CN115745833A - Preparation method of 4-alkyl-4' -cyanobiphenyl - Google Patents
Preparation method of 4-alkyl-4' -cyanobiphenyl Download PDFInfo
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- CN115745833A CN115745833A CN202211363361.3A CN202211363361A CN115745833A CN 115745833 A CN115745833 A CN 115745833A CN 202211363361 A CN202211363361 A CN 202211363361A CN 115745833 A CN115745833 A CN 115745833A
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- alkyl
- cyanobiphenyl
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- biphenyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 17
- 239000004305 biphenyl Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000005893 bromination reaction Methods 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- -1 alkyl lithium Chemical compound 0.000 claims description 10
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000010517 secondary reaction Methods 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 abstract description 4
- 150000008282 halocarbons Chemical class 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 239000011261 inert gas Substances 0.000 description 20
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 16
- KAWPTSPOSZBAHH-UHFFFAOYSA-N 1-bromo-4-(4-butylphenyl)benzene Chemical group C1=CC(CCCC)=CC=C1C1=CC=C(Br)C=C1 KAWPTSPOSZBAHH-UHFFFAOYSA-N 0.000 description 11
- UADBHFTWQBWLOF-UHFFFAOYSA-N [Li].CCCC[Cu]CCCC Chemical compound [Li].CCCC[Cu]CCCC UADBHFTWQBWLOF-UHFFFAOYSA-N 0.000 description 10
- PJPLBHHDTUICNN-UHFFFAOYSA-N 4-(4-butylphenyl)benzonitrile Chemical group C1=CC(CCCC)=CC=C1C1=CC=C(C#N)C=C1 PJPLBHHDTUICNN-UHFFFAOYSA-N 0.000 description 9
- 239000005209 4-Butyl-4'-cyanobiphenyl Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- OARBGVNQCYYPKT-UHFFFAOYSA-N 1-bromo-4-(4-ethylphenyl)benzene Chemical group C1=CC(CC)=CC=C1C1=CC=C(Br)C=C1 OARBGVNQCYYPKT-UHFFFAOYSA-N 0.000 description 3
- RJQRJLCQHIMUQO-UHFFFAOYSA-N 1-bromo-4-(4-heptylphenyl)benzene Chemical group C1=CC(CCCCCCC)=CC=C1C1=CC=C(Br)C=C1 RJQRJLCQHIMUQO-UHFFFAOYSA-N 0.000 description 3
- MYWLXURJCXISCT-UHFFFAOYSA-N 1-bromo-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(Br)C=C1 MYWLXURJCXISCT-UHFFFAOYSA-N 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 3
- DLLIPJSMDJCZRF-UHFFFAOYSA-N 4-(4-ethylphenyl)benzonitrile Chemical group C1=CC(CC)=CC=C1C1=CC=C(C#N)C=C1 DLLIPJSMDJCZRF-UHFFFAOYSA-N 0.000 description 3
- ZGOWXOZNUNZPAV-UHFFFAOYSA-N 4-(4-heptylphenyl)benzonitrile Chemical group C1=CC(CCCCCCC)=CC=C1C1=CC=C(C#N)C=C1 ZGOWXOZNUNZPAV-UHFFFAOYSA-N 0.000 description 3
- QIBWMVSMTSYUSK-UHFFFAOYSA-N 4-(4-methylphenyl)benzonitrile Chemical group C1=CC(C)=CC=C1C1=CC=C(C#N)C=C1 QIBWMVSMTSYUSK-UHFFFAOYSA-N 0.000 description 3
- OMYYOIIFAWKWGG-UHFFFAOYSA-N [Li].CC[Cu]CC Chemical compound [Li].CC[Cu]CC OMYYOIIFAWKWGG-UHFFFAOYSA-N 0.000 description 3
- LQCYIQBYFCQMCH-UHFFFAOYSA-N [Li].C[Cu]C Chemical compound [Li].C[Cu]C LQCYIQBYFCQMCH-UHFFFAOYSA-N 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 2
- ILOYPIODPORGAZ-UHFFFAOYSA-N [Li]CCCCCCC Chemical compound [Li]CCCCCCC ILOYPIODPORGAZ-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of compound synthesis, and particularly discloses a preparation method of 4-alkyl-4' -cyanobiphenyl. The preparation method comprises the steps of carrying out bromination reaction on biphenyl serving as a raw material to obtain brominated biphenyl; the bromo-biphenyl and dialkyl copper lithium reagent are subjected to coupling reaction to obtain 4-alkyl-4 '-bromo-biphenyl, and further subjected to substitution reaction with metal cyanide to obtain 4-alkyl-4' -cyano-biphenyl. The preparation method of the 4-alkyl-4 '-cyanobiphenyl provided by the application is simple in process, mild in conditions, environment-friendly, capable of reducing the activity requirement on halogenated hydrocarbons, capable of effectively shortening the reaction route, capable of improving the production efficiency, capable of greatly reducing the material cost, capable of improving the yield and the raw material utilization rate, capable of effectively improving the product yield and purity from the aspects of reaction and post-treatment, and capable of finally preparing the 4-alkyl-4' -cyanobiphenyl with the yield of 92.5% and the purity of 99.7%.
Description
Technical Field
The invention belongs to the field of compound synthesis, and particularly relates to a preparation method of 4-alkyl-4' -cyanobiphenyl.
Background
The alkyl biphenyl nitrile as a liquid crystal material has excellent light stability and chemical stability, and also has the advantages of adjustable physical constants such as anisotropy, viscosity, birefringence and the like; these are excellent liquid crystal materials which can display at room temperature, and are a field of research which has attracted particular attention in recent years, and have attracted much attention from organic chemists.
At present, the main methods for preparing alkyl biphenylcarbonitriles include that biphenyl is used as a raw material, and four steps of Friedel-crafts acylation, hydrazine hydrate reduction, iodination and cyanation are carried out to prepare the alkyl biphenylcarbonitriles; or, the p-bromoaniline is used as a raw material and is subjected to diazotization, benzene coupling, friedel-crafts acylation, hydrazine hydrate reduction and cyanolysis synthesis reaction. However, when preparing alkyl biphenyl nitrile, the coupling reaction of bromine in p-brominated biphenyl is difficult to occur due to poor activity of biphenyl group in the prior art, and further the problem of low total reaction yield occurs. Therefore, it is of great significance to find a preparation method of the alkyl biphenyl nitrile so as to improve the purity and the yield of the product.
Disclosure of Invention
In view of this, the invention provides a method for preparing 4-alkyl-4' -cyanobiphenyl, which further improves the selectivity of the reaction by selecting specific solvents and reaction reagents, thereby further improving the product yield while improving the product purity.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of 4-alkyl-4' -cyanobiphenyl comprises the following steps:
carrying out bromination reaction on biphenyl to obtain brominated biphenyl;
carrying out coupling reaction on the brominated biphenyl and a dialkyl copper lithium reagent to obtain 4-alkyl-4' -brominated biphenyl;
carrying out substitution reaction on 4-alkyl-4 '-bromobiphenyl and metal cyanide to obtain 4-alkyl-4' -cyanobiphenyl;
wherein the structural formula of the dialkyl copper lithium reagent is R 2 CuLi, the structural formula of the 4-alkyl-4' -cyanobiphenyl is shown in the specification
R is C2-C7 straight-chain alkyl.
Compared with the prior art, the preparation method of the 4-alkyl-4 '-cyanobiphenyl provided by the invention comprises the steps of firstly preparing 4,4' -dibromobiphenyl by efficient bromination reaction, and then performing coupling reaction by using dialkyl copper lithium reagent and bromobiphenyl, wherein the conventional coupling reaction is difficult to occur due to poor activity of biphenyl groups in the bromobiphenyl, the problem of poor activity of the biphenyl groups in the bromobiphenyl is solved by preparing specific dialkyl copper lithium, and the dialkyl copper lithium is a mild nucleophilic reagent and has good selectivity.
The preferred method for preparing 4-alkyl-4' -cyanobiphenyl specifically comprises the following steps:
step a, reacting biphenyl, bromine, a first solvent and a catalyst serving as raw materials at the temperature of 30-50 ℃ for 1-6 h to obtain 4,4' -dibromobiphenyl;
b, reacting the dialkyl copper lithium, 4,4 '-dibromobiphenyl and a second solvent at the temperature of-10-70 ℃ for 2-5 h to obtain 4-alkyl-4' -bromobiphenyl;
and c, reacting the 4-alkyl-4 '-bromobiphenyl, cuprous cyanide and a third solvent at 150-180 ℃ for 4-10 h to obtain the 4-alkyl-4' -cyanobiphenyl.
Preferably, the method for preparing 4-alkyl-4' -cyanobiphenyl is carried out under an inert gas.
Preferably, the preparation method of the dialkyl lithium copper comprises the following steps: performing a first-stage reaction on metal lithium and chloralkane in a fourth solvent to obtain alkyl lithium; and carrying out secondary reaction on the alkyl lithium and cuprous iodide in a fifth solvent to obtain the dialkyl copper lithium.
Preferably, in step a, the catalyst is at least one of aluminum trichloride, zinc chloride or ferric trichloride.
Preferably, the molar ratio of biphenyl to catalyst is 1:0.01 to 0.1.
Preferably, in step a, the first solvent is at least one of tetrahydrofuran, ethyl acetate, methyl tert-butyl ether or petroleum ether.
Preferably, in the step a, the molar ratio of biphenyl to bromine is 1.
Preferably, in the step a, the mass-volume ratio of the biphenyl to the first solvent is 1:2-5, the units of mass are grams and the units of volume are milliliters.
Preferably, in the step b, the second solvent is a mixed solution of tetrahydrofuran and xylene with a volume ratio of 1:1-4.
The preferable second solvent can improve the selectivity of the bromine substitution in the dialkyl copper lithium to the brominated biphenyl, thereby reducing the generation of reaction byproducts and further improving the yield of the total product while improving the purity of the product.
Preferably, the 4,4' -dibromobiphenyl and the dialkyl copper lithium have a molar ratio of 1:1-2.
Preferably, the mass-to-volume ratio of the 4,4' -dibromobiphenyl to the second solvent is 1:3-5, the unit of mass is gram, and the unit of volume is milliliter.
Preferably, in step c, the third solvent is at least one of dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, sulfolane or xylene.
Preferably, the molar ratio of the 4-alkyl-4' -bromobiphenyl to the cuprous cyanide is 1:1-2.
Preferably, the mass-to-volume ratio of the 4-alkyl-4' -bromobiphenyl to the third solvent is 1:3-6, the unit of mass is gram, and the unit of volume is milliliter.
Preferably, the fourth solvent is at least one of tetrahydrofuran, anhydrous ethyl ether, methyl tert-butyl ether or petroleum ether; the temperature of the first-stage reaction is-40 ℃ to-20 ℃, and the time is 0.5h to 6h.
Preferably, the fifth solvent is at least one of tetrahydrofuran, anhydrous diethyl ether, dioxane, methyl tert-butyl ether, toluene, benzene or petroleum ether; the temperature of the secondary reaction is-70 ℃ to-20 ℃, and the time is 4h to 8h.
The preparation method of the 4-alkyl-4 '-cyanobiphenyl provided by the invention has the advantages of simple process, mild conditions and environmental friendliness, reduces the activity requirement on halogenated hydrocarbon, effectively shortens the reaction route, improves the production efficiency, greatly reduces the material cost, improves the yield and the raw material utilization rate, effectively improves the product yield and purity from the aspects of reaction and post-treatment, and finally prepares the 4-alkyl-4' -cyanobiphenyl with the yield of 92.5% and the purity of 99.7%.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The invention provides a preparation method of 4-butyl-4' -cyanobiphenyl, which comprises the following steps:
(1) preparation of 4,4' -dibromobiphenyl
Under the protection of inert gas, adding biphenyl (0.16 mol), bromine (0.336 mol), aluminum trichloride (0.0016 mol) and ethyl acetate (50 mL), stirring, and reacting at 30 ℃ for 6h to obtain 4,4' -dibromobiphenyl with the purity of 99.8 percent and the yield of 93 percent;
(2) preparation of dibutyl copper lithium
Setting metal lithium (0.3 mol) and chlorobutane (0.3 mol) in tetrahydrofuran (55 mL) solution at-40 ℃ for reaction for 0.5h to obtain butyl lithium, setting butyl lithium (0.28 mol) and cuprous iodide (0.14 mol) in dioxane (71 mL) at-70 ℃ for reaction for 4h to obtain dibutyl copper lithium;
(3) preparation of 4-butyl-4' -bromobiphenyl
Under the protection of inert gas, dibutyl copper lithium (0.14 mol), the prepared 4,4 '-dibromobiphenyl (0.14 mol) and a mixed solution of tetrahydrofuran (66 mL) and xylene (66 mL) with the volume ratio of 1:1 react for 2h at 70 ℃ to obtain 4-butyl-4' -bromobiphenyl, the purity of the product is 98.2%, and the yield is 89%;
(4) preparation of 4-butyl-4' -cyanobiphenyl
Under the protection of inert gas, 4-butyl-4 '-bromobiphenyl (0.12 mol), cuprous cyanide (0.12 mol) and dimethyl sulfoxide (208 mL) react for 4 hours at 180 ℃ to obtain 4-butyl-4' -cyanobiphenyl, the purity of the obtained product is 99.6%, and the yield is 92.5%.
Example 2
The invention provides a preparation method of 4-ethyl-4' -cyanobiphenyl, which comprises the following steps:
(1) preparation of 4,4' -dibromobiphenyl
Under the protection of inert gas, adding biphenyl (0.16 mol), bromine (0.448 mol), aluminum trichloride (0.016 mol) and methyl tert-butyl ether (123 mL) and stirring, reacting for 1h at 50 ℃ to obtain 4,4' -dibromobiphenyl with the purity of 99.2 percent and the yield of 91.2 percent;
(2) preparation of diethyl copper lithium
Setting metal lithium (0.7 mol) and chloroethane (0.7 mol) in tetrahydrofuran (92 mL) solution at-20 ℃ for reaction for 6h to obtain ethyl lithium, setting ethyl lithium (0.68 mol) and cuprous iodide (0.34 mol) in dioxane (174 mL) at-20 ℃ for reaction for 8h to obtain diethyl copper lithium;
(3) preparation of 4-ethyl-4' -bromobiphenyl
Under the protection of inert gas, reacting diethyl copper lithium (0.28 mol), 4,4 '-dibromobiphenyl (0.14 mol) and a mixed solution of tetrahydrofuran (43 mL) and xylene (172 mL) with the volume ratio of 1:4 at-10 ℃ for 5 hours to obtain 4-ethyl-4' -bromobiphenyl, wherein the purity of the product is 98.6%, and the yield is 85%;
(4) preparation of 4-ethyl-4' -cyanobiphenyl
Under the protection of inert gas, 4-ethyl-4 '-bromobiphenyl (0.11 mol), cuprous cyanide (0.22 mol) and dimethyl sulfoxide (87 mL) react for 10h at 150 ℃ to obtain 4-ethyl-4' -cyanobiphenyl, and the purity of the obtained product is 99.7%, and the yield is 90.1%.
Example 3
The invention provides a preparation method of 4-heptyl-4' -cyanobiphenyl, which comprises the following steps:
(1) preparation of 4,4' -dibromobiphenyl
Under the protection of inert gas, adding biphenyl (0.16 mol), bromine (0.4 mol), zinc chloride (0.01 mol) and petroleum ether (100 mL), stirring, and reacting at 40 ℃ for 2h to obtain 4,4' -dibromobiphenyl with the purity of 99.3 percent and the yield of 90 percent;
(2) preparation of lithium diheptyl copper
Setting metal lithium (0.8 mol) and chloro heptane (0.75 mol) in an anhydrous ether (204 mL) solution at-30 ℃ for reaction for 5h to obtain heptyl lithium, setting heptyl lithium (0.7 mol) and cuprous iodide (0.34 mol) in toluene (186 mL) at-50 ℃ for reaction for 5h to obtain diheptyl copper lithium;
(3) preparation of 4-heptyl-4' -bromobiphenyl
Under the protection of inert gas, reacting a mixed solution of lithium diheptyl copper (0.23 mol), 4,4 '-dibromobiphenyl (0.14 mol) and tetrahydrofuran (49 mL) and xylene (147 mL) with the volume ratio of 1:3 at 40 ℃ for 3 hours to obtain 4-heptyl-4' -bromobiphenyl, wherein the purity of the product is 97.9 percent, and the yield is 86 percent;
(4) preparation of 4-heptyl-4' -cyanobiphenyl
Under the protection of inert gas, 4-heptyl-4 '-bromobiphenyl (0.12 mol), cuprous cyanide (0.15 mol) and 1,3-dimethyl-2-imidazolidinone (199 mL) react for 6 hours at 160 ℃ to obtain the 4-heptyl-4' -cyanobiphenyl, wherein the purity of the obtained product is 99.5 percent, and the yield is 89.2 percent.
Example 4
The invention provides a preparation method of 4-butyl-4' -cyanobiphenyl, which comprises the following steps:
(1) preparation of 4,4' -dibromobiphenyl
Under the protection of inert gas, adding biphenyl (0.16 mol), bromine (0.336 mol), aluminum trichloride (0.0016 mol) and ethyl acetate (50 mL) and stirring, reacting for 6 hours at 30 ℃ to obtain 4,4' -dibromobiphenyl with the purity of 99.4 percent and the yield of 94 percent;
(2) preparation of dibutyl copper lithium
Setting metal lithium (0.3 mol) and chlorobutane (0.3 mol) in tetrahydrofuran (55 mL) solution at-40 ℃ for reaction for 0.5h to obtain butyl lithium, setting butyl lithium (0.28 mol) and cuprous iodide (0.14 mol) in dioxane (71 mL) at-70 ℃ for reaction for 4h to obtain dibutyl copper lithium;
(3) preparation of 4-butyl-4' -bromobiphenyl
Under the protection of inert gas, dibutyl copper lithium (0.14 mol), 4,4 '-dibromobiphenyl (0.14 mol) and xylene (132 mL) react for 2h at 70 ℃ to obtain 4-butyl-4' -bromobiphenyl, the purity of the product is 96.3%, and the yield is 78%;
(4) preparation of 4-butyl-4' -cyanobiphenyl
Under the protection of inert gas, 4-butyl-4 '-bromobiphenyl (0.1 mol), cuprous cyanide (0.1 mol) and dimethyl sulfoxide (173 mL) react at 180 ℃ for 4h to obtain 4-butyl-4' -cyanobiphenyl, wherein the purity of the obtained product is 98.7%, and the yield is 83.1%.
Example 5
The invention provides a preparation method of 4-butyl-4' -cyanobiphenyl, which comprises the following steps:
(1) preparation of 4,4' -dibromobiphenyl
Under the protection of inert gas, adding biphenyl (0.16 mol), bromine (0.336 mol), aluminum trichloride (0.0016 mol) and ethyl acetate (50 mL), stirring, and reacting at 30 ℃ for 6h to obtain 4,4' -dibromobiphenyl with the purity of 99.5 percent and the yield of 93.8 percent;
(2) preparation of dibutyl copper lithium
Setting metal lithium (0.3 mol) and chlorobutane (0.3 mol) in tetrahydrofuran (55 mL) solution at-40 ℃ for reaction for 0.5h to obtain butyl lithium, setting butyl lithium (0.28 mol) and cuprous iodide (0.14 mol) in dioxane (71 mL) at-70 ℃ for reaction for 4h to obtain dibutyl copper lithium;
(3) preparation of 4-butyl-4' -bromobiphenyl
Under the protection of inert gas, reacting a mixed solution of dibutyl copper lithium (0.14 mol), 4,4 '-dibromo biphenyl (0.14 mol) and tetrahydrofuran (22 mL) and xylene (110 mL) with the volume ratio of 1:5 at 70 ℃ for 2 hours to obtain 4-butyl-4' -bromobiphenyl, wherein the purity of the product is 97.2%, and the yield is 81%;
(4) preparation of 4-butyl-4' -cyanobiphenyl
Under the protection of inert gas, 4-butyl-4 '-bromobiphenyl (0.11 mol), cuprous cyanide (0.11 mol) and dimethyl sulfoxide (190 mL) react for 4 hours at 180 ℃ to obtain 4-butyl-4' -cyanobiphenyl, the purity of the obtained product is 98.6%, and the yield is 84.2%.
Comparative example 1
The present comparative example differs from example 1 in comparison with example 1 in that:
butyl lithium was used in the step (2) instead of dibutyl copper lithium to perform the next reaction, and the other steps were the same as in example 1. The intended target product is not obtained.
Comparative example 2
The present comparative example differs from example 1 in comparison with example 1 in that:
the specific operation of the step (3) is changed as follows:
(3) preparation of 4-butyl-4' -bromobiphenyl
Under the protection of inert gas, butyl lithium (0.28 mol), cuprous iodide (0.14 mol), 4,4 '-dibromobiphenyl (0.14 mol) and a mixed solution of tetrahydrofuran (66 mL) and xylene (66 mL) with the volume ratio of 1:1 react for 2h at 70 ℃ to obtain 4-butyl-4' -bromobiphenyl, wherein the purity of the product is 57%, and the yield is 43%; the other steps are the same as in example 1.
Comparative example 3
The invention provides a preparation method of 4-methyl-4' -cyanobiphenyl, which comprises the following steps:
(1) preparation of 4,4' -dibromobiphenyl
Under the protection of inert gas, adding biphenyl (0.16 mol), bromine (0.336 mol), aluminum trichloride (0.0016 mol) and ethyl acetate (50 mL), stirring, and reacting at 30 ℃ for 6h to obtain 4,4' -dibromobiphenyl with the purity of 99.3 percent and the yield of 94 percent;
(2) preparation of lithium dimethyl copper
Setting metal lithium (0.3 mol) and chloromethane (0.3 mol) in tetrahydrofuran (31 mL) solution at-40 ℃ for reaction for 0.5h to obtain methyllithium, setting methyllithium (0.28 mol) and cuprous iodide (0.14 mol) in dioxane (24 mL) at-70 ℃ for reaction for 4h to obtain dimethyl copper lithium;
(3) preparation of 4-methyl-4' -bromobiphenyl
Under the protection of inert gas, reacting dimethyl copper lithium (0.14 mol), 4,4 '-dibromo biphenyl (0.14 mol) and a mixed solution of tetrahydrofuran (66 mL) and xylene (66 mL) with the volume ratio of 1:1 at 70 ℃ for 2 hours to obtain 4-methyl-4' -bromobiphenyl, wherein the purity of the product is 97.1%, and the yield is 80%;
(4) preparation of 4-methyl-4' -cyanobiphenyl
Under the protection of inert gas, 4-methyl-4 '-bromobiphenyl (0.11 mol), cuprous cyanide (0.11 mol) and dimethyl sulfoxide (163 mL) react at 180 ℃ for 4h to obtain 4-methyl-4' -cyanobiphenyl, and the purity of the obtained product is 97.6%, and the yield is 79.2%.
The preparation method of the 4-alkyl-4 '-cyanobiphenyl provided by the invention has the advantages of simple process, mild conditions and environmental friendliness, reduces the activity requirement on halogenated hydrocarbon, effectively shortens the reaction route, improves the production efficiency, greatly reduces the material cost, improves the yield and the raw material utilization rate, effectively improves the product yield and purity from the aspects of reaction and post-treatment, and finally prepares the 4-alkyl-4' -cyanobiphenyl with the yield of 92.5% and the purity of 99.7%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of 4-alkyl-4' -cyanobiphenyl is characterized by comprising the following steps:
carrying out bromination reaction on biphenyl to obtain brominated biphenyl;
carrying out coupling reaction on the brominated biphenyl and a dialkyl copper lithium reagent to obtain 4-alkyl-4' -brominated biphenyl;
carrying out substitution reaction on 4-alkyl-4 '-bromobiphenyl and metal cyanide to obtain 4-alkyl-4' -cyanobiphenyl;
wherein the structural formula of the dialkyl copper lithium reagent is R 2 CuLi, the structural formula of the 4-alkyl-4' -cyanobiphenyl is
R is C2-C7 straight-chain alkyl.
2. The method for preparing 4-alkyl-4' -cyanobiphenyl according to claim 1, comprising the steps of:
step a, reacting biphenyl, bromine, a first solvent and a catalyst serving as raw materials at the temperature of 30-50 ℃ for 1-6 h to obtain 4,4' -dibromobiphenyl;
b, reacting the dialkyl copper lithium, 4,4 '-dibromobiphenyl and a second solvent at the temperature of-10-70 ℃ for 2-5 h to obtain 4-alkyl-4' -bromobiphenyl;
and c, reacting the 4-alkyl-4 '-bromobiphenyl, cuprous cyanide and a third solvent at 150-180 ℃ for 4-10 h to obtain the 4-alkyl-4' -cyanobiphenyl.
3. The method for producing 4-alkyl-4' -cyanobiphenyl according to any one of claims 1 or 2, wherein the method for producing lithium dialkylcopper comprises the steps of:
performing a first-stage reaction on metal lithium and chloralkane in a fourth solvent to obtain alkyl lithium; and carrying out secondary reaction on the alkyl lithium and cuprous iodide in a fifth solvent to obtain the dialkyl copper lithium.
4. The method for preparing 4-alkyl-4' -cyanobiphenyl according to claim 2, wherein in the step a, the catalyst is at least one of aluminum trichloride, zinc chloride or iron trichloride; and/or
In the step a, the first solvent is at least one of tetrahydrofuran, ethyl acetate, methyl tert-butyl ether or petroleum ether.
5. The method for preparing 4-alkyl-4' -cyanobiphenyl according to claim 2, wherein in step a, the molar ratio of biphenyl to bromine is 1; and/or
In the step a, the mass-to-volume ratio of the biphenyl to the first solvent is 1:2-5, the unit of mass is gram, and the unit of volume is milliliter.
6. The method for preparing 4-alkyl-4' -cyanobiphenyl according to claim 2, wherein in the step b, the second solvent is a mixed solution of tetrahydrofuran and xylene in a volume ratio of 1:1-4; and/or
The molar ratio of 4,4' -dibromobiphenyl to dialkyl copper lithium is 1:1-2; and/or
The mass-volume ratio of 4,4' -dibromobiphenyl to the second solvent is 1:3-5, the unit of mass is gram, and the unit of volume is milliliter.
7. The method of claim 2, wherein in step c, the third solvent is at least one of dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, sulfolane, or xylene; and/or
The molar ratio of the 4-alkyl-4' -bromobiphenyl to the cuprous cyanide is 1:1-2; and/or
The mass-volume ratio of the 4-alkyl-4' -bromobiphenyl to the third solvent is 1:3-6, the unit of mass is gram, and the unit of volume is milliliter.
8. The method of preparing 4-alkyl-4' -cyanobiphenyl according to claim 3, wherein the fourth solvent is at least one of tetrahydrofuran, dehydrated ether, methyl t-butyl ether or petroleum ether; and/or
The temperature of the first-stage reaction is-40 ℃ to-20 ℃, and the time is 0.5h to 6h.
9. The method of preparing 4-alkyl-4' -cyanobiphenyl according to claim 3, wherein the fifth solvent is at least one of tetrahydrofuran, dehydrated ether, dioxane, methyl tert-butyl ether, toluene, benzene, or petroleum ether; and/or
The temperature of the secondary reaction is-70 ℃ to-20 ℃, and the time is 4h to 8h.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015792A (en) * | 1988-04-22 | 1991-05-14 | Rhone-Poulenc Chimie | Preparation of 4,4'-dibromobiphenyl |
| US5998652A (en) * | 1997-01-21 | 1999-12-07 | Sumika Fine Chemicals Co., Ltd. | Process for preparing 2-cyanobiphenyl compound |
| US20050101063A1 (en) * | 2000-10-24 | 2005-05-12 | Tour James M. | Three-terminal field-controlled molecular devices |
| CN1876622A (en) * | 2005-06-07 | 2006-12-13 | 烟台万润精细化工有限责任公司 | Process for preparing alkylcyanobenzenes |
| CN103012201A (en) * | 2012-12-03 | 2013-04-03 | 滕州市悟通香料有限责任公司 | Synthetic method of 2-cyano-4'-methyl diphenyl |
| CN106518647A (en) * | 2015-09-11 | 2017-03-22 | 中国石油天然气股份有限公司 | synthesis method of alkyl salicylic acid |
| CN114395206A (en) * | 2022-01-25 | 2022-04-26 | 杨晓杰 | High-temperature-resistant engineering plastic and production method thereof |
-
2022
- 2022-11-02 CN CN202211363361.3A patent/CN115745833B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015792A (en) * | 1988-04-22 | 1991-05-14 | Rhone-Poulenc Chimie | Preparation of 4,4'-dibromobiphenyl |
| US5998652A (en) * | 1997-01-21 | 1999-12-07 | Sumika Fine Chemicals Co., Ltd. | Process for preparing 2-cyanobiphenyl compound |
| US20050101063A1 (en) * | 2000-10-24 | 2005-05-12 | Tour James M. | Three-terminal field-controlled molecular devices |
| CN1876622A (en) * | 2005-06-07 | 2006-12-13 | 烟台万润精细化工有限责任公司 | Process for preparing alkylcyanobenzenes |
| CN103012201A (en) * | 2012-12-03 | 2013-04-03 | 滕州市悟通香料有限责任公司 | Synthetic method of 2-cyano-4'-methyl diphenyl |
| CN106518647A (en) * | 2015-09-11 | 2017-03-22 | 中国石油天然气股份有限公司 | synthesis method of alkyl salicylic acid |
| CN114395206A (en) * | 2022-01-25 | 2022-04-26 | 杨晓杰 | High-temperature-resistant engineering plastic and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 未本美 等: "4-烷基-4′-氰基联苯的合成新方法", 《化学世界》, no. 03, pages 169 - 171 * |
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