CN108623429B - Method for preparing 1, 1' -binaphthyl - Google Patents
Method for preparing 1, 1' -binaphthyl Download PDFInfo
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- CN108623429B CN108623429B CN201810767030.3A CN201810767030A CN108623429B CN 108623429 B CN108623429 B CN 108623429B CN 201810767030 A CN201810767030 A CN 201810767030A CN 108623429 B CN108623429 B CN 108623429B
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- binaphthyl
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- bmim
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- halonaphthalene
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- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002608 ionic liquid Substances 0.000 claims abstract description 18
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 4
- 238000004440 column chromatography Methods 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000006578 reductive coupling reaction Methods 0.000 claims description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims 2
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 claims 1
- XREPTGNZZKNFQZ-UHFFFAOYSA-M 1-butyl-3-methylimidazolium iodide Chemical compound [I-].CCCCN1C=C[N+](C)=C1 XREPTGNZZKNFQZ-UHFFFAOYSA-M 0.000 claims 1
- HGGLDADJQQPKKC-UHFFFAOYSA-O 2-butyl-3-methyl-1h-imidazol-3-ium Chemical class CCCCC1=[NH+]C=CN1C HGGLDADJQQPKKC-UHFFFAOYSA-O 0.000 claims 1
- YMRPKBLFDBUOAJ-UHFFFAOYSA-N 5-butyl-2-methyl-1h-imidazole Chemical class CCCCC1=CN=C(C)N1 YMRPKBLFDBUOAJ-UHFFFAOYSA-N 0.000 claims 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- -1 butylmethylimidazolium tetrafluoroborate Chemical compound 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 3
- 239000012043 crude product Substances 0.000 abstract description 2
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SKCMXQYDXKUHEC-UHFFFAOYSA-N 5-(4-chlorobutyl)-2-methyl-1H-imidazole Chemical compound CC=1NC(=CN1)CCCCCl SKCMXQYDXKUHEC-UHFFFAOYSA-N 0.000 description 1
- JQWLAUJYCKFZQT-UHFFFAOYSA-N 5-butyl-2-methyl-1h-imidazole;hydrochloride Chemical compound [Cl-].CCCCC1=C[NH2+]C(C)=N1 JQWLAUJYCKFZQT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910006130 SO4 Inorganic materials 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 1, 1' -binaphthyl by using metal samarium to promote a 1-halonaphthalene coupling reaction under the catalysis of cupric salt in ionic liquid. Stirring 1-bromonaphthalene in ionic liquid [ bmim][BF4](butylmethylimidazolium tetrafluoroborate) and then adding metal samarium powder and anhydrous copper chloride powder in sequence. The reaction system is carried out under anhydrous conditions. Stirring at room temperature until the reaction is complete. The resulting reaction mixture was subjected to ionic liquid recovery. Separating the crude product by column chromatography to obtain 1, 1' -binaphthyl, and recrystallizing to obtain pure product with yield of 70-98%.
Description
Technical Field
The invention belongs to the field of transition metal catalytic synthesis, and particularly relates to a method for synthesizing 1, 1' -binaphthyl by catalyzing 1-halonaphthalene with cupric salt.
Background
1, 1' -binaphthyl compounds are important organic synthesis intermediates in the chemical industry, and have wide application in catalysis, pharmacy, chiral synthesis and photosensitive materials [ document 1. Zhang Li, Zheng Chen Cheng Yuan, etc.. chemical production and technology 2014,21(03):31-44+9 ]. For its synthesis, domestic research is relatively rare. The method of coupling 1-halonaphthalene is generally common, and The synthesis requires The 1-halonaphthalene cross-coupling catalyzed by noble metal such as palladium compound [ document 2.Nising C F, Schmid U K, Nieger M, The Journal of Organic Chemistry,2004,69:6830-6833 ]. In addition, the Grignard-reagent self-coupling type reaction is also one of the methods, but such methods usually require relatively complicated operating conditions [ reference 3. Tangjinpeng, Tang Yu, Yang, etc.. organic chemistry 2013,33(05): 1010-. Suzuki-type coupling reactions are also commonly used for the synthesis of such compounds [ document 5.Yaghi O M, et al. PCT Int Appl 2011014503,2011-02 ]. In recent years, nickel chloride or cuprous iodide can be used to couple a plurality of halogenated hydrocarbons under the promotion of metal samarium, but the coupling of 1-halonaphthalene is not realized [ document 6, ShowHuan, study on coupling reaction of metal samarium under the catalysis of transition metal, university of Qingdao science and technology, 2017 ].
Traditional chemical reactions and their related chemical industries are the major sources of serious pollution in the world today, and most of the pollution comes from the large amount of volatile organic solvents used in the reaction process, such as benzene, chlorinated alkanes, alcohols, ketones, etc. For the pollution of organic solvents, the search for green alternative solvents is an important research content. Among them, the organic reaction using ionic liquid as solvent is an important method in the current alternative solvent technology [ document 7. Jianping, Lidangting, Cold inflammation, etc. chemical engineering progress 2014,33(11):2815-2828 ].
The invention discloses a method for preparing 1, 1' -binaphthyl by using metal samarium to promote one-step coupling reaction of 1-halonaphthalene in a small amount of ionic liquid solvent under the catalysis of copper chloride, and the method is not reported in domestic and foreign documents.
Disclosure of Invention
The invention aims to provide a simple method for preparing 1, 1' -binaphthyl by coupling 1-halonaphthalene in an ionic liquid.
The technical scheme of the invention is as follows:
reductive coupling of 1-halonaphthalene to 1, 1' -binaphthyl using metallic samarium at room temperature in the presence of anhydrous cupric salt and [ bmim ] salt (butylmethylimidazolium salt), the general reaction formula of which is shown below:
in the formula, X is preferably Cl, Br, I, SO4(ii) a X' is preferably BF4,PF6,Cl,Br,I。
The specific technical scheme is as follows: stirring 1-chloronaphthalene in ionic liquid [ bmim][BF4](butylmethylimidazolium tetrafluoroborate) and then adding metal samarium powder and anhydrous copper chloride powder in sequence. Wherein the dosage of the ionic liquid isThe mass ratio of the 1-chloronaphthalene is 2-20 times; the dosage of samarium powder is 0.5 to 5 times of the molar ratio of the dosage of 1-chloronaphthalene; the molar ratio of the anhydrous copper chloride to the samarium powder is 0.05-0.5; the reaction system is carried out under anhydrous conditions.
Stirring at room temperature until the reaction is complete. And recovering the ionic liquid from the obtained reaction mixed liquid, and after the residue is subjected to post-treatment, separating by using a chromatographic column to obtain a pure product of the 1, 1' -binaphthyl with the yield of 70-98%.
The invention has the advantages and positive effects that:
the synthetic route is simple and efficient, 1' -binaphthyl can be obtained by only one-step reaction, the operation steps are few, no intermediate is required to be separated, the post-treatment process is simple, the product is easy to separate, and the operation requirement is greatly simplified; the reaction condition of the invention is easy to realize, the conditions of low temperature, high temperature, illumination, pressure, strong acid and strong alkali and the like are not needed, and the cupric salt with low cost is used as the catalyst, thereby avoiding the special requirements of biological catalysis, noble metal catalysis and the like; the reason why the cupric salt can obtain good coupling effect as the catalyst is probably because the cupric salt has better solubility in the ionic liquid [ bmim ] Cl (chlorobutyl methyl imidazole), and compared with the reagents such as cuprous iodide and the like, the cupric chloride has stable property and low price, avoids using iodine which is relatively expensive and has larger molecular weight, and has good atom economy; the samarium used in the invention has excellent reactivity, so that p-chlorophenol is successfully reduced and coupled into 1, 1' -binaphthyl, and in contrast, metal magnesium, zinc and the like are difficult to realize the conversion under similar conditions, and because samarium is a rare earth metal, the rare earth resource in China accounts for more than 90 percent of the world, the effective development and utilization of the rare earth metal have great significance to China; the p-chlorophenol used in the invention has low cost but is relatively inert in halogen phenol, and the preparation of binaphthyl by coupling reaction is difficult, or the yield is low or the reaction conditions are complex, so the invention has obvious technical progress on simplifying the process and reducing the cost; the ionic liquid used in the invention is a novel green solvent, can be fully recycled and reused, and further reduces the reaction cost, and the dosage of the ionic liquid is far less than that of a common organic solvent and is about 1/10, so that the process is simplified, and the concentration of a reaction system is improved, thereby enhancing the reaction effect.
Detailed Description
The following synthetic examples serve to further illustrate the invention, but are not meant to limit the invention.
Example 1
3g of freshly prepared samarium metal powder and 0.26g of anhydrous copper chloride were sequentially added to a dry reaction vessel and magnetically stirred. Then 4.1g of 1-chloronaphthalene, 10mL of butyl methyl imidazole tetrafluoroborate previously dehydrated and dried, were added in that order. The reaction is carried out at room temperature, the color of the reaction mixed solution is darkened within 5 hours, and the reaction is continued for 12 hours. Extracting the reaction liquid with ethyl acetate, and performing post-treatment to obtain a crude product of 1, 1' -binaphthyl. Then further column chromatography and purification by recrystallization gave 1, 1' -binaphthyl in 92% yield.
White solid, melting point 142-144 ℃.1HNMR(500MHz,CDCl3)δppm 7.24-7.31(1H,m),7.39(1H,d,J3(H)＝8.2Hz),7.42-7.52(2H,m),7.58(1H,t,J3(H)＝7.6Hz),7.91-7.98(2H,m),13C NMR(62.5MHz,CDCl3):125.5,125.9,126.1,126.7,127.9,128.0,128.3,133.0,133.6,138.6.
Adding dichloromethane into the residual liquid after ethyl acetate extraction, stirring, standing, transferring, combining, evaporating and recovering the solvent to obtain the recovered ionic liquid.
Example 2
1, 1' -binaphthyl was obtained in 87% yield by the method of example 1 using butylmethylimidazole chloride instead of tetrafluoroborate.
Example 3
By the method of example 1, [ bmim][BF4]After 5 times of repeated use, the conversion of the substrate can still be well realized, and the 1, 1' -binaphthyl is obtained with the yield of 82%.
Claims (5)
1. A method for synthesizing 1,1 '-binaphthyl is characterized in that under the catalysis of cupric salt, samarium is used in ionic liquid to promote one-step reduction coupling reaction of 1-halonaphthalene to prepare the 1, 1' -binaphthyl, and the preparation process comprises the following steps:
mixing and dissolving 1-halonaphthalene in ionic liquid under stirring, and then sequentially adding metal samarium powder and anhydrous cupric salt powder; the reaction system is carried out under the anhydrous condition, and is stirred at room temperature until the reaction is complete; recovering ionic liquid from the obtained reaction mixed liquid, and performing post-treatment on residues and column chromatography to obtain a pure 1, 1' -binaphthyl product;
the 1-halonaphthalene used is 1-chloronaphthalene; the ionic liquid is butyl methyl imidazole salt [ bmim ] X; the cupric salt is one or more of cupric chloride, cupric bromide, cupric iodide and cupric sulfate.
2. The method for synthesizing 1, 1' -binaphthyl according to claim 1, wherein the amount of the ionic liquid used is 2-20 times the amount of the 1-halonaphthalene; the dosage of the samarium powder is 0.5 to 5 times of the molar ratio of the dosage of the 1-halonaphthalene; the molar ratio of the anhydrous copper chloride to the samarium powder is 0.05-0.5.
3. The method of claim 1, 1' -binaphthyl synthesis using butylmethylimidazolium salt [ bmim ] X is one or more of [ bmim ] BF 4, [ bmim ] PF 6, [ bmim ] Cl, [ bmim ] Br, and [ bmim ] I.
4. The method of claim 1, 1' -binaphthyl synthesis using samarium as reductive coupling metal.
5. The method for synthesizing 1, 1' -binaphthyl according to claim 1, wherein the reaction process is a one-pot one-step reaction, the reaction temperature is room temperature, and the reaction solvent can be recovered.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265147A (en) * | 2008-05-08 | 2008-09-17 | 上海交通大学 | Method for preparing biaryl |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265147A (en) * | 2008-05-08 | 2008-09-17 | 上海交通大学 | Method for preparing biaryl |
Non-Patent Citations (5)
| Title |
|---|
| "A modified Cu(0)-Cu(I)-mediated Caryl-Caryl Ullmann coupling for the synthesis of biaryls";K. Yasamut et al.，;《Tetrahedron》;20160727;第72卷;第5994-6000页 * |
| "Coupling reaction of aryl halides promoted by NiCl2/PPh3 /Sm0";X.L. Zheng et al.，;《J. Chem. Research》;20021101;第11卷;第562-563页 * |
| "离子液体制备及其化工应用进展";蒋平平等;《化工进展》;20141231;第33卷(第11期);第2815-2828页 * |
| "联萘二甲酸的合成与拆分";申永存等;《武汉理工大学学报（交通科学与工程版）》;20120831;第36卷(第4期);第833-835，839页 * |
| "过渡金属催化下金属钐介入的偶联反应研究";肖淑焕;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20180115(第1期);第B014-69页 * |
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Inventor after: Qi Yan Inventor after: Song Bin Inventor after: Liu Yongjun Inventor after: Liu Shufeng Inventor before: Liu Yongjun Inventor before: Liu Shufeng Inventor before: Song Bin Inventor before: Qi Yan |
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Effective date of registration: 20240812 Address after: 256100 Yiyuan Economic Development Zone, Zibo City, Shandong Province Patentee after: SHANDONG XINQUAN PHARMACEUTICAL Co.,Ltd. Country or region after: China Address before: No. 53, Zhengzhou Road, North District, Qingdao, Shandong Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY Country or region before: China |