CN102757662B - Acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes, as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes with a structure with a general formula J shown in the specification, wherein R1 represents alkyl of 1-20 carbons or alkoxy of 1-20 carbons, and R2 represents amido, saturated 5-amido, saturated 6-amido and 6-heterocyclic amido of 1-20 carbons. According to the acylhydrazine containing 1,8-naphthalimide fluorescent dichroic dyes, by using 4-bromo-1,8-anhydride naphthalene as a parent, a heterocyclic amido is introduced in a 5 place for replacing a bromine atom to form a push-pull electronic system; an amido bond is introduced to effectively enhance the dissolubility of the dye in liquid crystal; and an acylhydrazine group is introduced to form an intramolecular hydrogen bond with ketonic oxygen on anhydride naphthalene, a five-membered ring structure is formed to enhance a conjugated system of dye molecules, and the dichroic ratio and the order parameter are increased; and an alkoxy chain is introduced to the end to ensure that the dissolubility of the dye in the liquid crystal is increased. A guest-host type liquid crystal display product using the dye as a guest body has the characteristics of high brightness, low energy consumption, colorful display and the like.

Description

One class contains 1 of hydrazides key, two tropism's dyestuff, its preparation method and the application of 8-naphthalimide fluorescent

Technical field

The class that the present invention relates in field of liquid crystal display " guest-master " type liquid-crystal display contains 1 of hydrazides key, 8-naphthalimide fluorescent two tropism's dyestuffs, its preparation method and application.

Background technology

" guest-master " type liquid crystal mode is that two tropism's dyestuffs are dissolved in the main body nematic liquid crystal as guest's body.Under the effect of extra electric field, dyestuff can rotate with the rotation of liquid crystal molecule, and then the dyestuff absorption spectrum is changed, thereby forms different GTGs and reach the purpose of demonstration.This display format only needs a slice polaroid or does not need polaroid, thereby has greatly improved light utilization efficiency.In recent years, fluorescence two tropism's dyestuffs replace two tropism's dyestuffs to use in " guest-master " display format, further having solved liquid crystal can not active illuminating, the shortcoming of low lightness, thereby the characteristics of traditional liquid-crystal display and emissive display can be integrated in one, become the lower electron device of a kind of energy consumption.

In the present invention the introducing of hydrazides group can with the naphthalene acid anhydride on ketonic oxygen form intramolecular hydrogen bond, the formation of five-membered ring structure has increased the conjugated system of dye molecule, improved dichroic than and order parameter.End has been introduced oxyalkyl chain, and the solubleness of dyestuff in liquid crystal is improved.

Summary of the invention

The object of the present invention is to provide the new fluorescence two tropism's dyestuffs of class, described dyestuff is to contain 1 of hydrazides key, and the 8-naphthoyl imide compounds has the structure of general formula J:

In general formula J:

R ₁The alkyl of 1-20 carbon or the alkoxyl group of 1-20 carbon,

R ₂Amido, saturated five yuan, hexa-atomic amido or the saturated hexa-member heterocycle amido of 1-20 carbon.

The present invention's purpose on the other hand is to provide the preparation method of fluorescence two tropism's dyestuffs of the invention described above, take compound 1(para-orientation phenylformic acid) as starting raw material, at first generate compound 2(para-orientation ethyl benzoate with ethanol synthesis), compound 2 obtains compound 3(para-orientation benzoyl hydrazine with the hydrazine hydrate reaction); Generate compound 5 with compound 4-bromo-1,8 naphthalene anhydride reactant, compound 5 and corresponding amine reaction, generate the target compound J that 4-replaces subsequently.

Concrete synthetic line figure is as follows:

Further aspect of the present invention provides the application of fluorescence two tropism's dyestuffs in making liquid crystal display product of the invention described above.The preferred guest-host type liquid-crystal display of wherein said liquid crystal display product.Particularly, be as the brilliant dyestuff of guest's body fluid, be applied to prepare the guest-host type liquid-crystal display.

Fluorescence two tropism's dye molecules of the present invention are with 4-bromo-1, and 8-naphthalene acid anhydride is parent, introduce heterocyclic amino group for 4 and replace bromine atoms to form pushing away-the La electron system; The introducing of amido linkage has effectively strengthened the solvability of dyestuff in liquid crystal; The introducing of hydrazides group can with the naphthalene acid anhydride on ketonic oxygen form intramolecular hydrogen bond, the formation of five-membered ring structure has increased the conjugated system of dye molecule, improved dichroic than and order parameter.End has been introduced oxyalkyl chain, and the solubleness of dyestuff in liquid crystal is improved.Using the characteristics such as such dyestuff is high as the guest-host type liquid crystal display product brightness of guest's body, energy consumption is low, display color is bright-coloured, is that a class has practical application fluorescence two tropism's dyestuffs.

Description of drawings

Accompanying drawing 2 width of the present invention,

Fig. 1 is the polarisation spectrum of dyestuff in liquid crystal E7 of embodiment 1; Wherein, a is the uv-absorbing wave spectrum, and b is the fluorescence wave spectrum;

Fig. 2 is the polarisation spectrum of dyestuff in liquid crystal E7 of embodiment 2; Wherein, a is the uv-absorbing wave spectrum, and b is the fluorescence wave spectrum.

Embodiment

At first the present invention provides the new fluorescence two tropism's dyestuffs of class, and described dyestuff is to contain 1 of hydrazides key, and the 8-naphthoyl imide compounds has the structure of general formula J:

In general formula J:

R ₁The alkyl of 1-20 carbon or the alkoxyl group of 1-20 carbon,

R ₂Amido, saturated five yuan, hexa-atomic amido or the saturated hexa-member heterocycle amido of 1-20 carbon.

In preferred technical scheme, R ₁Be selected from the straight chained alkyl of 4-8 carbon or the straight chain alkoxyl group of 4-8 carbon.Further, be preferably the straight chain alkoxyl group of 6-7 carbon.

In above-mentioned arbitrary technical scheme of the present invention, described R ₂Be preferably saturated five yuan, hexa-atomic amido or saturated hexa-member heterocycle amido.Further, be preferably saturated hexa-atomic amido or saturated hexa-member heterocycle amido.

The most preferably, fluorescence two tropism's dyestuffs of the present invention are selected from following compound:

4-morpholinyl-N-(4 '-hexyloxy) benzoyl diazanyl-1,8-naphthalimide (J1);

4-parathiazan base-N-(4 '-hexyloxy) benzoyl diazanyl-1,8-naphthalimide (J2);

4-hexahydropyridine base-N-(4 '-hexyloxy) benzoyl diazanyl-1,8-naphthalimide (J3).

Further illustrate the present invention with non-limiting example, but do not limit the present invention in any way.

If no special instructions, the present invention is with following method test dye performance: with dyestuff to be detected and liquid crystal according to certain mass than mixing, respectively test dye parallel with the liquid crystal cell alignment films with vertical direction on absorbance A and fluorescence intensity F.And calculate dyestuff according to following formula (1), (2), (3), (4) be absorbed with order parameter S in liquid crystal _A, dichroic compares D _AWith fluorescence order parameter S _F, dichroic compares D _F

$S_A=\frac{A_P-A_{\⊥}}{A_P+2A_{\⊥}}---\left(1\right)$

$D_A=\frac{A_P}{A_{\⊥}}---\left(2\right)$

$S_F=\frac{F_P-F_{\⊥}}{F_P+2F_{\⊥}}---\left(3\right)$

$D_F=\frac{F_P}{F_{\⊥}}---\left(4\right)$

Embodiment 1

4-morpholinyl-N-(4 '-hexyloxy) benzoyl diazanyl-1,8-naphthalimide (J1) synthetic

(1) to the preparation of hexyloxybenzoate ethyl ester (compound 2)

Add 2.22g(10mmol in the 25mL bottle with two necks) to hexyloxybenzoate, add 15mL ethanol and the 1mL vitriol oil, slowly be warming up to backflow under stirring, reaction 3h.Be poured into water standing, suction filtration, drying.Productive rate 86%.

(2) to the preparation of hexyloxy benzoyl hydrazine (compound 3)

Add 2.5g(10mmol in 50mL single port bottle) to hexyloxybenzoate ethyl ester (2), add the hydrazine hydrate of q.s, N ₂Protection is lower stirs, back flow reaction 2h.Be poured into water standing suction filtration, drying.Productive rate 76%.

(3) N-(is to the hexyloxy benzoylamino)-4-bromo-1, the preparation of 8-naphthalimide dyestuff (compound 5)

Add 331mg(1.2mmol in 50mL single port bottle) 4-bromo-1,8-naphthalene acid anhydride (4) adds 236mg(1mmol) to hexyloxy benzoyl hydrazine (3), the 30mL dehydrated alcohol, after back flow reaction 5h, directly vacuum rotary steam desolventizing, get light gray solid compound 5, productive rate 90%.

(4) 4-morpholinyl-N-(4 '-hexyloxy) benzoyl diazanyl-1,8-naphthalimide (compound J1) synthetic

Add 494mg(1mmol in 25mL single port bottle) compound 5,1mL morpholine and a small amount of catalyzer carbonic acid potassium and potassiumiodide, back flow reaction 2h.Directly be poured into water standing, suction filtration, drying.With methylene dichloride: ethyl acetate=50:3 column chromatography, separate to get compound J1, productive rate 90%, fusing point: 227.4-228.2 ℃.

TOF MS EI+ (m/z) (C ₂₉H ₃₁N ₃O ₅ ⁺): calculated value: 517.2035, experimental value: 517.203.

¹HNMR(CDCl ₃400MHz):δ(ppm):8.625(d,J=4.0Hz,1H),8.56(d,J=8.0Hz,1H),8.40(t,J ₁=8.0Hz,J ₂=12.0Hz,2H),7.73(t,J ₁=8.0Hz,J ₂=8.0Hz,1H),7.24(s,1H),6.94(d,J=8.0Hz,2H),4.02(t,J ₁=4.0Hz,J ₂=8.0Hz,2H),3.525(d,J=4.0Hz,4H),2.985(d,J=4.0Hz,4H),1.82(t,J ₁=4.0Hz,J ₂=8.0Hz,2H),1.48(t,J ₁=8.0Hz,J ₂=8.0Hz,2H),1.36(m,4H),0.920(t,J ₁=8.0Hz,J ₂=4.0Hz,3H).

Embodiment 2

4-parathiazan base-N-(4 '-hexyloxy) benzoyl diazanyl-1,8-naphthalimide (compound J2) synthetic

Replace morpholine with parathiazan, all the other synthetic methods are consistent with the step of synthetic J1 in embodiment 1.Column chromatography for separation, developping agent is methylene dichloride: ethyl acetate=50:3, gets orange solids.Productive rate is 83%.Fusing point: 254.8-255.2 ℃.

TOF MS EI+ (m/z) (C ₂₉H ₃₁N ₃O ₄S ⁺): calculated value: 517.2035, experimental value: 517.2035.

¹H?NMR(CDCl ₃,400MHz):δ(ppm):8.625(d,J=4.0Hz,1H),8.56(d,J=8.0Hz,1H),8.40(t,J ₁=8.0Hz,J ₂=12.0Hz,2H),7.73(t,J ₁=8.0Hz,J ₂=8.0Hz,1H),7.24(s,1H),6.94(d,J=8.0Hz,2H),4.02(t,J ₁=4.0Hz,J ₂=8.0Hz,2H),3.525(d,J=4.0Hz,4H),2.985(d,J=4.0Hz,4H),1.82(t,J ₁=4.0Hz,J ₂=8.0Hz,2H),1.48(t,J ₁=8.0Hz,J ₂=8.0Hz,2H),1.36(m,4H),0.920(t,J ₁=8.0Hz,J ₂=4.0Hz,3H).

Embodiment 3

4-hexahydropyridine base-N-(4 '-hexyloxy) benzoyl diazanyl-1,8-naphthalimide (compound J3) synthetic

Replace morpholine with parathiazan, all the other synthetic methods are consistent with the step of synthetic J1 in embodiment 1.Column chromatography for separation, developping agent is methylene dichloride: ethyl acetate=25:1, gets orange solids.Productive rate is 85%.Fusing point: 219.8-220.5 ℃.

TOF MS EI+ (m/z) (C ₃₀H ₃₃N ₃O ₄ ⁺): calculated value: 499.2479, experimental value: 499.2471.

¹H?NMR（CDCl ₃,400M?Hz）:δ(ppm):8.61(s,1H),8.57(d,J=8.0Hz,1H),8.50(d,J=8.0Hz,1H),8.38(d,J=8.0Hz,1H),7.95(d,J=8.0Hz,1H),7.65(t,J ₁=8.0Hz,J ₂=8.0Hz,1H),7.14(d,J=8.0Hz,1H),6.91(d,J=8.0Hz,2H),4.00(t,J ₁=8.0Hz,J ₂=8.0Hz,2H),3,235(d,J=4.0Hz,4H),1.89(t,J ₁=4.0Hz,J ₂=4.0Hz,4H),1.81(t,J ₁=8.0Hz,J ₂=8.0Hz,2H),1.735(d,J=4.0Hz,2H),1.48(t,J ₁=8.0Hz,J ₂=8.0Hz,2H),1.36(m,4H),0.92(t,J ₁=4.0Hz,J ₂=4.0Hz,3H).

Embodiment 4

The spectral quality test of dyestuff in solvent:

Ultra-violet absorption spectrum measure to use Hp 8453 ultraviolet-visible spectrophotometers (hewlette-packard), FP-6500 spectrophotofluorometer (Japanese JASCO company), BS-210S ten thousand/electronic balance (German Sartotius company).

Being mixed with concentration with the methylene dichloride constant volume is 1.0 * 10 ^-5The test soln of mol/L.Measure its ultraviolet-visible spectrum and fluorescence data.

The mensuration of the fluorescence quantum yield of dyestuff, with 4-butylamine base-N-normal-butyl-1,8-naphthalimide solution is benchmark (Φ F=0.81).Calculate by formula (5):

${\mathrm{\φ}}_{\left(\mathrm{sample}\right)}={\mathrm{\φ}}_{\left(s\tan \mathrm{dard}\right)}\×\frac{{\mathrm{Abs}}_{\left(s\tan \mathrm{dard}\right)}\×\mathrm{Fl}{u}_{\left(\mathrm{sample}\right)}}{{\mathrm{Abs}}_{\left(\mathrm{sample}\right)}\×{\mathrm{Flu}}_{\left(s\tan \mathrm{dard}\right)}}---\left(5\right)$

In formula: Φ _(sample), Φ _(standard)The fluorescence quantum yield that represents respectively testing sample and standard substance; Abs _(standard), Abs _(sample)The absorption value under excitation wavelength that represents respectively testing sample and standard substance; Flu _(sample), Flu _(standard)The fluorescence emission peak integral area that represents respectively testing sample and standard substance.

Test result to compound J1-J3 is as shown in table 1:

The Absorption and fluorescence data of table 1 dyestuff J1-J3 in methylene dichloride

Annotate: λ _maxRepresent maximum absorption wavelength, log ε represents molar extinction coefficient, δ _ARepresent the maximum absorption band peak width at half height, λ _emRepresent maximum emission wavelength, δ _FRepresent the maximum emission peak peak width at half height, Ф _FRepresent fluorescence quantum yield.

Can be found out by table 1 data, this series dyes maximum emission wavelength is positioned at visible region, the emission yellow-green fluorescence.

Embodiment 5

The polarisation spectrum property detection of dyestuff in liquid crystal:

Main body liquid crystal: select commercial liquid crystal E7 as the main body liquid crystal.

Liquid crystal cell: test consists of (the upper and lower base plate orientation is reversed 90 °) with liquid crystal cell by the two sheet glass substrates that the surface scribbles the orientation of polyimide agent, and box thickness is 7 μ m.

Testing method: it is 0.5%(w/w that dyestuff J1-J3 is mixed with concentration with liquid crystal respectively) liquid crystal compound.The mounted box test.Test calculates order parameter and the dichroic ratio of dyestuff according to formula (1), (2), (3), (4) after the uv-absorbing and fluorescence of parallel, vertical direction.

Polarization measurement result to compound is as shown in table 2:

The Absorption and fluorescence data of table 2 J series dyes in liquid crystal E7

Annotate: λ _maxRepresent maximum absorption wavelength, D _ARepresentative absorbs dichroic ratio, S _ARepresentative is absorbed with order parameter, λ _emRepresent maximum emission wavelength, D _FRepresent fluorescence dichroic ratio, S _FRepresent the fluorescence order parameter.

Can find out from Fig. 1 and Fig. 2, J1, the J2 dyestuff has obvious dichroism; Can find that from the data of table 2 J structural series dyestuff has higher order parameter and the fluorescence order parameter of being absorbed with in liquid crystal E7, can satisfy " host and guest " liquid-crystal display, using value is arranged.

Claims (2)

1. a class contains 1 of hydrazides key, and 8-naphthalimide fluorescent two tropism's dyestuffs have the structure of general formula J:

In general formula J: R ₁It is hexyloxy; R ₂Morpholinyl, parathiazan base or hexahydropyridine base.

2. the preparation method of fluorescence two tropism's dyestuffs claimed in claim 1, it is characterized in that take compound 1 as starting raw material, at first generates compound 2 with ethanol synthesis, and compound 2 obtains compound 3 with the hydrazine hydrate reaction; With compound 4 reacting generating compounds 5, compound 5 and corresponding amine reaction, generate the target compound J that 4-replaces subsequently,

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