CN102492429A - 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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- CN102492429A CN102492429A CN201110366152XA CN201110366152A CN102492429A CN 102492429 A CN102492429 A CN 102492429A CN 201110366152X A CN201110366152X A CN 201110366152XA CN 201110366152 A CN201110366152 A CN 201110366152A CN 102492429 A CN102492429 A CN 102492429A
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- 150000001875 compounds Chemical class 0.000 title abstract description 68
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 19
- 238000001308 synthesis method Methods 0.000 title 1
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 37
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 29
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical group [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 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
- 239000002994 raw material Substances 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229960004839 potassium iodide Drugs 0.000 claims description 7
- 235000007715 potassium iodide Nutrition 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 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
- 125000004432 carbon atom Chemical group C* 0.000 abstract 4
- 125000004093 cyano group Chemical group *C#N 0.000 abstract 2
- 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
- 238000000034 method Methods 0.000 description 44
- 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- 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
- 0 Cc1c(CO)c(O)c(C)c(*)c1* Chemical compound Cc1c(CO)c(O)c(C)c(*)c1* 0.000 description 9
- 230000008014 freezing Effects 0.000 description 9
- 238000007710 freezing Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-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
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 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
- 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
- 230000007935 neutral effect Effects 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
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 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
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- QRMPKOFEUHIBNM-UHFFFAOYSA-N CC1CCC(C)CC1 Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-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-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity 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
- 239000012071 phase 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
- 102100027324 2-hydroxyacyl-CoA lyase 1 Human genes 0.000 description 1
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HAPRQTRXSCRJSW-UHFFFAOYSA-N C=CC(OCCCCCCOc1ccc(CC(O)=O)cc1)=O Chemical compound C=CC(OCCCCCCOc1ccc(CC(O)=O)cc1)=O HAPRQTRXSCRJSW-UHFFFAOYSA-N 0.000 description 1
- HEOPQXJWXUGRRN-UHFFFAOYSA-N C=CC(OCCCOc1ccc(CC(O)=O)cc1)=O Chemical compound C=CC(OCCCOc1ccc(CC(O)=O)cc1)=O HEOPQXJWXUGRRN-UHFFFAOYSA-N 0.000 description 1
- NXXJBZFBTWQVEU-UHFFFAOYSA-N ClCOBr.P Chemical compound ClCOBr.P NXXJBZFBTWQVEU-UHFFFAOYSA-N 0.000 description 1
- 101001009252 Homo sapiens 2-hydroxyacyl-CoA lyase 1 Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NRCCSDVEUWXOMG-UHFFFAOYSA-N OC(CCc1ccc(C=O)cc1)=O Chemical compound OC(CCc1ccc(C=O)cc1)=O NRCCSDVEUWXOMG-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N OC(c(cc1)ccc1O)=O Chemical compound OC(c(cc1)ccc1O)=O FJKROLUGYXJWQN-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
- 230000002950 deficient 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
- 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
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 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
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- 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 as the follow: wherein A1 and A2 independently are as the follow, 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 as the follow, 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 as the follow, D2 is -C2H4- or -C4H8-, E is as the follow, 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 and use liquid crystalline cpd, specifically, the present invention relates to a kind of novel polymerizable liquid crystalline cpd and compound 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; See from macroscopical physical properties; The flowability, the viscosity that had both had liquid; Have the crystalline anisotropy again, can double refraction, Bragg reflection, diffraction and rotation effect take place, also can under outer field action, produce hot light, electric light or magneto-optic effect as crystal.Now, liquid crystal more and more is widely used as a kind of new function material, and liquid-crystal display (LCD) is because its volume is little, in light weight, function is low, radiationless and display quality advantages of higher, has obtained development at full speed in recent years.
Yet also there is the defective of self in LCD, and such as the anisotropy at visual angle and less field range, when vergence direction was observed, contrast gradient obviously descended, sometimes even gray-scale inversion and serious problems such as color drift can occur.The visual angle is more little, and optical anisotropy is more little, and vision is big more, and optical anisotropy is big more, and the visual angle problem is mainly derived from the optical anisotropy of liquid crystal molecule.Usually; Liquid crystal indicator (LCD) is made up of liquid crystal pond and two Polarizers that are disposed at its both sides; For enlarge field angle, eliminate painted, or according to display format adjustment phase differential; How between liquid crystal pond and Polarizer, to dispose as optically anisotropic a kind of optical compensation material, thus the quality of raising display image.In the optical compensation sheet material of liquid crystal indicator (LCD), can use and have birefringent macromolecule membrane; For example by after implementing trend on the polymerisable liquid crystal material and handling, utilize ultraviolet ray to make its sclerosis and the birefringent macromolecule membrane that has that optically anisotropic body constituted of fixed orientation state is used as the optical compensation sheet material that LCD uses.
Preparation good optical anisotropic films needs good polymerisable liquid crystal monomer.And this liquid crystal monomer needs lower melting point, near room temperature or room temperature, presents mesomorphic phase; Colourless and have light, electricity, a chemicalstability etc.
In view of this, special proposition the present invention.
Summary of the invention
First purpose 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 purpose of the present invention; A kind of novel polymerizable liquid crystalline cpd is provided, and its general formula is:
In the said structure general formula, A1, A2 do respectively independently
Wherein Q1, Q2 be independently respectively-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R wherein
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 does
Or-C
2H
4-, or-C
4H
8-;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
Preferred polymerisable liquid crystal compound of the present invention is represented with formula (Ia):
In the said general formula (Ia), A1, A2 do respectively independently
Wherein Q1, Q2 be independently respectively-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R wherein
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of C1, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 is
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
In the said general formula (Ia), preferred:
A1, A2 are
, and wherein Q1, Q2 are-H;
B
1For-(CH
2)
m-, m=3 or 6 wherein;
B
2For-(CH
2)
n-, n=3 or 6 wherein;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-Cl, methyl, cyanic acid.
In the said general formula (Ia), preferred:
M and n are 3 or 6 simultaneously;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Be divided into-H.
Among the present invention, the preparation method of the compound of said general formula (Ia) may further comprise the steps:
(1) preparation midbody
(2) preparation midbody
(3) preparation
Wherein: i is 0 or 1, and j is 0 or 1; When i was 0, j was 1; When i was 1, j was 0.
In the preparing method's of above-mentioned general formula (Ia) compound the step (1), Cl-B
1-OH with
The condition of reaction be: catalyzer is a potassiumiodide, and solvent is the second alcohol and water, and temperature of reaction is 80～90 ℃, 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 ℃ of condition, drip A
1-Cl adds back insulation 5 hours, obtains
Said acid binding agent is nitrogenous amine or nitrogen heterocyclic ring compounds, is preferably pyridine and triethylamine, and said stopper is preferably 2, the 6-toluene di-tert-butyl phenol.
Preferred polymerisable liquid crystal compound provided by the invention is represented with formula (Ib):
In the said general formula (Ib), A1, A2 do respectively independently
Wherein Q1, Q2 be independently respectively-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R wherein
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 is
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
In the said general formula (Ib), preferred:
A1, A2 are
, and wherein Q1, Q2 are-H;
B
1For-(CH
2)
m-, m=3 or 6 wherein;
B
2For-(CH
2)
n-, n=3 or 6 wherein;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-Cl, methyl, cyanic acid.
In the said general formula (Ib), preferred:
M and n are 3 or 6 simultaneously;
Cl, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Be divided into-H.
Among the present invention, the preparation method of the compound of said general formula (Ib) may further comprise the steps:
Wherein: x is 0 or 2.
Preferred polymerisable liquid crystal compound of the present invention is represented with formula (Ic):
In the said general formula (Ic), A1, A2 do respectively independently
Wherein Q1, Q2 be independently respectively-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R wherein
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 is
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
In the said general formula (Ic), preferred:
A1, A2 are
, and wherein Q1, Q2 are-H;
B
1For-(CH
2)
m-, m=3 or 6 wherein;
B
2For-(CH
2)
n-, n=3 or 6 wherein;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-Cl, methyl, cyanic acid.
In the said general formula (Ic), preferred:
M and n are 3 or 6 simultaneously;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Be divided into-H.
The preparation method of said general formula (Ic) compound may further comprise the steps:
(1) preparation midbody
(2) preparation midbody
(3) preparation
Wherein, p is 0,1 or 2, and q is 0,1 or 2;
Q is 2 when p is 0;
Q is 1 when p is 0;
Q is 1 when p is 1;
Q is 0 when p is 2;
Q is 0 when p is 0.
Preferred polymerisable liquid crystal compound of the present invention is represented with formula (Id):
In the said general formula (Id), A1, A2 do respectively independently
Wherein Q1, Q2 be independently respectively-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R wherein
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 is-C
2H
4-, or-C
4H
8-;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
In the said general formula (Id), preferred:
A1, A2 are
, and wherein Q1, Q2 are-H;
B
1For-(CH
2)
m-, m=3 or 6 wherein;
B
2For-(CH
2)
n-, n=3 or 6 wherein;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-Cl, methyl, cyanic acid.
In the said general formula (Id), preferred:
M and n are 3 or 6 simultaneously;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Be divided into-H.
Among the present invention, the preparation method of said general formula (Id) compound may further comprise the steps:
(1) be starting raw material with
, preparation
(2) be raw material with
:
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 that is not disclosed as yet of brand new; Compare with this compounds of conventional similar structures; Novel polymerizable liquid crystalline cpd provided by the invention is colourless; Have good light, electricity, chemicalstability, fusing point is lower, and low temperature polymerization property is better.
Secondly, in the preparation process, the synthetic route simplicity of design is reasonable, and reaction conditions is all comparatively gentle; Reaction process is simple and safe controlled, and related the reaction pair temperature of reaction and the tolerance in reaction times are stronger, is easy to realize; And synthetic needed plant and instrument also belongs to common instrument, and intermediate product is easy to separate, and cost is low; Yield is high, is suitable for suitability for industrialized production, is with a wide range of applications.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the target compound of embodiment 19 preparations;
Fig. 2 is the nucleus magnetic hydrogen spectrum of the target compound of embodiment 27 preparations;
Fig. 3 is the nucleus magnetic hydrogen spectrum of the target compound of embodiment 28 preparations;
Fig. 4 is the nucleus magnetic hydrogen spectrum of the target compound of embodiment 36 preparations.
Embodiment
Following embodiment can make those skilled in the art more fully understand the present invention, but does not limit the present invention in any way.
Synthetic
Be furnished with mechanical stirring, in the 2L four-hole bottle of condensing surface, dropping into p-hydroxyphenylaceticacid 1mol, 3-propylene chlorohydrin 1.1mol, potassiumiodide 0.15mol, sodium hydroxide 2.1mol, ethanol 500ml, water 500ml.Heated and stirred then, temperature is controlled at 80～90 ℃, is incubated 30h after the gentle reflux.Middle control reaction finishes, and earlier ethanol is steamed, and adds 400ml water again.Reduce to room temperature, the dropping massfraction is 30% hydrochloric acid, is acidified to ph=1.Suction filtration; Filter cake washing 2 times; Obtain light yellow or the white solid product; Use ethanol-10 ℃ of crystallizations again, obtain 167g
In the 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 ℃, drips acrylate chloride.Add the back and under this temperature, be incubated 5h again.Then, add 100ml water, stir 10min.Separatory, washing organic phase 3 times.Use anhydrous sodium sulfate drying; The solvent evaporate to dryness obtains
and records the high-efficient liquid phase color spectral purity: 95%, and yield 90%.
(2) synthetic
midbody
Be furnished with mechanical stirring, in the 2L four-hole bottle of condensing surface, dropping into PARA HYDROXY BENZALDEHYDE 122g (1mol), 3-propylene chlorohydrin 103.4g (1.1mol), potassiumiodide 25g (0.15mol), sodium hydroxide 44g (1.1mol), ethanol 500ml, water 500ml.Heated and stirred then, temperature is controlled at 80～90 ℃, is incubated 36h after the gentle reflux.Middle control reaction finishes, and earlier ethanol is steamed, and adds 400ml water again.Reduce to room temperature, the dropping massfraction is 30% hydrochloric acid, is acidified to ph=6.Suction filtration, filter cake washing 2 times obtains light yellow or the white solid product, 50 ℃ of oven dry of product.
In the solid of oven dry, add methylene dichloride 500ml, vinylformic acid 93.6g (1.3mol), DCC268g (1.3mol) .DMAP0.5g, stirring at room insulation 12h.Middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 1.5L washes once, drying, and evaporate to dryness adding toluene is crossed silicagel column once then.Use 700ml ethanol freezing and crystallizing once, oven dry obtains 164g white solid
HPLC:96.3%.
In the 250Ml reaction flask; Add
23.4g (0.1mol), THF50ml, ethanol 50ml; Stir; Reduce to 0 ℃, drip and contain POTASSIUM BOROHYDRIDE 97MIN 5.4g (0.1mol) the 30ml aqueous solution, add and rise to stirring at room 4h.Dropwise 5 % Hydrogen chloride stirs 10min to ph=3.Add water 300ml, methylene dichloride 100ml extracts product.Organic phase washing 3 times, drying, solvent evaporated obtains white solid.50 ℃ of oven dry obtain 22.6g
HPLC:96.9%.
In the 250Ml reaction flask; Add compound
23.6g (0.1mol) and
18g (0.11mol); Methylene dichloride 100ml; DCC26.8g (0.13mol); DMAP0.1g; Stirring at room reaction 12h, middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 150ml washes once, drying, and evaporate to dryness adding toluene is crossed silicagel column once then.Solvent evaporated obtains 31.7g light yellow solid
HPLC:95.6%.
In the 250Ml reaction flask; Add
0.1mol, THF50ml, ethanol 50ml; Stir; Reduce to 0 ℃, drip the 30ml aqueous solution that contains POTASSIUM BOROHYDRIDE 97MIN 5.4g (0.1mol), add and rise to stirring at room 4h.Dropwise 5 % Hydrogen chloride stirs 10min to pH=3.Add water 300ml, methylene dichloride 100ml extracts product.Organic phase washing 3 times; Dry; Solvent evaporated; Obtain white solid, 50 ℃ of oven dry obtain 33.7g
HPLC:96.8%.
(3) synthetic title product
In reaction flask, add 150ml methylene dichloride, 0.068mol
0.068mol
DMAP 0.5g, stir.At 20～30 ℃, add DCC21.1g (0.1mol), temperature control 20-30 ℃ and be incubated more than the 12h.Middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 150ml washes once, drying, and evaporate to dryness adding toluene is crossed 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. title product then.HPLC：97.24％。
Through
1The HMR method characterizes institute's synthetic compound, 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
Present embodiment adopts the compound method of embodiment 1; Be with the difference of embodiment 1: p-hydroxyphenylaceticacid and 3-propylene chlorohydrin are incubated 40h in the step (1) after 80～90 ℃ of gentle reflux; Acid binding agent triethylamine in the step (1) is changed to pyridine,
in embodiment 1 step (2) is changed to
with
in embodiment 1 step (2) is changed to
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
among the embodiment 1 is changed to
Embodiment 4:
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
is changed to
is changed to
among the embodiment 1 is changed to
Embodiment 5
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
in the step (2) is changed to
with
in embodiment 1 step (1) is changed to
Embodiment 6
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
in embodiment 1 step (2) is changed to
is changed to
Embodiment 7
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
in embodiment 1 step (1) is changed to
Embodiment 8
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be: with in embodiment 1 step (2)
Be changed to Cl-C
18H
36-OH.
Embodiment 9
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
in the step (2) is changed to
with
in embodiment 1 step (1) is changed to
Embodiment 10
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
in the step (2) is changed to
with
in embodiment 1 step (1) is changed to
Embodiment 11
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
in the step (2) is changed to
with
in embodiment 1 step (1) is changed to
Embodiment 12
Synthetic
Present embodiment adopts the compound method of embodiment 1 and the difference of embodiment 1 to be:
in the step (2) is changed to
with
in embodiment 1 step (1) is changed to
Embodiment 13
Synthetic
Synthetic route:
Be furnished with mechanical stirring, in the 2L four-hole bottle of condensing surface, 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.Heated and stirred then, temperature is controlled at 80～90 ℃, is incubated 36h after the gentle reflux.Middle control reaction finishes, and earlier ethanol is steamed, and adds 400ml water again.Reduce to room temperature, the dropping massfraction is 30% hydrochloric acid, is acidified to ph=6.Suction filtration, filter cake washing 2 times obtains light yellow or the white solid product, 50 ℃ of oven dry of product.
In the solid of oven dry, add methylene dichloride 500ml, vinylformic acid 93.6g (1.3mol), DCC 268g (1.3mol), DMAP0.5g, stirring at room insulation 12h.Middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 1.5L washes once, drying, and evaporate to dryness adding toluene is crossed silicagel column once then.Use 700ml ethanol freezing and crystallizing once, oven dry obtains 165g white solid
HPLC:96.4%.
In reaction flask, add 38.5g compound
methyl-phenoxide 200ml; Stir; Be cooled to 0 ℃; Slowly add the 26.6g aluminum chloride, stir 1h, rise to stirring at room 2h then.Add 150ml5% Hydrogen chloride hydrolysis 30min.Separatory; Washing methyl-phenoxide layer is to neutral; Anhydrous sodium sulfate drying; Solvent evaporated obtains red solid
26.5g, HPLC91.3%
In the 250ML reaction flask; Add compound
0.1mol and
0.11mol; Methylene dichloride 100ml; DCC26.8g (0.13mol); DMAP0.1g; Stirring at room reaction 12h, middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 150ml washes once, drying, and evaporate to dryness adding toluene is crossed silicagel column once then.Solvent evaporated obtains 29.5g light yellow solid
HPLC:95.7%.
In the 250Ml reaction flask; Add
0.1mol, THF50ml, ethanol 50ml; Stir; Reduce to 0 ℃, drip and contain POTASSIUM BOROHYDRIDE 97MIN 5.4g (0.1mol) the 30ml aqueous solution, add and rise to stirring at room 4h.Dropwise 5 % Hydrogen chloride stirs 10min to ph=3.Add water 300ml, methylene dichloride 100ml extracts product.Organic phase washing 3 times; Dry; Solvent evaporated; Obtain white solid, 50 ℃ of oven dry obtain 32.1g
HPLC:96.9%.
In reaction flask, add 0.068mol
150ml methylene dichloride, 0.068mol
DMAP 0.5g, stir.At 20～30 ℃, add DCC21.1g (0.1mol), temperature control 20-30 ℃ and be incubated more than the 12h.Middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 150ml washes once, drying, and evaporate to dryness adding toluene is crossed 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% then.
Through
1The HMR method characterizes institute's synthetic compound, 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
Present embodiment adopts the compound method of embodiment 13 and the difference of embodiment 13 to be:
is changed to
Embodiment 15
Synthetic
Present embodiment adopts the compound method of embodiment 13 and the difference of embodiment 13 to be:
is changed to
be changed to
and be changed to
Synthetic
Present embodiment adopts the compound method of embodiment 13 and the difference of embodiment 13 to be:
is changed to
is changed to
Embodiment 17
Synthetic
Present embodiment adopts the compound method of embodiment 13 and the difference of embodiment 13 to be:
is changed to
Embodiment 18
Synthetic
Present embodiment adopts the compound method of embodiment 13 and the difference of embodiment 13 to be:
is changed to
Embodiment 19
Synthetic
(1) synthetic intermediate
In the 250ML reaction flask; Add compound 0.1mol
and 0.11mol
methylene dichloride 100ml; DCC26.8g (0.13mol); DMAP0.1g; Stirring at room reaction 12h, middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 150ml washes once, drying, and evaporate to dryness adding toluene is crossed silicagel column once then.Solvent evaporated obtains 36.5g light yellow solid
HPLC:96.7%.
In reaction flask, add 36.5g compound
methyl-phenoxide 100ml; Stir; Be cooled to 0 ℃; Slowly add the 13.5g aluminum chloride, stir 1.5h, rise to room temperature then.Add 100ml 5% Hydrogen chloride hydrolysis 10min.Separatory; Washing methyl-phenoxide layer is to 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 condensing surface, dropping into PHB 1mol, 3-propylene chlorohydrin 1.1mol, potassiumiodide 0.15mol, sodium hydroxide 2.1mol, ethanol 500ml, water 500ml.Heated and stirred then, temperature is controlled at 80～90 ℃, is incubated 36h after the gentle reflux.Middle control reaction finishes, and earlier ethanol is steamed, and adds 400ml water again.Reduce to room temperature, the dropping massfraction is 30% hydrochloric acid, is acidified to ph=1.Suction filtration; Filter cake washing 2 times; Obtain light yellow or the white solid product; Use ethanol-10 ℃ of crystallizations again, obtain 166.2g
yield 84.7%.
In the 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 ℃, drips acrylate chloride.Add the back and under this temperature, be incubated 5h again.Then, add 100ml water, stir 10min.Separatory, washing organic phase 3 times.Use anhydrous sodium sulfate drying; The solvent evaporate to dryness obtains
and records the high-efficient liquid phase color spectral purity: 95%, and yield 90%.
(3) synthetic title product:
In reaction flask, add 0.068mol
150ml methylene dichloride, 0.068mol
DMAP 0.5g, stir.At 20～30 ℃, add DCC21.1g (0.1mol), temperature control 20-30 ℃ and be incubated more than the 12h.Middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 150ml washes once, drying, and evaporate to dryness adding toluene is crossed 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 then
HPLC:97.24%, DSC detects Mp:56.2 ℃.
Embodiment 20
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in embodiment 19 steps (2) is changed to
Embodiment 21
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in embodiment 19 steps (1) is changed to
Embodiment 22
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in the step (2) is changed to
with
in embodiment 19 steps (1) is changed to
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in embodiment 19 steps (2) is changed to
HPLC:97.24%, DSC detect Mp:56.26～61.03 ℃.
Synthetic
Present embodiment adopts the compound method of embodiment 19; Be with the difference of embodiment 19:
in embodiment 19 steps (2) is changed to
is changed to
HPLC:93.4%, DSC detects Mp:45.37～50.26 ℃.
Embodiment 25
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in the step (2) is changed to
with
in embodiment 19 steps (1) is changed to
HPLC:95.24%, DSC detect Mp:50.56～53.32 ℃.
Embodiment 26
Synthetic
Present embodiment adopts the compound method of embodiment 19; Be with the difference of embodiment 19: be changed to
HPCL:97.4% with
is changed to
in the step (2) with
in embodiment 19 steps (1) is changed to
, DSC detects Mp:56.59～58.81 ℃
Embodiment 27:
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in embodiment 19 steps (2) is changed to
DSC detects Mp:50.2 ℃.
Embodiment 28:
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be: be changed to
DSC and detect Mp:56.6 ℃
in embodiment 19 steps (1) is changed in
step (2)
.
Embodiment 29
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in embodiment 19 steps (1) is changed to
Embodiment 30
Synthetic
(1) preparation
In the reaction flask that nitrogen protection device is housed, drop into, bromo chloromethyl ether phosphonium salt 41.1g, THF100ml is cooled to 0 ℃, and nitrogen protection adds the 16.5g potassium tert.-butoxide down, 0 ℃ of insulation 1h.17.8g
is dissolved among the 50mlTHF; Temperature control is lower than 10 ℃; Drip to reaction flask, rise to room temperature behind the stirring 2h.Add 300ml water, the 300ml petroleum ether and stirring is extracted product.Washing organic layer 2 times behind the anhydrous sodium sulfate drying, is crossed silicagel column, and sherwood oil is towards post.Solvent evaporated obtains white solid
GC 85.5%.
is dissolved in 100THF with above-mentioned solid; Add 5% hydrochloric acid 20ml, reflux 3h.Hydrolysis finishes.Reduce to room temperature, add water 200ml, ETHYLE ACETATE 150ml extracts product.The washing ethyl acetate layer is to neutral, and anhydrous sodium sulfate drying spends the night.Solvent evaporated gets light yellow solid compound 18.1g
GC 92.4%.
The compound method of product obtains
GC:93.6% according to two step of front.
(2) preparation title product
In reaction flask; Add 3.1g magnesium powder; THF50ml splashes into 1g
and adds initiation reaction.After to be triggered;
28g is dissolved in 50mlTHF, slowly splashes in the reaction flask at 10～20 ℃.Stirring at room 1h then.
21g is dissolved in 50ml toluene, drops in the reaction flask at 20～30 ℃.Add stirring at room 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.The toluene layer washing is extremely neutral.
In the toluene feed liquid, add the 1g p-methyl benzenesulfonic acid, 10ml terepthaloyl moietie adds reflux dewatering 7h.Reaction finishes, and reduces to room temperature, adds the 5g sodium hydrogencarbonate, and the 200ml washing is to neutral.The 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%.
29.1g
is dissolved in 100ml ethanol and the 50ml toluene; Add 1.5g 5%Pd/C; Nitrogen replacement 3 times; Hydrogen exchange 3 times, 30 ℃ of atmospheric hydrogenation 16h.Reaction finishes, filtration catalizer, evaporate to dryness alcohol solvent.Add 2 times of ethanol freezing and crystallizings and obtain 23.5g white crystal
GC99.6%
Is being furnished with mechanical stirring; In the 2L four-hole bottle of condensing surface, drop into
(1mol), 3-propylene chlorohydrin 103.4g (1.1mol); Potassiumiodide 25g (0.15mol); Sodium hydroxide 44g (1.1mol), ethanol 500ml, water 500ml.Heated and stirred then, temperature is controlled at 80～90 ℃, is incubated 36h after the gentle reflux.Middle control reaction finishes, and earlier ethanol is steamed, and adds 400ml water again.Reduce to room temperature, the dropping massfraction is 30% hydrochloric acid, is acidified to ph=6.Suction filtration, filter cake washing 2 times obtains white solid, in 50 ℃ of oven dry.In the solid leukoplast of oven dry, add methylene dichloride 500ml, vinylformic acid 93.6g (1.3mol), DCC 268g (1.3mol), DMAP0.5g, stirring at room insulation 12h.Middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 1.5L washes once, drying, and evaporate to dryness adding toluene is crossed silicagel column once then.Use 700ml ethanol freezing and crystallizing once, oven dry obtains 164g white solid
HPLC:96.3%.
In reaction flask, add 20g
50ml methylene dichloride; 100ml concentration is 80% formic acid; Reflux 3h, reaction finishes.Reducing to room temperature adds the 50ml methylene dichloride again and stirs.Behind the separatory dichloromethane layer is washed till neutrality with 5% sodium bicarbonate water; Solvent evaporated obtains light yellow solid
18.9g, GC95.6%.
In the 250Ml reaction flask; Add 0.1mol
THF50ml; Ethanol 50ml stirs, and reduces to 0 ℃; Dropping contains POTASSIUM BOROHYDRIDE 97MIN 5.4g (0.1mol) the 30ml aqueous solution, adds and rises to stirring at room 4h.Dropwise 5 % Hydrogen chloride stirs 10min to ph=3.Add water 300ml, methylene dichloride 100ml extracts product.Organic phase washing 3 times; Dry; Solvent evaporated; Obtain white solid, 50 ℃ of oven dry obtain 22.6g
HPLC:96.9%.
In reaction flask, add 0.068mol
150ml methylene dichloride, 0.068mol
DMAP0.5g, stir.At 20～30 ℃, add DCC21.1g (0.1mol), temperature control 20-30 ℃ and be incubated more than the 12h.Middle control is reacted the suction filtration that finishes and is leached solid.Filtrating 150ml washes once, drying, and evaporate to dryness adding toluene is crossed 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% then.
Through
1The HMR method characterizes institute's synthetic compound, 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
Present embodiment adopts the compound method of embodiment 24; Be with the difference of embodiment 24: omit the step (1) among the embodiment 24; Be raw material directly,
in the step (2) among the embodiment 12 changed into
can obtain title product with
.
Embodiment 32
Synthetic
Present embodiment adopts the compound method of embodiment 24 and the difference of embodiment 24 to be:
in the step (2) is changed to
is changed to
Embodiment 33
Synthetic
Present embodiment adopts the compound method of embodiment 24; Be with the difference of embodiment 24: omit the step (1) among the embodiment 24; Be raw material directly,
in the step (2) be changed to
with
in the step (2) is changed to
with
in the step (2) among the embodiment 12 changes
into
Embodiment 34
Synthetic
Present embodiment adopts the compound method of embodiment 24 and the difference of embodiment 24 to be:
in the step (2) is changed to
with
in the step (1) is changed to
Synthetic
Present embodiment adopts the compound method of embodiment 24 and the difference of embodiment 24 to be:
in the step (2) is changed to
with
in the step (1) is changed to
Embodiment 36
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in embodiment 19 steps (1) is changed to that
is changed to
step (2)
is changed to
be changed to
Embodiment 37
Synthetic
Present embodiment adopts the compound method of embodiment 19 and the difference of embodiment 19 to be:
in embodiment 19 steps (1) is changed to that
is changed to
step (2)
is changed to
be changed to
HPLC97.4%, DSC detects mp:69.15-71.87 ℃.
Embodiment 38
Present embodiment adopts the compound method of embodiment 1; Be with the difference of embodiment 1:
among the embodiment 1 is changed to following raw material respectively, obtains different title products:
Embodiment 39
Present embodiment adopts the compound method of embodiment 13; Be with the difference of embodiment 13:
is changed to following raw material, obtained different products respectively:
Embodiment 40
This experimental example adopts the compound method of embodiment 19; Be with the difference of embodiment 19:
in embodiment 19 steps (1) is changed to following raw material, obtained different products respectively:
Embodiment 41
Method according to embodiment 34; Be with the difference of embodiment 34:
changed into following raw material, obtained different title products respectively:
Claims (19)
1. novel polymerizable liquid crystalline cpd, its general formula is:
Wherein, A1, A2 do respectively independently
Q1, Q2 be respectively independently-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 does
Or-C
2H
4-, or-C
4H
8-;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
2. novel polymerizable liquid crystalline cpd according to claim 1 is characterized in that, said general formula is (Ia):
Wherein, A1, A2 do respectively independently
Q1, Q2 be respectively independently-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 is
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
3. novel polymerizable liquid crystalline cpd according to claim 2 is characterized in that, in the said general formula (Ia):
A1, A2 are
, and wherein Q1, Q2 are-H;
B
1For-(CH
2)
m-, m=3 or 6 wherein;
B
2For-(CH
2)
n-, n=3 or 6 wherein;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-Cl, methyl, cyanic acid.
4. novel polymerizable liquid crystalline cpd according to claim 3 is characterized in that, in the said general formula (Ia):
M and n are 3 or 6 simultaneously;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Be divided into-H.
5. the preparation method of a claim 2,3 or 4 described liquid crystalline cpds is characterized in that said preparation method may further comprise the steps:
(1) preparation midbody
(2) preparation midbody
(3) preparation
Wherein: when i is 0 or 1, j is 0 or 1; When i was 0, j was 1; When i was 1, j was 0.
6. preparation method according to claim 5 is characterized in that, in the step (1),
Cl-B
1-OH with
The condition of reaction be: catalyzer is a potassiumiodide, and solvent is the second alcohol and water, and temperature of reaction is 80～90 ℃, 30～40 hours reaction times.
7. preparation method according to claim 5 is characterized in that, in the step (1),
And A
1The condition of-Cl reaction is: in dichloromethane solvent, add
Acid binding agent and stopper stir, and under 0～10 ℃ of condition, drip A
1-Cl adds back insulation 5 hours, obtains
Said acid binding agent is nitrogenous amine or nitrogen heterocyclic ring compounds, is preferably pyridine and triethylamine, and said stopper is preferably 2, the 6-toluene di-tert-butyl phenol.
8. novel polymerizable liquid crystalline cpd according to claim 1 is characterized in that, said general formula is (Ib):
Wherein, A1, A2 do respectively independently
Q1, Q2 be respectively independently-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 is
E does
R
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
9. novel polymerizable liquid crystalline cpd according to claim 8 is characterized in that, in the said general formula (Ib):
A1, A2 are
, and wherein Q1, Q2 are-H;
B
1For-(CH
2)
m-, m=3 or 6 wherein;
B
2For-(CH
2)
n-, n=3 or 6 wherein;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-Cl, methyl, cyanic acid.
10. novel polymerizable liquid crystalline cpd according to claim 9 is characterized in that, in the said general formula (Ib):
M and n are 3 or 6 simultaneously;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Be divided into-H.
11. the preparation method of a claim 8,9 or 10 described liquid crystalline cpds is characterized in that said preparation method may further comprise the steps:
Wherein: x is 0 or 2.
12. novel polymerizable liquid crystalline cpd according to claim 1 is characterized in that, said structural formula is (Ic):
Wherein, A1, A2 do respectively independently
Q1, Q2 be respectively independently-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 is
E does
R
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
13. novel polymerizable liquid crystalline cpd according to claim 12 is characterized in that, in the said general formula (Ic):
A1, A2 are
, and wherein Q1, Q2 are-H;
B
1For-(CH
2)
m-, m=3 or 6 wherein;
B
2For-(CH
2)
n-, n=3 or 6 wherein;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-Cl, methyl, cyanic acid.
14. novel polymerizable liquid crystalline cpd according to claim 13 is characterized in that, in the said general formula (Ic):
M and n are 3 or 6 simultaneously;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Be divided into-H.
15. the preparation method of a claim 12,13 or 14 described liquid crystalline cpds is characterized in that said preparation method may further comprise the steps:
(1) preparation midbody
(2) preparation midbody
(3) preparation
Wherein, p is 0,1 or 2, and q is 0,1 or 2;
Q is 2 when p is 0;
Q is 1 when p is 0
Q is 1 when p is 1;
Q is 0 when p is 2;
Q is 0 when p is 0.
16. novel polymerizable liquid crystalline cpd according to claim 1 is characterized in that, said general formula is (Id):
Wherein, A1, A2 do respectively independently
Q1, Q2 be respectively independently-H or-CH
3
B
1For-(CH
2)
m-or-CH
2(CF
2)
mCH
2-, m=2～18 wherein;
B
2For-(CH
2)
n-or-CH
2(CF
2)
nCH
2-, n=2～18 wherein;
C1, C2 do respectively independently
R
1～R
4Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon, cyanic acid ,-CF
3Or-OCF
3
D1 is
D2 is-C
2H
4-or-C
4H
8-;
E does
R
5～R
8Respectively be independently-H ,-F ,-the straight chain alkoxyl group of Cl, the straight chained alkyl of 1～7 carbon, 1～7 carbon ,-CN ,-CF
3, or-OCF
3
17. novel polymerizable liquid crystalline cpd according to claim 16 is characterized in that, in the said general formula (Id):
A1, A2 are
, and wherein Q1, Q2 are-H;
B
1For-(CH
2)
m-, m=3 or 6 wherein;
B
2For-(CH
2)
n-, n=3 or 6 wherein;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Respectively be independently-H ,-F ,-Cl, methyl, cyanic acid.
18. novel polymerizable liquid crystalline cpd according to claim 17 is characterized in that, in the said general formula (Id):
M and n are 3 or 6 simultaneously;
C1, C2 do
R wherein
1～R
4For-H;
E does
R wherein
5～R
8Be divided into-H.
19. the preparation method of a claim 16,17 or 18 described liquid crystalline cpds is characterized in that said preparation method may further comprise the steps:
(1) be starting raw material with
, preparation
(2) be raw material with
:
Wherein, h is 0 or 2.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160376401A1 (en) * | 2012-02-03 | 2016-12-29 | 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 |
| US11118011B2 (en) | 2009-10-11 | 2021-09-14 | Rutgers, The State University Of New Jersey | Biocompatible polymers for medical devices |
| 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 |
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| Publication number | Publication date |
|---|---|
| CN102492429B (en) | 2014-08-20 |
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