JOURNAL OF CHEMICAL RESEARCH 2014 267
13
Conclusions
7.48 (d, J=8.4 Hz, 4H); C NMR (100 MHz, CDCl ): δ146.7, 139.8,
3
1
26.6, 94.4. HRMS calcd for C H I O S: 469.8334, found: 469.8335.
12 8 2 2
In conclusion, we report here the intermolecular desulfitative
homocoupling of sodium arylsulfinate with high reactivity
and selectivity. This method provides an alternative route to
symmetrical diaryl sulfone derivatives. The transformation has
been promoted by copper(II) salts under mild condition.
Di(4-methylphenyl)sulfone: White solid, m.p. 156–157 °C
4
0
1
(
lit. 156 °C) H NMR (400 MHz, CDCl ): δ 7.81 (d, J=7.6 Hz, 4H),
3
13
7.20 (d, J=7.6 Hz, 4H), 2.39 (s, 6 H); C NMR (100 MHz, CDCl ): δ
3
140.2, 139.9, 130.1, 129.8, 21.1; HRMS calcd for C H O S: 246.0715,
14
14
2
found: 246.0717.
41
Di-(3-methylphenyl)sulfone: White solid, m.p. 96–97 °C (lit. 94–
Experimental
1
95 °C) H NMR (400 MHz, CDCl ): δ 7.80 (s, 2H), 7.76 (d, J=7.6 Hz,
3
1
3
All solvents were purified and dried according to standard methods
prior to use. The quantitative analysis of the reaction products was
performed on an Agilent 6890/5975 GC/MS instrument with a
programmable split/splitless injector. The injector-port temperature
was set at 270 °C. The oven-temperature programme was initially
2H), 7.67 (t, J=7.6 Hz, 2H), 7.19 (d, J=7.6 Hz, 2H), 2.62 (s, 6H); C
NMR (100 MHz, CDCl ): δ 163.3, 147.8, 131.6, 130.1, 129.0, 126.2,
22.3. HRMS calcd for C H O S: 246.0715, found: 246.0716.
3
1
4
14
2
41
Di-(2-methylphenyl)sulfone: White solid, m.p. 106–108 °C (lit. 104–
1
105 °C) H NMR (400 MHz, CDCl ): δ 7.46–7.50 (m, 6H), 7.43 (dd,
3
13
–1
J=6.0, 1.2 Hz, 2H), 2.35 (s, 6H); C NMR (100 MHz, CDCl ): δ 153.7,
set at 80 °C and ramped to 220 °C at 5.0 °C min , and maintained at
20 °C for 2.0 min at each step. Proton NMR spectra were recorded
3
143.4, 130.8, 130.1, 129.0, 127.4, 22.8. HRMS calcd for C H O S:
2
14 14
2
2
46.0715, found: 246.0719.
,1′-Dinaphthyl sulfone: White solid, m.p. 185–187 °C (lit. 185–
in CDCl on a Bruker AVANCE III 400 MHz spectrometer. Proton
3
42
1
chemical shifts are reported in parts per million (ppm) relative to
tetramethylsilane (TMS) with the residual solvent peak as the internal
reference. Multiplicities are reported as: singlet (s), doublet (d),
triplet (t) and multiplet (m). HRMS (EI) data were collected on High
Resolution mass spectrometer(MAT 900 XL, Thermo Finnigan, USA).
1
186 °C) H NMR (400 MHz, CDCl ): 8.27–8.30 (m, 4H), 7.94–7.97
3
(
m, 2H), 7.48–7.52 (m, 4H), 7.69 (d, J=8.4 Hz, 3H), 7.35–7.38 (m, 2H).
1
3
C NMR (100 MHz, CDCl ): 146.6, 143.6, 137.6, 132.1, 129.8, 128.9,
3
127.7, 126.8, 125.9, 125.0. HRMS calcd for C H O S: 318.0715, found:
20 14 2
13
318.0720.
C NMR spectra were recorded at 100 MHz using TMS as internal
42
2
,2′-Dinaphthylsulfone: White solid, m.p. 172–173 °C (lit. 174 °C)
standard. All materials were purchased from common commercial
sources and used without additional purification.
1
H NMR (400 MHz, CDCl ): δ 8.42 (s, 2H), 8.00–8.15 (m, 8H), 7.81–
3
13
7.86 (m, 4H); C NMR (100 MHz, CDCl ): δ 149.7, 137.6, 132.9, 129.7,
3
Typical procedure for the products
1
27.9, 126.9, 125.8, 125.4, 125.2, 126.6. HRMS calcd for C H O S:
2
0
14
2
A mixture of the sodium arylsulfinate (1 mmol), Cu(OAc) (0.5 mmol)
318.0715, found: 318.0718.
2
4
3
and CH CN (1 mL) was stirred at 60 °C in air for 3 h. After this, the
2,2′-Bipyridinylsulfone: White solid, m.p. 211–213 °C (lit. 216 °C)
H NMR (400 MHz, CDCl ): δ 8.88 (d, J=8.0 Hz, 2H), 8.71 (d,
3
1
mixture was cooled to room temperature and filtered through a filter
paper. The organic phases were evaporated under reduced pressure and
the residue was subjected to flash column chromatography (silica gel,
ethyl acetate/petroleum ether=1/10) to obtain the desired product.
3
13
J=8.0 Hz, 2H), 7.85 (t, J=7.2 Hz, 2H), 7.12 (t, J=7.2 Hz, 2H);
C
NMR (100 MHz, CDCl ): δ 176.3, 159.6, 146.6, 133.9, 127.2. HRMS
3
calcd for C H N O S: 220.0306, found: 220.0309.
14
14
2
2
1
1
All products are known compounds and were characterised by H
2,2′-Bithiophenyl sulfone: Colourless oil; H NMR (400 MHz,
13
13
NMR, C NMR and HRMS.
CDCl ): δ 7.67–7.71 (m, 4H), 7.44 (d, J=7.2 Hz, 2H); C NMR
3
3
4
Di(4-methoxyphenyl)sulfone: White solid, m.p. 129–131 °C (lit.
(100 MHz, CDCl ): δ 157.7, 146.4, 142.8, 141.9. HRMS calcd for
3
1
1
28–130 °C); H NMR (400 MHz, CDCl ): δ 7.80 (d, J=8.4 Hz, 4H),
C H O S : 229.9530, found: 229.9533.
3
8
6
2 3
13
7.28 (d, J=8.4 Hz, 4H), 3.94 (s, 6H); C NMR (100 MHz, CDCl ): δ
3
1
77.7, 163.4, 128.9, 124.8, 59.2; HRMS calcd for C H O S: 278.0613,
Received 25 December 2013; accepted 23 February 2014
Paper 1302365 doi: 10.3184/174751914X13946336636551
Published online: 6 May 2014
14
14
4
found: 278.0615.
Diphenyl sulfone: White solid, m.p. 126–127 °C (lit. 125–126 °C) H
NMR (400 MHz, CDCl3): δ 7.93–7.96 (m, 4H), 7.47–7.57 (m, 6H).
3
4
1
13
C
NMR (100 MHz, CDCl ): δ 141.8, 133.3, 129.4, 127.7. HRMS calcd for
3
References
C H O S: 218.0402, found: 218.0409.
12
10
2
1
2
3
N.S. Simpkins, Sulfones in organic synthesis. Pergamon Press, Oxford,
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S. Patai, Z. Rappoport and C.J.M. Stirling, eds, The chemistry of sulfones
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Med. Chem. Lett., 2006, 16, 934.
35
Di(4-cyanophenyl)sulfone: Yellow solid, m.p. 231–232 °C (lit. 232–
1
1
2
(
33 °C); H NMR (400 MHz, CDCl ): δ 7.99 (d, J=8.4 Hz, 4H), 7.79
3
13
d, J=8.4 Hz, 4H); C NMR (100 MHz, CDCl ): δ 173.8, 160.4, 129.7,
3
1
20.0, 116.9; HRMS calcd for C H N O S: 268.0306, found: 268.0310.
14
8
2
2
3
4
Di(4-nitrophenyl)sulfone: Yellow solid, m.p. 271–273 °C (lit. 275–
1
277 °C); H NMR (400 MHz, CDCl ): δ 8.36 (d, J=8.8 Hz, 4H), 7.91
3
4
5
6
T. Otzen, E.G. Wempe, B. Kunz, R. Bartels, G. Lehwark-Yvetot, W.
Hänsel, K.J. Schaper and J.K. Seydel, J. Med. Chem., 2004, 47, 240.
Z.-Y. Sun, E. Botros, A.-D. Su, Y. Kim, E. Wang, N.Z. Baturay and C.-H.
Kwon, J. Med. Chem., 2000, 43, 4160.
M. Artico, R. Silvestri, E. Pagnozzi, B. Bruno, E. Novellino, G. Greco,
S. Massa, A. Ettorre, A.G. Loi, F. Scintu and P. La Colla, J. Med. Chem.,
2000, 43, 1886.
13
(d, J=8.8 Hz, 4H); C NMR (100 MHz, CDCl ): δ 151.8, 145.9, 129.6,
3
1
25.0; HRMS calcd for C H N O S: 308.0103, found: 308.0110.
12
8
2
6
3
6
Di(4-fluorophenyl)sulfone: Yellow solid, m.p. 97–98 °C (lit. 96–
1
98 °C); H NMR (400 MHz, CDCl ): δ 7.76 (dd, J=8.8 Hz, J=4.8 Hz,
3
13
4H), 7.24 (dd, J=8.8 Hz, J=4.8 Hz, 4H); C NMR (100 MHz, CDCl3):
δ 167.8 (d, JCF =242 Hz), 145.7 (d, JCF =3.6 Hz), 129.2 (d, JCF =7.6 Hz),
7
P. Laidlaw, D. Bethell, S.M. Brown, G. Watson, D.J. Willock and G.J.
Hutchings, J. Mol. Catal. A: Chem., 2002, 178, 205.
1
14.7 (d, JCF =20.8 Hz); HRMS calcd for C H F O S: 254.0213, found:
12
8
2
2
8
9
10
X. Zhou, J. Luo, J. Liu, S. Peng and G.-J. Deng, Org. Lett., 2011, 13, 1432.
G.-W. Wang and T. Miao, Chem. Eur. J., 2011, 17, 5787.
R. Chen, S. Liu, X. Liu, L. Yang and G.-J. Deng, Org. Biomol. Chem., 2011,
9, 7675.
2
54.0215.
Di(4-chlorophenyl)sulfone: Colourless solid, m.p. 145–147 °C (lit.
3
7
1
146–147 °C); H NMR (400 MHz, CDCl ): δ 7.88 (d, J=8.4 Hz, 4H),
3
13
7.85 (d, J=8.4 Hz, 4H); C NMR (100 MHz, CDCl ): δ 144.1, 138.1,
3
11 M. Wu, J. Luo, F. Xiao, S. Zhang, G.-J. Deng and H.-A. Luo, Adv. Synth.
Catal., 2012, 354, 335.
12 M. Wang, D. Li, W. Zhou and L. Wang, Tetrahedron, 2012, 68, 1926.
131.6, 127.3. HRMS calcd for C H Cl O S: 285.9622, found: 285.9626.
12 8 2 2
38
Di(4-bromophenyl)sulfone: White solid, m.p. 170–171 °C (lit.
1
13 M. Behrends, J. Sävmarker, P.J.R. Sjöberg and M. Larhed, ACS Catal.,
172 °C); H NMR (400 MHz, CDCl ): δ 7.84 (d, J=8.0 Hz, 4H), 7.40
3
13
2011, 1, 1455.
(d, J=8.0 Hz, 4H); C NMR (100 MHz, CDCl ): δ 138.9, 137.8, 128.0,
3
14 J. Liu, X. Zhou, H. Rao, F. Xiao, C.-J. Li and G.-J. Deng, Chem. Eur. J.,
126.4. HRMS calcd for C H Br O S: 373.8612, found: 373.8617.
12
8
2
2
2011, 17, 7996.
39
Di(4-iodophenyl)sulfone: Colourless solid, m.p. 201–203 °C (lit.
15
W. Chen, X. Zhou, F. Xiao, J. Luo and G.-J. Deng, Tetrahedron Lett., 2012,
53, 4347.
1
2
01–202 °C); H NMR (400 MHz, CDCl ): δ 7.97 (d, J=8.4 Hz, 4H),
3
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