CN105152896B - Method for preparing 1, 4-diphenyl-2-benzophenone - Google Patents
Method for preparing 1, 4-diphenyl-2-benzophenone Download PDFInfo
- Publication number
- CN105152896B CN105152896B CN201510541681.7A CN201510541681A CN105152896B CN 105152896 B CN105152896 B CN 105152896B CN 201510541681 A CN201510541681 A CN 201510541681A CN 105152896 B CN105152896 B CN 105152896B
- Authority
- CN
- China
- Prior art keywords
- diphenyl
- formula
- isosorbide
- nitrae
- butene
- 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
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000012965 benzophenone Substances 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims 3
- 239000000376 reactant Substances 0.000 claims 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- ZBVQEUUTPTVMHY-UHFFFAOYSA-N phenyl-(2-phenylphenyl)methanone Chemical class C=1C=CC=C(C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 ZBVQEUUTPTVMHY-UHFFFAOYSA-N 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- NNSUABWOUMCGLN-UHFFFAOYSA-N (2,5-diphenylphenyl)-phenylmethanone Chemical compound C=1C(C=2C=CC=CC=2)=CC=C(C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 NNSUABWOUMCGLN-UHFFFAOYSA-N 0.000 description 6
- GBUFRJCGZJNUSB-JXMROGBWSA-N (e)-1,4-diphenylbut-3-en-1-one Chemical compound C=1C=CC=CC=1C(=O)C\C=C\C1=CC=CC=C1 GBUFRJCGZJNUSB-JXMROGBWSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical class O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- -1 1,4-diphenyl-2-benzoylbenzene compound Chemical class 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000004210 ether based solvent Chemical class 0.000 description 1
- 230000001506 immunosuppresive effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000014508 negative regulation of coagulation Effects 0.000 description 1
- 230000000324 neuroprotective effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- JLUBUPKHHQVJFE-UHFFFAOYSA-N pent-4-en-2-ynal Chemical class C=CC#CC=O JLUBUPKHHQVJFE-UHFFFAOYSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
(一)技术领域(1) Technical field
本发明涉及一种1，4-二苯基-2-苯甲酰基苯的制备方法。The invention relates to a preparation method of 1,4-diphenyl-2-benzoylbenzene.
(二)背景技术(2) Background technology
含有三联苯结构的化合物具有免疫抑制,抗氧化,神经保护活性以及抗血栓和抗凝血活性等多种生物活性；同时，在液晶材料方面有着广泛应用。其中，1，4-二苯基-2-苯甲酰基苯是重要的有机合成中间体，目前有关该化合物主要是通过二苯基取代的戊烯炔醛与苯乙醛的分子间的[4+2]环合反应制备，但该方法存在使用价格较贵的金属催化剂及原料不宜得等缺点。因此，开发该化合物新的合成方法并研究其抗肿瘤的应用具有重要的理论意义和实际应用价值。Compounds containing terphenyl structure have various biological activities such as immunosuppressive, antioxidative, neuroprotective, antithrombotic and anticoagulant activities; at the same time, they are widely used in liquid crystal materials. Wherein, 1,4-diphenyl-2-benzoylbenzene is an important organic synthesis intermediate, and the present compound is mainly through the intermolecular interaction between diphenyl substituted pentenynal and phenylacetaldehyde [4 +2] Preparation by cyclization reaction, but this method has the disadvantages of using expensive metal catalysts and unsuitable raw materials. Therefore, developing a new synthesis method of this compound and studying its anti-tumor application has important theoretical significance and practical application value.
(三)发明内容(3) Contents of the invention
本发明采用如下技术方案：The present invention adopts following technical scheme:
本发明提供了一种式(II)所示的1，4-二苯基-2-苯甲酰基苯的制备方法，所述方法为：The present invention provides a kind of preparation method of 1,4-diphenyl-2-benzoylbenzene shown in formula (II), described method is:
将式(I)所示的(E)-1，4-二苯基-3-丁烯-1-酮在惰性有机溶剂中，在碱性物质作用下，在70～130℃温度下搅拌反应2～25小时，反应结束后，反应液后处理制得式(II)所示的1，4-二苯基-2-苯甲酰基苯；(E)-1,4-diphenyl-3-buten-1-one represented by formula (I) is stirred and reacted at a temperature of 70-130°C in an inert organic solvent under the action of an alkaline substance After 2 to 25 hours, after the reaction, the reaction solution is post-treated to obtain 1,4-diphenyl-2-benzoylbenzene represented by formula (II);
所述式(I)所示的(E)-1，4-二苯基-3-丁烯-1-酮与碱性物质的物质的量之比为1：0.4～2.0，优选为1：0.8～1.0。The ratio of the amount of (E)-1,4-diphenyl-3-buten-1-one represented by the formula (I) to the basic substance is 1:0.4-2.0, preferably 1: 0.8～1.0.
本发明所述的惰性有机溶剂选自取代苯类或醚类溶剂，优选为下列之一：甲苯或二氧六环。The inert organic solvent in the present invention is selected from substituted benzene or ether solvents, preferably one of the following: toluene or dioxane.
所述的惰性有机溶剂的体积用量以式(I)所示的(E)-1，4-二苯基-3-丁烯-1-酮的质量计为5～20mL/g。The volumetric usage of the inert organic solvent is 5-20 mL/g based on the mass of (E)-1,4-diphenyl-3-buten-1-one represented by formula (I).
所述的碱性物质为无机碱或有机碱；优选为碳酸铯或叔丁醇钾。The alkaline substance is an inorganic base or an organic base; preferably cesium carbonate or potassium tert-butoxide.
本发明的反应温度优选90～130℃。The reaction temperature in the present invention is preferably 90 to 130°C.
反应时间优选10～25小时，更优选13～20小时。The reaction time is preferably 10 to 25 hours, more preferably 13 to 20 hours.
所述反应液后处理方法为：反应结束后，反应液加水，用二氯甲烷萃取，合并有机层，浓缩除去溶剂后剩余物经柱层析分离，以石油醚、二氯甲烷体积比4:1的混合溶剂为洗脱剂，收集含有目标化合物的洗脱液，洗脱液减压蒸馏，干燥得到式(II)所示的1，4-二苯基-2-苯甲酰基苯。The post-treatment method of the reaction solution is: after the reaction, add water to the reaction solution, extract with dichloromethane, combine the organic layers, concentrate and remove the solvent, and the residue is separated by column chromatography, and the volume ratio of sherwood oil and dichloromethane is 4: The mixed solvent of 1 is the eluent, the eluate containing the target compound is collected, the eluate is distilled under reduced pressure, and dried to obtain 1,4-diphenyl-2-benzoylbenzene represented by formula (II).
更具体的，优选本发明方法按以下步骤进行：More specifically, preferred method of the present invention carries out according to the following steps:
将式(I)所示的(E)-1，4-二苯基-3-丁烯-1-酮在惰性有机溶剂中，在碱性物质作用下，在90～130℃温度下搅拌反应10～25小时，反应结束后，反应液加水，用二氯甲烷萃取，合并有机层，浓缩除去溶剂后剩余物经柱层析分离，以石油醚、二氯甲烷体积比4:1的混合溶剂为洗脱剂，收集含有目标化合物的洗脱液，洗脱液减压蒸馏，干燥得到式(II)所示的1，4-二苯基-2-苯甲酰基苯；所述的碱性物质为碳酸铯或叔丁醇钾；所述的惰性有机溶剂为下列之一：甲苯或二氧六环；所述式(I)所示的(E)-1，4-二苯基-3-丁烯-1-酮与碱性物质的物质的量之比为1：0.8～1.0。(E)-1,4-diphenyl-3-buten-1-one represented by formula (I) is stirred and reacted at a temperature of 90-130°C in an inert organic solvent under the action of an alkaline substance After 10 to 25 hours, after the reaction is over, add water to the reaction solution, extract with dichloromethane, combine the organic layers, concentrate and remove the solvent, and the residue is separated by column chromatography. As an eluent, collect the eluent containing the target compound, distill the eluent under reduced pressure, and dry to obtain 1,4-diphenyl-2-benzoylbenzene shown in formula (II); the basic The substance is cesium carbonate or potassium tert-butoxide; the inert organic solvent is one of the following: toluene or dioxane; (E)-1,4-diphenyl-3 shown in the formula (I) -Buten-1-one: The ratio of the amount of the basic substance is 1:0.8-1.0.
本发明开发了1，4-二苯基-2-苯甲酰基苯化合物的新的制备方法，该工艺反应条件温和，操作方便，成本低，不需要使用价格昂贵的金属催化剂，催化剂来源易得，有着广泛的工业应用前景。The present invention develops a new preparation method of 1,4-diphenyl-2-benzoylbenzene compound, the process has mild reaction conditions, convenient operation, low cost, no need to use expensive metal catalysts, and the source of catalysts is easy to obtain , has broad industrial application prospects.
(四)具体实施方式(4) Specific implementation methods
下面将通过实施例对本发明作进一步的说明，但本发明的保护范围不限于此。The present invention will be further described below through examples, but the protection scope of the present invention is not limited thereto.
实施例1：化合物(II)的制备Embodiment 1: the preparation of compound (II)
在反应容器中加入(E)-1，4-二苯基-3-丁烯-1-酮(I)(0.2001g，0.9002mmol)，碳酸铯(0.2796g，0.7967mmol)，在1，4－二氧六环(2mL)中混合，90℃油浴中搅拌反应13小时；反应结束后，加水，用二氯甲烷萃取，合并有机层，浓缩后剩余物用柱层析分离(洗脱剂为石油醚：二氯甲烷:＝4:1，V:V)，收集Rf值0.3～0.35的洗脱液，减压蒸馏，干燥得到目标化合物(II)，0.1293g，收率为73％。Add (E)-1,4-diphenyl-3-buten-1-one (I) (0.2001g, 0.9002mmol) and cesium carbonate (0.2796g, 0.7967mmol) in a reaction vessel, and at 1,4 - Mixed with dioxane (2mL), stirred and reacted in an oil bath at 90°C for 13 hours; after the reaction was completed, water was added, extracted with dichloromethane, the organic layers were combined, and the residue was separated by column chromatography after concentration (eluent Petroleum ether: dichloromethane:=4:1, V:V), collect the eluent with R f value of 0.3～0.35, distill under reduced pressure, dry to obtain target compound (II), 0.1293g, yield is 73% .
1H NMR(500MHz,CDCl3)δ7.83(dd,J＝8.0,2.0Hz,1H),7.76(d,J＝2.0Hz,1H),7.73-7.71(m,2H),7.69-7.67(m,2H),7.59(d,J＝8.0Hz,1H),7.50-7.47(m,2H),7.46-7.42(m,1H),7.41-7.39(m,1H),7.33-7.29(m,4H),7.26-7.22(m,2H),7.20-7.17(m,1H) 1 H NMR (500MHz, CDCl 3 ) δ7.83 (dd, J = 8.0, 2.0Hz, 1H), 7.76 (d, J = 2.0Hz, 1H), 7.73-7.71 (m, 2H), 7.69-7.67 ( m,2H),7.59(d,J＝8.0Hz,1H),7.50-7.47(m,2H),7.46-7.42(m,1H),7.41-7.39(m,1H),7.33-7.29(m, 4H),7.26-7.22(m,2H),7.20-7.17(m,1H)
实施例2：Example 2:
将碳酸铯改为叔丁醇钾(0.0831g，0.7405mmol)，其他操作同实施例1，得到目标化合物(II)，0.1151g，收率为65％。The cesium carbonate was changed to potassium tert-butoxide (0.0831g, 0.7405mmol), and other operations were the same as in Example 1 to obtain the target compound (II), 0.1151g, with a yield of 65%.
实施例3：Example 3:
将溶剂1，4－二氧六环改为甲苯，其他操作同实施例1，得到目标化合物(II)，0.1062g，收率为60％。The solvent 1,4-dioxane was changed to toluene, and other operations were the same as in Example 1 to obtain the target compound (II), 0.1062 g, with a yield of 60%.
实施例4：Example 4:
将反应温度降低到70℃，其他操作同实施例1，得到目标化合物(II)，0.0318g，收率为18％。The reaction temperature was lowered to 70° C., and the other operations were the same as in Example 1 to obtain the target compound (II), 0.0318 g, with a yield of 18%.
实施例5：Example 5:
将反应温度升高到130℃，其他操作同实施例1，得到目标化合物(II)，0.1169g，收率为66％。The reaction temperature was raised to 130° C., and other operations were the same as in Example 1 to obtain the target compound (II), 0.1169 g, with a yield of 66%.
实施例6：Embodiment 6:
将碳酸铯的量改为0.1206g，0.3702mmol，其他操作同实施例1，得到目标化合物(II)，0.0867g，收率为49％。The amount of cesium carbonate was changed to 0.1206g, 0.3702mmol, and other operations were the same as in Example 1 to obtain the target compound (II), 0.0867g, with a yield of 49%.
实施例7：Embodiment 7:
将碳酸铯的量改为0.4824g，1.4808mmol，其他操作同实施例1，得到目标化合物(II)，0.0921g，收率为52％。The amount of cesium carbonate was changed to 0.4824g, 1.4808mmol, and other operations were the same as in Example 1 to obtain the target compound (II), 0.0921g, with a yield of 52%.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510541681.7A CN105152896B (en) | 2015-08-28 | 2015-08-28 | Method for preparing 1, 4-diphenyl-2-benzophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510541681.7A CN105152896B (en) | 2015-08-28 | 2015-08-28 | Method for preparing 1, 4-diphenyl-2-benzophenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105152896A CN105152896A (en) | 2015-12-16 |
| CN105152896B true CN105152896B (en) | 2017-04-12 |
Family
ID=54794006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510541681.7A Active CN105152896B (en) | 2015-08-28 | 2015-08-28 | Method for preparing 1, 4-diphenyl-2-benzophenone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105152896B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126934A (en) * | 2011-01-13 | 2011-07-20 | 山东大学 | Paraterphenyl derivative and application thereof to preparation of antitumor medicaments |
-
2015
- 2015-08-28 CN CN201510541681.7A patent/CN105152896B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126934A (en) * | 2011-01-13 | 2011-07-20 | 山东大学 | Paraterphenyl derivative and application thereof to preparation of antitumor medicaments |
Non-Patent Citations (2)
| Title |
|---|
| Lewis Acid-Catalyzed [4 + 2] Benzannulation between Enynal Units and Enols or Enol Ethers: Novel Synthetic Tools for Polysubstituted Aromatic Compounds Including Indole and Benzofuran Derivatives;Naoki Asao et al.;《J. Org. Chem.》;20060608;第71卷;5249-5253 * |
| 三联苯类化合物合成方法的研究进展;石巍等;《有机化学》;20150228;第35卷(第2期);第362－372页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105152896A (en) | 2015-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106632214B (en) | A kind of synthetic method of cannabinoid compound | |
| CN110818743A (en) | Preparation method and application of a cyclometallic platinum complex with aggregation-induced luminescence properties | |
| JP2019214584A (en) | Halogenated compound and production method of fullerene derivative | |
| Micheletti et al. | New electron-donor and-acceptor architectures from benzofurazans and sym-triaminobenzenes: Intermediates, products and an unusual nitro group shift | |
| JP2023535329A (en) | Method for producing deuterated aromatic compounds and deuterated reaction composition | |
| CN107163028A (en) | A kind of benzamides Hedgehog inhibitor and its preparation method and application | |
| CN104151243A (en) | Method for preparing multi-substituted acridine derivative with high efficiency | |
| CN105152896B (en) | Method for preparing 1, 4-diphenyl-2-benzophenone | |
| JP5963140B2 (en) | Asymmetric dehydration condensation agent | |
| CN107827705A (en) | A kind of single arylation method of dichloro benzene-like compounds | |
| CN105175241B (en) | Terphenyls compound and its preparation method and application | |
| CN108689892B (en) | 3-sulfonylation-indanone compound and preparation method thereof | |
| CN107513056A (en) | A kind of synthetic method of the quinolines of the group containing tetrahydrofuran | |
| CN108069835A (en) | A kind of chiral helicene with dinaphthol structure and preparation method thereof | |
| CN104402839B (en) | A kind of (E)-2,4,5-trisubstituted-(1-propenyl)oxazole ring compound and its preparation method | |
| CN104341403B (en) | A kind of 2,5-bis-heterocyclic substituted naphthyl alkane derivatives and preparation method thereof | |
| CN114436918A (en) | Cyclobut-1-enamine compound, preparation method thereof and application thereof in medicines | |
| CN113416162A (en) | Double-chiral binaphthyl O-N-N tridentate ligand and preparation method thereof | |
| CN109096226A (en) | It is the hydrocarbon activation process or acetoxylation of aryl for being oriented to base with 2,1,3- diazosulfide | |
| CN110563701A (en) | N-2-pyrimidine-2-azido-3- (2,2,6, 6-tetramethylpiperidinyloxy) indoline and preparation and application thereof | |
| CN111704630A (en) | 3-Aroyl naphthisoxazole or 3-aroyl anthraisoxazole derivatives and synthesis method thereof | |
| CN109096225A (en) | It is the hydrocarbon activation halogenating reaction method of aryl for being oriented to base with 2,1,3- diazosulfide | |
| CN110862348A (en) | A kind of synthetic method of 6-nitrile phenanthridine compounds | |
| CN115433180B (en) | Polycyclic compound and organic electroluminescent device thereof | |
| CN105153111B (en) | 4- methoxyl groups -3 '-(2- Thenoyls) -4 '-(2- thiophene) biphenyl and its preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201012 Address after: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee after: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. Address before: The city Zhaohui six districts Chao Wang Road Hangzhou City, Zhejiang province 310014 18 Patentee before: ZHEJIANG University OF TECHNOLOGY Effective date of registration: 20201012 Address after: 221300 north side of Qingnian East Road, Yunhe Town, Pizhou City, Xuzhou City, Jiangsu Province Patentee after: Pizhou Runhong Industry Co.,Ltd. Address before: 510000 unit 2414-2416, building, No. five, No. 371, Tianhe District, Guangdong, China Patentee before: GUANGDONG GAOHANG INTELLECTUAL PROPERTY OPERATION Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240904 Address after: 221399 North of Jiefang East Road, Pizhou City, Xuzhou City, Jiangsu Province Patentee after: Xuzhou Jiasheng Real Estate Co.,Ltd. Country or region after: China Address before: 221300 north side of Qingnian East Road, Yunhe Town, Pizhou City, Xuzhou City, Jiangsu Province Patentee before: Pizhou Runhong Industry Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |