CN105254787B - Polyphenylacetylene containing hydrazone and preparation method thereof - Google Patents
Polyphenylacetylene containing hydrazone and preparation method thereof Download PDFInfo
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- CN105254787B CN105254787B CN201510590237.4A CN201510590237A CN105254787B CN 105254787 B CN105254787 B CN 105254787B CN 201510590237 A CN201510590237 A CN 201510590237A CN 105254787 B CN105254787 B CN 105254787B
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- polyphenylacetylene
- containing hydrazone
- hydrazone
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Abstract
The present invention relates to a kind of polyphenylacetylene containing hydrazone and preparation method thereof.The structural formula of such polyphenylacetylene containing hydrazone is：, n=30 ~ 500.Such polymer can regulate and control realize the effectively reversible upset of side chain Z/E configurations by acid/base in organic solvent.It can be widely applied to the intellectual material such as molecular switch field.Significance is respectively provided with basic research and the exploitation of new material, application field.
Description
Technical field
It is particularly a kind of to be realized in acid/base regulation and control the present invention relates to a kind of polyphenylacetylene containing hydrazone and preparation method thereof
Polyphenylacetylene containing hydrazone of the reversible upset of side chain Z/E configurations and preparation method thereof.
Background technology
Polyphenylacetylene and its derivative are because of its excellent electric conductivity, liquid crystal liquid crystal property, photism, helicity, optical nonlinearity etc.
Had a good application prospect in fields such as light, electricity, biology, chiral separation and asymmetry catalysis, receive the extensive pass of people
Note.In polyphenylacetylene main chain, there are four kinds of possible conformations in single double bond alternating：trans-transoid、trans-cisoid、cis- transoidWithcis-cisoid, thus main chain has dynamic.By the dynamic phase of stimulating responsive and polyphenylacetylene main chain
With reference to design prepares intelligent response type polyphenylacetylene and can not only assign the novel feature of material while can also further widen
The application field of material.Polyphenylacetylene of the discoveries such as Yashima with cyclodextrin or crown ether side base can pass through host-guest interaction
（E. Yashima, et al.,Macromolecules, 2003, 36, 6599-6606; E. Yashima, et al.,Macromolecules, 2011, 44, 3217-3226）And pass through acid-base function (E. with carboxyl polyphenylacetylene
Yashima, et al., Nature, 1999,399,449-451) and realize the identification of the chiral molecule of polyphenylacetylene；And band
The helicity for having the polyphenylacetylene of riboflavin side base then has oxidationreduction response（E. Yashima, et al.,Polym. Chem., 2010, 1, 841-848）.Tang Benzhong etc.（B. Z. Tang et al.,Polymer, 2011,
52, 5290-5301）It was found that the polyphenylacetylene with azobenzene lateral group shows photo-isomerisable phenomenon.(the T. such as Kakuchi
Kakuchi, et al., Macromolecules, 2011,44,4249-4257) and find the polyphenylacetylene energy with urea groups
It is enough that anion is responded, and with the display different colours of different sizes of anion size.Honk recklessly etc. (Y. Hu, et al.,J. Polym. Sci., Part A, Polym. Chem.,2013,51,5248-5256) report the polyphenyl with amino
The behavior of acetylene para Toluic Acid response.Zhang Afang etc. (Afang Zhang, et al.,Macromolecules, 2014,
47,3288-3296) report the first spiral polyphenylacetylene with temperature sensitivity.Although substantial amounts of polyphenylacetylene by
Report, but the polyphenylacetylene of new structure how is further designed, the relation between research synthesis, structure and performance three, enter
One step realizes function and the intellectuality of polyphenylacetylene, is still the important topic of carbene research field.
In numerous excitant response primitives, wherein hydrazone compounds are because its synthesis is simple, performance and various structures
The features such as change, is in fields such as organic synthesis, pharmaceutical chemistry, supramolecular chemistry, dynamic covalent chemical, dyestuff and electron transport materials
Possess research application value and receive much concern.Research to hydrazone compounds at present is concentrated mainly on identifying, being golden for zwitterion
Belong to super-molecule assembling body and photoisomerization etc..Applied in ion identification, such as Xiang etc. (Y. Xiang, et al.,Org. Lett, 2006,8,2863-2866) hydrazone molecule and F can be passed through- Deprotonation occurs for ionic interaction, causes
Red shift occurs in ultraviolet spectra, the purpose of monitoring F- ions is reached with this.Li etc. (Q. Li, et al.,J. Photochem. Photobiol., B, 2011,103,140-144) and pass through hydrazone molecule and Cu2+Interaction occur Fluorescence Increasing so as to
Detect Cu2+.In supramolecular chemistry, using double hydrazones or more hydrazone systems and metal ion（Such as Ag+、Pb2+Deng）It is coordinated
Act on and form orderly metal supermolecular assembly, and assembly can be adjusted by both stoichiometric proportions.Together
When, Courtot etc. (P. Courtot, et al.,Bull. Soc. Chim. Fr., 1975,2538-2542) research hair
The E/Z configurations that -2 fragrant hydrazone of tri- carbonyls of 1,2,3- now can be achieved by illumination or heating change.Recently, Aprahamian seminars will
Carbonyl in pyridine groups substitution -2 fragrant hydrazone of 1,2,3- tri- carbonyl with stronger hydrogen bond receptor, design have synthesized a row pH drivings
Hydrazone quasi-molecule switch, and have studied different rotor（Such as hydrogen-based, methyl, cyano group, ethoxycarbonyl (I. Aprahamian, et
al., Beilstein J. Org. Chem. 2012, 8, 872-876))）And different rotor（Such as quinoline (I.
Aprahamian, et al., Angew. Chem. Int. Ed.2011, 50, 1841-1844)）, different kinds of aromatic ring (I.
Aprahamian, et al., J. Am. Chem. Soc.2011,133,9812-9823), different push-and-pull electron groups
(I. Aprahamian, et al., Chem. Commun. 2012,48,10490-10492)) to configuration reversal speed
Influence, research finds that hydrazone quasi-molecule can realize reversible upset, and stationary part pair when having moderate hydrogen bond receptor in rotor
The power of intramolecular hydrogen bond has and necessarily influenceed, and then can have influence on configuration reversal speed.
However, all researchs to hydrazone quasi-molecule, also focus primarily upon small molecule systems at present, the research to polymer hydrazone
Also it is rarely reported, and relative to small molecule devices, polymer-based material has good processing characteristics and system stability.Cause
This, by rational MOLECULE DESIGN, can flexibly reconcile the sensitiveness and polyphenyl second that external boundary stimulates using hydrazone structure of functional groups
Alkynes unique structure and performance characteristics, prepare new polyphenylacetylene containing hydrazone, in basic research and the exploitation of new material, application field
It is respectively provided with significance.
The content of the invention
An object of the present invention is to provide a kind of polyphenylacetylene containing hydrazone.
The second object of the present invention is the preparation method for providing such compound.
This method is that the pyridylacetic acid ester compounds with hydrogen bond receptor and p-aminophenyl acetylene are even by diazotising
Connection reaction prepares the monomer of phenylacetylene containing hydrazone, then obtains polyphenylacetylene containing hydrazone by polymerization, and specific reaction equation is：
。
According to above-mentioned reaction mechanism, the present invention adopts the following technical scheme that：
A kind of polyphenylacetylene containing hydrazone, it is characterised in that the general structure of the polyphenylacetylene containing hydrazone is：
Wherein n=30 ~ 500, m=1 ~ 10, r=0 ~ 3.
A kind of method for preparing above-mentioned a kind of polyphenylacetylene containing hydrazone, it is characterised in that this method concretely comprises the following steps：Will
Pyridylacetic acid ester compounds with hydrogen bond receptor prepare phenylacetylene containing hydrazone with p-aminophenyl acetylene by Diazotization-coupling reaction
Monomer, then homopolymer polyphenylacetylene containing hydrazone obtained from being polymerize；The described esterification of the pyridylacetic acid with hydrogen bond receptor is closed
The structural formula of thing is：
Wherein m=1 ~ 10, r=0 ~ 3.
The preparation method of the above-mentioned polyphenylacetylene containing hydrazone, it is characterised in that the preparation side of the monomer of phenylacetylene containing hydrazone
Method is：
A. by the aqueous solution of p-aminophenyl acetylene and hydrochloric acid 0 ~ 5oStirred 30 ~ 45 minutes under conditions of C, p-aminophenyl
Acetylene and HCl mol ratio are 1：（2~5）；It is slowly added dropwise sodium nitrite in aqueous solution again, p-aminophenyl acetylene and natrium nitrosum
Mol ratio is 1:1, continue the h of reaction 0.5 ~ 1, you can obtain diazonium salt solution；
B. the pyridine with hydrogen bond receptor or imidazoleacetic acid ester compounds are pressed 1 with sodium acetate：（2~10）Mol ratio it is molten
Pressed in second alcohol and water（5~10）：The in the mixed solvent that 1 volume ratio is made into, and 0 ~ 5oStirred 1 hour under C；
C. diazonium salt solution obtained by step a is slowly dropped into step b resulting solutions, diazol closes with pyridylacetic acid esterification
The mol ratio of thing is 1.2:1, it is added dropwise, continues the h of reaction 0.5 ~ 1, frozen water is added into reaction solution, then at ambient temperature
Stirring reaction is stayed overnight；Reaction solution is extracted with DCM, after organic phase is dried with anhydrous magnesium sulfate, is spin-dried for solvent, then through undue
The monomer of phenylacetylene containing hydrazone is obtained from purification.
The preparation method of the above-mentioned polyphenylacetylene containing hydrazone, it is characterised in that monomer polymerization concretely comprises the following steps：In indifferent gas
Under atmosphere protection, the rhodium metal catalyst of the monomer of phenylacetylene containing hydrazone and catalytic amount is dissolved in solvent, adds the second of 0.05 ~ 0.1mL tri-
Amine, 30 ~ 80o2 ~ 24 h are reacted under the conditions of C, solvent is spin-dried for after completion of the reaction, polyphenylacetylene containing hydrazone is obtained through separating-purifying.
The preparation method of the above-mentioned polyphenylacetylene containing hydrazone, it is characterised in that described rhodium metal catalyst is：[Rh(nbd)
Cl]2、[Rh(cod)Cl]2、[Rh(tfb)Cl]2Or Rh (nbd) (BPh4)。
The preparation method of the above-mentioned polyphenylacetylene containing hydrazone, it is characterised in that described solvent be tetrahydrofuran, dioxane,
Toluene, chloroform or methanol.
Resulting materials of the present invention have good acid/base response, and the Z/E configurations of side base can be achieved under acid/base regulation and control
Upset.Such material can be widely applied to the intellectual material such as molecular switch field.Preparation method provided by the invention, reaction condition
Gently, easily implement.
Brief description of the drawings
The nucleus magnetic hydrogen spectrum that Fig. 1 is PPA-Et of the present invention characterizes（Chloroform 23oC, 500MHz）.
The nucleus magnetic hydrogen spectrum that Fig. 2 is PPA-TEG of the present invention characterizes（Chloroform 23oC, 500MHz）.
Fig. 3 is the UV spectrum of PPA-Et, PPA-TEG of the present invention and corresponding monomer PA-Et, PA-TEG in dichloromethane
Figure.It can be seen that similar with monomer, polymer can still realize the reversible upset of side base configuration by acid-base function.
Embodiment
With reference to instantiation, the present invention is further elaborated, but these embodiments be merely to illustrate the present invention without
For limiting the scope of the present invention.In addition, it is to be understood that after the content of the invention illustrated has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Embodiment 1：
The present invention relates to PPA-Et preparation synthesis.
1. the synthesis of monomer
（a）By the aqueous solution of hydrochloric acid（175.33 mg, 4.81 mmol）It is added to p-aminophenyl acetylene（550 mg,
1.85 mmol）In, 45 min are stirred under conditions of ice salt bath, are slow added into（0~5oC）Natrium nitrosum (165.90 mg,
2.4 mmol）The aqueous solution, this dropwise addition process continue for an hour, and obtain diazol A.
（b）By 2- pyridineacetates（550 mg, 1.85 mmol）, sodium acetate（971.1 mg, 11.84 mmol）It is molten
In ethanol/water（6 : 1）In the mixed solvent, after stirring 1 h under ice salt bath, be slowly added to diazol A, this process continues 1
h;20mL frozen water is added, is stirred at room temperature to complete reaction；Reaction solution dichloromethane（DCM）Aqueous phase extracted, anhydrous magnesium sulfate
After organic phase is dried, solvent, n-hexane are spin-dried for：Dichloromethane=2:1 pair of crude product carries out chromatography over CC and obtains PA-
Et, structural formula are：
2. polymer P PA-Et synthesis
By PA-Et（0.28 g, 0.95 mmol）Protected in nitrogen, dry THF be then added dropwise and is dissolved,
Protected again with nitrogen.Catalyst [Rh (nbd) Cl] is added after being completely dissolved2 (7.16mg）With two drop TEA.By whole body
System is protected with nitrogen, is reacted in 30 DEG C of nitrogen, and the reaction time is 24 hours.Reaction is sunk after terminating to crude product
Drop, centrifugation, and be dried with vacuum drier, obtain the mg of polymer P PA-Et 136, the % of yield 48.8.By accompanying drawing 21H
NMR (CDCl3): δ= 1.30 (3H, CH3), 4.12-4.20 (2H, CH2), 7.07-8.33 (6H, CH), 14.54
(1H, NH) understands that proof has obtained target product.
Embodiment 2：
The present invention relates to PPA-TEG preparation synthesis
3. the synthesis of monomer
(a) by pyridine hydrochloride（1.0 g, 5.76 mmol）, triethylamine（0.70 g, 3.94 mmol）It is dissolved in dichloromethane
Alkane, ice salt bath, the lower 1- ethyls of nitrogen protection-（3- dimethylaminopropyls）Carbodiimide hydrochloride（1.484 g, 7.7
mmol）, Triethylene glycol ethyl ether（1.23 g, 6.9 mmol）Added after being dissolved in a small amount of DCM, ice salt bath, stirred under nitrogen atmosphere
8 h are until reaction is complete；Reaction solution dichloromethane（DCM）Aqueous phase extracted, after organic phase is dried anhydrous magnesium sulfate, rotation
Dry solvent, DCM carry out chromatography over CC to crude product and obtain product B.
(b) by 25% hydrochloric acid（458.70 mg, 12.58mmol）Be added drop-wise to p-aminophenyl acetylene (848.8 mg,
Solution is kept in 4.84mmol), during dropwise addition 0oBelow C, stirred at this temperature after being added dropwise 45 minutes.It is first fast again
It is slow afterwards to be added dropwise（0~5oC）NaNO2(434.03 mg, 6.28mmol) solution, process, which is added dropwise, in this needs a hour.
(c) by B（1.2 g, 4.04mmol）, sodium acetate（2.12 g,25.85mmol）It is dissolved in ethanol/water（6 : 1）'s
In the mixed solvent, after stirring 1 h under ice salt bath, diazol A is slowly added to, this process continues 1 h;Add 50mL frozen water, room temperature
Lower stirring is reacted to complete；Reaction solution dichloromethane（DCM）Aqueous phase extracted, after organic phase is dried anhydrous magnesium sulfate,
It is spin-dried for solvent, n-hexane：Ethyl acetate=8:1 pair of crude product carries out chromatography over CC and obtains monomer PA-TEG.Structural formula is：
4. polymer P PA-TEG synthesis
By PA-TEG（0.20 g, 0.47 mmol）Protected in nitrogen, dry THF is then added dropwise its is molten
Solution, is protected with nitrogen again.Catalyst [Rh (nbd) Cl] is added after being completely dissolved2 (3.54mg) and two drop TEA.Will be whole
Individual system is protected with nitrogen, is reacted in 30 DEG C of nitrogen, and the reaction time is 24 hours.Reaction is entered after terminating to crude product
Row sedimentation, centrifugation, and be dried with vacuum drier, polymer P PA-TEG138 mg. are obtained by accompanying drawing 31H NMR
(CDCl3): δ= 0.99 (3H, CH3), 3.40 (10H, CH2), 4.32 (2H, CH2), 7.27-8.48 (10H,
), CH 14.07 (1H, NH) understand that proof has obtained target product.
Claims (6)
1. a kind of polyphenylacetylene containing hydrazone, it is characterised in that the general structure of the polyphenylacetylene containing hydrazone is：
R=CmH2m+1, Chol, MeO (CH2CH2O)rCH2CH2, EtO (CH2CH2O)rCH2CH2
Wherein n=30~500, m=1~10, r=0~3.
A kind of 2. method for preparing a kind of polyphenylacetylene containing hydrazone according to claim 1, it is characterised in that the tool of this method
Body step is：Pyridylacetic acid ester compounds with hydrogen bond receptor are prepared with p-aminophenyl acetylene by Diazotization-coupling reaction
The monomer of phenylacetylene containing hydrazone, then homopolymer polyphenylacetylene containing hydrazone obtained from being polymerize；The described pyridine with hydrogen bond receptor
The structural formula of acetate compound is：
R=CmH2m+1, Chol, MeO (CH2CH2O)rCH2CH2, EtO (CH2CH2O)rCH2CH2
Wherein m=1~10, r=0~3.
3. the preparation method of the polyphenylacetylene according to claim 2 containing hydrazone, it is characterised in that the described list of phenylacetylene containing hydrazone
The preparation method of body is：
A. the aqueous solution of p-aminophenyl acetylene and hydrochloric acid is stirred 30~45 minutes under conditions of 0~5 DEG C, p-aminophenyl acetylene
Mol ratio with HCl is 1：(2~5)；Mole of sodium nitrite in aqueous solution, p-aminophenyl acetylene and natrium nitrosum is slowly added dropwise again
Than for 1:1, continue 0.5~1h of reaction, you can obtain diazonium salt solution；
B. the pyridylacetic acid ester compounds with hydrogen bond receptor and sodium acetate are pressed 1：The mol ratio of (2~10) is dissolved in second alcohol and water
By (5~10)：The in the mixed solvent that 1 volume ratio is made into, and stirred 1 hour at 0~5 DEG C；
C. diazonium salt solution obtained by step a is slowly dropped into step b resulting solutions, diazol and pyridylacetic acid ester compounds
Mol ratio is 1.2:1, it is added dropwise, continues 0.5~1h of reaction, frozen water is added into reaction solution, then stir at ambient temperature
Reaction is overnight；Reaction solution is extracted with DCM, after organic phase is dried with anhydrous magnesium sulfate, is spin-dried for solvent, then carry by separation
It is pure to obtain the monomer of phenylacetylene containing hydrazone.
4. the preparation method of the polyphenylacetylene according to claim 2 containing hydrazone, it is characterised in that the specific steps of monomer polymerization
For：Under inert atmosphere protection, the rhodium metal catalyst of the monomer of phenylacetylene containing hydrazone and catalytic amount is dissolved in solvent, adds 0.05
~0.1mL triethylamines, 2~24h is reacted under the conditions of 30~80 DEG C, solvent is spin-dried for after completion of the reaction, is contained through separating-purifying
Hydrazone polyphenylacetylene.
5. the preparation method of the polyphenylacetylene according to claim 4 containing hydrazone, it is characterised in that described rhodium metal catalyst
For：[Rh(nbd)Cl]2、[Rh(cod)Cl]2、[Rh(tfb)Cl]2Or Rh (nbd) (BPh4)。
6. the preparation method of the polyphenylacetylene according to claim 4 containing hydrazone, it is characterised in that described solvent is tetrahydrochysene furan
Mutter, dioxane, toluene, chloroform or methanol.
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| CN106117425B (en) * | 2016-03-03 | 2018-08-17 | 上海大学 | Alcoxyl ether and aldehyde group modified polyphenylacetylene derivative and preparation method thereof |
| CN106432693B (en) * | 2016-05-14 | 2019-04-02 | 上海大学 | The poly- isocyanide derivative and preparation method thereof of the temperature-induced reversible regulation of helical conformation |
| CN108569998B (en) * | 2018-04-20 | 2021-11-05 | 上海大学 | Multiple stimulus response type aryl hydrazone compound and preparation method thereof |
| CN111825800B (en) * | 2020-06-08 | 2023-02-10 | 上海大学 | Spiral polyphenylacetylene derivative with self-assembly characteristic, assembly and preparation method thereof |
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| CN1644596A (en) * | 2004-08-19 | 2005-07-27 | 上海复旦天臣新技术有限公司 | Poly(p-phenyl acetylene derivative, its preparation and use |
| CN102276768A (en) * | 2011-06-07 | 2011-12-14 | 哈尔滨工程大学 | Preparation method and application method of polyphenylacetylene derivative |
| CN104557601A (en) * | 2015-01-19 | 2015-04-29 | 天水师范学院 | Monomer for identifying halogen anions, polymer and preparation method of monomer and polymer |
| CN104693062A (en) * | 2015-03-13 | 2015-06-10 | 哈尔滨工程大学 | Phenylacetylene derivative with ester group on lateral base band and preparation, polymerization and application methods |
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| CN1644596A (en) * | 2004-08-19 | 2005-07-27 | 上海复旦天臣新技术有限公司 | Poly(p-phenyl acetylene derivative, its preparation and use |
| CN102276768A (en) * | 2011-06-07 | 2011-12-14 | 哈尔滨工程大学 | Preparation method and application method of polyphenylacetylene derivative |
| CN104557601A (en) * | 2015-01-19 | 2015-04-29 | 天水师范学院 | Monomer for identifying halogen anions, polymer and preparation method of monomer and polymer |
| CN104693062A (en) * | 2015-03-13 | 2015-06-10 | 哈尔滨工程大学 | Phenylacetylene derivative with ester group on lateral base band and preparation, polymerization and application methods |
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