Copper(i)-mediated synthesis of β-hydroxysulfones from styrenes and sulfonylhydrazides: An electrochemical mechanistic study

Article abstract of DOI:10.1039/c6ra19190h

Copper(i) halides were used as mediators in the synthesis of β-hydroxysulfones via the oxysulfonylation of styrenes using sulfonylhydrazides. The feature of the developed process lies in the combination of a copper(i) salt with oxygen - the stoichiometric oxidant. Copper(ii) species are responsible for the oxidation of sulfonylhydrazides, they are generated in small amounts in the O₂/Cu(i)/Cu(ii) redox system, which is formed during the reaction. The combination of these three components enables one to obtain in the case of α-methylstyrenes only β-hydroxysulfones and in the case of α-unsubstituted styrenes, β-hydroxysulfones as the main products and β-ketosulfones as the by-products. With good yields β-hydroxysulfones were prepared by reduction of the reaction mixture containing both products β-hydroxysulfones and β-ketosulfones with NaBH₄. An electrochemical study revealed that the Cu(i)/Cu(II) pair can serve as an effective mediator of β-hydroxysulfones formation via redox processes.

Full text of DOI:10.1039/c6ra19190h

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Copper (I)-mediated synthesis of β-hydroxysulfones from styrenes
and sulfonylhydrazides. Electrochemical mechanistic study
Received 00th January 20xx,
Accepted 00th January 20xx
ab
a
ab
a
Alexander O. Terent’ev,* Olga M. Mulina, Dmitry A. Pirgach, Dmitry V. Demchuk, Mikhail A.
a
a
Syroeshkin and Gennady I. Nikishin
DOI: 10.1039/x0xx00000x
Copper (I) halides were used as mediators in the β-hydroxysulfones synthesis through oxysulfonylation of styrenes with
the use of sulfonylhydrazides. The feature of the developed process lies in the combination of copper (I) salt with oxygen
www.rsc.org/
—
stoichiometric oxidant. Copper (II) species are responsible for the oxidation of sulfonylhydrazides, they are generated in
a small amount in the O /Cu(I)/Cu(II) redox system, which is formed during the reaction. The combination of these three
2
components enables to obtain in the case of α-methylstyrenes only β-hydroxysulfones and in the case of α-unsubstituted
styrenes β-hydroxysulfones as the main products and β-ketosulfones as the byproducts. With good yields β-
hydroxysulfones were prepared by reduction of the reaction mixture containing both products β-hydroxysulfones and β-
4
ketosulfones with NaBH . Electrochemical study revealed that the Cu (I)/Сu(II) pair can serve as effective mediator of β-
hydroxysulfones formation via redox processes.
Introduction
The latter method is applied for the synthesis of structures
containing β-hydroxysulfone moiety predominantly at tertiary
β-Hydroxysulfones are of great interest as structural units of
16
1
2
carbon atom, which cannot be further oxidized (Scheme 1, eq. 2) .
antifungal and antitumor compounds, they are known as
3
For sulfonylation of unsaturated compounds without additional
inserting oxygen into the molecule a number of oxidants are
intermediates in the synthesis of lactones and unsymmetrical
4
alkenes . Traditionally β-hydroxysulfones are obtained through
1
7,18
19
20
21
22
5
-8
exploited: Cu(OAc)
2
,
CAN , NBS ,
K
2
S
O
2
8
,
peroxides ,
nucleophilic addition of sulfinates to epoxides , reduction of β-
2
3
24,25
9
,10
11
I /TBHP and TBAI/TBHP
2
systems. It is well-known that oxygen
ketosulfones
and hydroxylation of α, β-unsaturated sulfones .
is an ideal environment-friendly oxidant, which offers fascinating
industrial and academic prospects. In oxidative transformations in
most cases it is used in cooperation with transition metals salts and
For the last years several oxidative strategies for β-hydroxysulfones
preparation from olefins were established. In these reports air and
1
2,13,14
thermally low stable
PPh (Scheme 1, eq. 1) or sulfonylhydrazides with O
salts were required.
sulfinic acids in combination with O
2
and
26-29
1
5
complexes
.
3
2
and Fe (III)
In this context, we disclosed the process of styrenes
oxysulfonylation by utilizing sulfonylhydrazides in the presence of
O /Cu(I) system, leading to β-hydroxysulfones. During the reaction
2
the O /Cu(I)/Cu(II) system is formed with a small amount of Cu(II)
2
that is confirmed by the near absence of specific for Cu(II) species
colour. As a result, β-hydroxysulfones 3 as main products and β-
ketosulfones 4 as byproducts are formed (Scheme 2).
Results and discussion
The synthesis of β-hydroxysulfones 3aa-3fe and β-ketosulfones 4aa-
4
ab from styrenes 1a-1j with the use of sulfonylhydrazides 2a-2e
was conducted in СH CN, СH CN–H O, THF, THF–H with
/Cu(I)/Cu(II) redox system. This system resulted from
3
3
2
2
O
Scheme 1 Recent works for oxysulfonylation of styrenes.
O
2
transformations of CuCl, CuBr, CuI in aerobic conditions (Scheme 2).
Our preliminary studies were focused on the reaction of styrene 1a
with sulfonylhydrazide 2a, leading to 1-phenyl-2-tosylethanol 3aa
and 1-phenyl-2-tosylethanone 4aa formation. We examined the
influence of Cu (I) salt counteranion, oxygen source (air oxygen or
a.
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
Leninsky Prospect 47, Moscow, 119991, Russian Federation. E-mail:
terentev@ioc.ac.ru; Fax: (+7)499-1355328
b.
D.I. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya square,
Moscow, 125047, Russian Federation
Electronic Supplementary Information (ESI) available: [NMR spectra of all
†
9
8% oxygen) and solvent type (Table 1) on 3aa yield.
synthesized compounds]. See DOI: 10.1039/x0xx00000x
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Scheme 2 Oxysulfonylation of styrenes 1a-1j with the use of sulfonylhydrazides 2a-2e (in the codification of 3 and 4 the first letter index
refers to the styrene 1 moiety, the second letter index to the hydrazide 2 moiety).
Table 1 Screening of the reaction conditions.
Ratio
mole Cu(I) / mole 1a)
CuBr (2)
Oxygen source
Solvent
a
a
Total yield
3aa and 4aa (%)
42
Entry
Time (h)
Yield 3aa (%)
Yield 4aa (%)
a
(
1
2
3
7
air
air
air
air
air
air
air
air
air
air
СH
СH
СH
3
3
3
CN–H
CN–H
CN–H
2
2
2
O
O
O
28
25
14
15
10
27
16
5
7
CuCl (2)
CuI (2)
40
27
65
46
15
53
32
41
28
91
23
78
80
7
17
b
4
7 + 12
7 + 12
7 + 12
7 + 12
7 + 12
7 + 12
7 + 12
7 + 12
7 + 12
7
CuBr (2)
CuBr (2)
CuBr (0.2)
CuBr (5)
CuBr (2)
CuBr (2)
CuBr (2)
CuBr (2)
CuBr (0.2)
CuBr (2)
CuBr (2)
СH CN–H O
38 (61)
30
3
3
3
3
2
2
2
2
c
5
СH
СH
СH
CN–H
CN–H
CN–H
O
O
O
6
7
8
9
10
36
17
12
13
10
36
8
СH CN
3
20
THF
28
1
1
1
1
0
1
2
3
THF–H
2
O
18
О
2
3
СH CN–H
2
O
55 (85)
15
О2
СH CN–H O
3
3
3
2
2
2
О
О
2
2
СH
СH
CN–H
CN–H
O
O
43 (71)
50(77)
35
30
c
4
1
7 + 12
General procedure: to the solution of styrene 1a (300 mg, 2.88 mmol) in 25 ml (СH
3 2 3 2
CN–H O (5:1), СH CN, THF, THF–H O (5:1)) Cu (I) salt
(
0.58-14.4 mmol, molar ratio 0.2-5 mol of salt / mol 1a) and sulfonylhydrazide 2a (537 mg, 2.88 mmol, molar ratio 1 mol 2a / mol 1a) were
a
1
added. The mixture was stirred for 7 h at 40°C. The yield was determined by H NMR using 1,4-dinitrobenzene as an internal standard,
b
c
4
isolated yield after reduction with NaBH is in parentheses. 7 h at 40°C, then 12 h at 20-25°С. 7 h at 80 °C, then 12 h at 20-25°С.
Entries 1-3 indicated that among copper (I) halides, CuBr, CuCl and Decreasing (entry 6) or increasing (entry 7) of molar ratio of CuBr
CuI, usage of CuBr afforded the highest total yield of per mol 1a in comparison with previous entries resulted in reduced
oxysulfonylation products and the yield of desired product 3aa for 7 yield of the desired product. Employing СH
hours. When the reaction was performed for more prolonged time in place of СH CN–H (5:1) negatively influenced reaction
entry 4) yield of 3aa reached 38%. Heating the reaction mixture for efficiency (entries 8-10). In entry 11 air oxygen was replaced for
the first 7 hours to 80°C (entry 5) didn’t increase yield of 3aa. 98% oxygen, as a result 3aa yield was improved to 55%, total yield
3 2
CN, THF, THF-H O (5:1)
3
2
O
(
2
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of oxysulfonylation products in this case reached 91%. Attempts completed and then carried out reduction of ketosulfones using
failed (entries 12-14) of increasing desired product yield through NaBH (Scheme 3). As a result, β-hydroxysulfones 3 were obtained
4
modification of molar ratio of CuBr per mol 1a, temperature and in 52-89% overall yield in two steps (Entries 4, 11, 13, 14 in Table 1
reaction time, compared to entry 11 conditions, in which the best and Table 2).
result was obtained; total yield of 3aa and 4aa in these experiments
didn't exceed 80%.
With the optimized reaction conditions in hand (entry 11, Table 1),
scope of this copper-mediated oxysulfonylation reaction was
investigated. A number of β-hydroxysulfones 3aa-3ab were formed
in 32-65% yield, β-ketosulfones 4aa-4ab were observed as
4
Scheme 3 Reduction of β-ketosulfones with NaBH .
byproducts in 18-33% yield (Table 2).
This oxysulfonylation reaction was also examined by applying of α-
methylstyrenes (Table 3). A variety of α-methylstyrenes bearing
either electron withdrawing or electron donating substituents on
the aryl ring worked well under conditions of entry 11 (Table 1) and
target β-hydroxysulfones were formed in most cases in good yields.
It is important to note that in the reactions of
methylsulfonylhydrazide with styrene 1a, and octene-1 or
cyclohexene with sulfonylhydrazide 2a oxysulfonylation products
were not observed in measurable yields.
Table 2 Structure and yield of β-hydroxysulfones 3 and β-
a
ketosulfones 4 .
OH
O
S
OH
O
S
O
O
3
aa, 55% (85%)
3ba, 37% (54%)
O
O
S
O
O
S
The structures of all synthesized hydroxysulfones
3 and
O
O
1
13
ketosulfones 4 were confirmed with H, C NMR spectroscopy,
elemental analysis, HRMS and IR spectroscopy.
4
aa, 36%
4ba, 18%
a
Table 3 Structure and yield of β-hydroxysulfones 3 .
OH
O
S
OH
O
S
OH
O
S
OH
O
S
O
O
O
O
Cl
3
fa, 92%
3ga, 90%
3
ca, 53% (72%)
3da, 65% (89%)
OH
O
S
OH
O
S
O
O
S
O
O
S
O
O
O
O
Br
2
O N
3
ha, 93%
3ia, 89%
OH
O
OH
O
S
4
ca, 23%
4da, 31%
S
Br
OH
O
S
OH
O
S
O
O
I
I
MeO
O
O
3ja, 90%
3fc, 52%
Cl
OH
O
S
OH
O
S
3
ea, 32% (52%)
3ab, 40% (62%)
OMe
NO
2
O
O
S
O
O
S
O
O
O
3fd, 85%
3fe, 36%
O
a
Cl
Isolated yield.
Proposed reaction mechanism
4
ea, 24%
4ab, 25%
a
1
The yield was determined by H NMR using 1,4-dinitrobenzene as
To study plausible reaction mechanism the investigation of redox
an internal standard; isolated yield after reduction with NaBH
4
is in
properties of oxygen, styrene 1a, p-toluenesulfonylhydrazide 2a
parentheses.
3 2
and CuBr in CH CN–H O (5:1) solution with the use of cyclic
In all examples hydroxysulfone is predominantly formed
independently from the properties of a substituent on the benzene
ring. In most cases molar ratio of hydroxysulfone 3 / ketosulfone 4
is 2:1. It is well-known that ketones can be easily reduced into
voltammetry (CV) was carried out. Tetrabutylammonium
perchlorate was chosen as a supporting electrolyte. Obtained CV
curves are shown in Fig. 1.
3
0-32
corresponding alcohols
. That’s why in order to transform β-
ketosulfones 4, byproducts, into desired β-hydroxysulfones 3 we
filtered the reaction mixture from CuBr after the reaction
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is formed after the fragmentation of species generated from the
5
5
56-58
reaction of peroxyradical C with Cu(I) ions or oxygen
.
Cu (II)
OH
Ts
TsNHNH
2
Ph
Ts
3aa
2a
Ts
OOH
A
Ph
Ph
D
Ph
O
2
1a
X-H
OO
Ts
Ts
Ph
O
2
C
B
O
Ts
Ts
Ph
Ph
OH
4aa
E
Figure 1 CV curves for 2.0 mmol/L solutions of CuBr (red), p-
toluenesulfonylhydrazide 2a (blue), styrene 1a (black) and aerated
Ts
Ph
2
H O
3aa
- H
4 4 3 2
supporting solution (grey) in 0.1M Bu NClO in CH CN–H O (5:1) on
a working glassy-carbon electrode (d = 1.7 mm) under scan rate 100
mV/s.
Cu (I)
Scheme 4 Plausible oxysulfonylation mechanism on the
Oxidizing properties of oxygen are evidenced in reducing in
relatively early potentials, the peak on CV curve with potential -1.10
V is responsible for its reduction. Chemically irreversible styrene 1a
oxidation takes place in far region with maximum at 1.90 V and runs
into discharge of the background. Chemically irreversible peak at
example of the reaction of styrene 1a and p-
toluenesulfonylhydrazide 2a
.
The fact that using of octene-1 and cyclohexene as starting reagents
didn’t lead to the formation of oxysulfonylation products can be
explained with low stability of C-centered alkyl radical generated
after addition of tosyl radical A to double bond.
1.35 V is responsible for oxidation of p-toluenesulfonylhydrazide 2a,
therefore we can conclude that its oxidation goes rather more
easily than oxidation of styrene.
Chemically and electrochemically reversible peak with Е1/2 = 0.55 V
corresponds to oxidation of Cu (I) into Cu (II). It takes place in the
Conclusions
potential range between oxygen reduction and
p-
In summary, we have demonstrated a novel copper-mediated
oxysulfonylation of styrenes using sulfonylhydrazides for synthesis
of corresponding β-hydroxysulfones in 32-93% yield. In the case of
α-unsubstituted styrenes β-ketosulfones are formed as the
byproducts. Applying of α-methylstyrenes in this methodology gives
β-hydroxysulfones as single products in high yield. Moreover, using
voltammetry, experimental data and previous reports, plausible
reaction pathway was proposed. Coupling of two starting reagents
toluenesulfonylhydrazide 2a oxidation. It means that in
experimental conditions Cu (I)/Сu (II) pair can serve as effective
mediator of p-toluenesulfonylhydrazide 2a oxidation by oxygen.
On the basis of obtained experimental data and previous studies of
reactions proceeding through generation of S-centered radicals
3
3-35
from sulfonylhydrazides
oxysulfonylation process (Scheme 4). Cu(I) ions are oxidized to Cu(II)
, we proposed the pathway of
3
6-40
in the presence of oxygen, it is confirmed by numerous kinetic
41-44
proceeds under the action of O /Cu(I)/Cu(II) redox system. The
2
studies of this process
. Almost colourless solution during the
distinguishing feature of the work lies in the combination of oxygen
reaction evidences for a small amount of Cu(II). Afterwards, as a
and a copper (I) salt, which is oxidized to copper (II) on a limited
scale, that makes it possible to obtain β-hydroxysulfones as the
main products.
result of a successive oxidation of hydrazide 2a under the action of
20, 33, 34
Cu(II)
Ts) is generated, which reacts with styrene 1a forming C-centered
, oxygen or peroxyradical C, S-centered tosyl radical A
(
2
0
benzyl radical B . On the next step radical B is trapped with oxygen
forming peroxyradical C. Then, after abstraction of hydrogen atom
from a hydrogen donor X-H (NH and CH) peroxyradical C transforms
Experimental
4
5
into hydroperoxide D , which gives the main product 3aa after the NMR spectra were registered on Bruker Avance II 300 MHz
4
6-51
reduction
centered benzyl radical B oxidation by Cu(II) species to the solvent peaks as an internal standard set to δ 7.25 and δ 77.0
. Alcohol 3aa can be also formed due to the C- instrumental. Chemical shifts are measured relative to residual
5
2-54
intermediate cation E followed by its hydroxylation
3 6
. Ketone 4aa (CDCl ), δ 2.50 and δ 39.51 (DMSO-d ). IR spectra were recorded on
a FT-IR spectrometer. High resolution mass spectra (HRMS) were
4
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measured using electrospray ionization (ESI). The measurements chromatography on SiO
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DOI: 10.1039/C6RA19190H
ARTICLE
5
9
2
with elution using PE-EA in a linear
were done in a positive ionmode (interface capillary voltage 4500 gradient of the latter from 0 to 10 vol %.
6
2
V); the mass ratio was from m/z 50 to 3000 Da; external/internal 1-Isopropyl-4-vinylbenzene (1с) . 4-iso-Propylbenzaldehyde (3.0
calibration was done with Electrospray Calibrant Solution. A syringe g, 20.2 mmol) gave the title compound as a colourless oil (2.2 g,
1
injection was used for solutions in CH
3
CN (flow rate 3 μL/min). 15.2 mmol, 75%). H NMR (CDCl
3
), δ: 1.24 (d, J = 6.9 Hz, 6 H), 2.80-
Nitrogen was applied as a dry gas; interface temperature was set at 2.96 (m, 1 Н), 5.17 (dd, J = 10.9, 1.1 Hz, 1 H), 5.69 (dd, J = 17.6, 1.1
80 °C. The TLC analyses were carried out on standard silica-gel Hz, 1 H), 6.68 (dd, J = 17.6, 10.9 Hz, 1 H), 7.17 (d, J = 8.1 Hz, 2 Н),
1
1
3
3
chromatography plates. The melting points were determined on a 7.33 (d, J = 8.0 Hz, 2 Н). C NMR (CDCl ), δ: 23.9, 33.9, 112.8, 126.2,
Kofler hot-stage apparatus. Chromatography was performed on 126.6, 135.2, 136.7, 148.6.
6
3
silica gel (63-200 mesh).
1-Chloro-4-isopropenylbenzene (1g) . 4-Chloroacetophenone (3.0
Vinylbenzene (1a), 1-methyl-2-vinylbenzene (1b), 1-tert-butyl-4- g, 19.4 mmol) gave the title compound as a colourless oil (2.3 g,
1
vinylbenzene (1d), 1-chloro-4-vinylbenzene (1e), isopropenyl- 15.1 mmol, 78%). H NMR (CDCl
benzene (1f), p-toluenesulfonohydrazide (2a), 4-iso-propylbenz- (s, 1 H), 7.29 (d, J = 8.6 Hz, 2 H), 7.39 (d, J = 8.6 Hz, 2 H). C NMR
aldehyde, 4-chloroacetophenone, 4-bromoacetophenone, 4- (CDCl ), δ: 21.7, 112.9, 126.8, 128.3, 133.1, 139.6, 142.1.
3
), δ: 2.13 (s, 3 H), 5.10 (s, 1 H), 5.36
13
3
6
4
nitroacetophenone, 4-methoxyacetophenone, 4-iodobenzene- 1-Bromo-4-isopropenylbenzene (1h) . 4-Bromoacetophenone (3.0
sulfonylchloride, 4-bromobenzenesulfonylchloride, 4-methoxy- g, 15.1 mmol) gave the title compound as a colourless oil (2.1 g,
1
benzenesulfonylchloride, 4-nitrobenzenesulfonylchloride, methyltri- 10.6 mmol, 70%). H NMR (CDCl
3
), δ: 2.13 (s, 3 H), 5.11 (s, 1 H), 5.36
13
phenylphosphonium bromide, t-BuOK,
ammonium perchlorate, CuBr, CH CN, THF, CHCl
petroleum ether (PE, 40/70), ethyl acetate (EA), hydrazine hydrate 1-Isopropenyl-4-nitrobenzene (1i) . 4-Nitroacetophenone (3.0 g,
64% w/w water solution of hydrazine) were purchased from 18.2 mmol) gave the title compound as a yellow oil (1.9 g, 11.8
Na
2
SO
4
,
tetra-butyl- (s, 1 H), 7.33 (d, J = 8.6 Hz, 2 H), 7.45 (d, J = 8.6 Hz, 2 H). C NMR
3
3
, CH
2
Cl , MeOH, (CDCl ), δ: 21.6, 113.0, 121.3, 127.1, 131.2, 140.1, 142.2.
2
3
6
5
(
1
3
commercial sources and were used as is. 1-iso-Propyl-4- mmol, 65%). H NMR (CDCl ), δ: 2.17 (s, 3 H), 5.28 (s, 1 H), 5.51 (s, 1
1
3
vinylbenzene (1c), 1-chloro-4-isopropenylbenzene (1g), 1-bromo-4- H), 7.57 (d, J = 8.9 Hz, 2 H), 8.15 (d, J = 8.9 Hz, 2 H). C NMR (CDCl
isopropenylbenzene (1h), 1-nitro-4-isopropenylbenzene (1i), 1- δ: 21.5, 116.3, 123.5, 126.2, 141.5, 146.9, 147.6.
3
),
6
6
methoxy-4-isopropenylbenzene (1j) were synthesized via Wittig 1-Isopropenyl-4-methoxybenzene (1j) . 4-Methoxyacetophenone
6
0
reaction according to the literature . 4-Iodobenzenesulfono- (3.0 g, 20.0 mmol) gave the title compound as white solid (2.4 g,
6
6
hydrazide (2b), 4-bromobenzenesulfonohydrazide (2c), 4-methoxy- 16.0 mmol, 80%). White solid, m.p. = 30.5-31.0°С (lit. m.p. = 32.0-
1
3
benzenesulfonohydrazide (2d), 4-nitrobenzenesulfonohydrazide 32.5°С). H NMR (CDCl ), δ: 2.15 (s, 3 H), 3.82 (s, 3 H), 5.01 (s, 1 H),
6
1
13
(
2e) were synthesized according to the literature .
5.30 (s, 1 H), 6.88 (d, J = 8.8 Hz, 2 H), 7.43 (d, J = 8.8 Hz, 2 H).
C
3
Cyclic voltammetry (CV) were implemented on an IPC-Pro NMR (CDCl ), δ: 21.9, 55.2, 110.6, 113.5, 126.6, 133.7, 142.5, 159.1.
computer-assisted potentiostat manufactured by Econix (scan rate
error 1.0%, potential setting 0.25 mV). The experiments were Synthesis of sulfonylhydrazides 2b-2e.
6
1
performed in a 10-ml five-neck glass conic electrochemical cell with Following the literature procedure
the THF (20 ml) solution
a water jacket for thermostatting. CV curves were recorded using a containing corresponding arylsulfonyl chloride (4-iodobenzene-
three-electrode scheme. The working electrode was a disc glassy- sulfonylchloride, 4-bromobenzenesulfonylchloride, 4-methoxy-
carbon electrode (d = 1.7 mm). A platinum wire served as an benzenesulfonylchloride, 4-nitrobenzenesulfonylchloride, 5.0 g,
auxiliary electrode. A saturated calomel electrode was used as the 16.5-24.2 mmol) was cooled in an ice-water bath to 5 °C. Hydrazine
reference electrode and was linked to the solution by a bridge with hydrate (64% w/w water solution of hydrazine, 2.1-3.0 g; 41.2-60.5
a porous ceramic diaphragm filled with background electrolyte. The mmol) was slowly added while stirring. Then, the reaction mixture
tested solutions were thermostatted at 25±0.5 °С. In a typical case, was stirred at 5 °C for 30 min, diluted with THF (20 ml), washed with
5
ml solution was utilized and the depolarizer concentration was 2 water (3×5 ml), and dried over Na
2
SO
4
. The solvent was removed
–1
mmol∙L . The working electrode was polished before recording under reduced pressure (10-20 torr) to give pure products 2b-2e.
6
7
each CV curve.
4-Iodobenzenesulfonohydrazide (2b) . 4-Iodobenzenesulfonyl-
chloride (5.0 g, 16.5 mmol) gave the title compound as white solid
6
7
Synthesis of styrenes 1c, 1g-1j.
(4.3 g, 14.5 mmol, 88%). White solid, m.p. = 173.0-175.0°С (lit.
6
0
1
Following the literature procedure
6
to the solution of m.p. = 162.0°С). H NMR (DMSO-d ), δ: 4.16 (br s, 2 H), 7.56 (d, J =
13
methyltriphenylphosphonium bromide (14.3-19.1 g, 39.9-53.4 8.4 Hz, 2 H), 7.98 (d, J = 8.9 Hz, 2 H), 8.46 (s, 1 H). C NMR (DMSO-
mmol) in THF (50 ml) t-BuOK (4.8-6.5 g, 43.1-57.7 mmol) was added ), δ: 100.7, 129.4, 137.8, 137.9. Calculated for С IN S С: 24.17
d
6
6
Н
7
2 2
О
while vigorous stirring in Ar atmosphere for 10 minutes. The %, Н: 2.37 %, I: 42.57 %, N: 9.40 %, S: 10.76 %. Found С: 24.23 %, Н:
+
mixture was stirred for 1 hour at room temperature. Then, the 2.45 %, I: 42.18 %, N: 9.21 %, S: 10.57 %. HRMS (ESI) m/z [M+Na] :
+
corresponding carbonyl compound (4-iso-propylbenzaldehyde, 4- Calculated for [С
6
Н
7
IN
2
NaО
2
S] : 320.9171. Found: 320.9167. IR
-1
chloroacetophenone,
4-bromoacetophenone,
4-nitroaceto- (KBr), ν, cm : 3366, 3291, 1571, 1321, 1158, 1085, 1007, 933, 814,
phenone or 4-methoxyacetophenone, 3.0 g, 15.1-20.2 mmol) was 737, 642, 556.
6
8
added. The mixture was stirred for 24 hours at room temperature. 4-Bromobenzenesulfonohydrazide (2c)
.
4-Bromobenzene-
After that it was diluted with CH
3×15 ml), and dried over Na SO . The solvent was removed under white solid (4.5 g, 18.0 mmol, 92%). White solid, m.p. = 114.0-
reduced pressure (10-20 torr). Styrenes 1c, 1g-1j were isolated by 116.0°С (lit. m.p. = 113.0-114.0°С). H NMR (DMSO-d
2 2
Cl (180 ml), washed with water sulfonylchloride (5.0 g, 19.6 mmol) gave the title compound as
(
2
4
6
8
1
6
), δ: 4.20 (br
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ARTICLE
s, 2 H), 7.73 (d, J = 8.6 Hz, 2 H), 7.80 (d, J = 8.6 Hz, 2 H), 8.50 (s, 1 H). mixture, and NaBH
Journal Name
(molar ratio 3 mol / mol 4aa, 4ba, 4ca, 4da,
4
1
3
C NMR (DMSO-d
6
), δ: 126.5, 129.7, 132.0, 137.5.
4ea, 4ab) was added while vigorous stirring. The mixture was
6
9
4
-Methoxybenzenesulfonohydrazide (2d) . 4-Methoxybenzene- stirred for 3 h at 0-5°C. The solvent was removed under reduced
sulfonylchloride (5.0 g, 24.2 mmol) gave the title compound as pressure (10-20 torr). The residue was diluted with EA (50 ml) and
white solid (4.6 g, 23.0 mmol, 95%). White solid, m.p. = 107.0- washed with water (2×5 ml), brine (3×5 ml) and again water (2×5
6
9
1
1
3
8
1
4
09.0°С (lit. m.p. = 105.0-110.0°С). H NMR (DMSO-d
6
), δ: 3.83 (s,
ml), dried over Na
10-20 torr). The desired products 3aa, 3ba, 3ca, 3da, 3ea, 3ab
were isolated by chromatography on SiO with elution using PE-EA
in a linear gradient of the latter from 10 to 40 vol %.
-[(4-Methylphenyl)sulfonyl]-1-phenylethanol (3aa)
2 4
SO and concentrated under reduced pressure
H), 3.92 (br s, 1 H), 7.12 (d, J = 8.8 Hz, 2 H), 7.74 (d, J = 8.8, 2 H),
(
13
.21 (s, 1 H). C NMR (DMSO-d
62.4.
6
), δ: 55.7, 114.2, 129.5, 129.8,
2
6
9
-Nitrobenzenesulfonohydrazide (2e) . 4-Nitrobenzenesulfonyl-
70
2
.
White
chloride (5.0 g, 22.6 mmol) gave the title compound as yellow solid
70
solid, m.p. = 68.5-70.0 °С. (lit. m.p. = 68.5−69.5 °C). Yield 85%. R
=
6
9
f
(
3.7 g, 16.9 mmol, 75%). Yellow solid, m.p. = 150.0-152.0°С (lit.
1
0
3 3
.26 (TLC, PE:EA, 5:1). H NMR (CDCl ), δ: 2.45 (s, 3 H, CH ), 3.31
1
6
m.p. = 152.0-157.0°С). H NMR (DMSO-d ): δ 4.34 (br s, 2 H), 8.05
(
dd, J = 14.3, 1.8 Hz, 1 Н), 3.47 (dd, J = 10.0, 14.3 Hz, 1 H), 3.76 (d, J
13
(
d, J = 8.9 Hz, 2 H), 8.42 (d, J = 8.9 Hz, 2 H), 8.75 (s, 1 H). C NMR
DMSO-d ): δ 124.2, 129.2, 144.2, 149.7.
=
7
2
1
2.0 Hz, 1 H), 5.23 (ddd, J = 10.3, 2.0, 1.8 Hz, 1H), 7.23-7.32 (m, 5Н),
(
6
13
.37 (d, J = 8.1 Hz, 2 H), 7.82 (d, J = 8.1 Hz, 2 H). C NMR (CDCl
1.6, 63.9, 68.4, 125.6, 127.9, 128.2, 128.6, 130.0, 136.1, 140.7,
45.1. Calculated for С15 S С: 65.19 %, Н: 5.84 %, S: 11.60 %.
3
), δ:
General procedure 1. Preparation of 3aa and 4aa.Optimization of
the reaction conditions for oxysulfonylation of styrene 1a with
sulfonylhydrazide 2a (Table 1).
16 3
Н О
+
Found С: 65.12 %, Н: 5.78 %, S: 11.66 %. HRMS (ESI) m/z [M+Na] :
+
Calculated for [С15
Н
16NaО
3
S] : 299.0718. Found: 299.0712. IR (KBr),
To the solution of styrene 1a (300 mg, 2.88 mmol) in 25 ml (СH
O (5:1), СH CN, THF, THF–H O (5:1)) Cu (I) salt (0.58-14.4 mmol,
molar ratio 0.2-5 mol of salt mol 1a) and p-
toluenesulfonylhydrazide 2a (537 mg, 2.88 mmol, molar ratio 1 mol
a / mol 1a) were added. The mixture was stirred in the air, in
3
CN–
-1
ν, cm : 3496, 1391, 1286, 1167, 1137, 1087, 1064, 1020, 998, 834,
H
2
3
2
8
18, 779, 747, 706, 640, 555, 537, 514, 500, 462.
/
70
1
-(2-Methylphenyl)-2-[(4-methylphenyl)sulfonyl]ethanol (3ba)
.
70
White solid, m.p. = 118.0-120.0 °С (lit. m.p. = 116.1−118.0 °C ).
2
1
Yield 54%. R
f 3
= 0.34 (TLC, PE:EA, 3:1). H NMR (CDCl ), δ: 2.08 (s, 3
oxygen atmosphere for 7 h at 40°C, for 7 h at 80°C, then for 12
hours at room temperature.
H), 2.46 (s, 3 H), 3.22 (dd, J = 14.5, 1.3 Hz, 1 Н), 3.39 (dd, J = 14.5,
9
2
7
2
1
.8 Hz, 1 Н), 3.69 (s, 1 H), 5.42 (d, J = 9.8 Hz, 1 Н), 7.07 (dd, J = 7.2,
Treatment of the reaction mixture containing 3aa and 4aa.
After that the solvent was removed under reduced pressure (10-20
torr). The reaction residue was diluted with a mixture of solvents
.0 Hz, 1 Н), 7,11 -7.24 (m, 2 Н), 7.38 (d, J = 8.1 Hz, 2 Н), 7.48 (dd, J =
13
3
.2, 1.7 Hz, 1 Н), 7.85 (d, J = 8.1 Hz, 2 Н). C NMR (CDCl ), δ: 18.5,
1.6, 62.9, 65.0, 125.2, 126.5, 127.9, 128.0, 130.0, 130.5, 133.6,
36.0, 138.7, 145.2. Calculated for С16 S С: 66.18 %, Н: 6.25 %,
PE/CHCl
the precipitate using SiO
washed with a mixture of solvents PE/CHCl
/2/2 (3×30 mL). The combined organic phases were concentrated
3
/EA in volume ratio 1/2/2 (50 mL) and then filtered from
(d=20 mm, h=80mm). The precipitate was
/EA in volume ratio
18 3
Н О
2
S: 11.04 %. Found С: 66.15 %, Н: 6.21 %, S: 10.89 %. HRMS (ESI) m/z
+
+
S]
3
[
M+Na] : Calculated for [С16
Н
18NaО
3
: 313.0874. Found:
1
-1
3
1
5
1
13.0869. IR (KBr), ν, cm : 3517, 1299, 1287, 1247, 1236, 1199,
189, 1170, 1158, 1142, 1086, 1047, 857, 803, 758, 749, 721, 638,
64, 518, 506, 456.
under reduced pressure (10-20 torr). The yields of 3aa and 4aa
1
were determined by H NMR using 1,4-dinitrobenzene as an
internal standard.
-(4-Isopropylphenyl)-2-[(4-methylphenyl)sulfonyl]ethanol (3ca).
White solid, m.p. = 92.5-95.0 °С. Yield 72%. R
f
= 0.39 (TLC, PE:EA,
6
:1). H NMR (DMSO-d ), δ: 1.16 (d, J = 6.9 Hz, 6 Н), 2.39 (s, 3 H),
General procedure 2. Synthesis of β-hydroxysulfones 3aa-3ab and
1
3
2
1
β-ketosulfones 4aa-4ab (Table 2). To the solution of styrene 1a-1e
.83 (m, J = 6.9 Hz, 1 Н), 3.50 (dd, J = 14.5, 3.7 Hz, 1 Н), 3.67 (dd, J =
4.5, 8.5 Hz, 1 Н), 4.96 (ddd, J = 8.5, 4.7, 3.7 Hz, 1 Н), 5.52 (d, J = 4.7
(
300 mg, 1.87-2.88 mmol) in 25 ml СH
mmol, molar ratio 2 mol / mol 1a-1e) and sulfonylhydrazide 2a-2b
1.87-2.88 mmol, molar ratio 1 mol 2 / mol 1a-1e) were added. The 8.2 Hz, 2 Н), 7.75 (d, J = 8.2 Hz, 2 Н). C NMR (DMSO-d ), δ: 21.0,
3 2
CN–H O (5:1) CuBr (3.74-5.76
Hz, 1 Н), 7.13 (d, J = 8.2 Hz, 2 Н), 7.20 (d, J = 8.2 Hz, 2 Н), 7.38 (d, J =
1
3
(
6
mixture was stirred in oxygen atmosphere for 7 h at 40°C, then for 23.9, 33.1, 63.0, 67.8, 126.0, 126.1, 127.8, 129.4, 137.6, 140.5,
2 hours at room temperature. After that the reaction mixture was 143.7, 147.6. Calculated for С18 S С: 67.89 %, Н: 6.96 %, S:
1
22 3
Н О
treated as described above (General procedure 1). The yields of 10.07 %. Found С: 67.87 %, Н: 7.01 %, S: 10.14 %. HRMS (ESI) m/z
+
+
3
aa, 3ba, 3ca, 3da, 3ea, 3ab and 4aa, 4ba, 4ca, 4da, 4ea, 4ab were [M+Na] : Calculated for [С18
Н
22NaО
3
S]
: 341.1187. Found:
-1
1
3
1
5
1
41.1178. IR (KBr), ν, cm : 3500, 2966, 1410, 1302, 1287, 1253,
170, 1140, 1086, 1052, 1001, 862, 851, 822, 776, 734, 635, 597,
68, 547, 532, 509, 471, 449.
determined by H NMR using 1,4-dinitrobenzene as an internal
standard. The products 3aa, 3ba, 3ca, 3da, 3ea, 3ab and 4aa, 4ba,
4
ca, 4da, 4ea, 4ab were isolated by chromatography on SiO with
2
-(4-tert-Butylphenyl)-2-[(4-methylphenyl)sulfonyl]ethanol (3da).
elution using PE-EA in a linear gradient of the latter from 10 to 40
vol %.
White solid, m.p. = 106.0-107.0 °С. Yield 89%. R = 0.40 (TLC, PE:EA,
:1). H NMR (DMSO-d ), δ: 1.24 (s, 9 H), 2.39 (s, 3 H), 3.50 (dd, J =
6
f
1
3
1
8
4.6, 3.8 Hz, 1 Н), 1H), 3.67 (dd, J = 14.6, 8.5 Hz, 1 Н), 4.96 (ddd, J =
.5, 4.7, 3.8 Hz, 1 Н), 5.52 (d, J = 4.7 Hz, 1 Н), 7.20 (d, J = 8.2 Hz, 2
General procedure 3. Synthesis of β-hydroxysulfones 3aa-3ab
4
using NaBH (Table 2, yield in parentheses). After the reaction the
Н), 7.28 (d, J = 8.2 Hz, 2 Н), 7.37 (d, J = 8.1 Hz, 2 Н), 7.75 (d, J = 8.1
mixture was treated as described above (General procedure 1).
Afterwards the residue was diluted with 10 ml of THF-MeOH (1:1)
13
6
Hz, 2 Н). C NMR (DMSO-d ), δ: 21.0, 31.1, 34.1, 62.9, 67.7, 124.8,
6
| J. Name., 2012, 00, 1-3
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1
25.8, 127.7, 129.4, 137.6, 140.0, 143.6, 149.8. Calculated for 21.6, 23.5, 34.3, 63.5, 126.9, 128.6, 129.6, 129.7, 133.7, 135.8,
S С: 68.64 %, Н: 7.28 %, S: 9.64 %. Found С: 68.57 %, Н: 145.2, 156.1, 187.6. Calculated for С18 S С: 68.33 %, Н: 6.37 %,
.94 %, S: 9.51 %. HRMS (ESI) m/z [M+Na] : Calculated for S: 10.13 %. Found С: 67.86 %, Н: 6.82 %, S: 9.70 %. HRMS (ESI) m/z
С
19
Н
24
О
3
20 3
Н О
+
6
+
-1
+
+
[С
19
Н
24NaО
3
S] : 313.0874. Found: 313.0869. IR (KBr), ν, cm : 3521, [M+Na] : Calculated for [С18
Н20NaО
3
S] : 339.1031. Found:
-1
2
8
1
962, 1303, 1289, 1242, 1174, 1140, 1113, 1087, 1057, 864, 844, 339.1025. IR (KBr), ν, cm : 2953, 1686, 1311, 1290, 1183, 1142,
23, 773, 737, 636, 579, 543, 528, 506.
1084, 828, 549.
7
0
-(4-Chlorophenyl)-2-[(4-methylphenyl)sulfonyl]ethanol (3ea)
.
1-(4-tert-Butylphenyl)-2-[(4-methylphenyl)sulfonyl]ethanone
7
0
White solid, m.p. = 89.5-92.5 °С (lit. m.p. = 88.0−91.0 °C). Yield (4da). White solid, m.p. = 98.5-101.0 °С. Yield 31%. R
= 0.49 (TLC,
), δ: 1.34 (s, 9 H), 2.44 (s, 3 H), 4.69 (s, 2
.55 (dd, J = 14.6, 4.0 Hz, 1 Н), 3.67 (dd, J = 14.6, 8.2 Hz, 1 Н), 4.97 H), 7.32 (d, J = 7.9 Hz, 2 H), 7.48 (d, J = 8.2 Hz, 2 H), 7.76 (d, J = 7.9
f
1
1
5
f 6 3
2%. R = 0.28 (TLC, PE:EA, 3:1). H NMR (DMSO-d ), δ: 2.40 (s, 3 H), PE:EA, 3:1). H NMR (CDCl
3
1
3
(ddd, J = 8.2, 5.0, 4.0 Hz, 1 Н), 5.70 (d, J = 5.0 Hz, 1 Н), 7.32 (s, 4H), Hz, 2 H), 7.88 (d, J = 8.2 Hz, 2 H). C NMR (CDCl
3
), δ: 21.7, 31.0,
), 35.2, 63.6, 125.8, 128.6, 129.3, 129.8, 133.3, 135.9, 145.2, 158.3,
S С: 69.06 %, Н: 6.71 %, S: 9.70 %.
1
3
7.39 (d, J = 8.1 Hz, 1 Н), 7.75 (d, J = 8.1 Hz, 1 Н). C NMR (DMSO-d
6
δ: 21.0, 62.6, 67.3, 127.8, 128.0, 128.1, 129.4, 131.9, 137.5, 141.9, 187.6. Calculated for С19
43.8. Calculated for С15 S С: 57.97 %, Н: 4.86 %, Cl: 11.41 %, Found С: 69.01 %, Н: 6.65 %, S: 9.59 %. HRMS (ESI) m/z [M+Na] :
S: 10.32 %. Found С: 57.95 %, Н: 4.93 %, Cl: 11.34 %, S:10.25 %. Calculated for [С19
22 3
Н О
+
1
Н15ClО
3
+
Н22NaО
3
S] : 353.1187. Found: 353.1182. IR
+
+
-1
HRMS (ESI) m/z [M+Na] : Calculated for: [С15Н15ClNaО S] : (KBr), ν, cm : 1681, 1314, 1290, 1141, 1083, 828, 768, 590, 549,
3
-1
3
1
5
2
33.0328. Found: 333.0323. IR (KBr), ν, cm : 3485, 1311, 1300, 516.
7
1
287, 1160, 1145, 1138, 1087, 1076, 1064, 1013, 813, 714, 562, 1-(4-Chlorophenyl)-2-[(4-methylphenyl)sulfonyl]ethanone (4ea)
.
7
1
11, 502.
White solid, m.p. = 128.0-130.5 °С (lit. m.p. = 137.0–138.0 °C).
1
-[(4-Iodophenyl)sulfonyl]-1-phenylethanol (3ab). White solid, Yield 24%. R
f
= 0.46 (TLC, PE:EA, 3:1). H NMR (CDCl
3
), δ: 2.45 (s, 3
1
m.p. = 108.0-112.0 °С. Yield 62%. R
DMSO-d ), δ: 3.55 (dd, J = 14.6, 3.3 Hz, 1 Н), 3.76 (dd, J = 14.6, 9.2 7.74 (d, J = 8.2 Hz, 2 H), 7.90 (d, J = 8.6 Hz, 2 H). C NMR (CDCl
Hz, 1 Н), 5.00 (ddd, J = 9.2, 4.8, 3.3 Hz, 1 Н), 5.62 (d, J = 4.8 Hz, 1 Н), 21.7, 63.7, 128.5, 129.2, 129.9, 130.7, 134.1, 135.6, 141.0, 145.5,
f
= 0.32 (TLC, PE:EA, 5:1). H NMR H), 4.68 (s, 2 H), 7.34 (d, J = 8.2 Hz, 2 H), 7.45 (d, J = 8.6 Hz, 2 H),
1
3
(
6
3
), δ:
7
.19-7.34 (m, 5 H), 7.65 (d, J = 8.4 Hz, 2 Н), 7.99 (d, J = 8.4 Hz, 2 Н). 187.0. Calculated for С15
Н
13ClО
3
S С: 58.35 %, Н: 4.24 %, Cl: 11.48 %,
1
3
C NMR (DMSO-d
3 3
37.8, 140.3, 142.9. Calculated for С14Н13IО S С: 43.31 %, Н: 3.38 %, HRMS (ESI) m/z [M+Na] : Calculated for [С15Н13ClNaО S] : 331.0172.
6
), δ: 62.6, 67.9, 101.9, 126.1, 127.4, 128.2, 129.5, S: 10.38 %. Found С: 58.37 %, Н: 4.31 %, Cl: 10.98 %, S: 9.93 %.
+
+
1
-1
I: 32.69 %, S: 8.26 %. Found С: 43.28 %, Н: 3.31 %, I: 32.32 %, S: 8.09 Found: 331.0166. IR (KBr), ν, cm : 1679, 1589, 1315, 1290, 1277,
+
+
S]
%
. HRMS (ESI) m/z [M+Na] : Calculated for [С14
Н
13INaО
3
:
1148, 1091, 1083, 1004, 784, 759, 724, 537, 507.
-1
4
1
2
10.9528. Found: 410.9522. IR (KBr), ν, cm : 3464, 1384, 1303, 2-[(4-Iodophenyl)sulfonyl]-1-phenylethanone (4ab). White solid,
1
270, 1135, 1083, 1061, 1003, 993, 817, 745, 701, 566, 549, 531.
m.p. = 125.0-127.0 °С. Yield 25%. R
f
= 0.38 (TLC, PE:EA, 5:1). H NMR
7
1
-[(4-Methylphenyl)sulfonyl]-1-phenylethanone (4aa) . White (CDCl ), δ: 4.73 (s, 2 H), 7.49 (t, J = 7.2 Hz, 2 H), 7.56-7.68 (m, 3H),
3
7
1
13
solid, m.p. = 102.5-104.5 °С (lit.
m.p. = 102.0–103.0 °C). Yield 7.87-7.95 (m, 4H). C NMR (CDCl
3
), δ: 63.2, 102.5, 128.9, 129.2,
1
36%. R
f
= 0.73 (TLC, PE:EA, 2:1). H NMR (CDCl
3
), δ: 2.43 (s, 3 H), 4.73 129.9, 134.5, 135.5, 138.3, 138.4, 187.8. Calculated for С14Н11IО S
3
(
s, 2 H), 7.32 (d, J = 8.2 Hz, 2 H), 7.46 (dd, J = 7.5, 7.3 Hz, 2 H), 7.61 С: 43.54 %, Н: 2.87 %, I: 32.86 %, S: 8.30 %. Found С: 43.58 %, Н:
+
(
t, J = 7.5 Hz, 1 H), 7.77 (d, J = 8.2 Hz, 2 H), 7.94 (d, J = 7.3 Hz, 2 H). 3.01 %, I: 32.65 %, S: 8.25 %. HRMS (ESI) m/z [M+Na] : Calculated
1
3
+
-1
C NMR (CDCl
35.7, 135.8, 145.2, 188.1. Calculated for С15
.14 %, S: 11.69 %. Found С: 65.57 %, Н: 5.34 %, S: 11.59 %. HRMS
3
), δ: 21.6, 63.5, 128.5, 128.7, 129.2, 129.7, 134.2, for [С14
3
Н11INaО S] : 408.9371. Found: 408.9366. IR (KBr), ν, cm :
1
5
14 3
Н О
S С: 65.67 %, Н: 1677, 1563, 1379, 1314, 1273, 1151, 1002, 756, 741, 727, 565, 516.
+
+
(ESI) m/z [M+Na] : Calculated for [С15
Н
14NaО
3
S] : 297.0561. Found: General procedure 4. Synthesis of β-hydroxysulfones 3fa-3fe
97.0556. IR (KBr), ν, cm : 1680, 1596, 1320, 1271, 1150, 1087, (Table 3). To the solution of styrene 1f-1j (300 mg, 1.52-2.54 mmol)
93, 750, 739, 686, 590, 535, 503.
in 25 ml СH CN–H O (5:1) CuBr (3.04-5.08 mmol, molar ratio 2 mol /
-(2-Methylphenyl)-2-[(4-methylphenyl)sulfonyl]ethanone (4ba) mol 1f-1j) and sulfonylhydrazide 2a-2e (1.52-2.54 mmol, molar ratio
-
1
2
9
1
3
2
7
2
72
.
White solid, m.p. = 108-110 °С (lit. m.p. = 109-111 °С). Yield 1 mol 2 / mol 1f-1j) were added. The mixture was stirred in oxygen
1
1
f 3
8%. R = 0.37 (TLC, PE:EA, 3:1). H NMR (CDCl ), δ: 2.45 (s, 6 H), 4.70 atmosphere for 7 h at 40°C, then for 12 hours at room temperature.
(
s, 2 H), 7.23-7.31 (m, 2 H), 7.31-7.36 (m, 2 H), 7.39-7.46 (m, 1 H), After that the reaction mixture was treated as described above
1
3
7
.71-7.79 (m, 3 H). C NMR (CDCl
3
), δ: 21.4, 21.6, 65.5, 125.8, (General procedure 1). The desired products 3fa, 3ga, 3ha, 3ia, 3ja,
1
28.4, 129.7, 130.3, 132.2, 132.7, 135.7, 136.0, 139.9, 145.1, 190.5. 3fc, 3fd, 3fe were isolated by chromatography on SiO with elution
2
16 3
Calculated for С16Н О S С: 66.64 %, Н: 5.59 %, S: 11.12 %. Found С: using PE-EA in a linear gradient of the latter from 10 to 40 vol %.
+
73
6
6.38 %, Н: 5.80 %, S: 11.29 %. HRMS (ESI) m/z [M+Na] : Calculated 1-[(4-Methylphenyl)sulfonyl]-2-phenylpropan-2-ol (3fa) . White
+
-1
73
3
for [С16Н16NaО S] : 311.0718. Found: 311.0714. IR (KBr), ν, cm : solid, m.p. = 99.5-100.5 °С (lit. m.p. = 103–104 °C). Yield 92%. Rf=
1
2
5
1
956, 2910, 1685, 1314, 1291, 1142, 1084, 978, 823, 761, 747, 556, 0.64 (TLC, PE:EA, 2:1). H NMR (CDCl ), δ: 1.71 (d, J = 1.1 Hz, 3 H),
17.
-(4-Isopropylphenyl)-2-[(4-methylphenyl)sulfonyl]ethanone
3
2.39 (s, 3 H), 3.61 (dd, J = 14.6, 1.1 Hz, 1 H), 3.72 (d, J = 14.6, 1.1 Hz,
1 H), 4.66 (br s, 1 H), 7.14-7.24 (m, 5 H), 7.26-7.34 (m, 2 H), 7.49
1
3
(
f
3
4ca). White solid, m.p. = 127.0-129.5 °С. Yield 23%. R = 0.43 (TLC, (dd, J = 8.2, 1.0 Hz, 2 H). C NMR (CDCl ), δ: 21.5, 30.7, 66.6, 73.0,
1
PE:EA, 3:1). H NMR (CDCl
3
), δ: 1.26 (d, J = 7.0 Hz, 6 H), 2.43 (s, 3 H), 124.5, 127.0, 127.4, 128.1, 129.6, 137.3, 144.4. Calculated for
.97 (m, J = 7.0 Hz, 1 H), 4.69 (s, 2 H), 7.32 (2d, J = 8.2, 8.4 Hz, 4 H), С Н О S С: 66.18 %, Н: 6.25 %, S: 11.04 %. Found С: 66.23 %, Н:
.76 (d, J = 8.2 Hz, 2 H), 7.87 (d, J = 8.4 Hz, 2 H). C NMR (CDCl
2
7
1
6 18 3
13
+
3
), δ: 6.06 %, S: 11.12 %. HRMS (ESI) m/z [M+Na] : Calculated for
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DOI: 10.1039/C6RA19190H
ARTICLE
Journal Name
+
-1
[
С
16
Н
18NaО
3
S] : 313.0874. Found: 313.0879. IR (KBr), ν, cm : 3500, 9.03 %. Found С: 50.78 %, Н: 4.31 %, Br: 22.48 %, S: 9.02 %. HRMS
+
+
2
1
2
973, 1451, 1355, 1300, 1268, 1247, 1182, 1155, 1119, 1081, 1036, (ESI) m/z [M+Na] : Calculated for [С15
Н
15BrNaО
Found: 376.9821. IR (KBr), ν, cm : 3507, 1576, 1392, 1312, 1295,
-(4-Chlorophenyl)-1-[(4-methylphenyl)sulfonyl]propan-2-ol (3ga). 1270, 1149, 1122, 1084, 1067, 1010, 942, 821, 775, 765, 714, 701,
= 0.68 (TLC, PE:EA, 2:1). 579, 545, 528, 411.
), δ: 1.62 (s, 3 H), 2.39 (s, 3 H), 3.55 (d, J = 14.8 Hz, 1 1-[(4-Methoxyphenyl)sulfonyl]-2-phenylpropan-2-ol (3fd) . White
3
S] : 376.9823.
-1
024, 1017, 947, 858, 813, 767, 707, 637, 570, 555, 532, 509, 477.
White solid, m.p. = 142-144 °С. Yield 90%. R
f
1
16
H NMR (CDCl
H), 3.69 (d, J = 14.8 Hz, 1H,), 7.07 (d, J = 8.7 Hz, 2 H) 7.15 (d, J = 8.7 solid, m.p. = 87.5-89 °С (lit. m.p. = 90.5-92.5 °C). Yield 85%. R
3
1
6
f
=
13
1
Hz, 2 H) 7.15 (d, J = 8.3 Hz, 2 H), 7.41 (d, J = 8.3 Hz, 2 H). C NMR 0.45 (TLC, PE:EA, 2:1). H NMR (CDCl
CDCl ), δ: 21.5, 30.9, 66.3, 72.7, 126.2, 127.5, 128.2, 129.7, 133.1, 14.7 Hz, 1 H), 3.70 (d, J = 14.7 Hz, 1H), 3.82 (s, 3 H), 6.81 (d, J = 8.9
37.0, 142.8, 144.7. Calculated for С16 S С: 59.16 %, Н: 5.28 Hz, 2 H), 7.11-7.24 (m, 3 H), 7.25-7.31 (m, 2 H), 7.50 (d, J = 8.9 Hz,
3
), δ: 1.68 (s, 3 H), 3.58 (d, J =
(
3
1
Н17ClО
3
1
3
%
, Cl: 10.91 %, S: 9.87 %. Found С: 58.99 %, Н: 5.29 %, Cl: 11.04 %, 2H). C NMR (CDCl
3
), δ: 30.8, 55.6, 66.7, 73.0, 114.2, 124.6, 127.1,
S] : 128.2, 129.7, 131.8, 144.5, 163.5. Calculated forС16 S С: 62.72
47.0485. Found: 347.0479.IR (KBr), ν, cm : 3496, 1308, 1302, %, Н: 5.92 %, S: 10.47 %. Found С: 62.81 %, Н: 5.95 %, S: 10.46 %.
+
+
S: 9.98 %. HRMS (ESI) m/z [M+Na] : Calculated for [С16
Н
17ClNaО
3
18 4
Н О
-1
3
1
2
+
+
252, 1158, 1128, 1082, 1044, 849, 771, 645, 543, 522, 460.
4
HRMS (ESI) m/z [M+Na] : Calculated for [С16Н18NaО S] : 329.0824.
-1
-(4-Bromophenyl)-1-[(4-methylphenyl)sulfonyl]propan-2-ol (3ha) Found: 329.0813. IR (KBr), ν, cm : 3501, 1594, 1497, 1307, 1295,
1
6
16
.
Light-brown solid, m.p. = 160.5-163 °С (lit. m.p. = 164.0-166.0 1261, 1249, 1151, 1117, 1079, 1026, 830, 758, 697, 570, 529, 480,
1
°
f 6
C). Yield 93%. R = 0.29 (TLC, PE:EA, 3:1). H NMR (DMSO-d ), δ: 1.55 468.
1
6
(
s, 3 H), 2.37 (s, 3 H), 3.77 (d, J = 14.8 Hz, 1 H), 3.84 (d, J = 14.8 Hz, 1 1-[(4-Nitrophenyl)sulfonyl]-2-phenylpropan-2-ol (3fe)
.
White
1
3
16
H), 7.24-7.35 (m, 6 H), 7.52 (d, J = 8.0 Hz, 2 H). C NMR (DMSO-d
δ: 21.0, 30.0, 66.0, 71.5, 119.8, 127.5, 127.6, 129.2, 130.3, 138.2, 0.25 (TLC, PE:EA, 3:1). H NMR (DMSO-d
6
), solid, m.p. = 177.5-179.5 °С (lit. m.p. = 187-190 °C). Yield 36%. R
f
=
1
6
), δ: 1.61 (s, 3 H), 3.93-4.05
3
Н17BrО S С: 52.04 %, Н: 4.64 %, Br: (m, 2 H), 5.44 (s, 1 H), 7.08-7.23 (m, 3 H), 7.31-7.39 (m, 2 H), 7.96 (d,
1
43.4, 145.4. Calculated for С16
13
2
1.64 %, S: 8.68 %. Found С: 52.14 %, Н: 4.73 %, Br: 21.12 %, S: 8.47 J = 8.7 Hz, 2 H), 8.29 (d, J = 8.7 Hz, 2 H). C NMR (DMSO-d
6
), δ: 29.9,
S] : 65.8, 71.6, 123.7, 124.9, 126.4, 127.5, 129.4, 146.3, 146.6, 149.7.
S С: 56.06 %, Н: 4.70 %, N: 4.36%, S: 9.98
+
+
%
. HRMS (ESI) m/z [M+Na] : Calculated for [С16Н17BrNaО
3
-1
3
1
1
90.9979. Found: 390.9974. IR (KBr), ν, cm : 3489, 1251, 1158, Calculated for С15
Н
15NО
5
127, 1081, 771, 639, 585, 540, 522, 486.
%. Found С: 56.04 %, Н: 4.85 %, N: 4.21%, S: 9.96 %. HRMS (ESI) m/z
1
6
.
+
+
-[(4-Methylphenyl)sulfonyl]-2-(4-nitrophenyl)propan-2-ol (3ia)
[M+Na] : Calculated for [С15
Н
15NNaО
5
S] : 344.0569. Found:
1
6
-1
White solid, m.p. = 137.5-138.5 °С (lit.
m.p.= 140.0-142.0 °C). 344.0563. IR (KBr), ν, cm : 3492, 1525, 1350, 1305, 1148, 1121,
1
Yield 89%. R
f
= 0.40 (TLC, PE:EA, 2:1). H NMR (DMSO-d
6
), δ: 1.57 (s, 1083, 849, 771, 742, 579, 525.
3
H), 2.33 (s, 3 H), 3.84 (d, J = 14.8 Hz, 1 H), 4.01 (d, J = 14.8 Hz, 1 H),
.71 (s, 1 H), 7.25 (d, J = 8.0 Hz, 2 H), 7.51 (d, J = 8.0 Hz, 2 H), 7.64
5
1
3
Acknowledgements
(
d, J = 8.9 Hz, 2 H), 8.02 (d, J = 8.8 Hz, 2 H). C NMR (DMSO-d
6
), δ:
1.0, 30.5, 65.7, 71.8, 122.6, 126.7, 127.7, 129.2, 138.1, 143.6,
46.1, 153.7. Calculated for С16 S С: 57.30 %, Н: 5.11 %, N:
.18%, S: 9.56 %. Found С: 57.28 %, Н: 5.08 %, N: 4.16%, S: 9.48 %.
2
1
4
This work was supported by the Russian Science Foundation
Н
17NО
5
(Grant 14-23-00150).
+
+
5
HRMS (ESI) m/z [M+Na] : Calculated for [С16Н17NNaО S] : 358.0725.
-1
Found: 358.0713. IR (KBr), ν, cm : 3480, 1520, 1349, 1310, 1301, References
1291, 1268, 1147, 1121, 1084, 855, 815, 757, 537, 518.
1
.
H. Eto, Y. Kaneko, S. Takeda, M. Tokizawa, S. Sato, K. Yoshida, S.
Namiki, M. Ogawa, K. Maebashi, K. Ishida, M. Matsumoto and T.
Asaoka, Chem. Pharm. Bull., 2001, 49, 173.
1-[(4-Methylphenyl)sulfonyl]-2-(4-methoxyphenyl)propan-2-ol
1
6
16
(3ja) . White solid, m.p. = 90-93 °С (lit. m.p. = 94.5-95.5 °C).
1
Yield 90%. R
f 3
= 0.25 (TLC, PE:EA, 3:1). H NMR (CDCl ), δ: 1.66 (s, 3 2. B. J. A. Furr, Horm. Res., 1989, 32, 69.
H), 2.37 (s, 3 H), 3.54 (d, J = 14.5 Hz, 1 H), 3.67 (d, J = 14.5 Hz 1 H), 3. T. Sato, Y. Okumura, J. Itai and T. Fujisawa, Chem. Lett., 1988,
3
.74 (s, 3 H), 6.68 (d, J = 8.8 Hz, 2 H), 7.16 (d, J = 8.3 Hz, 2 H), 7.17
17, 1537.
13
4
5
.
.
M. Julia and J.-M. Paris, Tetrahedron Lett., 1973, 14, 4833.
N. Suryakiran, T. Srikanth Reddy and Y. Venkateswarlu, J. Sulfur
Chem., 2007, 28, 513.
(
d, J = 8.8 Hz, 2 H), 7.47 (d, J = 8.3 Hz, 2 H). C NMR (CDCl
3
), δ: 21.5,
0.7, 55.2, 66.8, 72.8, 113.5, 125.8, 127.5, 129.6, 136.6, 137.4,
44.3, 158.7. Calculated for С17 S С: 63.73 %, Н: 6.29 %, S:
0.01 %. Found С: 63.88 %, Н: 6.29 %, S: 10.01 %. HRMS (ESI) m/z
3
1
1
20 4
Н О
6
.
A. K. Maiti and P. Bhattacharyya, Tetrahedron, 1994, 50, 10483.
+
+
7. D. J. Berrisford, P. A. Lovell, N. R. Suliman and A. Whiting, Chem.
Commun., 2005, 5904.
[M+Na] : Calculated for [С17
Н
20NaО
4
S]
: 343.0980. Found:
-
1
3
1
5
1
43.0975. IR (KBr), ν, cm : 3472, 1607, 1598, 1514, 1309, 1292,
251, 1183, 1146, 1120, 1083, 1032, 832, 823, 810, 766, 676, 557,
36, 513.
8
.
S. Narayana Murthy, B. Madhav, V. Prakash Reddy, K. Rama Rao
and Y. V. D. Nageswar, Tetrahedron Lett., 2009, 50, 5009.
M. C. Bernabeu, P. Bonete, F. Caturla, R. Chinchilla and C.
Nájera, Tetrahedron: Asymmetry, 1996, 7, 2475.
9
.
1
6
-[(4-Bromophenyl)sulfonyl]-2-phenylpropan-2-ol (3fс) . Yellow
1
6
solid, m.p. = 153-156 °С (lit. m.p. = 153.0-153.5 °C). Yield 52%. R
f
=
10. P. Bertus, P. Phansavath, V. Ratovelomanana-Vidal, J. P. Genêt,
1
0.40 (TLC, PE:EA, 3:1). H NMR (DMSO-d
6
), δ: 1.60 (s, 3 H), 3.86 (s, 2
A. R. Touati, T. Homri and B. B. Hassine, Tetrahedron Lett., 1999,
4
0, 3175.
11. A. L. Moure, R. G. Arrayas and J. C. Carretero, Chem. Commun.,
011, 47, 6701.
2. W. Autenrieth, Liebigs Ann. Chem., 1890, 259, 362.
H), 4.75 (br s, 1 H), 7.11-7.23 (m, 3 H), 7.33-7.39 (m, 2 H), 7.62 (d, J
1
3
=
8.6 Hz, 2 H), 7.70 (d, J = 8.6 Hz, 2 H). C NMR (DMSO-d
6.1, 71.7, 125.0, 126.4, 127.1, 127.6, 129.8, 131.7, 140.6, 146.5.
S С: 50.71 %, Н: 4.26 %, Br: 22.49 %, S:
6
), δ: 29.9,
2
6
1
Calculated for С15Н15BrО
3
8
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6RA19190H
ARTICLE
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DOI: 10.1039/C6RA19190H