手性有机碱在水油两相体系制手性含硫吲哚化合物的应用转让专利
申请号 : CN201510431625.8
文献号 : CN106366032B
文献日 : 2019-04-30
发明人 : 李灿 , 陈萍 , 刘龑
申请人 : 中国科学院大连化学物理研究所
摘要 :
权利要求 :
1.手性有机碱在水油两相体系制手性含硫吲哚化合物的应用,其特征在于:所述手性有机碱为以下A-F物质的一种或两种以上;
其催化体系为在水油两相中使用手性有机碱催化硫醇对吲哚的不对称硫化方法;
制备手性含硫吲哚化合物反应式和条件如下:
式中:
温度:0℃至室温;
溶剂:水作为溶剂,加入有机溶剂以便将底物溶解;
时间:12-96小时;
碱:无机碱;
催化剂:手性有机碱,也称为手性有机碱催化剂;
所述R1为甲基、苯基或氢,R2为苯基、1位萘基、1位噻吩基、C5烷基或含有取代基的苯环,苯环上的取代基为F、Cl、Br,Me、MeO、CF3、NO2中的一种,取代基个数为1,R3为F或Me,R4为三苯基甲基,Ts为对甲基苯磺酰基。
2.如权利要求1所述的应用,其特征在于:
反应步骤为:在反应容器中投入手性有机碱催化剂,手性有机碱催化剂为底物对甲基苯磺酰基吲哚用量的1-20mol%,再加入相对于底物对甲基苯磺酰基吲哚用量的2到5倍摩尔当量的无机碱,然后加入对甲基苯磺酰基吲哚和硫醇化合物,对甲基苯磺酰基吲哚与硫醇的比为1/2-1/1.1,于此混合物中加入有机溶剂溶解,相对于每0.1mmol底物对甲基苯磺酰基吲哚有机溶剂的加入量为200微升至2毫升,再加入水,相于每0.1mmol底物对甲基苯磺酰基吲哚水的加入量为0.5毫升至4毫升,将此反应体系置于0℃至室温进行反应,反应结束后,分离纯化得产物。
3.如权利要求2所述的应用,其特征在于:
反应结束后,先加入相对于反应体系体积用量2倍至5倍范围的饱和食盐水,再用乙酸乙酯萃取,合并有机相,除去溶剂后直接柱层析分离得到纯的产物。
4.如权利要求1或2所述的应用,其特征在于:所用的无机碱为碳酸钠、碳酸钾、碳酸氢钠、氢氧化钠、氢氧化钾、碳酸铯或磷酸钾中的一种或二种以上。
5.如权利要求1或2所述的应用,其特征在于:反应中无机碱使用量和甲基苯磺酰基吲哚摩尔比为2:1,底物取对甲基苯磺酰基吲哚与硫醇的比为1/2-1/1.1,底物取甲基苯磺酰基吲哚与催化剂的摩尔比例是10:1。
6.如权利要求1或2所述的应用,其特征在于:反应所用的有机溶剂为甲苯、二氯甲烷、异丙醇、四氢呋喃、三氯甲烷、1,2二氯乙烷中的一种或二种以上。
7.如权利要求1或2所述的应用,其特征在于:所述反应式为对甲基苯磺酰基吲哚和三苯硫醇,无机碱为碳酸钠,溶剂为三氯甲烷和大量的水作为溶剂时,温度为0℃时,催化剂为奎宁丁硫脲衍生催化剂所述结果最佳。
8.如权利要求7所述的应用,其特征在于:当对甲基苯磺酰基吲哚底物用量为0.2mmol时,三氯甲烷的用量为200微升,水的用量为4毫升。
说明书 :
手性有机碱在水油两相体系制手性含硫吲哚化合物的应用
技术领域
背景技术
Tetrahedron Lett.2014,55,486-489.(d)Khorshidi A.;Shariati S.RSC Adv.2014,4,
41469-41475)。因此,合成具有光学纯的3位含硫吲哚类仍然是一个挑战。
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Jing L.-H;Qin D.-B.Tetrahedron Lett.2015,56,2867-2870)。
发明内容
具体实施方式
1
=0.5,CHCl3).H NMR(400MHz,CDCl3)δ7.86(d,J=7.1Hz,1H),7.60(s,1H),7.35(dt,J=
6.5,3.9Hz,6H),7.32-7.28(m,1H),7.25-7.21(m,1H),7.18(d,J=7.1Hz,2H),7.15-7.00(m,13H),4.82(s,1H),2.06(s,3H).13C NMR(101MHz,CDCl3)δ144.8,143.3,135.4,130.6,
130.1,129.4,128.0,127.9,127.7,126.6,126.0,121.2,120.5,119.4,113.9,110.2,77.4,-
77.1,76.8,69.7,46.8,12.4.高分辨质谱{HRMS(ESI)m/z[M+Cl] }计算为(calcd.for)C35H29ClNS:530.1709,found:530.1714.
95:5at 0.5mL/min,λ=254nm,tminor=16.7min,tmajor=18.7min);[α]20D=+37.40(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.77(d,J=7.6Hz,1H),7.65(s,1H),7.37(dd,J=6.7,
2.9Hz,6H),7.32–7.27(m,2H),7.18-7.04(m,13H),7.01(d,J=8.6Hz,2H),4.81(s,1H),
2.09(s,3H).13C NMR(101MHz,CDCl3)δ144.6,141.8,135.4,131.6,130.7,130.1,129.4,
129.2,127.9,127.8,126.7,121.4,120.1,119.6,113.6,110.4,69.7,46.0,12.4.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C35H28Cl2NS:564.1320,found:564.1339.[0088]
Daicel AD-H column);正己烷:异丙醇=95:5,流速为0.5毫升每分钟,检测波长为254纳米,主要峰的保留时间为14.4分钟,另一个对映体的保留时间为18.7分钟(n-hexane/i-PrOH 95:5at 0.5mL/min,λ=254nm,tmajor=16.9min,tminor=24.7min);[α]20D=+194.39(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ8.15(dd,J=7.9,1.0Hz,1H),7.80(d,J=7.7Hz,
1H),7.66(s,1H),7.48-7.37(m,6H),7.21(d,J=7.5Hz,1H),7.17-7.01(m,12H),7.00-6.87(m,2H),5.37(s,1H),2.33(s,3H).13C NMR(101MHz,CDCl3)δ144.3,139.4,135.4,132.7,
131.4,131.2,130.0,129.1,127.8,127.3,127.1,126.6,126,121.2,120.2,119.4,111.9,
110.3,69.3,44.0,13.5.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C35H28Cl2NS:564.1320,found:564.1339.
0.3mL/min,λ=254nm,tmajor=30.8min,tminor=34.5min);[α]20D=+65.80(c 0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.77(d,J=7.2Hz,1H),7.68(s,1H),7.37(ddd,J=8.0,5.4,2.7Hz,
6H),7.29(t,J=5.5Hz,2H),7.18-7.10(m,10H),7.09-7.05(m,1H),7.00(s,1H),6.98–6.90(m,2H),4.82(s,1H),2.16(s,3H).13C NMR(101MHz,CDCl3)δ145.2,144.5,135.4,133.48,
130.7,130.1,129.4,129.1,127.9,127.9,127.8,126.7,126.0,121.5,120.0,119.7,
113.6,110.4,69.7,46.2,12.5.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C35H28Cl2NS:564.1320,found:564.1343.
254纳米,主要峰的保留时间为15.3分钟,另一个对映体的保留时间为18.6分钟(n-hexane/i-PrOH 95:5at 0.5mL/min,λ=254nm,tmajor=15.3min,tminor=18.6min);[α]20D=+66.00
1
(c 0.5,CHCl3).H NMR(400MHz,CDCl3)δ7.76(d,J=7.5Hz,1H),7.62(s,1H),7.38-7.30(m,
6H),7.27(d,J=6.6Hz,1H),7.22(s,1H),7.15-7.05(m,12H),6.70(t,J=8.7Hz,2H),4.79(s,1H),2.07(s,3H).13C NMR(101MHz,CDCl3)δ162.4,160.0,144.6,139.0,135.4,130.1,
129.4,129.3(d,J=8Hz),127.9,127.7,126.6,121.4,120.2,119.6,114.6(d,J=22Hz),
19
110.35,69.7,45.9,12.4. F NMR(377MHz,CDCl3)δ-115.74.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C35H29ClNS:548.1615,found:548.1624.
20
0.5mL/min,λ=254nm,tminor=16.9min,tmajor=19.9min);[α] D=+66.00(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.78(d,J=7.6Hz,1H),7.65(s,1H),7.38(dd,J=6.7,3.0Hz,6H),
7.32(dd,J=8.1,3.4Hz,1H),7.27-7.24(m,1H),7.18-7.12(m,12H),7.03(d,J=8.5Hz,
2H),4.81(s,1H),2.09(s,3H).13C NMR(101MHz,CDCl3)δ144.6,142.3,135.5,130.9,130.1,
129.6,129.46,128,127.8,126.7,121.5,120.1,119.8,119.6,113.5,110.4,69.8,46.1,
12.4.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C35H28BrClNS:608.0814,found:608.0834.
254纳米,主要峰的保留时间为20.4分钟,另一个对映体的保留时间为28.3分钟(n-hexane/i-PrOH 95:5at 0.3mL/min,λ=254nm,tmajor=20.4min,tminor=28.3min);[α]20D=+137.19(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ8.50(d,J=7.9Hz,1H),7.74(d,J=7.8Hz,1H),
7.67(s,1H),7.45(dd,J=8.0,1.5Hz,6H),7.33(t,J=7.7Hz,3H),7.21(d,J=7.6Hz,1H),
7.17–7.07(m,11H),5.76(s,1H),2.25(s,3H).13C NMR(101MHz,CDCl3)δ144.3,139.3,
135.3,132.4,131.5,130.9,130.0,127.7,127.2,126.2,126.1(q,J=7Hz),124.3(q,J=
273Hz),121.2,120.1,119.3,112.40,110.3,69.1,43.2,13.4,13.34.19F NMR(377MHz,CDCl3)δ-57.01.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C36H28ClF3NS:
598.1583,found:598.1599.
0.3mL/min,λ=254nm,t minor=33.7min,tmajor=36.0min);[α]20D=+9.20(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.91–7.84(m,1H),7.55(s,1H),7.36(dt,J=7.0,4.0Hz,6H),
7.33-7.28(m,1H),7.23(dd,J=6.7,1.8Hz,1H),7.16-7.09(m,12H),6.91(d,J=8.0Hz,
2H),4.81(s,1H),2.24(s,3H),2.02(s,3H).13C NMR(101MHz,CDCl3)δ144.8,140.4,135.6,
135.5,130.6,130.2,129.5,128.8127.8,127.7,126.5,121.2,120.6,119.4,113.9,110.2,
69.7,46.5,21.0,12.3.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C36H31ClNS:
544.1866,found:544.1878.
0.5mL/min,λ=254nm,tmajor=13.7min,tminor=23.4min);[α]20D=+174.99(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ8.06(d,J=7.7Hz,1H),7.72(d,J=7.6Hz,1H),7.64(s,1H),7.38(dd,J=6.7,3.0Hz,5H),7.29(q,J=4.5Hz,2H),7.21(d,J=7.3Hz,1H),7.14-7.01(m,
11H),6.93(t,J=7.0Hz,1H),6.77(d,J=7.5Hz,1H),5.03(s,1H),2.21(s,3H),1.75(s,
3H).13C NMR(101MHz,CDCl3)δ144.6,140.1,135.2,135.0,131.2,130.1,129.9,129.9,
129.4,127.9,127.6,126.5,126.0,125.2,121.2,120.1,119.3,110.2,69.4,43.9,19.8,
13.4.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C36H31ClNS:544.1866,found:
544.1890.
95:5at 0.5mL/min,λ=254nm,tmajor=21.0min,tminor=25.7min);[α]20D=+6.80(c 0.5,
1
CHCl3).H NMR(400MHz,CDCl3)δ7.86(d,J=7.2Hz,1H),7.59(s,1H),7.36(dd,J=6.7,
2.9Hz,6H),7.24(d,J=7.0Hz,1H),7.19-7.03(m,13H),6.63(d,J=8.7Hz,2H),4.80(s,
1H),3.71(s,3H),2.02(s,3H).13C NMR(101MHz,CDCl3)δ157.9,144.8,135.6,135.5,130.5,
130.1,128.0,127.8,127.7,126.5,121.2,120.5,119.4,114.1,113.4,110.2,69.7,55.3,
46.1,12.3.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C36H31ClNOS:560.1815,found:560.1825.
90:10at 1.0mL/min,λ=254nm,tmajor=8.6min,tminor=14.6min);[α]20D=+61.20(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ8.37–8.28(m,1H),7.70(s,1H),7.54(d,J=8.0Hz,1H),
7.52-7.43(m,6H),7.39(dd,J=8.0,1.2Hz,1H),7.30(d,J=7.7Hz,1H),7.20-7.02(m,
12H),7.01-6.93(m,1H),6.00(s,1H),2.25(s,3H).13C NMR(101MHz,CDCl3)δ148.3,144.2,
135.8,135.4,131.7,131.4,131.4,129.9,127.9,127.1,126.8,126.7,124.2,121.5,
119.7,119.5,111.8,110.4,69.2,41.6,12.8.HRMS(ESI)m/z[M+Cl]-calcd.for
C35H28ClN2O2S:575.1560,found:575.1567.
0.3mL/min,λ=254nm,tmajor=40.7min,tminor=43.9min);[α]20D=+84.79(c=0.5,CHCl3).1HNMR(400MHz,CDCl3)δ8.09(d,J=7.2Hz,1H),7.91(d,J=7.1Hz,1H),7.67(d,J=8.0Hz,
1H),7.54(d,J=8.2Hz,1H),7.48(d,J=9.0Hz,2H),7.43-7.35(m,6H),7.27(td,J=7.6,
3.7Hz,2H),7.21(d,J=8.0Hz,1H),7.19-7.06(m,4H),7.04-6.99(m,8H),5.73(s,1H),2.12(s,3H).13C NMR(101MHz,CDCl3)δ144.5,137.4,135.2,133.8,131.5,130.7,130.0,128.5,
127.9,127.8,127.7,127.0,126.5,125.4,125.1,125.0,123.5,121.1,120.2,119.5,
112.9,110.3,69.3,43.0,13.3.HRMS(ESI)m/z[M+Cl]-calcd.for C39H31ClNS:580.1866,found:580.1869.
0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.71(d,J=7.8Hz,1H),7.62(s,1H),7.39–7.32(m,
6H),7.28(d,J=4.1Hz,1H),7.20-7.10(m,10H),7.10-7.06(m,1H),7.04(dd,J=5.2,
1.1Hz,1H),6.70(dd,J=5.0,3.6Hz,1H),6.65-6.58(m,1H),4.98(d,J=0.7Hz,1H),1.97(s,3H).13C NMR(101MHz,CDCl3)δ148.0,144.7,135.5,131.1,130.1,127.7,127.4,126.7,
126.3,125.4,124.5,121.4,120.5,119.4,113.7,110.2,69.9,42.1,12.1.HRMS(ESI)m/z[M+Cl]-calcd.for C33H27ClNS2:536.1273,found:536.1278.
17.8min,tmajor=19.2min);[α]20D=+15.00(c 0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.56(s,
1H),7.51(dd,J=10.2,2.4Hz,1H),7.35(dd,J=6.8,2.9Hz,6H),7.17(t,J=5.2Hz,2H),
7.15-7.03(m,13H),6.85(td,J=9.0,2.5Hz,1H),4.77(s,1H),2.04(s,3H).13C NMR(101MHz,CDCl3)δ158.9,156.5,144.6,143.0,132.7,131.8,130.0,128.2,127.8,127.7,
126.6,126.2,110.6(d,J=10Hz),110.1,109.3(d,J=26Hz)105.5(d,J=24Hz),69.8,
46.6,12.5.19F NMR(377MHz,CDCl3)δ-122.75.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C35H28ClFNS:548.1615,found:548.1639.
15.2min);[α]20D=+89.99(c 0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.58(s,1H),7.51(s,
1H),7.37(dt,J=13.0,7.3Hz,6H),7.30(dd,J=10.9,4.2Hz,1H),7.18(d,J=7.2Hz,2H),
7.16-7.10(m,9H),7.05(dt,J=8.3,6.7Hz,3H),6.94(d,J=8.2Hz,1H),4.82(s,1H),2.47(s,3H),2.05(s,3H).13C NMR(101MHz,CDCl3)δ144.8,143.3,133.7,130.8,130.2,129.5,
128.5,128.1,127.9,127.7,126.6,125.9,122.8,120.1,113.6,109.9,69.7,46.821.8,
12.4.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C36H31ClNS:544.1866,found:
544.1885.
73.9min,tminor=78.7min);[α]20D=-0.8(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.80(s,
1H),7.40–7.35(m,6H),7.30-7.24(m,3H),7.17-7.08(m,14H),7.00-6.94(m,2H),4.76(s,
1H).13C NMR(101MHz,CDCl3)δ144.7,143.3,136.4,130.1,129.5,128.2,128.2,127.7,
126.6,126.4,123.4,122.1,119.9,119.4,118.0,111.08,69.4,47.1.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C34H27ClNS:516.1553,found:516.1571.
0.5mL/min,λ=254nm,tminor=15.8min,tmajor=36.1min);[α]20D=+95.59(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ8.16(d,J=7.7Hz,1H),7.86(s,1H),7.45(d,J=7.8Hz,1H),7.36-
7.21(m,7H),7.08-7.10(m,10H),7.03(dd,J=8.3,6.1Hz,3H),6.92-6.95(m,5H),6.87-
6.79(m,2H),4.91(s,1H).13C NMR(101MHz,CDCl3)δ144.6,142.9,136.5,135.6,132.5,
129.7,129.4,128.9,128.7,128.6,128.6,128.2,128.0,127.9,127.4,127.4,126.4,
126.1,122.6,122.5,120.0,113.9,111.0,69.845.9.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C40H31ClNS:592.1866,found:592.1893.
0.5mL/min,λ=254nm,tmajor=9.9min,tminor=14.7min);[α]20D=+198.79(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.82(d,J=7.1Hz,1H),7.57(s,1H),7.42(d,J=7.2Hz,6H),7.28-
7.10(m,12H),3.47(d,J=8.5Hz,1H),2.14(t,J=12.0Hz,1H),1.94(s,3H),1.16-1.01(m,
1H),0.86-0.96(m,1H),0.51(d,J=6.4Hz,3H),0.33(d,J=6.3Hz,3H).13C NMR(101MHz,CDCl3)δ145.3,135.9,130.4,130.1,127.7,126.5,121.2,120.4,119.2,113.3,110.3,
100.0,68.8,46.3,41.1,26.0,23.7,20.7,12.1.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C33H33ClNS:510.2022,found:510.2046
0.5mL/min,λ=254nm,tmajor=9.4min,tminor=15.3min);[α]20D=+219.38(c=0.5,CHCl3).1H NMR(400MHz,CDCl3)δ7.66(s,2H),7.50-7.42(m,6H),7.32-7.27(m,1H),7.25-7.14(m,
9H),7.14-7.05(m,2H),3.42(dd,J=11.6,4.0Hz,1H),2.08(s,3H),1.99-1.81(m,1H),
1.30–1.16(m,2H),0.88(dt,J=13.6,6.3Hz,2H),0.76(ddd,J=13.5,9.0,5.2Hz,1H),0.60(t,J=7.3Hz,3H).13C NMR(101MHz,CDCl3)δ145.3,130.8,130.1,129.4,128.0,128.0,
127.7,126.5,121.1,119.2,113.5,110.3,68.7,42.5,37.3,30.4,22.2,14.0,12.3.高分辨质谱{HRMS(ESI)m/z[M+Cl]-}计算为(calcd.for)C33H33ClNS:510.2022,found:510.2046.[0105]
stationary phase HPLC analysis using Daicel AD-H column);正己烷:异丙醇=97:3,流速为0.5毫升每分钟,检测波长为254纳米,主要峰的保留时间为90.2分钟,另一个对映体的保留时间为41.7分钟(n-hexane/i-PrOH 97:3at 0.3mL/min,λ=254nm,t minor=
41.7min,tmajor=90.2min);1H NMR(400MHz,CDCl3)δ7.42(d,J=7.3Hz,6H),7.29–7.09(m,
11H),7.09–6.94(m,3H),6.68(dd,J=13.1,7.1Hz,3H),6.44(d,J=7.7Hz,1H),3.75-3.62(m,1H),3.58(d,J=5.5Hz,1H),3.02–2.88(m,1H),0.91(d,J=6.6Hz,3H).13C NMR(101MHz,CDCl3)δ144.7,141.7,130.1,129.3,128.1,127.8,127.7,127.6126.8,126.7,126.1,
122.2,119.0,110.4,69.7,59.2,50.5,50.0,14.7.高分辨质谱{HRMS(ESI)m/z[M+Na]+}计算为(calcd.for)C35H31NNaS:520.2075,found:520.2086.
254nm,t minor=16.8min,t major=29.6min);1H NMR(400MHz,CDCl3)δ7.48-7.27(m,5H),
6.95(t,J=7.6Hz,1H),6.61(d,J=7.7Hz,1H),6.40(t,J=7.5Hz,1H),5.96(d,J=7.5Hz,
1H),4.25–4.13(m,2H),4.02(dd,J=11.5,7.2Hz,1H),2.02(d,J=5.4Hz,1H),1.30(d,J=
6.3Hz,3H).13C NMR(101MHz,CDCl3)δ150.9,144.5,129.1,128.7,128.4,127.8,127.5,
125.6,118.6,110.1,58.7,52.1,43.4,16.1.高分辨质谱{HRMS(ESI)m/z[M+Na]+}计算为(calcd.for)C16H18NS:256.1160,found:256.1162.