CN113683559B - 一种制备杂环邻碘硫醚的方法 - Google Patents

一种制备杂环邻碘硫醚的方法 Download PDF

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CN113683559B
CN113683559B CN202110951282.3A CN202110951282A CN113683559B CN 113683559 B CN113683559 B CN 113683559B CN 202110951282 A CN202110951282 A CN 202110951282A CN 113683559 B CN113683559 B CN 113683559B
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张士磊
胡敏
胡延维
姜远锐
方春辉
祝文静
陈鑫
黄加文
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Abstract

本发明公开了一种制备杂环邻碘硫醚的方法，以杂环硫酚与邻二碘苯为底物，在金属氢化物存在下、溶剂中反应，制备杂环邻碘硫醚。传统的无金属C‑S偶联反应，需要预先制备碘鎓、硫鎓前体等活性物种，制备成本高、难度大。本发明在氢化钠作用下，邻二碘苯能够与硫酚反应合成杂环邻碘硫醚。邻二碘苯原料价廉易得、反应温和；同时，杂环邻碘硫醚可以进行下一步广泛转化，制备多样的1,2‑二取代苯，为复杂的天然产物和药物分子合成提供了一条简捷途径。

Description

一种制备杂环邻碘硫醚的方法
技术领域
本发明属于有机合成，具体涉及一种制备杂环邻碘硫醚的方法。
背景技术
众多科学家对芳基硫醚化合物的建设已做出了重大努力，且取得可观的成果。传统上，通过预功能化的芳烃(如芳基卤化物)与硫醇或二硫化物通过金属催化（主要有钯、铜、铁、镍、钴、铑等）的交叉偶联反应获得芳基硫化物，是一种十分有效的C-S构建方法。然而，与成熟的C-O、C-N等金属催化交叉偶联反应相比，C-S间的金属偶联并不是那么顺利，有机硫试剂由于硫元素的特殊电性容易与金属催化剂形成过度配位，造成金属催化剂中毒失活。因此，大部分已知的金属催化C-S偶联的方法均要求十分严苛的反应条件，需强碱(如t-BuONa)、或特定的空气敏感型、高成本配体以及高温（80-140℃）等，这类方法实用性较差。因此，需要寻找形成C-S键更好的替代方案。
发明内容
本发明公开了一种制备杂环邻碘硫醚的方法，为一种底物易得、条件温和、原子利用率高的新方法，解决了无过渡金属偶联反应难以大规模应用的难题，是目前此领域重要的研究方向。
本发明采用如下技术方案：
一种制备杂环邻碘硫醚的方法，以杂环硫酚与邻二碘苯为底物，在金属氢化物存在下、溶剂中反应，得到杂环邻碘硫醚。
本发明中，杂环硫酚的化学结构式为RSH；
邻二碘苯的化学结构式如下：
Figure 137254DEST_PATH_IMAGE001
杂环邻碘硫醚的化学结构式如下：
Figure 918128DEST_PATH_IMAGE002
所述R为杂环或者取代杂环，杂环或者取代杂环含有氮、氧、硫中的一种或几种；取代杂环的取代基为卤素、烷基、卤素烷基、氰基、硝基、烷氧基、苯基、氨基、酰氨基等；进一步的，杂环硫酚结构式中的环可以为一个，也可以为多个，至少包括一个杂环。
本发明公开的杂环硫酚与邻二碘苯的反应在金属氢化物存在下、溶剂中进行，无需其他物质，室温下反应1～4小时，得到产物杂环邻碘硫醚为单一产物。
本发明中，金属氢化物为氢化钠、氢化钾、氢化钙、氢化锂等；金属氢化物的用量为杂环硫酚摩尔量的3～5倍，优选为4倍。进一步的，邻二碘苯的用量为杂环硫酚摩尔量的1～3倍。
本发明中，溶剂为二甲基乙酰胺DMA、四氢呋喃THF、乙腈CH3CN、乙二醇二甲醚DME、甲苯Toluene中的一种或几种，优选为THF和DMA，两者体积比优选为（3～8）∶1。
氢化钠从化学结构上看，形式非常简单，市面上购买的氢化钠价格十分低廉，使用很方便。因此，从成本经济上讲，氢化钠一直很受化学家们喜爱。但是氢化钠的应用范围十分有限，虽然氢化钠本身是一个蕴藏很大能量的物种，但是想要很好的发挥其活性，使其成为还原剂，仍然需要不断努力的探索。本发明公开的NaH作用邻二碘苯用于合成杂环邻碘硫醚产物，无需过渡金属，无需额外碘源，更具有实用价值。
附图说明
图1为化合物3ac的核磁谱图。
具体实施方式
本发明以杂环硫酚与邻二碘苯为底物，在金属氢化物以及溶剂存在下，即可完成反应，高收率得到产物杂环邻碘硫醚，无需其他物质，解决了现有技术需要金属催化剂、格式试剂等问题。
本发明涉及的原料都是现有产品，可市购，也可根据现有方法制备。
核磁谱图1H NMR使用Agilent 400 MHz和Bruker 400 MHz仪器测定，13C NMR使用Bruker 400 MHz仪器测定，样品溶剂为CDCl3或氘代DMSO，其溶剂中含有TMS内标。LR-MS质谱仪为ESI源。TLC监测使用烟台黄海化工厂生产的薄层硅胶板，快速柱层析使用硅胶为200-300目。试剂均为市售分析纯或化学纯，无特殊说明，直接使用。无水溶剂均为重蒸溶剂或市售干燥溶剂（百灵威）。
实施例一
Figure 700140DEST_PATH_IMAGE003
室温下，将NaH（1.2 mmol, 4.0 equiv）称量于反应瓶中，悬于无水THF（0.8 mL）中磁力搅拌，在搅拌过程中滴加杂环硫酚1（0.3 mmol, 1.0 equiv，溶于0.2 mL DMA），加完后在室温下搅拌3min，然后加入二碘苯2a（0.6 mmol, 2.0 equiv，溶于0.2mL THF），继续在室温下搅拌，TLC监测反应。反应完成后，加入冰水和四氢呋喃淬灭反应，乙酸乙酯萃取3次，合并有机层，饱和NaCl溶液洗涤，无水硫酸钠干燥，过滤，旋干溶剂，加入硅胶粉拌样，快速柱层析分离，得到杂环邻碘硫醚产品3，常规计算收率。
产物结构式下方的收率为分离收率，标注的时间为TLC监测反应完全的时间。图1为产物3ac的核磁谱图。
化合物1为杂环硫酚，其结构式可根据产物确定，将产物中的含碘苯环更换为H即可，比如产物3ac对应的原料杂环硫酚的结构式如下：
Figure 806636DEST_PATH_IMAGE004
产物3ad对应的原料杂环硫酚的结构式如下：
Figure 918773DEST_PATH_IMAGE005
其余产物-原料杂环硫酚照上规律，所有杂环硫酚都为现有产品。
产物数据表征
Figure 768917DEST_PATH_IMAGE006
1H NMR (400 MHz, CDCl3) δ 8.45 (ddd, J = 4.8, 1.7, 0.7 Hz, 1H), 7.98(dd, J = 7.9, 1.3 Hz, 1H), 7.67 (dd, J = 7.7, 1.6 Hz, 1H), 7.49 (td, J = 7.8,1.9 Hz, 1H), 7.38 (td, J = 7.6, 1.3 Hz, 1H), 7.14 – 6.97 (m, 2H), 6.88 (d, J= 8.1 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 159.79, 150.00, 140.56, 136.99,136.97, 135.82, 130.42, 129.39, 122.12, 120.44, 107.41。
Figure 139855DEST_PATH_IMAGE007
1H NMR (400 MHz, CDCl3) δ 8.40 (d, J = 1.3 Hz, 1H), 7.99 (d, J = 7.8Hz, 1H), 7.68 (d, J = 7.6 Hz, 1H), 7.46 (dd, J = 8.5, 2.0 Hz, 1H), 7.40 (t, J= 7.5 Hz, 1H), 7.09 (t, J = 7.4 Hz, 1H), 6.82 (d, J = 8.5 Hz, 1H). 13C NMR(101 MHz, CDCl3) δ 157.96, 148.69, 140.72, 136.74, 136.45, 136.07, 130.79,129.52, 128.86, 122.69, 107.68。
Figure 151674DEST_PATH_IMAGE008
1H NMR (400 MHz, CDCl3) δ 8.62 (s, 1H), 8.49 (d, J = 1.2 Hz, 1H), 8.00(d, J = 7.9 Hz, 1H), 7.69 (d, J = 7.5 Hz, 1H), 7.60 (dd, J = 8.5, 1.8 Hz,1H), 7.40 (t, J = 7.5 Hz, 1H), 7.09 (t, J = 7.4 Hz, 1H), 6.76 (d, J = 8.5 Hz,1H), 6.65 (d, J = 8.4 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 158.60, 150.85,140.75, 139.49, 136.32, 136.17, 130.86, 129.54, 123.09, 117.14, 107.80。
Figure 975273DEST_PATH_IMAGE009
1H NMR (400 MHz, CDCl3) δ 8.70 (d, J = 5.0 Hz, 1H), 8.02 (dd, J = 7.9,1.2 Hz, 1H), 7.77 (dd, J = 7.7, 1.5 Hz, 1H), 7.43 (td, J = 7.6, 1.3 Hz, 1H),7.29 (d, J = 5.0 Hz, 1H), 7.14 (td, J = 7.8, 1.6 Hz, 1H). 13C NMR (101 MHz,CDCl3) δ 173.25, 159.96, 156.22 (d, J = 37.4 Hz), 140.50, 136.87, 134.23,131.32, 129.24, 120.2 (d, J = 276.7 Hz), 112.57, 108.77. 19F NMR (377 MHz,CDCl3) δ -70.22。
Figure 97950DEST_PATH_IMAGE010
1H NMR (400 MHz, CDCl3) δ 7.76 (dd, J = 7.8, 1.3 Hz, 1H), 7.58 (dd, J= 5.4, 1.2 Hz, 1H), 7.35 (dd, J = 3.6, 1.2 Hz, 1H), 7.22 – 7.13 (m, 2H), 6.83(td, J = 7.7, 1.5 Hz, 1H), 6.75 (dd, J = 8.0, 1.5 Hz, 1H). 13C NMR (101 MHz,CDCl3) δ 143.96, 139.35, 137.46, 132.57, 130.50, 128.87, 128.50, 126.93,126.52, 94.88。
Figure 323395DEST_PATH_IMAGE011
1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 7.9 Hz, 1H), 7.62 (d, J = 7.7Hz, 1H), 7.58 – 7.51 (m, 5H), 7.36 (t, J = 7.6 Hz, 1H), 7.06 (t, J = 7.5 Hz,1H). 13C NMR (101 MHz, CDCl3) δ 152.79, 140.65, 135.02, 133.97, 133.53,132.93, 131.27, 130.54, 129.89, 129.83, 129.58, 124.41, 104.86。
Figure 506115DEST_PATH_IMAGE012
1H NMR (400 MHz, CDCl3) δ 7.74 (d, J = 7.7 Hz, 1H), 7.21 (s, 1H), 7.17– 7.09 (m, 2H), 6.82 (t, J = 7.4 Hz, 1H), 6.55 (d, J = 7.7 Hz, 1H), 3.62 (s,3H). 13C NMR (101 MHz, CDCl3) δ 140.63, 139.54, 137.81, 130.64, 129.00,127.44, 127.21, 124.35, 95.65, 33.96。
实施例二
Figure 646371DEST_PATH_IMAGE013
室温下，将NaH（0.9 mmol, 3.0 equiv）称量于反应瓶中，悬于无水THF（0.8 mL）中磁力搅拌，在搅拌过程中滴加吡啶硫酚1a（0.3 mmol, 1.0 equiv，溶于0.2 mL DMA），加完后在室温下搅拌3min，然后加入二碘苯2a（0.6 mmol, 2.0 equiv，溶于0.2mL THF），继续在室温下搅拌，TLC监测反应。反应完成后，加入冰水和四氢呋喃淬灭反应，乙酸乙酯萃取3次，合并有机层，饱和NaCl溶液洗涤，无水硫酸钠干燥，过滤，旋干溶剂，加入硅胶粉拌样，快速柱层析分离，得到杂环邻碘硫醚产品3ac，常规计算收率为65%。
室温下，将KH（4.0 equiv）称量于反应瓶中，悬于无水THF（0.8 mL）中磁力搅拌，在搅拌过程中滴加吡啶硫酚1a（0.3 mmol, 1.0 equiv，溶于0.2 mL DMA），加完后在室温下搅拌3min，然后加入二碘苯2a（0.6 mmol, 2.0 equiv，溶于0.2mL THF），继续在室温下搅拌，反应24小时后，加入冰水和四氢呋喃淬灭反应，乙酸乙酯萃取3次，合并有机层，饱和NaCl溶液洗涤，无水硫酸钠干燥，过滤，旋干溶剂，加入硅胶粉拌样，快速柱层析分离，得不到杂环邻碘硫醚产品3ac。
室温下，将CaH2（2.0 equiv）称量于反应瓶中，悬于无水THF（0.8 mL）中磁力搅拌，在搅拌过程中滴加吡啶硫酚1a（0.3 mmol, 1.0 equiv，溶于0.2 mL DMA），加完后在室温下搅拌3min，然后加入二碘苯2a（0.6 mmol, 2.0 equiv，溶于0.2mL THF），继续在室温下搅拌，TLC监测反应。反应完成后，加入冰水和四氢呋喃淬灭反应，乙酸乙酯萃取3次，合并有机层，饱和NaCl溶液洗涤，无水硫酸钠干燥，过滤，旋干溶剂，加入硅胶粉拌样，快速柱层析分离，得到杂环邻碘硫醚产品3ac，常规计算收率为19%。
室温下，将NaH（1.2 mmol, 4.0 equiv）称量于反应瓶中，悬于无水THF（0.6 mL）中磁力搅拌，在搅拌过程中滴加吡啶硫酚1a（0.3 mmol, 1.0 equiv，溶于0.2 mL DMA），加完后在室温下搅拌3min，然后加入二碘苯2a（0.6 mmol, 2.0 equiv，溶于0.2mL THF），继续在室温下搅拌，TLC监测反应。反应完成后，加入冰水和四氢呋喃淬灭反应，乙酸乙酯萃取3次，合并有机层，饱和NaCl溶液洗涤，无水硫酸钠干燥，过滤，旋干溶剂，加入硅胶粉拌样，快速柱层析分离，得到杂环邻碘硫醚产品3ac，常规计算收率为71%。
本发明对杂环化合物的硫酚进行研究，发现NaH当量为4.0 equiv时，杂环硫酚能很好的与二碘苯反应，产率均在中等以上，产物可直接应用，解决了无过渡金属偶联大规模应用的难题，展现了反应的实用性和工业化应用前景；进一步的，该产物邻位碘具有很大的应用价值，还可以进一步进行广泛的转化，如邻碘可以在Pd催化下与苯硼酸、苯硫酚、苯乙炔等发生偶联反应，制备多样的2-取代苯硫酚，此外，邻碘可以在金属催化下发生分子内成环反应。本发明利用邻二碘苯在NaH作用下，与杂环硫酚发生亲核反应生成杂环邻碘硫醚产物，该方法无需过渡金属参与即完成了C-S键偶联，操作简便，无金属试剂残留、污染等问题，具有很重要的应用前景。

Claims (2)

1.一种制备杂环邻碘硫醚的方法，其特征在于，以杂环硫酚与邻二碘苯为底物，在氢化钠存在下、溶剂中反应，制备杂环邻碘硫醚；杂环硫酚的化学结构式为RSH；邻二碘苯的化学结构式如下：
Figure 290127DEST_PATH_IMAGE001
杂环邻碘硫醚的化学结构式如下：
Figure 676109DEST_PATH_IMAGE002
所述R为以下取代基中的一种：
Figure DEST_PATH_IMAGE003
Figure 157644DEST_PATH_IMAGE004
氢化钠的用量为杂环硫酚摩尔量的4倍；邻二碘苯的用量为杂环硫酚摩尔量的2倍。
2.根据权利要求1所述制备杂环邻碘硫醚的方法，其特征在于，溶剂为二甲基乙酰胺、四氢呋喃、乙腈、乙二醇二甲醚、甲苯中的一种或几种。
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