Bis-amidopyrrolyl receptors based on anthracene and carbazole

Article abstract of DOI:10.1080/10610270903304434

A new set of diamide receptors containing anthracene and carbazole bridging subunits and either pyrrole or phenyl substituents were synthesised. The four systems produced in this way were shown to bind representative anions in DMSO-d₆ solution and in the solid state. A higher relative affinity for two test oxoanions, namely dihydrogen phosphate and benzoate, over chloride anion was seen in solution, with the anions in question being studied in the form of their respective tetrabutylammonium salts. However, the specifics of the anion recognition process were seen to depend on structure, with the pyrrole-containing systems displaying higher relative affinities than their corresponding phenyl-containing congeners, and the carbazole receptors proving more effective than the anthracene analogues. Such observations provide support for the notion that both the carbazole NH and the pyrrolic NH protons play an important role in stabilising the receptor-bound anions in solution. Structural analyses of several anion complexes of the diamidopyrrole carbazole receptor reveal that this is not necessarily the case in the solid state; specifically, the pyrrole NH protons are seen to interact with the amide oxygen of another molecule. The net result is an extended one-dimensional coordination polymer.

Full text of DOI:10.1080/10610270903304434

Supramolecular Chemistry
Vol. 22, No. 2, February 2010, 135–141
Bis-amidopyrrolyl receptors based on anthracene and carbazole
Dustin E. Gross, Vinay Mikkilineni, Vincent M. Lynch and Jonathan L. Sessler*
Department of Chemistry and Biochemistry, Institute for Cellular and Molecular Biology, The University of Texas, 1 University
Station-A5300, Austin, TX 78712-0165, USA
(Received 24 July 2009; final version received 30 August 2009)
A new set of diamide receptors containing anthracene and carbazole bridging subunits and either pyrrole or phenyl
substituents were synthesised. The four systems produced in this way were shown to bind representative anions in DMSO-d6
solution and in the solid state. A higher relative affinity for two test oxoanions, namely dihydrogen phosphate and benzoate,
over chloride anion was seen in solution, with the anions in question being studied in the form of their respective
tetrabutylammonium salts. However, the specifics of the anion recognition process were seen to depend on structure, with
the pyrrole-containing systems displaying higher relative affinities than their corresponding phenyl-containing congeners,
and the carbazole receptors proving more effective than the anthracene analogues. Such observations provide support for the
notion that both the carbazole NH and the pyrrolic NH protons play an important role in stabilising the receptor-bound
anions in solution. Structural analyses of several anion complexes of the diamidopyrrole carbazole receptor reveal that this is
not necessarily the case in the solid state; specifically, the pyrrole NH protons are seen to interact with the amide oxygen of
another molecule. The net result is an extended one-dimensional coordination polymer.
Keywords: supramolecular chemistry; anion recognition; carbazole; pyrrole; amides
Considerable effort has been devoted to the synthesis and
studies of new open-chain anion receptors in recent years
(1–3). Many of these receptors, including several of our
own (4), have taken advantage of the basic pyridine
biscarboxamide strategy first pioneered by Crabtree (5, 6),
and then exploited so effectively by a number of research
groups (7–14). Noteworthy in this context are the
contributions of Gale and co-workers who have exten-
sively studied 2,5-diamidopyrrole-based receptors (15).
Separate from this carbazole and indole, ‘pyrrole-like’
binding motifs have emerged recently as a new scaffold
(16) for the construction of various anion receptors
(17–34). Jurczak and co-workers (18) introduced
diaminocarbazoles, such as 1,8-diamino-3,6-dichlorocar-
bazole, as promising building blocks for preparing various
diamide anion receptors, which in separate work were
further elaborated to incorporate a diazo chromophore
(20). In this report, we detail the combination of pyrrole
amides with carbazole to produce the bisamidopyrrole
carbazole derivative 1, and show that it acts as a new anion
receptor. Also included in this study is a description of the
synthesis and anion recognition behaviour of the
bisamidobenzene derivative 2, as well as the bisamido-
pyrrole anthracene receptor 3 and its phenyl derivative 4
(Scheme 1). This series provides a congruent set of
analogues that contain binding pockets of similar
geometry and size but which provide a varying number
of NH-bond donors. All systems of this study were found
to display good selectivity for test carboxylate and
phosphate anions relative to chloride anion; however, the
absolute and relative binding affinities were found to vary
with the specific structure.
Amidocarbazole receptors 1 and 2 were synthesised
via condensation of the key precursor 1,8-diamino-3,
6-dibutylcarbazole 5 with excess pyrrolyl chloride and
benzoyl chloride, respectively (Scheme 2). Diamine 5 was
synthesised in four steps from carbazole. First, acylation
using butyryl chloride in 1,2-dichloroethane afforded
3,6-dibutyrylcarbazole 6 in an unoptimised yield of 42%.
Subsequent reduction afforded dibutylcarbazole 7 in 50%
yield. Nitration in acetic acid and acetic anhydride provided
the dinitro compound 8 along with minor amounts of the
mononitro derivative, which could be separated by tedious
column chromatography. Finally, palladium-catalysed
hydrogenation of 8 led to diamine 5. It was subsequently
found that the mixture of mono- and dinitro products could
be subjected to hydrogenation conditions to yield 5
containing minor quantities of monoamine 9. Since this
latter mixture could be readily separated using column
chromatography, we currently favour this alternative
sequence. The resulting diamine was then reacted with
the appropriate acid chloride to yield receptors 1,8-
di(pyrrolylamido)-3,6-dibutylcarbazole 1 and 1,8-di(ben-
zoylamido)-3,6-dibutylcarbazole 2. Receptors 1 and 2 were
characterised by single-crystal X-ray diffraction and the
resulting structures are shown in Figure 1.
*Corresponding author. Email: sessler@mail.utexas.edu
ISSN 1061-0278 print/ISSN 1029-0478 online
q 2010 Taylor & Francis
DOI: 10.1080/10610270903304434
http://www.informaworld.com

136
D.E. Gross et al.
(benzoate and dihydrogen phosphate), at least in DMSO-
d6 solution.
The carbazole-containing receptors 1 and 2 displayed
binding trends similar to those seen for anthracene
receptors; however, the binding affinities were generally
greater in the case of the oxoanions and reduced in the case
of chloride. In the case of 1 vs. 2, the effect of switching
from pyrrole to phenyl substitution on the Ka values was
not as great as for 3 and 4. For instance, when the pyrrole
groups were replaced with benzene (i.e. passing from 1 to
2), the affinity for benzoate was reduced by a factor of c.2
(Ka ¼ 1600 vs. 790 M21), whereas the corresponding
reduction in the Ka for phosphate was even less
(Ka ¼ 2000 vs. 1400 M21). In addition, receptor 1
displayed a reduced selectivity for dihydrogen phosphate
over benzoate than did receptor 3. Nevertheless, it is
important to underscore that for both 1 and 2, dihydrogen
phosphate proved to be the most strongly bound of the
three test anions considered in this study.
The trends seen in the case of the diamide receptors
1–4 are not reproduced completely in the case of the
monoamidopyrrolyl-functionalised receptor 10. This
control system showed an increased affinity for chloride
compared to receptor 1, as well as a decreased affinity for
the two test oxoanions. This relative increase in chloride
affinity may reflect the more open binding pocket present
in receptor 10 relative to the more constrained system 1,
which is expected to be characterised by a less flexible
anion binding cavity.
Scheme 1. Compounds considered in this study.
Additionally, the isolated monoamine product 9 was
reacted with pyrrole-2-carboxylic acid chloride to yield 1-
pyrrolylamido-3,6-dibutylcarbazole 10. Receptors 3 and 4
were synthesised by the reaction of 1,9-diaminoanthracene
(35) with excess pyrrole-2-carboxylic acid chloride and
benzoyl chloride, respectively.
NMR spectroscopic analyses were used to quantify the
interaction of receptors 1–4 and anions. For these studies,
DMSO-d6 was chosen as the solvent due to the poor
solubility of the anthracene derivatives in other aprotic
media. The anions were used in the form of their respective
tetrabutylammonium salts.
X-ray quality crystals of 1·acetate (Figure 2) and
1·chloride (Figure 3) were obtained by the slow
evaporation of ethyl acetate solutions containing 1 with
excess tetrabutylammonium fluoride (a species that may
have promoted the hydrolysis of ethyl acetate and
production of the acetate anion) and chloride, respectively.
As evidenced by the crystal structure, the receptor binds
these two anions in a 1:1 stoichiometry. However,
interestingly, the pyrrolic NH protons do not participate
in anion binding in the solid state. Instead, these protons
are involved in the formation of a hydrogen-bonded
network with the amide oxygen of another molecule of 1
(see Figures 2 and 3). This results in a one-dimensional
coordination polymer, a geometric motif that was noted
rather early in the study of pyrrole amide compounds (36).
However, in contrast with at least some of the antecedent
pyrrole amide systems recorded in the literature, we do not
believe that the X-ray structures of 1·acetate and 1·chloride
are representative of the binding mode operative in DMSO-
d6 solution for these or other typical anions. This
conclusion is based on the fact that demonstrable downfield
shifts in the pyrrolic NH proton resonance are seen for
benzoate and dihydrogen phosphate (0.34 and 1.67 ppm,
respectively).
Receptor 3 was found to bind chloride anion weakly,
but bind the two test oxoanions of this study, namely
benzoate and dihydrogen phosphate, with greater affinity
(see Table 1). In the case of dihydrogen phosphate, the
measured Ka proved to be 2600 M21, a value that was
almost 10 times larger than that of benzoate. This
phosphate-over-benzoate (and chloride) selectivity was
reduced when the pyrroles were replaced by phenyl
groups, i.e. in the case of 4; here, lower affinities were seen
across the board, with dihydrogen phosphate displaying a
Ka that was approximately twice that of chloride, whereas
the latter was bound with essentially the same affinity as
that of benzoate within error. On this basis, we conclude
that replacing the more acidic pyrrolic NH proton by a CH
proton serves to reduce not just the affinity (the Ka of
dihydrogen phosphate was reduced from 2600 to 160 M21
)
but the anion selectivity as well. This leads us to propose
that the presence of the pyrrolic NH is important in
stabilising the bound form of the two test oxoanions
In conclusion, a set of new amidopyrrole and
amidophenyl receptors based on anthracene and carbazole

Supramolecular Chemistry
137
Scheme 2. Synthesis of receptors 1, 2 and 10
were synthesised and shown to bind anions in DMSO-d6
solution and in the solid state. These receptors demonstrate
a higher relative affinity for oxoanions over chloride anion
in solution. An analysis of the specific Ka values, which are
Table 1. Association constants (Ka’s) for receptors 1–4 and 10
with selected anions in DMSO-d6.a
1
2
3
4
10
Chloride
Benzoate
Dihydrogen phosphate
,50
1600
2000
,50
790
1400
80
310
2600
83
65
160
280
190
880
a Ka’s in units of M21; anions used in the form of their tetrabutylammo-
nium salts; host concentration, 4–5 mM.
Figure 1. Ball and stick representation of single-crystal X-ray
diffraction structures for 1 (left) and 2 (right).

138
D.E. Gross et al.
Figure 2. Single-crystal X-ray diffraction structure of 1·OAc;
most hydrogen atoms and the tetrabutylammonium cation have
been removed for clarity.
Figure 3. Single-crystal X-ray diffraction structure of 1·Cl;
most hydrogen atoms and the tetrabutylammonium cation have
been removed for clarity.
seen to vary with structure, provides support for the notion
that the carbazole NH and pyrrolic NH protons play an
important role in stabilising the receptor-bound anions in
the solution. However, in the case of the carbazole-based
receptor, the ‘loss’ of the pyrrolic NH protons (i.e. moving
from 1 to 2) does not affect the affinity for dihydrogen
phosphate all that significantly, a result that serves to make
receptor 2, where phenyl subunits replace the pyrroles,
more selective than its pyrrole-containing congener, 1.
Nevertheless, as would be expected for a system
containing a greater number of available NH donor
groups, this latter system (i.e. 1) actually displays a
higher for-anion affinity than 2. Similar overall anion
affinity effects were also seen in the case of 3 vs. 4.
In contrast, the monoamide control, 10, displays a
different selectivity pattern than is seen for any of the
bisamides 1–4.
R1 ¼ 0.1205, wR2 ¼ 0.2284, R indices (all data):
R1 ¼ 0.2027, wR2 ¼ 0.2655.
Crystal data for 2 CCDC 736625 C34H35N3O2,
Mr ¼ 517.65, T ¼ 153(2) K, triclinic, space group ¼ P-1,
˚
a ¼ 9.5944(8), b ¼ 9.9023(10), c ¼ 14.8310(15) A, b ¼
3
99.086(4)8, V ¼ 1385.6(2) A , rcalc ¼ 1.241 Mg/m3,
˚
m ¼ 0.077 mm21, Z ¼ 2, reflections collected: 9412,
independent reflections: 6133 (Rint ¼ 0.0448), final R
indices [I . 2sI]: R1 ¼ 0.0687, wR2 ¼ 0.1134, R indices
(all data): R1 ¼ 0.1576, wR2 ¼ 0.1433.
Crystal data for 1·OAc CCDC 736626 C48H72N6O4,
Mr ¼ 797.12, T ¼ 153(2) K, triclinic, space group ¼ P-1,
˚
a ¼ 8.8867(6), b ¼ 15.0233(10), c ¼ 17.1840(12) A,
3
b ¼ 87.019(3)8, V ¼ 2236.5(3) A , rcalc ¼ 1.184 Mg/m3,
˚
m ¼ 0.076 mm21, Z ¼ 2, reflections collected: 15,930,
independent reflections: 9967 (Rint ¼ 0.0527), final R
indices [I . 2sI]: R1 ¼ 0.0830, wR2 ¼ 0.1450, R indices
(all data): R1 ¼ 0.1952, wR2 ¼ 0.1815.
Crystal data for 1·Cl CCDC 736627 C46H69ClN6O2,
Mr ¼ 773.52, T ¼ 153(2) K, triclinic, space group ¼ P-1,
Experimental
1H NMR spectroscopic titrations
˚
a ¼ 12.6727(3), b ¼ 14.9621(6), c ¼ 25.2379(12) A,
3
b ¼ 75.550(2)8, V ¼ 4493.5(3) A , rcalc ¼ 1.143 Mg/m3,
A Varian Mercury 400 MHz NMR spectrometer was used
1
to measure the H NMR shifts of the NH proton of the
˚
m ¼ 0.128 mm21, Z ¼ 4, reflections collected: 30,522,
independent reflections: 20,063 (Rint ¼ 0.0383), final R
indices [I . 2sI]: R1 ¼ 0.0717, wR2 ¼ 0.1340, R indices
(all data): R1 ¼ 0.1645, wR2 ¼ 0.1742. Portions of two
n-butyl groups were disordered. One group was on a host
molecule and the other was on a cation. The disorder was
modelled separately but in the same manner for both groups.
The site occupancy factor for one component of the
disordered group was assigned the variable x, while the site
occupancy factor for the other component was assigned
(1 2 x). A common isotropic displacement parameter was
refined for the methylene atoms and a second isotropic
displacement parameter was refined for the methyl carbon
atoms. The geometry of the two groups was restrained to be
equivalent throughout the refinement. In this way, the site
occupancy for the major component of the disorder on the
host molecule refined to 55(2)%. The site occupancy factor
amides. Solutions of 1–4 and 10 were titrated with
tetrabutylammonium salts of chloride, dihydrogen phos-
phate and benzoate salt at 258C in DMSO-d6. The titration
data were plotted as D ppm vs. concentration of the guest
and fit to a 1:1 binding equation developed by Wilcox (37),
using the nonlinear curve-fitting procedure available in the
Origin software package.
X-ray crystallographic data
Crystal datafor1CCDC736624C30H33N5O2, Mr ¼ 495.61,
T ¼ 153(2) K, monoclinic, space group ¼ P21/c,
˚
a ¼ 21.3540(4), b ¼ 12.9300(5), c ¼ 9.1350(9) A,
3
b ¼ 95.084(2)8, V ¼ 2512.3(3) A , rcalc ¼ 1.310 Mg/m3,
˚
m ¼ 0.084 mm21, Z ¼ 4, reflections collected: 7850,
independent reflections: 7852, final R indices [I . 2sI]:

Supramolecular Chemistry
139
for the major component of the cation refined to 65(2)%. The
atoms of the disordered groups were refined anisotropically
with their displacement parameters restrained to be
approximately isotropic.
758C for 1 h and 1008C for 1 h. After cooling, the solvent
was evaporated off under reduced pressure, and the
product was purified via column chromatography over
silica gel using CH2Cl2 as the eluent; this yielded 3,6-
dibutyl-1,8-dinitrocarbazole 7 in 55% yield. 1H NMR
(400 MHz; CDCl3) d 11.20 (bs, 1H), 8.24 (s, 2H), 8.22 (s,
2H), 2.88 (t, J ¼ 7.6 Hz, 4H), 1.74 (m, J ¼ 7.6 Hz, 4H),
1.43 (m, J ¼ 7.5 Hz, 4H), 0.98 (t, J ¼ 7.4 Hz, 6H). 13C
NMR (100 MHz; CDCl3) d 135.9 (CH), 132.5 (CH), 132.3
(CH), 127.5 (CH), 125.9 (CH), 123.3 (CH), 35.2 (CH2),
33.9 (CH2), 22.2 (CH2), 13.9 (CH3). HRMS (ESI) calcd
for C20H22N3O4 [M2H]2: 368.1609, found: 368.1616.
3,6-Dibutyrylcarbazole (6)
To a mixture of carbazole (30 g, 0.179 mol) and aluminium
chloride (53 g) in 1,2-dichloroethane (500 ml), butyryl
chloride (43 ml) was added slowly. The reaction was then
stirred at 658C for 5 h and then quenched with water and
aqueous HCl solution. The organic solvents were removed
under reduced pressure, and the residue was dissolved in
warm chloroform and subsequently crystallised upon
cooling. This afforded 4 in the form of colourless crystals
in 42% yield. 1H NMR (400 MHz; CDCl3) d 8.79 (d,
J ¼ 1.6 Hz, 2H), 8.68 (bs, 1H), 8.15 (dd, J ¼ 1.6 Hz,
J ¼ 8.4 Hz, 2H), 7.49 (d, J ¼ 8.4 Hz, 2H), 3.11 (t,
J ¼ 7.4 Hz, 4H), 1.86 (m, J ¼ 7.4 Hz, 4H), 1.07 (t,
J ¼ 7.4 Hz, 6H). 13C NMR (400 MHz; CDCl3) d 199.9
(CvO), 142.7 (CH), 130.1 (CH), 127.0 (CH), 123.3 (CH),
121.6 (CH), 110.8 (CH), 40.5 (CH2), 18.2 (CH2), 14.0
(CH3). HRMS (ESI) calcd for C20H20NO2 [M2H]2:
306.1493, found: 306.1500.
1,8-Diamino-3,6-dibutylcarbazole (5)
To a solution of 3,6-dibutyl-1,8-dinitrocarbazole (200 mg,
0.54 mmol) in acetonitrile (200 ml), 10% palladium on
carbon was added. The air in the flask was evacuated, and
the reaction was exposed to H2. The reaction was allowed
to proceed overnight and the yellow solution turned black.
The resulting solution was filtered through celite and
the solvent was evaporated off under reduced pressure.
The crude product obtained in this way was purified via
column chromatography over silica gel using 1–2%
MeOH in CH2Cl2 as the eluent. This gave 8 in 79% yield
1
(132 mg). H NMR (400 MHz; CDCl3) d 7.87 (bs, 1H),
3,6-Dibutylcarbazole (7)
7.33 (s, 2H), 6.13 (d, J ¼ 1.2 Hz, 2H), 3.13 (bs, 4H), 2.69
(t, J ¼ 7.6 Hz, 4H), 1.66 (m, J ¼ 7.6 Hz, 4H), 1.38 (m,
J ¼ 7.5 Hz, 4H), 0.94 (t, J ¼ 7.4 Hz, 6H). 13C NMR
(100 MHz; CDCl3) d 134.7 (CH), 130.1 (CH), 129.2 (CH),
124.7 (CH), 113.3 (CH), 111.67 (CH), 35.7 (CH2), 34.4
(CH2), 22.4 (CH2), 14.0 (CH3). HRMS (ESI) calcd for
C20H28N3 [M þ H]þ: 310.2284, found: 310.2277.
Zinc (200 g) and mercuric chloride (20 g) were added to
400 ml water containing concentrated hydrochloric acid
(26 ml). After stirring for 20 min, additional concentrated
hydrochloric acid was added slowly (400 ml), followed
by 3,6-dibutyrylcarbazole (16 g, 52 mmol). Toluene
(200 ml) was added to the reaction mixture, which was
then heated at reflux for 96 h. The toluene layer was
separated off and all volatiles were removed under
reduced pressure. The resulting light brown solid was
purified by column chromatography over silica gel using
2:1 hexanes/DCM as the eluent; this produced 5 in a yield
1-Amino-3,6-dibutylcarbazole (9)
1-Nitro-3,6-dibutylcarbazole (side product from nitration
of 5) was dissolved in acetonitrile and 10% palladium on
carbon was added. The air in the flask was evacuated, and
the reaction was exposed to H2. The reaction was allowed
to proceed overnight and the yellow solution turned black.
The solution was filtered through celite and the solvent
was evaporated off under reduced pressure. 1H NMR
(400 MHz; CDCl3) d 7.8 (s, 1H), 7.71 (bs, 1H), 7.39 (s,
1H), 7.30 (d, J ¼ 8.4 Hz, 1H), 7.19 (dd, J ¼ 8.0 Hz,
J ¼ 1.4 Hz, 1H), 6.63 (s, 1H), 3.16 (bs 2H), 2.76 (t,
J ¼ 7.6 Hz 2H), 7.69 (t, J ¼ 7.6 Hz 2H), 1.68 (m, 4H),
1.40 (m, 4H), 0.95 (m, 6H). 13C NMR (90 MHz; CDCl3) d
138.5 (CH), 135.0 (CH), 134.0 (CH), 129.9 (CH), 129.0
(CH), 126.3 (CH), 124.5 (CH), 124.3 (CH), 119.7 (CH),
113.6 (CH), 111.5 (CH), 110.7 (CH), 35.8 (CH2), 35.7
(CH2), 34.5 (CH2), 34.4 (CH2), 22.4 (CH2), 22.4 (CH2),
14.1 (CH3), 14.1 (CH3). HRMS (ESI) calcd for C20H27N2
[M þ H]þ: 295.2171, found: 295.2169.
1
of 50%. H NMR (400 MHz; CDCl3) d 7.89 (s, 2H), 7.77
(bs, 1H), 7.28 (dd, J ¼ 8 Hz and 0.4 Hz, 2H), 7.24 (dd,
J ¼ 8 Hz and 1.2 Hz), 2.81 (t, J ¼ 7.8 Hz, 4H), 1.74 (m,
J ¼ 7.6 Hz, 4H), 1.44 (m, J ¼ 7.5 Hz, 4H), 1.00 (t,
J ¼ 7.4 Hz, 6H). 13C NMR (400 MHz; CDCl3) d 138.2
(CH), 133.7 (CH), 126.4 (CH), 123.3 (CH), 119.5 (CH),
110.2 (CH), 35.7 (CH2), 34.5 (CH2), 22.4 (CH2), 14.0
(CH3). HRMS (ESI) calcd for C20H24N [M2H]2:
278.1912, found: 278.1914.
3,6-Dibutyl-1,8-dinitrocarbazole (8)
3,6-Dibutylcarbazole (204 mg, 0.7 mmol) was dissolved
in acetic anhydride (25 ml) and acetic acid (10 ml). Nitric
acid (0.19 ml, 4.5 mmol) was added dropwise.
The resulting solution was then heated at 658C for 2 h,

140
D.E. Gross et al.
1,8-Diamidopyrrolyl-3,6-dibutylcarbazole (1)
1,9-Diamidopyrrolylanthracene (3)
A solution of 1,8-diamino-3,6-dibutylcarbazole (500 mg,
1.62 mmol) and pyrrolyl chloride (800 mg) in CH2Cl2 was
stirred overnight. The solvent was evaporated and the
product was purified via column chromatography with 1%
MeOH in CH2Cl2. The product was precipitated from
1,9-Diaminoanthracene (35) (710 mg, 3.4 mmol) and
pyrrole-2-carboxylic acid chloride (1.4 g) were dissolved
in CH2Cl2 (40 ml). The resulting mixture was stirred for
15 h and then quenched with methanol (40 ml). All volatile
solvents were removed under vacuum, yielding a green
solid. The solid was washed with consecutive aliquots of
methanol and water to yield a light green solid, which was
1
CH2Cl2 in 78% yield. H NMR (400 MHz; DMSO-d6) d
11.73 (bs, 2H), 10.20 (bs, 1H), 9.92 (bs, 2H), 7.77 (s, 2H),
7.44 (s, 2H), 7.15 (s, 2H), 7.00 (s, 2H), 6.22 (d, J ¼ 3.2 Hz,
2H), 2.76 (t, J ¼ 7.4 Hz, 4H), 1.68 (m, J ¼ 7.2 Hz, 4H),
1.39 (m, J ¼ 7.5 Hz, 4H), 0.95 (t, J ¼ 7.0 Hz, 6H). 13C
NMR (100 MHz; DMSO-d6) d 158.3 (CvO), 132.8 (CH),
131.7 (CH), 126.0 (CH), 124.3 (CH), 122.46 (CH), 122.43
(CH), 120.7 (CH), 115.9 (CH), 111.7 (CH), 108.9 (CH),
34.9 (CH2), 33.8 (CH2), 21.8 (CH2), 13.9 (CH3). HRMS
(ESI) calcd for C30H33N5O2Na [M þ Na]þ: 518.2538,
found: 518.2527.
1
dried under vacuum to afford product 3 in 71% yield. H
NMR (500 MHz; DMSO-d6) d 11.70 (bs, 2H), 10.04 (s,
2H), 9.00 (s, 1H), 8.64 (s, 1H), 7.96 (d, J ¼ 6.8 Hz, 2H),
7.81 (d, J ¼ 5.6 Hz, 2H), 7.56 (dd, J ¼ 6.8 Hz and
J ¼ 1.2 Hz, 2H), 7.21 (m, 2H), 6.99 (m, 2H), 6.19 (m,
2H). 13C NMR (125 MHz; DMSO-d6) d 159.8 (CvO),
133.5 (CH), 131.8 (CH), 126.6 (CH), 126.4 (CH), 126.1
(CH), 125.5 (CH), 125.0 (CH), 122.4 (CH), 121.2 (CH),
117.1 (CH), 111.8 (CH), 108.9 (CH). HRMS (ESI) calcd
for C24H19N4O2 [M þ H]þ: 395.1509, found: 395.1503;
calcd for C24H18N4O2Na [M þ Na]þ: 417.1327, found:
417.1322.
1-Amidopyrrolyl-3,6-dibutylcarbazole (10)
A solution of 1-amino-3,6-dibutylcarbazole (90 mg) and
pyrrolyl chloride in CH2Cl2 was stirred overnight. The
solvent was evaporated off and the product was purified
via column chromatography over silica gel, using CH2Cl2
1,9-Diphenylamidoanthracene (4)
1,9-Diaminoanthracene (35) (110 mg, 0.53 mmol), ben-
zoyl chloride (350 ml) and pyridine (200 ml) were
dissolved in CH2Cl2 (25 ml). The resulting mixture was
stirred for 15 h and then quenched with water (50 ml)
causing a white precipitate. The precipitate was collected
by filtration and washed successively with water and
methanol. The resulting white solid was dried under
1
as the eluent (yield 85%). H NMR (400 MHz; CDCl3) d
9.70 (bs, 1H), 9.24 (bs, 1H), 7.90 (s, 1H), 7.84 (s, 1H), 7.75
(s, 1H), 7.25 (d, J ¼ 8.0 Hz, 1H), 7.22 (dd, J ¼ 8.0 Hz,
J ¼ 1.6 Hz, 1H), 6.98 (m, 1H), 6.92 (d, J ¼ 1.2 Hz, 1H),
6.80 (bs, 1H), 6.26 (m, 1H), 2.77 (q, J ¼ 8.0 Hz, 4H), 1.69
(m, 4H), 1.41 (m, 4H), 0.96 (m, 6H). 13C NMR (100 MHz;
CDCl3) d 158.9 (CH), 138.9 (CH), 133.9 (CH), 133.8
(CH), 131.5 (CH), 126.9 (CH), 126.3 (CH), 125.4 (CH),
123.5 (CH), 122.7 (CH), 120.9 (CH), 119.5 (CH), 118.6
(CH), 117.2 (CH), 111.1 (CH), 110.5 (CH), 110.3 (CH),
35.7 (CH2), 35.4 (CH2), 34.5 (CH2), 34.3 (CH2), 22.4
(CH2), 22.4 (CH2), 14.0 (CH3). HRMS (ESI) calcd for
C25H28N3O [M2H]2: 386.2234, found: 386.2238.
1
vacuum to afford 4 in 93% yield. H NMR (500 MHz;
DMSO-d6) d 10.60 (bs, 2H), 8.92 (s, 1H), 8.70 (s, 1H),
8.06–8.01 (m, 6H), 7.70 (d, J ¼ 6.8 Hz, 2H), 7.61–7.57
(m, 4H), 7.41 (t, J ¼ 7.8 Hz, 4H). 13C NMR (125 MHz;
DMSO-d6) d 166.3 (CvO), 134.8 (CH), 133.9 (CH),
131.8 (CH), 131.4 (CH), 128.3 (CH), 127.8 (CH), 127.3
(CH), 126.8 (CH), 126.2 (CH), 125.4 (CH), 122.9 (CH),
117.97 (CH). HRMS (ESI) calcd for C28H19N2O2
[M2H]2: 415.1445, found: 415.1452.
1,8-Diphenylamido-3,6-dibutylcarbazole (2)
Acknowledgements
A solution of 1,8-diamino-3,6-dibutylcarbazole (90 mg,
0.3 mmol) and benzoyl chloride in CH2Cl2 was stirred
overnight. The solvent was evaporated off under reduced
pressure to give the product. 1H NMR (400 MHz; DMSO-
d6) d 10.32 (bs, 3H), 8.02 (d, J ¼ 7.2 Hz, 4H), 7.79 (s, 2H),
7.61–7.51 (m, 8H), 2.74 (t, J ¼ 7.4 Hz, 4H), 1.67 (m,
J ¼ 7.2 Hz, 4H), 1.37 (m, J ¼ 7.5 Hz, 4H), 0.93 (t,
J ¼ 7.0 Hz, 6H). 13C NMR (100 MHz; DMSO-d6) d 165.7
(CH), 134.8 (CH), 132.9 (CH), 132.0 (CH), 131.7 (CH),
128.4 (CH), 128.0 (CH), 124.4 (CH), 122.6 (CH), 121.2
(CH), 116.4 (CH), 35.0 (CH2), 33.9 (CH2), 21.9 (CH2),
13.9 (CH3). HRMS (ESI) calcd for C34H35N3O2Na
[MþNa]þ: 540.2634, found: 540.2622.
This work was supported by the National Institutes of Health
(grant GM 58907 to J.L.S.) and the University of Texas at Austin
(undergraduate fellowship to V.M.L.).
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