Synthesis of sulfur-containing vicinal aminoalcohols on the basis of N-(oxiran-2-ylmethyl)amines

Article abstract of DOI:10.1134/S1070428013080113

The reaction of (methanediyldibenzene-4,1-diyl)dimethanethiol, (oxydibenzene-4,1-diyl)dimethanethiol, biphenyl-4,4′-diyldimethanethiol with 1-(oxiran-2-ylmethyl)piperidine and N-(oxiran-2-ylmethyl)-N-ethylaniline afforded the corresponding sulfur-containi

Full text of DOI:10.1134/S1070428013080113

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 8, pp. 1165−1167. © Pleiades Publishing, Ltd., 2013.
Original English Text © A.S. Galstyan, E.G. Mesropyan, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 8, pp. 1182−1184.
Synthesis of Sulfur-Containing Vicinal Aminoalcohols
on the Basis of N-(Oxiran-2-ylmethyl)amines
A. S. Galstyan and E. G. Mesropyan
Yerevan State University, Yerevan, 0025 Armenia
e-mail: a_galstyan@ysu.am
Received January 30, 2013
Abstract—The reaction of (methanediyldibenzene-4,1-diyl)dimethanethiol, (oxydibenzene-4,1-diyl)dimethanethiol,
biphenyl-4,4’-diyldimethanethiol with 1-(oxiran-2-ylmethyl)piperidine and N-(oxiran-2-ylmethyl)-N-ethylaniline
afforded the corresponding sulfur-containing vicinal aminoalcohols resulting from the opening of the oxirane ring
in keeping with Krasusky rule.
DOI: 10.1134/S1070428013080113
The development of synthetic ways to sulfur-contain-
ing compounds is topical for many among them possess
a wide range of physiological action: vasorelaxant,
analgesic, antitumor, bactericidal, sedative action [1],
they are used in the synthesis of rubber as regulators or
inhibitors of polymerization [2]. Organic oxides underlie
the production of 2-propanol derivatives that can serve as
building blocks in designing the molecules of natural and
biologically active organic compounds [3–6]. Formerly
basing on allyl glycidyl ether 4-(oxiran-2-ylmethyl)mor-
pholine and 1-(oxiran-2-ylmethyl)piperidine we obtained
derivatives of 2-propanol and butan-4-olide [7–12].
Herewereportonthestudyofthereactionsof1-(oxiran-
2-ylmethyl)piperidine (Ia) and N-(oxiran-2-ylmethyl)-
N-ethylaniline (Ib) with (methanediyldibenzene-4,1-
diyl)dimethanethiol (II), (oxydibenzene-4,1-diyl)-
dimethanethiol (III), and biphenyl-4,4'-diyldimethane-
thiol (IV). Epoxides Ia, Ib in ethanol at the reagents
ratio 2.2:1 formed compounds V–VII (see the scheme)
as a mixture of diastereomers, but the 1Н and 13С NMR
spectra contain a single set of signals probably due to the
remoteness of the asymmetric sites.
OH
OH
II
R
S
S
S
R
R
Vа, Vb
O
OH
OH
EtOH, Py
III
R
R
S
S
R
O
VIа, VIb
Iа, Ib
OH
OH
IV
S
R
VIIа, VIIb
R = piperidine (а), NEtPh (b).
1165

GALSTYAN, MESROPYAN
1166
1
The structure and the composition of compounds syn-
1580 (C=C, Ar). H NMR spectrum, δ, ppm: 1.13 t
(6H, CH3, J 7.0 Hz), 2.45 m (4H, CH2N), 3.18 d.d (2H,
CH2S), 3.22–3.51 m (6H, CH2S, CH2N), 3.71 s (4H,
ArCH2S), 3.83 m (2H, OCH), 3.89 s (2H, ArCH2Ar),
4.33 d (2H, OH), 6.52 t.t (2Hp, J 7.2 , 1.1 Hz), 6.62 m
(4Hо), 7.08 m (8Hm), 7.19 m (4Harom.). 13C NMR spec-
trum, δ, ppm: 11.11, 35.80, 35.84, 40.57, 44.92, 55.02,
67.91, 111.38, 114.74, 128.23, 128.41, 128.59, 135.74,
138.99, 147.42. Found, %: C 72.51; H 7.77; N 4.25; s
10.19. C37H46N2O2S2. Calculated, %: C 72.27; H 7.54;
N 4.54; s 10.40.
thesized were established from IR, 1H, 13С NMR spectra
and elemental analyses. It was confirmed that under the
action of the mentioned dithiols the epoxide ring opened
in keeping with Krasusky rule [13].
EXPERIMENTAL
1Н NMR spectra were registered at 30°C on a spec-
trometer Varian Mercury-300 (300 MHz) in DMSO-d6,
internal reference HMDS. IR spectra were registered on
a spectrophotometer Nicolet Ftir Nexus from thin films.
The homogeneity and purity of compounds obtained was
checked by TLC on plates with unfixed layer (Al2O3–
starch, 20:1), development in iodine vapor. N-(Oxiran-2-
ylmethyl)amines Ia, Ib were obtained by procedure [7].
3,3'-{[4,4'-Oxybis(4,1-phenylene)bis(methylene)]-
bis(sulfanediyl)}bis[1-(piperidin-1-yl)propan-2-ol]
(VIa) was eluted with a mixture ethanol–hexane, 1 : 8.
Yield 2.0 g (73 %), nD20 1.5780. Rf 0.56 (ethanol–octane,
1:8). IR spectrum, ν, cm–1: 3380 (OH), 3030 (HC=, Ar),
1600 (C=C,Ar). 1H NMR spectrum, δ, ppm: 1.38–1.70 m
(12H, CH2 in piperidine), 2.20–2.52 m (16H, CH2N,
CH2S), 3.72 m (6H, OCH, SCH2Ar), 3.93–420 br.s
(2H, OH), 6.88 m (4H, Ar), 7.21 m (4H, Ar). 13C NMR
spectrum, δ, ppm: 23.73, 25.39, 35.48, 35.79, 54.33,
63.43, 67.03, 117.94, 129.86, 133.15, 155.36. Found,
%: C 66.39; H 7.90; N 5.38; S 11.52. C30H44N2O3S2.
Calculated, %: C 66.14; H 8.14; N 5.14; S 11.77.
Derivatives of 2-propanol V–VII. General proce-
dure.Amixture of 5 mmol of dithiol, 11 mmol of epoxide,
0.1 ml of pyridine, and 10 ml of ethanol was stirred for
18 h at room temperature and 5 min more at 70–75°C.
Then the mixture was filtered, the solvent from the filter-
ate was distilled off in a vacuum, the residue was diluted
with 10 ml of hexane and heated for 5 min at 60–65°C.
After cooling the viscous substance was separated from
the solution and dried in a vacuum to dryness and then it
was subjected to column (35 × 2.0 cm) chromatography
on Al2O3. All compounds save VIIa were nondistillable
viscous substances.
3,3'-{[4,4'-Oxybis(4,1-phenylene)bis(methylene)]
bis(sulfanediyl)}bis{1-[ethyl(phenyl)amino]-propan-
2-ol} (VIb) was eluted with a mixture ethanol–hexane,
1:3. Yield 1.96 g (71%), nD25 1.6242. Rf 0.43 (ethanol–
hexane, 3:9). IR spectrum, ν, cm–1: 3350 (OH), 3095,
3065, 3045, 3035 (HC=, Ar); 1600, 1580 (C=C, Ar).
1H NMR spectrum, δ, ppm: 1.13 t (6H, CH3, Et, J 7.0 Hz),
2.45 m (4H, CH2N), 3.18 d.d (2H, CH2S, J 15.1, 7.1 Hz),
3.22–3.51 m (6H, CH2S, CH2N), 3.71 s (4H, SCH2Ar),
3.83 m (2H, OCH), 4.33 d (2H, OH, J 4.8 Hz), 6.52 t.t
(2Hp, J 7.2, 1.1 Hz), 6.62 m (4Hо), 6.89 m (4Harom),
7.08 m (4Hm), 7.25 m (4Harom). Found, %: C 70.38;
H 7.45; N 4.24; S 10.67. C36H44N2O3S2. Calculated, %:
C 70.09; H 7.19; N 4.54; S 10.40.
3,3'-{[4,4'-Methylenebis(4,1-phenylene)bis-
(methylene)]bis(sulfanediyl)}bis[1-(piperidin-1-yl)
propan-2-ol] (Va) was eluted with a mixture ethanol–
22
hexane, 1:15. Yield 1.82 g (67%), nD 1.5808. Rf 0.57
(ethanol–hexane, 1:15). IR spectrum, ν, cm–1: 3450 (OH),
3030 (HC=, Ar), 1600 (C=C, Ar). 1H NMR spectrum, δ,
ppm: 1.38–1.70 m (12H, CH2 in piperidine), 2.20–2.52 m
(16H, CH2N, CH2S), 3.72 m (6H, OCH,ArCH2S), 3.81 s
(2H, ArCH2Ar), 3.93–4.28 br.s (2H, OH), 7.12 m,7.21 m
(8H,Ar). 13C NMR spectrum, δ, ppm: 23.69, 25.34, 35.81,
35.81, 35.85, 35.88, 40.58, 54.30, 63.40, 66.89, 128.19,
128.59, 135.96, 138.90. Found, %: C 68.83; H 8.34;
N 5.42; S 11.64. C31H46N2O2S2. Calculated, %: C 68.59;
H 8.54; N 5.16; S 11.81.
3,3'-{[Biphenyl-4,4'-diylbis(methylene)]bis-
(sulfanediyl)}bis[1-(piperidine-1-yl)propan-2-ol]
(VIIa) was extracted with hot octane from the residue
after the distillation of the solvent from the reaction
mixture. On cooling the octane solution white crystals
precipitated that were filtered off. Yield 1.93 g (73%), mp
81°С (octane). Rf 0.51 (ethanol–octane, 1:2). IR spectrum,
ν, cm–1: 3380 (OH), 3030 (HC=, Ar), 1600 (C=C, Ar).
1H NMR spectrum, δ, ppm: 1.38–1.70 m (12H, CH2 in
piperidine), 2.20–2.62 m (16H, CH2N, CH2S), 3.78 m
3,3'-{[4,4'-Methylenebis(4,1-phenylene)bis(-
methylene)]bis(sulfanediyl)}bis{1-[ethyl(phenyl)
amino]-propan-2-ol} (Vb) was eluted with a mixture
ethanol–hexane, 1:15. Yield 1.93 g (63%), nD19 1.6217.
Rf 0.53 (ethanol–hexane, 1:15). IR spectrum, ν, cm–1:
3400 (OH), 3095, 3065, 3045, 3035 (HC=, Ar), 1600,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 8 2013

SYNTHESIS OF SULFUR-CONTAINING VICINAL AMINOALCOHOLS
1167
V.I., Zh. Org. Khim., 2000, vol. 36, p. 1033.
(6H, OCH, SCH2Ar), 3.95–4.25 br.s (2H, OH), 7.38 m
(4Harom), 7.54 m (4Harom). 13C NMR spectrum, δ, ppm:
12.00, 13.34, 23.60, 25.20, 35.76, 35.00, 54.23, 63.20,
66.00, 126.12, 138.49. Found, %: C 67.87; H 8.66;
N 5.01; S 12.29. C30H44N2O2S2. Calculated, %: C 68.14;
H 8.39; N 5.30; S 12.13.
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3,3'-{[Biphenyl-4,4'-diylbis(methylene)]
bis(sulfanediyl)}bis{1-[ethyl(phenyl)amino]propan-
2-ol} (VIIb) was eluted with a mixture ethanol–octane,
1 : 2. Yield 2.07 g (69%), nD19 1.6189. Rf 0.55 (ethanol–
octane, 1 : 1). IR spectrum, ν, cm–1: 3400 (OH), 3095,
3065, 3045, 3035 (HC=, Ar); 1605, 1580 (C=C, Ar).
1H NMR spectrum, δ, ppm: 1.15 t (6H, CH3, Et, J 7.0 Hz),
3.17 d.d (2H, CH2S, J 5.1, 7.1 Hz), 3.20–3.53 m (6H,
CH2S, CH2N), 3.71 s (4H, SCH2Ar), 3.83 m (2H, OCH),
4.33 br.s (2H, OH), 6.52 t.t (2Hp, J 7.2, 1.1 Hz), 6.62 m
(4Hо), 7.38 m (4Hm), 7.54 m (4H,Ar). Found, %: C 72.24;
H 7.11; N 4.38; S 10.95. C36H44N2O2S2. Calculated, %:
C 71.96; H 7.38; N 4.66; S 10.67.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 8 2013