Magnetically separable copper ferrite nanoparticles-catalyzed synthesis of diaryl, alkyl/aryl sulfones from arylsulfinic acid salts and organohalides/boronic acids

Article abstract of DOI:10.1002/adsc.201301003

A recyclable, inexpensive, non-toxic and environmentally benign catalytic system comprised of magnetically separable copper ferrite (CuFe ₂O₄) nanoparticles has been developed for the synthesis of diaryl, alkyl/aryl sulfones. Arylsulfinic acid salts are coupled with various alkyl/aryl halides/boronic acids to afford the corresponding diaryl, alkyl/aryl sulfones in good to excellent yields under the identical catalytic system. A wide range of functional group tolerance, with facile recovery of the catalyst by application of an external magnetic field, and consistently high catalytic efficiency for five consecutive cycles render the protocol operationally attractive.

Full text of DOI:10.1002/adsc.201301003

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DOI: 10.1002/adsc.201301003
Magnetically Separable Copper Ferrite Nanoparticles-Catalyzed
Synthesis of Diaryl, Alkyl/Aryl Sulfones from Arylsulfinic Acid
Salts and Organohalides/Boronic Acids
B. T. V. Srinivas,a Vikas S. Rawat,a Kavitha Konda,a and Bojja Sreedhara,*
a
Inorganic & Physical Chemistry Division, Indian Institute of Chemical Technology (Council of Scientific & Industrial
Research), Hyderabad – 500607, India
Fax : (+91)-40-2716-0921; e-mail: sreedharb@iict.res.in
Received: November 11, 2013; Published online: March 3, 2014
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201301003.
Abstract: A recyclable, inexpensive, non-toxic and cal catalytic system. A wide range of functional
environmentally benign catalytic system comprised group tolerance, with facile recovery of the catalyst
of magnetically separable copper ferrite (CuFe2O4) by application of an external magnetic field, and con-
nanoparticles has been developed for the synthesis sistently high catalytic efficiency for five consecutive
of diaryl, alkyl/aryl sulfones. Arylsulfinic acid salts cycles render the protocol operationally attractive.
are coupled with various alkyl/aryl halides/boronic
acids to afford the corresponding diaryl, alkyl/aryl Keywords: boron; copper; nanoparticles; sulfones;
sulfones in good to excellent yields under the identi- sulfur
Introduction
oxidation-sensitive moieties. Some recent methods
are the coupling of sulfinic acid salts with aryl halide
Aryl sulfones are valuable moieties found in various and/or aryltriflates,[32] the coupling of arylboronic
pharmaceuticals, agrochemicals, and polymeric com- acids with sulfonyl chlorides,[33] and coupling of aryl-
pounds.[1] In particular, their unique bioactivities have boronic acids with sulfinic acid salts.[34] More recently
attracted considerable interest in medicinal chemis- the Pd-catalyzed and also metal-free arylation of sul-
try.[1a,2–24] (please see the Supporting Information) finic acid sodium salts with diaryliodonium salts has
Apart from these, they also form an important class also been developed.[35] However, these methods have
of intermediates in organic synthesis,[25] that exhibit limited application due to the use of toxic/or expen-
interesting chemical properties[26] and have many in- sive transition metals, low functional group tolerance,
dustrial applications.[27]
limited availability of substrate, low yields, particular-
Over the years various methods have been devel- ly with aryl bromides/or other halides and heterocy-
oped for the synthesis of sulfones. However, the ma- clic substrates, longer reaction times, and dry reaction
jority of them are associated with one or more limita- conditions. Moreover, non-recyclability of catalysts
tions. The sulfonylation approach is limited to elec- limited their scope in large or industrial scale produc-
tron-rich substrates and also suffers from formation of tions. In the context of environmental benign, effi-
a mixture of isomeric products.[28] Oxidation process- cient and clean manufacturing processes, the develop-
es, on the other hand, depend on the availability of ment of new protocols for the synthesis of aryl sul-
sulfides or sulfoxides.[29] Harsh reaction conditions fones is therefore highly desirable.
and lower yields in the case of sulfinate-sulfone rear-
Magnetic nanoparticles have emerged as a useful
rangements[30] and low compability of various func- group of heterogeneous catalysts that are robust with
tional groups on using organometallic reagents[31] are high surface area and readily availability. Separation
further limitations.
of magnetic nanoparticles is simple and is an attrac-
Recently, a significant improvement in this arena tive alternative to filtration or centrifugation and en-
has been made by using copper or palladium com- hances reusability, making the catalyst environmental-
plexes as catalysts, under neutral or weakly basic re- ly benign, cost-effective and promising for industrial
action conditions and hence compatible with various applications. With our experience in sulfone chemis-
functional groups like olefin, amine and other acid- or try[36a–c] and as a part of our ongoing research program
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B. T. V. Srinivas et al.
in the field of magnetic nanoparticles as catalysts,[36d–g]
the application of “magnetic CuFe2O4 nanoparticles”
in the synthesis of aryl sulfones has been explored.[37]
CuFe2O4 nanoparticles are of spinel-type structure
having catalytically active copper centers, that have
been used in several applications including the recent-
ly reported azide-alkyne cycloadditions,[38] epoxide-
openings,[39] and Ullmann-type couplings.[40] To the
Table 1. Optimization of reaction conditions for the reaction
of iodobenzene 1a with sodium para-toluenesulfinate 2a.[a]
Entry Ligand
Solvent
Yield [%][b]
À
best of our knowledge, CuFe2O4-catalyzed C S cou-
pling has not been studied so far.
1
2
3
4
5
6
7
8
–
DMF
DMF
DMF
32
43
46
33
40
58
31
78
43
71
32
l-proline
2,2’-bipyridine
(S)-(À)-1,1’-bi(2-naphthol) DMF
Results and Discussion
acetylacetone
DMF
DMF
DMF
DMF
DMF
DMSO
toluene
picolinic acid
To begin with we investigated the traditional cross-
coupling reaction of iodobenzene (1a) and sodium
para-toluenesulfinate (2a) as a model substrates using
CuFe2O4 catalyst in DMF at 1108C for synthesis of 1-
methyl-4-(phenylsulfonyl)benzene (3a).
8-hydroxyquinoline
1,10-phenanthroline
TMEDA
9
10
11
12
13
14
15
16
17
18
19
20
21
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
The initial reaction resulted in a 32% yield of 3a.
To further optimize the reaction conditions, the fol-
lowing reaction variables were examined: the pres-
ence or absence of ligands, solvents, and reaction tem-
perature and the results are presented in Table 1. As
compared to the initial run (Table 1, entry 1), the ad-
dition of 1,10-phenanthroline as ligand significantly
improved the yield to 78% of 3a in DMF (Table 1,
entry 8). Furthermore, the bidentate N-ligands like
2,2’-bipyridine, TMEDA, or 1,10-phenanthroline
(Table 1, entries 3, 8 and 9) gave good results com-
pared to other ligands used in our model reaction and
hence it is interpreted that these ligands can stabilize
the generated intermediate copper species in this
transformation. Among various solvents used in opti-
mization studies (Table 1, entries 7–15), the best re-
sults were obtained by using polar aprotic solvents
such as N,N-dimethylformamide (DMF) and dimethyl
sulfoxide (DMSO) (Table 1, entries 1–10) and this can
be attributed to the good solubility of sodium arylsul-
finic acid salts in these solvents over others. The reac-
tion in solvents like toluene, 1,4-dioxane, THF, water
1,4-dioxane 34
THF
0
0
0
water
PEG 400
DMF
DMF
DMF
DMF
DMF
DMF
0[c]
40[d]
0[e]
10[f]
32[g]
48[h]
[a]
Reaction conditions: iodobenzene (1 mmol), sodium
para-toluenesulfinate (1.2 mmol), ligand (10 mol%) and
CuFe2O4 catalyst (10 mol%) in solvent (2 mL) at 1108C
for 12 h. TMEDA=tetramethylethylenediamine.
Isolated yield.
Reaction with Fe3O4 (10 mol%) nanoparticles as catalyst.
Reaction with CuO (10 mol%) nanoparticles as catalyst.
Without catalyst.
[b]
[c]
[d]
[e]
[f]
Temp. =258C.
Temp. =608C.
Temp. =808C.
[g]
[h]
and PEG 400 resulted in significantly lower yields that no reaction took place without the catalyst
(Table 1, entries 11–15) of 3a. (Table 1, entry 18). Lowering the temperature to 25,
Carrying out the reaction without exclusion of air 60, and 808C resulted in substantially lower yields of
or moisture or under an Ar or N2 atmosphere resulted 10, 32, and 48%, respectively of 3a (Table 1, en-
in almost the same yield of 3a; which makes this pro- tries 19–21).
cess advantageous and operationally simple. Use of
After establishing the optimized reaction condi-
excess amounts of ligand or catalyst and longer reac- tions, i.e., 1.0 equiv. of organohalide, 1.2 equiv. of aryl-
tion times did not afford any better results. Moreover, sulfinic acid salt, 10 mol% of CuFe2O4 and 10 mol%
to understand the role of iron in the present catalytic of 1,10-phenanthroline in DMF at 1108C, we further
system, we carried out two independent reactions explored the generality and functional group compati-
with 10 mol% of nano Fe3O4 and nano CuO catalysts bility of this reaction on various structurally diverse
under the optimized reaction conditions. No yield was organohalides, and the results are shown in Table 2.
observed with nano Fe3O4 (Table 1, entry 16) whereas
As can be seen from the Table 2, the reaction pro-
nano CuO (Table 1, entry 17) afforded 40% of the de- ceeds smoothly with various aryl or alkyl halides with
sired product; clearly showing that Cu is the active sodium para-toluenesulfinate (2a) and/or sodium ben-
catalytic center in this reaction. It is worth mentioning zenesulfinate (2b) to afford aryl sulfones 3a–3t in
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Magnetically Separable Copper Ferrite Nanoparticles-Catalyzed Synthesis
Table 2. Scope of synthesis of arylsulfones 3 from various organohalides 1.[a]
[a]
Reaction conditions: organohalide (1 mmol), arylsulfinic acid salt (1.2 mmol), 1,10-phenanthroline (10 mol%) and
CuFe2O4 catalyst (10 mol%) in DMF (2 mL) at 1108C for 12 h.
Isolated yield.
[b]
good to excellent yields. The reaction also showed ex- 3f, 3g, and 3l that are obtained in good yields of 71%,
cellent tolerance for various functional groups like 91%, 82%, and 67%, respectively. It was seen that
ether, nitro, aldehyde, nitrile, and carboxyl.
the reactions with organobromine compounds were
Notably, regardless of their electronic or steric slightly more sluggish resulting in lower yields of the
properties, there is no appreciable difference in the corresponding aryl sulfones and this can be attributed
yield with either of the two arylsulfinic acid sodium to the low leaving group property of bromine.
salts. Moreover, the aromatic substituents have only
During the catalytic synthesis of aryl heteroaryl sul-
a minor effect on the outcome of the reaction, for in- fones, the basic N-atom present in these substrates
stance, aryl halides having a strong electron-donating can deactivate the catalyst via binding with the active
substituent such as OMe in 1-iodo-4-methoxybenzene catalytic sites. Hence, it is worthwhile to mention that
and a strong electron-withdrawing substituent such as the present protocol can also be extended to synthe-
F in 1-bromo-4-fluorobenzene provide the desired size aryl heteroaryl sulfones that are of special inter-
diaryl sulfones 3d and 3I in high yields of 83% and est for the development of new drug molecules.
82%, respectively. However, the outcome of the reac- CuFe2O4 has shown excellent catalytic activity with
tion is favoured for aryl halides having electron-with- heteroaryl halides and gave the corresponding aryl
drawing substituents. Steric hindrance also does not heteroaryl sulfones in good to excellent yields, for ex-
cause any problem in the reaction, as seen from 3e, ample, 2-bromothiazole, 2-bromopyridine and 3-bro-
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Table 3. Scope of synthesis of diaryl sulfones 3 from various boronic acids 4.[a]
[a]
Reaction conditions: boronic acid (1 mmol), arylsulfinic acid salt (1.2 mmol), 1,10-
phenanthroline (10 mol%) and CuFe2O4 catalyst (10 mol%) in DMF (2 mL) at
1108C for 12 h.
Isolated yield.
[b]
[c]
Reaction of para-tolueneboronic acid with sodium benzenesulfinate.
moquinoline afforded the corresponding desired matic compounds containing various functional
products 3p, 3q and 3r in good yields of 84%, 87%, groups via an oxidative strategy.[43,44] Based on the
and 82%, respectively.[41] Notably, alkyl halides like 1- previous reports on copper-catalyzed cross-coupling
bromohexane and 2-bromopropane also showed ex- reactions between arylsulfinic salts and boronic acids
cellent conversion to the corresponding alkyl aryl sul- to synthesize diaryl sulfones,[34] we thought to investi-
fones 3s and 3t with yields of 91% and 88%, respec- gate the feasibility of analogous cross-coupling reac-
tively. The alkylsulfinic acid salts, like methanesulfinic tions under our optimized reaction conditions with
acid sodium salt did not afford the desired product the present catalytic system. To our delight the cross-
under these reaction conditions. Even the reactions coupling between phenylboronic acid (4a) and sodium
with aryl chlorides were also unfruitful.
para-toluenesulfinate (2a) under the optimized reac-
tion conditions resulted in a 75% yield of 3a
(Scheme 1).
Aryl Sulfones via Coupling of Boronic Acids with
Arylsulfinic Salts
Notably this was one of the foremost advantages of
the present protocol over existing methods as earlier
no single catalytic system was used for two different
Boronic acids are very common chemicals and are protocols and also as reported by Batey et al., there is
commercially available. Moreover, these can be easily no need to add any oxidant or dehydrating agent in
synthesized from aryl halides, triflates and tosylates this method.[34b]
or by direct borylation of arenes by an iridium-cata-
We further explored the scope and functional group
[42]
À
lyzed C H bond activation procedure.
Further- compatibility of this protocol on various structurally
more, the boronic acids have been used as a coupling diverse boronic acids, and the results are shown in
partner with various nucleophiles to synthesize aro- Table 3.
Scheme 1. The cross-coupling between phenylboronic acid (4a) and sodium para-toluenesulfinate (2a).
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A variety of arylboronic acids was subjected to the (1a) with sodium para-toluenesulfinate (2a) and an
optimized reaction condition to couple with arylsul- analogous, cross-coupling of phenylboronic acid (4a)
finic acid salts to afford the corresponding diaryl sul- with sodium para-toluenesulfinate (2a) separately
fones with moderate to excellent yields. Both elec- under the optimized reaction conditions for five con-
tron-rich and electron-deficient substituents on boron- secutive cycles.
ic acids have only minor influence on the reaction
After completion of the reaction, the reaction mix-
outcome. A variety of functional groups was also well ture was cooled to room temperature, and the catalyst
tolerated under the reaction conditions. It is notewor- easily separated from the reaction mixture by apply-
thy to mention that despite the tendency to get poly- ing an external magnetic field, then the reaction prod-
merized, the trans-2-phenylvinylboronic acid coupled uct was extracted with ethyl acetate. The reaction vial
with sodium para-toluenesulfinate (2a) and resulted with catalyst was dried in an oven and subjected to
in the corresponding (E)-1-methyl-4-(styrylsulfonyl)- a second run of the sulfonylation by charging with the
benzene (3v) with 65% yield. It is also worth men- same substrates. The results of five runs showed
tioning that no product was observed by the self-cou- almost consistent yields. The yields from the second
pling of boronic acids or aryl halides.
to fifth cycle for sulfonylation of iodobenzene were
78%, 78%, 76%, and 76%, respectively and those of
sulfonylation of phenylboronic acid were 75%, 74%,
72%, and 72%, respectively.
Recycling of the Catalyst
Finally, we studied the recyclability of the catalytic
system (Table 4). For this, we subjected the CuFe2O4 Synthesis and Characterization of Catalyst (Nano-
nanoparticles to the cross-coupling of iodobenzene CuFe2O4)
The CuFe2O4 nanoparticles were prepared according
Table 4. Recovery and reuse of CuFe2O4 nanoparticles for
the sulfonylation of iodobenzene (1a)[a] and phenylboronic
to the literature procedure and characterized by X-
ray diffraction (XRD), transmission electron micros-
copy (TEM), X-ray photoelectron spectroscopy
(XPS) and atomic absorption spectroscopy (AAS).[37]
XRD spectra of fresh and used CuFe2O4 nanoparti-
cles are shown in Figure 1.
acid (4a)[b]
.
Run
1st
2nd
3rd
4th
5th
Average
Yield [%][a,c]
Yield [%][b,c]
78
75
78
75
78
74
76
72
76
72
77
73
The XRD patterns are characteristic of tetragonal
CuFe2O4 (JCPDS card No. 34-0425) with good crystal-
linity. The XRD analysis shows that the metal oxides
present are in the form of the spinel structure of
CuFe2O4 (d=2.53, 2.98, 1.49, 1.61 ꢁ). The particle
size was calculated by means of the Debye–Scherrer
formula based on the full width at half-maximum of
the highest intensity diffraction peak at 2q=35.68 and
was found to be ~18 nm and is in agreement with
[a]
Reaction conditions: iodobenzene (1 mmol), sodium
para-toluenesulfinate (1.2 mmol), 1,10-phenanthroline
(10 mol%) and CuFe2O4 catalyst (10 mol%) in DMF
(2 mL) at 1108C for 12 h.
Reaction conditions: phenylboronic acid (1 mmol),
sodium para-toluenesulfinate (1.2 mmol), 1,10-phenan-
throline (10 mol%) and CuFe2O4 catalyst (10 mol%) in
DMF (2 mL) at 1108C for 12 h.
[b]
[c]
Isolated yield.
Figure 1. X-ray diffraction patterns of the CuFe2O4 nanoparticles (a) used in the coupling of sodium para-toluenesulfinate
with iodobenzene, (b) used in the coupling of sodium para-toluenesulfinate with phenylboronic acid after the 5th cycle and
(c) fresh catalyst.
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Figure 2. TEM images of CuFe2O4 nanoparticles (a) used in the coupling of sodium para-toluenesulfinate with iodobenzene,
(b) used in the coupling of sodium para-toluenesulfinate with phenylboronic acid after the 5th cycle, (c) fresh catalyst ob-
served at 120 kV and (d) average size distribution.
TEM analysis (Figure 2), which shows mainly nano- and 723.7 eV (Figure 3, C), respectively. The binding
particles with a particle size in the range of 10–30 nm. energy peaks for Fe 2p of both the fresh and used cat-
Notably, the morphology and size of the particles alyst could be deconvoluted into two peaks. The
were unaltered even after five catalytic cycles, which peaks centered at 710 eV and 722.6 eV correspond to
correlates well with retention of catalytic activity Fe 2p3/2 and Fe 2p1/2 and are due to Fe in +2 oxida-
after recycling. The SAED images also confirm the tion state. The peaks centered around 712.3 and
crystalline nature of both the fresh and used magnetic 724.5 eV, corresponding to Fe 2p3/2 and Fe 2p1/2, re-
nanoparticles. The oxidation states of the elements in spectively, and are consistent with typical values for
CuFe2O4 nanoparticles were characterized by XPS, as the ferric oxides. The copper content in the catalyst,
shown in Figure 3.
was determined to be 27.3% by AAS. The leaching of
The survey scan of CuFe2O4 nanoparticles shows the metal after the five cycles was determined by
characteristic peaks for C 1s (285 eV), O 1s (535 eV), AAS and was found to be negligible. (0.048%).
Fe 2p (710 eV), and Cu 2p (935 eV; Figure 3, A). The
high resolution narrow scans for Cu 2p in CuFe2O4
displays binding energy peaks for 2p3/2 and 2p1/2, at Conclusions
934.2 and 953.3 eV (Figure 3, B), clearly showing that
copper is in its +2 oxidation state. Likewise the high- In conclusion, we have developed an efficient and en-
resolution narrow scan for Fe 2p in CuFe2O4 reveals vironmental friendly catalytic system using magneti-
Fe 2p3/2 and Fe 2p1/2 binding-energy peaks at 710.0 cally separable CuFe2O4 nanoparticles for the cross-
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Magnetically Separable Copper Ferrite Nanoparticles-Catalyzed Synthesis
Figure 3. XPS spectra of CuFe2O4 nanoparticles (a) used in the coupling of sodium para-toluenesulfinate with iodobenzene,
(b) used in the coupling of sodium para-toluenesulfinate with phenylboronic acid after the 5th cycle, and (c) fresh catalyst.
(A) XPS survey scans, (B) high-resolution spectra for Cu 2p and (C) high-resolution spectra for Fe 2p.
coupling between arylsulfinic acid salts with various recyclability of the catalytic system makes the reac-
alkyl or/aryl halide/and boronic acids to generate the tion economically and potentially viable for commer-
corresponding aryl sulfones under similar reaction cial applications. To the best of our knowledge it is
À
conditions. The catalyst is magnetically separable and the first report on the C S coupling with CuFe2O4
eliminates the requirement of nano catalyst centrifu- magnetic nanoparticles. Furthermore, this protocol
gation after completion of the reaction, which is an can be extended for the synthesis of vinyl sulfones.
additional sustainable attribute of this protocol. The
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to the vial and the reaction was conducted as described
above. The decanted organic layer was extracted with water
twice then the organic layers were washed with brine, dried
over anhydrous Na2SO4 and concentrated under vacuum.
The crude product was loaded on a silica gel column and
eluted with hexane and ethyl acetate as eluting mixture to
afford the pure product.
Experimental Section
General Information
All chemicals were purchased from Sigma–Aldrich and S.D
Fine Chemicals, Pvt. Ltd. India and used as received. The
particle size and morphology of the samples were studied
using a Philips TECNAI F12 FEI transmission electron mi-
croscope (TEM). The X-ray powder diffraction (XRD) pat-
terns were recorded on a Rigaku diffractometer with Cu Ka
radiation. XPS measurements were obtained on
a KRATOS-AXIS 165 instrument equipped with dual alu-
minium–magnesium anodes using Mg Ka radiation (hn=
1253.6 eV) operated at 5 kV and 15 mA with pass energy
80 eV and an increment of 0.1 eV. The samples were de-
gassed out for several hours in the XPS chamber to mini-
mize air contamination to the sample surface. To overcome
the charging problem, a charge neutralizer of 2 eV was ap-
plied and the binding energy of C 1s core level (BE =
284.6 eV) of adventitious hydrocarbon was used as a stan-
dard. The XPS spectra were fitted using a non-linear square
method with the convolution of Lorentzian and Gaussian
functions after a polynomial background was subtracted
from the raw spectra. The IR spectra of all compounds were
recorded on a Perkin–Elmer, Spectrum GX FTIR spectrom-
eter. The IR values are reported in reciprocal centimeters
(cmÀ1). ESI mass spectra were recorded on a Finnigan LCQ
Advantagemax spectrometer. High-resolution mass spectra
(HR-MS) were recorded on a QSTAR XL Hybrid MS/MS
mass spectrometer using ESI-QTOF mass spectrometry. All
the glassware was dried before use. Ethyl acetate, hexane
and acetone were distilled before use. Silica gel (100–200
mesh) was used for column chromatography and reactions
were monitored by thin layer chromatography (TLC) car-
ried out on 0.25 mm silica gel coated glass plates 60F254
using UV light as visualizing agent and iodine or KMnO4 so-
lution followed by heating as developing agent. 1H NMR
spectra were recorded at 300 MHz. The chemical shifts are
expressed (ppm), referenced to TMS (0.00 ppm) peak. The
following abbreviations were used to designate chemical
shift multiplicities: s=singlet, br=broad, d=doublet, t=
triplet, q=quartet, m=multiplet. 13C NMR spectra were re-
corded at 75 MHz. The chemical shifts are expressed (in
ppm), reported from the central peak of deuterochloroform
(77 ppm). The 13C NMR spectra are proton decoupled.
Fe3O4 [<50 nm particle size (TEM), ꢀ98%] and CuO (<
50 nm particle size) were purchased from Sigma–Aldrich.
Characterization Data of Compounds
1-Methyl-4-(phenylsulfonyl)benzene (3a):[35c] Colorless solid;
yield: 180 mg (78%); mp 126–1288C (Lit.[35c] 127–1298C).
IR (KBr): n=547, 577, 652, 685, 728, 758, 816, 1019, 1069,
1105, 1155, 1302, 1386, 1446, 1593, 1743, 2924, 3424 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=2.39 (s, 3H), 7.29 (d, 2H,
J=8.1 Hz), 7.46–7.57 (m, 3H), 7.83 (d, 2H, J=8.1 Hz),
7.90–7.96 (m, 2H); 13C NMR (75 MHz, CDCl3): d=21.5,
127.4, 127.6, 129.1, 129.8, 132.9, 138.5, 141.8, 144.1; ESI-MS:
m/z=233 (M+H)+, 255 (M+Na)+; ESI-HR-MS: m/z=
233.0626 (M+H)+, calcd. for C13H13O2S: 233.0630.
Sulfonyldibenzene (3b):[35c] Colorless solid; yield: 166 mg
(76%); mp 120–1228C (Lit.[35c] 122–1248C). IR (KBr): n=
426, 559, 587, 686, 727, 761, 995, 1021, 1067, 1103, 1154,
1312, 1446, 1475, 1579, 1743, 1902, 1969, 2852, 2922, 3062,
3422 cmÀ1 1H NMR (300 MHz, CDCl3): d=7.48–7.53 (m,
;
4H), 7.54–7.60 (m, 2H), 7.93–7.98 (m, 4H); 13C NMR
(75 MHz, CDCl3): d=127.5, 129.2, 133.1, 141.5; ESI-MS: m/
z=219 (M+H)+, 241 (M+Na)+; ESI-HR-MS: m/z=
219.0466 (M+H)+, calcd. for C12H11O2S: 219.0474.
1,2-Dimethyl-4-tosylbenzene (3c):[45a] White solid; yield:
232 mg (89%); mp 54–568C (Lit.[45a] 558C). IR (KBr): n=
441, 546, 576, 650, 685, 727, 757, 816, 995, 1018, 1068, 1104,
1154, 1309, 1399, 1446, 1592, 1656, 1727, 1925, 2852, 2921,
1
2959, 3061, 3423 cmÀ1; H NMR (300 MHz, CDCl3): d=2.28
(s, 3H), 2.29 (s, 3H), 2.38 (s, 3H), 7.23 (d, 1H, J=7.9 Hz),
7.28 (d, 2H, J=8.1 Hz), 7.63–7.69 (m, 2H), 7.81 (d, 2H, J=
8.1 Hz); 13C NMR (75 MHz, CDCl3): d=19.7, 19.9, 21.5,
125.0, 127.4, 128.2, 129.7, 130.2, 137.9, 139.0, 139.0, 142.6,
143.7; ESI-MS: m/z=261 (M+H)+; ESI-HR-MS: m/z=
261.0937 (M+H)+, calcd. for C15H17O2S: 261.0943.
1-Methoxy-4-tosylbenzene (3d):[34a] Yellow solid; yield:
218 mg (83%); mp 101–1038C (Lit.[34a] 100–1028C). IR
(KBr): n=551, 632, 678, 711, 803, 831, 1018, 1071, 1106,
1150, 1180, 1264, 1295, 1317, 1412, 1457, 1494, 1596, 1743,
1916, 2924, 2971, 3095, 3448 cmÀ1
;
1H NMR (300 MHz,
CDCl3): d=2.39 (s, 3H), 3.84 (s, 3H), 6.95 (d, 2H, J=
8.8 Hz), 7.28 (d, 2H, J=8.1 Hz), 7.80 (d, 2H, J=8.1 Hz),
7.86 (d, 2H, J=8.8 Hz); 13C NMR (75 MHz, CDCl3): d=
21.4, 55.5, 114.3, 127.3, 129.6, 129.7, 133.4, 139.3, 143.6,
163.1; ESI MS: m/z=263 (M+H)+, 285 (M+Na)+; ESI-
HR-MS: m/z=263.0730 (M+H)+, calcd. for C14H15O3S:
263.0736.
General Procedure for the Synthesis of Diaryl, Alkyl/
Aryl Sulfones
CuFe2O4 (24 mg, 0.1 mmol) was added to a mixture of orga-
nohalide (1 mmol) or boronic acid (1 mmol), arylsulfinic
acid salt (1.2 mmol) and 1,10-phenanthroline (0.1 mmol) in
2 mL DMF in a pressure tube, and stirred at 1108C for 12 h.
After completion of the reaction, ethyl acetate (5 mL) was
added to the reaction mixture. An external magnetic field
applied using a magnet outside the reaction vial to accumu-
late catalyst then the organic layer decanted, the aforemen-
tioned procedure was followed 2 more times with ethyl ace-
tate. The separated catalyst with vial was dried in an oven.
For the subsequent run, fresh starting materials were added
1-Tosylnaphthalene (3e):[28d] White solid; yield: 200 mg
(71%); mp 100–1028C (Lit.[28d] 102–1048C). IR (KBr): n=
446, 504, 542, 580, 648, 688, 739, 773, 810, 970, 1016, 1083,
1131, 1153, 1196, 1307, 1400, 1504, 1592, 1654, 1735, 1920,
2853, 2923, 3060, 3421 cmÀ1 1H NMR (300 MHz, CDCl3):
;
d=2.34 (s, 3H), 7.23–7.27 (m, 2H), 7.50–7.64 (m, 3H), 7.85
(d, 2H, J=8.3 Hz), 7.89 (d, 1H, J=8.1 Hz), 8.07 (d, 1H, J=
8.1 Hz), 8.48–8.51 (m, 1H), 8.64 (d, 1H, J=8.6 Hz);
13C NMR (75 MHz, CDCl3, DMSO-d6): d=19.4, 122.0,
122.8, 125.1, 125.4, 125.9, 126.5, 127.4, 127.7, 128.0, 132.1,
812
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Adv. Synth. Catal. 2014, 356, 805 – 817

FULL PAPERS
Magnetically Separable Copper Ferrite Nanoparticles-Catalyzed Synthesis
133.4, 133.9, 136.6, 142.2; ESI-MS: m/z=283 (M+H)+, 305
(M+Na)+; ESI-HR-MS: m/z=283.0773 (M+H)+, calcd. for
C17H15O2S: 283.0787.
1498C). IR (KBr): n=407, 537, 594, 664, 724, 760, 842, 1001,
1072, 1108, 1156, 1182, 1291, 1308, 1394, 1446, 1594, 1726,
2853, 2924, 2956, 3060 cmÀ1 1H NMR (300 MHz, CDCl3):
;
2-Tosylbenzaldehyde (3f): White solid; yield: 237 mg
(91%); mp 72–738C (Lit.[32b] 73–748C). IR (KBr): n=461,
506, 574, 652, 705, 731, 771, 814, 1045, 1088, 1119, 1157,
1184, 1258, 1314, 1396, 1449, 1493, 1589, 1692, 1922, 2923,
d=7.36–7.62 (m, 8H), 7.70 (d, 2H, J=8.4 Hz), 7.92–8.06 (m,
4H); 13C NMR (75 MHz, CDCl3): d=127.2, 127.6, 127.8,
128.1, 128.5, 129.0, 129.2, 133.1, 139.1, 140.0, 141.6, 146.1;
ESI-MS: m/z=295 (M+H)+; ESI-HR-MS: m/z=295.0780
(M+H)+, calcd. for C18H15O2S: 295.0787.
3083, 3449 cmÀ1 1H NMR (300 MHz, CDCl3): d=2.41 (s,
;
3H), 7.33 (d, 2H, J=8.1 Hz), 7.68–7.83 (m, 4H), 7.98–8.05
(m, 1H), 8.14–8.22 (m, 1H), 10.86 (s, 1H); 13C NMR
(75 MHz, CDCl3): d=21.5, 127.4, 129.3, 129.3, 130.1, 130.2,
133.6, 133.7, 138.3, 142.6, 144.9, 189.4; ESI-MS: m/z=283
(M+Na)+; ESI-HR-MS: m/z=283.0384 (M+Na)+, calcd.
for C14H12O3NaS: 283.0399.
4-Methyl-2-tosylbenzaldehyde (3l): Pale yellow solid;
yield: 184 mg (67%); mp 120–1228C. IR (KBr): n=456, 508,
574, 632, 654, 708, 789, 819, 884, 1049, 1088, 1150, 1200,
1310, 1405, 1448, 1492, 1594, 1695, 1743, 1940, 2779, 2854,
2922, 3373 cmÀ1 1H NMR (300 MHz, CDCl3): d=2.41 (s,
;
3H), 2.51 (s, 3H), 7.32 (d, 2H, J=8.1 Hz), 7.50 (d, 1H, J=
7.9 Hz), 7.77 (d, 2H, J=8.1 Hz), 7.93 (d, 1H, J=7.9 Hz),
8.01 (s, 1H), 10.79 (s, 1H); 13C NMR (75 MHz, CDCl3): d=
21.5, 21.7, 127.3, 129.4, 129.7, 130.1, 131.2, 134.2, 138.5,
142.3, 144.7, 145.2, 189.1; ESI-MS: m/z=275 (M+H)+, 297
(M+Na)+; ESI-HR-MS: m/z=297.0543 (M+Na)+, calcd.
for C15H14O3NaS: 297.0555.
2-(Phenylsulfonyl)benzaldehyde (3g):[45b] White solid;
yield: 202 mg (82%); mp 90–928C (Lit.[45b] 92.0–93.58C). IR
(KBr): n=450, 484, 561, 585, 680, 734, 1087, 1119, 1152,
1188, 1313, 1397, 1445, 1473, 1579, 1700, 1963, 2767, 2853,
2889, 2922, 3069, 3448 cmÀ1 1H NMR (300 MHz, CDCl3):
;
d=7.52–7.57 (m, 2H), 7.59–7.64 (m, 1H), 7.72–7.80 (m,
2H), 7.89–7.92 (m, 2H), 8.01–8.05 (m, 1H), 8.19–8.22 (m,
1H), 10.85 (s, 1H); 13C NMR (75 MHz, CDCl3): d=127.3,
129.0, 129.4, 129.4, 129.5, 133.6, 133.7, 133.8, 141.3, 142.1,
189.2; ESI-MS: m/z=269 (M+Na)+; ESI-HR-MS: m/z=
269.0230 (M+Na)+, calcd. for C13H10O3NaS: 269.0242.
1-Tosyl-3-(trifluoromethyl)benzene (3h):[34a] Yellow solid;
yield: 279 mg (93%); mp 80–828C (Lit.[34a] 81–838C). IR
(KBr): n=493, 540, 576, 666, 696, 725, 806, 905, 1066, 1107,
1-[4-(Phenylsulfonyl)phenyl]ethanone (3m):[45d] Yellow
solid; yield: 177 mg (68%); mp 131–1338C (Lit.[32d] 132–
1348C). IR (KBr): n=456, 496, 555, 591, 628, 702, 766, 846,
961, 1070, 1104, 1161, 1254, 1299, 1322, 1359, 1396, 1446,
1581, 1685, 1937, 2855, 2923, 3039, 3089, 3447 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=2.62 (s, 3H), 7.49–7.64 (m,
3H), 7.96 (d, 2H, J=7.6 Hz), 8.01–8.10 (m, 4H); 13C NMR
(75 MHz, CDCl3): d=26.8, 127.7, 127.9, 129.0, 129.4, 133.6,
140.2, 140.6, 145.3, 196.6; ESI-MS: m/z=283 (M+Na)+;
ESI-HR-MS: m/z=261.0583 (M+H)+, calcd. for C14H13O3S:
261.0579.
1136, 1326, 1402, 1437, 1489, 1598, 1927, 2922, 3449 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=2.41 (s, 3H), 7.34 (d, 2H,
J=8.2 Hz), 7.65 (t, 1H, J=7.8 Hz), 7.80 (d, 1H, J=7.8 Hz),
7.85 (d, 2H, J=8.2 Hz), 8.11 (d, 1H, J=7.8 Hz), 8.19 (s,
1H); 13C NMR (75 MHz, CDCl3): d=21.5, 124.5, 127.8,
129.6, 130.0, 130.1, 130.7, 131.7, 137.5, 143.2, 144.8; ESI-MS:
m/z=323 (M+Na)+; ESI-HR-MS: m/z=301.0491 (M+H)+,
calcd. for C14H12O2F3S: 301.0504.
1-Nitro-4-(phenylsulfonyl)benzene (3n):[35c] Yellow solid;
yield: 200 mg (76%); mp 140–1428C (Lit.[35c] 143–1458C).
IR (KBr): n=475, 560, 604, 680, 733, 854, 922, 1006, 1067,
1103, 1154, 1300, 1354, 1449, 1475, 1529, 1582, 1606, 1745,
1802, 2854, 2925, 3099, 3446 cmÀ1
;
1H NMR (300 MHz,
1-Fluoro-4-(phenylsulfonyl)benzene (3i):[35c] Colorless
solid; yield: 194 mg (82%); mp 111–1128C (Lit.[35c] 112–
1138C). IR (KBr): n=405, 454, 546, 575, 653, 686, 730, 757,
841, 1002, 1068, 1102, 1152, 1236, 1291, 1318, 1403, 1447,
CDCl3): d=7.52–7.68 (m, 3H), 7.98 (d, 2H, J=7.6 Hz), 8.14
(d, 2H, J=8.3 Hz), 8.35 (d, 2H, J=8.3 Hz); 13C NMR
(75 MHz, CDCl3): d=124.4, 127.9, 128.9, 129.6, 134.0, 139.9,
147.2, 150.2; ESI-MS: m/z=286 (M+Na)+; ESI-HR-MS: m/
z=286.0148 (M+Na)+, calcd. for C12H9NO4NaS: 286.0150.
1491, 1586, 1916, 2922, 3073, 3100, 3451 cmÀ1 1H NMR
;
(300 MHz, CDCl3): d=7.15–7.21 (m, 2H), 7.49–7.54 (m,
2H), 7.56–7.60 (m, 1H), 7.92–7.99 (m, 4H); 13C NMR
(75 MHz, CDCl3): d=116.5 (d, J=22.50 Hz), 127.4, 129.3,
130.4 (d, J=9.88 Hz), 133.2, 137.5 (d, J=2.74 Hz), 141.3,
165.4 (d, J=255.74 Hz); ESI-MS: m/z=259 (M+Na)+; ESI-
1-Methyl-4-[(4-nitrophenyl)sulfonyl]benzene
(3o):[45e]
Yellow solid; yield: 244 mg (88%); mp 163–1658C (Lit.[45e]
164–1658C). IR (KBr): n=443, 494, 545, 592, 655, 684, 738,
815, 857, 1012, 1035, 1068, 1104, 1157, 1300, 1349, 1403,
1528, 1592, 1693, 2862, 2914, 3036, 3065, 3103, 3448 cmÀ1
;
HR-MS:
m/z=259.0194
(M+Na)+,
calcd.
for
1H NMR (300 MHz, CDCl3): d=2.42 (s, 3H), 7.35 (d, 2H,
J=8.1 Hz), 7.85 (d, 2H, J=8.1 Hz), 8.11 (d, 2H, J=8.6 Hz),
8.33 (d, 2H, J=8.6 Hz); 13C NMR (75 MHz, CDCl3, DMSO-
d6): d=20.9, 123.8, 127.3, 128.1, 129.6, 136.2, 144.7, 146.9,
149.5; ESI-MS: m/z=300 (M+Na)+; ESI-HR-MS: m/z=
278.0487 (M+H)+, calcd. for C13H12O4NS: 278.0481.
C12H9O2FNaS: 259.0199.
4-Tosylbenzonitrile (3j):[34a] Yellow solid; yield: 222 mg
(86%); mp 129–1318C (Lit.[34a] 129–1318C). IR (KBr): n=
419, 472, 521, 562, 610, 637, 669, 704, 780, 813, 844, 976,
1015, 1069, 1102, 1154, 1185, 1287, 1320, 1396, 1456, 1489,
1593, 1661, 1741, 1932, 2231, 2852, 2922, 2958, 3093,
3411 cmÀ1 1H NMR (300 MHz, CDCl3): d=2.42 (s, 3H),
;
2-Tosylthiazole (3p): Yellow solid; yield: 201 mg (84%);
mp 124–1268C. IR (KBr): n=470, 540, 583, 672, 705, 733,
813, 965, 1012, 1052, 1090, 1146, 1169, 1295, 1329, 1400,
1468, 1592, 1662, 1740, 1940, 2413, 2853, 2923, 2956, 3049,
7.34 (d, 2H, J=8.7 Hz), 7.79 (d, 2H, J=8.7 Hz), 7.83 (d,
2H, J=8.3 Hz), 8.04 (d, 2H, J=8.3 Hz); 13C NMR (75 MHz,
CDCl3): d=21.5, 116.6, 117.1, 127.9, 128.0, 130.2, 132.9,
136.9, 145.1, 146.1; ESI-MS: m/z=280 (M+Na)+; ESI-HR-
MS; m/z=280.0406 (M+Na)+, calcd. for C14H11NO2NaS:
280.0408.
3123, 3448 cmÀ1 1H NMR (300 MHz, CDCl3): d=2.43 (s,
;
3H), 7.37 (d, 2H, J=8.1 Hz), 7.65 (d, 1H, J=2.9 Hz), 7.95
(d, 1H, J=2.9 Hz), 7.99 (d, 2H, J=8.1 Hz); 13C NMR
(75 MHz, CDCl3): d=21.7, 124.6, 125.6, 128.7, 130.1, 135.7,
145.2, 145.6; ESI-MS: m/z=240 (M+H)+, 262 (M+Na)+;
4-(Phenylsulfonyl)-1,1’-biphenyl (3k):[45c] Pale yellow
solid; yield: 265 mg (90%); mp 150–1518C (Lit.[45c] 148–
Adv. Synth. Catal. 2014, 356, 805 – 817
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813

FULL PAPERS
B. T. V. Srinivas et al.
ESI-HR-MS:
C10H10O2NS2: 240.0147.
m/z=240.0150
(M+H)+,
calcd.
for
7.46–7.50 (m, 2H), 7.66 (d, 1H, J=15.4 Hz), 7.83 (d, 2H,
J=8.1 Hz); 13C NMR (75 MHz, CDCl3): d=21.5, 127.5,
127.6, 128.4, 129.0, 129.9, 131.0, 132.4, 137.6, 141.9, 144.3;:
ESI-MS: m/z=259 (M+H)+; ESI-HR-MS: m/z=259.0788
(M+H)+, calcd. for C15H15O2S: 259.0787.
2-Tosylpyridine (3q):[45d] Yellow solid; yield: 203 mg
(87%); mp 101–1028C (Lit.[45e] 102–1038C). IR (KBr): n=
436, 542, 580, 655, 736, 769, 815, 899, 989, 1040, 1070, 1121,
1168, 1294, 1317, 1427, 1451, 1492, 1593, 1667, 1740, 1935,
1-Methyl-4-{[4-(trifluoromethyl)phenyl]sulfonyl}benzene
(3w):[34a] Yellow solid; yield: 174 mg (58%); mp 106–1078C
(Lit.[34a] 105–1078C). IR (KBr): n=588, 659, 716, 815, 843,
1058, 1156, 1293, 1323, 1405, 1451, 1495, 1597, 1741, 1934,
2854, 2924, 3055, 3447 cmÀ1 1H NMR (300 MHz, CDCl3):
;
d=2.41 (s, 3H), 7.33 (d, 2H, J=8.1 Hz), 7.40–7.50 (m, 1H),
7.86–8.02 (m, 3H), 8.19 (d, 1H, J=7.7 Hz), 8.62–8.73 (m,
1H); 13C NMR (75 MHz, CDCl3): d=21.4, 121.8, 126.7,
128.7, 129.6, 135.7, 137.9, 144.7, 150.2, 158.8; ESI MS: m/z=
234 (M+H)+, 256 (M+Na)+; ESI-HR-MS: m/z=234.0578
(M+H)+, calcd. for C12H12O2NS: 234.0583.
2854, 2925, 3060, 3107, 3455 cmÀ1
;
1H NMR (300 MHz,
CDCl3): d=2.41 (s, 3H), 7.33 (d, 2H, J=8.0 Hz), 7.75 (d,
2H, J=8.0 Hz), 7.84 (d, 2H, J=8.0 Hz), 8.06 (d, 2H, J=
8.0 Hz);. 13C NMR (75 MHz, CDCl3): d 21.5, 123.0 (q, J=
273.07 Hz), 126.3 (q, J=3.63 Hz), 127.8, 127.9, 130.1, 134.5
(q, J=32.96 Hz), 137.4, 144.8, 145.5; ESI-MS: m/z=301
(M+H)+, 323 (M+Na)+; ESI-HR-MS: m/z=323.03161
(M+Na)+, calcd. for C14H11O2F3NaS: 323.0324.
3-Tosylquinoline (3r):[45f] Yellow solid; yield: 234 mg
(82%); mp 166–1678C (Lit.[45f] 165–1708C); IR (KBr): n=
406, 473, 550, 679, 755, 787, 815, 918, 1017, 1091, 1149, 1310,
1363, 1452, 1492, 1590, 1742, 2854, 2925, 3447 cmÀ1
;
1-(4-Tosylphenyl)ethanone (3x):[45d] Yellow solid; yield:
168 mg (61%); mp 146–1488C. IR (KBr): n=540, 581, 664,
767, 820, 959, 1011, 1073, 1156, 1182, 1257, 1317, 1462, 1594,
1H NMR (300 MHz, CDCl3): d=2.40 (s, 3H), 7.33 (d, 2H,
J=8.0 Hz), 7.68 (t, 1H, J=7.8 Hz), 7.87 (t, 1H, J=7.8 Hz),
7.91 (d, 2H, J=8.2 Hz), 7.96 (d, 1H, J=8.3 Hz), 8.16 (d,
1H, J=8.3 Hz), 8.79–8.83 (m, 1H), 8.26 (d, 1H, J=1.9 Hz);
13C NMR (75 MHz, CDCl3): d=21.5, 126.3, 127.7, 128.2,
129.0, 129.5, 130.1, 132.5, 135.0, 136.5, 137.9, 144.8, 147.0,
149.1; ESI-MS: m/z=284 (M+H)+; ESI-HR-MS: m/z=
284.0734 (M+H)+, calcd. for C16H14O2NS: 284.0739.
1687, 2854, 2924, 3093, 3447 cmÀ1
;
1H NMR (300 MHz,
CDCl3): d=2.40 (s, 3H), 2.61 (s, 3H), 7.32 (d, 2H, J=
8.1 Hz), 7.84 (d, 2H, J=8.1 Hz), 8.00–8.06 (m, 4H);
13C NMR (75 MHz, CDCl3): d=21.5, 26.8, 127.7, 127.8,
128.9, 130.0, 137.6, 140.0, 144.7, 145.7, 196.7; ESI-MS: m/z=
297 (M+Na)+; ESI-HR-MS: m/z=275.0734 (M+H)+,
calcd. for C15H15O3S: 275.0736.
1-(Hexylsulfonyl)-4-methylbenzene (3s):[45g] Liquid; yield:
219 mg (91%). IR (KBr): n=522, 565, 629, 721, 816, 1088,
1145, 1215, 1316, 1460, 1493, 1598, 1741, 2862, 2928,
3426 cmÀ1 1H NMR (300 MHz, CDCl3): d=0.83–0.87 (m,
;
3H), 1.22–1.28 (m, 4H), 1.32–1.38 (m, 2H), 1.65–1.72 (m,
2H), 2.45 (s, 3H), 3.03–3.08 (m, 2H), 7.36 (d, 2H, J=
8.0 Hz), 7.78 (d, 2H, J=8.0 Hz); 13C NMR (75 MHz,
CDCl3): d=13.9, 21.6, 22.2, 22.6, 27.9, 31.1, 56.4, 128.0,
129.8, 136.2, 144.5; ESI-MS: m/z=241 (M+H)+, 263 (M+
Na)+; ESI-HR-MS: m/z=241.1251 (M+H)+, calcd. for
C13H21O2S: 241.1256.
Acknowledgements
BTVS and VSR thank the Council of Scientific and Industrial
Research, New Delhi, India for the award of a Senior Re-
search Fellowship (SRF).
1-(Isopropylsulfonyl)-4-methylbenzene (3t):[45h] White
solid; yield: 175 mg (88%); mp 76–77 (Lit.[45 h] 788C). IR
(KBr): n=454, 557, 641, 717, 817, 1019, 1087, 1141, 1262,
References
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1307, 1464, 1596, 2932, 2980, 3424 cmÀ1; H NMR (300 MHz,
[1] a) C. F. Sturino, G. OꢂNeill, N. Lachance, M. Boyd, C.
Berthelette, M. Labelle, L. Li, B. Roy, J. Scheigetz, N.
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CDCl3): d=1.29 (d, 6H, J=6.8 Hz), 2.45 (s, 3H), 3.14–3.20
(m, 1H), 7.36 (d, 2H, J=8.0 Hz), 7.76 (d, 2H, J=8.0 Hz);
13C NMR (75 MHz, CDCl3): d=15.6, 21.4, 55.4, 128.9, 129.5,
133.8, 144.4; ESI-MS: m/z=199 (M+H)+, 221 (M+Na)+;
ESI-HR-MS: m/z=199.0785 (M+H)+, calcd. for C10H15O2S:
199.0787.
4-Tosylphenol (3u):[45i] Colorless solid; yield: 182 mg
(73%); mp 140–1418C (Lit.[45i] 140–1428C). IR (KBr): n=
554, 637, 683, 707, 811, 840, 1015, 1069, 1104, 1149, 1240,
1286, 1377, 1445, 1583, 1647, 1742, 1914, 2853, 2924, 3160,
3458 cmÀ1 1H NMR (300 MHz, CDCl3): d=2.38 (s, 3H),
;
6.90 (d, 2H, J=8.2 Hz), 7.28 (d, 2H, J=8.0 Hz), 7.71–7.85
(m, 4H); 13C NMR (75 MHz, CDCl3): d=21.4, 116.1, 127.1,
129.7, 129.8, 132.1, 138.8, 143.9, 160.7; ESI-MS: m/z=249
(M+H)+, 271 (M+Na)+; ESI-HR-MS: m/z=249.0570 (M+
H)+, calcd. for C13H13O3S: 249.0579.
(E)-1-Methyl-4-(styrylsulfonyl)benzene (3v):[45j] White
solid; yield: 168 mg (65%); mp 118–1208C (Lit.[45j] 118–
1208C). IR (KBr): n=479, 536, 660, 745, 815, 969, 1081,
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1H NMR (300 MHz, CDCl3): d=2.43 (s, 3H), 6.85 (d, 1H,
J=15.4 Hz), 7.34 (d, 2H, J=8.1 Hz), 7.37–7.42 (m, 3H),
814
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