Synthesis and spectral properties of 4-amino-and 4-acetylamino-N- arylnaphthalimides containing electron-donating groups in the N-aryl substituent

Article abstract of DOI:10.1007/s11172-009-0160-x

A method for the synthesis of N-aryl-substituted 4-amino-and 4-acetylaminonaphthalimide derivatives with mono-and dialkoxy groups or a 15-crown-5 moiety in the N-aryl substituent is described. The introduction of electron-donating alkoxy groups into the benzene ring of the N-aryl fragment results in fluorescence quenching of the naphthalimide chromophore, which is most pronounced in the spectra of N-acetyl derivatives. The photophysical properties of the synthesized 4-amino-and 4-acetylaminonaphthalimides depend on the solvent polarity and its specific solvating ability due to H-bonding. The crown-containing compounds are promising fluorescent chemosensors for metal cations. ; 2009 Springer Science+Business Media, Inc.

Full text of DOI:10.1007/s11172-009-0160-x

Russian Chemical Bulletin, International Edition, Vol. 58, No. 6, pp. 1233—1240, June, 2009
1233
Synthesis and spectral properties of
4ꢀaminoꢀ and 4ꢀacetylaminoꢀNꢀarylnaphthalimides
containing electronꢀdonating groups in the Nꢀaryl substituent
P. A. Panchenko,a Yu. V. Fedorov,a O. A. Fedorova,a V. P. Perevalov,b and G. Jonusauskasc
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: fedorova@ineos.ac.ru
bD. I. Mendeleev Russian University of Chemistry and Technology,
9 Miusskaya pl., 125047 Moscow, Russian Federation.
Fax: +7 (495) 609 29 64
cCentre de Physique Moléculaire Optique et Hertzienne (CPMOH),
Université Bordeaux 1, UMR CNRS 5798
351 Cours de la Libération, 33405 Talence, France
A method for the synthesis of Nꢀarylꢀsubstituted 4ꢀaminoꢀ and 4ꢀacetylaminonaphthalimide
derivatives with monoꢀ and dialkoxy groups or a 15ꢀcrownꢀ5 moiety in the Nꢀaryl substituent
is described. The introduction of electronꢀdonating alkoxy groups into the benzene ring of the
Nꢀaryl fragment results in fluorescence quenching of the naphthalimide chromophore, which
is most pronounced in the spectra of Nꢀacetyl derivatives. The photophysical properties of the
synthesized 4ꢀaminoꢀ and 4ꢀacetylaminonaphthalimides depend on the solvent polarity and its
specific solvating ability due to Hꢀbonding. The crownꢀcontaining compounds are promising
fluorescent chemosensors for metal cations.
Key words: naphthalimide, 15ꢀcrownꢀ5, fluorescence, hydrogen bond, UVꢀVis absorption
spectra, fluorescent sensors, 4ꢀnitronaphthalic anhydride, photoinduced charge transfer.
Organic luminophores on the base of naphthalimide
are of the great practical significance. They are used as
dyes for natural and synthetic fibers,1 optical brighteners,1
laser dyes,2 fluorescent dichroic dyes,3 reagents for lumiꢀ
nescent defectoscopy.1 Recently, on the base of naphthalꢀ
imides, electroluminescent materials known as integral
parts of the organic lightꢀemitting diodes have been
obtained.4—6 It was also found that some naphthalimide
derivatives possess antitumor activity due to their ability
to cause the photochemical cleavage of nucleic acids.7—10
The photophysical properties of naphthalimide
derivatives evoke strong interest of researchers not only
due to a variety of practical applications. Electronꢀdeficient
properties of the naphthalimide ring in the excited state
make these compounds appropriate models for studying
the processes of photoinduced electron transfer widespread
in nature.8,11 Based on naphthalimide, the systems where
electron excitation energy transfer can be realized were
obtained and studied.12—14 In most cases, naphthalimide
derivatives possess solvatochromism, which allows studies
of the effect of the solvent nature on spectral properties.
Owing to the fact that naphthalimide derivatives
are efficient luminophores, it seems very attractive to use
them as signaling elements for the construction of various
types of molecular devices. Thus, examples of fluorescent
sensors for cations and anions containing naphthalimide
residue are documented.15—33 Introduction of an ionoꢀ
phore into a naphthalimide derivative from the side of the
electronꢀdonating substituent R1 located in the position 4
of the naphthalene ring is the common feature in the
design of such sensors.
In the present work, a method for the synthesis of
4ꢀaminoꢀ and 4ꢀacetylaminonaphthalimide derivatives
containing a crownꢀether receptor in the Nꢀaryl fragment
R2 is developed. The known compounds where R2 is
phenyl or 4ꢀmethoxyphenyl group as well as previously
unknown benzodioxane derivatives (R2 is the benzoꢀ
dioxane residue) were synthesized for comparative analyꢀ
sis of the influence of the electronꢀdonating groups on the
spectral parameters.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1199—1206, June, 2009.
1066ꢀ5285/09/5806ꢀ1233 © 2009 Springer Science+Business Media, Inc.

1234
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
Panchenko et al.
Scheme 1
(conc.)
Yield of the products (%): 94 (4a), 88 (4b), 95 (4c), 67 (4d), 92 (5a), 87 (5b), 95 (5c), 94 (5d), 75 (6a), 86 (6b), 62 (6c), 74 (6d)
Synthesis. For the synthesis of naphthalimide derivaꢀ
tives, acenaphthene (1) produced in industrial scale from
coal tar34 was used as the starting compound. 4ꢀAminoꢀ
and 4ꢀacetylamino naphthalimide derivatives 5a—d and
6a—d were prepared according to Scheme 1.
Scheme 2
Nitration of acenaphthene (1) and subsequent oxidaꢀ
tion of 4ꢀnitro derivative 2 with sodium bichromate in
acetic acid resulted in 4ꢀnitrophthalic anhydride 3.35—37
The next steps involved conventional acylation of priꢀ
mary aromatic amines 7a—d with 4ꢀnitrophthalic anhyꢀ
dride (3), reduction of the nitro group in 4ꢀnitronaphthalꢀ
imides 4a—d, and acylation of amines 5a—d with acetic
anhydride according to common methods.38—40
6ꢀAminoꢀ2,3ꢀdihydrobenzo[b][1,4]ꢀdioxin (7c) was
prepared in three steps from catechol (8) using a known
procedure41 (Scheme 2).
i. Na2CO3, glycerol, Δ; ii. HNO3 (dilute), 60 °C; iii. N2H4, Ni, EtOH, Δ.
Crownꢀcontaining amine 7d in the form of hydroꢀ
chloride is commercially available. Free amine 7d was
generated in situ in the acylation with anhydride 3 by
addition of sodium acetate to the reaction mixture.
The structures of the compounds synthesized were
established based on the data from 1H NMR and UV
spectroscopy and confirmed by the data from elemental
analysis.
naphthalimides 5a—d and 6a—d is due to the charge transꢀ
fer from the electronꢀdonating amino or acylamino group
to the carbonyl groups of the carboximide fragment.1
Study of spectral properties. Longꢀwavelength band
in the absorption spectra of 4ꢀaminoꢀ and 4ꢀacetylaminoꢀ
R = H, Ac

NꢀArylꢀsubstituted naphthalimides
ελ•10–3
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
1235
I/Imax
a
b
1.0
35
30
6a
5a
0.8
0.6
0.4
6a
25
20
5a
15
10
5
0.2
250
300
350 400 450
500 550 λ/nm
350
400
450 500 550
600 650 λ/nm
Fig. 1. Absorption spectra (a) and fluorescence emission spectra (b) of compounds 5а and 6а in acetonitrile; С5a = 3.2•10–5 mol•L–1
С6a = 1.8•10–5 mol•L–1, λex = 365 nm.
,
between the Nꢀaryl fragment and the naphthalimide
moiety.
The absorption spectra of 4ꢀaminoꢀ and 4ꢀacetylꢀ
aminoꢀNꢀphenylnaphthalimides (5a and 6a) in acetoniꢀ
trile are shown in Fig. 1, a as an example.
The intensity of the fluorescence depends on the presꢀ
ence of the electronꢀdonating group in the benzene ring.
The introduction of one methoxy group into the phenyl
ring decreases the quantum yield of 4ꢀacetylaminoꢀ
Nꢀphenylnaphthalimide 6a from 0.85 to 0.030, and the
presence of two methoxy groups in compounds 6c,d
reduces the quantum yield to a few thousandths (Table 1).
In the series of amino derivatives, the annulation of
dioxane or crownꢀether moieties with the benzene ring
(compounds 5c,d) does not lead to such significant
changes, the quantum yield decreases only slightly.
Based on the analysis of the literature data,15—33 the
quenching of the fluorescence can probably be explained
by assuming that in the excited state S1 nonradiative
deactivation due to the charge transfer from the Nꢀaryl
substituent to the naphthalimide chromophore competes
with the fluorescence. The increase in the electronꢀ
donating properties of the Nꢀaryl residue due to the presꢀ
The replacement of the amino group in 5a by the
acetylamino group in 6a reduces the electronꢀdonating
properties of the nitrogen atom at the naphthalimide fragꢀ
ment resulting in a hypsochromic shift of the charge transꢀ
fer band by 50 nm in the absorption spectrum. The fluoꢀ
rescence spectra are also shifted hypsochromically
(Fig. 1, b). Thus, 4ꢀaminoꢀsubstituted compound 5a has
yellowꢀgreenish fluorescence, while 6a is a luminophore
with bluish fluorescence.
In the series of compounds 5a—d and 6a—d, the effect
of the nature of the Nꢀaryl substituent on spectralꢀfluoꢀ
rescence properties was analyzed. The fluorescence quanꢀ
tum yields and maxima in the absorption and emission
abs
spectra (λmax and λmaxfl) in acetonitrile are listed in
Table 1. The introduction of the electronꢀdonating groups
abs
in the benzene ring does not virtually change λmax and
λmaxfl. This observation allows assumption that in the
ground state only very weak πꢀelectron interaction exists
Scheme 3
Table 1. Spectral properties of 5a—d and 6a—d
in acetonitrile at 20 °C
abs
fl
fl
Comꢀ
pound
λ
λ
ϕ
max
max
nm
5a
5b
5c
5d
6a
6b
6c
6d
416
416
415
413
366
370
366
366
523
515
522
521
457
455
454
456
0.52
0.43
0.46
0.43
0.85
0.030
0.0048
0.0030
R = H, Ac
ED is an electronꢀdonating group

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
Panchenko et al.
ence of the alkoxy groups will increase the probability of
the nonradiative deactivation of the excited state S1 and
as a result, the fluorescence quantum yield will decrease
(Scheme 3).
The fluorescence spectra of all compounds mentioned
in Tables 2 and 3 always shift bathochromically with the
increase in the solvent polarity and its ability to form
hydrogen bonds. In all cases, the longestꢀwavelength fluoꢀ
rescence band were observed in water (~560 nm for the
4ꢀamino derivatives and ~480 nm for the 4ꢀacetylamino
derivatives). The shortestꢀwavelength fluorescence was
observed in diethyl ether (~500 nm for the 4ꢀamino
derivatives and ~440 nm for the 4ꢀacetylamino derivaꢀ
tives). It is also possible to assume that the excited state
formed upon charge transfer is less polar in the case of
Photophysical properties of the compounds syntheꢀ
sized depend considerably on the nature of the solvent.
The absorption and emission fluorescence spectra of
4ꢀaminoꢀ and 4ꢀacetylaminonaphthalimides 5a,c,d and
6a,c,d were recorded in eleven different solvents, includꢀ
ing five aprotic and six protic solvents. The Stokes shifts
(Δν), fluorescence quantum yields (ϕfl), and lifetime of the
excited states (τs) were also determined (Tables 2 and 3).
These data show that the increase in the solvent
polarity resulted in the increase in the Stokes shifts. This
suggests that the excited state S1 has a higher dipole
moment (compared with S0) and results from charge transꢀ
fer from the amino or acetylamino group in position 4 of
the naphthalene moiety to the carbonyl groups of the
imide residue.
acetylamines than for the amines, since in the latter the
fl
solvent change leads to larger changes in λmax
.
The position of the bands in the absorption spectra,
apparently, depends on two factors: the polarity of the
solvent and its capacity for hydrogen bonding. An
increase in the polarity leads to bathochromic shift of
the absorption band, but in contrast, the formation of the
hydrogen bond resulted in a short wavelength shift due to
Table 2. Absorption and fluorescence spectral data for 4ꢀaminonaphthalimides 5a—d in different solvents
at 20 °C
abs
fl
fl
Comꢀ
pound
Solvent (ε)
λ
λ
(λ
)
Δν
ϕ
τ
s
/ns
max
max
exc
/nm (lgελ)
/nm
/cm–1
5a
5c
5d
Propylene carbonate (65.0)
Dimethyl sulfoxide (46.5)
Acetonitrile (36.0)
Dimethoxyethane (7.2)
Diethyl ether(4.2)
Water (78.4)
Methanol (32.6)
Ethanol (24.5)
nꢀButanol (17.5)
nꢀHeptanol (11.1)
nꢀDecanol (7.2)
Propylene carbonate (65.0)
Dimethyl sulfoxide (46.5)
Acetonitrile (36.0)
Dimethoxyethane (7.2)
Diethyl ether (4.2)
Water (78.4)
Methanol (32.6)
Ethanol (24.5)
nꢀButanol (17.5)
nꢀHeptanol (11.1)
nꢀDecanol (7.2)
Propylene carbonate (65.0)
Dimethyl sulfoxide (46.5)
Acetonitrile (36.0)
Dimethoxyethane (7.2)
Diethyl ether (4.2)
Water (78.4)
Methanol (32.6)
Ethanol (24.5)
nꢀButanol (17.5)
nꢀHeptanol (11.1)
nꢀDecanol (7.2)
421 (4.15)
437 (4.14)
416 (4.03)
419 (4.14)
413 (4.12)
434 (4.13)
434 (4.19)
437 (4.15)
439 (4.18)
438 (4.23)
437 (4.18)
418 (4.22)
436 (4.19)
415 (4.24)
418 (4.19)
411 (4.18)
433 (3.90)
433 (4.27)
436 (4.22)
438 (4.23)
437 (4.22)
435 (4.19)
418 (4.22)
436 (4.19)
413 (4.23)
417 (4.19)
411 (3.65)
431 (4.22)
432 (4.24)
435 (4.41)
438 (4.28)
437 (4.20)
435 (4.21)
531 (420)
4921
4330
4918
4487
4253
5184
4659
4296
4157
4104
4051
4912
4383
4939
4430
4331
5174
4645
4314
4174
4086
4085
4876
4383
5019
4450
4291
5249
4698
4367
4174
4086
4121
0.50
0.46
0.52
0.47
0.50
0.091
0.30
0.39
0.43
0.50
0.52
0.52
0.52
0.46
0.49
0.55
0.09
0.29
0.40
0.44
0.48
0.51
0.49
0.50
0.43
0.47
0.54
0.089
0.28
0.35
0.40
0.46
0.47
9.9
9.2
9.5
9.4
9.8
2.8
4.0
7.5
8.0
8.6
8.9
9.6
9.0
9.4
9.1
9.6
2.8
6.1
7.4
7.8
8.6
8.8
9.2
8.8
9.0
8.9
9.7
2.7
6.0
7.3
7.7
8.4
8.8
539 (440)
523 (415)
516 (420)
501 (415)
560 (430)
544 (430)
538 (430)
537 (430)
534 (410)
531 (410)
526 (420)
539 (430)
522 (415)
513 (420)
500 (430)
558 (430)
542 (430)
537 (430)
536 (430)
532 (430)
529 (430)
525 (420)
539 (430)
521 (415)
512 (420)
499 (420)
557 (430)
542 (430)
537 (430)
536 (430)
532 (420)
530 (420)

NꢀArylꢀsubstituted naphthalimides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
1237
Table 3. Absorption and fluorescence spectral data for 4ꢀaminonaphthalimides 6a—d in different solvents at 20 °C
abs
fl
fl
Comꢀ
pound
Solvent (ε)
λ
λ
(λ
)
Δν
ϕ
τ *
max
max
exc
s
/nm (lgελ)
/nm
/cm–1
6a
6c
6d
Propylene carbonate (65.0)
Dimethyl sulfoxide (46.5)
Acetonitrile (36.0)
Dimethoxyethane (7.2)
Diethyl ether (4.2)
Water (78.4)
Methanol (32.6)
Ethanol (24.5)
nꢀButanol (17.5)
nꢀHeptanol (11.1)
nꢀDecanol (7.2)
Propylene carbonate (65.0)
Dimethyl sulfoxide (46.5)
Acetonitrile (36.0)
Dimethoxyethane(7.2)
Diethyl ether (4.2)
Water (78.4)
Methanol (32.6)
Ethanol (24.5)
nꢀButanol (17.5)
nꢀHeptanol (11.1)
nꢀDecanol (7.2)
Propylene carbonate (65.0)
Dimethyl sulfoxide (46.5)
Acetonitrile (36.0)
Dimethoxyethane (7.2)
Diethyl ether (4.2)
Water (78.4)
Methanol (32.6)
Ethanol (24.5)
nꢀButanol (17.5)
nꢀHeptanol (11.1)
nꢀDecanol (7.2)
369 (4.32)
371 (4.32)
366 (4.27)
369 (4.34)
368 (4.32)
356 (4.35)
364 (4.33)
366 (4.37)
369 (4.41)
371 (4.37)
372 (4.33)
368 (4.20)
371 (4.21)
366 (4.23)
369 (4.25)
368 (4.23)
356 (4.19)
363 (4.22)
366 (4.23)
368 (4.29)
371 (4.19)
371 (4.19)
368 (4.20)
371 (4.18)
366 (4.24)
369 (4.24)
368 (3.72)
356 (4.26)
363 (4.16)
366 (4.17)
369 (4.21)
370 (4.20)
371 (4.21)
460 (330)
460 (330)
457 (330)
449 (330)
440 (330)
482 (320)
473 (320)
467 (320)
465 (320)
462 (320)
460 (320)
456 (370)
465 (370)
454 (360)
446 (370)
439 (370)
480 (360)
470 (360)
461 (360)
458 (360)
454 (370)
453 (370)
457 (370)
464 (370)
456 (365)
448 (370)
441 (370)
481 (360)
469 (360)
462 (365)
460 (370)
456 (370)
455 (370)
5361
5215
5441
4829
4447
7343
6331
5909
5595
5309
5143
5244
5449
5296
4679
4395
7257
6272
5630
5340
4928
4879
5292
5402
5393
4779
4498
7300
6226
5677
5361
5097
4976
0.75
0.69
0.85
0.69
0.67
0.73
0.77
0.66
6.3
3.6
6.5
5.9
6.1
6.8
7.0
6.7
6.3
6.2
6.2
0.81
0.75
0.76
0.012
0.0072
0.0048
0.0020
0.0018
0.0030
0.0032
0.0026
0.0030
0.0049
0.0085
0.0096
0.0041
0.0030
0.0013
0.0016
0.0017
0.0025
0.0023
0.0057
0.0099
0.0075
90
78
61
35
35
52
65
75
40
54
100
48
65
27
19
19
30
32
27
21
27
30
* For compound 6a lifetime value τ is given in ns, for compound 6c,d — in ps.
s
abs
specific solvation of the polar ground state. Thus in the
series of aprotic solvents, diethyl ether (ε = 4.2) —
dimethoxyethane (ε = 7.2) — acetonitrile (ε = 36.0) —
propylene carbonate (ε = 65.0), longꢀwavelength bands
in the absorption spectra of the 4ꢀaminoꢀ and the
4ꢀacetylamino derivatives undergo a bathochromic
shift. The different pattern is observed in protic solvents.
the increase in the solvent polarity, instead λmax shifts
hypsochromically. Apparently, the solvent polarity is of
less importance for the acetylamino derivatives as their
molecules possess smaller dipole moments.
It should be noted that in DMSO, unlike other aprotic
solvents, the absorption spectra of amines and acetylꢀ
amines are observed in an abnormally longꢀwavelength
region. Apparently, this could be explained by specific
solvation due to hydrogen bonding between the hydrogen
atoms of the amino or acetylamino groups and the oxygen
atoms of the DMSO molecules bearing relatively high
partial negative charge.
Determination of the fluorescence quantum yields in
the aprotic solvents shows that the change in the solvent
influences the quantum yield of the compounds, but no
clear pattern could be established. In the protic solvents,
a tendency was noted for decreasing the fluorescence
quantum yield and lifetime of the excited state of 4ꢀaminoꢀ
naphthalimides with increasing the ability of the solvent
abs
In the case of the 4ꢀamino derivatives, λmax shifts
bathochromically on going from decanol to butanol (the
solvent polarity is the critical factor). On going from buꢀ
abs
tanol to methanol, λmax undergoes hypsochromic shifts
(the ability of the solvent to form hydrogen bonds begins
dominate). The absorption spectrum of the amino derivaꢀ
tives in water is almost in the same position as in methaꢀ
nol. The latter is likely due to the fact that on going from
methanol to water not only polarity of the solvent, but
also its ability to specific solvation increase dramatically.
abs
No initial increase in λmax of 4ꢀacetylamines in the
series of solvents from decanol to water is observed with

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Panchenko et al.
fl
ethanol (ϕ = 0.95)43 as standards. The fluorescence quantum
for hydrogen bonding. This regularity is not observed in
the series of 4ꢀNꢀacyl derivatives (Tables 2 and 3).
yields were calculated by Equation (1)44
Thus, we synthesized naphthalimide derivatives conꢀ
taining monoalkoxy and dialkoxy groups and a 15ꢀcrownꢀ5
moiety in the Nꢀaryl substituent. It was found that the
introduction of an electronꢀdonating substituent into
the Nꢀphenyl ring leads to quenching of fluorescence
in the series of 4ꢀamino and 4ꢀacetylaminonaphthalimides
caused by redistribution of the charge in the excited state
between the naphthalimide chromophore (acceptor) and
the Nꢀaryl moiety (donor). It was also found that the
substituents in the benzene ring do not affect the position
of the longꢀwavelength band in the absorption spectra,
which suggests certain independence of the πꢀsystems of
the naphthalimide residue and the Nꢀaryl moiety in the
ground state. The influence of the nature of the solvent
on spectral properties of the series of the synthesized
compounds was analyzed.
The observed effect of the fluorescence quenching
caused by the introduction of the crownꢀether moiety
into the Nꢀphenyl ring of 4ꢀamino and 4ꢀacetylaminoꢀ
naphthalimides suggests the existence of sensor properties
of the corresponding crown ether derivatives with respect
to metal cations. For this type of compounds, one should
expect the fluorescence enhancement upon cation binding
by the crownꢀether moiety since the complex formation
decreases electronꢀdonating properties of the oxygen
atoms at the benzene rings. Study of the complexation
in the series of crown etherꢀcontaining naphthalimide
derivatives will be the subject of our further research.
(1)
,
where ϕifl and ϕ fl are quantum yields of analytical and standard
0
samples, respectively, Di and D0 are absorbance of the analytical
and standard samples, respectively, Si and S0 are areas under the
curves of the fluorescence spectra for analytical and standard
samples, respectively, ni and n0 are refractive indices for analytiꢀ
cal and standard samples, respectively.
The solvents of the spectrophotometric grade (Aldrich,
Acros) were used for the spectroscopic studies as purchased.
The timeꢀresolved fluorescence spectra were measured
on a Chromex 250 spectrograph coupled to a streak camera
Hamamatsu 5680 equipped with a fast sweep unit M5676 with
temporal resolution of 2 ps. Excitation pulses were generated by
optical parametric generator pumped by fundamental beam
derived from a femtosecond laser Tiꢀsapphire Femtopower
Compact Pro. All excited state lifetimes were obtained using
a depolarized excitation light. The highest pulse energy of
fluorescence excitation did not exceed 100 nJ, average power
of an excitation beam was 0.1 mW at a pulse repetition rate of
1 kHz focused into a spot with a diameter 0.1 mm in the 10 mm
long fused quartz cell. The fluorescence kinetics were later fitted
by the LevenbergꢀMarquardt leastꢀsquare curveꢀfitting method
using a solutions of the differential equations describing the
evolution in time of a single excited state and neglecting
depopulation of the ground state:
dI/dt = Gauss(t0,Δt,A) – I(t)/τ,
where I(t) is fluorescence intensity, τ is lifetime of the excited
state, Gauss is the Gauss profile of the excitation pulse, t0 is time
position of its maximum, Δt is the pulse width, A is the pulse
amplitude. Initial conditions: I(—∞) = 0. Typically, the fit shows
Experimental
a χ value better than 10–4 and a correlation coefficient
2
1Н NMR spectra were recorded on a VarianꢀXRꢀ400 spectroꢀ
meter (400 MHz) in deuteriated chloroform, pyridine, DMSO,
and acetonitrile. Chemical shifts were determined relative to
hexamethyldisiloxane with accuracy of 0.01 ppm, the coupling
constants with accuracy of 0.1 Hz. The assignment of the proton
signals Н(2), Н(3), Н(5), and Н(7) for compounds 4c,d, 5c,d,
and 6b—d is based on theoretical calculations that were made
using ACD/Labs 6.0 program package.
R > 0.999. The uncertainty of the lifetime was better than 1%.
Routinely, the fluorescence accumulation time in our measureꢀ
ments did not exceed 90 s.
Compounds 236, 337, 4a38, 4b38, 5a39, 5b39, 6a40, 7c41, 841
,
941 were synthesized according to the known methods. The
structures of the compounds were confirmed by coincidence of
the melting points with the literature data.
Acylation of amines 7a—d with 4ꢀnitronaphthalic anhydride.
(general procedure).38 To a suspension of 4ꢀnitronaphthalic
anhydride (3) (6.00 g, 25.0 mmol) in glacial acetic acid (75 mL),
the corresponding amine (50.0 mmol) was added and the mixture
was refluxed for 1.5 h. The crystalline product was filtered off,
washed on a filter with 5% hydrochloric acid, hot 10% aqueous
Na2CO3, distilled water, and ethanol. The product was dried
at 80 °C.
2ꢀ(2,3ꢀDihydrobenzo[b][1,4]dioxinꢀ6ꢀyl)ꢀ6ꢀnitroꢀ
2,3ꢀdihydrobenzo[d,e]isoquinolineꢀ1,3(1Н)ꢀdione (4c). Comꢀ
pound 4c were prepared using the general procedure from 3
(1.60 g) and 6ꢀaminoꢀ2,3ꢀdihydrobenzo[b][1,4]dioxin 7c
(2.00 g) in glacial acetic acid (15 mL) in a yield of 2.36 g (95%),
m.p. 300—302 °C. 1H NMR (DMSOꢀd6), δ: 4.28 (br.s, 4 Н,
–СH2–СH2–); 6.82 (dd, 1 Н, Н(14), J = 8.3 Hz, J = 2.2 Hz);
6.93 (d, 1 Н, Н(10), J = 2.2 Hz); 6.96 (d, 1 Н, Н(13),
J = 8.3 Hz); 8.06—8.12 (m, 1 Н, Н(6)); 8.52—8.59 (m, 2 Н,
Н(2), Н(3)); 8.60 (d, 1 Н, Н(7), J = 7.3 Hz); 8.72 (d, 1 Н, Н(5),
Melting points were determined in open capillaries and are
uncorrected.
Elemental analysis was carried out at the Laboratory of
physicochemical methods of analysis of the Department
of Chemistry, the M.V. Lomonosov Moscow State University.
Thinꢀlayer chromatography was performed on precoated
plates Sorbfil UVꢀ254 in benzene—ethanol or chloroform solvent
systems. Silica gel 60 (Fluka) was used for column chromatoꢀ
graphy.
The absorption spectra were measured on a VarianꢀCary
spectrophotometer. The fluorescence spectra were measured on
a FluoroMaxꢀ3 spectrofluorimeter. The observed fluorescence
was recorded at a right angle to the excitation beam. All measured
fluorescence spectra were corrected for the nonꢀuniformity of
detector spectral sensitivity. The fluorescence quantum yields
were determined in aerated solutions at 20 1 °C using quinine
fl
sulfate in 1 N sulfuric acid (ϕ = 0.55)42 and Rodamine 6G in

NꢀArylꢀsubstituted naphthalimides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 6, June, 2009
1239
J = 8.6 Hz). Found (%): С, 63.73; Н, 3.05; N, 7.44. C20H12N2O6.
Calculated (%): С, 63.83; Н, 3.21; N, 7.44.
Nꢀ(2ꢀ(4ꢀMethoxyphenyl)ꢀ1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Нꢀbenzoꢀ
[d,e]isoquinolinꢀ6ꢀyl)acetamide (6b). Compound 6b was prepared
according to the general procedure from 4ꢀaminoꢀNꢀ(4ꢀmethoxyꢀ
phenyl)naphthalimide (5b) (1.26 g) and acetic anhydride
(5.0 mL) in a yield of 1.23 g (86%), m.p. 334—337 °C. 1Н NMR
(Руꢀd5) δ: 3.49 (s, 3 H, CH3CO—); 4.72 (s, 3 H, —OCH3);
8.15—8.19 (m, 2 H, H(11), H(13)); 8.57—8.61 (m, 2 H, H(10),
H(14)); 8.70 (dd, 1 H, H(6), J = 7.3 Hz, J = 8.6 Hz); 9.65 (d,
1 H, H(3), J = 8.1 Hz); 9.72 (dd, 1 H, H(7), J = 1.0 Hz,
J = 7.3 Hz); 9.78 (d, 1 H, H(2), J = 8.1 Hz); 9.83 (dd, 1 H,
H(5), J = 1.0 Hz, J = 8.6 Hz); 12.11 (br.s, 1 H, —NH—CO—).
UV (MeCN), λmax/nm (log ε): 365 (4.60). Found (%): С, 69.96;
Н, 4.42; N, 7.84. C21H16N2O4. Calculated (%): С, 69.99; Н, 4.48;
N, 7.77.
Nꢀ[2ꢀ(2,3ꢀDihydrobenzo[b][1,4]dioxinꢀ6ꢀyl)ꢀ1,3ꢀdioxoꢀ
2,3ꢀdihydroꢀ1Нꢀbenzo[d,e]isoquinolinꢀ6ꢀyl]acetamide (6c) was
prepared according to the general procedure from 4ꢀaminoꢀ
naphthalimide 5c (0.50 g) and acetic anhydride (1.8 mL) in a
yield of 0.35 g (62 %), m.p. 310—313 °C. 1Н NMR (DMSOꢀd6)
δ: 2.30 (s, 3 H, CH3CO—); 4.32 (br.s, 4 H, —CH2—CH2—);
6.81 (dd, 1 H, H(14), J = 2.3 Hz, J = 8.3 Hz); 6.90 (d, 1 H,
H(10), J = 2.3 Hz); 6.96 (d, 1 H, H(13), J = 8.3 Hz); 7.91 (dd,
1 H, H(6), J = 7.3 Hz, J = 8.6 Hz); 8.33 (d, 1 H, H(3), J = 8.3 Hz);
8.48 (d, 1 H, H(2), J = 8.3 Hz); 8.53 (dd, 1 H, H(7), J = 0.8 Hz,
J = 7.3 Hz); 8.74 (dd, 1 H, H(5), J = 0.8 Hz, J = 8.6 Hz); 10.32
(br.s, 1 H, —NH—CO—). Found (%): С, 68.11; Н, 4.10;
N, 7.46. C22H16N2O5. Calculated (%): С, 68.04; Н, 4.15; N, 7.21.
Nꢀ[2ꢀ(1,4,7,10,13ꢀPentaoxaꢀ2,3,5,6,8,9,11,12ꢀoctahydroꢀ
benzo[b]cyclopentadecynꢀ15ꢀyl)ꢀ1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Нꢀ
benzo[d,e]isoquinolinꢀ6ꢀyl]acetamide (6d). Compound 6d was
prepared by the general procedure from 4ꢀaminonaphthalimide
5d (0.15 g) and acetic anhydride (0.5 mL) in a yield of 0.12 g
(74 %), m.p. 308—311 °C. 1Н NMR (DMSOꢀd6) δ: 2.31 (s, 3 H,
CH3CO—); 3.61—3.71 (m, 8 H, C(17)H2, C(18)H2, C(19)H2,
C(20)H2); 3.75—3.81 (m, 2 H, C(16)H2); 3.81—3.87 (m, 2 H,
C(21)H2); 4.01—4.09 (m, 2 H, C(15)H2); 4.12—4.19 (m, 2 H,
C(22)H2); 6.89 (dd, 1 H, H(14), J = 2.3 Hz, J = 8.3 Hz); 7.00
(d, 1 H, H(10), J = 2.3 Hz); 7.07 (d, 1 H, H(13), J = 8.3 Hz);
7.88—7.95 (m, 1 H, H(6)); 8.33 (d, 1 H, H(3), J = 8.3 Hz); 8.49
(d, 1 H, H(2), J = 8.3 Hz); 8.54 (d, 1 H, H(7), J = 7.3 Hz);
8.75 (d, 1 H, H(5), J = 8.6 Hz); 10.33 (br.s, 1 H, —NH—CO—).
Found (%): С, 64.61; Н, 5.27; N, 5.42. C28H28N2O8. Calcuꢀ
lated (%): С, 64.61; Н, 5.42; N, 5.38.
6ꢀNitroꢀ2ꢀ(1,4,7,10,13ꢀpentaoxaꢀ2,3,5,6,8,9,11,12ꢀoctaꢀ
hydrobenzo[b]cyclopentadecynꢀ15ꢀyl)ꢀ2,3ꢀdihydrobenzo[d,e]ꢀ
isoquinolineꢀ1,3(1Н)ꢀdione (4d). Nitro derivative 4d was prepared
according to the general procedure form 4ꢀnitronaphtalic
anhydride 3 (0.38 g), amine hydrochloride 7d (1.00 g) and sodium
acetate (0.28 g) in glacial acetic acid (15 mL) in a yield of 0.53 g
(67%), m.p. 258—261 °C. 1Н NMR(Руꢀd5), δ: 4.77—4.93 (m,
12 H, C(16)H2, C(17)H2, C(18)H2, C(19)H2, C(20)H2, C(21)H2);
5.17—5.21 (m 4 H, C(15)H2, C(22)H2); 8.16 (d, 1 H, H(13),
J = 8.3 Hz); 8.28 (dd, 1 H, H(14), J = 2.3 Hz, J = 8.3 Hz); 8.39
(d, 1 H, H(10), J = 2.3 Hz); 8.96 (dd, 1 H, H(6), J = 7.3 Hz,
J = 8.6 Hz); 9.54 (d, 1 H, H(3), J = 8.1 Hz); 9.79 (d, 1 H,
H(2), J = 8.1 Hz); 9.82 (d, 1 H, H(7), J = 8.6 Hz); 9.83 (d,
1 H, H(5), J = 8.6 Hz). Found (%): С, 61.47; Н, 4.72; N, 5.41.
C26H24N2O9. Calculated (%): С, 61.41; Н, 4.76; N, 5.51.
Reduction of 4ꢀnitronaphtalimide derivatives (general proceꢀ
dure).39 To a suspension of a 4ꢀnitronaphthaliminde derivative
(4.0 mmol) in ethanol (20 mL) a solution of SnCl2•2H2O
(6.45 g) in concentrated HCl (5 mL, ρ 1.18 g•mL–1) was added
dropwise with stirring at 50 °C. The mixture was refluxed for
1.5 h. The reaction mixture was poured into water (50 mL), the
precipitate that formed was filtered off, washed with water, 1%
aqueous NaOH (for the removal of tin), then with water and
ethanol. The product was dried at 80 °C.
6ꢀAminoꢀ2ꢀ(2,3ꢀdihydrobenzo[b][1,4]dioxinꢀ6ꢀyl)ꢀ
2,3ꢀdihydrobenzo[d,e]isoquinolineꢀ1,3(1Н)ꢀdione (5c) was preꢀ
pared according to the general procedure from nitro derivative
4c (2.36 g) and SnCl2•2H2O (10.16 g) in concentrated HCl
(7.5 mL) to give compound 5c in the yield of 2.07 g (95%),
m.p. 350—352 °C. 1H NMR (DMSOꢀd6), δ: 4.30 (br.s, 4 Н,
–СH2–СH2–); 6.73 (dd, 1 H, H(14), J = 8.3 Hz, J = 2.3 Hz);
6.82 (d, 1 H, H(10), J = 2.3 Hz); 6.87 (d, 1 H, H(13), J = 8.3 Hz);
6.94 (d, 1 H, H(3), J = 8.6 Hz); 7.43 (br.s, 2 H, NH2); 7.63—7.71
(m, 1 H, H(6)); 8.18 (d, 1 H, H(2), J = 8.6 Hz); 8.42 (d, 1 H,
H(7), J = 7.3 Hz); 8.65 (d, 1 H, H(5), J = 8.3 Hz). Found (%):
С, 69.32; Н, 3.92; N, 8.09. C20H14N2O4. Calculated (%):
С, 69.36; Н, 4.07; N, 8.09.
6ꢀAminoꢀ2ꢀ(1,4,7,10,13)ꢀpentaoxaꢀ2,3,5,6,8,9,11,12ꢀoctaꢀ
hydrobenzo[b]cyclopentadecynꢀ15ꢀyl)ꢀ2,3ꢀdihydrobenzo[d,e]ꢀ
isoquinolineꢀ1,3(1Н)ꢀdione (5d). Compound 5d was obtained
according to the general procedure from nitro derivative 4d
(0.53 g) and SnCl2•2H2O (1.68 g) in concentrated HCl
(1.2 mL) in a yield of 0.47 g (94%), m.p. 308—311 °C. 1H NMR
(DMSOꢀd6), δ: 3.61—3.71 (m, 8 H, C(17)H2, C(18)H2, C(19)H2,
C(20)H2); 3.75—3.81 (m, 2 H, C(16)H2); 3.81—3.86 (m, 2 Н,
C(21)H2); 4.02—4.08 (m, 2 H, C(15)H2); 4.12—4.18 (m, 2 H,
C(22)H2); 6.81 (dd, 1 H, H(14), J = 8.3 Hz, J = 2.3 Hz); 6.90
(d, 1 H, H(3), J = 8.6 Hz); 6.92 (d, 1 H, H(10), J = 2.3 Hz);
7.04 (d, 1 H, H(13), J = 8.3 Hz); 7.32 (br.s, 2 H, NH2);
7.65—7.71 (m, 1 H, H(6)); 8.20 (d, 1 H, H(2), J = 8.6 Hz); 8.44
(d, 1 H, H(7), J = 7.3 Hz); 8.65 (d, 1 H, H(5), J = 8.3 Hz).
Found (%): С, 65.39; H, 5.34; N, 5.85. C26H26N2O7. Calcuꢀ
lated (%): С, 65.26; Н, 5.48; N, 5.85.
This work was financially supported by the Russian
Foundation for Basic Research (Project 09ꢀ03ꢀ93116) and
National Center for Scientific Research (CNRS program
PICS 3904).
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Received November 27, 2008