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CN110746597B - Ruthenium-based catalyst Ru-PPh2CO, preparation method and application - Google Patents

Ruthenium-based catalyst Ru-PPh2CO, preparation method and application Download PDF

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CN110746597B
CN110746597B CN201910993208.0A CN201910993208A CN110746597B CN 110746597 B CN110746597 B CN 110746597B CN 201910993208 A CN201910993208 A CN 201910993208A CN 110746597 B CN110746597 B CN 110746597B
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熊兴泉
韩骞
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Huaqiao University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40Polyamides containing oxygen in the form of ether groups
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    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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Abstract

The invention discloses a ruthenium-based catalyst Ru-PPh2CO, preparation method and application thereof, wherein the application is based on ruthenium-based catalyst Ru-PPh2And the polyamide is prepared by the amidation polymerization reaction between dimethyl dicarboxylate and alkyl diamine under the catalysis of CO. The ruthenium-based catalyst Ru-PPh prepared by the invention2CO, the high-efficiency synthesis of polyamide is realized under the heating condition. Research results show that the reaction temperature is 120 ℃, the catalyst dosage is 1 mol%, anisole is solvent, the reaction time is 48 hours, the optimal reaction condition of the polymerization system is provided, the yield is up to 85%, and the molecular weight of the obtained polyamide is 8000-17000. In a substrate development experiment, a series of dicarboxylic acid dimethyl esters with different structures react with a series of alkyl diamines to synthesize corresponding polyamide, and the result shows that the yield of most products is over 80 percent and the product has good substrate selectivity.

Description

Ruthenium-based catalyst Ru-PPh2CO, preparation method and application
Technical Field
The invention belongs to the technical field of organic catalysis and polymer synthesis, and particularly relates to a ruthenium-based catalyst Ru-PPh2CO, a preparation method and application.
Background
Natural and synthetic polyamides play an important role in the biological and materials fields. Natural polyamide compounds include proteins and polypeptides, which are substances that are essential components of life. Synthetic polyamide is an important conventional engineering plastic and has many excellent properties, such as good mechanical properties, good heat resistance, good electrical insulation, self-lubricity, and the like. Thus, polyamides have many applications in plastics, fibers and coatings. Therefore, the synthesis method of polyamide with high efficiency, high speed and stability has been a hot problem in industrial production and scientific research.
Up to now, there are many synthetic methods for polyamides, the most traditional and industrial synthetic method being high temperature melt polymerization using dicarboxylic acids (and dicarboxylic acid derivatives) and diamines. However, the disadvantages of this process are evident in the severe reaction conditions (high reaction temperature or high reaction vacuum requirement) and the production of stoichiometrically equivalent amounts of harmful by-products (hydrogen halides) during the reaction. With the progress of polyamide research, chemists have also developed various methods for synthesizing polyamides by constructing amide bonds using other functional groups, including ring-opening polymerization of caprolactam, aminolysis polymerization of diesters of specific structures, and polycondensation of diisocyanates and dicarboxylic acids or diamines.
Although the reported methods can be used to prepare polyamide with high yield, there still exist many limitations, such as harsh reaction conditions, complicated reaction operation, long reaction time, and environmental friendliness.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a ruthenium-based catalyst Ru-PPh2CO, a preparation method and application, and solves the problems in the background technology.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provides a ruthenium-based catalyst Ru-PPh2CO, having the formula:
Figure BDA0002238938400000021
the second technical scheme adopted by the invention for solving the technical problems is as follows: provides a ruthenium-based catalyst Ru-PPh2The preparation method of CO comprises the following synthetic route:
Figure BDA0002238938400000022
the preparation method specifically comprises the following steps:
1) bis [ 2-diphenylphosphinoethyl)]Mixing amine hydrochloride, toluene and 10% NaOH solution, stirring at 30-40 deg.C under nitrogen atmosphere for 20-30min, separating organic phase, and adding MgSO4Drying;
2) the organic phase dried in step 1) and RuHCl (CO) (PPh)3)3Mixing, heating to 110-130 ℃ in a nitrogen atmosphere, stirring for 2h, cooling to 30-40 ℃, and stirring for 1-2 h;
3) filtering, separating and precipitating, washing with toluene for three times, and drying in a vacuum drying oven at 40-50 deg.C overnight to obtain pale yellow solid which is ruthenium-based catalyst Ru-PPh2CO。
In a preferred embodiment of the present invention, in the step 1), bis [ 2-diphenylphosphinoethyl ] is used]Amine hydrochloride, toluene, 10% NaOH solution and RuHCl (CO) (PPh)3)3The dosage ratio of the components is 2-2.5g, 40-50mL, 10-12mL and 3.5-3.6 g.
The third technical scheme adopted by the invention for solving the technical problems is as follows: provides a ruthenium-based catalyst Ru-PPh2The application of CO is used for preparing polyamide by amidation polymerization reaction between dimethyl dicarboxylate and alkyl diamine.
In a preferred embodiment of the invention, the preparation of the polyamide comprises the following steps:
1) dimethyl dicarboxylate, alkyl diamine or aryl diamine, anisole and the ruthenium-based catalyst Ru-PPh2CO is sequentially placed in the reaction bottles, all gas in the system is replaced by nitrogen through the double-row pipe, and the air in the reaction bottles is completely replaced by nitrogen flow;
2) adding t-BuOK accounting for 20 percent of the total mass of the dicarboxylic acid dimethyl ester, the alkyl diamine or the aryl diamine under the nitrogen flow, and heating and stirring at the temperature of 110-120 ℃ for 48 hours;
3) after the reaction is finished, the solvent is removed by screwing, the solid residue is dissolved in DMF, the mixture is slowly dripped into a toluene solvent in stirring, a crude product is obtained by filtration, and a pure polyamide product is obtained by further precipitation separation; the molecular weight of the polyamide is 8000-17000.
In a preferred embodiment of the present invention, in the step 1), the ratio of the amount of dimethyl dicarboxylate, alkyl diamine or aryl diamine, and anisole is 2.5 mmol: 2.5-3.0mL, and the Ru-PPh catalyst is Ru-PPh2The amount of CO used is 1% of the total amount of dimethyl dicarboxylate, alkyl diamine or aryl diamine.
In a preferred embodiment of the present invention, the structural formula of the dimethyl dicarboxylate includes:
Figure BDA0002238938400000031
in a preferred embodiment of the present invention, the formula of the alkyl diamine comprises:
Figure BDA0002238938400000032
in a preferred embodiment of the present invention, the structural formula of the polyamide includes:
Figure BDA0002238938400000041
compared with the background technology, the technical scheme has the following advantages:
the invention adopts dimethyl dicarboxylate to replace dicarboxylic acid in the traditional reaction system, and adopts Ru-PPh2A method for preparing macromolecular polyamide by catalyzing dimethyl dicarboxylate and diamine with CO catalyst under mild condition. Compared with the reported reaction system which takes dimethyl dicarboxylate and alkyl diamine as raw materials and takes HCl or sodium hydroxide and the like as catalystsThe temperature is high (230 ℃), the vacuum degree is required (0.093-0.1 Mpa), and the byproduct hydrogen chloride gas exists, namely the Ru-PPh ruthenium-based catalyst used in the invention2The CO has the advantages of high catalytic activity, high yield (up to 92 percent), no generation of a strong-acid by-product hydrogen chloride and the like, and the reaction process is simple to operate, has low corrosivity on production equipment, conforms to the requirements of a green synthesis process and has good industrial prospect.
Detailed Description
Example 1
This example is a ruthenium-based catalyst Ru-PPh2Production of CO
1) To a 100mL two-necked flask was added 2.1g of bis [ 2-diphenylphosphinoethyl]Amine hydrochloride, 40mL toluene and 10mL 10% NaOH solution, stirred at 40 ℃ for 20min under nitrogen, then the organic phase was separated and MgSO4Drying;
2) a dry two-necked flask was charged with the organic phase dried in step one and 3.6g of RuHCl (CO) (PPh)3)3Heating to 120 ℃ in nitrogen atmosphere, stirring for 2h, cooling to 40 ℃, and stirring for 1.7 h;
3) filtering and separating the precipitate, washing with toluene for three times, wherein the amount of toluene used for each washing is 10mL, drying in a vacuum drying oven at 50 ℃ overnight, and obtaining a pale yellow solid, namely the ruthenium-based catalyst Ru-PPh2CO, of the formula:
Figure BDA0002238938400000051
example 2
Ru-PPh catalyst prepared in example 12CO, catalyzing amidation polymerization reaction between dicarboxylic acid dimethyl ester and alkyl diamine to prepare polyamide P1, and the method specifically comprises the following steps:
1) 2.5mmol of triethylene glycol-functionalized dicarboxylic acid dimethyl ester, 2.5mmol of 1, 6-hexanediamine, 3mL of anisole and 1 mol% of ruthenium-based catalyst Ru-PPh2Placing CO in the reaction bottles in sequence, replacing all gas in the system with nitrogen through the double-row pipe, and using nitrogen flow to replace the reaction bottlesThe replacement of the middle air is complete;
2) adding 20 mol% of t-BuOK under nitrogen flow, and then heating and stirring for 48h at 120 ℃;
3) after the reaction is finished, the solvent is spun off, the solid residue is dissolved in 10mL of DMF, the solution is slowly dripped into a toluene solvent in stirring, a crude product is obtained by filtration, and the crude product is vacuum-dried after suction filtration to obtain 0.87g of a target polyamide product with the yield of 85%;
the prepared polyamide has the structural formula
Figure BDA0002238938400000061
4) The molecular weight of the polyamide is determined by GPC, while the structure of the polyamide is determined by FT-IR and1h NMR, infrared test by KBr tablet pressing method, GPC test with DMF as mobile phase,1the H NMR test solvent was DMSO-d 6.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3309,3076,2931,1660,1568,1548,1440, 1368,1294,1122,1097,1064,713,684.1H NMR(400MHz,DMSO)δ8.13-7.90(m),7.72-7.04 (m),4.26-4.01(m),3.85(dd),3.75(s),3.62-3.36(m),3.23(s),2.29(s),1.82-1.15(m)。
Example 3
This example differs from example 2 in that: this example is the preparation of a polyamide P2 (formula:
Figure BDA0002238938400000062
2.5mmol of diethylene glycol functionalized dicarboxylic acid dimethyl ester, 2.5mmol of 1, 6-hexanediamine and 1 mol% of Ru-PPh2The CO catalyst and 3mL of anisole are added in portions to a polymerization bottle. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by screwing, then the mixture is dissolved in 10mL of DMF, the mixture is slowly dripped into the toluene solvent in stirring, after suction filtration, vacuum drying is carried out to obtain 0.81g of the target polyamide product,the yield thereof was found to be 89%.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3296,3082,2933,1651,1548,1440,1386, 1294,1105,1064,830,713.1H NMR(400MHz,DMSO)δ8.62(dd),8.12-6.98(m),4.24-3.98 (m),3.93-3.37(m),3.31-3.12(m),2.31(d),2.15-0.99(m)。
Example 4
This example differs from example 2 in that: this example is the preparation of a polyamide P3 (formula:
Figure BDA0002238938400000071
2.5mmol of ethylene glycol-functionalized dicarboxylic acid dimethyl ester, 2.5mmol of 1, 6-hexanediamine and 1 mol% of Ru-PPh2The CO catalyst and 3mL of anisole are added in portions to a polymerization bottle. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by spinning, and then the mixture is dissolved in 10mL of DMF, and the mixture is slowly dripped into a toluene solvent in stirring, and after suction filtration and vacuum drying, 0.68g of target polyamide product is obtained, and the yield is 85%.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3367,3078,2929,1654,1560,1360,1120, 1066,879,781,717.1H NMR(400MHz,DMSO)δ8.51(d),8.07-7.03(m),4.65-3.91(m),3.67 (s),3.57(s),3.37-3.12(m),2.61(t),2.29(d),1.81-0.97(m)。
Example 5
This example differs from example 2 in that: this example is the preparation of a polyamide P4 (formula:
Figure BDA0002238938400000081
2.5mmol polyethylene glycol functionalized dicarboxylic acid dimethyl ester, 2.5mmol1, 6-hexanediamine and 1 mol% Ru-PPh2The CO catalyst and 3mL of anisole are added in portions to a polymerization bottle. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by spinning, and then the mixture is dissolved in 10mL of DMF, and the mixture is slowly dripped into a toluene solvent in stirring, and after suction filtration and vacuum drying, the target polyamide product 1.08g is obtained, and the yield is 92%.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3437,3113,3086,2924,2877,1606,1546, 1508,1404,1305,1257,1143,1101,1060,1037,991,929,850,790,698,651,632,528.1H NMR (400MHz,DMSO)δ7.75(d),7.47(d),7.11(d),6.76(dH),4.13-3.97(m),3.83-3.66(m),3.32(s), 2.29(s),1.54(d),1.24(s)。
Example 6
This example differs from example 2 in that: this example is the preparation of a polyamide P5 (formula:
Figure BDA0002238938400000082
2.5mmol of dimethyl propanedicarboxylate, 2.5mmol of ethylene glycol diamine and 1 mol% of Ru-PPh2The CO catalyst and 3mL of anisole are added in portions to a polymerization bottle. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by spinning, and then the mixture is dissolved in 10mL of DMF, and the mixture is slowly dripped into a toluene solvent in stirring, and after suction filtration and vacuum drying, 0.38g of target polyamide product is obtained, and the yield is 75%.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3296,3080,2928,2872,1645,1539,1311,1095,804.1H NMR(400MHz,DMSO)δ8.33-7.94(m),3.57-3.32(m),3.29-2.92(m),2.69- 2.58(m)。
Example 7
This example differs from example 2 in that: this example is the preparation of a polyamide P6 (formula:
Figure BDA0002238938400000091
2.5mmol dimethyl butanedicarboxylate, 2.5mmol ethylene glycol diamine and 1 mol% Ru-PPh2The CO catalyst and 3mL of anisole are added into the polymerization bottle in batches. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by spinning, and then the mixture is dissolved in 10mL of DMF, and the mixture is slowly dripped into a toluene solvent in stirring, and after suction filtration and vacuum drying, 0.48g of target polyamide product is obtained, and the yield is 89%.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3296,3082,2941,1633,1560,1419,1141, 690.1H NMR(400MHz,DMSO)δ8.34-7.84(m),3.70-3.04(m),2.41-2.05(m)。
Example 8
This example differs from example 2 in that: this example is the preparation of a polyamide P7 (formula:
Figure BDA0002238938400000092
2.5mmol of dimethyl pentanedicarboxylate, 2.5mmol of ethylene glycol diamine and 1 mol% of Ru-PPh2The CO catalyst and 3mL of anisole are added in portions to a polymerization bottle. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by spinning, and then the mixture is dissolved in 10mL of DMF, and the mixture is slowly dripped into a toluene solvent in stirring, and after suction filtration and vacuum drying, 0.45g of target polyamide product is obtained, and the yield is 78%.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3257,3090,2945,2875,1631,1560,1425,1400,1143,1035,742.1H NMR(400MHz,DMSO)68.06(dd),3.31(dd),2.17-1.46(m)。
Example 9
This example differs from example 2 in that: this example is the preparation of a polyamide P8 (formula:
Figure BDA0002238938400000101
2.5mmol of dimethyl pentanedicarboxylate, 2.5mmol of ethylene glycol diamine and 1 mol% of Ru-PPh2The CO catalyst and 3mL of anisole are added in portions to a polymerization bottle. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by spinning, and then the product is dissolved in 10mL of DMF, and the solution is slowly dripped into the stirred toluene solvent, and after suction filtration and vacuum drying, 0.41g of the target polyamide product is obtained, and the yield is 67%.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3306,2078,2939,2866,1735,1637,1552, 1437,1276,1138,729,678.1H NMR(400MHz,DMSO)68.06(d),3.79-3.03(m),2.33-0.99 (m)。
Example 10
This example differs from example 2 in that: this example is the preparation of a polyamide P9 (formula:
Figure BDA0002238938400000102
dimethyl dicarboxylate with the temperature of 2.5mmol, 2.5mmol ethylene glycol diamine and 1mol percent Ru-PPh2The CO catalyst and 3mL of anisole are added in portions to a polymerization bottle. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by spinning, and then the mixture is dissolved in 10mL of DMF, and the mixture is slowly dripped into a toluene solvent in stirring, and after suction filtration and vacuum drying, 0.61g of target polyamide product is obtained, wherein the yield is 85%.
Of the compoundThe characterization results were as follows: FT-IR (KBr disc) cm-1:3296,3084,2922,2850,1637,1560,1145,700.1H NMR(400MHz,DMSO)δ8.35-7.63(m),3.72-2.90(m),2.04(s),1.79(s),1.58-1.06 (m)。
Example 11
This example differs from example 2 in that: this example is the preparation of a polyamide P10 (formula:
Figure BDA0002238938400000111
2.5mmol of dimethyl decanedicarboxylate, 2.5mmol of ethylene glycol diamine and 1 mol% of Ru-PPh2The CO catalyst and 3mL of anisole are added in portions to a polymerization bottle. All the gas in the system was replaced by nitrogen through the double row pipe. Then, 20 mol% t-BuOK was added under a nitrogen stream. Then heating and stirring at 120 ℃ for 48 h. After the reaction is finished, the solvent is removed by spinning, and then the mixture is dissolved in 10mL of DMF, and the mixture is slowly dripped into a toluene solvent in stirring, and after suction filtration and vacuum drying, 0.65g of target polyamide product is obtained, and the yield is 87%.
The characterization results of this compound are as follows: FT-IR (KBr disc) cm-1:3298,3082,2924,2850,1641,1560,1467, 1413,1145,719,698.1H NMR(400MHz,DMSO)δ7.82(s),3.20(dd),2.04(s),1.34(d)。
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.

Claims (7)

1. Ruthenium-based catalyst Ru-PPh2Use of CO, characterized in that: for preparing polyamide by amidation polymerization between dimethyl dicarboxylate and alkyl diamine, and ruthenium-based catalyst Ru-PPh2The structural formula of CO is:
Figure DEST_PATH_IMAGE002
the preparation method comprises the following steps:
1) dimethyl dicarboxylate, alkyl diamine, anisole and the ruthenium-based catalyst Ru-PPh2CO is sequentially placed in the reaction bottles, all gas in the system is replaced by nitrogen through the double-row pipe, and the air in the reaction bottles is completely replaced by nitrogen flow;
the dosage ratio of the dicarboxylic acid dimethyl ester, the alkyl diamine and the anisole is 2.5 mmol: 2.5 mmol: 2.5-3.0mL, the ruthenium-based catalyst Ru-PPh2The amount of CO is 1 percent of the total amount of the dimethyl dicarboxylate and the alkyl diamine;
2) adding t-BuOK accounting for 20 percent of the total mass of the dimethyl dicarboxylate and the alkyl diamine under the nitrogen flow, and heating and stirring at 110-120 ℃ for 48 h;
3) after the reaction is finished, the solvent is removed by screwing, the solid residue is dissolved in DMF, the mixture is slowly dripped into a toluene solvent in stirring, a crude product is obtained by filtration, and a pure polyamide product is obtained by further precipitation separation; the molecular weight of the polyamide is 8000-17000.
2. The ruthenium-based catalyst Ru-PPh according to claim 12Use of CO, characterized in that the dimethyl dicarboxylate has the formula:
Figure DEST_PATH_IMAGE004
3. the ruthenium-based catalyst Ru-PPh according to claim 12Use of CO, wherein the alkyldiamine has the formula:
Figure DEST_PATH_IMAGE006
4. the ruthenium-based catalyst Ru-PPh according to claim 12Use of CO, ofCharacterized in that the structural formula of the polyamide comprises:
Figure DEST_PATH_IMAGE008
Figure DEST_PATH_IMAGE010
Figure DEST_PATH_IMAGE012
Figure DEST_PATH_IMAGE014
Figure DEST_PATH_IMAGE016
Figure DEST_PATH_IMAGE018
Figure DEST_PATH_IMAGE020
Figure DEST_PATH_IMAGE022
Figure DEST_PATH_IMAGE024
or
Figure DEST_PATH_IMAGE026
5. The ruthenium-based catalyst Ru-PPh according to claim 12Use of CO, characterized in that: the ruthenium-based catalyst Ru-PPh2The synthesis route of CO is as follows:
Figure DEST_PATH_IMAGE028
6. the ruthenium-based catalyst Ru-PPh according to claim 12The application of CO is characterized in that: the ruthenium-based catalyst Ru-PPh2The preparation method of CO is characterized by comprising the following steps:
1) bis [ 2-diphenylphosphinoethyl)]Mixing amine hydrochloride, toluene and 10% NaOH solution, stirring at 30-40 deg.C under nitrogen atmosphere for 20-30min, separating organic phase, and adding MgSO4Drying;
2) the organic phase dried in step 1) and RuHCl (CO) (PPh)3)3Mixing, heating to 110-130 ℃ in a nitrogen atmosphere, stirring for 2h, cooling to 30-40 ℃, and stirring for 1-2 h;
3) filtering, separating and precipitating, washing with toluene for three times, and drying in a vacuum drying oven at 40-50 deg.C overnight to obtain pale yellow solid which is ruthenium-based catalyst Ru-PPh2CO。
7. The ruthenium-based catalyst Ru-PPh according to claim 62Use of CO, characterized in that: the bis [ 2-diphenylphosphinoethyl group]Amine hydrochloride, toluene, 10% NaOH solution, and RuHCl (CO) (PPh)3)3The dosage ratio of the components is 2-2.5 g: 40-50 mL: 10-12 mL: 3.5-3.6 g.
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