CN102784660A - Supported metal palladium catalyst, its preparation and its application - Google Patents
Supported metal palladium catalyst, its preparation and its application Download PDFInfo
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Abstract
The invention discloses a supported metal palladium catalyst, its preparation method and its use. The metal loading amount of the catalyst is 1.0-5.0wt%, the specific surface area of the catalyst is 300-900m<2>/g, the pore volume of the catalyst is 0.3-1.0cm<3>/g, the pore diameter of the catalyst is 3.0-10.0nm, and the metal particle diameter of the catalyst is 1.0-8.0nm. In the invention, the preparation of the high-stability metal catalyst with uniform and controllable dimension is realized through a three-step method. The supported metal palladium catalyst can be used for the dynamic kinetic resolution of a secondary alcohol through combining with a lipase, and the catalytic performance of the supported metal palladium catalyst is further better than that of supported metal palladium catalysts prepared through traditional dipping reduction methods. The supported metal palladium catalyst has the advantages of realization of the efficient resolution of the secondary alcohol in a one-pot reaction system, multiple repeated use, and substantial cost reduction.
Description
Technical field
The present invention relates to catalyst field, specifically, relate to a kind of supported metal palladium catalyst and preparation method thereof and combine biology enzyme to be used for the purposes of secondary alcohol Dynamic Kinetic Resolution.
Background technology
Chipal compounds is at medicine, and association areas such as agricultural chemicals and biology have a wide range of applications.Its pharmacological action of the chipal compounds of isomorphism type does not have huge difference, and the chipal compounds that how to obtain individual isomer becomes the research focus of various countries' chemistry researcher.At present, the Kinetic Resolution method is the topmost method of chipal compounds that obtains individual isomer, but its maximum conversion rate is merely 50% in theory.1997, St ü rmer designed the reaction system of the efficient resolving chiral compound that transition metal complex combines with biology enzyme, i.e. Dynamic Kinetic Resolution technology.This method has broken through the restriction of the highest 50% conversion ratio of Kinetic Resolution method, and its theoretical yield finally can reach 100%.Cause the extensive concern of researcher after this method proposes, reported use Al after the Williams seminar, Rh, the compound of Ir and PFL enzyme coupling Dynamic Kinetic Resolution benzyl carbinol, its best result uses Rh
2(OAc)
4As the racemic catalyst, the conversion ratio of benzyl carbinol has reached 60%, and the ee value of product has reached 98%.Though use the homogeneous phase organic metal to have higher catalytic efficiency as the racemic catalyst, there are problems such as product separation difficulty, post-processing step are loaded down with trivial details all the time in homogeneous catalysis system.Simultaneously, organo-metallic catalyst is generally relatively more expensive, has more limited its extensive use.Therefore, seek out a kind of efficient racemization performance that has, the catalyst of recyclable utilization again, with the system of biology enzyme coupling Dynamic Kinetic Resolution chipal compounds be to realize the chiral resolution key in application.
Summary of the invention
The object of the present invention is to provide a kind of supported metal palladium catalyst and preparation method thereof, for existing metallic catalyst field increases one type of new varieties.
Another object of the present invention is in order the purposes of above-mentioned this catalyst to be provided, it is combined to be used for the Dynamic Kinetic Resolution of secondary alcohol with biology enzyme.
The object of the invention can be realized through following technical scheme.
A kind of supported metal palladium catalyst is characterized in that: its content of metal is 1.0-5.0wt%, and specific area is 300-900m
2/ g, pore volume are 0.3-1.0cm
3/ g, the aperture is 3.0-10.0nm, the metallic particles diameter is 1.0-8.0nm.
The preparation method of above-mentioned this supported metal palladium catalyst comprises the steps:
(1) under inert gas shielding, palladium salt is dissolved in the oleyl amine, obtaining concentration is the palladium salting liquid of 0.5-10mg/mL, with 3-5 ℃/min temperature programming to 50-80 ℃; With mass concentration is that the oleyl amine solution of the tert-butylamine borine of 8-15% is poured in the above-mentioned palladium salting liquid, and the mol ratio of tert-butylamine borine and palladium is 8:1-20:1; With above-mentioned solution with 1-5 ℃/min temperature programming to 80-120 ℃; Kept 10-100 minute at 80-120 ℃ then; Add 1-3 times of volume absolute ethyl alcohol after being cooled to room temperature, centrifugation, products obtained therefrom is dispersed in and forms metal concentration in the n-hexane is the solution of 0.05-0.6mg/mL;
(2) under 0-30 ℃, mesoporous silicon oxide SBA-15 is immersed in the above-mentioned solution, the mass ratio that mesoporous silicon oxide SBA-15 and GOLD FROM PLATING SOLUTION belong to is 200-300:1, the ultrasonic 1-5h of 20-50W, centrifugation, washing, 80-120 ℃ of vacuum drying 1-5h;
(3) solid-to-liquid ratio of step (2) products obtained therefrom according to 10-30mg/mL added in the toluene, add the MTES of 2-20% volume again, 50-120 ℃ of reflux 1-15h promptly obtains supported metal palladium catalyst.
Said palladium salt is palladium inorganic salts or organic salt, like palladium acetylacetonate.
Product with the present invention's preparation carries out structural characterization through following means: (X-ray diffraction XRD), carries out the structures of samples analysis to X-ray diffraction on Japan Rigaku D/Max-RB of science type X-ray diffractometer; Transmission electron microscope photo obtains under 200kV at Japanese JEOL JEM2010 type high-resolution-ration transmission electric-lens.
Supported metal palladium catalyst of the present invention can combine to be used for the Dynamic Kinetic Resolution of secondary alcohol with biology enzyme, and catalytic performance is much better than the supported metal palladium catalyst of traditional immersion reduction method preparation.Not only realized in the one pot reaction system efficient fractionation, and can be repeatedly used, greatly reduced cost secondary alcohol.
Description of drawings
Fig. 1 is the TEM photo of the sample of the embodiment of the invention 1 preparation.
Fig. 2 is the XRD spectra of the sample of the embodiment of the invention 1 preparation.
The specific embodiment
Is further detailed, clear, the intactly explanation of doing how to realize below in conjunction with specific embodiment to the present invention, and listed embodiment only further explains the present invention, does not therefore limit the present invention.
Agents useful for same is chemical pure in the embodiment of the invention.
(1) under inert gas shielding, 75mg (0.246mmol) palladium acetylacetonate is added in the 15mL oleyl amine, be stirred to dissolving; In 10 minutes, above-mentioned solution is warmed up to 60 ℃ with 4 ℃/min program.300mg (3.46mmol) tert-butylamine borine is dissolved in the 3.5mL oleyl amine, pours into fast in the above-mentioned palladium salting liquid.Solution with 3 ℃/min temperature programming to 90 ℃, was kept 60 minutes at 90 ℃ then.Add the 30mL absolute ethyl alcohol after being cooled to room temperature, be dispersed in the 125mL n-hexane behind the 8000rmp centrifugation product.
(2) under 25 ℃ with 0.3g mesoporous silicon oxide SBA-15 with 50mL step 1 Metal Palladium solution impregnation (containing the 10mg palladium), ultrasonic 2 hours of 30W, 8000rmp centrifugalizes product, washing with alcohol, 90 ℃ of vacuum drying 4 hours.
(3) step 2 product is added 20mL toluene, add the 2.5mL MTES, 70 ℃ of reflux 10 hours promptly obtain supported metal palladium catalyst.Its metal Pd load capacity is 3.0wt%, and specific area is 612m
2/ g, pore volume are 1.0cm
3/ g, the aperture is 3.1nm.
Fig. 1 is the TEM photo of the prepared sample of present embodiment, and metal Pd nano particle average diameter is 4.5nm from the visible gained sample of photo, and is dispersed in the carrier mesoporous silicon oxide SBA-15 duct.
Fig. 2 is the XRD spectra of the prepared sample of present embodiment, has regular meso-hole structure by the visible sample of little angle XRD spectra, by metal Pd high degree of dispersion in the visible sample of wide-angle XRD figure spectrum.
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 98%, and optical purity is 99.5%, and chemical purity is 99% ester.
(1) under inert gas shielding, 75mg (0.246mmol) palladium acetylacetonate is added in the 20mL oleyl amine, be stirred to dissolving; In 10 minutes, above-mentioned solution is warmed up to 60 ℃ with 4 ℃/min program.300mg (3.46mmol) tert-butylamine borine is dissolved in the 3.5mL oleyl amine, pours into fast in the above-mentioned palladium salting liquid.Solution with 3 ℃/min temperature programming to 90 ℃, was kept 60 minutes at 90 ℃ then.Add the 30mL absolute ethyl alcohol after being cooled to room temperature, be dispersed in the 125mL n-hexane behind the 8000rmp centrifugation product.
(2) under 25 ℃ with 0.3g carrier mesoporous silicon oxide SBA-15 with 50mL step 1 Metal Palladium solution impregnation (containing the 10mg palladium), ultrasonic 2 hours of 30W, 8000rmp centrifugalizes product, washing with alcohol, 90 ℃ of vacuum drying 4 hours.
(3) step 2 product is added 20mL toluene, add the 2.5mL MTES, 70 ℃ of reflux 10 hours promptly obtain supported metal palladium catalyst.Its metal Pd load capacity is 2.8wt%, and specific area is 620m
2/ g, pore volume are 1.0cm
3/ g, the aperture is 3.3nm.
Metal Pd nano particle average diameter is 3.0nm from the visible gained sample of the TEM photo of sample, and is dispersed in the carrier mesoporous silicon oxide SBA-15 duct.
Embodiment 4
The Dynamic Kinetic Resolution that embodiment 3 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 96%, and optical purity is 99.6%, and chemical purity is 95% ester.
(1) under inert gas shielding, the 75mg palladium acetylacetonate is added in the 10mL oleyl amine, be stirred to dissolving; In 10 minutes, above-mentioned solution is warmed up to 60 ℃.300mg tert-butylamine borine is dissolved in the 3.5mL oleyl amine, pours into fast in the above-mentioned palladium salting liquid.Solution with 3 ℃/min temperature programming to 90 ℃, was kept 60 minutes at 90 ℃ then.Add the 30mL absolute ethyl alcohol after being cooled to room temperature, be dispersed in the 125mL n-hexane behind the 8000rmp centrifugation product.
(2) under 25 ℃ with 0.3g mesoporous silicon oxide SBA-15 with 50mL step 1 Metal Palladium solution impregnation, ultrasonic 2 hours of 30W, 8000rmp centrifugalizes product, washing with alcohol, 90 ℃ of vacuum drying 4 hours.
(3) step 2 product is added 20mL toluene, add the 2.5mL MTES, 70 ℃ of reflux 10 hours promptly obtain supported metal palladium catalyst.Its metal Pd load capacity is 3.0wt%, and specific area is 615m
2/ g, pore volume are 0.8cm
3/ g, the aperture is 3.0nm.
Metal Pd nano particle average diameter is 6.0nm from the visible gained sample of the TEM photo of sample, and part is dispersed in the carrier mesoporous silicon oxide SBA-15 duct, and part is dispersed in carrier mesoporous silicon oxide SBA-15 outer surface.
Embodiment 6
The Dynamic Kinetic Resolution that embodiment 5 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 93%, and optical purity is 99.6%, and chemical purity is 97% ester.
Embodiment 7
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 60 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 90%, and optical purity is 99.6%, and chemical purity is 99% ester.
Embodiment 8
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 80 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 98%, and optical purity is 99.6%, and chemical purity is 96% ester.
Embodiment 9
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 90 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 99%, and optical purity is 99.5%, and chemical purity is 92% ester.
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.01MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 99%, and optical purity is 99.9%, and chemical purity is 82% ester.
Embodiment 11
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.02MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 99%, and optical purity is 99.8%, and chemical purity is 90% ester.
Embodiment 12
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.04MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 97%, and optical purity is 99.8%, and chemical purity is 93% ester.
Embodiment 13
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL toluene, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 96%, and optical purity is 99.6%, and chemical purity is 91% ester.
Embodiment 14
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL dimethyl formamide, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 97%, and optical purity is 99.5%, and chemical purity is 92% ester.
Embodiment 15
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL isopropyl alcohol, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 70%, and optical purity is 99.8%, and chemical purity is 99% ester.
Embodiment 16
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic 4-chlorophenethylol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 99%, and optical purity is 99.4%, and chemical purity is 99% ester.
Embodiment 17
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic 4-methylbenzene of 0.5mmol ethanol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 97%, and optical purity is 99.4%, and chemical purity is 99% ester.
Embodiment 18
The Dynamic Kinetic Resolution that embodiment 1 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic 4-methoxybenzene of 0.5mmol ethanol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 96%, and optical purity is 99.4%, and chemical purity is 99% ester.
Embodiment 19
The 25mg palladium acetylacetonate is added in the 50mL chloroform, be stirred to dissolving.Under 25 ℃ with 0.3g mesoporous silicon oxide SBA-15 with above-mentioned palladium salt solution impregnation 3 hours, 150 ℃ of dryings 4 hours.220 ℃ down with 10% hydrogen-argon-mixedly went back raw sample 2 hours, promptly obtain the supported metal palladium catalyst that tradition dipping method of reducing prepares.
The Dynamic Kinetic Resolution that embodiment 19 described catalyst is combined to be used for secondary alcohol with biology enzyme.That is: in the agitated reactor of 10mL, add the racemic benzyl carbinol of 0.5mmol, 5mL n-hexane, 60mg supported metal palladium catalyst, 100mg Novozym 435 biology enzymes and 1.5mmol vinyl acetate.With 5% hydrogen-argon-mixedly charge and discharge 4-5 time with the air in the replacement reaction kettle, at last the hydrogen partial pressure in the still is controlled at 0.03MPa.Agitated reactor is placed 70 ℃ of oil bath pan reactions 12 hours, be cooled to room temperature, centrifugation uses 0.2 μ m filter to filter supernatant liquor, carries out chromatography.Obtaining conversion ratio is 78%, and optical purity is 99.6%, and chemical purity is 80% ester.
Embodiment 21
Combine the supported metal palladium catalyst of Dynamic Kinetic Resolution benzyl carbinol to centrifugalize being used among the embodiment 2 with biology enzyme, with being applied in the reaction described in the embodiment 2 for the second time after the washing with alcohol.Obtaining conversion ratio is 97%, and optical purity is 99.6%, and chemical purity is 99% ester.
Embodiment 22
Combine the supported metal palladium catalyst of Dynamic Kinetic Resolution benzyl carbinol to centrifugalize being used among the embodiment 21 with lipase, with being applied to for the third time in the reaction described in the embodiment 2 after the washing with alcohol.Obtaining conversion ratio is 98%, and optical purity is 99.6%, and chemical purity is 99% ester.
Embodiment 23
Combine the supported metal palladium catalyst of Dynamic Kinetic Resolution benzyl carbinol to centrifugalize being used among the embodiment 22 with biology enzyme, with being applied in the reaction described in the embodiment 2 for the 4th time after the washing with alcohol.Obtaining conversion ratio is 97%, and optical purity is 99.7%, and chemical purity is 99% ester.
Embodiment 24
Combine the supported metal palladium catalyst of Dynamic Kinetic Resolution benzyl carbinol to centrifugalize being used among the embodiment 23 with biology enzyme, with being applied in the reaction described in the embodiment 2 for the 5th time after the washing with alcohol.Obtaining conversion ratio is 98%, and optical purity is 99.6%, and chemical purity is 99% ester.
Embodiment 25
Combine the supported metal palladium catalyst of Dynamic Kinetic Resolution benzyl carbinol to centrifugalize being used among the embodiment 24 with biology enzyme, with being applied in the reaction described in the embodiment 2 for the 6th time after the washing with alcohol.Obtaining conversion ratio is 97%, and optical purity is 99.5%, and chemical purity is 99% ester.
Can find out that from experimental result the supported metal palladium catalyst of the present invention's preparation can combine to be used for the Dynamic Kinetic Resolution of secondary alcohol with biology enzyme, catalytic performance is much better than the supported metal palladium catalyst of traditional immersion reduction method preparation.Not only realized in the one pot reaction system efficient fractionation, and can be repeatedly used, greatly reduced cost secondary alcohol.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.So everyly do not break away from the equivalence of accomplishing under the disclosed spirit of the present invention or revise, all fall into the scope of the present invention's protection.
Claims (6)
1. supported metal palladium catalyst, it is characterized in that: its content of metal is 1.0-5.0wt%, specific area is 300-900m
2/ g, pore volume are 0.3-1.0cm
3/ g, the aperture is 3.0-10.0nm, the metallic particles diameter is 1.0-8.0nm.
2. the described supported metal palladium catalyst of claim 1, it is characterized in that: its content of metal is 2.8-3.0wt%, specific area is 612-620m
2/ g, pore volume are 0.8-1.0cm
3/ g, the aperture is 3.0-3.3nm, the metallic particles diameter is 3.0-6.0nm.
3. the preparation method of the said supported metal palladium catalyst of claim 1 is characterized in that: comprise the steps:
(1) under inert gas shielding, palladium salt is dissolved in the oleyl amine, obtaining concentration is the palladium salting liquid of 0.5-10mg/mL, with 3-5 ℃/min temperature programming to 50-80 ℃; With mass concentration is that the oleyl amine solution of the tert-butylamine borine of 8-15% is poured in the above-mentioned palladium salting liquid, and the mol ratio of tert-butylamine borine and palladium is 8:1-20:1; With above-mentioned solution with 1-5 ℃/min temperature programming to 80-120 ℃; Kept 10-100 minute at 80-120 ℃ then; Add 1-3 times of volume absolute ethyl alcohol after being cooled to room temperature, centrifugation, products obtained therefrom is dispersed in and forms metal concentration in the n-hexane is the solution of 0.05-0.6mg/mL;
(2) under 0-30 ℃, mesoporous silicon oxide SBA-15 is immersed in the above-mentioned solution, the mass ratio that mesoporous silicon oxide SBA-15 and GOLD FROM PLATING SOLUTION belong to is 200-300:1, the ultrasonic 1-5h of 20-50W, centrifugation, washing, 80-120 ℃ of vacuum drying 1-5h;
(3) solid-to-liquid ratio of step (2) products obtained therefrom according to 10-30mg/mL added in the toluene, add the MTES of 2-20% volume again, 50-120 ℃ of reflux 1-15h promptly obtains supported metal palladium catalyst.
4. the preparation method of the described supported metal palladium catalyst of claim 3, it is characterized in that: said palladium salt is palladium inorganic salts or organic salt.
5. the preparation method of the described supported metal palladium catalyst of claim 3, it is characterized in that: said palladium salt is palladium acetylacetonate.
6. claim 1 or 2 described supported metal palladium catalysts combine to be used for the Dynamic Kinetic Resolution of secondary alcohol with lipase.
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| CN106824181A (en) * | 2017-02-24 | 2017-06-13 | 安徽师范大学 | Nanotube-palladium composite material and preparation method thereof |
| CN109395721A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | Load type palladium catalyst and preparation method thereof |
| CN110354852A (en) * | 2018-03-26 | 2019-10-22 | 中国科学院大连化学物理研究所 | A kind of support type rhodium base catalyst, preparation method and in synthesis gas C2Application in oxycompound |
| CN110465311A (en) * | 2019-08-22 | 2019-11-19 | 青岛大学 | A kind of bismuth sulfide-palladium composite nano materials, preparation method and application |
| CN111905826A (en) * | 2020-08-20 | 2020-11-10 | 河南师范大学 | Preparation method and application of heterogeneous yeast supported chiral metal ruthenium catalyst |
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| CN102078818A (en) * | 2010-12-27 | 2011-06-01 | 中南民族大学 | Catalyst using SBA-16 molecular sieve as carrier, and preparation method and application thereof |
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| CN106824181A (en) * | 2017-02-24 | 2017-06-13 | 安徽师范大学 | Nanotube-palladium composite material and preparation method thereof |
| CN109395721A (en) * | 2017-08-16 | 2019-03-01 | 王学彬 | Load type palladium catalyst and preparation method thereof |
| CN110354852A (en) * | 2018-03-26 | 2019-10-22 | 中国科学院大连化学物理研究所 | A kind of support type rhodium base catalyst, preparation method and in synthesis gas C2Application in oxycompound |
| CN110354852B (en) * | 2018-03-26 | 2021-05-25 | 中国科学院大连化学物理研究所 | Supported rhodium-based catalyst, preparation method thereof and method for preparing C from synthesis gas2Use in oxygenates |
| CN110465311A (en) * | 2019-08-22 | 2019-11-19 | 青岛大学 | A kind of bismuth sulfide-palladium composite nano materials, preparation method and application |
| CN110465311B (en) * | 2019-08-22 | 2022-03-18 | 青岛大学 | Bismuth sulfide-palladium composite nanomaterial, preparation method and application |
| CN111905826A (en) * | 2020-08-20 | 2020-11-10 | 河南师范大学 | Preparation method and application of heterogeneous yeast supported chiral metal ruthenium catalyst |
| CN111905826B (en) * | 2020-08-20 | 2023-03-31 | 河南师范大学 | Preparation method and application of heterogeneous yeast supported chiral metal ruthenium catalyst |
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