Synthesis of N-Aryl-1,5,3-dithiazepanes and N-Aryl-1,5,3-dithiazocanes in the presence of samariumand cobalt-containing catalysts

Article abstract of DOI:10.1134/S1070428012040215

Efficient procedures were developed for the synthesis of N-aryl-1,5,3-dithiazepanes and N-aryl- 1,5,3-dithiazocanes by cyclocondensation of anilines with formaldehyde and α,ω-dithiols (etane-1,2-dithiol and propane-1,3-dithiol), as well as by transaminati

Full text of DOI:10.1134/S1070428012040215

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 4, pp. 588–593. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © N.N. Murzakova, K.I. Prokof’ev, T.V. Tyumkina, A.G. Ibragimov, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48,
No. 4, pp. 590–595.
Synthesis of N-Aryl-1,5,3-dithiazepanes
and N-Aryl-1,5,3-dithiazocanes in the Presence of Samarium-
and Cobalt-Containing Catalysts
N. N. Murzakova, K. I. Prokof’ev, T. V. Tyumkina, and A. G. Ibragimov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: natali-mnn@mail.ru
Received October 22, 2011
Abstract—Efficient procedures were developed for the synthesis of N-aryl-1,5,3-dithiazepanes and N-aryl-
1,5,3-dithiazocanes by cyclocondensation of anilines with formaldehyde and α,ω-dithiols (etane-1,2-dithiol and
propane-1,3-dithiol), as well as by transamination of N-tert-butyl-1,5,3-dithiazepane or N-tert-butyl-1,5,3-di-
thiazocane with aromatic amines in the presence of samarium and cobalt complexes.
DOI: 10.1134/S1070428012040215
One of the most widely known and simplest
procedures for the synthesis of practically important
[1–3] heterocycles of the dithiazinane series is based
on classical [4] cyclocondensation of primary amines
with hydrogen sulfide and formaldehyde [5–10]. Pub-
lished data on the synthesis of bicyclic [11–15] and
N-substituted dithiazepanes [16, 17] are considerably
scantier. Ito and Sekiya [16] reported on the synthesis
of N-hydroxy-1,5,3-dithiazepane (I) by cyclocondensa-
tion of hydroxylamine hydrochloride with ethane-1,2-
dithiol and formaldehyde. Another approach to the
synthesis of dithiazepane II is based on recyclization
of 5-tert-butylhexahydro-1,3,5-triazin-2-one with
ethane-1,2-dithiol in the presence of BF3·2HOAc [17]
(Scheme 1). There are almost no data on preparative
procedures for the synthesis of N-aryl-1,5,3-dithiaz-
epanes and N-aryl-1,5,3-dithiazocanes.
(ethane-1,2-dithiol and propane-1,3-dithiol). We ex-
amined in detail the effects of the solvent nature,
reactant ratio, temperature, and reaction time on the
yield of cyclocondensation products from aniline,
formaldehyde, and ethane-1,2-dithiol. Aniline reacted
with CH2O and ethane1,2-dithiol at a molar ratio of
1 : 2 : 1 in chloroform at 20°C to give ~65% of
N-phenyl-1,5,3-dithiazepane (IIIa) in 6 h (Scheme 2).
With a view to improve the yield of IIIa, the reaction
was carried out in the presence of Cu, Co, Mn, Ti, Hf,
V, Fe, Sm, and Ni salts and complexes, which were
used by us previously [18] to catalyze the synthesis of
N-substituted 1,3,5-dithiazinanes. Among the exam-
ined catalysts, only Sm(NO3)3 ·6H2O ensured forma-
tion of heterocycle IIIa in 88% yield in 0.5 h (see
table). Therefore, all subsequent heterocyclizations of
anilines with formaldehyde and ethane-1,2-dithiol
were carried out in the presence of 5 mol % of
Sm(NO3)3·6H2O as catalyst.
Taking into account the data of [16, 17], we tried to
synthesize N-aryl-1,5,3-dithiazepanes and N-aryl-
1,5,3-dithiazocanes by cyclocondensation of primary
aromatic amines with formaldehyde and α,ω-dithiols
Under analogous conditions [5 mol % of Sm(NO3)3·
6H2O, 20°C, 0.5 h, CHCl3 as solvent] heterocycliza-
Scheme 1.
H
N
O
S
S
S
N
NH
HONH2 ·HCl, CH2O
t-Bu
SH
N
OH
N
Bu-t
HS
S
I
II
588

SYNTHESIS OF N-ARYL-1,5,3-DITHIAZEPANES AND N-ARYL-1,5,3-DITIAZOCANES
589
Scheme 2.
S
S
NH2
R
[Co], 20°C
SH
R
+
+
2CH2O
N
( )n
HS
( )n
IIIa–IIIi, n = 1; IVa–IVi, n = 2
R = H (a), 3-Me (b), 4-Me (c), 2-MeO (d), 3-MeO (e), 4-MeO (f), 2-O2N (g), 3-O2N (h), 4-O2N (i).
tion of m- and p-toluidines with formaldehyde and
ethane-1,2-dithiol gave 3-(3- and 4-methylphenyl)-
1,5,3-dithiazepanes IIIb and IIIc in 73 and 79% yield,
respectively. Likewise, from o-, m-, and p-methoxy-
anilines we obtained 59–87% of the corresponding
3-(methoxyphenyl)-1,5,3-dithiazepanes IIId–IIIf. The
cyclocondensation with isomeric nitroanilines afforded
68–79% of N-(nitrophenyl) derivatives IIIg–IIIi.
We also tried to elucidate the possibility for selec-
tive synthesis of 1,5,3-dithiazocane derivatives by
analogous reaction. For this purpose, propane-1,3-di-
thiol was involved in catalytic heterocyclization with
aromatic amines and formaldehyde. The reaction of
aniline with CH2O and propane-1,3-dithiol (1:2:1) at
room temperature in the absence of a catalyst gave
10% of a product which was identified as 3-phenyl-
1,5,3-dithiazocane (IVa). The yield of IVa was im-
proved to 48% using 5 mol % of Sm(NO3)3·6H2O as
catalyst (CHCl3, 3 h, 20°C). The best results were
obtained with the use of Co(acac)2 which ensured
formation of 66% of compound IVa in 3 h at 20°C.
Under analogous conditions, heterocyclizations of
m- and p-toluidines, o-, m-, and p-methoxyanilines,
and o-, m-, and p-nitroanilines with formaldehyde and
propane-1,3-dithiol selectively produced the corre-
sponding N-aryl-1,5,3-dithiazocanes IVb–IVi in 69–
95% yield (Scheme 2).
1
In the H NMR spectrum of IIIa, signals from
protons on C2 and C4 appeared as sharp singlets at
δ 4.80 ppm, while the 6-H and 7-H protons resonated
at δ 3.08 ppm, indicating fast ring inversion on the
NMR time scale. The 13C NMR spectrum contained
signals at δC 54.92 and 35.78 ppm due to carbon atoms
in the dithiazepane ring.
We presumed that N-aryl-1,5,3-dithiazepanes III
are obtained in the cyclocondensation with ethane-
1,2-dithiol and formaldehyde via initial formation of
1,3,6-oxadithiepane which then undergoes recycliza-
tion by the action of aromatic amine in the presence of
the selected catalyst. This assumption was verified by
reacting 1,3,6-oxadithiepane with aniline, m-toluidine,
o-methoxyaniline, and p-nitroaniline in the presence of
Sm(NO3)3 ·6H2O (reactant molar ratio 10 :10 :0.5,
20°C, CHCl3, 3 h). In all cases, the corresponding
N-aryl-1,5,3-dithiazepanes IIIa, IIIb, IIId, and IIIi
were formed in 74, 76, 70, and 82% yield, respectively,
which was confirmed by NMR data. In the 13C NMR
spectrum of 1,3,6-oxadithiepane carbon atoms in the
SCH2CH2S fragment resonated at δC 31.90 ppm, and
the SCH2O carbon signal appeared at δC 66.17 ppm.
After addition of an equimolar amount of aniline con-
taining 5 mol % of Sm(NO3)3·6H2O, signals assigned
to 1,3,6-oxadithiepane disappeared from the 13C NMR
spectrum, and those typical of 1,5,3-dithiazepanes ap-
peared instead at δC 35.27 and 54.52 ppm. Presumably,
catalytic opening of the oxadithiepane ring under the
conditions given in [17–19] is followed by nucleo-
philic addition of aromatic amine to the carbenium ion
thus generated, leading to complex B through interme-
diate A. In the final step, intramolecular cyclization
yields N-aryl-1,5,3-dithiazepane (Scheme 3).
The 1H NMR spectrum of compound IVa contained
a triplet at δ 2.74 ppm due to protons on C6 and C8,
methylene protons on C2 and C4 gave a sharp singlet at
δ 4.78 ppm, and protons on C7 resonated as a multiplet
at δ 1.79 ppm.
In continuation of our previous study on the syn-
thesis of N-aryl-1,3,5-dithiazinanes by catalytic trans-
amination of N-methyl-1,3,5-dithiazinane with aromat-
ic amines [18], we examined analogous transamination
of N-tert-butyl-1,5,3-dithiazepane with anilines in the
presence of catalysts based on transition and rare-earth
Yields of N-phenyl-1,5,3-dithiazepane (IIIa) in the reaction
of aniline with formaldehyde and ethane-1,2-dithiol (reac-
tant ratio 1:2:1) in the presence of different catalysts
(5 mol %; 20°C, 0.5 h, CHCl3)
Catalyst
IIIa, %
Catalyst
IIIa, %
Sm(NO3)3·6H2O
Cp2TiCl2
88
75
72
70
66
MnCl2
59
52
49
45
07
Cp2HfCl2
VO(acac)2
NiCl2
CuCl2
FeCl3 ·6H2O
CoCl2
No catalyst
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

MURZAKOVA et al.
590
Scheme 3.
S
S
SH
+
2CH2O
O
HS
–H2O
MLn
S
S
ArNH2
MLn
S
LnM
S
O
MLn
S
O
O
S
CH2
H2C
S
S
S
S
S
H
CH2
N
Ar
H
–H2O, –MLn
O
N
H
N
S
MLn
Ar
Ar
A
B
III
M = Sm, Ti, Cu, Co, Mn, Hf, V, Ni.
Scheme 4.
S
S
NH2
R
[M]
R
+
t-Bu
N
N
( )n
–t-BuNH2
( )n
S
S
IIIa, IIIb, IIIe, IIIh, n = 1
IVa, IVb, IVe, IVh, n = 2
R = H (a), 3-Me (b), 3-MeO (e), 3-O2N (h).
metals with a view to develop a new selective proce-
dure for the synthesis of N-aryl-1,5,3-dithiazepanes
(Scheme 4).
N-tert-butyl-1,5,3-dithiazocane with aniline, m-tolu-
idine, m-methoxyaniline, and m-nitroaniline in the
presence of Sm(NO3)3·6H2O (20°C, 3 h, CHCl3).
Preliminary experiments showed that the reaction
of aniline with an equimolar amount of N-tert-butyl-
1,5,3-dithiazepane without a catalyst (CHCl3, 20°C,
3 h) leads to the formation of N-phenyl-1,5,3-dithiaz-
epane (IIIa) in a poor yield (~8%). To raise the yield
of compound IIIa, the reaction was carried out in the
presence of Cu, Pd, Co, Zr, Ti, Hf, V, Fe, and Sm salts
and complexes [18]. Among the examined catalysts,
Sm(NO3)3·6H2O (5 mol %) revealed the highest cata-
lytic activity, and N-phenyl-1,5,3-dithiazepane (IIIa)
was obtained in 78% yield. Under the developed con-
ditions [5 mol % of Sm(NO3)3 · 6 H2O, 20°C, 3 h,
CHCl3], m-toluidine and m-methoxyaniline reacted
with N-tert-butyl-1,5,3-dithiazepane to produce
N-(3-methylphenyl)- and N-(3-methoxyphenyl)-1,5,3-
dithiazepanes IIIb and IIIe in 70 and 73% yield,
respectively. Likewise, the transamination of N-tert-
butyl-1,5,3-dithiazepane with m-nitroaniline selec-
tively afforded 64% of N-(3-nitrophenyl)-1,5,3-dithia-
zepane (IIIh). The same procedure was successfully
used to synthesize difficultly accessible N-aryl-1,5,3-
dithiazocanes IV (yield 63–86%) by transamination of
EXPERIMENTAL
The progress of reactions was monitored by TLC
on Silufol UV-254 plates; spots were developed with
iodine vapor. The products were analyzed by HPLC on
an Altex-330 chromatograph (USA) equipped with
a UV detector (λ 340 nm). The 1H and 13C NMR spec-
tra were recorded on a Bruker Avance 400 spectrom-
eter at 400.13 and 100.62 MHz, respectively, from
solutions in CDCl3 using standard Bruker procedures.
GC–MS analysis was performed on Finnigan-4021
(HP-5 glass capillary column, 50 m×0.25 mm; carrier
gas helium; oven temperature programming from 50 to
300°C at a rate of 5 deg/min, injector temperature
280°C; ion source temperature 250°C; electron impact,
70 eV) and Shimadzu QP-2010Plus instruments
(Supelco PTE-5 capillary column, 30 m×0.25 mm).
Silica gel KSK (100–200 μm) was used for column
chromatography; eluent hexane–chloroform–ethyl
acetate (5:1:1).
N-Aryl-1,5,3-dithiazepanes and N-aryl-1,5,3-di-
thiazocanes (general procedures). a. Cyclocondensa-
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SYNTHESIS OF N-ARYL-1,5,3-DITHIAZEPANES AND N-ARYL-1,5,3-DITIAZOCANES
591
tion of aromatic amines with formaldehyde and
ethane-1,2-dithiol or propane-1,3-dithiol. A Schlenk
flask equipped with a magnetic stirrer was charged at
20°C under argon with 20 mmol of formaldehyde and
10 mmol of ethane-1,2-dithiol or propane-1,3-dithiol,
the mixture was stirred for 30 min, 5 ml of chloroform,
0.5 mmol of Sm(NO3)3 ·6H2O, and 10 mmol of the
corresponding aromatic amine were added, and the
mixture was stirred for 30 min at 20°C.
CH3), 4.53 s (4H, CH2), 6.67–7.87 m (4H, Harom).
13C NMR spectrum, δC, ppm: 33.48 (C6, C7), 53.66
(C15), 58.93 (C2, C4), 111.35 (C11), 115.76 (C13), 123.05
(C10), 128.96 (C12), 144.78 (C9), 147.20 (C8). Found,
%: C 54.13; H 6.09; N 5.59; S 26.05. C11H15NOS2.
Calculated, %: C 54.74; H 6.26; N 5.80; S 26.57.
3-(3-Methoxyphenyl)-1,5,3-dithiazepane (IIIe).
1
Yield 89%, Rf 0.77, mp 109–110°C. H NMR spec-
trum, δ, ppm: 2.61–2.73 m (4H, CH2), 3.42 s (3H,
CH3), 4.47 s (4H, CH2), 6.71–7.53 m (4H, Harom).
13C NMR spectrum, δC, ppm: 33.95 (C6, C7), 52.00
(C15), 60.97 (C2, C4), 109.89 (C11), 112.43 (C12),
119.97 (C13), 124.77 (C9), 144.55 (C10), 147.32 (C8).
Mass spectrum, m/z (Irel, %): 241 (20) [M]+, 77 (70)
[C6H5]+, 106 (40) [C7H6O]+, 120 (100) [C7H6ON]+,
135 (60) [C8H9NO]+, 180 (10) [C9H11NOS]+, 208 (80)
[C11H15NOS]+. Calculated: M 241.37.
b. Transamination of N-tert-butyl-1,5,3-dithiazep-
ane or N-tert-butyl-1,5,3-dithiazocane with aromatic
amines. A Schlenk flask equipped with a magnetic
stirrer was charged under argon with 10 mmol of
N-tert-butyl-1,5,3-dithiazepane or N-tert-butyl-1,5,3-
dithiazocane, 5 ml of chloroform, 0.5 mmol of
Sm(NO3)3·6H2O, and 10 mmol of the corresponding
amine were added, and the mixture was stirred for
3 h at 20°C.
3-(4-Methoxyphenyl)-1,5,3-dithiazepane (IIIf).
1
3-Phenyl-1,5,3-dithiazepane (IIIa). Yield 88%,
Yield 79%, Rf 0.62, mp 118–120°C. H NMR spec-
1
Rf 0.44, mp 99–100°C. H NMR spectrum, δ, ppm:
trum, δ, ppm: 2.64–2.81 m (4H, CH2), 3.51 s (3H,
CH3), 4.39 s (4H, CH2), 6.59–7.12 m (4H, Harom).
13C NMR spectrum, δC, ppm: 34.28 (C6, C7), 51.93
(C15), 59.99 (C2, C4), 113.33 (C9, C13), 125.07 (C10,
C12), 143.98 (C11), 148.01 (C8). Found, %: C 54.33;
H 6.18; N 5.47; S 26.38. C11H15NOS2. Calculated, %:
C 54.74; H 6.26; N 5.80; S 26.57.
3.08 s (4H, CH2), 4.80 s (4H, CH2), 6.91–7.35 m (5H,
H
arom). 13C NMR spectrum, δC, ppm: 35.78 (C6, C7),
54.92 (C2, C4), 115.93 (C9, C13), 119.95 (C11), 129.30
(C10, C12), 145.83 (C8). Mass spectrum, m/z (Irel, %):
211 (12) [M]+, 77 (10) [C6H5]+, 91 (15) [C6H5N]+, 137
(100) [C7H7NS]+, 165 (95) [C9H12NS]+. Found, %:
C 56.46; H 6.10; N 6.24; S 30.15. C10H13NS2. Calcu-
lated, %: C 56.83; H 6.20; N 6.63; S 30.34. M 211.35.
3-(2-Nitrophenyl)-1,5,3-dithiazepane (IIIg). Yield
1
67%, Rf 0.65, mp 81–83°C. H NMR spectrum, δ,
3-(3-Methylphenyl)-1,5,3-dithiazepane (IIIb).
Yield 72%, Rf 0.64, mp 121–123°C. H NMR spec-
ppm: 2.66–2.99 m (4H, CH2), 4.46 s (4H, CH2), 6.67–
7.87 m (4H, Harom). 13C NMR spectrum, δC, ppm:
34.51 (C6, C7), 59.65 (C2, C4), 110.55 (C11), 114.71
(C13), 122.45 (C10), 129.01 (C12), 145.92 (C9), 147.20
(C8). Mass spectrum, m/z (Irel, %): 256 (20) [M]+, 122
(70) [C6H4NO2]+, 136 (40) [C6H4N2O2]+, 181 (100)
[C7H8N2O2S]+, 210 (100) [C9H10N2O2S]+. Calculated:
M 256.35.
1
trum, δ, ppm: 2.38 s (3H, CH3), 3.10 s (4H, CH2),
4.81 s (4H, CH2), 6.79–7.23 m (4H, Harom). 13C NMR
spectrum, δC, ppm: 21.83 (CH3), 35.91 (C6, C7), 55.06
(C2, C4), 112.29 (C13), 116.69 (C9), 120.93 (C11),
129.08 (C10), 138.90 (C12), 145.95 (C8). Mass spec-
trum, m/z (Irel, %): 225 (12) [M]+, 91 (70) [C7H7]+, 106
(100) [C7H8N]+, 119 (100) [C8H9N]+, 165 (40)
[C11H14NS]+. Calculated: M 225.38.
3-(3-Nitrophenyl)-1,5,3-dithiazepane (IIIh). Yield
1
79%, Rf 0.68, mp 76–78°C. H NMR spectrum, δ,
3-(4-Methylphenyl)-1,5,3-dithiazepane (IIIc).
Yield 70%, Rf 0.75, mp 120–122°C. H NMR spec-
ppm: 2.74–2.79 m (4H, CH2), 4.14 s (4H, CH2), 7.12–
7.74 m (4H, Harom). 13C NMR spectrum, δC, ppm:
35.45 (C6, C7), 61.59 (C2, C4), 109.43 (C11), 113.55
(C13), 121.13 (C9), 128.73 (C12), 143.67 (C10), 147.01
(C8). Found, %: C 46.63; H 4.72; N 10.57; S 25.00.
C10H12N2O2S2. Calculated, %: C 46.85; H 4.72;
N 10.93; S 25.02.
1
trum, δ, ppm: 2.33 s (3H, CH3), 3.91 s (4H, CH2),
4.89 s (4H, CH2), 6.53–6.67 m (4H, Harom). 13C NMR
spectrum, δC, ppm: 21.77 (C14), 35.83 (C6, C7), 54.95
(C2, C4), 114.76 (C9, C13), 119.43 (C10, C12), 139.04
(C11), 148.74 (C8). Found, %: C 58.40; H 6.23; N 6.07;
S 28.19. C11H15NS2. Calculated, %: C 58.62; H 6.71;
N 6.21; S 28.46.
3-(4-Nitrophenyl)-1,5,3-dithiazepane (IIIi). Yield
1
73%, Rf 0.55, mp 91–92°C. H NMR spectrum, δ,
3-(2-Methoxyphenyl)-1,5,3-dithiazepane (IIId).
Yield 65%, Rf 0.71, mp 112–114°C. H NMR spec-
trum, δ, ppm: 2.71–2.95 m (4H, CH2), 3.35 s (3H,
ppm: 2.79–2.90 m (4H, CH2), 4.30 s (4H, CH2), 6.91–
7.85 m (4H, Harom). 13C NMR spectrum, δC, ppm:
36.41 (C6, C7), 59.75 (C2, C4), 111.92 (C9, C13), 124.25
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 4 2012

MURZAKOVA et al.
592
(C10, C12), 138.90 (C11), 149.52 (C8). Found, %:
C 46.33; H 4.41; N 10.52; S 24.99. C10H12N2O2S2. Cal-
culated, %: C 46.85; H 4.72; N 10.93; S 25.02.
29.00 (C7), 32.14 (C6, C8), 55.24 (C16), 55.59 (C2, C4),
100.32 (C10), 103.91 (C12), 107.91 (C14), 130.07 (C13),
147.20 (C9), 160.74 (C11). Found, %: C 56.21; H 6.50;
N 5.13; S 25.08. C12H17N2OS2. Calculated, %:
C 56.44; H 6.71; N 5.48; S 25.11.
3-Phenyl-1,5,3-dithiazocane (IVa). Yield 95%,
1
Rf 0.77, mp 96–98°C. H NMR spectrum, δ, ppm:
3-(4-Methoxyphenyl)-1,5,3-dithiazocane (IVf).
Yield 80%, Rf 0.79, mp 97–98°C. H NMR spectrum,
1.79–1.84 m (2H, CH2), 2.74 t (4H, CH2, J = 5.6 Hz),
4.78 s (4H, CH2), 6.88–7.37 m (5H, Harom). 13C NMR
spectrum, δC, ppm: 29.00 (C7), 29.16 (C6, C8), 55.16
(C2, C4), 114.66 (C12), 119.58 (C14), 120.94 (C11),
128.78 (C13), 143.31 (C10), 144.38 (C9). Mass spec-
trum, m/z (Irel, %): 225 (10) [M]+, 77 (20) [C6H5]+,
91 (80) [C6H5N]+, 107 (20) [C5H7N]+, 120 (100)
[C8H10N]+. Calculated: M 225.38.
1
δ, ppm: 1.81 m (2H, CH2), 2.73 t (4H, CH2, J =
5.6 Hz), 3.80 s (3H, CH3), 4.76 s (4H, CH2), 6.81–
7.27 m (4H, Harom). 13C NMR spectrum, δC, ppm:
29.99 (C7), 32.26 (C6, C8), 55.65 (C16), 57.04 (C2, C4),
114.36 (C11, C13), 114.89 (C10, C14), 137.34 (C9),
152.85 (C12). Found, %: C 56.41; H 6.38; N 5.24;
S 25.03. C12H17N2OS2. Calculated, %: C 56.44;
H 6.71; N 5.48; S 25.11.
3-(3-Methylphenyl)-1,5,3-dithiazocane (IVb).
1
Yield 88%, Rf 0.90, mp 77–79°C. H NMR spectrum,
3-(2-Nitrophenyl)-1,5,3-dithiazocane (IVg). Yield
δ, ppm: 1.79 m (2H, CH2), 2.43 s (3H, CH3), 2.76 t
(4H, CH2, J = 5.6 Hz), 4.78 s (4H, CH2), 6.76–7.28 m
(4H, Harom). 13C NMR spectrum, δC, ppm: 22.21 (C15),
29.05 (C7), 32.29 (C6, C8), 56.70 (C2, C4), 111.01 (C14),
113.25 (C12), 119.66 (C13), 129.23 (C11), 139.04 (C10),
143.47 (C9). Mass spectrum, m/z (Irel, %): 239 (20)
[M]+, 91 (80) [C7H7]+, 105 (100) [C7H7N]+, 150 (50)
[C8H9NS]+, 180 (100) [C10H16NS]+. Calculated:
M 239.40.
1
69%, Rf 0.55, mp 91–92°C. H NMR spectrum, δ,
ppm: 1.57 m (2H, CH2), 2.63 m (4H, CH), 4.52 s (4H,
CH2), 6.77–7.74 m (4H, Harom). 13C NMR spectrum,
δC, ppm: 38.67 (C7), 29.47 (C6, C8), 55.46 (C2, C4),
114.81 (C10, C14), 116.85 (C12), 126.92 (C11, C13),
136.02 (C9). Mass spectrum, m/z (Irel, %): 270 (20)
[M]+, 122 (80) [C6H4NO2]+, 136 (100) [C6H4N2O2]+,
150 (40) [C7H6N2O2]+, 196 (20) [C8H8N2O2S]+. Cal-
culated: M 270.37.
3-(4-Methylphenyl)-1,5,3-dithiazocane (IVc).
1
3-(3-Nitrophenyl)-1,5,3-dithiazocane (IVh). Yield
Yield 81%, Rf 0.88, mp 70–72°C. H NMR spectrum,
1
75%, Rf 0.60, mp 63–64°C. H NMR spectrum, δ,
δ, ppm: 1.83 m (2H, CH2), 2.36 s (3H, CH3), 2.71 t
(4H, CH2, J = 5.6 Hz), 4.72 s (4H, CH2), 6.80–7.29 m
(4H, Harom). 13C NMR spectrum, δC, ppm: 22.04 (C15),
30.42 (C7), 32.92 (C6, C8), 56.77 (C2, C4), 114.30
(C14, C16), 126.51 (C11, C13), 138.98 (C12), 142.90
(C9). Found, %: C 60.13; H 7.08; N 5.43; S 26.62.
C12H17NS2. Calculated, %: C 60.20; H 7.16; N 5.85;
S 26.79.
ppm: 1.92 m (2H, CH2), 2.28 m (4H, CH2), 4.51 s (4H,
CH2), 7.01–8.23 m (5H, CH). 13C NMR spectrum, δC,
ppm: 27.99 (C7), 32.00 (C6, C8), 53.98 (C2, C4), 111.33
(C14), 118.85 (C12), 121.27 (C10), 129.80 (C11), 138.90
(C9), 141.60 (C13). Found, %: C 48.50; H 5.15;
N 10.21; S 23.52. C11H17N2O2S2. Calculated, %:
C 48.86; H 5.22; N 10.36; S 23.72.
3-(4-Nitrophenyl)-1,5,3-dithiazocane (IVi). Yield
3-(2-Methoxyphenyl)-1,5,3-dithiazocane (IVd).
1
1
86%, Rf 0.53, mp 81–83°C. H NMR spectrum, δ,
Yield 66%, Rf 0.56, mp 83–85°C. H NMR spectrum,
ppm: 1.84 m (2H, CH2), 2.72 t (4H, CH2, J = 6,
5.6 Hz), 4.78 s (4H, CH2), 7.93–8.22 m (4H, Harom).
13C NMR spectrum, δC, ppm: 29.17 (C7), 31.77 (C6,
C8), 56.56 (C2, C4), 112.87 (C10, C14), 125.72 (C11,
C13), 139.63 (C12), 148.70 (C9). Found, %: C 48.31;
H 5.18; N 10.10; S 23.29. C11H17N2O2S2. Calculated,
%: C 48.86; H 5.22; N 10.36; S 23.72.
δ, ppm: 1.82 m (2H, CH2), 2.66 m (4H, CH2), 3.77 s
(3H, CH3), 4.72 s (4H, CH2), 6.77–7.74 m (4H, Harom).
13C NMR spectrum, δC, ppm: 29.17 (C7), 30.36 (C6,
C8), 53.79 (C16), 55.16 (C2, C4), 106.33 (C11), 127.61
(C14), 129.93 (C13), 131.57 (C12), 144.81 (C9), 160.42
(C10). Mass spectrum, m/z (Irel, %): 255 (20) [M]+, 107
(10) [C7H7O]+, 121 (70) [C7H7NO]+, 135 (25)
[C8H9NO]+, 149 (100) [C9H11NO]+. Calculated:
M 255.40.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 11-03-00101-a, 11-03-97011-r_Povolzh’e_a).
3-(3-Methoxyphenyl)-1,5,3-dithiazocane (IVe).
1
Yield 83%, Rf 0.71, mp 94–95°C. H NMR spectrum,
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7.28 m (4H, Harom). 13C NMR spectrum, δC, ppm:
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