CN102020553B - P-alkyl group substituted-4-fluorophenylacetic acid, synthesis method and application thereof - Google Patents
P-alkyl group substituted-4-fluorophenylacetic acid, synthesis method and application thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- WLJVXDMOQOGPHL-UHFFFAOYSA-N benzyl-alpha-carboxylic acid Natural products OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229960003424 phenylacetic acid Drugs 0.000 claims description 9
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical class FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012312 sodium hydride Substances 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims 3
- 229940125782 compound 2 Drugs 0.000 claims 3
- 229940126214 compound 3 Drugs 0.000 claims 2
- 229940125898 compound 5 Drugs 0.000 claims 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000012074 organic phase Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 238000001035 drying Methods 0.000 description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 16
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 16
- 239000012071 phase Substances 0.000 description 16
- -1 phenyl ethylidene Chemical group 0.000 description 15
- 238000005406 washing Methods 0.000 description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 12
- 238000003810 ethyl acetate extraction Methods 0.000 description 12
- 238000010025 steaming Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- WACNXHCZHTVBJM-UHFFFAOYSA-N 1,2,3,4,5-pentafluorobenzene Chemical compound FC1=CC(F)=C(F)C(F)=C1F WACNXHCZHTVBJM-UHFFFAOYSA-N 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 6
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- MMMSLDCYNRWIFQ-UHFFFAOYSA-N C(C)(=O)Cl.FC1=CC(=C(C(=C1F)CCC)F)F Chemical compound C(C)(=O)Cl.FC1=CC(=C(C(=C1F)CCC)F)F MMMSLDCYNRWIFQ-UHFFFAOYSA-N 0.000 description 3
- GDWMSQWFMDVPKL-UHFFFAOYSA-N C(C)(=O)O.FC1=CC(=C(C(=C1F)CCC)F)F Chemical compound C(C)(=O)O.FC1=CC(=C(C(=C1F)CCC)F)F GDWMSQWFMDVPKL-UHFFFAOYSA-N 0.000 description 3
- BYBBQOCHEZFTAJ-UHFFFAOYSA-N C(C)(=O)O.FC1=CC(=C(C(=C1F)CCCCC)F)F Chemical compound C(C)(=O)O.FC1=CC(=C(C(=C1F)CCCCC)F)F BYBBQOCHEZFTAJ-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000005233 alkylalcohol group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- LICXYXFHPNVJOA-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-pent-1-enylbenzene Chemical compound FC1=C(C(=C(C(=C1C=CCCC)F)F)F)F LICXYXFHPNVJOA-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- WTEASDSUHZARIQ-UHFFFAOYSA-N C(C)(=O)Cl.FC1=CC(=C(C(=C1F)CCCCC)F)F Chemical compound C(C)(=O)Cl.FC1=CC(=C(C(=C1F)CCCCC)F)F WTEASDSUHZARIQ-UHFFFAOYSA-N 0.000 description 2
- DULCUDSUACXJJC-UHFFFAOYSA-N Ethyl phenylacetate Chemical compound CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- ARAOLTCZMIFYMK-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-prop-1-enylbenzene Chemical compound CC=CC1=C(F)C(F)=C(F)C(F)=C1F ARAOLTCZMIFYMK-UHFFFAOYSA-N 0.000 description 1
- POPHPQHEFYSJBE-UHFFFAOYSA-N 1-butyl-2,3,4,5,6-pentafluorobenzene Chemical compound CCCCC1=C(F)C(F)=C(F)C(F)=C1F POPHPQHEFYSJBE-UHFFFAOYSA-N 0.000 description 1
- NYFMNAWBGBWIIZ-UHFFFAOYSA-N 1-butyl-2,3,5,6-tetrafluoro-4-(2-phenylethyl)benzene Chemical compound CCCCC1=C(C(=C(C(=C1F)F)CCC2=CC=CC=C2)F)F NYFMNAWBGBWIIZ-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- ATPPNMLQNZHDOG-UHFFFAOYSA-N 2-fluoro-2-phenylacetic acid Chemical class OC(=O)C(F)C1=CC=CC=C1 ATPPNMLQNZHDOG-UHFFFAOYSA-N 0.000 description 1
- MPWSKEPOAYHXNW-UHFFFAOYSA-N 3-butyl-1,2,4,5-tetrafluorobenzene Chemical compound CCCCC1=C(F)C(F)=CC(F)=C1F MPWSKEPOAYHXNW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- NTOYVZQILGQSBY-UHFFFAOYSA-N CCCCCC.C(CCCC)C1=C(C(=C(C(=C1F)F)F)F)F Chemical compound CCCCCC.C(CCCC)C1=C(C(=C(C(=C1F)F)F)F)F NTOYVZQILGQSBY-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a p-alkyl group substituted-4-fluorophenylacetic acid, a synthesis method and an application thereof. The compound has the following structural formula, wherein R is C2-6 alkyl group. The synthesis method of the compound is simple, is suitable for industrial production and can be used for preparing liquid crystal compounds.
Description
Technical field
The present invention relates to a kind of to alkyl replacement-tetra fluoro benzene acetic acid, synthetic method and purposes.
Background technology
Liquid-crystal display (LCDs) appears at the initial stage of 20 century 70s at first as the display device of counter and digital clock.Among spreading to daily life from word processor (word processor) and individual literal assistant (PDAs) to notebook computer, desktop computer and TV.Huge industry is being grown in LCD industry.For Thin Film Transistor-LCD (TFT LCDs), in order to stand firm and constantly to enlarge market share in TV market, the sharpness of its animation, high brightness and high-speed response are very important.
For the liquid crystal that is applied to LCD, it should have good chemical stability, photochemical stability, thermostability, and the good stability of anti-electric field and electromagnetic interference.In addition, it should have low-viscosity, low threshold voltage, high-contrast, and working temperature is wide as far as possible up and down in room temperature.Owing to must mix use with other composition, it should have good compatibility.In brief, for high-quality LCD, liquid crystal must possess suitable physical properties: wide nematic temperature range, high resistivity, suitable double refractive inde and high dielectric anisotropy.
People's expectation has more synthetic liquid crystal raw material, can synthesize to have wide nematic temperature range, so that have low-viscosity and high resistivity, can as the component of TFT liquid crystal, the character of liquid crystal material be improved.
Summary of the invention
The object of the invention provides a kind of to alkyl replacement-tetra fluoro benzene acetic acid, synthetic method and purposes.
Of the present invention have following structural formula to alkyl replacement-tetra fluoro benzene acetic acid:
Wherein, R is the alkyl of C2-6.
Synthetic method to alkyl replacement-tetra fluoro benzene acetic acid of the present invention
Method of the present invention can adopt reaction formula to be described below:
Wherein R1 is the alkyl of C1-5, and R is the alkyl of C2-6
A) Mg, THF; C
nH
2nO, tetrahydrofuran (THF); B) P
2O
5, C
6H
14C) H
2, Pd/C (5%); D) K
2CO
3, NCCH
2COOEt, N-Methyl pyrrolidone) NaOH, H
2O.
Specifically by following 1)-5) step obtain:
(1) in organic solvent and under the reflux temperature, five bromofluorobenzenes and reactive magnesium 0.5-2 hour, be cooled to room temperature, reaction obtained 1-pentafluorophenyl group R in 0.1-1.0 hour under the aldehyde reflux temperature of dropping C2-6
1The alkyl alcohol that replaces; Wherein, the mol ratio of the aldehyde of five bromofluorobenzenes, magnesium and C2-6 is 1: 1～1.3: 0.8～1.2.Reaction product can adopt the method purifying such as organic solvent extraction, distillation.
(2) in organic solvent and during room temperature to 50 ℃, the 1-pentafluorophenyl group R that step (1) is obtained
1(noting the length variations of the alkyl) alkyl alcohol that replaces and Vanadium Pentoxide in FLAKES reaction obtained the penta fluoro benzene of 2-R alkenyl substituted, described 1-pentafluorophenyl group R in 1-2 hour
1The alkyl alcohol that replaces and the mol ratio of Vanadium Pentoxide in FLAKES are 1: 1-4.
(3) in organic solvent, the penta fluoro benzene of the product 2-R alkenyl substituted that step (2) obtains and the Pd/C that contains 5% weight Pd are at logical H
2Under 1-5MPa, react the penta fluoro benzene that got the R replacement in 1-4 hour, wherein, the penta fluoro benzene of 2-R alkenyl substituted and the weight ratio of 5%Pd/C are 1: 8～10.
(4) product in the step (3) and N-Methyl pyrrolidone, sodium hydride, ethyl cyanoacetate get 2-cyano group-2,3,5 90-120 ℃ of reaction 1-3 hour after the acidifying, 6-tetrafluoro-4-R base Phenylacetic acid ethylester; The mol ratio of described R base penta fluoro benzene and sodium hydride, ethyl cyanoacetate is 1: 1.5～3: 1.5～3;
(5) product in the step (4) and aqueous sodium hydroxide solution obtain 2,3,5 70-100 ℃ of lower reaction acidifying after 12-24 hour, 6-tetrafluoro-4-R base toluylic acid; Described 2-cyano group-2,3,5, the mol ratio of 6-tetrafluoro-4-R base Phenylacetic acid ethylester and sodium hydroxide is 1: 4-8; Aqueous sodium hydroxide solution concentration is 5-10%.
Wherein, R is described as defined above; Described organic solvent is tetrahydrofuran (THF) (THF), normal hexane, CH
2Cl
2, CH
3Cl or sherwood oil.
Compound of the present invention is simple synthetic method not only, and this fluorophenylacetic acid that contains can be used as intermediate and be converted into easily tetrafluoro phenyl ethylidene, synthetic all kinds of novel liquid crystals, and having widely, industrial use is suitable for preparing liquid crystalline cpd.Especially be fit to preparation 4-(2,3,5,6-tetrafluoro-R substituting group styroyl) phenylformic acid-4 '-the fluorinated liquid crystal compound of fluoro-4-Biphenyl Ester, wherein, R is C
2-6Alkyl.This liquid crystal has wide nematic temperature range owing to have the tetrafluoro phenyl ethylidene that alkyl replaces, and may have low-viscosity and high resistivity, can as the component of TFT liquid crystal, the character of liquid crystal material be improved.
Embodiment
Following examples help and understand the present invention, but are not limited to content of the present invention.(take n=3,4,5 as example)
Embodiment 12,3,5,6-tetrafluoro-4-propylbenzene acetic acid synthetic
1,1-pentafluorophenyl group propyl alcohol
In being arranged, the 500mL there-necked flask of nitrogen protection adds THF (70mL); magnesium chips (9.43g, 0.35mol) stirs the lower five bromofluorobenzenes (75g that drips; 0.3mol); reflux 1.5 hours is cooled to room temperature, drips propionic aldehyde (15.82g; 0.273mol; THF70mL), reflux 2 hours obtains black liquor.Add saturated ammonium chloride solution (300mL) after the cooling and stirred 0.5 hour, use the ethyl acetate extraction inorganic phase, merge organic phase, use anhydrous sodium sulfate drying, desolventizing, underpressure distillation, collect 72-74 ℃/4mmHg, get 45g1-pentafluorophenyl group propyl alcohol, Y=73%.MS(m/z，％)：266(M
+，4.09)，197(100.00)。
2,2-propenyl penta fluoro benzene
In the 250mL there-necked flask, add normal hexane (150mL), 1-pentafluorophenyl group propyl alcohol (44g, 0.195mol), Vanadium Pentoxide in FLAKES (72g, 0.507mol) is heated with stirring to 50 ℃ of reactions and finished in 2 hours, filter, get the hexane solution of 2-propenyl penta fluoro benzene.
3, propyl group penta fluoro benzene
Change the solution in the above-mentioned steps over to autoclave, and adding Pd/C (5%, 4g), logical H
2/ 3MPa, reaction in 4 hours finishes.Normal hexane is removed in distillation, gets colourless transparent liquid propyl group penta fluoro benzene 31.6g, Y=78%.MS(m/z，％)：210(M
+，26.52)，181(100.00)。
4,2-cyano group-2,3,5,6-tetrafluoro-4-propylbenzene ethyl acetate
In the 100mL there-necked flask, add dry N-Methyl pyrrolidone (20mL), NaH (0.96g, 60%), stir the lower ethyl cyanoacetate (2.7g) that slowly drips, until without Bubble formation, drip propyl group penta fluoro benzene (2.5g, 0.012mol), dropwise and be heated to 110 ℃, reaction in 2 hours finishes.Be cooled to room temperature, in reaction solution, add concentrated hydrochloric acid adjusting pH＜3, a large amount of muddy and phase-splittings occur, add water to muddy the disappearance, use the ethyl acetate extraction inorganic phase, merge organic phase, clear water washing three times times, anhydrous sodium sulfate drying, steaming desolventizes, and column chromatography gets transparent liquid 2-cyano group-2,3,5,6-tetrafluoro-4-propylbenzene ethyl acetate 3g, Y=82.4%.MS(m/z，％)：303(M
+，3.59)，202(100.00)。
5,2,3,5,6-tetrafluoro-4-propylbenzene acetic acid
2-cyano group-2,3,5, and 6-tetrafluoro-4-propylbenzene ethyl acetate (2.86g, 0.0094mol) and the NaOH aqueous solution (6.3%, 35mL), in the 100mL there-necked flask, be heated with stirring to 90 ℃, reacted 18 hours.Be cooled to room temperature, add concentrated hydrochloric acid to emitting without bubble, regulate pH＜3, a large amount of white solids appear, suction filtration, filter cake clear water washed twice, dry, use the sherwood oil recrystallization, get white plates solid 2,3,5,6-tetrafluoro-4-propylbenzene acetic acid 1.66g, purity 99.5%, productive rate (Y)=70%.MS(m/z，％)：250(M
+，97.7)，177(100.00)。
19F NMR(CDCl
3，500MHz)，δ(ppm)：-144.20(dd，2F)，-145.10(dd，2F)。
Of the present invention 2,3,5,6-tetrafluoro-4-propylbenzene acetic acid can be for the synthesis of liquid crystalline cpd 4-(2,3,5,6-tetrafluoro-4-n-propylbenzene ethyl) phenylformic acid-4 '-fluoro-4-Biphenyl Ester: 6,2-(2,3,5,6-tetrafluoro-4-propyl group phenyl) methyl phenyl ketone is synthetic
2,3,5,6-tetrafluoro-4-propylbenzene acetic acid (11g, 0.044mol), SOCl
240mL is heated to backflow in the single port bottle, finish after one hour, generates 2,3,5,6-tetrafluoro-4-propylbenzene Acetyl Chloride 98Min., steams and removes sulfur oxychloride.In there-necked flask, add AlCl
3(8.8g, 0.067mol), benzene 30mL drips 2,3,5,6-tetrafluoro-4-propylbenzene Acetyl Chloride 98Min. in the time of 0 ℃, make temperature remain on 0-5 ℃, and half an hour, afterreaction finished.Reactant is joined in the frozen water of hydrochloric acid and stirred 10 minutes, the ethyl acetate extraction inorganic phase use in layering, the merging organic phase, and wash respectively organic phase with dilute NaOH solution and water, behind the anhydrous sodium sulfate drying, steaming desolventizes.Column chromatography gets product 2-(2,3,5,6-tetrafluoro-4-propyl group phenyl) methyl phenyl ketone 11g, Y=80.7%.MS(m/z，％)：310(M
+，0.15)，105(100.00)。
7,2-(2,3,5,6-tetrafluoro-4-propyl group phenyl) ethylbenzene is synthetic
Add 2-(2,3,5,6-tetrafluoro-4-propyl group phenyl) methyl phenyl ketone (3.4g, 0.01mol) in there-necked flask, trifluoroacetic acid 12g drips triethyl silicane (3g, 0.026mol) under the magnetic agitation, and room temperature reaction finished in 18 hours.Add saturated Na
2CO
3With excessive trifluoroacetic acid, layering merges organic phase with the ethyl acetate extraction inorganic phase in the solution, clear water washing organic phase, use anhydrous sodium sulfate drying, steaming desolventizes, and column chromatography gets product 2-(2,3,5,6-tetrafluoro-4-propyl group phenyl) ethylbenzene 1.2g, Y=40.5%.MS(m/z，％)：296(M
+，18.30)，91(100.00)。
8,2-(2,3,5,6-tetrafluoro-4-propyl group phenyl) ethylamino benzonitrile acyl chlorides is synthetic
In there-necked flask, add CH
2Cl
210mL, anhydrous AlCl
3(0.16g, 1.2mmol) is cooled to 0 ℃, drips oxalyl chloride (0.25g, 2mmol), then drips and uses 10mLCH
2Cl
22-(2,3,5, the 6-tetrafluoro-4-propyl group phenyl) ethylbenzene (0.3g, 1mmol) of dilution, 1.5 hours afterreactions of magnetic agitation finish.Reaction system joined in the beaker that trash ice (12g) and calcium chloride (0.5g) are housed and stirred ten minutes, CH is used in layering
2Cl
2Extract inorganic phase, merge organic phase, with dilute NaOH solution and clear water washing, use anhydrous sodium sulfate drying, room temperature is revolved and is evaporated partial solvent, gives over to for subsequent use.
9,4-(2,3,5,6-tetrafluoro-4-n-propylbenzene ethyl) phenylformic acid-4 '-fluoro-4-biphenyl ester synthesis
In there-necked flask, add 4 '-fluoro-4-xenol (0.19g, 1mmol), CH
2Cl
210mL, triethylamine (0.2g, 2mmol) is cooled to 0 ℃, drips the solution of acid chloride in the above-mentioned steps, and 1 hour afterreaction of magnetic agitation finishes.With hydrochloric acid soln 30mL and the clear water washing of 0.1mol/L, organic phase is collected in layering, uses anhydrous sodium sulfate drying respectively, and steaming desolventizes.Column chromatography gets white solid 4`-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-propylbenzene ethyl) benzoic ether 0.35g, Y=68.6% behind the recrystallization.MS(m/z，％)：510(M
+，5.23)，323(100.00)。
1HNMR(CDCl
3，400MHz)，δ(ppm)：0.94-0.98(t，3H，J＝7.4Hz)，1.59-1.68(m，2H)，2.67-2.71(t，2H，J
1＝7.4Hz，J
2＝7.4Hz)，2.99-3.05(m，4H)，7.11-7.16(m，2H)，7.27-7.30(m，2H)，7.32-7.34(d，2H，J＝8.0Hz)，7.52-7.56(m，2H)，7.57-7.60(m，2H)，8.13-8.15(d，2H，J＝8.4Hz)。
19FNMR(CDCl
3，500MHz)，δ(ppm)：-147.10--147.02(m，2F)，-146.57--146.50(m，2F)，-116.57--116.54(m，1F)。
Embodiment 22,3,5,6-tetrafluoro-4-butylbenzene acetic acid synthetic
1,1-pentafluorophenyl group butanols is synthetic
In being arranged, the 500mL there-necked flask of nitrogen protection adds THF (70mL); magnesium chips (10.2g, 0.38mol) stirs the lower five bromofluorobenzenes (80g that drips; 0.32mol) and 50mL THF; reflux 1.5 hours is cooled to room temperature, drips butyraldehyde (19.8g; 0.275mol; THF70mL), reflux 2 hours obtains black liquor.Add saturated ammonium chloride solution (320mL) after the cooling and stirred 0.5 hour, use the ethyl acetate extraction inorganic phase, merge organic phase, the clear water washing, use anhydrous sodium sulfate drying, desolventizing, underpressure distillation, collect 78-80 ℃/4mmHg of cut, get 56.2g1-pentafluorophenyl group butanols, Y=85.1%.MS(m/z，％)：240(M
+，3.51)，197(100.00)。
2, the crotyl penta fluoro benzene is synthetic
In the 250mL there-necked flask, add normal hexane (180mL), 1-pentafluorophenyl group butanols (52.8g, 0.22mol), Vanadium Pentoxide in FLAKES 81g, 0.57mol), be heated with stirring to 50 ℃ of reactions and finished in 2 hours, filter, get the hexane solution of crotyl penta fluoro benzene.
3, the butyl penta fluoro benzene is synthetic
Change the solution in the above-mentioned steps over to autoclave, and adding Pd/C (5%, 4g), logical H
2/ 2.2MPa, reaction in 4 hours finishes.Most of normal hexane is removed in distillation, gets the hexane solution 47.1g of colourless transparent liquid normal-butyl penta fluoro benzene, content 70%.
4,2-cyano group-2,3,5,6-tetrafluoro-4-butylbenzene ethyl acetate synthetic
In the 100mL there-necked flask, add dry N-Methyl pyrrolidone (150mL), NaH (6.7g, 60%, 0.28mol), stir the lower ethyl cyanoacetate (31.6g that slowly drips, 0.28mol), until without Bubble formation, drip normal-butyl penta fluoro benzene hexane solution (45g, 70%), dropwise and be heated to 110 ℃, reaction in 2 hours finishes.Be cooled to room temperature, in reaction solution, add salt acid for adjusting pH＜3, use the ethyl acetate extraction inorganic phase, merge organic phase, clear water washing three times, anhydrous sodium sulfate drying, steaming desolventizes, 140-150 ℃ of cut collected in the 2mm/Hg underpressure distillation, gets light yellow transparent liquid 2-cyano group-2,3,5,6-tetrafluoro-4-butylbenzene ethyl acetate 35g, Y=80%.MS(m/z，％)：317(M
+，3.59)，202(100.00)。
5,2,3,5,6-tetrafluoro-4-butylbenzene acetic acid synthetic
2-cyano group-2,3,5, and 6-tetrafluoro-4-butylbenzene ethyl acetate (24.8g, 0.079mol) and the NaOH aqueous solution (6.3%, 280mL), in the 500mL there-necked flask, be heated with stirring to 90 ℃, reacted 18 hours.Be cooled to room temperature, add concentrated hydrochloric acid to emitting without bubble, regulate pH＜3, a large amount of white solids occur, suction filtration, filter cake clear water washed twice, drying is used the sherwood oil recrystallization, gets white crystal 2,3,5,6-tetrafluoro-4-butylbenzene acetic acid 18.9g, Y=90%.MS(m/z，％)：264(M
+，80.97)，222(100.00)。
Of the present invention 2,3,5,6-tetrafluoro-4-butylbenzene acetic acid can be for the preparation of 4 '-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-butylbenzene ethyl) benzoic acid ester compounds:
6,2-(2,3,5,6-tetrafluoro-4-butyl phenyl) methyl phenyl ketone is synthetic
2,3,5,6-tetrafluoro-4-butylbenzene acetic acid (16g, 0.06mol), SOCl
230mL is heated to backflow in the single port bottle,, finish after one hour, generate 2,3,5,6-tetrafluoro-4-butylbenzene Acetyl Chloride 98Min., remove most of solvent.In there-necked flask, add AlCl
3(12g, 0.09mol), benzene 20mL drips 2,3,5,6-tetrafluoro-4-propylbenzene Acetyl Chloride 98Min. in the time of 0 ℃, make temperature remain on 0-5 ℃, and half an hour, afterreaction finished.Reactant is joined in the frozen water of hydrochloric acid and stirred 10 minutes, the ethyl acetate extraction inorganic phase use in layering, the merging organic phase, and wash respectively organic phase with dilute NaOH solution and water, behind the anhydrous sodium sulfate drying, steaming desolventizes.Column chromatography gets product 2-(2,3,5,6-tetrafluoro-4-butyl phenyl) methyl phenyl ketone 17g, Y=87%.MS(m/z，％)：324(M
+，0.32)，105(100.00)。
7,2-(2,3,5,6-tetrafluoro-4-butyl phenyl) ethylbenzene is synthetic
Add 2-(2,3,5,6-tetrafluoro-4-butyl phenyl) methyl phenyl ketone (5g, 0.015mol) in there-necked flask, trifluoroacetic acid 17g drips triethyl silicane (4.5g, 0.039mol) under the magnetic agitation, and room temperature reaction finished in 18 hours.Add saturated Na
2CO
3With excessive trifluoroacetic acid, layering merges organic phase with the ethyl acetate extraction inorganic phase in the solution, clear water washing organic phase, use anhydrous sodium sulfate drying, steaming desolventizes, and column chromatography gets product 2-(2,3,5,6-tetrafluoro-4-butyl phenyl) ethylbenzene 1.2g, Y=25.8%.MS(m/z，％)：310(M
+，6.10)，91(100.00)
8,2-(2,3,5,6-tetrafluoro-4-butyl phenyl) ethylamino benzonitrile acyl chlorides is synthetic
In there-necked flask, add CH
2Cl
210mL, anhydrous AlCl
3(0.2g, 1.6mmol) is cooled to 0 ℃, drips oxalyl chloride (0.33g, 2.6mmol), then drips and uses 10mLCH
2Cl
22-(2,3,5, the 6-tetrafluoro-4-butyl phenyl) ethylbenzene (0.5g, 1.3mmol) of dilution, 1.5 hours afterreactions of magnetic agitation finish.Reaction system joined in the beaker that trash ice (15g) and calcium chloride (0.6g) are housed and stirred ten minutes, CH is used in layering
2Cl
2Extract inorganic phase, merge organic phase, with dilute NaOH solution and clear water washing, use anhydrous sodium sulfate drying, room temperature is revolved and is evaporated partial solvent, gives over to for subsequent use.
9,4 '-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-butylbenzene ethyl) phenylformic acid ester synthesis
In there-necked flask, add 4 '-fluoro-4-xenol (0.24g, 1.3mmol), CH
2Cl
210mL, triethylamine (0.26g, 2.6mmol) is cooled to 0 ℃, drips the solution of acid chloride in the above-mentioned steps, and 1 hour afterreaction of magnetic agitation finishes.With hydrochloric acid soln 30mL and the clear water washing of 0.1mol/L, organic phase is collected in layering, uses anhydrous sodium sulfate drying respectively, and steaming desolventizes.Column chromatography, behind the recrystallization white solid 4 '-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-butylbenzene ethyl) benzoic ether 0.42g, Y=60%.MS(m/z，％)：524(M
+，5.46)，337(100.00)。
1HNMR(CDCl
3，400MHz)，δ(ppm)：0.92-0.96(t，3H，J＝7.4Hz)，1.32-1.41(m，2H)，1.54-1.59(m，2H)，2.69-2.73(t，2H，J＝7.6Hz)，2.98-3.05(m，4H)，7.12-7.16(m，2H)，7.27-7.30(m，2H)，7.32-7.34(d，2H，J＝8.0Hz)7.52-7.56(m，2H)，7.58-7.61(m，2H)，8.13-8.15(d，2H，J＝8.4Hz)，
19FNMR(CDCl
3，500MHz)，δ(ppm)：-147.10--147.02(m，2F)，-146.65--146.57(m，2F)，-116.57--116.55(m，1F)。
Embodiment 32,3,5,6-tetrafluoro-4-amylbenzene acetic acid synthetic
1,1-pentafluorophenyl group amylalcohol is synthetic
In being arranged, the 500mL there-necked flask of nitrogen protection adds THF (70mL); magnesium chips (10.2g, 0.38mol) stirs the lower five bromofluorobenzenes (80g that drips; 0.32mol) and 50mL THF; reflux 1.5 hours is cooled to room temperature, drips valeral (23.6g; 0.275mol; THF70mL), reflux 2 hours obtains black liquor.Add saturated ammonium chloride solution (320mL) after the cooling and stirred 0.5 hour, use the ethyl acetate extraction inorganic phase, merge organic phase, the clear water washing, use anhydrous sodium sulfate drying, desolventizing, underpressure distillation, collect 92-98 ℃/3mmHg of cut, get 46g1-pentafluorophenyl group amylalcohol, Y=56%.MS(m/z，％)：254(M
+，1.38)，197(100.00)。
2, the pentenyl penta fluoro benzene is synthetic
In the 250mL there-necked flask, add normal hexane (150mL), 1-pentafluorophenyl group amylalcohol (39.5g, 0.16mol), Vanadium Pentoxide in FLAKES (57.4g, 0.4mol) is heated with stirring to 50 ℃ of reactions and finished in 2 hours, filter, get the hexane solution of pentenyl penta fluoro benzene.
3, the amyl group penta fluoro benzene is synthetic
Change the solution in the above-mentioned steps over to autoclave, and adding Pd/C (5%, 4g), logical H
2/ 2MPa, reaction in 4 hours finishes.Most of normal hexane is removed in distillation, gets the hexane solution 32.6g of colourless transparent liquid normal-butyl penta fluoro benzene, content 70%.
4,2-cyano group-2,3,5,6-tetrafluoro-4-amylbenzene ethyl acetate synthetic
In the 100mL there-necked flask, add dry N-Methyl pyrrolidone (80mL), NaH (5.48g, 60%, 0.14mol), stir the lower ethyl cyanoacetate (15.5g that slowly drips, 0.14mol), until without Bubble formation, drip n-pentyl penta fluoro benzene hexane solution (30g, 70%), dropwise and be heated to 110 ℃, reaction in 2 hours finishes.Be cooled to room temperature, in reaction solution, add salt acid for adjusting pH＜3, use the ethyl acetate extraction inorganic phase, merge organic phase, clear water washing three times, anhydrous sodium sulfate drying, steaming desolventizes, 140-150 ℃ of cut collected in the 2mm/Hg underpressure distillation, gets light yellow viscous liquid 2-cyano group-2,3,5,6-tetrafluoro-4-amylbenzene ethyl acetate 18g, Y=62%.MS(m/z，％)：331(M
+，1.69)，259(100.00)。
5,2,3,5,6-tetrafluoro-4-amylbenzene acetic acid synthetic
2-cyano group-2,3,5, and 6-tetrafluoro-4-amylbenzene ethyl acetate (12g, 0.036mol) and the NaOH aqueous solution (6.3%, 130mL), in the 500mL there-necked flask, be heated with stirring to 90 ℃, reacted 18 hours.Be cooled to room temperature, add concentrated hydrochloric acid to emitting without bubble, regulate pH＜3, a large amount of white solids occur, suction filtration, filter cake clear water washed twice, drying, recrystallization gets white crystal 2,3,5,6-tetrafluoro-4-amylbenzene acetic acid 6.7g, Y=67%.MS(m/z，％)：278(M
+，73.89)，176(100.00)。
Of the present invention 2,3,5,6-tetrafluoro-4-amylbenzene acetic acid can for the preparation of liquid crystalline cpd 4 '-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-amylbenzene ethyl) benzoic ether: 6,2-(2,3,5,6-tetrafluoro-4-amyl group phenyl) methyl phenyl ketone is synthetic
2,3,5,6-tetrafluoro-4-amylbenzene acetic acid (4g, 0.014mol), SOCl
215mL is heated to backflow in the single port bottle, finish after one hour, generates 2,3,5,6-tetrafluoro-4-amylbenzene Acetyl Chloride 98Min., removes most of solvent.In there-necked flask, add AlCl
3(2.6,0.02mol), benzene 10mL drips 2,3,5,6-tetrafluoro-4-amylbenzene Acetyl Chloride 98Min. in the time of 0 ℃, make temperature remain on 0-5 ℃, and half an hour, afterreaction finished.Reactant is joined in the frozen water of hydrochloric acid and stirred 10 minutes, the ethyl acetate extraction inorganic phase use in layering, the merging organic phase, and wash respectively organic phase with dilute NaOH solution and water, behind the anhydrous sodium sulfate drying, steaming desolventizes.Column chromatography gets product 2-(2,3,5,6-tetrafluoro-4-amyl group phenyl) methyl phenyl ketone 2.5g, Y=51.4%.MS(m/z，％)：338(M
+，0.32)，105(100.00)。
7,2-(2,3,5,6-tetrafluoro-4-amyl group) ethylbenzene is synthetic
Add 2-(2,3,5,6-tetrafluoro-4-amyl group phenyl) methyl phenyl ketone (1.6g, 4.7mmol) in there-necked flask, trifluoroacetic acid 6g drips triethyl silicane (1.4g, 12mmol) under the magnetic agitation, and room temperature reaction finished in 18 hours.Add saturated Na
2CO
3With excessive trifluoroacetic acid, layering merges organic phase with the ethyl acetate extraction inorganic phase in the solution, clear water washing organic phase, use anhydrous sodium sulfate drying, steaming desolventizes, and column chromatography gets product 2-(2,3,5,6-tetrafluoro-4-amyl group phenyl) ethylbenzene 0.3g, Y=20%.MS(m/z，％)：324(M
+，6.82)，203(100.00)
8,2-(2,3,5,6-tetrafluoro-4-amyl group phenyl) ethylamino benzonitrile acyl chlorides is synthetic
In there-necked flask, add CH
2Cl
210mL, anhydrous AlCl
3(0.1g, 0.8mmol) is cooled to 0 ℃, drips oxalyl chloride (0.16g, 1.3mmol), then drips and uses 10mLCH
2Cl
22-(2,3,5, the 6-tetrafluoro-4-amyl group phenyl) ethylbenzene (0.2g, 0.6mmol) of dilution, 1.5 hours afterreactions of magnetic agitation finish.Reaction system joined in the beaker that trash ice (15g) and calcium chloride (0.6g) are housed and stirred ten minutes, CH is used in layering
2Cl
2Extract inorganic phase, merge organic phase, with dilute NaOH solution and clear water washing, use anhydrous sodium sulfate drying, room temperature is revolved and is evaporated partial solvent, gives over to for subsequent use.
9,4 '-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-amylbenzene ethyl) phenylformic acid ester synthesis
In there-necked flask, add 4 '-fluoro-4-xenol (0.12g, 0.65mmol), CH
2Cl
210mL, triethylamine (0.2g, 2mmol) is cooled to 0 ℃, drips the solution of acid chloride in the above-mentioned steps, and 1 hour afterreaction of magnetic agitation finishes.With hydrochloric acid soln 30mL and the clear water washing of 0.1mol/L, organic phase is collected in layering, uses anhydrous sodium sulfate drying respectively, and steaming desolventizes.Column chromatography, behind the recrystallization white solid 4 '-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-amylbenzene ethyl) benzoic ether 0.16g, Y=50%.MS(m/z，％)：538(M
+，5.02)，351(100.00)。
1HNMR(CDCl
3，500MHz)，δ(ppm)：0.89～0.92(t，3H，J
1＝7.0，J
2＝6.6)，1.33～1.37(m，2H)，1.58～1.62(m，2H)，2.68～2.71(t，2H，J
1＝7.4，J
2＝7.6)，2.98～3.01(d，2H，J＝6.8)，3.04～3.05(m，2H)，7.12～7.156(t，2H，J
1＝8.6，J
2＝8.6)，7.28～7.30(d，2H，J＝8.5)，7.32～7.34(d，2H，J＝8.1)，7.53～7.56(m，2H)，7.58～7.60(d，2H，J＝8.5)，8.13～8.15(d，2H，J＝8.0)，
19FNMR(CDCl
3，500MHz)，δ(ppm)：-147.09～-147.02(m，2F)，-146.66～-146.59(m，2F)，-116.57～-116.55(m，1F)。
The transformation temperature of embodiment 4 liquid crystalline cpds
The phase transformation of the liquid crystalline cpd of embodiment 1-3 and temperature are by the XPV-230E polarizing microscope observation of rectangular optical instrument factory with XPH-300 microscope hot stage controller, amplify 100 times, polarisation 90 degree, starting temperature is 90～100 ℃, heat-up rate is 4 ℃/min to 180 ℃ subsequently, then is down to room temperature in the fast cooling mode of hot platform.
The transformation temperature of liquid crystalline cpd under table 1 polarizing microscope
The liquid crystalline cpd transformation temperature/℃
n＝3 C 136.3 N 173.0 I 157.4 104 C
n＝4 C 127.8 S 133.8 N 163 I 154.7 N 113 C
n＝5 C 120 N 162.5 I 153.5 N 110 C
Liquid crystalline cpd 1,2 and 3 represents respectively 4-(2 successively, 3,5,6-tetrafluoro-4-n-propylbenzene ethyl) phenylformic acid-4 '-fluoro-4-Biphenyl Ester, 4 '-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-butylbenzene ethyl) benzoic ether and 4 '-fluoro-xenol 4-(2,3,5,6-tetrafluoro-4-n-amylbenzene ethyl) benzoic ether.
Claims (5)
1. one kind to alkyl replacement-tetra fluoro benzene acetic acid, has following structural formula:
Wherein, R is C
2-6Alkyl.
2. the synthetic method to alkyl replacement-tetra fluoro benzene acetic acid as claimed in claim 1 is characterized in that adopting following 1)-5) step obtain:
1), in organic solvent and under the reflux temperature, five bromofluorobenzenes and reactive magnesium 0.5-2 hour, be cooled to room temperature, drip C
2-6Aldehyde, reaction obtained compound 1 in 0.1-1.0 hour under the reflux temperature;
Wherein, five bromofluorobenzenes, magnesium and C
2-6The mol ratio of aldehyde be 1: 1～1.3: 0.8～1.2;
2), in organic solvent and during room temperature to 50 ℃, compound 1 and Vanadium Pentoxide in FLAKES reaction that step (1) is obtained obtained compound 2 in 1-2 hour, and the mol ratio of described compound 1 and Vanadium Pentoxide in FLAKES is 1: 1～4;
3), in organic solvent, the product compound 2 that step (2) obtains and the Pd/C that contains 5% weight Pd are at logical H
2Under 1-5MPa, reacted 1-4 hour to get compound 3, wherein, the weight ratio of compound 2 and 5%Pd/C is 1: 8～10;
4), the product in the step (3) and N-Methyl pyrrolidone, sodium hydride, ethyl cyanoacetate get compound 4 90-120 ℃ of reaction 1-3 hour after the acidifying; Described compound 3 is 1: 1.5～3: 1.5～3 with the mol ratio of sodium hydride, ethyl cyanoacetate;
5) product, step 4) and aqueous sodium hydroxide solution obtain compound 5 70-100 ℃ of lower reaction acidifying after 12-24 hour; The mol ratio of described compound 4 and sodium hydroxide is 1: 4-8; Aqueous sodium hydroxide solution concentration is 5-10%;
Described R
1Be C
1-5Alkyl; Described R is C
2-6Alkyl.
3. the synthetic method to alkyl replacement-tetra fluoro benzene acetic acid as claimed in claim 2 is characterized in that described organic solvent is tetrahydrofuran (THF), normal hexane, CH
2Cl
2, CH
3Cl or sherwood oil.
4. the purposes to alkyl replacement-tetra fluoro benzene acetic acid as claimed in claim 1 is characterized in that for the preparation of liquid crystalline cpd.
5. purposes as claimed in claim 4, it is characterized in that above-mentioned liquid crystalline cpd be 4-(2,3,5,6-tetrafluoro-R substituting group styroyl) phenylformic acid-4 '-fluorinated liquid crystal of fluoro-4-Biphenyl Ester, wherein, R is C
2-6Alkyl.
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| GB2121406A (en) * | 1982-05-11 | 1983-12-21 | Secr Defence | Liquid crystal cyanophenylethanes |
| US4583826A (en) * | 1981-10-14 | 1986-04-22 | Hoffmann-La Roche Inc. | Phenylethanes |
| CN1066458A (en) * | 1992-06-04 | 1992-11-25 | 中国科学院上海有机化学研究所 | Contain liquid crystalline cpd of perfluoro-benzene-ring and preparation method thereof |
| CN1183403A (en) * | 1997-12-15 | 1998-06-03 | 中国科学院上海有机化学研究所 | Liquid crystal compound contg. cyclohexyl and perfluoro benzene ring and preparing process thereof |
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| GB2121406A (en) * | 1982-05-11 | 1983-12-21 | Secr Defence | Liquid crystal cyanophenylethanes |
| CN1066458A (en) * | 1992-06-04 | 1992-11-25 | 中国科学院上海有机化学研究所 | Contain liquid crystalline cpd of perfluoro-benzene-ring and preparation method thereof |
| CN1183403A (en) * | 1997-12-15 | 1998-06-03 | 中国科学院上海有机化学研究所 | Liquid crystal compound contg. cyclohexyl and perfluoro benzene ring and preparing process thereof |
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