First approach to nitrogen-containing fused aromatic hydrocarbons as targets for organoelectronics utilizing a new transformation of O-protected diaryl methanols

Article abstract of DOI:10.1002/chem.200901947

A new concise approach for the construction of heteroatom analogues of polycyclic aromatic benzo[g]- quinoline, benzo[b]carbazole, and pyrido[ b]carbazole systems via diaryl methanols is described. This transformation involves formation of a central benzene ring fused to two aromatic 5- or 6- membered rings of pyrrole and/or pyridine by using a combination of two aromatic aldehydes, of which at least one contains a ring nitrogen. Analysis of the UV and fluorescent properties,

Full text of DOI:10.1002/chem.200901947

DOI: 10.1002/chem.200901947
First Approach to Nitrogen-Containing Fused Aromatic Hydrocarbons as
Targets for Organoelectronics Utilizing a New Transformation of
O-Protected Diaryl Methanols
Piotr Bałczewski,*[a, b] Agnieszka Bodzioch,[a] Ewa Rꢀzycka-Sokołowska,[b]
˙
Bernard Marciniak,[b] and Paweł Uznan´ski[a]
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Chem. Eur. J. 2010, 16, 2392 – 2400

FULL PAPER
Abstract: A new concise approach for
the construction of heteroatom ana-
logues of polycyclic aromatic benzo[g]-
quinoline, benzo[b]carbazole, and pyri-
do[b]carbazole systems via diaryl meth-
anols is described. This transformation
involves formation of a central benzene
ring fused to two aromatic 5- or 6-
membered rings of pyrrole and/or pyri-
dine by using a combination of two ar-
omatic aldehydes, of which at least one
contains a ring nitrogen. Analysis of
the UV and fluorescent properties,
Stokes shifts, quantum yields in solu-
tion, and p-stacking interactions in the
crystal structures of the new materials
was performed. These polycyclic aro-
matic compounds show potential as
small-molecule organoelectronic mate-
rials.
Keywords: aromatic substitution ·
cyclization · energy conversion ·
fluorescence · synthetic methods
Introduction
structing linearly fused polyACTHNGUTERNNU(G hetero)aromatic systems I–III is
based on the formation of the central six-membered aromat-
ic ring from two existing ArI and ArII rings of independent
aromatic aldehydes.[14] For first time we apply our recently
discovered reaction, in which the corresponding O-benzyl-
protected diaryl methanol is transformed directly into elec-
tron-rich hexahydroxylated anthracene system IV by a mul-
tistage mechanism in a one-pot procedure under acidic con-
ditions.[15]
Over the past few years, nitrogen-containing fused aromatic
systems have been a subject of interest in several areas,
from biologically active substances[1–3] to new materials in
organoelectronics.[4–7] For instance, carbazole-containing
molecules, such as indoloACTHUNRGTNE[NUG 3,2-b]carbazoles, have been widely
used as materials for constructing high-mobility organic
field-effect transistors (OFETs),[8] the main logic units in
electronic circuits, in which they usually function as either
switches or amplifiers. Bisindenocarbazoles[9] were used in
construction of organic light-emitting diodes (OLEDs),[10]
whereas 2,2’-bispyridyl derivatives found application in lu-
minescent solar concentrators (LSCs). Due to these interest-
ing properties, a number of synthetic approaches to benzo-
carbazole,[11] benzoquinoline,[5] pyridocarbazole,[6] and other
carbazole systems[7] have been described. Progress in the
area of small molecules for organic electronic devices has
also been recently reviewed.[12,13]
Results and Discussion
In the synthesis of benzoquinoline derivative 5, as an exam-
ple of system I, key derivative 4 was obtained from o-bro-
moaldehyde 1 (Scheme 1). In contrast to literature reports
Scheme 1. Synthesis of benzoquinoline derivative 5. Conditions:
i) HOCH2CH2OH/4-MeC6H4SO3H (cat.), benzene, reflux, 4h, 94%; ii) n-
Herein, we demonstrate novel, concise, and low-cost syn-
theses of three nitrogen-containing systems I–III, which
have potential applications as materials in organic electron-
ics. These new systems contain nitrogen atoms in their ArI
and/or ArII aromatic rings. The present approach to con-
BuLi, ꢀ788C, 10 min, THF followed by 3,4,5-C6H (OMe)3CHO, ꢀ78!
2A
(24 h, toluene, 90% yield, cat. p-TsOH),[16,17] the use of cata-
lytic amounts of p-TsOH to protect the aldehyde group in 1
with ethylene glycol in our system gave only trace amounts
of 2 after 17 h. The use of 0.5 equivalents of the acidic cata-
lyst was sufficient to complete the reaction within only 4 h
in benzene, in very good 92% yield. A Br/Li exchange reac-
tion with nBuLi followed by condensation with 3,4,5-trime-
thoxybenzaldehyde afforded diaryl methanol 3 in 69%
yield. Further protection of the OH group in 3 with benzyl
bromide gave 4 in 83% yield. An attempt to transform 4
into 5 in methanol (HCl, 15 equiv, 1n) resulted in deprotec-
tion of the 1,3-dioxolane function to give the free aldehyde
´
[a] Prof. P. Bałczewski, A. Bodzioch, Dr. P. Uznanski
Department of Heteroorganic Chemistry
Department of Engineering of Polymer Materials
Center of Molecular and Macromolecular Studies
Polish Academy of Sciences
´
Sienkiewicza 112, 90-363 Łꢁdz (Poland)
Fax : (+48)426847126
E-mail: pbalczew@bilbo.cbmm.lodz.pl
[b] Prof. P. Bałczewski, Dr. E. Rꢁz˙ycka-Sokołowska, Dr. B. Marciniak
Institute of Chemistry and Environmental Protection
Jan Długosz University
Armii Krajowej 13/15, 42-200 Cze˛stochowa (Poland)
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P. Bałczewski et al.
group, and afforded only 5% of desired product 5 after
72 h. When methanol was replaced with acetone, compound
5 was obtained in 27% yield after 72 h, accompanied by
substrate 4 (44% yield). Finally, the use of a large excess
(30 equiv) of 1n HCl and extention of the reaction time to
5 d gave 5 in a satisfactory and reproducible yield of 53%
(Table 1).
In the approach to nitrogen-containing fused aromatics of
type II (Scheme 2), we synthesized the unknown 1,3-dioxa-
benzocarbazole system 9 by starting from diaryl methanol 7,
which was obtained in 66% yield from two independent ar-
omatic aldehydes, that is, protected 6-bromopiperonal 6 and
N-methylindole-2-carboxaldehyde. After further protection
of the OH group in diaryl methanol 7 with benzyl bromide,
obtained derivative 8 underwent cyclization to give new
system 9 under acidic conditions in methanol, with almost
100% purity (Table 1). Replacing methanol with acetone
ensured better solubility of 8 and allowed the reaction time
Scheme 2. Synthesis of benzocarbazole derivative 9. Conditions: i) nBuLi,
ꢀ788C, 10 min, THF followed by N-methylindole-2-carboxaldehyde,
ꢀ78!08C, 66%; ii) NaH, RT, 30 min, THF followed by C6H5CH2Br
(1.5 equiv), KI (5%), 18h, RT, 79%; iii) 1n HCl, acetone, 30 min, RT,
99%.
to be shortened from 24 h to 0.5 h. Moreover, the use of
other acidic reagents, such as p-TsOH, Lewis acids (ZnCl2
or SnCl2·2H2O), or strong acidic ion-exchange resins (Am-
berlite IR 120, Amberlyst 15), also afforded carbazole 9 in
almost quantitative yields (Table 2)
Table 1. Structures of final products 5, 9, 12, and 13 obtained by acidic trans-
formation of diaryl methanols.
Table 2. Reaction conditions for the quantitative transformation of 1,3-
dioxolane 8 into 1,3-dioxabenzocarbazole system 9.
Substrates
Intermediates
Final products
Acid
Solvent
t [h]
T
1n HCl
MeOH
acetone
acetone
acetone
acetone
acetone
24
0.5
2
1.5
19
24
RT
RT
RT
RT
RT
RT
Amberlite IR 120
Amberlyst 15
p-TsOH
ZnCl2
SnCl2·2H2O
A combination of two nitrogen-containing aldehydes
(protected 2-bromo-3-pyridinecarboxyaldehyde 2 and N-
methylindole-2-carboxyaldehyde) afforded diaryl methanol
10 in 59% yield. Compound 10 is a key substrate in the syn-
thesis of pyridocarbazole 12 in example system III
(Scheme 3). An attempt to transform O-benzyl-protected
derivative 11 into system 12 in the presence of 1n HCl in
methanol or HF in acetone gave the desired product in of
13 and 18% yield, respectively, after 72 h. With HCl, prod-
uct 12 was accompanied by the starting material, whereas
with HF a complex mixture was observed. When methanol
was replaced with acetone, compound 12 was afforded in
34% yield after the same reaction time (Table 1).
Scheme 3. Synthesis of pyridocarbazole derivative 12. Conditions:
i) nBuLi, ꢀ788C, 10 min, THF followed by N-methylindole-2-carboxalde-
hyde, ꢀ78!08C, 59%; ii) NaH, RT, 30 min, THF followed by
C6H5CH2Br (1.5 equiv), KI (5%), 18h, RT, 99%; iii) 1n HCl, acetone,
3d, RT, 34%.
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Nitrogen-Containing Fused Aromatic Hydrocarbons
FULL PAPER
Attempted synthesis of the bis(benzocarbazole) system by
using two equivalents of 7 and a,a’-dibromo-p-xylene unex-
pectedly afforded 13 in a one-pot reaction catalyzed by
trace amounts of HBr that originated from hydrolysis of the
dibenzyl substrate (Scheme 4, Table 1). Compound 13 can
be used as a benzylating reagent for other diaryl methanols.
Figure 1, there are three such intramolecular bonds, that is,
ꢀ
ꢀ
C18A H18A···O3A (C18A H18A=1.04(2), H18A···O3A=
2.44(2), C18A···O3A=3.027(3) ꢂ; C18A-H18A-O3A=
ꢀ
ꢀ
115(2)8),
H18F···O3B=2.48(2),
C18B H18F···O3B
(C18B H18F=0.93(2),
C18B···O3B=2.999(3) ꢂ;
C18B-
ꢀ
ꢀ
H18F-O3B=115(2)8), and C25A H25A···O3A (C25A
H25A=0.93, H25A···O3A=2.44, C25A···O3A=2.762(2) ꢂ;
C25A-H25A-O3A=1008). The two first bonds generate an
S(6) graph-set motif[18] and the last bond forms a motif with
a graph set of S(5). As mentioned above, there are also two
ꢀ
intermolecular C H···O hydrogen bonds in the crystal struc-
ture; the first one is from the C19A benzyloxy atom of the
molecule at (x, y, z) via H19A to the O2A 1,3-dioxolane
ꢀ
ring atom of the molecule at (1ꢀx, ꢀy, ꢀz) (C19A H19A=
1.04(2), H19A···O2A=2.58(2), C19A···O2A=3.597(3) ꢂ;
C19A-H19A-O2A=168(2)8), which forms the graph-set
dimer centered at (0.5,0,0) (motif d in Figure 2a). The
Scheme 4. Synthesis of benzocarbazole derivative 13. Conditions: i) NaH,
RT, 30 min, THF followed by a,a’-dibromo-p-xylene, 18h, RT, 39%.
ꢀ
second one, that is, the C H···O intermolecular interaction
Molecular and crystal structure of 9: In the structure of 9
there are two symmetry-independent molecules A and B in
the asymmetric unit (Figure 1). The geometric parameters
of these two molecules are similar; the bond lengths are the
same within 3s and the bond angles differ by less than 18. In
each symmetry-independent molecule of 9, the fused carba-
zole and methylenedioxybenzene rings are practically
planar, with the largest deviations from planarity of
ꢀ0.063(3) and 0.240(4) being for atoms C1A and C1B. Ben-
zyloxy atoms O3A and O3B and methyl atoms C18A and
C18B are nearly coplanar with the planes of these rings,
whereas benzyloxy atoms C19A and C19B are more copla-
nar with the planes formed by atoms C20A–C25A and
C20B–C25B, respectively. The dihedral angles between the
plane of benzene ring and the plane formed by the fused
rings are 76.10(7) and 60.57(8)8 in A and B, respectively.
The structure of 9 contains both intra- and intermolecular
ꢀ
weak hydrogen bonds of type C H···O. As can be seen in
Figure 2. a, b) Parts of the crystal structure of 9 showing the intermolecu-
2
ꢀ
lar C H···O hydrogen bonds that form the R2 (18) graph-set dimers
(motif d), and the C(10) chains (motif e). Molecules A and B are depict-
ed by black and grey, respectively. Other interactions: f) Cg1A···Cg1A(i)
;
g) Cg2B···Cg2B(iv); h) Cg4A···Cg1B(iii); i) Cg1B···Cg4A(iii); j) Cg2A···Cg1-
B(iii); k) Cg1B···Cg2A(iii); l) Cg4A···Cg3B(iii); m) Cg3B···Cg4A(iii); p) C21B
ꢀ
H21B···Cg2A(iv)
C21B···Cg2A=3.565(3) ꢂ;
(C21B H21B=0.93,
H21B···Cg2A=2.85,
ꢀ
ꢀ
C21B-H21B-Cg2A=1358);
q) C25B
H25B···Cg1A(iii) (C25B H25B=0.93, H25B···Cg1A=2.89, C25B···Cg1A=
ꢀ
(v)
ꢀ
ꢀ
3.586(3) ꢂ; C25B-H25B-Cg1A=1338); r) C22A H22A···Cg3B (C22A
H22A=0.93, H22A···Cg3B=2.82, C22A···Cg3B=3.582(3) ꢂ; C22A-
H22A-Cg3B=1408). Symmetry codes: (i) ꢀx, ꢀy, ꢀz; (iii) 1ꢀx, ꢀy, 1ꢀz;
(iv) ꢀx, 1ꢀy, 1ꢀz; (v) ꢀx, ꢀy, 1ꢀz. The centroids of the aromatic rings
(Cg; see Figure 1) are denoted by small black spheres. Distances between
the ring centroids lie in the range of 3.835(1)–4.435(2) ꢂ and interplanar
angles lie in the range of 0.00–7.348. Hydrogen atoms not involved in the
interactions have been omitted for clarity.
Figure 1. Views of molecules A (right) and B (left) in the crystal struc-
ture of 9, showing the atom numbering schemes. Displacement ellipsoids
are drawn at the 30% probability level and hydrogen atoms are shown as
small spheres of arbitrary radius. Cg denotes the centroid of the aromatic
rings. The dashed lines depict intramolecular hydrogen bonds that gener-
ate the S(5) and S(6) graph-set motifs.
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P. Bałczewski et al.
between the methyl group (atoms C18B–H18E) of the mole-
cule at (x, y, z) and the 1,3-dioxolane ring (atom O2B) at (x,
1+y, z) generates a C(10) chain running parallel to the
Bearing in mind that the materials that give p stacking in
the solid state are particularly attractive because they often
lead to devices with high charge-carrier mobilities,[19–22] and
taking into account the fact that in the crystal structure of 9
the slipped p-stacking is predominant (similarly to the re-
ꢀ
[010] direction (C18B H18E=0.96(2), H18E···O2B=
2.59(3),
C18B···O2B=3.094(3) ꢂ;
C18B-H18E-O2B=
113(2)8; motif e in Figure 2b).
It is also worth emphasizing that modification of the mo-
lecular structure of the carbazole molecule by replacing one
cently synthesized and crystallized tetraphenylbisACHTUNGTRENNUNG(indolo-
{1,2-a})quinoline,[23] which exhibited field-effect mobilities as
ACHTUNGTRENNUNG
high as 1.0 cm2 Vꢀ1 sꢀ1), we can suppose that this newly syn-
thesized carbazole derivative will turn out to be a promising
material for device applications, particularly in the area of
organic field-effect transistors (OFETs).
Compounds 5, 9, and 12 revealed very interesting photo-
physical properties and spectacular fluorescence (Figure 4).
The absorption spectrum of 5 in chloroform displayed three
broad bands with maxima at l=237, 277, and 365 nm
ꢀ
ꢀ
of the C H and N H protons by benzyloxy and methyl
groups, respectively, results first in transformation of the ar-
rangement of aromatic rings from herringbone in the unsub-
stituted carbazole (Figure 3a) to a more parallel arrange-
Figure 4. Fluorescence of compounds 5, 9, and 12 in solution (CDCl3)
before and after UV exposure.
(emax =2.9ꢃ104 mꢀ1 cmꢀ1, l=277 nm; Figure 5, grey lines).
The spectrum of 9 was more structured and displayed many
distinct spectral features (e=4.2ꢃ104 mꢀ1 cmꢀ1, l=279 nm;
Figure 5, black lines). The excitation spectra matched the
absorption spectra for both compounds (Figures 6 and 7),
which shows that internal conversion from the upper excited
singlet states to the lowest ones proceeded with unit quan-
tum efficiency. Compounds 5 and 9 strongly emit greenish
(lmax. =479 nm) and bluish (lmax. =410 nm) fluorescence with
quantum yields of 0.24 (5) and 0.21 (9). In comparison with
5, compound 12 revealed much more intense green fluores-
cence at lmax =453 nm at the same concentration of 1.5–1.7ꢃ
10ꢀ4 molLꢀ1 in chloroform (Figure 8).
Figure 3. Packing structures of 9 and carbazole in the crystal structures.
a) Herringbone packing diagram of carbazole with a space-filling model.
b) Columnar stacks of 9 with a space-filling model for planar moiety 1
and a ball-and-stick model for the benzyloxy substitutent. All hydrogen
atoms have been omitted for clarity.
ment in 9 (Figure 3b), followed by elimination of intermo-
ꢀ
lecular interactions of type N H···p
(arene) and appearance
ꢀ
of the above-mentioned C H···O interactions. The arrange-
ment results from a lack of the edge-to-face p···p interac-
tions between the aromatic rings of the planar fused moiety
of molecule 9 (moiety 1) and the presence of slipped face-
to-face p···p interactions between them (interactions f–m in
Figure 2a and b). These interactions connect the planar moi-
eties of 1 into columns in which the two adjacent A mole-
cules (and also two adjacent B molecules) are rotated by
1808, whereas the A and B molecules are rotated by about
1108 relative to each other.
Figure 5. UV/Vis absorption (left) and fluorescence emission spectra
(right) of 5 and 9 in chloroform.
Moreover, the benzene rings of sterically demanding ben-
zyloxy substitutents in the structure of 9 are arranged so
ꢀ
that they form edge-to-face C H···p interactions p–r (Fig-
ure 2a and b) with the aromatic rings of moieties 1.
The Stokes shift, defined as the difference between the
spectral positions of the band maxima of the luminescence
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Nitrogen-Containing Fused Aromatic Hydrocarbons
FULL PAPER
The Stokes shift for carbazole derivative 9 amounted to just
n˜ =860 cmꢀ1, whereas pyridine derivative 5 had an excep-
tionally high value of n˜ =4500 cmꢀ1, which indicates that the
ground and fluorescence states might have different geome-
tries. A further contribution to the longer emission wave-
length of 5 might result from its higher electric dipole
moment in the excited state distorting the local dielectric
properties of the solvent. The Stokes shift for 12 also had a
high value of n˜ =3435 cmꢀ1. Both compounds with high
Stokes shifts constitute excellent base materials for further
structure optimization towards luminescent solar concentra-
tors,[24] which require large values for both the Stokes shift
and quantum yield, and which significantly reduce the costs
of photovoltaic power generation by decreasing the required
surface area of expensive silicon photovoltaic cells.
Figure 6. Absorption, fluorescence excitation, and fluorescence emission
spectra of 5 in chloroform (solid lines) and toluene (dotted lines).
Conclusion
We synthesized three nitrogen-containing polycyclic fused
aromatic systems of benzo[g]quinoline, benzo[b]carbazole,
and pyrido[b]carbazole, which are potential small-molecule
organoelectronic materials, by using for the first time a
transformation of O-protected diaryl methanols. In this new
approach to synthesis of linearly fused polycyclic heteroaro-
matics, a newly formed central benzene ring is fused to two
aromatic five- or six-membered rings of pyrrole or pyridine
by using a combination of two independent aromatic alde-
hydes, of which at least one contains a ring nitrogen atom.
Easy access to the latter, a one-pot procedure in the final
step, and the possibility of further extending this reaction to
other heteroaromatic systems constitute undoubted advan-
tages of the new transformation, especially in the context of
the need to develop low-cost manufacturing methods in or-
ganoelectronic materials chemistry.
Figure 7. Absorption, fluorescence excitation, and fluorescence emission
spectra of 9 in chloroform.
Experimental Section
General: The 1H NMR (200 MHz) and 13C NMR (50 MHz) spectra were
recorded by using a Bruker AV 200 spectrometer. The mass spectra of
pure compounds were obtained by using a Finigan Mat 95 spectrometer.
Melting points were determined by using Boetius apparatus. UV/Vis ab-
sorption spectra were obtained by using a Specord S600 diode array spec-
trophotometer with 5 cm cuvettes. RT excitation and emission spectra
were acquired by using a Perkin–Elmer LS50 luminescence spectrometer.
Quantum yields were calculated by using quinine sulfate dihydrate in
0.1n HClO4 as the standard reference material (F=0.59).[25] Column
chromatography was performed on Merck silica gel (F254 60, 270–400
mesh). Organic solvents were purified by standard procedures.
Figure 8. Absorption (left) and fluorescence emission (right) spectra of
12 in chloroform.
and appropriate absorption, is significantly distinct for 5 and
9 (Figures 6 and 7). Generally, 0–0 transitions for nonpolar
and stiff molecules have almost the same energy, but in
many cases they do not correspond to the maxima positions.
The Stokes shift is then larger and increases with solvent po-
larity if a molecule has a larger dipole moment in the excit-
ed state. It also depends upon geometry changes between
the ground and fluorescence states. Figure 6 shows that for
compound 5, the large Stokes shift is not due to a specific
solute–solvent interaction (amine–protic solvent molecule)
but is rather influenced by the above-mentioned factors that
change the population of vibronic states in the molecule.
2-Bromo-3-(1,3-dioxolan-2-yl)pyridine 1: p-TsOH (0.4 g) and ethylene
glycol (0.6 mL) were added to a solution of 2-bromo-3-pyridinecarboxal-
dehyde (1 g, 5.38 mmol) in benzene (50 mL). The resulting mixture was
heated at reflux for 4 h with a Dean–Stark trap for the azeotropic remov-
al of water. After evaporation of the solvent, the residue was diluted
with ethyl acetate (100 mL) and washed with water (50 mL), NaHCO3
(50 mL), and again with water (50 mL). The organic layer was dried
(MgSO4) and then filtered. The solvent was removed under vacuum to
leave colorless needles (yield 92%, 1.14 g). M.p. 50–518C (lit. 49–
508C[16,17]); 1H NMR (C6D6, 200 MHz): d=3.35–3.54 (m, 4H;
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P. Bałczewski et al.
OCH2CH2O), 5.97 (s, 1H; OCHO), 6.50–6.56 (m, 1H; Py-H), 7.55–7.59
(m, 1H; Py-H), 7.94–7.97 ppm (m, 1H; Py-H); 13C NMR (C6D6,
50 MHz): d=66.03 (s, OCH2CH2O), 102.65 (s, OCHO), 123.38 (s, CPy-H),
135.36 (s, CPy-CHOCH2CH2O), 136.92 (s, CPy-H), 143.77 (s, CPy-Br),
151.22 ppm (s, CPy-H); MS (CI, isobutane): m/z: 230 [M+1]+ (79Br)
(100); 232 [M+1]+ (81Br) (98); HRMS (EI, 70 eV): m/z calcd for
C8H8NBrO2: 228.973851; found: 228.973730.
tate and washed with water (3ꢃ20 mL). The organic layer was dried
(MgSO4) and then filtered. The solvent was removed to give the crude
product, which was purified by using column chromatography (hexane/
acetone 2:1).
2-[(Benzyloxy)(3,4,5-trimethoxyphenyl)methyl]-3-(1,3-dioxolan-2-yl)pyri-
dine 4: Yield: 83%, yellow oil. 1H NMR (C6D6, 200 MHz): d=3.33–3.54
(m, 4H; OCH2CH2O), 3.44 (s, 6H; m-ArO
ArOCH3), 4.61 (d, 2J(H,H)=11.82 Hz, 1HA; CHAHBPh), 4.71 (d, 2J-
(H,H)=11.82 Hz, 1HB; CHAHBPh), 6.24 (s, 1H; OCHO), 6.37 (s, 1H;
ACHTUGNTRENUN(GN CH3)2), 3.82 (s, 3H; p-
General procedure for the synthesis of diaryl methanols 3, 7, and 10: 1,3-
Dioxolane 2 or 6 (1 mmol) was dissolved in dry THF (8 mL) at ꢀ788C,
then nBuLi in hexanes (2.3m, 1.1 mmol) was added. The resulting mix-
ture was stirred for 15 min under argon. The corresponding aldehyde
(3,4,5-trimethoxybenzaldehyde or N-methylindole-2-carboxaldehyde;
1.2 mmol) in dry THF (3 mL) was added at ꢀ788C and stirring was con-
tinued for 3 h while the temperature was raised from ꢀ788C to RT. Satu-
rated aqueous NH4Cl was added and the solvent was evaporated. The
residue was diluted with ethyl acetate (50 mL) and washed with water
(3ꢃ20 mL). The organic layer was dried (MgSO4) and then filtered. The
solvent was removed under vacuum to give 3 or 7 as a crude product that
was purified by using column chromatography (n-hexane/ethyl acetate
2:1).
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
CHOBn), 6.70–6.76 (m, 1H; Pyr-H), 7.07 (s, 2H; o-Ar-H), 7.12–7.14 (m,
2H; Ar-H), 7.16 (s, 2H; Ar-H), 7.39–7.46 (m, 1H; Ar-H), 7.86–7.91 (m,
1H; Py-H), 8.48–8.51 ppm (m, 1H; Py-H); 13C NMR (C6D6, 125 MHz):
d=56.44 (s, m-ArACHTNUTRGNEUNG(OCH3)2), 61.09 (s, p-ArOCH3), 65.84 (s, OCH2CH2O),
65.89 (s, OCH2CH2O), 72.18 (s, OCHOH), 83.69 (s, OCH2Ph), 100.89 (s,
OCHO), 106.56 (s, 2ꢃo-CAr-H), 123.34 (s, CPy-H), 128.51 (s, p-Ph), 128.97
(s, m-Ph), 129.22 (s, o-Ph), 133.41 (s, CAr-CHOCH2CH2O), 136.24 (s, CAr
-
CHOBn), 137.13 (s, p-CAr-OCH3), 139.73 (s, ipso-Ph), 139.73 (s, ipso-
CAr), 150.65 (s, CPy-H), 154.76 (s, 2ꢃm-CAr-OCH3), 159.92 ppm (s, CAr
-
CHOBn); MS (CI, isobutane): m/z: 438 [M+1]+ (100); 376
[M+1ꢀHOCH2CH2OH]+ (12); 286 [M+1ꢀPhCH2OH]+ (33); HRMS
(EI, 70 eV): m/z calcd for C25H27NO6: 437.183837; found: 437.184430.
[3-(1,3-Dioxolan-2-yl)pyridin-2-yl](3,4,4-trimethoxyphenyl) methanol 3:
Yield: 69%. M.p.72–748C; 1H NMR (C6D6, 200 MHz): d=3.20–3.45 (m,
5H; OCH2CH2O, OH), 3.35 (s, 6H; m-ArACHTNUTRGEN(UNG OCH3)2), 3.80 (s, 3H; p-
2-{(Benzyloxy)[6-(1,3-dioxolan-2-yl)-1,3-benzodioxol-5-yl]methyl}-1-
methyl-1H-indole 8: Yield: 77%, yellow oil. 1H NMR (C6D6, 200 MHz):
3
ArOCH3), 5.78 (s, 1H; OCHO), 6.43 (s, 1H; CHOH), 6,76 (s, 2H; o-Ar-
d=3.31 (s, 3H; CH3), 3.19–3.55 (m, 4H; OCH2CH2O), 4.45 (d, J
N
3
H), 6.67–6.71 (m, 1H; Py-H), 7.76–7.79 (m, 1H; Py-H), 8.25–8.29 ppm
11.47 Hz, 1H; OCH2Ph), 4.61 (d, JACHTUNTRGNENUG(H,H)=11.47 Hz, 1H; OCH2Ph), 5.32
(m, 1H; Py-H); 13C NMR (C6D6, 50 MHz): d=56.47 (s, m-Ar
ACHTUNGTRENNUNG
(s, 2H; OCH2O), 6.02 (s, 1H; OCHO), 6.15 (s, CH, CHOBn), 6.65 (s,
1H; ArH), 6.38 (s, 1H; ArH), 7.04–7.09 (m, 1H; ArH), 7.12 (s, 1H;
ArH), 7.19–7.31 (m, 4H; ArH), 7.37 (s, 1H; ArH), 7.51 (s, 1H; ArH),
7.57–7.87 ppm (m, 1H; ArH); 13C NMR (C6D6, 50 MHz): d=31.75 (s,
CH3), 64.36 (s, OCH2CH2O), 77.34 (s, CHOBn), 98.21 (s, OCH2Ph),
-
CHOCH2CH2O), 135.52 (s, CPy-H), 139.77 (s, p-CAr-OCH3), 148.91 (s,
CPy-H), 154 (s, 2x m-CAr-OCH3), 160.51 ppm (s, CPy-CHOH); MS (CI, iso-
butane): m/z: 348 [M+1]+ (100); 330 [M+1ꢀH2O]+ (33); 286
[M+1ꢀH2OꢀCH2CH2O]+ (11); HRMS (EI, 70 eV); m/z calcd for
C18H21NO6: 347.136887; found: 347.136830.
101.62 (s, OCH2O), 105.28 (s, OCHO), 109.30 (s, CAr-H), 115.14 (s, CAr
-
H), 120.00 (s, CAr-H), 120.53 (s, CAr-H), 121.49 (s, CAr-H), 124.32 (s, CAr
-
H), 125.44 (s, CAr-H), 126.90 (s, p-Ph), 127.15 (s, m-Ph), 127.70 (s, o-Ph),
129.49 (s, C-CHOCH2CH2O), 138.39 (s, ipso-Ph), 138.57 (s, ipso-CAr),
144.87 (s, CAr-NMe), 147.14 (s, OCH2O-C), 149.01 (s, C-OCH2O),
152.90 ppm (s, CAr-CHOBn); MS (CI, isobutane): m/z: 444 [M+1]+ (56);
336 [M+1ꢀPhCH2OH]+ (100); HR MS (EI, 70 eV): m/z calcd for
C27H25NO5: 443.173273; found: 443.173720.
[6-(1,3-Dioxolan-2-yl)-1,3-benzodioxol-5-yl](1-methyl-1H-indol-2-yl)me-
thanol 7: Yield: 66%. M.p. 137–1398C; 1H NMR (C6D6, 200 MHz): d=
2.64 (d, 3J
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
7.02–7.06 (m, 1H; Ind-H), 7.15–7.27 (m, 2H; Ind-H), 7.72 (s, 1H; Ar-H),
7.63–7.68 ppm (m, 1H; Ind-H); 13C NMR (C6D6, 50 MHz): d=30.51 (s,
CH3), 65.56 (s, OCH2CH2O), 67.17 (s, CHOH), 102.03 (s, OCH2O),
102.55 (s, OCHO), 108.15 (s, CAr-H), 109.48 (s, CAr-H), 109.99 (s, CInd-H),
120.60 (s, CInd-H), 121.94 (s, CInd-H), 122.51 (s, CInd-H), 130.36 (s, C-
CHOCH2CH2O), 136.65 (s, C-CHOH), 139.34 (s, MeN-CAr), 141.95 (s,
CAr–NMe), 148.37 (s, OCH2O-C), 149.53 ppm (s, C-OCH2O); MS (CI,
isobutane): m/z: 354 [M+1]+ (100); 336 [M+1ꢀH2O]+ (73); 292
[M+1ꢀH2OꢀCH2CH2O]+ (30); HRMS (EI, 70 eV): Calcd for
C20H19NO5 353.126323; Found 353.126200.
2-[Benzyloxy-(3-[1,3]dioxolan-2-yl-pyridin-2-yl)-methyl]-1-methyl-1H-
1
indole 11: Yield: 99%, yellow oil. H NMR (C6D6, 200 MHz): d=3.39 (s,
3H; CH3), 3.21–3.54 (m, 4H; OCH2CH2O), 4.46 (d, 3J
ACHTUNGTRENNUNG
1HA; OCHAHBPh), 4.66 (d, 3J
ACHTUNGTRENNUNG
(s, 1H; OCHO), 6.47 (s, CH, CHOBn), 6.54 (s, 1H; ArH), 6.78–6.84 (m,
1H; ArH), 7.06–7.22 (m, 5H; ArH), 7.32–7.36 (m, 2H; ArH), 7.55–7.59
(m, 1H; ArH), 7.99–8.03 (m, 1H; ArH), 8.42–8.45 ppm (m, 1H; ArH);
13C NMR (C6D6, 50 MHz): d=31.05 (s, CH3), 65.83 (s, OCH2CH2O),
65.90 (s, OCH2CH2O), 72.43 (s, CHOBn), 80.18 (s, OCH2Ph), 100.43 (s,
CAr-H), 104.47 (s, OCHO), 110.20 (s, CAr-H), 120.47 (s, CAr-H), 122.03 (s,
CAr-H), 122.81 (s, CAr-H), 123.93 (s, CAr-H), 129.49 (s, CPhH), 134.65 (s, C-
CHOCH2CH2O), 136.78 (s, CAr-H), 138.64 (s, ipso-CAr), 138.19 (s, MeN-
CAr), 139.65 (s, CAr-NMe), 147.14 (s, OCH2O-C), 150.43 (s, CArH),
158.01 ppm (s, CAr-CHOBn); MS (EI, 70 eV): m/z: 400 [M]+ (30); 292
[MꢀPhCH2OH]+ (100); HRMS (EI, 70 eV): m/z calcd for C25H24N2O3:
400.182715; found: 400.17910.
[3-(1,3-Dioxolan-2-yl)pyridin-2-yl](1-methyl-1H-indol-2-yl) methanol 10:
Yield: 59%, yellow oil. H NMR (C6D6, 200 MHz): d=3.08–3.37 (m, 5H;
1
OCH2CH2O, OH), 3.55 (s, 3H; CH3), 5.74 (s, 1H; OCHO), 5.80 (s, 1H;
ArH) 5.89 (s, 1H; CHOH), 6.61–6.76 (m, 2H; ArH), 7.04–7.21 (m, 2H;
ArH), 7.47–7.52 (m, 1H; ArH), 7.77–7.82 (m, 1H; ArH), 8.24–8.27 ppm
(m, 1H; ArH); 13C NMR (C6D6, 50 MHz): d=30.66 (s, CH3), 65.47 (s,
OCH2CH2O), 65.59 (s, OCH2CH2O), 66.49 (s, CHOH), 100.62 (s, CAr-H),
102.12 (s, OCHO), 110.26 (s, CAr-H), 120.53 (s, CAr-H), 121.91 (s, CAr-H),
122.78 (s, CAr-H), 123.46 (s CAr-H,), 132.61 (s, C-CHOCH2CH2O), 135.13
(s, CAr-H), 139.38 (s, MeN-CAr), 141.91 (s, CAr -NMe), 148.59 (s, CAr-H),
158.08 ppm (s, C-CHOH); MS (EI, 70 eV): m/z: 310 [M]+ (85); 292
[MꢀH2O]+ (51); 249 [MꢀOCH2CH2OH]+ (39); HRMS (EI, 70 eV): m/z
calcd for C18H18N2O3: 310.131742; found: 310.132160.
10-(Benzyloxy)-6,7,8-trimethoxybenzo[g]quinoline 5: Diaryl methanol 4
(0.244 g, 0563 mmol) was dissolved in acetone (30 mL), then aqueous
HCl (1n, 17 mL) was added. The mixture was stirred at ambient temper-
ature for 5 d, then extracted with ethyl acetate (50 mL) before the organ-
ic layer was washed with water (20 mL), aqueous NaHCO3 (20 mL), and
again with water (20 mL), then dried (MgSO4). The solvent was removed
and the product was purified by using column chromatography (petro-
leum ether/acetone 2:1) to give the pure product (yield 53%, 0.113 g).
1H NMR (C6D6, 200 MHz): d=3.86 (s, 3H; OCH3), 4.02 (s, 3H; OCH3),
4.13 (s, 3H; OCH3), 5.63 (s, 2H; OCH2Ph), 7.31–7.39 (m, 5H; Ph), 7.57–
7.61 (m, 2H; Ar-H), 8.28–8.34 (m, 2H; Ar-H), 8.98–9.01 ppm (m, 2H;
Ar-H); 13C NMR (C6D6, 50 MHz): d=55.64 (s, OCH3), 61.13 (s, OCH3),
61.34 (s, OCH3), 77.53 (s, OCH2Ph), 96.42 (s, CAr-H), 115.68 (s, CAr-H),
119.72 (s, CAr-H), 125.09 (s, CAr-OMe), 125.36 (s, CAr-OMe), 125.80 (s,
General procedure for the synthesis of O-benzyl-protected diaryl metha-
nols 4, 8, and 11: A solution of the corresponding diaryl methanol 3 or 7
(1 mmol) in THF (5 mL) was added to a suspension of NaH (1.1 mmol,
60% in mineral oil) and KI (0.05 mmol) in dry THF (3 mL) at RT. The
resulting mixture was stirred for 30 min, then benzyl bromide (1.5 mmol)
was added. Stirring was continued for 18 h at the same temperature.
After evaporation of the solvent, the residue was diluted with ethyl ace-
2398
www.chemeurj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 2392 – 2400

Nitrogen-Containing Fused Aromatic Hydrocarbons
FULL PAPER
¯
CAr-OMe), 127.91 (s, p-Ph), 128.35 (s, 2ꢃo-Ph), 128.60 (s, 2ꢃm-Ph),
136.90 (s, CAr-H), 137.55 (s, ipso-Ph), 138.20 (s, C), 141.08 (s, C), 146.72
(s, C), 149.57 (s, C), 149.88 (s, C-H), 153.27 ppm (s, C-OCH2Ph); MS (CI,
isobutane): m/z: 376 [M+1]+ (100); HRMS (EI, 70 eV): m/z calcd for
C23H19NO4: 375.147058; found: 375.145820.
Crystallographic data for 9: C25H19NO3; Mr =418.43; triclinic; P1; a=
11.2834(7), b=11.5421(7), c=17.5873(11) ꢂ; a=71.108(5), b=79.767(5),
g=60.877(6)8; V=1892.6(2) ꢂ3; Z=4; 1calcd =1.339 gcmꢀ3; F
ACTHUNRTGNE(GNU 000)=800;
crystal size 0.33ꢃ0.25ꢃ0.12 mm. Diffraction data were collected at
290(2) K by using an Xcalibur 3 diffractometer equipped with a CCD de-
tector (MoKa radiation, q range 2.38–25.198). The structure was solved by
direct methods and refined by full-matrix least-squares on F2 with
SHELX-97.[26] Carbon, nitrogen, and oxygen atoms were refined aniso-
tropically, all aromatic hydrogen atoms were positioned geometrically
and constrained to ride on their parent atoms with C H distances of
0.93 ꢂ and with Uiso values of 1.2Ueq(C); all other H atoms were located
in difference maps and refined isotropically to give C H distances in the
range 0.92(2)–1.06(2) ꢂ. R=0.040, wR=0.1040, S=1.09 for 4352 unique
reflections with I>2s(I) and 566 parameters.
5-(Benzyloxy)-6-methyl-6H-[1,3]benzodioxoloACTHNUTRGENUG[N 3,2-b]carbazole 9: Diaryl
methanol 8 (0.062 g, 0.140 mmol) was dissolved in acetone (4 mL) and
then aqueous HCl (1n, 2 mL) was added. The mixture was stirred at am-
bient temperature for 0.5 h, then extracted with ethyl acetate (20 mL)
before the organic layer was washed with water (5 mL), aqueous
NaHCO3 (5 mL), and again with water (5 mL), and then dried (MgSO4).
The solvent was removed to give the pure product (yield 98%, 0.052 g).
M.p. 154–1558C; 1H NMR (C6D6, 200 MHz): d=3.59 (s, 3H; CH3), 4.80
(s, 2H; OCH2Ph), 5.39 (s, 2H; OCH2O), 6.99–7.03 (m, 2H; Ar-H), 7.13–
7.22 (m, 4H; Ar-H), 7.24–7.43 (m, 3H; Ar-H), 8.08–8.11 (m, 2H; Ar-H),
7.83 ppm (s, 1H; Ar-H); 1H NMR (CDCl3, 200 MHz): d=4.10 (s, 3H;
CH3), 5.14 (s, 2H; OCH2Ph), 6.05 (s, 2H; OCH2O), 7.24–7.35 (m, 4H;
Ar-H), 7.44–7.62 (m, 7H; Ar-H), 8.11–8.18 ppm (m, 2H; Ar-H);
13C NMR (CDCl3, 50 MHz): d=31.32 (s, CH3), 76.67 (s, OCH2Ph), 96.94
(s, OCH2O), 96.93 (s, CAr-H), 100.87 (s, CAr-H), 104.00 (s, CAr-H), 108.20
(s, CAr-H),113.83 (s, CAr-H), 118.90 (s, CAr-H), 120.32 (s, CAr-H), 122.97 (s,
C), 124.01 (s, C), 125.74 (s, C), 125.74 (s, C), 126.71 (s, CAr-H), 127.59 (s,
2ꢃo-Ph), 128.14 (s, p-C6H5), 128.67 (s, 2ꢃm-C6H4), 131.34 (s, ipso-Ph),
137.08 (s, C), 137.17 (s, C), 143.61 (s, C), 145.76 (s, C), 147.62 ppm (s, C);
MS (CI, isobutane): m/z: 382 [M+1]+ (100); 192 [M+1ꢀCH2Ph]+ (58);
HRMS (EI, 70 eV): m/z calcd for C25H19NO3: 381.136493; found:
381.136260.
ꢀ
ꢀ
CCDC-688739 (9) contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif.
Acknowledgements
Scientific work was financed from the science resources in 2008–2010 as
a research grant (N204 02232/0620). Authors thank Mr. M. Maciejczyk
for carrying out the synthesis of 13 in the framework of his M.Sc. thesis.
11-Benzyloxy-10-methyl-10H-pyridoACTHNUTRGNEUGN[2,3-b]carbazole 12: Diaryl methanol
11 (0.062 g, 0.140 mmol) was dissolved in acetone (3 mL), then aqueous
HCl (1n, 1.5 mL) was added. The mixture was stirred at ambient temper-
ature for 3 d, then extracted with ethyl acetate (20 mL) before the organ-
ic layer was washed with water (5 mL), aqueous NaHCO3 (5 mL), and
again with water (5 mL), and then dried (MgSO4). The solvent was re-
moved and the product was purified by using column chromatography
(petroleum ether/acetone 2:1) to give pure 12 (yield 34%, 0.01 g).
1H NMR (C6D6, 200 MHz): d=3.62 (s, 3H; CH3), 5.69 (s, 2H; OCH2Ph),
6.89–6.95 (m, 2H; ArH), 7.13–7.25 (m, 4H; ArH), 7.36–7.43 (m, 1H;
ArH), 7.61–7.65 (m, 2H; ArH), 7.91–7.96 (m, 1H; ArH), 8.03 (s, 1H;
ArH), 8.05–8.09 (m, 1H; ArH), 8.90–8.94 ppm (m, 1H; ArH); 13C NMR
(C6D6, 50 MHz): d=32.07 (s, CH3), 78.13 (s, OCH2Ph), 102.36 (s, CAr-H),
109.44 (s, CAr-H), 114.32 (s, CAr-H), 118.92 (s, CAr-H), 120.15 (s, CAr-H),
121.84 (s, CAr-H), 123.64 (s, CAr-H), 135.42 (s, C), 137.05 (s, CAr-H),
139.43 (s, CAr-NMe), 145.46 (s, C), 149.30 (s, CArH), 155.75 (s, C),
161.26 ppm (s, C); MS (EI, 70 eV): m/z: 338 [M]+ (30); 247
[MꢀCH2Ph]+ (100); HRMS (EI, 70 eV): m/z calcd for C23H18N2O:
338.141913; found: 338.140810.
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5-[(4-Bromomethyl)benzyloxy]-6-methyl-6H-[1,3]benzodioxoloACTHNUGTRNEUNG[3,2-b]car-
bazole 13: A solution of diaryl methanol 7 (0.666 g, 1.894 mmol) in THF
(7 mL) was added to a suspension of NaH (0.1 g, 4.168 mmol; 60% in
mineral oil) in dry THF (8 mL) at RT. The resulting mixture was stirred
for 30 min, then a,a’-dibromo-p-xylene (0.499 g, 1.894 mmol) was added
and stirring was continued for 18 h at the same temperature. After evap-
oration of the solvent, the residue was diluted with ethyl acetate and
washed with water (3ꢃ20 mL). The organic layer was dried (MgSO4) and
then filtered. The solvent was removed to give the crude product, which
was purified by using column chromatography (petroleum oil/acetone
2:1) to give 13 as a dark solid (yield 39%, 0.148 g). 1H NMR (C6D6,
200 MHz): d=3.56 (s, 3H; N-CH3), 4.01 (s, 2H; CH2Br), 4.72 (s, 2H;
OCH2Ph), 5.38 (s, 2H; OCH2O), 6.82 (s, 1H; Ar-H), 7.01–7.44 (m, 5H;
ArH), 7.81 (s, 1H; Ar-H), 8.10–8.12 ppm (m, 2H; Ar-H); 13C NMR
(CDCl3, 50 MHz): d=31.73 (s, CH3), 76.76 (s, OCH2Ph), 98.05 (s,
OCH2O), 101.67 (s, CArH), 105.30 (s, CArH), 109.31 (s, CArH), 115.21 (s,
CArH), 120.07 (s, CArH), 121.51 (s, CArH); 124.29 (s, CArH), 125.33 (s,
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CArH), 127.13 (s, CArH), 130.18 (s, C), 132.49 (s, C), 138.50 (s, CArH),
144.84 (s, C), 147.16 (s, C); 149.04 ppm (s, CAr); MS (CI, isobutane): m/z:
474 [M
(Br79)+1]+ (5); 476 [M
E
[M+1ꢀBrCH2Ph]+ (30); 292 [M+1ꢀBrCH2PhCH2]+ (100); HRMS (EI,
70 eV): m/z calcd for C26H20NO3Br: 473.062666; found: 473.062320.
Chem. Eur. J. 2010, 16, 2392 – 2400
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
2399

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Published online: February 1, 2010
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