Novel fluorescent dyes by the extension of the core of perylenetetracarboxylic bisimides

Article abstract of DOI:10.1002/(sici)1099-0690(200001)2000:2<365::aid-ejoc365>3.0.co;2-r

Core-extended perylenetetracarboxylic bisimides were prepared by Diels- Alder reaction followed by reduction, or by nitration followed by cyclisation. Highly fluorescent dyes were obtained with absorption regions from the visible to the NIR. Applications

Full text of DOI:10.1002/(sici)1099-0690(200001)2000:2<365::aid-ejoc365>3.0.co;2-r

FULL PAPER
Novel Fluorescent Dyes by the Extension of the Core of
Perylenetetracarboxylic Bisimides
Heinz Langhals*[a] and Susanne Kirner[a]
Dedicated to Prof. Dr. C. Rüchardt on the occasion of his 70th birthday
Keywords: Fluorescent dyes / Perylenes / Heterocycles / NIR dyes
Core-extended perylenetetracarboxylic bisimides were
prepared by Diels–Alder reaction followed by reduction, or
by nitration followed by cyclisation. Highly fluorescent dyes
were obtained with absorption regions from the visible to the
NIR. Applications for solar energy harvesting, and quantum
counters were suggested.
Perylene dyes such as perylene-3,4:9,10-tetracarboxylic
bisimides 1, exhibit unusually good properties such as high
photostabilities and high fluorescence quantum yields.[1]
The introduction of solubilizing groups such as tert-bu-
tylaryl[2] groups or long-chain sec-alkyl groups (“swallow-
tail” substituents[3]) render the dyes soluble in organic sol-
vents. The extension of the aromatic core of perylene is a
modern topic in chemistry; see for example ref.[4] The reac-
tion of perylene itself to form benzperylenedicarbox-
imides[5] as well as the anellation of perylene-3,4-dicarbox-
imide with heterocycles has been studied in preceding pap-
ers.[6] However, such extensions of 1 are unknown.
The DielsϪAlder reaction of perylene with maleic anhy-
dride proceeds easily[1,7,8] so that a complete conversion is
obtained within 10 min at 190Ϫ200°C. The bisimide 1 is
less electron-rich than perylene and therefore less reactive
and gives insignificant yields in this reaction. However, a
prolongation of the reaction time to 4 d, and a simul-
taneous aromatization with chloranil led to a yield of some
70% of the benzperylenebisimide anhydrides 2. This reac-
[a]
Institut für Organische Chemie der Universität München,
Butenandtstraße 5-13 (Haus F), D-81377 München, Germany
Fax: (internat.) ϩ 49-(0)89/2180-7640
E-mail: Langhals@lrz.uni-muenchen.de
Eur. J. Org. Chem. 2000, 365Ϫ380
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ193X/00/0102Ϫ365 $ 17.50ϩ.50/0
365

H. Langhals, S. Kirner
FULL PAPER
The unknown 1-nitroperylenebisimides (6) are key inter-
mediates for the preparation of heterocyclic anellated dyes.
Literature procedures[14][15] for the nitration of perylene de-
rivatives have not been tested for the preparation of 6 be-
cause the regiospecific mononitration of 1 was required and
proceeded with N2O4 in CH2Cl2 according to ref.[16] A cata-
lytic amount of methanesulfonic acid further increases the
yield of 6 to 90%. An excess of nitration reagent is recom-
mended, since small amounts of dinitration products are
more easily removed than any remaining starting material
(1). The low reactivity of the perylene bisimides towards
electrophiles is also demonstrated by the attempted bromin-
ation of 1, where no reaction could be observed with bro-
mine, even at 100°C. A large excess of bromine (150 mol/
mol of 1) and the addition of potassium carbonate[17] (14
mol/mol of 1) was required to prepare 8 (86%).
Compound 6 was reduced to amine 9 by iron powder and
hydrochloric acid in either ethanol or THF. The reduction
with formic acid[18] or triethyl ammonium formate[19] and
palladium on carbon is an alternative. However, catalyst
poisoning must be excluded. The amine 9 may be alkylated
to 10 with formic acid or formaldehyde (LeuckartϪWallach
reaction or EschweilerϪClarke reaction, respectively).
However, better results were obtained by a reaction with
methyl iodide, KOH powder, and benzyl triethyl am-
monium chloride.
The analogous nitration of the anhydride imide 16[20]
gave an analytically pure mixture of the two isomers 17a
and 18a. Their low solubility and similar chromatographic
properties makes their separation difficult. The mixture was
therefore directly reduced to a mixture of the amines 17b
and 18b, which exhibit very low and also very similar chro-
matographic migrations. This mixture of the amines was
then directly converted into the dimethylamino derivatives
17c and 18c, which could be separated by column chroma-
tography.
tion is not affected by the addition of Lewis acids such as
AlCl3. In contrast to perylene peri-anhydrides, the anhy-
dride 2 is sensitive to moisture and slowly forms the free
acid, but can be regenerated by heating. Compound 2 may
be further condensed with primary amines to form the trisi-
mides 3 or with peri-diaminonaphthalene to give 15. A
combination of dicyclohexyl carbodiimide and trifluoro-
acetic acid gives a novel reagent which favours the conden-
sation appreciably. Each component alone supports the re-
action, however their combination is appreciably more ef-
fective. The anhydride 2, after ring opening with ethanol or
the free acid, can easily be transformed to the diethyl ester
(4) with ethyl iodide and DBU. No ester could be obtained
with ethanol and catalytic amounts of mineral acid. The
anhydride 2 or the free acid can be transformed to the
benzperylene bisimide 5 with the reaction of copper powder
in refluxing quinoline in analogy to ref.[9] A decar-
boxylation with copper(I) oxide gave varying yields.
The reaction of the nitro compound 6 with a phosphor-
ous ester yields a mixture of 7 and 12, which can be easily
separated by column chromatography. Compound 7 is of
interest as a label for transphosphorylation reactions. 12a
and 12b are of general interest as monofunctionalized fluor-
escent labels for electrophiles because the pyrrole nitrogen
atom can be easily deprotonated with DBU and forms a
strong nucleophile. Examples of alkylations (methyl iodide
and benzyl bromide) and acylations (acetyl chloride and
benzoyl chloride) of 12a and 12b are therefore given. The
reaction of 12a with bromoacetic acid ethyl ester is of spe-
cial interest for an umpolung of the reagent because label-
ling can proceed with nucleophiles via the carboxyl ester
group.
The reaction of the nitro compound 6 with sulfur in
The DielsϪAlder reaction of 1 proceeds even more easily DMF forms a mixture of the two sulfur-containing hetero-
with the strong dienophile N-phenyltriazolinedione[10Ϫ13] cycles, 11 and 13 which can be separated by column chro-
and forms directly the rearomatized 14 in low yield (5%). matography (45% and 40% isolated yield, respectively). Two
An addition of chloranil as an oxidant improves the syn- other derivatives of 11 have been prepared by another
thesis of 14 appreciably (25% yield) and the reaction is over route,[21][22] the heterocycle 13 is new. The solvent N-meth-
within 24 h.
ylpyrrolidone increases the reaction rate appreciably and
366
Eur. J. Org. Chem. 2000, 365Ϫ380

Novel Fluorescent Dyes by the Extension of the Core of Perylenetetracarboxylic Bisimides
FULL PAPER
favours the formation of 11. An increase of the reaction
temperature, for example in refluxing DMF, also favours
the formation of 11 (71%), so that no 13 could be detected.
Figure 3. UV/Vis absorption and fluorescence spectra of 14a (color
coordinates x ϭ 0.2489, y ϭ 0.3507, Y ϭ 59.04, 2°, normlight C
at Tmin ϭ 0.1) in chloroform
Figure 1. UV/Vis absorption and fluorescence spectra of 2a (color
coordinates x ϭ 0.3767, y ϭ 0.4315, Y ϭ 96.49, 2°, normlight C
at Tmin ϭ 0.1) in chloroform compared to 1a [R1 ϭ CH(C6H13)2,
half of the molar absorptivity of 1a] (···)
Figure 4. UV/Vis absorption and fluorescence spectra of 5a (color
coordinates x ϭ 0.3658, y ϭ 0.4150, Y ϭ 97.29, 2°, normlight C
at Tmin ϭ 0.1) in chloroform
tion at 468 nm, fluorescence quantum yield 74%; see
Figure 1.
Even the condensation of 2 with primary amines to form
3 does not notably alter the spectra: absorption at 465 nm,
Figure 2. UV/Vis absorption and fluorescence spectra of 3a (color
coordinates x ϭ 0.3637, y ϭ 0.4156, Y ϭ 97.40, 2°, normlight C
at Tmin ϭ 0.1) in chloroform; (···): solid-state fluorescence
The structured UV/Vis absorption of the benzperylenebi- fluorescence quantum yield 45% for 3a or 3b; see Figure 2.
simide 5 (468 nm) is hypsochromically shifted by about An intense solid-state fluorescence was observed both for
60 nm compared to 1; see Figure 4. Compound 5 is highly 3a and 3b, as well as additional absorptions in the near UV
fluorescent (77% quantum yield of 5a in chloroform[23]); see (372 nm). The latter are even more pronounced for 15,
Figure 4. The electron-withdrawing ester group in 4 affects which has a further extended π system; see Figure 7. There
these spectra only slightly (466 nm) and the fluorescent is also a weaker absorption for 15 at long wavelengths in
quantum yield is similarly high (85% quantum yield of 4a the visible region (500Ϫ650 nm). Compound 15 exhibits no
in chloroform). The ester groups are expected to act mainly fluorescence. All dyes are highly lightfast; they can be ir-
inductive electron-withdrawing because steric interactions radiated for weeks with direct solar radiation in solution
should place their π system orthogonal to the chromophore. without detectable decomposition.
The anhydride group in 2 may additionally act as meso-
Whereas the effect of the electron-withdrawing substitu-
merically electron-withdrawing because of the planarity in ents of 2 and 4 on the UV/Vis spectra is only negligible,
2, but this is also of little influence to the spectra: absorp- strong electron donors such as the nitrogen atoms in 14
Eur. J. Org. Chem. 2000, 365Ϫ380
367

H. Langhals, S. Kirner
FULL PAPER
Figure 5. UV/Vis absorption and fluorescence spectra of 11a (color
coordinates x ϭ 0.3711, y ϭ 0.3808, Y ϭ 90.66, 2°, normlight C
at Tmin ϭ 0.1) in chloroform; (···): solid-state fluorescence
Figure 7. UV/Vis absorption and fluorescence spectra of 15a (color
coordinates x ϭ 0.4091, y ϭ 0.3951, Y ϭ 64.71, 2°, normlight C
at Tmin ϭ 0.1) in chloroform
Figure 8. UV/Vis absorption spectrum of 10a (color coordinates
x ϭ 0.2142, y ϭ 0.3240, Y ϭ 29.78, 2°, normlight C at Tmin ϭ 0.1)
in chloroform
Figure 6. UV/Vis absorption spectrum of 13a (color coordinates
x ϭ 0.3091, y ϭ 0.4071, Y ϭ 53.01, 2°, normlight C at Tmin ϭ 0.1)
in chloroform
ane: 580 nm) and strong fluorescence (DMF: 768 nm, etha-
cause a pronounced bathochromic absorption at 600 nm; nol: 764 nm, chloroform: 725 nm, cyclohexane: 670 nm).
see Figure 3. This broad and only slightly structured band Obviously, the inductive effect of the methyl groups in 10
reaches even the NIR. Interestingly, there is a strong fluor- causes an additional bathochromic shift; see Figure 8. The
escence of 14 far into the NIR which is of interest for the dye 10 is not only of interest because of the strong NIR
modern information technology.
fluorescence, but there is an appreciable light absorption
The UV/Vis absorption spectrum of the nitro compound from the UV throughout the visible region so that the mo-
6 is nearly identical with the spectrum of 1, but 6 does not lar coefficient of extinction never drops below
exhibit fluorescence. The low influence of electron acceptor 4200 L·molϪ1·cmϪ1. Such fluorescent dyes are of interest
substituents on the spectra of 1 corresponds to the influence for quantum counter applications, which integrate light
of substituents in 5. On the other hand, the reduction of 6 quanta of any wavelengths in the visible to fluorescent light
to 9 switches the substituent from an electron acceptor to in the NIR. On the other hand, the broad absorption
an electron donor and causes a pronounced bathochromic throughout the visible region makes this dye also of interest
shift (571 nm in chloroform). Compound 9 is positively sol- for light harvesting systems. Unfortunately, 10 has no
vatochromic both in absorption (ethanol: 600 nm, cyclohex- anchor group for such applications. More suitable therefore
ane: 556 nm) and fluorescence (ethanol: 761 nm, cyclohex- are the structurally related perylene derivatives, 17c and
ane: 633 nm). A positive solvatochromism is also obtained 18c, which exhibit similar UV/Vis spectra; see Figure 9.
for the dimethylamino derivative 10 in absorption (DMF: Their anhydride rings may serve as anchor groups for cat-
624 nm, ethanol: 613 nm, chloroform: 614 nm, cyclohex- ions such as Ti4ϩ with an oxygen affinity, for example with
368
Eur. J. Org. Chem. 2000, 365Ϫ380

Novel Fluorescent Dyes by the Extension of the Core of Perylenetetracarboxylic Bisimides
FULL PAPER
drogen peroxide until the light brown color disappeared. The or-
ganic phase was removed and the oxidation product, nitric acid,
was determined by titration with NaOH, using phenolphthalein as
the indicator.
Nitration of 1. ؊ General Procedure: The calculated amount of
N2O4 in dichloromethane was added to a solution of the perylene-
3,4;9,10-bis(dicarboximide), dissolved in a minimal amount of di-
chloromethane (1 mol of N2O4 per mol of 1). A few drops of meth-
anesulfonic acid were added and the red solution was stirred at
room temperature until nearly all of the fluorescent starting mate-
rial was converted (controlled by DC; 5Ϫ12 h). The solvent was
removed in vacuo and the residue purified by column separation
(silica gel, toluene). The dinitrated, nonfluorescent reaction prod-
uct eluted first, followed by the nonfluorescent mononitration
product, and the highly fluorescent starting material. Generally, the
dinitrated product can be more easily separated than the starting
bis(imide) from the mononitration product, so the application of
an excess of the reagent for nitration and a complete reaction is
recommended. However, for imide anhydrides 16 the starting mate-
rial can be more easily removed from 17a and 18a than dinitration
products, so a molar ratio of 1:0.8Ϫ0.9 for 16/N2O4 is recom-
mended. The nitration of 1 proceeds slowly if not catalyzed. Only
60% of 6a was obtained after 72 h reaction time, whereas more than
90% of 6a was isolated after 5 h reaction time with the addition of
methanesulfonic acid.
Figure 9. UV/Vis absorption spectrum of a mixture of 17c and 18c
(color coordinates x ϭ 0.2761, y ϭ 0.1731, Y ϭ 23.54, 2°, norm-
light C at Tmin ϭ 0.1) in chloroform
ring opening to the dicarboxylate. Indeed, dye 17c can be
used as a sensitizer in the Gräzel[24][25] TiO2 electrovoltaic
solar cell, and attains an overall conversion of 0.5% from
solar radiation to electrical energy.[26] Interestingly, the
structurally similar dye 18c is completely inactive in this
cell. Further details of this work will be reported elsewhere.
The UV/Vis spectra of 12a are similar to the spectra of 1
and only slightly bathochromically shifted. A further substi-
tution of the nitrogen atom causes slightly bathochromic
N,NЈ-Bis(1-butylpentyl)-1-nitroperylene-3,4:9,10-bis(dicarboximide)
(6b): N,NЈ-Bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide)
(1b, 2.00 g, 3.12 mmol) was dissolved to give a nearly saturated
solution in dichloromethane. An N2O4 solution in dichloromethane
(37 mL, 0.085 , 3.15 mmol) and methanesulfonic acid (0.02 mL,
30 mg, 0.30 mmol) were added, and the solution was stirred at
room temperature for 5Ϫ6 h. The solvent and the remaining N2O4
shifts for alkylation (R5 ϭ alkyl) and slightly hypsochromic were removed by distillation, and the residue was taken up in tolu-
shifts for acylation (R5 ϭ acyl). The fluorescence quantum
yields of 12 are between 62 and 99% so that 12 can be taken
as a light-stable fluorescent-labelling reagent because of its
simple monofunctionaliszation.
ene and purified by column separation (silica gel, toluene). Yield
2.1 g (98%) of 6b as a dark red powder, m.p. 304°C. Ϫ Rf (silica
gel, toluene) ϭ 0.31. Ϫ Rf (silica gel, toluene/acetone, 10:1) ϭ 0.77.
Ϫ IR (KBr): ν˜ ϭ 2957 cmϪ1 (m), 2930 (m), 2861 (m), 1702 (s),
1662 (s), 1596 (s), 1581 (w), 1537 (s), 1467 (w), 1455 (w), 1427 (w),
The UV/Vis spectra of the thiopheno derivative 11 exhi-
1406 (m), 1350 (m), 1338 (s), 1254 (m), 1183 (w), 1170 (w), 855
bit a hypsochromic shift of 12 nm compared to 1, and the
(w), 812 (m), 717 (m). Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 489 nm
structure of the spectra are similar; see Figure 5. The fluor-
escence quantum yield is 71% in solution and there is an
intense solid-state fluorescence; see Figure 5. The more sul-
(30740), 523 (46060). Ϫ 1H NMR (CDCl3): δ ϭ 0.83 (t, 12 H,
CH3), 1.20Ϫ1.34 (m, 16 H, CH2), 1.86 (mC, 4 H, CHϪCH2), 2.21
(mC, 4 H, CHϪCH2), 5.15 (mC, 2 H, NϪCH), 8.23 (d, J ϭ 8.1 Hz,
fur-rich 13 exhibits a similar absorption as 11, but there is 1 H, perylene), 8.50 (d, J ϭ 8.2 Hz, perylene), 8.67Ϫ8.79 (m, 5 H,
perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.01, 22.58, 29.08, 31.94,
an additional broad structureless band at 611 nm, so that a
32.04, 54.92, 55.20, 124.02, 124.48, 126.70, 127.54, 127.94, 129.13,
brilliant green solution of the dye is obtained; see Figure 6.
129.39, 129.51, 132.95, 135.50, 147.72. Ϫ MS (70 eV): m/z (%): 689
Dye 13 does not exhibit fluorescence and is appreciably less
(11), 688 (47), 687 (100) [Mϩ], 670 (10), 630 (6), 564 (7), 563 (31),
stable than all the other prepared dyes. The lack of fluor-
562 (77), 561 (80) [Mϩ Ϫ C9H18], 546 (5), 544 (7), 516 (7), 448 (5),
escence and the broadness of the absorption may be taken
438 (8), 437 (32), 436 (61), 435 (87) [Mϩ Ϫ 2 ϫ C9H18], 418 (5),
as an indicator that the bathochromic absorption of 13 is a
result of a charge-transfer-transition. Bathochromically
shifted absorptions have previously been observed with 1,2-
dithiin, and were discussed in terms of πϪπ* tran-
sitions,[27][28] or interactions with vacant 3d orbitals.[29]
406 (7), 405 (8), 402 (11), 392 (6), 391 (26), 390 (68), 389 (10) [Mϩ
Ϫ 2 ϫ C9H18 Ϫ NO2], 373 (5), 372 (11), 364 (10), 362 (13), 345
(8), 344 (20). Ϫ C42H45N3O6 (687.8): calcd. C 73.34, H 6.59,
N 6.11; found C 73.44, H 6.67, N 6.22.
N,NЈ-Bis(1-hexylheptyl)-1-nitroperylene-3,4:9,10-bis(dicarboximide)
(6a): N,NЈ-Bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarboximide)
(1a, 2.07 g, 2.75 mmol), a 0.198  N2O4 solution (14.0 mL,
2.77 mmol N2O4), and methanesulfonic acid (0.05 mL, 74 mg,
0.77 mmol) were stirred at room temperature for 7 h. The solvent
was removed by vacuum distillation and the residue purified by
column separation (silica gel, toluene). Yield 2.04 g (93%) of 6a as
a dark red powder, m.p. 121°C. Ϫ Rf (silica gel, chloroform): 0.84.
Experimental Section
N2O4 Solution: N2O4 gas was prepared by strong heating of
Pb(NO3)2, and was introduced into dichloromethane until satu-
ration was obtained. For the determination of the concentration of
N2O4, 10.0 mL of the solution was shaken with 10 mL of 30% hy-
Eur. J. Org. Chem. 2000, 365Ϫ380
369

H. Langhals, S. Kirner
Ϫ Rf (silica gel, toluene): 0.63. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (m), 1059 (w), 1034 (w), 857 (w), 810 (m), 740 (w). Ϫ 1H NMR (CDCl3):
FULL PAPER
2927 (m), 2856 (m), 1702 (s), 1660 (s), 1596 (s), 1581 (w), 1537 (m),
1467 (w), 1426 (w), 1406 (m), 1349 (m), 1338 (s), 1251 (m), 1178
(w), 1112 (w), 855 (w), 812 (m), 746 (m). Ϫ 1H NMR (CDCl3): δ ϭ
δ ϭ 0.80 (t, J ϭ 6.4 Hz, 6 H, CH3), 1.20Ϫ1.30 (m, 16 H, CH2),
1.84 (mC, 2 H, CHϪCH2), 2.13Ϫ2.26 (m, 2 H, CHϪCH2), 5.13 (tt,
3
3J1 ϭ 5.6 Hz, J2 ϭ 9.2 Hz, 1 H, NϪCH), 8.22 and 8.25 (d each,
0.81 (t, 12 H, CH3), 1.16Ϫ1.31 (m, 32 H, CH2), 1.83 (mC, 4 H, J ϭ 8.3 Hz, 1 H, perylene), 8.58 (d, J ϭ 8.1 Hz, 1 H, perylene),
CHϪCH2), 2.20 (mC, 4 H, CHϪCH2), 5.14 (mC, 2 H, NϪCH), 8.68Ϫ8.80 (m, 5 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.0,
8.25 (d, J ϭ 8 Hz, 1 H, perylene), 8.57 (d, J ϭ 8 Hz, 1 H, perylene),
22.5, 26.9, 29.1, 31.7, 32.2, 32.3, 55.1, 55.4, 118.6, 119.5, 119.8,
8.63Ϫ8.79 (m, 5 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.02, 120.6, 124.1, 124.6, 125.0, 125.4, 126.5, 126.8, 127.6, 127.9, 128.2,
22.57, 26.88, 29.16, 31.73, 32.26, 32.35, 39.24, 55.01, 55.29, 124.02, 128.6, 128.8, 128.9, 129.0, 129.4, 130.8, 131.1, 131.2, 131.5, 132.1,
124.48, 126.51, 126.69, 127.57, 127.95, 129.15, 129.40, 129.52,
133.2, 133.5, 134.5, 134.7, 134.9, 137.4, 147.3, 148.1, 158.3, 158.8,
132.97, 135.52, 147.75. Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 490 nm 159.1, 159.4, 167.7. Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 359 nm (6410),
(30820), 523 (46100). Ϫ MS (70 eV): m/z (%): 801 (18), 800 (62), 452 (9100), 489 (25750), 519 (38050). Ϫ MS (70 eV): m/z (%): 620
799 (100) [Mϩ], 783 (7), 782 (13), 714 (6), 620 (14), 619 (56), 618 (9), 619 (41), 618 (100) [Mϩ], 439 (21), 438 (93), 437 (79), 436 (88)
(98), 617 (87) [Mϩ Ϫ C13H26], 601 (5), 600 (7), 448 (6), 438 (16), [Mϩ Ϫ C13H26], 407 (7), 406 (10) [Mϩ Ϫ C13H26 Ϫ NO], 392 (15),
437 (59), 436 (71), 435 (93) [Mϩ Ϫ 2 ϫ C13H26], 418 (6),416 (5), 391 (36) [Mϩ Ϫ C13H26 Ϫ NO2 ϩ H], 365 (5), 364 (5) [Mϩ
Ϫ
407 (8), 406 (10), 405 (11), 404 (6), 403 (5), 402 (8), 392 (14), 391 C13H26 Ϫ C2O3], 363 (5), 318 (5) [Mϩ Ϫ C13H26 Ϫ C2O3 Ϫ NO2].
(36), 390 (76), 389 (10) [Mϩ Ϫ 2 ϫ C13H26 Ϫ NO2], 372 (8), 364
Ϫ C37H34N2O7 (618.7): calcd. C 71.83, H 5.54, N 4.53; found
(9), 362 (11), 345 (6), 344 (14). Ϫ C50H61N3O6 (800.1): calcd. C 71.69, H 5.82, N 4.31.
C 75.06, H 7.69, N 5.25; found C 75.24, H 7.68, N 5.12.
Reaction
of
N,NЈ-Bis(1-hexylheptyl)-1-nitroperylene-3,4:9,10-
N,NЈ-Bis(2,5-di-tert-butylphenyl)-1-nitroperylene-3,4:9,10-bis-
(dicarboximide) (6c): Compound 1c (800 mg, 1.04 mmol) was dis-
solved in dichloromethane to give a nearly saturated solution. A
0.05  N2O4 solution (21.0 mL, 1.05 mmol N2O4) and methanesul-
fonic acid (0.05 mL, 74 mg, 0.77 mmol) were added. The mixture
was stirred at room temperature for 4 h, the solvent and unchanged
N2O4 were removed by distillation and the residue was taken up in
chloroform and purified by column separation (silica gel, chloro-
form). Yield 800 mg (94%) of 6c as a dark red crystal powder, m.p.
> 300°C. Ϫ Rf (silica gel/chloroform): 0.45. Ϫ IR (KBr): ν˜ ϭ 3077
cmϪ1 (m), 2963 (m), 2869 (w), 1712 (s), 1675 (s), 1596 (s), 1539
(m), 1503 (w), 1466 (w), 1423 (m), 1402 (m), 1343 (s), 1252 (m),
1201 (s), 1003 (w),977 (w), 822 (m), 812 (m), 750 (m), 728 (w). Ϫ
1H NMR (CDCl3): δ ϭ 1.289 and 1.295 (s each, 18 H), 1.313 and
1.316 (s each, 18 H), 6.990 (s, 2 H, phenyl), 7.467 and 7.483 (dd
bis(dicarboximide) (6a) with Triethyl Phosphite: Compound 6a
(150 mg, 0.188 mmol) was dissolved in triethyl phosphite (5 mL,
4.84 g, 29.1 mmol) and heated under argon at 130°C for 5 h (until
no non fluorescent starting material, 6a, could be detected by
TLC), precipitated by adding in 1  HCl (150 mL), and stirred at
room temperature for 16 h to hydrolyse the triethyl phosphite. The
precipitate was collected by vacuum filtration (dark red precipi-
tate), dried and purified by column separation (alumina, chloro-
form). Ϫ First Fraction: yield 43 mg (26%) of 7a, m.p. 61Ϫ63°C.
Ϫ Rf (Al2O3, chloroform): 0.82. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (s),
2928 (s), 2857 (m), 1698 (s), 1659 (s), 1592 (s), 1578 (w), 1456 (m),
1446 (m), 1404 (m Ϫ s), 1340 (s), 1250 (m Ϫ s), 1176 (w), 1110 (w),
1045 (m, PϪOϪEt), 1020 (m, PϪOϪEt), 978 (m, br., PϪOϪEt),
1
814 (m), 749 (m). Ϫ H NMR (CDCl3): δ ϭ 0.78 and 0.79 (t each,
J ϭ 6.4 Hz, 12 H, CH3), 1.15Ϫ1.38 (m, 38 H, 16 ϫ CH2 ϩ 2 ϫ
OϪCH2ϪCH3), 1.82 (mC, 4 H, CHϪCH2), 2.20 (mC, 4 H,
3
4
each, JCH ϭ 8.5 and 8.3 Hz, JCH ϭ 2.3 Hz, 2 H, phenyl), 7.596
3
and 7.607 (d each, JCH ϭ 8.5 Hz, 2 H, phenyl), 8.317 and 8.324
3
CHϪCH2), 4.21 (mC, 4 H, OϪCH2ϪCH3), 5.15 (tt, J1 ϭ 9.3 Hz,
(d each, J ϭ 8.1 Hz, 1 H, perylene), 8.672 and 8.699 (s each, 1 H,
perylene), 8.751Ϫ8.885 (m, perylene). Ϫ 13C NMR (CDCl3): δ ϭ
31.18, 31.76, 34.25, 34.28, 35.55, 35.58, 123.39, 124.17, 124.30,
124.49, 124.77, 125.18, 126.54, 126.71, 126.76, 127.20, 127.22,
127.46, 127.56, 127.87, 127.89, 128.22, 128.89, 129.00, 129.34,
129.38, 129.72, 129.75, 129.86, 129.89, 131.63, 131.89, 132.21,
132.22, 133.36, 133.41, 133.44, 135.96, 143.75, 143.79, 147.81,
150.25, 150.27, 150.40, 150.42, 162.85, 163.69, 163.77, 164.09. Ϫ
UV/Vis (CHCl3): λmax (Erel.) ϭ 369 nm (0.08), 457 (0.20), 490
(0.65), 524 (1.0). Ϫ MS (70 eV): m/z (%): 757 (5), 756 (18), 755
(55), 754 (100) [Mϩ Ϫ C4H9], 714 (7), 710 (7), 709 (16), 708 (10)
[Mϩ Ϫ C4H9ϪNO2], 699 (7). Ϫ C48H40N3O6 (754.86): calcd.
754.2917; found 754.2949 (MS). Ϫ C52H49N3O6 (812.0): calcd.
C 76.92, H 6.08, N 5.18; found C 74.69, H 5.98, N 5.02.
3J2 ϭ 5.7 Hz, 2 H, NϪCH), 8.61Ϫ8.78 (m, 5 H, perylene), 9.14 (br.
d, J ϭ 13.81 Hz, 1 H, perylene), 9.27 (d, J ϭ 8.1 Hz, 1 H, perylene).
3
Ϫ
13C NMR (CDCl3): δ ϭ 13.96, 16.24 (d, JPC ϭ 6.2 Hz, CH3),
22.50, 26.84, 29.12, 31.68, 32.28, 32.32, 54.72, 54.82, 63.41 (d,
2JCP ϭ 6.5 Hz), 123.52, 125.20, 126.44, 127.47, 127.67, 127.69,
128.43, 129.95 (d, JPC ϭ 2.4 Hz), 132.87, 133.19, 135.13, 140.95 (d,
1JCP ϭ 9.4 Hz), 163.33, 164.64. Ϫ 31P NMR (CDCl3): δ ϭ 18.21.
Ϫ UV/Vis (CHCl3): λmax (Erel.) ϭ 375 nm (0.03), 434 (0.06), 463
(0.26), 493 (0.69), 529 (1.0). Ϫ Fluorescence (chloroform): λmax
(Irel.) ϭ 548 nm (1.0), 590 (0.66), 643 (0.18). Ϫ Fluorescence quan-
tum yield (1.03 ϫ 10Ϫ6 mol/L in CHCl3, reference N,NЈ-bis(1-hex-
ylheptyl)perylene-3,4:9,10-bis(dicarboximide) (1a) with Φ ϭ 100%,
λexcit. ϭ 490 nm) ϭ 91%. Ϫ MS (70 eV): m/z (%): 892 (18), 891
(60), 890 (100) [Mϩ], 874 (6), 873 (10) [Mϩ Ϫ OH], 755 (14), 754
Nitration of N-(1-Hexylheptyl)perylene-3,4:9,10-tetracarboxylic 3,4-
Anhydride 9,10-Imide (16a): Compound 16a (100 mg, 0.175 mmol)
was dissolved in dichloromethane (50 mL). A 0.030  solution of
N2O4 in dichloromethane (5.50 mL, 0.165 mmol N2O4) and meth-
anesulfonic acid (0.05 mL, 74 mg, 0.77 mmol) were added. The
mixture was stirred at room temperature for 4 h, the solvent re-
moved by distillation, and the residue purified by column separ-
ation (silica gel, chloroform/7% acetic acid or dichloromethane/2%
acetic acid). Yield 83 mg (77%) of a mixture of 17a and 18a as a
dark red powder, m.p. 189Ϫ191°C. Ϫ Rf (silica gel, dichlorometh-
(25) [Mϩ Ϫ PO(OEt)2 ϩ H], 710 (10), 709 (27), 708 (36) [Mϩ
Ϫ
C13H26], 573 (14), 572 (15) [Mϩ Ϫ C13H26 Ϫ PO(OEt)2 ϩ H], 528
(6), 527 (19), 526 (38) [Mϩ Ϫ 2 ϫ C13H26], 471 (17), 470 (9), 469
(9) [Mϩ Ϫ 2 ϫ C13H26 Ϫ C4H9], 453 (14), 452 (7), 435 (7), 392
(10), 391 (30), 390 (44) [Mϩ Ϫ 2 ϫ C13H26 Ϫ PO(OEt)2 ϩ H]. Ϫ
C54H71N2O7P (891.1): calcd. C 72.78, H 8.03, N 3.14; found
C 71.93, H 8.40, N 3.10. Ϫ Second Fraction: Yield 91.0 mg (63%)
of 12a, m.p. 204Ϫ205°C. Ϫ Rf (Al2O3, chloroform): 0.42. Ϫ IR
(nujol): ν˜ ϭ 2955 cmϪ1 (s), 2927 (s), 2854 (s), 1693 (s), 1656 (s),
1607 (m), 1561 (m), 1460 (s), 1411 (w), 1377 (m), 1339 (w), 1287
ane/2% acetic acid): 0.73. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (w), 2927 (m), 1256 (w), 1207 (w), 1191 (w), 1164 (w), 1141 (w), 1117 (w),
(m), 2857 (w), 1778 (s), 1739 (m), 1705 (m), 1662 (s), 1598 (s), 1538 845 (w), 804 (m), 743 (m), 725 (w). Ϫ H NMR (CDCl3): δ ϭ 0.79
1
(m), 1456 (w), 1405 (w), 1354 (w), 1322 (s), 1248 (m), 1161 (w), (t, 12 H, CH3), 1.21Ϫ1.40 (m, 32 H, CH2), 1.93 (mC, 4 H,
370
Eur. J. Org. Chem. 2000, 365Ϫ380

Novel Fluorescent Dyes by the Extension of the Core of Perylenetetracarboxylic Bisimides
FULL PAPER
CHϪCH2), 2.32 (mC, 4 H, CHϪCH2), 5.32 (mC, 2 H, NϪCH),
8.80 (d, J ϭ 7.0 Hz, 1 H, perylene), 8.85 (d, J ϭ 7.2 Hz, 1 H, per-
ylene), 8.92 (d, J ϭ 7.9 Hz, 2 H, perylene), 8.99 (s, 1 H, perylene),
Fluorescence (chloroform): λmax ϭ 541 nm, 575. Ϫ Fluorescence
quantum yield (1.03 ϫ 10Ϫ6 mol/L in CHCl3, reference N,NЈ-bis(1-
hexylheptyl)perylene-3,4:9,10-bis(dicarboximide) (1a) with Φ ϭ
9.04 (s, 1 H, perylene), 10.66 (s, 1 H, NH). Ϫ 13C NMR (CDCl3): 100%, λexcit. ϭ 490 nm) ϭ 84%. Ϫ MS (70 eV): m/z (%): 656 (12),
δ ϭ 14.10, 22.73, 29.35, 33.12, 54.04, 54.88, 119.87, 120.14,
655 (27) [Mϩ], 638 (9), 531 (5), 530 (19), 529 (29) [Mϩ Ϫ C9H18],
120.63,121.75, 123.70, 124.56, 124.69, 127.24, 127.68, 128.38, 512 (8), 416 (9), 405 (12), 404 (49), 403 (100) [Mϩ Ϫ 2 ϫ C9H18],
128.83, 130.93, 132.84, 133.75, 165.20, 165.64, 166.52. Ϫ UV/Vis
(CHCl3): λmax (ε) ϭ 457 nm (19300), 490 (43490), 524 (80280). Ϫ
Fluorescence (chloroform): 539 nm, 575. Ϫ MS (70 eV): m/z (%):
768 (15), 767 (27) [Mϩ], 751 (5), 750 (10), 587 (8), 586 (24), 585
(29) [Mϩ Ϫ C13H26], 568 (7), 416 (8), 405 (13), 404 (51), 403 (97)
[Mϩ Ϫ 2 ϫ C13H26], 386 (14), 358 (7). Ϫ C50H61N3O4 (768.0):
calcd. C 78.19, H 8.01, N 5.47; found C 77.98, H 8.16, N 5.51.
387 (6), 386 (17), 359 (7), 358 (12). Ϫ C42H45N3O4 (655.8): calcd.
C 76.92, H 6.92, N 6.41; found C 76.95, H 6.98, N 6.30.
Methylation of 12b. ؊ Method A: Compound 12b (100 mg,
0.153 mmol) was dissolved in ethanol (10 mL), deprotonated with
85% KOH powder (17.0 mg, 0.258 mmol, dark violet solution).
Iodomethane (0.500 mL, 1.14 g, 8.0 mmol) was added, the mixture
stirred at room temperature for 16 h, the ethanol was removed by
distillation, the residue taken up in chloroform, washed repeatedly
with water, dried (MgSO4), concentrated by vacuum distillation
and purified by column separation (silica, chloroform). Yield 93 mg
(91%) of 12d as a cherry-red powder. Ϫ Method B: N,NЈЈ-bis(1-
butylpentyl)pyrrolo[2,3,4,5-hik]perylene-3,4:8,9-bis(dicarboximide)
(12b, 100 mg, 0.153 mmol) was dissolved in ethanol (10 mL), de-
protonated with 85% KOH powder (17.0 mg, 0.258 mmol, violet
solution), concentrated by vacuum distillation and taken up in N-
methylpyrrolidone. Iodomethane (0.100 mL, 0.230 g, 1.60 mmol)
was added. The mixture was stirred at room temperature for 12 h
and poured in water. Ethanol was added until the N-methylpyrroli-
done dissolved and the solution was stirred at room temperature
for 16 h to age the precipitate which was further purified as was
described for Method A. Ϫ Yield 93 mg (91%) of 12d as a cherry-
red powder, m.p. > 300°C. Ϫ Rf (silica gel, chloroform): 0.61. Ϫ
Rf (Al2O3, chloroform): 0.77. Ϫ IR (KBr): ν˜ ϭ 2956 cmϪ1 (m),
2929 (m), 2860 (m), 1695 (s), 1653 (s), 1604 (m), 1558 (w), 1457 (w),
1444 (w), 1423 (m), 1392 (w), 1380 (w), 1350 (m), 1312 (s), 1258
(m), 1222 (w), 1175 (w), 1135 (w), 1130 (w), 1115 (w), 1110 (w),
Reaction of N,NЈ-Bis(1-butylpentyl)-1-nitroperylene-3,4:9,10-bis-
(dicarboximide) (6b) with Triethyl Phosphite: Compound 6b
(300 mg, 0.437 mmol) in triethyl phosphite (10.0 mL, 9.69 g,
58.3 mmol) was heated under argon at 130°C for 3 h (until no non-
fluorescent starting material 6b could be detected by TLC), precipi-
tated by pouring in 1  HCl (100 mL), and stirred at room tem-
perature for 16 h to hydrolyse the triethyl phosphite. The dark red
precipitate was collected by vacuum filtration, dried and purified
by column separation (alumina activity II, chloroform/1% ethanol).
Ϫ First Fraction: Yield 109 mg (32%) of N,NЈ-bis(1-butylpen-
tyl)perylene-3,4:9,10-bis(dicarboximide)-1-diethylphosphonate
(7b), m.p. 122Ϫ124°C. Ϫ Rf (Al2O3, chloroform): 0.62. Ϫ IR
(KBr): ν˜ ϭ 2957 cmϪ1 (m), 2929 (m), 2862 (w), 1699 (s), 1660 (s),
1592 (m), 1446 (w, br.), 1404 (m), 1340 (m), 1253 (m), 1106 (w),
1044 (m, PϪOϪEt), 1020 (m, PϪOϪEt), 970. (w br., PϪOϪEt),
1
814 (m), 750 (w). Ϫ H NMR (CDCl3): δ ϭ 0.85 and 0.86 (each t,
J ϭ 6.9 Hz, 12 H, CH3), 1.15Ϫ1.38 (m, 22 H, 8·CH2
ϩ
2·OϪCH2ϪCH3), 1.83Ϫ1.94 (m, 4 H, CHϪCH2), 2.21Ϫ2.33 (m, 4
H, CHϪCH2), 4.24 (mC, 4 H, OϪCH2ϪCH3), 5.20 (mC, 2 H,
1
900 (w), 845 (w), 804 (m), 741 (m). Ϫ H NMR (CDCl3): δ ϭ 0.84
3
NϪCH) 8.65Ϫ8.83 (m, 5 H, perylene), 9.18 (br. d, JPH
ϭ
(t, J ϭ 6.9 Hz, 12 H, CH3), 1.24Ϫ1.42 (m, 16 H, CH2), 1.88Ϫ1.96
(m, 4 H, CHϪCH2), 2.28Ϫ2.38 (m, 4 H, CHϪCH2), 4.50 (s, 3 H,
NϪCH3 ), 5.32 [m, 2 H, CH-(CH2)2], 8.82 (s, 2 H, perylene), 8.93
(d, J ϭ 8.1 Hz, 2 H, perylene), 8.97 (s, 2 H, perylene). Ϫ 13C NMR
(CDCl3): δ ϭ 14.1, 22.7, 29.3, 32.4, 35.5 [NϪCH3 ], 54.8, 119.7,
122.0, 124.0, 124.8, 132.9, 135.5. Ϫ UV/Vis (CHCl3): λmax (ε) ϭ
410 nm (1890), 435 (7080), 465 (18730), 494 (40320), 530 (78790).
Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 540 nm (1.0), 578
(0.68), 621 (0.11). Ϫ Fluorescence quantum yield (9.60 ϫ 10Ϫ7 mol/
l in CHCl3, reference N,NЈ-bis(1-hexylheptyl)perylene-3,4:9,10-
bis(dicarboximide) (1a) with Φ ϭ 100%, λexcit. ϭ 490 nm) ϭ 56%.
Ϫ MS (70 eV): m/z (%): 670 (19), 669 (41) [Mϩ], 653 (7), 652 (13)
[Mϩ Ϫ OH], 545 (5), 544 (18), 543 (29) [Mϩ Ϫ C9H18], 527 (5),
526 (10) [Mϩ Ϫ C9H18 Ϫ OH], 430 (9), 419 (11), 418 (51), 417
(100) [Mϩ Ϫ 2 ϫ C9H18], 401 (5), 400 (16) [Mϩ Ϫ 2 ϫ C9H18
ϪOH], 373 (8), 372 (15). Ϫ C43H47N3O4 (669.9): calcd. C 77.10,
H 7.07, N 6.27; found C 76.74, H 7.38, N 6.08.
14.02 Hz, 1 H, perylene), 9.31 (d, J ϭ 8.1 Hz, 1 H, perylene). Ϫ
3
13C NMR (CDCl3): δ ϭ 14.06, 16.32 (d, JPC ϭ 5.6 Hz, CH3),
2
22.63, 29.13, 32.05, 32.09, 54.73, 54.84, 63.50 (d, JPC ϭ 6.5 Hz),
123.61, 125.22, 126.50, 127.53, 127.72, 128.49, 130.03 (d, J ϭ
1
2.6 Hz), 132.94, 133.26, 135.21, 141.03 (d, JPC ϭ 8.8 Hz). Ϫ
31P NMR (CDCl3): δ ϭ 18.22. Ϫ UV/Vis (CHCl3): λmax (ε) ϭ
349 nm (3950), 433 (4980), 464 (16040), 493 (38360), 529 (54680).
Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 551 nm (1.0), 589
(0.82), 642 (0.18). Ϫ MS (70 eV): m/z (%): 780 (14), 779 (51), 778
(100) [Mϩ], 762 (9), 761 (17) [Mϩ Ϫ OH], 749 (5) [Mϩ Ϫ C2H5],
721 (6) [Mϩ Ϫ C4H9], 654 (10), 653 (32), 652 (54) [Mϩ Ϫ C9H18],
635 (9), 623 (5) [Mϩ Ϫ C9H18 Ϫ C2H5], 528 (8), 527 (28), 526 (66)
[Mϩ Ϫ 2 ϫ C9H18], 499 (8), 498 (11) [Mϩ Ϫ 2 ϫ C9H18 Ϫ C2H4],
472 (8), 471 (30), 470 (17), 469 (17) [Mϩ Ϫ 2 ϫ C9H18 Ϫ C4H9],
454 (9), 453 (28), 452 (13), 407 (6), 391 (5), 390 (6).
C46H55N2O7P: calcd. 778.3747, found 778.3738 (MS).
Ϫ
Ϫ
C46H55N2O7P (778.9): calcd. C 70.93, H 7.12, N 3.60; found
C 70.07, H 7.22, N 3.57. Ϫ Second Fraction: Yield 160 mg (56%) of Benzylation of N,NЈ-Bis(1-hexylheptyl)pyrrolo[2,3,4,5-hik]perylene-
12b, m.p. > 300°C. Ϫ Rf (Al2O3 neutral, chloroform): 0.24. Ϫ IR
3,4:8,9-bis(dicarboximide) (12a). ؊ Method A: Compound 12a
(KBr): ν˜ ϭ 2957 cmϪ1 (m), 2928 (m), 2860 (m), 1693 (s), 1656 (s), (100 mg, 0.130 mmol) was dissolved in ethanol (10 mL) and depro-
1606 (m), 1560 (m), 1538 (w), 1457 (m), 1437 (m), 1411 (m), 1379 tonated with 85% KOH powder (11.0 mg, 0.167 mmol). Benzyl bro-
(m), 1336 (m), 1286 (s), 1258 (m), 1207 (w), 1193 (w), 1137 (w), mide (222 mg, 1.30 mmol) was added and the mixture stirred at
1114 (w), 845 (w), 805 (m), 744 (m). Ϫ 1H NMR (CDCl3): δ ϭ room temperature for 12 h, concentrated and purified by column
0.82 (t, 12 H, CH3), 1.23Ϫ1.40 (m, 16 H, CH2), 1.93 (mC, 4 H,
separation (silica gel, petroleum ether/chloroform, 5:1 and then
CHϪCH2), 2.33 (mC, 4 H, CHϪCH2), 5.33 (mC, 2 H, NϪCH), with chloroform). Yield 83.0 mg (74%) of 12e as a red powder. Ϫ
8.72 (mC, 4 H, perylene), 8.97 (br. s, 1 H, perylene), 9.00 (br. s, 1
Method B: Compound 12a (100 mg, 0.130 mmol) was dissolved in
THF (10 mL) and deprotonated with DBU (30.0 mg, 0.197 mmol).
H, perylene), 10.30 (s, 1 H, NH). Ϫ 13C NMR (CDCl3): δ ϭ 14.03,
22.59, 27.09, 29.30, 31.79, 32.25, 54.92, 119.78, 120.41, 122.02, Benzyl bromide (222 mg, 1.30 mmol) was added and the mixture
122.45, 123.98, 124.90, 127.87, 128.61, 133.11, 133.72. Ϫ UV/Vis
(CHCl3): λmax (ε) ϭ 457 nm (18330), 489 (41140), 523 (75450). Ϫ
was stirred at room temperature until the starting material could
not be detected by TLC, concentrated, and purified as was de-
Eur. J. Org. Chem. 2000, 365Ϫ380
371

H. Langhals, S. Kirner
FULL PAPER
scribed for Method A. Yield 97 mg (87%) of 12e, m.p. 134Ϫ135°C.
Ϫ Rf (silica gel, chloroform): 0.62. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1
with 2  HCl as soon as no starting material could be detected by
TLC. The excess bromoacetic ester was dissolved with the addition
(m), 2927 (s), 2856 (m), 1693 (s), 1655 (s), 1604 (m), 1559 (m), 1455 of acetone. The red precipitate was collected by vacuum filtration,
(w), 1444 (w), 1424 (m), 1401 (w), 1380 (w), 1351 (m), 1303 (s), dried and purified by column separation (silica gel, chloroform).
1258 (w), 1205 (w), 1167 (w), 1114 (w), 1028 (w), 848 (w), 806 (m), Yield 95 mg (81%) of 12g as a bright red powder, m.p. 110Ϫ111°C.
743 (m), 705 (w). Ϫ 1H NMR (CDCl3): δ ϭ 0.79 (t, J ϭ 7 Hz, 12 H, Ϫ Rf (silica gel, chloroform): 0.56. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (s),
CH3), 1.23Ϫ1.68 (m, 32 H, CH2), 1.89Ϫ1.96 (m, 4 H, CHϪCH2),
2926 (s), 2856 (s), 1749 (m), 1694 (s), 1654 (s), 1605 (s), 1560 (m),
2.29Ϫ2.33 (m, 4 H, CHϪCH2), 5.26Ϫ5.36 [m, 2 H, CH(CH2)2], 1480 (w), 1459 (m), 1446 (w), 1425 (s), 1403 (w), 1377 (w), 1350
5.94 (s, 2 H, CH2Ϫphenyl), 7.28Ϫ7.30 (m, 5 H, phenyl), 8.75Ϫ8.89 (w), 1316 (s, br), 1295 (m), 1257 (w), 1204 (m, br, sh. w), 1168 (m),
(m, 6 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.0, 22.6, 27.1,
1115 (w), 1035 (w, sh.), 900 (w), 850 (w), 805 (s), 742 (m). Ϫ
29.3, 31.8, 32.6, 50.3 (CH2Ϫphenyl), 54.9, 118.4, 119.1, 119.6, 1H NMR (CDCl3): δ ϭ 0.80 (t, J ϭ 6.7 Hz, 12 H, CH3), 1.21Ϫ1.37
121.6, 122.3, 123.0, 123.8, 124.7, 127.0, 127.6, 128.3, 128.6, 129.3, (m, 35 H, CH2 ϩ CH3), 1.87Ϫ1.93 (m, 4 H, CHϪCH2), 2.28Ϫ2.36
132.6, 134.8, 136.1, 164.0, 165.0, 166.2. Ϫ UV/Vis (CHCl3): λmax (m, 4 H, CHϪCH2), 4.31 (q, J ϭ 7.2 Hz, 2 H, OϪCH2ϪCH3), 5.30
(ε) ϭ 406 nm (4840), 435 (10770), 463 (23660), 493 (46140), 528 (mC, 2 H, NϪCH), 5.53 (s, 2 H, NϪCH2ϪCO2Et), 8.80Ϫ8.91 (m,
(86280). Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 537 nm (1.0),
577 (0.45), 623 (0.10). Ϫ Fluorescence quantum yield (8.66 ϫ
10Ϫ7 mol/L in CHCl3, reference N,NЈ-bis(1-hexylheptyl)perylene-
6 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.0, 14.2, 22.6, 27.0,
29.3, 31.8, 32.6, 47.3, 54.9, 62.6, 118.1, 118.9, 120.1, 121.8, 122.0,
122.5, 123.2, 124.1, 125.0, 127.9, 128.7, 133.0, 135.4, 164.1, 165.1,
166.3, 167.4. Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 405 nm (3240), 431
3,4:9,10-bis(dicarboximide) (1a) with
Φ ϭ 100%, λexcit. ϭ
490 nm) ϭ 62%. Ϫ MS (70 eV): m/z (%): 859 (20), 858 (59), 857 (9250), 460 (23340), 490 (46420), 525 (89690). Ϫ Fluorescence
(97) [Mϩ], 841 (16), 840 (28) [Mϩ Ϫ OH], 772 (5) [Mϩ Ϫ C6H12 ], (chloroform): λmax ϭ 535 nm, 570. Ϫ MS (70 eV): m/z (%): 855
768 (7), 767 (15) [Mϩ Ϫ C7H7], 677 (14), 676 (39) [Mϩ Ϫ C9H18],
(18), 854 (53), 853 (89) [Mϩ], 837 (10), 836 (16) [Mϩ Ϫ OH], 768
(6) [Mϩ Ϫ C6H13], 673 (14), 672 (37), 671 (30) [Mϩ Ϫ C13H26], 655
659 (9), 658 (15) [Mϩ Ϫ C6H12 Ϫ OH], 586 (9), 585 (10) [Mϩ
C7H7], 507 (5), 506 (10), 495 (22), 494 (69), 493 (100) [Mϩ Ϫ 2 ϫ
C9H18], 476 (10), 416 (5), 404 (16), 403 (29) [Mϩ Ϫ 2 ϫ C9H18
Ϫ
(5), 654 (10) [Mϩ Ϫ C13H26 Ϫ OH], 587 (5) [[Mϩ Ϫ C13H26
Ϫ
Ϫ
C6H13], 503 (5), 502 (11) [Mϩ Ϫ C13H27 Ϫ 2 ϫ C6H13], 491 (18),
C7H7], 386 (5). Ϫ C57H67N3O4 (858.2): calcd. C 78.78, H 7.87, 490 (59), 489 (100) [Mϩ Ϫ 2 ϫ C13H26], 462 (9), 444 (8), 417 (12),
N 4.90; found C 78.89, H 7.68, N 4.88.
416 (35) [Mϩ Ϫ CO2Et], 373 (5). Ϫ C54H67N3O6 (854.1): calcd.
C 75.94, H 7.96, N 4.92; found C 75.77, H 7.96, N 4.83.
N,NЈЈ-Bis(1-butylpentyl)-NЈ-benzylpyrrolo[2,3,4,5-hik]perylene-
NЈ-Acetyl-N,NЈЈ-bis(1-hexylheptyl)pyrrolo[2,3,4,5-hik]perylene-
3,4:8,9-bis(dicarboximide) (12h): Compound 12a (56 mg,
0.07 mmol) was dissolved in THF, deprotonated with DBU (17 mg,
0.11 mmol), acylated with acetyl chloride (12 mg, 0.15 mmol)
(color changes from bluish-violet to red), poured into water
(50 mL), and allowed to stand for 16 h. The product was collected
by vacuum filtration, dried, and purified by column separation
(chloroform/silica gel). Yield 43 mg (73%) of 12h as a bright
red powder, m.p. > 300°C. Ϫ Rf (silica gel, chloroform): 0.62.
Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (s), 2926 (s), 2854 (s), 1726 (w,
CH3ϪCϭO), 1700 (s), 1675 (w), 1658 (s, br), 1608 (m), 1600 (w),
1563 (m), 1550 (w), 1523 (w), 1457 (w), 1419 (m), 1399 (w), 1376
(m), 1366 (m), 1347 (m), 1312 (s), 1305 (s, sh), 1256 (m), 1206 (w),
1184 (w), 1169 (w), 1094 (w), 1026 (w), 925 (w), 902 (w), 849 (m),
806 (s), 740 (s), 617 (w). Ϫ 1H NMR (CDCl3): δ ϭ 0.81 (t, J ϭ
7 Hz, 12 H, CH3), 1.20Ϫ1.37 (m, 32 H, CH2), 1.95 (mC, 4 H,
CHϪCH2), 2.30 (mC, 4 H, CHϪCH2), 3.11 (s, 3 H, CH3ϪCO),
5.27 [mC, 2 H, CHϪ(CH2)2], 8.61 (d, J ϭ 7.9 Hz, 2 H, perylene),
8.71 (br. d, 2 H, perylene), 9.10 (s, 2 H, perylene). Ϫ 13C NMR
(CDCl3): δ ϭ 14.0, 22.6, 25.9 (CH3ϪCO), 27.1, 29.3, 31.8, 32.6,
55.1, 121.3, 122.0, 122.2, 123.0, 123.3, 124.1, 124.2, 125.8, 129.6,
130.2, 133.2, 133.3, 143.2, 163.3, 164.3, 165.4, 169.6 (CH3ϪCϭO).
Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 408 nm (7460), 432 (17740), 452
(15730), 482 (46350), 517 (86180). Ϫ Fluorescence (chloroform):
λmax ϭ 526 nm, 562. Ϫ Fluorescence quantum yield (8.09 ϫ
10Ϫ7 mol/L in CHCl3, reference N,NЈ-bis(1-hexylheptyl)perylene-
3,4:8,9-bis(dicarboximide)
(12f):
N,NЈЈ-Bis(1-butylpentyl)pyr-
rolo[2,3,4,5-hik]perylene-3,4:8,9-bis(dicarboximide) (12b, 40 mg,
0.06 mmol) was dissolved in THF, deprotonated with DBU (19 mg,
0.13 mmol), alkylated with benzyl bromide (25 mg, 0.15 mmol)
analogous to Method B for 12a (2 h), and poured into 2  HCl
(50 mL). The excess benzyl bromide was dissolved by the addition
of acetone. The product was collected by vacuum filtration, dried
and purified by column separation (silica gel activity IV/chloro-
form). Yield 35 mg (77%) of 12f as a bright red powder, m.p.
212Ϫ213°C. Ϫ Rf (silica gel, chloroform): 0.42. Ϫ IR (KBr): ν˜ ϭ
2956 cmϪ1 (m), 2928 (m), 2861 (m), 1693 (s), 1654 (s), 1604 (m),
1560 (m), 1456 (w), 1444 (w), 1425 (m), 1402 (w), 1380 (w), 1351
(w), 1305 (s, br.), 1259 (w), 1174 (w), 806 (m), 743 (m), 703 (w). Ϫ
1H NMR (CDCl3): δ ϭ 0.84 (t, J ϭ 7.0 Hz, 12 H, CH3), 1.21Ϫ1.42
(m, 16 H, CH2), 1.87Ϫ1.98 (m, 4 H, CHϪCH2), 2.28Ϫ2.36 (m,
4 H, CHϪCH2), 5.30 (tt, 3J1 ϭ 9.1 Hz, 3J2 ϭ 5.9 Hz, 2 H, NϪCH),
5.99 (s, 2 H, NϪCH2Ϫphenyl), 7.31Ϫ7.36 (m, 5 H, phenyl),
8.80Ϫ8.90 (m, 6 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.1,
22.7, 29.3, 32.3, 50.4 (CH2Ϫphenyl), 54.8, 118.5, 119.3, 119.8,
121.6, 121.9, 122.3, 123.1, 124.0, 124.8, 127.1, 127.7, 128.4, 128.6,
129.3, 132.8, 135.0, 136.2, 164.1, 165.2, 166.3. Ϫ UV/Vis (CHCl3):
λmax (ε) ϭ 434 nm (9320), 465 (22820), 493 (45250), 529 (85900).
Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 543 nm (1.0), 580
(0.50), 624 (0.05). Ϫ MS (70 eV): m/z (%): 747 (15), 746 (55), 745
(100) [Mϩ], 729 (9), 728 (16) [Mϩ Ϫ OH], 621 (8), 620 (25), 619
(32) [Mϩ Ϫ C9H18], 603 (65), 602 (11), 506 (9), 495 (15), 494 (57),
493 (94) [Mϩ Ϫ 2 ϫ C9H18], 476 (6), 92 (5), 91 (77) [C7H7]. Ϫ
C49H51N3O4 (746.0): calcd. C 78.90, H 6.89, N 5.63; found C 78.51,
H 6.86, N 5.61.
3,4:9,10-bis(dicarboximide) (1a) with
Φ ϭ 100%, λexcit. ϭ
484 nm) ϭ 99%. Ϫ MS (70 eV): m/z (%): 811 (14), 810 (47), 809
(79) [Mϩ], 793 (8), 792 (13) [Mϩ Ϫ OH], 769 (8), 768 (30), 767 (54)
[Mϩ Ϫ CH2ϭCϭO], 751 (5), 750 (9), 724 (5), 629 (15), 628 (40),
627 (49) [Mϩ Ϫ C13H26], 610 (6), 587 (7), 586 (24), 585 (30) [Mϩ
Ϫ C13H26 Ϫ CH2ϭCϭO], 568 (5), 447 (10), 446 (29), 445 (47) [Mϩ
NЈ-(Ethoxycarbonylmethyl)-N,NЈЈ-bis(1-hexylheptyl)pyrrolo[2,3,4,5-
hik]perylene-3,4:8,9-bis(dicarboximide) (12g): Compound 12a
(105 mg, 0.137 mmol) was dissolved in tetrahydrofuran (15 mL), Ϫ 2 ϫ C13H26], 416 (8), 405 (15), 404 (62), 403 (100) [Mϩ Ϫ 2 ϫ
deprotonated with DBU (31.0 mg, 0.204 mmol), alkylated with
bromoacetic acid ethyl ester (46.0 mg, 0.277 mmol, color changes
C13H26ϪCH2ϭCϭO], 387 (5), 386 (13), 358 (5). Ϫ C52H63N3O5
(810.1): calcd. C 77.10, H 7.84, N 5.19; found C 76.99, H 7.72,
from blue-violet to red within a few minutes), immediately acidified N 5.14.
372
Eur. J. Org. Chem. 2000, 365Ϫ380

Novel Fluorescent Dyes by the Extension of the Core of Perylenetetracarboxylic Bisimides
FULL PAPER
NЈ-Acetyl-N,NЈЈ-bis(1-butylpentyl)pyrrolo[2,3,4,5-hik]perylene-
3,4:8,9-bis(dicarboximide) (12i): Compound 12b (48.0 mg,
0.0730 mmol) was dissolved in THF, deprotonated with DBU
(22.0 mg, 0.145 mmol), acylated with acetyl chloride (10.0 mg,
0.128 mmol), analogously to 12h, precipitated with water, collected
by vacuum filtration, dried, and purified by column separation (sil-
ica gel, dichloromethane). Yield 35 mg (69%) of 12i as a bright-red
powder, m.p. > 300°C. Ϫ Rf (silica gel, chloroform): 0.23. Ϫ IR
(KBr): ν˜ ϭ 2957 cmϪ1 (m), 2929 (m), 2861 (w), 1724 (w, CH3ϪCϭ
O), 1698 (s), 1656 (s), 1608 (m), 1565 (w), 1420 (m), 1397 (w), 1376
(w), 1348 (w), 1313 (s), 1258 (m), 1209 (w), 1188 (w), 1114 (w),
(100) [Mϩ], 855 (8), 854 (14) [Mϩ Ϫ OH], 691 (13), 690 (40), 689
(41) [Mϩ Ϫ C13H26], 672 (7) [Mϩ Ϫ C13H26 Ϫ OH], 509 (10), 508
(32), 507 (42) [Mϩ Ϫ 2 ϫ C13H26], 418 (6), 404 (6), 106 (5), 105
(76) [C6H6ϪCO]. Ϫ C57H65N3O5 (872.2): calcd. C 78.50, H 7.51,
N 4.82; found C 78.53, H 7.66, N 4.63.
1-Bromo-N,NЈ-bis(1-hexylheptyl)perylene-3,4:9,10-bis-
(dicarboximide) (8a): Compound 1a (200 mg, 0.265 mmol) was dis-
solved in chlorobenzene. Bromine (1.00 mL, 3.14 g, 39.3 mmol) and
anhydrous potash (520 mg, 3.77 mmol) were added. The mixture
was stirred (24 h, 60°C), concentrated and purified by column sep-
aration (silica gel, chloroform). Yield 190 mg (86%) of 8a as a dark
red powder, m.p. 136Ϫ138°C. Ϫ Rf (silica gel, chloroform): 0.79.
Ϫ IR (KBr): ν˜ ϭ 2956 cmϪ1 (m), 2926 (s), 2856 (m), 1702 (s), 1660
(s), 1593 (s), 1458 (w), 1400 (m), 1387 (w), 1334 (s), 1245 (m), 1178
(w), 1108 (w), 848 (w), 810 (m), 745 (m). Ϫ 1H NMR (CDCl3): δ ϭ
0.80 (t, J ϭ 6.6 Hz, 12 H, CH3), 1.21Ϫ1.35 (m, 32 H, CH2), 1.84
(mC, 4 H, CHϪCH2), 2.22 (mC, 4 H, CHϪCH2), 5.09Ϫ5.22 (m,
2 H, NϪCH), 8.59 (d, J ϭ 8.1 Hz, 2 H, perylene), 8.66 (mC, 3 H,
perylene), 8.90 (s, 1 H, perylene), 9.76 (d, J ϭ 8.3 Hz, 1 H, per-
ylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.0, 22.6, 26.9, 29.2, 31.7, 32.3,
32.4, 54.8, 55.0, 120.9, 123.0, 123.7, 127.1, 128.1, 128.8, 129.0,
130.8, 131.4, 133.5, 133.9, 163.3, 164.4. Ϫ UV/Vis (CHCl3): λmax
(ε) ϭ 381 nm (3970), 430 (4170), 458 (15420), 488 (41500), 524
(64700). Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 540 nm (1.0),
582 (0.61), 634 (0.13). Ϫ Fluorescence quantum yield (1.00 ϫ
10Ϫ6 mol/L in CHCl3, reference N,NЈ-bis(1-hexylheptyl)perylene-
1
1030 (w), 849 (w), 808 (m), 742 (m), 618 (w), 579 (w). Ϫ H NMR
(CDCl3): δ ϭ 0.87 (t, J ϭ 7.0 Hz, 12 H, CH3), 1.27Ϫ1.45 (m, 16 H,
CH2), 1.90Ϫ2.01 (m, 4 H, CHϪCH2), 2.25Ϫ2.37 (m, 4 H,
CHϪCH2), 3.09 (s, 3 H, CH3ϪCON), 5.27 (mC, 2 H, NϪCH), 8.59
(d, J ϭ 7.8 Hz, 2 H, perylene), 8.69 (br. d, 2 H, perylene), 9.08 (s,
2 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.1, 22.7, 25.8, 29.3,
32.2, 55.0, 121.1, 121.9, 122.2, 122.8, 123.2, 124.1, 125.7, 129.5,
130.2, 133.0, 133.2, 163.3, 164.3, 165.4, 169.6 (CH3ϪCϭO). Ϫ UV/
Vis (CHCl3): λmax (ε) ϭ 278 nm (23260), 409 (8690), 432 (19170),
452 (16930), 483 (47680), 517 (86920). Ϫ Fluorescence (chloro-
form): λmax (Irel.) ϭ 531 nm (1.0), 567 (0.74), 612 (0.15). Ϫ MS
(70 eV): m/z (%): 699 (12), 698 (47), 697 (100) [Mϩ], 681 (6), 680
(15) [Mϩ Ϫ OH], 655 (6) [Mϩ Ϫ CH2ϭCϭO], 640 (6), 573 (12),
572 (38), 571 (53) [Mϩ Ϫ C9H18], 554 (8), 447 (9), 446 (33), 445
(57) [Mϩ Ϫ 2 ϫ C9H18], 416 (8), 405 (11), 404 (19), 403 (65) [Mϩ
Ϫ 2 ϫ C9H18ϪCH2ϭCϭO], 387 (5), 386 (15), 359 (5), 358 (8). Ϫ
C44H47N3O5 (697.9): calcd. C 75.73, H 6.79, N 6.02; found C 75.66,
H 6.79, N 5.99.
3,4:9,10-bis(dicarboximide) (1a) with
488 nm) ϭ 93%. Ϫ MS (70 eV): m/z (%): 834 (67), 832 (60) [Mϩ],
754 (100) [Mϩ Ϫ Br], 653 (22), 652 (31), 651 (26), 650 (21) [Mϩ
Φ ϭ 100%, λexcit. ϭ
Ϫ
C13H26], 574 (12), 573 (29), 572 (31) [Mϩ Ϫ C13H26 Ϫ Br], 471
(32), 470 (47), 469 (29), 468 (36) [Mϩ Ϫ 2 ϫ C13H26], 392 (18), 391
(51), 390 (73) [Mϩ Ϫ 2 ϫ C13H26 Ϫ Br]. Ϫ C50H61BrN2O4 (834.0):
calcd. C 72.01, H 7.37, N 3.36, Br 9.58; found C 71.89, H 7.26,
N 3.26, Br 9.52.
Attempted Acylation of N,NЈЈ-Bis(1-butylpentyl)pyrrolo[2,3,4,5-
hik]perylene-3,4:8,9-bis(dicarboximide) (12b) without Addition of a
Base: Compound 12b (48.0 mg, 0.0730 mmol) was dissolved in
toluene. Acetyl chloride (30.0 mg, 0.385 mmol) was added and the
mixture was stirred at room temperature for 24 h. No formation of
12i could be detected by TLC.
Attempted Bromination of N,NЈ-Bis(1-hexylheptyl)perylene-
3,4:9,10-bis(dicarboximide) (1a) without Catalysis: Compound 1a
(200 mg, 0.265 mmol) and bromine (1.00 mL, 3.14 g, 39.3 mmol)
were heated under reflux in chlorobenzene for 12 h. No formation
of 1-bromo-N,NЈ-bis(1-hexylheptyl)perylene-3,4;9,10-bis(dicarbox-
imide) (8a) could be detected by TLC.
NЈ-Benzoyl-N,NЈЈ-bis(1-hexylheptyl)pyrrolo[2,3,4,5-hik]perylene-
3,4:8,9-bis(dicarboximide) (12j): Compound 12a (80.0 mg,
0.104 mmol) was dissolved in THF, deprotonated with DBU
(25.0 mg, 0.164 mmol), acylated with benzoyl chloride (44.0 mg,
0.314 mmol, colour changes from blue-violet to dark red within a
few minutes) and poured into water (50 mL). Acetone (10 mL) was
added and the mixture was allowed to stand for 16 h. The precipi-
tate was collected by vacuum filtration, dried and purified by col-
umn separation (silica gel, chloroform), analogously to 12h. Yield
84.0 mg (92%) of 12i as a bright-red powder, m.p. 181Ϫ183°C. Ϫ
Rf (silica gel, chloroform): 0.51. Ϫ IR (KBr): ν˜ ϭ 2956 cmϪ1 (s),
2928 (s), 2856 (s), 1697 (s), 1658 (s), 1609 (m), 1565 (m), 1465 (w),
1457 (w), 1440 (w), 1421 (m), 1394 (w), 1349 (m), 1313 (s, br.), 1257
(m, br.), 1205 (w), 1169 (w), 808 (m), 743 (m). Ϫ 1H NMR
(CDCl3): δ ϭ 0.80 (t, J ϭ 6.8 Hz, 12 H, CH3), 1.21Ϫ1.33 (m, 32 H,
CH2), 1.86Ϫ1.92 (m, 4 H, CHϪCH2), 2.22Ϫ2.30 (m, 4 H,
1-Amino-N,NЈ-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarb-
oximide) (9a) by Reduction with Iron and Hydrochloric Acid (A):
Compound 6a (100 mg, 0.125 mmol) and iron (50.0 mg,
0.893 mmol) were dispersed in ethanol (or n-butyl alcohol or
THF). Concd. HCl (0.5 mL) was added. The mixture was heated
under reflux (10Ϫ30 min) until no 6a could be detected (TLC) and
the product was precipitated with water. The solid was collected by
vacuum filtration, dried, and purified by column separation (silica
gel, chloroform and alumina, chloroform). Yield 78.0 mg (81%) of
9a as a dark-blue powder (physical data see B below).
CHϪCH2), 5.21Ϫ5.28 [m, 2 H, NϪCH(CH2)2], 7.71 (t, J ϭ 7.6 Hz, 1-Amino-N,NЈ-bis(1-hexylheptyl)perylene-3,4:9,10-bis(dicarb-
2 H, phenyl), 7.87 (t, J ϭ 7.5 Hz, 1 H, phenyl), 7.92 (d, J ϭ 6.9 Hz,
oximide) (9a) by Reduction with Triethylammonium Formate and
2 H, phenyl), 8.61Ϫ8.76 (m, 6 H, perylene). Ϫ 13C NMR (CDCl3): Palladium/Carbon (B): Compound 6a (20.0 mg, 0.025 mmol) was
δ ϭ 14.0, 22.6, 27.0, 29.3, 31.8, 32.5, 55.0, 121.6, 122.4, 122.8, dissolved in THF. Triethylamine (0.200 mL, 145 mg, 1.44 mmol)
123.0, 123.5, 123.8, 124.3, 126.0, 129.3, 129.4, 130.3, 133.4, 133.5,
and palladium/carbon (5 mg, 5%) were added. The mixture was
133.9, 134.6, 163.6, 164.2, 164.6, 165.4, 169.1 (phenylϪCϭO). Ϫ heated under reflux (30 min, to remove any catalyst poison). For-
UV/Vis (CHCl3): λmax (ε) ϭ 407 nm (7050), 431 (17430), 450 mic acid (0.040 mL, 48.8 mg, 1.06 mmol) and additional pal-
(14760), 480 (43820), 514 (80820). Ϫ Fluorescence (chloroform): ladium/carbon (5 mg, 5%) was added. The mixture was heated un-
λmax ϭ 523 nm, 560. Ϫ Fluorescence quantum yield (8.40 ϫ
10Ϫ7 mol/L in CHCl3, reference N,NЈ-bis(1-hexylheptyl)perylene- by TLC. The purification was carried out analogously to A. Ϫ
3,4:9,10-bis(dicarboximide) (1a) with 100%, λexcit. Yield 14.0 mg (73%) of 9a as a dark blue powder, m.p. 93Ϫ95°C.
484 nm) ϭ 98%. Ϫ MS (70 eV): m/z (%): 873 (20), 872 (62), 871 Ϫ Rf (silica gel, chloroform): 0.34. Ϫ Rf (Al2O3, chloroform): 0.54.
der reflux (15Ϫ30 min) until no starting material could be detected
Φ
ϭ
ϭ
Eur. J. Org. Chem. 2000, 365Ϫ380
373

H. Langhals, S. Kirner
FULL PAPER
Ϫ IR (KBr): ν˜ ϭ 3349 cmϪ1 (m, NϪH), 3245 (w, NϪH), 2955 (m), dissolved in THF. Iron (50.0 mg, 0.893 mmol) and concd. hydro-
2926 (s), 2856 (m), 1693 (s), 1651 (s, br.), 1615 (s), 1602 (s), 1590 chloric acid (0.5 mL) were added. The mixture was heated under
(s), 1573 (s), 1565 (m), 1512 (w), 1465 (m), 1428 (s), 1397 (w), 1373 reflux until no red, non fluorescent starting material was detectable
(m), 1339 (s), 1312 (m), 1269 (m, CϪN), 1253 (m), 1180 (w), 1125 by TLC (ca. 15 min). The dye was precipitated with water and a
1
(w), 845 (w), 809 (s), 750 (m), 725 (w). Ϫ H NMR (CDCl3): δ ϭ small amount of 2  HCl, collected by vacuum filtration and dried
0.79 (t, J ϭ 6.8 Hz, 12 H, CH3), 1.20Ϫ1.28 (m, 32 H, CH2), (9b) and dissolved in dichloromethane. 85% KOH powder
1.79Ϫ1.86 (m, 4 H, CHϪCH2), 2.20Ϫ2.27 (m, 4 H, CHϪCH2), (30.0 mg,
0.456 mmol),
benzyltriethylammonium
chloride
5.17Ϫ5.20 (m, 2 H, NϪCH), 5.24 (s, 2 H, NH2), 8.16 (s, 1 H, per-
ylene), 8.40Ϫ8.47 (m, 3 H, perylene), 8.59 (mC, 2 H, perylene), 8.81
(10.0 mg, 0.044 mmol) and methyl iodide (0.10 mL, 0.228 mg,
1.61 mmol) were added. The mixture was vigorously stirred at
(d, J ϭ 8.2 Hz, 2 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.0, room temperature for 16 h, diluted with dichloromethane, repeat-
22.6, 26.9, 29.2, 31.7, 32.4, 54.6, 115.5, 121.2, 122.8, 123.8, 127.3,
128.4, 129.7, 132.7, 135.1, 136.1, 146.1 (CϪNH2). Ϫ UV/Vis
(CHCl3): λmax (ε) ϭ 276 nm (24540), 420 (10090), 571 (31070). Ϫ
Fluorescence (chloroform): λmax ϭ 684 nm. Ϫ MS (70 eV): m/z
(%): 771 (11), 770 (39), 769 (75) [Mϩ], 753 (5), 752 (8) [Mϩ Ϫ OH],
edly washed with water, dried with MgSO4, concentrated, and puri-
fied by column separation (silica gel, chloroform and silica gel, di-
chloromethane). Yield 70.0 mg (70%) of 10b as a dark bluish-green
powder, m.p. 170Ϫ172°C. Ϫ Rf (silica gel, chloroform): 0.50. Ϫ Rf
(silica gel, dichloromethane): 0.76. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1
589 (7), 588 (22), 587 (23) [Mϩ Ϫ C13H26], 570 (6), 418 (6), 407 (m), 2927 (m), 2858 (w), 1694 (s), 1654 (s), 1612 (w), 1588 (s),
(13), 406 (58), 405 (100) [Mϩ Ϫ 2 ϫ C13H26], 388 (5), 360 (6). Ϫ 1510 (w), 1458 (w), 1405 (m), 1361 (w), 1332 (s), 1253 (m), 1194
C50H63N3O4 (770.1): calcd. C 77.99, H 8.25, N 5.46; found C 77.77,
H 8.07, N 5.47.
(w), 1128 (w), 1100 (w), 810 (m), 751 (w). Ϫ 1H NMR (CDCl3):
δ ϭ 0.86 (t, J ϭ 7.1 Hz, 12 H, CH3), 1.20Ϫ1.40 (m, 16 H, CH2),
1.87 (mC, 4 H, CHϪCH2), 2.27 (mC, 4 H, CHϪCH2), 3.04 (s, 6 H,
NϪCH3), 5.20 (mC, 2 H, NϪCH), 8.48Ϫ8.72 (m, 6 H, perylene),
9.02 (d, J ϭ 8.4 Hz, 1 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ
14.06, 22.67, 29.15, 32.16, 43.58 [N(CH3)2], 54.49, 120.28, 121.28,
123.78, 124.18, 124.77, 127.32, 129.15, 129.45, 133.70, 135.08,
135.70, 152.10 (CϪNMe2). Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 278 nm
(22490), 436 (15700), 615 (23570). Ϫ Fluorescence (chloroform):
λmax ϭ 725 nm. Ϫ MS (70 eV): m/z (%): 687 (12), 686 (47), 685
(100) [Mϩ], 560 (13), 559 (2) [Mϩ Ϫ C9H19], 435 (7), 434 (25), 433
(36) [Mϩ Ϫ 2 ϫ C9H19], 418 (5). Ϫ C44H51N3O4 (685.9): calcd.
C 77.05, H 7.49, N 6.13; found C 77.05, H 7.84, N 5.80.
N,NЈ-Bis(1-hexylheptyl)-1-dimethylaminoperylene-3,4:9,10-bis-
(dicarboximide) (10a). ؊ Methylation According to Eschweiler؊
Clarke (A): 1-Amino-N,NЈ-bis(1-hexylheptyl)perylene-3,4:9,10-
bis(dicarboximide) (9a, 34.0 mg, 0.044 mmol) was dissolved in for-
mic acid with the addition of small amounts of DMF; 35% aqueous
formaldehyde solution (ca. 0.5 mL) was added. The mixture was
heated under reflux with stirring (24 h, 85°C), precipitated with
water, and made alkaline with Na2CO3. The dark precipitate was
collected by vacuum filtration, dried, and purified by column sep-
aration (silica gel, chloroform). The yields varied considerably.
Yield 21.0 mg (60%) of 10a. Physical data see below.
1-Amino-N-(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic 3,4-An-
hydride 9,10-Imide (17b) and 12-Amino-N-(1-hexylheptyl)perylene-
3,4:9,10-tetracarboxylic 3,4-Anhydride 9,10-Imide (18b) by Re-
duction with Iron and Hydrochloric Acid (A): A mixture (100 mg,
0.162 mmol) of 1-nitro-N-(1-hexylheptyl)perylene-3,4:9,10-tetra-
carboxylic 3,4-anhydride 9,10-imide (17a) and 12-nitro-N-(1-hex-
ylheptyl)perylene-3,4:9,10-tetracarboxylic 3,4-anhydride 9,10-imide
(18a) was dissolved in a mixture (30 mL) of chloroform/ethanol
(1:3) or THF. Iron (64.0 mg, 1.14 mmol) and concd. HCl (0.5 mL)
were added and the mixture was heated under reflux for 30 min,
cooled and poured into 2  HCl. Acetone was added to obtain a
homogeneous solution (not necessary for THF). The solution was
heated to boiling to remove chloroform, the precipitate (dark solid)
was collected by vacuum filtration and dried. The thus obtained
mixture of 17b and 18b as a dark blue powder was used without
further purification. For physical data see B below.
1-Dimethylamino-N,NЈ-bis(1-hexylheptyl)perylene-3,4:9,10-bis-
(dicarboximide) (10a). ؊ Methylation with Methyl Iodide: Com-
pound 9a (50.0 mg, 0.065 mmol) was dissolved in toluene (or di-
chloromethane). 85% KOH powder (15.0 mg, 0.228 mmol), benzyl-
triethylammonium chloride (5.00 mg, 0.022 mmol), and methyl
iodide (0.040 mL, 0.091 mg, 0.642 mmol) were added. The mixture
was stirred at room temperature for 16 h, diluted with the solvent
used (or tert-butyl methyl ether), washed three times with water,
dried with MgSO4, and purified by column separation (silica gel,
chloroform and silica gel, dichloromethane). The bluish-green
monomethylated product and the blue starting material were ob-
tained after elution of the main fraction. Yield 40.0 mg (77%) of
10a as a dark green solid, m.p. 72Ϫ74°C. Ϫ Rf (silica gel, chloro-
form): 0.63. Ϫ Rf (silica gel, dichloromethane): 0.83. Ϫ IR (KBr):
ν˜ ϭ 2954 cmϪ1 (m), 2925 (s), 2855 (s), 1694 (s), 1654 (s), 1612 (w),
1588 (s), 1509 (w), 1458 (w), 1405 (m), 1361 (w), 1332 (s), 1249
(m), 1192 (w), 1128 (w), 1058 (w), 948 (w), 846 (w), 809 (m), 750
(m), 724 (w), 702 (w). Ϫ 1H NMR (CDCl3): δ ϭ 0.81 (t, J ϭ
6.6 Hz, 12 H, CH3), 1.21Ϫ1.29 (m, 32 H, CH2), 1.84 (mC, 4 H,
CHϪCH2), 2.23 (mC, 4 H, CHϪCH2), 3.02 (s, 6 H, NϪCH3), 5.17
(mC, 2 H, NϪCH), 8.50Ϫ8.63 (m, 6 H, perylene), 9.00 (d, J ϭ
8.3 Hz, 1 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.01, 22.57,
26.90, 26.93, 29.21, 29.24, 31.75, 32.41, 43.54 [N(CH3)2], 54.53,
54.72, 120.23, 121.24, 123.75, 124.13, 124.72, 127.28, 128.54,
129.10, 129.40, 130.85, 131.31, 131.41, 132.02, 133.66, 135.04,
135.65, 152.06 (CϪNMe2), 163.92, 164.80. Ϫ UV/Vis (CHCl3):
λmax (Erel.) ϭ 436 nm (0.62), 614 (1.0). Ϫ Fluorescence (chloro-
form): λmax ϭ 725 nm. Ϫ MS (70 eV): m/z (%): 799 (18), 798 (59),
797 (100) [Mϩ], 616 (9), 615 (8) [Mϩ Ϫ C13H26], 434 (14), 433 (18)
[Mϩ Ϫ 2 ϫ C13H26]. Ϫ C52H67N3O4 (798.1): calcd. C 78.26, H 8.46,
N 5.26; found C 76.34, H 7.42, N 6.03.
1-Amino-N-(1-hexylheptyl)perylene-3,4:9,10-tetracarboxylic 3,4-An-
hydride 9,10-Imide (17b) and 12-Amino-N-(1-hexylheptyl)perylene-
3,4:9,10-tetracarboxylic 3,4-Anhydride 9,10-Imide (18b) by Re-
duction with Triethylammonium Formate and Palladium/Carbon (B):
A mixture (100 mg, 0.162 mmol) of 17a and 18a was dissolved in
THF. Triethylamine (1.30 mL, 0.940 mg, 9.33 mmol) and pal-
ladium/carbon (15 mg) were added, and the mixture was heated
under reflux for 30 min (removing catalyst poison). Formic acid
(0.26 mL, 316 mg, 6.87 mmol) and a second portion of palladium/
carbon (30 mg) were added. The mixture was refluxed until no
starting material could be detected by TLC (ca. 30 min), filtered
and purified as is described for A above. The thus obtained mixture
of 17b and 18b (a dark blue powder) was used without further
purification. M.p. 292Ϫ294°C. Ϫ Rf (silica gel, dichloromethane/
2% acetic acid): 0.15Ϫ0.40. Ϫ Rf (silica gel, chloroform/10% acetic
acid): 0.60. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (m), 2927 (m), 2856 (m),
1764 (s), 1725 (m), 1698 (s), 1655 (s), 1617 (m), 1604 (m), 1590 (s),
N,NЈ-Bis(1-butylpentyl)-1-(dimethylamino)perylene-3,4:9,10-bis-
(dicarboximide) (10b): Compound 6b (100 mg, 0.146 mmol) was
374
Eur. J. Org. Chem. 2000, 365Ϫ380

Novel Fluorescent Dyes by the Extension of the Core of Perylenetetracarboxylic Bisimides
1561 (m), 1509 (w), 1459 (w), 1428 (m), 1399 (w), 1373 (m),
FULL PAPER
3
4 H, CHϪCH2), 2.52 (mC, 4 H, CHϪCH2), 5.12 [tt, J1 ϭ 9.4 Hz,
1351 (m), 1327 (s), 1284 (w), 1249 (m), 1202 (w), 1175 (w), 1135 3J2 ϭ 5.7 Hz, 2 H, CHϪ(CH2)2], 8.44 (s, 2 H, perylene), 8.51Ϫ8.58
(w), 1110 (w), 1035 (m), 100 (m), 805 (m), 742 (m). Ϫ 1H NMR (m, 4 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.4, 23.0, 29.5,
(CDCl3): δ ϭ 0.83 (t, J ϭ 6.4 Hz, 6 H, CH3), 1.23- 1.40 (m, 16 H, 32.4, 55.3, 124.4, 127.1, 129.0, 129.2, 131.3, 131.9, 1132.9, 133.1,
CH2), 1.86 (mC, 2 H, CHϪCH2), 2.23 (mC, 2 H, CHϪCH2), 133.2, 162.9, 163.6, 164.1, 164.6, 168.1. Ϫ UV/Vis (CHCl3): λmax
5.12Ϫ5.19 (m, 1 H, NϪCH), 5.35 (s, 2 H, NH2), 8.16 (br. s, 1 H, (ε) ϭ 403 nm (8580), 426 (12290), 450 (18390), 478 (29080), 611
perylene), 8.46Ϫ8.66 (m, 5 H, perylene), 8.87 (br. s, 1 H, perylene).
Ϫ UV/Vis (CHCl3): λmax (Erel.) ϭ 416 nm (0.38), 568 (1.0). Ϫ Flu- (100) [Mϩ], 687 (5) [Mϩ Ϫ OH], 581 (5), 580 (13), 579 (29), 578
orescence (chloroform): λmax ϭ 664 nm. Ϫ MS (70 eV): m/z (%):
(23) [Mϩ Ϫ C9H18], 561 (6), 466 (5), 465 (11), 455 (11), 454 (31),
590 (5), 589 (23), 588 (50) [Mϩ], 571 (5) [Mϩ Ϫ OH], 408 (15), 407 453 (69), 452 (89) [Mϩ Ϫ 2 ϫ C9H18], 435 (6), 422 (10), 421 (29),
(56), 406 (100) [Mϩ Ϫ C13H26], 391 (6) [Mϩ Ϫ C13H26 ϩ Hϩ 420 (40) [Mϩ Ϫ 2 ϫ C9H18 Ϫ S], 410 (6), 409 (14), 408 (7), 407
NH2], 362 (6) [Mϩ Ϫ C13H26 Ϫ CO2], 334 (10) [Mϩ Ϫ C13H26 (17), 403 (14), 382 (8), 381 (6), 376 (8), 375 (10), 332 (5). Ϫ
(12030). Ϫ MS (70 eV): m/z (%): 707 (6), 706 (20), 705 (49), 704
Ϫ
Ϫ C2O3].
C42H44N2O4S2 (705.0): calcd. C 71.56, H 6.29, N 3.97, S 9.10;
found C 71.75, H 6.31, N 3.93, S 9.18. Ϫ Second Fraction: Yield
49 mg (47%) of 11b as a bright orange powder, m.p. > 300°C. Ϫ
Rf (silica gel, chloroform): 0.54. Ϫ IR (KBr): ν˜ ϭ 2957 cmϪ1 (s),
2929 (s), 2860 (s), 1698 (s), 1660 (s), 1622 (w), 1598 (m), 1561 (m),
1467 (w), 1453 (w), 1428 (m), 1403 (w), 1364 (w), 1350 (m), 1307
(s), 1247 (m), 1200 (w), 1183 (w), 1171 (w), 1155 (w), 1121 (w),
1106 (m), 1089 (w), 915 (w), 850 (m), 808 (s), 743 (s), 736 (w), 633
1-Dimethylamino-N-(1-hexylheptyl)perylene-3,4:9,10-tetracarb-
oxylic 3,4-Anhydride 9,10-Imide (17c) and 12-Dimethylamino-N-(1-
hexylheptyl)perylene-3,4:9,10-tetracarboxylic 3,4-Anhydride 9,10-
Imide (18c): A mixture (58.0 mg, 0.099 mmol) of 17b and 18b was
dissolved in dimethylformamide (7 mL). Formic acid (2 mL) and
aqueous formaldehyde solution (1 mL, 37%) were added under ar-
gon. The mixture was heated under reflux, under argon, with stir-
ring (24 h, 105°C) and poured into 1  HCl (bluish-green precipi-
tate). The precipitate was collected by vacuum filtration, washed
with water, dried and purified by column separation (silica gel,
chloroform/5% acetic acid) with the exclusion of daylight. Yield
43 mg (71%) of 17c and 18c. Ϫ Rf (silica gel, chloroform/3% acetic
acid): 0.50. Ϫ The separation of the two isomers proceeded by col-
umn chromatography (silica gel, chloroform/1% acetic acid). Ϫ
First Fraction: 17c. Ϫ Rf (silica gel, chloroform/1% acetic acid):
0.17. Ϫ UV/Vis (CHCl3): λmax (Erel.) ϭ 442 nm (0.70), 626 (1.0). Ϫ
1H NMR (CDCl3): δ ϭ 0.83 (t, J ϭ 6.4 Hz, 6 H, CH3), 1.23Ϫ1.32
(m, 16 H, CH2), 1.81Ϫ1.91 (m, 2 H, CHϪCH2), 2.22Ϫ2.29 (m, 2
H, CHϪCH2), 3.05 (s, 6 H, NϪCH3), 5.21 (mC, 1 H, NϪCH),
8.48Ϫ8.57 (m, 4 H, perylene), 8.64Ϫ8.68 (mC, 2 H, perylene), 8.95
(d, J ϭ 8.3 Hz, 1 H, perylene). Ϫ MS (70 eV): m/z (%): 618 (9),
617 (43), 616 (100) [Mϩ], 599 (8) [Mϩ Ϫ OH], 436 (11), 435 (49),
434 (93) [Mϩ Ϫ C13H26]. Ϫ Second Fraction: 18c. Ϫ Rf (silica gel,
chloroform/1% acetic acid): 0.11. Ϫ UV/Vis (CHCl3): λmax (Erel.) ϭ
442 nm (0.71), 483 (0.35), 634 (1.0). Ϫ 1H NMR (CDCl3): δ ϭ 0.84
1
(w), 599 (w), 592 (w), 540 (w). Ϫ H NMR (CDCl3): δ ϭ 0.87 (t,
J ϭ 7.0 Hz, 12 H, CH3), 1.44Ϫ1.31 (m, 16 H, CH2), 1.94Ϫ2.00 (m,
4 H, CHϪCH2), 2.32Ϫ2.40 (m, 4 H, CHϪCH2), 5.28 [m, 2 H,
CHϪ(CH2)2], 8.64 (d, J ϭ 8.1 Hz, 2 H, perylene), 8.72 (br. d, J ϭ
8.1 Hz, 2 H, perylene), 9.10 (s, 2 H, perylene). Ϫ 13C NMR
(CDCl3): δ ϭ 14.1, 22.7, 29.3, 32.2, 55.0, 122.7, 123.2, 126.0, 128.6,
130.8, 131.0, 132.7, 137.9 (CϪSϪC). Ϫ UV/Vis (CHCl3): λmax
(ε) ϭ 391 nm (3020), 415 (10000), 440 (27400), 469 (48990), 501
(83110). Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 511 nm (1.0),
548 (0.57), 590 (0.13). Ϫ Fluorescence quantum yield (CHCl3, 7.67
ϫ 10Ϫ7 mol/l in CHCl3, reference N,NЈ-bis(1-hexylheptyl)perylene-
3,4:9,10-bis(dicarboximide) (1a) with Φ ϭ 100%, λexcit. ϭ 490 nm):
71%. Ϫ Solid-state fluorescence: λmax ϭ 584 nm. Ϫ MS (70 eV):
m/z (%): 673 (12), 672 (25) [Mϩ], 655 (7) [Mϩ Ϫ OH], 548 (8), 547
(25), 546 (29) [Mϩ Ϫ C9H18], 529 (7), 433 (7), 422 (18), 421 (57),
420 (100) [Mϩ Ϫ 2 ϫ C9H18], 404 (8), 403 (21), 376 (9), 375 (15). Ϫ
C42H44N2O4S (672.9): calcd. C 74.94, H 6.59, N 4.16, S 4.77; found
C 74.69, H 6.60, N 4.95, S 4.95.
(t, J ϭ 6.4 Hz, 6 H, CH3), 1.24Ϫ1.26 (m, 16 H, CH ), 1.80Ϫ1.90 Reaction of N,NЈ-Bis(1-hexylheptyl)-1-nitroperylene-3,4:9,10-bis-
(m, 2 H, CHϪCH2), 2.21Ϫ2.27 (m, 2 H, CHϪCH2), 3.08 (s, 6 H, (dicarboximide) (6a) with Sulfur in DMF: Sulfur (16 mg,
NϪCH3), 5.19 (mC, 1 H, NϪCH), 8.51Ϫ8.68 (m, 6 H, perylene), 0.50 mmol) was allowed to react with compound 6a (0.10 g,
8.80 (d, J ϭ 8.3 Hz, 1 H, perylene). Ϫ m/z (%): 618 (8), 617 (36), 0.13 mmol) in DMF (10 mL, 130°C) analogously to 6b. Yield
616 (100) [Mϩ], 435 (25), 434 (49) [Mϩ Ϫ C13H26].
43.0 mg (40%) of 13a and 47.0 mg (45%) of 11a as a bright orange
powder. Physical data see below.
Reaction of N,NЈ-Bis(1-butylpentyl)-1-nitroperylene-3,4:9,10-bis-
(dicarboximide) (6b) with Sulfur: Sulfur (20.0 mg, 0.63 mmol) was
Reaction of N,NЈ-Bis(1-hexylheptyl)-1-nitroperylene-3,4:9,10-bis-
completely dissolved in DMF (10 mL) by heating (80Ϫ90°C). (dicarboximide) (6a) with Sulfur in N-Methylpyrrolidone: Sulfur
Compound 6b (100 mg, 0.15 mmol) was added under argon. The
mixture was heated under reflux (10 h, 120Ϫ130°C) until no start-
(160 mg, 4.9 mmol) was dissolved in N-methylpyrrolidone (12 mL,
70°C). Compound 6a (0.50 g, 0.62 mmol) was added under argon.
ing material could be detected by TLC, cooled down to below The mixture was heated (130°C, ca. 75 min, until the starting mate-
100°C, and poured into a mixture of water and 2  HCl (2:1, ca.
100 mL; dark precipitate). The precipitate was collected by vacuum
filtration, washed with water, dried at 70°C, and purified by col-
umn separation (silica gel, CHCl3). Ϫ First Fraction: This fraction
was dissolved in petroleum ether and the excess sulfur was com-
pletely removed by column separation (silica gel, petroleum ether,
ca. 2 L, until no sulfur could be detected if the eluent was evapo-
rated). The green, main fraction was then eluted with chloroform.
rial 6a could not be detected by TLC) and poured into water
(150 mL). The precipitate was collected by vacuum filtration,
washed with water, dried, and purified by column separation (silica
gel, chloroform). Ϫ First Fraction: Yield 130 mg (25%) of 13a as a
dark green powder (residues of sulfur were removed as was de-
scribed for 13b), m.p. 158Ϫ160°C. Ϫ Rf (silica gel, chloroform):
0.72. Ϫ IR (KBr): ν˜ ϭ 2955cmϪ1 (s), 2926 (s), 2856 (s), 1701 (s),
1699 (s), 1660 (s), 1589 (m), 1467 (w), 1457 (m), 1415 (w), 1401
Yield 42 mg (42%) of 13b, m.p. > 300°C. Ϫ Rf (silica gel, chloro- (m), 1385 (m), 1337 (m), 1303 (m), 1252 (m), 1182 (w), 1115 (w),
1
form): 0.63. Ϫ IR (KBr): ν˜ ϭ 2958 cmϪ1 (m), 2928 (m), 2856 (m),
923 (w), 850 (m), 810 (m), 747 (w). Ϫ H NMR (CDCl3): δ ϭ 0.81
1697 (s), 1660 (s), 1653 (s), 1590 (m), 1466 (s), 1457 (s), 1415 (w), (t, J ϭ 7.0 Hz, 12 H, CH3), 1.21Ϫ1.33 (m, 32 H, CH2), 1.78Ϫ1.85
1402 (w), 1384 (m), 1339 (w), 1305 (m), 1263 (w), 1251 (m), 1187
(m, 4 H, CHϪCH2), 2.18Ϫ2.25 (m, 4 H, CHϪCH2), 5.14 [tt, 3J1 ϭ
(w), 1112 (w), 848 (w), 810 (m), 747 (w). Ϫ 1H NMR (CDCl3): δ ϭ 9.4 Hz, 3J2 ϭ 5.6 Hz, 2 H, CHϪ(CH2)2], 8.49 (br. s, 2 H, perylene),
0.83 (t, J ϭ 7.0 Hz, 12 H, CH3), 1.29 (mC, 16 H, CH2), 2.21 (mC, 8.60 (br. s, 4 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.1, 22.6,
Eur. J. Org. Chem. 2000, 365Ϫ380
375

H. Langhals, S. Kirner
FULL PAPER
26.9, 29.2, 31.8, 32.3, 55.0, 124.1, 126.8, 128.6, 131.6, 132.8, 133.0.
dichloromethane): 0.43. Ϫ IR (KBr): ν˜ ϭ 2962 cmϪ1 (m), 2869 (w),
Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 397 nm (9250), 424 (12580), 450
1708 (s), 1673 (s), 1597 (m), 1562 (w), 1501 (w), 1429 (m), 1399
(18660), 478 (29550), 611 (13540). Ϫ MS (70 eV): m/z (%): 819 (8), (w), 1365 (m), 1351 (w), 1316 (m), 1242 (m, br.), 1184 (w), 1168
818 (24), 817 (56), 816 (100) [Mϩ], 799 (6), 637 (5), 636 (14), 635 (w), 1130 (w), 820 (w), 810 (w), 746 (w), 732 (w), 606 (w). Ϫ
(28), 634 (27) [Mϩ Ϫ C13H26], 455 (9), 454 (24), 453 (47), 452 (64)
1H NMR (CDCl3): δ ϭ 1.32, 1.33, 1.34, and 1.35 (each s, 36 H,
4
[Mϩ Ϫ 2ϫ C13H26], 422 (7), 421 (20), 420 (21) [Mϩ Ϫ 2 ϫ·C13H26 CH3), 7.12 and 7.17 (each d, JCH ϭ 2.1 and 2.2 Hz, 2 H, phenyl),
3
4
Ϫ S], 409 (6), 407 (7), 403 (8). Ϫ C50H60N2O4S2 (817.2): calcd. 7.48 and 7.50 ( each dd, JCH ϭ 8.5 Hz, JCH ϭ 2.3 and 2.5 Hz, 2
C 73.49, H 7.40, N 3.43, S 7.85; found C 73.38, H 7.26, N 3.36, H, phenyl), 7.62 and 7.63 (each d, JCH ϭ 8.5 and 8.8 Hz, 2 H,
3
S 7.91. Ϫ Second Fraction: Yield 295 mg (60%) of 11a as a bright
orange powder, m.p. 263Ϫ265°C. Ϫ Rf (silica gel, chloroform): perylene). Ϫ 13C NMR (CDCl3): δ ϭ 31.21, 31.79, 34.28, 35.58,
0.67. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (s), 2927 (s), 2857 (s), 1701 (s),
35.61, 122.83, 122.86, 123.19, 123.25, 123.50, 123.64, 123.78,
phenyl), 8.96Ϫ9.06 (m, 4 H, perylene), 9.41 and 9.44 (each s, 2 H,
1662 (s), 1625 (w), 1560 (m), 1467 (w), 1456 (w), 1428 (m), 1402 123.83, 126.33, 126.39, 126.47, 126.61, 127.80, 127.99, 128.12,
(w), 1363 (m), 1347 (m), 1306 (s), 1246 (m), 1199 (w), 1167 (w), 128.79, 128.89, 130.06, 130.13, 131.82, 131.96, 132.90, 133.62,
1110 (w), 911 (w), 846 (w), 807 (s), 741 (m), 629 (w), 597 (w), 582 133.77, 138.41 (CϪSϪC), 138.44 (CϪSϪC), 143.68, 143.76,
(w), 535 (w), 512 (w). Ϫ 1H NMR (CDCl3): δ ϭ 0.81 (t, J ϭ 7.0 Hz, 150.18, 150.24, 164.42, 164.50, 164.89, 164.98. Ϫ UV/Vis (CHCl3):
12 H, CH3), 1.23Ϫ1.36 (m, 32 H, CH2), 1.95 (mC, 4 H, CHϪCH2), λmax (ε) ϭ 283 nm (16070), 416 (11440), 441 (29980), 469 (54950),
2.30 (mC, 4 H, CHϪCH2), 5.28 [mC, 2 H, CHϪ(CH2)2], 8.62 (d,
J ϭ 8.1 Hz, 2 H, perylene), 8.71 (br. d, 2 H, perylene), 9.09 (br. s, (1.0), 545 (0.50), 587 (0.11). Ϫ MS (70 eV): m/z (%): 796 (3) [Mϩ],
2 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 13.8, 22.74, 26.9, 29.1, 742 (5), 741 (18), 740 (53), 739 (100) [Mϩ Ϫ C4H9], 682 (3) [Mϩ Ϫ
31.6, 32.4, 54.9, 122.5, 122.9, 125.7, 126.7, 127.3, 128.9, 129.6, 2 ϫ C4H9]. Ϫ C52H48N2O4S: calcd. 796.3335, found 796.3328
503 (93610). Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 514 nm
130.7, 132.5, 137.7 (CϪSϪC), 163.3, 163.6, 164.4, 164.8. Ϫ UV/
Vis (CHCl3): λmax (ε)
(MS). Ϫ C52H48N2O4S (797.0): calcd. C 78.36, H 6.07, N 3.51,
284 nm (14620), 316 (4750), 392 S 4.02; found C 77.60, H 6.17, N 3.43, S 3.84.
ϭ
(2800, sh.), 415 (9850), 439 (26980), 468 (49580), 501 (84720). Ϫ
Fluorescence (chloroform): λmax (Irel.) ϭ 511 nm (1.0), 548 (0.36),
590 (0.10). Ϫ Solid-state fluorescence: λmax ϭ 650 nm. Ϫ MS
N,NЈ-Bis(1-hexylheptyl)benzoperylene-1Ј,2Ј:3,4:9,10-hexacarboxylic
1Ј,2Ј-Anhydride 3,4:9,10-Bis(imide) (2a): Compound 1a (1.50 g,
1.99 mmol) was dissolved in molten maleic anhydride (95°C) with
the addition of a few ml of acetone (or chloroform; for removing
crystals of maleic anhydride from the reflux condenser). Chloranil
(970 mg, 3.98 mmol) was added. The mixture was heated (bath
140°C) in an open reaction vessel until the reaction temperature
(70 eV): m/z (%): 786 (5), 785 (13), 784 (24) [Mϩ], 767 (5) [Mϩ
Ϫ
OH], 604 (11), 603 (29), 602 (29) [Mϩ Ϫ C13H26], 433 (6), 423 (5),
422 (19), 421 (57), 420 (100) [Mϩ Ϫ 2 ϫ C13H26], 403 (12), 375
(6). Ϫ C50H60N2O4S (785.1): calcd. C 76.49, H 7.70, N 3.57, S 4.08;
found C 76.21, H 7.56, N 3.56, S 4.08.
Reaction
3,4:9,10-bis(dicarboximide) (6c) with Sulfur: Sulfur (24.0 mg,
0.750 mmol) was dissolved in DMF (10 mL, 90°C). Compound 6c from the condenser while refluxing). The reaction was cooled, dis-
of
N,NЈ-Bis(2,5-di-tert-butylphenyl)-1-nitroperylene- reached 125°C and heated for 4 d in a flask fitted with a reflux
condenser (the solvent removed any crystals of maleic anhydride
(100 mg, 0.123 mmol) was added under argon. The mixture was
heated at 120°C (17 h, until the starting material, 6c, could not be
detected by TLC), cooled down to below 100°C and poured, while
persed in acetone while still warm, poured into 2  HCl (250 mL)
and stirred at room temperature for 16 h (ageing of the precipitate).
The precipitate was collected by vacuum filtration, repeatedly
still warm, into a mixture of water and 2  HCl (100 mL, 2:1). The washed with water, dried, dissolved in chloroform and purified by
precipitate was collected by vacuum filtration, dried, and purified
by column separation (silica gel, dichloromethane). Ϫ First Frac-
tion: 56.0 mg (55%) of 13c. If the reaction temperature was 153°C,
the yield of 13c dropped to 0%. M.p. > 300°C. Ϫ Rf (silica gel,
column separation (silica gel). The excess of chloranil and 1a were
completely eluted with chloroform, while the main fraction was
eluted with a mixture of chloroform and 1Ϫ5% acetic acid. Yield
1.20 g (71%) of 2a as a dark yellow powder, m.p. > 200°C (dec.).
chloroform): 0.36. Ϫ Rf (silica gel, dichloromethane): 0.47. Ϫ IR Ϫ Rf (silica gel, chloroform/acetic acid, 10:1): 0.81. Ϫ Rf (silica gel,
(KBr): ν˜ ϭ 2962 cmϪ1 (m), 2869 (w), 1710 (s), 1673 (s), 1589 (s), chloroform): 0.00Ϫ0.70. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (m), 2927 (s),
1500 (w), 1464 (w), 1394 (s), 1363 (w), 1340 (m), 1314 (m), 1296
2857 (m), 1847 (w), 1776 (w), 1703 (s), 1661 (s), 1625 (w), 1597
(w), 1252 (s), 1201 (m), 1169 (w), 1134 (w), 983 (w). 821 (w), (m), 1487 (w), 1419 (m), 1396 (w), 1366 (w), 1320 (s), 1268 (m),
1
810 (m), 755 (w), 740 (w), 629 (w). Ϫ H NMR (CDCl3): δ ϭ 1.31 1171 (m), 1016 (w), 954 (w), 912 (w), 847 (w), 812 (m), 763 (w),
(s, 18 H, CH3), 1.33 (s, 9 H, CH3), 1.34 (s, 9 H, CH3), 7.01 and 749 (w), 718 (w). Ϫ 1H NMR (CDCl3): δ ϭ 0.80 (t, J ϭ 6.8 Hz,
4
7.03 (each d, JCH ϭ 2.0 Hz, 2 H, phenyl), 7.485 and 7.488 (each 12 H, CH3), 1.10Ϫ1.42 (m, 32 H, CH2), 1.88Ϫ2.00 (m, 4 H,
3
4
dd, JCH ϭ 8.5 Hz, JCH ϭ 2.0 and 2.3 Hz, 2 H, phenyl), 7.61 and
7.62 (each d, 3JCH ϭ 8.5, 2 H, phenyl), 8.61 and 8.62 (each s, 2 H), NϪCH), 9.22 (br. s, 2 H, perylene), 9.45 (d, J ϭ 8.4 Hz, 2 H, per-
8.71Ϫ8.76 (m, 4 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 31.62, ylene), 10.25 (s, 2 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.0,
32.18, 34.69, 35.97, 123.71, 124.29, 124.39, 126.51, 127.04, 127.10, 22.6, 27.0, 29.2, 31.7, 32.4, 55.5, 123.3, 124.6, 124.9, 127.3, 127.9,
127.59, 127.63, 128.75, 128.86, 131.42, 131.93, 131.96, 132.23, 128.7, 129.0, 129.5, 130.9, 131.6, 133.5, 162.2. Ϫ UV/Vis (CHCl3):
CHϪCH2), 2.23Ϫ2.41 (m, 4 H, CHϪCH2), 5.28 (mC, 2 H,
133.26, 133.32, 133.4, 133.46, 143.74, 150.28, 163.56, 164.04. Ϫ λmax (ε) ϭ 332 nm (18060), 370 (8380), 413 (10970), 438 (30610),
UV/Vis (CHCl3): λmax (ε) ϭ 271 nm (17510), 400 (5730), 426 468 (44930). Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 481 nm
(8480), 451 (13730), 480 (22740), 612 (9490). Ϫ MS (70 eV): m/z
(%): 830 (7), 829 (17), 828 (28) [Mϩ], 774 (7), 773 (23), 772 (53),
771 (100) [Mϩ Ϫ C4H9], 739 (7) [Mϩ Ϫ S]. Ϫ C52H48N2O4S2: calcd.
(0.99), 508 (1.0), 550 (0.56). Ϫ Fluorescence quantum yield
(1.13·10Ϫ6 mol/L in CHCl3, reference tetramethyl perylene-
3,4,9,10-tetracarboxylate with Φ ϭ 100%, λexcit. ϭ 440 nm) ϭ 74%.
828.3055; found 828.3097 (MS). Ϫ C52H48N2O4S2 (829.1): calcd. Ϫ MS (70 eV): m/z (%): 850 (7), 849 (21), 848 (36) [Mϩ], 669 (20),
C 75.33, H 5.84, N 3.38, S 7.74; found C 74.59, H 5.69, N 3.30, 668 (64), 667 (100), 666 (25) [Mϩ Ϫ C13H26], 497 (7), 488 (5), 487
S 7.09. Ϫ Second Fraction: Yield 29.0 mg (30%; at a reaction tem-
perature of 153°C: 139 mg, 71%) of 10c as a bright orange powder,
m.p. > 300°C. Ϫ Rf (silica gel, chloroform): 0.32. Ϫ Rf (silica gel,
(24), 486 (87), 485 (91), 484 (27) [Mϩ Ϫ 2 ϫ C13H26], 468 (5), 467
(16), 415 (5), 414 (14), 413 (24), 412 (10), [Mϩ Ϫ 2 ϫ C13H26
Ϫ
C2O3], 395 (12).
376
Eur. J. Org. Chem. 2000, 365Ϫ380

Novel Fluorescent Dyes by the Extension of the Core of Perylenetetracarboxylic Bisimides
FULL PAPER
N,NЈ-Bis(1-butylpentyl)benzoperylene-1Ј,2Ј:3,4:9,10-hexacarboxylic
1Ј,2Ј-Anhydride 3,4:9,10-Bis(imide) (2b): Compound 1b (500 mg,
0.779 mmol), dissolved in molten maleic anhydride (95°C), a few
stirred at room temperature for 16 h (for the ageing of the precipi-
tate). The precipitate was collected by vacuum filtration, dried, and
purified by column separation (silica gel, chloroform). Yield
ml of acetone (or chloroform) and chloranil (380 mg, 1.56 mmol) 100 mg (85%) of 4a as a bright orange powder. Physical data see be-
were allowed to react, and purified as was described for 2a. Yield
450 mg (77%) of 2b as a bright orange powder, m.p. > 300°C. Ϫ
Rf (silica gel, chloroform): 0.00Ϫ0.12. Ϫ Rf (silica gel, chloroform/
acetic acid 10:1): 0.83. Ϫ IR (KBr): ν˜ ϭ 2957 cmϪ1 (m), 2930 (m),
2870 (m), 1848 (w), 1777 (w), 1732 (m), 1705 (s), 1664 (s), 1626 (w),
1597 (m), 1488 (w), 1466 (w), 1417 (m), 1372 (m, sh), 1320 (s), 1297
(w), 1267 (m), 1217 (m, sh), 1172 (m), 1123 (w), 1017 (w), 847 (w),
low.
N,NЈ-Bis(1-hexylheptyl)benzoperylene-1Ј,2Ј:3,4:9,10-hexacarboxylic
1Ј,2Ј-Bis(ethyl ester) 3,4:9,10-Bis(imide) (4a) from 2a: Compound
2a (108 mg, 0.127 mmol) was dissolved in chloroform. Ethanol (ca.
2 mL) was added. The mixture was concentrated and allowed to
react with DBU and ethyl iodide as was described above. Yield
100 mg (85%) of 4a as a bright orange powder, m.p. 273Ϫ275°C.
Ϫ Rf (silica gel, chloroform): 0.65. Ϫ IR (KBr): ν˜ ϭ 2956 cmϪ1
(m), 2927 (s), 2857 (m), 1727 (m, ester CϭO), 1705 (s), 1662 (s),
1626 (w), 1597 (m), 1466 (w), 1415 (m), 1372 (m), 1345 (w), 1320
(s), 1297 (w), 1273 (m), 1216 (m), 1168 (m), 1129 (w), 1074 (w),
1019 (w), 846 (w), 810 (m), 759 (w), 747 (w). Ϫ 1H NMR (CDCl3):
δ ϭ 0.81 (t, J ϭ 6.8 Hz, 12 H, CH3), 1.20Ϫ1.36 (m, 32 H, CH2),
1.59 (t, J ϭ 7.1 Hz, 6 H, OϪCH2ϪCH3), 1.95Ϫ1.99 (m, 4 H,
CHϪCH2), 2.29Ϫ2.36 (m, 4 H, CHϪCH2), 4.73 (q, J ϭ 7.2 Hz,
4 H, OϪCH2ϪCH3), 5.26 (tt, 3J1 ϭ 6.0 Hz, 3J2 ϭ 8.8 Hz, 2 H,
NϪCH), 9.01 (br. d, 2 H, perylene), 9.12 (d, J ϭ 8.4 Hz, 2 H, per-
ylene), 9.44 (s, 2 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.0, 14.3
(OϪCH2ϪCH3), 22.6, 27.1, 29.3, 31.8, 32.5, 55.2, 63.1
(OϪCH2ϪCH3), 122.8, 123.3, 125.2, 126.3, 131.5, 132.8, 166.6
(COOEt). Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 388 nm (5360), 411
(16700), 436 (43460), 466 (69070). Ϫ Fluorescence (chloroform):
λmax (Irel.) ϭ 476 nm (1.0), 506 (0.57), 547 (0.08). Ϫ Fluorescence
quantum yield (1.18 ϫ 10Ϫ6 mol/L in CHCl3, reference tetramethyl
1
812 (m), 761 (w), 748 (w). Ϫ H NMR (CDCl3): δ ϭ 0.86 (t, J ϭ
7.0 Hz, 12 H, CH3), 1.27Ϫ1.42 (m, 16 H, CH2), 1.90Ϫ2.02 (m, 4 H,
CHϪCH2), 2.28Ϫ2.38 (m, 4 H, CHϪCH2), 5.29 (mC, 2 H,
NϪCH), 9.22 (d, J ϭ 8,1 Hz, 2 H, perylene), 9.43 (d, J ϭ 8.5 Hz,
2 H, perylene), 10.24 (s, 2 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ
14.0, 22.6, 29.2, 32.1, 55.4, 123.3, 124.6, 124.9, 127.3, 127.9, 129.0,
133.5, 162.2. Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 304 nm (21010), 332
(18180), 370 (5350), 412 (11220), 437 (33900), 467 (54190). Ϫ Flu-
orescence (chloroform): λmax (Irel.) ϭ 477 nm (1.0), 504 (0.81), 548
sh (0.23). Ϫ Fluorescence quantum yield (1.13·10Ϫ6 mol/L in
CHCl3, reference tetramethyl perylene-3,4,9,10-tetracarboxylate
with Φ ϭ 100%, λexcit. ϭ 440 nm) ϭ 73%. Ϫ MS (70 eV): m/z (%):
738 (5), 737 (19), 736 (38) [Mϩ], 679 (6) [Mϩ Ϫ C4H9], 613 (12),
612 (49), 611 (100), 610 (28) [Mϩ Ϫ C9H18], 497 (9), 487 (16), 486
(60), 485 (96), 484 (42) [Mϩ Ϫ 2 ϫ C9H18], 467 (10) [Mϩ Ϫ 2 ϫ
C9H18 Ϫ OH], 414(9), 413 (21), 412 (10) [Mϩ Ϫ 2 ϫ C9H18
Ϫ
C2O3], 395 (8).
N,NЈ-Bis(2,5-di-tert-butylphenyl)benzoperylene-1Ј,2Ј:3,4:9,10-hexa-
carboxylic 1Ј,2Ј-Anhydride 3,4:9,10-Bis(imide) (2c): Compound 1c
perylene-3,4,9,10-tetracarboxylate with
Φ ϭ 100%, λexcit. ϭ
440 nm) ϭ 85%. Ϫ MS (70 eV): m/z (%): 924 (13), 923 (39), 922
(300 mg, 0.392 mmol), dissolved in molten maleic anhydride (66) [Mϩ], 905 (7) [Mϩ Ϫ OH], 743 (6), 742 (26), 741 (63), 740 (56)
(95°C), a few ml of acetone (or chloroform) and chloranil (240 mg,
[Mϩ Ϫ C13H26], 667 (9) [Mϩ Ϫ C13H26 Ϫ C3H5O2], 577 (6), 560
0.984 mmol) were allowed to react as was described for 2a, and (21), 559 (55), 558 (100) [Mϩ Ϫ 2 ϫ C13H26], 486 (18), 485 (50)
purified by column separation (silica gel). The forerun was eluted
with chloroform/10% ethanol and the main fraction with chloro-
form/10% acetic acid. Yield 230 mg (67%) of 2c as a dark yellow
powder, m.p. > 300°C. Ϫ Rf (silica gel, chloroform/10% ethanol):
0.00Ϫ0.16. Ϫ Rf (silica gel, chloroform/10% acetic acid): 0.55. Ϫ
IR (KBr): ν˜ ϭ 3437 cmϪ1 (s), 2964 (m), 2871 (w), 1847 (w), 1778
(w), 1714 (s), 1674 (s), 1627 (w), 1598 (m), 1486 (w), 1413 (m), 1365
(m), 1330 (m), 1297 (w), 1264 (m), 1216 (m), 812 (m), 764 (w), 746
(w). Ϫ 1H NMR (CDCl3): δ ϭ 1.35Ϫ1.36 (m, 36 H, CH3), 7.13
and 7.18 (each s, 2 H, phenyl), 7.54 (d, 3JCH ϭ 8.1 Hz, 2 H, phenyl),
[Mϩ Ϫ 2 ϫ C13H26 Ϫ C3H5O2], 467 (8), 466 (8), 414 (6), 413 (7),
397 (8), 396 (14), 368 (6), 339 (7), 322 (10), 313 (7). Ϫ C58H70N2O8
(923.2): calcd. C 75.46, H 7.64, N 3.03; found C 75.34, H 7.52,
N 3.04.
N,NЈ-Bis(1-butylpentyl)benzoperylene-1Ј:2Ј,3:4,9:10-hexacarboxylic
1Ј,2Ј-Bis(ethyl ester) 3,4:9,10-Bis(imide) (4b). ؊ Preparation from
the Free Acid: N,NЈ-Bis(1-butylpentyl)benzoperylene-1Ј,2Ј:3,4:9,10-
hexacarboxylic acid 3,4:9,10-bis(imide) (30 mg, 0.04 mmol, by hy-
drolysis of 2b) was dissolved in THF and allowed to react with
DBU (65 mg, 0.42 mmol) and ethyl iodide (65 mg, 0.42 mmol) as
was described for 4a and purified by column separation (silica gel
activity III .. IV, chloroform). Yield 27 mg (84%) of 4b as a high
orange powder, m.p. > 300°C. Ϫ Rf (silica gel, chloroform): 0.41.
Ϫ IR (KBr): ν˜ ϭ 2957 cmϪ1 (m), 2930 (m), 2871 (m), 1732 (m,
ester CϭO), 1705 (s), 1663 (s), 1626 (w), 1597 (m), 1466 (w), 1415
(m), 1372 (m), 1362 (w), 1320 (s), 1296 (w), 1270 (m), 1214 (m),
1173 (w), 1131 (w), 1020 (w), 811 (m), 760 (w), 748 (w). Ϫ 1H NMR
(CDCl3): δ ϭ 0.88 (t, J ϭ 6.7 Hz, 12 H, CH3), 1.36Ϫ1.40 (m, 16 H,
CH2), 1.59 (t, J ϭ 7.2 Hz, 6 H, OϪCH2ϪCH3), 1.94Ϫ2.03 (m, 4 H,
CHϪCH2), 2.30Ϫ2.39 (m, 4 H, CHϪCH2), 4.69 (q, J ϭ 7.2 Hz,
4 H, OϪCH2ϪCH3 ), 5.27 (mC, 2 H, NϪCH), 9.00 (br. d, J ϭ
7.4 Hz, 2 H, perylene), 9.10 (d, J ϭ 8.5 Hz, 2 H, perylene), 9.43 (s,
3
7.67 (d, JCH ϭ 8.5 Hz, 2 H, phenyl), 9.35 and 9.38 (each d, J ϭ
7.7 and 7.4 Hz, 2 H, perylene), 9.57 and 9.62 (each d, J ϭ 8.4 Hz, 2
H, perylene), 10.40 and 10.45 (each s, 2 H, perylene). Ϫ 13C NMR
(CDCl3): δ ϭ 31.23, 31.84, 34.35, 35.66, 123.71, 123.80, 124.98,
125.04, 125.19, 126.21, 126.27, 126.73, 127.58, 127.67, 128.21,
128.35, 128.85, 129.02, 129.07, 129.42, 129.67, 129.74, 131.61,
131.66, 132.17, 132.59, 134.01, 134.18, 143.77, 143.81, 150.43,
150.48, 162.18, 162.25, 163.81 163.86, 164.28, 164.34. Ϫ UV/Vis
(CHCl3): λmax (ε) ϭ 288 nm (17560), 333 (16460), 367 (5460), 413
(11020), 438 (31590), 468 (47990). Ϫ Fluorescence (chloroform):
λmax (Irel.) ϭ 479 nm (1.0), 508 (0.87), 547 (0.39). Ϫ MS (70 eV):
m/z (%): 806 (6), 805 (27), 804 (58), 803 (100) [Mϩ Ϫ C4H9].
N,NЈ-Bis(1-hexylheptyl)benzoperylene-1Ј,2Ј:3,4:9,10-hexacarboxylic
2 H, perylene).
Ϫ
13C NMR (CDCl3):
δ
ϭ
14.1, 14.3
1Ј,2Ј-Bis(ethyl ester) 3,4:9,10-Bis(imide) (4a). ؊ Preparation from (OϪCH2ϪCH3), 22.7, 29.3, 32.2, 55.1, 63.1 (OϪCH2ϪCH3),
the Free Acid: N,NЈ-Bis(1-hexylheptyl)benzoperylene-1Ј,2Ј:3,4:9,10-
122.8, 123.3, 125.1, 126.3, 127.1, 131.5, 132.8, 163.3, 163.6, 164.5,
hexacarboxylic acid 3,4:9,10-bis(imide) (110 mg, 0.127 mmol, by
166.6 (COOEt). Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 302 nm (30880),
hydrolysis of 2a) was dissolved in THF and deprotonated with 334 (20880), 388 (2620), 411 (13980), 437 (40500), 466 (65340). Ϫ
DBU (60.0 mg, 0.395 mmol). Ethyl iodide (100 mg, 0.641 mmol)
was added. The mixture was stirred at room temperature for 16 h,
poured into water (150 mL), weakly acidified with 2  HCl, and
Fluorescence (chloroform): λmax (Irel.) ϭ 478 nm (1.0), 508 (0.60),
548 (0.09). Ϫ MS (70 eV): m/z (%): 812 (8), 811 (28), 810 (51) [Mϩ],
793 (8) [Mϩ Ϫ OH], 753 (6), 745 (6), 686 (19), 685 (49), 684 (46)
Eur. J. Org. Chem. 2000, 365Ϫ380
377

H. Langhals, S. Kirner
FULL PAPER
[Mϩ Ϫ C9H18], 667 (5), 612 (7), 611 (15) [Mϩ Ϫ C9H18 Ϫ C3H5O2],
29.3, 30.1 (cyclohexyl), 31.8, 32.5, 51.9 (NϪCHcyclohexyl), 55.3,
560 (18), 559 (59), 558 (100) [Mϩ Ϫ 2 ϫ C9H18], 487 (5), 486 (22), 122.6, 123.3, 124.0, 126.6, 126.8, 127.2, 132.4, 167.8 (5-ring-CϭO).
485 (57) [Mϩ Ϫ 2 ϫ C9H18 Ϫ C3H5O2], 484 (5), 467 (7), 442 (5),
414 (8), 413 (13). Ϫ C50H54N2O4 (811.0): calcd. C 74.05, H 6.71, (16940), 358 (28370), 372 (37350), 410 (15310), 435 (38930), 465
Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 274 nm (28070), 316 (14660), 332
N 3.45; found C 74.09, H 6.77, N 3.38.
(60230). Ϫ Fluorescence (chloroform): λmax (Irel.) ϭ 480 nm (1.0),
509 (0.60), 548 (0.11). Ϫ Fluorescence quantum yield (7.92 ϫ
10Ϫ7 mol/L in CHCl3, reference tetramethyl perylene-3,4,9,10-
tetracarboxylate with Φ ϭ 100%, λexcit. ϭ 440 nm) ϭ 45%. Ϫ MS
(70 eV): m/z (%): 931 (12), 930 (18), 929 (52) [Mϩ], 913 (5), 912
(11) [Mϩ Ϫ OH], 845 (8), 844 (16) [Mϩ Ϫ C6H13], 760 (6), 751 (6),
750 (23), 749 (66), 748 (100), 747 (39) [Mϩ Ϫ C13H26], 730 (8), 664
(5), 663 (7), 662 (5),568 (25), 567 (60), 566 (74), 565 (63) [Mϩ Ϫ 2
ϫ C13H26], 522 (7), 486 (5), 485 (25), 484 (59), 483 (32) [Mϩ Ϫ 2
ϫ C13H26 Ϫ C6H10], 466 (13), 441 (8), 182 (7). Ϫ C60H71N3O6
(930.2): calcd. C 77.47, H 7.69, N 4.52; found C 77.27, H 7.57,
N 4.49.
N,NЈ-Bis(2,5-di-tert-butylphenyl)benzoperylene-1Ј:2Ј,3:4,9:10-hexa-
carboxylic 1Ј,2Ј-Bis(ethyl ester) 3,4:9,10-Bis(imide) (4c). ؊ Prep-
aration from the Free Acid: N,NЈ-Bis(2,5-di-tert-butylphenyl)benzo-
perylene-1Ј,2Ј:3,4:9,10-hexacarboxylic acid 3,4:9,10-bis(imide)
(50 mg, 0.060 mmol, by hydrolysis of 2c) was dissolved in THF and
allowed to react with DBU (35 mg, 0.23 mmol) and ethyl iodide
(45 mg, 0.29 mmol) as was described for 6a, and purified by col-
umn separation (silica gel, chloroform/3% ethanol). Yield 41 mg
(78%) of 4c as a yolk-yellow powder, m.p. > 300°C. Ϫ Rf (silica
gel, chloroform): 0.24. Ϫ Rf (Al2O3/chloroform): 0.88. Ϫ Rf (silica
gel, chloroform/3% ethanol): 0.67. Ϫ IR (KBr): ν˜ ϭ 3080 cmϪ1
(w), 2963 (m), 2907 (w), 2870 (w), 1732 (m, Ester-CϭO), 1715 (s), N,NЈЈ-Bis(1-hexylheptyl)-NЈ-2,5-di-tert-butylphenylbenzoperylene-
1675 (s), 1628 (w), 1598 (m), 1486 (w), 1466 (w), 1411 (s), 1372 (s), 1Ј,2Ј:3,4:9,10-tris(dicarboximide) (3b): Compound 2a (60.0 mg,
1363 (m), 1330 (s), 1296 (w), 1270 (m), 1255 (m), 1212 (s), 1182 0.0710 mmol), 2,5-di-tert-butylaniline (100 mg, 0.488 mmol), and
(w), 1164 (w), 1142 (w), 1131 (w), 1094 (w), 1075 (w), 1019 (w),
820 (w), 812 (m), 761 (w), 746 (w). Ϫ H NMR (CDCl3): δ ϭ 1.27 fluoroacetic acid (1 drop) was added. The mixture was heated un-
(s, 12 H, CH3), 1.32Ϫ1.35 (m, 24 H, CH3), 1.57 and 1.61 (each t, der reflux (24 h), diluted with chloroform, repeatedly washed with
DCC (75.0 mg, 0.364 mmol) were dissolved in chloroform. Tri-
1
J
ϭ
7.1 Hz, 6 H, OϪCH2ϪCH3), 4.66Ϫ4.78 (m, 4 H,
water, concentrated, and purified by column separation (silica gel,
chloroform followed by neutral alumina, petroleum ether/3%
chloroform). Yield 50 mg (70%; Yield 50% after 4 days reaction
time, if only DCC or only trifluoroacetic acid were applied) 3b as
a bright yellow solid, m.p. 285Ϫ287°C. Ϫ Rf (silica gel, chloro-
form): 0.66. Ϫ IR (KBr): ν˜ ϭ 2956 cmϪ1 (m), 2927 (m), 2858 (w),
1774 (w, CϭO 5-membered-ring-imide), 1720 (s, CϭO 5-mem-
4
OϪCH2ϪCH3), 7.12 (d, JCH ϭ 2.3 Hz, 0.8 H, phenyl), 7.35 (br.
d, 1.2 H, phenyl), 7.47 and 7.50 (each dd, JCH ϭ 8.5 Hz, JCH
2.2 Hz, 2 H, phenyl), 7.60 (d, JCH ϭ 8.5 Hz, 1.2 H, phenyl), 7.64
(d, JCH ϭ 8.5 Hz, 0.8 H, phenyl), 9.07Ϫ9.15 (m, 2.8 H, perylene),
3
4
ϭ
3
3
9.22 (d, J ϭ 8.2 Hz, 0.8 H, perylene), 9.45 (d, J ϭ 8.3 Hz, 0.8 H,
perylene), 9.58 (s, 1.0 H, perylene), 9.723 (s, 0.6 H, perylene). Ϫ
13C NMR (CDCl3):
δ
ϭ
14.53 (OϪCH2ϪCH3), 14.62 bered-ring-imide), 1707 (m), 1664 (s), 1627 (w), 1596 (w), 1523 (w),
(OϪCH2ϪCH3), 31.42, 31.48, 32.01, 34.54, 34.60, 35.78, 35.87, 1505 (w), 1459 (w), 1413 (m), 1366 (m), 1320 (s), 1272 (w), 1241
63.49 (OϪCH2ϪCH3), 63.62 (OϪCH2ϪCH3), 123.02, 123.19, (w), 1204 (w), 1169 (w), 1112 (w), 972 (w), 946 (w), 848 (w), 813
1
123.27, 123.88, 123.99, 124.18, 124.44, 124.58, 125.65, 126.29,
126.57, 126.77, 126.99, 127.23, 127.85, 127.94, 128.47, 128.90,
129.17, 130.29, 130.58, 131.69, 132.20, 132.27, 132.40, 132.64,
132.74, 133.26, 134.09, 143.79, 144.06, 150.52, 150.60, 164.36,
164.49, 164.67, 164.88, 166.90 (COOEt), 167.02 (COOEt). Ϫ UV/
(w), 767 (w), 749 (w), 725 (w), 662 (w). Ϫ H NMR (CDCl3): δ ϭ
0.80 (t, J ϭ 6.6 Hz, 12 H, CH3), 1.20Ϫ1.43 (m, 50 H, CH2 of the
alkyl side-chain ϩ CH3 of the tert-butyl groups at 1.34 and
1.40 ppm), 1.92 (mC, 4 H, CHϪCH2), 2.32 (mC, 4 H, CHϪCH2),
4
5.28 (mC, 2 H, NϪCHtridec.), 7.19 (d, JCH ϭ 1.9 Hz, 1 H, phenyl),
Vis (CHCl3): λmax (ε) ϭ 289 nm (30820), 300 (31060), 334 (27410), 7.53 (dd, JCH ϭ 8.6 Hz, 4JH ϭ 2.1 Hz, 1 H, phenyl), 7.64 (d,
3
386 (4860), 411 (17630), 437 (47320), 467 (76150). Ϫ Fluorescence
(chloroform): λmax (Irel.) ϭ 476 nm (1.0), 509 (0.50), 549 (0.08). Ϫ
3JCH ϭ 8.6 Hz, 1 H, phenyl), 9.16 (br. d, 2 H, perylene), 9.40 (d,
J ϭ 8.4 Hz, 2 H, perylene), 10.52 (s, 2 H, perylene). Ϫ 13C NMR
(CDCl3): δ ϭ 14.03, 22.57, 26.99, 29.23, 31.19, 31.76 (CMe3), 31.81
MS (70 eV): m/z (%): 887 (5), 879 (20), 878 (60), 877 (100) [Mϩ
Ϫ
C4H9], 57 (9) [C4H9]. Ϫ C56H49N2O8 (878.01): calcd. 877.3489; (CMe3), 32.42, 34.33 (CMe3), 35.32 (CMe3), 55.27, 123.51, 124.07,
found 877.3428 (MS). Ϫ C60H58N2O8 (935.1): calcd. C 77.07,
H 6.25, N 3.00; found C 76.38, H 6.50, N 2.99.
125.19, 127.27, 127.74, 127.95, 128.20, 128.30, 128.54, 128.94,
129.94, 130.70, 133.35, 146.24 (Raromatic), 150.45 (Raromatic), 163.07,
163.60, 164.31, 164.69, 168.64 (5-ring-CϭO). Ϫ UV/Vis (CHCl3):
λmax (ε) ϭ 264 nm (27410), 273 (29750), 376 (40280), 410 (15240),
436 (38980), 466 (60980). Ϫ Fluorescence (chloroform): λmax
(Irel.) ϭ 478 nm (1.0), 510 (0.62), 550 (0.17). Ϫ Fluorescence quan-
tum yield (1.13 ϫ 10Ϫ6 mol/L in CHCl3, reference tetramethyl per-
ylene-3,4,9,10-tetracarboxylate with Φ ϭ 100%, λexcit. ϭ 440 nm) ϭ
45%. Ϫ MS (70 eV): m/z (%): 1037 (19), 1036 (49), 1035 (67) [Mϩ],
1020 (6), 1019 (6), 1018 (8) [Mϩ Ϫ OH], 856 (19), 855 (58), 854
(100), 853 (52) [Mϩ Ϫ C13H26], 838 (6), 836 (6), 674 (19), 673 (56),
672 (75), 671 (40) [Mϩ Ϫ 2 ϫ C13H26], 658 (6), 657 (22), 656 (48)
[Mϩ Ϫ 2 ϫ C13H26 Ϫ OH], 638 (8), 617 (8), 616 (15), 615 (6), 614
(11) [Mϩ Ϫ 2 C13H26 Ϫ C4H9], 601 (7), 600(14), 583 (8), 582 (19),
561 (14), 560 (34) [Mϩ Ϫ 2 ϫ C13H26 Ϫ C4H9 Ϫ C4H7], 558 (8)
[Mϩ Ϫ 2 ϫ C13H26 Ϫ C4H9 Ϫ C4H9], 542 (5), 419 (5). Ϫ
C68H81N3O6 (1036.4): calcd. C 78.81, H 7.88, N 4.05; found
C 78.63, H 8.12, N 4.04.
N,NЈЈ-Bis(1-hexylheptyl)-NЈ-cyclohexylbenzoperylene-
1Ј,2Ј:3,4:9,10-tris(dicarboximide) (3a): Compound 2a (100 mg,
0.118 mmol), cyclohexylamine (114 mg, 1.15 mmol) and quinoline
(10 mL) were refluxed (6 h, bath 160°C), cooled, poured into 2 
HCl (100 mL), stirred at room temperature for several h (ageing of
the brown precipitate), collected by vacuum filtration, dried, and
purified by column separation (silica gel, chloroform). Yield 71 mg
(66%) 3a as an orange yellow powder, m.p. > 300°C. Ϫ Rf (silica
gel, chloroform): 0.63. Ϫ IR (KBr): ν˜ ϭ 2954 cmϪ1 (s), 2928 (s),
2857 (s), 1765 (m, CϭO of the 5-membered-ring imide), 1709 (s),
1666 (s), 1625 (w), 1596 (m), 1523 (w), 1456 (m), 1414 (m), 1366
(s), 1348 (w), 1318 (s), 1272 (w), 1240 (m), 1203 (w), 1175 (m), 1107
(w), 945 (m), 846 (w), 811 (m), 766 (m), 747 (w), 660 (w), 640 (w),
529 (w), 436 (w). Ϫ 1H NMR (CDCl3): δ ϭ 0.83 (t, J ϭ 7.0 Hz,
12 H, CH3), 1.27Ϫ1.43 (m, 37 H, CH2), 2.04Ϫ2.12 (m, 8 H, CH2),
3
3
2.33Ϫ2.51 (m, 6 H, CH2), 4.37 (tt, JCH-AE ϭ 3.5 Hz, JCH-AA
12.2 Hz, 1 H, NϪCHcyclohexyl), 5.30 (mC, 2 H, NϪCHtridec.), Dye 15a: Compound 2a (100 mg, 0.115 mmol) and 1,8-diamino-
8.89Ϫ8.98 (m, 4 H, perylene), 10.02 (s, 2 H, perylene). Ϫ 13C NMR
naphthalene (180 mg, 1.14 mmol) were dissolved in diethylene gly-
(CDCl3): δ ϭ 14.1, 22.6, 25.4 (cyclohexyl), 26.3 (cyclohexyl), 27.1, col monomethyl ether (15 ml; or quinoline), heated under reflux
ϭ
378
Eur. J. Org. Chem. 2000, 365Ϫ380

Novel Fluorescent Dyes by the Extension of the Core of Perylenetetracarboxylic Bisimides
(5 h, 150°C), poured into water (150 ml; or into 2  HCl if quino- 100%, λexcit. ϭ 440 nm) ϭ 77%. Ϫ MS (70 eV): m/z (%): 780 (8),
FULL PAPER
line is used), stirred at room temperature for 16 h (dark brown pre-
cipitate). The precipitate was collected by vacuum filtration, dried,
and purified by column separation (silica gel, added to the column
with pure chloroform, eluted with 1. chloroform, 2. dichlorometh-
ane 3. petroleum ether/chloroform, 4:1). Yield 80 mg (71%) of 15a
as a dark red powder, m.p. > 300°C. Ϫ Rf (silica gel, chloroform):
0.60. Ϫ Rf (silica gel, dichloromethane): 0.53. Ϫ IR (KBr): ν˜ ϭ
2955 cmϪ1 (m), 2926 (s), 2856 (m), 1707 (s), 1661 (s), 1625 (w),
1595 (w), 1524 (w), 1456 (m), 1408 (m), 1367 (m), 1350 (m), 1347
(w), 1322 (s), 1260 (w), 1238 (m), 1170 (w), 827 (m), 812 (m), 770
779 (28), 778 (52) [Mϩ], 761 (6) [Mϩ Ϫ OH], 598 (17), 597 (48),
596 (45) [Mϩ Ϫ C13H26], 427 (6), 416 (20), 415 (70), 414 (100) [Mϩ
Ϫ 2 ϫ C13H26], 397 (11). Ϫ C52H62N2O4 (779.08): calcd. C 80.17,
H 8.02, N 3.60; found C 80.08, H 8.11, N 3.59.
N,NЈ-Bis(1-butylpentyl)-1,3-dioxo-2-phenylbenzo[4,10]anthra[1,9,8-
cdef][1,2,4]triazolo[1,2-a]cinnoline-5,6:11,12-bis(dicarboximide)
(14b): N,NЈ-Bis(1-butylpentyl)perylene-3,4:9,10-bis(dicarboximide)
(1b, 100 mg, 0.156 mmol), 4-phenyl-1,2,4-triazoline-3,5-dione
(273 mg, 1.56 mmol) and chloranil (38.0 mg, 0.156 mmol) in dried
toluene were refluxed for 24 h, concentrated, and purified by col-
umn separation (silica gel, chloroform for removing 1b and di-
chloromethane for the elution of 14b; 14b has a higher Rf value in
chloroform than 1b; the chromatography can be accelerated by the
addition of 1% ethanol or acetone). Yield 32 mg (25%; the yield
without the addition of chloranil is 6 mg, 5%) of 14b as a green
solid, m.p. > 300°C. Ϫ Rf (silica gel, chloroform): 0.18. Ϫ Rf (silica
gel, dichloromethane): 0.39. Ϫ IR (KBr): ν˜ ϭ 3109 cmϪ1 (w,
CϪHarom.), 2956 (m), 2929 (m), 2861 (w), 1773 (m, CϭO triazole
ring), 1726 (s, CϭO triazole ring), 1702 (s), 1661 (s), 1600 (m), 1577
(m), 1502 (m), 1458 (w), 1421 (m), 1394 (s), 1378 (m), 1339 (m),
1301 (m), 1282 (w), 1241 (w), 1184 (w), 985 (w), 927 (w), 850 (w),
810 (m), 744 (m), 731 (w), 688 (w), 645 (w), 537 (w), 503 (w). Ϫ
1H NMR (CDCl3): δ ϭ 0.84 (t, J ϭ 7.0 Hz, 12 H, CH3), 1.15Ϫ1.40
(m, 16 H, CH2), 1.84 (mC, 4 H, CHϪCH2), 2.15 (mC, 4 H,
1
(m), 759 (w), 748 (w), 664 (w). Ϫ H NMR (CDCl3): δ ϭ 0.87 (t,
J ϭ 6.7 Hz, 12 H, CH3), 1.34 (mC, 16 H, CH2), 1.51 (mC, 16 H,
CH2), 2.12 (mC, 4 H, CHϪCH2), 2.47 (mC, 4 H, CHϪCH2), 5.36
(mC, 2 H, NϪCH), 6.84 (br. d, J ϭ 28.3 Hz, 1 H, naphthalene),
7.15 (dd, 3J1
ϭ
3J2 ϭ 7.8 Hz, 1 H, naphthalene), 7.26Ϫ7.37 (m,
3 H, naphthalene), 7.85 (br. d, 1 H, naphthalene), 8.70 (br. d, J ϭ
8.5 Hz, 2 H, perylene), 8.78 (d, J ϭ 8.3 Hz, 1 H, perylene), 8.82 (d,
J ϭ 8.3 Hz, 1 H, perylene), 10.02 (br. s, 1 H, perylene), 10.24 (br.
s, 1 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.2, 22.8, 27.3, 29.5,
32.0, 32.6, 55.2 (only the signals of the alkyl side-chain even after
4096 scans at 75.47 MHz because of the low solubility of the am-
ine). Ϫ UV/Vis (CHCl3): λmax (ε) ϭ 277 nm (22410), 296 (22950),
322 (19280), 367 (32150), 379 (sh., 32150), 386 (44420), 410
(14230), 436 (31720), 464 (47670), 518 (br., 13240), 587 (sh., 6440).
Ϫ MS (70 eV): m/z (%): 973 (8), 972 (29), 971 (76), 970 (100) [Mϩ],
790 (11), 789 (26), 788 (23) [Mϩ Ϫ C13H26], 704 (6), 608 (20), 607
(71), 606 (60), [Mϩ Ϫ 2 ϫ C13H26]. Ϫ C64H66N4O5 (971.3): calcd.
C 79.15, H 6.85, N 5.77; found C 78.87, H 6.68, N 5.68.
3
3
CHϪCH2), 5.07 [tt, J1 ϭ 6.0 Hz, J2 ϭ 9.0 Hz, 2 H, CH (CH2)2],
7.48 (t, J ϭ 7.2 Hz, 1 H, phenyl), 7.57 (t, J ϭ 7.2 Hz, 2 H, phenyl),
7.70 (d, J ϭ 7.2 Hz, 2 H, phenyl), 8.12 (d, J ϭ 8.1 Hz, 2 H, per-
ylene), 8.33 (br. d, J ϭ 7.9 Hz, 2 H, perylene), 9.23 (s, 2 H, per-
ylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.0, 22.6, 29.1, 31.9, 55.0, 116.9,
123.5, 125.0, 126.1, 126.4, 129.1, 129.4, 130.0, 132.6, 133.5, 143.3
(CϭO triazole ring). Ϫ UV/Vis (CHCl3): λmax (Erel.) ϭ 291 nm
(1.0), 346 (0.19), 396 (0.12), 419 (0.21), 443 (0.41), 649 (0.26). Ϫ
Fluorescence (chloroform): λmax ϭ 756 nm, 866, 885 sh. Ϫ MS
(70 eV): m/z (%): 817 (17), 816 (57), 815 (100) [Mϩ], 798 (8) [Mϩ
Ϫ OH], 691 (8), 690 (18), 689 (20) [Mϩ Ϫ C9H18], 672 (6), 565 (11),
N,NЈ-Bis(1-hexylheptyl)benzoperylene-3,4:9,10-bis(dicarboximide)
(5a). ؊ Decarboxylation of 2a with Copper Powder: Compound 2a
(50 mg, 0.060 mmol) and copper powder (40 mg, 0.64 mmol) were
heated in quinoline under argon (4 h, 180°C), cooled, poured into
2  HCl, and stirred at room temperature for 16 h (dark brown
precipitate). The precipitate was collected by vacuum filtration,
dried and purified by column separation (silica gel, chloroform).
Yield 17 mg (38%) of 5a as a yellow to orange powder. Physical 564 (27), 563 (33) [Mϩ Ϫ 2 ϫ C9H18], 429 (6), 418 (12), 417 (43),
data see below.
416 (53) [Mϩ Ϫ 2 ϫ C9H18 Ϫ C6H5NCO Ϫ CO], 399 (12), 391 (6),
390 (10), 388 (7). Ϫ C50H49N5O6 (816.0): calcd. C 73.60, H 6.05,
N 8.58; found C 72.13, H 6.25, N 8.38.
N,NЈ-Bis(1-hexylheptyl)benzoperylene-3,4:9,10-bis(dicarboximide)
(5a). ؊ Decarboxylation of 2a with Copper(I) Oxide: Compound
2a (50 mg, 0.060 mmol) and copper(I) oxide (Cu2O, 40 mg,
0.28 mmol) were heated in quinoline under argon at 180°C for 4 h,
cooled, poured into 2  HCl, and stirred at room temperature for
16 h (dark brown precipitate). The precipitate was collected by vac-
uum filtration, dried, and purified by column separation (silica gel,
chloroform; the yields were very variable). Yield 16 mg (36%) of 5a
N,NЈ-Bis(1-hexylheptyl)-1,3-dioxo-2-phenylbenzo[4,10]-
anthra[1,9,8-cdef][1,2,4]triazolo[1,2-a]cinnoline-5,6:11,12-dis(di-
carboximide) (14a): N,NЈ-Bis(1-hexylheptyl)perylene-3,4:9,10-
bis(dicarboximide) (1a, 100 mg, 0.133 mmol), 4-phenyl-1,2,4-tri-
azolin-3,5-dion (180 mg, 1.03 mmol) and chloranil (32.5 mg,
0.133 mmol) were heated under reflux in dry toluene for 24 h, con-
as a yellow to orange powder, m.p. 289Ϫ291°C. Ϫ Rf (silica gel, centrated, and purified by column separation (silica gel, chloroform
chloroform): 0.82. Ϫ IR (KBr): ν˜ ϭ 2955 cmϪ1 (m), 2927 (s), 2857 for removing of 1a and dichloromethane for the elution of 14a).
(m), 1703 (s), 1662 (s), 1627 (w), 1597 (m), 1498 (w), 1460 (w), 1411 Yield 32 mg (25%) of 14a as a green solid, m.p. > 300°C. Ϫ Rf
(wϪm), 1362 (m), 1317 (s), 1258 (wϪm), 1234 (w), 1179 (w), 1163 (silica gel, chloroform): 0.32. Ϫ Rf (silica gel, dichloromethane):
(w), 1119 (w), 930 (w), 844 (w), 809 (m), 790 (w), 747 (wϪm), 724 0.56. Ϫ IR (KBr): ν˜ ϭ 2954 cmϪ1 (m), 2927 (mϪs), 2856 (m), 1773
1
(w), 642 (w), 590 (w), 456 (w). Ϫ H NMR (CDCl3): δ ϭ 0.83 (t, (m, CϭO triazole ring), 1726 (s, CϭO triazole ring), 1702 (s), 1661
J ϭ 6.6 Hz, 12 H, CH3), 1.25Ϫ1.38 (m, 32 H, CH2), 1.93Ϫ2.02 (s), 1600 (m), 1577 (m), 1502 (m), 1458 (w), 1421 (m), 1394 (s),
(m, 4 H, CHϪCH2), 2.31Ϫ2.41 (m, 4 H, CHϪCH2), 5.32 [m, 2 H,
1378 (m), 1339 (m), 1300 (mϪs), 1243 (w), 1178 (w), 1118 (w), 1028
CH(CH2)2], 8.61 (s, 2 H, perylene), 9.01 (br. d, 2 H, perylene), 9.16 (w), 975 (w), 928 (w), 851 (w), 809 (m), 744 (m), 730 (w), 694 (w),
1
(d, J ϭ 8.6 Hz, 2 H, perylene), 9.29 (br. s, 2 H, perylene). Ϫ
645 (w), 536 (w), 503 (w). Ϫ H NMR (CDCl3): δ ϭ 0.84 (t, J ϭ
13C NMR (CDCl3): δ ϭ 14.0, 22.6, 27.0, 29.3, 31.8, 32.5, 55.0, 6.7 Hz, 12 H, CH3), 1.22Ϫ1.40 (m, 32 H, CH2), 1.84 (mC, 4 H,
3
3
122.9, 123.5, 124.4, 127.1, 129.1, 130.0, 132.9. Ϫ UV/Vis (CHCl3):
CHϪCH2), 2.18 (mC, 4 H, CHϪCH2), 5.09 [tt, J1 ϭ 6.2 Hz, J ϭ
λmax (ε) ϭ 279 nm (30160), 287 (33410), 300 (28250), 388 (4740), 9.0 Hz, 2 H, CH(CH2)2], 7.51 (t, J ϭ 7.3 Hz, 1 H, phenyl), 7.60 (t,
413 (17100), 439 (46000), 468 (75910). Ϫ Fluorescence (chloro-
form): λmax (Irel.) ϭ 477 nm (1.0), 510 (0.58), 549 (0.13). Ϫ Fluor-
escence quantum yield (CHCl3, 5.34 ϫ 10Ϫ7 mol/l in CHCl3, refer-
J ϭ 7.5 Hz, 2 H, phenyl), 7.70 (d, J ϭ 7.7 Hz, 2 H, phenyl), 8.13
(d, J ϭ 8.2 Hz, 2 H, perylene), 8.33 (br. d, J ϭ 7.3 Hz, 2 H, per-
ylene), 9.24 (s, 2 H, perylene). Ϫ 13C NMR (CDCl3): δ ϭ 14.1,
22.6, 27.0, 29.2, 31.8, 32.2, 55.1, 116.9, 123.5, 125.0, 126.1, 126.4,
ence tetramethyl perylene-3,4,9,10-tetracarboxylate with
Φ ϭ
Eur. J. Org. Chem. 2000, 365Ϫ380
379

H. Langhals, S. Kirner
FULL PAPER
[11]
[12]
[13]
[14]
J. Sauer, B. Schröder, Chem. Ber. 1967, 100, 678Ϫ684.
129.2, 129.4, 130.0, 132.6, 133.5, 143.4 (CϭO triazole ring). Ϫ UV/
Vis (CHCl3): λmax (ε) ϭ 291 nm (53140), 347 (10900), 357 (10270),
396 (7030), 419 (12120), 443 (22870), 650 (14610). Ϫ Fluorescence
(chloroform): λmax ϭ 753 nm, 868, 882 sh. Ϫ MS (70 eV): m/z (%):
930 (5), 929 (22), 928 (65), 927 (100) [Mϩ], 910 (6) [Mϩ Ϫ OH],
747 (10), 746 (19), 745 (17) [Mϩ Ϫ C13H26], 565 (12), 564 (25), 563
(25) [Mϩ Ϫ 2 ϫ C13H26], 418 (7), 417 (25), 416 (30) [Mϩ Ϫ 2 ϫ
C13H26 Ϫ C6H5NCO Ϫ CO], 399 (7). Ϫ C58H65N5O6 (928.2): calcd.
C 75.05, H 7.06, N 7.55; found C 74.84, H 7.26, N 7.49.
M. Zander, Chem. Ber. 1974, 107, 1406Ϫ1408.
M. Zander, Chem.-Ztg. 1975, 99, 92Ϫ93.
W. Seidenfaden, D. Pawellek, D. Houben-Weyl, Methoden der
Org. Chem. (Houben-Weyl) 4. Aufl. 1971, vol. 10/1, p. 488.
V. I. Rogovik, E. I. Shirokii, A. V. ElЈtsov, Zh. Org. Khim. 1980,
16, 867Ϫ872; J. Org. Chem. USSR (Enlg. Transl.) 1980, 16,
762Ϫ766.
J. I. G. Cadogan, M. Cameron-Wood, Proc. Chem. Soc. 1962,
361.
L. Feiler, H. Langhals, K. Polborn, Liebigs Ann. 1995,
1229Ϫ1244.
I. D. Entwistle, A. E. Jackson, R. A. W. Johnstone, R. T. Tel-
ford, J. Chem. Soc., Perkin Trans. 1 1977, 443Ϫ444.
N. A. Cortese, R. F. Heck, J. Org. Chem. 1977, 42, 3491Ϫ3494.
H. Kaiser, J. Lindner, H. Langhals, Chem. Ber. 1991, 124,
529Ϫ535.
[15]
[16]
[17]
[18]
[19]
[20]
Acknowledgments
This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie. We thank Prof. Grätzel
for the investigations with the TiO2 cell.
[21]
[22]
T. I. Solomentseva, V. I. Rogovik, T. A. Chibisova, V. F. TravenЈ,
B. I. Stepanov, Zh. Org. Khim. 1986, 22, 1050Ϫ1054; J. Org.
Chem. USSR (Engl. Transl.) 1986, 22, 943Ϫ946.
Free perylene-3,4:9,10-tetracarboxylic acid and its derivatives,
have been reported for this synthesis. It is more probable that
a ring closure to bis(anhydrides) proceeded under the reaction
conditions because of the instability of the free acid; compare
ref.[1]
[1]
H. Langhals, Heterocycles 1995, 40, 477Ϫ500.
[2]
H. Langhals, D.O.S. 3016764 (April 30, 1980); Chem. Abstr.
1982, 96, P70417x.
[3]
[23]
˚
H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991,
H. Langhals, J. Karolin, L. B.-A. Johansson, J. Chem. Soc.,
333, 733Ϫ748.
Faraday Trans. 1998, 94, 2919Ϫ2922.
[4]
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