CN116496201A - 一种氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法 - Google Patents

一种氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法 Download PDF

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CN116496201A
CN116496201A CN202310095824.0A CN202310095824A CN116496201A CN 116496201 A CN116496201 A CN 116496201A CN 202310095824 A CN202310095824 A CN 202310095824A CN 116496201 A CN116496201 A CN 116496201A
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余富朝
张明帅
陈龙坤
刘卓源
刘东汉
孙瑜琳
张志来
宋思雨
彭孟林
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Abstract

本发明公开了一种氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法，本发明在反应器中加入化合物1、化合物2、溶剂、催化剂、添加剂，在25～60℃的油浴锅中反应12.0h，薄层色谱监测反应进程，直至反应完全；然后用乙酸乙酯和水萃取3‑4次，收集合并有机相并用饱和食盐水洗涤，收集有机相后用无水硫酸钠干燥，减压蒸出溶剂，残渣用硅胶柱层析分离纯化得到1‑氮杂螺环[4.4]壬‑2‑烯‑4,6‑二酮类化合物和3a,7a‑二羟基‑六氢‑4H‑吲哚‑4‑酮类化合物；本发明具有收率高、分离方便，并具有高效性、温和性和低成本经济性，具有较大的工业化应用价值。

Description

一种氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备 方法
技术领域
本发明属于有机合成技术领域，具体涉及一种1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物和3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物的制备方法。
背景技术
螺环化合物是非常有价值的结构单元和重要的药效团，广泛存在于各种天然产物和药物中。此外，由于螺环碳原子的刚性结构，螺环化合物在光致变色、手性催化等方面也具有广阔的用途，比如不对称催化领域(Acc.Chem.Res.2018,41,581)表现出优异的催化性能。在传感和生物成像方面(Adv.Funct.Mater.2016,26,8128–8136)表现出良好的荧光特性和双光子特性。氮杂螺环酮类化合物是一类重要的医药和新药研发中间体，也是最重要的杂环骨架之一，它构成了许多天然生物碱和药物的核心结构。具有广泛的生物活性，例如抗菌、抗氧化(J.Org.Chem.2016,81,7898-7907)。因此，此类螺骨架的构建受到了化学家的广泛关注。
现有的合成氮杂螺环酮骨架的手段往往需要对底物进行预官能团化(引入卤素以及导向基团等)，增加了底物在合成上的难度，并且导向基团后期的脱除也限制了该类反应的进一步发展。这些合成手段所使用的底物一般需要多步合成，限制了所得骨架的多样性。如Shi课题组在2016年报道了，通过手性金鸡纳生物碱催化环烯胺酮、靛红和丙二腈的不对称三组分[3+3]环化构建了氮杂螺环酮骨架(J.Org.Chem.2016,81,7898-7907)，但还是存在许多不足，主要是底物范围不广、官能团耐受性不高的问题。2022年Xu课题组报道了以拟吲哚和α,β-不饱和硝基烯烃为原料，通过Rh催化的C-H活化/[3+2]螺环反应，构建氮杂螺环酮骨架(J.Org.Chem.2022,87,6179-6188)。但其合成存在着原料复杂、反应温度较高的问题。特别是构建1-氮杂螺环[4.4]壬-2-烯-4,6-二酮骨架的研究很少。
另一方面，吲哚酮类化合物同样是一类特殊骨架，广泛存在于大量天然产物和合成药物中。如藤黄碱(Sceletium tortuosum)，可作为血清素再摄取抑制剂；另一方面，在天然产物、药物、杀虫剂和其他生物活性分子中也发现了吲哚酮，它们具有抗肿瘤、抗高血压、抗过敏和其他出色的生物活性(Tetrahedron,2016,72,5314-5322.)。常见的吲哚酮类化合物的合成方法主要以茚三酮为原料来构建吲哚酮骨架。如，2012年，Hojatollah Jafaryan课题组报到的在无溶剂条件下，由茚三酮、伯胺和1，3-二羰基化合物反应一锅法构建吲哚酮(J.Heterocyclic Chem.,2012,49,217-220)。2014年Subbu Perumal课题组也报道了烯胺酮、苯胺和茚三酮以等摩尔比的三组分多米诺反应构建吲哚骨架(Green Chem.,2014,16,1297–1304)。而以碘鎓试剂作为合成原料却极其少见。此外由于吲哚骨架中苯或吡咯单位之间的选择性以及吲哚的过度还原，使得吲哚酮的合成更加的困难。近年来，通过金属和有机催化对喹胺的分子间环加成和分子内环加成构建氢化吲哚酮骨架类化合物也取得了一定的研究进展(Chem.Commun.,2021,57,8496–8499)，但仍然存在诸多的问题。
因此开发更加简捷、高效的合成手段用以解决现有氮杂螺环酮类化合物和吲哚酮类化合物在合成当中面临的底物合成复杂、官能团化受限、反应条件不够温和以及后期难以工业化等现实性等问题具有重大意义。据我们所知，到目前为止，通过简单易得的氮芳基烯胺酮化合物和碘鎓试剂化合物合成-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物和3a,7a-二羟基-六氢-4H-吲哚-4-酮类衍生物还未见专利和文献报道。
发明内容
为了解决现有技术不足，本发明提供了一种简单高效的氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法。
为解决上述技术问题，本发明采用的技术方案是：在反应器中加入化合物1、化合物2、溶剂、催化剂、添加剂，在25～60℃油浴条件下反应1～12h，薄层色谱监测反应进程，直至反应完全；然后用乙酸乙酯和水萃取3-4次，收集合并有机相并用饱和食盐水洗涤，收集有机相后用无水硫酸钠干燥，减压浓缩，残渣用硅胶柱层析分离纯化得到化合物3或化合物4，即3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物或1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物；
其中R1选自取代或未取代芳基、杂芳基、烷基、苯乙烯基；R2选自氢原子、甲基、苯基；R3选自氢原子、取代或未取代芳基、杂芳基、烷基、苄基；R4选自烷基、苯基；
或者R1和R2共价连接形成带有取代基的6元环；
所述化合物1与化合物2的摩尔比为1:1～4。
制备3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物时，催化剂选自二氯(五甲基环戊二烯基)合钌(III)二聚体、二氯(五甲基环戊二烯基)合铑(III)二聚体；制备1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物时，催化剂选自二氯(五甲基环戊二烯基)合铱(III)二聚体、二氯(五甲基环戊二烯基)合铑(III)二聚体，化合物1与催化剂的摩尔比为1:0.01～0.03；
制备3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物时，添加剂选自氧化银、碳酸银、三氧化钒银、六氟锑酸银、醋酸银、四氟硼酸银；制备1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物时，添加剂选自硝酸银、三氟乙酸银、氯化银、三氟甲磺酸银，氟化银；化合物1与添加剂的摩尔比为1:1～3
制备3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物时，溶剂选自1,4-二氧六环、二甲基亚砜、乙腈、甲苯、丙酮、二甲苯、乙酸乙酯、硝基甲烷；制备1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物时，溶剂为水与乙腈、甲苯、丙酮、乙酸乙酯、硝基甲烷、中的一种，化合物1与水的摩尔比为1:2～6。
所述化合物1按常规方法制备，例如参照Zheng B X,She M T,Long W,et al.Asmall-sized benzothiazole–indolium fluorescent probe:the study of interactionspecificity targeting c-MYC promoter G-quadruplex structures and live cellimaging.Chemical Communications,2020,56(95):15016-15019.文献中方法制得。
所述化合物2按常规方法制备，例如参照Moriarty R M,Tyagi S,Ivanov D,etal.The mechanism of 1,4alkyl group migration in hypervalent halonium ylides:The stereochemical course.Journal of the American Chemical Society,2008,130(24):7564-7565.文献方法制备。
本发明与现有技术相比，具有以下优点：
1、本发明合成的3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物或1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物是一类全新的杂环化合物；
2、原料广泛且简单易得，操作安全简便；
3、本发明的合成方法简洁高效，一步反应构建目标产物，反应条件温和，操作简便，环境友好，产率高等特点，克级反应收率良好，具有工业生产潜力；
4、所得目标产物化合物结构多样性丰富，对特殊结构的底物也能够适用；
附图说明
图1为化合物3f的单晶结构图；
图2为化合物4g的单晶结构图。
具体实施方式
下面通过实施例对本发明作进一步详细说明，但本发明保护范围不局限于所述内容，实施例中试剂如无特殊说明，均为常规市售试剂或按常规方法制得的试剂。
实施例1：
在15mL反应管中加入化合物1(E)-1-苯基-3-(对-甲苯氨基)-丙-2-烯-1-酮(0.5mmol)、Ag2O(0.75mmol)、二氯(五甲基环戊二烯基)合钌(III)二聚体(0.01mmol)，加入硝基甲烷(2mL)后加入化合物2 5,5-二甲基-2-(苯基-λ3-碘烷基)环己烷-1,3-二酮(1mmol)，在磁力搅拌下加热至40℃反应12h；TLC监测反应，待原料点完全消失后，然后用乙酸乙酯和水萃取3次，收集合并有机相并用饱和食盐水洗涤，收集有机相后有机相用无水Na2SO4进行干燥，将经过干燥的液体浓缩蒸干，之后对浓缩蒸干物进行硅胶柱层析分离，柱色谱分离采用的溶剂为石油醚/乙酸乙酯的混合溶剂，收集洗脱液干燥，得白色固体3a，收率84％，反应如下：
产品3a的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；白色固体:165mg,产率84％；熔点＝147–148℃；1H NMR(600MHz,DMSO-d6)δ＝7.66(s,3H,ArH and C＝CH),7.49(d,J＝35.4Hz,3H,ArH),7.34(s,2H,ArH),7.14(s,2H,ArH,ArH),6.43(s,1H,OH),5.56(s,1H,OH),2.61(s,1H,CH2),2.27(s,3H,ArCH3),2.16–1.90(m,3H,CH2),0.98(s,3H,CH3),0.84(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.6,187.5,150.3,139.9,136.5,134.4,131.2,129.9,129.9,128.8,128.1,128.6,128.6,121.9,121.9,118.5,102.9,83.5,51.3,48.1,35.4,32.0,25.7,20.9；HRMS(TOF ES+):m/zcalcd for C24H25NO4[(M+H)+],392.1856,found,392.1861.
下述实施例制备方法同实施例1；
实施例2：不同在于化合物1为(E)-1-(4-(甲基磺酰基)苯基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品3b的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1Rf＝0.2；黄色固体:146mg,产率62％；熔点＝142–143℃；1H NMR(600MHz,DMSO-d6)δ＝7.99(d,J＝7.9Hz,2H,ArH),7.88(d,J＝7.9Hz,2H,ArH),7.76(s,1H,C＝CH),7.37(d,J＝8.0Hz,2H,ArH),7.15(d,J＝8.0Hz,2H,ArH),6.49(s,1H,OH),5.64(s,1H,OH),3.26(s,3H,CH3),2.64(d,J＝12.0Hz,1H,CH2),2.27(s,3H,ArCH3),2.15(d,J＝11.6Hz,1H,CH2),2.07(d,J＝14.3Hz,1H,CH2),1.95(d,J＝14.2Hz,1H,CH2),0.99(s,3H,CH3),0.84(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.48,186.01,151.44,144.41,142.47,136.21,134.80,129.86,129.40,127.56,122.12,118.22,103.26,83.27,51.24,48.09,43.87,35.45,31.98,25.70,20.89；HRMS(TOF ES+):m/z calcd for C25H27NO6S[(M+H)+],470.1632,found,470.1644.
实施例3：不同在于化合物1为(E)-1-(4-溴苯基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品3c的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；黄色固体:189mg,产率80％；熔点＝157–158℃；1H NMR(600MHz,DMSO-d6)δ＝7.73(s,1H,C＝CH),7.67–7.59(m,4H,ArH),7.36(d,J＝7.8Hz,2H,ArH),7.15(d,J＝8.1Hz,2H,ArH),6.45(s,1H,OH),5.58(s,1H,OH),2.62(d,J＝11.7Hz,1H,CH2),2.27(s,3H,ArCH3),2.14(d,J＝12.0Hz,1H,CH2),2.06(d,J＝14.3Hz,1H,CH2),1.93(d,J＝14.2Hz,1H,CH2),0.98(s,3H,CH3),0.84(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.6,186.3,150.7,139.0,136.4,134.6,131.8,131.8,130.7,130.7,129.9,129.9,124.7,121.9,121.9,118.2,103.0,83.4,51.2,48.1,35.4,32.0,25.7,20.9；HRMS(TOF ES+):m/z calcd for C24H24BrNO4[(M+H)+],470.0961,found,470.0967.
实施例4：不同在于化合物1为(E)-1-(萘-2-基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品3d的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:158mg,产率71％；熔点＝119–120℃；1H NMR(600MHz,DMSO-d6)δ8.31(s,1H),8.11(d,J＝7.8Hz,1H,ArH),8.00–7.96(m,2H,ArH),7.84(s,1H,C＝CH),7.72(d,J＝8.4Hz,1H,ArH),7.62–7.57(m,2H,ArH),7.37(d,J＝7.4Hz,2H,ArH),7.14(d,J＝7.4Hz,2H,ArH),6.45(s,1H,OH),5.62(s,1H,OH),2.69(d,J＝11.7Hz,1H,CH2),2.27(s,3H,ArCH3),2.19(d,J＝11.8Hz,1H,CH2),2.09(d,J＝14.1Hz,1H,CH2),1.98(d,J＝14.0Hz,1H,CH2),1.02(s,3H,CH3),0.87(s,3H,CH3)；13C NMR(151MHz,DMSO-d6)δ206.7,187.5,150.7,137.2,136.6,134.5,134.4,132.7,129.9,129.9,129.6,128.8,128.4,128.0,127.9,127.0,125.7,121.9,121.9,118.7,103.0,83.6,51.3,48.1,35.5,32.1,25.7,20.9；HRMS(TOF ES+):m/z calcd for C28H27NO4[(M+H)+],442.2013,found,442.2022.
实施例5：不同在于化合物1为(E)-1-(4-甲氧基苯基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品3e的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:173mg,产率82％；熔点＝97–98℃；1H NMR(600MHz,DMSO-d6)δ＝7.69(d,J＝7.4Hz,2H,ArH),7.67(s,1H,C＝CH),7.36(d,J＝8.0Hz,2H,ArH),7.15(d,J＝8.0Hz,2H,ArH),7.00(d,J＝8.2Hz,2H,ArH),6.39(s,1H,OH),5.52(s,1H,OH),3.82(s,3H,ArOCH3),2.61(d,J＝11.8Hz,1H,CH2),2.28(s,3H,ArCH3),2.15(d,J＝11.9Hz,1H,CH2),2.04(d,J＝14.3Hz,1H,CH2),1.90(d,J＝14.3Hz,1H,CH2),0.98(s,3H,CH3),0.84(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.65,186.50,161.87,149.45,136.71,134.17,132.33,130.65,130.65,129.88,129.88,121.71,121.71,118.55,114.03,114.03,102.65,83.65,55.76,51.29,48.02,35.36,32.05,25.73,20.88；HRMS(TOF ES+):m/z calcd for C25H27NO5[(M+H)+],422.1962,found,422.1965.
实施例6：不同在于化合物1为(E)-1-(4-硝基苯基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品3f的结构、形态、熔点、核磁、高分辨质谱数据如下,化合物3f的单晶结构图见图1；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；黄色固体:171mg,产率78％；熔点＝168–169℃；1H NMR(600MHz,DMSO-d6)δ＝8.29(d,J＝8.2Hz,2H,ArH),7.89(d,J＝8.3Hz,2H,ArH),7.78(s,1H,C＝CH),7.38(d,J＝8.1Hz,2H,ArH),7.16(d,J＝8.0Hz,2H,ArH),6.53(s,1H,OH),5.68(s,1H,OH),2.66(d,J＝11.8Hz,1H,CH2),2.28(s,3H,ArCH3),2.16(d,J＝11.7Hz,1H,CH2),2.09(d,J＝14.2Hz,1H,CH2),1.97(d,J＝14.0Hz,1H,CH2),1.01(s,3H,CH3),0.86(s,3H,CH3)；13CNMR(150MHz,DMSO-d6)δ＝206.43,185.57,151.66,148.82,145.77,136.15,134.87,129.86,129.86,129.86,129.86,124.03,124.03,122.09,122.09,118.25,103.36,83.21,51.25,48.09,35.43,31.95,25.70,20.89；HRMS(TOF ES+):m/z calcd for C24H24N2O6[(M+H)+],437.1707,found,437.1720.
实施例7：不同在于化合物1为(E)-1-(噻吩-2-基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品3g的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:159mg,产率80％；熔点＝159–160℃；1H NMR(600MHz,DMSO-d6)δ＝8.10(s,1H,C＝CH),7.88(d,J＝3.8Hz,1H,C＝CH),7.82(d,J＝5.0Hz,1H,C＝CH),7.42(d,J＝8.1Hz,2H,ArH),7.19(s,1H,C＝CH),7.17(t,J＝4.1Hz,2H,ArH),6.43(s,1H,OH),5.54(s,1H,OH),2.59(d,J＝11.9Hz,1H,CH2),2.29(s,3H,ArCH3),2.14(d,J＝11.7Hz,1H,CH2),2.04(d,J＝14.2Hz,1H,CH2),1.90(d,J＝13.7Hz,1H,CH2),0.97(s,3H,CH3),0.83(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.5,178.2,149.0,144.6,136.6,134.5,131.8,130.8,129.9,129.9,128.6,122.1,122.1,118.0,102.6,83.7,51.2,48.1,35.4,32.1,25.7,20.9；HRMS(TOF ES+):m/z calcd for C22H23NO4S[(M+H)+],398.1421,found,398.1427.
实施例8：不同在于化合物1为(E)-1-(呋喃-2-基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品3h的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:156mg,产率81％；熔点＝179–180℃；1H NMR(600MHz,DMSO-d6)δ＝8.31(s,1H,C＝CH),7.88(s,1H,C＝CH),7.40(d,J＝8.0Hz,2H,C＝CH),7.20(d,J＝8.0Hz,2H,ArH),7.16(d,J＝3.5Hz,1H,ArH),6.65(s,1H,ArH),6.45(s,1H,OH),5.51(s,1H,OH),2.58(d,J＝11.9Hz,1H,CH2),2.30(s,3H,ArCH3),2.13(d,J＝10.8Hz,1H,CH2),2.03(d,J＝14.2Hz,1H,CH2),1.86(d,J＝14.0Hz,1H,CH2),0.96(s,3H,CH3),0.82(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.56,173.09,153.22,149.43,146.11,136.48,134.73,130.02,130.02,122.06,122.06,117.88,115.70,112.36,102.46,83.46,51.13,48.09,35.55,32.03,25.66,20.91；HRMS(TOF ES+):m/z calcd for C22H23NO5[(M+H)+],382.1649,found,382.1659.
实施例9：不同在于化合物1为(E)-1-((1r，3r，5r，7r)-金刚烷-2-基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品3i的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；白色固体:150mg,产率67％；熔点＝194–195℃；1H NMR(600MHz,DMSO-d6)δ＝8.05(s,1H,C＝CH),7.31(d,J＝8.0Hz,2H,ArH),7.17(d,J＝8.0Hz,2H,ArH),6.15(s,1H,OH),5.14(s,1H,OH),2.37(d,J＝11.6Hz,1H,CH2),2.28(s,3H,ArCH3),2.06(d,J＝13.0Hz,1H,CH2),1.98–1.94(m,4H,CH2 and CH),1.89–1.85(m,6H,CH2),1.74(d,J＝11.9Hz,3H,CH),1.69–1.64(m,4H,CH2),0.94(s,3H,CH3),0.79(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.90,198.37,146.29,136.74,134.06,129.84,129.84,122.02,122.02,117.59,101.02,84.45,50.97,48.00,45.20,36.60,36.60,36.60,36.60,35.78,32.26,28.37,28.37,28.37,28.37,28.37,25.55,20.88；HRMS(TOF ES+):m/z calcd forC28H35NO4[(M+H)+],450.2639,found,450.2636.
实施例10：不同在于化合物1为(1E，4E)-1-苯基-5-(对甲苯基氨基)戊-1,4-二烯-3-酮，所得产品3j的结构、形态、熔点、红外、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；黄色固体:173mg,产率83％；熔点＝197–198℃；1H NMR(600MHz,DMSO-d6)δ＝8.65(s,1H,C＝CH),7.78(d,J＝7.4Hz,2H,ArH),7.66(d,J＝15.5Hz,1H,C＝CH),7.48(s,1H,ArH),7.47(s,1H,C＝CH),7.43(t,J＝7.4Hz,2H,ArH),7.41–7.38(m,2H,ArH),7.22(d,J＝8.1Hz,2H,ArH),6.45(s,1H,OH),5.48(s,1H,OH),2.54(d,J＝12.0Hz,1H,CH2),2.31(s,3H,ArCH3),2.14–2.09(m,2H,CH2),1.80(d,J＝14.0Hz,1H,CH2),0.96(s,3H,CH3),0.84(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.7,180.8,148.7,138.7,136.8,135.8,134.1,130.0,129.9,129.9,129.2,129.2,128.7,128.7,124.0,122.0,121.1,121.1,103.1,83.1,51.2,48.1,35.6,32.0,25.7,20.9；HRMS(TOF ES+):m/zcalcd for C26H27NO4[(M+H)+],418.2013,found,418.2028.
实施例11：不同在于化合物1为(E)-1-苯基-3-(对甲苯基氨基)丁-2-烯-1-酮，所得产品3k的结构、形态、熔点、红外、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；黄色油状物:142mg,产率70％；1H NMR(600MHz,DMSO-d6)δ＝7.51–7.48(m,2H,ArH),7.46–7.43(m,1H,ArH),7.40(t,J＝7.1Hz,2H,ArH),7.24(q,J＝8.3Hz,4H,ArH),5.93(s,1H,OH),5.27(s,1H,OH),2.64(d,J＝11.6Hz,1H,CH2),2.32(s,3H,ArCH3),2.16(d,J＝13.5Hz,1H,CH2),2.06(d,J＝9.4Hz,1H,CH2),1.72(d,J＝15.9Hz,1H,CH2),1.45(s,3H,CH3),1.03(s,3H,CH3),0.75(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝207.43,189.50,161.51,142.72,137.92,133.30,130.34,130.00,130.00,129.76,129.76,128.57,128.57,127.80,127.80,115.18,100.63,84.31,50.99,47.76,35.15,32.21,25.55,21.12,16.51；HRMS(TOF ES+):m/z calcd for C25H27NO4[(M+H)+],406.2013,found,406.2013.
实施例12：不同在于化合物1为(E)-3-氨基-1,3-二苯基丙-2-烯-1-酮，所得产品3l的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；黄色固体:125mg,产率66％；熔点＝214–215℃；1H NMR(600MHz,DMSO-d6)δ＝10.15(s,1H,NH),7.58(t,J＝8.1Hz,3H,ArH),7.52(d,J＝7.4Hz,2H,ArH),7.48(d,J＝8.1Hz,3H,ArH),7.39(t,J＝7.8Hz,2H,ArH),2.48(s,1H,CH2),2.39(d,J＝14.1Hz,1H,CH2),2.24(d,J＝16.3Hz,1H,CH2),2.18(d,J＝14.0Hz,1H,CH2),1.24(s,3H,CH3),1.12(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝208.0,193.5,189.4,180.8,139.2,132.5,132.3,130.5,129.5,129.5,129.0,129.0,128.9,128.9,128.4,128.4,107.6,79.6,52.5,46.3,33.8,29.3,29.2；HRMS(TOF ES+):m/z calcd for C23H23NO4[(M+H)+],378.1700,found,378.1702.
实施例13：不同在于化合物1为5,5-二甲基-3-(对甲苯基氨基)环己-2-烯-1-酮，所得产品3m的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；白色固体:116mg,产率65％；熔点＝183–184℃；1H NMR(600MHz,DMSO-d6)δ＝7.24(q,J＝8.1Hz,4H,ArH),6.11(s,1H,OH),5.35(s,1H,OH),2.54(s,1H,CH2),2.49(s,1H,CH2),2.32(s,3H,ArCH3),2.22(d,J＝15.9Hz,1H,CH2),2.07(d,J＝11.5Hz,1H,CH2),1.89(t,J＝15.4Hz,3H,CH2),1.68(d,J＝13.7Hz,1H,CH2),1.00(s,3H,CH3),0.95(s,3H,CH3),0.90(s,3H,CH3),0.73(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝207.6,189.1,165.7,137.2,133.6,129.8,129.8,128.8,128.8,112.5,102.8,81.2,51.1,50.4,48.2,37.6,34.7,34.3,32.0,29.9,26.9,25.4,21.1；HRMS(TOF ES+):m/z calcd forC23H29NO4[(M+H)+],384.2169,found,384.2171.
实施例14：不同在于化合物1为(E)-3-(苄氨基)-1-苯基丙-2-烯-1-酮，所得产品3n的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；白色固体:141mg,产率72％；熔点＝145–146℃；1H NMR(600MHz,DMSO-d6)δ＝7.49(s,1H,ArH),7.48(s,1H,C＝CH),7.45(d,J＝7.1Hz,1H,ArH),7.40(d,J＝7.3Hz,2H,ArH),7.37–7.33(m,5H,ArH),7.28(d,J＝6.8Hz,1H,ArH),5.82(s,1H,OH),5.36(s,1H,OH),4.52–4.40(m,2H,CH2),2.58(d,J＝11.8Hz,1H,CH2),2.11(d,J＝11.6Hz,1H,CH2),2.01(d,J＝14.0Hz,1H,CH2),1.77(d,J＝14.0Hz,1H,CH2),0.98(s,3H,CH3),0.82(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝207.3,186.1,154.3,140.5,138.3,130.7,129.0,129.0,128.7,128.7,128.6,128.6,128.2,128.2,127.9,115.6,101.2,83.2,51.2,48.0,46.4,35.3,32.1,25.7；HRMS(TOF ES+):m/z calcd for C24H25ClNO4[(M+H)+],392.1856,found,392.1857.
实施例15：不同在于化合物1为(E)-1-苯基-3-((3,4,5-三甲氧基苯基)氨基)丙-2-烯-1-酮，所得产品3o的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；白色固体:196mg,产率84％；熔点＝177–178℃；1H NMR(600MHz,DMSO-d6)δ＝7.69(s,1H,C＝CH),7.67(d,J＝7.7Hz,2H,ArH),7.53(t,J＝7.4Hz,1H,ArH),7.46(t,J＝7.5Hz,2H,ArH),6.80(s,2H,ArH),6.49(s,1H,OH),5.57(s,1H,OH),3.76(s,6H,ArCH3),3.63(s,3H,ArCH3),2.62(d,J＝11.7Hz,1H,CH2),2.16(d,J＝11.7Hz,1H,CH2),1.96(dd,J＝31.2,13.9Hz,2H,CH2),1.00(s,3H,CH3),0.83(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.8,187.4,153.2,151.2,139.9,135.8,134.9,131.4,128.8,128.8,128.8,128.8,128.8,128.8,118.2,103.1,101.7,83.5,60.5,56.6,56.6,51.4,47.9,35.4,32.1,25.7；HRMS(TOF ES+):m/z calcd for C26H29NO7[(M+H)+],468.2017,found,468.2023.
实施例16：不同在于化合物1为(E)-1-苯基-3-(丙氨基)丙-2-烯-1-酮，所得产品3p的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色油状物:86mg,产率50％；1H NMR(600MHz,DMSO-d6)δ＝7.53–7.51(m,2H,ArH),7.47(d,J＝7.2Hz,1H,ArH),7.43(d,J＝7.6Hz,2H,ArH),7.41(s,1H,C＝CH),5.75(s,1H,OH),5.25(s,1H,OH),3.25–3.22(m,2H,CH2),2.58(d,J＝12.0Hz,1H,CH2),2.11–2.07(m,2H,CH2),1.74(d,J＝13.7Hz,1H,CH2),1.57–1.53(m,2H,CH2),1.02(s,3H,CH3),0.88(t,J＝7.4Hz,3H,CH3),0.83(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝207.5,185.7,154.4,140.7,130.5,128.6,128.6,128.2,128.2,114.9,101.1,83.3,51.1,48.0,43.0,35.4,32.3,25.7,20.0,14.1；HRMS(TOF ES+):m/z calcd for C20H25NO4[(M+H)+],344.1856,found,344.1861.
实施例17：不同在于化合物1为(E)-4-(萘-2-基)-1-苯基丁-2-烯-1-酮，所得产品3q的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:176mg,产率82％；熔点＝107–108℃；1H NMR(600MHz,DMSO-d6)δ＝8.11(s,1H,ArH),7.97(s,2H,ArH),7.66(s,1H,C＝CH),7.66–7.60(m,3H,ArH),7.59–7.54(m,3H,ArH),7.46(d,J＝7.2Hz,1H,ArH),7.41(d,J＝7.4Hz,2H,ArH),6.14(s,1H,OH),5.68(s,1H,OH),2.75(d,J＝11.8Hz,1H,CH2),2.35(d,J＝13.9Hz,1H,CH2),2.19(d,J＝11.8Hz,1H,CH2),1.94(d,J＝14.0Hz,1H,CH2),1.05(s,3H,CH3),0.79(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.9,187.1,155.1,140.0,134.9,134.5,131.0,128.70,128.7,128.7,128.6,128.5,128.5,128.5,128.4,127.2,126.8,126.6,126.0,117.6,104.0,83.5,51.4,47.9,35.4,32.2,25.5；HRMS(TOF ES+):m/z calcd forC27H25NO4[(M+H)+],428.1856,found,428.1858.
实施例18：不同在于化合物1为(E)-3-(环己基氨基)-1-苯基丙-2-烯-1-酮，所得产品3r的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；黄色油状物:100mg,产率52％；1H NMR(600MHz,DMSO-d6)δ＝7.51–7.49(m,2H,ArH),7.46(d,J＝7.1Hz,1H,ArH),7.44(s,2H,ArH),7.43(s,1H,C＝CH),5.80(s,1H,OH),5.22(s,1H,OH),2.58(d,J＝11.8Hz,1H,CH2),2.10(t,J＝11.1Hz,2H,CH2),1.85(d,J＝11.2Hz,1H,CH2),1.77–1.70(m,4H,CH2),1.55(d,J＝10.1Hz,1HC-CH),1.37–1.19(m,4H,CH2),1.18–1.08(m,2H,CH2),1.02(s,3H,CH3),0.82(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝207.5,185.6,151.2,140.7,130.5,128.7,128.7,128.2,128.2,114.9,101.6,83.4,52.0,51.1,48.6,35.4,34.3,33.7,32.2,25.9,25.9,25.6,25.0；HRMS(TOF ES+):m/z calcd for C23H29NO4[(M+H)+],384.2169,found,384.2168.
实施例19：不同在于化合物1为(E)-3-((2-氯苯基)氨基)-1-苯基丙-2-烯-1-酮，所得产品3s的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:100mg,产率49％；熔点＝77–78℃；1H NMR(600MHz,DMSO-d6)δ＝7.75(s,1H,C＝CH),7.68(d,J＝7.1Hz,2H,ArH),7.54(t,J＝7.3Hz,1H,ArH),7.48(d,J＝6.3Hz,4H,ArH),7.39(d,J＝8.9Hz,2H,ArH),6.56(s,1H,OH),5.62(s,1H,OH),2.61(d,J＝12.0Hz,1H,CH2),2.18–2.14(m,2H,CH2),1.95(d,J＝14.2Hz,1H,CH2),0.99(s,3H,CH3),0.85(s,3H,CH3)；13C NMR(151MHz,DMSO-d6)δ＝206.4,187.9,149.5,139.6,138.0,131.5,129.3,129.3,128.9,128.9,128.8,128.7,128.7,122.7,122.7,119.4,103.0,83.5,51.3,47.9,35.5,32.0,25.7；HRMS(TOF ES+):m/z calcd forC24H22F3NO4[(M+H)+],412.1310,found,412.1316.
实施例20：不同在于化合物2为5-苯基-2-(苯基-λ3-碘烷基)环己烷-1,3-二酮，所得产品3t的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:165mg,75％；熔点＝100–101℃；1H NMR(600MHz,DMSO-d6)δ＝7.76(s,1H,ArH),7.75(s,1H,C＝CH),7.55(t,J＝7.4Hz,1H,ArH),7.50(d,J＝7.3Hz,3H,ArH),7.35(d,J＝8.1Hz,2H,ArH),7.29(d,J＝7.1Hz,3H,ArH),7.22(d,J＝7.3Hz,1H,ArH),7.16(d,J＝6.1Hz,1H,ArH),7.12(d,J＝8.0Hz,2H,ArH),6.76(s,1H,OH),5.65(s,1H,OH),3.06–2.96(m,1H,C-CH),2.94–2.88(m,2H,CH2),2.54(d,J＝12.8Hz,1H,CH2),2.29(d,J＝14.9Hz,1H,CH2),2.24(s,3H,ArCH3)；13C NMR(150MHz,DMSO-d6)δ＝205.9,187.6,150.6,143.1,139.8,136.5,134.4,131.3,129.9,129.9,129.1,129.1,128.8,128.8,128.7,128.7,127.2,127.2,123.0,121.8,121.8,118.4,102.1,83.9,45.9,44.3,44.2,20.9；HRMS(TOF ES+):m/z calcd for C28H25NO4[(M+H)+],440.1856,found,440.1868.
实施例21：不同在于化合物2为2-(苯基-λ3-碘烷基)环庚烷-1,3-二酮，所得产品3u的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色油状物:80mg,产率42％；1H NMR(600MHz,DMSO-d6)δ＝7.78(s,1H,C＝CH),7.67(d,J＝7.3Hz,2H,ArH),7.53(d,J＝8.4Hz,1H,ArH),7.48–7.45(m,4H,ArH),7.16(d,J＝8.0Hz,2H,ArH),6.59(s,1H,OH),5.74(s,1H,OH),2.38–2.34(m,2H,CH2),2.27(s,3H,ArCH3),1.72–1.67(m,2H,CH2),1.44–1.38(m,2H,CH2),1.18(d,J＝7.2Hz,2H,CH2)；13C NMR(150MHz,DMSO-d6)δ＝209.8,187.3,152.3,134.0,137.0,135.0,131.4,130.1,130.1,128.6,128.6,128.2,128.2,122.6,122.6,116.5,95.4,87.6,36.0,26.7,22.1,20.9,14.6；HRMS(TOF ES+):m/z calcd for C23H23NO4[(M+H)+],378.1700,found,378.1706.
实施例22：不同在于化合物2为4,4-二甲基-2-(苯基-λ3-碘烷基)环己烷-1,3-二酮，所得产品3v的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色油状物:151mg,产率77％；1H NMR(600MHz,DMSO-d6)δ＝7.80(s,1H,C＝CH),7.59(d,J＝7.1Hz,2H,ArH),7.50(d,J＝7.2Hz,1H,ArH),7.46(d,J＝7.7Hz,2H,ArH),7.43(d,J＝8.3Hz,2H,ArH),7.17(d,J＝8.1Hz,2H,ArH),6.68(s,1H,OH),5.47(s,1H,OH),2.28(s,3H,CH3),2.05–2.01(m,1H,CH2),1.75(d,J＝12.6Hz,1H,CH2),1.52–1.45(m,2H,CH2),1.08(s,6H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝212.1,188.0,152.2,140.5,135.0,131.1,130.1,130.1,128.9,128.9,128.3,128.3,122.5,122.5,119.5,115.6,99.8,84.3,44.1,32.2,30.9,27.3,26.4,20.9；HRMS(TOF ES+):m/z calcdfor C24H25NO4[(M+H)+],392.1856,found,392.1857.
实施例23
在15mL厚壁耐压管中加入化合物1(0.5mmol)、AgNO3(0.5mmol)、二氯(五甲基环戊二烯基)合铑(III)二聚体(0.0125mmol)、H2O(1.5mmol)，加入硝基甲烷(2mL)后加入化合物2(0.75mmol)，在磁力搅拌下加热至40℃下反应12h；TLC监测反应，待原料点完全消失后，然后用乙酸乙酯萃取3次，收集合并有机相并用饱和食盐水洗涤，收集有机相后有机相用无水Na2SO4进行干燥，将经过干燥的液体浓缩蒸干，之后对浓缩蒸干物进行硅胶柱层析分离，柱色谱分离采用的溶剂为石油醚/乙酸乙酯的混合溶剂，收集洗脱液干燥，得黄色固体4a，收率83％，反应方程式如下：
产品4a的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色固体:155mg,产率83％；熔点＝135–136℃；1H NMR(600MHz,CDCl3)δ＝8.83(s,1H,C＝CH),7.78(d,J＝7.7Hz,2H,ArH),7.51(t,J＝7.4Hz,1H,ArH),7.43(t,J＝7.6Hz,2H,ArH),7.24(d,J＝8.0Hz,2H,ArH),7.16(d,J＝7.9Hz,2H,ArH),2.87(d,J＝16.6Hz,1H,CH2),2.51(d,J＝14.6Hz,1H,CH2),2.39(s,3H,ArCH3),2.18–2.09(m,2H,CH2),1.30(s,3H,CH3),0.66(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.9,191.6,188.2,171.1,139.6,138.4,135.5,132.1,130.4,130.4,129.0,129.0,128.0,128.0,126.3,126.3,111.6,88.0,51.0,43.2,32.8,29.8,29.7,21.2；HRMS(TOF ES+):m/z calcdfor C24H23NO3[(M+H)+],374.1751,found,374.1754.
下述实施例制备方法同实施例23；
实施例24：不同在于化合物1为(E)-1-联苯基-3-(对-甲苯氨基)-丙-2-烯-1-酮，所得产品4b的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色固体:155mg,产率73％；熔点＝190–191℃；1H NMR(600MHz,CDCl3)δ＝8.88(s,1H,C＝CH),7.92–7.85(m,2H,ArH),7.68–7.60(m,4H,ArH),7.49–7.43(m,2H,ArH),7.41–7.36(m,1H,ArH),7.26(s,1H,ArH),7.24(s,1H,ArH),7.20–7.14(m,2H,ArH),2.89(d,J＝16.5Hz,1H,CH2),2.53(d,J＝14.6Hz,1H,CH2),2.40(s,3H,ArCH3),2.15(d,J＝14.9Hz,2H,CH2),1.31(s,3H,CH3),0.67(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝205.0,191.6,187.7,171.2,144.9,140.4,139.6,137.0,135.5,130.4,130.4,129.7,129.7,128.9,128.9,127.9,127.3,127.3,126.7,126.7,126.3,126.3,111.8,88.1,51.0,43.2,32.8,29.9,29.7,21.2；HRMS(TOF ES+):m/z calcd for C30H27NO3[(M+H)+],450.2064,found,450.2065.
实施例25：不同在于化合物1为(E)-1-(萘-2-基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品4c的结构、形态、熔点、核磁、高分辨质谱数据如下：
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；Brown solid:166mg,产率75％；熔点＝208–209℃；1HNMR
(600MHz,CDCl3)δ＝8.88(s,1H,C＝CH),8.34(s,1H,ArH),7.96(d,J＝8.1Hz,1H,ArH),7.88–7.84(m,3H,ArH),7.56–7.51(m,2H,ArH),7.25(d,J＝10.3Hz,2H,ArH),7.17(d,J＝7.9Hz,2H,ArH),2.90(d,J＝16.7Hz,1H,CH2),2.53(d,J＝14.7Hz,1H,CH2),2.40(s,3H,ArCH3),2.18–2.14(m,2H,CH2),1.31(s,3H,CH3),0.68(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.8,191.4,187.9,170.9,139.4,135.5,135.3,135.0,132.2,130.2,130.2,130.0,129.3,127.6,127.5,127.5,126.2,126.1,126.1,125.1,111.7,87.8,50.8,43.0,32.6,29.7,29.5,21.0；HRMS(TOF ES+):m/z calcd for C28H25NO3[(M+H)+],452.0856,found,452.0860.
实施例26：不同在于化合物1为(E)-1-(4-硝基苯基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品4d的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:154mg,产率73％；熔点＝158–159℃；1H NMR(600MHz,CDCl3)δ＝8.93(s,1H,C＝CH),8.28(d,J＝8.6Hz,2H,ArH),7.91(d,J＝8.4Hz,2H,ArH),7.27(s,1H,ArH),7.26(s,1H,ArH),7.17(d,J＝7.9Hz,2H,ArH),2.81(d,J＝16.7Hz,1H,CH2),2.50(d,J＝14.8Hz,1H,CH2),2.41(s,3H,ArCH3),2.18–2.14(m,2H,CH2),1.29(s,3H,CH3),0.63(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.4,191.2,186.2,171.3,149.5,143.5,140.2,135.1,130.5,130.5,129.9,129.9,126.4,126.4,123.1,123.1,111.1,88.4,51.0,43.1,32.9,29.6,29.6,21.2；HRMS(TOF ES+):m/z calcd for C24H22N2O5[(M+H)+],419.1601,found,419.1610.
实施例27：不同在于化合物1为(E)-1-(4-三氟甲基苯基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品4e的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色固体:151mg,产率68％；熔点＝150–151℃；1H NMR(600MHz,CDCl3)δ＝8.89(s,1H,C＝CH),7.87(d,J＝7.9Hz,2H,ArH),7.69(d,J＝8.0Hz,2H,ArH),7.26(d,J＝9.1Hz,2H,ArH),7.17(d,J＝8.3Hz,2H,ArH),2.84(d,J＝16.7Hz,1H,CH2),2.51(d,J＝14.6Hz,1H,CH2),2.40(s,3H,ArCH3),2.15(d,J＝15.8Hz,2H,CH2),1.29(s,3H,CH3),0.64(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.6,191.3,187.0,171.4,141.3,140.0,135.3,133.3(C-F,J＝32.5Hz),130.5,130.5,129.3,129.3,126.4,126.4,125.0(C-F,J＝3.6Hz),124.9(C-F,J＝3.8Hz),123.8(C-F,J＝272.4Hz),111.3,88.3,51.0,43.2,32.9,29.7,29.7,21.2；HRMS(TOF ES+):m/z calcd for C25H22FNO3[(M+H)+],442.1625,found,442.1630.
实施例28：不同在于化合物1为(E)-1-(苯并[d][1,3]二氧代醇-5-基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品4f的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色固体:150mg,产率72％；熔点＝171–172℃；1H NMR(600MHz,CDCl3)δ＝8.83(s,1H,C＝CH),7.47(d,J＝7.7Hz,1H,ArH),7.33(s,1H,ArH),7.24(d,J＝7.8Hz,2H,ArH),7.15(d,J＝7.9Hz,2H,ArH),6.85(d,J＝8.0Hz,1H,ArH),6.02(s,2H,CH2),2.87(d,J＝16.7Hz,1H,CH2),2.50(d,J＝14.6Hz,1H,CH2),2.39(s,3H,ArCH3),2.14(dd,J＝15.4,8.9Hz,2H,CH2),1.30(s,3H,CH3),0.67(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝205.1,191.5,186.4,171.2,151.1,147.5,139.5,135.5,132.6,130.4,130.4,126.2,126.2,125.5,111.8,109.3,107.6,101.6,88.0,51.0,43.2,32.8,29.9,29.8,21.2；HRMS(TOF ES+):m/z calcd for C25H23NO5[(M+H)+],418.1649,found,418.1652.
实施例29：不同在于化合物1为(E)-1-(噻吩-2-基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品4g的结构、形态、熔点、核磁、高分辨质谱数据如下，化合物4g的单晶结构图见图2；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色固体:126mg,产率66％；熔点＝168–169℃；1H NMR(600MHz,CDCl3)δ＝8.94(s,1H,C＝CH),8.43–8.41(m,1H,C＝CH),7.61(dd,J＝5.1,1.1Hz,1H,C＝CH),7.24(d,J＝8.0Hz,2H,ArH),7.16–7.15(m,2H,ArH),7.14–7.13(m,1H,C＝CH),2.89(d,J＝16.6Hz,1H,CH2),2.55(d,J＝14.7Hz,1H,CH2),2.40(s,3H,ArCH3),2.18–2.15(m,2H,CH2),1.33(s,3H,CH3),0.66(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.7,190.7,178.6,171.8,144.6,139.6,135.4,133.7,133.2,130.3,130.3,128.0,126.2,126.2,111.7,88.3,51.0,43.3,32.7,29.7,29.7,21.1；HRMS(TOF ES+):m/z calcdfor C22H21NO3S[(M+H)+],380.1315,found,380.1317.
实施例30：不同在于化合物1为(E)-1-((1r，3r，5r，7r)-金刚烷-2-基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品4h的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:4,Rf＝0.2；黄色固体:100mg,产率46％；熔点＝222–223℃；1H NMR(600MHz,CDCl3)δ＝8.83(s,1H,C＝CH),7.21(d,J＝7.9Hz,2H,ArH),7.12(d,J＝8.1Hz,2H,ArH),2.86(d,J＝16.3Hz,1H,CH2),2.53(d,J＝14.4Hz,1H,C-CH),2.38(s,3H,ArCH3),2.15–2.09(m,2H,CH2),2.05–2.04(m,3H,CH2 and C-CH),2.00(d,J＝12.2Hz,3H,CH2 and C-CH),1.93(d,J＝11.8Hz,3H,CH2),1.78(d,J＝12.3Hz,3H,CH2),1.73(d,J＝12.3Hz,3H,CH2),1.31(s,3H,CH3),0.58(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝205.1,200.3,190.2,173.2,139.5,135.7,130.3,130.3,126.6,126.6,112.3,88.5,51.1,45.2,43.4,36.7,36.7,36.7,36.0,36.0,36.0,32.9,29.7,29.5,28.2,28.2,28.2,21.2；HRMS(TOF ES+):m/z calcd forC28H33NO3[(M+H)+],432.2533,found,432.2543.
实施例31：不同在于化合物1为(1E，4E)-1-苯基-5-(对甲苯基氨基)戊-1,4-二烯-3-酮，所得产品4i的结构、形态、熔点、红外、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:154mg,产率77％；熔点＝231–232℃；1H NMR(600MHz,CDCl3)δ＝8.92(s,1H,C＝CH),7.86(d,J＝15.8Hz,1H,C＝CH),7.76(d,J＝15.9Hz,1H,C＝CH),7.67–7.65(m,2H,ArH),7.37(d,J＝5.2Hz,3H,ArH),7.24(d,J＝7.9Hz,2H,ArH),7.14(d,J＝8.0Hz,2H,ArH),2.88(d,J＝16.6Hz,1H,CH2),2.52(d,J＝14.5Hz,1H,CH2),2.39(s,3H,ArCH3),2.16(t,J＝15.7Hz,2H,CH2),1.35(s,3H,CH3),0.67(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.6,192.8,183.0,170.1,142.1,139.7,135.4,135.3,130.4,130.4,130.1,128.8,128.8,128.6,128.6,126.2,126.2,124.2,113.0,88.2,51.1,43.2,32.8,29.8,29.8,21.2；HRMS(TOF ES+):m/z calcd for C26H25NO3[(M+H)+],400.1907,found,400.1904.
实施例32：不同在于化合物1为(E)-1-(2,4-二氯苯基)-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品4j的结构、形态、熔点、红外、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色固体:110mg,产率50％；熔点＝144–145℃；1H NMR(600MHz,CDCl3)δ＝8.81(s,1H,C＝CH),7.41(d,J＝1.8Hz,1H,ArH),7.33–7.28(m,3H,ArH),7.25(d,J＝12.6Hz,2H,ArH),7.16(d,J＝7.9Hz,2H,ArH),2.79(d,J＝16.5Hz,1H,CH2),2.46(d,J＝14.7Hz,1H,CH2),2.40(s,3H,ArCH3),2.11(d,J＝15.7Hz,2H,CH2),1.26(s,3H,CH3),0.61(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.1,191.2,185.7,169.8,140.0,137.6,136.2,135.2,132.0,130.5,130.5,129.7,129.6,127.1,126.4,126.4,111.9,88.1,50.9,43.0,32.8,29.6,29.6,21.2；HRMS(TOF ES+):m/z calcd forC24H21Cl2NO3[(M+H)+],442.0971,found,442.0977.
实施例33：不同在于化合物1为(E)-1,3-二苯基-3-(对甲苯基氨基)丙-2-烯-1-酮，所得产品4k的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:151mg,产率67％；熔点＝195–196℃；1H NMR(600MHz,CDCl3)δ＝7.71(d,J＝7.6Hz,2H,ArH),7.43(t,J＝7.5Hz,1H,ArH),7.33(t,J＝7.6Hz,2H,ArH),7.24(d,J＝7.9Hz,3H,ArH),7.17(t,J＝7.6Hz,2H,ArH),7.05–6.99(m,4H,ArH),2.84(d,J＝16.2Hz,1H,CH2),2.61(d,J＝14.4Hz,1H,CH2),2.27(s,3H,ArCH3),2.19(d,J＝14.4Hz,1H,CH2),2.05(d,J＝16.2Hz,1H,CH2),1.26(s,3H,CH3),0.48(s,3H,CH3)；13CNMR(151MHz,CDCl3)δ＝205.9,192.2,189.6,181.1,139.0,138.7,134.2,132.2,130.3,129.8,129.8,129.8,129.8,129.7,129.4,129.4,129.0,129.0,128.1,128.1,127.9,127.9,110.5,86.9,51.3,43.5,32.9,29.5,29.2,21.2；HRMS(TOF ES+):m/z calcd forC30H27NO3[(M+H)+],450.2064,found,450.2065.
实施例34：不同在于化合物1为5,5-二甲基-3-(对甲苯基氨基)环己-2-烯-1-酮，所得产品4l的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:106mg,产率63％；熔点＝223–224℃；1H NMR(600MHz,CDCl3)δ＝7.28(d,J＝6.9Hz,2H,ArH),7.14(d,J＝7.7Hz,2H,ArH),2.74(d,J＝16.0Hz,1H,CH2),2.52(d,J＝14.4Hz,1H,CH2),2.45(d,J＝6.2Hz,1H,CH2),2.42(s,3H,ArCH3),2.34(d,J＝16.5Hz,1H,CH2),2.26(d,J＝17.1Hz,2H,CH2),2.05–1.98(m,2H,CH2),1.25(s,3H,CH3),1.10(s,3H,CH3),1.04(s,3H,CH3),0.35(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝205.3,190.0,189.5,183.9,140.4,133.0,130.6,130.6,129.2,129.2,106.2,86.6,51.5,51.1,42.7,38.8,33.6,33.0,29.2,28.7,28.4,28.4,21.3；HRMS(TOF ES+):m/zcalcd for C23H27NO3[(M+H)+],366.2064,found,366.2065.
实施例35：不同在于化合物1为(E)-3-氨基-1,3-二苯基丙-2-烯-1-酮，所得产品4m的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:139mg,产率38％；熔点＝202–203℃；1H NMR(600MHz,CDCl3)δ＝7.72(d,J＝7.7Hz,2H,ArH),7.53(d,J＝7.7Hz,2H,ArH),7.50–7.46(m,2H,ArH),7.39–7.34(m,4H,ArH),6.44(s,1H,NH),2.74(d,J＝15.9Hz,1H,CH2),2.59(d,J＝14.2Hz,1H,CH2),2.17(d,J＝2.3Hz,1H,CH2),2.07(d,J＝14.2Hz,1H,CH2),1.31(s,3H,CH3),1.05(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝206.9,193.0,190.1,180.8,138.3,132.6,132.4,130.0,129.5,129.5,128.8,128.8,128.3,128.3,128.0,128.0,109.7,79.5,51.9,46.9,33.5,29.6,28.7；HRMS(TOF ES+):m/z calcd for C23H21NO3[(M+H)+],360.1594,found,360.1592.
实施例36：不同在于化合物1为(E)-3-(苄氨基)-1-苯基丙-2-烯-1-酮，所得产品4n的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；白色固体:86mg,产率46％；熔点＝118–119℃；1H NMR(600MHz,CDCl3)δ＝8.49(s,1H,C＝CH),7.70(d,J＝7.6Hz,2H,ArH),7.48–7.44(m,4H,ArH),7.39(t,J＝7.5Hz,2H,ArH),7.35(d,J＝7.0Hz,2H,ArH),4.56(d,J＝14.1Hz,1H,CH2),4.42(d,J＝14.1Hz,1H,CH2),2.97(d,J＝15.9Hz,1H,CH2),2.51(d,J＝14.6Hz,1H,CH2),2.18(d,J＝15.9Hz,1H,CH2),2.09(d,J＝14.6Hz,1H,CH2),1.36(s,3H,CH3),1.11(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.1,190.4,188.0,170.7,138.3,132.3,131.9,129.5,129.5,129.4,129.3,129.3,128.9,128.9,127.8,127.8,110.6,87.0,51.9,50.3,43.1,32.7,30.4,29.6；HRMS(TOF ES+):m/z calcd for C24H23NO3[(M+H)+],374.1751,found,374.1756.
实施例37：不同在于化合物1为(E)-3-((4-羟基苯基)氨基)-1-苯基丙-2-烯-1-酮，所得产品4o的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:1,Rf＝0.2；黄色固体:88mg,产率50％；熔点＝211–212℃；1H NMR(600MHz,CDCl3)δ＝8.74(s,1H,OH),7.77(s,2H,C＝CH and ArH),7.52(s,1H,ArH),7.44(s,2H,ArH),7.27(s,1H,ArH),7.14(s,2H,ArH),6.90(s,2H,ArH),2.81(d,J＝16.3Hz,1H,CH2),2.53(d,J＝14.7Hz,1H,CH2),2.12(t,J＝18.7Hz,2H,CH2),1.27(s,3H,CH3),0.57(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.7,191.7,188.9,171.7,157.4,138.3,132.3,130.3,129.0,129.0,128.7,128.7,128.1,128.1,116.6,116.6,111.1,88.2,51.1,43.2,33.0,29.5,29.4；HRMS(TOF ES+):m/z calcd for C23H21NO4[(M+H)+],376.1543,found,376.1546.
实施例38：不同在于化合物1为(E)-3-(环己基氨基)-1-苯基丙-2-烯-1-酮，所得产品4p的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:120mg,产率66％；熔点＝199–200℃；1H NMR(600MHz,CDCl3)δ＝8.89(s,1H,C＝CH),7.74(d,J＝7.4Hz,2H,ArH),7.49(t,J＝7.3Hz,1H,ArH),7.41(t,J＝7.7Hz,2H,ArH),3.08(t,J＝11.8Hz,1H,C-CH),2.93(d,J＝16.2Hz,1H,CH2),2.52(d,J＝14.7Hz,1H,CH2),2.27(d,J＝12.1Hz,1H,CH2),2.15(d,J＝16.1Hz,1H,CH2),2.06(d,J＝14.4Hz,1H,CH2),1.93(t,J＝11.8Hz,3H,CH2),1.73(d,J＝12.7Hz,1H,CH2),1.62–1.54(m,2H,CH2),1.36(s,3H,CH3),1.33–1.19(m,3H),1.15(s,3H,CH3)；13C NMR(150MHz,CDCl3)δ＝204.6,189.9,188.0,168.5,138.5,131.8,128.9,128.9,127.8,127.8,110.1,88.0,58.0,50.5,43.7,35.1,33.5,32.5,30.4,29.7,25.9,25.8,24.9；HRMS(TOF ES+):m/z calcd for C23H27NO3[(M+H)+],366.2064,found,366.2066.
实施例39：不同在于化合物1为(E)-3-((2-氯苯基)氨基)-1-苯基丙-2-烯-1-酮，所得产品4q的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；黄色固体:98mg,产率50％；熔点＝89–90℃；1H NMR(600MHz,DMSO-d6)δ＝9.31(s,1H,C＝CH),7.68(d,J＝7.5Hz,2H,ArH),7.58(d,J＝8.3Hz,3H,ArH),7.47(t,J＝7.7Hz,2H,ArH),7.38(d,J＝8.2Hz,2H,ArH),2.65(d,J＝17.5Hz,1H,CH2),2.33(dd,J＝32.8,16.1Hz,2H,CH2),2.18(d,J＝14.9Hz,1H,CH2),1.25(s,3H,CH3),0.72(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝206.6,192.2,187.3,171.9,138.8,136.8,133.4,132.5,130.1,130.1,129.1,129.1,128.6,128.6,127.9,127.9,111.6,87.0,51.0,43.0,32.8,30.2,30.2；HRMS(TOF ES+):m/z calcd for C23H20ClNO3[(M+H)+],394.1204,found,394.1213.
实施例40：不同在于化合物2为5-苯基-2-(苯基-λ3-碘烷基)环己烷-1,3-二酮，所得产品4r的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:2,Rf＝0.2；黄色固体:137mg,产率65％；熔点＝172–173℃；1H NMR(600MHz,DMSO-d6)δ＝9.48(s,1H,C＝CH),7.72(d,J＝7.6Hz,2H,ArH),7.58(t,J＝7.4Hz,1H,ArH),7.49(t,J＝7.7Hz,2H,ArH),7.41(d,J＝7.6Hz,1H,ArH),7.37(t,J＝7.6Hz,2H,ArH),7.35–7.31(m,3H,ArH),7.28(d,J＝8.1Hz,1H,ArH),7.25(d,J＝8.2Hz,2H,ArH),3.59–3.52(m,1H,C-CH),2.98–2.89(m,2H,CH2),2.84–2.79(m,1H,CH2),2.57(dd,J＝15.0,10.8Hz,1H,CH2),2.35(s,3H,ArCH3)；13C NMR(150MHz,DMSO-d6)δ＝205.5,192.6,187.3,169.9,143.0,138.8,137.4,135.1,132.5,130.9,130.9,129.2,129.2,129.2,129.2,128.6,128.6,127.6,127.6,127.4,122.2,122.2,112.3,84.5,44.7,38.2,37.5,20.9；HRMS(TOF ES+):m/z calcd for C28H23NO3[(M+H)+],422.1751,found,422.1772.
实施例41：不同在于化合物2为2-(苯基-λ3-碘烷基)环庚烷-1,3-二酮，所得产品4s的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:4,Rf＝0.2；白色固体:112mg,产率60％；熔点＝187–188℃；1H NMR(600MHz,CDCl3)δ＝8.95(s,1H,C＝CH),7.76(d,J＝7.6Hz,2H,ArH),7.53(t,J＝7.4Hz,1H,ArH),7.44(t,J＝7.6Hz,2H,ArH),7.22(d,J＝8.0Hz,2H,ArH),7.05(d,J＝8.0Hz,2H,ArH),3.18–3.13(m,1H,CH2),2.66–2.60(m,2H,CH2),2.37(s,3H,ArCH3),2.19–2.11(m,3H,CH2),1.77–1.69(m,2H,CH2)；13C NMR(150MHz,CDCl3)δ＝200.3,191.0,188.3,168.0,138.5,137.9,135.2,132.1,130.4,130.4,128.9,128.9,128.0,128.0,123.1,123.1,111.6,85.4,38.9,33.1,25.1,21.0,19.2；HRMS(TOF ES+):m/z calcd for C23H21NO3[(M+H)+],360.1594,found,360.1609.
实施例42：不同在于化合物2为4,4-二甲基-2-(苯基-λ3-碘烷基)环己烷-1,3-二酮，所得产品4t的结构、形态、熔点、核磁、高分辨质谱数据如下；
V石油醚/V乙酸乙酯＝1:3,Rf＝0.2；白色固体:148mg,产率79％；熔点＝200–201℃；1H NMR(600MHz,DMSO-d6)δ＝9.23(s,1H,C＝CH),7.69(d,J＝7.6Hz,2H,ArH),7.56(t,J＝7.4Hz,1H,ArH),7.47(t,J＝7.6Hz,2H,ArH),7.30(d,J＝7.9Hz,2H,ArH),7.12(d,J＝7.9Hz,2H,ArH),2.46–2.42(m,1H,CH2),2.33(s,3H,ArCH3),2.28–2.25(m,1H,CH2),2.23–2.18(m,1H,CH2),1.79–1.75(m,1H,CH2),1.12(s,3H,CH3),0.94(s,3H,CH3)；13C NMR(150MHz,DMSO-d6)δ＝213.3,193.4,187.3,171.5,139.0,138.6,135.5,132.4,130.7,130.7,129.1,129.1,128.5,128.5,125.1,125.1,112.1,84.9,45.8,33.5,27.1,25.2,24.0,21.0；HRMS(TOF ES+):m/z calcd for C24H23NO3[(M+H)+],374.1751,found,374.1765。

Claims (7)

1.一种氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法，其特征在于：在反应器中加入化合物1、化合物2、溶剂、催化剂、添加剂，在25～60℃油浴条件下反应1～12h，薄层色谱监测反应进程，直至反应完全；然后用乙酸乙酯和水萃取3-4次，收集合并有机相并用饱和食盐水洗涤，收集有机相后用无水硫酸钠干燥，减压浓缩，残渣用硅胶柱层析分离纯化得到化合物3或化合物4，即3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物或1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物；
其中R1选自取代或未取代芳基、杂芳基、烷基、苯乙烯基；R2选自氢原子、甲基、苯基；R3选自氢原子、取代或未取代芳基、杂芳基、烷基、苄基；R4选自烷基、苯基；
或者R1和R2共价连接形成带有取代基的6元环。
2.根据权利要求1所述的氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法，其特征在于：芳基的取代基选自卤素、硝基、三氟甲基、甲基、甲氧基、甲基磺酰基。
3.根据权利要求1所述的氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法，其特征在于：制备3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物时，催化剂选自二氯(五甲基环戊二烯基)合钌(III)二聚体、二氯(五甲基环戊二烯基)合铑(III)二聚体；
制备1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物时，催化剂选自二氯(五甲基环戊二烯基)合铱(III)二聚体、二氯(五甲基环戊二烯基)合铑(III)二聚体。
4.根据权利要求1所述的氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法，其特征在于：制备3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物时，添加剂选自氧化银、碳酸银、三氧化钒银、六氟锑酸银、醋酸银、四氟硼酸银；
制备1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物时，添加剂选自硝酸银、三氟乙酸银、氯化银、三氟甲磺酸银，氟化银。
5.根据权利要求1所述的氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法，其特征在于：制备3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物时，溶剂选自1,4-二氧六环、二甲基亚砜、乙腈、甲苯、丙酮、二甲苯、乙酸乙酯、硝基甲烷；
制备1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物时，溶剂为水与乙腈、甲苯、丙酮、乙酸乙酯、硝基甲烷中的一种，化合物1与水的摩尔比为1:2～6。
6.根据权利要求1所述的氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法，其特征在于：化合物1与化合物2的摩尔比为1:1～4，化合物1与催化剂的摩尔比为1:0.01～0.03，化合物1与添加剂的摩尔比为1:1～3。
7.权利要求1-6任一项所述的氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法制得的3a,7a-二羟基-六氢-4H-吲哚-4-酮类化合物或1-氮杂螺环[4.4]壬-2-烯-4,6-二酮类化合物。
CN202310095824.0A 2023-02-10 2023-02-10 一种氮杂螺环酮类化合物和二羟基氢化吲哚类化合物的制备方法 Pending CN116496201A (zh)

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