Anthracene carboxyimides and their dimers

Article abstract of DOI:10.1002/chem.200701844

Soluble anthracenedicarboxyimides have been prepared and undergo a photodimerisation of the anthracene skeleton, which is important for their application as antitumour agents, such as azonafides. Reaction under strongly alkaline conditions causes C-C coup

Full text of DOI:10.1002/chem.200701844

DOI: 10.1002/chem.200701844
Anthracene Carboxyimides and Their Dimers
[a]
HeinzLanghals,* Gertrud Schçnmann, and Kurt Polborn
Abstract: Soluble anthracenedicarboxyimides have been prepared and undergo a
photodimerisation of the anthracene skeleton, which is important for their applica-
tion as antitumour agents, such as azonafides. Reaction under strongly alkaline
Keywords: anthracene derivatives ·
antitumor agents · dyes/pigments ·
fluorescence spectroscopy · photo-
chemistry
À
conditions causes C C coupling to form soluble dimeric fluorescent dyes with
bathochromic absorption and fluorescence in the NIR region. These dyes are of
special interest because of their absorption at longer wavelengths.
Introduction
with oxalyl chloride and aluminium chloride in a ratio of
1.0:5.2:2.0 following the procedure of Liebermann and
Zsuffa[4] to prepare aceanthrenequinone** (2; Scheme 1).
This method proved to give better results than other litera-
ture procedures.[5] The reported sublimation of 2 cannot be
recommended for purification.[4,5a] However, 2 remains as a
very pure, bright-orange, shiny and only sparingly soluble
solid with an intense solid-state fluorescence if anthroic
acid, formed as a byproduct of the synthesis, is completely
removed by means of an alkali. Compound 2 is of interest
as a fluorescent pigment (for its UV/Vis spectrum, see
Figure 1).
Quinone 2 was condensed with hydroxylamine following a
reported procedure to give the regioisomeric oximes 4 and 5
as a 45:55 mixture.[4] The recrystallisation procedure report-
ed for this mixture cannot be recommended for purifica-
tion.[4,5f] The regioisomers were used in the subsequent reac-
tion without separation because interconversion was expect-
ed with the tautomeric nitroso compounds as intermediates
(c.f. ref. [6]). The mixture of 4 and 5 exhibits a strong fluo-
rescence both in solution and in the solid state (see the com-
plicated solid-state fluorescence spectrum in Figure 2). The
oximes can be used as fluorescent pigments because of their
rather low solubility in the majority of solvents. Beckmann
rearrangement of the mixture with concentrated sulfuric
acid led to 6a in a yield of 73% and so separation of the iso-
meric oximes proved unnecessary.
Anthracene-1,9-dicarboxyimides 6 are of special interest as
basic structural elements of antitumour agents, such as az
ACHTREoUNG n-
afides.[1] The chemical behaviour of these substances has not
yet attracted interest in spite of their importance in medical
applications and neither has their strong fluorescence or
photostability. Furthermore, dicarboxyimides 6 are suitable
starting materials for the synthesis of Aceanthrene Green
dyes (7 and 8),[2] which are used as an emerald-green textile
dye (C.I. 71125) and a green pigment.[3] These dyes are of
special interest because of their absorption at longer wave-
lengths. On the other hand, the poor solubility of anthracene
and its dimeric derivatives is an important obstacle to their
investigation and application in homogeneous solution.
Thus, soluble derivatives would be a significant develop-
ment.
Results and Discussion
Anthracene (1) is a suitable starting material for the synthe-
sis of 6. The complete synthesis is reported because of some
improvements and corrections. We treated anthracene (1)
[a] Prof. Dr. H. Langhals, Dr. G. Schçnmann, Dr. K. Polborn+
Department of Chemistry
Compound 2 can be oxidised to anhydride 3 as an alterna-
tive route for the preparation of the anthracenedicarboxy-
AHCTREiUNG mides. Anhydride 3 is highly fluorescent both in solution
LMU University of Munich
Butenandtstr. 13
81377 Munich (Germany)
Fax: (+49)89-2180-77700
E-mail: Langhals@lrz.uni-munchen.de
[+] Author responsible for X-ray crystal structure analysis
[**] The IUPAC name for aceanthrenequinone is aceanthrylene-1,2-
dione.
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FULL PAPER
Scheme 1. Synthesis of anthracene and Aceanthrene Green derivatives. Reagents and conditions: i) (COCl)2, AlCl3; ii) H2O2; iii) NH2OH; iv) H2SO4;
v) RNH2; vi) and vii) KOH; viii) (CH3)2CACTHREGNU(CH2NH2)2; ix) 1,2-C6H4CAHTRE(UGN NH2)2; x), xi) and xii) hn; xiii) 1. KOH; 2. CH3I.
(81% fluorescence quantum yield in chloroform) and in the
solid state. The orange fluorescence of the solid has not
been reported before and makes the substance of special in-
terest as a fluorescence pigment because of its low solubility
and rather high photostability (Figure 3). Dicarboxyimide
6a was prepared by using a modified literature proce-
AHCTREUNG
dure;[2b,c] anhydride 3 was evaporated several times with
concentrated ammonia, however, traces of the starting mate-
rial were difficult to remove. Thus, the synthesis of 6a by
the Beckmann rearrangement of 4 and 5 is preferred.
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H. Langhals et al.
than other six-membered-ring carboxyimides, such as peryle-
nedicarboxyimides.[8] Thus, an acidic workup should be
avoided. The introduction of solubilising swallow-tail sub-
stituents,[9] such as in 6g or the 2,5-di-tert-butylphenyl sub-
stituent in 6j,[10] resulted in readily soluble materials, howev-
er, even simple long-chain alkyl substituents, such as in 6d,
increase the solubility sufficiently for the majority of appli-
cations. X-ray crystal structure analysis was conducted for
6d (Figure 4). The high tendency for crystallisation of 6d
Figure 1. UV/Vis absorption (left) and fluorescence spectra (middle) of 2
in chloroform. Dashed line: solid-state fluorescence spectrum.
Figure 4. X-ray crystal structure of 6d.
was necessary because of photodecomposition (see below).
The anthracene unit of 6d forms one plane and the carboxy-
AHCTREiUNG mide another, twisted at an angle of 58 with respect to the
first. The aliphatic substituent is folded downward and
forms a third plane beneath the aromatic unit with a zigzag
chain.
Figure 2. UV/Vis absorption (left) and fluorescence spectra (middle) of
the mixture of 4 and 5 in chloroform. Dashed line: Solid-state fluores-
cence spectrum.
The anthracenedicarboxyimides are sensitive to daylight
and form the hitherto unknown regioisomeric dimers 10 and
11.[11–14] Their structures were assigned by NMR spectrosco-
py; further isomers could not be detected. The conversion
of 6 into 10 and 11 in daylight reaches a photostationary
equilibrium because of the greater hypsochromic absorption
of the latter. A filter solution of naphthalene-1,8-dicarboxy-
late excludes the hypsochromic UV light (cutoff wavelength
324 nm), and thus allows a complete conversion of 6 into 10
and 11, as indicated by the disappearance of the fluores-
cence. Pure dimerisation products were obtained if the sol-
vent was evaporated during irradiation with this filtered
light. Dissociation of 10 and 11 to starting material 6 can
also proceed thermally, however, this back reaction did not
go to completion and typical yields of 90% were obtained.
The derivatives of 6 in homogeneous solution absorb at
shorter wavelengths and fluoresce with quantum yields close
to 100%. Many derivatives, such as 6b, exhibit strong fluo-
rescence in the solid state (Figure 5).
Figure 3. UV/Vis absorption (left) and fluorescence spectra (middle) of 3
in chloroform. Dashed line: Solid-state fluorescence spectrum.
However, anhydride 3 can be used as a starting material
for the general preparation of 6 by condensation with pri-
mary amines. Ethyl derivative 6b was prepared from 3 and
an aqueous ethylamine solution by a modified procedure;[2d]
the butyl, pentyl and hexyl derivatives (6c, 6d and 6e, re-
spectively) were also obtained from 3 and the pure amines.
The other derivatives of 6 were synthesised from 3 and the
corresponding amines in the presence of imidazole.[7] The di-
carboxyimides are more sensitive towards mineral acids
The photodimerisation of 6 is important because some of
its derivatives are used as tumour static materials.[1] Howev-
er, the dimerisation proceeds even with ambient room light.
Different tumour static activities are expected for 6, 10 and
11, respectively, so care has to be taken in relation to the
effect of common daylight.
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Anthracene Carboxyimides
FULL PAPER
interconverted by crystallisation. The maroon modification
exhibits a very bathochromic solid-state fluorescence.
The UV/Vis absorption of 6 is successively bathochromi-
cally shifted by the replacement of one carbonyl group for
an imino group, to form 12, and by the further extension of
the p system in 13 (Figures 7 and 8, respectively). Com-
pound 13 exhibits a fluorescence quantum yield of 48% in
solution. Both 12 and 13 form photodimerisation products
14/15 and 16/17, respectively.
Figure 5. UV/Vis absorption (left) and fluorescence spectra (middle) of
6b in chloroform. Dashed line: Solid-state fluorescence spectrum.
One of the carbonyl groups in 6 can be replaced with the
related imino group when 3 is condensed with neopentane-
diamine. Only one of the two regioisomers was obtained
and its structure was established by X-ray crystal structure
analysis (Figure 6). The aromatic core of 12 is planar as one
Figure 7. UV/Vis absorption (solid line, left) and fluorescence (solid line,
right) spectra of 12 in chloroform. Dashed line: Solid-state fluorescence
spectrum. The absorption spectrum of 6b (dotted line) is shown for com-
parison.
Figure 8. UV/Vis absorption (solid line, left) and fluorescence (solid line,
right) spectra of 13 in chloroform. Dashed lines: Solid-state fluorescence
spectra of both modifications. The absorption spectrum of 6b (dotted
line) is shown for comparison.
Figure 6. X-ray crystal structure of 12.
Compounds 6 are starting materials for the synthesis of
Aceanthrene Green (7) by KOH melt; dicarboxyimide 6a
can be converted into 7a.[2a,b,9] Alternatively, the mixture of
oximes 4 and 5 can be directly converted into 7a, although
the conditions used for this reaction are strongly alkaline,
whereas acidic conditions are commonly used in the Beck-
mann rearrangement.[16] The simple interconversion of such
oximes[6] via intermediate nitroso compounds may therefore
be of importance. Compound 8a is formed as a byproduct
of the reaction with the alkali melt in a ratio of 1:8 with re-
spect to 7a. This ratio is higher than that reported in a pre-
vious investigation in which 6a was the starting material.[15]
might expect. The dicarboxamidine unit is twisted and the
bond lengths to the anthracene core are longer than the cor-
responding bonds in 6d. The p system of 6 can be further
extended by the condensation of 3 with 1,2-phenylenedi-
ACHTREUNGamine to obtain 13, in which the orientation of the amidine
unit is opposite to that in 12, as established by NMR spec-
troscopy. The amidine from 3 and 1,2-phenylenediamine has
already been reported as a maroon powder with a melting
point of 2348C.[15] A second bright-orange modification of
13 was also found with a melting point of 2288C and a pro-
nounced solid-state fluorescence. Both modifications can be
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H. Langhals et al.
Only 7 was detected in the reaction of N-alkylated or N-ary-
lated derivatives of 6 with the alkali melt (monitored by
TLC and NMR spectroscopy), in accordance with the earlier
chloroform was used as the lipophilic phase in contact with
aqueous 10% hydrogen peroxide. The concentration of
H2O2 should not exceed this value because at higher concen-
trations, such as 30%, the material will be destroyed with
foaming. This method cannot be applied to 6g because the
contact of the vat with chloroform causes spontaneous de-
composition to the starting material. Thus, this vat was oxi-
dised conventionally with air.
The main component Acenanthrene Green 7a and the
minor component 8a form emerald-green solutions with an
intense fluorescence in the visible and NIR regions
(Figure 10 for the similar spectra of 7d). The solid-state
investigation.[15]
.
The alkali-induced coupling of 6 results first in the forma-
tion of a red vat of the green vat dye 7 and is thus complete-
ly different from the formation of other carboxyimides, such
as perylenetetracarboxydiimides. The vat can be conserved
if the alkali melt is allowed to cool and solidify. A dihy-
droaromatic and electrically neutral structure was previously
suggested for this vat,[15] however, such a structure is not in
accordance with the properties of the material. Electropho-
resis indicated a quickly migrating anion for the red materi-
al, which is readily soluble in water and only sparingly solu-
ble in lipophilic solvents. However, more lipophilic than hy-
drophilic properties would be expected for the suggested
structure. Moreover, the suggested structure contains sp3
centres that would be in electronic isolation and thus a hyp-
sochromic UV/Vis absorption, such as that observed for
simple anthracene derivatives would be expected, whereas
the red vat exhibits a bathochromic absorption (Figure 9).
Figure 10. UV/Vis absorption (left) and fluorescence spectra (middle) of
7d in chloroform, together with the solid-state fluorescence spectrum
(right).
fluorescence is bathochromically shifted with respect to that
in chloroform. The solubility of 7a is relatively low and can
be appreciably increased by the attachment of long-chain
alkyl groups to the nitrogen atoms (7b–7 f); the solubility of
7e and 7 f is high enough for the majority of applications.
The solubilising effect of the swallow-tail substituent in 7g is
so pronounced that the material was obtained as a green oil.
Perylenetetracarboxydiimides can be partially hydrolysed
with KOH in tert-butyl alcohol. Derivatives 7 proved to be
completely inert towards this reagent and also remained un-
affected by acids. However, KOH in tert-butyl alcohol indu-
ces a reversible colour change in 7 from green to violet.
This coloured material can be trapped with methyl iodide to
form the methylated derivative 9; addition of the dipolar
aprotic DMSO did not lead to an improvement in the yield.
Alkylation of the aromatic nucleus under these simple reac-
tion conditions was unexpected. The novel chromophore 9
forms bright-orange crystals with an intense solid-state fluo-
rescence and a fluorescence quantum yield in solution of
27% (Figure 11).
Figure 9. UV/Vis absorption spectra of 6g (left) in chloroform, the vat
from the alkali melt of 6g (middle, dashed) in water and 7g in chloro-
form (right).
The investigation of the structure of the vat is rather compli-
cated because slow oxidation of the vat of 6a in aqueous so-
lution leads to insoluble 7a and 8a and this prevents a pre-
cise NMR spectroscopic investigation; acidification or
warming results in the formation of starting material 6. N-
Alkylation of 6 renders the vat more lipophilic so that 6g
becomes soluble in organic solvents. However, contact of
this vat with chloroform results in the spontaneous forma-
tion of the starting material. Oxidation of the vat is delayed
by the addition of pyridine as a trap for nucleophilic free
radicals, whereas formate as a trap for electrophilic free rad-
icals has no effect. Ascorbic acid prevents the formation of
7 and 8.
The vat of 6a can be oxidised by a stream of air,[2,15] how-
ever, several days are required for this to occur and lumps
of the insoluble dye are formed that occlude the starting
material, thus leading to a reduction in the yield. Better re-
sults were obtained in a stirred two-phase system in which
Conclusion
Compounds 6 have proven to be versatile basic starting ma-
terials for developing compounds for pharmaceutical appli-
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Anthracene Carboxyimides
FULL PAPER
177 (11), 176 (73) [MÀ2CO]+, 175 (12), 174 (10), 150 (11)
[MÀ2COÀC2H2]+, 149 (3), 116 (4), 98 (2), 88 (24), 87 (6), 75 (8); ele-
mental analysis calcd (%) for C16H8O2: C 82.75, H 3.47; found: C 80.60,
H 3.50.
Aceanthrenequinone oxime, mixture of isomers 4 and 5:[2] Anhydrous
sodium carbonate (2.20 g, 20.8 mmol) was added to a suspension of
aceanthrenequinone (2, 4.82 g, 20.8 mmol) and hydroxylamine hydrochlo-
ride (1.44 g, 20.7 mmol) in ethanol (50 mL, 96%). The mixture was
heated at reflux with stirring for 30 min (colour change from orange to
ochre-yellow), collected by vacuum filtration (G4 glass filter), washed
with distilled water and dried over calcium chloride to give an ochre elec-
trostatically charging powder. (4.66 g, 91%; lit.:[2] 100%). M.p. 2518C
decomp (lit.:[2] 2518C); Rf (silica gel; CHCl3)=0.03; 1H NMR (CDCl3,
600 MHz): isomer 4 (C=O in p-position of proton 10-H): d=7.68 (m,
2H; aromatic H), 7.84 (m, 1H; aromatic H), 7.93 (d, J=6.6 Hz, 1H; aro-
matic H), 8.10 (d, J=8.7 Hz, 1H; aromatic H), 8.20 (d, J=8.5 Hz, 1H;
aromatic H), 8.83 (s, 1H; aromatic H), 9.06 ppm (d, J=8.5 Hz, 1H; aro-
matic H); isomer 5 (C=NOH in p-position of proton 10-H): 1H NMR
(CDCl3): d=7.68 (m, 2H; aromatic H), 7.78 (m, 1H; aromatic H), 8.10
(d, J=8.7 Hz, 1H; aromatic H), 8.16 (d, J=8.5 Hz, 1H; aromatic H),
8.35 (d, J=6.6 Hz, 1H; aromatic H), 8.73 (s, 1H; aromatic H), 9.19 ppm
(d, J=8.7 Hz, 1H; aromatic H); IR (KBr): n˜ =3248 (m, OH), 3050 (w),
2850 (w), 1705 (s, C=O), 1635 (m, C=N), 1619 (m, C=C), 1576 (m, C=C),
1530 (w, C=C), 1456 (s, OH), 1394 (w), 1225 (w), 1178 (w), 1158 (w),
1079 (w), 1021 (m), 999 (m), 877 (s), 793 (m), 738 (m), 630 (w), 561 (w),
491 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=342 (sh) (3.457), 361 (3.548),
393 (3.461), 407 (sh) (3.429), 432 (3.428), 463 nm (sh) (2.979); fluores-
cence (CHCl3): lmax =481 nm; solid-state fluorescence: lmax =485, 524,
543, 614 nm; MS (70 eV): m/z (%): 248 (12), 247 (63) [M]+, 233 (2), 232
(16), 231 (69), 230 (99) [MÀOH]+, 205 (3), 204 (26), 203 (100)
[MÀOHÀHCN]+, 202 (59) [MÀOHÀCO]+, 201 (30), 200 (2), 190 (3),
187 (4), 178 (3), 177 (8), 176 (27), 175 (22) [203ÀCO]+, 174 (12), 151 (4),
150 (7), 149 (5), 115 (7), 101 (16), 88 (21), 87 (15), 75 (7), 74 (4).
Anthracene-1,9-dicarboxylic anhydride (3):[5a] An aqueous hydrogen per-
oxide solution (46.3 mL, 30%) was slowly added with stirring to acean-
threnequinone (2, 9.25 g, 39.8 mmol) in 1,4-dioxane (200 mL) and 2n
aqueous NaOH (55.5 mL) at reflux. The free anthracene-1,9-dicarboxylic
acid was precipitated by the addition of distilled water (200 mL) and 2n
sulfuric acid (400 mL), and was allowed to stand for 16 h. The light-
yellow precipitate was transformed into the orange anhydride, which was
collected by vacuum filtration (G4 glass filter), dissolved in 2n aqueous
KOH, separated from insoluble material by filtration (G4 glass filter),
precipitated by the dropwise addition of concentrated hydrochloric acid,
collected by vacuum filtration (D4 glass filter), repeatedly washed with
distilled water and dried in air at 1158C to give an orange electrostatical-
ly charging powder (10.15 g, 97%; lit.:[5a] 100% crude material). M.p.
285–2908C (lit.:[5a] 2908C); Rf (silica gel; CHCl3)=0.40; 1H NMR
(CDCl3): d=7.72 (m, 1H; aromatic H), 7.80 (m, 1H; aromatic H), 7.92
(m, 1H; aromatic H), 8.19 (d, J=8.4 Hz, 1H; aromatic H), 8.48 (d, J=
8.4 Hz, 1H; aromatic H), 8.78 (d, J=7.0 Hz, 1H; aromatic H), 8.97 (s,
1H; aromatic H), 9.75 ppm (d, J=9.1 Hz, 1H; aromatic H); 13C NMR
(CDCl3): d=125.8, 126.3, 127.2, 129.9, 132.3, 135.7, 136.4, 137.9 ppm; IR
(KBr): n˜ =3050 (w), 1760 (s, C=O), 1720 (s, C=O), 1622 (w, C=C), 1561
(s, C=C), 1535 (m, C=C), 1432 (w), 1365 (w), 1285 (w), 1268 (w), 1249
Figure 11. UV/Vis absorption (left) and fluorescence spectra (middle) of
9d in chloroform. Dashed line: Solid-state fluorescence spectrum.
cations and as switchable and NIR fluorescent dyes. The
dyes are formed from 6 by reaction under strongly alkaline
À
conditions, which causes C C coupling to form soluble di-
meric fluorescent dyes with bathochromic absorption and
fluorescence in the NIR region. These dyes are of special in-
terest because of their absorption at longer wavelengths.
Experimental Section
General: IR spectra were recorded with a Perkin–Elmer 1420 Ratio Re-
cording Infrared Spectrometer, FT 1000; UV/Vis/NIR spectra were re-
corded with Bruins Omega 20. Fluorescence spectra were recorded with
a Perkin–Elmer FS 3000 spectrophotometer and are totally corrected.
NMR spectroscopy was performed by using a Varian Vnmrs 600 spec-
trometer (600 MHz). Mass spectra were recorded with a Finnigan MAT
95 spectrometer.
Aceanthrenequinone (2):[4] Anthracene (1, 10.00 g, 56.11 mmol), oxalyl
chloride (25 mL, 37 g, 0.30 mol: Caution: toxic!), carbon disulfide
(75 mL) and sublimed anhydrous aluminium chloride (7.93 g, 59.5 mmol)
were stirred under argon with ice-cooling for 2 h (black, viscous materi-
al), treated with further carbon disulfide (75 mL) and aluminium chloride
(7.32 g, 54.9 mmol), stirred for a further 4 h, allowed to stand for 16 h
and hydrolysed by the addition of aqueous 2n HCl (200 mL). Carbon di-
sulfide was removed by distillation (b.p. 428C, bath temperature=50–
708C; Caution! Highly inflammable) and the residue collected by
vacuum filtration (G4 glass filter, orange powder), twice extracted with a
2.5% aqueous solution of potassium carbonate (100 mL each at 708C
and 30 min, vacuum filtration, G4 glass filter), washed with distilled
water (100 mL) and a small amount of methanol and dried at 1158C in
air to give an orange, electrostatically charging powder with a strong
solid-state fluorescence (9.74 g, 75%; lit.:[4] 9.00 g, 69%). M.p. 263–2658C
(lit.:[4] 2708C); Rf (silica gel; CHCl3)=0.58; 1H NMR ([D6]DMSO/
CDCl3, 10:1): d=7.78 (m, 1H; aromatic H), 7.90 (m, 2H; aromatic H),
8.07 (d, J=6.7 Hz, 1H; aromatic H), 8.38 (d, J=8.5 Hz, 1H; aromatic
H), 8.52 (d, J=8.4 Hz, 1H; aromatic H), 9.01 (d, J=8.5 Hz, 1H; aromat-
ic H), 9.17 ppm (s, 1H; aromatic H); 13C NMR ([D6]DMSO/CDCl3,
10:1): d=121.2, 122.9, 123.5, 126.5, 127.1, 127.4, 127.9, 128.0, 129.8, 130.3,
132.2, 132.4, 134.0, 145.7, 187.4 (C=O), 188.3 ppm (C=O); IR (KBr): n˜ =
3051 (w), 1735 (s, C=O), 1707 (s, C=O), 1626 (w, C=C), 1576 (s, C=C),
1529 (w, C=C), 1454 (w), 1436 (w), 1339 (w), 1282 (w), 1226 (w), 1152
(w), 1086 (m), 1016 (w), 919 (w), 883 (w), 752 (m), 741 (m), 700 (w), 483
(w), 411 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=348 (sh) (3.558), 365
(3.804), 382 (sh) (3.678), 404 (3.695), 462 (sh) (3.122), 502 nm (sh)
(2.648); fluorescence (CHCl3): lmax (Irel)=481 (1), 512 (0.81), 557 nm (sh)
(0.28); solid-state fluorescence: lmax =485, 575 (sh), 606 nm; MS (70 eV):
m/z (%): 233 (9), 232 (55) [M]+, 205 (16), 204 (100) [MÀCO]+, 178 (3),
À
À
(w), 1160 (w), 1139 (m, C O), 1086 (m, C O), 1054 (w), 1010 (m), 940
(w), 863 (w), 794 (m), 745 (m), 733 (m), 511 cmÀ1 (w); UV/Vis (CHCl3):
lmax (loge)=269 (4.704), 358 (3.657), 376 (4.037), 414 (3.848), 435 (3.913),
459 nm (3.784); fluorescence (CHCl3): lmax (Irel)=481 (1), 513 (0.80),
553 nm (sh) (0.28); fluorescence quantum yield (CHCl3, reference pery-
lene-3,4,9,10-tetracarboxylic tetramethyl ester[17] with F=1.0): 81%;
solid-state fluorescence: lmax =485, 525, 605 nm; MS (70 eV): m/z (%):
249 (17), 248 (100) [M]+, 205 (8), 204 (52) [MÀCO2]+, 177 (7), 176 (50)
[MÀCO2ÀCO]+, 175 (8), 174 (7), 150 (8), 124 (3), 88 (18), 87 (5), 75 (7).
Anthracene-1,9-dicarboxyimide (6a)[5b,c] from anthracene-1,9-dicarboxyl-
ic anhydride (3):[5b] Anthracene-1,9-dicarboxylic anhydride (3520 mg,
2.09 mmol) was heated with aqueous concentrated ammonia (50 mL) for
1 h and then evaporated three times with concentrated ammonia to com-
plete the reaction. The reaction mixture was suspended in distilled water,
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H. Langhals et al.
collected by vacuum filtration (G4 glass filter), washed with distilled
water and dried in air at 1308C to give an ochre electrostatically charging
powder (440 mg, 85%). M.p. 288–2948C (lit.:[5b] 293–2948C); Rf (silica
gel; CHCl3)=0.16; 1H NMR ([D6]DMSO/CDCl3, 10:1): d=7.71 (m, 1H;
aromatic H), 7.86 (m, 2H; aromatic H), 8.30 (d, J=9.0 Hz, 1H; aromatic
H), 8.62 (2d, J=7.0 Hz, 2H; aromatic H), 9.21 (s, 1H; aromatic H), 9.94
(d, J=9.3 Hz, 1H; aromatic H), 11.70 ppm (s, 1H; NH); 13C NMR
([D6]DMSO/CDCl3, 10:1): d=114.9, 122.6, 125.5, 125.9, 126.3, 129.0,
129.3, 129.9, 131.1, 131.9, 132.4, 132.6, 135.6, 136.9, 163.4 (C=O),
165.6 ppm (C=O); IR (KBr): n˜ =3185 (m), 3067 (m), 2922 (w), 2850 (w),
1687 (s, C=O), 1678 (s, C=O), 1653 (w), 1622 (w, C=C), 1563 (s, C=C),
1532 (m, C=C), 1435 (m), 1397 (m), 1368 (m), 1313 (m), 1281 (m), 1251
(w), 1235 (m), 1153 (w), 909 (w), 858 (w), 799 (w), 746 (w), 733 (m), 677
(w), 625 (w), 505 (w), 416 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=360
(3.570), 379 (3.928), 416 (3.785), 437 (3.900), 462 nm (3.752); fluorescence
(CHCl3): lmax (Irel)=494 (1), 518 nm (0.91); solid-state fluorescence:
lmax =485 (sh), 524, 597, 633 nm (sh); MS (70 eV): m/z (%): 248 (17), 247
(100) [M]+, 246 (6), 219 (10) [MÀCO]+, 204 (4), 203 (13), 202 (3), 191
(3), 190 (8), 177 (3), 176 (10), 175 (3), 163 (3), 150 (3), 124 (3), 110 (4),
88 (7), 87 (3), 75 (3).
chloroform (250 mL), shaken with 2n HCl and distilled water, evaporat-
ed, purified by column chromatography (silica gel, chloroform, exclusion
of light because otherwise dimers would be formed), rapidly evaporated,
dried in an argon gas stream and then in a medium vacuum and stored
under argon in the dark. The product was obtained as a bright golden-
yellow powder with yellow solid-state fluorescence (3.53 g, 73%). M.p.
140–1428C; Rf (silica gel, CHCl3)=0.39; 1H NMR (CDCl3): d=1.01 (m,
3H; CH3), 1.49 (m, 2H; CH2CH3), 1.76 (m, 2H; NCH2CH2), 4.24 (m,
2H; NCH2), 7.58 (m, 1H; aromatic H), 7.67 (m, 1H; aromatic H), 7.78
(m, 1H; aromatic H), 8.05 (d, J=8.5 Hz, 1H; aromatic H), 8.27 (d, J=
8.4 Hz, 1H; aromatic H), 8.69 (d, J=7.1 Hz, 1H; aromatic H), 8.73 (s,
1H; aromatic H), 9.95 ppm (d, J=9.2 Hz, 1H; aromatic H); 13C NMR
(CDCl3): d=14.3 (CH3), 20.9 (CH2), 30.7 (CH2), 40.9 (NCH2), 115.8,
123.0, 125.8, 126.8, 127.2, 128.5, 129.2, 130.1, 131.6, 132.8, 133.8, 134.0,
135.4, 136.6, 164.1 (C=O), 165.6 ppm (C=O); IR (KBr): n˜ ==3067 (w),
3040 (w), 2951 (m), 2935 (m), 2872 (m), 1689 (s, C=O), 1642 (s, C=O),
1621 (m, C=C), 1563 (s, C=C), 1533 (m, C=C), 1433 (m), 1401 (m), 1370
(m), 1354 (m), 1313 (m), 1279 (m), 1220 (m), 1204 (m), 1150 (m), 1111
(s), 903 (m), 861 (m), 828 (m), 797 (m), 750 (s), 741 (s), 662 (w), 625 (w),
544 (w), 516 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=361 (3.196), 380
(3.616), 416 (3.505), 436 (3.631), 459 nm (3.486); fluorescence (CHCl3):
lmax (Irel)=484 (1), 514 (0.79), 556 nm (sh) (0.23); fluorescence quantum
yield (CHCl3, reference perylene-3,4,9,10-tetracarboxylic tetramethyl
ester[17] with F=100%): 100%, solid-state fluorescence: lmax =535 nm;
MS (70 eV): m/z (%): 304 (19), 303 (87) [M]+, 286 (16) [MÀOH]+, 274
(6), 262 (6), 261 (36), 260 (16) [MÀC3H7]+, 259 (8), 248 (22), 247 (100)
[MÀC4H8]+, 231 (6), 230 (7) [247ÀOH]+, 219 (5), 204 (5)
[MÀC4H9NCO]+, 203 (11) [204ÀH]+, 202 (8), 190 (5), 177 (9), 176 (14)
[204ÀCO]+, 150 (2), 88 (4) [176ÀC7H4]+; elemental analysis calcd (%)
for C20H17NO2: C 79.19, H 5.65, N 4.62; found: C 79.45, H 5.67, N 4.53.
Anthracene-1,9-dicarboxyimide (6a) from aceanthrenequinone oxime (4
and 5):[2d] Finely powdered aceanthrenequinone oxime (4 and 5, 450 mg,
1.82 mmol) was heated with concentrated sulfuric acid (3 mL, 30 min) at
1008C (colour change from brown to cherry-red), allowed to cool, diluted
with distilled water, collected by vacuum filtration (G4 glass filter),
washed with distilled water and dried in air at 1308C to give an ochre
electrostatically charging powder (330 mg, 73%; lit.:[2d] nearly quantita-
tive). M.p. 285–2928C (lit.:[2d] 293–2948C); Rf (silica gel; CHCl3)=0.16;
for further spectroscopic data see above.
N-Ethylanthracene-1,9-dicarboxyimide (6b): Compound
3
(1.94 g,
N-Pentylanthracene-1,9-dicarboxyimide (6d): Compound
3
(4.00 g,
7.82 mmol) in aqueous ethylamine solution (75 mL, 70%) was heated at
reflux for 1.5 h (bath 1508C), treated with further ethylamine solution
(25 mL, 70%), heated at reflux for 3.5 h, and cautiously acidified with
concentrated HCl. The product was collected by vacuum filtration (G4
glass filter), thoroughly washed with small amounts of distilled water,
dried in air at 1158C, purified by column chromatography (silica gel,
chloroform, exclusion of light because otherwise dimers would be
formed), rapidly evaporated, dried in an argon gas stream and then in a
medium vacuum and stored in the dark under argon. The product was
obtained as a bright golden-yellow powder with lemon-yellow solid-state
fluorescence (1.63 g, 76%). M.p. 184–1868C; Rf (silica gel; CHCl3)=0.30;
1H NMR ([D6]DMSO/CDCl3, 10:1): d=1.31 (t, J=7.0 Hz, 3H; CH3),
4.23 (q, J=6.9 Hz, 2H; NCH2CH3), 7.72 (t, J=7.1 Hz, 1H; aromatic H),
7.88 (m, 2H; aromatic H), 8.31 (d, J=8.0 Hz, 1H; aromatic H), 8.61 (d,
J=8.5 Hz, 1H; aromatic H), 8.69 (d, J=7.0 Hz, 1H; aromatic H), 9.22 (s,
1H; aromatic H), 9.95 ppm (d, J=9.1 Hz, 1H; aromatic H); 13C NMR
([D6]DMSO/CDCl3, 10:1): d=13.1 (CH3), 34.9 (CH2), 118.5, 121.9, 125.6,
126.0, 126.2, 127.8, 128.6, 130.0, 131.2, 132.0, 132.7, 133.2, 135.5, 136.9,
162.7 (C=O), 164.3 ppm (C=O); IR (KBr): n˜ =3050 (w), 2980 (w), 2935
(w), 1685 (s, C=O), 1653 (s, C=O), 1640 (s, C=O), 1621 (w, C=C), 1560 (s,
C=C), 1533 (m, C=C), 1456 (m), 1437 (m), 1400 (m), 1368 (m), 1351 (m),
1312 (s), 1247 (m), 1231 (m), 1146 (w), 1103 (m), 900 (w), 875 (w), 855
(w), 795 (m), 747 (m), 732 (s), 539 cmÀ1 (m); UV/Vis (CHCl3): lmax
(loge)=361 (3.514), 380 (3.914), 416 (3.790), 437 (3.913), 460 nm (3.771);
fluorescence (CHCl3) lmax (Irel)=486 (1), 516 (0.81), 556 nm (sh) (0.29);
fluorescence quantum yield (CHCl3, reference perylene-3,4,9,10-tetracar-
boxylic tetramethyl ester[17] with F=100%): 44%; solid-state fluores-
cence: lmax =537, 606 nm (sh); MS (70 eV): m/z (%): 276 (20), 275 (94)
[M]+, 274 (9), 260 (17) [MÀCH3]+, 259 (5), 248 (19), 247 (100)
[MÀC2H4]+, 246 (7), 233 (8), 231 (9), 230 (4) [247ÀOH]+, 219 (7), 205
(11), 204 (9) [MÀC2H5NCO]+, 203 (22) [204ÀH]+, 202 (9), 190 (9), 177
(19), 176 (27) [204ÀCO]+, 175 (9), 174 (6), 150 (7), 116 (7), 88 (29)
[176ÀC7H4]+, 75 (6); elemental analysis calcd (%) for C18H13NO2: C
78.53, H 4.76, N 5.09; found: C 78.62, H 4.86, N 4.83.
16.1 mmol) and n-pentylamine (65 mL, 0.56 mol) were heated at reflux
under argon for 3 h, evaporated and further treated as described 6c. The
product was obtained as bright-orange, analytically pure crystals with a
strong solid-state fluorescence (2.60 g 51%). M.p. 133–1358C; Rf (silica
gel; CHCl3)=0.57; 1H NMR (CDCl3): d=0.93 (m, 3H; CH3), 1.45 (m,
4H; (CH2)2CH3), 1.76 (m, 2H; CH2CH2N), 4.22 (m, 2H; CH2N), 7.62 (m,
1H; aromatic H), 7.71 (m, 1H; aromatic H), 7.80 (m, 1H; aromatic H),
8.08 (d, J=6.3 Hz, 1H; aromatic H), 8.33 (d, J=7.6 Hz, 1H; aromatic
H), 8.74 (d, J=5.8 Hz, 1H; aromatic H), 8.80 (s, 1H; aromatic H),
10.01 ppm (d, J=8.0 Hz, 1H; aromatic H); 13C NMR (CDCl3): d=14.1
(CH3), 22.4, 27.9, 29.3, 40.5 (CH2N), 116.0, 123.3, 125.9, 126.9, 127.3,
128.7, 129.3, 130.1, 131.7, 132.5, 132.9, 133.8, 135.4, 136.6, 164.2 (C=O),
165.7 ppm (C=O); IR (KBr): n˜ =3063 (w), 2950 (s), 2936 (m), 2872 (m),
2849 (m), 1685 (s, C=O), 1644 (s, C=O), 1619 (s, C=C), 1561 (s, C=C),
1533 (s, C=C), 1431 (s), 1400 (s), 1371 (s), 1348 (s), 1310 (s), 1279 (m),
1268 (m), 1221 (m), 1193 (m), 1150 (s), 1109 (s), 964 (w), 915 (m), 883
(m), 864 (m), 797 (s), 750 (s), 737 (s), 664 (m), 626 (m), 528 (m),
435 cmÀ1 (m); UV/Vis (CHCl3): lmax (loge)=361 (3.433), 380 (3.889), 416
(3.778), 436 (3.910), 460 nm (3.760); fluorescence (CHCl3): lmax (Irel)=
484 (1), 513 (0.77), 559 nm (sh) (0.21); solid-state fluorescence: lmax
=
474, 505, 523, 610 nm; MS (70 eV): m/z (%): 318 (23), 317 (100) [M]+,
300 (11) [MÀOH]+, 274 (5), 261 (33), 260 (15) [MÀC4H9]+, 248 (24), 247
(90) [MÀC5H10]+, 230 (6) [247ÀOH]+, 219 (4), 204 (4) [MÀC5H9NCO]+,
203 (9), 202 (7), 190 (4), 177 (8), 176 (11) [204ÀCO]+, 88 (3)
[176ÀC7H4]+; elemental analysis calcd (%) for C21H19NO2: C 79.47, H
6.03, N 4.41; found: C 79.43, H 5.93, N 4.32.
Crystal data for 6d: The crystal structure was determined with an Enraf-
Nonius CAD4 diffractometer with MoKa radiation and a highly oriented
graphite crystal as monochromator. C21H19NO2, Mr =317.37, a=
11.525(5), b=15.794(6), c=9.563(4) Š, b=113.16(2)8, volume=
1600.4(11) Š3, Z=4, 1calcd =1.317 gcmÀ3
, , monoclinic,
m=0.084 mmÀ1
space group P21/c (Nr. 14). Data collection: single crystal 0.40”0.47”
0.53 mm3 (orange block); w data collection, scan width 0.80+0.35tanq;
maximal collection time 90 s for each reflex, number of reflections: 2344
(collected), 2223 (independent), 1739 (observed) [I>2s(I)], no correc-
tion for absorption, structure solution with SHELXS86, refinement with
SHELXL93,[18] 218 parameters, R1 =0.0499(2s(I)), wR2 =0.1386(2s(I)),
N-Butylanthracene-1,9-dicarboxyimide (6c): Compound
3
(3.96 g,
16.0 mmol) in n-butylamine (100 mL, 1.01 mol) and toluene (10 mL) was
heated at reflux under argon for 2.5 h. The mixture was evaporated at
normal pressure (dark-red residue) and the residue was suspended in
5296
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 5290 – 5303

Anthracene Carboxyimides
FULL PAPER
2
weighing w=1/[s2Fo +0.0693], GOF=1.080, max. and min. residual elec-
(m, 2H; (CH2)CHN), 5.27 (m, 1H; (CH2)2CHN), 7.61 (m, 1H; aromatic
H), 7.72 (m, 1H; aromatic H), 7.81 (m, 1H; aromatic H), 8.10 (d, J=
8.4 Hz, 1H; aromatic H), 8.33 (d, J=8.4 Hz, 1H; aromatic H), 8.72 (d,
J=6.9 Hz, 1H; aromatic H), 8.81 (s, 1H; aromatic H), 9.96 ppm (d, J=
9.1 Hz, 1H; aromatic H); 13C NMR (CDCl3) d=14.0 (CH3), 22.6, 27.0,
29.3, 31.8, 32.6, 54.6 (NCHR2), 125.5, 126.4, 127.0, 128.5, 128.8, 129.7,
131.0, 132.6, 134.6, 135.8 ppm; IR (KBr): n˜ =3050 (w), 2955 (m), 2925 (s),
2855 (m), 1689 (s, C=O), 1653 (s, C=O), 1617 (w, C=C), 1563 (m, C=C),
1533 (m, C=C), 1457 (m), 1430 (m), 1399 (m), 1369 (m), 1309 (m), 1280
(m), 1243 (m), 1212 (m), 1191 (m), 1150 (w), 1114 (m), 895 (w), 793 (w),
750 (w), 730 (m), 624 (w), 610 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=
361 (2.628), 380 (3.016), 415 (2.929), 435 (3.051), 459 nm (2.898); fluores-
cence (CHCl3): lmax (Irel)=481 (1), 512 nm (0.78); solid-state fluores-
cence: lmax =485, 524, 632 nm; MS (70 eV): m/z (%): 430 (10), 429 (33)
[M]+, 344 (3) [MÀC6H13]+, 260 (6), 248 (45), 247 (100) [MÀC13H26]+, 230
(7) [247ÀOH]+, 205 (4), 204 (2) [MÀC13H27NCO]+, 203 (4), 202 (5), 177
(3), 176 (3) [204ÀCO]+; elemental analysis calcd (%) for C29H35NO2: C
81.08, H 8.21, N 3.29; found: C 80.90, H 8.29, N 3.14.
À3
tron density 0.310/À0.182 eŠ
CCDC 679419 contains the supplementary crystallographic data for 6d.
These data can be obtained free of charge from the Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
.
N-Hexylanthracene-1,9-dicarboxyimide (6e): Compound
3
(4.10 g,
16.5 mmol) and n-hexylamine (120 mL, 0.908 mol) were allowed to react
as described for 6d for 1 h 45 min. The product was obtained as bright-
yellow crystals with an intense solid-state fluorescence (4.42 g, 81%).
1
M.p. 109–1108C; Rf (silica gel; CHCl3)=0.56; H NMR (CDCl3): d=0.89
(m, 3H; CH3), 1.40 (m, 6H; (CH2)3CH3), 1.78 (m, 2H; CH2CH2N), 4.25
(m, 2H; CH2N), 7.61 (m, 1H; aromatic H), 7.71 (m, 1H; aromatic H),
7.81 (m, 1H; aromatic H), 8.10 (d, J=7.8 Hz, 1H; aromatic H), 8.33 (d,
J=8.4 Hz, 1H; aromatic H), 8.74 (d, J=7.1 Hz, 1H; aromatic H), 8.81 (s,
1H; aromatic H), 10.01 ppm (d, J=9.2 Hz, 1H; aromatic H); 13C NMR
(CDCl3): d=14.1 (CH3), 22.6, 26.8, 28.1, 31.6, 40.7 (CH2N), 115.6, 122.7,
125.5, 126.4, 126.9, 128.4, 128.9, 129.7, 131.2, 132.5, 133.4, 133.6, 135.0,
136.2, 163.7 (C=O), 165.2 ppm (C=O); IR (KBr): n˜ =3120 (w), 3060 (w),
2957 (s), 2925 (s), 2853 (s), 1685 (s, C=O), 1644 (s, C=O), 1620 (m, C=C),
1561 (s, C=C), 1532 (s, C=C), 1452 (m), 1431 (s), 1402 (m), 1370 (m),
1353 (s), 1312 (s), 1279 (m), 1253 (m), 1219 (m), 1190 (m), 1149 (m),
1111 (s), 914 (m), 862 (m), 798 (s), 752 (s), 737 (s), 660 (w), 621 (w), 559
(w), 528 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=361 (3.269), 380 (3.591),
416 (3.484), 436 (3.596), 460 nm (3.464); fluorescence (CHCl3): lmax
(Irel)=481 (1), 512 nm (0.77); solid-state fluorescence: lmax =560 nm; MS
(70 eV): m/z (%): 332 (23), 331 (100) [M]+, 314 (9) [MÀOH]+, 274 (4),
262 (6), 261 (31), 260 (15), 259 (6), 248 (24), 247 (81) [MÀC6H12]+, 230
(6) [247ÀOH]+, 219 (4), 204 (4) [MÀC6H13NCO]+, 203 (8), 202 (6), 190
(4), 177 (6), 176 (9) [204ÀCO]+; elemental analysis calcd (%) for
C22H21NO2: C 79.73, H 6.39, N 4.23; found: C 79.30, H 6.28, N 4.33.
N-(2-Ethylphenyl)anthracene-1,9-dicarboxyimide (6h): Compound
3
(2.06 g, 8.30 mmol), 2-ethylaniline (2.01 g, 16.6 mmol), zinc acetate dihy-
drate (330 mg) and imidazole (10 g) were allowed to react (4 h) as de-
scribed for 6 f. The product was obtained as a brightly shining yellowish-
orange powder with a strong solid-state fluorescence (1.31 g, 45%). M.p.
175–1768C; Rf (silica gel, CHCl3)=0.21; 1H NMR (CDCl3): d=1.18 (t,
J=7.7 Hz, 3H; CH3), 2.57 (q, J=7.5 Hz, 2H; CH2CH3), 7.27 (d, J=
7.4 Hz, 1H; aromatic H), 7.41 (m, 1H; aromatic H), 7.49 (m, 2H; aro-
matic H), 7.65 (m, 1H; aromatic H), 7.81 (m, 2H; aromatic H), 8.17 (d,
J=8.4 Hz, 1H; aromatic H), 8.45 (d, J=7.6 Hz, 1H; aromatic H), 8.83
(d, J=7.0 Hz, 1H; aromatic H), 8.93 (s, 1H; aromatic H), 9.98 ppm (d,
J=9.1 Hz, 1H; aromatic H); 13C NMR (CDCl3): d=13.9 (CH3), 24.1
(CH2), 115.5, 122.8, 125.6 (CH), 126.7 (CH), 127.0 (CH), 127.1 (CH),
127.2, 128.8 (CH), 129.18 (CH), 129.11, 129.2 (CH), 129.7 (CH), 131.6
(CH), 132.6, 133.9, 134.9 (CH), 134.8, 135.5 (CH), 136.8 (CH), 141.4,
163.8 (C=O), 165.4 ppm (C=O); IR (KBr): n˜ =3060 (w), 2970 (w), 2935
(w), 2875 (w), 1695 (s, C=O), 1658 (s, C=O), 1623 (m, C=C), 1563 (s, C=
C), 1532 (m, C=C), 1493 (m), 1454 (m), 1430 (m), 1392 (m), 1370 (m),
1320 (m), 1254 (m), 1214 (s), 1197 (m), 1148 (m), 1054 (w), 888 (m), 860
(w), 795 (m), 751 (s), 735 (s), 659 (m), 493 cmÀ1 (w); UV/Vis (CHCl3):
lmax (loge)=361 (3.294), 380 (3.623), 418 (3.538), 438 (3.651), 462 nm
(3.521); fluorescence (CHCl3): lmax (Irel)=481 (1), 512 nm (0.77); solid-
state fluorescence: lmax =486, 524, 544 (sh), 600, 630 nm (sh); MS
(70 eV): m/z (%): 352 (16), 351 (66) [M]+, 335 (24), 334 (91) [MÀOH]+,
323 (17), 322 (71) [MÀC2H5]+, 319 (24), 306 (12), 291 (16), 247 (11), 204
(5) [MÀC2H5ÀC6H4ÀNCO]+, 203 (9), 202 (12), 177 (11), 176 (24)
[204ÀCO]+, 175 (11), 150 (10) [176ÀC2H2]+, 121 (43), 106 (100), 101
(13); elemental analysis calcd (%) for C24H17NO2: C 82.03, H 4.88, N
3.99; found: C 82.47, H 5.17, N 4.15.
N-Nonylanthracene-1,9-dicarboxyimide (6 f): Compound
3
(2.03 g,
8.18 mmol), n-nonylamine (2.07 g, 14.4 mmol) and zinc acetate dihydrate
(350 mg) in imidazole (9 g) were heated under argon at 1508C for 4 h.
The resulting mixture was treated dropwise with concentrated HCl whilst
still warm and then added to chloroform, separated from the red HCl
phase, extracted with a small amount of 2n HCl, dried, evaporated and
purified by fast pressure-induced column chromatography (silica gel,
chloroform, exclusion of light), rapidly evaporated, dried in a stream of
argon and then in a medium vacuum and stored in the dark. The product
was obtained as a bright-yellow powder with a strong solid-state fluores-
cence (2.00 g, 65%). M.p. 141–1438C; Rf (silica gel; CHCl3)=0.67;
1H NMR (CDCl3): d=0.85 (m, 3H; CH3), 1.38 (m, 12H; (CH2)6CH3),
1.77 (m, 2H; NCH2CH2), 4.26 (m, 2H; NCH2), 7.63 (m, 1H; aromatic
H), 7.72 (m, 1H; aromatic H), 7.81 (m, 1H; aromatic H), 8.11 (d, J=
8.4 Hz, 1H; aromatic H), 8.35 (d, J=8.4 Hz, 1H; aromatic H), 8.75 (d,
J=7.1 Hz, 1H; aromatic H), 8.82 (s, 1H; aromatic H), 10.02 ppm (d, J=
9.2 Hz, 1H; aromatic H); 13C NMR (CDCl3): d=14.0 (CH3), 22.6, 27.2,
28.1, 29.2, 29.4, 29.5, 31.8, 40.6 (CH2N), 122.6, 125.4, 126.4 126.8, 128.3,
128.6, 129.6, 131.2, 132.2, 132.8, 133.4, 134.9, 136.1, 162.3 (C=O),
165.1 ppm (C=O); IR (KBr): n˜ =3068 (w), 2957 (m), 2926 (s), 2854 (m),
1685 (s, C=O), 1660 (s, C=O), 1601 (w, C=C), 1560 (m, C=C), 1534 (w,
C=C), 1462 (w), 1452 (w), 1394 (w), 1355 (s), 1311 (w), 1280 (w), 1243
(w), 1170 (w), 1109 (w), 902 (w), 820 (w), 778 (w), 750 (m), 712 (w),
605 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=361 (3.457), 380 (3.722), 416
(3.590), 437 (3.696), 461 nm (3.555); fluorescence (CHCl3): lmax (Irel)=
485 (1), 513 nm (0.77); solid-state fluorescence: lmax =536, 635 nm (sh);
MS (70 eV): m/z (%): 374 (26), 373 (100) [M]+, 356 (7) [MÀOH]+, 261
(29), 260 (17) [MÀC8H17]+, 248 (29), 247 (72) [MÀC9H18]+, 230 (7)
[247ÀOH]+, 205 (5), 204 (5) [MÀC9H19NCO]+, 203 (10), 202 (7), 177 (9),
176 (10) [204ÀCO]+; elemental analysis calcd (%) for C25H27NO2: C
80.40, H 7.29, N 3.75; found: C 80.41, H 7.30, N 3.79.
N-(2,3-Dimethylphenyl)anthracene-1,9-dicarboxyimide (6i): Compound 3
(1.99 g, 8.02 mmol), 2,3-dimethylaniline (1.98 g, 16.3 mmol), zinc acetate
dihydrate (370 mg) and imidazole (10 g) were allowed to react (4 h) as
described for 6 f. The product was obtained as orange crystals with
yellow solid-state fluorescence (1.57 g, 56%). M.p. 290–2918C; Rf (silica
gel; CHCl3)=0.24; 1H NMR (CDCl3): d=2.11 (s, 3H; CH3), 2.48 (s, 3H;
CH3), 7.36 (m, 2H; aromatic H), 7.65 (m, 1H; aromatic H), 7.80 (m, 2H;
aromatic H), 7.89 (m, 1H; aromatic H), 8.16 (d, J=7.7 Hz, 1H; aromatic
H), 8.44 (d, J=8.3 Hz, 1H; aromatic H), 8.82 (d, J=7.1 Hz, 1H; aromat-
ic H), 8.93 (s, 1H; aromatic H), 9.98 ppm (d, J=9.1 Hz, 1H; aromatic
H); 13C NMR (CDCl3): d=14.6 (CH3), 20.9 (CH3), 113.6, 123.2, 126.0,
126.3, 126.5, 126.9, 127.1, 127.4, 127.5, 127.8, 129.5, 130.2, 130.9, 131.3,
132.0, 133.0, 134.4, 135.9, 137.2, 138.6, 163.0 (C=O), 163.5 ppm (C=O);
IR (KBr): n˜ =3070 (w), 2920 (w), 1718 (m), 1695 (w), 1680 (s, C=O),
1660 (s, C=O), 1602 (w, C=C), 1565 (m, C=C), 1535 (w, C=C), 1472 (m),
1452 (w), 1392 (w), 1366 (s), 1321 (m), 1267 (m), 1239 (m), 1215 (m),
1200 (w), 1152 (w), 884 (w), 777 (m), 753 (m), 738 (m), 710 (m), 610 (w),
557 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=361 (3.539), 380 (3.946), 418
(3.857), 438 (3.986), 463 nm (3.839); fluorescence (CHCl3): lmax (Irel)=
483 (1), 513 nm (0.76); solid-state fluorescence: lmax =484, 523, 540 (sh),
631 nm; MS (70 eV): m/z (%): 352 (11), 351 (46) [M]+, 337 (8), 336 (36),
335 (25), 334 (100) [MÀOH]+, 319 (11), 306 (6) [334ÀCO]+, 291 (8), 230
N-(1-Hexylheptyl)anthracene-1,9-dicarboxyimide (6g): Compound
3
(1.94 g, 7.82 mmol), 1-hexylheptylamine (2.22 g, 11.1 mmol), zinc acetate
dihydrate (350 mg) and imidazole (10 g) were allowed to react (4 h) as
described for 6 f. The product was obtained as yellow crystals with a
brightly shining yellow solid-state fluorescence (2.15 g, 64%). M.p.
2458C, Rf (silica gel, toluene)=0.80; 1H NMR (CDCl3): d=0.79 (t, J=
6.8 Hz, 6H; CH3), 1.26 (m, 16H; (CH2)4), 1.88 (m, 2H; (CH2)CHN), 2.28
Chem. Eur. J. 2008, 14, 5290 – 5303
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5297

H. Langhals et al.
(3), 202 (4), 176 (14), 175 (3), 168 (3); elemental analysis calcd (%) for
C24H17NO2: C 82.03, H 4.88, N 3.99; found: C 82.23, H 5.07, N 3.99.
[247ÀOH]+, 219 (7), 205 (11), 204 (9) [MÀC2H5NCO]+, 203 (22)
[204ÀH]+, 202 (9), 190 (9), 177 (19), 176 (27) [204ÀCO]+, 175 (9), 174
(6), 150 (7), 116 (7), 88 (29) [176ÀC7H4]+, 75 (6).
N-(2,5-Di-tert-butylphenyl)anthracene-1,9-dicarboxyimide (6j): Com-
pound 3 (1.98 g, 7.98 mmol), 2,5-di-tert-butylaniline (2.37 g, 11.5 mmol),
zinc acetate dihydrate (350 mg) and imidazole (10 g) were allowed to
react (4 h) as described for 6 f. The product was obtained as bright
N-Butylanthracene-1,9-dicarboxyimide dimers 10c and 11c: Compound
6c (200 mg, 6.6 mmol) was allowed to react according to the general pro-
cedure for photodimerisation. The product was obtained as a pale-yellow
powder (200 mg, ꢀ100%). M.p. 170–1728C; Rf (silica gel; CHCl3)=0.50;
1H NMR (CDCl3): d=1.03 (t, J=7.3 Hz, 6H; CH3), 1.49 (m, 4H;
CH2CH3), 1.76 (q, J=7.1 Hz, 4H; NCH2CH2), 4.24 (m, 4H; NCH2), 4.79
(s, 1H), 4.80 (s, 1H), 6.77 (m, 1H; aromatic H), 6.84 (m, 1H; aromatic
H), 6.98 (m, 5H; aromatic H), 7.10 (m, 1H; aromatic H), 7.25 (m, 1H;
aromatic H), 7.48 (m, 3H; aromatic H), 7.78 (m, 1H; aromatic H),
7.81 ppm (m, 1H; aromatic H); 13C NMR (CDCl3): d=14.3 (CH3), 20.8
(CH2), 30.8 (CH2), 40.7 (NCH2), 58.3, 62.4 (CH), 62.5 (CH), 123.3, 123.5,
126.0, 126.2, 127.1, 127.3, 127.4, 127.57, 127.63, 127.8, 128.0, 128.7, 130.0,
132.5, 133.9, 140.2, 140.5, 140.7, 141.1, 141.4, 142.2, 142.7, 163.7 (C=O),
163.8 (C=O), 173.9 (C=O), 174.1 ppm (C=O); IR (KBr): n˜ =3068 (w),
2960 (m), 2932 (m), 2872 (w), 1709 (s, C=O), 1667 (s, C=O), 1602 (w, C=
C), 1481 (w, C=C), 1462 (m), 1452 (m), 1433 (w), 1390 (m), 1355 (s), 1322
(w), 1275 (w), 1239 (m), 1190 (w), 1139 (w), 1099 (m), 939 (w), 819 (w),
779 (w), 755 (m), 708 (m), 671 (w), 610 cmÀ1 (m); UV/Vis (CHCl3): lmax
(loge)=264 (4.123) (sh), 302 (3.512), 313 nm (3.466); MS (70 eV): m/z
(%): 304 (19), 303 (87) [M]+, 286 (16) [MÀOH]+, 274 (6), 262 (6), 261
(36), 260 (16) [MÀC3H7]+, 259 (8), 248 (22), 247 (100) [MÀC4H8]+, 231
(6), 230 (7) [247ÀOH]+, 219 (5), 204 (5) [MÀC4H9NCO]+, 203 (11)
[204ÀH]+, 202 (8), 190 (5), 177 (9), 176 (14) [204ÀCO]+, 150 (2), 88 (4)
[176ÀC7H4]+.
N-Pentylanthracene-1,9-dicarboxyimide dimers 10d and 11d: Compound
6d (200 mg, 6.3 mmol) was allowed to react according to the general pro-
cedure for photodimerisation. The product was obtained as a pale-yellow
powder (200 mg ꢀ100%). M.p. 159–1628C; Rf (silica gel; CHCl3)=0.62;
1H NMR (CDCl3): d=0.96 (m, 6H; CH3), 1.45 (m, 8H; (CH2)2CH3), 1.79
(m, 4H; CH2CH2N), 4.25 (m, 4H; CH2N), 4.81 (s, 1H), 4.82 (s, 1H), 6.79
(m, 1H; aromatic H), 6.86 (m, 1H; aromatic H), 7.01 (m, 5H; aromatic
H), 7.11 (m, 1H; aromatic H), 7.27 (m, 1H; aromatic H), 7.45 (m, 3H;
aromatic H), 7.80 (m, 1H; aromatic H), 7.83 ppm (m, 1H; aromatic H);
13C NMR (CDCl3): d=12.2 (CH3), 20.5, 26.0, 27.4, 38.6 (CH2N), 55.9,
60.1 (CH), 60.2 (CH), 121.0, 121.2, 123.6, 123.9, 124.8, 125.1, 125.1, 125.3,
125.3, 125.4, 125.7, 126.4, 127.7, 130.2, 131.6, 137.9, 138.2, 138.4, 138.8,
139.1, 139.9, 140.4, 161.3 (C=O), 161.4 (C=O), 171.6 (C=O), 171.8 ppm
(C=O); IR (KBr): n˜ =3069 (w), 2957 (m), 2930 (m), 2860 (w), 1709 (s,
C=O), 1668 (s, C=O), 1602 (w, C=C), 1481 (w, C=C), 1462 (w), 1452 (w),
1434 (w), 1390 (w), 1355 (m), 1309 (w), 1262 (w), 1241 (w), 1187 (w),
1141 (w), 1102 (m), 1073 (w), 819 (w), 779 (w), 756 (w), 709 (w), 670 (w),
610 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=266 (4.733), 300 (3.619), 313
(3.591), 360 (3.233), 380 (3.584), 415 (3.466), 437 (3.595), 461 nm (3.446);
MS (70 eV): m/z (%): 318 (23), 317 (100) [M]+, 300 (11) [MÀOH]+, 274
(5), 261 (33), 260 (15) [MÀC4H9]+, 248 (24), 247 (90) [MÀC5H10]+, 230
(6) [247ÀOH]+, 219 (4), 204 (4) [MÀC5H9NCO]+, 203 (9), 202 (7), 190
(4), 177 (8), 176 (11) [204ÀCO]+, 88 (3) [176ÀC7H4]+.
golden-yellow crystals with
64%). M.p. 335–3378C; Rf (silica gel; CHCl3)=0.73; 1H NMR (CDCl3):
d=1.31 (s, 9H; C(CH3)3), 1.34 (s, 9H; C(CH3)3), 7.07 (d, J=2.2 Hz, 1H;
a strong solid-state fluorescence (2.22 g,
A
ACHTREUNG
aromatic H), 7.47 (dd, J1 =8.4, J2 =2.2 Hz, 1H; aromatic H), 7.61 (d, J=
8.5 Hz, 1H; aromatic H), 7.66 (m, 1H; aromatic H), 7.83 (m, 2H; aro-
matic H), 8.17 (d, J=8.6 Hz, 1H; aromatic H), 8.45 (d, J=8.4 Hz, 1H;
aromatic H), 8.84 (d, J=7.2 Hz, 1H; aromatic H), 8.93 (s, 1H; aromatic
H), 9.97 (d, J=9.3 Hz, 1H; aromatic H); 13C NMR (CDCl3): d=31.3
(CH3), 31.7 (CH3), 34.3 (CACHTREUN(G CH3)3), 35.5 (CACHTREU(NG CH3)3), 113.4, 123.1, 125.6,
126.1, 126.6, 127.0, 128.1, 128.7, 129.0, 129.2, 129.7, 131.5, 132.6, 133.5,
133.85, 133.92, 135.3, 136.6, 143.7, 150.0, 164.7 (C=O), 166.5 ppm (C=O);
IR (KBr): n˜ =3050 (w), 2963 (m), 2910 (w), 2875 (w), 1700 (s, C=O),
1662 (s, C=O), 1621 (w, C=C), 1563 (s, C=C), 1532 (m, C=C), 1430 (m),
1398 (m), 1372 (m), 1318 (m), 1279 (w), 1251 (w), 1213 (m), 1185 (w),
1176 (w), 1145 (w), 1055 (w), 895 (w), 840 (w), 796 (w), 752 (w), 736 (m),
722 (w), 667 (w), 625 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=361
(3.583), 379 (3.868), 416 (3.753), 436 (3.873), 462 nm (3.731); fluorescence
(CHCl3): lmax (Irel)=481 (1), 512 nm (0.77); fluorescence quantum yield
(CHCl3, reference perylene-3,4,9,10-tetracarboxylic tetramethyl ester[17]
with F=100%): 92%; solid-state fluorescence: lmax =529, 559 nm (sh);
MS (70 eV): m/z (%): 435 (2) [M]+, 380 (5), 379 (28), 378 (100)
[MÀC4H9]+, 363 (5), 362 (12), 346 (3), 279 (5), 167 (10), 149 (33), 112
(4), 111 (5), 109 (3), 105 (3), 97 (7), 95 (5), 91 (4), 85 (10), 83 (17), 81 (6),
71 (11), 69 (11), 57 (18), 55 (12); elemental analysis calcd (%) for
C30H29NO2: C 82.73, H 6.71, N 3.22; found: C 82.77, H 6.66, N 3.22.
Dimerisation of the anthracene-1,9-dicarboxyimides—preparation of the
optical filter solution and apparatus for irradiation: A solution was pre-
pared with naphthalene-1,8-dicarboxylic anhydride and KOH pellets (ef-
ficient exclusion of carbonate) in distilled water so that an extinction of
4–5 cmÀ1 was obtained between 250 and 320 nm; cutoff wavelength=
324 nm and absorptivity E=1 per cm at 329 nm. The extinction must be
low for l>360 nm. The anthracene-1,9-dicarboxyimides to be dimerised
were dissolved in chloroform in standard NMR tubes (5 mm diameter),
placed in the centre of the beaker and irradiated from the side through
the filter solution by using a 150 W tungsten wire bulb lamp.
Photoreaction of anthracene-1,9-dicarboxyimides to form 10 and 11—
general procedure: Compounds 6 (200 mg, about 0.5–0.7 mmol depend-
ing on the substituents on the nitrogen atoms of 6) to be dimerised were
dissolved in chloroform (1 mL or more) in a standard NMR tube (inner
diameter 4 mm). The tube was sealed and irradiated through the filter so-
lution of dipotassium naphthalene-1,8-dicarboxylate for several days until
fluorescence had completely disappeared. The NMR tube was then
opened and irradiation was continued until complete evaporation.
N-Ethylanthracene-1,9-dicarboxyimide dimers 10b and 11b: Compound
6b (200 mg, 7.3 mmol) was allowed to react according to the general pro-
cedure for photodimerisation. The product was obtained as a pale-yellow
powder (200 mg ꢀ100%). M.p. 173–1758C; Rf (silica gel; CHCl3)=0.34;
1H NMR (CDCl3): d=0.90 (m, 6H; CH3), 4.23 (m, 2H; NCH2CH3), 4.33
(m, 2H; NCH2CH3), 4.81 (s, 1H), 4.83 (s, 1H), 6.78 (m, 1H; aromatic
H), 6.86 (m, 1H; aromatic H), 7.00 (m, 5H; aromatic H), 7.12 (m, 1H;
aromatic H), 7.51 (m, 3H; aromatic H), 7.72 (m, 1H; aromatic H), 7.81
(m, 1H; aromatic H), 7.83 ppm (m, 1H; aromatic H); 13C NMR (CDCl3):
d=13.9 (CH3), 36.1 (CH2), 58.2, 62.4 (CH), 123.6, 125.96, 126.04, 127.4,
127.6, 128.0, 129.2, 130.0, 131.3, 132.5, 132.8, 135.5, 140.2, 140.7, 141.2,
143.2, 144.0, 165.3 (C=O), 173.7 ppm (C=O); IR (KBr): n˜ =3079 (w),
2980 (w), 2936 (w), 1707 (m, C=O), 1666 (s, C=O), 1603 (w, C=C), 1560
(w), 1482 (w, C=C), 1452 (w), 1437 (w), 1388 (w), 1371 (w), 1356 (m),
1312 (w), 1250 (m), 1231 (w), 1138 (w), 1096 (m), 824 (w), 796 (w), 780
(w), 751 (w), 732 (w), 708 (w), 670 (w), 609 cmÀ1 (w); UV/Vis (CHCl3):
lmax (loge)=264 (4.026) (sh), 300 (3.366), 313 nm (3.280); MS (70 eV):
m/z (%): 276 (20), 275 (94) [M]+, 274 (9), 260 (17) [MÀCH3]+, 259 (5),
248 (19), 247 (100) [MÀC2H4]+, 246 (7), 233 (8), 231 (9), 230 (4)
N-Hexylanthracene-1,9-dicarboxyimide dimers 10e and 11e: Compound
6e (200 mg, 6.0 mmol) was allowed to react according to the general pro-
cedure for photodimerisation. The product was obtained as a pale-yellow
powder (200 mg, ꢀ100%). M.p. 165–1668C; Rf (silica gel; CHCl3)=0.89;
1H NMR (CDCl3): d=0.91 (m, 6H; CH3), 1.40 (m, 12H; (CH2)3CH3),
1.78 (m, 4H; CH2CH2N), 4.25 (m, 4H; CH2N), 4.80 (s, 1H), 4.82 (s, 1H),
6.77 (m, 1H; aromatic H), 6.85 (t, J=7.1 Hz, 1H; aromatic H), 6.98 (m,
5H; aromatic H), 7.10 (t, J=7.7 Hz, 1H; aromatic H), 7.27 (m, 1H; aro-
matic H), 7.48 (m, 3H; aromatic H), 7.79 (m, 1H; aromatic H), 7.81 ppm
(m, 1H; aromatic H); 13C NMR (CDCl3): d=14.5 (CH3), 23.1, 27.2, 28.7,
32.0, 40.9 (CH2N), 58.3, 62.4 (CH), 62.6 (CH), 123.3, 123.5, 126.0, 126.2,
127.2, 127.3, 127.4, 127.6, 127.6, 127.8, 128.0, 128.7, 130.0, 132.5, 133.9,
140.2, 140.5, 140.67, 140.70, 141.2, 141.4, 142.2, 142.7, 163.6 (C=O), 163.8
(C=O), 173.9 (C=O), 174.1 ppm (C=O); IR (KBr): n˜ =2957 (m), 2930 (s),
2858 (m), 1708 (s, C=O), 1667 (s, C=O), 1602 (w, C=C), 1462 (w, C=C),
1434 (w), 1390 (w), 1355 (s), 1250 (w), 1182 (w), 1140 (w), 1101 (w), 1073
(w), 820 (w), 779 (w), 757 (w), 709 (w), 671 (w), 610 cmÀ1 (m); UV/Vis
(CHCl3): lmax (loge)=265 (4.418), 301 (3.302), 313 nm (3.154); MS (FAB,
5298
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 5290 – 5303

Anthracene Carboxyimides
FULL PAPER
3-nitrobenzyl alcohol): m/z: 685 [M+Na]+, 663 [M]+; MS (70 eV): m/z
(%): 332 (23), 331 (100) [M]+, 314 (9) [MÀOH]+, 274 (4), 262 (6), 261
(31), 260 (15), 259 (6), 248 (24), 247 (81) [MÀC6H12]+, 230 (6)
[247ÀOH]+, 219 (4), 204 (4) [MÀC6H13NCO]+, 203 (8), 202 (6), 190 (4),
177 (6), 176 (9) [204ÀCO]+.
N-(2,3-Dimethylphenyl)anthracene-1,9-dicarboxyimide dimers 10i and
11i: Compound 6i (200 mg, 5.7 mmol) was allowed to react according to
the general procedure for photodimerisation. The product was obtained
as a pale-yellow powder (200 mg, ꢀ100%). M.p. 290–2928C; Rf (silica
gel; CHCl3)=0.29; 1H NMR (CDCl3): d=2.00 (s, 3H; CH3), 2.40 (s, 6H;
CH3), 2.49 (s, 3H; CH3), 5.03 (m, 2H), 6.95–7.52 (m, 18H; aromatic H),
7.87 ppm (m, 2H; aromatic H); 13C NMR (CDCl3): d=14.5 (CH3), 14.9
(CH3), 20.9 (CH3), 58.9, 62.5 (CH), 62.9 (CH), 123.2, 126.3, 127.1, 127.2,
127.6, 128.0, 128.3, 128.9, 131.3, 133.0, 134.5, 134.7, 138.7, 139.0, 140.5,
141.5, 142.5, 164.5 (C=O), 165.1 (C=O), 174.6 (C=O), 175.3 ppm (C=O);
IR (KBr): n˜ =3071 (w), 2924 (w), 1718 (s, C=O), 1681 (s, C=O), 1602 (w,
C=C), 1472 (m, C=C), 1453 (w), 1365 (s), 1322 (w), 1267 (m), 1239 (m),
1153 (w), 1048 (w), 912 (w), 884 (w), 835 (w), 818 (w), 777 (m), 756 (m),
738 (w), 708 (w), 610 (w), 558 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=
264 (4.525), 301 (3.639), 312 (3.628), 379 (3.415), 414 (3.314), 437 (3.446),
462 nm (3.296); MS (70 eV): m/z (%): 352 (11), 351 (46) [M]+, 337 (8),
336 (36), 335 (25), 334 (100) [MÀOH]+, 319 (11), 306 (6) [334ÀCO]+,
291 (8), 230 (3), 202 (4), 176 (14), 175 (3), 168 (3).
N-Nonylanthracene-1,9-dicarboxyimide dimers 10 f and 11 f: Compound
6 f (200 mg, 5.4 mmol) was allowed to react according to the general pro-
cedure for photodimerisation. The product was obtained as a pale-yellow
powder (200 mg, ꢀ100%). M.p. 151–1538C; Rf (silica gel; CHCl3)=0.76;
1H NMR (CDCl3): d=0.86 (m, 6H; CH3), 1.26–1.42 (m, 24H;
(CH2)6CH3), 1.76 (m, 4H; NCH2CH2), 4.23 (m, 4H; NCH2), 4.79 (s, 1H),
4.80 (s, 1H), 6.75 (m, 1H; aromatic H), 6.84 (m, 1H; aromatic H), 6.92–
7.01 (m, 5H; aromatic H), 7.09 (m, 1H; aromatic H), 7.26 (m, 1H; aro-
matic H), 7.45 (m, 3H; aromatic H), 7.79 (m, 1H; aromatic H), 7.81 ppm
(m, 1H; aromatic H); 13C NMR (CDCl3): d=13.5 (CH3), 22.1, 26.6, 27.7,
28.7, 28.8, 29.0, 31.3, 40.0 (CH2N), 57.3, 61.4 (CH), 61.6 (CH), 122.3,
125.0, 125.2, 126.2, 126.3, 126.6, 126.8, 127.0, 127.7, 129.0, 131.5, 132.9,
139.5, 139.7, 140.2, 140.4, 162.8 (C=O), 172.9 (C=O), 173.1 ppm (C=O);
IR (KBr): n˜ =2927 (m), 2856 (m), 1707 (s, C=O), 1663 (s, C=O), 1462 (w,
C=C), 1391 (w), 1356 (m), 1242 (w), 1170 (w), 1102 (w), 820 (w), 778 (w),
752 (w), 710 (w), 606 cmÀ1 (m); UV/Vis (CHCl3): lmax (loge)=266 (sh)
(4.214), 303 (3.059), 313 nm (3.068); MS (70 eV): m/z (%): 374 (26), 373
(100) [M]+, 356 (7) [MÀOH]+, 261 (29), 260 (17) [MÀC8H17]+, 248 (29),
247 (72) [MÀC9H18]+, 230 (7) [247ÀOH]+, 205 (5), 204 (5)
[MÀC9H19NCO]+, 203 (10), 202 (7), 177 (9), 176 (10) [204ÀCO]+.
N-(2,5-Di-tert-butylphenyl)anthracene-1,9-dicarboxyimide dimers 10j
and 11j: Compound 6j (200 mg, 4.6 mmol) was allowed to react accord-
ing to the general procedure for photodimerisation. The product was ob-
tained as a pale-yellow powder (200 mg, ꢀ100%). M.p. >3008C; Rf
(silica gel; CHCl3)=0.83; 1H NMR (CDCl3): d=1.24 (m, 20H), 1.44 (s,
6H), 1.61 (m, 10H), 4.94 (m, 1H), 5.11 (m, 1H), 6.75 ppm (m, 1H; aro-
matic H); 13C NMR (CDCl3): d=31.6 (CH3), 31.7 (CH3), 32.3 (CH3), 32.6
(CH3), 36.5 (CCAHTRE(UNG CH3)3), 58.4, 63.8 (CH), 64.2 (CH), 125.1, 125.1, 125.97,
N-(1-Hexylheptyl)anthracene-1,9-dicarboxyimide dimers 10g and 11g:
Compound 6g (200 mg, 4.7 mmol) was allowed to react according to the
general procedure for photodimerisation. The product was obtained as a
pale-yellow powder (200 mg, ꢀ100%). M.p. 142–1448C; Rf (silica gel;
126.01, 127.2, 127.6, 127.8, 128.7, 129.1, 129.6, 130.1, 135.0 ppm; IR
(KBr): n˜ =3069 (w), 2963 (m), 2869 (w), 1719 (s, C=O), 1679 (s, C=O),
1601 (w, C=C), 1481 (w, C=C), 1462 (w), 1394 (w), 1360 (s), 1321 (w),
1251 (m), 1204 (w), 1158 (w), 1054 (w), 910 (w), 836 (m), 778 (w), 755
(w), 735 (w), 709 (w), 674 (w), 616 cmÀ1 (w); UV/Vis (CHCl3): lmax
(loge)=265 (4.460), 303 (3.701), 315 (3.664), 379 (3.370), 416 (3.283), 436
(3.386), 460 nm (3.253); MS (70 eV): m/z (%): 435 (2) [M]+, 380 (5), 379
(28), 378 (100) [MÀC4H9]+, 363 (5), 362 (12), 346 (3), 279 (5), 167 (10),
149 (33), 112 (4), 111 (5), 109 (3), 105 (3), 97 (7), 95 (5), 91 (4), 85 (10),
83 (17), 81 (6), 71 (11), 69 (11), 57 (18), 55 (12).
1
toluene)=0.90; H NMR (CDCl3): d=0.84 (m, 12H; CH3), 1.20–1.45 (m,
32H; (CH2)4), 1.88 (m, 8H; (CH2)CHN), 2.34 (m, 8H; (CH2)CHN), 4.82
(s, 2H), 5.18–5.32 (m, 2H; (CH2)2CHN), 6.77 (m, 1H; aromatic H), 6.84
(m, 1H; aromatic H), 6.90–7.04 (m, 5H; aromatic H), 7.08 (m, 1H; aro-
matic H), 7.27 (m, 1H; aromatic H), 7.38 (m, 2H; aromatic H), 7.47 (m,
1H; aromatic H), 7.77 (s, 1H; aromatic H), 7.79 ppm (s, 1H; aromatic
H); 13C NMR (CDCl3): d=14.5 (CH3), 23.0, 27.4, 29.6, 32.3, 42.5, 54.7
(NCHR2), 58.5, 62.7 (CH), 123.8, 124.1, 125.1, 125.7, 126.0, 127.2, 127.4,
127.4, 127.6, 127.8, 128.8, 130.1, 132.3, 133.7, 140.7, 140.9, 141.1, 141.4,
143.4, 143.6 ppm; IR (KBr): n˜ =2955 (m), 2926 (s), 2856 (m), 1708 (s, C=
O), 1666 (s, C=O), 1462 (s, C=C), 1402 (w), 1353 (m), 1320 (w), 1245
(m), 1180 (w), 1105 (w), 1072 (w), 881 (w), 819 (w), 778 (w), 752 (w), 710
(w), 670 (w), 612 cmÀ1 (m); UV/Vis (CHCl3): lmax (loge)=266 (4.647),
301 (3.622), 314 (3.585), 380 (3.518), 410 (3.395), 434 (3.556), 458 (3.492),
489 (3.262), 526 nm (3.474); MS (70 eV): m/z (%): 430 (10), 429 (33)
[M]+, 344 (3) [MÀC6H13]+, 260 (6), 248 (45), 247 (100) [MÀC13H26]+, 230
(7) [247ÀOH]+, 205 (4), 204 (2) [MÀC13H27NCO]+, 203 (4), 202 (5), 177
(3), 176 (3) [204ÀCO]+.
N-(2-Ethylphenyl)anthracene-1,9-dicarboxyimide dimers 10h and 11h:
Compound 6h (200 mg, 5.7 mmol) was allowed to react according to the
general procedure for photodimerisation. The product was obtained as a
pale-yellow powder (200 mg, ꢀ100%). M.p. 148–1508C; Rf (silica gel;
CHCl3)=0.30; 1H NMR (CDCl3): d=1.13 (m, 3H; CH3), 1.47 (m, 3H;
CH3), 2.41 (m, 2H; CH2CH3), 2.81 (m, 2H; CH2CH3), 5.01 (m, 1H), 5.03
(m, 1H), 6.95–7.02 (m, 7H; aromatic H), 7.10–7.18 (m, 3H; aromatic H),
7.41 (m, 3H; aromatic H), 7.50–7.56 (m, 7H; aromatic H), 7.84–7.86 ppm
(m, 2H; aromatic H); 13C NMR (CDCl3): d=14.4 (CH3), 14.5 (CH3), 24.3
(CH2), 24.7 (CH2), 59.7, 60.0, 63.1 (CH), 63.6 (CH), 124.2, 124.9, 127.3,
127.4, 127.6, 127.9, 128.0, 128.3, 129.0, 129.6, 130.0, 134.3, 134.5, 141.3,
141.9, 142.7, 143.4 ppm; IR (KBr): n˜ =3066 (w), 3034 (w), 2968 (w), 2932
(w), 2875 (w), 1718 (s, C=O), 1679 (s, C=O), 1600 (w, C=C), 1491 (w, C=
C), 1452 (m), 1363 (s), 1321 (w), 1264 (m), 1234 (w), 1208 (w), 1145 (w),
1055 (w), 910 (w), 852 (w), 779 (w), 757 (m), 735 (m), 707 (w), 615 cmÀ1
(m); UV/Vis (CHCl3): lmax (loge)=262 (4.294), 301 (3.610), 316 (3.594),
380 (2.913), 412 (2.726), 437 (2.898), 463 nm (2.700); MS (70 eV): m/z
(%): 352 (16), 351 (66) [M]+, 335 (24), 334 (91) [MÀOH]+, 323 (17), 322
(71) [MÀC2H5]+, 319 (24), 306 (12), 291 (16), 247 (11), 204 (5) [MÀC2H5-
C6H4-NCO]+, 203 (9), 202 (12), 177 (11), 176 (24) [204ÀCO]+, 175 (11),
150 (10) [176ÀC2H2]+, 121 (43), 106 (100), 101 (13).
Amidine 12 from anthracene-1,9-dicarboxylic anhydride and neopentane-
diamine: Compound 3 (1.27 g, 5.12 mmol), neopentanediamine (5 mL,
48.9 mmol) and distilled water (30 mL) were stirred at room temperature
under argon for 1 h and then heated at reflux with stirring for 3 h (bath
temperature 1708C, orange material). The mixture was allowed to cool,
collected by vacuum filtration (G4 glass filter), washed with small
amounts of distilled water and purified by pressure-induced flash chro-
matography in the dark (silica gel, chloroform). The yellow fluorescent
main fraction was rapidly evaporated, dried in a stream of argon, then in
a medium vacuum and stored in the dark; dimers 14 and 15 would be
formed in daylight. The product was obtained as a bright-yellow powder
with a strong solid-state fluorescence (1.77 g, 79%). M.p. 175–1778C; Rf
(silica gel; CHCl3)=0.10; 1H NMR (CDCl3): d=1.10 (s, 6H; CH3), 3.49
(s, 2H; CH2N), 3.82 (s, 2H; CH2N), 7.59 (m, 2H; aromatic H), 7.72 (m,
1H; aromatic H), 8.04 (d, J=7.9 Hz, 1H; aromatic H), 8.16 (d, J=
8.2 Hz, 1H; aromatic H), 8.69 (d, J=7.4 Hz, 1H; aromatic H), 8.72 (s,
1H; aromatic H), 10.00 ppm (d, J=9.2 Hz, 1H; aromatic H); 13C NMR
(CDCl3): d=24.8 (CH3), 27.7 (CH2N), 50.9 (CH2N=), 57.8 (CACHTREUNG(CH3)2),
113.3, 116.1, 125.1, 125.5, 126.0, 127.1, 127.5, 128.9, 129.3, 129.9, 131.5,
132.3, 132.7, 134.9, 146.4 (C=N), 163.9 ppm (C=O); IR (KBr): n˜ =3125
(w), 3060 (w), 2960 (w), 2950 (w), 2847 (w), 1661 (s, C=O), 1631 (s, C=
N), 1603 (s, C=C), 1562 (m, C=C), 1533 (w, C=C), 1428 (m), 1369 (m),
1355 (w), 1330 (w), 1298 (m), 1261 (s), 1196 (m), 1169 (m), 1144 (m),
1091 (w), 1023 (w), 895 (m), 790 (m), 731 (m), 668 (m), 532 cmÀ1 (w);
UV/Vis (CHCl3): lmax (loge)=253 (4.476), 271 (4.795), 368 (3.408), 381
(3.643), 387 (3.773), 419 (sh) (3.666), 445 (3.870), 466 (3.895), 497 nm (sh)
(3.633); fluorescence (CHCl3): lmax (Irel)=518 (1), 558 (0.59), 601 nm (sh)
(0.32); solid-state fluorescence: lmax =555 nm; MS (70 eV): m/z (%): 316
(3), 315 (23), 314 (100) [M]+, 313 (12), 300 (7), 299 (33) [MÀCH3]+, 284
(9), 271 (10) [99ÀCO]+, 259 (10), 258 (27) [MÀC4H8]+, 246 (9), 231 (19),
230 (59) [258ÀCO]+, 203 (15), 202 (32) [MÀC5H10NCO]+, 201 (13), 176
(6) [202ÀCN]+, 175 (7); elemental analysis calcd (%) for C21H18N2O: C
80.23, H 5.77, N 8.91; found: C 79.96, H 5.80, N 8.95.
Chem. Eur. J. 2008, 14, 5290 – 5303
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5299

H. Langhals et al.
Crystal data for 12: The crystal structure was determined with an Enraf-
Nonius CAD4 diffractometer with MoKa radiation and a highly oriented
graphite crystal as monochromator. C21H18N2O; Mr =314.37; a=9.134(3),
b=10.189(2), c=16.816(4) Š; b=101.22(3)8; V=1535.1(7) Š3; Z=4;
1calcd =1.360 gcmÀ3; m=0.085 mmÀ1; monoclinic; space group P21/c (Nr.
14). Data collection: single crystal 0.10”0.40”0.47 mm3 (yellow plate);
w data collection, scan width 0.50+0.35tanq; maximal collection time
90 s for each reflex, number of reflections: 2275 (collected), 2120 (inde-
pendent), 1641 (observed) [I>2s(I)], minimal correction for absorption,
structure solution with SHELXS86, refinement with SHELXL93,[18] 219
H, 7’-H, cis isomer 8a), 8.05 (t, J=6.74 Hz, 2H; 7-H, 7’-H, trans isomer
7a), 8.63 (m, 4H; 3-H, 3’-H, 5-H, 5’-H, trans isomer 7a), 8.90 (m, 4H; 2-
H, 2’-H, trans isomer 7a; 3-H, 3’-H, cis isomer 8a), 9.03 (d, J=8.76 Hz,
2H; 2-H, 2’-H, cis isomer 8a), 9.87 (d, J=8.08 Hz, 2H; 8-H, 8’-H, cis
isomer 8a), 9.99 ppm (d, J=9.43 Hz, 2H; 8-H, 8’-H, trans isomer 7a); IR
(KBr): n˜ =3067 (w), 2850 (w), 1674 (s, C=O), 1655 (m, C=O), 1583 (w),
1565 (m), 1534 (m), 1426 (m), 1394 (w), 1371 (w), 1331 (w), 1282 (w),
1259 (w), 1236 (w), 1164 (w), 813 (w), 775 (w), 745 (w), 651 (w), 591 (w),
574 (w), 518 (w), 420 cmÀ1 (w); UV/Vis (DMSO): lmax (loge)=285
(4.556), 300 (sh) (4.497), 419 (3.940), 442 (sh) (3.901), 578 (sh) (3.807),
635 (4.100), 691 nm (4.269); fluorescence (DMSO): lmax =750 nm; solid-
state fluorescence: lmax =796 nm; MS (70 eV): m/z (%): 491 (22), 490
(61) [M]+, 422 (18), 421 (56), 420 (12), 419 (13), 373 (10), 352 (11), 350
(13), 349 (10), 348 (11), 247 (22), 222 (12), 217 (11), 194 (24), 178 (13),
176 (18), 175 (15), 174 (22), 173 (20), 172 (10), 168 (10), 167 (10), 165
(19), 161 (12), 63 (11), 44 (100), 32 (17), 28 (88); MS: m/z calcd for
C32H14N2O4: 490.0953; found: 490.0967 (MS).
parameters, R1 =0.0462(2s(I)), wR2 =0.1293(2s(I)), weighing w=ACHTRE1UNG /
2
[s2Fo +0.0621], GOF=1.108, max. and min. residual electron density
À3
0.170/À0.168 eŠ
.
CCDC 204452 contains the supplementary crystallographic data for 12.
These data can be obtained free of charge from the Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Amidine 13 from anthracene-1,9-dicarboxylic anhydride and o-phenyl-
Dimer 7b: Solid 85% KOH (3.90 g, 59.1 mmol) and compound 6b
(750 mg, 2.72 mmol) were allowed to react as was described for 7a and
8a (225–2358C, 10 min). The melt was treated with distilled water
(400 mL) and oxidised by passing air over it for 1 d. The product was col-
lected by vacuum filtration (G4 glass filter), washed with distilled water,
dried at 1158C, purified by flash chromatography (silica gel, starting with
a concentrated solution of 7b in chloroform, elution with toluene and
collection by the addition of tert-butyl methyl ether to the chloroform),
evaporated and extracted with ethanol for one week to give the product
as a dark-green powder and violet crystals (210 mg, 28%). M.p. >3508C;
Rf (silica gel; CHCl3)=0.01; Rf (silica gel; CHCl3/n-butanol 40:1)=0.32;
1H NMR (CDCl3): d=1.46 (t, J=6.8 Hz, 6H; CH3), 4.37 (q, J=6.9 Hz,
4H; CH2N), 7.58 (m, 2H; aromatic H), 7.80 (m, 2H; aromatic H), 8.18
(d, J=7.2 Hz, 2H; aromatic H), 8.32 (d, J=8.2 Hz, 2H; aromatic H),
8.56 (d, J=7.3 Hz, 2H; aromatic H), 9.95 ppm (d, J=8.8 Hz, 2H; aro-
matic H); 13C NMR (CDCl3): d=13.9 (CH3), 36.5 (CH2), 116.3, 124.4,
126.3, 127.4, 127.7, 127.9, 129.2, 130.3, 130.9, 131.6, 133.6, 134.5, 163.0
(C=O), 164.5 ppm (C=O); IR (KBr): n˜ =3125 (w), 2978 (w), 2934 (w),
2875 (w), 2854 (w), 1685 (s, C=O), 1648 (s, C=O), 1583 (w, C=C), 1565
(m, C=C), 1539 (w, C=C), 1436 (m), 1432 (w), 1399 (w), 1387 (w), 1375
(w), 1355 (w), 1323 (m), 1279 (w), 1254 (w), 1238 (w), 1106 (m), 962 (w),
813 (m), 774 (m), 630 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=257
(4.750), 285 (4.562), 299 (4.608), 376 (3.718), 424 (3.847), 543 (sh) (3.409),
586 (sh) (3.904), 639 (4.349), 696 nm (4.601); fluorescence (CHCl3):
lmax =730 nm; MS (70 eV): m/z (%): 548 (7); 547 (37), 546 (100) [M]+,
531 (6), 519 (8), 518 (22) [MÀC2H4]+, 504 (5), 503 (6), 491 (6), 490 (19)
[MÀ2C2H4]+, 476 (10), 475 (8), 474 (4), 448 (8), 447 (11), 446 (8), 433
(5), 420 (11), 419 (5), 377 (5), 376 (5), 375 (7), 374 (4), 373 (4), 364 (5),
362 (7), 349 (6), 348 (6), 188 (4), 187 (8), 174 (9), 85 (25), 83 (40), 47 (7);
MS: m/z calcd for C36H22N2O4: 546.1580; found: 546.1580; elemental
analysis calcd (%) for C36H22N2O4: C 79.11, H 4.06, N 5.13; found: C
78.00, H 4.61, N 5.05.
ACHTREUNGenediamine: Compound 3 (560 mg, 2.26 mmol) and o-phenylenediamine
(1.56 g, 14.4 mmol) in acetic acid (100 mL) were heated at reflux under
argon for 3 h (dark-red solution). The mixture was then evaporated in
vacuo and purified by pressure-induced flash chromatography in the dark
(silica gel, chloroform). The reddish-orange fluorescent main fraction was
rapidly evaporated, dried in a stream of argon and then in a medium
vacuum and stored in the dark; dimers 16 and 17 would be formed in
daylight. The product was obtained as a bright-red, analytically pure
powder with a reddish-orange solid-state fluorescence (260 mg, 36%).
Recrystallisation from chloroform gave reddish-brown needles. M.p.
2288C; Rf (silica gel, CHCl3)=0.75; 1H NMR (CDCl3): d=7.51 (m, 2H;
aromatic H), 7.64 (m, 1H; aromatic H), 7.76 (m, 1H; aromatic H), 7.89
(m, 1H; aromatic H), 7.97 (m, 1H; aromatic H), 8.09 (d, J=8.4 Hz, 1H;
aromatic H), 8.40 (d, J=8.4 Hz, 1H; aromatic H), 8.63 (m, 1H; aromatic
H), 8.69 (s, 1H; aromatic H), 8.91 (d, J=7.1 Hz, 1H; aromatic H),
10.64 ppm (d, J=9.1 Hz, 1H; aromatic H); 13C NMR (CDCl3): d=114.9,
116.0 (CH), 120.2 (CH), 123.1, 125.3 (CH), 125.5 (CH), 125.7 (CH),
126.4, 126.7 (CH), 128.0 (CH), 129.5 (CH), 129.6, 130.5 (CH), 131.0,
131.5, 132.5, 133.4 (CH), 133.7 (CH), 136.5 (CH), 144.1, 150.1 (C=N),
160.8 ppm (C=O); IR (KBr): n˜ =3050 (w), 2930 (w), 1690 (s, C=O), 1622
(m, C=N), 1559 (m, C=C), 1532 (m, C=C), 1522 (m, C=C), 1450 (m),
1403 (s), 1371 (w), 1362 (m), 1331 (m), 1299 (w), 1272 (m), 1214 (m),
1157 (w), 1058 (w), 878 (w), 748 (s), 714 (m), 442 cmÀ1 m; UV/Vis
(CHCl3): lmax (loge)=366 (3.469), 385 (3.535), 461 (3.998), 482 (4.098),
508 nm (3.927); fluorescence (CHCl3): lmax (Irel)=554 (0.79), 589 nm (1);
fluorescence quantum yield (CHCl3, reference perylene-3,4,9,10-tetracar-
boxylic tetramethyl ester[17] with F=100%): 48%; solid-state fluores-
cence (bright-red powder): lmax =607, 680 nm (sh); solid-state fluores-
cence (reddish-brown needles): lmax =578, 670 nm; MS (70 eV): m/z (%):
322 (2), 321 (20), 320 (100) [M]+, 319 (12), 292 (3) [MÀCO]+, 291 (8),
290 (3), 289 (1), 265 (1), 264 (1), 160 (6) [M]2+, 146 (10) [MÀCO]2+, 145
(10), 133 (1), 132 (2), 131 (2), 118 (2); elemental analysis calcd (%) for
C22H12N2O: C 82.49, H 3.78, N 8.75; found: C 82.52, H 4.08, N 8.66.
Dimer 7c: Solid 85% KOH (4.05 g, 61.4 mmol) and N-butylanthracene-
1,9-dicarboxyimide (6c, 1.00 g, 3.30 mmol) were allowed to react as was
described for 7a and 8a (225–2358C, 14 min). The melt was cautiously
treated with 10% hydrogen peroxide (120 mL), treated with chloroform
(200 mL) to form a lower layer and weakly stirred for 20 min so that the
phase separation between the cherry-red aqueous phase and the dark-
green chloroform phase remained visible. The chloroform phase was col-
lected and the aqueous phase was treated a further two times with
chloroform in the same manner. The combined organic phases were
washed with distilled water, evaporated and the residue extracted with
methanol until the extract remained colourless. The extracting solvent
was changed to chloroform to collect 7c, evaporated, purified by flash
column chromatography (silica gel, chloroform for elution and ethyl ace-
tate for collection), evaporated and extracted with methanol for 2 d to
give the product as an analytically pure, dark-green powder (110 mg,
Synthesis of the dimers 7 and 8:
Aceanthrene Green (7a and 8a): Solid 85% KOH (30.01 g, 454.7 mmol)
was heated in a nickel crucible at 150–1558C (temperature control of the
melt by a thermocouple). Aceanthrenequinone oxime (4 and 5, 6.01 g,
24.3 mmol) was then added in portions with efficient stirring (stainless
steel stirrer) and allowed to react for 15 min. The mixture was then
cooled to room temperature, treated with distilled water (150 mL), trans-
ferred to a large vessel because of the formation of foam, treated with
30% acetic acid (63 mL) and 30% hydrogen peroxide (200 mL) and al-
lowed to stand in air for 6 d. The product was collected by vacuum filtra-
tion (G4 glass filter), washed with a small amount of distilled water,
dried in air at 1158C, finely pulverised, extracted with ethanol for 2 d
(the extract turned from red to colourless) and dried in air at 1158C
(5.89 g, 99%; lit.:[2] 90%). M.p. >3008C, Rf (silica gel, CHCl3)=0.00 for
the main product 7a; Rf (silica gel, CHCl3)=0.03 for the byproduct 8a;
1H NMR (CDCl3/F3CCOOD): d=7.49 (t, J=6.06 Hz, 2H; 6-H, 6’-H, cis
isomer 8a), 7.63 (d, J=6.74 Hz, 2H; 5-H, 5’-H, cis isomer 8a), 7.86 (t,
J=8.08 Hz, 2H; 6-H, 6’-H, trans isomer 7a), 7.94 (t, J=6.74 Hz, 2H; 7-
1
11%). M.p. >3508C; Rf (silica gel, CHCl3)=0.16; H NMR (CDCl3): d=
1.06 (t, J=7.3 Hz, 6H; CH3), 1.53 (m, 4H; CH2CH3), 1.83 (m, 4H;
CH2CH2N), 4.28 (m, 4H; CH2N), 7.56 (m, 2H; aromatic H), 7.77 (m,
2H; aromatic H), 8.14 (d, J=7.8 Hz, 2H; aromatic H), 8.28 (d, J=
8.6 Hz, 2H; aromatic H), 8.54 (d, J=7.8 Hz, 2H; aromatic H), 9.92 ppm
5300
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 5290 – 5303

Anthracene Carboxyimides
FULL PAPER
(d, J=8.8 Hz, 2H; aromatic H); 13C NMR (CDCl3): d=14.3 (CH3), 21.0
(CH2), 30.7 (CH2), 41.2 (CH2N), 116.2, 122.4, 124.3, 127.1, 127.5, 127.9,
129.2, 130.0, 130.8, 130.9, 131.5, 133.4, 133.5, 134.2, 163.1 (C=O),
164.5 ppm (C=O); IR (KBr): n˜ =2962 (m), 2932 (w), 2871 (w), 1683 (s,
C=O), 1644 (s, C=O), 1583 (m, C=C), 1567 (s, C=C), 1538 (m, C=C),
1438 (w), 1435 (m), 1401 (w), 1389 (m), 1344 (w), 1326 (m), 1198 (w),
1112 (m), 812 (m), 773 (m), 730 (w), 574 cmÀ1 (w); UV/Vis (CHCl3): lmax
(loge)=258 (4.807), 287 (4.610), 300 (4.666), 372 (sh) (3.719), 423
(3.875), 583 (sh) (3.928), 640 (4.426), 696 nm (4.678); fluorescence
(CHCl3): lmax =740 nm; MS (70 eV): m/z (%): 604 (10), 603 (44), 602
(100) [M]+, 586 (9), 585 (20) [MÀOH]+, 547 (9), 546 (10) [MÀC4H8]+,
529 (8) [546ÀOH]+, 505 (5), 504 (12), 503 (3) [MÀC4H9NCO]+, 491 (12),
490 (20) [MÀ2C4H8], 420 (7), 419 (7), 374 (5), 373 (5), 348 (5); elemental
analysis calcd (%) for C40H30N2O4: C 79.72, H 5.02, N 4.65; found: C
79.86, H 5.08, N 4.79.
7c and further purified by column chromatography (silica gel, chloro-
form) and extracted with methanol until a colourless extract was given.
The product was obtained as an analytically pure, dark-green powder
(17.8 mg, 7%). M.p. 293–2958C; Rf (silica gel; CHCl3)=0.32; Rf (silica
gel; CHCl3/1-butanol, 40:1)=0.75; 1H NMR (CDCl3): d=0.88 (t, J=
6.4 Hz, 6H; CH3), 1.36 (m, 24H; (CH2)6CH3), 1.83 (quintet, J=7.0 Hz,
4H; CH2CH2N), 4.24 (t, J=7.4 Hz, 4H; CH2N), 7.47 (m, 2H; aromatic
H), 7.72 (m, 2H; aromatic H), 7.98 (d, J=7.8 Hz, 2H; aromatic H), 8.11
(d, J=8.6 Hz, 2H; aromatic H), 8.40 (d, J=7.8 Hz, 2H; aromatic H),
9.84 ppm (d, J=8.9 Hz, 2H; aromatic H); 13C NMR (CDCl3): d=14.5
(CH3), 23.1 (CH2), 27.8 (CH2), 28.6 (CH2), 29.7 (CH2), 29.9 (CH2), 30.1
(CH2), 32.3 (CH2), 41.5 (CH2N), 116.0, 122.3, 124.1, 126.9, 127.3, 127.8,
129.1, 129.8, 130.7, 131.3, 133.1, 133.2, 134.1, 163.0 (C=O), 164.4 ppm (C=
O); IR (KBr): n˜ =3122 (w), 3084 (w), 3040 (w), 2955 (m), 2923 (s), 2854
(s), 1687 (s, C=O), 1644 (s, C=O), 1583 (m, C=C), 1567 (s, C=C), 1538
(m, C=C), 1467 (m), 1433 (s), 1400 (m), 1388 (m), 1356 (m), 1341 (m),
1326 (m), 1278 (m), 1252 (m), 1234 (m), 1183 (w), 1154 (w), 1114 (s),
1077 (w), 880 (w), 812 (s), 772 (s), 725 (m), 655 (w), 637 (w), 573 cmÀ1
(w); UV/Vis (CHCl3): lmax (loge)=258 (4.783), 287 (4.582), 301 (4.633),
371 (sh) (3.660), 425 (3.834), 584 (sh) (3.905), 640 (4.404), 696 nm
(4.660); fluorescence (CHCl3): lmax =736 nm; MS (70 eV): m/z (%): 745
(3), 744 (15), 743 (58), 742 (100) [M]+, 726 (5), 725 (10) [MÀOH]+, 630
(4), 629 (4), 618 (11), 617 (22), 616 (6) [MÀC9H18]+, 599 (2), 505 (6), 504
(9), 503 (4), 493 (3), 492 (9), 491 (18), 490 (13) [MÀ2C9H18]+, 446 (3),
445 (3), 432 (4), 421 (4), 420 (7), 419 (5), 375 (3), 374 (4), 349 (3), 174
(4), 173 (5), 83 (3), 57 (3), 55 (6); elemental analysis calcd (%) for
C50H50N2O4: C 80.83, H 6.78, N 3.77; found: C 81.07, H 7.03, N 3.75.
Dimer 7d: Solid 85% KOH (21.12 g, 340 mmol) and compound 6d
(4.92 g, 15.5 mmol) were allowed to react as was described for 7c. The
product was obtained as an analytically pure, turquoise powder (1.09 g,
22%). M.p. 345–3488C; Rf (silica gel; CHCl3)=0.18; 1H NMR (CDCl3):
d=0.97 (t, J=7.0 Hz, 6H; CH3), 1.47 [m, 8H; (CH2)2CH3], 1.84 (quintet,
J=7.3 Hz, 4H; CH2CH2N), 4.29 (m, 4H; CH2N), 7.59 (m, 2H; aromatic
H), 7.79 (m, 2H; aromatic H), 8.19 (d, J=7.8 Hz, 2H; aromatic H), 8.34
(d, J=8.6 Hz, 2H; aromatic H), 8.58 (d, J=7.8 Hz, 2H; aromatic H),
9.94 ppm (d, J=8.7 Hz, 2H; aromatic H); 13C NMR (CDCl3): d=14.1
(CH3), 22.5 (CH2), 27.9 (CH2), 29.5 (CH2), 41.0 (CH2N), 115.9, 122.1,
124.1, 126.9, 127.3, 127.5, 128.8, 129.8, 130.5, 130.6, 131.2, 133.1, 133.3,
134.0, 162.8 (C=O), 164.2 ppm (C=O); IR (KBr): n˜ =3070 (w), 2957 (m),
2931 (w), 2870 (w), 1685 (s, C=O), 1647 (s, C=O), 1583 (w, C=C), 1568
(m, C=C), 1539 (m, C=C), 1434 (m), 1421 (w), 1388 (m), 1343 (w), 1326
(m), 1256 (w), 1238 (w), 1192 (w), 1111 (m), 812 (m), 773 (m), 730 (w),
575 (w), 430 cmÀ1 (w); UV/Vis (CHCl3): lmax (loge)=256 (4.805), 286
(4.624), 300 (4.662), 361 (sh) (3.791), 376 (3.851), 422 (3.937), 495 (3.323),
532 (3.541), 585 (sh) (3.995), 639 (4.423), 696 nm (4.672); fluorescence
(CHCl3): lmax =738 nm; solid-state fluorescence: lmax =791 nm; MS
(70 eV): m/z (%): 632 (11), 631 (45), 630 (100) [M]+, 614 (5), 613 (11)
[MÀOH]+, 562 (5), 561 (13), 560 (8) [MÀC5H10]+, 543 (3) [560ÀOH]+,
505 (5), 504 (10), 492 (6), 491 (13), 490 (17) [MÀ2C5H10]+, 445 (3)
[490ÀCOÀOH]+, 420 (6), 419 (5) [560ÀC5H11NCOÀCO]+, 376 (2)
[MÀ2C5H11NCOÀCO]+, 375 (4), 374 (4), 373 (4), 362 (3), 349 (4), 348
(3); elemental analysis calcd (%) for C42H34N2O4: C 79.98, H 5.43, N
4.44; found: C 80.07, H 5.52, N 4.28.
Dimer 7g: Solid 85% KOH (10.25 g, 155.3 mmol) and compound 6g
(70 mg, 0.16 mmol) were allowed to react (238–2408C, 1 h 50 min) as de-
scribed for 7c. The cold melt was cautiously dissolved in a 1:1:1 mixture
of water, methanol and ethanol and oxidised by a stream of air bubbles
(1 d). The precipitate was collected by vacuum filtration (D4 glass filter)
and dissolved in a mixture of petroleum ether and methanol. The green
phase of petroleum ether was collected, extracted with methanol, evapo-
rated and purified by column chromatography (silica gel, n-hexane/tolu-
ene, 1:1) to give the product as a bright-green, highly viscous oil (3.2 mg,
5%). Rf (silica gel; toluene/n-hexane, 1:1)=0.42; 1H NMR (CDCl3): d=
0.81 (t, J=7.0 Hz, 12H; CH3), 1.30 (m, 32H; (CH2)4CH3), 1.94 [m, 4H;
(CH2)CHN], 2.35 (m, 4H; (CH2)CHN), 5.33 (m, 2H; (CH2)2CHN), 7.79
(m, 2H; aromatic H), 7.90 (m, 2H; aromatic H), 8.55 (d, J=7.8 Hz, 2H;
aromatic H), 8.77 (d, J=8.9 Hz, 2H; aromatic H), 8.86 (d, J=7.8 Hz,
2H; aromatic H), 10.00 ppm (d, J=9.1 Hz, 2H; aromatic H); 13C NMR
(CDCl3): d=14.0 (CH3), 22.6 (CH2), 27.0 (CH2), 29.3 (CH2), 31.8 (CH2),
32.6 (CH2), 45.8 (NCHR2), 113.4, 124.7, 127.6, 127.8, 128.0, 128.8, 130.5,
130.8, 131.0, 132.8, 133.6, 134.5 ppm; IR (film): n˜ =2955 (m), 2925 (s),
2856 (m), 1691 (s, C=O), 1652 (s, C=O), 1567 (m, C=C), 1539 (m, C=C),
1456 (w), 1421 (m), 1388 (w), 1377 (w), 1344 (w), 1323 (m), 1279 (w),
1227 (w), 1162 (w), 1117 (w), 884 (w), 813 (m), 774 (m), 730 (m),
668 cmÀ1 (w); UV/Vis (CHCl3): lmax =257, 286, 301, 364 (sh), 385 (sh),
423, 580 (sh), 638, 694 nm; fluorescence (CHCl3): lmax =729 nm; MS
(70 eV): m/z (%): 857 (5), 856 (21), 855 (64), 854 (100) [M]+, 838 (3),
837 (4) [MÀOH]+, 769 (2), 675 (4), 674 (13), 673 (22), 672 (17)
[MÀC13H26]+, 656 (3), 655 (4), 588 (3), 504 (4), 503 (6), 494 (3), 493 (11),
492 (33), 491 (55), 490 (57) [MÀ2C13H26]+, 489 (3), 475 (4), 474 (6), 473
(5), 446 (6), 445 (10), 444 (3), 421 (7), 420 (14), 419 (7), 375 (4), 374 (6),
373 (5), 349 (3), 173 (3), 167 (3), 149 (8), 125 (3), 111 (6), 97 (11), 83
(13), 71 (12), 69 (19), 57 (20), 56 (11), 55 (27); MS: m/z calcd for
C58H66N2O4: 854.5023; found: 854.5046.
Dimer 7e: Solid 85% KOH (5.00 g, 75.7 mmol) and compound 6e
(1.26 g, 3.80 mmol) were allowed to react as was described for 7c. The
product was obtained as an analytically pure, green powder (200 mg,
16%). M.p. 325–3278C; Rf (silica gel; CHCl3)=0.19; Rf (silica gel;
CHCl3/1-butanol, 40:1)=0.66; 1H NMR (CDCl3): d=0.94 (t, J=6.9 Hz,
6H; CH3), 1.46 (m, 12H; (CH2)3CH3), 1.82 (m, 4H; CH2CH2N), 4.22 (t,
J=7.6 Hz, 4H; CH2N), 7.42 (m, 2H; aromatic H), 7.69 (m, 2H; aromatic
H), 7.90 (d, J=7.8 Hz, 2H; aromatic H), 8.03 (d, J=8.6 Hz, 2H; aromat-
ic H), 8.34 (d, J=7.8 Hz, 2H; aromatic H), 9.81 ppm (d, J=8.8 Hz, 2H;
aromatic H); 13C NMR (CDCl3): d=14.5 (CH3), 23.1 (CH2), 27.4 (CH2),
28.5 (CH2), 32.1 (CH2), 41.5 (CH2N), 115.9, 122.2, 124.0, 126.8, 127.2,
127.8, 129.1, 129.6, 130.6, 130.7, 131.2, 133.0, 134.0, 162.9 (C=O),
164.3 ppm (C=O); IR (KBr): n˜ =3122 (w), 3045 (w), 2955 (m), 2929 (m),
2857 (m), 1685 (s, C=O), 1647 (s, C=O), 1583 (m, C=C), 1565 (s, C=C),
1539 (m, C=C), 1433 (m), 1420 (m), 1400 (w), 1386 (m), 1343 (m), 1325
(m), 1255 (w), 1236 (w), 1187 (w), 1112 (m), 883 (w), 812 (m), 773 (m),
728 (m), 574 cmÀ1 (m); UV/Vis (CHCl3): lmax (loge)=257 (4.790), 286
(4.593), 300 (4.651), 360 (sh) (3.649), 376 (3.652), 422 (3.836), 585 (sh)
(3.933), 639 (4.421), 696 nm (4.676); fluorescence (CHCl3): lmax =736 nm;
MS (70 eV): m/z (%): 660 (13), 659 (48), 658 (100) [M]+, 642 (9), 641
(10) [MÀOH]+, 588 (4), 576 (8), 575 (19), 574 (8) [MÀC6H12]+, 505 (7),
504 (11), 492 (8), 491 (16), 490 (17) [MÀ2C6H12]+, 446 (3), 445 (4), 432
(4), 421 (4), 420 (7), 419 (6), 375 (4), 374 (5), 373 (4), 349 (4), 348 (4),
174 (3); elemental analysis calcd (%) for C44H38N2O4: C 80.22, H 5.81, N
4.25; found: C 80.41, H 6.03, N 4.31.
Tests for the hydrolysis of dimers 7 and 8: Test for the acid hydrolysis of
Aceanthrene Green (7a and 8a): Aceanthrene Green (7a and 8a,
160 mg, 0.33 mmol) was treated with concentrated sulfuric acid (30 mL),
heated with stirring at (1208C, 3 h), allowed to cool, diluted with distilled
water (200 mL), collected by vacuum filtration (G5 glass filter), washed
with a small amount of distilled water and dried at 1158C. TLC analysis
(silica gel, chloroform) indicated a complete decomposition of the start-
ing material (no green spot).
Dimer 7 f: Solid 85% KOH (6.00 g, 90.0 mmol) and compound 6 f
(250 mg, 0.67 mmol) were allowed to react (225–2358C) as described for
Test for alkaline hydrolysis of Aceanthrene Green (7a and 8a): Acean-
threne Green (7a and 8a, 170 mg, 0.35 mmol) was suspended in tert-butyl
Chem. Eur. J. 2008, 14, 5290 – 5303
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H. Langhals et al.
alcohol (50 mL) with heating, treated with 85% solid KOH (1.06 g,
16.0 mmol), heated at reflux for 2 h, hydrolysed by the addition of a 1:1
mixture of acetic acid and concentrated HCl, diluted to a volume of
100 mL with distilled water, collected by vacuum filtration (G4 glass
filter) and dried at 1158C. The material proved to be identical to the
starting material according to IR, MS and UV/Vis spectroscopic analyses.
with 85% solid KOH (170 mg, 2.57 mmol, colour change from green to
violet), stirred for further 10 min (bath temperature 1508C), evaporated
in vacuo, treated with iodomethane (13 mL, 208 mmol), allowed to stand
for 24 h and purified by flash chromatography (silica gel, chloroform).
The TLC Rf value and the mass spectrum of the orange red material ob-
tained were identical to the above mentioned reaction in tert-butyl alco-
hol/DMSO. For further characterisation see above.
Test for the N-alkylation of the Aceanthrene Green (7a and 8a): Acean-
threne Green (7a and 8a, 110 mg, 0.22 mmol), potassium carbonate
(1.00 g, 5.64 mmol) and 1-bromoheptane (1.06 mL, 6.72 mmol) were
heated at reflux in anhydrous DMF(10 mL) for 24 h. The mixture was al-
lowed to cool, poured into distilled water (10 mL), acidified with 2n
HCl, stirred for 45 min and collected by vacuum filtration. Only traces of
an emerald-green material could be detected (Rf (silica gel; CHCl3)=
0.47). More than 14 byproducts were detected.
Acknowledgements
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
Reaction of dimers 7 with alkali: Reaction of 7 with KOH in tert-butyl al-
cohol: Dimers 7b–e (3 mg, ca. 0.05 mmol) under argon was dispersed in
tert-butyl alcohol (60 mL), heated at reflux for 2 h, treated with 85%
solid KOH (1.00 g, 15.2 mmol; spontaneous colour change from green to
violet), heated at reflux for a further 50 min, quenched by acidification
with a mixture of acetic acid/2n HCl (2:1), collected by vacuum filtration
(G4 glass filter), washed with distilled water and dried at 1158C in air.
The unchanged starting material was obtained in all cases according to
IR, TLC and MS analyses.
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Reaction of 7 with KOH in tert-butyl alcohol/DMSO: Dimers 7b–e
(100 mg, ca. 0.16 mmol) was dispersed in a mixture of DMSO (15 mL)
and tert-butanol (15 mL) under argon. The mixture was heated at reflux
for 2 h, treated with 85% solid KOH (120 mg, 1.82 mmol; spontaneous
colour change from dark-green to violet), and further treated as was de-
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according to IR, TLC and MS analyses.
Methylation of the violet intermediate of the reaction of 7d with KOH
in tert-butyl alcohol/DMSO to form 9d: Dimer 7d (160 mg, 0.25 mmol)
was dissolved in a mixture of DMSO (25 mL) and tert-butyl alcohol
(25 mL) at 1308C (bath temperature), treated with 85% solid KOH
(170 mg, 2.57 mmol; spontaneous colour change from dark-green to
violet), heated at reflux for 1 h, evaporated in vacuo, treated with iodo-
methane (13 mL, 208 mmol), stirred at room temperature for 16 h,
evaporated (reddish-brown residue), evaporated in vacuo and purified by
flash chromatography (silica gel, chloroform). The product was obtained
as bright-orange crystals with a strong solid-state fluorescence (14 mg,
9%). M.p. 132–1358C; Rf (silica gel; CHCl3)=0.65; 1H NMR (CDCl3):
d=0.90 (t, J=6.9 Hz, 6H; CH3), 1.37 (m, 8H; (CH2)2), 1.66 (m, 4H;
CH2CH2N), 1.72 (s, 6H; CH3), 4.03 (m, 4H; CH2N), 7.19 (d, J=7.9 Hz,
2H; aromatic H), 7.59 (dt, Jt =7.4, Jd =1.3 Hz, 2H; aromatic H), 7.71 (m,
2H; aromatic H), 7.79 (dd, J1 =7.7, J2 =1.5 Hz, 2H; aromatic H), 8.14 (d,
J=7.7 Hz, 2H; aromatic H), 8.75 ppm (dd, J1 =8.2, J2 =1.0 Hz, 2H; aro-
matic H); 13C NMR (CDCl3): d=14.0 (CH3), 22.4 (CH2), 27.8 (CH2), 29.2
(CH2), 40.7 (CH3), 41.7 (CH2N), 45.3 (Cq), 122.6 (CH), 124.3, 125.0, 128.0
(CH), 129.3 (CH), 130.4 (CH), 130.6 (CH), 130.7 (CH), 133.8, 134.8,
137.6, 144.4, 163.5 (C=O), 174.0 ppm (C=O); IR (KBr): n˜ =2958 (m),
2929 (m), 2859 (w), 1723 (s, C=O), 1678 (s, C=O), 1626 (m, C=C), 1449
(m), 1432 (m), 1386 (m), 1360 (s), 1334 (m), 1291 (w), 1258 (w), 1229
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(w), 1207 (w), 1178 (w), 1107 (m), 1079 (w), 851 (w), 766 (m), 745 cmÀ1
;
UV/Vis (CHCl3): lmax (loge)=256 (4.504), 267 (sh) (4.495), 351 (3.802),
378 (sh) (3.436), 447 (2.433), 474 nm (2.509); fluorescence (CHCl3): lmax
(Irel)=511 (sh) (0.80), 543 nm (1); fluorescence quantum yield (CHCl3,
reference perylene-3,4,9,10-tetracarboxylic tetramethyl ester[17] with F=
100%): 27%; solid-state fluorescence: lmax (Irel)=555 (1), 584 nm (sh)
(0.83); MS (70 eV): m/z (%): 662 (13), 661 (46), 660 (92) [M]+, 647 (11),
646 (46), 645 (100) [MÀCH3]+, 631 (6), 630 (13), 548 (6), 547 (14)
[MÀC5H11NCO]+, 534 (6), 533 (26), 532 (65) [MÀC5H11NCOÀCH3]+,
505 (8), 504 (19) [532ÀCO]+, 435 (13), 434 (14) [MÀ2C5H11NCO]+, 363
(6), 217 (49) [434À217]+, 189 (27), 182 (20), 181 (16); MS: m/z calcd for
C44H40N2O4: 660.2988; found: 660.2991; elemental analysis calcd (%) for
C44H40N2O4: C 79.98, H 6.10; found: C 76.84, H 6.17.
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Methylation of the violet intermediate of the reaction of 7d with KOH
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5302
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Anthracene Carboxyimides
FULL PAPER
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Received: November 23, 2007
Published online: April 17, 2008
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5303