Electrophilic intramolecular cyclization of functional dervatives of unsaturated compounds: VII. Synthesis of 5-arylsulfanyl-6-phenylpiperidin-2-ones in the absence of salt additives and their selective reduction and oxidation

Article abstract of DOI:10.1134/S1070428015020165

Cinnamylacetamides reacted with arylsulfenyl chlorides in chloroform in the absence of LiClO₄ affording 5-(arylsulfanyl)-6-phenylpiperidin-2-ones. Their reduction with a system LiAlH₄-AlCl₃ resulted in 3-(tolylsulfanyl)-1,

Full text of DOI:10.1134/S1070428015020165

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2015, Vol. 51, No. 2, pp. 226–230. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © N.M. Tsizorik, A.I. Vas’kevich, R.I. Vas’kevich, M.V. Vovk, 2015, published in Zhurnal Organicheskoi Khimii, 2015, Vol. 51, No. 2,
pp. 237–241.
Electrophilic Intramolecular Cyclization of Functional
Dervatives of Unsaturated Compounds:
VІІ.* Synthesis of 5-Arylsulfanyl-6-phenylpiperidin-2-ones
in the Absence of Salt Additives
and Their Selective Reduction and Oxidation
N. M. Tsizorika, A. I. Vas’kevichb, R. I. Vas’kevicha, and M. V. Vovka
a Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine
b National Technical University of Ukraine “KPI,”
pr. Pobedy 37, Kiev, 03056 Ukraine
e-mail: vaskevich@ioch.kiev.ua
Received October 15, 2014
Abstract—Cinnamylacetamides reacted with arylsulfenyl chlorides in chloroform in the absence of LiClO4
affording 5-(arylsulfanyl)-6-phenylpiperidin-2-ones. Their reduction with a system LiAlH4–AlCl3 resulted in 3-
(tolylsulfanyl)-1,2-diphenylpiperidine, and with Raney nickel, in 1-aryl-6-phenylpiperidin-2-ones. The latter
treated with LiAlH4–AlCl3 were converted into 1-aryl-2-phenyl-piperidines. The oxidation of 5-(arylsulfanyl)-
6-phenylpiperidin-2-ones with hydrogen peroxide in acetone led to the formation of 5-sulfinyl-, and with
oxone, to 5-sulfonyl derivatives.
DOI: 10.1134/S1070428015020165
In our earlier report [2] on the study of reactions
between arylsulfenyl chlorides with amides of
unsaturated carboxylic acids we described the syn-
thesis of 5-arylsulfanyl-6-phenylpiperidin-2-ones by
the sulfa-nyl cyclization of cinnamylacetamides in
acetic acid in the presence of lithium perchlorate. It
was shown later by examples of styrylacetamide [3]
and cyclohex-2-en-acetamide [1] that the cyclization
occurred also in the environment possessing a high
ionizing ability (acetic acid and nitromethane) using
additives of strong electrolytes, e.g., lithium per-
chlorate. The reaction carried out in the less polar
chloroform resulted in the addition of the electrophilic
reagent to the С=С bond. Taking into consideration the
features of behavior in the arylsulfenylation reactions
of the S-cinnamyl-substituted nucleophilic systems
[4, 5] that consist in the formation in chloroform along
with minor addition products also the products of the
electrophilic cyclization we regarded as expedient to
study under these conditions the reactions of
cinnamylacetamides 1а–1d with arylsulfenyl chlorides
2а–2c.
Scheme 1.
O
O
_
R
S
Cl
R
Ph
Ar
N
N
H
ArSCl
+
+
H
CHCl3
S
Ph
N
R
O
Ar
1a_1d
2a_2c
A
3a_3g
1, R = Bu (а), Bn (b), Ph (c), 4-MeOC6H4 (d); 2, Ar = Ph (а), 4-MeC6H4 (b), 4-NO2C6H4 (c); 3, Ar = Ph, R = Bu (а), Bn (b),
Ph (c); R = Ph, Ar = 4-MeC6H4 (d), 4-NO2C6H4 (e); R = 4-MeOC6H4, Ar = Ph (f), 4-MeC6H4 (g).
* For communication VI, see [1].
226

ELECTROPHILIC INTRAMOLECULAR CYCLIZATION OF FUNCTIONAL ...VІІ.
227
Scheme 2.
1. LiAlH4_AlCl3
S
2. HCl
+
NH
_
Me
Ph
Cl
Ph
4
3c, 3d, 3f
1. LiAlH4_AlCl3
2. HCl
Ni-Ra
MeOH
+
NH
_
Ph
N
O
Ph
Cl
R
R
5a, 5b
6a, 6b
R = Ph (а), 4-MeOС6Н4 (b).
Amides 1а–1d in chloroform at 15°С readily
reacted with sulfenyl chlorides 2а–2c to give 5-(aryl-
sulfanyl)-6-phenylpiperidin-2-ones 3а–3g in 78–92%
yields. The analysis of the reaction mixtures by 1H NMR
and HPLC-MS showed that they lacked the addition
products. It is noteworthy that in contrast to the
previously used conditions (acetic acid–LiClO4) [2], in
the case of 4-nitrophenylsulfenyl chloride 2с the side
formation of pyran-2-iminium salts is excluded.
Presumably the observed intramolecular cyclization in
the solvent of low polarity is governed by the special
features of the structure of the cinnamyl fragment
whose phenyl substituent efficiently stabilizes the epi-
sulfonium intermediate А. Therefore the attack on it by
the nitrogen atom of the amide group becomes more
possible than the attack of the chloride anion (Scheme 1).
The identity of the physicochemical charactreistics of
the samples of compounds 3а–3g obtained under these
conditions and in the presence of the system acetic
acid–LiClO4 [2] shows the analogy in the stereocontrol
of the process and the trans-configuration of the
arylsulfanyl and phenyl substituents.
Bifunctional 5-arylsulfanyl-6-phenylpiperidin-2-ones
3а–3g containing the carbonyl and sulfanyl groups
sensitive to the action of reducing agents and also the
sulfanyl group capable of oxidation are convenient
models for the investigation of the selectivity of these
processes. Therewith in the syntheses of analogs of
natural and bioactive compounds the cyclosulfeny-
lation procedure is a widely used practice followed by
the reductive removal of the sulfanyl groups [9–12].
By the example of piperidinones 3с, 3d, and 3f we
demonstrated the possibility of both partial and
complete reduction of both functional groups. For
instance, treating compound 3d with the system
LiAlH4–AlCl3 led to the mild selective reduction of the
carbonyl group to form 3-(tolylsulfanyl)-1,2-diphenyl-
piperidine that was isolated in a 83% yield as hydro-
chloride 4 (Scheme 2). Its IR spectrum lacked the
absorption band of the С=О group, and in the 13С NMR
spectrum the singlet of the atom С6 was shifted upfield
(58.69 ppm).
In turn, at the reduction of compounds 3с and 3f
with Raney nickel the elimination of the
phenylsulfanyl group occurred to afford 1-aryl-6-
phenylpiperidin-2-ones 5а and 5b whose further
treatment with LiAlH4 in the presence of AlCl3
provided 1-aryl-2-phenylpiperidines isolated as
2-Piperidone ring is known to be present in the
structure of many alkaloids and physiologically active
compounds [6–8]. Therefore the development of
versatile modification of the piperidine ring is topical.
Scheme 3.
O
S
O
O
S
H2O2, Δ
KHSO5
Ar
Ar
3c_3e
H
MeOH_H2O
acetone
Ph
N
R
O
Ph
N
R
O
7, 8
9a_9c
R = Ph, Ar = 4-MeC6H4 (7), 4-NO2C6H4 (8); 9, R = Ph, Ar = Ph (a), 4-MeC6H4 (b), 4-NO2C6H4 (c).
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TSIZORIK et al.
228
hydrochlorides 6а and 6b. The obtained processes are
preparatively feasible as compared to the published
description of multistage reactions requiring special
conditions and reagents for the prepration of 1,6-
diphenylpiperidin-2-one [13, 14] and 1-aryl-2-phenyl-
piperidines [15, 16].
tographed on silica gel, eluent hexane–ethyl acetate, 1 : 2,
and the solid residue (compounds 3c–3g) was filtered
off, dried in air, and crystallized from ethanol.
Physicochemical constants of compounds obtained
are consistent with those published in [2]. Yields 87%
(3а), 89% (3b), 78% (3c), 85% (3d), 88% (3e), 90%
(3f), 92% (3g).
Compounds containing a sulfanyl group are key
object for the synthesis of chemically and biologically
important sulfoxides and sulfones [17–20]. At the
treatment of pyrimidines 3d and 3e with hydrogen
peroxide in acetone the arylsulfanyl fragment readily
oxidized to a sulfoxide. Taking into account the chiral
character of the latter this transformation affords
compounds 7 and 8, where each compound consists of
a mixture of diastereomers А and B, ~1 : 1 (Scheme 3).
These diastereomeric mixtures were separated by the
crystallization from a mixture hexane–benzene, 1 : 1,
and the individual substances were characterized. In
the 1H NMR spectrum of diastereomer А the signals of
the methane protons H5 and H6 appear at 4.90–5.18
and 3.06–3.26 ppm, in the spectrum of diastereomer B,
at 5.63–5.74 and 3.01–3.14 ppm respectively. In the
13С NMR spectrum of isomers А characteristic signals
are those of C5 (67.62–67.76 ppm) and С6 (64.00–
64.17 ppm), and for isomers B, of С5 (68.49–
68.53 ppm) and С6 (61.78–62.27 ppm).
3-[(4-Methylphenyl)sulfanyl]-1,2-diphenyl-pipe-
ridinium chloride (4). To a slurry of 152 mg (0.4 mmol)
of LiAlH4 and 534 mg (0.4 mmol) of aluminum
chloride in 25 mL of ethyl ether was added 500 mg
(0.133 mmol) of piperidinone 3d, and the mixture was
stirred at room temperature for 2 h. Then the reaction
mixture was treated in succession with 15 mL of 10%
NaOH, 10 mL of 10% HCl, the organic layer was
extracted with chloroform (3 × 10 mL), the extract was
dried with anhydrous Na2SO4, evaporated, the residue
was dissolved in 10 mL of dioxane, and saturated with
gaseous HCl. The solution was evaporated, the solid
residue was crystallized from ethyl ether. Yield 83%,
mp 102–103°С. IR spectrum, ν, cm–1: 3415, 2485,
1
1490. H NMR spectrum (CDCl3), δ, ppm: 1.62–1.85
m (1H, СH), 1.91–2.03 m (1H, СH), 2.25 s (3H, СH3),
2.40–2.51 m (1H, СH), 3.14–3.30 m (1H, СH), 3.38–
3.52 m (1H, СH), 3.71–3.83 m (1H, СH), 4.14–4.36 m
(2H, 2СH), 6.81–7.29 m (12HAr), 7.45–8.53 m (2HAr),
13.95 s (1H, NH). 13С NMR spectrum (CDCl3), δ,
ppm: 20.99 (СH3), 22.76 (С5), 31.66 (С4), 47.98 (С3),
58.69 (С6), 77.33 (С2), 127.85, 129.13, 129.39, 129.55,
129.58, 132.18, 134.22, 138.27, 140.73 (СAr). Mass
spectrum: m/z 360.1 [M + 1]+. Found, %: С 72.70; H
6.57; N 3.59. C24H26СlNS. Calculated, %: С 72.79; H
6.62; N 3.54. M 359.99.
The selective conversion of 5-sulfanylpiperidones
3c–3e into the corresponding sulfones was carried out
using oxone. Its double excess is optimum for the
preparation of 5-(arylsulfonyl)-1,6-diphenyl-piperidin-
2-ones 9а–9с in 97–98% yields.
EXPERIMENTAL
1-Aryl-6-phenylpiperidin-2-ones (5a and 5b). To
a solution of 2 mmol of piperidinone 3c and 3f in
15 mL of methanol at 20°С while stirring was added 7 g
of activated Raney nickel. The reaction mixture was
strred for 5 h, the precipitate was filtered off, the
filtrate was evaporated, the residue was crystallized
from hexane.
IR spectra were recorded on a spectrophotometer
1
Vertex 70 from pellets with KBr. H and 13С NMR
spectra were registered on a spectrometer Varian
VXR-400 (399.97 and 125.74 MHz respectively),
internal reference TMC. HPLC-MS measurements
were performed on an instrument Agilent 1100
\DAD\HSD\VLG 119562.
1,6-Diphenylpiperidin-2-one (5a). Yield 89%, mp
124–125°С (mp 125–127°С [13]).
5-Arylsulfanyl-1-R-6-phenylpiperidin-2-ones (3а–
3g). To a solution of 2 mmol of amide 1а–1d in 10 mL
of chloroform was added dropwise while stirring at
15°С a solution of 2 mmol of arylsulfenyl chloride 2а–
2c in 5 mL of chloroform. The reaction mixture was
stirred for 12 h and evaporated in a vacuum. To the
residue 10 mL of hexane was added, the formed oily
substances (compounds 3а and 3b) were chroma-
1-(4-Methoxyphenyl)-6-phenylpiperidin-2-one
(5b). Yield 91%, mp 140–141°С. IR spectrum, ν, cm–1:
1
3435, 1650 (С=О), 1509. H NMR spectrum (CDCl3),
δ, ppm: 1.63–2.0 m (3H, СH), 2.25–2.35 m (1H, СH),
2.57–2.74 m (2H, СH), 3.69 s (3H, ОСH3), 4.90–4.93
m (1H, СH), 6.73 d (2HAr, J 8.8 Hz), 7.00 d (2HAr, J
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ELECTROPHILIC INTRAMOLECULAR CYCLIZATION OF FUNCTIONAL ...VІІ.
229
8.4 Hz), 7.16–7.30 m (5HAr). 13С NMR spectrum
(CDCl3), δ, ppm: 17.17 (С4), 31.88 (С3), 32.18 (С5),
54.90 (ОСH3), 64.99 (С6), 113.72, 126.59, 127.03,
127.98, 128.04, 134.74, 141.06, 157.51 (СAr), 170.64
(С2). Mass spectrum: m/z 282.2 [M + 1]+. Found, %: С
76.90; H 6.77; N 4.95. C18H19NO2. Calculated, %: С
76.84; H 6.81; N 4.98. M 281.35.
was recrystallized from water. Diastereomers were
separated by fractional crystallization from a mixture
hexane–benzene, 1 : 1.
5-[(4-Methylphenyl)sulfinyl]-1,6-diphenyl-pipe-
ridin-2-one (7). Diastereomer А. Yield 38%, mp 174–
1
175°С. IR spectrum, ν, cm–1: 1650 (С=О). H NMR
spectrum (CDCl3), δ, ppm: 1.95–2.07 m (1H, СH),
2.33–2.48 m (4H, СH3 + СH), 2.61–2.72 m (1H, СH),
2.87–2.98 m (1H, СH), 3.06–3.13 m (1H, СH), 4.91 d
(1H, СH, J 4.8 Hz), 7.01 d (2HAr, J 7.6 Hz), 7.08 d
(2HAr, J 6.8 Hz), 7.18–7.37 m (8HAr), 7.45 d (2HAr, J
8 Hz). 13С NMR spectrum (CDCl3), δ, ppm: 16.39
(С4), 21.38 (СH3), 29.69 (С3), 64.00 (С6), 67.62 (С5),
124.90, 126.76, 126.87, 126.94, 128.21, 128.84
128.92, 130.13, 138.17, 139.27, 141.51, 142.45 (СAr),
169.80 (С2). Mass spectrum: m/z 390.0 [M + 1]+.
Found, %: С 73.87; H 5.83; N 3.69. C24H23NО2S.
Calculated, %: С 74.00; H 5.95; N 3.60. M 389.51.
1-Aryl-2-phenylpiperidinium chlorides (6а and
6b). To a slurry of 137 mg (0.36 mmol) of LiAlH4 and
480 mg (0.36 mmol) of aluminum chloride in 25 mL
of ethyl ether was added 0.12 mmol of piperidinone 3c
and 3f, and the mixture was stirred at room
temperature for 2 h. Then the reaction mixture was
treated in succession with 15 mL of 10% NaOH, 10 mL
of 10% HCl, the organic layer was extracted with
chloroform (3 × 10 mL), the extract was dried with
anhydrous Na2SO4, evaporated, the residue was
dissolved in 10 mL of dioxane, and saturated with
gaseous HCl. The solution was evaporated, the solid
residue was crystallized from ethyl ether.
Diastereomer B. Yield 31%, mp 164–165°С. IR
1
spectrum, ν, cm–1: 1650 (С=О). H NMR spectrum
1,2-Diphenylpiperidinium chloride (6а). Yield
85%, mp 174–175°С. IR spectrum, ν, cm–1: 3434,
2945, 2409, 1492. 1H NMR spectrum (CDCl3), δ, ppm:
1.72–1.99 m (2H, 2СH), 2.08–2.19 m (2H, СH2),
2.89–2.99 m (1H, СH), 3.08–3.19 m (1H, СH), 3.41–
3.52 m (1H, СH), 3.83 d (1H, СH, J 11.2 Hz), 4.31 t
(1H, СH, J 10.4 Hz), 7.08–7.26 m (6HAr), 7.51–7.75 m
(4HAr), 13.82 s (1H, NH). 13С NMR spectrum (CDCl3),
δ, ppm: 22.90 (С4), 23.49 (С5), 31.58 (С3), 59.83 (С6),
73.41 (С2), 128.70, 128.91, 129.31, 129.57, 134.95,
140.99 (СAr). Mass spectrum: m/z 238.2 [M – HCl + 1]+.
Found, %: С 74.49; H 7.34; N 5.11. C17H20СlN.
Calculated, %: С 74.57; H 7.36; N 5.12. M 273.80.
(CDCl3), δ, ppm: 1.45–1.55 m (1H, СH), 2.33–2.45 m
(4H, СH3 + СH), 2.72–2.78 m (2H, СH2), 3.02–3.06 m
(1H, СH), 5.70–5.74 m (1H, СH), 7.18–7.37 m
(12HAr), 7.63 d (2HAr, J 8 Hz). 13С NMR spectrum
(CDCl3), δ, ppm: 17.33 (С4), 21.42 (СH3), 28.84 (С3),
62.27 (С6), 68.53 (С5), 125.17, 126.62, 127.18, 127.23,
127.93, 128.89 129.02, 130.19, 138.73, 138.98,
141.89, 142.85 (СAr), 169.11 (С2). Mass spectrum: m/z
390.0 [M + 1]+. Found, %: С 74.12; H 5.91; N 3.53.
C24H23NО2S. Calculated, %: С 74.00; H 5.95; N 3.60.
M 389.51.
5-[(4-Nitrophenyl)sulfinyl]-1,6-diphenyl-pipe-
ridin-2-one (8). Diastereomer А. Yield 42%, mp 178–
1
1-(4-Methoxyphenyl)-2-phenylpiperidinium
179°С. IR spectrum, ν, cm–1: 1653 (С=О), 1520. H
chloride (6b). Yield 88%, mp 187–188°С. IR
NMR spectrum (CDCl3), δ, ppm: 1.84–1.95 m (1H,
СH), 2.28–2.40 m (1H, СH), 2.53–2.72 m (1H, СH),
2.80–2.95 m (1H, СH), 3.13–3.26 m (1H, СH), 5.12–
5.18 m (1H, СH), 6.95–7.03 m (2HAr), 7.10–7.38 m
(8HAr), 7.62–7.73 m (2HAr), 8.26–8.35 m (2HAr). 13С
NMR spectrum (CDCl3), δ, ppm: 16.75 (С4), 30.32
(С3), 64.17 (С6), 67.76 (С5), 124.09, 125.39, 126.57,
126.81, 126.84, 128.36 128.65, 128.91, 138.42,
140.72, 148.65, 149.47 (СAr), 169.18 (С2). Mass
spectrum: m/z 421.2 [M + 1]+. Found, %: С 65.80; H
4.70; N 6.63. C23H20N2О4S. Calculated, %: С 65.70; H
4.79; N 6.66. M 420.48.
1
spectrum, ν, cm–1: 3431, 2429, 1515, 1268. H NMR
spectrum (CDCl3), δ, ppm: 1.68–2.16 m (4H, СH2 +
2СH), 2.81–2.92 m (1H, СH), 3.01–3.15 m (1H, СH),
3.39–3.51 m (1H, СH), 3.65 s (3H, ОСH3), 3.73–3.82
m (1H, СH), 4.23–4.37 m (1H, СH), 6.63–6.71 m
(2HAr), 7.09–7.20 m (3HAr), 7.51–7.70 m (4HAr), 13.57
s (1H, NH). Mass spectrum: m/z 268.2 [M – HCl + 1]+.
Found, %: С 71.20; H 7.28; N 4.64. C18H22СlNО.
Calculated, %: С 71.12; H 7.30; N 4.61. M 303.83.
5-Arylsulfinyl-1,6-diphenylpiperidin-2-ones (7
and 8). To a solution of 3 mL of 30% hydrogen
peroxide in 15 mL of acetone was added 0.1 mmol of
piperidinone 3d and 3e, and the mixture was stirred at
50°С for 5 h. The solution was evaporated, the residue
Diastereomer B. Yield 36%, mp 169–170°С. IR
1
spectrum, ν, cm–1: 1651 (С=О), 1521, 1344. H NMR
spectrum (CDCl3), δ, ppm: 1.62–1.74 m (1H, СH),
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TSIZORIK et al.
230
2.12–2.26 m (1H, СH), 2.77–2.92 m (2H, СH2), 3.04–
3.14 m (1H, СH), 5.63–5.70 m (1H, СH), 7.11–7.36 m
(10HAr), 7.92 d (2HAr, J 8 Hz), 8.38 d (2HAr, J 7.6 Hz).
13С NMR spectrum (CDCl3), δ, ppm: 17.71 (С4), 28.90
(С3), 61.78 (С6), 68.49 (С5), 124.46, 126.02, 126.63,
127.18, 127.38, 128.26 129.04, 129.11, 138.28,
141.55, 149.64, 149.97 (СAr), 168.58 (С2). Mass
spectrum: m/z 421.2 [M + 1]+. Found, %: С 65.78; H
4.75; N 6.70. C23H20N2О4S. Calculated, %: С 65.70; H
4.79; N 6.66. M 420.48.
(1H, СH), 2.90–3.01 m (1H, СH), 3.57–3.64 m (1H,
СH), 5.54 s (1H, СH), 7.14–7.38 m (10HAr), 8.11 d
(2HAr, J 8 Hz), 8.38 d (2HAr, J 8 Hz). Mass spectrum:
m/z 437.1 [M + 1]+. Found, %: С 63.33; H 4.60; N
6.39. C23H20N2О5S. Calculated, %: С 63.29; H 4.62; N
6.42. M 436.48.
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(9а–9с). To a solution of 0.08 mmol of piperidinone
3с–3е in 10 mL of methanol was added while stirring 1 g
(0.17 mmol) of oxone dissolved in 5 mL of water. The
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(9а). Yield 98%, mp 151–152°С. IR spectrum, ν, cm–1:
1
1674 (С=О). H NMR spectrum (CDCl3), δ, ppm:
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2.15–2.23 m (2H, СH2), 2.59–2.69 m (1H, СH), 2.88–
2.99 m (1H, СH), 3.44–3.50 m (1H, СH), 5.53 s (1H,
СH), 7.10–7.34 m (10HAr), 7.49–7.59 m (2HAr), 7.63–
7.70 m (1HAr), 7.91 d (2HAr, J 7.2 Hz). 13С NMR
spectrum (CDCl3), δ, ppm: 17.89 (С4), 28.49 (С3),
61.82 (С6), 64.68 (С5), 125.91, 126.60, 126.90, 127.94,
128.32, 128.76 128.82, 129.24, 133.96, 136.88,
139.41, 141.87 (СAr), 169.38 (С2). Mass spectrum: m/z
392.2 [M + 1]+. Found, %: С 70.51; H 5.39; N 3.61.
C23H21NО3S. Calculated, %: С 70.56; H 5.41; N 3.58.
M 391.48.
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Ohgon, M., Ueno, M., and Nishizawa, Y., Epilepsia,
2011, vol. 52, p. 1331.
9. Ohsawa, T., Ihara, M., Fukumoto, K., and Kametani, T.,
J. Org. Chem., 1983, vol. 48, p. 3644.
10. Nicolaou, K.C., Seitz, S.P., Sipio, W.J., and Blount, J.F.,
J. Am. Chem. Soc., 1979, vol. 101, p. 3884.
11. Francoise, T., Grierson, D.S., and Husson, H.-P.,
Tetrahedron Lett., 1990, vol. 31, p. 523.
12. Koriyama, Y., Nozawa, A., and Hayakawa, R.,
5-(Tosylsulfonyl)-1,6-diphenylpiperidin-2-one
(9b). Yield 97%, mp 159–160°С. IR spectrum, ν, cm–1:
1
1652 (С=О). H NMR spectrum (CDCl3), δ, ppm:
Tetrahedron, 2002, vol. 58, p. 9621.
2.14–2.23 m (2H, СH2), 2.44 s (3H, СH3), 2.57–2.67 m
(1H, СH), 2.85–2.97 m (1H, СH), 3.43–3.48 m (1H,
СH), 5.51 s (1H, СH), 7.14–7.36 m (12HAr), 7.78 d
(2HAr, J 8 Hz). 13С NMR spectrum (CDCl3), δ, ppm:
18.22 (С4), 21.52 (СH3), 28.76 (С3), 62.09 (С6), 65.01
(С5), 126.14, 126.80, 127.09, 128.12, 128.62, 128.97
129.04, 130.11, 134.10, 139.86, 142.19, 145.38 (СAr),
169.67 (С2). Mass spectrum: m/z 406.2 [M + 1]+.
Found, %: С 71.13; H 5.68; N 3.41. C24H23NО3S.
Calculated, %: С 71.08; H 5.72; N 3.45. M 405.51.
13. Bennet, D.J., Blake, A.J., Cooke, P.A., Gadfrey, C.R.A.,
Pickering, P.L., Simpkins, N.S., Walker, M.D., and
Wilson, C., Tetrahedron, 2004, vol. 60, p. 4491.
14. Fuwa, H., Kaneko, A., Sugimoto, Y., Tomita, T.,
Iwatsubo, T., and Sasaki, M., Heterocycles, 2006, vol. 70,
p. 101.
15. Lewis, F.D., Wagner-Brennan, J.M., and Miller, A.M.,
Canad. J. Chem., 1999, vol. 77, p. 595.
16. Giera, D.S., Siskert, M., and Scneider, C., Org. Lett.,
2008, vol. 10, p. 4259.
17. Soladie, G., Synthesis, 1981, p. 185.
5-[(4-Nitrophenyl)sulfonyl]-1,6-diphenyl-pipe-
18. Madeslaire, M., Tetrahedron, 1986, vol. 42, p. 5459.
19. Carreno, M.C., Chem. Rev., 1995, vol. 95, p. 1717.
20. Prilezhaeva, E.N., Russ. Chem. Rev., 2000, vol. 69, p. 367.
ridin-2-one (9с). Yield 98%, mp 197–198°С. IR
1
spectrum, ν, cm–1: 1657 (С=О). H NMR spectrum
(CDCl3), δ, ppm: 2.19–2.36 m (2H, СH2), 2.65–2.75 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 51 No. 2 2015