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MedChemComm
Page 2 of 6
DOI: 10.1039/C7MD00017K
COMMUNICATION
Journal Name
1.1 General procedure for the synthesis of (aralkylsulfanyl) (s, 3H, CH3O); 13C NMR (100MHz, DMSO-d6) δ 167.17, 159.85,
acetic acids 3a-3l
.
142.29, 136.94, 133.04, 132.82, 130.30, 129.23, 129.10,
The mercaptoacetic acid was added to a solution of sodium 120.74, 114.35, 59.63, 55.56; HR-MS (ESI-) m/z 331.0718 [M-
methoxide. Then halogenated alkane (40mmol) was added H]-, found 331.0681 [M-H]-.
slowly, and the mixture heated to reflux. The reaction mixture Data for 4-(trifluoromethyl) benzyl-4-carboxystyryl sulfone
was poured into crushed ice, and neutralized with HCl
(
5f): white solid (55%); mp 158-159°C ; 1H NMR (400MHz,
solution. The precipitated crystalline solid was filtered off, DMSO-d6) δ 13.21 (s, 1H, COOH), 7.40-8.00 (m, 10H, ArH,
washed and dried. The crude product were purified by column CH=CH), 4.75 (s, 2H, ArCH2SO2).
chromatography.
1.2 General procedure for the synthesis of (aralkylsulfonyl) yellow solid (46%); mp 62-63°C; 1H NMR (400MHz, DMSO-d6) δ
acetic acids 4a-4l 13.16 (s, 1H, COOH), 7.35-7.98 (m, 11H, ArH, CH=CH), 4.55-
Data for 1-phenyl-ethyl-4-carboxystyryl sulfone (5g): faint
.
The (aralkysulfanyl) acetic acid was added to H2O2 solution and 4.60 (m, 1H, ArCHSO2), 1.67-1.69 (d, 3H, CH3); 13C NMR
the resulting solution heated to reflux. The reaction mixture (100MHz, DMSO-d6) δ 167.16, 143.19, 136.93, 134.26, 133.06,
was poured into crushed ice. And the precipitated crystalline 130.26, 130.09, 129.31, 129.04, 128.78, 127.64, 63.55, 14.57;
solid was filtered off, washed and dried. Purification of the HR-MS (ESI+) m/z 317.0769 [M+H]+, found 339.0678 [M+Na]+.
crude residue afforded the desired compound.
1.3 General Procedure for the synthesis of styryl benzyl- mp 138-139°C; 1H NMR (400MHz, DMSO-d6) δ 7.35-7.99 (m,
sulfones 5a-5l.
11H, ArH, CH=CH), 4.58 (s, 2H, ArCH2SO2); 13C NMR (100MHz,
Data for Benzyl-4-carboxystyryl sulfone (5h): white solid (86%);
The aromatic aldehyde (10mmol) and benzylamine (0.2ml) DMSO-d6) δ 167.15, 142.42, 136.90, 133.08, 131.63, 130.30,
were added to a solution of the (aralkylsulfonyl) acetic acid 129.25, 129.09, 129.02 , 128.86, 60.26; HR-MS (ESI+) m/z
(10mmol) in acetic acid (20ml) and the resulting solution was 303.0613 [M+H]+, found 325.0527 [M+Na]+.
heated to reflux until the absence of (aralkylsulfonyl) acetic Data for 4-Chlorobenzyl-styryl sulfone (5i): white solid (55%);
acid (checked by TLC). The reaction vessel was cooled in an ice mp 144-145°C; 1H NMR (400MHz, DMSO-d6) δ 7.30-7.70 (m,
bath. And the precipitated crystalline solid was filtered off, 11H, ArH, CH=CH), 4.59 (s, 2H, ArCH2SO2); 13C NMR (100MHz,
washed with cold methanol, and dried under vacuum to obtain DMSO-d6) δ 144.01, 133.76, 133.36, 132.82, 131.61, 129.54,
the crude product. Purification of the crude residue by column 129.21, 128.89, 128.42 , 126.42, 59.51; HR-MS (ESI+) m/z
chromatography (petroleum ether/ethyl acetate) to afford the 293.0325 [M+H]+, found 315.0217 [M+Na]+.
desired compound.
Data for 4-Chlorobenzyl-4-methylstyryl sulfone (5j): white solid
Data for (4-(trifluoromethoxyl) benzyl-4-carboxystyryl sul-fone (45%); mp 144-145°C; 1H NMR (400MHz, DMSO-d6) δ 7.24-7.58
(
5a): white solid (47%); 1H NMR (400 MHz, DMSO-d6) δ 13.22 (m, 10H, ArH, CH=CH), 4.57 (s, 2H, ArCH2SO2), 2.34 (s, 3H,
(s, 1H, COOH), 7.36-8.05 (m, 10H, ArH, CH=CH), 4.75 (s, 2H, CH3), HR-MS (ESI+) m/z 307.0481 [M+H]+, found 328.9213
ArCH2SO2); HR-MS (ESI+) m/z 387.0436 [M+H]+, found [M+Na]+.
409.0340 [M+Na]+.
Data for 4-Chlorobenzyl-4-methoxylstyryl sulfone (5k): white
Data for 4-Fluorobenzyl-4-carboxystyryl sulfone (5b): white solid (43%); mp 144-145°C; 1H NMR (400MHz, DMSO-d6) δ
solid (52%); 1H NMR (400 MHz, DMSO-d6) δ 13.18 (s, 1H, 6.99-7.66 (m, 10H, ArH, CH=CH), 4.54 (s, 2H, ArCH2SO2), 3.81
COOH), 7.19-7.99 (m, 10H, ArH, CH=CH), 4.60 (s, 2H, (s, 3H, OCH3); 13C NMR (100MHz, DMSO-d6) δ 162.09, 143.88,
ArCH2SO2); 13C NMR (100MHz, DMSO-d6) δ 167.15, 163.90, 133.69, 133.33, 131.11, 128.84, 128.59, 125.32, 123.38,
161.47, 142.62, 136.86, 133.67, 130.30, 129.28, 128.82, 114.99, 59.70, 55.86; HR-MS (ESI+) m/z 323.0430 [M+H]+,
125.46, 115.80, 59.29; HR-MS (ESI+) m/z 321.0519 [M+H]+, found 344.9188 [M+Na]+.
found 343.0424 [M+Na]+.
Data for 4-Chlorobenzyl-4-phenylstyryl sulfone (5l): white solid
Data for 4-methylbenzyl-4-carboxystyryl sulfone (5c): white (64%); mp 144-145°C; 1H NMR (400MHz, DMSO-d6) δ 7.34-7.80
solid (56%); 1H NMR (400MHz, DMSO-d6) δ 13.19 (s, 1H, (m, 15H, ArH, CH=CH), 4.60 (s, 2H, ArCH2SO2); 13C NMR
COOH), 7.22-7.30 (m, 10H, ArH, CH=CH), 4.52 (s, 2H, (100MHz, DMSO-d6) δ 143.51, 143.07, 139.49, 133.75, 133.37,
ArCH2SO2), 2.28 (s, 3H, CH3); 13C NMR (100MHz, DMSO-d6) δ 131.91, 129.89, 129.52, 128.90, 128.60, 128.48, 127.70,
167.15, 142.27, 138.22, 136.93, 133.06, 131.47, 130.30, 127.26, 126.26, 59.56; HR-MS (ESI+) m/z 369.0638 [M+H]+,
129.46, 129.24, 129.10, 125.98, 60.00, 21.22; HR-MS (ESI-) m/z found 391.0529 [M+Na]+.
315.0769 [M-H]-, found 315.0734 [M-H]-.
1.4 Procedure for the synthesis of 5m.
Data for 4-tert-butylbenzyl-4-carboxystyryl sulfone (5d): white The cinnamaldehyde (10mmol) and piperidine (0.1ml) were
solid (45%); mp 179-180°C; 1H NMR (400MHz, DMSO-d6) δ added to a solution of the ((4-chlorobenzyl) sulfonyl) acetic
13.13 (s, 1H, COOH), 7.29-7.99 (m, 10H, ArH, CH=CH), 4.52 (s, acid (10mmol) in pyridine (10ml) and the resulting solution
2H, ArCH2SO2), 1.25 (s, 9H, C(CH3)3); 13C NMR (100MHz, DMSO- heated to reflux until the absence of (aralkylsulfonyl) acetic
d6) δ 167.16, 151.31, 142.32, 136.96, 133.06, 131.35, 130.29, acid (checked by TLC). The reaction vessel was cooled in an ice
129.29, 129.25, 125.82, 125.68, 59.91, 34.76, 31.49; HR-MS bath. And the precipitated crystalline solid was filtered off,
(ESI+) m/z 359.1239 [M+H]+, found 381.1140 [M+Na]+.
washed with cooled isopropanol, and dried under vacuum to
Data for 4-methoxybenzyl-4-carboxystyryl sulfone (5e): white obtain the crude product. Purification of the crude residue by
solid (55%); mp 155-156°C; 1H NMR (400MHz, DMSO-d6) δ column chromatography (petroleum ether/ethyl acetate) to
6.90-7.99 (m, 10H, ArH, CH=CH), 4.50 (s, 2H, ArCH2SO2), 3.73 afford the desired compound.
2 | J. Name., 2012, 00, 1-3
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