ꢀ
Z. Dzambaski et al. / Tetrahedron 69 (2013) 9819e9825
9824
169.7 (COlactam), 188.9 (COketone); HRMS: calcd for C12H11ClNO2S
(DMSO-d6,125.8 MHz): Z-isomer
CCl), 128.7 (m-Ph), 129.4 (o-Ph), 133.4 (p-Ph), 136.48 (C1ePh), 151.5
(C]), 173.4 (COlactam), 187.3 (COketone); E-isomer 31.4 (CH2S), 34.4
d 32.3 (CH2S), 33.9 (CH3),100.6 (]
[MþH]þ 268.0194, found 268.0183.
d
4.5.3. (Z)-(5-Chloro-3-methyl-4-oxothiazolidin-2-ylidene)-N-(2-
phenylethyl)ethanamide (9g). Compound 9g was obtained from 5d
(CH3), 98.3 (]CCl), 127.7 (m-Ph), 128.0 (o-fenil), 130.9 (p-Ph), 138.7
(C1ePh), 157.3 (C]), 174.4 (COlactam), 191.3 (COketone); HRMS (ESI):
C
(58.5 mg; 0.2 mmol) and SOCl2 (26.2 mg; 16
m
L; 0.22 mmol) in
12H11ClNO2S [MþH]þ 268.0194, found 268.0196.
toluene (5 mL) according to the general procedure (reaction time
1 h) as a yellow solid (29.3 mg; 48%); mp 89e92 ꢀC; Rf¼0.45 (tol-
4.6.3. (E)-2-Chloro-2-(3-methyl-4-oxothiazolidin-2-ylidene)-N-phe-
nylethanamide (10c). Compound 10c was obtained from 5c
(200.0 mg; 0.757 mmol) and SOCl2 (99.0 mg; 61 mL; 0.832 mmol) in
uene/ethyl acetate 7:3); IR (ATR):
n
¼3314, 3083, 3028, 2943, 1726,
1651, 1585, 1463, 1337, 1293, 1226, 1122, 1028, 811, 741, 703 cmꢁ1
;
1H NMR (CDCl3, 500 MHz):
3H, CH3), 3.58 (m, broad, 2H, NCH2), 5.48 (s, 1H, ]CH), 5.57 (s, 1H,
d
2.84 (t, 2H, CH2Ph, J¼7.0 Hz), 3.16 (s,
CH2Cl2 (24 mL) according to the general procedure (reaction time
6 h) as a white solid (123.5 mg; 58%); mp 115e116 ꢀC (decomposes);
CHS), 5.78 (s, broad, 1H, NH) 7.18e7.35 (m, 5H, Ph); 13C NMR (CDCl3,
Rf¼0.63 (toluene/acetone 7:3); IR (ATR):
1702, 1639, 1598, 1520, 1436, 1312, 1209, 1124, 1058, 1008, 889, 752,
689 cmꢁ1; 1H NMR (DMSO-d6, 500 MHz):
3.52 (s, 3H, CH3), 3.79 (s,
n
¼3374, 3060, 2962, 2932,
125.8 MHz):
d 30.5 (CH3), 35.6 (CH2Ph), 40.6 (NCH2), 56.2 (CHS),
95.0 (]CH),126.5 (p-Ph), 128.6 (o-Ph),128.7 (m-Ph), 138.6 (C1ePh),
150.2 (C]), 166.0 (COamide), 169.1 (COlactam); HRMS: calcd for
d
2H, CH2S), 7.10 (t, 1H, p-Ph, J¼7.2 Hz), 7.32 (m, 2H, m-Ph), 7.62 (d,
C
14H16ClN2O2S [MþH]þ 311.0616, found 311.0616.
2H, o-Ph, J¼8.5 Hz), 9.65 (s, 1H, NHamide); 13C NMR (DMSO-d6,
125.8 MHz):
d 31.4 (CH2S), 34.3 (CH3), 92.6 (]CCl), 121.3 (o-Ph),
4.6. General procedure for the synthesis of vinyl chlorides
10aef
124.0 (p-Ph), 128.4 (m-Ph), 138.2 (C1ePh), 151.5 (C]), 162.9 (COa-
mide), 174.2 (COlactam); HRMS: calcd for C12H12ClN2O2S [MþH]þ
283.0302, found 283.0306.
Thionyl chloride (0.11 mmol) was added to a stirred solution of 5
(0.1 mmol) in CH2Cl2 (2.3e3.5 mL), which was cooled at ꢁ10 ꢀC. The
stirring was continued at ꢁ10 ꢀC for 15e30 min and then at rt until
the disappearance of the starting material (TLC). The solvent and
the excess thionyl chloride were evaporated under reduced pres-
sure. The crude product was purified by column chromatography
(gradient petrol ether (bp 60e80 ꢀC)/ethyl acetate).
4.6.4. (E)-2-Chloro-2-(3-methyl-4-oxothiazolidin-2-ylidene)-N-(2-
phenylethyl)ethanamide (10d). Compound 10d was obtained from
5d (100.0 mg; 0.342 mmol) and SOCl2 (44.8 mg; 27 mL; 0.377 mmol)
in CH2Cl2 (12 mL) according to the general procedure (reaction time
25 min) as a yellow solid (57.6 mg; 54%); mp 97e98 ꢀC (de-
composes); Rf¼0.67 (toluene/acetone 7:3); IR (ATR):
2027, 2932, 1720, 1669, 1518, 1457, 1343, 1300, 1243, 1124, 873, 750,
703 cmꢁ1 1H NMR (CDCl3, 500 MHz):
2.87 (t, 2H, CH2Ph,
n
¼3368, 3060,
4.6.1. (E)-Ethyl
ethanoate (10a). Compound 10a was obtained from 5a (174.4 mg;
0.802 mmol) and SOCl2 (105.1 mg; 62 L; 0.883 mmol) in CH2Cl2
2-chloro-2-(3-methyl-4-oxothiazolidin-2-ylidene)
;
d
J¼7.0 Hz), 3.59 (s, 3H, CH3), 3.58e3.62 (m, 2H, NCH2), 3.64 (s, 2H,
m
CH2S), 6.61 (broad s, 1H, NHamide), 7.20e7.33 (m, 5H, Ph); 13C NMR
(20 mL) according to the general procedure (reaction time 5 h) as
(CDCl3, 125.8 MHz): d 32.0 (CH2S), 34.5 (CH3), 35.7 (CH2Ph), 41.3
a yellow solid (112.0 mg; 59%); mp 118e120 ꢀC; Rf¼0.60 (petrol
(NCH2), 94.0 (]CCl), 126.6 (p-Ph), 128.7 (o-Ph), 128.8 (m-Ph), 138.6
ether/ethyl acetate 7:3); IR (KBr):
n
¼3426, 2968, 2931, 1723, 1674,
(C1ePh), 150.1 (C]), 164.3 (COamide), 173.9 (COlactam); 1H NMR
1532, 1297, 1222, 1117, 1055, 1021, 871, 758 cmꢁ1
;
1H NMR (CDCl3,
(DMSO-d6, 500 MHz):
d
2.77 (t, 2H, CH2Ph, J¼7.7 Hz), 3.36e3.39 (m,
200 MHz):
d
1.36 (t, 3H, CH3CH2, J¼7.0 Hz), 3.64 (s, 3H, NCH3), 3.70
2H, NCH2), 3.46 (s, 3H, CH3), 3.72 (s, 2H, CH2S), 7.18e7.32 (m, 5H,
(s, 2H, CH2S), 4.29 (q, 2H, OCH2, J¼7.0 Hz); 13C NMR (CDCl3,
Ph), 8.11 (t, 1H, NHamide, J¼5.7 Hz); 13C NMR (DMSO-d6, 125.8 MHz):
50.3 MHz):
d
14.1 (CH3CH2), 31.8 (CH2S), 34.7 (NCH3), 61.9 (OCH2),
d 31.3 (CH2S), 34.2 (CH3), 35.1 (CH2Ph), 41.1 (NCH2), 93.0 (]CCl),
93.0 (]CCl), 153.5 (C]), 165.1 (COester), 173.8 (COlactam); 1H NMR
126.2 (p-Ph), 128.3 (o-Ph), 128.7 (m-Ph), 139.3 (C1ePh), 149.6 (C]),
163.8 (COamide), 174.1 (COlactam); HRMS: calcd for C14H16ClN2O2S
[MþH]þ 311.0616, found 311.0623.
(DMSO-d6, 200 MHz):
d
1.24 (t, 3H, CH3CH2, J¼7.3 Hz), 3.49 (s, 3H,
NCH3), 3.86 (s, 2H, CH2S), 4.20 (q, 2H, OCH2, J¼7.3 Hz); 13C NMR
(DMSO-d6, 50.3 MHz):
d 14.4 (CH3CH2), 31.7 (CH2S), 34.6 (NCH3),
61.6 (OCH2), 90.6 (]CCl),155.6 (C]),164.6 (COester),174.5 (COlactam);
4.6.5. (E)-Ethyl
ethanoate (10e). Compound 10e was obtained from 5e (62.9 mg;
0.214 mmol) and SOCl2 (28.1 mg; 17 L; 0.236 mmol) in CH2Cl2
2-chloro-2-(3-benzyl-4-oxothiazolidin-2-ylidene)
HRMS: calcd for C8H11ClNO3S [MþH]þ 236.0143, found 236.0132.
m
4.6.2. (Z)- and (E)-2-Chloro-2-(3-methyl-4-oxothiazolidin-2-
(5 mL) according to the general procedure (reaction time 5 h) as
ylidene)-1-phenylethanone (10b). Compound 10b was obtained
a white oil (39.1 mg; 58%); Rf¼0.45 (petrol ether/ethyl acetate 8:2);
from 5b (149.6 mg; 0.6 mmol) and SOCl2 (78.5 mg; 47
m
L;
IR (ATR):
n
¼3056, 3031, 2976, 2925, 1730, 1666, 1516, 1261, 1158,
0.66 mmol) in CH2Cl2 (15 mL) according to the general procedure
(reaction time 5 h) as a yellow solid (109.6 mg; 68%; mixture of
isomers: Z/E 60:40 molar ratio); mp 93e96 ꢀC; Rf¼0.38 (petrol
1055, 861, 724, 694 cmꢁ1; 1H NMR (CDCl3, 500 MHz):
d 1.32 (t, 3H,
CH3, J¼7.2 Hz), 3.79 (s, 2H, CH2S), 4.25 (q, 2H, OCH2, J¼7.2 Hz), 5.55
(s, 2H, CH2Ph), 7.15 (d, 2H, o-Ph, J¼7.0 Hz), 7.26 (t, 1H, p-Ph,
ether/ethyl acetate 8:2); IR (ATR)
n
¼3434, 3059, 2981, 1725, 1640,
1H NMR
3.07 (s, 3H, CH3), 3.91 (s, 2H, CH2S),
7.55 (m, 2H, m-Ph), 7.65 (t, 1H, p-Ph, J¼7.5 Hz), 7.96 (d, 2H, o-Ph,
J¼7.0 Hz); E-isomer 3.76 (s, 3H, CH3), 3.77 (s, 2H, CH2S), 7.48 (m,
2H, m-Ph), 7.55 (t, 1H, p-Ph, J¼7.8 Hz), 7.72 (d, 2H, o-Ph, J¼7.5 Hz);
13C NMR (CDCl3, 125.8 MHz): Z-isomer
32.2 (CH2S), 34.1 (CH3),
J¼7.5 Hz), 7.33 (m, 2H, m-Ph); 13C NMR (CDCl3, 125.8 MHz):
d 14.2
1533, 1485, 1415, 1346, 1237, 1118, 1004, 917, 702 cmꢁ1
(CDCl3, 500 MHz): Z-isomer
;
(CH3), 31.7 (CH2S), 48.7 (CH2Ph), 62.1 (OCH2), 93.4 (]CCl), 126.1 (o-
Ph), 127.4 (p-Ph), 128.7 (m-Ph), 136.3 (C1ePh), 152.2 (C]), 165.1
(COester), 174.2 (COlactam); HRMS: calcd for C14H15ClNO3S [MþH]þ
312.0456, found 312.0453.
d
d
d
4.6.6. (Z)-Ethyl
(10f). Compound 10f was obtained from 5f (51.1 mg; 0.25 mmol)
and SOCl2 (32.0 mg; 20 L; 0.28 mmol) in CH2Cl2 (7 mL) according
to the general procedure (reaction time 3 h) as a white oil (25.3 mg;
45%); Rf¼0.58 (petrol ether/ethyl acetate 7:3); IR (KBr): ¼3439,
3257, 2982, 2934, 1730, 1671, 1597, 1312, 1281, 1230, 1185, 1053, 760,
2-chloro-2-(4-oxothiazolidin-2-ylidene)ethanoate
102.5 (]CCl), 128.5 (m-Ph), 129.4 (o-Ph), 133.4 (p-Ph), 136.3
(C1ePh), 149.0 (C]), 172.6 (COlactam), 187.8 (COketone); E-isomer
m
d
31.6 (CH2S), 34.8 (CH3), 100.2 (]CCl), 127.8 (m-Ph), 128.2 (o-Ph),
131.1 (p-Ph), 138.3 (C1ePh), 155.6 (C]), 173.9 (COlactam), 192.3
(COketone); 1H NMR (DMSO-d6, 500 MHz): Z-isomer
2.83 (s, 3H,
CH3), 4.09 (s, 2H, CH2S), 7.45e7.84 (m, 5H, Ph); E-isomer 3.56 (s,
3H, CH3), 3.90 (s, 2H, CH2S), 7.45e7.84 (m, 5H, Ph); 13C NMR
n
d
d
712 cmꢁ1; 1H NMR (CDCl3, 200 MHz):
d
1.33 (t, 3H, CH3, J¼7.2 Hz),
3.78 (s, 2H, CH2S), 4.27 (q, 2H, OCH2, J¼7.2 Hz),10.42 (s,1H, NH); 13
C