CN104558056A - Preparation and application of novel isopropyl zirconocene complex - Google Patents

Preparation and application of novel isopropyl zirconocene complex Download PDF

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CN104558056A
CN104558056A CN201410764877.8A CN201410764877A CN104558056A CN 104558056 A CN104558056 A CN 104558056A CN 201410764877 A CN201410764877 A CN 201410764877A CN 104558056 A CN104558056 A CN 104558056A
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catalyst
reaction
zirconium
isopropyl
sulfonic acid
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邱仁华
张小红
许新华
李宁波
陈锦杨
王勰
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Hunan University
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Abstract

The invention provides a novel metallocene catalyst and a green catalytic synthesis method of a polyarylate substituted 1,3-dicarbonyl compound developed by the catalyst. Zirconium atoms in the metallocene catalyst are connected with each other through two isopropyl-substituted cyclopentadienyl rings to display tetravalence; the zirconium atoms are coordinated with three hydrones; and the overall organic zirconium cationic part and the corresponding anions form an ion bond. The green synthesis method comprises the following steps: with a 1,3-dicarbonyl compound with active hydrogen as a reaction raw material, and aryl alcohol as an alkylation agent, carrying out intramolecular dehydration alkylation reaction under catalysis of perfluorooctane sulfonate isopropyl cyclopentadienyl zirconium; and obtaining a series of multiaryl-substituted 1,3-dicarbonyl compounds at a relatively low temperature and high yield. The method has the main advantages of being mild in reaction condition, simple to test and operate, high in yield and the like; the reaction is suitable for kinds of 1,3-dicarbonyl derivatives and different aryl alcohol; with perfluorooctane sulfonate isopropyl cyclopentadienyl zirconium as a catalyst, the catalyst can be recycled and used for a plurality of times; and meanwhile, the sole by-product is water, and has the advantages of being green, free of pollution and the like.

Description

A kind of preparation and application of novel isopropyl Zirconocenes
[technical field]
The invention belongs to catalysis organic synthesis field, specifically a kind of novelthe preparation method of isopropyl Zirconocenes and the green catalysis synthetic method of 1,3-dicarbonyl compound that replaces of a kind of polyaryl.To have 1,3-dicarbapentaborane of active hydrogen for reaction raw materials, aryl alcohol is alkylating reagent, under the luxuriant zirconium catalysis of perfluoro octyl sulfonic acid isopropyl, through the alkylated reaction of intermolecular dehydration.
[background technology]
The alkylated reaction of 1,3-dicarbonyl compound is the method for the important structure C-C key of a class.The method is at first under base catalysis, with halogenated hydrocarbons, carboxylate, phosphate or carbonic ester etc. for alkylating reagent, and 1,3-Dicarbonyl derivatives generation alkylated reaction, thus form C-C key.The shortcoming of the method take alkali as catalyst, and have a large amount of all kinds of accessory substances to produce, Atom economy is poor, unfriendly to environment, and therefore the application of the method is subject to great restriction (J.Org.Chem.2003,68,1575 simultaneously; Org.Lett.2004,6,763.).In recent decades, domestic and international chemists have carried out continuous exploration to such reaction, find when using alcoholic compound to replace above alkylating reagent, unique accessory substance of reaction is water, there is eco-friendly advantage, be applicable to needs (Green Chem.2011,13,1244 of social development; Tetrahedron Lett.2010,51,1847; Org.Lett.2007,9,311.).But the group of leaving away because the hydroxyl in alcohol is difficult, the carrying out smoothly of reaction needs have a large amount of bronsted acid or lewis acid to exist in system.Therefore, bronsted acid is reduced or lewis acidic consumption is most important.Recently, chemist reports the alkylated reaction of all kinds of catalyst 1,3-Dicarbonyl derivatives and alcohol.Phosphotungstic acid, Trimethylsilyl trifluoromethanesulfonate, TFMS yttrium, Bismuth triflate, perfluorophenyl boron, indium trichloride, ferric trichloride, trifluoromethane sulfonic acid etc. as catalytic amount all can be used as Louis acid acid or bronsted acid catalysis 1, alkylated reaction (Eur.J.Org.Chem.2008,4999 of 3-dicarbonyl compound and alcohol; Tetrahedron Lett.2010,51,5454; Tetrahedron Lett.2007,48,3969; Synthesis.2010,21,3715; Angew.Chem.Int.Ed.2006,45,793; Tetrahedron Lett.2009,50,1490; Org.Lett.2007,9,825.).These methods have the advantages such as catalyst amount is few, accessory substance is water, reaction raw materials is easy to get.But also there is catalyst simultaneously easily absorb water, the shortcoming such as need to react in anhydrous conditions.Also limit this type of application of reaction in organic synthesis equally.
Therefore, in the present invention, we adopt the chlorine atom of the luxuriant zirconium dichloride of strong electrophilic anion metathesis diisopropyl, have synthesized isopropyl zirconium complex, we are applied to 1,3-dicarbapentaborane and alcohol alkylated reaction using isopropyl Zirconocenes as lewis acid catalyst further; At present, 1,3-dicarbonyl compound open source literature and patent application of polyaryl replacement is not also prepared both at home and abroad about the catalysis of isopropyl Zirconocenes.
[summary of the invention]
The object of the present invention is to provide one novelthe preparation method of isopropyl Zirconocenes and the green catalysis synthetic method of 1,3-dicarbonyl compound that replaces of a kind of polyaryl.The method uses the luxuriant zirconium of perfluoroalkyl (aryl) sulfonic acid isopropyl to be catalyst, and catalysis is to have 1,3-dicarbapentaborane of active hydrogen for reaction raw materials, and aryl alcohol is the alkylated reaction of alkylating reagent.Because this type of catalyst has air and Thermodynamically stable, water resistant, antioxygen and high catalytic activity, the advantage such as repeatedly to reclaim, thus simplify experimental implementation, improve the productive rate etc. of target product.Meanwhile, this accessory substance reacting unique is water, has the advantages such as green non-pollution.
To achieve the above object of the invention, the present invention proposes following technical scheme:
Luxuriant for dichloro diisopropyl zirconium is dissolved in THF, N 2add the THF solution of perfluorinated sulfonic acid silver under protection, room temperature lucifuge stirs 1-2h.Filter, filtrate adds n-hexane, until layering.Put into refrigerator freezing 12h, separate out perfluorinated sulfonic acid isopropyl luxuriant zirconium (I) catalyst.
In above-mentioned synthetic method, the preferred trifluoromethayl sulfonic acid root of the luxuriant zirconium of catalyst perfluorinated sulfonic acid isopropyl (I) complex anion ( -oSO 2cF 3), perchlorate (ClO 4 -), perfluoro butyl sulfonate radical ( -oSO 2c 4f 9), pentafluorophenyl group sulfonate radical ( -oSO 2c 6f 5), perfluoro octyl sulfonic acid root ( -oSO 2c 8f 17) in one.
In above-mentioned synthetic method, described catalyst is cationic isopropyl Zirconocenes, and structural formula is as follows:
To have 1,3-dicarbonyl compound of active hydrogen for reaction raw materials, aryl alcohol is alkylating reagent, under the luxuriant zirconium of perfluoro octyl sulfonic acid isopropyl (I) catalysis, through intermolecular dehydration, alkylated reaction occurs.This reaction is effectively carried out at a lower temperature, and high productivity obtains 1, the 3-dicarbonyl compound that a series of polyaryl replaces.
In above-mentioned synthetic method, the preferred acetylacetone,2,4-pentanedione (R of described 1,3-dicarbapentaborane 1=R 2=CH 3), dibenzoyl methane (R 1=R 2=Ph), benzoyl acetone (R 1=Ph, R 2=CH 3), 1, hydroresorcinol [R 1-R 2=(CH 2) 3], 5,5-dimethyl-1, hydroresorcinol, ethyl acetoacetate (R 1=CH 3, R 2=OCH 2cH 3), ethyl benzoylacetate (R 1=Ph, R 2=OCH 2cH 3).
In above-mentioned synthetic method, described aryl alcohol is benzhydrol (R 3=R 4=Ph), 2-methyldiphenyl methyl alcohol (R 3=Ph, R 4=2-CH 3ph), 4-methyldiphenyl methyl alcohol (R 3=Ph, R 4=4-CH 3ph), 4-methoxyl group benzhydrol (R 3=Ph, R 4=4-OCH 3ph), 4-chlorodiphenyl methyl alcohol (R 3=Ph, R 4=4-ClPh), 4,4 '-dichloro methyl alcohol (R 3=R 4=4-ClPh), 4,4 '-difluoro diphenyl methanol (R 3=R 4=4-FPh), methylbenzyl alcohol (R 3=CH 3, R 4=Ph).
In above-mentioned synthetic method, described solvent is the one in carrene, oxolane, acetonitrile, DMSO, DMF.
In above-mentioned synthetic method, reaction temperature is 40-60 DEG C.
In above-mentioned synthetic method, catalyst amount is 5mol%-10mol%.
In above-mentioned synthetic method, the reaction time is 4-12h.
In above-mentioned synthetic method, catalyst at least can recycle 5 times.
Perfluoro octyl sulfonic acid isopropyl zirconocene catalyst provided by the present invention, the advantage such as there is air and Thermodynamically stable, water resistant, antioxygen and high catalytic activity, can repeatedly reclaim.By this catalyst application in the alkylated reaction of 1,3-dicarbonyl compound and aryl alcohol, these reaction raw materials wide material sources, target product productive rate is higher, and reaction condition is gentle, and experimental implementation is easy, and wide application range of substrates is general; Accessory substance is water, green non-pollution.
[accompanying drawing explanation]
fig. 1shown in be the path of 1,3-dicarbonyl compound that synthesis polyaryl provided by the invention replaces figure.
[detailed description of the invention]
The anti-route of alkylation of perfluoroalkyl provided by the present invention (aryl) sulfonic acid isopropyl luxuriant zirconium catalysis 1,3-dicarbonyl compound and aryl alcohol, refers to accompanying drawing 1: raw material 1,3-dicarbonyl compound, aryl alcohol and catalyst are added in reaction vessel, adds solvent, do not need N 2protection, reacts 4-12h, obtains target compound through column chromatography for separation under the environment of 40-60 DEG C.
Below in conjunction with concrete preparation example, the present invention will be further described: below in conjunction with concrete preparation example, the present invention will be further described:
Prepared by perfluoroalkyl (aryl) sulfonic acid isopropyl zirconocene catalyst:
preparation example 1
The preparation of the luxuriant zirconium of catalyst perfluoroalkyl (aryl) sulfonic acid isopropyl: luxuriant for dichloro diisopropyl zirconium is dissolved in THF, N 2add the THF solution of perfluoro octyl sulfonic acid silver under protection, room temperature lucifuge stirs: 1h.Filter, filtrate adds n-hexane, until layering.Put into refrigerator freezing 12h, separate out complex solid, productive rate 60%.
preparation example 2
Luxuriant zirconium (the X=OSO of catalyst perfluoro octyl sulfonic acid isopropyl 2c 6f 5) preparation: luxuriant for dichloro diisopropyl zirconium is dissolved in acetonitrile, N 2add the acetonitrile solution of perfluorophenyl sulfonic acid silver under protection, room temperature lucifuge stirs: 1.5h.Filter, filtrate adds n-hexane, until layering.Put into refrigerator freezing 12h, separate out complex solid, productive rate 61%.
preparation example 3
Luxuriant zirconium (the X=OSO of catalyst perfluoro octyl sulfonic acid isopropyl 2c 4f 9) preparation: luxuriant for dichloro diisopropyl zirconium is dissolved in acetone, N 2add the acetone soln of perfluoro butyl sulfonic acid silver under protection, room temperature lucifuge stirs: 2h.Filter, filtrate adds n-hexane, until layering.Put into refrigerator freezing 12h, separate out complex solid, productive rate 64%.
The alkylated reaction preparation example of perfluoroalkyl (aryl) sulfonic acid isopropyl luxuriant zirconium catalysis 1,3-dicarbonyl compound and aryl alcohol:
preparation example 1
Dibenzoyl methane (0.5mmol) is added, benzhydrol (0.55mmol), the luxuriant zirconium (X=OSO of perfluoro octyl sulfonic acid isopropyl in 10mL reaction tube 2c 8f 17) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-benzhydryl-1,3-diphenyl propane-1,3-diketone, productive rate 95%.
preparation example 2
Dibenzoyl methane (0.5mmol) is added, 2-methyldiphenyl methyl alcohol (0.55mmol), the luxuriant zirconium (X=OSO of perfluoro butyl base sulfonic acid isopropyl in 10mL reaction tube 2c 4f 9) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-(phenyl-2-aminomethyl phenyl) methyl isophthalic acid, 3-diphenyl propane-1,3-diketone, productive rate 91%.
preparation example 3
Dibenzoyl methane (0.5mmol) is added, 4-methyldiphenyl methyl alcohol (0.55mmol), the luxuriant zirconium (X=OSO of perfluorophenyl sulfonic acid isopropyl in 10mL reaction tube 2c 6f 5) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-(phenyl-4-aminomethyl phenyl) methyl isophthalic acid, 3-diphenyl propane-1,3-diketone, productive rate 93%.
preparation example 4
Dibenzoyl methane (0.5mmol) is added, 4-methoxyl group benzhydrol (0.55mmol), the luxuriant zirconium (X=OSO of perfluorophenyl sulfonic acid isopropyl in 10mL reaction tube 2cF 3) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-(phenyl-4-methoxyphenyl) methyl isophthalic acid, 3-diphenyl propane-1,3-diketone, productive rate 87%.
preparation example 5
Dibenzoyl methane (0.5mmol) is added, 4-chlorodiphenyl methyl alcohol (0.55mmol), the luxuriant zirconium (ClO of perfluoro butyl sulfonic acid isopropyl in 10mL reaction tube 4) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-(phenyl-4-chlorphenyl) methyl isophthalic acid, 3-diphenyl propane-1,3-diketone, productive rate 93%.
preparation example 6
Dibenzoyl methane (0.5mmol) is added, 4,4 '-dichloro methyl alcohol (0.55mmol), the luxuriant zirconium (ClO of perchloric acid isopropyl in 10mL reaction tube 4) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-(4,4 '-dichlorophenyl) methyl isophthalic acid, 3-diphenyl propane-1,3-diketone, productive rate 90%.
preparation example 7
Dibenzoyl methane (0.5mmol) is added, 4,4 '-difluoro diphenyl methanol (0.55mmol), the luxuriant zirconium (X=OSO of perfluoro octyl sulfonic acid isopropyl in 10mL reaction tube 2c 8f 17) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-(4,4 '-difluorodiphenyl base) methyl isophthalic acid, 3-diphenyl propane-1,3-diketone, productive rate 95%.
preparation example 8
Dibenzoyl methane (0.5mmol) is added in 10mL reaction tube, methylbenzyl alcohol (0.55mmol), the luxuriant zirconium of perfluoro butyl sulfonic acid isopropyl (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-phenyl methyl-1,3-diphenyl propane-1,3-diketone, productive rate 88%.
preparation example 9
Acetylacetone,2,4-pentanedione (0.5mmol) is added, benzhydrol (0.55mmol), the luxuriant zirconium (X=OSO of perfluorophenyl sulfonic acid isopropyl in 10mL reaction tube 2c 6f 5) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 3-benzhydryl pentane-2,4-diketone, productive rate 93%.
preparation example 10
Benzoyl acetone (0.5mmol) is added, benzhydrol (0.55mmol), the luxuriant zirconium (X=OSO of trifluoromethayl sulfonic acid isopropyl in 10mL reaction tube 2cF 3) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-benzhydryl-1-phenyl butane-1,3-diketone, productive rate 88%.
preparation example 11
Ethyl benzoylacetate (0.5mmol) is added, benzhydrol (0.55mmol), the luxuriant zirconium (X=OSO of perfluoro octyl sulfonic acid isopropyl in 10mL reaction tube 2c 8f 17) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-benzhydryl-ethyl benzoylacetate, productive rate 95%.
preparation example 12
Ethyl acetoacetate (0.5mmol) is added, benzhydrol (0.55mmol), the luxuriant zirconium (X=OSO of perfluoro octyl sulfonic acid isopropyl in 10mL reaction tube 2c 8f 17) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-benzhydryl-ethyl acetoacetate, productive rate 93%.
preparation example 13
1 is added, hydroresorcinol (0.5mmol), 4,4 '-dichloro methyl alcohol (0.55mmol), the luxuriant zirconium (X=OSO of perfluoro butyl sulfonic acid isopropyl in 10mL reaction tube 2c 4f 9) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 2-(4,4 '-dichlorophenyl) hexahydrotoluene-1,3-diketone, productive rate 70%.
preparation example 14
5,5-dimethyl-1 is added, hydroresorcinol (0.5mmol), benzhydrol (0.55mmol), the luxuriant zirconium (X=OSO of perfluorophenyl sulfonic acid isopropyl in 10mL reaction tube 2c 6f 5) (0.025mmol) and carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, and except desolventizing, residue adds 10mL carrene, and collect solid catalyst to recycle, this process in triplicate.Last filtrate revolves steaming, through column chromatography for separation, obtains white solid 5,5-dimethyl-2-diphenylmethyl butylcyclohexane-1,3-diketone, productive rate 65%.
In order to further illustrate the superiority of the inventive method, select following catalyst system and catalyzing as a comparison case.
comparative example 1
Dibenzoyl methane (0.5mmol) is added, benzhydrol (0.55mmol), anhydrous FeCl in 10mL reaction tube 3(0.025mmol) with carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, except desolventizing, through column chromatography for separation, obtains white solid 2-benzhydryl-1,3-diphenyl propane-1,3-diketone, productive rate 92%.
comparative example 2
Dibenzoyl methane (0.5mmol) is added, benzhydrol (0.55mmol), anhydrous AlCl in 10mL reaction tube 3(0.025mmol) with carrene (2mL), 60 DEG C add thermal agitation.Reaction terminates rear cooling, and filtrate revolves steaming, except desolventizing, through column chromatography for separation, obtains white solid 2-benzhydryl-1,3-diphenyl propane-1,3-diketone, productive rate 88%.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (6)

1. a cationic isopropyl Zirconocenes catalyst, its structural formula is (I); The luxuriant ring that wherein zirconium atom is replaced by two isopropyls connects, display tetravalence; Zirconium atom and three water molecule coordination, whole organic zirconium cationic moiety forms ionic bond with corresponding anion; Wherein the preferred trifluoromethayl sulfonic acid root of anion X ( -oSO 2cF 3), perchlorate (ClO 4 -), perfluoro butyl sulfonate radical ( -oSO 2c 4f 9), pentafluorophenyl group sulfonate radical ( -oSO 2c 6f 5), perfluoro octyl sulfonic acid root ( -oSO 2c 8f 17) in one.
2. catalyst according to claim 1 (I), its synthetic method is: luxuriant for dichloro diisopropyl zirconium is dissolved in THF, acetonitrile, the one in acetone, N 2add the THF of perfluoroalkyl or aryl sulfonic acid silver under protection, acetonitrile, a kind of solution in acetone, room temperature lucifuge stirs 1-2h.Filter, filtrate adds n-hexane, until layering.Put into refrigerator freezing 12h, separate out complex solid.
3. the catalyst (I) according to claim 1 and 2, the a kind of of exploitation synthesizes 1 of polyaryl replacement, the method of 3-dicarbonyl compound, its principal character: to have 1 of active hydrogen, 3-dicarbonyl compound is reaction raw materials, aryl alcohol is alkylating reagent, at isopropyl Zirconocenes (I) under catalyst, through the alkylated reaction of intermolecular dehydration, effectively carry out at a lower temperature, high productivity obtains 1, the 3-dicarbonyl compound (II) that a series of polyaryl replaces, and product structure formula is (II).
4. synthetic method according to claim 3, is characterized in that, the preferred acetylacetone,2,4-pentanedione (R of described reaction raw materials 1,3-dicarbapentaborane 1=R 2=CH 3), dibenzoyl methane (R 1=R 2=Ph), benzoyl acetone (R 1=Ph, R 2=CH 3), 1, hydroresorcinol [R 1-R 2=(CH 2) 3], 5,5-dimethyl-1, hydroresorcinol, ethyl acetoacetate (R 1=CH 3, R 2=OCH 2cH 3), ethyl benzoylacetate (R 1=Ph, R 2=OCH 2cH 3).
5. synthetic method according to claim 3, is characterized in that, described aryl alcohol is benzhydrol (R 3=R 4=Ph), 2-methyldiphenyl methyl alcohol (R 3=Ph, R 4=2-CH 3ph), 4-methyldiphenyl methyl alcohol (R 3=Ph, R 4=4-CH 3ph), 4-methoxyl group benzhydrol (R 3=Ph, R 4=4-OCH 3ph), 4-chlorodiphenyl methyl alcohol (R 3=Ph, R 4=4-ClPh), 4,4 '-dichloro methyl alcohol (R 3=R 4=4-ClPh), 4,4 '-difluoro diphenyl methanol (R 3=R 4=4-FPh), methylbenzyl alcohol (R 3=CH 3, R 4=Ph).
6. synthetic method according to claim 3, is characterized in that, described solvent is the one in carrene, oxolane, acetonitrile, DMSO, DMF; Described reaction condition is: reaction temperature is 40-60 DEG C, and catalyst amount is 5mol%-10mol%, and the reaction time is 4-12h, and catalyst at least can recycle 5 times.
CN201410764877.8A 2014-12-11 2014-12-11 Preparation and application of novel isopropyl zirconocene complex Pending CN104558056A (en)

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CN107089912A (en) * 2017-05-16 2017-08-25 湖南大学 A kind of method that metallocene complex selective catalysis synthesizes mandelic acid ester type compound
CN107790186A (en) * 2017-11-07 2018-03-13 山西医科大学 A kind of new decamethyl Zirconocenes and its preparation method and application
CN107790186B (en) * 2017-11-07 2020-10-30 山西医科大学 Novel decamethyl cyclopentadienyl zirconium complex and preparation method and application thereof
CN109012744A (en) * 2018-09-20 2018-12-18 四川文理学院 A kind of method of visible light photocatalytic degradation nitrogen oxides
CN109012744B (en) * 2018-09-20 2021-06-11 四川文理学院 Method for degrading nitrogen oxide by visible light catalysis

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