CN109180639B - Substituted naphthalimide derivative, preparation method and application thereof - Google Patents
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Abstract
The invention discloses a substituted naphthalimide derivative and a preparation method and application thereof, and the derivative has a general formula D structure, wherein R1 is selected from one of n-butyl, phenyl, p-tolyl and p-ethylphenyl, and R2 is selected from one of ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl. The fluorescent dichroic dye designed and prepared by the invention not only can stabilize the nematic phase, but also can increase the transition temperature (T) from the nematic phase to isotropyNI) And increase the temperature range of the liquid crystal phase. A series of 1, 8-naphthalic anhydride fluorescent dichroic liquid crystal dyes are designed and synthesized, and the fluorescent dichroic liquid crystal dyes are novel in structure, easy to obtain raw materials, environment-friendly and green; the dye has the maximum absorption wavelength of 404nm and the maximum emission wavelength of 509nm, presents blue fluorescence, the fluorescence quantum yield can reach 0.81 at most, the maximum absorption order parameter is 0.69, and the maximum fluorescence order parameter is 0.68. Has practical value in guest-host type liquid crystal display.
Description
Technical Field
The invention relates to a substituted naphthalimide derivative, a preparation method and application thereof, belonging to the field of display materials.
Background
There are many ways to acquire human information, but more than 70% of the information is obtained by visual means, so that the information display technology plays an important role. Among the many display modes, the "guest-host" liquid crystal display (GH-LCD) is the most light-utilizing display mode because it requires only one or even no polarizer for operation, which greatly increases the light source utilization compared to other display modes in which two polarizers are necessary. In addition, the GH-LCD has the characteristics of wide visual angle, bright color, high brightness, suitability for special environments and the like.
In the GH-LCD display mode, the most important is the research on the guest dichroic dye, which needs to satisfy the requirement of having a sufficiently high dichroic ratio; good solubility in the host liquid crystal and does not interfere with the properties of the host liquid crystal; however, due to the structural limitation of fluorescent dyes, the number of fluorescent dichroic dyes which really meet the actual requirements is small, and most of the fluorescent dichroic dyes are modified from the determined parent substance on the basis of previous researches, but the research on the naphthalic anhydride mostly stays at the end of the last century and is not advanced.
Disclosure of Invention
In order to solve the problem of lack of a fluorescent dichroic dye with good performance in the prior art, the invention provides the fluorescent dichroic liquid crystal dye which has yellow green fluorescence, high fluorescence quantum yield, good dichroic ratio and order parameters in liquid crystal E7, wide temperature range, high birefringence value, is easy to dissolve in main liquid crystal E7, can reduce the response time of liquid crystal E7 and is suitable for liquid crystal display products.
A substituted naphthalimide derivative has the following chemical molecular structure general formula:
wherein R1 is selected from one of n-butyl, phenyl, p-tolyl and p-ethylphenyl, and R2 is selected from one of ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl.
Further, the R1 is preferably selected from one of n-butyl, phenyl and p-tolyl, and R2 is selected from one of ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl.
Another technical object of the present invention is to provide the method for preparing the fluorescent dichroic liquid crystal dye, comprising the steps of: preparation of
The method comprises the steps of taking 4-bromo-1, 8-naphthalic anhydride as a raw material, firstly reacting with corresponding alkylamine or phenylamine to generate 4-bromo-1, 8-naphthalimide, then reacting with piperazine or p-hydroxypiperidine to generate 4-piperazine-1, 8-naphthalimide or 4-p-hydroxypiperidine-1, 8-naphthalimide, and then reacting with corresponding alkyl bicyclohexanoic acid respectively to generate the fluorescent dichroic liquid crystal dye.
The alkylamine and the phenylamine are selected from one of n-butylamine, aniline, toluidine and ethylaniline. The alkyl bicyclohexyl formic acid is one of ethyl bicyclohexyl formic acid, n-propyl bicyclohexyl formic acid, n-butyl bicyclohexyl formic acid, n-pentyl bicyclohexyl formic acid and n-hexyl bicyclohexyl formic acid.
The specific synthetic route is as follows:
further, 4-bromo-1, 8-naphthalic anhydride is dissolved in ethanol or ethylene glycol monomethyl ether solution, n-butylamine or phenylamine with equal mass is added, reflux reaction is carried out until the reaction is complete, and suction filtration is carried out to obtain 4-bromo-1, 8-naphthalimide (compound 2).
Further, the compound 2 and excessive p-hydroxypiperidine are refluxed and reacted in the ethylene glycol monomethyl ether solvent until the reaction is completed, and the 4-p-hydroxypiperidine-1, 8-naphthalimide (compound 3) is obtained by suction filtration, washing and drying
Further, the compound 3 and the alkyl dicyclohexyl are dissolved in a dichloromethane solvent, and the molar ratio of the compound 3 to the alkyl dicyclohexyl is 1: 1, adding a proper amount of Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) as catalysts, reacting at normal temperature until the reaction is complete, removing the solvent by rotary evaporation, using a mixture of ethyl acetate and petroleum ether as a developing agent, and performing silica gel column chromatography separation to obtain the dichroic liquid crystal dye.
In another aspect, the present invention provides the use of the above derivatives as fluorescent dichroic dyes. The dye is a dye having a liquid crystal phase.
The invention also provides application of the fluorescent dichroic dye in manufacturing liquid crystal display products. The liquid crystal display product is a guest-host type liquid crystal display. The dye is used as guest liquid crystal dye and is applied to preparing guest-host liquid crystal displays.
In another aspect, the present invention provides a guest-host liquid crystal display, wherein the liquid crystal display uses the fluorescent bidirectional dye as guest liquid crystal dye.
In addition, the liquid crystal dye also has a liquid crystal phase and has a larger liquid crystal phase temperature range. The liquid crystal is mainly smectic phase liquid crystal, nematic phase liquid crystal or cholesteric phase liquid crystal. The addition of E7 shortened the response time of the mixed liquid crystal. The addition of E7 lowers the threshold voltage of the mixed liquid crystal and reduces the power consumption of the liquid crystal display.
The invention has the beneficial effects that: the invention takes 1, 8-naphthalic anhydride as a parent to synthesize the fluorescent dichroic dye containing 4- (p-alkyl dicyclohexyl) -1, 8-naphthalic anhydride, and designs a new structure of the fluorescent dichroic dye; the new structural compound can stabilize nematic phase and increase the transition temperature (T) from nematic phase to isotropic phaseNI) Thereby increasing the width of the liquid crystal phase and having a larger liquid crystal phase temperature range. The maximum absorption wavelength of the series of compounds is 404nm, the maximum fluorescence emission wavelength is close to 509nm, and yellow green fluorescence is presented. The absorption order parameter is 0.54-0.69, the absorption dichroic ratio is 4.53-7.82, the fluorescence order parameter is 0.66-0.68, and the fluorescence dichroic ratio is 6.88-7.24, which meets the application requirements of the guest-host type liquid crystal display.
Drawings
FIG. 1 is a differential thermal scanning calorimetry plot of D1 lc compounds prepared in the examples;
FIG. 2 is a differential thermal scanning calorimetry plot of the D2 and D3 liquid crystalline compounds prepared in the examples.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
Synthesis of fluorescent dichroic dye D1
(1) Synthesis of 4-bromo-N-N-butyl-1, 8-naphthalimide (Compound 2)
2771mg (10mmol) of 4-bromo-1, 8-naphthalic anhydride and 30mL of anhydrous ethanol are added into a 100mL single-neck bottle, 1.48mL (12mmol) of n-butylamine is added under stirring at room temperature, the mixture is heated and refluxed for reaction for 2 hours, and filtration, washing with ethanol and drying are carried out to obtain 2412mg of light white solid with the yield of 73%.
(2) Synthesis of 4-hydroxypiperidine-N-N-butyl-1, 8-naphthalimide (Compound 3)
1328mg (4mmol) of the compound 4-bromo-N-N-butyl-1, 8-naphthalimide is added into a 50ml two-neck flask, 15ml of ethylene glycol monomethyl ether is added as a solvent, 1213mg (12mmol) of p-hydroxypiperidine is slowly added dropwise into the reaction system, the completion of the reaction is detected by a dot plate, and the reaction is completed after about 2 hours. Suction filtration, washing and drying gave 1037mg of a bright yellow solid in 74% yield.
(3) Synthesis and characterization of target Compound D1
In a 50mL two-necked flask, the ratio of 1: 1, adding 4-p-hydroxypiperidine-N-N-butyl-1, 8-naphthalimide and pentyldicyclohexyl formic acid, adding dichloromethane, adding slightly excessive dicyclohexyl carbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) into a reaction system, reacting for 2h at normal temperature, and separating and purifying by using a silica gel column chromatography, wherein the eluent is dichloromethane: methanol 20: 1(V/V) to give a yellow solid, yield: 60 percent. Melting point: 171.91 ℃, clearing point: 310.4 ℃. + ESI MS (M + H): c39H54N2O4Calculating the value: 615.4117, found: 615.4145.
1H NMR(400MHz,CDCl3)δ8.58(d,J＝7.2Hz,1H),8.51(d,J＝8.0Hz,1H),8.37 (d,J＝8.4Hz,1H),7.69(t,J＝7.8Hz,1H),7.22(d,J＝8.1Hz,1H),5.15-5.03(m,1H), 4.21–4.13(m,2H),3.46-3.38(m,J＝8.4Hz,2H),3.22–3.15(m,2H),2.42-2.34(m,J ＝11.9Hz,1H),2.27–2.17(m,2H),2.04–1.94(m,3H),1.83-1.77(m,J＝13.5Hz,3H), 1.74–1.67(m,3H),1.59(s,2H),1.50–1.36(m,6H),1.30-1.25(m,J＝9.6Hz,7H), 1.17-1.13(m,4H),1.08–1.01(m,4H),0.96(t,J＝7.3Hz,3H),0.87(t,J＝7.2Hz,3H).13C NMR(126MHz,CDCl3)δ175.60,164.46,164.00,156.15,132.43,131.04,130.06, 129.83,126.28,125.68,123.33,116.79,115.05,68.53,55.74,50.53,43.87,43.25, 42.56,40.08,37.88,37.43,34.93,33.56,32.23,31.09,30.27,30.01,29.70,29.41, 29.17,26.65,25.46,24.69,22.70,20.41,14.11,13.86.
example 2
Synthesis and characterization of fluorescent dichroic dye D2
(4) Synthesis of 4-bromo-N-p-tolyl-1, 8-naphthalimide (Compound 2)
2771mg (10mmol) of 4-bromo-1, 8-naphthalic anhydride and 30mL of ethylene glycol monomethyl ether are added into a 100mL single-mouth bottle, 1072mg (10mmol) of p-toluidine is added under stirring at room temperature, the mixture is heated and refluxed for reaction for 1h, and the mixture is filtered and dried to obtain 2628mg of light brown solid with the yield of 72%.
(5) Synthesis of 4-hydroxypiperidinyl-N-p-tolyl-1, 8-naphthalimide
Except for replacing 4-bromo-N-N-butyl-1, 8-naphthalimide by 4-bromo-N-p-tolyl-1, 8-naphthalimide, the synthesis steps and the purification method are the same as the step (2), so that bright yellow solid is obtained, and the yield is 64%.
(6) Synthesis of target Compound D2
The same procedure as in step (3) was repeated except that 4-hydroxypiperidine-N-N-butyl-1, 8-naphthalimide was used instead of 4-piperazine-N-N-butyl-1, 8-naphthalimide, and the eluent was petroleum ether: ethyl acetate ═ 3: 1(V/V) to give a yellow-green solid, yield: and 47 percent. Melting point: 220.6 ℃, clearing point: 271.3 ℃. + ESI MS (M + H): c42H52N2O4Calculating the value: 649.3961, found: 649.3989.
1H NMR(400MHz,CDCl3)δ8.65(d,J＝7.1Hz,1H),8.57(d,J＝8.1Hz,1H),8.44 (d,J＝8.4Hz,1H),7.75(d,1H),7.36(d,J＝8.1Hz,2H),7.28(d,J＝7.3Hz,1H),7.21 (d,J＝8.1Hz,2H),5.06-5.18(m,1H),3.43-3.52(m,2H),3.29–3.21(m,2H),2.46(s, 3H),2.32-2.28(t,J＝7.9Hz,1H),2.26–2.19(m,2H),2.06(d,J＝10.3Hz,3H), 1.83-1.79(m,3H),1.72(d,J＝9.8Hz,3H),1.61(s,2H),1.49–1.41(m,2H),1.31-1.26 (m,J＝11.3Hz,7H),1.19-1.14(m,3H),1.10-1.03(m,J＝14.9Hz,4H),1.01-0.97(d,J ＝11.6Hz,2H),0.90(t,J＝5.1Hz,3H).13C NMR(126MHz,CDCl3)δ175.61,164.71, 164.21,156.49,154.33,138.36,132.96,132.87,131.47,130.46,130.26,130.02, 128.34,126.41,125.75,123.44,116.74,115.12,50.52,43.88,43.26,42.58,37.89, 37.44,33.96,33.57,32.71,32.23,31.10,30.19,30.02,29.43,29.26,29.18,26.65, 26.29,24.75,22.70,21.30,14.11.
example 3
Synthesis and characterization of fluorescent dichroic dye D3
(7) Synthesis of 4-bromo-N-phenyl-1, 8-naphthalimide
2771mg (10mmol) of 4-bromo-1, 8-naphthalic anhydride and 30mL of ethylene glycol monomethyl ether are added into a 100mL single-mouth bottle, 1.12mL (12mmol) of aniline is added under stirring at room temperature, the mixture is heated and refluxed for reaction for 2 hours, and then the mixture is filtered and dried to obtain 2203mg of light brown solid with the yield of 63%.
(8) Synthesis of 4-p-hydroxypiperidinyl-N-p-tolyl-1, 8-naphthalimide
Except for replacing 4-bromo-N-N-butyl-1, 8-naphthalimide by 4-bromo-N-phenyl-1, 8-naphthalimide, the synthesis steps and the purification method are the same as the step (2), so that bright yellow solid is obtained, and the yield is 62%.
(9) Synthesis and characterization of target Compound D3
The procedure is the same as in step (3) except that 4-hydroxypiperidine-N-phenyl-1, 8-naphthalimide is used instead of 4-piperazine-N-N-butyl-1, 8-naphthalimide, and the eluent is petroleum ether: ethyl acetate ═ 3: 1(V/V) to give a yellow-green solid, yield: and 43 percent. Melting point: 149.8 ℃, clearing point: 286.7 deg.C. + ESI MS (M + H): c41H50N2O4Calculating the value: 635.3804, found: 635.3822.
1H NMR(400MHz,CDCl3)δ8.65(d,J＝7.2Hz,1H),8.57(d,J＝8.1Hz,1H),8.45 (d,J＝8.4Hz,1H),7.81–7.72(m,1H),7.57(t,J＝7.5Hz,2H),7.49(t,J＝7.4Hz,1H), 7.33(d,J＝7.3Hz,2H),7.28(t,J＝4.0Hz,2H),5.11(s,1H),3.49(s,2H),3.31–3.19 (m,2H),2.33–2.27(m,1H),2.26–2.19(m,2H),2.06(d,J＝10.8Hz,3H),1.87–1.79 (m,3H),1.77–1.71(m,3H),1.61(s,2H),1.46(dd,J＝25.1,12.7Hz,2H),1.35–1.24 (m,7H),1.17(s,3H),1.12–1.03(m,4H),1.02–0.94(m,2H),0.90(t,J＝6.9Hz,3H).13C NMR(126MHz,CDCl3)δ175.65,164.65,164.16,156.57,135.67,132.93,131.52, 130.55,130.30,129.31,128.71,128.55,126.42,125.78,123.41,116.68,115.16, 68.57,50.53,43.88,43.26,42.58,37.90,37.44,33.57,32.24,31.08,30.02,29.39, 29.20,26.66,22.72,14.11.
determination of the properties of the fluorescent dichroic dyes of the present invention:
(1) spectral properties of the dyes in dichloromethane test:
dye test concentration: the concentration of the dye in different solvents is 1.0X 10-5mol/L。
Fluorescence quantum yield phi of dyeFDetermination of the value: based on a quinothionine sulfate solution. Calculating by substituting formula (1):
in the formula: phi(sample)、Φ(standard)Respectively representPhi of sample and standardFA value; abs(standard)、Abs(sample)Respectively representing the absorbance of the standard substance and the sample under the excitation wavelength; flu (sample) and flu (standard) represent the integrated areas of the fluorescence spectra of the sample and the standard, respectively.
The results of the tests for compounds D1-D3 are as follows:
TABLE 1 UV and fluorescence data for dyes D1-D3 in methylene chloride
(2) Polarization spectral property test of dye in liquid crystal:
the bulk liquid crystal was E7, and the cell thickness was 20 μm. The dye B is mixed into the liquid crystal according to the mass concentration of 0.5% (w/w) and packed. Respectively testing the absorbance A of the dye and the liquid crystal box alignment film in the parallel direction‖And absorbance A in the vertical direction⊥Fluorescence intensity in parallel direction F‖And fluorescence intensity F in the vertical direction⊥(ii) a And calculating the absorption order parameter S of the dye in the liquid crystal according to the following formulas (2), (3), (4) and (5)ADichroic ratio DAAnd fluorescence order parameter SFDichroic ratio DF：
The results of the polarization spectrum test of the dyes D1-D3 are as follows:
TABLE 2 polarized UV and polarized fluorescence data for dyes D1-D3 in liquid crystal E7
D1-D3 showed better dichroic ratio and order parameter in liquid crystal E7. The absorption order parameter is 0.54-0.69, the absorption dichroic ratio is 4.53-7.82, the fluorescence order parameter is 0.66-0.68, and the fluorescence dichroic ratio is 6.88-7.24, so that the practical application requirement of guest-host display is met.
(3) Liquid crystal behavior of fluorescent dichroic liquid crystal dyes
The prepared liquid crystal compound was subjected to differential thermal scanning to obtain a differential thermal scanning calorimetry map, as shown in FIGS. 1 and 2.
(4) Effect of fluorescent dichroic liquid Crystal dye D on threshold Voltage and response time of host liquid Crystal E7
The mixtures of liquid crystals E7 and E7+ D (D added in an amount of 0.5 wt%) were tested for response time and threshold voltage data, as shown in Table 3.
TABLE 3 response time and threshold Voltage data Table for mixtures of liquid crystals E7 and E7+ D
The addition of compound D reduces the response time of the host liquid crystal, and the addition of compound D reduces the threshold voltage of the host liquid crystal.
Claims (10)
1. A substituted naphthalimide derivative has the following chemical molecular structure general formula:
wherein R1 is selected from one of n-butyl, phenyl, p-tolyl and p-ethylphenyl, and R2 is selected from one of ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl.
2. A process for the preparation of substituted naphthalimide derivatives according to claim 1, comprising the steps of:
taking 4-bromo-1, 8-naphthalic anhydride as a raw material, firstly reacting with corresponding alkylamine or phenylamine to generate 4-bromo-1, 8-naphthalimide, then reacting with p-hydroxypiperidine to generate 4-p-hydroxypiperidine-1, 8-naphthalimide, and then reacting with corresponding alkyl bicyclohexanoic acid respectively to generate the fluorescent dichroic liquid crystal dye;
the alkyl amine and the phenyl amine are selected from one of n-butylamine, aniline, toluidine and ethylaniline, and the alkyl bicyclohexyl formic acid is selected from one of ethyl bicyclohexyl formic acid, n-propyl bicyclohexyl formic acid, n-butyl bicyclohexyl formic acid, n-pentyl bicyclohexyl formic acid and n-hexyl bicyclohexyl formic acid.
3. Use of the derivative of claim 1 as a fluorescent dichroic dye.
4. Use according to claim 3, characterized in that the dye is a dye having a liquid crystalline phase.
5. Use of the compound of claim 1 as a liquid crystal dye.
6. Use of a compound according to claim 1 as a liquid crystal material.
7. Use of the compound of claim 1 for the manufacture of liquid crystal display products.
8. The use of claim 7, wherein said liquid crystal display product is a guest-host type liquid crystal display.
9. A guest-host liquid crystal display characterized by using the compound of claim 1 as a guest liquid crystal dye.
10. A liquid crystal material which is a mixed liquid crystal of the derivative of claim 1 and a liquid crystal E7.
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Citations (6)
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| CN1902180A (en) * | 2003-11-14 | 2007-01-24 | 巴斯福股份公司 | Use of 4-cyano-naphthalene-1,8-dicarboximide derivatives and related compounds to protect organic material from the damaging effects of light |
| CN101942211A (en) * | 2010-09-21 | 2011-01-12 | 大连理工大学 | Naphthalimide fluorescent dichroic dye containing aromatic ester group and application thereof |
| CN101942210A (en) * | 2010-09-21 | 2011-01-12 | 大连理工大学 | 4-amido-1,8-naphthalimide derivative fluorescent dichroic dye and application thereof |
| CN102757662A (en) * | 2012-07-03 | 2012-10-31 | 大连理工大学 | Acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes, as well as preparation method and application thereof |
| CN106478599A (en) * | 2016-09-12 | 2017-03-08 | 大连理工大学 | One class contains the fluorescence dichroic dye of 4 piperazinyl, 1,8 naphthalimide, its preparation method and application |
| CN106520139A (en) * | 2016-09-13 | 2017-03-22 | 大连理工大学 | Liquid crystal compound containing 4-(biphenyl acetenyl)-1,8 naphthalimide, preparing method and application |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1902180A (en) * | 2003-11-14 | 2007-01-24 | 巴斯福股份公司 | Use of 4-cyano-naphthalene-1,8-dicarboximide derivatives and related compounds to protect organic material from the damaging effects of light |
| CN101942211A (en) * | 2010-09-21 | 2011-01-12 | 大连理工大学 | Naphthalimide fluorescent dichroic dye containing aromatic ester group and application thereof |
| CN101942210A (en) * | 2010-09-21 | 2011-01-12 | 大连理工大学 | 4-amido-1,8-naphthalimide derivative fluorescent dichroic dye and application thereof |
| CN102757662A (en) * | 2012-07-03 | 2012-10-31 | 大连理工大学 | Acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes, as well as preparation method and application thereof |
| CN106478599A (en) * | 2016-09-12 | 2017-03-08 | 大连理工大学 | One class contains the fluorescence dichroic dye of 4 piperazinyl, 1,8 naphthalimide, its preparation method and application |
| CN106520139A (en) * | 2016-09-13 | 2017-03-22 | 大连理工大学 | Liquid crystal compound containing 4-(biphenyl acetenyl)-1,8 naphthalimide, preparing method and application |
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