CN101993330A - Method for preparing multi-substituted cyclopentadiene and substituted indene - Google Patents
Method for preparing multi-substituted cyclopentadiene and substituted indene Download PDFInfo
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- CN101993330A CN101993330A CN2009101697125A CN200910169712A CN101993330A CN 101993330 A CN101993330 A CN 101993330A CN 2009101697125 A CN2009101697125 A CN 2009101697125A CN 200910169712 A CN200910169712 A CN 200910169712A CN 101993330 A CN101993330 A CN 101993330A
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Abstract
The invention relates to a method for synthesizing multi-substituted cyclopentadiene and substituted indene. The method comprises the following steps of: reacting (substituted) cyclopentenone or indanone with a Grignard reagent; and then carrying out hydrolysis reaction treated with an active hydrogen atom-containing reagent. Through the method, multi-substituted cyclopentenone and substituted indene can be widely prepared. The active hydrogen atom-containing reagent is water, alcohol or phenol. Because of the improvement of the active hydrogen atom-containing reagent, the ratio of double bond products in a ring is greatly improved and the reaction controllability is greatly enhanced.
Description
Technical field
The present invention relates to the synthetic method of polysubstituted cyclopentadiene and replacement indenes, belong to the organic synthesis field.
Technical background
Cyclopentadiene or have the compound of cyclopentadiene ring structure such as the substitutive derivative of indenes, tetrahydroindene, fluorenes etc. is one of part important in the organic synthesis.This part after forming compound with transition metal atoms, the catalytic field that can be widely used in.Metallocene compound, the mono-metallocene compound that forms with fourth officer family metal (titanium, zirconium, hafnium) particularly, in the presence of promotor, can catalysis in olefine polymerization, resulting polymer performance is better than the polymerisate of traditional catalyst greatly.Simultaneously, this metallocene catalyst has the controllability of height, can be by adjusting the substituted radical on the part, the electronic effect in equilibrium polymerization active centre and stereoeffect, thereby regulation and control polymerization behavior and polymer performance.Therefore, the synthetic compound that has the cyclopentadiene of different substituents or have a cyclopentadiene ring structure (as indenes, tetrahydroindene, fluorenes etc.) has great importance to olefinic polymerization industry and polymerization catalyzed theoretical investigation.
From the petroleum cracking product, can obtain a small amount of cyclopentadiene and methyl cyclopentadiene, and polysubstituted cyclopentadiene is gone up substantially and can not simply be obtained from natural resource.
Mono-substituted cyclopentadiene can prepare by simple steps, is handled through ionization reagent (as lithium alkylide, sodium Metal 99.5 etc.) by cyclopentadiene, again with the halohydrocarbon effect, can obtain mono-substituted cyclopentadiene, see figure (2) (J.Chem.Soc., 1959,1757).May there be three kinds of isomer in single substituted-cyclopentadienyl that even now obtains, but when general further application, after ionization reagent (as lithium alkylide, sodium Metal 99.5 etc.) effect, combines with transition metal atoms again, and this difference can be eliminated.
And use similar method, during by the two substituted-cyclopentadienyl of single substituted-cyclopentadienyl preparation, product will become more complicated (Tetrahedron, 1965,21,2313).Not only there is the isomer of position of double bond in product, and two substituent relative positions also can increase the number of isomer, and promptly two substituting groups exist 1,2-and 1, and two kinds of replacement situations of 3-are seen figure (3).Since 1,2-and 1, the cyclopentadiene physical properties that 3-replaces is very approaching, and methods such as use distillation can not be separated it.So concerning target product only be wherein a kind of synthetic, this method is worthless.
US5144095 has reported and has utilized phase-transfer-catalyzed reactions, replaces and trisubstituted cyclopentadiene by the cyclopentadiene preparation is two, and used substituting group is the tertiary butyl.This method can only prepare two the replacement and the substituent substituted-cyclopentadienyl of trisubstituted big steric hindrance.Because when the single substituted-cyclopentadienyl of preparation, can generate two substitution products inevitably, although can separate by distillation.If the substituting group steric hindrance is less simultaneously, have 1 in two substitution products, 2-and 1, two kinds of substitution products of 3-, big steric hindrance substituting group can avoid 1, the generation of 2-substitution product.In preparation during three substituted-cyclopentadienyls, reaction conditions than the two substitution product harshnesses of preparation many, the while product contains two substitution products of significant proportion.CN97109765.8 has also reported the use phase-transfer catalyst, carries out polysubstituted synthetic route by cyclopentadiene, comprises two, three, four replacements, and substituting group has used non-tertiary alkyl groups such as sec.-propyl.By process modification, make the selectivity that replaces number be greatly improved, yet, do not mention in the patent about the position of substitution, particularly the selectivity of two replacements and trisubstituted the position of substitution.
CN00103315.8 has reported the method for synthetic polysubstituted cyclopentadiene, and following and n-Butyl Lithium reaction adds alkynes with bis cyclopentadienyl zirconium dichloride low temperature, adds aldehyde and aluminum chloride again, obtains polysubstituted cyclopentadiene derivant after the reaction.
CN03157352.5 has reported cyclopentadiene or substituted-cyclopentadienyl, particularly the tetramethyl-ring pentadiene is synthetic, with gamma-pyrone or replacement gamma-pyrone is reaction raw materials, the catalytic reduction in the presence of Lewis acid, and product obtains through dewatering under acidic conditions after the hydrolysis.The processing method that is provided can make the yield by gamma-pyrone or synthetic cyclopentadiene of replacement gamma-pyrone or substituted-cyclopentadienyl reach more than 65%, and technology is simplified greatly.
CN200410029714.1 has reported the synthetic method of a kind of cyclopentadiene or substituted-cyclopentadienyl, it is characterized in that having used Lewis acid in cyclopentenone or the substituted cyclopentene ketone catalytic reduction reaction process, the yield of synthetic cyclopentadiene of cyclopentenone or substituted cyclopentene ketone or substituted-cyclopentadienyl is improved greatly, and preparation technology obtains simplifying simultaneously.
US5329056 has reported a kind of method for preparing polysubstituted cyclopentadiene, sees figure (4), uses a vinyl ketone and a vinyl metallic compound reaction to obtain a tertiary alcohol, and dehydration, cyclisation obtain substituted-cyclopentadienyl then.US6388151 also describes similar synthetic method.
US5723708 has reported under the condition that is existed with solid acid catalyst by the beta-unsaturated ketone with ad hoc structure that through dehydration-cyclisation, obtain the method for substituted-cyclopentadienyl, characteristics are productive rate height in gas phase, raw material cheapness, shortcoming are that reaction conditions is relatively harsher.
US5434324 has described the method for preparing substituted-cyclopentadienyl by Grignard reagent and cyclopentenone effect, sees figure (5).The characteristics of this method are to increase an alkyl in the carbonyl position of original cyclopentenone.By Grignard reagent and carbonyl effect, obtain cyclopentenol through aquation, obtain substituted-cyclopentadienyl after the dehydration.
US5856541 improves above-mentioned synthetic method.After Grignard reagent and cyclopentenone effect, carry out quantitative aquation, promptly add the water of equivalent, can be without cyclopentenol, and directly obtain the product substituted-cyclopentadienyl.But the solvent for use system is comparatively complicated, generally needs to use the ether solvent of specified proportion and the mixture of varsol, the problem of the difficulties in dispersion that is produced when avoiding adding water.Even if solvent is suitable, in reaction process, caking still might appear in system, influences yield, even interrupts reaction.
In addition, these two kinds of methods have a common shortcoming, and promptly there is unwanted by product in final product, sees figure (6).The elimination of hydrogen atom may occur on the substituted alkyl, forms exocyclic double bond product (exo-).And the target product of wishing is cyclic olefinic bond product (endo-).And the exocyclic double bond product occupies sizable ratio usually, generally can reach 30-40%.
The cyclopentenone that has various substituted radicals can prepare (Helv.Chim.Acta.1974,57,2106 easily, at an easy rate; J.Organomet.Chem.1983,243,119), be used to prepare the indone that replaces indenes and can prepare (J.Am.Chem.Soc., 1950,72,3286) easily, by above-mentioned patented method, can prepare polysubstituted cyclopentadiene and indenes.Yet there are two important defectives in this method.At first, the controllability of preparation process is low, and in adding the water process, very easily caking or gel cause reaction to be interrupted; In addition, though reactant generally can transform fully, the reaction pair target product selectivity is low, has a large amount of exocyclic double bonds (exo-) by product in the product.
The present inventor finds, used to comprise that water, alcohol, phenol etc. contain the reagent of reactive hydrogen atom, or the mixture of mentioned reagent, with the product effect of Grignard reagent and substituted cyclopentene ketone or indone,, form two keys to eliminate the magnesium alkoxide group.When only making water as the reagent of reactive hydrogen atom, exocyclic double bond by product ratio is higher in the product, and promptly target product selectivity is poor.When using alcohol or phenol, the selectivity of target product significantly improves.
Summary of the invention
At the defective of prior art, the invention provides the method for a kind of synthetic polysubstituted cyclopentadiene and replacement indenes.The cyclic olefinic bond proportion of products is improved greatly, simultaneously, promoted the controllability of reaction greatly.
The method of a kind of synthetic polysubstituted cyclopentadiene of the present invention or replacement indenes, this method is by reaction raw materials substituted cyclopentene ketone or replace indone Yu Geshi reagent react, handles with the reagent A that contains reactive hydrogen atom again, obtains polysubstituted cyclopentadiene or replaces indenes; Described reaction raw materials substituted cyclopentene ketone replaces indone by shown in 3,4 formulas by shown in 1,2 formulas;
R in the formula
1～R
10Identical or different, for hydrogen atom or contain the saturated or undersaturated alkyl of 1-20 carbon atom; R
1～R
10In randomly cyclization or the not cyclization of adjacent substituted radical, described Grignard reagent structure is R
0MgX, it is optional for the Grignard reagent of commodity or by reacting the Grignard reagent that generates, R
0For containing the saturated or undersaturated alkyl of 1-20 carbon atom, X is F, Cl, Br or I;
Described A reagent is the reagent that contains reactive hydrogen atom.
Reaction process is represented by following formula 1a, 1b:
Used Grignard reagent can be the Grignard reagent of commodity among the present invention, the Grignard reagent that also can be to use halohydrocarbon and magnesium effect to generate.
The synthetic method that the present invention adopts is divided into four steps, and 1, synthetic (the commodity in use Grignard reagent does not then comprise this step) of Grignard reagent; 2, Grignard reagent and substituted cyclopentene ketone or the reaction of replacement indone; 3, add the reagent that contains reactive hydrogen atom; 4, separate.
The first step of synthetic method is the synthetic of Grignard reagent.Grignard reagent uses halohydrocarbon and MAGNESIUM METAL to act on generation under ether solvent.The alkyl of halohydrocarbon is the saturated or undersaturated alkyl that contains 1-20 carbon atom, comprises alkyl, thiazolinyl, alkynyl and aromatic hydrocarbon group, and halogen atom is F, Cl, Br or I atom.In the reaction process, the magnesium powder is placed the reaction flask of anhydrous and oxygen-free, add a certain amount of ether solvent, at room temperature drip the ether solvent solution of halogenated alkane, rate of addition is advisable to keep reaction system to reach faint backflow.After dropwising, back flow reaction a few hours.Ether solvent can use ether or tetrahydrofuran (THF), and the present invention preferably uses tetrahydrofuran (THF).
Second step of synthetic method is dissolved in substituted cyclopentene ketone or replacement indone in the mixed solvent of ether solvent or ether solvent and saturated alkane solvent, and the usage ratio of ether solvent and saturated alkane solvent is 1: 0 to 1: 4.Above-mentioned solution is dropped in the grignard reagent solution at low temperatures.After dropwising, stirring at room stoichiometric number hour.The solvent of dissolving substituted cyclopentene ketone or replacement indone can be selected the mixed solvent of tetrahydrofuran (THF) and hexane for use, and the present invention preferably uses tetrahydrofuran (THF), and the mol ratio of employed Grignard reagent and substituted cyclopentene ketone or replacement indone is 1.
In the 3rd step of synthetic method, add reagent or its solution that contains reactive hydrogen atom to above-mentioned reaction system.At room temperature, reagent or its drips of solution that slowly will contain reactive hydrogen atom add in the above-mentioned reaction system, and the dropping process is noted the whipped state that keeps good.After drip finishing, back flow reaction a few hours.The described reagent that contains reactive hydrogen atom is that water or contain is no more than the alcohol of 10 carbon atoms or is no more than the phenol of 20 carbon atoms, or its two or many persons' mixture, can directly drop to reaction system, also can drop to reaction system by wiring solution-forming.Preferably replace water as the reagent that contains reactive hydrogen atom, most preferably use dehydrated alcohol or anhydrous methanol with alcohol or phenol.Can improve the ratio of cyclic olefinic bond product in the product effectively.The another one vital role be since alcohol or phenol and reaction intermediate be Grignard reagent and carbonyl the adduct action temperature with, can avoid system gel or caking in the reaction process, therefore reacting balance is carried out, the employed reagent A that contains reactive hydrogen atom and the mol ratio of Grignard reagent are 1.
The 4th step of synthetic method is separated product.A kind of method is at first to cross the solid matter filter out in the system, and liquid portion can obtain product after with solvent evaporation; Also can use the acid treatment reaction mixture, separate organic phase, remove and desolvate, can obtain product.
Among the present invention, detect product structure use GC-MS and
1H-NMR.
The present invention prepares polysubstituted cyclopentadiene and replaces indenes.The transformation efficiency height of reaction raw materials, the controllability of reaction improves greatly, solved the phenomenon of reaction caking or gel well, has improved the ratio of cyclic olefinic bond product in the product that is target product greatly.
Embodiment
Embodiment 1 preparation 1-methyl-3-normal-butyl cyclopentadiene
Fully 250 milliliters of there-necked flasks of oven dry are put into the stirring magneton, place oil bath, vacuumize nitrogen wash, three times repeatedly.Adding adds 2.7 gram magnesium through 20 milliliters of the dry tetrahydrofuran of the deoxygenation that dewaters, and starts and stirs.Drip the tetrahydrofuran solution (n-butyl bromide 13.7 grams, 25 milliliters of tetrahydrofuran (THF)s) of n-butyl bromide, rate of addition gentle boil occurs with reaction system and is advisable.After dripping end, 80 ℃ of oil baths made the reaction system back flow reaction 1 hour.Change oil and bathe to ice-water bath, reaction system is cooled to 0 ℃, 9.6 gram methyl cyclopentene ketone/50 milliliters of tetrahydrofuran (THF)s slowly drip.After dropwising, stirred overnight at room temperature.Slowly drip 3.2 gram anhydrous methanols under the room temperature.After dropwising, changing ice-water bath is oil bath, back flow reaction 1.5 hours, and cooling is handled with dilute hydrochloric acid, separates oil phase, with 10 milliliters of extracted with diethyl ether waters 2 times.Merge organic phase.Use anhydrous sodium sulfate drying, filter, remove with rotatory evaporator and desolvate.
Embodiment 2 preparation 1-methyl-3-normal-butyl cyclopentadiene
Implementation process is with embodiment 1.Difference is that the reagent that contains reactive hydrogen atom is dehydrated alcohol 4.6 grams.
Embodiment 3 preparations 1,2,3,4,5-pentamethyl-cyclopentadiene
Fully 250 milliliters of there-necked flasks of oven dry are put into the stirring magneton, place ice bath, vacuumize nitrogen wash, three times repeatedly.Add 23mL Grignard reagent (methylmagnesium-chloride, 22% tetrahydrofuran solution), start and stir.9.4 gram tetramethyl-ring pentenone/50 milliliters of tetrahydrofuran (THF)s slowly drip.After dropwising, stirred overnight at room temperature.Slowly drip 1.2 gram deionized waters under the room temperature.After dropwising, changing ice-water bath is oil bath, back flow reaction 1.5 hours, and cooling is handled with dilute hydrochloric acid, separates oil phase, with 10 milliliters of extracted with diethyl ether waters 2 times.Merge organic phase.Use anhydrous sodium sulfate drying, filter, remove with rotatory evaporator and desolvate.
Embodiment 4 preparations 1,2,5,7-tetramethyl-indenes
Fully 250 milliliters of there-necked flasks of oven dry are put into the stirring magneton, place ice bath, vacuumize nitrogen wash, three times repeatedly.Add 18mL Grignard reagent (methylmagnesium-chloride, 22% tetrahydrofuran solution), start and stir.8.7 restrain 2,5,7-trimethylammonium indone/50 milliliters of tetrahydrofuran (THF)s slowly drip.After dropwising, stirred overnight at room temperature.Slowly drip 0.9 gram deionized water under the room temperature.After dropwising, changing ice-water bath is oil bath, back flow reaction 1.5 hours, and cooling is handled with dilute hydrochloric acid, separates oil phase, with 10 milliliters of extracted with diethyl ether waters 2 times.Merge organic phase.Use anhydrous sodium sulfate drying, filter, remove with rotatory evaporator and desolvate.
Comparative Examples 1 preparation 1-methyl-3-normal-butyl cyclopentadiene (according to patent US5856541 scheme implementation)
Fully 500 milliliters of there-necked flasks of oven dry are put into the stirring magneton, place oil bath, vacuumize nitrogen wash, three times repeatedly.Adding adds 5.5 gram magnesium through 20 milliliters of the dry tetrahydrofuran of the deoxygenation that dewaters, and starts and stirs.Drip the tetrahydrofuran solution (n-butyl bromide 27.4 grams, 50 milliliters of tetrahydrofuran (THF)s) of n-butyl bromide, rate of addition gentle boil occurs with reaction system and is advisable.After dripping end, 80 ℃ of oil baths made the reaction system back flow reaction 2 hours.Change oil and bathe to ice-water bath, reaction system is cooled to 0 ℃, 19.2 gram methyl cyclopentene ketone (0.2mol)/50 milliliter hexane-15 milliliter tetrahydrofuran (THF)s slowly drip.After dropwising, stirring at room 2 hours adds the 60mL hexane, slowly adds 3.6 gram deionized waters (0.2mol).Changing ice-water bath is oil bath, back flow reaction 1 hour, and cooling, solids removed by filtration is used the ether washing leaching cake, revolves to steam to remove to desolvate.(reaction that adds the water step needs control meticulously, to avoid system gel or caking)
Comparative Examples 2 preparation 1-methyl-3-normal-butyl cyclopentadiene (according to patent US5856541 scheme implementation)
Fully 500 milliliters of there-necked flasks of oven dry are put into the stirring magneton, place ice-water bath, vacuumize nitrogen wash, three times repeatedly.Adding 105mL commodity grignard reagent (normal-butyl chlorination magnesium 20wt%, tetrahydrofuran (THF) 50wt%, toluene 30wt%, 1.71M 0.18mol), starts and stirs.Reaction system is cooled to 0 ℃, and 16.8 gram methyl cyclopentene ketone (0.175mol)/50 milliliter hexane-15 milliliter tetrahydrofuran (THF)s slowly drip.After dropwising, stirring at room 2 hours adds the 60mL hexane, slowly adds 3.15 gram deionized waters (0.175mol).Changing ice-water bath is oil bath, back flow reaction 1 hour, and cooling, solids removed by filtration is used the ether washing leaching cake, revolves to steam to remove to desolvate.(reaction that adds the water step needs control meticulously, to avoid system gel or caking)
The results are shown in Table 1:
Table 1
Claims (9)
1. a synthetic polysubstituted cyclopentadiene or replace the method for indenes, it is characterized in that, this method is by reaction raw materials substituted cyclopentene ketone or replace indone Yu Geshi reagent react, handles with the reagent A that contains reactive hydrogen atom again, obtains polysubstituted cyclopentadiene or replaces indenes; Described reaction raw materials substituted cyclopentene ketone replaces indone by shown in 3,4 formulas by shown in 1,2 formulas;
R in the formula
1～R
10Identical or different, for hydrogen atom or contain the saturated or undersaturated alkyl of 1-20 carbon atom; R
1～R
10In randomly cyclization or the not cyclization of adjacent substituted radical, described Grignard reagent structure is R
0MgX, it is optional for the Grignard reagent of commodity or by reacting the Grignard reagent that generates, R
0For containing the saturated or undersaturated alkyl of 1-20 carbon atom, X is F, Cl, Br or I;
The described A reagent that contains reactive hydrogen atom is water, be no more than the alcohol of 10 carbon atoms, be no more than the phenol of 20 carbon atoms, or its two or many persons' mixture.
2. the method for synthetic polysubstituted cyclopentadiene according to claim 1 or replacement indenes is characterized in that, the mol ratio of employed Grignard reagent and substituted cyclopentene ketone or replacement indone is 1.
3. the method for synthetic polysubstituted cyclopentadiene according to claim 1 or replacement indenes is characterized in that the employed reagent A that contains reactive hydrogen atom and the mol ratio of Grignard reagent are 1.
4. the method for synthetic polysubstituted cyclopentadiene according to claim 1 or replacement indenes is characterized in that the employed reagent A that contains reactive hydrogen atom is to contain the alcohol that is no more than 10 carbon atoms.
5. the method for synthetic polysubstituted cyclopentadiene according to claim 4 or replacement indenes is characterized in that the employed reagent A that contains reactive hydrogen atom is anhydrous methanol or dehydrated alcohol.
6. the method for synthetic polysubstituted cyclopentadiene according to claim 1 or replacement indenes is characterized in that, carries out in the mixed solvent that is reflected at ether solvent and saturated alkane solvent of substituted cyclopentene ketone or replacement indone and Grignard reagent.
7. the method for synthetic polysubstituted cyclopentadiene according to claim 6 or replacement indenes is characterized in that the usage ratio of ether solvent and saturated alkane solvent is 1: 0 to 1: 4.
8. the method for synthetic polysubstituted cyclopentadiene according to claim 6 or replacement indenes is characterized in that solvent for use is the mixed solvent of tetrahydrofuran (THF) and hexane.
9. the method for synthetic polysubstituted cyclopentadiene according to claim 7 or replacement indenes is characterized in that solvent for use is a tetrahydrofuran (THF).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054540A (en) * | 2019-05-16 | 2019-07-26 | 海门瑞一医药科技有限公司 | A kind of preparation method of pentamethylcyclopentadiene |
| CN111154498A (en) * | 2020-01-19 | 2020-05-15 | 西安瑞联新材料股份有限公司 | Preparation method of liquid crystal compound containing 1, 5-indan and difluoromethoxy bridge |
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| US5329056A (en) * | 1993-01-19 | 1994-07-12 | Albemarle Corporation | Preparation of substituted cyclopentadienes |
| US5434324A (en) * | 1993-10-15 | 1995-07-18 | Albemarle Corporation | Preparation of alkylcyclopentadienes |
| US5856541A (en) * | 1995-02-17 | 1999-01-05 | Witco Gmbh | Process for preparing 1 3-disubstituted cyclopentadienyl ligands and transition metal complexes thereof |
| DE19934234A1 (en) * | 1999-07-21 | 2001-02-01 | Targor Gmbh | Simplified preparation of substituted cyclopentadienes comprises reacting Grignard reagents with substituted cyclopent-2-ene-1-ones, with protonization/dehydration step effected with alcohol in absence of water or aqueous acid |
| CN1653021A (en) * | 2002-04-10 | 2005-08-10 | 巴塞尔聚烯烃股份有限公司 | Preparation of substituted indenes |
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2009
- 2009-08-28 CN CN2009101697125A patent/CN101993330A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5329056A (en) * | 1993-01-19 | 1994-07-12 | Albemarle Corporation | Preparation of substituted cyclopentadienes |
| US5434324A (en) * | 1993-10-15 | 1995-07-18 | Albemarle Corporation | Preparation of alkylcyclopentadienes |
| US5856541A (en) * | 1995-02-17 | 1999-01-05 | Witco Gmbh | Process for preparing 1 3-disubstituted cyclopentadienyl ligands and transition metal complexes thereof |
| DE19934234A1 (en) * | 1999-07-21 | 2001-02-01 | Targor Gmbh | Simplified preparation of substituted cyclopentadienes comprises reacting Grignard reagents with substituted cyclopent-2-ene-1-ones, with protonization/dehydration step effected with alcohol in absence of water or aqueous acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054540A (en) * | 2019-05-16 | 2019-07-26 | 海门瑞一医药科技有限公司 | A kind of preparation method of pentamethylcyclopentadiene |
| CN111154498A (en) * | 2020-01-19 | 2020-05-15 | 西安瑞联新材料股份有限公司 | Preparation method of liquid crystal compound containing 1, 5-indan and difluoromethoxy bridge |
| CN111154498B (en) * | 2020-01-19 | 2021-10-22 | 西安瑞联新材料股份有限公司 | Preparation method of liquid crystal compound containing 1, 5-indan and difluoromethoxy bridge |
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