Synthesis and spectroscopic properties of S-,O-substituted naphthoquinone dyes

Article abstract of DOI:10.1080/10426501003598671

New S-,O-substituted naphthoquinone compounds (3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, 15) were synthesized via vinilic substitution. 2,3-Dichloro-1,4- naphthoquinone gave 3a and 4b with 4,4'-thiobisbenzenethiol, respectively. Compounds 6 and 7c were obtained from the reaction of 2,3-dichloro-1,4- naphthoquinone with cyclohexylmercaptane. The compounds 9d and 10 were prepared from the reaction of 2,3-dichloro-1,4-naphthoquinone with 6-mercapto-1-hexanol. Compounds 12, 13c, 14d, and 15 were synthesized from the reaction of 2,3-dichloro-1,4-naphthoquinone with 1,6-hexanedithiol. Their structures were characterized by micro analysis, FT-IR, ¹H NMR, ¹³C NMR, MS, UV-Vis, and fluorescence spectroscopy. Copyright Taylor & Francis Group, LLC.

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Phosphorus, Sulfur, and Silicon and the
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Synthesis and Spectroscopic Properties
of S-,O-Substituted Naphthoquinone
Dyes
a
a
Cemil Ibis & Nahide Gulsah Deniz
a
Faculty of Engineering, Department of Chemistry , Istanbul
University , Avcilar-Istanbul, Turkey
Published online: 03 Nov 2010.
To cite this article: Cemil Ibis & Nahide Gulsah Deniz (2010) Synthesis and Spectroscopic Properties
of S-,O-Substituted Naphthoquinone Dyes, Phosphorus, Sulfur, and Silicon and the Related Elements,
185:11, 2324-2332
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Phosphorus, Sulfur, and Silicon, 185:2324–2332, 2010
Copyright ꢀ
Taylor & Francis Group, LLC
C
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426501003598671
SYNTHESIS AND SPECTROSCOPIC PROPERTIES
OF S-,O-SUBSTITUTED NAPHTHOQUINONE DYES
Cemil Ibis and Nahide Gulsah Deniz
Faculty of Engineering, Department of Chemistry, Istanbul University,
Avcilar-Istanbul, Turkey
New S-,O-substituted naphthoquinone compounds (3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, 15) were
synthesized via vinilic substitution. 2,3-Dichloro-1,4-naphthoquinone gave 3a and 4b with
ꢀ
4
,4 -thiobisbenzenethiol, respectively. Compounds 6 and 7c were obtained from the reaction
of 2,3-dichloro-1,4-naphthoquinone with cyclohexylmercaptane. The compounds 9d and
0 were prepared from the reaction of 2,3-dichloro-1,4-naphthoquinone with 6-mercapto-1-
hexanol. Compounds 12, 13c, 14d, and 15 were synthesized from the reaction of 2,3-dichloro-
,4-naphthoquinone with 1,6-hexanedithiol. Their structures were characterized by micro
1
1
1
13
analysis, FT-IR, H NMR, C NMR, MS, UV-Vis, and fluorescence spectroscopy.
Keywords Fluorescence spectroscopy; heterocyclic compounds; 1,4-naphthoquinone; spec-
troscopic method; synthesis; thioethers
INTRODUCTION
Quinonic compounds are of great importance to understand different processes that
are related to biology. Macrocyclic thioethers could be useful for treatment of heavy-metal
1
poisoning as potential of heavy-metal receptors. Quinone-containing thio-crown ethers
represent a coupled system in which two mechanisms mutually influence each other, and
which might add to our understanding of the analogous biologically active compounds.
Naphthoquinones have been used to treat burns, cuts, and a variety of skin diseases
2
worldwide. Sulfur-containing naphthoquinones have been the subject of much interest
3
4
5
6
for a number of years due to anti-inflammatory, antibacterial, antifungal, and antiviral
biological activities. It is also well known that quinone-bearing macrocycles have great
7
potential as antibiotics and antitumor agents.
Naphthoquinone pigments typically demonstrate varible colors as a result of changes
in pH; hence, they are widely used in the chemical industry for the production of dyes,
medicines, food, etc. Naphthoquinone derivatives are yellow, orange, and purple-red pig-
8
ments, with UV absorptions at 214, 275, and 520 nm, respectively. Cosmetics such as
lipstick, rouge, and face powder made with naphthoquinone dyes possess the advantages of
having strong, stable coloring properties as well as certain antiphlogistic, antibacterial, and
9
antiviral properties. Some thioquinone dye molecules are employed as organic nonlinear
Received 17 September 2009; accepted 4 January 2010.
We thank the Research Fund of the Istanbul University for financial support of this work.
Address correspondence to Cemil Ibis, Faculty of Engineering, Department of Chemistry, Istanbul Univer-
sity, 34320 Avcilar-Istanbul, Turkey. E-mail: ibiscml@istanbul.edu.tr
2
324

S-,O-SUBSTITUTED NAPHTHOQUINONE DYES
2325
optical (NLO) materials,10 organic photoconductors (OPC), and emitters for electrolumi-
nescence (EL).11
In recent years, several S-,O-substituted naphthoquinone compounds have been syn-
11
thesized. S-,S-substituted naphthoquinone compounds have been prepared by the reactions
of 2,3-dichloro-1,4-naphthoquinone with alkyl chain mercaptan, cycloalkyl mercaptan, aryl
mercaptan, etc.1
2,13
The aim of this study was the synthesis and characterization of new
S-,O-substituted naphthoquinone compounds.
RESULTS AND DISCUSSION
ꢁ
The reaction of 2,3-dichloro-1,4-naphthoquinone with 4,4 -thiobisbenzenethiol
in ethanol in the presence of Na2CO3 gave 3a and 4b, respectively. Compounds
6
and 7c were obtained from the reaction of 2,3-dichloro-1,4-naphthoquinone with
cyclohexylmercaptan in ethanol. Mono(thio)substituted naphthoquinone 9d and
bis(thio)substituted naphthoquinone 10 compounds were obtained from the reaction
of 2,3-dichloro-1,4-naphthoquinone with 6-mercapto-1-hexanol. The reaction of 2,3-
dichloro-1,4-naphthoquinone with 1,6-hexanedithiol gave thioether compounds 12, 13c,
14d, and 15 in ethanol. It was shown that interesting heterocylic compounds 12 and 15
could be obtained from the reaction of long alkyl chain dithiol 11 with 2,3-dichloro-1,4-
naphthoquinone. Isolation and identification proved that a cyclization reaction had taken
place, yielding the compound 12 (Scheme 1).
The ESI mass spectrum of the compound 12 displayed a molecular ion peak at m/z
+
13
(
%) 305 (100) [M] . The C NMR spectra of compound 12 gave a single carbonyl signal
at 179.0 ppm (C O). Compound 13c was a S-,O-substituted naphthoquinone compound.
While compound 13c was formed, two chloro atoms were replaced with ethoxy groups,
which acted as a nucleophilic compound. On the contrary, these two chloro atoms were
not substituted in the compound 14d. The 1 C NMR spectra of compound 14d gave two
carbonyl signals at 174.0 and 178.9 ppm (C O), while compound 15 showed a carbonyl
signal at 177.8 ppm (C O) (Figure 1).
3
In the ESI mass spectrum of the compound 14d, the respective molecular ion peak
+
was observed at m/z (%) 531 (100) [M] . The cleavage of the chloro ion from compound
14d of the molecular ion gave a fragment at m/z (%) 493 (100), which was the base peak.
δC =177.84
δC = 34.38
δC = 177.84
δC =147.80
O
O
S
S
S
S
O
O
δC =147.80
δC = 177.84
δC = 29.64
δC = 177.84
δ =27.06
C
Figure 1 Distinctive δc values of compound 15.

2326
C. IBIS AND N. G. DENIZ
O
O
S
S
S
2
R
O
O
6
7
O
O
O
SH
S
R
1
S
5
O
R2
2
1
R
HS-R -SH
Cl
Cl
O
2
3
O
O
O
S
R1
S
O
1
3
R3
R
O
4
HS-(CH ) -OH
2
6
8
R1
R2
R3
3
, 4, 7, 9, 13, 14
O
O
S
(CH ) -OH
a
S
S
C H O-
2
6
S
(CH ) -OH
2
5
2
6
3
b
c
Cl
Cl
R
S-(CH ) -OH
2 6
O
C H O-
O
2
5
9
1
0
d
O
O
O
O
(
CH2)6
S
S
S
S
(
CH2)6
2
2
R
R
HS-(CH ) -SH
2
6
O
O
O
1
1
1
3
1
1
2
O
O
O
O
O
(
CH2)6
(CH )
2 6
S
S
S
S
3
3
S
R
R
S
(
CH2)6
O
O
1
4
1
5
Scheme 1
The respective molecular ion peak was observed at m/z (%) 609 (100) for compound 15 in
the mode of ESI.
2
,5-Diethoxy- and 2,6-diethoxybenzoquinone compounds have been prepared previ-
6
ously in the presence of an aliphatic base such as ethanol. In this study, S-,O-substituted-
1,4-naphthoquinone compounds 3a, 7c, and 13c have been obtained from the reactions of
2,3-dichloro-1,4-naphthoquinone with thiol in ethanol, which have been formed as side
products. Ethanol acted as a O-nuchleophilic compound in these reactions.
1
3
C NMR spectra of compound 6 gave a carbonyl signal at 178.2 ppm (C O).
1
Compound 7c showed two carbonyl signals at 178.1 and 178.7 ppm (C O). The H
NMR spectra of the compound 7c in CDCl3 displayed distinct signals with appropriate

S-,O-SUBSTITUTED NAPHTHOQUINONE DYES
2327
Table I Fluorescence data of the compounds 3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, and 15
Compound
Solvent
λmax(ex) (nm)
λmax(em) (nm)
3
4
6
7
9
1
1
1
1
1
a
b
CHCl3/MeOH (1:1)
CHCl3/MeOH (1:1)
CHCl3
245, 334
259, 342
261, 345
266, 307, 358
261, 347
253, 341
257
260
251
265, 345
412
407
395
405
397
414
406
407
c
d
0
2
3c
4d
5
CHCl3
CHCl3/MeOH (1:1)
CHCl3/MeOH (1:1)
CHCl3/MeOH (1:1)
CHCl3/MeOH (1:1)
CHCl3/MeOH (1:1)
CHCl3/MeOH (1:1)
309, 377
425
multiples. The triplet (J = 7.32 Hz) accounting for three protons centered at 1.22 ppm
was assigned to the protons of the methyl group. The multiplet in the region of 1.41–1.54
ppm, accounting for 10 protons, was assigned to the methylene protons. The two methylene
protons of (-O-CH2) grouping resonated as a quartet centered at 4.75 ppm. The aromatic
region corresponds to four protons at 7.70 (t, J = 7.81 Hz), 7.75 (t, J = 5.37 Hz), 8.07 (dd,
J = 6.83 and J = 7.39 Hz), and 8.13 ppm (dd, J = 6.83 and J = 7.39 Hz).
Fluorescence is an important property of quinone compounds for the use of organic
materials.1 The new naphthoquinone compounds 3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, and
4,15
15 showed the fluorescence property. The fluorescence excitation and emission maxima of
the synthesized compounds in CHCl3 or CHCl3/MeOH solution are summarized in Table I.
Figure 2 shows the excitation (1, 2) and the emission (3) spectra of 9d in CHCl3/MeOH.
The first and second bands at 261, 347 nm were assigned to the excited bands, and the third
band at 397 nm was the emission band at room temperature.
CONCLUSION
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.
The structures of products were determinated by microanalysis and spectroscopic data
1
13
such as FT-IR, H NMR, C NMR, MS, and UV/Vis. All these new compounds gave
spectroscopic data in accordance with the proposed structures.
Figure 2 The excitation (1, 2) and emission (3) bands of 9d in CHCl3/MeOH at rt.

2328
C. IBIS AND N. G. DENIZ
EXPERIMENTAL
Melting points were measured on a Buchi B-540 melting point apparatus. Elemental
analyses were performed on a Thermo Finnigan Flash EA 1112 Elemental analyser. Infrared
spectra were recorded in KBr pellets in Nujol mulls on a Perkin Elmer Precisely Spectrum
One FT-IR spectrometer. UV spectra in chloroform solution were recorded on a Perkin
1
13
Elmer Lambda 35 UV/Vis spectrometer. H and C NMR spectra were recorded on a Varian
Unity Inova operating at 500 MHz. Mass spectra were obtained on a Thermo Finnigan
LCQ Advantage MAX LC/MS/MS spectrometer according to ESI probe. Fluorescence
spectra were run on a Varıan Cary Eclipse Fluorescence Spectrophotometer. Excitation
−4
and emission spectra were measured for 10 M solutions for all compounds in CHCl3
and MeOH/CHCl3 (1:1) at rt. Excitation and emission slit widths were set at 5 or 10 nm.
Products were isolated by column chromatography on silica gel (Fluka Silica gel 60,
particle size 63–200 µm) TLC plates, silica 60F254 (Merck, Darmstadt), and detection with
ultraviolet light (254 nm). All chemicals were reagent grade and were used without further
purification. Moisture was excluded from the glass apparatus using CaCl2 drying tubes.
General Procedure for the Synthesis of S-,O-Subtituted
Naphthoquinone Compounds (3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, 15)
Sodium carbonate was dissolved in ethanol (20 mL), and equimolar amounts of 2,3-
dichloro-1,4-naphthoquinone and thiols were added slowly. Without heating, the mixture
was stirred for 24 h. The color of the solution quickly changed, and the extent of the
reaction was monitored by TLC. Chloroform (30 mL) was added to the reaction mixture.
The organic layer was separated, 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.
ꢀ
4
,4 -Thiobisbenzylsulfanyl[2,2’:e]-diethoxy[3,3’]-bis(1,4-naphthoquione) (3a)
ꢁ
Compound 3a was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with 4,4 -
thiobisbenzenethiol 2 (1.2 g, 4.4 mmol) according to the above general procedure.
−1
Red oil, yield: 0.4 g (14%). Rf : 0.75 (CHCl3). IR (KBr pellet, cm ): 3059 (Ar-H),
920, 2851 (C-H), 1669 (C O), 1591 (C C). UV-vis[CHCl3, λ(logε)]: 204(3.4), 242(3.9),
2
3
1
43(3.0), 465(3.2) nm. H NMR (499.74 MHz, CDCl3): δ = 1.32 (t, J = 6.83 Hz, 6H,
CH3), 4.21 (q, 4H, O-CH2), 6.81–7.15 (m, 8H, Harom), 7.25 (t, J = 5.32 Hz, 2H, Hnapht),
7
.31 (t, J = 5.84 Hz, 2H, Hnapht), 7.75 (dd, J = 5.85 Hz, J = 5.86 Hz, 2H, Hnapht), 8.05
13
ppm (dd, J = 5.86 Hz, J = 5.86 Hz, 2H, Hnapht). C NMR (125.66 MHz, CDCl3): δ =
13.0 (CH3), 30.8 (O-CH2), 126.4, 127.7, 129.0, 129.3 (CHarom), 130.3, 133.1 (Carom), 161.8
+
(
C S), 170.2 ( C O), 190.2, 208.0 ppm (C O). MS [+ESI]: m/z 651 [M] . Anal.
Calcd for C36H26O6S3 (M, 650.79): C, 66.44; H, 4.02; S, 14.78. Found: C, 66.60; H, 4.14;
S, 14.09.
ꢀ
4
,4 -Thiobisbenzylsulfanyl[2,2’:e]-dichloro[3,3’]-bis(1,4-naphthoquinone) (4b)
ꢁ
Compound 4b was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with 4,4 -
thiobisbenzenethiol 2 (1.2 g, 4.4 mmol) according to the general procedure above.

S-,O-SUBSTITUTED NAPHTHOQUINONE DYES
2329
−1
Red oil, yield: 0.9 g (32%). Rf : 0.50 (CHCl3). IR (KBr pellet, cm ): 3068 (Ar-H),
922, 2851 (C-H), 1664 (C O), 1589 (C C). UV-vis[CHCl3, λ(logε)]: 204(3.5), 257(4.0),
2
1
3
44(3.1), 460(3.3) nm. H NMR (499.74 MHz, CDCl3): δ = 7.01–7.45 (m, 8H, Harom),
7
.62 (t, J = 5.37 Hz, 2H, Hnapht), 7.71 (t, J = 5.84 Hz, 2H, Hnapht), 7.93 (dd, J = 7.33
13
Hz, J = 7.32 Hz, 2H, Hnapht), 8.15 ppm (dd, J = 6.84 Hz, J = 6.83 Hz, 2H, Hnapht).
C
NMR (125.66 MHz, CDCl3): δ = 126.3, 130.5, 130.7, 133.0 (CHarom), 131.6, 131.6, 134.3
(
[
Carom), 140.3 ( C S), 147.0 ( C Cl), 177.7, 179.1 ppm (C O). MS [+ESI]: m/z 563
+
M-2Cl] . Anal. Calcd for C32H16O4S3Cl2 (M, 631.58): C, 60.85; H, 2.55; S, 15.23. Found:
C, 60.60; H, 2.14; S, 15.09.
2,3-Bis(cyclohexylsulfanyl)-1,4-naphthoquinone (6)
Compound 6 was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with cyclo-
hexylmercaptan 5 (0.51 g, 4.4 mmol) according to the general procedure above.
◦
−1
Red solid, yield: 0.9 g (53%). M.p. 57–58 C. Rf : 0.75 (CHCl3). IR (KBr pellet, cm ):
062 (Ar-H), 2926, 2851 (C-H), 1659 (C O), 1592 (C C). UV-vis[CHCl3, λ(logε)]:
3
2
(
1
39(3.8), 278(3.7), 345(3.0), 469(3.5) nm. H NMR (499.74 MHz, CDCl3): δ = 1.21–2.23
m, 20H, CH2), 3.91–4.05 (m, 2H, S-CH<), 7.65 (dd, J = 5.37 Hz, J = 5.86 Hz, 2H,
13
Harom), 8.12 ppm (dd, J = 5.86 Hz, J = 5.85 Hz, 2H, Harom). C NMR (125.66 MHz,
CDCl3): δ = 24.5, 24.9, 33.0 (CH2), 46.0 (CH), 125.9, 132.3 (CHarom), 132.0 (Carom), 147.7
+
+
(
C S), 178.2 ppm (C O). MS [+ESI]: m/z 386 [M] , 303 [M-(C6H11)] . Anal. Calcd
for C22H26O2S2 (M, 386.57): C, 68.35; H, 6.78; S, 16.58. Found: C, 68.45; H, 7.13; S,
6.61.
1
2
-(1-Cyclohexylsulfanyl)-3-(1-ethoxy)-1,4-naphthoquinone (7c)
Compound 7c was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with cyclo-
hexylmercaptan 5 (0.51 g, 4.4 mmol) according to the general procedure above.
−1
Dark red oil, yield: 0.4 g (28%). Rf : 0.50 (CHCl3). IR (KBr pellet, cm ): 3069 (Ar-
H), 2983, 2936 (C-H), 1676, 1660 (C O), 1592, 1563 (C C). UV-vis[CHCl3, λ(logε)]:
1
2
39(2.8), 273(3.8), 340(3.8), 468(3.2) nm. H NMR (499.74 MHz, CDCl3): δ = 1.22 (t,
J = 7.32 Hz, 3H, CH3), 1.41–1.54 (m, 10H, CH2), 4.40–4.52 (m, 1H, S-CH<), 4.75 (q,
H, O-CH2), 7.70 (t, J = 7.81 Hz, 1H, Harom), 7.75 (t, J = 5.37 Hz, 1H, Harom), 8.07 (dd,
2
J = 6.83 Hz, J = 7.39 Hz, 1H, Harom), 8.13 ppm (dd, J = 6.83 Hz, J = 7.39 Hz, 1H, Harom).
13
C NMR (125.66 MHz, CDCl3): δ = 14.9 (CH3), 24.6, 25.0, 32.9 (CH2), 43.9 (CH), 69.6
(
(
O-CH2), 125.8, 125.9, 132.4, 132.5 (CHarom), 129.8, 132.8 (Carom), 132.2 ( C S), 155.6
+
+
C O), 178.1, 178.7 ppm (C O). MS [+ESI]: m/z 317 [M] , 234 [M-(C6H11)] . Anal.
Calcd for C18H20O3S1 (M, 316.42): C, 68.32; H, 6.37; S, 10.13. Found: C, 68.37; H, 6.94;
S, 10.34.
2-(6-Sulfanyl-1-hexanol)-3-chloro-1,4-naphthoquinone (9d)
Compound 9d was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with 6-
mercapto-1-hexanol 8 (0.59 g, 4.4 mmol) according to the general procedure above.
−1
Red oil, yield: 0.4 g (28%). Rf : 0.67 (3CH2Cl2:1EtAc). IR (KBr pellet, cm ):
3
401 (OH), 3065 (Ar-H), 2930, 2856 (C-H), 1661 (C O), 1592, 1570 (C C), 707 (C-Cl).
1
UV-vis[CHCl3, λ(logε)]: 235(3.3), 247(3.2), 253(3.4), 281(3.5), 334(3.2), 470(3.0) nm. H
NMR (499.74 MHz, CDCl3): δ = 1.22–1.41 (m, 4H, CH2), 1.52 (m, 2H, S-CH2-CH2),

2330
C. IBIS AND N. G. DENIZ
1
2
1
.74 (m, 2H, CH2-CH2-OH), 3.32 (t, J = 6.83 Hz, 2H, S-CH2), 3.65 (t, J = 7.33 Hz,
H, CH2-OH), 4.42 (s, 1H, OH), 7.80 (t, J = 7.32 Hz, 1H, Harom), 7.92 (t, J = 7.32 Hz,
H, Harom), 8.05 (dd, J = 7.81 Hz, J = 7.32 Hz, 1H, Harom), 8.10 ppm (dd, J = 6.83 Hz,
13
J = 7.39 Hz, 1H, Harom). C NMR (125.66 MHz, CDCl3): δ = 28.2, 28.4 (CH2), 30.3
(S-CH2-CH2), 32.5 (CH2-CH2-OH), 34.8 (S-CH2), 62.8 (CH2-OH), 126.8, 126.9, 133.4,
1
34.2 (CHarom), 130.8, 131.2 (Carom), 147.8 ( C S), 156.7 ( C Cl), 178.6, 179.8 ppm
+
(
C O). MS[+ESI]: m/z 325 [M] . Anal. Calcd for C16H17O3S1Cl1 (M, 324.82): C, 59.16;
H, 5.27; S, 9.87. Found: C, 59.40; H, 5.38; S, 9.28.
2,3-Bis(6-sulfanyl-1-hexanol)-1,4-naphthoquinone (10)
Compound 10 was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with 6-
mercapto-1-hexanol 8 (0.59 g, 4.4 mmol) according to the general procedure above.
◦
Red solid, yield: 1.1 g (59%). Mp 70.1–70.5 C. Rf : 0.30 (3CH2Cl2:1EtAc). IR
−1
(
(
KBr pellet, cm ): 3382 (OH), 3071 (Ar-H), 2932, 2858 (C-H), 1660 (C O), 1591, 1545
C C). UV-vis[CHCl3, λ(logε)]: 235(3.2), 240(3.3), 276(3.7), 336(3.1), 459(3.0) nm. H
1
NMR (499.74 MHz, DMSO-d6): δ = 1.21–1.42 (m, 8H, CH2), 1.53 (m, 4H, S-CH2-CH2),
.62 (m, 4H, CH2-CH2-OH), 3.25 (t, J = 6.83 Hz, 4H, S-CH2), 3.46 (t, J = 7.33 Hz, 4H,
CH2-OH), 4.32 (s, 2H, OH), 7.80 (dd, J = 7.32 Hz, J = 6.83 Hz, 2H, Harom), 7.95 ppm (dd,
1
13
J = 7.80 Hz, J = 6.84 Hz, 2H, Harom). C NMR (125.66 MHz, CDCl3): δ = 24.2, 24.3
(CH2), 27.4 (S-CH2-CH2), 29.3 (CH2-CH2-OH), 33.8 (S-CH2), 61.7 (CH2-OH), 125.8,
1
32.4 (CHarom), 132.0 (Carom), 146.8 ( C S), 178.0 ppm (C O). MS[-ESI]: m/z 404
+
[M-OH] . Anal. Calcd for C22H30O4S2 (M, 422.61): C, 62.52; H, 7.15; S, 15.17. Found:
C, 62.55; H, 7.09; S, 15.32.
2,3,4,5,6,7-Hexahydronaphtho[2,3-e][1,8]dithionine-9,14-dione (12)
Compound 12 was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with 1,6-
hexanedithiol 11 (0.66 g, 4.4 mmol) according to the general procedure above.
◦
Red solid, yield: 0.4 g (30%). Mp 138–139 C. Rf : 0.75 (CHCl3). IR (KBr pellet,
−1
cm ): 3065 (Ar-H), 2922, 2852 (C-H), 1667, 1653 (C O), 1590 (C C). UV-vis[CHCl3,
λ(logε)]: 229(3.1), 239(3.2), 268(3.5), 343(3.1), 469(3.4) nm. H NMR (499.74 MHz,
1
CDCl3): δ = 1.31–1.52 (m, 4H, CH2), 1.73 (m, 4H, CH2), 3.25 (t, J = 6.34 Hz, 4H,
S-CH2), 7.51 (dd, J = 7.32 Hz, J = 6.84 Hz, 2H, Harom), 8.05 ppm (dd, J = 5.86 Hz, J =
1
3
8
3
.78 Hz, 2H, Harom). C NMR (125.66 MHz, CDCl3): δ = 23.7 (CH2), 24.0 (S-CH2-CH2),
3.0 (S-CH2), 126.2, 132.7 (CHarom), 131.6 (Carom), 149.1 ( C S), 179.0 ppm (C O).
MS [+ESI]: m/z 305 [M] , 271 [M-S] . Anal. Calcd for C16H16O2S2 (M, 304.43): C,
3.12; H, 5.29; S, 21.06. Found: C, 62.98; H, 5.20; S, 21.43.
+
+
6
7,8,9,10,11,12-Hexahydrodinaphtho[2,2’-e]-diethoxy[3,3’][1,8]
dithionine-5,14,19,20-tetrone (13c)
Compound 13c was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with 1,6-
hexanedithiol 11 (0.66 g, 4.4 mmol) according to the general procedure above.
−1
Dark red oil, yield: 0.4 g (16%). Rf : 0.30 (CHCl3). IR (KBr pellet, cm ): 3071
(
2
7
Ar-H), 2918, 2849 (C-H), 1658 (C O), 1589 (C C). UV-vis[CHCl3, λ(logε)]: 224(3.2),
1
32(3.3), 239(3.4), 266(3.5), 444(3.5) nm. H NMR (499.74 MHz, CDCl3): δ = 1.12 (t, J =
.32 Hz, 3H, CH3), 1.21–1.54 (m, 4H, CH2), 1.62–1.75 (m, 4H, S-CH2-CH2), 3.24 (t, J =

S-,O-SUBSTITUTED NAPHTHOQUINONE DYES
2331
7
(
.32 Hz, 4H, S-CH2), 3.42 (t, J = 7.32 Hz, O-CH2), 7.60 (t, J = 5.86 Hz, 2H, Harom), 7.65
t, J = 6.83 Hz, 2H, Harom), 7.96 (dd, J = 8.29 Hz, J = 8.79 Hz, 2H, Harom), 8.05 ppm (dd,
J = 7.80 Hz, J = 6.84 Hz, 2H, Harom). C NMR (125.66 MHz, CDCl3): δ = 13.0 (CH3),
7.1 (CH2), 28.6 (S-CH2-CH2), 33.7 (S-CH2), 68.3 (O-CH2), 126.3, 132.4 (CHarom), 131.9
13
2
(
[
Carom), 148.1 ( C S), 174.0 ( C O), 177.9, 178.8 ppm (C O). MS [+ESI]: m/z 550
+
M] .Anal. Calcd for C30H30O6S2 (M, 550.69): C, 65.43; H, 5.49; S, 11.64. Found: C,
65.09; H, 5.19; S, 11.24.
7,8,9,10,11,12-Hexahydrodinaphtho[2,2’:e]-dichloro[3,3’][1,8]
dithionine-5,14,19,20-tetrone (14d)
Compound 14d was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with
1
,6-hexanedithiol 11 (0.66 g, 4.4 mmol) according to the general procedure above.
−1
Red oil, yield: 0.3 g (13%). Rf : 0.60 (CHCl3). IR (KBr pellet, cm ): 3076 (Ar-H),
924, 2853 (C-H), 1671, 1658 (C O), 1589 (C C), 705 (C-Cl). UV-vis[CHCl3, λ(logε)]:
2
2
1
7
1
29(3.1), 239(3.2), 267(3.5), 315(3.1), 446(3.3) nm. H NMR (499.74 MHz, CDCl3): δ =
.21–1.55 (m, 4H, CH2), 1.64–1.75 (m, 4H, S-CH2-CH2), 3.31 (t, J = 7.81 Hz, 4H, S-CH2),
.65 (t, J = 5.37 Hz, 2H, Harom), 7.70 (t, J = 6.83 Hz, 2H, Harom), 8.00 (dd, J = 8.78 Hz,
13
J = 8.30 Hz, 2H, Harom), 8.06 ppm (dd, J = 7.81 Hz, J = 7.32 Hz, 2H, Harom). C NMR
(
125.66 MHz, CDCl3): δ = 27.0 (CH2), 29.1 (S-CH2-CH2), 33.0 (S-CH2), 126.2, 126.3,
132.8, 133.1 (CHarom), 130.2, 131.6 (Carom), 139.0 ( C S), 148.1 ( C Cl), 174.0, 178.9
+
+
ppm (C O). MS [+ESI]: m/z 531 [M] , 493 [M-Cl] .Anal. Calcd for C26H20O4S2Cl2 (M,
31.48): C, 58.75; H, 3.79; S, 12.06. Found: C, 58.59; H, 3.49; S, 12.24.
5
7,8,9,10,11,12,21,22,23,24,25,26-Dodecahydrodinaphtho[2,3-e:2 ’, 3’-n]
[1,8,11,18]tetrathiacyclotetracosine-5,14,19,28-tetrone (15)
Compound 15 was synthesized from the reaction of 1 (1.0 g, 4.4 mmol) with 1,6-
hexanedithiol 11 (0.66 g, 4.4 mmol) according to the general procedure above.
◦
Red solid, yield: 0.7 g (26%). Mp 176–177 C. Rf : 0.50 (CHCl3). IR (KBr pel-
−1
let, cm ): 3065 (Ar-H), 2922, 2851 (C-H), 1660 (C O), 1590 (C C). UV-vis[CHCl3,
1
λ(logε)]: 225(3.0), 232(3.1), 241(3.5), 456(3.6) nm. H NMR (499.74 MHz, CDCl3): δ =
1
7
4
(
[
.21–1.40 (m, 8H, CH2), 1.49–1.65 (m, 8H, S-CH2-CH2), 3.22 (t, J = 7.32 Hz, 8H, S-CH2),
.63 (dd, J = 5.85 Hz, J = 5.85 Hz, 4H, Harom), 7.97 ppm (dd, J = 5.37 Hz, J = 5.86 Hz,
13
H, Harom). C NMR (125.66 MHz, CDCl3): δ = 27.0 (CH2), 29.6 (S-CH2-CH2), 34.3
S-CH2), 132.0 (Carom), 125.9, 132.5 (CHarom), 147.8 ( C S), 177.8 ppm (C O). MS
+
+ESI]: m/z 609 [M] . Anal. Calcd for C32H32O4S4 (M, 608.87): C, 63.12; H, 5.29; S,
2
1.06. Found: C, 63.40; H, 5.48; S, 21.28.
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1