Synthesis and Reactivity of 5-Heterotruxenes Containing Sulfur or Nitrogen as the Heteroatom

Article abstract of DOI:10.1021/acs.joc.9b01397

This paper presents an alternative path for the synthesis of 5-thiatruxene and the synthetic approach for 5-azatruxene not known so far. A new method for 5-thiatruxene improves the overall reaction yield from 17.5 to 22.6%, diminishes the synthesis time and costs by reducing synthetic steps from 5 to 2, and simplifies the isolation of intermediate and final products. The overall reaction yield for 5-azatruxene is 32.4%. The typical reactivity of both aromatic systems is also demonstrated. Recent research results suggest the use of 5-thiatruxene as the acceptor subunit of soluble blue emitters.

Full text of DOI:10.1021/acs.joc.9b01397

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Article
Synthesis and reactivity of 5-heterotruxenes
containing sulfur or nitrogen as heteroatom
Krzysztof Górski, Justyna Mech-Piskorz, Barbara Lesniewska,
Oksana Pietraszkiewicz, and Marek Pietraszkiewicz
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01397 • Publication Date (Web): 01 Sep 2019
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The Journal of Organic Chemistry
Synthesis and reactivity of 5-heterotruxenes containing sulfur or
nitrogen as heteroatom
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Krzysztof Górski*, Justyna Mech-Piskorz*, Barbara Leśniewska, Oksana Pietraszkiewicz, Marek
Pietraszkiewicz
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Institute of Physical Chemistry, Polish Academy of Sciences; Kasprzaka 44/52, 01-224 Warsaw, Poland
KEYWORDS: truxene, heterotruxene, thiatruxene, azatruxene, synthesis, reactivity, condensation, photocyclization,
alkylation
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ABSTRACT: This paper presents an alternative path of the synthesis of 5-thiatruxene and the synthetic approach for 5-
azatruxene, not known so far. New method for 5-thiatruxene improves an overall reaction yield from 17.5% to 22.6%,
diminishes the synthesis time and costs by reducing synthetic steps from 5 to 2, and simplifies the isolation of intermediate
and final products. The overall reaction yield for 5-azatruxene is 32.4%. The typical reactivity of both aromatic systems is also
demonstrated. Recent research results suggest the use of 5-thiatruxene as the acceptor subunit of soluble blue emitters.1
detect of ions,33,34 explosives35-38 and biologically active
INTRODUCTION
substances.39-41
Truxene is the name of an aromatic hydrocarbon
The nonsymmetrical truxenes containing one or two
consisting of seven condensed rings – three five-membered
different heteroatoms are interesting and relatively little
and four six-membered. Actually, this name is used to
known subclass of truxenes. Currently known
describe the entire family of aromatic compounds that are
representatives of this class of substances are: 5,10-
heteroanalogues of the starting hydrocarbon (Figure 1).
dithiatruxene-15-one,42 5,10-diazatruxene-15-one43 and its
Currently, there are many papers, which describe the
derivatives,44 5-oxatruxene45 and 5-thiatruxene.46 5-
synthesis and physicochemical properties of parent
Thiatruxene was also used to develop stable donor-
hydrocarbon,2-6 and its symmetrical heteroderivatives
acceptor emitters,1 which fulfill requirements for blue
containing nitrogen,7-11 oxygen,12,13 silicon,14 phosphorus15
emitters used in HD displays. In this paper we present an
alternative synthetic route leading to 5-thiatruxene
or sulfur atom 16,17
derivative SCC, and protocol enabling the preparation of
soluble derivative of 5-azatruxene, NCC. Possible
functionalizations, for both π-electronic systems, are also
presented.
RESULTS AND DISCUSSION
5–Thiatruxene
Photocyclization was successfully applied to the
synthesis of 5-oxatruxene.45 There was an idea of adopting
photocyclization procedure for obtaining another 5-
Figure 1. Structure of heterotruxenes.
heterotruxenes, especially containing sulfur or nitrogen.
Initially, an interest of this class of compounds resulted
Application of this synthetic route in 5-thiatruxene
from the possibility of their use for liquid crystal
synthesis, would lead to the shortening of the preparation
displays.12,18-20 However, the progress of optoelectronics
procedure, increase of the overall reaction yield and
and the demand for new stable materials significantly
decrease the production costs. First step of the synthesis
influenced the development of truxene chemistry. Many
blue fluorescent emitters containing truxene moiety are
was direct lithiation of benzo[b]thiophene 1a in
tetrahydrofuran (Scheme 1). Afterwards, the obtained
known and have been used successfully in Organic Light
organolithium compound 2a reacted with iodine to form 2-
21-24
Emitting Diodes or lasers.
The latest reports indicate
iodobenzo[b]thiophene 3a. The synthesis of iododerivative
3a is necessary to perform successful nucleophilic addition
to carbonyl group of the ketone 4. Reaction between 2a and
4 in tetrahydrofuran did not lead to the alcohol 5a. This is
mostly caused by the fact that the ketone 4 in a polar
solvents occurs in the enol form, which efficiently
protonates generated organolithium compound 2a. On the
other hand, direct lithiation of benzo[b]thiophene 1a in
nonpolar solvents, such as toluene, by using n-butyllithium,
is hard to carry out without other reagents. To avoid both
obstacles, 3a was synthesized in tetrahydrofuran and then
reacted with n-butyllithium in toluene to form the
truxene as a core in third generation OLED emitters. The
presence of 5,10,15-triazatruxene in D-A3 system, results in
strong couplings of particular oscillation states of the
singlet and triplet levels, resulting in a significant reduction
of an emission time.25 Truxenes may exhibit semiconductor
properties depending on the heteroatom introduced into
the π-electronic system.26,27 5,10,15-Triazatruxene28-31 and
5,10,15-trithiatruxene32 were used as a charge transporting
materials in a prototype solar cells. Truxenes in general
were used to develop fluorescent sensors that are able to
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organometallic compound 2a. The alcohol 5a, obtained by without further purification. Reaction of 5a in the presence
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nucleophilic addition, was very sensitive to acidic media
and underwent dehydration even on the surface of the silica
gel. Due to the high reactivity of 5a, this compound was used
of methanesulfonic acid in boiling 1,2-dichloroethane led to
the formation of the trimeric compound 6a.
Scheme 1. Synthesis of SCC and NCC via photocyclisation approach.
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The next step in the synthesis of SCC was
photocyclization. Irradiation of 6a with the UV-C light in the
presence of iodine induced conversion of 6a into 7a. The
obtained insoluble brown solid was used to alkylation
without further purification. Introduction of four ethyl
groups into 5-thiatruxene core was conducted in
dimethylformamide saturated with argon. The final
product, SCC, was isolated from the reaction mixture by
column chromatography. Overall yield of this synthetic
route was 22.6%, which is higher of about 5% from that
already known in literature.45 SCC possess good solubility in
most of organic solvents, which facilitate further
functionalization of 5-thiatruxene core. SCC underwent
characteristic reactions for both aromatic systems and
sulfides. Treatment of SCC with bromine allows
introduction up to three bromine atoms into the 5-
thiatruxene core, 8 (Scheme 2) which can be further
exchanged by using lithiation or organopalladium
chemistry. 8 oxidized by m-chloroperbenzoic acid led to the
formation of sulfone 9. In a presence of oxidizers, such as
hydrogen peroxide or m-chloroperbenzoic acid, SCC can be
converted into sulfoxide (OS)CC as racemic mixture or
sulfone (O2S)CC. Oxygenated 5-thiatruxenes, due to
ambipolar character of the molecules, possess good
solubility in both polar and nonpolar solvents. This
property may cause some problems during purification of
those substances, which results in lower reaction yield.
Introduction of one sulfur atom into the truxene core breaks
its symmetry, allowing monofunctionalization of 5-
thiatruxene system. For example, sulfone (O2S)CC in a
presence
of
lithium
2,2,6,6-tetramethylpiperidide
underwent direct lithiation. Generated organolithium
compound, after reaction with iodine, forms iododerivative
10, which is useful reagent for further functionalization of
5-thiatruxene core.
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Scheme 2 Reactivity of SCC.
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5–Azatruxene
Scheme 3 Condensation process of 11
Another target, among the family of non-symmetrical
heterotruxenes, was the synthesis of 5-azatruxene. Our
experience, gained in the synthesis of previous compounds,
5-oxa- and 5-thiatruxene was utilized in the first approach.
Due to the lower reactivity of 1b, in comparison to 1a, the
direct lithiation was carried out in boiling ether in the
presence of an excess of n-butyllithium. The generated
organometallic derivative 2b reacted with iodine to form
3b. The addition of the organolithium compound 2b to the
ketone 4 was done in toluene, analogously as in the case of
SCC. The obtained alcohol 5b showed higher tendency to
dehydration, compared to the sulfur analogue 5a. The
trimer 6b, created after dehydration of the 5b, appeared to
be relatively unstable, which was observed as slowly
darkening in contact with air. The high reactivity of 6b can
be explained by the presence of nitrogen atom, whose
donating properties increase the electron density of the π-
electron system, which in turn, significantly destabilizes the
HOMO level, making 6b more prone to oxidation. The
photocyclisation of trimer 6b, performed immediately after
isolation, leads to a black substance. The following
ethylation resulted in trace amount of NCC. Due to the high
reactivity of trimer 6b, an efficient synthesis of NCC, by
using photocyclization, turned out to be impossible. The
synthesis of NCC needed an alternative path. The
introduction of a nitrogen atom into an aromatic system can
be accomplished, for example, by the use of catalytic N-
arylation,47 reduction of nitro compounds48 or
decomposition of aryl azides.49 The first step of the new
synthetic pathway was the cyclotrimerization of 2'-
bromoacetophenone 11, leading to the bromoderivative 12.
Unfortunately, despite many attempts, the condensation of
11 in trifluoromethanesulfonic acid at 130°C turned out to
Table 1. Optimization of condensation process of 17.
Conditions
Reaction yield
for 12
HCl, HC(OEt3) (1.2eq), benzene
HSO3Cl, DCM
5%
0%
HSO3Cl, Si(OEt)4 (1eq), DCM
HSO3Cl, Si(OEt)4 (2eq), DCM
32%
75%
Our studies showed that the condensation of 11, leading
to 12, can be performed without using very strong
trifluoromethanesulfonic acid and high temperatures (
Scheme 3). The direct application of the methods used
during the cyclotrimerization of acetophenone, for example,
condensation in the presence of ethyl orthoformate and
hydrogen chloride did not lead to satisfactory yields (Table
1).51 One of the factors affecting the result of the reaction is
the lower reactivity of the ketone 11, compared to
acetophenone, therefore the use of a stronger acid should
generate enol form 11’ in a higher concentration, increasing
the condensation yield. Chlorosulfonic acid plays a double
role in the cyclotrimerization reaction. Firstly,
chlorosulfonic acid, as a strong acid, is responsible for the
shift of the keto-enol equilibrium and condensation of 11.
Secondly, the presence of the reactive Cl–S bond is
responsible for binding water, produced during the
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be difficult to repeat. The obtained reaction yield was
40%, which was about half as low as in the literature one.
For this reason, it was necessary to optimize the
cyclotrimerization of 11.
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cyclotrimerization. Unfortunately, the chlorosulfonic acid These types of systems are very susceptible to
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alone does not induce condensation at room temperature,
however, the introduction of tetraethoxysilane to the
reaction mixture allows to obtain 12 with a yield reaching
75%. It turns out that tetraethoxysilane present in the
reaction mixture, acts not only as a scavenger of produced
water. Lowering the condensation temperature from 130°C
to 25°C suggests a significant reduction of activation energy.
Thus the conclusion is that, the tetraethoxysilane increases
the reactivity of 11 in the condensation reaction.
Interaction between 11 and tetraethoxysilane results in
silyl ether of the enol form (Scheme 4).
electrophilic attack, because of the stabilizing properties of
the silicon atom towards the cation in the β position.52 The
reaction between ether 13 and protonated ketone 11’’
resulted in dimer formation 15, which in turn reacted with
11’’ giving the trimer 17. As a result of following
electrocyclization and elimination, 12 was obtained as a
final product. Strong acid and tetraethoxysilane can be also
generated In situ by performing condensation in ethanol in
presence of silicon tetrachloride.53
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Scheme 4. Condensation mechanism in a presence of tetraethoxysilane.
The next step of the synthetic route was a single lithiation
of 12, leading to an organometallic compound 20, which
afterwards reacted with tosyl azide, to form
monoaziderivative 21 (Scheme 5). The isolation of the
product by column chromatography turned out to be
problematic, because both substrates and byproducts
possessed similar polarity to 21. The solution of this
obstacle was thermal decomposition of reaction mixture in
boiling 1,2-dichlorobenzene.
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Scheme 5. Synthesis of NCC and its bromoderivative 27.
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Nitrene 22, created during thermolysis, underwent
shaped structure is chemically and physically stable which
is crucial in construction of new materials for
optoelectronic application. This was confirmed by recent
studies involving (SO2)CC, where the obtained emissive
materials reveal high external quantum efficiencies at
brightness up to 10 000 cd/m2 and good thermal stability.1
The synthetic route for unknown so far compound, NCC,
opens a new research field in truxene-based donor-
acceptor systems. In D-A molecules, heterotruxenes can act
both as a donor (NCC) or acceptor ((SO2)CC). In this case,
essential is the adjustment of energy levels of individual
heterotruxene subunits, which is possible by introduction
of particular heteroatom, or changing its oxidation state, as
in the case of sulfur. Fast, effective and remarkable yield
performance was developed, as described in this paper,
giving rise to better accessibility of new truxene compounds
which will have a great impact on the advanced organic
electronics. The crystallographic and other experimental
data placed in the electronic supporting info will be
discussed in detail in a separate paper.
insertion into the C–H bond of the central benzene ring to
form the carbazole derivative 23. At this step, the product
of thermal decomposition 23, was separated from the
substrates of the previous reaction. The final step was
alkylation of 23 to give the N-ethylderivative 24.The
bromoderivative 24 was double lithiated and generated
organometallic compound 25 was used in the reaction with
pentan-3-one to form alcohol 26. Diol 26 in the presence of
a boron trifluoride underwent cyclization leading to NCC. In
order to obtain higher reaction yield, the temperature
during cyclization had to be controlled. Every drop of
borontrifluorideetherate added to the reaction mixture,
significantly increased the temperature. The uncontrolled
reaction resulted in the creation of elimination byproducts,
which reduced the yield and made the isolation of NCC
difficult. In this case separation of the reaction mixture
using liquid chromatography with reversed-phase polarity
was necessary. The presence of one nitrogen atom allowed
selective and efficient functionalization of the 5-azatruxene
core, e.g. the reaction with N-bromosuccinimide resulted in
monobromoderivative 27 formation. 27 can be used to the
further functionalization of 5-azatruxene core.
EXPERIMENTAL
General Information. All solvents used were analytical
grade. Toluene and tetrahydrofuran used in lithiation
reaction were freshly distilled from LiAlH4 under argon
CONCLUSIONS
Numerous synthetic steps and low reaction yield are the
obvious obstacles to get new heterotruxene compounds.
Application of completely new synthetic approach, or
optimization of the synthesis of already known
heterotruxenes is one of the goals of this research
considering benefits from this class of compounds. The star-
atmosphere.
Benzo[b]thiophene,
indan-1-one,
2’-
bromoacetophenone and tetraethoxysilane were delivered
with ABCR. Mass spectra was collected at Applied
Biosystems 4000Q TRAP with electron impact as ionization
method. 1H and 13C NMR spectra were measured at Bruker
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DRX 500MHz in CD2Cl2 or C6D6. Shift of the residual peak of
solvents was taken as an internal chemical shift.
NMR (126 MHz, CD2Cl2) δ: 144.5, 143.7, 143.5, 142.3, 140.3,
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140.2, 139.5, 139.4, 136.7, 133.9, 133.1, 126.2, 125.4, 124.9,
124.2, 123.7, 123.3, 123.3, 123.2, 123.0, 121.5, 120.2, 120.0,
42.7, 38.3; HRMS (EI – TOF) m/z (M+): Calcd for C26H18S
362.1129; Found 362.1117; Elemental analysis (%). Calcd
for C26H18S: C 86.15, H 5.01; Found: C 86.21, H 4.98
2-(indan-2-ylideno)-indan-1-one
4.45 To 100 mL of
–
methanol 26.4 g (0.2 mol) of indan-1-one, 89.2 mL
(d = 0.964 g/mL, 0.4 mmol) of tetraethoxysilane and
10.68 mL (d = 1.836 g/mL, 0.2 mol) of H2SO4 was added.
Mixture turns to yellow. After 5 days of stirring at room
temperature the mixture was filtrated. The solid was
washed with methanol until colorless filtrate was obtained.
Crude product was purified by Soxhlet extraction with
toluene and filtrated. 12.44 g of 4 as a pale yellow solid state
was obtained with a yield 50.57 %. 1H NMR analysis
confirms the structure of the compound.
10,10,15,15-tetraethyl-5-thiatruxene – SCC. To 3.65 mL of
hexane 1.32 g (3.65 mmol) of 3-(3-(benzo[b]thiophene-2-
yl)-1H-inden-2-yl)-1H-indene 6a and 92.7 mg (0.365
mmol) of iodine was added, then the irradiation of mixture
with UV-C lamp (55 W) was started. After 3 h solvent was
evaporated and brown solid was collected. Next it was
suspended in 18.25 mL of dimethylformamide (saturated
with argon in 0°C for 1 h). Afterwards 1.8 g (32.16 mmol) of
shredded KOH and 2.4 mL (32.16 mmol, d = 1.46 g/mL) of
ethyl bromide was added. After 24 h of stirring 20 mL of
water was added to the brown solution. The mixture was
extracted three times with 10 mL of dichloromethane,
combined organic phases were dried over MgSO4 and
evaporated. Crude product was purified via column
chromatography using silica gel as the stationary phase and
10% dichloromethane in hexane as eluent to obtain
880.42 mg (51.2%) of SCC as a white solid, mp 207-209°C.
1H NMR (500 MHz, CD2Cl2) δ: 8.95 (d, J = 8.1 Hz, 1H), 8.37
(d, J = 7.1 Hz, 1H), 8.20 – 8.16 (m, 1H), 8.06 (dd, J = 7.7, 1.0
Hz, 1H), 7.60-7.51 (m, 5H), 7.48-7.40 (m, 3H), 3.13 (dq, J =
14.4, 7.2 Hz, 2H), 3.00 (dq, J = 14.6, 7.3 Hz, 2H), 2.34-2.26
(m, 4H), 0.24 (t, J = 7.3 Hz, 6H), 0.22 (t, J = 7.3 Hz, 6H); 13C
NMR (126 MHz, CD2Cl2) δ: 152.0, 151.9, 145.9, 142.5, 140.7,
140.4, 140.1, 137.7, 135.7, 134.3, 132.70, 132.68, 127.08,
127.05, 126.9, 126.6, 126.4, 125.9, 124.1, 123.9, 123.1,
122.3, 122.1, 121.5, 58.8, 57.8, 29.7, 29.4, 8.5, 8.4; HRMS (EI
– TOF) m/z (M+): Calcd for C34H32S 472.2225, Found
472.2215; Elemental analysis (%). Calcd for C34H32S: C
86.39, H 6.82; Found: C 86.44, H 6.88.
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2-iodobenzo[b]thiophene – 3a. To 20 mL of tetrahydrofuran,
2.68 g (20 mmol) of benzo[b]thiophene 1 was added. The
obtained mixture was cooled to -40ºC and 12 mL (2.5 M, 30
mmol) of n-butyllithium solution in hexane was added, then
white participate was formed. After 1 h of stirring in
constant temperature the solution of 7.62 g (30 mmol) of
iodine in 20 mL of THF was added, then the solution was
elevated to room temperature. After extraction with 50 mL
of saturated aq solution of Na2S2O3 and 20 mL of ethyl
acetate, organic layer was separated, dried over MgSO4 and
evaporated. Crude 2-iodobenzo[b]thiophene 3 (5.2 g
~100%) as a white solid was taken to the next step without
further purification. NMR analysis is in accordance with
literature data.54 1H NMR (500 MHz, CDCl3) δ: 7.41-7.45 (m,
2H), 7.64 (s, 1H), 7.81- 7.92 (m, 2H)13C NMR (126 MHz,
CDCl3) δ: 79.3, 121.3, 122.4, 124.5, 124.6, 133.9, 140.9,
144.5
3-(3-(benzo[b]thiophene-2-yl)-1H-inden-2-yl)-1H-indene
6a. To 60 mL of toluene, freshly distillated from LiAlH4
under argon atmosphere, 5.2 (20 mmol) 2-
–
g
iodobenzo[b]thiophene 3a was added. Obtained mixture
was cooled to -78oC and 8 mL (2.5 M, 20 mmol) of n-
butyllithium solution in hexane was added, then white
participate was formed. After 10 min the solution of 4.92 g
(20 mmol) 2-(indan-2-ylideno)-indan-1-one 4 in 100 mL of
toluene was added dropwise within 1 h. After that the
solution was slowly elevated to room temperature (~1 h).
There was a change of the color to dark red. After 3 h NH4Cl
solution (1.07 g, 20 mmol, in 20 mL of water) and 100 mL of
dichloromethane was added. Organic phase was separated
and evaporated. Obtained dark oil residue was dissolved in
20 mL of 1,2-dichloroethane followed by the addition of 2.4
g (20 mmol) of MgSO4 and 1.3 mL (d = 1.48 g/mL, 20 mmol)
methanesulphonic acid. After 30 min of stirring in reflux, to
cool down, the mixture, 40 mL of water and 60 mL of
dichloromethane, was added. Organic phase was separated
and water phase was extracted 3 times with 30 mL of
dichloromethane. Combined organic phases were dried
over MgSO4 and evaporated. Crude product was purified via
column chromatography using silica gel as the stationary
phase and 10% dichloromethane in hexane to obtain 3.20 g
(44.1%) of a final product 6a as a white solid, m.p. 194°C. 1H
NMR (500 MHz, CD2Cl2) δ: 7.78 – 7.72 (m, 3H), 7.58 (d, J =
7.3 Hz, 1H), 7.48 (d, J = 7.4 Hz, 1H), 7.43 (s, 1H), 7.39 (td, J =
7.5, 0.5 Hz, 1H), 7.35 – 7.27 (m, 3H), 7.16 (d, J = 7.5 Hz, 1H),
7.13 (td, J = 7.4, 1 Hz, 1H), 7.05 (td, J = 7.5, 0.5 Hz, 1H), 6.64
(t, J = 2.2 Hz, 1H), 3.95 (s, 2H), 3.53 (d, J = 2.1 Hz, 2H); 13C
5-oxo-10,10,15,15-tetraethyl-5-thiatruxene – (SO)CC. To the
mixture of acetic acid and dichloromethane (11 mL and 4
mL respectively), 130 mg (0.275 mmol) of SCC and 0.102
mL (0.825 mmol) of a 30% aqueous solution of hydrogen
peroxide was added. After 24 h, 10 mL of water and 10 mL
of dichloromethane were added. The organic layer was
washed with an aqueous NaHCO3 solution, dried over
MgSO4, filtrated and evaporated. The crude product was
adsorbed at SiO2 and purified via column chromatography
using silica gel as a stationary phase and 5% → 20% ethyl
acetate in hexane as an eluent. After evaporation of the
fractions, the product was dissolved in methanol and
aqueous NaCl was added. The obtained white solid (mp.
194-196°C) was collected by filtration to give 79 mg
(58.8%) of the product (SO)CC. 1H NMR (500 MHz, CD2Cl2)
δ: 8.59 – 8.52 (m, 2H), 8.38 (dd, J = 6.0, 2.4 Hz, 1H), 8.12 (dd,
J = 7.5, 0.9 Hz, 1H), 7.73 (t, J = 7.4Hz, 1H), 7.60 (t, J = 7.4 Hz,
1H), 7.56 – 7.44 (m, 6H), 3.04 – 2.87 (m, 4H), 2.32 – 2.14 (m,
4H), 0.33 (t, J = 7.4 Hz, 3H), 0.28 (t, J = 7.3 Hz, 3H), 0.19 (t, J
= 7.3 Hz, 3H), 0.16 (t, J = 7.3 Hz, 3H); 13C NMR (126 MHz,
CD2Cl2) δ: 153.3, 152.7, 146.0, 145.3, 145.2, 145.0, 143.3,
139.1, 138.5, 137.00, 136.98, 133.9, 132.3, 129.1, 129.0,
128.6, 128.2, 127.9, 127.8, 127.1, 125.4, 124.5, 122.9, 122.6,
58.8, 57.8, 30.4, 30.0, 29.5, 29.5, 8.9, 8.8, 8.71, 8.68; HRMS
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(EI – TOF) m/z (M+):Calcd for C34H32SO 488.2174, Found mL (4 mmol d = 3.119 g/mL) of bromine was added. The
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488.2172; Elemental analysis (%). Calcd for C34H32OS: C
83.56, H 6.60; Found: C 83.71, H 6.68.
mixture was heated to the boiling temperature- the solution
became muddy. After 1 h it was cooled down, to add 20 mL
of hexane and then continuously cooled down to reach 0°C.
The mixture was filtered to get 8 as a white solid. Step II
(oxidation): The obtained bromination product 8 was
dissolved in 10 mL of dichloromethane and 737 mg (3
mmol, C = 70%) of water-stabilized m-chloroperbenzoic
acid were added. After 1 h the whole mixture was
evaporated and the solid residue obtained was washed with
aqueous NaOH solution, 280 mg (6 mmol) in 10 mL of water,
and mixture of 10 mL of water and 20 mL of methanol. After
drying, 904 mg (91%) of 9 in a form of white solid were
obtained. NMR analyzes are in accordance with literature
data.46 1H NMR (500 MHz, CDCl3) δ: 8.56 (d, J = 1.1 Hz 1H),
8.55 (d, J=8.5 Hz,1H), 8.18 (d, J = 8.3 Hz, 1H), 7.85 (d, J = 8.1
Hz, 1H), 7.75 (dd, J = 8.1 Hz, 1.3 Hz, 1H), 7.58–7.64 (m, 4H),
2.70–2.86 (m, 4H), 2.12–2.25 (m, 4H), 0.31 (t, J = 7.2 Hz, 6H),
0.27 (t, J=7.2 Hz, 6H); 13C NMR (126 MHz, CDCl3) δ:155.5,
154.5, 146.7, 144.7, 145.6, 139.3, 137.0, 136.8, 135.3, 133.6,
132.7, 131.2, 130.7, 130.6, 130.3, 128.3, 127.0, 126.7, 126.6,
126.1, 125.6, 124.3, 123.9, 123.8, 58.9, 57.8, 29.8, 29.7, 8.9,
8.8; HRMS (EI – TOF) m/z (M+): Calcd for C34H29SO2Br3
737.9438, Found 737.9405; Elemental analysis (%). Calcd
for C34H29O2SBr3: C 55.08, H 3.94; Found C 55.16, H 3.98.
5,5-dioxo-10,10,15,15-tetraethyl-5-thiatruxene – (SO2)CC.
283.6 mg (0.6 mmol) of SCC and 443.75 mg (1.8 mmol,
70%) of m-chloroperbenzoic acid were introduced into 5
mL of dichloromethane. After 1 h, 5 mL (3 M) of aqueous
NaOH solution was added. The organic layer was separated,
the aqueous layer was washed with 5 mL dichloromethane
and the combined extracts were dried over MgSO4, filtrated,
evaporated and dried in vacuo to give 283.2 mg (93.61%) of
white solid, mp 221-223°C. NMR analyzes are in accordance
with literature data.46 1H NMR (500 MHz, CDCl3) δ: 8.68 –
8.77 (m, 1H). 8.45 (d, J = 8.1 Hz, 1H), 8.37 (d, J = 7.3 Hz,
1H),8.00 (dd, J = 7.6, 1.3 Hz, 1H), 7.72 (ddd, J = 8.3, 7.4, 1.4
Hz, 1H), 7.59 (td, J = 7.5, 0.7 Hz, 1H), 7.43 – 7.52 (m, 6H),
2.89 (m, J = 14.0, 7.2 Hz, 4H), 2.21 (m, J = 14.1, 7.4 Hz, 4H),
0.27 (t, J = 7.3, 12H); 13C NMR (126 MHz, CDCl3) δ:153.2,
152.3, 146.3, 145.5, 145.2, 139.9, 138.4, 138.1, 136.6, 133.2,
131.9, 129.6, 129.4, 129.3, 128.6, 127.8, 127.6, 127.4, 126.9,
125.3, 125.0, 122.6, 122.5, 122.0, 58.3, 57.3, 29.7, 29.6, 8.8,
8.7; HRMS (EI – TOF) m/z (M+):Calcd for C34H32SO2
504.2123, Found 504.2128; Elemental analysis (%). Calcd
for C34H32O2S: C 80.92, H 6.39; Found: C 81.06, H 6.47.
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6-iodo-5,5-dioxo-10,10,15,15-tetraethyl-5-thiatruxene – 10.
To 1 mL of tetrahydrofuran 0.204 mL (1.2 mmol,
d = 0.83 g/mL) 2,2,6,6-tetramethylpiperidine was added
and cooled to -78°C. After that 0.48 mL (1.2 mmol, 2.5 M) of
a solution of n-butyllithium in hexane was added and the
mixture was elevated to room temperature. White solid
precipitation was obtained in one minute. The mixture was
kept at constant temperature 10 min and then cooled down
and the solution of 302.5 mg (0.6 mmol) of (SO2)CC in 6 mL
of tetrahydrofuran was added. The mixture was dark green
at this step. After 0.5 h, 304.8 mg (1.2 mmol) of iodine was
added and the mixture was elevated to room temperature,
followed by the addition of 600 mg of Na2S2O3 and 5 mL of
water. The organic phase was separated, whereas the
aqueous layer was extracted with 6 mL of ethyl acetate. The
combined extracts were dried over MgSO4 and evaporated
to give 373.2 mg (98.7%) of a gray-brown solid. In order to
obtain a pure analytical sample, the product 10 was purified
via column chromatography using silica gel as a stationary
phase and 20% ethyl acetate in hexane solution as an eluent.
In this way, iododerivative 10 was obtained in the form of a
pale yellow solid, m.p. 231°C.1H NMR (500 MHz, CD2Cl2) δ:
8.69 (d, J = 7.8 Hz, 1H), 8.51 (d, J = 8.1 Hz, 1H), 8.39 (d, J =
7.1 Hz, 1H), 8.00 (d, J = 7.7 Hz, 1H), 7.56 – 7.46 (m, 6H), 7.41
(t, J = 7.9 Hz, 1H), 2.95 – 2.89 (m, 2H), 2.88 – 2.76 (m, 2H),
2.30 – 2.16 (m, 4H), 0.29 – 0.26 (m, 6H), 0.26 – 0.23 (m, 6H);
13C NMR (126 MHz, CDCl3) δ: 153.0, 152.4, 148.2, 147.3,
146.5, 144.4, 143.2, 140.6, 137.8, 134.2, 131.4, 131.1,
129.94, 129.85, 129.6, 129.2, 127.8, 127.6, 127.3, 125.8,
125.2, 123.0, 122.7, 100.4, 58.8, 57.8, 30.00, 29.9, 8.9, 8.8;
HRMS (EI – TOF) m/z (M+): Calcd for C34H31SO2I 630.1090,
Found 630.1104 . Elemental analysis (%). Calcd for
C34H31O2SI: C 64.76, H 4.96; Found: C 64.69, H 4.97.
1,3,5-tri(2-bromophenyl)benzene – 12. To 15 mL of
dichloromethane 1.35 mL (10 mmol, d = 1.476 g/mL) of 2'-
bromoacetophenone, 666 μL (10 mmol, d = 1.753 g/mL) of
chlorosulfonic acid and 2.94 mL (20 mmol, d = 1.032 g/mL)
of tetraethoxysilane was added. There was a change in the
color of the solution to red, which was darkening with time.
After 48 h, 10 mL (1 M) aqueous Na2CO3 solution was
added. The produced silica was filtered on Celite and
washed 3 times with 10 mL of dichloromethane. The
organic phase was separated, dried over MgSO4, filtrated
and evaporated. The crude product was suspended in 5 mL
of a 20 % solution of acetone in hexane and filtered to give
1.36 g (75%) of 12 as a pale yellow solid, mp 158-160°C.55
NMR analysis is in accordance with literature data.56 1H
NMR (400MHz, CDCl3) δ: 7.69 (d, J = 7.8 Hz, 3H), 7.51-7.26
(m, 9H), 7.22 (m, 3H); 13C NMR (99MHz, CDCl3) δ: 142.3,
140.9, 133.6, 131.9, 130.1, 129.4, 128.0, 122.9; LR MS FD:
543.80 (M+).
Tosyl azide. To the solution of water and acetone (300 mL
and 500 mL respectively) 71.5 g (1.1 mol) of NaN3 was
added. Than the solution of 190.7 g (1 mol) of p-
toluenesulfonyl chloride in 500 mL of acetone was added
quickly during intense stirring. The mixture was heated up,
what results in the formation of a two-phase system. After
2 h, the acetone was evaporated under reduced pressure, in
temperature not exceeding 35°C. The aqueous layer was
extracted with 200 mL of dichloromethane and the
separated organic layer was washed with 2×200 mL of
water and dried over Na2SO4, then was filtrated and
evaporated not exceeding 35°C. 195.24 g (99%) of a
colorless liquid was obtained.57 NMR analysis is in
accordance with literature data.58 1H NMR (300 MHz, CDCl3)
δ: 7.80 (d, J=8.4 Hz, 2H), 7.38 (d, J=8.7 Hz, 2H), 2.45 (s, 3H);
13C NMR (75 MHz. CDCl3) δ: 146.0, 135.1, 130.0, 127.2, 21.6.
2,8,12-tribromo-5,5-dioxo-10,10,15,15-tetraethyl-5-
thiatruxene – 9. Step I (bromination): 472 mg (1 mmol) of
SCC was dissolved in 10 mL of dichloromethane and 0.207
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1,3-(2-bromophenyl)-9-ethylcarbazole – 24. Step I (bromine dark brown. Next the solution was slowly elevated to room
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to azide exchange): To 20 mL of tetrahydrofuran, 2.715 g
(5 mmol) of 1,3,5-tri(2-bromophenyl)benzene 12 was
added. Obtained mixture was cooled down to -78oC and
2.1 mL (2.5 M, 5.25 mmol) of n-butyllithium solution in
hexane was added - mixture turns brown. After 1 h of
stirring in constant temperature 1 g (5.5 mmol) tosyl azide
was added. Color of the solution becomes dark brown. Then
the mixture was slowly elevated to room temperature. After
12 h the 5.25 mL (1 M) of aq solution of NH4Cl and 10 mL of
dichloromethane was added. Organic phase was separated
whereas water phase was extracted with 10 mL of
dichloromethane. Mixed organic phases were dried over
MgSO4 and evaporated. Crude product was purified via
column chromatography using silica gel as the stationary
phase and 10% dichloromethane in hexane as eluent to
obtain 2.39 g of monoazide derivative 21 in the form of pale
yellow oil. The product was contaminated with substrates.
Step II (nitrene insertion): 21 was dissolved in 4.74 mL of
o-dichlorobenzene and the mixture was heated to
temperature 180°C. The mixture turns dark brown. After
1 h the reaction was cooled to room temperature and crude
product was purified via column chromatography using
silica gel as a stationary phase and hexane→10%
dichloromethane in hexane→5% ethyl acetate in hexane as
an eluent. Obtained 1.48 g of carbazole derivative 23 as a
pale orange solid was used in the next step. Step III
(carbazole alkylation): To 6.2 mL of dimethylsulphoxide,
1.48 g (3.1 mmol) of 23 and 347.22 mg (6.2 mmol) of
shredded KOH was added. After that 0.465 mL (6.2 mmol,
d = 1.46 g/mL) of ethyl bromide was added dropwise. After
24 h 6.2 mL of water and 6.2 mL of dichloromethane was
added. Organic phase was separated, whereas water phase
was extracted with 6.2 mL of dichloromethane. Mixed
organic phases were dried over MgSO4 and evaporated.
Crude product was purified via column chromatography
using silica gel as a stationary phase and 5→10%
dichloromethane in hexane as an eluent. 1.46 g (58% after
3 steps) of 24 as a white solid was obtained, m.p. 175°C. 1H
NMR (500 MHz, CD2Cl2) δ: 8.20 (d, J = 1.8 Hz, 1H), 8.14 (d, J
= 7.73 Hz, 1H), 7.76 (dd, J = 8.1, 1.3 Hz, 1H), 7.72 (dd, J = 8.1,
1.1 Hz, 1H), 7.59 (dd, J = 8.1, 2.5 Hz, 1H), 7.53 (dd, J = 7.6, 1.7
Hz, 1H), 7.48 (m, 2H), 7.42 (m, 2H), 7.36 (ddd, J = 10.0, 6.1,
2.1 Hz, 1H), 7.29 (d, J = 1.8 Hz, 1H), 7.26 (ddd, J= 1H), 7.23
(ddd, J = 8.0, 7.4, 1.7 Hz, 1H), 3.99 (dq, J = 14.3, 7.1 Hz, 1H),
3.84 (dq, J = 14.4, 7.2 Hz, 1H), 1.03 (t, J =7.2Hz, 3H); 13C NMR
(126 MHz, CD2Cl2) δ: 143.1, 141.5, 141.2, 136.6, 133.5,
132.7, 132.3, 132.2, 131.8, 130.2, 130.0, 128.8, 127.8, 127.6,
126.4, 125.4, 124.3, 124.2, 123.4, 123.4, 121.0, 120.5, 119.7,
109.5, 39.1, 14.3; HRMS (EI – TOF) m/z (M+): Calcd for
C26H19NBr2 502.9884, Found 502.9870; Elemental analysis
(%). Calcd for C26H19Br2N: C 61.81, H 3.79, N 2.77; Found: C
61.87, H 3.81, N 2.71.
temperature. After 12 h the 3 mL (1 M) of aq solution of
NH4Cl and 10 mL dichloromethane was added. Organic
phase was separated and water phase was extracted with
10 mL of dichloromethane. Mixed organic phases were
dried over MgSO4 and evaporated. Crude product was
dissolved in toluene and adsorbed with 4 g of silica gel.
Product was purified via column chromatography using
silica gel (40 g) as a stationary phase and 3→10% ethyl
acetate in hexane as an eluent to obtain 503 mg (64.6%)of
26 as a colorless oil. Step II (rings formation): To 10 mL of
dichloromethane, freshly distilled from H2SO4, 518.6 mg
(1 mmol) of 26 was added. Obtained mixture was cooled to
0oC and 0.278 mL of Et2O-BF3, freshly distilled under argon
atmosphere, was slowly added. Mixture turns yellow, and
started darkening during the reaction. After 30 min 1 mL of
methanol was added and solution was evaporated. Crude
product was purified via column chromatography using
aluminum oxide as stationary phase and hexane as an
eluent to obtain 404.7 mg (86.5%) of NCC as a white solid,
mp 181-182 °C. (In the case of many byproducts, presented
in the reaction mixture after step II, purification with RP18
as stationary phase and acetonitrile as eluent is necessary).
1H NMR (500 MHz, C6D6) δ: 8.67 (d, J = 7.9 Hz, 1H), 8.43 (d, J
= 7.9 Hz, 1H), 7.86 (d, J = 7.6 Hz, 1H), 7.44 – 7.20 (m, 9H),
4.33 (q, J = 7.0 Hz, 2H), 3.11 (m, 4H), 2.17 (m, 4H), 0.67 (t, J
= 7.0 Hz, 3H), 0.42 (t, J = 7.3 Hz, 6H), 0.32 (t, J = 7.3 Hz, 6H);
13C NMR (126 MHz, C6D6) δ: 151.5, 151.2, 145.3, 145.0,
143.3, 142.0, 140.6, 139.0, 132.8, 127.9, 126.6, 126.4, 126.2,
126.0, 125.6, 125.3, 124.9, 123.6, 122.8, 122.5, 122.3, 122.2,
120.2, 112.2, 58.2, 56.9, 42.1, 30.0, 29.8, 12.5, 8.6, 8.4; HRMS
(EI – TOF) m/z (M+): Calcd for C36H37N 483.2926, Found
483.2916; : Elemental analysis (%). Calcd for C36H37N: C
89.39, H 7.71, N 2.90; Found: C 89.45, H 7.73. N 2.87.
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8-bromo-5,10,10,15,15-pentaethyl-5-azatruxene – 27. 43.5
mg (0.09 mmol) of NCC and 24 mg (0.135 mmol) of N-
bromosuccinimide was added to 4.5 mL dichloromethane.
The progress of the reaction was monitored on TLC. After
4 h 10 mL of dichloromethane and 10 mL of saturated
aqueous NaHCO3 solution were added. The phases were
separated and the organic phase was dried over MgSO4 and
evaporated. The solid residue was suspended in methanol
and filtered to give 50.46 mg (~100%) of 27 as a white
solid. 1H NMR (500 MHz, CD2Cl2) δ: 8.65 (s, 1H), 8.30 (d, J =
7.8 Hz, 1H), 7.91 (d, J = 7.6 Hz, 1H), 7.62 (dd, J = 8.5, 1.4 Hz,
1H), 7.57 – 7.34 (m, 7H), 4.72 (q, J = 7.0 Hz, 2H), 3.02 (dq, J
= 14.4, 7.2 Hz, 2H), 2.91 (dq, J = 14.3, 7.2 Hz, 2H), 2.27 (dq, J
= 14.4, 7.2 Hz, 4H), 0.97 (t, J = 7.0 Hz, 3H), 0.25 (t, J = 7.3 Hz,
6H), 0.18 (t, J = 7.3 Hz, 6H); 13C NMR (126 MHz, CD2Cl2) δ:
152.0, 151.5, 145.4, 144.7, 144.3, 142.0, 140.5, 139.6, 133.5,
128.3, 127.7, 127.4, 127.0, 126.7, 126.5, 126.1, 124.1, 122.8,
122.7, 122.6, 121.8, 114.0, 113.2, 58.7, 57.4, 43.1, 30.4, 30.0,
13.1, 8.8, 8.7; HRMS (EI – TOF) m/z (M+): Calcd for
C36H36NBr 561.2031, Found 561.2038; Elemental analysis
(%). Calculated for C36H36 BrN: C 76.86, H 6.45, N 2.49;
Found: C 76.95, H 6.51, N 2.43.
5,10,10,15,15-pentaethyl-5-azatruxene – NCC. Step I (diol
synthesis): To 10 mL of tetrahydrofuran, 757 mg (1.5
mmol) of 1,3-(2-bromophenyl)-9-ethylcarbazole 24 was
added. Obtained mixture was cooled down to -78oC. Than
1.2 mL (2.5 M, 3 mmol) of n-butyllithium solution in hexane
was added. The mixture turns to yellow. After 20 min of
stirring at constant temperature 0.32 mL (d = 0.815 g/mL,
3 mmol) of pentan-3-one was added. The solution turns to
ASSOCIATED CONTENT
Supporting Information.
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Crystal structures and NMR are available free of charge via the
Internet at http://pubs.acs.org.
Symmetric Cyclooctatetraindoles: Exploring the
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Potential as Electron-Rich Skeletons with
Extended π-Systems. Org. Lett. 2014, 16 (11),
2942–2945.
AUTHOR INFORMATION
(9)
Sanguinet, L.; Williams, J. C.; Yang, Z.; Twieg, R. J.;
Mao, G.; Singer, K. D.; Wiggers, G.; Petschek, R. G.
Synthesis and Characterization of New
Truxenones for Nonlinear Optical Applications.
Chem. Mater. 2006, 18, 4259–4269.
Corresponding Authors
*kgorski@ichf.edu.pl ORCID ID 0000-0002-6439-2651
*jmech@ichf.edu.pl ORCID ID 0000-0002-4778-7918
All authors have given approval to the final version of the
manuscript.
9
(10) Bura, T.; Leclerc, N.; Bechara, R.; Lévêque, P.;
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Heiser,
T.;
Ziessel,
R.
Triazatruxene-
Diketopyrrolopyrrole
Dumbbell-Shaped
ACKNOWLEDGMENTS
Molecules as Photoactive Electron Donor for
High-Efficiency Solution Processed Organic Solar
Cells. Adv. Energy Mater. 2013, 3 (9), 1118–1124.
This work was supported by National Science Centre (grant no.
FUGA 4, 2015/16/S/ST4/00427), and in part by the Institute
of Physical Chemistry, Polish Academy of Sciences.
(11) Robertson, N.; Parsons, S.; MacLean, E. J.; Coxall,
R. A.; Mount, A. R. Preparation, X-Ray Structure
and Properties of a Hexabrominated, Symmetric
Indole Trimer and Its TCNQ Adduct: A New Route
to Functional Molecular Systems. J. Mater. Chem.
2000, 10 (9), 2043–2047.
REFERENCES
(1)
Maciejczyk, M. R.; Zhang, S.; Hedley, G. J.;
Robertson, N.; Samuel, I. D. W.; Pietraszkiewicz,
M. Monothiatruxene-Based, Solution-Processed
Green, Sky-Blue, and Deep-Blue Organic Light-
Emitting Diodes with Efficiencies Beyond 5%
Limit. Adv. Funct. Mater. 2018, 1807572, 1–13.
(12) Destrade, C.; Tinh, N. H.; Mamlok, L.; Malthete, J.
Trioxatruxenesꢀ: A New Family of Disc-Like
Mesogens with a Complex Polymorphism. Mol.
Cryst. Liq. Cryst. 1984, 114, 139–150.
(2)
Tisch, T. L.; Lynch, T. J.; Dominguez, R.
Polymetallic
Compounds
of
Extended
(13) Kaida, H.; Satoh, T.; Nishii, Y.; Hirano, K.; Miura, M.
Polyaromatic Ligands. Rhenium and Manganese
Carbonyl Derivatives of Truxene. J. Organomet.
Chem. 1989, 377, 265–273.
Synthesis
of
Benzobis-
and
Benzotrisbenzofurans by Palladium-Catalyzed
Multiple Intramolecular C–H/C–H Coupling.
Chem. Lett. 2016, 45 (9), 1069–1071.
(3)
(4)
Dehmlow, E. V.; Kelle, T. Synthesis of New
Truxene Derivatives: Possible Precursors of
Fullerene Partial Structures? Synth. Commun.
1997, 27 (11), 2021–2031.
(14) Ogaki, T.; Ohta, E.; Oda, Y.; Sato, H.; Matsui, Y.;
Kumeda, M.; Ikeda, H. Intramolecular Triple
Cyclization Strategy for Sila- and Oxa-Analogues
of Truxene with Long-Lived Phosphorescence.
Asian J. Org. Chem. 2017, 6 (3), 290–296.
Li, L.-L.; Hu, P.; Wang, B.-Q.; Yu, W.-H.; Shimizu, Y.;
Zhao, K.-Q. Synthesis and Mesomorphism of
Ether-Ester Mixed Tail C3-Symmetrical Truxene
Discotic Liquid Crystals. Liq. Cryst. 2010, 37 (5),
499–506.
(15) Kojima, T.; Furukawa, S.; Tsuji, H.; Nakamura, E.
Synthesis of Triphosphatruxene via Sextuple
Aromatic Nucleophilic Substitution and Simple
Isolation of Stereoisomers. Chem. Lett. 2014, 43
(5), 676–677.
(5)
(6)
(7)
Amick, A. W.; Scott, L. T. Trisannulated Benzene
Derivatives
by
Acid
of
Catalyzed
Cyclic
Aldol
Ketones.
Cyclotrimerizations
Methodology Development and Mechanistic
Insight. J. Org. Chem. 2007, 72 (9), 3412–3418.
(16) Bergman, J.; Egestad, B. Cyclotrimerization of
3(2H)-Benzo[b]Furanone,
Acetoxybenzo[b]Thiophene
Benzo[b]Selenophenone in Trifluoroacetic Acid.
3-
and
3(2H)-
Kao, M.-T.; Chen, J.-H.; Chu, Y.-Y.; Tseng, K.-P.;
Hsu, C.-H.; Wong, K.-T.; Chang, C.-W.; Hsu, C.-P.;
Liu, Y.-H. Facile Synthesis of 5,10,15-Hexaaryl
Truxenes: Structure and Properties. Org. Lett.
2011, 13 (7), 1714–1717.
Chem. Scr. 1986, 26 (2), 287–292.
(17) Bergman, J.; Egestad, B. Cyclocondensation of
3(2H)-Benzo[b]Thiophenone and Oxidation
Products Obtained During These Reaction.
Tetrahedron 1986, 42 (2), 763–773.
Manini, P.; d’Ischia, M.; Milosa, M.; Prota, G. Acid-
Promoted Competing Pathways in the Oxidative
Polymerization of 5,6-Dihydroxyindoles and
(18) Tinh, N. H.; Cayuela, R.; Destrade, C.; Malthete, J.
Trithiatruxenes: A Family of Disc-like Mesogens
with a New Polymorphism. Mol. Cryst. Liq. Cryst.
1985, 122, 141–149.
Related
Compounds:
Straightforward
Cyclotrimerization Routes to Diindolocarbazole
Derivatives. J. Org. Chem. 1998, 63 (20), 7002–
7008.
(19) Cayuela, R.; Nguyen, H. T.; Destrade, C.; Levelut, A.
M. Two Families of Trithiatruxene Derivatives.
Mol. Cryst. Liq. Cryst. 1989, 177, 81–91.
(8)
Wang, F.; Li, X.-C.; Lai, W.-Y.; Chen, Y.; Huang, W.;
Wudl, F. Synthesis and Characterization of
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 10 of 12
(20) Tinh, N. H.; Malthete, J.; Destrade, C. Reentrant Triazatruxene-Based Organic Dyes Containing a
1
2
3
4
5
6
7
8
Phenomenon in Disc-Like Liquid Crystal. Mol.
Cryst. Liq. Cryst. 1981, 64, 291–298.
Rhodanine-3-Acetic Acid Acceptor for Dye-
Sensitized Solar Cells. Dye. Pigment. 2015, 113,
737–742.
(21) Yao, C.; Yu, Y.; Yang, X.; Zhang, H.; Huang, Z.; Xu,
X.; Zhou, G.; Yue, L.; Wu, Z. Effective Blocking of
the Molecular Aggregation of Novel Truxene-
Based Emitters with Spirobifluorene and
Electron-Donating Moieties for Furnishing
Highly Efficient Non-Doped Blue-Emitting
OLEDs. J. Mater. Chem. C 2015, 3 (22), 5783–
5794.
(30) Ramos, F. J.; Rakstys, K.; Kazim, S.; Grätzel, M.;
Nazeeruddin, M. K.; Ahmad, S. Rational Design of
Triazatruxene-Based Hole Conductors for
Perovskite Solar Cells. RSC Adv. 2015, 5 (66),
53426–53432.
9
(31) Rakstys, K.; Abate, A.; Dar, M. I.; Gao, P.;
Jankauskas, V.; Jacopin, G.; Kamarauskas, E.;
Kazim, S.; Ahmad, S.; Grätzel, M.; et al.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(22) Lai, W.-Y.; Xia, R.; He, Q.-Y.; Levermore, P. A.;
Huang, W.; Bradley, D. D. C. Enhanced Solid-State
Luminescence and Low-Threshold Lasing from
Starburst Macromolecular Materials. Adv. Mater.
2009, 21 (3), 355–360.
Triazatruxene-Based
Hole
Transporting
Materials for Highly Efficient Perovskite Solar
Cells. J. Am. Chem. Soc. 2015, 137 (51), 16172–
16178.
(23) Tsiminis, G.; Wang, Y.; Shaw, P. E.; Kanibolotsky,
A. L.; Perepichka, I. F.; Dawson, M. D.; Skabara, P.
J.; Turnbull, G. A.; Samuel, I. D. W. Low-Threshold
Organic Laser Based on an Oligofluorene
Truxene with Low Optical Losses. Appl. Phys. Lett.
2009, 94 (24), 243304-(1-3).
(32) Xiao, Q.; Sakurai, T.; Fukino, T.; Akaike, K.;
Honsho, Y.; Saeki, A.; Seki, S.; Kato, K.; Takata, M.;
Aida,
T.
Propeller-Shaped
Fused
Oligothiophenes: A Remarkable Effect of the
Topology of Sulfur Atoms on Columnar Stacking.
J. Am. Chem. Soc. 2013, 135 (49), 18268–18271.
(24) Wang, Y.; Tsiminis, G.; Yang, Y.; Ruseckas, A.;
Kanibolotsky, A. L.; Perepichka, I. F.; Skabara, P.
J.; Turnbull, G. A.; Samuel, I. D. W. Broadly
Tunable Deep Blue Laser Based on a Star-Shaped
Oligofluorene Truxene. Synth. Met. 2010, 160
(13–14), 1397–1400.
(33) Yang, P.-C.; Wen, H.-W.; Huang, C.-W.; Zhu, Y.-N.
Synthesis and Chemosensory Properties of Two-
Arm
Truxene-Functionalized
Conjugated
Polyfluorene Containing Terpyridine Moiety. RSC
Adv. 2016, 6 (90), 87680–87689.
(34) Yuan, M.-S.; Liu, Z.-Q.; Fang, Q. Donor-and-
(25) dos Santos, P. L.; Ward, J. S.; Congrave, D. G.;
Batsanov, A. S.; Eng, J.; Stacey, J. E.; Penfold, T. J.;
Monkman, A. P.; Bryce, M. R. Triazatruxene: A
Rigid Central Donor Unit for a D–A3 Thermally
Activated Delayed Fluorescence Material
Acceptor
Substituted
Truxenes
as
Multifunctional Fluorescent Probes. J. Org. Chem.
2007, 72 (21), 7915–7922.
(35) Xu, Y.; Wu, X.; Chen, Y.; Hang, H.; Tong, H.; Wang,
L. Star-Shaped Triazatruxene Derivatives for
Rapid Fluorescence Fiber-Optic Detection of
Nitroaromatic Explosive Vapors. RSC Adv. 2016,
6 (38), 31915–31918.
Exhibiting
Sub-Microsecond
Reverse
Intersystem Crossing and Unity Quantum Yield
via Multiple Singlet–Triplet State Pairs. Adv. Sci.
2018, 5 (6), 1700989 (1-9).
(36) Earmrattana,
N.;
Sukwattanasinitt,
M.;
(26) Grisorio, R.; Iacobellis, R.; Listorti, A.; De Marco,
L.; Cipolla, M. P.; Manca, M.; Rizzo, A.; Abate, A.;
Gigli, G.; Suranna, G. P. Rational Design of
Molecular Hole-Transporting Materials for
Perovskite Solar Cells: Direct versus Inverted
Device Configurations. ACS Appl. Mater.
Interfaces 2017, 9 (29), 24778–24787.
Rashatasakhon, P. Water-Soluble Anionic
Fluorophores from Truxene. Dye. Pigment. 2012,
93 (1), 1428–1433.
(37) Sam-ang, P.; Raksasorn, D.; Sukwattanasinitt, M.;
Rashatasakhon, P. A Nitroaromatic Fluorescence
Sensor from a Novel Tripyrenyl Truxene. RSC
Adv. 2014, 4 (101), 58077–58082.
(27) Rakstys, K.; Paek, S.; Gao, P.; Gratia, P.; Marszalek,
T.; Grancini, G.; Cho, K. T.; Genevicius, K.;
Jankauskas, V.; Pisula, W.; et al. Molecular
Engineering of Face-on Oriented Dopant-Free
Hole Transporting Material for Perovskite Solar
Cells with 19% PCE. J. Mater. Chem. A 2017, 5
(17), 7811–7815.
(38) Xu, Y.; Wu, X.; Chen, Y.; Hang, H.; Tong, H.; Wang,
L. Fiber-Optic Detection of Nitroaromatic
Explosives
Triazatruxene-Based
with
Solution-Processable
Hyperbranched
Conjugated Polymer Nanoparticles. Polym. Chem.
2016, 7 (27), 4542–4548.
(39) Wang, K.-R.; An, H.-W.; Han, D.; Qian, F.; Li, X.-L.
Fluorescence Quenching of Triazatruxene-Based
Glycocluster Induced by Peanut Agglutinin
Lectin. Chinese Chem. Lett. 2013, 24 (6), 467–470.
(28) Andrikaityte, E.; Simokaitiene, J.; Tomkeviciene,
A.; Grazulevicius, J. V.; Jankauskas, V. Synthesis
and Properties of Triindole-Based Monomers
and Polymers. Mol. Cryst. Liq. Cryst. 2014, 590,
121–129.
(40) Wang, K.-R.; Wang, Y.-Q.; An, H.-W.; Zhang, J.-C.;
Li, X.-L. A Triazatruxene-Based Glycocluster as a
(29) Qian, X.; Lu, L.; Zhu, Y.-Z.; Gao, H.-H.; Zheng, J.-Y.
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Page 11 of 12
The Journal of Organic Chemistry
Fluorescent Sensor for Concanavalin A. Chem. - A
Eur. J. 2013, 19 (8), 2903–2909.
and Applications Development. European J. Org.
Chem. 2012, 2012 (11), 2127–2131.
1
2
3
4
5
6
7
8
9
(41) Huang, W.; Smarsly, E.; Han, J.; Bender, M.;
Seehafer, K.; Wacker, I.; Schröder, R. R.; Bunz, U.
H. F. Truxene-Based Hyperbranched Conjugated
(50) Feng, X.; Wu, J.; Enkelmann, V.; Müllen, K. Hexa-
Peri-Hexabenzocoronenes by Efficient Oxidative
Cyclodehydrogenation: The Role of the
Oligophenylene Precursors. Org. Lett. 2006, 8
(6), 1145–1148.
Polymers:
Fluorescent
Micelles
Detect
Explosives in Water. ACS Appl. Mater. Interfaces
2017, 9 (3), 3068–3074.
(51) Khotina, I. A.; Consonni, R.; Kushakova, N. S.;
Porzio, W.; Giovanella, U.; Kovalev, A. I.;
Babushkina, M. A.; Peregudov, A. S.; Destri, S.
Branched Polyphenylenes and Phenylene
Dendrimersꢀ: NMR and Optical Studies. Eur.
Polym. J. 2013, 49 (12), 4224–4237.
(42) Kobayashi, K.; Suzue, N.; Ishii, R.; Kamiya, R.;
Wakabayashi, H. Reactions of Ninhydrin with
Benzo[b]Thiophenes. Heterocycles 2009, 78 (10),
2467–2475.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(43) El-Sayed, M. T.; Wessjohann, L.; Porzel, A.;
Hilgeroth,
A.
Diazatruxenes
from
the
(52) Lambert, J. B.; Zhao, Y.; Emblidge, R. W.; Salvador,
Condensation Reaction of Indoles with
Ninhydrin. J. Heterocycl. Chem. 2016, 54 (2),
1077–1083.
L. A.; Liu, X.; So, J.-H.; Chelius, E. C. The β Effect of
Silicon and Related Manifestations of
σ
Conjugation. Acc. Chem. Res. 1999, 32 (2), 183–
190.
(44) Benito-Hernández, A.; El-Sayed, M. T.; López
Navarrete, J. T.; Ruiz Delgado, M. C.; Gómez-Lor,
(53) Trawny, D.; Quennet, M.; Rades, N.; Lentz, D.;
Paulus, B.; Reissig, H.-U. Syntheses, Structures
and Conformational Dynamics of 1,3,5-Tris(3′′-
B.
Fused
Donor-Acceptor
π-Conjugated
Diazatruxenones: Synthesis and Electronic
Properties. Org. Chem. Front. 2018, 5 (11), 1748–
1755.
Ethynylbiphenyl-2′-Yl)Benzene
Derivatives.
European J. Org. Chem. 2015, 2015 (21), 4667–
4674.
(45) Górski, K.; Mech-Piskorz, J.; Noworyta, K.;
Leśniewska, B.; Pietraszkiewicz, M. Efficient
Synthesis of 5-Oxatruxene and the Unusual
Influence of Oxygen Heteroatom on Its Physico-
Chemical Properties. New J. Chem. 2018, 42,
5844–5852.
(54) L’Helgoual’ch, J. M.; Seggio, A.; Chevallier, F.;
Yonehara, M.; Jeanneau, E.; Uchiyama, M.;
Mongin, F. Deprotonative Metalation of Five-
Membered Aromatic Heterocycles Using Mixed
Lithium-Zinc Species. J. Org. Chem. 2008, 73 (1),
177–183.
(46) Maciejczyk, M. R.; Williams, J. A. G.; Robertson, N.;
Pietraszkiewicz, M. Monothiatruxene: A New
Versatile Core for Functional Materials. RSC Adv.
2017, 7 (78), 49532–49535.
(55) Pietraszkiewicz, M.; Maciejczyk, M. R.; Górski, K.
P. Sposób Wytwarzania Pochodnych 1,3,5-
Triarylobenzenu i Truksenu. 404606, 2013.
(47) Jiang, Q.; Duan-Mu, D.; Zhong, W.; Chen, H.; Yan,
(56) Maciejczyk, M.; Pietraszkiewicz, M.; Górski, K.
Process for Preparing Derivatives of 1,3,5-
Triarylbenzene and Truxene, 2015.
H.
Amino-Directed
RhIII-Catalyzed
C–H
Activation Leading to One-Pot Synthesis of N–H
Carbazoles. Chem. - A Eur. J. 2013, 19 (6), 1903–
1907.
(57) Curphey,
T.
J.
Preparation
of
P-
Toluenesulfonylazide. A Cautionary Note. Org.
Prep. Proced. Int. 1981, 13 (2), 112–115.
(48) Kim, M.; Lee, J. Y. Synthesis of 2- and 4-
Substituted
Correlation of Substitution Position with
Photophysical Properties and Device
Carbazole
Derivatives
and
(58) Waser, J.; Gaspar, B.; Nambu, H.; Carreira, E. M.
Hydrazines and Azides via the Metal-Catalyzed
Hydrohydrazination and Hydroazidation of
Olefins. J. Am. Chem. Soc. 2006, 128 (35), 11693–
11712.
Performances of Host Materials. Org. Electron.
2013, 14 (1), 67–73.
(49) Ullah, E.; Mcnulty, J.; Robertson, A. Highly
Chemoselective
Mono-Suzuki
Arylation
Reactions on All Three Dichlorobenzene Isomers
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