Synthesis, characterization of N-, S-, O-substituted naphthoand benzoquinones and a structural study

Article abstract of DOI:10.1007/s12039-012-0252-2

The new series of N-, S-, O-substituted 1,4-naphthoquinone and S-, O-substituted 1,4- benzoquinone compounds were synthesized via vinylic substitution. Compounds 3 and 4 were synthesized from the reaction of 1 with 2. Compounds 6, 7 and 8 were synthesized from reaction of 1 with 5. Compounds 10 and 11 were obtained from the reaction of 1 with 9. Compounds 13 and 14 were synthesized from the reaction of 1 with 12. Compounds 16 and 17 were obtained from the reaction of 15 with 2. Photochemical and electrochemical properties of N-, S-, O-substituted quninone compounds were determined by using fluorescence spectroscopy and cyclic voltammetry. Crystal structure of 2-(7-sulphanyl-4- methyl-coumarinyl)-3-(1-ethoxy)- 1,4-naphthoquinone 13 was determined by X-ray diffraction method. Indian Academy of Sciences.

Full text of DOI:10.1007/s12039-012-0252-2

c
J. Chem. Sci. Vol. 124, No. 3, May 2012, pp. 657–667. ꢀ Indian Academy of Sciences.
Synthesis, characterization of N-, S-, O-substituted naphtho-
and benzoquinones and a structural study
CEMIL IBIS∗ and NAHIDE GULSAH DENIZ
Engineering Faculty, Department of Chemistry, Division of Organic Chemistry, Istanbul University,
34320, Avcilar Istanbul Turkey
e-mail: ibiscml@istanbul.edu.tr
MS received 2 May 2011; revised 22 November 2011; accepted 13 December 2011
Abstract. The new series of N-, S-, O-substituted 1,4-naphthoquinone and S-, O-substituted 1,4-
benzoquinone compounds were synthesized via vinylic substitution. Compounds 3 and 4 were synthesized
from the reaction of 1 with 2. Compounds 6, 7 and 8 were synthesized from reaction of 1 with 5. Compounds 10
and 11 were obtained from the reaction of 1 with 9. Compounds 13 and 14 were synthesized from the reaction
of 1 with 12. Compounds 16 and 17 were obtained from the reaction of 15 with 2. Photochemical and elec-
trochemical properties of N-, S-, O-substituted quninone compounds were determined by using fluorescence
spectroscopy and cyclic voltammetry. Crystal structure of 2-(7-sulphanyl-4-methyl-coumarinyl)-3-(1-ethoxy)-
1,4-naphthoquinone 13 was determined by X-ray diffraction method.
Keywords. 1,4-Naphthoquinone; p-chloranil; fluorescence spectroscopy; cyclic voltametry;
X-ray diffraction.
1. Introduction
anticancer and antitumour activity.8 Naphthoquinone
derivatives are an important class of naturally occur-
ring compounds as they have favourable antimicrobial,
antiparasitic, and phytotoxic activities.9,10 The biologi-
cal activity of quinones results from their ability to
accept one or two electrons to form the corresponding
radical anion or dianion species, and also their acid-
base properties. Electron-attracting or -donating sub-
stituents modulate the redox properties of quinones, i.e.,
their variable ability to accept electrons. The molecu-
lar basis of quinone toxicity is the enzyme-catalysed
reduction to semiquinone radicals, which then reduce
oxygen to superoxide anion radicals thereby regener-
ating the quinone.11 Further need for a study of the
aryl amino-1,4-naphthoquinones is illustrated by the
observation that the ortho-amino quinoid unit is present
in many antitumour antibiotics such as actinomycins,
mitomycin C, porfiromycin, and streptonigrin.12
It has been reported that some N-, S-, O-subsituted
naphtho- and benzoquinone compounds were syn-
thesized from 2,3-dichloro-1,4-naphthoquinone or p-
chloranil.13–15 In an earlier study by Prescott et al.
the antitumour activity of 2,2-Hydrazobis(3-chloro-1,4-
naphthoquinone) were investigated.16 Novel vitamin K3
analogues were synthesized and evaluated for their anti-
cancer activity by Chen et al.17 N-substituted enaminones
were synthesized from 1,4-naphthoquinones by Parr
et al.18 We describe here the synthesis of some naphtho-
Quinones are naturally occurring compounds with spe-
cific characteristics that have a great impact on the li-
ving cell. The ability to carry electrons makes them an
important component of photosynthetic and respiratory
electron transfer chain.1 They are considered as com-
ponents of biological electron transfer chains located in
the membranes of mitochondria, bacteria and chloro-
plasts. Quinones are good electron acceptors and are
known to be efficient quenchers of singlet state donor
fluorescence of various fluorophores.2 The current data
are consistent with an electron transfer mechanism,3
and the quenching efficiency is dependent on the redox
potentials of the corresponding quinone–hydroquinone
system. From the perspectives of designing magnetic
materials4 and understanding photo-physical proper-
ties,5 the co-ordination chemistry of quinones is also
very important. The quinones also find application as
electrode material.6
Depending on the molecular structure, some qui-
nones can be used as vitamin sor drugs.7 It is re-
cognized that the quinone nucleus and the substituents
are both essential to develop specific biochemical func-
tions. So, when the quinonic ring is substituted by an
appropriate alkylchain, these compounds can exhibit
∗For correspondence
657

658
Cemil Ibis and Nahide Gulsah Deniz
and benzoquinone compounds and characterization ultraviolet light (254 nm). All chemicals were reagent
of their structures by using micro analysis, FT-IR, grade and used without further purification. Moisture
1H-NMR, 13C-NMR, MS, UV-Vis. Photo- and electro- was excluded from the glass apparatus using CaCl2 dry-
chemical properties of N-, S-, O-substituted naphtho- ing tubes. Solvents, unless otherwise specified, were of
and benzoquinone compounds were investigated by reagent grade and distilled once prior to use.
using fluorescence spectroscopy and cyclic voltamme-
try method. The single crystal structure of compound
13 was determined by X-ray diffraction method.
2.2 Fluorescence measurements
Fluorescence spectra were run on a VARIAN Cary
Eclipse Fluorescence Spectrophotometer. Excitation
and emission spectra were measured for 10−4 M solu-
tions for all compounds in MetOH/CHCl3 (1:1) at room
temperature. Excitation and emission slit widths were
set at 10 nm.
2. Experimental
2.1 General
Melting points were measured on a Buchi B-540
melting point apparatus. Elemental analyses were
performed on a Thermo Finnigan Flash EA 1112 Ele-
mental analyser. Infrared (IR) spectra were recorded
in KBr pellets in Nujol mulls on a Perkin Elmer Pre-
cisely Spectrum One FTIR spectrometry. UV spec-
tra in CHCl3, THF and MetOH were recorded on
2.3 Crystal structure determination and refinement
Red crystals of compound suitable for X-ray diffraction
analysis were obtained by slow evaporation of an ethyl-
acetate solution at room temperature. A red crystal of
compound 13, C22H16O5S1, having approximate dimen-
sions of 0.50 × 0.30 × 0.10 mm was mounted on a glass
fibre. All measurements were made on a Rigaku R-Axis
Rapid-S imaging plate area detector with graphite
monochromated Mo–Kα radiation (λ = 0.71073 Å).
The data were collected at room temperature to a
maximum 2θ value of 60.3◦. Experimental conditions
were summarized in table 1. The structure was solved
1
Perkin Elmer Lambda 35 UV/VIS Spectrometer. H
and 13C NMR spectra were recorded on VarianUNI-
TYINOVA operating at 500 MHz. Mass spectra were
obtained on a Thermo Finnigan LCQ Advantage MAX
LC/MS/MS spectrometer according to ESI probe. Pro-
ducts were isolated by column chromatography on Silica
gel (Fluka Silica gel 60, particle size 63–200 μm). TLC
plates silica 60F254 (Merck, Darmstadt), detection with
Table 1. Crystal data and refinement parameters for compound 13.
CCDC deposit number
Empirical formula
Crystal colour, habit
Formula weight
Temperature
CCDC 724897
C22H16O5S
Red, block
392.43
293(2) K
Wavelength
Crystal system
Space group
0.71073 Å
Triclinic
P–1
Cell dimensions
a = 8.4474(2) Å, b = 9.1257(1) Å
c = 11.9197(2) Å, α = 84.474(4)◦
β = 84.506(4)◦, γ = 80.473(4)◦
´
Volume
899.00(3) Å3
Z
2
Density (calculated)
Absorption coefficient
F000
1.450 mg/m3
0.213 mm−1
408.00
Index ranges
−10 ≤ h ≤ 11, −12 ≤ k ≤ 12
−16 ≤ l ≤ 16
71430
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness of fit indicator
Final R indices [I >2σ(I)]
Largest diff. peak and hole
5254 [Rint = 0.042]
4958/0/253
1.095
R1 = 0.056, wR2 = 0.098
0.47 and −0.46 e.Å−3

Synthesis of new heteroatom substituted naphtho- and benzoquinone compounds
659
by SIR 9219 and refined with CRYSTALS.20 The
non-hydrogen atoms were refined anisotropically. H
atoms were located in geometrically idealized positions
C-H = 0.95(6) Å and treated as riding and Uiso(H) =
1.2Ueq(C). The selected bond distances, bond and tor-
sion angles for compound 13 were listed in tables 2
and 3, respectively. Drawings were performed with the
program ORTEP-III21 with 50% probability displace-
ment elipsoide for compound 13 in figure 1. Crys-
tallographic data (excluding structure factors) for the
structure reported in this paper have been deposited
with the Cambridge Crystallographic Data Centre as
supplementary publication no. CCDC-724897 for 13.22
Table 3. Selected bond and torsion angles (◦) for com-
pound 13.
Bond
angle
Torsion
angle
Atom
Atom
C1-C2-C3
C2-C3-C4
C2-C3-O2
C1-C10-O1
S1-C1-C10
C1-S1-C11
C18-O4-C19 121.7(2)
O4-C18-O5
C2-O3-C21
121.4(2)
117.1(1)
121.2(2)
120.8(2)
115.3(1) C15-C17-C18-O5
104.0(8) C18-O4-C19-C20
C3-C2-C1-C10
O1-C10-C1-C2
O2-C3-C2-O3
C10-C1-S1-C11
−5.7(3)
−176.1(2)
3.2(3)
134.4(1)
173.3(2)
176.5(1)
−5.3(3)
C15-17-C18-O4
C11-S1-C1-C2
C1-C2-C3-O2
116.6(2)
124.5(2)
−49.4(2)
−171.3(2)
2.4 Cyclic voltammetry measurements
p-chloranil and nucleophile compounds were added
slowly to this solution for synthesis of compounds 3,
4, 6, 7, 8, 10, 11, 16 and 17. Without heating, the mix-
ture was stirred for 24 h. In addition, 2,3-dichloro-1,4-
naphthoquinone and thiols were stirred for 12 h in a
mixture solution of ethanol (25 mL) with triethlyamine
(1 mL) for the synthesis of compounds 13 and 14.
The colour of the solution quickly changed and the
extent of the reaction was monitored by TLC. Chloro-
form (30 mL) was added to the reaction mixture. The
organic layer was washed with water (4 × 30 mL), and
dried with Na2SO4. After the solvent was evaporated
the residue was purified by column chromatography on
silica gel (scheme 1).
Electrochemical cyclic voltammetry measurements
were performed at room temperature in an airtight
three-electrode cell by using a glassy carbon electrode
(GCE) with a 0.071 cm2 surface area as the work-
ing electrode, a platinum wire served as the counter
electrode and a Ag/AgCl (in a saturated KCl solu-
tion) reference electrode. The cell was driven with
a computer controlled system of a Gamry Reference
600 Model potentiostat/galvanostat. The solutions were
deoxygenated by bubbling nitrogen through them for
approximately 5 min. The surface of the working elec-
trode was polished with deagglomerated alumina (a
particle size of 0.05 micron) before each run. The elec-
trochemical reaction vessel was charged with 10 mL an
DMF solution of 1, 3, 4, 6, 7, 8, 10, 11, 13, 14, 15,
16 and 17 (1 × 10−4 M) and tetrabutyl ammonium per-
chlorate (0.1 M) as the electrolyte. Measurements were
made over a potential range between 0 and −2 V for
1, 3, 4, 6, 8, 10, 11, 15, +1.0 and −2.5 V for 7, 0
and −2.5 V for 13, 0 and −1.8 V for 14, 16, 17 with a
scan rate of 0.1 V s−1. Voltammetric parameters for all
compounds are summarized in table 6.
2.5a 2-(11-Sulphanyl-1-undecanol)-3-ethoxy-1,4-
naphthoquinone (3): Compound 3 was synthesized
from the reaction of 1 (1 g, 4.4 mmol) with 2 (0.9 g,
4.4 mmol) according to method 1. Red oil, Yield:
0.6 g (34%). Rf : 0.50 [CH2Cl2/EtAc (4:1)]. IR (KBr
pellet, cm−1): 3410 (OH), 3070 (Ar-H), 2925, 2851
1
(C-H), 1661 (C=O), 1591, 1543 (C=C). H NMR
(499.74 MHz, CDCl3): δ = 1.2 (t, J = 6.84 Hz, 3H,
CH3), 1.3–1.4 (m, 14H, CH2), 1.45–1.6 (m, 2H, S-CH2-
CH2), 1.7 (m, 2H, CH2-CH2-OH), 3.1 (t, J = 7.32 Hz,
2H, S-CH2), 3.6 (t, J = 6.83 Hz, 2H, CH2-OH), 3.7
(s, 1H, OH), 4.4 (q, 2H, O-CH2), 7.60 (t,J = 6.34 Hz,
1H, Harom), 7.65 (t, J = 5.37 Hz, 1H, Harom), 7.95
(dd, J = 6.34 Hz, J = 6.83 Hz, 1H, Harom), 8.05 ppm
(dd, J = 5.37 Hz, J = 5.37 Hz, 1H, Harom). 13C NMR
(125.66 MHz, CDCl3): δ = 14.89 (CH3), 24.73, 27.60,
27.67, 28.04, 28.10, 28.38, 28.40 (CH2), 28.52 (S-
CH2-CH2), 29.41 (CH2-CH2-OH), 33.33 (S-CH2),
61.97 (CH2-OH), 68.88 (O-CH2), 125.35, 125.56,
132.49, 132.54 (CHarom), 126.16, 132.75 (Carom),
133.07 (=C-S), 156.75 (=C-O), 178.85, 181.85 ppm
(C=O). MS[+ESI]: m/z 405 [M]+, 359 [M−45]+.
Anal. Calcd. for C23H32O4S1 (M, 404.57): C, 68.28; H,
7.97; S, 7.92. Found: C, 68.30; H, 6.88; S, 7.98.
2.5 Synthesis procedures
Method 1: Sodium carbonate (1.52 g) was dissolved
(60 mL) in ethanol. 2,3-dichloro-1,4-naphthoquinone or
Table 2. Selected bond distances (Å) for compound 13.
Atom
Distance
Atom
Distance
C1-C2
C2-C3
C1-S1
C11-S1
C15-C16
C21-C22
1.354(2)
1.495(3)
1.762(2)
1.765(2)
1.509(3)
1.505(4)
C3-O2
C10-O1
C2-O3
C18-O5
C18-O4
C19-O4
1.212(2)
1.220(2)
1.338(3)
1.209(3)
1.376(2)
1.375(2)

660
Cemil Ibis and Nahide Gulsah Deniz
Figure 1. The crystal structure of 13. Displacement ellipsoids are plotted
at the 50% probability level (symmetry transformations used to generate
equivalent atoms: (i)- x, -y, -z).
2.5b 2,3-Bis(11-sulphanyl-1-undecanol)-1,4-naphthoquinone (CH2-CH2-OH), 33.96 (S-CH2), 62.01 (CH2-OH),
(4): Compound 4 was synthesized from the reaction 125.82, 132.38 (CHarom), 132.06 (Carom), 146.89 (=C-
of 1 (1 g, 4.4 mmol) with 2 (0.9 g, 4.4 mmol) accord- S), 178.01 ppm (C=O). MS[+ESI]: m/z 563 [M]+, 546
ing to method 1. Orange solid. M.p.: 76–77◦C. Yield: [M−17]+. Anal. Calcd. for C32H50O4S2 (M, 562.88):
1.3 g (53%). Rf : 0.32 [CH2Cl2/EtAc (4:1)]. IR (KBr C, 68.28; H, 8.95; S, 11.39. Found: C, 68.40; H, 9.08;
pellet, cm−1): 3314 (OH), 3062 (Ar-H), 2913, 2847 S, 11.28.
1
(C-H), 1665 (C=O), 1588, 1512 (C=C). H NMR
(499.74 MHz, CDCl3): δ = 1.1–1.3 (m, 28H, CH2),
2.5c [2,3-Cyclo-(2-butylamino)ethanesulphanyl]-1,4-
naphthoquinone (6): Compound 6 was synthesized
from the reaction of 1 (1 g, 4.4 mmol) with 5 (0.58 g,
4.4 mmol) according to method 1. Purple solid. M.p.:
125–126◦C. Yield: 0.4 g (31%). Rf : 0.60 (CH2Cl2). IR
(KBr pellet, cm−1): 3069 (Ar-H), 2955, 2928, 2860 (C-
1.3–1.4 (m, 4H, S-CH2-CH2), 1.5–1.6 (m, 4H, CH2-
CH2-OH), 3.2 (t, J = 7.32 Hz, 4H, S-CH2), 3.6 (t,
J = 6.35 Hz, 4H, CH2-OH), 3.8 (s, 2H, OH), 7.60
(dd, J = 5.86 Hz, J = 5.85 Hz, 2H, Harom), 7.97 ppm
(dd, J = 5.36 Hz, J = 5.86 Hz, 2H, Harom). 13C NMR
(125.66 MHz, CDCl3): δ = 24.74, 27.69, 28.10, 28.39,
28.43, 28.46, 28.54 (CH2), 29.44 (S-CH2-CH2), 31.79
1
H), 1657, 1624 (C=O), 1587, 1532 (C=C). H NMR
O
O
O
O
O
(CH2)8
S
S
S
S
S
(CH2)8
+
S
(CH2)8
CH3
O
O
10
11
O
O
HS-(CH2)8-SH
O
S
S-(CH2)11-OH
OC2H5
9
CH3
OC2H5
O
HS-(CH2)11-OH
O
HS
O
O
O
Cl
12
2
13
CH3
3
O
Cl
O
S-(CH2)11-OH
S-(CH2)11-OH
O
O
O
1
S
CH3
S
O
4
HS-(CH2)2-NH-(CH2)3-CH3
O
O
5
O
14
CH3-(CH2)3
O
(CH2)3-CH3
O
O
O
O
S-(CH2)2-NH-(CH2)3-CH3
Cl
S-CH2-CH2-N
N
CH2
+
+
CH2
S
Cl
Cl
O
O
O
7
6
8
Scheme 1. Synthesis of compounds 3, 4, 6, 7, 8, 10, 11, 13 and 14.

Synthesis of new heteroatom substituted naphtho- and benzoquinone compounds
661
(499.74 MHz, CDCl3): δ = 0.8 (t, J = 7.32 Hz, 3H, N-CH2-CH2), 3.3 (t, J = 6.84 Hz, 2H, S-CH2), 3.7
CH3), 1.2–1.4 (m, 2H, CH2), 1.6–1.7 (m, 2H, N-CH2- (t,J = 6.84 Hz, 2H, N-CH2), 3.8 (m, 1H, NH), 7.55
CH2), 2.9 (t, J = 6.81 Hz, 2H, N-CH2-CH2), 3.3 (t, J = (t, J = 5.86 Hz, 1H, Harom), 7.60 (t, J = 5.79 Hz, 1H,
7.81 Hz, 2H, S-CH2), 3.5 (t, J = 6.84 Hz, 2H, N-CH2),
H
arom), 7.85 (dd, J = 5.85 Hz, J = 5.37 Hz, 1H, Harom),
7.50 (t, J = 7.32 Hz, 1H, Harom), 7.55 (t, J = 7.81 Hz, 7.96 ppm (dd, J = 5.86 Hz, J = 5.37 Hz, 1H, Harom).
1H, Harom), 7.85 (dd, J = 6.84 Hz, J = 6.85 Hz, 1H, 13C NMR (125.66 MHz, CDCl3): δ = 12.89 (CH3),
H
arom), 7.95 ppm (dd, J = 7.32 Hz, J = 6.84 Hz, 1H, 19.37 (CH2), 28.68 (NH-CH2-CH2), 31.83 (S-CH2),
arom). 13C NMR (125.66 MHz, CDCl3): δ = 12.89 48.38 (NH-CH2-CH2), 51.63 (NH-CH2), 124.80,
H
(CH3), 19.08 (CH2), 23.45 (N-CH2-CH2), 30.28 (S- 125.94, 126.00, 131.51, 131.84, 132.64 (CHarom,Carom),
CH2), 49.17 (N-CH2-CH2), 54.22 (N-CH2), 120.38, 139.07 (=C-S), 145.32 (=C-Cl), 179.24, 182.21 ppm
124.57, 125.52, 131.18, 131.30, 131.56 (CHarom, Carom), (C=O). MS[+ESI]: m/z 325 [M]+ Anal. Calcd. for
132.26 (=C-S), 145.13 (=C-N), 176.80, 178.82 ppm C16H18O2S1N1Cl1 (M, 323.84): C, 59.34; H, 5.60; N,
(C=O). MS[+ESI]: m/z 288 [M]+, 232 [M−56]+. 4.32; S, 9.90. Found: C, 59.40; H, 5.48; N, 4.55, S, 9.78.
Anal. Calcd. for C16H17O2S1N1 (M, 287.38): C, 66.87;
H, 5.96; N, 4.87; S, 11.15. Found: C, 64.40; H, 5.88;
N, 4.85; S, 11.18.
2.5f 2,3,4,5,6,7,8,9-Octahydronaphtho[2,3-e][1,10]
dithionine-11,16-dione (10): Compound 10 was
obtained from the reaction of 1 (1 g, 4.4 mmol) with
9 (0.78 g, 4.4 mmol) according to method 1. Orange
solid. M.p.: 170–171◦C. Yield: 0.52 g (35%). Rf :
0.65 (CHCl3). IR (KBr pellet, cm−1): 3068 (Ar-H),
2930, 2897, 2850 (C-H), 1665 (C=O), 1594 (C=C).
1H NMR (499.74 MHz, CDCl3): δ = 1.1–1.2 (m, 8H,
CH2), 1.6 (m, 4H, S-CH2-CH2), 3.2 (t, J = 5.86 Hz,
4H, S-CH2), 7.65 (dd, J = 5.37 Hz, J = 6.84 Hz, 2H,
2.5d [2-(Butylamino)ethanesulphanyl][2,2ꢁ]-dichloro[3,
3ꢁ]-bis(1,4-naphthoquinone) (7): Compound 7 was
synthesized from the reaction of 1 (1 g, 4.4 mmol)
with 5 (0.58 g, 4.4 mmol) according to method 1.
Black solid. M.p.: 97–98◦C. Yield: 1.1 g (48%). Rf :
0.40 (EtAc). IR (KBr pellet, cm−1): 3069 (Ar-H),
2957, 2928, 2871 (C-H), 1662 (C=O), 1592, 1556
1
(C=C). H NMR (499.74 MHz, CDCl3): δ = 0.9 (t,
H
arom), 8.05 ppm (dd, J = 7.32 Hz, J = 6.84 Hz, 2H,
arom). 13C NMR (125.66 MHz, CDCl3): δ = 21.96,
J = 7.32 Hz, 3H, CH3), 1.1–1.4 (m, 2H, CH2), 1.6–
1.7 (m, 2H, N-CH2-CH2), 3.0 (t, J = 6.81 Hz, 2H,
N-CH2-CH2), 3.8 (t, J = 7.32 Hz, 2H, S-CH2), 4.1
(t, J = 6.84 Hz, 2H, N-CH2), 7.50 (t, J = 5.84 Hz,
1H, Harom), 7.65 (t, J = 6.83 Hz, 1H, Harom), 7.95
(dd, J = 5.32 Hz, J = 5.85 Hz, 1H, Harom), 8.10 ppm
(dd, J = 5.32 Hz, J = 5.84 Hz, 1H, Harom). 13C NMR
(125.66 MHz, CDCl3): δ = 12.70 (CH3), 18.81 (CH2),
22.78 (N-CH2-CH2), 29.39 (S-CH2), 43.72 (N-CH2-
CH2), 67.18 (N-CH2), 125.77, 125.84, 127.80, 131.33,
H
24.19 (CH2), 26.62 (S-CH2-CH2), 35.41 (S-CH2),
126.21, 132.09, 132.60 (CHarom,
C
arom), 149.99 (=C-S),
177.63 ppm (C=O). MS [+ESI]: m/z 333 [M]+. Anal.
Calcd. for C18H20O2S2 (M, 332.48): C, 65.02; H, 6.06;
S, 19.28. Found: C, 65.10; H, 6.36; S, 19.13.
2.5g 7,8,9,10,11,12,13,14,23,24,25,26,27,28,29,30-
Hexadecahydrodinaphtho[2,3-e:2ꢁ,3ꢁ-n] [1,10,13,22]
131.51, 131.87 (CHarom,
Carom), 133.90 (=C-S), 143.29
tetrathiacyclotetracosine-5,16,21,32-tetrone
(11):
(=C–Cl), 148.89 (=C-N), 179.60, 183.43 ppm (C=O).
MS[+ESI]: m/z 478 [M−37]+, 441 [M−73]+. Anal.
Calcd. for C26H21O4S2N1Cl2 (M, 514.43): C, 60.70; H,
4.11; N, 2.72; S, 12.46 Found: C, 60.68; H, 4.08; N,
2.65, S, 12.28.
Compound 11 was obtained from the reaction of 1
(1 g, 4.4 mmol) with 9 (0.78 g, 4.4 mmol) according to
method 1. Red solid. M.p.: 134–135◦C. Yield: 1.4 g
(48%). Rf : 0.48 (CHCl3). IR (KBr pellet, cm−1): 3069
(Ar-H), 2923, 2851 (C-H), 1654 (C=O), 1590, 1454
(C=C). 1H NMR (499.74 MHz, CDCl3): δ = 1.2–1.40
(m, 16H, CH2), 1.4–1.6 (m, 8H, S-CH2-CH2), 3.2 (t,
J = 7.32 Hz, 8H, S-CH2), 7.60 (dd, J = 5.85 Hz, J =
5.37 Hz, 4H, Harom), 7.95 ppm (dd, J = 5.85 Hz, J =
5.86 Hz, 4H, Harom). 13C NMR (125.66 Hz, CDCl3):
δ 27.36, 27.82 (CH2), 29.27 (S-CH2-CH2), 34.00 (S-
CH2), 125.85, 132.05, 132.41 (CHarom, Carom), 147.00
(=C-S), 177.95 ppm (C=O). MS [+ESI]: m/z 665
[M]+. Anal. Calcd. for C36H40S4O4 (M, 664.97): C,
65.02; H, 6.06; S, 19.28. Found: C, 65.05; H, 6.10; S,
19.25.
2.5e 2-[2-(Butylamino)ethanesulphanyl]-3-chloro-1,
4-naphthoquinone (8): Compound 8 was synthesized
from the reaction of 1 (1 g, 4.4 mmol) with 5 (0.58 g,
4.4 mmol) according to method 1. Black solid. M.p.:
110–111◦C. Yield: 0.3 g (21%). Rf : 0.45 (CH2Cl2).
IR (KBr pellet, cm−1): 3344 (NH), 3068 (Ar-H),
2956, 2929, 2870 (C-H), 1659 (C=O), 1591, 1557
1
(C=C). H NMR (499.74 MHz, CDCl3): δ = 0.8 (t,
J = 7.32 Hz, 3H, CH3), 1.1–1.5 (m, 2H, CH2), 1.6–
1.7 (m, 2H, N-CH2-CH2), 3.1 (t, J = 7.81 Hz, 2H,

662
Cemil Ibis and Nahide Gulsah Deniz
2.5h 2-(7-Sulphanyl-4-methyl-coumarinyl)-3-(1-ethoxy)- 3H, CH3), 1.2–1.3 (m, 42H, CH2), 1.4–1.5 (m, 6H,
1,4-naphthoquinone (13): Compound 13 was synthe- S-CH2-CH2), 1.7 (s, 3H, OH), 3.0 (t, J = 7.32 Hz, 6H,
sized from the reaction of 1 (0.5 g, 2.2 mmol) with 12 S-CH2), 3.6 (t, J = 6.83 Hz, 6H, HO-CH2), 4.2 ppm
(0.42 g, 2.2 mmol) according to method 1. Red cry- (q, 2H, O-CH2-CH3). 13C NMR (125.66 MHz, CDCl3):
stal. M.p.: 194–195 ◦C. Yield: 0.35 g (40%). Rf : 0.65 δ = 14.77 (CH3), 24.74, 24.76, 24.77, 27.66, 27.68,
(CH2Cl2). IR (KBr pellet, cm−1): 3071 (Ar-H), 2918, 27.71, 28.14, 28.39, 28.15, 28.42, 28.43, 28.46, 28.48,
2849 (C-H), 1720, 1667 (C=O), 1600, 1551 (C=C). 1H 28.51, 28.54, 28.56, 28.58, 29.21, 29.44, 29.49 (CH2),
NMR (499.74 MHz, CDCl3): δ = 1.2 (t, J = 6.83 Hz, 31.79 (S-CH2-CH2), 31.93 (HO-CH2-CH2), 32.01,
3H, O-CH2-CH3), 2.3 (s, 3H, CH3), 4.5 (q, 2H, O-CH2- 33.55, 33.88 (S-CH2), 61.96 (HO-CH2), 68.76 (O-
CH3), 6.1 (s, 1H, CH), 7.1 (t, J = 5.60 Hz, 1H, Harom), CH2), 130.67, 141.37, 146.18 (=C-S), 155.68 (=C-O),
7.2 (t, J = 6.84 Hz, 2H, Harom), 7.4 (dd, J = 7.84 Hz, 173.99, 177.72 ppm (C=O). MS [−ESI]: m/z 758
J = 7.32 Hz, 1H, Harom), 7.65 (dd, J = 6.34 Hz, [M]+, 712 [M−45]+. Anal. Calcd. for C41H74O6S3 (M,
J = 5.83 Hz, 2H, Harom), 8.00 (dd, J = 7.32 Hz, J = 759.23): C, 64.86; H, 9.82; S, 12.66. Found: C, 64.90;
6.84 Hz, 1H, Harom). 13C NMR (125.66 MHz, CDCl3): H, 9.76; S, 12.43.
δ = 14.81 (O-CH2-CH3), 17.54 (CH3), 69.82 (O-CH2),
117.31, 123.69, 123.80 125.79, 125.98, 126.52, 130.37,
131.03, 132.78, 133.30 (CHarom, Carom), 113.57 (CH),
2.5k 2,3,5,6-Tetrakis(11-sulphanyl-1-undecanol)-1,4-
115.79 (=C-CH3), 139.21 (=C-S), 150.93 (S-Carom),
benzoquinone (17): Compound 17 was synthesized
152.59 (=C-O), 159.79 (C=O), 178.62, 180.18 ppm
from the reaction of 15 (0.6 g, 2.4 mmol) with 2
(C=O). MS[+ESI]: m/z 393 [M]+, 365 [M−28]+.
(1.96 g, 9.5 mmol) according to method 1. Yellow-
Anal. Calcd. for C22H16O5S1 (M, 392.43): C, 67.33; H,
green solid. M.p.: 85–86◦C. Yield: 1.4 g (63%). Rf :
4.11; S, 8.17. Found: C, 67.41; H, 4.08; S, 8.25.
0.45 [EtAc/CH2Cl2 (2:1)]. IR (KBr pellet, cm−1): 3279
(OH), 2917, 2848 (C-H), 1656 (C=O), 1484 (C=C).
1H NMR (499.74 MHz, CDCl3): δ = 1.1–1.3 (m, 56H,
2.5i 2,3-Bis(7-sulphanyl-4-methyl-coumarinyl)-1,4
CH2), 1.3–1.4 (m, 8H, S-CH2-CH2), 1.52 (s, 4H, OH),
3.0 (t, J = 7.32 Hz, 8H, S-CH2), 3.6 (t, J = 6.34 Hz,
8H, HO-CH2). 13C NMR (125.66 MHz, CDCl3): δ =
24.76, 27.74, 28.18, 28.43, 28.51, 28.52, 28.59 (CH2),
29.54 (S-CH2-CH2), 31.80 (HO-CH2-CH2), 33.38 (S-
CH2), 62.02 (HO-CH2), 145.07 (=C-S), 173.35 ppm
(C=O). MS [+ESI]: m/z 918 [M]+. Anal. Calcd. for
C50H92O6S4 (M, 917.54): C, 65.45; H, 10.10; S, 13.97.
Found: C, 65.50; H, 10.26; S, 13.23.
-naphthoquinone (14): Compound 14 was synthe-
sized from the reaction of 1 (0.5 g, 2.2 mmol) with
12 (0.42 g, 2.2 mmol) according to method 1. Dark
brown solid. M.p.: 270–271◦C. Yield: 0.6 g (51%).
Rf : 0.45 (CH2Cl2). IR (KBr pellet, cm−1): 3080
(Ar-H), 2972, 2950 (C-H), 1733, 1660 (C=O), 1601,
1
1546 (C=C). H NMR (499.74 MHz, CDCl3): δ =
2.3 (s, 6H, CH3), 6.2 (s, 2H, CH), 7.2 (dd, J =
7.81 Hz, J = 8.3 Hz, 2H, Harom), 7.4 (d, J = 8.3 Hz,
4H, Harom) ,7.7 (dd, J = 5.86 Hz, J = 5.85 Hz, 2H,
H
arom) 7.95 ppm (dd, J = 5.85 Hz, J = 5.37 Hz,
2H, Harom). 13C NMR (125.66 MHz, CDCl3): δ =
17.57 (CH3), 114.32 (CH), 117.27 (=C-CH3), 118.36,
124.20, 124.88, 126.58, 131.45, 133.37, 137.22, 147.38
(CHarom, Carom), 150.74 (=C-S), 152.59 (S-C=), 159.00
(C=O), 177.13 ppm (C=O). MS[−ESI]: m/z 538
[M]+. Anal. Calcd. for C30H18O6S2 (M, 538.601): C,
66.90; H, 3.36; S, 11.90. Found: C, 66.71; H, 3.18; S,
11.85.
3. Results and discussion
The reaction of 2,3-dichloro-1,4-naphthoquinone 1
with 11-mercapto-1-undecanol 2 in ethanol in the pre-
sence of Na2CO3 gave S, O-substituted-1,4-naphtho-
quinone 3 and S, S-substituted-1,4-naphthoquinone 4.
Ethoxy substituted mono(thio)-1,4-naphthoquinone 13
and bis(thio)substituted-1,4-naphthoquinone 14 were
obtained from the reaction of 1 with 12 in EtOH/
Na2CO3. In these reactions, mono(thio)-substituted
compounds containing chlorine atom derivatives were
not observed potentially due to the decreased thiol
amount in the medium of the reaction, while the ethoxy
derivatives of mono(thio)-substituted compounds were
obtained successfully. While compounds 3 and 13 were
formed, one chloro atom was replaced with ethoxy
groups, which acted as a nucleophilic compound.
2.5j 2,3,6-Tris(11-sulphanyl-1-undecanol)-5-ethoxy-1,
4-benzoquinone (16): Compound 16 was synthe-
sized from the reaction of 15 (0.6 g, 2.4 mmol) with
2 (1.96 g, 9.5 mmol) according to method 1. Yellow-
brown solid. M.p.: 60–61◦C. Yield: 0.5 g (27%). Rf :
0.65 [EtAc/CH2Cl2 (2:1)]. IR (KBr pellet, cm−1): 3311
(OH), 2917, 2849 (C-H), 1659 (C=O), 1567 (C=C). 1H
NMR (499.74 MHz, CDCl3): δ = 1.1 (t, J = 7.32 Hz,

Synthesis of new heteroatom substituted naphtho- and benzoquinone compounds
663
Compounds 6, 7 and 8 were obtained from the reac- was observed at m/z (%) 918 (100) for compound 17 in
tion of 1 with 2-(butylamino)ethanethiol 5. For com- the mode of ESI.
pounds 6 and 7, no bands were observed in the region
3200–3450 cm−1 attributable to the streching vibration
of the bonded NH group, indicating that the forma-
3.1 Absorption and fluorescence spectroscopy
tion of cyclization reaction had taken place yielding
the compounds 6. It was shown that interesting hete-
rocylic compounds 10 and 11 could be obtained from
the reaction of 2,3-dichloro-1,4-naphthoquinone 1 with
long alkyl chain dithiol 9. Isolation and identifica-
tion proved that a cyclization reaction had taken place,
yielding the compound 10 and intramolecular cycliza-
tion to yield heterocyclic diquinone 11 (scheme 1). The
ethoxy substituted-tris(thio)-1,4-benzoquinone 16 and
tetrakis(thio)-substituted-1,4-benzoquinone 17 com-
pounds were obtained from the reaction of p-chloranil
15 with 11-mercapto-1-undecanol 2 via vinilic substi-
tution (scheme 2).
The absorption parameters of compounds 3, 4, 6, 7, 8,
10, 11, 13, 14, 16 and 17 in different solutions were
reported in table 4. The electronic absorption spectra
of 6, 7, 8 showed the expected naphthoquinone bands
in the UV region around 240–248 nm and 300–347 nm
(π–π* electronic transitions) in chloroform. In addi-
tion, a third energy transition appeared as a broad
band in the visible region between 451 and 554 nm
(see table 4). This absorption was typical of amino-
substituted benzoquinones, naphthoquinones and
anthraquinones and is assigned to charge transfer (CT)
transitions and weak n–π* transitions of the carbonyl
group in the quinone.23 A broad band in the visible
region at 535 nm in tetrahydrofurane, 554 nm in chlo-
roform and 549 nm in methanol for compound 6 show
strong bathochromic shift relative to compounds 7 and
8. This bathochromic shift was due to N,S-substituted
cyclo group in quinone unit of compound 6. The
absorption spectra of 13 and 14 display the intense
bands having maxima between 278 and 331 nm and a
shoulder of lower intensity between 451 and 463 nm.
Ethoxy substituted naphthoquinone compound 13 was
considerably red-shifted at 243 and 329 nm in the UV
region relative to compound 14 which absorbs around
at 237 and 326 nm, respectively in THF.
The fluorescence excitation and emission maxima
of compounds 3, 4, 6, 7, 8, 10, 11, 13, 14, 16 and
17 in CHCl3/MetOH (1:1) solution were summarized
in table 5. Fluorescence is an important property of
quinone compounds for the use of organic materi-
als.24,25 The spectrum was composed of two broad
bands and comparable to those of the similar com-
pounds.26,27
Figure 2 shows the excitation and the emission of 13
in CHCl3/MetOH (1:1). The first band at 327 nm was
the fluorescence characteristic of the coumarin ring sub-
stituted naphthoquinone assigned to the excited band
and the second band at 398 nm was emission band at
room temperature.
FT-IR spectrum in KBr showed the following impor-
tant absorption bands. In the IR spectra of synthe-
sized compounds two typical strong quinonic car-
bonyl absorptions were observed between at 1654 and
1667 cm−1. Compounds 13 and 14 gave strong and
sharp carbonyl bands at 1667, 1660 cm−1 and at 1720,
1733 cm−1 which were due to coumarine ring. The NH
absorption appeared at 3344 cm−1 for compound 8. The
IR spectra of compounds 3, 4, 16 and 17 showed broad
bands at 3410, 3314, 3312 and 3279 cm−1 for the -OH
streching, respectively.
The 1H spectrum of the products in CDCl3 displayed
1
distinct signals with appropriate multiplets. H NMR
signal of the hydrogen atoms of the methylene group (S-
CH2) adjacent to the sulphur atom in compound 11 was
shifted to a higher field and displayed triplet at 3.2 ppm
(J = 7.32 Hz). The 13C NMR spectra of compound 13
gave two carbonyl signals at 178.62 and 180.18 ppm
(C=O) while compound 14 showed one carbonyl signal
at 177.3 ppm (C=O) in naphthoquinone unit.
The positive ion mode of ESI mass spectrum of the
compound 3 and the respective molecular ion peak was
observed at m/z (%) 405 (100) [M]+. The cleavage of
ethoxy group from compound 3 of the molecular ion
gave to rise fragment F1 at m/z (%) 359 (100) which
was the base peak. The respective molecular ion peak
O
O
O
HS-(CH2)11-OH
Cl
Cl
Cl
Cl
HO-(CH2)11-S
H5C2O
S-(CH2)11-OH
S-(CH2)11-OH
HO-11(CH2)-S
HO-11(CH2)-S
S-(CH2)11-OH
S-(CH2)11-OH
2
+
O
O
O
15
16
17
Scheme 2. Synthesis of compounds 16 and 17.

664
Cemil Ibis and Nahide Gulsah Deniz
Table 4. UV-Vis data of compounds 3, 4, 6, 7, 8, 10, 11, 13, 14, 16 and 17 in different solvents.
Compound
λa (logε)
λb (logε)
λc (logε)
3
4
241(4.2), 266(4.2) 335(3.5),
443(3.5)
241(4.5), 281(4.5) 335(4.0),
467(3.9)
241(4.2), 273(4.2) 338(3.5),
457(3.4)
242(4.2), 281(4.2) 344(3.6),
471(3.6)
238(3.7), 264(3.8) 333(3.1),
444(2.9)
241(3.9), 276(3.9) 343(3.3),
460(3.3)
6
7
239(4.2), 298(4.3) 535(3.4)
236(3.9), 339(3.3) 471(2.9)
240(3.5), 300(3.7) 554(2.9)
241(4.2), 345(3.6) 483(3.2)
236(3.6), 298(3.8) 549(2.9)
223(3.8), 267(3.6) 341(3.1),
460(2.7)
8
10
246(3.8), 342(2.9) 451(2.8)
245(3.0), 266(2.9) 312(2.5),
449(2.3)
241(3.6), 270(2.7) 343(3.0),
462(3.0)
243(3.6), 281(3.5) 329(3.5),
451(2.6)
237(4.0), 326(4.0) 451(3.1)
248(3.4), 347(3.3) 451(2.9)
248(3.7), 269(3.7) 315(3.2),
453(3.1)
257(3.8), 279(4.0) 344(3.4),
467(3.4)
244(4.5), 282(4.5) 331(4.5),
463(3.6)
240(3.5), 267(3.4) 326(3.5),
462(2.6)
–
247(3.8), 266(3.7) 313(3.2),
445(3.1)
-
11
13
14
241(3.7), 278(3.7) 330(3.7),
450(2.7)
222(4.3), 279(3.6) 326(3.7)
16
17
225(3.7), 245(3.9) 396(3.5)
223(3.2), 241(3.1) 401(2.8)
229(4.4), 244(4.4) 401(3.9)
225(3.5), 240(3.7) 405(3.5)
210(4.0), 245(4.0) 396(3.7)
210(3.6), 240(3.7) 401(3.5)
aTHF; b CHCl3; cMetOH.
(–); 8 and 11 were dissolved in MetOH
3.2 X-ray study
The standard average C–C bond distance in a flat
six carbon atom containing aromatic ring is 1.395(1)
Å. The double bond distance of C1–C2 was 1.354(2)
Å in 13, which was smaller than expected due to sub-
stituents such as =O. The double bond length of the
quinone moiety agreed well with corresponding dis-
tance in a similar compound.28 Crystal data and refine-
ment parameters for compound 13 were summarized in
table 1. The selected bond distances, bond and torsion
angles for compound 13 are listed in tables 2 and 3,
respectively. The bond lengths of C3-O2, C10-O1 and
C18-O5 were 1.212(2) Å, 1.220(2) Å, and 1.209(1)
Å, respectively, typical of C=O bonds. In the com-
pound 13, C–C–C and C–C–O angles were very close
to 120◦, as expected for sp2 hybridized atoms. In the
structure of the compound, the Ueq values of the C
atoms of the ethoxy chain generally increase on going
The compound 13 was crystallized in the triclinic
crystal system (space group P-1) with the unit cell
parameters a = 8.4474(2) Å, b = 9.1257(1) Å, c =
11.9197(2) Å, α = 84.474(4)◦, β = 84.506(4)◦, γ =
80.473(4)◦, V = 899.00(3) Å3, Z = 2. The structure
was solved by direct methods (SIR92) and refined to
the residual index R1 = 0.056. Drawings were pre-
pared with the program ORTEP-III21 with 50% prob-
ability displacement elipsoide for compound 13 in
figure 1.
Table 5. Fluorescence data of the compounds 3, 4, 6, 7, 8,
10, 11, 13, 14, 16 and 17.
λmax(ex.)
(nm)
λmax(em.)
(nm)
Compound
Solvent (1:1)
3
4
6
7
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
CHCl3/MetOH
221
220
226, 268
246
249
261
245
327
327
221
455
456
453, 535
494
497
417
494
398
390
457
8
10
11
13
14
16
17
Figure 2. The excitation (I) and emission (II) spectra of 13
(2 × 10−4 M) in CHCl3/MetOH (1:1) at room temperature.
222
458

Synthesis of new heteroatom substituted naphtho- and benzoquinone compounds
665
from C21 to C22, reflecting libration of the chain. The DMF to explore the substituent effects on their redox
both rings of naphthoquinone unit were planar with a potentials. The voltammetric data of these compounds;
maximum deviations of 0.0157(1) Å (plane 1 = C1-
cathodic peak potentials (Epc), anodic peak potentials
C2-C3-C4-C9-C10) and 0.0045(1) Å (plane 2 = C4-
(Epa) versus glassy carbon electrode (GCE), half-wave
C5-C6-C7-C8-C9). The substituted coumarine ring was
planar with a maximum deviation of 0.0024(1) Å (plane
3 = C11-C12-C13-C14-C19-C20) and 0.0139(1) Å
(plane 4 = C14-C15-C17-C18-O4-C19). Dihedral
angles were 64.54(1)◦ between planes 1 and 3,
63.61(1)◦ between planes 2 and 4.
peak potentials (E1/2), the difference between the first
oxidation and reduction processes ( Ep) and cathodic
vs. anodic peak current ratio (ipc/ipa) were shown in
table 6. Experiments using a glassy carbon electrode
were performed in order to investigate the electrooxi-
dizable groups and to complete the information in the
presence of proton sources. Additional oxidation waves
were discernible.
Electrochemical study, cyclic voltammetry was per-
formed in aprotic medium and the unsubstituted
quinones 2,3-dichloro-1,4-naphthoquinone 1 and p-
3.3 Electrochemical study
Cyclic voltammetry measurements of 1, 3, 4, 6, 7,
8, 10, 11, 13, 14, 15, 16 and 17 were performed in chloranil 15 were used as standarts. Compounds 1 and
Table 6. Voltammetric parameters in DMF/TBAP 0.1 M, v = 0.1 V s−1
Compound
.
a
−(Epc)a
−(Epa)a
−(E1/2
)
(
Ep)b
(ipc/ipa)c
2,3-Dichloro-1,4-naphthoquinone 1
0.287d
1.074d
0.730d
0.408d
0.592d
1.349
0.540d
1.187
0.804d
1.367
0.815d
1.277
1.916
2.258
0.550d
0.872
0.506d
1.213
0.564d
0.848
0.473d
1.088
1.898
2.185
0.283d
0.909
1.271
0.403d
1.129
0.374d
1.039
0.189d
0.973d
0.644d
0.353d
0.536d
–
0.238
1.023
0.687
0.381
0.564
–
0.498
–
0.765
–
0.097
0.099
0.085
0.055
0.055
–
0.075
–
0.077
–
0.992
2.034
1.659
1.141
1.624
–
1.254
–
1.028
–
p-chloranil 15
3
4
6
7
0.465d
–
0.726d
–
0.502d
1.796
–
0.658
–
–
0.313
–
–
1.058
–
–
–
–
–
–
8
0.255d
0.594
0.433d
–
0.403
–
0.470
–
0.513
–
0.438
–
0.295
–
0.073
–
0.102
–
0.069
–
1.055
–
1.238
–
1.109
–
1.057
–
10
11
13
0.463d
–
0.403d
–
–
–
–
–
–
–
–
–
14
0.209d
–
0.246
–
–
0.364
–
0.337
–
0.073
–
–
0.077
–
0.073
–
0.946
–
–
1.004
–
1.085
–
–
16
17
0.325d
–
0.301d
–
aPeak potential (V vs. Ag/AgCl) at room temperature as determined by cyclic voltammetry at a GC electrode and given with-
out iR drop correction, E1/2 (approximated by (Epa + Epc)/2) in V vs. Ag/AgCl; supporting electrolyte tetrabutyl ammonium
perchlorate (0.1 M) in DMF, scan rate 0.1 V s−1 concentration of compounds 10−4 M. b(Epa – Epc) in V. cCathodic vs. anodic
peak current ratio. dReversible wave

666
Cemil Ibis and Nahide Gulsah Deniz
Figure 3. Cyclic voltammogram of compounds 4, 10 and 13 in DMF
obtained by using tetrabutyl ammonium perchlorate (0.1 M) as the supporting
electrolyte at scan rate of v = 0.1 V s−1
.
15 showed behaviour typical of quinones in aprotic representing in table 6, were observed at a scan rate 0.1
medium.29,30 Two reversible one-electron waves were Vs−1 for compounds 4, 6, 8, 10, 11, 16 and 17. The
observed. The first reversible reduction wave was, for redox behaviour of compounds 3, 7, 13 and 14 was very
1, −0.287 V vs. Ag/AgCl, represented the addition of different. Three reduction waves were observed for 3
one electron to the quinone core to form a semiquinone and 14, and four reduction waves were observed for 7
anion radical. Furthermore, if we consider that the ratio and 13. Cyclic voltammogram of compounds 4, 10 and
of the cathodic to anodic peak current was near 1 13 in DMF was given in figure 3. The intensity of the
(ipc/ipa = 0.99 for compound 1), it could be proposed two quinone reduction waves has decreased, the quasi-
that 2,3-dichloro-1,4-naphthoquinone 1 is transformed reversible character of the second wave has almost dis-
to a stable semiquinone anion radical (Q·−). In the case appeared for 3, 7, 13 and 14. The potentials for reduc-
of more negative reduction process (second cathodic tions were more negative for 3, 4, 6, 7, 8, 10, 11, 13 and
and first anodic peak), the largest difference between 14 according to 2,3-dichloro-1,4-naphthoquinone 1.
the cathodic and anodic peak potential (Epa–Epc
=
99.7 mV) (see in table 6) suggests that the reduction of
the semiquinone anion radical (Q−) to the dianion (Q2−)
was partially controlled by the electronic transference 4. Conclusions
and by diffusion. These oxidation-reduction reactions
could be represented by the following equations:31
The aim of this study was to synthesize and charac-
terize some naphthoquinone and benzoquinone 3, 4,
6, 7, 8, 10, 11, 13, 14, 16 and 17 compounds. Their
structures were determined by using micro analysis,
·−
Q + e−
Q
−2
(reversible)
−−−ꢀ
ꢁ−−−
Q·− + e−
Q
(quasi − reversible).
1
−−−ꢀ
FT-IR, H-NMR, 13C-NMR, MS, UV-Vis. Photo- and
ꢁ−−−
electrochemical properties of N-, S-, O-substituted
naphthoquninone and S-, O-substituted benzoquinone
compounds were investigated by using fluorescence
spectroscopy and electrochemical method (cyclic
voltammetry). The crystal structure of compound
13 was determined by X-ray diffraction method.
These compounds possess high solubility in various
organic solvents such as chloroform, dichloromethane,
tetrahydrofurane and are insoluble in water.
For this electrochemical reaction, the standard poten-
tial was also estimated from the difference between
both the anodic and cathodic peak potential: E1/2
=
−1.027 V (vs. SCE),31 in our study, E1/2 = −1.024 V
(vs. GCE) in table 6 for 1. The cyclic voltammogram
of p-chloranil 15 exhibits an anodic peak related to
the oxidation of HQ−, presents a cathodic peak related
to reduction of p-chloranil (Q) to reduced p-chloranil
(HQ−).
The reversibility of this redox couple (Ipc ≈ Ipa) sug-
gests that the dianion was also stable in the time scale of
the voltammetric experiments. The ratio of the cathodic
to anodic peak current was near 1 for compounds 3, 4,
6, 7, 8, 10, 11, 13, 14, 16 and 17. Two reduction waves
Acknowledgement
We thank the Research Project Fund of Istanbul Univer-
sity for financial support to carry out this work.

Synthesis of new heteroatom substituted naphtho- and benzoquinone compounds
667
References
18. Parr R W and Reiss J A 1984 Austr. J. Chem. 37(2) 389
19. Altomare A, Cascarano G, Giacovazzo C, Guagliardi A,
Burla M, Polidori G and Camalli M 1994 J. Appl. Cryst.
27 435
20. Watkin D J, Prout C K, Carruthers J R and Betteridge J R
1996 Crystals Issue 10, P W Chemical Crystallography
Laboratory, Oxford, UK
1. Kinoshita S, Koura Y, Kariya H, Ohsaki N and Watanabe
T 1999 Pest. Sci. 55(6) 659
2. Scherbak N, Strid A and Eriksson L A 2005 Chem. Phys.
Lett. 414 243
3. Sutovsky Y, Likhtenshtein G I and Bittner S 2003 Tetra-
hedron 59 2939
21. Farrugia L J 1997 J. Appl. Cryst. 30 565
22. Crystallographic data (excluding structure factors) for
the structures in this paper have been deposited in
the Cambridge Crystallographic Data Centre as sup-
plementary publication number CCDC 724897 for 13.
Copies of the data can be obtained, free of charge, via
www.ccdc.cam.ac.uk/conts/retrieving.html or from the
Cambridge Crystallographic Data Centre, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223
336033. E-mail: deposit@ccdc.cam.ac.uk.
23. Win T and Bittner S 2005 Tetrahedron Lett. 46 3229
24. Kuroda S, Oda M, Takamatsu H, Hatakeyama H, Noda
C, Zhang Y, Miyatake R, Thanh N C, Yanagida A,
Kyougoku M and Kawakami T 2007 Sci. Tec. Adv.
Mater. 8 306
4. Hasegawa T, Mochida T, Kondo R, Kagoshima K, Iwasa
Y, Akutagawa T, Nakamura, T and Saito G 2000 Phys.
Review B 62 10059
5. Cormier R A, Posey M R, Bell W L and Fonda H N 1989
Tetrahedron 45(15) 4831
6. Chia V K F, Soriaga M P and Hubbard A T 1983 J. Phys.
Chem. 87(2) 232
7. Slana G B C A, Azevedo M S, Lopes R S C, Lopes C C
and Cardoso J N 2006 Beilst. J. Org. Chem. 2 1
8. Ibis C and Gunes Z O 2008 Dyes Pigments 77(1) 39
9. Wang W, Li T, Milburn R, Yates J, Hinnant E, Luzzio
M J, Noble S A and Attardo G 1998 Bioorg. Med. Chem.
Lett. 8 1579
10. Thines E, Anke H and Sterner O 1998 J. Nat. Prod. 61
306
25. Umadevi M, Ramasubbu A, Vanelle
P
and
Ramakrishnan V 2003 J. Raman Spectrosc. 34 112
26. Ibis C and Ayla S S 2008 Arkivoc 6 29
27. Ibis C and Deniz N G 2010 Phosporus Sulfur Silicon
185 2324
11. Boudalis
A K, Policand X, Sournia-Saquet A,
Donnadieu B and Tuchaques J P 2008 Inorg. Chim.
Acta 361 1681
12. Behforouz M, Haddad J, Cai W and Gu Z 1998 J. Org.
Chem. 63(2) 343
28. Boudalis
A K, Policand X, Sournia-Saquet A,
Donnadieu B and Tuchagues J P 2008 Inorg. Chim.
Acta 361 1681
13. Fieser L F and Brown R H 1949 J. Am. Chem. Soc. 71
3609
29. Ibis C, Ayla S S and Deniz N G 2010 Asian J. Chem.
22(8) 6195
30. Abreu F C, Lopes A O, Pereira M A, Simone C A and
Goulart M O F 2002 Tetrahedron Lett. 43 8153
31. Gozales F J 1998 Electroanalysis 10(9) 638
14. Sayil C and Ibis C 2010 Russ. J. Org. Chem. 46(2) 209
15. Tandon V K and Maurya H K 2009 Hceterocycles 77(1) 611
16. Prescott B 1969 J. Med. Chem. 12 181
17. Chen C, Liu Y Z, Shia K S and Tseng H Y 2002 Bioorg.
Med. Chem. Lett. 12(19) 2729