in the air at 110°C to yield
(0.56 g, 50%) a reddish orange colored powder with a melting
point of 219-222°C. This product did not dissolve in ether, or
benzene, but was slightly soluble in water. The IR spectrum of
the product shown in Figure 13.
:.
17
DISCUSSION
There are two possible precursors to sesquixanthydrol.
Both are alcohols, the structures are shown as (I) and (II).
OCH
H CO
3
3
OCH 3
H CO
3
(II)
(I )
Of these two precursors, (I) is much more viable, as (II) is
formed only with great difficulty.
In considering synthetic routes to sesquixanthydrol the
most promising method utilized a
ring closure reaction. 22
pyridine hydrochloride appears to be the most effective ring
closure agent for
this reaction.
Since the alcohol
(II)
eXhibits large steric hindrance due to the methoxy groups, the
conditions for ring closur. of compound (II) were extremely
difficult to optimize. The synthetic route from alcohol (II)
was abandoned at this point and attempts were directed toward
a synthesis of alcohol(I), for which steric factors are less
extreme.
2,2' , 6' ,2", 6"-dimethoxytriphenylcarbinol
is
very acid
sensitive. It formed appreciable amounts of the deep purple
'--~
18
cation even in distilled water. In ethyl ether, its initial
colorless solution rapidly changed to purple while evaporating
the ether in the atmosphere. It is water soluble, but also
slightly soluble in ether and benzene. Not only is it a deep
purple color but also a high adhesive ability as well. At low
pH, it will lose two of its methoxy groups and form one oxygen
bridge.
It is important to protect the central carbonium ion in
ring substitution reactions. since the central carboxyl group
is extremely active and easy to oxidize, it must be protected
by a group such as benzyl or n-butyl. Two Grignard reagents,
benzyl magnesium chloride and butyl magnesium bromide, were
successfully made and successfully reacted with sesquixanthyl
fluoroborate
forming
benzyl
sesquixanthene
and
butyl
sesquixanthene. The protection of the central carbon seemed
perfect.
Two routes were designed to synthesize tris-4,4'4"-amino
sesquixanthene. One involved the synthesis of tris-4, 4' 4"­
nitro sesquixanthene intermediate, and then, the subsequent
reduction of the nitro groups to amino groups.
The other
involved halogenation of the phenyl rings first, then utilized
the benzyne mechanism to replace the halogens by amino groups.
The halogenation followed by benzyne elimination-addition was
expected to give a
higher yield of the desired product,
4,4',4"-triamino sesquixanthene.
Nitration or halogenation were expected to be easy to
19
carry out. Theoretically, the ether groups should be strongly
activating. On the other hand, when the central carbon carries
a
positive
change,
the
rings
should
be
deactivated
with
respect to electrophilic sUbstitution.
Bromination of benzyl sesquixanthene in ethyl ether was
unsuccessful. When benzyl sesquixanthene was allowed to stand
with bromine for three days,
the reactants retained their
yellow color and looked the same as the starting material even
in the presence of ferric chloride. We believe that 1,1',1"­
bromo benzyl sesquixanthene should be white.
Bromination
of
benzyl
sesquixanthene
and
butyl
sesquixanthene by bromine vapor was successful. The product of
the bromination reaction was analyzed by IR.
spectrum,
Figures 7 and 8,
From the IR
it was impossible to determine
which isomer was produced.
Normally, the substitution pattern is identified by two
bands in IR spectrum, the stronger absorption bands are below
900 cm1 • These out-of-plane bending and ring puckering bands
are very intense. The overtone and combination bands at 2000­
1600 cm1 are also useful. Unfortunately, this type of band
analysis is suitable only for simple aromatic ring systems.
For complicated aromatic compounds, these two areas cannot
offer
reliable
identification. D
Using
a
high
resolution
instrument and relatively pure samples, the C-Br stretch will
appear
at
690-515
instruments. 24
em-I,
but
cannot be
observed with most
20
The
product
obtained
from
bromination
of
benzyl
sesquixanthene could not be identified by its IR spectrum, but
could be identified by the Bielstein test. 2S The green flame
indicated that bromination had occurred. When the same method
was applied to the bromination of sesquixanthyl fluoroborate,
the Bielstein test was negative,
changed color.
Neither the IR
even though the reactant
(IR Figure 15)
nor chemical
tests could prove that a reaction had occurred.
Since a
better
synthesis method
to
brominate benzyl
sesquixanthene could not be find, we tried to nitrate benzyl
and butyl sesquixanthenes. We utilized a mixture of three
parts
nitric
acid
and
one
part
sUlfuric
acid.
At
room
temperature, benzyl sesquixanthene dissolved instantly, but
the product became pitch like at about 80 De. What substitute
was formed is unknown. After this procedure failed to give the
desired product, we tried concentrated nitric acid. It seems
that nitration in cold nitric acid was very slow, even after
twenty
hours.
In
hot
nitric
acid
benzyl
sesquixanthene
dissolved faster and a reaction occurred. The product obtained
from
nitration
was
also
green.
After
neutralization
and
filtration, the cotton-like product was analyzed by IR. From
the IR spectrum shown in Figure 14, there was no stretching
peak at 1600-1500 cm- I and 1300-1250 cm- I •
Around 3447 cm- I ,
there is a large peak, which represents the 0-8 stretch. Since
these peaks
are all
located within the area of
aromatic
absorption, we cannot be sure whether nitration was successful
21
or not.
Nitration of benzyl sesquixanthene was not successful.
From the IR spectrum, Figure 10, we can see that two peaks
appear at 3406 and 3476 em-I, and it doesn't show CSp2_B stretch
in the range 3000-2900 cm l
•
Obviously, the protecting group
was too weak to withstand oxidation by nitric acid.
Oxidation
permanganate
of
was
benzyl
sesquixanthene
difficult.
Basic,
with
neutral,
potassium
and
acidic
reaction conditions were attempted, and different ratios of
potassium permanganate to benzyl sesquixanthene were tried.
Generally, oxidation by potassium permanganate occurs rapidly
in basic solution. Treatment with potassium permanganate in
basic
solution
failed.
Boiling
for
twenty-four
hours
in
neutral solution also failed. Although potassium permanganate
will slowly decompose in acidic conditions, its high oxidation
ability was critical in this reaction.
oxidation occurred
after sUlfuric acid was added and the reaction occurred very
rapidly. According to IR Figure 19, the wide peak at 3500 em-I
may be due to moisture. The peak at 3081 em-I was aromatic C-B
stretch.
The
aromatic
absorption
peak
at
1600.8
cm- l
was
smaller. Since the IR spectrum shows methylene CSp3-B stretch,
there are two possibilities. One is that the sample was not
pure
enough,
oxidation.
the
In
other
the
IR
was
that
spectrum,
it
was
the
not
cleaved
aromatic
by
major
characteristic peak 1600 cm l was less intense. Other peaks,
such as 1464 and 1047 cm- l were unchanged. c-o-c absorption at
22
1267 cm-1 was also present.
The oxidation product was barely soluble in non-polar
organic
common
solvents,
NMR
however
solvent
after
these product
did dissolved
several
Al though
days.
in
several
solutions were prepared for NMR analysis, none of these gave
satisfactory results because they were too dilute.
sesquixanthyl
fluoroborate
seemed
easier
to
nitrate.
Although neither IR and NKR spectrums can distinctly indicate
that the -HOz function group was present, we can say that
nitration was successful. This conclusion is based upon both
the iron (II) hydroxide test Z6 and the sodium fusion testZ7 ,
both showing positive reSUlts.
Further,
nitration
fluorescence
showed
more
intense
the product after
than
the
un­
nitrated material.
The reaction to reduce -NOz to -NHz was unsuccessful,
although the color of the product after reduction changed from
yellow to orange and to reddish orange. Neither the IR, NMR
spectrum, nor chemical tests indicated success. There was no
evidence of a color change caused by the SUbstituting amino
group. If -NHz was successfully attached on the aromatic ring,
it would be expected to be mostly meta substitution because of
-0- group attached at both ortho position. If an amino group
occupies the
color change. Z8
meta position, the compound would not show a
23
CONCLUSION
synthesis of a bromine-substituted sesquixanthene was
successful. In the bromination reaction, the sesquixanthene
whose central carbon was protected showed better results in
terms
of
higher yield
and
fluorescence
central carbon was not protected.
than
those
whose
But in cleavage of the
protective group, an improved oxidation method needs to be
developed.
synthesizing nitro-substituted sesquixanthene was also
successful.
This
succeeded whether or not
the molecule's
central carbon was well-protected. Nitro-sesquixanthene has
high
fluorescence
nonpolar solvents.
and
high
solubility
in
both polar
and
24
REFERENCES
1.
Lund, H., J. Am. Chem. Soc.
2.
Bunikiene, L.; Ramanauskas, E., Chem. Abstr. 69, 113233W,
1969.
3.
Liu, Shaopu and Liu, zhongfang, Fenxi Huaxue, 10, 464,
1982; Chem. Abstr. 97, 229295, 1982.
4.
Dobkina, B. M.; ZUbynina, K. B.; Nadezhdina, G. B., Khim.
Metody Anal. Niobiya Splavov Ego Osn. 58, 1970.
5.
prabhu, B. N.; Khopkar, S. M., Talanta, 25, 109, 1978.
6.
Kuznetsov, V. I.; Kleschel'skaya, E. I., Agrokhimiya (2),
148, 1970, Chem. Abstr. 73, 41531z, 1970.
7.
Badischi Anilin' soda-Fabrik A.-G. (by H. Finkenauer; H.
Ottervach) British Patent 902110, 1972; Chem. Abstr. 57,
p12664b. 1962.
8.
Antropov. L. I.; Kozlob, E. I.; Barmachenko. I. B., Chem.
Abstr. 82, 46714g, 1975.
9.
Soares, V. M.; Rodrigues, R. A., Chem. Abstr. 94, 76101,
1981.
10.
Brazier, J. N.; stephen, W. I., Analytica Chimica Acta
33, 625, 1965.
11.
Rao, N. V.; Dutt,
150688X, 1971.
12.
Coulter, A. K.; Schuster, I. I.; Kurland, R. J. J. Am.
Chem.Soc. 87, 2278, 1965.
13.
Ohla, G. A., Angew. Chem. Int. Ed. 12, 173, 1973.
14.
Theilacker, W.; Schulz, H.;Baumgarte, U. ;Drossler, H.
G.; Rohde, W.; Thater, F. ; Uffmann, U., Angew. Chem. 69,
322, 1957.
15.
Conant, J. B.; Sloan, A. W., J. Am. Chem. Soc. 45, 2466,
1923.
16.
Neunhoeffer,
1958.
V.
0.; Haase,
V.,
H.,
49, 1346, 1927.
Chem.
J.
Abstr.
Chem.
74,
Ber.,
105686v,
91,
1801,
25
17.
Soares, V. M.; Rodriques, R. A., Chem. Abstr. 94, 76101,
1981.
18.
Fold, V.: Hawes,
J. Chem. Soc. 2102, 1951.
19.
Deno, N. C.; Jaruzel, J.; Schrieseim, A. J.,J. Org. Chem.
19, 155, 1954.
20.
Oldrich Valcl, M. Se.; Irena Memcova; Valelav CUk, CRC
Handbook of Triatylmethane and Xanthene Dyes. 4, 291,
CRC Press, Boca Raton, FL, 1981.
21.
Oldrich Valel, M. Se.; Irena Memcova: Valclav Cuk, CRC
Handbook of Triarymethane and Xanthene Dyes. 3, 233,
CRC Press, Boca Raton, FL, 1981.
22.
Vanallen J. V., J. org. Chem., 23, 1679, 1958.
23.
Koji Nakanishi; Phillippa H. Solomon, Infrared Absorption
Spectroscopy, 1977, page 20.
24.
Douglas, C. N.; Michael P. D., J. Org. Chem. 65, 1977.
25.
Williamson K. L., Macroscale and Microscale
Experiments, D.C. Heath, Lexington, MA, 1989.
26.
Williamson K. L., Macroscale and Microseale organic
Experiments, D.C. Heath, Lexington, MA, 1989, page
660.
27.
Williamson K. L., Macroscale and Microscale organic
Experiments, D.C. Heath, Lexington, MA, 1989, page 649.
28.
Lucas J.; Pressman D, principles and Practice in organic
Chemistry, wiley, New York, 1949, page 429.
29.
Slocum, D.W., and Jennings, C.A. J. Org. Chem. 14, 3653,
1976.
organic
26
,,1~1"fi'
~,~
.
f'll"
'111'
:l
l·~
Figure 1:
IR spectrum of 2,6,2',6',2",6"­
hexamethoxytriphenylcarbinol
(KBr pellet)
200
Q)
(J
~
ro
+oJ
1I
100
~
N
C,\l
......-l
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.
l;")
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Q')
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c:\l
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C'-:J
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r­
c:"'JC\2
C'
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~
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~~
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I
-----,---­
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3000
2000
c:l_­
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o
IR spectrum No.1
..
_
......-l
C";)
C'­
c:o
t:O
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C\l
_
......-l
WavenuITlbers (crn-l)
L--___
ee
co
Res= 2 cln-l
2,6,2' .6' .2" .6" - hexarnethoxytriphenylcarbinol
.....-l
-----,
1000
I
27
t'"
~tll
lIJ~'I>.
. ilr,l
~'jl~
"l~1
1'1
,.
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Fiqure 2:
IR spectrum of 9-(2,6-dimethoxyphenyl)-1,8­
I'"
j
"h
dimethoxyxanthydrol
'.I'
(KBr pellet)
100
~
--I
o
~
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r.;>J
CJ
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+J
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2000
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rn
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1000
Wavenurnbers (cnl.-l)
Ir spectrulU No.2
Res= 2 clll.-1
9--(2.6--diIllethoxyphenyl)--1,B-diuH:·thoxyxanthydrol
toxpAq~u.x~nbs.s ~O mnx~oeds UI
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a.
Transmittance
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ll
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Figure 4:
IR spectrum of fluroboric sesquixanthene
(KBr pellet)
':~ .II
, . ;!~
."
i'
I
I
200
lD
co
C»
Q.)
(;)
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ccC\l
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3000
IR spectrull:.l. No.4
2000
Wavenurnbers (crn.-1)
Res= 2 clTI-l
f'luroboric Sesquixanthene
'I
I
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c:o
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U":I
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1000
ceo
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(~etted .za)l)
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r.tJ
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32
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Figure 7:
XR spectrum of the product obtained from the
bromination of benzyl sesquixanthene
,
1
'_:1
, : :i'''~1
:~ iWi;
I:!
J'II'.;<
w
, t'I~
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f~"
(KBr pellet)
~
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r.JJ
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33
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.
~:
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l
QJl~~!'io
ti
lr:~""
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ij,-,,,,,Ii!
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Figure 8:
IR
spectrum
~~il~
il~'
f~i~
i~li!
I: 'gl~
I
:~~
1
J .',"
11 ".
;::
~~I
: ,,.JIll,!
I:'~I':
product
obtained
bromination of butyl sesquixanthene
I~:
!,L
'::~r,~
of
(KBr pellet)
from
the
"'i
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<":>
'--­
It
=:s
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0
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l!tal~ -­
1275.8 -
0
773.4 -
622 -
872. '7 -
1115.8 -
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N
0
Transn1ittance
J
I
34
~..\
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.....
w,:'1
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~~
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;
•
Figure 9:
IR spectrum of the product obtained from the
oxidation of benzyl trinitrosesquixanthene
'
I~
"'J'
,JllP'li~
,(1
II
'ilflil
II~
!~ ~~:
I~
.,.
)"1'"
~' ",-,
~;~
f!~
(KBr pellet)
--~
I
ex:::>
0)
CO
CO
<:t>
(.) 90
....,
~
~
.
........
o-­
CO
~
+->
.~
C":l
S
rn
IN
o
"<:t4(.....
t>:I
o
CO
CO
C\l
C\l
['"­
to::J
Q
CO
o
o
~
E-<
c:o
-­
I
I
...-j4
.....-i
eJM~
~ r-­
0-1
~~
........
.....-i
3000
IR spectruIU No.9
2000
Wavenurnbers (crn-l)
Res= 2 crn-l
3,3' ,3"--Tribrcnnosesquixanthene
C":l
l'­
"<:t4
0
.....-i
1000
35
i
~,~'l~~
~
,
'~,.,
'1"11
tl'~:
I~:
~:~~I
Figure 10:
IR spectrum of the product obtained from the
nitration of fluoroboric sesquixanthene
~
~r"
:1
I
I~.~~".~.':
j~
-~.
I~
I ·~
;~~:
~.~~:
~,
t~
~~;
~~~
~
(KBr pellet)
S
~
~
r+
~
(';J
00
~
~
~
en
:::l
t'tI
=r
c-+­
::l
~
~
~
....
I
~
S
(')
N
II
~
0
0
0
~
0
0
0
""'"
--
I
S
(';J
-
\tI
~
00
0
0
0
~
=
0­ N
<1
\tI
~
~
00
t'tI
[Jl
~
~
::0
~
0
~
.
[,(]
0
~
~
::l....
I ~. 0Z
~
(1
I~
....
~
~
0
~
~
I
3054.1 -
559.3 -
784 -
1549.7 1465.8 1338.5 1259.4 1164 1~.'Z5- -
1633.B -
0
0
lV
Transmittance
0
....
36
Fiqure 11:
IR spectrum of the product obtained from the
reduction of fluoroboric tribromosesquixanthene
(KBr pellet)
30
At"
-I
I.
~
20
v
Q
~
~
~
~
S
rn
0:>
.....
+-'
10
1:::1
e
r-­
ol:'-:I
~
lD
lD
to
0
Eo-<
C7J ......
"......ll
C'j
•
~
~
a:JC"':l
..0­
~
'"i"
......
o
q
'lQ
I
N
-.t'
~
l,Q
.'
l--I
~
-
~
C\}
co
f;'?
~
-­
3000
IR spectruIll No.ll
2000
Wavenunl.bers (CIll- 1)
1000
Res= 2 cln-l
Reduction of fluoroboric trinitrosesquixanthene
~
"""-'I.
tC:l
CO
l'­
C":J
o:l
.0
lQ
37
~1
~
';;+0'
it'
Ii
Figure 12:
IR spectrum of the product obtained from the
nitration of butyl sesquixanthene
(KBr pellet)
-
C,.:I
~
o
a
o
o
o
o
o
559.3
--------=1
2964.4­ -
3091.7 ­
Transn1ittance
38
'
~.~l
'1.,1
~.~
l,tl
~r:'
Figure 13:
IR
spectrum
of
the
product
obtained
~:~:' ::
r
~<
the reduction of butyl sesquixanthene
:1
".
!r,.~
-
.. Ot.f
(KBr pellet)
from
-I
40
C":l
C:l
C\l
.....-l
Q.I
e..;,
c::
~
-­S
~
0')
..0
U')
0:>
20
COI~
~
~c»
I
- I cO-~lO
ll?
C"1Y.l N
~co.....t:t4......-i
ct:l
t:1
ro
lQ
C\l
.,.......jc:.o
~
co
h
Eo-<
aD "'"
c:J
.,.......j
o
C':l
-­
C:O';.I
t:O
~
~
~
o
-­
..0
o
~
C'?
co
I
3000
2000
Wavenurnbers (crn-i)
I
1000
IR spectrum No.13 Res= 2 cln-l
The product of butyl sesquixanthene nitration reduction
40
Figure 15:
IR spectrum of the product obtained from the
bromination
sesquixanthene
(KBr pellet)
of
fluoroboric
<Ii
:=
::r<Ii
~
D
~
i'<
....
~
00
1
I<'C
00
,Q
S
0
0
0­
.,
~
..,....
('j
~.
11
0
0'
0
11
0
~
I
10"""
S
('j
('~
II
1'.ll
('D
~
C,i1
.,...0
'Z
S
11
~
~
(0
('j
~
1'.ll
~
-~
~
I
-S
0
0
0
~
0'" t-J
('U 0
~ 0
0
0
S
~
D
('U
<:
~
~
0
~
0
0
3054.1 -
0
559.3 -
ftat9­ -
1164 -
1259.4 -
1465.8 1338.5 -
1550.7 -
10~~?P'§ -
1636.5 -
0
Transmittance
ro
~
0
41
Figure 16.
NMR spectrum of the solvent CDC1
Reference:
TMS
3
or'
'T'
'H SPEC TRUll NO. :
SAMPLE: _lIoch.LOUI1.0fJL
_
~:~~~:~::~:~~~::---==l
AMPlITUOE:
SPECTRUM:
• __ l_ .....__ ~
INTEGRAL' __ .. _. __ .. _.
_
H, LEVEL :
I
" " I _TUJOTIlIIi"J
H.lUEL:
.
_
CAIN:
L~
. .. -_.
SWUl' WIDTN:
. .ftNr i~ , . '\
'llTE" ... :
I
lewl • •
.
i"]
J
SWUI' "ME:
.,
10.0
'0
•
10
••
70
1--11.3 ' ••CF.CooH P,.id,nll.' P"idino.,1 pil.ill...."l
--S....!.CHCI.
A.-H
~CHO'
AI : A_lie .iel
I
'
10
•
­
SO
CH.Cf.
_ _ _..,....
"-0
-1==
C<CH·­
'-­
I
1
HC - CH
I
0
DATE:
04/15/9)
I
SEC
OpEIIATOR :
.0
••
,-Doo••n.
]0
1.0
•••
•
);
10
(CH.l.SO
(CH",CO C,eloll......
"""T_ _---:C:;H,::.=OH
CH.plI
I
I
-CH,O-­
I --
CH,
co+- -
CH"cr'
----~H.C."C
-I
CH, A,
-CH N - ­
-C-CH,O--C CH.',':"
~-C CH.-C
- ­ CCH;O­
-CCH.N­
-CH.
- AI CH, 0 ­
- ~C CH, C - ­
-'C CH, It·
-HC"C
-A,CH.N-­
NH .m,,,"
I
ItH am'no
I
0130011 SO!!!C
I
UMA_II! :
- CH.·St-i­
1.. .
I
HIT.ACHI PERKIN ELM!!'"
CHaR' MO. . . ., _
$70{,.·08
r
'H SP£C fllUIl NO. :
SAIIPU :
_
_Jl~tb.loul.lonL
-­
IIlFUlNC£ : -~.
SOLVlNT :
~
_
I
CONC: -----------.----------i
AIlPlITUD£ :
SPlClIIUIi :
1 __ . _
'NllGllAl .
_
-­
H,UYU:
I .. I ' - I [II t:a:J
H.UV£l:
_
5AIN:
LiLI....!!I...J
SWl~ WIDTH:
. .. ----_
. ......
•
IIi~
'llfU ... :
I
10.0
'0
•
10
••
70
f-I '.3 ".CF ,COOH P"id,n.I.1 P,.id,no" I ';IridiMlIII
C. •. CHC'.
A.·H
-+-CHO'
I
10
I
I - - C. Cit,
HC - eH
AI : A_lie
'iet
­
• '0
CH.C'.
",0
1'---­
•. , . " ,
I
'.,.,
]
J
SWUP Tllll:
DllDO/I 'OUC 0
DATl:
i
SIC
04/15/9)
OPlIIATOII :
40
p-
I
I
••
n.
O....
30
1.0
•••
•
1;"
10
(CH, I, SO
(CH,I,CO C'eloh.....
CH.OH
CH,P"
-CH,O-­
I -- -I+- CH, CO
CH'-cr'
----~H.C.,.C
1I[IIUIlS :
- CH.-St+­
CH, A.
-CH.N-­
C CH,O--C CH, ,. ~- C CH, C ....""'...
- ­ CCH,O­
-CCH,N­
-CH •...•
- " , CH. 0 ­
- ~C CH,C-­
-·CCH. OJ­ -HC:C
-A.CH,N-­
tlG
NH Im,dn
I
IIH
I
I
I
I
.....
HITACHI PERt<IN ELM!:R
CHAII' NO.• ~,.aa
~J'.~
42
Fiqure 17:
NMR spectrum of deuterated acetone
Reference:
TMS
,
.
r
'H SPEC nUll NO. :
2
_
SAIIPLE : __~=!'_~~!~!...
lIE, EIlENCE : _.!"S
SOLYEN' :
CONC:
. __ .
AlIl'LnUOE :
snC'RUII:
I
_
~
_
1]
~
INTEGRAL'
H. lEvn :
I .. 1-' i
Ito LEVEL:
_
CAIN:
'il lULl
c..-- r .!I-J
swnl' WIDTH:
----_
.F1UE"e&iwh:
...:-:l!!1--. l!!!l-'" ....
I
1:J
-=]
.wnl' flIIE:
I!I :t001l SOSEC 0
DATE:
10_0
'0
•
10
••
1-, l.:t ,-.C',COOH p,.idinel.1 P,'id.... ' ~ I
----I-- CHO
~
"" : A_lie 'itt
~
70
10
•
C, ,.CHCI,
A,·H
­
40
:
HC - Cit
-----+--­
I
10
]0
•••
•
10
t··
:.IS
11111".115 :
(CH,', SO
(CH, ,,CO C'cloht.....
CH,PIl
- CH,COT - CH,-C-.-­ - CH,'SIT­
",,0
CzCH,--­
I
SEC
OPER,,'OR:
so
CH,Cr,
Pjl'idintl,1l
I
04/15/9]
-
-CH,O-­
-I
----.:H,C~C
CH,A,
-CH,H-­
-C-CH,O--CCH,"'­
~_CCH'C]m;""',,,
- ­ CCH.O­
-CCH,H­
-CH,
-'I<CH,O­
-~CCH,C--·C CH, N­ -ItC;C
....idn
-A, CH,-N-­
ino
HH-­
I
IIH
I
I
I
I
....
HITACHI PERM IN ELMI!R
CH'"
NO.'~J.aa
~".~
43
Figure 18:
NMR spectrum of 9-(2,6-dimethoxyphenyl)-1,8­
dimethoxyxanthydrol
Solvent:
CDC13
Reference:
THS
..
.
'
'H SPECTRUM
S~NPlE
N~
:
)
:
_
9-12.6-dl~~tho.yhpenyll
1.8-dl~~tho.y.anthydrol
REFlRlNCl : -~
SOLVENT:
JlCJ:.L,
CONC:
_
AIiPLITUDl :
SPlCTAUN:
INTlGAAl'
I
.......;
_
.l1
~
H,LEvn:
1'II.rll'lllALJ
",Lun:
II
'00
90
. ..
80
70
II
.10
60
II "'.CF,COOHp"id.n.(.' P"Nlinll ,I Pjl'i41inel'I
C, ,.CHCI,
I
A,H
CH,C',
I
-
I
-~.
AI: A_tie: " ••
NH ,m,61.
II
40
....
, 0
1.0
ICH, ),50
11,0
I
-
-CH,O-­
I
-CH N - ­
--C-CH,O--CCH",---=­
CCH;O­
--CCH,H-­
CH, 0 ­
- =C CH,C-­
I
-
-"C C11, 11­
Ar CHI N- ­
I
I
-I
CN"C1
~-CCH'C
-CH,
II
fm
I
its...
I ­j
'1
i:J
•
I
l:l!I:n!IOI _ OJ
aWup TllIl:
11300/1 10UC 0
DATl :
SIC
04/15/9J
OPlRATOR:
,.I
A!IIU.S :
-CH,
----.:H,C~C
CH, fI,
•
s
(CH,I,CO C'clah.....
- CH,COT -
-- ­_......
i II
FILTER HI;
•
10
':ID~~i~ ·ITJ
SWl:
I
~
CH,Ph
C=CH'-I-­
He - CH
l1li1
I::tIt
_
CAIN:
be
IS
-Ite;c
Imlf'O
IIH
HITACHI PERt<lN
ELM~R
CNa., "0. . . ., _
l7D(u'08
44
Fiqure 19:
NMR spectrum of sesquixanthydrol
Solvent:
CDC~
Reference:
TMS
.
'
'H 5PlCTRuM NO. :
,
SAMPLE: ..5uquLulltheu __
II
I m~~:~':'::_~"_1
II
AII'LITUDI :
I'ICTIIUM :
I"TEGllAl .
.1.l ..
_
H
_
H, LEVU:
I " I . i UL:l_iAl
_
No LUll:
CAl" :
LiLl...!lI...J
IWU' WIDT":
.• ..iT."".----_
. ....
.HI 'T'
•
10.0
'0
•
10
••
70
1-11.3 ".Cr.COOH P,.idin.I.1 p,.idine" I P'......"I
CoH•.CHCI.
A.H
I
-+-CHO
.ift
•
II
]
I
llILllI!IT :::J
IWU' TlIII:
11300/IS0nc
DAU:
0
'~C
05/01")
OplRATOII :
10
~ O _
•
40
••
'-O....n.
3
a
1.0
•••
•
1.0
t'·
IIfllAlIllS :
(CH.I.50
(CH.I,CO C'elo/l......
T.5
CH.OH
CH,pIl
c. CH.-- - - CH, CO, - CH,-C-:-r- ­ CH,-StT-CH,O-----.:H,C-C
1
HC - eH
CH,
-CH N - ­
- C CH,O--C CH, ~ • ...:....
~-C CH, C-r.:"_mbe
- - C(H;O-CCH,N-CH,·il"""
- A. eH. 0 - ~CCH,C--~CCH,,,-HGC
_idn
-A.CH,·N-tonino
CH,C'.
t- -,
I
'" : ' - l i e
flLUII III:
i
NH--
I
11,0
I
I
I
I
I
I
.
- A'-I
,
,
IfH
HfTACHI PERI<IN
~eA
CMllt 1m, . . ., _
S7'I1(' ••.,
45
Figure 20:
NMR spectrum of benzyl sesquixanthene
Solvent:
CDC~
Reference:
THS
.
'
'.
rT'
'H SPEC TRUll NO.:
5
SAIIPLE :
•
Benoyl Selqul •• nthene
I
UFUlNCE : __ nts
SOLVENT: __ • __ .Da:.l,..
COMC :
._ ..... ' ,...
_
_
AMPLITUDE :
SPlC TRUll:
11
INTEGllAl . ::::..:~~~~:~:==
N.LEVEl :
I • I . I llLiDLJ
H, LEvn :
1
S'lIM:
LITTI!lJ
-----""
_......
I
SWUP WIDTH:
r 7 JT::I
•
II
II
'IL TUI ... :
to
•
10
••
70
1-11.3 ' ••C' ,COOH P"id.n.f.1 P"id'Ilf' rI Pjl'i4lilttf'"
C, ,.CHCI,
A, M­
-4-CHO
I
I
I
I
J
T­
II
IWUP TillE:
113OO/l505(C 0
10
•
­
40
I
. .--. I
HC - CII - - - - - l . . ­
NH ,mid..
z.o
] 0
11,0
C· CH, - - ­
-
SIC
-CH,O­
•••
•
A. CH, 0 ­
-
Ar
I1"'
10
t·
IIUI"-" :
ICH,I, SO
(CHoI,CO C'elah......
TU
CH,P"
- CN,'It;-­
- CIl, CO T - CH,-C­
-
::-t
-I
--':H'CJ~
CH, AI
-CI1,N-­
--CCH.O--CCH,·~I~-CCH'C
CCH,O­
-CCH,N­
-CH,
I
I
05/04/9)
OPlR"TOR:
50
CH,CI,
I
AI: "-lie , ...
I
lbLL"I.J
DATE:
100
T
•
""mb...
- : C CH,C-­
~CCH. N­
-IlCoC
M- ­
NH ,mlllO
I
HITACHI PERKIN ELM!!'"
CNallT
110.'.,_
J71YJO ••~
'H SPECTRUII NO.:
5
SAMPLE: __ . __ • __ ••__ •
_
'"nayl S••qul.anth.nl
I
REFERENCE: _ llIS
SOLVENT: _._._.Da:l,...
CONC: ..
..... " ... _
I
AIIPlITUDE :
SPlCTRUM: .... .!.~_._.
IHTEGUl . __ ._.~_ ••
II
H,LEYU:
II
r·. _---y0...-_.
,..
H, LEYU : ....
_
_
J JaLJI
._
U'N:
I
l!
ULIi!lJ
SWUP WIDT":
I
,
_....let.,.
_......
'0
•
10
l-11.3".Cf.COOHp,,;d,n.C.1
l "' r'" ------"-­­
_......' I
_
••
A, H
., ~ . ~
I
..c ..,.
70
.
P"id,nt'11 Pjl'ilI"","
I
C, ,.CHCI,
,I
60
~
•
50
~~,
CH,CI,
C'CH I
-­
I
I
H,O
II
c:nLtJIIIlI. :J
SWUP TillE:
1l300/150UC 0
DATE:
100
L:J
,-;,.....
•flLI'TER• HI:
SIC
0510419]
OPERATOR:
40
t··
10
]0
.~o.,.~··
',",I" •<"......
-II <~..I,I,"'",..'
' - ,",'<
••
z0
T.S
(eH·
CH,O - ­
I'-
CCH O-CCH 0 ­
- CH, CO.!...
-
-ell
'"H'' '-.I.--.:H,C~C
~ ~H, C~
-C
C
-". eH ,0'_
CIl",,"':"­
_ " , CH N.:""<
·e eH.
H.
,",'­
I' - ­
-lIe;c
RElla-liS:
::-I
... - CH"St;­
-
C
bNH·m,no
HITACHI PERK IN ELM!!'R
I
CH.·il"."mb...
J
I
CHIIT 110. . . ., _
~,.
•••
46
Figure 21:
N.MR spectrum of butyl sesquixanthene
Solvent:
CDCl3
Reference:
TMS
T'
'1'
'H SPECTRUM NO.:
6
SAMPLE: _._. __
--­
Butyl lesquixlnthene
REfERENCE:
SOLVENT:
CONC :
I
THS
AMPLITUDE:
SPECTRUM:
INTEGRAL: _
DCCl,
..
_
L __.
_
H, LEVEL:
I -. I.A I ,... LiAI
j
H.LEVEL:
lOAIN:
[2! 1·'.-1
... "'" ........
J..... r::r
-,. ....
•• •
­
SWEEP WIDTH:
C I Ar:r:r
•
fiLTER Ib:
I
10.0
'.0
•
'.0
••
II
7.0
'.0
I 1.3 ".Cf,COOH P,ridi.,C.I P,rid;."71 P,ridMteI"I
C,H•.CHCI,
Ar'H
-....;-------11
I
•
5.0
CH,C',
HC • eH
I
--­
-­
AJ : AP'CIMtlC IIftl
HH ",ud"
4.0
I
AI
I
3.0
Z.O
•••
•
I-
\.0
~
(CH,I,SO
(CH,I,CO C,c/oll.u••
CH,OH
tH,Pft
CH,'COT - CH,·C.....!.
-I-':H'CU
-, CH,O­ - CH."A, -tH N-­
-ttH.O--C·CH,·_,~ --C·CH,·C
I
-CCH.N-­ ~
-C CH,C-­
--CCH,H­
-HC:C
-A,CH
·N-­
I t
NH ,m,na
CCH,O­
CH, 0 ­
I
••
p-D"u.I
",0
C· CH,
_
-
­
Ib
J
..
X
r ;0. I =:J
I CiG
SWEEP TIME:
C1300/150SEC 0
DATE :
J
1
SIC
05104/9 )
OPERATOR:
REMARkS:
TIIS
~
- CH, ·St"":'""
-CH, m,mblll
-
I
HITACHI PERKIN ELMER
CHAR' MO.
1"'_
.C7.".,~
47
Figure 22:
HMR spectrum of the product obtained from the
bromination of benzyl sesquixanthene
Solvent:
Deuterated acetone
Reference:
TMS
'H SPECnUM HO
SAMPLE
I
~ ----------n-------1
'en.yl trlbrOGlo
8eequlManthene
UnRINCE : __ ~
=, _ _
SOLVENT:
CONC:
----------------------1
AII'L1 TUDE :
SPECTIlUII:
INTEGIlAl' _­
•
~~
_
L
_
H. LEVU:
" - T t i l l Il"
j
"J
H, LEVEL:
•
SAIN:
~
-_ /!!!it",
SWU, WIOT":
I
.-:-t"'.
•'IL••T[II• HI;
.
L:J
_
tDLI:!!!KI __ ]
II
SWU, TIllE:
.3OO/15051t 0
DATI:
1
SIC
OVI~/lJ
OPERA TOil :
10.0
to
10
70
10
60
t·
IlfllA1l1lS :
TU
::-I
- CH,'St;­
a.· a..... hC
Il~.
""-'LH' ,=»ERMfN ELMI!R
CHal' 110. • • r _
T7"''''06
48
Figure 23:
NMR spectrum of the product obtained from the
nitration of fluoroboric sesquixanthene
Solvent:
Deuterated acetone
Reference:
THS
..
•
'H SPECTIIUM NO. :
SAIIPLE : •
.. _. __
Fluoroborlc Trlnllro·
•••qul ••nthene
III.UINCE : __ .!!!~
~:~~~N.~~~~~~~_~._.~
AIIPLITUDE :
SPICTRUII: .
U •• __ ._.
INTEGIIAl : .... !_~_ .._.
I
I
",LEVU:
'.0
•
10
••
---l--CHO'
70
.0
•
I---I
,oe,
­
50
c-Ul!llJ
. ..---_
. --""
-
I
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P£R~IN
ELMER
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YILIN QIAO
, hereby submit this thesis to Emporia
state University as partial fulfillment of the requirements
for
an advanced degree.
I
agree that the library of the
University may make it available for use in accordance with
its regulations governing materials of this type. I further
agree that quoting,
this
document
os
photocopying, or other reproduction of
allowed
(including teaching)
for
private
study,
scholarship
and research purposes of a
nonprofit
nature. No copying which involves potential financial gain
will be allowed without written permission of the author.
LLf/;i/} 0 laD
Signature of Author
September 1st, 1994
Date