Vicinal acetylenic derivatives of 2-amino-1,4-naphthoquinone as key precursors of heterocyclic quinones

Article abstract of DOI:10.1007/s11172-012-0084-8

The Pd-catalyzed reaction between 3-acetylamino-2-bromo-1,4-naphthoquinones and Cu^I acetylides prepared in situ gave 3-acetylamino-2-alkynyl-1, 4-naphthoquinones, which were transformed into benz[f]indole-4,9-dione and benzo[g]quinoline-5,10-dione derivatives.

Full text of DOI:10.1007/s11172-012-0084-8

Russian Chemical Bulletin, International Edition, Vol. 61, No. 3, pp. 582—588, March, 2012
582
Vicinal acetylenic derivatives of 2ꢀaminoꢀ1,4ꢀnaphthoquinone
as key precursors of heterocyclic quinones
M. S. Shvartsberg, E. A. Kolodina, N. I. Lebedeva, and L. G. Fedenok
Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences,
3 ul. Institutskaya, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383) 330 7350. Eꢀmail: shvarts@kinetics.nsc.ru
The Pdꢀcatalyzed reaction between 3ꢀacetylaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinones and CuI
acetylides prepared in situ gave 3ꢀacetylaminoꢀ2ꢀalkynylꢀ1,4ꢀnaphthoquinones, which were
transformed into benz[f]indoleꢀ4,9ꢀdione and benzo[g]quinolineꢀ5,10ꢀdione derivatives.
Key words: 1,4ꢀnaphthoquinones, bromoarenes, alkynes, organocopper compounds, heteroꢀ
cyclization, benz[f]indoleꢀ4,9ꢀdiones, benzo[g]quinolineꢀ5,10ꢀdiones.
Many biologically active compounds of the natural and
coupling products with terminal acetylenes in the convenꢀ
tional Sonogashira reaction,23 but reacts with CuI acetylꢀ
ides in the presence of the Pd complex as the catalyst.24
Unlike compound 1, neither 3ꢀaminoꢀ2ꢀbromoꢀ (2) nor
3ꢀaminoꢀ2ꢀiodoꢀ1,4ꢀnaphthoquinone (3) react with CuI
acetylides under the same conditions. We suggested that
a decrease in the reactivity of compounds 2 and 3 is assoꢀ
ciated with the formation of the pushꢀpull conjugated sysꢀ
synthetic origin, for example, serotonin,1 physostigmine,2
arbidol,3 indometacine,4 quinine,5 20(S)ꢀcamptothecin,6
and arylquinolines7 contain the indole or quinoline moiety.
Due to the high efficiency of the search for new biologiꢀ
cally active indole and quinoline derivatives, the parent
heterocycles, in the first turn indole, can be considered as
privileged structures.8,9 In 1970s, catalytic methods were
developed for the replacement of halogen atoms in aroꢀ
matic compounds by acetylenic groups.10—13 Later on,
a general methodology was elaborated for the design of
various multinuclear fused heterocycles starting from funcꢀ
tionalized orthoꢀ and periꢀsubstituted arylacetylenes. In
terms of this methodology, methods for the synthesis
of indoles and quinolines by the heterocyclization of
orthoꢀacetylenic derivatives of arylamines or ꢀamides were
developed and are widely used.14—17 However, the appliꢀ
cation of this method to the synthesis of indoleꢀ and quinꢀ
oline quinones, i.e., compounds in which the quinone ring
is fused directly to the heterocycle, is virtually unstudied
since the methods for the introduction of acetylenic subꢀ
stituents into the quinone ring are poorly developed. Meanꢀ
while, a number of compounds exhibiting pronounced biꢀ
ological activity, e.g. mitomycin,18 EO 9,19 streptonigrin,20
and marcanines21 contain the indole quinone or quinoline
quinone moiety.
tem
and the resulting increase in the
electron density on the C(2) atom. Obviously, Nꢀacetylꢀ
ated analogs should be more active because the +M effect
of the amido group is much weaker. The difference in the
electron density on the C(2) atom of compound 2 and its
Nꢀacetyl derivative 4 is confirmed by their 13C NMR spectra.
The signal of the C(2) atom in the spectrum of amide 4 is
shifted downfield by 29 ppm with respect to this signal in
the spectrum of amine 2. The experiment showed that
3ꢀacetylaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (4) and
its iodineꢀcontaining analog 5 exothermically react
with CuI acetylides in the presence of Pd(PPh3)2Cl2 in
a DMSO—CHCl3 mixture even at 20 C. 3,5ꢀBis(acetylꢀ
amino)ꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (6), in which the
benzene ring is potentially activated toward the electroꢀ
philic substitution, also readily reacts with CuI acetylides.
To develop a facile and versatile method for the synthesis
of 3ꢀacetylaminoꢀ2ꢀalkynylꢀ1,4ꢀnaphthoquinones 7 and 8,
we combined the preparation of copper acetylides from
terminal acetylenes 9 and the subsequent crossꢀcoupling
in a oneꢀpot process (Scheme 1, Table 1).
In the present study, we developed a general method
for the synthesis of vicꢀacetylenic derivatives of 2ꢀaminoꢀ
naphthoquinone and showed that they can undergo hetꢀ
erocyclization to form benz[f]indoleꢀ4,9ꢀdiones and benzoꢀ
[g]quinolineꢀ5,10ꢀdiones. The first results of the present
study have been published in the preliminary communiꢀ
cation.22
Acetylides, including those unstable in the solid state,
were synthesized by the reaction of acetylenes 9 with equivꢀ
alent amounts of CuI and Et3N in DMSO. Then bromo
derivatives 4 or 6 and the catalyst were added, and the
crossꢀcoupling was performed, which took 15—40 min. In
In fact, 2ꢀbromoꢀ1,4ꢀnaphthoquinone (1) containing
the halogen atom in the quinone ring does not give crossꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 580—586, March, 2012.
1066ꢀ5285/12/6103ꢀ582 © 2012 Springer Science+Business Media, Inc.

2ꢀAlkynylꢀ3ꢀaminoꢀ1,4ꢀnaphthoquinones
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 3, March, 2012
583
Scheme 1
Scheme 2
i. NaOH, dioxane, aqueous solution of EtOH.
10: R = CH2OTHP (a), CH(OH)Pri (b)
Scheme 3
Table 1. Crossꢀcoupling of bromineꢀcontaining naphthoꢀ
quinones 4 and 6 with terminal acetylenes 9
Comꢀ
pound
R1
R2
Yield (%)
7a
7b
7c
7d
7e
7f
7g
7h
8a
8b
8c
8d
Ph
H
H
H
H
H
H
H
H
NHAc
NHAc
NHAc
NHAc
73
81
65
82
83
73
73
77
85
90
92
93
4ꢀO2NC6H4
CH2OTHP*
CH2CH2OH
CH(OH)Pri
C(OH)Me2
C(cycloꢀPr)(Me)OH
1ꢀHydroxycyclohexyl
Ph
CH2OTHP*
C(OH)Me2
1ꢀHydroxycyclohexyl
* THP is tetrahydropyranꢀ2ꢀyl.
i. NH3, aqueous solution of dioxane.
the absence of the Pd catalyst, the reaction proceeded
much more slowly and was accompanied by the formation
of byꢀproducts. This synthesis is actually the oneꢀpot twoꢀ
step crossꢀcoupling of amidoquinonyl bromides with terꢀ
minal acetylenes.
Acetamidonaphthoquinonyl acetylenes 7 are easily
Nꢀdeacetylated in dioxane at 5—12 C when treated with
a 1% aqueous ethanol solution of NaOH (Scheme 2).
The precursor of acetylenes 7, viz., bromo derivative 4,
was synthesized from 1,4ꢀnaphthoquinone 11 (Scheme 3).
The treatment of quinone 11 with bromine in AcOH in
the presence of I2 at 118 C afforded 2,3ꢀdibromo derivaꢀ
tive 12.25 One of the halogen atoms in dibromide 12 was
replaced by the amino group using aqueous NH3 in diꢀ
oxane. Then product 2 was treated with Ac2O in the presꢀ
ence of a catalytic amount of H2SO4 in CHCl3 at 50 C to
prepare compound 4.
quinone 11 was nitrated with a mixture of NaNO3 and
H2SO4 at 0—40 C.26 The bromination of nitro quinone
13 afforded nitro dibromide 14, and the nitro group in the
latter was reduced with SnCl2 in a AcOH—HCl mixture at
70 C. The amino group at position 5 of compound 15
promotes the nucleophilic attack predominantly on posiꢀ
tion 3.16 In accordance with this fact, the reaction of 15
with aqueous NH3 produced almost exclusively individual
3,5ꢀdiaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (16). The
acetylation of diamine 16 was performed in two steps. In
the first step (Ac2O, H2SO4, dioxane, 50 C), 5ꢀacetylꢀ
aminoꢀ3ꢀaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (17) was
obtained. The latter was transformed into diacetyl derivaꢀ
tive 6 under the conditions of the acetylation of amine 2.
The proposed methods for the synthesis of bromo deꢀ
rivatives 4 and 6 and their crossꢀcoupling with terminal
acetylenes 9, as a whole, provide a preparatively simple
and versatile route from naphthoquinone 11 to vicꢀacetyꢀ
3,5ꢀDiacetylaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (6)
was synthesized in a similar way (Scheme 4). Naphthoꢀ

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Russ.Chem.Bull., Int.Ed., Vol. 61, No. 3, March, 2012
Shvartsberg et al.
Scheme 4
Scheme 5
lenic derivatives of 2ꢀacetylaminoꢀ and 2ꢀaminonaphthoꢀ
quinones 7, 8, and 10. We demonstrated the key role
of these acetylenes as precursors of nitrogenꢀcontaining
heterocyclic quinones by performing the synthesis of
benz[f]indoleꢀ4,9ꢀdiones and benzo[g]quinolineꢀ5,10ꢀ
diones.
It is known that the cyclization of oꢀalkynylarylamines
or ꢀamides to indoles is catalyzed by transition metal salts
and complexes and strong bases.27 Under drastic condiꢀ
tions of cyclization, naphthoquinone derivatives are unꢀ
stable. Hence, it was important to find out whether these
compounds are, in principle, able to undergo cyclization
under relatively mild conditions. We succeeded in perꢀ
forming the cyclization of a number of the synthesized
amido acetylenes 7a,c,f—h and 8c,d to the corresponding
indole quinones 18a—e and 19a,b in the presence of an
equimolar amount of anhydrous K2CO3 powder in MeCN
at 80 C (Scheme 5, Table 2).
The reaction is completed within 15—40 min. The
heterocyclization is accompanied by the deacylation to
give 2ꢀsubstituted benz[f]indoleꢀ4,9ꢀdiones 18 and 19. In
the case of substrates containing the tertiary alcohol group
7f—h and 8c,d, the reaction involves the dehydration to
form alkenylꢀsubstituted derivatives 18 and 19. Under the
reaction conditions used, 2ꢀalkynylꢀ3ꢀaminonaphthoꢀ
quinones do not undergo cyclization. The fact that the
cyclization of these compounds does not proceed under
mild conditions is apparently attributed to the characterꢀ
istic features of their conjugation system. The possibility
of cyclization depends on the delocalization of the negaꢀ
tive charge, which appears on the ꢀC atom of the acetylꢀ
enic substituent in the course of the nucleophilic addition
of the amino group. The polarization of the C(2)=C(3)
double bond and an increase in the electron density on the
C(2) atom hinder delocalization and, consequently, interꢀ
fere with the reaction. In addition, it cannot be ruled out
that the nucleophilic attack on the triple bond is preceded
by its deprotonation, which is more probable in the case of
amide substrates.
Table 2. Cyclization of amido acetylenes 7 and 8 to indole quinones 18 and 19
Starting
compound
Product
R1
R2
R3
Yield
(%)
7a
7c
7f
7g
7h
8c
8d
18a
18b
18c
18d
18e
19a
19b
Ph
H
H
H
H
H
Ph
73
43
65
53
70
75
40
CH2OTHP
C(OH)Me2
C(OH)Me(cycloꢀPr)
1ꢀHydroxycyclohexyl
C(OH)Me2
CH2OTHP
C(Me)=CH2
C(cycloꢀPr)=CH2
Cyclohexꢀ1ꢀenyl
C(Me)=CH2
Cyclohexꢀ1ꢀenyl
NHAc
NHAc
1ꢀHydroxycyclohexyl

2ꢀAlkynylꢀ3ꢀaminoꢀ1,4ꢀnaphthoquinones
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 3, March, 2012
585
It should be noted that the method used for the cyclꢀ
ization of amido acetylenes 7 and 8 is not versatile. The
cyclization of certain amido acetylenes, for example, of
7d,e and 8b, was accompanied by side reactions and resinꢀ
ification and gives indole quinones in low yields.
cedure. This method was used to synthesize piperidine
derivative 23 from ketone 20 (see Scheme 7).
Scheme 7
The proposed method for the crossꢀcoupling of bromoꢀ
quinonylamides with terminal acetylenes is a key to the
annulation of naphthoquinone not only to the pyrrole ring
but also to the sixꢀmembered pyridine ring. Previously, we
have performed the cyclization of 3ꢀaminoꢀ2ꢀ(4ꢀmethylꢀ
3ꢀoxopentenyl)ꢀ1,4ꢀnaphthoquinone (20) using HCl in
an organic solvent and prepared 4ꢀchloroꢀ2ꢀisopropylꢀ
benzo[g]quinolineꢀ5,10ꢀdione (21).28 The most facile and
efficient method for the synthesis of such acetylenic precurꢀ
sors of quinoline quinones involves the condensation of bromo
amide 4 with secondary acetylenic alcohols 9 followed by the
deacylation and selective oxidation of the resulting amino
alcohol with active MnO2. Ketone 20 was synthesized
from bromo derivative 4 in a total yield of 62% (Scheme 6).
Scheme 6
i. Dioxane.
Therefore, amido acetylenes of type 7, which are proꢀ
duced by the crossꢀcoupling of amido bromide 4 with secꢀ
ondary acetylenic alcohols, can be used as precursors of
4ꢀhaloꢀ1ꢀazaanthraquinones. The presence of a labile
halogen atom in the latter compounds provides the ability
to introduce various functional groups into these heteroꢀ
cyclic quinones.
The nature of the halogen atom in quinoline quinoꢀ
nes 21 can have a considerable effect on their reactivity
toward nucleophiles. The chlorine atom is easily replaced
in the reactions with such nucleophiles as amines and
phenols.28 In the catalytic crossꢀcoupling, bromides and
iodides are active, whereas chlorides are inactive.23 Since
we showed that it is, in principle, possible to construct the
pyridine ring based on acylethynylamines, which were preꢀ
pared from bromo derivatives 4, it was of interest to study
the prospects of the functionalization of the resulting
4ꢀhaloꢀ1ꢀazaanthraquinones. For this purpose, we perꢀ
formed the synthesis of 4ꢀbromoꢀ2ꢀisopropylbenzo[g]ꢀ
quinolineꢀ5,10ꢀdione (22). As expected, the reaction of
ketone 20 with HBr under the same conditions as those
used in the reaction with HCl affords bromoazaanthraꢀ
quinone 22 (Scheme 7). However, we failed to isolate
compound 22 in the analytically pure form due apparently
to its insufficient stability. Nevertheless, according to the
TLC data, compound 22 is the major reaction product,
and its structure was confirmed by 1H NMR spectroscopy.
The replacement of the bromine atom in compound 22
without its isolation can be performed by the oneꢀpot proꢀ
Experimental
1
The H NMR spectra were recorded on a Bruker DPXꢀ200
spectrometer (200 MHz) in CDCl3. The 13C NMR spectra were
measured on a Bruker AVꢀ300 spectrometer (75 MHz) in
DMSOꢀd6. The IR spectra were recorded on a Bruker Vector 22
instrument in CHCl3. The course of the reactions was monitored
and the purity of the compounds was checked by TLC on Silufol
UV 254 plates.
5ꢀNitroꢀ1,4ꢀnaphthoquinone (13) was synthesized according
to a known procedure26 in 78% yield, m.p. 167—168 C (MeOH).
2,3ꢀDibromoꢀ1,4ꢀnaphthoquinone (12) was synthesized by the
bromination of 1,4ꢀnaphthoquinone (11) according to a known
procedure29 in 93% yield, m.p. 216—217 C (toluene).
2,3ꢀDibromoꢀ5ꢀnitroꢀ1,4ꢀnaphthoquinone (14) was synꢀ
thesized as described for dibromide 12 starting from nitroꢀ
quinone 13 in 78% yield, m.p. 209—210 C (1,2ꢀdichloroꢀ
ethane—hexane).29

586
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Shvartsberg et al.
5ꢀAminoꢀ2,3ꢀdibromoꢀ1,4ꢀnaphthoquinone (15). A solution
Me); 5.73 (br.s, 2 H, NH2); 7.55—7.95 (m, 2 H, H(7), H(8));
8.90—9.00 (m, 1 H, H(6)); 11.50 (br.s, 1 H, NH).
of SnCl2•2H2O (22.4 g, 99.0 mmol) in concentrated HCl (26 mL)
was added dropwise to a suspension of compound 14 (6.7 g,
18.0 mmol) in AcOH (130 mL) under Ar at 50 C. The reaction
mixture was stirred at 70 C for 15 min and then cooled. Water
(0.5 L) and a solution of FeCl3•6H2O (31.3 g, 116.0 mmol) in
water (0.4 L) were successively added, and the reaction mixture
was stirred for 30 min. The precipitate was filtered off, washed
with water, and dried. The yield of amine 15 was 5.7 g (93%),
m.p. 225 C (decomp., toluene—hexane). Found (%): C, 36.00;
H, 1.83; Br, 48.08. C10H5Br2NO2. Calculated (%): C, 36.29;
H, 1.52; Br, 48.28. 1H NMR, : 6.76 (br.s, 2 H, NH2); 6.97 (dd,
1 H, H(6), J1 = 8.3 Hz, J2 = 1.1 Hz); 7.35—7.50 (m, 1 H, H(7));
7.55 (dd, 1 H, H(8), J1 = 7.3 Hz, J2 = 1.1 Hz). IR, /cm–1: 1610,
1670 (C=O); 3360, 3500 (NH2).
Step 2. The acetylation of monoamide 17 (1.0 g, 3.0 mmol)
with Ac2O (2.2 g, 2.0 mL, 21.5 mmol) in CHCl3 (40 mL), which
was performed as described for compound 2, afforded 3,5ꢀbisꢀ
(acetylamino)ꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone in a yield of 1.1 g
(97%) (6), m.p. 275 C (decomp., toluene). Found (%): C, 47.78;
H, 3.25; Br, 25.65. C14H11BrN2O4. Calculated (%): C, 47.88;
H, 3.16; Br, 22.75. 1H NMR, : 2.29 (s, 6 H, Ac); 7.55 (br.s, 1 H,
3ꢀNH); 7.65—7.80 (m, 1 H, H(7)); 7.94 (dd, 1 H, H(8), J1 = 7.6 Hz,
J2 = 1.2 Hz); 9.08 (dd, 1 H, H(6), J1 = 8.6 Hz, J2 = 1.2 Hz);
11.45 (br.s, 1 H, 5ꢀNH). IR, /cm–1: 1620,1645, 1675, 1710
(C=O); 3310, 3375 (NH).
Crossꢀcoupling of 3ꢀacetylaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinoꢀ
nes 4 and 6 with terminal acetylenes 9 (general procedure). Copꢀ
per iodide (0.35 g, 1.8 mmol) was added to DMSO (10 mL), and
this was stirred under argon at 20 C for 10 min. Then Et3N
(0.18 g, 0.25 mL, 1.8 mmol) and terminal acetylene 9 (2.0 mmol)
were added. After 10 min, a solution of bromide 4 or 6 (1.5 mmol)
and Pd(PPh3)2Cl2 (10 mg) in anhydrous CHCl3 (5 mL)
were added. The reaction mixture was stirred at 20 C for
15—40 min (until the completion of the reaction), diluted with
CHCl3 (100 mL) containing AcOH (0.5 mL), and poured into
water (0.4 L) acidified with AcOH (1 mL). The precipitate was
filtered off and washed with CHCl3. The organic layer was sepaꢀ
rated, and the aqueous layer was extracted with CHCl3. The
combined chloroform extracts were washed with water and dried
with MgSO4. The solvent was removed in vacuo. Product 7 or 8
was recrystallized from hexane, cooled, filtered off, and washed
with a small amount of diethyl ether (see Table 1).
3ꢀAminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (2). A mixture of diꢀ
bromide 12 (8.0 g, 20.0 mmol), dioxane (130 mL), and 25%
aqueous NH3 (110 mL) was stirred at 25—30 C for 2.5 h and then
poured into water (1.5 L). The precipitate was filtered off, washed
with water, and dried in air. The yield of product 2 was 5.8 g (91%),
m.p. 204—205 C (toluene, cf. lit. data25). 13C NMR, : 101.4
(C(2)); 126.1, 126.4, 132.6, 132.8 (C(5), C(6), C(7), C(8)); 129.6,
132.2 (C(4a), C(8a)); 148.8 (C(3)); 175.1, 178.7 (C(1), C(4)).
3,5ꢀDiaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (16). The aminaꢀ
tion of compound 15 (4.0 g, 12.0 mmol) was performed as deꢀ
scribed for amine 2. The yield of product 16 was 3.0 g (93%),
m.p. 260 C (decomp., toluene). Found (%): C, 44.83; H, 2.60;
Br, 29.59. C10H7BrN2O2. Calculated (%): C, 44.97; H, 2.64;
Br, 29.92. 1H NMR, : 5.68 (br.s, 2 H, NH2); 6.64 (br.s, 2 H, NH2);
6.84 (dd, 1 H, H(6), J1 = 8.4 Hz, J2 = 1.1 Hz); 7.35—7.50 (m, 1 H,
H(7)); 7.55 (dd, 1 H, H(8), J1 = 7.3 Hz, J2 = 1.1 Hz). IR, /cm–1
:
3ꢀAcetylaminoꢀ2ꢀphenylethynylꢀ1,4ꢀnaphthoquinone (7a).
M.p. 186—187 C (decomp., EtOH).24
1610 (C=O); 3340, 3450 (NH2); 3315, 3430 (NH2).
3ꢀAcetylaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (4). The acetylꢀ
ating reagent, which was prepared by shacking Ac2O (2.4 g,
2.3 mL, 24.3 mmol), concentrated H2SO4 (0.10—0.15 mL), and
CHCl3 (2 mL), was added with stirring to a solution of amine 2
(1.5 g, 5.9 mmol) in anhydrous CHCl3 (75 mL). The reaction
mixture was heated at 50 C for 45 min, cooled, and poured into
water (0.5 L). The organic layer was separated, and the aqueous
layer was extracted with CHCl3. The combined extracts were
washed with water and dried with MgSO4. The solvent was reꢀ
moved in vacuo. Toluene was added to the residue, and the
solvent was again removed in vacuo. This operation was repeated
several times. After recrystallization of the solid residue from
a mixture of CHCl3 and toluene, amide 4 was isolated in a yield
of 1.0 g (62%), m.p. 226—227 C (cf. lit. data25). 13C NMR, :
23.0 (Me); 126.7, 126.9, 134.5 (C(5), C(6), C(7), C(8)); 130.3
(C(2)); 130.7, 130.9 (C(4a), C(8a)); 144.6 (C(3)); 168.1 (CO
(Ac)); 177.8, 178.1 (C(1), C(4)).
3,5ꢀBis(acetylamino)ꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (6). Step 1.
5ꢀAcetylaminoꢀ3ꢀaminoꢀ2ꢀbromoꢀ1,4ꢀnaphthoquinone (17).
A solution of diamine 16 (1.1 g, 4.0 mmol) and Ac2O (4.3 g,
4.0 mL, 42.0 mmol) in anhydrous dioxane (75 mL) acidified
with concentrated H2SO4 (0.05 mL) was stirred at 60 C for
15 min, cooled, diluted with water, and extracted with CHCl3.
The extract was washed with water and dried with MgSO4. The
solvent was removed in vacuo. The yield of compound 17 conꢀ
taining a small amount of diamide 6 was obtained in a yield of
1.2 g (97%). M.p. compound 17 260 C (decomp., toluene).
Found (%): C, 47.00; H, 2.95; Br, 25.30. C12H9BrN2O3. Calcuꢀ
lated (%): C, 46.63; H, 2.93; Br, 25.85. 1H NMR, : 2.29 (s, 3 H,
3ꢀAcetylaminoꢀ2ꢀ(4ꢀnitrophenylethynyl)ꢀ1,4ꢀnaphthoquinone
(7b). M.p. 222—223 C (decomp., EtOAc). Found (%): C, 66.59;
H, 3.09. C20H12N2O5. Calculated (%): C, 66.67; H, 3.36.
1H NMR, : 2.35 (s, 3 H, Ac); 7.65—7.85 (m, 4 H, H(6), H(7),
PhNO2); 8.05—8.30 (m, 5 H, H(5), H(8), PhNO2, NH). IR,
/cm–1: 1668, 1730 (C=O); 2203 (CC); 3358 (NH).
3ꢀAcetylaminoꢀ2ꢀ[3ꢀ(tetrahydropyranꢀ2ꢀyloxy)propꢀ1ꢀynꢀ1ꢀ
yl]ꢀ1,4ꢀnaphthoquinone (7c). M.p. 139—140 C (toluene).
Found (%): C, 67.92; H, 5.68; N, 4.30. C20H19NO5. Calculatꢀ
ed (%): C, 67.98; H, 5.42; N, 3.96. 1H NMR, : 1.50—1.90
(m, 6 H, (CH2)3); 2.27 (s, 3 H, Ac); 3.50—3.65 and 3.80—3.95
(both m, 2 H, OCH2); 4.60 (d, 2 H, CCCH2, J = 0.8 Hz); 4.95
(br.s, 1 H, OCHO); 7.70—7.80 (m, 2 H, H(6), H(7)); 7.94 (br.s,
1 H, NH); 8.00—8.20 (m, 2 H, H(5), H(8)). IR, /cm–1: 1666,
1730 (C=O); 2223 (CC); 3365 (NH).
3ꢀAcetylaminoꢀ2ꢀ(4ꢀhydroxybutꢀ1ꢀynꢀ1ꢀyl)ꢀ1,4ꢀnaphthoꢀ
quinone (7d). M.p. 163—164 C (toluene). Found (%): C, 68.07;
H, 4.59; N, 5.02. C16H13NO4. Calculated (%): C, 67.84; H, 4.63;
N, 4.94. 1H NMR, : 2.30 (s, 3 H, Ac); 2.79 (т, 2 H, CCCH2, J =
= 5.3 Hz); 3.60—3.90 (m, 3 H, CH2, OH); 7.65—7.85 (m, 2 H,
H(6), H(7)); 8.00—8.20 (m, 3 H, H(5), H(8), NH). IR, /cm–1
:
1699, 1705, 1717 sh (C=O); 2222 (CC); 3362 (NH); 3486 w (OH).
3ꢀAcetylaminoꢀ2ꢀ(3ꢀhydroxyꢀ4ꢀmethylpentꢀ1ꢀynꢀ1ꢀyl)ꢀ1,4ꢀ
naphthoquinone (7e). M.p. 148—149 C (toluene).28
3ꢀAcetylaminoꢀ2ꢀ(3ꢀhydroxyꢀ3ꢀmethylbutꢀ1ꢀynꢀ1ꢀyl)ꢀ1,4ꢀ
naphthoquinone (7f). M.p. 160—161 C (toluene). Found (%):
C, 68.44; H, 5.11; N, 4.94. C17H15NO4. Calculated (%): C, 68.68;
1
H, 5.09; N, 4.71. H NMR, : 1.61 (s, 6 H, Me); 2.28 (s, 3 H,
Ac); 2.47 (br.s, 1 H, OH); 7.70—7.80 (m, 2 H, H(6), H(7)); 7.97

2ꢀAlkynylꢀ3ꢀaminoꢀ1,4ꢀnaphthoquinones
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 3, March, 2012
587
(br.s, 1 H, NH); 8.05—8.20 (m, 2 H, H(5), H(8)). IR, /cm–1
1669, 1727 (C=O); 2219 (CC); 3365 (NH); 3498 br (OH).
:
extracted with CH2Cl2. The organic extract was washed with water
and dried with MgSO4, and the solvent was removed in vacuo.
The product was crystallized in hexane and filtered off. The yield
of compound 10c was 0.24 g (80.0%), m.p. 129—130 C (diethyl
ether). Found (%): C, 69.28; H, 5.53; N, 4.48. C18H17NO4.
Calculated (%): C, 69.44; H, 5.50; N, 4.50. 1H NMR, : 1.60—1.90
(m, 6 H, (CH2)3); 3.45—3.60 and 3.80—3.95 (both m, 2 H,
OCH2); 4.60 (s, 2 H, CCCH2); 4.85—4.95 (m, 1 H, OCHO);
5.95 (br.s, 2 H, NH2); 7.55—7.80 (m, 2 H, H(6), H(7)); 8.00—8.15
(m, 2 H, H(5), H(8)). IR, /cm–1: 1645, 1677 (C=O); 2217
(CC); 3384, 3502 (NH2).
3ꢀAcetylaminoꢀ2ꢀ(3ꢀhydroxyꢀ3ꢀcyclopropylbutꢀ1ꢀynꢀ1ꢀyl)ꢀ
1,4ꢀnaphthoquinone (7g). M.p. 134—135 C (toluene). Found (%):
C, 70.80; H, 5.46; N, 4.46. C19H17NO4. Calculated (%):
1
C, 70.58; H, 5.30; N, 4.33. H NMR, : 0.40—0.80 (m, 4 H,
(CH2)2); 1.15—1.30 (m, 1 H, CH); 1.66 (s, 3 H, Me); 2.28 (s, 3 H,
Ac); 2.60 (br.s, 1 H, OH); 7.65—7.80 (m, 2 H, H(6), H(7)); 7.97
(br.s, 1 H, NH); 8.00—8.15 (m, 2 H, H(5), H(8)). IR, /cm–1
1667, 1723 (C=O); 2218 (CC); 3366 (NH); 3585 br (OH).
:
3ꢀAcetylaminoꢀ2ꢀ(1ꢀhydroxycyclohexylethynyl)ꢀ1,4ꢀnaphꢀ
thoquinone (7h). M.p. 164—165 C (toluene). Found (%):
C, 71.13; H, 5.87; N, 4.33. C20H19NO4. Calculated (%): C, 71.20;
H, 5.68; N, 4.15. 1H NMR, : 1.50—1.80 and 1.95—2.10
(both m, 10 H, (CH2)5); 2.28 (s, 3 H, Ac); 2.67 (br.s, 1 H, OH);
7.65—7.80 (m, 2 H, H(6), H(7)); 7.97 (br.s, 1 H, NH); 8.00—8.15
(m, 2 H, H(5), H(8)). IR, /cm–1: 1667, 1727 (C=O); 2215
(CC); 3366 (NH); 3492 s (OH).
3ꢀAminoꢀ2ꢀ(3ꢀhydroxyꢀ4ꢀmethylpentꢀ1ꢀynꢀ1ꢀyl)ꢀ1,4ꢀnaphthoꢀ
quinone (10b). Amino alcohol 10b was synthesized as described
for amine 10a, m.p. 143—144 C.28
3ꢀAminoꢀ2ꢀ(4ꢀmethylꢀ3ꢀoxopentꢀ1ꢀynꢀ1ꢀyl)ꢀ1,4ꢀnaphthoꢀ
quinone (20). A mixture of amino alcohol 10b (0.7 g, 2.6 mmol)
and activated MnO2 (7.0 g) in anhydrous CHCl3 (90 mL) was
stirred at 20 C for 30—40 min (until the competion of the reacꢀ
tion). The precipitate was filtered off and thoroughly washed
with CHCl3. The solvent was removed in vacuo, and the residue
was crystallized in hexane. The yield was 0.6 g (85.7%), m.p.
145—146 C (toluene—hexane).28
Indoles 18 and 19 (general procedure). A mixture of amide
7a—h or 8c,d (0.8 mmol), freshly calcined K2CO3 powder
(0.8 mmol), and MeCN (30 mL) was stirred at 80 C until the
competion of the reaction. Then the reaction mixture was cooled
and filtered. The filtrate was diluted with water (0.2 L) acidified
with AcOH (1 mL) and extracted with CHCl3. The extract was
washed with water and dried with MgSO4. The solvent was reꢀ
moved in vacuo. Product 18 or 19 was isolated by chromatoꢀ
graphy on SiO2 using CH2Cl2, a toluene—CHCl3 mixture, or
a toluene—AcOEt mixture as the eluent (see Table 2).
2ꢀPhenylbenz[f]indoleꢀ4,9ꢀdione (18a). M.p. 305—306 C
(toluene—diethyl ether). Found (%): C, 79.07; H, 4.05; N, 4.94.
C18H11NO2. Calculated (%): C, 79.11; H, 4.06; N, 5.12. 1H NMR,
: 7.09 (s, 1 H, H(3)); 7.30—7.55 (m, 3 H, Ph); 7.65—7.75
(m, 4 H, H(6), H(7), Ph); 8.10—8.25 (m, 2 H, H(5), H(8));
10.25 (br.s, 1 H, NH). IR, /cm–1: 1654 (C=O); 3428 (NH).
2ꢀ(Tetrahydropyranꢀ2ꢀyloxy)benz[f]indoleꢀ4,9ꢀdione (18b).
M.p. 166—167 C (toluene—diethyl ether). Found (%): C, 69.52;
H, 5.65; N, 4.69. C18H17NO4. Calculated (%): C, 69.44; H, 5.50;
N, 4.50. 1H NMR, : 1.50—2.00 (m, 6 H, (CH2)3); 3.50—3.70 and
3.90—4.05 (both m, 2 H, CH2O); 4.65—4.80 (m, 1 H, OCHO);
4.75 (d, 2 H, CH2O, J = 3.4 Hz); 6.65 (s, 1 H, H(3)); 7.60—7.75
(m, 2 H, H(6), H(7)); 8.05—8.20 (m, 2 H, H(5), H(8)); 9.95
(br.s, 1 H, NH). IR, /cm–1: 1693 (C=O); 3420 (NH).
2ꢀIsopropenylbenz[f]indoleꢀ4,9ꢀdione (18c). M.p. 168—169 C
(toluene—hexane). Found (%): C, 75.69; H, 4.92; N, 5.97.
C15H11NO2. Calculated (%): C, 75.93; H, 4.67; N, 5.90.
1H NMR, : 2.15 (s, 3 H, Me); 5.21 (d, 1 H, =CHa, J = 1.4 Hz);
5.48 (s, 1 H, =CHb); 6.82 (d, 1 H, H(3), J = 2.4 Hz); 7.60—7.75
(m, 2 H, H(6), H(7)); 8.05—8.20 (m, 2 H, H(5), H(8)); 9.55
(br.s, 1 H, NH). IR, /cm–1: 1653 (C=O); 3432 (NH).
3,5ꢀBis(acetylamino)ꢀ2ꢀphenylethynylꢀ1,4ꢀnaphthoquinone
(8a). M.p. 148—149.5 C (decomp., toluene). Found (%): C, 70.96;
H, 4.63; N, 7.29. C22H16N2O4. Calculated (%): C, 70.96; H, 4.33;
N, 7.52. 1H NMR, : 2.24 and 2.33 (both s, 6 H, Ac); 7.30—7.45
(m, 3 H, Ph); 7.50—7.65 (m, 2 H, Ph); 7.65—7.80 (m, 1 H,
H(7)); 7.80—7.95 (m, 1 H, H(8)); 7.98 (br.s, 1 H, 3ꢀNH);
8.95—9.10 (m, 1 H, H(6)); 11.63 (br.s, 1 H, 5ꢀNH). IR, /cm–1
1635, 1670, 1710 (C=O); 2207 (CC); 3310, 3380 (NH).
:
3,5ꢀBis(acetylamino)ꢀ2ꢀ[3ꢀ(tetrahydropyranꢀ2ꢀyloxy)propꢀ
1ꢀynꢀ1ꢀyl]ꢀ1,4ꢀnaphthoquinone (8b). M.p. 118 C (decomp.,
toluene). Found (%): C, 64.09; H, 5.19; N, 7.03. C22H22N2O6.
Calculated (%): C, 64.38; H, 5.40; N, 6.83. 1H NMR, : 1.60—1.90
(m, 6 H, (CH2)3); 2.27 and 2.28 (both s, 6 H, Ac); 3.45—3.60 and
3.75—3.95 (both m, 2 H, OCH2); 4.59 (s, 2 H, CCCH2); 4.93 (br.s,
1 H, OCHO); 7.60—7.80 (m, 1 H, H(7)); 7.86 (dd, 1 H, H(8),
J1 = 7.5 Hz, J2 = 1.2 Hz); 7.95 (br.s, 1 H, 3ꢀNH); 9.03 (dd,
1 H, H(6), J1 = 8.5 Hz, J2 = 1.2 Hz); 11.57 (br.s, 1 H, 5ꢀNH).
IR, /cm–1: 1634, 1668, 1707 (C=O); 2227 (CC); 3302,
3370 (NH).
3,5ꢀBis(acetylamino)ꢀ2ꢀ(3ꢀhydroxyꢀ3ꢀmethylbutꢀ1ꢀynꢀ1ꢀyl)ꢀ
1,4ꢀnaphthoquinone (8c). M.p. 170 C (decomp., toluene—diꢀ
ethyl ether). Found (%): C, 64.19; H, 5.18; N, 8.02. C19H18N2O5.
1
Calculated (%): C, 64.40; H, 5.12; N, 7.90. H NMR, ): 1.61
(s, 6 H, Me); 2.28 and 2.29 (both s, 6 H, Ac); 2.72 (br.s, 1 H, OH);
7.65—7.80 (m, 1 H, H(7)); 7.84 (dd, 1 H, H(8), J = 7.6 Hz,
J = 1.3 Hz); 7.99 (br.s, 1 H, 3ꢀNH); 9.03 (dd, 1 H, H(6) J = 8.5 Hz,
J = 1.3 Hz); 11.59 (br.s, 1 H, 5ꢀNH). IR, /cm–1: 1634, 1666,
1707 (C=O); 2217 (CC); 3303, 3369 (NH); 3496 w (OH).
3,5ꢀBis(acetylamino)ꢀ2ꢀ(1ꢀhydroxycyclohexylethynyl)ꢀ1,4ꢀ
naphthoquinone (8d). M.p. 172—173 C (toluene—diethyl ether).
Found (%): C, 67.11; H, 5.41; N, 7.24. C22H22N2O5. Calculatꢀ
ed (%): C, 66.99; H, 5.62; N, 7.10. 1H NMR, : 1.50—1.80 and
1.95—2.10 (both m, 10 H, (CH2)5); 2.29 (s, 6 H, Ac); 2.75 (br.s,
1 H, OH); 7.65—7.90 (m, 2 H, H(7), H(8)); 7.97 (br.s, 1 H,
3ꢀNH); 9.03 (dd, 1 H, H(6), J = 8.5 Hz, J = 1.2 Hz); 11.61 (br.s,
1 H, 5ꢀNH). IR, /cm–1: 1633, 1666, 1712 (C=O); 2213 (CC);
3299, 3370 (NH), 3496 w (OH).
3ꢀAminoꢀ2ꢀ[3ꢀ(tetrahydropyranꢀ2ꢀyloxy)propꢀ1ꢀynꢀ1ꢀyl]ꢀ
1,4ꢀnaphthoquinone (10a). A solution of NaOH (0.06 g, 1.5 mmol)
in aqueous EtOH (1 : 1, v/v, 10 mL) was gradually added with
stirring to a solution of amide 7c (0.34 g, 0.9 mmol) in dioxane
(20 mL) at 5—12 C for 1.5 h until the starting compound was conꢀ
sumed. The reaction mixture was diluted with water (0.3 L) and
2ꢀ(1ꢀCyclopropylvinyl)benz[f]indoleꢀ4,9ꢀdione (18d). M.p.
177—178 C (toluene). Found (%): C, 77.72; H, 5.13; N, 5.21.
C17H13NO2. Calculated (%): C, 77.55; H, 4.98; N, 5.32. 1H NMR,
: 0.55—0.70 and 0.80—0.95 (both m, 4 H, (CH2)2); 1.60—1.80
(m, 1 H, CH); 5.13 (d, 1 H, C=CHa, J = 2.3 Hz); 5.51 (s, 1 H,
C=CHb); 6.99 (d, 1 H, H(3), J = 2.4 Hz); 7.60—7.75 (m, 2 H,
H(6), H(7)); 8.05—8.20 (m, 2 H, H(5), H(8)); 9.75 (br.s, 1 H,
NH). IR, /cm–1: 1655 (C=O); 3434 (NH).

588
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 3, March, 2012
Shvartsberg et al.
2ꢀ(Cyclohexꢀ1ꢀenyl)benz[f]indoleꢀ4,9ꢀdione (18e). M.p.
5. V. V. Kouznetsov, L. Y. Vargas Mendez, C. M. Melendez
Gomez, Curr. Org. Chem., 2005, 9, 141.
6. W. Du, Tetrahedron, 2003, 59, 8649.
245—246 C (toluene—diethyl ether). Found (%): C, 77.73;
H, 5.56; N, 5.14. C18H15NO2. Calculated (%): C, 77.96; H, 5.45;
N, 5.05. 1H NMR, : 1.55—1.85 (m, 4 H, (CH2)2, cyclohexenyl);
2.15—2.45 (m, 4 H, CH2—C=C—CH2); 6.35—6.45 (m, 1 H,
HC=C); 6.73 (d, 1 H, H(3), J = 2.3 Hz); 7.55—7.75 (m, 2 H,
H(6), H(7)); 8.05—8.20 (m, 2 H, H(5), H(8)); 9.90 (br.s, 1 H,
NH). IR, /cm–1: 1647 (C=O); 3432 (NH).
8ꢀAcetylaminoꢀ2ꢀisopropenylbenz[f]indoleꢀ4,9ꢀdione (19a).
M.p. 191—192 C (toluene). Found (%): C, 69.30; H, 5.08;
N, 9.74. C17H14N2O3. Calculated (%): C, 69.38; H, 4.80; N, 9.52.
1H NMR, : 2.14 (s, 3 H, Me); 2.29 (s, 3 H, Ac); 5.23 (d, 1 H,
=CHa, J = 1.5 Hz); 5.46 (s, 1 H, =CHb); 6.78 (d, 1 H, H(3),
J = 2.4 Hz); 7.55—7.70 (m, 1 H, H(6)); 7.93 (dd, 1 H, H(5),
J1 = 7.6 Hz, J2 = 1.2 Hz); 8.97 (dd, 1 H, H(7), J1 = 8.5 Hz,
J2 = 1.2 Hz); 9.33 (br.s, 1 H, H(1)); 12.18 (br.s, 1 H, 8 NH). IR,
/cm–1: 1628, 1669, 1695 (C=O); 3432 (NH).
8ꢀAcetylaminoꢀ2ꢀ(cyclohexꢀ1ꢀenyl)benz[f]indoleꢀ4,9ꢀdione
(19b). M.p. 149—150 C (toluene—hexane). Found (%): C, 71.95;
H, 5.50; N, 8.26. C20H18N2O3. Calculated (%): C, 71.84;
H, 5.43; N, 8.38. 1H NMR, : 1.60—1.85 (m, 4 H, (CH2)2,
cyclohexenyl); 2.15—2.40 (m, 7 H, Ac, CH2—C=C—CH2);
6.25—6.35 (m, 1 H, C=CH); 6.69 (d, 1 H, H(3), J = 2.3 Hz);
7.55—7.70 (m, 1 H, H(6)); 7.92 (dd, 1 H, H(5), J1 = 7.6 Hz,
J2=1.2 Hz); 8.97 (dd, 1 H, H(7), J1 = 8.6 Hz, J2 = 1.2 Hz); 9.25
(br.s, 1 H, H(1)); 12.23 (br.s, 1 H, 8 NH). IR, /cm–1: 1623,
1668, 1696 (C=O); 3435 (NH).
7. A. Capelli, G. Pericot Mohr, A. Gallelli, G. Cuiliani,
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2ꢀIsopropylꢀ4ꢀpiperidinobenzo[g]quinolineꢀ5,10ꢀdione (23).
A HBr solution (9—10 mL, 1.5—1.7 mmol of HBr), which was
prepared by saturation of CHCl3 with gaseous HBr, was added to
a solution of compound 20 (0.2 g, 0.75 mmol) in anhydrous
CHCl3 (7 mL) under Ar for 2—3 min. The reaction mixture was
stirred at 20 C for 7—10 h. During this period of time, the same
HBr solution (8 mL, 1.4—1.5 mmol of HBr) was additionally
added in three portions. Then the solvent and an excess of HBr
were removed under an argon flow, the residue was dissolved in
dioxane (10 mL), and piperidine (3.4 h, 4.0 mL, 40.0 mmol) was
added. The reaction mixture was stirred at 20 C for 30 min and
diluted with water (0.3 L). The product was extracted with
CHCl3. The organic extract was washed with water and dried
with MgSO4. The solvent was removed in vacuo, and the residue
was chromatographed on SiO2 (a toluene—ethylacetate mixꢀ
ture, 5 : 1, as the eluent). The yield of product 23 was 0.10 g
(40%), m.p. 123—124 C (diethyl ether—hexane).30
17. G. Abbiati, A. Arcadi, F. Marinelli, E. Rossi, M. Verdecꢀ
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Received April 14, 2011;
in revised form January 23, 2012