Synthesis of dithiaza- and dioxadithiazacycloalkanes by cyclothiomethylation of arylamines with formaldehyde and α,ω-dithiols

Article abstract of DOI:10.1007/s10593-016-1975-7

New derivatives of 1,5,3-dithiazepanes and macroheterocycles were synthesized by a three-component cyclothiomethylation of arylamines with formaldehyde and α,ω-dithiols. The sorption properties of 3-phenyl-1,5,3-dithiazepane and 6-phenyl-1,11-dioxa-4,8-dithia-6-azacyclotridecane applicable for the extraction of Ag(I) and Pd(II) ions from nitric acid solutions at room temperature were studied by a static method.

Full text of DOI:10.1007/s10593-016-1975-7

DOI 10.1007/s10593-016-1975-7
Chemistry of Heterocyclic Compounds 2016, 52(10), 840–848
Synthesis of dithiaza- and dioxadithiazacycloalkanes by
cyclothiomethylation of arylamines
with formaldehyde and α,ω-dithiols
Guzel R. Khabibullina1*, Ekaterina S. Fedotova1, Ekaterina S. Meshcheryakova1,
Tatyana M. Buslaeva2, Vnira R. Akhmetova1, Askhat G. Ibragimov1
1 Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
141 Oktyabrya Ave., Ufa 450075, Russia; е-mail: khabibguzel@gmail.com
2 M. V. Lomonosov Institute of Fine Chemical Technologies, Moscow Technological University,
78 Vernadskogo Ave., Moscow 119454, Russia; е-mail: buslaevatm@mail.ru
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2016, 52(10), 840–848
Submitted June 10, 2016
Accepted August 21, 2016
New derivatives of 1,5,3-dithiazepanes and macroheterocycles were synthesized by a three-component cyclothiomethylation of
arylamines with formaldehyde and α,ω-dithiols. The sorption properties of 3-phenyl-1,5,3-dithiazepane and 6-phenyl-1,11-dioxa-4,8-
dithia-6-azacyclotridecane applicable for the extraction of Ag(I) and Pd(II) ions from nitric acid solutions at room temperature were
studied by a static method.
Keywords: arylamines, 1,5,3-dithiazepanes, catalysis, cyclothiomethylation, macroheterocycles, multicomponent reaction, sorption of
silver(I) and palladium(II).
Multicomponent1,2 and domino reactions3 are widely
used as tools of organic synthesis, since they are
compatible with the main principles of green chemistry,4
allowing to decrease the number of technological steps and
to reduce waste.
An example of multicomponent reactions is the
cyclothiomethylation of amines with formaldehyde and
H2S in water,5,6 enabling the construction of 1,3,5-
dithiazinanes,7 1,3,5-thiadiazinanes,8 and in the case of
bifunctional amines also fused and macrocyclic
heterocycles.9,10 Some of the heterocycles obtained by the
aforementioned methods have exhibited antifungal11 and
anti-inflammatory activity,12 are used as pharmaceuticals,13
insecticides (buprofezin), herbicides, and bactericides.
Besides that, such compounds are used as transition metal
complexes.14
The objective of this work was to synthesize new
derivatives of dithiaza- and dioxadithiazacycloalkanes by
multicomponent cyclothiomethylation reactions of aryl-
amines with formaldehyde and α,ω-dithiols, to study the
reactivity trends in these processes and to determine the
sorption ability of the obtained compounds.
It was recently shown for the case of amino alcohols19
and carboxylic acid hydrazides20 that, depending on the
structure of the starting α,ω-dithiols, the three-component
cyclothiomethylation followed the scheme of [n+2n+n]
cyclocondensation. The reaction of anilines with 1,2-ethane-
and 1,3-propanedithiols in the presence of Sm and Co
complexes proceeded as a [1+2+1] cyclocondensation.21
In order to expand the range of applicability of these
reactions and to synthesize new types of dithiaza-
cycloalkanes, we studied the reaction of arylamines with
formaldehyde and α,ω-dithiols. This reaction can proceed by
several routes (Scheme 1): route a – intermolecular
cyclocondensation of amines with the formation of two C–N
bonds and two С–S bonds involving one molecule of
amine, two molecules of СН2О, and one molecule of dithiol
according to a [1+2+1] scheme; route b – intermolecular
Dithiazacycloalkanes, in particular 1,5,3-dithiazinanes
and 1,5,3-dithiazepanes, have a strong affinity for binding
iridium(III), iridium(IV),15 platinum(II), platinum(IV),16 and
palladium(II)17 ions from hydrochloric acid and chloride
solutions, as well as silver(I) and mercury(II) from nitric
acid solutions.18
0009-3122/16/52(10)-0840©2016 Springer Science+Business Media New York
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Chemistry of Heterocyclic Compounds 2016, 52(10), 840–848
[2+4+2] cyclocondensation of two amine molecules, four
Nitro derivatives of benzocrown ethers are known to exhibit
high selectivity for the extraction of palladium(II) ions
from hydrochloric acid solutions.22 Based on these data, as
well as in order to extend the practical applicability of
dithiazacycloalkanes, the synthesis of dithiazacycloalkane
nitro derivatives was performed with various functional
substituents in the aromatic ring. It was experimentally
established that the nitro-substituted arylamines 4a–g
readily underwent intermolecular [1+2+1] cycloconden-
sation with СН2О and 1,2-ethanedithiol, forming 1,5,3-di-
thiazepanes 5a–g in 74–93% yields (Scheme 3). Taking
into account the solubility of the starting arylamines, the
synthesis of compounds 5а–e was performed in ethyl acetate,
compound 5f – in chloroform, and compound 5g – in
acetone.
СН2О molecules, and two dithiol molecules forming
heterochain-containing N,S-macroheterocycles; route c –
intermolecular [3+6+3] cyclocondensation.
Scheme 1
Scheme 3
R2
R2
HS
R1
R1
S
S
SH
NH2 + 2 CH2O
N
Solvent
20°C, 3–4 h
4a g
–
5a g
–
Cyclothiomethylation of aniline (1) with formaldehyde
and 1,2-ethanedithiol in 1:2:1 molar ratio of the starting
materials and ~20°С temperature without using solvents
was complete in 3 h and gave 3-phenyl-1,5,3-dithiazepane
(2а) in 77% yield (Scheme 2). 1,3-Propanedithiol and
3,6-dioxa-1,8-octanedithiol participated in a multicom-
ponent reaction with aniline (1) and СН2О under analogous
solvent-free conditions, forming 3-phenyl-1,5,3-dithiazo-
cane (2b) and 6-phenyl-1,11-dioxa-4,8-dithia-6-azacyclotri-
decane (3) in 73 and 70% yields, respectively. Thus, the
multicomponent cyclothiomethylation of aniline (1) with
formaldehyde and 1,2-ethane-, 1,3-propanedithiol, or 3,6-di-
oxa-1,8-octanedithiol under solvent-free conditions followed
the route a with the formation of [1+2+1] cycloconden-
sation products. It should be added that, in contrast to
arylamines, amino alcohols reacted with СН2О and
1,3-propane- or 1,4-butanedithiol according to route b, but
with 4,4'-dimercaptodiphenyloxide – by route c.19
4, 5 a R1 = H, R2 = 2-NO2 (86%); b R1 = H, R2 = 3-NO2 (78%);
1
2
1
2
c
d
R = H, R = 4-NO2 (85%); R = 4-Me, R = 3-NO2 (85%);
e R1 = 2-Me, R2 = 3-NO2 (74%); f R1 = 4-F, R2 = 3-NO2 (93%);
g R1 = 4-OH, R2 = 3-NO2 (86%)
1Н NMR spectra of N-aryl-1,5,3-dithiazepanes 5b–g
featured signals of NCH2S and SCH2CH2 protons as
narrow singlets. A non-equivalence of geminal methylene
protons located between the N and S atoms of dithiazepane
rings was observed in compound 5а, probably due to the
influence of nitro group present at the ortho position, while
the NCH2S protons were observed as two singlets at 4.58
and 4.60 ppm.
Monocrystals of dithiazacycloalkanes 2а,b and 5d,g
were obtained, and their structure was confirmed by X-ray
structural analysis (Fig. 1).
According to the data of X-ray structural analysis, 1,5,3-
dithiazepane ring of compound 2а assumed a "twist-boat"
conformation in the crystal structure, while in compound
5d this ring had a "twist" conformation, and in compound
5g it had a "boat" conformation with the S(1) and S(2)
sulfur atoms deviating from ring plane by –0.864(4) and
–0.788(3) Å, respectively. The 1,5,3-dithiazocane ring in
compound 2b assumed a "twist-chair" conformation. It
should be noted that the N-aryl substituent in
dithiazacycloalkanes 2а,b and 5d,g was axially oriented
relative to the plane of heterocyclic moiety, while in
compounds 2а,b the angle between the average planes of
these rings was equal to 63.835(6) and 69.019(6)°,
respectively. An intramolecular hydrogen bond between
the hydroxy group proton and the oxygen atom of aromatic
nitro group occurred in compound 5g, with the О–Н···О
distance equal to 1.992(5) Å.
Scheme 2
HS
S
S
( )n
SH
PhNH2
1
+
2 CH2O
Ph N
( )n
20°C, 3–4 h
2a n = 1
b n = 2
HS
SH
S
S
O
O
O
2
Ph
N
20°C, 3–4 h
3
The developed one-pot synthesis allowed to obtain
dithiazacycloalkanes 2а,b, 3 in sufficiently high yields
without using solvents and catalysts, which is desirable
according to the principles of green chemistry.
Furthermore, the only by-product in this reaction was
water.
In order to synthesize dithiazacycloalkanes 6a–е, 7а–d
containing heterocycles of various sizes, aliphatic α,ω-di-
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Chemistry of Heterocyclic Compounds 2016, 52(10), 840–848
Figure 1. Molecular structures of compounds 2a,b and 5d,g according to data of X-ray structural analysis, with atoms represented by
thermal vibration ellipsoids of 50% probability.
thiols (1,3-propane-, 1,4-butane-, 1,5-pentane-, 1,6-hexane-,
and 1,8-octanedithiols) were used in reactions
with nitroanilines 4f,g and СН2О.
Scheme 5
HS
SH
O
2
O2N
R
SmCl3·6H2O (5 mol %)
It was found that the reactions with nitroaniline 4f under
the conditions described above (CHCl3, 20°С) gave dithiaza-
cycloalkanes 6a–e in yields that decreased from 73 to 24%
upon increasing the alkyl chain length in the starting α,ω-di-
thiols. A higher yield of the necessary macroheterocyclic
compounds could be obtained by performing the reactions
of nitroanilines 4f,g with α,ω-dithiols in the presence of
SmCl3·6H2O catalyst at 40°С (Scheme 4). Our proposed
reaction conditions allowed to obtain the dithiaza-
cycloalkanes 6a–е and 7а–d in 56–91% yields. The use of
other catalysts (Sm(NO3)3·6H2O, CuCl2·2H2O, FeCl3·6H2O,
NiCl2·6H2O, CoCl2·6H2O) under the same conditions gave
the target compounds 6a–е, 7а–d in 50–68% yields.
+
CHCl3 (for 8a) or
Me2CO (for 8b)
40°C, 3–4 h
NH2
O2N
2 CH2O
4f,g
S
O
R
N
S
8 a R = F
b R = OH
O
The structure of compounds 8а,b was proved by spectral
methods. The protons of NCH2S methylene groups in
compounds 3 and 8а,b gave 1H NMR signals as singlets in
Scheme 4
1
O2N
the upfield region at 5.07–5.13 ppm. A characteristic H
2 CH2O
SmCl3·6H2O (5 mol %)
NMR feature for all compounds 3, 8а,b was the appearance
of SCH2CH2O methylene group protons at 2.66–2.70 and
3.89–3.92 ppm, respectively, as triplets with JHH = 4.5 or
4.6 Hz, and the OCH2CH2O protons as a singlet at 3.68–
3.72 ppm.
R
NH2
HS
+
6a e
– ) or
CHCl3 (for
SH
( )n
Me2CO (for 7a–d)
4f,g
40°C, 3–4 h
Yields, %
Besides that, monocrystals were obtained for
compounds 3 and 8b and X-ray structural analysis was
performed (Fig. 2). It was shown that the 1,11-dioxa-
4,8-dithia-6-azacyclotridecane moiety of compound 3 had a
"chair-twist-chair" conformation, while in compound 8b it
6
7
O2N
S
S
(R = F) (R = OH)
R
N
a (n = 2)
b (n = 3)
90
73
76
71
56
91
67
57
67
–
( )n
6a–e, 7a–d
c
(n = 4)
had
a
"boat-twist-chair" conformation. The N-aryl
d (n = 5)
e (n = 7)
substituents in molecules of compounds 3, 8b occupied an
equatorial position relative to the planes of heterocyclic
moieties. The average ring planes in compounds 3, 8b formed
angles of 21.689(7)° and 51.804(6)°, respectively. The struc-
ture of compound 8b featured an intramolecular О–Н···О
hydrogen bond, the length of which was 1.799(12) Å.
However, despite the substantial differences of geometry
between the considered compounds, their crystals
belonged to the same monoclinic lattice type with Р21/с
space group.
The cyclothiomethylation reaction of arylamines 4f,g
with СН2О and 3,6-dioxa-1,8-octanedithiol in the presence
of SmCl3·6H2O as catalyst enabled the synthesis of new
macroheterocycles 8а,b (Scheme 5). Cyclothiomethylation
of nitroanilines 4f,g was performed depending on the
solubility of the starting compounds either in chloroform
or acetone at 40°С, giving the target compounds 8а,b in 74
and 78% yields.
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Chemistry of Heterocyclic Compounds 2016, 52(10), 840–848
Figure 2. The molecular structures of compounds 3 and 8b according to X-ray structural analysis data, with atoms represented by
thermal vibration ellipsoids of 50% probability.
Considering that palladium(II) ions serve as a soft Lewis
acid according to the Pearson concept and form stable
complexes with S- and S,N-containing molecules, we
estimated the sorption ability of dithiazacycloalkanes 2а
and 3 with respect to Pd(II) and Ag(I) ions in 0.1–4.0 М
HNO3 solutions under static conditions. At НNO3
concentrations of less than 0.1 М palladium(II) nitrates are
not stable,23 but changing the acid concentration in the
range of 0.1–2.0 М did not substantially affect the extent of
presence of SmCl3·6H2O as a catalyst. Analysis by IR and
electronic spectroscopy allowed to establish that the
sorption process from nitric acid solutions involved
complex formation between the palladium ions and
molecules of saturated bicyclic S,N-containing hetero-
cycles, forming metal–nitrogen bonds. It was shown that
the sorption of Pd(II) and Ag(I) ions from aqueous nitric
acid solutions occurred irreversibly, thus the use of
3-phenyl-1,5,3-dithiazepane and 6-phenyl-1,11-dioxa-4,8-di-
thia-6-azacyclotridecane for the concentration of Pd(II)
and Ag(I) ions is of practical value only for analytical
purposes.
palladium(II)
extraction.
Increasing
the
НNO3
concentration to 4.0 М resulted in a lower sorption
capacity. The starting concentration of metal ions was
varied in the range from 4·10–4 to 1.3·10–2 mol/l. It should
be noted that when the Pd(II) ion concentration in the
solution was changed to 10–3 mol/l, the degree of
extraction by compounds 2а and 3 was 100 and 72%, while
the sorption capacity was 0.48 and 0.34 mmol/g,
respectively. At Pd(II) ion concentration of 10–2 mol/l the
values of sorption capacity were 1.76 mmol/g for
compound 2а and 1.37 mmol/g for compound 3.
The difficulty of Pd(II) ion desorption from the sorbent
phase upon treatment with 14% aqueous ammonia and 5%
solution of thiourea in 0.1 М HCl indirectly confirmed that
the sorption process partially involved the formation of
coordination complexes with nitrogen. The sorption
capacity for Ag(I) ions (10–2 mol/l in 0.1 М HNO3) was
equal to 7.40 mmol/g for compound 2а and 3.93 mmol/g
for compound 3, which was lower than in the case of
bisheterocyclic compounds.17,18
Thus, the three-component cyclothiomethylation of
arylamines with formaldehyde and aliphatic α,ω-dithiols
occurred as a [1+2+1] cyclocondensation. Aniline reacted
with СН2О and 1,2-ethane-, 1,3-propanedithiols, as well as
with 3,6-dioxa-1,8-octanedithiol under solvent-free condi-
tions in the absence of a catalyst, giving high yields of
N-phenyl-substituted 1,5,3-dithiazepane, 1,5,3-dithiazocane,
and 6-phenyl-1,11-dioxa-4,8-dithia-6-azacyclotridecane. The
reaction of substituted anilines with СН2О and 1,2-ethane-
dithiol at 20°С provided 1,5,3-dithiazepanes, while α,ω-di-
thiols (1,3-propane-, 1,4-butane-, 1,5-pentane-, 1,6-hexane-,
1,8-octanedithiols and 3,6-dioxa-1,8-octanedithiol) formed
dithiazacycloalkanes and dioxadithiazacyclotridecane in the
Experimental
IR spectra were recorded on a Bruker Vertex 70v
spectrometer. The spectra of oily products (compounds 5e,
6b–e, 7b–d) were recorded for thin films, the spectra of
powders (the rest of the compounds except 5с) – in KBr
pellets, the spectrum of compound 5с – in a Nujol mull.
UV spectra were recorded on a Perkin Elmer Lambda 750
UV/Vis spectrometer in CHCl3 over the wavelength range
of 200–1000 nm, cuvette thickness 0.2 cm. 1Н and
13С NMR spectra were acquired on a Bruker Ascend 500
spectrometer (500 and 125 MHz, respectively, compounds 2a,
3, 5a) and Bruker Avance 400 spectrometer (400 and 100 MHz,
respectively, the rest of the compounds). Homonuclear
1
(NOESY, H–1H COSY) and heteronuclear (1H–13C HSQC,
1H–13C HMBC) 2D NMR spectra of compounds 5f,g, 6a,с,
7b, 8a,b were acquired on a Bruker Ascend 500
1
spectrometer (500 MHz for Н nuclei, 125 MHz for 13С
nuclei). The solvents were DMSO-d6 (compounds 5b,g)
and CDCl3 (the rest of the compounds). Solvent signals
were used as internal standard (DMSO-d6: 2.50 ppm for
1Н nuclei, 39.5 ppm for 13С nuclei; CDCl3: 7.28 ppm for
1Н nuclei, 77.1 ppm for 13С nuclei). 19F NMR spectra
(470 MHz) were acquired on a Bruker Avance 500 spectro-
meter in CDCl3, with СFCl3 as internal standard. Mass
spectra in MALDI-TOF mode were recorded on a Bruker
Autoflex III MALDI-TOF spectrometer, using α-cyano-
4-hydroxycinnamic and 2,5-dihydrobenzoic acid matrices,
the sample was prepared by dried-droplet method with
chloroform (1:10). The mass spectrum of compound 3 in
843

Chemistry of Heterocyclic Compounds 2016, 52(10), 840–848
electrospray ionization mode was recorded on a Shimadzu
Aniline (1) (0.09 ml, 1 mmol) was then added dropwise
and the mixture was stirred at room temperature for 3–4 h.
The product was evaporated on a rotary evaporator and
purified by column chromatography.
LCMS-2010 EV liquid chromato-mass spectrometer (sample
introduction by syringe, 0.1 ml/min, eluent MeCN–H2O,
75:25) in positive and negative ion recording modes at
capillary potentials of 4.5 and –3.5 kV, respectively. The
interface capillary temperature was 250°С, the voltage on the
interface capillary was 25 ÷ –25 V. The nebulizer gas (N2)
flow was 1.5 l/min. The high-frequency lenses (Q-array)
voltage was 5 ÷ –5 V. The elemental composition of С, Н,
and N was determined on a Сarlo Erba 1106 elemental
analyzer. The sulfur content was determined by the
Schoeniger method.24 Melting points were determined with
a RNMK 80/2617 apparatus (Kofler bench). The analysis
of reaction products by gas-liquid chromatography was
performed on a Chrom-5 chromatograph with flame
ionization detector, with SE-30 (5%) stationary phase on
Chromaton N-AW-HMDS support (2400 × 3 mm packed
steel column, temperature program 50–270°С, 8°С/min,
helium as carrier gas). The GC–MS analysis of compounds
5с,d was performed on a Shimadzu GC 2010 gas
chromatograph with GCMS-QP2010 Ultra mass spectral
detector (Shimadzu, Japan) with Supelco 5ms capillary
column (60 m × 0.25 mm × 0.25 μm), helium as carrier
gas. The injector and interface temperatures were 260°С, the
ion source temperature was 200°С. The ionization method was
by electron impact at 70 eV. Individual compounds were
isolated by chromatography on KSK silica gel (50–160 μm).
The eluent used for column chromatography is indicated in
the descriptions of the obtained compounds next to the Rf
values. Analysis by TLC was performed on Silufol W-254
plates, visualization with iodine vapor. The concentration
of palladium(II) in aqueous solutions was determined by
spectrophotometric method with tin(II) chloride on a
KFK-3-01 spectrophotometric colorimeter according to a
published procedure,26 the concentration of silver(I) was
determined titrimetrically, using Volhard method.27
3-Phenyl-1,5,3-dithiazepane (2а).21а Yield 0.17 g
(77%), colorless crystals, mp 42–44°С (hexane–CHCl3,
1:2), Rf 0.78 (hexane–CHCl3, 1:2). UV spectrum, λmax, nm:
1
259.86. Н and 13C NMR spectra were analogous to those
reported in the literature.21а
3-Phenyl-1,5,3-dithiazocane (2b).21а Yield 0.16 g
(73%), colorless crystals, mp 83–85°С (PhH–CHCl3, 1:1),
1
Rf 0.80 (PhH–CHCl3, 1:1). Н and 13C NMR spectra were
analogous to those reported in the literature.21а Found, m/z:
226.476 [М+Н]+. С11Н16NS2. Calculated, m/z: 226.072.
6-Phenyl-1,11-dioxa-4,8-dithia-6-azacyclotridecane (3).
Yield 0.21 g (70%), colorless crystals, mp 102–104°С
(cyclo-C6H12–СН2Сl2, 1:1), Rf 0.48 (cyclo-C6H12–СН2Сl2,
1:1). UV spectrum, λmax, nm: 261.07. IR spectrum, ν, cm–1:
695 (C–S), 755 (C–S–C), 1071 (C–O–C), 1113 (C–N), 1142
(C–O–C), 1205 (C–N), 1270 (C–O–C), 2854 (CH2), 2889
1
(C–H), 2922 (CH2). Н NMR spectrum, δ, ppm (J, Hz):
2.70 (4H, t, J = 4.5, 2SCH2CH2O); 3.72 (4H, s, O(CH2)2O);
3.91 (4H, t, J = 4.5, 2SCH2CH2O); 5.13 (4H, s,
SCH2NCH2S); 6.82–7.31 (5H, m, H Ph). 13C NMR
spectrum,
δ,
ppm:
29.4
(2SCH2CH2O);
55.2
(SCH2NCH2S); 70.3 (O(CH2)2O); 74.8 (2SCH2CH2O);
113.4 (C Ph); 118.3 (C Ph); 129.2 (C Ph); 145.7 (C Ph).
Mass spectrum, m/z (Irel, %): 300 (100) [M+H]+. Found,
m/z: 300.095 [М+Н]+. С14Н22NО2S2. Calculated, m/z: 300.109.
Found, %: С 56.27; Н 6.98; N 4.74; S 21.56. С14Н21NО2S2.
Calculated, %: С 56.15; Н 7.07; N 4.68; S 21.41.
Cyclothiomethylation of nitroanilines 4a–g with
СН2О and 1,2-ethanedithiol (General method). A mixture
of 1,2-ethanedithiol (0.08 ml, 1 mmol) and 37% formalin
(0.15 ml, 2 mmol) was stirred for 30 min at room
temperature. A solution of nitroaniline 4a–g (1 mmol) in
the appropriate solvent (5 ml) (compounds 4а–e – EtOAc,
compound 4f – CHCl3, compound 4g – Me2CO) was added
dropwise and the mixture was stirred for 3–4 h at room
temperature. The product was evaporated on a rotary
evaporator and purified by column chromatography.
The starting arylamines and α,ω-dithiols with ≥98%
assay and aqueous formaldehyde (37% formalin) were
purchased from Acros and used without additional purifi-
cation. Aqueous palladium(II) and silver(I) solutions were
prepared from Pd(NO3)2·2Н2О that was synthesized by a
published procedure,25 AgNO3 of chemically pure grade
(GOST 1277-76, produced by PZCM-Vtormet, Russia) and
HNO3 of chemically pure grade.
IR absorption spectra for solid complexes of compounds
2а and 3 with Pd(II) or Ag(I) ions were recorded for KBr
pellets on a Bruker Eq.55 FT-IR spectrometer over the
range of 200–4000 cm–1. The electronic absorption spectra
for solutions containing complexes of compounds 2а and 3
with Pd(II) or Ag(I) ions were recorded on a Specord
Helios UV-Visible spectrophotometer over the wavelength
range of 200–800 nm, cuvette thickness 1 cm. The diffuse
reflectance spectra (DRS) for solid samples of complexes
formed by compounds 2а and 3 with Pd(II) or Ag(I) ions
were recorded on a Specord М-40 spectrometer.
3-(2-Nitrophenyl)-1,5,3-dithiazepane (5а). Yield 0.22 g
(86%), yellow powder, mp 80–82°С (PhH–Me2CO, 2:1)
(mp 81–83°С21а), Rf 0.90 (PhH–Ме2CO, 2:1). IR spectrum,
ν, cm–1: 579 (C–S), 746 (C–S–C), 881 (C–N), 1124 (C–N),
1151 (C–N), 1456 (CH2), 2854 (CH2), 2926 (CH2). 1Н NMR
spectrum, δ, ppm (J, Hz): 2.89 (4H, s, S(CH2)2S); 4.58 (2H,
s, NCHaxHeqS) and 4.60 (2H, s, NCHaxHeqS); 6.80 (1H, t,
J = 7.5, H Ar); 7.03 (1H, d, J = 8.5, H Ar); 7.53 (1H, t,
J = 7.5, H Ar); 8.22 (1H, d, J = 8.5, H Ar). 13C NMR
spectrum, δ, ppm: 31.2 (S(CH2)2S); 45.8 (SCH2NCH2S);
114.8 (C Ar); 117.0 (C Ar); 127.0 (C Ar); 133.3 (C Ar);
136.1 (C Ar); 143.2 (C Ar). Found, m/z: 255.074 [M–H]+.
C10H11N2O2S2. Calculated, m/z: 255.026. Mass spectrum,
m/z: 280.554 [M+Na+H]+, 255.074 [M–H]+. Found, %:
С 46.77; Н 4.80; N 11.02; S 25.32. C10H12N2O2S2.
Calculated, %: С 46.85; H 4.72; N 10.93; S 25.02.
Cyclothiomethylation of aniline (1) (General method).
A mixture of 1,2-ethanedithiol, 1,3-propanedithiol, or 3,6-dioxa-
1,8-octanedithiol (1 mmol) and 37% formalin (0.15 ml,
2 mmol) was stirred for 30 min at room temperature.
3-(3-Nitrophenyl)-1,5,3-dithiazepane (5b).21а Yield
0.20 g (78%), yellow powder, mp 110–112°С (PhH–
844

Chemistry of Heterocyclic Compounds 2016, 52(10), 840–848
Me2CO, 1:1), Rf 0.93 (PhH–Me2CO, 1:1). IR spectrum,
(CHCl3–EtOАс, 1:1). IR spectrum, ν, cm–1: 590 (C–S), 623
ν, cm–1: 579 (C–S), 623 (C–S), 667 (C–H), 735 (C–S–C), 881
(C–S), 641 (C–S), 735 (C–S–C), 816 (C–H), 1142 (C–N),
–
(C–N), 1105 (C–N), 1135 (C–N), 1222 (C–N), 1244 (C–N),
1219 (C–N), 1240 (C–N), 1276 (C–F), 1346 (NO2 ), 1416
–
–
1275 (C–N), 1346 (NO2 ), 1428 (CH2), 1456 (CH2), 1522
(C–H), 1455 (CH2), 1540 (NO2 ). 1Н NMR spectrum, δ, ppm
–
(NO2 ), 2855 (CH2), 2924 (CH2). 1Н NMR spectrum, δ, ppm
(J, Hz): 3.09 (4H, s, S(CH2)2S); 4.77 (4H, s, SCH2NCH2S);
7.13–7.55 (3H, m, H Ar). 13C NMR spectrum, δ, ppm
(J, Hz): 35.5 (s, S(CH2)2S); 54.8 (s, SCH2NCH2S); 112.0 (d,
(J, Hz): 3.08 (4H, s, S(CH2)2S); 4.91 (4H, s, SCH2NCH2S);
7.40 (1H, d, J = 8.0, H Ar); 7.52 (1H, t, J = 8.2, H Ar); 7.65
(1H, d, J = 8.8, H Ar); 7.70 (1H, s, H Ar). 13C NMR
spectrum, δ, ppm: 34.1 (S(CH2)2S); 53.7 (SCH2NCH2S);
109.9 (C Ar); 113.4 (C Ar); 122.4 (C Ar); 130.4 (C Ar);
146.3 (C Ar); 149.1 (C Ar). Found, m/z: 255.009 [M–H]+.
C10H11N2O2S2. Calculated, m/z: 255.026. Found, %: С 46.91;
Н 4.67; N 10.98; S 24.92. C10H12N2O2S2. Calculated, %:
С 46.85; H 4.72; N 10.93; S 25.02.
2
4JCF = 2.0, C Ar); 118.9 (d, JCF = 102.0, C Ar); 122.3 (d,
3JCF = 7.0, C Ar); 137.4 (s, C Ar); 142.2 (s, C Ar); 149.3 (d,
1JCF = 256.0, C–F). 19F NMR spectrum, δ, ppm: –130.0.
Found, m/z: 273.008 [M–H]+. С10Н10FN2О2S2. Calculated,
m/z: 273.017. Found, %: С 43.69; Н 4.09; N 10.17; S 23.54.
С10Н11FN2О2S2. Calculated, %: С 43.78; H 4.04; N 10.21;
S 23.38.
3-(4-Nitrophenyl)-1,5,3-dithiazepane (5с).21a Yield
0.22 g (85%), yellow powder, mp 148–150°С, Rf 0.93
(PhH–Me2CO, 2:1). IR spectrum, ν, cm–1: 610 (C–S), 754
(C–S–C), 830 (C–H), 1113 (C–N), 1146 (C–N), 1218 (C–N),
1273 (C–N), 1322 (C–N), 1459 (CH2), 2854 (CH2), 2924
4-(1,5,3-Dithiazepan-3-yl)-2-nitrophenol (5g). Yield
0.23 g (86%), red crystals, mp 186–188°С, Rf 0.90 (CHCl3–
EtOH, 2:1). UV spectrum, λmax, nm: 258, 453. IR spectrum,
ν, cm–1: 567 (C–H), 618 (C–S), 681 (C–S), 755
(C–S–C), 817 (C–H), 861 (C–H), 1079 (C–OH), 1200 (C–N),
1227 (C–N), 1251 (C–N), 1304 (CH2), 1423 (CH2), 1531
1
(CH2). Н NMR spectrum, δ, ppm (J, Hz): 3.09 (4H, s,
–
1
S(CH2)2S); 4.84 (4H, s, SCH2NCH2S); 6.90 (2H, d, J = 9.2,
H Ar); 8.20 (2H, d, J = 9.2, H Ar). 13C NMR spectrum,
δ, ppm: 35.4 (S(CH2)2S); 53.6 (SCH2NCH2S); 113.8
(C Ar); 125.7 (C Ar); 139.6 (C Ar); 150.4 (C Ar). Mass
spectrum, m/z (Irel, %): 256 [M]+ (85), 223 [M–SH]+ (48),
106 [C6Н4NHСН3]+ (93), 78 [C6H6]+ (100). Found, %:
С 46.76; Н 4.79; N 10.85; S 25.14. C10H12N2O2S2.
Calculated, %: С 46.85; H 4.72; N 10.93; S 25.02.
(NO2 ), 2854 (CH2), 2924 (CH2), 3083 (=C–H). Н NMR
spectrum, δ, ppm (J, Hz): 3.07 (4H, s, S(CH2)2S); 4.79 (4H,
s, SCH2NCH2S); 7.06 (1Н, d, J = 7.6, H Ar); 7.27 (1H, dd,
1J = 7.4, 2J = 2.4, H Ar); 7.38 (1H, d, J = 2.4, H Ar); 8.31
(1H, s, OH). 13C NMR spectrum, δ, ppm: 34.3 (S(CH2)2S);
54.5 (SCH2NCH2S); 111.3 (C Ar); 120.1 (C Ar); 124.8
(C Ar); 136.9 (C Ar); 138.4 (C Ar); 145.8 (C Ar). Found, m/z:
271.013 [M–H]+. С10Н11N2О3S2. Calculated, m/z: 271.021.
Found, %: С 44.18; Н 4.39; N 10.32; S 23.43.
С10Н12N2О3S2. Calculated, %: С 44.10; H 4.44; N 10.29;
S 23.55.
Cyclothiomethylation of nitroanilines 4f,g with СН2О
and aliphatic α,ω-dithiols (General method). A mixture of
the appropriate α,ω-dithiol (1 mmol) and 37% formalin
(0.15 ml, 2 mmol) was stirred for 30 min at room
temperature. Then a solution of nitroaniline 4f,g (1 mmol)
and SmCl3·6H2O (0.02 g, 5 mol %) in 5 ml of suitable
solvent (compound 4f – CHCl3, compound 4g – Me2CO)
was added dropwise. The mixture was stirred for 3–4 h at
40°С, then evaporated on a rotary evaporator. The product
was purified by column chromatography.
3-(4-Methyl-3-nitrophenyl)-1,5,3-dithiazepane (5d). Yield
0.23 g (85%), yellow crystals, mp 146–148°С, Rf 0.93 (PhH–
EtOAc–Me2CO, 1:2:1). IR spectrum, ν, cm–1: 632 (C–S), 731
–
(C–S–C), 1138 (C–N), 1214 (C–N), 1341 (NO2 ), 1524
(NO2–), 2856 (CH3). 1Н NMR spectrum, δ, ppm (J, Hz): 2.52
(3H, s, CH3); 3.07 (4H, s, S(CH2)2S); 4.77 (4H, s,
SCH2NCH2S); 7.03–7.06 (1H, m, H Ar); 7.24–7.51 (2H,
m, H Ar). 13C NMR spectrum, δ, ppm: 19.6 (CH3); 35.5
(S(CH2)2S); 54.5 (SCH2NCH2S); 111.3 (C Ar); 120.2
(C Ar); 124.1 (C Ar); 133.4 (C Ar); 144.4 (C Ar); 149.6
(C Ar). Mass spectrum, m/z (Irel, %): 270 [M]+ (100), 237
[M–SH]+ (59), 106 [C6Н4NHСН3]+ (73), 78 [C6H6]+ (75).
Found, %: С 48.81; Н 5.17; N 10.28; S 23.79. C11H14N2O2S2.
Calculated, %: С 48.87; Н 5.22; N 10.36; S 23.72.
3-(4-Fluoro-3-nitrophenyl)-1,5,3-dithiazocane (6a).
Yield 0.26 g (90%), yellow powder, mp 125–127°С, Rf 0.80
(PhH–EtOAc, 4:1). IR spectrum, ν, cm–1: 624 (C–S), 705
(C–S), 733 (C–S–C), 812 (C–H), 847 (C–N), 970 (C–H), 1148
3-(2-Methyl-3-nitrophenyl)-1,5,3-dithiazepane (5e).
Yield 0.20 g (74%), yellow oil, Rf 0.85 (PhMe–EtOAc–
Me2CO, 1:2:1). IR spectrum, ν, cm–1: 638 (C–S), 734 (C–S–C),
809 (C–H), 1125 (C–N), 1202 (C–N), 1281 (C–N), 1350
–
–
(C–N), 1241 (C–N), 1282 (C–F), 1350 (NO2 ), 1540 (NO2 ).
1Н NMR spectrum, δ, ppm (J, Hz): 1.83–1.89 (2H, m,
SCH2CH2CH2S); 2.71 (4H, t, J = 5.8, SCH2CH2CH2S); 4.77
(4H, s, SCH2NCH2S); 7.13–7.52 (3H, m, H Ar). 13C NMR
spectrum, δ, ppm (J, Hz): 29.1 (s, SCH2CH2CH2S); 31.9 (s,
SCH2CH2CH2S); 56.7 (s, SCH2NCH2S); 109.6 (d,
–
–
1
(NO2 ), 1468 (CH3), 1525 (NO2 ), 2867 (CH3). Н NMR
spectrum, δ, ppm (J, Hz): 2.45 (3H, s, CH3); 3.12 (4H, s,
S(CH2)2S); 4.62 (4H, s, SCH2NCH2S); 7.32 (1H, t, J = 6.4,
H Ar); 7.63 (1H, d, J = 6.4, H Ar); 7.69 (1H, d, J = 6.4,
H Ar). 13C NMR spectrum, δ, ppm: 14.5 (CH3); 37.6
(S(CH2)2S); 58.9 (SCH2NCH2S); 120.3 (C Ar); 126.7
(C Ar); 127.5 (C Ar); 128.8 (C Ar); 150.7 (C Ar); 151.6
(C Ar). Found, m/z: 269.041 [M–H]+. C11H13N2O2S2.
Calculated, m/z: 269.042. Found, %: С 48.93; Н 5.14;
N 10.28; S 23.63. C11H14N2O2S2. Calculated, %: С 48.87;
Н 5.22; N 10.36; S 23.72.
2
4JCF = 3.0, C Ar); 119.0 (d, JCF = 21.9, C Ar); 119.9 (d,
3JCF = 7.2, C Ar); 137.9 (s, C Ar); 139.9 (s, C Ar); 148.9 (d,
1JCF = 255.7, C–F). Found, m/z: 289.220 [М+Н]+.
С11Н14FN2О2S2. Calculated, m/z: 289.048. Found, %:
С 45.78; Н 4.60; N 9.67; S 22.11. С11Н13FN2О2S2.
Calculated, %: С 45.82; H 4.54; N 9.71; S 22.24.
3-(4-Fluoro-3-nitrophenyl)-1,5,3-dithiazepane
(5f).
3-(4-Fluoro-3-nitrophenyl)-1,5,3-dithiazonane (6b).
Yield 0.22 g (73%), yellow oil, Rf 0.82 (PhH–ЕtOАс, 3:1).
Yield 0.25 g (93%), yellow powder, mp 158–160°С, Rf 0.79
845

Chemistry of Heterocyclic Compounds 2016, 52(10), 840–848
IR spectrum, ν, cm–1: 596 (C–S), 755 (C–S–C), 815 (C–H),
SCH2CH2(CH2)4CH2CH2S);
2.56–2.60
(4H,
m,
1140 (C–N), 1219 (С–N), 1243 (С–N), 1273 (C–F), 1348
SCH2(CH2)6CH2S); 4.63 (4H, s, SCH2NCH2S); 7.18–7.22
(2H, m, H Ar); 7.58–7.59 (1H, m, H Ar). 13C NMR
spectrum, δ, ppm (J, Hz): 28.8 (s, S(CH2)3CH2CH2(CH2)3S);
29.0 (s, S(CH2)2CH2(CH2)2CH2(CH2)2S); 29.8 (s,
SCH2CH2(CH2)4CH2CH2S); 31.6 (s, SCH2(CH2)6CH2S);
54.3 (s, SCH2NCH2S); 111.6 (br. s, C Ar); 118.8 (d,
–
–
(NO2 ), 1418 (C–H), 1454 (CH2), 1538 (NO2 ), 1672
1
(C=C), 2854 (CH2), 3065 (CH2). Н NMR spectrum, δ,
ppm (J, Hz): 1.71 (4H, br. s, SCH2CH2CH2CH2S); 2.56
(4H, br. s, SCH2(CH2)2CH2S); 4.61–4.63 (4H, m,
SCH2NCH2S); 7.18–7.22 (2H, m, H Ar); 7.56 (1H, br. s,
H Ar). 13C NMR spectrum, δ, ppm (J, Hz): 28.8 (s,
SCH2CH2CH2CH2S); 31.1 (s, SCH2(CH2)2CH22S); 54.4 (s,
SCH2NCH2S); 111.7 (br. s, C Ar); 118.9 (d, JCF = 22.0,
C Ar); 122.0 (d, 3JCF = 7.2, C Ar); 137.4 (s, C Ar); 143.0 (s,
2JCF = 17.5, C Ar); 121.8 (d, JCF = 2.2, C Ar); 137.4 (s,
3
C Ar); 143.2 (s, C Ar); 149.1 (d, 1JCF = 205.7, C–F). Found,
m/z: 358.155 [М]+. С16Н23FN2О2S2. Calculated, m/z:
358.118. Found, %: С 53.67; Н 6.54; N 7.75; S 17.76.
С16Н23FN2О2S2. Calculated, %: С 53.61; H 6.47; N 7.81;
S 17.89.
1
C Ar); 149.1 (d, JCF = 257.0, C–F). Found, m/z: 302.202
[M]+. С12Н15FN2О2S2. Calculated, m/z: 302.056. Found, %:
С 47.71; Н 5.07; N 9.19; S 21.33. С12Н15FN2О2S2.
Calculated, %: С 47.66; H 5.00; N 9.26; S 21.21.
4-(1,5,3-Dithiazocan-3-yl)-2-nitrophenol (7a). Yield
0.26 g (91%), red crystals, mp 167–169°С, Rf 0.69 (PhH–
3-(4-Fluoro-3-nitrophenyl)-1,5,3-dithiazecane (6c). Yield
0.23 g (76%), yellow oil, Rf 0.83 (PhH–CH2Cl2–ЕtOAc,
3:1:1). IR spectrum, ν, cm–1: 597 (C–S), 734 (C–S–С), 815
(C–H), 1139 (C–N), 1217 (C–N), 1243 (C–N), 1348 (CH2),
Me2CO,
4:1).
IR
spectrum,
ν,
cm–1:
561
(C–H), 587 (C–S), 669 (C–H), 757 (C–S–C), 821 (C–H),
1077 (C–OH), 1143 (C–N), 1215 (C–N), 1308 (CH2), 1426
(CH2), 1537 (NO2–), 2853 (CH2), 2925 (CH2), 3019 (=C–H).
1Н NMR spectrum, δ, ppm (J, Hz): 1.85 (2H, q, J = 5.8,
SCH2CH2CH2S); 2.72 (4H, t, J = 5.8, SCH2CH2CH2S);
4.77 (4H, s, SCH2NCH2S); 7.16–7.54 (3H, m, H Ar); 10.22
(1H, s, OH). 13C NMR spectrum, δ, ppm (J, Hz): 29.1
(SCH2CH2CH2S); 32.1 (SCH2CH2CH2S); 56.7 (SCH2NCH2S);
107.3 (C Ar); 120.6 (C Ar); 124.3 (C Ar); 133.8 (C Ar);
136.8 (C Ar); 148.5 (C Ar). Found, m/z: 287.095 [М+Н]+.
С11Н15N2О3S2. Calculated, m/z: 287.052. Found, %:
С 46.21; Н 4.87; N 9.84; S 22.23. С11Н14N2О3S2.
Calculated, %: С 46.14; H 4.93: N 9.78; S 22.39.
–
1419 (C–H), 1456 (CH2), 1537 (NO2 ), 2854 (CH2),
1
2925 (CH2). Н NMR spectrum, δ, ppm (J, Hz): 1.49–
1.51 (2H, m, S(CH2)2CH2(CH2)2S); 1.62 (4H, br. s,
SCH2CH2CH2CH2CH2S); 2.51–2.60 (4H, m, SCH2(CH2)3CH2S);
4.62 (4H, s, SCH2NCH2S); 7.17–7.22 (2H, m, H Ar); 7.57 (1H,
br. s, H Ar). 13C NMR spectrum, δ, ppm (J, Hz): 28.0 (s,
S(CH2)2CH2(CH2)2S); 29.4 (s, SCH2CH2CH2CH2CH2S); 31.4
(s, SCH2(CH2)3CH2S); 54.4 (s, SCH2NCH2S); 111.6 (br. s,
2
3
C Ar); 118.9 (d, JCF = 21.9, C Ar); 121.9 (d, JCF = 7.0,
C Ar); 137.3 (s, C Ar); 143.0 (s, C Ar); 149.1 (d,
1JCF
=
256.5, C–F). Found, m/z: 317.333 [M+H]+.
4-(1,5,3-Dithiazonan-3-yl)-2-nitrophenol (7b). Yield
0.20 g (67%), red oil, Rf 0.83 (PhH–Ме2CO, 5:1). IR
spectrum, ν, cm–1: 561 (C–H), 587 (C–S), 669 (C–H), 756
(C–S–C), 822 (C–H), 887 (C–H), 1077 (C–OH), 1142
(C–N), 1215 (C–N), 1308 (CH2), 1426 (CH2), 1537 (NO2 ),
2854 (CH2), 3019 (=C–H). Н NMR spectrum, δ, ppm:
С13Н18N2О2S2. Calculated, m/z: 317.079. Found, %:
С 49.43; Н 5.37; N 8.94; S 20.39. С13Н17N2О2S2.
Calculated, %: С 49.35; H 5.42; N 8.85; S 20.27.
–
3-(4-Fluoro-3-nitrophenyl)-1,5-dithia-3-azacycloundecane
(6d). Yield 0.24 g (71%), yellow oil, Rf 0.88 (PhH–CH2Cl2–
ЕtOAc, 4:1:1). IR spectrum, ν, cm–1: 670 (C–S), 736 (C–S–C),
815 (C–H), 1150 (C–N), 1220 (C–N), 1244 (C–N), 1272
1
1.69 (4H, br. s, SCH2CH2CH2CH2S); 2.56 (4H, br. s,
SCH2(CH2)2CH2S); 4.57–4.60 (4H, m, SCH2NCH2S); 7.08–
7.10 (1H, m, H Ar); 7.28–7.30 (1H, m, H Ar); 7.58 (1H, s,
H Ar); 10.21 (1Н, s, ОН). 13C NMR spectrum, δ, ppm: 28.8
(SCH2CH2CH2CH2S); 31.1 (SCH2(CH2)2CH2S); 54.5
(SCH2NCH2S); 110.5 (C Ar); 120.6 (C Ar); 127.4 (C Ar);
133.5 (C Ar); 140.2 (C Ar); 149.2 (C Ar). Found, m/z:
299.153 [M–H]+. С12Н15N2О3S2. Calculated, m/z: 299.052.
Found, %: С 47.89; Н 5.44; N 9.40; S 21.23. С12Н16N2О3S2.
Calculated, %: С 47.98; H 5.37; N 9.33; S 21.35.
4-(1,5,3-Dithiazecan-3-yl)-2-nitrophenol (7c). Yield
0.18 g (57%), red oil, Rf 0.88 (PhH–Ме2CO, 6:1). IR
spectrum, ν, cm–1: 561 (C–H), 588 (C–S), 669 (C–H), 757
(C–S–C), 822 (C–H), 1077 (C–OH), 1141 (C–N), 1215 (C–N),
1307 (CH2), 1427 (CH2), 1537 (NO2), 2856 (CH2). 1Н NMR
spectrum, δ, ppm: 1.46–1.48 (2H, m, S(CH2)2CH2(CH2)2S);
1.58–1.61 (4H, m, SCH2CH2CH2CH2CH2S); 2.49–2.57 (4H, m,
SCH2(CH2)3CH2S); 4.58 (4H, s, SCH2NCH2S); 7.08–7.10
(1H, m, H Ar); 7.28–7.31 (1H, m, H Ar); 7.58 (1H, s, H Ar);
10.21–10.23 (1H, m, OH). 13C NMR spectrum, δ, ppm: 28.0
(S(CH2)2CH2(CH2)2S); 29.4 (SCH2CH2CH2CH2CH2S); 31.4
(SCH2(CH2)3CH2S); 54.4 (SCH2NCH2S); 110.3 (C Ar); 120.5
(C Ar); 127.3 (C Ar); 133.4 (C Ar); 140.3 (C Ar); 149.2
(C Ar). Found, m/z: 313.143 [М–Н]+. С13Н17N2О3S2.
–
–
(C–F), 1347 (NO2 ), 1420 (C–H), 1458 (CH2), 1537 (NO2 ),
2854 (CH2), 2924 (CH2). 1Н NMR spectrum, δ, ppm: 1.33–
1.40 (4H, m, S(CH2)2CH2CH2(CH2)2S); 1.62 (4H, br. s,
SCH2CH2(CH2)2CH2CH2S); 2.51–2.61 (4H, m, SCH2(CH2)4CH2S);
4.62 (4H, s, SCH2NCH2S); 7.18–7.23 (2H, m, H Ar); 7.57
(1H, br. s, H Ar). 13C NMR spectrum, δ, ppm (J, Hz): 28.4 (s,
S(CH2)2CH2CH2(CH2)2S); 29.7 (s, SCH2CH2(CH2)2CH2CH2S);
31.5 (s, SCH2(CH2)4CH2S); 54.3 (s, SCH2NCH2S); 111.6
2
(br. s, C Ar); 118.9 (d, JCF = 21.9, C Ar); 121.9 (d,
3JCF = 5.7, C Ar); 137.3 (s, C Ar); 143.1 (s, C Ar); 149.1 (d,
1JCF = 255.9, C–F). Found, m/z: 331.225 [М+Н]+.
С14Н20FN2О2S2. Calculated, m/z: 331.095. Found, %:
С 50.96; Н 5.74; N 8.55; S 19.30. С14Н19FN2О2S2.
Calculated, %: С 50.89; H 5.80; N 8.48; S 19.41.
3-(4-Fluoro-3-nitrophenyl)-1,5-dithia-3-azacyclotride-
cane (6e). Yield 0.20 g (56%), yellow oil, Rf 0.88 (PhH–
CH2Cl2–ЕtOAc, 5:1:1). IR spectrum, ν, cm–1: 756 (C–S), 814
(C–H), 1077 (C–N), 1243 (C–N), 1271 (C–F), 1347 (NO2–),
–
1420 (C–H), 1460 (CH2), 1536 (NO2 ), 2853 (CH2), 2925
1
(CH2). Н NMR spectrum, δ, ppm: 1.25–1.30 (4H, m,
S(CH2)3CH2CH2(CH2)3S);
1.34–1.37
(4H,
m,
S(CH2)2CH2(CH2)2CH2(CH2)2S); 1.59–1.62 (4H, m,
846

Chemistry of Heterocyclic Compounds 2016, 52(10), 840–848
Calculated, m/z: 313.068. Found, %: С 49.58; Н 5.84;
J = 4.6, 2SCH2CH2O); 5.07 (4H, s, SCH2NCH2S); 7.07
(1H, d, J = 9.2, H Ar); 7.33–7.34 (1H, m, H Ar); 7.59 (1H,
d, J = 2.8, H Ar); 10.15 (1H, s, OH). 13C NMR spectrum, δ,
ppm: 29.2 (2SCH2CH2O); 55.1 (SCH2NCH2S); 70.2
(OCH2CH2O); 74.8 (2SCH2CH2O); 107.0 (C Ar); 120.3
(C Ar); 124.6 (C Ar); 133.7 (C Ar); 139.5 (C Ar); 148.1
(C Ar). Found, m/z: 359.120 [M–H]+. C14H19N2O5S2.
Calculated, m/z: 359.074. Found, %: С 46.72; Н 5.63;
N 7.69; S 17.65. C14H20N2O5S2. Calculated, %: C 46.65;
H 5.59; N 7.77; S 17.79.
A study of the sorption properties of compounds 2а
and 3. The sorption properties of compounds 2а, 3 were
studied by static method of separately weighed samples at
20 0.5°С temperature at the stirring rate of 800 rpm (MM 2А
magnetic stirrer) and phase contact duration of 20 min for
palladium(II), 60 min for silver(I).
X-ray structural study of compounds 2a,b, 3, 5d,g,
8b. Crystals of compounds suitable for X-ray structural
analysis were obtained by slow evaporation of eluent at
room temperature: compound 2a – n-C6H14–CHCl3, 1:2;
compound 2b – PhH–CHCl3, 1:1; compound 3 – cyclo-
C6H12–СН2Сl2, 1:1; compound 5d – PhH–EtOAc–Me2CO,
1:2:1; compound 5g – CHCl3–EtOH, 2:1; compound 8b –
PhH–CH2Cl2–Ме2CO, 4:1:1. The study was performed on
an Xcalibur Gemini diffractometer, equipped with an Eos
CCD detector (graphite monochromator, MoKα radiation,
λ 0.71073 Å, ω-scanning, 2θmax 62°). The data collection
and processing were performed by using the CrysAlisPro
software from Oxford Diffraction Ltd.28 The structures
were solved by direct method and refined by full-matrix
method of least squares in anisotropic approximation for
non-hydrogen atoms. The hydrogen atoms were localized
by differential Fourier synthesis and refined isotropically.
The calculations were performed with SHELX software.29
The complete X-ray diffraction dataset was deposited at the
Cambridge Crystallographic Data Center (deposits ССDC
1471862 (compound 2a), CCDC 1471855 (compound 2b),
CCDC 1471853 (compound 3), CCDC 1474965
(compound 5d), CCDC 1471945 (compound 5g), and
CCDC 1471852 (compound 8b)).
N 8.85; S 20.52. С13Н18N2О3S2. Calculated, %: С 49.66;
H 5.77; N 8.91; S 20.40.
4-(1,5-Dithia-3-azacycloundecanyl)-2-nitrophenol (7d).
Yield 0.22 g (67%), red oil, Rf 0.88 (PhH–CH2Cl2–Ме2CO,
4:1:1). IR spectrum, ν, cm–1: 561 (C–H), 587 (C–S), 663 (C–S),
672 (C–H), 757 (C–S–C), 822 (C–H), 1076 (C–OH), 1142 (C–N),
1205 (C–OH), 1237 (C–N), 1304 (CH2), 1425 (CH2), 1536 (NO2–),
1
2854 (CH2), 2924 (CH2). Н NMR spectrum, δ, ppm (J, Hz):
1.34–1.35 (4H, m, S(CH2)2CH2CH2(CH2)2S); 1.54–1.57 (4H, m,
SCH2CH2(CH2)2CH2CH2S); 2.47–2.53 (4H, m, SCH2(CH2)4CH2S);
4.57 (4H, s, SCH2NCH2S); 7.07 (1H, d, J = 8.8, H Ar); 7.27 (1H,
d, J = 8.8, H Ar); 7.56 (1H, s, H Ar); 10.19 (1H, s, OH). 13C NMR
spectrum, δ, ppm: 28.4 (S(CH2)2CH2CH2(CH2)2S); 29.7
(SCH2CH2(CH2)2CH2CH2S); 31.5 (SCH2(CH2)4CH2S); 54.4
(SCH2NCH2S); 110.3 (C Ar); 120.5 (C Ar); 127.3 (C Ar);
133.4 (C Ar); 140.3 (C Ar); 149.0 (C Ar). Found, m/z:
329.215 [М+Н]+. С14Н21N2О3S2. Calculated, m/z: 329.099.
Found, %: С 51.27; Н 6.09; N 8.61; S 19.43. С14Н20N2О3S2.
Calculated, %: С 51.20; H 6.14; N 8.53; S 19.52.
Cyclothiomethylation of nitroanilines 4f,g with СН2О
and 3,6-dioxa-1,8-octanedithiol (General method). A
mixture of 3,6-dioxa-1,8-octanedithiol (0.16 ml, 1 mmol)
and 37% formalin (0.15 ml, 2 mmol) was stirred for 30 min
at room temperature. Then a solution of nitroaniline 4f,g
(1 mmol) and SmCl3·6H2O (0.02 g, 5 mol %) in 5 ml of
suitable solvent (compound 4f – CHCl3, compound 4g –
Me2CO) was added dropwise. The mixture was stirred for 3–
4 h at 40°С, the product was then evaporated on a rotary
evaporator and purified by column chromatography.
3-(4-Fluoro-3-nitrophenyl)-1,11-dioxa-4,8-dithia-6-aza-
cyclotridecane (8a). Yield 0.27 g (74%), yellow powder,
mp 114–117°С, Rf 0.76 (PhH–ЕtOAc, 1:2). IR spectrum, ν,
cm–1: 549 (C–H), 592 (C–S), 686 (C–S), 707 (C–H), 756
(C–S–C), 807 (C–H), 1072 (C–O–C), 1112 (C–N), 1138
–
(C–O–C), 1215 (C–N), 1245 (NO2 ), 1266 (C–O–C),
–
1281 (C–F), 1349 (NO2 ), 1386 (O–H), 1422 (C–OH),
1450 (CH2), 1539 (NO2–). 1Н NMR spectrum, δ, ppm (J, Hz):
2.69 (4H, t, J = 4.6, 2SCH2CH2O); 3.71 (4H, s,
OCH2CH2O); 3.92 (4H, t, J = 4.6, 2SCH2CH2O); 5.11 (4H,
s, SCH2NCH2S); 7.15–7.22 (2H, m, H Ar); 7.60–7.62 (1H,
m, H Ar). 13C NMR spectrum, δ, ppm (J, Hz): 29.2
(2SCH2CH2O); 55.0 (SCH2NCH2S); 70.2 (OCH2CH2O);
This work was performed with financial support from
the Russian Foundation for Basic Research (projects No.
14-03-00240-а, No. 14-03-97023-r_Povolzhye_a) and the
Ministry of Education and Science of the Russian
Federation (grant NSh-6651.2016.3).
4
74.8 (2SCH2CH2O); 109.5 (d, JCF = 2.2, C Ar); 118.7 (d,
3
2JCF = 17.4, C Ar); 119.8 (d, JCF = 5.5, C Ar); 137.5 (d,
J
CF = 6.1, C Ar); 142.5 (s, C Ar); 148.5 (d, 1JCF = 203.6, C Ar).
19F NMR spectrum, δ, ppm: –132.9. Found, m/z: 361.039
[М–Н]+. С14Н18FN2О4S2. Calculated, m/z: 361.069. Found, %:
С 46.45; Н 5.22; N 7.81; S 17.76. С14Н19FN2О4S2.
Calculated, %: C 46.39; H 5.28; N 7.73; S 17.69.
The structural studies of compounds were performed at
the Collective Usage Center "Agidel" at the Institute of
Petrochemistry and Catalysis of the Russian Academy of
Sciences.
4-(1,11-Dioxa-4,8-dithia-6-azacyclotridecanyl)-2-nitro-
phenol (8b). Yield 0.28 g (78%), red powder, mp 126–
129°С, Rf 0.90 (PhH–CH2Cl2–Ме2CO, 4:1:1). IR spectrum,
ν, cm–1: 561 (C–H), 585 (C–S), 649 (C–S), 756 (C–S–C),
821 (C–H), 847 (C–N), 1075 (C–OH), 1114 (C–N), 1140
(C–O–C), 1206 (C–N), 1237 (C–N), 1280 (C–O–C), 1349
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