CN107312045A - A kind of preparation method of substituted cyclopentadienyl metallocene compound - Google Patents
A kind of preparation method of substituted cyclopentadienyl metallocene compound Download PDFInfo
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- CN107312045A CN107312045A CN201710595426.XA CN201710595426A CN107312045A CN 107312045 A CN107312045 A CN 107312045A CN 201710595426 A CN201710595426 A CN 201710595426A CN 107312045 A CN107312045 A CN 107312045A
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Abstract
The present invention relates to a kind of preparation method of substituted cyclopentadienyl metallocene compound, using cyclopentadiene compound and the rich vinyl compound of group compounds of aldehydes and ketones reaction generation, then with metal hydride effect generation substituted cyclopentadienyl salt, further metallocene compound is obtained with the reaction of Group IV metal halide.Compared with prior art, the present invention has the advantages that product yield high, easy to operate, good economy performance, is adapted to industrial production.
Description
Technical field
The present invention relates to the preparation method of the metallocene compound of new structure, more particularly, to a kind of substituted-cyclopentadienyl
The preparation method of base metallocene compound.
Background technology
Metallocene compound is by transition metal or thulium and at least one cyclopentadiene or cyclopentadiene
Derivative constitutes a class organometallic complex as part, and prepared by the production that it is widely used in polyolefin, with catalysis
The advantages of active high, applicable monomer is more, single active sites, polymer architecture are accurately controlled (metallocene catalyst and its alkene
Polymer, Chemical Industry Press, 2000).In in the past few decades, people are by changing the substituent on luxuriant ring, design
Go out various new part, and then synthesize a variety of metallocene complexes (Chem.Rev.2000,100,1205).With on luxuriant ring
The change of substituent, the physical property and chemical property of its corresponding metal complex can also change therewith, and these changes master
If because receiving the electronics caused by luxuriant ring hydrogen atom is replaced by other groups and the influence of steric hindrance
(Chem.Rev.2000,100,1253)。
Most of metallocene catalyst preparation method produces corresponding lithium salts using n-BuLi and ligand reaction, then and
Metal halide reaction obtains product (US.Patent 6,252,098；US.Patent 6,175,027；
J.Am.Chem.Soc.1998,120,2308；Organmetallics,1999,18,1873；Organmetallics,2000,
19,420)。
Document report, is reacted by n-BuLi and metal halide first, the double normal-butyl dihalide of generation, then and is matched somebody with somebody
Precursor reactant obtains metallocene compound (Organometallics 1999,18,1583；Polyhedron2005,24,1325).
Can also be by first synthesizing M (NH2)4Metallocene compound (Organometallics 1996,14,5 is prepared with ligand reaction again；
US Patent 8,013,177)。
There is the structure of some parts more special, the sodium salt (Journal of respective ligand can be directly prepared by metallic sodium
of Organometallic Chemistry 2009,694,1059)。
In summary, the synthetic method of metallocene catalyst is always the focus of research, and for alkali metal or alkaline earth gold
Category hydride, especially lithium hydride, sodium hydride and ligand reaction produce corresponding cyclopentadienyl group salt and prepare metallocene compound
Patent report is not found also.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of product yield high, behaviour
Make the convenient, preparation method of the substituted cyclopentadienyl metallocene compound of good economy performance.
The purpose of the present invention can be achieved through the following technical solutions：
The preparation method of substituted cyclopentadienyl metallocene compound, the structure of the metallocene compound prepared is such as
Under：
Preparation process is comprised the steps of：
The ring penta 2 that the hydride reaction of the first step, substituted fulvene compound and alkali metal or alkaline-earth metal is replaced
Alkenyl salt；
Second step, the derivative of substituted cyclopentadienyl group salt further with Group IV halide or Group IV halide is anti-
Metallocene compound should be obtained.Process is as follows：
In formula：" * " is identified to represent with 0-4 non-hydrogen substituent on five-membered ring, and non-hydrogen substituent is excellent independently of each other
Choosing containing 1 carbon atom~30 carbon atom containing hetero atom or without heteroatomic alkyl；R1And R2Separately selected from hydrogen,
Containing 1 carbon atom~30 carbon atom containing hetero atom or without heteroatomic alkyl；BHn(n=1 or 2) represent alkali metal or
The hydride of alkaline-earth metal.M represents Group IV metal：X represents halogen.
M is transition metal, selected from titanium, zirconium or hafnium.
The preferred zirconiums of M or hafnium.
The number of the connected non-hydrogen substituent of five-membered ring of described band " * " mark is 0-2,
It is preferred that 0 or 1.
The number of the connected non-hydrogen substituent of five-membered ring identified as optimal preferred embodiment, band " * " is 0.
The connected non-hydrogen substituent of five-membered ring of described band " * " mark is independently preferably containing 1 carbon atom~15 carbon
Atom containing hetero atom or without heteroatomic alkyl.
More preferably containing 1 carbon atom~10 carbon atom containing hetero atom or without heteroatomic alkyl.
As optimal preferred embodiment, 1 carbon atom~10 carbon atom containing hetero atom or without heteroatomic
Alkyl comprising methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, 1- ethyl propyls, cyclopenta, cyclohexyl, methoxyl group,
Ethyoxyl, pyridine, picolyl, phenyl, 1- phenyl propyls, 4- tert-butyl-phenyls, 4- aminomethyl phenyls, 3,5- 3,5-dimethylphenyls,
4,4- xenyls or naphthyl.
Described R1And R2Separately selected from hydrogen, containing 1 carbon atom~15 carbon atom containing hetero atom or without miscellaneous
The alkyl of atom.
More preferably hydrogen, containing 1 carbon atom~10 carbon atom containing hetero atom or without heteroatomic alkyl.
As optimal preferred embodiment, 1 carbon atom~10 carbon atom containing hetero atom or without heteroatomic
Alkyl includes methyl, ethyl, propyl group, cyclopenta, cyclohexyl, pyridine, phenyl, 4- aminomethyl phenyls, 4- propyl group phenyl, 4- butyl
Benzene, 4- tert-butyl-phenyls, benzyl, 4- fluorophenyls, 4- trifluoromethyls or 3- trifluoromethyls.
Described alkali metal or the hydride of alkaline-earth metal be selected from lithium hydride, sodium hydride, hydrofining, calcium hydride, beryllium hydride,
Magnesium hydride,
Lithium hydride, sodium hydride, hydrofining preferably are selected from,
As optimal preferred embodiment, selected from lithium hydride, sodium hydride.
It is preferred that, X represents chlorine.
The derivative of Group IV halide be four (dimethyl amido) zirconiums, tetraethoxy zirconium, four (ethyl-methyl amido) zirconiums,
Four zirconium-n-propylates, four zirconium iso-propoxides, four (dimethyl amido) titaniums, purity titanium tetraethoxide, four (ethyl-methyl amido) titaniums, four normal propyl alcohols
It is titanium, titanium tetraisopropylate, four (dimethyl amido) hafniums, tetraethoxy hafnium, four (ethyl-methyl amido) hafniums, four normal propyl alcohol hafniums, four different
Propyl alcohol hafnium；Two (dimethyl amido) zirconium dichlorides, diethoxy zirconium dichloride, two (ethyl-methyl amido) zirconium dichlorides, two are just
Propoxyl group zirconium dichloride, diisopropanol epoxide zirconium dichloride, two (dimethyl amido) titanium chloride, diethoxy titanium chloride,
Two (ethyl-methyl amido) titanium chloride, two positive propoxy titanium chloride, diisopropoxy titanium chloride, two (dimethyl amidos)
Hafnium dichloride, diethoxy hafnium dichloride, two (ethyl-methyl amido) hafnium dichlorides, two positive propoxy hafnium dichlorides or diisopropyl
Epoxide hafnium dichloride.
In step (1), reaction is carried out under the conditions of -20~25 DEG C in organic solvent under dry inert gas protection, is taken
The molar ratio of the fulvene compound and alkali metal in generation or the hydride of alkaline-earth metal is 1：1~1.5：1, react stirred overnight
Substituted cyclopentadienyl group salt is filtrated to get afterwards.
The organic solvent used in above-mentioned steps is selected from ether, methyl tertiary butyl ether(MTBE), benzene, toluene, paraxylene, adjacent diformazan
The one or more of mixture of benzene, meta-xylene, mesitylene, tetrahydrofuran, 2- methyltetrahydrofurans.
In step (2), reaction is carried out under the conditions of -50~25 DEG C in organic solvent under dry inert gas protection, is taken
The molar ratio of the cyclopentadienyl group salt in generation and Group IV halide or the derivative of Group IV halide is 2：1, reacted
Filtered after night stirring, mother liquor drains solvent and obtains metallocene compound.
The organic solvent used in above-mentioned steps is selected from ether, methyl tertiary butyl ether(MTBE), benzene, toluene, paraxylene, adjacent diformazan
The one or more of mixture of benzene, meta-xylene, mesitylene, tetrahydrofuran, 2- methyltetrahydrofurans.
Compared with prior art, raw material stability used in the method that the present invention is used is good, it is easy to quantitative, convenient behaviour
Make, the present invention has product yield high, good economy performance, is adapted to industrial advantage.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
The preparation method of substituted cyclopentadienyl metallocene compound, the structure of the metallocene compound prepared is such as
Under：
Preparation process is comprised the steps of：
The ring penta 2 that the hydride reaction of the first step, substituted fulvene compound and alkali metal or alkaline-earth metal is replaced
Alkenyl salt；
Second step, the derivative of substituted cyclopentadienyl group salt further with Group IV halide or Group IV halide is anti-
Metallocene compound should be obtained.Process is as follows：
In formula：" * " is identified to represent with 0-4 non-hydrogen substituent on five-membered ring, and non-hydrogen substituent is excellent independently of each other
Choosing containing 1 carbon atom~30 carbon atom containing hetero atom or without heteroatomic alkyl；
R1And R2Separately selected from hydrogen, containing 1 carbon atom~30 carbon atom containing hetero atom or without heteroatomic
Alkyl；
BHn(n=1 or 2) represents the hydride of alkali metal or alkaline-earth metal.
M represents Group IV metal, can be titanium, zirconium, hafnium
It is preferred that, M be zirconium, hafnium,
X represents halogen, such as chlorine.
The number of the connected non-hydrogen substituent of five-membered ring of " * " mark is individual for 0-2, preferably 0 or 1, more preferred
Embodiment is 0.
The connected non-hydrogen substituent of five-membered ring that band " * " is identified is independently preferably containing 1 carbon atom~15 carbon atom
Containing hetero atom or without heteroatomic alkyl；
More preferably containing 1 carbon atom~10 carbon atom containing hetero atom or without heteroatomic alkyl,
As the alkyl most preferably preferred embodiment, used comprising methyl, ethyl, propyl group, isopropyl, normal-butyl,
Isobutyl group, 1- ethyl propyls, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, pyridine, picolyl, phenyl, 1- phenyl propyls,
4- tert-butyl-phenyls, 4- aminomethyl phenyls, 3,5- 3,5-dimethylphenyls, 4,4- xenyls or naphthyl.
R1And R2Separately selected from hydrogen, containing 1 carbon atom~15 carbon atom containing hetero atom or without heteroatomic
Alkyl,
More preferably hydrogen, containing 1 carbon atom~10 carbon atom containing hetero atom or without heteroatomic alkyl,
As most preferably preferred embodiment, selected alkyl comprising methyl, ethyl, propyl group, cyclopenta, cyclohexyl,
Pyridine, phenyl, 4- aminomethyl phenyls, 4- propyl group phenyl, 4- butyl benzenes, 4- tert-butyl-phenyls, benzyl, 4- fluorophenyls, 4- fluoroforms
Base phenyl or 3- trifluoromethyls.
The hydride of alkali metal or alkaline-earth metal is selected from lithium hydride, sodium hydride, hydrofining, calcium hydride, beryllium hydride, hydrogenation
Magnesium,
Lithium hydride, sodium hydride, hydrofining preferably are selected from,
More preferably from lithium hydride, sodium hydride.
The derivative of Group IV halide be four (dimethyl amido) zirconiums, tetraethoxy zirconium, four (ethyl-methyl amido) zirconiums,
Four zirconium-n-propylates, four zirconium iso-propoxides, four (dimethyl amido) titaniums, purity titanium tetraethoxide, four (ethyl-methyl amido) titaniums, four normal propyl alcohols
It is titanium, titanium tetraisopropylate, four (dimethyl amido) hafniums, tetraethoxy hafnium, four (ethyl-methyl amido) hafniums, four normal propyl alcohol hafniums, four different
Propyl alcohol hafnium；Two (dimethyl amido) zirconium dichlorides, diethoxy zirconium dichloride, two (ethyl-methyl amido) zirconium dichlorides, two are just
Propoxyl group zirconium dichloride, diisopropanol epoxide zirconium dichloride, two (dimethyl amido) titanium chloride, diethoxy titanium chloride,
Two (ethyl-methyl amido) titanium chloride, two positive propoxy titanium chloride, diisopropoxy titanium chloride, two (dimethyl amidos)
Hafnium dichloride, diethoxy hafnium dichloride, two (ethyl-methyl amido) hafnium dichlorides, two positive propoxy hafnium dichlorides or diisopropyl
Epoxide hafnium dichloride.
In step (1), reaction is carried out under the conditions of -20~25 DEG C in organic solvent under dry inert gas protection, is taken
The molar ratio of the fulvene compound and alkali metal in generation or the hydride of alkaline-earth metal is 1：1~1.5：1, react stirred overnight
Substituted cyclopentadienyl group salt is filtrated to get afterwards.
The organic solvent used in above-mentioned steps is selected from ether, methyl tertiary butyl ether(MTBE), benzene, toluene, paraxylene, adjacent diformazan
The one or more of mixture of benzene, meta-xylene, mesitylene, tetrahydrofuran, 2- methyltetrahydrofurans.
In step (2), reaction is carried out under the conditions of -50~25 DEG C in organic solvent under dry inert gas protection, is taken
The molar ratio of the cyclopentadienyl group salt in generation and Group IV halide or the derivative of Group IV halide is 2：1, reacted
Filtered after night stirring, mother liquor drains solvent and obtains metallocene compound.
The organic solvent used in above-mentioned steps is selected from ether, methyl tertiary butyl ether(MTBE), benzene, toluene, paraxylene, adjacent diformazan
The one or more of mixture of benzene, meta-xylene, mesitylene, tetrahydrofuran, 2- methyltetrahydrofurans.
Following examples will be helpful to those skilled in the art and further understand the present invention, but not limit in any form
The present invention.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made.These belong to protection scope of the present invention.
Embodiment 1
The synthesis of 6,6- dimethyl fulvenes
500mL ethanol is added into reactor, 16.9g metallic sodiums (0.735mol) are added portionwise, is stirred 2 hours, is added
50.0g cyclopentadiene (0.765mol) is added dropwise in 38.7g acetone (0.666mol), room temperature, is stirred overnight.100mL acetic acid and 500mL
Water quenching is gone out reaction, standing, and point liquid takes organic phase, is crude product, distills, and obtains target product 45.5g, separates yield 65%.1H
NMR(500MHz,CDCl3):δ6.36-6.38(m,2H),6.24-6.26(m,2H),1.85(s,6H)。
Embodiment 2
The synthesis of 3,6,6- trimethyl fulvene
The 12.6g ortho-chlorotolu'enes (0.1mol) added in embodiment 1 are changed to 14.2g o-chloro-anisoles (0.1mol),
Other conditions are constant, and distillation obtains target product 47.2g, separate yield 51%.1H NMR(500MHz,CDCl3):δ6.43-
6.48(m,2H),6.27(s,1H),2.06(s,3H),1.85(s,6H)。
Embodiment 3
The synthesis of 3,4,6,6- tetramethyl fulvene
The 50.0g cyclopentadiene (0.765mol) added in embodiment 1 is changed to 72.0g 1,2- diformazans basic ring penta 2
Alkene (0.765mol), other conditions are constant, distillation, obtain target product 67.2g, separate yield 50%.1H NMR(500MHz,
CDCl3):δ6.43-6.47(m,2H),2.03(s,6H),1.92(s,6H)。
Embodiment 4
The synthesis of 3- isopropyl -6,6- dimethyl fulvenes
The 50.0g cyclopentadiene (0.765mol) added in embodiment 1 is changed to 62.6g 3- isopropylcyclopentadienes
(0.765mol), other conditions are constant, distillation, obtain target product 88.8g, separate yield 62%.1H NMR(500MHz,
CDCl3):δ 6.48 (d, J=12.5Hz, 2H), 6.26 (s, 1H), 2.51 (s, 1H), 1.85 (s, 6H), 1.15 (s, 6H).
Embodiment 5
The synthesis of 3- normal-butyl -6,6- dimethyl fulvenes
The 50.0g cyclopentadiene (0.765mol) added in embodiment 1 is changed to 93.5g 3- normal-butyl cyclopentadiene
(0.765mol), other conditions are constant, distillation, obtain target product 97.2g, separate yield 60%.1H NMR(500MHz,
CDCl3):δ 6.48 (d, J=18.0Hz, 2H), 6.24 (s, 1H), 2.57 (s, 2H), 1.85 (s, 6H), 1.39-1.43 (m,
4H),1.01(s,3H)。
Embodiment 6
The synthesis of the 3- tert-butyl group -6,6- dimethyl fulvenes
The 50.0g cyclopentadiene (0.765mol) added in embodiment 1 is changed to 93.5g 3- tert-butylcyclopentadienes
(0.765mol), other conditions are constant, distillation, obtain target product 80.7g, separate yield 50%.1H NMR(500MHz,
CDCl3):δ 6.49 (d, J=8.0Hz, 2H), 6.26 (s, 1H), 1.84 (s, 6H), 1.47 (s, 9H).
Embodiment 7
The synthesis of 6,6- diphenyl fulvene
500mL ethanol is added into reactor, 16.9g metallic sodiums (0.735mol) are added portionwise, is stirred 2 hours, is added
50.0g cyclopentadiene (0.765mol) is added dropwise in the propiophenones of 121.4g bis- (0.666mol), room temperature, is stirred overnight.100mL acetic acid and
500mL water quenchings are gone out reaction, standing, and point liquid takes organic phase, is crude product, rotates, and methanol mashing, filtering obtains target product
104.3g, separates yield 68%.1H NMR(500MHz,CDCl3):δ7.25-7.40(m,10H),6.18-6.23(m,4H)。
Embodiment 8
The synthesis of the 3- tert-butyl group -6,6- diphenyl fulvene
The 50.0g cyclopentadiene (0.765mol) added in embodiment 7 is changed to 93.5g 3- tert-butylcyclopentadienes
(0.765mol), while adding 15.2g pyrrolidines (0.2145mol), other conditions are constant, obtain target product 102.8g, point
From yield 54%.1H NMR(500MHz,CDCl3):δ7.25-7.40(m,10H),6.23-6.41(m,3H),1.47(s,9H)。
Embodiment 9
The synthesis of 6- methyl -6- phenyl fulvene
500mL ethanol is added into reactor, 16.9g metallic sodiums (0.735mol) are added portionwise, is stirred 2 hours, is added
50.0g cyclopentadiene (0.765mol) is added dropwise in the propiophenones of 79.9g bis- (0.666mol), room temperature, is stirred overnight.100mL acetic acid and
500mL water quenchings are gone out reaction, standing, and point liquid takes organic phase, is crude product, rotates, and methanol mashing, filtering obtains target product
79.4g, separates yield 70%.1H NMR(500MHz,CDCl3):δ6.90-7.25(m,5H),5.83-6.02(m,4H),2.16
(s,3H)。
Embodiment 10
The synthesis of 1- propyl-cyclopentadienyl lithium salts
Under nitrogen atmosphere, tetrahydrofuran 100mL, lithium hydride 0.8g (0.1mol) are added, less than 0 DEG C, dropwise addition is cooled to
10.6g 6,6- dimethyl fulvene (0.1mol), are slowly increased to room temperature, are stirred overnight, filtering, take solid, obtain product 11.2g,
Yield>99%.
Embodiment 11
The synthesis of 1- propyl group -3- methyl cyclopentadienyl lithium salts
The 10.6g 6,6- dimethyl fulvenes (0.1mol) added in embodiment 10 are changed to 12.0g 3,6,6- front threes
Base fulvene (0.1mol), other conditions are constant, obtain product 12.2g, yield 97%.
Embodiment 12
The synthesis of 1- propyl group -3,4- dimethylcyclo-pentadienyl lithium salts
The 10.6g 6,6- dimethyl fulvenes (0.1mol) added in embodiment 10 are changed to 13.4g 3,4,6,6- tetra-
Methyl fulvene (0.1mol), other conditions are constant, obtain product 13.7g, yield 98%.
Embodiment 13
The synthesis of 1,3- diisopropyl cyclopentadiene
The 10.6g 6,6- dimethyl fulvenes (0.1mol) added in embodiment 10 are changed to 14.8g 1- isopropyl -6,
6- dimethyl fulvenes (0.1mol), other conditions are constant, obtain product 15.2g, yield 99%.
Embodiment 14
The synthesis of 1- normal-butyl -3- isopropylcyclopentadienyl lithium salts
The 10.6g 6,6- dimethyl fulvenes (0.1mol) added in embodiment 10 are changed to 16.2g 3- normal-butyl -6,
6- dimethyl fulvenes (0.1mol), other conditions are constant, obtain product 16.6g, yield 99%.
Embodiment 15
The synthesis of the 1- tert-butyl group -3- isopropylcyclopentadienyl lithium salts
The 10.6g 6,6- dimethyl fulvenes (0.1mol) added in embodiment 10 are changed to the 16.2g 3- tert-butyl group -6,
6- dimethyl fulvenes (0.1mol), other conditions are constant, obtain product 16.0g, yield 95%.
Embodiment 16
The synthesis of 6,6- hexichol cyclopentadienyl group lithium salts
The 10.6g 6,6- dimethyl fulvenes (0.1mol) added in embodiment 10 are changed to 23.0g 6,6- diphenyl
Fulvene (0.1mol), other conditions are constant, obtain product 23.3g, yield 98%.
Embodiment 17
The synthesis of the 3- tert-butyl group -6,6- hexichol cyclopentadienyl group lithium salts
The 10.6g 6,6- dimethyl fulvenes (0.1mol) added in embodiment 10 are changed to the 28.6g 3- tert-butyl group -6,
6- diphenyl fulvene (0.1mol), other conditions are constant, obtain product 26.2g, yield 90%.
Embodiment 18
The synthesis of 5- phenethyl cyclopentadienyl group lithium salts
Under nitrogen atmosphere, tetrahydrofuran 100mL, sodium hydride 1.3g (0.05mol) are added, less than 0 DEG C, dropwise addition is cooled to
17.0g 6- methyl -6- phenyl fulvene (0.1mol), is slowly increased to room temperature, is stirred overnight, filtering, takes solid, obtains product
17.7g, yield 98%.
Embodiment 19
The synthesis of double (3- isopropylcyclopentadienyls) hafnium dichlorides
Under nitrogen atmosphere, ether 100mL, 3.2g hafnium tetrachloride (0.01mol) is added into reactor, -30 are cooled to
Below DEG C, 2.3g 1- propyl-cyclopentadienyls lithiums (0.02mol) are added, room temperature is slowly increased to, stirred 17 hours, diatomite is crossed,
Mother liquor is taken, it is product 3.7g, yield 80% to drain solvent.1H NMR(500MHz,CDCl3):δ5.69-5.81(m,8H),
3.23-3.27 (m, 2H), 1.45 (d, J=7.5Hz, 12H).
Embodiment 20
The synthesis of double (3- isopropylcyclopentadienyls) zirconium dichlorides
The 3.2g hafnium tetrachlorides (0.01mol) added in embodiment 18 are changed to 2.3g zirconium chlorides (0.1mol), its
His condition is constant, obtains product 3.1g, yield 82%.1H NMR(500MHz,CDCl3):δ5.69-5.81(m,8H),3.23-
3.27 (m, 2H), 1.45 (d, J=7.5Hz, 12H).
Embodiment 21
The synthesis of double (1- propyl group -3- methyl cyclopentadienyls) hafnium dichlorides
Under nitrogen atmosphere, ether 100mL, 3.2g hafnium tetrachloride (0.01mol) is added into reactor, -30 are cooled to
Below DEG C, 2.6g 1- propyl group -3- methyl cyclopentadienyls lithiums (0.02mol) are added, room temperature is slowly increased to, stirred 17 hours, mistake
Diatomite, takes mother liquor, and it is product 3.9g, yield 82% to drain solvent.1H NMR(500MHz,CDCl3):δ5.70-5.80
(m, 6H), 3.23-3.27 (m, 2H), 2.06 (d, J=5.0Hz, 6H), 1.45 (d, J=7.5Hz, 12H).
Embodiment 22
The synthesis of double (1- propyl group -3- methyl cyclopentadienyls) zirconium dichlorides
The 3.2g hafnium tetrachlorides (0.01mol) added in embodiment 20 are changed to 2.3g zirconium chlorides (0.1mol), its
His condition is constant, obtains product 3.1g, yield 82%.1H NMR(500MHz,CDCl3):δ5.70-5.80(m,6H),3.23-
3.27 (m, 2H), 2.06 (d, J=5.0Hz, 6H), 1.45 (d, J=7.5Hz, 12H).
Embodiment 23
The synthesis of double (1,3- diisopropyls cyclopentadienyl group) hafnium dichlorides
Under nitrogen atmosphere, ether 100mL, 3.2g hafnium tetrachloride (0.01mol) is added into reactor, -30 are cooled to
Below DEG C, 3.1g 1 is added, 3- diisopropyl cyclopentadienyl group lithiums (0.02mol) are slowly increased to room temperature, stirred 17 hours, mistake
Diatomite, takes mother liquor, and it is product 3.7g, yield 68% to drain solvent.1H NMR(500MHz,CDCl3):δ5.70-5.80(m,
8H), 3.22-3.27 (m, 4H), 2.06 (d, J=5.0Hz, 6H), 2.12 (d, J=5.0Hz, 6H), 1.52 (d, J=7.5Hz,
12H), 1.44 (d, J=7.5Hz, 12H).
Embodiment 24
The synthesis of double (1,3- diisopropyls cyclopentadienyl group) zirconium dichlorides
The 3.2g hafnium tetrachlorides (0.01mol) added in embodiment 20 are changed to 2.3g zirconium chlorides (0.1mol), its
His condition is constant, obtains product 3.2g, yield 70%.1H NMR(500MHz,CDCl3):δ5.70-5.80(m,8H),3.22-
3.27 (m, 4H), 2.06 (d, J=5.0Hz, 6H), 2.12 (d, J=5.0Hz, 6H), 1.52 (d, J=7.5Hz, 12H), 1.44
(d, J=7.5Hz, 12H).
Embodiment 25
The synthesis of double (6,6- hexichol cyclopentadienyl group) hafnium dichlorides
Under nitrogen atmosphere, ether 100mL, 3.2g hafnium tetrachloride (0.01mol) is added into reactor, -30 are cooled to
Below DEG C, 4.8g 6 is added, 6- hexichol cyclopentadienyl group lithiums (0.02mol) are slowly increased to room temperature, stirred 17 hours, cross silicon
Diatomaceous earth, takes mother liquor, and it is product 5.7g, yield 80% to drain solvent.1H NMR(500MHz,CDCl3):δ7.20-8.05(m,
20H),5.76-5.88(m,8H)。
Embodiment 26
The synthesis of double (6,6- hexichol cyclopentadienyl group) zirconium dichlorides
The 3.2g hafnium tetrachlorides (0.01mol) added in embodiment 20 are changed to 2.3g zirconium chlorides (0.1mol), its
His condition is constant, obtains product 5.2g, yield 83%.1H NMR(500MHz,CDCl3):δ7.20-8.05(m,20H),5.76-
5.88(m,8H)。
Embodiment 27
The preparation method of substituted cyclopentadienyl metallocene compound, the structure of the metallocene compound prepared is such as
Under：
Preparation process is comprised the steps of：
The first step, under dry inert gas protection, controlling reaction temperature is -20 DEG C, substituted fulvene compound and alkali
The hydride of metal is 1 in molar ratio：1 is reacted in ether, and substituted ring penta 2 is filtrated to get after reaction stirred overnight
Alkenyl salt；
Second step, under dry inert gas protection, controlling reaction temperature is -50 DEG C, and substituted cyclopentadienyl group salt enters
One step is 2 in molar ratio with Group IV halide：1 is reacted in toluene, is answered and is filtered after stirred overnight, mother liquor drains solvent
Obtain metallocene compound.
Whole process is as follows：
In formula：Identify " * " and represent that, with 0-4 non-hydrogen substituent on five-membered ring, preferably 0-2 is individual, more preferred 0 or
1, most preferably 0.
Non-hydrogen substituent independently of each other preferably containing 1 carbon atom~30 carbon atom containing hetero atom or without hetero atom
Alkyl；It is preferred that containing 1 carbon atom~15 carbon atom containing hetero atom or without heteroatomic alkyl, and more preferably contain 1
Carbon atom~10 carbon atom containing hetero atom or without heteroatomic alkyl,
Methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl are included as the alkyl preferred embodiment, used
Base, 1- ethyl propyls, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, pyridine, picolyl, phenyl, 1- phenyl propyls, uncle 4-
Butyl phenyl, 4- aminomethyl phenyls, 3,5- 3,5-dimethylphenyls, 4,4- xenyls or naphthyl.
In the present embodiment, mark " * " is represented on five-membered ring with 1 1- phenyl propyl.
R1And R2Separately selected from hydrogen, containing 1 carbon atom~30 carbon atom containing hetero atom or without heteroatomic
Alkyl；
Preferably, R1And R2Separately selected from hydrogen, containing 1 carbon atom~15 carbon atom containing hetero atom or be free of
Heteroatomic alkyl, and more preferably hydrogen, containing 1 carbon atom~10 carbon atom containing hetero atom or without heteroatomic alkyl,
As most preferably preferred embodiment, selected alkyl comprising methyl, ethyl, propyl group, cyclopenta, cyclohexyl,
Pyridine, phenyl, 4- aminomethyl phenyls, 4- propyl group phenyl, 4- butyl benzenes, 4- tert-butyl-phenyls, benzyl, 4- fluorophenyls, 4- fluoroforms
Base phenyl or 3- trifluoromethyls.
In the present embodiment, R1For methyl, R2For 4- trifluoromethyls.
BHn(n=1 or 2) represents the hydride of alkali metal or alkaline-earth metal, selected from lithium hydride, sodium hydride, hydrofining, hydrogen
Change calcium, beryllium hydride, magnesium hydride, lithium hydride, sodium hydride, hydrofining preferably are selected from, more preferably from lithium hydride, sodium hydride.
Lithium hydride is used in the present embodiment.
M represents Group IV metal, can be titanium, zirconium, hafnium.Zirconium chloride is used in the present embodiment.
Embodiment 28
The preparation method of substituted cyclopentadienyl metallocene compound, the structure of the metallocene compound prepared is such as
Under：
Preparation process is comprised the steps of：
The first step, under dry inert gas protection, controlling reaction temperature is -20 DEG C, substituted fulvene compound and alkali
The hydride of metal is 1 in molar ratio：1 is reacted in ether, and substituted ring penta 2 is filtrated to get after reaction stirred overnight
Alkenyl salt,
Second step, under dry inert gas protection, controlling reaction temperature is -50 DEG C, and substituted cyclopentadienyl group salt enters
The derivative of one step and Group IV halide is 2 in molar ratio：1 is reacted in toluene, is answered and is filtered after stirred overnight, mother liquor
Drain solvent and obtain metallocene compound.
Whole course of reaction is as follows：
In formula：Identify " * " and represent that, with 0-4 non-hydrogen substituent on five-membered ring, preferably 0-2 is individual, more preferred 0 or
1, most preferably 0.
Non-hydrogen substituent independently of each other preferably containing 1 carbon atom~30 carbon atom containing hetero atom or without hetero atom
Alkyl；It is preferred that containing 1 carbon atom~15 carbon atom containing hetero atom or without heteroatomic alkyl, and more preferably contain 1
Carbon atom~10 carbon atom containing hetero atom or without heteroatomic alkyl,
Methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl are included as the alkyl preferred embodiment, used
Base, 1- ethyl propyls, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, pyridine, picolyl, phenyl, 1- phenyl propyls, uncle 4-
Butyl phenyl, 4- aminomethyl phenyls, 3,5- 3,5-dimethylphenyls, 4,4- xenyls or naphthyl.
In the present embodiment, mark " * " represents to carry 4- aminomethyl phenyls, 3,5- 3,5-dimethylphenyls on five-membered ring.
R1And R2Separately selected from hydrogen, containing 1 carbon atom~30 carbon atom containing hetero atom or without heteroatomic
Alkyl；
Preferably, R1And R2Separately selected from hydrogen, containing 1 carbon atom~15 carbon atom containing hetero atom or be free of
Heteroatomic alkyl, and more preferably hydrogen, containing 1 carbon atom~10 carbon atom containing hetero atom or without heteroatomic alkyl,
As most preferably preferred embodiment, selected alkyl comprising methyl, ethyl, propyl group, cyclopenta, cyclohexyl,
Pyridine, phenyl, 4- aminomethyl phenyls, 4- propyl group phenyl, 4- butyl benzenes, 4- tert-butyl-phenyls, benzyl, 4- fluorophenyls, 4- fluoroforms
Base phenyl or 3- trifluoromethyls.
In the present embodiment, R1For cyclopenta, R2For 4- tert-butyl-phenyls.
BHn(n=1 or 2) represents the hydride of alkali metal or alkaline-earth metal, selected from lithium hydride, sodium hydride, hydrofining, hydrogen
Change calcium, beryllium hydride, magnesium hydride, lithium hydride, sodium hydride, hydrofining preferably are selected from, more preferably from lithium hydride, sodium hydride.
Magnesium hydride is used in the present embodiment.
M represents Group IV metal, and the derivative of the Group IV halide of use can be four (dimethyl amido) zirconiums, tetrem
Epoxide zirconium, four (ethyl-methyl amido) zirconiums, four zirconium-n-propylates, four zirconium iso-propoxides, four (dimethyl amido) titaniums, purity titanium tetraethoxide,
Four (ethyl-methyl amido) titaniums, four normal propyl alcohol titaniums, titanium tetraisopropylate, four (dimethyl amido) hafniums, tetraethoxy hafnium, four (ethyls
Methylamino) hafnium, four normal propyl alcohol hafniums, four isopropanol hafniums；Two (dimethyl amido) zirconium dichlorides, diethoxy zirconium dichloride, two
(ethyl-methyl amido) zirconium dichloride, two positive propoxy zirconium dichlorides, diisopropanol epoxide zirconium dichloride, two (dimethyl amidos)
Titanium chloride, diethoxy titanium chloride, two (ethyl-methyl amido) titanium chloride, two positive propoxy titanium chloride, diisopropyl
Epoxide titanium chloride, two (dimethyl amido) hafnium dichlorides, diethoxy hafnium dichloride, two (ethyl-methyl amido) dichlorides
Hafnium, two positive propoxy hafnium dichlorides or diisopropoxy hafnium dichloride.
Two (ethyl-methyl amido) hafnium dichlorides are used in the present embodiment.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of preparation method of substituted cyclopentadienyl metallocene compound, it is characterised in that this method uses following steps：
(1) the cyclopentadienyl group salt that the fulvene compound of substitution and the hydride reaction of alkali metal or alkaline-earth metal are replaced；
(2) derivatives reaction of the cyclopentadienyl group salt of substitution and Group IV halide or Group IV halide obtains metallocene
Compound；
The molecular formula of described substituted fulvene compound and the metallocene compound prepared is respectively：
2. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to claim 1, it is characterised in that
In the molecular formula of described fulvene compound, " * " represents to carry 0-4 non-hydrogen substituent on five-membered ring, and non-hydrogen substituent phase
Mutually independently preferably containing 1 carbon atom~30 carbon atom containing hetero atom or without heteroatomic alkyl；R1And R2Independently
Ground be selected from hydrogen, containing 1 carbon atom~30 carbon atom containing hetero atom or without heteroatomic alkyl.
3. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to claim 1, it is characterised in that
In the molecular formula of described fulvene compound, the number of the connected non-hydrogen substituent of five-membered ring of " * " mark is 0-2, preferably 0
It is individual or 1, more preferably 0.
4. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to claim 1, it is characterised in that
In the molecular formula of described fulvene compound, the connected non-hydrogen substituent of five-membered ring of " * " mark is independently preferably containing 1 carbon original
Son~15 carbon atoms containing hetero atom or without heteroatomic alkyl, more preferably containing containing 1 carbon atom~10 carbon atom
Hetero atom or without heteroatomic alkyl.
5. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to claim 1, it is characterised in that
In the molecular formula of described fulvene compound, R1And R2Separately containing selected from hydrogen, containing 1 carbon atom~15 carbon atom
Hetero atom or without heteroatomic alkyl, and more preferably hydrogen, containing 1 carbon atom~10 carbon atom containing hetero atom or without miscellaneous
The alkyl of atom.
6. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to any one of claim 1-5,
Characterized in that,
" * " represent five-membered ring on carry containing hetero atom or without heteroatomic alkyl include methyl, ethyl, propyl group, isopropyl,
Normal-butyl, isobutyl group, 1- ethyl propyls, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, pyridine, picolyl, phenyl, 1- benzene
Base propyl group, 4- tert-butyl-phenyls, 4- aminomethyl phenyls, 3,5- 3,5-dimethylphenyls, 4,4- xenyls or naphthyl；
R1And R2What is represented includes methyl, ethyl, propyl group, cyclopenta, cyclohexyl, pyrrole containing hetero atom or without heteroatomic alkyl
Pyridine, phenyl, 4- aminomethyl phenyls, 4- propyl group phenyl, 4- butyl benzenes, 4- tert-butyl-phenyls, benzyl, 4- fluorophenyls, 4- trifluoromethyls
Phenyl or 3- trifluoromethyls.
7. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to claim 1, it is characterised in that
Group IV halide is the chloride of the chloride, preferably zirconium or hafnium of titanium, zirconium or hafnium；
The derivative of Group IV halide be four (dimethyl amido) zirconiums, tetraethoxy zirconium, four (ethyl-methyl amido) zirconiums, four just
Propyl alcohol zirconium, four zirconium iso-propoxides, four (dimethyl amido) titaniums, purity titanium tetraethoxide, four (ethyl-methyl amido) titaniums, four normal propyl alcohol titaniums,
Titanium tetraisopropylate, four (dimethyl amido) hafniums, tetraethoxy hafnium, four (ethyl-methyl amido) hafniums, four normal propyl alcohol hafniums, four isopropanols
Hafnium；Two (dimethyl amido) zirconium dichlorides, diethoxy zirconium dichloride, two (ethyl-methyl amido) zirconium dichlorides, two positive third oxygen
Base zirconium dichloride, diisopropanol epoxide zirconium dichloride, two (dimethyl amido) titanium chloride, diethoxy titanium chloride, two (second
Ylmethyl amido) titanium chloride, two positive propoxy titanium chloride, diisopropoxy titanium chloride, two (dimethyl amido) dichloros
Change hafnium, diethoxy hafnium dichloride, two (ethyl-methyl amido) hafnium dichlorides, two positive propoxy hafnium dichlorides or diisopropoxy
Hafnium dichloride.
8. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to claim 1, it is characterised in that
Described alkali metal or the hydride of alkaline-earth metal are selected from lithium hydride, sodium hydride, hydrofining, calcium hydride, beryllium hydride or magnesium hydride,
It is preferred that lithium hydride, sodium hydride or hydrofining, more preferably from lithium hydride or sodium hydride, more preferably lithium hydride.
9. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to claim 1, it is characterised in that
In step (1), reaction is carried out under the conditions of -20~25 DEG C in organic solvent under dry inert gas protection, substituted fulvene
The molar ratio of the hydride of compound and alkali metal or alkaline-earth metal is 1：1~1.5：1, filtered after reacting stirred overnight
To substituted cyclopentadienyl group salt, the organic solvent of use is selected from ether, methyl tertiary butyl ether(MTBE), benzene, toluene, paraxylene, neighbour
The one or more of mixture of dimethylbenzene, meta-xylene, mesitylene, tetrahydrofuran, 2- methyltetrahydrofurans.
10. a kind of preparation method of substituted cyclopentadienyl metallocene compound according to claim 1, its feature exists
In in step (2), reaction is carried out under the conditions of -50~25 DEG C in organic solvent under dry inert gas protection, substituted ring
The molar ratio of pentadienyl salt and Group IV halide or the derivative of Group IV halide is 2：1, react stirred overnight
After filter, mother liquor drains solvent and obtains metallocene compound, and the organic solvent of use is selected from ether, methyl tertiary butyl ether(MTBE), benzene, first
Benzene, paraxylene, ortho-xylene, meta-xylene, mesitylene, tetrahydrofuran, 2- methyltetrahydrofurans are one or more of to be mixed
Compound.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1245806A (en) * | 1998-08-20 | 2000-03-01 | 拜尔公司 | Catalyst based on metal fulvene compounding ingredient |
Non-Patent Citations (2)
| Title |
|---|
| WAYNE A. KING ET AL.: "Absolute Metal-Ligand σ Bond Enthalpies in Group 4 Metallocenes A Thermochemical, Structural, Photoelectron Spectroscopic, and abInitio Quantum Chemical Investigation", 《J. AM. CHEM. SOC.》 * |
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