CN105884837A - Synthetic method of non-bridged half-titanocene complex - Google Patents
Synthetic method of non-bridged half-titanocene complex Download PDFInfo
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- CN105884837A CN105884837A CN201410560122.6A CN201410560122A CN105884837A CN 105884837 A CN105884837 A CN 105884837A CN 201410560122 A CN201410560122 A CN 201410560122A CN 105884837 A CN105884837 A CN 105884837A
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- cyclopentadienyl titanium
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Abstract
The invention discloses a synthetic method of a non-bridged half-titanocene complex. The structural formula of the non-bridged half-titanocene complex is as follows. The synthetic method comprises the following steps: a reaction is carried out between N-[2-(aminomethyl)phenyl]-N,N-dimethylamine and cyclohexanol with a (pentamethylcyclopentadienyl)iridium(III) chloride dimer and sodium bicarbonate as catalysts, and 2-(cyclohexylaminomethyl)-N,N-dimethylamine is obtained; a reaction is carried out between 2-(cyclohexylaminomethyl)-N,N-dimethylamine and n-butyllithium, and mixed liquor containing 2-(cyclohexylaminomethyl)-N,N-dimethylaniline lithium salt is obtained; finally, a reaction is carried out between the mixed liquor containing 2-(cyclohexylaminomethyl)-N,N-dimethylaniline lithium salt and pentamethylcyclopentadienyltitanium trichloride (IV), and the non-bridged half-titanocene complex is obtained. The method has the advantages of simple synthesis steps, few by-products, and simple method.
Description
Technical field
The present invention relates to non-bridged single cyclopentadienyl titanium complex and catalyst manufacturing technology field, the synthetic method of specifically a kind of non-bridged single cyclopentadienyl titanium complex containing 2-(cyclohexylamine methyl)-DMA part.
Background technology
Polyolefine material is one of the most widely used synthesizing polymeric material in the daily production of people and life.In recent years, people sharply increase for the demand of High performance polyolefin material, and increasing research worker is devoted to develop high performance new olefin homogeneous polymerization catalyst.Wherein metallocene catalyst is as the homogenous olefin polymerization catalyst of a new generation, compared with conventional Ziegler catalyst, has higher activity.Simultaneously, metallocene catalyst can also be by changing the substituent group on metallocene complex part, and then change catalytic performance and the polyolefinic microstructure of gained of metallocene complex, therefore can be used to manufacture high performance polyolefine material, such as syndiotactic polypropylene, isotactic polypropylene, random polypropylene, linear low density polyethylene, linear high-density polyethylene, syndiotactic polytyrene, ethylene/1-hexene copolymer, cyclic olefine copolymer, optical activity oligomer, polymethylene cyclenes etc..
In metallocene catalyst, non-bridged single cyclopentadienyl titanium complex has the openst Coordination Space, the coordination with the comonomer of bigger steric hindrance is conducive to insert, may be used for catalyzed ethylene, propylene and high alpha-olefin (such as 1-hexene) copolymerization and styrene homopolymerization etc., the type being suitable for catalysed olefin polymerization is the most, is one of the focus of current metallocene catalyst research field.In these are studied, how obtaining the non-bridged single cyclopentadienyl titanium complex that kind is more, be easier to synthesize becomes emphasis and the difficult point of research.But contain the report of the non-bridged single cyclopentadienyl titanium complex of 2-(cyclohexylamine methyl)-DMA part at present also seldom, and synthesis step is complicated, and by-product is many.
Summary of the invention
The defect existed for above-mentioned prior art or deficiency, it is an object of the invention to, it is provided that the synthetic method of the non-bridged single cyclopentadienyl titanium complex containing 2-(cyclohexylamine methyl)-DMA part that a kind of method is easy, practical.
In order to realize above-mentioned task, the present invention takes following technical solution:
The synthetic method of a kind of non-bridged single cyclopentadienyl titanium complex, it is characterised in that comprise the following steps:
(1) in toluene solution, use N-(2-aminomethyl) phenyl)-N, N dimethylamine and Hexalin react under dichloro (pentamethylcyclopentadiene base) closes iridium (III) dimer and sodium bicarbonate catalysis, obtain 2-((cyclohexylamino) methyl)-DMA.
(2) in toluene solution, use above-mentioned 2-(cyclohexylamine methyl)-DMA and n-BuLi to react, obtain the mixed liquor containing 2-(cyclohexylamine methyl)-DMA lithium salts.
(3) in toluene solution, use above-mentioned containing 2-(cyclohexylamine methyl)-N, mixed liquor and pentamethylcyclopentadiene base titanous chloride. (IV) of accelerine lithium salts react, and obtain a kind of non-bridged single cyclopentadienyl titanium complex, and its structural formula is as follows:
As preferably, in described synthetic method, in step (1), reaction condition is: reaction is carried out under nitrogen protection, and reaction temperature is 95 DEG C, and the response time is 18-24h.
As preferably; in described synthetic method; in step (2); reaction condition is: under nitrogen protection, is dissolved in toluene by 2-(cyclohexylamine methyl)-DMA; the hexane solution taking n-BuLi is slowly dropped in above-mentioned solution; after adding, at-30 DEG C, first stir 2h, be then warmed to room temperature stirring 3h.
As preferably; in described synthetic method; in step (3); reaction condition is: under nitrogen protection; the toluene solution of pentamethylcyclopentadiene base titanous chloride. (IV) is slowly dropped to containing 2-(cyclohexylamine methyl)-N; in the mixed liquor of accelerine lithium salts, after adding, reactant mixture is warming up to 55 DEG C of stirring reaction 25-30h.
Compared with prior art, it is an advantage of the current invention that: synthesis step of the present invention is simple, and by-product is few, method is easy.
Detailed description of the invention
The present invention is described in further detail for the embodiment be given below in conjunction with inventor.
According to the present invention containing 2-(cyclohexylamine methyl)-N, the non-bridged single cyclopentadienyl titanium complex synthetic method of accelerine part, inventor provides following example, it should be noted that, these embodiments are mainly used in those skilled in the art's a further understanding of the present invention, the invention is not restricted to these embodiments.
Embodiment 1:
1.1 reaction scheme
1.2 synthesis step
(1) under nitrogen protection; in 10mL toluene, add 0.080g (0.1mmol) dichloro (pentamethylcyclopentadiene base) close iridium (III) dimer and 0.008g (0.1mmol) sodium bicarbonate; then 1.501g (10mmol) N-(2-aminomethyl) phenyl is taken)-N; N dimethylamine and 1.002g (10mmol) Hexalin join in above-mentioned solution, are warming up to 95 DEG C of stirring 18h after adding.Boil off solvent and obtain yellow solid, with column chromatography (silica gel, hexane, ethyl acetate, triethylamine eluent) 2-((cyclohexylamino) the methyl)-DMA solid 2.022g (8.7mmol, 87%) of isolated yellow.
Elementary analysis: C15H24N2Theoretical value (%): C, 77.53；H, 10.41；N, 12.06.Measured value (%): C, 77.82；H, 10.21；N, 12.16.
Magnetic resonance spectroscopy: (1H-NMR, CDCl3, 400MHz, 6 (ppm)): 7.34-7.01 (m, 4H), 3.81 (s, 2H), 2.72 (s, 6H), 2.54-2.44 (m, 1H), 1.94-1.90 (m, 2H), 1.76-1.71 (m, 2H), 1.64-1.60 (m, 1H), 1.36-1.05 (m, 6H).
(2) under nitrogen protection; by 0.465g (2mmol) 2-(cyclohexylamine methyl)-N; accelerine is dissolved in 20mL toluene; the hexane solution (2.08mmol, 1.6mol/L) taking 1.3mL n-BuLi is slowly dropped in above-mentioned solution, after adding; at-30 DEG C, first stir 2h; then it is warmed to room temperature stirring 3h, obtains the mixed liquor containing 2-(cyclohexylamine methyl)-DMA lithium salts.
(3) under nitrogen protection; will be containing the 20mL toluene solution of 0.579g (2mmol) pentamethylcyclopentadiene base titanous chloride. (IV); it is slowly dropped to above-mentioned containing 2-(cyclohexylamine methyl)-N; in the mixed liquor of accelerine lithium salts; after adding; reactant mixture is warming up to 55 DEG C of stirring reaction 25h; boil off toluene; add 10mL dichloromethane; it is filtered to remove lithium chloride; boil off solvent and obtain yellow solid, be recrystallized to give 0.660g (1.36mmol, 68%) orange-yellow powder with hexanes/ch mixed solvent.
Elementary analysis: C25H38Cl2N2The theoretical value (%) of Ti: C, 61.87；H, 7.89；N, 5.77.Measured value (%): C, 61.98；H, 7.99；N, 5.66.
Magnetic resonance spectroscopy: (1H-NMR, CDCl3, 400MHz, 6 (ppm)): 7.35-7.02 (m, 4H), 5.84 (s, 2H), 5.45 (m, 1H), 2.02 (s, 6H), 1.92 (s, 15H), 1.77-0.85 (m, 10H).
Data above confirms to have synthesized the non-bridged single cyclopentadienyl titanium complex containing 2-(cyclohexylamine methyl)-DMA part according to embodiment 1, and its structural formula is as follows:
Embodiment 2:
The other the same as in Example 1, difference is: in step (1), the response time is 21h, obtains 2-((cyclohexylamino) methyl)-DMA 2.068g (8.9mmol, 89%).
Embodiment 3:
The other the same as in Example 1, difference is: in step (1), the response time is 24h, obtains 2-((cyclohexylamino) methyl)-DMA 2.091g (9.0mmol, 90%).
Embodiment 4:
The other the same as in Example 1, difference is: in step (3), and reactant mixture is warming up to 55 DEG C of stirring reaction 28h, must contain 2-(cyclohexylamine methyl)-N, non-bridged single cyclopentadienyl titanium complex 0.680g (1.4mmol, 70%) of accelerine part.
Embodiment 5:
The other the same as in Example 1, difference is: in step (3), and reactant mixture is warming up to 55 DEG C of stirring reaction 30h, must contain 2-(cyclohexylamine methyl)-N, non-bridged single cyclopentadienyl titanium complex 0.689g (1.42mmol, 71%) of accelerine part.
Claims (4)
1. the synthetic method of a non-bridged single cyclopentadienyl titanium complex, it is characterised in that comprise the following steps:
(1) in toluene solution, N-(2-aminomethyl) phenyl is used)-N, N dimethylamine and Hexalin are at dichloro (pentamethyl
Cyclopentadienyl group) close and react under iridium (III) dimer and sodium bicarbonate catalysis, obtain 2-((cyclohexylamino) first
Base)-DMA.
(2) in toluene solution, above-mentioned 2-(cyclohexylamine methyl)-DMA and n-BuLi is used to carry out instead
Should, obtain the mixed liquor containing 2-(cyclohexylamine methyl)-DMA lithium salts.
(3) in toluene solution, the above-mentioned mixed liquor containing 2-(cyclohexylamine methyl)-DMA lithium salts is used
React with pentamethylcyclopentadiene base titanous chloride. (IV), obtain a kind of non-bridged single cyclopentadienyl titanium complex, its structural formula
As follows:
2. the synthetic method of non-bridged single cyclopentadienyl titanium complex as claimed in claim 1, it is characterised in that described step
Suddenly in (1), reaction condition is: reaction is carried out under nitrogen protection, and reaction temperature is 95 DEG C, and the response time is 18-24
h。
3. the synthetic method of non-bridged single cyclopentadienyl titanium complex as claimed in claim 1, it is characterised in that described step
Suddenly in (2), reaction condition is: under nitrogen protection, and 2-(cyclohexylamine methyl)-DMA is dissolved in first
In benzene, the hexane solution taking n-BuLi is slowly dropped in above-mentioned solution, after adding, first stirs 2h at-30 DEG C,
Then stirring 3h it is warmed to room temperature.
4. the synthetic method of non-bridged single cyclopentadienyl titanium complex as claimed in claim 1, it is characterised in that described step
Suddenly in (3), reaction condition is: under nitrogen protection, by molten for the toluene of pentamethylcyclopentadiene base titanous chloride. (IV)
Liquid is slowly dropped in the mixed liquor containing 2-(cyclohexylamine methyl)-DMA lithium salts, and after adding, reaction is mixed
Compound is warming up to 55 DEG C of stirring reaction 25-30h.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102161682A (en) * | 2011-02-01 | 2011-08-24 | 吉林大学 | Non-bridged N-substituted aryllamino mono-titanocene compound and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102161682A (en) * | 2011-02-01 | 2011-08-24 | 吉林大学 | Non-bridged N-substituted aryllamino mono-titanocene compound and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| KEFENG LIU等: ""Synthesis, characterization, and catalytic properties of new half-sandwich zirconium(IV) complexes"", 《DALTON TRANSACTIONS》 * |
| KEN-ICHI FUJITA等: ""N-Alkylation of amines with alcohols catalyzed by a Cp*Ir complex"", 《TETRAHEDRON LETTERS》 * |
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Application publication date: 20160824 |