CN109180483A - A method of synthesis hexamethyl terphenyl dimethyl ester - Google Patents
A method of synthesis hexamethyl terphenyl dimethyl ester Download PDFInfo
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- CN109180483A CN109180483A CN201811072485.XA CN201811072485A CN109180483A CN 109180483 A CN109180483 A CN 109180483A CN 201811072485 A CN201811072485 A CN 201811072485A CN 109180483 A CN109180483 A CN 109180483A
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- CN
- China
- Prior art keywords
- hexamethyl
- methyl
- terphenyl
- dimethyl ester
- trimethylbenzene
- Prior art date
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Links
- -1 terphenyl dimethyl ester Chemical compound 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000003786 synthesis reaction Methods 0.000 title claims description 16
- 230000015572 biosynthetic process Effects 0.000 title claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 150000002367 halogens Chemical class 0.000 claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical class CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical class COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- QAQWVXQGPGEZFR-UHFFFAOYSA-N 3-chloro-2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1Cl QAQWVXQGPGEZFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 2
- GTPNXFKONRIHRW-UHFFFAOYSA-N 2-iodo-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(I)C(C)=C1 GTPNXFKONRIHRW-UHFFFAOYSA-N 0.000 claims 1
- 150000001555 benzenes Chemical class 0.000 claims 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- FYGHSUNMUKGBRK-UHFFFAOYSA-N trimethylbenzene Natural products CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003011 anion exchange membrane Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 description 2
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 2
- ZEIAOZOEKLAWBR-UHFFFAOYSA-N 3-[4-(3-carboxyphenyl)phenyl]benzoic acid Chemical class OC(=O)C1=CC=CC(C=2C=CC(=CC=2)C=2C=C(C=CC=2)C(O)=O)=C1 ZEIAOZOEKLAWBR-UHFFFAOYSA-N 0.000 description 1
- VUVHCRZIUORPEG-UHFFFAOYSA-N 3-bromo-2,4,6-trimethylbenzoic acid Chemical class CC1=CC(C)=C(C(O)=O)C(C)=C1Br VUVHCRZIUORPEG-UHFFFAOYSA-N 0.000 description 1
- XJMMPYLOVYSIHP-UHFFFAOYSA-N 3-iodo-2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1I XJMMPYLOVYSIHP-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000001911 terphenyls Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application involves a kind of methods for synthesizing hexamethyl terphenyl dimethyl ester, the method includes the following steps: S1: in an inert atmosphere, at a temperature of -40 DEG C to -50 DEG C and in the case where there are nucleopilic reagent, make 2 that meta position is replaced by single halogen, 4,6- methyl trimethylbenzenes react 3-5 hours with trialkyl borate in the first organic solvent, obtain 3- boronate -2,4,6- methyl trimethylbenzenes；And S2: in an inert atmosphere, and under reflux conditions, make 3- boronate -2,4,6- methyl trimethylbenzene reacts 16-19 hours in a second organic solvent with benzene, inorganic base and catalyst that contraposition is replaced by double halogens, obtains the hexamethyl terphenyl dimethyl ester.The beneficial effects of the present application are as follows the synthetic method of the application synthesizes hexamethyl terphenyl dimethyl ester as raw material using the cheap paradibromobenzene being easy to get, cost is significantly reduced.
Description
Technical field
This application involves technical field of organic synthesis.Specifically, this application involves a kind of synthesis hexamethyl terphenyls two
The method of methyl esters.
Background technique
The hydroxide of HMT-PBI is conducting polymer HMT-PMBI, can be used for preparing alkaline anion-exchange membrane
(AAEM), in a fuel cell, making fuel cell have many advantages, such as efficiently low emission.In addition, AAEM can be also used in water electrolysis
In, for energy storage.AAEM fuel cell compared with existing Proton Exchange Membrane Fuel Cells, have the advantages that it is many potential, therefore
AAEM is developed into the emphasis of people's research, wherein [1,1':4', 1 "-terphenyl] -3,3 "-dicarboxylic acids, 2,2 ", 4,4 ", 6,
6 "-hexamethyls-, 3,3 "-dimethyl esters (HMTE, hereinafter referred hexamethyl terphenyl dimethyl ester) are a weights for synthesizing HMT-PMBI
Want intermediate monomer.
Chinese invention patent application CN106255715A reports a kind of method for synthesizing hexamethyl terphenyl dimethyl ester,
Synthetic route is as follows:
In the synthetic method that the document discloses, with 2,4,6- trimethylbenzoic acids for starting material, it is sequentially prepared centre
Then body M1, that is, 3- bromo- 2,4,6- trimethylbenzoic acids and intermediate M2, that is, 3- bromo- 2,4,6- methyl trimethylbenzenes make
The bromo- 2,4,6- methyl trimethylbenzene of 3- reacts to synthesize hexamethyl with 1,4- phenylene hypoboric acid (also known as to benzene hypoboric acid)
Terphenyl dimethyl ester.The yield of final step is 60%.This synthetic method is disadvantageous in that: (1) to benzene hypoboric acid at
This is higher, can reduce product profit.
For this purpose, this field is continuously needed the process route for developing a kind of synthesis hexamethyl terphenyl dimethyl ester of economy, section
About cost.
Summary of the invention
The method of the synthesis hexamethyl terphenyl dimethyl ester for being designed to provide a kind of economy of the application, thus on solving
The technical issues of stating in the prior art.Specifically, the synthetic method of the application is bromo- by intermediate M2, that is, 3- by two-step method
2,4,6- methyl trimethylbenzenes are converted to aryl boric acid, take aryl boric acid by double halogens with contraposition cheap and easy to get
The benzene in generation reacts, and target product hexamethyl terphenyl dimethyl ester is made.
In order to solve it is above-mentioned in the prior art the technical issues of, the application provide following technical scheme.
In the first aspect, the application provides a kind of method for synthesizing hexamethyl terphenyl dimethyl ester, the method includes
Following step:
S1: in an inert atmosphere, at a temperature of -40 DEG C to -50 DEG C and in the case where there are nucleopilic reagent, make meta position
It is small that the 2,4,6- methyl trimethylbenzene replaced by single halogen with trialkyl borate reacts 3-5 in the first organic solvent
When, obtain 3- boronate -2,4,6- methyl trimethylbenzene；And
S2: in an inert atmosphere, and under reflux conditions, making 3- boronate -2,4,6- methyl trimethylbenzene with it is right
Benzene, inorganic base and the catalyst that position is replaced by double halogens react 16-19 hours in a second organic solvent, obtain the hexamethyl
Terphenyl dimethyl ester；
Wherein, 2,4, the 6- methyl trimethylbenzenes that the meta position is replaced by single halogen include 2,4,6- trimethyl of 3- bromine
The chloro- 2,4,6- methyl trimethylbenzene of methyl benzoate, 3- or the iodo- 2,4,6- methyl trimethylbenzene of 3-；
Wherein, contraposition includes paradibromobenzene, to iodine hexichol or p-dichlorobenzene by the benzene that double halogens replace.
In a specific embodiment, the nucleopilic reagent includes devise a stratagem lithium.
In a kind of embodiment of first aspect, step S1 further includes in make that meta position replaces by single halogen 2,4,6- tri-
After methyl toluate reacts 3-5 hours in the first organic solvent with trialkyl borate, control gained reaction mixing
The temperature of object is lower than 30 DEG C, adds water into gained reaction mixture and concentrated hydrochloric acid, stratification are used in combination at water phase and organic phase
First organic solvent aqueous phase extracted merges organic phase and uses saturated common salt water washing later, is concentrated under reduced pressure and after dry organic phase
Obtain the 3- boronate -2,4,6- methyl trimethylbenzene.
In a kind of embodiment of first aspect, step S2 further includes making 3- boronate -2,4,6- trimethylbenzoic acid
It, will after methyl esters reacts 16-19 hours with benzene, inorganic base and catalyst that contraposition is replaced by double halogens in a second organic solvent
The temperature of gained reaction mixture is reduced to 50 ± 5 DEG C, is subsequently poured into the second that percentage by volume is 40% and temperature is 50 ± 5 DEG C
In alcohol solution, continue to be cooled to 25 ± 5 DEG C, suction filtration obtains yellow crude, recrystallizes the yellow crude in ethyl acetate
And the hexamethyl terphenyl dimethyl ester is obtained after drying.
In a kind of embodiment of first aspect, in step sl, 2,4, the 6- front threes for replacing meta position by single halogen
Yl benzoic acid methyl esters reacts 3 hours with trialkyl borate in the first organic solvent；And/or in step s 2, make 3- boric acid
Benzene, inorganic base and the catalyst that base -2,4,6- methyl trimethylbenzene and contraposition are replaced by double halogens are in the second organic solvent
Middle reaction 16 hours.
In a kind of embodiment of first aspect, first solvent includes tetrahydrofuran；And/or it is described second molten
Agent includes dioxane.
In a kind of embodiment of first aspect, in step sl, the meta position replaced by single halogen 2,4,6- tri-
2,4, the 6- trimethylbenzoic acids that methyl toluate is replaced by meta position by single halogen and oxalyl chloride react to prepare,
Described in the 2,4,6- trimethylbenzoic acid that is replaced by single halogen of meta position include 3- bromine 2,4,6- trimethylbenzoic acid, 3- chloro- 2,
4,6- trimethylbenzoic acid or the iodo- 2,4,6- trimethylbenzoic acid of 3-.
In a kind of embodiment of first aspect, in step s 2, the trialkyl borate includes three isopropyl of boric acid
Ester.
In a kind of embodiment of first aspect, in step s 2, the inorganic base includes potassium carbonate, sodium carbonate, carbon
One or more of potassium hydrogen phthalate or sodium bicarbonate；And/or the catalyst includes four (triphenyl phosphorus) palladiums.
It in a kind of embodiment of first aspect, in step sl, is counted on the basis of molal quantity, the boric acid alkyl ester
It is excessive for the 2,4,6- methyl trimethylbenzene that the meta position is replaced by single halogen.
It in a kind of embodiment of first aspect, in step s 2, is counted on the basis of molal quantity, 3- boronate -2,4,
6- methyl trimethylbenzene is 2-2.5:1 by the benzene usage ratio that double halogens replace with contraposition.
Compared with prior art, the beneficial effects of the present application are as follows the synthetic method of the application is easy to get using cheap
Paradibromobenzene synthesizes hexamethyl terphenyl dimethyl ester as raw material, significantly reduces cost.
Specific embodiment
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise in the application it is all use term "comprising"s, " comprising ", or " having " composition may include appoint
What additional additive, auxiliary material or compound.On the contrary, come out to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
Separate member listed or any combination thereof.
A kind of method of the synthesis hexamethyl terphenyl dimethyl ester for being designed to provide economy of the application, specifically synthesizes road
Line is as follows:
Compared with the synthetic route of the prior art, the application's the difference is that first by intermediate M2, that is, 3- bromo- 2,
4,6- methyl trimethylbenzene is converted to intermediate M3 i.e. 3- boronate -2,4,6- methyl trimethylbenzene.Then, then make
3- boronate -2,4,6- methyl trimethylbenzene are reacted with cheap paradibromobenzene, to iodine hexichol or p-dichlorobenzene,
Obtain hexamethyl terphenyl dimethyl ester.
Embodiment
Below in conjunction with the embodiment of the present invention, clear and complete description is carried out to technical solution of the present invention.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.Actual conditions are not specified in the following example
Experimental method according to conventional methods and conditions, or is selected according to product manual.
Embodiment 1
The present embodiment is related to synthesizing 3- bromo- 2, and 4,6- trimethylbenzoic acids, synthetic route is as follows:
The specific experiment process of the embodiment is as described below.
2,4,6- trimethylbenzoic acid 200g, acetic acid 2940g are added into 5L four-hole bottle and opens stirring, ice bath is cooled to 20
± 2 DEG C, start acetic acid (840g) solution that bromine is added dropwise, react micro- heat release, control temperature is no more than 30 DEG C to dripping (about
0.5h).25 ± 2 DEG C of heat preservation 1.5h (middle control Liao≤0.5 1, Yuan) after dripping off.
After middle control is qualified, reaction solution is poured into the 5%Na of 7L2SO3In solution, white solid is precipitated, 25 ± 2 DEG C of stirring 2h,
It filters, solid is eluted with 500g water.Obtain wet product 640g.
Wet product to be thrown into 5L bottles, 1500ml80% ethanol water recrystallization is added, 70 DEG C of dissolved clarifications are cooled to 25 DEG C,
It filters, 80 DEG C of convection ovens of product dry to obtain 240g white solid M1, (middle control 2, main Han Liang≤97%).
Embodiment 2
The present embodiment is related to synthesizing 3- bromo- 2, and 4,6- methyl trimethylbenzenes, synthetic route is as follows:
The specific experiment process of the embodiment is as described below.
Under nitrogen protection, 246gM1, methylene chloride are put into 5L bottles, 25 ± 5 DEG C of dropwise addition oxalyl chlorides, 1h is dripped
Finishing, 25 ± 5 DEG C of the reaction was continued 2h, then revolving removes methylene chloride, rejoin new methylene chloride 1000g dissolution, 25 ± 5 DEG C
Under be added dropwise in 1000g methanol, react 2h, (middle control 1, raw material < 0.5%).
After middle control is qualified, revolving solvent to dry, addition 500g methylene chloride, sodium bicarbonate solution 200ml washing 1 time is satisfied
It being washed to pH=7 or so with saline solution 200ml, organic phase 50g anhydrous sodium sulfate is dry, it is spin-dried for obtaining 250g intermediate M2, (in
Control 2, main Han Liang≤98%).
Embodiment 3
The embodiment is related to synthesizing 3- boronate -2,4, and 6- methyl trimethylbenzene, synthetic route is as follows:
The specific experiment process of the embodiment is as described below.
Under nitrogen protection, 514g M2 (2mol), 414g (2.2mol) triisopropyl borate ester, 2.5g tetrahydrofuran are thrown
Enter 10L four-hole bottle, is cooled to -40 DEG C.It is added dropwise butyl lithium (1.1L, 2mol/L), controls temperature between -40 DEG C~-50 DEG C, drop
Add about 1 hour, is added dropwise reaction 1 hour and samples, about 3 hours end of reaction.
It controls temperature and is lower than 30 DEG C, 2L water quenching is added dropwise and goes out, adds 0.5L concentrated hydrochloric acid, stirs 1 hour, stratification, water
Layer is primary with the extraction of 500ml tetrahydrofuran again, and organic phase merges, saturated salt solution 500ml washing.Separate organic phase reduced pressure
To dry, addition 2L n-hexane stirring, filtering is filtered by filter cake again with n-hexane mashing (40~45 DEG C, stir 1 hour).Filter cake
It is dried in 50 DEG C or less air blast, obtains white solid 400g M3 (yield 90%, purity 98%).
Embodiment 4
The present embodiment is related to synthesizing hexamethyl using 3- boronate -2,4,6- methyl trimethylbenzene and paradibromobenzene
Terphenyl dimethyl ester, synthetic route are as follows:
The specific experiment process of the embodiment is as described below.
Under nitrogen protection, by 111g M3 (0.5mol), 47g paradibromobenzene (0.2mol), 138g potassium carbonate (1mol) and
2.2L dioxane is put into 5L bottles, and 7g (6mmol) four (triphenyl phosphorus) palladium is added after replacing 3 times in nitrogen, is warming up to reflux, instead
It answers 16 hours.
50 ± 5 DEG C are cooled to, is poured into 50 ± 5 DEG C of ethanol water (40%), continues to be cooled to 25 ± 5 DEG C, filter
It obtains yellow crude 90g, 1L re-crystallizing in ethyl acetate is added and obtains wet product 65g, 50 DEG C of vacuum drying ovens are dried to obtain 52g white solid
Body HMTE (main content 98%, yield 60%).
Embodiment 5
The present embodiment is related to synthesizing hexamethyl using 3- boronate -2,4,6- methyl trimethylbenzene and paradiiodobenzene
Terphenyl dimethyl ester.
The specific experiment process of the embodiment is as described below.
Under nitrogen protection, by 111g M3 (0.5mol), 66g paradiiodobenzene (0.2mol), 138g potassium carbonate (1mol) and
2.2L dioxane is put into 5L bottles, and 7g (6mmol) four (triphenyl phosphorus) palladium is added after replacing 3 times in nitrogen, is warming up to reflux, instead
It answers 16 hours.
50 ± 5 DEG C are cooled to, is poured into 50 ± 5 DEG C of ethanol water (40%), continues to be cooled to 25 ± 5 DEG C, filter
It obtains yellow crude 90g, 1L re-crystallizing in ethyl acetate is added and obtains wet product 75g, 50 DEG C of vacuum drying ovens are dried to obtain 58g white solid
Body HMTE (main content 98%, yield 68%).
Embodiment 6
The present embodiment is related to synthesizing hexamethyl using 3- boronate -2,4,6- methyl trimethylbenzene and paracide
Terphenyl dimethyl ester.
The specific experiment process of the embodiment is as described below.
Under nitrogen protection, by 111g M3 (0.5mol), 29.5g paracide (0.2mol), 138g potassium carbonate (1mol) and
2.2L dioxane is put into 5L bottles, and 7g (6mmol) four (triphenyl phosphorus) palladium is added after replacing 3 times in nitrogen, is warming up to reflux, instead
It answers 16 hours.
50 ± 5 DEG C are cooled to, is poured into 50 ± 5 DEG C of ethanol water (40%), continues to be cooled to 25 ± 5 DEG C, filter
It obtains yellow crude 90g, 1L re-crystallizing in ethyl acetate is added and obtains wet product 60g, 50 DEG C of vacuum drying ovens are dried to obtain 50g white solid
Body HMTE (main content 98%, yield 58%).
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying creative labor.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and modifies within all scope of the present application.
Claims (10)
1. a kind of method for synthesizing hexamethyl terphenyl dimethyl ester, the method includes the following steps:
S1: in an inert atmosphere, at a temperature of -40 DEG C to -50 DEG C and in the case where there are nucleopilic reagent, make meta position by list
2,4, the 6- methyl trimethylbenzenes that halogen replaces react 3-5 hours with trialkyl borate in the first organic solvent, obtain
To 3- boronate -2,4,6- methyl trimethylbenzene；And
S2: in an inert atmosphere, and under reflux conditions, making 3- boronate -2,4,6- methyl trimethylbenzene and contraposition by
Benzene, inorganic base and the catalyst that double halogens replace react 16-19 hours in a second organic solvent, obtain the hexamethyl three
Benzene dimethyl ester；
Wherein, 2,4, the 6- methyl trimethylbenzenes that the meta position is replaced by single halogen include 2,4,6- trimethylbenzene first of 3- bromine
The chloro- 2,4,6- methyl trimethylbenzene of sour methyl esters, 3- or the iodo- 2,4,6- methyl trimethylbenzene of 3-；
Wherein, contraposition includes paradibromobenzene, to iodine hexichol or p-dichlorobenzene by the benzene that double halogens replace.
2. as described in claim 1 synthesis hexamethyl terphenyl dimethyl ester method, which is characterized in that step S1 further include
The 2,4,6- methyl trimethylbenzene for replacing meta position by single halogen reacts in the first organic solvent with trialkyl borate
After 3-5 hours, the temperature of control gained reaction mixture is lower than 30 DEG C, and water and dense salt are added into gained reaction mixture
Acid, stratification is at water phase and organic phase, and with the first organic solvent aqueous phase extracted, merges and uses saturated salt solution after organic phase
Washing is concentrated under reduced pressure and obtains the 3- boronate -2,4,6- methyl trimethylbenzene after dry organic phase.
3. the method for synthesis hexamethyl terphenyl dimethyl ester as described in claim 1, which is characterized in that step S2 further includes making
Benzene, inorganic base and the catalyst that 3- boronate -2,4,6- methyl trimethylbenzene is replaced with contraposition by double halogens have second
After being reacted 16-19 hours in solvent, the temperature of gained reaction mixture is reduced to 50 ± 5 DEG C, is subsequently poured into volume hundred
In the ethanol water that score is 40% and temperature is 50 ± 5 DEG C, continue to be cooled to 25 ± 5 DEG C, suction filtration obtains yellow crude, makes
The yellow crude obtains the hexamethyl terphenyl dimethyl ester after recrystallizing and dry in ethyl acetate.
4. the method for synthesis hexamethyl terphenyl dimethyl ester as claimed in any one of claims 1-3, which is characterized in that in step
In rapid S1,2,4, the 6- methyl trimethylbenzenes and trialkyl borate for replacing meta position by single halogen are in the first organic solvent
Middle reaction 3 hours；And/or in step s 2, make 3- boronate -2,4,6- methyl trimethylbenzene and contraposition are by double halogens
Substituted benzene, inorganic base and catalyst reacts 16 hours in a second organic solvent.
5. the method for synthesis hexamethyl terphenyl dimethyl ester as claimed in any one of claims 1-3, which is characterized in that described
First solvent includes tetrahydrofuran；And/or second solvent includes dioxane.
6. the method for synthesis hexamethyl terphenyl dimethyl ester as claimed in any one of claims 1-3, which is characterized in that in step
In rapid S1,2,4, the 6- methyl trimethylbenzenes that the meta position is replaced by single halogen replaced by meta position by single halogen 2,4,
6- trimethylbenzoic acid and oxalyl chloride react to prepare, wherein 2,4, the 6- trimethylbenzene first that the meta position is replaced by single halogen
Acid includes 3- bromine 2,4,6- trimethylbenzoic acid, the chloro- 2,4,6- trimethylbenzoic acid of 3- or the iodo- 2,4,6- trimethylbenzene first of 3-
Acid.
7. the method for synthesis hexamethyl terphenyl dimethyl ester as claimed in any one of claims 1-3, which is characterized in that in step
In rapid S2, the trialkyl borate includes triisopropyl borate ester.
8. the method for synthesis hexamethyl terphenyl dimethyl ester as claimed in any one of claims 1-3, which is characterized in that in step
In rapid S2, the inorganic base includes one or more of potassium carbonate, sodium carbonate, saleratus or sodium bicarbonate；And/or institute
Stating catalyst includes four (triphenyl phosphorus) palladiums.
9. the method for synthesis hexamethyl terphenyl dimethyl ester as claimed in any one of claims 1-3, which is characterized in that in step
In rapid S1, counted on the basis of molal quantity, 2,4, the 6- front threes that the boric acid alkyl ester is replaced relative to the meta position by single halogen
It is excessive for yl benzoic acid methyl esters.
10. the method for synthesis hexamethyl terphenyl dimethyl ester as claimed in any one of claims 1-3, which is characterized in that
It in step S2, is counted on the basis of molal quantity, 3- boronate -2,4,6- methyl trimethylbenzene is replaced with contraposition by double halogens
Benzene usage ratio is 2-2.5:1.
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| KR20100007617A (en) * | 2008-07-14 | 2010-01-22 | 덕산하이메탈(주) | Heterocyclic derivatives containing nitrogen and organic electroluminescent devices comprising the same |
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| KR20100007617A (en) * | 2008-07-14 | 2010-01-22 | 덕산하이메탈(주) | Heterocyclic derivatives containing nitrogen and organic electroluminescent devices comprising the same |
| CN106255715A (en) * | 2014-04-15 | 2016-12-21 | 西蒙·弗雷泽大学 | The ionene that hydroxide is stable |
| CN106565761A (en) * | 2016-11-15 | 2017-04-19 | 贵州大学 | Preparing technology for 4-carboxyphenylboronic acid |
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