Toward Soluble 5,10-Diheterotruxenes: Synthesis and Reactivity of 5,10-Dioxatruxenes, 5,10-Dithiatruxenes, and 5,10-Diazatruxenes

Article abstract of DOI:10.1021/acs.joc.9b03387

The following work presents three general approaches allowing, for the first time, the synthesis of 5,10-diheterotruxene derivatives containing two identical heteroatoms, namely, oxygen OOC, nitrogen NNC, or sulfur SSC. Two of described pathways involve the photocyclization of the corresponding triene 2 as a key step leading to a heptacyclic aromatic system. The third approach is based on the acidic condensation between ninhydrin 14 and benzo[b]heteroole 15. Typical functionalizations of the 5,10-diheterotruxene core have also been presented. In addition, the article discusses the advantages and limitations of the three suggested paths for receiving specific 5,10-diheterotruxene derivatives because the universal method suitable for obtaining molecules with any type of heteroatoms is not known so far.

Full text of DOI:10.1021/acs.joc.9b03387

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Article
Towards Soluble 5,10-Diheterotruxenes: Synthesis and
Reactivity of 5,10-Dioxa-, 5,10-Dithia- and 5,10-Diazatruxenes
Krzysztof Górski, Justyna Mech-Piskorz, Barbara Le#niewska,
Oksana Pietraszkiewicz, and Marek Pietraszkiewicz
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b03387 • Publication Date (Web): 17 Mar 2020
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The Journal of Organic Chemistry
Towards Soluble 5,10-Diheterotruxenes: Synthesis and
Reactivity of 5,10-Dioxa-, 5,10-Dithia- and 5,10-Diazatruxenes
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Krzysztof Górski*, Justyna Mech-Piskorz*, Barbara Leśniewska, Oksana Pietraszkiewicz, Marek
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Pietraszkiewicz
Institute of Physical Chemistry, Polish Academy of Sciences; Kasprzaka 44/52, 01-224 Warsaw, Poland
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KEYWORDS: truxene, heterotruxene, thiatruxene, diheterotruxene, azatruxene, oxatruxene, synthesis, reactivity,
condensation, photocyclization, alkylation, bromination, lithiation
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ABSTRACT: The following work presents three general approaches allowing for the first time the synthesis of 5,10-
diheterotruxene derivatives containing two identical heteroatoms, namely oxygen OOC, nitrogen NNC or sulfur SSC.
Two of described pathways involve the photocyclisation of the corresponding triene 2 as a key step leading to
heptacyclic aromatic system. The third approach is based on the acidic condensation between ninhydrin 14 and
benzo[b]heteroole 15. Typical functionalizations of 5,10-diheterotruxene core have been also presented. In addition, the
article discusses the advantages and limitations of the three suggested paths for receiving specific 5,10-diheterotruxene
derivatives, because the universal method suitable for obtaining molecules with any type of heteroatoms is not known
so far.
conductivity, so that 5,10,15-triazatruxene40-53 and
INTRODUCTION
5,10,15-trithiatruxene54 derivatives have been used as
Truxenes are a family of heptacyclic carbo- and
hole transporting materials in prototype photovoltaic
heteroaromatic systems. Currently, the synthesis of
devices. A relatively new class of aromatic systems based
truxene1-5 and its triheteroanalogues6-9 as well as their
on the truxene core are 5-hetero- and 5,10-
reactivity10-20 are well known. In the 80s, liquid crystal
diheterotruxenes. The synthesis and reactivity of
properties of some alkyl derivatives invoked an interest
5-heterotruxenes has been described for compounds
in this class of substances, in particular of truxene,21,22
containing
nitrogen,55
oxygen
and56
sulfur.57
5,10,15-trioxatruxene23 and 5,10,15-trithiatruxene.24,25
Currently, truxenes are used in optoelectronics as blue
emitters,26-30 or in lasing media31-34, exhibit non-linear
properties.35-38 For example, the use of 5,10,15-
triazatruxene as a donor subunit in the D-A3 system
significantly reduced the time of Thermally Activated
Delayed Fluorescence (TADF).39 Nevertheless, not only
the emissive properties of truxenes have been practically
used. It is noteworthy that the presence of heteroatoms
in the truxene π-electron system allows the modulation
of physicochemical properties, including electric
5-Thiatruxene derivatives were also used to develop
deep blue emitters used in the prototype OLED device
characterized by high stability.58 In the case of 5,10-
dihetero compounds, only the carbonyl derivatives are
known, namely: 5,10-dithiatruxen-15-one,59 5,10-
diazatruxen-15-one60 which can be applied as ambipolar
semiconductors.61 Due to the fact that the synthesis,
reactivity
and
physicochemical
properties
of
nonsymmetric heterotruxenes are barely known, there is
still a lot to explore.
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Scheme 1. The first and the second approach to synthesis of 5,10-diheterotruxenes through photocyclization.
Scheme 2. The third approach to synthesis 5,10-diheterotruxenes through ketone intermediate and synthesis of the
alcohols 16b,c.
heterotruxenes,56,55
the
obtaining
of
5,10-
diheterotruxenes demands slightly different approach.
5,10–Dioxatruxene, OOC
The work on the soluble derivatives of 5,10-
diheterotruxenes began with the synthesis of ethylated
5,10-dioxatruxene OOC. The first and the most
promising attempt to obtain OOC was a synthesis
according to the route III, Scheme 2. During acidic
condensation between 14 and 15a the ketone 13a was
formed, but in a trace amount, therefore, alternative
synthetic routes had to be developed. Alternative
synthetic strategy of OOC is based on photocyclization
of 2a which enables the formation of 5,10-dioxatruxene
1a, Scheme 1. As a result of alkylation, 1a is converted to
diethylated derivative, OOC. The trimer 2a can be
synthesized in two different ways. Route I is based on
addition of organolithium compound 6a to indan-1-one
4. The resulting alcohol 3a undergoes dehydratation in
the presence of strong acidic media for example
methanesulfonic acid. Another approach, route II, uses a
palladium catalyzed cross-coupling reaction between 8a
Scheme 3. Synthesis of the soluble 5,10-dihetrotruxenes:
OOC, SSC and NNC and their reactivity.
RESULTS AND DISCUSSION
Scheme
1 and Scheme 2 present three general
procedures, route I, II and III, leading to the formation
of 5,10-diheterotruxene core. Despite the very useful
knowledge gained during the synthesis of 5-
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The Journal of Organic Chemistry
and 9a. Due to the availability of reagents and the ease efficiency of the addition to the carbonyl group. The
1
of synthesis of the corresponding precursors, route I
seems to be the most appropriate for synthesis of OOC.
Research leading to OOC began with the synthesis of
dimer 7a (route I). The first approach that could enable
the formation of 7a, was the addition of an
organolithium compound 21 to benzo[b]furan-3-one 20
leading to alcohol 19, which after dehydratation can be
converted into final compound,.7a, Scheme 4. However,
due to the significant shift of equilibrium into the enol
form 20’, the nucleophilic addition carried out in toluene
was unsuccessful, leading mainly to benzo[b]furan 15a
and the deprotonation product 22. Therefore, it was
necessary to develop an alternative synthesis path
resulting hydroxyl derivative 3a was then treated with
methanesulfonic acid which initiated dehydration, finally
leading to the formation of trimer 2a. Directly after the
isolation, trimer 2a was irradiated with UV-C light in the
presence of catalytic amount of iodine which leads to the
photocyclization product 1a. As obtained, nearly
insoluble, orange solid containing 1a was used in the
next step, Scheme 3. Alkylation of 5,10-dioxatruxene 1a
under argon atmosphere, in the basic environment
results in the formation of soluble derivative, OOC. The
introduction of two ethyl groups to the aromatic system
of 1a significantly increased its solubility. However
solubility of 1a is much lower corresponding to
tetraethylated derivative of 5-oxatruxene. The described
effect is a consequence of increased intermolecular
interactions occurring between benzo[b]furan subunits
(Figure S1).
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leading
to
the
desired
biaryl
system
7a.
5,10–Dithiatruxene
Route III, Scheme 2 was successfully applied in the
synthesis of ketone 13b.59 The use of methanesulfonic
acid in 1,2-dichloroethane allows to increase the reaction
yield from 68% to 74%. Due to very low solubility of 13b,
the carbonyl group does not undergo reduction,
preventing quick conversion of 13b to 1b and then to
SSC. The first synthetic approach, leading to a soluble
derivative of 5,10-dithiatruxene SSC, was analogous to
OOC synthesis (route I, Scheme 1). Biaryl 7b, obtained
from the Suzuki reaction between 8b and 24 (Scheme 5),
was subjected to direct lithiation in order to obtain an
organometallic compound 6b which, after reacting with
iodine, leads to monoiododerivative 5b. However, very
low solubility of 5b in toluene caused iodine to lithium
exchange insufficient. Generation of the organolithium
compound 6b in toluene became complicated and its
addition to the ketone 4 was impossible to achieve.
Replacement of an iodine atom with a bromine one did
not significantly change the solubility of the compound.
On the other hand, the addition to the carbonyl group in
tetrahydrofuran leads only to the protonation of the
organolithium compound 5b. For this reason, it was
necessary to use an alternative synthetic path, enabling
the preparation of trimer 2b. The trimer 2b, can also be
obtained by palladium catalyzed cross-coupling route II,
Scheme 1. For this purpose, the generated organolithium
compound 11b was reacted with indan-1-one, 4. After
the subsequent dehydration of alcohol 10b,
bromoderivative 9b was formed. Reaction between
boronic acid 8b and 9b in the presence of the base and
the palladium catalyst led to both trimer 2b and traces of
5,10-dithiatruxene 1b. In addition to the expected
products, a large amount of colored byproducts was also
created. The unexpected course of the described
transformation could be a consequence of the acidic
Scheme 4. Reaction of 18 with benzo[b]furan-3-one 20.
To perform successful synthesis of 7a, well known arene
transformation, called Suzuki reaction, was applied,
Scheme 5. As a result of reaction between ketone 20 and
trifluoromethanesulfonic anhydride in the presence of
triethylamine, triflate 23 was obtained. Cross-coupling
reaction of 23 with 8a, led to biaryl 7a. It should be
mentioned that the esterification ought to be carried out
in solvents such as chlorinated hydrocarbons, which do
not react with trifluoromethanesulfonic acid, present in
triflic anhydride as impurity.
Scheme 5. Synthesis of biaryls 7a and 7b.
The biaryl 7a underwent direct lithiation in the presence
of n-butyllithium in tetrahydrofuran, route I, Scheme 1.
Lithiation of derivative 7a is easier than lithiation of
benzo[b]furan 15a, which results from coordination of
the lithium atom with the external oxygen atom of the
neighboring
benzo[b]furan
subunit.
Generated
organolithium derivative 6a after reaction with iodine,
led to a iododerivative 5a. As a result of lithiation of 5a
in toluene, an organometallic compound is obtained,
which afterwards reacted with ketone 4, leads to the
alcohol 3a. The nucleophilic addition turns out to be very
sensitive to temperature, therefore the indan-1-one-4
solution should be added very slowly to increase the
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nature of the hydrogen atoms in 1H-indene subunit of
trimer 2b, which may undergo ionization under Suzuki
reaction conditions (Scheme 6). Formed reactive anion
25, could undergo further transformations leading to
colored byproducts present in the reaction mixture.
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Scheme 6. Ionization of trimer 2b
To confirm or disprove proposed explanation of the
reaction course, the trimer 30 with protected by ethyl
groups indene subunit, was synthesized (Scheme 7). The
first step was the alkylation of 9b which led to a mixture
of two isomeric ethylated products 28 : 29 in a ratio of ~
1:5.
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Scheme 7. Synthesis of trimer 30.
The composition of the reaction mixture after alkylation
can be estimated by analysis of the spatial structure of
the intermediate anion 27. Possible structures differ in
the places were the bromoethane attack occurs, leading
to the generation of the expected product 28 and the
side product 29. A seemingly more crowded position,
located closer to the benzo[b]thiophene subunit, turns
out to be much more susceptible to the attack of the
alkylating agent (Figure 1). This is directly related with
the flat structure of the benzo[b]thiophene subunit. In
order to obtain the lowest possible molecular energy,
which is equivalent to achieving the most effective
electron coupling between π-electron systems, the whole
molecule is flattened as much as possible. Such
orientation of aromatic subunits leads to the more stable
carbanion 27’ resulting in a smooth approach of the
alkylating agent. Attack on an adjacent position to the
ethyl group is more difficult due to the steric hindrance.
Bromoderivative 28 underwent palladium catalysed
cross-coupling with boronic acid 8b, despite the
presence of the ethyl moieties. This process leads to the
trimer 30, traces of SSC and a large number of colored
by-products. A similar reaction result in the case of 2b or
30, indicated its instability in Suzuki coupling conditions
associated with the electronic structure rather than their
ionization capability. Photocyclization of trimer 2b in the
presence of iodine in hexane, under UV-C light,
that the obtained compound is a cyclic product 31
(Scheme 8). Low solubility of 31 in hexane prevents
subsequent reaction with iodine leading to 5,10-
dithiatruxsene 1b. For this reason, it was necessary to use
toluene solvent as the proper environment for
photocyclization of 2b. 2b was irradiated with UV-C light
and the obtained orange solid was subjected to
alkylation reaction leading to diethylderivative of 5,10-
dithiatruxene, SSC.
Scheme 8. Probable structure of 31.
Scheme 1, led to an insoluble substance which did not
undergo alkylation. Mass spectrometry analysis suggests
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Figure 1. Structure of anion 27 and possible attacks of alkylating agent
5,10–Diazatruxene
easily carried out in the presence of 3 eq. of bromine in
dichloromethane, while using the excess of bromine
results in up to five bromine atoms in 5,10-diazatruxene
core, 18. Bromoderivatives, 17 and 18, can be used for
further functionalization in order to tune the
The known in the literature acidic condensation of
ninhydrin with indoles seems to be the only way leading
to the 5,10-diazatruxene core (route I, Scheme 1).60,61
Photocyclisation approach, successful in 5-azatruxene
synthesis, was not suitable due to the high reactivity of
the trimer 2c. What is more, the nitrene insertion,
successfully used in the synthesis of 5-azatruxene core, in
this case leads to a complicated mixture of products.55 In
the presence of strong protic acid, ninhydrin 14
undergoes condensation with indole derivative 15c
leading to ketone 13c. In contrast to previously
discussed carbonyl compound 13b, ketone 13c has two
ethyl groups, as solubilizing agent, allowing Wolff–
Kizhner reduction. Surprisingly, the most problematic
step in the synthesis of soluble derivative NNC, turns out
to be the double ethylation of the methylene group.
Ethylation of 5,10-diethyl-5,10-diazatruxene 1c, carried
out in the same conditions as previously used in the
synthesis of OOC and SSC, leads to multiple, colored
products. This rather unusual behavior of 1c in alkaline
conditions suggests decomposition of anions formed in
the reaction environment. Numerous experiments have
made it possible to obtain the desired structure of NNC.
1c was alkylated at -40 °C in dimethylformamide,
saturated with argon. Despite lower temperature, than in
the case of OOC and SSC, amount of bromoethane
during ethylation increased from 4.4 eq to 20.8 eq. Such
conditions were dictated by the faster conversion of
unstable anions. Also, the order of adding reagents has
changed. The alkylating agent was added first into the
reaction mixture, followed by the addition of the base.
The described procedure finally allows for the synthesis
of NNC, but still with a relatively low reaction yield, i.e.
14%. Further experiments enabled a distinct increase in
the alkylation yield up to 45.1%. To achieve such a result,
n-butyllithium at -78 °C was added as the ionizing agent.
All soluble 5,10-diheterotruxene derivatives (OOC, SSC
and NNC) underwent a characteristic reaction for
aromatic systems, namely electrophilic substitution.
Triple bromination, leading to 17 (Scheme 3), can be
physicochemical
properties
for
optoelectronic
application. Another possible way to modify the 5,10-
diheterotruxene core is to use the reactivity of the
carbonyl group present in compounds 13a-c. Despite
poor solubility of ketones 13b,c, their reactions with
organometallic compounds such as ethylmagnesium
bromide at elevated temperature resulted in efficient
conversion to 16b,c.
CONCLUSIONS
The presented three general methods for creating the
5,10-diheterotruxene skeleton, presented in this paper,
allow the introduction of two heteroatoms of the same
type. During the synthesis of diheterotruxenes the
particular attention should be paid to the
photocyclization approach, presented at Scheme 1 (route
I
and II). Due to the availability of reagents,
benzo[b]heterools, further exploration of the
diheterotruxene family is possible. What's more, it can be
used in the synthesis of novel diheterotruxenes having
two different heteroatoms. The dramatically low
solubility of the appropriate reagents in the most
common solvents was the most serious obstacle to
obtain unsubstituted 5,10-diheterotruxenes. Hence the
special attention has been paid to the matter of
solubility. Good solubility connected with increased
aggregation of 5,10-diheterotruxenes in the solid state,
comparing 5-heterotruxenes, suggests the use of OOC,
SSC and NNC derivatives as a solution processible
organic semiconductors. In turn, the functionalization of
positions 2, 8, 13 and 15, allows the synthesis of new
fluorophores for optoelectronics industry, or for
detection of volatile substances. The presented synthetic
approach,
leading
to
unsymmetrical
5,10-
diheterotruxenes, also opens the possibility of synthesis
of other hard-to-reach soluble condensed aromatic and
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heteroaromatic systems. The crystallographic and Benzo[b]furan-3-yl trifluoromethanesulfonate – 23. To 5
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spectroscopic experimental data, placed in the electronic
supporting info, will be discussed in detail in a separate
paper.
mL of dichloromethane distilled from H2SO4, 670 mg (5
mmol) of benzo[b]furan-3(2H)-one 20 and 1.05 mL (7.5
mmol, d = 0.735 g/mL) of triethylamine distilled from
CaH2 was added. The solution, kept under argon, turned
red and then was cooled to -40 °C. Next, 1.26 mL (7.5
mmol, d = 1.667 g/mL) of trifluoromethanesulfonic
anhydride was added slowly and the mixture was
brought to room temperature. After about 0.5 h, 5 mL of
water was added, the organic layer was separated, and
the aqueous phase was extracted with 5 mL of
dichloromethane. The combined extracts were dried over
MgSO4 and evaporated. The crude product was purified
via column chromatography using silica gel as stationary
phase and 10% dichloromethane in hexane solution as
eluent to give 1.05 g of a light yellow liquid, with the
reaction yield of 80%. The analysis is consistent with the
literature data.63 1H NMR (300 MHz, CDCl3) δ: 7.38 (td, J
= 7.2, 1.3 Hz, 1H), 7.44 (td, J = 7.2, 1.3 Hz, 1H), 7.54 (dd, J
= 7.2, 1.3 Hz, 1H), 7.65 (dd, J = 7.2. 1.3 Hz, 1H), 7.84 (s,
1H); 13C{1H} NMR (50 MHz, CDCl3) δ: 111.2, 118.1, 118.8,
120.2, 124.1, 126.2, 134.1, 135.3, 153.2.
EXPERIMENTAL
General Information. All solvents used were of
analytical grade. Toluene and tetrahydrofuran used in
lithiation reaction were freshly distilled from LiAlH4 under
argon atmosphere. Benzo[b]thiophene, benzo[b]furan,
indole, indan-1-one, were delivered from ABCR. All
reaction requiring heating were carried out using a
heating mantle. OSRAM UV-C Puritec HNS L 2G11, 55 W,
lamp was the source of UV-C radiation during the
photocyclization. The photocyclization was carried out
directly in the reaction vessel. Emission spectrum of the
UV-C lamp can be found in SI. Mass spectra were
collected at Applied Biosystems 4000Q TRAP with
electron impact as ionization method. 1H and 13C{1H}
NMR spectra were measured at Bruker DRX 500MHz in
CD2Cl2 or CDCl3. Shift of the residual peak of solvents
was taken as an internal chemical shift. Absorption and
emission spectra were measured for diluted samples
(absorbance below 0.1). Dichloromethane used as a
solvent was distilled prior to the experiment. Absorption
was recorder using spectrophotometer UV 2401,
Shimazu, Japan. Emission spectra were collected using
Fluorolog FL3-22, Horiba Jobin Yvon, France. Quantum
yield values were obtained by the absolute method using
an integrating sphere. Calculations were performed
using DFT theory with b3lyp/6-31g(d,p) set for molecules
in a vacuum.
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Benzo[b]furan-2-ylboronic acid – 8a. To 40 mL of
tetrahydrofuran, 4.4 mL (40 mmol, d = 1.072 g/mL) of
benzo[b]furan 15a was added and the mixture was
cooled to -78 °C and 16 mL (40 mmol, 2.5 M) of a
solution of n-butyllithium in hexane was added - a white
precipitate appeared. After 1 h, the mixture was brought
to room temperature and cooled again to -78 °C. Then 5
mL (45 mmol, d = 0.932 g/mL) of trimethylborate was
added and the obtained solution was slowly elevated to
room temperature. After that 10 mL of aqueous HCl (1:9,
HCl : water) was added to the mixture and extracted
three times with 40 mL of dichloromethane. The
combined extracts were dried over MgSO4 and
evaporated. The obtained solid residue was treated with
40 mL of hexane, cooled to 0 °C and filtered. 4.41 g of
white solid as a final product was obtained, with the
reaction yield of 68%. The analysis is consistent with the
literature data.64 1H NMR (500 MHz, d6-DMSO:D2O/95:5)
δ: 7.71 (d, J =8.0 Hz, 1H), 7.60 (d, J =8.5 Hz, 1H), 7.50 (s,
1H), 7.37 (t, J = 8.0 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H); 13C{1H}
NMR (125 MHz, d6-DMSO:D2O 95:5) δ: 156.4, 127.6,
125.3, 122.5, 121.8, 117.5, 111.4.
Benzofuran-3(2H)-one – 20. 7.61 g (50 mmol) of
phenoxyacetic acid was dissolved in 50 mL of thionyl
chloride and was refluxed. After 4 hours, the mixture was
cooled and excess of thionyl chloride was evaporated
under reduced pressure. The liquid residue was dissolved
in 50 mL of dichloromethane. The obtained solution was
added to a suspension of 13 g (98 mmol) of anhydrous
aluminum chloride in 50 mL of dichloromethane cooled
to 0 ° C. After 15 min from the addition of the acid
chloride, the mixture was brought to room temperature
and after a further 30 min the solution was poured onto
ice. The organic layer was separated, while aqueous layer
was extracted three times with 50 mL of
dichloromethane. Next, combined extracts were dried
over MgSO4 and evaporated. The crude product was
purified via column chromatography, using silica gel as
stationary phase and 10% ethyl acetate in hexane
solution as eluent, to give 2.41 g of a yellow solid, with
the reaction yield of 36%. The mp. 97 ° C is consistent
with literature data.62 1H NMR (400 MHz, CDCl3) δ: 7.80-
7.51 (m, 2H), 7.23-6.99 (m, 2H), 4.65 (d, J=15.6 Hz, 2H).
3-(Benzo[b]furan-2-yl)benzo[b]furan – 7a. To 60 mL of a
mixture of xylene
:
ethanol (2:1) under argon
atmosphere, 810 mg (5 mmol) of benzo[b]furan-2-
ylboronic acid 8a, 1.33 g (5 mmol) of benzo[b]furan-3-yl
trifluoromethanesulfonate 23, 231.12 mg (0.2 mmol) of
Pd(PPh3)4 and 7.5 mL (15 mmol, 2 M) of an aqueous
solution of K2CO3 was added and then solution was
refluxed. The mixture turned muddy light brown. After 21
hours, reaction was cooled and evaporated to dryness.
The crude product was purified via column
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The Journal of Organic Chemistry
chromatography using silica gel as stationary phase and chromatography using silica gel as stationary phase and
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hexane as eluent to give 625 mg of a white solid, with
the reaction yield of 53%. The mp. was 85 °C. H NMR
hexane → 10% solution of dichloromethane in hexane →
15% solution of ethyl acetate in hexane as eluent to
obtain 370 mg of 2a as white solid, with the reaction
yield of 53%. Step II (photocyclisation and alkylation): To
1.06 l of hexane, 370 mg (1.06 mmol) of 2a and 26.71 mg
(0.106 mmol) of iodine were added. Than the solution
was irradiated with UV-C light. After 1 h the reaction
mixture was concentrated, and the resulting orange
precipitate was filtered. The obtained material was then
suspended in 5.3 mL of dimethylformamide (saturated
with argon at 0 °C for 1 h) and 0.35 mL (4.66 mmol, d =
1.46 g/mL) of ethyl bromide and 0.26 g (4.66 mmol) of
ground KOH was added with stirring. After 24 h, 5.8 mL
of water was added and the mixture was extracted three
times with 2.9 mL of dichloromethane. Combined
organic layers was dried over MgSO4 and evaporated.
The crude product was purified via column
chromatography using silica gel as stationary phase and
10% solution of dichloromethane in hexane as eluent to
obtain 183 mg of a white solid, with the reaction yield of
1
(500 MHz, CD2Cl2) δ: 8.18 (s, 1H), 8.03–7.99 (m, 1H), 7.64
(broad d, J = 7.52 Hz, 1H), 7.60 (m, 1H), 7.55 (dd, J = 8.0,
0.7 Hz, 1H), 7.44–7.40 (m, 2H), 7.32 (dt, J = 7.81, 1.35, 1H),
7.27 (dt, J = 7.85, 1.02, 1H), 7.10 (s, 1H); 13C{1H} NMR (126
MHz, CD2Cl2) δ: 155.5, 148.1, 143.2, 129.3, 128.9, 125.6,
124.8, 123.9, 123.4, 121.1, 112.2, 111.6, 111.2, 102.9;
HRMS (EI–TOF) m/z (M+): calcd for C16H10O2, 234.0681;
found, 234.0684; elemental analysis (%): calcd for
C16H10O2: C, 82.04; H, 4.30. Found: C, 82.91; H, 4.88.
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2-Jodo-3-(benzo[b]furan-2-ylo)benzo[b]furan – 5a. To 6
mL of tetrahydrofuran, 702 mg (3 mmol) of 3-
(benzo[b]furan-2-yl)benzo[b]furan 7a was added and
then cooled to -40 °C and 1.8 mL (4.5 mmol, 2.5 M)
solution of n-butyllithium in hexane was added - the
mixture grew muddy and turned green. After 1 h, 1.14 g
(4.5 mmol) of iodine was added and the mixture was
brought to room temperature. Then 3 mL of a saturated
Na2SO3 aqueous solution and 6 mL of dichloromethane
were added. After discoloration of the mixture, the
phases were separated, the aqueous layer was extracted
with 6 mL of dichloromethane and the combined
extracts were dried over MgSO4 and evaporated. The
solid residue was suspended in 6 mL of methanol and
filtrated to give 1.02 g of a light yellow solid, with the
reaction yield of 94%.1H NMR (500 MHz, CD2Cl2) δ: 8.18–
8.13 (m, 1H), 7.71–7.68 (m, 1H), 7.63 (dd, J = 8.1, 0.7 Hz,
1H), 7.57–7.55 (m, 1H), 7.43 (d, J = 0.9 Hz, 1H), 7.39–7.34
(m, 3H), 7.32 7.28 (dt, J = 7.2, 1.1, 1H); 13C{1H} NMR (126
MHz, CD2Cl2) δ: 158.6, 154.9, 149.3, 128.7, 126.6, 125.6,
125.0, 124.1, 123.6, 121.4, 121.2, 120.0, 111.5, 111.3,
104.6, 97.5;HRMS (EI–TOF) m/z (M+): calcd for C16H9IO2,
359.9647; fund, 359.9639; elemental analysis (%): calcd
for C16H9IO2: C, 53.36; H, 2.52. Found: C, 54.04; H, 2.74.
1
43%. The mp. was 230 °C. H NMR (500 MHz, CDCl3) δ:
8.41 (d, J = 7.53 Hz, 1H), 8.34 (d, J = 7.16 Hz, 1H), 8..33 (d,
J = 7.18 Hz, 1H), 7.78 (d, J = 7.78 Hz, 1H), 7.76 (d, J = 7.55
Hz, 1H), 7.57–7.44 (m, 6H), 7.39 (td, J = 7.4, 1.0 Hz, 1H),
2.84 – 2.77 (m, 2H), 2.42–2.28 (m, 2H), 0.27 (t, J = 7.25Hz,
6H); 13C{1H} NMR (126 MHz, CDCl3) δ 157.0, 156.3, 151.2,
150.4, 149.4, 144.1, 139.7, 127.3, 126.8, 126.4, 125.9,
123.7, 123.6, 123.4, 123.0, 122.4, 122.3, 122.2, 122.1,
121.9, 115.8, 112.1, 111.8, 109.1, 59.1, 30.6, 8.7; HRMS
(EI–TOF) m/z (M+): calcd for C29H22O2, 402.1620; found,
402.1636 (M+); elemental analysis (%): calcd for C29H22O2:
C, 86.54; H, 5.51. Found: C, 86.44; H, 6.01.
2,3-Dibromobenzo[b]thiophene – 12b. 45.7 g (341 mmol)
of benzo[b]thiophene 15b was dissolved in 480 mL of
chloroform and then 39 mL (755 mmol, d = 3.1028 g/mL)
of bromine was slowly added. After 20 h, 60.9 mL of
dichloromethane and 60.9 mL of saturated aqueous
solution of Na2S2O3 were added. The organic layer was
separated, dried over MgSO4 and evaporated. Obtained
oil was treated with 250 mL of hexane and cooled in the
freezer. After solidifying, the mixture was brought to
room temperature and the resulting precipitate was
filtered off. The filtrate was concentrated and re-cooled,
and the formed solid was filtered. (The process was
repeated several times, because there was still a lot of
product in the post-crystallization liquor.) Finally, 83.58 g
of a white solid, with the reaction yield of 84%, was
obtained. The mp. was 54 °C. The analysis is consistent
with the literature data.65 1H NMR (400 MHz, CDCl3) δ:
7.72 (d, J = 8.0 Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H), 7.41-7.36
(m, 2H); 13C{1H} NMR (75.5 MHz, CDCl3) δ: 139.1, 137.7,
125.9, 125.7, 123.5, 122.1, 114.4, 111.9
15,15-diethyl-5,10-dioxatruxene – OOC. Step I (synthesis
of trimer 2a): To 12 mL of toluene, 720 mg (2 mmol) of
2-iodo-3-(benzo[b]furan-2-yl)benzo[b]furan
5a
was
added and the mixture was cooled to -78 °C. Next, 0.8
mL (2 mmol, 2.5 M) of n-butyllithium in hexane was
added - the solution turned yellow. After 10 min, 264 mg
(2 mmol) of indan-1-one 4 dissolved in 10 mL of
anhydrous toluene was slowly added and then brought
to room temperature. After 1.5 h, an NH4Cl aqueous
solution (107 mg in 2 mL water) was added, the phases
were separated and the organic layer was evaporated.
The mixture was then dissolved in 2 mL of 1,2-
dichloroethane and 0.13 mL (2 mmol, d = 1.48 g/mL) of
CH3SO3H and 240 mg of MgSO4 was added followed by
boiling. After 0.5 h the mixture was cooled, 4 mL of water
and 6 mL of dichloromethane were added, the organic
layer was separated, dried over MgSO4 and evaporated.
The crude product was purified via column
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The Journal of Organic Chemistry
Page 8 of 17
3-Bromobenzo[b]thiophene
tetrahydrofuran, 16.06
–
24. To 55 mL of
(55 mmol) of 2,3-
(100 MHz, CDCl3) δ: 140.8, 140.4, 139.4, 137.7, 137.3,
130.8, 125.5, 125.0, 124.9, 124.7, 124.5, 123.7, 123.2,
123.1, 122.3, 121.6.
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8
g
dibromobenzo[b]thiophene 12b was added and cooled
to -40 °C, followed by slowly addition of 22 mL (55
mmol, 2.5 M) of a solution of n-butyllithium in hexane.
After addition, the mixture turned yellow and the
precipitate appeared. After 1 h stirring, at constant
temperature, 22 mL of water was added to the solution,
the organic layer was separated, whereas the aqueous
layer was extracted two times with 55 mL of
dichloromethane. Then combined extracts were dried
over MgSO4 and evaporated. The crude product was
distilled under reduced pressure to give 10.43 g of a
colorless liquid, with the reaction yield of 89%. The
analysis is consistent with the literature data.66 1H NMR
(300 MHz, CDCl3) δ: 7.88-7.86 (m, 2H), 7.52-7.41 (m, 3H).
2-Jodo-3-(benzo[b]thien-2-yl)benzo[b]thiophene – 5b. To
3 mL of tetrahydrofuran, 399 mg (1.5 mmol) of 3-
(benzo[b]thien-2-yl)benzo[b]thiophene 7b was added.
Then solution was cooled to -40 °C and 0.9 mL (2.25
mmol, 2.5 M) of a solution of n-butyllithium in hexane
was added - the mixture turned purple and after a while
a pink precipitate was formed. After 1 h, 571.3 mg (2.25
mmol) of iodine was added and solution was brought to
room temperature. After warming, 1.5 mL of a saturated
aqueous Na2SO3 solution and 3 mL of dichloromethane
were added. After discoloration of the mixture, the
phases were separated, the aqueous layer was extracted
with 3 mL of dichloromethane and the combined
extracts were dried over MgSO4 and evaporated. The
solid residue was suspended in 3 mL of methanol and
filtered to give 547.4 mg of a light yellow solid, with the
reaction yield of 93%. The mp. was 165 °C. 1H NMR (500
MHz, CD2Cl2) δ: 7.93 (d, J = 8.3 Hz, 1H), 7.91 (d, J = 8.3
Hz, 1H), 7.82 (t, J = 8.4 Hz, 2H), 7.47 (s, 1H), 7.46–7.40 (m,
2H), 7.39–7.32 (m, 2H); 13C{1H} NMR (126 MHz, CD2Cl2) δ:
144.0, 141.0, 140.1, 139.0, 136.9, 136.5, 126.0, 125.4,
125.3, 125.1, 124.9, 124.3, 123.1, 122.6, 121.9, 84.3; HRMS
(EI–TOF) m/z (M+): calcd for C16H9IS2, 391.9190; found,
391.9193; elemental analysis (%): calcd for C16H9IS2: C,
48.99; H, 2.31. Found: C, 48.45; H, 2.41.
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Benzo[b]thien-2-ylboronic acid – 8b. To 40 mL of
tetrahydrofuran, 5.36 g (40 mmol) of benzo[b]thiophene
15b was added and then the mixture was cooled to -78
°C. Next, 16 mL (40 mmol, 2.5 M) of a solution of n-
butyllithium in hexane was added - a white precipitate
appeared. After 1 h, the mixture was brought to room
temperature and cooled again to -78 °C. Then 5 mL (45
mmol, d = 0.932 g/mL) of trimethylborate was added
and obtained solution was slowly elevated to room
temperature. After that 10 mL of aqueous HCl (1:9, HCl :
water) was added to the mixture and extracted three
times with 40 mL of dichloromethane. Combined extracts
were dried over MgSO4 and evaporated. The solid
residue was treated with 40 mL of hexane, cooled to 0 °C
and filtered. 5.49g of a white solid, with the reaction yield
of 77%, was obtained. The analysis is consistent with the
literature data.67 1H NMR (500 MHz, acetone-d6) δ 7.99-
7.93 (m, 2H), 7.91 (m, 1H), 7.59 (s, 2H), 7.41-7.33 (m, 2H);
13C{1H} NMR (126 MHz, acetone-d6) δ 143.4, 140.8, 132.6,
124.8, 124.0, 123.8, 122.2.
3-(3-Bromobenzo[b]thien-2-yl)-1H-indene – 9b. To 60 mL
of
toluene,
2.92
g
(10
mmol)
of
2,3-
dibromobenzo[b]thiophene 12b was added and then the
obtained solution was cooled to -78 °C. After that, 4 mL
(10 mmol, 2.5 M) of a solution of n-butyllithium in
hexane was added - a white precipitate appeared. After
30 min, a solution of 1.32 g (10 mmol) of indan-1-one 4
in 20 mL of toluene was slowly added - after a while, the
precipitate dissolves. The solution transferred to room
temperature turned yellow. After 1 h, 10 mL (10 mmol, 1
M) of an aqueous NH4Cl was added. The aqueous layer
was extracted with 60 mL of dichloromethane and then
the combined extracts were evaporated. Obtained
residue was dissolved in 10 mL of 1,2-dichloroethane
and 0.973 mL (15 mmol, d = 1.48 g/mL) of CH3SO3H and
1.2 g of MgSO4 were added. The solution was refluxed 30
min and then cooled. 5 mL (10 mmol, 2 M) of a K2CO3
aqueous solution and 5 mL of dichloromethane were
added. The organic layer was separated, dried over
MgSO4 and evaporated. The solid residue was dissolved
in 10 mL of dichloromethane and 20 mL of methanol was
added. Then dichloromethane was slowly evaporated.
The resulting white solid was collected by filtration to
give 2.4 g, with the reaction yield of 73%. The mp. was
3-(Benzo[b]thien-2-yl)benzo[b]thiophene – 7b. To 12 mL
of tetrahydrofuran under argon atmosphere, 123 mg (1
mmol) of 3-bromobenzo[b]thiophene 24, 178 mg (1
mmol) of benzo[b]thien-2-ylboronic acid 8b, 7mg (0.04
mmol) of palladium(II) chloride, 42 mg (0.16 mmol) of
triphenylphosphine and 1.5 mL (3 mmol, 2 M) of K2CO3
aqueous solution was added, then obtained solution was
kept under reflux. The mixture turned muddy light brown
that changed into red-brown as the reaction proceeded.
After 3h, the solution was cooled and evaporated to
dryness. The crude product was purified via column
chromatography using silica gel as stationary phase and
hexane as eluent. 126.5 mg of a white solid, with the
reaction yield of 48%, was obtained. The analysis is
consistent with the literature data.68 1H NMR (400 MHz,
CDCl3) δ: 8.31 (d, J = 8.00 Hz, 1H), 7.98 (d, J = 7.60
Hz,1H), 7.93 ( d, J = 7.60 Hz, 1H), 7.89 (d, J = 7.60 Hz, 1H),
7.66 (s, 1H), 7.62 (s, 1H), 7.56–7.41 (m, 4H); 13C{1H} NMR
1
109 °C. H NMR (500 MHz, CD2Cl2) δ: 7.91 (d, J = 8.1 Hz,
1H), 7.88 (d, J = 7.9 Hz, 1H), 7.60 (d, J = 7.5 Hz, 1H), 7.58
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The Journal of Organic Chemistry
(d, J = 7.3 Hz, 1H), 7.55 – 7.50 (m, 1H), 7.48 – 7.43 (m, 3-(3-bromobenzo[b]thien-2-yl)-1H-indene 9b, 924.45
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5
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7
8
1H), 7.34 (dd, J = 7.4, 6.9 Hz, 1H), 7.30 (td, J = 7.4, 0.9 Hz,
1H), 7.00 (t, J = 2.1 Hz, 1H), 3.64 (d, J = 2.0 Hz, 2H);
13C{1H} NMR (126 MHz, CD2Cl2) δ: 144.2, 143.6, 139.0,
138.3, 137.7, 136.8, 133.2, 126.6, 125.9, 125.8, 125.6,
124.4, 123.7, 122.7, 121.4, 106.9, 39.3; HRMS (EI–TOF)
m/z (M+): calcd for C17H9SBr, 325.9725; found, 325.9760;
elemental analysis (%): calcd for C17H9SBr: C, 62.40; H,
3.39. Found: C, 62.74; H, 3.83.
mg (0.8 mmol) of Pd(PPh3)4, were added and after the
dissolution of the substrates, 15 mL (30 mmol, 2 M) of
K2CO3 aqueous solution was introduced. The solution
was refluxed under argon atmosphere. The mixture
turned muddy dark brown. After 24 h, it was cooled, the
organic layer was separated and evaporated. The crude
product was purified via column chromatography using
silica gel as stationary phase and hexane → 4% solution
of dichloromethane in hexane (after collecting the
substrate) as eluent. The obtained product was dissolved
in 15 mL of dichloromethane and very slowly evaporated.
Then 30 mL of methanol was added. The precipitate was
collected by filtration to give 1.91 g of a white solid, with
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3-(3-Bromobenzo[b]thien-2-yl)-1,1-diethyl-1H-indene
–
28, 3-(3-Bromobenzo[b]thien-2-yl)-1,3-diethyl-1H-indene
– 29. To 50 mL of dimethylformamide (saturated with
argon at 0 °C for 1h), 3.27 g (10 mmol) of 3-(3-
bromobenzo[b]thien-2-yl)-1H-indene 9b was added
followed by the addition of 2.46 g (44 mmol) of
shredded potassium hydroxide and 3.28 mL (44 mmol, d
= 1.46 g/mL) of bromoethane - the mixture turned dark
yellow. After stirring for 24 h, 50 mL of water was added
and the mixture was extracted three times with 50 mL of
hexane. The organic layer was dried over MgSO4 and
evaporated The crude product was purified via column
chromatography using silica gel as stationary phase and
petroleum ether as eluent to obtain 351 mg of 28, as a
white solid, with the reaction yield of 92%. The mp was
91 °C. Without changing the eluent (petroleum ether)
1.89 g of 29, with the reaction yield of 49%, as a white
solid, was obtained. The mp was 59 °C. 28 has slightly
larger Rf (SiO2 / hexane) compared to 29 and changed
color to orange after irradiation with UV-C light. For 28:
1H NMR (400 MHz, CDCl3) δ: 7.89 (d, J = 8.0 Hz, 1H), 7.84
(d, J = 7.9 Hz, 1H), 7.50 (dd, J = 9.5, 5.5 Hz, 2H), 7.46 –
7.39 (m, 1H), 7.32 – 7.26 (m, 3H), 6.71 (s, 1H), 2.05 – 1.84
(m, 4H), 0.70 (t, J = 7.4 Hz, 6H); 13C{1H} NMR (101 MHz,
CDCl3) δ: 150.8, 147.0, 143.6, 139.0, 138.2, 135.1, 133.1,
126.7, 126.0, 125.7, 125.5, 123.9, 122.6, 122.2, 121.4,
107.1, 58.7, 30.5, 9.4; HRMS (EI–TOF) m/z (M+): calcd for
C21H19SBr, 382.0391; found, 382,0392; elemental analysis
(%): calcd for C21H19SBr: C, 65.80; H, 5.00. Found: C, 65.91;
H, 5.11. For 29: 1H NMR (400 MHz, CDCl3) δ: 7.78 (ddd, J
= 8.1, 1.1, 0.7 Hz, 1H), 7.66 – 7.63 (m, 1H), 7.63 – 7.59 (m,
1H), 7.41 – 7.37 (m, 1H), 7.34 (dd, J = 7.0, 1.0 Hz, 1H),
7.33 – 7.28 (m, 2H), 7.25 (td, J = 7.2, 1.8 Hz, 1H), 6.56 (t, J
= 1.6 Hz, 1H), 2.77 (dq, J = 14.6, 7.3 Hz, 1H), 2.63 – 2.53
(m, 2H), 2.43 – 2.30 (m, 1H), 1.32 (t, J = 7.4 Hz, 3H), 0.74
(t, J = 7.3 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ: 150.1,
146.0, 145.1, 141.5, 140.1, 136.1, 133.4, 127.9, 125.6,
125.2, 125.1, 124.0, 122.8, 122.1, 119.8, 105.1, 58.7, 29.7,
20.9, 12.5, 9.4; HRMS (EI–TOF) m/z (M+): calcd for
C21H19SBr, 382.0391; found, 382,0390; elemental analysis
(%): calcd for C21H19SBr C, 65.80; H, 5.00. Found: C, 65.74;
H, 5.08.
1
the reaction yield of 50%. The mp. was 180 °C. H NMR
(500 MHz, CD2Cl2) δ: 8.04 – 8.01 (m, 1H), 7.96 – 7.93 (m,
1H), 7.80 (d, J = 7.8 Hz, 1H), 7.78 – 7.75 (m, 1H), 7.51 –
7.48 (m, 1H), 7.48 – 7.44 (m, 2H), 7.40 (s, 1H), 7.38 – 7.37
(m, 1H), 7.35 (dd, J = 7.7, 1.3 Hz, 1H), 7.33 – 7.29 (m, 1H),
7.21 – 7.14 (m, 2H), 6.75 (t, J = 2.1 Hz, 1H), 3.54 (d, J = 2.0
Hz, 2H); 13C{1H} NMR (126 MHz, CD2Cl2) δ: 144.7, 144.6,
141.2, 140.7, 140.6, 139.7, 138.2, 137.8, 137.4, 137.0,
129.0, 126.9, 125.9, 125.8, 125.7, 125.3, 125.1, 125.1,
124.7, 124.4, 124.0, 123.0, 122.8, 121.3, 39.7. HRMS (EI–
TOF) m/z (M+): calcd for C25H16S2, 380.0693; found,
380.0698; elemental analysis (%): calcd for C25H16S2: C,
78.91; H, 4.24. Found: C, 78.57; H, 4.49.
15,15-Diethyl-5,10-dithiatruxene – SSC. 95 mg (0.25
mmol) of trimer 2b and 9.53 mg (0.0375 mmol) of iodine
were dissolved in 250 mL of toluene, and irradiated with
UV-C light. After
3 h the reaction mixture was
evaporated, the resulting orange solid was suspended in
5 mL of methanol and filtered. Obtained material was
then suspended in 1.25 mL of dimethylformamide
(saturated with argon at 0 °C for 1 h) and 0.082 mL (1.1
mmol, d = 1.46 g/mL) of bromoethane and 61 mg (1.1
mmol) of shredded potassium hydroxide were added.
After stirring for 24 h, 5 mL of water was added and
obtained solution was extracted three times with 2.5 mL
of dichloromethane. The organic layer was dried over
MgSO4 and evaporated. The crude product was purified
via column chromatography using silica gel as stationary
phase and 1 → 10% solution of dichloromethane in
hexane as eluent to obtain 51 mg of a white solid, with
1
the reaction yield of 47%. The mp. was 255 °C. H NMR
(400 MHz, CDCl3) δ: 8.97 (d, J = 8.0 Hz, 1H), 8.75 (d, J =
8.0 Hz, 1H), 8.19–8.16 (m, 1H), 8.13–8.09 (m, 2H), 7.76–
7.70 (m, 1H), 7.65–7.61 (m, 2H), 7.60–7.53 (m, 3H), 7.50–
7.45 (m, 1H), 3.12 (dq, J = 14.5, 7.3 Hz, 2H), 2.41 (dq, J =
14.8, 7.4 Hz, 2H), 0.29 (t, J = 7.3 Hz, 6H); 13C{1H} NMR
(126 MHz, CDCl3) δ: 151.7, 144.6, 141.0, 140.2, 139.6,
135.0, 134.9, 134.5, 134.3, 132.3, 131.4, 129.8, 127.5,
127.4, 126.6, 126.6, 126.1, 125.4, 124.8, 124.5, 123.5,
123.3, 122.4, 121.7, 60.1, 30.3, 9.3; HRMS (EI–TOF) m/z
3-(3-(Benzo[b]thien-2-yl)benzo[b]thien-2-yl)-1H-indene –
2b. To 120 mL of tetrahydrofuran, 1.78 g (10 mmol) of
benzo[b]thien-2-ylboronic acid 8b, 3.27 g (10 mmol) of
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(M+): calcd for C29H22S2, 434.1163; found, 434.1160; 7.16 (t, J = 7.3 Hz, 1H), 4.79 (q, J = 7.2 Hz, 2H), 4.63 (q, J =
1
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elemental analysis (%): calcd for C29H22S2: C, 80.14; H,
5.10. Found: C, 80.04; H, 5.32.
7.1 Hz, 2H), 1.62 (t, J = 7.2 Hz, 3H), 1.29 (t, J = 7.1 Hz, 3H);
13C{1H} NMR (126 MHz, CD2Cl2) δ: 194.9, 145.2, 144.6,
142.7, 139.1, 137.9, 135.2, 134.3, 128.6, 127.1, 126.6,
126.6, 125.7, 124.1, 123.9, 123.6, 123.1, 123.1, 123.0,
121.0, 120.6, 116.8, 115.4, 111.9, 109.9, 42.3, 41.8, 16.0,
14.4; HRMS (EI–TOF) m/z (M+): calcd for C29H22N2O,
414.1732; found, 414.1721; elemental analysis (%): calcd
for C29H22N2O: C, 84.03; H, 5.35; N, 6.76. Found: C, 84.44;
H, 5.88; N, 6.51.
5,10–Dithiatruxene–15–one – 13b. 1.34 g (10 mmol) of
benzo[b]thiophene 15b was dissolved in 20 mL of 1,2-
dichloroethane, followed by the addition of 890 mg (5
mmol) of ninhydrin 14 and 1.29 mL (20 mmol) of
methanesulfonic acid. The solution was stirred for 0.5 h
at room temperature and refluxed. After 3 h, it was
cooled and left overnight. Formed participate was
filtrated, washed with 20 mL of dichloromethane and 20
mL of methanol to obtain 1.45 g of an orange solid, with
the reaction yield of 74%. The NMR analysis is in
accordance with the literature data.59 1H NMR (500 MHz,
CDCl3) δ: 9.95 (d, J = 8.6 Hz, 1H), 8.60 (d, J = 7.9 Hz, 1H,),
8.05 (d, J = 7.9 Hz,1H), 7.95 (d, J = 7.9 Hz, 1H), 7.80 (d, J =
7.3 Hz, 1H), 7.75 (d, J = 7.3 Hz, 1H), 7.69 (t, J = 7.3 Hz,
1H), 7.63-7.57 (m, 4H), 7.37 (t, J = 6.7 Hz, 1H); elemental
analysis (%): calcd for C25H12OS2: C, 76.50; H, 3.08. Found:
C, 76.74; H, 3.11.
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5,10–Diethyl–5,10–diazatruxene – 1c. 207 mg (0.5 mmol)
of 5.10-diethyl-5.10-diazatruxene-15-one 13c was
dissolved in 4 mL of ethylene glycol, then 0.121 mL (2.5
mmol, d = 1.032 g/mL) of hydrazine monohydrate was
added. Obtained mixture was refluxed under argon
atmosphere and left overnight. Then the solution was
cooled and 112 mg (2 mmol) of potassium hydroxide
was added. After 0.5 h of refluxing under argon
atmosphere the mixture was cooled and 4 mL of
aqueous ammonium chloride solution (0.5 M) was
added. The light yellow participate was filtered off. The
crude product was purified via column chromatography
using silica gel as stationary phase and 20%
dichloromethane in hexane as eluent to obtain 192.2 mg
of a white solid, with the reaction yield of 96%. The mp.
was 169 °C. 1H NMR (500 MHz, CD2Cl2) δ: 8.43 (d, J = 8.1
Hz, 1H), 8.19 (d, J = 7.6 Hz, 1H), 8.05 (d, J = 7.8 Hz, 1H),
7.73 (d, J = 7.3 Hz, 1H), 7.70 (d, J = 8.1 Hz, 1H), 7.62 (d, J
= 8.1 Hz, 1H), 7.55–7.46 (m, 3H), 7.40–7.36 (m, 2H), 7.31
(t, J = 7.3 Hz, 1H), 4.97 (q, J = 7.2 Hz, 2H), 4.89 (q, J = 7.1
Hz, 2H), 4.47 (s, 2H), 1.73 (t, J = 7.2 Hz, 3H), 1.35 (t, J =
7.1 Hz, 3H); 13C{1H} NMR (126 MHz, CD2Cl2) δ: 143.8,
142.5, 141.9, 141.4, 139.0, 139.0, 137.1, 126.9, 125.3,
124.7, 124.6, 124.6, 124.4, 124.0, 122.7, 122.5, 121.0,
120.5, 120.2, 119.4, 114.4, 111.8, 109.8, 109.4, 42.5, 41.8,
38.0, 16.3, 14.6; HRMS (EI–TOF) m/z (M+): calcd for
C29H24N2, 400.1939; found, 400.1931; elemental analysis
(%): calcd for C29H24N2: C, 86.97; H, 6.04; N, 6.99. Found:
C, 87.06; H, 6.18; N, 6.76.
N-ethylindole – 15c. To 50 mL of dimethylformamide,
11.7 g (100 mmol) of indole and 8.4 g (150 mmol) of
potassium hydroxide were added, and the mixture was
cooled to 0 °C. After 20 min 22.8 mL (150 mmol, d = 1.46
g/mL) of bromoethane was added. After stirring for 24 h,
100 mL of water was added and the solution was
extracted with 6 x 50 mL of hexane. The combined
extracts were washed with 50 mL of brine, dried over
MgSO4, and evaporated. 14.35 g of a colorless liquid,
with the reaction yield of c.a. 100%, was obtained. The
analysis is in accordance with the literature data.69 1H
NMR (300 MHz, CDCl3) δ: 7.72 (d, J = 7.8 Hz, 1H), 7.45 (d,
J = 8.1 Hz, 1H), 7.30 (t, J = 8.1 Hz, 1H), 7.22–7.17 (m, 2H),
6.59 (d, J = 3.9 Hz, 1H), 4.29 (q, J = 7.2 Hz, 2H), 1.58 (t, J =
7.2 Hz, 3H); 13C{1H} NMR (75 MHz, CDCl3) δ: 16.0, 41.4,
101.5, 109.7, 119.7, 121.5, 121.8, 127.5, 129.2, 136.2.
5,10–Diethyl–5,10–diazatruxene–15–one – 13c. 10.74 g
(74 mmol) of N-ethylindole 15c was dissolved in 74 mL
of 1,2-dichloroethane, followed by the addition of 6.59 g
(37 mmol) of ninhydrin 14 and 4.79 mL (74 mmol) of
methanesulfonic acid. The solution was stirred for 0.5 h
at room temperature and refluxed. After 2.5 h, it was
cooled and left overnight. Then 74 mL of water were
added, the organic layer was separated, and the aqueous
layer was extracted two times with 37 mL of
dichloromethane. The combined extracts were dried over
MgSO4 and evaporated. The crude product was purified
via column chromatography using silica gel as stationary
phase and 20% → 40% dichloromethane solution in
hexane as eluent to obtain 4.75 g of a dark brown solid,
5,10,15,15–Tetraethyl–5,10–diazatruxene – NNC. 1.6 g (4
mmol) of 5,10–diethyl–5,10–diazatruxene 1c was
suspended in 40 mL of tetrahydrofuran and cooled to -
78 °C. Then 2 mL (5 mmol, 2.5 M) of n-butyllithium
solution in hexane was added – mixture turned orange.
After 0.5 h in constant temperature, 0.375 mL (5 mmol,
d = 1.46 g/mL) of bromoethane was added and the
temperature was slowly raised to room temperature and
then lowered again to -78 °C. The whole procedure of n-
butyllithium addition followed by addition of
bromoethane was repeated two times. After warming the
mixture to room temperature the solvent was
evaporated. The crude product was purified via column
chromatography using silica gel as stationary phase and
5% dichloromethane in hexane as eluent to obtain 822.8
1
with the reaction yield of 31%. The mp. was 188 °C. H
NMR (500 MHz, CD2Cl2) δ: 9.37 (d, J = 7.9 Hz, 1H), 8.30
(d, J = 8.2 Hz, 1H), 7.60 (dd, J = 7.1, 0.6 Hz, 1H), 7.58–7.49
(m, 5H), 7.42 (dt, J = 7.5, 1.2 Hz, 1H), 7.35–7.31 (m, 2H),
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mg of a white solid, with the reaction yield of 45%. The 138.7, 138.2, 128.6, 125.7, 125.4, 124.9, 124.7, 124.2,
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7
8
mp. was 170 °C. 1H NMR (500 MHz, CD2Cl2) δ: 8.56 (d, J =
8.0 Hz, 1H), 8.42 (d, J = 8.1 Hz, 1H), 7.91 (d, J = 7.7 Hz,
1H), 7.72 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 8.1 Hz, 1H), 7.55–
7.46 (m, 3H), 7.43 (dt, J = 7.6, 1.1 Hz, 1H), 7.40–7.36 (m,
1H), 7.33 (t, J = 7.5 Hz, 2H), 5.02 (q, J = 7.2 Hz, 2H), 4.83
(q, J = 7.0 Hz, 2H), 3.11 – 3.01 (m, 2H), 2.33 (dq, J = 14.6,
7.4 Hz, 2H), 1.72 (t, J = 7.2 Hz, 3H), 1.00 (t, J = 7.0 Hz, 3H),
0.23 (t, J = 7.3 Hz, 6H); 13C{1H} NMR (126 MHz, CD2Cl2) δ:
150.9, 145.3, 144.0, 141.9, 141.8, 139.2, 138.3, 126.7,
125.2, 124.9, 124.7, 124.2, 124.2, 123.8, 122.9, 122.6,
122.0, 120.8, 120.6, 119.8, 114.9, 112.6, 110.3, 110.2, 58.7,
42.9, 41.9, 29.8, 16.1, 13.4, 8.9; HRMS (EI–TOF) m/z (M+):
calcd for C33H32N2, 456.2565; found, 456.2560; elemental
analysis (%): calcd for C33H32N2: C, 86.80; H, 7.06; N, 6.13.
Found: C, 86.92; H, 7.15; N, 5.93.
123.4, 123.3, 123.0, 122.4, 120.7, 120.0, 117.1, 114.6,
112.1, 110.8, 109.6, 85.7, 42.5, 41.8, 31.1, 16.2, 13.8, 8.9;
HRMS (EI–TOF) m/z (M+): calcd for C31H28N2O, 444.2202;
found, 444.2206; elemental analysis (%): calcd for
C31H28N2O: C, 83.75; H, 6.35; N, 6.30. Found: C, 83.68; H,
6.24; N, 6.25.
9
General procedure for synthesis of bromoderivatives 17:
1 mmol of soluble 5,10-diheterotruxene (OOC, SSC or
NNC) was dissolved in 1 mL of dichloromethane at 0 °C
and 0.16 mL (3.1 mmol, 3.1 eq) of bromine was slowly
added. After 1 h 10 mL of methanol was added dropwise
and the formed participate was filtrated to get
bromoderivatives 17.
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2,8,13-Tribromo-15,15-diethyl-5,10-dithiatruxene – 17b.
General procedure for synthesis of alcohols 16: 0.25
mmol of 13 was suspended in 1 mL of anhydrous
toluene followed by addition of 0.1 mL (0.3 mmol, 1.2 eq)
of a solution of ethylmagnesium bromide in diethyl ether
(3 M). After 0.5 h in reflux mixture was cooled to room
641 mg, as white solid was obtained, with the reaction
1
yield of 96%. The mp. was >300 °C. H NMR (500 MHz,
CD2Cl2) δ: 9.15 (s, 1H), 8.85 (d, J = 5.0 Hz, 1H), 8.44 (d, J
= 8.6 Hz, 1H), 8.38 (d, J = 1.4 Hz, 1H), 8.34 (s, 1H), 8.03
(d, J = 8.2 Hz, 1H), 7.96 (d, J = 8.5 Hz, 1H), 7.74 – 7.68
(m, 2H), 2.94 (dq, J = 14.7, 7.5 Hz, 2H), 2.40 (dq, J = 14.6,
7.4 Hz, 2H), 0.27 (t, J = 7.3 Hz, 6H); HRMS (EI–TOF) m/z
(M+): calcd for C29H19Br3S2, 667.8478; found, 667.8476;
elemental analysis (%): calcd for C29H19Br3S2: C, 51.89; H,
2.85. Found: C, 52.01; H, 2.99. Due to low solubility
13C{1H} NMR cannot be measured.
temperature and
5 mL of water and 5 mL of
dichloromethane were added. Collected organic phase
was dried over MgSO4 and then evaporated to obtain
alcohols 16.
5-Hydroxy-15-ethyl-5,10-dithiatruxene – 16b. 99 mg as a
pale yellow solid, with the reaction yield of 94%, was
1
obtained. H NMR (500 MHz, CD2Cl2) δ: 9.36 (d, J = 8.0
2,8,13-Tribromo-5,10,15,15-tetraethyl-5,10-diazatruxene
Hz, 1H), 8.47 (d, J = 8.0 Hz, 1H), 7.97 (d, J = 7.9 Hz, 1H),
7.90 (d, J = 7.6 Hz, 1H), 7.82 (d, J = 7.4 Hz, 1H), 7.62 (t, J =
7.5 Hz, 1H), 7.58 (d, J = 7.3 Hz, 1H), 7.55 – 7.51 (m, 1H),
7.50 (d, J = 7.4 Hz, 1H), 7.46 (t, J = 7.2 Hz, 2H), 7.38 (t, J =
7.3 Hz, 1H), 2.65 (dq, J = 14.6, 7.3 Hz, 1H), 2.40 (dq, J =
14.9, 7.6 Hz, 1H), 0.24 (t, J = 7.4 Hz, 3H); 13C{1H} NMR
(126 MHz, CD2Cl2) δ: 149.0, 142.7, 140.2, 139.3, 139.0,
134.6, 134.6, 134.3, 131.5, 131.5, 131.1, 130.6, 129.3,
128.1, 127.9, 126.8, 126.6, 125.5, 125.0, 124.4, 123.2,
123.1, 122.7, 121.8, 86.1, 30.4, 8.6; HRMS (EI–TOF) m/z
(M+): calcd for C27H18OS2, 422.0799; found, 422.0791;
elemental analysis (%): calcd for C27H18OS2: C, 76.74; H,
4.29. Found: C, 76.81; H, 4.38. 1H NMR signal from OH
group proton was not visible.
– 17c. 635 mg as a white solid, with the reaction yield of
92%, was obtained. The mp. was 145°C. H NMR (500
1
MHz, CD2Cl2) δ: 8.61 (d, J = 1.2 Hz, 1H), 8.50 (d, J = 1.4
Hz, 1H), 7.73 (d, J = 8.2 Hz, 1H), 7.62 (dd, J = 8.7, 1.6 Hz,
2H), 7.60 – 7.56 (m, 2H), 7.55 (dd, J = 8.3, 1.8 Hz, 1H),
7.53 (d, J = 8.6 Hz, 1H), 4.91 (q, J = 7.1 Hz, 2H), 4.74 (q, J
= 7.0 Hz, 2H), 2.95 (dq, J = 14.5, 7.3 Hz, 2H), 2.29 (dq, J =
14.6, 7.3 Hz, 2H), 1.71 (t, J = 7.2 Hz, 3H), 0.99 (t, J = 7.0
Hz, 3H), 0.22 (t, J = 7.3 Hz, 6H); 13C{1H} NMR (126 MHz,
CD2Cl2) δ: 153.2, 145.8, 142.4, 140.5, 140.5, 138.8, 129.8,
127.6, 127.1, 126.5, 126.3, 125.9, 125.5, 125.3, 123.3,
119.4, 113.9, 113.9, 113.0, 111.8, 109.8, 59.1, 43.0, 42.2,
30.3, 16.0, 13.5, 8.8; HRMS (EI–TOF) m/z (M+): calcd for
C33H29Br3N2, 689.9881; found, 689.9875; elemental
analysis (%): calcd for C33H29Br3N2: C, 57.17; H, 4.22; N,
4.04. Found: C, 57.06; H, 4.18; N, 4.11.
15-Hydroxy-5,10,15-triethyl-5,10-diazatruxene
–
16c.
106.7 mg as a pale yellow solid, with the reaction yield of
96%, was obtained. 1H NMR (500 MHz, CD2Cl2) δ: 8.92 (d,
J = 7.9 Hz, 1H), 8.38 (d, J = 8.1 Hz, 1H), 7.78 (d, J = 7.6 Hz,
1H), 7.67 (d, J = 8.1 Hz, 1H), 7.62 (dd, J = 7.3, 0.6 Hz, 1H),
7.56 (d, J = 8.1 Hz, 1H), 7.54 – 7.50 (m, 1H), 7.48 – 7.44
(m, 1H), 7.44 – 7.40 (m, 1H), 7.39 – 7.34 (m, 1H), 7.32 –
7.29 (m, 1H), 7.29 – 7.26 (m, 1H), 4.96 – 4.87 (m, 2H), 4.84
– 4.75 (m, 2H), 2.74 (dq, J = 14.7, 7.4 Hz, 1H), 2.51 (dq, J =
14.7, 7.4 Hz, 1H), 2.41 (s, 1H), 1.70 (t, J = 7.2 Hz, 3H), 1.13
(t, J = 7.1 Hz, 3H), 0.51 (t, J = 7.4 Hz, 3H); 13C{1H} NMR
(126 MHz, CD2Cl2) δ: 149.6, 145.0, 143.5, 1141.8, 140.6,
2,7,8,12,13-Pentabromo-5,10,15,15-tetraethyl-5,10-
diazatruxene – 18. 456.6 mg (1 mmol) of NNC was
dissolved in 1 mL of dichloromethane and 0.26 mL (5.1
mmol, 5.1 eq)of bromine was slowly added. After 0.5 h
10 mL of methanol was added dropwise and formed
participate was filtrated to obtain 808.5 mg of white
solid, with the reaction yield of 95%. The mp. was 195 °C.
1H NMR (500 MHz, CD2Cl2) δ: 8.73 (s, 1H), 8.58 (s, 1H),
7.96 (s, 1H), 7.90 (s, 1H), 7.70 (d, J = 7.4 Hz, 1H), 7.64 (s,
1H), 7.55 (dd, J = 8.2, 1.7 Hz, 1H), 4.82 (m, 2H), 4.71 (m,
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Wiśniewska, of the Institute of Physical Chemistry of the
Polish Academy of Sciences, for measurements of thermal
properties.
2H), 2.89 (dq, J = 14.6, 7.3 Hz, 2H), 2.29 (dq, J = 14.3, 7.2
Hz, 2H), 1.71 (t, J = 7.2 Hz, 3H), 1.00 (t, J = 7.0 Hz, 3H),
0.21 (t, J = 7.3 Hz, 6H); 13C{1H} NMR (126 MHz, CD2Cl2) δ:
143.5, 143.5, 141.5, 138.8, 129.9, 129.9, 128.1, 127.0,
126.0, 125.3, 124.3, 123.6, 123.4, 123.4, 123.4, 120.3,
119.8, 117.1, 116.0, 114.9, 114.9, 109.0, 59.2, 43.2, 42.2,
30.3, 16.0, 13.5, 8.8; HRMS (EI–TOF) m/z (M+): calcd for
C33H27Br5N2, 845.8091; found, 845.8082; elemental
analysis (%): calcd for C33H27Br5N2: C, 46.57; H, 3.20; N,
3.29. Found: C, 46.96; H, 3.34; N, 3.18.
1
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5
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7
8
REFERENCES
(1)
(2)
(3)
Dehmlow, E. V.; Kelle, T. Synthesis of New
Truxene Derivatives: Possible Precursors of
Fullerene Partial Structures? Synth. Commun.
1997, 27 (11), 2021–2031.
9
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
Gómez-Lor, B.; de Frutos, Ó.; Ceballos, P. A.;
Thierry, G.; Echavarren, A. M. Synthesis of New
C3h and C3v Truxene Derivatives. European J.
Org. Chem. 2001, 2001 (11), 2107–2114.
ASSOCIATED CONTENT
Supporting Information.
The supporting information is available free of charge on
the ACS publication website.
Kimura, M.; Kuwano, S.; Sawaki, Y.; Fujikawa, H.;
Noda, K.; Taga, Y.; Takagi, K. New 9-Fluorene-
Type Trispirocyclic Compounds for Thermally
Stable Hole Transport Materials in OLEDs. J.
Mater. Chem. 2005, 15, 2393–2398.
Crystallographic information on OOC in dichloromethane
(CIF)
Crystallographic information on SSC in dichloromethane
(CIF)
(4)
(5)
(6)
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.
Crystallographic information on NNC in methanol (CIF)
Crystallographic information on 13b in chlorobenzene (CIF)
Crystallographic information on 13c in dichloromethane
(CIF)
Amick, A. W.; Scott, L. T. Trisannulated Benzene
Derivatives
Cyclotrimerizations
by
Acid
of
Catalyzed
Cyclic
Aldol
Ketones.
Crystallographic information on 1c in methanol (CIF)
Crystallographic information on 1c in acetonitrile (CIF)
Crystallographic information on 1c in acetone (CIF)
Crystal structures and NMR (PDF)
Methodology Development and Mechanistic
Insight. J. Org. Chem. 2007, 72 (9), 3412–3418.
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.
Emission spectrum of the UV-C lamp (PDF)
Absorption vs emission spectrum and quantum yield of
5,10-diheterotruxenes in CH2Cl2
(7)
Ginnari-Satriani, L.; Casagrande, V.; Bianco, A.;
Ortaggi, G.; Franceschin, M. A Hydrophilic
Three Side-Chained Triazatruxene as a New
Strong and Selective G-Quadruplex Ligand.
Org. Biomol. Chem. 2009, 7 (12), 2513–2516.
Calculated energy diagram
AUTHOR INFORMATION
Corresponding Authors
(8)
(9)
Gómez-Lor, B.; Echavarren, A. M. Synthesis of a
Triaza Analogue of Crushed-Fullerene by
Intramolecular Palladium-Catalyzed Arylation.
Org. Lett. 2004, 6 (17), 2993–2996.
*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.
Kaida, H.; Satoh, T.; Nishii, Y.; Hirano, K.; Miura,
M.
Synthesis
of
Benzobis-
and
ACKNOWLEDGMENTS
Benzotrisbenzofurans by Palladium-Catalyzed
Multiple Intramolecular C–H/C–H Coupling.
Chem. Lett. 2016, 45 (9), 1069–1071.
This work was supported by National Science Centre (FUGA
4, grant no. 2015/16/S/ST4/00427), and in part by the
Institute of Physical Chemistry, Polish Academy of Sciences.
The Authors cordially thank MSc Eng. Agnieszka
(10)
Pei, J.; Wang, J.-L.; Cao, X.-Y.; Zhou, X.-H.;
Zhang, W.-B. Star-Shaped Polycyclic Aromatics
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Based
on
Oligothiophene-Functionalized
(19)
Lai, W.-Y.; He, Q.-Y.; Zhu, R.; Chen, Q.-Q.;
Huang, W. Kinked Star-Shaped
1
2
3
4
5
6
7
8
9
Truxene: Synthesis, Properties, and Facile
Emissive Wavelength Tuning. J. Am. Chem. Soc.
2003, 125 (33), 9944–9945.
Fluorene/Triazatruxene Co-Oligomer Hybrids
with Enhanced Functional Properties for High-
Performance, Solution-Processed, Blue Organic
Light-Emitting Diodes. Adv. Funct. Mater. 2008,
18 (2), 265–276.
(11)
(12)
Yuan, M.-S.; Liu, Z.-Q.; Fang, Q. Donor-and-
Acceptor
Multifunctional Fluorescent Probes. J. Org.
Chem. 2007, 72 (21), 7915–7922.
Substituted
Truxenes
as
(20)
(21)
(22)
Gómez-Lor, B.; Hennrich, G.; Alonso, B.; Monge,
A.; Gutiérrez-Puebla, E.; Echavarren, A. M. A
Redox-Active C3-Symmetric Triindole-Based
Triazacyclophane. Angew. Chemie - Int. Ed.
2006, 45 (27), 4491–4494.
Cao, X.-Y.; Liu, X.-H.; Zhou, X.-H.; Zhang, Y.;
Jiang, Y.; Cao, Y.; Cui, Y.-X.; Pei, J. Giant
Extended
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
π-Conjugated
Dendrimers
Containing
the 10,15-Dihydro-5H-
Diindeno[1,2-a;1′,2′-c]Fluorene Chromophore:
Synthesis, NMR Behaviors, Optical Properties,
and Electroluminescence. J. Org. Chem. 2004,
69 (18), 6050–6058.
Destrade, C.; Malthete, J.; Tinh, N. H.;
Gasparoux,
H.
Truxene
Derivatives:
Temperature
Inverted
Nematic-Columnar
Sequence in Disc-Like Mesogens. Phys. Lett. A
1980, 78 (1), 82–84.
(13)
(14)
Cao, X.-Y.; Zi, H.; Zhang, W.; Lu, H.; Pei, J. Star-
Shaped and Linear Nanosised Molecules
Functionalized
Hexabenzocoronene: Synthesis and Optical
Properties. J. Org. Chem. 2005, 70 (9), 3645–
3653.
Warmerdam, T. W.; Nolte, R. J. M.; Drenth, W.;
Van Miltenburg, J. C.; Frenkel, D.; Zijlstra, R. J. J.
Discotic Liquid Crystals: Physical Parameters of
with
Hexa-Peri-
Some
2,3,7,8,12,13-
Hexa(Alkanoyloxy)Truxenes. Observation of a
Re-Entrant Isotropic Phase in a Pure Disc-like
Mesogen. Liq. Cryst. 1988, 3 (8), 1087–1104.
de Frutos, Ó.; Gómez-Lor, B.; Granier, T.;
Monge, M. Á.; Gutiérrez-Puebla, E.; Echavarren,
A. M. Syn-Trialkylated Truxenes: Building
Blocks That Self-Associate by Arene Stacking.
Angew. Chemie - Int. Ed. 1999, 38 (1–2), 204–
207.
(23)
(24)
(25)
(26)
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.
(15)
(16)
Liu, L.; Telfer, S. G. Systematic Ligand
Modulation Enhances the Moisture Stability
and Gas Sorption Characteristics of Quaternary
Metal-Organic Frameworks. J. Am. Chem. Soc.
2015, 137 (11), 3901–3909.
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.
Cayuela, R.; Nguyen, H. T.; Destrade, C.;
Levelut, A. M. Two Families of Trithiatruxene
Derivatives. Mol. Cryst. Liq. Cryst. 1989, 177,
81–91.
Lin, T.-C.; Tsai, B.-K.; Huang, T.-Y.; Chien, W.;
Liu, Y.-Y.; Li, M.-H.; Tsai, M.-Y. Synthesis and
Two-Photon Absorption Properties of Ladder-
Type Chromophores with Functionalized
Pyrazine Units Fused as the End-Groups. Dye.
Pigment. 2015, 120 (28), 99–111.
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
(17)
(18)
Cao, X.-Y.; Zhou, X.-H.; Zi, H.; Pei, J. Novel Blue-
Light-Emitting
Hyperbranched and Zigzag Type Copolymers:
Synthesis, Optical Properties, and Investigation
of Thermal Spectral Stability. Macromolecules
2004, 37 (24), 8874–8882.
Novel
Spirobifluorene
Truxene-Based
and
Emitters
Electron-Donating
with
Truxene-Containing
Moieties for Furnishing Highly Efficient Non-
Doped Blue-Emitting OLEDs. J. Mater. Chem. C
2015, 3 (22), 5783–5794.
(27)
Zhao, B.; Liu, B.; Png, R. Q.; Zhang, K.; Lim, K. A.;
Luo, J.; Shao, J.; Ho, P. K. H.; Chi, C.; Wu, J. New
Discotic Mesogens Based on Triphenylene-
Fused Triazatruxenes: Synthesis, Physical
Properties, and Self-Assembly. Chem. Mater.
2010, 22 (2), 435–449.
Shao, J.; Guan, Z.; Yan, Y.; Jiao, C.; Xu, Q.-H.;
Chi, C. Synthesis and Characterizations of Star-
Shaped Octupolar Triazatruxenes-Based Two-
Photon Absorption Chromophores. J. Org.
Chem. 2011, 76 (3), 780–790.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 14 of 17
(28)
(29)
(30)
Feng, G.-L.; Lai, W.-Y.; Ji, S.-J.; Huang, W. Demir, H. V. Ultralow-Threshold up-Converted
1
2
3
4
5
6
7
8
Synthesis of Novel Star-Shaped Carbazole-
Functionalized Triazatruxenes. Tetrahedron
Lett. 2006, 47 (39), 7089–7092.
Lasing in Oligofluorenes with Tailored Strong
Nonlinear Absorption. J. Mater. Chem. C 2015,
3 (46), 12018–12025.
Lai, W.-Y.; He, Q.-Y.; Chen, D.-Y.; Huang, W.
Synthesis and Characterization of Starburst 9-
Phenylcarbazole/Triazatruxene Hybrids. Chem.
Lett. 2008, 37 (9), 986–987.
(38)
(39)
Li, F.; Zhao, B.; Chen, Y.; Zhang, Y.; Wang, T.;
Xue, S. Synthesis, Characterization, and
Nonlinear Optical (NLO) Properties of Truxene-
Cored Diphenylamine Derivatives. Spectrochim.
Acta Part A Mol. Biomol. Spectrosc. 2017, 185,
20–26.
9
Lai, W.-Y.; Zhu, R.; Fan, Q.-L.; Hou, L.-T.; Cao, Y.;
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
Huang,
Triazatruxenes: Microwave-Enhanced Synthesis
and Highly Efficient Pure Deep-Blue
W.
Monodisperse
Six-Armed
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 Exhibiting Sub-Microsecond Reverse
Intersystem Crossing and Unity Quantum Yield
via Multiple Singlet–Triplet State Pairs. Adv. Sci.
2018, 5 (6), 1700989 (1-9).
Electroluminescence. Macromolecules 2006, 39
(11), 3707–3709.
(31)
(32)
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).
(40)
(41)
(42)
García-Frutos, E. M.; Gutierrez-Puebla, E.;
Monge, M. A.; Ramírez, R.; de Andrés, P.; de
Andrés, A.; Ramírez, R.; Gómez-Lor, B. Crystal
Structure and Charge-Transport Properties of
N-Trimethyltriindole: Novel p-Type Organic
Semiconductor Single Crystals. Org. Electron.
physics, Mater. Appl. 2009, 10 (4), 643–652.
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.
Ruiz, C.; Arrechea-Marcos, I.; Benito-
Hernández, A.; Gutiérrez-Puebla, E.; Monge, M.
A.; López Navarrete, J. T.; Ruiz Delgado, M. C.;
Ortiz, R. P.; Gómez-Lor, B. Solution-Processed
N-Trialkylated Triindoles for Organic Field
Effect Transistors. J. Mater. Chem. C 2018, 6 (1),
50–56.
(33)
(34)
Sang, M.; Cao, S.; Yi, J.; Huang, J.; Lai, W.-Y.;
Huang, W. Multi-Substituted Triazatruxene-
Functionalized Pyrene Derivatives as Efficient
Organic Laser Gain Media. RSC Adv. 2016, 6
(8), 6266–6275.
Ma, L.; Wu, Z.; Zhou, G.; Yuan, F.; Yu, Y.; Yao, C.;
Ning, S.; Hou, X.; Li, Y.; Wang, S.; et al. The
Molecular Picture of Amplified Spontaneous
Emission of Star-Shaped Functionalized-
Truxene Derivatives. J. Mater. Chem. C 2015, 3
(27), 7004–7013.
Gallego-Gõmez, F.; García-Frutos, E. M.;
Villalvilla, J. M.; Quintana, J. A.; Gutiérrez-
Puebla, E.; Monge, A.; Díaz-García, M. A.;
Gomez-Lor, B. Very Large Photoconduction
Enhancement upon Self-Assembly of a New
Triindole Derivative in Solution-Processed
Films. Adv. Funct. Mater. 2011, 21 (4), 738–745.
(35)
(36)
(37)
Ji, L.; Fang, Q.; Yuan, M.-S.; Liu, Z.-Q.; Shen, Y.-
X.; Chen, H.-F. Switching High Two-Photon
Efficiency: From 3,8,13-Substituted Triindole
Derivatives to Their 2,7,12-Isomers. Org. Lett.
2010, 12 (22), 5192–5195.
(43)
(44)
Han, T.; Bulut, I.; Méry, S.; Heinrich, B.; Lévêque,
P.; Leclerc, N.; Heiser, T. Improved Structural
Order by Side-Chain Engineering of Organic
Small Molecules for Photovoltaic Applications.
J. Mater. Chem. C 2017, 5, 10794–10800.
Wang, L.; Fang, Q.; Lu, Q.; Zhang, S.-J.; Jin, Y.-Y.;
Liu, Z.-Q. Octupolar (C3 and S4) Symmetric
Benito-Hernández, A.; Pandey, U. K.; Cavero, E.;
Termine, R.; García-Frutos, E. M.; Serrano, J. L.;
Golemme, A.; Gómez-Lor, B. High Hole
Mobility in Triindole-Based Columnar Phases:
Removing the Bottleneck of Homogeneous
Cyclized
Indole
Derivatives:
Syntheses,
Structures, and NLO Properties. Org. Lett.
2015, 17 (17), 4164–4167.
Guzelturk, B.; Kanibolotsky, A. L.; Orofino-Pena,
C.; Laurand, N.; Dawson, M. D.; Skabara, P. J.;
ACS Paragon Plus Environment

Page 15 of 17
The Journal of Organic Chemistry
Macroscopic Orientation. Chem. Mater. 2013, Multifunctional
Poly-N-Vinylcarbazole
1
2
3
25 (2), 117–121.
Interlayer in Perovskite Solar Cells for High
Stability and Efficiency: A Test with New
Triazatruxene-Based
Materials. J. Mater. Chem. A 2017, 5 (5), 1913–
1918.
(45)
Reig, M.; Puigdollers, J.; Velasco, D. Molecular
Order of Air-Stable p-Type Organic Thin-Film
Transistors by Tuning the Extension of the π-
Conjugated Core: The Cases of Indolo[3,2-
b]Carbazole and Triindole Semiconductors. J.
Mater. Chem. C 2015, 3 (3), 506–513.
Hole
Transporting
4
5
6
7
(54)
Xiao, Q.; Sakurai, T.; Fukino, T.; Akaike, K.;
Honsho, Y.; Saeki, A.; Seki, S.; Kato, K.; Takata,
8
9
M.;
Aida,
T.
Propeller-Shaped
Fused
(46)
(47)
Shelton, S. W.; Chen, T. L.; Barclay, D. E.; Ma, B.
Solution-Processable Triindoles as Hole
Selective Materials in Organic Solar Cells. ACS
Appl. Mater. Interfaces 2012, 4 (5), 2534–2540.
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
Oligothiophenes: A Remarkable Effect of the
Topology of Sulfur Atoms on Columnar
Stacking. J. Am. Chem. Soc. 2013, 135 (49),
18268–18271.
Kim, G. W.; Lampande, R.; Choe, D. C.; Bae, H.
W.; Kwon, J. H. Efficient Hole Injection Material
for Low Operating Voltage Blue Fluorescent
Organic Light Emitting Diodes. Thin Solid Films
2015, 589, 105–110.
(55)
(56)
Górski, K.; Mech-Piskorz, J.; Leśniewska, B.;
Pietraszkiewicz,
O.;
Pietraszkiewicz,
M.
Synthesis and Reactivity of 5-Heterotruxenes
Containing Sulfur or Nitrogen as the
Heteroatom. J. Org. Chem. 2019, 84, 11553–
11561.
(48)
(49)
Zhang, F.; Yang, X.; Cheng, M.; Li, J.; Wang, W.;
Wang, H.; Sun, L. Engineering of Hole-Selective
Contact for Low Temperature-Processed
Carbon Counter Electrode-Based Perovskite
Solar Cells. J. Mater. Chem. A 2015, 3 (48),
24272–24280.
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.
Calió, L.; Momblona, C.; Gil-Escrig, L.; Kazim, S.;
Sessolo, M.; Sastre-Santos, Á.; Bolink, H. J.;
Ahmad, S. Vacuum Deposited Perovskite Solar
Cells Employing Dopant-Free Triazatruxene as
the Hole Transport Material. Sol. Energy Mater.
Sol. Cells 2017, 163, 237–241.
(57)
(58)
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.
Maciejczyk, M. R.; Zhang, S.; Hedley, G. J.;
Robertson, N.; Samuel, I. D. W.; Pietraszkiewicz,
(50)
(51)
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.
M.
Monothiatruxene-Based,
Solution-
Processed Green, Sky-Blue, and Deep-Blue
Organic Light-Emitting Diodes with Efficiencies
Beyond 5% Limit. Adv. Funct. Mater. 2019, 29
(6), 1807572.
Rakstys, K.; Abate, A.; Dar, M. I.; Gao, P.;
Jankauskas, V.; Jacopin, G.; Kamarauskas, E.;
Kazim, S.; Ahmad, S.; Grätzel, M.; et al.
(59)
(60)
Kobayashi, K.; Suzue, N.; Ishii, R.; Kamiya, R.;
Wakabayashi, H. Reactions of Ninhydrin with
Benzo[b]Thiophenes. Heterocycles 2009, 78
(10), 2467–2475.
Triazatruxene-Based
Hole
Transporting
Materials for Highly Efficient Perovskite Solar
Cells. J. Am. Chem. Soc. 2015, 137 (51), 16172–
16178.
El-Sayed, M. T.; Wessjohann, L.; Porzel, A.;
Hilgeroth, A. Diazatruxenes from the
Condensation Reaction of Indoles with
Ninhydrin. J. Heterocycl. Chem. 2016, 54 (2),
1077–1083.
(52)
(53)
Petrikyte, I.; Zimmermann, I.; Rakstys, K.;
Daskeviciene, M.; Malinauskas, T.; Jankauskas,
V.; Getautis, V.; Nazeeruddin, M. K. Efficiency
Enhancement of Perovskite Solar Cells via
Incorporation of Phenylethenyl Side Arms into
(61)
Benito-Hernández, A.; El-Sayed, M. T.; López
Navarrete, J. T.; Ruiz Delgado, M. C.; Gómez-
Lor, B. Fused Donor-Acceptor π-Conjugated
Diazatruxenones: Synthesis and Electronic
Properties. Org. Chem. Front. 2018, 5 (11),
Indolocarbazole-Based
Hole
Transporting
Materials. Nanoscale 2016, 8 (16), 8530–8535.
Su, P.-Y.; Huang, L.-B.; Liu, J.-M.; Chen, Y.-F.;
Xiao, L.-M.; Kuang, D.-B.; Mayor, M.; Su, C.-Y. A
ACS Paragon Plus Environment

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Page 16 of 17
1748–1755.
(66)
(67)
(68)
Xiong, Y.; Qiao, X.; Wu, H.; Huang, Q.; Wu, Q.;
Li, J.; Gao, X.; Li, H. Syntheses and Properties of
Nine-Ring-Fused Linear Thienoacenes. J. Org.
Chem. 2014, 79 (3), 1138–1144.
1
2
3
4
5
6
7
8
(62)
Wu, D.; Mei, H.; Tan, P.; Lu, W.; Zhu, J.; Wang,
W.; Huang, J.; Li, J. Total Synthesis of the 2-
Arylbenzo[b]Furan-Containing
Products from Artocarpus. Tetrahedron Lett.
2015, 56 (29), 4383–4387.
Natural
Molander, G. A.; Cavalcanti, L. N.; Canturk, B.;
Pan, P. S.; Kennedy, L. E. Efficient Hydrolysis of
Organotrifluoroborates via Silica Gel and
Water. J. Org. Chem. 2009, 74 (19), 7364–7369.
(63)
(64)
Morice, C.; Garrido, F.; Mann, A.; Suffert, J.
Palladium Assisted Substitution of 3-
Benzo[b]Furan Triflates. Synlett 2002, 2 (3),
501–503.
9
Yang, Y.; Oldenhuis, N. J.; Buchwald, S. L. Mild
and General Conditions for Negishi Cross-
Coupling Enabled by the Use of Palladacycle
Precatalysts. Angew. Chemie - Int. Ed. 2013, 52
(2), 615–619.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
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37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Knapp, D. M.; Gillis, E. P.; Burke, M. D. A
General Solution for Unstable Boronic Acids:
Slow-Release Cross-Coupling from Air-Stable
MIDA Boronates. J. Am. Chem. Soc. 2009, 131
(20), 6961–6963.
(69)
Lane, B. S.; Brown, M. A.; Sames, D. Direct
Palladium-Catalyzed C-2 and C-3 Arylation of
Indoles:
A
Mechanistic
Rationale
for
(65)
Yue, D.; Larock, R. C. Synthesis of 2,3-
Disubstituted
Palladium-Catalyzed
Cyclization of Terminal Acetylenes. J. Org.
Chem. 2002, 67 (6), 1905–1909.
Regioselectivity. J. Am. Chem. Soc. 2005, 127
(5), 8050–8057.
Benzo[b]Thiophenes
Coupling
via
Anphilic
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