Synthesis of Emissive Heteroacene Derivatives via Nucleophilic Aromatic Substitution

Article abstract of DOI:10.1021/acs.joc.9b02523

A synthetic approach for preparing a variety of heterocyclic tetrahydropentacene derivatives via nucleophilic aromatic substitution reactions of bidentate nucleophiles and tetrafluoroterephthalonitrile was developed. X-ray crystallography of several products revealed that the compounds containing oxygen and nitrogen heteroatoms are highly planar and engage in π-stacking, while the compounds containing sulfur are bent and do not stack as effectively. The compounds were also highly emissive, and the heteroatom had a significant impact on the emission and electrochemical properties.

Full text of DOI:10.1021/acs.joc.9b02523

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Article
Synthesis of Emissive Heteroacene Derivatives
via Nucleophilic Aromatic Substitution
Lana K. Hiscock, Chengzhang Yao, William G. Skene, Louise N. Dawe, and Kenneth Edward Maly
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b02523 • Publication Date (Web): 25 Oct 2019
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The Journal of Organic Chemistry
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Synthesis of Emissive Heteroacene Derivatives via Nucleophilic
Aromatic Substitution
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Lana K. Hiscock,† Chengzhang Yao,‡ W. G. Skene,‡ Louise N. Dawe,† and Kenneth E. Maly*†
†Department of Chemistry and Biochemistry, Wilfrid Laurier University, 75 University Ave. W., Waterloo, ON, N2L 3C5,
Canada
‡Département de Chimie, Université de Montréal, CP 6128, Centre-ville, Montreal, QC, H3C 3J7, Canada
Supporting Information Placeholder
CN
CN
XH
F
F
F
F
X
Y
Y
X
SNAr
+
YH
CN
CN
X, Y = O, NR, S
ABSTRACT: A synthetic approach for preparing a variety of heterocyclic tetrahydropentacene derivatives via nucleophilic aromatic
substitution reactions of bidentate nucleophiles and tetrafluoroterephthalonitrile was developed. X-ray crystallography of several
products revealed that the compounds containing oxygen and nitrogen heteroatoms are highly planar and engage in π-stacking, while
the compounds containing sulfur are bent and they do not stack as effectively. The compounds were also highly emissive and the
heteroatom had a significant impact on the emission and electrochemical properties.
INTRODUCTION
Scheme 1. Synthesis of Compound 1.
Polycyclic aromatic hydrocarbons (PAHs) are the focus of
CN
intense research interest. This is in part because of their π-
conjugated structures that make them suitable for use in organic
electronics and as dyes.1–5 More recently, attention has focused
on heteroaromatic PAHs because the heteroatom substitution
can influence the electronic properties, stability, and solid state
packing, which collectively in turn, impact the overall device
performance.6–8
CN
O
O
O
O
OH
OH
F
F
F
F
K2CO3
+
DMF, 
CN
CN
1
The nucleophilic aromatic substitution approach using
tetrafluoroterephthalonitrile could be extended to a variety of
tetrahydroheteropentacene systems. However, the reaction
scope of bidentate nucleophiles with TFN has received little
attention. In one example, TFN was reacted with a number of
bidentate arene nucleophiles derivatives using ultrasound
conditions.19 Analogs in which the oxygen atoms of the
nucleophile are replaced with N or S were reported, including
dihydrophenazine (2) and thianthrene (3).
Dicyanotetraoxapentacene (DCTOP, 1) is
a
planar,
pentacyclic compound that resembles a heteropentacene. It is
readily prepared by nucleophilic aromatic substitution using
catechol and tetrafluoroterephthalonitrile (TFN) (Scheme 1).
This motif has been used for the preparation of rigid,
macromolecular networks such as polymers with intrinsic
microporosity,9–13 covalent organic frameworks,14,15 as well as
cyclodextrin-based polymers for wastewater treatment.16,17 In
these examples, the DCTOP moiety serves primarily as a rigid
linker. Recently, we showed that dialkoxyphenyl DCTOP
derivatives exhibit columnar mesophases and they have
CN
H
N
CN
S
S
F
F
F
F
N
H
aggregation-induced emission.18
Given the interesting
CN
CN
properties of these materials, their similarity to heteroacenes,
and their potential as luminescent dyes, there is an interest in
exploring this synthetic approach for the preparation of other
heteroacene analogs.
3
2
However, these reactions have not been extended to the
corresponding heteropentacene analogs. In another example,
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Swager and coworkers reported that dithiophenol reacts with
Page 2 of 9
isolated. The reaction mixture turned a dark purple and a red
solid was obtained upon workup. The red solid was a mixture
of products where the major component was compound 9
(Scheme 3), which was isolated in 50% yield. In compound 9,
one equivalent of 2-aminophenol reacts as expected, but the
second equivalent does not undergo the final cyclization by
nucleophilic aromatic substitution (Scheme 3). The structure of
9 was confirmed by X-ray crystallography (see Supporting
Information).
1
2
3
4
5
6
7
8
TFN and related polyfluorinated benzene derivatives and they
demonstrated that this nucleophilic aromatic substitution
reaction can be reversible.20 Further, nucleophilic aromatic
substitution on brominated naphthalene diimides and related
imides with a variety of bidentate aromatic nucleophiles has
been successfully used to prepare extended imide-
functionalized heteroacene derivatives, suggesting the that this
approach could be used to access other types of heteroacenes.21–
23
9
The dark purple colour of the reaction mixture was attributed
to deprotonation of the cyclized phenoxazine intermediate,
which likely deactivates the para position to nucleophilic
substitution, explaining why full cyclization to form 4a was
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In this study, we report nucleophilic aromatic substitution
reactions with TFN and a variety of bidentate nucleophiles to
prepare several novel heterocyclic tetrahydropentacene
derivatives that behave as luminescent dyes (Figure 1,
compounds 1, 4-7). We also demonstrate that the heteroatom
substitution in these systems has a dramatic impact on the solid-
state structures, the emission, and the electrochemical
properties of these materials.
unsuccessful.
To test this hypothesis, the reaction was
conducted in the absence of base in DMSO. Under these
conditions, difluorophenoxazine 10 was formed in quantitative
yield. However, the desired compound 4a was not observed.
Scheme 3. Attempted Synthesis of 4a.
CN
CN
CN
CN
H
N
OH
F
F
F
F
K2CO3
O
O
O
O
O
O
O
O
+
DMF, 
NH2
N
H
O
N
CN
CN
CN
4a
CN
1
Et
CN
5
not formed
DMSO

CN
R
N
CN
O
S
O
O
O
F
quant.
CN
N
R
O
N
N
H
O
O
F
F
CN
Et
CN
CN
NH2
9
4a
4b
4c
R = H
R = Et
R = C10H21
6
N
50%
H
CN Et
N
CN
S
10
To circumvent the deactivation that results from the amide ion
of 10 under basic conditions, we sought to test the reactivity of
corresponding N-alkyl amino phenols 12b and 12c.
Compounds 12b and 12c were prepared via acetylation,
followed by reduction using LiAlH4 (Scheme 4). Gratifyingly,
the reaction of 12b and 12c with TFN in the presence of K2CO3
in DMF gave the targeted pentacyclic systems 4b and 4c as red,
crystalline solids in good yields. Furthermore, reacting 12b
with TFN in DMSO in the absence of base furnished the
corresponding N-ethylphenoxazine (13) in 80% yield.
N
S
Et
CN
7
Figure 1. Target compounds in this study.
RESULTS AND DISCUSSION
Compound 1 was prepared as according to literature
procedures by reacting catechol with TFN in DMF in the
presence of K2CO3.24 It is noteworthy that the preparation of
the corresponding dibenzodioxin (8), where only one equivalent
of catechol reacts with TFN, can be prepared under similar
conditions with THF as the solvent (Scheme 2).
The preparation of dibenzodioxin 8 and N-ethylphenoxazine
13 demonstrate that the reaction with TFN can be controlled so
that nucleophilic aromatic substitution to produce cyclic
products only occurs on one side of the molecule. This result is
consistent with the notion that the first two nucleophilic
aromatic substitution reactions occur readily and the product of
this reaction is less activated towards further substitution
because of the electron-donating heteroatoms. However, by
altering the reaction conditions, these compounds can react
further, opening up the possibility of producing a variety of
compounds with varied heteroatom substitution patterns. To
demonstrate that sequential nucleophilic aromatic substitution
reactions can be used to produce dissymmetric heteropentacene
Scheme 2. Synthesis of dibenzodioxin 8.
CN
CN
K2CO3
OH
OH
F
F
F
F
O
O
F
F
+
THF, 
74%
CN
CN
8
For our initial attempts to prepare the corresponding
diazadioxapentacene analog (compound 4a), we employed the
same reaction conditions using commercially available 2-
aminophenol. Unfortunately, the desired product was not
analogs, dibenzodioxin
8
was reacted with N-ethyl-
2aminophenol to furnish compound 5 in 66% yield (Scheme 5).
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The Journal of Organic Chemistry
compounds 1, 4c, 6, and 7 were grown and they were studied
1
2
3
4
5
6
7
8
by single crystal X-ray diffraction. Compound 1 is known, and
the crystal structure was recently reported from crystals grown
from acetonitrile.14 In our hands, crystals of 1 that were suitable
for X-ray diffraction were grown by the slow evaporation of a
solution in mesitylene, yielding a crystal structure that agreed
with the previously reported structure. The polycyclic
compound is highly planar with a root mean squared deviation
from planarity of 0.039 Å. Each molecule engages in π-
stacking interactions with four neighbouring molecules; two
molecules each above and below the plane of the aromatic
system (See Supporting Information.)
Scheme 4. Synthesis of compounds 4b-c and 13.
Ac2O, EtOAc
OH
OH
OH
NH
LiAlH4
THF
or
NH2
NHR
C9H19COCl
THF, pyridine
9
O
R
10
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12b
12c
R=Et, 81%
R=C10H21, 80%
11b
11c
R=CH3, 89%
R=C9H19, 80%
CN
We were unsuccessful in growing crystals of ethyl-
substituted 4b that were suitable for X-ray diffraction.
However, we were able to grow crystals of the corresponding
decyl-substituted derivative (4c) by the slow diffusion of
acetonitrile into a saturated chlorobenzene solution. Compound
4c crystallized in a triclinic space group (P-1) with one
molecule per unit cell. Similar to 1, the polycyclic core of 4c
was highly planar with a root mean squared deviation from
planarity of 0.099 Å (Figure 2). The packing of 4c shows
stacking where the central ring interacts with the terminal ring
of an adjacent molecule at a distance of 3.84 Å and shift of 1.37
Å (See Supporting Information).
F
F
F
CN
CN
R
N
O
F
4b
4c
R=Et, quant.
R=C10H21, 84%
CN
N
R
O
K2CO3, DMF
CN
CN
O
F
F
OH
F
F
F
F
+
DMSO, 
N
NHEt
Et
CN
CN
80%
13
Finally, we explored the introduction of sulfur atoms into
these heterocyclic systems, given that thiolates are highly
nucleophilic. To this end, N-ethyl-2-aminothiophenol was
prepared by reduction of 2-methyl benzothiazole25 and reacted
with tetrafluoroterephthalonitrile and dibenzodioxin 8 to
furnish compounds 6 and 7 in moderate yields (Scheme 5). In
contrast to 4b,c the analogous reaction to form 7 produced two
major products (TLC) of very similar Rf which proved
inseparable by column chromatography. Crystallisation of the
mixture from THF yielded compound 7, confirmed by X-ray
crystallography, while the second component, thought to be the
corresponding syn isomer, eludes full purification.
Figure 2. Crystal structure of compound 4c with 50% displacement
ellipsoids. Views (a) and (b) rotated by 90°.
Scheme 5. Synthesis of compounds 5-7.
Crystals of 6 were grown from ethyl acetate via the slow
evaporation. Unlike the highly planar compounds 1 and 4c, the
introduction of a sulfur atom leads to a bent structure (Figure
3). It nonetheless still engages in π-stacking interactions with
centroid distances of 3.60 and 3.63 Å with respect to the
terminal dibenzodioxin and central dicyanobenzene rings.
CN
CN
O
O
F
F
K2CO3
OH
O
O
O
N
+
DMF, 100 o
66%
C
NH
Et
12b
CN
CN
CN Et
8
5
Cl
CN
S
K2CO3
O
O
F
F
NH2
SH
O
O
+
DMF, 100 o
54%
C
N
CN
CN Et
6
Cl
CN
Et
CN
S
NH2
SH
K2CO3
F
F
F
F
N
+
DMF, 100 o
45%
C
S
N
CN Et
7
CN
In order to gain insight into the molecular geometry of these
compounds and explore their solid state packing, crystals of
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Figure 3. Crystal structure of compound 6 with 50% displacement
ellipsoids.
In contrast, the fluorescence quantum yields of thin films
are significantly lower (see Supporting Information). This is
consistent with conventional aggregation caused quenching.
From the absorption and emission spectra, two patterns are
apparent. First, substitution of oxygen atoms for nitrogen atoms
leads to a red shift in both the absorption and emission spectra.
For example, compound 1 shows an emission maximum of 478
nm, compound 5 (bearing one nitrogen) has an emission
maximum of 556 nm, and compound 4b (bearing two nitrogen
atoms) has an emission maximum of 615 nm. Interestingly,
replacement of oxygen atoms by sulfur atoms has only very
slight influence on the absorption and emission spectra, i.e. 4b
vs. 7 and 5 vs. 6. However, the quantum yield of fluorescence
decreases when sulfur atoms are introduced. This is expected
owing to increased spin orbit coupling with the heavier atom,
resulting in increased deactivation of the singlet excited state by
intersystem crossing.
1
2
3
4
5
6
7
8
Crystals of compound 7 were grown from the slow
evaporation of a solution in THF. Similar to compound 6, the
sulfur-containing rings adopt a nonplanar geometry with a fold
angle of 40.06(8)° (Figure 4). However, in contrast to
compounds 1, 4c, and 6, there are no discernible π-stacking
interactions in the solid state. This is possibly because the bent
structure impedes the close approach of neighboring aromatic
rings.
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Figure 4. Crystal structure of 7 with 50% displacement ellipsoids.
The colours of the compounds prepared in this series range
from yellow to orange-red and they are highly emissive in
solution. We therefore investigated their emission in both
solution and the solid state. The collective absorption and
emission spectra are shown in Figure 5 with emission data
summarized in Table 1.
Table 1. Emission data of the Tetrahydroheteroacenes in
chloroform.
1
4b
5
6
7
Φa
78%
44%
34%
23%
32%
(430)
(495)
(470)
(465)
(495)
(excitatio
n λ, nm)b
Figure 5. Normalized absorption (solid line) emission (symbol)
spectra for 1 (▬, ), 4b (▬, ), 5 (▬, ▲), 6 (▬, ♦), and 7 (▬, )
measured in chloroform. Inset: solutions in chloroform irradiated
with a hand-held UV lamp.
Abs.
430
475
390
495
615
470
470
555
450
460
580
450
495
615
470
(nm)c
Em.
(nm)d
e
The redox properties of the compounds were investigated by
both cyclic voltammetry and square wave voltammetry in
dichloromethane (see Supporting Information). Compound 1
showed no clear oxidation wave over the potential range
scanned, while compound 5 showed a quasi-reversible two-
electron oxidation peak at 595 mV vs. ferrocene. In contrast,
compounds 4b and 7 each showed two reversible oxidation
peaks with oxidation potentials of 265 and 780 mV for 4b and
515 and 835 mV for 7. Compound 6 showed a single one-
electron quasi-reversible oxidation at 725 mV. The non-
reversible oxidation behavior of 6 and 7 is further supported by
electrochemically produced products that were observed in the
reverse wave of the anodic voltammogram. Overall, the
observed order of the oxidation potentials is consistent with the
calculated HOMO energies (see Supporting Information).
a
b
Measured with a calibrated integrating sphere. Value in
parentheses is the excitation wavelength used for measuring the
quantum yields. c Absorption maximum. d Emission maximum.
e Excitation wavelength for measuring the emission spectrum.
The fluorescence quantum yields in chloroform range from
23% to 78%, confirming that these compounds are all emissive
in solution. Owing to the compounds’ small Stokes shift in
solution, exciting at their absorption maximum would truncate
the emission spectrum. This would result in erroneously low
emission yields. Excitation wavelengths shorter than the
corresponding absorption maximum of the compounds were
therefore used for measuring the Φfl in solution. These were
done to ensure that the full emission spectrum was measured.
Accurate Φfl are expected with this approach, especially since
the emission yield is independent of the excitation wavelength.
CONCLUSIONS
In summary, we report a synthetic approach to heterocyclic
tetrahydropentacene derivatives via nucleophilic aromatic
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The Journal of Organic Chemistry
substitution using tetrafluoroterephthalonitrile. Using this
mixture heated to reflux. After 12 h, the reaction was cooled to
0 °C and sodium sulfate decahydrate (Na2SO4·10H2O) was
added in small portions, over approximately 25 min, until
hydrogen evolution subsided. Aqueous ammonium chloride
was then added until neutral, and the emulsion thus obtained
filtered through a pad of Celite®, washing the filter cake with
diethyl ether. The volatiles were then removed in vacuo, the
residue partitioned between ether and H2O, and the aqueous
layer extracted with ether (3 x 20 mL). The pooled organic
extracts were washed with saturated aqueous NaHCO3 (20 mL),
brine (20 mL), dried over MgSO4, filtered, and concentrated in
vacuo. The residue was recrystallized from chloroform (−20
°C) to give the product as white needles (1.10 g, 81%), stored
at −20 °C to slow decomposition. mp (CHCl3) = 105 °C (dec.);
1H NMR (400 MHz, CDCl3) δ: 6.87-6.83 (m, 1H), 6.70-6.60
(m, 3H), 4.12 (br s, 2H), 3.15 (q, J = 7.2 Hz, 2H), 1.27 (t, J =
7.0 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ: 143.7, 137.1,
121.6, 117.8, 114.3, 112.7, 38.9, 14.8. Analytical data agrees
with literature values.27
1
2
3
4
5
6
7
8
approach, we were able to access several different heterocyclic
compounds containing O, N, and S. X-ray crystallography
reveals that the N and O-containing compounds (1 and 4) were
highly planar and they exhibited some π-stacking in the solid
state. Meanwhile, the sulfur containing compounds 6 and 7
were bent and they exhibited less π-stacking. All the
compounds were highly emissive in solution with the
heteroatom substitution significantly affecting the absorption
and emission in addition to the absolute quantum yields. While
all the compounds were electroactive, they could only be
oxidized. Similar to the spectroscopic properties, the oxidation
potential and the electrochemical reversibility of
tetrahydropentacene derivatives were also contingent on their
heteroatom.
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EXPERIMENTAL
Synthetic Procedures
General
N-(2-hydroxyphenyl)decanamide (11c): To a 250 mL
round bottomed flask was added 2-aminophenol (2.50 g, 22.9
mmol, 1.0 eq), THF (100 mL), pyridine (4.1 mL, 50 mmol, 2.2
eq). This was stirred until dissolution, and decanoyl chloride
(4.8 mL, 23 mmol, 1.0 eq) was added dropwise causing a
precipitate which dissolved by the end of addition. This was left
to stir under N2 overnight (18 h). Volatiles were removed in
vacuo, and the residue was partitioned between chloroform and
water. The aqueous layer was extracted with chloroform (2 x 25
mL) and the pooled organic solvents washed with 1 M HCl (25
mL), H2O (25 mL), dried over MgSO4, filtered, and
concentrated in vacuo. The crude solid thus obtained was
recrystallized from aqueous methanol to yield N-(2-
hydroxyphenyl)decanamide as a white fluffy solid (4.39 g,
73%). mp (MeOH/H2O) = 67-68 °C (lit. 71 °C);28 1H NMR (400
MHz, CDCl3) δ: 8.96 (s, 1H), 7.92 (s, 1H), 7.14-7.06 (m, 2H),
6.97 (d, J = 7.8 Hz, 1H), 6.84 (t, J = 7.6 Hz, 1H), 2.42 (t, J =
7.5 Hz, 2H), 1.75-1.68 (m, 2H), 1.35-1.24 (m, 14H), 0.87 (t, J
= 6.7 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3) δ: 173.7,
148.6, 127.0, 125.6, 122.0, 120.3, 119.7, 37.0, 31.8, 29.4, 29.3,
29.2, 29.1, 25.7, 22.6, 14.0.
1H and 13C spectra were recorded on an Agilent Technologies
Varian 300 MHz Unity Inova NMR Spectrometer or 400 MHz
NMR Spectrometer using the indicated deuterated solvents
purchased from Sigma-Aldrich. Chemical shifts are reported in
δ scale downfield from the peak for tetramethylsilane. High
resolution mass spectra were recorded at the Centre Régional
de Spectrométrie de Masse à l’Université de Montréal using an
Agilent LC-MSD TOF spectrometer. All reagents and starting
materials were purchased from Sigma-Aldrich and used as
purchased. Anhydrous solvents were dispensed using a custom-
built solvent system from Glasscontour (Irvine, CA) which used
purification columns packed with activated alumina and
supported copper catalyst. Oven-dried glassware was used for
all reactions that were performed under nitrogen. Melting points
were determined on a Mel-Temp® Electrothermal melting
point apparatus and are uncorrected.
N-(2-hydroxyphenyl)acetamide (11b): To a 500 mL round
bottomed flask was added 2-aminophenol (5.00 g, 45.8 mmol,
1.0 eq), EtOAc (100 mL), followed by acetic anhydride (4.70
mL, 50.4 mmol, 1.1 eq). This was stirred at room temperature
for 4 h, diethyl ether (100 mL) was added and the mixture
cooled to ~5 °C. The precipitate was collected as a grey powder
via suction filtration, washing with diethyl ether. The crude
product was recrystallized from aqueous ethanol as off-white
plates (6.11 g, 89%). mp (EtOH/H2O) = 208-209 °C (lit. mp =
2-(N-decylamino)phenol (12c): To a 250 mL two-neck
round-bottomed flask, equipped with a reflux condenser under
N2 and equipped with an addition funnel, was added lithium
aluminum hydride (0.915 g, 24.1 mmol, 2.0 eq) and THF (60
mL), and this was cooled to 0 °C. A solution of N-(2-
hydroxyphenyl)decanamide 11c (3.17 g, 12.0 mmol, 1.0 eq) in
THF (35 mL) was then added dropwise via addition funnel to
the cold reaction flask over 15 minutes. The ice bath was then
replaced with an oil bath and the mixture gradually brought to
reflux for 12 h, after which time the mixture was cooled to 0 °C
and quenched via cautious addition of Na2SO4•10H2O in small
portions. The mixture was then brought to neutral pH with
saturated NH4Cl (pH paper), filtered through Celite®, and
concentrated in vacuo. The residue was dissolved in EtOAc (50
mL), washed with saturated NaHCO3 (20 mL), H2O (20 mL),
and brine (40 ml). The organic layer was dried over Na2SO4,
filtered, and concentrated in vacuo to give the aminophenol as
a purple solid, which was used for the following reactions
1
209 °C); H NMR (400 MHz, CD3OD) δ:7.57 (d, J = 7.6 Hz,
1H), 7.01-6.98 (m, 1H), 6.86-6.78 (m 2H), 2.17 (s, 3H);
13C{1H} NMR (100 MHz, CD3OD) δ: 172.2, 149.7, 127.1,
126.8, 123.9, 120.6, 117.3, 23.4. Analytical data agrees with
literature values.26
2-(N-ethylamino)phenol (12b): To a dry, 250 mL three-
neck round bottomed flask, equipped with a dried stir bar,
condenser,
and
N2
inlet,
was
added
N-(2-
hydroxyphenyl)acetamide 11b (1.50 g, 9.92 mmol, 1.0 eq) and
THF (75 mL). This was then cooled to 0 °C, and lithium
aluminum hydride (1.0 M in THF, 19.8 mL, 2.0 eq) was added
dropwise, pausing as appropriate for hydrogen evolution. The
ice bath was then replaced with an oil bath and the reaction
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without further purification (2.40 g, 80%). mp (hexanes) = 65
°C (dec.); H NMR (400 MHz, CDCl3) δ: 6.90-6.84 (m, 1H),
(APCI) m/z: [M]+ Calc. for C14H5N3OF2 269.0401; Found
269.0391.
1
1
2
3
4
5
6
7
8
9
6.72-6.62 (m, 3H), 4.46 (br s, 2H), 3.13-3.10 (m, 2H), 1.68-1.61
(m, 2H), 1.45-1.29 (m, 14H), 0.90 (t, J = 6.6 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ: 143.7, 137.2, 121.5, 117.6, 114.3,
112.5, 44.5, 31.9, 29.6, 29.5, 29.4, 29.3, 27.2, 22.6, 14.1.
10-ethyl-2,3-difluoro-10H-phenoxazine-1,4-
dicarbonitrile (13): To a 25 mL pear-shaped flask was added
tetrafluoroterephthalonitrile (559 mg, 2.79 mmol, 1.0 eq),
followed by DMSO. This was warmed to dissolution (50 °C)
and 2-(ethylamino)phenol 12b (383 mg, 2.79 mmol, 1.0 eq) was
added in portions. This was stirred at room temperature for 24
h, after which time H2O (60 mL) was added and the solid
collected via suction filtration, washing with water. The powder
thus obtained was recrystallised from acetonitrile to furnish the
product as long, orange needles (665 mg, 80%). mp (MeCN) =
223-225 °C; 1H NMR (400 MHz, CDCl3) δ: 7.05 (t, J = 7.6 Hz,
1H), 6.96 (t, J = 7.6 Hz, 1H), 6.91-6.89 (m, 1H), 6.85-6.83 (m,
1H), 4.04 (q, J = 6.9 Hz, 2H), 1.38 (t, J = 6.9 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ: 147.8 (t, JC−F = 3.3 Hz), 146.4 (dd,
JC−F = 255.0, 13.5 Hz), 145.5, 143.0 (dd, JC−F = 255.8, 14.9 Hz),
135.8 (dd, JC−F = 3.3, 1.4 Hz), 131.0, 126.1, 125.0, 117.0, 116.6,
111.2 (d, JC−F = 3.6 Hz), 108.7 (d, JC−F = 3.9 Hz), 95.7 (dd, JC−F
= 16.6, 3.0 Hz), 93.5 (d, JC−F = 17.1 Hz), 46.6, 13.7; 19F NMR
(376 MHz, CDCl3) δ: -135.4 (d, J = 21 Hz), -140.5 (d, J = 21
Hz); HRMS (ESI) m/z: [M+H]+ Calc. for C16H10F2N3O
298.0786; Found 298.0791.
7,14-diethyl-7,14-dihydrobenzo[5,6][1,4]oxazino[2,3-
b]phenoxazine-6,13-dicarbonitrile (4b): To a 25 mL round
bottomed flask, under N2, was added 2-(N-ethylamino)phenol
12b (120 mg, 0.875 mmol, 2.0 eq), tetrafluoroterephthalonitrile
(88 mg, 0.44 mmol, 1.0 eq), DMF (5 mL), and finally K2CO3
(726 mg, 5.25 mmol, 6.0 eq). This was stirred and heated to
100 °C for 24 h in an oil bath, after which time the mixture was
cooled to rt and poured into H2O (75 mL). After cooling
overnight, the precipitate was collected as a red solid which was
recrystallized from chloroform-methanol (172 mg, 100%). mp
> 260 °C; Rf (50% EtOAc/Hexanes) = 0.33; 1H NMR (400 MHz,
CDCl3) δ: 7.03-6.84 (m, 8H), 3.94 (t, J = 7.0 Hz, 4H), 1.28 (t, J
= 7.0 Hz, 6H); 13C{1H} NMR (100 MHz, CDCl3) δ: 148.0,
147.5, 132.7, 131.5, 125.3, 124.4, 118.9, 116.5, 112.9, 95.0,
48.7, 13.2; HRMS (ESI) m/z: [M+H]+ Calc. for C24H19N4O2
395.1503; Found 395.1505.
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
7,14-didecyl-7,14-dihydrobenzo[5,6][1,4]oxazino[2,3-
b]phenoxazine-6,13-dicarbonitrile (4c): To a 50 mL round-
bottomed flask was added tetrafluoroterephthalonitrile (225
mg, 1.12 mmol, 1.0 eq), K2CO3 (1.24 g, 8.96 mmol, 8.0 eq), and
DMF (20 mL). This was placed under N2 and 12c (560 mg, 2.25
mmol, 2.0 eq) was added in portions. The mixture was heated
to 100 °C in an oil bath. After 24 h, the mixture was cooled,
poured into H2O (125 mL), and the red solid collected via
suction filtration, washing with H2O. This was then
recrystallised from toluene-methanol to yield the product as a
red, microcrystalline solid (583 mg, 84%). mp = 145-146 °C;
1H NMR (400 MHz, CDCl3) δ: 7.03-6.99 (m, 2H), 6.94-6.89
(m, 4H), 6.83 (d, J = 7.9 Hz, 2H), 3.88 (t, J = 7.5 Hz, 4H), 1.70-
1.62 (m, 4H), 1.33-1.21 (m, 28H), 0.86 (t, J = 6.8 Hz, 6H);
13C{1H} NMR (100 MHz, CDCl3) δ: 147.7, 147.4, 133.1, 131.8,
125.2, 124.1, 118.6, 116.4, 112.9, 94.7, 53.1, 31.8, 29.47, 29.45,
29.2, 29.1, 27.4, 26.2, 22.6, 14.1.
2-(2-aminophenoxy)-3-fluoro-10H-phenoxazine-1,4-
dicarbonitrile (9): To a 50 mL round-bottomed flask, under N2,
was added tetrafluoroterephthalonitrile (600 mg, 3.00 mmol,
1.0 eq), 2-aminophenol (654 mg, 6.00 mmol, 2.0 eq), dry DMF
(20 mL), and finally K2CO3 (3.32 g, 24.0 mmol, 8.0 eq). The
mixture was heated to 65 °C in an oil bath and quickly became
a deep purple colour; this was left to stir 20 h. The reaction
mixture was cooled to rt, then H2O was then added effecting
precipitation of a reddish-brown solid, collected via suction
filtration, and triturated with acetonitrile yielding a mixture of
products (400 mg) from which a single crystal (DMF) subjected
to X-ray diffraction identified that component as the title
compound. IR(ATR) νmax = 3445, 3360, 3279, 2250, 2236,
1626, 1570, 1499, 1466, 1383, 1287, 1196, 1173, 1033, 996,
749, 731 cm-1; HRMS (ESI) m/z: [M+H]+ Calc. for
C20H12FN4O2 359.0939; Found 359.0949.
2,3-difluoro-10H-phenoxazine-1,4-dicarbonitrile (10): To
a 250 mL round-bottomed flask was added 2-aminophenol
(1.43 g, 13.1 mmol, 1.0 eq), tetrafluoroterephthalonitrile (2.62
g, 13.1 mmol, 1.0 eq), and DMSO (65 mL). This was equipped
with a drying tube (CaSO4) and stirred at rt for 18 h, by which
time a bright orange solid had precipitated. H2O (200 mL) was
added to effect full precipitation and the product was collected
via suction filtration (3.50 g, 100%). This powdery solid could
be recrystallised from hot DMF to afford long orange needles.
2,3-difluorodibenzo[b,e][1,4]dioxine-1,4-dicarbonitrile
(8): To a 250 mL single neck round-bottomed flask was added
catechol (2.00 g, 18.2 mmol, 1 eq), tetrafluoroterephthalonitrile
(3.64 g, 18.2 mmol, 1 eq), and potassium carbonate (7.53 g, 54.5
mmol, 3 eq) followed by dry THF (150 mL). The flask was
equipped with a condenser under N2 and the mixture was heated
in an oil bath at reflux with stirring for 2 h, then stirred at rt for
8 h. After this time H2O (150 mL) was added to effect
crystallization of the product and the mixture was cooled to ~5
°C. The yellow suspension was suction filtered, washed three
times with H2O and dried to give the product as a yellow
powdery solid which was recrystallised from DME to give the
product as very light-yellow plates (3.62 g, 74%). mp (DME) =
209-210 °C; 1H NMR (400 MHz, CDCl3) δ: 7.09-7.02 (m, 4H);
13C{1H} NMR (75 MHz, CDCl3) δ: 145.7 (dd, JC−F = 261.4,
15.8 Hz), 141.4 (t, J = 3.5 Hz), 139.3, 126.4, 117.1, 107.7 (d,
JC−F = 1.9 Hz), 96.7 (dd, JC−F = 11.2, 7.8 Hz); 19F NMR (376
MHz, CDCl3) δ: -134.7. Analytical data agrees with literature
values.29
1
mp (DMF) > 260 °C. H NMR (400 MHz, DMSO-d6) δ: 9.58
(s, 1H), 6.90 (s, 2H), 6.81 (s, 2H); 13C{1H} NMR (100 MHz,
acetone-d6) δ: 145.8 (dd, JC−F = 250.1, 13.6 Hz), 144.6, 142.4
(dd, JC−F = 248.1, 14.7 Hz), 142.3, 135.4, 128.8, 126.8, 124.8,
116.7, 116.3, 110.5 (d, JC−F = 3.4 Hz), 109.5 (d, JC−F = 3.5 Hz),
95.6 (d, JC−F = 15.8 Hz), 89.7 (d, JC−F = 18.9 Hz); 19F NMR
(282 MHz, acetone-d6) δ: −142.3 (d, J = 20 Hz), −148.16 (d, J
= 20 Hz); IR (ATR) νmax: 3157 (w), 3113 (w), 3063 (w), 2951,
2898, 2239, 2230, 1470, 1288, 1023, 993, 759 cm-1; HRMS
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The Journal of Organic Chemistry
14-ethyl-14H-benzo[5,6][1,4]dioxino[2,3-b]phenoxazine-
125.2, 125.1, 124.9, 124.5, 120.4, 116.5, 116.4, 112.0, 111.0,
102.9, 97.2, 48.4, 13.9; HRMS (ESI) m/z: [M+H]+ Calc. for
C22H14N3O2S 384.0801; Found 384.0788.
1
2
3
4
5
6
7
8
6,13-dicarbonitrile (5): To a 50 mL round-bottomed flask was
added difluoride 8 (905 mg, 3.35 mmol, 1.0 eq) and DMF (15
mL) under N2. K2CO3 (1.85 g, 13.4 mmol, 4.0 eq) was then
added, followed by 2-(N-ethylamino)phenol 12b (459 mg, 3.35
mmol, 1.0 eq). This was heated to 100 °C for 24 h in an oil bath,
after which time the orange mixture was cooled, poured into
H2O, and then filtered. The collected precipitate was
recrystallised from toluene-methanol to yield the title
compound as an orange crystalline solid (851 mg, 70%). mp
7,14-diethyl-7,14-dihydrobenzo[5,6][1,4]thiazino[2,3-
b]phenothiazine-6,13-dicarbonitrile (7): To a 25 mL two-
neck round-bottomed flask, under N2, was added
tetrafluoroterephthalonitrile (158 mg, 0.791 mmol, 1.0 eq),
K2CO3 (1.66 g, 6.32 mmol, 8.0 eq) and dry DMF (10 mL). A
solution of 2-(N-ethylamino)thiophenol 14 (300 mg, 1.58
mmol, 2.0 eq) in DMF (5 mL) was then added dropwise. After
addition was complete the orange mixture was heated to 100 °C
for 12 h in an oil bath, turning dark red in colour. The mixture
was cooled, diluted with H2O (100 mL), and the precipitate
collected via suction filtration, washing with H2O, then cold
methanol. Recrystallisation of this material from THF provided
the desired product as a bright orange solid (150 mg, 0.352
mmol, 45%). mp (THF) > 260 °C; Rf = 0.40 (50%
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
(PhMe/MeOH)
=
241 °C (dec.); Rf
=
0.38 (50%
CHCl3/hexanes); 1H NMR (400 MHz, CDCl3) δ: 7.04-6.84 (m,
8H), 3.96 (q, J = 6.9 Hz, 2H), 1.29 (t, J = 6.9 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3) δ: 146.9, 146.7, 140.1, 140.0, 139.6,
137.1, 133.6, 132.0, 125.8, 125.49, 125.46, 124.5, 118.4, 1170,
116.9, 116.8, 116.3, 112.1, 109.9, 48.2, 13.1; HRMS (ESI) m/z:
[M+H] Calc. for C22H14N3O3 368.1030; Found 368.1037.
1
2-(N-ethylamino)thiophenol hydrochloride (14): To a dry
250 mL three-neck round-bottomed flask equipped with a
reflux condenser was added dry THF (75 mL), solid lithium
aluminum hydride (2.54 g, 66.8 mmol, 1.0 eq), and this was
cooled to 0 °C (ice bath) under N2. To the stirred suspension
was added a solution of 2-methylbenzothiazole (9.97 g, 66.8
mmol, 1.0 eq) in dry THF (10 mL), dropwise. After addition
was complete, the ice bath was replaced with an oil bath and the
mixture heated to reflux for 3 h. The yellow mixture was cooled
to 0 °C and decomposed (carefully) with wet THF (15 mL THF,
5 mL H2O). The pH was then brought to ≈2-3 (pH paper) with
concentrated HCl (9-10 mL) and the mixture filtered through
Celite®, washing with Et2O. The crude solution was dried over
MgSO4, filtered, and concentrated in vacuo to give a yellow
viscous oil which was dissolved in iPrOH and concentrated HCl
(5.9 mL) was added dropwise with stirring. Addition of Et2O
just until cloudy, followed by cooling overnight (−15 °C) gave
the product as a light yellow crystals, collected by suction
filtration, and washing with cold Et2O (7.10 g, 37.4 mmol,
CH2Cl2/hexanes); H NMR (400 MHz, C6D6) δ: 6.83-6.80 (m,
4H), 6.63 (t, J = 7.4 Hz, 2H), 6.51 (d, J = 8.2 Hz, 2H), 3.75 (q,
J = 7.0 Hz, 4H), 0.88 (t, J = 7.0 Hz, 6H); 13C{1H} NMR (100
MHz, CDCl3) δ: 144.1, 143.6, 136.7, 128.4, 127.4, 126.1, 124.7,
120.8, 114.5, 105.9, 49.3, 14.4; HRMS (ESI) m/z: [M+H]+
Calc. for C24H19N4S2 427.1046; Found 427.1047.
X-Ray Crystallography
Data were collected at 110(2) K on a Kappa Nonius CCD
diffractometer with Cu Kα radiation (1, 4c and 6) or on a Bruker
APEX-II CCD diffractometer with Mo Kα radiation (7 and 9.)
While data collection and integration for 1, 4c, 6 and 9 were
straight-forward, crystals of 7 were not of excellent quality and
data processing was non-trivial. Multiple integrations were
attempted using Rigaku’s CrysAlisPro software, with the data
treated as generated from a single crystal, a two-domain twin, a
multi-component twin, and a multi-crystal. While all yielded
the same unit cell dimensions and contents, the most
satisfactory model, wherein all non-hydrogen atoms were
treated anisotropically without restraints, was obtained for the
integrated data of the multi-crystal second component.
Using Olex230, the structures of 1, 4c, 6, 7, and 9 were solved
with the ShelXT31 structure solution program using intrinsic
phasing and refined with the ShelXL32 refinement package
using least squares minimisation. For all structures all non-
hydrogen atoms were introduced in difference map positions
and refined anisotropically, while hydrogen atoms were
introduced in calculated positions and refined on a riding
model, except for N-H hydrogen atoms in the model for 9,
which were introduced in difference map positions, and refined
isotropically. Solvent was disordered over a special position.
During growth, crystals of 6 were in contact with DMF, ethyl
acetate, chloroform, acetonitrile, and possibly water. A sensible
solvent model could not be achieved, and the solvent
contribution was treated with a solvent mask (PLATON
SQUEEZE33.) The solvent contribution was omitted from the
formula, and hence was not included in the calculation of other
intensive properties (ex. molecular weight; density.)
Crystallographic data are summarized in Table S1.
1
56%). mp (iPrOH/Et2O) = 123-124 °C; H NMR (400 MHz,
D2O) δ: 7.66 (ddt, J = 4.6, 3.6, 1.2 Hz, 1H), 7.46-7.39 (m, 3H),
3.51 (qd, J = 7.3, 1.4 Hz, 2H), 1.33 (td, J = 7.3, 1.4 Hz, 3H);
13C{1H} NMR (100 MHz, D2O) δ: 135.7, 134.4, 130.1, 128.6,
124.9, 123.7, 46.6, 10.1.
12-ethyl-12H-benzo[5,6][1,4]dioxino[2,3-
b]phenothiazine-6,13-dicarbonitrile (6): To a 25 mL round-
bottomed flask was added dibenzodioxin difluoride 8 (1.42 g,
5.27 mmol, 1.0 eq), K2CO3 (2.91 g, 21.08 mmol, 4.0 eq), and
dry DMF (24 mL). This was placed under N2, and a solution of
2-(ethylamino)thiophenol hydrochloride 14 (1.00 g, 5.27 mmol,
1.0 eq) in DMF (15 mL) was added dropwise. The reaction
mixture was heated in an oil bath at 100 °C for 36h.
Subsequently, the mixture was cooled to room temperature,
poured into H2O (200 mL), and the precipitate collected via
suction filtration, washing with H2O. The crude solid thus
obtained was recrystallised from EtOAc to yield the product as
orange needles (1.10 g, 2.86 mmol, 54%). mp (EtOAc) = 243-
244 °C; 1H NMR (400 MHz, C6D6) δ: 6.83-6.78 (m, 2H), 6.64
(t, J = 7.5 Hz, 1H), 6.53-6.43 (m, 5H), 3.80 (q, J = 7.0 Hz, 2H),
0.92 (t, J = 7.0 Hz, 3H); 13C{1H} NMR (100 MHz, C6D6) δ:
143.3, 143.2, 140.1, 139.8, 139.4, 129.4, 128.0, 127.2, 126.2,
Emission Studies
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Page 8 of 9
measurements. CY thanks both MITACS and the Université de
Electronic absorption spectra were measured with a Varian
(Agilent) Cary 500 UV-vis-NIR spectrometer. Emission
measurements were made with an Edinburgh Instruments
FLSP-920 combined steady-state/time-resolved spectrometer.
Solutions for emission quantum yield measurements were
prepared with ꢀan absorbance of 0.1 at the corresponding
excitation wavelength. The samples were then purged with
nitrogen for at least 30 min., sealed, and then measured. An
appropriate cut-off filter was used for the Φem measurements to
remove the excitation frequency doubling from the recorded
emission. Three scans each with a dwell time of 1 sec/nm were
averaged.
1
2
3
4
5
6
7
8
Montréal for graduate scholarships. We also thank Dr. A. Furtos at
the Université de Montréal for mass spectrometric analyses. Dr.
Paul Boyle, Department of Chemistry X-Ray Facility, University
of Western Ontario, is acknowledged for X-ray crystallographic
data collections. Compute Canada (www.computecanada.ca) and
their partners, Compute Ontario (computeontario.ca) and WestGrid
(www.westgrid.ca), are also acknowledged for access to
computational resources and software for theoretical calculations.
9
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45
46
47
48
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AUTHOR INFORMATION
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Corresponding Author
* kmaly@wlu.ca.
Author Contributions
All authors have given approval to the final version of the
manuscript.
Notes
The authors declare no conflicts.
ACKNOWLEDGMENT
KEM and WGS are grateful to the Natural Sciences and
Engineering Research Council of Canada (NSERC) and the Canada
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Support Fund. LKH acknowledges an NSERC Postgraduate
Award (PGS-M) and an Ontario Graduate Scholarship for support.
WGS acknowledges Natural Sciences and Engineering Research
Council Canada and the Canada Foundation for Innovation for
equipment that supported the reported spectroscopic
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