Facile synthesis of diarylsulfones from arenes and 3CdSO4·xH2O via mechanochemistry

Article abstract of DOI:10.1016/j.tetlet.2019.151567

A variety of substituted diarylsulfones could be synthesized by simple arenes and 3CdSO₄·xH₂O in the presence of P₂O₅ under high-speed ball milling. It was suggest the aromatic sulfonation was performed by arene and in situ generated H₂SO₄, following-up by electrophilic substitution with another arene to give diarylsulfone.

Full text of DOI:10.1016/j.tetlet.2019.151567

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Facile synthesis of diarylsulfones from arenes and 3CdSO4·xH2O via mecha-
nochemistry
Shuai Qin, Pu Zhang, Yu-Jun Qin, Zhi-Xin Guo
PII:
S0040-4039(19)31366-8
DOI:
https://doi.org/10.1016/j.tetlet.2019.151567
TETL 151567
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Please cite this article as: Qin, S., Zhang, P., Qin, Y-J., Guo, Z-X., Facile synthesis of diarylsulfones from arenes
and 3CdSO4·xH2O via mechanochemistry, Tetrahedron Letters (2019), doi: https://doi.org/10.1016/j.tetlet.
2019.151567
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Facile synthesis of diarylsulfones from arenes
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and 3CdSO4·xH2O via mechanochemistry
Shuai Qin, Pu Zhang*, Yu-Jun Qin, Zhi-Xin Guo*

1
Tetrahedron Letters
journal homepage: www.elsevier.com
Facile synthesis of diarylsulfones from arenes and 3CdSO4·xH2O via mechanochemistry
Shuai Qin, Pu Zhang, Yu-Jun Qin, and Zhi-Xin Guo*
Department of Chemistry, Renmin University of China, Beijing 100873, China
ARTICLE INFO
ABSTRACT
Article history:
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Accepted
A variety of substituted diarylsulfones could be synthesized by simple arenes and
3CdSO4·xH2O in the presence of P2O5 under high-speed ball milling. It was suggest the
aromatic sulfonation was performed by arene and in situ generated H2SO4, following-
up by electrophilic substitution with another arene to give diarylsulfone.
Available online
.
Keywords:
Mechanochemistry
Arenes
2009 Elsevier Ltd. All rights reserved.
3CdSO4·xH2O
Sulfones
———
 Corresponding authors. E-mail: gzhixin@ruc.edu.cn, zhangpu@ruc.edu.cn

2
Tetrahedron Letters
Diarylsulfones are one of the most significant synthetic
was setting as 4 hours, the yields increased sharply from 45% to
52% and 63% along with the frequency was elevated from 20 to
25 and 28 Hz, respectively. However, when the reaction time was
setting as 6 or 7 hours, the yields were almost the same with the
molecules which have found wide utilities in pharmaceuticals,
agrochemicals, and functional materials [1-4]. In the meantime,
diarylsulfones are also important intermediates in organic
transformation [5]. Traditionally, these sulfones were synthesized
via aromatic sulfonating [6-10], the oxidation of sulfides and
sulfoxides [11-13], and transition-metal catalyzed arylation of
sulfinate salts [14-15]. Despite their usefulness, these methods
have some limitations, such as harsh reaction conditions, requiring
prefunctionalized starting materials, or employing high
temperature, expensive catalysts, toxic solvents. Although a
number of new methods have been developed recently [16-19],
development of a general, facile, and efficient synthetic protocol
to diarylsulfone is still highly desirable.
Table 1. The choice and optimization of sulfate salts*
Entry
1
Sulfate
MgSO4
Molar ratio†
1:2:3
Yield (%)‡
trace
14
2
MgSO4·H2O
1:2:3
3
1:6:3
35
4
1:7:3
43
In recent years, mechanochemical organic methodologies have
been explored as a powerful tool for organic chemists [20-26]. The
application of mechanical forces to solvent-free or solventless
reaction mixtures through the use of ball-mills offers many
advantages over traditional solvent-based strategies. During our
continuous exploration of high-speed ball milling (HSBM)
reactions [27-32], we recently found that by taking
Bi(NO3)2·9H2O or Fe(NO3)3·9H2O as the nitrification reagents,
MgSO4 or P2O5 as the auxiliaries, respectively, arenes could be
nitrated in excellent yields under HSBM condition. In this context,
acetophenones could also be converted to diacylfuroxans in high
or moderate yields [32]. While the nitrate salts with P2O5 together
can perform the aromatic nitration very well, likewise, we propose
that the combination of certain sulphate salt with P2O5 may also
achieve the aromatic sulfonation. Herein, we report an
unprecedented synthesis of diarylsulfones by reacting arenes with
3CdSO4·xH2O and P2O5 under HSBM condition.
5
1:8:3
31
6
1:7:4
33
7
1:3.5:11
1:2:3
5
8
MgSO4·7H2O
Na2SO4
N.D.
trace
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
10
9
1:2:3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
Na2SO4·10H2O
Fe2(SO4)3
1:2:3
1:2:3
FeSO4·7H2O
CoSO4·7H2O
NiSO4·6H2O
ZnSO4·7H2O
CdSO4
1:2:3
1:2:3
1:2:3
1:2:3
1:2:3
3CdSO4·xH2O
1:2:3
1:2:6
14
During our studies, a stainless milling beaker of 2.5 mL along
with one stainless milling ball (ø = 6.0 mm) was used. The
mechanochemical reaction was performed in a MM400 mixer mill
at 28 Hz for 5 hours at room temperature. Biphenyl was chosen as
the standard substrate to screen if any reaction could be performed.
Initially, the molar ratios of the biphenyl, sulfate salt, and P2O5
were fixed as 1:2:3. All the reagents were added to the stainless
milling beaker (2.5 mL), along with one stainless milling ball (ø =
6.0 mm). The beaker was sealed and milled at 28 Hz for 5 hours
in the MM400 mixer mill (Table 1, entries 1, 2, 8–17, 32–34, 41).
When anhydrous sulfates were employed, no or only trace amount
of 4,4'-sulfonyldibiphenyl was observed (Table 1, entries 1, 9, 11,
16, and 33). For hydrated sulfates with relatively large amount
crystal waters, the result was almost the same (Table 1, entries 8,
10, 12–15, and 32). However, when MgSO4·H2O, 3CdSO4·xH2O
(x ≈ 1, the same below), and CaSO4·0.5H2O was taking as sulfate,
4,4'-sulfonyldibiphenyl could be obtained in 14%, 10%, and 12%
yield, respectively (Table 1, entries 2, 17, and 34). For these three
sulfates, the HSBM reaction condition was further optimized by
adjusting the molar ratios of each sulfate and P2O5 related to
biphenyl to a variety of values, in order to get higher yield (Table
1, entries 2–7, 17–31, and 34–40). By keeping the molar ratios of
biphenyl, MgSO4·H2O, and P2O5 as 1:7:3, 43% of the desired
sulfone could be obtained. When the molar ratios of biphenyl,
CaSO4·0.5H2O, and P2O5 were 1:4:3, 39% of the corresponding
sulfone could be obtained. Most gratifyingly, when the molar
ratios of biphenyl, 3CdSO4·xH2O, and P2O5 were kept as 1:3.5:11,
72% of 4,4'-sulfonyldibiphenyl was obtained. In this case,
3CdSO4·xH2O was chosen as the appropriate sulfate and the molar
ratios of substituent/3CdSO4·xH2O/P2O5 = 1:3.5:11 were selected
for the HSBM reaction in the further studies.
1:2:7
28
1:2:8
50
1:3:10
1:3:11
1:3:12
1:3.5:11
1:3..5:12
1:4:12
1:4:13
1:4:14
1:5:13
1:5:14
1:5:15
1:2:3
65
52
63
72
61
59
64
60
58
62
55
3CdSO4·8H2O
CaSO4
N.D.
trace
12
1:2:3
CaSO4·0.5H2O
1:2:3
1:3:3
24
1:4:3
39
1:5:3
31
1:6:3
20
1:4:4
28
1:3.5:11
1:2:3
8
CaSO4·2H2O
trace
* See ESI for reaction details; † Molar ratio = biphenyl: sulfate: P2O5;
‡ Yields were determined by 1HNMR; N.D. = Not detected.
It was reported that mechanochemistry process parameters
usually have a strong influence on the outcomes [33-40]. In order
to obtain the best HSBM reaction condition, the combined
assessment of the grinding time and vibration frequency as well as
the influence of ratios between the milling ball and the milling
materials were carried out, respectively. When the reaction time
frequency at 25 and 28 Hz, respectively. This implies that
compared with vibration frequency, the grinding time is more
important in this HSBM reaction (Figure 1(a) and Table S1 in
ESI).

3
It was also reported that the weight ratio between the milling
ball and the milling materials was another key parameter for the
yields of the ball milling
para/ortho diarylsulfones in good to excellent yields. Mono-
halogen substituted arenes also gave similar results (Table 2,
entries 4-6). All of the mono-substituted
reaction [35-40]. In the HSBM
arenes above gave para-substituted sulfones as
reaction, stainless steel balls
the major products accompanied with small
with different sizes were investigated under the same reaction
condition (Figure 1(b), Table S2 in ESI). Obviously, when the ratio
between the milling ball and the milling materials was 3.7 (the
ball’s diameter is 6.0 mm), the best yield of 72% was obtained,
indicating that the best weight ratio between the milling ball and
the milling materials is around 3.7. Combining with the results of
assessment of the grinding time and vibration frequency, the best
HSBM condition for this ball-milling reaction is grinding 5 hours
under the vibration frequency of 28 Hz with the weight ratio of 3.7
between the milling ball and the milling materials.
amount of ortho-substituted counterparts, implying these
regioselectivity outcomes were determined by the steric
hinderance effect. In this context, biphenyl (Table 2, entry 1) and
methylthiobenzene (Table 2, entry 8) resulted in only para
diarylsulfones, most probably due to the relative big steric effect
of the phenyl and methylthio group, respectively. However, mono-
substituted arenes with deactivating substituents such as nitro,
cyano, acetyl, acetylamino, and ethoxycarbonyl all failed to give
the desired products, almost all the starting arenes were recovered.
These results agree well with the synthesis of sulfones in
traditional solution chemistry by taking either benzenesulfonic
acid or benzenesulfonyl chloride as electrophilic reagents [6-10],
implying an electrophilic substitution process may be involved in
the HSBM process. For those arenes with multi-substituents, m-
dimethylbenzene (Table 2, entry 10), 1,2-dimethoxybenzene
(Table 2, entry 16), and 2,6-dichlorotoluene (Table 2, entry 17)
resulted in only one regioisomer, respectively. For the three 2-
halogenotoluenes (Table 2, entries 11 – 13), 2-fluorotoluene
shown specific regioisomerization and only the 4,4'- sulfone was
obtained (Table 2, entry 11). It was reported that when these 2-
halogenotoluenes were sulfonated, the degree of 5-substitution
decreased from ~ 90% for the fluoro, to ~ 70% for the chloro, and
to ~ 60% for the bromo compound, respectively [41]. Thus the
directing effect of the fluoro is more dominant than those of chloro
and bromo. This maybe the reason for the specific regioisomerism
of 2-fluorotoluene in the reaction. All of the other substrates gave
more than one regioisomers, and the distribution should be
resulted from the balance of the electronic
Figure 1. Optimization of mechanochemical parameters. (a)
Influence of time/frequency; (b) Influence of the weight ratios of
milling ball/milling materials.
Various substituted arenes were tested as substrates under the
optimized conditions. Table 2 summarizes the results. Arenes with
only one activating substituent such as methyl (Table 2, entry 2),
ethyl (Table 2, entry 3), and methoxy (Table 2, entry 7) gave
Table 2. Various diarylsulfones formed via the mechanochemical reaction*
Entry
Arene
Sulfone and yield**
O
Ph
Ph
S
Ph
1
O
1a, 72% (65%)
O
S
Me
O
Me
Et
Me
Me
2
3
4
5
6
Me
S
O
2a, 68% (60%)
O
2b, 23% (16%)
3b, 15%
Et
O
S
O
S
Et
Et
Et
O
3a, 74%
O
F
O
S
O
F
F
F
F
S
O
4a, 49% (43%)
O
4b, 13% (10%)
5b, 14%
O
S
Cl
Br
O
S
Cl
Cl
Br
Cl
Cl
O
5a, 53%
O
O
S
O
S
Br
Br
Br
O
6a, 59%
O
6b, 16%
O
S
MeO
O
OMe
MeO
OMe
7
8
9
MeO
S
O
7a, 80%
O
7b, 15%
O
S
SMe
Me
MeS
SMe
O
8a, 52%
Me
Me
Me
Me
Me
O
S
O
Me
Me
Me
S
Me
O
O
9a, 85%
9b, 11%
Me Me
O
Me
Me
10
11
12
Me
S
Me
O
10a, 74%
Me
F
Me
Me
O
S
F
F
O
11a, 61%
Cl
Cl
Me
Cl
Me
Me
Me
O
S
O
S
O
Me
Me
Cl
Me
Cl
S
Cl
Cl
O
O
O
12a, 33%
12b, 28%
12c, 16%

4
Tetrahedron
Br
Br
Me
Br
Me
Me
Me
Br
O
S
O
S
O
S
13
14
Me
Me
Br
Me
Br
Br
Br
Br
O
O
O
13a, 39%
13b, 31%
13c, 20%
Br Br
O
Br
OMe
OMe OMe
O
MeO
Br
O
MeO
S
OMe
MeO
S
Br
S
O
O
O
14a, 48%
(42%)
14b, 33%
(28%)
14c, 10%
(8%)
Me Me
O
Me Br
O
Me
Br
15
16
Br
S
Br
Br
S
Me
O
O
15a, 45%
15b, 26%
MeO
OMe
OMe
MeO
OMe
O
MeO
S
O
16a, 70%
Cl Cl
O
Cl
Cl
17
18
Cl
S
Cl
O
17a, 57%
O
S
S
S
O
S
18a, 46%
* See ESI for reaction details. The yields in the brackets were from the PTEF milling beakers. ** Isolated yields.
character of the substituent groups. This results agree well with
Rao’s report by taking K2S2O8 as sulfonating reagents in solution
chemistry [13]. It is worth to mention that the only regioisomeric
diarylsulfones obtained in this research may be further converted
to fused diaryl sulfones, which show a great significance due to
their prospective application in pharmaceutical and material areas
[36]. In addition, aromatic heterocyclics such as thiophene could
also be converted to the corresponding sulfone with a good yield
(Table 2, entry 18), implying that heterocyclic sulfones could also
be obtained by this HSBM method. In the meantime, this reaction
could also be performed well in big PTFE milling beaker (35 mL)
with a PTFE ball (entries, 1, 2, 4, and 14).
Figure 2. FT-IR (black) and Raman (red) spectrum of the white
solid.
The FTIR spectrum obtained is almost the same with pristine
Cd3(PO4)2 measured by He et al [37]. Basically, the peak at 1012
cm-1 as well as the should peak at 1065 cm-1 can be assigned to the
asymmetric stretching modes of P=O group. The peak around 550
cm-1 is the asymmetric bending modes of O-P-O [38].
Correspondingly, the symmetric stretching modes of P-O bands is
at 940 cm-1 in the Raman spectrum [39]. The above spectroscopic
results strongly suggest the existence of phosphate anion in the
tested substance. Considering the only possible metal existed in
the solid was Cadmium, and Cd3(PO4)2 could not be dissolved in
water, therefore, the white solid should contain Cd3(PO4)2 as the
dominant component. Combined with 4- biphenyl sulfonic acid
separated above, a plausible mechanism for HSBM sulfonation
reaction is depicted in Scheme 1.
As far as we know, this is the first observation for the synthesis
of diarylsulfones via HSBM reaction. Since the above
experimental results imply an electrophilic substitution process,
we suggest that the aromatic sulfonic acid should be the key
intermediate. In order to obtain this intermediate, the HSBM
reaction by taking biphenyl as substituent was re-investigated.
Since aromatic sulfonic acid may have relatively large solubility
in methanol, the reaction mixture was extracted with methanol.
The solvent was removed via rot-vap, and the residue was purified
by column chromatography using dichloromethane/methanol
(15:1, v/v) as eluent. A white solid was obtained, the structure of
which was confirmed as 4-biphenyl sulfonic acid by 1H NMR, 13
NMR, and HRMS (ESI).
C
To make the mechanism of this HSBM reaction more clearly,
the changing of the inorganic components (3CdSO4·xH2O and
P2O5) involved after the HSBM reaction was also investigated.
After the standard HSBM reaction procedure, the reaction mixture
was extracted thoroughly by chloroform in order to remove any
organic components. Then the residue was rinsed with 20 mL of 5
N NaOH solution for a while and then centrifuged. The resulting
solid was fully dried to give a white solid. FT-IR and Raman
spectroscopy was employed to investigate its possible structure,
respectively (Figure 2).
Scheme 1. Plausible mechanism for HSBM sulfonation reaction
by taking biphenyl as substituent
As shown in Scheme 1, firstly, 3CdSO4·xH2O reacted with
P2O5 to produce H2SO4 (a). The biphenyl was sulfonated by this in
situ generated H2SO4 to give 4-biphenyl sulfonic acid (b).
Accordingly, 4-biphenyl sulfonic acid reacted with another
biphenyl through electrophilic substitution process to give the final
product of 4,4'-sulfonyldibiphenyl (c). The in situ generated water
during the reaction was adsorbed by the excessive P2O5 to produce
phosphoric acid (d). This process would move water from the
products which would also promoted the HSBM reaction forward.

5
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Supplementary data to this article can be found online at XXX.

6
Tetrahedron
Highlights
 Solvent-free
mechanochemical
synthesis of sulfones
 3CdSO4·xH2O as the alterative
reagent instead of sulfonic acid
 Facile, safe, and eco-friendly method
with high yield
Declaration
The authors declare no competing financial
interest