Sulfur-containing derivatives of 1,4-naphthoquinone, part 2: Sulfenyl derivative synthesis

Article abstract of DOI:10.1002/hc.20157

Sulfenylchlorides, sulfenates, and sulfenamides of 1,4-naphthoquinone were synthesized, and different methods of their syntheses were investigated. Synthesized sulfenates and sulfenamides are stable due to the large electron-withdrawing potential of the c

Full text of DOI:10.1002/hc.20157

Heteroatom Chemistry
Volume 16, Number 7, 2005
Sulfur-Containing Derivatives
of 1,4-Naphthoquinone, Part 2:
Sulfenyl Derivative Synthesis
Maryna V. Stasevych, Maxym Yu. Plotnikov, Mykola O. Platonov,
Svitlana I. Sabat, Rostyslav Ya. Musyanovych,
and Volodymyr P. Novikov
Department of Technology of Biologically Active Substances, Pharmacy and Biotechnology,
Institute of Chemistry and Chemical Technology, National University “Lviv Polytechnic,”
Bandera Str. 12, 79013, Lviv-13, Ukraine
Received 21 April 2005; revised 18 July 2005
the base of the naphthoquinone possess a high an-
ABSTRACT: Sulfenylchlorides, sulfenates, and sulfe-
tioxidant, anticancer, and cytostatic activity.
namides of 1,4-naphthoquinone were synthesized,
Compounds of the bivalent sulfur such as
and different methods of their syntheses were in-
sulfenylchlorides and sulfenamides have a high re-
vestigated. Synthesized sulfenates and sulfenamides
action ability that conditions their wide use within
are stable due to the large electron-withdrawing
organic synthesis. Due to high polarity and lability
potential of the conjugated quinonic system. Ob-
of S Cl, S N bonds, they easily react with both nu-
tained mono- and bi-functional sulfenderivatives
cleophilic and electrophilic reagents, and thus may
are very important in organic synthesis of dif-
be to used for synthesis of sulfur compounds with
ꢀ
C
ferent new heterocyclic compounds.
2005 Wiley
carbon and heteroatom bonds such as sulfides, disul-
fides, sulfinamides, sulfenates, sulfonates, sulfochlo-
rides, aminosulfonics, thioammonium, and sodium
salts.
Periodicals, Inc. Heteroatom Chem 16:587–598, 2005; Pub-
lished online in Wiley InterScience (www.interscience.
wiley.com). DOI 10.1002/hc.20157
Bifunctional sulfenylic derivatives that contain
other functional groups(Cl, Br, C O, S Cl, ClC O,
ClC N, CCl3, CF2Cl, and others) are used in the syn-
thesis of different heterocyclic compounds.
Further, sulfenylchlorides and sulfenamides are
used in macromolecular chemistry as monomers [1],
in the production of such widely known biologically
active preparations such as phtalan, captan [2,3], eu-
paren, euparen–M [4,5], as well as in the production
of pharmaceutical preparations [3,8], and vulcaniz-
ing agents [9,10–14], what makes their perspective
clear in the practical sense.
INTRODUCTION
Recently, pharmaceutics and scientists have been
greatly interested in sulfenic-containing substances
because they are synthones for further conversions
and they are compounds with a wide spectrum
of biological activity. Besides, derivatives of 1,4-
naphthoquinone have been revealed as bacterio-
static, antiviral, and fungistatic active. The drugs on
Our purpose is the synthesis of compounds,
which combine a naphthoquinone and sulfenylic
fragments that would expand the spectrum of bio-
logical action.
Correspondence to: Volodymyr P. Novikov; e-mail: vnovikov@
polynet.lviv.ua.
2005 Wiley Periodicals, Inc.
c
ꢀ
587

588 Stasevych et al.
RESULTS AND DISCUSSION
Chlorination of sulfides 3a–h, 6, 9 led to reac-
tion mixtures of sulfenylchlorides 4a–h, 7, respec-
tively and by-products 5a–h, 8, 2 which are dif-
ficult to separate by chromatography on silica gel
(Scheme 2).
It is known that sulfuryl chloride slowly reacts
with aromatic disulfides. In the case of electron-
withdrawing groups in ortho to para position, the
reaction does not take place.
We have investigated some methods of synthe-
sis of the new sulfenylic derivatives of 1,4-
naphthoquinone, which are not described in the lit-
erature before.
Synthesis of the Sulfenylchlorides of
1,4-Naphthoquinone
Parfyonov and Fomin [21] established that
triphenylphosphine carbamide, tertiary amines, and
amides of carbonic acids are effective catalysts of
the chlorinolysis of aromatic disulfides. Authors have
suggested a mechanism of the catalysis.
Various attempts to use these methods for disul-
fides, thiols, and sulfides at room temperature have
failed. At the boiling of reaction mixture, the chlo-
rination of alkyl groups and aromatic system and
the elimination of aminosubstitutes were also ob-
served. It decreased yields of sulfenylchlorides to
20–30%. The synthesis of 2,3-disulfenylchloride-1,4-
naphthoquinone takes longer, than in the case of
chlorination of bis-disulfide by chlorine.
N-Chlorosuccinimide was used as a chlorinating
agent to avoid such side effects. The reaction is easily
completed under room temperature without form-
ing by-products, and succinimide is easy to separate
from a reaction mixture.
In order to obtain sulfenylchlorides 4a–h, 7, we
used amino-, chloro-, thiols 10a–h, 12; synthesis of
these compounds has been realized in the two differ-
ent ways [20]. The reaction was carried out similarly,
as described in [22,23], in inert solvents (Scheme 3).
The formation of the products was observed after 25–
35 min: sulfenylchloride dissolves, and succinimide
precipitates.
In the literature, various methods of the synthesis
of sulfenylchlordies [15–17] are described. The main
methods consist in chlorinolysis of disulfides, thiols,
and sulfides. For activation of S S, S H, and C S
bonds and to carry out chlorinolysis in many cases,
it is necessary to select a catalyst, which would be
able to increase electrophilic properties of the bonds
in combination with an effective chlorinating agent.
It is known [18] that sulfuryl chloride in chlori-
nolysis of disulphides is more effective than chlorine.
Excess amount of chlorine leads to the formation of
polychlorides RSCl2SCl2R and RSCl3 [19], which are
unstable and pollute sulfenylchlorides. The reaction
is carried out in anhydrous chloroform or carbon
tetrachloride.
We have investigated the chlorinolysis of thiols,
disulfides, and sulfides of 1,4-naphthoquinone under
the action of the some chlorinating agents—chlorine,
sulfuryl chloride, and N-chlorosuccinimide with and
without catalytic conditions.
Chlorinolysis of sulfur-containing derivatives of
1,4-naphthoquinone by chlorine and sulfuryl chlo-
ride was carried out with different ratios of reagents.
In the case of thiols, 1:1.4 was found to be the best
ratio. When a smaller amount of chlorine is used,
poor yields of sulfenylchloride are obtained, and a
larger portion of disulfide is formed.
Therefore, sulfenylchlorides are better syn-
thesized by the interaction of thiols with N-
chlorosuccinimide or chlorine in inert solvents at
room temperature. Yields of obtained sulfenylchlo-
rides are 59–75%.
Chlorinolysis of disulfides and sulfides does not
work at room temperature. Under long time boil-
ing with excess amount of chlorine or sulfuryl
chloride, the decomposition of disulfide and sul-
fide bonds and chlorination of aromatic ring and
in a side chain were observed. One exception was
2,3-disulfenylchloride-1,4-naphthoquinone (2), ob-
tained from bis-disulfide 1 [20] (Scheme 1).
Synthesis of Sulfenates of 1,4-Naphthoquinone
It is known that esters of sulfenic acids have been
obtained by the reaction of sulfenylchlorides with
alcoholate (phenolate) or alcohol (phenol) in the
presence of the base [15,24–26]. The reaction is not
always facile. Obtained sulfenates can react with
sulfenylchloride-forming disulfides and other by-
products due to high nucleophility of sulfur. The re-
action of sulfenylchlorides with a strong electron-
withdrawing group at the sulfur atom is more facile.
This reduces the nucleophility of the sulfur atom.
SCHEME 1

Sulfur-Containing Derivatives of 1,4-Naphthoquinone, Part 2: Sulfenyl Derivative Synthesis 589
SCHEME 2
We carried out synthesis of sulfenates 13–19a–
naphthoquinone are stable substances. This is ex-
plained by the influence of a conjugated quinonic
system with a large electron-withdrawing potential.
d, 20a–d, 21a–d by the interaction of sulfenylchlo-
rides 4a–h, 7, 2 with aliphatic alcohol and phenols
in dry inert solvents in the presence of triethylamine
(Scheme 4).
The esters of sulfenic acids are labile com-
pounds [15, 24–26]. Synthesized sulfenates of 1,4-
Synthesis of the Sulfenamides of the
1,4-Naphthoquinone
We carried out the synthesis of the sulfenamides
22a–c, 23–29a–c, 30a–c by the interaction of ob-
tained sulfenylchlorides with the primary, secondary,
alkyl, and aryl amines in the presence of triethy-
lamine (Scheme 5). Such a reaction occurred with
high yields and without formation of by-products
quickly under mild conditions.
Sulfenamides have been obtained by an alter-
native synthesis, which form disulfides [20] and
primary, secondary alkyl, and aryl amines in the
presence of silver nitrate similar to [27]. Sulfe-
namide dissolves, and silver mercaptide precipitates
(Scheme 6).
This method is less acceptable because ini-
tial disulfides are difficult to purify, and the reac-
tion is carried out under harder conditions in pro-
tonic solvents. This reduces yields and purity of
SCHEME 3

590 Stasevych et al.
heterocyclic compounds with different functional
groups.
EXPERIMENTAL
Melting points were measured on a Nagema melting
point apparatus and are uncorrected. 1H NMR spec-
tra were recorded on Varian VXR (300 MHz) spec-
trometer as solutions in DMSO-d6 with as an internal
standard. IR spectra were recorded on Specord M80
in the tablets of KBr. Materials used were disulfides,
thiols, and sulfides [20].
General Procedure of Sulfenylchloride-
1,4-naphthoquinones Synthesis 4a–h, 7
from Thiols 10a–h, 12
Method A. 0.05 mol of thiol and 0.05 mol of N-
chlorosuccinimide were suspended in carbon tetra-
chloride. The reaction mixture was left at room tem-
perature for 24 h and filtered. The precipitate was
washed by small amount of carbon tetrachloride.
The filtrate was evaporated. Residue was recrystal-
lized from benzene.
SCHEME 4
sulfenamides. The structures of the obtained com-
pounds were confirmed by NMR, IR, and the element
analysis.
Prepared mono- and bi-functional sulfenyl
derivatives are useful for the synthesis of the
Method B. 0.05 mol of thiol (or 2) was sus-
pended in carbon tetrachloride, and 0.1 mol of
cl2(solution in CCl4) was added. The reaction mix-
ture was left at room temperature for 24 h and
filtered. The precipitate was washed by small
amount of carbon tetrachloride. The filtrate evapo-
rated. Residue was recrystallized from benzene. 2,3-
Disulfenylchloride-1,4-naphthoquinone 2 was ob-
tained from 1. See method B.
See Table 1 for yields and elemental analysis of
sulfenylchlorides 4a–h, 7, 2 obtained from 10a–h,
12, 1.
General Procedure of the Synthesis of Sulfenates
of 1,4-Naphthoquinone 13–19a–d, 20a–d,
21a–d from the Sulfenylchlorides 4a–h, 2, 7
The mixture of alcohol or phenol (0.2 mol) and tri-
ethylamine (0.2 mol) was stirred for 10 min in ben-
zene. Benzene solution of sulfenylchloride (0.2 mol)
was added. The reaction mixture was left at room
temperature for 24 h, then warmed up to 40◦C for 5–
6 h. The reaction mixture was evaporated. Residue
was recrystallized from hexane.
See Table 2 for yields and elemental details of
sulfenates 13–19a–d, 20a–d, 21a–d obtained from
sulfenchlorides 4a–h, 2, 7.
SCHEME 5

Sulfur-Containing Derivatives of 1,4-Naphthoquinone, Part 2: Sulfenyl Derivative Synthesis 591
SCHEME 6
in benzene. Benzene solution of sulfenylchloride
(0.025 mol) was added. The reaction mixture was
left at room temperature for 24 h, then was warmed
up to 40◦C for 5–6 h. The reaction mixture was
evaporated. Residue was recrystallized from
hexane.
General Procedure of Sulfenamide-1,4-
naphthoquinones Synthesis 22a–c, 23–29a–c,
30a–c from the Sulfenylchlorides 4a–h, 2, 7 (A)
and Disulfides 1, 31–33a–h (B)
Method A. The mixture of amine (0.025 mol)
and triethylamine (0.025 mol) was stirred for 10 min
TABLE 1 Sulfenylchlorides 4a–h, 7, 2 from 10a–h, 12, 1
Calculated Found (%)
Yield (%)
A/B
C
H
S
Cl
N
4a
4b
4c
4d
4e
4g
4h
7
66/63
59/54
68/65
72/75
67/65
73/72
62/61
63/66
62/63
56.85
56.91
61.44
61.32
58.53
58.42
54.28
54.29
60.86
60.79
54.87
54.76
52.45
52.36
46.36
46.31
41.25
41.31
4.77
4.80
6.30
6.37
4.58
4.46
3.90
3.87
3.19
3.21
2.59
2.61
2.14
2.17
1.56
1.58
1.38
1.34
10.84
10.67
9.11
11.99
11.84
10.07
10.11
11.52
11.54
11.44
11.39
11.23
11.29
20.25
20.31
15.53
15.63
27.36
27.41
24.35
24.41
4.74
4.65
3.98
3.91
4.55
4.60
4.52
4.56
4.44
4.46
4.00
4.01
4.50
4.42
9.01
10.42
10.46
10.35
10.42
10.15
10.18
9.16
9.21
9.97
9.89
12.37
12.42
22.02
22.01
2

592 Stasevych et al.
TABLE 2 Sulfenates 13–19a–d, 20a–d, 21a–d from sulfenchlorides 4a–h, 2, 7
Calculated Found (%)
Yield (%)
A/B
C
H
S
N
Cl
13a
13b
13c
13d
14a
14b
14c
14d
15a
15b
15c
15d
16a
16b
16c
16d
17a
17b
17c
17d
18a
18b
18c
18d
19a
19b
19c
19d
20a
70
73
72
71
73
69
72
74
68
72
74
73
76
71
74
69
73
76
72
78
67
69
70
68
71
72
69
71
73
61.83
61.85
62.93
62.98
63.92
63.96
67.97
68.01
64.84
64.87
65.68
65.70
66.45
66.49
69.85
69.81
63.35
63.40
64.33
64.37
65.23
65.19
69.02
69.04
59.00
59.03
60.17
60.23
61.24
61.20
65.38
65.40
65.53
65.51
66.44
66.42
67.24
67.32
70.76
70.71
59.05
59.00
60.08
60.11
61.04
61.06
64.79
64.82
51.88
51.91
53.64
53.61
55.22
55.23
60.67
60.69
51.88
51.83
5.88
5.94
6.27
6.31
6.63
6.72
5.42
5.46
6.95
6.98
7.25
7.28
7.53
7.49
6.37
6.41
5.65
5.60
6.03
6.07
6.39
6.37
5.24
5.27
4.95
4.91
5.37
5.35
5.74
5.78
4.66
4.61
4.21
4.27
4.65
4.67
5.05
5.00
4.05
4.01
3.05
3.08
3.92
3.95
4.31
4.35
3.46
3.52
2.77
2.79
3.38
3.39
3.92
3.95
2.86
2.90
2.77
2.76
11.00
11.02
10.50
10.47
10.04
10.07
9.07
9.09
9.62
9.64
9.23
4.81
4.75
4.59
4.61
4.38
4.36
3.96
3.93
4.20
4.26
4.03
4.01
3.87
3.91
3.54
3.49
4.62
4.64
4.41
4.38
4.23
4.21
3.83
3.85
4.59
4.60
4.39
4.41
4.20
4.23
3.81
3.82
4.60
4.58
4.30
4.35
4.13
4.10
3.75
3.78
4.05
4.01
3.89
3.85
3.75
3.78
3.43
3.41
4.05
4.10
3.89
3.91
3.75
3.69
3.43
3.45
9.21
8.87
8.82
8.11
8.13
10.57
10.58
10.10
10.07
9.67
9.62
8.77
8.72
10.50
10.47
10.04
10.05
9.62
9.64
8.73
8.68
10.30
10.34
9.85
9.89
9.45
9.50
8.59
8.63
9.27
9.31
8.91
8.93
8.58
8.62
7.86
7.91
12.59
12.61
11.93
11.96
11.34
11.36
10.12
10.14
12.59
12.61
13.92
13.90
13.19
13.15
12.54
12.62
11.19
11.21
13.92
13.96
(Continued)

Sulfur-Containing Derivatives of 1,4-Naphthoquinone, Part 2: Sulfenyl Derivative Synthesis 593
TABLE 2 Continued
Yield (%)
Calculated Found (%)
A/B
72
76
75
74
70
76
73
C
H
S
N
Cl
20b
20c
20d
21a
21b
21c
21d
53.64
53.67
55.22
55.25
60.67
60.73
51.05
51.09
54.18
54.22
56.78
56.81
65.01
65.06
3.38
3.42
3.92
3.96
2.86
2.90
3.57
3.62
4.55
4.59
5.36
5.43
3.47
3.50
11.93
11.91
11.34
11.36
10.12
10.15
22.71
22.76
20.66
20.68
18.95
18.93
15.78
15.84
13.19
13.14
12.54
12.49
11.19
11.21
Method B. 0.027 mol of silver nitrate was
tion; solvent was removed to give a residue which
was recrystallized from hexane.
dissolved in 100 mL of methanol. The solution was
cooled in an ice bath; an equivalent amount of disul-
fide was added. The reaction mixture was left at con-
stant stirring for 15 min. Then 0.027 mol of amine
was added, and mixture was stirred overnight. Pre-
cipitated silver mercaptide was removed by filtra-
See Table 3 for yields and elemental details
of sulfenamides 22a–c, 23–29a–c, 30a–c from
sulfenylchlorides 4a–h, 2, 7 (A) and disulfides 1, 31–
33a–h (B) and Table 4 for NMR, IR data of the syn-
thesized compounds.
TABLE 3 Sulfenamides 22a–c, 23–29a–c, 30a–c from Sulfenylchlorides 4a–h, 2, 7 (A) and Disulfides 1, 31-33a-h (B)
Calculated Found (%)
Yield (%)
A/B
C
H
S
N
Cl
23a
23b
23c
24a
24b
24c
25a
25b
25c
26a
26b
26c
67/54
64/52
69/56
60/52
67/52
71/60
72/59
70/56
75/63
76/62
74/63
73/59
62.48
62.47
57.92
57.89
64.85
64.81
66.25
66.18
62.40
62.43
68.16
68.14
68.96
68.93
65.64
65.61
70.56
70.62
67.37
67.41
63.66
63.62
69.21
69.19
5.59
5.67
4.86
4.83
4.08
4.11
7.02
7.06
6.40
6.38
5.72
5.68
8.05
8.01
7.51
7.60
6.91
6.87
6.79
6.74
6.19
6.21
5.53
5.49
11.12
11.10
11.04
11.07
10.82
10.85
9.31
9.38
9.25
9.27
9.10
9.13
8.00
8.05
7.97
7.91
7.85
7.84
8.99
8.97
8.94
8.91
8.80
8.85
9.71
9.75
9.65
9.67
9.45
9.43
8.13
8.15
8.09
8.05
7.95
7.93
6.99
6.95
6.96
7.01
6.86
6.91
7.86
7.95
7.81
7.91
7.69
7.76
(Continued)

594 Stasevych et al.
TABLE 3 Continued
Calculated Found (%)
S
Yield (%)
A/B
C
H
N
Cl
27a
27b
27c
28a
28b
28c
29a
29b
29c
22a
22b
22c
30a
30b
30c
71/63
72/59
70/61
73/65
74/60
69/58
65/61
72/69
71/65
74/67
69/61
73/66
71/68
73/64
72/65
63.66
63.78
59.98
59.89
65.56
65.62
69.21
69.25
65.56
65.52
70.95
70.91
63.23
63.19
59.92
59.89
64.94
64.92
58.53
58.48
54.28
54.32
60.86
60.92
61.82
61.95
55.08
55.12
65.32
65.24
6.19
6.08
5.59
5.56
4.95
4.91
5.53
5.62
4.95
4.97
4.33
4.38
4.80
4.83
4.27
4.24
3.72
3.78
4.58
4.48
3.90
3.79
3.19
3.25
6.23
6.18
5.14
5.24
3.99
4.01
8.94
8.91
8.90
8.95
8.75
8.79
8.80
8.82
8.75
8.71
8.61
8.67
8.04
8.09
8.00
8.10
7.88
7.81
7.86
7.71
7.81
7.64
7.58
7.69
7.62
7.64
7.69
7.52
7.43
7.02
6.92
6.99
6.92
6.88
6.85
4.55
4.52
4.52
4.63
4.44
4.47
7.21
7.28
7.14
7.10
6.93
6.96
8.89
8.83
8.84
8.91
8.71
7.92
8.69
10.42
10.36
10.35
10.22
10.15
10.07
16.50
16.56
16.34
16.48
15.85
15.77
11.52
11.57
11.44
11.48
11.23
11.19
TABLE 4 NMR, IR Data of the Synthesized Compounds
Formula,
mp ( ◦C)
1H ( δ, ppm)
IR (cm−1
)
4aa
4ba
C10H6NSClO2
116
C14H14NSClO2
124
C18H22NSClO2
156
7.63–8.29 (6H, m, ArH and NH2)
1655 (C O), 1358
(tert-N)
1650 (C O), 1350
(tert-N)
1.08 (12H, t, CH3), 3.41 (8H, q, CH2), 7.66; 7.56 (4H, td,
CHAr), 8.12; 8.05 (4H, dd, CHAr
)
4ca
0.84 (12H, t, 3 JHH = 9.3 Hz, CH3), 1.32 (16H, m, CH2), 3.06
1655 (C O), 1360
(8H, m, CH2), 8.03; 8.04 (4H, td, CHAr), 8.12; 8.17
(tert-N)
(4H, dd, CHAr
1.31 (12H, m, CH2), 3.71 (8H, m, CH2), 7.46; 7.78
(4H, td, CHAr), 7.98; 8.17 (4H, dd, CHAr
δ 3.49 (16H, m, CH2morpholine), 7.56; 7.67 (4H, td, CHAr), 8.02;
8.05 (4H, dd, CHAr
δ 7.05 (10H, m, Ar), 7.33 (2H, s broad, NH), 7.62; 7.82
)
4da
4ea
4ga
C14H18NSClO2
117
C14H12NSClO3
134
C16H10NSClO2
162
C16H9NSCl2O2
145
1620, 1656 (C O),
1340 (tert-N)
1612, 1648 (C O),
1355 (tert-N)
3160 ( NH ), 1610,
1650 (C O)
3160 ( NH ), 1612,
1648 (C O)
)
)
(4H, td, CHAr), 7.66; 8.05 (4H, dd, CHAr
)
4ha
6.94 (4H, d, 3 JHH = 8.4 Hz, CHAr), 7.1 (4H, d, 3 JHH = 8.4 Hz,
CHAr), 7.41 (2H, s broad, NH), 7.63; 7.70 (4H, td, CHAr),
8.16; 8.19 (4H, dd, CHAr
δ 7.79 (2H, m, CHAr), 8.08; 8.16 (2H, dd, CHAr), 8.51
(1H, s, SH)
7.65 (4H, tm, CHAr), 8.22 (4H, dd, CHAr)
)
7a
2a
C10H4SCl2O2
105
C10H4S2O2Cl2
195
1650 (C O)
1650 (C O)
(Continued)

Sulfur-Containing Derivatives of 1,4-Naphthoquinone, Part 2: Sulfenyl Derivative Synthesis 595
TABLE 4 Continued
Formula,
mp ( ◦C)
1H ( δ, ppm)
IR (cm−1
)
13aa
C11H9NSO3
86
7.63; 7.75 (2H, td, CHAr), 7.98; 8.01 (2H, dd, CHAr); 6.7
(2H, s, NH2); 2.7 (3H, s, OCH3)
2813 (OCH3),1655
(C O), 1358 (tert-N),
1590 (NH2)
1640 (C O),1560
(NH2), 1370 (CH3)
1648 (C O), 1610
(NH2), 1370
13ba
13ca
C12H11NSO3
7.66; 7.56 (4H, td, CHAr), 8.12; 8.05 (4H, dd, CHAr); 6.73
(2H, s, NH2); 3.97 (2H, q, CH2); 1.1 (3H, s, CH3)
7.45; 7.79 (4H, td, CHAr), 7. 91; 8.15 (4H, dd, CHAr);
0.80–0.85 (6H, dt, 2CH3); 2.14–2.30 (1H, m, CH);
3.50–3.53 (2H, m, OCH2); 6,71 (2H, s, NH2)
92
C13H13NSO3
87
(C(CH3)2)
13da
14aa
14ba
C16H12NSO3
121
C15H17NSO3
91
C16H19NSO3
98
7.71; 7.65 (4H, td, CHAr), 8.07; 8.01 (4H, dd, CHAr); 6.69
1652 (C O), 1590
(NH2), 1580 (Ar)
2817 (OCH3), 1648
(C O)
1665 (C O), 1380
(CH3)
(2H, s, NH2); 6,89–7.12 (5H, m, CHAr
)
7.56; 7.67 (4H, td, CHAr), 8.17; 8.10 (4H, dd, CHAr); 3.44–3.49
(4H, m, N(CH2)2); 2.78 (3H, s, OCH3); 1.13 (6H, t, 2CH3)
7.72; 7.63 (4H, td, CHAr), 8.12; 8.04 (4H, dd, CHAr); 3.98
(2H, m, OCH2); 3.44–3.49 (4H, m, N(CH2)2); 3.96
(2H, q, OCH2)
7.66; 7.56 (4H, td, CHAr), 8.08; 8.01 (4H, dd, CHAr); 3.56–3.57
(2H, m, OCH2); 3.44–3.49 (4H, m, N(CH2)2); 2.23–2.35
(1H, m, CH); 1.08 (6H, t, 2CH3); 0.78–0.81 (6H, dt, 2CH3)
7.78; 7.64 (4H, td, CHAr), 8.18; 8.11 (4H, dd, CHAr); 7.01–7.26
(5H, m, CHAr); 3.6 (4H, q, N(CH2)2); 1.13 (6H, t, 2CH3)
7.65; 7.57 (4H, td, CHAr), 8.14; 8.07 (4H, dd, CHAr); 3.03–3.21
(4H, m, 2CH2); 2.75 (3H, s, OCH3); 1.23–1.41 (4H, m,
2CH2); 0.8–0.98 (6H, t, 2CH3)
7.81; 7.69 (4H, td, CHAr), 8.15; 8.08 (4H, dd, CHAr); 3.95–4.00
(2H, m, OCH2); 3.08–3.13 (4H, m, N(CH2)2); 1.23–1.39
(8H, m, 4CH2); 1.10 (3H, t, CH3); 0.86–0.91 (6H, t, 2CH3)
7.70; 7.61 (4H, td, CHAr), 8.10; 8.02 (4H, dd, CHAr); 3.57–3.61
(2H, m, OCH2); 3.09–3.12 (4H, m, N(CH2)2); 2.23–2.35
(1H, m, CH); 1.24–1.39 (8H, m, 4CH2); 0.82–0.90 (6H, t,
2CH3)
14ca
C17H21NSO3
113
1648 (C O), 1354
(C(CH3)2)
14da
15aa
C20H19NSO3
110
C19H25NSO3
78
1650 (C O), 1500 (Ar)
2810 (OCH3), 1660
(C O), 1380 (CH3)
15ba
15ca
C20H27NSO3
92
1610 (C O), 1375
(CH3)
C21H29NSO3
98
1650 (C O), 1470
(CH3), 1385
(C(CH3)2)
15da
16aa
16ba
16ca
C24H27NSO3
101
7.45; 7.56 (4H, td, CHAr), 8.22; 8.12 (4H, dd, CHAr); 7.03–7.35
(5H, m, CHAr); 3.1–3.14 (4H, m, N(CH2)2); 1.27–1.42
(8H, m, 4CH2); 0.84–0.98 (6H, m, 2CH3)
7.71; 7.64 (4H, td, CHAr), 8.20; 8.16 (4H, dd, CHAr); 3.65–3.85
(4H, m, N(CH2)2); 2.76 (3H, s, OCH3); 1.24–1.54
(6H, m, 2CH3)
7.63; 7.52 (4H, td, CHAr), 8.12; 8.02 (4H, dd, CHAr); 3.69–3.83
(4H, m, N(CH2)2); 4.01 (2H, m, OCH2); 1.27–1.41
(6H, m, 2CH3); 1.19 (3H, t, CH3)
7.56; 7.47 (4H, td, CHAr), 8.02; 8.05 (4H, dd, CHAr); 3.68–3.84
(4H, m, N(CH2)2); 3.55–3.57 (2H, m, OCH2); 2.28–2.42
(1H, m, CH); 1.31–1.48 (6H, m, 2CH3); 0.87–0.89
(6H, dt, 2CH3)
1650 (C O), 1575 (Ar),
1375 (CH3)
C16H17NSO3
119
2810 (OCH3), 1660
(C O), 1362 (tert-N)
C17H19NSO3
118
1661 (C O), 1470
(CH3), 1345 (tert-N)
C18H21NSO3
130
1645 (C O), 1380
(C(CH3)2), 1342
(tert-N)
16da
17aa
17ba
17ca
C21H19NSO3
125
7.66; 7.58 (4H, td, CHAr), 7.98; 8.01 (4H, dd, CHAr); 7.06–7.42
(5H, m, CHAr); 3.73–3.86 (4H, m, N(CH2)2); 1.27–1.43
(6H, m, 2CH3)
7.66; 7.56 (4H, td, CHAr), 8.12; 8.05 (4H, dd, CHAr); 3.63–3.71
(4H, m, N(CH2)2); 3.33–3.51 (4H, m, –O(CH2)2); 2.76
(3H, s, OCH3)
7.65; 7.79 (4H, td, CHAr), 8.12; 8.05 (4H, dd, CHAr); 3.96
(2H, q, OCH2); 3.61–3.72 (4H, m, N(CH2)2); 3.38–3.51
(4H, m, –O(CH2)2); 1.15 (3H, t, CH3)
7.71; 7.62 (4H, td, CHAr), 7.98; 8.01 (4H, dd, CHAr); 3.55–3.61
(2H, m, CH2); 3.51–3.55 (4H, m, N(CH2)2); 3.38–3.47
(4H, m, –O(CH2)2); 2.27–2.35 (1H, m, CH); 0.87–0.94
(6H, dt, 2CH3)
1655 (C O), 1570 (Ar),
1352 (tert-N)
C15H15NSO4
142
2819 (OCH3), 1649
(C O), 1340 (tert-N),
C16H17NSO4
131
1661 (C O), 1450
(CH3), 1348 (tert-N)
C17H19NSO4
120
1645 (C O), 1390
(C(CH3)2), 1360
(tert-N)
(Continued)

596 Stasevych et al.
TABLE 4 Continued
Formula,
mp ( ◦C)
1H ( δ, ppm)
IR (cm−1
)
17da
18aa
18ba
18ca
C20H17NSO4
135
7.47; 7.68 (4H, td, CHAr), 8.10; 8.03 (4H, dd, CHAr); 7.01–7.36
(5H, m, CHAr); 3.55–3.67 (4H, m, N(CH2)2); 3.41–3.52
(4H, m, –O(CH2)2)
7.79; 7.81 (4H, td, CHAr), 8.15; 8.05 (4H, dd, CHAr); 7.98
(1H, s, NH); 7.06–7.45 (5H, m, CHAr); 2.85
(3H, s, OCH3)
7.66; 7.56 (4H, td, CHAr), 8.12; 8.05 (4H, dd, CHAr); 7.83
(1H, s, NH); 7.07–7.27 (5H, m, CHAr); 3.96 (2H, t, CH2);
1.1 (3H, t, CH3)
7.60; 7.74 (4H, td, CHAr), 8.03; 8.07 (4H, dd, CHAr); 7.9 (1H, s,
NH); 7.07–7.27 (5H, m, CHAr); 3.55–3.58 (2H, m,
OCH2); 2.35–2.41 (1H, m, CH); 0.82–0.84 (6H, dt, 2CH3)
7.66; 7.56 (4H, td, CHAr), 8.12; 8.05 (4H, dd, CHAr); 7.95 (1H,
1651 (C O), 1500 (Ar),
1362 (tert-N)
C17H13NSO3
124
3160 ( NH ), 2820
(OCH3), 1649
(C O), 1600 (Ar)
3158 ( NH ), 1660
(C O), 1500 (Ar),
1470 (CH3)
3175( NH ), 1654
(C O), 1520 (Ar),
1381 (C(CH3)2)
3160 ( NH ), 1648
(C O), 1610 (Ar)
3175 ( NH ), 2812
(OCH3), 1658
(C O), 1450 (Ar)
3170 ( NH ), 1651
(C O), 1450 (Ar),
1374 (CH3)
C18H15NSO3
128.5
C19H17NSO3
131–132
18da
19aa
C22H15NSO3
147
C17H12NClSO3
135.5
s broad, NH); 7.01–7.44 (10H, m broad, CHAr
)
7.66; 7.78 (4H, td, CHAr), 8.08; 8.02 (4H, dd, CHAr); 7.86
(1H, s, NH); 7.36 (2H, d, CHAr); 7.01 (2H, d, CHAr); 2.84
(3H, s, OCH3)
7.66; 7.56 (4H, td, CHAr), 8.12; 8.05 (4H, dd, CHAr); 7.89
(1H, s, NH); 7.35 (2H, d, CHAr); 7.02 (2H, d, CHAr); 3.98
(2H, q, OCH2); 1.1 (3H, t, CH3)
7.79; 7.83 (4H, td, CHAr), 8.03; 8.12 (4H, dd, CHAr); 7.75
(1H, s, NH); 7.41 (2H, d, CHAr); 7.09 (2H, d, CHAr);
3.58–3.62 (2H, m, OCH2); 2.25–2.35 (1H, m, CH);
0.82–0.84 (6H, m, 2CH3)
19ba
19ca
C18H14NClSO3
149
C19H16NClSO3
136–137
3175 ( NH ), 1660
(C O), 1510 (Ar),
1370 (C(CH3)2)
19da
20aa
20ba
20ca
C22H14NClSO3
7.45; 7.51 (4H, td, CHAr), 7.97; 8.05 (4H, dd, CHAr); 7.94 (1H,
3160 ( NH ), 1648
(C O), 1600 (Ar)
2810 (OCH3), 1652
(C O)
1645 (C O), 1380
(CH3)
141
C11H7SClO3
82
C12H9SClO3
86
C13H11SClO3
79
s, NH); 6.94–7.09 (4H, m, CHAr); 7.34–7.44 (5H, m, CHAr
7.56; 7.68 (4H, td, CHAr), 8.02; 8.08 (4H, dd, CHAr); 2.82
(3H, s, OCH3)
)
7.79; 7.65 (4H, td, CHAr), 8.21; 8.11 (4H, dd, CHAr); 3.98
(2H, t, CH2); 1.20 (3H, t, CH3)
7.68; 7.58 (4H, td, CHAr), 8.14; 8.09 (4H, dd, CHAr); 3.61–3.65
(2H, m, OCH2); 2.24–2.42 (1H, m, CH); 0.8–0.85
(6H, m, 2CH3)
1660 (C O), 1370
(C(CH3)2)
20da
21aa
21ba
21ca
C16H9SClO3
91
C12H10S2O4
131
C14H14S2O4
127
C16H18S2O4
135
7.79; 7.64 (4H, td, CHAr), 8.11; 8.05 (4H, dd, CHAr); 7.06–7.28
1648 (C O), 1450 (Ar)
(5H, m, CHAr
)
7.64; 7.54 (4H, td, CHAr), 8.09; 8.05 (4H, dd, CHAr); 2.79
(3H, s broad, OCH3)
7.49; 7.56 (4H, td, CHAr), 8.19; 8.07 (4H, dd, CHAr); 3.93
(4H, q, OCH2); 1.14 (3H, t, CH3)
7.68; 7.59 (4H, td, CHAr), 8.14; 8.07 (4H, dd, CHAr); 3.57–3.60
(4H, m, 2OCH2); 2.28–2.43 (1H, m, CH); 0.85–0.91
(6H, m, 2CH3)
2815 (OCH3), 1650
(C O)
1648 (C O), 1440
(CH3)
1660 (C O), 1365
(C(CH3)2)
21da
22ab
22bb
22cb
23ab
C22H14S2O4
145
C15H14NClSO2
88
C14H12NClSO3
101
C16H16NClSO2
118
7.77; 7.62 (4H, td, CHAr), 8.09; 8.03 (4H, dd, CHAr); 7.03–7.34
1648 (C O), 1510 (Ar)
(10H, m broad, CHAr
)
7.45; 7.51 (4H, td, CHAr), 8.14; 8.09 (4H, dd, CHAr); 1.97–2.41
(4H, m, N(CH2)2); 1.08–1.57 (6H, m, 3CH2)
7.79; 7.83 (4H, td, CHAr), 8.11; 8.02 (4H, dd, CHAr); 3.54–3.7
(4H, m, N(CH2)2); 2.34–2.49 (4H, m, –O(CH2)2)
7.66; 7.58 (4H, td, CHAr), 8.12; 8.06 (4H, dd, CHAr); 7.24–7.54
(5H, m, CHAr); 7.82 (1H, s, NH)
7.68; 7.59 (4H, td, CHAr), 7.97; 8.05 (4H, dd, CHAr); 6.72
(2H, s, NH2); 1.96–2.37 (4H, m, N(CH2)2); 1.08–1.54
(6H, m, 3CH2)
7.77; 7.62 (4H, td, CHAr), 8.11; 8.08 (4H, dd, CHAr); 6.8
(2H, s, NH2); 3.56–3.72
(4H, m, N(CH2)2); 3.56–3.72 (4H, m, –O(CH2)2)
7.79; 7.65 (4H, td, CHAr), 7.99; 8.02 (4H, dd, CHAr); 6.83
1661 (C O), 1350
(tert-N)
1658 (C O), 1355
(tert-N)
3160 ( NH ), 1648
(C O), 1500 (Ar)
1651 (C O), 1358
(tert-N)
C15H16N2SO2
93
23bb
23cb
C14H14N2SO3
124–125
1661 (C O), 1340
(tert-N)
C16H12N2SO2
145
3160 ( NH ), 1660
(C O), 1350 (tert-N),
1510 (Ar)
(2H, s, NH2); 7.24–7.32 (5H, m, CHAr
)
(Continued)

Sulfur-Containing Derivatives of 1,4-Naphthoquinone, Part 2: Sulfenyl Derivative Synthesis 597
TABLE 4 Continued
Formula,
mp ( ◦C)
1H ( δ, ppm)
IR (cm−1
)
24ab
24bb
C19H24N2SO2
78
7.66; 7.78 (4H, td, CHAr), 8.21; 8.11 (4H, dd, CHAr); 3.44–3.49
(4H, m, N(CH2)2); 1.96–2.41 (4H, m, N(CH2)2);
1.44–1.57 (4H, m, –O(CH2)2); 1.12 (6H, s, 2CH3)
7.68; 7.58 (4H, td, CHAr), 8.02; 8.07 (4H, dd, CHAr); 3.57–3.68
(4H, m, –O(CH2)2); 3.48–3.52 (4H, m, N(CH2)2);
2.36–2,47 (4H, m, N(CH2)2); 1.21 (6H, s, 2CH3)
7.66; 7.58 (4H, td, CHAr), 8.06; 8.12 (4H, dd, CHAr); 7.24–7.54
(5H, m, CHAr); 3.48 (4H, q, N(CH2)2); 1.18 (6H, s, 2CH3)
7.47; 7.56 (4H, td, CHAr), 7.98; 8.02 (4H, dd, CHAr); 3.09–3.12
(4H, q, N(CH2)2); 1.96–2.41 (4H, m, N(CH2)2);
1.12–1.35 (8H, q, 4CH2); 0.86–0.91 (6H, m, 2CH3)
7.73; 7.64 (4H, td, CHAr), 8.02; 8.05 (4H, dd, CHAr); 3.09–3.11
(4H, m, N(CH2)2); 2.35–2.47 (4H, m, N(CH2)2);
1.24–1.34 (8H, m, 4CH2); 0.84–0.94 (6H, m, 2CH3);
3.55–3.59 (4H, m, –O(CH2)2)S
7.66; 7.56 (4H, td, CHAr), 8.22; 8.10 (4H, dd, CHAr); 7.24–7.54
(5H, m, CHAr); 3.09–3.11 (4H, q, N(CH2)2); 1.24–1.38
(8H, q, 4CH2); 0.84–0.94 (6H, m, 2CH3)
7.56; 7.62 (4H, td, CHAr), 8.03; 8.07 (4H, dd, CHAr); 1.95–3.2
(8H, m, N(CH2)2); 1.08–1.56 (12H, q, 6CH2)
7.47; 7.65 (4H, td, CHAr), 8.02; 8.06 (4H, dd, CHAr); 3.7–3.83
(4H, m, N(CH2)2); 3.55–3.68 (4H, m, –O(CH2)2);
2.35–2.47 (4H, m, N(CH2)2); 1.29–1.47 (6H, m, 2CH3)
7.98; 8.02 (4H, td, CHAr), 8.06; 8.12 (4H, dd, CHAr); 7.24–7.53
(5H, m, CHAr); 3.73–3.82 (4H, m, N(CH2)2); 1.32–1.4
(6H, m, 2CH3)
7.79; 7.65 (4H, td, CHAr), 8.02; 8.05 (4H, dd, CHAr); 3.55–3.67
(4H, m, N(CH2)2); 3.38–3.45 (4H, m, –O(CH2)2); 1.96–2.3
(4H, m, N(CH2)2); 1.1–1.25 (6H, m, 3CH2)
1654 (C O),
1340(tert-N)
C18H22N2SO3
99–101
1645 (C O), 1355
(tert-N)
24cb
25ab
C20H20N2SO2
116
C23H32N2SO2
91
3170 ( NH ), 1656
(C O), 1590 (Ar)
1651 (C O), 1375
(CH3), 1355 (tert-N)
25bb
25cb
C22H30N2SO3
121
1659 (C O), 1381
(CH3), 1340 (tert-N)
C24H28N2SO2
136
3163 ( NH ), 1660
(C O), 1580 (Ar)
26ab
26bb
C20H24N2SO2
112
C19H22N2SO3
124
1645 (C O), 1360
(tert-N)
1655 (C O), 1351
(tert-N)
26cb
27ab
C21H20N2SO2
126
3160 ( NH ), 1662
(C O), 1500 (Ar)
C19H22N2SO3
89
1652 (C O), 1351
(tert-N)
27bb
27cb
28ab
C18H20N2SO4
114–115
C20H18N2SO3
129
C21H20N2SO2
109
7.73; 7.64 (4H, td, CHAr), 8.02; 8.07 (4H, dd, CHAr); 3.53
1660 (C O), 1340
(tert-N)
1648 (C O), 1500 (Ar),
1351 (tert-N)
3161( NH ), 1650
(C O), 1600 (Ar),
1350 (tert-N)
3175 ( NH ), 1645
(C O), 1580 (Ar),
1340 (tert-N)
3171 ( NH ), 1662
(C O), 1510 (Ar),
3160 ( NH ), 1650
(C O), 1580 (Ar),
1350 (tert-N)
3162 ( NH ), 1660
(C O), 1575 (Ar),
1360 (tert-N)
3175 ( NH ), 1648
(C O), 1575 (Ar)
1650 (C O), 1358
(tert-N)
1658 (C O), 1360
(tert-N)
(16H, m, CH2morpholine
7.73; 7.64 (4H, td, CHAr), 8.11; 8.02 (4H, dd, CHAr); 7.26–7.42
(5H, m, CHAr); 3.49 (8H, m, CH2morpholine
)
)
7.45; 7.51 (4H, td, CHAr), 8.14; 8.09 (4H, dd, CHAr); 7.07–7.3
(5H, m, CHAr); 6.3 (1H, s, NH); 1.96–2.41
(4H, m, N(CH2)2); 1.09–1.52 (6H, m, 3CH2)
7.49; 7.56 (4H, td, CHAr), 8.19; 8.07 (4H, dd, CHAr); 7.08–7.29
(5H, m, CHAr); 6.78 (1H, s, NH); 3.55–3.7
28bb
C20H18N2SO3
123
(4H, m, –O(CH2)2); 2.34–2.46 (4H, m, N(CH2)2)
7.66; 7.56 (4H, td, CHAr), 8.12; 8.05 (4H, dd, CHAr); 7.07–7.54
(10H, m, CHAr); 6.85 (1H, s, NH)
7.68; 7.61 (4H, td, CHAr), 8.22; 8.15 (4H, dd, CHAr); 6.89 (1H,
s, NH); 7.08 (2H, d, CHAr); 7.36 (2H, d, CHAr); 1.96–2.41
(4H, m, N(CH2)2); 1.09–1.52 (6H, m, 3CH2)
7.73; 7.64 (4H, td, CHAr), 8.06; 8.12 (4H, dd, CHAr); 7.75 (1H,
s, NH); 7.08 (2H, d, CHAr); 7.35 (2H, d, CHAr); 3.58–3.67
(4H, m, –O(CH2)2); 2.34–2.49 (4H, m, N(CH2)2)
7.98; 8.02 (4H, td, CHAr), 8.12; 8.05 (4H, dd, CHAr); 7.13–7.54
(9H, m broad, CHAr); 6.98 (1H, s, NH)
7.79; 7.65 (4H, td, CHAr), 7.99; 8.01 (4H, dd, CHAr); 1.96–2.41
(8H, m broad, N(CH2)2); 1.09–1.52 (12H, m broad, 6CH2)
7.41; 7.53 (4H, td, CHAr), 8.17; 8.11 (4H, dd, CHAr); 2.34–2.48
(8H, m broad, N(CH2)2); 3.55–3.68 (8H, m broad,
–O(CH2)2)
28cb
29ab
C22H16N2SO2
141
C21H19N2SO2Cl
116
29bb
C20H17N2SO3Cl
129
29cb
30ab
30bb
C22H15N2SO2Cl
151
C20H24N2S2O2
143
C18H20N2S2O4
164
30cb
C22H16N2S2O2
158
7.63; 7.51 (4H, td, CHAr), 8.10; 8.02 (4H, dd, CHAr); 7.23–7.54
(8H, m broad, CHAr); 6.89 (2H, s broad, NH)
3175 ( NH ), 1661
(C O), 1575 (Ar)
1H NMR solvents: aCHCl3; bDMSO.

598 Stasevych et al.
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Vol. 5, p. 424.
[17] Kuhl, E. The Chemistry of the Sulfenic Acids; Thieme:
Stuttgart, 1973, p. 4; Synthesis 1970, 561; Synthesis
1971, 563, 617.
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