CN112457263A - 一种合成芳基砜衍生物的新方法 - Google Patents
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- 239000012043 crude product Substances 0.000 claims abstract description 27
- 150000001336 alkenes Chemical class 0.000 claims abstract description 19
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
本发明公开了一种合成芳基砜衍生物的新方法,该方法的合成过程为:在玻璃反应容器中,加入喹喔啉‑2(1H)‑酮类化合物、烯烃、芳基亚磺酸盐和氧化剂,以水做溶剂,在70℃条件下油浴反应24小时,粗产物经柱层析分离纯化后制得所述芳基砜衍生物。本发明发展了一种绿色的烯烃双官能团化反应,一步构建高度官能团化的芳基砜衍生物。该反应以水为溶剂且无需添加金属催化剂,符合绿色化学的发展需要。
Description
技术领域
本发明属于有机合成化学领域,具体涉及一种制备芳基砜类化合物的新方法。
背景技术
烯烃的双官能团化反应是向烯烃中同时引入两个官能团的重要方法,可增加分子的复杂性,具有重要的研究价值。目前,经过几十年的发展,烯烃的双官能团化反应取得了长足的进步,许多化合物被发展为烯烃双官能团化反应的合成子,如酰卤(C.-G.Li,et al,Org.Lett.,2017,19,512-515;S.-M.Xu,et al,Org.Chem.Front.,2017,4,1331-1335)、CF3SO2Na(L.Zou,et al,Green Chem.,2019,21,3362-3369)、羧酸(B.Du,et al,Adv.Synth.Catal.,2017,359,1684-1690)、硅烷(Y.Yang,et al,Angew.Chem.Int.Ed.,2017,56,7916-7919;J.Hou,et al,Angew.Chem.Int.Ed.,2018,57,17220-17224)、酰胺(Y.Ge,et al,Chem.Commun.,2020,56,12656-12659)和有机硼酸(Q.Liang,et al,ACSCatal.,2020,10,2633-2639;T.M.Perrone,et al,ChemCatChem,2019,11,5814-5820)等。然而烯烃的双官能团化反应通常需要金属催化剂和有机溶剂的参与,这样既增加了反应成本又增加了环境污染的风险,同时微量金属元素的去除限制了这些方法在医药领域的应用。因此,发展廉价、绿色的烯烃双官能团化反应具有重要的研究价值。
砜类化合物在医药化工领域具有重要的应用价值,许多砜类化合物不仅表现出优良的生物活性,而且能用作制备磺胺、硫醚等化合物的前体分子。目前,砜类化合物的合成方法有很多,但都存在一种或几种缺陷,如产率低、选择性不好、反应条件苛刻、添加金属催化剂等(Y.Wu,et al,Org.Lett.,2020,22,7164-7168;Y.Xiong,et al,Org.Lett.,2018,20,6250-6254;X.Meng,et al,Org.Lett.,2020,22,6827-6831;H.S.Dutta,et al,Adv.Synth.Catal.,2019,361,5534-5529;N.Meng,et al,J.Org.Chem.,2020,85,6888-6896;W.Wu,et al,Org.Lett.,2017,19,2825-2828),极大的限制了这些方法的应用。因此发展绿色实用的芳基砜类化合物的合成方法是亟待解决的科学问题。
在有机合成中,大量易燃、易挥发有机溶剂的使用给环境带来了很大危害。与传统溶剂相比,水作为有机反应溶剂具有独特的优势。首先,水具有安全、廉价、无毒、无污染等特点,契合现代绿色化学的理念;其次,由于大多数有机物在水中的溶解度较小,当反应本身冷却到室温时,反应产物可析出或分层,后处理过程极为简便。因此,水作为有机溶剂展现出了很好的前景。目前,以水为反应溶剂实现烯烃的双官能团化反应构建芳基砜衍生物的方法还没有报道。
发明内容
本发明的目的在于针对目前烯烃双官能团化反应和芳基砜衍生物合成方法的局限性,提供一种以水为反应溶剂实现烯烃的双官能团化反应构建芳基砜衍生物的新方法。
本发明思路:以烯烃、喹喔啉-2(1H)-酮、芳基亚磺酸盐为原料,以过硫酸钾为氧化剂,水为溶剂,在70℃条件下发生自由基加成反应,一步构建高度官能团化的芳基砜衍生物。该反应的官能团容忍性好、操作简便、产率优良、无需金属催化剂和有机溶剂的参与,符合绿色化学的要求。
本发明的目的通过如下技术方案实现。
一种合成芳基砜衍生物的新方法,包含如下操作步骤:
在玻璃反应容器中,按比例加入喹喔啉-2(1H)-酮类化合物、烯烃、芳基亚磺酸盐和氧化剂,以水做溶剂,在70℃~110℃条件下油浴反应12~48小时,粗产物经柱层析分离纯化后制得所述芳基砜衍生物。
进一步地,制备芳基砜衍生物的化学反应方程式如下所示:
式中,R1选自6,7-二甲基、6,7-二氯、6-溴、6-氟;
R2选自乙基、4-甲基苄基、4-叔丁基苄基、炔丙基、1-戊烯基中的一种以上;
R3选自苯基、2-氯苯基、3-氯苯基、4-氯苯基、4-氟苯基、4-叔丁基苯基、4-苯基苯基、4-甲氧基苯基、4-三氟甲基苯基、苄基、1-溴丁基、1-溴丙基中的一种以上;
R4选自4-甲基、4-苯基、4-氟、4-溴、4-三氟甲基、4-甲氧基、1-萘基、2-萘基、2-氯、3-氯、3-三氟甲基、3-溴、3,5-二氟、2-噻吩、5-溴-2-噻吩中的一种以上。
进一步地,所述氧化剂为过硫酸钾、TBHP(特丁基氢过氧化物)、TBPB(过氧化苯甲酸叔丁酯)、醋酸碘苯中的一种或一种以上,优选为过硫酸钾。
进一步地,所述氧化剂与喹喔啉-2(1H)-酮类化合物的投料摩尔比为1~3:1,优选为2:1。
进一步地,所述烯烃与喹喔啉-2(1H)-酮类化合物的投料摩尔比为1~2:1,优选为2:1。
进一步地,所述芳基亚磺酸盐与喹喔啉-2(1H)-酮类化合物的投料摩尔比为1~2:1,优选为2:1。
进一步地,所述溶剂为水、乙腈或水和乙腈的混合溶剂,优选为纯水为溶剂。
进一步地,所述芳基砜制备方法反应时间为12~48小时,优选反应24小时。
进一步地,所述芳基砜目标产物的纯化方法为柱层析,以二氯甲烷、乙酸乙酯与石油醚的混合溶剂为洗脱剂,乙酸乙酯和石油醚的体积比为1:2~20,或二氯甲烷和石油醚的体积比为10:1~3,优选乙酸乙酯与石油醚体积比为1:3的混合溶剂为展开剂。
本发明的原理为:以过硫酸钾为氧化剂,首先氧化芳基亚磺酸盐形成砜基自由基,砜基自由基进而与烯烃发生自由基加成反应,形成烷基自由基中间体,烷基自由基中间体进攻喹喔啉-2(1H)-酮衍生物的C3位,最后氧化脱氢得芳基砜衍生物。
与现有技术相比,本发明具有如下优点及有益效果:
(1)本发明实现了水相下烯烃、喹喔啉-2(1H)-酮和芳基亚磺酸盐的高效双官能团化反应,构建了一系列不易制备的芳基砜衍生物。此外,底物普适性好、选择性单一、操作简便等是反应的主要特点;
(2)本发明利用自由基对烯烃的加成反应一步完成了芳基砜衍生物的构建,具有较高的实用性和步骤经济性,为其大量的制备与应用提供了可能性。
附图说明
图1、图2是实施例1所得目标产物的氢谱和碳谱;
图3、图4是实施例2所得目标产物的氢谱和碳谱;
图5、图6是实施例3所得目标产物的氢谱和碳谱;
图7、图8是实施例4所得目标产物的氢谱和碳谱;
图9、图10是实施例5所得目标产物的氢谱和碳谱;
图11、图12是实施例6所得目标产物的氢谱和碳谱。
具体实施方式
下面通过具体实施例对本发明作进一步的描述,但本发明的保护范围及实施方式不限于此。
实施例1
在试管中依次加入0.3毫摩尔1-乙基喹喔啉-2(1H)-酮、0.6毫摩尔苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=3:1)。最后得到纯净的1-乙基-3-(1-苯基-2-(苯磺酰基)乙基)喹喔啉-2(1H)-酮,产率为82%。
所得目标产物的氢谱、碳谱如图1和图2所示,结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.86-7.77(m,3H),7.52(ddd,J=8.6,7.4,1.5Hz,1H),7.37-7.29(m,6H),7.23(dd,J=8.0,6.7Hz,3H),7.20-7.17(m,1H),5.31(dd,J=9.9,3.4Hz,1H),4.81(dd,J=14.4,9.9Hz,1H),4.24(m,J=14.4,7.1Hz,1H),4.15(m,J=13.9,7.1Hz,1H),3.67(dd,J=14.4,3.4Hz,1H),1.31(t,J=7.2Hz,3H);
13C NMR(125MHz,CDCl3)δ157.4,153.3,139.3,138.5,133.0,132.3,131.9,130.2,130.2,128.8,128.7,128.3,127.5,123.3,113.3,59.4,41.9,37.5,12.3;
HRMS(ESI)m/z:calcd for C24H22N2NaO3S[M+Na]+441.1244;found 441.1248.
经以上表征数据推断目标化合物的结构如下:
实施例2
在试管中依次加入0.3毫摩尔1-乙基喹喔啉-2(1H)-酮、0.6毫摩尔苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔2-氯苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=3:1)。最后得到纯净的3-(1-(2-氯苯基)-2-(苯磺酰基)乙基)-1-乙基喹喔啉-2(1H)-酮,产率为74%。
所得目标产物的氢谱、碳谱如图3和图4所示,结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.91(m,J=6.8,2.1Hz,2H),7.85(dd,J=8.0,1.4Hz,1H),7.55(ddd,J=8.6,7.4,1.5Hz,1H),7.45-7.28(m,6H),7.16-7.09(m,2H),7.05(td,J=7.5,1.3Hz,1H),5.76(dd,J=10.4,2.6Hz,1H),4.72(dd,J=14.5,10.5Hz,1H),4.29-4.15(m,2H),3.47(dd,J=14.5,2.6Hz,1H),1.32(t,J=7.2Hz,3H);
13C NMR(125MHz,CDCl3)δ156.7,153.5,139.3,136.1,134.2,133.25,132.3,132.1,130.5,130.3,129.0,128.9,128.7,128.5,126.9,123.4,113.5,58.5,38.4,37.6,12.4;
HRMS(ESI)m/z:calcd for C24H21ClN2NaO3S[M+Na]+475.0854;found 475.0856.
经以上表征数据推断目标化合物的结构如下:
实施例3
在试管中依次加入0.3毫摩尔1-乙基喹喔啉-2(1H)-酮、0.6毫摩尔苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔4-甲氧基苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=2:1)。最后得到纯净的1-乙基-3-(1-(4-甲氧基苯基)-2-(苯磺酰基)乙基)喹喔啉-2(1H)-酮,产率为63%。
所得目标产物的氢谱、碳谱如图5和图6所示,结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.88-7.78(m,3H),7.57-7.53(m,1H),7.39-7.27(m,7H),6.78(d,J=8.8Hz,2H),5.28(dd,J=9.7,3.7Hz,1H),4.78(dd,J=14.4,9.8Hz,1H),4.28(dd,J=13.9,7.1Hz,1H),4.17(dd,J=13.9,7.1Hz,1H),3.77(s,3H),3.68(dd,J=14.4,3.7Hz,1H),1.35(t,J=7.2Hz,3H);
13C NMR(125MHz,CDCl3)δ158.9,157.6,153.3,139.4,133.0,132.4,131.9,130.4,130.2,130.1,129.4,128.8,128.3,123.3,114.1,113.3,59.5,55.2,41.2,37.4,12.3;
HRMS(ESI)m/z:calcd for C25H24N2NaO4S[M+Na]+471.1349;found 471.1354.
经以上表征数据推断目标化合物的结构如下:
实施例4
在试管中依次加入0.3毫摩尔1-乙基喹喔啉-2(1H)-酮、0.6毫摩尔苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔4-三氟甲基苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=4:1)。最后得到纯净的1-乙基-3-(2-(苯磺酰基)-1-(4-三氟甲基苯基)乙基)喹喔啉-2(1H)-酮,产率为86%。
所得目标产物的氢谱、碳谱如图7和图8所示,结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.83-7.77(m,3H),7.57-7.53(m,1H),7.50-7.45(m,4H),7.32(m,J=20.3,18.8,11.2,7.8Hz,5H),5.38(dd,J=8.9,4.6Hz,1H),4.70(dd,J=14.5,8.9Hz,1H),4.30-4.21(m,1H),4.16(dd,J=13.9,7.1Hz,1H),3.74(dd,J=14.5,4.6Hz,1H),1.31(t,J=7.2Hz,3H);
13C NMR(125MHz,CDCl3)δ156.7,153.2,142.3,139.2,133.2,132.3,131.9,130.6,130.3,129.6(q,J=32.5Hz),128.9,128.8,128.1,125.6(q,J=3.8Hz),123.9(q,J=271.3Hz),123.5,113.4,59.0,41.9,37.5,12.2;
HRMS(ESI)m/z:calcd for C25H21F3N2NaO3S[M+Na]+509.1118;found 509.1121.
经以上表征数据推断目标化合物的结构如下:
实施例5
在试管中依次加入0.3毫摩尔1-乙基-6,7-二甲基喹喔啉-2(1H)-酮、0.6毫摩尔苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=4:1)。最后得到纯净的1-乙基-6,7-二甲基-3-(1-苯基-2-(苯磺酰基)乙基)喹喔啉-2(1H)-酮,产率为83%。
所得目标产物的氢谱、碳谱如图9和图10所示,结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.85-7.76(m,2H),7.54(s,1H),7.37-7.28(m,5H),7.17(m,J=25.6,7.2Hz,3H),6.97(s,1H),5.25(dd,J=9.7,3.6Hz,1H),4.76(dd,J=14.4,9.7Hz,1H),4.19(dq,J=14.3,7.2Hz,1H),4.09(m,J=14.2,7.2Hz,1H),3.64(dd,J=14.4,3.7Hz,1H),2.40(s,3H),2.35(s,3H),1.27(d,J=7.3Hz,5H);
13C NMR(125MHz,CDCl3)δ156.1,153.4,140.1,139.3,138.9,133.0,132.3,130.9,130.3,130.0,128.8,128.7,128.3,128.3,127.4,113.8,59.5,41.9,37.3,20.6,19.1,12.4;
HRMS(ESI)m/z:calcd for C26H26N2NaO3S[M+Na]+469.1557;found 469.1560.
经以上表征数据推断目标化合物的结构如下:
实施例6
在试管中依次加入0.3毫摩尔1-乙基-6-溴喹喔啉-2(1H)-酮、0.6毫摩尔苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=4:1)。最后得到纯净的6-溴-1-乙基-3-(1-苯基-2-(苯磺酰基)乙基)喹喔啉-2(1H)-酮,产率为76%。
所得目标产物的氢谱、碳谱如图11和图12所示,结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.92(d,J=2.3Hz,1H),7.84-7.80(m,2H),7.59(dd,J=8.9,2.3Hz,1H),7.41-7.31(m,5H),7.23–7.16(m,3H),7.10(d,J=8.9Hz,1H),5.29(dd,J=10.2,3.3Hz,1H),4.73(dd,J=14.4,10.2Hz,1H),4.20(dq,J=14.4,7.2Hz,1H),4.14-4.07(m,1H),3.61(dd,J=14.4,3.3Hz,1H),1.29(t,J=7.2Hz,3H);
13C NMR(125MHz,CDCl3)δ158.9,153.0,139.3,138.1,133.2,133.1,132.9,132.6,131.1,128.9,128.8,128.3,128.3,127.6,115.8,114.8,59.3,41.9,37.7,12.3;
HRMS(ESI)m/z:calcd for C24H21BrN2NaO3S[M+Na]+519.0349;found 519.0351.
经以上表征数据推断目标化合物的结构如下:
实施例7
在试管中依次加入0.3毫摩尔1-(4-甲基苄基)喹喔啉-2(1H)-酮、0.6毫摩尔苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=4:1)。最后得到纯净的1-(4-甲基苄基)-3-(1-苯基-2-(苯磺酰基)乙基)喹喔啉-2(1H)-酮,产率为77%。
所得目标产物的结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.88-7.83(m,2H),7.77(dd,J=8.0,1.4Hz,1H),7.42-7.37(m,3H),7.35-7.33(m,1H),7.30-7.24(m,5H),7.23-7.20(m,2H),7.11(q,J=8.2Hz,4H),5.47(d,J=15.5Hz,1H),5.37(dd,J=10.0,3.4Hz,1H),5.22(d,J=15.5Hz,1H),4.84(dd,J=14.4,10.0Hz,1H),3.69(dd,J=14.4,3.4Hz,1H),2.32(s,3H);
13C NMR(125MHz,CDCl3)δ157.6,154.1,139.3,138.5,137.5,133.1,132.4,132.3,132.0,130.2,130.1,129.5,128.9,128.8,128.3,128.3,127.5,127.0,1235,114.3,59.4,45.8,42.1,21.0;
HRMS(ESI)m/z:calcd for C30H26N2NaO3S[M+Na]+517.1557;found 517.1559.
经以上表征数据推断目标化合物的结构如下:
实施例8
在试管中依次加入0.3毫摩尔1-炔丙基喹喔啉-2(1H)-酮、0.6毫摩尔苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=4:1)。最后得到纯净的3-(1-苯基-2-(苯磺酰基)乙基)-1-炔丙基喹喔啉-2(1H)-酮,产率为80%。
所得目标产物的结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.82-7.79(m,2H),7.75(dd,J=8.0,1.3Hz,1H),7.57-7.52(m,1H),7.37-7.32(m,5H),7.29-7.27(m,3H),7.22(t,J=7.3Hz,2H),7.17(t,J=7.2Hz,1H),5.28(dd,J=10.1,3.2Hz,1H),5.05(dd,J=17.4,2.5Hz,1H),4.79-4.74(m,2H),3.63(dd,J=14.4,3.3Hz,1H),2.30(t,J=2.5Hz,1H);
13C NMR(125MHz,CDCl3)δ157.2,152.9,139.1,138.2,133.1,132.2,131.4,130.4,130.1,128.9,128.8,128.3,128.3,127.6,123.9,114.0,76.6,73.4,59.4,42.1,31.5;
HRMS(ESI)m/z:calcd for C25H20N2NaO3S[M+Na]+451.1087;found 451.1091.
经以上表征数据推断目标化合物的结构如下:
实施例9
在试管中依次加入0.3毫摩尔1-乙基喹喔啉-2(1H)-酮、0.6毫摩尔4-三氟甲基苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=4:1)。最后得到纯净的1-乙基-3-(1-苯基-2-((4-(三氟甲基)苯基)磺酰基)乙基)喹喔啉-2(1H)-酮,产率为83%。
所得目标产物的结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.92(d,J=8.2Hz,2H),7.72(dd,J=8.0,1.4Hz,1H),7.56-7.47(m,3H),7.33(ddd,J=15.3,8.3,1.3Hz,3H),7.25-7.16(m,4H),5.34(dd,J=9.7,3.8Hz,1H),4.80(dd,J=14.6,9.7Hz,1H),4.22(m,J=14.4,7.2Hz,1H),4.13(m,J=13.8,7.1Hz,1H),3.75(dd,J=14.6,3.9Hz,1H);
13C NMR(125MHz,CDCl3)δ156.9,153.1,142.8,137.9,134.5(q,J=32.5Hz),132.0,131.7,130.2(d,J=71.3Hz),128.9,128.8,128.3,127.6,125.7(q,J=3.8Hz),123.5,122.8(q,J=271.3Hz),113.4,59.3,42.0,37.4 12.1;
HRMS(ESI)m/z:calcd for C25H21F3N2NaO3S[M+Na]+509.1118;found 509.1123.
经以上表征数据推断目标化合物的结构如下:
实施例10
在试管中依次加入0.3毫摩尔1-乙基喹喔啉-2(1H)-酮、0.6毫摩尔4-甲氧基苯基亚磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=2:1)。最后得到纯净的1-乙基-3-(1-苯基-2-((4-甲氧基苯基)磺酰基)-1-苯基乙基)喹喔啉-2(1H)-酮,产率为76%。
所得目标产物的结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.79(dd,J=8.0,1.3Hz,1H),7.77-7.69(m,2H),7.55-7.50(m,1H),7.39-7.35(m,2H),7.34-7.30(m,1H),7.24(t,J=7.5Hz,3H),7.18(t,J=7.3Hz,1H),6.72-6.65(m,2H),5.27(dd,J=10.3,2.9Hz,1H),4.81(dd,J=14.3,10.4Hz,1H),4.25-4.10(m,2H),3.63(s,3H),3.62-3.59(m,1H),1.31(t,J=7.2Hz,3H);
13C NMR(125MHz,CDCl3)δ163.1,157.4,153.2,138.7,132.4,131.8,130.6,130.5,130.2,130.1,128.7,128.2,127.4,123.2,114.0,113.2,59.6,55.3,42.1,37.4,12.2;
HRMS(ESI)m/z:calcd for C25H24N2NaO4S[M+Na]+471.1349;found 471.1352.
经以上表征数据推断目标化合物的结构如下:
实施例11
在试管中依次加入0.3毫摩尔1-乙基喹喔啉-2(1H)-酮、0.6毫摩尔1-萘磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=4:1)。最后得到纯净的1-乙基-3-(2-(萘-1-磺酰基)-1-苯基乙基)喹喔啉-2(1H)-酮,产率为85%。
所得目标产物的结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ8.80(d,J=8.7Hz,1H),8.19(dd,J=7.3,1.0Hz,1H),7.67(m,J=3.7,3.1Hz,2H),7.55(d,J=8.1Hz,1H),7.41(ddd,J=15.6,11.8,4.3Hz,2H),7.30(t,J=7.7Hz,3H),7.21-7.07(m,6H),5.35(dd,J=10.3,2.7Hz,1H),5.05(dd,J=14.3,10.3Hz,1H),4.12-3.98(m,2H),3.76(dd,J=14.3,2.8Hz,1H),1.23(t,J=7.2Hz,3H);
13C NMR(125MHz,CDCl3)δ156.6,153.0,138.6,134.5,134.0,133.7,131.7,131.6,130.8,130.1,129.9,129.0,128.7,128.6,128.5,128.2,127.4,126.7,124.4,123.9,123.0,112.9,59.0,42.0,37.3,12.3;
HRMS(ESI)m/z:calcd for C28H24N2NaO3S[M+Na]+491.1400;found 491.1401.
经以上表征数据推断目标化合物的结构如下:
实施例12
在试管中依次加入0.3毫摩尔1-乙基喹喔啉-2(1H)-酮、0.6毫摩尔2-噻吩磺酸钠、0.6毫摩尔过硫酸钾、0.6毫摩尔苯乙烯,随后加入2毫升水,于70℃条件下搅拌反应,24小时后停止反应,冷却至室温并过滤,滤液用乙酸乙酯萃取3次,合并有机相并使用无水硫酸镁干燥,过滤并减压旋蒸得粗产物,最后经柱层析分离纯化,所用柱层析洗脱液为石油醚和乙酸乙酯的混合溶剂(石油醚:乙酸乙酯=4:1)。最后得到纯净的1-乙基-3-(1-苯基-2-(噻吩-2-磺酰基)乙基)喹喔啉-2(1H)-酮,产率为60%。
所得目标产物的结构表征数据如下所示:
1H NMR(500MHz,CDCl3)δ7.85(dd,J=8.0,1.0Hz,1H),7.62-7.60(m,1H),7.56-7.52(m,1H),7.45(dd,J=4.9,0.9Hz,1H),7.38(d,J=7.4Hz,2H),7.34(t,J=7.6Hz,1H),7.27(dd,J=8.8,3.7Hz,3H),7.20(t,J=7.3Hz,1H),6.92-6.87(m,1H),5.37(dd,J=9.7,3.4Hz,1H),4.90(dd,J=14.4,9.7Hz,1H),4.29(m,J=14.3,7.2Hz,1H),4.23-4.13(m,1H),3.75(dd,J=14.4,3.5Hz,1H),1.33(t,J=7.2Hz,3H);
13C NMR(125MHz,CDCl3)δ157.2,153.4,140.4,138.5,134.5,133.8,132.4,132.0,130.3,130.2,128.8,128.3,127.6,127.5,123.4,113.3,60.6,42.2,37.5,12.3;
HRMS(ESI)m/z:calcd for C22H20N2NaO3S2[M+Na]+447.0808;found 447.0809.
经以上表征数据推断目标化合物的结构如下:
上述实施方式为本发明方法的部分实施例,但这并不限制本发明的具体实施方式,其它的任何未背离本发明的精神实质与原理下所作的取代基替换、基本骨架改变、条件简化均应归属为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种合成芳基砜衍生物的新方法,其特征在于,包含如下步骤:
在玻璃反应容器中,加入喹喔啉-2(1H)-酮类化合物、烯烃、芳基亚磺酸盐和氧化剂,以水做溶剂,在70℃~110℃条件下油浴反应24小时,粗产物经柱层析分离纯化后制得所述芳基砜衍生物。
3.根据权利要求1或2所述的制备方法,其特征在于,所述氧化剂为过硫酸钾、TBHP(特丁基氢过氧化物)、TBPB(过氧化苯甲酸叔丁酯)、醋酸碘苯中的一种或一种以上;所述氧化剂与喹喔啉-2(1H)-酮类化合物的投料摩尔比为1~3:1。
4.根据权利要求1或2所述的制备方法,其特征在于,所述烯烃与喹喔啉-2(1H)-酮类化合物的投料摩尔比为1~2:1。
5.根据权利要求1或2所述的制备方法,其特征在于,所述芳基亚磺酸盐与喹喔啉-2(1H)-酮类化合物的投料摩尔比为1~2:1。
6.根据权利要求1或2所述的制备方法,其特征在于,所述溶剂为水、乙腈或水和乙腈的混合溶剂。
7.根据权利要求1或2所述的制备方法,其特征在于,所述芳基砜的制备方法反应时间为12~48小时。
8.根据权利要求1或2所述的制备方法,其特征在于,所述芳基砜目标产物的纯化方法为柱层析,以二氯甲烷、乙酸乙酯与石油醚的混合溶剂为洗脱剂。
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