CN107312045B - Preparation method of substituted cyclopentadienyl metallocene compound - Google Patents
Preparation method of substituted cyclopentadienyl metallocene compound Download PDFInfo
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- C07F17/00—Metallocenes
Abstract
The invention relates to a preparation method of a substituted cyclopentadienyl metallocene compound, which adopts the reaction of a cyclopentadiene compound and an aldehyde ketone compound to generate a fulvene compound, then reacts with a metal hydride to generate a substituted cyclopentadienyl salt, and further reacts with a group IV metal halide to obtain the metallocene compound. Compared with the prior art, the method has the advantages of high product yield, convenient operation, good economy and the like, and is suitable for industrial production.
Description
Technical Field
the invention relates to a preparation method of a metallocene compound with a novel structure, in particular to a preparation method of a substituted cyclopentadienyl metallocene compound.
background
Metallocene compounds are organometallic complexes composed of transition metal elements or rare earth metal elements and at least one cyclopentadiene or cyclopentadiene derivative as ligands, which are widely used in the production and preparation of polyolefins and have the advantages of high catalytic activity, multiple applicable monomers, single active site, precise control of polymer structure, etc. (metallocene catalysts and olefin polymers thereof, chemical industry publishers, 2000). In the past decades, various metallocene complexes have been synthesized by designing various novel ligands by changing substituents on the metallocene ring (chem. Rev.2000,100, 1205). The physical and chemical properties of the corresponding metal complexes change with the change of substituents on the metallocene ring, mainly due to the electronic and steric hindrance caused by the replacement of the hydrogen atom on the metallocene ring by other groups (chem. rev.2000,100, 1253).
Most metallocene catalyst preparation processes use n-butyllithium reacted with a ligand to produce the corresponding lithium salt, which is then reacted with a metal halide to give the product (U.S. Pat. No. 6,252,098; U.S. Pat. No. 6,175,027; J.Am.chem.Soc.1998,120, 2308; Organmetalllics, 1999,18,1873; Organmetalllics, 2000,19,420).
The literature reports that metallocene compounds are obtained by first reacting n-butyllithium with a metal halide to form bis-n-butyl dihalide and then with a ligand (Organometallics 1999,18,1583; polyhydron 2005,24,1325). Or by first synthesizing M (NH)2)4and then reacted with a ligand to prepare a metallocene compound (Organometallics 1996,14, 5; U.S. Pat. No. 3, 8,013,177).
Some ligands have a specific structure, and sodium salts of the corresponding ligands can be prepared directly from sodium metal (Journal of Organometallic Chemistry 2009,694,1059).
In view of the above, the synthesis method of metallocene catalyst has been the focus of research, and no patent report on the production of metallocene compound by reacting alkali metal or alkaline earth metal hydride, especially lithium hydride, sodium hydride and ligand to produce corresponding cyclopentadienyl salt has been found.
Disclosure of Invention
The present invention aims at providing a process for preparing substituted cyclopentadienyl metallocene compounds with high yield, convenient operation and good economy.
the purpose of the invention can be realized by the following technical scheme:
The preparation method of the substituted cyclopentadienyl metallocene compound comprises the following steps:
The preparation process comprises the following steps:
A first step of reacting a substituted fulvene compound with a hydride of an alkali metal or alkaline earth metal to give a substituted cyclopentadienyl salt;
In the second step, the substituted cyclopentadienyl salt is further reacted with a group IV halide or a group IV halide derivative to obtain a metallocene compound. The process is as follows:
In the formula: the symbol "-" denotes a heteroatom-containing or heteroatom-free alkyl radical which carries from 0 to 4 non-hydrogen substituents on the five-membered ring and which, independently of one another, preferably contains from 1 to 30 carbon atoms; r1And R2each independently selected from hydrogen, heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 30 carbon atoms; BHn(n ═ 1 or 2) represents a hydride of an alkali metal or an alkaline earth metal. M represents a group IV metal: x represents a halogen.
M is a transition metal selected from titanium, zirconium or hafnium.
m is preferably zirconium or hafnium.
The number of the non-hydrogen substituents connected with the five-membered ring with the mark is 0 to 2,
Preferably 0 or 1.
In a most preferred embodiment, the number of non-hydrogen substituents attached to the five-membered ring with an "x" designation is 0.
The non-hydrogen substituents attached to said five-membered ring with an "-" designation are independently preferably heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 15 carbon atoms.
more preferred are heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 10 carbon atoms.
As the most preferable embodiment, the heteroatom-containing or heteroatom-free alkyl group of 1 to 10 carbon atoms includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 1-ethylpropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, pyridine, picolyl, phenyl, 1-phenylpropyl, 4-tert-butylphenyl, 4-methylphenyl, 3, 5-dimethylphenyl, 4-biphenyl or naphthyl.
Said R1and R2each independently selected from hydrogen, a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 15 carbon atoms.
More preferred are hydrogen, heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 10 carbon atoms.
As the most preferable embodiment, the heteroatom-containing or heteroatom-free alkyl group of 1 to 10 carbon atoms includes methyl, ethyl, propyl, cyclopentyl, cyclohexyl, pyridine, phenyl, 4-methylphenyl, 4-propylphenyl, 4-butylbenzene, 4-tert-butylphenyl, benzyl, 4-fluorophenyl, 4-trifluoromethylphenyl or 3-trifluoromethylphenyl.
The hydride of the alkali metal or the alkaline earth metal is selected from lithium hydride, sodium hydride, potassium hydride, calcium hydride, beryllium hydride and magnesium hydride,
Preferably selected from lithium hydride, sodium hydride, potassium hydride,
In a most preferred embodiment, the metal is selected from lithium hydride and sodium hydride.
preferably, X represents chlorine.
The group IV halide derivatives are tetrakis (dimethylamino) zirconium, tetraethoxyzirconium, tetrakis (ethylmethylamino) zirconium, tetra-n-propoxytrianium, tetraisopropanozirconium, tetrakis (dimethylamino) titanium, tetraethoxytitanium, tetrakis (ethylmethylamino) titanium, tetra-n-propoxytitanium, tetraisopropanotitanium, tetrakis (dimethylamino) hafnium, tetraethoxyhafnium, tetrakis (ethylmethylamino) hafnium, tetra-n-propoxyaldium, tetraisopropanohafnium; bis (dimethylamino) zirconium dichloride, diethoxy zirconium dichloride, bis (ethylmethylamino) zirconium dichloride, bis (n-propoxy) zirconium dichloride, diisopropoxy zirconium dichloride, bis (dimethylamino) titanium dichloride, diethoxy titanium dichloride, bis (ethylmethylamino) titanium dichloride, bis (n-propoxy) titanium dichloride, diisopropoxy titanium dichloride, bis (dimethylamino) hafnium dichloride, diethoxy hafnium dichloride, bis (ethylmethylamino) hafnium dichloride, bis (n-propoxy) hafnium dichloride, or diisopropoxy hafnium dichloride.
In the step (1), the reaction is carried out in an organic solvent at the temperature of-20-25 ℃ under the protection of dry inert gas, and the feeding molar ratio of the substituted fulvene compound to the hydride of the alkali metal or the alkaline earth metal is 1: 1-1.5: 1, the reaction was stirred overnight and filtered to give the substituted cyclopentadienyl salt.
The organic solvent adopted in the step is one or a mixture of more of diethyl ether, methyl tert-butyl ether, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, tetrahydrofuran and 2-methyltetrahydrofuran.
in the step (2), the reaction is carried out in an organic solvent at-50-25 ℃ under the protection of dry inert gas, and the feeding molar ratio of the substituted cyclopentadienyl salt to the IV group halide or the IV group halide derivative is 2: 1, stirring the reaction overnight, filtering, and pumping the solvent out of the mother liquor to obtain the metallocene compound.
The organic solvent adopted in the step is one or a mixture of more of diethyl ether, methyl tert-butyl ether, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, tetrahydrofuran and 2-methyltetrahydrofuran.
Compared with the prior art, the method has the advantages of good stability of the used raw materials, easy quantification and convenient operation, and the method has the advantages of high product yield, good economy and suitability for industrial production.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The preparation method of the substituted cyclopentadienyl metallocene compound comprises the following steps:
The preparation process comprises the following steps:
A first step of reacting a substituted fulvene compound with a hydride of an alkali metal or alkaline earth metal to give a substituted cyclopentadienyl salt;
In the second step, the substituted cyclopentadienyl salt is further reacted with a group IV halide or a group IV halide derivative to obtain a metallocene compound. The process is as follows:
In the formula: the symbol "-" denotes a heteroatom-containing or heteroatom-free alkyl radical which carries from 0 to 4 non-hydrogen substituents on the five-membered ring and which, independently of one another, preferably contains from 1 to 30 carbon atoms;
R1And R2Each independently selected from hydrogen, heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 30 carbon atoms;
BHn(n ═ 1 or 2) represents a hydride of an alkali metal or an alkaline earth metal.
M represents a group IV metal, which may be titanium, zirconium, hafnium
Preferably, M is zirconium, hafnium,
X represents a halogen such as chlorine.
the number of non-hydrogen substituents attached to the five-membered ring identified by "-" is 0 to 2, preferably 0 or 1, and more preferably 0.
The non-hydrogen substituents attached to the five-membered ring with the "-" designation are independently preferably heteroatom-containing or heteroatom-free alkyl groups containing from 1 carbon atom to 15 carbon atoms;
More preferably a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 10 carbon atoms,
As a most preferred embodiment, the alkyl group employed comprises methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 1-ethylpropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, pyridine, picolyl, phenyl, 1-phenylpropyl, 4-tert-butylphenyl, 4-methylphenyl, 3, 5-dimethylphenyl, 4-biphenyl or naphthyl.
R1and R2Each independently selected from hydrogen, heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 15 carbon atoms,
more preferably hydrogen, a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 10 carbon atoms,
As a most preferred embodiment, the alkyl group selected comprises methyl, ethyl, propyl, cyclopentyl, cyclohexyl, pyridine, phenyl, 4-methylphenyl, 4-propylphenyl, 4-butylbenzene, 4-tert-butylphenyl, benzyl, 4-fluorophenyl, 4-trifluoromethylphenyl or 3-trifluoromethylphenyl.
The hydride of an alkali metal or an alkaline earth metal is selected from the group consisting of lithium hydride, sodium hydride, potassium hydride, calcium hydride, beryllium hydride, magnesium hydride,
Preferably selected from lithium hydride, sodium hydride, potassium hydride,
More preferably from lithium hydride or sodium hydride.
The group IV halide derivatives are tetrakis (dimethylamino) zirconium, tetraethoxyzirconium, tetrakis (ethylmethylamino) zirconium, tetra-n-propoxytrianium, tetraisopropanozirconium, tetrakis (dimethylamino) titanium, tetraethoxytitanium, tetrakis (ethylmethylamino) titanium, tetra-n-propoxytitanium, tetraisopropanotitanium, tetrakis (dimethylamino) hafnium, tetraethoxyhafnium, tetrakis (ethylmethylamino) hafnium, tetra-n-propoxyaldium, tetraisopropanohafnium; bis (dimethylamino) zirconium dichloride, diethoxy zirconium dichloride, bis (ethylmethylamino) zirconium dichloride, bis (n-propoxy) zirconium dichloride, diisopropoxy zirconium dichloride, bis (dimethylamino) titanium dichloride, diethoxy titanium dichloride, bis (ethylmethylamino) titanium dichloride, bis (n-propoxy) titanium dichloride, diisopropoxy titanium dichloride, bis (dimethylamino) hafnium dichloride, diethoxy hafnium dichloride, bis (ethylmethylamino) hafnium dichloride, bis (n-propoxy) hafnium dichloride, or diisopropoxy hafnium dichloride.
In the step (1), the reaction is carried out in an organic solvent at the temperature of-20-25 ℃ under the protection of dry inert gas, and the feeding molar ratio of the substituted fulvene compound to the hydride of the alkali metal or the alkaline earth metal is 1: 1-1.5: 1, the reaction was stirred overnight and filtered to give the substituted cyclopentadienyl salt.
The organic solvent adopted in the step is one or a mixture of more of diethyl ether, methyl tert-butyl ether, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, tetrahydrofuran and 2-methyltetrahydrofuran.
In the step (2), the reaction is carried out in an organic solvent at-50-25 ℃ under the protection of dry inert gas, and the feeding molar ratio of the substituted cyclopentadienyl salt to the IV group halide or the IV group halide derivative is 2: 1, stirring the reaction overnight, filtering, and pumping the solvent out of the mother liquor to obtain the metallocene compound.
the organic solvent adopted in the step is one or a mixture of more of diethyl ether, methyl tert-butyl ether, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, tetrahydrofuran and 2-methyltetrahydrofuran.
The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Synthesis of 6, 6-dimethylfulvene
500mL of ethanol was added to the reactor, 16.9g of metallic sodium (0.735mol) was added in portions, stirred for 2 hours, 38.7g of acetone (0.666mol) was added, 50.0g of cyclopentadiene (0.765mol) was added dropwise at room temperature, and stirred overnight. 100mL of acetic acid and 500mL of water are quenched for reaction, the mixture is stood and separated, an organic phase is taken as a crude product, distillation is carried out, 45.5g of a target product is obtained, and the separation yield is 65%.1H NMR(500MHz,CDCl3):δ6.36-6.38(m,2H),6.24-6.26(m,2H),1.85(s,6H)。
example 2
Synthesis of 3,6, 6-trimethylfulvene
the amount of 12.6g of o-chlorotoluene (0.1mol) added in example 1 was changed to 14.2g of o-chloroanisole (0.1mol), and the desired product was obtained by distillation in a yield of 51% under otherwise unchanged conditions.1H NMR(500MHz,CDCl3):δ6.43-6.48(m,2H),6.27(s,1H),2.06(s,3H),1.85(s,6H)。
Example 3
Synthesis of 3,4,6, 6-tetramethyl fulvene
50.0g of cyclopentadiene (0.765mol) added in example 1 was changed to 72.0g of 1, 2-dimethylcyclopentadiene (0.765mol), and distillation was carried out under the same conditions to obtain 67.2g of the objective product with an isolated yield of 50%.1H NMR(500MHz,CDCl3):δ6.43-6.47(m,2H),2.03(s,6H),1.92(s,6H)。
Example 4
synthesis of 3-isopropyl-6, 6-dimethyl fulvene
While changing 50.0g of cyclopentadiene (0.765mol) added in example 1 to 62.6g of 3-isopropylcyclopentadiene (0.765mol), the distillation was carried out under the same conditions to obtain 88.8g of the objective product in an isolated yield of 62%.1H NMR(500MHz,CDCl3):δ6.48(d,J＝12.5Hz,2H),6.26(s,1H)，2.51(s,1H),1.85(s,6H)，1.15(s,6H)。
example 5
Synthesis of 3-n-butyl-6, 6-dimethyl fulvene
By changing 50.0g of cyclopentadiene (0.765mol) added in example 1 to 93.5g of 3-n-butylcyclopentadiene (0.765mol) and distilling the mixture under the same conditions, 97.2g of the objective product was obtained with an isolated yield of 60%.1H NMR(500MHz,CDCl3):δ6.48(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)。
Example 6
Synthesis of 3-tert-butyl-6, 6-dimethyl fulvene
The 50.0g of cyclopentadiene (0.765mol) charged in example 1 was changed to 93.5g of 3-tert-butylcyclopentadiene (0.765mol), and distillation was carried out under the same conditions to obtain 80.7g of the objective product with an isolated yield of 50%.1H NMR(500MHz,CDCl3):δ6.49(d,J＝8.0Hz,2H),6.26(s,1H),1.84(s,6H),1.47(s,9H)。
Example 7
synthesis of 6, 6-diphenyl fulvene
500mL of ethanol was added to the reactor, 16.9g of metallic sodium (0.735mol) was added in portions, stirred for 2 hours, 121.4g of diphenylacetone (0.666mol) was added, 50.0g of cyclopentadiene (0.765mol) was added dropwise at room temperature, and stirred overnight. 100mL of acetic acid and 500mL of water are quenched for reaction, the mixture is placed still and separated, an organic phase is taken as a crude product, rotary evaporation is carried out, methanol is used for pulping, and filtration is carried out, so that 104.3g of a target product is obtained, and the separation yield is 68%.1H NMR(500MHz,CDCl3):δ7.25-7.40(m,10H),6.18-6.23(m,4H)。
Example 8
Synthesis of 3-tert-butyl-6, 6-diphenyl fulvene
50.0g of cyclopentadiene (0.765mol) charged in example 7 was changed to 93.5g of 3-tert-butylcyclopentadiene (0.765mol), and 15.2g of pyrrolidine (0.2145mol) was added simultaneously with the other conditions, to obtain 102.8g of the objective product isolated in 54% yield.1H NMR(500MHz,CDCl3):δ7.25-7.40(m,10H),6.23-6.41(m,3H),1.47(s,9H)。
example 9
Synthesis of 6-methyl-6-phenyl fulvene
500mL of ethanol was added to the reactor, 16.9g of metallic sodium (0.735mol) was added in portions, and stirred for 2 hours, 79.9g of diphenylacetone (0.666mol) was added, 50.0g of cyclopentadiene (0.765mol) was added dropwise at room temperature, and stirred overnight. 100mL of acetic acid and 500mL of water are quenched for reaction, the mixture is placed still and separated, an organic phase is taken as a crude product, the crude product is steamed in a rotary mode, methanol is pulped, and the filtration is carried out, so that 79.4g of a target product is obtained, and the separation yield is 70%.1H NMR(500MHz,CDCl3):δ6.90-7.25(m,5H),5.83-6.02(m,4H),2.16(s,3H)。
Example 10
Synthesis of 1-propylcyclopentadienyl lithium salt
Adding 100mL of tetrahydrofuran and 0.8g (0.1mol) of lithium hydride under the nitrogen atmosphere, cooling to below 0 ℃, dropwise adding 10.6g of 6, 6-dimethyl fulvene (0.1mol), slowly raising to room temperature, stirring overnight, filtering, and taking solid to obtain 11.2g of a product with the yield of more than 99%.
Example 11
Synthesis of 1-propyl-3-methylcyclopentadienyl lithium salt
10.6g of 6, 6-dimethylfulvene (0.1mol) added in example 10 was changed to 12.0g of 3,6, 6-trimethylfulvene (0.1mol), and the other conditions were unchanged to give 12.2g of the product in 97% yield.
Example 12
Synthesis of 1-propyl-3, 4-dimethylcyclopentadienyl lithium salt
10.6g of 6, 6-dimethylfulvene (0.1mol) added in example 10 was changed to 13.4g of 3,4,6, 6-tetramethylfulvene (0.1mol), and the other conditions were not changed to give 13.7g of the product in 98% yield.
Example 13
Synthesis of 1, 3-diisopropylpentadiene
10.6g of 6, 6-dimethylfulvene (0.1mol) added in example 10 was changed to 14.8g of 1-isopropyl-6, 6-dimethylfulvene (0.1mol), and the other conditions were unchanged to give 15.2g of the product in 99% yield.
Example 14
Synthesis of 1-n-butyl-3-isopropyl cyclopentadienyl lithium salt
10.6g of 6, 6-dimethylfulvene (0.1mol) added in example 10 was changed to 16.2g of 3-n-butyl-6, 6-dimethylfulvene (0.1mol), and the other conditions were not changed to give 16.6g of the product in 99% yield.
Example 15
Synthesis of 1-tert-butyl-3-isopropylcyclopentadienyl lithium salt
10.6g of 6, 6-dimethylfulvene (0.1mol) added in example 10 was changed to 16.2g of 3-tert-butyl-6, 6-dimethylfulvene (0.1mol), and the other conditions were unchanged to give 16.0g of the product in 95% yield.
Example 16
synthesis of 6, 6-diphenylcyclopentadienyl lithium salt
The 10.6g of 6, 6-dimethylfulvene (0.1mol) added in example 10 was changed to 23.0g of 6, 6-diphenylfulvene (0.1mol), and the other conditions were unchanged to give 23.3g of the product in 98% yield.
Example 17
Synthesis of 3-tert-butyl-6, 6-diphenylcyclopentadienyl lithium salt
10.6g of 6, 6-dimethylfulvene (0.1mol) added in example 10 was changed to 28.6g of 3-tert-butyl-6, 6-diphenylfulvene (0.1mol), and the other conditions were unchanged to give 26.2g of the product in 90% yield.
Example 18
synthesis of 5-phenethylcyclopentadienyl lithium salt
Under nitrogen atmosphere, 100mL of tetrahydrofuran and 1.3g (0.05mol) of sodium hydride are added, the temperature is reduced to below 0 ℃, 17.0g of 6-methyl-6-phenyl fulvene (0.1mol) is added dropwise, the mixture is slowly raised to the room temperature, stirred overnight and filtered to obtain a solid, and 17.7g of a product with the yield of 98% is obtained.
Example 19
Synthesis of bis (3-isopropylcyclopentadienyl) hafnium dichloride
Adding 100mL of diethyl ether and 3.2g of hafnium tetrachloride (0.01mol) into a reactor under the nitrogen atmosphere, cooling to below-30 ℃, adding 2.3g of 1-propylcyclopentadienyl lithium (0.02mol), slowly raising the temperature to room temperature, stirring for 17 hours, passing through kieselguhr, taking mother liquor, and pumping out the solvent to obtain 3.7g of a product, wherein the yield is 80%.1H NMR(500MHz,CDCl3):δ5.69-5.81(m,8H),3.23-3.27(m,2H),1.45(d,J＝7.5Hz,12H)。
example 20
Synthesis of bis (3-isopropylcyclopentadienyl) zirconium dichloride
The amount of 3.2g of hafnium tetrachloride (0.01mol) charged in example 18 was changed to 2.3g of zirconium tetrachloride (0.1mol), and the other conditions were not changed to obtain 3.1g of a product in 82% yield.1H NMR(500MHz,CDCl3):δ5.69-5.81(m,8H),3.23-3.27(m,2H),1.45(d,J＝7.5Hz,12H)。
Example 21
Synthesis of bis (1-propyl-3-methylcyclopentadienyl) hafnium dichloride
Adding 100mL of diethyl ether and 3.2g of hafnium tetrachloride (0.01mol) into a reactor under the nitrogen atmosphere, cooling to below-30 ℃, adding 2.6g of 1-propyl-3-methylcyclopentadienyl lithium (0.02mol), slowly raising the temperature to room temperature, stirring for 17 hours, passing through kieselguhr, taking mother liquor, and pumping out the solvent, namely 3.9g of a product with the yield of 82%. 1H NMR (500MHz, CDCl)3):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)。
Example 22
Synthesis of bis (1-propyl-3-methylcyclopentadienyl) zirconium dichloride
The amount of 3.2g of hafnium tetrachloride (0.01mol) charged in example 20 was changed to 2.3g of zirconium tetrachloride (0.1mol), and the other conditions were not changed to obtain 3.1g of a product in 82% yield.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)。
Example 23
Synthesis of bis (1, 3-diisopropylcyclopentadienyl) hafnium dichloride
100mL of diethyl ether and 3.2g of hafnium tetrachloride (0.01mol) are added into a reactor under the nitrogen atmosphere, the temperature is reduced to below minus 30 ℃, 3.1g of 1, 3-diisopropyl cyclopentadienyl lithium (0.02mol) is added, the temperature is slowly raised to the room temperature, the mixture is stirred for 17 hours, the mother liquor is taken out after passing through diatomite, the solvent is extracted, namely 3.7g of the product, and the yield is 68%.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)。
Example 24
Synthesis of bis (1, 3-diisopropylcyclopentadienyl) zirconium dichloride
The amount of 3.2g of hafnium tetrachloride (0.01mol) charged in example 20 was changed to 2.3g of zirconium tetrachloride (0.1mol), and the other conditions were not changed to obtain 3.2g of a product in 70% yield.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)。
example 25
Synthesis of bis (6, 6-diphenylcyclopentadienyl) hafnium dichloride
Adding 100mL of diethyl ether and 3.2g of hafnium tetrachloride (0.01mol) into a reactor under the nitrogen atmosphere, cooling to below-30 ℃, adding 4.8g of 6, 6-diphenylcyclopentadienyl lithium (0.02mol), slowly raising the temperature to room temperature, stirring for 17 hours, passing through kieselguhr, taking mother liquor, and pumping out the solvent to obtain 5.7g of a product, wherein the yield is 80%.1H NMR(500MHz,CDCl3):δ7.20-8.05(m,20H),5.76-5.88(m,8H)。
Example 26
Synthesis of bis (6, 6-diphenylcyclopentadienyl) zirconium dichloride
The amount of 3.2g of hafnium tetrachloride (0.01mol) charged in example 20 was changed to 2.3g of zirconium tetrachloride (0.1mol), and the other conditions were not changed to obtain 5.2g of a product in 83% yield.1H NMR(500MHz,CDCl3):δ7.20-8.05(m,20H),5.76-5.88(m,8H)。
Example 27
the preparation method of the substituted cyclopentadienyl metallocene compound comprises the following steps:
The preparation process comprises the following steps:
In the first step, under the protection of dry inert gas, the reaction temperature is controlled to be-20 ℃, and the molar ratio of substituted fulvene compound to alkali metal hydride is 1: 1, reacting in ether, stirring overnight, and filtering to obtain substituted cyclopentadienyl salt;
And secondly, under the protection of dry inert gas, controlling the reaction temperature to be-50 ℃, and further mixing the substituted cyclopentadienyl salt and the IV group halide according to the mol ratio of 2: 1 in toluene, stirring overnight, filtering, and pumping the solvent out of the mother liquor to obtain the metallocene compound.
The whole process is as follows:
in the formula: the symbol "-" indicates that the five-membered ring has 0 to 4 non-hydrogen substituents, preferably 0 to 2, more preferably 0 or 1, and most preferably 0.
The non-hydrogen substituents are independently preferably heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 30 carbon atoms; preferably a heteroatom-containing or heteroatom-free alkyl group containing from 1 carbon atom to 15 carbon atoms, and more preferably a heteroatom-containing or heteroatom-free alkyl group containing from 1 carbon atom to 10 carbon atoms,
As a preferred embodiment, the alkyl group employed comprises methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 1-ethylpropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, pyridine, picolyl, phenyl, 1-phenylpropyl, 4-tert-butylphenyl, 4-methylphenyl, 3, 5-dimethylphenyl, 4-biphenyl or naphthyl.
In this example, the symbol "+" indicates that the five-membered ring has 1-phenylpropyl group.
R1And R2Each independently selected from hydrogen, heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 30 carbon atoms;
Preferably, R1And R2Each independently selected from hydrogen, a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 15 carbon atoms, and more preferably from hydrogen, a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 10 carbon atoms,
as a most preferred embodiment, the alkyl group selected comprises methyl, ethyl, propyl, cyclopentyl, cyclohexyl, pyridine, phenyl, 4-methylphenyl, 4-propylphenyl, 4-butylbenzene, 4-tert-butylphenyl, benzyl, 4-fluorophenyl, 4-trifluoromethylphenyl or 3-trifluoromethylphenyl.
In this embodiment, R1Is methyl, R2Is 4-trifluoromethylphenyl.
BHn(n ═ 1 or 2) represents a hydride of an alkali metal or an alkaline earth metal, and is selected from the group consisting of lithium hydride, sodium hydride, potassium hydride, calcium hydride, beryllium hydride and magnesium hydride, preferably from the group consisting of lithium hydride, sodium hydride and potassium hydride, and more preferably from the group consisting of lithium hydride and sodium hydride.
Lithium hydride is used in this example.
m represents a group IV metal, and may be titanium, zirconium or hafnium. Zirconium chloride was used in this example.
Example 28
the preparation method of the substituted cyclopentadienyl metallocene compound comprises the following steps:
The preparation process comprises the following steps:
In the first step, under the protection of dry inert gas, the reaction temperature is controlled to be-20 ℃, and the molar ratio of substituted fulvene compound to alkali metal hydride is 1: 1 in ether, stirring the reaction overnight, filtering to obtain substituted cyclopentadienyl salt,
And secondly, under the protection of dry inert gas, controlling the reaction temperature to be 50 ℃ below zero, and further mixing the substituted cyclopentadienyl salt and the derivative of the IV group halide according to the mol ratio of 2: 1 in toluene, stirring overnight, filtering, and pumping the solvent out of the mother liquor to obtain the metallocene compound.
The whole reaction process is as follows:
in the formula: the symbol "-" indicates that the five-membered ring has 0 to 4 non-hydrogen substituents, preferably 0 to 2, more preferably 0 or 1, and most preferably 0.
The non-hydrogen substituents are independently preferably heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 30 carbon atoms; preferably a heteroatom-containing or heteroatom-free alkyl group containing from 1 carbon atom to 15 carbon atoms, and more preferably a heteroatom-containing or heteroatom-free alkyl group containing from 1 carbon atom to 10 carbon atoms,
As a preferred embodiment, the alkyl group employed comprises methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 1-ethylpropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, pyridine, picolyl, phenyl, 1-phenylpropyl, 4-tert-butylphenyl, 4-methylphenyl, 3, 5-dimethylphenyl, 4-biphenyl or naphthyl.
in this example, the symbol "+" indicates that the five-membered ring has 4-methylphenyl and 3, 5-dimethylphenyl groups.
R1and R2Each independently selected from hydrogen, heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 30 carbon atoms;
preferably, R1And R2each independently selected from hydrogen, a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 15 carbon atoms, and more preferably from hydrogen, a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 10 carbon atoms,
As a most preferred embodiment, the alkyl group selected comprises methyl, ethyl, propyl, cyclopentyl, cyclohexyl, pyridine, phenyl, 4-methylphenyl, 4-propylphenyl, 4-butylbenzene, 4-tert-butylphenyl, benzyl, 4-fluorophenyl, 4-trifluoromethylphenyl or 3-trifluoromethylphenyl.
In this embodiment, R1Is cyclopentyl, R2Is 4-tert-butylphenyl.
BHn(n-1 or 2) represents a hydride of an alkali metal or an alkaline earth metal selected from lithium hydride, sodium hydride, and hydrogen hydridePotassium, calcium hydride, beryllium hydride, magnesium hydride, preferably from lithium hydride, sodium hydride, potassium hydride, more preferably from lithium hydride, sodium hydride.
Magnesium hydride is used in this example.
M represents a group IV metal, and the group IV halide derivative to be used may be tetrakis (dimethylamino) zirconium, tetraethoxyzirconium, tetrakis (ethylmethylamino) zirconium, tetra-n-propoxzirconium, tetraisopropanozirconium, tetrakis (dimethylamino) titanium, tetraethoxytitanium, tetrakis (ethylmethylamino) titanium, tetra-n-propoxytitanium, tetraisopropanotitanium, tetrakis (dimethylamino) hafnium, tetraethoxyhafnium, tetrakis (ethylmethylamino) hafnium, tetra-n-propoxyalkyl hafnium, tetraisopropanohafnium; bis (dimethylamino) zirconium dichloride, diethoxy zirconium dichloride, bis (ethylmethylamino) zirconium dichloride, bis (n-propoxy) zirconium dichloride, diisopropoxy zirconium dichloride, bis (dimethylamino) titanium dichloride, diethoxy titanium dichloride, bis (ethylmethylamino) titanium dichloride, bis (n-propoxy) titanium dichloride, diisopropoxy titanium dichloride, bis (dimethylamino) hafnium dichloride, diethoxy hafnium dichloride, bis (ethylmethylamino) hafnium dichloride, bis (n-propoxy) hafnium dichloride, or diisopropoxy hafnium dichloride.
Bis (ethylmethylamino) hafnium dichloride was used in this example.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (16)
1. a method for preparing a substituted cyclopentadienyl metallocene compound, characterized in that it comprises the following steps:
(1) Reacting the substituted fulvene compound with an alkali metal or alkaline earth metal hydride selected from lithium hydride, sodium hydride, potassium hydride, calcium hydride, beryllium hydride or magnesium hydride to give a substituted cyclopentadienyl salt;
(2) Reacting the substituted cyclopentadienyl salt with a group IV halide or a derivative of a group IV halide to obtain a metallocene compound;
The molecular formulas of the substituted fulvene compound and the metallocene compound prepared by the substituted fulvene compound are respectively as follows:
Wherein "-" represents a five-membered ring having 0 to 4 non-hydrogen substituents independently selected from heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 30 carbon atoms; r1And R2Each independently selected from hydrogen, heteroatom-containing or heteroatom-free alkyl groups containing from 1 to 30 carbon atoms; m represents a group IV metal; x represents a halogen;
The derivative of the halide of group IV is bis (dimethylamino) zirconium dichloride, diethoxy zirconium dichloride, bis (ethylmethylamino) zirconium dichloride, di-n-propoxybutyronium dichloride, diisopropoxybirconium dichloride, bis (dimethylamino) titanium dichloride, diethoxy titanium dichloride, bis (ethylmethylamino) titanium dichloride, di-n-propoxytitanium dichloride, diisopropoxytitanium dichloride, bis (dimethylamino) hafnium dichloride, diethoxy hafnium dichloride, bis (ethylmethylamino) hafnium dichloride, di-n-propoxydihafnium dichloride or diisopropoxydihafnium dichloride.
2. The method according to claim 1, wherein the number of the non-hydrogen substituents attached to the five-membered ring indicated by "X" is 0 to 2.
3. The method according to claim 1, wherein the number of the non-hydrogen substituents attached to the five-membered ring indicated by "X" is 0 or 1.
4. The method according to claim 1, wherein the number of the non-hydrogen substituents attached to the five-membered ring indicated by "X" is 0.
5. the method of claim 1, wherein the non-hydrogen substituent attached to the five-membered ring is independently selected from the group consisting of a heteroatom-containing alkyl group having 1 to 15 carbon atoms and a heteroatom-free alkyl group.
6. the method of claim 1, wherein the non-hydrogen substituent attached to the five-membered ring is independently selected from the group consisting of a heteroatom-containing alkyl group having 1 to 10 carbon atoms and a heteroatom-free alkyl group.
7. The method according to claim 1, wherein R is1And R2Each independently selected from hydrogen, a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 15 carbon atoms.
8. The method according to claim 1, wherein R is1And R2Each independently selected from hydrogen, a heteroatom-containing or heteroatom-free alkyl group containing from 1 to 10 carbon atoms.
9. The process for producing a substituted cyclopentadienyl metallocene compound according to any one of claims 1 to 8, wherein,
"x" indicates that the heteroatom-containing or heteroatom-free alkyl group carried on the five-membered ring includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, or 1-ethylpropyl;
R1And R2Heteroatom-containing or heteroatom-free alkyl groups include methyl, ethyl or propyl.
10. The method of claim 1, wherein the group IV halide is a chloride of titanium, zirconium or hafnium.
11. the method of claim 1, wherein the group IV halide is a chloride of zirconium or hafnium.
12. The method of claim 1, wherein the alkali metal or alkaline earth metal hydride is selected from the group consisting of lithium hydride, sodium hydride and potassium hydride.
13. The method of claim 1, wherein the alkali metal or alkaline earth metal hydride is selected from lithium hydride and sodium hydride.
14. The method of claim 1, wherein the alkali metal or alkaline earth metal hydride is selected from lithium hydride.
15. The method for preparing a substituted cyclopentadienyl metallocene compound according to claim 1, wherein in the step (1), the reaction is carried out in an organic solvent under the protection of dry inert gas at-20 to 25 ℃, and the feeding molar ratio of the substituted fulvene compound to the hydride of the alkali metal or the alkaline earth metal is 1: 1-1.5: 1, stirring the mixture overnight, and filtering to obtain the substituted cyclopentadienyl salt, wherein the adopted organic solvent is one or a mixture of more of diethyl ether, methyl tert-butyl ether, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, tetrahydrofuran and 2-methyltetrahydrofuran.
16. The method for preparing a substituted cyclopentadienyl metallocene compound according to claim 1, wherein in the step (2), the reaction is performed in an organic solvent under the protection of dry inert gas at-50 to 25 ℃, and the feeding molar ratio of the substituted cyclopentadienyl salt to the group IV halide or the derivative of the group IV halide is 2: 1, stirring the mixture overnight for reaction, filtering the mixture, and pumping the solvent out of the mother liquor to obtain the metallocene compound, wherein the adopted organic solvent is one or a mixture of more of diethyl ether, methyl tert-butyl ether, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, tetrahydrofuran and 2-methyltetrahydrofuran.
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| 6,6-二烷基富烯与有机锂的反应—双(取代环戊二烯基)钛、锆衍生物的合成;陈寿山等;《化学学报》;19900531(第5期);494页第2段、化学反应式，第496页最后1段，第497页第1段 * |
| Absolute Metal-Ligand σ Bond Enthalpies in Group 4 Metallocenes A Thermochemical, Structural, Photoelectron Spectroscopic, and abInitio Quantum Chemical Investigation;Wayne A. King et al.;《J. Am. Chem. Soc.》;19990105;第121卷;356页右栏第2段，357页左栏第1段 * |
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