CN111849507A - Fluorine-containing liquid crystal molecule with cholesterol as chiral center and preparation method thereof - Google Patents
Fluorine-containing liquid crystal molecule with cholesterol as chiral center and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-containing liquid crystal molecule with cholesterol as a chiral center and a preparation method thereof, belonging to the technical field of liquid crystal materials. The chiral liquid crystal compound is obtained by a multi-step reaction, and the general formula of the compound is expressed as follows: (C)27H45O)(C7H2O2)(CH2)n(C13H8O3)(CH2)m(COOCH＝CH2) Wherein m is more than or equal to 3 and less than or equal to 9; the range of n is more than or equal to 3 and less than or equal to 9. The invention adopts the raw material containing F, greatly improves the HTP value (27 mu m) of the cholesterol chiral molecule‑1) The application width of the liquid crystal molecules taking cholesterol as the chiral center is greatly widened, so that the value of the liquid crystal molecules taking cholesterol as the chiral center in the field of optical materials is enlarged, the raw material cost is saved, and the synthesis process is optimized.
Description
Technical Field
The invention relates to a fluorine-containing liquid crystal molecule with cholesterol as a chiral center and a preparation method thereof, belonging to the technical field of liquid crystal materials.
Background
In chemistry, molecules that are identical in composition but that are spatially structurally mirror images of each other (enantiomers) are referred to as chiral molecules. Liquid crystals are an oriented fluid between isotropic liquids and fully ordered crystals, and have both liquid mobility and anisotropic properties such as birefringence. When the material crystal is heated and melted or dissolved by solvent, although the rigidity of the solid substance is lost to obtain the fluidity of the liquid material, the ordered arrangement and the periodically staggered arrangement of the crystalline material are partially preserved to form a helical structure, and the vibration direction of the polarized light is gradually twisted by an angle when the polarized light passes through the liquid crystal, and the liquid crystal is called chiral liquid crystal.
In 1922, the french chemist Friedel found that optically active substances could induce the transformation of nematic liquid crystals into cholesteric liquid crystals. The ester derivative of cholesterol is the earliest chiral liquid crystal and is used as a chiral additive in nematic liquid crystal display materials. Since then, the research interest of scholars at home and abroad on small molecule liquid crystal compounds containing chiral groups is increasingly active, and many liquid crystal compounds with cholesteric phase or chiral smectic phase have been synthesized, and the properties and applications of the liquid crystal compounds are intensively researched. However, the research on chiral liquid crystal polymers and chiral liquid crystal elastomers is started under the background, and after the micromolecule chiral liquid crystal compounds with excellent electrical and optical characteristics are polymerized, a wider application space is created for chiral liquid crystal materials.
At present, extensive research on the synthesis and application of chiral liquid crystal materials has been carried out in China. In the aspect of chiral additives for liquid crystals, how to develop novel efficient, green and low-cost chiral additives is a challenge for liquid crystal researchers. The research on the ferroelectric liquid crystal is vigorously carried out, and a solid foundation is laid for the development of high-performance liquid crystal materials and the development of liquid crystal displays in China. As a kind of functionalized liquid crystal material, the chiral liquid crystal polymer has wide prospect in the field of information recording and storage by using the unique performance thereof. The chiral liquid crystal elastomer integrates elasticity and liquid crystal property, and has potential application value in the fields of piezoelectric materials, nonlinear optical materials and the like. It is believed that in the near future, chiral liquid crystal materials must find wide application in more fields with the continuing efforts of numerous liquid crystal researchers.
The efficiency of chiral doping can be quantified by the "helical twisting power", i.e., the HTP value, defined by the formula where the doping concentration is small, where p is the pitch of the induced helix and x is the mole fraction of the doping. The formula is HTP ═ 1/px, and as a goal, high HTP values are desirable, with the mole fraction x of dopant used being as small as possible, thereby producing maximum helicity. The helicity is given by the number of pitches p of the helix, which can be in the wavelength range uv-vis-nir. The cholesterol chiral material has a small HTP value, and other molecules with high HTP values have high cost, complex synthesis method and narrow market available range.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a fluorine-containing liquid crystal molecule with cholesterol as a chiral center and a preparation method thereof, which solves the problem of low HTP value of the chiral molecule with cholesterol as the chiral center.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a fluorine-containing liquid crystal molecule with cholesterol as a chiral center has the following structural formula:
wherein m is more than or equal to 3 and less than or equal to 9; the range of n is more than or equal to 3 and less than or equal to 9.
A method for preparing fluorine-containing liquid crystal molecules with cholesterol as a chiral center comprises the following steps:
(1) and synthesis of an intermediate A:
(1.1) 4' -hydroxybiphenyl-4-carboxylic acid and m (m is more than or equal to 3 and less than or equal to 9) chlorohydrin are used as reaction raw materials to react, and a reaction system is NaOH/N product aI, EtOH/H2O, dilute HCl to obtain a product a, and the knot of the product aThe formula is expressed as follows:
(1.2) reacting the product of the product a and acryloyl chloride as raw materials to obtain an intermediate A, wherein the system is a dioxane/triethylamine system, and the structural formula of the intermediate A is expressed as follows:
(2) and synthesis of an intermediate B:
(2.1) carrying out esterification reaction by using chiral cholesterol and F-containing p-hydroxybenzoic acid as raw materials, wherein the reaction system is xylene/p-toluenesulfonic acid to obtain a product b, and the structural formula of the product b is expressed as follows:
(2.2) reacting the product B with N (N is more than or equal to 3 and less than or equal to 9) chlorohydrin serving as raw materials to obtain an intermediate B, wherein the reaction system is NaOH/N product aI, and EtOH/H2O, and the structural formula of intermediate B is expressed as follows:
(1) performing esterification reaction on the intermediate A and the intermediate B to finally obtain a target product, wherein the reaction system is DCC/DMAP, N2A tetrahydrofuran system having the formula:
as a preferred example, product a is prepared by the following steps: adding a certain mass of 4 '-hydroxybiphenyl-4-carboxylic acid into 5-6 times of absolute ethyl alcohol, heating in an oil bath to 60 ℃ for dissolution, then adding deionized water with the mass of 1/2 times of the absolute ethyl alcohol, then slowly adding NaOH with the molar number of 2.5-3.0 times of that of the 4' -hydroxybiphenyl-4-carboxylic acid into the whole system, and continuing to react for 1h at 60 ℃ after the system is changed from colorless to light yellow and transparent; adding sodium iodide accounting for 2 percent of the mass of the 4 '-hydroxybiphenyl-4-carboxylic acid as a phase transfer catalyst, slowly dripping m (m is more than or equal to 3 and less than or equal to 9) of m-membered chlorohydrin with the mole number of 1.3 times of that of the 4' -hydroxybiphenyl-4-carboxylic acid into the whole system, and carrying out reflux reaction at the temperature of 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8-10% dilute hydrochloric acid, adjusting the pH value to 2-3, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3-4 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 50 ℃ for 24hours to obtain a product a, wherein the product a is white powder.
As a preferred example, intermediate a is prepared by the following steps: adding a certain mass of the product a into a 1, 4-dioxane solvent with the mass being 6 times that of the product a, adding triethylamine with the mole number being 1.5 times that of the product a while stirring, and cooling in an ice water bath (0-2 ℃); slowly dripping acryloyl chloride of which the mole number is 0.9 time that of the product a into a reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, preparing 2-3 ℃ ionized water with 5 times of the mass of the 1, 4-dioxane solvent, pouring the reaction liquid into the ionized water, separating out a large amount of white precipitate, filtering, recrystallizing the precipitate for 2-3 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 50 ℃ for 24hours to obtain an intermediate A, wherein the intermediate A is white powder.
As a preferred example, product b is prepared by the following steps: : adding a certain mass of cholesterol into xylene with the mass of 8 times, mechanically stirring, adding 3, 5-difluoro-4-hydroxybenzoic acid with the mole number of 1.2 times that of the cholesterol, continuously stirring fully, adding p-toluenesulfonic acid monohydrate with the mass of 2% of the cholesterol as a catalyst, heating to 140 ℃, carrying out reflux reaction for 24hours, cooling to room temperature, pouring out xylene waste on the upper layer, adding ethyl acetate with the mass of 2 times that of the xylene to carry out ultrasonic dissolution on massive precipitates on the lower layer, carrying out washing liquid treatment by using a sodium bicarbonate aqueous solution with the mass of 5% of the same mass of the ethyl acetate after complete dissolution, carrying out liquid separation treatment, pouring out a water layer on the lower layer, carrying out rotary evaporation on an organic layer to remove ethyl acetate, then pouring absolute ethyl alcohol with the mass of the same xylene to carry out recrystallization, carrying out co-recrystallization for 2-3 times, filtering, carrying out vacuum drying at 50 ℃ for 24hours to obtain a product b, and product b is a yellowish brown powder.
As a preferred example, intermediate B is prepared by the following steps: adding a certain mass of the product b into absolute ethyl alcohol with the mass 5-6 times that of the product b, heating the mixture in an oil bath at 60 ℃ for dissolution, then adding deionized water with the mass 1/2 of the absolute ethyl alcohol, then slowly adding NaOH with the molar number 1.2 times that of the product b into the whole system, and continuing to react for 1h at 60 ℃ after the system becomes light yellow and transparent; adding sodium iodide accounting for 2% of the mass of the product b as a phase transfer catalyst into a reaction system, slowly dripping n (n is more than or equal to 3 and less than or equal to 9) of n-membered chlorohydrin with the mole number of 1.3 times that of the product b into the whole system, and after finishing dripping, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% -10% dilute hydrochloric acid, adjusting the pH value to 2-3, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3-4 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 50 ℃ for 24hours to obtain an intermediate B, wherein the intermediate B is white powder.
As a preferred example, intermediate a and intermediate B are fed in a molar ratio n (B) to n (d) of 1.05:1 to a tetrahydrofuran solvent having a mass 4 times that of the mixture of intermediate a and intermediate B; under the protection of nitrogen, adding 1.9 times of dicyclohexylcarbodiimide and 0.03 times of 4-dimethylaminopyridine into the reaction system, stirring, and reacting at normal temperature for 12 hours; and after the reaction is finished, filtering to remove the generated white precipitate, performing rotary evaporation on the filtrate to remove tetrahydrofuran, then performing 3-4 times of recrystallization on the product by using absolute ethyl alcohol, filtering, and performing vacuum drying at 50 ℃ for 24hours to obtain the final product, wherein the final product is white powder.
The invention has the beneficial effects that: the invention adopts the raw material containing F, greatly improves the HTP value (27 mu m) of the cholesterol chiral molecule-1) The application width of the liquid crystal molecules taking cholesterol as the chiral center is greatly widened, so that the value of the liquid crystal molecules taking cholesterol as the chiral center in the field of optical materials is enlarged, the raw material cost is saved, and the synthesis process is optimized.
Drawings
FIG. 1 shows the final product containing F when m is 3 and n is 3 in the present invention1A HNMR map;
FIG. 2 shows the product of the present invention containing no F when m is 3 and n is 31A HNMR map;
FIG. 3 shows F-containing final products of the present invention when m is 9 and n is 91A HNMR map;
FIG. 4 shows the product of the present invention containing no F when m is 9 and n is 91A HNMR map;
FIG. 5 shows F-containing final products of the present invention when m is 9 and n is 31A HNMR map;
FIG. 6 shows the product of the present invention containing no F when m is 9 and n is 31A HNMR map;
FIG. 7 shows F-containing final products of the present invention when m is 3 and n is 91A HNMR map;
FIG. 8 shows the product of the present invention containing no F when m is 3 and n is 91HNMR atlas.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purpose and the efficacy of the invention easily understood, the invention is further described with reference to the following embodiments.
Example one
(C27H45O)(C7F2H2O2)(CH2)3(C13H8O3)(CH2)3(COOCH＝CH2) The structure and synthesis of (1):
step a: adding 42.85g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid into 215g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 107.5g of deionized water, then slowly adding 20g (0.5mol) of sodium hydroxide into a reaction system, continuing to react for 1h at 60 ℃, and gradually changing the reaction system from colorless to light yellow; adding 0.857g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 24.6g (0.26mol) of 3-chloro-1-propanol into the reaction system, and after dropwise adding is finished, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% dilute hydrochloric acid, adjusting the pH value of the reaction solution to be 2, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery product a, wherein the weight of the product a is about 44.1g after weighing, and the yield is about 81%;
step b: weighing 27.2g (0.1mol) of the product a, adding the product a into 163.2g of 1, 4-dioxane solvent, adding 15.2g (0.15mol) of triethylamine while stirring, and cooling in an ice water bath (0 ℃); slowly dripping 8.15g (0.09mol) of acryloyl chloride into the reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, pouring the reaction solution into 816g of ionized water at the temperature of 2 ℃, separating out a large amount of white precipitate, filtering, recrystallizing the precipitate for 2 times by using absolute ethyl alcohol, filtering, and drying in a vacuum drying oven at the temperature of 50 ℃ for 24hours to obtain an intermediate A which is white powder, wherein the weight of the intermediate A is about 29.4g, and the yield is about 90%;
step c: adding 77.3g (0.2mol) of cholesterol into 618.4g of dimethylbenzene, mechanically stirring, then adding 41.8g (0.24mol) of 3, 5-difluoro-4-hydroxybenzoic acid into the reaction system, uniformly stirring, adding 1.546g of p-toluenesulfonic acid monohydrate as a catalyst into the reaction system, heating to 140 ℃ for reflux reaction for 24hours, cooling to room temperature after the reaction is finished, pouring out xylene waste serving as an upper layer solvent, pouring 1236.8g of ethyl acetate into lower-layer caking sediment, ultrasonically dissolving, washing with a 5% sodium bicarbonate aqueous solution with the same mass of ethyl acetate, carrying out liquid separation treatment, pouring out a lower-layer aqueous layer, carrying out rotary evaporation on the obtained organic layer to remove ethyl acetate, pouring the rest product into anhydrous ethanol with the same mass of xylene for recrystallization for 3 times, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a product b in a soil yellow powder shape, after weighing, the mass is about 89g, and the yield is about 82%;
step d: adding 54.3g (0.1mol) of the product c into 325g of absolute ethyl alcohol, heating the mixture in an oil bath to 60 ℃ for dissolution, then adding 162.5g of deionized water, then slowly adding 4.8g (0.12mol) of sodium hydroxide into a reaction system, continuing to react for 1hour at 60 ℃, gradually changing the reaction system from colorless to orange yellow, and after the system becomes light yellow and transparent; adding 1.086g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 12.3g (0.13mol) of 3-chloro-1-propanol into the reaction system, and after dropwise adding, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, adjusting the pH value of the reaction solution to 2 by using 8% dilute hydrochloric acid, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, filtering, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery intermediate B, weighing the intermediate B to obtain 49g of the intermediate B by mass, and obtaining the yield of 82%;
step e: adding 28.0g (0.0856mol) of the intermediate A and 49g (0.0815mol) of the intermediate B into 307.7g of tetrahydrofuran solvent, protecting with nitrogen, adding 19.6g of dicyclohexylcarbodiimide and 0.33g of 4-dimethylaminopyridine into a reaction system, stirring, and reacting for 12 hours at normal temperature; after the reaction is finished, filtering to remove the generated white precipitate, carrying out rotary evaporation on the filtrate to remove tetrahydrofuran to obtain a pre-target product, then recrystallizing the pre-target product for 3 times by using absolute ethyl alcohol, drying for 24hours in a vacuum drying oven at 50 ℃ to obtain a white powdery final product, weighing the final product to obtain 60.3g of white powder, and obtaining the yield of 81 percent.
Comparative example 1
(C27H45O)(C7H4O2)(CH2)3(C13H8O3)(CH2)3(COOCH＝CH2) The structure and synthesis of (1):
step a: adding 42.85g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid into 215g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 107.5g of deionized water, then slowly adding 20g (0.5mol) of sodium hydroxide into a reaction system, continuing to react for 1h at 60 ℃, and gradually changing the reaction system from colorless to light yellow; adding 0.857g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 24.6g (0.26mol) of 3-chloro-1-propanol into the reaction system, and after dropwise adding is finished, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% dilute hydrochloric acid, adjusting the pH value of the reaction solution to be 2, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery product a, wherein the weight of the product a is about 44.1g after weighing, and the yield is about 81%;
step b: weighing 27.2g (0.1mol) of the product a, adding the product a into 163.2g of 1, 4-dioxane solvent, adding 15.2g (0.15mol) of triethylamine while stirring, and cooling in an ice water bath (0 ℃); slowly dripping 8.15g (0.09mol) of acryloyl chloride into the reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, pouring the reaction solution into 816g of ionized water at the temperature of 2 ℃, separating out a large amount of white precipitate, filtering, recrystallizing the precipitate for 2 times by using absolute ethyl alcohol, filtering, and drying in a vacuum drying oven at the temperature of 50 ℃ for 24hours to obtain an intermediate A which is white powder, wherein the weight of the intermediate A is about 29.4g, and the yield is about 90%;
step c: adding 77.3g (0.2mol) of cholesterol into 618.4g of dimethylbenzene, mechanically stirring, adding 33.1g (0.24mol) of p-hydroxybenzoic acid into the reaction system, uniformly stirring, adding 1.546g of p-toluenesulfonic acid monohydrate as a catalyst into the reaction system, heating to 140 ℃, refluxing and reacting for 24hours, cooling to room temperature after the reaction is finished, pouring out an upper layer solvent xylene waste, pouring 1236.8g of ethyl acetate into a lower layer caking precipitate, ultrasonically dissolving, washing with a 5% sodium bicarbonate aqueous solution with the same mass of ethyl acetate, carrying out liquid separation treatment, pouring out a lower layer of water, carrying out rotary evaporation on the obtained organic layer to remove ethyl acetate, pouring the rest product into anhydrous ethanol with the same mass of xylene for recrystallization for 3 times, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a product b which is a soil yellow powder, weighing the product b to be about 77.0g, the yield is about 76%;
step d: adding 50.7g (0.1mol) of the product c into 304.2g of absolute ethyl alcohol, heating the mixture in an oil bath to 60 ℃ for dissolution, then adding 152.1g of deionized water, then slowly adding 4.8g (0.12mol) of sodium hydroxide into a reaction system, continuing to react for 1hour at 60 ℃, gradually changing the reaction system from colorless to orange yellow, and after the system becomes light yellow and transparent; adding 1.0g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 12.3g (0.13mol) of 3-chloro-1-propanol into the reaction system, and after dropwise adding, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, adjusting the pH value of the reaction solution to 2 by using 8% dilute hydrochloric acid, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, filtering, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery intermediate B, weighing, and obtaining the intermediate B with the mass of about 46.2g and the yield of about 82%;
step e: adding 28.0g (0.0856mol) of the intermediate A and 46.0g (0.0815mol) of the intermediate B into 296.0g of tetrahydrofuran solvent, protecting with nitrogen, adding 19.6g of dicyclohexylcarbodiimide and 0.33g of 4-dimethylaminopyridine into a reaction system, stirring, and reacting at normal temperature for 12 hours; after the reaction is finished, white precipitate is filtered and removed, tetrahydrofuran is removed from filtrate through rotary evaporation to obtain a pre-target product, then the pre-target product is recrystallized for 3 times by using absolute ethyl alcohol, and the obtained product is dried in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery final product, wherein the weight of the final product is about 56.2g, and the yield is about 79%.
Example two:
(C27H45O)(C7F2H2O2)(CH2)9(C13H8O3)(CH2)9(COOCH＝CH2) The structure and synthesis of (1):
step a: adding 42.85g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid into 215g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 107.5g of deionized water, then slowly adding 20g (0.5mol) of sodium hydroxide into a reaction system, continuing to react for 1h at 60 ℃, and gradually changing the reaction system from colorless to light yellow; adding 0.857g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 46.5g (0.26mol) of 9-chloro-1-nonanol into the reaction system, and after dropwise adding is finished, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% dilute hydrochloric acid, adjusting the pH value of the reaction solution to be 2, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery product a, wherein the weight of the product a is about 60.6g after weighing, and the yield is about 85%;
step b: weighing about 35.6g (0.1mol) of the product a, adding the product a into 213.6g of 1, 4-dioxane solvent, stirring, adding 15.2g (0.15mol) of triethylamine, and cooling in an ice water bath (0 ℃); slowly dripping 8.15g (0.09mol) of acryloyl chloride into the reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, pouring the reaction solution into 1068g of 2 ℃ ionized water, immediately precipitating a large amount of white precipitate, filtering, recrystallizing for 2 times by using absolute ethyl alcohol, filtering, drying for 24hours in a 50 ℃ vacuum drying oven to obtain an intermediate A of white powder, wherein the weight of the intermediate A is about 37.5g, and the yield is about 91%;
step c: adding 77.3g (0.2mol) of cholesterol into 618.4g of dimethylbenzene, mechanically stirring, then adding 41.8g (0.24mol) of 3, 5-difluoro-4-hydroxybenzoic acid into the reaction system, uniformly stirring, then adding 1.546g of p-toluenesulfonic acid monohydrate into the reaction system, heating to 140 ℃ for reflux reaction for 24hours, cooling to room temperature after the reaction is finished, pouring out xylene waste serving as an upper layer solvent, pouring 1236.8g of ethyl acetate into lower-layer agglomeration precipitate, ultrasonically dissolving, then washing an organic layer by using 5% sodium bicarbonate aqueous solution with the same mass, carrying out liquid separation treatment, pouring out a lower-layer aqueous layer, carrying out rotary evaporation on the obtained organic layer to remove ethyl acetate, pouring the rest product into absolute ethyl alcohol with the same mass as the dimethylbenzene for recrystallization for 3 times, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a product b which is earthy yellow powder, weighing about 89g, the yield is about 82%;
step d: adding 54.3g (0.1mol) of the product c into 325g of absolute ethyl alcohol, heating the mixture in an oil bath to 60 ℃ for dissolution, then adding 162.5g of deionized water, then slowly adding 4.8g (0.12mol) of sodium hydroxide into the reaction system, continuing to react for 1h at 60 ℃, gradually changing the reaction system from colorless to orange yellow, adding 1.086g of sodium iodide into the reaction system as a phase transfer catalyst after the system becomes light yellow and transparent, then slowly adding 23.2g (0.13mol) of 9-chloro-1-nonanol into the reaction system, and after finishing the dropwise addition, carrying out reflux reaction for 24h at 80 ℃; after the reaction is finished, adjusting the pH value of the reaction solution to 2 by using 8% dilute hydrochloric acid, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, filtering, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery intermediate B, weighing the intermediate B to obtain 56g, and obtaining the yield of 82%;
step e: adding 35.2g (0.0858mol) of the intermediate A and 56g (0.0818mol) of the intermediate B into 365.0g of tetrahydrofuran solvent, protecting with nitrogen, adding 19.6g of dicyclohexylcarbodiimide and 0.33g of 4-dimethylaminopyridine into a reaction system, stirring, and reacting for 12 hours at normal temperature; after the reaction is finished, insoluble substances are removed by filtration, filtrate is subjected to rotary evaporation to remove tetrahydrofuran to obtain a pre-target product, the pre-target product is recrystallized for 3 times by using ethanol, and the product is dried in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery final product, wherein the weight of the final product is about 70.5g, and the yield is about 80%.
Comparative example two:
(C27H45O)(C7H4O2)(CH2)9(C13H8O3)(CH2)9(COOCH＝CH2) The structure and synthesis of (1):
step a: adding 42.85g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid into 215g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 107.5g of deionized water, then slowly adding 20g (0.5mol) of sodium hydroxide into a reaction system, continuing to react for 1h at 60 ℃, and gradually changing the reaction system from colorless to light yellow; adding 0.857g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 46.5g (0.26mol) of 9-chloro-1-nonanol into the reaction system, and after dropwise adding is finished, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% dilute hydrochloric acid, adjusting the pH value of the reaction solution to be 2, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery product a, wherein the weight of the product a is about 60.6g after weighing, and the yield is about 85%;
step b: weighing about 35.6g (0.1mol) of the product a, adding the product a into 213.6g of 1, 4-dioxane solvent, stirring, adding 15.2g (0.15mol) of triethylamine, and cooling in an ice water bath (0 ℃); slowly dripping 8.15g (0.09mol) of acryloyl chloride into the reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, pouring the reaction solution into 1068g of 2 ℃ ionized water, immediately precipitating a large amount of white precipitate, filtering, recrystallizing for 2 times by using absolute ethyl alcohol, filtering, drying for 24hours in a 50 ℃ vacuum drying oven to obtain an intermediate A of white powder, wherein the weight of the intermediate A is about 37.5g, and the yield is about 91%;
step c: 77.3g (0.2mol) of cholesterol were added to 618.4g of xylene, mechanically stirred, then 33.1g (0.24mol) of 4-hydroxybenzoic acid was added to the reaction system, after stirring evenly, adding 1.546g of p-toluenesulfonic acid monohydrate into the reaction system, heating to 140 ℃, carrying out reflux reaction for 24h, after the reaction is finished, cooling to room temperature, pouring out xylene waste serving as an upper solvent, pouring 1236.8g of ethyl acetate into the lower-layer caked precipitate, performing ultrasonic dissolution, then washing the organic layer with 5% sodium bicarbonate aqueous solution with the same mass, separating the liquid, pouring the lower water layer, performing rotary evaporation on the obtained organic layer to remove ethyl acetate, pouring the residual product into anhydrous ethanol with the same mass as xylene for recrystallization for 3 times, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a product b in a yellowish powder shape, weighing the product b to obtain 89g of the mass, and obtaining the yield of 82 percent;
step d: adding 50.7g (0.1mol) of the product c into 304.2g of absolute ethyl alcohol, heating the mixture in an oil bath to 60 ℃ for dissolution, then adding 152.1g of deionized water, then slowly adding 4.8g (0.12mol) of sodium hydroxide into a reaction system, continuing to react for 1hour at 60 ℃, gradually changing the reaction system from colorless to orange yellow, and after the system becomes light yellow and transparent; adding 1.0g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 23.2g (0.13mol) of 9-chloro-1-nonanol into the reaction system, and after dropwise adding, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, adjusting the pH value of the reaction solution to 2 by using 8% dilute hydrochloric acid, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, filtering, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery intermediate B, weighing the intermediate B to obtain 53.2g, wherein the yield is about 82%;
step e: adding 35.2g (0.0858mol) of the intermediate A and 53.1g (0.0818mol) of the intermediate B into 353.2g of tetrahydrofuran solvent, protecting with nitrogen, adding 19.6g of dicyclohexylcarbodiimide and 0.33g of 4-dimethylaminopyridine into the reaction system, stirring, and reacting for 12 hours at normal temperature; after the reaction is finished, insoluble substances are removed by filtration, filtrate is subjected to rotary evaporation to remove tetrahydrofuran to obtain a pre-target product, the pre-target product is recrystallized for 3 times by using ethanol, and the product is dried in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery final product, the weight of the final product is about 68.1g, and the yield of the final product is about 80%.
Example three:
(C27H45O)(C7F2H2O2)(CH2)3(C13H8O3)(CH2)9(COOCH＝CH2) The structure and synthesis of (1):
step a: adding 42.85g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid into 215g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 107.5g of deionized water, then slowly adding 20g (0.5mol) of sodium hydroxide into a reaction system, continuing to react for 1h at 60 ℃, and gradually changing the reaction system from colorless to light yellow; adding 0.857g of sodium iodide into the reaction system, slowly dripping 46.5g (0.26mol) of 9-chloro-1-nonanol into the reaction system, and after finishing dripping, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% dilute hydrochloric acid, adjusting the pH value of the reaction solution to be 2, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery product a, wherein the weight of the product a is about 60.6g after weighing, and the yield is about 85%;
step b: weighing about 35.6g (0.1mol) of the product a, adding the product a into 213.6g of 1, 4-dioxane solvent, stirring, adding 15.2g (0.15mol) of triethylamine, and cooling in an ice water bath (0 ℃); slowly dripping 8.15g (0.09mol) of acryloyl chloride into the reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, pouring the reaction solution into 1068g of 2 ℃ ionized water, immediately precipitating a large amount of white precipitate, filtering, recrystallizing for 2 times by using absolute ethyl alcohol, and drying in a 50 ℃ vacuum drying oven for 24hours to obtain an intermediate A of white powder, wherein the weight of the intermediate A is about 37.5g, and the yield is about 91%;
step c: adding 77.3g (0.2mol) of cholesterol into 618.4g of dimethylbenzene, mechanically stirring, adding 33.1g (0.24mol) of p-hydroxybenzoic acid into the reaction system, uniformly stirring, adding 1.546g of p-toluenesulfonic acid monohydrate as a catalyst into the reaction system, heating to 140 ℃, refluxing and reacting for 24hours, cooling to room temperature after the reaction is finished, pouring out an upper layer solvent xylene waste, pouring 1236.8g of ethyl acetate into a lower layer caking precipitate, ultrasonically dissolving, washing with a 5% sodium bicarbonate aqueous solution with the same mass of ethyl acetate, carrying out liquid separation treatment, pouring out a lower layer of water, carrying out rotary evaporation on the obtained organic layer to remove ethyl acetate, pouring the rest product into anhydrous ethanol with the same mass of xylene for recrystallization for 3 times, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a product b which is a soil yellow powder, weighing the product b to be about 77.0g, the yield is about 76%;
step d: adding 54.3g (0.1mol) of the product c into 325g of absolute ethyl alcohol, heating the mixture in an oil bath to 60 ℃ for dissolution, then adding 162.5g of deionized water, then slowly adding 4.8g (0.12mol) of sodium hydroxide into the reaction system, continuing to react for 1h at 60 ℃, gradually changing the reaction system from colorless to orange yellow, adding 1.086g of sodium iodide into the reaction system as a phase transfer catalyst after the system becomes light yellow and transparent, then slowly dropwise adding 12.3g (0.13mol) of 3-chloro-1-propanol into the reaction system, and after the dropwise adding is finished, carrying out reflux reaction for 24h at 80 ℃; after the reaction is finished, adjusting the pH value of the reaction solution to 2 by using 8% dilute hydrochloric acid, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery intermediate B, wherein the weight of the intermediate B is 49g, and the yield is 82%;
step e: adding 35.1g (0.0.0856mol) of the intermediate A and 49g (0.0815mol) of the intermediate B into 336.4g of tetrahydrofuran solvent, protecting with nitrogen, adding 19.6g of dicyclohexylcarbodiimide and 0.33g of 4-dimethylaminopyridine into a reaction system, stirring, and reacting at normal temperature for 12 hours; after the reaction is finished, insoluble substances are removed by filtration, filtrate is subjected to rotary evaporation to remove tetrahydrofuran to obtain a pre-target product, then the pre-target product is recrystallized for 3 times by using ethanol, and the obtained product is dried in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery final product, wherein the weight of the final product is about 86.2g, and the yield is about 80%.
Comparative example three:
(C27H45O)(C7H4O2)(CH2)3(C13H8O3)(CH2)9(COOCH＝CH2) The structure and synthesis of (1):
step a: adding 42.85g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid into 215g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 107.5g of deionized water, then slowly adding 20g (0.5mol) of sodium hydroxide into a reaction system, continuing to react for 1h at 60 ℃, and gradually changing the reaction system from colorless to light yellow; adding 0.857g of sodium iodide into the reaction system, slowly dripping 46.5g (0.26mol) of 9-chloro-1-nonanol into the reaction system, and after finishing dripping, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% dilute hydrochloric acid, adjusting the pH value of the reaction solution to be 2, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery product a, wherein the weight of the product a is about 60.6g after weighing, and the yield is about 85%;
step b: weighing about 35.6g (0.1mol) of the product a, adding the product a into 213.6g of 1, 4-dioxane solvent, stirring, adding 15.2g (0.15mol) of triethylamine, and cooling in an ice water bath (0 ℃); slowly dripping 8.15g (0.09mol) of acryloyl chloride into the reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, pouring the reaction solution into 1068g of 2 ℃ ionized water, immediately precipitating a large amount of white precipitate, filtering, recrystallizing for 2 times by using absolute ethyl alcohol, and drying in a 50 ℃ vacuum drying oven for 24hours to obtain an intermediate A of white powder, wherein the weight of the intermediate A is about 37.5g, and the yield is about 91%;
step c: adding 77.3g (0.2mol) of cholesterol into 618.4g of dimethylbenzene, mechanically stirring, adding 33.1g (0.24mol) of p-hydroxybenzoic acid into the reaction system, uniformly stirring, adding 1.546g of p-toluenesulfonic acid monohydrate as a catalyst into the reaction system, heating to 140 ℃, refluxing and reacting for 24hours, cooling to room temperature after the reaction is finished, pouring out an upper layer solvent xylene waste, pouring 1236.8g of ethyl acetate into a lower layer caking precipitate, ultrasonically dissolving, washing with a 5% sodium bicarbonate aqueous solution with the same mass of ethyl acetate, carrying out liquid separation treatment, pouring out a lower layer of water, carrying out rotary evaporation on the obtained organic layer to remove ethyl acetate, pouring the rest product into anhydrous ethanol with the same mass of xylene for recrystallization for 3 times, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a product b which is a soil yellow powder, weighing the product b to be about 77.0g, the yield is about 76%;
step d: adding 50.7g (0.1mol) of the product c into 304.2g of absolute ethyl alcohol, heating the mixture in an oil bath to 60 ℃ for dissolution, then adding 152.1g of deionized water, then slowly adding 4.8g (0.12mol) of sodium hydroxide into a reaction system, continuing to react for 1hour at 60 ℃, gradually changing the reaction system from colorless to orange yellow, and after the system becomes light yellow and transparent; adding 1.0g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 12.3g (0.13mol) of 3-chloro-1-propanol into the reaction system, and after dropwise adding, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, adjusting the pH value of the reaction solution to 2 by using 8% dilute hydrochloric acid, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, filtering, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery intermediate B, weighing, and obtaining the intermediate B with the mass of about 46.2g and the yield of about 82%;
step e: adding 35.1g (0.0856mol) of the intermediate A and 46.0g (0.0815mol) of the intermediate B into 324.1g of tetrahydrofuran solvent, protecting with nitrogen, adding 19.6g of dicyclohexylcarbodiimide and 0.33g of 4-dimethylaminopyridine into a reaction system, stirring, and reacting at normal temperature for 12 hours; after the reaction is finished, insoluble substances are removed by filtration, filtrate is subjected to rotary evaporation to remove tetrahydrofuran to obtain a pre-target product, then the pre-target product is recrystallized for 3 times by using ethanol, and the obtained product is dried in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery final product, the weight of the final product is about 62.3g, and the yield of the final product is about 80%.
Example four
(C27H45O)(C7F2H2O2)(CH2)9(C13H8O3)(CH2)3(COOCH＝CH2) The structure and synthesis of (1):
step a: adding 42.85g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid into 215g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 107.5g of deionized water, then slowly adding 20g (0.5mol) of sodium hydroxide into the reaction system, continuing to react for 1hour at 60 ℃, and gradually changing the reaction system from colorless to light yellow; adding 0.857g of sodium iodide into a reaction system, slowly dripping 24.6g (0.26mol) of 3-chloro-1-propanol into the reaction system, and after finishing dripping, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% dilute hydrochloric acid, adjusting the pH value of the reaction solution to be 2, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery product a, wherein the weight of the product a is about 44.1g after weighing, and the yield is about 81%;
step b: weighing about 27.2g (0.1mol) of the product a, adding the product a into 163.2g of 1, 4-dioxane solvent, stirring, adding 15.2g (0.15mol) of triethylamine, and cooling in an ice water bath (0 ℃); slowly dripping 8.15g (0.09mol) of acryloyl chloride into the reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, pouring the reaction solution into 816g of ionized water at the temperature of 2 ℃, immediately separating out a large amount of white precipitate, filtering, recrystallizing the precipitate for 2 times by using absolute ethyl alcohol, filtering, and drying in a vacuum drying oven at the temperature of 50 ℃ for 24hours to obtain an intermediate A in a white powder shape, wherein the weight of the intermediate A is about 29.4g, and the yield is about 90%;
step c: 77.3g (0.2mol) of cholesterol were added to 618.4g of xylene, mechanically stirred, then 41.8g (0.24mol) of 3, 5-difluoro-4-hydroxybenzoic acid was added to the reaction system, after stirring evenly, adding 1.546g of p-toluenesulfonic acid monohydrate into the reaction system, heating to 140 ℃, carrying out reflux reaction for 24h, after the reaction is finished, cooling to room temperature, pouring out xylene as an upper solvent, pouring 1236.8g of ethyl acetate into the lower caked precipitate, performing ultrasonic dissolution, then washing the organic layer with 5% sodium bicarbonate water solution with the same mass, carrying out liquid separation treatment, carrying out rotary evaporation on the obtained organic layer to remove ethyl acetate, pouring the residual product into anhydrous ethanol with the same mass as xylene for recrystallization for 3 times, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a yellowish-brown powdery product b, weighing the product b to obtain 89g, and obtaining the yield of 82%;
step d: adding 54.3g (0.1mol) of the product c into 325g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 162.5g of deionized water, then slowly adding 4.8g (0.12mol) of sodium hydroxide into the reaction system, continuing to react for 1hour at 60 ℃, gradually changing the reaction system from colorless to orange yellow, and after the system becomes light yellow and transparent; adding 1.086g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 23.2g (0.13mol) of 9-chloro-1-nonanol into the reaction system, and after dropwise adding, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, adjusting the pH value of the reaction solution to 2 by using 8% dilute hydrochloric acid, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, filtering, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery intermediate B, weighing the intermediate B to obtain 56g, and obtaining the yield of 82%;
step e: adding 28.0g (0.0858mol) of the intermediate A and 56.0g (0.0818mol) of the intermediate B into 308.7g of tetrahydrofuran solvent, protecting with nitrogen, adding 19.6g of dicyclohexylcarbodiimide and 0.33g of 4-dimethylaminopyridine into a reaction system, stirring, and reacting for 12 hours at normal temperature; after the reaction is finished, insoluble substances are removed by filtration, filtrate is subjected to rotary evaporation to remove tetrahydrofuran to obtain a pre-target product, then the pre-target product is recrystallized for 3 times by using ethanol, and the obtained product is dried in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery final product, wherein the weight of the final product is about 47g, and the yield is about 81%.
Comparative example No. four
(C27H45O)(C7H4O2)(CH2)9(C13H8O3)(CH2)3(COOCH＝CH2) The structure and synthesis of (1):
step a: adding 42.85g (0.2mol) of 4' -hydroxybiphenyl-4-carboxylic acid into 215g of absolute ethyl alcohol, heating the mixture to 60 ℃ in an oil bath, then adding 107.5g of deionized water, then slowly adding 20g (0.5mol) of sodium hydroxide into the reaction system, continuing to react for 1hour at 60 ℃, and gradually changing the reaction system from colorless to light yellow; adding 0.857g of sodium iodide into a reaction system, slowly dripping 24.6g (0.26mol) of 3-chloro-1-propanol into the reaction system, and after finishing dripping, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% dilute hydrochloric acid, adjusting the pH value of the reaction solution to be 2, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, and drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery product a, wherein the weight of the product a is about 44.1g after weighing, and the yield is about 81%;
step b: weighing about 27.2g (0.1mol) of the product a, adding the product a into 163.2g of 1, 4-dioxane solvent, stirring, adding 15.2g (0.15mol) of triethylamine, and cooling in an ice water bath (0 ℃); slowly dripping 8.15g (0.09mol) of acryloyl chloride into the reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, pouring the reaction solution into 816g of ionized water at the temperature of 2 ℃, immediately separating out a large amount of white precipitate, filtering, recrystallizing the precipitate for 2 times by using absolute ethyl alcohol, filtering, and drying in a vacuum drying oven at the temperature of 50 ℃ for 24hours to obtain an intermediate A in a white powder shape, wherein the weight of the intermediate A is about 29.4g, and the yield is about 90%;
step c: 77.3g (0.2mol) of cholesterol were added to 618.4g of xylene, mechanically stirred, then 33.1g (0.24mol) of 4-hydroxybenzoic acid was added to the reaction system, after stirring evenly, adding 1.546g of p-toluenesulfonic acid monohydrate into the reaction system, heating to 140 ℃, carrying out reflux reaction for 24h, after the reaction is finished, cooling to room temperature, pouring out xylene waste serving as an upper solvent, pouring 1236.8g of ethyl acetate into the lower-layer caked precipitate, performing ultrasonic dissolution, then washing the organic layer with 5% sodium bicarbonate aqueous solution with the same mass, separating the liquid, pouring the lower water layer, performing rotary evaporation on the obtained organic layer to remove ethyl acetate, pouring the residual product into anhydrous ethanol with the same mass as xylene for recrystallization for 3 times, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a product b in a yellowish powder shape, weighing the product b to obtain 89g of the mass, and obtaining the yield of 82 percent;
step d: adding 50.7g (0.1mol) of the product c into 304.2g of absolute ethyl alcohol, heating the mixture in an oil bath to 60 ℃ for dissolution, then adding 152.1g of deionized water, then slowly adding 4.8g (0.12mol) of sodium hydroxide into a reaction system, continuing to react for 1hour at 60 ℃, gradually changing the reaction system from colorless to orange yellow, and after the system becomes light yellow and transparent; adding 1.0g of sodium iodide serving as a phase transfer catalyst into a reaction system, slowly dropwise adding 23.2g (0.13mol) of 9-chloro-1-nonanol into the reaction system, and after dropwise adding, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, adjusting the pH value of the reaction solution to 2 by using 8% dilute hydrochloric acid, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3 times by using absolute ethyl alcohol, filtering, drying in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery intermediate B, weighing the intermediate B to obtain 53.2g, wherein the yield is about 80%;
step e: adding 28.0g (0.0858mol) of the intermediate A and 53.0g (0.0818mol) of the intermediate B into 308.7g of tetrahydrofuran solvent, protecting with nitrogen, adding 19.6g of dicyclohexylcarbodiimide and 0.33g of 4-dimethylaminopyridine into a reaction system, stirring, and reacting for 12 hours at normal temperature; after the reaction is finished, insoluble substances are removed by filtration, filtrate is subjected to rotary evaporation to remove tetrahydrofuran to obtain a pre-target product, then the pre-target product is recrystallized for 3 times by using ethanol, and the obtained product is dried in a vacuum drying oven at 50 ℃ for 24hours to obtain a white powdery final product, wherein the weight of the final product is about 47g, and the yield is about 81%.
Tables one and two are summarized by combining examples one to four and comparative examples one to four.
TABLE I HTP value comparison of molecules before and after F modification
As can be seen from the table I, compared HTP values measured before and after F is contained in the cholesteryl chirality molecules with different carbon chains, the HTP value of the cholesteryl chirality molecules is greatly improved by introducing F.
Comparison of the addition amounts of the chiral agents before and after modification of TABLE II F
HTP values corresponding to target molecules containing F and not containing F and chiral addition amount required for forming specific screw pitch in cholesteric liquid crystal (chiral molecules are matched with RM242 liquid crystal), and it can be seen that for the cholesteric liquid crystal with specific screw pitch, due to the introduction of F, the use amount of chiral additives is greatly reduced.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A fluorine-containing liquid crystal molecule with cholesterol as a chiral center is characterized in that the structural formula of the liquid crystal molecule is expressed as follows:
wherein m is more than or equal to 3 and less than or equal to 9; the range of n is more than or equal to 3 and less than or equal to 9.
2. The method for preparing fluorine-containing liquid crystal molecules with cholesterol as a chiral center according to claim 1, which comprises the following steps:
(1) and synthesis of an intermediate A:
(1.1) 4' -hydroxybiphenyl-4-carboxylic acid and m (m is more than or equal to 3 and less than or equal to 9) chlorohydrin are used as reaction raw materials to react, and a reaction system is NaOH/NaI and EtOH/H2O, dilute HCl to obtain a product a, wherein the structural formula of the product a is expressed as follows:
(1.2) reacting the product of the product a and acryloyl chloride as raw materials to obtain an intermediate A, wherein the system is a dioxane/triethylamine system, and the structural formula of the intermediate A is expressed as follows:
(2) and synthesis of an intermediate B:
(2.1) carrying out esterification reaction by using chiral cholesterol and F-containing p-hydroxybenzoic acid as raw materials, wherein the reaction system is xylene/p-toluenesulfonic acid to obtain a product b, and the structural formula of the product b is expressed as follows:
(2.2) reacting the product B with N (N is more than or equal to 3 and less than or equal to 9) chlorohydrin serving as raw materials to obtain an intermediate B, wherein the reaction system is NaOH/N product aI, and EtOH/H2O, and the structural formula of intermediate B is expressed as follows:
(3) performing esterification reaction on the intermediate A and the intermediate B to finally obtain a target product, wherein the reaction system is DCC/DMAP, N2A tetrahydrofuran system having the formula:
3. the method for preparing fluorine-containing liquid crystal molecules taking cholesterol as a chiral center according to claim 2, wherein the product a is prepared by the following steps: adding a certain mass of 4 '-hydroxybiphenyl-4-carboxylic acid into 5-6 times of absolute ethyl alcohol, heating in an oil bath to 60 ℃ for dissolution, then adding deionized water with the mass of 1/2 times of the absolute ethyl alcohol, then slowly adding NaOH with the molar number of 2.5-3.0 times of that of the 4' -hydroxybiphenyl-4-carboxylic acid into the whole system, and continuing to react for 1h at 60 ℃ after the system is changed from colorless to light yellow and transparent; adding sodium iodide accounting for 2 percent of the mass of the 4 '-hydroxybiphenyl-4-carboxylic acid as a phase transfer catalyst, slowly dripping m (m is more than or equal to 3 and less than or equal to 9) of m-membered chlorohydrin with the mole number of 1.3 times of that of the 4' -hydroxybiphenyl-4-carboxylic acid into the whole system, and carrying out reflux reaction at the temperature of 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8-10% dilute hydrochloric acid, adjusting the pH value to 2-3, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3-4 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 50 ℃ for 24hours to obtain a product a, wherein the product a is white powder.
4. The method for preparing fluorine-containing liquid crystal molecules with cholesterol as a chiral center according to claim 3, wherein the intermediate A is prepared by the following steps: adding a certain mass of the product a into a 1, 4-dioxane solvent with the mass being 6 times that of the product a, adding triethylamine with the mole number being 1.5 times that of the product a while stirring, and cooling in an ice water bath (0-2 ℃); slowly dripping acryloyl chloride of which the mole number is 0.9 time that of the product a into a reaction system, removing the ice water bath after finishing dripping, and continuously reacting for 12 hours at normal temperature; after the reaction is finished, preparing deionized water with the mass of 2-3 ℃ which is 5 times that of the 1, 4-dioxane solvent, pouring the reaction liquid into the deionized water, separating out a large amount of white precipitate, filtering, recrystallizing the precipitate for 2-3 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 50 ℃ for 24hours to obtain an intermediate A, wherein the intermediate A is white powder.
5. The method for preparing fluorine-containing liquid crystal molecules taking cholesterol as a chiral center according to claim 2, wherein the product b is prepared by the following steps: : adding a certain mass of cholesterol into xylene with the mass of 8 times, mechanically stirring, adding 3, 5-difluoro-4-hydroxybenzoic acid with the mole number of 1.2 times that of the cholesterol, continuously stirring fully, adding p-toluenesulfonic acid monohydrate with the mass of 2% of the cholesterol as a catalyst, heating to 140 ℃, carrying out reflux reaction for 24hours, cooling to room temperature, pouring out xylene waste on the upper layer, adding ethyl acetate with the mass of 2 times that of the xylene to carry out ultrasonic dissolution on massive precipitates on the lower layer, carrying out washing liquid treatment by using a sodium bicarbonate aqueous solution with the mass of 5% of the same mass of the ethyl acetate after complete dissolution, carrying out liquid separation treatment, pouring out a water layer on the lower layer, carrying out rotary evaporation on an organic layer to remove ethyl acetate, then pouring absolute ethyl alcohol with the mass of the same xylene to carry out recrystallization, carrying out co-recrystallization for 2-3 times, filtering, carrying out vacuum drying at 50 ℃ for 24hours to obtain a product b, and product b is a yellowish brown powder.
6. The method for preparing fluorine-containing liquid crystal molecules with cholesterol as a chiral center according to claim 5, wherein the intermediate B is prepared by the following steps: adding a certain mass of the product b into absolute ethyl alcohol with the mass 5-6 times that of the product b, heating the mixture in an oil bath at 60 ℃ for dissolution, then adding deionized water with the mass 1/2 of the absolute ethyl alcohol, then slowly adding NaOH with the molar number 1.2 times that of the product b into the whole system, and continuing to react for 1h at 60 ℃ after the system becomes light yellow and transparent; adding sodium iodide accounting for 2% of the mass of the product b as a phase transfer catalyst into a reaction system, slowly dripping n (n is more than or equal to 3 and less than or equal to 9) of n-membered chlorohydrin with the mole number of 1.3 times that of the product b into the whole system, and after finishing dripping, carrying out reflux reaction at 80 ℃ for 24 hours; after the reaction is finished, acidifying the reaction system by using 8% -10% dilute hydrochloric acid, adjusting the pH value to 2-3, fully stirring, filtering to obtain a precipitate, washing the precipitate by using a large amount of deionized water, recrystallizing the precipitate for 3-4 times by using absolute ethyl alcohol, filtering, and drying in vacuum at 50 ℃ for 24hours to obtain an intermediate B, wherein the intermediate B is white powder.
7. The method for producing a fluorine-containing liquid crystal molecule having cholesterol as a chiral center according to claim 4 and/or 6, wherein the intermediate A and the intermediate B are added to a tetrahydrofuran solvent having a mass 4 times that of the mixture of the intermediate A and the intermediate B at a molar ratio n (B) n (d) of 1.05: 1; under the protection of nitrogen, adding 1.9 times of dicyclohexylcarbodiimide and 0.03 times of 4-dimethylaminopyridine into the reaction system, stirring, and reacting at normal temperature for 12 hours; and after the reaction is finished, filtering to remove the generated white precipitate, performing rotary evaporation on the filtrate to remove tetrahydrofuran, then performing 3-4 times of recrystallization on the product by using absolute ethyl alcohol, filtering, and performing vacuum drying at 50 ℃ for 24hours to obtain the final product, wherein the final product is white powder.
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