One-step synthesis of unsymmetrical N -Alkyl- N '-aryl perylene diimides

Article abstract of DOI:10.1021/jo500945k

An efficient and facile protocol for the synthesis of unsymmetrical N-alkyl-N'-aryl perylene diimides is reported that circumvents the need for multiple reaction steps. A number of unsymmetrical perylene diimides containing a solubilizing swallowtail alky

Full text of DOI:10.1021/jo500945k

Note
pubs.acs.org/joc
One-Step Synthesis of Unsymmetrical N‑Alkyl‑N′‑aryl Perylene
Diimides
Maxwell J. Robb, Brandon Newton, Brett P. Fors, and Craig J. Hawker*
Department of Chemistry and Biochemistry, Materials Department, and Materials Research Laboratory, University of California,
Santa Barbara, California 93106, United States
S
* Supporting Information
ABSTRACT: An efficient and facile protocol for the synthesis
of unsymmetrical N-alkyl-N′-aryl perylene diimides is reported
that circumvents the need for multiple reaction steps. A number
of unsymmetrical perylene diimides containing a solubilizing
swallowtail alkyl group and a variety of substituted aryl groups
can be prepared in a single step from a simple mixture of amines.
Scheme 1. Synthesis of Unsymmetrical PDIs
erylene diimides (PDIs) are a class of materials that have
Pfound widespread use in a number of diverse fields.
Originally developed as industrial pigments, their outstanding
properties including high photochemical stability, fluorescence
quantum yields near unity, propensity to self-assemble, and
strong electron-accepting character have propelled PDIs toward
applications in (multi)chromophoric systems,1 supramolecular
chemistry,2 and organic electronics.3
Unsymmetrical PDIs bearing unique substituents at each
imide position constitute an important subgroup within this
class of materials due to their significant synthetic versatility.
For example, incorporation of an alkyl group at one imide
position imparts good solubility, while a unique substituent on
the other imide nitrogen can be utilized to direct assembly or as
a handle for further derivatization and the construction of more
sophisticated structures. For the former, branched “swallowtail”
alkyl amines, such as 1-hexylheptyl amine, are routinely
employed for their advantageous solubility properties.4
Typically, unsymmetrical PDIs are synthesized according to a
multistep process (Scheme 1).5 First, perylene dianhydride is
reacted with an alkyl amine of one type, resulting in a
symmetrical PDI. In a second step, one of the imides is
converted back into an anhydride in a statistical hydrolysis
reaction that often proceeds with difficulty. This second step
results in an average yield of 44% from bis(1-hexylheptyl)-
PDI.6 In the third and final step, reaction of the perylene
monoimide monoanhydride with a second amine affords the
unsymmetrical PDI product. Using a less common protocol, a
limited number of alkyl/alkyl7 and aryl/aryl8 unsymmetrical
PDIs have also been prepared in one step from a mixture of
amines; however, the reaction is usually reported to be
unsuccessful for mixed alkyl/aryl systems. Traditionally, this
mixed approach results almost exclusively in the formation of
the two symmetrical PDIs due to the difference in reactivity of
the amines with perylene dianhydride.3b To the best of our
knowledge, there are only two reports in the literature of this
type of transformation, both of which resulted in the desired
unsymmetrical product in ∼10% yield.9
Recently, we developed a synthetic procedure that facilitates
the preparation of unsymmetrical N-alkyl-N′-aryl PDIs in a
single reaction step from a stoichiometric mixture of the
corresponding alkyl and aryl amines in ca. 40% yield after
purification.10 Given the significant difference in pKa (and
nucleophilicity) of alkyl versus aryl amines, it is indeed
surprising that reasonable yields could be achieved from a
simple mixture of reactants. In this note, we examine the scope
and utility of this one-step reaction of a mixture of alkyl and
aryl amines with perylene dianhydride for the preparation of
unsymmetrical PDIs.
Received: April 29, 2014
© XXXX American Chemical Society
A
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We began by studying the reaction of perylene dianhydride
with a mixture of aniline and 1-hexylheptyl amine 1 under a
variety of reaction conditions (Table 1). Using imidazole as the
emphasize the unique efficacy of using imidazole for these
imidization reactions.
Based on the results above, the statistical nature of the one-
step reaction was investigated in greater detail by performing
the reaction in a stepwise fashion (Scheme 2). A similar
Table 1. Comparison of Reaction Conditions for the One-
a
Step Synthesis of an Unsymmetrical PDI
Scheme 2. Stepwise Synthesis of an Unsymmetrical PDI by
Sequential Addition of Aniline and Alkyl Amine 1
b
entry
solvent
imidazole
temp (°C) reaction time (h) yield (%)
1
130
130
130
130
130
130
130
2
2
42
42
8
strategy for the synthesis of unsymmetrical alkyl/aryl PDIs has
been reported previously employing several different reaction
conditions with mixed results.11 It is interesting to note that the
expected distribution of products resulting from a purely
statistical reaction performed in a stepwise fashion is the same
as the one-step reaction: alkyl/alkyl (symmetrical, 25%), alkyl/
aryl (unsymmetrical, 50%), and aryl/aryl (symmetrical, 25%).
In direct contrast to the results obtained using a one-step
procedure, we found that the isolated yield of the desired
unsymmetrical PDI was significantly reduced to 15−20% when
the reaction was performed in a stepwise process (with ∼40%
bisalkyl PDI being obtained). Furthermore, the order of amine
addition did not influence the outcome of the reaction. Imide
formation was also found to be irreversible under the reaction
conditions.12 These results suggest a possible synergistic
interaction between the alkyl and aryl amines as well as
imidazole that provides a distinct advantage in this single step
procedure.
In order to probe the transformation further, a set of control
experiments was performed using 1,8-naphthalic anhydride as a
model substrate, and reaction progress was monitored by gas
chromatography (Figure 1). A series of reactions were
conducted under the standard imidization conditions employed
above using a mixture of 1 equiv of each amine with respect to
the substrate in imidazole at 130 °C. Remarkably, we found
that the phenyl naphthalimide is formed rapidly under these
conditions (at ∼50% yield). Moreover, despite ca. 0.5 equiv of
remaining aniline, the amount of phenyl naphthalimide does
not change over the course of the reaction. In contrast, the alkyl
amine reacts relatively slowly, converting the remaining
anhydride into the alkyl naphthalimide product over ca. 1 h.
Additionally, the rate of formation of the alkyl naphthalimide
product was found to be independent of the swallowtail amine
concentration. These findings indicate that nucleophilic attack
of the amine is not responsible for controlling the rate of
imidization. It is important to point out that the phenyl
naphthalimide and alkyl naphthalimide products were isolated
in excellent yield when the reaction was performed exclusively
with either aniline or 1, respectively. Furthermore, we
hypothesized that acid/base equilibria may be important in
influencing the extent of reaction observed for the aryl amine.
c
2
imidazole
3
4
5
6
N-methylimidazole
N-methylimidazole
DMAP
2
21
2
27
27
29
2
DMAP
7
d
7
DMF
3
a
Reaction conditions: 1 equiv of perylene dianhydride, 1 equiv of 1, 1
b
equiv of aniline, 60−70 equiv of solvent. Isolated yield after
c
chromatographic separation. With 2 equiv each of 1 and aniline.
d
With 10 equiv of imidazole used.
solvent at 130 °C, we were pleased to find that the
unsymmetrical product was formed and could be readily
isolated via silica gel column chromatography in 42% yield. As
expected, the bisalkyl PDI is also obtained while the poor
solubility of the bisaryl PDI prohibits its isolation. It is also
worth noting that imidization proceeded smoothly in the
absence of Zn(OAc)2, which is often used as a catalyst. The
isolated yield of the unsymmetrical PDI approaches the
theoretically expected yield of 50% resulting from a statistical
distribution of symmetrical (i.e., alkyl/alkyl, aryl/aryl) and
unsymmetrical products. Surprisingly, the same results are
achieved when the reaction is performed using 2 equiv of each
amine with respect to perylene dianhydride, suggesting a
negligible dependence on the nucleophilicity of the amine
under these conditions. Conversely, when the reaction is
performed using alternative conditions, the yield of the desired
unsymmetrical PDI is significantly reduced. For example, the
reaction proceeds much more slowly in N-methylimidazole
(NMI) with the unsymmetrical product being formed in only
27% yield after extended reaction times (Table 1, entry 4).
Comparatively, the reaction is accelerated when 4-dimethyl-
aminopyridine (DMAP) is employed; however, the overall
yield of the unsymmetrical PDI is approximately the same as
with NMI. This disparity is even more apparent when
traditional solvents like DMF are employed (Table 1, entry
7), resulting in negligible quantities of the unsymmetrical
product and nearly exclusive formation of the symmetrical PDI
in accordance with previous literature reports. These findings
B
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Table 2. One-Step Synthesis of Unsymmetrical PDIs Using a
a
Variety of Substituted Anilines
Figure 1. Model reactions performed for varying amounts of time and
analyzed by GC demonstrate rapid reaction of aniline and relatively
slow reaction of the alkyl amine. The net result is an approximately
equal mixture of aryl- and alkyl-substituted products. Reaction
conditions: 1.0 equiv of 1,8-naphthalic anhydride, 1.0 equiv of aniline,
1.0 equiv of 1, 35 equiv of imidazole, 130 °C.
Indeed, the addition of acetic acid or Hunig’s base was
̈
demonstrated to systematically change the extent of reaction of
aniline and the corresponding conversion of the alkyl amine
with similar kinetic profiles being observed (see Table S1 in the
Supporting Information).
a
Reaction conditions: 1.0 equiv of perylene dianhydride, 1.1 equiv of
aryl amine, 1.1 equiv of 1, 70 equiv of imidazole, 130 °C, 2−3 h.
b
c
Isolated yield (average of two runs). With 1.1 equiv of Hunig’s base
̈
With this information and the successful demonstration of
the one-step protocol for the synthesis of unsymmetrical PDIs,
we set out to evaluate the scope of this method with a variety of
substituted aniline derivatives. This facile one-step procedure
was successfully applied to prepare a number of unsymmetrical
PDIs using a wide range of aniline starting materials (Table 2).
Both electron-rich and electron-deficient anilines were
successfully employed, providing similar yields of the unsym-
metrical PDIs and demonstrating the robustness of this
strategy. Importantly, unsymmetrical PDIs containing diverse
functional groups can be prepared in a straightforward fashion
allowing for subsequent chemical modification to suit a variety
of applications. For example, unsymmetrical PDIs containing
aryl halides (Table 2, entries 2 and 3) amenable to Pd-catalyzed
cross-coupling reactions and those bearing polymerizable
(Table 2, entry 6) as well as nucleophilic or electrophilic
groups (Table 2, entries 4 and 7, respectively) are readily
accessed. Each of these materials is easily isolated by simple
chromatographic techniques in high purity, and the reaction is
scalable. To demonstrate the latter point, the unsymmetrical
PDI containing an aryl bromide functional group (Table 2,
entry 2) was prepared on gram scale.
This one-step protocol for the synthesis of unsymmetrical
alkyl/aryl PDIs provides several advantages over the commonly
employed multistep procedure. First, the yields for several
previously reported PDIs are higher when accessed via the one-
step protocol presented here. For example, utilizing 1 and 4-
aminobenzoic acid, our method yielded 40% of the desired
unsymmetrical product (Table 2, entry 7), while the previously
reported synthesis gave only 25% after three steps.13 Similar
overall yields were attained previously for the unsymmetrical
PDIs prepared using aniline (28%),14 4-iodoaniline (33%),15
and 4-aminostyrene (14%).16 In addition to improved yields,
used.
this one-step method enhances the accessibility of many
important unsymmetrical PDI molecules by decreasing both
the time and resources required for their preparation.
In conclusion, an efficient and facile protocol for the
preparation of unsymmetrical perylene diimides (PDIs) has
been successfully demonstrated. Unsymmetrical PDIs contain-
ing a swallowtail solubilizing group and aryl substituents with a
variety of functional groups can be prepared in a single step
from a simple mixture of amines using imidazole as the reaction
medium. This protocol provides significant advantages over the
traditional three-step methodology commonly employed to
access these types of valuable materials.
EXPERIMENTAL SECTION
■
Materials. All reactions were carried out under an argon
atmosphere. All reagents from commercial sources were used without
further purification unless otherwise stated. Aniline was fractionally
distilled under reduced pressure. The 4-iodoaniline was purified by
recrystallization from hexanes. The 1-hexylheptylamine6b was prepared
according to the literature and purified by vacuum distillation prior to
use.
Instrumentation. All compounds were characterized by 1H NMR
spectroscopy, IR spectroscopy, and mass spectrometry. Due to the
limited solubility of perylene diimides, 13C NMR spectra are reported
only for new compounds. Copies of the NMR and mass spectra (FD)
can be found in the Supporting Information. NMR spectra were
recorded using a 500 or 600 MHz spectrometer. All 1H NMR
experiments are reported in δ units, parts per million (ppm), and were
measured relative to the signals for residual chloroform (7.26 ppm),
dichloromethane (5.32 ppm), or tetrahydrofuran (1.73 and 3.58 ppm)
in deuterated solvent. All 13C NMR spectra were measured in
deuterated solvents and are reported in ppm relative to the signals for
C
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residual chloroform (77.16 ppm) or tetrahydrofuran (25.37 and 67.57
ppm). Mass spectrometry was performed on a quadrupole/time-of-
flight tandem mass spectrometer (ESI) or a time-of-flight mass
spectrometer (EI and FD). IR spectra were recorded using an
attenuated total reflectance (ATR) sampling accessory. GC analyses
were performed using a Restek SHRXI-5MS column (15 m, 0.25 mm
i.d.) and FID detector.
General Procedure A. A 50 mL round-bottom flask equipped
with a magnetic stir bar was charged with perylene-3,4,9,10-
dianhydride, imidazole, and the aryl amine (if a solid). The vessel
was sealed with a rubber septum and purged with argon for 5 min. The
aryl amine (if a liquid) and 1-hexylheptylamine (d = 0.79 g/mL) were
then added via syringe. The contents of the flask were briefly mixed,
and the vessel was immersed in an oil bath maintained at 130 °C for
the indicated amount of time. At the conclusion of the reaction, the
vessel was allowed to cool to room temperature, dichloromethane
(DCM) was added (25 mL), and the mixture was briefly sonicated.
The mixture was diluted with DCM (100 mL) and washed with
aqueous HCl (2M, 100 mL), using a small amount of isopropyl
alcohol to break an emulsion if necessary. The aqueous layer was
extracted with DCM (2 × 100 mL), and the combined organic
fractions were dried over MgSO4, filtered, concentrated with silica gel,
and purified by column chromatography.
dissolved in DCM. The crude reaction mixture was analyzed directly
by GC.
General Procedure F. General procedure E was used with the
following modification: after the vessel was sealed, either acetic acid or
N,N-diisopropylethylamine was added via syringe.
N-(4-Fluorophenyl)-N′-(1-hexylheptyl)perylene-3,4,9,10-tetra-
carboxylic Diimide (Table 2, entry 1). Following general procedure A,
a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (392 mg,
0.999 mmol), imidazole (4.7 g, 69 mmol), 4-fluoroaniline (0.10 mL,
1.1 mmol), and 1-hexylheptylamine (0.28 mL, 1.1 mmol) was heated
at 130 °C for 2.5 h. The crude product was purified by column
chromatography (50−100% DCM/hexanes followed by 0−10%
EtOAc/DCM) to provide the title compound as a red solid (310
mg, 46%): Rf = 0.31 (DCM); 1H NMR (600 MHz, CD2Cl2) δ 0.84 (t,
J = 6.8 Hz, 6H), 1.19−1.38 (m, 16H), 1.84−1.91 (m, 2H), 2.19−2.29
(m, 2H), 5.16 (tt, J = 9.6, 4.3 Hz, 1H), 7.28 (t, J = 8.5 Hz, 2H), 7.34−
7.39 (m, 2H), 8.57−8.68 (m, 8H) ppm; 13C NMR (125 MHz, CDCl3)
δ 14.2, 22.7, 27.2, 29.4, 31.9, 32.5, 55.1, 116.6 (d, J = 23 Hz), 123.0,
123.1, 123.3, 123.5, 124.3, 126.2, 126.5, 129.4, 129.6, 130.6 (d, J = 8.7
Hz), 130.9 (d, J = 3.3 Hz), 131.0, 131.7, 134.0, 135.0, 162.4 (d, J = 248
Hz), 163.5, 164.4 ppm; IR (solid, cm−1) 3341, 3305, 3099, 2925, 2856,
1697, 1653, 1593, 1341, 1246; HRMS (EI, m/z) calcd for
[C43H39FN2O4]+ (M+), 666.2894; found, 666.2900.
In all cases, bis(1-hexylheptyl)perylene-3,4,9,10-tetracarboxylic
diimide (bisalkyl PDI) is the first product to elute from the column
(Rf,DCM = 0.86), while the second species to elute is the unsymmetrical
PDI. The bisalkyl PDI is easily removed by first eluting with 50−100%
DCM in hexanes, followed by elution of the unsymmetrical product
with a slightly stronger eluent (typically 0−10% EtOAc in DCM).
General Procedure B. General procedure A was used with the
following modification: after the vessel was sealed with a rubber
septum, N,N-diisopropylethylamine was added via syringe.
General Procedure C (Stepwise Addition of Amines). A 50
mL round-bottom flask equipped with a magnetic stir bar was charged
with perylene-3,4,9,10-dianhydride and imidazole. The vessel was
sealed with a rubber septum and purged with argon for 5 min. Either
aniline or 1-hexylheptylamine was then added via syringe. The
contents of the flask were briefly mixed, and the vessel was immersed
in an oil bath maintained at 130 °C. After 2 h, the other amine (either
aniline or 1-hexylheptylamine) was added via syringe, and the reaction
was continued for another 2 h. At the conclusion of the reaction, the
vessel was allowed to cool to room temperature, dichloromethane
(DCM) was added (25 mL), and the mixture was briefly sonicated.
The mixture was diluted with DCM (100 mL) and washed with
aqueous HCl (2 M, 100 mL), using a small amount of isopropyl
alcohol to break an emulsion if necessary. The aqueous layer was
extracted with DCM (2 × 100 mL), and the combined organic
fractions were dried over MgSO4, filtered, concentrated with silica gel,
and purified by column chromatography.
General Procedure D. A 50 mL round-bottom flask equipped
with a magnetic stir bar was charged with 1,8-naphthalic anhydride and
imidazole. The vessel was sealed with a rubber septum and purged
with argon for 5 min, followed by the addition of the amine via syringe.
The vessel was immersed in an oil bath maintained at 130 °C for the
indicated amount of time. At the conclusion of the reaction, the vessel
was allowed to cool to room temperature. The contents were dissolved
in DCM (100 mL) and washed with aqueous HCl (2 M, 100 mL),
using a small amount of isopropyl alcohol to break an emulsion if
necessary. The aqueous layer was extracted with DCM (2 × 100 mL),
and the combined organic fractions were dried over MgSO4, filtered,
concentrated with silica gel, and purified by column chromatography.
General Procedure E (Model Reactions for GC Analysis). A 13
× 100 mm test tube equipped with a magnetic stir bar was charged
with 1,8-naphthalic anhydride and imidazole. The tube was sealed with
a screw cap containing a Teflon septum, and the vessel was purged
with argon for 5 min. Aniline and 1-hexylheptylamine were then added
by syringe, and the tube was immersed in an oil bath maintained at
130 °C for the indicated amount of time. At the conclusion of the
reaction, the vessel was quickly cooled under a stream of water,
dodecane was added as an internal standard, and the contents were
N-(4-Bromophenyl)-N′-(1-hexylheptyl)perylene-3,4,9,10-tetra-
carboxylic Diimide (Table 2, entry 2). Following general procedure A,
a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (1.40 g, 3.57
mmol), imidazole (19 g, 280 mmol), 4-bromoaniline (736 mg, 4.28
mmol), and 1-hexylheptylamine (1.10 mL, 4.35 mmol) was heated at
130 °C for 2 h. The crude product was purified by column
chromatography (50−100% DCM/hexanes) to provide the title
compound as a red solid (1.01 g, 39%): Rf = 0.43 (DCM); 1H
NMR (600 MHz, CDCl3) δ 0.83 (t, J = 7.0 Hz, 6H), 1.17−1.38 (m,
16H), 1.82−1.92 (m, 2H), 2.20−2.30 (m, 2H), 5.19 (tt, J = 9.4, J = 5.8
Hz, 1H), 7.23−7.26 (m, 2H), 7.69−7.72 (m, 2H), 8.63−8.76 (m, 8H)
ppm; 13C NMR (125 MHz, CDCl3) δ 14.2, 22.7, 27.2, 29.4, 31.9, 32.5,
55.1, 123.1, 123.1, 123.4, 123.6, 124.4, 126.3, 126.6, 129.5, 129.8,
130.6, 131.1, 131.8, 132.8, 134.1, 134.1, 135.2, 163.3, 164.5 ppm; IR
(solid, cm−1) 3345, 3309, 2924, 2855, 1698, 1657, 1592, 1340, 1252,
1175; HRMS (ESI, m/z) calcd for [C43H39BrN2O4 + Na]+ (M + Na)+,
749.1991; found, 749.1978.
N-(4-Iodophenyl)-N′-(1-hexylheptyl)perylene-3,4,9,10-tetra-
carboxylic Diimide (Table 2, entry 3). Following general procedure A,
a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (392 mg,
0.999 mmol), imidazole (4.7 g, 69 mmol), 4-iodoaniline (241 mg, 1.10
mmol), and 1-hexylheptylamine (0.28 mL, 1.1 mmol) was heated at
130 °C for 2 h. The crude product was purified by column
chromatography (50−100% DCM/hexanes followed by 0−10%
EtOAc/DCM) to provide the title compound as a red solid (268
mg, 35%): Rf = 0.47 (DCM); 1H NMR (600 MHz, CDCl3) δ 0.83 (t, J
= 6.9 Hz, 6H), 1.17−1.40 (m, 16H), 1.83−1.92 (m, 2H), 2.20−2.30
(m, 2H), 5.18 (tt, J = 9.3, 5.9 Hz, 1H), 7.09−7.14 (m, 2H), 7.88−7.93
(m, 2H), 8.61−8.74 (m, 8H) ppm; IR (solid, cm−1) 3345, 3313, 3067,
2953, 2923, 2854, 1697, 1655, 1339, 1251; HRMS (EI, m/z) calcd for
[C43H39IN2O4]+ (M+), 774.1955; found, 774.1947.
N-(4-Hydroxyphenyl)-N′-(1-hexylheptyl)perylene-3,4,9,10-tetra-
carboxylic Diimide (Table 2, entry 4). Following general procedure A,
a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (392 mg,
0.999 mmol), imidazole (4.6 g, 68 mmol), 4-aminophenol (119 mg,
1.09 mmol), and 1-hexylheptylamine (0.27 mL, 1.1 mmol) was heated
at 130 °C for 2.75 h. The crude product was purified by column
chromatography (50−100% CHCl3/hexanes followed by 0−5%
MeOH/CHCl3) followed by precipitation in MeOH. Filtration using
a 0.45 μm nylon membrane provided the title compound as a red
1
powder (278 mg, 42%): Rf = 0.26 (95/5 CHCl3/MeOH); H NMR
(600 MHz, THF-d8) δ 0.85 (t, J = 7.0 Hz, 6H), 1.20−1.43 (m, 16H),
1.81−1.92 (m, 2H), 2.26−2.37 (m, 2H), 5.19 (tt, J = 9.6, 5.4 Hz, 1H),
6.82−6.89 (m, 2H), 7.11−7.19 (m, 2H), 8.40−8.57 (m, 9H) ppm; 13C
NMR (125 MHz, THF-d8) δ 14.6, 23.7, 28.0, 30.4, 32.9, 33.4, 55.2,
116.2, 116.3, 124.3, 124.4, 125.1, 127.2, 127.3, 128.2, 130.4, 130.5,
130.9, 131.7, 132.2, 135.3, 135.4, 158.6, 164.0 ppm; IR (solid, cm−1)
D
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3415, 3111, 2952, 2924, 2856, 1693, 1655, 1593, 1514, 1344; HRMS
(EI, m/z) calcd for [C43H40N2O5]+ (M+), 664.2937; found, 664.2943.
N-(4-Ethoxyphenyl)-N′-(1-hexylheptyl)perylene-3,4,9,10-tetra-
carboxylic Diimide (Table 2, entry 5). Following general procedure A,
a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (409 mg,
1.04 mmol), imidazole (5.5 g, 81 mmol), 4-ethoxyaniline (0.17 mL, 1.3
mmol), and 1-hexylheptylamine (0.30 mL, 1.2 mmol) was heated at
130 °C for 2 h. The crude product was purified by column
chromatography (50−100% DCM/hexanes followed by 0−10%
EtOAc/DCM) to provide the title compound as a red solid (295
mg, 41%): Rf = 0.22 (DCM); 1H NMR (600 MHz, CD2Cl2) δ 0.84 (t,
J = 6.9 Hz, 6H), 1.18−1.39 (m, 16H), 1.47 (t, J = 6.9 Hz, 3H), 1.81−
1.90 (m, 2H), 2.19−2.29 (m, 2H), 4.13 (q, J = 6.9 Hz, 2H), 5.17 (tt, J
= 9.3, 5.8 Hz, 1H), 7.04−7.10 (m, 2H), 7.22−7.28 (m, 2H), 8.60−8.69
(m, 8H) ppm; 13C NMR (125 MHz, CDCl3) δ 14.2, 15.0, 22.7, 27.1,
29.4, 31.9, 32.5, 55.0, 63.9, 115.4, 123.1, 123.3, 123.5, 124.2, 126.4,
126.6, 127.4, 129.6, 129.6, 129.8, 131.1, 131.8, 131.9, 134.3, 135.0,
159.3, 163.5, 163.8, 164.6 ppm; IR (solid, cm−1) 3349, 3305, 3099,
2656, 2928, 2857, 1694, 1655, 1591, 1246; HRMS (EI, m/z) calcd for
[C45H44N2O5]+ (M+), 692.3250; found, 692.3251.
N-(4-Vinylphenyl)-N′-(1-hexylheptyl)perylene-3,4,9,10-tetra-
carboxylic Diimide (Table 2, entry 6). Following general procedure A,
a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (392 mg,
0.999 mmol), imidazole (4.8 g, 70 mmol), 4-aminostyrene (0.13 mL,
1.1 mmol), and 1-hexylheptylamine (0.28 mL, 1.1 mmol) was heated
at 130 °C for 2 h. The crude product was purified by column
chromatography (50−100% DCM/hexanes followed by 0−10%
EtOAc/DCM) to provide the title compound as a red solid (274
mg, 41%): Rf = 0.37 (DCM); 1H NMR (600 MHz, CDCl3) δ 0.83 (t, J
= 6.8 Hz, 6H), 1.18−1.39 (m, 16H), 1.83−1.92 (m, 2H), 2.20−2.30
(m, 2H), 5.19 (tt, J = 9.6, 5.9 Hz, 1H), 5.35 (d, J = 11.0 Hz, 1H), 5.84
(d, J = 17.6 Hz, 1H), 6.81 (dd, J = 17.6, 10.9 Hz, 1H), 7.30−7.34 (m,
2H), 7.59−7.63 (m, 2H), 8.64−8.77 (m, 8H) ppm; IR (solid, cm−1)
3345, 3309, 2924, 2856, 1773, 1732, 1697, 1655, 1592, 1341; HRMS
(EI, m/z) calcd for [C45H42N2O4]+ (M+), 674.3145; found, 674.3131.
N-(4-Oxycarbonyl)-N′-(1-hexylheptyl)perylene-3,4,9,10-tetra-
carboxylic Diimide (Table 2, entry 7). Following general procedure B,
a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (385 mg,
0.981 mmol), imidazole (4.7 g, 69 mmol), 4-aminobenzoic acid (148
mg, 1.08 mmol), 1-hexylheptylamine (0.27 mL, 1.1 mmol), and N,N-
diisopropylethylamine (0.19 mL, 1.1 mmol) was heated at 130 °C for
2.5 h. The crude product was purified by column chromatography
(50−100% DCM/hexanes followed by 0−4% AcOH/DCM) followed
by precipitation in MeOH. Filtration using a 0.45 μm nylon membrane
provided the title compound as a red powder (281 mg, 41%): Rf =
0.43 (95/5 DCM/AcOH); 1H NMR (600 MHz, THF-d8) δ 0.85 (t, J
= 6.8 Hz, 6H), 1.20−1.42 (m, 16H), 1.85−1.92 (m, 2H), 2.27−2.36
(m, 2H), 5.18 (tt, J = 9.2, 4.7 Hz, 1H), 7.54 (d, J = 7.9 Hz, 2H), 8.18
(d, J = 7.9 Hz, 2H), 8.41−8.59 (m, 8H), 11.48 (br s, 1H) ppm; IR
(solid, cm−1) 3511, 3076, 2952, 2924, 2855, 1694, 1649, 1592, 1577,
1339; HRMS (EI, m/z) calcd for [C44H40N2O6]+ (M+), 692.2886;
found, 692.2869.
mmol) was heated at 130 °C. After 2 h, 1-hexylheptylamine (0.41 mL,
1.6 mmol) was added via syringe and the reaction was continued for
another 2 h. The crude product was purified by column
chromatography (50−100% DCM/hexanes followed by 0−10%
EtOAc/DCM) to provide the title compound as a red solid (108
mg, 15%). Spectral data were the same as those reported above (Table
2, entry 8).
N-Phenyl-N′-(1-hexylheptyl)perylene-3,4,9,10-tetracarboxylic Dii-
mide (Stepwise Procedure, Method B). Following general procedure
C, a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (413 mg,
1.05 mmol), imidazole (4.1 g, 60 mmol), and 1-hexylheptylamine
(0.27 mL, 1.1 mmol) was heated at 130 °C. After 2 h, aniline (0.15
mL, 1.6 mmol) was added via syringe and the reaction was continued
for another 2 h. The crude product was purified by column
chromatography (50−100% DCM/hexanes followed by 0−10%
EtOAc/DCM) to provide the title compound as a red solid (136
mg, 20%). Spectral data were the same as those reported above (Table
2, entry 8).
N-Phenyl-1,8-naphthalimide. Following general procedure D, a
mixture of 1,8-naphthalic anhydride (218 mg, 1.10 mmol), imidazole
(4.1 g, 60 mmol), and aniline (0.12 mL, 1.3 mmol) was heated at 130
°C for 2.5 h. The crude product was purified by column
chromatography (0−60% EtOAc/hexanes) to provide the title
compound as a white solid (286 mg, 95%): Rf = 0.35 (30/70
EtOAc/hexanes); 1H NMR (600 MHz, CDCl3) δ 7.30−7.36 (m, 2H),
7.45−7.52 (m, 1H), 7.52−7.59 (m, 2H), 7.80 (t, J = 7.1 Hz, 2H), 8.28
(dd, J = 8.2, 1.2 Hz, 2H), 8.66 (dd, J = 7.2, 1.2 Hz, 2H) ppm; 13C
NMR (150 MHz, CDCl3) δ 123.0, 127.2, 128.7, 128.8, 128.8, 129.5,
131.7, 131.9, 134.4, 135.6, 164.5 ppm; IR (solid, cm−1) 3355, 3325,
3074, 1698, 1659, 1583, 1499, 1435, 1354, 1234; MS (EI, m/z) calcd
for [C18H11NO2]+ (M+), 273.08; found, 273.08.
N-(1-Hexylheptyl)-1,8-naphthalimide. Following general proce-
dure D, a mixture of 1,8-naphthalic anhydride (204 mg, 1.03 mmol),
imidazole (3.8 g, 56 mmol), and 1-hexylheptylamine (0.31 mL, 1.2
mmol) was heated at 130 °C for 3 h. The crude product was purified
by column chromatography (0−20% EtOAc/hexanes) to provide the
title compound as a slightly yellow oil (380 mg, 97%): Rf = 0.55 (15/
1
85 EtOAc/hexanes); H NMR (600 MHz, CDCl3) δ 0.81 (t, J = 7.0
Hz, 6H), 1.15−1.37 (m, 16H), 1.78−1.86 (m, 2H), 2.18−2.27 (m,
2H), 5.17 (tt, J = 9.5, 5.8 Hz, 1H), 7.75 (t, J = 7.7 Hz, 2H), 8.20 (dd, J
= 8.3, 1.2 Hz, 2H), 8.58 (m, 2H) ppm; 13C NMR (125 MHz, CDCl3)
δ 14.1, 22.7, 27.0, 29.3, 31.9, 32.5, 54.6, 122.8, 123.5, 127.0, 128.5,
130.9, 131.6, 131.7, 133.6, 164.5, 165.5 ppm; IR (DCM, cm−1) 3349,
3317, 3063, 2924, 2855, 1699, 1657, 1588, 1338, 1237; HRMS (EI, m/
z) calcd for [C25H33NO2]+ (M+), 379.2511; found, 379.2518.
ASSOCIATED CONTENT
* Supporting Information
■
S
Spectral data for all compounds and results of acid/base
experiments. This material is available free of charge via the
Internet at http://pubs.acs.org.
N-Phenyl-N′-(1-hexylheptyl)perylene-3,4,9,10-tetracarboxylic Dii-
mide (Table 2, entry 8). Following general procedure A, a mixture of
perylene-3,4,9,10-tetracarboxylic dianhydride (393 mg, 1.00 mmol),
imidazole (4.8 g, 70 mmol), aniline (0.10 mL, 1.1 mmol), and 1-
hexylheptylamine (0.28 mL, 1.1 mmol) was heated at 130 °C for 2 h.
The crude product was purified by column chromatography (50−
100% DCM/hexanes followed by 0−10% EtOAc/DCM) to provide
the title compound as a red solid (265 mg, 41%): Rf = 0.27 (DCM);
1H NMR (600 MHz, CD2Cl2) δ 0.84 (t, J = 6.9 Hz, 6H), 1.19−1.38
(m, 16H), 1.81−1.90 (m, 2H), 2.19−2.29 (m, 2H), 5.17 (tt, J = 9.3,
5.7 Hz, 1H), 7.33−7.39 (m, 2H), 7.51−7.55 (m, 1H), 7.56−7.63 (m,
2H), 8.59−8.72 (m, 8H) ppm; IR (solid, cm−1) 3341, 3305, 3101,
3063, 2923, 2855, 1771, 1696, 1653, 1342; HRMS (EI, m/z) calcd for
[C43H40N2O4]+ (M+), 648.2988; found, 648.2976.
AUTHOR INFORMATION
Corresponding Author
*E-mail: hawker@mrl.ucsb.edu.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the MRSEC program of the National Science
Foundation (Award No. DMR-1121053) and the AFOSR
MURI program (FA9550-12-1-0002) for partial financial
support. M.J.R. gratefully acknowledges UC Regents, CSP
Technologies, and the DOE Office of Science Graduate
Fellowship Program (DOE-SCGF, administered by ORISE-
ORAU under Contract No. DE−AC05−06OR23100). B.N.
thanks the RISE Internship Program provided through the
N-Phenyl-N′-(1-hexylheptyl)perylene-3,4,9,10-tetracarboxylic Dii-
mide (Stepwise Procedure, Method A). Following general procedure
C, a mixture of perylene-3,4,9,10-tetracarboxylic dianhydride (429 mg,
1.09 mmol), imidazole (3.5 g, 51 mmol), and aniline (0.10 mL, 1.1
E
dx.doi.org/10.1021/jo500945k | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
(11) (a) Shibano, Y.; Umeyama, T.; Matano, Y.; Tkachenko, N. V.;
Lemmetyinen, H.; Imahori, H. Org. Lett. 2006, 8, 4425−4428. (b) Li,
X.; Sinks, L. E.; Rybtchinski, B.; Wasielewski, M. R. J. Am. Chem. Soc.
2004, 126, 10810−10811. (c) Aigner, D.; Borisov, S. M.; Klimant, I.
Anal. Bioanal. Chem. 2011, 400, 2475−2485.
UCSB Materials Research Laboratory. B.P.F. thanks the
California NanoSystems Institute for the Elings Prize Fellow-
ship in Experimental Science. We are also grateful to Dr Javier
Read de Alaniz for helpful discussions.
(12) No reaction was observed by 1H NMR spectroscopy after
resubjecting the product to the imidization conditions in the presence
of 2-ethylhexylamine.
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