CN111377830A - Synthetic method of compound with biphenyl dimer structure - Google Patents
Synthetic method of compound with biphenyl dimer structure Download PDFInfo
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Abstract
The invention provides a synthetic method of a compound with a biphenyl dimer structure shown in a formula A. The synthesis method takes 1, 5-dibromo-pentane and 4-bromobenzaldehyde as raw materials, and prepares the compound shown in the formula A through Grignard reaction, coupling and other steps. The method has the advantages of low raw material price, high yield, convenient purification and suitability for industrial production.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a synthetic method of a compound with a biphenyl dimer structure.
Background
It is well known that the flexo electro-optic effect can be used as a mode of a liquid crystal display. The most common examples of such effects are the ULH and USH effects. The liquid crystal device adopting the ULH mode has the response speed of 100 microseconds, and compared with the ULH mode, the USH mode can achieve a better dark state and can obtain a wide visual angle range. The conventional liquid crystal display mode requires a liquid crystal material having a large value of dielectric anisotropy to reduce the driving voltage of the display. However, different from ULH/USH modes, in order to prevent the helical structure of the liquid crystal from being separated under an electric field, the liquid crystal material is often required to have a dielectric anisotropy value as small as possible: meanwhile, in order to reduce the driving voltage, the liquid crystal material is required to have a large flexible electrical coefficient.
The dimer liquid crystal compound has larger flexoelectric coefficient and lower dielectric anisotropy, and is suitable for the application of a newly developed ULH (uniform horizontal helix, Unifoam LyingHelix)/USH (uniform vertical helix Unifoam StandingHelix) mode.
The invention application with the publication number of CN106608842A discloses a synthetic method of a compound with a biphenyl dimer structure, but the method has the advantages of low yield, high raw material cost and difficult purification, and in view of the fact that the dimer has high practical value and wide application prospect, a synthetic method which has low raw material price, high yield, convenient purification and suitability for industrialization needs to be developed.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a synthetic method of a compound with a biphenyl dimer structure, which has the advantages of low raw material price, high yield and convenient purification and is suitable for industrial production.
The technical scheme of the invention is as follows:
the invention provides a synthetic method of a biphenyl dimer material shown as a formula A, which comprises the following steps:
1) reacting a compound of formula 2
Dissolving the compound with an organic solvent to obtain a mixed solution of the compound shown in the formula 2 for later use;
2) mixing Mg and I2Dissolving the mixture with an organic solvent, dropwise adding 1/4-1/2 volume of the mixed solution of the compound of the formula 2 prepared in the step 1) under the protection of inert gas, heating to reflux after initiating the reaction, dropwise adding the rest of the mixed solution of the compound of the formula 2, performing reflux reaction for 5-8 hours, and dropwise adding the compound of the formula 1 at 35-45 DEG C
Mixing the mixed solution with an organic solvent to form a mixed solution, and reacting for 1-5 hours;
3) reacting a compound of formula 4
Dissolving by using an organic solvent, dropwise adding strong acid, adding alkylsilane at the temperature of 10-50 ℃, reacting for 5-15 hours, then heating to 65-95 ℃, and reacting for 0.5-20 hours to obtain a compound shown in the formula 5;
4) reacting a compound of formula 6
Dissolving the compound shown in the formula 5 with an organic solvent, water and an inorganic base, adding a catalyst under the protection of inert gas, heating to 72-80 ℃, and carrying out reflux reaction for 1-6 hours to obtain the compound shown in the formula A.
The organic solvent is selected from one or more of tetrahydrofuran, diethyl ether and methyl tert-butyl ether, and tetrahydrofuran is further preferred.
The molar ratio of the compound of the formula 1, the compound of the formula 2 and the compound of the formula 3 in the step 2) is (1-2): (1-3): (2-6), and more preferably 1:3: 6.
The organic solvent in step 3) is selected from one or more of tetrahydrofuran, diethyl ether, dichloromethane, chloroform and dichloroethane, and dichloromethane is further preferred.
The alkylsilane in the step 3) is selected from one or more of trimethylsilane, triethylsilane, tripropylsilane and diethylsilane, and is further preferably triethylsilane.
The strong acid in the step 3) is selected from one or more of sulfuric acid, hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, boron trifluoride diethyl etherate and boron tribromide, and is further preferably trifluoroacetic acid or/and boron trifluoride diethyl etherate.
The organic solvent in step 4) is selected from one or more of toluene, ethanol, tetrahydrofuran and isopropanol, and is further preferably toluene and/or ethanol.
The inorganic base in the step 4) is one or more selected from sodium bicarbonate, sodium carbonate, potassium carbonate, disodium hydrogen phosphate, sodium hydroxide and potassium hydroxide, and is preferably sodium bicarbonate.
The catalyst in the step 4) is one or more selected from dichloro di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (II) (Pd-132), bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, and is further preferably dichloro di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (II) (Pd-132).
Has the advantages that: the synthesis method provided by the invention has the advantages of reasonable whole process design, strong operability, cheap and easily-obtained raw materials, convenience in purification and higher yield, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a mass spectrum of Compound 4.
FIG. 2 is a mass spectrum of Compound 5.
FIG. 3 is the nuclear magnetic map of Compound A.
Detailed Description
Example 1
1) Adding 192.5g of Mg and 2g of iodine into a 5L reaction bottle, fully dissolving with 2.5L of tetrahydrofuran, dropwise adding 1/3 of a mixed solution formed by mixing 50mL of 1, 5-dibromo-pentane and 250mL of tetrahydrofuran under the protection of nitrogen, heating to reflux after initiating a reaction, dropwise adding the rest of the mixed solution, carrying out reflux reaction for 6 hours, controlling the temperature to be 35 ℃, dropwise adding a mixed solution obtained by dissolving 250g of p-bromo-benzaldehyde with 250mL of tetrahydrofuran, and reacting for 3 hours;
after the reaction is finished, 700mL of 10% dilute hydrochloric acid is dropwise added into the reaction liquid, the pH of the reaction liquid is adjusted to be below 2, the temperature of the reaction liquid is controlled to be below 30 ℃, 2L of water is added for dilution, ethyl acetate is used for extraction, organic layers are combined, the organic layers are washed by saturated sodium bicarbonate water solution until the pH is 6-7, then water is used for washing until the pH is neutral, drying and concentration are carried out, a gray solid product is obtained, 1L of petroleum ether is used for pulping, and then a mixed solvent consisting of 50mL of ethanol and 250mL of petroleum ether is used for pulping for three times at room temperature, so that 75g of a white solid powder product is obtained, and the yield is: 25.38 percent;
2) 583g of trifluoroacetic acid, 90g of 1, 7-bis (4-bromophenyl) heptane-1, 7-diol and triethylsilane are added into a 2.5L reaction flask, the mixture is reacted for 11 hours at room temperature under the protection of nitrogen, the temperature is raised to 80 ℃, the reaction is carried out for 12 hours, after the reaction is finished, the trifluoroacetic acid is distilled out, 500mL of water is added, 300mL of petroleum ether and 200mL of petroleum ether are used for extraction twice, organic layers are combined, the mixture is washed to be neutral by water, and after concentration, the distillation is carried out under reduced pressure, 77g of brown transparent solution is obtained after the bottom distillation is kept, the yield is: 91.8 percent;
3) 0.4L of toluene, 0.2L of ethanol and 0.2L of water are added into a 2.5L reaction bottle, 77g of 1, 7-bis (4-bromophenyl) heptane, 55.2g of (4-cyanophenyl) boric acid and 63g of sodium bicarbonate are added under the condition of continuous stirring, Pd-132 is added under the condition of nitrogen protection, the temperature is increased to reflux, the reflux reaction is carried out for 4 hours, the mixture is cooled, the mixture is kept stand and separated, an aqueous layer is extracted by 250mL of × 3 toluene, an organic layer is concentrated, 1.5L of toluene is used as a mobile phase for column chromatography to obtain 114g of light red solid, and the obtained crude product is recrystallized by using dichloromethane and ethanol according to the volume ratio of 2: 15 to obtain 75g of white solid product, wherein the yield is 88%.
Example 2
1) Adding 192.5g of Mg and 2g of iodine into a 5L reaction bottle, uniformly mixing with 2.5L of tetrahydrofuran, dropwise adding 1/2 of a mixed solution formed by mixing 50mL of 1, 5-dibromo-pentane and 250mL of tetrahydrofuran under the protection of nitrogen, heating to reflux after initiating a reaction, dropwise adding the rest of the mixed solution, carrying out reflux reaction for 6 hours, controlling the temperature to be 45 ℃, dropwise adding a mixed solution obtained by dissolving 250g of a compound (4-bromobenzaldehyde) of the formula 1 with 250mL of tetrahydrofuran, and reacting for 4.5 hours;
after the reaction is finished, 700mL of 10% dilute hydrochloric acid is dropwise added into the reaction liquid, the pH of the reaction liquid is adjusted to be below 2, the temperature of the reaction liquid is controlled to be below 30 ℃, 2L of water is added for dilution, ethyl acetate is used for extraction, organic layers are combined, the organic layers are washed by saturated sodium bicarbonate water solution until the pH is 6-7, then water is used for washing until the pH is neutral, drying and concentration are carried out to obtain a gray solid product, 1L of petroleum ether is used for pulping, and then a mixed solvent consisting of 50mL of ethanol and 250mL of petroleum ether is used for pulping for three times at room temperature to obtain 72.3g of a white solid powder product, wherein the yield is as follows: 24.47%;
2) 583g of trifluoromethanesulfonic acid, 62g of 1, 7-bis (4-bromophenyl) heptane-1, 7-diol and 109.3g of triethylsilane are added into a reaction bottle, the mixture is reacted for 11 hours at room temperature under the protection of nitrogen, the temperature is raised to 85 ℃, the reaction is carried out for 10 hours, the trifluoromethanesulfonic acid is distilled out, 500mL of water is added, 300mL of petroleum ether and 200mL of petroleum ether are used for extraction twice, organic layers are combined, the mixture is washed to be neutral by water, and after concentration, reduced pressure distillation is carried out, 53g of brown transparent solution is obtained after the bottom distillation is kept, and the yield is as follows: 91.7 percent;
3) adding 0.4L of toluene, 0.2L of ethanol and 0.2L of water into a 2.5L reaction bottle, adding 50g of 1, 7-bis (4-bromophenyl) heptane, 55.2g of (4-cyanophenyl) boric acid and 40g of sodium bicarbonate under the condition of continuous stirring, adding Pd-132 under the condition of nitrogen protection, heating to reflux, carrying out reflux reaction for 4 hours, cooling, standing for liquid separation, extracting an aqueous layer with 250mL of × 3 toluene, concentrating an organic layer, carrying out column chromatography by using 1.5L of toluene as a mobile phase to obtain 77.6g of light red solid, and recrystallizing the obtained crude product by using dichloromethane and ethanol at a volume ratio of 2: 15 to obtain 51g of white solid product with the yield of 87.2%.
Example 3
1) Adding 144g of Mg and 2g of iodine into a 2.5L reaction bottle, uniformly mixing with 1L of diethyl ether, dropwise adding 1/3 of a mixed solution formed by mixing 12.3mL of 1, 5-dibromo-pentane and 65mL of tetrahydrofuran under the protection of nitrogen, heating to reflux after initiating a reaction, dropwise adding the rest of the mixed solution, carrying out reflux reaction for 6 hours, controlling the temperature to be 25 ℃, dropwise adding a mixed solution obtained by dissolving 185g of (4-bromobenzaldehyde) with 185mL of tetrahydrofuran, and reacting for 3 hours;
after the reaction is finished, 700mL of 10% dilute hydrochloric acid is dropwise added into the reaction liquid, the pH of the reaction liquid is adjusted to be below 2, the temperature of the reaction liquid is controlled to be 30 ℃, 1L of water is added for dilution, ethyl acetate is used for extraction, organic layers are combined, the organic layers are washed by saturated sodium bicarbonate aqueous solution until the pH is 6, then the organic layers are washed by water until the pH is neutral, drying and concentration are carried out, a gray solid product is obtained, 1L of petroleum ether is used for pulping, and then mixed solvent consisting of 50mL of ethanol and 250mL of petroleum ether is used for pulping for three times at room temperature, 56g of white solid powder product is obtained, and the yield is: 25.34 percent;
2) adding 432g of trifluoroacetic acid, 73g of 1, 7-bis (4-bromophenyl) heptane-1, 7-diol and 87.2g of diethylsilane into a reaction bottle, reacting at room temperature for 11 hours under the protection of nitrogen, heating to 80 ℃, reacting for 12 hours, distilling out the trifluoroacetic acid, adding 500mL of water, extracting twice with 300mL of 200mL of petroleum ether, combining organic layers, washing with water to be neutral, concentrating, distilling under reduced pressure, and keeping a bottom to obtain 62g of brown transparent solution, wherein the yield is as follows: 91.2 percent;
3) 0.2L of isopropanol, 0.1L of methanol and 500mL of water are added into a 2.5L reaction bottle, 32g of 1, 7-bis (4-bromophenyl) heptane, 28.4g of (4-cyanophenyl) boric acid and 29.6g of sodium bicarbonate are added under the condition of continuous stirring, tetrakis (triphenylphosphine) palladium is added under the condition of nitrogen protection, the mixture is heated to reflux and refluxed for 4 hours, the mixture is cooled, kept stand and separated, an aqueous layer is extracted by 250mL of × 3 toluene, an organic layer is concentrated, 1.5L of toluene is used as a mobile phase for column chromatography to obtain 47g of light red solid, and then dichloromethane and ethanol are used for recrystallizing the obtained crude product in a volume ratio of 2: 15 to obtain 31g of white solid product, wherein the yield is 87.6%.
Claims (9)
1. A method for synthesizing a compound with a biphenyl dimer structure is characterized by comprising the following steps:
1) reacting a compound of formula 2
Dissolving the compound with an organic solvent to obtain a mixed solution of the compound shown in the formula 2 for later use;
2) mixing Mg and I2Dissolving the mixture with an organic solvent, dropwise adding 1/4-1/2 volume of the mixed solution of the compound of the formula 2 prepared in the step 1) under the protection of inert gas, heating to reflux after initiating the reaction, dropwise adding the rest of the mixed solution of the compound of the formula 2, performing reflux reaction for 5-8 hours, and dropwise adding the compound of the formula 1 at 35-45 DEG C
Mixing the mixed solution with an organic solvent to form a mixed solution, and reacting for 1-5 hours;
3) reacting a compound of formula 4
Dissolving by using an organic solvent, dropwise adding strong acid, adding alkylsilane at the temperature of 10-50 ℃, reacting for 5-15 hours, then heating to 65-95 ℃, and reacting for 0.5-20 hours to obtain a compound shown in the formula 5;
4) reacting a compound of formula 6
Dissolving the compound shown in the formula 5 with an organic solvent, water and an inorganic base, adding a catalyst under the protection of inert gas, heating to 72-80 ℃, and carrying out reflux reaction for 1-6 hours to obtain the compound shown in the formula A.
2. The method for synthesizing a compound having a biphenyl dimer structure according to claim 1, wherein the organic solvent of step 2) is one or more selected from tetrahydrofuran, diethyl ether, and methyl tert-butyl ether.
3. The method for synthesizing a compound having a biphenyl dimer structure according to claim 1, wherein the molar ratio of the compound of formula 1, the compound of formula 2, and the compound of formula 3 in step 2) is (1-2): (1-3): (2-6).
4. The method for synthesizing a compound having a biphenyl dimer structure according to claim 1, wherein the organic solvent of step 3) is one or more selected from tetrahydrofuran, diethyl ether, dichloromethane, chloroform, and dichloroethane.
5. The method for synthesizing a compound having a biphenyl dimer structure according to claim 1, wherein the alkylsilane of step 3) is one or more selected from trimethylsilane, triethylsilane, tripropylsilane, and diethylsilane.
6. The method for synthesizing a compound having a biphenyl dimer structure according to claim 1, wherein the strong acid of step 3) is one or more selected from sulfuric acid, hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, boron trifluoride diethyl etherate, and boron tribromide diethyl ether.
7. The method for synthesizing a compound having a biphenyl dimer structure according to claim 1, wherein the organic solvent of step 4) is one or more selected from toluene, ethanol, tetrahydrofuran, and isopropanol.
8. The method for synthesizing a compound having a biphenyl dimer structure according to claim 1, wherein the inorganic base in step 4) is one or more selected from sodium bicarbonate, sodium carbonate, potassium carbonate, disodium hydrogen phosphate, sodium hydroxide, and potassium hydroxide.
9. The method for synthesizing a compound having a biphenyl dimer structure according to claim 1, wherein the catalyst in step 4) is one or more selected from dichloro di-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (II), bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, and [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608842A (en) * | 2015-10-23 | 2017-05-03 | 江苏和成显示科技股份有限公司 | Method for preparing dimer containing benzonitrile terminal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106608842A (en) * | 2015-10-23 | 2017-05-03 | 江苏和成显示科技股份有限公司 | Method for preparing dimer containing benzonitrile terminal |
Non-Patent Citations (3)
| Title |
|---|
| ANAMARIJA KNEŽEVIĆ 等: "Fine-tuning the effect of π-π interactions on the stability of the NTB phase", 《SOFT MATTER》 * |
| CHEN, DONG 等: "Chiral heliconical ground state of nanoscale pitch in a nematic liquid crystal of achiral molecular dimers", 《PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA》 * |
| MARTHA A 等: "Synthesis of ocimin, A 1,5-diene, by a bis-grignard reaction", 《SYNTHETIC COMMUNICATIONS》 * |
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