Synthesis and characterization of nitrogen and sulfur containing 1,4-naphthoquinones

Article abstract of DOI:10.1080/10426507.2013.796475

New N,S-disubstituted naphthoquinones were synthesized by reactions of S- and N-nucleophiles with 2,3-dichloro-1,4-naphthoquinone. 2-(Hexadecylthio)-3- (phenylamino)-naphthalene-1,4-dione 5a was synthesized by reaction of 2-chloro-3-(phenylamino)-naphthal

Full text of DOI:10.1080/10426507.2013.796475

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Phosphorus, Sulfur, and Silicon and the Related
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SYNTHESIS AND CHARACTERIZATION OF NITROGEN AND
SULFUR CONTAINING 1,4-NAPHTHOQUINONES
a
b
a
Cigdem Sayil , Semih Kurban & Cemil Ibis
a
Istanbul University, Faculty of Engineering, Department of Chemistry , 34320 , Avcilar-
Istanbul , Turkey
b
Real Kom., Sakarya Mah., Türbe Cad., No: 2 , 34050 , Eyüp-Istanbul , Turkey
Accepted author version posted online: 26 Jul 2013.
To cite this article: Phosphorus, Sulfur, and Silicon and the Related Elements (2013): SYNTHESIS AND CHARACTERIZATION OF
NITROGEN AND SULFUR CONTAINING 1,4-NAPHTHOQUINONES, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2013.796475
To link to this article: http://dx.doi.org/10.1080/10426507.2013.796475
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SYNTHESIS AND CHARACTERIZATION OF NITROGEN AND SULFUR
CONTAINING 1,4-NAPHTHOQUINONES
a *
Cigdem SAYIL , Semih KURBAN and Cemil IBIS
b
a
a
Istanbul University, Faculty of Engineering, Department of Chemistry, 34320 Avcilar-Istanbul,
Turkey.
b
Real Kom., Sakarya Mah., Türbe Cad., No: 2 , 34050 Eyüp-Istanbul, Turkey
Abstract New N,S-disubstituted naphthoquinones were synthesized by reactions of S- and N-
nucleophiles with 2,3-dichloro-1,4-naphthoquinone. 2-(Hexadecylthio)-3-(phenylamino)-
naphthalene-1,4-dione 5a was synthesized by reaction of 2-chloro-3-(phenylamino)-naphthalene-
1
,4-dione 3a with hexadecanethiol 4a. The structures of the new synthesized naphthoquinone
1
13
derivatives were determined by micro analyses and spectroscopic methods (FT-IR, H NMR, C
NMR, MS and UV/Vis.). Photo- and electrochemical properties of selected compounds were
investigated by using fluorescence spectroscopy and the cyclovoltammetry method.
Key Words N,S-Disubstituted naphthoquinones; spectroscopic properties; fluorescence
spectroscopy; cyclovoltammetry
1
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Address correspondence to Cigdem Sayil, Faculty of Engineering, Department of Chemistry,
Istanbul University, 34320 Avcilar-Istanbul, Turkey. E-mail: sayil@istanbul.edu.tr
INTRODUCTION
1
-4
It has been reported that some N-, S- and N,S-subsituted 1,4-naphthoquinones were
synthesized from 2,3-dichloro-1,4-naphthoquinone. 1,4-Naphthoquinone derivatives in general,
and those possessing an amino group in particular, have stimulated enormous interest due to their
biological activities, including antiproliferative, antiallergic, antifungal, antibacterial, antitumoral
3
,5-9
properties e.t.c.
However, the value of quinones is not restricted to biological activity.
1
0-13
Quinoidal compounds are also used as dyes, photo-conductors and magnetic materials.
Primary and secondary aliphatic amines, cyclic amines and anilines substituted with
electron-donating groups, are quite reactive and afford high yields of the corresponding
aminoquinones. Treatment of 2,3-dichloro-1,4-naphthoquinone with amines affords mono amino
1
4
derivatives. Both halogen atoms can be replaced by using nitrogen containing heterocycles.
Naphthoquinone pigments typically exhibit variable colors, and are widely used in the
cosmetic industry for the production of cosmetic dyes. Naphthoquinone dyes possess the
1
5,16
advantages of having strong, stable coloring properties.
There is an US patent about
manufacturing of some organomercapto-substituted quinones which can be used as oil-soluble
1
7
fungicidal sprays for plants.
2
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Fluorescence is an important photochemical property of quinones for the use as organic
2
,18-20
materials.
,4-naphthoquinones. The fluorescence excitation and emission maxima of N- and N,S-
substituted-1,4-naphthoquinones in trichloromethane, methanol or aqueous solutions at room
There are, however, few reports on fluorescence studies of N-, and S-substituted-
1
21-25
temperature have been reported.
A plethora of quinones is known, the electrochemistry of which has been widely
1
8,26
studied.
There are some reports on electrochemical studies of N-, S-, and O-substituted
4
,21,23
naphthoquinones.
As the bioreduction of quinones is influenced by their redox properties,
the understanding of how structural features of the quinones are related to these properties is an
important step to comprehend their mechanism of action and predict modifications to improve
2
7
their biological activity.
2
3-
We have earlier reported the synthesis of new sulfur containing 1,4-naphthoquinones.
4
5,28-29
The goal of the presented work is to continue the study on this subject by synthesizing
nitrogen and sulfur containing hetero-1,4-naphthoquinones and characterization of their
1
13
structures by using microanalysis, FT-IR, H NMR, C NMR, mass, and UV/Vis spectroscopy.
Photo- and electrochemical properties of selected compounds were investigated by using
fluorescence spectroscopy and the cyclovoltammetry method.
RESULTS AND DISCUSSION
Syntheses
In the course of our work, we prepared the amino and thio derivatives of 1,4-
naphthoquinone. The precursors, 2-alkylamino-3-chloro-naphthoquinones 3a-i and 2-chloro-3-
3
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alkylsulfanyl-1,4-naphthoquinone 7a-b required for the synthesis of 5a-i, 6a-i and 11a-f, have
been synthesized according to Scheme 1. The reaction of 2,3-dichloro-1,4-naphthoquinone 1
with alkanethiols 4a-b afforded mixtures of 2-chloro-3-alkylsulfanyl-1,4-naphthoquinones (53–
5
5%) 7a,b, 2,3-bis-alkylsulfanyl-1,4-naphthoquinones (21–26%) 8a,b and 2-ethoxy-3-
alkylsulfanyl-1,4-naphthoquinones (10–12%) 9a,b. This reaction involves nucleophilic
displacement of chloride ions in 2,3-dichloro-1,4-naphthoquinone 1 with sulfur nucleophile (1:1)
resulting in the formation of 7a,b, 8a,b. Nucleophilic displacement of chloride in 2,3-dichloro-
1
,4-naphthoquinone 1 with ethoxide from the solvent, instead of the sulfur nucleophile resulted
exclusively in the formation of 2-ethoxy-3-alkylsulfanyl-1,4-naphthoquinones 9a,b as shown in
Scheme 1. In the meantime, 2-chloro-3-(hexadecylthio)naphthalene-1,4-dione 7a was newly
synthesized as precursor in this study. The reactions of 2,3-dichloro-1,4-naphthoquinone 1 with
aromatic amines 2a-i resulted in the formation of 2-arylamino-3-halo-1,4-naphthoquinones 3a-i
as main products.
<Scheme 1>
Firstly, we studied the reactions of 2,3-dichloro-1,4-naphthoquinone 1 with different aryl
amines 2a-i and alkanethiols 4a,b in the presence or absence of a base and synthesized with
previously reported 2-arylamino-3-halo-1,4-naphthoquinones 3a-i and 2-chloro-3-alkylsulfanyl-
2
8-32
1
,4-naphthoquinones 7a,b utilized precursors.
. Aryl amines with enhanced nucleophilicity
replaced only one chlorine substituent upon reaction with 2,3-dichloro-1,4-naphthoquinone 1,
due to electronic enrichment of the quinone system. To achieve the substitution of the second
4
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3
chlorine atom, an electron-withdrawing effect must be imposed on the quinone ring or a
3
3
4
catalyst must be used.
The second synthetic step towards the desired novel products 5a-i, 6a-i and 11a-f was
achieved with good yields by reaction of alkanethiols 4a,b with 2-arylamino-3-halo-1,4-
naphthoquinones 3a-i and primary alkyl amines 10a-c with 2-chloro-3-alkylsulfanyl-1,4-
naphthoquinones 7a,b. The reaction conditions for the synthesis of 2,3-disubstituted 1,4-
naphthoquinones are reported in Table 1. Both aromatic amines and aliphatic thiols smoothly
substituted one chlorine atom of 1, producing the mono-substituted derivatives 3 and 7, but
aromatic amines react with 1 to yield 3a-i with higher yields (70–95%) compared to aliphatic
thiols which result in the formation 7a,b (53–55%).
<Table 1>
FT-IR and NMR Spectra
1 13
All products were identified by FT-IR, H NMR, C NMR, MS, and UV/Vis spectroscopic
data. The IR spectra of 5a-i, 6a-i and 11a-f exhibit typical strong quinone carbonyl absorption
–
between 1628 and 1669 cm . The NH stretching vibration appeared between 3288 and 3322 cm
1
–
1
1
The H NMR spectra of 5a-i and 6a-i appeared as double-doublets and triplet of triplets
.
between at δ 7.96–8.10 (2H) and 7.52–7.68 (2H) which could be distinguished. These were
H
attributed to naphthalene protons, as expected from such non-symmetric systems and the NH
proton was observed as triplet at 6.64–6.56 ppm for 5c, 6c and the other derivatives of 5 and 6 as
singlet at between 7.52 and 7.91 ppm. Two different carbonyl signals appear at around 180 ppm
1
in the C NMR spectra of 11a-f as expected and the structures of 5g-i were also confirmed by
3
5
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1
3
2
C NMR APT spectra in the present study. The protons of SCH have close values of the
1
chemical shift as triplet at around 2.50 ppm. In the H NMR spectra of 11c and 11f, the vinylic
protons are observed as multiplets at 5.26–5.28.
Absorption and Fluorescence Spectroscopy
The absorption spectra of compounds 5a-i, 6a-i and 11a-f were measured in the nonpolar
solvent petroleum ether and in the more polar solvent trichloromethane. The molar absorption
coefficients were determined in the solvents and the data are presented in Table 2.
<Table 2>
In the absorption spectra of the 2,3-bis-donor-substituted 1,4-naphthoquinones 5a-i and 6a-
i, the π-π* character of the longest wavelength band was indicated by its intensity and its
displacement to longer wavelengths in the polar solvent trichloromethane. In view of the
sensitivity of this band towards the electron-donating strength of the donor atom, it is reasonable
to assume that the transition involves electron-density transfer from the donor group to the
3
5
quinone system, as in the similarly substituted benzoquinones and anthraquinones.
The electronic absorption spectra of 5a-i and 6a-i showed the expected benzene and
naphthoquinone bands in the UV region at around 232–243 nm (λ ) and at 281–289 nm (λ ). In
addition, another lower energy band appeared in the visible region centered between 485–539
nm (λ ) in trichloromethane. 5h, 6h and 5i, 6i having an electron-donor substituent (OCH ) were
1
2
3
3
observed at the longest wavelength. The absorption spectra of 5a, 5c, 5h, 5i and 11a-c in
trichloromethane solution are shown in Fig.1 and Fig.2. Furthermore, the synthesized dyes of
aliphatic derivatives 11a-f show the characteristic long wavelength thio-substituted quinone π-π*
6
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broad transition at 478–492 nm in trichloromethane. As illustrated in the Table 2, in the
absorption spectra of the compounds 5a-i, 6a-i and 11a-f considerable differences depending on
the substituent in the naphtoquinone fragment were observed. The anilino-derivatives (5a-i, 6a-i)
absorb at longer wavelengths than the aliphatic derivatives (11a-f).
<
Figure 1>
Figure 2>
<
In general, the light fastness properties of phenylaminonaphthalene derivatives always
showed better photochemical stability than their alkylamino counterparts. Derivatives of 5a-i and
1
1,35
6
a-i approached commercial acceptability in this respect (on polyester substrates).
It is known that 2-donor- and 2,3-bis-donor-substituted 1,4-naphthoquinones evidently can
3
5
provide almost the full spectral range of colors shown in Table 1. Both mass spectra and
elemental analyses confirm the molecular formula of the products 5a-i, 6a-i and 11a-f.
The fluorescence excitation and emission maxima of compounds 3a,b, 3g, 5a,b, 5e-g, 6b-
d, 6h-i, and 11c-e in trichloromethane solution are summarized in Table 3. The spectrum was
composed of two excitation bands and two emission bands comparable to those of the similar
2
1-25
compounds.
<Table 3>
Electrochemical Study
Cyclovoltammetry measurements of 5g, 6b, 6h, 11c and 11d were performed in aprotic
medium (DMF) to explore the substituent effects on their redox potentials. The voltammetric
data of these compounds i. e. cathodic peak potentials (Epc) and anodic peak potentials (Epa
)
7
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versus a glassy carbon electrode (GCE), half-wave potentials (E1/2), the difference between the
p
first oxidation and reduction processes (E ) and cathodic vs. anodic peak current ratio (ipc/ipa) are
shown in Table 4. Experiments using a glassy carbon electrode were performed in order to
investigate the electro-oxidizable groups and to complete the information in the presence of
proton sources. Additional oxidation waves were discernible.
<Table 4>
2
,3-Dichloro-1,4-naphthoquinone 1 was used as standard. Compound 1 showed behaviors
2
3,36
typical of quinones in aprotic medium.
Two reversible one-electron waves are observed for
−
1. The first reversible reduction wave is due to the formation of a semiquinone anion radical Q
−
−
Q (reversible)]. In the case of more negative reduction processes, the reduction
[
Q + e
−
2−
of the semiquinone anion radical Q to the dianion Q [Q + e
−
−
2−
Q (quasi-reversible)]
3
7
possibly was partially controlled by the electronic transference and by diffusion. The
reversibility of this redox couple (Ipc ≈ Ipa) suggests that the dianion was also stable in the time
scale of the voltammetric experiments. The ratio ipc/ipa was near 1 for compounds 6h and 11d.
−
1
Two reduction waves were observed for 5g, 6h, 11c and 11d at a scan rate of 0.1 Vs (see Table
4
). The redox behavior of compound 6b was different. Three reduction waves were observed for
b. The cyclovoltamogram of compound 6b in DMF is given in Fig. 3.
6
<Figure 3>
EXPERIMENTAL
All chemicals and solvents were obtained commercially and used without purification.
Products were isolated by column chromatography on SiO (Fluka Kieselgel 60, particle size 63
2
8
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~
200 ꢀm). TLC plates: silica 60F254 (Merck, Darmstadt), detection with ultraviolet light (254
nm). The precursors 3a-i, 7b and by-products 8a,b and 9a,b were synthesized from 1,4-
naphthoquinone 1 and aromatic amines or alkyl thiols according to the procedures reported in the
literatures and confirmed by melting points, elemental analyses, FT-IR spectroscopy by
2
8-32
comparison with published data.
Methods
Melting points were measured on a Büchi B-540 melting point apparatus and are
uncorrected. Elemental analyses were performed with a Thermo Finnigan Flash EA 1112
–
elemental analyzer. IR (cm ) spectra were recorded in KBr pellets or Nujol mulls on a Perkin
1
Elmer Precisely Spectrum One FTIR spectrometer. NMR spectra (CDCl
3
) were recorded on a
1
13
Varian UNITY INOVA instrument operating at 499.74 MHz for H and at 125.66 MHz for C.
Mass spectra were obtained on a Thermo Finnigan LCQ Advantage MAX LC/MS spectrometer
according to ESI probe. UV spectra in chloroform and petroleum ether solution were recorded on
Perkin Elmer Lambda 35 UV/vis Spectro. Fluorescence spectra were run on a VARIAN Cary
Eclipse Fluorescence Spectrophotometer. Excitation and emission spectra were measured for
−
4
1
3
0 M solutions for all compounds in CHCl at room temperature. Excitation and emission slit
widths were set at 5 nm.
Cyclovoltammetry Measurements
Cyclovoltammetry measurements were performed at room temperature in an airtight three-
2
electrode cell by using a glassy carbon electrode (GCE) with a 0.071 cm surface area as the
9
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working electrode, a platinum wire served as the counter electrode and a Ag/AgCl (in a saturated
KCl solution) 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 electrode
was polished with de-agglomerated alumina (a particle size of 0.05 micron) before each run. The
electrochemical reaction vessel was charged with 10 mL of a DMF solution of 5g, 6b, 6h, 11c
−
and 11d (1 × 10 M) and tetrabutylammonium perchlorate (0.1 M) as the electrolyte.
4
Measurements were made over a potential range between 0.5V and −2.0V for 6h, 11d, 0.0V and
−
1.5V for 5g, 11c, 1.0 and −2.0V for 6b with a scan rate of 0.1V s . Voltammetric parameters
1
−
for all compounds are summarized in Table 4.
General Procedure for the Preparation of Hetero-1,4-naphthoquinones
Equimolar amounts of 2,3-dichloro-1,4-naphthoquinone
1
or monosubstituted
naphthoquinone derivatives 3, 7 and N- or S-nucleophilic compounds 2a-i, 4a-b, 10a-c in abs.
EtOH (50 mL) were stirred at different temperatures using base, where required (Table 1). The
color of the solution quickly changed and the extent of the reaction was monitored by TLC.
CHCl
with water (4×30 mL), and dried with Na
and the residue was subjected to column chromatography on silica gel using suitable solvents
Table 1).
Scheme 1 represents the reaction of 2,3-dichloro-1,4-naphthoquinone 1 with aromatic
amines, aliphatic amines and aliphatic thiols, yielding the desired novel 2-arylamino-3-
3
(30 mL) was added to the reaction mixture. The organic layer was separated and washed
2
SO . The resulting solution was concentrated in vacuo
4
(
10
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alkylsulfanyl-1,4-naphthoquinones
5
and 6, and 2-alkylamino-3-alkylsulfanyl-1,4-
naphthoquinones derivatives of 11, respectively. The composition and properties of the
corresponding products are summarized in Table 1.
Experimental and spectroscopic data of compounds 5a–5i and 6a–6i are compiled in the
“SUPPLENTAL MAERIALS” file
2
-(Hexadecylthio)-3-(phenylamino)naphthalene-1,4-dione (5a): Compound 5a
was synthesized from 0.20g (0.704 mmol) 2-chloro-3-(phenylamino)naphthalene-1,4-dione 3a
and 0.182g (0.704 mmol) hexadecanethiol 4a using triethylamine as base according to the
general procedure. IR: 3310 (NH), 3052 (CHarom.), 2914, 2849 (CHaliph.), 1665, 1634 (C=O),
1
1
2
7
591, 1555 (C=C). H NMR: 0.79–0.83 (t, 3H, J = 6.83 Hz, CH
3
), 1.07–1.30, 1.51–1.59 (m,
), 6.94–6.95 (d, 2H, J = 7.32 Hz, CHarom), 7.05–
.08 (t, 1H, J = 7.32 Hz, CHarom), 7.23–7.26 (t, 2H, J = 7.31 Hz, CHarom), 7.59 (t, 1H, J = 7.56
2 2
8H, CH ), 2.49–2.52 (t, 2H, J = 7.32 Hz, SCH
Hz, CHnapht), 7.66 (t, 1H, J = 7.56 Hz, CHnapht), 7.73 (bs, 1H, NH), 7.99 (d, 1H, J = 7.56 Hz,
1
3
CHnapht), 8.08 (d, 1H, J = 7.56 Hz, CHnapht). C NMR: 14.1 (CH
CH ), 33.1 (SCH ), 117.4, 121.4, 127.4 (CHarom), 123.5 (SCnapht), 129.6 (NHCnapht), 125.6,
25.8, 131.6, 132.5 (CHnapht), 133.4, 137.5 (Cnapht), 144.0 (NHC), 179.4, 180.0 (C=O). MS
3
), 21.6, 28.0, 28.6, 29.2, 31.0
(
2
2
1
+
+ESI): m/z = 506 [M] , C32
(
2
H43NO S (505.75). Calcd.: C 75.99; H 8.57; N 2.77; S 6.34. Found:
C 75.02; H 8.61; N 2.59; S 6.12.
2
-(Octadecylthio)-3-(phenylamino)naphthalene-1,4-dione (6a): Compound 6a
was synthesized from 0.15g (0.528 mmol) 2-chloro-3-(phenylamino)naphthalene-1,4-dione 3a
and 0.15g (0.528 mmol) octadecanethiol 4b using triethylamine as base according to the general
11
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procedure. IR: 3309 (NH), 3052 (CHarom.), 2913, 2849 (CHaliph.), 1665, 1634 (C=O), 1591, 1554
1
(
C=C). H NMR: 0.79–0.83 (t, 3H, J = 6.83 Hz, CH
3
), 1.08–1.36, 1.50–1.61 (m, 32H, CH
), 6.94–6.95 (d, 2H, J = 7.81 Hz, CHarom), 7.06–7.09 (t, 1H,
J = 7.32 Hz, CHarom), 7.23–7.27 (t, 2H, J = 6.83 Hz, CHarom), 7.56 (t, 1H, J = 7.64 Hz, CHnapht),
2
),
2
.49–2.52 (t, 2H, J = 7.32 Hz, SCH
2
7
1
.66 (t, 1H, J = 7.64 Hz, CHnapht), 7.73 (bs, 1H, NH), 7.99 (d, 1H, J = 7.33 Hz, CHnapht), 8.08 (d,
1
H, J = 7.33 Hz, CHnapht). C NMR: 14.2 (CH
3
3 2
), 21.6, 27.6, 28.6, 29.4, 31.0 (CH ), 33.2
(
SCH
2
), 117.4, 121.4, 127.4 (CHarom), 123.5 (SCnapht), 129.7 (NHCnapht), 125.6, 125.8, 131.7,
1
5
9
32.5 (CHnapht), 133.4, 137.5 (Cnapht), 144.0 (NHC), 179.4, 180.0 (C=O). MS (+ESI): m/z =
+
34[M] , C34
H47NO
2
S (533.81). Calcd.: C 76.50; H 8.87; N 2.62; S 6.01. Found: C 76.45; H
.73; N 2.55; S 6.33.
2
-Chloro-3-(hexadecylthio)naphthalene-1,4-dione (7a): Compound 7a was
synthesized from 1.00g (4.404 mmol) 2,3-dichloro-1,4-naphthoquinone 1 and 1.138g (4.404
mmol) hexadecanethiol 4a using Na
2
CO
3
as base according to the general procedure. IR: 2915,
1
848 (CHaliph.), 1671 (C=O), 1590, 1523 (C=C). H NMR: 0.79–0.82 (t, 3H, J = 6.83 Hz, CH
2
3
),
1
.13–1.42, 1.49–1.62 (m, 28H, CH
2
), 3.30–3.33 (t, 2H, J = 7.32 Hz, SCH
2
), 7.63–7.68 (m, 2H,
1
3
CHnapht), 7.99–8.07 (m, 2H, CHnapht). C NMR: 13.1 (CH
3
), 21.6, 27.6, 28.5, 29.4, 30.9 (CH
2
),
3
3.3 (SCH
2
), 138.7 (SCnapht), 148.4 (ClCnapht), 126.2, 126.3, 130.3, 131.6, (CHnapht), 132.7, 133.1
+
napht), 174.0, 178.8 (C=O). MS (+ESI): m/z = 450 [M+H] , C26
(
C
H37ClO
2
S (449.09). Cald.: C,
6
9.54; H, 8.30; S, 7.14. Found: C, 69.78; H, 8.45; S, 6.85.
2
-(Hexadecylthio)-3-(hexylamino)naphthalene-1,4-dione (11a): Compound 11a
was synthesized from 0.10g (0.222 mmol) 2-chloro-3-(hexadecylthio)naphthalene-1,4-dione 7a
12
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2 3
and 0.022g (0.222 mmol) hexylamine 10a using Na CO as base according to the general
procedure. IR: 3292 (NH), 3050 (CHarom.), 2918, 2849 (CHaliph.), 1670, 1625 (C=O), 1590, 1551
1
(
C=C). H NMR: 0.79–0.85 (t, 6H, J = 6.83 Hz, CH
3
), 1.12–1.37, 1.57–1.63 (m, 28H, CH
), 3.81–3.84 (t, 2H,
2
), 7.53 (bs, 1H, NH), 7.52 (t, 1H, J = 7.32 Hz, CHnapht), 7.63 (t, 1H, J = 7.32
2
),
1
.12–1.37, 1.46–1.53 (m, 8H, CH2(hexyl)), 2.71–2.74 (t, 2H, J= 7.32 Hz, SCH
2
J = 7.32 Hz, NHCH
1
Hz, CHnapht), 7.93 (d, 1H, J = 7.32 Hz, CHnapht), 8.07 (d, 1H, J = 7.32 Hz, CHnapht). C NMR:
3
1
4
4.2, 14.3 (CH
3 2
), 22.8, 22.9, 26.7, 29.1, 29.5, 29.6, 29.8, 29.9, 30.1, 30.9, 31.7, 32.1, 33.9 (CH ),
6.4 (SCH
2
), 128.4 (SCnapht), 134.1 (NHCnapht), 126.6, 126.8, 132.1, 134.8 (CHnapht), 130.9, 136.6
+
napht), 181.7, 181.8 (C=O). MS (+ESI): m/z = 514 [M] , C32
(
C
H51NO
2
S (513.83). Calcd.: C,
7
4.80; H, 10.00; N, 2.73; S, 6.24. Found: C, 75.46; H, 10.54; N, 2.89; S, 6.02.
2
-[(2-Morpholinoethyl)amino]-3-(octadecylthio)naphthalene-1,4-dione (11b):
Compound 11b was synthesized from 0.10g (0.209 mmol) 2-chloro-3-
octadecylthio)naphthalene-1,4-dione 7b and 0.027 mL (0.209 mmol) 4-(2-aminoethyl)-
(
morpholine 10b using Na
2
CO
3
as base according to the general procedure. IR: 3201 (NH), 3049
1
CHarom.), 2917, 2848 (CHaliph.), 1678, 1624 (C=O), 1588, 1538 (C=C). H NMR: 0.79–0.82 (t,
(
3
H, J = 6.83 Hz, CH
3
), 1.12–1.31, 1.44–1.53 (m, 32H, CH
N), 2.72–2.75 (t, 2H, J = 7.32 Hz, SCH
.68 (t, 4H, J = 4.88 Hz, CH2morpholine), 3.90–3.93 (q, 2H, J = 5.37 Hz, NHCH ), 7.20–7.22 (t,
H, J = 5.86 Hz, NH), 7.50 (t, 1H, J = 7.32 Hz, CHnapht), 7.64 (t, 1H, J = 7.32 Hz, CHnapht), 7.93
2
), 2,44–2.45 (t, 4H, J = 4.39 Hz,
CH2morpholine), 2.57–2.59 (t, 2H, J = 5.86 Hz, CH
2
2
), 3.66–
3
1
2
1
3
(
3
d, 1H, J = 7.81 Hz, CHnapht), 8.07 (d, 1H, J = 7.81 Hz, CHnapht). C NMR: 13.1 (CH ), 21.6,
2
2 2
7.8, 28.4, 29.0, 31.0 (CH ) 33.9 (SCH ), 41.0, 56.1 (CH2morph.aliph.), 52.1, 66.1 (CH2morph.cyclo),
1
29.8 (SCnapht), 133.4 (NHCnapht), 125.3, 125.5 (CHnapht), 130.9, 132.8 (Cnapht), 180.6, 180.8
13
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+
C=O). MS (+ESI): m/z = 571 [M] , C34
(
H
54
N
2
O
3
S (570.87). Cald.: C, 71.53; H, 9.53; N, 4.91; S,
5
.62 Found: C, 71.58; H, 9.89; N, 4.97; S, 5.32.
(
E)-2-(Hexadecylthio)-3-(octadec-9-en-1-ylamino)naphthalene-1,4-dione (11c):
Compound 11c was synthesized from 0.10g (0.222 mmol) 2-chloro-3-
hexadecylthio)naphthalene-1,4-dione 7a with 0.059g (0.222 mmol) octadec-9-enylamine 10c
(
using Na
2
CO
3
as base according to the general procedure. IR: 3290 (NH), 3050 (CHarom.), 2920,
1
849 (CHaliph.), 1671, 1645 (C=O), 1591, 1552 (C=C). H NMR: 0.79–0.82 (t, 6H, J = 6.83 Hz,
2
CH
3
), 1.12–1.35, 1.47–1.53, 1.90–1.92 (m, 28H, CH
–CH=CH–CH
), 5.26–5.27 (m, 2H, CH=CH), 5.31 (bs, 1H, NH),
.52 (t, 1H, J = 7.56 Hz, CHnapht), 7.63 (t, 1H, J = 7.56 Hz, CHnapht), 7.94 (d, 1H, J = 7.81 Hz,
2
), 1.12–1.35, 1.57–1.62 (m, 24H,
CH2(oleyl)), 1.90–1.96 (m, 4H, J = 7.32 Hz, CH
SCH ), 3.80–3.83 (t, 2H, J = 7.32 Hz, NHCH
2
2
), 2.71–2.74 (t, 2H, J = 7.32 Hz,
2
2
7
1
3
3
CHnapht), 8.07 (d, 1H, J = 7.81 Hz, CHnapht). C NMR: 14.2, 14.3 (CH ), 22.8, 27.0, 27.4, 28.8,
2
1
2 2
9.1, 30.1 32.1, 32.8, 35.3, 39.5 (CH ), 46.4 (SCH ),126.4 (SCnapht), 134.2 (NHCnapht), 126.6,
26.8, 130.0, 130.2 (CHnapht), 130.2, 132.2 (Cnapht), 134.8 (CHoleyl), 181.6, 181.7 (C=O). MS
+
+ESI): m/z = 681 [M+H] , C44
(
H73NO
2
S (680.14). Calcd.: C, 77.70; H, 10.82; N, 2.06; S, 4.71.
Found: C, 77.18; H, 11.42; N, 2.11; S, 4.66.
-(Hexylamino)-3-(octadecylthio)naphthalene-1,4-dione (11d): Compound 11d
was synthesized from 0.10g (0.209 mmol) 2-chloro-3-(octadecylthio)naphthalene-1,4-dione 7b
and 0.021g (0.209 mmol) hexylamine 10a using Na CO as base according to the general
2
2
3
procedure. IR: 3293 (NH), 3051(CHarom.), 2917, 2848 (CHaliph.), 1670, 1625 (C=O), 1590, 1551
1
C=C). H NMR: 0.80–0.85 (t, 6H, J = 6.83 Hz, CH
(
3
), 1.15–1.37, 1.57–1.63 (m, 32H, CH
2
),
1
.15–1.37, 1.46–1.53 (m, 8H, CH2(hexyl)), 2.71–2.74 (t, 2H, J = 7.32 Hz, SCH
2
), 3.81–3.84 (t, 2H,
14
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J = 7.32 Hz, NHCH
Hz, CHnapht), 7.93 (d, 1H, J = 7.81 Hz, CHnapht), 8.07 (d, 1H, J = 7.81 Hz, CHnapht). C NMR:
4.2, 14,3 (CH ), 22.8, 22.9, 26.7, 29.1, 29.5, 29.6, 29.8, 29.9, 30.1, 30.9, 31.7, 32.1, 35.3
CH ),46.4 (SCH
2
), 7.53 (bs, 1H, NH), 7.52 (t, 1H, J = 7.81 Hz, CHnapht), 7.63 (t, 1H, J = 7.81
1
3
1
3
(
2
2
), 128.2 (SCnapht), 134.2 (NHCnapht), 126.6, 126.8, 132.1, 134.8 (CHnapht), 130.9,
+
36.6 (Cnapht), 181.7, 181.8 (C=O). MS (+ESI): m/z = 542 [M] , C34
1
H55NO
2
S (541.89). Calcd.:
C, 75.36; H, 10.23; N, 2.58; S, 5.92. Found: C, 76.02; H, 10.69; N, 2.87; S, 5.76.
2
-(Hexadecylthio)-3-[(2-morpholinoethyl)amino]naphthalene-1,4-dione
(11e):
Compound 11e was synthesized from 0.10g (0.222 mmol)
2-chloro-3-
(
hexadecylthio)naphthalene-1,4-dione 7a and 0.028 mL (0.222 mmol) 4-(2-aminoethyl)-
morpholine 10b using Na
2
CO
3
as base according to the general procedure. IR: 3280 (NH), 3050
1
CHarom.), 2921–2851 (CHaliph.), 1672–1629 (C=O), 1556 (C=C). H NMR: 0.79–0.82 (t, 3H, J =
(
6
.83 Hz, CH
3
), 1.15–1.31, 1.44–1.54 (m, 28H, CH
N), 2.72–2.75 (t, 2H, J = 7.32 Hz, SCH
.69 (t, 4H, J = 4.88 Hz, CH2morpholine), 3.90–3.93 (q, 2H, J = 5.37 Hz, NHCH ), 7.20–7.23 (t,
H, J = 5.86 Hz, NH), 7.51 (t, 1H, J = 6.83 Hz, CHnapht), 7.64 (t, 1H, J = 6.83 Hz, CHnapht), 7.93
2
), 2,44–2.46 (t, 4H, J = 4.39 Hz,
CH2morpholine), 2.57–2.59 (t, 2H, J = 5.86 Hz, CH
2
2
), 3.67–
3
1
2
1
3
(
3
d, 1H, J = 7.81 Hz, CHnapht), 8.07 (d, 1H, J = 7.81 Hz, CHnapht). C NMR: 13.1 (CH ), 21.6,
2
2 2
7.8, 28.5, 29.0, 31.0 (CH ) 33.9 (SCH ), 41.0, 56.1 (CH2morph.aliph.), 52.1, 66.1 (CH2morph.cyclo),
1
28.8 (SCnapht), 133.4 (NHCnapht), 125.2, 125.5 (CHnapht), 130.9, 132.8 (Cnapht), 180.6, 180.8
+
C=O). MS (+ESI): m/z = 543 [M+H] , C32
(
H
50
N
2
O
3
S (542.35). Calcd.: C, 70.81; H, 9.28; N,
5
.16; S, 5.91. Found: C, 70.88; H, 9.76; N, 5.24; S, 5.57.
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(
E)-2-(Octadec-9-en-1-ylamino)-3-(octadecylthio)naphthalene-1,4-dione
(11f):
Compound 11f was synthesized from 0.10g (0.209 mmol)
2-chloro-3-
(
octadecylthio)naphthalene-1,4-dione 7b and 0.056g (0.209 mmol) octadec-9-enylamine 10c
using Na
2
CO
3
as base according to the general procedure. IR: 3291 (NH), 3052 (CHarom.), 2921,
1
849 (CHaliph.), 1671, 1629 (C=O), 1590, 1552 (C=C). H NMR: 0.78–0.82 (t, 6H, J = 6.83 Hz,
2
CH
3
), 1.12–1.35, 1.47–1.53, 1.89–1.92 (m, 32H, CH
2
), 1.12–1.35, 1.56–1.63 (m, 24H,
), 3.81–
CH2(oleyl)), 1.90–1.96 (m, 4H, CH
2
–CH=CH–CH ), 2.71–2.74 (t, 2H, J = 7.32 Hz, SCH
2
2
3
.83 (t, 2H, J = 7.32 Hz, NHCH
2
), 5.26–5.28 (m, 2H, CH=CH), 5.31 (bs, 1H, NH), 7.52 (t, 1H, J
=
7.56 Hz, CHnapht), 7.62 (t, 1H, J = 7.56 Hz, CHnapht), 7.93 (d, 1H, J = 7.81 Hz, CHnapht), 8.06
1
d, 1H, J = 7.81 Hz, CHnapht). C NMR: 14.2, 14.3 (CH
3
(
3
), 22.9, 24.9, 27.0, 27.4, 27.5, 29.1,
3
1
0.9, 32.1, 32.8, 35.3 (CH ), 46.4 (SCH
2
2
), 126.6 (SCnapht), 134.2 (NHCnapht), 126.6, 126.9, 130.2,
30.9 (CHnapht), 131.2, 134.1 (Cnapht), 134.8 (CHoleyl), 180.6, 181.7 (C=O). MS (+ESI): m/z = 709
+
M+H] , C46
[
H
77NO
2
S (708.20). Calcd.: C, 78.02; H, 10.96; N, 1.98; S, 4.53. Found: C, 78.23; H,
1
0.75; N, 2.02; S, 4.66.
CONCLUSION
We have designed and synthesized new N,S-disubstituted naphthoquinones and completely
1
13
characterized them by CHN analyses, FT-IR, Mass, H NMR, C NMR and UV/Vis
spectroscopy. Photo- and electrochemical properties of selected compounds were investigated by
using fluorescence spectroscopy and the cyclovoltammetry method. The obtained new products
were stable naphthoquinone dyes. These compounds may attract attention as organic dyes
because of their high solubility in various organic solvents such as chloroform, dichloromethane,
etc., and their red color in the solid state.
16
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ACKNOWLEDGEMENTS. This work was supported by the Research Fund of the Istanbul
University.
Supplemental Materials
Characterization Data for Compounds 5 and 6
2
-(Hexadecylthio)-3-(phenylamino)naphthalene-1,4-dione (5a): Compound 5a was
synthesized from 0.20g (0.704 mmol) 2-chloro-3-(phenylamino)naphthalene-1,4-dione 3a and
.182g (0.704 mmol) hexadecanethiol 4a using triethylamine as base according to the general
0
procedure. IR: 3310 (NH), 3052 (CHarom.), 2914, 2849 (CHaliph.), 1665, 1634 (C=O), 1591, 1555
1
(
C=C). H NMR: 0.79–0.83 (t, 3H, J = 6.83 Hz, CH
3
), 1.07–1.30, 1.51–1.59 (m, 28H, CH
), 6.94–6.95 (d, 2H, J = 7.32 Hz, CHarom), 7.05–7.08 (t, 1H,
J = 7.32 Hz, CHarom), 7.23–7.26 (t, 2H, J = 7.31 Hz, CHarom), 7.59 (t, 1H, J = 7.56 Hz, CHnapht),
2
),
2
.49–2.52 (t, 2H, J = 7.32 Hz, SCH
2
7
1
.66 (t, 1H, J = 7.56 Hz, CHnapht), 7.73 (bs, 1H, NH), 7.99 (d, 1H, J = 7.56 Hz, CHnapht), 8.08 (d,
1
H, J = 7.56 Hz, CHnapht). C NMR: 14.1 (CH
3
3 2
), 21.6, 28.0, 28.6, 29.2, 31.0 (CH ), 33.1
(
SCH
2
), 117.4, 121.4, 127.4 (CHarom), 123.5 (SCnapht), 129.6 (NHCnapht), 125.6, 125.8, 131.6,
1
32.5 (CHnapht), 133.4, 137.5 (Cnapht), 144.0 (NHC), 179.4, 180.0 (C=O). MS (+ESI): m/z = 506
+
[
M] , C32
H43NO
2
S (505.75). Calcd.: C 75.99; H 8.57; N 2.77; S 6.34. Found: C 75.02; H 8.61; N
2
.59; S 6.12.
2
-[(4-Fluorophenyl)amino]-3-(hexadecylthio)naphthalene-1,4-dione (5b): Compound
5
b was synthesized from 0.20g (0.662 mmol) 2-chloro-3-[(4-fluorophenyl)amino]naphthalene-
,4-dione 3b and 0.171g (0.662 mmol) hexadecanethiol 4a using triethyl amine as base
1
according to the general procedure. IR: 3296 (NH), 3051 (CHarom.), 2915, 2849 (CHaliph.), 1665,
17
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1
1
631 (C=O), 1556 (C=C). H NMR: 0.79–0.82 (t, 3H, J = 6.83 Hz, CH
3
), 1.09–1.33, 1.49–1.57
), 7.65 (bs, 1H, NH), 6.91–6.94 (m, 2H,
CHarom), 6.95–6.97 (m, 2H, Hz, CHarom), 7.57 (t, 1H, J = 7.56 Hz, CHnapht), 7.67 (t, 1H, J = 7.56
(
2 2
m, 28H, CH ), 2.50–2.53 (t, 2H, J = 7.32 Hz, SCH
1
3
Hz, CHnapht), 7.98 (d, 1H, J = 7.08 Hz, CHnapht), 8.08 (d, 1H, J = 7.08 Hz, CHnapht). C NMR:
1
3.0 (CH ), 21.7, 27.6, 28.3, 28.7, 30.9 (CH ), 33.0 (SCH ), 114.1, 123.6 (CHarom), 116.7
3
2
2
(
(
(
SCnapht), 129.5 (NHCnapht), 125.6, 125.8, 131.7, 132.5, (CHnapht), 133.5, 133.6 (Cnapht), 144.4
+
NHC), 157.9–159.8 (d, FCarom), 179.3, 179.9 (C=O). MS (+ESI): m/z = 524 [M] , C32
H42FNO
2
S
523.74). Calcd.: C 73.38; H 8.08; N 2.67; S 6.12. Found: C 73.66; H 8.08; N 2.68; S 6.18.
-[(4-Fluorobenzyl)amino]-3-(hexadecylthio)naphthalene-1,4-dione (5c): Compound 5c
was synthesized from 0.20g (0.633 mmol) 2-(4-fluorobenzylamino)-3-chloronaphthalene-1,4-
dione 3c and 0.163g (0.633 mmol) hexadecanethiol 4a using Na CO as base according to the
2
2
3
general procedure. IR: 3306 (NH), 3052 (CHarom.), 2913, 2849 (CHaliph.), 1669 (C=O), 1551–
1
1
503 (C=C). H NMR: 0.79–0.82 (t, 3H, J = 6.84 Hz, CH
3
), 1.10–1.26, 1.40–1.52 (m, 28H,
), 5.01–5.02 (d, 2H, J = 5.85 Hz, NHCH ), 6.96–7.00
m, 2H, CHarom), 7.18–7.23 (m, 2H, Hz, CHarom), 6.55 (t, 1H, J = 5.87 Hz, NH), 7.51 (t, 1H, J =
CH
2
), 2.67–2.70 (t, 2H, J = 7.32 Hz, SCH
2
2
(
7
1
.57 Hz, CHnapht), 7.65 (t, 1H, J = 7.57 Hz, CHnapht), 7.93 (d, 1H, J = 7.56 Hz, CHnapht), 8.06 (d,
1
H, J = 7.56 Hz, CHnapht). C NMR: 13.0 (CH
3
3 2
), 21.6, 27.6, 28.3, 28.7, 30.9 (CH ), 34.1
(
SCH
2
), 48.1 (NHCH ), 114.7, 128.2 (CHarom), 129.3 (SCnapht), 133.7 (NHCnapht), 125.4, 125.6,
2
1
31.1, 131.2 (CHnapht), 132.7, 133.0 (Cnapht), 133.2 (Carom), 160.3–162.3 (d, FCarom), 179.3, 179.9
+
C=O). MS (+ESI): m/z = 538 [M] , C33
(
2
H44FNO S (537.77). Calcd.: C 73.70; H 8.25; N 2.60; S
5
.96. Found: C 74.52; H 8.43; N 2.68; S 5.74.
18
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2
-(Hexadecylthio)-3-(naphthalen-2-ylamino)naphthalene-1,4-dione (5d): Compound
d was synthesized from 0.20g (0.599 mmol) 2-chloro-3-(naphthalen-3-ylamino)naphthalene-
,4-dione 3d and 0.155g (0.599 mmol) hexadecanethiol 4a using Na CO as base according to
5
1
2
3
the general procedure. IR: 3288 (NH), 3052 (CHarom.), 2916, 2849 (CHaliph.), 1661, 1628 (C=O),
1
588 (C=C). H NMR: 0.79–0.81 (t, 3H, J = 6.84 Hz, CH
1
3
), 1.02–1.26, 1.49–1.55 (m, 28H,
CH
2
), 2.44–2.47 (t, 2H, J = 7.32 Hz, SCH
2
), 7.14–7.18 (m, 2H, CHnaphthyl), 7.26 (bs, 1H,
CHnaphthyl), 7.32–7.41 (m, 2H, CHnaphthyl), 7.69–7.73 (m, 2H, CHnaphthyl), 7.57–7.68 (m, 2H,
CHnapht), 7.91 (bs, 1H, NH), 8.01 (d, 1H, J = 7.08 Hz, CHnapht), 8.10 (d, 1H, J = 7.08 Hz,
1
3
3 2 2
CHnapht). C NMR: 13.1 (CH ), 21.6, 27.5, 28.3, 28.7, 30.9 (CH ), 32.7 (SCH ), 117.9, 121.0,
1
25.6, 126.5, 127.2, 129.6 (CHnaphthyl), 131.7, 134.5 (Cnaphthyl), 121.0 (SCnapht), 126.0 (NHCnapht),
1
26.7, 127.2, 132.1 (CHnapht), 132.6, 134.5 (Cnapht), 143.5 (NHC), 179.5, 180.1 (C=O). MS
+
+ESI): m/z = 556 [M+H] , C36
(
H45NO
2
S (556.58). Calcd.: C 77.79; H 8.16; N 2.52; S 5.77.
Found: C 77.65; H 8.75; N 2.49 S 5.10.
2
-(Hexadecylthio)-3-(o-tolylamino)naphthalene-1,4-dione (5e): Compound 5e was
synthesized from 0.10g (0.335 mmol) 2-(o-tolylamino)-3-chloronaphthalene-1,4-dione 3e and
.086g (0.335 mmol) hexadecanethiol 4a using Na CO as base according to the general
0
2
3
procedure. IR: 3304 (NH), 3050 (CHarom.), 2916, 2849 (CHaliph.), 1664, 1633 (C=O), 1587, 1552
1
C=C). H NMR: 0.80–0.83 (t, 3H, J = 6.83 Hz, CH
(
(
3
), 1.09–1.35, 1.46–1.54 (m, 28H, CH
2
), 2.26
s, 3H, CH3arom), 2.51–2.54 (t, 2H, J = 7.32 Hz, SCH
2
), 6.83–6.85 (d, 1H, J = 7.81 Hz, CHarom),
7
1
8
.04–7.12 (m, 2H, CHarom), 7.13–7.16 (d, 1H, J = 6.83 Hz, CHarom), 7.52 (bs, 1H, NH), 7.56 (t,
H, J = 7.57 Hz, CHnapht), 7.67 (t, 1H, J = 7.57 Hz, CHnapht), 7.98 (d, 1H, J = 7.81 Hz, CHnapht),
1
3
3
.08 (d, 1H, J = 7.81 Hz, CHnapht). C NMR: 13.1 (CH ), 17.3 (CH3arom), 22.7, 28.3, 28.6, 29.3,
19
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3
1
1
2
2 2
1.9 (CH ), 33.7 (SCH ), 115.4, 124.9, 129.3, 129.8, (CHarom), 123.1 (SCnapht), 124.6 (NHCnapht),
25.5, 125.8, 130.8,132.6 (CHnapht), 131.5 (Carom), 133.4, 136.6 (Cnapht), 145.6 (NHC), 179.4,
+
79.7 (C=O). MS (+ESI): m/z = 520 [M] , C33
H45NO
2
S (519.78). Calcd.: C 76.25; H 8.73; N
.69; S 6.17. Found: C 76.49; H 9.68; N 2.60; S 6.02.
2
-(Hexadecylthio)-3-(m-tolylamino)naphthalene-1,4-dione (5f): Compound 5f was
synthesized from 0.10g (0.335 mmol) 2-(m-tolylamino)-3-chloronaphthalene-1,4-dione 3f and
.086g (0.335 mmol) hexadecanethiol 4a using Na CO as base according to the general
0
2
3
procedure. IR: 3305 (NH), 3053 (CHarom.), 2916, 2849 (CHaliph.), 1656, 1645 (C=O), 1587, 1546
1
C=C). H NMR: 0.80–0.82 (t, 3H, J = 6.34 Hz, CH
(
(
3
), 1.09–1.32, 1.44–1.51 (m, 28H, CH
2
), 2.28
bs, 3H, CH3arom), 2.51–2.54 (t, 2H, J = 7.32 Hz, SCH
2
), 6.75 (bs, 1H, CHarom), 6.75–6.77 (d, 1H,
J = 6.35 Hz, CHarom), 6.88–6.90 (d, 1H, J = 7.32 Hz, CHarom), 7.12–7.15 (t, 1H, J = 7.81 Hz,
CHarom), 7.56 (t, 1H, J = 7.08 Hz, CHnapht), 7.67 (t, 1H, J = 7.08 Hz, CHnapht), 7.72 (bs, 1H, NH),
1
3
.00 (d, 1H, J = 7.56 Hz, CHnapht), 8.08 (d, 1H, J = 7.56 Hz, CHnapht). C NMR: 13.1 (CH
8
3
),
2
0.4 (CH3arom), 21.6, 27.6, 28.3, 28.7, 31.0 (CH ), 32.7 (SCH ), 117.1, 118.5, 122.0, 127.2
2
2
(
CHarom), 118.5 (SCnapht), 124.4 (NHCnapht), 125.5, 125.8, 131.6, 132.6 (CHnapht), 133.4 (Carom),
+
29.7, 137.4 (Cnapht), 144.1 (NHC), 179.4, 180.0 (C=O). MS (+ESI): m/z = 521 [M+H] ,
1
33 2
C H45NO S (519.78). Calcd.: C 76.25; H 8.73; N 2.69; S 6.17. Found: C 76.11; H 9.31; N 2.91;
S 6.40.
2
-(Hexadecylthio)-3-(p-tolylamino)naphthalene-1,4-dione (5g): Compound 5g was
synthesized from 0.20g (0.67 mmol) 2-chloro-3-(p-tolylamino)naphthalene-1,4-dione 3g, 0.172g
(
(
0.67 mmol) hexadecanethiol 4a and K
2
CO
3
as base according to the general procedure. IR: 3322
1
NH), 3051 (CHarom.), 2915, 2849 (CHaliph.), 1659, 1637 (C=O), 1591, 1547 (C=C). H NMR:
20
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0
.81–0.83 (t, 3H, J = 6.83 Hz, CH
3 2
), 1.08–1.36, 1.54 (m, 28H, CH ), 2.27 (s, 3H, CH3arom), 2.50–
2
.54 (t, 2H, J = 7.32 Hz, SCH ), 6.84–6.85 (d, 2H, J = 8.3 Hz, CHarom), 7.03–7.05 (d, 2H, J = 8.3
2
Hz, CHarom), 7.56 (t, 1H, J = 8.46 Hz, CHnapht), 7.65 (t, 1H, J = 8.05 Hz, CHnapht), 7.71 (bs, 1H,
1
NH), 8.00 (d, 1H, J = 7.32 Hz, CHnapht), 8.07 (d, 1H, J = 7.32 Hz, CHnapht). C NMR: 13.1
3
(
(
3 2 2
CH ), 20.0 (CH3arom), 21.6, 27.6, 28.3, 28.7, 30.9 (CH ), 32.9 (SCH ), 121.6, 125.6, 125.8, 128.0
CHarom), 116.3 (SCnapht), 129.7 (NHCnapht), 131.6, 133.4, 133.5 (CHnapht), 135.0 (Carom), 129.7,
+
33.5 (Cnapht), 144.5 (NHC), 179.8, 179.9 (C=O). MS (+ESI): m/z = 521 [M+H] , C33
1
H45NO
2
S
(
519.78). Calcd.: C 76.25; H 8.73; N 2.69; S 6.17. Found: C 76.57; H 8.39; N 2.66; S 6.48.
-(Hexadecylthio)-3-[(4-methoxyphenyl)amino]naphthalene-1,4-dione
Compound 5h was synthesized from 0.20g (0.64 mmol) 2-(4-methoxyphenylamino)-3-
chloronaphthalene-1,4-dione 3h and 0.165g (0.64 mmol) hexadecanethiol 4a using K CO as
2
(5h):
2
3
base according to the general procedure. IR: 3291 (NH), 3051 (CHarom.), 2916, 2848 (CHaliph.),
1
665, 1629 (C=O), 1589, 1512 (C=C), H NMR: 0.80–0.81 (t, 3H, J = 6.83 Hz, CH
1
1
3
), 1.10–1.31,
.55 (m, 28H, CH
2
), 2.50-2.53 (t, 2H, J = 7.32 Hz, SCH
2
), 3.75 (bs, 3H, OCH3 arom), 6.80 (d, 2H,
J = 7.81 Hz, CHarom), 6.94 (d, 2H, J = 8.79 Hz, CHarom), 7.55 (t, 1H, J = 7.56 Hz, CHnapht), 7.64
t, 1H, J = 7.56 Hz, CHnapht), 7.66 (bs, 1H, NH), 7.97 (d, 1H, J = 7.32 Hz, CHnapht), 8.08 (d, 1H,
(
1
J = 7.32 Hz, CHnapht). C NMR: 14.3 (CH
3
3
), 20.4 (OCH3arom), 29.7, 29.8, 29.9, 32.1 (CH
2
), 34.3
(
(
(
SCH ), 126.8, 127.0, 124.8, 113.9 (CHarom), 116.3 (SCnapht), 124.8 (NHCnapht), 132.7, 134.7
2
CHnapht), 131.9, 130.9 (Carom), 133.9, 146.3 (Cnapht), 157.3 (NHC), 180.8, 181.0 (C=O). MS
+
+ESI): m/z = 537 [M+H] , C33
H45NO
3
S (535.80). Calcd.: C 73.98; H 8.47; N 2.61; S 5.98.
Found: C 74.55; H 8.15; N 2.59; S 5.71.
21
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2
-[(3,5-Dimethoxyphenyl)amino]-3-(hexadecylthio)naphthalene-1,4-dione
Compound 5i was synthesized from 0.20 g (0.582 mmol) 2-(3,5-dimethoxyphenylamino)-3-
chloronaphthalene-1,4-dione 3i and 0.150g (0.582 mmol) hexadecanethiol 4a using Na CO as
(5i):
2
3
base according to the general procedure. IR: 3316 (NH), 3051 (CHarom.), 2915, 2848 (CHaliph.),
1
664, 1632 (C=O), 1593, 1553 (C=C). H NMR: 0.79–0.81 (t, 3H, J = 6.83 Hz, CH
1
1
3
1
7
3
), 1.09–1.31,
.55 (m, 28H, CH
2
), 2.42–2.45 (t, 2H, J = 7.32 Hz, SCH
2
), 3.73 (bs, 3H, OCH3 arom), 3.75 (bs,
H, OCH3arom), 6.38 (d, 1H, J = 7.32 Hz, CHarom), 6.40 (bs, 1H, J = 7.32 Hz, CHarom), 6.83 (d,
H, J = 7.32 Hz, CHarom), 7.54 (t, 1H, J = 7.56 Hz, CHarom), 7.64 (t, 1H, J = 7.56 Hz, CHnapht),
1
3
.66 (bs, 1H, NH), 7.96 (d, 1H, J = 7.56 Hz, CHnapht), 8.07 (d, 1H, J = 7.56 Hz, CHnapht). C
), 22.9 (OCH3arom), 28.9, 29.6, 29.8, 29.9, 32.1 (CH ), 34.0 (SCH ), 103.3,
9.0(CHarom), 121.0 (SCnapht), 134.0 (NHCnapht), 124.9, 126.6, 132.5, 134.5 (CHnapht), 131.0,
NMR: 14.3 (CH
3
2
2
9
1
14.8 (Carom), 146.8, 153.7 (Cnapht), 158.5 (NHC), 180.8, 180.9 (C=O). MS (+ESI): m/z = 567
+
M+H] , C34
[
H47NO
4
S (565.82). Calcd.: C 72.17; H 8.77; N 2.48; S 5.67. Found: C 72.04; H
8
.22; N 2.33; S 5.00.
2
-(Octadecylthio)-3-(phenylamino)naphthalene-1,4-dione (6a): Compound 6a was
synthesized from 0.15g (0.528 mmol) 2-chloro-3-(phenylamino)naphthalene-1,4-dione 3a and
.15g (0.528 mmol) octadecanethiol 4b using triethylamine as base according to the general
0
procedure. IR: 3309 (NH), 3052 (CHarom.), 2913, 2849 (CHaliph.), 1665, 1634 (C=O), 1591, 1554
1
(
C=C). H NMR: 0.79–0.83 (t, 3H, J = 6.83 Hz, CH
3
), 1.08–1.36, 1.50–1.61 (m, 32H, CH
), 6.94–6.95 (d, 2H, J = 7.81 Hz, CHarom), 7.06–7.09 (t, 1H,
J = 7.32 Hz, CHarom), 7.23–7.27 (t, 2H, J = 6.83 Hz, CHarom), 7.56 (t, 1H, J = 7.64 Hz, CHnapht),
.66 (t, 1H, J = 7.64 Hz, CHnapht), 7.73 (bs, 1H, NH), 7.99 (d, 1H, J = 7.33 Hz, CHnapht), 8.08 (d,
2
),
2
.49–2.52 (t, 2H, J = 7.32 Hz, SCH
2
7
22
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1
H, J = 7.33 Hz, CHnapht). C NMR: 14.2 (CH
3
1
3 2
), 21.6, 27.6, 28.6, 29.4, 31.0 (CH ), 33.2
(
SCH ), 117.4, 121.4, 127.4 (CHarom), 123.5 (SCnapht), 129.7 (NHCnapht), 125.6, 125.8, 131.7,
2
1
5
9
32.5 (CHnapht), 133.4, 137.5 (Cnapht), 144.0 (NHC), 179.4, 180.0 (C=O). MS (+ESI): m/z =
+
34[M] , C34
H47NO
2
S (533.81). Calcd.: C 76.50; H 8.87; N 2.62; S 6.01. Found: C 76.45; H
.73; N 2.55; S 6.33.
2
-[(4-Fluorophenyl)amino]-3-(octadecylthio)naphthalene-1,4-dione (6b): Compound
6
b was synthesized from 0.10 g (0.331 mmol) 2-chloro-3-((4-fluorophenyl)amino)naphthalene-
,4-dione 3b and 0.095 g (0.331 mmol) octadecanethiol 4b using triethylamine as base according
1
to the general procedure. IR: 3296 (NH), 3051 (CHarom.), 2914, 2849 (CHaliph.), 1664, 1631
1
C=O), 1589, 1541 (C=C). H NMR: 0.79–0.83 (t, 3H, J = 6.83 Hz, CH
(
(
3
), 1.09–1.32, 1.50–1.57
m, 32H, CH
2
), 2.50–2.53 (t, 2H, J = 7.32 Hz, SCH
2
), 7.67 (bs, 1H, NH), 6.91–6.94 (m, 2H,
CHarom), 6.95–6.97 (m, 2H, Hz, CHarom), 7.56 (t, 1H, J = 7.57 Hz, CHnapht), 7.67 (t, 1H, J = 7.57
1
Hz, CHnapht), 7.98 (d, 1H, J = 7.56 Hz, CHnapht), 8.07 (d, 1H, J = 7.56 Hz, CHnapht). C NMR:
3
1
4.3 (CH ), 22.9, 28.8, 29.5, 30.0, 32.1 (CH ), 34.2(SCH ), 115.4, 124.6 (CHarom), 117.9
3
2
2
(
(
(
SCnapht), 130.8 (NHCnapht), 126.8, 127.1, 132.9, 133.7 (CHnapht), 134.7, 134.8(Cnapht), 145.6
+
NHC), 159.1–161.1 (d, FCarom), 180.5, 181.1 (C=O). MS (+ESI): m/z = 552[M] , C34
H46FNO
2
S
551.32). Calcd.: C 74.01; H 8.40; N 2.54; S 5.81. Found: C 74.38; H 9.02; N 2.74; S 5.70.
2
-[(4-Fluorobenzyl)amino]-3-(octadecylthio)naphthalene-1,4-dione (6c): Compound 6c
was synthesized from 0.10g (0.316 mmol) 2-(4-fluorobenzylamino)-3-chloronaphthalene-1,4-
dione 3c and 0.09g (0.316 mmol) octadecanethiol 4b using Na CO as base according to the
general procedure. IR: 3308 (NH), 3053(CHarom.), 2912, 2849 (CHaliph.), 1669 (C=O), 1591,
2
3
23
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1
1
2
2
551(C=C). H NMR: 0.79–0.82 (t, 3H, J = 6.83 Hz, CH
3
), 1.10–1.26, 1.40–1.51 (m, 32H, CH
), 5.01–5.02 (d, 2H, J = 5.86 Hz, NHCH ), 6.96–7.00 (m,
H, CHarom), 7.19–7.24 (m, 2H, Hz, CHarom), 6.55 (t, 1H, J = 5.86 Hz, NH), 7.52(t, 1H, J = 7.57
2
),
.67–2.69 (t, 2H, J = 7.32 Hz, SCH
2
2
Hz, CHnapht), 7.65 (t, 1H, J = 7.57 Hz, CHnapht), 7.94 (d, 1H, J = 7.49 Hz, CHnapht), 8.07 (d, 1H, J
1
7.49 Hz, CHnapht). C NMR: 14.3 (CH
3
=
3 2 2
), 22.9, 29.1, 29.8, 30.1, 32.1 (CH ), 35.4(SCH ),
4
1
9.4(NHCH ), 115.9, 129.4 (CHarom), 131.0 (SCnapht), 134.8 (NHCnapht), 126.7, 126.9, 132.1,
2
32.4 (CHnapht), 133.1, 133.9 (Cnapht), 134.3 (Carom), 160.3–162.3 (d, FCarom), 180.4, 181.5 (C=O).
+
MS (+ESI): m/z = 566[M] , C35
H48FNO
2
S (565.82). Calcd.: C 74.29; H 8.55; N 2.48; S 5.67.
Found: C 74.37; H 9.27; N 2.69; S 5.45.
2
-(Naphthalen-2-ylamino)-3-(octadecylthio)naphthalene-1,4-dione (6d): Compound 6d
was synthesized from 0.10g (0.299 mmol) 2-chloro-3-(naphthalen-3-ylamino)naphthalene-1,4-
dione 3d and 0.085g (0.299 mmol) octadecanethiol 4b using Na CO as base according to the
2
3
general procedure. IR: 3289 (NH), 3053 (CHarom.), 2914, 2848 (CHaliph.), 1666, 1628 (C=O),
1
589, 1541 (C=C). H NMR: 0.79–0.82 (t, 3H, J = 6.83 Hz, CH
1
3
3
), 1.02–1.25, 1.49–1.54 (m,
2H, CH
2
), 2.44–2.47 (t, 2H, J = 7.32 Hz, SCH
2
), 7.14–7.16 (m, 2H, CHnaphthyl), 7.27(bs, 1H,
CHnaphthyl), 7.32–7.41 (m, 2H, CH naphthyl), 7.69–7.73 (m, 2H, CHnaphthyl), 7.57–7.68 (m, 2H,
CHnapht), 7.91 (bs, 1H, NH), 8.01 (d, 1H, J = 7.08 Hz, CHnapht), 8.10 (d, 1H, J = 7.08 Hz,
1
3
3 2 2
CHnapht). C NMR: 13.1 (CH ), 21.6, 28.0, 28.6, 29.2, 30.9 (CH ), 32.7 (SCH ), 117.8, 121.0,
1
25.7, 126.5, 127.2, 129.6 (CHnaphthyl), 131.7, 134.5 (Cnaphthyl), 121.0 (SCnapht), 126.0 (NHCnapht),
1
26.7, 127.2, 132.1 (CHnapht), 132.6, 134.5 (Cnapht), 143.5 (NHC), 179.5, 180.1 (C=O). MS
+
+ESI): m/z = 585 [M] , C38
(
H49NO
2
S (583.87). Calcd.: C 78.17; H 8.46; N 2.40; S 5.49. Found:
C 78.27; H 9.32; N 2.46 S 5.25.
24
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ACCEPTED MANUSCRIPT
2
-(Octadecylthio)-3-(o-tolylamino)naphthalene-1,4-dione (6e): Compound 6e was
synthesized from 0.10g (0.335 mmol) 2-(o-tolylamino)-3-chloronaphthalene-1,4-dione 3e and
.096g (0.335 mmol) octadecanethiol 4b using Na CO as base according to the general
0
2
3
procedure. IR: 3305 (NH), 3050 (CHarom.), 2915, 2849 (CHaliphatic), 1665, 1633 (C=O), 1587,
1
553 (C=C). H NMR: 0.80–0.83 (t, 3H, J = 6.34 Hz, CH
1
3
), 1.09–1.35, 1.45–1.53 (m, 32H,
), 6.84–6.85 (d, 1H, J = 7.81
CH
2
), 2.26 (s, 3H, CH3arom), 2.51–2.54 (t, 2H, J = 7.32 Hz, SCH
2
Hz, CHarom), 7.04–7.12 (m, 2H, CHarom), 7.14–7.16 (d, 1H, J = 7.32 Hz, CHarom), 7.52 (bs, 1H,
NH), 7.55 (t, 1H, J = 7.57 Hz, CHnapht), 7.67 (t, 1H, J = 7.57 Hz, CHnapht), 7.98 (d, 1H, J = 7.81
1
Hz, CHnapht), 8.08 (d, 1H, J = 7.81 Hz, CHnapht). C NMR: 13.0 (CH
3
3
), 17.3 (CH3arom), 21.6,
2
1
8.1, 28.6, 29.2, 31.0 (CH ), 32.9 (SCH ), 115.4, 124.9, 129.3, 129.8 (CHarom), 123.1 (SCnapht),
2 2
24.6 (NHCnapht), 125.5, 125.8, 130.8,132.6 (CHnapht), 131.5 (Carom), 133.4, 136.6 (Cnapht), 145.6
+
NHC), 179.4, 179.7 (C=O). MS (+ESI): m/z = 547 [M] , C35
(
H
49NO
2
S (547.83). Calcd.: C
7
6.73; H 9.02; N 2.56; S 5.85. Found: C 77.79; H 9.12; N 2.75; S 5.73.
2
-(Octadecylthio)-3-(m-tolylamino)naphthalene-1,4-dione (6f): Compound 6f was
synthesized from 0.10g (0.335 mmol) 2-(m-tolylamino)-3-chloronaphthalene-1,4-dione 3f and
.096g (0.335 mmol) octadecanethiol 4b using Na CO as base according to the general
0
2
3
procedure. IR: 3295 (NH), 3049 (CHarom.), 2913, 2850 (CHaliph.), 1665, 1630 (C=O), 1587, 1560
1
C=C). H NMR: 0.80–0.82 (t, 3H, J = 6.83 Hz, CH
(
(
3
), 1.08–1.32, 1.45–1.53 (m, 32H, CH
2
), 2.28
bs, 3H, CH3arom), 2.50–2.53 (t, 2H, J = 7.32 Hz, SCH
2
), 6.75 (bs, 1H, CHarom), 6.75–6.76 (d, 1H,
J = 6.35 Hz, CHarom), 6.88–6.90 (d, 1H, J = 7.81 Hz, CHarom), 7.12–7.15 (t, 1H, J = 7.57 Hz,
CHarom), 7.56 (t, 1H, J = 7.56 Hz, CHnapht), 7.67 (t, 1H, J = 7.56 Hz, CHnapht), 7.71 (bs, 1H, NH),
1
3
7
3
.99 (d, 1H, J = 8.78 Hz, CHnapht), 8.08 (d, 1H, J = 8.78 Hz, CHnapht). C NMR: 14.3 (CH ),
25
ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
2
2 2
1.6 (CH3arom), 22.9, 28.8, 29.4, 29.9, 32.1 (CH ), 34.0 (SCH ), 118.3, 119.7, 123.2, 128.5
(
CHarom), 119.7 (SCnapht), 125.6 (NHCnapht), 126.8, 127.0, 132.8, 133.8 (CHnapht), 134.6 (Carom),
+
30.9, 138.6 (Cnapht), 145.3 (NHC), 180.7, 181.2 (C=O). MS (+ESI): m/z = 549 [M+H] ,
1
35 2
C H49NO S (547.83). Calcd.: C 76.73; H 9.02; N 2.56; S 5.85. Found: C 76.66; H 8.84; N 2.49;
S 5.89.
2
-(Octadecylthio)-3-(p-tolylamino)naphthalene-1,4-dione (6g): Compound 6g was
synthesized from 0.15g (0.50 mmol) 2-chloro-3-(p-tolylamino)naphthalene-1,4-dione 3g and
0
.143g (0.50 mmol) octadecanethiol 4b using K
2
CO
3
as base according to the general procedure.
1
IR: 3325 (NH), 3052 (CHarom.), 2916, 2849 (CHaliph.), 1658, 1636 (C=O), 1591, 1547 (C=C). H
NMR: 0.80–0.84 (t, 3H, J = 6.83 Hz, CH
3
), 1.08–1.36, 1.53 (m, 32H, CH
), 6.84–6.86 (d, 2H, J = 8.3 Hz, CHarom), 7.04–7.05
d, 2H, J = 8.3 Hz, CHarom), 7.56 (t, 1H, J = 7.56 Hz, CHnapht), 7.65 (t, 1H, J = 7.56 Hz, CHnapht),
2
), 2.27 (s, 3H,
CH3arom), 2.50–2.53(t, 2H, J = 7.32 Hz, SCH
2
(
1
3
7
.71 (bs, 1H, NH), 7.99 (d, 1H, J = 7.32 Hz, CHnapht), 8.07 (d, 1H, J = 7.32 Hz, CHnapht). C
), 21.2 (CH3arom), 22.9, 28.7, 29.3, 29.6, 29.8, 29.9,32.1 (CH ), 34.1 (SCH ),
22.9, 126.8, 127.0 (CHarom), 117.5 (SCnapht), 134.7 (NHCnapht), 129.3, 132.8, 134.8 (CHnapht),
NMR: 14.3 (CH
3
2
2
1
1
36.3 (Carom), 131.0, 133.8 (Cnapht), 145.8 (NHC), 181.1, 181.2 (C=O). MS (+ESI): m/z = 549
+
M+H] , C35
[
H49NO
2
S (547.83). Calcd.: C 76.73; H 9.02; N 2.56; S 5.85. Found: C 76.15; H
9
.40; N 2.41; S 5.75.
2
-[(4-Methoxyphenyl)amino]-3-(octadecylthio)naphthalene-1,4-dione (6h): Compound
h was synthesized from 0.20g (0.637 mmol) 2-(4-methoxyphenylamino)-3-chloronaphthalene-
,4-dione 3h and 0.183g (0.637 mmol) octadecanethiol 4b using K CO as base according to the
6
1
2
3
26
ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
general procedure. IR: 3293 (NH), 3053 (CHarom.), 2915, 2847 (CHaliph.), 1665, 1629 (C=O),
1
1
589, 1512 (C=C), H NMR: 0.80–0.81 (t, 3H, J = 6.83 Hz, CH
3
), 1.09–1.32, 1.52 (m, 32H,
), 3.78 (bs, 3H, OCH3 arom), 6.80 (d, 2H, J = 8.79 Hz,
CHarom), 6.93 (d, 2H, J = 7.81 Hz, CHarom), 7.54 (t, 1H, J = 7.56 Hz, CHnapht), 7.64 (t, 1H, J =
.56 Hz, CHnapht), 7.65 (bs, 1H, NH), 7.98 (d, 1H, J = 7.56 Hz, CHnapht), 8.07 (d, 1H, J = 7.56
2 2
CH ), 2.50–2.52 (t, 2H, J = 7.32 Hz, SCH
7
1
Hz, CHnapht). C NMR: 4.7 (CH
3
3 2 2
), 14.3 (OCH3arom), 29.7, 29.8, 29.9, 32.1 (CH ), 34.3 (SCH ),
1
26.8, 127.0, 124.8, 113.9 (CHarom), 116.3 (SCnapht), 131.9 (NHCnapht), 132.7, 134.7 (CHnapht
)
,
130.9 (Carom), 133.9, 146.2 (Cnapht), 157.3 (NHC), 180.8, 181.0 (C=O). MS (+ESI): m/z = 565
+
M+H] , C35
[
H49NO
3
S (563.85). Calcd.: C 74.56; H 8.76; N 2.28; S 5.69. Found: C 75.12; H
8
.43; N 2.55; S 5.75.
2
-[(3,5-Dimethoxyphenyl)amino]-3-(octadecylthio)naphthalene-1,4-dione (6i): Compound 6i
was synthesized from 0.20g (0.582 mmol) 2-(3,5-dimethoxyphenylamino)-3-chloronaphthalene-
,4-dione 3i and 0.167g (0.582 mmol) octadecanethiol 4b using Na CO as base according to the
1
2
3
general procedure. IR: 3316 (NH), 3051 (CHarom.), 2915, 2848 (CHaliph.), 1664, 1632 (C=O),
1
1
593, 1553 (C=C). H NMR: 0.79–0.83 (t, 3H, J = 6.83 Hz,CH
3
), 1.09–1.32, 1.56 (m, 32H,
), 3.73 (bs, 3H, OCH3arom), 3.75 (bs, 3H, OCH3arom),
.37 (d, 1H, J = 7.32 Hz, CHarom), 6.41 (bs, 1H, J = 7.32 Hz, CHarom),6.82 (d, 1H, J = 7.32 Hz,
CHarom), 7.55 (t, 1H, J = 7.56 Hz, CHarom), 7.64 (t, 1H, J = 7.56 Hz, CHnapht), 7.66 (bs, 1H, NH),
2 2
CH ), 2.42–2.45 (t, 2H, J = 7.32 Hz, SCH
6
1
3
7
.96 (d, 1H, J = 7.56 Hz, CHnapht), 8.07 (d, 1H, J = 7.56 Hz, CHnapht). C NMR: 4.7 (CH
OCH3arom), 28.9, 29.6, 29.8, 29.9, 32.1 (CH ), 34.0 (SCH ), 103.3, 99.0 (CHarom), 121.0
SCnapht), 134.0 (NHCnapht), 124.9, 126.6, 132.5, 134.5 (CHnapht), 131.0, 114.8 (Carom), 146.8,
3
), 14.3
(
(
2
2
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+
53.7 (Cnapht), 158.5 (NHC), 180.8, 181.0 (C=O). MS (+ESI): m/z = 595 [M+H] , C36
1
4
H51NO S
(
593.88). Calcd.: C 72.81; H 8.66; N 2.36; S 5.40. Found: C 72.31; H 9.02; N 2.09; S 5.50.
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