CN1966488A - Preparation method of benzonitrile monomer liquid crystal - Google Patents
Preparation method of benzonitrile monomer liquid crystal Download PDFInfo
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- CN1966488A CN1966488A CN 200610070269 CN200610070269A CN1966488A CN 1966488 A CN1966488 A CN 1966488A CN 200610070269 CN200610070269 CN 200610070269 CN 200610070269 A CN200610070269 A CN 200610070269A CN 1966488 A CN1966488 A CN 1966488A
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- cyclohexyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 title claims abstract description 27
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- -1 4- (trans-4' -substituted cyclohexyl) benzonitrile Chemical class 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 238000001953 recrystallisation Methods 0.000 claims description 10
- ZCJAYDKWZAWMPR-UHFFFAOYSA-N 1-chloro-2-fluorobenzene Chemical compound FC1=CC=CC=C1Cl ZCJAYDKWZAWMPR-UHFFFAOYSA-N 0.000 claims description 9
- GDHXJNRAJRCGMX-UHFFFAOYSA-N 2-fluorobenzonitrile Chemical compound FC1=CC=CC=C1C#N GDHXJNRAJRCGMX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical group [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007818 Grignard reagent Substances 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 4
- 238000003379 elimination reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 238000005502 peroxidation Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000007333 cyanation reaction Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention relates to a method for preparing benzonitrile monomer liquid crystal, and belongs to the technical field of preparation methods of monomer liquid crystal. The preparation method of the benzonitrile monomer liquid crystal is characterized in that the synthesis route of the benzonitrile monomer liquid crystal is shown as the formula , wherein R is C1～C10N-0 or 2, m-0 or 1, a-cyclohexyl, Y, Z-F or H atom, with the proviso that at least one of Y, Z is an F atom. The preparation method takes the formula (II) as a raw material, and can obtain the product with high yield through high-temperature cyanation. The preparation method has the advantages of simple process route, relatively mild reaction conditions, low production cost and environmental friendliness, and is particularly suitable for industrial production of the fluorine-containing 4- (trans-4' -substituted cyclohexyl) benzonitrile monomer liquid crystal on the benzene ring.
Description
Technical field:
The present invention relates to a kind of method for preparing benzene nitrile monomer liquid crystal, belong to the preparation method of monomer liquid crystal
Technical field.
Background technology:
4-(trans-4 '-substituted cyclohexyl) benzene nitrile monomer liquid crystal since itself Δ ε value greatly, solvability is good, thereby has a wide range of applications in TN, STN mixed liquid crystal.But it is long that its traditional synthesis process exists operational path, raw materials used danger, shortcomings such as production cost height.Merck patent DE3939116 discloses a kind of method: will under-70 ℃ with BuLi
The ortho position metal ionization of fluorine, obtain through series reaction such as carbonylations again
The used BuLi of this preparation technology is extremely inflammable and explosive, and-70 ℃ industrial being difficult to of temperature condition reaches; And the DE4327749 of Merck house journal disclosed synthetic (
) route is:
Wherein used highly basic LDA is inflammable and explosive equally.The route of disclosed a kind of synthetic such monomer liquid crystal of the US4917819 of Chisso house journal is:
Obviously, it is very long that it makes each route, can increase very big production cost undoubtedly.And Chisso company
The US4468340 patent adopts I
2/ HIO
3Make iodination reagent, cyaniding then obtains
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, providing a kind of can reduce production costs, and reduces the preparation method that the synthetic 4-of industrial production needs (trans-4 '-substituted cyclohexyl) benzene nitrile monomer liquid crystal is satisfied in environmental pollution.
Purpose of the present invention can reach by following measures:
A kind of preparation method of benzene nitrile monomer liquid crystal, its special character is that the synthetic route of this benzene nitrile monomer liquid crystal is
Wherein R is C
1～C
10Straight chained alkyl, n=0 or 2, m=0 or 1, the A=cyclohexyl, Y, Z=F or H atom, but Y have one at least for the F atom among the Z, reacting used cyanating reagent is cuprous cyanide, raw material is
The consumption of cuprous cyanide is 1～4 times of feed molar number, and reaction solvent is high boiling polar aprotic solvent N,N-dimethylacetamide or tetramethylene sulfone or their mixed solvent, and the cyanogenation temperature is 160～260 ℃, preferred 200～210 ℃; 4～10 hours reaction times, preferred 4～5 hours.
The present invention compared with prior art has following positively effect:
(1) avoided inflammable, explosive alkaline such as BuLi, LDA to use among the preparation technology, made preparation technology have more security;
(2) reduce reactions steps, shortened synthesis cycle, thereby reduced production cost;
(3) avoided a large amount of spent acid, exhaust gas discharging, reduced the pollution to environment, used raw material is environmentally friendly.
The preparation method of 4-disclosed by the invention (trans-4 '-substituted cyclohexyl) benzene nitrile monomer liquid crystal is applicable to:
4-(trans-4 '-alkyl-cyclohexyl)-2-fluorobenzonitrile, alkyl=C
1～C
10Straight chained alkyl, structural formula:
4-(trans-4 '-alkyl-cyclohexyl)-2,6-difluorobenzonilyile, alkyl=C
1～C
10Straight chained alkyl, structural formula:
4-[is trans-4 '-(trans-4 " alkyl-cyclohexyl) cyclohexyl]-the 2-fluorobenzonitrile, alkyl=C
1～C
10Straight chained alkyl, structural formula:
4-[is trans-4 '-(trans-4 " alkyl-cyclohexyl) cyclohexyl]-2,6-difluorobenzonilyile, alkyl=C
1～C
10Straight chained alkyl, structural formula:
4-" trans-4 '-[2 " (anti--the 4_-alkyl-cyclohexyl) ethyl] the cyclohexalene base " 2-F-benzene nitrile, alkyl=C
1～C
10Straight chained alkyl, structural formula:
2,6-two fluoro-4-" trans-4 '-[2 " (anti--the 4_-alkyl-cyclohexyl) ethylene group] cyclohexyl " the benzene nitrile, alkyl=C
1～C
10Straight chained alkyl, structural formula
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)-2,6-two fluorochlorobenzenes [structural formula:
Preparation
The magnesium chips of 12.2g (0.5mol) is added in the 1L there-necked flask, 113.7g (0.5mol) 2,6-two fluoro-4-bromochlorophenes are miscible in the 300ml tetrahydrofuran (THF), be added dropwise in the there-necked flask a little, be warming up to 70 ℃, initiation reaction, drip remaining 2,6-two fluoro-4-bromochlorophene solution dropwise, and insulation refluxed 1 hour.70.0g (0.5mol) is dissolved in the 100ml tetrahydrofuran (THF) the propyl group pimelinketone, splash in the Grignard reagent that above-mentioned reaction obtains, dropwise, be incubated 1 hour, add hydrolysis in the dilute hydrochloric acid then, with 100ml 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, obtain 4-(4 '-propyl group tetrahydrobenzene)-2,6-two fluorochlorobenzene 121g, [structural formula:
], GC:95%.
With 121g 4-(4 '-propyl group tetrahydrobenzene)-2,6-two fluorochlorobenzenes, 35g Raney's nickel, 700ml toluene add in the 1L autoclave, and hydrogen is defeated to try hard to keep and held 20atm in the still, in 50 ℃ of insulations 5 hours, then, the cooling release, the elimination Raney's nickel is sloughed toluene, obtains suitable, anti-blended
4-(4 '-the propyl group cyclohexyl)-2,6-two fluorochlorobenzene 120g, [structural formula:
GC:95%.
In the 1L reaction flask, add the 400ml ethylene dichloride, lower the temperature 5 ℃, add 58.7g (0.44mol) aluminum chloride.Add the 72.0g sherwood oil then, temperature is controlled at below 5 ℃, be added dropwise to suitable, the trans blended 4-that the above-mentioned reaction of 120g (0.47mol) obtains (4 '-propyl group cyclohexyl)-2,6-two fluorochlorobenzenes were in 0～5 ℃ of insulation 7 hours, pour hydrolysis in the frozen water into, organic phase is washed to neutrality, sloughs ethylene dichloride, and 130～140 ℃ fraction is collected in underpressure distillation under 20Pa again, obtain 96e 4-(trans-4 '-propyl group cyclohexyl)-2,6-two fluorochlorobenzenes [structural formula:
], GC:94%.
1.2: product 4-(trans-4 '-propyl group cyclohexyl)-2, the 6-difluorobenzonilyile [structural formula:
Preparation:
With 96.0g (0.35mol) 4-(trans-4 '-propyl group cyclohexyl) 2,6-two fluorochlorobenzenes, 68.65g (0.7mol) cuprous cyanide, 400ml tetramethylene sulfone, add in the 1L there-necked flask, stirring is warming up to 200 ℃, is incubated 7 hours, reduces to room temperature, add 300ml toluene, cross inorganic salt such as filtering to remove CuCl, filtrate is sloughed toluene with 500ml washing three times.160～180 ℃ fraction is collected in underpressure distillation under 20Pa again.
Again with underpressure distillation gained fraction with the sherwood oil recrystallization of 1ml/1g product 3 times,-25 ℃ of filtrations, the resulting white crystal of recrystallization is with petroleum ether dissolution, cross the appropriate amount of alumina column chromatography, slough sherwood oil then, vacuum-drying obtains 59.8g 4-(trans-4 '-propyl group cyclohexyl)-2,6-difluorobenzonilyile elaboration, [structural formula
], GC:99.9%, mp:53.4～55.0 ℃.
Embodiment 2:
2.1: raw material 4-" trans-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethylene group] cyclohexyl " the 2-fluorochlorobenzene, [structural formula:
] preparation:
With 123g's (0.5mol)
And 104.7g (0.5mol)
The Grignard reagent react, make
Use the tosic acid of 8.6g (0.05mol) to dewater then, obtain
Carry out double-bond hydrogenation with Raney Ni, obtain suitable, the anti-blended of 170g
GC:95% uses the aluminum chloride of 58.7g (0.44mol) then, uses the mixed solvent recrystallization three times of 1ml toluene and 1mol industrial alcohol/1g product again the condition transition of 72g sherwood oil＜5 ℃, obtains 136g
4-" trans-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethylene group] cyclohexyl " the 2-fluorochlorobenzene, structural formula:
GC:99.5%.
2.2: product 4-" trans-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethyl] cyclohexyl " the 2-fluorobenzonitrile [structural formula:
] preparation
With the 4-of 136g (0.37mol) " trans by-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethylene group] cyclohexyl " the 2-fluorochlorobenzene; 66.23g (0.74mol) cuprous cyanide; 450ml tetramethylene sulfone, add in the 1L there-necked flask, stir and be warming up to 210 ℃; be incubated 7 hours; reduce to room temperature, adding 400ml toluene, elimination inorganic salt; wash three times, slough toluene.Fraction more than 210 ℃ is collected in underpressure distillation under 20Pa again.
The fraction recrystallization of sherwood oil consumption with the 1ml/1g product to obtaining, the resulting white crystal of recrystallization is with petroleum ether dissolution, cross the appropriate amount of alumina chromatography column, slough sherwood oil, vacuum-drying, obtain 84.4g 4-" trans by-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethylene group] cyclohexyl " the 2-fluorobenzonitrile, structural formula:
GC:99.1%, mp:64.2 ℃, cp:169.6 ℃.
Embodiment 3:
3.1: according to the similarity method of embodiment 2.1, can obtain following compounds
4-" trans-4 '-[2 " (anti--4_-ethyl cyclohexyl) ethylene group] cyclohexyl " the 2-fluorochlorobenzene, GC:99.5%, yield: 75%, structural formula:
4-" trans-4 '-[2 " (anti--4_-butyl cyclohexyl) ethylene group] cyclohexyl " the 2-fluorochlorobenzene, GC:99.5%, yield: 74%, structural formula:
3.2: according to the similarity method of embodiment 2.2, can obtain the compound of following monomer liquid crystal
4-" trans-4 '-[2 " (anti--4_-ethyl cyclohexyl) ethylene group] cyclohexyl " the 2-fluorobenzonitrile, mp:70.6 ℃, cp:145.6 ℃, [structural formula:
].
4-" trans-4 '-[2 " (anti--4_-butyl cyclohexyl) ethylene group] cyclohexyl " 2-fluoro-benzene nitrile, mp:54.9 ℃, cp:165.7 ℃, [structural formula:
].
Embodiment 4:
4.1: according to embodiment 1.1 similarity methods, can obtain following compounds
4-(anti--4 '-amyl group cyclohexyl)-2,6-two fluorochlorobenzenes, GC:94%, yield: 76%, [structural formula:
].
4-(anti--4 '-propyl group cyclohexyl)-2,6-two fluorochlorobenzenes, GC:95%, yield: 78%, [structural formula:
].
4.2: according to embodiment 1.2 similarity methods, can obtain following monomer liquid crystal
4-(anti--4 '-amyl group cyclohexyl)-2, the 6-difluorobenzonilyile, mp:57 ℃, cp:-63.3 ℃, [structural formula:
].
4-(anti--4 '-propyl group cyclohexyl)-2, the 6-difluorobenzonilyile, mp:35～39 ℃, cp:-11 ℃, [structural formula:
].
Embodiment 5:
5.1: according to embodiment 2.1 similarity methods, can obtain following compounds
4-[is anti--4 '-(anti--4 " propyl group cyclohexyl) cyclohexyl]-2,6-two fluorochlorobenzenes, mp:75.4～78.0 ℃, cp:139.8～140.3 ℃, GC:99.4%, yield: 75%, [structural formula:
]
4-[is anti--4 '-(anti--4 " the propyl group cyclohexyl) cyclohexyl]-the 2-fluorochlorobenzene, GC:95%, yield: 76%[structural formula:
].
4-[is anti--4 '-(anti--4 " amyl group cyclohexyl) cyclohexyl]-2,6-two fluorochlorobenzenes, mp:66.5～68.3 ℃, cp:136.2～136.4 ℃, GC:99.5%, yield: 75%, [structural formula:
]
5.2: the similar preparation method according to embodiment 2.2 can obtain following monomer liquid crystal
4-[is anti--4 '-(anti--4 " propyl group cyclohexyl) cyclohexyl]-2, the 6-difluorobenzonilyile, mp:89～90 ℃, cp:165 ℃, [structural formula:
].
4-[is anti--4 '-(anti--4 " the propyl group cyclohexyl) cyclohexyl]-the 2-fluorobenzonitrile, mp:19.2 ℃, cp:7.2 ℃, [structural formula:
].
4-[is anti--4 '-(anti--4 " amyl group cyclohexyl) cyclohexyl]-2, the 6-difluorobenzonilyile, mp:74～75 ℃, cp:161.7～162 ℃, [structural formula:
].
Claims (8)
1, a kind of preparation method of benzene nitrile monomer liquid crystal is characterized in that the synthetic route of this benzene nitrile monomer liquid crystal is
Wherein R is C
1～C
10Straight chained alkyl, n=0 or 2, m=0 or 1, the A=cyclohexyl, Y, Z=F or H atom, but Y have one at least for the F atom among the Z, reacting used cyanating reagent is cuprous cyanide, raw material is
2, press the preparation method of the described a kind of benzene nitrile monomer liquid crystal of claim 1, the consumption that it is characterized in that cuprous cyanide is 1～4 times of feed molar number, reaction solvent is high boiling polar aprotic solvent N, N-N,N-DIMETHYLACETAMIDE or tetramethylene sulfone or their mixed solvent, temperature of reaction is 160～260 ℃, 4～10 hours reaction times.
3,, it is characterized in that preferred 200～210 ℃ of the temperature of cyanogenation by the preparation method of the described a kind of benzene nitrile monomer liquid crystal of claim 2.
4, by the preparation method of the described a kind of benzene nitrile monomer liquid crystal of claim 2, it is characterized in that preferred 4～5 hours of reaction times.
5, by the preparation method of the described a kind of benzene nitrile monomer liquid crystal of claim 2, it is characterized in that raw material 4-(trans-4 '-propyl group cyclohexyl)-2,6-two fluorochlorobenzenes [structural formula:
] the preparation method as follows
(1) magnesium chips is added in the bottle, 2,6-two fluoro-4-bromochlorophenes are miscible in tetrahydrofuran (THF), are added dropwise in the bottle, are warming up to 60-80 ℃, and reaction drips 2,6-two fluoro-4-bromochlorophene solution, 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, be incubated 1 hour, add hydrolysis in the dilute hydrochloric acid then,, merge organic phase with toluene extraction three times, 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, organic phase is washed to neutrality, sloughs toluene, obtains 4-(4 '-propyl group tetrahydrobenzene)-2,6-two fluorochlorobenzenes, [structural formula:
];
(3) with 4-(4 '-propyl group tetrahydrobenzene)-2,6-two fluorochlorobenzenes, Raney's nickel, toluene add in the autoclave, and hydrogen is defeated to try hard to keep and held 20atm in the still, in 40-60 ℃ of insulation 4-6 hour, then, and the cooling release, the elimination Raney's nickel is sloughed toluene, obtains suitable, anti-blended
4-(4 '-the propyl group cyclohexyl)-2,6-two fluorochlorobenzenes, [structural formula:
];
(4) in the reaction flask, add ethylene dichloride, lower the temperature 5-8 ℃, add aluminum chloride, add sherwood oil then, temperature is controlled at below 5 ℃, be added dropwise to suitable, the trans blended 4-that above-mentioned reaction obtains (4 '-propyl group cyclohexyl)-2,6-two fluorochlorobenzenes were in 0～5 ℃ of insulation 6-8 hour, pour hydrolysis in the frozen water into, organic phase is washed to neutrality, sloughs ethylene dichloride, and 130～140 ℃ fraction is collected in underpressure distillation under 20Pa again, obtain 4-(trans-4 '-propyl group cyclohexyl)-2,6-two fluorochlorobenzenes [structural formula:
].
6, by the preparation method of the described a kind of benzene nitrile monomer liquid crystal of claim 2, it is characterized in that product 4-(trans-4 '-propyl group cyclohexyl)-2, the 6-difluorobenzonilyile [structural formula:
] preparation:
(1) with 4-(trans-4 '-propyl group cyclohexyl) 2,6-two fluorochlorobenzenes, cuprous cyanide, tetramethylene sulfone, add in the bottle, stir and be warming up to 180-220 ℃, be incubated 6-8 hour, reduce to room temperature, add toluene, cross inorganic salt such as filtering to remove CuCl, filtrate water is given a baby a bath on the third day after its birth inferior, slough toluene, 160～180 ℃ fraction is collected in underpressure distillation under 20Pa again;
(2) again with underpressure distillation gained fraction with sherwood oil recrystallization 3 times ,-25 ℃ of filtrations, the resulting white crystal of recrystallization is with petroleum ether dissolution, peroxidation aluminium column chromatography is sloughed sherwood oil, vacuum-drying then, obtain 4-(trans-4 '-propyl group cyclohexyl)-2,6-difluorobenzonilyile elaboration, [structural formula
].
7,, it is characterized in that raw material 4-" trans by-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethylene group by the preparation method of the described a kind of benzene nitrile monomer liquid crystal of claim 2] cyclohexyl " the 2-fluorochlorobenzene, [structural formula:
] preparation:
With
With
The Grignard reagent react, make
With the tosic acid dehydration, obtain then
Carry out double-bond hydrogenation with Raney Ni, obtain suitable, anti-blended
Use aluminum chloride then, use the mixed solvent recrystallization three times of toluene and industrial alcohol product again the condition transition of sherwood oil＜5 ℃, obtain
4-" trans-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethylene group] cyclohexyl " the 2-fluorochlorobenzene, structural formula:
8,, it is characterized in that product 4-" trans by-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethyl by the preparation method of the described a kind of benzene nitrile monomer liquid crystal of claim 2] cyclohexyl " the 2-fluorobenzonitrile [structural formula:
] preparation
(1) with 4-" trans by-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethylene group] cyclohexyl " the 2-fluorochlorobenzene; cuprous cyanide, tetramethylene sulfone adds in the bottle; stir and be warming up to 200-220 ℃; be incubated 6-8 hour, reduce to room temperature, adds toluene; elimination inorganic salt; wash three times, slough toluene, again the fraction of underpressure distillation collection more than 210 ℃ under 20Pa;
(2) with the fraction recrystallization of sherwood oil to obtaining, the resulting white crystal of recrystallization is crossed the appropriate amount of alumina chromatography column with petroleum ether dissolution, slough sherwood oil, vacuum-drying, 4-" trans by-4 '-[2 " (anti--4_-propyl group cyclohexyl) ethylene group] cyclohexyl " the 2-fluorobenzonitrile, structural formula:
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| CN107573212A (en) * | 2017-10-13 | 2018-01-12 | 河北美星化工有限公司 | The synthetic method of trans 4 alkyl-cyclohexyl benzene structure liquid crystal intermediates and monomer |
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| CN1308271C (en) * | 2006-02-15 | 2007-04-04 | 南京高恒精细化工有限公司 | Preparation method of liquid crystal chemicals 4-propyl cyclohexyl benzene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107573212A (en) * | 2017-10-13 | 2018-01-12 | 河北美星化工有限公司 | The synthetic method of trans 4 alkyl-cyclohexyl benzene structure liquid crystal intermediates and monomer |
| CN107573212B (en) * | 2017-10-13 | 2020-08-04 | 宁夏中星显示材料有限公司 | Synthesis method of trans-4-alkyl cyclohexyl benzene structure liquid crystal intermediate and monomer |
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