CN108329189B - Method for synthesizing 4,4' -dibromo-p-terphenyl - Google Patents
Method for synthesizing 4,4' -dibromo-p-terphenyl Download PDFInfo
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- CN108329189B CN108329189B CN201810187746.6A CN201810187746A CN108329189B CN 108329189 B CN108329189 B CN 108329189B CN 201810187746 A CN201810187746 A CN 201810187746A CN 108329189 B CN108329189 B CN 108329189B
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- RYHHUPOBLAATEI-UHFFFAOYSA-N 1-bromo-4-(4-bromo-4-phenylcyclohexa-1,5-dien-1-yl)benzene Chemical group C1=CC(Br)=CC=C1C1=CCC(Br)(C=2C=CC=CC=2)C=C1 RYHHUPOBLAATEI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 32
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012043 crude product Substances 0.000 claims abstract description 30
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 68
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000012065 filter cake Substances 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 16
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 15
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims 2
- 239000011541 reaction mixture Substances 0.000 abstract description 14
- 239000000047 product Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 4
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229930184652 p-Terphenyl Natural products 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- QARVLSVVCXYDNA-IDEBNGHGSA-N bromobenzene Chemical group Br[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 QARVLSVVCXYDNA-IDEBNGHGSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- -1 p-terphenyl compound Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application relates to a method for synthesizing 4,4' -dibromo-p-terphenyl, which comprises the following steps: reacting terphenyl, liquid bromine and at least one organic solvent at a temperature of 100 ℃ and 110 ℃ for 24-48 hours in the absence of a catalyst to obtain a first reaction mixture, wherein the molar ratio of the terphenyl to the liquid bromine is 1: (2.25-2.75); cooling to 25-30 ℃, washing by using methanol, and filtering to obtain a first crude product; purifying the first crude product to obtain the product 4,4' -dibromo-p-terphenyl. The method has the advantages that no catalyst is adopted, the yield is still up to 70%, the cost is reduced, the post-treatment process is simplified, and the technical support is provided for realizing the industrial production of the 4,4' -dibromo-p-terphenyl.
Description
Technical Field
The application relates to the technical field of organic synthesis. In particular, the application relates to a method for synthesizing 4,4' -dibromo-p-terphenyl.
Background
The p-terphenyl compound has the advantages of good light, heat, electricity and chemical stability, adjustable anisotropy, viscosity, double refraction and other physical constants and the like. Compared with other liquid crystal building units formed by connecting two or more benzene rings through ester, amide, azo and other groups, the liquid crystal building units have the advantages, and are widely applied to liquid crystal terminal display devices (LCDs) and polymer blue light materials for preparing Light Emitting Diodes (LEDs).
At present, 4,4' -dibromo-p-terphenyl is an important intermediate for synthesizing p-terphenyl compounds, biphenyl liquid crystals and some organic electroluminescent materials. In a known synthesis method, for example, U.S. Pat. No. US7544842B1 discloses that p-terphenyl as a raw material, liquid bromine as a brominating agent, trichlorobenzene as a solvent, and iodine as a catalyst are reacted at 100 ℃ to obtain 4,4' -dibromo-p-terphenyl with a yield of 69%. Japanese patent JP2008247788 discloses that terphenyl and liquid bromine are used as solvents, iodine is used as a catalyst, 4' -dibromo-p-terphenyl is obtained through reaction at 130 ℃, and the yield is 68%. These higher yield processes all require additional catalyst addition, increasing the cost of synthesis.
For this reason, there is a strong need in the art for a new method for synthesizing 4,4' -dibromo-p-terphenyl to solve at least the above problems.
Disclosure of Invention
The present application aims to provide a novel method for synthesizing 4,4' -dibromo-p-terphenyl, which solves the technical problems in the prior art.
The application provides a method for synthesizing 4,4' -dibromo-p-terphenyl, which comprises the following steps:
s1: reacting terphenyl, liquid bromine and at least one organic solvent at a temperature of 100 ℃ and 110 ℃ for 24-48 hours in the absence of a catalyst to obtain a first reaction mixture, wherein the molar ratio of the terphenyl to the liquid bromine is 1: (2.25-2.75); s2: cooling the first reaction mixture to 25-30 ℃, washing the first reaction mixture by using methanol, and filtering the first reaction mixture to obtain a first crude product; and S3: purifying the first crude product to obtain the product 4,4' -dibromo-p-terphenyl.
In some embodiments, the at least one organic solvent required for the synthesis reaction is selected from bromobenzene, trichlorobenzene, dichloroethane, acetonitrile, vinegar or combinations thereof.
In some embodiments, at least a portion of the vapor produced by the reaction of terphenyl and liquid bromine is refluxed to the reactor by cryocondensation, and at least a portion of the vapor is treated by a tail gas treatment unit.
In some embodiments, the cryocondensation temperature is from-10 to 0 ℃.
In some embodiments, step S2 includes cooling the first reaction mixture to 25-30 ℃, pouring the cooled first reaction mixture into methanol, stirring for 0.3-0.8 hours, filtering, washing the filter cake at least once with methanol, and filtering to obtain the first crude product.
In some embodiments, step S2 includes cooling the first reaction mixture to 25-30 ℃, washing with aqueous sodium sulfite or sodium hydroxide, washing with methanol, and filtering to obtain a first crude product.
In some embodiments, purifying the first crude product comprises oven drying the first crude product in an oven at 50-70 ℃ for 1-3 hours to obtain a second crude product.
In some embodiments, the second crude product is recrystallized at least twice using toluene or decalin to obtain a third crude product.
In some embodiments, the second crude product is poured into toluene or decalin and heated under reflux for 12 hours, the filter cake after heat filtration is then added into toluene or decalin and heated under reflux for 4 hours, and a third crude product is obtained after heat filtration.
In some embodiments, the third crude product is oven dried at 70-90 ℃ for 12-36 hours to provide 4,4' -dibromo-p-terphenyl.
Compared with the prior art, the preparation method has the beneficial effects that no catalyst is adopted, the yield is still up to 70%, the cost is reduced, the post-treatment process is simplified, and the technical support is provided for realizing the industrial production of the 4,4' -dibromo-p-terphenyl.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. these are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
Definition of terms
As used herein, the term "catalyst" refers to a substance that is capable of changing (increasing or decreasing) the chemical reaction rate of a reactant in a chemical reaction without changing the chemical equilibrium, and whose mass and chemical properties are not changed before or after the chemical reaction.
As used herein, the term "derivative" refers to a more complex product derived from a simple compound in which a hydrogen atom or group of atoms is replaced with another atom or group of atoms.
As used herein, the term "yield" refers to the amount of product obtained in a chemical reaction. The yield is usually expressed as a percentage of the theoretical yield of the reaction.
The method for synthesizing 4,4' -dibromo-p-terphenyl comprises the following steps: reacting terphenyl, liquid bromine and at least one organic solvent at a temperature of 100 ℃ and 110 ℃ for 24-48 hours in the absence of a catalyst to obtain a first reaction mixture, wherein the molar ratio of the terphenyl to the liquid bromine is 1: (2.25-2.75). In the embodiment of the application, the catalyst such as iodine, iron powder and the like is not used, the yield is still as high as 70 percent, and the synthesis cost is reduced. In a preferred embodiment, terphenyl and liquid bromine in a molar ratio of 1 (2.5-2.6) are mixed, and then an organic solvent is added to react at a temperature of 100 ℃ and 110 ℃ for 36-42 hours. Higher temperature can reduce reaction time, and the midbody conversion is more complete, but too high temperature can improve the control degree of difficulty of reaction, reduces the simple operation nature. In some embodiments, the terphenyl is dissolved by using an organic solvent, mechanical impurities in the terphenyl are removed by filtration, then liquid bromine is added, stirred and mixed, and the temperature is raised to 100 ℃ and 110 ℃ for reaction for 24-48 hours.
During the reaction, due to the higher temperature (100-2) Volatilized or distilled out with the generated hydrogen bromide vapor, reducing the content of the reactants. Thus, in some embodiments, at least some of the Br produced by heating terphenyl and liquid bromine using cryocondensation is2The steam is condensed back to the reactor, where the temperature of the cryocondensation can be-10 to 0 ℃. And additionally at least part of Br2And the hydrogen bromide vapor may be treated by a tail gas treatment device that, in a non-limiting embodiment, includes a buffer bottle for treating the water of the hydrogen bromide vapor and preventing back-suction of water.
In some embodiments, the at least one organic solvent required for the synthesis reaction is selected from bromobenzene, trichlorobenzene, dichloroethane, acetonitrile, vinegar or combinations thereof. In a preferred embodiment, the organic solvent is bromobenzene which does not contain chlorine with high toxicity, so that the over-standard chlorine content in the product caused by insufficient post-treatment is avoided.
The molar ratio is 1: (2.25-2.75) the terphenyl and liquid bromine react at 100 ℃ and 110 ℃ as follows:
the reaction is basically complete after 24-48 hours of reaction. And cooling the obtained reaction liquid of the terphenyl and the liquid bromine to 25-30 ℃, washing by using methanol, and filtering to obtain a first crude product. In some embodiments, after cooling the obtained reaction solution of terphenyl and liquid bromine to 25-30 ℃, pouring the reaction solution of terphenyl and liquid bromine into excessive methanol, wherein the volume of the methanol is 1.5-2 times of the volume of the reaction solution, stirring for 0.3-0.8 hours, filtering, washing the filter cake at least once with methanol, and filtering to obtain the first crude product. In some embodiments, the reaction mixture of terphenyl and liquid bromine is washed with aqueous sodium sulfite or aqueous sodium hydroxide to remove excess liquid bromine from the solution prior to pouring the reaction mixture into excess methanol. Since the aqueous sodium sulfite solution may contain chloride ions, it is not suitable to wash with the aqueous sodium sulfite solution when the chlorine content is particularly required.
The first crude product after methanol washing is subjected to a series of purification steps to obtain the product 4,4' -dibromo-p-terphenyl. In some embodiments, purifying the first crude product comprises: firstly, drying the first crude product in a forced air oven at 50-70 ℃ for 1-3 hours to obtain a second crude product. Secondly, recrystallizing the second crude product at least twice by using toluene to obtain a third crude product, wherein in an unlimited embodiment, the second crude product is poured into the toluene for heating reflux for 12 hours during primary recrystallization, and a filter cake after thermal filtration is rinsed once by using the toluene and then is dried by pumping; and during secondary recrystallization, adding the pumped filter cake into toluene, heating and refluxing for 4 hours, rinsing the filter cake once by using toluene after heat filtration, and pumping to obtain a third crude product. And finally, drying the third crude product in a blast oven at 70-90 ℃ for 12-36 hours to obtain the product 4,4' -dibromo-p-terphenyl, wherein the yield is about 70%, and the purity is more than 99%. In some embodiments, the use of decalin in place of toluene used in the recrystallization can reduce the intermediate impurity content of the crude product to below 0.1%. The purification method has the advantages of simple and easily obtained raw materials, simple and convenient operation steps and contribution to industrial production.
In some embodiments, impurities in the filtrate generated in the recrystallization purification process are mainly intermediates of the reaction, and liquid bromine can be added into the filtrate for reaction, so that the yield is improved.
Examples
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The reagents and raw materials used are commercially available unless otherwise specified. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples, the sources of the raw materials used are as follows:
terphenyl, purity 99%;
liquid bromine with the purity of 99 percent is purchased from Jiangsu Qiangsheng functional chemistry Limited company;
bromobenzene with purity of 99% is purchased from Shanghai Kai Kogyo Co., Ltd;
methanol with purity of 99 percent, Shanghai Jun Fine chemical Co., Ltd;
toluene with purity of 99 percent, Shanghai Jun Fine chemical Co., Ltd.
Example 1:
100g of terphenyl and 1L of bromobenzene are added into a 2L reaction bottle, 174g of liquid bromine is added under stirring, and the temperature is raised to 105 ℃ for reaction for 40 hours. At least part of Br generated by heating terphenyl and liquid bromine by means of low-temperature (-10-0 ℃) condensation2Condensing the steam and refluxing to the reaction flask, and at least partially adding Br2And hydrogen bromide vapor is absorbed using water.
After cooling to 25 ℃, the reaction mixture of terphenyl and liquid bromine was poured into 2L of methanol, stirred for 0.5 hour, filtered and the filter cake was washed at least once more with 800mL of methanol. After filtration, the filter cake was dried in a forced air oven at 60 ℃ for 2 hours. And adding the dried crude product into 200mL of methylbenzene, refluxing and pulping for 12 hours, rinsing the filter cake once by using 200mL of methylbenzene after hot filtration, and draining. The drained filter cake is added into 200mL of toluene for reflux and pulping for 4 hours, and after hot filtration, the filter cake is rinsed once with 200mL of toluene and then drained. The obtained filter cake is put into a blast oven and dried for 24 hours at the temperature of 80 ℃ to obtain 118g of off-white solid which is the product of 4,4' -dibromo-p-terphenyl, and the yield is 70 percent.
Example 2:
in a first example, 4,4' -dibromo-p-terphenyl was prepared by the following method:
100g of terphenyl and 1L of bromobenzene are added into a 2L reaction bottle, 174g of liquid bromine is added under stirring, and the temperature is raised to 100 ℃ for reaction for 40 hours. At least part of Br generated by heating terphenyl and liquid bromine by means of low-temperature (-10-0 ℃) condensation2Condensing the steam and refluxing to the reaction flask, and at least partially adding Br2And hydrogen bromide vapor is absorbed using water.
After cooling to 25 ℃, the reaction mixture of terphenyl and liquid bromine was poured into 2L of methanol, stirred for 0.5 hour, filtered and the filter cake was washed at least once more with 800mL of methanol. After filtration, the filter cake was dried in a forced air oven at 60 ℃ for 2 hours. And adding the dried crude product into 200mL of methylbenzene, refluxing and pulping for 12 hours, rinsing the filter cake once by using 200mL of methylbenzene after hot filtration, and draining. The drained filter cake is added into 200mL of toluene for reflux and pulping for 4 hours, and after hot filtration, the filter cake is rinsed once with 200mL of toluene and then drained. The obtained filter cake was put into a forced air oven and dried at 80 ℃ for 24 hours to obtain 117g of off-white solid which is the product of 4,4' -dibromo-p-terphenyl with the yield of 69.4%.
Example 3:
100g of terphenyl and 1L of bromobenzene are added into a 2L reaction bottle, 174g of liquid bromine is added under stirring, and the temperature is raised to 110 ℃ for reaction for 40 hours. At least part of Br generated by heating terphenyl and liquid bromine by means of low-temperature (-10-0 ℃) condensation2Condensing the steam and refluxing to the reaction flask, and at least partially adding Br2And hydrogen bromide vapor is absorbed using water.
After cooling to 25 ℃, the reaction mixture of terphenyl and liquid bromine was poured into 2L of methanol, stirred for 0.5 hour, filtered and the filter cake was washed at least once more with 800mL of methanol. After filtration, the filter cake was dried in a forced air oven at 60 ℃ for 2 hours. And adding the dried crude product into 200mL of methylbenzene, refluxing and pulping for 12 hours, rinsing the filter cake once by using 200mL of methylbenzene after hot filtration, and draining. The drained filter cake is added into 200mL of toluene for reflux and pulping for 4 hours, and after hot filtration, the filter cake is rinsed once with 200mL of toluene and then drained. The obtained filter cake is put into a blast oven and dried for 24 hours at the temperature of 80 ℃ to obtain 119g of off-white solid which is the product of 4,4' -dibromo-p-terphenyl, and the yield is 70.6%.
1 H NMR：
Proton NMR data were obtained using 400MHz Bruker DRX.
As shown in FIG. 1, by1H NMR analysis the product obtained in example 1,1H NMR(400MHz):δ(ppm)7.79(4H,s),7.69(8H,d)。
the embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (1)
1. A method for synthesizing 4,4 '-dibromo-p-terphenyl, characterized in that the 4,4' -dibromo-p-terphenyl is prepared by the following method:
s1: adding 100g of terphenyl and 1L of bromobenzene into a 2L reaction bottle, adding 174g of liquid bromine under stirring, heating to 110 ℃ for reaction for 40 hours, and heating at least part of Br generated by terphenyl and liquid bromine in a low-temperature condensation mode2Condensing the steam and refluxing to the reaction flask, and at least partially adding Br2And hydrogen bromide vapor is absorbed with water; wherein the low-temperature condensation temperature is-10-0 ℃;
s2: after cooling to 25 ℃, pouring the reaction liquid of terphenyl and liquid bromine into 2L of methanol, stirring for 0.5 hour, filtering, and washing the filter cake at least once again by using 800mL of methanol; drying the filtered filter cake for 2 hours at 60 ℃ by using a blast oven, adding the dried crude product into 200mL of methylbenzene for refluxing and pulping for 12 hours, rinsing the filter cake once by using 200mL of methylbenzene after heat filtration, and then pumping to dry; and adding the drained filter cake into 200mL of methylbenzene for refluxing and pulping for 4 hours, rinsing the filter cake with 200mL of methylbenzene after hot filtration, draining, putting the obtained filter cake into a forced air oven, and drying for 24 hours at 80 ℃ to obtain the 4,4' -dibromo-p-terphenyl.
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