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·1496· 精细化工 FINE CHEMICALS 第 36 卷

Hz, 1H, CH), 3.81 (s, 3H, CH 3 ), 3.67 (s, 3H, CH 3 ); 4.6 mm), V(正己烷)∶V(异丙醇)=80∶20, 1.0 mL/min,
13
CNMR (125 MHz, CDCl 3 ), δ: 169.2, 168.6, 167.0, λ=210 nm, t r (major)=9.97 min, t r (minor)=12.16 min];
153.6, 137.5, 136.1, 133.9, 132.0, 131.2, 130.5, 130.1, [α] D =+73.2(c=0.020 mol/L, CHCl 3 )。
25
128.2, 127.7, 126.1, 56.9, 53.5, 53.4, 52.9; MS(ESI),
+
+
m/Z: 558([M+Na] ), 574([M+K] )。Anal. Calcd. for 二乙基-2-(((5-(2,4-二氯苯基)-1,3,4-噻二唑-2-
C 20 H 15 Cl 4 N 3 O 4 S(%): C, 44.88; H, 2.82; N, 7.85; 基)氨基)(苯基)甲基)丙二酸酯(Ⅳe)：白色固体，产
–1
Found: C, 44.67; H, 2.69; N, 7.73。 率 57%， 熔点 129~130 ℃；IR (KBr)， /cm : 3209,
(–)- 二甲 基 -2-((2,3- 二氯 苯基 )((5-(2,4- 二氯苯 3005, 2980, 2916, 1655, 1544, 1496, 1259, 1232, 1170,
1
1095, 979, 829; HNMR (500 MHz, CDCl 3 ), δ: 8.12 (d,
基)-1,3,4-噻二唑-2-基)氨基)甲基)丙二酸酯〔(–)-Ⅳb〕：
J = 8.6 Hz, 1H, NH), 7.45 (s, 1H, ArH), 7.40~7.29 (m,
e.e.值(HPLC) 82.9%[Daicel Chiralpak IA 柱 (250 6H, ArH), 7.19 (s, 1H, ArH), 5.57 (s, 1H, CH),
mm×4.6 mm), V(正己烷)∶V(异丙醇)=80∶20, 1.0 4.20~4.19 (m, 4H, 2CH 2 ), 3.98 (s, 1H, CH), 1.20~1.15
13
mL/min, λ=210 nm, t r (major)=19.61 min, t r(minor)= (m, 6H, 2CH 3 ); CNMR (125 MHz, CDCl 3 ), δ: 170.2,
25
17.51 min]; [α] D =－73.5(c=0.017 mol/L, CHCl 3 )。 168.1, 166.8, 152.9, 137.9, 135.9, 132.0, 131.2, 130.1,
128.9, 128.3, 127.6, 126.7, 62.3, 62.0, 59.5, 57.2, 14.0,
二甲基-2-(((5-(4-氯苯基)-1,3,4-噻二唑-2-基)氨
+
+
13.9; MS(ESI), m/Z: 494([M+H] ), 516([M+Na] )。
基)(2,3-二氯苯基)甲基)丙二酸酯(Ⅳc)：白色固体， Anal. Calcd. for C 22 H 21 Cl 2 N 3 O 4 S(%): C, 53.45; H,
–1
产率 57%，熔点 184~185 ℃；IR (KBr)， /cm : 3419, 4.28; N, 8.50; Found: C, 53.32; H, 4.16; N, 8.45。
3323, 2945, 2916, 1741, 1498, 1450, 1280, 1236, 1161, (–)-二乙基-2-(((5-(2,4-二氯苯基)-1,3,4-噻二唑-
1
1037, 979, 831; HNMR (500 MHz, DMSO-d 6 ), δ:
8.85 (d, J = 8.6Hz, 1H, NH), 7.76 (d, J = 8.6Hz, 2H, 2-基)氨基)(苯基)甲基)丙二酸酯〔(–)-Ⅳe〕：e.e.值
ArH), 7.60~7.52 (m, 4H, ArH), 7.41 (t, J = 8.0 Hz, 1H, (HPLC)>99%[Daicel Chiralpak IA柱(250 mm×4.6 mm),
ArH), 5.99 (t, J = 8.6 Hz, 1H, CH), 4.24 (d, J = 9.1Hz, V(正己烷)∶V(异丙醇)=70∶30, 1.0 mL/min, λ=270 nm,
1H, CH), 3.66 (s, 3H, CH 3 ), 3.52 (s, 3H, CH 3 ); 25
13 t r (major)=5.34 min, t r(minor)=6.54 min]; [α] D =83.6
CNMR (125 MHz, DMSO-d 6 ), δ: 167.6, 167.3, 166.7,
156.8, 139.5, 134.9, 132.4, 131.3, 130.6, 129.8, 129.7, (c=0.021 mol/L, CHCl 3 )。
128.9, 128.6, 127.9, 55.8, 55.4, 53.3, 53.2; MS(ESI), 二乙 基 -2-((3,4- 二氯苯 基 )((5-(2,4- 二氯 苯
+
m/Z: 502([M+H] )。Anal. Calcd. for C 20 H 16 Cl 3 N 3 O 4 S 基)-1,3,4-噻二唑-2-基)氨基)甲基)丙二酸酯(Ⅳf)：白
(%): C, 47.97; H, 3.22; N, 8.39; Found: C, 47.77; H, 色固体，产率 66%；熔点 218~220 ℃；IR (KBr)，
3.42; N, 8.59。 /cm : 3223, 3007, 2978, 2916, 1653, 1543, 1473,
–1
1
(–)-二甲基-2-(((5-(4-氯苯基)-1,3,4-噻二唑-2-基) 1293, 1230, 1162, 1072, 981, 825; HNMR (500 MHz,
氨基)(2,3-二氯苯基)甲基)丙二酸酯〔(–)-Ⅳc〕：e.e. CDCl 3 ), δ: 8.13 (d, J = 8.6 Hz, 1H, NH), 7.51 (s, 1H),
7.47 (d, J = 2.3 Hz, 1H, ArH), 7.42 (d, J =8.6 Hz, 1H,
值(HPLC) 95.6%[Daicel Chiralpak IA 柱(250 mm×
ArH), 7.33~7.30 (m, 2H, ArH), 7.19~7.17 (d, J =
4.6 mm), V(正己烷)∶V(异丙醇)=75∶25, 1.0 mL/min, 8.6 Hz, 1H, ArH), 5.64 (dd, J = 4.6、4.6 Hz, 1H, CH),
λ=210 nm, t r (major)=18.31 min, t r (minor)=23.47 min]; 4.22~4.20 (m, 4H, 2CH 2 ), 3.91 (d, J = 4.6 Hz, 1H,
25
[α] D =－37.2(c=0.019 mol/L, CHCl 3 )。
13
CH), 1.26~1.16 (m, 6H, 2CH 3 ); CNMR (125 MHz,
二甲基-2-((2,3-二氯苯基)((5-(3-氟苯基)-1,3,4- CDCl 3 ), δ: 169.3, 168.0, 166.4, 153.4, 138.6, 136.1,
噻二唑-2-基)氨基)甲基)丙二酸酯(Ⅳd)：白色固体， 133.1, 132.5, 132.0, 131.3, 130.8, 130.1, 128.8, 128.1,
–1
产率 57%，熔点 179~180 ℃；IR (KBr)， /cm : 3400, 127.7, 126.2, 62.6, 62.3, 57.9, 56.6, 14.0, 13.9; MS
+
+
2953, 2920, 2848, 1640, 1558, 1506, 1489, 1350, 1271, (ESI), m/Z: 563 ([M+H] ), 585([M+Na] ), 601 ([M+
+
1
1180, 862, 785; HNMR (500 MHz, DMSO-d 6 ), δ: K] )。Anal. Calcd. for C 22 H 19 Cl l4 N 3 O 4 S(%): C, 46.91;
8.89 (d, J = 8.2Hz, 1H, NH), 7.61~7.49 (m, 5H, ArH), H, 3.40; N, 7.46; Found: C, 46.81; H, 3.50; N, 7.76。
7.42 (t, J = 7.8Hz, 1H, ArH), 7.31 (t, J = 8.7Hz, 1H, (–)-二乙基-2-((3,4-二氯苯基 )((5-(2,4-二氯苯
ArH), 6.01 (t, J = 8.7Hz, 1H, CH), 4.25 (d, J = 9.2Hz,
1H, CH), 3.66 (s, 3H, CH 3 ), 3.53 (s, 3H, CH 3 ); 基)-1,3,4-噻二唑-2-基)氨基)甲基)丙二酸酯〔(–)-Ⅳ
13 f 〕： e.e. 值 (HPLC) 88.0%[Daicel Chiralpak IA 柱
CNMR (125 MHz, DMSO-d 6 ), δ: 167.7, 167.3, 166.6,
156.7, 139.5, 132.4, 131.8, 131.4, 130.6, 128.79, 117.1, (250 mm×4.6 mm), V(正己烷)∶V(异丙醇)=75∶25,
19
113.4, 55.8, 53.3, 53.2; FNMR(200 MHz, DMSO-d 6 ), 1.0 mL/min, λ=270 nm, t r(major)=8.61 min, t r (minor)=
+
+
δ: 112.0; MS(ESI), m/Z: 484([M+H] ), 506([M+Na] ), 10.11 min]; [α] D =－47.2(c=0.014 mol/L, CHCl 3 )。
25
+
522([M+K] )。Anal. Calcd. for C 20 H 16 Cl 2 FN 3 O 4 S(%): 二乙基-2-(((5-(2,4-二氯苯基)-1,3,4-噻二唑-2-
C, 49.60; H, 3.33; N, 8.68; Found: C, 49.56; H, 3.27; 基)氨基)(2,3-二甲氧基苯基)甲基)丙二酸酯(Ⅳg)：白
N, 8.58。
色固体，产率 55%；熔点 141~143 ℃；IR (KBr)，
(+)-二甲基-2-((2,3-二氯苯基)((5-(3-氟苯基)-
–1
/cm : 3383, 3366, 2951, 2916, 1666, 1537, 1481,
1,3,4-噻二唑-2-基)氨基)甲基)丙二酸酯〔(+)-Ⅳd〕：
1
1271, 1221, 1166, 1064, 983, 823; HNMR (500 MHz,
e.e.值(HPLC) >99%[Daicel Chiralpak IA 柱(250 mm× CH 3 OD), δ: 7.94 (d, J = 8.6 Hz, 1H, ArH), 7.60 (d, J =