CN113024438A - 一种制备氧化吲哚类衍生物的绿色方法 - Google Patents
一种制备氧化吲哚类衍生物的绿色方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/34—Oxygen atoms in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/10—Spiro-condensed systems
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
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- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
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Abstract
本发明涉及绿色有机合成技术领域,提供了一种制备氧化吲哚类衍生物的绿色方法,其制备过程为:以具有不同官能团的吲哚类化合物为原料,在室温、敞口、中性条件下,采用MBrx(M为Fe2+、Fe3+、Ce3+等)为催化剂,X=2或3,过氧化氢为唯一氧化剂,原位生成活性溴(RBS),催化合成氧化吲哚类衍生物。本发明所述方法通过使用MBrx(如FeBr2、CeBr3等)为催化剂,避免了使用昂贵或复杂的催化剂,绿色环保,安全,简单高效,反应条件温和,底物适用范围广,具有较好的应用前景,有望在有机合成、精细化工和制药工业中得到广泛应用。
Description
技术领域
本发明涉及一种制备氧化吲哚类衍生物的绿色方法,属于绿色化学和有机合成技术领域。
背景技术
氧化吲哚类衍生物是一类重要的含氮杂环化合物,具有一定的药物作用和广泛的生物活性,是许多天然产物以及药物活性分子的中间体,也是一种重要的精细化工原料,在医药、生物化学以及材料化学领域中有着广泛的应用。
目前已开发了许多针对吲哚环系的氧化剂,包括N-溴代丁二酰亚胺(NBS)、间氯过氧苯甲酸(m-CPBA)、次氯酸叔丁酯(t-BuOCl)、二甲基亚砜(DMSO/H+)、高碘酸钠(NaIO4)、金属催化法(如Pb(OAc)4、OsO4)、过氧单磺酸钾(Oxone-KBr)和酶转化(如卤过氧化物酶),但这些方法仍存在不足之处,如使用不安全,对环境不友好。Pb(OAc)4和OsO4是毒性极强的重金属氧化剂,对人体健康和环境构成重大的威胁;而t-BuOCl是一种不稳定、易燃、有害的液体,此外,t-BuOCl需要随后的酸处理来完成重排;NBS通常在酸性条件下使用(AcOH–H2O),不可避免地产生相应的丁二酰亚胺副产物,需要通过柱层析纯化。大多数方法都受到非绿色性、不安全和/或较差的底物范围的限制。
因此,开发一种绿色、安全、廉价、适用范围广的制备氧化吲哚类衍生物的方法意义重大。
发明内容
针对上述现有技术中存在的问题,本发明提供了一种制备氧化吲哚类衍生物的绿色方法,该方法简单、经济、绿色环保、适用性广泛,适于规模化生产。
本发明的技术方案如下:
以吲哚化合物为原料,在室温、敞口、中性条件下,以MBrx(M为Fe2+、Fe3+、Ce3+等)为催化剂,过氧化氢为唯一氧化剂,催化合成氧化吲哚类衍生物。
反应以官能团化吲哚为原料,所述官能团可为烷烃、烯烃、炔烃、脂环烃(如4氢β-咔啉)、富电子芳烃、酯、呋喃、噻吩、吡啶、吡咯以及其他杂环等不同取代基,也可为常用的保护基团包括Boc、Cbz、TBS、Bn、Ac、Bu、Bz、Piv、iPr和TIPS等。
所述催化剂为FeBr2、FeBr3、CeBr3以及FeSO4-KBr、FeCl3-KBr、Fe(NO3)3-KBr、Ce(NO3)3-KBr、CeCl3-KBr、Ce(OTf)3-KBr等金属(Fe2+、Fe3+、Ce3+等)和溴化物的组合中的任意一种。
所述反应所用过氧化氢浓度为3-30%,过氧化氢与吲哚类化合物的摩尔比为2-5:1。
所述反应于溶剂中进行,所用溶剂为四氢呋喃、乙腈、叔丁醇以及其它与水互溶的溶剂中的任意一种与水组成的混合溶剂。
所述反应的较佳反应时间为2-3h。
所述反应的处理方法为,反应结束后用Na2S2O3溶液淬灭,采用有机溶剂(如乙酸乙酯、二氯甲烷)萃取。收集有机相,无水硫酸钠干燥,过滤,浓缩,即得氧化吲哚类衍生物。
本发明具有以下有益效果:
本发明首次实现了以H2O2为氧化剂的广泛底物合成和放大量制备氧化吲哚类衍生物的绿色方法。在中性条件下由MBrx-H2O2原位生成RBS催化合成氧化吲哚类衍生物。本发明避免了使用昂贵且复杂的催化剂,反应条件温和,反应过程简单,产率高,安全环保,符合绿色化学理念,适用性更加广泛,具有广阔的发展前景和应用前景。
附图说明
图1和图2是实施例1的1H-NMR及13C-NMR谱图
图3和图4是实施例2的1H-NMR及13C-NMR谱图
图5和图6是实施例3的1H-NMR及13C-NMR谱图
图7和图8是实施例4的1H-NMR及13C-NMR谱图
图9和图10是实施例5的1H-NMR及13C-NMR谱图
图11和图12是实施例8的1H-NMR及13C-NMR谱图
图13和图14是实施例10的1H-NMR及13C-NMR谱图
图15和图16是实施例12的1H-NMR及13C-NMR谱图
图17和图18是实施例13的1H-NMR及13C-NMR谱图
图19和图20是实施例20的1H-NMR及13C-NMR谱图
具体实施方式
下面结合具体实施例对本发明进行进一步说明。以下实施例只用于解释本发明,但不应解释为限制本发明的范围。应当指出的是,在不脱离本发明构思的前提下,对本发明公开的内容可以做出若干调整和改进,这些都属于本发明的保护范围。
实施例1:
将THF/H2O(10/1)47mL、1a(1g,8.54mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.85mmol,0.18g)或CeBr3(0.68mmol,0.26g),H2O2水溶液(30%,18.8mmol,1.9mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物1b(产率:FeBr2:66%;CeBr3:49%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.22(brs,1H),7.25–7.16(m,2H),7.01(td,J=7.5,1.0Hz,1H),6.92–6.85(m,1H),3.54(s,2H).13C-NMR(100MHz,CDCl3)δ:178.3,142.7,128.0,125.4,124.7,122.4,110.0,36.4.IR3139.5,3074.8,1680.7,1616.1,1470.1,1386.8,1329.0,1231.9,1202.6,863.3,734.7,672.1,541.8cm-1;HRMS(CI+)(m/z)calcd.for C8H7NO[M]+133.0522;found 133.0526.
实施例2:
将THF/H2O(10/1)42mL、2a(1g,7.63mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.76mmol,0.16g)或CeBr3(0.61mmol,0.23g),H2O2水溶液(30%,16.8mmol,1.7mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物2b(产率:FeBr2:53%;CeBr3:58%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:7.30–7.18(m,2H),7.02(td,J=7.5,1.0Hz,1H),6.79(d,J=7.8Hz,1H),3.48(s,2H),3.18(s,3H).13C-NMR(100MHz,CDCl3)δ:175.1,145.2,127.9,124.5,124.3,122.4,108.1,35.8,26.2.IR3388.3,3057.4,1695.9,1611.2,1464.8,1346.0,1263.0,1125.9,1089.0,753.7,655.4cm-1;HRMS(CI+)(m/z)calcd.for C9H9NO[M]+147.0679;found 147.0687.
实施例3:
将THF/H2O(10/1)27mL、3a(1g,4.83mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.48mmol,0.10g)或CeBr3(0.39mmol,0.15g),H2O2水溶液(30%,10.6mmol,1.1mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物3b(产率:FeBr2:55%;CeBr3:56%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:7.37–7.23(m,6H),7.17(td,J=7.8,1.2Hz,1H),7.01(td,J=7.5,1.0Hz,1H),6.74(d,J=7.8Hz,1H),4.93(s,2H),3.62(s,2H).13C-NMR(100MHz,CDCl3)δ:175.1,144.3,135.9,128.8,127.8,127.6,127.4,124.5,124.4,122.4,109.1,43.7,35.7.IR 3442.7,3032.4,2920.0,1701.4,1608.3,1460.6,1347.8,1224.2,1195.5,1162.1,877.0,737.6,600.9,615.1,544.7cm-1;HRMS(CI+)(m/z)calcd.for C15H13NO[M]+223.0992;found 223.0996.
实施例4:
将THF/H2O(10/1)42mL、4a(1g,7.63mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.76mmol,0.16g)或CeBr3(0.61mmol,0.23g),H2O2水溶液(30%,16.8mmol,1.7mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物4b(产率:FeBr2:84%;CeBr3:78%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:8.90(brs,1H),7.12(t,J=7.8Hz,1H),6.84(d,J=7.8Hz,1H),6.74(d,J=7.7Hz,1H),3.42(s,2H),2.25(s,3H).13C-NMR(100MHz,CDCl3)δ:178.0,142.3,134.4,128.0,124.3,123.6,107.4,35.4,18.7.IR 3082.4,2911.8,2836.9,1722.4,1663.3,1463.3,1463.0,1317.4,1258.7,761.9cm-1;HRMS(CI+)(m/z)calcd.for C9H9NO[M+H]+148.0757;found 148.0759.
实施例5:
将THF/H2O(10/1)3mL、5a(1g,6.71mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.67mmol,0.14g)或CeBr3(0.54mmol,0.20g),H2O2水溶液(30%,14.8mmol,1.5mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物5b(产率:FeBr2:71%;CeBr3:74%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:7.13(dd,J=7.7,5.3Hz,1H),6.68(ddd,J=10.1,8.1,2.4Hz,1H),6.52(dd,J=8.9,2.4Hz,1H),3.44(s,2H),3.15(s,3H).13C-NMR(100MHz,CDCl3)δ:175.4,161.8(d,JC,F=243Hz),146.6(d,JC,F=11.5Hz),125.1(d,JC,F=9.5Hz),119.6(d,JC,F=3Hz),108.2(d,JC,F=22Hz),96.8(d,JC,F=27.5Hz),35.2,26.3.IR 3063.5,2952.7,2921.4,1712.2,1659.5,1616.1,1501.2,1459.5,1374.3,1334.7,1294.6,1259.7,1209.9,1121.7,1065.7,961.3,869.2,799.2,651.8,608.7cm-1;HRMS(CI+)(m/z)calcd.for C9H9FNO[M+NH4]+183.0928;found183.0929.
实施例6:
将THF/H2O(10/1)42mL、6a(1g,7.63mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.76mmol,0.16g)或CeBr3(0.61mmol,0.23g),H2O2水溶液(30%,16.8mmol,1.7mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物6b(产率:FeBr2:87%;CeBr3:89%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.69(s,1H),7.21(t,J=7.6Hz,2H),7.07–7.00(m,1H),6.96(d,J=7.8Hz,1H),3.49(q,J=7.7Hz,1H),1.52(d,J=7.7Hz,3H).13C-NMR(100MHz,CDCl3)δ:182.2,141.5,131.3,127.9,123.8,122.4,110.0,41.3,15.3.IR 3150.6,1680.2,1613.9,1461.6,1332.4,1215.4,1169.6,791.3,741.7,657.3,543.9cm-1;HRMS(CI+)(m/z)calcd.for C9H9NO[M]+147.0679;found 147.0687.
实施例7:
将THF/H2O(10/1)19mL、7a(1g,3.43mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.34mmol,0.07g)或CeBr3(0.27mmol,0.10g),H2O2水溶液(30%,7.6mmol,0.77mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物7b(产率:FeBr2:80%;CeBr3:71%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:7.30–7.20(m,2H),7.03(td,J=7.5,1.0Hz,1H),6.83–6.78(m,1H),3.78(d,J=1.2Hz,2H),3.18(s,3H),1.32(s,3H),0.71(s,9H),-0.08(s,3H),-0.15(s,3H).13C-NMR(100MHz,CDCl3)δ:179.3,143.8,133.2,127.8,123.2,122.2,107.7,68.2,50.7,26.1,25.6,18.4,18.0,-5.5,-5.7.IR 2933.4,2857.9,1714.4,1612.4,1465.8,1377.5,1347.7,1253.2,1106.6,842.1,777.0,746.4cm-1;HRMS(CI+)(m/z)calcd.for C17H27NO2Si[M+H]+306.1884;found306.1893.
实施例8:
将THF/H2O(10/1)17mL、8a(1g,3.03mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.30mmol,0.06g)或CeBr3(0.24mmol,0.09g),H2O2水溶液(30%,6.7mmol,0.68mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物8b(产率:FeBr2:79%;CeBr3:85%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.44(d,J=10.9Hz,1H),7.26–7.20(m,1H),7.10(t,J=7.5Hz,1H),7.06–7.00(m,1H),6.97(dd,J=7.8,4.4Hz,1H),4.79–4.57(m,1H),3.87–3.66(m,5H),2.55(ddd,J=14.6,12.7,9.0Hz,1H),2.44–2.31(m,1H),1.45(d,J=12.6Hz,9H).13C-NMR(100MHz,CDCl3)δ:178.4,178.3,172.6,172.3,154.4,153.5,140.10,140.07,133.3,133.1,128.8,123.2,123.1,122.4,110.6,81.0,59.1,58.7,55.4,54.8,53.2,52.6,52.4,52.3,40.5,39.6,28.4.IR 3254.5,2977.0,1697.3,1619.3,1470.4,1207.1,1161.5,900.4,739.3cm-1;HRMS(CI+)(m/z)calcd.for C18H22N2O5[M]+346.1523;found 346.1530.
实施例9:
将THF/H2O(10/1)16mL、9a(1g,2.95mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.30mmol,0.06g)或CeBr3(0.24mmol,0.09g),H2O2水溶液(30%,6.5mmol,0.66mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物9b(产率:FeBr2:9b:43.3%,9c:21.7%;CeBr3:9b:37.5%,9c:37.5%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.49(brs,1H),7.28–6.83(m,4H),4.15–3.50(m,3H),2.55–1.87(m,6H),1.60–1.20(m,11H).13C-NMR(100MHz,CDCl3)δ:181.0,155.5,154.7,141.1,128.8,128.4,125.0,123.0,122.4,122.3,119.4,110.5,110.2,80.1,61.9,56.3,45.5,34.8,31.3,28.5,21.9,16.9.IR 3248.4,2973.0,2940.2,2248.8,1688.0,1620.0,1470.5,1393.6,1336.9,1262.6,1231.3,1166.2,1122.6,1027.4,884.2,868.8,735.8,638.2cm-1;HRMS(CI+)(m/z)calcd.for C20H25N3O3[M]+355.1890;found 355.1895.
实施例10:
将THF/H2O(10/1)22mL、10a(1g,4.01mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.40mmol,0.09g)或CeBr3(0.32mmol,0.12g),H2O2水溶液(30%,8.8mmol,0.90mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物10b(产率:FeBr2:77%;CeBr3:91%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.63(brs,1H),7.20–7.14(m,3H),7.13–6.99(m,4H),6.92(td,J=7.6,1.1Hz,1H),6.75(d,J=7.7Hz,1H),5.29(s,1H),4.52(td,J=8.3,6.9Hz,1H),4.43(td,J=9.2,5.4Hz,1H),2.90(ddd,J=12.5,9.4,6.9Hz,1H),2.38(ddd,J=12.5,8.0,5.4Hz,1H).13C-NMR(100MHz,CDCl3)δ:180.3,139.9,136.6,131.2,127.8,127.6,127.5,125.4,124.7,122.2,109.7,87.5,67.3,59.8,38.1.IR 3223.7,2882.3,1702.2,1618.0,1471.7,1219.5,1061.4,479.9,704.8cm-1;HRMS(CI+)(m/z)calcd.for C17H15NO2[M+H]+266.1176;found 266.1178.
实施例11:
将THF/H2O(10/1)38mL、11a(1g,6.89mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.69mmol,0.15g)或CeBr3(0.55mmol,0.21g),H2O2水溶液(30%,15.2mmol,1.55mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物11b(产率:FeBr2:88%;CeBr3:98%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:7.29–7.19(m,2H),7.04(t,J=7.5Hz,1H),6.81(d,J=7.8Hz,1H),3.41(q,J=7.7Hz,1H),3.19(s,3H),1.46(d,J=7.7Hz,3H).13C-NMR(100MHz,CDCl3)δ:178.6,143.9,130.6,127.8,123.4,122.3,107.9,40.5,26.1,15.3.IR 3502.9,2971.9,2932.9,1702.7,1610.2,1463.8,1345.9,1255.6,1093.2,754.0cm-1;HRMS(CI+)(m/z)calcd.for C10H11NO[M]+161.0835;found 161.0845.
实施例12:
将THF/H2O(10/1)25mL、12a(1g,4.52mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.45mmol,0.10g)或CeBr3(0.36mmol,0.14g),H2O2水溶液(30%,9.9mmol,1.02mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物12b(产率:FeBr2:95%;CeBr3:87%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:7.36–7.31(m,4H),7.29(ddt,J=8.9,5.5,1.7Hz,2H),7.19(tt,J=7.7,1.1Hz,1H),7.06(td,J=7.5,1.0Hz,1H),6.76(d,J=7.8Hz,1H),4.95(s,2H),3.57(q,J=7.6Hz,1H),1.58(d,J=7.7Hz,3H).13C-NMR(100MHz,CDCl3)δ:178.8,143.1,136.1,130.7,128.8,127.8,127.6,127.3,123.6,122.5,109.0,43.7,40.6,15.7.IR 2053.9,2972.5,2927.4,1706.7,1608.9,1480.9,1458.4,1350.9,1166.5,973.7,743.8,699.8cm-1;HRMS(CI+)(m/z)calcd.for C16H25NO[M]+237.1148;found237.1150.
实施例13:
将THF/H2O(10/1)20mL、13a(1g,3.63mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.36mmol,0.08g)或CeBr3(0.29mmol,0.11g),H2O2水溶液(30%,8.0mmol,0.82mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物13b(产率:FeBr2:85%;CeBr3:84%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.68(s,1H),7.26–7.16(m,2H),7.01(td,J=7.5,1.0Hz,1H),6.94(d,J=7.7Hz,1H),3.88–3.76(m,2H),3.62(t,J=6.4Hz,1H),2.23(dq,J=13.8,6.2Hz,1H),2.11(dq,J=13.5,6.6Hz,1H),0.87(s,9H),0.01(d,J=4.7Hz,6H).13C-NMR(100MHz,CDCl3)δ:181.6,142.0,129.6,127.9,124.4,122.1,110.0,59.8,43.1,33.3,26.0,18.3,-5.36,-5.41.IR 3205.7,2934.0,2858.4,1703.7,1619.6,1469.9,1248.4,1101.1,946.0,833.4,776.1,742.8,661.9cm-1;HRMS(CI+)(m/z)calcd.for C16H25NO2Si[M]+291.1649;found 291.1645.
实施例14:
将THF/H2O(10/1)18mL、14a(1g,3.30mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.33mmol,0.07g)或CeBr3(0.26mmol,0.10g),H2O2水溶液(30%,7.3mmol,0.74mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物14b(产率:FeBr2:82%;CeBr3:73%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:10.2(s,1H),7.10(t,J=8.5Hz,2H),6.99(t,J=7.5Hz,1H),3.96–3.79(m,2H),3.65(t,J=6.6Hz,1H),2.70(q,J=7.6Hz,2H),2.25–2.10(m,2H),1.30(t,J=7.6Hz,3H),0.89(brs,9H),0.04(d,J=4.2Hz,6H).13C-NMR(100MHz,CDCl3)δ:182.1,140.3,129.5,127.4,125.8,122.2,121.7,59.9,43.3,33.6,26.0,24.0,18.4,14.2,-5.3,-5.4.IR 3184.4,2954.1,2928.8,2860.7,1703.7,1623.1,1455.0,1389.1,1333.2,1258.4,1203.0,1104.3,1078.7,1006.2,946.0,837.2,750.9,671.5cm-1;HRMS(CI+)(m/z)calcd.for C18H30NO2Si[M+H]+320.2040;found 320.2038.
实施例15:
将THF/H2O(10/1)18mL、15a(1g,3.25mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.33mmol,0.07g)或CeBr3(0.26mmol,0.10g),H2O2水溶液(30%,7.3mmol,0.74mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物15b(产率:FeBr2:86%;CeBr3:97%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.34(d,J=32.3Hz,1H),7.40–7.30(m,6H),7.18(t,J=7.8Hz,1H),7.12–6.98(m,1H),6.90–6.85(m,1H),5.18–5.00(m,2H),3.76–3.27(m,3H),2.92(s,3H),2.30–2.05(m,2H).13C-NMR(100MHz,CDCl3)δ:180.4,180.1,156.2,141.8,136.9,136.7,129.2,128.9,128.5,128.0,127.8,124.3,123.9,122.5,122.4,110.0,67.2,67.1,46.3,45.7,43.8,34.8,34.2,28.4,28.2.IR 3218.6,2930.1,1698.6,1618.3,1471.8,1403.2,1188.0,1135.8,739.1,695.2cm-1;HRMS(CI+)(m/z)calcd.for C19H20N2O3[M]+324.1468;found 124.1465.
实施例16:
将THF/H2O(10/1)20mL、16a(1g,3.65mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.37mmol,0.08g)或CeBr3(0.29mmol,0.11g),H2O2水溶液(30%,8.0mmol,0.82mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物16b(产率:FeBr2:83%;CeBr3:96%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.42–9.07(m,1H),7.50–7.10(m,2H),7.01(t,J=7.5Hz,1H),6.91(brs,1H),3.68–3.21(m,3H),2.84(brs,3H),2.30–1.98(m,2H),1.42(s,9H).13C-NMR(100MHz,CDCl3)δ:180.5,180.2,155.8,141.8,141.7,129.4,129.2,128.1,124.5,124.0,122.5,110.0,109.9,79.7,79.6,46.0,45.8,43.9,34.4,28.5.IR 3233.7,3056.1,2978.2,2932.4,1692.9,1620.7,1472.5,1396.9,1326.2,1264.6,1230.0,1163.3,1050.4,877.1,733.3cm-1;HRMS(CI+)(m/z)calcd.for C16H23N2O3[M+H]+291.1703;found 291.1705.
实施例17:
将THF/H2O(10/1)18mL、17a(1g,3.29mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.33mmol,0.07g)或CeBr3(0.26mmol,0.10g),H2O2水溶液(30%,7.2mmol,0.74mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物17b(产率:FeBr2:78%;CeBr3:92%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.58(d,J=35.9Hz,1H),7.06–6.59(m,3H),3.73(s,3H),3.63–3.15(m,3H),2.80(s,3H),2.13(brs,2H),1.39(brs,9H).13C-NMR(100MHz,CDCl3)δ:180.5,180.1,155.7,135.3,130.5,112.6,112.2,111.5,110.2,79.5,55.8,45.9,45.6,44.3,34.3,28.4.IR 3233.6,2956.4,2923.1,2870.8,1689.4,1605.0,1483.3,1451.7,1395.1,1367.0,1302.6,1269.0,1205.0,1146.4,1033.0,874.8,809.8,759.4,646.3,606.4cm-1;HRMS(CI+)(m/z)calcd.forC17H25N2O4[M+H]+321.1809;found 321.1817.
实施例18:
将THF/H2O(10/1)14mL、18a(1g,2.45mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.25mmol,0.05g)或CeBr3(0.20mmol,0.08g),H2O2水溶液(30%,5.4mmol,0.55mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物18b(产率:FeBr2:90%;CeBr3:92%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:8.83(d,J=44.5Hz,1H),7.48–7.11(m,6H),7.05–6.80(m,3H),5.15–4.03(m,3H),3.66–3.27(m,4H),2.80–2.50(m,1H),2.49–1.95(m,1H),1.63–1.33(m,9H).13C-NMR(100MHz,CDCl3)δ:180.5,180.2,171.9,171.8,155.8,141.6,141.3,138.0,129.6,129.3,129.0,128.4,128.3,128.1,127.5,123.9,122.5,110.0,109.8,81.1,56.8,56.5,52.1,52.0,51.7,42.8,42.0,31.5,28.5.IR 3271.1,2923.2,2867.1,1696.5,1619.9,1464.1,1363.6,1326.6,1247.7,1220.7,1160.6,1007.7,863.3,745.0,699.0,667.0cm-1;HRMS(CI+)(m/z)calcd.for C24H28N2O5[M]+424.1993;found 424.1993.
实施例19:
将THF/H2O(10/1)19mL、19a(1g,3.47mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.35mmol,0.08g)或CeBr3(0.28mmol,0.11g),H2O2水溶液(30%,7.6mmol,0.78mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物19b(产率:FeBr2:76%;CeBr3:87%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.84–9.45(m,1H),7.44–7.04(m,2H),7.03–6.73(m,2H),5.22–3.87(m,3H),3.46–3.13(m,1H),2.89–2.69(m,3H),2.40–2.20(m,1H),2.00–1.92(m,4H),1.91(s,1.5H),1.66(s,1.5H).13C-NMR(100MHz,CDCl3)δ:179.8,179.5,179.0,172.6,172.1,171.8,170.6,170.4,142.5,142.2,141.9,129.1,128.5,128.1,128.0,127.9,124.5,123.7,123.6,122.3,122.19,122.16,110.4,110.0,109.9,64.0,63.9,63.4,53.0,43.3,43.0,42.1,28.9,28.74,28.67,26.8,22.2,22.1,20.73,20.70,20.60.IR3223.1,2955.9,2924.5,1707.9,1621.5,1472.4,1403.3,1372.4,1334.8,1231.2,1102.8,1039.0,980.8,752.7,664.7,600.7cm-1;HRMS(CI+)(m/z)calcd.for C16H21N2O4[M+H]+305.1496;found305.1510.
实施例20:
将THF/H2O(10/1)20mL、20a(1g,3.67mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.37mmol,0.08g)或CeBr3(0.29mmol,0.11g),H2O2水溶液(30%,8.1mmol,0.82mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物20b(产率:FeBr2:75%;CeBr3:93%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.46(d,J=34.7Hz,1H),7.26–7.10(m,2H),7.08–6.91(m,2H),3.93–3.50(m,4H),2.41(dt,J=12.6,8.3Hz,1H),2.15–2.00(m,1H),1.48(d,J=24.4Hz,9H).13C-NMR(100MHz,CDCl3)δ:180.7,180.4,154.6,140.5,140.4,133.2,132.8,128.5,123.0,122.8,110.3,80.0,79.9,54.4,53.9,53.5,52.5,45.6,45.3,36.4,35.6,28.6,28.5.IR 3211.4,2975.0,1691.4,1620.0,1472.1,1399.8,1338.8,1224.0,1166.4,1126.2,878.2,735.9,576.9cm-1;HRMS(CI+)(m/z)calcd.for C16H20N2O3[M]+288.1468;found 288.1473.
实施例21:
THF/H2O(10/1)17mL、21a(1g,3.07mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.31mmol,0.06g)或CeBr3(0.25mmol,0.09g),H2O2水溶液(30%,6.7mmol,0.69mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物21b(产率:FeBr2:81%;CeBr3:94%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.00(s,1H),7.76(d,J=8.0Hz,2H),7.36(d,J=7.9Hz,2H),7.20(td,J=7.5,1.6Hz,1H),7.01–6.90(m,2H),6.88(d,J=7.7Hz,1H),3.71(dt,J=9.4,7.5Hz,1H),3.60–3.50(m,2H),3.46(d,J=9.8Hz,1H),2.45(s,3H),2.29(dt,J=12.6,7.9Hz,1H),2.10–2.00(m,1H).13C-NMR(100MHz,CDCl3)δ:179.5,144.0,140.0,133.3,132.8,129.9,128.6,127.8,123.2,123.1,110.2,56.0,53.0,47.4,36.3,21.7.IR 3283.3,1710.9,1617.0,1471.9,1337.9,1224.2,1157.6,1015.2,1015.2,811.3,747.1,662.8,590.7,548.8cm-1;HRMS(CI+)(m/z)calcd.forC18H18N2O3S[M+H]+343.1111;found 343.1118.
实施例22:
THF/H2O(10/1)26mL、22a(1g,4.67mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.47mmol,0.10g)或CeBr3(0.37mmol,0.14g),H2O2水溶液(30%,10.3mmol,1.05mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物22b(产率:FeBr2:68%;CeBr3:82%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.82–9.66(m,1H),7.21(qd,J=7.8,1.2Hz,1H),7.12(dd,J=7.6,4.2Hz,1H),7.05–6.91(m,2H),4.03–3.91(m,1H),3.90–3.75(m,2H),3.76–3.55(m,1H),2.49–2.33(m,1H),2.27–2.01(m,4H).13C-NMR(100MHz,CDCl3)δ:180.5,179.5,169.8,169.6,140.9,140.6,132.4,131.7,128.7,128.6,122.9,122.8,122.5,110.5,110.4,55.4,53.6,53.5,51.9,46.7,45.2,36.4,35.0,22.6,22.4.IR 3197.1,1709.1,1612.9,1460.1,1418.9,1338.9,1190.0,728.3cm-1;HRMS(CI+)(m/z)calcd.for C13H14N2O2[M]+230.1050;found 230.1059.
实施例23:
THF/H2O(10/1)24mL、23a(1g,4.35mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.44mmol,0.09g)或CeBr3(0.35mmol,0.13g),H2O2水溶液(30%,9.6mmol,0.98mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物23b(产率:FeBr2:75%;CeBr3:86%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.54(d,J=21.5Hz,1H),7.22(t,J=7.8Hz,1H),7.14(dd,J=7.6,3.4Hz,1H),7.02(t,J=7.6Hz,1H),6.95(d,J=7.8,1H),3.94–3.54(m,7H),2.41(ddt,J=16.6,11.7,5.3Hz,1H),2.15–2.00(m,1H).13C-NMR(100MHz,CDCl3)δ:180.5,180.2,155.6,155.5,140.6,140.5,132.6,132.3,128.6,123.0,122.9,122.7,110.4,54.3,54.0,53.4,52.8,52.7,52.5,45.8,45.3,36.4,35.5.IR 3229.3,1679.2,1618.1,1456.2,1388.8,1191.4,1128.1,744.7cm-1;HRMS(CI+)(m/z)calcd.for C13H14N2O3[M]+246.0999;found 246.1002.
实施例24:
THF/H2O(10/1)21mL、24a(1g,3.84mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.38mmol,0.08g)或CeBr3(0.31mmol,0.12g),H2O2水溶液(30%,8.5mmol,0.86mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物24b(产率:FeBr2:86%;CeBr3:83%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.60–9.42(m,1H),6.85(d,J=8.4Hz,1H),6.74(brs,2H),3.96–3.51(m,10H),2.45–2.30(m,1H),2.15–2.00(m,1H).13C-NMR(100MHz,CDCl3)δ:180.4,180.1,156.13,156.07,155.5,133.9,133.8,133.7,112.7,112.5,110.7,110.6,110.3,110.1,55.8,54.3,53.9,53.8,52.9,52.7,45.7,45.2,36.3,35.5.IR 3225.7,2953.1,1684.2,1450.5,1388.8,1307.9,1193.0,1033.2,812.6,729.5cm-1;HRMS(CI+)(m/z)calcd.for C14H16N2O4[M]+276.1105;found 276.1108.
实施例25:
THF/H2O(10/1)16mL、25a(1g,2.94mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.29mmol,0.06g)或CeBr3(0.24mmol,0.09g),H2O2水溶液(30%,8.5mmol,0.86mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物25b(产率:FeBr2:69%;CeBr3:90%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.75(brs,1H),7.52–7.36(m,2H),7.18(td,J=7.7,1.2Hz,1H),7.08–6.90(m,4H),5.16(dd,J=10.2,7.8Hz,1H),4.32(d,J=10.1Hz,1H),4.05(d,J=10.1Hz,1H),3.72(s,3H),2.60(dd,J=12.6,10.4Hz,1H),2.40(dd,J=12.7,8.1Hz,1H).13C-NMR(100MHz,CDCl3)δ:176.9,171.3,162.5,140.1,137.2,132.3,130.90,130.87,128.8,127.4,123.0,122.2,110.7,59.6,57.6,53.7,52.6,38.4.IR 3209.6,2953.6,2921.1,2876.8,1715.7,1608.5,1520.2,1470.9,1430.1,1396.3,1341.4,1267.6,1204.2,1100.8,1032.2,910.7,854.6,731.7,672.0cm-1;HRMS(CI+)(m/z)calcd.for C18H17N2O4S[M+H]+357.0904;found 357.0915.
实施例26:
THF/H2O(10/1)11mL、26a(1g,2.06mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.21mmol,0.04g)或CeBr3(0.16mmol,0.06g),H2O2水溶液(30%,4.5mmol,0.46mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物26b(产率:FeBr2:59%;CeBr3:57%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:9.43(brs,1H),7.35–7.20(m,2H),7.14(t,J=7.7Hz,1H),6.98–6.78(m,4H),4.66(d,J=13.8Hz,1H),3.67(s,1H),3.58–3.38(m,2H),2.93(s,3H),2.35–2.20(m,1H),2.11(brs,1H),0.93–0.88(m,21H).13C-NMR(100MHz,CDCl3)δ:182.1,165.2,141.4,137.3,129.3,129.0,128.7,128.4,126.6,125.0,122.4,109.9,59.3,54.2,52.8,39.2,38.5,17.9,11.9.IR 3221.3,2934.8,2863.8,1712.1,1613.7,1523.7,1464.1,1391.0,1336.8,1289.1,1265.3,1191.4,1104.5,1058.9,1003.1,921.0,882.1,849.8,807.7,743.5,680.6,649.4cm-1;HRMS(CI+)(m/z)calcd.for C26H39N2O3SSi[M+H]+487.2445;found487.2438.
实施例27:
THF/H2O(10/1)21mL、27a(1g,3.92mmol)依次加入圆底烧瓶中,搅拌均匀,然后向二者混合物中依次加入FeBr2(0.39mmol,0.08g)或CeBr3(0.31mmol,0.12g),H2O2水溶液(30%,8.6mmol,0.88mL),在室温下搅拌反应3h。反应完成后用Na2S2O3溶液(0.1M)淬灭反应,用乙酸乙酯萃取。合并有机相后,无水硫酸钠干燥,过滤,减压浓缩,即可得目标产物26b(产率:FeBr2:70%;CeBr3:88%)。该化合物的表征数据如下:1H-NMR(400MHz,CDCl3)δ:8.64(brs,1H),7.30–7.20(m,2H),7.06(td,J=7.6,1.0Hz,1H),6.95(d,J=7.7Hz,1H),4.26–4.07(m,2H),3.81(d,J=9.8Hz,1H),2.64(ddd,J=12.5,9.3,7.4Hz,1H),2.09(ddd,J=12.6,7.8,5.1Hz,1H),2.00(d,J=12.1Hz,1H),1.65(dd,J=12.0,4.3Hz,1H),1.48(d,J=12.0Hz,1H),1.43–1.27(m,2H),1.15–0.94(m,3H),0.91–0.64(m,3H).13C-NMR(100MHz,CDCl3)δ:180.6,140.0,132.1,128.0,124.7,122.8,110.1,90.1,66.4,56.6,40.6,39.4,31.1,27.4,26.2,25.5.IR 3224.6,2925.3,1705.0,1618.6,1471.3,1344.1,1222.4,1073.1,750.4cm-1;HRMS(CI+)(m/z)calcd.for C17H21NO2[M+H]+272.1645;found 272.1649.
本发明的研究工作得到南方海洋科学与工程广东省实验室(广州)香港分部(SMSEGL20Sc01-B)的支持,向其致谢。
Claims (10)
3.根据权利要求1所述的方法,其特征在于,所述催化剂为FeBr2、FeBr3、CeBr3以及FeCl3-KBr、Fe(NO3)3-KBr、FeSO4-KBr、CeCl3-KBr、Ce(NO3)3-KBr、Ce(OTf)3-KBr等金属和溴化物的组合中的任意一种。
4.根据权利要求1所述的方法,其特征在于,所述氧化剂为过氧化氢,浓度为3-30%。
5.根据权利要求1所述的方法,其特征在于,所述反应所用溶剂为有机溶剂:水(1:3)—纯有机溶剂,所述有机溶剂为四氢呋喃、乙腈、叔丁醇以及其它与水互溶的溶剂中的任意一种,溶剂与吲哚类化合物用量的比例为5ml/1mmol。
6.根据权利要求1所述的方法,其特征在于,所述吲哚类化合物与氧化剂的摩尔比为1:2-5;所述吲哚类化合物与催化剂的摩尔比为1:0.02-0.2。
7.根据权利要求1所述的方法,其特征在于,所述反应温度为室温。
8.根据权利要求1所述的方法,其特征在于,所述反应在pH为中性条件下进行。
9.根据权利要求1所述的方法,其特征在于,所述反应较佳反应时间为2-3h。
10.根据权利要求1所述的方法,其特征在于,反应结束后,Na2S2O3溶液淬灭,采用乙酸乙酯萃取,收集有机相,无水硫酸钠干燥,过滤,浓缩,即得氧化吲哚类衍生物。
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