CN1966608A - Method for preparing biphenyl monomer liquid crystal by using cross-coupling reaction - Google Patents
Method for preparing biphenyl monomer liquid crystal by using cross-coupling reaction Download PDFInfo
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- CN1966608A CN1966608A CN 200610070270 CN200610070270A CN1966608A CN 1966608 A CN1966608 A CN 1966608A CN 200610070270 CN200610070270 CN 200610070270 CN 200610070270 A CN200610070270 A CN 200610070270A CN 1966608 A CN1966608 A CN 1966608A
- Authority
- CN
- China
- Prior art keywords
- biphenyl
- liquid crystal
- propyl group
- monomer liquid
- toluene
- Prior art date
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Links
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 title claims abstract description 34
- 239000004305 biphenyl Substances 0.000 title claims abstract description 30
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006880 cross-coupling reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 84
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- ZCJAYDKWZAWMPR-UHFFFAOYSA-N 1-chloro-2-fluorobenzene Chemical compound FC1=CC=CC=C1Cl ZCJAYDKWZAWMPR-UHFFFAOYSA-N 0.000 claims description 7
- TYBHZVUFOINFDV-UHFFFAOYSA-N 2-bromo-6-[(3-bromo-5-chloro-2-hydroxyphenyl)methyl]-4-chlorophenol Chemical compound OC1=C(Br)C=C(Cl)C=C1CC1=CC(Cl)=CC(Br)=C1O TYBHZVUFOINFDV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 aryl boric acid Chemical compound 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 150000002940 palladium Chemical class 0.000 claims description 6
- 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 description 5
- 239000000047 product Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- GJPUXKDUNLNCRU-UHFFFAOYSA-N B(O)(O)O.C(C)C1=CC=CC=C1 Chemical compound B(O)(O)O.C(C)C1=CC=CC=C1 GJPUXKDUNLNCRU-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 4
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- UAGWMIDWWYHFNL-UHFFFAOYSA-N 1,1'-biphenyl;dicyclohexylphosphane Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C1CCCCC1PC1CCCCC1 UAGWMIDWWYHFNL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007818 Grignard reagent Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 241000237502 Ostreidae Species 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- ZOROAHFBYYBDJJ-UHFFFAOYSA-N boric acid propylbenzene Chemical compound B(O)(O)O.C(CC)C1=CC=CC=C1 ZOROAHFBYYBDJJ-UHFFFAOYSA-N 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 2
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims description 2
- 238000003379 elimination reaction Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 150000004795 grignard reagents Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 235000020636 oyster Nutrition 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical group C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 238000005502 peroxidation Methods 0.000 claims 1
- 235000015598 salt intake Nutrition 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000006193 diazotization reaction Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XTCLDSFWDBMXKQ-XYPYZODXSA-N CC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1Cl Chemical compound CC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1Cl XTCLDSFWDBMXKQ-XYPYZODXSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing biphenyl monomer liquid crystal by using cross coupling reaction, the structure of which is represented by formula , wherein n is 1 or 2, R1＝C1～C10Straight chain alkyl radical, R2F or C1～C10Straight chain alkyl or OCF3A ═ cyclohexyl or phenyl, X, Y, Z, W ═ F or H atoms, and at least one of X and Y is an F atom. The method takes a chemical formula (II) as a raw material, and the raw material and a chemical formula (III) are subjected to cross coupling reaction under the catalytic action of palladium to generate various biphenyl monomer liquid crystals. The preparation method has the advantages of simple process, mild reaction conditions and low production cost, and is environment-friendly, so the preparation method is particularly suitable for industrial production of the fluorine-containing 4- (4' -alkylcyclohexyl) biphenyl monomer liquid crystal on the benzene ring.
Description
Technical field
The present invention relates to a kind of method for preparing biphenyl-like monomer liquid crystal, especially a kind of method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal belongs to preparation method's technical field of monomer liquid crystal.
Background technology
4-(4 '-alkyl-cyclohexyl) biphenyl-like monomer liquid crystal generally all has low fusing point, and high clearing point and lower viscosity are simultaneously, good with other monomer liquid crystal consistencies.So in the liquid-crystal display of STN type, a large amount of application is arranged.The nineteen eighty-three Merck US4545922 of house journal discloses a kind of preparation method of fluorine-containing biphenyl-like monomer liquid crystal:
This synthetic route exists many shortcomings:
1, nitrated, the diazotization reaction on the phenyl ring has a large amount of side reaction generations, directly causes product yield low;
2, nitrated and diazotization reaction has a large amount of spent acid, exhaust gas discharging, and environment is polluted;
3, synthetic route is unreasonable, with
For raw material carries out synthetic route nitrated, that diazotization is produced product, can cause high production cost.
The patent DE4220082 in 1993 of Merck company discloses another synthetic route:
Though this synthetic route has been avoided many by products such as direct nitrated, diazotization, the high pollution reaction, used highly basic BuLi is extremely inflammable and explosive for the phenyl ring metal ionization, and also is difficult to reach on-70 ℃ the temperature of reaction condition industrial production.
Summary of the invention
The objective of the invention is to overcome the shortcoming that above-mentioned prior art exists, provide a kind of and can reduce production costs, reduce pollution, satisfy the preparation method of synthetic 4-(4 '-alkyl-cyclohexyl) biphenyl-like monomer liquid crystal of industrial production needs environment.
Purpose of the present invention can reach by following measure:
Utilize cross-coupling reaction to prepare the method for biphenyl-like monomer liquid crystal, its special character is that the synthetic route of this biphenyl-like monomer liquid crystal is
Promptly use the aryl boric acid that has substituent aryl chloride complex and multiple replacement to carry out cross-coupling reaction to prepare required biphenyl-like monomer liquid crystal.
Wherein A=cyclohexyl or phenyl, X, Y, Z, W=F or H atom, X, Y have at least one to be F atom, n=1 or 2, R
1=C
1～C
10, R
2=F or OCF
3Or C
1～C
10The used catalyzer of cross-coupling reaction is PdCl
2, Pd (OAC)
2, Pd (NO
3)
2Deng palladium salt,
Wherein preferred PdCl
2The consumption of palladium salt is a raw material in the reaction
0.1 of mole number～2 ‰, wherein preferred 0.8-1.2 ‰;
The part of palladium catalyst salt is tricyclohexyl phosphine, tri-butyl phosphine, two diamantane normal-butyl phosphines, biphenyl dicyclohexyl phosphine etc., wherein preferred tri-butyl phosphine; The part consumption is 1～3 times of palladium salt mole number, wherein preferred 3 times; The alkali that reacts used is Na
2CO
3, KOH, K
3PO
43H
2O, KF etc., wherein preferred KF; Reaction solvent is the mixed solvent of organic solvent such as THF, DMF, DMA and water, the mixed solvent of wherein preferred THF and water; 70～110 ℃ of temperature of reaction, wherein preferred 70-80 ℃; 4～10 hours reaction times, wherein preferred 5-6 hour.
The present invention compared with prior art has following positively effect:
(1) avoided inflammable, explosive alkaline such as n-Butyl Lithium (BuLi), diisopropylamine lithium (LDA) to use in the preparation route, made preparation technology's enforcement have more security;
(2) reduced a series of loaded down with trivial details steps such as nitrated, diazotization in the past technology, on the basis of existing raw material, only promptly obtained target product, shortened synthesis cycle, thereby reduced production cost by a step cross-coupling reaction;
(3) owing to avoided nitrated, the diazotization reaction of phenyl ring, thereby significantly reduced spent acid, exhaust gas discharging, reduced pollution, so more feasible on industrial production to environment.
The preparation method of 4-disclosed by the invention (4 '-alkyl-cyclohexyl) biphenyl-like monomer liquid crystal is applicable to following monomer liquid crystal:
2,3 ', 4 '-three fluoro-4-(anti--the 4-alkyl-cyclohexyl) biphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
2,6,3 ', 4 ', 5 '-five fluoro-4-(anti--the 4-alkyl-cyclohexyl) biphenyl [structural formula:
2,6,3 ', 5 '-tetrafluoro-4 '-trifluoromethoxy-4-(anti--the 4-alkyl-cyclohexyl) biphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
2,3 ', 5 '-three fluoro-4 '-trifluoromethoxy-4-(anti--the 4-alkyl-cyclohexyl) biphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
2,3 ', 4 ', 5 '-tetrafluoro-4-(anti--the 4-alkyl-cyclohexyl) biphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
2,6,3 ', 4 ', 5 '-five fluoro-4-(anti--the 4-alkyl-cyclohexyl) biphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
2-fluoro-4 '-alkyl-4-(anti--the 4-alkyl-cyclohexyl) biphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
4-alkyl-2 '-fluoro-4 " alkyl [1,1 '; 4 ', 1 "] terphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
3,4,2 ', 6 '-tetrafluoro-(anti--4 '-(anti--4 '-alkyl dicyclohexyl) biphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
3,4,5,2 ', 6 '-five fluoro-(anti--4 '-(anti--4 " the alkyl dicyclohexyl) biphenyl [structural formula:
], R=C
1～C
10Straight chained alkyl.
Embodiment
Below provide the specific embodiment of the present invention, be used for that the invention will be further described, but the present invention is not limited to following embodiment.
Embodiment 1:
1.1: raw material 4-(trans-4 '-propyl group cyclohexyl)-2-fluorochlorobenzene [structural formula:
] preparation
The magnesium chips of 12.2g (0.5mol) is added in the 1L there-necked flask, and 104.8g (0.5mol) 2-fluoro-is miscible in the 300ml tetrahydrofuran (THF) to bromochlorophene, is added dropwise in the there-necked flask a little, be warming up to 70 ℃, initiation reaction drips remaining 2-fluoro-to bromochlorophene solution, dropwise, insulation refluxed 1 hour.70.0g (0.5mol) is dissolved in the 100ml tetrahydrofuran (THF) the propyl group pimelinketone, splashes in the Grignard reagent that above-mentioned reaction obtains, dropwise insulation 1.5 hours, add hydrolysis in the dilute hydrochloric acid then, with 600ml toluene extraction three times, merge organic phase, be washed to neutrality, the p-methyl benzenesulfonic acid of 8.6g (0.05mol) is added in the above-mentioned toluene solution, temperature rising reflux divides water to toluene not have in mutually till the tangible water, cooling, and organic phase is washed to neutrality, slough toluene, get 120g
4-(4 '-the propyl group tetrahydrobenzene)-the 2-fluorochlorobenzene [structural formula:
], GC:95%.
120g 4-(4 '-propyl group tetrahydrobenzene)-2-fluorochlorobenzene, 35g Raney's nickel, 700ml toluene are added in the 1L autoclave, and hydrogen was defeated to try hard to keep and is held 20atm in the still, in 50 ℃ of insulations 5 hours, then, cooling release, elimination Raney's nickel, slough toluene, obtain suitable, the anti-blended of 120g
4-(4 '-the propyl group cyclohexyl)-the 2-fluorochlorobenzene [structural formula:
GC:95%.
In the 1L reaction flask, add the 400ml ethylene dichloride, lower the temperature 5 ℃, add 62.7g (0.47mol) aluminum chloride, add the 76.3g sherwood oil then, temperature is controlled at below 5 ℃, is added dropwise to suitable, the trans blended 4-of the above-mentioned 120g that obtains (0.47mol) (4 '-propyl group cyclohexyl)-2-fluorochlorobenzene, in 0～5 ℃ of insulation 6-8 hour, pour hydrolysis in the frozen water into, organic phase is washed to neutrality, sloughs ethylene dichloride, the fraction of underpressure distillation collection more than 130 ℃ under 20Pa obtains 97.2g again
4-(trans-4 '-propyl group cyclohexyl)-2-fluorochlorobenzene [structural formula:
], GC:95%, yield: 80%.
Use similar preparation method, can obtain following compound:
4-(trans-4 '-amyl group cyclohexyl) 2-fluorochlorobenzene [structural formula:
], GC:95%, yield: 80%.
4-(trans-4 '-ethyl cyclohexyl) 2-fluorochlorobenzene [structural formula:
], GC:96%, yield: 81.5%.
1.2: product 2-fluoro-4 '-ethyl-4-(4 " the propyl group cyclohexyl) biphenyl [structural formula:
] preparation:
With 89.0g (0.35mol0's) 4-(trans-4 '-propyl group cyclohexyl) 2-fluorochlorobenzene, 52.4g (0.35mol) to ethylbenzene boric acid, 20.3g Potassium monofluoride (0.35mol), 9.3g (0.035mol) Tetrabutyl amonium bromide, the 850ml tetrahydrofuran (THF), 170ml water adds in the 2L there-necked flask, adds 62mg (3.5 * 10 again
-4Mol) Palladous chloride, 0.14g (70 * 10
-4Mol) tri-butyl phosphine, stirring is warming up to 60-80 ℃, room temperature is reduced in insulation backflow 4-6 hour then, adds 500ml toluene, wash three times to neutral, slough toluene, obtain 106g oily matter crude product, again underpressure distillation under 20Pa, collect the fraction of top temperature more than 190 ℃, obtain 97.5g oyster white oily matter.
With the sherwood oil recrystallization of 1ml/1g 2～3 times, the resulting white crystal of recrystallization is with petroleum ether dissolution, and an amount of excessively aluminium sesquioxide chromatography column is sloughed sherwood oil then, and vacuum-drying obtains 74.2g
2-fluoro-4 '-ethyl-4-(anti--4 " the propyl group cyclohexyl) biphenyl [structural formula
2-fluoro-4 '-ethyl-4-(anti--4-amyl group cyclohexyl) biphenyl [structural formula:
2-fluoro-4 '-amyl group-4-(anti--4-amyl group cyclohexyl) biphenyl [structural formula:
]，mp：29℃，cp：131℃。
Embodiment 2:
2.1: raw material 4 '-propyl group-3-fluoro-4-chlordiphenyl [structural formula:
] preparation
With 73.8g (0.45mol) to propylbenzene boric acid, the 2-fluorine of 93.8g (0.45mol) is to bromochlorophene, the potassium hydroxide of 100.8g (1.8mol), 2.25g hexaoxacyclooctadecane-6 (0.009mol)-6, the 400ml tetrahydrofuran (THF), 400ml water adds in the 2L there-necked flask, adds 1.1g (9 * 10 again
-4Mol) four triphenylphosphines close palladium, stir and are warming up to 70 ℃, and insulation refluxed 2 hours, reduced to room temperature, add 400ml toluene, add dilute hydrochloric acid and be acidified to slightly acidic, tell organic phase, be washed to neutrality, slough toluene, crude product obtains 89.5g with the industrial alcohol recrystallization of 2ml/1g
4 '-propyl group-3-fluoro-4-chlordiphenyl [structural formula:
] GC:99.5%.
2.2:4-ethyl-2 '-fluoro-4 " propyl group (1,1 '; 4 ', 1 ") terphenyl [structural formula:
] preparation
With 4 of 87g (0.35mol) '-propyl group-3-fluoro-4-chlordiphenyl, 52.4g (0.35mol) to ethylbenzene boric acid, 20.3g (0.35mol) Potassium monofluoride, 9.3g Tetrabutyl amonium bromide (0.035mol), the 850ml tetrahydrofuran (THF), 170ml water joins in the 2L there-necked flask, adds 62mg (3.5 * 10 again
-4Mol) Palladous chloride, 0.14g (7 * 10
-4Mol) tri-butyl phosphine is warming up to 70 ℃, and insulation refluxed 5 hours, and cooling adds 500ml toluene, washes three times to neutral, sloughs toluene, obtains the 111g yellow oil.
(dehydrated alcohol/sherwood oil=2/1, v/v), resulting white crystal dissolves with an amount of toluene, crosses the appropriate amount of alumina chromatography column, sloughs toluene, in 90 ℃ of following vacuum-dryings 5 hours, obtains 89g with the mixed solvent recrystallization of dehydrated alcohol and sherwood oil
4-ethyl-2 '-fluoro-4 " propyl group (1,1 ' 34 ', 1 ") terphenyl [structural formula
]GC：99.9％，mp：78.8～80.1℃，cp：132.2～132.3℃。
Embodiment 3:
3.1: according to the similarity method of embodiment 1.1, can obtain following compounds
2,6-two fluoro-4-(anti-, anti--4 '-the propyl group dicyclohexyl) chlorobenzene [structural formula:
]，mp：75.4～78.0℃，cp：139.8～140.3℃。
2,6-two fluoro-4-(anti-, anti--4 '-the amyl group dicyclohexyl) chlorobenzene [structural formula:
3.2: according to the similarity method of embodiment 1.2, can obtain the compound of following monomer liquid crystal:
3,4,2 ', 6 '-tetrafluoro-4 '-(4 '-the propyl group dicyclohexyl) biphenyl [structural formula:
3,4,5,2 ', 6 '-five fluoro-4 '-(4 '-the amyl group dicyclohexyl) biphenyl [structural formula:
Embodiment 4:
According to the similarity method of embodiment 1.2, can obtain the compound of following monomer liquid crystal:
2,6-two fluoro-4 '-trifluoromethoxy-4-(4-amyl group cyclohexyl) biphenyl [structural formula:
], mp:86 ℃, cp:67 ℃.
2,6-two fluoro-4 '-trifluoromethoxy-4-(4-propyl group cyclohexyl) biphenyl [structural formula:
], mp:86 ℃, cp:67 ℃.
Embodiment 5:
According to the similarity method of embodiment 1.2, can obtain the compound of following monomer liquid crystal:
2,3 ', 4 '-three fluoro-4-(anti--4-propyl group cyclohexyl) biphenyl [structural formula:
], mp:42 ℃, cp:59 ℃.
2,3 ', 4 '-three fluoro-4-(anti--4-amyl group cyclohexyl) biphenyl [structural formula:
], mp:17 ℃, cp:52 ℃.
2,6,3 ', 4 '-tetrafluoro-4-(anti--4-propyl group cyclohexyl) biphenyl [structural formula:
], mp:81 ℃, cp:19 ℃.
2,6,3 ', 4 '-tetrafluoro-4-(anti--4-amyl group cyclohexyl) biphenyl [structural formula:
], mp:72 ℃, cp:34 ℃.
Embodiment 6:
According to the similarity method of embodiment 1.2, can obtain the compound of following monomer liquid crystal:
2,3 ', 4 ' 5 '-tetrafluoro-4-(anti--4-amyl group cyclohexyl) biphenyl [structural formula:
], mp:63 ℃, cp:37 ℃.
2,3 ', 4 ' 5 '-tetrafluoro-4-(anti--4-propyl group cyclohexyl) biphenyl [structural formula:
], mp:64 ℃, cp:25 ℃.
2,6,3 ', 4 ' 5 '-five fluoro-4-(anti--4-amyl group cyclohexyl) biphenyl [structural formula:
], mp:114 ℃.
Claims (9)
1, utilize cross-coupling reaction to prepare the method for biphenyl-like monomer liquid crystal, the structure representative formula of this biphenyl-like monomer liquid crystal is:
, wherein, n=1 or 2, R
1=C
1～C
10Straight chained alkyl, R
2=F or OCF
3Or C
1～C
10Straight chained alkyl, A=cyclohexyl or phenyl, X, Y, Z, W=F or H atom, at least one is the F atom for X, Y, it is characterized in that the synthetic of this biphenyl-like monomer liquid crystal
The aryl boric acid that use has substituent aryl chloride complex and multiple replacement carries out cross-coupling reaction to prepare required biphenyl-like monomer liquid crystal
Route is
2,, it is characterized in that the used raw material of cross-coupling reaction is for being by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 1
With
The catalyzer that reacts used is PdCl
2Or Pd (OAC)
2Or Pd (NO
3)
2Palladium salt; The used part of catalyzer is tricyclohexyl phosphine or tri-butyl phosphine or two diamantane normal-butyl phosphines or biphenyl dicyclohexyl phosphine; The alkali that reacts used is Na
2CO
3Or KOH or K
3PO
43H
2O or KF; The solvent that reacts used is the mixed solvent of THF or DMF or DMA organic solvent and water; 4～10 hours reaction times, 70～110 ℃ of temperature of reaction, the consumption of catalysts palladium salt is a raw material
0.1 of mole number～2 ‰.
3, by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 2, it is characterized in that reacting the preferred PdCl of catalyst system therefor
2, the preferred tri-butyl phosphine of part of reaction catalyst system therefor palladium salt reacts the used preferred KF of alkali, reacts the used preferred THF of solvent and the mixed solvent of water.
4,, it is characterized in that palladium salt consumption is a raw material in the reaction by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 2
The 0.8-1.2 ‰ of mole number.
5,, it is characterized in that the preferred 70-80 of temperature of reaction ℃, preferred 5-6 of reaction times hour by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 2.
6, by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 2, it is characterized in that raw material 4-(trans-4 '-propyl group cyclohexyl)-2-fluorochlorobenzene [structural formula:
] preparation
(1) magnesium chips is added in the bottle, the 2-fluoro-is miscible in tetrahydrofuran (THF) to bromochlorophene, is added dropwise in the bottle, is warming up to 70 ℃, and initiation reaction drips the 2-fluoro-to bromochlorophene solution, and insulation refluxed 1 hour;
(2) will be dissolved in the tetrahydrofuran (THF) the propyl group pimelinketone, splash in the Grignard reagent that above-mentioned reaction obtains, dropwise insulation 1-2 hour, add hydrolysis in the dilute hydrochloric acid then, with toluene extraction three times, merge organic phase, be washed to neutrality, p-methyl benzenesulfonic acid is added in the above-mentioned toluene solution, temperature rising reflux divides water to toluene not have in mutually till the tangible water, cooling, and organic phase is washed to neutrality, slough toluene,
4-(4 '-the propyl group tetrahydrobenzene)-the 2-fluorochlorobenzene [structural formula:
];
(3) 4-(4 '-propyl group tetrahydrobenzene)-2-fluorochlorobenzene, Raney's nickel, toluene are added in the autoclave, hydrogen is defeated to try hard to keep and is held 20atm in the still, when 40-60 ℃ of insulation 4-6, then, and the cooling release, the elimination Raney's nickel is sloughed toluene, obtains suitable, anti-blended
4-(4 '-the propyl group cyclohexyl)-the 2-fluorochlorobenzene [structural formula:
];
(4) in the reaction flask, add ethylene dichloride, lower the temperature 5 ℃, add aluminum chloride, add sherwood oil then, temperature is controlled at below 5 ℃, is added dropwise to above-mentioned suitable, the trans blended 4-that obtains (4 '-propyl group cyclohexyl)-2-fluorochlorobenzene, in 0～5 ℃ of insulation 6-8 hour, pour hydrolysis in the frozen water into, organic phase is washed to neutrality, sloughs ethylene dichloride, fraction more than 130 ℃ is collected in underpressure distillation under 20Pa again, obtain 4-(trans-4 '-propyl group cyclohexyl)-2-fluorochlorobenzene [structural formula:
].
7, by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 2, it is characterized in that product 2-fluoro-4 '-ethyl-4-(4 " propyl group cyclohexyl) biphenyl [structural formula:
] preparation:
(1) with 4-(trans-4 '-propyl group cyclohexyl) 2-fluorochlorobenzene, to ethylbenzene boric acid, Potassium monofluoride, Tetrabutyl amonium bromide, tetrahydrofuran (THF), water adds in the bottle, add Palladous chloride again, tri-butyl phosphine stirs and is warming up to 60-80 ℃, room temperature is reduced in insulation backflow 4-6 hour then, adds toluene, wash three times to neutral, slough toluene, obtain the oily matter crude product, the fraction of top temperature more than 190 ℃ collected in underpressure distillation under 20Pa again, obtains oyster white oily matter;
(2) with sherwood oil recrystallization 2～3 times, the resulting white crystal of recrystallization is with petroleum ether dissolution, and an amount of excessively aluminium sesquioxide chromatography column is sloughed sherwood oil then, vacuum-drying, obtain 2-fluoro-4 '-ethyl-4-(anti--4 " propyl group cyclohexyl) biphenyl [structural formula
].
8, by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 2, it is characterized in that raw material 4 '-propyl group-3-fluoro-4-chlordiphenyl [structural formula:
] preparation
Will be to propylbenzene boric acid, the 2-fluorine is to bromochlorophene, potassium hydroxide, hexaoxacyclooctadecane-6-6, tetrahydrofuran (THF), water add in the bottle, add four triphenylphosphines again and close palladium, stir and be warming up to 70 ℃, insulation refluxed 2 hours, reduce to room temperature, add toluene, add dilute hydrochloric acid and be acidified to slightly acidic, tell organic phase, be washed to neutrality, slough toluene, crude product obtains with the industrial alcohol recrystallization
4 '-propyl group-3-fluoro-4-chlordiphenyl [structural formula:
].
9, by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 2, it is characterized in that 4-ethyl-2 '-fluoro-4 " propyl group (1,1 '; 4 ', 1 ") terphenyl [structural formula:
] preparation
With 4 '-propyl group-3-fluoro-4-chlordiphenyl, to ethylbenzene boric acid, Potassium monofluoride, Tetrabutyl amonium bromide, tetrahydrofuran (THF), water, join in the bottle, add Palladous chloride, tri-butyl phosphine again, be warming up to 70 ℃, insulation refluxed 5 hours, cooling, add toluene, wash three times to neutral, slough toluene, obtain yellow oil;
With the mixed solvent recrystallization of dehydrated alcohol and sherwood oil (dehydrated alcohol/sherwood oil=2/1, v/v), resulting white crystal dissolves with toluene, peroxidation aluminium chromatography column is sloughed toluene, in 90 ℃ of following vacuum-dryings 5 hours, obtains
4-ethyl-2 '-fluoro-4 " propyl group (1,1 ' 34 ', 1 ") terphenyl [structural formula
].
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