CN101775024A - Method for preparing ionic chiral dopant containing isosorbitol primitive - Google Patents
Method for preparing ionic chiral dopant containing isosorbitol primitive Download PDFInfo
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- CN101775024A CN101775024A CN201010022966A CN201010022966A CN101775024A CN 101775024 A CN101775024 A CN 101775024A CN 201010022966 A CN201010022966 A CN 201010022966A CN 201010022966 A CN201010022966 A CN 201010022966A CN 101775024 A CN101775024 A CN 101775024A
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- isosorbide
- benzoic acid
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Abstract
The invention relates to a method for preparing an ionic chiral dopant containing isosorbitol primitives, which comprises the steps of: putting weighing di-[(S)-4-chloromethyl benzoic acid] hexahydro-furo [3, 2-b] furan-ester and acetonitrile in a three-mouth neck flask, adding triethylamine at the room temperature, stirring the mixture, raising the temperature to the reaction temperature of 60-85 DEG C for reacting for 3-5h, pouring the reactant into acetone to separate a product out, washing the product with acetone, removing the acetone by steaming, drying the product, and recrystallizing by using chloroform for recrysta llization to obtain a white solid. The invention has the advantages of simplicity, low cost and suitability for industrial production. The prepared substance has a wide application prospect in the fields of nonlinear optics, quick optical switches, micro-electronics, liquid crystals, and the like.
Description
Technical field
The invention belongs to the preparation field of ionic chiral dopant, particularly relate to a kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive.
Background technology
Chirality is a ubiquitous phenomenon in nature and the life entity.The chirality problem is significant to the development of related disciplines such as life science, pharmaceutical chemistry, (polymer) Materials science.Chiral dopant is introduced in the liquid crystal, promoted the development and the application of novel liquid crystal material and nonlinear optical material greatly.Chiral dopant is owing to have chiral radicals, can induce nematic liquid crystal to form cholesteryl phase or chiral nematic phase liquid crystal, induce liquid crystal molecule to form spiral helicine arrangement, thereby make liquid crystal material have unique optical property, have broad application prospects in fields such as nonlinear optics, fast optical switch based, microelectronics.
Invention now and the chiral dopant that uses have polarity or ionic compound molecule seldom, and have polarity or ionic chiral dopant has material impact to the polarity liquid crystal molecule, also can produce material impact to the surface property of composition system.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive, and this method is simple, and is with low cost, is suitable for suitability for industrialized production.
Chemical equation of the present invention is as follows:
The present invention has synthesized the ionic chiral dopant that contains the Isosorbide primitive with Isosorbide for chiral radicals design: two-[(S) 4-triethylamine ylmethyl phenylformic acid)] hexahydro furyls are [3,2-b] furans-esters (C4) also; Compound structure is as follows:
A kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive of the present invention comprises:
Get two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also [3,2-b] furans-ester (C3) and acetonitrile be in there-necked flask, add triethylamine under the room temperature, stir and be warming up to temperature of reaction 60-85 ℃, reaction 3-5h, reactant is poured in the acetone, product is separated out, and uses washing with acetone, boils off acetone, with the product oven dry, behind the chloroform recrystallization, get white solid.
Described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-esters (C3) and acetonitrile is 1: 10-30.
Described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-esters (C3) and triethylamine is 1: 2-5.
Adopt thin-layer chromatography detection reaction process, developping agent is a toluene: acetone=20: 1.
Described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-ester, acetonitrile, triethylamine is 1: 10: 2.4.
Described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-ester, acetonitrile, triethylamine is 1: 20: 3.
Described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-ester, acetonitrile, triethylamine is 1: 30: 5.
The present invention has broad application prospects in fields such as nonlinear optics, fast optical switch based, microelectronics, liquid crystal.
The present invention characterizes by the structure to dopant compound such as IR, NMR, UV and ultimate analysis.Studied the photochemical properties of synthetic chiral dopant by specific rotation and circular dichroism spectrum.
As seen from Figure 1, be that significantly positive health effect and the negative health effect of pausing of pausing appears in chiral raw material synthetic doping agent C4 with the Isosorbide.Positive CD absorption peak appears in C3 at the 227nm place, negative CD absorption peak occurs at the 245nm place; Positive CD absorption peak appears in C4 in 222nm, negative CD absorption peak occurs at the 240nm place.Illustrate that cationic structural can influence the opticity of compound.Introduce cation group in molecule after, the wavelength at doping agent maximum absorption band place moves to short wavelength's direction.The circular dichroism of doping agent shows that institute's synthetic doping agent has good chirality.
Beneficial effect
Preparation method of the present invention is simple, and is with low cost, is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 contains the circular dichroism spectrum of the ionic chiral dopant of Isosorbide primitive;
The infrared spectrogram of Fig. 2 C4 compound.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Take by weighing two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also the acetonitrile of [3,2-b] furans-ester (C3) 0.015mol and 0.15mol in the 150ml there-necked flask, add 3.63g (0.036mol) triethylamine under the room temperature, stir and be warming up to 85 ℃, reaction 3h.With thin-layer chromatography detection reaction process, developping agent is a toluene: acetone=20: 1.After reaction is finished, reactant is poured in the acetone, product is separated out.Wash twice with acetone again.Boil off acetone, with the product oven dry, get white solid 7.59g behind the chloroform recrystallization, fusing point is 118.9 ℃ (seeing accompanying drawing 2), and yield is 82.0%.The infrared spectra of product shows, 1719cm
-1Be the antisymmetric stretching vibration of the two key C=O of carbonyl carbon oxygen, 1637cm
-1, 1484cm
-1Be the C=C skeletal vibration on the phenyl ring, 1273cm
-1About be the vibration absorption peak of ehter bond.
Embodiment 2
Take by weighing two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also the acetonitrile of [3,2-b] furans-ester (C3) 0.015mol and 0.30mol in the 150ml there-necked flask, add 3.63g (0.045mol) triethylamine under the room temperature, stir and be warming up to 85 ℃, reaction 3h.With thin-layer chromatography detection reaction process, developping agent is a toluene: acetone=20: 1.After reaction is finished, reactant is poured in the acetone, product is separated out.Wash twice with acetone again.Boil off acetone, with the product oven dry, get white solid 8.12g behind the chloroform recrystallization, fusing point is 118.9 ℃ (seeing accompanying drawing 2), and yield is 87.7%.The infrared spectra of product shows, 1719cm
-1Be the antisymmetric stretching vibration of the two key C=O of carbonyl carbon oxygen, 1637cm
-1, 1484cm
-1Be the C=C skeletal vibration on the phenyl ring, 1273cm
-1About be the vibration absorption peak of ehter bond.
Embodiment 3
Take by weighing two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also the acetonitrile of [3,2-b] furans-ester (C3) 0.015mol and 0.45mol in the 150ml there-necked flask, add 3.63g (0.075mol) triethylamine under the room temperature, stir and be warming up to 85 ℃, reaction 3h.With thin-layer chromatography detection reaction process, developping agent is a toluene: acetone=20: 1.After reaction is finished, reactant is poured in the acetone, product is separated out.Wash twice with acetone again.Boil off acetone, with the product oven dry, get white solid 8.22g behind the chloroform recrystallization, fusing point is 118.9 ℃ (seeing accompanying drawing 2), and yield is 88.8%.The infrared spectra of product shows, 1719cm
-1Be the antisymmetric stretching vibration of the two key C=O of carbonyl carbon oxygen, 1637cm
-1, 1484cm
-1Be the C=C skeletal vibration on the phenyl ring, 1273cm
-1About be the vibration absorption peak of ehter bond.
Embodiment 4
Take by weighing two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also the acetonitrile of [3,2-b] furans-ester (C3) 0.015mol and 0.15mol in the 150ml there-necked flask, add 3.63g (0.036mol) triethylamine under the room temperature, stir and be warming up to 60 ℃, reaction 12h.After reaction is finished, reactant is poured in the acetone, product is separated out.Wash twice with acetone again.Boil off acetone, with the product oven dry, get white solid 6.58g behind the chloroform recrystallization, fusing point is 118.9 ℃ (seeing accompanying drawing 2), and yield is 71.1%.The infrared spectra of product shows, 1719cm
-1Be the antisymmetric stretching vibration of the two key C=O of carbonyl carbon oxygen, 1637cm
-1, 1484cm
-1Be the C=C skeletal vibration on the phenyl ring, 1273cm
-1About be the vibration absorption peak of ehter bond.
Take by weighing two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also the acetonitrile of [3,2-b] furans-ester (C3) 0.015mol and 0.15mol in the 150ml there-necked flask, add 3.63g (0.036mol) triethylamine under the room temperature, stir and be warming up to 70 ℃, reaction 9h.After reaction is finished, reactant is poured in the acetone, product is separated out.Wash twice with acetone again.Boil off acetone, with the product oven dry, get white solid 6.88g behind the chloroform recrystallization, fusing point is 118.9 ℃ (seeing accompanying drawing 2), and yield is 74.3%.The infrared spectra of product shows, 1719cm
-1Be the antisymmetric stretching vibration of the two key C=O of carbonyl carbon oxygen, 1637cm
-1, 1484cm
-1Be the C=C skeletal vibration on the phenyl ring, 1273cm
-1About be the vibration absorption peak of ehter bond.
Embodiment 6
Take by weighing two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also the acetonitrile of [3,2-b] furans-ester (C3) 0.015mol and 0.45mol in the 150ml there-necked flask, add 3.63g (0.075mol) triethylamine under the room temperature, stir and be warming up to 65 ℃, reaction 10h.After reaction is finished, reactant is poured in the acetone, product is separated out.Wash twice with acetone again.Boil off acetone, with the product oven dry, get white solid 8.12g behind the chloroform recrystallization, fusing point is 118.9 ℃ (seeing accompanying drawing 2), and yield is 87.7%.The infrared spectra of product shows, 1719cm
-1Be the antisymmetric stretching vibration of the two key C=O of carbonyl carbon oxygen, 1637cm
-1, 1484cm
-1Be the C=C skeletal vibration on the phenyl ring, 1273cm
-1About be the vibration absorption peak of ehter bond.
The spectral signature of ionic chiral dopant of the present invention (C4)
Two-[(S) 4-triethylamine ylmethyl phenylformic acid)] hexahydro furyls are [3,2-b] furans-esters (C4) 341 type polarimeters of adopting PERKINELMER company to produce also, pipe range 100mm, and wavelength 589nm, 20 ℃ of temperature are made solvent with DMF.Two-[(S) 4-triethylamine ylmethyl phenylformic acid)] the hexahydro furyls also specific rotation of [3,2-b] furans-esters (C4) see Table 1.
Table 1 contains the specific rotation data of the ionic chiral dopant (C4) of Isosorbide primitive
The J-810 type circular dichroism spectrometer that adopts JASCO company to produce, 20 ℃ of temperature are made solvent with acetonitrile.The circular dichroism spectrum that contains the ionic chiral dopant of Isosorbide primitive is seen Fig. 1.
Claims (7)
1. preparation method who contains the ionic chiral dopant of Isosorbide primitive comprises:
Get two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also [3,2-b] furans-ester and acetonitrile be in there-necked flask, add triethylamine under the room temperature, stir and be warming up to temperature of reaction 60-85 ℃, reaction 3-5h, reactant is poured in the acetone, product is separated out, and uses washing with acetone, boils off acetone, with the product oven dry, behind the chloroform recrystallization, get white solid.
2. a kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive according to claim 1, it is characterized in that: described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-ester and acetonitrile is 1: 10-30.
3. a kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive according to claim 1, it is characterized in that: described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-ester and triethylamine is 1: 2-5.
4. a kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive according to claim 1 is characterized in that: adopt thin-layer chromatography detection reaction process, developping agent is a toluene: acetone=20: 1.
5. a kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive according to claim 1, it is characterized in that: described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-ester, acetonitrile, triethylamine is 1: 10: 2.4.
6. a kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive according to claim 1, it is characterized in that: described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-ester, acetonitrile, triethylamine is 1: 20: 3.
7. a kind of preparation method who contains the ionic chiral dopant of Isosorbide primitive according to claim 1, it is characterized in that: described two-[(S)-4-chloromethyl benzoic acid)] hexahydro furyl also mol ratio of [3,2-b] furans-ester, acetonitrile, triethylamine is 1: 30: 5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI414527B (en) * | 2010-10-06 | 2013-11-11 | Ind Tech Res Inst | Isosorbide derivatives and liquid crystal displays comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI414527B (en) * | 2010-10-06 | 2013-11-11 | Ind Tech Res Inst | Isosorbide derivatives and liquid crystal displays comprising the same |
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Application publication date: 20100714 |