CN1228293C - Triphenyl diacetylene compound with reaction and liquid crystal polymer containing the compound - Google Patents
Triphenyl diacetylene compound with reaction and liquid crystal polymer containing the compound Download PDFInfo
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- CN1228293C CN1228293C CN 01134217 CN01134217A CN1228293C CN 1228293 C CN1228293 C CN 1228293C CN 01134217 CN01134217 CN 01134217 CN 01134217 A CN01134217 A CN 01134217A CN 1228293 C CN1228293 C CN 1228293C
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- ethynyl
- cholesterol
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Abstract
The present invention relates to a triphenyl diacetylene compound with reactivity shown in the following general formula (I). In the formula, Ra and Rb are independently selected from H, acryloyl and epoxy group under the condition that Ra and Rb can not be simultaneously selected from H; L1 and L2 are independently selected from -(CH2)n-, -O-(CH2)m- and -O-(CH2)m-O-, wherein n is an integer of 0 to 12; m is an integer of 1 to 12; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 and R12 are independently selected from H, C1-6 alkyl and halogen. The triphenyl diacetylene compound of the present invention and cholesterol liquid crystal can carry out copolymerization so as to manufacture a cholesterol reflective polarizing plate with large reflection wave width.
Description
Technical field
The present invention relates to the two acetylides of the reactive triphenyl of a kind of tool, particularly relating to a kind of is the liquid crystalline polymers of monomer gained with this compound, and it can be used for making and has the wide cholesterol type reflection Polarizer of wide reflection wave.
Background technology
Cholesterol type light polarizing film (Cholesteric polarizer) can reflect the light wave of specific wavelength, the mean refractive index n of its reflection kernel wavelength X, film
AveThe pitch P (pitch length) of arranging with cholesterol liquid crystal has following relation:
λ＝n
ave×P
The wide Δ λ of reflection wave (reflection bandwidth) is then relevant with the optical anisotropy's Δ n (birefringence, or title degree of birefringence, optical anisotropy) and the pitch P of film, and relational expression is as follows:
Δλ＝Δn×P
This kind cholesterol type light polarizing film can be applicable in the liquid-crystal display, improves the light service efficiency.
The method for making of cholesterol liquid crystal macromolecule is, the optically active liquid crystal monomer of tool (chiralliquid crystal monomer) is mixed with the liquid crystal monomer of non-optical activity (non-chiral), forms through UV rayed or heated polymerizable.The big I of pitch is controlled by the blending ratio of optically active liquid crystal monomer of tool and non-optical active liquid crystal monomer, increases the monomeric ratio of tool optically active liquid crystal, and then reflection wave moves toward the short wavelength.
The wide about 40-50nm of the ripple that cholesterol liquid crystal macromolecule reflected that general liquid crystal monomer material aggregates into, wide being not enough to of this reflection wave is applied in the liquid-crystal display.Need have bigger reflection wave wide as the application in the liquid-crystal display, reflection wavelength need be contained 400-700nm.It is wide that existing many researchs are devoted to improve the reflection wave of cholesterol liquid crystal macromolecule.
For example, U.S. the patent No. 6,016,177 provide a kind of multi-layer coated method, it is that side chain type cholesterol liquid crystal macromolecule with the thermal change type is dissolved in the solvent, coats on the base material of handling through orientation, behind heating, drying, coat another kind of cholesterol liquid crystal macromolecule solution again, and then heating, drying.The first layer cholesterol liquid crystal macromolecule has different pitch with second layer cholesterol liquid crystal macromolecule, therefore has bigger reflection wave wide.Yet, to reach the reflection of total visible light scope in this way, need the cholesterol liquid crystal macromolecule of coating more than three layers or three layers, the processing procedure program is complicated.
U.S. the patent No. 5,948, and 831 provide the manufacture method of the wide cholesterol liquid crystal macromolecule film of the wide reflection wave of a kind of individual layer.It uses two kinds of liquid crystal materials with differential responses, and a kind of is reactive nematic liquid crystal, and another kind is reactive cholesterol liquid crystal.Nematic liquid crystal does not have the characteristic of reflecting light, its with can form helical arrangement structure (helical structure) after cholesterol liquid crystal mixes with reflecting light characteristic, fix the arrangement of this spirane structure through UV rayed polymerizable.Because these two kinds of liquid crystal have different reactivities, reactive bigger cholesterol liquid crystal can diffuse to sensitive surface in polymerization process, cause the pitch distribution gradient of the cholesterol polymeric membrane after the polymerization, if add the dyestuff that absorbs UV light in prescription, then effect is more obvious.Though this method can make the wide increase of reflection wave, need to add the dyestuff that absorbs UV light, and the UV irradiation time is very long.
In recent years, other has many researchs to be conceived to the change of liquid crystal molecule chemical structure, and to improve the optical anisotropy, the reflection wave that increases cholesterol liquid crystal whereby is wide (according to formula Δ λ=Δ n * P).Two acetylene compound (the triphenyl diethynyl compound of triphenyl; Bis-tolane), the conjugate length of its liquid crystal core is long, therefore has high optical anisotropy, in general greater than 0.3.Table 1 shows the chemical structure and the bibliography of the two acetylene compounds of known triphenyl.Yet the two acetylene compounds of these triphenyls do not have reactivity, can't aggregate into polymer, therefore can't film forming.
The two acetylides of the known triphenyl of table 1
Summary of the invention
The object of the present invention is to provide the two acetylides of a kind of triphenyl, it is a nematic liquid crystal;
Another object of the present invention is to provide a kind of triphenyl two acetylides, it has reactivity, can carry out polyreaction to form film;
Another object of the present invention is to provide the high optically anisotropic triphenyl of a kind of tool two acetylides, it can be used as the material of making cholesterol type reflecting type polarizing plate, in order to the dilution cholesterol liquid crystal, so that the pitch increase, and it is wide to increase reflection wave;
Another object of the present invention is to provide a kind of liquid-crystal composition, it at room temperature has mesomorphic phase;
Another object of the present invention is to provide a kind of liquid crystalline polymers, it can be used for preparing cholesterol type reflecting type polarizing plate;
Another object of the present invention is to provide a kind of and can under room temperature, operate and have the wide cholesterol type reflecting type polarizing plate of wide reflection wave;
Another object of the present invention is to provide a kind of liquid crystal indicator that can under room temperature, operate.
For achieving the above object, the two acetylides of reactive triphenyl of the present invention are shown in following general formula (I):
In the formula
R
aAnd R
bBe independently selected from H, acryl (acryloyl), reach epoxy group(ing), condition is R
aAnd R
bBe not H simultaneously;
L
1And L
2Be independently selected from-(CH
2)
n-,-O-(CH
2)
m-and-O-(CH
2)
n-O-, wherein n is the integer of O to 12, m is 1 to 12 integer; And
R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11And R
12Be independently selected from H, C
1-6Alkyl and halogen.
Liquid crystalline polymers of the present invention can be a homopolymer or a multipolymer, can be used for making liquid crystal indicator, preferably is used to make the liquid crystal indicator that comprises cholesterol liquid crystal Polarizer, reflector or colored filter.Homopolymer is to be got through polyreaction by the two acetylides of triphenyl of the present invention.Multipolymer then is to be got through copolymerization by the two acetylides of triphenyl of the present invention and other monomers, and these other monomers comprise a liquid crystalline cpd, comprise a cholesterol liquid crystal altogether.
Liquid-crystal composition of the present invention can be used for making Polarizer or other elements of LCD, and this liquid-crystal composition comprises:
(a) the two ethine liquid crystal compounds of the triphenyl of the present invention of 10wt% to 98wt%; And
(b) other liquid crystalline cpds of 2wt% to 90wt%.
The present invention relates to the two acetylides of the reactive triphenyl of tool shown in a kind of following general formula (I);
In the formula
R
aAnd R
bBe independently selected from H, acryl (H
2C=CH-(C=O)-) and epoxy group(ing), condition is R
aAnd R
bBe not H simultaneously;
L
1And L
2Be independently selected from-(CH
2)
n-,-O-(CH
2)
m-and-O-(CH
2)
m-O-, wherein n is 0 to 12 integer, m is 1 to 12 integer; And
R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11And R
12Be independently selected from H, C
1-6Alkyl and halogen, wherein halogen is F, Cl or Br.
According to the preferable embodiment of the present invention, in the general formula (I), n is preferably 0 to 6 integer; M is preferably the integer of 1-6; R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
9, R
10, R
11And R
12In have one at least for H, for example have at least one to be C
1-6Alkyl.
The two acetylides of triphenyl of the present invention belong to the nematic liquid crystal molecule, and have high optical anisotropy (Δ n) in visible-range.Owing to the two acetylides of triphenyl of the present invention have high optical anisotropy, so it is suitable for the material as making cholesterol liquid crystal Polarizer, in order to the dilution cholesterol liquid crystal, so that the pitch increase, and it is wide to increase reflection wave.
Therefore, the present invention also provides a kind of liquid-crystal composition, and it comprises: (a) the two ethine liquid crystal compounds of the triphenyl of the present invention of the general formula of 10wt% to 98wt% (I); And (b) other liquid crystalline cpds of 2wt% to 90wt%, they are different with composition (a).The preferable prescription of above-mentioned liquid-crystal composition can be: (a) the two ethine liquid crystal compounds of the triphenyl of the general formula of 80wt% to 98wt% (I); And (b) other liquid crystalline cpds of 2wt% to 20wt%.Better prescription can be: (a) the two ethine liquid crystal compounds of the triphenyl of the general formula of 90wt% to 98wt% (I); And (b) other liquid crystalline cpds of 2wt% to 10wt%.Be fit to the above-mentioned liquid crystal with the two acetylide blending of triphenyl of the present invention, can be a kind of independent liquid crystal or be two or more the liquid crystal compound that liquid crystal constituted.Above-mentioned liquid crystal preferably includes a cholesterol liquid crystal, and it can be independent cholesterol liquid crystal or can be the liquid crystal compound that contains cholesterol liquid crystal.
According to preferable embodiment of the present invention, after the two acetylides of a kind of triphenyl of the present invention and a kind of cholesterol liquid crystal blending, the liquid-crystal composition of gained at room temperature has the cholesterol liquid crystal phase, therefore is suitable at room temperature operating.
In the two acetylide structures of triphenyl of the present invention, at least one terminal group is acryl or epoxy group(ing), therefore has reactivity, can carry out polyreaction.
Therefore, also to provide a kind of be the liquid crystalline polymers that monomer carries out the polymerization gained with the two acetylides of the triphenyl shown in the general formula (I) in the present invention.This liquid crystalline polymers can be a homopolymer or a multipolymer.Homopolymer is to be got through polyreaction by the two acetylides of the triphenyl of general formula (I).Multipolymer then is to be got through copolymerization by the two acetylides of the triphenyl of general formula (I) and other monomers (preferably liquid crystal).
According to preferable embodiment of the present invention, the two acetylides of general formula of the present invention (I) triphenyl elder generation and a cholesterol liquid crystal blending carry out polyreaction then and obtain multipolymer.Its ratio can be, the usage ratio of the two acetylides of triphenyl and cholesterol liquid crystal be 10wt% to 98wt% than 2wt% to 90wt%, be preferably 80wt% to 98wt% than 2wt% to 20wt%, be more preferred from 90wt% to 98wt% than 2wt% to 10wt%.
Above-mentioned liquid-crystal composition of the present invention and liquid crystalline polymers all can be used for making liquid crystal indicator.Moreover, general formula of the present invention (I) but the liquid crystal copolymer film forming of two acetylides of triphenyl and cholesterol liquid crystal and has reflectivity (it is wide to have wide reflection wave) in the scope of visible light, therefore be suitable for making cholesterol type reflecting type polarizing plate.This cholesterol type reflecting type polarizing plate can be form of film or liquid crystal cell form.
Description of drawings
For purpose of the present invention, feature and advantage can be become apparent, several embodiment cited below particularly, and conjunction with figs. are described in detail below.
Fig. 1 to Fig. 7 is the synthesis flow of liquid crystalline cpd M1 to M7 in the embodiment of the invention;
Fig. 8 shows the optical anisotropy of the two acetylide M5 of triphenyl of the present invention and the relation of wavelength;
Fig. 9 shows the optical anisotropy of the two acetylide M6 of triphenyl of the present invention and the relation of wavelength;
Figure 10 shows the optical anisotropy of the two acetylide M7 of triphenyl of the present invention and the relation of wavelength;
Figure 11 shows liquid crystalline polymers of the present invention (M2: M7=5%: the made penetration of cholesterol liquid crystal light polarizing film under different wave length 95%);
Figure 12 shows liquid crystalline polymers of the present invention (M2: M7=10%: the made penetration of cholesterol liquid crystal light polarizing film under different wave length 90%).
Embodiment
Embodiment
Reagent chemicals:
All medicines all do not change into company available from Merck, Aldrich, Lancaster or Tokyo, and are purified and directly use.All solvents are available from Merck or Fisher company.Anhydrous tetrahydro furan (THF) is with sodium metal drying, and adding benzophenone Benzophenone is an indicator.
Testing method:
In order to identify or assess the liquid crystal monomer or the polymer property of gained, adopt following testing tool:
(1) nuclear magnetic resonance spectrometer (Nuclear Magnetic Resonance Spectrometer:NMR):
Be to use Varian 300MHz nuclear magnetic resonance analyser.Use CDCl
3Be solvent, chemical shift unit is ppm, and it is Hz that constant unit is closed in the corner, and with tetramethylsilane (TMS) as internal reference (δ=0.00ppm).Symbol s represents unimodal (singlet), and d represents doublet (doublet), and t represents triplet (triplet), and q represents quartet (quartet), and m represents multiplet (multiplet);
(2) elementary errors scanning calorimeter (Differential Scanning Calorimeter; DSC):
Be to use SEIKO SSC5200 DSC and gauger/thermal analyzer (Computer/Thermal Analyzer), other uses liquid nitrogen cooling system (liquid nitrogen coolingaccessary).Temperature is done correction with In, takes a sample 5 to 10 milligrams, and heating or cooling scanning speed are 10 ℃/min.The phase transition of specimen (phase transition) temperature is got its extreme value, and it is second-order transition temperature (glass transitiontemperature) that polymkeric substance is got its maximum point of inflection (infection);
(3) polarizing microscope (Optical Polarizing Microscope; POM):
Be to use Ziess Axiophot type opticmicroscope, enlargement ratio is 40 to 800 times.Other uses Mettler FP82 type well heater and Mettler FP80 type thermostat;
(4) thin-layer chromatographic analysis (Thin Layer Chromatography; TLC):
Be to use Merck 5735DC Silica gel 60F-254 type aluminium back of the body thin slice, and examine and determine with UV lamp (UVGL-25 type).
Synthesizing of compound:
The synthesis flow of all compounds all is plotted in Fig. 1 to Fig. 7.Its synthesis step is specified in the back:
Embodiment 1: synthon M1 cholesterol 4-[3-(2-oxa-cyclopropyl) propoxy-] the benzene first
Acid esters (cholesteryl 4-[3-(2-oxiranyl) propoxy] benzoate)
Synthesis step please refer to Fig. 1.
Step 1: synthetic 5-bromine amylene (5-bromopentene) (1)
With 1, pentamethylene bromide (1,5-dibromopentane) 100g (0.41mol) is positioned over and loads onto liquid adding bottle and still tube in the 200ml two-neck bottle respectively, still tube connects the 100ml round-bottomed bottle, add 50g HMPT (the inferior phosphorus triamide of hexamethyl, hexamethyl phosphoroustriamide) in the liquid adding bottle (0.28mol).Heat behind the two-neck bottle to 180 ℃, this system is airtight, and dropwise add HMPT, and round-bottomed bottle is sentenced the liquid nitrogen cooling, and reaction does not steam to there being solution, takes out and collects liquid, and with the silicone tube column chromatography purification, elutriant is a normal hexane.Productive rate 50%.
Step 2: synthetic 4-(4-pentenyl oxygen base) phenylformic acid (4-(4-pentenyloxy) benzoicacid) (3)
With 5-bromine amylene (1) 15g (0.1mol) and 4-hydroxy-benzoic acid ethyl ester (ethyl4-hydroxybenzoate) 20g (0.12mol) and salt of wormwood 27.6g (0.2mol) with the fine (GH of second
3CN) be dissolved in the round-bottomed bottle reflux 24 hours.After the cooling, concentrate and remove acetonitrile, add entry 200ml and potassium hydroxide 5g (0.13mol), be heated to 90 ℃ of reactions 24 hours.After the cooling, with the acidifying of 6N aqueous hydrochloric acid, with extracted with diethyl ether three times, organic layer concentrates the back to be separated with the chromatography tubing string, elutriant be ethyl acetate and normal hexane (1: 2, V/V).Productive rate 70%.
Step 3: synthetic 4-[3-(2-oxa-cyclopropyl) propoxy-] and phenylformic acid (4-[3-(2-oxiranyl) propoxy] benzoic acid) (4)
4-(4-pentenyl oxygen base) phenylformic acid (3) 7.5g (36mmol) is dissolved in the round-bottomed bottle with methylene dichloride (300ml), dropwise add the MCPBA be dissolved in methylene dichloride (150ml) (-the chlorine peroxybenzoic acid, meta-chloroperoxybenzoic acid) (25g, 73mmol, 50%) in, reaction is 24 hours under the room temperature.After the end, dropwise add sodium thiosulfate solution, with extracted with diethyl ether three times, after dry the concentrating, with the silicone tube column chromatography purification, elutriant be ethyl acetate and normal hexane (1: 2, v/v).Get productive rate 72%.
Step 4: synthetic cholesterol 4-[3-(2-oxa-cyclopropyl) propoxy-] and benzoic ether (cholesteryl 4-[3-(2-oxiranyl) propoxy] benzoate) (M1)
With 4-[3-(2-oxa-cyclopropyl) propoxy-] phenylformic acid (4) 3.6g (16.2mmol), DCC (1, the 3-dicyclohexylcarbodiimide, 1,3-dicyclohexylcarbodiimide) 3.7g (18mmol), cholesterol 7.5g (20mmol), with DMAP (4-dimethylaminopyridine, 4-dimethyl-aminopyridine) 0.18g (1.6mmol) is dissolved in methylene dichloride (200ml) in round-bottomed bottle, reacts 24 hours down in dry environment.Concentrate and remove solution, separate with the chromatography tubing string, elutriant is ethyl acetate and normal hexane (1: 2).Get product productive rate 56%.
Embodiment 2: synthon M2 cholesterol [4-6-acryl oxygen base hexyloxy] benzoic ether (cholesteryl-[4-(6-acryloyloxyhexoxy)] benzoate).
Step 1: phenylformic acid ethyl ester (ethyl-4-(6-bydroxyhexyl-1-oxy) benzoate) (5) synthetic 4-(6-hydroxyl hexyl-1-oxygen base) oxygen base)
Synthesis step please refer to Fig. 2.
Get 6-Mecoral 8.2g (60mmol), 4-hydroxy-benzoic acid ethyl ester 5.0g (30mmol) and salt of wormwood 12.4g (90mmol) are dissolved in the 150ml acetonitrile reflux 24 hours.Concentrate and to remove acetonitrile, with the acetate dissolving, organic layer washing three times, dry concentrating, with the silicone tube column chromatography purification, elutriant be ethyl acetate and normal hexane (1: 4, v/v).Get colourless liquid.Productive rate 85%.
Step 2: synthetic 4-(6-hydroxyl hexyl-oxygen base) phenylformic acid (4-(6-hydroxyhexyl-1-oxy) benzoic acid) (6)
Compound (5) 8.00g (30mmol), NaOH 1.4g (35mmol) are positioned in the 500ml round-bottomed bottle, add 300ml distilled water, reflux continues reaction 2 hours again to transparent fully.Finish the back and get white solid,, get white solid with the methyl alcohol recrystallize with hcl acidifying.Productive rate 87%.
Step 3: synthetic 4-(6-acryl oxygen base hexyloxy) phenylformic acid (4-(6-acryloyloxyhexoxy) benzoic acid) (7)
Compound (6) 4.0g (16.8mmol), 4 times of equivalent anhydrous triethylamines and 100ml anhydrous methylene chloride are positioned in the 150ml round-bottomed bottle, under the ice bath, dropwise add two times of equivalent acrylate chlorides (acryloyl chloride) 3.0g (33.6mmol), be back to room temperature reaction 24 hours.Solution splashes in the 100ml ice, concentrate so that extracted with diethyl ether is dry, with the silicone tube column chromatography purification, elutriant be ethyl acetate and normal hexane (1: 3, v/v).Productive rate 65%.
Step 4: synthetic cholesterol [4-(6-acryl oxygen base hexyloxy) benzoic ether (cholesteryl-[4-(6-acryloyloxyhexoxy)] benzoate) (M2)
4-(6-acryl oxygen base hexyloxy) phenylformic acid (7) 12g (0.041mol), DCC 10.3g (0.05mol), cholesterol 19.7g (0.051mol) and DMAP 1g (9mmol) are dissolved in methylene dichloride (500ml) in round-bottomed bottle, reacted 24 hours down in dry environment.Concentrate and to remove solution, separate with the chromatography tubing string, elutriant be ethyl acetate and normal hexane (1: 5, v/v).Get product productive rate 28%.
Embodiment 3: synthon M32-3-[4-(2-2-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethyl) phenoxy group] the propyl group propylene oxide (2-3-[4-(2-2-ethyl-4-[2-(4-propylphenyl) 1-ethynyl] phenyl-1-ethyl) phenoxy] propyl oxirane).
Synthesis step please refer to Fig. 3.
Step 1: synthetic 1-iodo-4-(4-pentenyl oxygen base) benzene (1-iodo-4-(4-pentenyloxy) benzene) (8)
5-bromine amylene (1) 18g (0.12mol), iodophenol (iodophenol) 22g (0.1mol), salt of wormwood 27.6g (0.2mol) are placed round-bottomed bottle with potassiumiodide 0.5g (3mmol), add acetonitrile (800ml) dissolving, heat and refluxed 24 hours.Concentrate and to remove acetonitrile, with ether dissolution, organic layer washing three times, dry concentrating, with the silicone tube column chromatography purification, elutriant is ethyl acetate and normal hexane 1: 4.Get white solid.Productive rate 91%.
Step 2: Synthetic 2-methyl-4-[4-pentenyl oxygen base] phenyl]-the 3-butyne-2-alcohol
(2-methyl-4-[4-(4-pentenyloxy)phenyl]-3-butyn-2-ol)(9)
With 1-iodo-4-(4-pentenyl oxygen base) benzene (8) 20g (69.4mmole), 8.4g the methyl of 2-(0.1mole)-3-butyne-2-alcohol (2-methyl-3-butyn-2-ol) and 500ml triethylamine (triethylamine) are inserted in the round-bottomed bottle, under nitrogen respectively with the triphenyl phosphine (triphenylphosphine) of 1.27g (4.68mmole), 0.49g closing the cupric iodide (copper (I) iodide) of palladium (II) (bis (triphenylphosphine) palladium (II) chloride) and 0.66g (3.47mmole), chlorination (0.69mmole) two (triphenyl phosphine) adds reflux one day.Most triethylamine is taken out with the rotation thickner in the cooling back, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating,, obtain a brown transparent oily liquid with silicone tube column chromatography (20% hexane/ethyl acetate wash-out) purifying.Productive rate 91%.
Step 3: synthetic 1-(1-ethynyl)-4-(4-pentenyl oxygen base) benzene (1-(1-ethynyl)-4-(4-pentenyloxy) benzene) (10)
With 2-methyl-4-[4-(4-pentenyl oxygen base) phenyl]-3-butyne-2-alcohol (9) 12.5g (51mmole) and 1,4-diox (1,4-dioxane) 250ml inserts in the round-bottomed bottle, again potassium hydroxide (KOH) 3.4g (61mol) is added, add behind the distributive pipe leniently reflux and brush with nitrogen, acetone and some 1 were arranged after about 4-5 hour, the 4-diox is by blowing in the reaction flask to distributive pipe, add entry after the cooling, again with hexane extraction three times, the organic phase that merges is cleaned with saturated aqueous common salt again, and the organic layer of gained filters through anhydrous magnesium sulfate drying.With silicone tube column chromatography (normal hexane wash-out) purifying.Productive rate 85%.
Step 4: Synthetic 2-methyl-4-(4-propyl group phenyl)-3-butyne-2-alcohol (2-methyl-4-(4-propylphenyl)-3-butyn-2-ol) (11)
1-bromo-4-propylbenzene (1-bromo-4-propylbenzene) 13.3g (66.8mmole), 2-methyl-3-butyne-2-alcohol (2-methyl-3-butyn-2-ol) 8.0g (95mmole) and triethylamine 350ml are inserted in the round-bottomed bottle, under nitrogen, respectively palladium (II) 0.47g (0.68mmole) and cupric iodide 0.64g (3.34mmole) adding, reflux one day are closed in triphenyl phosphine 1.23g (4.7mmole), chlorination two (triphenyl phosphine).Most triethylamine is taken out with the rotation thickner in the cooling back, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating,, obtain a brown transparent oily liquid with silicone tube column chromatography (20% hexane/ethyl acetate wash-out) purifying.Productive rate 90%.
Step 5: synthetic 1-(1-ethynyl)-4-propylbenzene (1-(1-ethynyl)-4-propylbenzene) (12)
With 2-methyl-4-(4-propyl group phenyl)-3-butyne-2-alcohol (11) 15.9g (79mmole) and 1,4-diox 250ml inserts in the round-bottomed bottle, again potassium hydroxide (KOH) 4.0g (71mol) is added, add behind the distributive pipe leniently reflux and brush with nitrogen, acetone and some 1 are arranged after about 4.5 hours, the 4-diox is by blowing in the reaction flask to distributive pipe, add entry after the cooling, again with hexane extraction three times, the organic phase that merges is cleaned with saturated aqueous common salt again, the organic layer of gained filters through anhydrous magnesium sulfate drying.With silica gel chromatographic analysis (normal hexane wash-out) purifying.Productive rate 95%.
Step 6: synthetic 4-iodo-2-ethylaniline (4-iodo-2-ethylaniline) (13)
2-ethylaniline 21.8 grams (0.18mol) are placed round-bottomed bottle, add iodine 47.5 grams (0.187mol), lime carbonate 23.3 gram (0.233mol) and 100ml water respectively, at room temperature stirred one hour, in 5 minutes postcooling of 60-70 ℃ of heating.Add entry and extracted with diethyl ether, the gained organic layer concentrates with anhydrous magnesium sulfate drying, is that 10 to 1 elutriant is done the stratography of silica gel tubing string with normal hexane than ethyl acetate.Get dark brown liquid.Productive rate 97%.
Step 7: Synthetic 2-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] and aniline (2-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] aniline) (14)
4-iodo-2-ethylaniline (13) 6g (24.29mmole), 1-(1-ethynyl)-4-propylbenzene (12) 3.5g (24.3mmol) and 250ml triethylamine are inserted-round-bottomed bottle in, under nitrogen, respectively palladium (II) 0.143g (0.204mmole) and cupric iodide 78mg (0.4048mmole) adding, reflux-sky are closed in triphenyl phosphine 0.386g (1.518mmole), chlorination two (triphenyl phosphine).Take out most triethylamine after the cooling, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, with chromatographic analysis (20% hexane/ethyl acetate wash-out) purifying, obtain a brown liquid with silica gel.Productive rate 70%.
Step 8: Synthetic 2-ethyl-1-iodo-4-[2-(4-propyl group phenyl)-1-ethynyl] and benzene (2-ethyl-1-iodo-4-[2-(4-propylphenyl)-1-ethynyl] benzene) (15)
2-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl with the dilution of a small amount of tetrahydrofuran (THF)] aniline (14) 3.2g (12.8mmole) is cooled to the concentrated hydrochloric acid that adds 3.1ml (51.2mmol) after 0-5 ℃, stirred 5 minutes, add 5.2ml (25.6mmole) Sodium Nitrite frozen water solution (1g/3ml) again, under identical temperature, stirred 5-10 minute, (64mmol potassium iodide aqueous solution (3g/1ml) stirred under identical temperature 2-3 hour to add the 9.5ml of ice bath again.The product of gained is cleaned with saturated aqueous sodium thiosulfate, water and saturated aqueous common salt with normal hexane dilution back, the organic layer of gained filters through anhydrous magnesium sulfate drying, after concentrating, with chromatographic analysis (normal hexane wash-out) purifying, obtain a weak yellow liquid with silica gel.Productive rate 85%.
Step 9: Synthetic 2-ethyl-1-2-[4-(4-pentenyl oxygen base) phenyl]-1-ethynyl-4-[2-(4-propyl group phenyl)-1-ethynyl] benzene (2-ethyl-1-2-[4-(4-pentenyloxy) phenyl]-1-ethynyl-4-[2-(4-propylphenyl)-1-ethynyl] benzene) (16)
With 2-ethyl-1-iodo-4-[2-(4-propyl group phenyl)-1-ethynyl] benzene (15) 0.52g (1.39mmole), 1-(1-ethynyl)-4-(4-pentenyl oxygen base) benzene (10) 0.288g (1.53mmol) and triethylamine 50ml insert in the round-bottomed bottle, under nitrogen, respectively palladium (II) 0.01g (0.014mmole) and cupric iodide 0.13g (0.1mmol) adding, reflux one day are closed in triphenyl phosphine 0.026g (0.07mole), chlorination two (triphenyl phosphine).Take out most of triethylamine after the cooling, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, with chromatographic analysis (20% hexane/ethyl acetate wash-out) purifying, obtain a brown liquid with silica gel.Productive rate 98%.
Step 10: Synthetic 2-3-[4-2-2-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl] phenoxy group] propyl group oxyethane (2-3-[4-(2-2-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy] propyloxirane) (M3)
With 2-ethyl-1-2-[4-(4-pentenyl oxygen base) phenyl]-1-ethynyl-4-[2-(4-propyl group phenyl)-1-ethynyl] benzene (16) 0.15g (0.35mmol) is dissolved in the round-bottomed bottle with methylene dichloride (5ml), dropwise add the MCPBA 0.18g (1mmol that is dissolved in methylene dichloride (5ml), 50%) in, reaction is 24 hours under the room temperature.After the end, dropwise add sodium thiosulfate solution, with extracted with diethyl ether three times, after dry the concentrating, with the silicone tube column chromatography purification, elutriant is ethyl acetate and normal hexane 1: 2.Get productive rate 48%.
Embodiment 4: phenoxy group synthon M4 2-3-[4-(2-3-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl-] phenyl-1-ethynyl)] propyl group oxyethane
(2-3-[4-(2-3-ethyl-4-[2-(4-propylphenyl)-1-ethynyl]phenyl-1-ethynyl)phenoxy]propyloxirane)
Synthesis step please refer to the 4th figure.
Step 1: Synthetic 2-ethyl-4-[2-(4-pentenyl oxygen base phenyl)-1-ethynyl] and aniline (2-ethyl-4-[2-(4-pentenyloxyphenyl)-1-ethyny]] aniline) (17)
4-iodo-2-ethylaniline (13) 4.5g (18mmole), 1-(1-ethynyl)-4-(4-pentenyl oxygen base) benzene (10) 3.7g (20mmol) and 200ml triethylamine are inserted in the round-bottomed bottle, under nitrogen, respectively palladium (II) 0.14g (0.2mmole) and cupric iodide 0.19g (1.0mmole) adding, reflux one day are closed in triphenyl phosphine 0.37g (1.4mmole), chlorination two (triphenyl phosphine).Take out most triethylamine after the cooling, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, with chromatographic analysis (5: 1 hexane/ethyl acetate wash-outs) purifying, obtain a brown liquid with silica gel.Productive rate 71%.
Step 2: Synthetic 2-ethyl-1-iodo-4-[2-(4-pentenyl oxygen base phenyl)-1-ethynyl] and benzene (2-ethyl-1-iodo-4-[2-(4-pentenyloxyphenyl)-1-ethynyl] benzene) (18)
Will be with 2-ethyl-4-[2-(4-pentenyl oxygen base the phenyl)-1-ethynyl of a small amount of tetrahydrofuran (THF) dilution] aniline (17) 4.3g (14.1mmole) is cooled to the concentrated hydrochloric acid that adds 10ml (0.12mol) after 0-5 ℃, stirred 5 minutes, add Sodium Nitrite frozen water solution 2.9g (42mmol/10ml water) again, under identical temperature, stirred 5-10 minute, the potassium iodide aqueous solution 23.4g (0.14mol/10ml water) that adds ice bath again stirred 2-3 hour under identical temperature.The product of gained is cleaned with saturated aqueous sodium thiosulfate, water and saturated aqueous common salt with normal hexane dilution back, the organic layer of gained filters through anhydrous magnesium sulfate drying, after concentrating, with chromatographic analysis (normal hexane wash-out) purifying, obtain a weak yellow liquid with silica gel.Productive rate 70%.
Step 3: Synthetic 2-ethyl-4-2-[4-(4-pentenyl oxygen base) phenyl]-1-ethynyl-1-[2-(4-propyl group phenyl)-1-ethynyl] benzene (2-ethyl-4-2-[4-(4-pentenyloxy) phenyl]-1-ethynyl-1-[2-(4-propylphenyl)-1-ethynyl] benzene) (19)
With 2-ethyl-1-iodo-4-[2-(4-pentenyl oxygen base phenyl)-1-ethynyl] benzene (18) 2.8g (6.6mmole), 1-(1-ethynyl)-4-propylbenzene (12) 1.4g (10mmol) and triethylamine 100ml insert in the round-bottomed bottle, under nitrogen, respectively palladium (II) 0.049g (0.07mmole) and cupric iodide 0.095g (0.5mmole) adding, reflux one day are closed in triphenyl phosphine 0.09g (0.35mmol), chlorination two (triphenyl phosphine).Take out most triethylamine after the cooling, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, with chromatographic analysis (5: 1 hexane/ethyl acetate wash-outs) purifying, obtain a brown liquid with silica gel.Productive rate 60%.
Step 4: Synthetic 2-3-[4-(2-3-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group] propyl group oxyethane (2-3-[4-(2-3-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy] propyloxirane) (M4)
With 2-ethyl-4-2-[4-(4-pentenyl oxygen base) phenyl]-1-ethynyl-1-[2-(4-propyl group phenyl)-1-ethynyl] benzene (19) 0.1g (0.23mmol) is dissolved in the round-bottomed bottle with methylene dichloride (5ml), dropwise add the MCPBA 0.1g (0.6mmol that is dissolved in methylene dichloride (5ml), 50%), reacted 24 hours under the room temperature.After the end, dropwise add sodium thiosulfate solution, with extracted with diethyl ether three times, after dry the concentrating, with the silicone tube column chromatography purification, elutriant is ethyl acetate and normal hexane 1: 2.Get productive rate 30%.
Embodiment 5: synthon M5 vinylformic acid 6-[4-(2-2-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group] polyhexamethylene (6-[4-(2-2-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy] hexylacrylate)
Synthesis step please refer to Fig. 5.
Step 1: synthetic 6-(4-iodine phenoxy group)-1-hexanol (6-(4-iodophenoxy)-1-hexanol) (20)
6-Mecoral 25g (0.18mmol), iodophenol 48.4g (0.22mol), salt of wormwood 60.8g (0.44mol) are placed round-bottomed bottle with potassiumiodide 3.3g (0.02mol), add acetonitrile (480ml) dissolving, heat and refluxed 24 hours.Concentrate and to remove acetonitrile, with ether dissolution, organic layer washing three times, dry concentrating, with the silicone tube column chromatography purification, elutriant be ethyl acetate and normal hexane (1: 6, v/V).Get white solid.Productive rate 88%.
Step 2: oxygen base synthetic 4-4-[(6-hydroxyl hexyl)] phenyl-2-methyl-3-butyne-2-alcohol (4-4-[(6-hydroxyhexyl) oxy] phenyl-2-methyl-3-butyn-2-ol) (21)
6-(4-iodine phenoxy group)-1-hexanol (20) 22g (69mmole), 2-methyl-3-butyne-2-alcohol 8.4g (0.1mole) and 600ml triethylamine are inserted in the round-bottomed bottle, under nitrogen, respectively the cupric iodide adding of palladium (II) and 0.67g (3.5mmole), reflux one day are closed in the triphenyl phosphine of 1.3g (4.8mmole), the chlorination two (triphenyl phosphine) of 0.48g (0.69mole).Most triethylamine is taken out with the rotation thickner in the cooling back, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, (5: purifying l hexane/ethyl ester ethyl ester wash-out) obtains a brown transparent oily liquid with chromatographic analysis with silica gel.Productive rate 94%.
Step 3: synthetic 6-[4-(1-ethynyl) phenoxy group]-the 1-hexanol (6-[4-(1-ethynyl) phenoxy]-1-hexanol) (22)
With 4-4-[(6-hydroxyl hexyl) the oxygen base] phenyl-2-methyl-3-butyne-2-alcohol (21) 22.4g (81mmole) and 1,4-diox 220ml inserts in the round-bottomed bottle, again potassium hydroxide (KOH) 5.6g (0.1mol) is added, add behind the distributive pipe leniently reflux and brush with nitrogen, acetone and some 1 were arranged after about 4-5 hour, the 4-diox is by blowing in the reaction flask to distributive pipe, add entry after the cooling, again with hexane extraction three times, the organic phase that merges is cleaned with saturated aqueous common salt again, the organic layer of gained filters through anhydrous magnesium sulfate drying.With silica gel chromatographic analysis (5: 1 hexane/ethyl acetate wash-outs) purifying.Productive rate 70%.
Step 4: synthetic 6-[4-(2-2-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group]-the 1-hexanol (6-[4-(2-2-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy]-1-hexanol) (23)
With 2-ethyl-1-iodo-4-[2-(4-propyl group phenyl)-1-ethynyl] benzene (15) 12.1g (32.3mmole), 6-[4-(1-ethynyl) phenoxy group]-1-hexanol (22) 6.2g (28mole) and triethylamine 450ml insert in the round-bottomed bottle, under nitrogen, respectively palladium (II) 0.21g (0.3mmole) and cupric iodide 0.29g (1.5mmole) adding, reflux one day are closed in triphenyl phosphine 0.55g (2.1mmole), chlorination two (triphenyl phosphine).Most triethylamine is taken out with the rotation thickner in the cooling back, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, with chromatographic analysis (5: 1 hexane/ethyl acetate wash-outs) purifying, obtain a brown transparent oily liquid with silica gel.Productive rate 62%.
Step 5: acrylic acid synthesizing 6[4-(2-2-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group] polyhexamethylene (6-[4-(2-2-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy] hexyl acrylate) (M5)
With compound 6-[4-(2-2-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group]-1-hexanol (23) 8.1g (17mmol), anhydrous triethylamine (10.1ml, 70mmol) be positioned in the 500ml round-bottomed bottle with the 200ml anhydrous methylene chloride, under the ice bath, dropwise add acrylate chloride 3.2g (35mmol), be back to room temperature reaction 24 hours.Solution splashes in the 100ml ice, concentrates so that extracted with diethyl ether is dry, and with the silicone tube column chromatography purification, elutriant is ethyl acetate and normal hexane 1: 3.Productive rate 84%.
Fig. 8 shows the optical anisotropy of M5 and the relation of wavelength.As seen from the figure, when M5 was 550nm at wavelength, the optical anisotropy was about 0.35.
Embodiment 6: synthon M6 vinylformic acid 6-[4-(2-3-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group] polyhexamethylene (6-[4-(2-3-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy] hexyl acrylate)
Synthesis step please refer to Fig. 6.
Step 1: synthetic 6-4-[2-(4-amino-3-ethylphenyl)-1-ethynyl] and phenoxy group-1-hexanol (6-4-[2-(4-amino-3-ethylphenyl)-1-ethynyl] phenoxy-1-hexanol) (24)
With 6-[4-(1-ethynyl) phenoxy group]-1-hexanol (22) 10.0g (46.0mmole), 4-iodo-2-ethylaniline (13) 12.5g (51.0mole) and 450ml triethylamine insert in the round-bottomed bottle, under nitrogen, respectively the chlorination two (triphenyl phosphine) of the triphenyl phosphine of 0.9g (3.6mmole), 0.36g (0.5mmole) is closed the cupric iodide adding of palladium (II) and 0.5g (2.6mmole), in 50 ℃ of reacting by heating one day.Most of triethylamine is taken out with the rotation thickner in the cooling back, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, with chromatographic analysis (2: 1 hexane/ethyl acetate wash-outs) purifying, obtain a brown transparent oily liquid with silica gel.Productive rate 61%.
Step 2: synthetic 6-4-[2-(3-ethyl-4-iodophenyl)-1-ethynyl] and phenoxy group-1-hexanol (6-4-[2-(3-ethyl-4-iodophenyl)-1-ethynyl] phenoxy-1-hexanol) (25)
Will be with 6-4-[2-(4-amino-3-the ethylphenyl)-1-ethynyl of a small amount of tetrahydrofuran (THF) dilution] phenoxy group-1-hexanol (24) 3.5g (10mmole) is cooled to the concentrated hydrochloric acid that adds 4.1ml (50mmol) after 0-5 ℃, stirred 5 minutes, add 2.1g (31mmole) nitrous again and complete sodium frozen water solution (1g/3ml), under identical temperature, stirred 5-10 minute, add 10g (60mmole) potassium iodide aqueous solution (1g/1ml) of ice bath again, under identical temperature, whisk 2-3 hour.The product of gained is cleaned with saturated aqueous sodium thiosulfate, water and saturated aqueous common salt with normal hexane dilution back, the organic layer of gained filters through anhydrous magnesium sulfate drying, after concentrating, with chromatographic analysis (5: 1 hexane/ethyl acetate wash-outs) purifying, obtain a weak yellow liquid with silica gel.Productive rate 65%.
Step 3: synthetic 6-[4-(2-3-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group]-the 1-hexanol (6-[4-(2-3-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy]-1-hexanol) (26)
With 6-4-[2-(3-ethyl-4-iodophenyl)-1-ethynyl] phenoxy group-1-hexanol (25) 1.6g (3.6mmole), 1-(1-ethynyl)-4-propylbenzene (12) 0.5g (3.6mole) and 80ml triethylamine insert in the round-bottomed bottle, under nitrogen, respectively triphenyl phosphine 0.07g (0.25mmole), chlorination two (triphenyl phosphine) are closed palladium (II) 0.025g (0.036mmole) and cupric iodide 0.03g (0.18mmole) adding, 70 ℃ of reacting by heating one day.Most of triethylamine is taken out with the rotation thickner in the cooling back, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, with chromatographic analysis (5: 1 hexane/ethyl acetate wash-outs) purifying, obtain a brown transparent oily liquid with silica gel.Productive rate 78%.
Step 4: acrylic acid synthesizing 6-[4-(2-3-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group] polyhexamethylene (6-[4-(2-3-ethyl-4-[2-(4-propylphenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy] hexylacrylate) (M6)
With 6-[4-(23-ethyl-4-[2-(4-propyl group phenyl)-1-ethynyl] phenyl-1-ethynyl) phenoxy group]-1-hexanol (26) 1.2g (2.6mmol), anhydrous triethylamine (1.5ml, 10mmol) be positioned in the 100ml round-bottomed bottle with the 40ml anhydrous methylene chloride, under the ice bath, dropwise add acrylate chloride 0.47ml (5.2mmol), be back to room temperature reaction 24 hours.Solution splashes in the 50ml ice, concentrate so that extracted with diethyl ether is dry, with the silicone tube column chromatography purification, elutriant be ethyl acetate and normal hexane (1: 3, v/v).Productive rate 97%.
Fig. 9 shows the optical anisotropy of M6 and the relation of wavelength.As seen from the figure, when M6 was 550nm at wavelength, the optical anisotropy was about 0.34.
Embodiment 7: synthon M7 vinylformic acid 6-[4-(2-4[2-(4[6-(acryl oxygen base) hexyl] oxygen base phenyl)-1-ethynyl]-2-ethylphenyl-1-ethynyl) phenoxy group] polyhexamethylene (6-[4-(2-4[2-(4[6-(acryloyloxy) hexyl] oxyphenyl)-1-ethynyl]-2-ethylphenyl-1-ethynyl) phenoxy] hexyl acrylate)
Synthesis step please refer to Fig. 7.
Step 1: Synthetic 2-ethyl-1,4-diiodo-benzene (2-ethyl-1,4-diiodobenzene) (27)
2-ethyl-4-Iodoaniline (13) 10.0g (40mmole) is cooled to the concentrated hydrochloric acid that adds 20.0ml (240mmol) after 0-5 ℃, stirred 5 minutes, add 5.52g (80mmole) Sodium Nitrite frozen water solution (1g/3ml) again, under identical temperature, stirred 5-10 minute, potassiumiodide 33.2g (200mmole) aqueous solution (1g/ml) that adds ice bath again stirred 2-3 hour under identical temperature.The product of gained is cleaned with saturated aqueous sodium thiosulfate, water and saturated aqueous common salt with normal hexane dilution back, the organic layer of gained filters through anhydrous magnesium sulfate drying, after concentrating, with chromatographic analysis (5: 1 hexane/ethyl acetate wash-outs) purifying, obtain a weak yellow liquid with silica gel.Productive rate 86%.
Step 2: synthetic 6-(4-2-[2-ethyl-4-(2-4-[(6-hydroxyl hexyl) oxygen base] phenyl-1-ethynyl) phenyl]-1-ethynyl phenoxy group)-the 1-hexanol (6-(4-2-[2-ethyl-4-(2-4-[(6-hydroxyhexyl) oxy] phenyl-1-ethynyl) phenyl]-1-ethynylphenoxy)-1-hexanol) (28)
With 2-ethyl-1,4-diiodo-benzene (27) 6.0g (16.8mmole), 6-[4-(1-ethynyl) phenoxy group]-1-hexanol (22) 9.0g (41mole) and triethylamine 400ml insert in the round-bottomed bottle, the cupric iodide that respectively triphenyl phosphine 0.76g (2.9mmole), chlorination two (triphenyl phosphine) is closed palladium (II) 0.29g (0.4mmole) and 0.4g (2.1mmole) under nitrogen adds reflux one day.Most of triethylamine is taken out with the rotation thickner in the cooling back, add the ether dilution, clean with saturated aqueous ammonium chloride, water and saturated aqueous common salt again, the organic layer of gained is through anhydrous magnesium sulfate drying, filter, after concentrating, with chromatographic analysis (2: 1 hexane/ethyl acetate wash-outs) purifying, obtain a brown transparent oily liquid with silica gel.Productive rate 81%.
Step 3: acrylic acid synthesizing 6-[4-(2-4-[2-(4-[6-(acryl oxygen base) hexyl] oxygen base phenyl)-1-ethynyl]-2-ethylphenyl-1-ethynyl) phenoxy group] polyhexamethylene (6-[4-(2-4[2-(4-[6-(acryloyloxy) hexyl] oxyphenyl)-1-ethynyl]-2-ethylphenyl-1-ethynyl) phenoxy] hexyl acrylate) (M7)
With 6-(4-2-[2-ethyl-4-(2-4-[(6-hydroxyl hexyl) oxygen base] phenyl-1-ethynyl] phenyl)-1-ethynyl phenoxy group)-1-hexanol (28) 9.0g (16.7mmol), anhydrous triethylamine 19.4ml (134mmol) be positioned in the 500ml round-bottomed bottle with the 300ml anhydrous methylene chloride, under the ice bath, dropwise add acrylate chloride 6.1ml (67mmol), be back to room temperature reaction 24 hours.Solution splashes in the 50ml ice, concentrates so that extracted with diethyl ether is dry, and with the silicone tube column chromatography purification, elutriant is ethyl acetate and normal hexane 1: 3.Productive rate 88%.
Figure 10 shows the optical anisotropy of M7 and the relation of wavelength.As seen from the figure, when M7 was 550nm at wavelength, the optical anisotropy was about 0.35.
Monomer M 1 and M2 prepared in the foregoing description are known cholesterol liquid crystal molecule, and monomer M 3 to M7 is the two ethine liquid crystal compounds of novel triphenyl of the present invention, and it is observed down in polarizing microscope and learns, belongs to the nematic liquid crystal molecule.The NMR of monomer M 1 to M7 identifies and is shown in Table 2 phase inversion temperature such as table 3.Table 4 shows chemical structural formula, mesomorphic phase temperature and the Δ n of liquid crystal monomer M3 to M7 of the present invention.By table 3 and table 4 as can be known, the two acetylides (M3-M7) of triphenyl of the present invention are nematic liquid crystal, and it has high optical anisotropy (Δ n) under 550nm.
The NMR spectrum of table 2 monomer M 1 to M7
| Monomer | 1H NMR(CDCl 3，TMS，ppm) |
| M1 | (0.6-1.8 m, 41H, cholesterol), 1.96 (m, 4H ,-CH 2-CH 2＝CHCH 2-)，2.43(m，2H， CH 2＝CHC H 2-)，2.49-2.80(m，2H，C H 2OCH-)，2.97(m，1H，CH 2OC H-)， 4.04(t，2H，phO-C H 2-)，4.78(m，1H，phOC H(CH 2-) 2)，5.38(m，1H， C＝C H-), 6.87 (d, 2H, aromatics protons), 7.96 (d, 2H, aromatics protons) |
| M2 | 0.60-2.00(m，49H，-CH 3，CH 2-CH 2-CH 2-, cholesterol), 2.42 (d, 2H, O-C H-C＝CH-)，3.98(t，2H，phO-C H 2-)，4.14(t，2H，(O)CO-C H 2-)， 4.80(m，1H，CH 2-C H＝C-)，5.38(d，1H，-COO-C H-)，5.81(d，1H， -C H＝C-COOR)，6.10(m，1H，CH 2＝C H-), 6.40 (d, 1H ,-CH=C-COOR), 6.86,7.95 (2d, 4H, aromatics protons) |
| M3 | 0.85 (t, 3H, terminal Ph-CH 2CH 2-C H 3), 1.22 (t, 3H side direction Ph-CH 2-C H 3)， 1.51-1.58(m，4H，Ph-CH 2-C H 2-CH 3，PhO-CH 2C H 2CH 2-CH)，1.85(m，2H， -PhO-CH 2-CH 2C H 2-CH-)，2.41(m，1H，-PhO-CH 2-CH 2CH 2-CH＝C H 2), 2.49 (t, 2H, terminal Ph-CH 2CH 2-CH 3)，2.67(m，1H，-PhO-CH 2-CH 2CH 2-CH＝CH 2), 2.76 (q, 2H side direction Ph-CH 2-CH 3)，2.90(m，1H，-PhO-CH 2-CH 2CH 2-C H-CH 2)， 3.91(m，2H，Ph-OC H 2-CH 2-), 6.76 (d, 2H, aromatics protons), 7.60 (d, 2H, aromatics protons), 7.23-7.37 (m, 7H, aromatics proton) |
| M4 | 0.93 (t, 3H, terminal Ph-CH 2CH 2-C H 3), 1.30 (t, 3H side direction Ph-CH 2-C H 3)， 1.58-1.69(m，4H，Ph-CH 2-C H 2-CH 3，PhO-CH 2C H 2CH 2-CH)，1.94(m，2H， -PhO-CH 2-CH 2CH 2-CH-)，2.50(m，1H，-PhO-CH 2-CH 2CH 2-CH＝C H 2), 2.59 (t, 2H, terminal Ph-C H 2CH 2-CH 3)，2.77(m，1H，-PhO-CH 2-CH 2CH 2-CH＝C H 2), 2.85 (q, 2H side direction Ph-C H 2-CH 3)，3.00(m，1H，-PhO-CH 2-CH 2CH 2-C H＝CH 2)， 4.00(m，2H，Ph-OC H 2-CH 2-), 6.95 (d, 2H, aromatics protons), 7.20 (d, 2H, aromatics protons), 7.26-7.47 (m, 7H, aromatics proton) |
| M5 | 0.94 (t, 3H, terminal Ph-CH 2CH 2-C H 3), 1.31 (t, 3H side direction Ph-CH 2-C H 3)， 1.45-1.81(m，10H，PhO-CH 2-C H 2-C H 2-C H 2C H 2-, terminal Ph-CH 2-C H 2CH 3), 2.60 (t, 2H, terminal Ph-CH 2CH 2-CH 3), 2.87 (q, 2H side direction Ph-CH 2-CH 3)， 3.96(t，2H，PhO-C H 2-)，4.17(t，2H，(O)CO-C H 2-)，5.80(d， 1H，-CH＝C-COOR)，6.15(m，1H，CH 2＝C H-)，6.40(d，1H，-C H=C-COOR), 6.86 (d, 2H, the aromatics proton), (7.17 d, 2H, aromatics proton), 7.32 (s, 1H, the aromatics proton), 7.39-7.48 (m, 6H, the aromatics proton) |
| M6 | 0.93 (t, 3H, terminal Ph-CH 2CH 2-C H 3), 1.29 (t, 3H side direction Ph-CH 2-C H 3)， 1.40-1.80(m，8H，-PhO-CH 2-C H 2C H 2C H 2C H 2-), 2.58 (t, 2H, terminal Ph-C H 2CH 2-CH 3), 2.85 (q, 2H side direction Ph-C H 2-CH 3)，3.96(t，2H，PhO-CH 2-)， 4.15(t，2H，(O)CO-CH 2-)，5.81(d，1H，-C H＝C-COOR)，6.12(m，1H， CH 2＝C H-)，6.36(d，1H，-C H=C-COOR), 6.85 (d, 2H, aromatics protons), 7.10-7.50 (m, 7H, aromatics proton) |
| M7 | 1.27(t，3H，PhCH 2C H 3)，1.29-1.47(m，8H PhOCH 2-CH 2-C H 2-C H 2-CH 2-)， 1.67-1.81(m，8H PhOCH 2-C H 2-CH 2-CH 2-C H 2-)，2.85(q，2H PhC H 2CH 3)， 3.95(t，4H，PhO-C H 2-)，4.15(t，4H，C(O)O-C H 2-)，5.79(d， 2H，-C H＝C-COOR)，6.10(m，1H，CH 2＝C H-)，6.38(d，2H，-C H=C-COOR), 6.84 (d, 4H, aromatics protons), (7.36 s, 1H, aromatics proton), (7.40-7.45 m, 6H, aromatics proton) |
Each monomer phase inversion temperature of table 3
| Monomer | Phase inversion temperature (℃) |
| M1 | C 139.0 N*229.2I I 227.4 N*98.3C |
| M2 | C 87.8 I I 87.8 C |
| M3 | C 82.1 N 158.1 I I 144.9 N 40.6 C |
| M4 | C 93.8 N 162.3 I I 157.4 N 1.6 C |
| M5 | N 92.3 I I 89.5 N |
| M6 | N 90.6 I I 83.1 N |
| M7 | C 57.2 N 93.3 I I 90.8 N |
C: liquid crystal (crystal), N: nematic (nematic), N*: cholesterol type (cholesteric), I: equal tropism (isotropic)
The chemical structural formula of table 4 liquid crystal monomer of the present invention M3 to M7, mesomorphic phase temperature and Δ n
R
1, R
2, R
3, R
4, R
7, R
8, R
9, R
10, R
11And R
12Be H
Embodiment 8: liquid-crystal composition (I)
With liquid crystal monomer M5 of the present invention and known liquid crystal monomer M2, M8 (having two acryls, structure such as following), carry out blending with the ratio of table 5.The mesomorphic phase temperature of each liquid-crystal composition is as shown in table 5.As shown in Table 5, nematic liquid crystal monomer M 5 of the present invention in blending after the cholesterol liquid crystal M2, the mesomorphic phase of composition all betides room temperature range, zero pour (C-N*point) is lower than Range of measuring temp, so do not manifest, and each liquid-crystal composition is cholesterol liquid crystal (with spectrophotometer (Spectrophotometer) test, being confirmed from reflection spectrum).In addition, its equal tropism's liquid all betides about 100 ℃, so great potentiality are arranged in business-like operation.
Table 5 liquid-crystal composition M5: M2: the ratio of M8 blending and phase inversion temperature
| Ratio | Phase inversion temperature (℃) | Ratio | Phase inversion temperature (℃) |
| 8/1/1 | N*92.3T I 88.6N* | 4/2/4 | N*104.7I I 97.9N* |
| 7/1/2 | N*100.0I I 96.3N* | 3/2/5 | N*111.4I I 106.8N* |
| 6/1/3 | N*90.7T I 86.9N* | 2/2/6 | N*109.4I I 102.9N* |
| 5/1/4 | N*94.5I I 90.4N* | 1/2/7 | N*109.4I I 103.7N* |
| 4/1/5 | N*103.7I I 91.2N* | 6/3/1 | N*115.9I I 114.7N* |
| 3/1/6 | N*90.7I I 84.7N* | 5/3/2 | N*133.2I I 127.6N* |
| 2/1/7 | N*89.6I I 84.9N* | 4/3/3 | N*114.1I I 108.6N* |
| 1/1/8 | N*96.2I I 91.8N* | 3/3/4 | N*120.3I I 115.1N* |
| 7/2/1 | N*100.0I I 94.7N* | 1/3/6 | N*114.7I I 114.4N* |
| 6/2/2 | N*116.6I I 113.4N* | 4/5/1 | N*134.3I I 131.4N* |
| 5/2/3 | N*89.2I I 81.0N* |
Embodiment 9: liquid-crystal composition (II)
Liquid crystal monomer M7 of the present invention and known liquid crystal monomer M2 are carried out blending with the ratio of table 6.The phase inversion temperature of liquid-crystal composition is as shown in table 6.As shown in Table 6, M7 monomer of the present invention with the cholesterol liquid crystal blending after, its zero pour (C-N*point) drops to (actual value is lower than test specification, so do not manifest) below freezing, so the mesomorphic phase of this composition all betides under the room temperature range.And each liquid-crystal composition judges that according to the reflection spectrum of gained it is cholesterol liquid crystal with spectrophotometer (Spectrophotometer) test.
Table 6 liquid-crystal composition M2: the ratio of M7 blending and phase inversion temperature
| M2∶M7 | Phase inversion temperature (℃) |
| 5％∶95％ | N*105.4I I 88.5N* |
| 10％∶90％ | N*102.9I I 101.2N* |
| 15％∶85％ | N*105.2I I 103.0N* |
| 20％∶80％ | N*108.5I I 89.8N* |
| 30％∶70％ | N*114.6I I 112.4N* |
| 40％∶60％ | N*126.4I I 124.8N* |
Embodiment 10: make cholesterol type reflecting type polarizing plate
(1) film:
With PVA (polyvinyl acetate, polyvinyl acetate) or PI (polyimide, polyimide) solution coat (as TAC (triacetyl cellulose, triacetylcellulose) film or glass), and is heated to proper temperature and makes solvent evaporates on clean base material.Above-mentioned test piece with the flannelette friction, to reach the orientation effect, is obtained alignment film (orientation membrane).
With M7 and M2 respectively with weight percent 95%: 5% and mix at 90%: 10%, and the light initiator Irgacure 369 (Ciba Geigy) of adding total solid weight per-cent 3-5%, be dissolved in the cyclopentanone (cyclopentanone), make that solid content is 20%.
Above-mentioned two kinds of M7/M2 sepages are all coated on the alignment film.Test piece is heated to 80 ℃ kept 2 minutes, under nitrogen environment with UV light (energy 480mJ/cm
2) make its ridgeization, obtain Polarizer.
(2) liquid crystal cell:
PVA or PI solution coat on two clean sheet glass, and are heated to proper temperature and make solvent evaporates.Above-mentioned test piece with the flannelette friction, to reach the orientation effect, is obtained alignment film.
With the parallel reverse placement of alignment film, press from both sides 25 microns spacers, envelope frame glue is finished liquid crystal cell.
M7 and M2 respectively with weight percent 95%: 5% and mix at 90%: 10%, and are added the light initiator Irgacure 369 (Ciba Geigy) of total solid weight per-cent 3-5%, be dissolved in the cyclopentanone, make that solid content is 20%.
Above-mentioned two kinds of M7/M2 solution are poured in the liquid crystal cell respectively.Liquid crystal cell is heated to 80 ℃ kept 2 minutes, with UV light (energy 16J/cm
2) make its sclerosis.
Figure 11 shows the penetration of M2/M7 (5%: 95%) the prepared cholesterol liquid crystal Polarizer of polymkeric substance (liquid crystal cell) under each wavelength.Figure 12 shows the penetration of M2/M7 (10%: 90%) the prepared cholesterol liquid crystal Polarizer of polymkeric substance (liquid crystal cell) under each wavelength.By Figure 11 and Figure 12 as can be known, by the made reflecting type polarizing plate of liquid crystalline polymers of the present invention, have good reflectivity properties, and the reflected light frequency range is contained whole visible-range.
Claims (18)
1. two acetylides of the reactive triphenyl of tool shown in the following general formula (I):
Wherein
R
aAnd R
bBe independently selected from H, acryl and epoxy group(ing), condition is R
aAnd R
bBe not H simultaneously;
L
1And L
2Be independently selected from-(CH
2)
n-,-O-(CH
2)
m-and-O-(CH
2)
m-O-, wherein n is 0 to 6 integer, m is 1 to 6 integer; And
R
5-R
8Be independently selected from H and C
1-6Alkyl;
R
1-R
4And R
9-R
12Be hydrogen.
2. compound as claimed in claim 1, wherein R
5, R
6, R
7And R
8In have one at least for C
1-6Alkyl.
3. liquid crystalline polymers, it is a homopolymer or a multipolymer, wherein this homopolymer is to be got through polyreaction by the two acetylides of triphenyl as claimed in claim 1, and this multipolymer is to be got through copolymerization by the two acetylides of triphenyl as claimed in claim 1 and other monomers.
4. liquid crystalline polymers as claimed in claim 3, wherein said liquid crystalline polymers are a multipolymer, and described other monomers comprise a liquid crystalline cpd.
5. liquid crystalline polymers as claimed in claim 4, wherein said liquid crystalline cpd comprises a cholesterol liquid crystal.
6. liquid crystalline polymers as claimed in claim 5, the two acetylides of wherein said triphenyl as claimed in claim 1 are that 10wt% to 98wt% is than 2wt% to 90wt% with the usage ratio of described cholesterol liquid crystal.
7. liquid crystalline polymers as claimed in claim 6, the two acetylides of wherein said triphenyl as claimed in claim 1 are that 80wt% to 98wt% is than 2wt% to 20wt% with the usage ratio of described cholesterol liquid crystal.
8. liquid crystalline polymers as claimed in claim 7, the two acetylides of wherein said triphenyl as claimed in claim 1 are that 90wt% to 98wt% is than 2wt% to 10wt% with the usage ratio of described cholesterol liquid crystal.
9. liquid-crystal composition, it comprises:
(a) the two acetylides of the triphenyl as claimed in claim 1 of 10wt% to 98wt%; And
(b) liquid crystal of 2wt% to 90wt%, they are different with composition (a).
10. liquid-crystal composition as claimed in claim 9, wherein said liquid crystal comprises a cholesterol liquid crystal.
11. liquid-crystal composition as claimed in claim 10, it comprises:
(a) the two acetylides of the triphenyl as claimed in claim 1 of 80wt% to 98wt%; And
(b) liquid crystal of 2wt% to 20wt%, they are different with composition (a).
12. liquid-crystal composition as claimed in claim 11, it comprises:
(a) the two acetylides of the triphenyl as claimed in claim 1 of 90wt% to 98wt%; And
(b) liquid crystal of 2wt% to 10wt%, they are different with composition (a).
13. a cholesterol type reflecting type polarizing plate, it comprises liquid crystalline polymers as claimed in claim 5.
14. cholesterol type reflecting type polarizing plate as claimed in claim 13, it is a form of film.
15. cholesterol type reflecting type polarizing plate as claimed in claim 13, it is the liquid crystal cell form.
16. a liquid crystal indicator, it comprises liquid crystalline polymers as claimed in claim 3.
17. liquid crystal indicator as claimed in claim 16, wherein said liquid crystalline polymers are a multipolymer, it is to be got through copolymerization by two acetylides of triphenyl as claimed in claim 1 and a cholesterol liquid crystal monomer.
18. a liquid crystal indicator, it comprises liquid-crystal composition as claimed in claim 9.
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|---|---|---|---|
| CN 01134217 CN1228293C (en) | 2001-10-26 | 2001-10-26 | Triphenyl diacetylene compound with reaction and liquid crystal polymer containing the compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01134217 CN1228293C (en) | 2001-10-26 | 2001-10-26 | Triphenyl diacetylene compound with reaction and liquid crystal polymer containing the compound |
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| CN1228293C true CN1228293C (en) | 2005-11-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005255578A (en) * | 2004-03-10 | 2005-09-22 | Fuji Photo Film Co Ltd | Compound, liquid crystal composition and optical material |
| CN1307284C (en) * | 2004-08-03 | 2007-03-28 | 江苏傲伦达科技实业股份有限公司 | Alkyl cyclohexyl alkynes liquid crystal compound and its preparation method |
| WO2011035863A1 (en) | 2009-09-25 | 2011-03-31 | Merck Patent Gmbh | Components for high-frequency technology and liquid crystal media |
| DE102010035730A1 (en) | 2009-09-28 | 2011-04-07 | Merck Patent Gmbh | Polymerizable compounds and their use in liquid crystal displays |
| JP5826759B2 (en) * | 2009-10-30 | 2015-12-02 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Polymerizable LC material and polymer film with negative optical dispersion |
| TWI440701B (en) | 2010-07-23 | 2014-06-11 | Lg Chemical Ltd | Reflective polarizing plate and display device |
| JP6158169B2 (en) * | 2011-04-27 | 2017-07-05 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Compounds for liquid crystal media and their use for high frequency components |
| JP6299969B2 (en) | 2013-04-17 | 2018-03-28 | Jnc株式会社 | Polymerizable compound having conjugated bond, liquid crystal composition, and liquid crystal display device |
| CN113861855A (en) * | 2021-09-30 | 2021-12-31 | 芜湖徽氏新材料科技有限公司 | PI adhesive tape for protecting lithium battery tab |
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