CN1962660A - Process for preparing photoresponsive azobenaene-perylene - Google Patents
Process for preparing photoresponsive azobenaene-perylene Download PDFInfo
- Publication number
- CN1962660A CN1962660A CN 200610129505 CN200610129505A CN1962660A CN 1962660 A CN1962660 A CN 1962660A CN 200610129505 CN200610129505 CN 200610129505 CN 200610129505 A CN200610129505 A CN 200610129505A CN 1962660 A CN1962660 A CN 1962660A
- Authority
- CN
- China
- Prior art keywords
- perylene
- massfraction
- solution
- acid
- carboxylic acid
- 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
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a preparing method of optical respond azo-benzene-anthrimide compound in the photoelectric energy transmission material preparing technology, which is characterized by the following: preparing symmetrical or asymmmetrical substituted azo-benzene-anthrimide compound; preparing symmetrical azo-benzene-anthrimide compound through reacting carboxylic acid anhydride and amino-azo-benzene; disposing asymmetrical azo-benzene-anthrimide compound through KOH solution; opening the acid anhydride bond on one side to react with dodecylamine; separating to react with amino azo-benzene to obtain the product.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen benzide-perylene diimide compound-materials of optical Response wide range absorption, belong to light, electric energy transition material technology of preparing.
Background technology
Azo-compound is a compounds that contains azo-group-N=N-, and it contains unsaturated π key, can produce π → π in ultraviolet-visible spectrum
*Or n → π
*Transition has strong absorption peak.Nitrogen benzide belongs to aromatic azo compound, under the illumination effect, stereoisomerism takes place change, and utilizes the incident light wavelength can regulate the photochemical equilibrium of nitrogen benzide.Azobenzene polymer becomes one of the research focus in light responsive material field because of it having good application prospects aspect following optical communication and the light guide.Utilize the photic cis-trans isomerization character of azo chromophore in the polymkeric substance, the variation by sterie configuration or moment of dipole can cause the structure of polymkeric substance and performance to change.Therefore, azobenzene polymer has good prospects for application in fields such as optical storage, photoswitch, holographic grating, optical modulation, biosensors.
The perylene diimide compound has special condensed ring structure, good chemically-resistant, fast light chemical stability, high energy gap and electron affinity, great visible light optical extinction coefficient and high fluorescence quantum yield, thereby become one of focus of organic semiconductor material research.The perylene diimide compound especially has application prospects in fields such as solar cell, electroluminescent, biological fluorescent labeling and molecule photoelectric materials in electrooptical device.The conjugated system of perylene diimide compounds, solubleness, absorption spectrum, fluorescence efficiency, microscopic appearance with and unique photoelectric property, all can be subjected to N, N ' position replaces the influence of material.Though only introduce solubleness and the color that aliphatic chain or fragrant chain can Gai Shan perylene diimide compounds at N the position of substitution, less for its photoelectric characteristic influence.Therefore, by chemical modification method, the perylene diimide compound of preparation difference in functionality replacement material not only can improve some defectives of its inherent, and can produce in various degree influence to its inherent photoelectric properties, and therefore expands its range of application.
Summary of the invention
The object of the present invention is to provide a kind of photoresponsive azobenaene-perylene preparation methods.It is extensive that this method has raw material sources, preparation productive rate advantages of higher.It is fast to obtain to have optical Response speed, good solubility and film-forming properties, microtexture in a tubular form, the photoelectric conversion material of bar-shaped and sheet aggregate, be applied to the organic photovoltaic battery field.
The present invention is realized by following technical proposals, a kind of photoresponsive azobenaene-perylene preparation methods, described nitrogen benzide-perylene diimide compounds comprise the nitrogen benzide-perylene diimide compounds of symmetry replacement and the nitrogen benzide-perylene diimide compounds of asymmetric replacement, it is characterized in that comprising following process:
(1) preparation process of the nitrogen benzide-perylene diimide compounds of symmetry replacement:
3,4,9,10-N, the preparation of N nitrogen benzide — perylene diimide: be mixed with quinoline solution according to the aminoazobenzene of 0.01～0.1g/ml and the ratio of 0.008～0.08g/ml De perylene tetracarboxylic acid acid anhydride.In every milliliter of quinoline solution, add 0.01～0.018g zinc acetate catalyst, stir in 190～220 ℃ of following condensing refluxes, react after 6～10 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, if do not observe fluorescence, promptly proved response has reached terminal point.Be cooled to 60 ℃ after reaction finishes, add the absolute ethyl alcohol and stirring washing, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with dehydrated alcohol and massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 3,4,9,10-N, N nitrogen benzide-perylene diimides.
(2) preparation process of the nitrogen benzide-perylene diimide compounds of asymmetric replacement:
(1) 3,4,9,10-perylene tetracarboxylic acid-3, the preparation of 4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium: at 80～90 ℃ of following ， the perylene tetracarboxylic acid acid anhydride being dissolved in massfraction is 5% KOH solution, be mixed with the solution that concentration is 0.01～0.1g/ml, in 3～4h, drip massfraction then and be 10% H
3PO
4Solution is 4.5～5.0 up to the pH of system value.Continue reaction 1 hour, be cooled to room temperature then, suction filtration is used the deionized water repetitive scrubbing, is colourless up to filtrate, and vacuum-drying is 24 hours under the product 0.1MPa, obtains 3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium.
(2) 3,4-acid anhydrides-9, the preparation of 10-N ' dodecyl-perylene diimides: according to 3 of the lauryl amine of 0.01～0.1g/ml and 0.008～0.08g/ml, 4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium ratio is mixed with the aqueous solution, reacts 1 hour.Heat up then 70 ℃ and reacted 1.5～2 hours, after the reaction, add with above-mentioned liquor capacity ratio be that 1.2: 1～1.5: 1 massfraction is 10% HCl solution, 80 ℃ of following acidifyings 1 hour, be cooled to room temperature, filter.It is in the 10%KOH solution that filter cake is dissolved in 50～100ml massfraction 90 ℃ the time, reacts 2 hours, adds 0.1gKCl in every milliliter of KOH solution then, leaves standstill cooling, filters.Filter cake is respectively 8% KCl and 2% K with massfraction
2CO
3Aqueous solution repetitive scrubbing, colourless up to filtrate, filter cake fully is dissolved in 95 ℃ the hot water filtered while hot; The adding massfraction is 10% HCl solution in filtrate, handled 1～1.5 hour down at 90 ℃, and cold filtration, recrystallization in oil of mirbane, vacuum-drying is 24 hours under the 0.1MPa, obtains 3,4-acid anhydrides-9,10-N ' dodecyl-perylene diimides.
(3) 3,4-N dodecyls-9, the preparation of 10-N ' nitrogen benzide-perylene diimides: according to 3 of 0.0085～0.085g/ml, 4-acid anhydrides-9, the ratio of the aminoazobenzene of 10-N ' Shi Er Wan Ji perylene diimide and 0.01～0.1g/ml is mixed with quinoline solution.In every milliliter of quinoline solution, add 0.008～0.015g zinc acetate catalyst, stir in 180～220 ℃ of following condensing refluxes, react after 4～10 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, if do not observe fluorescence, promptly proved response has reached terminal point.Be cooled to 60 ℃ after reaction finishes, add the absolute ethyl alcohol and stirring washing, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with dehydrated alcohol and massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 3,4-N dodecyl-9,10-N ' nitrogen benzide-perylene diimides.
According to above-mentioned method, be raw material with normal hexyl Amine, n-octyl amine, octadecylamine respectively, can make 3,4-N hexane-9,10-N ' nitrogen benzide-perylene diimides, 3,4-N octane-9,10-N ' nitrogen benzide-perylene diimides, 3,4-N octadecyl-9,10-N ' nitrogen benzide-perylene diimides.
The wide range that the present invention obtains symmetry and asymmetric replacement absorbs, the controlled nitrogen benzide-perylene diimide compound-materials of photoinduction.It is characterized in that: the conjugated system of the introducing Shi De perylene diimide compound of azobenzene group, solubleness, microtexture changes, and then influences its photoelectric property.The nitrogen benzide-perylene diimide compounds that make with present method have outstanding advantages such as solvability and good film-forming property, microtexture and photoelectric properties are adjustable.These nitrogen benzide-perylene diimide compounds are at N, solubleness in the N dimethyl formamide is 0.25～0.8mg/ml, under microstate in a tubular form, the charateristic avsorption band red shift 5～8nm of bar-shaped and sheet aggregate perylene diimide, wavelength is to have photoresponse feature fast under the UV-irradiation of 365nm.
Embodiment
Embodiment 1:
3,4,9,10-N, the preparation of N nitrogen benzide-perylene diimides: respectively 0.48g perylene tetracarboxylic acid acid anhydride and 0.6g aminoazobenzene are dissolved in the 20ml quinoline, two kinds of solution are fully mixed, add the 0.36g zinc acetate, stir in 195 ℃ of following condensing refluxes, react after 7 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 20ml absolute ethyl alcohol and stirring after 1 hour, cooling suction filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with 30ml dehydrated alcohol and 20ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 0.64g 3,4,9,10-N, N nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.25mg/ml, and the charateristic avsorption band red shift 7nm of aggregate ， perylene diimide in the form of sheets under microstate is to have photoresponse feature fast under the UV-irradiation of 365nm at wavelength.
Embodiment 2:
3,4,9,10-N, the preparation of N nitrogen benzide-perylene diimides: 1.8g perylene tetracarboxylic acid acid anhydride and 2.25g aminoazobenzene are dissolved in the 25ml quinoline, and two kinds of solution are fully mixed, add the 0.6g zinc acetate, stir in 210 ℃ of following condensing refluxes, react after 10 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 23ml absolute ethyl alcohol and stirring after 1 hour, cooling suction filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with 40ml dehydrated alcohol and 25ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 2.4g3, and 4,9,10-N, N nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.27mg/ml, and the charateristic avsorption band red shift 8nm of aggregate ， perylene diimide in the form of sheets under microstate is to have photoresponse feature fast under the UV-irradiation of 365nm at wavelength.
Embodiment 3:
3,4,9,10-N, the preparation of N nitrogen benzide-perylene diimides: 1.92g perylene tetracarboxylic acid acid anhydride and 2.4g aminoazobenzene are dissolved in the 15ml quinoline, and two kinds of solution are fully mixed, add the 0.34g zinc acetate, stir in 220 ℃ of following condensing refluxes, react after 8 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 30ml absolute ethyl alcohol and stirring after 1 hour, cold filtration, filter cake 35ml are that 5% KOH solution washing is colourless to filtrate with dehydrated alcohol and 20ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 2.56g3, and 4,9,10-N, N nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.28mg/ml, and the charateristic avsorption band red shift 7nm of aggregate ， perylene diimide in the form of sheets under microstate is to have photoresponse feature fast under the UV-irradiation of 365nm at wavelength.
Embodiment 4:
(1) 3,4,9,10-perylene tetracarboxylic acid-3, the preparation of 4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium: 0.8g perylene tetracarboxylic acid acid anhydride in 85～90 ℃ of KOH solution that fully are dissolved in 40ml massfraction 5%, is dripped the 30ml massfraction and be 10% H then in 3～4h
3PO
4Solution is 4.7 up to the pH of system value.Continue reaction 1 hour, be cooled to room temperature then, suction filtration is used the deionized water repetitive scrubbing, is colourless up to filtrate, and product obtains 0.75g3 70 ℃ of vacuum-dryings 24 hours under 0.1MPa, and 4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium.
(2) 3,4-acid anhydrides-9, the preparation of 10-N ' dodecyl-perylene diimides: with 0.9g lauryl amine and 0.72g 3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium is scattered in respectively in the 25ml aqueous solution, and two kinds of solution thorough mixing reacted 1 hour, heat up then 70 ℃ and reacted 2 hours, after the reaction, add the HCl solution of 60ml10%, 80 ℃ of following acidifyings 1 hour, be cooled to room temperature, suction filtration.It is 10% KOH solution that filter cake is added the 80ml massfraction, handles 2 hours at 90 ℃, adds 8gKCl then, leaves standstill cooling, suction filtration.Filter cake is that 8% KCl and 20ml massfraction are 2% K with the 20ml massfraction
2CO
3The solution repetitive scrubbing, colourless up to filtrate, filter cake fully is dissolved in 100ml95 ℃ the hot water filtered while hot; Be to add in the filtrate in 10% the HCl solution the 100ml massfraction, handled 1.5 hours cold filtration at 90 ℃ down, recrystallization in oil of mirbane, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 0.63g3,4-acid anhydrides-9,10-N ' dodecyl-perylene diimides.
(3) 3,4-N dodecyl-9, the preparation of 10-N ' nitrogen benzide-perylene diimides: with 0.5g 3,4-acid anhydrides-9,10-N ' dodecyl-perylene diimides and 0.6g aminoazobenzene are scattered in respectively in the 20ml quinoline, two kinds of solution thorough mixing add the 0.36g zinc acetate, stir in 185 ℃ of following condensing refluxes.React after 4 hours, with dropper sampling, join massfraction and be in 5% the KOH solution, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 30ml absolute ethyl alcohol and stirring after 1 hour, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with 20ml dehydrated alcohol and 20ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 0.475g 3,4-N dodecyl-9,10-N ' nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.67mg/ml, is the charateristic avsorption band red shift 5nm of bar-shaped aggregate ， perylene diimide under microstate, at wavelength is to have photoresponse feature fast under the UV-irradiation of 365nm.
Embodiment 5:
(1) 3,4,9,10-perylene tetracarboxylic acid-3, the preparation of 4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium: it is in 5% the KOH solution that 2g perylene tetracarboxylic acid acid anhydride fully is dissolved in the 40ml massfraction in 85～90 ℃, Dropwise 35 ml massfraction is 10% H in 3～4h then
3PO
4Solution is 4.6 up to the pH of system value.Continue reaction 1 hour, be cooled to room temperature then, suction filtration is used the deionized water repetitive scrubbing, is colourless up to filtrate, and product vacuum-drying 24 hours under 70 ℃ of 0.1MPa obtains 1.9g 3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium.
(2) 3,4-acid anhydrides-9, the preparation of 10-N ' dodecyl-perylene diimides: with 1.65g lauryl amine and 1.32g3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium is scattered in respectively in the 20ml aqueous solution, and two kinds of solution thorough mixing reacted 1 hour, heat up then 70 ℃ and reacted 2 hours, after the reaction, adding 50ml massfraction was 10% HCl solution, 80 ℃ of following acidifyings 1 hour, be cooled to room temperature, suction filtration.It is that 10% KOH solution was handled 2 hours at 90 ℃ that filter cake is added the 65ml massfraction, adds 6.5gKCl then, leaves standstill cooling, suction filtration.Filter cake is that 8% KCl and 20ml massfraction are 2% K with the 25ml massfraction
2CO
3The solution repetitive scrubbing, colourless up to filtrate, filter cake fully is dissolved in 90ml95 ℃ the hot water filtered while hot; Be to add in the filtrate in 10% the HCl solution the 90ml massfraction, handled 1.5 hours cold filtration at 90 ℃ down, recrystallization in oil of mirbane, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.15g 3,4-acid anhydrides-9,10-N ' dodecyl-perylene diimides.
(3) 3,4-N dodecyls-9, the preparation of 10-N ' nitrogen benzide-perylene diimides: with 1.1g 3,4-acid anhydrides-9,10-N ' dodecyl-perylene diimides and 1.3g aminoazobenzene are scattered in respectively in the 18ml quinoline, and two kinds of solution thorough mixing add the 0.35g zinc acetate, stir in 195 ℃ of following condensing refluxes, react after 5 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 23ml absolute ethyl alcohol and stirring after 1 hour, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with 20ml dehydrated alcohol and 20ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.045g3,4-N dodecyl-9,10-N ' nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.68mg/ml, is the charateristic avsorption band red shift 6nm of bar-shaped aggregate ， perylene diimide under microstate, at wavelength is to have photoresponse feature fast under the UV-irradiation of 365nm.
Embodiment 6:
(1) 3,4,9,10-perylene tetracarboxylic acid-3, the preparation of 4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium: it is in 5% the KOH solution that 2.4g perylene tetracarboxylic acid acid anhydride fully is dissolved in the 30ml massfraction in 85～90 ℃, drips the 28ml massfraction then and be 10% H in 3～4h
3PO
4Solution is 4.5 up to the pH of system value.Continue reaction 1 hour, be cooled to room temperature then, suction filtration is used the deionized water repetitive scrubbing, is colourless up to filtrate, and product vacuum-drying 24 hours under 70 ℃ of 0.1MPa obtains 2.28g 3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium.
(2) 3,4-acid anhydrides-9, the preparation of 10-N ' dodecyl-perylene diimides: with 2.22g lauryl amine and 1.78g3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium is scattered in respectively in the 18ml aqueous solution, and two kinds of solution thorough mixing reacted 1 hour, heat up then 70 ℃ and reacted 2 hours, after the reaction, adding 54ml massfraction was 10% HCl solution, 80 ℃ of following acidifyings 1 hour, be cooled to room temperature, suction filtration.It is that 10% KOH solution was handled 2 hours at 90 ℃ that filter cake is added the 75ml massfraction, adds 7.5gKCl then, leaves standstill cooling, suction filtration.Filter cake is that 8% KCl and 30ml massfraction are 2% K with the 25ml massfraction
2CO
3The solution repetitive scrubbing, colourless up to filtrate, filter cake fully is dissolved in 100ml95 ℃ the hot water filtered while hot; Be to add in the filtrate in 10% the HCl solution the 100ml massfraction, handled 1.5 hours cold filtration at 90 ℃ down, recrystallization in oil of mirbane, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.55g 3,4-acid anhydrides-9,10-N ' dodecyl-perylene diimides.
(3) 3,4-N dodecyls-9, the preparation of 10-N ' nitrogen benzide-perylene diimides: with 1.47g 3,4-acid anhydrides-9,10-N ' dodecyl-perylene diimides and 1.73g aminoazobenzene are scattered in respectively in the 13ml quinoline, and two kinds of solution thorough mixing add the 0.34g zinc acetate, stir in 210 ℃ of following condensing refluxes, react after 7 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 20ml absolute ethyl alcohol and stirring after 1 hour, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with 20ml dehydrated alcohol and 20ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.4g3,4-N dodecyl-9,10-N ' nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.65mg/ml, is the charateristic avsorption band red shift 6nm of pipe, bar-shaped aggregate ， perylene diimide under microstate, at wavelength is to have photoresponse feature fast under the UV-irradiation of 365nm.
Embodiment 7:
(1) 3,4,9,10-perylene tetracarboxylic acid-3, the preparation of 4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium: 1.8g perylene tetracarboxylic acid acid anhydride in 85～90 ℃ of KOH solution that fully are dissolved in 30ml massfraction 5%, is dripped the 25ml massfraction and be 10% H then in 3～4h
3PO
4Solution is 4.6 up to the pH of system value.Continue reaction 1 hour, be cooled to room temperature then, suction filtration is used the deionized water repetitive scrubbing, is colourless up to filtrate, and product vacuum-drying 24 hours under 70 ℃ of 0.1MPa obtains 1.7g3, and 4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium.
(2) 3,4-acid anhydrides-9, the preparation of 10-N ' octadecyl-perylene diimides: with 2.4g octadecylamine and 1.6g3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium is scattered in respectively in the 33ml aqueous solution, and two kinds of solution thorough mixing reacted 1 hour, heat up then 70 ℃ and reacted 2 hours, after the reaction, adding 80ml massfraction was 10% HCl solution, 80 ℃ of following acidifyings 1 hour, be cooled to room temperature, suction filtration.It is that 10% KOH solution was handled 2 hours at 90 ℃ that filter cake is added the 90ml massfraction, adds 9gKCl then, leaves standstill cooling, suction filtration.Filter cake is that 8% KCl and 20ml massfraction are 2% K with the 25ml massfraction
2CO
3The solution repetitive scrubbing, colourless up to filtrate, filter cake fully is dissolved in 100ml95 ℃ the hot water filtered while hot; Be to add in the filtrate in 10% the HCl solution the 100ml massfraction, handled 1.5 hours cold filtration at 90 ℃ down, recrystallization in oil of mirbane, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.47g 3,4-acid anhydrides-9,10-N ' octadecyl-perylene diimides.
(3) 3,4-N octadecyls-9, the preparation of 10-N ' nitrogen benzide-perylene diimides: with 0.98g 3,4-acid anhydrides-9,10-N ' Shi Ba Wan Ji perylene diimide and 1.4g aminoazobenzene are scattered in respectively in the 25ml quinoline, and two kinds of solution thorough mixing add the 0.45g zinc acetate, stir in 200 ℃ of following condensing refluxes, react after 6 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 40ml absolute ethyl alcohol and stirring after 1 hour, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with 25ml dehydrated alcohol and 20ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 0.91g3,4-N octadecyl-9,10-N ' nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.78mg/ml, is the charateristic avsorption band red shift 5nm of pipe, bar-shaped aggregate ， perylene diimide under microstate, at wavelength is to have photoresponse feature fast under the UV-irradiation of 365nm.
Embodiment 8:
(1) 3,4,9,10-perylene tetracarboxylic acid-3, the preparation of 4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium: in 85～90 ℃ of KOH solution that fully are dissolved in 40ml massfraction 5%, Dropwise 35 ml massfraction is 10% H in 3～4h then with 2.4g perylene tetracarboxylic acid acid anhydride
3PO
4Solution is 4.5 up to the pH of system value.Continue reaction 1 hour, be cooled to room temperature then, suction filtration is used the deionized water repetitive scrubbing, and certainly being colourless to filtrate, product vacuum-drying 24 hours under 70 ℃ of 0.1MPa obtains 2.3g 3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium.
(2) 3,4-acid anhydrides-9, the preparation of 10-N ' hexane-perylene diimides: with 2.4g normal hexyl Amine and 1.44g 3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium is scattered in respectively in the 20ml aqueous solution, and two kinds of solution thorough mixing reacted 1 hour, heat up then 70 ℃ and reacted 2 hours, after the reaction, add the HCl solution of 50ml10%, 80 ℃ of following acidifyings 1 hour, be cooled to room temperature, suction filtration.It is 10% KOH solution that filter cake is added the 80ml massfraction, handles 2 hours at 90 ℃, adds 8gKCl then, leaves standstill cooling, suction filtration.Filter cake is that 8% KCl and 20ml massfraction are 2% K with the 20ml massfraction
2CO
3The solution repetitive scrubbing, colourless up to filtrate, filter cake fully is dissolved in 100ml95 ℃ the hot water filtered while hot; Be to add in the filtrate in 10% the HCl solution the 100ml massfraction, handled 1.5 hours cold filtration at 90 ℃ down, recrystallization in oil of mirbane, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.34g 3,4-acid anhydrides-9,10-N ' hexane-perylene diimides.
(3) 3,4-N hexanes-9, the preparation of 10-N ' nitrogen benzide-perylene diimides: with 1.26g 3,4-acid anhydrides-9,10-N ' Ji Wan perylene diimide and 1.8g aminoazobenzene are scattered in respectively in the 20ml quinoline, and two kinds of solution thorough mixing add the 0.45g zinc acetate, stir in 200 ℃ of following condensing refluxes, react after 7 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 30ml absolute ethyl alcohol and stirring after 1 hour, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with 20ml dehydrated alcohol and 20ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.18g3,4-N hexane-9,10-N ' nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.5mg/ml, is charateristic avsorption band red shift 5 nm of bar-shaped aggregate ， perylene diimide under microcosmic volt attitude, at wavelength is to have photoresponse feature fast under the UV-irradiation of 365nm.
Embodiment 9:
(1) 3,4,9,10-perylene tetracarboxylic acid-3, the preparation of 4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium: it is in 5% the KOH solution that 1.9g perylene tetracarboxylic acid acid anhydride fully is dissolved in the 40ml massfraction in 85～90 ℃, Dropwise 35 ml massfraction is 10% H in 3～4h then
3PO
4Solution is 4.6 up to the pH of system value.Continue reaction 1 hour, be cooled to room temperature then, suction filtration is used the deionized water repetitive scrubbing, is colourless up to filtrate, and product vacuum-drying 24 hours under 70 ℃ of 0.1MPa obtains 1.8lg 3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium.
(2) 3,4-acid anhydrides-9, the preparation of 10-N ' octane-perylene diimides: with 1.9g n-octyl amine and 1.52g3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium is scattered in respectively in the 48ml aqueous solution, and two kinds of solution thorough mixing reacted 1 hour, heat up then 70 ℃ and reacted 2 hours, after the reaction, adding 30ml massfraction was 10% HCl solution, 80 ℃ of following acidifyings 1 hour, be cooled to room temperature, suction filtration.It is that 10% KOH solution was handled 2 hours at 90 ℃ that filter cake is added the 65ml massfraction, adds 6.5g KCl then, leaves standstill cooling, suction filtration.Filter cake is that 8% KCl and 20ml massfraction are 2% K with the 25ml massfraction
2CO
3The solution repetitive scrubbing, colourless up to filtrate, filter cake fully is dissolved in 90ml95 ℃ the hot water filtered while hot; Be to add in the filtrate in 10% the HCl solution the 90ml massfraction, handled 1.5 hours down at 90 ℃, cold filtration, recrystallization in oil of mirbane, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.43g3,4-acid anhydrides-9,10-N ' octane-perylene diimides.
(3) 3,4-N octanes-9, the preparation of 10-N ' nitrogen benzide-perylene diimides: with 1.28g3,4-acid anhydrides-9,10-N ' Xin Wan perylene diimide and 1.6g aminoazobenzene are scattered in respectively in the 15ml quinoline, and two kinds of solution thorough mixing add the 0.45g zinc acetate, stir in 210 ℃ of following condensing refluxes, react after 8 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, do not observe fluorescence, reaction reaches terminal point.Be cooled to 60 ℃ after reaction finishes, add the 35ml absolute ethyl alcohol and stirring after 1 hour, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with 20ml dehydrated alcohol and 20ml massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 1.2g 3,4-N octane-9,10-N ' nitrogen benzide-perylene diimides.Product is at N, and the solubleness in the N dimethyl formamide is 0.58mg/ml, is the charateristic avsorption band red shift 6nm of bar-shaped aggregate ， perylene diimide under microstate, at wavelength is to have photoresponse feature fast under the UV-irradiation of 365nm.
Claims (2)
1. photoresponsive azobenaene-perylene preparation methods, described nitrogen benzide-perylene diimide compound comprise nitrogen benzide-perylene diimide compound that symmetry replaces, and it is characterized in that comprising following process:
Be mixed with quinoline solution according to the aminoazobenzene of 0.01～0.1g/ml and the ratio of 0.008～0.08g/ml De perylene tetracarboxylic acid acid anhydride.In every milliliter of quinoline solution, add 0.01～0.018g zinc acetate catalyst, stir in 190～220 ℃ of following condensing refluxes, react after 6～10 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, if do not observe fluorescence, promptly proved response has reached terminal point; Be cooled to 60 ℃ after reaction finishes, add the absolute ethyl alcohol and stirring washing, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with dehydrated alcohol and massfraction, are washed till neutrality with deionized water at last; Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 3,4,9,10-N, N nitrogen benzide-perylene diimides.
2. photoresponsive azobenaene-perylene preparation methods, described nitrogen benzide-perylene diimide compound comprises the nitrogen benzide-perylene diimide compound of asymmetric replacement, it is characterized in that comprising following process:
(1), 3,4,9,10-perylene tetracarboxylic acid-3, the preparation of 4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium: at 80～90 ℃ of following ， the perylene tetracarboxylic acid acid anhydride being dissolved in massfraction is 5% KOH solution, be mixed with the solution that concentration is 0.01～0.1g/ml, in 3～4h, drip massfraction then and be 10% H
3PO
4Solution is 4.5～5.0 up to the pH of system value; Continue reaction 1 hour, be cooled to room temperature then, suction filtration is used the deionized water repetitive scrubbing, is colourless up to filtrate, and vacuum-drying is 24 hours under the product 0.1MPa, obtains 3,4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium;
(2), 3,4-acid anhydrides-9, the preparation of 10-N ' dodecyl-perylene diimides: according to 3 of the lauryl amine of 0.01～0.1g/ml and 0.008～0.08g/ml, 4,9,10-perylene tetracarboxylic acid-3,4-acid anhydrides-9-carboxylic acid-10-carboxylic acid potassium ratio is mixed with the aqueous solution, reacts 1 hour; Heat up then 70 ℃ and reacted 1.5～2 hours, after the reaction, add with above-mentioned liquor capacity ratio be that 1.2: 1～1.5: 1 massfraction is 10% HCl solution, 80 ℃ of following acidifyings 1 hour, be cooled to room temperature, filter; It is in the 10%KOH solution that filter cake is dissolved in 50～100ml massfraction 90 ℃ the time, reacts 2 hours, adds 0.1gKCl in every milliliter of KOH solution then, leaves standstill cooling, filters.Filter cake is respectively 8% KCl and 2% K with massfraction
2CO
3Aqueous solution repetitive scrubbing, colourless up to filtrate, filter cake fully is dissolved in 95 ℃ the hot water filtered while hot; The adding massfraction is 10% HCl solution in filtrate, handled 1～1.5 hour down at 90 ℃, and cold filtration, recrystallization in oil of mirbane, vacuum-drying is 24 hours under the 0.1MPa, obtains 3,4-acid anhydrides-9,10-N ' dodecyl-perylene diimides;
(3), 3,4-N dodecyl-9, the preparation of 10-N ' nitrogen benzide-perylene diimides: according to 3 of 0.0085～0.085g/ml, 4-acid anhydrides-9, the ratio of the aminoazobenzene of 10-N ' Shi Er Wan Ji perylene diimide and 0.01～0.1g/ml is mixed with quinoline solution; In every milliliter of quinoline solution, add 0.008～0.015g zinc acetate catalyst, stir in 180～220 ℃ of following condensing refluxes, react after 4～10 hours,, join massfraction and be in 5% the KOH solution with dropper sampling, if do not observe fluorescence, promptly proved response has reached terminal point; Be cooled to 60 ℃ after reaction finishes, add the absolute ethyl alcohol and stirring washing, cold filtration, filter cake are that 5% KOH solution washing is colourless to filtrate with dehydrated alcohol and massfraction, are washed till neutrality with deionized water at last.Use the chloroform extraction product, vacuum-drying is 24 hours under 70 ℃ of 0.1MPa, obtains 3,4-N dodecyl-9,10-N ' nitrogen benzide-perylene diimides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101295053A CN100445283C (en) | 2006-11-22 | 2006-11-22 | Process for preparing photoresponsive azobenaene-perylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101295053A CN100445283C (en) | 2006-11-22 | 2006-11-22 | Process for preparing photoresponsive azobenaene-perylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962660A true CN1962660A (en) | 2007-05-16 |
| CN100445283C CN100445283C (en) | 2008-12-24 |
Family
ID=38081906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101295053A Expired - Fee Related CN100445283C (en) | 2006-11-22 | 2006-11-22 | Process for preparing photoresponsive azobenaene-perylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100445283C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091654A (en) * | 2010-11-19 | 2011-06-15 | 中国科学院化学研究所 | Organic semiconductor visible light photocatalyst with membrane structure and preparation method and application thereof |
| CN105749978A (en) * | 2016-03-14 | 2016-07-13 | 大连理工大学 | Preparation method and application of perylene bisimide based organometallic polymer with visible-light photocatalytic performance |
| CN109942603A (en) * | 2019-05-06 | 2019-06-28 | 湖南科技大学 | Photoswitch spiro-pyrans-imide compound preparation and its application |
| CN115124555A (en) * | 2022-05-11 | 2022-09-30 | 扬州工业职业技术学院 | Perylene bisimide derivative-based dioxygenase fluorescent material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH365537A (en) * | 1957-12-24 | 1962-11-15 | Sandoz Ag | Use of perylene derivatives for dyeing in bulk |
| DE1257096B (en) * | 1962-08-16 | 1967-12-28 | Basf Ag | Use of two new modifications of perylene-3, 4, 9, 10-tetracarboxylic acid-bis- (4-phenylazo) -phenylimide as pigments |
| GB1056299A (en) * | 1964-05-07 | 1967-01-25 | Basf Ag | Production of dyes of the perylenetetracarboxylic imide series |
| DE3017185A1 (en) * | 1980-05-05 | 1981-11-19 | Hoechst Ag, 6000 Frankfurt | PERYLENE-3,4,9,10-TETRACARBONIC ACID MONOANHYDRIDE MONOIMIDES, METHOD FOR PRODUCING SUCH A COMPOUND AND THEIR USE |
| DE3309060A1 (en) * | 1983-03-14 | 1984-09-20 | Hoechst Ag, 6230 Frankfurt | PERYLENE-3,4,9,10-TETRACARBONIC ACID MONOANHYDRIDE MONOIMID AND MONOIMIDAZOLIDE COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| EP1266222A2 (en) * | 2000-03-14 | 2002-12-18 | Genigma Corporation | Visually detectable dye labelled biomolecules for analysis |
-
2006
- 2006-11-22 CN CNB2006101295053A patent/CN100445283C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091654A (en) * | 2010-11-19 | 2011-06-15 | 中国科学院化学研究所 | Organic semiconductor visible light photocatalyst with membrane structure and preparation method and application thereof |
| CN102091654B (en) * | 2010-11-19 | 2012-08-08 | 中国科学院化学研究所 | Organic semiconductor visible light photocatalyst with membrane structure and preparation method and application thereof |
| CN105749978A (en) * | 2016-03-14 | 2016-07-13 | 大连理工大学 | Preparation method and application of perylene bisimide based organometallic polymer with visible-light photocatalytic performance |
| CN109942603A (en) * | 2019-05-06 | 2019-06-28 | 湖南科技大学 | Photoswitch spiro-pyrans-imide compound preparation and its application |
| CN109942603B (en) * | 2019-05-06 | 2021-08-10 | 湖南科技大学 | Preparation and application of optical switch spiropyran-perylene bisimide compound |
| CN115124555A (en) * | 2022-05-11 | 2022-09-30 | 扬州工业职业技术学院 | Perylene bisimide derivative-based dioxygenase fluorescent material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100445283C (en) | 2008-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2014508132A (en) | Wavelength-converting perylene diester chromophore and luminescent film | |
| CN100445283C (en) | Process for preparing photoresponsive azobenaene-perylene | |
| JP2013084952A (en) | Wavelength conversion film including pressure sensitive adhesive layer for improving photovoltaic collection efficiency | |
| CN110156749B (en) | Asymmetric 9, 10-bithienylanthracene fluorescent compound and preparation method and application thereof | |
| CN113462383B (en) | Room-temperature phosphorescent material based on cellulose and preparation method and application thereof | |
| CN108947766B (en) | Fluorine-containing tetraphenylethylene compound and preparation method and application thereof | |
| CN105669650A (en) | Gelator and preparation method thereof as well as supramolecular metal hydrogel using gelator and preparation method and application of supramolecular metal hydrogel | |
| CN110194952A (en) | A kind of synthetic method of the orange-yellow luminous carbon quantum dot of manganese ion doping | |
| CN111944517B (en) | Conjugated hepta-boron dipyrrole fluorescent dye and synthetic method thereof | |
| CN113571645A (en) | DJ type methylamine-free narrow band gap two-dimensional double-layer hybrid perovskite material and preparation method thereof | |
| JP2013084872A (en) | Wavelength conversion film having pressure sensitive adhesive layer for increasing photovoltaic light collection efficiency | |
| CN116355612A (en) | High-efficiency yellow light-emitting and thermal quenching resistant metal halide perovskite luminescent material, and preparation method and application thereof | |
| Zang et al. | Helix-sense-selective polymerization of substituted acetylenes by using an isolated Rh chiral initiator with an amino acid ligand | |
| Xie et al. | A H-aggregating fluorescent probe for recognizing both mercury and copper ions based on a dicarboxyl-pyridyl bifunctionalized difluoroboron dipyrromethene | |
| CN116375598B (en) | 4,4' -Azo dibenzoate phenanthroline dye eutectic and preparation method thereof | |
| CN108409600B (en) | Preparation method of p- (3-chloro-4-fluorophenylazo) aniline | |
| CN114686212B (en) | Mn-doped two-dimensional organic-inorganic hybrid perovskite BDACdBr 4 Single crystal/powder material, and preparation method and application thereof | |
| CN114605659A (en) | Cd-MOF material with double-spiral structure and preparation method and application thereof | |
| CN114133391A (en) | Mother nucleus substituted naphthalene diimide electrochemical polymerization monomer and preparation method thereof | |
| CN111410624B (en) | Asymmetric naphthalene-pyrrole hybrid diarylethene compound and application thereof | |
| CN115241379A (en) | Silicon phthalocyanine J-aggregated film, preparation method thereof and application thereof in near-infrared photoelectric detector | |
| CN115010763A (en) | Circular polarization phosphorescence platinum (II) complex and preparation method and application thereof | |
| CN102827444A (en) | Two-dimensional resonance energy transfer system of perylene-polyvinylcarbazole and hydrotalcite and construction method thereof | |
| Wang et al. | A Universal Approach for Potassium‐Passivated 2D Perovskites | |
| CN109456344B (en) | (-) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine beta-diketone samarium complex and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081224 Termination date: 20091222 |