Reaction of hexafl uoro-N-(4-N,N-dialkylaminophenyl)- 1,4-naphthoquinon-4- imines with primary amines

Article abstract of DOI:10.1134/S1070428013110092

Amination of 2,3,5,6,7,8-hexafl uoro-N-(4-N,N-dialkylaminophenyl)-1,4- naphthoquinon-4-imines with primary amines led to the formation of 3-amino derivatives, which further underwent cyclization into 7-alkyl(aryl)- 1,2,3,4,6-pentafl uoro-5H-benzo[a]phenazin-5-ones. The spectral properties of compounds obtained were examined. Pleiades Publishing, Ltd., 2013.

Full text of DOI:10.1134/S1070428013110092

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1617−1622. © Pleiades Publishing, Ltd., 2013.
Original English Text © L.V. Ektova, A.D. Bukhtoyarova, I.P. Chuikov, I.V. Beregovaya, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49,
No. 11, pp. 1638−1643.
Reaction of Hexafluoro-N-(4-N,N-Dialkylaminophenyl)-
1,4-naphthoquinon-4-imines with Primary Amines
L. V. Ektova, A. D. Bukhtoyarova, I. P. Chuikov, and I. V. Beregovaya
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences,
Novosibirsk, 630090 Russia
е-mail: bad@nioch.nsc.ru
Received February 11, 2013
Abstract—Amination of 2,3,5,6,7,8-hexafluoro-N-(4-N,N-dialkylaminophenyl)-1,4-naphthoquinon-4-imines with
primary amines led to the formation of 3-amino derivatives, which further underwent cyclization into 7-alkyl(aryl)-
1,2,3,4,6-pentafluoro-5Н-benzo[а]phenazin-5-ones. The spectral properties of compounds obtained were examined.
DOI: 10.1134/S1070428013110092
The oxidative amination of N-aryl-1,4-naphthoquinon-
4-imine is known to proceed [1, 2] with the introduction
of the amino group into the position 2. The arising
2-aryl(alkyl)amino derivatives of naphthoquinonimines
exhibits a high tuberculocidal activity [2]. It was also
shown [3] that 2,5-diarylamino-N-aryl-1,4-benzoqui-
nonimines enter into the reaction of oxidative heterocy-
clization, and therewith the arylamino group located in
the ortho-position to the carbonyl group undergoes the
cyclization into a phenoxazinonimine derivative, and the
arylamino group in the ortho-position to the C=N group
is involved in the formation of phenazinone derivative.
The derivatives of phenazinones and phenoxazinonones
possess a strong fluorescence [4].
rivatives of N-aryl-1,4-naphthoquinon-4-imines Iа, Ib.
Taking into account the high nucleophilic lability of
fluorine atoms in quinone derivatives (see, e.g., [6]), it
was expectable that the reactions of compounds Iа, Ib
provide a possibility of their further functionalization.
In this study we investigated the products of reactions of
naphthoquinonimines 2,3,5,6,7,8-hexafluoro derivatives
Iа, Ib with primary aromatic and aliphatic amines.
In contrast to the nonfluorinated analogs quinonimines
Iа, Ib react with the 4-substituted aniline derivatives
and also with n-butylamine at maintaining for a short
time (3–5 h) in organic solvent (ethanol, DMF) at room
temperature with the formation of two substances. One
among them is the product of a replacement of a fluorine
atom in the position 3 of the quinone fragment of the
We formerly [5] synthesized polyfluorinated de-
F
F
F
O
N
F
F
O
2
F
F
F
F
F
F
F
3
NH2R,
Et3N
F
F
F
1
12
N
11
8
4
+
10
NHR
5
7
N
9
Alk2N
O
6
N
NAlk2
NAlk2
R
F
IIIа_IIIe
IIа_IIe
Iа, Ib
I, Alk = Me (a), Et (b); II, III, Alk = Me, R = 4-Me2NC6H4 (a), 4-CH3OC6H4 (b), C4H9 (c); Alk = Et, R = 4-Et2NC6H4 (d), C4H9 (e).
1617

EKTOVA et al.
1618
contain two sets of signals indicating the existence of a
dynamic equilibrium between Z- and E-isomers [5], the
19F NMR spectra of all 3-amino substituted pentafluoro-
4-(4-N,N-dialkylaminophenyl)-1,4-naphthoquinon-4-
imines IIа–IIe contain only the signals of a single spatial
isomer. Therewith the signal of F2 atom is observed as a
broadened singlet in the range 13–16 ppm for 3-arylamino
derivatives IIа, IIb, IId and at –1.6 and –1.8 ppm for
3-butylamino derivatives IIc, IIe. The signals of fluorine
atoms of the tetrafluororbenzene ring are multiplets at
22 ppm for F8 and 11–12 ppm for the atoms F6 and F7. The
chemical shift of the atom F5 in the 19F NMR spectra of
these compounds is shifted downfield to 39 ppm and it is
located in the same region as the shift of the corresponding
atom in the Е-isomers of initial compounds Ia, Ib suggest-
ing that in compounds IIa, IIb the substituent at the imine
nitrogen atom is directed to the tetrafluorobenzene ring.
Same as in the spectra of compounds Ia, Ib no coupling
was observed here between the atom F5 and Н2', Н6' of
the 4-dialkylaminophenyl group. Therefore we examined
compound IIc for the presence of the nuclear Overhauser
effect in the 1Н NMR spectrum at the selective irradiarion
of the fluorine atoms. Weak positive effects were found
for atoms Н2', Н6' of the 4-dimethylaminophenyl group
at the irradiation of the atom F5, for the atom Н1 of the
butyl group, at the irradiation of the atom F2. This result
confirms the spatial proximity of these nuclei.
molecule for the amino group (compounds IIа–IIe), the
second one, the corresponding 1,2,3,4,6-pentafluoro-7-
R-5Н-benzo[a]phenazin-5-one IIIа–IIIe. It was shown
by a special experiment that compound IIe under the
reaction conditions is transformed into benzophenazine
IIIe. Therefore the benzophenazines are the cyclization
products of N-arylnaphthoquinonimines IIа–IIe.
The cyclization apparently proceeds through an intra-
molecular attack of the ortho-position of the hydrocarbon
aromatic ring of N-arylnaphthoquinonimines IIа–IIe
with the spatially close amine residue followed by the
oxidation of the air oxygen. A similar mechanism was
formerly suggested for the formation of 2-arylamino-5-
arylphenazin-3-ones at the oxidation of N-phenyl-2,5-
diarylamino-1,4-benzoquinonimines [7].
The structure of compounds obtained was established
using the combination of the spectral data. In the high
resolution mass spectra the intensive peaks of molecular
ions were registered, whose m/z values corresponded
to calculated ones. IR spectra of compounds IIа–IIe,
IIIа–IIIe contained in the region 1550–1650 cm–1 the
absorption bands of the stretching vibrations of the C=O
and C=N groups, and in the spectra of compounds IIа–IIe
an absorption band characteristic of the NH group was
additionally present.
Chemical shifts and spin-spin coupling constants
1
19
in the H and F NMR spectra of compounds IIа–IIe,
IIIа–IIIe are in agreement with the assumed structures.
In the 19F NMR spectra of 1,2,3,4,6-pentafluorobenzo
phenazinones IIIc, IIIe the chemical shifts of the F of
the polyfluorinated benzene ring and of F6 are close in
values to those in the spectrum of 1,2,3,4,6-pentafluoro-
9-diethylamino-5Н-benzo[a]phenoxazin-5-one [8]. The
assignment of the signals in the 19F NMR spectra was
performed based on the analysis of coupling constants
typical for polyfluorinated benzenes and analogous to
those observed in the spectra of unsubstituted imines Iа,
Ib [5]. The location of the amine substituent in the posi-
tion 3 of compounds IIа–IIe, which follows from the
conversion of IIа–IIe into IIIа–IIIe, was confirmed by an
example of compound IIe using 13С NMR spectroscopy.
For instance, in the 13С NMR spectrum of compound
In order to interpret the experimental results on the
regioselectvity of the amination of compounds Ia, Ib we
carried out quantum-chemical calculations by the density
functional method. Assuming that the reaction proceeds
through the intermediate formation of σ-complexes we
considered the complexes formed by compound Ia with
a model nucleophile, ammonia molecule. In the PBE/3z
approximation that we had previously [5] applied to the
calculation of this class compounds we failed to obtain
σ-complexes corresponding to the addition at the posi-
tion 2. Therefore, we performed the calculations in the
approximation CAMB3LYP/6-31G*. The total and rela-
tive (with respect to the most stable complex) energies of
the localized σ-complexes are compiled in Table 1. The
digit in the notations corresponds to the position of the
substitution, and the letter corresponds to the position of
the substituent at the C=N bond. The higher stability of
the σ-complexes 3Е and 3Z compared with 2E and 2Z
may govern the proceeding of the reaction at the position
3 of compounds Ia, Ib. The higher stability of 3Е than 3Z
suggests that the prevailing conformation of the product
IIe the signal of the atom С1 appears as a doublet with
2
the constant 2JC F 18 Hz characteristic of JCF [9]. The
identification of this constant was proved by an experi-
ment with its selective decoupling.
1
2
Unlike initial compounds Iа, Ib whose 19F
NMR
spectra at room temperature and especially at cooling
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

REACTION OF HEXAFLUORO-N-(4-N,N-DIALKYLAMINOPHENYL)-...
1619
1
Table 1. Total Etot (а.u.) and relative ΔE (kcal mol− ) energies of
σ-complexes of quinonimine Iа with NH3
compounds IIа–IIc and 580–600 nm for IId, IIe that are
subjected to a blue shift of 80–100 nm with respect to the
longwave absorption maxima of initial compounds Ia, Ib.
Note that in the nonfluorinated 2-aryl-amino-N-aryl-1,4-
naphthoquinon-4-imines also a blue shift of the longwave
absorption maxima of 20–30 nm was observed with
respect to the λmax of N-(4-N,N-dialkylaminophenyl)-
1,4-naphthoquinon-4-imines [10].
σ-complex
PBE/3z
Etot
CAMB3LYP/6-31G*
ΔE
Etot
ΔE
2E
2Z
3E
3Z
–
–1531.49126
–1531.49719
–1531.50528
8.8
5.1
0
–
–1531.09061
0
In the electron absorption spectra of pentafluoro-
benzophenazinones IIIа–IIIe two absorption maxima are
present in the visible region at 540–550 and 570–580 nm.
–1531.07847 7.6 –1531.49981
3.4
is determined already at the stage of the formation of the
σ-complex.
Compounds IIIа–IIIe are luminescent in the solu-
tions of organic solvents, the luminescence maximum is
in the region 598–603 nm, and the Stockes shift value is
20–28 nm (Table 2).
However the occurrence of the cyclization reaction
requires the presence of Z-isomers of compounds IIа,
IIb. Therefore, we calculated the relative stability and
the energy of the mutual transformations of the Z- and
E-isomers of the model N-(4-N,N-dimethylaminophenyl)-
3-methylaminopentafluoro-1,4-naphthoquinon-4-imine
(IIf, Alk = Me, R = NHMe), a reaction product of
compound Ia with NH2Me. In the approximation PBE/3z
its E-isomer is more stable than the Z-isomer by 4.5 kcal
mol−1, and the activation energy of the transformation of
E into Z amounts to 15.1 kcal mol−1. A close value of the
relative stability of the isomers (4.3 kcal mol−1) was also
obtained on the calculation level CAMB3LYP/6-31G*.
Thus the reaction of hexafluoro-4-(4-N,N-
dialkylaminophenyl)-1,4-naphthoquinon-4-imines with
primary amines results in the formation of 3-amino-
substituted pentafluoronaphthoquinonimines which
undergo cyclization into pentafluorobenzophenazinones.
EXPERIMENTAL
The spectral investigations were performed in the
Chemical Service Center of the shared access of the
Siberian Branch of the Russian Academy of Sciences.
The results obtained are in keeping with the pres-
ence in the NMR spectra of 3-amino-substituted
1,4-naphthoquinon-4-imines IIa, IIb exclusively of the
signals of Е-isomers; the possibility of the cyclization of
IIа–IIe into IIIа–IIIe is apparently due to the rather low
inversion barrier.
IR spectra of compounds obtained were recorded on
a spectrophotometer Vector 22 from pellets with KBr,
electron absorption spectra, on a spectrophotometer
Hewlett Packard 4853 from solutions in CHCl3. The
fluorescence of the studied compounds in the chloroform
solutions was measured on a spectrofluorimeter Cary
Eclipse Varian equipped with a pulse xenon lamp and a
scheme of the luminescence registration at an angle of
90° with the excitation and emission slits of 5 nm, quartz
The electron absorption spectra of 3-amino deriva-
tives of polyfluorinated naphthoquinonimines contain
strong absorption bands in the region 560–580 nm for
Table 2. Spectral properties of 1,2,3,4,6-pentafluoro-7-R-5Н-benzo[a]phenazin-5-ones IIIа–IIIe in chloroform solution
Excitation
λmax, nm
Emission
λmax, nm
Compound no.
Absorption λmax, nm (logε)
λphl – λabs, nm
Iphl., rel.units.а
IIIa
IIIb
IIIc
IIId
IIIe
543 (4.16), 577 (4.11)
541 (4.53), 575 (4.50)
536 (4.50), 570 (4.50)
546 (4.57), 579 (4.58)
539 (4.38), 573 (4.54)
544, 576
544, 578
536, 573
544, 576
544, 575
602
603
598
599
598
25
28
28
20
25
194
700
541
555
947
аAt excitation on the longwave maximum.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

EKTOVA et al.
1620
cells 10 mm thick, at room temperature. The operating
solution concentration at the registering the excitation and
emission spectra was 2.5 × 10–6 mol l−1. NMR spectra
were registered from solutions of compounds in CDCl3
on spectrometers Bruker AV-300 [operating frequencies
300.13 (1Н) and 282.36 MHz (19F)], AV-600 [operat-
ing frequencies 600.30 (1Н), 564.84 (19F), 150.94 MHz
(13С)], and АV-400 [(1Н) 400.13 MHz]. Before the NOE
experiment the solution was flushed with argon. The re-
sidual signal of the solvent protons (δH 7.24, δC 77.0 ppm)
served as internal reference, the chemical shifts of 19F
were measured with respect to external reference С6F6.
The 13С NMR spectra were registered with decoupling
from protons. Mass spectra were recorded on instruments
DFS and Finnigan MAT-8200 (the molecular mass and
composition of compounds were determined from the
precise value of the molecular ion mass).
(IIа) was isolated. Yield 0.100 g (40%), t.decomp.
330°С. IR spectrum, ν, cm–1: 3350 (NH), 1646 (С=О),
1610 (С=N), 1579 (С=С). Н NMR spectrum, δ, ppm:
1
2.92 s (6Н, 2СН3), 3.04 s (6Н, 2СН3), 6.61 d (2Нarom
,
J 9 Hz), 6.67 d (2Нarom, J 9 Hz), 6.83 d (2Нarom, J 9 Hz),
7.05 m (2Нarom), 7.79 br.s (1Н, NH). 19F NMR spectrum,
δ, ppm: 11.4 m (1F, F7), 12.2 m (1F, F6), 14.2 s (1F, F2),
22.1 m (1F, F8), 39.1 m (1F, F5). EAS (СНСl3), λmax, nm
(logε): 571 (4.20). Found [M]+ 500.1635. С26Н21F5N4О.
Calculated M 500.1630.
From the red zone 1,2,3,4,6-pentafluoro-7-(4-N,N-
dimethylaminophenyl)-9-dimethylamino-5Н-benzo[a]
phenazin-5-one (IIIа) was isolated. Yield 0.099 g (40%),
t.decomp. 350°С. IR spectrum, ν, cm–1: 1620 (С=О), 1564
(С=N), 1523 (С=С). 1Н NMR spectrum, δ, ppm: 2.95 s
(6Н, 2СН3), 3.10 s (6Н, 2СН3), 5.82 d (1H, Н8, J 2 Hz),
6.75 m (1Н, Н10), 6.86 d (2Нarom, J 9 Hz), 7.21 d (2Нarom
,
19
Quantum-chemical calculations were carried out in
approximations PBE/3z and CAMB3LYP/6-31G* using
PRIRODA[11] and GAMESS [12] software, respectively.
The complete optimization of the geometric parameters
was carried out, the localization of the transition state of
the Z-E-isomerization was confirmed by the calculation
by the eigenvalues of the Hesse matrix and by the calcula-
tion of the intrinsic reaction coordinate (IRC).
J 9 Hz), 7.73 d (1H, H11, J 9 Hz). F NMR spectrum,
δ, ppm: 7.8 m (1F, F3), 8.0 s (1F, F6), 9.7 m (1F, F2),
18.4 m (1F, F4), 25.7 m (1F, F1). Found [M]+ 498.1479.
С26Н19F5N4О. Calculated M 498.1474.
Reaction of 2,3,5,6,7,8-hexafluoro-N-(4-N,N-
dimethylaminophenyl)-1,4-naphthoquinon-4-imine
(Iа) with p-anisidine. To a slurry of 0.190 g (0.5 mmol)
of compound Iа and 0.120 g (1 mmol) of p-anisidine in 30
ml of DMF was added 0.07 ml of triethylamine, and the
mixture was stirred for 5 h at 20°С. The reaction mixture
was poured in water, the separated precipitate was filtered
off, washed with water, and dried, then it was dissolved in
CHCl3 and subjected to column chromatography on silica
gel, gradient elution with a mixture CCl4–CHCl3 (CHCl3
gradient from 10 to 100 vol%). From the blue zone initial
compound Ia was isolated, yield 0.025 g (13%).
The progress of reaction was monitored and the purity
of compounds was checked by TLC on Silufol UV-254
plates (eluent chloroform), preparative chromatography
was carried out on columns packed with silica gel KSK
(L 50–100 μm).
All reactions were performed in air.
Reaction of 2,3,5,6,7,8-hexafluoro-N-(4-N,N-
dimethylaminophenyl)-1,4-naphthoquinon-4-imine
(Iа) with 4-N,N-dimethylaminoaniline. To a solution
of 0.190 g (0.5 mmol) of compound Ia in 50 ml of
ethanol was added 0.110 g (0.5 mmol) of 4-N,N-
dimethylaminoaniline and 0.14 ml (0.5 mmol) of
triethylamine, the reaction mixture was maintained for 3
h at 20°С, then it was poured in water, and 10 g of NaCl
was added. The separated precipitate was filtered off,
washed with water, and dried, then it was dissolved in
CHCl3 and subjected to column chromatography on silica
gel, gradient elution with a mixture CCl4–CHCl3 (CHCl3
gradient from 10 to 100 vol%). From the blue zone initial
compound Ia was isolated, yield 0.010 g (5%).
From the violet zone 2,5,6,7,8-pentafluoro-3-(4-
methoxyphenylamino)-N-(4-N,N-dimethyl-ami-
nophenyl)-1,4-naphthoquinon-4-imine (IIb) was isolat-
ed. Yield 0.096 g (39%), mp 160–162°С. IR spectrum, ν,
cm–1: 3434 (NH), 1649 (С=О), 1622 (С=N), 1609 (С=С).
1Н NMR spectrum, δ, ppm: 3.02 s (6Н, 2СН3), 3.80 s
(3Н, OСН3), 6.62 d (2Нarom, J 8 Hz), 6.84 m (4Нarom),
7.08 m (2Нarom), 7.77 br.s (1Н, NH). 19F NMR spectrum,
δ, ppm: 11.6 m (1F, F7), 12.7 m (1F, F6), 15.8 s (1F, F2),
22.4 m (1F, F8), 39.3 m (1F, F5). EAS (СНСl3), λmax, nm
(logε): 579 (4.69). Found [M]+ 487.1301. С25Н18F5N3О2.
Calculated M 487.1314.
From the light red zone 1,2,3,4,6-pentafluoro-7-
(4-methoxyphenyl)-9-dimethylamino-5Н-benzo[а]
phenazin-5-one (IIIb) was isolated. Yield 0.077 g (32%),
From the violet zone 2,5,6,7,8-pentafluoro-3-
(4-N,N-dimethylaminophenylamino)-N-(4-N,N-
dimethylaminophenyl)-1,4-naphthoquinon-4-imine
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

REACTION OF HEXAFLUORO-N-(4-N,N-DIALKYLAMINOPHENYL)-...
1621
t.decomp. >330°С. IR spectrum, ν, cm–1: 1618 (С=О),
1552 (С=N). Н NMR spectrum, δ, ppm: 2.91 s (6Н,
added 0.130 g (0.5 mmol) of 4-N,N-diethylaminoaniline
sulfate and 0.14 ml of triethylamine, and the reaction
mixture was maintained for 3 h at 20°С, then it was
poured in water, and 10 g of NaCl was added. The sepa-
rated precipitate was filtered off, washed with water, and
dried, then it was dissolved in CHCl3 and subjected to
column chromatography on silica gel, gradient elution
with a mixture CCl4–CHCl3 (CHCl3 gradient from 10 to
100 vol%). From the blue zone initial compound Ib was
isolated, yield 0.014 g (7%).
1
2СН3), 3.90 s (3Н, OСН3), 5.62 d (1Н, Н8, J 2.5 Hz),
6.72 d.d (1Н, Н10, J 9, 2.5 Hz), 7.08 m (2Нarom), 7.31 m
(2Нarom), 7.67 d (1Н, Н11', J 9 Hz). 19F NMR spectrum,
δ, ppm: 8.0 m (1F, F3), 8.2 s (1F, F6), 10.0 m (1F, F2),
19.0 m (1F, F4), 25.9 m (1F, F1). Found [M]+ 485.1162.
С25Н16F5N3О2. Calculated M 485.1157.
Reaction of 2,3,5,6,7,8-hexafluoro-N-(4-N,N-
dimethylaminophenyl)-1,4-naphthoquinon-4-imine
(Iа) with butylamine. To a solution of 0.192 g (0.5 mmol)
of compound Iа in 100 ml of ethanol was added 0.1 ml (1
mmol) of butylamine, 0.14 ml of triethylamine, and the
reaction mixture was maintained for 3 h at 20°С, then it
was poured in water, and 10 g of NaCl was added. The
separated precipitate was filtered off, washed with water,
and dried, then it was dissolved in CHCl3 and subjected
to column chromatography on silica gel, gradient elution
with a mixture CCl4–CHCl3 (CHCl3 gradient from 10 to
100 vol%).
From the violet zone 2,5,6,7,8-pentafluoro-3-
(4-N,N-diethylaminophenylamino)-N-(4-N,N-
diethylaminophenyl)-1,4-naphthoquinon-4-imine
(IId) was isolated. Yield 0.061 g (22%), t.decomp.
169–171°С. IR spectrum, ν, cm–1: 3294 (NH), 1644
1
(С=О), 1609 (С=N), 1574 (С=С). Н NMR spectrum,
δ, ppm: 1.16 t (6Н, 2СН3, J 7 Hz), 1.21 t (6Н, 2СН3,
J 7 Hz), 3.35 q (4Н, 2СН2, J 7 Hz), 3.41 q (4Н, 2СН2,
J 7 Hz), 6.61 m (4Нarom), 6.84 d (2Нarom, J 9 Hz), 7.03 m
(2Нarom), 7.81 br.s (1Н, NH). 19F NMR spectrum, δ,
ppm: 11.0 m (1F, F7), 11.9 m (1F, F6), 13.4 s (1F, F2),
21.9 m (1F, F8), 39.3 m (1F, F5). EAS (СНСl3), λmаx, nm
(logε): 599 (4.16). Found [M]+ 556.2250. С30Н29F5N4О.
Calculated M 556.2256.
From the violet zone 2,5,6,7,8-pentafluoro-3-
(butylamino)-N-(4-N,N-dimethylamino-phenyl)-1,4-
naphthoquinon-4-imine (IIc) was isolated. Yield 0.171
g (78%), mp 149–150°С. IR spectrum, ν, cm–1: 3347
(NH), 1644 (С=О), 1607 (С=N), 1591 (С=С). 1Н NMR
spectrum, δ, ppm: 0.94 t (3Н, СН3, J 7 Hz), 1.41 m (2Н,
СН2), 1.61 m (2Н, СН2), 3.00 s (6Н, 2СН3), 3.58 m (2Н,
СН2), 6.12 br.s (1Н, NH), 6.60 d (2Нarom, J 9 Hz), 6.78 d
(2Нarom, J 9 Hz). 19F NMR spectrum, δ, ppm: –1.6 s
(1F, F2), 11.4 m (1F, F7), 11.9 m (1F, F6), 22.2 m (1F,
F8), 38.6 m (1F, F5). EAS (СНСl3), λmax, nm (logε): 564
(4.04). Found [M]+ 437.15270. С22Н20F5N3О. Calculated
M 437.15264.
From the red zone 1,2,3,4,6-pentafluoro-7-(4-N,N-
diethylaminophenyl)-9-diethylamino-5Н-benzo[a]
phenazin-5-one (IIId) was isolated. Yield 0.086 g
(25%), t.decomp. 267–268°С. IR spectrum, ν, cm–1: 1614
1
(С=О), 1560 (С=N), 1517 (С=С). Н NMR spectrum,
δ, ppm: 1.07 t (6Н, 2СН3, J 7 Hz), 1.19 t (6Н, 2СН3,
J 7 Hz), 3.27 q (4Н, 2СН2, J 7 Hz), 3.41 q (4Н, 2СН2,
J 7 Hz), 5.80 s (1H, Н8), 6.74 m (3Н, 2Нarom, Н10), 7.13 m
(2Нarom), 7.69 d (1Н, Н11, J 9 Hz). 19F NMR spectrum, δ,
ppm: 7.6 m (1F3), 7.8 s (1F, F6), 9.5 m (1F2), 18.7 m (1F,
F4), 25.4 m (1F, F1). Found [M]+ 554.2097. С30Н27F5N4О.
Calculated M 554.2100.
From the red zone 1,2,3,4,6-pentafluoro-7-butyl-
9-dimethylamino-5Н-benzo[а]phenazin-5-one (IIIc)
was isolated. Yield 0.010 g (5%), mp 241–243°С. IR
spectrum, ν, cm–1: 1618 (С=О), 1561 (С=N), 1517
Reaction of 2,3,4,5,6,7,8-hexafluoro-N-(4-N,N-
diethylaminophenyl)-1,4-naphthoquinon-4-imine (Ib)
with butylamine. To a solution of 0.206 g (0.5 mmol)
of compound Ib in 50 ml of ethanolа was added 0.1 ml
(1 mmol) of butylamine, 0.14 ml triethylamine, and the
reaction mixture was maintained for 3 h at 20°С, then it
was poured in water, and 10 g of NaCl was added. The
separated precipitate was filtered off, washed with water,
and dried, then it was dissolved in CHCl3 and subjected
to column chromatography on silica gel, gradient elution
with a mixture CCl4–CHCl3 (CHCl3 gradient from 10 to
100 vol%).
1
(С=С). Н NMR spectrum, δ, ppm: 0.93 t (3Н, СН3,
J 7 Hz), 1.56 m (2Н, СН2), 2.07 m (2Н, СН2), 3.17 s
(6Н, 2СН3), 4.28 m (2Н, СН2), 6.29 d (1H, Н8, J 2 Hz),
6.82 d.d (1Н, Н10, J 9, 2 Hz), 7.65 d (1Н, Н11, J 9 Hz).
19F NMR spectrum, δ, m.d: 3.3 s (1F, (F6), 8.0 m (1F, F3),
10.1 m (1F, F2), 19.0 m (1F, F4), 25.8 m (1F, F1). Found
[M]+ 435.1356. С22Н20F5N3О. Calculated M 435.1365.
Reaction of 2,3,5,6,7,8-hexafluoro-N-(4-N,N-
diethylaminophenyl)-1,4-naphthoquinon-4-imine (Ib)
with 4-N,N-diethylaminoaniline. To a solution of 0.206
g (0.5 mmol) of compound Ib in 50 ml of ethanol was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

EKTOVA et al.
1622
From the violet zone 2,5,6,7,8-pentafluoro-3-
ml of ethanol was heated at 60°С for 5 h, the solution was
evaporated to dryness and chromatographed on a column
packed with silica gel, gradient elution with a mixture
CCl4–CHCl3 (CHCl3 gradient from 10 to 100 vol%).
From the red zone compound IIIe was isolated. Yield
0.083 g (68%), mp 224–225°С.
(butylamino)-N-(4-N,N-diethylaminophenyl)-1,4-
naphthoquinon-4-imine (IIe) was isolated. Yield
0.173 g (74%), mp 130–132°С. IR spectrum, ν, cm–1:
3345 (NH), 1649 (C=O), 1605 (C=N), 1585 (C=C).
1Н NMR spectrum, δ, ppm: 0.95 t (3H, СH3, J 7 Hz),
1.172 t (6H, 2 CH3, J 7 Hz), 1.40 m (2H, CH2), 1.64 m
(2H, CH2), 3.37 q (4H, 2CH2, J 7 Hz), 3.57 m (2H, CH2),
REFERENCES
6.1 br.s (1H, NH), 6.57 d (2Harom, J 9 Hz), 6.77 d (2Harom
,
1. Calo, V., Todesco, P.E. Chem. Commun., 1968, p. 571;
Afanas’eva, G.N. and Tsoi, E.V., Khim. Geterotsikl. Soedin.,
1991, p. 786.
2. Clark, J.H. and English, J.P., US Patent 2769.821, 1956.
3. Burmistrov, K.S., Glukh, A.N., and Toropin, N.V., Russ.
J. Org. Chem., 2005, vol. 41, p. 959.
4. Krasovitskii, B.M. and Bolotin, B.M., Organicheskie lyu-
minofory (Organic Phosphors), Moscow: Khimiya, 1976,
p. 129.
5. Ektova, L.V., Bukhtoyarova, A.D., Bagryanskaya, I.Yu.,
Beregovaya, I.V., and Chuikov, I.P., Russ. J. Org. Chem.,
2013, vol. 49, p. 1035.
6. Troshkova, N.M., Goryunov, L.I., Gatilov, Y.V., Nevin-
sky, G.A., and Shteingarts, V.D., J. Fluor. Chem., 2010,
vol. 131, p. 70.
7. Tsoi, E.V., Afanas’eva, G.B., Chupakhin, O.N., Khim.
Geterotsikl. Soedin., 1984, p. 330.
8. Gerasimova, T.N., Kolchina, E.F., Kargapolova, I.Yu.,
Fokin, E.P., Russ. J. Org. Chem., 1997, vol. 33, p. 796.
9. Wray, V., J. Chem. Soc., Perkin, Trans. II, 1978, p. 855.
10. Issa, I.M., El, Samahy, A.A., Issa, R.M., El, Kashef, H.S.
Rev. Roum. Chim., 1978, vol. 23, p. 617.
11. Laikov, D.N., Ustynyuk, Yu.A. Izv. Ross. Akad. Nauk,.
Ser. Khim., 2005, 804; Laikov, D.N. Chem. Phys. Lett.,
1997, vol. 281, p. 151.
J 9 Hz). 13С NMR spectrum, δ, ppm: 12.8 (2C, CH3), 14.0
(1C, CH3), 20.1 (1C, CH2), 33.0 (1C, CH2), 44.7 (1C,
CH2), 44.8 (2C, CH2), 111.9, 123.5 (C2', C6', C3', C5'),
113.9, 116.0 (C4а, C8а), 137.6, 139.9, 140.6, 147.9 (C3,
C4, C1', C4'), 139.4 (C2, 1JCF 238 Hz), 142.2 (C6, 1JCF 259,
2JCF 17, 12 Hz), 142.6 (C7, JCF 260, JCF 17, 12 Hz),
1
2
143.4 (C5, JCF 263, JCF 12 Hz), 147.0 (C8, JCF 267,
2JC 1 Hz), 170.7 (C1, JCF 18 Hz). 19F NMR spectrum,
1
2
1
2
δ, ppm: –1.8 s (1F, F2), 10.9 m (1F, F7), 11.5 m (1F, F6),
21.9 m (1F, F8), 38.8 m (1F, F5). EAS (СНСl3), λmax, nm
(logε): 583 (4.10). Found [M]+ 465.1828. C24H24F5N3O.
Calculated M 465.1834.
From the red zone 1,2,3,4,6-pentafluoro-7-butyl-
9-diethylamino-5Н-benzo[а]phenazin-5-one (IIIe)
was isolated. Yield 0.021 g (9%), mp 224–225°С. IR
spectrum, ν, cm–1: 1614 (С=О), 1556 (С=N), 1499 (С=С).
1Н NMR spectrum, δ, ppm: 1.05 t (3Н, СН3, J 7 Hz),
1.31 t (6Н, 2СН3,J 7 Hz), 1.56 m (2Н, СН2), 2.07 m (2Н,
СН2), 3.53 m (4Н, 2СН2), 4.27 m (2Н, СН2), 6.37 d (1H,
Н8, J 2 Hz), 6.83 d.d (1Н, Н10, J 9, 2 Hz), 7.67 d (1Н,
Н11, J 9 Hz). 19F NMR spectrum, δ, ppm: 6.1 s (1F, F6),
10.9 m (1F, F3), 13.0 m (1F, F2), 21.9 m (1F, F4), 28.5 m
(1F, F1). Found [M]+ 463.1671. С24Н22F5N3О. Calculated
M 463.1678.
12. Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T.,
Gor-don, M.S., Jensen, J.H., Koseki, S., Matsunaga, N.,
Nguyen, K.A., , Su, S.J., Windus, T.L., Dupuis, M., Mont-
gomery, J.A., J. Comput. Chem., 1993, vol. 14, p. 1347.
Cyclization of 2,5,6,7,8-pentafluoro-3-(butylamino)-
N-(4-N,N-diethylaminophenyl)-1,4-naphtho-quinon-
4-imine (IIe).Asolution of 0.124 g of compound IIe in 50
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013