CN110003207A - The imide fluorescent dye and preparation method thereof that a kind of gulf position phenoxy group replaces - Google Patents
The imide fluorescent dye and preparation method thereof that a kind of gulf position phenoxy group replaces Download PDFInfo
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- CN110003207A CN110003207A CN201910158886.5A CN201910158886A CN110003207A CN 110003207 A CN110003207 A CN 110003207A CN 201910158886 A CN201910158886 A CN 201910158886A CN 110003207 A CN110003207 A CN 110003207A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- 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
Abstract
The present invention relates to the imide fluorescent dyes and preparation method thereof that a kind of gulf position phenoxy group replaces.The imide fluorescent dye general structure that class gulf position phenoxy group replaces is as follows, by the condensation reaction of n-propylamine and chloro acid anhydrides, improves the imido solubility of reaction intermediate chloro.By phenol and the imido nucleophilic substitution of chloro, the imide compound of phenoxy group substitution is obtained.It hydrolyzes the acid imide of gulf position phenoxy group modification to obtain the acid anhydrides of gulf position phenoxy group modification.The acid anhydrides and trimethylaniline or three hydrophilic chain aniline condensations of gulf position phenoxy group modification, obtain final imide derivatives.Synthetic method of the present invention is simple, easily operated and have preferably solubility property relatively.The imide dye that gulf position phenoxy group containing three hydrophilic chains replaces has aggregation-induced emission behavior, has biggish application prospect in photoelectricity and bio-sensing field.
Description
Technical field
The present invention relates to luminescent dye preparation method technical field, the acyl replaced more particularly to a kind of gulf position phenoxy group
Imines fluorescent dye and preparation method thereof.
Background technique
Light emitting dye molecules are a kind of pi-conjugated molecules with very high fluorescence quantum efficiency, based on its distinctive optics and
Electronic property is imitated in artificial photosystem, fluorescence probe, biosensor, organic semiconductor, organic photovoltaic battery and organic field
Transistor etc. is answered all to be with a wide range of applications.
Acid imide is as a kind of function organic dyestuff, because it is with the property such as excellent light shine, solvent resistant and high temperature resistant
Can, it produces and is widely applied in traditional fields such as plastic processing, pigment colorant and synthetic fibers.Further, since its
Molecule has rigid coplanar structure, molecular modification can be carried out by introducing different groups, so that special knot easily be prepared
The molecule of structure and property.Imide dye molecule can be by with specific direction and reversible nonbonding weak interaction
(effect of π-π overlapping, hydrogen bond, coordinate bond etc.) forms super-molecule assembling body, such as vesica, nano wire, nanotube and spiral knot
Structure.Therefore in science frontiers such as organic photoelectrical material, drug delivery, bioluminescence imaging, fluorescence probe, nir dye exploitations
Field also receives extensive research and application.
Acid imide is the abbreviation of tetracarboxylic acid diimide, since the big π-of its phenyl ring is pi-conjugated and phenyl ring connects outside
P- it is pi-conjugated become flatness greatly, the high organic compound of intramolecular conjugated degree, and have excellent stability
And photoelectric properties.By being chemically modified to acid imide molecule, to regulate and control the self assembly behavior and aggregation of such compound
State property matter is one of the important method for obtaining the acid imide material with novel photoelectric properties.Imido method of modifying
There are two types of general, first is that DE3016765-A was proposed, substituent group is introduced on backbone N-atom, can improve its solubility, but
Due to and have not been changed electronics conjugate action in plane, therefore the modification of amine position its optical property is influenced it is weaker.Second is that
What DE3545004-A was proposed modifies acid imide gulf position, this can not only improve the solubility of molecule, and can pass through
Change electron conjugated state to adjust its optical property.By modifying acid imide, synthesizing new functionality fluorescence
Imide derivatives will further widen its application prospect.
Summary of the invention
It is an object of the invention to: by MOLECULE DESIGN, two are prepared for using nucleophilic addition-elimination reaction of amine and acid anhydrides
Kind imide derivatives.Both derivatives all have preferably solubility property, wherein 1,6,7,12- tetra- (4- benzene oxygen
Base)-N, (3,4,5- tri- (3- { 2- [2- (ethyoxyl) ethyoxyl] the ethyoxyl } -1- propyl)-phenyl -3,4:9,10- of N '-two
Imide dye has aggregation-induced emission phenomenon, provides very promising luminescent material for photoelectricity and bio-sensing field.
Gulf position phenoxy group substituted imides fluorescent dye general structure of the invention is as follows:
Gulf position phenoxy group substituted imides Dyestuff synthesis route of the invention, steps are as follows:
The preparation method for the imide fluorescent dye that gulf position of the invention replaces: in argon gas protection atmosphere, 1,6,7,
(4- the phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride of 12- tetra- and zinc acetate and tri- (3- of 3,4,5- trimethylaniline or 3,4,5-
{ 2- [2- (ethyoxyl) ethyoxyl] ethyoxyl } -1- propyl)-aniline is added in quinoline solution, at 160~180 DEG C, contracts
Close reaction；It then cools to room temperature, 10vol% hydrochloric acid solution is added, solid is precipitated and filters, washing obtained solid to pH value is
Neutrality obtains solid 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two (3,4,5- trimethyl) phenyl -3,4:9,10- after dry
Acid imide or 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two ((3- { 2- [2- (ethyoxyl) ethyoxyl] ethoxy of 3,4,5- tri-
Base } -1- propyl)-phenyl -3,4:9,10- acid imide.
It is preferred that (4- the phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride of 1,6,7,12- tetra- and zinc acetate and 3,4,5- trimethylbenzene
The molar ratio of amine or 3,4,5- tri- (3- { 2- [2- (ethyoxyl) ethyoxyl] ethyoxyl } -1- propyl)-aniline is in 1:(2~3):
(1~3).
The condensation reaction time is preferably 18~for 24 hours.
(4- the phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride of 1,6,7,12- tetra- (II) of the invention the preparation method is as follows:
A) n-propylamine and the chloro- 3,4:9,10- tetracarboxylic acid dianhydride of 1,6,7,12- tetra- are according to molar ratio in (20~30): 1 is added
Into water and isopropyl alcohol mixture, argon gas is protected under atmosphere, and 8~10h is reacted under the conditions of 60~70 DEG C；It is cooled to room temperature
Afterwards, concentrated hydrochloric acid is added dropwise is precipitated product, filters, and washes, dry, N is prepared, N '-dipropyl -1,6,7,12- tetra- is chloro-
3,4:9,10- acid imide；
B) the chloro- 3,4:9,10- acid imide of the N that will be prepared in step a), N '-dipropyl -1,6,7,12- four and benzene
Phenol, potassium carbonate are 1:(5~6 in molar ratio): (5~6) are added in N-Methyl pyrrolidone solution, argon gas protect atmosphere in
It is reacted under 110~120 DEG C of heating conditions；It then cools to room temperature, the hydrochloric acid solution of 8vol% is added to Precipitation, filters,
Washing, it is dry, N, N '-dipropyl -1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- acid imides are prepared；
C) in argon gas protection atmosphere, the N that will be prepared in step b), N '-dipropyl -1,6,7,12- tetra- (4- benzene oxygen
Base) -3,4:9,10- acid imide is added in water and aqueous isopropanol, in the catalysis of potassium hydroxide (0.11~0.15g/ml)
Effect is lower to carry out basic hydrolysis；It reacts, then cools to room temperature under the conditions of 90~110 DEG C, be added 10vol%'s
Hydrochloric acid solution is filtered, is washed, 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetra- are prepared in drying to Precipitation
Carboxylic dianhydride.
It is preferred that water and isopropyl alcohol mixture volume ratio are 1:1 in the step a).
It is preferred that the reaction time is 8~10h in the step b).
It is preferred that the dosage volume ratio of isopropyl alcohol and water is (10~12): 1 in the step c)；The concentration of potassium hydroxide is
0.11~0.15 g/ml；Reaction time is 10~12h.
Reaction synthesis process of the present invention is all relatively simple, easily operated, and can expand to other several similar chemical combination
The synthesis of object.The imide derivatives replaced with different gulf positions and amine position can be synthesized in this way.
The present invention passes through the condensation reaction of n-propylamine and chloro acid anhydrides, and it is imido to improve reaction intermediate chloro
Solubility.By phenol and the imido nucleophilic substitution of chloro, the imide compound of phenoxy group substitution is obtained.
It hydrolyzes the acid imide of gulf position phenoxy group modification to obtain the acid anhydrides of gulf position phenoxy group modification.The acid of gulf position phenoxy group modification
Acid anhydride and trimethylaniline or three hydrophilic chain aniline condensations obtain final new imide compound.
Synthetic method of the present invention is simple, easily operated.The solubility for two kinds of novel imide compounds being prepared
It has a distinct increment relative to four chloro acid anhydrides of raw material tool, reason is: first, the substitution of gulf position 4- phenoxy group increases
The bending degree of plane is to reduce the interaction of pi-pi bond；Second, the three of solubilising are introduced on imido nitrogen-atoms
Methylaniline and three hydrophilic chain aniline.The imide dye that gulf position phenoxy group containing three hydrophilic chains replaces is in visible light
There is UV absorption at 572nm, there is fluorescent emission at 592nm.When water and tetrahydrofuran solvent system are assembled, with aggregation
Growth, fluorescence intensity increase.The property of this aggregation-induced emission will make it in organelle dyeing, pathogen identification, cell
The life such as long period tracer and photodynamic therapy field generates biggish potential using value.
Beneficial effects of the present invention are described as follows:
(1) 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two (3,4,5- trimethyl) phenyl -3,4:9,10- acid imide
Dyestuff and 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two ((3- { 2- [2- (ethyoxyl) ethyoxyl] ethyoxyl }-of 3,4,5- tri-
1- propyl)-phenyl -3,4:9,10- imide dye synthetic method it is simple, it is easily operated and have it is relatively preferably molten
Solve performance.And two novel fluorescence dyestuffs of the application preparation are determined by nuclear-magnetism and mass spectral characteristi.
(2) 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two ((3- { 2- [2- (ethyoxyl) ethyoxyl] ethoxy of 3,4,5- tri-
Base } -1- propyl)-phenyl -3,4:9,10- imide dye is self-assembled into aggregation in water and tetrahydrofuran.By glimmering
The measurement of light spectrum, when water content is enhanced to 99% by 85%, fluorescence intensity increases to original 3 times, and it is poly- to show that it has
Collect Enhancement of Fluorescence (attached drawing 1), this characteristic there will be biggish application prospect in photoelectricity and bio-sensing field.
Detailed description of the invention
Fig. 1, compound V fluorescence intensity change with aggregation extent；
The nuclear magnetic spectrogram of Fig. 2, compound VIII；
The flight time mass spectrum figure of Fig. 3, compound VIII；
The nuclear magnetic spectrogram of Fig. 4, compound III；
The flight time mass spectrum figure of Fig. 5, compound III；
The nuclear magnetic spectrogram of Fig. 6, compound V；
The flight time mass spectrum figure of Fig. 7, compound V.
Specific embodiment
The embodiment of the present invention is illustrated using following steps, but is defined not as condition of the invention, all restrictions with
Subject to claim.
Steps are as follows for the embodiment of the present invention:
(4- the phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride of raw material 1,6,7,12- tetra- (II) the preparation method is as follows:
The preparation of the chloro- 3,4:9,10- acid imide (VII) of N, N '-dipropyl -1,6,7,12- four:
N-propylamine and the chloro- 3,4:9,10- tetracarboxylic acid dianhydride (VI) of 1,6,7,12- tetra- are according to molar ratio in (20~30): 1 plus
Entering to water and isopropanol volume ratio is in 1:1 solution, and argon gas is protected under atmosphere, and 8~10h is reacted under the conditions of 60~70 DEG C；It is cold
But to after room temperature, concentrated hydrochloric acid, which is added dropwise, is precipitated product, filters, and washes, dry, is prepared N, N '-dipropyl -1,6, and 7,
The chloro- 3,4:9,10- acid imide of 12- tetra-.
The preparation of N, N '-dipropyl -1,6,7,12- four (4- phenoxy group) -3,4:9,10- acid imide (VIII):
The chloro- 3,4:9,10- acid imide (VII) of the N that will be prepared in step a, N '-dipropyl -1,6,7,12- four,
Phenol and potassium carbonate are 1:(5~6 in molar ratio): (5~6) are added in N-Methyl pyrrolidone solution, and argon gas protects atmosphere
It is interior, under the catalytic action of potassium carbonate, 8~10h is reacted under 110~120 DEG C of heating conditions.After being cooled to room temperature, it is added
The hydrochloric acid solution of 8vol% is filtered, is washed, N, N '-dipropyl -1,6,7,12- tetra- (4- are prepared in drying to Precipitation
Phenoxy group) -3,4:9,10- acid imide.
The preparation of (4- the phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride of 1,6,7,12- tetra- (II):
Argon gas is protected in atmosphere, the N that will be prepared in step b, N '-dipropyl -1,6,7,12- tetra- (4- phenoxy groups) -
3,4:9,10- acid imide (VIII) are added in water and aqueous isopropanol, in urging for potassium hydroxide (0.11~0.15g/ml)
Change effect is lower to carry out basic hydrolysis.The dosage volume ratio for controlling isopropyl alcohol and water is (10~12): 1, in 90~110 DEG C of items
10~12 h are reacted under part.After being cooled to room temperature, the hydrochloric acid solution of 10vol% is added to Precipitation, suction filtration is washed, and it is dry,
1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride is prepared.
1,6,7,12- tetra- (4- phenoxy group)-N, N '-two (3,4,5- trimethyl) phenyl -3,4:9,10- acid imide
(III) and 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two ((3- { 2- [2- (ethyoxyl) ethyoxyl] ethoxy of 3,4,5- tri-
Base } -1- propyl)-phenyl -3,4:9,10- acid imide (V) preparation:
In argon gas protection atmosphere, 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride (II) and acetic acid
Zinc and 3,4,5- trimethylaniline (I) or 3,4,5- tri- (3- { 2- [2- (ethyoxyl) ethyoxyl] ethyoxyl } -1- propyl)-benzene
Amine (IV) is according to molar ratio in 1:(2~3): (1~3) is added in quinoline solution, and temperature is controlled at 160~180 DEG C, in acetic acid
Under zinc catalytic action, stirring condensation reaction 18~for 24 hours；After being cooled to room temperature, the hydrochloric acid solution of 10vol% is added, solid is precipitated
And filter, washing obtained solid to pH value is neutrality, obtains solid 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two after dry
(3,4,5- trimethyl) phenyl -3,4:9,10- acid imide or 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two (3,4,5- tri-
(3- { 2- [2- (ethyoxyl) ethyoxyl] ethyoxyl } -1- propyl)-phenyl -3,4:9,10- acid imide.
Concrete example is as follows:
Embodiment 1:(compound VII)
N, N '-dipropyl -1,6,7, the 12- tetra- chloro- imido synthesis of 3,4:9,10-: just by (14g, 237mmol)
It is 1:1 that propylamine and the chloro- 3,4:9,10- tetracarboxylic dianhydride of (5 g, 9.43mmol) 1,6,7,12- tetra-, which are added to 250ml volume ratio,
Water and aqueous isopropanol in；In argon atmosphere, reactant is in 65 DEG C of stirring 9h；After being cooled to room temperature, 30mL is added dropwise
Concentrated hydrochloric acid is filtered, is washed, drying obtains orange solids.Product solubility is smaller, without purifying, directly carries out anti-in next step
It answers.
Embodiment 2:(compound VII)
N, N '-dipropyl -1,6,7, the 12- tetra- chloro- imido synthesis of 3,4:9,10-: just by (7g, 117mmol)
Propylamine and the chloro- 3,4:9,10- tetracarboxylic dianhydride of (3.10 g, 5.83mmol) 1,6,7,12- tetra- are added to 120ml volume ratio and are
In the water and aqueous isopropanol of 1:1；In argon atmosphere, reactant is in 60 DEG C of stirring 8h；After being cooled to room temperature, it is added dropwise
15mL concentrated hydrochloric acid is filtered, is washed, drying obtains orange solids.
Embodiment 3:(compound VII)
N, N '-dipropyl -1,6,7, the 12- tetra- chloro- imido synthesis of 3,4:9,10-: by (3.39g, 56.58mmol)
N-propylamine and the chloro- 3,4:9,10- tetracarboxylic dianhydride of (1g, 1.89mmol) 1,6,7,12- tetra- be added to 50ml volume ratio and be
In the water and aqueous isopropanol of 1:1.In argon atmosphere, reactant is in 70 DEG C of stirring 10h.After being cooled to room temperature, it is added dropwise
30mL concentrated hydrochloric acid is filtered, is washed, drying obtains orange solids.
Embodiment 4:(compound VIII)
N, N ' the imido synthesis of-dipropyl -1,6,7,12- four (4- phenoxy group) -3,4:9,10-: will (3.67g,
The chloro- 3,4:9,10- acid imide of N 6mmol), N '-dipropyl -1,6,7,12- four, 4.22g potassium carbonate and (2.82g,
Phenol 30mmol) is added in 80mL N-Methyl pyrrolidone.In argon atmosphere, reactant is in 120 DEG C of stirring 8h.It is cold
But to after room temperature, reactant is poured onto the hydrochloric acid solution of (400ml, 8vol-%), is filtered, washing, drying obtain aubergine
Solid.It prepares column chromatography and obtains product (n-hexane: methylene chloride=1:2).1H-NMR(400MHz,CDCl3,300K,
TMS): δ=8.18 (s, 4H, ArH), 7.26 (d, 8H, ArH), 7.11 (m, 4H, ArH), 6.94 (d, 8H, ArH) .4.05 (t,
4H,-CH2-),1.70(m, 4H,-CH2-),0.95(t,6H,-CH3) (attached drawing 2).MS:C54H38N2O8:842.26；found:
843.25[M+H+] (attached drawing 3).
Embodiment 5:(compound VIII)
N, N ' the imido synthesis of-dipropyl -1,6,7,12- four (4- phenoxy group) -3,4:9,10-: will (18.35g,
The chloro- 3,4:9,10- acid imide of N 30mmol), N '-dipropyl -1,6,7,12- four, 23.22g potassium carbonate and (15.24g,
Phenol 162mmol) is added in 400mL N-Methyl pyrrolidone.In argon atmosphere, reactant is in 110 DEG C of stirring 9h.
After being cooled to room temperature, reactant is poured onto the hydrochloric acid solution of (2L, 8vol-%), filters, washes, drying obtains aubergine
Solid.Purifying and characterization such as embodiment 4.
Embodiment 6:(compound VIII)
N, N '-dipropyl -1,6,7, the 12- tetra- imido synthesis of (4- phenoxy group) -3,4:9,10-: will (6.12g,
The chloro- 3,4:9,10- acid imide of N 10mmol), N '-dipropyl -1,6,7,12- four, 8.293g potassium carbonate and (5.65g,
Phenol 30mmol) is added in 130mL N-Methyl pyrrolidone.In argon atmosphere, reactant is in 120 DEG C of stirring 8h.It is cold
But to after room temperature, reactant is poured onto the hydrochloric acid solution of (650ml, 8vol-%), is filtered, washing, drying obtain aubergine
Solid.Purifying and characterization such as embodiment 4.
Embodiment 7:(compound II)
The synthesis of 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride: by 80g potassium hydroxide and 50mL water
Be added to four (4- phenoxy group) -3,4:9,10- acid imide of (2.95g, 3.5mmol) N, N '-dipropyl -1,6,7,12- and
In the suspension of 500mL isopropanol.In argon atmosphere, 90 DEG C are stirred at reflux 12h.After being cooled to room temperature, reactant is toppled over
Into the hydrochloric acid solution of (1.2L, 10vol-%), filters, washes, drying obtains mulberry solid.Product solubility is smaller, no
It is purified, directly progress next step reaction.
Embodiment 8:(compound II)
The synthesis of 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride: by 23g potassium hydroxide and 15mL water
Be added to four (4- phenoxy group) -3,4:9,10- acid imide of (0.843g, 1mmol) N, N '-dipropyl -1,6,7,12- and
In the suspension of 180mL isopropanol.In argon atmosphere, 110 DEG C are stirred at reflux 10h.After being cooled to room temperature, reactant is toppled over
Into the hydrochloric acid solution of (350ml, 10vol-%), filters, washes, drying obtains mulberry solid.
Embodiment 9:(compound II)
The synthesis of 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride: by 46g potassium hydroxide and 30mL water
Be added to four (4- phenoxy group) -3,4:9,10- acid imide of (1.69g, 2mmol) N, N '-dipropyl -1,6,7,12- and
In the suspension of 330mL isopropanol.In argon atmosphere, 100 DEG C are stirred at reflux 11h.After being cooled to room temperature, reactant is toppled over
Into the hydrochloric acid solution of (1.2L, 10vol-%), filters, washes, drying obtains mulberry solid.
Embodiment 10:(compound III)
The imido conjunction of 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two (3,4,5- trimethyl) phenyl -3,4:9,10-
At: by (1g, 1.316mmol) 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydrides, (469mg,
3.47mmol) 3,4,5- trimethyls-aniline and the zinc acetate of (257.56mg, 1.404mmol) are added in 30mL quinoline.?
In argon atmosphere, reactant is in 165 DEG C of stirring 20h.After being cooled to room temperature, it is mixed that 10vol%HCl (100mL) is added to reaction
It closes in object, filters, dilute hydrochloric acid is washed, washed, is dried and is obtained red solid.It prepares column chromatography and obtains product (methylene chloride: second
Acetoacetic ester: methanol=45:4:2).1H NMR(400MHz,CDCl3) δ=8.22 (s, 4H), 7.25 (dd, 8H), 7.09 (t, 4H),
6.94 (d, 8H), 6.89 (s, 4H), 2.29 (s, 12H), 2.20 (s, 6H) (attached drawing 4).MS:C66H46N2O8:994.33；
found:995.38[M+H+] (attached drawing 5).
Embodiment 11:(compound III)
The imido conjunction of 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two (3,4,5- trimethyl) phenyl -3,4:9,10-
At: by (5g, 6.58mmol) 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydrides, (1.779g,
13.16mmol) 3,4,5- trimethyls-aniline and the zinc acetate of (1.207g, 6.58mmol) are added in 150mL quinoline.?
In argon atmosphere, reactant stirs for 24 hours at 180 DEG C.After being cooled to room temperature, it is mixed that 10vol%HCl (500mL) is added to reaction
It closes in object, filters, dilute hydrochloric acid is washed, washed, is dried and is obtained red solid.Purifying and characterization such as embodiment 10.
Embodiment 12:(compound III)
The imido conjunction of 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two (3,4,5- trimethyl) phenyl -3,4:9,10-
At: by (200 mg, 0.263mmol) 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydrides, (106.5mg,
0.789mmol) 3,4,5- trimethyls-aniline and the zinc acetate of (144.78mg, 0.789mmol) are added in 6mL quinoline.?
In argon atmosphere, reactant is in 160 DEG C of stirring 18h.After being cooled to room temperature, 10vol%HCl (20mL) is added to reaction mixing
It in object, filters, dilute hydrochloric acid is washed, washed, is dried and is obtained red solid.Purifying and characterization such as embodiment 10.
Embodiment 13:(compound V)
1,6,7,12- tetra- (4- phenoxy group)-N, N '-two ((3- { 2- [2- (ethyoxyl) ethyoxyl] ethoxy of 3,4,5- tri-
Base } -1- propyl)-phenyl -3,4:9, the imido synthesis of 10-: by (684mg, 0.9mmol) 1,6,7,12- tetra- (4- benzene oxygen
Base) -3,4:9,10- tetracarboxylic acid dianhydride, (1.464g, 2.376mmol) (3- { 2- [2- (ethyoxyl) ethyoxyl] of 3,4,5- tri-
Ethyoxyl } -1- propyl) zinc acetate of-aniline and (175.2mg, 0.96mmol) is added in 18mL quinoline.In argon atmosphere
Interior, reactant is in 180 DEG C of stirring 18h.After being cooled to room temperature, 10vol%HCl (150mL) is added in reaction mixture,
It filters, dilute hydrochloric acid is washed, washed, is dried and is obtained red solid.Prepare column chromatography obtain product (methylene chloride: ethyl acetate:
Methanol=45:4:2).1H NMR(400MHz,CDCl3, 300K, TMS): δ=8.21 (s, 4H, ArH in perylene
ring),7.25(m,8H,ArH), 7.09(m,4H,ArH),6.95(m,8H,ArH),6.88(s,4H,ArH),3.68-3.46
(m,72H,36x-OCH2-),2.70(m, 12H,6x ArCH2-),1.85(m,8H,4x ArCH2CH2-),1.78(m,4H,2x
ArCH2CH2), 1.20 (t, J=7.00Hz, 6H, 2x CH3), 1.17 (t, J=7.00Hz, 12H, 4x CH3) (attached drawing 6).
MS:C114H142N2O26:1954.99；found: 1977.93[M+Na+] (attached drawing 7).
Embodiment 14:(compound V)
1,6,7,12- tetra- (4- phenoxy group)-N, N '-two ((3- { 2- [2- (ethyoxyl) ethyoxyl] ethoxy of 3,4,5- tri-
Base } -1- propyl)-phenyl -3,4:9, the imido synthesis of 10-: by (7.6mg, 10mmol) 1,6,7,12- tetra- (4- benzene oxygen
Base) -3,4:9,10- tetracarboxylic acid dianhydride, (12.32g, 20mmol) (3- { 2- [2- (ethyoxyl) ethyoxyl] ethoxy of 3,4,5- tri-
Base } -1- propyl) zinc acetate of-aniline and (1.835 mg, 10mmol) is added in 200mL quinoline.In argon atmosphere, instead
Object is answered to stir for 24 hours at 160 DEG C.After being cooled to room temperature, 10vol%HCl (1.5L) is added in reaction mixture, filters, is dilute
Salt pickling, washing, drying obtain red solid.Purifying and characterization such as embodiment 13.
Embodiment 15:(compound V)
1,6,7,12- tetra- (4- phenoxy group)-N, N '-two ((3- { 2- [2- (ethyoxyl) ethyoxyl] ethoxy of 3,4,5- tri-
Base } -1- propyl)-imido the synthesis of phenyl -3,4:9,10-: by (the 4- benzene oxygen of (380mg, 0.5mmol) 1,6,7,12- tetra-
Base) -3,4:9,10- tetracarboxylic acid dianhydride, (0.924g, 1.5mmol) (3- { 2- [2- (ethyoxyl) ethyoxyl] second of 3,4,5- tri-
Oxygroup } -1- propyl) zinc acetate of-aniline and (275 mg, 1.5mmol) is added in 10mL quinoline.In argon atmosphere, instead
Answer object in 175 DEG C of stirring 20h.After being cooled to room temperature, 10vol%HCl (90mL) is added in reaction mixture, filters, is dilute
Salt pickling, washing, drying obtain red solid.Purifying and characterization such as embodiment 13.
Claims (8)
1. the imide fluorescent dye that a kind of gulf position phenoxy group replaces, it is characterised in that the general structure of the imide dye
It is as follows:
2. the preparation method for the imide fluorescent dye that a kind of gulf position phenoxy group of claim 1 replaces, it is characterized in that: in argon
In gas shielded atmosphere, 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydride and zinc acetate and 3,4,5- trimethyls
Aniline or 3,4,5- tri- (3- { 2- [2- (ethyoxyl) ethyoxyl] ethyoxyl } -1- propyl)-aniline are added in quinoline solution,
160~180 DEG C, carry out condensation reaction；It then cools to room temperature, 10vol% hydrochloric acid solution is added, solid is precipitated and filters, water
Washing obtained solid to pH value is neutrality, obtains solid 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two (3,4,5- front threes after dry
Base) phenyl -3,4:9,10- acid imide or 1,6,7,12- tetra- (4- phenoxy group)-N, N '-two ((3- { 2- [2- (second of 3,4,5- tri-
Oxygroup) ethyoxyl] ethyoxyl } -1- propyl)-phenyl -3,4:9,10- acid imide.
3. method according to claim 2, it is characterized in that: 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid two
Acid anhydride and zinc acetate and 3,4,5- trimethylaniline or (3- { 2- [2- (ethyoxyl) ethyoxyl] the ethyoxyl } -1- third of 3,4,5- tri-
Base)-aniline molar ratio in 1:(2~3): (1~3).
4. method according to claim 2, it is characterized in that: the condensation reaction time be 18~for 24 hours.
5. method according to claim 2, it is characterized in that described 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acids
Dianhydride the preparation method is as follows:
A) n-propylamine and the chloro- 3,4:9,10- tetracarboxylic acid dianhydride of 1,6,7,12- tetra- are added to water in (20~30): 1 according to molar ratio
In isopropyl alcohol mixture, argon gas is protected under atmosphere, and 8~10h is reacted under the conditions of 60~70 DEG C；After being cooled to room temperature, by
Being added dropwise to concentrated hydrochloric acid is precipitated product, filters, and washes, dry, is prepared N, N '-dipropyl -1,6, and 7,12- tetra- chloro- 3,4:
9,10- acid imide；
The chloro- 3,4:9,10- acid imide of the b) N that will be prepared in step a), N '-dipropyl -1,6,7,12- four and phenol,
Potassium carbonate is 1:(5~6 in molar ratio): (5~6) are added in N-Methyl pyrrolidone solution, and argon gas is protected in atmosphere 110
It is reacted under~120 DEG C of heating conditions；It then cooling to room temperature, 8vol% hydrochloric acid solution is added to Precipitation, suction filtration is washed,
It is dry, N, N '-dipropyl -1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- acid imides are prepared；
C) in argon gas protection atmosphere, the N that will be prepared in step b), N '-dipropyl -1,6,7,12- tetra- (4- phenoxy groups) -3,
4:9,10- acid imide are added in water and aqueous isopropanol, and basic hydrolysis is carried out under the catalytic action of potassium hydroxide；
It reacts, then cools to room temperature under the conditions of 90~110 DEG C, the hydrochloric acid solution of 10vol% is added to Precipitation, filters, water
It washes, it is dry, 1,6,7,12- tetra- (4- phenoxy group) -3,4:9,10- tetracarboxylic acid dianhydrides are prepared.
6. method as claimed in claim 6, it is characterized in that water and isopropyl alcohol mixture volume ratio are 1 in the step a):
1。
7. method as claimed in claim 6, it is characterized in that the reaction time is 8~10h in the step b).
8. method as claimed in claim 6, it is characterized in that in the step c), the dosage volume ratio of isopropyl alcohol and water is (10
~12): 1；The concentration of potassium hydroxide is 0.11~0.15g/ml；Reaction time is 10~12h.
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| CN112724137A (en) * | 2021-01-19 | 2021-04-30 | 河南大学 | Perylene bisimide derivative and preparation method and application thereof |
| CN114380826A (en) * | 2022-01-21 | 2022-04-22 | 吉林大学 | Perylene porous organic salt material with stable photo-thermal property and preparation method and application thereof |
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| CN111521593A (en) * | 2020-05-12 | 2020-08-11 | 中国农业大学 | Rapid visual detection method based on water-soluble perylene bisimide derivative |
| CN111521593B (en) * | 2020-05-12 | 2021-05-11 | 中国农业大学 | Rapid visual detection method based on water-soluble perylene bisimide derivative |
| CN111875731A (en) * | 2020-07-09 | 2020-11-03 | 上海慧翌新材料科技有限公司 | Porous high-fluorescence polyacrylate microsphere and preparation method thereof |
| CN111875731B (en) * | 2020-07-09 | 2023-01-03 | 上海慧翌新材料科技有限公司 | Porous high-fluorescence polyacrylate microsphere and preparation method thereof |
| CN112724137A (en) * | 2021-01-19 | 2021-04-30 | 河南大学 | Perylene bisimide derivative and preparation method and application thereof |
| CN114380826A (en) * | 2022-01-21 | 2022-04-22 | 吉林大学 | Perylene porous organic salt material with stable photo-thermal property and preparation method and application thereof |
| CN114380826B (en) * | 2022-01-21 | 2024-02-23 | 吉林大学 | Perylene porous organic salt material with stable light and heat properties, and preparation method and application thereof |
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