CN1966608B - Method for preparing biphenyl-like monomer liquid crystal using cross-coupling reaction - Google Patents
Method for preparing biphenyl-like monomer liquid crystal using cross-coupling reaction Download PDFInfo
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- CN1966608B CN1966608B CN2006100702705A CN200610070270A CN1966608B CN 1966608 B CN1966608 B CN 1966608B CN 2006100702705 A CN2006100702705 A CN 2006100702705A CN 200610070270 A CN200610070270 A CN 200610070270A CN 1966608 B CN1966608 B CN 1966608B
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Abstract
The invention relates to a way to prepare biphenyl metamer mesophase through crossed coupling reaction. The representative structure formula is (I) of which n stands for 1 or 2, R1 stands for C1-C10 linear chain alkane, R2 stands for F or C1-C10 linear chain alkane or OCF3, A stands for cyclohexyl or phenyl, X,Y,Z,W stands for F or H atom, at least one of X and Y is F atom. The method in the invention adopts (II) as the material and palladium as the catalyst, (II) and (III) react to produce different kinds of biphenyl metamer mesophase; the reaction is crossed coupling reaction. The inventionhas simple procedures, mild reacting conditions, low cost and environment-friendly, it's especially applicable to the production of 4-(4'-aldl cyclohexyl) biphenyl metamer mesophase whose benzene ring contains fluoric.
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:
], R=C
1～C
10Straight chained alkyl.
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, hydrogen is defeated to try hard to keep and is held 20atm in the still, in 50 ℃ of insulations 5 hours, then, the cooling release, the elimination Raney's nickel is sloughed toluene, obtain suitable, the anti-blended 4-of 120g (4 '-propyl group cyclohexyl)-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
], mp:41.0～41.4 ℃, cp:114.9～115.1 ℃, GC:99.9%.Use similar preparation method, can obtain following monomer liquid crystal:
2-fluoro-4 '-ethyl-4-(anti--4-amyl group cyclohexyl) biphenyl [structural formula:
], mp:37.2～38 ℃, cp:117.8～118 ℃.
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:
], mp:66.5～68.3 ℃, cp:136.2～136.4 ℃.
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:
], mp:133 ℃, cp:242 ℃.
3,4,5,2 ', 6 '-five fluoro-4 '-(4 '-the amyl group dicyclohexyl) biphenyl [structural formula:
], mp:156 ℃, cp:211 ℃.
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 (8)
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 aryl boric acid that in this biphenyl-like monomer liquid crystal synthetic use has substituent aryl chloride complex and a multiple replacement carries out cross-coupling reaction to prepare required biphenyl-like monomer liquid crystal, synthetic route is
Wherein the used raw material of cross-coupling reaction is
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 part consumption is 1-3 a times of palladium salt mole number; 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 ‰.
2. by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 1, it is characterized in that reacting catalyst system therefor is PdCl
2, the part of reaction catalyst system therefor palladium salt is a tri-butyl phosphine, and the alkali that reacts used is KF, and the solvent that reacts used is the mixed solvent of THF and water.
3. by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 1, it is characterized in that palladium salt consumption is a raw material in the reaction
The 0.8-1.2 ‰ of mole number.
4. by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 1, it is characterized in that temperature of reaction is 70-80 ℃, the reaction times is 5-6 hour.
5. by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 1, 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 pressure keeps 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 ℃, be 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, slough ethylene dichloride, fraction more than 130 ℃ is collected in underpressure distillation under 20Pa again, obtains 4-(trans-4 '-propyl group cyclohexyl)-2-fluorochlorobenzene, structural formula
6. by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 1, 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, and vacuum-drying obtains
2-fluoro-4 '-ethyl-4-(anti--4 " the propyl group cyclohexyl) biphenyl, structural formula
7. by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 1, 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:
8. by the described method of utilizing cross-coupling reaction to prepare biphenyl-like monomer liquid crystal of claim 1, it is characterized in that 4-ethyl-2 '-fluoro-4 " the propyl group 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 wherein, v/v, resulting white crystal dissolves with toluene, and peroxidation aluminium chromatography column is sloughed toluene, in 90 ℃ of following vacuum-dryings 5 hours, obtain 4-ethyl-2 '-fluoro-4 " propyl group terphenyl, structural formula
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| CN1594333A (en) * | 2004-06-25 | 2005-03-16 | 大连理工大学 | Process for synthesizing liquid crystal compound by catalytic cross-coupling of diphenyl-phosphino- palladium acetate |
| CN1686972A (en) * | 2005-03-22 | 2005-10-26 | 大连理工大学 | Cross couple method for synthesizing compound of liquid crystal from 2-2 phenyl phosphine ethanol through palladium catalysis |
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2006
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| DE4220065A1 (en) * | 1992-06-19 | 1993-12-23 | Merck Patent Gmbh | Linear poly:cyclic pyrimidine and 2-phenyl-5-bromo-pyrimidine cpds. - aare useful in liquid crystal medium and as intermediates |
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| EP1160233B1 (en) * | 2000-06-02 | 2004-07-21 | Sharp Kabushiki Kaisha | Novel terphenyl compounds |
| CN1594333A (en) * | 2004-06-25 | 2005-03-16 | 大连理工大学 | Process for synthesizing liquid crystal compound by catalytic cross-coupling of diphenyl-phosphino- palladium acetate |
| CN1686972A (en) * | 2005-03-22 | 2005-10-26 | 大连理工大学 | Cross couple method for synthesizing compound of liquid crystal from 2-2 phenyl phosphine ethanol through palladium catalysis |
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| 郭孟萍 等.PO环钯配合物的合成及对Suzuki交叉偶联反应的催化性能.《应用化学》.2006,480-483. |
| 郭孟萍等.P N配位的环钯配合物催化Suzuki偶联合成含氟液晶化合物的研究.《分子催化》.2006 |
| 郭孟萍等.P,N配位的环钯配合物催化Suzuki偶联合成含氟液晶化合物的研究.《分子催化》.2006,203-206. * |
| 郭孟萍等.PO环钯配合物的合成及对Suzuki交叉偶联反应的催化性能.《应用化学》.2006,480-483. * |
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| CN1966608A (en) | 2007-05-23 |
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