An Unprecedented Photochemical Reaction for Anthracene-Containing Derivatives

Article abstract of DOI:10.1002/cphc.201600783

A series of anthracene-containing derivatives have been synthesised and characterised. The photochemical behaviour of these derivatives have been investigated by ¹H NMR spectroscopy. An unprecedented photolysis reaction for anthracene-containing derivatives was observed in the case of anthracenes directly armed with a -CH₂O-R group upon UV irradiation. The photolysis reaction process has been demonstrated to occur in three steps. Firstly, the anthracene-containing derivatives are converted into the corresponding endoperoxide intermediate upon UV irradiation in the presence of air; then, the endoperoxide intermediate is decomposed to the corresponding starting compound and 9-anthraldehyde; finally, 9-anthraldehyde is further oxidised to anthraquinone. Additionally, the photolysis reaction of anthracene-containing derivatives is significantly promoted in the presence of a thiacalix[4]arene platform.

Full text of DOI:10.1002/cphc.201600783

Accepted Article
Title: An Unprecedented Photochemical Reaction for Anthracene-Containing Deri-
vatives
Authors: Jiang-Lin Zhao; Xue-Kai Jiang; Chong Wu; Chuang-Zeng Wang; Xi Zeng;
Carl Redshaw; Takehiko Yamato
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ChemPhysChem
10.1002/cphc.201600783
FULL PAPER
An Unprecedented Photochemical Reaction for Anthracene-
Containing Derivatives
Jiang-Lin Zhao,[a] Xue-Kai Jiang,[a] Chong Wu,[a] Chuan-Zeng Wang,[a] Xi Zeng,[b] Carl Redshaw,[c] and
Takehiko Yamato*[a]
Abstract: A series of anthracene-containing derivatives (1, 2, 3 and
4) have been synthesized and characterized. The photochemical
behaviour of these derivatives have been investigated by 1H NMR
spectroscopies. An unprecedented photolysis reaction for
anthracene-containing derivatives was firstly observed in the case of
anthracenes directly armed with a –CH2O–R group upon UV
irradiation. The photolysis reaction process has been demonstrated
to be occurred in three steps. Firstly, the anthracene-containing
derivatives are converted to the corresponding endoperoxide
intermediate upon UV irradiation in the presence of air; and then, the
endoperoxide intermediate is decomposed to the corresponding
starting compound and 9-anthraldehyde; finally, 9-anthraldehyde is
further oxidised to anthraquinone. Additionally, the photolysis
reaction of anthracene-containing derivatives is significantly
promoted in the presence of a thiaxalix[4]arene platform.
stable endoperoxides upon UV light irradiation.5
Additionally, the reverse of the above two reactions can be
achieved either thermally or by irradiation with deep UV-
light (Scheme 1).
Scheme 1. The reported photochemical reaction.
Herein, we report an unprecedented photochemical
reaction for anthracene-containing derivatives based on
thiacalix[4]arene. A series of anthracene derivatives (
1, 2, 3
Introduction
and functionalized at the 9–position has been
4
)
synthesized, for which the anthracene moiety was
employed as the photoactive unit. Further studies showed
that the above four compounds underwent favourable
decomposition upon UV irradiation following a pathway
different to the conventional dimerization or endoperoxide
formation. Furthermore, the unexpected photolysis reaction
Photochemical reactions have found widespread utility in
both bio- and polymer science given that the use of light as
a “reagent” is considered an ideal external control element
for in situ chemical manipulation, i.e. it is clean,
inexpensive, acts as very invasive switching stimulus and
there is no need to add external chemical species.1
Furthermore, it can be applied remotely and switched on
and off as needed.2 Of the many photochemical reaction
systems known, the photochemistry of anthracene-
of
anthracene-containing derivatives
based
on
thiacalix[4]arene (
1
,
2
and 3) was significantly promoted in
the presence of a thiacalix[4]arene platform. To the best of
our knowledge, such a photolyzed photochemical reaction
has not been reported previously. We expect that the
observed photolysis reaction will provide us a more efficent
and convenient protection and deprotection method in
thiacalixarene chemistry.
containing derivatives has drawn particular interest.3
A
great number of investigations suggest that there are two
kinds of predominant photoreactions based on anthracene-
containing derivatives: 1) a cycloaddition of the central ring
of the anthracene forming dimerized anthracene-containing
derivatives upon UV light irradiation;3,4 2) anthracene-
containing derivatives can trap singlet oxygen and form
Results and Discussion
Synthesis and characterization
[a]
Dr. J.-L. Zhao, Dr. X.-K. Jiang, Dr. C. Wu, Dr. C.-Z. Wang, Dr. Prof.
T. Yamato
Di-substituted compound 2 could be obtained in 70% yield by
the stereoselective O-alkylation of compound 1a6 with 9-
(bromomethyl)anthracene7 in the presence of Cs2CO3 in acetone
(Scheme 2). Interestingly, when 9-(bromomethyl)anthracene was
replaced by 9-(chloromethyl)-anthracene8 in this reaction, a
mixture of mono-substituted compound 1 and di-substituted
compound 2 were obtained even in the presence of a large
excess of 9-(chloromethy1)anthracene. This strongly suggested
that the stereoselective O-alkylation of 1a was a two-step
process. The structures of mono-substituted compound 1 and di-
Department of Applied Chemistry, Faculty of Science and
Engineering
Saga University
Honjo-machi 1, Saga 840-8502 Japan
E-mail: yamatot@cc.saga-u.ac.jp
Prof. X. Zeng
Key Laboratory of Macrocyclic and Supramolecular Chemistry of
Guizhou Province
Guizhou University
Guiyang, Guizhou, 550025, China.
Dr. C. Redshaw
Department of Chemistry
The University of Hull
[b]
[c]
1
substituted compound 2 were confirmed by H NMR, 13C NMR
1
Cottingham Road, Hull, Yorkshire HU6 7RX, UK
and MS spectra (Figure S5~S10, ESI†). The H NMR spectrum
of compound 2 exhibited two singlets for the tert-butyl protons at
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Scheme 2. The synthesis of thiacalix[4]arene derivatives mono-substituted compound 1 and di-substituted compound 2.
up-field positions, viz0.07 and 0.90 ppm; two singlets for the
CH2 protons at 4.95 ppm (OCH2-Ph) and 5.95 ppm (OCH2-
Anthracene); two singlets for the thiacalix[4]arene aromatic
protons at 7.07 ppm and 7.38 ppm (Figure S8), all of which
was indicative of a C2-symmmetric di-substituted structure of
compound 2 for the 1,3-alternate conformation. In contrast, the
1H NMR spectrum of compound 1 showed three singlets for the
tert-butyl protons (0.36,0.76 and 1.25 ppm) and the relative
intensity was 2: 1: 1, indicating a mono-substituted structure for
compound 1 (Fig. S5, see ESI†).
anthracene groups. In other words, an unexpected photolysis
reaction was firstly observed in the photochemical reaction of
anthracene-containing derivatives. Furthermore, the third group
of proton signals (δ 7.80~7.82 and 8.31~8.34 ppm, green
coloured peaks) which corresponded to anthraquinone 610
gradually increased upon increasing the irradiation time (1.0 h to
2.0 h). This strongly suggested that the 9-anthraldehyde 5 was
further oxidised to the anthraquinone 6.11 The proposed
photolysis route of anthracene-containing di-substituted
compound 2 is shown in Scheme 3. For detail characterization
information of the photoproducts, see Figure S17~S21 (ESI†).
Similar phenomenon was observed in the case of mono-
substituted compound 1 except a shorter photolysis time was
required as shown in Figure S2 (ESI†).
Photochemical reaction studies
The use of 1H NMR spectroscopy allowed the photochemical
reaction processes of these anthracene-containing derivatives to
be investigated. A 6 mM solution of di-substituted compound 2 in
CDCl3 was irradiated by UV light under air. Figure S1 (ESI†)
showed the 1H NMR spectra of di-substituted compound 2 under
different conditions. In the absence of stimulation, the proton
signals at  = 9.20, 8.48, 7.98, 7.56 and 7.36~7.46 ppm were
ascribed to the anthracene moiety of di-substituted compound 2,
and two singlets at = 4.95 and 5.95 ppm belonged to the linker
–CH2– of di-substituted compound 2 (Detail information in Figure
S8, ESI†). Upon irradiation, the intensity of di-substituted
compound 2’s peaks (black coloured peaks, Figure S1, ESI†)
gradually diminished with the concomitant appearance of
compound mono-substituted compound 1 (peaks at  = 9.35,
8.52, 8.03, 7.55~7.65 and 7.46~7.53 ppm were ascribed to the
anthracene moiety of mono-substituted compound 1, blue
coloured peaks, Figure S1). In other words, di-substituted
compound 2 was gradually decomposed to mono-substituted
compound 1. After irradiation for 2 h, all of the peaks which
corresponded to compound 1 and 2 had completely disappeared.
However, we could not observe the presence of the conventional
photodimerization or endoperoxide products, i.e. the signal for
the bridgehead H10 proton of anthracene should be shifted up-
field, due to the loss of aromaticity at the central anthracene
ring.3,4,5 Instead, it was replaced by two sets of unexpected new
signals: one group of proton signals ( 5.49, 6.96, 7.32, 7.63,
7.68 and 7.97 ppm, red coloured peaks) which corresponded to
the starting compound 1a6, and another group of proton signals
( 7.56, 7.69, 8.08, 8.72, 9.00 and 11.55 ppm, orange coloured
peaks) which corresponded to 9-anthraldehyde 59. All of the
observed evidence indicated that the anthracene linker had
undergone a cleavage at the middle of anthracene–CH2O–1a;
Scheme 3. Proposed photolysis route of compound 2.
In order to further investigate this rare photolysis
phenomenon, compound 3 possessing a similar structure but
different substituent (a di-ester) in the opposite site was
employed (Scheme 4). Interestingly,
a
totally similar
phenomenon was also observed upon the UV irradiation 2 h,
such that 3 was decomposed to the corresponding starting
compound 3a and 9-anthraldehyde 5 during the first stage.
Subsequently, 9-anthraldehyde 5 was further converted to
compound
2 had been decomposed by eliminating the
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ChemPhysChem
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photolyzable photochemical phenomenon based on anthracene-
containing derivatives as observed herein. It noteworthy to point
out that the only difference between compounds 1, 2, 3 and the
other reported anthracene-containing compounds is the linker
between anthracene moiety and R platform. This strongly
suggested that the anthracene–CH2O–R structure played an
important role during the photo-decomposition. The photolysis
behaviour only occurred in the case of anthracene moiety
directly armed with an –CH2O–R group.
Reference compound 4, which was prepared by O-alkylation
of 4-tert-butyl-2,6-dimethylphenol (4a)14 with 9-(bromomethyl)-
anthracene in the presence of Cs2CO3, was employed to further
study the process of this photolysis reaction (Scheme 5). The
proton signals of anthracene moiety (7.47–7.51, 8.03, 8.40
and 8.50 ppm) and benzene ring (ppm) appeared at up-
field positions, indicating a  interaction between these two
moieties for compound 4 to form an efficient shielding effect. As
expected, 4 was finally decomposed to the stating compound 4a
and 9-anthraldehyde 5 upon the irradiation. Subsequently, 9-
anthraldehyde 5 was further converted to the anthraquinone 6
(Figure S4, ESI†). The only difference between the reference
compound 4 and the thiacalix[4]arene anthracene-containing
derivatives (1, 2 and 3) was the photodecomposition time.
Compounds 2 and 3 took about two hours to complete the
photolysis reaction, compound 1 took about one hour given
there is one anthracene group in compound 1 (Figure 2a).
However, reference compound 4 needed more than five hours to
complete the photolysis reaction (Figure 2b). This suggested
Scheme 4. The synthetic route of thiacalix[4]arene derivative 3.
anthraquinone 6 during the second stage. The proposed
photolysis process of anthracene-containing compound 3 is
totally same with compound 1 and 2 (Figure S3, ESI†). Recently,
a similar phenomenon was observed by Wirz and coworkers in
fluorescein analogues as photoremovable protecting groups.
The photoremovable protecting groups was converted to 3,6-
dihydroxy-9H-xanthen-9-one and 6-hydroxy-3-oxo-3H-xanthene-
9-carboxylic acid upon irradiation at ~520 nm about 24h.16
Consequently, it prompted us to propose that the anthracene
group can also be acted as a photoremovable protection group
and more efficient (~2 hour).
Furthermore, the photolysis reaction prerequisites were
discussed. According to our recent work12a and that of
others12b,c,d,e, such as the anthracene-containing derivatives
(R1,R2, R3, R4 and R5, Figure 1) bearing different linkers
between the anthracene moiety and a thiacalix[4]arene or other
platform only gave the conventional photodimerization or
endoperoxide photo-products upon UV irradiation. To the best of
our knowledge, there are no reports relating to such a
Figure 2. The conversion yield versus reaction time of a 6 mM CDCl3 solution
of a) 1, 2 and 3; b) 4 under irradiation at room temperature.
Figure 1. The reported anthracene-containing derivatives.
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Conclusions
In conclusion, the synthesis of a series of anthracene derivatives
(1, 2, 3 and 4) functionalized at the 9–position is reported, and
their photochemical behaviour has been investigated by 1H NMR
spectroscopy. We have observed that a rare photolysis reaction
of anthracene-containing derivatives occurred in the case of
anthracenes directly armed with a –CH2O–R group upon UV
irradiation. Furthermore, the photolysis process has been
demonstrated to occur in three steps. Firstly, the anthracene-
containing derivatives are converted to the endoperoxide
intermediate upon UV irradiation in the presence of air; and then,
the endoperoxide intermediate is decomposed to the
corresponding starting compound and 9-anthraldehyde; finally,
9-anthraldehyde is further oxidised to anthraquinone.
Additionally, the photolysis reaction of anthracene-containing
derivatives is significantly promoted in the presence of a
thiaxalix[4]arene platform.
Fast (~ 2 hours), clean (light as “reagent”) and controllable
(irradiation can be switched at will) are the favourable features
associated with this photolysis process. It has the potential
applications as a protection and deprotection method in the
(thia)calixarene chemistry to introduce different substituents or
construct, such as A, B, C, D systems. Current studies are
aimed at exploiting this reaction.
Scheme 5. Proposed photolysis route of compound 4.
that the photo-decomposition of the anthracene-containing
derivatives was significantly promoted by the presence of a
thiaxalix[4]arene platform.
On the other hand, the longer photolysis time of 4 provided us
with more information about this photolysis process. Interestingly,
when compound 4 was irradiated at the beginning for 1h, it was
not directly decomposed, but almost quantitatively initially
converted to an intermediate 7 (blue square, Figure 2b and blue
peaks, Figure S4, ESI†), and then 7 started to be decomposed
to the starting compound 4a and 9-anthraldehyde 5 (red triangle,
Figure 2b and Figure S4, ESI†). Although 1H NMR spectroscopic
analysis of the intermediate 7 was possible:  = 1.26 (9 H, s, t-
Bu), 1.90 (6 H, s, CH3), 5.69 (1 H, s, CHOO), 5.91 (2 H, s, CH2),
6.88 (2 H, s, Ar-H), 7.16 (2 H, d, J = 7.5 Hz, Anthracene-H), 7.25
(2 H, t, J = 7.4 Hz, Anthracene-H), 7.39 (2 H, t, J = 7.5 Hz,
Anthracene-H) and 7.79 (2 H, d, J = 7.8 Hz, Anthracene-H) ppm
(detail information, Figure S25, ESI†), it was decomposed too
quickly to further analysis via 13C NMR or MS spectroscopy.
However, when compound 1, 2, 3 and 4 was irradiated at 365
nm under an N2 atmosphere. No detectable changes were
observed in the 1H NMR spectra, even after irradiating the
compounds for 6 h. Subsequently, comparison with reported
results,3,4,5 prompted us to propose a [4 + 2] cycloaddition with
singlet oxygen in this system during the first stage. The [4 + 2]
photosensitized oxygenation involving the cycloaddition of 1O2
(singlet oxygen, an excited state of molecular oxygen which was
generated from ambient air by directly irradiation with UV–
light.)15 on the electron-rich carbons of the central anthracene
ring had occurred. Thus, we proposed the possible structure for
this intermediate as the endoperoxide photo-product 7 (Scheme
5). The photolysis reaction rate of reference compound 4 was
slow down due to the presence of interaction between
anthracene and benzene ring. The opportunity of the
Experimental Section
General procedures
Unless otherwise stated, all reagents used were purchased from
commercial sources and were used without further purification. All
solvents used were dried and distilled by the usual procedures prior to
use. All melting points (Yanagimoto MP-S1) are uncorrected. 1H NMR
and 13C NMR spectra were recorded on a Varian-400MR-vnmrs 400 with
SiMe4 as an internal reference: J-values are given in Hz. Mass spectra
were obtained with
a
Nippon Denshi JMS-HX110A Ultrahigh
Performance mass spectrometer at 75 eV using a direct-inlet system.
Elemental analyses were performed by Yanaco MT-5. UV-vis spectra
were recorded using a Shimadzu UV-3150UV-vis-NIR spectrophotometer.
Materials
Compound
1a,6a
compound
3a,13
compound
4a,14
9-
(chloromethy1)anthracene8 and 9-(bromomethyl)anthracene7 were
prepared following the reported procedures.
Synthesis of thiacalix[4]arene derivative (1 and 2).
A mixture of 1a (200 mg, 0.221 mmol) and Cs2CO3 (720 mg, 2.21
mmol) in dry acetone (30 mL) was heated at reflux for 1 h under Ar. Then
9-(chloromethy1)anthracene (501 mg, 2.21 mmol) was added, and the
mixture was heated at reflux for 17 h. The resulting solution was cooled
and diluted with water and extracted with CHCl3. The organic layer was
separated and dried (MgSO4) and condensed under reduced pressure to
give a yellow solid. The residue was purified by column chromatography
(CH2Cl2 : haxane = 1:5 to 1:3), gave the desired products 1 (16 mg,
5.7%) and 2 (22 mg, 7.7%) as colourless prisms.
1,3-alternate-25,27-Dibenzyloxy-26-(anthrylmethyl)oxy-28-hydroxy-5,
11,17,23- tetra-tert-butyl-2,8,14,20-tetrathiacalix[4]arene (1): mp 249–
250 °C; 1H NMR (400 MHz, CDCl3) δ 0.36 (18 H, s, tBu), 0.76 (9 H, s,
tBu), 1.25 (9 H, s, tBu), 4.87 (2 H, d, J = 10.6 Hz, OCH2-Ph), 5.31 (2 H, d,
J = 10.5 Hz, OCH2-Ph), 6.10 (2 H, s, OCH2- Anthryl), 6.83 (2 H, d, J = 2.4
Hz, Ar-H), 7.02 (1 H, s, OH), 7.13 (2 H, d, J = 2.4 Hz, Ar-H), 7.30–7.41 (6
H, m, Ph-H), 7.50 (2 H, s, Ar-H), 7.46–7.53 (2 H, m, Anthryl-H), 7.58 (2 H,
s, Ar-H), 7.55–7.65 (6 H, m, Anthryl -H and Ph-H ), 8.03 (2 H, d, J = 8.3
1
cycloaddition of O2 on the electron-rich carbons of the central
anthracene ring was decreased. On the other side, the
photochemical reaction rate could be greatly enhanced in the
presence of thiacalix[4]arene platform because it served as a
host to capture oxygen.12a Finally, the whole photolysis process
was proposed as shown in Scheme 5.
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Photoreaction: Procedure and Characterization
Procedure
Irradiation at 365 nm were performed with a UV lamp (ASONE Handy
Hz, Anthryl-H), 8.52 (1 H, s, Anthryl-H), 9.35 (2 H, d, J = 8.9 Hz, Anthryl-
H) ppm; 13C NMR (100 MHz, CDCl 3) δ 30.4, 30.5, 31.4, 33.5, 33.6, 34.0,
69.4, 121.8, 125.0, 126.1, 126.5, 127.9, 128.0, 128.1, 128.3, 128.5,
128.5, 128.9, 128.9, 131.6, 133.3, 133.6, 133.7, 136.0, 137.1, 141.9,
146.1, 146.8, 155.8, 157.4, 159.4 ppm; FABMS m/z [M+H]+ Calcd for
C69H71O4S4 (1091.4); Found 1091.3. Elemental Anal. Calcd for
C69H70O4S4·H2O: C, 74.69%; H, 6.54%. Found: C, 75.09%; H, 6.42%.
UV Lamp, SLUV-4).
A 6 mM solution of anthracene containing
derivatives in CDCl3 was irradiated at 365 nm (1~6 h). The 1H NMR
spectrum was recorded after the irradiation and the temperature of the
NMR probe was kept constant at 25 C.
A similar procedure using 9-(bromomethyl)anthracene was followed
Characterization of photoproducts (Known compounds)
for the synthesis of product 2 (198mg, 70%).
25,27-Dibenzyloxy-5,11,17,23-tetra-tert-butyl-2,8,14,20-tetrathia-
calix[4]arene-26,28-diol (1a).6a colourless prisms, mp 250–252°C. 1H
NMR (400 MHz, CDCl3) δ 0.79 (18 H, s, tBu), 1.34 (18 H, s, tBu), 5.49 (4
H, s, OCH2Ph), 6.96 (4 H, s, Ar-H), 7.32 (6 H, t, J = 6.9Hz, Ph-H,), 7.63
(4 H, d, J = 6.9Hz, Ph-H), 7.68(4 H, s, Ar-H), 7.97 (2 H, s, OH) ppm.
1,3-alternate-25,27-Dibenzyloxy-26,28-bis[(anthrylmethyl)oxy]-5,11,
17,23-tetra- tert-butyl-2,8,14,20-tetrathiacalix[4]arene (2): mp 253–254°C.
1H NMR (400 MHz, CDCl3) δ 0.07 (18 H, s, tBu), 0.90 (18 H, s, tBu), 4.95
(4 H, s, OCH2-Ph), 5.95 (4 H, s, OCH2- Anthryl), 7.07 (4 H, s, Ar-H), 7.38
(4 H, s, Ar-H), 7.36 ~ 7.46 (10 H, m, Ph-H & Anthryl-H), 7.56 (4 H, t, J =
8.0 Hz Anthryl-H), 7.65 (4 H, d, J = 6.9 Hz, Ph-H), 7.98 (4 H, d, J = 8.4
Hz, Anthryl-H), 8.48 (2 H, s, Anthryl-H), 9.20 (4 H, d, J = 8.9 Hz, Anthryl-
H) ppm; 13C NMR (100 MHz, CDCl 3) δ 30.2, 31.1, 33.2, 33.8, 68.8, 75.3,
124.9, 126.0, 126.3, 127.8, 128.0, 128.2, 128.4, 128.8, 128.9, 129.1,
129.3, 131.5, 131.9, 134.7, 134.8, 137.9, 145.3, 159.5, 159.6 ppm;
FABMS: m/z: [M+H]+ Calcd for C84H81O4S4 (1281.5); Found 1281.4.
Elemental Anal. Calcd for C84H80O4S4·2H2O: C 76.56, H 6.42%. Found: C,
76.23, H, 6.00%
9-Anthraldehyde.9 yellow solid, mp 114–116°C. 1H NMR (400 MHz,
CDCl3) δ 7.56 (2 H, t, J = 7.6 Hz), 7.69 (2 H, t, J = 7.6 Hz), 8.08 (2 H, d, J
= 8.4 Hz), 8.72 (1 H, s), 9.00 (2 H, d, J = 8.8 Hz), 11.55 (1 H, s, -CHO)
ppm; 13C NMR (CDCl 3) δ 123.5, 125.7, 129.2, 129.3, 131.1, 132.1, 135.3,
193.0 ppm.
Anthraquinone.10 yellow needles, mp 282–284°C. 1H NMR (400 MHz,
CDCl3) δ 7.80–7.82 (4 H, m), 8.31–8.34 (4 H, m) ppm; 13C NMR (100
MHz, CDCl 3) δ 127.2, 133.6, 134.1, 183.2 ppm.
Synthesis of thiacalix[4]arene derivative (3).
25,27-Di[(ethoxycarbonyl)methoxy]-5,11,17,23-tetra-tert-butyl-
2,8,14,20-tetrathiacalix[4]arene-26,28-diol (3a).13 colourless prisms,
mp 268–269°C. 1H NMR (400 MHz, CDCl3) δ 0.78 (18H, s, tBu), 1.33
(18H, s, tBu), 1.38 (6 H, t, J = 7.2Hz, -CH2CH3), 4.42 (4 H, q, J = 7.1Hz, -
CH2CH3), 5.29 (4 H, s, -OCH2-), 6.92 (4 H, s, Ar-H), 7.67 (4 H, s, Ar-H),
8.02 (2 H, s, OH) ppm; 13C NMR (100 MHz, CDCl 3) δ14.3, 30.8, 31.5,
34.0, 34.2, 61.3, 70.3, 122.0, 129.1, 132.6, 134.7, 142.7, 148.5, 154.9,
155.7, 169.0 ppm.
A mixture of 3a (1.00 g, 1.12 mmol) and Cs2CO3 (3.65 g, 11.20 mmol)
in dry acetone (150 mL) was heated at reflux for 1 h under Ar. Then 9-
(bromomethyl)anthracene (0.91 g, 3.36 mmol) was added and the
mixture heated at reflux for an additional 24 h. The resulting solution was
cooled and diluted with water and extracted with CH2Cl2. The organic
layer was separated and dried (MgSO4) and condensed under reduced
pressure to give a yellow solid. The residue was purified by column
chromatography (CHCl3) to afford the desired product 3 (1.18 g, 83%) as
a yellow powder.
1,3-alternate-25,27-Bis[(ethoxycarbonyl)methoxy]-26,28-bis[(anthryl-
methyl)oxy]-5,11,17,23–tetra-tert-butyl-2,8,14,20-tetrathiacalix[4]arene
(3): mp 248–251°C. 1H NMR (400 MHz, CDCl3) δ 0.05 (18 H, s, tBu),
1.32 (18 H, s, tBu), 1.38–1.35 (6 H, m, CH2CH3), 4.30 (4 H, q, J = 7.1Hz,
CH2CH3), 4.66 (4 H, s, OCH2COO-), 5.94 (4 H, s, OCH2-Anthryl), 7.00 (4
H, s, Ar-H), 7.42 (4 H, t, J = 7.8 Hz, Anthryl-H ), 7.53 (4 H, t, J = 8.4 Hz,
Anthryl-H ), 7.66 (4 H, s, Ar-H), 7.96 (4 H, d, J = 8.2 Hz, Anthryl-H), 8.46
(2 H, s, Anthryl-H), 9.16 (4 H, d, J = 8.7 Hz, Anthryl-H) ppm; 13C NMR
(100 MHz, CDCl 3) δ 14.3, 30.2, 31.3, 33.2, 34.2, 60.6, 69.1, 69.2, 124.9,
126.0, 126.3, 127.7, 128.3, 128.5, 128.8, 128.9, 131.6, 131.8, 134.2,
135.4, 145.6, 145.9, 158.2, 159.5, 168.1 ppm; FABMS: m/z: [M]+ Calcd
for C78H80O8S4 (1272.4736); Found 1272.4739. Elemental Anal. Calcd.
for C78H80O8S4·H2O: C, 72.52; H, 6.40%. Found: C, 72.73, H, 6.24%.
4-(tert-Butyl)-2,6-dimethylphenol (4a).14 1H NMR (100 MHz, CDCl3)
δ 1.28 (9H, s, tBu), 2.24 (6 H, s, CH3), 4.45 (1 H, s, OH), 6.99 (2 H, s, Ar-
H) ppm.
9-((4-(tert-Butyl)-2,6-dimethylphenoxy)methyl)-9,10-dihydro-9,10-
epidioxyanthracene (7): 1H NMR (100 MHz, CDCl3) δ = 1.26 (9 H, s,
tBu), 1.90 (6 H, s, CH3), 5.69 (1 H, s, CHOO), 5.91 (2 H, s, CH2), 6.88 (2
H, s, Ar-H), 7.16 (2 H, d, J = 7.5 Hz, Anthracene-H), 7.24 (2 H, d, J = 7.4
Hz, Anthracene-H), 7.39 (2 H, t, J = 7.5 Hz, Anthracene-H), 7.79 (2 H, d,
J = 7.8 Hz, Anthracene-H) ppm.
Acknowledgements
Synthesis of reference compound (4).
This work was performed under the Cooperative Research
Program of “Network Joint Research Center for Materials and
Devices (In-stitute for Materials Chemistry and Engineering,
Kyushu Universi-ty)”. We would like to thank the OTEC at Saga
University and the International Cooperation Projects of Guizhou
Province (No. 20137005) for financial support. The EPSRC is
thanked for a travel grant (to CR).
A mixture of 4a (178 mg, 1.0 mmol) and Cs2CO3 (1.63 g, 5.0 mmol) in
dry acetone (30 mL) was heated at reflux for 1 h under Ar. Then 9-
(bromomethyl)anthracene (271 mg, 1.0 mmol) was added and the
mixture heated at reflux for an additional 20 h. The resulting solution was
cooled and diluted with water and extracted with CH2Cl2. The organic
layer was separated and dried (MgSO4) and condensed under reduced
pressure to give a yellow solid. The residue was purified by column
chromatography (CH2Cl2 : haxance = 1:3) to afford the desired product 4
(350 mg, 95%) as a light yellow solid.
Keywords: Thiacalix[4]arene • Photolysis • Anthracene•
9-((4-(tert-Butyl)-2,6-dimethylphenoxy)methyl)anthracene (4): yellow
solid, mp 110–111°C. 1H NMR (400 MHz, CDCl3) δ 1.30 (9 H, s, t-Bu),
2.23 (6 H, s, CH3), 5.87 (2 H, s, OCH2-Anthryl), 7.01 (2 H, s, Ar-H), 7.47–
7.51 (4 H, m, Anthryl-H ), 8.03 (2 H, d, J = 8.1 Hz, Anthryl-H), 8.40 (2 H,
d, J = 8.4 Hz, Anthryl-H), 8.50 (1 H, s, Anthryl-H) ppm; 13C NMR (100
MHz, CDCl3) δ 17.3, 31.5, 34.1, 67.1, 124.5, 125.0, 125.9, 126.1, 128.6,
129.0, 130.2, 131.0, 131.5, 146.5, 154.6 ppm; FABMS: m/z: [M-H]+ Calcd
for C27H27O (367.2062); Found 367.2063.
Decomposition
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An unprecedented photolysis
reaction for anthracene-containing
derivatives was observed. The
reaction prerequisites and the photo-
decompositon process for this
photolysis reaction have been
investigated.
Jiang-Lin Zhao,[a] Xue-Kai Jiang,[a]
Chong Wu,[a] Chuan-Zeng Wang,[a] Xi
Zeng,[b] Carl Redshaw,[c] and Takehiko
Yamato*[a]
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An Unprecedented Photochemical
Reaction for Anthracene-Containing
Derivatives
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