CN109180639A - The naphthalimide derivative that one kind replaces, preparation method and application - Google Patents
The naphthalimide derivative that one kind replaces, preparation method and application Download PDFInfo
- Publication number
- CN109180639A CN109180639A CN201811034145.8A CN201811034145A CN109180639A CN 109180639 A CN109180639 A CN 109180639A CN 201811034145 A CN201811034145 A CN 201811034145A CN 109180639 A CN109180639 A CN 109180639A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- fluorescence
- formic acid
- application
- dyestuff
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/08—Naphthalimide dyes; Phthalimide dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
- C09K19/3483—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a non-aromatic ring
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13725—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on guest-host interaction
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal (AREA)
Abstract
The invention discloses the naphthalimide derivatives and its preparation method and application that one kind replaces, with general formula D structure, wherein R1 is selected from normal-butyl, phenyl, p-methylphenyl and to one of ethylbenzene, and R2 is selected from one of ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl.The fluorescence dichroic dye that the present invention designs preparation can not only stablize nematic phase, but also can increase nematic phase to isotropic transition temperature (TNI), and increase the temperature range of liquid crystalline phase.Design has synthesized a series of 1,8- naphthalene anhydride class fluorescence dichroism liquid crystalline dyes, structure novel, and raw material is easy to get, environment-friendly and green；Blue-fluorescence is presented in 404nm, maximum emission wavelength 509nm in the dyestuff maximum absorption wavelength, and fluorescence quantum yield reaches as high as 0.81, and absorption maximum order parameter is that 0.69 maximum fluorescence order parameter is 0.68.With the practical value in guest-host type liquid crystal display.
Description
Technical field
The present invention relates to the naphthalimide derivatives and its preparation method and application that one kind replaces, and belong to display material neck
Domain.
Background technique
There are many kinds of the acquisition modes of human information, but be more than 70% information is obtained by visual pathway, because
This information display technology has acted as highly important role.In numerous display patterns, " guest-master " liquid crystal display (GH-LCD)
The highest display pattern of light source utilization rate because it only need at work it is a piece of even without polaroid, this compared to
Other must be with for the display pattern of two panels polaroid, and it greatly improves the utilization rates of light source.In addition to this, GH-LCD is also
The features such as bright in luster with wide viewing angle, brightness is high, can be suitably used for particular surroundings.
In GH-LCD display pattern, most important is exactly the research of guest's body dichroic dye, and this kind of dyestuff needs to meet
There is sufficiently high dichroic ratio；There is good solubility in bulk liquid crystal, and does not interfere the property of bulk liquid crystal；But due to
The structure of fluorescent dye limits, and the fluorescence dichroic dye for really meeting actual requirement is few, and is studied in forefathers mostly
On the basis of, determining parent is transformed, but is to rest on the end of last century and do not have mostly for the research of naphthalene anhydride
Progress.
Summary of the invention
For solve the problems, such as it is existing in the prior art lack fluorescence dichroic dye of good performance, the present invention provides
A kind of presentation yellow-green fluorescence has high-fluorescence quantum yield, shows in liquid crystal E7 preferable dichroic ratio and orderly
Parameter, the liquid crystal for having wide temperature range, the sound for having high birefringence value, being soluble in bulk liquid crystal E7, liquid crystal E7 capable of being reduced
Between seasonable, suitable for the fluorescence dichroism liquid crystalline dyes of liquid crystal display product.
The naphthalimide derivative that one kind replaces has chemical molecular general structure below:
Wherein, R1 is selected from normal-butyl, phenyl, p-methylphenyl and to one of ethylbenzene, R2 be selected from ethyl, n-propyl,
One of normal-butyl, n-pentyl, n-hexyl.
Further, the R1 preferably is selected from one of normal-butyl, phenyl and p-methylphenyl, R2 be selected from ethyl, n-propyl,
One of normal-butyl, n-pentyl, n-hexyl.
Another technical object of the present invention is to provide the method for above-mentioned fluorescence dichroism liquid crystalline dyes, including following step
It is rapid: preparation
It with bromo- 1, the 8- naphthalene anhydride of 4- for raw material, is first reacted with corresponding alkylamine or phenyl amine, generates 4- bromo- 1,8 naphthoyls
Imines, then reacted with piperazine or to hydroxy piperidine, it is sub- to hydroxy piperidine -1,8 naphthoyl to generate 4- piperazine -1,8 naphthalimide or 4-
Amine, then reacted respectively with corresponding alkyl bicyclic hexane formic acid, generate the fluorescence dichroic liquid crystal dyestuff.
The alkylamine and phenyl amine is selected from one of n-butylamine, aniline, toluidines and ethylbenzene amine.The alkyl
Bis cyclohexane formic acid is selected from ethyl dicyclohexyl formic acid, n-propyl dicyclohexyl formic acid, normal-butyl dicyclohexyl formic acid, n-pentyl
One of dicyclohexyl formic acid and n-hexyl dicyclohexyl formic acid.
Specific synthetic line is as follows:
Further, bromo- 1, the 8- naphthalene anhydride of 4- is dissolved in ethyl alcohol or ethylene glycol monomethyl ether solution, the amount of substance such as adds
N-butylamine or phenyl amine, back flow reaction to fully reacting filter to obtain bromo- 1, the 8- naphthalimide (compound 2) of 4-.
Further, compound 2 with it is excessive to hydroxy piperidine in glycol monoethyl ether solvent back flow reaction to having reacted
Entirely, it filters, washing, dry 4- is to hydroxy piperidine base -1,8- naphthalimide (compound 3)
Further, compound 3 and alkyl bicyclic hexyl are dissolved in dichloromethane solvent, compound 3 and alkyl bicyclic
It is 1:1 that hexyl, which obtains molar ratio, adds suitable dicyclohexylcarbodiimide (DCC) and 4- dimethylamino naphthyridine (DMAP) is made
Catalyst, normal-temperature reaction to fully reacting, revolving remove solvent, make solvent, silicon with the mixture of ethyl acetate and petroleum ether
Plastic column chromatography separates up to the dichroism liquid crystalline dyes.
Another aspect of the present invention provides application of the above-mentioned derivative as fluorescence dichroic dye.The dyestuff is tool
There is the dyestuff of liquid crystalline phase.
Another aspect of the present invention provides application of the above-mentioned fluorescence dichroic dye in manufacture liquid crystal display product.It is described
Liquid crystal display product be guest-host type liquid crystal display.As guest's body liquid crystalline dyes, applied to preparing guest-host type liquid crystal display.
Further aspect of the present invention is designed to provide a kind of guest-host type liquid crystal display, and the liquid crystal display is with this
The invention two tropism dyestuff of fluorescence is as guest's body liquid crystalline dyes.
In addition, liquid crystalline dyes of the invention also have liquid crystalline phase, there is biggish liquid crystal phase temperature range.The liquid crystal master
It to be smectic liquid crystal, nematic liquid crystal or cholesteric liquid crystal.It is added in E7 and shortens the response time of mixed liquid crystal.It is added
The threshold voltage that mixed liquid crystal is reduced in E7 reduces the power consumption of liquid crystal display.
Beneficial effects of the present invention: the present invention contains 4- (to alkyl bicyclic hexyl base) -1 by parent synthesis of 1,8- naphthalene anhydride,
8- naphthalene anhydride class fluorescence dichroic dye, devises fluorescence dichroic dye new construction；Novel compound application can be steady
Determine nematic phase, and nematic phase can be increased to isotropic transition temperature (TNI), to increase the width of liquid crystalline phase, have compared with
Big liquid crystal phase temperature range.The maximum absorption wavelength of the series compound is 404nm, and maximum emission wavelength is close
Yellow-green fluorescence is presented in 509nm.Absorption order parameter is 0.54-0.69, and absorption dichroic ratio is 4.53-7.82, and fluorescence is orderly
Parameter is 0.66-0.68, and fluorescence dichroic ratio is 6.88-7.24, meets the application requirement of guest-host type liquid crystal display.
Detailed description of the invention
Fig. 1 is the D1 LCD compound differential scanning calorimetric figure prepared in embodiment；
Fig. 2 is D2, D3 the LCD compound differential scanning calorimetric figure prepared in embodiment.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Embodiment 1
The synthesis of fluorescence dichroic dye D1
(1) synthesis of bromo- N- normal-butyl -1, the 8- naphthalimide (compound 2) of 4-
Bromo- 1, the 8- naphthalene anhydride of 2771mg (10mmol) 4- is added in 100mL single port bottle, 30mL dehydrated alcohol is stirred in room temperature
Lower addition 1.48mL (12mmol) n-butylamine is mixed, temperature rising reflux reacts 2h, and filtering is dry with ethanol washing, and it is shallowly white to obtain 2412mg
Color solid, yield 73%.
(2) synthesis of 4- hydroxy piperidine-N- normal-butyl -1,8- naphthalimide (compound 3)
Bromo- N- normal-butyl -1, the 8- naphthalimide 1328mg (4mmol) of compound 4- is added in 50ml two mouth flask, adds
Enter 15ml glycol monoethyl ether as solvent, hydroxy piperidine 1213mg (12mmol) will be slowly added dropwise to reaction system, contact plate
The performance for detecting reaction, after about 2 hours, reaction is completed.It filters, wash, being dried to obtain bright yellow solid 1037mg, producing
Rate 74%.
(3) synthesis and characterization of target compound D1
In 50mL two-mouth bottle by the amount of the substance of 1:1 be added 4- to hydroxy piperidine-N- normal-butyl -1,8- naphthalimide and
Amyl dicyclohexyl formic acid is added methylene chloride, then slightly excessive dicyclohexylcarbodiimide (DCC) is added into reaction system
With 4-dimethylaminopyridine DMAP, normal-temperature reaction 2h, separating-purifying is carried out with silica gel column chromatography, eluent is methylene chloride:
Methanol=20:1 (V/V), obtains yellow solid, yield: 60%.Fusing point: 171.91 DEG C, clearing point: 310.4 DEG C.+ESI MS(M+
H): C39H54N2O4, calculated value: 615.4117, measured value: 615.4145.
1H NMR(400MHz,CDCl3) δ 8.58 (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.
Embodiment 2
The synthesis and characterization of fluorescence dichroic dye D2
(4) synthesis of the bromo- N- p-methylphenyl -1,8- naphthalimide (compound 2) of 4-
Bromo- 1, the 8- naphthalene anhydride of 2771mg (10mmol) 4-, 30mL glycol monoethyl ether, in room are added in 100mL single port bottle
Temperature is added with stirring 1072mg (10mmol) para-totuidine, and temperature rising reflux reacts 1h, and it is solid to obtain 2628mg light brown for filtration drying
Body, yield 72%.
(5) synthesis of 4- hydroxy piperidine base-N- p-methylphenyl -1,8- naphthalimide
Except being replaced outside bromo- N- normal-butyl -1, the 8- naphthalimide of 4- with bromo- N- p-methylphenyl -1, the 8- naphthalimide of 4-, close
At step and the same step of method of purification (2), bright yellow solid, yield 64% are obtained.
(6) synthesis of target compound D2
In addition to sub- with 4- hydroxy piperidine-N- normal-butyl -1,8- naphthalimide replacement 4- piperazine-N- normal-butyl -1,8- naphthoyl
Outside amine, the same step of remaining step (3), eluent is petroleum ether: ethyl acetate=3:1 (V/V) obtains greenish yellow solid, yield:
47%.Fusing point: 220.6 DEG C, clearing point: 271.3 DEG C.+ ESI MS (M+H): C42H52N2O4, calculated value: 649.3961, actual measurement
Value: 649.3989.
1H NMR(400MHz,CDCl3) δ 8.65 (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.
Embodiment 3
The synthesis and characterization of fluorescence dichroic dye D3
(7) synthesis of the bromo- N- phenyl -1,8- naphthalimide of 4-
Bromo- 1, the 8- naphthalene anhydride of 2771mg (10mmol) 4-, 30mL glycol monoethyl ether, in room are added in 100mL single port bottle
Temperature is added with stirring 1.12mL (12mmol) aniline, and temperature rising reflux reacts 2h, filters, dry, obtains 2203mg light tan solid, produces
Rate 63%.
(8) synthesis of the 4- to hydroxy piperidine base-N- p-methylphenyl -1,8- naphthalimide
Except with outside bromo- N- phenyl -1,8- naphthalimide replacement bromo- N- normal-butyl -1, the 8- naphthalimide of 4- of 4-, synthesis is walked
The rapid and same step of method of purification (2), obtains bright yellow solid, yield 62%.
(9) synthesis and characterization of target compound D3
In addition to replacing 4- piperazine-N- normal-butyl -1,8- naphthalimide with 4- hydroxy piperidine-N- phenyl -1,8- naphthalimide
Outside, the same step of remaining step (3), eluent is petroleum ether: ethyl acetate=3:1 (V/V) obtains greenish yellow solid, yield:
43%.Fusing point: 149.8 DEG C, clearing point: 286.7 DEG C.+ ESI MS (M+H): C41H50N2O4, calculated value: 635.3804, actual measurement
Value: 635.3822.
1H NMR(400MHz,CDCl3) δ 8.65 (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.
The property of fluorescence dichroic dye of the invention measures:
(1) the spectral property test of dyestuff in methylene chloride:
Dye test concentration: concentration of the dyestuff in different solvents is 1.0 × 10-5mol/L。
Dye fluorescence quantum yield ΦFThe measurement of value: on the basis of giving repeated exhortations solution by sulfuric acid quinoline.Substitution formula (1) calculates:
In formula: Φ(sample)、Φ(standard)Respectively represent the Φ of sample, reference substanceFValue；Abs(standard)、Abs(sample)
Respectively represent the absorbance of reference substance under excitation wavelength, sample；Flu (sample) and Flu (standard) respectively represent sample,
The fluorescence spectrum integral area of reference substance.
To compound D1-D3, test result is as follows:
The ultraviolet and fluorescence data of 1. dyestuff D1-D3 of table in methylene chloride
(2) polarization spectrum property test of the dyestuff in liquid crystal:
Bulk liquid crystal is E7, and liquid crystal cell box is with a thickness of 20 μm.The ratio for being 0.5% (w/w) according to mass concentration by dyestuff B
Simultaneously mounted box is incorporated into liquid crystal.Absorbance A in test dye and liquid crystal cell alignment films parallel direction respectively‖In vertical direction
Absorbance A⊥, fluorescence intensity F in parallel direction‖With the fluorescence intensity F in vertical direction⊥；And according to the following formula (2),
(3), (4), (5) calculate absorption order parameter S of the dyestuff in liquid crystalA, dichroic ratio DAWith fluorescence order parameter SF, two to
Color ratio DF:
Test result is as follows for dyestuff D1-D3 polarization spectrum:
Polarized UV and polarized fluorescence data of the 2. dyestuff D1-D3 of table in liquid crystal E7
D1-D3 shows preferable dichroic ratio and order parameter in liquid crystal E7.Absorption order parameter is 0.54-
0.69, absorption dichroic ratio is 4.53-7.82, and fluorescence order parameter is 0.66-0.68, and fluorescence dichroic ratio is 6.88-7.24,
Meet host and guest and shows application request.
(3) liquid crystal behavior of fluorescence dichroic liquid crystal dyestuff
Differential scanning is carried out to the liquid-crystal compounds of preparation, obtains its differential scanning calorimetric figure, as shown in Figure 1, 2.
(4) influence of the fluorescence dichroic liquid crystal dyestuff D to bulk liquid crystal E7 threshold voltage and response time
Response time and the threshold voltage data of the mixture of liquid crystal E7 and E7+D (additional amount of D is 0.5wt%) are tested,
As shown in table 3.
The response time of the mixture of table 3 liquid crystal E7 and E7+D and threshold voltage data table
The addition of compound D reduces the response time of bulk liquid crystal, and the addition of compound D reduces bulk liquid crystal
Threshold voltage.
Claims (10)
1. the naphthalimide derivative that one kind replaces has chemical molecular general structure below:
Wherein, R1 is selected from normal-butyl, phenyl, p-methylphenyl and to one of ethylbenzene, and R2 is selected from ethyl, n-propyl, positive fourth
One of base, n-pentyl, n-hexyl.
2. the preparation method of substituted naphthalimide derivative described in claim 1, comprising the following steps:
It with bromo- 1, the 8- naphthalene anhydride of 4- for raw material, is first reacted with corresponding alkylamine or phenyl amine, generation 4- bromo- 1,8 naphthalimides,
Again and to hydroxy piperidine react, generate 4- to hydroxy piperidine -1,8 naphthalimide, then respectively with corresponding alkyl bicyclic hexane first
Acid reaction, generates the fluorescence dichroic liquid crystal dyestuff；
The alkylamine and phenyl amine is selected from one of n-butylamine, aniline, toluidines and ethylbenzene amine.The alkyl bicyclic
It is bicyclic that hexane formic acid is selected from ethyl dicyclohexyl formic acid, n-propyl dicyclohexyl formic acid, normal-butyl dicyclohexyl formic acid, n-pentyl
One of hexyl formic acid and n-hexyl dicyclohexyl formic acid.
3. application of the derivative described in claim 1 as fluorescence dichroic dye.
4. application according to claim 3, which is characterized in that the dyestuff is the dyestuff with liquid crystalline phase.
5. application of the compound described in claim 1 as liquid crystalline dyes.
6. application of the compound described in claim 1 as liquid crystal material.
7. application of the compound described in claim 1 in manufacture liquid crystal display product.
8. application according to claim 7, which is characterized in that the liquid crystal display product is guest-host type liquid crystal display
Device.
9. a kind of guest-host type liquid crystal display, it is characterised in that using compound described in claim 1 as guest's body liquid crystalline dyes.
10. a kind of liquid crystal material, the liquid crystal material is the mixed liquid crystal of derivative and liquid crystal E7 described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811034145.8A CN109180639B (en) | 2018-09-05 | 2018-09-05 | Substituted naphthalimide derivative, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811034145.8A CN109180639B (en) | 2018-09-05 | 2018-09-05 | Substituted naphthalimide derivative, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109180639A true CN109180639A (en) | 2019-01-11 |
| CN109180639B CN109180639B (en) | 2020-06-02 |
Family
ID=64914816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811034145.8A Expired - Fee Related CN109180639B (en) | 2018-09-05 | 2018-09-05 | Substituted naphthalimide derivative, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109180639B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2018
- 2018-09-05 CN CN201811034145.8A patent/CN109180639B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109180639B (en) | 2020-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106520139B (en) | Containing -1,8 naphthalimide liquid-crystal compounds of 4- (biphenyl acetenyl), preparation method and application | |
| CN109336814A (en) | The naphthalimide derivative that one kind replaces containing 4- (alkyl bicyclic hexyl), preparation method and application | |
| CN106632239B (en) | A kind of isolonglifolane ketone group hexahydro quinazoline -2- amine schiff's base type fluorescent material and its synthetic method and application | |
| JP6792899B1 (en) | Phenylethynylborone dipyrromethene-based fluorescent dichroic liquid crystal compound and its use | |
| CN109762000A (en) | Based on the spirooxazine H-like ion fluorescent probe compounds and its synthetic method of 1,8- naphthalimide unit and application | |
| US11629157B2 (en) | Fluoro-boron pyrrole liquid crystal compounds containing 8-(bisphenylethynyl)-ester group flexible multiple ring, preparation method and use thereof | |
| CN106478599B (en) | One kind contains the fluorescence dichroic dye of 4- piperazinyl -1,8- naphthalimide, preparation method and application | |
| CN101942210B (en) | 4-amido-1,8-naphthalimide derivative fluorescent dichroic dye and application thereof | |
| CN104357063B (en) | Liquid crystalline cpd, its preparation method and application containing 4-(biphenyl ethynyl)-1,8-naphthalene dintrile | |
| CN102757662B (en) | Acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes, as well as preparation method and application thereof | |
| CN109180639A (en) | The naphthalimide derivative that one kind replaces, preparation method and application | |
| CN104293356B (en) | A kind of liquid crystalline cpd is as high birefringence rate liquid crystal material or improving the application in liquid crystal host degree of birefringence | |
| CN110117235A (en) | The compound and its preparation method and application of color shifting properties is caused with aggregation-induced emission and power | |
| CN109096188B (en) | Compound containing 4- (p-phenylethynyl) -1, 8-naphthalic anhydride, preparation method and application thereof | |
| CN112321619B (en) | 8- (diphenylethynyl) -ester group-containing boron-fluorine pyrrole compound and synthesis and application thereof | |
| CN109097028A (en) | Ester type compound of one kind phenylacetylene base containing 4- and its preparation method and application | |
| CN104194398B (en) | One class contains fluorescence dichroic dye, its preparation method and the application of 4-(to hydroxy piperidine base)-1,8-naphthalene dintrile | |
| CN109180654B (en) | Compound containing N-normal alkyl-4-phenylethynyl-1, 8-naphthalimide and preparation method and application thereof | |
| CN106433185B (en) | Fluorescence dichroic dye of the one kind containing 3 (biphenyl acetenyls) for acenaphthene simultaneously [1,2 b] quinoxaline, its preparation method and application | |
| CN102816454B (en) | Ester group containing 1,8-naphthalimide fluorescent dichroic dye, preparation method and application thereof | |
| CN105061320B (en) | A kind of acylhydrazone of imidazoles three, it is used as application of luminous organic material and preparation method thereof | |
| CN110128455A (en) | A kind of preparation method of borneol ester group phenylacetylene base BODIPY class pH fluorescence probe | |
| CN109134370B (en) | Substituted 4-phenylethynyl-1, 8-naphthalimide compound, preparation method and application thereof | |
| CN106928175B (en) | A kind of fluorescent pigment and preparation method thereof | |
| CN106519733B (en) | One kind contains the benzanthrone liquid crystalline dyes of 3 bit substituents, its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200602 Termination date: 20210905 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |