CN108251101A - A kind of photochromic compound and preparation method thereof - Google Patents
A kind of photochromic compound and preparation method thereof Download PDFInfo
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- CN108251101A CN108251101A CN201611240791.0A CN201611240791A CN108251101A CN 108251101 A CN108251101 A CN 108251101A CN 201611240791 A CN201611240791 A CN 201611240791A CN 108251101 A CN108251101 A CN 108251101A
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Abstract
The present invention provides a kind of photochromic compounds and preparation method thereof.Photochromic compound stability of the present invention is good, fatigue resistance is high, is swift in response, and high sensitivity；Meanwhile the active higher reactive group of photochromic compound of the present invention, convenient for it is connect with polymer, and then make its material processing performance more excellent, further expanded its application range and performance, additionally it is possible to be further used for preparing photo luminescent devices.Meanwhile the method for the present invention mild condition, yield is high, is easy to largely prepare production.Further, photo luminescent devices provided by the present invention include photoluminescent compounds of the present invention and/or its derivative, thus with good stability, and can realize quick response.
Description
Technical field
The present invention relates to embedded photoluminescent material field, in particular to a kind of photochromic compound and its preparation side
Method.
Background technology
Photochromic material is a kind of novel functional material, in the light action by certain specific wavelength and some strength
Under, it will make its molecular structure that respective change occur, and it thus be caused to change the absorption peak of light, i.e., its color also can phase
It should change, and this transformation is generally reversible.This photochromism can be substantially summarised as：Certain compound is by certain
Under the light action of a little specific wavelengths, a series of compound caused by photochemical reactions occurs, can have significantly with former compound
Two kinds of different colors (i.e. absorption peak).Otherwise product when acting on by the irradiation of the light of another specific wavelength or for heat again
Change back to compound.Invertibity is the vital criterion that photochromic reactions have.Thus light-induced variable
Color characteristic, the mankind are more and more deep to the research of photochromic material, the type of corresponding photochromic compound also by
It is cumulative more.
Just had from 1867 with the relevant report of photochromic material, cause the whole world concern be from photochromic material
Be suggested for the first time can operate with record and storage optical information after.While its unlimited prospect is seen, more and more personnel open
Beginning is engaged in the research of this cause and continuous effort, and achievement in research is also increasingly abundanter, more photochromic compounds
Occur therewith, for example fulgide, spiral shell piperazine, spiral shell are muttered, diarylethene, azo compound are come out one after another.Since science and technology is sent out
It reaches, U.S., day, Fa Deng states become the leader that photochromic material is studied, while Japan takes the lead in being applied in civilian industry
In, also produce huge economic benefit.
In recent years, as science and technology continues to develop, the mankind more concerns have been turned to make by photochromic material to
Produce optical information gene material, light sensation is adjusted and control material, modifier chip material, optical storage information material, optics device
Part material etc..Since photochromic material cost of material is cheap, more businessman's favors are received in production and life；And
And such material belongs to green material, the health and environment to people will not all damage；Further, it can be with
Life for the mankind increases the variation of countless colors, enriches everybody living space.
China researcher also achieves tremendous development in terms of the research of photochromic material, has designed and synthesized a kind of new
Type spiral shell Do piperazine molecules, and through overtesting confirm thermal stability and information storage effect it is all fine, the recyclable write-in of information and
Erasing is the big feature of one, has at home and abroad shown wide market value.
Current photochromic compound has following a few major class：Spiral shell adjoins class compound of muttering, azobenzene derivative, naphthoxy
Analog derivative, the liquor-saturated analog derivative of prisoner's essence, purpurine analog derivative.The heat that the photochromic compounds of function admirable should have
Mechanical stability, good fatigue resistance is quickly reactive, the characteristics such as high sensitivity.
The achievement in research of domestic and international photochromic compounds in recent years is carefully analyzed, disclosure satisfy that the change of more than element
It is few in number to close objects system, how to develop the common recognition that excellent organic photochromic dyestuff is current researcher.Then,
It is the Discoloration mechanism of further deep layer research photochromic compounds.People are not well understood by its colourshifting process, are
Its colourshifting process is best understood from, needs to carry out lot of experiments using increasingly advanced various analysis means, more need
Theoretic creation is carried out, new concept, new model, new theory and new method is proposed, scientifically illustrates organic photochromic
Close colourshifting process, excitation process and the excited state of object.Finally, organic light-induced variable is further studied on the basis of above research
Production process, the production technology of color compound reduce production cost and are allowed to enter application field as early as possible.
In view of this, it is special to propose the present invention.
Invention content
The first object of the present invention is to provide a kind of photochromic compound, the photochromic compound stability
Well, fatigue resistance is high, is swift in response, and high sensitivity；Meanwhile photochromic compound of the present invention is active higher anti-
Group is answered, convenient for remaining is connect with polymer, makes it more excellent in material processing performance, this has also further expanded it
Application range simultaneously optimizes its performance.
The second object of the present invention is to provide a kind of preparation method of photochromic compound, the method for the present invention condition temperature
It is high with, yield, it is easy to largely prepare production.
Third object of the present invention is to provide the application of the photochromic compound, the photochromic chemical combination of the present invention
Object is with good stability, fatigue resistance, and is swift in response, high sensitivity, it is thus possible to be further used for preparing photic
Luminescent device.
Fourth object of the present invention is to provide a kind of photo luminescent devices, and the photo luminescent devices include the present invention
Photoluminescent compounds and/or its derivative, thus it is with good stability, and can realize quick response.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of photochromic compound, the compound structure are as follows：
Wherein, R1- R7It is independently hydrogen, with or without heteroatomic C1- C20Linear chain or branch chain alkane
Base, cycloalkyl, substituted cycloalkyl, aryl or substituted aryl.
Optionally, in photochromic compound of the present invention, R1For hydrogen, with or without heteroatomic C1- C6It is straight
Chain or branched alkyl, with or without heteroatomic C1- C6Linear chain or branch chain alkyl amino, with or without
Heteroatomic C1- C6Linear chain or branch chain alkyl carboxyl, with or without heteroatomic C1- C6Linear chain or branch chain
Alkyl methyl or with or without heteroatomic C1- C6Linear chain or branch chain alkyl ethyl ester.
R2、R3It is independently hydrogen, with or without heteroatomic C1- C12Linear or branched alkyl group, cycloalkanes
Base, substituted cycloalkyl, aryl or substituted aryl；
R4- R7It is independently hydrogen, with or without heteroatomic C1- C6Linear or branched alkyl group, cycloalkanes
Base, substituted cycloalkyl.
Optionally, in photochromic compound of the present invention, R1For hydrogen, C1- C6Linear or branched alkyl group or C1- C6's
Linear or branched alkyl group amino；
R2、R3It is independently hydrogen, with or without heteroatomic C1- C6Linear or branched alkyl group, cycloalkanes
Base, substituted cycloalkyl；
R4- R7It is independently hydrogen, C1- C6Linear or branched alkyl group, cycloalkyl, substituted cycloalkyl.
Meanwhile the present invention also provides the preparation method of the photochromic compound, described method includes following steps：
After compound I and compound II are heated reaction in a solvent, it is cooled to room temperature, then adds under agitation
Second solvent, obtains sediment, by sediment filtration drying to get to product；
Compound I structures are as follows：
Wherein, R8For hydrogen, with or without heteroatomic C1- C6Linear or branched alkyl group；R9- R14It is only respectively
Vertical is hydrogen, with or without heteroatomic C1- C20Linear or branched alkyl group, cycloalkyl, substituted cycloalkyl, aryl
Or substituted aryl；
Compound II structures are as follows：H2NR15R16；
Wherein, R15With or without heteroatomic C1- C20Linear or branched alkyl group, cycloalkyl, substitution cycloalkanes
Base, aryl or substituted aryl；
R16For-NH2,-COOH ,-COOCH3,-COOEt or-H.Optionally, in preparation method of the present invention, R8For hydrogen,
C1- C6Linear or branched alkyl group；R9、R10It is independently hydrogen, with or without heteroatomic C1- C12Straight chain
Or branched alkyl, cycloalkyl, substituted cycloalkyl, aryl or substituted aryl；R11- R14Be independently hydrogen, carry or
Without heteroatomic C1- C6Linear or branched alkyl group, cycloalkyl, substituted cycloalkyl；
R15For with or without heteroatomic C1- C6Linear or branched alkyl group；
R16For-NH2,-COOH ,-COOCH3,-COOEt or-H.
Optionally, in preparation method of the present invention, the solvent is one or more of methanol, ethyl alcohol, propyl alcohol, isopropanol
Mixed solvent.
Optionally, in preparation method of the present invention, the heating reaction is is heated to flowing back and react overnight.
Optionally, in preparation method of the present invention, second solvent is water.
Further, the application the present invention also provides the photochromic compound in photo luminescent devices are prepared.
Likewise, present invention provides a kind of photo luminescent devices, institute of the present invention is included in the photo luminescent devices
State the derivative of photoluminescent compounds and/or the photoluminescent compounds.
Compared with prior art, beneficial effects of the present invention are：
(1) photochromic compound stability of the present invention is good, fatigue resistance is high, is swift in response, and high sensitivity；Together
When, by its Discoloration mechanism of further experimental study, colourshifting process has established good theoretical foundation for its application；Into
One step, the active higher reactive group of photochromic compound of the present invention, convenient for by photochromic compound with polymerizeing
Object connects, and makes its application in material processing performance and molecular device manufacture more excellent；
(2) the method for the present invention mild condition, yield is high, is easy to largely prepare production.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described.
Fig. 1 is a kind of reacting flow chart of compound provided by the invention；
Fig. 2 is a kind of nuclear-magnetism detection figure of compound provided by the invention；
Fig. 3 is a kind of fluoroscopic examination figure of compound provided by the invention；
Fig. 4 is chemical constitution conversion figure in a kind of photoluminescent process of compound provided by the invention；
Fig. 5 is that a kind of structure reversible transition of compound provided by the invention detects spectrogram；
Fig. 6 is a kind of cytotoxicity test figure of compound provided by the invention；
Fig. 7 is a kind of targeted imaging test chart of compound provided by the present invention.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Photochromic compound of the present invention,It is a type rhodamine
The compound of structure, each substituent group is as follows in compound：
Preferably, R1For hydrogen, C1- C6Linear or branched alkyl group or C1- C6Linear or branched alkyl group amino, example
Such as, R1Can be hydrogen, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl group, tertiary butyl, amyl, 1- methyl fourths
Base, 2- methyl butyls, 3- methyl butyls, 1,1- dimethyl propyls, 1,2- dimethyl propyls, 2,2- dimethyl propyls,
1- ethyl propyls, neopentyl, hexyl, first yldeneamino, ethyleneimino, propylidene amino, butylidene amino, pentylidene ammonia
Base, hexylidene amino, methylene carboxyl, ethylidene carboxyl, propylidene carboxyl, methylene carbomethoxy, ethylidene carbomethoxy, Asia third
Base carbomethoxy, butylidene carbomethoxy, methylene ethoxycarbonyl, ethylidene ethoxycarbonyl, propylidene ethoxycarbonyl or butylidene carbomethoxy
Deng；
Preferably, R2、R3It is independently hydrogen, with or without heteroatomic C1- C6Linear chain or branch chain alkane
Base, cycloalkyl, substituted cycloalkyl, for example, R2、R3Independently can be hydrogen, methyl, ethyl, propyl, isopropyl, butyl,
Sec-butyl, isobutyl group, tertiary butyl, amyl, 1- methyl butyls, 2- methyl butyls, 3- methyl butyls, 1,1- dimethyl propylenes
Base, 1,2- dimethyl propyls, 2,2- dimethyl propyls, 1- ethyl propyls, neopentyl, hexyl, methylenecyclopentyl, methyl
Replace cyclopenta or hexyl etc.；
Preferably, R4- R7It is independently hydrogen, C1- C6Linear or branched alkyl group, cycloalkyl, substituted cycloalkyl,
For example, R4- R7Be independently hydrogen methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl group, tertiary butyl, amyl,
1- methyl butyls, 2- methyl butyls, 3- methyl butyls, 1,1- dimethyl propyls, 1,2- dimethyl propyls, 2,2- diformazans
Base propyl, 1- ethyl propyls, neopentyl, hexyl, methylenecyclopentyl, methyl substitution cyclopenta or hexyl etc..
Further, photoluminescent compounds of the present invention can be byWith(i.e. H2NR15R16) (II) pass through cyclization
Reaction is prepared；
Wherein, in raw material I, it is preferred that R8For hydrogen, C1- C6Linear or branched alkyl group, for example, R8Can be hydrogen, first
Base, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl group, tertiary butyl, amyl, 1- methyl butyls, 2- methyl butyls,
3- methyl butyls, 1,1- dimethyl propyls, 1,2- dimethyl propyls, 2,2- dimethyl propyls, 1- ethyl propyls, new penta
Base or hexyl etc.；
Preferably, R9、R10It is independently hydrogen, with or without heteroatomic C1- C6Linear chain or branch chain alkane
Base, cycloalkyl, substituted cycloalkyl, for example, R9、R10Independently can be hydrogen, methyl, ethyl, propyl, isopropyl, butyl,
Sec-butyl, isobutyl group, tertiary butyl, amyl, 1- methyl butyls, 2- methyl butyls, 3- methyl butyls, 1,1- dimethyl propylenes
Base, 1,2- dimethyl propyls, 2,2- dimethyl propyls, 1- ethyl propyls, neopentyl, hexyl, methylenecyclopentyl, methyl
Replace cyclopenta or hexyl etc.；
Preferably, R11- R14It is independently hydrogen, C1- C6Linear or branched alkyl group, cycloalkyl, substituted cycloalkyl,
For example, R11- R14It is independently hydrogen methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl group, tertiary butyl, penta
Base, 1- methyl butyls, 2- methyl butyls, 3- methyl butyls, 1,1- dimethyl propyls, 1,2- dimethyl propyls, 2,2-
Dimethyl propyl, 1- ethyl propyls, neopentyl, hexyl, methylenecyclopentyl, methyl substitution cyclopenta or hexyl etc..
In raw material II, it is preferred that R15Can be methylene, ethylidene, propylidene, isopropylidene, butylidene, Asia Zhong Ding
Base, isobutylidene, sub- tertiary butyl, pentylidene, sub- neopentyl, hexylidene etc.；
R16For-NH2,-COOH ,-COOCH3,-COOEt or-H；Further, photic hair provided by the present invention
Optical compounds can also be further in photo-chemical processes, computer components, high image resolution microfilm, multilayer stock, protection
It is applied in the fields such as glasses, anti-false sign, coating and printing ink industry or photolytic activity biomolecule.
Specifically, can using the photoluminescent compounds as functional material, directly prepare corresponding function element or
Person directly applies；Or the photoluminescent compounds can also further be reacted with other compounds, its derivative is obtained,
Obtained derivative is prepared into corresponding device or directly application again.
Embodiment 1
Respectively with compound(R8=R9=R10=H, R11=R12=R13=R14=
Ethyl, i.e. rhodamine B) it is raw material I and ethylenediamine (i.e. R15For ethylidene, R16For amino) it is raw material II, preparation structure is as follows
Photoluminescent compoundsReaction equation can refer to Fig. 1, and specific preparation flow is such as
Under：
10mmol rhodamine Bs, 20mL ethyl alcohol and 16mL ethylenediamines are added in round-bottomed flask, and back flow reaction is stayed overnight,
Room temperature is subsequently cooled to, then adds water into reaction solution under agitation, obtains white precipitate, filters, obtains white filter cake
As product.
It is 64.17% to be computed products collection efficiency, and product nuclear-magnetism test map is as shown in Figure 2.
Embodiment 2
It is reacted according to raw material compound I, II identical in embodiment 1, prepares the photic hair of product in the same manner as in Example 1
Optical compounds, specific preparation flow are as follows：
5mmol rhodamine Bs, 10mL ethyl alcohol and 8mL ethylenediamines are added in round-bottomed flask, and is refluxed overnight reaction, then
It is cooled to room temperature, then adds water into reaction solution under agitation, obtain white precipitate, filter, obtaining white filter cake is
Product.It is 74.69% to be computed products collection efficiency, and product nuclear-magnetism detection figure is identical with collection of illustrative plates in embodiment 1.
Embodiment 3
It is reacted according to raw material compound I, II identical in embodiment 1, prepares the photic hair of product in the same manner as in Example 1
Optical compounds, specific preparation flow are as follows：
20mmol rhodamine Bs, 40mL ethyl alcohol and 32mL ethylenediamines are added in round-bottomed flask, and is refluxed overnight reaction, so
Postcooling then adds water into reaction solution, obtains white precipitate, filter, obtain white filter cake i.e. under agitation to room temperature
For product.It is 47.77% to be computed products collection efficiency, and product nuclear-magnetism detection figure is identical with collection of illustrative plates in embodiment 1.
Embodiment 4
Respectively with compound(R8=C2H5, R9=R10=CH3, R11=R13
=H, R12=R14=C2H5, i.e. rhodamine 6G) and it is raw material I and butylamine (i.e. R15For sub- normal-butyl, R16For hydrogen) it is raw material II, system
The following photoluminescent compounds of standby structure,It is specific to prepare stream
Journey is as follows：
5mmol rhodamine 6Gs, 10mL ethyl alcohol and 8mL butylamine are added in round-bottomed flask, and back flow reaction is stayed overnight, then
It is cooled to room temperature, then adds water into reaction solution under agitation, obtain white precipitate, filter, obtaining white filter cake is
Product.It is 71.38% to be computed products collection efficiency.
Embodiment 5
Respectively with compound(R8=CH3, R9=R10=H, R11=R12=R13
=R14=H, i.e. Rhodamine 123) it is raw material I and propylamine (i.e. R15For sub- n-propyl, R16For hydrogen) it is raw material II, preparation structure is such as
Under photoluminescent compounds,Specific preparation flow is as follows：
5mmol Rhodamine 123s, 10mL ethyl alcohol and 8mL amine are added in round-bottomed flask, and back flow reaction is stayed overnight, then
It is cooled to room temperature, then adds water into reaction solution under agitation, obtain white precipitate, filter, obtaining white filter cake is
Product.It is 68.10% to be computed products collection efficiency.
Embodiment 6
Respectively with compound(R8=H, R9=R10=H, R11=R12=
R13=R14=H, i.e. rhodamine 110) it is raw material I and tert-butylamine (i.e. R15For sub- tertiary butyl, R16For hydrogen) it is raw material II, prepare knot
Structure is followingPhotoluminescent compounds, specific preparation flow is such as
Under：
5mmol rhodamines 110,10mL ethyl alcohol and 8mL butylamine are added in round-bottomed flask, and back flow reaction is stayed overnight, so
Postcooling then adds water into reaction solution, obtains white precipitate, filter, obtain white filter cake i.e. under agitation to room temperature
For product.It is 64.49% to be computed products collection efficiency.
Experimental example 1
(1) photoluminescence experiment
The product of a concentration of 1 μM of embodiment 1(being denoted as RbN) solution, is used in combination
The laser irradiation different time (0-20s) of 325nm, then using 500nm as excitation wavelength, scanning range 520-680nm is surveyed
Fixed corresponding fluorescent spectrum curve, as a result as shown in Fig. 3 (A).Using laser irradiation time as abscissa, with the fluorescence at 608nm
It is worth and obtains Fig. 3 (B) for ordinate drafting curve.
By the testing result twice of Fig. 2 it is found that when 325nm laser irradiation times are 0s, RbN does not almost have at 608nm
There is fluorescence, with the growth of 325nm laser irradiation times, fluorescence of the RbN at 608nm constantly enhances, and reaches most after about 15s
Greatly.Illustrate that, with the irradiation of 325nm laser, the RbN of no fluorescence has been gradually converted into fluorescence(being denoted as RbNH).Fig. 4 can refer to by the reversible transition process of RbN to RbNH.
Further experiment shows after the RbN solution being irradiated by 325nm places a period of time, can spontaneously by
RbNH structures are changed into RbN, and fluorescence disappears, this reversible process can be repeatedly presented repeatedly, as shown in Figure 5.
This property of RbN can make its prolonged stable storage, because all there are photooxidations point for most of dyestuffs
The shortcomings that solution, and RbN only by 325nm excitation be changed into RbNH structures when, just have further by photooxidation decompose can
Energy.
(2) fluorescence probe is tested
As bioprobe in use, when not having induced with laser, RbN is nearly free from fluorescence, to the light of biological tissue
Toxicity is almost nil, only when there is detection to need, artificially laser controlling its be changed into RbNH and just provide fluorescence signal, it is and general
Rhodamine, also have under visible light fluorescence signal generation, it is inevitable to the light toxic side effect of biological sample.Thus
As it can be seen that there is apparent advantage as bioprobe RbN.
RbN and rhodamine B (Rb) are compared under natural light to the light toxic side effect of cell, specific experiment side by MTT experiment
Method is as follows：The HeLa cells of in vitro culture are with 1.0 × 105The density of cell/mL is inoculated in the culture plate in 96 holes, is then placed
In saturated humidity incubator in, cultivated at 37 DEG C, after cell monolayer is paved with bottom hole, be separately added into final concentration of 5 μM
Probe RbN solution and Rb solution are put into cell incubator for a period of time after (0,2,4,6,8,10min), and masking foil package is placed on
It is cultivated 1 day or so in cell incubator, 96 orifice plates is taken out after cell adherent growth, suck supernatant, added in PBS and gently wash
It washs, then sucks supernatant.Fresh RPMI 1640 culture mediums 180ul is added in per hole, the MTT for adding the 5mg/mL prepared in advance is molten
Liquid 20ul continues to be placed on 37 DEG C, 5%CO2Cell incubator in culture 4h after carefully suck liquid in hole.150 μ are added in per hole
L DMSO, the low-speed oscillation 5-15min on shaking table, Shi formazans fully dissolve.Finally, it is surveyed at enzyme-linked immunosorbent assay instrument 490nm
The light absorption value in each hole is measured, records the testing result per hole, cell survival rate is calculated, with time for exposure horizontal axis, with cell survival rate
It draws a diagram for the longitudinal axis and observes the toxicity of probe.(in every group of control column of Fig. 6, left side column is thin for RbN as shown in Figure 6 for test result
Born of the same parents' survival survival rate, right side column are Rb cell survival rates).
By the results of comparison of Fig. 6 it is found that with the growth of time for exposure, the cell survival rate of Rb groups is significantly lower than RbN groups
Cell.
(3) common location experiment proves that probe RbN has Mitochondrially targeted imaging function
Experimental method：The HeLa cells of in vitro culture are with 1.0 × 105The density of cell/mL is inoculated in the culture plate in 24 holes
In, in the saturated humidity incubator being then placed into, after being cultivated 12 hours at 37 DEG C, add in final concentration of 5 μM of probe RbN
Solution and business lysosome, mitochondria, nuclear staining agent (LysoTracker, MitoTacker, Hochest) hydroponics after,
It is irradiated, and utilized complete under Leica TCS SP5 laser confocal microscopes with the light of 325nm and respective excitation wavelength respectively
Into fluorescence imaging experiments.
As shown in fig. 7, RbN is mainly distributed in mitochondria, calculated by common location, we obtain RbN and are contaminated with mitochondria
The common location coefficients R r of toner MitoTacker is up to 0.9051, illustrates that RbN can target the mitochondria in cell well.
By the above-mentioned experimental result of experimental example 1 it is found that photochromic compound of the present invention has good photochromism
Can, while also there is excellent stability；Meanwhile cytotoxicity is low, can be used as biological fluorescent labeling, while have good
Good specific biological organ targeted imaging performance.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of photochromic compound, which is characterized in that the compound structure is as follows：
Wherein, R1- R7It is independently hydrogen, with or without heteroatomic C1- C20Linear or branched alkyl group, ring
Alkyl, substituted cycloalkyl, aryl or substituted aryl.
2. photochromic compound according to claim 1, which is characterized in that R1For hydrogen, with or without hetero atom
C1- C6Linear or branched alkyl group, with or without heteroatomic C1- C6Linear chain or branch chain alkyl amino, band
Have or without heteroatomic C1- C6Linear chain or branch chain alkyl carboxyl, with or without heteroatomic C1- C6
Linear chain or branch chain alkyl methyl base or with or without heteroatomic C1- C6Linear chain or branch chain alkyl
Ethoxycarbonyl；
R2、R3It is independently hydrogen, with or without heteroatomic C1- C12Linear or branched alkyl group, cycloalkyl, take
Substituted naphthene base, aryl or substituted aryl；
R4- R7It is independently hydrogen, with or without heteroatomic C1- C6Linear or branched alkyl group, cycloalkyl or
Person's substituted cycloalkyl.
3. photochromic compound according to claim 2, which is characterized in that R1For hydrogen, C1- C6Linear chain or branch chain alkane
Base or C1- C6Linear or branched alkyl group amino；
R2、R3It is independently hydrogen, with or without heteroatomic C1- C6Linear or branched alkyl group, cycloalkyl or
Substituted cycloalkyl；
R4- R7It is independently hydrogen, C1- C6Linear or branched alkyl group, cycloalkyl or substituted cycloalkyl.
4. the preparation method of any one of the claim 1-3 photochromic compounds, which is characterized in that the method packet
Include following steps：
After compound I and compound II are heated reaction in a solvent, it is cooled to room temperature, then adds in second under agitation
Solvent obtains sediment, by sediment filtration drying, as product；
Compound I structures are as follows：
Wherein, R8For hydrogen, with or without heteroatomic C1- C6Linear or branched alkyl group；R9- R14Independently
For hydrogen, with or without heteroatomic C1- C20Linear or branched alkyl group, cycloalkyl, substituted cycloalkyl, aryl or
Substituted aryl；
Compound II structures are as follows：H2NR15R16；
Wherein, R15With or without heteroatomic C1- C20Linear or branched alkyl group, cycloalkyl, substituted cycloalkyl, virtue
Base or substituted aryl；
R16For-NH2,-COOH ,-COOCH3,-COOEt or-H.
5. preparation method according to claim 4, which is characterized in that R8For hydrogen, C1- C6Linear or branched alkyl group；R9、
R10It is independently hydrogen, with or without heteroatomic C1- C12Linear or branched alkyl group, cycloalkyl, substitution cycloalkanes
Base, aryl or substituted aryl；R11- R14It is independently hydrogen, with or without heteroatomic C1- C6Straight chain or
Branched alkyl, cycloalkyl, substituted cycloalkyl；
R15For with or without heteroatomic C1- C6Linear or branched alkyl group；
R16For-NH2,-COOH ,-COOCH3,-COOEt or-H.
6. preparation method according to claim 4, which is characterized in that the solvent is methanol, ethyl alcohol, propyl alcohol, isopropanol
One or more of mixed solvent.
7. preparation method according to claim 4, which is characterized in that the heating reaction is is heated to flowing back and react
Night.
8. preparation method according to claim 4, which is characterized in that second solvent is water.
9. application of any one of the claim 1-3 photochromic compounds in photo luminescent devices are prepared.
10. a kind of photo luminescent devices, which is characterized in that any one of claim 1-3 is included in the photo luminescent devices
The derivative of the photoluminescent compounds and/or the photoluminescent compounds.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194037A (en) * | 1995-08-30 | 1998-09-23 | 康宁股份有限公司 | Photochromic spiroxazines, compositions and articles containing them |
| CN1339031A (en) * | 1999-02-17 | 2002-03-06 | 康宁股份有限公司 | Naphthopyrans and phenanthropyrans annelated in C5-C6 with a bicyclic group, and compositions and (CO) polymer matrices containing them |
-
2016
- 2016-12-28 CN CN201611240791.0A patent/CN108251101A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1194037A (en) * | 1995-08-30 | 1998-09-23 | 康宁股份有限公司 | Photochromic spiroxazines, compositions and articles containing them |
| CN1339031A (en) * | 1999-02-17 | 2002-03-06 | 康宁股份有限公司 | Naphthopyrans and phenanthropyrans annelated in C5-C6 with a bicyclic group, and compositions and (CO) polymer matrices containing them |
Non-Patent Citations (2)
| Title |
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| HAICHUANG LAN ET AL.: "The synergic control of photocyclization and fluorescence in a pH-gated photochromic system", 《DYES AND PIGMENTS》 * |
| HUGO MONTENEGRO ET AL.: "The mechanism of the photochromic transformation of spirorhodamines", 《PHOTOCHEM. PHOTOBIOL. SCI.》 * |
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