Perylene monoanhydride diester: a versatile intermediate for the synthesis of unsymmetrically substituted perylene tetracarboxylic derivatives

Article abstract of DOI:10.1016/j.tetlet.2008.11.084

A soluble perylene monoanhydride diester has been designed and synthesized. It was successfully utilized as an efficient intermediate for the synthesis of the first unsymmetric perylene tetracarboxylic tetraester and a series of unsymmetric perylene diest

Full text of DOI:10.1016/j.tetlet.2008.11.084

Tetrahedron Letters 50 (2009) 853–856
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Perylene monoanhydride diester: a versatile intermediate for the synthesis
of unsymmetrically substituted perylene tetracarboxylic derivatives
*
Chenming Xue, Runkun Sun, Rana Annab, Douha Abadi, Shi Jin
Center for Engineered Polymeric Materials and Department of Chemistry, College of Staten Island and the Graduate Center, The City University of New York Staten Island, NY
10314, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
A soluble perylene monoanhydride diester has been designed and synthesized. It was successfully uti-
lized as an efficient intermediate for the synthesis of the first unsymmetric perylene tetracarboxylic tet-
raester and a series of unsymmetric perylene diester monoimides in good to excellent yields. Its
application in synthesis of unsymmetric perylene diimides was also demonstrated. Availability of such
a versatile intermediate would enable the convenient integration of perylene tetracarboxylic tetraesters
and perylene biester monoimides into intricate functional molecular systems.
Received 22 August 2008
Revised 20 November 2008
Accepted 21 November 2008
Available online 27 November 2008
Ó 2009 Published by Elsevier Ltd.
Perylene tetracarboxylic acid-based dyes are under intense
investigations due to their promising applications. In particular,
N,N0-disubstituted perylene tetracarboxylic diimides (PDIs) have
been widely used as lightfast colorants,1 highly efficient fluoro-
phores,2 the electron acceptor in solar cells,3 the active component
in field effect transistors,4 liquid crystalline materials5, and versa-
tile building block in self-assembly.6 Structurally related tetraest-
ers of perylene tetracarboxylic acids (PTEs) were also reported as
liquid crystals,7 fluorescent dyes,2b the electron acceptor in light
harvesting systems,8 and light emitting diodes.9 Similar to PDIs,
PTEs have appreciable electron-accepting power, and are capable
voltaic materials. In order for
a
donor/acceptor organic
photovoltaic system to achieve the optimal energy conversion effi-
ciency, the electron acceptor should have an appropriate electron
affinity that matches the electron donor.20 Among three types of
perylene derivatives, PTEs are the weakest electron acceptors,
while PDIs are the most powerful ones. Thus, being able to use
PTEs or PEIs to replace the PDIs in photovoltaic systems provides
a unique way to tune the electron-accepting power of the acceptor
for the best possible conversion efficiency, in addition to the sub-
stantially improved solubility in common organic solvents. This
calls for the capacity to access unsymmetrically substituted PTEs
and PEIs. Herein, we report the design and synthesis of perylene
tetracarboxylic monoanhydride diester 1. It can serve as a versatile
intermediate for the synthesis of unsymmetric PTEs and PEIs, as
well as PDIs.
of forming perylene
p
-stacks in both solutions10 and the solid
state.11 Recently, perylene tetracarboxylic diester monoimides
(PEIs), where an imide and two ester groups connect to the same
perylene core, have also attracted considerable attention as more
soluble alternatives to PDIs.12 Nevertheless, comparing with PDIs,
the scope of applications of PTEs and PEIs is rather limited. Reports
on PTEs are limited to symmetrically substituted tetraesters,
whereas PEIs have been explored only in the form of simple alkyl
derivatives recently. In contrast, besides simple symmetrically
substituted derivatives, PDIs have also been extensively incorpo-
rated into complex molecular and supramolecular architec-
Compound 1 is intrinsically unsymmetric. The reactivity differ-
ence between the anhydride and the ester groups is great enough
for a nucleophile to selectively attack the anhydride group. Two
flexible decyl groups provide the necessary solubility in organic
solvents, which facilitates purification and characterization.
O
O
O
O
O
O
tures.13–18 This is probably because there are
a number of
RO
RO
RO
RO
OR
OR
methods by which unsymmetrically substituted PDIs can be read-
ily accessed.19 Contrarily, systematic synthetic strategies for PEIs
have not been well developed, and there are no reports on unsym-
metrically substituted PTEs. From a materials scientist’s point of
view, it is important to be able to integrate PTEs and PEIs into more
structurally intricate systems, especially those with light harvest-
ing capabilities, considering the surging interest in organic photo-
O
O
O
1
2
R = decyl
It was envisioned that 1 could be prepared from a symmetri-
cally tetrasubstituted PTE 2 via either basic or acidic hydrolysis.
The acid-catalyzed route is chosen because of its potential high
yield as depicted in Scheme 1A. First, an acid-catalyzed hydrolysis
reaction is a reversible reaction. Therefore, even if the initial ester
bond cleavages did not occur at the ‘right’ positions, they could be
* Corresponding author. Tel.: +1 718 982 3890; fax: +1 718 982 3910.
E-mail address: jin@mail.csi (S. Jin).
0040-4039/$ - see front matter Ó 2009 Published by Elsevier Ltd.
doi:10.1016/j.tetlet.2008.11.084

854
C. Xue et al. / Tetrahedron Letters 50 (2009) 853–856
Table 1
O
O
Condensation of 1 with amines
RO
RO
OH
OH
+ ROH
O
O
O
R'N
O
O(CH2)9CH3
O(CH2)9CH3
O
O
O
O
imidazole
heat
A
B
+
H2O
2
1
1 + R'NH2
RO
HO
OH
OR
+ ROH
Entry R0NH2
Reaction
condition
Product (% yield)
O
O
O
O
.
O
N
O
TsOH H2O
2
1
OR
OR
n
-dodecane/tolene (5/1)
NH2
95 °C, 5 h
1
2
120 °C, 3 h
R = decyl
(3a, 99%)
Scheme 1.
O
O
HN
O
‘‘corrected” through the esterification-hydrolysis equilibrium. Sec-
ond, at a relative high temperature (typically >90 °C), a unimolec-
ular cyclization reaction occurs rapidly giving a six-membered
cyclic anhydride once two carboxyl groups formed from a 2 mole-
cule are at the ‘correct’ positions. This removes 1 out of the ester-
ification-hydrolysis equilibrium and contributes to a high yield. To
obtain the highest possible yield, further hydrolysis of the ester
groups in 1 must also be avoided. One approach is to use a solvent
that dissolves 2 well but hardly dissolves 1 at the reaction temper-
ature. In this way, 1 may precipitate from the solution upon its for-
mation, which slows down the further cleavage of the ester groups
in 1. It has been found that a mixture of n-dodecane and toluene
(5:1 v/v) is well suitable for this purpose. Finally, reaction time
must also be controlled to maximize the yield of 1. The optimized
reaction condition is given in Scheme 1B. A high concentration
(ꢀ0.62 M) of 2 and 1 equiv of p-toluenesulfonic acid monohydrate
(TsOHꢁH2O, serving as the acid catalyst and the water source) re-
acted at 95 °C for 5 h giving 1 in a satisfactory (74%) isolated yield.
Compound 2 was prepared in an excellent yield (97%) according to
a slightly modified literature procedure.21
OR
OR
Ammonium
decanoate
120 °C, 1 h
O
(3b, 88%)
O
O
O
N
O
OR
OR
HO
3
4
130 °C, 3 h,
H2N
OH
DMAP
(3c, 85%)
O
O
O
N
O
HO
HO
OR
OR
OH
130 °C,
H2N
OH
1.5 h
(3d, 79%)
R = decyl.
The identity of 1 has been confirmed by 1H NMR, FT-IR, HRMS,
and UV (see Supplementary data). 1 dissolves in various common
organic solvents such as chloroform, dichloromethane, toluene,
acetone, THF, and pyridine. Although its room temperature solubil-
ity in most solvents (except chloroform) is low (ꢀ10ꢂ4 M), the
solubility increases substantially in warm or hot solvents. In mol-
ten imidazole, a widely used solvent for imidization reactions of
perylene anhydrides, 1 dissolves considerably at 100 °C affording
a bright red solution at about 10ꢂ2 M concentration. This implies
that the condensation of 1 with primary amines will be smoother
than that of perylene tetracarboxylic dianhydride which is insolu-
ble in any organic solvents.
To demonstrate the applicability of 1 for the synthesis of unsym-
metric PEIs, it was condensed with four amines as shown in Table 1.
Four new PEIs were obtained in good to excellent yields, which con-
firms the suitability of 1 as a precursor of unsymmetric PEIs. It is
worth mentioning that a large excess of amine is not necessary to
achieve a high yield. This is practically important especially when
the primary amine must be prepared by a multi-step synthesis.
When a less reactive amine (entry 3) is used, the reaction can be
significantly accelerated by adding 4-dimethyl-aminopyridine
(DMAP) (Supplementary data). The use of DMAP as the general acyl-
ation catalyst is well documented. However, to the best of our
knowledge, it has not been applied to the reactions involving pery-
lene anhydrides. Probably, this is because the low solubility of
perylene tetracarboxylic dianhydride was the major limiting factor
for most of such reactions. For 1, such a solubility limitation is lifted
so that the nucleophilic attack to carbonyl may become the rate-lim-
iting step which can be catalyzed by DMAP.
the successful installation of substituents at imide nitrogen atom
of 3b. Due to the mild acidity of the imide proton, nucleophilic sub-
stitution reactions of 3b can be carried out after deprotonation.
However, in many cases, the Mitsunobu reaction with an alcohol
is preferred as alcohols are often more readily available than their
halide/sulfonate or amine counterparts. Two such reactions are
presented in Scheme 2 with good yields.
In addition to serving as the less electron deficient, more soluble
alternatives to PDIs, PEIs can also be converted to perylene tetra-
carboxylic monoimide monoanhydrides which are the precursors
of unsymmetric PDIs. The ester groups in a PEI are less stable than
the six-membered cyclic imide group, and thus can be selectively
cleaved under either acidic or basic conditions. The feasibility of
O
O
O
N
O
O(CH2)9CH3
O(CH2)9CH3
THF
R
ROH + Ph3P + DIAD + 3b
RT, 7 days
ROH =
OH , 3e, 76.2%
, 3f, 79.3%
H3C(H2C)17
H3C(H2C)17
H3C(H2C)17
O
O
O
OH
DIAD: diisopropyl azodicarboxylate
PEIs 3b, 3c, and 3d can serve as reactive intermediates that can
be readily integrated into a larger structure. This is illustrated by
Scheme 2.

C. Xue et al. / Tetrahedron Letters 50 (2009) 853–856
855
O
O
.
O
N
O
O
O
O
O
N
O
TsOH H2O
toluene
OR
OR
100 °C, 2h
H3C(H2C)9
H3C(H2C)9
H3C(H2C)9
H3C(H2C)9
93.2%
4
Scheme 3.
O
O
O
1. [PhCH2N(CH3)3]+OH-
THF, 50°C, 10 h
H3C(H2C)9O
H3C(H2C)9O
O(CH2CH2O)3CH3
O(CH2CH2O)3CH3
CH3(OCH2CH2)3OH
+
1
2. CH3(OCH2CH2)3OTs
CH3CN, 50°C, 10 h
O
5
Scheme 4.
further converted to unsymmetric PDIs. The ability to access
unsymmetric PEIs, PTEs, and PDIs would enable molecular engi-
neering of complex organic functional systems having the electron
acceptor with tuneable electron affinity, which may lead to the
optimum optoelectronic performance.
Table 2
The first reduction potentials of perylene tetracarboxylic derivatives versus Fc/Fc+
Compound
E1 (V)
Compound
E1 (V)
1
2
4
5
6
ꢂ1.162
ꢂ1.589
ꢂ0.988
ꢂ1.568
ꢂ1.044
3a
3b
3c
3d
3e
3f
ꢂ1.311
ꢂ1.256
ꢂ1.255
ꢂ1.214
ꢂ1.333
ꢂ1.284
Acknowledgments
This research was financially supported by the 3M Non-tenured
Faculty grant and Petroleum Research Foundation. Partial support
from PSC-CUNY Research Award Program is also gratefully
acknowledged.
this transformation is supported by the high-yield reaction shown
in Scheme 3.
Supplementary data
Another unique application of 1 is that it can act as the precur-
sor of unsymmetric PTEs. The availability of 1 made it possible to
synthesize the first unsymmetrically substituted PTE 5, as outlined
in Scheme 4. The good overall yield (80%) signifies the effectiveness
of 1 as the precursor of unsymmetric PTEs.
Supplementary data (detailed experimental procedures, spec-
troscopic data and NMR spectra of final products) associated with
this article can be found, in the online version, at doi:10.1016/
j.tetlet.2008.11.084.
Finally, electron-accepting powers of different perylene tetra-
carboxylic acid derivatives were examined electrochemically. Their
first reduction potential values are listed in Table 2. For the pur-
pose of comparison, the first reduction potential of PDI 65d with
the structure shown below was also measured. As expected, the
perylene monoimide monoanhydride 4 is more electron deficient
than 6, as the anhydride group is more electron withdrawing than
the imide group. For the same reason, the electron affinity of 1 is
greater than that of PEIs. The two PTEs, 2 and 5, are the least elec-
tron-deficient materials due to four least electron-withdrawing
ester groups. As expected, six PEIs exhibit intermediate electron
affinity between the PTEs and PDI 6. It is quite interesting to ob-
serve that the difference in first reduction potential values among
PEIs is as great as 0.119 V. Evidently, the availability of unsymmet-
ric PEIs and PTEs as PDI alternatives will allow one to tune the
acceptor electron affinity to a considerable degree, which may help
minimize the energy loss during the electron transfer from the
donor to the acceptor in an organic photovoltaic system.20
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