CN114292385B - Nitrogen-containing porous organic polymer composite material and preparation method and application thereof - Google Patents
Nitrogen-containing porous organic polymer composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen-containing porous organic polymer composite material, and a preparation method and application thereof. Specifically, the invention takes aluminum trichloride as a catalyst, and 2, 6-bis (benzimidazole) pyridine and biphenyl are copolymerized to obtain a porous organic polymer, and ruthenium trichloride is loaded on the polymer by taking the porous organic polymer as a carrier through coordination action to obtain a composite material. The material can efficiently catalyze the cross-coupling reaction of the secondary alcohol and the primary alcohol to synthesize the beta-alkylated secondary alcohol compound. The catalyst system has wide functional group tolerance, and after the catalyst is continuously recycled for a plurality of times, the catalyst system still maintains high catalytic activity and the metal ruthenium is not leached out.
Description
Technical Field
The invention belongs to the technical field of catalytic chemistry, and relates to preparation of a nitrogen-containing porous organic polymer composite material and a method for synthesizing a beta-alkylated secondary alcohol compound by catalyzing cross-coupling reaction of secondary alcohol and primary alcohol.
Background
Alcohol compounds are very important in the organic synthesis and chemical industries. Conventional routes to beta-alkylated alcohols from secondary alcohols typically require a multi-step process involving oxidation of the secondary alcohol, alkylMetallization of halides and reduction of beta-alkylated ketones. The reaction of an alcohol as alkylating agent with another alcohol has been considered as a green direct process for obtaining beta-alkylated alcohols, H during the transition metal catalyzed reaction 2 And/or H 2 O is produced as a by-product, has high atom utilization efficiency and is harmless to the environment. Wherein the cross-coupling reaction of secondary alcohol and primary alcohol is carried out mainly by dehydrogenation-condensation-hydrogenation step, and alpha, beta-unsaturated ketone, alpha-alkylated ketone and beta-alkylated secondary alcohol are selectively obtained. Various homogeneous catalytic systems using metal complexes of Ru, ir, pd, cu, co and Mn have been developed for the beta-alkylation of secondary alcohols with primary alcohols. However, there is a need in the art for improvements in reducing metal contamination and catalyst recovery performance.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of a nitrogen-containing porous organic polymer composite material and a beta-alkylated secondary alcohol compound synthesized by catalyzing cross-coupling reaction of secondary alcohol and primary alcohol. The porous organic polymer containing nitrogen is prepared by using 2, 6-bis (benzimidazole) pyridine and biphenyl as polymerization monomers through a simple method. The polymer is loaded with metal ruthenium to obtain a composite material which is used as a catalyst, and the composite material catalyzes cross-coupling reaction of secondary alcohol and primary alcohol in toluene solvent to finally prepare the beta-alkylated secondary alcohol. In addition, in the reaction system, the composite material used as the catalyst can be recycled for more than 4 times, is still stable after 4 times of circulation, has no obvious reduction of the catalytic activity, and is an effective and efficient catalyst.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a porous organic polymer composite material containing nitrogen is prepared by pyridine compound and benzene compound, and then reacts with ruthenium salt to obtain the porous organic polymer composite material containing nitrogen; preferably, the nitrogen-containing porous organic polymer is prepared from a pyridine compound and a benzene compound under inert gas, and then reacted with ruthenium salt to obtain the nitrogen-containing porous organic polymer composite material. Preferably, the pyridine compound is 2, 6-bis (benzimidazole) pyridine; the benzene compound is biphenyl; the ruthenium salt is ruthenium trichloride.
The preparation method of the nitrogen-containing porous organic polymer composite material comprises the following steps: adding 2, 6-bis (benzimidazole) pyridine, biphenyl and aluminum trichloride into anhydrous chloroform under inert gas, then reacting for 15-30 hours, washing the obtained precipitate with water, dilute hydrochloric acid and an organic solvent to obtain a nitrogen-containing porous organic polymer, and then adding RuCl under the inert gas 3 And adding the nitrogen-containing porous organic polymer into absolute ethyl alcohol, and then refluxing and stirring for 8-15 hours to obtain the nitrogen-containing polymer supported metal ruthenium composite material.
In the technical scheme, the reaction is carried out for 15-30 hours at 50-65 ℃, then the obtained precipitate is washed by water, dilute hydrochloric acid, water, methanol and diethyl ether in sequence, and then the nitrogen-containing porous organic polymer is obtained by vacuum drying; and (3) refluxing and stirring for 8-15 hours, washing the obtained precipitate with water, dilute hydrochloric acid, water, methanol and diethyl ether in sequence, and then drying in vacuum to obtain the nitrogen-containing porous organic polymer composite material.
In the above technical solution, the inert gas is selected from any one of nitrogen and argon, preferably nitrogen; chloroform is used as an organic solvent; aluminum trichloride is the catalyst.
The invention discloses an application of the nitrogen-containing porous organic polymer composite material in preparing a recyclable catalyst or an application of the nitrogen-containing porous organic polymer composite material in catalyzing cross-coupling reaction of secondary alcohol and primary alcohol to synthesize a beta-alkylated secondary alcohol compound. The secondary alcohol is selected from any one of 1-phenethyl alcohol, 1- (4-chlorophenyl) alcohol, 1- (4-bromophenyl) alcohol, 1- (4-methylphenyl) alcohol, 1- (4-methoxyphenyl) alcohol, 1- (2-chlorophenyl) alcohol, 1- (2-methoxy) alcohol, 1- (2-methylphenyl) alcohol, 1- (3-methoxyphenyl) alcohol and 1- (3-methylphenyl) alcohol; the primary alcohol is selected from any one of benzyl alcohol, 4-chlorobenzyl alcohol, 4-trifluoromethyl benzyl alcohol, 4-methoxybenzyl alcohol, 4-tertiary butyl benzyl alcohol, 2-methylbenzyl alcohol, 2-methoxybenzyl alcohol, 3-methylbenzyl alcohol and 3-chlorobenzyl alcohol.
The invention discloses a method for synthesizing beta-alkylated secondary alcohol compounds by catalyzing cross-coupling reaction of secondary alcohol and primary alcohol by using the nitrogen-containing porous organic polymer composite material, which comprises the following steps:
mixing the secondary alcohol, the primary alcohol, the alkali, the nitrogen-containing porous organic polymer composite material and the solvent, and reacting for 4-12 hours at 100-140 ℃ under nitrogen to obtain the beta-alkylated secondary alcohol compound; further, after the reaction is finished, filtering to remove the composite catalyst, adding water, extracting with ethyl acetate, combining organic phases, drying the organic phases through anhydrous sodium sulfate, concentrating under reduced pressure, purifying the crude product through a silica gel column, and using petroleum ether and ethyl acetate as eluent to obtain the beta-alkylated secondary alcohol compound.
In the technical scheme, the preparation of the beta-alkylated secondary alcohol by the reaction of the secondary alcohol and the primary alcohol is carried out in the presence of alkali and in a nitrogen atmosphere; the dosage ratio of the secondary alcohol, the primary alcohol, the alkali and the nitrogen-containing porous organic polymer composite material is 1mmol (1-1.5 mmol), (0.3-1 mmol), (15-25 mg, preferably 1 mmol: 1.2 mmol: 0.5 mmol: 20 mg).
In the above technical scheme, the alkali is potassium hydroxide or cesium hydroxide.
In the technical scheme, the reaction temperature is 100-140 ℃.
In the technical scheme, the reaction time is 4-12 hours.
Compared with the prior art, the invention adopting the technical scheme has the following advantages:
(1) The invention discloses a preparation method of a nitrogen-containing porous organic polymer for the first time, which takes 2, 6-bis (benzimidazole) pyridine and biphenyl as monomers, chloroform as a solvent and aluminum trichloride as a catalyst; the polymer has good stability, large specific surface area and uniform pore size distribution;
(2) The nitrogen-containing porous organic polymer can be loaded with metal ruthenium, and the metal ruthenium has the characteristics of uniform distribution, trivalent valence and the like;
(3) The nitrogen-containing porous organic polymer supported metal ruthenium composite material disclosed by the invention can be applied to catalyzing cross coupling reaction of secondary alcohol and primary alcohol to synthesize beta-alkylated secondary alcohol compounds, and has the characteristics of high conversion efficiency, wide application range, green and mild reaction conditions and the like;
(4) After the catalytic reaction is finished, centrifuging the catalyst from the reaction system, washing and drying the catalyst, and then adding the catalyst into a new reaction system to perform the next reaction, wherein the nitrogen-containing polymer supported metal ruthenium composite material can be reused for 4 times, and the catalytic activity of the nitrogen-containing polymer supported metal ruthenium composite material is not obviously reduced.
Drawings
FIG. 1 is a scanning electron microscope image of a nitrogen-containing porous organic polymer material of the present invention.
FIG. 2 is a solid nuclear magnetic resonance spectrum of a nitrogen-containing porous organic polymer material of the present invention.
FIG. 3 is a nitrogen adsorption/desorption isotherm at 77K for a nitrogen-containing porous organic polymer and nitrogen-containing porous organic polymer supported metal ruthenium composite of the invention.
FIG. 4 is an N1 s photoelectron spectrum of a nitrogen-containing porous organic polymer and a nitrogen-containing porous organic polymer supported metal ruthenium composite of the invention, with an increased binding energy as a result of coordination between ruthenium and nitrogen, as compared to the photoelectron spectrum of nitrogen before and after metal loading.
FIG. 5 is an elemental distribution diagram of a nitrogen-containing porous organic polymer supported metal ruthenium composite of the invention illustrating uniform distribution of C, N, ru elements.
FIG. 6 is a graph showing the recycling efficiency of the nitrogen-containing porous organic polymer-supported metal ruthenium composite of the present invention as a catalyst for catalyzing the reaction of example 3, from which it can be seen that the catalyst maintains a higher efficiency without significant decrease during recycling.
Detailed Description
The invention will be further described with reference to the drawings and specific embodiments. Unless otherwise indicated, reagents, materials, instruments, and the like used in the following examples are all commercially available, and specific preparation procedures and test characterization are conventional techniques. In the nitrogen-containing porous organic polymer composite material disclosed by the invention, metal ruthenium is uniformly distributed on a nitrogen-containing polymer, and the substrate of the nitrogen-containing porous organic polymer composite material is the nitrogen-containing polymer, wherein the valence of the metal ruthenium is trivalent; preferably, the loading of ruthenium in the nitrogen-containing polymer supported metal ruthenium material is 2.5 wt% -3.5 wt%, preferably 2.9 wt% -3.3 wt%, and can be obtained by using the mass percentage between metal ruthenium and the nitrogen-containing polymer material.
Example 1
2, 6-bis (benzimidazole) pyridine (1 mmol), biphenyl (0.154 g, 1 mmol) and aluminum trichloride (10 mmol, 1.33, g) were added to anhydrous chloroform 20 mL under nitrogen atmosphere, then stirred at 58℃for 24 hours, after the reaction, the obtained precipitate was successively treated with water, dilute hydrochloric acid (HCl-H) 2 O, v/v=1:1), water, methanol, diethyl ether, and then vacuum-dried to obtain the nitrogen-containing porous organic polymer.
Example 2
RuCl is to be processed 3 (17 mg) and pyrazole polymer (200 mg) are added into a three-neck round bottom flask containing 25mL of absolute ethyl alcohol, liquid nitrogen freezing-air extraction-nitrogen charging-thawing are repeatedly carried out for three times, then reflux stirring is carried out for 12 hours, after the reaction is finished, solids are centrifugally separated, water, ethanol and diethyl ether are sequentially used for washing, and then vacuum drying is carried out, so that the corresponding nitrogen-containing polymer supported metal ruthenium composite material (the ruthenium load amount is 3.11 wt%) is obtained and is used as the catalyst of the following examples.
The above reaction is schematically shown below:
FIG. 1 is a scanning electron microscope image of the nitrogen-containing porous organic polymer material; FIG. 2 is a solid nuclear magnetic resonance spectrum of the nitrogen-containing porous organic polymer material; FIG. 3 is a nitrogen adsorption/desorption isotherm at 77K for the nitrogen-containing porous organic polymer and nitrogen-containing porous organic polymer supported metal ruthenium composite described above; FIG. 4 is an N1 s photoelectron spectrum of the above-described nitrogen-containing porous organic polymer and nitrogen-containing porous organic polymer supported metal ruthenium composite, with an increase in binding energy as a result of coordination between ruthenium and nitrogen, as compared to the photoelectron spectra of nitrogen before and after metal loading; fig. 5 is an element distribution diagram of the above nitrogen-containing porous organic polymer supported metal ruthenium composite, illustrating uniform distribution of C, N, ru element.
Example 3
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction, the nitrogen-containing polymer supported metal ruthenium composite is filtered and removed, water is added, extraction is carried out by ethyl acetate, the organic phases are combined, the organic phases are dried by anhydrous sodium sulfate and concentrated under reduced pressure, the crude product is purified by a silica gel column, petroleum ether and ethyl acetate are used as eluent, and the corresponding secondary alcohol is obtained, the HPLC yield is 93%, and the separation yield is 88%.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.34 – 7.26 (m, 4H), 7.26 – 7.20 (m, 3H), 7.15 (t, J = 6.2 Hz, 3H), 4.59 (dd, J = 7.4, 5.7 Hz, 1H), 2.65 (m, 2H), 2.23 (s, 1H), 2.14 – 1.86 (m, 2H). 13 C NMR (100 MHz, CDCl 3 , ppm): δ 144.7, 141.9, 128.54, 128.51, 128.45, 127.7, 126.0, 125.9, 73.9, 40.5, 32.1。
after the reaction is finished, separating the catalyst from the reaction system by a centrifugal mode, washing and drying the catalyst by water, methanol and diethyl ether, and then carrying out the next round of catalytic reaction; the catalyst was recycled according to the above procedure, and after 4 cycles, the activity remained high, see fig. 6.
On the basis of the above reaction process, the substrate was kept unchanged, and other conditions were changed to obtain the results as in Table 1.
TABLE 1 reaction conditions and product yields
In table 1, 1a (1 mmol), 2a (1.2 mmol), cat (20 mg), base (eq.), tolene (2 mL), HPLC yield (biphenyl as internal standard).
Example 4
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction, filtering to remove the nitrogen-containing polymer supported metal ruthenium composite, adding water, extracting with ethyl acetate, combining organic phases, drying the organic phases through anhydrous sodium sulfate, concentrating under reduced pressure, purifying the crude product through a silica gel column, and using petroleum ether and ethyl acetate as eluent to obtain the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.31 (d, J = 8.3 Hz, 2H), 7.28 (t, J = 7.7 Hz, 4H), 7.18 (t, J = 8.6 Hz, 3H), 4.69 – 4.62 (m, 1H), 2.77 – 2.61 (m, 2H), 2.09 (m, 1H), 1.98 (m, 1H), 1.81 (s, 1H). 13 C NMR (100 MHz, CDCl 3 , ppm): δ 143.2, 141.6, 133.4, 128.8, 128.6, 128.5, 127.4, 126.1, 73.3, 40.6, 32.1.
example 5
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.47 (d, J = 8.3 Hz, 2H), 7.28 (t, J = 7.5 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 7.18 (t, J = 8.3 Hz, 3H), 4.65 (dd, J= 7.6, 5.5 Hz, 1H), 2.78 – 2.61 (m, 2H), 2.16 – 2.05 (m, 1H), 2.03 – 1.93 (m, 1H), 1.77 (s, 1H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 142.7, 140.6, 130.7, 127.7, 127.6, 127.6, 126.8, 125.1, 125.1, 120.5, 72.3, 39.6, 31.0.
example 6
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.27 – 7.21 (m, 2H), 7.19 (s, 1H), 7.18 – 7.08 (m, 6H), 4.63 – 4.51 (m, 1H), 2.76 – 2.54 (m, 2H), 2.31 (s, 3H), 2.19 (s, 1H), 2.12 – 2.01 (m, 1H), 2.01 – 1.90 (m, 1H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 142.0, 141.7, 137.3, 129.2, 128.5, 128.4, 126.0, 125.9, 73.7, 40.4, 32.1, 21.2.
example 7
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.29 – 7.21 (m, 3H), 7.20 (d, J = 1.9 Hz, 1H), 7.15 (dd, J = 7.1, 5.3 Hz, 3H), 6.90 – 6.77 (m, 2H), 4.61 – 4.50 (m, 1H), 3.74 (s, 3H), 2.80 – 2.50 (m, 2H), 2.29 (s, 1H), 2.14 – 2.02 (m, 1H), 1.95 (m, 1H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 159.1, 141.9, 136.8, 128.5, 128.4, 127.3, 125.9, 113.9, 73.4, 55.3, 40.4, 32.1.
example 8
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (600 MHz, CDCl 3 ) δ 7.57 (dd, J = 7.7, 1.6 Hz, 1H), 7.34 – 7.30 (m, 1H), 7.29 – 7.25 (m, 3H), 7.23 – 7.19 (m, 3H), 7.17 (d, J = 7.3 Hz, 2H), 5.13 (dd, J = 8.4, 4.1 Hz, 1H), 2.93 – 2.81 (m, 1H), 2.74 (m, 1H), 2.15 – 1.99 (m, 2H), 1.85 (s, 1H).
13 C NMR (151 MHz, CDCl 3 ) δ 142.1, 141.8, 132.0, 129.6, 129.2, 128.6, 128.5, 128.4, 127.3, 127.2, 126.0, 125.4, 70.4, 39.1, 32.3.
example 9
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.45 (dd, J = 7.5, 1.4 Hz, 1H), 7.42 – 7.37 (m, 2H), 7.37 – 7.22 (m, 4H), 7.07 (t, J = 7.3 Hz, 1H), 6.96 (d, J = 8.2 Hz, 1H), 5.03 (s, 1H), 3.89 (s, 3H), 3.03 (s, 1H), 3.00 – 2.90 (m, 1H), 2.81 (m, 1H), 2.32 – 2.14 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 156.5, 142.2, 132.4, 128.5, 128.3, 126.9, 125.7, 120.7, 110.5, 70.1, 55.2, 38.8, 32.3.
example 10
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.43 (d, J = 7.5 Hz, 1H), 7.28 – 7.21 (m, 2H), 7.20 – 7.09 (m, 5H), 7.07 (d, J = 7.2 Hz, 1H), 4.83 (dd, J = 8.0, 4.5 Hz, 1H), 2.79 (m, 1H), 2.67 (m, 1H), 2.17 (s, 3H), 2.10 (s, 1H), 2.05 – 1.87 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 142.8, 141.9, 134.5, 130.5, 128.5, 128.4, 127.2, 126.3, 125.9, 125.2, 69.9, 39.5, 32.3, 18.9.
example 11
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.23 (dd, J = 14.1, 7.0 Hz, 3H), 7.16 (t, J = 9.4 Hz, 3H), 6.87 (d, J = 2.0 Hz, 2H), 6.77 (dd, J = 8.1, 1.8 Hz, 1H), 4.57 (dd, J = 7.1, 5.9 Hz, 1H), 3.73 (s, 3H), 2.75 – 2.53 (m, 2H), 2.42 (s, 1H), 2.14 – 1.88 (m, 2H).
13 C NMR (150 MHz, CDCl 3 , ppm): δ 159.8, 146.4, 141.9, 129.5, 128.5, 128.4, 125.9, 118.3, 113.0, 111.5, 73.7, 55.2, 40.4, 32.1.
19 F NMR (377 MHz, CDCl 3 , ppm): δ-63.3.
example 12
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.29 – 7.20 (m, 2H), 7.19 (d, J = 7.5 Hz, 1H), 7.14 (dd, J = 8.4, 4.0 Hz, 3H), 7.12 – 7.00 (m, 3H), 4.54 (m, 1H), 2.77 – 2.54 (m, 2H), 2.33 (s, 1H), 2.30 (s, 3H), 2.01 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 144.6, 141.9, 138.1, 128.5, 128.4, 128.4, 126.7, 125.9, 123.1, 73.8, 40.4, 32.1, 21.5.
example 13
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.34 (q, J = 6.2 Hz, 4H), 7.25 (dd, J= 16.2, 9.5 Hz, 3H), 7.11 (d, J = 8.3 Hz, 2H), 4.65 (t, J = 4.7 Hz, 1H), 2.82 – 2.54 (m, 2H), 2.19 – 1.88 (m, 3H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 144.6, 140.4, 131.7, 130.0, 128.7, 128.6, 127.9, 126.1, 73.9, 40.5, 31.5.
example 14
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.49 (d, J = 8.1 Hz, 2H), 7.31 (s, 1H), 7.28 (dd, J = 8.6, 2.1 Hz, 3H), 7.23 (t, J = 5.8 Hz, 3H), 4.59 (dd, J = 7.7, 5.5 Hz, 1H), 2.83 – 2.56 (m, 2H), 2.48 (s, 1H), 2.17 – 1.85 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 146.1, 144.4, 128.8, 128.7, 127.9, 126.0, 125.4, 125.4, 125.3, 125.3, 73.7, 40.1, 31.9.
example 15
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.34 (d, J = 2.3 Hz, 4H), 7.31 – 7.25 (m, 1H), 7.10 (dd, J = 8.1, 3.8 Hz, 2H), 6.83 (dd, J = 8.1, 5.8 Hz, 2H), 4.74 – 4.61 (m, 1H), 3.78 (s, 3H), 2.78 – 2.54 (m, 2H), 2.23 – 1.83 (m, 3H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 157.9, 144.8, 134.0, 129.5, 128.6, 127.7, 126.1, 114.0, 74.0, 55.4, 40.9, 31.3.
example 16
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.33 – 7.25 (m, 6H), 7.25 – 7.19 (m, 1H), 7.09 (d, J = 8.3 Hz, 2H), 4.60 (t, J = 6.5 Hz, 1H), 2.78 – 2.48 (m, 2H), 2.27 (s, 1H), 2.03 (m, 2H), 1.29 (s, 9H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 148.7, 144.7, 138.8, 128.5, 128.2, 127.6, 126.1, 125.3, 73.9, 40.5, 34.4, 31.5, 31.5.
example 17
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.27 (d, J = 4.4 Hz, 4H), 7.23 – 7.19 (m, 1H), 7.07 (dd, J = 5.9, 3.2 Hz, 4H), 4.60 (dd, J = 7.6, 5.5 Hz, 1H), 2.72 – 2.63 (m, 1H), 2.58 – 2.49 (m, 1H), 2.41 (s, 1H), 2.20 (s, 3H), 2.02 – 1.87 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 144.6, 140.1, 136.0, 130.2, 128.8, 128.5, 127.6, 125.99, 125.98, 74.1, 39.2, 29.4, 19.2.
example 18
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.28 (dd, J = 9.1, 5.2 Hz, 4H), 7.22 – 7.08 (m, 3H), 6.89 – 6.77 (m, 2H), 4.56 (dd, J = 8.3, 5.0 Hz, 1H), 3.74 (s, 3H), 2.70 (m, 2H), 2.65 (s, 1H), 2.07 – 1.91 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 157.4, 144.7, 130.1, 130.1, 128.3, 127.3, 127.2, 126.0, 120.7, 110.4, 73.6, 55.3, 39.3, 26.5.
example 19
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.38 – 7.19 (m, 5H), 7.20 – 7.12 (m, 1H), 6.72 (dd, J = 19.4, 7.1 Hz, 3H), 4.65 – 4.52 (m, 1H), 3.72 (s, 3H), 2.78 – 2.50 (m, 2H), 2.35 (s, 1H), 2.16 – 1.89 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 159.7, 144.7, 143.5, 129.4, 128.5, 127.60, 126.0, 120.9, 114.3, 111.2, 73.8, 55.1, 40.4, 32.1.
example 20
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.28 (s, 4H), 7.24 (d, J = 5.8 Hz, 1H), 7.13 (t, J = 7.7 Hz, 1H), 7.02 – 6.87 (m, 3H), 4.71 – 4.45 (m, 1H), 2.72 – 2.51 (m, 2H), 2.29 (s, 4H), 2.00 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 144.7, 141.8, 137.9, 129.3, 128.5, 128.3, 127.6, 126.6, 126.0, 125.5, 73.9, 40.5, 32.0, 21.5.
example 21
Adding secondary alcohol (1 mmol), primary alcohol (1.2 mmol), a nitrogen-containing polymer supported metal ruthenium composite material (20 mg) and potassium hydroxide (0.5 mmol) into a reaction tube provided with a magnetic stirrer 15 mL, adding 2 mL toluene, and repeating the steps of freezing with liquid nitrogen, pumping with air, filling with nitrogen and thawing for three times, and reacting in an oil bath at 130 ℃ for 12 hours; after the reaction was completed, the nitrogen-containing polymer-supported metal ruthenium composite was removed by filtration, water was added, extraction was performed with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The crude product was purified by column on silica gel using petroleum ether and ethyl acetate as eluent to give the corresponding secondary alcohol.
The nuclear magnetic data of the obtained product are as follows:
1 H NMR (400 MHz, CDCl 3 , ppm): δ 7.33 – 7.30 (m, 1H), 7.29 (s, 1H), 7.26 (dd, J = 11.3, 4.8 Hz, 2H), 7.17 – 7.10 (m, 3H), 7.00 (dt, J = 6.5, 1.7 Hz, 1H), 4.57 (t, J = 6.5 Hz, 1H), 2.60 (m, 2H), 2.41 (s, 1H), 2.10 – 1.86 (m, 2H).
13 C NMR (100 MHz, CDCl 3 , ppm): δ 144.4, 144.0, 134.1, 129.7, 128.6, 128.6, 127.8, 126.7, 126.1, 126.0, 73.7, 40.2, 31.7.
the isolation yields corresponding to the products of the above examples are shown in Table 2.
Table 2 example product yield
The precursor prepared by the method is a nitrogen-containing porous organic polymer, and the metal ruthenium in the prepared composite material is uniformly distributed on a polymer substrate, so that the composite material has high-efficiency catalytic efficiency for catalyzing the cross-coupling reaction of secondary alcohol and primary alcohol to synthesize beta-alkylated secondary alcohol compounds. The catalyst of the invention can reduce the pollution of metal to products and has recycling property, and the composite material loaded with metal on the functionalized nitrogen-containing porous organic polymer can show excellent catalytic performance in various reactions.
Claims (8)
1. A nitrogen-containing porous organic polymer composite material is characterized in that a pyridine compound and a benzene compound are used for preparing a nitrogen-containing porous organic polymer, and then the nitrogen-containing porous organic polymer composite material is obtained by reacting the nitrogen-containing porous organic polymer with ruthenium salt; the pyridine compound is 2, 6-bis (benzimidazole) pyridine; the benzene compound is biphenyl; the ruthenium salt is ruthenium trichloride.
2. The method for preparing a nitrogen-containing porous organic polymer composite material according to claim 1, comprising the steps of: under inert gas, preparing the nitrogen-containing porous organic polymer from pyridine compound and benzene compound, and then reacting with ruthenium salt to obtain the nitrogen-containing porous organic polymer composite material.
3. The method for preparing a nitrogen-containing porous organic polymer composite according to claim 2, wherein the preparation of the nitrogen-containing porous organic polymer is performed in an organic solvent, and an inorganic aluminum salt is used as a catalyst.
4. The method for preparing a nitrogen-containing porous organic polymer composite according to claim 3, wherein 2, 6-bis (benzimidazole) pyridine, biphenyl and inorganic aluminum salt are reacted in an organic solvent for 15 to 30 hours, and then the obtained precipitate is washed with water, dilute hydrochloric acid and the organic solvent to obtain the nitrogen-containing porous organic polymer.
5. The method for preparing a nitrogen-containing porous organic polymer composite material according to claim 2, wherein the nitrogen-containing porous organic polymer and the ruthenium salt are subjected to reflux reaction in a solvent to obtain the nitrogen-containing porous organic polymer composite material.
6. Use of the nitrogen-containing porous organic polymer composite according to claim 1 for the preparation of a recyclable catalyst.
7. The use of the nitrogen-containing porous organic polymer composite of claim 1 for catalyzing the cross-coupling reaction of a secondary alcohol and a primary alcohol to synthesize a β -alkylated secondary alcohol compound.
8. The use according to claim 7, wherein the secondary alcohol is selected from any one of 1-phenylethanol, 1- (4-chlorophenyl) ethanol, 1- (4-bromophenyl) ethanol, 1- (4-methylphenyl) ethanol, 1- (4-methoxyphenyl) ethanol, 1- (2-chlorophenyl) ethanol, 1- (2-methoxy) ethanol, 1- (2-methylphenyl) ethanol, 1- (3-methoxyphenyl) ethanol, 1- (3-methylphenyl) ethanol; the primary alcohol is selected from any one of benzyl alcohol, 4-chlorobenzyl alcohol, 4-trifluoromethyl benzyl alcohol, 4-methoxybenzyl alcohol, 4-tertiary butyl benzyl alcohol, 2-methylbenzyl alcohol, 2-methoxybenzyl alcohol, 3-methylbenzyl alcohol and 3-chlorobenzyl alcohol.
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