CN1686979A - Cross couple method for synthesizing compound of liquid crystal by 2-2 phenyl palladium phosphine ethylamine catalysis - Google Patents
Cross couple method for synthesizing compound of liquid crystal by 2-2 phenyl palladium phosphine ethylamine catalysis Download PDFInfo
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- CN1686979A CN1686979A CNA2005100461051A CN200510046105A CN1686979A CN 1686979 A CN1686979 A CN 1686979A CN A2005100461051 A CNA2005100461051 A CN A2005100461051A CN 200510046105 A CN200510046105 A CN 200510046105A CN 1686979 A CN1686979 A CN 1686979A
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Abstract
The present invention belongs to the field of fine chemical and material chemical technology, and provides a preparation method of catalytic cross-coupling reaction catalyst and technique for implementing catalytic reaction. The described catalyst is di-diphenylphosphinethamine palladium type complex. Its preparation method is simple and convenient, its activity is high and selectivity is good, it is stable in air. Said cross-coupling reaction is characterized by that under the condition of normal temperature, normal pressure and basicity the di-diphenylphosphinethamine palladium type complex can be used to catalyze 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 catalysis has the advantages of mild reaction conditions, good selectivity and the like, 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.
Hirakawa, M.I.M. et al report on a product of (η)5-(CH3)5Cp)RuCI(COD)/Ph2PCH2CH2NH2The catalyst system composed of KOH catalyzes the hydrogenation reaction of aromatic ketone and terminal epoxy compound in isopropanol solution, and has mild reaction condition and good selectivity. [ Hirakawa, M.I.M., Osaku, A., Ikariya, T., Organometallics, 20(2001)379-]。
Ito, M. et al utilization (η)5-(CH3)5CP)RuCl(COD)/Ph2PCH2CH2NH2/KOButThe system successfully realizes the reversible hydrogen transfer between the secondary alcohol and the ketone, and leads the chiral secondary alcohol to be rapidly racemized. [ Ito, M., Osaku, A., Kitahara, S., Hirakawa, M., Ikariya, T., Tetrahedron Lett., 44(40),2003，7521-7523]。
portnoy, M. et al synthesized Ph supported on high polymer2PCH2CH2NH2Type ligand of Pd (OAc)2Coordination was performed in 90% yield for Heck reaction of iodobenzene and bromobenzene. [ Mansour, A., Portnoy, M., Tetrahedron Lett., 44(10)], 2003, 2195-]。
Habtemariam, A. and the like synthesize a series of Pt (II) and Pd (II) complexes of a bis-diphenylphosphinoethylamine type, and the complexes have catalytic ring-closing and ring-opening effects and also show good anticancer activity. [ Habtemariaam, A., Watchman, B., Potter, B.S., Palmer, R., Parsons, S., Parkin, A., Sadler, P.S., J.chem.Soc., Dalton trains, 2001, 1306-
Under argonUnder protection, [ RuCI2(COD)]NAnd Ph2PCH2CH2NH2Reaction in NaOH isopropanol solution to obtain [ RuHCI (Ph)2PCH2CH2NH2)2]The complex is used as catalyst for acetophenone hydrogenation, and the conversion rate is as high as 100%. [ WO 2002022526 Valentin, R., Rene, C., Raphaeel, C., Haro1d, R., Kamaluddin, A., R., Eric, B., Hubert, M., 21, Mar 2002]
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, Ph2PCH2CH2NH2The dichloromethane solution of (3) was added dropwise with Na2PdCl4Is stirred for 14 hours to obtain a yellow precipitate, see reaction (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 cross-coupling reaction is catalyzed at room temperature or slightly higher reaction temperature, normal pressure and alkaline condition, the reaction condition is mild, and the selectivity is good.
3. The reaction product can be purified by simple 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. Thewhole 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.
At room temperature, add 1mmol of Na2PdCl4Dissolved in 10ml dichloromethane; 2mmol Ph was added to a constant pressure dropping funnel2PCH2CH2NH2Solution in 5ml dichloromethane. Dropping the solution into Na2PdCl4In the solution, stirring for 14 hours to generate yellow precipitate, and performing filter pressing and vacuum drying to obtain the product with the yield of 95 percent.
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 were placed 2ml of tetrahydrofuran, 1.0mmol of an aromatic bromide, 1.5mmol of arylboronic acid, 3.0mmol of an aqueous solution of potassium fluoride and 0.01mmol of a catalyst in this order. Stir at room temperature for a set time. Adding 5ml water, extracting the mixture with diethyl ether or ethyl acetate or n-hexane, washing with saturated NaCl solution and water, and removing anhydrous Mg2SO4Drying, filtering, evaporating the solvent to dryness to obtain a crude product, and purifying by column chromatography with a developing agent of n-hexane and ethyl acetate of 7: 1 to obtain a purified product. The results are shown in Table 1
TABLE 1 cis-PdCI2(Ph2PCH2CH2NH2)2Catalytic cross-coupling synthesis of biphenyl compound
Note: isolated yields are shown in the table.
Example 3: liquid crystal compound for synthesizing biphenyl TFT-LCD
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.
In a two-necked flask were placed 20ml of tetrahydrofuran, 5.0mmol of an aromatic bromide, 7.5mmol of an aromatic boric acid, 15mmol of an aqueous potassium fluoride solution and 0.05mmol of a catalyst in this order. Stirring at room temperature for a set time, adding 20ml water, 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 cis-Pd (Ph)2PCH2CH2NH2)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-catalyzed cross-coupling of bis-diphenylphosphinoethylamine is characterized by comprising the following steps: the palladium bis-diphenylphosphinoethylamine complex catalyzes the cross-coupling reaction between aromatic bromide and 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-catalyzed cross-coupling of bis-diphenylphosphinoethylamine according to claim 1, wherein the method comprises the following steps: the cross-coupling reaction is carried out at room temperature, normal pressure and under the alkaline condition; after the reaction, extracting by ethyl ether or ethyl acetate or n-hexane, evaporating the solvent to dryness to obtain a crude product, and separating by a column chromatography to obtain a pure product.
3. The method for synthesizing the liquid crystal compound by palladium-catalyzed cross-coupling of bis-diphenylphosphinoethylamine according to claim 1, wherein the method comprises the following steps: 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-catalyzed cross-coupling of bis-diphenylphosphinoethylamine according to claim 1, wherein the method comprises the following steps: 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 an R1 group, R1 is hydrogen, straight-chain alkyl with 1-12 carbons, cyclohexane and derivatives thereof, phenyl and derivatives thereof, alkoxy, carbonyl and other halogens.
5. The method for synthesizing the liquid crystal compound by palladium-catalyzed cross-coupling of bis-diphenylphosphinoethylamine according to claim 1, wherein the method comprises the following steps: 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-catalyzed cross-coupling of bis-diphenylphosphinoethylamine according to claim 1, wherein the method comprises the following steps: the catalyst is a palladium type diphenyl phosphine ethylamine complex, and is characterized in that:
(1) the ligand of palladium diphenylphosphinoethylamine catalyst is Ph2P(CH2)nNH2，n＝2-3；
(2) The complex is prepared from 1 mol of Na2PdCl4A yellow solid, PdCl, obtained by reaction with 2 moles of a diphenylphosphinoethylamine type ligand in dichloromethane at room temperature2(Ph2PCH2CH2NH2)2。
7. The method for synthesizing the liquid crystal compound by palladium-catalyzed cross-coupling of bis-diphenylphosphinoethylamine according to claim 1, wherein the method comprises the following steps: the alkali is potassium fluoride, potassium phosphate, potassium carbonate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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