CN104370681A - Synthesis method of vinyl-bridged dialkylindene compound - Google Patents
Synthesis method of vinyl-bridged dialkylindene compound Download PDFInfo
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Abstract
The invention relates to a synthesis method of a vinyl-bridged dialkylindene compound. The synthesis method comprises that indene or an alkyl substituent of indene and lithium alkylide are mixed in an alkane solution, the solution undergoes a reaction to produce an alkane solution of indene or alkyl-substituted indene-based lithium salt, o-dibromoalkane is added into the alkane solution so that a mixed solution is obtained, and an activator is added into the mixed solution so that the vinyl-bridged dialkylindene compound is obtained. The synthesis method has mild conditions, prevents low-temperature reaction, has high operationality and a high yield and is conducive to industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of dialkyl group indene compound of vinyl bridging, belong to the field of chemical synthesis.
Background technology
Metallocene is that transition metal is connected with cyclopentadiene and derivative thereof formed Organometallic complexes, and such catalyzer has single-activity site, and polymer molecular weight distribution relative narrower, has desirable physico-chemical property.Metallocene catalyst and activator N, N-3,5-dimethylphenyl four (pentafluorophenyl group) borate, coactivator triisobutyl aluminium is composite or in the polyreaction such as vinyl polymerization, Propylene polymerization, have very high catalytic activity with the catalyst system of methylaluminoxane (MAO) composite formation, is the focus of people's concern in the last few years.Two indenes alkylates of vinyl bridging are the important intermediate of synthesis metallocene catalyst, with 1,2-bis-indenyl ethane and homologue thereof are that the metallocene catalyst ethylene base bridging α-olefins of part synthesis has a wide range of applications in olefinic polyreaction, and its general structure as shown in Equation 1.
R in formula
1, R
2, R
3, R
4for H atom or C
1-C
6alkyl, R
5, R
6be selected from H and C respectively
1-C
4alkyl, and R
5and R
6carbon atom summation is not more than 4.
At present, many patents and document is had to describe 1, the synthetic method of 2-bis-indenyl ethane, such as: at J.OrganometallicChemistry, in 342 (1988) 21-29, the people such as S.Collins describe one and utilize 1,2-ethylene dibromide synthesizes 1, the method of 2-bis-indenyl ethane: with the indenyl lithium and 1 of two equal portions in THF/HMPA solution, 2-ethylene dibromide, react being slowly heated to room temperature from-78 DEG C, the yield obtaining final product after acetone/ethanol recrystallization is 65%.
At J.Am.Chem.Soc., in 109 (1987) 6544-6545, the people such as A.Ewen adopt the method similar to Collins, in tetrahydrofuran (THF) (THF) solution, the indenyl lithium and 1 of same use two equal portions, 2-ethylene dibromide, reacts being slowly heated to 25 DEG C from-90 DEG C, and the yield obtaining final product after ethyl alcohol recrystallization is 60%.
In patent EP-A-0485823, Hoechst have employed the method similar with Collins, change the solution of reaction, employing THF is solvent, after solution being slowly warming up to room temperature from-78 DEG C in the 5h process stirred, purify through pillar layer separation and obtain 1,2-bis-(2-methyl indenes) ethane of 49% yield.
In patent EP-A-0575875, Spherilene utilizes 4,7-dimethyl indenes to be starting raw material, and solution is warming up to 50 DEG C from-78 DEG C and after stirring 12h, obtains the not pure products of 48%.
At document Organometallics, in 10 (1991), the people such as Grossman with the ratio of indenyl lithium and glycol dibromide for 2.2:1, temperature of reaction be obtain under-78 DEG C to the condition of room temperature 54% 1,2-bis-indenyl ethane.
All there is obvious shortcoming in the reaction process of the above reaction, the yield of these building-up reactionss is generally on the low side, all be no more than 65%, wherein main by product is spiral shell indene compound, because the character of impurity and product is close, need to carry out separating-purifying by pillar layer separation method, and this is industrially worthless.In addition, in order to suppress the generation of by product, these reactions are all carry out under the condition of low temperature or even very low temperature, and create in large-scale industrial production and keep low-temp reaction condition to need the energy of at substantial, this is uneconomic aborning., above-mentioned reaction is improved for this reason, improve reaction efficiency, reduce energy consumption of reaction, increase its economy and just seem particularly important.
The present invention is by improving the method for reaction solvent system and interpolation activator, improve temperature of reaction, this reaction can be carried out under normal temperature condition, decrease the production of by product, significantly improve the yield of product, for the industrialization synthesis of the dialkyl group indene compounds of vinyl bridging provides a kind of new approach.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of dialkyl group indene compound of vinyl bridging, there is reaction conditions gentleness, feature that yield is high, contribute to the suitability for industrialized production of the dialkyl group indene compound realizing vinyl bridging.
The present invention is achieved by the following technical solutions:
A synthetic method for the dialkyl group indene compound of vinyl bridging, comprises the following steps:
(1) under protection of inert gas, alkyl substituents and the lithium alkylide of indenes or indenes react in alkane solvents, the alkane solution of the indenyl lithium salts that obtained indenyl lithium salts or alkyl replace;
(2), under protection of inert gas, in obtained above-mentioned alkane solution, add adjacent dibromoalkane hydrocarbon, stir and form uniform mixing solutions;
(3) under protection of inert gas, at above-mentioned mixed solution and dripping activator, the dialkyl group indene compound of Reactive Synthesis vinyl bridging;
Wherein, R is methyl, normal-butyl or the tertiary butyl; R
1, R
2, R
3, R
4be selected from H and C respectively
1-C
6alkyl; R
5, R
6be selected from H and C respectively
1-C
4alkyl, and R
5and R
6carbon atom summation is not more than 4.
Preferably, the temperature of reaction of step (1) is 0-100 DEG C; Reaction times is 1-8 hour.
Preferred, the temperature of reaction of step (1) is room temperature (25 DEG C); Reaction times is 2-4 hour.
Preferably, described rare gas element is selected from high pure nitrogen, high-purity argon gas and high-purity helium.
Preferably, in step (1), described alkane solvents is selected from Skellysolve A, normal hexane, normal heptane, octane and sherwood oil.The reaction of step (1) is not suitable for the solvent adopting strong polarity.
Preferably, in step (1), the mass ratio of the alkyl substituents of described alkane solvents and indenes or indenes is 5-50:1.
Preferably, in step (1), the molar ratio of the alkyl substituents of described lithium alkylide and indenes or indenes is 1-1.5:1; Be more preferably 1:1.
Preferably, in step (2), the mol ratio of the alkyl substituents of described adjacent dibromoalkane hydrocarbon and indenes or indenes is 0.5-0.8:1.
Preferably, in step (3), described activator is selected from ether, glycol dimethyl ether, tetrahydrofuran (THF), 2-methyl furan, 2,5-dimethyl furans, 2,3-cumarone polar solvent.
Preferably, in step (3), the mol ratio of the indenes in described activator and step (1) or the alkyl substituents of indenes is 0.1-1:1.
Preferably, in step (3), control the rate of addition of activator, control temperature of reaction is 0-100 DEG C, and activator drips and terminates rear continuation reaction 1-8 hour.Initial reaction stage, by controlling the dropping of activator, and then can reach the object controlling temperature of reaction, then needing outside temperature regulating device to carry out temperature control after reinforced.
Be more preferably, in step (3), activator dropwised in 1 hour, and temperature of reaction controls at 35 DEG C, and activator dropwises rear continuation reaction 2 hours.
Preferably, the method for described a kind of synthesis of vinyl bridging two indenyl compound is further comprising the steps of: reaction terminates to wash product afterwards, steams solvent afterwards, then carries out recrystallization to product, obtain white solid.
Preferably, the solvent of described recrystallization is the mixing solutions of ethanol and toluene.
Preferred, the volume ratio of described ethanol and toluene is 1-4:1.
The invention has the advantages that:
1) this synthetic route does not need low-temp reaction condition, at room temperature just can carry out, significantly reduce the energy consumption of reaction, makes the suitability for industrialized production of this route become possibility;
2) method being employed herein dropping activator, to control speed of reaction, makes speed of reaction controlled gently;
3) adopt the dialkyl group indene compound of present method synthesis of vinyl bridging not have by product spiral shell indenes to produce, product is easy to separating-purifying;
4) yield of product can reach 80% in the present invention, higher than existing various synthetic method.
Embodiment
Below by way of specific specific examples, technical scheme of the present invention is described.Should be understood that one or more method stepss that the present invention mentions do not repel and before and after described combination step, also to there is additive method step or can also insert additive method step between these steps clearly mentioned; Should also be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, but not be ordering or the enforceable scope of restriction the present invention of restriction various method steps, the change of its relativeness or adjustment, when changing technology contents without essence, when being also considered as the enforceable category of the present invention.
The invention provides a kind of synthetic method of dialkyl group indene compound of vinyl bridging, comprise the following steps:
(1) under protection of inert gas, alkyl substituents and the lithium alkylide of indenes or indenes react in alkane solvents, the alkane solution of the indenyl lithium salts that obtained indenyl lithium salts or alkyl replace;
(2), under protection of inert gas, in obtained above-mentioned alkane solution, add adjacent dibromoalkane hydrocarbon, stir and form uniform mixing solutions;
(3) under protection of inert gas, at above-mentioned mixed solution and dripping activator, the dialkyl group indene compound of Reactive Synthesis vinyl bridging;
Wherein, R is methyl, normal-butyl or the tertiary butyl; R
1, R
2, R
3, R
4be selected from H and C respectively
1-C
6alkyl; R
5, R
6be selected from H and C respectively
1-C
4alkyl, and R
5and R
6carbon atom summation is not more than 4;
In step (1), the mass ratio of the alkyl substituents of alkane solvent and indenes or indenes is 5-50:1.The molar ratio of the alkyl substituents of described lithium alkylide and indenes or indenes is 1-1.5:1; Be more preferably 1:1.The temperature of reaction of step (1) can at 0-100 DEG C, and the reaction times can at 1-8 hour; But from economical and industrialized angle, step of the present invention (1) is preferably at room temperature carried out, reaction times 2-4 hour.Alkane solvent in step (1) can be selected from the arbitrary of Skellysolve A, normal hexane, normal heptane, octane and sherwood oil or arbitrary combination.But the improper employing intensive polar solvent of step (1).
In step (2), the mol ratio of the alkyl substituents of described adjacent dibromoalkane hydrocarbon and indenes or indenes is 0.5-0.8:1; First by step (2), add adjacent dibromoalkane hydrocarbon in the alkane solution of the indenyl lithium salts replaced in the obtained indenyl lithium salts of step (1) or alkyl, stir and form uniform mixing solutions; And then dripping activator by step (3), such order of addition(of ingredients) is also the key point of present invention process.
Step (3) described activator is selected from ether, glycol dimethyl ether, tetrahydrofuran (THF), dimethyl furan, 2,5-dimethyl furans, 2,3-cumarone polar solvent.The mol ratio of the indenes in described activator and step (1) or the alkyl substituents of indenes is 0.1-1:1.In step (3), control the rate of addition of activator, control temperature of reaction is 0-100 DEG C, and activator drips and terminates rear continuation reaction 1-8 hour.By controlling the dropping of activator, and then the object controlling temperature of reaction can be reached.And activator drip terminate after, then need outside temperature control to make reaction continue to remain on 0-100 DEG C.Be more preferably, in step (3), temperature of reaction controls at 35 DEG C, and activator dropwises rear continuation reaction 2 hours.
The method of described a kind of synthesis of vinyl bridging two indenyl compound is further comprising the steps of: reaction terminates to wash product afterwards, steams solvent afterwards, then carries out recrystallization to product, obtain white solid.The solvent of described recrystallization is the mixing solutions of ethanol and toluene.Preferred, the volume ratio of described ethanol and toluene is 1-4:1.
Below by way of concrete enforcement, elaboration explanation is carried out to technical scheme of the present invention:
The synthesis of embodiment 1 compound 1,2-bis-indenyl ethane
(1) room temperature (25 DEG C), under nitrogen atmosphere protection, the indenes taking 111.6g (90wt%) adds in 1L normal hexane, measure the hexane solution that 394ml volumetric molar concentration is the n-Butyl Lithium of 2.2mol/L, it is slowly joined in above-mentioned solution, dropwise rear stirring reaction 2 hours, the hexane solution of obtained indenyl lithium salts;
(2) room temperature, under nitrogen atmosphere protection, measures 38ml ethylene dibromide and adds in the hexane solution of above-mentioned indenyl lithium salts, be uniformly mixed;
(3) under nitrogen protection, slowly drip the THF of 20ml to above-mentioned solution, controlling temperature of reaction is 35 DEG C, drips and terminates rear continuation reaction 2h;
(4) after reaction terminates, wash 3 times, steam after desolventizing, carry out recrystallization with the toluene/ethanol mixed solvent that volume ratio is 2:1 and obtain white solid 1,2-bis-indenyl ethane 90g, yield 80.5%.
The nuclear magnetic data of product is: product warp
1h-NMR (CDCl
3make solvent, 25 DEG C) characterize: δ=7.31 (d, 1H), 7.28 ~ 7.13 (m, 3H), 6.34 (s, 1H), 2.1 (s, 1H)
The synthesis of comparative example 1 compound 1,2-bis-indenyl ethane
The indenes taking 111.6g (90wt%) adds in 1L tetrahydrofuran solution, measure the hexane solution that volumetric molar concentration is the n-Butyl Lithium of 2.2mol/L, at-78 DEG C, it is slowly joined in above-mentioned solution, dropwise rear stirring reaction 2 hours, measure 36ml ethylene dibromide and add above-mentioned lithium salt solution, reaction 2h after washing 3 times, steams after desolventizing, carries out recrystallization obtain white solid 1 with the ethanol/toluene mixed solvent that volume ratio is 2:1,2-bis-indenyl ethane 45g, yield 40.5%.
Comparative example obtains the nuclear magnetic data of product with embodiment 1.
The THF adopted in comparative example adds as reaction solvent, and in embodiment 1, adopt alkanes to carry out lithiumation as reaction solvent, ethylene dibromide reaction is added after lithiumation violent in THF, must carry out under very low temperature, and side reaction is many, and to add ethylene dibromide in alkane solvents after lithiumation be nonreactive, the THF adding seldom amount plays the effect of catalyzer (activator), make reaction at normal temperatures controlled, can steadily carry out.
As can be seen from the above results, adopt the synthetic method of invention, just can obtain metallocene ligand 1,2-bis-indenyl ethane with high yield at ambient temperature, avoid the use of expensive solvent tetrahydrofuran (THF) and harsh low-temp reaction condition in comparative example.
The synthesis of embodiment 2 compound 1,2-bis-(2,4-dimethyl indenes) ethane
(1) room temperature, under nitrogen atmosphere protection, take 2 of 14.4g, 4-dimethyl indenes adds in 500mL hexane solution, measure the hexane solution that 100ml volumetric molar concentration is the lithium methide of 1mol/L, it is slowly joined in above-mentioned solution, dropwise rear stirring reaction 3 hours, the hexane solution of obtained 2,4-dimethylindenyl lithium salts;
(2) room temperature, under nitrogen atmosphere protection, measures 4.5ml ethylene dibromide and adds in the hexane solution of above-mentioned 2,4-dimethylindenyl lithium salts, be uniformly mixed;
(3) under nitrogen protection, the THF measuring 3ml is slowly added drop-wise in above-mentioned solution, and controlling temperature of reaction is 35 DEG C, drips and terminates rear continuation reaction 2h;
(4) after reaction terminates, wash 3 times, steam after desolventizing, carry out recrystallization with the ethanol/toluene mixed solvent that volume ratio is 2:1 and obtain white solid 1,2-bis-(2,4-dimethyl indenes) ethane 11.3g, yield 72%.
Nuclear magnetic data: product warp
1h-NMR (CDCl
3make solvent, 25 DEG C) characterize: δ=7.28 (d, 1H), 7.14 (d, 1H), 6.97 (t, 1H), 6.38 (s, 1H), 3.61 (q, 1H), 2.31 (s, 3H), 2.2 (s, 2H), 1.54 (d, 3H)
The synthesis of embodiment 3 compound 1,2-bis-(2,4,7-trimethylammonium indenes) ethane
(1) room temperature, under nitrogen atmosphere protection, 2,4, the 7-trimethylammonium indenes taking 79g add in 500mL normal heptane, measure the Skellysolve A solution that 500ml volumetric molar concentration is the lithium methide of 1mol/L, it is slowly joined in above-mentioned solution, dropwises rear stirring reaction 4 hours, obtained 2, the normal heptane of 4,7-trimethylindenyl lithium salts and the mixing solutions of Skellysolve A;
(2) room temperature, under nitrogen atmosphere protection, measures 34ml ethylene dibromide and adds in the normal heptane of above-mentioned 2,4,7-trimethylindenyl lithiums and the mixing solutions of Skellysolve A, be uniformly mixed;
(3) under nitrogen protection, the THF measuring 15ml is slowly added drop-wise in above-mentioned solution, and controlling temperature of reaction is 35 DEG C, drips and terminates rear continuation reaction 2h;
(4) after reaction terminates, wash 3 times, steam after desolventizing, carry out recrystallization with the ethanol/toluene mixed solvent that volume ratio is 4:1 and obtain white solid 1,2-bis-(2,4,7-trimethylammonium indenes) ethane 64.2g, yield 75%.
Nuclear magnetic data: product warp
1h-NMR (CDCl
3make solvent, 25 DEG C) characterize: δ=7.01 (d, 1H), 6.87 (d, 1H), 6.11 (s, 1H), 3.65 (q, 1H), 2.49 (s, 3H), 2.34 (s, 3H), 2.00 (s, 2H), 1.54 (d, 3H)
The synthesis of embodiment 4 compound 2,3-bis-indenes butane
(1) room temperature, under nitrogen atmosphere protection, the indenes taking 55.8g (90wt%) adds in 500mL hexane solution, measure the hexane solution that 200ml volumetric molar concentration is the n-Butyl Lithium of 2.2mol/L, it is slowly joined in above-mentioned solution, dropwise rear stirring reaction 2 hours, the hexane solution of obtained indenyl lithium salts;
(2) room temperature, under nitrogen atmosphere protection, 2, the 3-dibromobutanes measuring 46g add in the hexane solution of above-mentioned indenyl lithium salts, are uniformly mixed;
(3) under nitrogen protection, the 2-methyl furan measuring 20ml is slowly added drop-wise in above-mentioned solution, and controlling temperature of reaction is 35 DEG C, drips and terminates rear continuation reaction 2h;
(4) after reaction terminates, wash 3 times, steam after desolventizing, carry out recrystallization with the toluene/ethanol mixed solvent that volume ratio is 2:1 and obtain white solid 2,3-bis-indenes butane 43.9g, yield 71%.
The nuclear magnetic data of product is: product warp
1h-NMR (CDCl
3make solvent, 25 DEG C) characterize: δ=7.31 (d, 1H), 7.29 ~ 7.13 (m, 3H), 6.32 (s, 1H), 2.35 (q, 1H), 1.12 (d, 3H)
The synthesis of embodiment 5 compound 1,2-bis-(3-1-hexyl indenes) ethane
(1) room temperature, under nitrogen atmosphere protection, the 1-hexyl indenes taking 20g adds in 1.3L hexane solution, measure the hexane solution that 100ml volumetric molar concentration is the tert-butyl lithium of 1mol/L, it is slowly joined in above-mentioned solution, dropwise rear stirring reaction 3 hours, the hexane solution of obtained 1-hexyl indenyl lithium salts;
(2) room temperature, under nitrogen atmosphere protection, measures 4.5ml ethylene dibromide and adds in the hexane solution of above-mentioned 1-hexyl indenyl lithium salts, be uniformly mixed;
(3) under nitrogen protection, 2, the 3-cumarones measuring 10ml are slowly added drop-wise in above-mentioned solution, and controlling temperature of reaction is 35 DEG C, drip and terminate rear continuation reaction 2h;
(4) after reaction terminates, wash 3 times, steam after desolventizing, carry out recrystallization with the ethanol/toluene mixed solvent that volume ratio is 2:1 and obtain white solid 1,2-bis-(3-1-hexyl indenes) ethane 15.36g, yield 72.1%.
Nuclear magnetic data: product warp
1h-NMR (CDCl
3make solvent, 25 DEG C) characterize: δ=7.33 (d, 1H), 7.27 ~ 7.20 (m, 3H), 6.14 (s, 1H), 3.45 (q, 1H), 2,02 (s, 2H), 1.62 (m, 2H), 1.30 ~ 1.22 (m, 8H), 0.85 (t, 3H).
The synthesis of embodiment 6 compound 1,2-bis-indenyl ethane
Synthesis condition is identical with embodiment 1 except joining in lithium salt solution using 20ml glycol dimethyl ether as activator in step (3), after completion of the reaction, obtains white solid 1,2-bis-indenyl ethane 85.5g, yield 76.5%.
Embodiment 7
Synthesis condition is identical with embodiment 1, except selecting the hexane solution of tert-butyl lithium in step (1), after completion of the reaction, obtains white solid 1,2-bis-indenyl ethane 88.3g, yield 79%.
Nuclear magnetic data is with embodiment 1.
Embodiment 8 and embodiment 9
Embodiment 8 step (1) temperature of reaction 0 DEG C, embodiment 9 step (1) temperature of reaction 100 DEG C, other synthesis condition and embodiment 1, after completion of the reaction, embodiment 8 obtains white solid 1,2-bis-indenyl ethane 89g, yield 79.7%; Embodiment 9 obtains white solid 1,2-bis-indenyl ethane 58g, yield 51.9%.
Embodiment 8 and embodiment 9 product nuclear magnetic data are with embodiment 1.
Embodiment 10 and embodiment 11
Embodiment 10 step (3) temperature of reaction 0 DEG C, embodiment 11 step (3) temperature of reaction 100 DEG C; Other synthesis condition and embodiment 1, after completion of the reaction, embodiment 1 obtains white solid 1,2-bis-indenyl ethane 85g, yield 76.1%; Embodiment 11 obtains white solid 1,2-bis-indenyl ethane 53g, yield 47.4%.
Embodiment 10 and embodiment 11 product nuclear magnetic data are with embodiment 1.
Embodiment 12
Synthesis condition is identical with embodiment 1, except adding in step (1) hexane solution that 394ml concentration is the n-Butyl Lithium of 3.2mol/L, after completion of the reaction, obtains white solid 1,2-bis-indenyl ethane 80.3g, yield 71.9%.
Nuclear magnetic data is with embodiment 1.
Claims (13)
1. a synthetic method for the dialkyl group indene compound of vinyl bridging, comprises the following steps:
(1) under protection of inert gas, alkyl substituents and the lithium alkylide of indenes or indenes react in alkane solvents, the alkane solution of the indenyl lithium salts that obtained indenyl lithium salts or alkyl replace;
(2), under protection of inert gas, in obtained above-mentioned alkane solution, add adjacent dibromoalkane hydrocarbon, stir and form uniform mixing solutions;
(3) under protection of inert gas, at above-mentioned mixed solution and dripping activator, the dialkyl group indene compound of Reactive Synthesis vinyl bridging;
Wherein, R is methyl, normal-butyl or the tertiary butyl; R
1, R
2, R
3, R
4be selected from H and C respectively
1-C
6alkyl; R
5, R
6be selected from H and C respectively
1-C
4alkyl, and R
5and R
6carbon atom summation is not more than 4.
2. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 1, it is characterized in that, in step (1), the temperature of described reaction is 0-100 DEG C, and the reaction times is 1-8 hour.
3. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 2, it is characterized in that, in step (1), the temperature of described reaction is room temperature, reaction 2-4 hour.
4. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 1, it is characterized in that, in step (1), described alkane solvents is selected from Skellysolve A, normal hexane, normal heptane, octane and sherwood oil.
5. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 1, it is characterized in that, in step (1), the mass ratio of the alkyl substituents of described alkane solvents and indenes or indenes is 5-50:1.
6. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 1, it is characterized in that, in step (1), the molar ratio of the alkyl substituents of described lithium alkylide and indenes or indenes is 1-1.5:1.
7. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 1, it is characterized in that, in step (2), the mol ratio of the alkyl substituents of described adjacent dibromoalkane hydrocarbon and indenes or indenes is 0.5-0.8:1.
8. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 1, it is characterized in that, in step (3), described activator is selected from ether, glycol dimethyl ether, tetrahydrofuran (THF), dimethyl furan, 2,5-dimethyl furan and 2,3-cumarone.
9. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 8, is characterized in that, in step (3), the mol ratio of the indenes in described activator and step (1) or the alkyl substituents of indenes is 0.1-1:1.
10. the synthetic method of the dialkyl group indene compound of vinyl bridging as claimed in claim 8, it is characterized in that, in step (3), control the rate of addition of activator, control temperature of reaction is 0-100 DEG C, and activator drips and terminates rear continuation reaction 1-8 hour.
The synthetic method of the dialkyl group indene compound of 11. vinyl bridgings as claimed in claim 1, is characterized in that, further comprising the steps of: reaction terminates to wash product afterwards, steams solvent afterwards, then carries out recrystallization to product, obtain white solid.
The synthetic method of the dialkyl group indene compound of 12. vinyl bridgings as claimed in claim 11, it is characterized in that, the solvent of described recrystallization is the mixing solutions of toluene and ethanol.
The synthetic method of the dialkyl group indene compound of 13. vinyl bridgings as claimed in claim 12, is characterized in that, the volume ratio of described ethanol and toluene is 1-4:1.
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