CN1155679C - Liquid crystal compound contg. oligothiophene skeleton, preparing process thereof - Google Patents
Liquid crystal compound contg. oligothiophene skeleton, preparing process thereof Download PDFInfo
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- CN1155679C CN1155679C CNB021347727A CN02134772A CN1155679C CN 1155679 C CN1155679 C CN 1155679C CN B021347727 A CNB021347727 A CN B021347727A CN 02134772 A CN02134772 A CN 02134772A CN 1155679 C CN1155679 C CN 1155679C
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Abstract
The present invention relates to a liquid crystal compound containing an oligomerization thiophene skeleton, and a preparing method thereof. The compound has a molecular structural formula shown on the right side. The preparing method comprises: firstly, a tetrahydrofuran solution of DBr3T is added into a tetrahydrofuran solution of lithium diisopropylamine and stirred for a reaction; then, dry ice and diluted hydrochloric acid are added into the mixture; subsequently, THF and water are removed by filtering, and the filtering products are washed by water and dried; the products are added into a 1, 2-dichloroethane solution of sulfoxide chloride for a refluxing reaction; afterwards, the products and n-alkylamine are added to a methylene chloride solution for a reaction, and thus, coarse products are obtained after a solvent is removed; finally, the coarse products are separated by silica gel columns, and thus, a pure product is obtained. The liquid crystal compound containing an oligomerization thiophene skeleton has a smectic crystal property by the detection and the observation of a differential scanning calorimetry and a polarized light optical microscope.
Description
(1) technical field
The present invention relates to the synthesis technical field of organic polymer photoelectric material, specifically be meant liquid crystalline cpd that contains oligothiophene bone lattice and preparation method thereof.
(2) background technology
The high purity oligothiophene that the polymerization degree and polymerization position can be controlled, have definite molecular weight is not only " model " compound of research Polythiophene, self also is that a kind of πDian Zi with excellent light, electrical property is a conjugated compound.Because its excellent light, electrical property in recent years, are used as functional organic material and research and develop.Up to the present, according to the research and development target of oligothiophene, design, synthesized various Oligopoly thiophene derivatives as the photoelectric information functional organic materials.These Oligopoly thiophene derivatives mainly are used to the research of following several respects: (1) studies the relation of the electric conductivity of resulting ion free radical salt with conjugate length by electrochemical doping.Result of study shows, improves the conjugate length of oligothiophene, and electric conductivity also will improve thereupon.For example, the electric conductivity of 6 aggressiveness (6T) of thiophene is 10
0-10
-1Scm
-1, and the electric conductivity of 12 aggressiveness (4Oc12T) of thiophene reaches 10Scm
-1(2) the research and development oligothiophene is as the photoelectric characteristic of photoelectric conversion material.It is a kind of very excellent p N-type semiconductorN material that result of study demonstrates oligothiophene.(3) the research oligothiophene is as the characteristics of luminescence of luminous organic material.Generally speaking, oligothiophene is to be in crystalline state, but the most outstanding at present achievement in research is with the electroluminescent device of the unformed molecular material assembling with oligothiophene skeleton, by the conjugate length of control oligothiophene, can send the light of different wave length.Above-mentioned about oligothiophene as functional organic material, from the state of aggregation of molecule, only be confined to crystallization and unformed state.Over the past two years, the liquid crystal with oligothiophene bone lattice was subjected to investigator's close attention and great attention, especially liquid crystal research person and EL (electroluminescent) device investigator.Liquid crystal research person wishes that utilization has light, the electrical property πDian Zi is that the conjugated compound liquid crystal improves large vol storage demonstration function.And the El element investigator really comes into the market in order to make El element, needs height-oriented liquid crystal material to obtain polarized luminescence (polarized Luminescence).Though it is a lot of to have the organic low molecular and the macromolecular compound of liquid crystal property, up to the present, the liquid crystal with oligothiophene bone lattice does not but almost have.For light, the electrical property that makes full use of the oligothiophene excellence, enlarge the application prospect of oligothiophene as functional organic material, the liquid crystal that research and development have the oligothiophene skeleton is very tempting problem.
(3) summary of the invention
Purpose of the present invention is exactly the situation that lacks the liquid crystal with oligothiophene bone lattice that exists in the above-mentioned prior art in order to solve, and a kind of liquid crystalline cpd that contains oligothiophene bone lattice and preparation method thereof is provided.
The liquid crystalline cpd that contains oligothiophene bone lattice of the present invention is characterized in that it has following molecular structural formula, i.e. DNC
nDBr3T (n=8,16,18):
The chemical name of this material is N, N '-n alkyl-5,5 " two bromos-2,2 ': 5 ', 2 " three thiophene-4,4 " diamide (n=8,16,18).
The preparation method who contains the liquid crystalline cpd of oligothiophene bone lattice of the present invention is characterized in that it comprises the steps and processing condition:
The first step is at-78 ℃, N
2Protection down, with DBr3T (5,5 " two bromos-2,2 ': 5 ', 2 " three thiophene) tetrahydrofuran (THF) (THF) solution add in tetrahydrofuran (THF) (THF) solution of diisopropylamine lithium (LDA) stirring reaction 1～3 hour;
Second step added dry ice (CO in reaction soln
2), at-78 ℃, N
2Protection continues reaction 3～5 hours down, is warmed up to room temperature then, continues reaction 3～5 hours;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 5～8 hours, removed by filter THF and water, washing, drying;
The 4th step joined sulfur oxychloride (SOCl with product
2) 1, in the 2-dichloroethane solution, back flow reaction 5～8 hours is removed and to be desolvated;
The 5th the step with product respectively with the n alkylamine at 0 ℃, N
2Protection was reacted in dichloromethane solution 6～10 hours down, removed and desolvated, and obtained crude product, separated with silicagel column then, promptly got pure products DNC
nDBr3T (n=18,16,8).
In order to realize the present invention better, can add triethylamine earlier in the dichloromethane solution in the 5th step; Can be chloroform with the isolating washing fluid of silicagel column.
Above-mentioned preparation process can be expressed by following formula:
The present invention has following advantage and beneficial effect:
Utilize microscopical mensuration of differential scanning calorimetry and polarization optical and observation, find that the liquid crystalline cpd that contains oligothiophene bone lattice of the present invention demonstrates smectic liquid crystal character.Their phase-state change is as shown in the table:
DNC
nPhase inversion temperature and the enthalpy change of DBr3T (n=18,16,8)
| Compound | Tansition temperature [℃] and enthalpy change [kJmol -1] |
| DNC 8DBr3T | K 109(-) S A 126(-) I |
| DNC 16DBr3T | K 110(46) S A 127(3.6) I |
| DNC 18DBr3T | K 107(56) S A 123(3.7) I |
Annotate: K: crystallization, S
A: smectic liquid crystal, I: each homogeny liquid.
(4) embodiment
Embodiment one
The first step is at-78 ℃, N
2Protection down, with DBr3T (5,5 " two bromos-2,2 ': 5 '; 2 "-three thiophene, 2.0g, tetrahydrofuran (THF) 4.9mmol) (THF) solution (30ml) adds diisopropylamine lithium (LDA, 19.6mmol) tetrahydrofuran (THF) (THF, 20ml) in the solution, stirring reaction 1 hour;
Second step added excessive dry ice (CO in reaction soln
2), at-78 ℃, N
2Protection continues reaction 3 hours down, is warmed up to room temperature then, continues reaction 3 hours;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 5 hours, removed by filter THF and water, washing, drying;
The 4th step, (0.5g 1.0mmol) joined sulfur oxychloride (SOCl with above-mentioned product
2, 0.24g, 2.0mmol) 1, in the 2-dichloroethane solution (80ml), back flow reaction 5 hours is removed and to be desolvated;
The 5th step, (0.5g was 1.9mmol) at 0 ℃, N with above-mentioned product and octadecylamine
2Protection was reacted 6 hours in the dichloromethane solution (80ml) that adds triethylamine down, removed and desolvated, and obtained crude product, separated (washing fluid is a chloroform) with silicagel column then, promptly got pure products DNC
nDBr3T (n=18).
Embodiment two
The first step is at-78 ℃, N
2Protection down, with DBr3T (5,5 " two bromos-2,2 ': 5 '; 2 "-three thiophene, 3.0g, tetrahydrofuran (THF) 7.4mmol) (THF) solution (40ml) adds diisopropylamine lithium (LDA, 29.6mmol) tetrahydrofuran (THF) (THF, 30ml) in the solution, stirring reaction 2 hours;
Second step added excessive dry ice (CO in reaction soln
2), at-78 ℃, N
2Protection continues reaction 4 hours down, is warmed up to room temperature then, continues reaction 4 hours;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 6 hours, removed by filter THF and water, washing, drying;
The 4th step, (1.0g 2.0mmol) joined sulfur oxychloride (SOCl with above-mentioned product
2, 0.48g, 4.0mmol) 1, in the 2-dichloroethane solution (100ml), back flow reaction 7 hours is removed and to be desolvated;
The 5th step, (0.9g was 3.7mmol) at 0 ℃, N with above-mentioned product and hexadecylamine
2Protection was reacted 8 hours in dichloromethane solution (100ml) down, removed and desolvated, and obtained crude product, separated (washing fluid is a chloroform) with silicagel column then, promptly got pure products DNC
nDBr3T (n=16).
Embodiment three
The first step is at-78 ℃, N
2Protection down, with DBr3T (5,5 " two bromos-2,2 ': 5 '; 2 "-three thiophene, 2.5g, tetrahydrofuran (THF) 6.1mmol) (THF) solution (35ml) adds diisopropylamine lithium (LDA, 24.4mmol) tetrahydrofuran (THF) (THF, 25ml) in the solution, stirring reaction 3 hours;
Second step added excessive dry ice (CO in reaction soln
2), at-78 ℃, N
2Protection continues reaction 5 hours down, is warmed up to room temperature then, continues reaction 5 hours;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 8 hours, removed by filter THF and water, washing, drying;
The 4th step, (0.4g 0.8mmol) joined sulfur oxychloride (SOCl with above-mentioned product
2, 0.19g, 1.6mmol) 1, in the 2-dichloroethane solution (60ml), back flow reaction 8 hours is removed and to be desolvated;
The 5th step, (0.2g was 1.6mmol) at 0 ℃, N with above-mentioned product and eight alkylamines
2Protection was reacted 10 hours in the dichloromethane solution (80ml) that adds triethylamine down, removed and desolvated, and obtained crude product, separated (washing fluid is a chloroform) with silicagel column then, promptly got pure products DNC
nDBr3T (n=8).
The amount that adds reactant among the above embodiment, it is to determine: the consumption of at first freely determining initiator according to general organic synthesis method in common, secondly, the amount of the reactant of dosing is that the consumption according to initiator, the molecular weight of initiator and the molecular weight of the reactant of dosing calculate definite.As mentioned above, can realize the present invention preferably.
Claims (3)
1. contain the liquid crystalline cpd of oligothiophene bone lattice, it is characterized in that, it has following molecular structural formula, i.e. DNC
nDBr3T, n are 18,16,8
2. contain the preparation method of the liquid crystalline cpd of oligothiophene bone lattice, it is characterized in that, it comprises the steps and processing condition:
The first step is at-78 ℃, N
2Protection down adds in the tetrahydrofuran solution of diisopropylamine lithium stirring reaction 1～3 hour with the tetrahydrofuran solution of DBr3T;
Second step added dry ice in reaction soln, at-78 ℃, N
2Protection continues reaction 3～5 hours down, is warmed up to room temperature then, continues reaction 3～5 hours;
The 3rd step added dilute hydrochloric acid in reaction soln, continue reaction 5～8 hours, removed by filter tetrahydrofuran (THF) and water, washing, drying;
The 4th step joined 1 of sulfur oxychloride with product, and in the 2-dichloroethane solution, back flow reaction 5～8 hours is removed and desolvated;
The 5th step with product and n alkylamine at 0 ℃, N
2Protection was reacted in dichloromethane solution 6～10 hours down, removed and desolvated, and obtained crude product, separated with silicagel column then, promptly got pure products; In the described n alkylamine, n is 18,16,8.
3. the preparation method who contains the liquid crystalline cpd of oligothiophene bone lattice according to claim 2 is characterized in that, adds triethylamine in the dichloromethane solution in the 5th step earlier; With the isolating washing fluid of silicagel column is chloroform.
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| CNB021347727A CN1155679C (en) | 2002-09-20 | 2002-09-20 | Liquid crystal compound contg. oligothiophene skeleton, preparing process thereof |
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|---|---|---|---|
| CNB021347727A CN1155679C (en) | 2002-09-20 | 2002-09-20 | Liquid crystal compound contg. oligothiophene skeleton, preparing process thereof |
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| CN1155679C true CN1155679C (en) | 2004-06-30 |
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| US8329924B2 (en) | 2001-06-11 | 2012-12-11 | Vertex Pharmaceuticals (Canada) Incorporated | Compounds and methods for the treatment or prevention of Flavivirus infections |
| AP1753A (en) | 2001-06-11 | 2007-07-18 | Shire Biochem Inc | Thiophene derivatives as antiviral agents for flavvivirus infection |
| KR101058696B1 (en) | 2002-12-10 | 2011-08-22 | 바이로켐 파마 인코포레이티드 | Compounds and Methods for the Treatment or Prevention of Furabivirus Infections |
| EA201101492A1 (en) | 2006-11-15 | 2012-09-28 | Вирокем Фарма Инк. | TIOPHENE ANALOGUES FOR THE TREATMENT OR PREVENTION OF FLAVIVIRUS INFECTIONS |
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