CN1861607A - Fluorane kind derivant, its preparation and application - Google Patents
Fluorane kind derivant, its preparation and application Download PDFInfo
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- CN1861607A CN1861607A CN 200610050671 CN200610050671A CN1861607A CN 1861607 A CN1861607 A CN 1861607A CN 200610050671 CN200610050671 CN 200610050671 CN 200610050671 A CN200610050671 A CN 200610050671A CN 1861607 A CN1861607 A CN 1861607A
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Abstract
A fluorane derivative containing oxadiazole as side chain, its preparing process, and its application in preparing organic electroluminescent material, organic three-order non-linear optical material, and pressure-and heat-sensitive dyes are disclosed.
Description
(1) technical field
The present invention relates to a kind of fluorane kind derivant, the fluorane kind derivant of Han oxadiazole side chain particularly, and its production and application.
(2) background technology
The invention of fluorane based compound early.This compounds is mainly used in pressure-sensitive, heat sensitive dye, also is used to electroluminescent organic material now.Because its unique coloured light and gorgeous degree and superiority synthetic and application facet, and come into one's own, so far still in research and development.Owing to the existence of oxo bridge is arranged in the molecule, makes molecule keep rigid planar structure preferably, thereby produced intensive fluorescence.
The research of electroluminescent organic material and device is the key of plane technique of display research.Fluorane kind derivant is a kind of organic functions dye material that can send intense fluorescence.In the process of research, the contriver has found a kind of new fluorane kind derivant, it is the fluorane kind derivant of Han You oxadiazole side chain, this is good fluorescence chromonic materials of a class and organic non linear optical material, has the high and application performances such as coloured light and gorgeous degree uniqueness of fluorescence efficiency aspect molecular device.The fluorane compounds that can adopt high fluorescence efficiency in novel suspension system electroluminescent organic material host and guest luminous body structure is that host emitter is the precursor structure of luminescent material; Electric transmission Dan Yuan oxadiazole with high electron affinity is a guest emitter.The new organic fluorescent pigment that host emitter and guest emitter binding become to have the suspension system constitutional features.
Electroluminescent organic material, organic third order non-linear optical material etc. are the research and development focuses of functional pigmented material.About the molecular designing of electroluminescent organic material and organic third order non-linear optical material, the big pi-conjugated structure with intramolecular charge transport system (charge-transfer system) is basic constitutional features.Organic pigment molecule with big pi-conjugated structure has stronger photoelectricity coupling feature.Exist very closely between its electronic structure and geometric configuration and get in touch, the instantaneous variation that the geometry relaxation of the molecule that is caused by optical excitation originates from excited state π electric density is the bigger correction of wave function, so the instantaneous variation of whole molecular-excited state π electric charge is to cause that whole πDian Zi skeleton has the reason than strong nonlinearity optics polarizability.The organic luminophor of fluorane structure also is an electroluminescent organic material twinkler synthetic typical case intermediate.
(3) summary of the invention
The purpose of this invention is to provide a kind of new fluorane kind derivant and preparation and application.
The technical solution used in the present invention is as follows:
A kind of fluorane kind derivant, shown in (I),
Wherein, R1, R2 respectively do for oneself C1～C10 alkyl group, phenyl or substituent phenyl is arranged, described substituting group is alkyl group, nitro, the halogen of C1～C10.Wherein, the preferred ethyl of R1, n-propyl or normal-butyl, R2 preferable methyl or phenyl.
Material of Fluoran electroluminescent organic material provided by the present invention, being actually with the organic pigment fluorane is that luminescence center is that host emitter Yi oxadiazole analog derivative is that soluble conjugated polymerizable current carrier injection transmission body is a guest emitter, both bindings synthesize electroluminescent material, can regard that a kind of intramolecularly contains " suspension system " of organic pigment twinkler as.
The method of the described fluorane kind derivant of a kind of synthesis type (I) is: De oxadiazole derivative is in the presence of bronsted acid catalyst shown in 2-carboxyl-4 '-dialkyl amido-2 '-dihydroxy benaophenonel shown in the formula (II) and the formula (III), 50～80 ℃ of reactions 24～30 hours, with reaction product through secondary treatment, described secondary treatment is: with the reaction product cooled and filtered, reacted 5～25 hours at 50～90 ℃ with alkali lye and toluene after the filter cake washing, separatory is got toluene layer, obtains after the separating treatment suc as formula the fluorane kind derivant shown in (I).
In the synthetic method, the described amount of substance ratio that feeds intake is 2-carboxyl-4 '-dialkyl amido-2 '-dihydroxy benaophenonel ∶ oxadiazole derivative: bronsted acid catalyst is 8: 7～10: 400～480, and preferred 2-carboxyl-4 '-dialkyl amido-2 '-dihydroxy benaophenonel ∶ oxadiazole derivative is 8: 9: 400～480.
Reaction product in the above-mentioned reaction is normally poured reaction product reaction product cooling into trash ice in when secondary treatment, be stirred to cooled and filtered and get filter cake, described cooling so long as the way that the reaction product heat can be removed all be fine.After the common described washing the alkali lye that adds of filter cake and the amount of toluene alkali lye and 80～120ml toluene that should add 20～30ml 5% by the neutral filter cake of every 1g.
Described secondary treatment is recommended as: reaction product is poured in the trash ice, is stirred to coldly, filter, after the filter cake washing with alkali lye and toluene 60～80 ℃ of reactions 5～12 hours, separatory is got toluene layer, must be suc as formula the fluorane kind derivant shown in (I) after the separating treatment; Described alkali lye is sodium hydroxide, potassium hydroxide, ammoniacal liquor, magnesium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, aliphatic amide, arylamine, substituted aromatic amines.
Separating treatment recited above is recommended as and toluene layer is boiled off toluene promptly gets yellow solid, and yellow solid is washed with methyl alcohol, obtains white described fluorane kind derivant;
Further, described bronsted acid catalyst is one of following: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, organic aliphatic acid, organic aromatic acid, organic sulfonic acid, preferably sulfuric acid.
Fluorane kind derivant of the present invention has on 2 to have electron-withdrawing power De oxadiazole base and exist because 6 alkylaminos that strong electron donation arranged exist, and has strengthened intramolecular charge transport, and this structure is a dye material color bodies that hyperchromic effect is bigger.On this structure parent, connect corresponding auxochromous group or other color bodies, the material of fluoran fuctional pigments that just can synthesize specific function, for example, when functional pigmented materials such as synthetic organic third order non-linear optical material, electroluminescent material, described fluorane kind derivant Chang Zuowei color bodies.
Fluorane kind derivant preparation technology operational condition provided by the present invention is simple, easy to control, the convenient post-treatment of product, yield are higher, is an easy industrialized operational path.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Synthesizing of embodiment 1 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-diethylamino fluorane
(experiment is synthetic to add 2.5g in the there-necked flask of 50ml, 99%, 0.008mol) 2-carboxyl-4 '-diethylamino-2 '-dihydroxy benaophenonel and the 24ml vitriol oil (CP98%, 0.45mol), Deng dissolving fully below the postcooling to 5 ℃, add in batches 1.68g (experiment is synthetic, 97%, 0.009mol) 2-methyl-5-Dui Jia oxygen base Ben oxadiazole, begin to heat up.Pour in about 200ml trash ice after 24 hours in reaction under 60～70 ℃ of temperature, stir, filter, filter cake is washed till neutrality with 5% sodium hydrogen carbonate solution.Filter cake is poured in the 500ml four-hole bottle, added sodium hydroxide solution and the reaction of 200ml toluene of 50ml 5%, be warming up to 60～70 ℃, react after 6 hours.Separatory is got toluene layer, uses activated carbon decolorizing.Obtain 1.12g yellow solid compound 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-diethylamino fluorane after boiling off toluene, purity reaches more than 98%, and yield is 30.9%.Wash with methyl alcohol, obtain white solid, fusing point is 86～90 ℃, adds acid and can get red.
Its ir data is: 2969.43cm
-1Be methyl C-H stretching vibration, 1250.40cm
-1For the C-N stretching vibration causes, 1620.28cm
-1Be the absorption peak of phenyl ring, 1762.58cm
-1Be two keys of C=N and heterocycle.
Its
1H-NMR spectrum data are:
1HNMR (CDCl
3, ppm), the H proton adds up to 23.δ 8.08～δ 6.48 (m, 10H, the H on the phenyl ring), 3.38 (q, 4H, (CH
3CH
2)
2-), 2.54 (s, 3H, CH
3-), 1.18 (t, 6H, (CH
3CH
2)
2-).
Its ultimate analysis data are:
Calculated value (%): C, 71.52; H, 5.08; N, 9.27
Observed value (%): C, 71.50; H, 5.07; N, 9.31
Synthesizing of the amino fluorane of embodiment 2 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-di
(experiment is synthetic to add 2.7g in the there-necked flask of 50ml, 99%, 0.008mol) 2-carboxyl-4 '-di amino-2 '-dihydroxy benaophenonel and the 24ml vitriol oil (CP98%, 0.45mol), Deng dissolving fully below the postcooling to 5 ℃, add in batches 1.68g (experiment is synthetic, 97%, 0.009mol) 2-methyl-5-Dui Jia oxygen base Ben oxadiazole, begin to heat up.Pour in about 200ml trash ice after 30 hours in reaction under 60～70 ℃ of temperature, stir, filter, filter cake is washed till neutrality with 5% sodium hydrogen carbonate solution.Filter cake is poured in the 500ml four-hole bottle, added sodium hydroxide solution and the reaction of 200ml toluene of 50ml 5%, be warming up to 60～70 ℃, react after 8 hours.Separatory is got toluene layer, uses activated carbon decolorizing.Obtain the amino fluorane of 1.33g yellow solid compound 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-di after boiling off toluene, purity reaches more than 98%, and yield is 34.5%.Wash with methyl alcohol, obtain white solid, fusing point is 98～99 ℃, adds acid and can get red.
Its ir data is: 2969.91cm
-1Be methyl C-H stretching vibration, 1248.74cm
-1For the C-N stretching vibration causes, 1621.08cm
-1Be the absorption peak of phenyl ring, 1758.98cm
-1Be two keys of C=N and heterocycle.
Its
1H-NMR spectrum data are:
1HNMR (CDCl
3, ppm), the H proton adds up to 27.δ 8.08～δ 6.39 (m, 10H, the H on the phenyl ring), 3.38 (q, 4H, (CH
3CH
2CH
2)
2-), 2.36 (s, 3H, CH
3-), 1.37[m, 4H, (CH
3CH
2CH
2)
2-], 0.97[t, 6H, (CH
3CH
2CH
2)
2-].
Its ultimate analysis data are:
Calculated value (%): C, 72.35; H, 5.61; N, 8.73
Observed value (%): C, 72.50; H, 5.66; N, 8.70
Synthesizing of the amino fluorane of embodiment 3 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-di-n-butyl
(experiment is synthetic to add 3.0g in the there-necked flask of 50ml, 99%, 0.008mol) 2-carboxyl-4 '-di-n-butyl amino-2 '-dihydroxy benaophenonel and the 24ml vitriol oil (CP98%, 0.45mol), Deng dissolving fully below the postcooling to 5 ℃, add in batches 1.68g (experiment is synthetic, 97%, 0.009mol) 2-methyl-5-Dui Jia oxygen base Ben oxadiazole, begin to heat up.Pour in about 200ml trash ice after 28 hours in reaction under 75～80 ℃ of temperature, stir, filter, filter cake is washed till neutrality with 5% sodium hydrogen carbonate solution.Filter cake is poured in the 500ml four-hole bottle, added sodium hydroxide solution and the reaction of 200ml toluene of 50ml 5%, be warming up to 60～70 ℃, react after 20 hours.Separatory is got toluene layer, uses activated carbon decolorizing.Obtain the amino fluorane of 1.28g yellow solid compound 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-di-n-butyl after boiling off toluene, purity reaches more than 98%, and yield is 31.3%.Wash with methyl alcohol, obtain white solid, fusing point is 115～118 ℃, adds acid and can get red.
Its ir data is: 2958.02cm
-1Be methyl C-H stretching vibration, 1254.34cm
-1For the C-N stretching vibration causes, 1615.61cm
-1Be the absorption peak of phenyl ring, 1767.07cm
-1Be two keys of C=N and heterocycle.
Its
1H-NMR spectrum data are:
1HNMR (CDCl
3, ppm), the H proton adds up to 31.δ 8.08～δ 6.56 (m, 10H, the H on the phenyl ring), δ 3.28 (q, 4H, (CH
3CH
2CH
2CH
2)
2-), δ 2.47 (s, 3H, CH
3-), δ 1.57[m, 4H, (CH
3CH
2CH
2CH
2)
2-], δ 1.34[m, 4H, (CH
3CH
2CH
2CH
2)
2-], δ 0.96[t, 6H, (CH
3CH
2CH
2CH
2)
2-].
Its ultimate analysis data are:
Calculated value (%): C, 73.08; H, 6.09; N, 8.25
Observed value (%): C, 73.10; H, 6.06; N, 8.31.
Synthesizing of embodiment 4 2-(5-phenyl-1,3,4-oxadiazole-2-yl)-6-diethylamino fluorane
(experiment is synthetic to add 2.5g in the there-necked flask of 50ml, 99%, 0.008mol) 2-carboxyl-4 '-diethylamino-2 '-dihydroxy benaophenonel and the 24ml vitriol oil (CP98%, 0.45mol), Deng dissolving fully below the postcooling to 5 ℃, add in batches 2.22g (experiment is synthetic, 97%, 0.009mol) 2-phenyl-5-Dui Jia oxygen base Ben oxadiazole, begin to heat up.Pour in about 200ml trash ice after 26 hours in reaction under 60～75 ℃ of temperature, stir, filter, filter cake is washed till neutrality with 5% sodium hydrogen carbonate solution.Filter cake is poured in the 500ml four-hole bottle, added sodium hydroxide solution and the reaction of 200ml toluene of 50ml 5%, be warming up to 60～70 ℃, react after 15 hours.Separatory is got toluene layer, uses activated carbon decolorizing.Obtain 1.52g yellow solid compound 2-(5-phenyl-1,3,4-oxadiazole-2-yl)-6-diethylamino fluorane after boiling off toluene, purity reaches more than 98%, and yield is 36.8%.Wash with methyl alcohol, obtain white solid, fusing point is 113～116 ℃, adds acid and can get red.
Its ir data is: 2963.79cm
-1Be methyl C-H stretching vibration, 1261.38cm
-1For the C-N stretching vibration causes, 1618.38cm
-1Be the absorption peak of phenyl ring, 1759.40cm
-1Be two keys of C=N and heterocycle.
Its
1H-NMR spectrum data are:
1HNMR (CDCl
3, ppm), the H proton adds up to 25.δ 8.08～δ 6.48 (m, 15H, the H on the phenyl ring), 3.40 (q, 4H, (CH
3CH
2)
2-), 1.20 (t, 6H, (CH
3CH
2)
2-).
Its ultimate analysis data are:
Calculated value (%): C, 74.56; H, 4.85; N, 8.16
Observed value (%): C, 71.50; H, 4.77; N, 8.11.
Synthesizing of the amino fluorane of embodiment 5 2-(5-phenyl-1,3,4-oxadiazole-2-yl)-6-di
(experiment is synthetic to add 2.7g in the there-necked flask of 50ml, 99%, 0.008mol) 2-carboxyl-4 '-di amino-2 '-dihydroxy benaophenonel and the 24ml vitriol oil (CP98%, 0.45mol), Deng dissolving fully below the postcooling to 5 ℃, add in batches 2.22g (experiment is synthetic, 97%, 0.009mol) 2-phenyl-5-Dui Jia oxygen base Ben oxadiazole, begin to heat up.Pour in about 200ml trash ice after 30 hours in reaction under 60～70 ℃ of temperature, stir, filter, filter cake is washed till neutrality with 5% sodium hydrogen carbonate solution.Filter cake is poured in the 500ml four-hole bottle, added sodium hydroxide solution and the reaction of 200ml toluene of 50ml 5%, be warming up to 65～70 ℃, react after 10 hours.Separatory is got toluene layer, uses activated carbon decolorizing.Obtain the amino fluorane of 1.69g yellow solid compound 2-(5-phenyl-1,3,4-oxadiazole-2-yl)-6-di after boiling off toluene, purity reaches more than 98%, and yield is 38.8%.Wash with methyl alcohol, obtain white solid, fusing point is 148～152 ℃, adds acid and can get red.
Its ir data is: 2958.03cm
-1Be methyl C-H stretching vibration, 1281.96cm
-1For the C-N stretching vibration causes, 1617.45cm
-1Be the absorption peak of phenyl ring, 1764.40cm
-1Be two keys of C=N and heterocycle.
Its
1H-NMR spectrum data are:
1HNMR (CDCl
3, ppm), the H proton adds up to 29.δ 8.17～δ 6.37 (m, 15H, the H on the phenyl ring), 3.28 (q, 4H, (CH
3CH
2CH
2)
2-), 1.36[m, 4H, (CH
3CH
2CH
2)
2-], 0.96[t, 6H, (CH
3CH
2CH
2)
2-].
Its ultimate analysis data are:
Calculated value (%): C, 75.14; H, 5.34; N, 7.73
Observed value (%): C, 75.20; H, 5.36; N, 7.70.
Synthesizing of the amino fluorane of embodiment 6 2-(5-phenyl-1,3,4-oxadiazole-2-yl)-6-di-n-butyl
(experiment is synthetic to add 3.0g in the there-necked flask of 50ml, 99%, 0.008mol) 2-carboxyl-4 '-di-n-butyl amino-2 '-dihydroxy benaophenonel and the 24ml vitriol oil (CP98%, 0.45mol), Deng dissolving fully below the postcooling to 5 ℃, add in batches 2.22g (experiment is synthetic, 97%, 0.009mol) 2-phenyl-5-Dui Jia oxygen base Ben oxadiazole, begin to heat up.Pour in about 200ml trash ice after 28 hours in reaction under 60～70 ℃ of temperature, stir, filter, filter cake is washed till neutrality with 5% sodium hydrogen carbonate solution.Filter cake is poured in the 500ml four-hole bottle, added sodium hydroxide solution and the reaction of 200ml toluene of 50ml 5%, be warming up to 60～70 ℃, react after 8 hours.Separatory is got toluene layer, uses activated carbon decolorizing.Obtain the synthetic of the amino fluorane of 1.28g yellow solid compound 2-(5-phenyl-1,3,4-oxadiazole-2-yl)-6-di-n-butyl after boiling off toluene, purity reaches more than 98%, and yield is 31.3%.Wash with methyl alcohol, obtain white solid, fusing point is 169～172 ℃, adds acid and can get red.
Its ir data is: 2972.24cm
-1Be methyl C-H stretching vibration, 1266.20cm
-1For the C-N stretching vibration causes, 1617.04cm
-1Be the absorption peak of phenyl ring, 1752.98cm
-1Be two keys of C=N and heterocycle.
Its
1H-NMR spectrum data are:
1HNMR (CDCl
3, ppm), the H proton adds up to 33.δ 8.17～δ 6.39 (m, 15H, the H on the phenyl ring), 3.28 (q, 4H, (CH
3CH
2CH
2CH
2)
2-), 1.56[m, 4H, (CH
3CH
2CH
2CH
2)
2-], 1.35[m, 4H, (CH
3CH
2CH
2CH
2)
2-], 0.96[t, 6H, (CH
3CH
2CH
2CH
2)
2-].
Its ultimate analysis data are:
Calculated value (%): C, 75.66; H, 5.78; N, 7.36
Observed value (%): C, 75.60; H, 5.86; N, 7.31.
Synthesizing of embodiment 7 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-diethylamino fluorane
(experiment is synthetic to add 2.5g in the there-necked flask of 50ml, 99%, 0.008mol) 2-carboxyl-4 '-diethylamino-2 '-dihydroxy benaophenonel and 36ml trifluoromethanesulfonic acid (CP99.5%, 0.4mol), Deng dissolving fully below the postcooling to 5 ℃, add in batches 1.68g (experiment is synthetic, 97%, 0.009mol) 2-methyl-5-Dui Jia oxygen base Ben oxadiazole, begin to heat up.Pour in about 200ml trash ice after 24 hours in reaction under 60～70 ℃ of temperature, stir, filter, filter cake is washed till neutrality with 5% sodium hydrogen carbonate solution.Filter cake is poured in the 500ml four-hole bottle, added sodium hydroxide solution and the reaction of 200ml toluene of 50ml5%, be warming up to 60～70 ℃, react after 6 hours.Separatory is got toluene layer, uses activated carbon decolorizing.Obtain 0.96g yellow solid compound 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-diethylamino fluorane after boiling off toluene, purity reaches more than 98%, and yield is 26.5%.Wash with methyl alcohol, obtain white solid, fusing point is 86～90 ℃, adds acid and can get red.
The preparation and the performance measurement thereof of embodiment 8 organic electroluminescence devices
With 2-(the 5-methyl isophthalic acid that makes by embodiment 1 method, 3,4-oxadiazole-2-yl)-the amino fluorane of 6-di prepares organic electroluminescence device, electroluminescent device adopts bilayer structure: ITO/NPB (80nm)/2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-diethylin fluorane/Mg: Ag.Wherein, (5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-diethylin fluorane is a luminescent layer to 2-, and NPB is a hole transmission layer, and the magnesium silver alloys is a negative electrode.1 * 10
-4Under the Pa vacuum tightness, at first with NPB from quartz container vacuum moulding machine to handling on the clean ito glass, then with 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-diethylin fluorane evaporation is on the NPB layer, at last with the vacuum moulding machine of magnesium silver alloys on 2-(5-methyl isophthalic acid, 3,4-oxadiazole-2-yl)-6-diethylin fluorane film as negative electrode (sedimentation velocity is about 0.4nm/s).Luminosity is measured with luminance meter under the constantly increase condition of voltage that puts on the electroluminescent device.Current density and brightness increase with the increase of voltage, and when 18V, the brightness of device reaches maximum value 252cd/m
2When 15V, the efficient of device reaches maximum value 0.22lm/W.Luminous efficiency (lm/W) is by formula: 3.14159BS/ (VI) calculates, and wherein B is brightness (cd/m
2), S is the area (m of device
2), the voltage (V) of V for device is applied, I are the electric current (A) of voltage when being V.
Claims (10)
1. a fluorane kind derivant is characterized in that described derivative suc as formula shown in (I),
Wherein, R1, R2 respectively do for oneself C1～C10 alkyl group, phenyl or substituent phenyl is arranged, described substituting group is alkyl group, nitro, the halogen of C1～C10.
2. fluorane kind derivant as claimed in claim 1 is characterized in that described R1 is one of following: ethyl, n-propyl, normal-butyl.
3. fluorane kind derivant as claimed in claim 1 is characterized in that described R2 is one of following: methyl, phenyl.
4, a kind of synthetic method of fluorane kind derivant as claimed in claim 1, it is characterized in that described method is: De oxadiazole derivative shown in 2-carboxyl-4 '-dialkyl amido-2 '-dihydroxy benaophenonel shown in the formula (II) and the formula (III) is in the presence of bronsted acid catalyst, 50～80 ℃ of reactions 24～30 hours; With reaction product through secondary treatment, again must be after separating treatment suc as formula the fluorane kind derivant shown in (I), described secondary treatment is: with the reaction product cooled and filtered, reacted 5～25 hours at 50～90 ℃ with alkali lye and toluene after the filter cake washing, separatory is got toluene layer.
5, the synthetic method of fluorane kind derivant as claimed in claim 4, it is characterized in that the described amount of substance ratio that feeds intake is 2-carboxyl-4 '-dialkyl amido-2 '-dihydroxy benaophenonel ∶ oxadiazole derivative: bronsted acid catalyst is 8: 7～10: 400～480.
6, the synthetic method of fluorane kind derivant as claimed in claim 4, it is characterized in that described secondary treatment is: reaction product is poured in the trash ice, be stirred to cold, filter, reacted 5～12 hours at 60～80 ℃ with alkali lye and toluene after the filter cake washing, separatory is got toluene layer, must be after the separating treatment suc as formula the fluorane kind derivant shown in (I), described alkali lye is sodium hydroxide, potassium hydroxide, ammoniacal liquor, magnesium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, aliphatic amide, arylamine, substituted aromatic amines.
7, the synthetic method of fluorane kind derivant as claimed in claim 6, the amount of alkali lye that the filter cake after the described washing adds and toluene that it is characterized in that adds alkali lye and the 80～120ml toluene of 20～30ml 5% by every 1g filter cake.
8, the synthetic method of fluorane kind derivant as claimed in claim 4 is characterized in that described bronsted acid catalyst is one of following: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, organic aliphatic acid, organic aromatic acid, organic sulfonic acid.
9. the synthetic method of fluorane kind derivant as claimed in claim 4 is characterized in that described separating treatment promptly gets yellow solid for toluene layer is boiled off toluene, and yellow solid is washed with methyl alcohol, obtains white described fluorane kind derivant.
10. the application of fluorane kind derivant as claimed in claim 1 in electroluminescent organic material, organic third order non-linear optical material, pressure, heat sensitive dye material of fluoran fuctional pigments synthesize.
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| CN112250691A (en) * | 2020-11-18 | 2021-01-22 | 沈阳感光化工研究院有限公司 | Fluorane derivative probe for detecting hydrogen sulfide and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4680598A (en) * | 1985-04-18 | 1987-07-14 | Shin Nisso Kako Co., Ltd. | Chromogenic materials employing fluoran compounds |
| CA1280433C (en) * | 1985-10-08 | 1991-02-19 | Teijiro Kitao | Fluoran derivatives, process for preparation thereof and recording material containing the same |
| JP2854022B2 (en) * | 1989-07-25 | 1999-02-03 | 三井化学株式会社 | Fluoran compounds and recording materials containing said compounds |
| JPH04224990A (en) * | 1990-12-27 | 1992-08-14 | Fuji Photo Film Co Ltd | Fluoran compound |
| JPH05171051A (en) * | 1991-12-25 | 1993-07-09 | Yamamoto Chem Inc | Fluoran compound and recording material prepared using the same |
| AU679394B2 (en) * | 1994-10-18 | 1997-06-26 | Nippon Soda Co., Ltd. | Novel fluoran compound, intermediate, and chromogenic recording material |
| JPH09301979A (en) * | 1996-05-13 | 1997-11-25 | Yamamoto Chem Inc | Fluoran compound and color developing recording material by using the same |
-
2006
- 2006-05-10 CN CNB2006100506714A patent/CN100360537C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101689017B (en) * | 2007-04-27 | 2013-08-28 | 惠普开发有限公司 | Color forming compositions with fluoran leuco dye having latent developer |
| CN102408117A (en) * | 2010-09-21 | 2012-04-11 | 中国科学院福建物质结构研究所 | Cu3(CN)3NH3 crystal-based novel strong fluorescent material and preparation method thereof |
| CN102408117B (en) * | 2010-09-21 | 2015-03-04 | 中国科学院福建物质结构研究所 | Cu3(CN)3NH3 crystal-based strong fluorescent material and preparation method thereof |
| CN107098891A (en) * | 2017-06-02 | 2017-08-29 | 太原理工大学 | A kind of fluorescence falsification preventing material based on mechanical force-responsive |
| WO2021008346A1 (en) * | 2019-07-18 | 2021-01-21 | 江南大学 | Method for preparing electrical/temperature dual control bistable color-changing dye and microcapsule |
| US11655373B2 (en) | 2019-07-18 | 2023-05-23 | Jiangnan University | Method of preparing electric and temperature dual-control bi-stable color-changing dyes and microcapsules |
| CN112250691A (en) * | 2020-11-18 | 2021-01-22 | 沈阳感光化工研究院有限公司 | Fluorane derivative probe for detecting hydrogen sulfide and preparation method and application thereof |
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|---|---|
| CN100360537C (en) | 2008-01-09 |
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