CN114426533A - Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application - Google Patents
Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application Download PDFInfo
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- CN114426533A CN114426533A CN202111591820.9A CN202111591820A CN114426533A CN 114426533 A CN114426533 A CN 114426533A CN 202111591820 A CN202111591820 A CN 202111591820A CN 114426533 A CN114426533 A CN 114426533A
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- Prior art keywords
- substituted benzothiophene
- polyaryl
- thienyl
- acetone
- benzothiophene
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- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 title abstract description 8
- 238000006555 catalytic reaction Methods 0.000 title abstract description 5
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- FYRWCGOUVMAPMP-UHFFFAOYSA-N 1,3-di(thiophen-3-yl)propan-2-one Chemical compound C1=C(C=CS1)CC(=O)CC1=CSC=C1 FYRWCGOUVMAPMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000003814 drug Substances 0.000 claims abstract description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims description 3
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002474 experimental method Methods 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000003178 anti-diabetic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000002365 anti-tubercular Effects 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention belongs to the technical field of medicine technology and dye industry, and discloses a method for preparing polyaryl substituted benzothiophene by ruthenium catalysis and application thereof. The present invention uses relatively inexpensive ruthenium ([ RuCl ]2(p‑cymene)]2) As a catalyst, activating 1, 3-di (3-thienyl) acetone beta-H to synthesize a six-membered ring to generate polyaryl substituted benzothiophene; in the reaction process, no additive or oxidant is needed, and only simple alkali is used, and the reaction is carried out under mild reaction conditions. The synthesis method provided by the invention is simple, feasible, scientific, reasonable, green, environment-friendly, economical and practical, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of medicine technology and dye industry, and relates to a method for preparing polyaryl substituted benzothiophene by ruthenium catalysis and application of the polyaryl substituted benzothiophene.
Background
Benzothiophene and derivatives thereof are important organic synthesis intermediates and have important application in the fields of pesticides, medicines, dyes and the like. Benzothiophene is one of the dominant structures found in medicines, and has many physiological activities, such as antimicrobial, anti-inflammatory, anticancer, antioxidant, antidiabetic, antituberculosis and the like, so that the research of synthesizing benzothiophene compounds more simply and effectively is of great significance. The methods for synthesizing benzothiophene are various, for example, the traditional method is synthesis of styrene and hydrogen sulfide, or condensation of thiophene and benzene, but these methods have many synthesis steps, and if more groups are substituted on the ring, the difficulty is higher. The polycyclic aromatic hydrocarbon can be prepared by the C-H bond activation of the aromatic benzene ring catalyzed by the metal, but some reactions can be completed only by taking a certain amount of ligand or metal salt as an oxidant, and the metal salt is heavy metal (such as copper, silver and the like) salts which pollute the environment, so that the environment is polluted, and some transition metals are expensive (such as Pd catalysts and the like). Based on this, there is a need in the art for more environmentally friendly, green, economical methods for synthesizing benzothiophene derivatives.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing polyaryl substituted benzothiophene by ruthenium catalysis and application thereof, wherein the preparation method is that ruthenium ([ RuCl ] is cheap under mild conditions without additives and oxidants2(p-cymene)]2) A method for synthesizing polyaryl substituted benzothiophene as a catalyst.
The above purpose of the invention is realized by the following technical scheme:
the invention has a first object to claim polyaryl-substituted benzothiophenes having the structure shown in formula I:
the second object of the present invention is to claim a process for the preparation of the above-mentioned polyaryl-substituted benzothiophenes, which comprises: 1, 3-di (3-thienyl) acetone and diphenylacetylene are used as raw materials, and [ RuCl ] is added2(p-cymene)]2Heating, refluxing and reacting alkali and a nonpolar organic solvent for 36 hours at 100 ℃ in a nitrogen environment, and performing column chromatography separation to obtain polyaryl substituted benzothiophene; the 1, 3-di (3-thienyl) acetone and the diphenylacetyleneThe molar ratio is 2:1, [ RuCl2(p-cymene)]210 mol% of tolane, and the molar ratio of the alkali to the 1, 3-di (3-thienyl) acetone is 1: 1.
Further, the nonpolar organic solvent is dioxane.
Further, the alkali is K2CO3。
As a preferred embodiment of the invention, the preparation method of the polyaryl substituted benzothiophene comprises the following steps: 1, 3-di (3-thienyl) acetone, diphenylacetylene and [ RuCl2(p-cymene)]2Adding the mixture into a dioxane solution, adding dry potassium carbonate, heating and refluxing the mixture to 100 ℃ in a nitrogen environment, reacting for 36 hours, and performing column chromatography separation to obtain the polyaryl substituted benzothiophene.
The third purpose of the invention is to protect the application of the polyaryl substituted benzothiophene in the fields of medicine preparation and luminescent materials.
For example for luminescent materials
And (4) preparing.
Compared with the prior art, the invention has the beneficial effects that:
the present invention uses relatively inexpensive ruthenium ([ RuCl ]2(p-cymene)]2) As a catalyst, activating 1, 3-di (3-thienyl) acetone beta-H to synthesize a six-membered ring to generate a polyaryl substituted naphthalene derivative (polyaryl substituted benzothiophene); in the reaction process, no additive or oxidant is needed, and only simple alkali is used, and the reaction is carried out under mild reaction conditions. The synthesis method provided by the invention is simple, feasible, scientific, reasonable, green, environment-friendly, economical and practical, and is suitable for large-scale production.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
To a 25mL round bottom flask with magnetons was added tolane (18mg, 0.1mmol), the corresponding 1, 3-bis (3-thienyl) propanone (0.2mmol), catalyst [ RuCl ]2(p-cymene)]2(6mg, 10% mol), 4mL dioxane, then dried potassium carbonate (27mg, 0.2mmol), nitrogen gas was purged three times, heated to 100 ℃ for reflux reaction for 36 hours, and then separated by column chromatography (eluent: petroleum ether) to obtain the objective compound. The characterization is as follows.
6, 7-Diphenyl-5- (thienyl-3-methylene) benzo [ b]Thiophene: yield: 45%, melting point: 65-67 ℃.1H NMR(CDCl3,500MHz)δ7.71(s,1H),7.41(d,J＝5.4Hz,1H),7.35(d,J＝5.5Hz,1H),7.21-7.09(m,8H),6.98(d,J＝6.9Hz,2H),6.76(d,J＝4.8Hz,1H),6.68(s,1H),3.92(s,2H).13C NMR(CDCl3,126MHz)δ144.6,139.9,139.6,139.4,138.8,137.1,136.1,135.9,130.7,129.7,128.5,127.8,127.4(d,JC-Cl＝5.1Hz),127.0,126.4,125.1,123.9,123.3,121.3,115.0,112.7,35.0.
The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (7)
1. A polyaryl substituted benzothiophene characterized by the structure of formula I:
2. the process according to claim 1, wherein the reaction product of 1, 3-di (3-thienyl) acetone and the reaction product of the reaction mixture isDiphenylacetylene as raw material, [ RuCl ] was added2(p-cymene)]2Heating, refluxing and reacting alkali and a nonpolar organic solvent for 36 hours at 100 ℃ in a nitrogen environment, and performing column chromatography separation to obtain polyaryl substituted benzothiophene; the molar ratio of the 1, 3-di (3-thienyl) acetone to the diphenylacetylene is 2:1, [ RuCl2(p-cymene)]2Accounting for 10mol percent of the tolane, the molar ratio of the alkali to the 1, 3-di (3-thienyl) acetone is 1: 1.
3. The method according to claim 2, wherein the nonpolar organic solvent is dioxane.
4. The process according to claim 2, wherein the base is K2CO3。
5. The process for preparing polyarylation substituted benzothiophene of claim 2, wherein 1, 3-bis (3-thienyl) acetone, tolane and [ RuCl ]2(p-cymene)]2Adding the mixture into a dioxane solution, adding dry potassium carbonate, heating and refluxing the mixture to 100 ℃ in a nitrogen environment, reacting for 36 hours, and performing column chromatography separation to obtain the polyaryl substituted benzothiophene.
6. Use of a polyaryl-substituted benzothiophene as defined in any one of claims 1 to 5 in the manufacture of a medicament.
7. Use of a polyaryl-substituted benzothiophene as claimed in any one of claims 1 to 5 in the field of luminescent materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111591820.9A CN114426533A (en) | 2021-12-23 | 2021-12-23 | Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111591820.9A CN114426533A (en) | 2021-12-23 | 2021-12-23 | Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application |
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| Publication Number | Publication Date |
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| CN114426533A true CN114426533A (en) | 2022-05-03 |
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| CN202111591820.9A Pending CN114426533A (en) | 2021-12-23 | 2021-12-23 | Method for preparing polyaryl substituted benzothiophene through ruthenium catalysis and application |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093334A (en) * | 2011-02-22 | 2011-06-15 | 郑州大学 | Method for synthesizing condensed ring thiophene compounds |
| CN107935812A (en) * | 2017-12-13 | 2018-04-20 | 大连大学 | Ruthenium is catalyzed the method that alkyl arone prepares more virtue substitution naphthalene derivativeses with tolans reaction |
| CN107954821A (en) * | 2017-12-13 | 2018-04-24 | 大连大学 | A kind of ruthenium catalysis dibenzyl ketone prepares method and the application of more virtue substitution naphthalene derivativeses with interior alkynes cyclization |
| CN107973691A (en) * | 2017-12-13 | 2018-05-01 | 大连大学 | Ruthenium is catalyzed method and the application that aromatic ketone prepares more virtue substitution naphthalene derivativeses with tolans cyclization |
| CN109970703A (en) * | 2019-05-08 | 2019-07-05 | 玉林师范学院 | The preparation method and application of 1,3- heterocyclic substituted aromatic ketone |
-
2021
- 2021-12-23 CN CN202111591820.9A patent/CN114426533A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093334A (en) * | 2011-02-22 | 2011-06-15 | 郑州大学 | Method for synthesizing condensed ring thiophene compounds |
| CN107935812A (en) * | 2017-12-13 | 2018-04-20 | 大连大学 | Ruthenium is catalyzed the method that alkyl arone prepares more virtue substitution naphthalene derivativeses with tolans reaction |
| CN107954821A (en) * | 2017-12-13 | 2018-04-24 | 大连大学 | A kind of ruthenium catalysis dibenzyl ketone prepares method and the application of more virtue substitution naphthalene derivativeses with interior alkynes cyclization |
| CN107973691A (en) * | 2017-12-13 | 2018-05-01 | 大连大学 | Ruthenium is catalyzed method and the application that aromatic ketone prepares more virtue substitution naphthalene derivativeses with tolans cyclization |
| CN108017613A (en) * | 2017-12-13 | 2018-05-11 | 大连大学 | Ruthenium is catalyzed the method that heterocycle arone prepares more virtue substitution naphthalene derivativeses with tolans reaction |
| CN109970703A (en) * | 2019-05-08 | 2019-07-05 | 玉林师范学院 | The preparation method and application of 1,3- heterocyclic substituted aromatic ketone |
Non-Patent Citations (1)
| Title |
|---|
| RAJI REDDY, CHADA等: "[4 + 2] Benzannulation of 3-Alkenylpyrroles/Thiophenes with Propargylic Alcohols: Access to Substituted Indoles, Benzothiophenes, and Aza[5]helicenes" * |
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Application publication date: 20220503 |