CN102492429B - Novel polymerizable liquid crystal compound and synthesis method thereof - Google Patents
Novel polymerizable liquid crystal compound and synthesis method thereof Download PDFInfo
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- CN102492429B CN102492429B CN201110366152.XA CN201110366152A CN102492429B CN 102492429 B CN102492429 B CN 102492429B CN 201110366152 A CN201110366152 A CN 201110366152A CN 102492429 B CN102492429 B CN 102492429B
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- 150000001875 compounds Chemical class 0.000 title abstract description 29
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 19
- 238000001308 synthesis method Methods 0.000 title 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 17
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 235000007715 potassium iodide Nutrition 0.000 claims description 7
- 229960004839 potassium iodide Drugs 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- -1 nitrogenous amine Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 abstract 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 abstract 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract 2
- 238000010189 synthetic method Methods 0.000 description 39
- 239000007787 solid Substances 0.000 description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 0 CC1C(C)=C**C1 Chemical compound CC1C(C)=C**C1 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229960001866 silicon dioxide Drugs 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 230000008014 freezing Effects 0.000 description 9
- 238000007710 freezing Methods 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000284 extract Substances 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N COc1ccc(CO)cc1 Chemical compound COc1ccc(CO)cc1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- KZPCWHSKIBZFFS-UHFFFAOYSA-N COc1ccc(CO)cc1I Chemical compound COc1ccc(CO)cc1I KZPCWHSKIBZFFS-UHFFFAOYSA-N 0.000 description 1
- YBJKRDDULAFREP-UHFFFAOYSA-N Cc1c(CC(O)=O)ccc(C=O)c1 Chemical compound Cc1c(CC(O)=O)ccc(C=O)c1 YBJKRDDULAFREP-UHFFFAOYSA-N 0.000 description 1
- NXXJBZFBTWQVEU-UHFFFAOYSA-N ClCOBr.P Chemical compound ClCOBr.P NXXJBZFBTWQVEU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100070104 Mus musculus Hacl1 gene Proteins 0.000 description 1
- HJHAXUFHXPGMOO-UHFFFAOYSA-M O=Cc(cc1)ccc1O[Mn] Chemical compound O=Cc(cc1)ccc1O[Mn] HJHAXUFHXPGMOO-UHFFFAOYSA-M 0.000 description 1
- XXTKORQHKOYXIH-UHFFFAOYSA-N O=Cc1ccc(C2OCCO2)cc1 Chemical compound O=Cc1ccc(C2OCCO2)cc1 XXTKORQHKOYXIH-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005493 condensed matter Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 210000002706 plastid Anatomy 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a polymerizable liquid crystal compound. The general formula of the compound is shown in the description: wherein A1 and A2 independently are a group in the description, Q1 and Q2 independently are -H or -CH3, B1 is -(CH2)m- or -CH2(CF2)mCH2-, m is 2-18, B2 is -(CH2)n- or -CH2(CF2)nCH2-, n is 2-18, C1 and C2 respectively and independently are shown in the description, R1-R4 respectively and independently are -H, -F, -Cl, linear alkyl containing 1 to 7 carbon atoms, linear alkoxy containing 1 to 7 carbon atoms, cyano, -CF3 or -OCF3, D1 is shown in the description, D2 is groups shown in the description, -C2H4- or -C4H8-, E is shown in the description, R5-R8 respectively and independently are -H, -F, -Cl, linear alkyl containing 1 to 7 carbon atoms, linear alkoxy containing 1 to 7 carbon atoms, -CN, -CF3 or -OCF3.
Description
Technical field
The present invention relates to a kind of liquid-crystal display liquid crystalline cpd, specifically, the present invention relates to a kind of novel polymerizable liquid crystalline cpd and synthetic method thereof.
Background technology
Liquid crystal is as a kind of condensed matter, and its characteristic and structure are between solid crystals and isotropic liquid.It is a kind of liquid of order, from macroscopical physical properties, both there is mobility, the viscosity of liquid, there is again the anisotropy of crystal, can as crystal, there is double refraction, Bragg reflection, diffraction and rotation effect, also can under outer field action, produce thermo-optical, electric light or magneto-optic effect.Now, liquid crystal is more and more widely used as a kind of new function material, and liquid-crystal display (LCD), because its volume is little, lightweight, function is low, radiationless and display quality advantages of higher, has obtained development at full speed in recent years.
But LCD also exists the defect of self, such as the anisotropy at visual angle and less field range, in the time that vergence direction is observed, contrast gradient obviously declines, and sometimes even there will be the problems such as gray-scale inversion and serious color drift.Visual angle is less, and optical anisotropy is less, and vision is larger, and optical anisotropy is larger, and visual angle problem is mainly derived from the optical anisotropy of liquid crystal molecule.Conventionally, liquid crystal indicator (LCD) is made up of liquid crystal pond and two Polarizers that are disposed at its both sides, in order to expand field angle, to eliminate painted or adjust phase differential according to display format, how between liquid crystal pond and Polarizer, to configure as optically anisotropic a kind of optical compensation material, thereby improve the quality that shows image.In the optical compensation sheet material of liquid crystal indicator (LCD), can use and there is birefringent macromolecule membrane, for example, by after implementing trend process on polymerisable liquid crystal material, utilize ultraviolet ray to make its sclerosis and the optically anisotropic body of fixed orientation state forms has the optical compensation sheet material that birefringent macromolecule membrane uses as LCD and used.
Preparation good optical anisotropic films, needs good polymerisable liquid crystal monomer.And this liquid crystal monomer needs low melting point, present mesomorphic phase in room temperature or near room temperature; Colourless and there is optical, electrical, chemical stability etc.
In view of this, special proposition the present invention.
Summary of the invention
First object of the present invention is to provide a kind of novel polymerizable liquid crystalline cpd.
Another object of the present invention is to provide a kind of preparation method of novel polymerizable liquid crystalline cpd.
For realizing first object of the present invention, a kind of novel polymerizable liquid crystalline cpd is provided, its general formula is:
In said structure general formula, A1, A2 are respectively independently
wherein Q1, Q2 be independently respectively-H or-CH
3;
B
1for-(CH
2)
m-or-CH
2(CF
2)
mcH
2-, wherein m=2～18;
B
2for-(CH
2)
n-or-CH
2(CF
2)
ncH
2-, wherein n=2～18;
C1, C2 are respectively independently
wherein R
1～R
4be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon, cyano group ,-CF
3or-OCF
3;
D1 is
D2 is
or-C
2h
4-, or-C
4h
8-;
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon ,-CN ,-CF
3, or-OCF
3.
Preferred following general formula (Ia) expression for polymerisable liquid crystal compound of the present invention:
In described general formula (Ia), A1, A2 are respectively independently
wherein Q1, Q2 be independently respectively-H or-CH
3;
B
1for-(CH
2)
m-or-CH
2(CF
2)
mcH
2-, wherein m=2～18;
B
2for-(CH
2)
n-or-CH
2(CF
2)
ncH
2-, wherein n=2～18;
C1, C2 are respectively independently
wherein R
1～R
4be independently respectively-H ,-F ,-C1, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon, cyano group ,-CF
3or-OCF
3;
D1 is
D2 is
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon ,-CN ,-CF
3, or-OCF
3.
In described general formula (Ia), preferred:
A1, A2 are
wherein Q1, Q2 are-H;
B
1for-(CH
2)
m-, wherein m=3 or 6;
B
2for-(CH
2)
n-, wherein n=3 or 6;
C1, C2 are
wherein R
1～R
4for-H;
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, methyl, cyano group.
In described general formula (Ia), preferred:
M and n are 3 or 6 simultaneously;
C1, C2 are
wherein R
1～R
4for-H;
E is
wherein R
5～R
8be divided into-H.
In the present invention, the preparation method of the compound of described general formula (Ia), comprises the following steps:
(1) prepare intermediate
(2) prepare intermediate
(3) preparation
Wherein: i be 0 or 1, j be 0 or 1; In the time that i is 0, j is 1; In the time that i is 1, j is 0.
In the preparation method's of above-mentioned general formula (Ia) compound step (1), Cl-B
1-OH and
the condition of reaction be: catalyzer is potassiumiodide, and solvent is second alcohol and water, and temperature of reaction is 80～90 DEG C, 30～40 hours reaction times.
and A
1the condition of-Cl reaction is: in dichloromethane solvent, add
acid binding agent and stopper, stir, and under 0～10 DEG C of condition, drips A
1-Cl, adds rear insulation 5 hours, obtains
described acid binding agent is nitrogenous amine or nitrogen heterocyclic ring compounds, is preferably pyridine and triethylamine, and described stopper is preferably 2,6-toluene di-tert-butyl phenol.
Preferred following general formula (Ib) expression for polymerisable liquid crystal compound provided by the invention:
In described general formula (Ib), A1, A2 are respectively independently
wherein Q1, Q2 be independently respectively-H or-CH
3;
B
1for-(CH
2)
m-or-CH
2(CF
2)
mcH
2-, wherein m=2～18;
B
2for-(CH
2)
n-or-CH
2(CF
2)
ncH
2-, wherein n=2～18;
C1, C2 are respectively independently
wherein R
1～R
4be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon, cyano group ,-CF
3or-OCF
3;
D1 is
D2 is
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon ,-CN ,-CF
3, or-OCF
3.
In described general formula (Ib), preferred:
A1, A2 are
wherein Q1, Q2 are-H;
B
1for-(CH
2)
m-, wherein m=3 or 6;
B
2for-(CH
2)
n-, wherein n=3 or 6;
C1, C2 are
wherein R
1～R
4for-H;
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, methyl, cyano group.
In described general formula (Ib), preferred:
M and n are 3 or 6 simultaneously;
Cl, C2 are
wherein R
1～R
4for-H;
E is
wherein R
5～R
8be divided into-H.
In the present invention, the preparation method of the compound of described general formula (Ib), comprises the following steps:
Wherein: x is 0 or 2.
Preferred following general formula (Ic) expression for polymerisable liquid crystal compound of the present invention:
In described general formula (Ic), A1, A2 are respectively independently
wherein Q1, Q2 be independently respectively-H or-CH
3;
B
1for-(CH
2)
m-or-CH
2(CF
2)
mcH
2-, wherein m=2～18;
B
2for-(CH
2)
n-or-CH
2(CF
2)
ncH
2-, wherein n=2～18;
C1, C2 are respectively independently
wherein R
1～R
4be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon, cyano group ,-CF
3or-OCF
3;
D1 is
D2 is
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon ,-CN ,-CF
3, or-OCF
3.
In described general formula (Ic), preferred:
A1, A2 are
wherein Q1, Q2 are-H;
B
1for-(CH
2)
m-, wherein m=3 or 6;
B
2for-(CH
2)
n-, wherein n=3 or 6;
C1, C2 are
wherein R
1～R
4for-H;
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, methyl, cyano group.
In described general formula (Ic), preferred:
M and n are 3 or 6 simultaneously;
C1, C2 are
wherein R
1～R
4for-H;
E is
wherein R
5～R
8be divided into-H.
The preparation method of described general formula (Ic) compound, comprises the following steps:
(1) prepare intermediate
(2) prepare intermediate
(3) preparation
Wherein, p be 0,1 or 2, q be 0,1 or 2;
In the time that p is 0, q is 2;
In the time that p is 0, q is 1;
In the time that p is 1, q is 1;
In the time that p is 2, q is 0;
In the time that p is 0, q is 0.
Preferred following general formula (Id) expression for polymerisable liquid crystal compound of the present invention:
In described general formula (Id), A1, A2 are respectively independently
wherein Q1, Q2 be independently respectively-H or-CH
3;
B
1for-(CH
2)
m-or-CH
2(CF
2)
mcH
2-, wherein m=2～18;
B
2for-(CH
2)
n-or-CH
2(CF
2)
ncH
2-, wherein n=2～18;
C1, C2 are respectively independently
wherein R
1～R
4be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon, cyano group ,-CF
3or-OCF
3;
D1 is
D2 is-C
2h
4-, or-C
4h
8-;
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon ,-CN ,-CF
3, or-OCF
3.
In described general formula (Id), preferred:
A1, A2 are
wherein Q1, Q2 are-H;
B
1for-(CH
2)
m-, wherein m=3 or 6;
B
2for-(CH
2)
n-, wherein n=3 or 6;
C1, C2 are
wherein R
1～R
4for-H;
E is
wherein R
5～R
8be independently respectively-H ,-F ,-Cl, methyl, cyano group.
In described general formula (Id), preferred:
M and n are 3 or 6 simultaneously;
C1, C2 are
wherein R
1～R
4for-H;
E is
wherein R
5～R
8be divided into-H.
In the present invention, the preparation method of described general formula (Id) compound, comprises the following steps:
(1) with
for starting raw material, preparation
(2) with
for raw material:
Wherein, h is 0 or 2.
Beneficial effect of the present invention is:
Compound of the present invention is a kind of polymerisable liquid crystal compound being not yet disclosed of brand new, this type of Compound Phase ratio with conventional similar structures, novel polymerizable liquid crystalline cpd provided by the invention is colourless, there is good optical, electrical, chemical stability, fusing point is lower, and low temperature polymerization is better.
Secondly,, in preparation process, synthetic route simplicity of design is reasonable, reaction conditions is all comparatively gentle, reaction process is simple and safe controlled, and related reaction is stronger to the tolerance in temperature of reaction and reaction times, is easy to realize, and synthetic needed plant and instrument also belongs to common instrument, intermediate product is easy to separate, and cost is low, and yield is high, be suitable for suitability for industrialized production, be with a wide range of applications.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the target compound prepared of embodiment 19;
Fig. 2 is the nucleus magnetic hydrogen spectrum of the target compound prepared of embodiment 27;
Fig. 3 is the nucleus magnetic hydrogen spectrum of the target compound prepared of embodiment 28;
Fig. 4 is the nucleus magnetic hydrogen spectrum of the target compound prepared of embodiment 36.
Embodiment
The following examples can make the present invention of those skilled in the art's comprehend, but do not limit the present invention in any way.
Embodiment 1
Synthetic
Be furnished with mechanical stirring, in the 2L four-hole bottle of condenser, dropping into p-hydroxyphenylaceticacid 1mol, 3-propylene chlorohydrin 1.1mol, potassiumiodide 0.15mol, sodium hydroxide 2.1mol, ethanol 500ml, water 500ml.Then heated and stirred, temperature is controlled at 80～90 DEG C, is incubated 30h after gentle reflux.Middle control reaction is complete, first ethanol is steamed, then adds 400ml water.Be down to room temperature, the hydrochloric acid that dropping massfraction is 30%, is acidified to ph=1.Suction filtration, filter cake washing 2 times, obtains light yellow or white solid product, then uses ethanol-10 DEG C of crystallizations, obtains 167g
In 250ml four-hole bottle, add 0.1mol
100ml methylene dichloride, triethylamine 0.15mol, 2,6-toluene di-tert-butyl phenol 0.3g.Stir, temperature is controlled at 0～10 DEG C, drips acrylate chloride.After adding, at this temperature, be incubated again 5h.Then, add 100ml water, stir 10min.Separatory, washing organic phase 3 times.Use anhydrous sodium sulfate drying, solvent evaporate to dryness obtains
record high-efficient liquid phase color spectral purity: 95%, yield 90%.
(2) synthetic
intermediate
Be furnished with mechanical stirring, in the 2L four-hole bottle of condenser, dropping into p-Hydroxybenzaldehyde 122g (1mol), 3-propylene chlorohydrin 103.4g (1.1mol), potassiumiodide 25g (0.15mol), sodium hydroxide 44g (1.1mol), ethanol 500ml, water 500ml.Then heated and stirred, temperature is controlled at 80～90 DEG C, is incubated 36h after gentle reflux.Middle control reaction is complete, first ethanol is steamed, then adds 400ml water.Be down to room temperature, the hydrochloric acid that dropping massfraction is 30%, is acidified to ph=6.Suction filtration, filter cake washing 2 times, obtains light yellow or white solid product, 50 DEG C of oven dry of product.
In the solid of drying, add methylene dichloride 500ml, vinylformic acid 93.6g (1.3mol), DCC268g (1.3mol) .DMAP0.5g, stirring at room temperature insulation 12h.Middle control is reacted complete suction filtration and is leached solid.Filtrate 1.5L washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Use 700ml ethanol freezing and crystallizing once, dry and obtain 164g white solid
hPLC:96.3%.
In 250Ml reaction flask, add
23.4g (0.1mol), THF50ml, ethanol 50ml, stirs, and is down to 0 DEG C, drips and contains POTASSIUM BOROHYDRIDE 5.4g (0.1mol) the 30ml aqueous solution, adds and rises to stirring at room temperature 4h.Drip 5% dilute hydrochloric acid to ph=3, stir 10min.The 300ml that adds water, methylene dichloride 100ml extracts product.Organic phase washing 3 times, dry, solvent evaporated, obtains white solid.50 DEG C of oven dry, obtain 22.6g
hPLC:96.9%.
In 250Ml reaction flask, add compound
23.6g (0.1mol) with
18g (0.11mol), methylene dichloride 100ml, DCC26.8g (0.13mol), DMAP0.1g, stirring at room temperature reaction 12h, middle control is reacted complete suction filtration and is leached solid.Filtrate 150ml washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Solvent evaporated, obtains 31.7g light yellow solid
hPLC:95.6%.
In 250Ml reaction flask, add
0.1mol, THF50ml, ethanol 50ml, stirs, and is down to 0 DEG C, drips the 30ml aqueous solution that contains POTASSIUM BOROHYDRIDE 5.4g (0.1mol), adds and rises to stirring at room temperature 4h.Drip 5% dilute hydrochloric acid to pH=3, stir 10min.The 300ml that adds water, methylene dichloride 100ml extracts product.Organic phase washing 3 times, dry, solvent evaporated, obtains white solid, and 50 DEG C of oven dry, obtain 33.7g
hPLC:96.8%.
(3) synthetic target product
In reaction flask, add 150ml methylene dichloride, 0.068mol
0.068mol
dMAP 0.5g, stirs.At 20～30 DEG C, add DCC21.1g (0.1mol), temperature control 20-30 DEG C and be incubated 12h more than.Middle control is reacted complete suction filtration and is leached solid.Filtrate 150ml washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Then use 1 times of toluene and twice crystallization of 3 times of ethanol freezing and crystallizings to obtain 25.1g white plates crystal, i.e. target product.HPLC：97.24％。
Pass through
1hMR method characterizes the compound of synthesized, to confirm its structure.
1H?NMR(400MHz，DMSO-d6，ppm)δ
H：1.99(4H，-CH2-)，3.51(4H，-CH2-)，3.94(4H)，4.15(4H)，5.34(4H)，5.80(2H)，6.05(2H)，6.43(2H)，6.65(2H，J＝7.26Hz)，6.70(2H，J＝7.26Hz)，6.95(2H，J＝7.26Hz)，6.99(2H，J＝7.26Hz)，7.07(2H，J＝7.26Hz)，7.08(2H，J＝7.26Hz)。
Embodiment 2
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, be with the difference of embodiment 1: in step (1), p-hydroxyphenylaceticacid and 3-propylene chlorohydrin are incubated 40h after 80～90 DEG C of gentle reflux, acid binding agent triethylamine in step (1) is changed to pyridine, by embodiment 1 step (2)
be changed to
by in embodiment 1 step (2)
be changed to
Embodiment 3
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1
be changed to
Embodiment 4:
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1
be changed to
will
be changed to
will
be changed to
Embodiment 5
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1 step (1)
be changed to
by in step (2)
be changed to
Embodiment 6
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1 step (2)
be changed to
will
be changed to
Embodiment 7
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1 step (1)
be changed to
Embodiment 8
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1 step (2)
be changed to Cl-C
18h
36-OH.
Embodiment 9
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1 step (1)
be changed to
by in step (2)
be changed to
Embodiment 10
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1 step (1)
be changed to
by in step (2)
be changed to
Embodiment 11
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1 step (1)
be changed to
by in step (2)
be changed to
Embodiment 12
Synthetic
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1 step (1)
be changed to
by in step (2)
be changed to
Embodiment 13
Synthetic
Synthetic route:
Be furnished with mechanical stirring, in the 2L four-hole bottle of condenser, dropping into p methoxy phenol (1mol), 3-propylene chlorohydrin 103.4g (1.1mol), potassiumiodide 25g (0.15mol), sodium hydroxide 44g (1.1mol), ethanol 500ml, water 500ml.Then heated and stirred, temperature is controlled at 80～90 DEG C, is incubated 36h after gentle reflux.Middle control reaction is complete, first ethanol is steamed, then adds 400ml water.Be down to room temperature, the hydrochloric acid that dropping massfraction is 30%, is acidified to ph=6.Suction filtration, filter cake washing 2 times, obtains light yellow or white solid product, 50 DEG C of oven dry of product.
In the solid of drying, add methylene dichloride 500ml, vinylformic acid 93.6g (1.3mol), DCC 268g (1.3mol), DMAP0.5g, stirring at room temperature insulation 12h.Middle control is reacted complete suction filtration and is leached solid.Filtrate 1.5L washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Use 700ml ethanol freezing and crystallizing once, dry and obtain 165g white solid
hPLC:96.4%.
In reaction flask, add 38.5g compound
methyl-phenoxide 200ml, stirs, and is cooled to 0 DEG C, slowly adds 26.6g aluminum chloride, stirs 1h, then rises to stirring at room temperature 2h.Add 150ml5% dilute hydrochloric acid hydrolysis 30min.Separatory, washing methyl-phenoxide layer is extremely neutral, anhydrous sodium sulfate drying, solvent evaporated obtains red solid
26.5g, HPLC91.3%
In 250ML reaction flask, add compound
0.1mol with
0.11mol, methylene dichloride 100ml, DCC26.8g (0.13mol), DMAP0.1g, stirring at room temperature reaction 12h, middle control is reacted complete suction filtration and is leached solid.Filtrate 150ml washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Solvent evaporated, obtains 29.5g light yellow solid
hPLC:95.7%.
In 250Ml reaction flask, add
0.1mol, THF50ml, ethanol 50ml, stirs, and is down to 0 DEG C, drips and contains POTASSIUM BOROHYDRIDE 5.4g (0.1mol) the 30ml aqueous solution, adds and rises to stirring at room temperature 4h.Drip 5% dilute hydrochloric acid to ph=3, stir 10min.The 300ml that adds water, methylene dichloride 100ml extracts product.Organic phase washing 3 times, dry, solvent evaporated, obtains white solid, and 50 DEG C of oven dry, obtain 32.1g
hPLC:96.9%.
In reaction flask, add 0.068mol
150ml methylene dichloride, 0.068mol
dMAP 0.5g, stirs.At 20～30 DEG C, add DCC21.1g (0.1mol), temperature control 20-30 DEG C and be incubated 12h more than.Middle control is reacted complete suction filtration and is leached solid.Filtrate 150ml washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Then use 1 times of toluene and twice crystallization of 3 times of ethanol freezing and crystallizings to obtain 24.6g white plates crystal
hPLC:97.35%.
Pass through
1hMR method characterizes the compound of synthesized, to confirm its structure.
1H?NMR(400MHz，DMSO-d6，ppm)δ
H：1.99(4H，-CH2-)，3.51(2H，-CH2-)，3.94(4H)，4.15(4H)，5.34(2H)，5.80(2H，J＝5.25Hz)，6.05(2H，J＝5.25Hz)，6.43(2H，J＝5.25Hz)，6.65(2H，J＝7.26Hz)，6.84(2H，J＝7.26Hz)，6.95(2H，J＝7.26Hz)，7.04(2H，J＝7.26Hz)，7.34(2H，J＝7.26Hz)，8.07(2H，J＝7.26Hz)。
Embodiment 14
Synthetic
The present embodiment adopts the synthetic method of embodiment 13, and the difference of embodiment 13 is:
be changed to
Embodiment 15
Synthetic
The present embodiment adopts the synthetic method of embodiment 13, and the difference of embodiment 13 is: will
be changed to
be changed to
be changed to
Embodiment 16
Synthetic
The present embodiment adopts the synthetic method of embodiment 13, and the difference of embodiment 13 is: will
be changed to
be changed to
Embodiment 17
Synthetic
The present embodiment adopts the synthetic method of embodiment 13, and the difference of embodiment 13 is: will
be changed to
Embodiment 18
Synthetic
The present embodiment adopts the synthetic method of embodiment 13, and the difference of embodiment 13 is: will
be changed to
Embodiment 19
Synthetic
(1) synthetic intermediate
In 250ML reaction flask, add compound 0.1mol
with 0.11mol
methylene dichloride 100ml, DCC26.8g (0.13mol), DMAP0.1g, stirring at room temperature reaction 12h, middle control is reacted complete suction filtration and is leached solid.Filtrate 150ml washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Solvent evaporated, obtains 36.5g light yellow solid
hPLC:96.7%.
In reaction flask, add 36.5g compound
methyl-phenoxide 100ml, stirs, and is cooled to 0 DEG C, slowly adds 13.5g aluminum chloride, stirs 1.5h, then rises to room temperature.Add 100ml 5% dilute hydrochloric acid hydrolysis 10min.Separatory, washing methyl-phenoxide layer is extremely neutral, anhydrous sodium sulfate drying, solvent evaporated obtains red solid
25.2g, HPLC:93.2%.
(2) synthetic intermediate
Be furnished with mechanical stirring, in the 2L four-hole bottle of condenser, dropping into P-hydroxybenzoic acid 1mol, 3-propylene chlorohydrin 1.1mol, potassiumiodide 0.15mol, sodium hydroxide 2.1mol, ethanol 500ml, water 500ml.Then heated and stirred, temperature is controlled at 80～90 DEG C, is incubated 36h after gentle reflux.Middle control reaction is complete, first ethanol is steamed, then adds 400ml water.Be down to room temperature, the hydrochloric acid that dropping massfraction is 30%, is acidified to ph=1.Suction filtration, filter cake washing 2 times, obtains light yellow or white solid product, then uses ethanol-10 DEG C of crystallizations, obtains 166.2g
yield 84.7%.
In 250ml four-hole bottle, add 0.1mol
100ml methylene dichloride, triethylamine 0.15mol, 2,6-toluene di-tert-butyl phenol 0.3g.Stir, temperature is controlled at 0～10 DEG C, drips acrylate chloride.After adding, at this temperature, be incubated again 5h.Then, add 100ml water, stir 10min.Separatory, washing organic phase 3 times.Use anhydrous sodium sulfate drying, solvent evaporate to dryness obtains
record high-efficient liquid phase color spectral purity: 95%, yield 90%.
(3) synthetic target product:
In reaction flask, add 0.068mol
150ml methylene dichloride, 0.068mol
dMAP 0.5g, stirs.At 20～30 DEG C, add DCC21.1g (0.1mol), temperature control 20-30 DEG C and be incubated 12h more than.Middle control is reacted complete suction filtration and is leached solid.Filtrate 150ml washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Then use 1 times of toluene and twice crystallization of 3 times of ethanol freezing and crystallizings to obtain 36.2g white plates crystal
HPLC:97.24%, DSC detects Mp:56.2 DEG C.
Embodiment 20
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (2)
be changed to
Embodiment 21
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to
Embodiment 22
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to
by in step (2)
be changed to
Embodiment 23
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (2)
be changed to
HPLC:97.24%, DSC detects Mp:56.26～61.03 DEG C.
Embodiment 24
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (2)
be changed to
will
be changed to
hPLC:93.4%, DSC detects Mp:45.37～50.26 DEG C.
Embodiment 25
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to
by in step (2)
be changed to
HPLC:95.24%, DSC detects Mp:50.56～53.32 DEG C.
Embodiment 26
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to
by in step (2)
be changed to
be changed to
hPCL:97.4%, DSC detects Mp:56.59～58.81 DEG C
Embodiment 27:
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (2)
be changed to
dSC detects Mp:50.2 DEG C.
Embodiment 28:
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to
in step (2)
be changed to
dSC detects Mp:56.6 DEG C.
Embodiment 29
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to
Embodiment 30
Synthetic
(1) preparation
Drop into being equipped with in the reaction flask of nitrogen protection device, bromo chloromethyl ether phosphonium salt 41.1g, THF100ml, is cooled to 0 DEG C, adds 16.5g potassium tert.-butoxide under nitrogen protection, 0 DEG C of insulation 1h.By 17.8g
be dissolved in 50mlTHF, temperature control, lower than 10 DEG C, drops in reaction flask, after stirring 2h, rises to room temperature.Add 300ml water, 300ml petroleum ether and stirring is extracted product.Washing organic layer 2 times, after anhydrous sodium sulfate drying, crosses silicagel column, and sherwood oil rushes post.Solvent evaporated obtains white solid
gC 85.5%.
By above-mentioned solid
be dissolved in 100THF, add 5% hydrochloric acid 20ml, reflux 3h.Be hydrolyzed complete.Be down to room temperature, the 200ml that adds water, ethyl acetate 150ml extracts product.Washing ethyl acetate layer is to neutral, and anhydrous sodium sulfate drying spends the night.Solvent evaporated obtains light yellow solid compound 18.1g
gC 92.4%.
Obtain according to the synthetic method of two step products above
gC:93.6%.
(2) prepare target product
In reaction flask, add 3.1g magnesium powder, THF50ml, splashes into 1g
add initiation reaction.After to be triggered, will
28g is dissolved in 50mlTHF, slowly splashes in reaction flask at 10～20 DEG C.Then stirring at room temperature 1h.Will
21g is dissolved in 50ml toluene, drops in reaction flask at 20～30 DEG C.Add stirring at room temperature 5h.Then reaction solution is poured in the frozen water that 150ml contains 5% hydrochloric acid into low temperature hydrolysis 5min.Add 150ml methylbenzene extraction product.Toluene layer is washed to neutrality.
In toluene feed liquid, add 1g p-methyl benzenesulfonic acid, 10ml ethylene glycol, adds reflux dewatering 7h.React complete, be down to room temperature, add 5g sodium bicarbonate, 200ml is washed to neutrality.Toluene feed liquid is crossed direct silicagel column once, solvent evaporated.Use 3 times of ethanol freezing and crystallizings, obtain 29.1g white crystal compound
gC 98.7%.
By 29.1g
be dissolved in 100ml ethanol and 50ml toluene, add 1.5g 5%Pd/C, nitrogen replacement 3 times, hydrogen exchange 3 times, 30 DEG C of atmospheric hydrogenation 16h.React complete, filtration catalizer, evaporate to dryness alcohol solvent.Add 2 times of ethanol freezing and crystallizings to obtain 23.5g white crystal
gC99.6%
Be furnished with mechanical stirring, in the 2L four-hole bottle of condenser, dropping into
(1mol), 3-propylene chlorohydrin 103.4g (1.1mol), potassiumiodide 25g (0.15mol), sodium hydroxide 44g (1.1mol), ethanol 500ml, water 500ml.Then heated and stirred, temperature is controlled at 80～90 DEG C, is incubated 36h after gentle reflux.Middle control reaction is complete, first ethanol is steamed, then adds 400ml water.Be down to room temperature, the hydrochloric acid that dropping massfraction is 30%, is acidified to ph=6.Suction filtration, filter cake washing 2 times, obtains white solid, in 50 DEG C of oven dry.In the solid leukoplast of drying, add methylene dichloride 500ml, vinylformic acid 93.6g (1.3mol), DCC 268g (1.3mol), DMAP0.5g, stirring at room temperature insulation 12h.Middle control is reacted complete suction filtration and is leached solid.Filtrate 1.5L washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Use 700ml ethanol freezing and crystallizing once, dry and obtain 164g white solid
hPLC:96.3%.
In reaction flask, add 20g
50ml methylene dichloride, the formic acid that 100ml concentration is 80%, reflux 3h, reacts complete.Being down to room temperature adds 50ml methylene dichloride to stir again.After separatory, dichloromethane layer is washed to neutrality with 5% sodium bicarbonate, solvent evaporated obtains light yellow solid
18.9g, GC95.6%.
In 250Ml reaction flask, add 0.1mol
tHF50ml, ethanol 50ml, stirs, and is down to 0 DEG C, drips and contains POTASSIUM BOROHYDRIDE 5.4g (0.1mol) the 30ml aqueous solution, adds and rises to stirring at room temperature 4h.Drip 5% dilute hydrochloric acid to ph=3, stir 10min.The 300ml that adds water, methylene dichloride 100ml extracts product.Organic phase washing 3 times, dry, solvent evaporated, obtains white solid, and 50 DEG C of oven dry, obtain 22.6g
hPLC:96.9%.
In reaction flask, add 0.068mol
150ml methylene dichloride, 0.068mol
dMAP0.5g, stirs.At 20～30 DEG C, add DCC21.1g (0.1mol), temperature control 20-30 DEG C and be incubated 12h more than.Middle control is reacted complete suction filtration and is leached solid.Filtrate 150ml washes once, and dry, then evaporate to dryness adds toluene to cross silicagel column once.Then use 1 times of toluene and twice crystallization of 3 times of ethanol freezing and crystallizings to obtain 25.2g white crystal
hPLC:95.1%.
Pass through
1hMR method characterizes the compound of synthesized, to confirm its structure.
1H?NMR(400MHz，DMSO-d6，ppm)δ
H：1.62(2H，-CH2-)，1.99(4H，-CH2-)，2.55(2H，-CH2-)，3.51(2H，-CH2-)，3.94(4H)，4.15(4H)，5.34(2H)，5.80(2H，J＝5.25Hz)，6.05(2H，J＝5.25Hz)，6.43(2H，J＝5.25Hz)，6.65(2H，J＝7.26Hz)，6.72(2H，J＝7.26Hz)，6.95(2H，J＝7.26Hz)，7.01(2H，J＝7.26Hz)，7.05(2H，J＝7.26Hz)，7.14(2H，J＝7.26Hz)。
Embodiment 31
Synthetic
The present embodiment adopts the synthetic method of embodiment 24, and the difference of embodiment 24 is: omit the step (1) in embodiment 24, directly with
for raw material, by step (2) in embodiment 12
change into
can obtain target product.
Embodiment 32
Synthetic
The present embodiment adopts the synthetic method of embodiment 24, and the difference of embodiment 24 is: by step (2)
be changed to
be changed to
Embodiment 33
Synthetic
The present embodiment adopts the synthetic method of embodiment 24, and the difference of embodiment 24 is: omit the step (1) in embodiment 24, directly with
for raw material, by step (2) in embodiment 12
change into
by in step (2)
be changed to
by in step (2)
be changed to
Embodiment 34
Synthetic
The present embodiment adopts the synthetic method of embodiment 24, and the difference of embodiment 24 is: by step (1)
be changed to
by in step (2)
be changed to
Embodiment 35
Synthetic
The present embodiment adopts the synthetic method of embodiment 24, and the difference of embodiment 24 is: by step (1)
be changed to
by in step (2)
be changed to
Embodiment 36
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to
be changed to
by step (2)
be changed to
be changed to
Embodiment 37
Synthetic
The present embodiment adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to
be changed to
by step (2)
be changed to
be changed to
HPLC97.4%, DSC detects mp:69.15-71.87 DEG C.
Embodiment 38
The present embodiment adopts the synthetic method of embodiment 1, and the difference of embodiment 1 is: by embodiment 1
be changed to respectively following raw material, obtain different target products:
Embodiment 39
The present embodiment adopts the synthetic method of embodiment 13, and the difference of embodiment 13 is: will
be changed to following raw material, obtained respectively different products:
Embodiment 40
This experimental example adopts the synthetic method of embodiment 19, and the difference of embodiment 19 is: by embodiment 19 steps (1)
be changed to following raw material, obtained respectively different products:
Embodiment 41
According to the method for embodiment 34, and the difference of embodiment 34 is: will
change following raw material into, obtained respectively different target products:
Claims (6)
1. a novel polymerizable liquid crystalline cpd, its general formula is:
Wherein, A1, A2 are respectively independently
q1, Q2 respectively independently Wei – H Huo – CH
3;
B
1wei – (CH
2)
m– Huo – CH
2(CF
2)
mcH
2–, wherein m=2～18;
B
2wei – (CH
2)
n– Huo – CH
2(CF
2)
ncH
2–, wherein n=2～18;
C1, C2 are respectively independently
r
1～R
4respectively independently Wei – H, – F, – Cl, the straight chained alkyl of 1～7 carbon, the straight chain alkoxyl group of 1～7 carbon, cyano group, – CF
3huo – OCF
3;
D1 is
D2 is
or
E is
or
wherein R
5～R
8respectively independently Wei – H, – F, – Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon straight chain alkoxyl group, – CN, – CF
3, Huo – OCF
3.
2. a preparation method for liquid crystalline cpd claimed in claim 1, is characterized in that, in described general formula, D2 is
described preparation method comprises the following steps:
(1) prepare intermediate
(2) prepare intermediate
(3) preparation
Wherein: i is that 0, j is 1.
3. preparation method according to claim 2, is characterized in that, in step (1),
Cl-B
1-OH and
the condition of reaction be: catalyzer is potassiumiodide, and solvent is second alcohol and water, and temperature of reaction is 80～90 DEG C, 30～40 hours reaction times.
4. preparation method according to claim 2, is characterized in that, in step (1),
and A
1the condition of-Cl reaction is: in dichloromethane solvent, add
acid binding agent and stopper, stir, and under 0～10 DEG C of condition, drips A
1-Cl, adds rear insulation 5 hours, obtains
described acid binding agent is nitrogenous amine or nitrogen heterocyclic ring compounds, and described stopper is 2,6-toluene di-tert-butyl phenol.
5. preparation method according to claim 4, is characterized in that, described acid binding agent is pyridine or triethylamine.
6. a preparation method for liquid crystalline cpd claimed in claim 1, is characterized in that, in described general formula, D2 is
described preparation method comprises the following steps:
(1) prepare intermediate
(2) prepare intermediate
(3) preparation
wherein, p is that 1, q is 1.
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| EP2486081B1 (en) | 2009-10-11 | 2018-12-05 | Rutgers, The State University of New Jersey | Biocompatible polymers for medial devices |
| CA2863203C (en) * | 2012-02-03 | 2020-03-24 | Rutgers, The State Of University Of New Jersey | Polymeric biomaterials derived from phenolic monomers and their medical uses |
| US11472918B2 (en) | 2012-02-03 | 2022-10-18 | Rutgers, The State University Of New Jersey | Polymeric biomaterials derived from phenolic monomers and their medical uses |
| US10774030B2 (en) | 2014-12-23 | 2020-09-15 | Rutgers, The State University Of New Jersey | Polymeric biomaterials derived from phenolic monomers and their medical uses |
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| TWI378992B (en) * | 2008-11-14 | 2012-12-11 | Chimei Innolux Corp | Liquid crystal composition for use in liquid crystal display |
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