CN105418481B - 一种3‑吲哚硫醚的制备方法 - Google Patents

一种3‑吲哚硫醚的制备方法 Download PDF

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CN105418481B
CN105418481B CN201510978857.5A CN201510978857A CN105418481B CN 105418481 B CN105418481 B CN 105418481B CN 201510978857 A CN201510978857 A CN 201510978857A CN 105418481 B CN105418481 B CN 105418481B
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罗美明
齐鸿
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Sichuan University
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Abstract

本发明以邦特盐为硫源制备3‑吲哚硫醚。在一定的温度下，以碘单质或氢碘酸及其盐为催化剂，二甲基亚砜为氧化剂，邦特盐为硫源，在无或有其它溶剂的条件下与吲哚类化合物反应制备3‑吲哚硫醚。该方法具有试剂廉价易得，反应条件温和，底物适用性广，所用试剂气味小、对环境污染小等特点。

Description

一种3-吲哚硫醚的制备方法
技术领域
本发明是关于制备3-吲哚硫醚的方法，该方法以二甲基亚砜为氧化剂、碘单质或碘化物为催化剂，邦特（Bunte）盐作为硫化试剂与吲哚类物质反应制备3-吲哚硫醚。
背景技术
作为取代吲哚中的重要一员，3-吲哚硫醚及其衍生物具有重要的医药价值。据报道，一些具有3-吲哚硫醚结构的药物分子对于HIV、肥胖、过敏、癌症和心脏病等有良好的疗效（Antiviral Chem. Chemother.2006, 17, 59、J. Med. Chem. 2006, 49, 3172、 J. Med. Chem.2004, 47, 6120、Nat. Rev. Drug Discovery 2005, 4, 664、J. Med. Chem.1989, 32, 1360）。除此之外，3-吲哚硫醚还是COX-2的有效抑制剂以及微管蛋白聚合的潜在抑制剂（J. Org. Chem. 2004, 69, 7688、J. Med. Chem. 2006, 49, 947）。合成3-吲哚硫醚的方法主要有三类：一是用硫化试剂直接对吲哚类物质进行硫化(US20040133014、CN102558020 A、 CN103288707A、 Synthesis2009, 9, 1520、Org. Lett.2004, 6, 819.)。由于吲哚环的富电性，这类方法使用得最多。在这类方法中很多使用了硫酚（醇）作为硫化试剂，气味大，毒性重，会对人体造成较大的伤害，也会污染环境；二是用亲核试剂对吲哚C3位进行亲核取代制备3-吲哚硫醚（Tetrahedron2008, 64,11625.），这种方法一般要求吲哚环的C2位和C3位同时有取代基存在，使用的亲核试剂硫酚（醇）要求过量，有时还需要相转移催化剂存在，条件比较苛刻，使用得最少; 三是由2-炔基-（取代）苯胺和二硫醚或硫氯在金属催化剂或相转移催化剂的作用下关环合成（Adv. Synth. Catal. 2009, 351, 2615、Adv. Synth. Catal. 2011, 353, 2739.)，这种方法对底物结构要求较为苛刻，适用范围窄。
邦特盐，即S-烷基或S-芳基硫代硫酸盐，来源丰富，有多种制备方法（J. Am. Chem. Soc. 1936, 58, 262；J. Org. Chem. 1955, 20, 475；Langmuir2010, 26, 9497；Org. Lett. 2014, 16, 1196；RSC Adv.2013, 3, 2650.）。一般的邦特盐都呈晶状固体，通常都味道很小或没有气味，很便于操作使用。邦特盐在有机合成反应（Org. Lett.2014,16, 1196；RSC Adv. 2015, 34, 27107；Langmuir 2004, 20, 6626；Langmuir2010, 26 ,7504；US6515114）、染料、化妆品、塑料以及记录材料中 （JP2003146828）、抗菌（Pharmazie1998, 53, 190；Langmuir2000, 16, 6555）等方面已有广泛应用。
发明内容
如前所述，虽然3-吲哚硫醚已有多种制备方法，但是它们都存在一定的局限性。本发明，以碘单质或氢碘酸及其盐为催化剂，以二甲基亚砜（DMSO）为氧化剂，以邦特盐为硫化试剂，在有或无其它溶剂的条件下与吲哚类物质发生反应生成3-吲哚硫醚。该方法具有试剂廉价易得，反应条件温和，底物适用性广，所用试剂气味小、对环境污染小等特点。
本发明的方法具有如下的反应通式：
其中：Z代表CH、N，R1代表H、C1-C20烷基，R2代表H、C1-C20烷基、C6-C20芳基、酯基，R3代表H、C1-C20烷基、C1-C20烷氧基、C6-C20芳基、酯基、卤素、硝基、氰基，R4代表C1-C20烷基、C6-C20芳基、C6-C20杂芳基。
本发明所需的氧化剂为二甲基亚砜。
本发明所需的溶剂为二甲基亚砜，或者二甲基亚砜与醚或酰胺的混合物，优选二甲基亚砜为溶剂。
本发明所需的催化剂为碘单质或氢碘酸及其盐。
本发明所需的催化剂用量为2-30 mol%，优选20 mol%。
本发明物料配比为邦特盐:催化剂:二甲基亚砜:吲哚类物质等于(1-5):(0.02-0.3):(≥1):1。
本发明所需的温度在50~150 oC，优选80 oC。
具体实施方式：
向反应瓶中加入吲哚、1-5倍摩尔当量的邦特盐、0.02-0.3倍摩尔当量的单质碘或氢碘酸及其盐、至少1摩尔当量的二甲基亚砜和溶剂。将反应体系搅拌并升温反应8-24 小时。反应结束后，用饱和硫代硫酸钠溶液稀释并洗涤反应液，并用二氯甲烷将所得混合液萃取，合并有机相，用水洗涤，再用无水硫酸钠干燥。蒸出溶剂后，以硅胶柱层析分离提纯得到最终产物3-吲哚硫醚。
与已有的合成方法相比，本发明具有如下的优点：
1. 本发明所用的硫化试剂邦特盐低毒、气味小、环境污染小、廉价易得；
2. 使用非金属碘单质作为催化剂，廉价环保；
3. 反应条件温和，后处理简单；
4. 底物适用范围广，适用于多种取代的吲哚。
实施例
以下的实施例，在于详细的说明本发明而非限制本发明。
实施例1：3-(3-甲氧基苯硫基)吲哚的制备
向25 mL的反应瓶中加入吲哚（46.8 mg，0.4 mmol），S-间甲氧基邦特盐（242 mg，1mmol，2.5 eq），单质碘（20 mg，0.08 mmol），二甲基亚砜（3 mL）。将反应体系搅拌并升温至80 oC反应12 h。反应结束后，用饱和硫代硫酸钠溶液稀释并洗涤反应液，并用二氯甲烷将所得混合液萃取四次，合并有机相，用水洗涤两次，并用无水硫酸钠干燥。最后蒸出溶剂，硅胶柱层析分离提纯（石油醚:乙醚/20:1-4:1），得到最终产物3-(间甲氧基苯基硫代)吲哚白色固体，(90 mg，产率88%)。熔点: 88-90 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 8.42(br s,1H), 7.63 (d, J = 8.0 Hz, 1H), 7.41-7.46 (m, 2H), 7.27-7.29 (m, 1H),7.16-7.20(m, 1H), 7.09 (t, J = 7.6 Hz, 1H), 6.68-6.72 (m, 2H), 6.61-6.63 (m,1H), 3.69 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 159.9, 140.9,136.5, 129.7,129.2, 123.2, 121.1, 119.7, 118.3, 110.7, 110.6, 110.4, 102.6, 55.3. HRMS(ESI): m/z calcd for C15H13NOS [M + H]+, 256.0796; found, 256.0798.
实施例2：3-苯硫基吲哚的制备
实验操作与实施例1相似，不同之处在于二甲基亚砜用量为78 mg (2.5 eq.),DMF（3 mL）为溶剂，得3-苯硫基-吲哚，产率84%。白色固体, 熔点: 152-153 oC . 1H NMR(CDCl3, 400 MHz, ppm): δ 8.37 (br s , 1H),7.37 (d, J = 7.6 Hz, 1H), 7.43-7.48(m,2H), 7.27-7.31 (t, J = 7.2 Hz,1H), 7.05-7.20（m, 6H). 13C NMR(CDCl3, 100MHz, ppm): δ 139.3, 136.6,130.8,129.8,128.8,126.0, 124.7, 123.2, 121.0,119.8, 111.7, 102.9. HRMS (ESI): m/z calcd for C14H11NS [M + H]+, 226.0690;found, 226.0693.
实施例3：3-(4-甲基苯硫基)-吲哚的制备
实验操作与实施例1相似，不同之处在于二甲基亚砜用量为78 mg (2.5 eq.),NMP（3 mL）为溶剂，得3-(4-甲基苯硫基)吲哚，产率88%。白色固体， 熔点: 124-126 oC .1H NMR (CDCl3, 400 MHz, ppm): δ 8.35 (br s 1H), 7.63 (d, J = 8.0 Hz, 1H),7.47 (s, 1H), 7.42-7.44 (d, J = 8.4 Hz, 1H), 7.25-7.29 (m, 1H), 7.17 (t, J =7.6 Hz,1H), 7.04(d, J = 8.0 Hz, 2H), 6.98 (d, J = 8.4 Hz, 2H). 2.26 (s, 3H).13C NMR (CDCl3, 100 MHz, ppm): δ 136.5, 135.6, 134.8, 130.6, 129.6, 129.2,126.4, 123.1, 120.9, 119.8, 111.7, 21.0. HRMS (ESI): m/z calcd for C15H13NS [M+ H]+, 240.0847; found, 240.0845.
实施例4：3-(4-氯苯硫基)吲哚的制备
实验操作与实施例1相似，不同之处在于二甲基亚砜用量为156 mg (5 eq.), 二氧六环（3 mL）为溶剂，得3-(4-氯苯硫基)吲哚，产率90%。白色固体， 熔点: 130-131 oC.1H NMR (CDCl3, 400 MHz, ppm): δ 8.44 (br s, 1H), 7.58(d, J=8.0Hz, 1H), 7.49(d,J=2.8Hz, 1H), 7.45 (d, J=8.0Hz, 1H), 7.29 (t, J=8.0Hz, 1H), 7.18 (t, J=8Hz, 1H), 7.11-7.14 (m, 2H), 7.01-7.04 (m, 2H). 13C NMR (CDCl3, 100 MHz, ppm):δ 137.9, 136.6, 130.8, 130.7, 128.9, 127.2, 123.3, 121.2, 119.6, 111.8,102.6. HRMS (ESI): m/z calcd for C14H10ClNS [M + H]+, 260.0301; found,260.0304.
实施例5：3-(4-溴苯硫基)吲哚的制备
实验操作同实施例1，得到3-(4-溴苯硫基)吲哚，产率92%。白色固体， 熔点: 142-144 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 8.36 (br s 1H), 7.53 (d, J = 8.0 Hz,1H), 7.43 (d, J = 5.6 Hz, 1H), 7.40(d, J = 8.0 Hz,1H), 7.20-7.24 (m, 3H),7.14 (t, J = 8.0 Hz,1H), 6.90-6.93(m,2H). 13C NMR (CDCl3, 100 MHz, ppm): δ138.7, 136.6, 131.8, 130.9, 129.0, 127.5, 123.4, 121.2, 119.6, 118.4, 111.8,102.4. HRMS (ESI): m/z calcd for C14H10BrNS [M + H]+, 303.9796; found,303.9799.
实施例6：3-(3-硝基苯硫基)吲哚的制备
实验操作与实施例1相似，不同之处在于用0.2 eq.氢碘酸代替碘单质，得到3-(3-硝基苯硫基)吲哚，产率82%。白色固体，熔点: 136-137 oC. 1H NMR(CDCl3, 400 MHz,ppm): δ 8.5 (br s, 1H), 7.88-7.92 (m, 2H), 7.54-7.57 (m, 2H), 7.48-7.50 (d, J = 8.4 Hz, 1H), 7.36 (d, J = 8.0 Hz,1H), 7.30 (t, J = 8.0 Hz, 2H), 7.19 (t, J = 7.6 Hz, 1H). 13C NMR (CDCl3, 100 MHz,ppm): δ 148.7, 142,7, 136.7, 131.5,131.4, 129.4, 128.6, 123.6, 121.4, 120.3, 119.8, 119.3, 112.0, 100.9. HRMS(ESI): m/z calcd for C14H10N2O2S [M + H]+, 271.0541; found, 271.0543.
实施例7：3-(4-三氟甲基苯硫基)吲哚的制备
实验操作同实施例1，得到3-(4-三氟甲基苯硫基)吲哚，产率95%。白色固体。 熔点: 130-132 oC . 1H NMR(CDCl3, 400 MHz, ppm): δ 8.51 (br s, 1H), 7.57 (d, J =8.0 Hz, 1H), 7.52 (d, J = 1.6 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.38 (d, J =8.0 Hz, 2H), 7.28-7.33 (m, 1H), 7.18-7.21 (m, 1H), 7.14 (d, J = 8.0 Hz, 2H).13CNMR (CDCl3, 100 MHz,ppm): δ 144.8, 136.7, 131.2, 128.9, 127.0, 126.8 (q,32.4 Hz), 125.8 (q, J = 3.7 Hz), 124.4 (q, J = 269.9 Hz), 123.5, 121.4,119.5, 111.9, 101.3. HRMS (ESI): m/z calcd for C15H10F3NS [M + H]+, 294.0564;found, 294.0566.
实施例8：3-(2-甲基- 4-氟苯硫基)吲哚的制备
实验操作与实施例1相似，不同之处在于用0.2 eq.碘化钾代替碘单质，得到3-(2-甲基-4-氟苯硫基)吲哚，产率95%。 黄色粘稠液体。1H NMR (CDCl3, 400 MHz, ppm): δ8.51（br s, 1H), 7.57 (d, J = 8.0 Hz, 1H), 7.46-7.50 (m,2H), 7.29 (m, J = 8.0Hz, 1H), 7.19 (t, J = 7.6 Hz, 1H), 7.05-7.08 (m,1H), 6.62-6.67 (m, 1H), 6.36-6.39 (dd, J 1 = 2.8 Hz, J 2 = 10.0 Hz, 1H), 2.44(s, 3H). 13C NMR (CDCl3, 100 MHz,ppm): δ 161.8 (d, J = 242.5 Hz), 140.9 (d, J = 7.6 Hz), 136.7, 131.2, 130.9(d, J = 8 Hz), 129.6 (d, J = 3 Hz), 129.0, 123.4, 121.3, 119.6, 112.0, 111.8,111.7, 111.1 (d, J = 21.3 Hz), 101.5, 19.2. HRMS (ESI): m/z calcd forC15H12FNS [M + H]+, 258.0753; found, 258.0755.
实施例9：3-(3-喹啉硫基)吲哚的制备
实验操作同实施例1，得到3-(3-喹啉硫基)吲哚，产率70%。黄色固体, 熔点: 196-198 oC . 1H NMR (DMSO-d6, 400 MHz, ppm): δ 11.84 (s, 1H), 8.67 (br s, 1H),7.93 (d, J = 8.0 Hz, 2H), 7.85 (s, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.64 (t,J =7.2 Hz, 1H), 7.48-7.54 (m, 2H), 7.42 (d, J = 8.0 Hz, 1H), 7.20 (t,J = 7.2 Hz,1H), 7.06 (t,J = 7.2 Hz, 1H). 13C NMR (DMSO-d6, 100 MHz, ppm): δ 148.6, 145.4,136.8, 133.1, 132.8, 130.9, 128.8, 128.7, 128.3, 127.8, 127.3, 127.1, 122.4,120.4, 118.1, 112.6, 97.8. HRMS (ESI): m/z calcd for C17H12N2S [M + H]+,277.0799; found, 277.0795.
实施例10：3-正丁硫基吲哚的制备
实验操作与实施例1相似，使用的邦特盐为1.5 eq，反应时间2 h，得到3-正丁硫基吲哚，产率85%。黄色粘稠液体。1H NMR (DMSO-d6, 400 MHz, ppm): δ 11.35 (br s, 1H),7.59 (d, J = 7.6 Hz, 1H), 7.49 (d, J = 2.4 Hz,1H), 7.42 (d, J = 8.0 Hz, 1H),7.07-7.15 (m, 2H), 2.63 (t, J = 6.8 Hz, 2H), 1.32-1.48 (m, 4H), 0.83 (t, J = 7.2 Hz, 3H). 13C NMR (DMSO-d6, 100 MHz, ppm): δ 136.3, 129.6, 129.4, 122.7,120.5, 119.5, 111.6, 106.2, 36.2, 32.1, 21.8, 13.8. HRMS (ESI): m/z calcd forC12H15NS [M + H]+, 206.1003; found, 206.1007.
实施例11：3-正辛硫基吲哚的制备
实验操作与实施例1相似，使用的邦特盐为1.5 eq，反应时间2 h，得到3-正辛硫基吲哚，产率86%。黄色液体。1H NMR(CDCl3, 400 MHz, ppm): δ 8.22 (br s, 1H), 7.78(d,J = 7.6 Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H), 7.32 (d, J = 2.4 Hz, 1H), 7.19-7.25 (m, 2H),2.70 (t, J = 7.2 Hz, 2H), 1.24-1.40 (m,12H), 0.87 (t, J = 6.4Hz, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 136.4, 129.5, 129.3, 122.7, 120.5,119.5, 106.3, 36.5, 31.9, 30.0, 29.3, 28.7. 20.6, 14.2. HRMS (ESI): m/z calcdfor C16H23NS [M + H]+, 262.1269; found, 262.1267.
实施例12：3-(乙氧羰基甲硫基)吲哚的制备
实验操作与实施例1相似，使用的邦特盐为1.5 eq，反应时间4 h，得到3-(乙氧羰基甲硫基)吲哚，产率74%。黄色液体。1H NMR(CDCl3, 400 MHz, ppm): δ 8.41 (br s, 1H),7.70 (d, J = 7.2 Hz, 1H), 7.37-7.39 (m, 2H), 7.20-7.25 (m, 2H), 4.05-4.11 (m,2H), 3.41(s, 2H), 1.16 (t, J = 7.2 Hz, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ170.7, 136.2, 130.5, 129.1, 123.0, 120.8, 119.2, 111.7, 104,6, 61.38, 39.0,14.2. HRMS (ESI): m/z calcd for C12H13NO2S [M + H]+, 236.0745; found, 236.0748.
实施例13：1-甲基-3-(3-甲氧基苯硫基)吲哚的制备
实验操作同实施例1，得到1-甲基-3-(3-甲氧基苯硫基)吲哚，产率89%。白色固体，熔点: 117-118 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 7.62 (d, J = 8.0 Hz, 1H),7.39 (d, J = 8.0 Hz, 1H), 7.34 (s, 1H), 7.30 (t, J = 8.0 Hz, 1H), 7.17 (t, J = 8.0 Hz, 1H), 7.07 (t, J = 7.6 Hz, 1H), 6.66-6.70 (m, 2H), 6.58-6.61 (m,1H),3.85 (s, 3H), 3.69 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ159.9, 141.4,137.7, 134.8, 130.0, 129.6, 122.7, 120.6, 119.8, 118.2, 110.6, 110.3, 109.8,100.4, 55.3, 33.3. HRMS (ESI): m/z calcd for C16H15NOS [M + H]+, 270.0953;found, 270.0956.
实施例14：2-甲基-3-(3-甲氧基苯硫基)吲哚的制备
实验操作同实施例1，得到2-甲基-3-(3-甲氧基苯硫基)吲哚，产率86%。白色固体,熔点: 73-75 oC .1H NMR (CDCl3, 400 MHz, ppm): δ 8.25(br s, 1H), 7.55 (d, J = 7.6 Hz, 1H), 7.33 (d, J=8.0 Hz, 1H), 7.19 (t, J = 6.8 Hz, 1H), 7.13 (t, J = 7.6 Hz, 1H), 7.07 (d, J = 7.6 Hz, 1H), 6.58-6.64 (m, 3H). 3.66 (s, 3H), 2.51(s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 159.5, 141.4, 141.1, 135.5, 130.3,129.7, 122.2, 120.8, 119.0, 118.0, 111.3, 110.8, 110.0, 55.1, 12.0. HRMS(ESI): m/z calcd for C16H15NOS [M + H]+, 270.0953; found, 270.0956.
实施例15：2-苯基-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似，得到2-苯基-3-(3-甲氧基苯硫基)吲哚，产率86%。白色固体, 熔点: 112-114 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 8.55 (br s, 1H), 7.76(s, 1H), 7.60 (d, J = 7.6 Hz, 1H), 7.65 (d, J = 8.0 Hz, 1H), 7.37-7.45 (m,4H), 7.28-7.30 (d, J = 8.0 Hz, 1H), 7.18 (t, J = 8.0 Hz, 1H), 7.09 (t, J = 8.0 Hz, 1H), 6.68-6.71 (m, 2H), 6.61(dd, J 1 = 2.4 Hz, J 2 = 8.4 Hz, 1H), 3.68(s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 160.0, 142.2, 140.9, 135.8, 131.5,131.3, 129.8, 128.9, 128.8, 128.2, 123.5, 121.3, 120.0, 118.1, 111.3, 110.3,99.2, 55.1. HRMS (ESI): m/z calcd for C21H17NOS [M + H]+, 332.1109; found,332.1106.
实施例16：5-甲氧基-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似，得到5-甲氧基-3-(3-甲氧基苯硫基)吲哚，产率90%。黄色油状液体。1H NMR (CDCl3, 400 MHz, ppm): δ 8.41 (s, 1H), 7.42 (d, J = 2.8 Hz,1H), 7.29 (t, J = 2.8 Hz, 1H), 7.07-7.13 (m, 2H), 6.92 (dd, J 1 = 2.4 Hz, J 2 = 8.8 Hz, 1H), 6.68 -6.72 (m, 2H), 6.63 (dd, J 1 = 2.4 Hz, J 2 = 8.8 Hz, 1H). 3.80(s, 3H), 3.70 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 160.0, 155.2, 141.1,131.6, 131.5, 130.1, 129.7, 118.1, 113.7, 112.6, 111.4, 110.3, 55.9, 55.3.HRMS (ESI): m/z calcd for C16H15NO2S [M + H]+, 285.0823.1269; found, 285.0826.
实施例17：5-甲基-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似，得到5-甲基-3-(3-甲氧基苯硫基)吲哚，产率84%。无色油状液体。1H NMR (CDCl3, 400 MHz, ppm): δ 8.36 (br s, 1H), 7.48 (d, J = 2.8 Hz,1H), 7.06-7.12 (m, 3H), 6.68-6.70 (m, 2H), 6.59-6.62 (m,2H), 3.69 (s, 3H),2.53 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 160.0, 141.0, 136.1, 130.6,129.6, 128.8, 123.7, 121.2, 120.9, 118.3, 117.4, 111.6, 110.3, 102.9, 55.3,16.5. HRMS (ESI): m/z calcd for C16H15NOS [M + H]+, 270.0953.; found, 270.0956.
实施例18：7-甲基-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例6相似，得到7-甲基-3-(3-甲氧基苯硫基)吲哚，产率86%。无色油状液体。1H NMR (CDCl3, 400 MHz, ppm): δ 8.36 (br s, 1H), 7.48 (d, J = 2.8 Hz,1H), 7.06-7.12 (m, 3H), 6.68-6.70 (m, 2H), 6.59-6.62 (m,2H), 3.69 (s, 3H),2.53 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 160.0, 141.0, 136.1, 130.6,129.6, 128.8, 123.7, 121.2, 120.9, 118.3, 117.4, 111.6, 110.3, 102.9, 55.3,16.5. HRMS (ESI): m/z calcd for C16H15NOS [M + H]+, 270.0953.; found, 270.0956.
实施例19：3-(3-甲氧基苯硫基)吲哚- 2-羧酸甲酯的制备
实验操作与实施例1相似，使用的邦特盐为3 eq，反应时间16 h，得到3-(3-甲氧基苯硫基)吲哚- 2-羧酸甲酯，产率66%。白色固体， 熔点: 154-155 oC . 1H NMR (CDCl3,400 MHz, ppm): δ 9.30 (br s, 1H), 7.60 (d, J = 8.0 Hz, 1H), 7.45 (d, J = 8.4Hz, 1H), 7.36 (t, J = 8.0 Hz, 1H), 7.15 (t, J = 7.6 Hz, 1H), 7.09 (t, J = 8.0Hz, 1H), 6.73-6.76 (m, 2H), 6.64 (dd, J 1 = 2.4 Hz, J 2 = 8.0 Hz, 1H), 3.94 (s,3H), 3.69 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 161.9, 159.9, 139.1,135.9, 130.0, 129.7, 128.7, 126.4, 121.9, 121.7, 119.8, 113.0, 112.2, 111.1,110.5, 55.3, 52.4. HRMS (ESI): m/z calcd for C17H15NO3S [M + H]+, 314.0851;found, 314.0855.
实施例20：4-溴-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似, 得到4-溴-3-(3-甲氧基苯硫基)吲哚，产率76%。白色固体, 熔点: 144-146 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 8.52 (br s, 1H), 7.51(d, J = 8.0 Hz, 1H), 7.38 (d, J = 8.0 Hz, 1H), 7.40 (d, J = 7.6 Hz, 1H), 7.12(d, J = 8.0 Hz, 1H), 7.07 (d, J = 8.0 Hz, 1H), 6.61-6.69 (m, 3H). 3.70 (s,3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 159.9, 142.7, 142.6, 137.8, 133.4,126.5, 126.3, 126.1, 124.1, 118.4, 114.7, 111.7, 111.2, 110.2, 103.5, 55.3.HRMS (ESI): m/z calcd for C15H12BrNOS [M + H]+, 333.9901; found, 333.9905.
实施例21：5-氟-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似，得到5-氟-3-(3-甲氧基苯硫基)吲哚，产率82%。无色油状液体。1H NMR (CDCl3, 400MHz, ppm): δ 8.44 (br s, 1H), 7.49 (s, 1H),7.32(dd,J 1 = 4.4 Hz, J 2 = 8.8 Hz, 1H), 7.25-7.28 (m, 1H), 7.08-7.12 (m, 1H), 6.97-7.02(m, 1H), 6.66-6.68 (m ,1H), 6.60-6.62 (m, 2H), 3.70 (s, 3H). 13C NMR (CDCl3,100 MHz, ppm): δ 160.0, 158.7 (d, J = 235.4 Hz), 140.5, 133.0, 132.6, 130.0(d, J=10Hz), 129.8, 118.4, 112.6 (d, J = 9.5 Hz), 111.8, 111.7 (d, J = 26.4Hz), 110.5, 104.7 (d, J = 24.1 Hz), 102.8 (d, J = 4.7 Hz), 55.3. HRMS (ESI):m/z calcd for C15H12FNOS [M + H]+, 274.0702; found, 274..0706.
实施例22：5-氯-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似，得到5-氯-3-(3-甲氧基苯硫基)吲哚，产率79%。白色固体, 熔点: 87-88 oC . 1H NMR (CDCl3, 400MHz, ppm): δ 8.48 (br s, 1H), 7.60 (d,J = 2.0 Hz, 1H), 7.45 (d, J = 2.4 Hz, 1H), 7.31 (d, J = 8.8 Hz, 1H), 7.20(dd, J 1 = 2.0 Hz, J 2 = 8.4 Hz, 1H), 7.09-7.14 (m, 1H), 6.69-6.71 (m, 1H),6.63-6.65 (m, 2H). 3.71 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm):δ 160.0, 140.4,134.9, 132.3, 130.4, 129.8, 127.0, 123.6, 119.1, 118.4, 112.8, 111.8, 110.4,102.4, 55.3. HRMS (ESI): m/z calcd for C15H12ClNOS [M + H]+, 290.0406; found,290.0409.
实施例23：5-溴-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似, 得到5-溴-3-(3-甲氧基苯硫基)吲哚，产率75%。白色固体, 熔点: 101-102 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 8.48 (s, 1H), 7.76 (s,1H), 7.48 (d, J = 2.4 Hz, 1H), 7.29-7.36 (m, 2H), 7.10 (t, J = 2.4 Hz, 1H),6.62-6.68 (m ,3H), 3.70 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 160.0,142.0, 135.2, 132.1, 131.0, 129.8, 126.1, 122.2, 118.3, 114.6, 113.2, 111.8,110.5, 102.4, 55.3. HRMS (ESI): m/z calcd for C15H12BrNOS [M + H]+, 333.9901;found, 333.9905.
实施例24：5-硝基-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似, 使用的邦特盐为3 eq，反应时间16 h，得到5-硝基-3-(3-甲氧基苯硫基)吲哚，产率70%。黄色固体, 熔点: 140-141 oC . 1H NMR (CDCl3, 400MHz, ppm): δ 8.89 (br s, 1H), 8.57 (d, J = 2.0 Hz, 1H), 8.16-8.18 (m, 1H),7.65-7.66 (d, J = 2.4 Hz, 1H), 7.50 (d, J = 8.8 Hz, 1H), 7.09-7.14 (m, 1H),6.69-6.71 (m, 1H), 6.64-6.66 (m, 2H), 3.71 (s, 3H). 13C NMR (CDCl3, 100 MHz,ppm): δ 160.1, 142.8, 139.5, 139.3, 134.0, 129.9, 129.0, 118.9, 118.8, 117.0,112.4, 112.1, 110.9, 106.3, 55.2. HRMS (ESI): m/z calcd for C15H12N2O3S [M + H]+, 301.0647; found, 301.0649.
实施例25：5-氰基-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似，使用的邦特盐为3 eq，反应时间16 h，得到5-氰基-3-(3-甲氧基苯硫基)吲哚，产率71%。白色固体, 熔点: 137-138 oC . 1H NMR (CDCl3, 400MHz, ppm): δ 9.0 (br s, 1H), 7.96 (s, 1H), 7.61 (d, J = 2.4 Hz, 1H), 7.46-7.52 (m, 2H), 7.12 (t, J = 8.0 Hz, 1H), 6.61-6.69 (m, 3H), 3.71 (s, 3H). 13CNMR (CDCl3, 100 MHz, ppm): δ 139.5, 138.4, 133.0, 129.9, 129.1, 126.1, 125.4,120.4, 118.7, 112.7, 112.1, 110.6,104.5 55.2. HRMS (ESI): m/z calcd forC16H12N2OS [M + H]+, 281.0749; found, 281.0746.
实施例26：3-(3-甲氧基苯硫基)吲哚-5-羧酸甲酯的制备
实验操作与实施例1相似, 得到3-(3-甲氧基苯硫基)吲哚-5-羧酸甲酯，产率76%。黄色固体, 熔点: 124-126 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 8.67 (br s, 1H),8.39 (s, 1H), 7.97-7.99 (m, 1H), 7.56 (d, J = 2.4 Hz, 1H), 7.45 (d, J = 8.8Hz, 1H), 7.09 (t, J = 8.8 Hz, 1H), 6.68 (d, J = 7.6 Hz, 1H), 6.60-6.64 (m,2H). 3.81 (s, 3H), 3.69 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 168.0,159.9, 140.4, 139.1, 132.3, 129.6, 128.9, 124.5, 123.1, 122.4, 118.3, 111.7,111.4, 104.4, 55.2, 52.0. HRMS (ESI): m/z calcd for C17H15NO3S [M + H]+,314.0851; found, 314.0855.
实施例27：3-(3-甲氧基苯硫基)吲哚-6-羧酸甲酯的制备
实验操作与实施例1相似, 得到3-(3-甲氧基苯硫基)吲哚-6-羧酸甲酯，产率70%。白色固体, 熔点: 130-131 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 8.74 (br s, 1H),8.21 (s, 1H), 7.85 (dd, J 1 = 1.2 Hz, J 2 = 8.4 Hz, 1H), 7.63-7.65 (m, 2H),7.07-7.11 (m, 1H), 6.60-6.68 (m, 3H), 3.94 (s, 3H), 3.68 (s, 3H). 13C NMR(CDCl3, 100 MHz, ppm): δ 168.0, 160.0, 140.3, 136.0, 134.0, 133.0, 129.8,125.0, 122.1, 119.5, 118.4, 114.2, 111.8, 110.6, 103.5, 54.8, 52.0. HRMS(ESI): m/z calcd for C17H15NO3S [M + H]+, 314.0851; found, 314.0855.
实施例28：6-氯-3-(3-甲氧基苯硫基)吲哚的制备
实验操作与实施例1相似, 得到6-氯-3-(3-甲氧基苯硫基)吲哚，产率78%。无色油状液体。1H NMR (CDCl3, 400 MHz, ppm): δ 8.43 (br s, 1H), 7.51 (d, J = 8.8 Hz,1H), 7.43 (d, J = 2.4 Hz, 1H), 7.39 (s,1H), 7.08-7.14 (m, 2H), 6.62-6.71 (m,3H), 3.7 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 160.0, 140.4, 136.9, 131.4,129.8, 129.1, 127.8, 121.8, 120.7, 118.4, 111.8, 111.7, 110.5, 103.1, 55.3.HRMS (ESI): m/z calcd for C15H12ClNOS [M + H]+, 290.0406; found, 290.0409.
实施例29：3-(3-甲氧基苯硫基)-7-氮杂吲哚的制备
实验操作与实施例1相似, 得到3-(3-甲氧基苯硫基)-7-氮杂吲哚，产率78%。白色固体, 熔点: 165-166 oC . 1H NMR (CDCl3, 400 MHz, ppm): δ 11.68 ( br s, 1H),8.41 (d, J = 4.4 Hz, 1H), 7.96-7.98 (m, 1H), 7.71 (d, J = 4 Hz, 1H), 7.17(dd, J 1 = 0.8 Hz, J 2 = 8.0 Hz, 1H), 7.10 (t, J = 7.6 Hz, 1H), 6.68-6.71 (m,1H), 6.61-6.66 (m, 2H), 3.69 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm): δ 160.1,149.4, 143.3, 140.5, 132.3, 129.7, 128.7, 122.4, 118.4, 116.9, 111.7, 110.7,101.1, 55.3. HRMS (ESI): m/z calcd for C14H12N2OS [M + H]+, 257.0749; found,257.0746.
实施例30: 5-氰基-3-对甲苯硫基吲哚的制备
实验操作与实施例1相似, 得到5-氰基-3-对甲苯硫基吲哚，产率79%。白色固体,熔点: 201-203 oC . 1H NMR (DMSO-d6, 400 MHz, ppm): δ 12.13 (br s, 1H), 7.90(dd, J 1 = 2.4 Hz, J 2 = 4.4 Hz, 1H), 7.77 (s, 1H), 7.63 (d, J = 8.4 Hz, 1H),7.46-7.48 (m, 1H), 7.01 (d, J = 8.0Hz, 2H), 6.96 (d, J = 7.6Hz, 2H), 2.20 (s,3H). 13C NMR (DMSO-d6, 100 MHz, ppm):δ 138.5, 134.6, 134.4, 129.5, 128.5,126.2, 124.7, 123.5, 120.0, 113.6, 102.3, 102.0, 79.2, 78.8, 78.5, 20.0. HRMS(ESI): m/z calcd for C16H12N2S [M + H]+, 265.0799; found, 265.0795.
实施例31:6-氯-3-对甲苯硫基吲哚的制备
实验操作与实施例1相似, 得到6-氯-3-对甲苯硫基吲哚，产率73%。无色油状液体。1H NMR (CDCl3, 400 MHz, ppm): δ 8.36 (br s, 1H), 7.50 (d, J = 8.4 Hz, 1H),7.47 (d, J = 2.4 Hz, 1H), 7.42 (d, J = 1.6 Hz, 1H), 7.12 (dd, J 1 = 2.0 Hz, J 2 = 8.4 Hz, 1H), 6.97-7.02 (m, 4H), 2.26 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm):δ 136.9, 135.1, 131.0, 129.7, 129.1, 127.8, 121.8, 120.7, 111.7, 104.2, 21.0.HRMS (ESI): m/z calcd for C15H12ClNS [M + H]+, 274.0457; found, 274.0453.
实施例32: 5-甲氧基-3-(3,4,5-三甲氧基苯硫基)吲哚-2-羧酸甲酯的制备
实验操作与实施例1相似, 使用的邦特盐为4 eq，反应时间16 h，得到5-甲氧基-3-(3,4,5-三甲氧基苯硫基)吲哚-2-羧酸甲酯，产率67%。白色固体，熔点:150-152 oC . 1HNMR(CDCl3, 400 MHz, ppm): δ9.46 (br s, 1H), 7.32 (d, J = 8.8Hz, 1H), 7.00(dd, J 1 = 8.8Hz, J 2 = 2.4 Hz, 1H ), 6.92 (d, J = 2.4Hz, 1H ), 6.47 (s, 2H),3.94 (s, 3H), 3.78 (s, 3H), 3.73 (s, 3H), 3.67 (s, 6H). 13C NMR (CDCl3, 100MHz, ppm): δ160.8, 154.3, 152.5, 135.4, 131.3, 130.2, 129.4, 127.4, 117.2,112.4, 109.3, 104.4, 100.3, 60.0, 55.2, 54.7, 51.3. HRMS (ESI): m/z calcd forC20H21NO6S [M + H]+, 404.1168; found, 404.1164。

Claims (6)

1.一种制备3-吲哚硫醚的方法，其特征是在一定的温度下，以碘单质或碘化物为催化剂，二甲基亚砜为氧化剂，邦特盐为硫源，与吲哚类化合物反应生成3-吲哚硫醚，该方法具有如下的反应通式：
其中：Z代表CH、N，R1代表H、C1-C20烷基，R2代表H、C1-C20烷基、C6-C20芳基、酯基，R3代表H、C1-C20烷基、C1-C20烷氧基、C6-C20芳基、酯基、卤素、硝基、氰基，R4代表C1-C20烷基、C6-C20芳基、C6-C20杂芳基。
2.根据权利要求1所述的方法，其特征在于碘化物是氢碘酸及其盐。
3.根据权利要求1所述的方法，其特征在于催化剂用量为2-30 mol%。
4.根据权利要求1所述的方法，该反应也可以在有其它溶剂的条件下进行，所用溶剂是极性非质子溶剂，选自二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮；或者是醚类溶剂，选自乙醚、四氢呋喃、二氧六环、乙二醇二甲醚；或者是它们的混合物。
5.根据权利要求1所述的方法，其特征在于物料配比为邦特盐:催化剂:二甲基亚砜:吲哚类物质等于(1-5):(0.02-0.3):(≥1):1。
6.根据权利要求1所述的方法，其特征在于反应温度为50-150 oC。
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