JOURNAL PRE-PROOF
4
.1.1 General procedure (A) for the synthesis of (Z)-2-imino-
7.03 (d, J = 8.2 Hz, 2H), 6.87 (d, J = 8.7 Hz, 2H), 6.50 (t, J = 2.0
13
(
5Z)-ylidene-N-substituted thiazolidines 11a-18a, 19b, 20c, 21c,
Hz, 1H), 4.46 (d, J = 2.0 Hz, 2H), 3.78 (s, 3H), 3.12 (s, 3H).
C
2
0d, and 22.
NMR δ 158.8, 156.9, 154.7, 129.3, 128.4, 126.3 (q, J = 3.8 Hz),
1
1
2
25.0 (q, J = 31.3 Hz), 124.8 (q, J = 269 Hz), 122.5, 120.2,
14.2, 59.4, 55.4, 33.0. FT-IR (neat, cm ): 3130, 2954, 2925,
To vigorously stirred silica gel (1.75g/mmol), a solution of
-1
propargyl amine (200 mg, 1.14 mmol) in CH Cl (0.2 mL) and
2
2
834, 1647, 1508, 1421, 1322, 1255, 1099, 848. HR-MS (m/z):
isothiocyanate (1.14 mmol) was added dropwise. The resulting
slurry was stirred at rt for 2 h. The resulting slurry was placed
directly on a column of silica gel and the crude reaction mixture
was purified by flash chromatography to afford the thiazolidine.
+
calc for [M+H] C H N OF S, 379.1086, found: 379.1092.
1
9
17
2
3
(Z)-N-(4-Methoxyphenyl)-5-((Z)-4-methoxybenzylidene)-3-
methylthiazolidin-2-imine (15a): Synthesized following general
procedure A, (200 mg, 1.14 mmol), purified by column
chromatography (ethyl acetate:hexanes
compound 15a (389 mg, 99%) as a colorless solid. m.p. 132-136
°C. H NMR: δ 7.19 (d, J = 8.7 Hz, 2H), 6.90 (d, J = 8.7 Hz, 2H),
6.87 – 6.81 (m, 4H), 6.46 (t, J = 1.9 Hz, 1H), 4.40 (d, J = 1.9 Hz,
2H), 3.80 (s, 3H), 3.78 (s, 3H), 3.10 (s, 3H). C NMR: δ 158.6,
156.8, 155.9, 145.1, 129.3, 128.7, 126.6, 123.2, 119.5, 114.3,
4
.1.2 General procedure (B) for the synthesis of (Z)-2-
= 1:4) to afford
substituted imino-5-((Z)-ylidene)- thiazolidin-4-ones 28-38.
1
The thiazoline (100 mg) was dissolved in CDCl (1 mL) and
3
left open to the atmosphere for 1-3 days. The resulting mixture
was concentrated and purified by column chromatography to
afford a yellow solid. The obtained solid was triturated with a
mixture of diethyl ether: hexanes (1:10, 1 mL) and filtered to
obtain the oxidized product.
1
3
-
1
114.1, 59.5, 55.5, 55.4, 33.1. FT-IR (neat, cm ): 3131, 2958,
2929, 2832, 1643, 1497, 1456, 1254, 1183, 1027, 835. HR-MS
+
(m/z): calc for [M+H] C H N O S, 341.1318, found: 341.1320.
1
9
20
2
2
(
Z)-N-Tolyl-5-((Z)-4-methoxybenzylidene)-3-
methylthiazolidin-2-imine (11a): Synthesized following
general procedure A, (200 mg, 1.14 mmol), purified by column
chromatography (ethyl acetate:hexanes 1:4) to afford
compound 11a (362 mg, 97%) as a light-yellow solid. m.p. 88-92
(Z)-N-(4-Bromophenyl)-5-((Z)-4-methoxybenzylidene)-3-
methylthiazolidin-2-imine (16a): Synthesized following general
procedure A, (200 mg, 1.14 mmol), purified by column
chromatography (ethyl acetate:hexanes
compound 16a (442 mg, 99%) as a colorless solid. m.p. 130-134
°C. H NMR δ 7.39 (d, J = 8.7 Hz, 2H), 7.18 (d, J = 8.7 Hz, 2H),
6.85 (dd, J = 10.0, 8.8 Hz, 4H), 6.47 (t, J = 2.0 Hz, 1H), 4.41 (d,
J = 2.0 Hz, 2H), 3.78 (s, 3H), 3.09 (s, 3H). C NMR: δ 158.8,
156.9, 150.7, 132.0, 129.3, 128.5, 125.9, 124.2, 120.0, 116.2,
=
= 1:4) to afford
1
°
6
C. H NMR: δ 7.20 (d, J = 8.8 Hz, 2H), 7.11 (d, J = 8.2 Hz, 2H),
.89 (d, J = 8.2 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 6.46 (t, J = 1.9
Hz, 1H), 4.43 – 4.34 (d, J = 1.9 Hz, 2H), 3.77 (s, 3H), 3.10 (s,
1
1
3
13
3
1
H), 2.34 (s, 3H). C NMR: δ 158.6, 156.4, 149.1, 132.7, 129.7,
29.3, 128.7, 126.6, 122.1, 119.5, 114.1, 59.5, 55.4, 33.1, 21.1.
-
1
-1
FT-IR (neat, cm ): 2950, 2920, 2832, 1647, 1602, 1505, 1286,
114.2, 59.5, 55.4, 33.0. FT-IR (neat, cm ): 3046, 2919, 2840,
1642, 1575, 1481, 1250, 1178, 953, 840. HR-MS (m/z): calc for
[M+H] C18
+
1
246, 1175, 1026, 957, 821. HR-MS (m/z): calc for [M+H]
+
C H N OS, 325.1369, found: 325.1374.
H
17
N
2
OSBr, 389.0318, found: 389.0321.
1
9
20
2
(
Z)-N-(4-Fluorophenyl)-5-((Z)-4-methoxybenzylidene)-3-
(Z)-N-(4-Chlorophenyl)-5-((Z)-4-methoxybenzylidene)-3-
methylthiazolidin-2-imine (17a): Synthesized following general
procedure A, (200 mg, 1.14 mmol), purified by column
methylthiazolidin-2-imine (12a): Synthesized following general
procedure A, (200 mg, 1.14 mmol), purified by column
chromatography (ethyl acetate:hexanes
compound 12a (375 mg, 99%) as a colorless solid. m.p. 112-116
C. H NMR: δ 7.19 (d, J = 8.8 Hz, 2H), 6.98 (t, J = 8.9 Hz, 2H),
.91 (dd, J = 8.9, 5.0 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 6.47 (t, J
2.0 Hz, 1H), 4.41 (d, J = 2.0 Hz, 2H), 3.77 (s, 3H), 3.09 (s,
H). C NMR δ 160.4, 158.7, 157.1, 147.8, 129.3, 127.4 (d, J =
06 Hz), 123.5 (d, J = 7.5 Hz), 119.8, 115.6 (d, J = 22.5 Hz),
14.2, 59.5, 55.4, 33.0. FT-IR (neat, cm ): 3016, 2965, 2930,
901, 2837, 1643, 1605, 1496, 1249, 1176, 1027, 959, 839. HR-
MS (m/z): calc for [M+H] C H N OFS, 329.1118, found:
29.1122.
=
1:4) to afford
chromatography (ethyl acetate:hexanes = 1:4) to afford
compound 17a (390 mg, 99%) as a colorless solid. m.p. 116-118
1
1
°
6
=
3
3
1
2
°C. H NMR δ 7.24 (d, J = 8.7 Hz, 2H), 7.19 (d, J = 8.7 Hz, 2H),
6.88 (dd, J = 15.8, 8.7 Hz, 4H), 6.48 (t, J = 1.9 Hz, 1H), 4.42 (d,
1
3
J = 2.0 Hz, 2H), 3.78 (s, 3H), 3.09 (s, 3H). C NMR: δ 158.8
1
3
157.0, 150.3, 129.3, 129.1, 128.5, 128.4, 125.9, 123.7, 120.0,
-
1
114.2, 59.5, 55.4, 33.0. FT-IR (neat, cm ): 3046, 2919, 2841,
-
1
1642, 1583, 1484, 1251, 1178, 1082, 841. HR-MS (m/z): calc for
+
[M+H] C18
H
17
N
2
OSCl, 345.0823, found: 345.0816.
+
1
8
17
2
(
Z)-N-(4-tert-Butylphenyl)-5-((Z)-4-methoxybenzylidene)-
-methylthiazolidin-2-imine (18a): Synthesized following
general procedure A, (200 mg, 1.14 mmol), purified by column
chromatography (ethyl acetate:hexanes 1:4) to afford
3
3
(Z)-N-(4-Nitrophenyl)-5-((Z)-4-methoxybenzylidene)-3-
methylthiazolidin-2-imine (13a): Synthesized following general
procedure A, (200 mg, 1.14 mmol), purified by column
chromatography (ethyl acetate:hexanes
=
compound 18a (400 mg, 95%) as a colorless solid. m.p. 146-149
1
=
1:4) to afford
°C. H NMR: δ 7.30 (d, J = 8.6 Hz, 2H), 7.21 (d, J = 8.8 Hz, 2H),
compound 13a (380 mg, 93%) as a yellow solid. m.p. 160-164
6.89 (d, J = 8.6 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 6.50 – 6.45 (t,
J = 2.0 Hz, 1H), 4.41 (d, J = 2.0 Hz, 2H), 3.78 (s, 3H), 3.11 (s,
3H), 1.33 (s, 9H). C NMR δ 158.6, 156.0, 148.7, 145.9, 129.7,
1
°
C. H NMR: δ 8.16 (d, J = 9.0 Hz, 2H), 7.17 (d, J = 8.7 Hz, 2H),
1
3
7
.03 (d, J = 9.0 Hz, 2H), 6.87 (d, J = 8.7 Hz, 2H), 6.53 (t, J = 2.0
13
Hz, 1H), 4.50 (d, J = 2.0 Hz, 2H), 3.78 (s, 3H), 3.14 (s, 3H).
C
128.8, 126.8, 125.9, 121.7, 119.5, 114.1, 59.4, 55.4, 34.4, 33.1,
-
1
NMR: δ 158.9, 157.8, 157.1, 129.2 128.2, 125.2, 122.7, 120.6,
31.6. FT-IR (neat, cm ): 3046, 2959, 2841, 1638, 1597, 1507,
-
1
+
1
1
(
14.2, 59.4, 55.4, 33.0. FT-IR (neat, cm ): 3019, 2921, 2834,
1250, 1177, 1035, 857, 816, 530. HR-MS (m/z): calc for [M+H]
638, 1567, 1493, 1318, 1248, 1174, 1105, 1030, 843. HR-MS
m/z): calc for [M+H] C H N O S, 356.1063, found: 356.1062.
C
22
H
26
N
2
OS, 367.1839, found: 367.1831.
+
1
8
17
3
3
(Z)-2-((4-Methylphenyl)imino)-5-((Z)-4-
(Z)-N-(4-Trifluromethylphenyl)-5-((Z)-4-methoxybenzyl-
methoxybenzylidene)-3-methylthiazolidin-4-one
(28):
idene)-3-methylthiazolidin-2-imine (14a): Synthesized
following general procedure A, (200 mg, 1.14 mmol), purified by
column chromatography (ethyl acetate:hexanes = 1:4) to afford
Synthesized following general procedure B, (100 mg, 0.31
mmol), purified by column chromatography (ethyl
acetate:hexanes = 1:9) to afford compound 28 (24 mg, 23%) as a
light yellow solid. m.p. 152-154 °C. H NMR: δ 7.70 (s, 1H),
7.40 (d, J = 8.7 Hz, 2H), 7.19 (d, J = 7.9 Hz, 2H), 6.92 (m, 2H),
1
compound 14a (406 mg, 94%) as a colorless solid. m.p. 148-151
1
°
C. H NMR: δ 7.53 (d, J = 8.2 Hz, 2H), 7.19 (d, J = 8.7 Hz, 2H),