Synthesis of donor-σ-perylenebisimide-acceptor molecules having PEG swallowtails and sulfur anchors

Article abstract of DOI:10.1021/jo301701a

Donor-σ-Acceptor (D-σ-A) molecules, arrayed in a monolayer between electrodes, can serve as molecular rectifiers. Using perylene-3,4,9,10-tetracarboxylic bisimide (PBI) as the acceptor allows the attachment of the donor group to one imide nitrogen and a solubilizing swallowtail, normally a long (e.g., C₁₉) alkane connected at midchain, on the other. Such an alkyl tail facilitates the formation of Langmuir-Blodgett (LB) monolayers. We have employed several modified swallowtails to make new D-σ-A molecules: poly(ethylene glycol) (PEG) swallowtails with 6 ether oxygens or with 4 ether oxygens to promote hydrophilicity in orienting LB monolayers, and alkyl swallowtails ending with sulfur anchors (thioacetate, thiol, or methyl disulfide) to stabilize attachment of the D-σ-A molecules to gold electrodes. The preparation and characterization of D-σ-A molecules containing combinations of these swallowtails with pyrene, ferrocene, and tetramethylphenylenediamine donor groups is described.

Full text of DOI:10.1021/jo301701a

Article
pubs.acs.org/joc
Synthesis of Donor-σ-Perylenebisimide-Acceptor Molecules Having
PEG Swallowtails and Sulfur Anchors
Rajesh Kota, Ramakrishna Samudrala, and Daniell Lewis Mattern*
Department of Chemistry and Biochemistry, University of Mississippi, P.O. Box 1848, University, Mississippi 38677, United States
S
* Supporting Information
ABSTRACT: Donor-σ-Acceptor (D-σ-A) molecules, arrayed in a monolayer between electrodes, can serve as molecular
rectifiers. Using perylene-3,4,9,10-tetracarboxylic bisimide (PBI) as the acceptor allows the attachment of the donor group to one
imide nitrogen and a solubilizing swallowtail, normally a long (e.g., C19) alkane connected at midchain, on the other. Such an
alkyl tail facilitates the formation of Langmuir−Blodgett (LB) monolayers. We have employed several modified swallowtails to
make new D-σ-A molecules: poly(ethylene glycol) (PEG) swallowtails with 6 ether oxygens or with 4 ether oxygens to promote
hydrophilicity in orienting LB monolayers, and alkyl swallowtails ending with sulfur anchors (thioacetate, thiol, or methyl
disulfide) to stabilize attachment of the D-σ-A molecules to gold electrodes. The preparation and characterization of D-σ-A
molecules containing combinations of these swallowtails with pyrene, ferrocene, and tetramethylphenylenediamine donor groups
is described.
Chart 1. D-σ-A Molecules 1a−4a with a C19 Alkyl Swallowtail
INTRODUCTION
■
Rectification (the unidirectional flow of current) through a
Donor-σ-Acceptor (D-σ-A) molecule, where D is an electron-
donating group, A is an electron-accepting group, and σ is a
separating bridge of several bonds,1−3 was first proposed by
Aviram and Ratner in 1974.4 Such organic molecular rectifiers
have attracted attention as possible components of nanocircuits
that could replace present-day silicon-based semiconductor
devices.5
In the past quarter century, both experimental6−8 and
theoretical9,10 studies have described rectifying behavior of D-σ-
A molecules. To measure current through a potential D-σ-A
rectifier, it is convenient to assemble a monolayer of the
molecules and interrogate a collection of the monolayer
molecules aligned in parallel. Monolayers may be formed by
Langmuir−Blodgett (LB)6,11−13 or self-assembled monolayer
(SAM)14−18 techniques. LB monolayers form when molecules
organize themselves on the surface of an aqueous/air interface.
To obtain a well-ordered LB monolayer, suitable for lifting onto
a bottom electrode for electrical studies, an alkyl tail typically is
attached to one end of the D-σ-A molecule to give it a
hydrophobic end that will prefer to be in the air.1 In contrast,
formation of a SAM typically involves attaching a sulfur anchor
to one end of the D-σ-A molecule, so that it will coordinate to
the bottom Au electrode. The top electrode can be a scanning
probe or can be created by evaporative metal techniques.5
We have previously described the synthesis (1a−4a, Chart
1)1 and LB film formation and monolayer electrical properties
(1a−3a)6 of several D-σ-A molecules based on perylene-
3,4,9,10-tetracarboxylic bisimide (PBI) as the acceptor. In order
to provide adequate solubility and the required hydrophobic
alkyl tail for LB film formation, a “swallowtail”, a long alkyl
chain connected at its center,1,19 is attached to one imide end.
(The letter a designates the C19 alkyl swallowtail shown; other
letters will designate different swallowtail targets.) The other
imide end holds the σ bridge to the donor group: pyrene (1a,
2a), ferrocene (3a), or tetramethylphenylenediamine (4a). A
Received: August 13, 2012
Published: October 10, 2012
© 2012 American Chemical Society
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well-packed LB film is not formed from 2a, but LB monolayers
of 1a and 3a, arranged between two electrodes in a “Au|D-σ-A|
Au” sandwich, rectify electric current; 3a has a rectification ratio
between 14 and 28 at 1 V.6
In 1a−4a, the donor end can be considered more polar than
the C19 alkyl swallowtail end (even in the case of the donor
pyrene, which is not particularly polar). It is therefore assumed
that the donor end will prefer the aqueous subphase of the LB
trough and will comprise the bottom of the monolayer, while
the swallowtail end will be in air and comprise the top face
(Figure 1a).1 To have control of the direction of electron
putative molecular flipping by coordinating the sulfur anchors
to the gold electrode (Figure 1b). Thiol anchors have a strong,
specific affinity toward gold17,18 and form good SAMs, but the
-SH group tends to be unstable, so thiols are often protected as
thioesters (e.g., S-acetyl25a) or cyanoethyl thioethers25b and
deprotected just before use. This strategy has been used to
stabilize rectifying layers of a D-π-A molecule with an SAc
anchor at the end of single alkyl tails of different lengths.26a,b S-
Acetyl anchors themselves are capable of generating SAMs on
gold, but the assembly process is slow and the properties of the
resulting films differ from those of thiol-derived SAMs.26c High-
quality SAMs can be formed from disulfides, but if these are
unsymmetrical (e.g., RS-SCH3), the coverage will differ from
SAMs made from the corresponding thiols (RSH) or
thioacetates (RSAc). Since SAMs to gold can be formed from
all three of the above-mentioned sulfur groups, they are
potential anchors for our D-σ-A molecules.
Here we report the synthesis of several D-σ-A molecules with
PEG swallowtails, intended to reverse the orientation of the
monolayers respective to the monolayers of molecules 1a−4a
and thereby reverse the direction of rectification, and D-σ-A
molecules with sulfur anchors at the ends of alkyl swallowtails,
to stabilize Au|D-σ-A|Au assemblies and sustain their
rectification ratios, as well as making D-σ-A molecules capable
of SAM formation. The formation and properties of
monolayers made from these molecules and the investigation
of their electrical properties will be described elsewhere.
RESULTS AND DISCUSSION
Unsymmetrical PBIs (8) are prepared from commercially
available perylenetetracarboxylic bisanhydride 5 (Scheme 1). In
Figure 1. (a) Proposed orientation of swallowtailed D-σ-A molecules
on an LB trough. (b) Stabilization with sulfur anchors of swallowtailed
D-σ-A molecules in one of the two possible orientations.
■
Scheme 1. General Procedure To Make Unsymmetrical PBIs
8
transport across the monolayer, we wanted to be able to reverse
the orientation of the LB film by changing the polarity of the
swallowtail. Swallowtails with hydrophilic poly(ethylene glycol)
(PEG) arms instead of alkyl arms would be more hydrophilic
than the donors and might thereby reverse the film’s
orientation and its direction of rectification (Figure 1a).
Fullerenes decorated with a PEG hemisphere20a and diblock
copolymers with a PEG block20b can be oriented into Langmuir
films in this way. In addition, PEG ether oxygens would provide
a less-insulating layer compared to the hydrocarbon swallow-
tails, and this might allow for a greater tunneling current
through the monolayer.
PEG tails are widely used to improve solubility,21 and like
alkyl swallowtails, various PEG tails have been used to improve
the solubility of perylenebisimides.22 PEG tails can impart
liquid crystalline characteristics to PBI compounds,23 which
improve π−π stacking, allowing dynamic reorganization and
easier processing. Cormier and Gregg23 reported liquid-
crystalline PBIs with branched propylimide-oligo(oxyethylene)
or phenethylimide-oligo(oxyethylene) side chains, while
Murray et al.24 synthesized PBIs with short poly(ethylene
oxide) tails. We planned to use a PEG swallowtail
corresponding to the skeleton of the C19 alkyl swallowtail.
We are also interested in stabilizing the monolayers after
their assembly into Au|D-σ-A|Au sandwiches. For example, the
rectification ratios of 1a and 3a decrease on repeated voltage
cycling, a phenomenon that is frequently seen in such systems.5
A possible explanation for this attenuation is that molecules
within the monolayer may flip their orientation in response to
the cycling electric field. The incorporation of sulfur anchor
groups at the ends of the swallowtail arms would inhibit the
principle, one anhydride group of 5 could condense with a
primary amine, R-NH2, to make the monoimide monoanhy-
dride 7, followed by condensation of the other anhydride group
with a second amine, R′-NH2, to make 8. In practice, the first
condensation under typical conditions (e.g., molten imidazole
and Zn(OAc)2) usually affords only symmetrical bisimide
6,1,27,28 which is nicely soluble if R-NH2 is a swallowtail. This
bisimide is then semihydrolyzed to the imide anhydride 7
before introduction of the second amine,1,29 which in our
system adds the donor group. The preparation of appropriate
swallowtail amines, R-NH2, was therefore the first step in
making the intermediates 7 required for the synthesis of the D-
σ-A targets.
Swallowtail Amines (13). The PEG swallowtail amine 13b
(Scheme 2) was prepared by double Williamson alkylation of
N,N-dibenzyl-protected serinol 10 with diethylene glycol
monomethyl ether tosylate 11, followed by hydrogenolysis of
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Scheme 2. Synthesis of PEG Swallowtail Imide Anhydride 7b
Scheme 3. Synthesis of Mixed-PEG Swallowtail Imide
Anhydride 7c
concern, however, since LiAlH437 in refluxing THF reduced the
N-alkoxy group to the desired primary amine 13c.
Our first attempt to obtain alkyl swallowtails with sulfur
anchors was via transformation of terminal hydroxyl groups
(Scheme 4). 11-Bromoundecanoic acid (21) was esterified and
then underwent TiCl4-catalyzed Claisen condensation38 and
decarboxylation to make the known dibromoketone 23.
Attempts to make the oxime of 23 were unsuccessful,
presumably because of side reaction at the bromines, so the
bromines were converted to hydroxyls by acetate substitution
and methanolysis, yielding the dihydroxyketone 24. In contrast
to 17, the intramolecular ketal is not favored in this larger
system. Reductive amination of 24 gave the desired amine 13d.
This amine was converted to its imide anhydride 7d via the
bisimide 6d before introduction of the thioacetate group (see
below).
We also pursued an alternative route to obtain alkyl
swallowtails with sulfur anchors that involved a swallowtail
amine with terminal vinyl groups, 13h (Scheme 5). 11-
Undecenoic acid (25) underwent esterification, followed by
Claisen condensation as before to give the divinyl ketone 2738
and then reductive amination to give 13h. Again, introduction
of the sulfur groups was delayed (see below) until after
formation of the corresponding imide anhydride 7h, prepared
via the bisimide 6h.
Perylenetetracarboxylic Monoimide Monoanhydrides
(7). The general approach for making imide anhydrides
outlined in Scheme 1 worked well for amines 13c, 13d, and
13h. They condensed with bisanhydride 5 to make symmetrical
bisimides 6c, 6d, and 6h, followed by semihydrolysis1,29,40 to
the monoimide monoanhydrides 7c, 7d, and 7h, as shown in
Schemes 3, 4, and 5, respectively. In the case of 13d, the
standard conditions for making the bisimide were too harsh,
but lowering the reaction temperature from 160° to 130°
resulted in a satisfactory yield of 6d.
the benzyl groups of the protected PEG amine 12, as described
previously.21 We had converted 13b to the symmetrical, water-
soluble PBI 6b as shown in Scheme 2; the water solubility of 6b
supported the idea that a single PEG swallowtail in a PBI would
be hydrophilic enough to seek the water side of an LB
monolayer. However, the troublesome solubility profile of the
crucial imide anhydride 7b prepared from 13b (see below)
prompted us to attempt an alternative, a “hybrid” swallowtail,
13c, that ended in a PEG segment for hydrophilicity in an LB
film but had alkyl character near to the imide nitrogen to
promote better solubility in organic solvents (Scheme 3). We
anticipated making amine 13c from dihydroxyketone 16, the
product of a Claisen condensation of δ-valerolactone 15. This
condensation, however, is known to give only the spiroketal 17
(a pheromone of the female olive fly).30 Ketal 17 is a
thermodynamic sink for 16, and various attempts to make 16
invariably produce 17 instead.31−36 No reactions have been
reported for 17; this is attributed to its stable nature. We
adopted Baker’s procedure30 for synthesizing 17 using a one-
step Claisen condensation of 15, and we then succeeded in
converting 17 to its oxime 18 in good yield, essentially
capturing 17 as it equilibrated with an open-chain form.
Williamson alkylation of the hydroxyls of 18 with methoxyethyl
tosylate 19 was accompanied by oxime alkylation, giving the
triple-alkylated 20. Alkylation of the oxime hydroxyl was not a
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Scheme 4. Synthesis of Sulfur-Anchored, Alkyl-Swallowtailed Imide Anhydrides 7e, 7f, and 7g
Scheme 5. Alternate Synthesis of Thioacetate-Anchored, Alkyl-Swallowtailed Imide Anhydride 7e
The swallowtails of 6d and 6h closely resemble alkyl
swallowtails, differing only in the presence of hydroxyl (6d)
or vinyl (6h) groups at the distal ends of the swallowtail arms.
A modification of the procedure was needed to prepare
intermediate 7c (Scheme 3), in which the swallowtail is PEG-
like for the five distal skeletal atoms of each arm, but alkyl for
the four skeletal atoms of each arm closest to the
perylenebisimide. The standard semihydrolysis conditions of
KOH in t-BuOH were unsuccessful with 6c, because the
reaction was too fast and both imides were hydrolyzed. A
change of solvent to ethanol, however, gave a satisfactory yield
(62%) of 7c. As hoped for, monoimide monoanhydride 7c, in
contrast to PEG analogue 7b, was soluble in organic solvents,
and hence we could easily verify its structure using NMR.
Difficulties arose when we attempted to prepare the
monoimide monoanhydride containing a full PEG swallowtail
(7b) by the standard method. The PEG-amine 13b converted
easily to PBI 6b (Scheme 2). However, in contrast to the alkyl-
like monoimide monoanhydrides 7c, 7d, and 7h, which had
been soluble in organic solvents and therefore easily isolated
following semihydrolysis, 7b was insoluble in common organic
solvents, complicating its purification. We were unable to
isolate adequate amounts of 7b by this method and therefore
turned to alternate methods.
In our hands, Troster’s method41 of making imide
̈
anhydrides directly from the monoanhydride monopotassium
salt (14) of 5 was not successful with the PEG amine 13b
(Scheme 2). The crude reaction mixture failed to show
anhydride carbonyl peaks in the infrared spectrum. (We also
tried Troster’s salt 14 with the dihydroxyalkyl swallowtail amine
̈
13d but obtained an intractable polar product.) Pasaogullari
and Demuth’s modified procedure42 employing Troster’s salt41
̈
also failed in preparing 7b.
Nagao and Misono’s method (lengthy refluxing of 5 with a
primary amine in a H2O/PrOH/Et3N mixture43) was able to
convert PEG amine 13b into imide anhydride 7b (Scheme 2).
However, compound 7b was not soluble in common organic
solvents, although it was soluble in basic solvents such as
morpholine, pyridine, and diethylamine. Due to its poor
solubility, it was difficult to verify its purity following
purification attempts by column chromatography; consistent
with the thermal instability of PEGs,44 sublimation was also
unsuccessful. Crude 7b was therefore used to carry the
synthesis forward. The Nagao−Misono method is generally
less useful for large alkyl swallowtails, presumably because of
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their poor solubility in the polar solvents, but we thought the
half-PEG, water-soluble amine 13c might be a worthy substrate.
However, only trace amounts of monoimide monoanhydride 7c
were obtained with this method (Scheme 3).
Scheme 6. Formation of Unsymmetrical PBI D-σ-A Targets
Introduction of Sulfur End Groups into Swallowtailed
Monoimide Monoanhydrides. With the hydroxyl-tipped
alkyl-swallowtailed imide anhydride 7d, tosylation and displace-
ment with thioacetate afforded the thioacetate-tipped 7e
(Scheme 4). This compound could also be obtained from the
vinyl-tipped imide anhydride 7h by a double radical-chain
addition of thioacetic acid45 to the terminal double bonds
(Scheme 5), a reaction that required dry solvents and an inert
atmosphere to obtain good yields. The route to thioacetyl-
tipped 7e was shorter via the divinyl swallowtail 13h compared
to the diol 13d, and the overall yield from starting C11 acid was
much better for the divinyl route (21%) compared to the diol
route (2%).
The bisthioacetate imide anhydride 7e was converted to the
dithiol imide anhydride 7f by treatment with acetyl chloride in
MeOH,46 which provided an acidic environment that promoted
methanolysis (Scheme 4). In turn, the dithiol 7f was converted
to the bis(methyldisulfide) 7g by treatment with methyl
methanethiosulfonate.47
Conversion of Monoimide Monoanhydrides 7 to
Unsymmetrical Bisimides. The condensation of perylene
monoimide monoanhydrides 7 with donor amines pyrenyl-
methyl (1-NH2), pyrenylbutyl (2-NH2), ferrocenylethyl (3-
NH2), or TMPDA-propyl (4-NH2) to make unsymmetrical
bisimides was straightforward (Scheme 6). Target D-σ-A
molecules 1b, 2b, 3b, and 4b, with the full PEG swallowtail,
were made by refluxing crude PEG imide anhydride 7b and the
appropriate donor amine in pyridine overnight. In contrast to
the precursor imide anhydride 7b, all of these PBI targets were
soluble in chloroform, and recrystallization (CHCl3/hexane)
followed by column chromatography (99:1 CHCl3/MeOH)
resulted in pure products. Target D-σ-A molecules 1c, 2c, 3c,
and 4c with mixed alkyl-PEG swallowtails were made by
refluxing crude imide anhydride 7c with the appropriate donor
amine in toluene. Target D-σ-A molecules 1e, 2e, 3e, and 4e,
containing thioacetate-anchored alkyl swallowtails, were made
by refluxing crude imide anhydride 7e with the appropriate
donor amine in toluene; in the case of the reaction of 4-NH2,
slow addition of the amine was required to suppress side
reaction of the thioacetates. We decided to utilize the other
two, less widely used sulfur anchor groups, thiol f and disulfide
g, with two of the donors, 1-NH2 and 3-NH2. Condensation of
imide anhydrides 7f and 7g with these amines gave targets 1f,
1g, 3f, and 3g.
Attempted Direct Condensation to Unsymmetrical
Bisimides. Although the final condensations shown in Scheme
6 were straightforward, the yields were disappointing (around
20%) for the PEG and mixed-PEG swallowtails b and c,
compared to the alkyl swallowtails e, f, and g (around 80%).
We therefore attempted an alternative “direct” condensation by
treating the bisanhydride 5 with PEG swallowtail amine 13b
combined with either 1-NH2 or 3-NH2. Such attempts to avoid
the isolation of the monoimide monoanhydride intermediate
are usually not very successful:32 even if both amines have
similar reactivity, there will be two symmetrical bisimide
products along with the desired crossed product, and these will
be difficult to separate. However, if only one of the amines is a
swallowtail, the separation problem may simplify since the
swallowtail may impart unusual solubility to bisimides
containing it;14 in this case, the direct procedure is much
simpler and shorter than the conventional route of Scheme 1.
In the event, treatment of 5 with 5- to 10-fold excesses of both
donor amine and 13b in either hot pyridine or imidazole for 1.5
d resulted in crude products from which no color was
extractable into CHCl3. Since the target PBIs are deep red
and soluble, the procedure was unsuccessful.
Carbonyl 13C Peaks. For PBIs with alkyl swallowtails (e.g.,
1a−4a), slow rotation about the N−CH bond, along with a
preferred conformation that places the CH bond in the plane of
the carbonyls, makes the two carbonyls nonequivalent on the
NMR time scale. This gives rise to two weak carbonyl peaks in
the 13C NMR spectrum.1 We observed similar nonequivalence
in the symmetrical PBIs that had alkyl tails tipped with hydroxyl
(6d) and vinyl (6h) groups and in imide anhydrides containing
those swallowtails (7d, 7h) or alkyl swallowtails tipped with
sulfur-containing groups (7e, 7f, 7g). Changing to a PEG
swallowtail apparently increases the rotation rate about the N−
CH bond, since only one signal was observed for the
swallowtail carbonyls in the bisimides 6b21 and 1b−4b. In
agreement, MM2 calculations of a model swallowtail with
oxygens γ to the N predicted a rotation barrier of 8.5 kcal/mol,
lower than the prediction for an alkyl swallowtail of 11.8 kcal/
mol.1 The hybrid alkyl-PEG swallowtail would be expected to
be dominated by its alkyl portion, and the symmetrical bisimide
6c indeed showed two carbonyl peaks. The results were not so
clear-cut for the imide anhydride 7c and the unsymmetrical
bisimides 1c−4c. One weak carbonyl peak could be one of a
pair, with the second peak coincident with a larger carbonyl
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ether fractions were concentrated by rotary evaporation to give 5.12 g
(71%) of a yellowish liquid, Rf (EtOAc) 0.47. H NMR (300 MHz,
peak from the other end of the molecule. Interestingly, this
same situation was observed in unsymmetrical bisimides with
sulfur-tipped swallowtails (1e−4e, 1g, 3g), in which the nature
of the swallowtail is clearly alkyl.
1
CDCl3) δ 7.39 (m, 4H), 7.28 (m, 4H), 7.20 (m, 2H), 3.78 (s, 4H),
3.55 (m, 20H), 3.37 (s, 6H), 3.10 (m, 1H). 13C NMR (75 MHz,
CDCl3) δ 140.8, 128.7, 128.1, 126.7, 72.0, 70.7, 70.6, 70.5, 70.4, 59.0,
56.2, 55.2. NMR spectra are in agreement with the literature.21
2,5,8,12,15,18-Hexaoxa-10-nonadecanamine (13b). The
N,N-dibenzyl PEG-amine 12 (4.00 g, 8.41 mmol) was dissolved in
110 mL of MeOH, and 2.5 g of 10% Pd/C catalyst was added. The
mixture was hydrogenated overnight in a Parr shaker at 55 psi of H2.
The reaction mixture was then filtered, and the solvent was removed
under reduced pressure to give 2.0 g (81%) of an oil, Rf (72:18:10
CONCLUSIONS
■
We report here the synthesis of 16 new D-σ-A molecules,
combining the PBI acceptor with three different donor groups
(with two different tether lengths for the pyrene donor) and
five different swallowtails. We tried several approaches for
constructing the required unsymmetrical perylene bisimide
architecture, and it is interesting that the approaches gave such
1
CH2Cl2/NH2OH(aq)/MeOH) 0.51. H NMR (300 MHz, CDCl3) δ
3.60 (m, 12H), 3.51 (m, 6H), 3.35 (m, 8H), 3.17 (m, 1H), 2.04 (s,
2H). 13C NMR (75 MHz, CDCl3) δ 72.0, 71.9, 70.6, 70.56, 70.51,
70.4, 59.1. IR (thin film) 3522, 3364, 3290, 2891 cm −1. NMR and IR
are in agreement with the literature.21
varied results. The Troster salt and direct condensation
̈
approaches, useful in some systems, were completely
unsuccessful here. The familiar semihydrolysis of PBIs 6 to
imide anhydrides 7 shown in Scheme 1 was the preferred route
for alkyl-like swallowtails, including the mixed alkyl-PEG 13c.
In contrast, the full PEG swallowtail amine 13b was best
managed with the basic equilibration method of Nagao and
Misono.
N,N′-Di[10-(2,5,8,12,15,18-hexaoxanonadecyl)]perylene-
3,4,9,10-bis(dicarboximide) (6b). PEG amine 13b (212 mg, 0.71
mmol), dianhydride 5 (128 mg, 0.32 mmol), imidazole (2.62 g), and
Zn(OAc)2 (catalytic amount) were heated at 165 °C overnight. The
reaction mixture solidified upon cooling and was dissolved in MeOH,
then run through a Sephadex column to obtain 75 mg (22%) of deep-
1
red waxy solid, Rf (2:1 MeOH/EtOAc) 0.70. H NMR (300 MHz,
EXPERIMENTAL SECTION
CDCl3) δ 8.63 (m, 4H), 8.58 (m, 4H), 5.72 (m, 2H), 4.19 (m, 4H),
3.99 (m, 4H), 3.72 (m, 4H), 3.61 (m, 12H), 3.56 (m, 8H), 3.42 (m,
8H), 3.28 (s, 12H). 13C NMR (75 MHz, CDCl3) δ 164.0, 134.6,
131.7, 129.7, 126.4, 123.6, 123.2, 72.0, 70.63, 70.62, 70.5, 69.4, 59.1,
52.2. IR (KBr) 1700 (CO), 1654 (CO) cm−1. NMR and IR are in
agreement with the literature.21
N-[10-(2,5,8,12,15,18-Hexaoxanonadecyl)]-3,4,9,10-peryle-
netetracarboxylic Acid 3,4-Anhydride 9,10-Imide (7b). To a
mixture of perylenedianhydride 5 (498 mg, 1.27 mmol) and the PEG
swallowtail amine 13b (372 mg, 1.25 mmol) in 40 mL of propanol and
water (1:1) was added triethylamine (1.68 g, 16.6 mmol), and the
reaction was heated for 15 d at 120 °C. The reaction mixture was
treated with excess 5% HCl at 120 °C for 10 min, cooled to room
temperature, filtered, and dried to give 0.70 g (82%) of the perylene
imide anhydride 7b as a waxy solid. Due to limited solubility, crude
material was carried further (see below), and no NMR data was
collected. IR (KBr) 1768 (s) (anhydride CO), 1733 (m) (anhydride
CO), 1693 (s) (imide CO), 1648 (s) (imide CO) cm−1.
HRMS (TOF MS ES+) calcd for C37H35NO11 669.2108; found
669.2109.
■
General Methods. Oxygen- and/or moisture-sensitive reactions
were carried out under N2 in glassware that was dried under vacuum
and purged with N2 prior to use. Reagents and solvents were
purchased from commercial vendors and used as received. 1H and 13
C
NMR spectra were recorded on 300 or 500 MHz spectrometers at 25
°C. IR spectra were obtained with an FTIR spectrometer.
Chromatography was performed using 60 Å silica gel.
2-(N,N-Dibenzylamino)-1,3-propanediol (10). 2-Aminopro-
pane-1,3-diol (5.21 g, 57.2 mmol) and anhydr potassium carbonate
(24.5 g, 177 mmol) were suspended in ethanol (200 mL). Benzyl
bromide (30.3 g, 177 mmol) was added dropwise over 30 min with
stirring. After the mixture had refluxed for 3 h, solids were separated by
filtration, and volatiles were removed under reduced pressure. The
residue was dissolved in EtOAc; the solution was washed with water,
aq NaHCO3, and brine and dried with anhyd MgSO4; and the solvent
was removed under reduced pressure. The crude mixture was purified
by recrystallization from 1:1.2 benzene/hexane to give 14.7 g (95%) of
1
white needles. H NMR (300 MHz, CDCl3) δ 7.40−7.25 (m, 10 H),
3.74 (s, 4 H), 3.69 (m, 2 H), 3.59 (m, 2 H), 2.99 (m, 3 H). 13C NMR
(75 MHz, CDCl3) δ 139.2, 128.8, 128.3, 127.3, 59.8, 59.7, 53.9. NMR
spectra are in agreement with the literature.21,48
1,7-Dioxaspiro[5.5]undecane (17). Sodium metal (1.15 g, 50.0
mmol) was dissolved in 50 mL of ethanol. To this was added dropwise
a solution of δ-valerolactone (15, 10.0 g, 100 mmol) in 15 mL of
ethanol at 0 °C, and then the mixture was refluxed for 5 h, cooled,
acidified with 5% HCl, and refluxed again for 30 min. The reaction
mixture was then co-distilled with water. The water distillate was
extracted with ether, which was then dried over anhyd MgSO4 and
2-(2-Methoxyethoxy) Ethyl Tosylate (11). To a solution of
diethyleneglycol monomethyl ether (4.35 g, 36.2 mmol) in 15 mL of
THF, cooled at 0 °C, was added NaOH (2.46 g, 61.5 mmol) dissolved
in 15 mL of water with vigorous stirring. To this mixture was added
dropwise a solution of tosyl chloride (8.28 g, 43.4 mmol) in 15 mL of
THF over 10 min at 0 °C. The reaction mixture was then raised to rt
and stirred for 1 h under N2. It was then extracted twice with 50 mL of
diethyl ether, and the organic layer was washed with 1 M aq NaOH
and water and dried with anhyd MgSO4. Solvent was removed under
reduced pressure to yield 9.0 g (91%) of colorless liquid 11. 1H NMR
(300 MHz, CDCl3) δ 7.81 (d, J = 6.0 Hz, 2H), 7.31 (d, J = 6.0 Hz,
2H), 4.17 (t, J = 6.0 Hz, 2H), 3.70 (t, J = 6.0 Hz, 2H), 3.58 (m, 2H),
3.47 (m, 2H), 3.34 (s, 3H), 2.42 (s, 3H). NMR spectrum is in
agreement with the literature.49
N,N-Dibenzyl-2,5,8,12,15,18-hexaoxa-10-nonadecanamine
(12). THF (50.0 mL) was added to NaH (60% suspension in mineral
oil) (0.80 g, 33.4 mmol), and the mixture was stirred to make a
suspension. A solution of 10 (4.12 g, 15.1 mmol) in 15 mL of THF
was then added dropwise under nitrogen, and after 30 min of stirring,
a solution of 11 (9.16 g, 33.4 mmol) in 20 mL of THF was added
dropwise. The reaction mixture was refluxed overnight, cooled, and
treated carefully with MeOH to destroy excess NaH. The solvent was
removed under reduced pressure and the resulting brown oil was
extracted 4 times with 20 mL portions of hot ether. The combined
1
concentrated to give 6.00 g (77%) of clear colorless liquid. H NMR
(500 MHz, CDCl3) δ 3.69 (d × t, J = 7.1, 14.0 Hz, 2H), 3.63 (m, 2H),
1.83 (m, 2H), 1.5 (m, 10H), consistent with the literature4 values. IR
(liquid film) 1652 cm−1.
1,9-Dihydroxy-5-nonanone Oxime (18). 1,7-Dioxaspiro[5.5]-
undecane (17, 6.00 g, 38.4 mmol), hydroxylamine hydrochloride (2.77
g, 39.9 mmol), and sodium acetate (3.24 g, 39.5 mmol) were added to
a mixture of 40 mL of ethanol and 30 mL of water, and the reaction
mixture was heated with constant stirring and a closed condenser to
prevent the escape of the volatile 17. This reaction was conducted at
40 °C for 6 h, 60 °C for 4 h, and then at 80 °C for 26 h. The reaction
mixture was cooled to rt, basified with aq NaHCO3, and extracted with
EtOAc (4 × 20 mL). The extraction was done with warm solvents to
encourage the removal of the water-soluble 18. The organic layer was
dried over anhyd MgSO4 and concentrated to give a viscous, colorless
liquid, which was purified by silica gel column chromatography (5:95
1
MeOH/EtOAc) to give 4.00 g (80%) of a viscous liquid. H NMR
(500 MHz, DMSO-d6) δ 10.17 (s, 1H), 4.37 (t, J = 5.0 Hz, 2H), 3.40−
3.33 (m, 4H), 2.20 (t, J = 8.0 Hz, 2H), 2.11−2.08 (t, J = 7.0 Hz, 2H),
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1.46−1.39 (m, 8H). 13C NMR (125 MHz, DMSO-d6) δ 159.0, 60.93,
60.91, 33.6, 33.1, 32.6, 27.0, 22.9, 22.2. IR (liquid film) 3400 (s), 1645
(s) cm−1. HRMS-ESI calcd for C9H19NO3Na 212.1263; found
212.1255.
123.0, 71.8, 71.2, 69.9, 59.0, 54.5, 32.1, 29.4, 23.5. HRMS (TOF MS
ES+) calcd for C39H39NO9Na 688.2523; found 688.2545.
Methyl 13-Bromo-2-(9-bromononyl)-3-oxotridecanoate
(22). A solution of 11-bromo undecanoic acid (21) (24.7 g, 93.0
mmol) and concd H2SO4 (5 mL) in MeOH (300 mL) was refluxed for
4 h. After most of the solvent was removed under reduced pressure,
water was added, and the mixture was extracted with ether. The ether
layer was washed with 5% NaHCO3, water, and brine, dried over
anhyd MgSO4, and concentrated by rotary evaporation to yield 20.9 g
(80.0%) of crude methyl undecanoate,51 which was used without
N-(2-Methoxyethoxy)-2,5,15,18-tetraoxanonadecan-10-one
Oxime (20). 1,9-Dihydroxynonan-5-one oxime (18, 1.50 g, 7.93
mmol) in 20 mL of THF was added dropwise at 0 °C to a solution of
NaH (60% in mineral oil, 1.40 g, 35.0 mmol) in 30 mL of THF, and
the resulting mixture was stirred for 30 min. To this was added 2-
methoxyethyl tosylate50 (7.80 g, 33.9 mmol) in 20 mL of THF
dropwise at 0 °C. Then the reaction mixture was refluxed for 12 h with
constant stirring. The reaction mixture was cooled to rt, and MeOH
was added dropwise to destroy the excess NaH. The mixture was
rotary evaporated, and the resulting crude product was extracted with
ether. The organic layer was concentrated to give a yellowish liquid,
which then was column chromatographed over silica gel eluting with
EtOAc to give 0.70 g (39%) of pure product as an oily liquid. 1H NMR
(300 MHz, CDCl3) δ 4.14 (t, J = 4.8 Hz, 2H), 3.62−3.53 (m, 10H),
3.48 (t, J = 6.6 Hz, 4H), 3.40 (s, 6H), 3.39 (s, 3H), 2.32 (t, J = 7.5 Hz,
2H), 2.17 (t, J = 7.2 Hz, 2H), 1.64−1.51 (m+t, J = 7.8 Hz, 8H). 13C
NMR (125 MHz, CDCl3) δ 161.3, 72.5, 72.1, 71.3, 71.27, 71.24, 70.2,
70.1, 59.2, 59.1, 33.9, 29.8, 29.4, 27.9, 23.2, 22.6. IR (liquid film) 1635
(w), 1456 (m) cm−1. HRMS (TOF MS ES+) calcd for C18H37NO6Na
386.2519; found 386.2520.
1
purification in the next step. H NMR was in agreement with the
literature.52
TiCl4 (8.07 g, 42.5 mmol) in toluene (50 mL) was added to a
stirred solution of methyl undecanoate (7.92 g, 28.4 mmol) and Bu3N
(9.46 g, 51.1 mmol) in toluene at −78 °C. After 1 h, the mixture was
raised to rt and stirred overnight. It was then quenched with water and
extracted twice with ether. The combined organic phase was washed
with water and brine, dried over MgSO4, and concentrated by rotary
evaporation. The resulting crude oil was purified by silica gel
chromatography (98:2 hexane/EtOAc) to give 8.3 g (56%) of 22 as
an oil. 1H NMR (300 MHz, CDCl3) δ 3.70 (s, 3H), 3.44−3.36 (m+t, J
= 6.0 Hz, 5H), 2.56−2.39 (m, 2H), 1.86−1.79 (m, 6H), 1.57−1.53 (m,
2H), 1.42−1.38 (m, 4H), 1.26 (m, 20H). 13C NMR (75 MHz, CDCl3)
δ 205.3, 170.3, 58.9, 52.2, 41.8, 33.9, 33.9, 32.7, 32.7, 29.3, 29.29,
29.28, 29.26, 29.25, 29.1, 28.7, 28.6, 28.12, 28.10, 23.4. IR 2987, 2854,
1745, 1716. HRMS (TOF MS ES+) calcd for C23H42Br2O3Na
547.1398; found 547.1407.
2,5,15,18-Tetraoxanonadecan-10-amine (13c). Compound 18
(700 mg, 1.93 mmol) was dissolved in THF on ice with constant
stirring. To this was added LAH (150 mg, 3.95 mmol), and the
reaction mixture was stirred for 10 min on ice and 2 d at reflux. The
LAH was quenched with EtOAc and then 10% NaOH, and the
resulting mixture was stirred for 20 min. The reaction mixture was
then filtered and extracted with EtOAc to give a colorless viscous
liquid, which was purified by silica gel column chromatography to give
1,21-Dibromoheneicosan-11-one (23). To a mixture of 22
(2.04 g, 3.88 mmol) in 60 mL of diethyl ether was added 10 mL of
satd NaOH (aq), and the mixture was refluxed overnight. The solvent
was removed under reduced pressure, and the aqueous layer was
extracted several times with ether. The organic layer was washed
several times with water and dried over anhyd MgSO4, and the solvent
was removed under reduced pressure to yield 1.5 g of crude powder,
which was purified by silica gel chromatography (97:3 hexane/EtOAc)
1
0.35 g (62%) of pure product as an oily liquid. H NMR (300 MHz,
CDCl3) δ 3.60−3.54 (m, 8H), 3.50 (t, J = 6.3 Hz, 4H), 3.39 (s, 6H),
3.19 (s, 2H+H2O) 2.85 (m, 1H), 1.66−1.54 (m, 4H), 1.51−1.41 (m,
8H). 13C NMR (125 MHz, CDCl3) δ 71.9, 71.3, 69.9, 59.0, 51.0, 37.7,
29.6, 22.6. IR (liquid film) 3369 (s), 1592 (m) cm−1. HRMS (TOF
MS ES+) calcd for C15H33NO4Na 314.2307; found 314.2283.
N,N′-Di[10-(2,5,15,18-tetraoxanonadecyl)]perylene-3,4,9,10-
bis(dicarboximide) (6c). A mixture of 13c (4.00 g, 13.7 mmol),
3,4,9,10-perylenetetracarboxylic dianhydride (5, 2.50 g, 6.37 mmol),
imidazole (10.0 g), and a catalytic amount of Zn(OAc)2 (127 mg) was
heated at 165 °C for 8 h. The reaction mixture solidified upon cooling
and was dissolved in CH2Cl2 and washed with 5% HCl (aq) followed
by brine solution. The organic layer was dried over anhyd MgSO4,
concentrated, and purified by neutral Al2O3 column chromatography
(CHCl3) followed by flash column chromatography over silica gel (1:9
MeOH/CH2Cl2) to give 3.51 g (59%) of pure product as a waxy solid.
1H NMR (300 MHz, CDCl3) δ 8.59−8.44 (m, 8H), 5.21−5.16 (m,
1
to give 1.1 g (65%) as a white solid, mp 50−53 °C. H NMR (300
MHz, CDCl3) δ 3.40 (t, J = 6.0 Hz, 4H), 2.40−2.36 (m, 4H), 1.87−
1.80 (m, 4H), 1.58−1.53 (m, 4H), 1.44−1.39 (m, 4H), 1.27 (m, 20H).
13C NMR (75 MHz, CDCl3) δ 211.5, 42.7, 33.9, 32.8, 29.35, 29.32,
29.2, 28.7, 28.1, 23.8. HRMS (TOF MS ES+) calcd for C21H40Br2ONa
489.1344; found 489.1347.
1,21-Dihydroxyheneicosan-11-one (24). A mixture of 23 (0.98
g, 2.09 mmol) and potassium acetate (616 mg, 6.28 mmol) in DMF
(15 mL) was stirred for 2 h at 60 °C under nitrogen. Solvent was
removed under reduced pressure to obtain crude diacetoxy ketone as a
white solid. 1H NMR (300 MHz, CDCl3) δ 4.05 (t, J = 9.0, 4H), 2.38
(t, J = 6.0 Hz, 4H), 2.04 (s, 6H), 1.61−1.30 (m, 8H), 1.27 (m, 24H).
13C NMR (75 MHz, CDCl3) δ 211.5, 171.1, 64.6, 42.7, 29.4, 29.37,
29.34, 29.2, 29.1, 28.5, 25.8, 23.8, 20.9. HRMS (TOF MS ES+) calcd
for C25H46O5Na 449.3243; found 449.3221.
2H), 3.51−3.40 (m, 24H), 3.29 (s, 12H), 2.35−2.22 (m, 4H), 1.94−
1.84 (m, 4H), 1.65−1.69 (m, 8H), 1.44−1.34 (m, 8H). 13C NMR (75
MHz, CDCl3) δ 164.3, 163.3, 134.2, 131.6, 130.9, 129.3, 126.1, 123.6,
122.9, 122.8, 71.8, 71.1, 69.8, 58.9, 54.3, 32.0, 29.3, 23.4. IR (KBr
pellet) 1697 (s), 1655 (s), 1595 (w) cm−1. HRMS (TOF MS ES+)
calcd for C54H70N2O12Na 961.4827; found 961.4847.
Crude diacetoxy ketone was treated with KOH (700 mg) in
methanol (20 mL) at 60 °C. The mixture was concentrated and
extracted with dichloromethane. The extract was washed twice with
water and dried over MgSO4. Evaporation of solvent gave pure
product as a white solid (0.40 g, 45%), which was used without
1
purification. H NMR (300 MHz, CDCl3) δ 3.66 (t, J = 6.0 Hz, 4H),
N-[10-(2,5,15,18-Tetraoxanonadecyl)]-3,4,9,10-perylenete-
tracarboxylic Acid 3,4-Anhydride 9,10-Imide (7c). A solution of
6c (500 mg, 0.532 mmol) in EtOH was treated with KOH as follows,
with monitoring by TLC. First 124 mg of KOH (2.21 mmol) was
added while the reaction was heated at 55 °C for 1 h, then 240 mg of
KOH (4.28 mmol) at 65 °C for 2 h, and finally 250 mg of KOH (4.46
mmol) at 75 °C for 2 h. The reaction mixture was then cooled to rt,
acidified with 5% HCl and extracted with CHCl3. The organic layer
was treated with brine, dried over anhyd MgSO4, and concentrated to
give a solid. This was purified by silica gel column chromatography
(5:95 MeOH/CHCl3) to give 220 mg (62%) of pure product as a
2.40 (t, J = 9.0, 4H), 1.63−1.54 (m, 10H), 1.29 (m, 24H). 13C NMR
(75 MHz, CDCl3) δ 211.7, 63.0, 42.8, 32.7, 29.5, 29.3, 29.2, 25.7, 23.8.
HRMS (TOF MS ES+) calcd for C21H42O3Na 365.3032; found
365.3055.
11-Aminoheneicosane-1,21-diol (13d). To a solution of 24
(3.57 g, 10.4 mmol) in 150 mL of isopropyl alcohol were added
NH4OAc (8.03 g, 104 mmol), Na(BH3)CN (655 mg, 10.4 mmol) and
crushed 4 Å molecular sieves in one portion under nitrogen, and the
mixture was stirred for 36 h at rt. The crushed molecular sieves were
removed via vacuum filtration, and water was added to the filtrate,
which was extracted twice with diethyl ether. The organic layer was
washed with 1 M NaOH and brine and dried over anhyd MgSO4 to
obtain a brown oil after concentration, which was purified by silica gel
chromatography (3:1:1 hexane/EtOAc/MeOH) to obtain 2.4 g of 13d
1
waxy solid. H NMR (300 MHz, CDCl3) δ 8.69−8.62 (m, 8H), 5.22
(m, 1H), 3.54−3.42 (m, 12H), 3.33 (s, 6H), 2.32−2.28 (m, 2H),
1.91−1.87 (m, 2H), 1.69−1.60 (m, 4H+H2O), 1.49−1.24 (m, 4H).
13C NMR (75 MHz, CDCl3) δ 163.4, 162.9, 135.3, 134.1, 131.2, 123.3,
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(69%) as a white solid, mp 99−100 °C. 1H NMR (300 MHz, CDCl3)
δ 3.68−3.64 (m, 4H), 2.68 (m, 1H), 1.61−1.54 (m, 6H), 1.34−1.30
(m, 34H). 13C NMR (75 MHz, CDCl3) δ 62.9, 51.3, 36.6, 32.7, 29.7,
29.6, 29.4, 29.38, 29.32, 25.8, 25.7. HRMS (TOF MS ES+) calcd for
C21H45NO2Na 366.3348; found 366.3371.
monoimide 7e (108 mg, 0.129 mmol) was deprotected by addition of
acetyl chloride (2 mL) at 0 °C to a solution in methanol (2 mL) and
dichloromethane (10 mL). After overnight stirring at rt the solvent
was removed in vacuum, and the residue was dissolved in 20 mL of
CHCl3. The solution was washed with 5% NaHCO3, dried over
MgSO4, concentrated under reduced pressure, and purified by silica
gel chromatography (1:99 MeOH/CHCl3) to yield 92 mg (95%) of
pure 7f as a waxy solid. 1H NMR (300 MHz, CDCl3) δ 8.75−8.69 (m,
8H), 5.23−5.18 (m, 1H), 2.53−2.48 (q, J = 9.0 Hz 4H), 2.30−2.24
(m, 2H), 1.87−1.82 (m, 2H), 1.59−1.55 (m, 4H), 1.36−1.24 (m,
30H). 13C NMR (75 MHz, CDCl3) δ 164.2, 163.1, 159.6, 136.0, 133.3,
133.2, 131.7, 131.5, 131.0, 130.0, 129.2, 126.4,126.2, 124.7, 123.8,
122.9, 122.0, 121.6, 118.7, 54.9, 34.0, 32.3, 29.5, 29.49, 29.48, 29.43,
29.0, 28.3, 26.9, 24.6. HRMS (TOF MS ES+) calcd for
C45H51NS2O5Na 772.3106; found 772.3124.
N-(1,21-Bis(methyldisulfanyl)heneicos-11-yl)-3,4,9,10-pery-
lenetetracarboxylic Acid 3,4-Anhydride 9,10-Imide (7g). To a
solution of 7f (47 mg, 0.063 mmol) in CH2Cl2 was added methyl
methanethiosulfonate (MMTS) (17.7 μL, 0.188 mmol) and triethyl-
amine (26.2 μL, 0.188 mmol) at room temperature. After 5 h of
stirring, the reaction mixture was washed with 5% HCl, water, and
brine, dried over MgSO4, concentrated under reduced pressure, and
purified by silica gel chromatography (1:99 MeOH/CHCl3) to give 92
mg (95%) of pure 7g as a waxy solid. 1H NMR (300 MHz, CDCl3) δ
8.67−8.50 (m, 8H), 5.22−5.16 (m, 1H), 2.66 (t, J = 9.0 Hz, 4H), 2.38
(s, 6H), 2.32−2.26 (m, 2H), 2.24−2.21 (m, 2H), 1.94−1.85 (m, 4H),
1.69−1.23 (m, 28H). 13C NMR (75 MHz, CDCl3) δ 164.3, 163.1,
159.7, 136.1, 133.3, 131.8, 131.5, 131.1, 129.3, 126.4, 126.2, 123.8,
123.0, 118.7, 54.9, 38.3, 32.3, 29.5, 29.47, 29.45, 29.41, 29.1, 28.4, 26.9,
23.3. HRMS (TOF MS ES+) calcd for C47H55NO5S4Na 864.2861;
found 864.2869.
N,N′-Bis(1,21-dihydroxyheneicos-11-yl)perylene-3,4,9,10-
bis(dicarboximide) (6d). A mixture of 1.14 g (2.91 mmol) of 5, 2.2 g
(6.4 mmol) of 13d, 5 g of imidazole, and a catalytic amount of zinc
acetate was heated with stirring at 130 °C for 6 h. The mixture was
then cooled, dissolved in CHCl3, and directly purified by column
chromatography on silica gel (CHCl3) to give 1.6 g (55%) of a deep
1
red, waxy solid. H NMR (300 MHz, CDCl3) δ 8.68−8.58 (m, 8H),
5.19 (m, 2H), 3.61 (t, J = 6.0 Hz, 8H), 2.30−2.23 (m, 4H), 1.92−1.83
(m, 4H), 1.55−1.48 (m, 12H), 1.30−1.23 (m, 56H). 13C NMR (75
MHz, CDCl3) δ 164.6, 163.5, 134.5, 131.9, 131.1, 129.5, 126.4, 123.8,
123.0, 63.0, 54.7, 32.7, 32.3, 29.49, 29.46, 29.42, 29.3, 26.9, 25.6.
HRMS (TOF MS ES+) calcd for C66H94N2O8Na 1065.6908; found
1065.6935.
N-(1,21-Dihydroxyheneicos-11-yl)-3,4,9,10-perylenetetra-
carboxylic Acid 3,4-Anhydride 9,10-Imide (7d). A mixture of 600
mg (0.57 mmol) of 6d, 97.0 mg (1.75 mmol) of 85% KOH pellets,
and 15 mL of t-BuOH was brought to reflux. After 1 h an additional 4
pellets of KOH were added, and heating was continued for an
additional 1 h. The reaction was monitored with TLC and stopped
after appropriate conversion had occurred. The mixture was poured,
with stirring, into a mixture of AcOH and 2 N HCl. The resulting
solution was extracted with chloroform, washed twice with water and
brine, and purified by silica gel chromatography using 19:1 CHCl3/
MeOH to obtain 178 mg (43%) of monoimide 7d as a waxy solid. 1H
NMR (500 MHz, CDCl3) δ 8.74−8.68 (m, 8H), 5.24−5.17 (m, 1H),
3.64−3.62 (m, 4H), 2.28−2.25 (m, 2H), 1.89−1.86 (m, 2H), 1.58−
1.35 (m, 6H), 1.34−1.25 (m, 28H). 13C NMR (125 MHz, CDCl3) δ
164.4, 163.3, 159.9, 135.2, 133.6, 133.5, 131.8, 131.1, 129.5, 126.8,
126.5, 124.6, 123.9, 123.1, 119.0, 63.0, 54.9, 32.7, 32.3, 29.48, 29.45,
29.42, 29.3, 26.9, 25.6. HRMS (TOF MS ES+) calcd for C45H51NO7Na
740.3563; found 740.3589.
N-(1,21-Diacetylthioheneicos-11-yl)- 3,4,9,10-perylenetetra-
carboxylic Acid 3,4-Anhydride 9,10-Imide (7e). Method A. Diol
monoimide 7d (50.2 mg, 0.070 mmol) was dissolved in 4 mL of
pyridine, and the reaction mixture was cooled to 0 °C. Tosyl chloride
(29.3 mg, 0.154 mmol) dissolved in pyridine was added dropwise at 0
°C, and the reaction mixture was stirred overnight at rt. When TLC
showed no starting material left, the reaction mixture was diluted with
CH2Cl2, washed with water and then brine, dried over anhyd MgSO4,
and concentrated by rotary evaporation to obtain 60.7 mg of crude
ditosylate monoimide that was used further without purification.
Ditosylate monoimide (50.3 mg, 0.049 mmol) and KSAc (13.9 mg,
0.123 mmol) were dissolved in 5 mL of DMF and stirred overnight at
120 °C. The solvent was removed under reduced pressure, and the
residue was dissolved in CH2Cl2, washed with water and then brine,
and dried over anhyd MgSO4. After rotary evaporation, the residue
was purified by silica gel chromatography (1:99 MeOH/CHCl3) to
yield 22 mg (54%) of pure 7e as a waxy solid.
Method B. Diene monoimide 7h (417 mg, 0.61 mmol) was
dissolved in 20 mL of toluene. To this solution were added thiolacetic
acid (0.17 mL, 2.4 mmol) and a catalytic amount of AIBN. The
solution was then refluxed for 1 h. The reaction was quenched by
addition of 1 M NaHCO3 and extracted with CHCl3. The organic
layer was washed three times with 1 M NaHCO3 and then brine,
concentrated under reduced pressure, and purified by silica gel
chromatography (1:99 MeOH/CHCl3) to yield 428 mg (84%) of pure
7e as a waxy solid. 1H NMR (500 MHz, CDCl3) δ 8.78−8.52 (m, 8H),
5.22−5.16 (m, 1H), 2.82 (t, J = 10.0 Hz, 4H), 2.30 (s+m, 6H + 2H),
1.89 (m, 2H), 1.53−1.50 (m, 4H) 1.35−1.22 (m, 28H). 13C NMR
(125 MHz, CDCl3) δ 195.9, 164.2, 163.1, 159.7, 136.1, 133.3, 131.8,
131.6, 131.1, 129.3, 129.5, 126.3, 124.7, 124.0, 123.8, 123.0, 118.8,
54.9, 32.3, 30.6, 29.49, 29.47, 29.44, 29.3, 29.1, 29.0, 28.7, 26.9. HRMS
(TOF MS ES+) calcd for C49H55NO7 S2Na 856.3318; found 856.3337.
N-(1,21-Dimercaptoheneicos-11-yl)-3,4,9,10-perylenetetra-
carboxylic Acid 3,4-Anhydride 9,10-Imide (7f). Dithioacetate
Methyl 2-(Non-8-enyl)-3-oxotridec-12-enoate (26). A solution
of 11-undecenoic acid (25) (45.7 g, 248 mmol) and concd H2SO4 (5
mL) in MeOH (600 mL) was refluxed for 6 h. After most of the
solvent was removed under reduced pressure, water was added, and
the mixture was extracted with ether. The ether layer was washed with
5% NaHCO3, water, and brine, dried over anhyd MgSO4, and
concentrated by rotary evaporation to yield 45 g (92%) of crude
methyl undecanoate, which was used without purification in the next
52
1
step. H NMR was in agreement with the literature.
TiCl4 (6.11 g, 32.2 mmol) in toluene (50 mL) was added to a
stirred solution of methyl undecanoate (5.16 g, 17.9 mmol) and Bu3N
(4.98 g, 26.9 mmol) in toluene at 0−5 °C. After 1 h, the mixture was
raised to rt and stirred overnight. It was then quenched with water and
extracted twice with ether. The combined organic phase was washed
with water and brine, dried over MgSO4, and concentrated by rotary
evaporation. The resulting crude oil was purified by silica gel
chromatography (98:2 hexane/EtOAc) to give 7.0 g (74%) of 26 as
an oil. 1H NMR (300 MHz, CDCl3) δ 5.85−5.76 (m, 2H), 5.03−4.91
(m, 4H), 3.72 (s, 3H), 3.46−3.41 (m, 1H), 2.54−2.46 (m, 2H), 2.07−
2.00 (m, 4H), 1.84−1.60 (m, 2H), 1.57−1.32 (m, 2H), 1.28−1.24 (m,
20H). 13C NMR (75 MHz, CDCl3) δ 205.4, 170.4, 139.1, 139.0,
114.16, 114.13, 58.9, 52.2, 41.8, 33.78, 33.75, 29.35, 29.31, 29.2, 29.1,
29.04, 29.00, 28.9, 28.88, 28.83, 28.2, 27.4, 23.4. IR 2927, 2855, 1747,
1717. HRMS (TOF MS ES+) calcd for C23H40O3Na 387.2875; found
387.2898.
Heneicosa-1,20-dien-11-one (27). To a solution of 26 (4.0 g,
7.6 mmol) in 100 mL of THF was added 20 mL of satd NaOH (aq),
and the mixture was refluxed overnight. The solvent was removed
under reduced pressure, and the aqueous layer was extracted several
times with ether. The organic layer was washed several times with
water and dried over anhyd MgSO4, and the solvent was removed
under reduced pressure to yield 3.0 g of crude powder, which was
purified by silica gel chromatography (97:3 hexane/EtOAc) to give
1
2.83 g (84%) of 27, mp 55−56 °C. H NMR (500 MHz, CDCl3) δ
5.87−5.81 (m, 2H), 5.03−4.94 (m, 4H), 2.43−2.39 (m, 4H), 2.08−
2.04 (m, 4H), 1.60−1.58 (m+s, 6H + H2O), 1.39−1.38 (m, 4H), 1.30
(m, 14H). 13C NMR (125 MHz, CDCl3) δ 211.8, 139.2, 114.1, 42.8,
33.8, 29.38, 29.33, 29.2, 29.0, 28.9, 23.8. IR 1698, 994, 915. HRMS
(TOF MS ES+) calcd for C21H38ONa 329.2820; found 329.2790.
9648
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Heneicosa-1,20-dien-11-amine (13h). To a solution of 27 (5.06
g, 16.5 mmol) in 150 mL of isopropyl alcohol were added NH4OAc
(12.7 g, 165 mmol), Na(BH3)CN (1.03g, 16.5 mmol), and crushed 4
Å molecular sieves in one portion under nitrogen, and the mixture was
stirred for 36 h at rt. The crushed molecular sieves were removed via
vacuum filtration, and deionized water was added to the filtrate, which
was extracted twice with diethyl ether. The organic layer was washed
with 1 M NaOH and brine and dried over anhyd MgSO4 to obtain a
brown oil after concentration, which was purified by silica gel
chromatography (3:1:1 hexane/EtOAc/MeOH) to obtain 3.7 g of 13h
(73%) as a white solid. 1H NMR (300 MHz, CDCl3) δ 5.89−5.76 (m,
2H), 5.04−4.92 (m, 4H), 2.69−2.67 (m, 1H), 2.09−2.02 (m, 4H),
1.41−1.38 (m, 10H), 1.36−1.21 (m, 20H). 13C NMR (75 MHz,
CDCl3) δ 139.1, 114.1, 51.2, 37.3, 33.8, 29.7, 29.5, 29.4, 29.1, 28.9,
26.0. HRMS (TOF MS ES+) calcd for C21H41NNa 330.3137; found
330.3166.
1341 (s), 1252 (m), 1110 (s) cm−1. HRMS (TOF MS ES+) calcd for
C54H46N2O10Na 905.3050; found 905.3077.
N-(2,5,8,12,15,18-Hexaoxanonadec-10-yl)-N′-(4-[1-pyrenyl]-
butyl)perylene-3,4,9,10-bis(dicarboximide) (2b). Prepared from
7b (102 mg, 0.152 mmol) and 4-pyrenylbutylamine (2-NH2, Toronto
Research Chemicals, 52.0 mg, 0.190 mmol). Elution with 99:1 CHCl3/
MeOH gave 26 mg (18%) of 2b as a waxy solid. 1H NMR (300 MHz,
CDCl3) δ 8.37−8.21 (m, 4H), 8.08−7.62 (m, 13H), 5.78−5.72 (m,
1H), 4.31−4.20 (m, 4H), 4.08−4.02 (m, 2H), 3.85−3.59 (m, 12H),
3.47 (t, J = 6.0 Hz, 4H), 3.31 (s, 6H), 3.14 (m, 2H), 1.95 (m, 4H). 13C
NMR (75 MHz, CDCl3) δ163.7, 163.0, 136.1, 133.8, 133.7, 130.9,
130.7, 130.3, 129.3, 128.4, 128.0, 127.3, 127.1, 126.8, 126.1, 125.4,
124.5, 124.4, 124.3, 123.0, 122.4, 122.3, 71.8, 70.5, 70.4, 70.3, 69.4,
58.9, 52.0, 40.2, 33.3, 28.8, 27.8. IR (KBr) 1692 (s), 1655 (s), 1595
(m), 1342 (s), 1253 (m), 1109 (s) cm−1. HRMS (TOF MS ES+) calcd
for C57H52N2O10Na 947.3520; found 947.3517.
N-(2-Ferrocenylethyl)-N′-(2,5,8,12,15,18-hexaoxanonadec-
10-yl)perylene-3,4,9,10-bis(dicarboximide) (3b). Prepared from
7b (119 mg, 0.178 mmol) and 3-ferrocenylethylamine1 (3-NH2, 51
mg, 0.22 mmol). Elution with 99.4:0.6 CHCl3/MeOH gave 47 mg
N,N′-Di(1,20-heneicosadien-11-yl)perylene-3,4,9,10-bis-
(dicarboximide) (6h). A mixture of 3.07 g (7.83 mmol) of 5, 5.06 g
(16.4 mmol) of 13h, 15 g of imidazole, and a catalytic amount of zinc
acetate was heated with stirring at 160 °C for 2 h. The mixture was
then cooled, dissolved in CHCl3, and directly purified by column
chromatography on silica gel (CHCl3) to give 3.9 g (74%) of a deep
1
(24%) of 3b as a waxy solid. H NMR (300 MHz, CDCl3) δ 8.59−
8.51 (m, 4H), 8.44−8.39 (m, 4H), 5.77−5.68 (q, 1H), 4.37 (m, 2H),
4.22 (m, 9H), 4.10 (s, 2H), 3.65 (m, 2H), 3.63−5.56 (m, 12H), 3.45−
3.44 (m, 4H), 3.28 (s, 6H), 2.82−2.77 (m, 2H). 13C NMR (75 MHz,
CDCl3) δ 163.6, 163.1, 134.4, 134.1, 131.2, 129.3, 129.1, 126.2, 126.0,
123.4, 123.0, 122.96, 122.92, 85.1, 71.8, 70.5, 70.4, 70.3, 68.6, 58.9,
52.1, 41.2, 27.7. IR (KBr) 1696 (s), 1655 (s), 1596 (m), 1342 (s),
1249 (m), 1105 (s) cm−1. HRMS (TOF MS ES+) calcd for
C49H48FeN2O10Na 903.2557; found 903.2574.
1
red, waxy solid. H NMR (300 MHz, CDCl3) δ 8.70−8.64 (m, 8H),
5.84−5.70 (m, 4H) 5.19 (m, 2H), 4.98−4.87 (m, 8H), 2.25 (m, 4H),
2.03−1.95 (m, 8H), 1.87 (m, 4H), 1.32−1.23 (m, 48H). 13C NMR
(125 MHz, CDCl3) δ 164.6, 163.5, 139.2, 134.4, 131.8, 131.1, 129.5,
126.4, 123.9, 123.0, 114.0, 54.7, 33.7, 32.3, 29.5, 29.4, 29.08, 29.01,
28.8, 26.9. HRMS (TOF MS ES+) calcd for C66H86N2O4Na 993.6485;
found 993.6491.
N-(3-[2,5-Bis(dimethylamino)phenyl]propyl)-N′-
(2,5,8,12,15,18-hexaoxanonadec-10-yl)perylene-4,5,9,10-bis-
(dicarboximide) (4b). Prepared from 7b (126 mg, 0.188 mmol) and
3-tetramethylphenylenediaminylpropylamine1 (4-NH2, 70.0 mg, 0.316
mmol). Elution with 49:1 CHCl3/MeOH gave 21 mg (13%) of 4b as a
waxy solid and 50 mg (31%) of an additional fraction containing a
trace impurity by TLC. 1H NMR (500 MHz, CDCl3) δ 8.57−8.51 (m,
4H), 8.42−8.35 (m, 4H), 7.05−7.03 (d, 1H), 6.71 (s, 1H), 6.56−6.55
(d, 1H), 5.75−5.69 (m, 1H), 4.32−4.30 (m, 2H), 4.20−4.23 (m, 2H),
3.97−4.01 (m, 2H), 3.64−3.57 (m, 12H), 3.44−3.42 (m, 4H), 3.28 (s,
6H), 2.89 (s, 8H), 2.62 (s, 6H) 2.19−2.13 (m, 2H). 13C NMR (75
MHz, CDCl3) δ 163.6, 163.0, 147.5, 143.1, 137.4, 134.0, 131.0, 129.2,
128.9, 125.9, 125.8, 123.2, 123.1, 122.8, 122.7, 120.6, 114.2, 111.3,
71.8, 70.5, 70.4, 70.3, 69.3, 58.9, 52.1, 45.8, 41.1, 40.9, 29.7, 28.6. IR
(KBr) 1698 (s), 1655 (s), 1596 (m), 1343 (s), 1107 (s) cm−1. HRMS
(TOF MS ES+) calcd for C50H56N4O10Na 895.3894; found 895.3890.
General Procedure for Bisimides D-σ-A Molecules with a
Mixed Swallowtail (R = c). Perylene monoimide monoanhydride
with a mixed alkyl-PEG swallowtail 7c and a donor amine were
dissolved in toluene and refluxed for 12 h to give the target
nonsymmetric bisimides 1c−4c. These were purified by neutral Al2O3
column chromatography (CHCl3) followed by silica gel column
chromatography (99:1 CHCl3/MeOH).
N-(1-Pyrenylmethyl)-N′-(2,5,15,18-tetraoxanonadec-10-yl)-
perylene-3,4,9,10-bis(dicarboximide) (1c). Pyrenylmethylamine
1-NH2 (35 mg, 0.15 mmol) and 7c (70.0 mg, 0.105 mmol) gave 30
mg (27%) of 1c as a waxy solid. 1H NMR (300 MHz, CDCl3) δ 8.41−
8.35 (d, J = 9.4 Hz, 3H), 8.16−8.13 (d, J = 7.9 Hz, 2H), 7.95 (d, J =
7.9 Hz, 2H), 7.74 (m, 8H), 7.54 (m, 2H), 5.86 (s, 2H), 5.23 (m, 1H),
3.47 (m, 12H), 3.31 (s, 6H), 2.34 (m, 2H), 1.99 (m, 2H), 1.68 (m,
4H), 1.46 (m, 4H). 13C NMR (75 MHz, CDCl3) δ 164.3, 163.2, 133.6,
133.3, 130.7, 130.6, 130.18, 130.15, 129.9, 128.7, 128.3, 127.4, 126.7,
125.6, 125.5, 125.2, 125.1, 124.8, 124.7, 124.4, 124.2, 123.9, 122.8,
122.6, 122.4, 122.2, 122.0, 71.8, 71.2, 69.8, 58.9, 54.5, 41.1, 32.2, 29.5,
23.6. IR (KBr) 1692 (s), 1655 (s), 1595 (s) cm−1. HRMS (TOF MS
ES+) calcd for C56H50N2O8Na 901.3465; found 901.3491.
N-(1,20-Heneicosadien-11-yl)-3,4,9,10-perylenetetracarbox-
ylic Acid 3,4-Anhydride-9,10 Imide (7h). A mixture of 1.24 g (1.27
mmol) of 6h, 215 mg (3.83 mmol) of 85% KOH pellets, and 50 mL of
t-BuOH was brought to reflux. After 1 h an additional 10 pellets of
KOH were added, and heating was continued for an additional 1 h.
The reaction was monitored with TLC and stopped after appropriate
conversion had occurred. The mixture was poured with stirring into a
mixture of 70 mL of AcOH and 40 mL of 2 N HCl. The resulting
solution was extracted with chloroform, which was washed twice with
water and once with brine, concentrated, and purified by silica gel
chromatography using CHCl3 to obtain 520 mg (59%) of monoimide
1
7h as a waxy solid. H NMR (500 MHz, CDCl3) δ 8.66−8.46 (m,
8H), 5.84−5.70 (m, 2H), 5.22−5.13 (m, 1H), 4.98−4.87 (m, 4H),
2.27−2.01 (m, 2H), 1.98−1.89 (m+m, 2H+4H), 1.37−1.25 (m, 24H).
13C NMR (125 MHz, CDCl3) δ 164.3, 163.2, 159.8, 139.1, 136.2,
133.4, 131.7, 129.4, 126.6, 126.4, 123.8, 123.0, 118.9, 114.0, 54.8, 33.7,
32.2, 29.46, 29.42, 29.3, 29.06, 29.03, 28.8, 26.9. HRMS (TOF MS
ES+) calcd for C45H47NO5Na 704.3352; found 704.3381.
General Procedure for Bisimide D-σ-A Molecules with a PEG
Swallowtail (R = b). Perylene monoimide monoanhydride with a
PEG swallowtail (7b) and a suitable donor amine were added to
pyridine and stirred under reflux for 12 h. Then the reaction mixture
was added to excess 5% HCl and extracted with CHCl3. The organic
layer was then washed with an excess of 10% K2CO3, dried over anhyd
Na2SO4, and rotary evaporated to give crude product, which was
purified by silica gel chromatography. Pyrenemethylamine (1-NH2)
was prepared by treating pyrenemethylammonium chloride (Aldrich)
with KOH (aq) and MeOH.
N-(2,5,8,12,15,18-Hexaoxanonadec-10-yl)-N′-(1-
pyrenylmethyl)perylene-3,4,9,10-bis(dicarboximide) (1b). Pre-
pared from 7b (98.0 mg, 0.146 mmol) and 1-pyrenylmethylamine (1-
NH2, 43.0 mg, 0.186 mmol). Elution with 99:1 CHCl3/MeOH gave
1
25 mg (19%) of 1b as a waxy solid. H NMR (500 MHz, CDCl3) δ
8.64−8.14 (m, 5H), 8.11−8.07 (d, 4H), 8.05−7.82 (m, 8H), 6.11 (s,
2H), 5.74−5.72 (m, 1H), 4.27−4.21 (m, 2H), 4.04−3.99 (m, 2H),
3.77−3.57 (m, 12H), 3.46−3.43 (m, 4H), 3.30 (s, 6H). 13C NMR (75
MHz, CDCl3) δ 163.5, 163.3, 133.8, 133.4, 131.0, 130.6, 130.2, 129.9,
128.6, 128.5, 128.3, 127.5, 126.8, 126.7, 125.5, 125.4, 125.3, 125.2,
124.9, 124.8, 124.5, 124.2, 124.0, 122.8, 122.4, 122.2, 71.8, 70.5, 70.4,
70.3, 69.4, 58.9, 52.1, 41.2. IR (KBr) 1692 (s), 1656 (s), 1595 (s),
N-[4-(1-Pyrenyl)butyl]-N′-(2,5,15,18-tetraoxanonadec-10-yl)-
perylene-3,4,9,10-bis(dicarboximide) (2c). Pyrenebutylamine (2-
NH2, 15 mg, 0.056 mmol) and 7c (25 mg, 0.038 mmol) gave 7.5 mg
(22%) of 2c as a waxy solid. 1H NMR (300 MHz, CDCl3) δ 8.64 (m,
2H), 8.45 (dxd, J = 9.0 Hz, 3.0 Hz, 4H), 8.34 (d, J = 9.0 Hz, 2H), 8.14
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(d, J = 9.0 Hz, 1H), 8.00−7.40 (m, 8H), 5.24 (m, 1H), 4.25 (s, 2H),
3.54−3.46 (m, 12H), 3.33 (s, 6H), 2.32−2.34 (m, 2H), 1.94−2.02 (m
+m, 2H + 4H), 1.60−1.69 (m, 6H + H2O), 1.44 (m, 4H). 13C NMR
(75 MHz, CDCl3) δ 164.6, 163.2, 143.4, 136.2, 134.2, 131.0, 130.5,
129.5, 128.3, 127.5, 127.3, 126.9, 126.2, 125.9, 125.5, 124.6, 124.5,
123.2, 122.8, 122.7, 122.6, 71.8, 71.2, 69.9, 59.0, 54.5, 40.3, 33.4, 32.1,
29.4, 28.6, 27.6, 23.5. HRMS (TOF MS ES+) calcd for C59H56N2O8Na
943.3934; found 943.3951.
N-(2-Ferrocenylethyl)-N′-(2,5,15,18-tetraoxanonadec-10-yl)-
perylene-3,4,9,10-bis(dicarboximide) (3c). Ferrocenylethylamine
3-NH2 (62 mg, 0.28 mmol) and 7c (80 mg, 0.12 mmol) in 5 mL of
toluene gave 21 mg (20%) of 3c as a waxy solid. 1H NMR (300 MHz,
CDCl3) δ 8.66−8.55 (m, 8H), 5.21 (m, 1H), 4.43−4.37 (m, 2H), 4.22
(s, 7H), 4.12 (s, 2H), 3.51−3.43 (m, 12H), 3.32 (s, 6H), 2.81−2.76
(m, 2H), 2.32−2.29 (m, 2H), 1.95−1.91 (m, 2H), 1.71−1.66 (m, 4H),
1.65−1.40 (m, 4H). 13C NMR (75 MHz, CDCl3) δ 163.4, 163.1,
134.6, 134.2, 131.3, 129.4, 126.4, 123.1, 123.06, 123.00, 85.0, 71.8,
71.2, 69.9, 68.6, 68.1, 67.4, 59.0, 54.5, 41.2, 32.1, 29.4, 27.7, 23.5. IR
(KBr) 1692 (s), 1656 (s), 1596 (s) cm−1. HRMS (TOF MS ES+) calcd
for C51H52FeN2O8Na 899.2972; found 899.2991.
N-(1,21-Diacetylthioheneicos-11-yl)-N′-(2-ferrocenylethyl)-
perylene-3,4,9,10-bis(dicarboximide) (3e). 3-NH2 (27.50 mg,
0.120 mmol) and 7e (50.1 mg, 0.06 mmol) gave 3e (54 mg) in 86%
1
yield as a waxy solid. H NMR (300 MHz, CDCl3) δ 8.69−8.53 (m,
8H), 5.23−5.18 (m, 1H), 4.40 (t, J = 6.0 Hz, 2H), 4.23 (s,7H), 4.16 (s,
2H), 2.85−2.76 (m, 6H), 2.31−2.25 (m, 6H + 2H), 1.92−1.85 (m,
2H), 1.60−1.47 (m, 4H), 1.32−1.22 (m, 28H). 13C NMR (75 MHz,
CDCl3) δ 196.0, 164.5, 163.1, 134.6, 134.2, 131.2, 129.4, 129.2, 126.3,
126.2, 123.0, 122.9, 85.0, 68.6, 68.1, 67.4, 54.7, 41.2, 32.3, 30.6, 29.5,
29.46, 29.44, 29.3, 29.1, 29.0, 28.7, 27.7, 26.9. HRMS (TOF MS ES+)
calcd for C61H68FeN2O6S2Na 1067.3768; found 1067.3789.
N-(1,21-Diacetylthioheneicos-11-yl)-N′-(3-[2-(N′,N′,N″,N″-
tetramethyl-1,4-benzenediaminyl)propyl)perylene-3,4,9,10-
bis(dicarboximide) (4e). 4-NH2 (7.96 mg, 0.036 mmol) and 7e
(30.0 mg, 0.036 mmol) gave 4e (26 mg) in 71% yield as a waxy solid.
1H NMR (300 MHz, CDCl3) δ 8.53−8.46 (m, 2H), 8.31−8.12 (m,
6H), 7.03−7.00 (d, J = 6.0 Hz, 1H), 6.70 (d, J = 3.0 Hz, 1H), 6.54−
6.50 (dxd, J = 9.0 Hz, 3.0 Hz, 1H), 5.21−5.14 (m, 1H), 4.25−4.20 (m,
2H), 2.88−2.78 (m, 10H), 2.60 (s, 6H), 2.29−2.28 (m, 8H), 2.16−
2.05 (m, 2H), 1.94−1.90 (m, 2H), 1.54−1.42 (m, 6H), 1.37−1.22 (m,
28H). 13C NMR (75 MHz, CDCl3) δ 195.8, 164.1, 162.6, 147.3, 143.0,
137.3, 133.7, 130.5, 129.0, 125.6, 122.7, 122.4, 120.4, 114.0, 111.1,
54.6, 45.7, 41.0, 33.9, 32.2, 30.5, 29.47, 29.43, 29.40, 29.37, 29.33, 29.0,
28.7, 28.4, 26.9. HRMS (TOF MS ES+) calcd for C62H76 N4O6S2Na
1059.5104; found 1059.5125.
N-(3-[2,5-Bis(dimethylamino)phenyl]propyl)-N′-(2,5,15,18-
tetraoxanonadec-10-yl)perylene-4,5,9,10-bis(dicarboximide)
(4c). TMPDA-propanamine 4-NH2 (80.0 mg, 0.361 mmol) and 7c
1
(120 mg, 0.180 mmol) gave 44 mg (28%) of 4c as a waxy solid. H
NMR (300 MHz, CDCl3) δ 8.66−8.56 (m, 8H), 7.06−7.04 (d, J = 6.0
Hz, 1H), 6.72−6.71 (d, J = 3.0 Hz, 1H), 6.58−6.55 (d × d, J = 10 Hz,
5.0 Hz, 1H), 5.23−5.21 (m, 1H), 4.35−4.32 (m, 2H), 3.54−3.45 (m,
12H), 3.33 (s, 6H), 2.90−2.89 (m, 6 + 2H), 2.63 (s, 6H), 2.31 (m,
N-(1,21-Dimercaptoheneicos-11-yl)-N′-([1-pyrenyl]methyl)-
perylene-3,4,9,10-bis(dicarboximide) (1f). 1-NH2 (18.50 mg,
0.080 mmol) and 7f (30.00 mg, 0.040 mmol) gave 1f (34 mg) in
1
2H), 2.14 (m, 2H), 1.92 (m, 2H), 1.67 (4H+H2O), 1.38 (m, 4H). 13
C
89% yield as a waxy solid. H NMR (300 MHz, CDCl3) δ 8.54−8.49
NMR (75 MHz, CDCl3) δ 164.5, 163.2, 147.5, 137.4, 131.2, 129.3,
126.4, 123.3, 122.98, 122.95, 120.6, 114.2, 111.3, 71.9, 71.2, 69.9, 58.9,
54.5, 45.8, 41.1, 40.8, 32.1, 29.4, 28.6, 23.5. IR (KBr) 1695 (s), 1655
(s), 1595 (s) cm−1. HRMS (TOF MS ES+) calcd for C52H60N4O8Na
891.4309; found 891.4333.
General Procedure for Bisimide D-σ-A Molecules with a
Dithioacetyl Swallowtail (R = e). A mixture of the perylene
monoimide monoanhydride with a dithioacetylalkyl swallowtail (7e)
and a 2- to 4-fold molar excess of the appropriate amine was refluxed
in toluene for 1−2 h. The reaction mixture was then cooled, washed
with 5% HCl followed by 10% K2CO3, dried over MgSO4, and
concentrated by rotary evaporation. Crude products were purified by
chromatography on silica gel (1:99 MeOH/CHCl3) to give red solids.
Melting points were difficult to obtain due to the deep color and waxy
nature of the materials.
N-(1,21-Diacetylthioheneicos-11-yl)-N′-([1-pyrenyl]methyl)-
perylene-3,4,9,10-bis(dicarboximide) (1e). 1-NH2 (20.7 mg,
0.090 mmol) and 7h (47.0 mg, 0.045 mmol) gave 33 mg (88%) of
pure 1e as a waxy solid. 1H NMR (300 MHz, CDCl3) δ 8.68−8.61 (m,
5H), 8.53−8.47 (m, 4H), 8.19−8.04 (m, 5H), 7.97−7.90 (m, 3H),
6.12 (s, 2H), 5.20 (m, 1H), 2.81 (t, J = 6.0 Hz, 4H), 2.30−2.25 (s+m,
6H + 2H), 1.88−1.85 (m, 2H), 1.53−1.45 (m, 4H), 1.30−1.19 (m,
28H). 13C NMR (75 MHz, CDCl3) δ 196.2, 164.8, 163.7, 134.7, 134.1,
131.6, 131.3, 130.8, 130.8, 130.3, 129.5, 129.3, 128.9, 127.9, 127.4,
127.3, 126.2, 126.2, 126.0, 125.3, 125.2, 124.9, 124.8, 124.7, 124.1,
123.3, 123.2, 122.9, 55.0, 41.6, 32.6, 30.8, 29.79, 29.75, 29.72, 29.6,
29.38, 29.31, 29.2, 29.0, 27.2. HRMS (TOF MS ES+) calcd for
C66H66N2O6 S2Na 1069.4260; found 1069.4248.
(m, 3H), 8.39 (d, J = 6.0 Hz, 2H), 8.26 (d, J = 9.0, 2H), 8.18 (d, J =
9.0, 2H), 8.03−7.70 (m, 8H), 5.98 (s, 2H), 5.20 (m, 1H), 2.50−2.43
(q, J = 6.0 Hz, 4H), 2.33−2.25 (m, 2H), 1.93−1.88 (m, 2H), 1.56−
1.48 (m, 4H), 1.31−1.18 (m, 30H). 13C NMR (75 MHz, CDCl3) δ
163.4, 134.2, 133.7, 131.3, 130.9, 130.49, 130.44, 130.0, 129.1, 128.9,
128.6, 127.6, 127.0, 125.8, 125.6, 125.0, 124.9, 124.58, 124.54, 124.3,
123.0, 122.8, 122.5, 54.7, 41.3, 33.9, 32.3, 29.55, 29.50, 29.47, 29.40,
28.9, 28.3, 27.0, 24.6. HRMS (TOF MS ES+) calcd for C62H62 N2O4
S2Na 985.4048; found 985.4070.
N-(1,21-Dimercaptoheneicos-11-yl)-N′-(2-ferrocenylethyl)-
perylene-3,4,9,10-bis(dicarboximide) (3f). 3-NH2 (18.30 mg,
0.080 mmol) and 7f (30.0 mg, 0.04 mg) gave 3f (33 mg) in 87%
1
yield as a waxy solid. H NMR (300 MHz, CDCl3) δ 8.69−8.60 (m,
8H), 5.20 (m, 1H), 4.43−4.38 (m, 2H), 4.24−4.21 (m, 7H), 4.11 (s,
2H), 2.79 (t, J = 9.0 Hz, 2H), 2.52−2.44 (q, J = 6.0 Hz, 4H), 2.33−
2.20 (m, 2H), 1.93−1.83 (m, 2H), 1.58−1.51 (m, 4H + H2O), 1.32−
1.22 (m, 30H). 13C NMR (75 MHz, CDCl3) δ 163.2, 134.7, 134.3,
131.8, 131.4, 131.1, 129.5, 129.4, 126.5, 126.3, 123.1, 123.0, 85.0, 69.1,
68.6, 68.3, 68.1, 67.5, 54.7, 41.2, 34.0, 32.3, 29.5, 29.46, 29.42, 29.0,
28.3, 27.8, 26.9, 24.6, 24.4. HRMS (TOF MS ES+) calcd for
C57H64FeN2O4S2Na 983.3556; found 983.3584.
N-(1,21-Bis(methyldisulfanyl)heneicos-11-yl)-N′-4-[1-
pyrenylmethyl])perylene-3,4,9,10-bis(dicarboximide) (1g). 1-
NH2 (21.97 mg, 0.095 mmol) and 7g (40.00 mg, 0.047 mmol) gave
1g (41 mg) in 82% yield as a waxy solid. 1H NMR (300 MHz, CDCl3)
δ 8.65−8.55 (m, 5H), 8.47−8.40 (m, 4H), 8.16−7.85 (m 8H), 6.09 (s,
2H), 5.20 (m, 1H), 2.65 (t, J = 6.0 Hz, 4H), 2.38 (s, 6H), 2.36−2.25
(m, 2H), 1.89 (m, 2H), 1.67−1.56 (m, 4H), 1.37−1.20 (m, 28H). 13C
NMR (125 MHz, CDCl3) δ 164.4, 163.2, 133.9, 133.5, 131.0, 130.8,
130.36, 130.33, 130.0, 128.9, 128.6, 128.5, 127.5, 126.9, 125.8, 125.58,
125.51, 125.4, 124.9, 124.8, 124.5, 124.3, 124.2, 122.9, 122.6, 122.3,
54.7, 41.2, 38.3, 32.4, 29.57, 29.51, 29.48, 29.42, 29.3, 29.1, 28.4, 27.0,
23.3. HRMS (TOF MS ES+) calcd for C64H66N2O4S4Na 1077.3803;
found 1077.3827.
N-(1,21-Bis(methyldisulfanyl)heneicos-11-yl)-N′-(2-
ferrocenylethyl)perylene-3,4,9,10-bis(dicarboximide) (3g). 3-
NH2 (21.76 mg, 0.095 mmol) and 7g (40.0 mg, 0.047 mmol) gave
3g (39 mg) in 79% yield as a waxy solid. 1H NMR (300 MHz, CDCl3)
δ 8.64−8.46 (m, 8H), 5.24−5.19 (m, 1H), 4.40 (t, J = 9.0 Hz, 2H),
4.30−4.21 (m, 7H), 4.12 (m, 2H), 2.79 (t, J = 9.0 Hz, 2H), 2.67 (t, J =
6.0 Hz, 4H), 2.41 (s, 6H), 2.30−2.26 (m, 2H), 1.94−1.87 (m, 2H),
N-(1,21-Diacetylthioheneicos-11-yl)-N′-(4-[1-pyrenyl]butyl)-
perylene-3,4,9,10-bis(dicarboximide) (2e). 2-NH2 (43.30 mg,
0.158 mmol) and 7e (66.00 mg, 0.079 mmol) gave 2e in 82% yield as
1
a waxy solid. H NMR (500 MHz, CDCl3) δ 8.46−7.52 (m, 17H),
5.26−5.18 (m, 1H), 4.17−4.12 (m, 2H), 3.12−3.07 (m, 2H), 2.81 (t, J
= 9.0 Hz, 4H), 2.32−2.27 (s+m 6H + 2H), 1.94−1.91 (m, 4H), 1.55−
1.45 (m, 6H), 1.37−1.23 (m, 28H). 13C NMR (75 MHz, CDCl3) δ
196.0, 164.4, 162.9, 136.1, 133.6, 130.8, 130.5, 130.3, 129.2, 128.9,
128.3, 127.9, 127.2, 127.0, 126.7, 126.0, 125.4, 125.3, 124.5, 124.38,
124.32, 124.2, 122.9, 122.4, 122.2, 122.1, 54.6, 40.1, 33.3, 32.3, 30.5,
29.55, 29.52, 29.48, 29.43, 29.3, 29.07, 29.05, 28.9, 28.7, 27.0. HRMS
(TOF MS ES+) calcd for C69H72N2O6S2Na 1111.4729; found
1111.4746.
9650
dx.doi.org/10.1021/jo301701a | J. Org. Chem. 2012, 77, 9641−9651

The Journal of Organic Chemistry
Article
1.67−1.60 (m, 4H), 1.37−1.25 (m, 28H). 13C NMR (75 MHz,
CDCl3) δ 164.3, 163.0, 134.4, 134.1, 131.7, 131.1, 130.9, 129.4, 129.1,
126.2, 126.1, 123.0, 122.98, 122.91, 85.1, 73.1, 69.6, 68.6, 68.1, 67.4,
54.8, 41.2, 38.3, 32.3, 29.5, 29.48, 29.42, 29.1, 28.4, 27.7, 26.9, 23.3.
HRMS (TOF MS ES+) calcd for C59H68FeN2O4S4Na 1075.3311;
found 1075.3282.
(22) Wicklein, A.; Lang, A.; Muth, M.; Thelakkat, M. J. Am. Chem.
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Discuss. 2006, 131, 221−234.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR spectra for new compounds. This material is
available free of charge via the Internet at http://pubs.acs.org.
(26) (a) Jaiswal, A.; Rajagopal, D.; Lakshmikantham, M. V.; Cava, P.;
Metzger, R. M. Phys. Chem. Chem. Phys. 2007, 9, 4007−4017.
(b) Girlando, A.; Sissa, C.; Terenziani, F.; Painelli, A.; Chwialkowska.,
A.; Ashwell, G. J. Chem. Phys. Chem. 2007, 8, 2195−2201.
AUTHOR INFORMATION
Corresponding Author
*E-mail: mattern@olemiss.edu.
Notes
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́
(c) Bethencourt, M. I.; Srisombat, L.; Chinwangso, P.; Lee, T. R.
Langmuir 2009, 25, 1265−1271.
(27) Chen, L. X.; Xiao, S.; Yu, L. J. Phys. Chem. B 2006, 110, 11730−
11738.
The authors declare no competing financial interest.
(28) Langhals, H.; Krotz, O.; Polborn, K.; Mayer, P. Angew. Chem.,
Int. Ed. 2005, 44, 2427−2428.
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ACKNOWLEDGMENTS
■
We gratefully acknowledge support from the National Science
Foundation, CHE 0848206. We thank Dr. Amal Dass and Mr.
Nuwan Kothalawala for their analytical assistance.
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NOTE ADDED AFTER ASAP PUBLICATION
■
After ASAP publication on October 22, 2012, corrections were
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