Synthesis of 5-aryl-1,4-naphthoquinone and 1-aryl-9,10-anthraquinone derivatives by cycloaddition of 1-(dimethoxyphenyl)-3-trimethylsiloxy-1,3- butadienes to 1,4-benzoquinones and 1,4-naphthoquinones

Article abstract of DOI:10.1023/B:RUJO.0000010560.88282.d3

The Diels-Alder reaction of new 1-(3,4-dimethoxyphenyl)- or 1-(2,4-dimethoxyphenyl)-2-R-3-trimethylsiloxy-1,3-butadienes with 2,5- and 2,6-dibromo-, and 2-bromo-6-methyl-1,4-benzoquinones regioselectively yields substituted 7-hydroxy-5-(dimethoxyphenyl)-1,4-naphthoquinones. By cycloaddition of the siloxydienes to naphthoquinone, bromonaphthoquinone, and juglone the corresponding substituted 3-hydroxy-1-(dimethoxyphenyl)-9,10-anthraquinones or their 4,4a-dihydro or 1,1a,4,4a-tetrahydro derivatives were obtained.

Full text of DOI:10.1023/B:RUJO.0000010560.88282.d3

Russian Journal of Organic Chemistry, Vol. 39, No. 10, 2003, pp. 1436 1450. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 10, 2003,
pp. 1508 1520.
Original Russian Text Copyright
2003 by Nechepurenko, Shul’ts, Tolstikov.
Synthesis of 5-Aryl-1,4-naphthoquinone
and 1-Aryl-9,10-anthraquinone Derivatives by Cycloaddition
of 1-(Dimethoxyphenyl)-3-trimethylsiloxy-1,3-butadienes
to 1,4-Benzoquinones and 1,4-Naphthoquinones
I. V. Nechepurenko, E. E. Shul’ts, and G. A. Tolstikov
Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 9, Novosibirsk, 630090 Russia
e-mail: niv@nioch.nsc.ru
Received November 20, 2002
Abstract The Diels Alder reaction of new 1-(3,4-dimethoxyphenyl)- or 1-(2,4-dimethoxyphenyl)-2-R-3-tri-
methylsiloxy-1,3-butadienes with 2,5- and 2,6-dibromo-, and 2-bromo-6-methyl-1,4-benzoquinones regio-
selectively yields substituted 7-hydroxy-5-(dimethoxyphenyl)-1,4-naphthoquinones. By cycloaddition of the
siloxydienes to naphthoquinone, bromonaphthoquinone, and juglone the corresponding substituted 3-hydroxy-
1-(dimethoxyphenyl)-9,10-anthraquinones or their 4,4a-dihydro or 1,1a,4,4a-tetrahydro derivatives were
obtained.
The presence of a polyhydroxy- or polymethoxy-
aromatic substituent is a characteristic feature of many
series of naturally occurring biologically active
compounds. Introduction of these pharmacophoric
fragments into quinone molecules is very interesting
from the practical viewpoint, specifically with a view
to create new pharmacological agents. For example,
such substituted 1-[hydroxy(methoxy)aryl]-9,10-an-
thraquinones as knipholone and gaboroquinones A
and B, isolated from plants of the Bulbine, Bulbinella,
Kniphofia (Asphodelacea), and Senna (Fabacea)
species, are known to exhibit antiplasmoid and wound
healing activities [1].
The Diels Alder reaction of siloxybutadienes with
quinones underlies a generally accepted method for
the synthesis of polyfunctional naphtho- and anthra-
quinones. We previously applied this approach to the
preparation of 5-aryl-7-hydroxy-1,4-naphthoquinones
and 1-aryl-3-hydroxy-9,10-anthraquinones [2]. Some
products synthesized in such a way were found to
exhibit a high activity as inhibitors of HIV reverse
transcriptase [3].
In the present work we continued our studies on
cycloaddition of 1-aryl-3-siloxydienes with quinones
and showed that 2-substituted 1-(dimethoxyphenyl)-3-
trimethylsiloxy-1,3-butadienes are convenient building
Scheme 1.
I, II, IV, V, R = H; III, VI, R = OMe; I, II, IV, V, R = OMe; III, VI, R = H; I, IV, X = H;
II, III, V, VI, X = CO2Et.
1070-4280/03/3910-1436$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS OF 5-ARYL-1,4-NAPHTHOQUINONE
1437
Scheme 2.
VII, VIII, XI, XII, Ar = 3,4-(MeO)2C6H3; IX, X, XIII, 2,4-(MeO)2C6H3.
blocks which make it possible to introduce hydroxy
and dimethoxyphenyl groups into a quinone molecule
in one step. The Diels Alder reaction of siloxybuta-
dienes with brominated benzo- and naphthoquinones
involves successive cycloaddition and dehydro-
bromination, leading to 3-hydroxy-1-(dimethoxy-
phenyl)naphtho- and -anthraquinones, respectively.
butadienes IV VI were synthesized in 66, 92, and
40% yield, respectively, by reaction of methyl styryl
ketones I III with chlorotrimethylsilane in the pres-
ence of anhydrous zinc(II) chloride and triethylamine
under argon (Scheme 1). Compounds IV VI undergo
decomposition on attempted distillation; therefore,
the crude products were purified by passing through
a layer of silica gel deactivated by microwave radia-
tion. Siloxydienes IV VI are yellow brown oils
which can be stored in an argon atmosphere.
The reaction of siloxydiene V with 2,6-dibromo-
benzoquinone or 2,5-dibromobenzoquinone in boiling
benzene occurs regioselectively and leads to formation
of 3-bromo-6-ethoxycarbonyl-7-hydroxy-5-(3,4-di-
methoxyphenyl)-1,4-naphthoquinone (VII) (38%)
or 2-bromo-6-ethoxycarbonyl-7-hydroxy-5-(3,4-di-
methoxyphenyl)-1,4-naphthoquinone (VIII) (36%),
respectively (Scheme 2, Table 1). Siloxydiene VI
reacts with dibromobenzoquinones at a lower rate;
Using the standard procedure [4], by crotonization
of 3,4-dimethoxybenzaldehyde with acetone we ob-
tained known (E)-4-(3,4-dimethoxyphenyl)-3-buten-
2-one (I) [5, 6] (Scheme 1). The reactions of 3,4- and
2,4-dimethoxybenzaldehydes with ethyl acetoacetate
afforded 4-(3,4- or 2,4-dimethoxyphenyl)-3-ethoxy-
carbonyl-3-buten-2-ones II and III in 63 and 78%
1
yield, respectively. According to the H NMR data,
each product was a mixture of Z and E isomers at
a ratio of (1.24 1.38):1.
Previously unknown 1-(3,4-dimethoxyphenyl)- and
1-(2,4-dimethoxyphenyl)-2-R-3-trimethylsiloxy-1,3-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

1438
NECHEPURENKO et al.
Table 1. Reactions of siloxydienes IV VI with quinones
Amounts of the reactants, g (mmol)
Reaction
time, h
Product, yield, g (%)
diene
V, 1.23 (3.51)
quinone
2,6-Dibromo-1,4-benzoquinone,
0.79 (2.98)
6
7.5
VII, 0.52 (38)
VIII, 0.50 (36)
IX, 0.14 (49)
X, 0.22 (33)a
V, 1.28 (3.66)
2,5-Dibromo-1,4-benzoquinone,
0.79 (2.98)
VI, 0.54 + 0.55 (0.77 + 0.79)
VI, 1.25 + 0.56 (1.71 + 0.76)
V, 1.06 (3.03)
2,6-Dibromo-1,4-benzoquinone,
0.17 (0.63)
22.5 + 8.5
22.5 + 14
8
2,5-Dibromo-1,4-benzoquinone,
0.38 (1.43)
2-Bromo-6-methyl-1,4-benzo-
quinone, 0.60 (2.98)
XII, 0.22 (19)
XI, 0.49 (42)
VI, 1.20 + 0.53 (1.71 + 0.76)
V, 1.14 (3.26)
2-Bromo-6-methyl-1,4-benzo-
quinone 0.29 (1.43)
21 + 14
7.5
XIII, 0.13 (23)
XIV, 0.54 (39)
2-Methoxy-1,4-benzoquinone,
0.41 (2.98)
XVI, 0.09 (7)
XV, 0.22 (18)
XVIIa + XVIIb, 0.25 (20)
(1:2.15)
VI, 1.49 + 0.73 (2.13 + 1.04)
IV, 0.93 (2.84)
2-Methoxy-1,4-benzoquinone,
0.20 (1.43)
22.5 + 8.5
XVIII, 0.12 (20)b
XIV, 0.29 (16)
2-Bromo-1,4-naphthoquinone,
0.83 (3.50)
8
8
XX, 0.74 (72)
IV, 1.24 (3.79)
Juglone, 0.61 (3.51)
XXII, 0.42 (31)
XXIII, 0.08 (6)
XXIV, 0.12 (9)
V, 1.25 (3.57)
1,4-Naphthoquinone, 0.47 (2.98)
Juglone, 0.52 (2.98)
7
XXVII, 0.10 (8)
XXVI, 0.26 (20)
XXVIII, 0.37 (29)
V, 1.28 (3.66)
7
XXX, 0.40 (30)
XXIX, 0.09 (7)
XXXI, 0.39 (29)
VI, 1.21 + 0.58 (1.73 + 0.83)
VI, 1.15 + 0.42 (1.64 + 0.60)
VI, 1.30 + 0.49 (1.86 + 0.70)
1,4-Naphthoquinone, 0.23 (1.43)
21 + 8.5
22.5 + 14
22.5 + 8.5
XXXII, 0.12 (20)c
XXXIII, 0.06 (10)d
XIV, 0.08 (9)
2-Bromo-1,4-naphthoquinone,
0.34 (1.43)
XXXII, 0.04 (6)
XXXIII, 0.06 (9)
XIV, 0.14 (11)
Juglone, 0.25 (1.43)
XXXIV, 0.10 (16)
XIV, 0.25 (18)
a
b
c
Yield on the reacted quinone 48%; conversion 68%.
Yield on the reacted quinone 27%; conversion 75%.
Yield on the reacted quinone 31%; conversion 65%.
Yield on the reacted quinone 16%.
d
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

SYNTHESIS OF 5-ARYL-1,4-NAPHTHOQUINONE
1439
Scheme 3.
XV XVII, Ar = 3,4-(MeO)2C6H3; XVIII, Ar = 2,4-(MeO)2C6H3; ratio XVIIa:XVIIb 1:2.5.
these reactions were carried out by heating 1 equiv of
the quinone with 1.15 1.49 equiv of diene VI in
boiling benzene for 22.5 h; an additional amount of
diene VI (0.4 0.6 equiv) was then added, and the
mixture was heated under reflux for 8.5 14 h more.
Under these conditions, the only products were com-
pounds IX (49%, from 2,6-dibromobenzoquinone)
and X (48%, from 2,5-dibromobenzoquinone).
The reaction of siloxybutadiene V with 2-bromo-
6-methyl-1,4-benzoquinone resulted in formation of
42% of 6-ethoxycarbonyl-5-(3,4-dimethoxyphenyl)-7-
hydroxy-2-methyl-1,4-naphthoquinone (XI) and 19%
of its 1a,8-dihydro derivative XII. Excess siloxydiene
VI reacted with the same quinone to afford naphtho-
quinone XIII in 23% yield. Also, cycloaddition
product of diene VI and ketone III, 4-acetyl-2,4-bis-
(ethoxycarbonyl)-3,5-bis(2,4-dimethoxyphenyl)-1-cy-
clohexenol (XIV) was isolated (yield 39%) as a single
stereoisomer.
Thus the structure of the Diels Alder adduct
derived from siloxydienes V and VI and 2,6- and
2,5-dibromobenzoquinones corresponds to such
mutual orientation of the diene and quinone in the
transition state, at which the bromine atom appears in
the para position with respect to the siloxy group
(orbital control). An analogous pattern in the addition
of 3-siloxydienes to haloquinones was observed in [7].
In the reactions of siloxydienes V and VI with
2-bromo-6-methyl-1,4-benzoquinone, the bromine
atom appears in the meta position with respect to
the siloxy group. Such orientation was typical of
1-(2-methoxyphenyl)-2-R-3-trimethylsiloxy-1,3-buta-
dienes [2]. In the latter case, the opposite regioselec-
tivity is likely to result from the predominant charge
control of the reaction; here, the interaction between
the positively charged C2 atom in the quinone and
C4 in the siloxydiene (which has a partial negative
charge) becomes crucial.
The reaction of siloxybutadiene V with methoxy-
benzoquinone in boiling benzene was not regioselec-
tive; the products were 2- and 3-methoxy-5-(3,4-di-
methoxyphenyl)-6-ethoxycarbonyl-7-hydroxy-1,4-
naphthoquinones XVIIa and XVIIIb (ratio 1:2.15),
3-methoxytetrahydronaphthoquinone XV, and
2-methoxydihydronaphthoquinone XVI (Scheme 3).
The position of the methoxy group in compounds XV
and XVI was established by converting them into
naphthoquinones XVIIb and XVIIa, respectively, via
dehydrogenation over Pd/C. The reaction of methoxy-
benzoquinone with excess siloxydiene VI, followed
by dehydrogenation over Pd/C, led to formation of
a mixture of 3-methoxynaphthoquinone XVIII (yield
27%) and cyclohexenol XIV (16%).
Diene IV reacted with 2-bromo-1,4-naphtho-
quinone (XIX) to give exclusively 3-hydroxy-1-(3,4-
dimethoxyphenyl)-9,10-anthraquinone (XX) in 72%
yield (Scheme 4). By reaction of diene IV with
juglone (XXI) we obtained 31% of 8-hydroxy-1-(3,4-
dimethoxyphenyl)-3-oxo-1,2,3,4-tetrahydro-9,10-an-
thraquinone (XXII). In addition, we succeeded in
isolating primary adduct XXIII (6%) and anthra-
quinone XXIV (9%).
The reaction of siloxydiene V with 1,4-naphtho-
quinone (XXV) in boiling benzene afforded 20% of
tetrahydroanthraquinone XXVI, 8% of dihydroanthra-
quinone XXVII, and 29% of anthraquinone XXVIII
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

1440
NECHEPURENKO et al.
Scheme 4.
Scheme 5.
XXV, XXVI XXVIII, R = H; XXI, XXIX XXXI, X = H.
1
(Scheme 5). Under analogous conditions, diene V
reacted with quinone XXI in a regioselective fashion;
the products were anthraquinone derivatives XXIX
(7%), XXX (30%), and XXXI (29%).
III (Table 2). In the H NMR spectrum of Z-II, the
signal from 4-H ( 7.43 ppm) is located in a stronger
field than the corresponding signal of the E isomer
( 7.53 ppm), which is consistent with the results of
calculations based on the additivity schemes [8]. In
the 13C NMR spectrum of Z-II, recorded in the mono-
resonance mode, the signal from C2 (CH3CO) at
As noted above, the Diels Alder reactions with
diene VI require a longer time and larger excess of
the diene, and the yields are lower than in the reac-
tions with diene V. The reactions of VI with naphtho-
quinone (XXV) and 2-bromo-1,4-naphthoquinone
(XIX) gave compounds XXXII (yield 31 and 6%,
respectively) and XXXIII (16 and 9%) (Scheme 6).
By reaction of siloxydiene VI with juglone (XXI)
we obtained anthraquinone XXXIV in as low as
16% yield. In all these reactions, 9 18% of cyclo-
hexenol XIV was also isolated.
194.3 ppm is split due to coupling with 4-H
(3JCH = 7 Hz), indicating cis arrangement of C2 and
4-H, while the ester carbonyl carbon atom is coupled
with 4-H through a constant JCH of 12.5 Hz, which
corresponds to trans arrangement of these atoms, in
keeping with published data [9].
Mutual orientation of substituents in the molecule
of cyclohexenol XIV was deduced from the 1H
NOESY spectrum. Protons of the acetyl group at C4
showed NOE with 3-H and 5-H; this means that the
latter are arranged cis. Therefore, compound XIV is
C
3
The structure of the products was determined by
analysis of their spectral data. We also performed
assignment of the Z and E isomers of ketones II and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

SYNTHESIS OF 5-ARYL-1,4-NAPHTHOQUINONE
1441
Scheme 6.
XIX, R = Br; XXV, R = H.
the product of endo-cycloaddition of the Z isomer of
III to siloxydiene VI.
respectively, due to deshielding effect of the carbonyl
group in the quinone fragment.
The IR and UV spectra and elemental analyses of
naphthoquinones VII XIII and XV XVIII and an-
thraquinones XX, XXII XXIV, and XXVI XXXIV
The position of the substituent (Br, Me, MeO) in
molecules VII, VIII, XI XIII, and XVIIb was deter-
mined on the basis of multiplicities of the carbonyl
carbon signals in the 13C NMR spectra recorded in
the monoresonance mode. The corresponding values
of JCH3 (Tables 5, 6) are typical of quinone systems
1
are given in Table 3, the H NMR spectra are given
in Table 4, and Tables 5 and 6 contain their 13C NMR
spectral parameters.
The 1H NOESY spectra of tetrahydronaphtho-
quinone XV and tetrahydroanthraquinone XXVI
revealed NOE between the 5-H and 4a-H protons and
1-H and 1a-H, respectively, indicating cis orientation
of these protons. The doublet signal from 5-H in the
spectrum of XV ( 4.28 ppm) is characterized by
[12]: J(C1 3-H) = 7 10 Hz, J(C1 8-H) = 3.5 5 Hz,
3
2J(C1 2-H) = 0.8 1.7 Hz. If the substituent is located
in position 2 (compounds VIII, XI, and XIII), the
signal from C1 is a doublet of doublets with coupling
constants of 7 and 4 Hz, while the C4 signal is
a doublet with J = 1.5 Hz. When the substuent
occupies position 3 (VII, XVIIb), the C1 signal
appears as a doublet of doublets with J = 4, 1.5 Hz,
while C4 gives a doublet with J = 7 Hz. In addition,
3
a coupling constant J5, 4a of 6 Hz. In the spectra of
XXVI and XXIX, the 1-H signal is a doublet ( 4.70
3
4.72 ppm) with a coupling constant J1, 1a of 1 2 Hz;
3
3
4
we determined the coupling constant J(C4 8-H) in
similar values of J5, 4a and J1, 1a were observed by
us previously [2, 10, 11].
naphthoquinones VII, VIII, and XVIIb (0.7 1.0 Hz),
3
as well as J(C1 2-CH3) = 0.9 Hz in XI.
1
The chemical shift of 1a-H in the H NMR spectra
The difference in the chemical shifts of the C1 and
C4 carbonyl carbon atoms in 3-bromonaphthoquinones
VII and IX is 6.0 to 6.1 ppm, whereas the corre-
sponding difference for 2-bromo derivatives VIII and
of dihydronaphthoquinones XII and XVI or of 4a-H
in the spectra of dihydroanthraquinones XXVII,
XXX, and XXXII ranges from 5.0 to 5.3 ppm; their
signals are doublets of doublets with coupling con-
1
stants of 5 and 3 Hz. The H NMR spectra of the
1
4
X is 2.9 to 2.7 ppm. The value of
(
,
for
C
3-methoxynaphthoquinone XVIIb is 5.7 ppm, aCnd) for
2-methoxy analog XVIIa, 3.6 ppm. The C1 and C4
carbonyl carbon signals in the spectrum of methoxy-
naphthoquinone XVIII differ by 6.3 ppm; therefore,
aromatic products, naphthoquinones VII XI, XIII,
XVIIb, and XVIII and anthraquinones XX, XXIV,
XXVIII, XXXI, XXXIII, and XXXIV are charac-
terized by downfield shift of the 8-H and 4-H signal,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

1442
NECHEPURENKO et al.
Table 2. 1H and 13C NMR spectra of ketones I III and siloxydienes IV VI in CDCl3
Comp.
no.
1H NMR spectrum, , ppm (J, Hz)
13C NMR spectrum, C, ppm
I
2.29 s (3H, CH3), 3.83 s (6H, OCH3), 6.52 d (1H, 27.0 (C1), 55.6, 55.7 (2 OCH3), 109.5 (C5 ), 110.9 (C2 ),
3-H, 16), 6.69 d (1H, 5 -H, 8), 7.00 d (1H, 2 -H,
2), 7.03 d.d (1H, 6 -H, 8; 2), 7.38 d (1H, 4-H, 16)
122.7 (C6 ), 124.9 (C3), 127.1 (C1 ), 143.1 (C4 ),
149.0 and 151.1 (C3, C4 ), 198.2 (C2)
IIa
1.25 t (3H, CH3), 2.32 s (3H, Z-CH3), 2.34 s 13.7 (Z-CH3), 13.8 (E-CH3), 26.1 (Z-C1), 31.0 (E-C1),
(3H, E-CH3), 3.83, 3.85 s (6H, Z-OCH3), 3.79,
3.80 s (6H, E-OCH3), 4.23 q (2H, CH2), 6.85 d
(1H, Z-5 -H, 8), 6.77 d (1H, E-5 -H, 8), 7.01 d
(1H, Z-2 -H, 2), 6.87 d (1H, E-2 -H, 2), 7.08 d.d
(1H, Z-6 -H, 8; 2), 6.94 d.d (1H, E-6 -H, 8; 2),
7.43 (1H, Z-4-H), 7.53 (1H, E-4-H)
55.6, 55.7 (2 OCH3), 61.4 (Z-CH2), 61.1 (E-CH2),
110.9 (C5 ), 111.7 (Z-C2 ), 112.0 (E-C2 ), 124.3
(Z-C6 ), 123.9 (E-C6 ), 125.4 (Z-C3), 125.5 (E-C3),
132.4 (Z-C1 ), 131.7 (E-C1 ), 140.9 (Z-C4), 140.2
(E-C4), 148.9, 151.0, 151.4 (C3 , C4 ), 168.0 d.t
(Z-CO2, JCH = 12.5, 3.0 Hz), 164.4 (E-CO2),
194.3 d.q (Z-C2, JCH = 7.0, 6.0 Hz), 203.6 s (E-C2)
IIIb
1.22 t (3H, Z-CH3), 1.26 t (3H, E-CH3), 2.34 s 13.7 (Z-CH3), 14.0 (E-CH3), 26.1 (Z-C1), 30.8 (E-C1),
(3H, Z-CH3), 2.67 s (3H, E-CH3), 3.77, 3.79 s
(6H, Z-OCH3), 3.76 s and 3.78 s (6H, E-OCH3),
4.23 q (2H, CH2), 6.39 d (1H, 3 -H, 2), 6.40 d.d
(1H, 5 -H, 8.5; 2), 7.17 d (1H, E-6 -H, 9), 7.33 d
(1H, Z-6 -H, 8.5), 7.83 s (1H, Z-4-H), 7.85 s (1H,
E-4-H)
55.1, 55.2, 55.1 (Z-OCH3, E-OCH3), 60.9 (E-CH2),
61.1 (Z-CH2), 104.9 (E-C5 ), 105.1 (Z-C5 ), 114.8
(Z-C1 ), 114.9 (E-C1 ), 130.2 (Z-C6 ), 131.2 (E-C6 ),
132.0 (C3), 136.0 (E-C4), 136.4 (Z-C4), 159.2, 163.0
(E-C2 , C4 ), 159.6, 163.3 (Z-C2 , C4 ), 164.8 (E-CO2),
168.2 (Z-CO2), 195.0 (Z-C2), 203.2 (E-C2)
IV
0.26 s [9H, (CH3)3SiO], 3.85 s and 3.88 s (6H, 0.1 [(CH3)3SiO], 55.7, 55.8 (2 OCH3), 95.8 (C3), 109.2
OCH3), 4.36 and 4.40 (2H, 4-H), 6.44 d (1H,
2-H, 15.5), 6.73 d (1H, 1-H, 15.5), 6.79 d (1H,
5 -H, 8), 6.93 d (1H, 2 -H, 2), 6.94 d.d (1H, 6 -H,
8, 2)
(C5 ), 111.2 (C2 ), 120.0 (C6 ), 124.5, 128.9 (C1, C2),
129.8 (C1 ), 148.9, 149.0 (C3, C4 ), 155.0 (C4)
V
0.25 s [9H, (CH3)3SiO], 1.19 t (3H, CH3), 3.81 s 0.2 [(CH3)3SiO], 13.7 (CH3), 61.1 (CH2), 55.6, 55.7
and 3.83 s (6H, OCH3), 4.21 q (2H, CH2), 4.41
(2H, 4-H), 6.86 m (3H, 1-H, 2 -H, 6 -H), 6.77 d
(1H, 5 -H, 9)
OCH3), 94.2 (C3), 110.9 (C5 ), 111.0 (C2 ), 121.7
(C6 ), 127.9 (C2), 128.6 (C1), 131.3 (C1 ), 148.6,
149.2 (C3 , C4 ), 152.4 (C4)
VI
0.26 s [9H, (CH3)3SiO], 1.16 t (3H, CH3), 3.70 s
and 3.78 s (6H, OCH3), 4.16 q (2H, CH2), 4.41
and 4.47 (2H, 4-H), 6.35 m (3H, 1-H, 3 -H,
5 -H), 7.17 m (1H, 6 -H)
a
Z:E isomer ratio 1.24:1. For the Z-CO2 and Z-C2 signals of II, J(C 4-H) values from the monoresonance spectrum are given.
Z:E isomer ratio 1.38:1.
b
3
compound XVIII was assigned the structure of
3-methoxy derivative.
is a doublet of triplets, J(C10 5-H) = 8 Hz and
3J(C10 4-H) = 1.3 Hz, and the signal at
184.2 ppm
C
Signals from the C9 and C10 carbonyl carbon atoms
in the 13C NMR spectra of tetrahydroanthraquinone
XXII and dihydroanthraquinone XXXII were as-
signed as follows. In the spectrum of XXII, the signal
(C9) is a doublet with J(C9 8-H) = 8 Hz. The C9 and
3
C10 signals of anthraquinone XXVIII were identified
by analysis of the COLOC spectrum. The signal at
182.4 ppm (C10) showed a cross peak with 4-H,
C
at
182.9 ppm (C10) is a doublet of triplets with
and the signal from C9 ( 180.9 ppm) was displaced
upfield due to effect ofCthe 1-aryl and 3-hydroxy
groups [2, 12].
C
3J(C10 5-H) = 3.8 Hz and 3J(C10 4-H) = 1 Hz;
the signal at
188.0 ppm (C9) is a doublet with
C
3J(C9 1-H) = 2.6 Hz. The carbonyl carbon signals
of dihydroanthraquinone XXXII are split in the
Thus the cycloaddition of 1-dimethoxyphenyl-3-tri-
methylsiloxy-1,3-butadienes to bromobenzoquinones
and naphthoquinones provides a convenient and regio-
following manner: the signal at
183.0 ppm (C10)
C
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

SYNTHESIS OF 5-ARYL-1,4-NAPHTHOQUINONE
1443
Table 3. Melting points, IR and UV spectra, elemental analyses, and molecular weights (mass spectral data) of naphtho-
quinones VII XIII and XV XVIII, anthraquinones XX, XXII XXIV, and XXVI XXXIV, and cyclohexenol XIV
Found, % (M+)
Calcd., % (M+)
Comp.
no.
IR spectrum,
UV spectrum,
nm (log )
mp,
C
Formula
1
, cm
,
max
C
H
C
H
VII
248 251 3350, 1732, 1678, 277 (4.01), 396 (3.00)
1574, 1251
54.8
3.5
C21H17O7Bra
C21H17O7Brb
54.7
3.7
VIII
IX
240 243 3350, 1738, 1680, 277 (4.04), 396 (3.01)
55.1
3.1
54.7
3.7
1655, 1570, 1517,
1228
209 210 3439, 1714, 1679, 278 (4.28), 393 (3.15),
1613, 1573, 1510, 520 (2.81)
1208, 1028
460.01576
C21H17O7Br
460.01581
X
187 189 3429, 1654, 1612, 276 (4.25), 398 (3.25)
1250, 1209
53.8
66.3
3.5
5.4
C21H17O7Brc
C22H20O7
54.7
66.7
3.7
5.1
XI
240 242 3364, 1732, 1664, 270 (4.39), 379 (3.31)
1609, 1576, 1251,
1223
XII
187 185 3435, 1655, 1514, 280 (3.84), 385 (3.38)
1263
65.3
66.1
64.7
5.6
5.2
6.7
C22H22O7
C22H20O7
C30H36O10
66.3
66.7
64.7
5.6
5.1
6.5
XIII
XIV
164 166 3366, 1734, 1666, 270 (4.53), 307 (3.72),
1575, 1210
380 (3.44)
80 82
3437, 1730, 1705,
1650, 1613, 1586,
1505, 1267, 1209
256 (4.12)
XV
154 155 3435, 1708, 1664, 234 (4.15), 257 (4.15)
1603, 1517, 1221
63.1
5.8
C22H24O8
C22H22O8
C22H20O8
63.4
5.8
XVI
173 175 3468, 1690, 1642, 235 (4.21), 275 (4.03),
1608, 1514, 1246 335 (3.54), 518 (3.04)
414.13098
414.13145
XVIIa/
XVIIb
253 257 3370, 1730, 1680, 271 (4.36), 400 (3.26)
412.11657
412.11720
412.11580
412.11580
1650, 1616, 1517,
1245, 1204
XVIII
XX
214 215 3522, 3408, 1732, 281 (4.24), 327 (3.65)
C22H20O8
1674, 1636, 1615,
1570, 1210
310 312 3414, 1668, 1593, 240 (4.37), 272 (4.45),
69.6
5.3
4.8
C22H16O5
C4H8O2
69.6
5.4
4.4
1564, 1518, 1289, 368 (3.49)
1251
XXII
172 174 3428, 1717, 1638, 278 (4.15), 420 (3.56),
1615, 1515, 1258 510 (3.36), 660 (3.00)
69.8
C22H18O6
C22H20O6
C22H16O6
C25H24O7
C25H22O7
69.8
XXIII
XXIV
XXVI
XXVII
212 214 3420, 1711, 1592, 231 (4.30), 275 (3.82),
380.12645
380.12598
1516, 1262
225 230 3416, 1634, 1592, 279 (4.20), 344 (3.71),
1516, 1252 410 (3.55), 656 (1.54)
202 204 3482, 1695, 1651, 226 (4.49), 250 (4.26),
1515, 1239 306 (3.57), 337 (3.50)
185 187 3435, 1664, 1513, 245 (4.41), 267 (4.13),
1291, 1241 331 (3.54)
344 (3.83), 654 (2.82)
376.09433
436.15184
434.13575
376.09468
436.15219
434.13654
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

1444
NECHEPURENKO et al.
Table 3. (Contd.)
Found, % (M+)
Calcd., % (M+)
Comp.
no.
IR spectrum,
UV spectrum,
nm (log )
mp,
C
Formula
1
, cm
,
max
C
H
C
H
XXVIII
XXIX
310 315 3374, 1731, 1670, 240 (4.40), 270 (4.50),
1563, 1518, 1251 370 (3.54)
432.12083
C25H20O7
C25H24O8
432.12089
3442, 1736, 1715, 230 (4.19), 259 (3.76),
1653, 1517, 1456, 348 (3.49)
1259
66.1
5.2
4.9
66.4
5.4
4.9
XXX
200 203 3444, 1654, 1618, 250 (4.29), 278 (4.10),
1512, 1455, 1238, 349 (3.48), 422 (3.61)
1219
65.8
C25H22O8
C25H20O8
66.7
XXXI
260 265 3311, 1733, 1663, 218 (4.23), 273 (4.04),
1638, 1571, 1516, 337 (3.51), 408 (3.45)
1250, 1223
448.11531
448.11580
XXXII
215 219 3646, 1663, 1337, 245 (4.41), 267 (4.13),
434.13920
432.12095
C25H22O7
C25H20O7
434.13654
432.12089
1293, 1206
331 (3.54)
XXXIII
220 221 3350, 1732, 1673, 240 (4.36), 274 (4.52),
1565, 1358, 1304, 313 (3.87), 376 (3.51)
1256, 1210, 1159
XXXIV
245 247 3436, 1733, 1613, 221 (4.53), 272 (4.32),
1506, 1466, 1210 406 (3.49)
66.8
4.3
C25H20O8
67.0
4.5
a
Found Br: 17.1%. Calculated Br: 17.3%.
Found Br: 17.7%. Calculated Br: 17.3%.
Found Br: 17.2%. Calculated Br: 17.3%.
b
c
Table 4. 1H NMR spectra of naphthoquinones VII XIII and XV XVIII, anthraquinones XX, XXII XXIV, and XXVI
XXXIV, and cyclohexenol XIV in CDCl3
Comp. no.
Chemical shifts , ppm (J, Hz)
VII
VIII
IX
0.82 t (3H, CH3CH2), 3.78 s and 3.90 s (6H, CH3O), 3.95 q (2H, CH3CH2), 7.44 s (1H, 2-H), 6.61 d (1H,
2 -H, 2), 6.59 d.d (1H, 6 -H, 8, 2), 6.86 d (1H, 5 -H, 8), 7.68 s (1H, 8-H), 10.71 s (1H, OH)
0.81 t (3H, CH3CH2), 3.60 s and 3.90 s (6H, CH3O), 3.95 q (2H, CH3CH2), 7.25 s (1H, 3-H), 6.62 d (1H,
2 -H, 2), 6.58 d.d (1H, 6 -H, 8, 2), 6.66 d (1H, 5 -H, 8), 7.76 s (1H, 8-H), 10.75 s (1H, OH)
0.83 t (3H, CH3CH2), 3.66 s and 3.83 s (6H, CH3O), 3.98 q (2H, CH3CH2), 7.68 s (1H, 2-H), 6.71 d.d
(1H, 5 -H, 2, 8), 6.72 d (1H, 3 -H, 1), 6.71 d (1H, 6 -H, 8), 7.77 s (1H, 8-H), 11.01 s (1H, OH)
0.87 t (3H, CH3CH2), 3.66 s and 3.83 s (6H, CH3O), 3.98 q (2H, CH3CH2), 7.24 s (1H, 3-H), 6.46 d.d
(1H, 5 -H, 2, 8), 6.50 s (1H, 3 -H), 6.72 d (1H, 6 -H, 8), 7.76 s (1H, 8-H), 11.13 s (1H, OH)
0.81 t (3H, CH3CH2), 2.00 s (3H, 2-CH3), 3.79 s and 3.88 s (6H, CH3O), 3.93 q (2H, CH3CH2), 6.74 s
(1H, 3-H), 6.63 d (1H, 2 -H, 2), 6.61 d.d (1H, 6 -H, 8, 2), 6.85 d (1H, 5 -H, 8), 7.63 s (1H, 8-H),
10.47 s (1H, OH)
X
XI
XII
1.20 t (3H, CH3CH2), 1.96 s (3H, 2-CH3), 3.48 m (2H, 8-H), 3.79 s and 3.85 s (6H, CH3O), 4.13 q (2H,
CH3CH3CH2), 5.02 d.d (1H, 1a-H, 3, 5), 6.54 s (1H, 3-H), 6.69 s (2H, 2 -H, 6 -H), 6.84 s (1H, 5 -H),
12.38 s (1H, OH)
XIII
0.83 t (3H, CH3CH2), 2.01 s (3H, 2-CH3), 3.66 s and 3.83 s (6H, CH3O), 3.97 q (2H, CH3CH2), 6.57 s
(1H, 3-H), 6.49 d.d (1H, 5 -H, 2, 8.5), 6.50 s (1H, 3 -H), 6.73 d (1H, 6 -H, 8.5), 7.85 s (1H, 8-H),
10.81 s (1H, OH)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

SYNTHESIS OF 5-ARYL-1,4-NAPHTHOQUINONE
1445
Table 4. (Contd.)
Comp. no.
Chemical shifts , ppm (J, Hz)
XIV
1.04 t (3H, CH3CH2OCO-2), 1.24 t (3H, CH3CH2OCO-4), 1.58 s (3H, CH3CO), 2.68 d.d (1H, 6-H, 19.5,
12), 2.93 d.d (1H, 6-H, 19.5, 6.5), 3.70 s and 3.76 s (12H, CH3O), 3.99 q (2H, CH3CH2OCO-2), 4.25 q
and 4.38 q (2H, CH3CH2OCO-4), 4.25 m (1H, 5-H), 5.31 s (1H, 3-H), 6.32 s (1H, 3 -H), 6.29 d.d
(1H, 5a -H, 2, 8.5), 6.46 d.d (1H, 5b -H, 2, 9), 7.08 d (1H, 6a -H, 8.5), 7.33 d (1H, 6b -H), 12.33 s
(1H, OH)
XV
0.99 t (3H, CH3CH2), 2.45 d.d (1H, 8b-H, 20, 9.5), 3.12 d (1H, 1a-H, 9.5, 6), 3.45 t (1H, 4a-H, 6), 3.60 d
(1H, 8a-H, 20), 3.35 s, 3.75 s, and 3.76 s (9H, CH3O), 4.00 q (2H, CH3CH2), 4.28 d (1H, 5-H, 6),
5.36 s (1H, 2-H), 6.26 s(1H, 2 -H), 6.28 s (1H, 6 -H), 6.60 s (1H, 5 -H), 12.49 s (1H, OH)
XVI
1.18 t (3H, CH3CH2), 3.45 m and 3.60 m (2H, 8-H), 3.73 s, 3.78 s, and 3.84 s (9H, CH3O), 4.11 q (2H,
CH3CH2), 5.03 d.d (1H, 1a-H, 3, 5), 5.85 s (1H, 2-H), 6.68 s (2H, 2 -H, 6 -H), 6.86 s (1H, 5 -H),
12.38 s (1H, OH)
XVIIa
XVIIb
XVIII
XX
0.80 t (3H, CH3CH2), 3.80 s and 3.89 s (9H, CH3O), 3.95 q (2H, CH3CH2), 5.90 s (1H, 2-H), 6.63 d (1H,
2 -H, 2), 6.57 d.d (1H, 6 -H, 8, 2), 6.84 d (1H, 5 -H, 8), 7.75 s (1H, 8-H), 10.45 s (1H, OH)
0.80 t (3H, CH3CH2), 3.80 s and 3.89 s (9H, CH3O), 3.95 q (2H, CH3CH2), 6.10 s (1H, 2-H), 6.63 d (1H,
2 -H, 2), 6.57 d.d (1H, 6 -H, 8, 2), 6.84 d (1H, 5 -H, 8), 7.72 s (1H, 8-H), 10.86 s (1H, OH)
0.83 t (3H, CH3CH2), 3.70 s, 3.79 s, and 3.83 s (9H, CH3O), 3.98 q (2H, CH3CH2), 6.09 s (1H, 2-H),
6.45 d.d (1H, 5 -H, 2, 8), 6.47 s (1H, 3 -H), 6.69 d (1H, 6 -H, 8), 7.71 s (1H, 8-H), 11.13 s (1H, OH)
3.85 s and 3.93 s (6H, CH3O), 6.81 d (1H, 2 -H, 2), 6.83 d.d (1H, 6 -H, 8, 2), 6.93 d (1H, 5 -H, 8), 7.04 d
(1H, 2-H, 3), 7.73 m and 7.76 m (2H, 6-H, 7-H), 7.78 d (1H, 4-H, 3), 8.11 m, 8.22 m (2H, 5-H, 8-H)
XXII
2.83 m (2H, 2-H), 3.34 d and 3.69 d (2H, 4-H, 23), 3.77 s and 3.81 s (6H, CH3O), 4.78 d.d (1H, 1-H, 4,
3), 6.55 d.d (1H, 6 -H, 8, 1.5), 6.68 d (1H, 2 -H, 1.5), 6.70 d (1H, 5 -H, 8), 7.02 d.d (1H, 7-H, 8, 2),
7.60 m (2H, 5-H, 6-H), 11.93 s (1H, OH)
XXIII
2.55 d.d (1H, 4-H, 16, 5.5), 2.71 m (2H, 2-H), 3.10 d.d (1H, 4-H, 16, 5.5), 3.50 m (1H, 1a-H), 3.67 m
(1H, 4a-H), 3.80 m (1H, 1-H), 3.77 s and 3.83 s (6H, CH3O), 6.47 d (1H, 2 -H, 2), 6.58 d.d (1H, 6 -H,
8, 1.5), 6.77 d (1H, 5 -H, 8), 7.26 d.d (1H, 7-H, 8, 1), 7.55 d.d (1H, 5-H, 8, 1), 7.62 t (1H, 6-H, 8),
11.62 s (1H, OH)
XXIV
XXVI
3.84 s and 3.93 s (6H, CH3O), 6.87 d (1H, 2 -H, 1.5), 6.92 d.d (1H, 6 -H, 8, 1.5), 6.97 d (1H, 5 -H, 8),
7.08 d (1H, 2-H, 2.5), 7.22 d (7-H, 8), 7.56 t (6-H, 8), 7.73 d (1H, 5-H, 8), 7.79 d (4-H, 2.5), 11.57 s
(1H, OH)
1.02 t (3H, CH3CH2), 2.42 d.d (1H, 4-H, 19, 11), 2.65 d.d (1H, 4-H, 19, 6.5), 3.32 d.d (1H, 1a-H, 4, 2),
3.43 d.d.d (1H, 4a-H, 11, 6.5, 4), 3.92 s and 3.93 s (6H, CH3O), 4.05 q (2H, CH3CH2), 4.70 d (1H,
1-H, 2), 6.63 d (1H, 6 -H, 8), 6.66 s (1H, 2 -H), 6.77 d (1H, 5 -H, 8), 7.74 m (2H, 6-H, 7-H), 8.03 m
(2H, 5-H, 6-H), 12.45 s (1H, OH)
XXVII
1.22 t (3H, CH3CH2), 3.63 d (1H, 4-H, 4.5), 3.70 d (1H, 4-H, 3), 3.76 s and 3.84 s (6H, CH3O), 4.18 q
(2H, CH3CH2), 5.25 d.d (1H, 4a-H, 4.5, 3), 6.65 s and 6.69 s (2H, 2 -H, 6 -H), 6.90 s (1H, 5 -H),
7.68 m (2H, 6-H, 7-H), 8.04 m (2H, 5-H, 6-H), 12.45 s (1H, OH)
XXVIII 0.90 t (3H, CH3CH2), 3.92 s and 3.95 s (6H, CH3O), 3.95 q (2H, CH3CH2), 6.72 d.d (1H, 6 -H, 8, 1.5),
6.74 d (1H, 2 -H, 1.5), 6.92 d (1H, 5 -H, 8), 7.71 s (1H, 4-H), 7.83 m (2H, 6-H, 7-H), 7.90 m and
8.10 m (2H, 5-H, 6-H), 11.48 s (1H, OH)
XXIX
1.02 t (3H, CH3CH2), 2.25 m and 2.59 m (2H, 4-H), 3.34 m (1H, 1a-H), 3.78 m (1H, 4a-H), 3.84 s and
3.85 s (6H, CH3O), 4.03 q (2H, CH3CH2), 4.72 d (1H, 1-H, 1), 6.64 d (1H, 6 -H, 8), 6.68 s (1H, 2 -H),
6.80 d (1H, 5 -H, 8), 7.27 d.d (1H, 7-H, 8, 1), 7.53 d.d (1H, 5-H, 8, 1), 7.85 t (1H, 6-H, 8), 11.90,
12.48 s (2H, OH)
XXX
1.20 t (3H, CH3CH2), 3.63 m (2H, 4-H), 3.78 s and 3.85 s (6H, CH3O), 4.16 q (2H, CH3CH2), 5.16 t (1H,
4a-H, 3.5), 6.70 s (2H, 2 -H, 6 -H), 6.90 s (1H, 5 -H), 7.15 d.d (1H, 7-H, 7.5, 2), 7.48 m (2H, 5-H,
6-H), 11.92 s and 12.39 s (2H, OH)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

1446
NECHEPURENKO et al.
Table 4. (Contd.)
Comp. no.
Chemical shifts , ppm (J, Hz)
XXXI
0.85 t (3H, CH3CH2), 3.83 s and 3.93 s (6H, CH3O), 3.95 q (2H, CH3CH2), 6.66 d (1H, 2 -H, 2), 6.70 d.d
(1H, 6 -H, 9, 2), 6.89 d (1H, 5 -H, 9), 7.23 d.d (1H, 7-H, 8, 1.5), 7.58 t (1H, 6-H, 8), 7.74 d.d (1H, 5-H,
8, 1.5), 7.92 s (1H, 4-H), 10.47 s and 12.40 s (2H, OH)
XXXII
XXXIII
XXXIV
1.23 t (3H, CH3CH2), 3.53 d (1H, 4-H, 5), 3.59 d (1H, 4-H, 3.5), 3.68 s and 3.73 s (6H, CH3O), 4.13 q
(2H, CH3CH2), 5.27 d.d (1H, 4a-H, 3.5, 5), 6.31 d (1H, 3 -H, 2), 6.42 d.d (1H, 5 -H, 2.5, 8.5), 7.35 d
(1H, 6 -H, 8.5), 7.63 m (2H, 6-H, 7-H), 7.95 m and 8.05 m (2H, 5-H, 8-H), 12.42 s (1H, OH)
0.85 t (3H, CH3CH2), 3.67 s and 3.80 s (6H, CH3O), 3.99 q (2H, CH3CH2), 6.54 s (1H, 3 -H), 6.51 d.d
(1H, 5 -H, 2, 8), 6.78 d (1H, 6 -H, 8), 7.70 m (2H, 6-H, 7-H), 7.70 m and 8.09 m (2H, 5-H, 8-H), 7.92 s
(1H, 4-H), 10.81 s (1H, OH)
0.86 t (3H, CH3CH2), 3.68 s and 3.87 s (6H, CH3O), 3.99 q (2H, CH3CH2), 6.53 s (1H, 3 -H), 6.51 d.d
(1H, 5 -H, 8, 2), 6.78 d (1H, 6 -H, 8), 7.21 d.d (1H, 7-H, 8, 1.5), 7.57 t (1H, 6-H, 8), 7.75 d.d (1H, 5-H,
8, 1.5), 7.90 s (1H, 4-H), 10.74 s and 12.49 s (2H, OH)
selective one-step route to 7-hydroxy-5-(dimethoxy-
phenyl)-1,4-naphthoquinone and 3-hydroxy-1-(di-
methoxyphenyl)-9,10-anthraquinone derivatives.
Methyl styryl ketones I III. 4-(3,4-Dimethoxy-
phenyl-3-buten-2-one (I) was obtained by crotoniza-
tion of acetone with 3,4-dimethoxybenzaldehyde.
Ketones II and III were synthesized by the Knoeve-
nagel condensation (Cope modification [4]) of ethyl
acetoacetate with 3,4-dimethoxybenzaldehyde or
2,4-dimethoxybenzaldehyde, respectively.
Ketone I. Yield 45%, bp 140 142 C (2 mm),
mp 95 98 C; published data: mp 85 86 C, 91 92 C
[5]; 85 86 C [6].
EXPERIMENTAL
The IR spectra were recorded on a Vector 22 spec-
trometer from samples prepared as KBr pellets. The
UV spectra were measured on an HP 8453 UV-Vis
spectrophotometer from solutions in ethanol with
4
1
a concentration c of 10 M. The H NMR spectra
were recorded on Bruker AC-200 (200.13 MHz) and
DRX-500 instruments (500.13 MHz). The 13C NMR
spectra were run on Bruker AC-200 (50.32 MHz;
JMOD) and DRX-500 spectrometers (125.76 MHz;
JMOD, monoresonance, COLOC, NOESY). Chloro-
form-d and DMSO-d6 were used as solvents (c = 5
10%) and internal reference. The progress of reactions
was monitored by TLC on Silufol UV-254 plates
using chloroform methanol (20:1) as eluent; spots
were visualized under UV light or by treatment with
gaseous ammonia. Column chromatography was per-
formed on KSK silica gel, 60 100 m, using petro-
leum ether (bp 70 100 C) diethyl ether (3:1), diethyl
ether, chloroform, or chloroform methanol (100:1) as
eluent. Dienes IV VI were purified using KSK silica
gel, 60 100 m, which was preliminarily dried for 3 h
at 120 C and deactivated by heating in a microwave
oven for 10 min at a power of 300 W.
Ketone II. Yield 63%, bp 190 195 C (1 mm); Z:E
isomer ratio 1.24:1 (1H NMR data); Z-II, mp 105
106 C (from diethyl ether); published data [15]:
bp 190 196 C (0.8 mm), mp 82.5 84.5 C (with no
regard to isomeric composition).
Ketone III. Yield 78%, bp 165 174 C (2 mm),
Z:E isomer ratio 1.38:1 (1H NMR data).
Typical procedure for the synthesis of siloxy-
butadienes IV VI. A solution of 32 mmol of ketone
I III in 20 ml of anhydrous acetonitrile and 12.20 ml
(96 mmol) of chlorotrimethylsilane were added in
succession to a suspension of 0.44 g (3 mmol) of
anhydrous zinc(II) chloride and 12.2 ml of triethyl-
amine while stirring at 80 C under argon. The mixture
was stirred for 5 h at 50 C, cooled, and diluted with
150 ml of dry diethyl ether. The precipitate was
filtered off, the filtrate was evaporated under reduced
pressure (water-jet pump), and the residue was treated
with 30 ml of dry diethyl ether. The ether solution
was passed through a layer of deactivated silica gel,
and the solvent was removed to obtain compounds
IV VI as a light brown oily substances.
2-Methoxy-1,4-benzoquinone was prepared by the
procedure described in [13]; 2,5- and 2,6-dibromo-
1,4-benzoquinones and 2-bromo-1,4-naphthoquinone
were synthesized by bromination of hydroquinone,
phenol, or 1-naphthol, respectively, followed by
oxidation according to the procedure reported in [14].
1-(3,4-Dimethoxyphenyl)-3-trimethylsiloxy-1,3-
butadiene (IV). Yield 66%; according to the 1H
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

SYNTHESIS OF 5-ARYL-1,4-NAPHTHOQUINONE
1447
Table 5. 13C NMR spectra of naphthoquinones VII XIII, XV, and XVI XVIII in CDCl3, , ppm (JCH, Hz)
Atom no.
C1
VII
VIII
IX
X
XIa
XIIa
181.6 d.d
(4.7, 0.8)
136.4
138.3
143.6
177.6 d.d
(8.9, 4.7)
136.4
135.7
143.0
181.8
177.8
183.6 d.d.q
(9.3, 3.4, 0.9)
137.0
185.6 m
C1a
C2
C3
C4
139.2
138.3
135.5
175.7
136.3b
135.8b
142.9
180.5
39.3
145.8
132.6
186.0 d
(1.7)
134.9
142.4
110.4
167.4
28.1
151.0
135.5
75.6 d.d
(7.8, 1.0)
120.8b
147.6
180.5 t
(0.9)
183.8 d
(5.1)
C4a
120.4b
147.0
121.2
145.1
121.6
164.0
117.2
121.4
144.1
122.4
163.7
116.8
120.6b
C5
146.0
C6
122.5b
163.2
115.9
122.5b
163.2
122.5b
C7
162.4
114.9
C8
117.0
CO2Et
CH3CH2
ArOCH3
C1
169.3
169.6
169.7
169.8
169.4
170.8
62.1, 13.1
55.8, 55.9
131.6
62.1, 13.1
55.8, 55.9
131.6
111.7
148.6
148.6
110.6
119.8
62.1, 13.1
55.3, 55.4
120.1
62.0, 13.0
55.3, 55.4
120.2
61.8, 13.0
55.7, 55.8
132.2
60.6, 13.9
55.6, 55.8
135.1
C2
111.8
157.4b
98.4
157.6c
98.2
111.8
112.5
C3
147.5c
148.3c
147.8b
148.4b
110.9
C4
148.6c
160.9b
104.1
160.8c
103.9
148.4c
C5
110.6
119.8
110.5
119.9
C6
128.1
128.1
120.3
Atom no.
C1
XIIIb
XV
XVI
XVIIa
XVIIb
XVIII
183.7 d.d
(10, 3.5)
137.3
151.1
133.6
184.1 d
(4.5)
122.2
143.3
123.2
195.2
180.0
179.7
183.4 d.d
(4.2, 1.7)
137.2
108.0
161.7
183.9
C1a
C2
C3
C4
41.6
111.7b
161.0
195.1
39.0
158.5
106.8
185.9
135.6
158.5
112.4
183.3
137.5
108.1
157.8
177.6
177.7 d.d
(7.3, 0.7)
119.5b
147.0
C4a
41.6
50.6
98.8
170.5
24.5
135.7
140.7
110.3
167.4
28.4
120.6b
145.3
121.9
144.5
125.4
164.5
115.5
C5
C6
122.0b
121.3b
163.7
115.4
C7
163.4
115.0
163.0
115.4
C8
CO2Et
CH3CH2
ArOCH3
170.0
61.8, 13.1
55.2, 55.4
170.9
170.8
169.1
61.9, 13.1
56.1, 58.8
169.7
170.1
60.4, 13.7
55.4, 55.6,
55.7
60.7, 13.9
55.7, 55.8,
56.1
61.9, 13.1
55.8, 56.0,
56.4
61.9, 13.1
55.3, 55.4,
55.5
C1
C2
C3
C4
C5
C6
119.8
157.8b
98.3
131.8
134.7
132.0
111.8
148.4c
148.5c
110.4
119.9
132.0
119.0
111.2b
148.0c
148.5c
110.8
112.7
111.4
160.8b
98.3
147.9b
148.5b
111.0
148.4c
148.5c
110.6
160.6b
103.9
128.2
161.8b
104.0
128.0
120.3
120.2
119.6
a
(2-CH3), ppm: 16.9 (XI), 15.7 (XII), 17.1 (XIII).
Alternative assignment is possible.
b,c
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

1448
NECHEPURENKO et al.
Table 6. 13C NMR spectra of anthraquinones XX, XXII XXIV, and XXVI XXXIV and cyclohexenol XIVa in CDCl3,
, ppm (J, Hz)
Atom no.
XXb
XXII
XXIII
XXIV
XXVI
XXVII
XXVIIIb
C1
147.2
123.5
124.9
161.7
113.0c
137.2
126.5d
134.9
133.9e
135.1e
127.0d
134.9
181.9
37.8
144.9
45.2
205.2
37.1
142.3
124.5
131.8
136.4
118.5
161.6
114.8
188.0 d
(2.6)
41.0
47.4c
45.8
211.2
39.6
147.7
123.6
125.2
160.2
113.4
137.3
124.8
132.8
135.6
118.0
162.3
116.7
187.8 s
42.8
53.9
98.8
169.6
29.2
36.8
144.8
137.5
100.4
167.5
28.8
142.9
123.0
130.0
157.8
112.8
136.2
126.1c
134.5d
133.5e
134.6e
126.7c
132.1d
180.9
C1a
C2
C3
C4
C4a
C5
43.7c
124.3
132.4
137.2
118.5d
161.4
116.43
205.2
39.5
127.4c
135.9d
134.5
134.5
126.7c
135.9d
195.1
126.5c
131.9d
133.5
133.7
126.1c
131.8d
182.7
C5a
C6
C7
C8
C8a
C9
C10
183.4
182.9 d.t
(3.8, 1)
202.5
183.0
(4.2)
196.5
183.8
182.4
CO2Et
CH3CH2
ArOCH3
C1
171.6
60.5, 13.7
55.9
170.9
60.7, 14.0
55.7, 55.8
134.9
165.5
60.6, 13.6
55.6, 55.9
130.9
56.24
132.8
113.3c
148.7f
148.7f
111.2
120.6
55.8
132.4
110.9
148.5c
149.4c
111.5
119.1
55.3, 55.8
136.1
55.8, 55.9
134.3
132.6
C2
111.4
111.8
111.2
112.6
112.6
C3
148.4e
149.2e
110.2
147.7c
148.4c
110.8
147.9e
149.1e
111.0
147.9e
148.0f
C4
148.5e
148.2f
C5
110.9
120.4
111.2
120.6
C6
118.9d
120.1
119.4
Atom no.
XXIX
XXX
XXXI
XXXII
XXXIIII
XXXIV
C1
42.4
53.2
99.5
168.8
29.6
36.5
124.4
135.4
137.2
118.9c
161.4
116.7
201.0
144.6
138.8
100.3
167.3
28.9
138.4
121.2
139.2
143.0
98.6
168.4
29.3
144.1
122.8
124.9
163.4
115.8
138.5
126.5c
132.6d
133.0e
134.2e
127.4c
135.3d
181.4
144.5
122.7
124.0
162.2
116.1
138.5
128.1
132.7
135.5
118.7
163.9
117.2
187.6
C1a
C2
C3
163.2c
116.1
132.8d
124.9
132.6d
135.7
118.8
162.4c
117.1
187.4
C4
C4a
C5
39.1
37.7
136.1
131.6
124.3
118.8
161.4
114.8
188.0
125.9c
131.8d
133.2e
133.5e
126.5c
132.1d
184.2 d
(8)
C5a
C6
C7
C8
C8a
C9
C10
195.8
182.9
181.9
183.0 d.t
(8, 1.3)
171.3
60.5, 13.9
55.1, 55.5
182.8
182.2
CO2Et
CH3CH2
ArOCH3
171.6
60.9, 14.0
55.9
170.7
60.8, 14.0
55.7, 55.9
169.8
62.1, 13.2
55.9
170.0
61.7, 13.1
55.3, 55.5
169.9
62.0, 13.1
55.4, 55.5
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 10 2003

SYNTHESIS OF 5-ARYL-1,4-NAPHTHOQUINONE
1449
Table 6. (Contd.)
Atom no.
XXIX
XXX
134.7
112.7
148.0c
148.5c
111.0
120.4
XXXI
XXXII
XXXIIII
XXXIV
C1
C2
C3
C4
C5
C6
133.1
111.1
147.4
147.4
111.8
119.5c
132.0d
111.9
148.6
148.6
110.6
119.9
121.3
158.7f
98.3
120.6
157.7f
98.4
120.9
157.8c
98.3
159.9f
104.4
133.5
160.6f
103.9
128.3
160.7c
103.8
124.7
a
13C NMR spectrum of XIV, C, ppm: 13.6, 13.8 (CH3CH2); 28.2 (CH3CO); 31.7 (C3); 33.7 (C6); 38.6 (C5); 54.8, 55.0, 55.1, 55.5
(ArOCH3); 60.0, 60.7 (CH3CH2); 68.0 (C4); 97.6, 98.3 (C3 ); 100.4 (C2); 103.7 (C5 ); 120.7, 121.6 (C1 ); 129.9, 130.8 (C6 ); 158.3,
158.5, 159.0, 160.0 (C2 , C4 ); 171.4, 171.5 (COO); 172.4 (C1); 203.7 (CO).
In DMSO-d6 at 80 C.
b
c f
Alternative assignment is possible.
NMR data, the product contained 19% of the initial
ketone and 85 wt % of the main substance.
by preparative thin-layer chromatography on silica
gel to isolate 60 mg of ketone II and 20 mg of
naphthoquinone XVIIa.
Ethyl 2-(3,4-dimethoxybenzylidene)-3-trimethyl-
siloxy-3-butenoate (V). Yield 92%, purity 100%
(1H NMR data).
Ethyl 2-(2,4-dimethoxybenzylidene)-3-trimethyl-
siloxy-3-butenoate (VI). Yield 40%, purity 50 wt %
(1H NMR data).
b. A fraction (0.20 g) containing ketone II and
compound XV was dissolved in 20 ml of toluene,
11 mg of 10% Pd/C was added, and the mixture was
heated for 3.5 h under reflux. The mixture was cooled
and filtered, the filtrate was evaporated, and the
residue was separated by preparative thin-layer chrom-
atography on silica gel to isolate 103 mg of ketone II
and 49 mg of naphthoquinone XVIIb.
The authors thank M.M. Shakirova (Laboratory of
Physicochemical Methods of Investigation, Novosi-
birsk Institute of Organic Chemistry) for recording
and interpreting the NMR spectra and helpful discus-
sion of the results.
Typical procedure for the Diels Alder reaction
of siloxydienes IV VI with quinones. A solution of
3 3.5 mmol of appropriate quinone and 1 1.25 equiv
of diene IV or V in 10 ml of benzene was refluxed
under argon for 5 8 h. In the reactions with diene
VI, a solution of 1.43 mmol of quinone and 1.15
1.49 equiv of VI was refluxed under argon for 22.5 h,
an additional 0.5 equiv of VI was added, and the
mixture was heated for 8.5 14 h more. The progress
of the reaction was monitored by TLC. The solvent
was distilled off on a rotary evaporator, and the
residue was recrystallized from diethyl ether to isolate
naphthoquinones VII, VIII, and XI or anthraquinones
XX, XXVIII, and XXX. The mother liquor was
subjected to column chromatography with successive
elution with petroleum ether (bp 70 100 C) diethyl
ether (3 : 1) and diethyl ether or chloroform and
chloroform methanol (100:1). Compounds VIII, XX,
and XXVIII were recrystallized from ethyl acetate,
and VII, IX XIII, XV XVIII, XXII XXIV, XXVI,
XXVII, and XXIX XXXIV, from diethyl ether. The
amounts of the reactants, reaction times, and yields of
the products are given in Table 1.
This study was financially supported by the Rus-
sian Foundation for Basic Research (project nos. 00-
03-32882 and 00-03-40135).
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