Synthesis and modification of substituted 2-azaanthraquinones

Article abstract of DOI:10.1515/znb-2010-0709

The cycloaddition-ring transformation reaction sequence of pyrido[1,2-a]pyrazines with substituted naphthoquinones furnished a series of new highly substituted azaanthraquinones. Whereas monosubstituted naphthoquinones were normally leading to two regioisomeric products, in some cases a preference for only one regioisomer was observed. The amino derivative 3b which was isolated as the main product proved to be suitable for further modifications at the primary amino group. The derivatives obtained possess groups capable of connecting the molecule with other substructures for applications as functional dyes. The newly synthesized azaquinones show strong and very broad absorptions between 400 and 600 nm in their UV/Vis spectra.

Full text of DOI:10.1515/znb-2010-0709

Synthesis and Modification of Substituted 2-Azaanthraquinones
Thomas Welzela, Dieter Weißa, Rainer Beckerta, and Helmar Go¨rlsb
a Institute of Organic and Macromolecular Chemistry, Friedrich Schiller University,
Humboldtstraße 10, 07743 Jena, Germany
b Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University,
August-Bebelstraße 2, 07743 Jena, Germany
Reprint requests to Prof. Dr. R. Beckert. E-mail: Rainer.Beckert@uni-jena.de
Z. Naturforsch. 2010, 65b, 833 – 842; received March 18, 2010
The cycloaddition-ring transformation reaction sequence of pyrido[1,2-a]pyrazines with substi-
tuted naphthoquinones furnished a series of new highly substituted azaanthraquinones. Whereas
monosubstituted naphthoquinones were normally leading to two regioisomeric products, in some
cases a preference for only one regioisomer was observed. The amino derivative 3b which was iso-
lated as the main product proved to be suitable for further modifications at the primary amino group.
The derivatives obtained possess groups capable of connecting the molecule with other substructures
for applications as functional dyes. The newly synthesized azaquinones show strong and very broad
absorptions between 400 and 600 nm in their UV/Vis spectra.
Key words: Azaanthraquinones, Ring Transformation, Cycloaddition, Functional Dyes
Introduction
In the past, we have reported an efficient synthesis
for highly substituted azaanthraquinones by a complex
cycloaddition/ring transformation cascade of the easily
accessible pyrido[1,2-a]pyrazines 1 [16] (Scheme 1).
The azaanthraquinones obtained feature the coexis-
tence of a 2,2ꢀ-bipyridine substructure and two vicinal
arylamino moieties.
Due to the fact that quinones have manifold appli-
cations as functional dyes, e. g. as a dark quencher
for polymerase chain reaction (“PCR”) [17], and as
electron-accepting parts in systems for studying arti-
ficial energy and electron transfer processes [18], there
is a need for new multifunctional derivatives. We have
now expanded our research to consider the reaction
of 1 with a series of substituted 1,4-naphthoquinones
which results in new azaanthraquinones.
The partial replacement of carbon by nitrogen in an-
thraquinone results in azaanthraquinones which can be
regarded as electronically distorted variants of the par-
ent compounds. These derivatives are rarely found in
nature, however, they are of special interest due to their
important physiological properties [1 – 4]. In addition,
many synthetic representatives show interesting bio-
logical effects [5 – 8]. 1- and 2-azaanthraquinones are
generally synthetically accessible, and successful pro-
cedures are available in the chemical literature [9 – 15].
A major drawback, however, is the fact that the sub-
stitutional variety at the trinuclear core is relatively
limited.
Scheme 1. Synthesis of starting ma-
terials 1 and their subsequent ring-
transformation reaction into azaan-
thraquinones 2 (the indices a, b,
c for the appropriate aryl moieties
are used below for all other azaan-
thraquinones).
c
0932–0776 / 10 / 0700–0833 $ 06.00 ꢀ 2010 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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T. Welzel et al. · Synthesis and Modification of Substituted 2-Azaanthraquinones
Scheme 3. Modifica-
tion reactions at the
primary amino group
of azaanthraquinone 3.
Scheme 4. Synthesis of substi-
tuted azaanthraquinones.
Results and Discussion
With respect to the applications of 2-azaanthraqui-
nones, for example as dark quencher or antenna sys-
tems, the presence of groups which are capable of con-
necting the molecule with other substructures is nec-
essary. Due to the fact that usually hydroxyl or car-
boxy groups have been employed, we tested the reac-
tions of 2-azaanthraquinones with halogeno alcohols,
propylene oxide, and succinic acid anhydride. Unfor-
tunately, this method failed, and the desired products
were formed only in traces. The low nucleophilic-
ity of both amino functions is most likely mainly re-
sponsible for this failure. Next, we made attempts to
synthesize derivatives which possess other functional
groups. To this end, pyrido[1,2-a]pyrazine1a was ring-
transformed with 5-aminonaphthoquinone in order to
obtain derivative 3a bearing the more reactive amino
function (Scheme 2). Unexpectedly, only one regioiso-
mer was isolated; the single crystal X-ray structure of
which is depicted in Fig. 1.
Fig. 1. Molecular structure of azaanthraquinone 3a in the
crystal.
Subsequently, the modification reactions of the
amino group of 3b with the reagents mentioned above
were successful, yielding derivatives 4–6b in moder-
ate up to good yields. In addition, the reaction with
propane sultone furnished derivative 7b, which fea-
tures water solubility (Scheme 3).
In order to study the regioselectivity of the ini-
tial Diels-Alder reaction, further 1,4-naphthoquinones
substituted in the 5-position were reacted with 1. How-
ever, neither the nitro- nor the iodo-substituted naph-
thoquinone showed any selectivity, giving only mix-
tures of 8ꢀ/8ꢀꢀ and 9ꢀ/9ꢀꢀ, respectively (Scheme 4).
We succeeded in obtaining single crystals of each
regioisomeric compound, which allowed structure de-
Scheme 2. Synthesis of amino-azaanthraquinones 3a and 3b.
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T. Welzel et al. · Synthesis and Modification of Substituted 2-Azaanthraquinones
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Fig. 2. Molecular struc-
tures of the nitro deriva-
tive 8cꢀꢀ (left) and the iodo
derivative 9aꢀ (right).
Scheme 5. Ring transfor-
mation of 1c with 6-sub-
stituted naphthoquinones.
terminations by X-ray diffraction analysis and, thus, a
reliable assignment (Fig. 2).
In further experiments, 5,8-dihydroxy-1,4-naphtho-
quinone (“naphthazarine”) was reacted with 1. As the
main product, 5,8-dihydroxy-2-aza-anthraquinone 10
was isolated in fair yield (Fig. 3). However, all attempts
to introduce further substructures at the OH groups by
reaction with ω-halogeno alcohols/ω-halogeno fatty
acids failed. A possible reason for this failure seems
to be the nature of the OH groups. As depicted in the
X-ray structure, the quinone carbonyl bonds are elon-
gated, and in parallel, both phenolic C–O bonds are
shortened. This fact is in agreement with data exist-
ing for chinizarine [19], indicating the existence of an
Fig. 3. Molecular structure of 5,8-dihydroxyazaanthraquin-
one 10a.
equilibrium between the 9,10- and 5,8-anthraquinone
structures in solution.
With respect to their reactivity towards 1, besides (Scheme 5). Interestingly, in the cases where R =
naphthoquinones substituted in the 5-position, func- CH3/CH2Br, two regioisomeric compounds were again
tionalized derivatives in the 6-position were also tested formed in a statistical distribution, whereas when
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T. Welzel et al. · Synthesis and Modification of Substituted 2-Azaanthraquinones
Scheme 6. Synthesis of azaanthraquinone 14 and its attempted ozonolysis reaction.
R = CH2OH, one regioisomer was clearly favored
(> 10 : 1). No structure determination was possible due
to the lack of single crystals. The hydroxymethyl func-
tion proved to be an excellent coupling group for its
use as a functional dye.
Another promising way to obtain coupling-active
functions should exist in the oxidation of hydroxy-
methyl derivatives to furnish the appropriate car-
boxylic acids. Since attempts to carry out this oxida-
tion failed completely, the derivative 14a containing a
double bond in its side chain was synthesized. It was
hoped that in a subsequent reaction this double bond
could be transformed via ozonolysis into acetone and
aldehyde (Scheme 6). Derivative 14a (two regioiso-
mers) was obtained by a [4+2] cycloaddition reaction
between myrcene and 1,4-benzoquinone [20] followed
by ring transformation with pyridopyrazine 1a. How-
ever, whe◦n employing typical conditions for ozonoly-
sis (−78 C, CH2Cl2, 10 min), all attempts to isolate
the desired product were in vain.
Fig. 4. Molecular structure of the palladium complex 16a.
Finally, starting from acetone, benzil and 1,4-benzo-
quinone, 6,7-diphenyl-1,4-naphthoquinone [21] was
synthesized and then ring transformed into derivative
15 (Scheme 4). Since this procedure might allow the
introduction of numerous functional groups, we are
also studying the chemistry of appropriate benzils.
Due to their polyfunctionality, the azaanthraquinon-
es synthesized here are not only powerful chromo-
phores, but also possess the prerequisites (bipyridine,
redox activity) to act as multifunctional ligands.
As a model reaction, 2a was treated with the al-
lyl palladium(II) chloride dimer in THF. A quantita-
Fig. 5. UV/Vis spectra of the derivatives 3a, 8aꢀ and 10a mea-
sured in CHCl3.
tive reaction forming a deep-red compound 16a took
place even at r. t. (Scheme 7). Interestingly, the ab-
sence/presence of TEA as a base showed no influence
on the formation of the product. Compound 16a proved
to be stable towards air and was further purified by col-
umn chromatography. The X-ray structure analysis ob-
tained from a single crystal clearly demonstrated that
the metal is coordinated only at the unsubstituted pyri-
dine substructure (Fig. 4). Obviously, the oxygen atom
Scheme 7. Synthesis of the palladium complex 16a.
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T. Welzel et al. · Synthesis and Modification of Substituted 2-Azaanthraquinones
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Table 1. Crystal data and data collection and refinement details for the X-ray structure determinations of 3a, 8cꢀꢀ, 9aꢀ, 10a and
16a.
Compound
Formula
3a
8cꢀꢀ
9aꢀꢀ
C30H19IN4O2
10a
16a
C30H21N5O2,
CHCl3
602.89
C30H17Br2N5O4,
CHCl3
790.67
C30H20N4O4,
C6H6O2, CHCl3
729.98
−90(2)
monoclinic
P21/c
10.1828(5)
22.4527(8)
14.6117(8)
90
100.774(2)
90
3281.8(3)
4
1.48
3.4
18624
C33H25ClN4O2Pd
Mw, g mol−1
T, ◦C
594.39
−90(2)
triclinic
651.42
−90(2)
monoclinic
P21/c
9.944(2)
23.364(5)
12.349(3)
90
95.65(3)
90
2855(1)
4
1.52
7.8
11870
3407
5918 / 0.0855
0.0829
0.1830
1.101
−90(2)
−90(2)
Crystal system
Space group
triclinic
triclinic
¯
¯
¯
P1
P1
P1
˚
a, A
9.664(3)
9.981(3)
15.973(5)
105.965(16)
97.011(17)
105.70(2)
1393.5(7)
2
1.44
3.7
4495
2452
8.8003(6)
11.4569(6)
15.8348(11)
106.125(3)
90.978(4)
90.398(4)
1533.38(17)
2
1.71
29.5
10594
5113
8.5103(5)
10.5368(8)
14.5961(9)
100.603(3)
104.944(4)
106.245(5)
1166.89(13)
2
1.69
14.1
8168
3544
˚
b, A
˚
c, A
α, deg
β, deg
γ, deg
3
˚
V, A
Z
ρ, g mol−1
µ, cm−1
Measured data
Data with I ≥ 2σ(I)
Unique data / Rint
R1 [I ≥ 2σ(I)]a
wR2 (all data)a
Sb
4778
7425 / 0.0592
0.0527
0.1292
1.008
3408 / 0.0372
0.0624
0.1719
6859 / 0.0282
0.0581
0.1800
5220 / 0.0599
0.0672
0.1652
1.040
1.023
1.022
−3
˚
∆ρfin (max / min), e A
CCDC no.
0.38 / −0.33
1.10 / −0.89
1.82 / −1.16
0.32 / −0.29
0.80 / −0.86
767539
767540
767541
767542
767543
a
2
R1 = ΣꢁFo|− |Fcꢁ/Σ|Fo|, wR2 = [Σw(Fo − Fc2)2/Σw(Fo2)2]1/2, w = [σ2(Fo2)+(aP)2+bP]−1, where P = (Max(Fo2, 0)+2Fc2)/3 and a and
b are constants adjusted by the program; S = GoF = [Σw(Fo − Fc2)2/(nobs − nparam)]1/2, where nobs is the number of data and nparam the
b
2
number of refined parameters.
of the quinone subunit sterically prevents the formation resolution mass spectra were recorded on a Finnigan MAT 95
XL-Trap. UV/Vis spectra were recorded on a Perkin-Elmer
Lambda 19 spectrophotometer. The IR spectra were obtained
on a Biorad FTS-25 instrument.
of a bipyridine complex.
All newly synthesized azaquinones are dark-blue
crystalline compounds. They show very broad absorp-
tions between 400 and 600 nm with high extinctions
in their UV/Vis spectra. The UV/Vis spectra of 3a, 8aꢀ
and 10a, are depicted in Fig. 5. Their chemical stabil-
ity, the presence of coupling-active groups, and their
spectral features mentioned above make them interest-
ing candidates for applications in antenna systems and
as dark quenchers for PCR.
Crystal structure determinations
The intensity data were collected on a Nonius KappaCCD
diffractometer, using graphite-monochromatized MoKα ra-
diation. Data were corrected for Lorentz and polarization,
but not for absorption [22, 23]. The structures were solved
by Direct Methods (SHELXS [24]) and refined by full-matrix
2
least-squares techniques against Fo (SHELXL-97 [25]). For
the amino groups of 3a, 8cꢀꢀ, 9aꢀ and 16a the hydrogen
atoms were located by difference Fourier syntheses and re-
fined isotropically. All other hydrogen atoms were included
at calculated positions with fixed thermal parameters. All
non-hydrogen atoms were refined anisotropically [25]. XP
(Siemens Analytical X-ray Instruments, Inc.) was used for
structure representations. Details of the structure determina-
tions are given in Table 1.
Experimental Section
The reagents employed in the following section were pur-
chased from commercial sources and used directly unless
otherwise stated. All solvents were of reagent grade and were
dried according to common practice and distilled prior to use.
Reactions were monitored by TLC using aluminum plates
coated with Al2O3 or SiO2 from Fluka. The 1H and 13C
CCDC-767539 (3a), 767540 (8cꢀꢀ), 767541 (9aꢀ), 767542
NMR spectra were obtained on Bruker AC 250 (250 MHz) or (10a), and 767543 (16a) contain the supplementary crystal-
DRC-400 (400 MHz) spectrometers; shifts are given relative lographic data for this paper. These data can be obtained free
to the signals of the solvent. Mass spectra were measured on of charge from The Cambridge Crystallographic Data Centre
a spectrometer SAQ 710 from Finnigan MAT, while the high- via www.ccdc.cam.ac.uk/data request/cif.
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T. Welzel et al. · Synthesis and Modification of Substituted 2-Azaanthraquinones
General procedure for ring transformation of pyrido[1,2-a]- 8 Hz, 2H), 7.24 (d, J = 8 Hz, 2H), 7.38 (t, J = 8 Hz, 1H), 7.46
pyrazines 1 with substituted naphthoquinones
(d, J = 8 Hz, 1H), 7.55 (d, J = 8 Hz, 1H), 7.70 – 7.75 (m, 2H),
7.92 (t, J = 8 Hz, 1H), 8.66 (d, J = 5 Hz, 1H), 9.21 (t, J =
8 Hz, 1H), 10.51 (s, 1H). – 13C NMR (CDCl3): δ = 20.8,
20.8, 34.4, 44.7, 60.3, 114.7, 117.6, 120.1, 120.4, 122.3,
124.5, 125.8, 126.7, 128.8, 129.2, 129.7, 130.0, 130.2, 130.9,
132.9, 133.2, 133.6, 134.3, 136.2, 138.0, 148.4, 148.9, 150.9,
156.6, 185.6, 188.2. – MS (FAB): m/z (%) = 569 (10) [M]+,
57 (100). – UV/Vis (CHCl3): λmax (lg ε) = 569 (3.9) nm. – IR
(ATR): ν = 2923, 1739, 1460, 1149 cm−1. – HRMS: m/z =
570.25306 (calcd. 570.25051 for C35H32N5O3, [M+H]+).
A solution of the pyrido[1,2-a]pyrazine 1 (1 mmol) and
the appropriate quinone (1 mmol) was heated under reflux in
50 mL of anhydrous methylene chloride, and the progress of
the reaction was monitored by TLC. Usually, reaction times
were between 12 and 30 h. The solvent was removed in
vacuo, and the residue was purified by chromatography on
silica gel.
6-Amino-3,4-bis(phenylamino)-1-pyridin-2-yl-benzo[g]-
isoquinoline-5,10-dione (3a)
6-(2-Hydroxypropyl)amino-1-pyridin-2-yl-3,4-bis(p-tolyl-
amino)-benzo[g]isoquinoline-5,10-dione (5b)
1
Dark-red crystals, yield: 60 %. – H NMR (CDCl3): δ =
6.88 (d, J = 6 Hz, 2H), 6.94 (s, 1H), 6.97 (d, J = 8 Hz,
2H), 7.10 – 7.44 (m, 11H), 7.51 (d, J = 8 Hz, 1H), 7.67
(d, J = 8 Hz, 1H), 7.90 (t, J = 8 Hz, 1H), 8.66 (d, J =
5 Hz, 1H), 10.37 (s, 1H). – 13C NMR ([D6]DMSO): δ =
113.6, 115.6, 118.8, 119.3, 120.8, 121.0, 122.4, 122.8, 123.3,
123.3, 123.8, 125.9, 127.8, 128.8, 129.4, 134.3, 135.1, 136.5,
139.7, 142.6, 148.7, 151.1, 151.6, 160.5, 183.8, 186.6. –
MS (EI): m/z (%) = 483 (100) [M]+, 405 (40), 242 (30). –
UV/Vis (CHCl3): λmax (lg ε) = 367 (3.6), 535 (4.0) nm. – IR
(ATR): ν = 3421, 2923, 1600, 1251 cm−1. – HRMS: m/z =
484.17769 (calcd. 484.17735 for C30H22N5O2, [M+H]+).
1 mmol of 3b was dissolved under argon together with a
catalytic amount of lithium bromide in 4 mL of propylene
oxide, and the mixture was stirred at r. t. for 7 d. The so-
lution was evaporated to dryness, and the residue was puri-
fied by chromatography on silica gel. Brown crystals, yield:
1
19 %. – H NMR (CDCl3): δ = 1.35 (m, 3H), 2.31 (s, 3H),
2.34 (s, 3H), 2.78 (m, 1H), 3.59 (m, 2H), 6.87 (s, 1H), 6.92
(d, J = 8 Hz, 2H), 7.01 (d, J = 8 Hz, 2H), 7.27 (d, J =
8 Hz, 2H), 7.40 – 7.55 (m, 7H), 7.79 (d, J = 8 Hz, 1H),
8.01 (t, J = 8 Hz, 1H), 8.52 (d, J = 8 Hz, 1H), 9.37 (s,
1H). – 13C NMR (CDCl3): δ = 18.3, 20.8, 20.9, 49.8, 68.3,
114.7, 117.7, 120.0, 120.4, 122.3, 124.6, 125.8, 126.8, 128.8,
129.3, 129.7, 130.1, 130.2, 130.9, 132.9, 133.3, 133.6, 134.3,
136.2, 137.9, 148.4, 149.0, 151.1, 156.6, 185.2, 188.0 ppm. –
MS (Micro-ESI): m/z (%) = 570 (100) [M+1]+. – UV/Vis
(CHCl3): λmax (lg ε) = 545 (3.9) nm. – IR (ATR): ν = 3401,
2924, 1567, 1421, 1111 cm−1. – HRMS: m/z = 570.25347
(calcd. 570.25051 for C35H32N5O3, [M+H]+).
6-Amino-1-pyridin-2-yl-3,4-bis(p-tolylamino)-benzo[g]-
isoquinoline-5,10-dione (3b)
Brown crystals, yield: 71 %. – 1H NMR (CDCl3): δ =
2.25 (s, 3H), 2.32 (s, 3H), 6.83 (d, J = 6 Hz, 2H), 6.88 (s, 1H),
6.92 (d, J = 8 Hz, 2H), 6.99 (d, J = 8 Hz, 2H), 7.10 (d, J =
8 Hz, 2H), 7.25 (d, J = 8 Hz, 2H), 7.28 (8. J = 6 Hz, 1H), 7.33
(d, J = 8 Hz, 1H), 7.36 (t, J = 8 Hz, 1H), 7.47 (d, J = 8 Hz,
1H), 7.64 (d, J = 8 Hz, 1H), 7.87 (t, J = 8 Hz, 1H), 8.63 (d,
J = 5 Hz, 1H), 10.51 (s, 1H). – 13C NMR (CDCl3): δ = 20.7,
20.8, 114.7, 116.4, 118.5, 120.0, 120.3, 122.4, 123.1, 123.3,
124.6, 127.5, 129.2, 130.0, 132.8, 133.6, 133.7, 135.1, 136.2,
136.9, 138.0, 148.0, 149.1, 150.3, 160.0, 184.2, 187.3. –
MS (EI): m/z (%) = 511 (100) [M]+, 433 (50), 91 (40). –
UV/Vis (CHCl3): λmax (lg ε) = 375 (3.8), 547 (4.1) nm. – IR
(ATR): ν = 3404, 2964, 1598, 1246 cm−1. – HRMS: m/z =
512.20870 (calcd. 512.20958 for C32H26N5O2, [M+H]+).
4-(5,10-Dioxo-1-(pyridin-2-yl)-3,4-bis(p-tolylamino)-5,10-
dihydrobenzo[g]isoquinolin-6-ylamino)-4-oxobutanoic acid
(6b)
1 mmol of 3b was dissolved with 3 mmol of succinic
acid anhydride in 20 mL of anhydrous toluene, and the mix-
ture was heated under reflux. The reaction was monitored by
TLC. After 30 h the solvent was removed in vacuo, and the
residue was purified by chromatography on silica gel. Dark-
red crystals, yield: 45 %. – 1H NMR (CDCl3): δ = 2.10 (m,
2H), 2.27 (s, 3H), 2.32 (s, 3H), 2.52 (m, 2H), 6.87 (d, J =
8 Hz, 2H), 7.02 (s, 1H), 7.04 (d, J = 8 Hz, 2H), 7.22 (d,
J = 8 Hz, 2H), 7.32 (d, J = 8 Hz, 2H), 7.43 – 7.74 (m, 5H),
6-(3-Hydroxytextitpropyl)amino-1-pyridin-2-yl-3,4-bis(p-
tolylamino)-benzo[g]isoquinoline-5,10-dione (4b)
A mixture of 0.01 mmol 3b and 0.07 g K2CO3 in 2 mL 7.83 (m, 1H), 8.60 (d, J = 5 Hz, 1H), 8.84 (m, 1H), 10.47
of 3-bromopropan-1-ol was heated with stirring at 80 ◦C for (s, 1H), 11.83 (s, 1H). – 13C NMR (CDCl3): δ = 20.8, 20.9,
80 h. After removing the liquid phase in vacuo the residue 29.2, 32.5, 114.7, 116.4, 118.5, 120.0, 120.3, 122.4, 123.1,
was purified by chromatography on silica gel. Red crystals, 123.3, 124.6, 127.5, 129.2, 130.0, 132.8, 133.6, 133.7, 135.1,
yield: 39 %. – 1H NMR (CDCl3): δ = 1.88 (m, 2H), 2.26 (s, 136.2, 136.9, 138.0, 143.2, 148.0, 149.1, 150.3, 160.0, 171.2,
3H), 2.29 (s, 3H), 2.78 (m, 2H), 3.59 (m, 2H), 6.79 (s, 1H), 177.2, 184.2, 187.3. – MS (EI): m/z (%) = 611 (10) [M]+,
6.95 (d, J = 8 Hz, 2H), 7.00 (d, J = 8 Hz, 2H), 7.11 (d, J = 511 (20), 107 (100). – UV/Vis (CHCl3): λmax (lg ε) = 398
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T. Welzel et al. · Synthesis and Modification of Substituted 2-Azaanthraquinones
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(3.4), 552 (3.9) nm. – IR (ATR): ν = 3410, 2924, 1704, 1514, 138.0, 139.4, 148.1, 148.8, 149.6, 158.2, 179.3, 183.2. – MS
1251 cm−1. – HRMS: m/z = 612.22246 (calcd. 612.22469 for (EI): m/z (%) = 513 (20) [M]+, 399 (15), 84 (100). – UV/Vis
C36H30N5O5, [M+H]+).
(CHCl3): λmax (lg ε) = 394 (3.6), 559 (4.0) nm. – IR (ATR):
ν = 3365, 2924, 1657, 1440, 1248 cm−1. – HRMS: m/z =
514.15274 (calcd. 514.15153 for C30H20N5O4, [M+H]+).
3-(5,10-Dioxo-1-(pyridin-2-yl)-3,4-bis(p-tolylamino)-5,10-
dihydrobenzo[g]isoquinolin-6-ylamino)propane-1-sulfonic
acid (7b)
3,4-Bis(4-bromophenylamino)-9-nitro-1-pyridin-2-yl-benzo-
[g]isoquinoline-5,10-dione (8cꢀ)
1 mmol of 3b was dissolved in 20 mL of anhydrous
toluene with 1 mmol of 1,3-propane sultone. The mixture
was heated under reflux for 20 h. The solvent was removed,
and the residue was purified by chromatography on silica gel.
Brown crystals, yield: 44 %. – 1H NMR (CDCl3): δ =
6.88 (d, J = 8 Hz, 2H), 6.90 (s, 1H), 7.20 – 7.31 (m, 5H),
7.34 (d, J = 8 Hz, 2H), 7.43 (t, J = 5 Hz, 1H), 7.63 (d, J =
8 Hz, 1H), 7.74 (d, J = 8 Hz, 1H), 7.86 (t, J = 8 Hz, 1H),
8.34 (d, J = 8 Hz, 1H), 8.64 (d, J = 5 Hz, 1H), 9.95 (s, 1H). –
13C NMR (CDCl3): δ = 113.4, 115.7, 117.2, 119.0, 120.6,
121.7, 122.0, 122.2, 125.1, 125.7, 127.5, 128.8, 129.9, 131.9,
132.0, 132.5, 132.7, 135.2, 135.5, 137.0, 145.3, 152.5, 154.4,
157.2, 183.1, 185.2. – MS (EI): m/z (%) = 671 (15) [M]+,
641 (20), 530 (50), 57 (100). – UV/Vis (CHCl3): λmax (lg
ε) = 380 (3.6), 545 (3.9) nm. – IR (ATR): ν = 3375, 2923,
1662, 1485, 1242 cm−1. – HRMS: m/z = 669.97180 (calcd.
669.97257 for C30H18Br2N5O4, [M+H]+).
1
Brown crystals, yield: 20 %. – H NMR ([D6]DMSO): δ =
1.82 (m, 2H), 2.20 (s, 3H), 2.47 (m, 2H), 2.22 (s, 3H), 3.43
(m, 2H), 6.85 (d, J = 6 Hz, 2H), 7.00 (d, J = 8 Hz, 2H), 7.03
(d, J = 8 Hz, 2H), 7.20 (d, J = 8 Hz, 1H), 7.31 (d, J = 8 Hz,
1H), 7.37 (m, 1H), 7.39 (d, J = 8 Hz, 2H), 7.55 – 7.58 (m,
2H), 7.89 (t, J = 8 Hz, 1H), 8.30 (s, 1H), 8.54 (d, J = 8 Hz,
1H), 9.02 (m, 1H), 9.84 (s, 1H). – 13C NMR ([D6]DMSO):
δ = 20.8, 20.9, 25.6, 41.7, 49.1, 113.8, 114.6, 118.6, 118.9,
121.0, 122.9, 123.2, 126.1, 126.2, 129.3, 129.8, 131.3, 132.3,
135.0, 135.5, 136.7, 137.2, 139.7, 148.8, 150.6, 150.8, 152.7,
160.3, 167.2, 184.2, 186.3. – MS (FAB): m/z (%) = 634 (30)
[M]+, 205 (100). – UV/Vis (CHCl3): λmax (lg ε) = 383 (3.5),
571 (3.9) nm. – IR (ATR): ν = 3414, 2924, 1591, 1510,
1179 cm−1. – HRMS: m/z = 634.21397 (calcd. 634.21242
for C35H32SN5O5, [M+H]+).
3,4-Bis(4-bromophenylamino)-6-nitro-1-pyridin-2-yl-benzo-
[g]isoquinoline-5,10-dione (8cꢀꢀ)
Brown crystals, yield: 28 %. – 1H NMR (CDCl3): δ =
6.89 (d, J = 8 Hz, 2H), 6.92 (s, 1H), 7.21 – 7.32 (m, 5H),
7.35 (d, J = 8 Hz, 2H), 7.41 (t, J = 5 Hz, 1H), 7.60 (d, J =
8 Hz, 1H), 7.73 (d, J = 8 Hz, 1H), 7.85 (t, J = 8 Hz, 1H),
8.35 (d, J = 8 Hz, 1H), 8.66 (d, J = 5 Hz, 1H), 9.98 (s, 1H)
ppm. – 13C NMR (CDCl3): δ = 113.6, 115.9, 117.1, 119.2,
120.8, 121.7, 122.0, 122.3, 125.0, 125.7, 127.5, 128.9, 130.1,
131.9, 132.0, 132.6, 132.7, 135.3, 135.6, 137.2, 145.1, 152.6,
154.3, 157.5, 183.4, 185.1. – MS (EI): m/z (%) = 671 (10)
[M]+, 641 (20), 530 (40), 57 (100). – UV/Vis (CHCl3): λmax
(lg ε) = 382 (3.6), 548 (3.9) nm. – IR (ATR): ν = 3402, 2921,
1660, 1484, 1242 cm−1. – HRMS: m/z = 669.97240 (calcd.
669.97257 for C30H18Br2N5O4, [M+H]+).
6/9-Nitro-3,4-bis(phenylamino)-1-pyridin-2-yl-benzo[g]-
isoquinoline-5,10-dione (8aꢀ)
1
Red crystals, yield: 45 %. – H NMR (CDCl3): δ = 6.95
(s, 1H), 7.06 (d, J = 8 Hz, 2H), 7.13 (d, J = 8 Hz, 2H), 7.17 –
7.45 (m, 8H), 7.57 (t, J = 8 Hz, 1H), 7.73 (t, J = 8 Hz,
1H), 8.08 (t, J = 8 Hz, 1H), 8.41 (d, J = 8 Hz, 1H), 8.76
(d, J = 5 Hz, 1H), 10.38 (s, 1H). – 13C NMR (CDCl3): δ =
118.4, 120.7, 120.8, 123.3, 123.4, 123.6, 124.3, 125.0, 125.6,
127.0, 128.4, 128.9, 129.0, 129.2, 129.6, 134.8, 135.0, 137.8,
138.0, 139.4, 148.1, 148.8, 149.5, 158.3, 179.6, 183.4. – MS
(EI): m/z (%) = 513 (10) [M]+, 209 (30), 57 (100). – UV/Vis
(CHCl3): λmax (lg ε) = 403 (3.6), 550 (4.0) nm. – IR (ATR):
ν = 3326, 2923, 1662, 1441, 1254 cm−1. – HRMS: m/z =
514.15284 (calcd. 514.15153 for C30H20N5O4, [M+H]+).
9-Iodo-3,4-bis(phenylamino)-1-pyridin-2-yl-benzo[g]-
isoquinoline-5,10-dione (9aꢀ)
Red crystals, yield: 49 %. – 1H NMR (CDCl3): δ = 6.83
(s, 1H), 7.00 – 7.34 (m, 11H), 7.35 (t, J = 6 Hz, 1H), 7.90 (d,
J = 8 Hz, 1H), 7.93 (t, J = 8 Hz, 1H), 8.15 (d, J = 8 Hz, 1H),
8.29 (d, J = 8 Hz, 1H), 8.66 (d, J = 5 Hz, 1H), 10.09 (s, 1H). –
13C NMR (CDCl3): δ = 92.1, 119.9, 120.2, 120.6, 123.2,
6/9-Nitro-3,4-bis(phenylamino)-1-pyridin-2-yl-benzo[g]-
isoquinoline-5,10-dione (8aꢀꢀ)
1
Red crystals, yield: 31 %. – H NMR (CDCl3): δ = 6.97 123.3, 123.6, 123.9, 125.6, 126.0, 127.3, 128.8, 129.6, 132.6,
(s, 1H), 7.00 (d, J = 8 Hz, 2H), 7.07 (d, J = 8 Hz, 2H), 7.17 – 135.9, 136.8, 137.0, 138.6, 140.3, 147.6, 148.6, 149.2, 152.1,
7.45 (m, 8H), 7.70 (t, J = 8 Hz, 1H), 7.81 (t, J = 8 Hz, 157.4, 184.1, 185.6. – MS (EI): m/z (%) = 594 (30) [M]+,
1H), 7.96 (t, J = 8 Hz, 1H), 8.30 (d, J = 8 Hz, 1H), 8.76 516 (10), 149 (100). – UV/Vis (CHCl3): λmax (lg ε) = 380
(d, J = 5 Hz, 1H), 10.38 (s, 1H). – 13C NMR (CDCl3): δ = (3.7), 531 (3.9) nm. – IR (ATR): ν = 3382, 2921, 1670, 1506,
116.1, 120.4, 121.1, 123.4, 123.5, 123.7, 124.1, 124.9, 125.6, 1250 cm−1. – HRMS: m/z = 595.06422 (calcd. 595.06310 for
127.0, 128.3, 128.9, 129.6, 129.7, 130.0, 134.6, 135.8, 137.6, C30H20IN4O2, [M+H]+).
Unauthenticated
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840
T. Welzel et al. · Synthesis and Modification of Substituted 2-Azaanthraquinones
6-Iodo-3,4-bis(phenylamino)-1-pyridin-2-yl-benzo[g]-
(s, 1H). – 13C NMR (CDCl3): δ = 22.0, 116.7, 119.2, 121.5,
122.1, 127.2, 127.6, 128.2, 129.0, 131.3, 131.8, 132.1, 132.4,
132.6, 132.9, 134.4, 136.0, 139.4, 140.6, 141.6, 143.6, 146.3,
150.0, 153.1, 157.8, 182.0, 184.4. – MS (EI): m/z (%) = 639
(30) [M]+, 398 (40), 91 (100). – UV/Vis (CHCl3): λmax (lg
ε) = 514 (4.0) nm. – IR (ATR): ν = 3253, 2922, 1653, 1484,
1261 cm−1. – HRMS: m/z = 639.00527 (calcd. 639.00315
for C31H21Br2N4O2, [M+H]+).
isoquinoline-5,10-dione (9aꢀꢀ)
1
Red crystals, yield: 25 %. – H NMR (CDCl3): δ = 6.97
(s, 1H), 7.00 – 7.38 (m, 11H), 7.39 (t, J = 6 Hz, 1H), 7.69
(d, J = 8 Hz, 1H), 7.90 (t, J = 8 Hz, 1H), 8.15 (d, J = 8 Hz,
1H), 8.29 (d, J = 8 Hz, 1H), 8.63 (d, J = 5 Hz, 1H), 10.15 (s,
1H). – 13C NMR (63 MHz, CDCl3): δ = 92.5, 120.0, 120.2,
120.6, 123.0, 123.2, 123.7, 123.8, 126.5, 126.7, 127.8, 128.8,
129.6, 133.4, 134.0, 136.8, 137.1, 138.4, 140.6, 147.6, 148.7,
150.3, 153.0, 158.9, 180.4, 185.2. – MS (EI): m/z (%) = 594
(100) [M]+, 516 (40), 209 (100). – UV/Vis (CHCl3): λmax
(lg ε) = 373 (3.8), 531 (4.0) nm. – IR (ATR): ν = 3382, 2922,
1656, 1472, 1225 cm−1. – HRMS: m/z = 595.06377 (calcd.
595.06310 for C30H20IN4O2, [M+H]+).
7/8-Bromomethyl-3,4-bis(4-bromophenylamino)-1-pyridin-
2-yl-benzo[g]isoquinoline-5,10-dione (12cꢀ)
Brown crystals, yield: 32 %. – 1H NMR (CDCl3): δ =
4.51 (s, 2H), 6.85 (d, J = 8 Hz, 2H), 6.99 (s, 1H), 7.16 –
7.33 (m, 4H), 7.41 (t, J = 6 Hz, 1H), 7.44 (d, J = 8 Hz,
2H), 7.61 (d, J = 8 Hz, 1H), 7.73 (d, J = 8 Hz, 1H), 7.91
(t, J = 8 Hz, 1H), 8.12 (s, 1H), 8.15 (d, J = 8 Hz, 1H), 8.67
(d, J = 5 Hz, 1H), 10.16 (s, 1H). – 13C NMR (CDCl3): δ =
29.7, 116.2, 120.8, 121.6, 122.9, 125.3, 126.4, 127.6, 129.0,
131.8, 132.5, 133.8, 134.9, 136.7, 137.3, 139.8, 141.0, 143.0,
144.8, 148.9, 158.6, 183.1, 188.4. – MS (EI): m/z (%) = 718
(10) [M]+, 149 (60), 57 (100). – UV/Vis (CHCl3): λmax (lg
ε) = 369 (3.7), 526 (4.0) nm. – IR (ATR): ν = 3245, 2923,
1653, 1484, 1263 cm−1. – HRMS: m/z = 716.91418 (calcd.
716.91367 for C31H20Br3N4O2, [M+H]+).
6,9-Dihydroxy-3,4-bis(phenylamino)-1-pyridin-2-yl-benzo-
[g]isoquinoline-5,10-dione (10a)
Red crystals, yield: 65 %. – 1H NMR (CDCl3): δ =
7.01 – 7.35 (m, 13H), 7.48 (t, J = 6 Hz, 1H), 7.66 (d, J =
8 Hz, 1H), 7.99 (t, J = 8 Hz, 1H), 8.67 (d, J = 5 Hz, 1H),
10.44 (s, 1H), 12.54 (s, 1H), 12.81 (s, 1H). – 13C NMR
(CDCl3): δ = 116.1, 118.4, 119.5, 120.4, 120.5, 120.7, 121.2,
123.2, 123.7, 124.0, 124.5, 125.9, 127.8, 128.2, 128.8, 129.2,
129.7, 137.3, 138.0, 140.0, 149.6, 149.8, 157.0, 157.5, 185.1,
189.7. – MS (EI): m/z (%) = 500 (40) [M]+, 422 (20), 91
(100). – UV/Vis (CHCl3): λmax (lg ε) = 389 (3.7), 570
(4.1) nm. – IR (ATR): ν = 3350, 2929, 2852, 1594, 1442,
1155 cm−1. – HRMS: m/z = 501.15514 (calcd. 501.15628
for C30H21N4O4, [M+H]+).
7/8-Bromomethyl-3,4-bis(4-bromophenylamino)-1-pyridin-
2-yl-benzo[g]isoquinoline-5,10-dione (12cꢀꢀ)
Brown crystals, yield: 35 %. – 1H NMR (CDCl3): δ =
4.55 (s, 2H), 6.86 (d, J = 8 Hz, 2H), 7.00 (s, 1H), 7.25 –
7.39 (m, 6H), 7.62 (t, J = 6 Hz, 1H), 7.75 (d, J = 8 Hz,
1H), 7.91 (t, J = 8 Hz, 1H), 8.09 (d, J = 8 Hz, 1H), 8.18
(s, 1H), 8.32 (d, J = 8 Hz, 1H), 8.65 (d, J = 5 Hz, 1H),
10.16 (s, 1H). – 13C NMR (CDCl3): δ = 30.1, 116.3, 120.8,
121.5, 122.9, 124.9, 126.5, 127.6, 129.0, 131.8, 132.4, 133.8,
134.8, 137.0, 136.9, 138.4, 141.1, 142.9, 144.4, 148.8, 158.1,
183.3, 187.9. – MS (EI): m/z (%) = 718 (15) [M]+, 654
(20), 57 (100). – UV/Vis (CHCl3): λmax (lg ε) = 378 (3.6),
535 (4.0) nm. – IR (ATR): ν = 3245, 2922, 1651, 1485,
1263 cm−1. – HRMS: m/z = 716.91420 (calcd. 716.91367
for C31H20Br3N4O2, [M+H]+).
3,4-Bis(4-bromophenylamino)-7/8-methyl-1-pyridin-2-yl-
benzo[g]isoquinoline-5,10-dione (11cꢀ)
Brown crystals, yield: 38 %. – 1H NMR (CDCl3): δ =
2.46 (s, 3H), 6.83 (s, 1H), 6.88 (d, J = 8 Hz, 2H), 7.14 –
7.55 (m, 8H), 7.77 (d, J = 8 Hz, 1H), 7.90 (s, 1H), 8.06 (d,
J = 8 Hz, 1H), 8.14 (m, 1H), 8.73 (d, J = 5 Hz, 1H), 10.38
(s, 1H). – 13C NMR (CDCl3): δ = 22.0, 116.6, 119.2, 121.4,
122.1, 127.2, 127.5, 128.2, 128.8, 131.3, 131.9, 132.1, 132.4,
132.6, 132.9, 134.3, 135.9, 139.4, 140.5, 141.6, 143.6, 146.3,
149.9, 153.2, 157.7, 181.8, 184.6. – MS (EI): m/z (%) = 639
(30) [M]+, 398 (50), 91 (100). – UV/Vis (CHCl3): λmax (lg
ε) = 514 (4.0) nm. – IR (ATR): ν = 3260, 2923, 1652, 1484, 3,4-Bis(4-bromophenylamino)-7/8-hydroxymethyl-1-
1260 cm−1. – HRMS: m/z = 639.00496 (calcd. 639.00315 pyridin-2-yl-benzo[g]isoquinoline-5,10-dione (13c)
for C31H21Br2N4O2, [M+H]+).
Brown crystals, yield: 65 %. – 1H NMR (CDCl3): δ =
4.77 (s, 2H), 5.30 (s, 1H), 6.84 (d, J = 8 Hz, 2H), 6.97
(s, 1H), 7.23 – 7.64 (m, 9H), 7.95 – 7.99 (m, 2H), 8.05 (d,
J = 8Hz, 1H), 8.67 (d, J = 5 Hz, 1H), 10.12 (s, 1H). –
3,4-Bis(4-bromophenylamino)-7/8-methyl-1-pyridin-2-yl-
benzo[g]isoquinoline-5,10-dione (11cꢀꢀ)
Brown crystals, yield: 40 %. – 1H NMR (CDCl3): δ = 13C NMR (CDCl3): δ = 63.6, 116.7, 120.1, 121.0, 121.6,
2.48 (s, 3H), 6.81 (s, 1H), 6.90 (d, J = 8 Hz, 2H), 7.10 – 122.0, 123.1, 123.9, 126.1, 126.7, 127.1, 131.8, 132.2, 132.5,
7.50 (m, 8H), 7.72 (d, J = 8 Hz, 1H), 7.92 (s, 1H), 8.04 (d, 132.8, 133.3, 137.2, 137.4, 139.8, 148.0, 148.3, 149.8, 149.9,
J = 8 Hz, 1H), 8.15 (m, 1H), 8.75 (d, J = 5 Hz, 1H), 10.45 152.7, 159.1, 180.8, 186.5. – MS (EI): m/z (%) = 656 (5)
Unauthenticated
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T. Welzel et al. · Synthesis and Modification of Substituted 2-Azaanthraquinones
841
[M]+, 397 (40), 171 (100). – UV/Vis (CHCl3): λmax (lg ε) = 7,8-Diphenyl-3,4-bis(phenylamino)-1-pyridin-2-yl-benzo-
512 (3.9) nm. – IR (ATR): ν = 3409, 2927, 1645, 1485, 1258, [g]isoquinoline-5,10-dione (15a)
1070 cm−1. – HRMS: m/z = 654.99783 (calcd. 654.99800 for
Red crystals, yield: 65 %. – 1H NMR (CDCl3): δ = 7.00 –
C31H21Br2N4O3, [M+H]+).
7.37 (m, 21H), 7.40 (t, J = 6Hz, 1H), 7.70 (d, J = 8 Hz, 1H),
7.91 (t, J = 8 Hz, 1H), 8.17 (s, 1H), 8.23 (s, 1H), 8.66 (d, J =
5 Hz, 1H), 10.50 (s, 1H). – 13C NMR (CDCl3): δ = 117.5,
7/8-(4-Methyl-pent-3-enyl)-3,4-bis(phenylamino)-1-pyridin-
2-yl-benzo[g]isoquinoline-5,10-dione (14aꢀ)
120.0, 120.1, 121.3, 122.3, 123.2, 123.6, 123.8, 125.5, 127.5,
127.6, 128.1, 128.2, 128.6, 128.8, 129.1, 129.4, 129.6, 129.7,
1
Red crystals, yield: 31 %. – H NMR (CDCl3): δ = 1.53
132.5, 133.3, 137.0, 138.5, 139.6, 139.7, 140.5, 145.6, 146.8,
(s, 3H), 1.68 (s, 3H), 2.35 (q, J = 7 Hz, 2H), 2.72 (t, J =
148.4, 150.0, 152.8, 159.3, 181.2, 186.6. – MS (EI): m/z
8 Hz, 2H), 5.12 (t, J = 8 Hz, 1H), 7.00 – 7.38 (m, 11H),
(%) = 620 (60) [M]+, 542 (50), 310 (50), 77 (100). – UV/Vis
7.40 (t, J = 6 Hz, 1H), 7.47 (d, J = 8 Hz, 1H), 7.64 (d,
(CHCl3): λmax (lg ε) = 354 (4.6), 529 (4.0) nm. – IR (ATR):
J = 8 Hz, 1H), 7.90 (t, J = 8 Hz, 1H), 7.95 (s, 1H), 8.07
ν = 3406, 2923, 1656, 1441, 1237 cm−1. – HRMS: m/z =
(d, J = 8 Hz, 1H), 8.66 (d, J = 5 Hz, 1H), 10.46 (s, 1H). –
621.22640 (calcd. 621.22905 for C42H29N4O2, [M+H]+).
13C NMR (CDCl3): δ = 17.7, 25.7, 29.3, 36.4, 120.0, 120.1,
122.8, 122.7, 122.8, 123.6, 123.7, 126.7, 126.8, 126.9, 127.2,
Allyl palladium(II) chloride complex of an azaanthraquinone
127.4, 128.8, 129.0, 129.2, 129.6, 131.8, 133.0, 133.7, 134.6,
(16a)
136.9, 138.6, 140.8, 148.6, 150.2, 159.6, 181.7, 186.8. – MS
(EI): m/z (%) = 550 (30) [M]+, 472 (10), 93 (100). – UV/Vis
To a solution of 0.1 mmol of 2a in 20 mL of anhydrous
(CHCl3): λmax (lg ε) = 523 (4.0) nm. – IR (ATR): ν = 3412,
2923, 1660, 1494, 1255 cm−1. – HRMS: m/z = 551.24257
(calcd. 551.24470 for C36H31N4O2, [M+H]+).
THF a solution of 0.05 mmol of allyl palladium(II) chloride
in THF was added dropwise. The mixture was stirred at r. t.
for 3 h. The solvent was removed, and the residue was pu-
rified by chromatography on silica gel. Red crystals, yield:
90 %. – 1H NMR (CDCl3): δ = 2.44 (m, 2H), 3.64 (m, 2H),
4.93 (m, 1H), 7.00 (s, 1H), 7.02 – 7.25 (m, 8H), 7.37 (t, J =
7 Hz, 1H), 7.44 (d, J = 7 Hz, 2H), 7.65 (d, J = 8 Hz, 1H), 7.77
(m, 2H), 7.93 (t, J = 8 Hz, 1H), 8.16 (d, J = 8 Hz, 1H), 8.25
(d, J = 8 Hz, 1H), 8.91 (m, 1H), 10.72 (s, 1H). – 13C NMR
(CDCl3): δ = 29.2, 29.7, 60.4, 111.8, 117.7, 120.3, 120.4,
122.4, 123.3, 123.5, 123.9, 124.3, 125.8, 126.8, 127.2, 129.0,
129.7, 133.5, 133.8, 134.6, 134.7, 137.5, 138.1, 140.2, 149.7,
151.7, 160.2, 181.1, 186.7. – MS (FAB): m/z (%) = 616 (70)
[Mcat]+, 574 (60), 469 (100). – UV/Vis (CHCl3): λmax (lg
ε) = 374 (3.8), 526 (4.0) nm. – IR (ATR): ν = 3409, 2919,
1654, 1562, 1290 cm−1. – HRMS: m/z = 611.10335 (calcd.
611.10269 for C33H25N4O2102Pd, [M]+).
7/8-(4-Methyl-pent-3-enyl)-3,4-bis(phenylamino)-1-pyridin-
2-yl-benzo[g]isoquinoline-5,10-dion (14aꢀꢀ)
1
Red crystals, yield: 35 %. – H NMR (CDCl3): δ = 1.56
(s, 3H), 1.70 (s, 3H), 2.35 (q, J = 7 Hz, 2H), 2.77 (t, J =
8 Hz, 2H), 5.15 (t, J = 8 Hz, 1H), 7.00 – 7.40 (m, 11H),
7.42 (t, J = 6 Hz, 1H), 7.51 (d, J = 8 Hz, 1H), 7.66 (d,
J = 8 Hz, 1H), 7.90 (t, J = 8 Hz, 1H), 7.99 (s, 1H), 8.05
(d, J = 8 Hz, 1H), 8.66 (d, J = 5 Hz, 1H), 10.44 (s, 1H). –
13C NMR (CDCl3): δ = 17.3, 25.2, 28.8, 35.7, 120.0, 120.1,
122.7, 122.9, 123.2, 123.6, 123.8, 126.4, 127.1, 127.5, 128.2,
128.7, 128.8, 129.0, 129.2, 129.6, 132.6, 133.1, 133.8, 134.9,
138.6, 140.7, 148.4, 148.7, 150.1, 159.6, 181.4, 187.2. – MS
(EI): m/z (%) = 550 (30) [M]+, 472 (10), 93 (100). – UV/Vis
(CHCl3): λmax (lg ε) = 364 (3.7), 521 (4.0) nm. – IR (ATR):
ν = 3412, 2922, 1658, 1494, 1261 cm−1. – HRMS: m/z =
551.24284 (calcd. 551.24470 for C36H31N4O2, [M+H]+).
Acknowledgement
We thank Roche Diagnostics GmbH, Penzberg, for gener-
ous support.
[1] A. Miljkovic, P. Mantle, D. Williams, B. Rassing, J.
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