Effective synthesis of n-aryl-substituted 1,5,3-dithiazepinanes and 1,5,3-dithiazocinanes

Article abstract of DOI:10.1007/s10593-012-1098-8

Selective methods were developed for the synthesis of N-aryl-1,5,3- dithiazepinanes and N-aryl-1,5,3-dithiazocinanes by transamination of N-tert-butyl-1,5,3-dithiazepinane or recyclization of 1-oxa-3,6- dithiacycloheptane and 1-oxa-3,7-dithiacyclooctane b

Full text of DOI:10.1007/s10593-012-1098-8

Chemistry of Heterocyclic Compounds, Vol. 48, No. 7, October, 2012 (Russian Original Vol. 48, No. 7, July, 2012)
EFFECTIVE SYNTHESIS OF N-ARYL-SUBSTITUTED
1,5,3-DITHIAZEPINANES AND 1,5,3-DITHIAZOCINANES
E. B. Rakhimova,1* I. V. Vasil'yeva1, L. M. Khalilov1,
A. G. Ibragimov1, and U. M. Dzhemilev1
Selective methods were developed for the synthesis of N-aryl-1,5,3-dithiazepinanes and N-aryl-
1,5,3-dithiazocinanes by transamination of N-tert-butyl-1,5,3-dithiazepinane or recyclization of 1-oxa-
3,6-dithiacycloheptane and 1-oxa-3,7-dithiacyclooctane by the action of aniline derivatives in the
presence of Sm(NO3)3·6H2O catalyst.
Keywords: arylamines, N-aryl-1,5,3-dithiazepinanes, N-aryl-1,5,3-dithiazocinanes, N-tert-butyl-1,5,3-di-
thiazepinane, 1-oxa-3,6-dithiacycloheptane, 1-oxa-3,7-dithiacyclooctane, catalysis, recyclization,
transamination.
Heterocyclic compounds containing nitrogen and sulfur atoms and belonging to the 1,3,5-dithiazinane,
1,3,5-thiadiazinane, and 1,5,3-dithiazepinane systems [1-8] have a set of useful properties [9-14] and are
promising for extensive practical application.
According to data in [15], N-alkyl-1,5,3-dithiazepinanes can be obtained by a three-component
condensation of 1,2-ethanedithiol, formaldehyde, and hydroxylamine or by reaction of 5-(tert-butyl)-2-oxo-
hexahydro-1,3,5-triazine with 1,2-ethanedithiol in the presence of BF3·2AcOH [16]. There are no published data
on the preparation of N-aryl-1,5,3-dithiazepinanes.
In order to develop a new preparative method for the synthesis of N-aryl-1,5,3-dithiazepinanes with
various structures, we investigated the reaction of N-tert-butyl-1,5,3-dithiazepinane and 1-oxa-3,6-dithia-
cycloheptane with isomeric aminophenols, aminothiophenols, and phenylenediamines by analogy with our
previously investigated catalytic transamination of N-methyl-1,3,5-dithiazinane by anilines [17].
Preliminary experiments indicated that among the tested salts and complexes of Fe, Co, Ti, Zr, Ni, Pd,
Sm, and Yb [17] the most active in the catalytic transamination of N-tert-butyl-1,5,3-dithiazepinane with the
above-mentioned arylamines is Sm(NO3)3·6H2O. All the subsequent experiments were therefore conducted with
this catalyst.
We established that under the developed conditions (5 mol% of Sm(NO3)3·6H2O, 20°C, 3 h, EtOH–
CHCl3), o- and p-aminophenols react with an equimolar amount of N-tert-butyl-1,5,3-dithiazepinane (1) or
1-oxa-3,6-dithiacycloheptane (2) with the selective formation of 2- (3) and 4-(1,5,3-dithiazepinan-3-yl)-
_______
*To whom correspondence should be addressed, e-mail: ink@anrb.ru.
1Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, Ufa 450075,
Russia.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1132-1139, July, 2012. Original
article submitted October 18, 2011.
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0009-3122/12/4807-1050©2012 Springer Science+Business Media New York

phenols (4) in yields of 51-85%. Under our chosen reaction conditions, m-aminophenol forms poorly soluble
compounds the identification of which has so far been difficult. In the absence of the catalyst, the selectivity of
the reaction is reduced, and the yield of the desired heterocycles 3 and 4 does not exceed 30%.
In the case of p-aminobenzoic and 5-aminosalicylic acids, we established that they react with an
equimolar amount of N-tert-butyl-1,5,3-dithiazepinane (1) or 1-oxa-3,6-dithiacycloheptane (2) under the
developed conditions, selectively forming 4-(1,5,3-dithiazepinan-3-yl)benzoic acid (5) or 5-(1,5,3-dithi-
azepinan-3-yl)-2-hydroxybenzoic acid (6), respectively, with yields of 57-76%.
NH2
S
S
R
R1
S
N
S
5 mol% Sm(NO3)3·6H2O
EtOH–CHCl3
X
R
1, 2
20°C, 3 h
R1
3–6
1 X = t-BuN; 2 X = O; 3 R = 2-OH, R1 = H; 4 R = 4-OH, R1 = H;
5 R = 4-CO2H, R1 = H; 6 R = 4-OH, R1 = 5-CO2H
In the reaction of p- and o-aminothiophenols with an equimolar amount of the dithiazepinane 1 or
oxadithiacycloheptane 2 under the above-mentioned conditions, 4-(1,5,3-dithiazepinan-3-yl)thiophenol (7) and
1,3,6,8-benzotrithiazecinane (8) are formed with high selectivity and with yields of 48-74%. In the absence of
catalyst this reaction proceeds nonselectively, with low yields of the targeted heterocycles 7 and 8.
1, 2
NH2
SH
NH2
S
H
N
S
S
[Sm]
HS
N
S
S
HS
8
7
1
The H NMR spectra of compounds 3-7 are characterized by broad signals of equal intensity in the
regions of 3.06-3.08 and 4.55-4.86 ppm, belonging to the methylene protons situated between the two sulfur
atoms and between the sulfur and nitrogen atoms, respectively.
The structures of the new N-aryl-1,5,3-dithiazepinanes 3-7 and 1,3,6,8-benzotrithiazecinane (8) were
established unambiguously on the basis of 2D NMR spectroscopy methods (COSY, NOESY, HSQC, HMBC),
and also by MALDI TOF mass spectrometry.
o-Phenylenediamine reacts with compounds 1 and 2 under the same conditions in a molar ratio of 1:2
with the selective formation of 3,3'-(1,2-phenylene)bis-1,5,3-dithiazepinane (9) with yields of 43 and 65%,
respectively. o-Phenylenediamine does not enter into the reaction in the absence of catalyst.
NH2
S
S
S
NH2
S
N
N
1, 2
(2 equiv.)
[Sm]
9
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Under the conditions of the reaction, we could not rule out the possibility of formation of a structural
isomer, the heterocycle 9' (Fig. 1). The choice between the heterocycles 9 and 9' was based on conformation
analysis. Thus, the presence of the o-phenylene bridge between the nitrogen atoms fixes the conformational
rigidity of the probable structure 9', in which the diastereotopic protons of the methylene bond between the
nitrogen and sulfur atoms must be distinguished due to the steric and anisotropic effects of the aromatic ring.
1
The presence of a singlet signal for the methylene group at 4.78 ppm in the H NMR spectrum demonstrates
unambiguously the equivalence of the methylene protons of the N─CH2─S group and the conformational
mobility of the seven-membered fragments of the molecule characteristic of structure 9. Thus, the formation of
3,3'-(1,2-phenylene)bis-1,5,3-dithiazepinane (9) is observed under our chosen conditions.
N
S
N
S
N
S
S
S
N
S
S
S
9'
9
Fig. 1. The structural isomers of the heterocycle 9.
Under the above-mentioned reaction conditions, m-phenylenediamine gives poorly soluble heterocyclic
compounds, while p-phenylenediamine does not enter into the reaction. To activate the N─H bond in
p-phenylenediamine we used the S8+NaOH reagent [18]. The initiating action of the sulfur arises from the fact
that the amine molecule solvates the sulfide ions generated from the sulfur and alkali with the formation of a
charge separation complex. It was found that p-phenylenediamine in the presence of this reagent reacts
effectively with N-tert-butyl-1,5,3-dithiazepinane (1) or 1-oxa-3,6-dithiacycloheptane (2) under the chosen
conditions with selective formation of 3,3'-(1,4-phenylene)bis-1,5,3-dithiazepinane (10) with yields of 45 and
66%.
H2N
NH2
S
S
1, 2
(2 equiv.)
N
N
S8, NaOH
[Sm]
S
S
10
Unlike p-phenylenediamine, 4,4'-diaminodiphenylmethane reacts with compounds 1 or 2 without
previous activation, leading to a selective formation of 3,3'-[methylenebis(1,4-phenylene)]bis-1,5,3-dithiaze-
pinane (11) with yields of 52 and 67%.
H2N
NH2
S
S
N
N
S
S
1, 2
(2 equiv.)
[Sm]
11
The probable mechanism of the catalytic transamination of N-tert-butyl-1,5,3-dithiazepinane (1) or
recyclization of 1-oxa-3,6-dithiacycloheptane (2) with the participation of aniline derivatives includes opening
of the initial heterocycles, nucleophilic addition of arylamines to the carbocation, and intramolecular cyclization
with formation of the desired heterocycles [19-23].
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The obtained results on the synthesis of N-aryl-1,5,3-dithiazepinanes made it possible to undertake
investigations directed at the development of methods for the preparation of N-aryl-1,5,3-dithiazocinanes by
catalytic recyclization of 1-oxa-3,7-dithiacyclooctane (12) with arylamines.
S
:
S
S
S
[Sm]
S
+
S
+
CH2
X
X
X
[Sm]
..
[Sm]
ArNH2
S
+CH2
S
S
S
S
:
S
..
NH
+
NH
–[Sm]
–H2X
N
X
Ar
Ar
Ar
H
[Sm]
X = t-BuN, O; [Sm] = Sm(NO3)3·6H2O
It was established that o- and p-aminophenols, p-aminothiophenol, p-aminobenzoic acid, and 4,4'-di-
aminodiphenylmethane enter into a reaction with 1-oxa-3,7-dithiacyclooctane (12) with the selective formation
of 2- (13) and 4-(1,5,3-dithiazocinan-3-yl)phenols (14), 4-(1,5,3-dithiazocinan-3-yl)thiophenol (15), 4-(1,5,3-di-
thiazocinan-3-yl)benzoic acid (16), and 3,3'-[methylenebis(1,4-phenylene)]bis-1,5,3-dithiazocinane (17). With
using 5 mol% of Sm(NO3)3·6Н2О in these reactions, the highest yields (61-83%) of the targeted heterocycles
13-17 were obtained under the conditions described above (20°C, 3 h, solvent CHCl3–EtOH or CHCl3). In the
absence of catalyst the yield of the targeted heterocycles did not exceed 20%. The structure of the N-aryl-
1
1,5,3-dithiazocinanes 13-17 was established from H and 13C NMR spectra with the use of 2D experiments
(COSY, NOESY, HSQC, HMBC) and also from MALDI TOF mass spectrometry.
S
O
S
12
OH
NH2
NH2
H2N
[Sm]
–H2O
NH2
R
S
S
S
S
OH
N
N
N
N
S
S
S
S
R
13
14, 15, 16
14 R = OH, 15 R = SH, 16 R = COOH
17
Thus, the catalytic transamination of N-tert-butyl-1,5,3-dithiazepinane and recyclization of 1-oxa-3,6-di-
thiacycloheptane and 1-oxa-3,7-dithiacyclooctane with aniline derivatives makes it possible to synthesize
heterocycles of N-aryl-1,5,3-dithiazepinane and N-aryl-1,5,3-dithiazocinane series with high yields and
selectivity.
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EXPERIMENTAL
The one-dimensional (1H, 13C), homonuclear (COSY, NOESY), and heteronuclear (HSQC, HMBC)
1
NMR spectra were recorded on a Bruker Avance 400 spectrometer (400 MHz for H nuclei, 100 MHz for 13C
nuclei) using standard Bruker procedures with TMS as standard. The mixing time for the NOESY experiments
was 0.3 sec. The mass spectra were recorded on a Bruker Autoflex III MALDI TOF/TOF instrument. The
melting points were determined on a RNMK 80/2617 apparatus. Elemental analysis of the samples was
performed on a Carlo Erba 1106 analyzer. The refractive index (nD20) was determined on an IRF-22
refractometer. The reactions were monitored by TLC on Sorbfil plates (PTSKh-AF-V) with development by I2
vapor. Silica gel KSK (100-200 μm) was used for column chromatography.
N-tert-Butyl-1,5,3-dithiazepinane (1). A mixture of a 37% aqueous formalin solution (14.8 ml, 0.2
mol) and 1,2-ethanedithiol (8.3 ml, 0.1 mol) was stirred for 1 h. Then tert-butylamine (10.4 ml, 0.1 mol) was
added to the reaction mixture dropwise, and the mixture was stirred at 20°C for 3 h. The reaction mixture was
extracted with CHCl3, and the extract was evaporated. Yield 12.4 g (65%). The physicochemical and spectral
characteristics of N-tert-butyl-1,5,3-dithiazepinane (1) agree with the published data [16].
1-Oxa-3,6-dithiacycloheptane (2). A mixture of a 37% aqueous formalin solution (14.8 ml, 0.2 mol)
and 1,2-ethanedithiol (8.3 ml, 0.1 mol) was stirred at 20°C for 3 h and extracted with CHCl3. The extract was
evaporated, and 1-oxa-3,6-dithiacycloheptane (2) was isolated. Yield 11.6 g (85%). Crystals, mp 42-44°C
1
(CHCl3). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.98 (4H, br. s, 4,5-СН2); 5.33 (4H, br. s, 2,7-СН2).
13C NMR spectrum (CDCl3), δ, ppm: 32.0 (C-4,5); 66.2 (С-2,7). Found, %: С 35.21; H 5.90; S 47.10. C4H8OS2.
Calculated, %: С 35.27; H 5.92; S 47.07.
Preparation of Compounds 3-11 (General Method). A. Transamination of N-tert-butyl-1,5,3-di-
thiazepinane (1) with aromatic amines: A mixture of N-tert-butyl-1,5,3-dithiazepinane (1) (0.191 g, 1 mmol, or
0.382 g, 2 mmol) (depending on the starting reagent molar ratio) and Sm(NO3)3·6H2O (0.022 g, 0.05 mmol) in
CHCl3 (5 ml) was stirred under an argon atmosphere at room temperature for 30 min, and the corresponding
amine (1 mmol) in EtOH or CHCl3 (5 ml) (depending on the solubility) was then added dropwise. The
p-phenylenediamine was first activated with sulfur and NaOH by the method given in [18] in order to form the
active complex. The reaction mixture was stirred at room temperature for 3 h. Then water (2 ml) was added, the
mixture was stirred for 30 min and extracted with CHCl3 (20 ml). The organic extract was evaporated, and the
residue was chromatographed on a column of SiO2.
B. Recyclization of 1-oxa-3,6-dithiacycloheptane (2) with aromatic amines. The reaction was conducted
similarly to method A, using 1-oxa-3,6-dithiacycloheptane (2) (0.136 g, 1 mmol or 0.272 g, 2 mmol).
2-(1,5,3-Dithiazepinan-3-yl)phenol (3). Yield 0.12 g (51%, method A), 0.17 g (75%, method B).
1
Crystals, mp 82-84°C (CHCl3), Rf 0.9 (Sorbfil, PhMe–EtOAc–Me2CO, 8:1:1). H NMR spectrum (CDCl3), δ,
ppm (J, Hz): 3.08 (4H, br. s, 6',7'-СН2); 4.55 (4H, br. s, 2',4'-СН2); 6.76 (1H, br. s, OH); 6.88 (1H, dd, J = 8.0,
J = 8.0, H-4); 6.97 (1H, d, J = 8.0, H-3); 7.14 (1H, dd, J = 8.0, J = 8.0, H-5); 7.52 (1H, d, J = 8.0, H-6).
13C NMR spectrum (CDCl3), δ, ppm: 38.0 (C-6',7'); 59.3 (C-2',4'); 114.6 (C-3); 120.3 (C-4); 124.6 (C-6); 127.7
(C-5); 136.8 (C-2); 151.6 (C-1). Found, m/z: 228.386 [M+H]+. C10H14NOS2. Calculated, m/z: 228.348. Found,
%: С 52.79; H 5.71; N 6.15; S 28.18. C10H13NOS2. Calculated, %: С 52.83; H 5.76; N 6.16; S 28.21.
4-(1,5,3-Dithiazepinan-3-yl)phenol (4). Yield 0.14 g (60%, method A), 0.20 g (85%, method B).
1
Crystals, mp 91-93°C (CHCl3), Rf 0.8 (Sorbfil, PhMe–EtOAc–Me2CO, 4:1:1). H NMR spectrum (CDCl3), δ,
ppm (J, Hz): 3.08 (4H, br. s, 6',7'-СН2); 4.73 (4H, br. s, 2',4'-СН2); 5.04 (1H, br. s, OH); 6.81 (2H, d, J = 8.0,
H-3,5); 6.89 (2H, d, J = 8.0, H-2,6). 13C NMR spectrum (CDCl3), δ, ppm: 36.0 (C-6',7'); 56.4 (C-2',4'); 116.1
(C-3,5); 118.7 (C-2,6); 140.5 (C-4); 149.8 (C-1). Found, m/z: 227.913 [M]+. C10H13NOS2. Calculated, m/z:
227.348. Found, %: С 52.80; H 5.73; N 6.14; S 28.20. C10H13NOS2. Calculated, %: С 52.83; H 5.76; N 6.16;
S 28.21.
4-(1,5,3-Dithiazepinan-3-yl)benzoic Acid (5). Yield 0.16 g (63%, method A), 0.20 g (76%, method B).
Crystals, mp 240-242°C (CHCl3). 1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 3.07 (4H, br. s, 6',7'-СН2); 4.86
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(4H, br. s, 2',4'-СН2); 6.98 (2H, d, J = 8.0, H-3,5); 7.81 (2H, d, J = 8.0, H-2,6); 12.34 (1H, br. s, COOH). 13C
NMR spectrum (DMSO-d6), δ, ppm: 34.2 (C-6',7'); 53.3 (C-2',4'); 114.9 (C-3,5); 120.6 (C-1); 130.9 (C-2,6);
149.0 (C-4); 167.7 (CООН). Found, m/z: 255.909 [M]+. C11H13NO2S2. Calculated, m/z: 255.358. Found, %:
С 51.69; H 5.10; N 5.44; S 25.07. C11H13NO2S2. Calculated, %: С 51.74; H 5.13; N 5.49; S 25.11.
5-(1,5,3-Dithiazepinan-3-yl)-2-hydroxybenzoic Acid (6). Yield 0.15 g (57%, method A), 0.18 g (67%,
1
method B). Crystals, mp 197-199°C (CHCl3). H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 3.06 (4H, br. s,
6',7'-СН2); 4.75 (4H, br. s, 2',4'-СН2); 6.87 (1H, d, J = 8.0, H-4); 7.21-7.24 (1H, m, H-6); 7.29 (1H, d, J = 8.0, H-
3). 13C NMR spectrum (DMSO-d6), δ, ppm: 34.5 (C-6',7'); 54.9 (C-2',4'); 113.5 (C-1); 116.9 (C-4); 117.8 (C-3);
125.3 (C-6); 138.1 (C-5); 155.1 (C-2); 172.3 (CООН). Found, m/z: 271.218 [M]+. C11H13NO3S2. Calculated,
m/z: 271.357. Found, %: С 48.63; H 4.77; N 5.11; S 23.65. C11H13NO3S2. Calculated, %: С 48.69; H 4.83;
N 5.16; S 23.63.
4-(1,5,3-Dithiazepinan-3-yl)thiophenol (7). Yield 0.11 g (45%, method A), 0.18 g (74%, method B).
1
Crystals, mp >197°C (decomp., CHCl3), Rf 0.8 (Sorbfil, PhMe–EtOAc–Me2CO, 8:1:1), H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 2.76 (1H, br. s, SH); 3.06 (4H, br. s, 6',7'-СН2); 4.76 (4H, br. s, 2',4'-СН2); 6.84 (2H, d,
J = 8.8, H-3,5); 7.43 (2H, d, J = 8.8, H-2,6). 13C NMR spectrum (CDCl3), δ, ppm: 37.7 (C-6',7'); 54.4 (C-2',4');
116.2 (C-3,5); 128.2 (C-4); 132.0 (C-2,6); 145.8 (C-1). Found, m/z: 242.332 [M-H]+. C10H12NS3. Calculated,
m/z: 242.415. Found, %: С 49.30; H 5.35; N 5.71; S 39.55. C10H13NS3. Calculated, %: С 49.34; H 5.38; N 5.75;
S 39.52.
20
1,3,6,8-Benzotrithiazecinane (8). Yield 0.12 g (48%, method A), 0.16 g (62%, method B). Oil, nD
1
1.5145, Rf 0.9 (Sorbfil, CHCl3–hexane, 5:1). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 2.84 (4H, br. s,
4,5-СН2); 4.44 (2H, br. s, 2-СН2); 4.82 (2H, br. s, 7-СН2); 6.49 (1H, d, J = 8.0, H-9); 6.74 (1H, t, J = 7.4, H-10); 6.98
(1H, t, J = 7.6, H-11); 7.08 (1H, d, J = 7.2, H-12). 13C NMR spectrum (CDCl3), δ, ppm: 32.4 (C-4,5); 52.3 (C-2);
55.7 (C-7); 108.7 (C-9); 120.3 (C-11); 122.5 (C-10); 125.6 (C-12); 127.7 (C-12a); 145.7 (C-8a). Found, m/z:
283.265 [M+K+H]+. C10H14KNS3. Calculated, m/z: 283.415. Found, %: С 49.30; H 5.33; N 5.72; S 39.57.
C10H13NS3. Calculated, %: С 49.34; H 5.38; N 5.75; S 39.52.
3,3'-(1,2-Phenylene)bis-1,5,3-dithiazepinane (9). Yield 0.15 g (43%, method A), 0.23 g (65%, method
B). Crystals, 210-212°С (CHCl3), Rf 0.9 (Sorbfil, C6H6–EtOH, 9:1). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz):
3.08 (8H, br. s, 6',6",7',7"-СН2); 4.78 (8H, br. s, 2',2",4',4"-СН2); 7.05-7.07 (2H, m, H-3,6); 7.19-7.22 (2H, m,
H-4,5). 13C NMR spectrum (CDCl3), δ, ppm: 37.3 (C-6',6",7',7"); 56.6 (C-2',2",4',4"); 122.1 (C-4,5); 124.0
(C-3,6); 142.1 (C-1,2). Found, m/z: 345.227 [M+H]+. C14H21N2S4. Calculated, m/z: 345.586. Found, %: С 48.77;
H 5.80; N 8.09; S 37.20. C14H20N2S4. Calculated, %: С 48.80; H 5.85; N 8.13; S 37.22.
3,3'-(1,4-Phenylene)bis-1,5,3-dithiazepinane (10). Yield 0.16 g (45%, method A), 0.23 g (66%,
method B). Crystals, mp 235-236°С (CHCl3), Rf 0.85 (Sorbfil, C6H6–EtOH, 9:1). 1H NMR spectrum (DMSO-d6),
δ, ppm (J, Hz): 3.07 (8H, br. s, 6',6",7',7"-СН2); 4.74 (8H, br. s, 2',2",4',4"-СН2); 7.36 (4H, br. s, H-2,3,5,6).
13C NMR spectrum (DMSO-d6), δ, ppm: 34.5 (C-6',6",7',7"); 54.7 (C-2',2",4',4"); 116.8 (C-2,3,5,6); 141.1
(C-1,4). Found, m/z: 344.269 [M]+. C14H20N2S4. Calculated, m/z: M 344.586. Found, %: С 48.79; H 5.82;
N 8.11; S 37.23. C14H20N2S4. Calculated, %: С 48.80; H 5.85; N 8.13; S 37.22.
3,3'-[Methylenebis(1,4-phenylene)]bis-1,5,3-dithiazepinane (11). Yield 0.23 g (52%, method A), 0.30 g
1
(67%, method B). Crystals, mp 145-147°С (CHCl3), Rf 0.80 (Sorbfil, C6H6–EtOH, 9:1). H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 3.07 (8H, br. s, 6",6'",7",7'"-СН2); 3.87 (2H, br. s, ArCH2Ar); 4.77 (8H, br. s,
2",2'",4",4'"-СН2); 6.87 (4H, d, J = 8.8, H-2,2',6,6'); 7.14 (4H, d, J = 8.8, H-3,3',5,5'). 13C NMR spectrum
(CDCl3), δ, ppm: 35.8 (C-6",6'",7",7'"); 40.1 (ArCH2Ar); 55.2 (C-2",2'",4",4'"); 116.1 (C-2,2',6,6'); 129.6
(C-3,3',5,5'); 133.1 (C-4,4'); 144.0 (C-1,1'). Found, m/z: 457.172 [M+Na]+. C21H26N2S4Na. Calculated, m/z:
457.708. Found, %: С 57.95; H 5.98; N 6.38; S 29.57. C21H26N2S4. Calculated, %: С 58.02; H 6.03; N 6.44; S
29.50.
1-Oxa-3,7-dithiacyclooctane (12). A 37% formalin solution (14.8 ml, 0.2 mol) and 1,3-propanedithiol
(10 ml, 0.1 mol) were placed in a round-bottom flask fitted with a stirrer. The mixture was stirred at 20°C for
3 h. The reaction mixture was extracted with CHCl3, and the extract was evaporated. Yield 8.4 g (55%). Oil,
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nD20 1.5715. 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.88 (2H, br. s, 5-СH2); 2.60 (4H, br. s, 4,6-СН2); 4.59
(4H, br. s, 2,8-СН2). 13C NMR spectrum (CDCl3), δ, ppm: 29.3 (С-5); 29.9 (C-4,6); 79.8 (С-2,8). Found, %:
С 39.92; H 6.68; S 42.72. C5H10OS2. Calculated, %: С 39.97; H 6.71; S 42.68.
1,5,3-Dithiazocinanes 13-17 (General Method). Depending on the molar ratio of the starting reagents,
1-oxa-3,7-dithiacyclooctane (12) (0.15 g, 1 mmol or 0.30 g, 3 mmol) in CHCl3 (5 ml) and Sm(NO3)3·6H2O
(0.022 g, 0.05 mmol) were placed in a Schlenk flask on a magnetic stirrer. The mixture was stirred at ~20°C for
30 min, and the corresponding arylamine (1 mmol) in EtOH or CHCl3 (5 ml) (depending on solubility) was
then added dropwise. The reaction mixture was stirred at ~20°C for 3 h, and H2O (2 ml) was added. The
mixture was stirred for 30 min and extracted with CHCl3 (20 ml). The chloroform fractions were
chromatographed on columns with SiO2.
20
2-(1,5,3-Dithiazocinan-3-yl)phenol (13). Yield 0.15 g (61%). Oil, nD 1.5673, Rf 0.80 (Sorbfil,
1
CHCl3–EtOAc–hexane, 1:5:1). H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.75-1.78 (2H, m, 7'-CH2);
2.54-2.58 (4H, m, 6',8'-CH2); 4.32-4.37 (4H, m, 2',4'-CH2); 6.42 (1H, br. s, ОH); 6.88 (1H, dd, J = 8.0, J = 8.0,
H-4); 6.96 (1H, d, J = 8.0, H-3); 7.11 (1H, d, J = 8.0, H-6); 7.22 (1H, dd, J = 8.0, J = 8.0, H-5). 13C NMR
spectrum (CDCl3), δ, ppm: 29.4 (C-7'); 30.7 (C-6',8'); 55.9 (C-2',4'); 115.0 (C-4); 120.3 (C-3); 125.2 (C-5);
127.4 (C-6); 135.4 (C-2); 151.3 (C-1). Found, m/z: 242.362 [M+H]+. C11H16NOS2. Calculated, m/z: 242.374.
Found, %: С 54.68; H 6.21; N 5.76; S 26.60. C11H15NOS2. Calculated, %: С 54.74; H 6.26; N 5.80; S 26.57.
4-(1,5,3-Dithiazocinan-3-yl)phenol (14). Yield 0.16 g (68%). Oil, nD20 1.6037, Rf 0.85 (Sorbfil, PhMe–
EtOAc–Me2CO, 4:1:1). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.79-1.83 (2H, m, 7'-CH2); 2.72 (4H, t, J = 5.8,
6',8'-CH2); 4.50 (1H, br. s, OH); 4.76 (4H, br. s, 2',4'-CH2); 6.80-6.85 (4H, m, H-2,3,5,6). 13C NMR spectrum
(CDCl3), δ, ppm: 28.9 (C-6',8'); 32.2 (C-7'); 57.0 (C-2',4'); 114.5 (C-3,5); 116.2 (C-2,6); 137.4 (C-4); 148.4
(C-1). Found, m/z: 242.351 [M+H]+. C11H16NOS2. Calculated, m/z: 242.374. Found, %: С 54.70; H 6.21; N
5.78; S 26.59. C11H15NOS2. Calculated, %: С 54.74; H 6.26; N 5.80; S 26.57.
4-(1,5,3-Dithiazocinan-3-yl)thiophenol (15). Yield 0.22 g (83%). Crystals, mp 273-274°С (CHCl3),
1
Rf 0.8 (Sorbfil, PhMe–EtOAc–Me2CO, 8:1:1). H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 1.66-1.69 (2H,
m, 7'-CH2); 2.62 (4H, t, J = 5.8, 6',8'-CH2); 4.85 (4H, br. s, 2',4'-CH2); 6.89 (2H, d, J = 8.8, H-3,5); 7.37 (2H, d,
J = 8.8, H-2,6). 13C NMR spectrum (DMSO-d6), δ, ppm: 28.4 (C-6',8'); 32.40 (C-7'); 55.6 (C-2',4'); 114.7
(C-3,5); 124.6 (C-4); 132.7 (C-2,6); 144.4 (C-1). Found, m/z: 256.251 [M–H]+. C11H14NS3. Calculated, m/z:
256.441. Found, %: С 51.28; H 5.82; N 5.41; S 37.40. C11H15NS3. Calculated, %: С 51.32; H 5.87; N 5.44;
S 37.36.
4-(1,5,3-Dithiazocinan-3-yl)benzoic Acid (16). Yield 0.21 g (76%). Crystals, mp 202-204°С (CHCl3).
1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 1.67-1.69 (2H, m, 7'-CH2); 2.63 (4H, t, J = 5.8, 6',8'-CH2); 4.89
(4H, br. s, 2',4'-CH2); 6.90 (2H, d, J = 8.8, H-3,5); 7.80 (2H, d, J = 8.8, H-2,6); 12.25 (1H, br. s, СООH).
13C NMR spectrum (DMSO-d6), δ, ppm: 27.9 (C-6',8'); 31.8 (C-7'); 55.0 (C-2',4'); 112.9 (C-3,5); 119.8 (C-1);
130.5 (C-2,6); 147.1 (C-4); 167.3 (COOH). Found, m/z: 270.250 [M+H]+. C12H16NO2S2. Calculated, m/z:
270.385. Found, %: С 53.47; H 5.56; N 5.18; S 23.86. C12H15NO2S2. Calculated, %: С 53.50; H 5.61; N 5.20;
S 23.81.
3,3'-[Methylenebis(1,4-phenylene)]bis-1,5,3-dithiazocinane (17). Yield 0.32 g (68%). Crystals, mp
175-176°С (CHCl3), Rf 0.9 (Sorbfil, PhMe–EtOAc–Me2CO, 8:1:1). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz):
1.77-1.83 (4H, m, 7'',7'"-CH2); 2.72 (8H, t, J = 5.8, 6'',6'",8",8'"-CH2); 3.88 (2H, br. s, ArCH2Ar); 4.76 (8H, br.
s, 2",2'",4",4'"-CH2); 6.85 (4H, d, J = 8.4, H-2,2',6,6'); 7.16 (4H, d, J = 8.4, H-3,3',5,5'). 13C NMR spectrum
(CDCl3), δ, ppm: 28.9 (C-6",6'",8",8'"); 32.1 (C-7",7'"); 40.0 (ArCH2Ar); 56.7 (C-2",2'",4",4'"); 113.3
(C-2,2',6,6'); 129.7 (C-3,3',5,5'); 132.0 (C-4,4'); 141.4 (C-1,1'). Found, m/z: 463.175 [M+H]+. C23H31N2S4.
Calculated, m/z: 463.761. Found, %: С 59.65; H 6.49; N 5.96; S 27.79. C23H30N2S4. Calculated, %: С 59.70;
H 6.53; N 6.05; S 27.72.
The work was carried out with financial support from the Russian Foundation for Basic Research
(projects 11-03-00101-a,11-03-97011-r_Povolzh'e_a ).
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