CN100372825C - 3,4-difluoro-2-methoxyl biphenyl derivative and its prepn process and application - Google Patents
3,4-difluoro-2-methoxyl biphenyl derivative and its prepn process and application Download PDFInfo
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- CN100372825C CN100372825C CNB2005100630740A CN200510063074A CN100372825C CN 100372825 C CN100372825 C CN 100372825C CN B2005100630740 A CNB2005100630740 A CN B2005100630740A CN 200510063074 A CN200510063074 A CN 200510063074A CN 100372825 C CN100372825 C CN 100372825C
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- FIJVWEAUZSIQRJ-UHFFFAOYSA-N 1,2-difluoro-3-methoxy-4-phenylbenzene Chemical group COC1=C(F)C(F)=CC=C1C1=CC=CC=C1 FIJVWEAUZSIQRJ-UHFFFAOYSA-N 0.000 title description 5
- 238000000034 method Methods 0.000 title description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004305 biphenyl Substances 0.000 claims abstract description 43
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 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 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- 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 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 7
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- DNXSLLIDTGLIHX-UHFFFAOYSA-N 1-bromo-3,4-difluoro-2-methoxybenzene Chemical compound COC1=C(F)C(F)=CC=C1Br DNXSLLIDTGLIHX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007818 Grignard reagent Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 9
- -1 3, 4-difluoro-2-methoxy biphenyl perylene derivative Chemical group 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 2
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The present invention discloses a 3, 4-difluoro-2-methoxyl group biphenyl perylene derivative and the preparation method and application. The structural formula of a 3, 4-difluoro-2-methoxy biphenyl perylene derivative provided by the present invention is a formula I, wherein R is an alkyl group, a is a right formula II, and m is equal to 0 or 1. A compound of the present invention introduces methoxy in a lateral direction of a biphenyl ring. The space volume of the base group is small, a couple distance is not long, and an average dipole direction is in a direction of a long shaft of a molecular. Therefore, the present invention is favorable to improve the dielectric anisotropy of compound moleculars in a molecular long shaft direction, can lower a melting point and can improve solubility. The present invention has wide application prospects in liquid crystal displays, particularly the field of TFT-LCD.
Description
Technical field
The present invention relates to organic compound and preparation method thereof and application, particularly relate to 3,4-difluoro-2-methoxyl biphenyl derivative and preparation method thereof, and this compound is in Application in LCD.
Background technology
Active matrix liquid crystal shows that (AM-LCD) invents in late nineteen seventies, but real applicationization is in the eighties mid-term.What mainly use at present is that tft liquid crystal shows (TFT-LCD), because its response speed is fast, colour picture display quality height, utilize this technology to realize the video image demonstration, be mainly used in TV, portable computer, desktop computer, pick up camera, mobile phone and various terminal display, become one of main direction of LCD development from now on.High speed development along with the TFT-LCD technology, TFT-LCD is more and more urgent to the requirement of high-performance liquid crystal material, especially for obtaining wideer operating temperature range, reduce driving voltage, realize the reduce power consumption of display device, the development dielectric anisotropy is big, and fusing point is low, and the wide high-performance liquid crystal material of mesomorphic temperature range is TFT with liquid crystal material research direction from now on.
People such as Gray have synthesized fluorine-containing Terphenyls compound and the cyclohexyl biphenyl compounds of side direction first and have been used for TFT--LCD (G.W.Gray, M.Hird etc, J.Chem.Soc.Perkin Trans.2,1989,2041～2053), though it is less that this compounds has nematic temperature range, the viscosity of broad, the fusing point height, solvability is bad.
Summary of the invention
The purpose of this invention is to provide a kind of 3,4-difluoro-2-methoxyl biphenyl derivative and preparation method thereof.
Provided by the present invention 3,4-difluoro-2-methoxyl biphenyl derivative, its structural formula are formula I,
Wherein, R is an alkyl;
A is
M=0 or 1.
R is preferably the alkyl that carbonatoms is 1-9, and as methyl, amyl group, nonyl etc., these alkyl can be straight chained alkyl or side chain.
More specifically, of the present invention 3, the 4-difluoro-2-methoxyl biphenyl derivative comprises:
4 '-methyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-ethyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-propyl group-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-butyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-amyl group-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-hexyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-heptyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-octyl group-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-nonyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-methylcyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the ethyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the propyl group cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the butyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the amyl group cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the hexyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the heptyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the octyl group cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the nonyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 "-and methyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and ethyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and propyl group-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and butyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and amyl group-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and hexyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and heptyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and octyl group-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and nonyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-the 5-methyl isophthalic acid, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-ethyl-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-propyl group-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-butyl-1,3 pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-amyl group-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-hexyl-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-heptyl-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-octyl group-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-nonyl-1, the 3-pyrimidine.
The preparation method of The compounds of this invention has two kinds of technical schemes:
Scheme one comprises the steps: 1) preparation 3,4-difluoro-2-methoxy boric acid: with 3,4-difluoro-2-methoxyl bromobenzene and MAGNESIUM METAL reaction generate Grignard reagent, with the trimethyl borate reaction, obtain structural formula after the hydrolysis suc as formula 3 of II, 4-difluoro-2-methoxy boric acid then; 2) preparation 3, the 4-difluoro-2-methoxyl biphenyl derivative: with structural formula suc as formula 3 of II, the compound of 4-difluoro-2-methoxy boric acid and structural formula such as formula III carries out linked reaction under catalyst action, obtain described 3, the 4-difluoro-2-methoxyl biphenyl derivative; Described catalyzer is that four (triphenylphosphines) close palladium;
Formula (II)
Wherein, step 2) temperature of reaction of described linked reaction is 90-100 ℃, and reaction solvent is benzene or dehydrated alcohol.Reaction equation is as follows:
Wherein, the definition of R, A, m is identical with formula I.
Scheme two comprises the steps: 1) the preparation structural formula is the compound of formula V: with structural formula is that compound and the MAGNESIUM METAL reaction of formula IV generates Grignard reagent, reacts with trimethyl borate then, obtains the compound that structural formula is formula V after the hydrolysis; 2) preparation 3, the 4-difluoro-2-methoxyl biphenyl derivative: with structural formula be the compound of formula V and structural formula suc as formula 3 of VI, 4-difluoro-2-methoxyl bromobenzene carries out linked reaction under catalyst action, obtain described 3, the 4-difluoro-2-methoxyl biphenyl derivative; Described catalyzer is that four (triphenylphosphines) close palladium;
Wherein, step 2) temperature of reaction of described linked reaction is 90-100 ℃, and reaction solvent is benzene or dehydrated alcohol.Reaction equation is as follows:
Another object of the present invention provides the purposes of The compounds of this invention.
The compounds of this invention has that Δ ε is big, and fusing point is low, the resistivity advantages of higher; it is a kind of well behaved liquid crystal display material; therefore, with of the present invention 3, the 4-difluoro-2-methoxyl biphenyl derivative is that the liquid crystal display material of main component also belongs to protection scope of the present invention.
The compounds of this invention has been introduced methoxyl group on the side direction of cyclohexyl biphenyl, because such group spatial volume is less, little and the average dipole direction of galvanic couple distance is in the molecular long axis direction, so not only help increasing the dielectric anisotropy of compound molecule in the molecular long axis direction, and can reduce fusing point, increase solvability, in liquid-crystal display, especially the TFT-LCD field has broad application prospects.
Embodiment
Embodiment 1, preparation 4 '-ethyl-3, the 4-difluoro-2-methoxyl biphenyl
1, preparation 3,4-difluoro-2-methoxy boric acid
In the 250ml there-necked flask, add 22.3g (0.1mol) 3,4-difluoro-2-methoxyl bromobenzene, the 50ml tetrahydrofuran (THF), 2.43g (0.1mol) MAGNESIUM METAL and 1～2 iodine, stirring reaction 1 hour after the initiation reaction at room temperature, system temperature is reduced to-70 ℃ with ethanol-liquid nitrogen system then, under this temperature, slowly drip 10.4g (0.1mol) trimethyl borate, dropwising the back makes it rise to room temperature naturally under agitation condition, dripping 10% HCl solution to pH value then is 1, is heated to 100 ℃ and refluxes 1 hour down.With behind the petroleum ether extraction water of 100ml * 3, use the saturated common salt water washing again reaction solution cooling back, spend the night with anhydrous sodium sulfate drying to neutral.Dried solution revolved steam solution, obtain 15.993,4-difluoro-2-methoxy boric acid, yield 85%.
2, preparation 4 '-ethyl-3, the 4-difluoro-2-methoxyl biphenyl
In the 250ml there-necked flask, add 15.9g (0.085mol) 3,4-difluoro-2-methoxy boric acid, 15.7g4-ethyl bromobenzene, 100ml benzene, 50ml dehydrated alcohol, 25g yellow soda ash, 6.6g water and 1.96g four (triphenylphosphine) close palladium, are heated to 90 ℃ of 24 hours postcooling that reflux down to room temperature.Tell organic phase,, merge the organic phase after washing, use anhydrous sodium sulfate drying to neutral with 50ml * 3 chloroform extraction waters.Dried solution revolved steam solution, obtain 15.8g4 '-ethyl-3,4-difluoro-2-methoxyl biphenyl, yield 75%.
DSC (differential scanning calorimeter): Cr13.1I;
IR：3010，2966，2933，2873，1614，1495，1471，1429，1408，1313，1279，1234，1176，1090，1049，958,891,839,806,698,654；
MS：248(M
+)，233,217,205,198,188,177,170,151,125，117，91，77，63，57，51。
The proof products therefrom is correct.
Can obtain with identical method:
4 '-methyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-propyl group-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-butyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-amyl group-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-hexyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-heptyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-octyl group-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-nonyl-3, the 4-difluoro-2-methoxyl biphenyl.
Embodiment 2, preparation 4 '-(trans-4 "-amyl group cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl
1, preparation 4 '-(trans-4 "-the amyl group cyclohexyl) phenylo boric acid
Add 30.9g (0.1mol) 4 '-(trans-4 "-amyl group cyclohexyl) bromobenzene in the 250ml there-necked flask; 50ml tetrahydrofuran (THF); 2.43g (0.1mol) MAGNESIUM METAL and 1～2 iodine; at room temperature stirred 1 hour after the initiation reaction; system temperature is reduced to-70 ℃ with ethanol-liquid nitrogen system then; slow dropping 10.4g (0.1mol) trimethyl borate under this temperature, dropwising the back makes it rise to room temperature naturally under agitation condition, dripping 10% HCl solution to pH value then is 1, is heated to 100 ℃ and refluxes 1 hour down.With behind the petroleum ether extraction water of 100ml * 3, use the saturated common salt water washing again reaction solution cooling back, spend the night with anhydrous sodium sulfate drying to neutral.Dried solution revolved steam solution, obtain 22.294 '-(trans-4 "-the amyl group cyclohexyl) phenylo boric acid, yield 81%.
2, preparation 4 '-(trans-4 "-the amyl group cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl
Add 22.2g (0.081mol) 4 '-(trans-4 "-amyl group cyclohexyl) phenylo boric acid in the 250ml there-necked flask; 18.1g (0.081mol) 3; 4-difluoro-2-methoxyl bromobenzene; 95ml benzene; 58ml dehydrated alcohol; 24g yellow soda ash, 6.2g water and 1.87g four (triphenylphosphine) close palladium, are heated to 90 ℃ of 24 hours postcooling that reflux down to room temperature.Tell organic phase,, merge the organic phase after washing, use anhydrous sodium sulfate drying to neutral with 45ml * 3 chloroform extraction waters.Dried solution revolved steam solution, obtain 24.1g4 '-(trans-4 "-amyl group cyclohexyl)-3,4-difluoro-2-methoxyl biphenyl, yield 78%.
DSC (differential scanning calorimeter): Cr56.9N (52.5) I.
IR; Wave number/cm
-1=2958,2920,2845,1614,1517,1495,1468,1406,1311,1281,1232,1178,1092,1043,958,891,839,810,766,727,671,586,528;
MS(m/z)：372(M
+)，259,246,233,217，201,183,177，151,127。
Proof gained compound is correct.
Can obtain with identical method:
4 '-(trans-4 "-methylcyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the ethyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the propyl group cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the butyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the hexyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the heptyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the octyl group cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the nonyl cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl.
Embodiment 3, preparation 4 "-amyl group-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl
In the 500ml there-necked flask, add 18.8g (0.1mol) embodiment 1 gained 3,4-difluoro-2-methoxy boric acid, 30.2g (0.1mol) 4 '-amyl group-4-bromo biphenyl, 150ml benzene, the 75ml dehydrated alcohol, 30g yellow soda ash, 10g water and 2.5g four (triphenylphosphine) close palladium, are heated to 100 ℃ of 24 hours postcooling that reflux down to room temperature.Tell organic phase,, merge the organic phase after washing, use anhydrous sodium sulfate drying to neutral with 80ml * 3 chloroform extraction waters.Dried solution revolved steam solution, obtain 27.5g4 "-propyl group-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl, yield 75%.
DSC (differential scanning calorimeter): Cr61.3I;
IR: wave number/cm
-1=2954,2931,2856,1915,1884,1610,1491,1468,1427,1408,1392,1315,1275,1230,1176,1092,1049,1005,957,833,808,769,696,571,519;
MS(m/z)：366(M
+)，309,293，291,264,244,238,217,204,175，65,147,133,115，90，89，77。
Proof gained compound is correct.
Can obtain with identical method:
4 "-and methyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-ethyl-3, the 4-difluoro-2-methoxyl (1,1 ', 4 ', 1 ") terphenyl,
4 "-and propyl group-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and butyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and hexyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and heptyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and octyl group-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl,
4 "-and nonyl-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl.
Embodiment 4, preparation 2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-propyl group-1, the 3-pyrimidine
1, preparation 4-(4 '-propyl group-2 ', 5 '-pyrimidyl) phenylo boric acid
In the 250ml there-necked flask, add 27.7g (0.1mol) 4-(4 '-bromophenyl)-4-propyl group-1, the 3-pyrimidine, the 50ml tetrahydrofuran (THF), 2.43g (0.1mol) MAGNESIUM METAL and 1～2 iodine, at room temperature stirred 1 hour after the initiation reaction, system temperature is reduced to-70 ℃ with ethanol-liquid nitrogen system then, under this temperature, slowly drip 10.4g (0.1mol) trimethyl borate, dropwising the back makes it rise to room temperature naturally under agitation condition, dripping 10% HCl solution to pH value then is 1, is heated to 100 ℃ of following back hydrolysis 1 hour.With behind the petroleum ether extraction water of 100ml * 3, use the saturated common salt water washing again reaction solution cooling back, spend the night with anhydrous sodium sulfate drying to neutral.Dried solution revolved steam solution, obtain 19.4g4-(4 '-propyl group-2 ', 5 '-pyrimidyl) phenylo boric acid, yield 80%.
2, the preparation 2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-propyl group-1, the 3-pyrimidine
In the 250ml there-necked flask, add 19.4g (0.08mol) 4-(4 '-propyl group-2 ', 5 '-pyrimidyl) phenylo boric acid, 17.7g (0.08mol) 3,4-difluoro-2-methoxyl bromobenzene, 95ml benzene, 58ml dehydrated alcohol, 24g yellow soda ash, 6.2g water and 1.87g four (triphenylphosphine) close palladium, are heated to 90 ℃ of 24 hours postcooling that reflux down to room temperature.Tell organic phase,, merge the organic phase after washing, use anhydrous sodium sulfate drying to neutral with 45ml * 3 chloroform extraction waters.Dried solution revolved steam solution, obtain 19.692-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-propyl group-1,3-pyrimidine, yield 72%.
DSC (differential scanning calorimeter): Cr86.2I;
IR: wave number/cm
-1=2968,2942,2836,2812,1612,1585,1570,1340,1528,1495,1470,1433,1392,1305,1281,1265,1228,1178,1093,1039,957,893,854,822,791,729,692,654,584,463;
MS(m/z)：340(M
+)，325，311,296,284,269,245,230,229,213，202,182,175,155,149,125，80，75。
Proof gained compound is correct.
Can obtain with identical method:
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-the 5-methyl isophthalic acid, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-ethyl-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-butyl-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-amyl group-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-hexyl-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-heptyl-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-octyl group-1, the 3-pyrimidine,
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-nonyl-1, the 3-pyrimidine.
Claims (6)
1.3 4-difluoro-2-methoxyl biphenyl derivative, its structural formula are formula I,
(formula I)
Wherein, R is the alkyl of carbonatoms 1-9;
A is
M=0 or 1.
2. according to claim 13, the 4-difluoro-2-methoxyl biphenyl derivative is characterized in that: described 3,4-two fluoro-2-alkoxyl group biphenyl derivatives are:
4 '-ethyl-3, the 4-difluoro-2-methoxyl biphenyl,
4 '-(trans-4 "-the amyl group cyclohexyl)-3, the 4-difluoro-2-methoxyl biphenyl,
4 "-and amyl group-3, the 4-difluoro-2-methoxyl-(1,1 ', 4 ', 1 ") terphenyl, or
2-(4 '-(3 ", 4 "-two fluoro-2 "-p-methoxy-phenyl) phenyl)-5-propyl group-1, the 3-pyrimidine.
3. claim 1 is described 3, and the preparation method of 4-difluoro-2-methoxyl biphenyl derivative comprises the steps:
1) preparation 3,4-difluoro-2-methoxy boric acid: with 3,4-difluoro-2-methoxyl bromobenzene and MAGNESIUM METAL reaction generate Grignard reagent, with the trimethyl borate reaction, obtain structural formula after the hydrolysis suc as formula 3 of II, 4-difluoro-2-methoxy boric acid then; 2) preparation 3, the 4-difluoro-2-methoxyl biphenyl derivative: with structural formula suc as formula 3 of II, the compound of 4-difluoro-2-methoxy boric acid and structural formula such as formula III carries out linked reaction under catalyst action, obtain described 3, the 4-difluoro-2-methoxyl biphenyl derivative; Described catalyzer is that four (triphenylphosphines) close palladium;
Formula (II) formula (III)
Wherein, R is the alkyl of carbonatoms 1-9;
A is
M=0,1 or 2.
4. preparation method according to claim 3 is characterized in that: step 2) temperature of described linked reaction is 90-100 ℃, reaction solvent is benzene or dehydrated alcohol.
5. claim 1 is described 3, and the preparation method of 4-difluoro-2-methoxyl biphenyl derivative comprises the steps:
1) the preparation structural formula is the compound of formula V: with structural formula is compound and the MAGNESIUM METAL reaction generation Grignard reagent of formula IV, with the trimethyl borate reaction, obtains the compound that structural formula is formula V after the hydrolysis then; 2) preparation 3, the 4-difluoro-2-methoxyl biphenyl derivative: with structural formula be the compound of formula V and structural formula suc as formula 3 of VI, 4-difluoro-2-methoxyl bromobenzene carries out linked reaction under catalyst action, obtain described 3, the 4-difluoro-2-methoxyl biphenyl derivative; Described catalyzer is that four (triphenylphosphines) close palladium;
Formula (IV) formula V formula (VI)
Wherein, R is the alkyl of carbonatoms 1-9;
A is
M=0 or 1.
6. preparation method according to claim 5 is characterized in that: step 2) temperature of reaction of described linked reaction is 90-100 ℃, reaction solvent is benzene or dehydrated alcohol.
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