Synthesis of amino sulfides in the presence of rare-earth and transition metal catalysts

Article abstract of DOI:10.1134/S1070428012070020

Efficient procedures have been developed for the synthesis of amino sulfides by aminomethylation of thiols with higher geminal diamines, thiomethylation of secondary amines with N,N-dimethylaminomethyl sulfides, and decyclization of 1,3,6-oxadithiepane or

Full text of DOI:10.1134/S1070428012070020

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2012, Vol. 48, No. 7, pp. 902–907. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © R.R. Khairullina, B.F. Akmanov, R.V. Kunakova, A.G. Ibragimov, 2012, published in Zhurnal Organicheskoi Khimii, 2012, Vol. 48,
No. 7, pp. 907–912.
Synthesis of Amino Sulfides in the Presence of Rare-Earth
and Transition Metal Catalysts
R. R. Khairullina, B. F. Akmanov, R. V. Kunakova, and A. G. Ibragimov
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences,
pr. Oktyabrya 141, Ufa, 450075 Bashkortostan, Russia
e-mail: ink@anrb.ru
Received November 7, 2011
Abstract—Efficient procedures have been developed for the synthesis of amino sulfides by aminomethylation
of thiols with higher geminal diamines, thiomethylation of secondary amines with N,N-dimethylaminomethyl
sulfides, and decyclization of 1,3,6-oxadithiepane or N-tert-butyl-1,5,3-dithiazepane with secondary amines in
the presence of rare-earth and transition metals.
DOI: 10.1134/S1070428012070020
Amino sulfides are commonly synthesized by
aminomethylation according to Mannich [1–9]. How-
ever, this method is not free from some restrictions
related to the use of aqueous formaldehyde solution,
elevated temperature, long reaction time, and relatively
poor yields [2, 7–9]. We recently [10] proposed an ef-
ficient procedure for the synthesis of N,N-dimethyl-
aminomethyl sulfides via aminomethylation of thiols
with accessible and low toxic N,N,N′,N′-tetramethyl-
methanediamine in the presence of SmCl3·6H2O as
catalyst.
With a view to extend the scope of application of
this reaction [10] and develop efficient methods for
the synthesis of various acyclic amino sulfides in the
present work we studied aminomethylation of thiols
with higher geminal diamines and performed thio-
methylation of secondary amines with N,N-dimethyl-
aminomethyl sulfides and decyclization of 1-oxa-3,6-
dithiacycloheptane and N-tert-butyl-1,5,3-dithiazepane
by the action of secondary amines in the presence of
catalysts based on transition (Cu, Fe, Co, Mn, Pd, V,
Zr, Ti) and rare-earth (Sm, Er, Yb, Eu) metal salts and
complexes. As higher geminal diamines we selected
4,4′-methylenedimorpholine (I), N,N,N′,N′-tetraethyl-
methanediamine (II), and N,N′-dibenzyl-N,N′-diphenyl-
methanediamine (III) which were prepared by amino-
methylation of the corresponding amines with
N,N,N′,N′-tetramethylmethanediamine [11].
Using the reaction of pentane-1-thiol with
4,4′-methylenedimorpholine (I) as model, we found
that, among the examined catalysts based on Cu, Sm,
Er, Eu, Fe, Co, Mn, Pd, V, Zr, and Ti salts and com-
plexes [10], the most active were SmCl3·6H2O (90%),
Sm(NO3)3 ·6H2O (85%), and CuCl (80%) at a thiol–
geminal diamine–catalyst ratio of 10:12:0.5 (60°C,
6 h, CHCl3, argon). The yield of N-(pentylsulfanyl-
methyl)morpholine (IVa) appreciably depended on the
metal nature. In the reaction of pentanethiol with di-
amine I in the presence of FeCl3·6H2O, AlCl3·6H2O,
and ZnCl2·2H2O the yield of IVa ranged from 55 to
65%, whereas in the absence of a catalyst the yield of
IVa did not exceed 35% in 48 h. Therefore, all subse-
quent reactions of thiols with higher geminal diamines
were carried out using SmCl3·6H2O as catalyst.
Under the above conditions (5 mol % of [Sm],
60°C, 6 h, CHCl3), aminomethylation of pentane-1-
Scheme 1.
R3
R1
R1
R1
R1
X
R1
R3SH, [Sm]
–R1R2NH
HS–X–SH, [Sm]
–R1R2NH
S
N
R2
N
R2
N
R2
N
R2
S
S
N
R2
IVa–IVc, Va–Vc, VIa–VIc
I–III
VIIa, VIIb, VIIIa, VIIIb, IXa, IXb
I, IV, VII, R1R2N = morpholin-4-yl; II, V, VIII, R1 = R2 = Et; III, VI, IX, R1 = Ph, R2 = PhCH2; R3 = C5H11 (a), i-Pr (b), Ph (c);
X = (CH2)2 (a), C6H4OC6H4 (b); [Sm] = SmCl3 ·6H2O.
902

SYNTHESIS OF AMINO SULFIDES
903
Scheme 2.
R1
CH2
N
R2
R1
R2
R1
R1
R1
R1
R3
R3SH
··
··
M
R3
N
R2
N
R2
N
N
N
R2
S
+
R1R2NH
H
S
R1
M
–M
R2
M
··
N
R2
M is catalyst.
thiol, propane-2-thiol, and phenylmethanethiol with di-
amines I–III at a molar ratio of 10:12 gave the corre-
sponding amino sulfides IVa–IVc, Va–Vc, and VIa–
VIc in 77–98% yield. High selectivity was observed in
the aminomethylation of α,ω-dithiols. The reaction
involved both thiol groups in the substrate (molar ratio
dithiol–diamine–[Sm] 10:22:0.5) with formation of
80–94% of bis-sulfides VIIa, VIIb, VIIIa, VIIIb,
IXa, and IXb (Scheme 1); in the absence of a catalyst,
the yield did not exceed 40% in 48 h.
ZnSO4 (70%), and Zn(OAc)2 (53%). In the absence of
a catalyst the yield of IVa did not exceed 15%. By
thiomethylation of secondary amines with N,N-di-
methylaminomethyl sulfides Xa–Xc, XIa, and XIb
(5 mol % ZnCl2·2H2O, 20°C, 6 h, CHCl3) we obtained
the corresponding amino sulfides IV–IX (yield ~98%).
The equilibrium was displaced toward formation of
IV–IX by removal of gaseous dimethylamine from the
reaction zone (bp 6.9°C [13]).
While studying the above reactions we found that
higher amino sulfides can be synthesized in high yield
by reaction of N-tert-butyl-1,5,3-dithiazepinane or
1,3,6-oxadithiepane with secondary amines (Scheme 4).
For example, the reaction of morpholine with N-tert-
butyl-1,5,3-dithiazepane (ratio morpholine–1,5,3-di-
thiazepane–catalyst 10:10 :0.5, 80°C, 6 h, CHCl3,
argon) afforded 90% of VIIa. The most active cata-
lysts in this reaction were FeCl3·6H2O (62%), SmCl3·
6H2O (85%), and YbF3 (90%). The yield of VIIa in
the absence of catalyst was 5%. Opening of the
1,3,6-oxadithiepane ring with secondary amines was
also selective (amine–1,3,6-oxadithiepane–catalyst
10:10:0.5, 20°C, 2 h, CHCl3, argon). The highest
catalytic activity was observed for SmCl3·6H2O (95%)
and YbF3 (98%) (40% in the absence of a catalyst).
The 1H and 13C NMR spectra of the aminomethyla-
tion products contained signals at δ 3.65–5.33 and
δC 54.03–68.11 ppm due to methylene protons and
carbon atom located between nitrogen and sulfur
(SCH2N). Their IR spectra displayed characteristic ab-
sorption bands at 646–647 cm–1, belonging to stretch-
ing vibrations of sulfide C–S bonds [12].
Presumably [2, 7–9], in the initial stage diamine
molecule is coordinated to the central metal ion in the
catalyst, and the subsequent attack by thiol of the com-
plex thus formed leads to amino sulfide according to
Scheme 2.
We tried to modify the developed procedure for the
synthesis of amino sulfides. For this purpose, secon-
dary amines were subjected to catalytic thiomethyla-
tion with N,N-dimethylaminomethyl sulfides X and XI
which were prepared by aminomethylation of mono-
and dithiols with N,N,N′,N′-tetramethylmethanedi-
amine (Scheme 3) [10]. Optimal conditions were found
for the reaction of morpholine with N,N-dimethyl-
(pentylsulfanyl)methanamine (Xa), leading to amino
sulfide IVa in 98% yield (ratio morpholine–Xa–
catalyst 10:10:0.5, 20°C, 6 h, CHCl3, argon). Here,
the most active catalysts were ZnCl2 ·2H2O (98%),
Thus the developed procedures for synthesis of
higher amino sulfides by aminomethylation of mono-
and dithiols with geminal diamines, as well as by thio-
methylation of secondary amines with N,N-dimethyl-
aminomethyl sulfides and by decyclization of
1,3,6-oxadithiepane (or N-tert-butyl-1,5,3-dithiaze-
pane) by the action of secondary amines, make it
possible to obtain difficultly accessible acyclic N,S-
containing heteroatom compounds in high yield.
Scheme 3.
R
Me
Me
Me
Me
X
Me
RSH, [Sm]
–Me2NH
HS–X–SH, [Sm]
–Me2NH
S
N
N
N
N
S
S
N
Me
Me
Me
Me
Me
Xa–Xc
XIa, XIb
R = C5H11 (a), i-Pr (b), Ph (c); X = (CH2)2 (a), C6H4OC6H4 (b); [Sm] = SmCl3 ·6H2O.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

KHAIRULLINA et al.
904
Scheme 4.
N,N,N′,N′-Tetraethylmethanediamine (II). Yield
50%, nD20 = 1.4386; published data [14]: nD20 = 1.4252.
IR spectrum, ν, cm–1: 2972–2874, 1467, 1452, 1379,
R1
R1
S
R1R2NH, [Sm]
–H2Q
N
R2
S
S
Q
N
1
R2
1215, 1066, 909, 734. H NMR spectrum, δ, ppm:
S
VIIa–IXa
0.95 t (12H, CH3), 2.54 q (8H, CH2CH3, J = 4.8 Hz),
2.85 s (2H, CH2). 13C NMR spectrum, δC, ppm: 11.80 s
(CH3), 45.00 s (CH3CH2), 82.09 s (CH2).
VIIa, R1R2N = morpholin-4-yl; VIIIa, R1 = R2 = Et; IXa, R1 =
Ph, R2 = PhCH2; Q = O, t-BuN; [Sm] = SmCl3 ·6H2O.
N,N′-Dibenzyl-N,N′-diphenylmethanediamine
(III). Yield 83%, nD20 = 1.5698. IR spectrum, ν, cm–1:
3025, 2924–2854, 1602, 1506, 1453, 1372, 1248,
1179, 1045, 989, 751, 694. 1H NMR spectrum, δ, ppm:
2.21 s (4H, CH2), 4.37 s (2H, CH2), 6.71–7.43 m (10H,
EXPERIMENTAL
The progress of reactions was monitored by TLC
on Sorbfil plates using hexane–ethyl acetate (2:1) as
eluent. The purity of the initial compounds was no less
than 99%. The solvents were purified according to the
H
arom). 13C NMR spectrum, δC, ppm: 60.42 s (C4, C4′),
77.35 s (C2), 113.40 s (C12, C12′, C16, C16′), 118.10 s
(C14, C14′), 127.34 s (C8, C8′), 127.70 s (C6, C6′, C10,
C10′), 128.66 s (C7, C7′, C9, C9′), 129.30 s (C13, C15,
C13′, C15′), 139.05 s (C5, C5′), 147.57 s (C11, C11′).
Found, %: C 85.61; H 6.98; N 7.41. C27H26N2. Cal-
culated, %: C 85.68; H 6.92; N 7.40.
Amino sulfides IVa–IVc, Va–Vc, VIa–VIc, VIIa,
VIIb, VIIIa, VIIIb, IXa, IXb (general procedure).
a. A mixture of 10 mmol of the corresponding thiol,
12 mmol of diamine I–III, and 0.5 mmol of SmCl3·
6H2O was stirred for 6 h at 60°C.
b. A mixture of 10 mmol of N,N-dimethylamino-
methyl sulfide, 10 mmol of secondary amine, and
0.5 mmol of ZnCl2·2H2O was stirred for 6 h at 20°C.
c. A mixture of 10 mmol of N-tert-butyl-1,5,3-
dithiazepane, 10 mmol of secondary amine, and
0.5 mmol of SmCl3·6H2O was stirred for 6 h at 80°C.
1
procedures described in [12]. The H and 13C NMR
spectra were recorded on a Bruker Avance-400 spec-
trometer at 300.13 and 100.62 MHz, respectively,
using CDCl3 as solvent (δC 77.10 ppm). The IR spectra
were measured on a Bruker Vertex 70 spectrometer
from samples dispersed in mineral oil. The mass spec-
tra of IVa–IVc, Vb, Vc, and VIa–VIc were obtained
on a Shimadzu LCMS-2010 EV instrument [atmos-
pheric pressure chemical ionization; APCI probe tem-
perature 500°C, heater temperature 200°C, vaporizer
temperature 250°C; liquid phase flow rate 0.05 ml×
min–1; nebulizing gas flow rate 2.5 ml/min; ion source
voltage (+) 4.5 kV, (–) 3 kV]. The mass spectra of
VIIa, VIIb, IXa, and IXb were recorded on a Bruker
MALDI–TOF Autoflex III spectrometer (Germany)
using α-cyano-4-hydroxycinnamic or 2,5-dihydroben-
zoic acid as matrix (a sample was prepared by the
dried drop method in chloroform, 1:10). The elemental
compositions were determined on a Carlo Erba-1106
analyzer. The melting points were determined on
a PHMK 80/2617 melting point apparatus. The refrac-
tive indices were measured on an IRF 454 BM refrac-
tometer. Individual products were isolated by chroma-
tography on KSK silica gel (50–160 μm).
d. A mixture of 10 mmol of 1,3,6-oxadithiepane,
10 mmol of secondary amine, and 0.5 mmol of
SmCl3·6H2O was stirred for 2 h at 20°C.
The products were isolated by column chromatog-
raphy on silica gel.
N-(Pentylsulfanylmethyl)morpholine (IVa). Yield
75% (a), 98% (b); nD20 = 1.4918, Rf 0.34. IR spectrum,
ν, cm–1: 2957–2688, 1452, 1376, 1312, 1237, 1117,
Diamines I–III (general procedure). A mixture of
10 mmol of the corresponding secondary amine,
30 mmol of N,N,N′,N′-tetramethylmethanediamine,
and 0.5 mmol of Sm(NO3)3·6H2O or CuCl as catalyst
was stirred for 10 h at 60°C. The product was isolated
from the reaction mixture by column chromatography
on silica gel.
1
1005, 939, 862, 775, 669. H NMR spectrum, δ, ppm:
0.88 m (3H, CH3), 1.33 m (4H, CH2), 1.58 m (2H,
CH2), 2.54–2.58 m (6H, CH2), 3.69 t (4H, CH2),
3.85 br.s (2H, CH2). 13C NMR spectrum, δC, ppm:
13.95 s (C8), 22.27 s (C7), 29.91 s (C6), 31.04 s (C5),
33.32 s (C4), 51.12 s (C9, C13), 63.06 s (C2), 66.77 s
(C10, C12). Mass spectrum, m/z (Irel, %): 204 (100)
[M + H]+. Found, %: C 59.12; H 10.24; N 6.87;
S 15.87. C10H21NOS. Calculated, %: C 59.07; H 10.41;
N 6.89; S 15.77. M 203.346.
4,4′-Methylenedimorpholine (I). Yield 90%, nD20
=
1.5653; published data [11]: nD20 = 1.5657. H NMR
spectrum, δ, ppm: 2.37 br.s (8H, CH2), 2.79 s (2H,
CH2), 3.57 br.s (8H, CH2). 13C NMR spectrum, δC,
ppm: 51.86 s (NCH2), 66.84 s (OCH2), 81.56 s
(NCH2N).
1
N-(Propan-2-ylsulfanylmethyl)morpholine
(IVb). Yield 70% (a), 96% (b); nD20 = 1.4942, Rf 0.52.
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SYNTHESIS OF AMINO SULFIDES
905
IR spectrum, ν, cm–1: 2958–2805, 1453, 1382, 1290,
1146, 1117, 1005, 862, 774, 614. 1H NMR spectrum, δ,
ppm: 1.17 d (6H, CH3, J = 6.8 Hz), 2.47 t (4H, CH2),
2.86 m (1H, CH), 3.59 t (4H, CH2), 3.73 s (2H, CH2).
13C NMR spectrum, δC, ppm: 23.82 s (C5, C5′), 35.47 s
(C4), 51.14 s (C6, C10), 60.86 s (C2), 66.67 s (C7, C9).
Mass spectrum, m/z (Irel, %): 176 (100) [M + H]+.
Found, %: C 54.72; H 9.73; N 8.02; S 18.37.
C8H17NOS. Calculated, %: C 54.81; H 9.78; N 7.99;
S 18.29. M 175.293.
data [5]: nD25 = 1.5500; Rf 0.46. IR spectrum, ν cm–1:
2971–2826, 1477, 1383, 1261, 1213, 1068, 994, 873,
1
742, 692, 620, 482. H NMR spectrum, δ, ppm: 1.01 t
(6H, CH3), 2.65 q (4H, CH2, J = 6.8 Hz), 4.62 s (2H,
CH2), 7.20 t (1H, Harom), 7.21 t (2H, H Harom), 7.50 d
(2H, Harom, J = 8.0 Hz). 13C NMR spectrum, δC, ppm:
12.81 s (C11, C11′), 46.50 s (C10, C10′), 63.48 s (C2),
126.46 s (C7), 128.86 s (C6, C8), 132.50 s (C5, C9),
137.81 s (C4). Mass spectrum, m/z (Irel, %): 196 (100)
[M + H]+. Found, %: C 67.87; H 8.74; N 7.31;
S 16.08. C11H17NS. Calculated, %: C 67.64; H 8.77;
N 7.17; S 16.42. M 195.325.
N-(Phenylsulfanylmethyl)morpholine (IVc).
Yield 65% (a), 92% (b); nD20 = 1.5630; published data
[5]: nD25 = 1.5809 [5]; Rf 0.33. IR spectrum, ν, cm–1:
2959–2826, 1583, 1478–1451, 1315–1262, 1116,
N-Benzyl-N-(pentylsulfanylmethyl)aniline (VIa).
Yield 78% (a), 25% (b); nD20 = 1.5852, Rf 0.56.
IR spectrum, ν, cm–1: 2955–2856, 1599, 1504, 1453,
1380, 1271, 1210, 1116, 1076, 950, 749–693. 1H NMR
spectrum, δ, ppm: 0.96 t (3H, CH3), 1.37 m (4H, CH2),
1.64 m (2H, CH2), 2.59 t (2H, CH2), 4.72 s (2H, CH2),
4.84 s (2H, CH2), 6.90 t (1H, Harom, J = 7.2 Hz), 6.97 d
(2H, H Harom, J = 8.0 Hz), 7.24–7.43 m (7H, Harom).
13C NMR spectrum, δC, ppm: 14.04 s (C8), 22.32 s
(C7), 30.04 s (C6), 31.18 s (C5), 31.85 s (C4), 53.88 s
(C15), 55.50 s (C2), 114.32 s (C10, C14), 118.41 s (C12),
127.02 s (C17, C21), 127.12 s (C19), 128.70 s (C11, C13),
129.24 s (C18, C20), 138.34 s (C16), 148.07 s (C9). Mass
spectrum, m/z (Irel, %): 300 (100) [M + H]+. Found, %:
C 76.32; H 8.64; N 4.66, S 10.38. C19H25NS. Calcu-
lated, %: C 76.20; H 8.41; N 4.68; S 10.71. M 299.475.
1
1006, 861, 744, 692, 603, 493. H NMR spectrum, δ,
ppm: 2.60 t (4H, CH2), 3.65 t (4H, CH2), 4.40 s (2H,
CH2), 7.18 t (1H, Harom), 7.26 t (2H, Harom), 7.47 d (2H,
H
arom, J = 8.0 Hz). 13C NMR spectrum, δC, ppm:
50.60 s (C10, C14), 66.60 s (C11, C13), 67.10 s (C2),
126.53 s (C7), 128.95 s (C6, C8), 131.54 s (C5, C9),
137.69 s (C4). Mass spectrum, m/z (Irel, %): 210 (100)
[M + H]+. Found, %: C 63.21; H 7.26; N 6.71; S 15.25.
C11H15NOS. Calculated, %: C 63.12; H 7.22; N 6.69;
S 15.32. M 209.309.
N-Ethyl-N-(pentylsulfanylmethyl)ethanamine
(Va). Yield 54% (a), 30% (b); nD20 = 1.4635, Rf 0.48.
IR spectrum, ν, cm–1: 2966–2823, 1459, 1381, 1269,
1209, 1112, 991, 753, 644. 1H NMR spectrum, δ, ppm:
0.88 m (3H, CH3), 1.05 t (6H, CH3), 1.32 m (4H, CH2),
1.57 m (2H, CH2), 2.53 t (2H, CH2), 2.58 q (4H, CH2,
J = 7.2 Hz), 4.09 br.s (2H, CH2). 13C NMR spectrum,
δC, ppm: 12.77 s (C10, C10′), 13.94 s (C8), 22.28 s (C7),
30.33 s (C6), 31.12 s (C5), 33.01 s (C4), 46.28 s (C9,
C9′), 58.41 s (C2). Found, %: C 63.61; H 12.51; N 7.14;
S 16.74. C10H23NS. Calculated, %: C 63.43; H 12.24;
N 7.40; S 16.93.
N-Benzyl-N-(propan-2-ylsulfanylmethyl)aniline
(VIb). Yield 75% (a), 20% (b); nD20 = 1.6065, Rf 0.78.
IR spectrum, ν, cm–1: 3061–2863, 1504, 1452, 1382,
1
1211, 1153, 953, 897, 749, 693, 511, 457. H NMR
spectrum, δ, ppm: 1.32 d (6H, CH3, J = 6.8 Hz),
2.98 m (1H, CH), 3.67 s (2H, CH2), 3.69 s (2H, CH2),
6.84 t (1H, Harom), 6.93 d (2H, Harom, J = 8.0 Hz), 7.25–
7.36 m (7H, Harom). 13C NMR spectrum, δC, ppm:
24.11 s (C5, C5′), 35.15 s (C4), 53.83 s (C6), 54.03 s
(C2), 114.25 s (C14, C18), 118.36 s (C16), 126.98 s (C8,
C12), 127.10 s (C10), 128.68 s (C15, C17), 129.23 s (C9,
C11), 138.41 s (C7), 148.10 s (C13). Mass spectrum, m/z
(Irel, %): 272 (100) [M + H]+. Found, %: C 75.44;
H 7.56; N 5.19; S 11.81. C17H21NS. Calculated, %:
C 75.23; H 7.80; N 5.16; S 11.81. M 271.421.
N-Ethyl-N-(propan-2-ylsulfanylmethyl)ethan-
amine (Vb). Yield 47% (a), 38% (b); nD20 = 1.4671,
Rf 0.66. IR spectrum, ν, cm–1: 2969–2821, 1460, 1382,
1
1273, 1211, 1066, 992, 753, 651. H NMR spectrum,
δ, ppm: 1.04 t (6H, CH3), 1.24 d (6H, CH3, J =
6.8 Hz), 2.56 q (4H, CH2, J = 7.2 Hz), 2.87 m (1H,
CH), 4.08 s (2H, CH2). 13C NMR spectrum, δC, ppm:
12.77 s (C7, C7′), 24.24 s (C5, C5′), 35.36 s (C4), 46.25 s
(C6, C6′), 56.27 s (C2). Mass spectrum, m/z (Irel, %):
161 (100) [M]+. Found, %: C 59.52; H 11.84; N 8.88;
S 19.76. C8H19NS. Calculated, %: C 59.57; H 11.87;
N 8.68; S 19.88. M 161.309.
N-Benzyl-N-(phenylsulfanylmethyl)aniline (VIc).
Yield 43% (a), 90% (b); nD20 = 1.6447, Rf 0.52. IR spec-
trum, ν, cm–1: 2962–2930, 1592, 1493, 1356, 1233,
1
1025, 839, 748–693, 584. H NMR spectrum, δ, ppm:
5.33 s (2H, CH2), 7.09–7.05 m (6H, Harom), 7.35–
7.24 m (9H, Harom). 13C NMR spectrum, δC, ppm:
61.02 s (C2), 121.70 s (C11, C11′, C15, C15′), 122.61 s
(C13, C13′), 127.13 s (C7), 128.92 s (C6, C8), 129.34 s
N-Ethyl-N-(phenylsulfanylmethyl)ethanamine
(Vc). Yield 59% (a), 76% (b); nD20 = 1.5485; published
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 7 2012

KHAIRULLINA et al.
906
(C12, C12′, C14, C14′), 132.63 s (C5, C9), 135.59 s (C4′),
146.57 s (C10, C10′). Mass spectrum, m/z (Irel, %): 305
(100) [M]+. Found, %: C 78.64; H 6.31; N 4.56;
S 10.49. C20H19NS. Calculated, %: C 78.65; H 6.27;
N 4.58; S 10.50. M 305.438.
C17′, C19, C19′), 46.52 s (C16, C16′, C18, C18′), 64.31 s (C2,
C14), 119.42 s (C6, C6′, C10, C10′), 131.79 s (C4, C12),
134.09 s (C5, C5′, C11, C11′), 156.10 s (C7, C9). Found,
%: C 65.65; H 7.85; N 6.71; S 15.93. C22H32N2OS2.
Calculated, %: C 65.30; H 7.97; N 6.92; S 15.85.
1,6-Bis(morpholin-4-yl)-2,5-dithiahexane (VIIa).
Yield 98% (a), 60% (b), 70% (c), 97% (d); mp 62–
65°C. IR spectrum, ν, cm–1: 2925–2862, 1456, 1376,
1314, 1290, 1143, 1113, 1004, 860, 775, 668. 1H NMR
spectrum, δ, ppm: 2.58 t (8H, CH2), 2.80 s (4H, CH2),
3.70 t (8H, CH2), 3.87 s (4H, CH2). 13C NMR spec-
trum, δC, ppm: 33.55 s (C4, C5), 51.17 s (C9, C13, C14,
C18), 63.20 s (C2, C7), 66.75 s (C10, C12, C15, C17). Mass
spectrum, m/z (Irel, %): 315.414 (78) [M + Na]+,
331.372 (100) [M + K]+. Found, %: C 49.35; H 8.24;
N 9.62; S 21.84. C12H24N2O2S2. Calculated, %:
C 49.28; H 8.27; N 9.58; S 21.93. M 292.463.
N,N′-Dibenzyl-N,N′-diphenyl-2,5-dithiahexane-
1,6-diamine (IXa). Yield 75% (a), 63% (b), 58% (c),
80% (d); mp 73–75°C, Rf 0.54. IR spectrum, ν, cm–1:
2924–2853, 1595, 1455, 1374, 1117, 1027, 949, 876,
1
761–738, 698, 548, 494. H NMR spectrum, δ, ppm:
2.67 s (4H, CH2), 4.59 s (4H, CH2), 4.61 s (4H, CH2),
6.80–6.95 m (6H, Harom), 7.15–7.37 m (14H, Harom).
13C NMR spectrum, δC, ppm: 32.41 s (C4, C5), 53.70 s
(C15, C15′), 55.82 s (C2, C7), 114.56 s (C10, C10′, C14,
C14′), 118.77 s (C12), 127.07 s (C17, C17′, C21, C21′),
127.20 s (C19, C19′), 127.70 s (C11, C11′, C13, C13′),
129.28 s (C18, C18′, C20, C20′), 137.99 s (C16, C16′),
147.85 s (C9, C9′). Mass spectrum, m/z (Irel, %):
483.285 (32) [M – H]+, 507.259 (39) [M + Na]+,
523.195 (100) [M + K]+. Found, %: C 74.28; H 6.46;
N 5.87; S 13.39. C30H32N2S2. Calculated, %: C 74.34;
H 6.65; N 5.78; S 13.23. M 484.721.
4,4′-[Oxybis(benzene-4,1-diylsulfanediylmethyl-
ene)]dimorpholine (VIIb). Yield 95% (a), 70% (b);
mp 112–115°C, Rf 0.47. IR spectrum, ν, cm–1: 2925–
2867, 1583, 1453, 1378, 1316, 1251, 1166, 1115, 1008,
1
861–836, 777, 666, 605, 516–494. H NMR spectrum,
N,N′-Dibenzyl-N,N′-[oxybis(benzene-4,1-diylsul-
fanediylmethylene)]dianiline (IXb). Yield 47% (a),
40% (b); mp 118–120°C. IR spectrum, ν, cm–1: 2923–
2854, 1595, 1503–1453, 1388, 1242, 1214, 1166, 956,
δ, ppm: 2.65 t (8H, CH2), 3.70 t (8H, CH2), 4.39 s (4H,
CH2), 6.93 d (4H, Harom), 7.48 d (4H, Harom). 13C NMR
spectrum, δC, ppm: 50.64 s (C16, C20, C21, C25), 66.65 s
(C17, C19, C22, C24), 68.11 s (C2, C14), 119.43 s (C6, C6′,
C10, C10′), 131.78 s (C4, C12), 133.95 s (C5, C5′, C11,
C11′), 156.07 s (C7, C9). Mass spectrum, m/z (Irel, %):
431.284 (100) [M – H]+. Found, %: C 61.11; H 6.45;
N 6.50; S 14.91. C22H28N2O3S2. Calculated, %:
C 61.08; H 6.52; N 6.48; S 14.82. M 432.601.
N,N,N′,N′-Tetraethyl-2,5-dithiahexane-1,6-di-
amine (VIIIa). Yield 40% (a), 20% (b), 31% (c), 20%
(d); nD20 = 1.5204, Rf 0.52. IR spectrum, ν, cm–1: 2969–
2820, 1459, 1383, 1271, 1211, 1066, 992, 753, 637.
1H NMR spectrum, δ, ppm: 1.07 m (12H, CH3), 2.61 q
(8H, CH2, J = 7.2 Hz), 2.76 s (4H, CH2), 4.16 s (4H,
CH2). 13C NMR spectrum, δC, ppm: 12.78 s (C10, C12,
C14, C16), 33.66 s (C4, C5), 46.22 s (C9, C11, C13, C15),
59.00 s (C2, C7). Found, %: C 54.65; H 10.44; N 10.60;
S 24.31. C12H28N2S2. Calculated, %: C 54.49; H 10.67;
N 10.59; S 24.25.
1
826, 746–690, 535. H NMR spectrum δ, ppm: 4.57 s
(4H, CH2), 4.98 s (4H, CH2), 6.69–6.91 m (10H,
H
arom), 7.23–7.32 m (14H, Harom), 7.45 d (4H, Harom,
J = 8.8 Hz). 13C NMR spectrum, δC, ppm: 54.19 s (C15,
C15′), 60.75 s (C7, C7′), 114.37 s (C10, C10′,C14, C14′),
118.73 s (C12, C12′), 119.46 s (C3, C3′, C22, C22′), 126.87
s (C17, C17′, C21, C21′), 127.17 s (C19, C19′), 128.67 s
(C11, C11′, C17, C17′), 129.19 s (C18, C18′, C20, C20′),
129.48 s (C5, C5′), 135.56 s (C4, C4′, C23, C23′), 137.98 s
(C16, C16′), 147.39 s (C9, C9′), 156.74 s (C2, C2′). Mass
spectrum, m/z (Irel, %): 623.160 (100) [M – H]+. Found,
%: C 76.98; H 5.65; N 4.22; S 10.30. C40H36N2OS2.
Calculated, %: C 76.89; H 5.81; N 4.48; S 10.26.
M 624.859.
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).
N,N′-[Oxybis(benzene-4,1-diylsulfanediyl-
methylene)]bis(N-ethylethanamine) (VIIIb). Yield
70% (a), 55% (b); nD20 = 1.6330, Rf 0.5. IR spectrum, ν,
cm–1: 2970–2827, 1595, 1483, 1382, 1238, 1165, 1088,
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