CN115197180B - Synthesis method of 3-selenofurans compound promoted by visible light - Google Patents
Synthesis method of 3-selenofurans compound promoted by visible light Download PDFInfo
- Publication number
- CN115197180B CN115197180B CN202210439256.7A CN202210439256A CN115197180B CN 115197180 B CN115197180 B CN 115197180B CN 202210439256 A CN202210439256 A CN 202210439256A CN 115197180 B CN115197180 B CN 115197180B
- Authority
- CN
- China
- Prior art keywords
- reaction
- formula
- visible light
- selenofuran
- diselenide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 claims abstract description 16
- OTJZCIYGRUNXTP-UHFFFAOYSA-N but-3-yn-1-ol Chemical class OCCC#C OTJZCIYGRUNXTP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 15
- 239000003480 eluent Substances 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 14
- -1 trifluoromethoxy, formyl Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 4
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000741 silica gel Substances 0.000 description 20
- 229910002027 silica gel Inorganic materials 0.000 description 20
- 239000000047 product Substances 0.000 description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 description 8
- 239000011669 selenium Substances 0.000 description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000005922 selenation reaction Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- UQCBQVRZVORINC-UHFFFAOYSA-N 1,4-diphenylbut-3-yn-1-ol Chemical compound C=1C=CC=CC=1C(O)CC#CC1=CC=CC=C1 UQCBQVRZVORINC-UHFFFAOYSA-N 0.000 description 3
- 238000010523 cascade reaction Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BONUMEZZJPMOAJ-UHFFFAOYSA-N 4-(4-methoxyphenyl)-1-phenylbut-3-yn-1-ol Chemical compound COC1=CC=C(C=C1)C#CCC(O)C1=CC=CC=C1 BONUMEZZJPMOAJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GZTDVVVCDMQHDK-UHFFFAOYSA-N 4-(4-methylphenyl)-1-phenylbut-3-yn-1-ol Chemical compound Cc1ccc(cc1)C#CCC(O)c1ccccc1 GZTDVVVCDMQHDK-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- RVUMDQJKBYZQCI-UHFFFAOYSA-N BrC1=CC=C(C=C1)C(CC#CC1=CC=CC=C1)O Chemical compound BrC1=CC=C(C=C1)C(CC#CC1=CC=CC=C1)O RVUMDQJKBYZQCI-UHFFFAOYSA-N 0.000 description 1
- LCSVGXLPLJTMHN-UHFFFAOYSA-N C=1C=C(Cl)C=CC=1C(O)CC#CC1=CC=CC=C1 Chemical compound C=1C=C(Cl)C=CC=1C(O)CC#CC1=CC=CC=C1 LCSVGXLPLJTMHN-UHFFFAOYSA-N 0.000 description 1
- HJNWXGNKELBIBG-UHFFFAOYSA-N ClC1=CC=C(C=C1)C#CCC(O)C1=CC=CC=C1 Chemical compound ClC1=CC=C(C=C1)C#CCC(O)C1=CC=CC=C1 HJNWXGNKELBIBG-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- BICXTKPJFREZMO-UHFFFAOYSA-N OC(CC#CC1=CC=C(C#N)C=C1)C1=CC=CC=C1 Chemical compound OC(CC#CC1=CC=C(C#N)C=C1)C1=CC=CC=C1 BICXTKPJFREZMO-UHFFFAOYSA-N 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- LCEFEIBEOBPPSJ-UHFFFAOYSA-N phenyl selenohypobromite Chemical compound Br[Se]C1=CC=CC=C1 LCEFEIBEOBPPSJ-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域Technical field
本发明涉及有机合成化学技术领域,具体为一种可见光促进3-硒基呋喃类化合物的合成方法。The invention relates to the technical field of organic synthetic chemistry, specifically a visible light-promoted synthesis method of 3-selenofuran compounds.
背景技术Background technique
呋喃是一类重要的有机芳杂环化合物,其结构存在于很多天然产物、药物和生物活性分子中,呈现出各种不同的生理活性((a)Org.Chem.Front.,2021,8,2608-2642.;(b)Int.J.Rev.Life Sci.,2012,2,7-16;(b)J.Food Biochem.,2018,42,e12597)。呋喃也是有重要价值的有机合成反应砌块以及高分子材料构建的基础骨架((a)ACS Catal.,2021,11,10058-10083;(b)Sustainable Chem.Ser.,2018,2,217-237.)。Furan is an important class of organic aromatic heterocyclic compounds. Its structure exists in many natural products, drugs and biologically active molecules, and exhibits various physiological activities ((a) Org.Chem.Front., 2021, 8, 2608-2642.; (b) Int. J. Rev. Life Sci., 2012, 2, 7-16; (b) J. Food Biochem., 2018, 42, e12597). Furan is also an important building block for organic synthesis reactions and the basic framework for the construction of polymer materials ((a) ACS Catal., 2021, 11, 10058-10083; (b) Sustainable Chem. Ser., 2018, 2, 217-237. ).
硒是人体中一种必须的微量元素。研究表明适量补充硒能起到防止器官老化与病变,延缓衰老,增强免疫,抵御疾病,抵抗有毒害重金属,减轻放化疗副作用,防癌抗癌的作用(Chem.Rev.2004,104,6255-6286)。此外,含硒化合物在有机合成、药物化学和材料科学领域有着广泛的应用。(Eur.J.Org.Chem.,2009,1649-1664)。Selenium is an essential trace element in the human body. Research shows that appropriate supplementation of selenium can prevent organ aging and lesions, delay aging, enhance immunity, resist diseases, resist toxic heavy metals, reduce the side effects of radiotherapy and chemotherapy, and prevent and fight cancer (Chem.Rev.2004,104,6255- 6286). In addition, selenium-containing compounds have extensive applications in the fields of organic synthesis, medicinal chemistry, and materials science. (Eur. J. Org. Chem., 2009, 1649-1664).
鉴于呋喃骨架和硒基独特的生物活性和理化性质,开发新型高效的合成策略构建含硒呋喃一直是合成化学家追求的目标。传统的合成方法通常在适宜硒化试剂存在下,使用过度金属和氧化剂,使预先制备的呋喃环上发生硒化得到目标化合物((a)AsianJ.Org.Chem.,2021,10,2975-2981;(b)Adv.Synth.Catal.,2021,363,3577-3584;(c)ChemistrySelect,2017,2,9227-9232;(d),Asian J.Org.Chem.,2015,4,875-878.)。此外,基于环化-硒化的串联反应策略也是构建含硒呋喃的有效手段。因为该方法可以同时构建呋喃骨架和形成C-Se键。例如,Gilson Zeni等人公开了一种苯基溴化硒诱导的2-炔基苯甲醚化合物环化/硒化反应合成3-硒基苯并呋喃化合物(J.Org.Chem.,2009,74,2153-2162.)。Benhur Godoi等人描述了在二硒醚存在下,CuI催化的2-炔基苯酚发生环化/硒化反应得到3-硒基苯并呋喃(Eur.J.Org.Chem.,2017,2017,6382-6389)。Luling Wu等人公开了一种共轭加成/环化/硒化的多米诺反应合成3-硒基呋喃化合物(Org.Biomol.Chem.,2012,10,3705-3714.)。最近,Suman De Sarkar等人公开了一种由高丙炔醇合成3-硒基呋喃的电化学方法(J.Org.Chem.,2021,86,16084-16094)。In view of the unique biological activities and physicochemical properties of the furan skeleton and selenium group, the development of new and efficient synthetic strategies to construct selenium-containing furans has always been the goal pursued by synthetic chemists. Traditional synthesis methods usually use transition metals and oxidants in the presence of appropriate selenization reagents to selenize the previously prepared furan ring to obtain the target compound ((a) Asian J. Org. Chem., 2021, 10, 2975-2981 ;(b)Adv.Synth.Catal.,2021,363,3577-3584;(c)ChemistrySelect,2017,2,9227-9232;(d),Asian J.Org.Chem.,2015,4,875-878. ). In addition, the tandem reaction strategy based on cyclization-selenation is also an effective means to construct selenium-containing furans. Because this method can simultaneously construct the furan skeleton and form C-Se bonds. For example, Gilson Zeni et al. disclosed a phenylselenium bromide-induced cyclization/selenation reaction of 2-alkynyl anisole compounds to synthesize 3-selenobenzofuran compounds (J.Org.Chem., 2009, 74,2153-2162.). Benhur Godoi et al. described the CuI-catalyzed cyclization/selenation reaction of 2-alkynylphenol in the presence of diselenide to obtain 3-selenobenzofuran (Eur.J.Org.Chem., 2017, 2017, 6382-6389). Luling Wu et al. disclosed a conjugate addition/cyclization/selenization domino reaction to synthesize 3-selenofuran compounds (Org. Biomol. Chem., 2012, 10, 3705-3714.). Recently, Suman De Sarkar et al. disclosed an electrochemical method for synthesizing 3-selenofuran from homopropynyl alcohol (J. Org. Chem., 2021, 86, 16084-16094).
如上所述,现有技术中公开了多种制备3-硒基呋喃的方法,但这些方法均存在一定的缺陷,例如需要昂贵的过渡金属和电化学反应装置、使用化学氧化剂和空气敏感的硒化试剂(ArSeX)以及反应条件苛刻等。As mentioned above, a variety of methods for preparing 3-selenofurans have been disclosed in the prior art, but these methods all have certain shortcomings, such as requiring expensive transition metals and electrochemical reaction devices, using chemical oxidants, and air-sensitive selenium. chemical reagent (ArSeX) and harsh reaction conditions.
可见光是一种清洁无污染的能源,近年来可见光促进的有机合成反应得到了极大的发展(M.-Y.Cao,X.Ren and Z.Lu,Tetrahedron Lett.,2015,56,3732)。然而文献调研表明,基于可见光参与的高炔丙基醇和二硒醚发生串联/硒化反应合成3-硒基呋喃方法至今未曾报道。基于上述原因,探索高效、环保、反应条件温和、官能团兼容性好以及成本低廉的合成3-硒基呋喃化合物的新方法仍具有重要的意义。这也正是本申请得以完成的基础和动力所在。Visible light is a clean and pollution-free energy source. In recent years, organic synthesis reactions promoted by visible light have been greatly developed (M.-Y.Cao, X.Ren and Z.Lu, Tetrahedron Lett., 2015, 56, 3732) . However, literature research shows that the method for the synthesis of 3-selenofuran based on the tandem/selenation reaction of homopropargyl alcohol and diselenide with the participation of visible light has not been reported so far. Based on the above reasons, it is still of great significance to explore new methods for the synthesis of 3-selenofuran compounds that are efficient, environmentally friendly, have mild reaction conditions, have good functional group compatibility, and are low-cost. This is also the basis and motivation for the completion of this application.
发明内容Contents of the invention
本发明的目的在于提供一种可见光促进3-硒基呋喃类化合物的合成方法,以解决上述背景技术中提出的问题。The object of the present invention is to provide a visible light-promoted synthesis method of 3-selenofuran compounds to solve the problems raised in the above background technology.
为实现上述目的,本发明提供如下技术方案:一种可见光促进3-硒基呋喃类化合物的合成方法,包括以下步骤:In order to achieve the above object, the present invention provides the following technical solution: a visible light-promoted synthesis method of 3-selenofuran compounds, including the following steps:
在有机溶剂中,以具有如式(I)所示结构的高炔丙醇衍生物,式(Ⅱ)所示结构的二硒醚为反应原料,在敞口和室温条件下,可见光照射下进行反应,反应结束后,将反应液减压除去溶剂得到粗产品,粗产品经过柱层析纯化得到式(Ⅲ)所示结构的3-硒基呋喃类化合物,反应方程式如下式所示:In an organic solvent, a high propargyl alcohol derivative with a structure shown in formula (I) and a diselenide with a structure shown in formula (II) are used as reaction raw materials, and the reaction is carried out in the open, at room temperature, and under visible light irradiation. reaction. After the reaction, the solvent is removed from the reaction solution under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain a 3-selenofuran compound with a structure shown in formula (III). The reaction equation is as follows:
其中,式(I)化合物为高炔丙醇衍生物,R1和R2各自独立地选自氢原子、C1~C10的直链或支链的烷基、C1~C6烷氧基、卤素、氰基、硝基、三氟甲基、三氟甲氧基、甲酰基。Wherein, the compound of formula (I) is a homopropargyl alcohol derivative, and R1 and R2 are each independently selected from a hydrogen atom, a C1-C10 linear or branched alkyl group, a C1-C6 alkoxy group, a halogen, and a cyano group. , nitro, trifluoromethyl, trifluoromethoxy, formyl.
式(Ⅱ)化合物为二芳基二硒醚或二烷基二硒醚,R3可以选自C1-C10直链或支链的烷基、苄基、一个或多个取代基取代的苯基,所述取代基选自C1~C10烷基、C1~C6烷氧基、卤素、氰基、硝基、三氟甲基、三氟甲氧基、羧基、羟基。The compound of formula (II) is a diaryl diselenide or a dialkyl diselenide, and R3 can be selected from a C1-C10 linear or branched alkyl group, a benzyl group, or a phenyl group substituted by one or more substituents, The substituent is selected from C1 to C10 alkyl, C1 to C6 alkoxy, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, carboxyl, and hydroxyl.
优选的,式(I)所示结构的2-炔基苯胺与式(II)所示结构的二硒醚的摩尔比为1∶0.5-1∶1,优选为1∶0.5。Preferably, the molar ratio of 2-alkynylaniline with the structure represented by formula (I) and diselenide with the structure represented by formula (II) is 1:0.5-1:1, preferably 1:0.5.
优选的,所述有机溶剂为二甲基亚砜、N,N-二甲基甲酰胺、乙酸乙酯、正己烷、四氢呋喃、1,4-二氧六烷、氯仿、1,2-二氯乙烷、四氯化碳、甲苯中的至少一种,优选N,N-二甲基甲酰胺(DMF)。Preferably, the organic solvent is dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate, n-hexane, tetrahydrofuran, 1,4-dioxane, chloroform, 1,2-dichloro At least one of ethane, carbon tetrachloride and toluene, preferably N,N-dimethylformamide (DMF).
优选的,所述可见光为荧光灯、钨灯,LED灯中的任意一种。Preferably, the visible light is any one of fluorescent lamps, tungsten lamps, and LED lamps.
优选的,反应的时间为30h-50h。Preferably, the reaction time is 30h-50h.
优选的,反应结束后,将反应液减压浓缩,将浓缩物通过柱色谱分离,以石油醚和乙酸乙酯体混合液为洗脱剂,其中石油醚:乙酸乙酯的体积比为(30~300):1,收集洗脱液,旋蒸溶剂后得到式(Ⅲ)所示的3-硒基呋喃。Preferably, after the reaction is completed, the reaction solution is concentrated under reduced pressure, and the concentrate is separated by column chromatography, using a mixture of petroleum ether and ethyl acetate as the eluent, wherein the volume ratio of petroleum ether:ethyl acetate is (30 ~300): 1. Collect the eluent and rotary evaporate the solvent to obtain 3-selenofuran represented by formula (III).
与现有技术相比,本发明至少具有以下优点:Compared with the prior art, the present invention at least has the following advantages:
(1)本发明可在空气条件下进行,操作简单。(1) The present invention can be carried out under air conditions and is simple to operate.
(2)本发明使用可见光作为能量来源,以空气中的氧气作为氧化剂,符合绿色化学要求。(2) The present invention uses visible light as the energy source and oxygen in the air as the oxidant, which meets the requirements of green chemistry.
(3)本发明不使用过渡金属催化剂和化学氧化剂,反应选择性高,产物易分离提纯,收率高。(3) The present invention does not use transition metal catalysts and chemical oxidants, has high reaction selectivity, easy separation and purification of the product, and high yield.
(4)本发明只需0.5当量的二硒醚,原子经济性好。(4) The present invention only requires 0.5 equivalents of diselenide and has good atom economy.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
本发明提供如下技术方案:一种可见光促进3-硒基呋喃类化合物的合成方法,包括以下步骤:The present invention provides the following technical solution: a visible light-promoted synthesis method of 3-selenofuran compounds, including the following steps:
在有机溶剂中,以具有如式(I)所示结构的2-炔基苯胺,式(Ⅱ)所示结构的二硒醚为反应原料,在敞口和室温条件下,可见光照射下进行反应,反应结束后,将反应液减压除去溶剂得到粗产品,粗产品经过柱层析纯化得到式(Ⅲ)所示结构的3-硒基呋喃类化合物,反应方程式如下式所示:In an organic solvent, 2-alkynylaniline with the structure shown in formula (I) and diselenide with the structure shown in formula (II) are used as reaction raw materials, and the reaction is carried out in the open and at room temperature under visible light irradiation. , after the reaction is completed, the solvent is removed from the reaction solution under reduced pressure to obtain a crude product. The crude product is purified by column chromatography to obtain a 3-selenofuran compound with a structure shown in formula (III). The reaction equation is as follows:
其中,式(I)化合物为高炔丙醇衍生物,R1和R2各自独立地选自氢原子、C1~C10的直链或支链的烷基、C1~C6烷氧基、卤素、氰基、硝基、三氟甲基、三氟甲氧基、甲酰基。Wherein, the compound of formula (I) is a homopropargyl alcohol derivative, and R1 and R2 are each independently selected from a hydrogen atom, a C1-C10 linear or branched alkyl group, a C1-C6 alkoxy group, a halogen, and a cyano group. , nitro, trifluoromethyl, trifluoromethoxy, formyl.
式(Ⅱ)化合物为二芳基二硒醚或二烷基二硒醚,R3可以选自C1-C10直链或支链的烷基、苄基、一个或多个取代基取代的苯基,所述取代基选自C1~C10烷基、C1~C6烷氧基、卤素、氰基、硝基、三氟甲基、三氟甲氧基、羧基、羟基。The compound of formula (II) is a diaryl diselenide or a dialkyl diselenide, and R3 can be selected from a C1-C10 linear or branched alkyl group, a benzyl group, or a phenyl group substituted by one or more substituents, The substituent is selected from C1 to C10 alkyl, C1 to C6 alkoxy, halogen, cyano, nitro, trifluoromethyl, trifluoromethoxy, carboxyl, and hydroxyl.
实施例1Example 1
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1,4-二苯基-3-丁炔-1-醇(0.2毫摩尔),二苯基二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=100/1),得到目标化合物64毫克,产率为85%。Under open conditions, add 1,4-diphenyl-3-butyn-1-ol (0.2 mmol) and diphenyl diselenide (0.1 mmol) into a 10 ml reaction tube equipped with a magnetic stirrer. mol), DMF (1 ml), after addition, place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube, and react at room temperature for 40 hours under open conditions. After the reaction is completed, remove the organic phase through a rotary evaporator. Solvent, and the residue was purified using a silica gel column (silica gel specifications were 200 mesh to 300 mesh, and the eluent was petroleum ether/ethyl acetate = 100/1) to obtain 64 mg of the target compound with a yield of 85%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ8.15(d,J=7.9Hz,2H),7.78(d,J=7.9Hz,2H),7.51(dd,J=14.1,6.8Hz,6H),7.42-7.23(m,5H),6.81(s,1H).13C NMR(100MHz,CDCl3):δ153.5,153.3,131.9,130.6,130.4,129.9,129.1,128.8,128.7,128.2,126.5,126.4,124.1,114.5,106.1.The NMR spectrum data of the obtained product are: 1 H NMR (400MHz, CDCl 3 ): δ8.15 (d, J = 7.9 Hz, 2H), 7.78 (d, J = 7.9 Hz, 2H), 7.51 (dd, J = 14.1 ,6.8Hz,6H),7.42-7.23(m,5H),6.81(s,1H). 13 C NMR (100MHz, CDCl 3 ): δ153.5,153.3,131.9,130.6,130.4,129.9,129.1,128.8,128.7 ,128.2,126.5,126.4,124.1,114.5,106.1.
实施例2Example 2
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1-苯基-4-(4’-甲基苯基)-3-丁炔-1-醇(0.2毫摩尔),二苯基二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=90/1),得到目标化合物65毫克,产率为83%。Under open conditions, add 1-phenyl-4-(4'-methylphenyl)-3-butyn-1-ol (0.2 mmol) into a 10 ml reaction tube equipped with a magnetic stirrer. After adding diphenyl diselenide (0.1 mmol) and DMF (1 ml), place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube and react at room temperature for 40 hours under open conditions. After the reaction is completed , remove the solvent from the organic phase through a rotary evaporator, and purify the residue with a silica gel column (silica gel specifications are 200 mesh to 300 mesh, and the eluent is petroleum ether/ethyl acetate = 90/1) to obtain 65 mg of the target compound. The yield was 83%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ7.90(d,J=7.9Hz,2H),7.68(d,J=7.9Hz,2H),7.38(t,J=7.6Hz,4H),7.27(t,J=7.4Hz,1H),7.30-7.19(m,5H),6.71(s,1H),2.39(s,3H).13C NMR(100MHz,CDCl3):δ153.3,152.6,137.8,131.6,129.6,129.0,128.8,128.3,127.4,127.3,126.2,125.9,123.8,113.7,104.6,21.1.The NMR spectrum data of the obtained product are: 1 H NMR (400MHz, CDCl 3 ): δ7.90 (d, J = 7.9 Hz, 2H), 7.68 (d, J = 7.9 Hz, 2H), 7.38 (t, J = 7.6 Hz, 4H), 7.27 (t, J = 7.4Hz, 1H), 7.30-7.19 (m, 5H), 6.71 (s, 1H), 2.39 (s, 3H). 13 C NMR (100MHz, CDCl 3 ): δ153.3,152.6,137.8,131.6,129.6,129.0,128.8,128.3,127.4,127.3,126.2,125.9,123.8,113.7,104.6,21.1.
实施例3Example 3
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1-苯基-4-(4’-甲氧基苯基)-3-丁炔-1-醇(0.2毫摩尔),二苯基二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=70/1),得到目标化合物65毫克,产率为80%。Under open conditions, add 1-phenyl-4-(4'-methoxyphenyl)-3-butyn-1-ol (0.2 mmol) into a 10 ml reaction tube equipped with a magnetic stirrer. , diphenyl diselenide (0.1 mmol), DMF (1 ml), after addition, place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube, and react at room temperature for 40 hours under open conditions. The reaction is completed. Afterwards, the solvent was removed from the organic phase through a rotary evaporator, and the residue was purified using a silica gel column (silica gel specifications were 200 mesh to 300 mesh, and the eluent was petroleum ether/ethyl acetate = 70/1) to obtain 65 mg of the target compound. , the yield is 80%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ8.01(d,J=8.7Hz,2H),7.82-7.60(m,2H),7.50-7.26(m,4H),6.99(d,J=8.8Hz,2H),6.79(s,1H),3.88(s,3H).13C NMR(100MHz,CDCl3):δ159.2,153.9,152.5,132.0,130.1,129.5,129.1,128.8,127.9,127.3,126.0,123.5,123.1,113.9,113.8,103.5,55.1.The NMR spectrum data of the obtained product are: 1 H NMR (400MHz, CDCl 3 ): δ8.01 (d, J = 8.7Hz, 2H), 7.82-7.60 (m, 2H), 7.50-7.26 (m, 4H), 6.99 (d, J=8.8Hz, 2H), 6.79 (s, 1H), 3.88 (s, 3H). 13 C NMR (100MHz, CDCl 3 ): δ159.2, 153.9, 152.5, 132.0, 130.1, 129.5, 129.1, 128.8 ,127.9,127.3,126.0,123.5,123.1,113.9,113.8,103.5,55.1.
实施例4Example 4
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1-苯基-4-(4’-氯苯基)-3-丁炔-1-醇(0.2毫摩尔),二苯基二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=100/1),得到目标化合物73毫克,产率为89%。Under open conditions, put 1-phenyl-4-(4'-chlorophenyl)-3-butyn-1-ol (0.2 mmol) into a 10 ml reaction tube equipped with a magnetic stirrer. After adding phenyl diselenide (0.1 mmol) and DMF (1 ml), place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube and react at room temperature for 40 hours under open conditions. After the reaction is completed, The solvent was removed from the organic phase through a rotary evaporator, and the residue was purified using a silica gel column (silica gel specifications were 200 mesh to 300 mesh, and the eluent was petroleum ether/ethyl acetate = 100/1) to obtain 73 mg of the target compound. The rate is 89%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ7.88(d,J=8.3Hz,2H),7.55(d,J=8.0Hz,2H),7.33-7.24(m,5H),7.22-7.08(m,5H),6.62(s,1H).13C NMR(100MHz,CDCl3):δ153.9,152.6,134.2,132.1,131.9,130.6,130.3,130.1,129.3,129.0,128.4,127.5,127.3,124.9,114.8,107.1.The obtained product NMR spectrum data are: 1 H NMR (400MHz, CDCl 3 ): δ7.88 (d, J = 8.3 Hz, 2H), 7.55 (d, J = 8.0 Hz, 2H), 7.33-7.24 (m, 5H) ),7.22-7.08(m,5H),6.62(s,1H). 13 C NMR (100MHz, CDCl 3 ): δ153.9,152.6,134.2,132.1,131.9,130.6,130.3,130.1,129.3,129.0,128.4, 127.5,127.3,124.9,114.8,107.1.
实施例5Example 5
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1-苯基-4-(4’-甲酯基苯基)-3-丁炔-1-醇(0.2毫摩尔),二苯基二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=60/1),得到目标化合物78毫克,产率为90%。Under open conditions, add 1-phenyl-4-(4'-methoxyphenyl)-3-butyn-1-ol (0.2 mmol) into a 10 ml reaction tube equipped with a magnetic stirrer. , diphenyl diselenide (0.1 mmol), DMF (1 ml), after addition, place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube, and react at room temperature for 40 hours under open conditions. The reaction is completed. Afterwards, the solvent was removed from the organic phase through a rotary evaporator, and the residue was purified using a silica gel column (silica gel specifications were 200 mesh to 300 mesh, and the eluent was petroleum ether/ethyl acetate = 60/1) to obtain 78 mg of the target compound. , the yield is 90%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ8.14-8.00(m,4H),7.79-7.72(m,2H),7.50-7.26(m,8H),6.75(s,1H),3.93(s,3H).13C NMR(100MHz,CDCl3):δ166.0,153.1,151.0,133.9,130.1,128.8,128.7,128.6,128.0,127.4,126.5,124.9,124.8,123.5,113.3,108.3,51.6.The NMR spectrum data of the obtained product are: 1 H NMR (400MHz, CDCl 3 ): δ8.14-8.00(m,4H),7.79-7.72(m,2H),7.50-7.26(m,8H),6.75(s, 1H), 3.93 (s, 3H). 13 C NMR (100MHz, CDCl 3 ): δ166.0,153.1,151.0,133.9,130.1,128.8,128.7,128.6,128.0,127.4,126.5,124.9,124.8,123.5,113.3 , 108.3,51.6.
实施例6Example 6
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1-苯基-4-(4’-氰基苯基)-3-丁炔-1-醇(0.2毫摩尔),二苯基二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=70/1),得到目标化合物72毫克,产率为90%。Under open conditions, add 1-phenyl-4-(4'-cyanophenyl)-3-butyn-1-ol (0.2 mmol) into a 10 ml reaction tube equipped with a magnetic stirrer. After adding diphenyl diselenide (0.1 mmol) and DMF (1 ml), place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube and react at room temperature for 40 hours under open conditions. After the reaction is completed , remove the solvent from the organic phase through a rotary evaporator, and purify the residue with a silica gel column (silica gel specifications are 200 mesh to 300 mesh, and the eluent is petroleum ether/ethyl acetate = 70/1) to obtain 72 mg of the target compound. The yield is 90%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ8.18(d,J=8.2Hz,2H),7.69(dd,J=13.0,8.2Hz,4H),7.40(t,J=7.7Hz,4H),7.36(t,J=7.6Hz,1H),7.35(d,J=5.2Hz,3H),6.69(s,1H).13C NMR(100MHz,CDCl3):δ155.5,151.3,135.9,133.3,132.8,131.9,130.7,130.4,130.0,129.8,128.8,127.3,125.4,120.0,115.6,111.7,111.4.The NMR spectrum data of the obtained product are: 1 H NMR (400MHz, CDCl 3 ): δ8.18 (d, J = 8.2 Hz, 2H), 7.69 (dd, J = 13.0, 8.2 Hz, 4H), 7.40 (t, J =7.7Hz, 4H), 7.36 (t, J = 7.6Hz, 1H), 7.35 (d, J = 5.2Hz, 3H), 6.69 (s, 1H). 13 C NMR (100MHz, CDCl 3 ): δ155. 5,151.3,135.9,133.3,132.8,131.9,130.7,130.4,130.0,129.8,128.8,127.3,125.4,120.0,115.6,111.7,111.4.
实施例7Example 7
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1-(4’-氯苯基)-4-苯基-3-丁炔-1-醇(0.2毫摩尔),二苯基二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=90/1),得到目标化合物71毫克,产率为87%。Under open conditions, put 1-(4'-chlorophenyl)-4-phenyl-3-butyn-1-ol (0.2 mmol) into a 10 ml reaction tube equipped with a magnetic stirrer. After adding phenyl diselenide (0.1 mmol) and DMF (1 ml), place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube and react at room temperature for 40 hours under open conditions. After the reaction is completed, The solvent was removed from the organic phase through a rotary evaporator, and the residue was purified using a silica gel column (silica gel specifications were 200 mesh to 300 mesh, and the eluent was petroleum ether/ethyl acetate = 90/1) to obtain 71 mg of the target compound. The rate is 87%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ8.06(d,J=7.9Hz,2H),7.65(d,J=8.5Hz,2H),7.45(dd,J=9.9,5.4Hz,4H),7.39(d,J=8.5Hz,2H),7.36-7.22(m,4H),6.75(s,1H).13C NMR(100MHz,CDCl3):δ154.5,152.9,134.5,132.6,132.0,131.3,130.3,130.0,129.5,129.1,129.0,128.2,127.5,126.1,115.1,107.1.The NMR spectrum data of the obtained product are: 1 H NMR (400MHz, CDCl 3 ): δ8.06 (d, J = 7.9 Hz, 2H), 7.65 (d, J = 8.5 Hz, 2H), 7.45 (dd, J = 9.9 ,5.4Hz,4H),7.39(d,J=8.5Hz,2H),7.36-7.22(m,4H),6.75(s,1H). 13 C NMR (100MHz, CDCl 3 ): δ154.5,152.9,134.5 ,132.6,132.0,131.3,130.3,130.0,129.5,129.1,129.0,128.2,127.5,126.1,115.1,107.1.
实施例8Example 8
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1-(4’-溴苯基)-4-苯基-3-丁炔-1-醇(0.2毫摩尔),二苯基二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=90/1),得到目标化合物74毫克,产率为82%。Under open conditions, put 1-(4'-bromophenyl)-4-phenyl-3-butyn-1-ol (0.2 mmol) into a 10 ml reaction tube equipped with a magnetic stirrer. After adding phenyl diselenide (0.1 mmol) and DMF (1 ml), place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube and react at room temperature for 40 hours under open conditions. After the reaction is completed, The solvent was removed from the organic phase through a rotary evaporator, and the residue was purified using a silica gel column (silica gel specifications were 200 mesh to 300 mesh, and the eluent was petroleum ether/ethyl acetate = 90/1) to obtain 74 mg of the target compound. The rate is 82%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ8.00(d,J=7.9Hz,2H),7.53(d,J=8.2Hz,2H),7.49(d,J=8.4Hz,2H),7.40-7.17(m,8H),6.69(s,1H).13C NMR(100MHz,CDCl3):δ153.0,151.7,131.9,131.73,130.1,129.1,128.2,128.1,128.0,127.3,126.6,125.9,125.0,121.7,113.8,105.8.The NMR spectrum data of the obtained product are: 1 H NMR (400MHz, CDCl 3 ): δ8.00 (d, J = 7.9 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.40-7.17 (m, 8H), 6.69 (s, 1H). 13 C NMR (100MHz, CDCl 3 ): δ153.0,151.7,131.9,131.73,130.1,129.1,128.2,128.1,128.0,127.3 ,126.6,125.9,125.0,121.7,113.8,105.8.
实施例9Example 9
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1,4-二苯基-3-丁炔-1-醇(0.2毫摩尔),二(4-甲基苯基)二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=90/1),得到目标化合物68毫克,产率为88%。Under open conditions, add 1,4-diphenyl-3-butyn-1-ol (0.2 mmol) and bis(4-methylphenyl) into a 10 ml reaction tube equipped with a magnetic stirrer. After adding diselenide (0.1 mmol) and DMF (1 ml), place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube and react at room temperature for 40 hours under open conditions. After the reaction is completed, the organic The solvent was removed from the phase by a rotary evaporator, and the residue was purified with a silica gel column (silica gel specifications were 200 mesh to 300 mesh, and the eluent was petroleum ether/ethyl acetate = 90/1) to obtain 68 mg of the target compound, with a yield of 88%.
所得产物核磁图谱数据为:7.87-7.60(m,5H),7.51-7.40(m,4H),7.28(d J=7.9Hz,2H),7.21-7.16(m,3H),6.69(s,1),2.32(s,3H).13C NMR(100MHz,CDCl3):δ152.1,149.6,135.7,136.2,133.8,133.0,132.9,130.7,130.1,129.0,128.9,128.8,127.3,125.1,114.7,106.3,21.6.The NMR spectrum data of the obtained product are: 7.87-7.60(m,5H),7.51-7.40(m,4H),7.28(d J=7.9Hz,2H),7.21-7.16(m,3H),6.69(s,1 ), 2.32 (s, 3H). 13 C NMR (100MHz, CDCl 3 ): δ152.1,149.6,135.7,136.2,133.8,133.0,132.9,130.7,130.1,129.0,128.9,128.8,127.3,125.1,114.7,10 6.3 ,21.6.
实施例10Example 10
反应方程式如下式所示:The reaction equation is as follows:
敞口条件下,向装有磁力搅拌子的10毫升反应管中装入1,4-二苯基-3-丁炔-1-醇(0.2毫摩尔),二(4-甲氧基苯基)二硒醚(0.1毫摩尔),DMF(1毫升),加毕,将23瓦白色紧凑型荧光灯放在距离反应管1厘米的地方,敞口条件下室温反应40小时,反应完成后,将有机相通过旋转蒸发器除去溶剂,残余物用硅胶柱进行纯化(硅胶规格为200目~300目,洗脱剂为石油醚/乙酸乙酯=90/1),得到目标化合物66毫克,产率为82%。Under open conditions, add 1,4-diphenyl-3-butyn-1-ol (0.2 mmol) and bis(4-methoxyphenyl) into a 10 ml reaction tube equipped with a magnetic stirrer. ) diselenide (0.1 mmol), DMF (1 ml), after addition, place a 23-watt white compact fluorescent lamp 1 cm away from the reaction tube, and react at room temperature for 40 hours under open conditions. After the reaction is completed, The solvent was removed from the organic phase using a rotary evaporator, and the residue was purified using a silica gel column (silica gel specifications were 200 mesh to 300 mesh, and the eluent was petroleum ether/ethyl acetate = 90/1) to obtain 66 mg of the target compound, yield is 82%.
所得产物核磁图谱数据为:1H NMR(400MHz,CDCl3):δ8.09(d,J=8.0Hz,2H),7.74(d,J=7.9Hz,2H),7.52-7.40(m,6H),7.39-7.25(m,2H),6.88(d,J=8.6Hz,2H),6.65(s,1H),3.82(s,3H).13C NMR(100MHz,CDCl3):δ150.1,153.5,152.3,134.6,131.3,130.9,129.3,128.9,128.5,126.6,124.7,121.6,115.8,113.6,108.7,56.1.The NMR spectrum data of the obtained product are: 1 H NMR (400MHz, CDCl 3 ): δ8.09 (d, J = 8.0 Hz, 2H), 7.74 (d, J = 7.9 Hz, 2H), 7.52-7.40 (m, 6H) ), 7.39-7.25 (m, 2H), 6.88 (d, J = 8.6Hz, 2H), 6.65 (s, 1H), 3.82 (s, 3H). 13 C NMR (100MHz, CDCl 3 ): δ 150.1, 153.5 ,152.3,134.6,131.3,130.9,129.3,128.9,128.5,126.6,124.7,121.6,115.8,113.6,108.7,56.1.
综上所述,本发明制备方法以高炔丙基醇和二硒醚为原料,以二甲基亚砜、N,N-二甲基甲酰胺、乙酸乙酯、正己烷、四氢呋喃、1,4-二氧六烷、氯仿、1,2-二氯乙烷、四氯化碳、甲苯中的至少一种,反应温度为室温,敞口条件下白色荧光灯照射,高效合成出3-硒基呋喃化合物,该方法与传统的合成方法相比,具有反应条件温和,在室温下可顺利进行;操作简单,所有操作均可在敞开体系中进行;同时本方法避免了使用昂贵的过渡金属催化剂、光催化剂和氧化剂,具有经济和绿色环保等特点。To sum up, the preparation method of the present invention uses high propargyl alcohol and diselenide as raw materials, dimethyl sulfoxide, N, N-dimethylformamide, ethyl acetate, n-hexane, tetrahydrofuran, 1,4 - At least one of dioxane, chloroform, 1,2-dichloroethane, carbon tetrachloride, and toluene, the reaction temperature is room temperature, and 3-selenofuran is efficiently synthesized under exposure to white fluorescent light Compounds, compared with traditional synthesis methods, this method has mild reaction conditions and can proceed smoothly at room temperature; the operation is simple, and all operations can be performed in an open system; at the same time, this method avoids the use of expensive transition metal catalysts, light Catalysts and oxidants are economical and environmentally friendly.
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art will understand that various changes, modifications, and substitutions can be made to these embodiments without departing from the principles and spirit of the invention. and modifications, the scope of the invention is defined by the appended claims and their equivalents.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210439256.7A CN115197180B (en) | 2022-04-25 | 2022-04-25 | Synthesis method of 3-selenofurans compound promoted by visible light |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210439256.7A CN115197180B (en) | 2022-04-25 | 2022-04-25 | Synthesis method of 3-selenofurans compound promoted by visible light |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115197180A CN115197180A (en) | 2022-10-18 |
CN115197180B true CN115197180B (en) | 2024-01-23 |
Family
ID=83575065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210439256.7A Active CN115197180B (en) | 2022-04-25 | 2022-04-25 | Synthesis method of 3-selenofurans compound promoted by visible light |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115197180B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117142997A (en) * | 2023-08-30 | 2023-12-01 | 南通大学 | A kind of visible light-promoted synthesis method of selenium-based dibenzocycloheptanone |
CN117304132B (en) * | 2023-09-15 | 2024-12-06 | 南通大学 | A method for synthesizing selenothiazoline compounds promoted by visible light |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113603653A (en) * | 2021-08-23 | 2021-11-05 | 南通大学 | A kind of visible light-promoted synthesis method of seleno-oxazolidine-2.4-dione |
-
2022
- 2022-04-25 CN CN202210439256.7A patent/CN115197180B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113603653A (en) * | 2021-08-23 | 2021-11-05 | 南通大学 | A kind of visible light-promoted synthesis method of seleno-oxazolidine-2.4-dione |
Also Published As
Publication number | Publication date |
---|---|
CN115197180A (en) | 2022-10-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN115197180B (en) | Synthesis method of 3-selenofurans compound promoted by visible light | |
CN108101734A (en) | A kind of method that ruthenium catalysis fluorine-containing aromatic ketone prepares more virtue substitution naphthalene derivativeses with tolans reaction | |
CN110386885A (en) | A kind of visible light promotion β-carbonyl sulphones preparation method | |
CN105085217B (en) | It is a kind of using copper as the synthetic method of catalyst benzfluorenone and its derivative | |
CN114380675A (en) | A kind of method that visible light induces the reaction of halogenated aromatic hydrocarbon and phenol compound to synthesize arylphenol | |
CN112159312B (en) | A kind of synthetic method of triarylmethane compound | |
CN108569942A (en) | A kind of preparation method of α-trifluoromethylthio substituted acetophenone class compound | |
CN109232525B (en) | Photocatalytic oxidation synthesis method of thioxanthone compound | |
CN107602452B (en) | A kind of synthetic method of 3-acyl pyridine compounds | |
CN116283707A (en) | Synthesis method of indole compound promoted by visible light | |
CN108864173B (en) | Process for converting substituted sodium aryl sulfinate to aryl tri-n-butyl tin | |
CN118908997A (en) | Preparation method and application of alpha-phosphonyl imine compound | |
CN106496091B (en) | A kind of 2 dicarbapentaborane substituted azole class compounds and preparation method thereof | |
CN115322100A (en) | Delta, epsilon-alkenyl ketone compound and preparation method and application thereof | |
CN115215778A (en) | Alpha-difluoro seleno methyl ketone derivative and preparation method thereof | |
CN116120326B (en) | A kind of α-methyldeoxy-codonopsis alkaloid compound and its synthesis method | |
CN110028438B (en) | A kind of synthetic method of 3-phenyl-3-indole trifluoromethyl acetone derivatives | |
CN115028568B (en) | Synthesis method of 3-selenoindole compound promoted by visible light | |
CN105801411B (en) | A kind of synthetic method of the aryl methyl ketone derivative of 2 aromatic acid base 1 | |
CN105820096B (en) | A kind of method for preparing substitution ethyl aryl sulfone | |
CN117088826B (en) | Synthesis method of polysubstituted oxazole promoted by visible light | |
CN118852084A (en) | A method for synthesizing selenoflavanones by promoting visible light | |
CN117142997A (en) | A kind of visible light-promoted synthesis method of selenium-based dibenzocycloheptanone | |
CN106977447B (en) | A kind of preparation method of the carbazole compound of the hydroxyl of symmetrical configuration | |
CN114524790A (en) | C2 alkynyl disubstituted 2H-chromene compound and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |