CN104844565A - 一种基于硫粉合成噻蒽的简便方法 - Google Patents
一种基于硫粉合成噻蒽的简便方法 Download PDFInfo
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- CN104844565A CN104844565A CN201510176702.XA CN201510176702A CN104844565A CN 104844565 A CN104844565 A CN 104844565A CN 201510176702 A CN201510176702 A CN 201510176702A CN 104844565 A CN104844565 A CN 104844565A
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- thianthrene
- sulphur powder
- sulfur powder
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- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 claims abstract description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 239000012074 organic phase Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000005864 Sulphur Substances 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000005029 thianthrenes Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
一种基于硫粉合成噻蒽的简便方法，将邻二碘苯0.5mmol,硫粉0.5mmol，碘化亚铜0.05 mmo，1,10-菲啰啉0.1mmol和碳酸钾1.0mmol称入25mL圆底烧瓶，加入磁子和2mL二甲基亚砜，所得有机相以无水Na2SO4干燥，过滤，所得滤液蒸除溶剂后，残余物通过硅胶柱层析分离提纯得到的噻蒽产物。该方法的优点是：1、原料简单，无需使用具有刺激性气味的硫酚或其衍生物；2、操作简便，无需任何无水无氧等特殊操作；3、反应条件温和，90摄氏度加热既可完成反应，适合放大合成。
Description
技术领域
本发明涉及一种环境友好的合成噻蒽的方法。
背景技术
噻蒽作为有机合成中间体，其主要特征是1,4-位含两个硫的双苯并杂环结构。这类化合物在有机化学领域具有重要的作用。同时，研究证实噻蒽及其衍生物具有多样的生物功能和药物活习惯，也是合成多种药物的关键中间体。目前已知的合成噻吩的方法是通过苯硫酚衍生物或者二苯硫醚衍生物为主要原料，通过铜催化的偶联反应关环得到目标产物。由于硫醚的合成也需要用到苯硫酚，因此这些方法直接或间接的地需要苯硫酚为原料，这类物质的的刺激性气味以及所使用中所带来的环境污染成为合成工艺的重大限制。因此，建立物使用硫酚类化合物的方法合成噻蒽类化合物具有重要意义。
发明内容
本发明的目的在于提供一种以硫粉为原料合成噻蒽的方法，该合成方法所需原料简单易得、环境友好、反应条件温和。
本发明是这样实现的，将邻二碘苯0.5mmol, 硫粉0.5mmol，碘化亚铜0.05 mmo，1,10-菲啰啉0.1mmol和碳酸钾1.0mmol称入25mL圆底烧瓶，加入磁子和2mL二甲基亚砜，90oC下加热12小时。反应结束后加入蒸馏水10mL，并以乙酸乙酯萃取。所得有机相以无水Na2SO4干燥，过滤。所得滤液蒸除溶剂后，残余物通过硅胶柱层析分离提纯得到的噻蒽产物。
本发明的技术效果是：直接使用环境友好的硫粉为硫源、廉价的铜盐为催化剂、反应操作简单、条件温和，适合放大生产。
附图说明
图1为本发明合成流程图。
图2为本发明中产物噻蒽的核磁共振氢谱。
图3为本发明中产物噻蒽的核磁共振碳谱。
具体实施方式
本发明是这样实现的，在25 mL的圆底烧瓶中加入邻二碘苯(0.5 mmol)、硫粉(0.5 mmol)、碘化亚铜(0.05 mmol)、1,10-菲啰啉(0.1 mmol)、碳酸钾(1 .0mmol)和二甲基亚砜(2 mL)。所得混合体系再90oC搅拌12小时。冷却至室温后向体系中加入10 mL水，然后用乙酸乙酯(3×10 mL)萃取，无水硫酸钠干燥。蒸除溶剂后，所得残余物以硅胶柱层析得到纯品，产率82%。反应式和数据如下图1所示。所得产物结构和纯度经过核磁共振氢谱和碳谱测试并和文献数据比较得以确定。
产物噻蒽的核磁共振氢谱和碳谱数据为：
1H NMR (CDCl3, 400 MHz), δ= 7.46 (q, 4 H, J = 5.6 Hz), 7.20 (q, 4 H, J = 5.6 Hz); 13C NMR (CDCl3, 100 MHz), δ= 135.6, 128.8, 127.7。
Claims (2)
1. 一种基于硫粉合成噻蒽的简便方法，其特征为：将邻二碘苯0.5mmol, 硫粉0.5mmol，碘化亚铜0.05 mmo，1,10-菲啰啉0.1mmol和碳酸钾1.0mmol称入25mL圆底烧瓶，加入磁子和2mL二甲基亚砜，90oC下加热12小时，反应结束后加入蒸馏水10mL，并以乙酸乙酯萃取，所得有机相以无水Na2SO4干燥，过滤，所得滤液蒸除溶剂后，残余物通过硅胶柱层析分离提纯得到的噻蒽产物。
2. 根据权利要求1所述的一种基于硫粉合成噻蒽的简便方法，其特征在于，以硫粉为原料，和邻二碘苯通过四次碳-硫偶联成环得到噻蒽产物。
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| CN201510176702.XA CN104844565B (zh) | 2015-04-15 | 2015-04-15 | 一种基于硫粉合成噻蒽的方法 |
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| CN104844565A true CN104844565A (zh) | 2015-08-19 |
| CN104844565B CN104844565B (zh) | 2017-03-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916090A (zh) * | 2017-03-29 | 2017-07-04 | 大连理工大学 | 一种基于九水硫化钠合成硫酚类化合物的制备方法 |
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2015
- 2015-04-15 CN CN201510176702.XA patent/CN104844565B/zh not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| CHUANZHOU TAO, ET AL.: "Ligand-Free Copper-Catalyzed Synthesis of Diaryl Thioethers from Aryl Halides and Thioacetamide", 《SYNLETT》 * |
| EDYTA M. BRZOSTOWSKA, ET AL.: "Polysulfane Antitumor Agents from o-Benzyne. An Odd-Even Alternation Found in the Stability of Products o-C6H4Sx (x=1-8)", 《J. ORG. CHEM.》 * |
| HSING-YING CHEN, ET AL.: "Use of Base Control To Provide High Selectivity between Diaryl Thioether and Diaryl Disulfide for C−S Coupling Reactions of Aryl Halides and Sulfur and a Mechanistic Study", 《ORGANOMETALLICS》 * |
| PENG ZHAO, ET AL.: "Cu-Catalyzed Synthesis of Diaryl Thioethers and S‑Cycles by Reaction of Aryl Iodides with Carbon Disulfide in the Presence of DBU", 《J. ORG. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106916090A (zh) * | 2017-03-29 | 2017-07-04 | 大连理工大学 | 一种基于九水硫化钠合成硫酚类化合物的制备方法 |
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Granted publication date: 20170329 Termination date: 20180415 |