peri-naphthalenediamines: XXXIV. 1,4,5,8-Tetrakis(dimethylamino)naphthalene: Alternative approaches to synthesis

Article abstract of DOI:10.1023/A:1019615206870

New methods were proposed for synthesizing 1,4,5,8-tetrakis(dimethylamino)naphthalene with an overall yield of 4 to 12% to replace the known procedure ensuring an overall yield of 2%. Catalytic hydrogenation was shown to be inapplicable for preparation of polyaminonaphthalenes from nitro compounds having 3 or 4 nitro gruops in the α-positions. Nucleophilic amination of 1,5-dinitronaphthalene in the system NH₂OH/NaOH/MeOH yields 1-amino-4-nitronaphthalene. The nitration of 1,5-bis(p-tolylsulfonylamino)-naphthalene leads to formation of 2,6-dinitro rather than 4,8-dinitro derivative, as it was believed formerly. This was confirmed by transformation of the latter into 1,2,5,6-tetrakis(dimethylamino)naphthalene. 3-Nitro, 2,6-dinitro, 2,6-diamino, and 2,4,6,8-tetranitro derivatives of 1,5-bis(dimethylamino)naphthalene, nitro and amino derivatives of 1,4,5-tris(dimethylamino)naphthalene, and 4,5-diamino-1,8-bis(methylamino)naphthalene were synthesized. By treatment with perchloric acid 1,4,5,8-tetrakis(dimethylamino)naphthalene was oxidized to 2,3-dihydroperimidinium salt.

Full text of DOI:10.1023/A:1019615206870

Russian Journal of Organic Chemistry, Vol. 38, No. 5, 2002, pp. 699 708. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 5, 2002,
pp. 737 746.
Original Russian Text Copyright
2002 by Sorokin, Ozeryanskii, Pozharskii.
peri-Naphthalenediamines:
XXXIV. 1,4,5,8-Tetrakis(dimethylamino)naphthalene:
Alternative Approaches to Synthesis*
V. I. Sorokin, V. A. Ozeryanskii, and A. F. Pozharskii
Rostov State University, ul. Zorge 7, Rostov-on-Don, 344090 Russia
e-mail: vv_ozer2@chimfak.rsu.ru
Received July 17, 2001
Abstract New methods were proposed for synthesizing 1,4,5,8-tetrakis(dimethylamino)naphthalene with
an overall yield of 4 to 12% to replace the known procedure ensuring an overall yield of 2%. Catalytic hydro-
genation was shown to be inapplicable for preparation of polyaminonaphthalenes from nitro compounds
having 3 or 4 nitro gruops in the -positions. Nucleophilic amination of 1,5-dinitronaphthalene in the system
NH2OH/NaOH/MeOH yields 1-amino-4-nitronaphthalene. The nitration of 1,5-bis(p-tolylsulfonylamino)-
naphthalene leads to formation of 2,6-dinitro rather than 4,8-dinitro derivative, as it was believed formerly.
This was confirmed by transformation of the latter into 1,2,5,6-tetrakis(dimethylamino)naphthalene. 3-Nitro,
2,6-dinitro, 2,6-diamino, and 2,4,6,8-tetranitro derivatives of 1,5-bis(dimethylamino)naphthalene, nitro and
amino derivatives of 1,4,5-tris(dimethylamino)naphthalene, and 4,5-diamino-1,8-bis(methylamino)naphthalene
were synthesized. By treatment with perchloric acid 1,4,5,8-tetrakis(dimethylamino)naphthalene was oxidized
to 2,3-dihydroperimidinium salt.
Physical and chemical properties of 1,8-bis(di-
methylamino)naphthalene (I, proton sponge ) have
been extensively studied [1]. However, analogous
properties of 1,4,5,8-tetrakis(dimethylamino)naphtha-
lene (II, double proton sponge ), which was syn-
thesized in 1991, remain almost unknown: only its
protonation [2] and oxidation [3] have been reported.
Nevertheless, functional derivatives of tetraamine II
could form the basis for synthesizing multidentate
organic bases, e.g., compound III.
The main reason which restricts the use of com-
pound II in chemical transformations is that it is
difficult to obtain. Staab et al. [2] proposed a multi-
step scheme for preparation of compound II in
an overall yield of 2% (Scheme 1). Taking into
account that perimidinone IV is obtained from 1,8-di-
aminonaphthalene in two steps, the overall number of
steps connecting the initial compound (1,8-diamino-
naphthalene) with target product II amounts to seven.
The goal of the present study was to develop alter-
native routes to tetraaminonaphthalene II. First of all,
we have found that the transformations shown in
Scheme 1 [2] are not always optimal. For example,
the synthesis of V from IV is more efficient when
the reaction is carried out in two steps through mono-
nitro derivative IX. In such a way, the yield of V is
raised to 44% against 33% in [2] (cf. [4]). Further-
more, the number of steps in Scheme 1 can be reduced
via direct transformation of VI into II through amine
X without loss in efficiency (see Experimental). Thus,
modification of the procedure given in [2] allowed
us to increase the overall yield of double proton
sponge II up to 3%.
____________
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 99-03-33133a).
1070-4280/02/3805-0699$27.00 2002 MAIK Nauka/Interperiodica

700
SOROKIN et al.
Scheme 1.
An alternative route to proton sponge II involves
tion of compound XIV by hydrogenation of 1,8-bis-
(dimethylamino)-4-nitronaphthalene (XV) over Pd/C
[8]. However, in the latter case the group being lost
is dimethylamino and its elimination occurs on pro-
longed reduction from amine XVI rather than from
compound XV. We failed to detect formation of tetra-
(XII) or triamino derivative (XVII) in the hydrogena-
tion of the corresponding nitro compounds. This
means that elimination of nitrogen-containing groups
occurs from some intermediate product. In fact,
1-amino-4,5-dinitronaphthalene (XVIII) can be ob-
tained by reduction of XIII in the system H2/Pd/C.
Therefore, the first stage of the process is reduction
of the least sterically hindered nitro group.
its most obvious precursor, 1,4,5,8-tetranitronaphtha-
lene (XI), as starting compound. However, we have
encountered with a number of difficulties while
developing this approach. First, the yield of XI from
1,5-dinitronaphthalene does not exceed 25% [5],
which makes the procedure insufficiently effective
at the startup. Second, our attempt to synthesize
1,4,5,8-tetraaminonaphthalene (XII) by catalytic
hydrogenation with hydrogen over Pd/C, N2H4 over
FeCl3/C, and N2H4 over Raney nickel rather than by
reduction of nitronaphthalene XI with tin(II) chloride
[6] resulted in formation of 1,5-diaminonaphthalene in
high yield instead of the expected tetraamino deriva-
tive; i.e., the hydrogenation was accompanied by
elimination of two nitrogen-containing groups. We
have found that an analogous transformation (to give
1,5-diaminonaphthalene) also occurs in the catalytic
hydrogenation of 1,4,5-trinitronaphthalene (XIII) in
which the nitro groups are arranged similarly. These
results suggest that the number of nitro groups and
their positions are the key factors responsible for the
observed elimination process: 1,5- and 1,8-dinitro-
naphthalenes are smoothly hydrogenated to the corre-
sponding diamines [7] (see Experimental). We have
found no published data on analogous transforma-
tions. Some similarity may be drawn with the forma-
XIV, R = NH2, R = H; XV, R = NO2, R = NMe2; XVI,
R = NH2, R = NMe2; XVII, R = NH2; XVIII, R = NO2.
Compound XVIII was also obtained in a small
yield by independent synthesis, via nucleophilic
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peri-NAPHTHALENEDIAMINES: XXXIV.
701
amination of 1,8-dinitronaphthalene in the system
NH2OH/NaOH/MeOH [9]. It should be noted that
monoamine XVIII is formed even in the presence of
a 10-fold amount of the aminating agent. We failed
to detect in the reaction mixture 1,8-diamino-4,5-di-
nitronaphthalene which we planned to use as precursor
of compound II.
One more example of elimination of nitrogen-
containing group was observed in the amination of
1,5-dinitronaphthalene performed under analogous
conditions (NH2OH/NaOH/MeOH). Contrary to the
expectations, we obtained 1-amino-4-nitronaphthalene
(XIX), i.e., nucleophilic replacement was accom-
panied by elimination of the nitro group. Presumably,
the replacement occurred in intermediate -adduct XX
as a result of hydride ion migration (cf. [10, 11]).
Barth et al. [3] previously synthesized an analogous
salt containing I3 as counterion by oxidation of proton
1
sponge II with iodine. The H NMR spectra of this
salt and salt XXI are almost similar. Up to now, no
formation of oxidation products was observed in the
synthesis of salts of diamine I derivatives, which
indicates strong donor properties of molecule II [2].
For instance, compound II smoothly gives the corre-
sponding salt with HBF4 which has no oxidizing
properties.
It seemed very promising to make use of previously
unknown 1,5-bis(dimethylamino)-4,8-dinitronaphtha-
lene (XXII) as precursor of II. For this purpose, it
was necessary to develop a convenient procedure for
synthesizing dinitrodiamine XXII. As a possible way
we examined nitration of 1,5-bis(dimethylamino)-
naphthalene (XXIII).
Insofar as we failed to obtain tetraamine XII by
catalytic hydrogenation, we synthesized it in more
than 80% yield from nitro compound XI by modified
procedure [6]. We were the first to characterize com-
pound XII in the pure state rather than its derivatives.
Unfortunately, our attempts to effect the transforma-
tion XII II with the aid of various alkylating agents
[MeI/KOH//DMSO (DMF), MeI/K2CO3/MeOH, and
Me2SO4/Na2CO3/H2O] were unsuccessful. The only
procedure which gave a positive result was the
so-called Quast method [12] utilizing the system
Me2SO4/NaH/THF. In this case the yield of II was
14%. We tried to isolate compound II as a salt with
perchloric acid but obtained dihydroperimidinium salt
XXI instead of the expected diperchlorate II 2HClO4.
However, there was no problem, for salt XXI, like
other dihydroperimidinium salts [13], can readily be
converted into tetraamine II with a high yield by the
action of NaBH4 in acetonitrile.
XXII, R = NO2, R = H; XXIII, R = R = H; XXIV, R = H,
R = NO2.
Compound XXIII was synthesized by (1) alkyla-
tion of 1,5-diaminonaphthalene with methyl iodide in
the system KOH/DMF (yield 84%) and (2) reductive
methylation of 1,5-diaminonaphthalene in the system
CH2O/NaBH4/H3O+ following the procedure reported
in [14] (yield 62%). Both these methods turned out
to be more efficient than that described in [15].
Treatment of diamine XXIII with 2 equiv of con-
centrated nitric acid in sulfuric acid at 0 C led to
formation of previously unknown nitronaphthalene
XXIV as the major product (yield 40%). Its structure
1
was unambiguously confirmed by the H NMR spec-
trum which displayed spin spin couplings between
2-H and 4-H (4J = 2.3 Hz) and between 4-H and 8-H
(5J = 0.8 Hz).
meta-Substitution by the action of nitrating mixture
is typical for most tertiary arylamines, e.g., for
N,N-dimethylaniline [16]. Under these conditions, the
nitration occurs with dication XXIII 2H+. In acetic
acid or acetonitrile, the major product was tetranitro
derivative XXV (30 32%) even when the nitration
was carried out using 2 equiv of HNO3. Thus, we
cannot accomplish selective nitration of neutral base
XXIII because of strong activation of the naphthalene
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 5 2002

702
SOROKIN et al.
ring by the dimethylamino groups. The same factor
was responsible for our failure to effect selective
transformation I VII [17].
effect of the ethylene bridge [19]) is readily hydrolyz-
ed to the corresponding amine in 10% hydrochloric
acid [20].
According to Nielsen et al. [18], amides XXVI and
XXVII which are less reactive 1,5-diaminonaphtha-
lene derivatives are selectively nitrated to the corre-
sponding dinitro compounds XXVIII and XXIX in
70% yield. However, as well as the authors of [18],
we failed to remove the N-acetyl groups from com-
pound XXVIII by acid or alkaline hydrolysis.
While attempting to reproduce the synthesis of
1,5-diamino-4,8-dinitronaphthalene from bis(p-tolyl-
sulfonyl) derivative XXIX, reported in [18], we have
found that the product obtained by nitration of XXVII
was assigned invalid structure. In the system HNO3
AcOH nitro groups enter positions 2 and 6 (to give
dinitro compound XXXIV) rather than 4 and 8 (as
was assumed in [18]). The nitration direction is con-
firmed by a series of consecutive transformations
including hydrolysis of XXXIV to diamine XXXV,
alkylation to XXXVI (the best results were obtained
in the system MeI/KOH/acetone or acetonitrile, yield
50%), reduction with SnCl2 in hydrochloric acid to
diamine XXXVII, and methylation of the latter with
dimethyl sulfate in H2O/Na2CO3. As a result, we
obtained 1,2,5,6-tetrakis(dimethylamino)naphthalene
(XXXVIII) which was described in [21]. It should be
noted that the above sequence leading to proton
sponge XXXVIII is much more efficient than the
procedure proposed in [21].
The best procedure for preparation of double
proton sponge II is now that developed by us starting
from 1,4,5-tris(dimethylamino)naphthalene (XXXIX)
[8]. In the present communication we describe
an alternative route to compound XXXIX which
is available directly from triamine XVII. The latter
is prepared by reduction of 1,4,5-trinitronaphthalene.
The proposed procedure is characterized by the same
efficiency as that described in [8], but it includes
two steps less. Here, one of the ways of effecting the
transformation XVII XXXIX, namely exhaustive
methylation in the system Me2SO4/Na2CO3/H2O
according to the modified procedure [22], is very
simple. It was also applied to a series of naphthyl-
amines (see Experimental). It should be noted that
triamine XXXIX is not oxidized with perchloric acid,
and stable perchlorate XXXIX HClO4 is obtained [8].
XXVI, R = Ac, R = H; XXVII, R = Ts, R = H; XXVIII,
R = Ac, R = NO2; XXIX, R = Ts, R = NO2.
A similar problem arose with nitro derivative XXX
which is obtained in 86% yield by nitration of acet-
amide XXXI. Compound XXX was readily alkylated
to give amide XXXII, but the N-acetyl group therein
remained unchanged under hydrolysis conditions
(10% or concentrated hydrochloric acid, 25% H2SO4,
10% KOH, K2CO3, NaOAc, piperidine in water or
ethanol). The observed behavior of nitroamides
XXVIII, XXX, and XXXII may be interpreted in
terms of steric shielding of the acetyl carbonyl group
by the bulky nitro group in the neighboring peri
position. Indeed, acenaphthene derivative XXXIII in
which the nitro and acetylamino groups are more
distant from each other (presumably, due to shrinking
XXXIX, R = H; XL, R = NO2; XLI, R = NH2.
XXX, R = H, R = NO2; XXXI, R = R = H; XXXII, R =
Me, R = NO2; XXXIV, R = Ts; XXXV, R = H; XXXVI,
R = NO2; XXXVII, R = NH2; XXXVIII, R = NMe2.
We expected that in acid medium compound
XXXIX will give rise to a cation stabilized by intra-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 5 2002

peri-NAPHTHALENEDIAMINES: XXXIV.
Synthetic routes to 1,4,5,8-tetrakis(dimethylamino)naphthalene (II)
703
Method
no.
Starting
compound
Number
of steps N
Overall yield
of II,
Efficiency,
Reaction sequence
%
%/N
0.3
0.4
1.3
1.7
1.6
1
1,8-Diamino-
naphthalene
1,8-Diamino-
naphthalene
1,5-Dinitro-
naphthalene
1,8-Diamino-
naphthalene
1,5-Dinitro-
naphthalene
IV
V
VI
V
VII
VI
7
7
3
7
6
2
(original)
VIII
II
1
(modified)
2
IV
II
IX
3
4
X
XI
XII
II
3
4
I
XV
XVI
II
XVII
XXXIX
12
10
XL
XIII
XL
XLI
XLI
XXXIX
II
molecular hydrogen bond, so that the nitration will
occur at the only vacant peri position. In fact, by
treatment of XXXIX with 1 equiv of nitric acid in
concentrated sulfuric acid at 30 C (4 min) we
succeeded in isolating for the first time 1,4,5-tris-
(dimethylamino)-8-nitronaphthalene (XL) in 40%
yield. Also, some tarry products were formed. The
best results were obtained when the nitration was
performed with the salt of XXXIX with HBF4. In this
case the yield of nitro derivative XL attained 50%.
The use of milder nitrating systems, e.g., HNO3/Ac2O
or NO2BF4/MeCN, resulted in strong tarring, and no
target product XL was isolated.
or Me2SO4/NaH/THF gives up to 30% of proton
sponge II. The best results were obtained by alkyla-
tion of XLI according to the modified procedure [22]
(Me2SO4/Na2CO3/H2O). In such a way, the yield of
II was raised to 40%. This procedure allowed us to
convert 1,8-diaminonaphthalene into compound I in
more than 90% yield without resorting to inert atmo-
sphere. Thus, it is the simplest and cheapest among all
known methods for synthesis of compound I (cf. [1]).
The principal results of the present study, as well as
comparative analysis of the proposed and previously
known approaches to tetraamine II, are given in table.
It is seen that, despite a number of steps, method
no. 3 turns out to be the most efficient. It combines
proton sponges I, XXXIX, and II into a single syn-
thetic sequence. On the other hand, method no. 2 may
be regarded as one of the most convenient, for it
includes the least number of steps.
Compound XL is the first proton sponge having
both donor and acceptor groups in differents rings
1
of the naphthalene system. Analysis of the H NMR
spectrum of perchlorate XL HClO4 in CD3CN
showed that the NH proton in XL H+, which is
involved in intramolecular hydrogen bond, is dis-
placed toward the 4-NMe2 group by 63% (calculated
from the corresponding coupling constants); however,
this displacement is not so strong as expected. A pos-
sible reason is that the 8-NO2 and 1-NMe2 groups are
not coplanar because of peri interaction. Compound
XL is a much weaker base than proton sponge I; its
pK1a value in DMSO is 5.0 (estimated by the trans-
protonation technique [8]) against to 7.5 for diamine I
[23]. These data suggest that the 1-dimethylamino
EXPERIMENTAL
1
The H NMR spectra were recorded on a Bruker
DPX-250 instrument at 250 MHz using tetramethyl-
silane as internal reference. The IR spectra were
obtained on a Specord 75IR spectrometer. The UV
spectra were measured on a Specord M-40 spectro-
photometer. Column chromatography was performed
using Al2O3 or silica gel L 40/100 m (Chemapol).
group which does not participate in intramolecular The progress of reactions and the purity of products
H-bonding deviates from the naphthalene ring plane
more strongly than the nitro group. Hence the latter
determines the reduced basicity of XL. The pKa value
of nitroamide XXX is even smaller: it is equal to 3.8.
Compound XL is smoothly reduced to amine XLI
with SnCl2 in hydrochloric acid (yield 80%), and
methylation of XLI with the system MeI/KOH/DMF
were monitored by TLC on Al2O3 and Silufol plates;
development with iodine vapor. The melting points
were determined in a sealed capillary using a PTP
device and were not corrected. Sodium hydride was
used as a 50% dispersion in mineral oil (Aldrich).
1,3-Dimethyl-6-nitroperimidin-2(1H)-one (IX).
The reaction was carried out following the procedure
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 5 2002

704
SOROKIN et al.
described in [4]. A solution of 0.35 g (5.1 mmol) of
NaNO2 in 2 ml of water was added to a solution of
1.06 g (5 mmol) of dimethylperimidinone IV [24] in
50 ml of glacial acetic acid. The mixture was stirred
for 1 h at 20 C, and the resulting orange suspension
was poured into 200 ml of water. The product was
filtered off, washed with water, dried at 100 C, and
recrystallized from toluene. Yield 1.08 g (84%).
Orange needles, mp 261 262 C (published data [4]:
The yield of X was not determined, for the amine
undergoes very fast oxidation on exposure to air. H
NMR spectrum (CDCl3), , ppm: 2.74 s (6H, NMe),
1
4.8 br.s (6H, NH), 6.60 d (2H, 3-H, 6-H, J2, 3
=
7.9 Hz), 6.66 d (2H, 2-H, 7-H).
Amine X was alkylated according to Quast [12].
It was dissolved in 40 ml of anhydrous THF, and
0.036 g (0.76 mmol) of NaH and 0.07 ml (0.74 mmol)
of dimethyl sulfate were added to the solution under
stirring in an inert atmosphere. The mixture was
stirred for 10 min at 25 C and for 6 h at 60 C, care-
fully diluted (while stirring) with 60 ml of 20%
aqueous KOH, and extracted with hexane (4 10 ml).
The extract was evaporated, and the residue was sub-
jected to column chromatography on Al2O3 (Brock-
man activity grade II; eluent ethyl acetate). From the
yellow fraction with Rf 0.50 we isolated 0.01 g (9%)
of 1,4,5,8-tetrakis(dimethylamino)naphthalene (II).
Yellow needles, mp 193 194 C (from pentane)
1
mp 262 C). IR spectrum (mineral oil), , cm : 1680
(C O); 1628, 1583 (C Carom); 1519, 1325 (NO2).
UV spectrum (MeOH), max, nm (log ): 255 (4.09),
276 (4.05), 345 (3.09).
1,3-Dimethyl-6,7-dinitroperimidin-2(1H)-one
(V). Concentrated nitric acid (d = 1.41), 0.14 ml
(2.2 mmol), was added in one portion to a solution of
0.5 g (1.9 mmol) of compound IX in 90 ml of AcOH,
stirred at 100 C. The bright orange mixture was
stirred for 1.5 h at 100 C and cooled to 20 C. The
product was filtered off and washed with acetic acid
and water on a filter. Yield 0.32 g (54%). Yellow
orange powder which did not melt below 340 C (pub-
lished data [2]: decomposes at 310 C). IR spectrum
1
(published data [2]: mp 193.5 C). H NMR spectrum
(CDCl3), , ppm: 2.76 s (24H, NMe2), 6.79 s (4H,
Harom). UV spectrum (EtOH), max, nm (log ): 245
(4.42), 361 (4.11), tail absorption up to 450 nm.
1
(mineral oil), , cm : 1691 (C O); 1625, 1580
Catalytic hydrogenation of 1,4,5,8-tetranitro-
naphthalene (XI). Compound XI was synthesized by
the procedure reported in [5]. Decomposition point
343 C (from acetone EtOH, 1:1). 1H NMR spec-
trum (DMSO-d6), , ppm: 8.82 s (4H, Harom). The
hydrogenation was performed at 25 C using 0.05 g
(0.16 mmol) of nitronaphthalene XI, 30 ml of MeOH,
and 0.05 g of the catalyst (2% Pd/C). After 15 h, the
mixture was filtered, and the solvent was removed to
obtain 0.023 g (90%) of 1,5-diaminonaphthalene. The
product was identical to a sample prepared by hydro-
genation of 1,5-dinitronaphthalene under analogous
conditions. Following the same procedure, from
1,8-dinitronaphthalene we obtained in 5 h 95% of
1,8-diaminonaphthalene.
(C Carom); 1519, 1321 (NO2).
General procedure for the reduction of
compounds with tin(II) chloride. Nitro compound,
0.05 g, was thoroughly mixed with 2 ml of EtOH,
and a solution of 2 equiv of SnCl2 2H2O in 3 ml
of concentrated hydrochloric acid was added to the
resulting solution or suspension. The mixture was
stirred for a definite time at a required temperature
(indicated below for each compound). The mixture
was then poured in portions into a large excess of
a concentrated solution of sodium hydroxide (on
cooling with ice), each time with stirring until tin
compounds dissolved completely. The product was
extracted into diethyl ether (peroxide-free), the extract
was evaporated, and the resulting amine was brought
into further transformations.
Catalytic hydrogenation of 1,4,5-trinitronaphta-
lene (XIII). Compound XIII was synthesized by
the procedure reported in [5]. 1H NMR spectrum
1,8-Bis(methylamino)-4,5-dinitronaphthalene
(VI) was synthesized from nitro derivative V by the
procedure described in [2]. mp 263 264 C (from
DMF) (published data [2]: decomposes at 235 C). IR
(DMSO-d6), , ppm: 8.10 t (1H, 7-H, J6, 7 = 7.9, J7, 8
=
8.6 Hz), 8.56 d (1H, 8-H, J6, 8 = 1.0 Hz), 8.62 m
(3H, 2-H, 3-H, 6-H, J2, 3 = 8.2 Hz). By hydrogenation
of XIII for 10 h at 20 C we obtained almost 100% of
1,5-diaminonaphthalene.
1
spectrum (mineral oil), , cm : 3340 (NH); 1600,
1500 (C Carom).
4,5-Diamino-1,8-bis(methylamino)naphthalene
(X) and its transformation into 1,4,5,8-tetrakis(di-
methylamino)naphthalene (II). Following the above
general procedure, nitronaphthylamine VI, 0.1 g
(0.36 mmol), was reduced with 1.2 g (4.6 mmol) of
SnCl2 2H2O (2.5 h, 25 C) to obtain tetraamine X.
When the hydrogenation was terminated after 3 h,
the solvent was removed, and the residue was sub-
jected to column chromatography on silica gel with
ethyl acetate as eluent, a bright yellow fraction was
collected (Rf 0.87) from which we isolated 10% of
1-amino-4,5-dinitronaphthalene (XVIII). Red crystals,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 5 2002

peri-NAPHTHALENEDIAMINES: XXXIV.
705
mp 245 246 C (from butanol) (cf. [25]). IR spectrum
XI was treated with 0.48 ml (5 mmol) of Me2SO4 in
the presence of 0.24 g (5 mmol) of NaH. The yield of
II was 0.014 g (14%). It was identical in physical
properties to a sample obtained by alkylation of com-
pound X. Treatment of the hexane extract with
0.055 ml (0.64 mmol) of 70% perchloric acid gave
0.028 g of a solid which was recrystallized from
methanol to obtain 6,7-bis(dimethylamino)-1,1,3-tri-
methyl-2,3-dihydro-1H-perimidinium diperchlorate
(XXI) as a grayish powder decomposing at 280
1
(mineral oil), , cm : 3485, 3370, 1640 (NH2); 1525,
1
1340 (NO2). H NMR spectrum (DMSO-d6), , ppm:
6.79 d (1H, 3-H, J2, 3 = 9.0 Hz), 7.71 t (1H, 7-H,
J6, 7 = 8.4 Hz), 7.78 br.s (2H, NH2), 8.30 m (2H, 2-H,
8-H), 8.65 d (1H, 6-H).
Amination of 1,8-dinitronaphthalene. The reac-
tion was carried out by the modified procedure [9]. To
a solution of 0.05 g (0.23 mmol) of 1,8-dinitronaph-
thalene in 5 ml of MeOH we added 0.1 g (1.4 mmol,
6 equiv) of NH2OH HCl and then 0.16 g (2.9 mmol)
of powdered KOH. The mixture was heated to the
boiling point and was refluxed for 1 h. The yellow
orange solution was poured into 20 ml of water, and
the bright yellow precipitate was filtered off and
subjected to column chromatography on Al2O3 of
Brockman activity grade III (eluent benzene ethyl
acetate, 2:1). An orange fraction, Rf 0.60, was col-
lected. We isolated 0.01 g (19%) of compound XVIII
which was identical to a sample obtained by incom-
plete hydrogenation of trinitronaphthalene XIII.
1
282 C. H NMR spectrum (CD3CN), , ppm: 3.04 d
(6H, 7-NMe2, JNH, NMe = 1.1 Hz), 3.19 d (6H,
6-NMe2, JNH, NMe = 3.5 Hz), 3.36 s (3H, 3-NMe),
3.53 br.s (6H, 1-NMe2), 4.85 s (2H, 2-H), 7.24 d
(1H, 4-H, J4, 5 = 8.7 Hz), 7.99 d (1H, 9-H, J8, 9
=
8.8 Hz), 8.04 m (2H, 5-H, 8-H), 18.27 br.s (1H, NH).
Addition of a small excess of NaBH4 to a solution
of salt XXI in acetonitrile at 25 C almost instanta-
neously gave 1,4,5,8-tetrakis(dimethylamino)naphtha-
lene (II) in nearly quantitative yield [13].
1,4,5,8-Tetrakis(dimethylamino)naphthalene bis-
(tetrafluoroborate) (II 2HBF4). Compound II,
0.02 g (0.067 mmol), was dissolved in 2 ml of ether,
0.016 ml (0.13 mmol) of 60% HBF4 was added, the
mixture was vigorously shaken for 2 min, and the
precipitate was separated by decanting and washed
with ether. Yield quantitative. Grayish powder,
mp 341 343 C (from methanol); published data [2]:
decomposition point 280 C. 1H NMR spectrum
(CD3CN), , ppm: 3.12 s (24H, NMe2), 8.12 s (4H,
Harom), 19.03 br.s (2H, NH).
Amination of 1,5-dinitronaphthalene. A solution
of 0.16 g (2.9 mmol) of powdered KOH in 5 ml of
MeOH was added in one portion to a suspension of
0.05 g (0.23 mmol) of 1,5-dinitronaphthalene and
0.1 g (1.4 mmol) of NH2OH HCl in 8 ml of MeOH.
The mixture was stirred for 2 h at 50 C and poured
into 30 ml of water, and the yellow precipitate was
filtered off and subjected to column chromatography
on Al2O3 of Brockman activity grade III (eluent
chloroform). A yellow fraction, Rf 0.30 was collected.
Yield of 1-amino-4-nitronaphthalene (XIX) 0.02 g
(46%), mp 190 191 C (published data [11]: 191 C).
1,5-Bis(dimethylamino)naphthalene (XXIII).
A solution of 1.58 g (0.01 mol) of 1,5-diaminonaph-
thalene in 20 ml of DMF was stirred for 3 min in
an inert atmosphere, 4.48 g (0.08 mol) of powdered
KOH was added, the mixture was stirred for 5 min,
and 5 ml (0.08 mol) of methyl iodide was added. The
mixture was stirred for 1 h at 20 C and for 1 h at
100 C, diluted with 100 ml of water, made alkaline by
adding ammonia until persistent odor, and extracted
with benzene (5 20 ml). The solvent was removed
from the extract to obtain 1.8 g (84%) of compound
XXIII as grayish crystals with mp 87 88 C (from
1H NMR spectrum (DMSO-d6), , ppm: 6.68 d (1H,
2-H, J2, 3 = 8.9 Hz), 7.54 d.d.d (1H, 6-H, J6, 8
=
0.7 Hz), 7.58 br.s (2H, NH2), 7.75 d.d.d (1H, 7-H,
J6, 7 = 7.4, J5, 7 = 1.4 Hz), 8.30 d.d (1H, 5-H, J5, 6
=
8.5 Hz), 8.39 d (1H, 3-H), 8.91 d.d (1H, 8-H).
1,4,5,8-Tetraaminonaphthalene (XII) and its
transformation into 1,4,5,8-tetrakis(dimethyl-
amino) naphthalene (II). Following the general
procedure (see above), nitronaphthalene XI was
reduced with tin(II) chloride (2.5 h, 40 C). Yield of
XII 82%, bluish powder which rapidly turns dark
on exposure to air and undergoes very ready oxidation
in solution, mp 160 162 C. The product is well
1
EtOH); published data [15]: mp 87 88 C. H NMR
spectrum (CDCl3), , ppm: 2.87 s (12H, NMe2),
7.05 d.d (2H, 2-H, 6-H, J2, 3 = 7.4, J2, 4 = 1.0 Hz),
7.38 d.d (2H, 3-H, 7-H, J3, 4 = 8.4 Hz), 7.92 d.d (2H,
4-H, 8-H).
Nitration of 1,5-bis(dimethylamino)naphthalene
(XXIII). a. Compound XXIII, 0.05 g (0.23 mmol),
was dissolved in 2 ml of H2SO4 (d = 1.84) at 0 C,
0.03 ml (0.047 mmol) of concentrated nitric acid
1
soluble in dilute mineral acids. H NMR spectrum
(CDCl3), , ppm: 4.1 br.s (8H, NH2), 6.57 s (4H,
Harom).
The alkylation of XII was carried out by a proce-
dure similar to the alkylation of amine X. Amine XII
prepared from 0.1 g (0.32 mmol) of nitro derivative
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 5 2002

706
SOROKIN et al.
1
(d = 1.41) was added, and the mixture was vigorously
stirred for 30 min at 0 C. It was then diluted with
15 ml of cold water, neutralized with concentrated
aqueous ammonia until persistent odor, and extracted
with chloroform (4 10 ml). The extract was
evaporated to a minimal volume and was applied to
a column charged with silica gel. The column was
eluted with chloroform, and an orange red fraction
with Rf 0.60 was collected, from which we isolated
0.024 g (40%) of 1,5-bis(dimethylamino)-3-nitronaph-
thalene (XXIV) as an oily substance which crystal-
lized on cooling to 0 C. Orange needles, mp 75 76 C
(NH); 1665 (C O); 1580, 1495 (C Carom). H NMR
spectrum (CDCl3), , ppm: 2.12 s (3H, COMe); 2.79 s
and 2.97 s (6H each, 4-NMe2 and 5-NMe2); 6.64 d,
6.99 d, 7.53 d, and 7.91 d (1H each, 6-H, 3-H, 2-H,
7-H, J2, 3 = 8.3, J6, 7 = 8.8 Hz); 7.54 s (1H, NH).
Found, %: C 61.02; H 6.43; N 17.51. C16N20N4O3.
Calculated, %: C 60.75; H 6.37; N 17.71.
1-(N-Acetylmethylamino)-4,5-bis(dimethyl-
amino)-5-nitronaphthalene (XXXII). Powdered
KOH, 0.019 g (0.33 mmol), and methyl iodide,
0.076 ml (1.2 mmol), were added to a solution of
0.095 g (0.3 mmol) of nitroamide XXX in 5 ml of
acetone. The mixture was stirred for 7 days at room
temperature, the solvent was removed, the residue
was dissolved in a small amount of chloroform, and
the solution was applied to a column charged with
Al2O3 of Brockman activity grade V. The column
was eluted with chloroform, and the first red fraction,
Rf 0.90, was collected, from which 0.094 g (95%)
of amide XXXII was isolated. Red orange leaflets,
mp 154 155 C (from octane). IR spectrum (mineral
1
(from MeOH). H NMR spectrum (CDCl3), , ppm:
2.91 s and 2.92 s (6H each, 5-NMe2 and 1-NMe2),
7.11 d.d (1H, 6-H, J6, 7 = 7.6, J6, 8 = 0.9 Hz), 7.52 d.d
(1H, 7-H, J7, 8 = 8.6 Hz), 7.71 d (1H, 2-H, J2, 4
2.3 Hz), 7.86 d.t (1H, 8-H), 8.85 d.d (1H, 4-H, J4, 8
=
=
0.8 Hz). UV spectrum (EtOH), max, nm (log ): 282
(4.10), 334 sh (3.57), 419 (3.55). Found, %: C 64.80;
H 6.58. C14H17N3O2. Calculated, %: C 64.85; H 6.61.
b. Compound XXIII, 0.05 g (0.23 mmol), was
dissolved in 2 ml of glacial acetic acid, 0.03 ml
(0.47 mmol) of concentrated nitric acid (d = 1.41)
was added at 20 C, and the mixture was stirred for
30 min at 20 C. The dark red solution was diluted
with 50 ml of water, and the precipitate was filtered
off, dried in air, and recrystallized from chloroform.
Yield of 1,5-bis(dimethylamino)-2,4,6,8-tetranitro-
naphthalene (XXV) 0.028 g (30%). Dark red crystals
with a yellow luster, decomposition point 218 219 C.
1H NMR spectrum (CDCl3), , ppm: 2.75 s (12H,
NMe2), 8.06 s (2H, Harom). UV spectrum (acetone),
max, nm (log ): 355 sh (3.77), 449 (3.55), 530 sh
(3.29). Found, %: C 42.62; H 3.55. C14H14N6O8.
Calculated, %: C 42.65; H 3.58. The nitration in the
system HNO3/MeCN gave 32% of compound XXV.
1
oil), , cm : 1670 (C O); 1580, 1510 (C Carom).
1H NMR spectrum (CDCl3), , ppm: 1.80 s (3H,
COMe); 2.83 s and 2.88 s (6H each, 1-NMe2 and
8-NMe2); 3.07 s (3H, CONMe); 6.72 d, 6.87 d,
7.13 d, and 7.52 d (1H each, 6-H, 3-H, 2-H, 7-H,
J2, 3 = 8.2, J6, 7 = 8.4 Hz). Found, %: C 61.52; H 6.44;
N 16.90. C17H22N4O3. Calculated, %: C 61.80;
H 6.71; N 16.96.
2,6-Dinitro-1,5-bis(p-tolylsulfonylamino)naph-
thalene (XXXIV), which was assigned in [18] the
structure of 4,8-dinitro derivative XXIX, was syn-
thesized by the procedure reported in [18] with the
difference that the product was filtered off after 2 days
rather than immediately after nitration. Yield 72%.
Lemon-yellow crystals with mp 262 263 C (from
aqueous pyridine) (cf. [18]). IR spectrum (mineral
Nitration of 4-acetamido-4,5-bis(dimethyl-
amino)naphthalene (XXXI). A mixture of 0.085 ml
(1.3 mmol) of HNO3 (d = 1.41) and 3 ml of concen-
trated sulfuric acid was added dropwise with vigorous
stirring to a solution of 0.36 g (1.3 mmol) of amide
XXXI [8] in 6 ml of concentrated sulfuric acid
(d = 1.84), cooled to 20 C. The red orange mixture
was stirred for 3 min at 20 C, poured onto 100 g
of crushed ice, neutralized with 55 ml of concentrated
aqueous ammonia, and extracted with chloroform.
By column chromatography on Al2O3 of Brockman
activity grade V (eluent chloroform) we isolated a red
fraction with Rf 0.43. Yield of 1-acetamido-4,5-bis-
(dimethylamino)-8-nitronaphthalene (XXX) 0.36 g
(86%). Dark red crystals with mp 161 163 C (from
1
oil), , cm : 3280 (NH); 1600, 1540 (C Carom);
1170, 1080 (SO2).
1,5-Diamino-2,6-dinitronaphthalene (XXXV).
The hydrolysis of compound XXXIV was carried out
as described in [18]. However, we failed to attain
the yield given in [18] (97%) by repeated experiments.
The yield of XXXV was 80%. In order to obtain
product XXXV as a readily filterable precipitate it
is advisable to pour the mixture into hot water with
special precautions.
1,5-Bis(dimethylamino)-2,6-dinitronaphthalene
(XXXVI). Diamine XXXV, 0.05 g (0.2 mmol), was
dissolved in 20 ml of acetone or acetonitrile, 0.09 g
(1.6 mmol) of powdered KOH was added, the dark
violet solution was stirred for 1 min, and 0.1 ml
1
octane). IR spectrum (mineral oil), , cm : 3240
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 5 2002

peri-NAPHTHALENEDIAMINES: XXXIV.
707
(1.6 mmol) of methyl iodide was added. The reaction
flask was tightly capped and was left to stand for
4 days with intermittent shaking. Additional amounts
of KOH and MeI (the same as above) were added, and
the mixture was kept for 4 days. The solvent was
evaporated, and the residue was washed with chloro-
form. The extract was subjected to a column charged
with silica gel, and the column was eluted with
chloroform to collect a bright orange fraction with
Rf 0.90. Yield of XXXVI 0.031 g (50%). Bright
orange leaflets with mp 170 171 C (from EtOH).
1H NMR spectrum (CDCl3 CCl4, 1 : 1), , ppm:
2.89 s (12H, NMe2), 7.62 d and 7.98 d (2H each,
4-H, 8-H, 3-H, 7-H, J3, 4 = 9.2 Hz). UV spectrum
(MeOH), max, nm (log ): 255 s (4.15), 282 (4.05),
328 (3.94), 433 (3.47). Found, %: C 54.86; H 4.92.
C14H16N4O4. Calculated, %: C 55.26; H 5.30.
1,4,5-Tris(dimethylamino)naphthalene (XXXIX)
was synthesized both as described in [8] and by the
following procedure. 1,4,5-Triaminonaphthalene
(XVII) [13], 0.5 g (2.9 mmol), was dissolved in
200 ml of anhydrous THF. The solution was stirred
for 5 min in an inert atmosphere, 2.2 g (46 mmol) of
powdered NaH was added, the mixture was heated to
the boiling point, and 4.4 ml (46 mmol) of Me2SO4
in 20 ml of THF was added dropwise with stirring to
the boiling mixture. The mixture was then refluxed
for 3 h, cooled to 20 C, diluted with 200 ml of con-
centrated aqueous sodium hydroxide, and vigorously
shaken. The organic phase was separated, and the
aqueous phase was extracted with hexane (2 50 ml).
The extracts were combined with the organic phase,
and the solvent was removed to obtain 0.3 g (60%) of
compound XXXIX as a reddish oily substance which
was identical to a sample prepared by the procedure
described in [8].
2,6-Diamino-1,5-bis(dimethylamino)naphthalene
(XXXVII) was synthesized from dinitro derivative
XXXVI, following the general procedure for reduc-
tion with tin(II) chloride (2 h, 25 C). Yield 85%.
Gray powder (relatively stable to oxidation with
atmospheric oxygen), mp 157 159 C. IR spectrum
1,4,5-Tris(dimethylamino)naphthalene hydro-
tetrafluoroborate (XXXIX HBF4) was synthesized
as described above for bis(hydrotetrafluoroborate)
II 2HBF4. Yield quantitative. Colorless powder,
mp 204 205 C (from MeOH).
1
(mineral oil), , cm : 3380, 3300 (NH2); 1630; 1600,
1
1500 (C Carom). H NMR spectrum (CDCl3), , ppm:
1,4,5-Tris(dimethylamino)-8-nitronaphthalene
(XL). Salt XXXIX HBF4, 0.2 g (0.6 mmol), was
dissolved at 20 C in 12 ml of concentrated sulfuric
acid (d = 1.84), and 0.04 ml (0.64 mmol) of concen-
trated nitric acid (d = 1.41) was added with stirring
at 20 C. The mixture was kept for 5 min with occa-
sional stirring, poured onto 80 g of ice, neutralized
with concentrated aqueous ammonia until persistent
odor, and extracted with chloroform (5 20 ml). The
solvent was removed from the extract, and the residue
was subjected to column chromatography on silica gel
using chloroform as eluent. A yellow brown fraction,
Rf 0.30, was collected. We isolated 0.088 g
(50%) of nitronaphthalene XL as an orange oily sub-
stance which crystallized on cooling to 0 C, mp 86
2.96 s (12H, NMe2), 3.9 br.s (4H, NH2), 6.96 d and
7.55 d (2H each, 3-H, 7-H, 4-H, 8-H, J3, 4 = 8.8 Hz).
General procedure for exhaustive alkylation of
naphthylamines with the system Me2SO4 Na2CO3
H2O. The alkylation was carried out by the modified
procedure [22]. To 1 mmol of naphthylamine we
added in succession dimethyl sulfate (4 mmol per
amino group), 5 ml of water, and Na2CO3 10H2O
in an amount equimolar to the dimethyl sulfate taken.
The mixture was vigorously stirred for 1 2 h at room
temperature until the initial compound disappeared
(TLC). The resulting suspension was neutralized with
concentrated aqueous ammonia until persistent odor
and was extracted with benzene. If necessary, the
product was purified by chromatography on Al2O3.
In such a way, the following compounds were syn-
thesized: I (yield 93%, from 1,8-diaminonaphthalene);
XXIII (65%, from 1,5-diaminonaphthalene), and
XXXIX (52%, from 1,4,5-triaminonaphthalene).
1
87 C (from MeOH). H NMR spectrum (CDCl3), ,
ppm: 2.55 s (6H, 1-NMe2), 2.74 br.s and 2.84 br.s
(6H each, 4-NMe2, 5-NMe2), 6.70 br.d and 6.93 br.d
(1H each, 3-H, 6-H, J2, 3 = 8.2, J6, 7 = 8.1 Hz), 7.21 d
and 7.34 d (1H each, 2-H, 7-H). UV spectrum (EtOH),
max, nm (log ): 355 (4.02), 420 sh (3.46). Found, %:
C 63.43; H 6.90. C16H22N4O2. Calculated, %:
C 63.56; H 7.33.
1,2,5,6-Tetrakis(dimethylamino)naphthalene
(XXXVIII). Amine XXXVII was alkylated with the
system Me2SO4/Na2CO3/H2O, following the above
general procedure. Yield of XXXVIII 60%. The prod-
uct was identical in physical and spectral parameters
Perchlorate XL HClO4. Yellowish needles. De-
1
1
composition point 222 223 C (from water). H NMR
to that described in [21]. H NMR spectrum (CDCl3),
spectrum (CD3CN), , ppm: 2.62 s (6H, 1-NMe2);
3.07 d (6H, 5-NMe2, JNH, NMe = 1.9 Hz); 3.17 d (6H,
4-NMe2, JNH, NMe = 3.3 Hz); 7.69 d, 7.81 d, 7.95 d,
, ppm: 2.72 s and 2.98 s (12H each, 2-NMe2,
6-NMe2, 1-NMe2, 5-NMe2), 7.27 d and 7.91 d (2H
each, 3-H, 7-H, 4-H, 5-H, J3, 4 = 9.1 Hz).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 5 2002

708
SOROKIN et al.
and 8.02 d (1H each, 2-H, 6-H, 7-H, 3-H, J2, 3 = 8.2,
J6, 7 = 8.4 Hz); 18.66 br.s (1H, NH). Found, %:
C 47.50; H 5.43; Cl 8.89. C16H23ClN4O6. Calculated,
%: C 47.70; H 5.76; Cl 8.80.
9. Organic Syntheses, Noland, W.E., Ed., New York:
Wiley, 1963, coll. vol. 4. Translated under the title
Sintezy organicheskikh preparatov, 1953, vol. 4,
pp. 376 377.
10. Gitis, S.S., Glaz, A.I., Grigor’ev, V.V., Kamin-
skii, A.Ya., Martynenko, A.S., and Saukov, P.I.,
Zh. Org. Khim., 1967, vol. 3, no. 9, pp. 1617 1620.
11. Makosza, M. and Bialecki, M., J. Org. Chem., 1998,
vol. 63, no. 15, pp. 4878 4888.
12. Quast, H., Risler, W., and Dollscher, G., Synthesis,
1-Amino-4,5,8-tris(dimethylamino)naphthalene
(XLI) was synthesized by reduction of nitro derivative
XL according to the general procedure (1 h, 25 C).
Yield 80%. Yellow oily substance which rapidly turns
1
green on exposure to air. IR spectrum (film), , cm :
3420, 3273 (NH2); 2913, 2847, 2806, 2760 (CH3);
1
1972, no. 10, p. 558.
1580, 1487 (C Carom). H NMR spectrum (CDCl3),
13. Ozeryanskii, V.A., Filatova, E.A., Sorokin, V.I., and
Pozharskii, A.F., Izv. Ross. Akad. Nauk, Ser. Khim.,
2001, no. 5, pp. 809 816.
, ppm: 2.68 s, 2.70 s, and 2.73 s (6H each, 4-NMe2,
8-NMe2, 5-NMe2); 6.52 d, 6.80 d, 6.82 d, and
7.04 d (1H each, 2-H, 3-H, 7-H, 6-H, J2, 3 = 8.1,
J6, 7 = 8.2 Hz).
14. Giumanini, A.G., Chiavari, G., Musiani, M.M., and
Rossi, P., Synthesis, 1980, no. 9, pp. 743 746.
Transformation of 1-amino-4,5,8-tris(dimethyl-
amino)naphthalene (XLI) into 1,4,5,8-tetrakis(di-
methylamino)naphthalene (II). Compound XLI was
alkylated following the general procedure with the
system Me2SO4/Na2CO3/H2O. Yield of II 40%. The
product was identical to samples of II prepared by
the other methods.
15. Zweig, A., Maurer, A., and Roberts, B.G., J. Org.
Chem., 1967, vol. 32, no. 5, pp. 1322 1329.
16. Brickman, M., Utley, J.H.P., and Ridd, J.H.,
J. Chem. Soc., 1965, no. 12, pp. 6851 6857.
17. Kurasov, L.A., Pozharskii, A.F., Kuz’menko, V.V.,
Klyuev, N.A., and Chernyshev, A.I., Zh. Org. Khim.,
1983, vol. 19, no. 3, pp. 590 597.
18. Nielsen, A.T., DeFusco, A.A., and Browne, T.E.,
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