Molecules 2019, 24, 1751
18 of 25
.91 (d, 2H, 3JHH = 8.4 Hz, PhSO Me). C NMR (100 MHz, 25 mg in 0.8 mL of CDCl , reference: CHCl
13
7
2
3
3
=
77.00 ppm), δ, ppm: 23.3 (2CH ), 43.5 (SO CH ), 87.9 (CH ) ), 111.6 (C ), 127.5, 128.4, 128.6, 129.2,
3 2 3 3 2 4
−
30.1, 132.4, 136.1, 139.0 (all CArAr’), 179.8 (C ), 204.4 (C=O). IR (in CCl ), cm : 955 m, 1051 m., 1157 s,
5 4
1
1
1
3
+
327 m., 1383 m., 1614 m., 1701 s. (C=O), 2932 w., 2982 w. HRMS, m/z, calculated for C H NaO S :
65.0818, found 365.0823 [M + Na] .
19
18
4
+
0 0
-(3 -Chlorophenyl)-2,2-dimethyl-4-[4 -(methylsulfonyl)phenyl]-furan-3(2H)-one (1o) Yield: 33%. Colorless
5
◦
1
crystals, m.p. 219–221 C. H NMR (400 MHz, 20 mg in 0.8 mL of CDCl , reference: CHCl = 7.26 ppm),
3
3
3
δ
3J
, ppm: 1.56 (s, 6H, 2CH ), 3.04 (s, 3H, SO CH ), 7.29 (d, 1H, J
= 7.8 Hz, PhCl), 7.38 (d, 1H,
3
2
3
HH
3
3
= 7.9 Hz, PhCl), 7.47 (d, 1H, J
= 8.0 Hz, PhCl), 7.51 (d, 2H, J
= 8.4 Hz, PhSO Me), 7.67
HH
HH
HH
2
3
13
(
s,1H, PhCl), 7.91 (d, 2H, J
= 8.4 Hz, PhSO Me). C NMR (100 MHz, 25 mg in 0.8 mL of CDCl3,
HH
2
reference: CHCl = 77.00 ppm), δ, ppm: 23.2 (2CH ), 44.4 (SO CH ), 88.1 (CH ) ), 112.4, 126.7, 127.6
3 2 3 3 2
3
−
2C), 128.0, 130.0, 130.1 (2C), 131.0, 132.3, 135.0, 135.6, 139.3, 177.8 (C ), 204.2 (C=O). IR (in CCl ), cm :
5 4
1
(
9
57 m., 1157 s. (SO ), 1330 s. (SO ), 1384 m., 1616 m., 1705 s. (C=O), 2931 w., 2982 w. (C-H). LCMS, m/z,
2 2
+
+
calculated for C H ClO S : 377.0609, found 377.0667 [M + H] .
19
18
4
0 0
-(4 -Chlorophenyl)-2,2-dimethyl-4-[4 -(methylsulfonyl)phenyl]-furan-3(2H)-one (1k) Yield: 9%. Colorless
5
◦
1
crystals, m.p. 223–225 C. H NMR (400 MHz, 20 mg in 0.8 mL of CDCl , reference: CHCl = 7.26 ppm),
3
3
3
δ
, ppm: 1.57 (s, 6H, 2CH ), 3.06 (s, 3H, SO CH ), 7.37 (d, 2H, J
= 8.8 Hz, PhCl), 7.51-7.56 (m, 4H,
= 5.4 Hz), 7.92 (d, 2H, J= 8.8 Hz, PhSO Me). C NMR (100 MHz,
3
2
3
HH
3
4
13
Ar), 7.53 (dd, 4H, J
= 8.8 Hz, J
HH
HH
2
2
5 mg in 0.8 mL CDCl , reference: CHCl = 77.00 ppm), δ, ppm: 23.3 (2CH ), 44.5 (SO CH ), 88.1
3 3 3 2 3
(
(
2
CH ) ), 112.0, 127.7 (2C), 129.2 (2C), 129.7 (2C), 130.2 (2C), 130.6, 135.9, 138.8, 139.3, 178.3 (C ), 204.2
3
2
5
−
C=O). IR (in CCl ), cm : 956 m., 1095 m., 1158 s. (SO ), 1329 s. (SO ), 1384 s., 1616 m., 1703 s. (C=O),
4 2 2
1
+
+
931 w., 2982 w.(C-H). LCMS, m/z calculated for C H ClO S : 377.0609, found 377.0679 [M + H] .
19 18 4
0 0
-(4 -Fluorophenyl)-2,2-dimethyl-4-[4 -(methylsulfonyl)phenyl]-furan-3(2H)-one (1h) Yield: 23%. Colorless
5
◦
1
crystals, m.p. 191–192 C. H NMR (400 MHz, 25 mg in 0.8 mL of CDCl , reference: CHCl = 7.26 ppm),
3
3
3
δ
, ppm: 1.57 (s, 6H, 2CH ), 3.06 (s, 3H, SO CH ), 7.09 (t, 2H, J
= 8.5 Hz, PhF), 7.52 (d, 2H,
3
2
3
HH
3J = 8.0 Hz, PhSO Me), 7.63 (dd, 2H, J = 8.8 Hz, J = 5.4 Hz, PhF), 7.92 (d, 2H, J = 8.0 Hz,
3
4
3
HH
2
HH
HF
HH
1
3
PhSO Me). C NMR (100 MHz, 25 mg in 0.8 mL of CDCl , reference: CHCl = 77.00 ppm),
3.3 (2CH ), 44.5 (SO CH ), 88.0 (CH ) ), 116.2 d (2C, J = 22.0 Hz), 126.3 (1C), 127.8 (2C), 130.2 (2C),
δ
, ppm:
2
3
3
2
2
1
(
1
3
2
3
3 2
CF
3
1
19
30.9 d (2C, J = 9.0 Hz), 136.1, 139.3, 165.1 d (1C, J = 255.4 Hz), 178.4 (C ), 204.2 (C=O). F NMR
CF CF 5
−
δ, ppm: -104.8. IR (in CCl ), cm : 955 m., 1157 s. (SO ) 1243 m., 1327 s. (SO ),
4 2 2
1
376 MHz, CDCl3)
+
383 m., 1613 m., 1704 s. (C=O), 2933 w. (C-H). LCMS, m/z, calculated for C H FO S : 361.0905,
1
9
18
4
+
found 361.0953 [M + H] .
3
.2.3. General Method for Preparation of Compounds 1q, 1v, and 1w
To an aqueous solution of 25% NH3 (5mL) 2,2-dimethyl-4-[4 -(chlorosulfonyl)phenyl]-5-
3 -chlorophenyl)furan-3(2H)-one (200 mg) in THF (5 mL) was added and mixture was stirred
0
0
(
at room temperature for 24 h. Then, water, ammonia and tetrahydrofuran were removed in vacuo on
a rotary evaporator, the solid residue was dissolved in ethanol, then silica gel (5 g) was added, and
ethanol was removed in vacuo. The silica gel with the product was washed on a Schott filter 3 times
with dichloromethane (5 mL each), after which the compound was washed off the filter by ethanol
◦
after removing the alcohol and vacuum drying (0.1 torr, 24 h, 50 C). For isolation and purification
of compounds the mixtures of n-hexane/ CH Cl /ethyl acetate (from 10:2:1 to pure ethyl acetate)
2
2
were applied.
0
0
5
-(3 -Chlorophenyl)-2,2-dimethyl-4-[4 -(aminosulfonyl)phenyl]-furan-3(2H)-one (1u) Yield: 150 mg, 79%.
◦
1
Colorless crystals, m.p. 198–200 C. H NMR (300 MHz, 15 mg in 0.6 mL of (CD ) CO, reference:
3
2
2
.05 ppm), δ, ppm: 1.54 (s, 6H, 2CH ), 6.63 (s, 2H, NH ), 7.45–7.62 (m, 3H, PhCl), 7.49 (d, 2H,
3 2
3
3
13
JHH = 8.4 Hz, PhSO Me), 7.68–7.71 (m, 1H, PhCl), 7.89 (d, 2H, J = 8.4 Hz, PhSO Me). CNMR
2
HH
2
(
75 MHz, 15 mg in 0.6 mL of (CD ) CO, reference: 206.26 ppm), δ, ppm: 204.54, 177.90, 144.07, 135.09,
3 2