CN112358432A - 一种吲哚类衍生物的合成方法 - Google Patents
一种吲哚类衍生物的合成方法 Download PDFInfo
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- CN112358432A CN112358432A CN202011204542.2A CN202011204542A CN112358432A CN 112358432 A CN112358432 A CN 112358432A CN 202011204542 A CN202011204542 A CN 202011204542A CN 112358432 A CN112358432 A CN 112358432A
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- 229940054051 antipsychotic indole derivative Drugs 0.000 title claims abstract description 8
- 238000010189 synthetic method Methods 0.000 title claims description 6
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- KURPPWHPIYBYBS-UHFFFAOYSA-N 2-ethenylaniline Chemical class NC1=CC=CC=C1C=C KURPPWHPIYBYBS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- -1 carbomethoxy group Chemical group 0.000 claims description 17
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- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 3
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
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- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
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- QNBUWOUWUWMJCB-UHFFFAOYSA-N 2-(4-chlorophenyl)-1-(4-methylphenyl)sulfonylindole Chemical compound ClC1=CC=C(C=C1)C=1N(C2=CC=CC=C2C=1)S(=O)(=O)C1=CC=C(C)C=C1 QNBUWOUWUWMJCB-UHFFFAOYSA-N 0.000 description 1
- OQYRJBWSMHCYCD-UHFFFAOYSA-N 2-(4-methoxyphenyl)-1-(4-methylphenyl)sulfonylindole Chemical compound COc1ccc(cc1)-c1cc2ccccc2n1S(=O)(=O)c1ccc(C)cc1 OQYRJBWSMHCYCD-UHFFFAOYSA-N 0.000 description 1
- TXWHUJXMGZIMFU-UHFFFAOYSA-N 2-(4-methylphenyl)-1-(4-methylphenyl)sulfonylindole Chemical compound CC1=CC=C(C=C1)C=1N(C2=CC=CC=C2C=1)S(=O)(=O)C1=CC=C(C)C=C1 TXWHUJXMGZIMFU-UHFFFAOYSA-N 0.000 description 1
- VSVHOUQNAJFYSX-UHFFFAOYSA-N 5-chloro-1-(4-methylphenyl)sulfonyl-2-phenylindole Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N1C2=CC=C(Cl)C=C2C=C1C1=CC=CC=C1 VSVHOUQNAJFYSX-UHFFFAOYSA-N 0.000 description 1
- PNLCYRPGWUBAGE-UHFFFAOYSA-N 5-fluoro-1-(4-methylphenyl)sulfonyl-2-phenylindole Chemical compound C1=CC(C)=CC=C1S(=O)(=O)N1C2=CC=C(F)C=C2C=C1C1=CC=CC=C1 PNLCYRPGWUBAGE-UHFFFAOYSA-N 0.000 description 1
- CKFBXGBEGVMBNA-UHFFFAOYSA-N C1(=CC=CC=C1)C=1N(C2=CC=C(C=C2C=1)C(F)(F)F)S(=O)(=O)C1=CC=C(C)C=C1 Chemical compound C1(=CC=CC=C1)C=1N(C2=CC=C(C=C2C=1)C(F)(F)F)S(=O)(=O)C1=CC=C(C)C=C1 CKFBXGBEGVMBNA-UHFFFAOYSA-N 0.000 description 1
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- HNRCQPUTZJXHCY-UHFFFAOYSA-N CC1=CC=C2C=C(N(C2=C1)S(=O)(=O)C1=CC=C(C)C=C1)C1=CC=CC=C1 Chemical compound CC1=CC=C2C=C(N(C2=C1)S(=O)(=O)C1=CC=C(C)C=C1)C1=CC=CC=C1 HNRCQPUTZJXHCY-UHFFFAOYSA-N 0.000 description 1
- VADSYUXXCUUROH-UHFFFAOYSA-N CCOC(C(C=C1)=CC=C1C1=CC2=CC=CC=C2N1S(C1=CC=C(C)C=C1)(=O)=O)=O Chemical compound CCOC(C(C=C1)=CC=C1C1=CC2=CC=CC=C2N1S(C1=CC=C(C)C=C1)(=O)=O)=O VADSYUXXCUUROH-UHFFFAOYSA-N 0.000 description 1
- KVOKFMJDMVRISU-UHFFFAOYSA-N ClC1=C(C=CC=C1)C=1N(C2=CC=CC=C2C=1)S(=O)(=O)C1=CC=C(C)C=C1 Chemical compound ClC1=C(C=CC=C1)C=1N(C2=CC=CC=C2C=1)S(=O)(=O)C1=CC=C(C)C=C1 KVOKFMJDMVRISU-UHFFFAOYSA-N 0.000 description 1
- WSLATPVIRRCIBY-UHFFFAOYSA-N ClC=1C=C(C=CC=1)C=1N(C2=CC=CC=C2C=1)S(=O)(=O)C1=CC=C(C)C=C1 Chemical compound ClC=1C=C(C=CC=1)C=1N(C2=CC=CC=C2C=1)S(=O)(=O)C1=CC=C(C)C=C1 WSLATPVIRRCIBY-UHFFFAOYSA-N 0.000 description 1
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- LCQMZZCPPSWADO-UHFFFAOYSA-N Reserpilin Natural products COC(=O)C1COCC2CN3CCc4c([nH]c5cc(OC)c(OC)cc45)C3CC12 LCQMZZCPPSWADO-UHFFFAOYSA-N 0.000 description 1
- QEVHRUUCFGRFIF-SFWBKIHZSA-N Reserpine Natural products O=C(OC)[C@@H]1[C@H](OC)[C@H](OC(=O)c2cc(OC)c(OC)c(OC)c2)C[C@H]2[C@@H]1C[C@H]1N(C2)CCc2c3c([nH]c12)cc(OC)cc3 QEVHRUUCFGRFIF-SFWBKIHZSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
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- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 229960003765 fluvastatin Drugs 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WFGFKKMCJSVSFO-UHFFFAOYSA-N methyl 1-(4-methylphenyl)sulfonyl-2-phenylindole-6-carboxylate Chemical compound COC(=O)c1ccc2cc(-c3ccccc3)n(c2c1)S(=O)(=O)c1ccc(C)cc1 WFGFKKMCJSVSFO-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002858 neurotransmitter agent Substances 0.000 description 1
- BJOIZNZVOZKDIG-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C([C]5C=CC(OC)=CC5=N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 BJOIZNZVOZKDIG-MDEJGZGSSA-N 0.000 description 1
- 229960003147 reserpine Drugs 0.000 description 1
- ULFRLSNUDGIQQP-UHFFFAOYSA-N rizatriptan Chemical compound C1=C2C(CCN(C)C)=CNC2=CC=C1CN1C=NC=N1 ULFRLSNUDGIQQP-UHFFFAOYSA-N 0.000 description 1
- 229960000425 rizatriptan Drugs 0.000 description 1
- MDMGHDFNKNZPAU-UHFFFAOYSA-N roserpine Natural products C1C2CN3CCC(C4=CC=C(OC)C=C4N4)=C4C3CC2C(OC(C)=O)C(OC)C1OC(=O)C1=CC(OC)=C(OC)C(OC)=C1 MDMGHDFNKNZPAU-UHFFFAOYSA-N 0.000 description 1
- 229940126586 small molecule drug Drugs 0.000 description 1
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IEHKWSGCTWLXFU-IIBYNOLFSA-N tadalafil Chemical compound C1=C2OCOC2=CC([C@@H]2C3=C([C]4C=CC=CC4=N3)C[C@H]3N2C(=O)CN(C3=O)C)=C1 IEHKWSGCTWLXFU-IIBYNOLFSA-N 0.000 description 1
- 229960000835 tadalafil Drugs 0.000 description 1
- KCFYEAOKVJSACF-UHFFFAOYSA-N umifenovir Chemical compound CN1C2=CC(Br)=C(O)C(CN(C)C)=C2C(C(=O)OCC)=C1CSC1=CC=CC=C1 KCFYEAOKVJSACF-UHFFFAOYSA-N 0.000 description 1
- 229960004626 umifenovir Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
- C07D409/04—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 directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
本发明公开了一种吲哚衍生物的合成方法，包括如下步骤：将原料邻乙烯基苯胺衍生物II溶于二甲基亚砜中，逐滴加入二氯亚砜，进行反应，得到吲哚类衍生物I；
Description
技术领域
本发明涉及一种吲哚类衍生物的合成方法。
背景技术
吲哚类化合物是自然界最为丰富的杂环化合物之一，具有重要的价值。1在近几十年的发展中，吲哚类化合物在化工、材料和医药等领域的应用越来越广泛。吲哚骨架广泛存在于具有生物活性的天然产物中，比如5-羟色胺作为神经递质广泛存在于哺乳动物组织中，利血平作为治疗高血压的常用药物。2此外，许多小分子药物中同样含有吲哚结构，例如他达拉非，利扎曲普坦，氟伐他汀和阿比多尔。3到目前为止，对于吲哚类衍合物的化学合成已有报道，但是在这些以邻乙烯基苯胺衍生物(II)化合物为原料的合成方法中，4并未见在二氯亚砜和二甲基亚砜的共同作用下形成吲哚衍生物(I)的报道。
具体见以下参考文献：
(1)(a)Nichols,D.E.；Nichols,C.D.Chem.Rev.2008,108,1614.(b)Taber,D.F.；Tirunahari,P.K.Tetrahedron 2011,67,7195.(c)Bandini,M.；Eichholzer,A.Angew.Chem.Int.Ed.2009,48,9608.
(2)(a)Daugan,A.；Grondin,P.；Ruault,C.；de Gouville,A.C.L.；Coste,H.；Linget,J.M.；Kirilovsky,J.；Hyafil,F.；Labaudiniere,R.J.Med.Chem.2003,46,4533.(b)Williamson,D.J.；Shepheard,S.L.；Hill,R.G.；Hargreaves,R.J.Eur.J.Pharmacol.1997,328.(c)Nakashima,A.；Ohtawa,M.；Iwasaki,K.；Wada,M.；Kuroda,N.；Nakashima,K.Life Sci.2001,69,1381.(d)Blaising,J.；Polyak,S.J.；Pecheur,E.I.Antivir.Res.2014,107,84.
(3)(a)Shu,D.X.；Song,W.Z.；Li,X.X.；Tang,W.P.Angew.Chem.Int.Ed.2013,52,3237.(b)Higuchi,K.；Kawasaki,T.Nat.Prod.Rep.2007,24,843.(c)Kochanowska-Karamyan,A.J.；Hamann,M.T.Chem.Rev.2010,110,4489.(d)Inman,M.；Moody,C.J.Chem.Sci.2013,4,29.
(4)(a)Hegedus,L.S.；Allen,G.F.；Bozell,J.J.；Waterman,E.L.J.Am.Chem.Soc.1978,100,5800.(b)Harrington,P.J.；Hegedus,L.S.；McDaniel,K.F.J.Am.Chem.Soc.1987,109,4335.(c)Manna,M.K.；Hossian,A.；Jana,R.Org.Lett.2015,17,672.(d)Youn,S.W.；Ko,T.Y.；Jang,M.J.；Jang,S.S.Adv.Synth.Catal.2015,357,227.(e)Fra,L.；Millán,A.；Souto,J.A.；
K.Angew.Chem.Int.Ed.2014,53,7349.(f)Jang,Y.H.；Youn,S.W.Org.Lett.2014,16,3720.(g)Ortgies,S.；Breder,A.Org.Lett.2015,17,2748.(h)Zhang,X.L.；Guo,R.Z.；Zhao,X.D.Org.Chem.Front.2015,2,1334.(i)Li,Y.L.；Li,J.；Ma,A.L.；Huang,Y.N.；Deng,J.J.Org.Chem.2015,80,3841.
发明内容
本发明的目的是克服现有技术的不足，提供一种简单实现分子内环化的吲哚类衍生物的合成方法。
本发明的技术方案概述如下：
一种吲哚类衍生物的合成方法，包括如下步骤：将原料邻乙烯基苯胺衍生物II溶于二甲基亚砜中，逐滴加入二氯亚砜，反应得到吲哚类衍生物I；
其中：
R1为氢原子、氟原子、氯原子、溴原子、甲酯基、甲基、三氟甲基或氰基；
R2为苯基、4-甲基苯、4-甲氧基苯基、4-氯苯基、3-氯苯基、2-氯苯基、4-氟苯基、4-三氟甲基苯基、4-乙酯基苯基、2-噻吩基或2-萘基；
R3为对甲苯磺酰基、甲磺酰基或4-氯苯磺酰基。
邻乙烯基苯胺衍生物(II)与二氯亚砜的摩尔比优选为1:3。
本发明具有操作简单，原料价廉易得，反应条件温和，反应时间短，收率理想等优点.
具体实施方式
二氯亚砜(SOCl2)为商业购买的分析纯的二氯亚砜。
二甲基亚砜(DMSO)为商业购买的绝对无水的二甲基亚砜(无水二甲基亚砜)。
实施例中所需要的反应原料，即邻乙烯基苯胺衍生物II，为参照文献方法制备。((1)Youn,S.W.；Ko,T.Y.；Jang,M.J.；Jang,S.S.Adv.Synth.Catal.2015,357,227.)
下面通过具体实施例对本发明作进一步的说明。
实施例1
2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-a的制备
将N-[2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-a(0.5mmol,174mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝5:95)分离得到白色固体159mg,收率为92％,熔点为145-147℃。1H NMR(600MHz,CDCl3)δ8.31(d,J＝8.4Hz,1H),7.52-7.47(m,2H),7.45-7.39(m,4H),7.37-7.32(m,1H),7.26-7.23(m,2H),7.02(d,J＝8.3Hz,2H),6.53(s,1H),2.27(s,3H).13C NMR(151MHz,CDCl3)δ144.5,142.2,138.3,134.8,132.5,130.6,130.4,129.2,128.7,127.5,126.8,124.8,124.3,120.7,116.7,113.6,21.5.HRMS(ESI)calcd for C21H17NNaO2S+[M+Na+]370.0878,found 370.0882.
实施例2
5-氯-2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-b的制备
将N-[4-氯-2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-b(0.5mmol,192mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体165mg,收率为83％,熔点为142-143℃。1H NMR(400MHz,CDCl3)δ8.23(d,J＝8.9Hz,1H),7.54-7.38(m,6H),7.30(dd,J＝8.9,2.1Hz,1H),7.24(d,J＝8.4Hz,3H),7.05(d,J＝8.2Hz,2H),6.47(s,1H),2.30(s,3H).13C NMR(101MHz,CDCl3)δ144.9,143.6,136.6,134.4,131.9,131.7,130.4,130.0,129.4,129.0,127.6,126.8,124.9,120.3,117.7,112.6,21.6.HRMS(ESI)calcd forC21H16 35ClNNaO2S+[M+Na+]404.0488,found404.0485.
实施例3
5-氟-2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-c的制备
将N-[4-氟-2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-c(0.5mmol,184mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝1:9)分离得到白色固体165mg,收率为91％,熔点为113-115℃。1H NMR(600MHz,CDCl3)δ8.25(dd,J＝8.9,4.5Hz,1H),7.51-7.39(m,5H),7.24(d,J＝8.4Hz,2H),7.12-7.02(m,4H),6.50(s,1H),2.30(s,3H).13C NMR(151MHz,CDCl3)δ160.2(d,1JC-F＝239.7Hz),144.7,144.0,134.6,134.5,132.1,131.6(d,3JC-F＝10.0Hz),130.3,129.3,128.9,127.6,126.8,117.9(d,3JC-F＝9.2Hz),113.2(d,4JC-F＝3.8Hz),112.5(d,2JC-F＝25.0Hz),106.3(d,2JC-F＝23.8Hz),21.5.HRMS(ESI)calcd forC21H16FNNaO2S+[M+Na+]388.0783,found 388.0781.
实施例4
6-溴-2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-d的制备
将N-[5-溴-2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-d(0.5mmol,214mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝1:9)分离得到白色固体186mg，收率为87％，熔点为156-157℃。1HNMR(600MHz,CDCl3)δ8.51(s,1H),7.48-7.36(m,6H),7.30(d,J＝8.3Hz,1H),7.25(d,J＝8.2Hz,2H),7.06(d,J＝8.2Hz,2H),6.48(s,1H),2.30(s,3H).13C NMR(151MHz,CDCl3)δ144.9,142.6,138.9,134.7,131.9,130.4,129.4,129.3,128.9,127.6,127.5,126.9,121.7,119.6,118.3,112.8,21.6.HRMS(ESI)calcd for C21H16 79BrNNaO2S+[M+Na+]449.9983,found 449.9981.
实施例5
6-氟-2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-e的制备
将N-[5-氟-2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-e(0.5mmol,184mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝1:9)分离得到白色固体168mg，收率为92％，熔点为103-105℃。1HNMR(600MHz,CDCl3)δ8.06(dd,J＝10.4,2.1Hz,1H),7.49-7.39(m,5H),7.36(dd,J＝8.5,5.4Hz,1H),7.27(d,J＝8.4Hz,2H),7.06(d,J＝8.1Hz,2H),7.02(td,J＝8.8,2.3Hz,1H),6.49(s,1H),2.30(s,3H).13C NMR(151MHz,CDCl3)δ161.7,160.1,144.8,142.4(d,4JC-F＝4.3Hz),138.6(d,3JC-F＝12.5Hz),134.7,132.1,130.4,129.3,128.7,127.5,126.9,126.7,121.3(d,3JC-F＝9.7Hz),112.8,112.6(d,2JC-F＝24.1Hz),104.0(d,2JC-F＝28.6Hz),21.5.HRMS(ESI)calcd for C21H16FNNaO2S+[M+Na+]388.0783,found 388.0782.
实施例6
6-甲氧羰基-2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-f的制备
将N-[5-甲氧羰基-2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-f(0.5mmol,204mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体181mg，收率为86％，熔点为165-166℃。1H NMR(600MHz,CDCl3)δ9.01(s,1H),7.97(d,J＝8.1Hz,1H),7.45(ddd,J＝20.2,15.4,7.5Hz,6H),7.30-7.21(m,2H),7.04(d,J＝8.2Hz,2H),6.56(s,1H),3.98(s,3H),2.27(s,3H).13C NMR(151MHz,CDCl3)δ167.4,145.2,144.9,137.7,134.6,134.2,131.8,130.4,129.4,129.1,127.6,126.9,126.5,125.6,120.4,118.3,113.1,52.3,21.6.HRMS(ESI)calcd for C23H19NNaO4S+[M+Na+]428.0932,found 428.0933.
实施例7
6-甲基-2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-g的制备
将N-[5-甲基-2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-g(0.5mmol,182mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体176mg，收率为98％，熔点为178-180℃。1HNMR(600MHz,CDCl3)δ8.12(s,1H),7.47(d,J＝4.6Hz,2H),7.40(s,3H),7.30(d,J＝7.8Hz,1H),7.24(t,J＝8.4Hz,2H),7.08(d,J＝7.7Hz,1H),7.02(d,J＝7.9Hz,2H),6.47(s,1H),2.51(s,3H),2.26(s,3H).13C NMR(151MHz,CDCl3)δ144.4,141.5,138.8,134.9,134.8,132.6,130.3,129.2,128.5,128.3,127.5,126.8,125.8,120.3,116.9,113.6,22.1,21.5.HRMS(ESI)calcd for C22H19NNaO2S+[M+Na+]384.1034,found 384.1038.
实施例8
5-三氟甲基-2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-h的制备
将N-[4-三氟甲基-2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-h(0.5mmol,209mg)溶于二甲基亚砜(1mL)中，滴入二氯亚砜(1.5mmol,179mg)，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体151mg，收率为73％，熔点为123-125℃。1H NMR(600MHz,CDCl3)δ8.43(d,J＝8.8Hz,1H),7.75(s,1H),7.52-7.39(m,5H),7.28(m,2H),7.08(d,J＝8.1Hz,2H),6.59(s,1H),2.31(s,3H).13C NMR(151MHz,CDCl3)δ145.1,143.7,139.7,134.8,131.6,130.6,130.0,129.5,129.1,127.6,126.8,126.5(q,2JC-F＝21.4Hz),125.4,121.4(q,4JC-F＝2.4Hz),118.1(q,4JC-F＝2.7Hz),116.7,112.7,21.5.HRMS(ESI)calcd for C22H16F3NNaO2S+[M+Na+]438.0752,found 438.0750.
实施例9
5-氰基-2-苯基-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-i的制备
将N-[4-氰基-2-[(1E)-2-苯基乙烯基]苯基]-4-甲基苯磺酰胺ll-i(0.5mmol,187mg)溶于二甲基亚砜(1mL)中，滴入二氯亚砜(1.5mmol,179mg)，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝20:80)分离得到白色固体121mg，收率为65％，熔点为118-119℃。1H NMR(600MHz,CDCl3)δ8.42(d,J＝8.7Hz,1H),7.80(d,J＝1.1Hz,1H),7.61(dd,J＝8.7,1.6Hz,1H),7.50-7.40(m,5H),7.25(d,J＝8.4Hz,2H),7.08(d,J＝8.1Hz,2H),6.57(s,1H),2.32(s,3H).13C NMR(151MHz,CDCl3)δ145.4,144.2,139.9,134.7,131.2,130.6,130.3,129.5,129.3,127.6,126.8,125.6,125.4,119.3,117.1,112.0,107.7,21.6.HRMS(ESI)calcd for C22H16N2NaO2S+[M+Na+]395.0830,found395.0833.
实施例10
2-(4-甲基苯基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-j的制备
将N-[2-[(1E)-2-(4-甲基苯基)乙烯基]苯基]-4-甲基苯磺酰胺ll-j(0.5mmol,182mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体167mg,收率为92％,熔点为101-103℃。1HNMR(400MHz,CDCl3)δ8.30(d,J＝8.4Hz,1H),7.41(t,J＝7.6Hz,3H),7.33(t,J＝7.2Hz,1H),7.28(d,J＝8.5Hz,3H),7.22(s,1H),7.03(d,J＝8.1Hz,2H),6.50(s,1H),2.43(s,3H),2.27(s,3H).13C NMR(101MHz,CDCl3)δ144.5,142.3,138.7,138.2,134.6,130.7,130.2,129.6,129.2,128.3,126.8,124.6,124.3,120.6,116.7,113.3,21.6,21.5.HRMS(ESI)calcd for C22H19NNaO2S+[M+Na+]384.1034,found 384.1038.
实施例11
2-(4-甲氧基苯基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-k的制备
将N-[2-[(1E)-2-(4-甲氧基苯基)乙烯基]苯基]-4-甲基苯磺酰胺ll-k(0.5mmol,190mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体170mg,收率为90％,熔点为135-137℃。1HNMR(400MHz,CDCl3)δ8.30(d,J＝8.9Hz,1H),7.42(d,J＝8.8Hz,1H),7.37-7.31(m,1H),7.25-7.27(m,3H),7.04(d,J＝8.1Hz,1H),6.95(d,J＝8.8Hz,1H),6.48(s,1H),3.89(s,1H),2.28(s,1H).13C NMR(101MHz,CDCl3)δ160.0,144.5,142.0,138.2,134.7,131.7,130.6,129.2,126.8,124.7,124.5,124.3,120.5,116.7,113.0,112.9,55.3,21.5.HRMS(ESI)calcd for C22H19NNaO3S+[M+Na+]400.0983,found 400.0986.
实施例12
2-(4-氯苯基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-l的制备
将N-[2-[(1E)-2-(4-氯苯基)乙烯基]苯基]-4-甲基苯磺酰胺ll-l(0.5mmol,192mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体178mg,收率为94％,熔点为138-140℃。1HNMR(600MHz,CDCl3)δ8.30(d,J＝8.4Hz,1H),7.43(dd,J＝8.5,2.4Hz,3H),7.40-7.34(m,3H),7.26(t,J＝8.0Hz,3H),7.03(d,J＝8.2Hz,2H),6.53(s,1H),2.27(s,3H).13C NMR(151MHz,CDCl3)δ144.7,140.8,138.4,134.8,134.6,131.5,130.9,130.5,129.3,127.9,126.8,125.1,124.5,120.8,116.7,114.0,21.5.HRMS(ESI)calcd for C21H16 35ClNNaO2S+[M+Na+]404.0488,found 404.0489.
实施例13
2-(3-氯苯基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-m的制备
将N-[2-[(1E)-2-(3-氯苯基)乙烯基]苯基]-4-甲基苯磺酰胺ll-m(0.5mmol,192mg)溶于二甲基亚砜(0.5mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白固体152mg,收率为79％，熔点为49-50℃。1HNMR(400MHz,CDCl3)δ8.30(d,J＝9.0Hz,1H),7.50-7.33(m,5H),7.25(dd,J＝11.2,5.0Hz,3H),7.04(d,J＝8.1Hz,2H),6.55(s,1H),2.28(s,3H).13C NMR(101MHz,CDCl3)δ144.8,140.4,138.4,134.5,134.2,133.4,130.3,130.0,129.4,128.8,128.8,128.7,126.8,125.2,124.5,121.0,116.7,114.3,21.6.HRMS(ESI)calcd for C21H16 35ClNNaO2S+[M+Na+]404.0488,found404.0488.
实施例14
2-(2-氯苯基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-n的制备
将N-[2-[(1E)-2-(2-氯苯基)乙烯基]苯基]-4-甲基苯磺酰胺ll-n(0.5mmol,192mg)溶于二甲基亚砜(0.5mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色油130mg,收率为68％。1HNMR(400MHz,CDCl3)δ8.30(dd,J＝8.4,0.7Hz,1H),7.54-7.26(m,9H),7.11(d,J＝8.0Hz,2H),6.64(s,1H),2.31(s,3H).13C NMR(101MHz,CDCl3)δ144.8,137.4,137.2,135.2,135.1,133.0,131.6,130.2,129.9,129.5,129.4,127.0,125.8,125.0,124.0,121.1,115.7,113.8,21.6.HRMS(ESI)calcd for C21H16 35ClNNaO2S+[M+Na+]404.0488,found 404.0485.
实施例15
2-(4-氟苯基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-o的制备
将N-[2-[(1E)-2-(4-氟苯基)乙烯基]苯基]-4-甲基苯磺酰胺ll-o(0.5mmol,184mg)溶于二甲基亚砜(0.5mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色油152mg,收率为83％。1HNMR(400MHz,CDCl3)δ8.31(d,J＝8.4Hz,1H),7.45(ddd,J＝8.8,5.8,2.8Hz,3H),7.36(ddd,J＝8.5,7.3,1.3Hz,1H),7.30-7.22(m,3H),7.10(t,J＝8.7Hz,2H),7.04(d,J＝8.0Hz,2H),6.51(s,1H),2.28(s,3H).13C NMR(101MHz,CDCl3)δ163.1(d,1JC-F＝249.5Hz),144.7,140.9,138.2,134.6,132.1(d,3JC-F＝8.3Hz),130.4,129.3,128.4(d,4JC-F＝3.4Hz),126.7,125.0,124.4,120.7,116.7,114.6(d,2JC-F＝21.6Hz),113.7,21.6.HRMS(ESI)calcd for C21H16FNNaO2S+[M+Na+]388.0783,found 388.0782.
实施例16
2-(4-三氟甲基苯基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-p的制备
将N-[2-[(1E)-2-(4-三氟甲基苯基)乙烯基]苯基]-4-甲基苯磺酰胺ll-p(0.5mmol,209mg)溶于二甲基亚砜(0.5mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体141mg,收率为68％,熔点为164-165℃。1H NMR(400MHz,CDCl3)δ8.31(dd,J＝8.4,0.6Hz,1H),7.66(q,J＝8.3Hz,4H),7.46(d,J＝7.7Hz,1H),7.39(ddd,J＝8.5,7.3,1.3Hz,1H),7.30-7.25(m,3H),7.04(d,J＝8.0Hz,2H),6.61(s,1H),2.28(s,3H).13C NMR(101MHz,CDCl3)δ144.9,140.5,138.5,136.1,134.3,130.4,129.4,126.7,125.4,124.6,124.5(q,4JC-F＝3.7Hz),121.0,116.7,115.0,21.6.HRMS(ESI)calcd for C22H16F3NNaO2S+[M+Na+]438.0752,found438.0756.
实施例17
2-(4-乙氧基羰基苯基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-q的制备
将N-[2-[(1E)-2-(4-乙氧基羰基苯基)乙烯基]苯基]-4-甲基苯磺酰胺ll-q(0.5mmol,210mg)溶于二甲基亚砜(0.5mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝10:90)分离得到白色固体155mg,收率为74％,熔点为118-119℃。1H NMR(400MHz,CDCl3)δ8.31(d,J＝8.4Hz,1H),8.11(d,J＝8.4Hz,2H),7.60(d,J＝8.3Hz,2H),7.45(d,J＝7.6Hz,1H),7.38(t,J＝7.3Hz,1H),7.29(d,J＝7.9Hz,1H),7.24(s,1H),7.04(d,J＝8.1Hz,2H),7.04(d,J＝8.1Hz,2H),6.61(s,1H),4.43(q,J＝7.1Hz,2H),2.28(s,3H),1.43(t,J＝7.1Hz,3H).13C NMR(101MHz,CDCl3)δ166.4,144.8,141.1,138.6,136.8,134.3,130.5,130.4,130.1,129.3,128.8,126.8,125.3,124.6,121.0,116.8,114.9,61.1,21.6,14.4.HRMS(ESI)calcd for C24H21NNaO4S+[M+Na+]442.1089,found 442.1088.
实施例18
2-(2-噻吩基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-r的制备
将N-[2-[(1E)-2-(2-噻吩基)乙烯基]苯基]-4-甲基苯磺酰胺ll-r(0.5mmol,178mg)溶于二甲基亚砜(0.5mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝5:95)分离得到白色固体119mg,收率为67％,熔点为90-91℃。1H NMR(400MHz,CDCl3)δ8.32(dd,J＝8.4,0.7Hz,1H),7.44(d,J＝7.8Hz,1H),7.40(dd,J＝5.1,1.2Hz,1H),7.38-7.30(m,4H),7.29-7.23(m,1H),7.11(dd,J＝5.1,3.6Hz,1H),7.05(d,J＝8.0Hz,2H),6.63(s,1H),2.28(s,3H).13C NMR(101MHz,CDCl3)δ144.7,138.3,134.9,134.0,132.4,130.6,129.9,129.4,127.1,127.0,126.8,125.2,124.3,120.8,116.5,114.5,21.6.HRMS(ESI)calcd for C19H15NNaO2S2 +[M+Na+]376.0442,found 376.0446.
实施例19
2-(2-萘基)-1-[(4-甲基苯基)磺酰基]-1H-吲哚l-s的制备
将N-[2-[(1E)-2-(2-萘基)乙烯基]苯基]-4-甲基苯磺酰胺ll-s(0.5mmol,200mg)溶于二甲基亚砜(0.5mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝5:95)分离得到白色固体191mg,收率为96％,熔点为152-153℃。1HNMR(600MHz,CDCl3)δ8.34(d,J＝8.3Hz,1H),7.88(t,J＝10.5Hz,4H),7.69(d,J＝8.3Hz,1H),7.55-7.50(m,2H),7.45(d,J＝7.6Hz,1H),7.36(t,J＝7.7Hz,1H),7.26(t,J＝14.4Hz,3H),6.99(d,J＝8.0Hz,2H),6.62(s,1H),2.25(s,3H).13C NMR(151MHz,CDCl3)δ142.2,138.5,134.7,134.7,133.3,132.7,130.7,130.2,129.2,128.8,128.6,128.2,127.9,126.9,126.8,126.6,126.4,124.9,124.4,120.8,116.7,114.2,21.5.HRMS(ESI)calcd forC25H19NNaO2S+[M+Na+]420.1034,found 420.1036.
实施例20
2-苯基-1-(甲基磺酰基)-1H-吲哚l-t的制备
将N-[2-[(1E)-2-(2-苯基)乙烯基]苯基]-甲磺酰胺ll-t(0.5mmol,137mg)溶于二甲基亚砜(0.5mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝5:95)分离得到白色固体126mg,收率为92％,熔点为120-122℃。1H NMR(600MHz,CDCl3)δ8.12(d,J＝8.0Hz,1H),7.59(d,J＝7.2Hz,1H),7.57-7.54(m,2H),7.45-7.40(m,3H),7.40-7.32(m,2H),6.70(s,1H),2.72(s,3H).13C NMR(151MHz,CDCl3)δ142.0,138.0,132.0,130.3,130.2,128.9,127.8,125.2,124.6,121.1,115.9,113.1,39.5.HRMS(ESI)calcd for C21H17NNaO2S+[M+Na+]370.0878,found 370.0882.
实施例21
2-苯基-1-[(4-氯苯基)磺酰基]-1H-吲哚l-u的制备
将N-[2-[(1E)-2-苯基乙烯基]苯基]-4-氯苯磺酰胺ll-u(0.5mmol,185mg)溶于二甲基亚砜(1mL)中，在0℃下逐滴加入二氯亚砜(1.5mmol,179mg)，在室温下反应直至TLC显示底物完全反应。用水(20mL)和二氯甲烷(20mL×3)萃取反应液，合并有机相，先用饱和碳酸氢钠洗涤有机相，再用饱和食盐水洗涤有机相，加入无水硫酸钠干燥，经柱层析(乙酸乙酯：石油醚＝5:95)分离得到白色固体177mg,收率为96％,熔点为186-188℃。1H NMR(600MHz,CDCl3)δ8.28(d,J＝8.4Hz,1H),7.53-7.39(m,6H),7.35(t,J＝7.7Hz,1H),7.28(d,J＝8.7Hz,3H),7.18(d,J＝8.6Hz,2H),6.55(s,1H).13C NMR(151MHz,CDCl3)δ142.1,140.2,138.3,135.9,132.1,130.7,130.3,128.9,128.9,128.2,127.7,125.1,124.7,121.0,116.7,114.2.HRMS(ESI)calcd for C20H14 35ClNNaO2S+[M+Na+]390.0331,found390.0336.
以上所述，仅是本发明的部分实施例而已，并非对本发明做任何形式上的限制，凡是依据本发明的技术实质对上述实施例作的任何简单的修改，等同变化与修饰，均属于本发明技术方案范围内。
Claims (1)
1.一种吲哚类衍生物的合成方法，其特征是包括如下步骤：将原料邻乙烯基苯胺衍生物(II)溶于二甲基亚砜中，逐滴加入二氯亚砜，反应得到吲哚类衍生物(I)；
其中：
R1为氢原子、氟原子、氯原子、溴原子、甲酯基、甲基、三氟甲基或氰基；
R2为苯基、4-甲基苯、4-甲氧基苯基、4-氯苯基、3-氯苯基、2-氯苯基、4-氟苯基、4-三氟甲基苯基、4-乙酯基苯基、2-噻吩基或2-萘基；
R3为对甲苯磺酰基、甲磺酰基或4-氯苯磺酰基。
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| CN104592086A (zh) * | 2015-01-31 | 2015-05-06 | 台州学院 | 一种通过铜盐催化制备吲哚类化合物的方法 |
| CN107118145A (zh) * | 2017-06-22 | 2017-09-01 | 中国科学技术大学 | 一种钯‑有机亚硝酸盐共同催化的环化合成吲哚的方法 |
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