866
Md. J. Uddin, P. N. P. Rao and E. E. Knaus
Vol. 40
3-(4-Methylphenyl)-4-(3-sulfonylazidophenyl)-2(5H)furanone
(7a).
3-(4-Ethoxylphenyl)-4-(3-sulfonylazidophenyl)-2(5H)furanone
(7c).
General Procedure.
Compound 7c was obtained as a yellow solid in 59% yield; mp
168-170 ºC; ir (film): 3050 (CHarom), 2950, 2850 (CHaliphatic),
2150 (N3), 1750 (furanone CO), 1340, 1160 (SO2) cm-1; 1H nmr
(deuteriochloroform): d 1.56 (t, J = 6.9 Hz, 3H, CH3), 4.31 (q, J =
7.3 Hz, 2H, ethoxy CH2), 5.18 (s, 2H, CH2), 7.11 (d, J = 8.7 Hz,
1H, 3-sulfonylazidophenyl H-6), 7.30 (d, J = 8.5 Hz, 2H, 4-
ethoxyphenyl H-3, H-5), 7.37-7.47 (m, 3H, 4-ethoxyphenyl H-2,
H-6; 3-sulfonylazidophenyl H-5), 7.77 (dd, J = 8.4, 2.2 Hz, 1H,
3-sulfonylazidophenyl H-4), 7.95 (d, J = 2.2 Hz, 1H, 3-sulfony-
lazidophenyl H-2); 13C nmr (deuteriochloroform): d 14.77
(CH3), 65.81 (ethoxy CH 2), 70.78 (CH2), 113.66 (4-
ethoxyphenyl C-3, C-5), 122.65 (4-ethoxyphenyl C-1), 123.64
(furanone C-3), 127.24, 131.04, 131.37, 137.11 (3-sulfonylazi-
dophenyl C-5, C-6, C-2, C-4), 129.34 (4-ethoxyphenyl C-2, C-6),
128.04, 130.24 (3-sulfonylazidophenyl C-1, C-3), 156.64, 157.07
(furanone C-4, 4-ethoxyphenyl C-4), 172.71 (CO)
Chlorosulfonic acid (1.0 mL, 15 mmol) was added drop wise to
a solution of 3-(4-methylphenyl)-4-phenyl-2(5H)furanone (6a,
0.42 g, 1.67 mmol) in chloroform (1 mL) at –5 ºC with vigorous
stirring. The cooling bath was removed and the reaction was
allowed to continue for 1 hour at 25 ºC at which time it was poured
very slowly into crushed ice (10 g). Extraction with ethyl acetate (3
x 20 mL), washing the combined organic extracts with water (3 x
30 mL), and removal of the solvent in vacuo afforded the corre-
sponding benzenesulfonyl chloride as a brown syrup, which was
dissolved in acetone (2 mL). This solution was added drop wise to
a stirred solution of sodium azide (0.065 g, 1.0 mmol) in aqueous
acetone (2 mL) at –5 ºC and the reaction mixture was stirred for 3
hours at 0 ºC. The solvent was removed in vacuo and water (10
mL) was added to the residue. Extraction with ethyl acetate (3 x 15
mL), drying the combined extracts (Na2SO4) and removal of the
solvent in vacuo gave a yellow syrup, which was purified by silica
gel column chromatography using ethyl acetate-hexane (2:1, v/v)
as eluant to afford 7a (0.15 g, 49%) as yellow needles; mp 108-110
ºC; ir (film): 3105, 3050 (CHarom), 2950, 2825 (CHaliphatic), 2113
(N3), 1733 (furanone CO), 1368, 1153 (SO2) cm-1; 1H nmr (deu-
teriochloroform): d 2.70 (s, 3H, CH3), 5.22 (s, 2H, CH2), 7.31 (d, J
= 7.6 Hz, 2H, 4-methylphenyl H-3, H-5), 7.41 (d, J = 7.6 Hz, 2H,
4-methylphenyl H-2, H-6), 7.40-7.49 (m, 2H, 3-sulfonylazi-
dophenyl H-5, H-6), 7.76 (dd, 1H, J = 7.9, 1.8 Hz, 3-sulfonylazi-
dophenyl H-4), 8.06 (d, J = 1.8 Hz, 2H, 3-sulfonylazidophenyl H-
2); 13C nmr (deuteriochloroform): d 20.34 (CH3), 70.82 (CH2),
123.85 (furanone C-3), 127.28, 129.34 (4-methylphenyl C-2, C-6;
C-3, C-5), 129.98, 131.14, 133.50, 135.20 (3-sulfonylazidophenyl
C-5, C-6, C-4, C-2), 128.97, 137.26, 130.12, 138.86 (4-
methylphenyl C-1, C-4; 3-sulfonylazidophenyl C-1, C-3), 158.05
(furanone C-4), 172.45 (CO).
Anal. Calcd. for C18H15N3O5S•1/3H2O: C, 55.23; H, 4.00; N,
10.73. Found: C, 55.09; H, 3.66; N, 10.75.
3-Phenyl-4-(4-sulfonylazidophenyl)-2(5H)furanone (7d).
Compound 7d was obtained as a pale yellow solid in 57%
yield; mp 120-122 ºC; ir (film): 3120, 3050 (CHarom), 2950, 2890
(CHaliphatic), 2115 (N3), 1750 (furanone CO), 1350, 1160 (SO2)
1
cm-1; H nmr (deuteriochloroform): d 5.24 (s, 2H, CH2), 7.26-
7.39 (m, 2H, phenyl H-2, H-6), 7.44-7.51 (m, 3H, phenyl H-3, H-
4, H-5), 7.70 (d, J = 8.5 Hz, 2H, 4-sulfonylazidophenyl H-2, H-
6), 7.85 (d, J = 8.5 Hz, 2H, 4-sulfonylazidophenyl H-3, H-5); 13
C
nmr (deuteriochloroform): d 70.91 (CH2), 124.05 (furanone C-3),
127.33, 127.43, 129.44, 130.56, 131.40 (4-sulfonylazidophenyl,
C-2, C-6; C-3, C-5 and phenyl C-2, C-6; C-4; C-3, C-5), 136.97
(phenyl C-1), 129.89, 138.39 (4-sulfonylazidophenyl C-4, C-1),
159.34 (furanone C-4), 172.23 (CO).
Anal. Calcd. for C16H11N3O4S: C, 56.30; H, 3.25; N, 12.31.
Found: C, 56.30; H, 3.14; N, 12.70.
Anal. Calcd. for C17H13N3O4S: C, 57.46; H, 3.69; N, 11.82.
Found: C, 57.44; H, 3.93; N, 11.59.
Compounds 7b-f were prepared using similar chlorosulfona-
tion and then azidation reactions as described above, where 6b-f
were used in place of 6a. The physical and spectral data for 7b-f
are listed below.
3-(4-Fluorophenyl)-4-(4-sulfonylazidophenyl)-2(5H)furanone
(7e).
Compound 7e was obtained as a pale yellow solid in 44%
yield; mp 134-136 ºC; ir (film): 3115, 3090 (CHarom), 2980,
2905, 2850 (CHaliphatic), 2125 (N3), 1745 (furanone CO), 1350,
3-(4-Methoxylphenyl)-4-(3-sulfonylazidophenyl)-2(5H)fura-
none (7b).
1
1150 (SO2) cm-1; H nmr (deuteriochloroform): d 5.20 (s, 2H,
CH2), 7.11 (d, JHCCF = 8.5 of d, JHCCH = 8.5 Hz, 2H, 4-fluo-
rophenyl H-3, H-5), 7.40 (d, JHCCH = 8.5 of d, JHCCCF = 5.4 Hz,
2H, 4-fluorophenyl H-2, H-6), 7.53 (d, J = 8.2 Hz, 2H, 4-sulfony-
lazidophenyl H-2, H-6), 7.96 (d, J = 8.2 Hz, 2H, 4-sulfonylazi-
dophenyl H-3, H-5); 13C nmr (deuteriochloroform): d 70.28
(CH2), 116.25 (d, JCCF = 22.0 Hz, 4-fluorophenyl C-3, C-5),
124.88 (furanone C-3), 128.17, 128.62 (4-sulfonylazidophenyl
C-2, C-6; C-3, C-5), 128.49 (4-fluorophenyl C-1), 131.01 (d,
JCCCF = 13.1 Hz, 4-fluorophenyl C-2, C-6), 137.11, 139.89 (4-
sulfonylazidophenyl C-4, C-1), 152.76 (furanone C-4), 163.27
(d, JCF = 250.4 Hz, 4-fluorophenyl C-4), 172.02 (CO).
Compound 7b was obtained as a pale yellow solid in 49%
yield; mp 163-165 ºC; ir (film): 3090, 3010 (CHarom), 2990, 2880
(CHaliphatic), 2135 (N3), 1740 (furanone CO), 1345, 1145 (SO2)
cm-1; 1H nmr (deuteriochloroform): d 4.07 (s, 3H, OCH3), 5.19 (s,
2H, CH2), 7.14 (d, J = 8.8 Hz, 1H, 3-sulfonylazidophenyl H-6),
7.30 (d, J = 7.9 Hz, 2H, 4-methoxyphenyl H-3, H-5), 7.33-7.50
(m, 3H, 4-methoxyphenyl H-2, H-6; 3-sulfonylazidophenyl H-5),
7.81 (dd, J = 9.0, 2.1 Hz, 1H, 3-sulfonylazidophenyl H-4), 7.96 (d,
J = 2.1 Hz, 1H, 3-sulfonylazidophenyl H-2); 13C nmr (deuteri-
ochloroform): d 56.61 (OCH3), 70.78 (CH2), 112.71 (4-
methoxyphenyl C-3, C-5), 122.86 (4-methoxyphenyl C-1), 123.59
(furanone C-3), 127.24, 131.10, 131.19, 137.10 (3-sulfonylazi-
dophenyl C-5, C-6, C-4, C-2), 129.34 (4-methoxyphenyl C-2, C-
6), 127.92, 130.18 (3-sulfonylazidophenyl C-1, C-3), 157.01,
157.17 (furanone C-4, 4-methoxyphenyl C-4), 172.68 (CO).
Anal. Calcd. for C17H13N3O5S: C, 54.98; H, 3.53; N, 11.31.
Found: C, 54.99; H, 3.59; N, 11.34.
Anal. Calcd. for C16H10FN3O4S: C, 53.48; H, 2.81; N, 11.69.
Found: C, 53.76; H, 2.66; N, 11.56.
3-(4-Chlorophenyl)-4-(4-sulfonylazidophenyl)-2(5H)furanone
(7f).
Compound 7f was obtained as a yellow syrup in 38% yield; ir
(film): 3050 (CHarom), 2990, 2850 (CHaliphatic), 2110 (N3), 1740