CsF-Celite
1587
were purified whenever necessary by column chromatography on silicagel using various solvent sys-
tems like CH Cl and petroleum ether, etc. as eluents, to afford pure thioethers or thioesters.
2
2
Benzyl phenyl sulfide (5)
ꢁ
ꢁ
1
Solid; mp 42–43 C (Ref. [31] 43–44 C); H NMR (250MHz, CDCl ): ꢁ ¼ 4.3 (s, 2H), 7.45–7.25 (m,
3
1
3
1
1
0H) ppm; C NMR (63 MHz, CDCl ): ꢁ ¼ 39.25, 126.45, 127.12, 128.44, 128.89, 129.52, 136.40,
3
þ
37.40 ppm; EIMS: m=z ¼ 200 (M ).
2
-Propyl 4-nitrophenyl sulfide (9)
ꢁ
ꢁ
1
Solid; mp 46–47 C (Ref. [34] 46–47 C); H NMR (250 MHz, CDCl ): ꢁ ¼ 1.40 (d, J ¼ 6.65 Hz, 6H),
3
1
3
3
.60 (m, 1H), 7.45 (d, J ¼ 8.92 Hz, 2H), 8.23 (d, J ¼ 8.92 Hz, 2H) ppm; C NMR (63 MHz, CDCl ):
3
þ
ꢁ
¼ 22.15, 36.64, 124.38, 127.62, 145.13, 147.55ppm; EIMS: m=z ¼ 197 (M ).
Allyl 4-nitrophenyl sulfide (10)
ꢁ
ꢁ
1
Solid; mp 38–39 C (Ref. [35a] 38–39 C); H NMR (250MHz, CDCl ): ꢁ ¼ 3.57 (m, 2H), 5.14–5.55
3
1
3
(m, 2H), 5.94 (m, 1H), 7.54 (d, J ¼ 9.10Hz, 2H), 8.08 (d, J ¼ 9.12Hz, 2H) ppm; C NMR (63 MHz,
þ
CDCl ): ꢁ ¼ 53.12, 119.01, 123.54, 125.92, 131.71, 145.00, 146.58 ppm; EIMS: m=z ¼ 195 (M ).
3
Ethyl 4-nitrophenyl sulfide (11)
ꢁ
ꢁ
1
Solid; mp 40–42 C (Ref. [35b] 42–43 C); H NMR (CDCl ): ꢁ ¼ 1.40 (t, J ¼ 7.53Hz, 3H), 3.00 (q,
3
1
3
J ¼ 7.36Hz, 2H), 7.31 (d, J ¼ 8.93Hz, 2H), 8.21 (d, J ¼ 8.80Hz, 2H) ppm; C NMR (63 MHz,
þ
CDCl ): ꢁ ¼ 13.73, 25.15, 123.77, 126.29, 144.63, 147.81 ppm; EIMS: m=z ¼ 183 (M ).
3
Benzyl 4-nitrophenyl sulfide (12)
ꢁ
ꢁ
1
Solid; mp 128–129 C (Ref. [33] 128–129 C); H NMR (250 MHz, CDCl ): ꢁ ¼ 4.22 (s, 2H), 7.36 (d,
3
3
1
J ¼ 9.10Hz, 2H), 7.00–7.51 (m, 5H), 8.43 (d, J ¼ 8.67 Hz, 2H) ppm; C NMR (63 MHz, CDCl ):
3
þ
ꢁ
¼ 37.41, 122.80, 126.35, 127.62, 128.88, 129.27, 135.42, 145.22, 147.35ppm; EIMS: m=z ¼ 245 (M ).
Phenylthio acetate (19, C H OS)
8
8
1
13
Liquid [42a, 42b]; H NMR (250 MHz, CDCl ): ꢁ ¼ 2.41 (s, 3H), 7.41–7.43 (m, 5H) ppm; C NMR
3
þ
(
63 MHz, CDCl ): ꢁ ¼ 30.11, 127.87, 129.12, 129.35, 134.37, 193.90ppm; EIMS: m=z ¼ 152 (M ).
3
Methyl 4-[(4-methoxyphenyl)thio]-4-oxobutanoate (20, C H O S)
1
2 14 4
1
Liquid; H NMR (250MHz, CDCl ): ꢁ ¼ 2.51 (t, J ¼ 6.00Hz, 2H), 3.21 (t, J ¼ 6.10Hz, 2H), 3.56 (s,
3
1
3
3
H), 3.62 (s, 3H), 6.98–7.15 (m, 4H) ppm; C NMR (63 MHz, CDCl ): ꢁ ¼ 31.21, 40.51, 52.22,
3
þ
5
5.54, 111.75, 117.69, 136.87, 160.22, 172.50, 196.23 ppm; EIMS: m=z ¼ 254 (M ).
4
-Methoxyphenylthio benzoate (23)
ꢁ
ꢁ
1
Solid; mp 96–98 C (Ref. [40] 97.5–99.5 C); H NMR (250 MHz, CDCl ): ꢁ ¼ 3.80 (s, 3H), 6.96–7.41
3
0
0
0
13
(
m, 4H, H-2,3,5,6), 7.45–7.60 (m, 3H, H-3 ,4 ,5 ) ppm; C NMR (63 MHz, CDCl ): ꢁ ¼ 55.45,
3
þ
1
15.15, 117.53, 127.42, 128.34, 133.35, 135.59, 136.59, 160.84, 190.95 ppm; EIMS: m=z ¼ 231 (M ).
4
-Nitrophenylthio benzoate (24)
ꢁ
0 0 0 0
13
,4 ,5 ), 7.72 (m, 2H, H-2,6), 8.03 (m, 2H, H-2 ,6 ), 8.30 (m, 2H, H-3,5) ppm; C NMR (63 MHz,
ꢁ
1
Solid; mp 125–127 C (Ref. [40] 126–127 C); H NMR (250MHz, CDCl ): ꢁ ¼ 7.58–7.66 (m, 3H, H-
3
0
3
CDCl ): ꢁ ¼ 123.88, 127.78, 128.69, 135.10, 135.80, 135.85, 136.25, 148.30, 188.01 ppm; EIMS:
3
þ
m=z ¼ 259 (M ).
1
,3-Benzoxazol-2-yl thiophene-2-carbothioate (26, C H NO S )
12 7 2 2
ꢁ
1
Solid; mp 110–112 C; H NMR (250MHz, CDCl ): ꢁ ¼ 7.01 (dd, J ¼ 3.74, 4.8 Hz, 1H), 7.44 (dd,
3
1
3
J ¼ 1.17, 4.75Hz, 1H), 8.22 (dd, J ¼ 1.29, 3.59Hz, 1H), 7.35 (m, 2H), 8.21 (m, 2H) ppm; C NMR