CN105195228A - Fe3O4-loaded chiral catalyst and preparation method and application thereof - Google Patents

Fe3O4-loaded chiral catalyst and preparation method and application thereof Download PDF

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CN105195228A
CN105195228A CN201510643236.1A CN201510643236A CN105195228A CN 105195228 A CN105195228 A CN 105195228A CN 201510643236 A CN201510643236 A CN 201510643236A CN 105195228 A CN105195228 A CN 105195228A
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chiral catalyst
catalyst
nanosphere
preparation
reaction
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CN105195228B (en
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李新娟
杨蓓蕾
贾献彬
胡志国
朱双营
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Henan Normal University
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Henan Normal University
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Abstract

The invention discloses a Fe3O4-loaded chiral catalyst and a preparation method and application thereof and belongs to the technical field of chiral catalysis and asymmetric synthesis. According to a technical scheme, the Fe3O4-loaded chiral catalyst is formed by copolymerizing Fe3O4 nanospheres each having a double-bonded surface and a chiral monomer having a chemical formula shown below; this catalyst has a structure shown below. The invention further discloses the preparation method of the Fe3O4-loaded chiral catalyst and application of the Fe3O4-loaded chiral catalyst in Diels-Alder cycloaddition reaction. The Fe3O4-loaded chiral catalyst may be separated by magnetic attraction as one end of a polymer chain is fixed to one magnetic Fe3O4 nanosphere insoluble in a reaction medium, via a covalent bond; this catalyst has the advantage that the catalyst a heterogeneous catalyst is easy to recover and reusable.

Description

A kind of Fe 3o 4load type chiral catalyst and its preparation method and application
Technical field
The invention belongs to chiral catalysis and asymmetric syntheses technical field, be specifically related to a kind of Fe 3o 4load type chiral catalyst and its preparation method and application.
Background technology
In recent years, Chiral Amine catalysis development rapidly, is the research topic of core in asymmetric organocatalysis synthesis, and the chemist of a lot of industrial quarters and academia drops into wherein to be studied.Chiral Amine load to be can yet be regarded as a kind of good method, such as, MacMillan chiral imidazole alkane ketone loaded on silica gel in 2006 by Jackie group, and by this catalyst application in Friedel-Crafts alkylated reaction and Diels-Alder cycloaddition reaction, catalyst can realize well reclaiming use, but the enantioselectivity of the catalyst of the relative non-catalytic of this catalyst reduces a lot.And magnetic nanoparticle has that specific area is large, Active sites is many, surface reaction activity is high, high adsorption capacity and the excellent properties such as catalytic efficiency is high, provide necessary condition for nano particle is used for catalyst, thus it has important application in catalysis.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of Fe 3o 4load type chiral catalyst and preparation method thereof, utilize this load type chiral catalyst in catalytic asymmetric reaction except obtaining the chiral product of high yield and highly-solid selectively, the feature that the Magneto separate repeating that can also realize catalyst recycles, reduces production cost, this Fe 3o 4load type chiral catalyst can be applicable in Diels-Alder cycloaddition reaction.
The present invention adopts following technical scheme, a kind of Fe for solving the problems of the technologies described above 3o 4load type chiral catalyst, it is characterized in that the Fe by surface being had double bond 3o 4nanosphere and chiral monomer the Fe that copolymerization is formed 3o 4load type chiral catalyst, it has following structure:
。
Fe of the present invention 3o 4the preparation method of load type chiral catalyst, is characterized in that concrete steps are: (1) surface has the Fe of double bond 3o 4the preparation of nanosphere, by the Fe of 1-5g 3o 4nanosphere joins in the round-bottomed flask that 100-500mL toluene is housed, stir after adding 3-(trimethoxysilyl) propyl acrylate of 5.23-52.25mL again, in 20-60 DEG C of reaction 24h after logical nitrogen 30min, respectively wash 5 times with ethyl acetate and ethanol after reacting completely, vacuum drying 48h obtains the Fe that surface has double bond 3o 4nanosphere, (2) Fe 3o 4the preparation of load type chiral catalyst, takes the Fe that surface has double bond 3o 4nanosphere 0.1-0.5g joins in reaction bulb, chiral monomer 1.209-6.047g is added successively after ultrasonic disperse 5-30min, dithiobenzoic acid cumenyl ester 10.85-54.27mg ﹑ azo-bis-isobutyl cyanide 1.33-6.67mg and dimethyl formamide 3.33-16.67mL, sealing after dissolving completely, oxygen in the mode removing system that employing freeze thawing is 5 times, reaction bulb is placed in oil bath pan in 40-100 DEG C of stirring reaction 24h, after reaction terminates, Magneto separate, solid product uses oxolane and each centrifugal three times of methyl alcohol successively, solid product is placed in vacuum drying chamber obtains load Macmillan chiral catalyst Fe in 30 DEG C of vacuum drying 48h 3o 4nanosphere.
Further restriction, described Fe 3o 4the concrete preparation process of nanosphere is: (1) takes FeCl 36H 2o and FeCl 24H 2o is placed in round bottom three-necked bottle, wherein FeCl 36H 2o and FeCl 24H 2the mol ratio of O is 2:1, then adds 200mL deionized water, stirs and uses nitrogen bubble, duration 10min; (2) FeCl is treated 36H 2o and FeCl 24H 2stop nitrogen bubble after O solid fully dissolves, continue stir and drip concentrated ammonia liquor under nitrogen atmosphere, stop as the pH=9 of mixed system dripping concentrated ammonia liquor, stir 20min under nitrogen atmosphere; (3) round bottom three-necked bottle is transferred in oil bath pan, after continuing to stir 30min under nitrogen atmosphere, stops agitating heating, stop logical nitrogen, be cooled to after room temperature until it, staticly settled; (4) solution left standstill in round bottom three-necked bottle is after one day, be placed in magnetic field and outwell supernatant liquor, then 5 times are respectively washed with deionized water and absolute ethyl alcohol, sediment to be transferred in surface plate and with ethanol by the flushes sediment that adheres in round bottom three-necked bottle in surface plate, sediment is spread out equably, outwell supernatant liquor after leaving standstill, cover filter paper and fix, then this surface plate being put into vacuum drying chamber in 40 DEG C of vacuum drying two days; (5) the abundant drying of the sediment in surface plate two days later, by another surface plate back-off on it, and magnet is positioned over the top of another surface plate, with this, impurity is separated with desired magnetic-particle, and collect magnetic-particle, this operating procedure obtains Fe to purify repeatedly 3o 4magnetic nanoparticle.
Further restriction, described Fe 3o 4concrete synthetic route in the preparation method of load type chiral catalyst is:
。
Fe of the present invention 3o 4the application of load type chiral catalyst in Diels-Alder cycloaddition reaction, wherein Fe 3o 4after load type chiral catalyst is reclaimed by Magnetic Isolation, repetitive cycling uses.
The present invention compared with prior art has the following advantages: the simple and environmental protection of the preparation method of (1) loaded catalyst; (2) magnetic nanoparticle has that specific area is large, Active sites is many, surface reaction activity is high and the excellent properties such as high adsorption capacity, reasonable stability is had: the polymer chain that (3) hang can improve the dispersiveness of particle in reaction medium by after itself and Macmillan chiral catalyst bonding, thus improve the catalytic activity of catalyst further, and high catalytic activity can be demonstrated as solubility line polymer carried catalyst; (4) because one end of polymer chain is being insoluble to the magnetic Fe of reaction medium with covalently immobolization 3o 4on nanosphere, be separated by magnet adsorption, there is heterogeneous catalysis and easily reclaim and reusable advantage.
Detailed description of the invention
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Fe 3o 4the preparation of nanosphere
(1) FeCl is taken 36H 2o and FeCl 24H 2o is placed in round bottom three-necked bottle, wherein FeCl 36H 2o and FeCl 24H 2the mol ratio of O is 2:1, then adds 200mL deionized water, stirs and uses nitrogen bubble, duration 10min; (2) FeCl is treated 36H 2o and FeCl 24H 2stop nitrogen bubble after O solid fully dissolves, continue stir and drip concentrated ammonia liquor under nitrogen atmosphere, stop as the pH=9 of mixed system dripping concentrated ammonia liquor, stir 20min under nitrogen atmosphere; (3) round bottom three-necked bottle is transferred in oil bath pan, after continuing to stir 30min under nitrogen atmosphere, stops agitating heating, stop logical nitrogen, be cooled to after room temperature until it, staticly settled; (4) solution left standstill in round bottom three-necked bottle is after one day, be placed in magnetic field and outwell supernatant liquor, then 5 times are respectively washed with deionized water and absolute ethyl alcohol, sediment to be transferred in surface plate and with ethanol by the flushes sediment that adheres in round bottom three-necked bottle in surface plate, sediment is spread out equably, outwell supernatant liquor after leaving standstill, cover filter paper and fix, then this surface plate being put into vacuum drying chamber in 40 DEG C of vacuum drying two days; (5) the abundant drying of the sediment in surface plate two days later, by another surface plate back-off on it, and magnet is positioned over the top of another surface plate, with this, impurity is separated with desired magnetic-particle, and collect magnetic-particle, this operating procedure obtains Fe to purify repeatedly 3o 4magnetic nanoparticle.
Embodiment 2
Surface has the Fe of double bond 3o 4the preparation of nanosphere
By the Fe of 2g 3o 4nanosphere joins and is equipped with in the 500mL round-bottomed flask of 200mL toluene, stir after adding 3-(trimethoxysilyl) propyl acrylate of 10.45mL again, after logical nitrogen 30min, 25 DEG C of reaction 24h, respectively wash 5 times with ethyl acetate and ethanol after reacting completely, vacuum drying 48h obtains the Fe that surface has double bond 3o 4nanosphere.
Embodiment 3
Surface has the Fe of double bond 3o 4the preparation of nanosphere
By the Fe of 1g 3o 4nanosphere joins and is equipped with in the 500mL round-bottomed flask of 100mL toluene, stir after adding 3-(trimethoxysilyl) propyl acrylate of 5.23mL again, after logical nitrogen 30min, 20 DEG C of reaction 24h, respectively wash 5 times with ethyl acetate and ethanol after reacting completely, vacuum drying 48h obtains the Fe that surface has double bond 3o 4nanosphere.
Embodiment 4
Surface has the Fe of double bond 3o 4the preparation of nanosphere
By the Fe of 5g 3o 4nanosphere joins and is equipped with in the 1000mL round-bottomed flask of 500mL toluene, stir after adding 3-(trimethoxysilyl) propyl acrylate of 52.25mL again, after logical nitrogen 30min, 60 DEG C of reaction 24h, respectively wash 5 times with ethyl acetate and ethanol after reacting completely, vacuum drying 48h obtains the Fe that surface has double bond 3o 4nanosphere.
Embodiment 5
Fe 3o 4the preparation of load type chiral catalyst
Take the Fe that surface has double bond 3o 4nanosphere 0.15g joins in reaction bulb, after ultrasonic disperse 5min, add chiral monomer 1.814g successively, dithiobenzoic acid cumenyl ester 16.28mg ﹑ azo-bis-isobutyl cyanide 2mg and dimethyl formamide 5mL, sealing after dissolving completely, oxygen in the mode removing system that employing freeze thawing is 5 times, reaction bulb is placed in oil bath pan in 70 DEG C of stirring reaction 24h, reaction terminates rear Magneto separate, solid product uses oxolane and each centrifugal three times of methyl alcohol successively, solid product is placed in vacuum drying chamber obtains load Macmillan chiral catalyst Fe in 30 DEG C of vacuum drying 48h 3o 4nanosphere.
Embodiment 6
Fe 3o 4the preparation of load type chiral catalyst
Take the Fe that surface has double bond 3o 4nanosphere 0.1g joins in reaction bulb, after ultrasonic disperse 10min, add chiral monomer 1.209g successively, dithiobenzoic acid cumenyl ester 10.85mg ﹑ azo-bis-isobutyl cyanide 1.33mg and dimethyl formamide 3.33mL, sealing after dissolving completely, oxygen in the mode removing system that employing freeze thawing is 5 times, reaction bulb is placed in oil bath pan in 40 DEG C of stirring reaction 24h, reaction terminates rear Magneto separate, solid product uses oxolane successively, each centrifugal three times of methyl alcohol, solid product is placed in vacuum drying chamber obtains load Macmillan chiral catalyst Fe in 30 DEG C of vacuum drying 48h 3o 4nanosphere.
Embodiment 7
Fe 3o 4the preparation of load type chiral catalyst
Take the Fe that surface has double bond 3o 4nanosphere 0.5g joins in reaction bulb, after ultrasonic disperse 30min, add chiral monomer 6.047g successively, dithiobenzoic acid cumenyl ester 45.27mg ﹑ azo-bis-isobutyl cyanide 6.67mg and dimethyl formamide 16.67mL, sealing after dissolving completely, oxygen in the mode removing system that employing freeze thawing is 5 times, reaction bulb is placed in oil bath pan in 100 DEG C of stirring reaction 24h, reaction terminates rear Magneto separate, solid product uses oxolane and each centrifugal three times of methyl alcohol successively, solid product is placed in vacuum drying chamber obtains load Macmillan chiral catalyst Fe in 30 DEG C of vacuum drying 48h 3o 4nanosphere.
Embodiment 8
The Fe of the obtained load Macmillan catalyst of the amount 10% of substrate materials is added in test tube 3o 4nanosphere, acetonitrile/water (0.6mL), trifluoroacetic acid (0.0114g, 0.1mmol), cyclopentadiene (0.168mL, 1.96mmol), cinnamic acid (0.0636mL, 0.48mmol), 24h is reacted under room temperature, thin-layer chromatography follows the tracks of reaction to terminal, after completion of the reaction, centrifugation, lower floor's solids with methanol washes 3 times, recycle and reuse, supernatant ether (3 × 10mL) extracts three times, merge organic phase, concentrated, pure addition compound product (benzinum: ethyl acetate=50:1) is obtained through column chromatography for separation, to weigh calculating productive rate, proton nmr spectra confirms target product.Appropriate NaBH is added in product 4, room temperature reaction 48h.30h reaction 75%.After completion of the reaction, be spin-dried for solvent, add q. s. methylene chloride, with distillation washing 3 times, collect organic phase, concentrate and obtain pure products (benzinum: ethyl acetate=16:1) through column chromatography for separation.By high performance liquid chromatography (HPLC) OJ-H chiral column separating chiral material, obtaining ee value is 41.5%, 99%.
Embodiment 9
The Fe3O4 nanosphere of the obtained load Macmillan catalyst of the amount 10% of substrate materials is added in test tube, water (0.6mL), trifluoroacetic acid (0.0114g, 0.1mmol), cyclopentadiene (0.168mL, 1.96mmol), cinnamic acid (0.0636mL, 0.48mmol), 24h is reacted under room temperature, thin-layer chromatography follows the tracks of reaction to terminal, after completion of the reaction, centrifugation, lower floor's solids with methanol fully washs 3 times, vacuum drying is reclaimed, supernatant ether (3 × 10mL) extracts three times, merge organic phase, concentrated, pure addition compound product (benzinum: ethyl acetate=50:1) is obtained through column chromatography for separation, to weigh calculating productive rate, proton nmr spectra confirms target product.Appropriate NaBH is added in product 4, room temperature reaction 48h.30h reaction 80%.After completion of the reaction, be spin-dried for solvent, add q. s. methylene chloride, with distillation washing 3 times, collect organic phase, concentrate and obtain pure products (benzinum: ethyl acetate=16:1) through column chromatography for separation.By high performance liquid chromatography (HPLC) OJ-H chiral column separating chiral material, obtaining ee value is 71.29%, 65.09%.
Embodiment 10
By the Fe of the load Macmillan catalyst of recovery in embodiment 8 3o 4nanosphere repeats embodiment 8 as chiral catalyst.30h reaction 75%.Obtaining ee value is 45%, 99%.
Embodiment 11
By the Fe of the load Macmillan catalyst of recovery in embodiment 9 3o 4nanosphere repeats embodiment 9 as chiral catalyst.30h reaction 70%.Obtaining ee value is 71.5%, 65%.
Embodiment 12
By the Fe of the load Macmillan catalyst of recovery in embodiment 10 3o 4nanosphere repeats embodiment 8 as chiral catalyst.30h reaction 80%.Obtaining ee value is 40%, 95%.
Embodiment 13
By the Fe of the load Macmillan catalyst of recovery in embodiment 11 3o 4nanosphere repeats embodiment 9 as chiral catalyst.30h reaction 75%.Obtaining ee value is 70.5%, 69%.
Embodiment above describes general principle of the present invention, principal character and advantage; the technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.

Claims (5)

1. a Fe 3o 4load type chiral catalyst, it is characterized in that the Fe by surface being had double bond 3o 4nanosphere and chiral monomer the Fe that copolymerization is formed 3o 4load type chiral catalyst, it has following structure:
。
2. a Fe according to claim 1 3o 4the preparation method of load type chiral catalyst, is characterized in that concrete steps are: (1) surface has the Fe of double bond 3o 4the preparation of nanosphere, by the Fe of 1-5g 3o 4nanosphere joins in the round-bottomed flask that 100-500mL toluene is housed, stir after adding 3-(trimethoxysilyl) propyl acrylate of 5.23-52.25mL again, in 20-60 DEG C of reaction 24h after logical nitrogen 30min, respectively wash 5 times with ethyl acetate and ethanol after reacting completely, vacuum drying 48h obtains the Fe that surface has double bond 3o 4nanosphere, (2) Fe 3o 4the preparation of load type chiral catalyst, takes the Fe that surface has double bond 3o 4nanosphere 0.1-0.5g joins in reaction bulb, chiral monomer 1.209-6.047g is added successively after ultrasonic disperse 5-30min, dithiobenzoic acid cumenyl ester 10.85-54.27mg ﹑ azo-bis-isobutyl cyanide 1.33-6.67mg and dimethyl formamide 3.33-16.67mL, sealing after dissolving completely, oxygen in the mode removing system that employing freeze thawing is 5 times, reaction bulb is placed in oil bath pan in 40-100 DEG C of stirring reaction 24h, after reaction terminates, Magneto separate, solid product uses oxolane and each centrifugal three times of methyl alcohol successively, solid product is placed in vacuum drying chamber obtains load Macmillan chiral catalyst Fe in 30 DEG C of vacuum drying 48h 3o 4nanosphere.
3. Fe according to claim 2 3o 4the preparation method of load type chiral catalyst, is characterized in that described Fe 3o 4the concrete preparation process of nanosphere is: (1) takes FeCl 36H 2o and FeCl 24H 2o is placed in round bottom three-necked bottle, wherein FeCl 36H 2o and FeCl 24H 2the mol ratio of O is 2:1, then adds 200mL deionized water, stirs and uses nitrogen bubble, duration 10min; (2) FeCl is treated 36H 2o and FeCl 24H 2stop nitrogen bubble after O solid fully dissolves, continue stir and drip concentrated ammonia liquor under nitrogen atmosphere, stop as the pH=9 of mixed system dripping concentrated ammonia liquor, stir 20min under nitrogen atmosphere; (3) round bottom three-necked bottle is transferred in oil bath pan, after continuing to stir 30min under nitrogen atmosphere, stops agitating heating, stop logical nitrogen, be cooled to after room temperature until it, staticly settled; (4) solution left standstill in round bottom three-necked bottle is after one day, be placed in magnetic field and outwell supernatant liquor, then 5 times are respectively washed with deionized water and absolute ethyl alcohol, sediment to be transferred in surface plate and with ethanol by the flushes sediment that adheres in round bottom three-necked bottle in surface plate, sediment is spread out equably, outwell supernatant liquor after leaving standstill, cover filter paper and fix, then this surface plate being put into vacuum drying chamber in 40 DEG C of vacuum drying two days; (5) the abundant drying of the sediment in surface plate two days later, by another surface plate back-off on it, and magnet is positioned over the top of another surface plate, with this, impurity is separated with desired magnetic-particle, and collect magnetic-particle, this operating procedure obtains Fe to purify repeatedly 3o 4magnetic nanoparticle.
4. Fe according to claim 2 3o 4the preparation method of load type chiral catalyst, is characterized in that described Fe 3o 4concrete synthetic route in the preparation method of load type chiral catalyst is:
。
5. Fe according to claim 1 3o 4the application of load type chiral catalyst in Diels-Alder cycloaddition reaction, wherein Fe 3o 4after load type chiral catalyst is reclaimed by Magnetic Isolation, repetitive cycling uses.
CN201510643236.1A 2015-10-08 2015-10-08 A kind of Fe3O4Load type chiral catalyst and its preparation method and application Expired - Fee Related CN105195228B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105854950A (en) * 2016-05-03 2016-08-17 河南师范大学 Supported chiral catalyst magnetic nanoparticles and preparation method and application thereof
CN115007203A (en) * 2022-04-13 2022-09-06 南京信息工程大学 Organic amine modified manganese dioxide catalyst and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1097011A (en) * 1993-06-26 1995-01-04 河南师范大学 A kind of medicine and preparation technology thereof who treats enteritis and ulcerative colitis
JP2010013392A (en) * 2008-07-03 2010-01-21 Tokyo Univ Of Science Manufacturing method and purification method of asymmetric diels-alder reaction product, and asymmetric catalyst and asymmetric catalyst mixture
CN103601856A (en) * 2013-11-08 2014-02-26 河南师范大学 Supported chiral catalyst polymer microspheres, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1097011A (en) * 1993-06-26 1995-01-04 河南师范大学 A kind of medicine and preparation technology thereof who treats enteritis and ulcerative colitis
JP2010013392A (en) * 2008-07-03 2010-01-21 Tokyo Univ Of Science Manufacturing method and purification method of asymmetric diels-alder reaction product, and asymmetric catalyst and asymmetric catalyst mixture
CN103601856A (en) * 2013-11-08 2014-02-26 河南师范大学 Supported chiral catalyst polymer microspheres, and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
VAN HOA NGUYEN ET AL.,: "Supercritical fluid mediated synthesis of poly(2-hydroxyethyl methacrylate)/Fe3O4 hybrid nanocomposite", 《MATERIALS SCIENCE AND ENGINEERING B》 *
张苏利: "负载手性催化剂的毛发状微球的制备及其在不对称合成反应中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105854950A (en) * 2016-05-03 2016-08-17 河南师范大学 Supported chiral catalyst magnetic nanoparticles and preparation method and application thereof
CN105854950B (en) * 2016-05-03 2019-01-18 河南师范大学 A kind of loaded chiral catalyst magnetic nano-particle and its preparation method and application
CN115007203A (en) * 2022-04-13 2022-09-06 南京信息工程大学 Organic amine modified manganese dioxide catalyst and preparation method and application thereof

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