Z. Zhong, P. Xu, J. Ma et al.
Tetrahedron xxx (xxxx) xxx
7.39 (d, 2 H, J ¼ 8.8 Hz), 7.46 (d, 2 H, J ¼ 9.2 Hz), 7.52 (d, 2 H,
TOF) m/z calculated for C12H9ClNaO3Sþ (M þ Na)þ 290.9853, found
J ¼ 8.8 Hz). 13C NMR (101 MHz, Chloroform-d)
d
141.31, 140.56,
290.9842.
138.56, 137.68, 129.92, 129.28, 128.93, 126.02. HRMS (ESI-TOF) m/z
calculated for
340.9241.
C
12H8Cl2NaO2Sþ2 (M
þ
Na)þ 340.9235, found
4.3.5. 4-Chlorophenyl 4-methylbenzenesulfonate (5e)
1H NMR (400 MHz, Chloroform-d)
d
7.71 (d, J ¼ 8.4 Hz, 2H), 7.33
(d, J ¼ 8.1 Hz, 2H), 7.26 (d, J ¼ 8.9 Hz, 2H), 6.94 (d, J ¼ 8.9 Hz, 2H),
2.46 (s, 3H). 13C NMR (101 MHz, Chloroform-d)
148.05, 145.72,
4.2.14. S-(thien-2-yl) 4-chlorobenzenesulfonothioate (3o)
1H NMR (400 MHz, Chloroform-d)
d
d
7.63 (dd, J ¼ 5.3, 1.3 Hz, 1H),
132.77, 131.96, 129.91, 129.73, 128.53, 123.81, 21.74. HRMS (ESI-TOF)
m/z calculated for C13H11ClNaO3Sþ (M þ Na)þ 305.0010, found
305.0000.
7.58e7.51 (m, 2H), 7.27 (d, J ¼ 9.2 Hz, 2H), 7.16 (dd, J ¼ 3.7, 1.3 Hz,
1H), 7.08 (dd, J ¼ 5.4, 3.7 Hz, 1H), 2.45 (s, 3H). 13C NMR (101 MHz,
Chloroform-d)
d 145.16, 139.41, 139.36, 135.16, 129.56, 128.37,
127.85, 125.27, 21.75. HRMS (ESI-TOF) m/z calculated for
C
4.3.6. 4-Bromophenyl 4-methylbenzenesulfonate (5f)
10H7ClNaO2Sþ3 (M þ Na)þ 312.9189, found 312.3608.
1H NMR (400 MHz, Chloroform-d)
d
7.71 (d, J ¼ 8.4 Hz, 2H),
7.46e7.37 (m, 2H), 7.34 (d, J ¼ 8.0 Hz, 2H), 6.88 (d, J ¼ 8.8 Hz, 2H),
2.47 (s, 3H). 13C NMR (101 MHz, Chloroform-d)
148.62, 145.68,
4.2.15. S-p-tolyl methanesulfonothioate (3p)
1H NMR (400 MHz, Chloroform-d)
7.63, 7.62, 7.61, 7.60, 7.60,
7.59, 7.32, 7.32, 7.32, 7.31, 7.30, 7.30, 7.30, 7.30, 7.30, 7.29, 7.28, 3.19,
2.44.13C NMR (101 MHz, Chloroform-d)
142.47, 136.17, 130.69,
d
d
132.73,132.02, 129.89, 128.53, 124.17, 120.58, 21.74. HRMS (ESI-TOF)
m/z calculated for C13H11BrNaO3Sþ (M þ Na)þ 348.9504, found
348.9496.
d
124.54, 47.20, 21.46. HRMS (ESI-TOF) m/z calculated for
C8H10NaO2Sþ2 (M þ Na)þ 225.0014, found 225.0009.
4.3.7. 4-Iodophenyl 4-methylbenzenesulfonate (5g)
1H NMR (400 MHz, Chloroform-d)
d
7.71 (dd, J ¼ 8.3, 1.5 Hz, 2H),
4.3. General procedure for the synthesis of compounds 5a-p
7.61 (dd, J ¼ 8.7, 1.9 Hz, 2H), 7.34 (d, J ¼ 8.0 Hz, 2H), 6.75 (d,
J ¼ 8.8 Hz, 2H), 2.46 (d, J ¼ 2.4 Hz, 3H). 13C NMR (101 MHz,
In an oven-dried undivided three-necked bottle (25 mL)
equipped with a stir bar, benzenesulfinate salt 1a (0.6 mmol),
phenols 4a (0.3 mmol), sodium iodide (0.2 equiv), MeCN (5 mL) was
added. The bottle was equipped with platinum plate
Chloroform-d)
d 149.47, 145.71, 138.75, 132.01, 129.92, 128.53,
124.51, 91.78, 21.78. HRMS (ESI-TOF) m/z calculated for
C
13H11INaO3Sþ (M þ Na)þ 396.9366, found 396.9359.
(10 mm
ꢀ
10 mm) as the anode and platinum plate
4.3.8. 4-Cyanophenyl 4-methylbenzenesulfonate (5h)
1H NMR (400 MHz, Chloroform-d)
7.72 (d, J ¼ 8.4 Hz, 2H), 7.63
(d, J ¼ 8.7 Hz, 2H), 7.36 (d, J ¼ 8.1 Hz, 2H), 7.14 (d, J ¼ 8.7 Hz, 2H),
2.47 (s, 3H). 13C NMR (101 MHz, Chloroform-d)
152.57, 146.15,
133.91, 131.83,130.07,128.46, 123.45, 117.74,111.20. HRMS (ESI-TOF)
m/z calculated for C14H11NNaO3Sþ (M þ Na)þ 296.0352, found
296.0339.
(10 mm ꢀ 10 mm) as the cathode. The reaction mixture was stirred
and electrolyzed at a constant current of 10 mA at room tempera-
ture for 4 h. After completion of the reaction, as indicated by TLC
and GC-MS, the pure product was obtained by flash column chro-
matography on silica gel (petroleum ether: ethyl acetate ¼ 40e30 :
1). The same procedure was applied to the production of other
compounds 5a-p.
d
d
4.3.9. 4-Nitrophenyl benzenesulfonate (5i)
4.3.1. p-tolyl benzenesulfonate (5a)
1H NMR (400 MHz, Chloroform-d)
d
8.21 (d, J ¼ 9.1 Hz, 2H), 7.88
1H NMR (400 MHz, Chloroform-d)
d
7.83 (d, J ¼ 7.5 Hz, 2H), 7.66
(d, J ¼ 7.1 Hz, 2H), 7.75 (t, J ¼ 7.5 Hz, 1H), 7.60 (t, J ¼ 7.9 Hz, 2H), 7.21
(t, J ¼ 7.5 Hz, 1H), 7.51 (t, J ¼ 7.7 Hz, 2H), 7.06 (d, J ¼ 8.3 Hz, 2H), 6.86
(d, J ¼ 9.1 Hz, 2H). 13C NMR (101 MHz, Chloroform-d)
d 153.81,
(d, J ¼ 8.5 Hz, 2H), 2.29 (s, 3H). 13C NMR (101 MHz, Chloroform-d)
146.28, 134.89, 134.83, 129.51, 128.45, 125.44, 123.20. HRMS (ESI-
TOF) m/z calculated for C12H9NNaO5Sþ (M þ Na)þ 302.0094, found
302.0319.
d
147.45, 137.11, 135.41, 134.26, 130.17, 129.18, 128.46, 122.01, 20.84.
HRMS (ESI-TOF) m/z calculated for C13H12NaO3Sþ (M þ Na)þ
271.0399, found 271.0395.
4.3.10. 4-Nitrophenyl 4-methylbenzenesulfonate (5j)
4.3.2. p-tolyl 4-methylbenzenesulfonate (5b)
1H NMR (400 MHz, Chloroform-d)
d
8.20 (d, J ¼ 9.1 Hz, 2H), 7.74
(d, J ¼ 8.4 Hz, 2H), 7.37 (d, J ¼ 8.0 Hz, 2H), 7.20 (d, J ¼ 9.2 Hz, 2H),
2.48 (s, 3H). 13C NMR (101 MHz, Chloroform-d)
153.93, 146.26,
1H NMR (400 MHz, Chloroform-d)
d
7.76e7.69 (m, 2H), 7.32 (d,
J ¼ 8.3 Hz, 2H), 7.09 (d, J ¼ 8.3 Hz, 2H), 6.90e6.84 (m, 2H), 2.47 (s,
3H), 2.33 (s, 3H). 13C NMR (101 MHz, Chloroform-d)
147.51, 145.17,
d
d
146.21, 131.75, 130.12, 128.48, 125.40, 123.22, 21.76. HRMS (ESI-TOF)
m/z calculated for C13H11NNaO5Sþ (M þ Na)þ 316.0250, found
316.0235.
136.92, 130.07, 129.68, 128.89, 128.54, 122.07, 21.70, 20.87. HRMS
(ESI-TOF) m/z calculated for C14H14NaO3Sþ (M þ Na)þ 280.0556,
found 280.0991.
4.3.11. 4-Nitrophenyl 4-chlorobenzenesulfonate (5k)
4.3.3. m-tolyl 4-methylbenzenesulfonate (5c)
1H NMR (400 MHz, Chloroform-d)
d
8.24 (d, J ¼ 9.1 Hz, 2H), 7.82
1H NMR (400 MHz, Chloroform-d)
d
7.73 (d, J ¼ 8.4 Hz, 2H), 7.32
(d, J ¼ 8.7 Hz, 2H), 7.57 (d, J ¼ 8.7 Hz, 2H), 7.23 (d, J ¼ 9.2 Hz, 2H). 13C
(d, J ¼ 8.2 Hz, 2H), 7.15 (t, J ¼ 7.9 Hz, 1H), 7.08e7.04 (m, 1H), 6.88 (s,
1H), 6.77e6.72 (m, 1H), 2.46 (s, 3H), 2.31 (s, 3H). 13C NMR (101 MHz,
NMR (101 MHz, Chloroform-d)
d 153.58, 146.41, 141.83, 133.24,
129.92, 129.84, 125.56, 123.15. HRMS (ESI-TOF) m/z calculated for
Chloroform-d)
d 149.61, 145.29, 139.97, 132.59, 129.71, 129.22,
C
12H8ClNNaO5Sþ (M þ Na)þ 335.9704, found 336.0381.
128.49, 127.86, 122.99, 119.13, 21.69, 21.23. HRMS (ESI-TOF) m/z
calculated for C14H14NaO3Sþ (M þ Na)þ 285.0556, found 280.0991.
4.3.12. 4-Nitrophenyl 4-fluorobenzenesulfonate (5l)
4.3.4. 4-Chlorophenyl benzenesulfonate (5d)
1H NMR (400 MHz, Chloroform-d)
d
8.23 (d, J ¼ 9.1 Hz, 2H), 7.91
1H NMR (400 MHz, Chloroform-d)
d
7.84 (d, J ¼ 7.3 Hz, 2H), 7.70
(dd, J ¼ 8.9, 4.9 Hz, 2H), 7.31e7.20 (m, 5H). 13C NMR (101 MHz,
(t, J ¼ 7.5 Hz, 1H), 7.55 (t, J ¼ 7.9 Hz, 2H), 7.26 (d, J ¼ 8.9 Hz, 2H), 6.93
Chloroform-d) d 165.08, 153.63, 131.47, 131.37, 125.54, 123.18, 117.13,
(d, J ¼ 8.9 Hz, 2H). 13C NMR (101 MHz, Chloroform-d)
d
147.98,
116.90. HRMS (ESI-TOF) m/z calculated for
C
12H8FNNaO5Sþ
135.03, 134.48, 132.89, 129.77, 129.29, 128.50, 123.75. HRMS (ESI-
(M þ Na)þ 319.9999, found 320.0185.
6