CN104117392A - Supported catalyst and preparation method thereof - Google Patents

Supported catalyst and preparation method thereof Download PDF

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Publication number
CN104117392A
CN104117392A CN201310157771.7A CN201310157771A CN104117392A CN 104117392 A CN104117392 A CN 104117392A CN 201310157771 A CN201310157771 A CN 201310157771A CN 104117392 A CN104117392 A CN 104117392A
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formula
compound
loaded catalyst
catalyst
slaine
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应安国
张群辉
蒋志斌
李维金
苏国平
陈文洁
胡华南
吕祖平
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JIANGSU HAIKUP BIOLOGICAL PHARMACEUTICAL Co Ltd
Zhejiang Hisoar Pharmaceutical Co Ltd
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JIANGSU HAIKUP BIOLOGICAL PHARMACEUTICAL Co Ltd
Zhejiang Hisoar Pharmaceutical Co Ltd
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Abstract

The invention provides a supported catalyst with the structural formula I shown in the specification. In the formula I, a carrier is superparamagnetic nanoparticles or superparamagnetic nanoparticles wrapped by silicon dioxide; M is metal ions, X<-> is inorganic or organic negative ions; R<1> is C1-C6 alkyl, halogen substituted C1-C6 alkyl, C6-C12 aryl, halogen or C1-C6 alkyl substituted C6-C12 aryl, halogen or C1-C4 alkoxy; R<2> and R<3> are respectively C1-C6 alkyl or C6-C12 aryl, or R<2> and R<3> are connected with each other to form -(CH2)3- or -(CH2)4-; a linker is a connector. The invention further discloses a preparation method of the supported catalyst. The supported catalyst can be used as a chiral catalyst for asymmetric epoxidation reaction.

Description

A kind of loaded catalyst and preparation method thereof
Technical field
The present invention relates to new chemical material and preparing technical field, specifically, relate to a kind of novel support type chiral catalyst and preparation method thereof, can be used in asymmetric epoxidation reaction.
Background technology
At medicine synthetic and agricultural chemicals synthetic in, asymmetric Epoxidation addition alkene becomes the important technology of the crucial chiral intermediate of preparation.The chiral epoxy compound obtaining more easily transfers the synthetic stripping and slicing of various chiralitys to, such as alcohol, glycol and amino alcohol etc.
As far back as 19th century, Salen manganese reagent (also referred to as Jacobsen-Katsuki catalyst) is just applied in the Enantoselective epoxidation of alkene with homogeneous catalyst form.
Consider the features such as the easy recovery reusability of heterogeneous catalysis is good and post processing is easy, a lot of chemists by Jacobsen-Katsuki catalyst cupport to various solids.Carrier generally comprises silica gel, diatomite, aluminium oxide, polymer and molecular sieve etc.
Although above method has solved the recovery problem of catalyst, the problem of also having brought catalytic effect to decline simultaneously.Research is found, may be that above carrier specific area is too little, and much the duct of catalyst inside can stop entering of reaction substrate and reagent, therefore causes the decline of reaction yield and enantioselectivity.
Therefore, the loaded catalyst of development of new is applied to the Enantoselective epoxidation reaction of alkene, has special meaning in the exploitation of organic synthesis, particularly green cleaning procedure.
Summary of the invention
The object of the invention is to provide a kind of novel imidazole type catalysis of functional ionic liquid agent based on chirality Salen reagent, the load of superparamagnetic nano particle, and the preparation method of this class catalyst is provided.
Superparamagnetic nano particle has obtained research application widely at biomedicine field.As catalyst carrier, it has two a little: the one, there is very bigger serface, and make the catalyst activity of load keep close with parent or identical; The 2nd, because it is magnetic, therefore can separate recovery catalyst by externally-applied magnetic field.
As everyone knows, ionic liquid is to be made up of organic cation and inorganic or organic anion, is the salt of liquid condition under room temperature or near room temperature.Ionic liquid has low volatility, low melting point, structure designability, broadening window, the good advantage such as electric conductivity and good solubility property, and it is all widely used in every field.In " ionic liquid-character, preparation and application " (Sinopec publishing house, 2006.7.1 publishes) book of writing at Deng Youquan, introduce the application of ionic liquid at all kinds of organic synthesis operating units.This book mode is by reference incorporated in the application.
If introduce " ion atmosphere " of ionic liquid on the chiral molecules of superparamagnetic nano load particulate load, can stablize epoxy reactive transition state, the activated energy barrier that reduces reaction, may make the activity keeping of catalyst even be better than the chiral catalysis ability before load.
According to object of the present invention, the invention provides the loaded catalyst shown in a kind of following structural formula I.Described loaded catalyst is the imidazole type functional ion liquid based on chirality Salen reagent, the load of superparamagnetic nano particle.
Wherein,
Carrier is the superparamagnetic nano particle of superparamagnetic nano particle or silica inclusion;
M is metal ion;
X -for inorganic or organic anion;
R 1for C 1～C 6the C that alkyl, halogen replace 1～C 6alkyl, C 6～C 12aryl (for example phenyl), halogen or C 1～C 6the C that alkyl replaces 6～C 12aryl (for example phenyl), halogen or C 1～C 4alkoxyl;
R 2and R 3be C independently of one another 1～C 6alkyl or C 6～C 12aryl (for example phenyl); Or R 2and R 3be connected to form-(CH 2) 3-or-(CH 2) 4-;
Linker is connector-O 3si-(CH 2) n-NH-C (O)-or-O 3si-(CH 2) n-, the integer that n is 1～7.
Described dotted line represents complex bonds.
Described alkyl can be straight or branched.
Described C 6～C 12aryl is preferably phenyl.
T-Bu represents the tert-butyl group.
Preferably, described carrier is the tri-iron tetroxide superparamagnetic nano particle of tri-iron tetroxide superparamagnetic nano particle or silica inclusion.
More preferably, described carrier is the tri-iron tetroxide superparamagnetic nano particle of silica inclusion.
Preferably, described M is Mn ion or Co ion; Described X -for Cl -, BF 4 -, PF 6 -, OTf -(TFMS root), NTf 2 -(two fluoroform sulfimide root), CH 3cOO -, CH 3cH 2cOO -, CH 3cH 2cH 2cOO -or CH 3cH (OH) COO -;
More preferably, described M is Mn ion; Described X -for BF 4 -, PF 6 -or NTf 2 -.
Preferably, described linker is-O 3si-(CH 2) 3-NH-C (O)-or-O 3si-(CH 2) 3-.
Preferably, described R 1for-CH 2cl or the tert-butyl group; R 2and R 3be phenyl simultaneously, or R 2and R 3be connected to form-(CH 2) 4-.
More preferably, loaded catalyst of the present invention is specially:
In addition, the present invention also provides a kind of preparation method of described loaded catalyst, it comprise with
Lower step:
(1) make formula III compound react and obtain formula II compound with formula IV compound;
(2) formula II compound is reacted with slaine and lithium chloride, and then carry out ion-exchange reactions with ionic liquid, obtain formula I compound;
Wherein, R is-CH 2-Y, Y is halogen;
Cation in described slaine is M;
Anion in described ionic liquid is X -;
Described carrier, R 1, R 2, R 3identical with description above with the definition of linker.
Preferably, described slaine is manganese metal salt or Cobalt salts; More preferably Mn (OAc) 24H 2o or Co (OAc) 24H 2o.
Preferably, described ionic liquid is NaX, KX or LiX.
Preferably, in step (1), the mol ratio of formula III compound and formula IV compound is 1:1～2; The solvent using is selected from carrene, oxolane and toluene; Reaction temperature is 10～110 DEG C; Reaction time is 12～96 hours.
Preferably, in step (2), the mol ratio of formula II compound and slaine is 1:1～1.5; The mol ratio of formula II compound and lithium chloride is 1:1～1.5; The solvent that formula II compound reacts with slaine and lithium chloride is selected from ethanol, methyl alcohol or toluene; Under reflux temperature, react 0.5～5 hour.
More preferably, in step (2), after formula II compound has reacted with slaine and lithium chloride, hold solid with externally-applied magnetic field, abandon liquid, gained solid is put into methyl alcohol and is refluxed and carry out ion-exchange reactions, reacts 0.5～5 hour under reflux temperature; The mol ratio of its Chinese style II compound and ionic liquid is 1:1～1.5.
What formula IV compound comprised can be respectively according to document (Journal of Catalysis, 2007,249,102-110 as shown in the formula 1 compound, formula 2 compounds, formula 3 compounds and formula 4 compounds; Journal of Catalysis, 2008,256,226-236) prepare.Document mode is by reference incorporated in the application.
Formula 5 compounds that formula III compound comprises can prepare according to document (Green Chemistry, 2012,14,201-208.).Formula 6 compounds that formula III compound comprises can prepare according to document (Adv.Synth.Catal.2006,348,1743-1751).These two sections of documents mode is by reference incorporated in the application.
Preferably, the preparation method's of loaded catalyst of the present invention concrete operations are as follows:
The imidazolium compounds (formula 5 compounds or formula 6 compounds) of the tri-iron tetroxide superparamagnetic nano particle load of silica inclusion being selected from the solvent of carrene, oxolane and toluene, 12～96 hour obtains corresponding formula 7 compounds in 10～110 DEG C of reactions with formula 1 compound, formula 2 compounds, formula 3 compounds or formula 4 compounds of 1.0～2.0 times of moles.In formula 7 compounds, add the manganese metal salt (Mn (OAc) of 1.0～1.5 times of moles 24H 2or Cobalt salts (Co (OAc) O) 24H 2o), then add again the lithium chloride of 1.0～1.5 moles, in ethanol, methyl alcohol or toluene solution, reflux 0.5～5 hour, cooling, hold solid with externally-applied magnetic field, abandon liquid, gained solid is put into methyl alcohol, reflux and carry out ion-exchange reactions with the ionic liquid (NaX or KX) of 1～1.5 times of mole, obtain corresponding formula I compound, its reaction equation is as follows:
In addition, the invention provides described loaded catalyst as chiral catalyst the purposes in asymmetric epoxidation reaction.
For example:
Make formula A compound obtain described formula B compound through asymmetric epoxidation reaction.
Described asymmetric epoxidation reaction carries out under oxidant, additive and described loaded catalyst exist; Described oxidant is selected from clorox, hydrogen peroxide or metachloroperbenzoic acid; Described additive is selected from PPNO(4-phenylpyridine nitrogen oxide) or NMO(N-methyl morpholine nitrogen oxide).
Described formula A compound is with jinggangmeisu fermentation byproduct (1L (1; 3; 4/2)-4-amino-6-methylol-1; 2; 3-phloroglucite is raw material; first react and obtain 1L-(1,3,4/2 by amido protecting; 6)-4-[benzyloxycarbonyl group (amino)]-6-C-(methylol)-1; 2,3-phloroglucite is then eliminated reaction and is obtained 1L (1R)-(1 under paratoluensulfonyl chloride effect; 3; 4/2)-4-[benzyloxycarbonyl group (amino)]-6-methylene-1,2,3-phloroglucite (formula A compound).
Raw materials used (the 1L (1 of the present invention, 3,4/2)-4-amino-6-methylol-1,2, the preparation method of 3-phloroglucite can reference literature " exploitation of jinggangmeisu and catabolite thereof " (surname rising sun duckweed etc., external medical antibiotic fascicle, 2005,26 (6): 275～278).Document mode is by reference incorporated in the application.
Compared with prior art, the present invention has following remarkable result:
(1) the invention provides a kind of novel loaded catalyst, it is the imidazole type functional ion liquid based on chirality Salen reagent, the load of superparamagnetic nano particle, has developed the new varieties of supported ion liquid, and load capacity is large.
(2) preparation technology of the present invention is simple, and equipment investment is few, and product yield is high.
(3) loaded catalyst provided by the invention has asymmetric Epoxidation catalytic activity, and it is convenient to reclaim with externally-applied magnetic field, can be used as catalyst be applied to various alkene, particularly synthetic without the Enantoselective epoxidation of functional olefines in.
Detailed description of the invention
Below with reference to embodiment, the present invention will be further described, and embodiments of the invention are only for technical scheme of the present invention is described, and non-limiting the present invention.
The described confirmation such as TEM, FT-IR, XRD, elementary analysis and ICP-AES for loaded catalyst.
TEM adopts JEOL JEM-2010 projection Electronic Speculum; FT-IR adopts the infrared instrument of Nicolete (pressing potassium bromide troche); XRD adopts Bruker XRD D8 powder diffractometer; Elementary analysis adopts Vario MICRO elemental analyser; ICP-AES adopts ICP-9000 (N+M) detector.
Embodiment 1
Experimental provision is mainly there-necked flask, in order to stir fully, adopts mechanical agitation, system nitrogen protection.By the formula 5 compound (14.8g that accurately weigh, 10mmol, in imidazoles 0.68mmol/g), formula 1 compound (12mmol) and 80mL toluene is placed in flask, flask is placed in oil bath, under high-speed stirred, back flow reaction 24 hours, adds externally-applied magnetic field, pouring liquid, then add the Mn (OAc) of 15mmol 24H 2o, 60mL absolute ethyl alcohol, refluxes and adds lithium chloride (15mmol) to continue back flow reaction 1 hour after 1 hour, adds magnetic field, and pouring liquid, adds 100mL methyl alcohol, NaBF 4(15mmol) back flow reaction is after 10 hours, adds magnetic field, pouring liquid, and gained solid-liquid is again with absolute ether washing 3 times, and dry 5 hours of 60 DEG C, vacuum, obtains faint yellow solid 14.1g.Obtaining catalyst loadings through elementary analysis is 0.58mmol/g, the amount of yield 85%(based on imidazoles).X-ray powder diffraction (XRD) data show that there is broad peak at 2 θ angles between 20～30 °, show the existence of silica inclusion layer; Infrared (FT-IR) shows: 3153cm -1and 3106cm -1represent respectively the C-H stretching vibration peak on imidazole ring, 1566cm -1and 1545cm -1represent the stretching vibration peak of the two keys of imidazole ring C=C, 1632cm -1represent the vibration peak of the two keys of C=N, 3000cm -1absworption peak represent the vibration peak of tertiary butyl groups, 1550cm -1represent the absworption peak of manganese.ICP-AES confirms that manganese load capacity is 0.53mmol/g.
Embodiment 2
Experimental provision is mainly there-necked flask, in order to stir fully, adopts mechanical agitation, system nitrogen protection.By the formula 5 compound (14.8g that accurately weigh, 10mmol, in imidazoles 0.68mmol/g), formula 2 compounds (15mmol) and 80mL toluene is placed in flask, flask is placed in oil bath, under high-speed stirred, back flow reaction 24 hours, adds externally-applied magnetic field, pouring liquid, then add the Mn (OAc) of 15mmol 24H 2o, 80mL absolute ethyl alcohol, refluxes and adds lithium chloride (15mmol) to continue back flow reaction 1 hour after 1 hour, adds magnetic field, and pouring liquid, adds 100mL methyl alcohol, LiNTf 2(15mmol) back flow reaction is after 24 hours, adds magnetic field, pouring liquid, and gained solid-liquid is again with absolute ether washing 3 times, and dry 5 hours of 60 DEG C, vacuum, obtains faint yellow solid 14.6g.Obtaining catalyst loadings through elementary analysis is 0.56mmol/g, the amount of yield 82%(based on imidazoles).X-ray powder diffraction (XRD) data show that there is broad peak at 2 θ angles between 20～30 °, show the existence of silica inclusion layer; Infrared (FT-IR) shows: 3155cm -1and 3110cm -1represent respectively the C-H stretching vibration peak on imidazole ring, 1568cm -1and 1546cm -1represent the stretching vibration peak of the two keys of imidazole ring C=C, 1632cm -1represent the vibration peak of the two keys of C=N, 3005cm -1absworption peak represent the vibration peak of tertiary butyl groups, 1548cm -1represent the absworption peak of manganese.ICP-AES confirms that manganese load capacity is 0.50mmol/g.
Embodiment 3
Experimental provision is mainly there-necked flask, in order to stir fully, adopts mechanical agitation, system nitrogen protection.By the formula 6 compound (15.6g that accurately weigh, 10mmol, in imidazoles 0.64mmol/g), formula 3 compounds (13mmol) and 80mL toluene is placed in flask, flask is placed in oil bath, under high-speed stirred, back flow reaction 24 hours, adds externally-applied magnetic field, pouring liquid, then add the Mn (OAc) of 15mmol 24H 2o, 80mL absolute ethyl alcohol, refluxes and adds lithium chloride (15mmol) to continue back flow reaction 1 hour after 1 hour, adds magnetic field, and pouring liquid, adds 110mL methyl alcohol, KPF 6(15mmol) back flow reaction is after 12 hours, adds magnetic field, pouring liquid, and gained solid-liquid is again with absolute ether washing 3 times, and dry 5 hours of 60 DEG C, vacuum, obtains faint yellow solid 13.9g.Obtaining catalyst loadings through elementary analysis is 0.61mmol/g, the amount of yield 95%(based on imidazoles).X-ray powder diffraction (XRD) data show that there is broad peak at 2 θ angles between 20～30 °, show the existence of silica inclusion layer; Infrared (FT-IR) shows: 3156cm -1and 3102cm -1represent respectively the C-H stretching vibration peak on imidazole ring, 1564cm -1and 1543cm -1represent the stretching vibration peak of the two keys of imidazole ring C=C, 1630cm -1represent the vibration peak of the two keys of C=N, 2996cm -1absworption peak represent the vibration peak of tertiary butyl groups, 1548cm -1represent the absworption peak of manganese.ICP-AES confirms that manganese load capacity is 0.59mmol/g.
Embodiment 4
Experimental provision is mainly there-necked flask, in order to stir fully, adopts mechanical agitation, system nitrogen protection.By the formula 6 compound (15.6g that accurately weigh, 10mmol, in imidazoles 0.64mmol/g), formula 4 compounds (15mmol) and 100mL carrene be placed in flask, flask is placed in oil bath, under high-speed stirred, back flow reaction 24 hours, adds externally-applied magnetic field, pouring liquid, then add the Co (OAc) of 15mmol 24H 2o, 120mL absolute ethyl alcohol, refluxes and adds lithium chloride (15mmol) to continue back flow reaction 1 hour after 1 hour, adds magnetic field, pouring liquid, add 100mL methyl alcohol, NaOTf (15mmol) back flow reaction, after 24 hours, is added magnetic field, pouring liquid, gained solid-liquid is again with absolute ether washing 3 times, and dry 5 hours of 60 DEG C, vacuum, obtains faint yellow solid 12.7g.Obtaining catalyst loadings through elementary analysis is 0.49mmol/g, the amount of yield 76%(based on imidazoles).X-ray powder diffraction (XRD) data show that there is broad peak at 2 θ angles between 20～30 °, show the existence of silica inclusion layer; Infrared (FT-IR) shows: 3155cm -1and 3105cm -1represent respectively the C-H stretching vibration peak on imidazole ring, 1568cm -1and 1548cm -1represent the stretching vibration peak of the two keys of imidazole ring C=C, 1630cm -1represent the vibration peak of the two keys of C=N, 3000cm -1absworption peak represent the vibration peak of tertiary butyl groups, 1430cm -1represent the absworption peak of cobalt.ICP-AES confirms that cobalt loading is 0.45mmol/g.
Embodiment 5
Experimental provision is mainly there-necked flask, in order to stir fully, adopts mechanical agitation, system nitrogen protection.By the formula 5 compound (14.8g that accurately weigh, 10mmol, in imidazoles 0.68mmol/g), formula 1 compound (12mmol) and 100mL oxolane be placed in flask, flask is placed in oil bath, under high-speed stirred, back flow reaction 18 hours, adds externally-applied magnetic field, pouring liquid, then add the Co (OAc) of 12mmol 24H 2o, 100mL absolute ethyl alcohol, refluxes and adds lithium chloride (12mmol) to continue back flow reaction 1 hour after 2 hours, adds magnetic field, pouring liquid, add 100mL methyl alcohol, KOAc (12mmol) back flow reaction, after 12 hours, is added magnetic field, pouring liquid, gained solid-liquid is again with absolute ether washing 3 times, and dry 5 hours of 60 DEG C, vacuum, obtains faint yellow solid 14.0g.Obtaining catalyst loadings through elementary analysis is 0.57mmol/g, the amount of yield 84%(based on imidazoles).X-ray powder diffraction (XRD) data show that there is broad peak at 2 θ angles between 20～30 °, show the existence of silica inclusion layer; Infrared (FT-IR) shows: 3160cm -1and 3108cm -1represent respectively the C-H stretching vibration peak on imidazole ring, 1570cm -1and 1550cm -1represent the stretching vibration peak of the two keys of imidazole ring C=C, 1636cm -1represent the vibration peak of the two keys of C=N, 3002cm -1absworption peak represent the vibration peak of tertiary butyl groups, 1431cm -1represent the absworption peak of cobalt.ICP-AES confirms that cobalt loading is 0.48mmol/g.
Embodiment 6
Experimental provision is mainly there-necked flask, in order to stir fully, adopts mechanical agitation, system nitrogen protection.By the formula 6 compound (15.6g that accurately weigh, 10mmol, in imidazoles 0.64mmol/g), formula 1 compound (15mmol) and 100mL carrene be placed in flask, flask is placed in oil bath, under high-speed stirred, back flow reaction 24 hours, adds externally-applied magnetic field, pouring liquid, then add the Mn (OAc) of 15mmol 24H 2o, 120mL absolute ethyl alcohol, refluxes and adds lithium chloride (15mmol) to continue back flow reaction 1 hour after 1 hour, adds magnetic field, and pouring liquid, adds 100mL methyl alcohol, KPF 6(15mmol) back flow reaction is after 24 hours, adds magnetic field, pouring liquid, and gained solid-liquid is again with absolute ether washing 3 times, and dry 5 hours of 60 DEG C, vacuum, obtains faint yellow solid 12.3g.Obtaining catalyst loadings through elementary analysis is 0.55mmol/g, the amount of yield 86%(based on imidazoles).X-ray powder diffraction (XRD) data show that there is broad peak at 2 θ angles between 20～30 °, show the existence of silica inclusion layer; Infrared (FT-IR) shows: 3156cm -1and 3105cm -1represent respectively the C-H stretching vibration peak on imidazole ring, 1568cm -1and 1550cm -1represent the stretching vibration peak of the two keys of imidazole ring C=C, 1630cm -1represent the vibration peak of the two keys of C=N, 3000cm -1absworption peak represent the vibration peak of tertiary butyl groups, 1548cm -1represent the absworption peak of manganese.ICP-AES confirms that manganese load capacity is 0.48mmol/g.
Embodiment 7
Experimental provision is mainly there-necked flask, in order to stir fully, adopts mechanical agitation, system nitrogen protection.By the formula 5 compound (14.8g that accurately weigh, 10mmol, in imidazoles 0.68mmol/g), formula 3 compounds (12mmol) and 80mL toluene is placed in flask, flask is placed in oil bath, under high-speed stirred, back flow reaction 24 hours, adds externally-applied magnetic field, pouring liquid, then add the Mn (OAc) of 15mmol 24H 2o, 60mL absolute ethyl alcohol, refluxes and adds lithium chloride (15mmol) to continue back flow reaction 1 hour after 1 hour, adds magnetic field, and pouring liquid, adds 100mL methyl alcohol, NaBF 4(15mmol) back flow reaction is after 10 hours, adds magnetic field, pouring liquid, and gained solid-liquid is again with absolute ether washing 3 times, and dry 5 hours of 60 DEG C, vacuum, obtains faint yellow solid 14.1g.Obtaining catalyst loadings through elementary analysis is 0.56mmol/g, the amount of yield 82%(based on imidazoles).X-ray powder diffraction (XRD) data show that there is broad peak at 2 θ angles between 20～30 °, show the existence of silica inclusion layer; Infrared (FT-IR) shows: 3153cm -1and 3106cm -1represent respectively the C-H stretching vibration peak on imidazole ring, 1566cm -1and 1545cm -1represent the stretching vibration peak of the two keys of imidazole ring C=C, 1632cm -1represent the vibration peak of the two keys of C=N, 3000cm -1absworption peak represent the vibration peak of tertiary butyl groups, 1550cm -1represent the absworption peak of manganese.ICP-AES confirms that manganese load capacity is 0.53mmol/g.
Embodiment 81L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), carrene (60mL), toluene (0.1mL) is interior mark, additive NMO (0.02mol), formula VI catalyst (0.002mol), under ice-water bath condition, add metachloroperbenzoic acid (0.04mol) reaction 2 hours in batches, room temperature 3 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (5.1g, yield 83%). 1H?NMR(400MHz,D 2O)(ppm):7.48(m,5H),5.12(s,2H),6.65(s,1H),3.19-3.65(m,4H),2.89(dd,1H,J=5.6,14Hz)。
Embodiment 91L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), carrene (60mL), toluene (0.1mL) is interior mark, add PPNO (0.02mol), formula IX catalyst (0.004mol), under ice-water bath condition, add a hydrogen peroxide (0.06mol) reaction 1 hour in batches, room temperature 5 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (4.8g, yield 78%). 1h NMR result is with embodiment 8.
Embodiment 101L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), carrene (60mL), toluene (0.1mL) is interior mark, add NMO (0.04mol), formula IX catalyst (0.002mol), under ice-water bath condition, add a hydrogen peroxide (0.1mol) reaction 1 hour in batches, room temperature 5 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (4.5g, yield 73%). 1h NMR result is with embodiment 8.
Embodiment 111L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), oxolane (60mL), toluene (0.1mL) is interior mark, add PPNO (0.1mol), formula IX catalyst (0.006mol), under ice-water bath condition, add a hydrogen peroxide (0.04mol) reaction 1 hour in batches, room temperature 8 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (4.2g, yield 68%). 1h NMR result is with embodiment 8.
Embodiment 121L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), oxolane (60mL), toluene (0.1mL) is interior mark, add PPNO (0.1mol), formula X catalyst (0.006mol), under ice-water bath condition, add a hydrogen peroxide (0.04mol) reaction 1 hour in batches, room temperature 10 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (3.7g, yield 60%). 1h NMR result is with embodiment 8.
Embodiment 131L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), oxolane (60mL), toluene (0.1mL) is interior mark, add NMO (0.1mol), formula XI catalyst (0.006mol), under ice-water bath condition, add a hydrogen peroxide (0.04mol) reaction 1 hour in batches, room temperature 8 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (4.3g, yield 70%). 1h NMR result is with embodiment 8.
Embodiment 141L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), oxolane (60mL), toluene (0.1mL) is interior mark, add PPNO (0.05mol), formula XII catalyst (0.006mol), under ice-water bath condition, add a hydrogen peroxide (0.04mol) reaction 1 hour in batches, room temperature 5 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (4.4g, yield 71%). 1h NMR result is with embodiment 8.
Embodiment 151L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), oxolane (60mL), toluene (0.1mL) is interior mark, add PPNO (0.1mol), formula XIII catalyst (0.006mol), under ice-water bath condition, add a hydrogen peroxide (0.04mol) reaction 1 hour in batches, room temperature 10 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (3.9g, yield 63%). 1h NMR result is with embodiment 8.
Embodiment 161L (1R)-(1,3,4/2)-[benzyloxycarbonyl group (amino)]-6-epoxy-1, the preparation of 2,3-phloroglucite (formula B compound)
In single port bottle, add formula A compound (5.9g, 0.02mol), carrene (60mL), toluene (0.1mL) is interior mark, add PPNO (0.02mol), formula XIV catalyst (0.004mol), under ice-water bath condition, add a hydrogen peroxide (0.06mol) reaction 1 hour in batches, room temperature 6 hours again, reaction finishes rear interpolation external magnetic field and reclaims catalyst, and liquid is successively with 1N sodium hydroxide solution, saturated common salt water washing, use again anhydrous magnesium sulfate drying, steam organic solvent, obtain formula B compound (4.4g, yield 72%). 1h NMR result is with embodiment 8.
It should be noted that, foregoing invention content and detailed description of the invention are intended to prove the practical application of technical scheme provided by the present invention, should not be construed as limiting the scope of the present invention.Those skilled in the art are in spirit of the present invention and principle, when doing various amendments, be equal to and replace or improve.

Claims (11)

1. the loaded catalyst shown in following structural formula I,
Wherein,
Carrier is the superparamagnetic nano particle of superparamagnetic nano particle or silica inclusion;
M is metal ion;
X -for inorganic or organic anion;
R 1for C 1～C 6the C that alkyl, halogen replace 1～C 6alkyl, C 6～C 12aryl, halogen or C 1～C 6the C that alkyl replaces 6～C 12aryl, halogen or C 1～C 4alkoxyl;
R 2and R 3be C independently of one another 1～C 6alkyl or C 6～C 12aryl; Or R 2and R 3be connected to form-(CH 2) 3-or-(CH 2) 4-;
Linker is connector-O 3si-(CH 2) n-NH-C (O)-or-O 3si-(CH 2) n-, the integer that n is 1～7.
2. loaded catalyst according to claim 1; wherein; described carrier is the tri-iron tetroxide superparamagnetic nano particle of tri-iron tetroxide superparamagnetic nano particle or silica inclusion, is preferably the tri-iron tetroxide superparamagnetic nano particle of silica inclusion.
3. loaded catalyst according to claim 1 and 2, wherein, described M is Mn ion or Co ion; Described X -for Cl -, BF 4 -, PF 6 -, OTf -, NTf 2 -, CH 3cOO -, CH 3cH 2cOO -, CH 3cH 2cH 2cOO -or CH 3cH (OH) COO -.
4. loaded catalyst according to claim 3, wherein, described M is Mn ion; Described X -for BF 4 -, PF 6 -or NTf 2 -.
5. according to the loaded catalyst described in any one in claim 1～4, wherein, described linker is-O 3si-(CH 2) 3-NH-C (O)-or-O 3si-(CH 2) 3-.
6. loaded catalyst according to claim 1 or 5, wherein, described R 1for-CH 2cl or the tert-butyl group; R 2and R 3be phenyl simultaneously, or R 2and R 3be connected to form-(CH 2) 4-.
7. according to the loaded catalyst described in claim 1 or 6, wherein, described loaded catalyst is specially:
or
8. a preparation method for the loaded catalyst described in any one in claim 1～7, is characterized in that, comprises the following steps:
(1) make formula III compound react and obtain formula II compound with formula IV compound;
(2) formula II compound is reacted with slaine and lithium chloride, and then carry out ion-exchange reactions with ionic liquid, obtain formula I compound;
Wherein, R is-CH 2-Y, Y is halogen;
Cation in described slaine is M;
Anion in described ionic liquid is X -;
Described carrier, R 1, R 2, R 3identical with claim 1 with the definition of linker.
9. preparation method according to claim 8, is characterized in that,
In step (1), the mol ratio of formula III compound and formula IV compound is 1:1～2; The solvent using is selected from carrene, oxolane and toluene; Reaction temperature is 10～110 DEG C; Reaction time is 12～96 hours;
In step (2), the mol ratio of formula II compound and slaine is 1:1～1.5; The mol ratio of formula II compound and lithium chloride is 1:1～1.5; The solvent that formula II compound reacts with slaine and lithium chloride is selected from ethanol, methyl alcohol or toluene; Under reflux temperature, react 0.5～5 hour; Preferably, described slaine is manganese metal salt or Cobalt salts, more preferably Mn (OAc) 24H 2o or Co (OAc) 24H 2o.
10. preparation method according to claim 8 or claim 9, it is characterized in that, in step (2), after formula II compound has reacted with slaine and lithium chloride, hold solid with externally-applied magnetic field, abandon liquid, gained solid is put into methyl alcohol backflow and is carried out ion-exchange reactions, reacts 0.5～5 hour under reflux temperature; The mol ratio of its Chinese style II compound and ionic liquid is 1:1～1.5; Preferably, described ionic liquid is NaX, KX or LiX.
Loaded catalyst in 11. claims 1～7 described in any one is the purposes in asymmetric epoxidation reaction as chiral catalyst.
CN201310157771.7A 2013-04-27 2013-04-27 Supported catalyst and preparation method thereof Pending CN104117392A (en)

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* Cited by examiner, † Cited by third party
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CN105879914A (en) * 2016-06-03 2016-08-24 湖南师范大学 Temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and preparation method thereof
CN106045804A (en) * 2016-06-03 2016-10-26 湖南师范大学 Method for realizing asymmetric oxidation reaction of thioether under aqueous-phase catalysis of chiral Salen Ti complex catalyst based on temperature-sensitive type ionic liquid
CN107552090A (en) * 2017-09-12 2018-01-09 石家庄学院 Immobilized quinine catalyst of a kind of pentaerythrite and its preparation method and application
CN107715909A (en) * 2017-09-13 2018-02-23 石家庄学院 A kind of Proline-Catalyzed agent of pentaerythrite support and preparation method and application

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* Cited by examiner, † Cited by third party
Title
QIANG ZHANG ET AL，: "A magnetic nanoparticle supported dual acidic ionic liquid: a "quasi-homogeneous" catalyst for the one-pot synthesis of benzoxanthenes", 《GREEN CHEMISTRY》 *
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105879914A (en) * 2016-06-03 2016-08-24 湖南师范大学 Temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and preparation method thereof
CN106045804A (en) * 2016-06-03 2016-10-26 湖南师范大学 Method for realizing asymmetric oxidation reaction of thioether under aqueous-phase catalysis of chiral Salen Ti complex catalyst based on temperature-sensitive type ionic liquid
CN105879914B (en) * 2016-06-03 2018-03-30 湖南师范大学 A kind of temperature sensitive type ionic liquid chirality Salen Ti composition catalysts and preparation method thereof
CN106045804B (en) * 2016-06-03 2019-01-11 湖南师范大学 A method of based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction
CN107552090A (en) * 2017-09-12 2018-01-09 石家庄学院 Immobilized quinine catalyst of a kind of pentaerythrite and its preparation method and application
CN107552090B (en) * 2017-09-12 2019-12-03 石家庄学院 A kind of quinine catalyst and its preparation method and application that pentaerythrite is immobilized
CN107715909A (en) * 2017-09-13 2018-02-23 石家庄学院 A kind of Proline-Catalyzed agent of pentaerythrite support and preparation method and application
CN107715909B (en) * 2017-09-13 2020-02-14 石家庄学院 Pentaerythritol-supported proline catalyst and preparation method and application thereof

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Application publication date: 20141029