CN1686972A - Cross couple method for synthesizing compound of liquid crystal from 2-2 phenyl phosphine ethanol through palladium catalysis - Google Patents
Cross couple method for synthesizing compound of liquid crystal from 2-2 phenyl phosphine ethanol through palladium catalysis Download PDFInfo
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- CN1686972A CN1686972A CNA2005100461066A CN200510046106A CN1686972A CN 1686972 A CN1686972 A CN 1686972A CN A2005100461066 A CNA2005100461066 A CN A2005100461066A CN 200510046106 A CN200510046106 A CN 200510046106A CN 1686972 A CN1686972 A CN 1686972A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 title claims description 13
- IGRYVBIEOQPIPA-UHFFFAOYSA-N C1(=CC=CC=C1)P.C(C)O Chemical compound C1(=CC=CC=C1)P.C(C)O IGRYVBIEOQPIPA-UHFFFAOYSA-N 0.000 title 1
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 20
- -1 biphenylyl Chemical class 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004327 boric acid Substances 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 3
- 150000004697 chelate complex Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 150000002431 hydrogen Chemical group 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- DVYOAKFBWYRJRC-UHFFFAOYSA-N C(C)O.C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound C(C)O.C1(=CC=CC=C1)PC1=CC=CC=C1 DVYOAKFBWYRJRC-UHFFFAOYSA-N 0.000 claims 1
- 101150003085 Pdcl gene Proteins 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 150000004768 bromobenzenes Chemical group 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- DVERFJXHCKPMNM-UHFFFAOYSA-N fluorophosphane Chemical compound PF DVERFJXHCKPMNM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention belongs to the field of fire chemical and material chemical technology, and provides a preparation method of cross-coupling reaction catalyst and technique for implementing catalytic reaction. The described catalyst is a di-diphenylphosphinethanol palladium type complex. Its preparation method is simple and convenient, its activity is high, selectivity is good, and it is stable in air. Said catalytic cross-coupling reaction can be implemented in organic solution under the condition of room temperature, normal pressure and basicity, the di-diphenylphosphinethanol palladium type complex can be used for catalyzing cross-coupling reaction between aromatic bromide and aromatic boric acid to produce biphenylyl type compound, in particular liquid crystal compound for biphenylyl type TFT-LCD.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering and material chemistry, and relates to a liquid crystal compound for synthesizing a TFT-LCD (thin film transistor-liquid crystal display), in particular to a green chemical technology for synthesizing the liquid crystal compound by using a coordination catalysis method.
Background
Many biarylenes have liquid crystalline properties and have been used in TFT-LCDs. The biaryl compound prepared by the classical organic synthesis method has long route, low total yield, poor selectivity and serious pollution. The coordination catalytic reaction has mild condition and good selectivity, and provides an important means for greening organic synthesis. The coordination catalysis method is mostly adopted for the green chemical industry accepted by the world at present.
Coupling reactions catalyzed by the zero-valent palladium complex, such as Heck reaction, Suzuki reaction, Stille reaction, Sonogashira reaction, Tsuji-Trost reaction and the like, are effective methods for forming C-C bonds in organic synthesis. Among them, Pd (PPh) was discovered by Suzuki in 19813)4The method for preparing asymmetric diaryl or polyaromatic hydrocarbon by catalyzing the cross coupling of aromatic bromide and aromatic boric acid forms CSP2-CSP2One of the important methods for aromatic bonding.
Phosphonium fluoride ligands, PPh, were first reported by Willis, J.C2CH2C(CF3)2OH and demonstrates that the ligand deprotonates under the action of a base while forming an P, O bidentate chelate complex with the transition metal: m (PPh)2CH2C(CF3)O)2Wherein M ═ Co2+，Ni2+，Pt2+，Pd2+。(Craigd，R.B.，Payne，M.N.，Willis*，C.J.，Inorg.Chem.，1985，24，3680-3687)
Pringle, P.G. et al reported the synthesis of bis-diphenylphosphine palladium ethoxide. 1.86mmol Ph at room temperature2P(CH2)2OH in 5ml CH2Cl2In (2), the solution is added dropwise to 0.89mmol of PdCI2(NCPh)2In 5ml of CH2Cl2The light yellow solution in (1) was stirred for 16 hours. After concentration to 1ml, 5ml of diethyl ether and5ml of petroleum ether (b.p.60-80 ℃ C.) gave tran-PdCI as a yellow solid2(PPh2CH2CH2OH)2The yield was 86%. The yellow solid is dissolved in ethanol solution, solid NaOH is added for deprotonation to obtain brown P, O bidentate chelate complex Pd (Ph)2PCH2CH2O)2。[Platt，A.W.G.，Pringle，P.G.，J.Chem.Soc.Dalton Trans.，1989，1193]
Disclosure of Invention
The invention aims to provide a catalyst and a method for synthesizing a biphenyl type liquid crystal compound for TFT-LCD by catalytic cross-coupling reaction.
The technical scheme of the invention is as follows:
1. catalyst synthesis method
At room temperature, Ph2PCH2CH2OH solution is dropped with Na2PdCl4Stirring the mixture at room temperature for 16 hours in dichloroethane solution to obtain a yellow precipitate tran-PdCI2(PPh2CH2CH2OH)2Dissolving in ethanol solution, adding solid NaOH, and reacting to obtain brown solid Pd (Ph)2PCH2CH2O)2See reaction formula (1).
2. Cross-coupling reaction
The reaction is carried out in an organic solvent at room temperature, see reaction formula (2).
The invention has the advantages that:
1. the catalyst has simple preparation method, high activity, good selectivity and stability in air.
2. The condition of catalyzing the cross-coupling reaction in the organic solvent at room temperature or slightly higher reaction temperature and normal pressure is mild, and the selectivity is good.
3. The reaction product is obtained by simple extraction, and the pure product is obtained by further purification through column chromatography.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the technical solutions.
Example 1: preparation of the catalyst
A ground plug with a crescent piston is arranged on one side opening of the 100ml three-mouth flask and is connected with vacuum/ultra-pure nitrogen. The other side opening is provided with a constant pressure dropping funnel. The flask was fitted with a stirring magnet and then stoppered, and the flask was mounted on a magnetic stirrer. The whole set of the apparatus is evacuated and filled with nitrogen for three times, and the subsequent operation is carried out according to the method for treating sensitive substances in the air.
0.89mmol of Na was addedunder stirring at room temperature2PdCl4Dissolved in 5ml dichloromethane; 1.86 mmolePh2PCH2CH2OH was dissolved in 5ml ethanol. Ph is2PCH2CH2OH solution is dropped with Na2PdCl4Stirring the solution for 16 hours at room temperature, performing filter pressing and vacuum drying to obtain a product tran-PdCI2(PPh2CH2CH2OH)2，The yield was 86%.
The obtained 0.15mmol of tran-PdCi2(PPh2CH2CH2OH)2Dissolving in ethanol, adding 2.5mmol NaOH to gradually turn the solution turbid, evaporating under reduced pressure after 1 hr to remove solvent, adding 5ml water, and press filtering to obtain brown solid Pd (Ph)2PCH2CH2O)2The yield was 21%.
Example 2: synthesis of biphenyl type compounds
A ground plug with a crescent piston is arranged on one side port of the 50ml two-port flask and is connected with vacuum ultra-pure nitrogen. The flask was fitted with a stirring magnet and then stoppered, and the flask was mounted on a magnetic stirrer. The whole set of the apparatus is evacuated and filled with nitrogen for three times, and the subsequent operation is carried out according to the method for treating sensitive substances in the air.
In a two-necked flask was added 2ml of tetrahydrofuran. 1.0mmol of aromatic bromide, 1.5mmol of arylboronic acid, 2ml of 3.0mmol of potassium phosphate aqueous solution and 0.01mmol of catalyst are added in sequence. Stirred at room temperature for a certain period of time. Extracting the reaction mixture with diethyl ether, ethyl acetate or n-hexane, washing the extractive solution with saturated NaCl solution and water, and adding Mg2SO4Drying, filtering and evaporating the solvent. Purifying the obtained crude product by column chromatography, wherein the developing agent is n-hexane and ethyl acetate which are 7: 1, and obtaining the product. The results are shown in Table 1
TABLE 1 Pd (Ph)2PCH2CH2O)2Catalytic cross-coupling synthesis of biphenyl compound
Note: isolated yields are shown in the table.
Example 3:
a ground plug with a crescent piston is arranged on one side port of the 100ml two-port flask and is connected with vacuum/ultra-pure nitrogen. The flask was fitted with a stirring magnet and then stoppered, and the flask was mounted on a magnetic stirrer. The whole set of the apparatus is evacuated and filled with nitrogen for three times, and the subsequent operation is carried out according to the method for treating sensitive substances in the air.
20ml of tetrahydrofuran, 5.0mmol of aromatic bromide, 7.5mmol of aromatic boric acid, 15mmol of potassium phosphate in water and 0.05mmol of catalyst were sequentially added into a two-neck flask. Stir at room temperature for a set time. Extracting the reaction mixture with diethyl ether or ethyl acetate or n-hexane, washing the extract with saturated NaCl solution, water, and Mg2SO4Drying, filtering and evaporating the solvent. Purifying the obtained crude product by column chromatography, wherein the developing agent is n-hexane and ethyl acetate which are 7: 1, and obtaining the product. The results are shown in Table 2
TABLE 2 Pd (Ph)2PCH2CH2O)2Liquid crystal compound for synthesizing TFT-LCD (thin film transistor-liquid crystal display) by catalytic cross-coupling
Note: isolated yields are shown in the table.
Claims (7)
1. A method for synthesizing a liquid crystal compound by palladium bis-diphenylphosphine ethanol catalysis cross-coupling is characterized by comprising the following steps: the bis-diphenylphosphine palladium-ethanol complex catalyzes the cross-coupling reaction between the aromatic bromide and the aromatic boric acid to generate the liquid crystal compound for the biphenyl TFT-LCD.
2. The method for synthesizing the liquid crystal compound by palladium bis-diphenylphosphine ethanolate catalytic cross-coupling according to claim 1, wherein: the cross-coupling reaction is carried out in an organic solvent under the conditions of room temperature, normal pressure and alkalinity; after the reaction, extracting by ethyl ether or ethyl acetate or n-hexane, evaporating the solvent to dryness to obtain a product, and further purifying by column chromatography to obtain a pure product.
3. The method for synthesizing the liquid crystal compound by palladium bis-diphenylphosphine ethanolate catalytic cross-coupling according to claim 1, wherein: the aromatic bromide is the derivative of bromobenzene substituted by R group at ortho-position and para-position, wherein R is hydrogen, straight-chain alkyl of 1-12 carbons, cyclohexane and derivatives thereof, phenyl and derivatives thereof, alkoxy, carbonyl and other halogens.
4. The method for synthesizing the liquid crystal compound by palladium bis-diphenylphosphine ethanolate catalytic cross-coupling according to claim 1, wherein: the aromatic boric acid is a derivative of phenylboronic acid, wherein the ortho-position and the para-position of the phenylboronic acid are substituted by R groups, wherein R is hydrogen, straight-chain alkyl with 1-12 carbons, cyclohexane, phenyl, alkoxy, carbonyl and other halogens.
5. The method for synthesizing the liquid crystal compound by palladium bis-diphenylphosphine ethanolate catalytic cross-coupling according to claim 1, wherein: the biphenyl type liquid crystal compound for TFT-LCD is generated by the reactant through cross coupling reaction.
6. The method for synthesizing the liquid crystal compound by palladium bis-diphenylphosphine ethanolate catalytic cross-coupling according to claim 1, wherein: the catalyst is a bis-diphenylphosphine ethanol palladium complex, which is characterized in that:
(1) the ligand of the palladium bis-diphenylphosphinoethanolate catalyst is Ph2P(CH2)nOH，n＝2-3；
(2) The complex is prepared from 1 mol of Na2PdCl4With 2 mol of diphenylphosphine ethanol type ligand at room temperature,The yellow solid, PdCl, obtained from the reaction in dichloromethane solution2(PPh2CH2CH2OH)2(ii) a It is dissolved in ethanol solution, and is added with powdery NaOH to remove proton to obtain brown P, O bidentate chelate complex Pd2+ square(Ph2PCH2CH2O)2。
7. The method for synthesizing the liquid crystal compound by palladium bis-diphenylphosphine ethanolate catalytic cross-coupling according to claim 1, wherein: the alkali is potassium phosphate, sodium carbonate and triethylamine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100461066A CN1686972A (en) | 2005-03-22 | 2005-03-22 | Cross couple method for synthesizing compound of liquid crystal from 2-2 phenyl phosphine ethanol through palladium catalysis |
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2005100461066A CN1686972A (en) | 2005-03-22 | 2005-03-22 | Cross couple method for synthesizing compound of liquid crystal from 2-2 phenyl phosphine ethanol through palladium catalysis |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966608B (en) * | 2006-11-20 | 2010-09-01 | 烟台万润精细化工股份有限公司 | Method for preparing biphenyl-like monomer liquid crystal using cross-coupling reaction |
| US8415504B2 (en) | 2010-11-24 | 2013-04-09 | Industrial Technology Research Institute | Catalyst carrier, catalyst thereon and C-C coupling method use the same |
| CN104744208A (en) * | 2015-02-04 | 2015-07-01 | 宜春学院 | Biphenyl-type fluorine-containing liquid crystal monomer as well as catalyst and preparation method thereof |
| CN106967443A (en) * | 2017-04-28 | 2017-07-21 | 烟台德润液晶材料有限公司 | The preparation method of alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds |
| EP4317201A4 (en) * | 2021-03-31 | 2024-09-18 | Mitsubishi Chem Corp | Polymerization catalyst for olefin-based polymer |
-
2005
- 2005-03-22 CN CNA2005100461066A patent/CN1686972A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966608B (en) * | 2006-11-20 | 2010-09-01 | 烟台万润精细化工股份有限公司 | Method for preparing biphenyl-like monomer liquid crystal using cross-coupling reaction |
| US8415504B2 (en) | 2010-11-24 | 2013-04-09 | Industrial Technology Research Institute | Catalyst carrier, catalyst thereon and C-C coupling method use the same |
| CN104744208A (en) * | 2015-02-04 | 2015-07-01 | 宜春学院 | Biphenyl-type fluorine-containing liquid crystal monomer as well as catalyst and preparation method thereof |
| CN106967443A (en) * | 2017-04-28 | 2017-07-21 | 烟台德润液晶材料有限公司 | The preparation method of alkyl cyclohexyl biphenyl nitrile liquid-crystal compounds |
| EP4317201A4 (en) * | 2021-03-31 | 2024-09-18 | Mitsubishi Chem Corp | Polymerization catalyst for olefin-based polymer |
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