CN102617779B - 2,3,4,5-tetraphenylsilole-based water-soluble polymer and its preparation method and use - Google Patents
2,3,4,5-tetraphenylsilole-based water-soluble polymer and its preparation method and use Download PDFInfo
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- CN102617779B CN102617779B CN201110030992.9A CN201110030992A CN102617779B CN 102617779 B CN102617779 B CN 102617779B CN 201110030992 A CN201110030992 A CN 201110030992A CN 102617779 B CN102617779 B CN 102617779B
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- 0 *[Si](C=Cc(cc1)ccc1NC(C=C)=O)(C(c1ccccc1)=C1c2ccccc2)C(c2ccccc2)=C1c1ccccc1 Chemical compound *[Si](C=Cc(cc1)ccc1NC(C=C)=O)(C(c1ccccc1)=C1c2ccccc2)C(c2ccccc2)=C1c1ccccc1 0.000 description 1
- POKHUSHIFCOQRO-OCEACIFDSA-N Nc1ccc(/C=C/[Si+](C(c2ccccc2)=C2c3ccccc3)C(c3ccccc3)=C2c2ccccc2)cc1 Chemical compound Nc1ccc(/C=C/[Si+](C(c2ccccc2)=C2c3ccccc3)C(c3ccccc3)=C2c2ccccc2)cc1 POKHUSHIFCOQRO-OCEACIFDSA-N 0.000 description 1
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Abstract
The invention discloses a 2,3,4,5-tetraphenylsilole-based water-soluble polymer and its preparation method and use. The 2,3,4,5-tetraphenylsilole-based water-soluble polymer has a general structural formula shown in the formula I. In invention, 2,3,4,5-tetraphenylsilole comonomers and water-soluble monomers undergo a free-radical copolymerization reaction to be synthesized into a series of water-soluble polymers having side chain structures formed of 2,3,4,5-tetraphenylsilole. The 2,3,4,5-tetraphenylsilole-based water-soluble polymer provided by the invention has good luminescence properties, can be dissolved in water, has good fluorescence quenching or fluorescence enhancement effects on certain specific groups or substances, and can realize chemical/biological detection in an aqueous solution. Therefore, the 2,3,4,5-tetraphenylsilole-based water-soluble polymer is a novel chemical/biological detection material.
Description
Technical field
The present invention relates to a kind of water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene and preparation method thereof and application.
Background technology
Common fluorescent substance just has fluorescence in organic solvent, and fluorescent quenching occurs when state of aggregation.Therefore the organic fluorescent substance for chemical/biological context of detection generally can only carry out at organic solvent, and the solubleness of more detected material in organic solvent is unsatisfactory, and thereby great majority have the material of vital activity can lose activity affect the reliability of detected result, so develop the emphasis that water miscible detection system becomes research in organic solvent.
It is low because thereby the hydrophobicity of chromophore causes them to tend to assemble fluorescence intensity in the aqueous solution to have water miscible organic fluorescence small molecules, therefore has equally many problem demanding prompt solutions, and a little less than luminous intensity, the sensitivity of detection is low etc.Water soluble fluorescence quantum dot and the soluble conjugated polymer of development attracted wide attention in recent years.
Water miscible quantum dot normally inorganic metal compound nano particle gives by finishing that it is water-soluble.But this compounds contains heavy metal, be there is certain pollution and can cause equally the active problem disappearing when having the biomolecule detection of vital activity in environment.And soluble conjugated polymer is amphipathic molecule, the conjugation ring body that main chain is rigidity, side chain is water soluble group.Linear molecule for this class rigid structure, the result of these two kinds effect balances of the hydrophobic interaction of conjugated main chain and flexible side-chains hydrophilic interaction is in the aqueous solution, to form state of aggregation, thereby also cause that fluorescence weakens, detection sensitivity declines, and when for biomolecule detection and biomolecules can not fully interact.
2,3,4,5-tetraphenyl-silicon heterocyclic pentylene is the special organic fluorescence small molecules of a class.They do not have fluorescence and in state of aggregation with when solid-state, just have very strong fluorescence in organic solvent.This is for they detect possibility is provided for the chemical/biological of water solution system.High fluorescent is given the detection sensitivity that this compounds is high.Yet in the aqueous assay system of the small molecules based on this compounds of having carried out so far or polymkeric substance, good dispersiveness is still the problem that needs solution.
Summary of the invention
The object of this invention is to provide a kind of water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene and preparation method thereof and application.
Water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene provided by the invention, is polymkeric substance shown in formula I,
(formula I)
In described formula I general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl, preferable methyl; R
2for hydroxyl, amino or sec.-propyl amido, preferred hydroxyl; R
3for hydrogen atom or methyl; M and n are the integer of 1-200, the integer of the preferred 1-50 of m, and more preferably 1, the integer of the preferred 1-50 of n specifically can be the integer of 48-144,53-144 or 48-53.
The method of the above-mentioned polymkeric substance of preparation provided by the invention under the condition that comprises the steps: to exist at radical initiator, is carried out copolyreaction with water-soluble monomer by compound shown in formula IV in organic solvent, reacts the complete described polymkeric substance that obtains.
In aforesaid method, described organic solvent is selected from least one in toluene, tetrahydrofuran (THF) and methylene dichloride, preferably tetrahydrofuran (THF); Described radical initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; Described water-soluble monomer is vinylformic acid, methacrylic acid, acrylamide or NIPA; The mol ratio of compound and water-soluble monomer shown in described radical initiator, formula IV is 0.1-0.3: 1-1.1: 1-100, specifically can be 0.2-0.3: 1: 80-100, preferably 0.2: 1: 40; In described copolyreaction step, temperature is 20-80 ℃, preferably 70 ℃; Time is 1-24 hour, preferably 24 hours.
Wherein, compound shown in described formula IV (monomer that also contains 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene) also belongs to protection scope of the present invention.
Shown in this formula IV, the general structure of compound is as follows:
(formula IV)
In described formula IV general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl, preferable methyl.
The method of compound shown in the above-mentioned formula IV of preparation provided by the invention, comprise the steps: under the condition of dicyclohexylcarbodiimide and DMAP existence, compound shown in formula III is reacted with vinylformic acid in organic solvent, react the complete described compound that obtains.
In aforesaid method, described organic solvent is selected from least one in toluene, tetrahydrofuran (THF) and methylene dichloride, preferably toluene; Compound shown in described dicyclohexylcarbodiimide, DMAP, formula III and acrylic acid mol ratio are 1-3: 0.01-0.1: 1-1.2: 1-10, preferably 1.5: 0.06: 1: 4; In described reactions steps, temperature is 20-80 ℃, preferably 25 ℃; Time is 1-20 hour, preferably 14 hours.
Wherein, compound shown in described formula III (also containing 2,3,4 of amino replacement, 5-tetraphenyl-silicon heterocyclic pentylene) also belongs to protection scope of the present invention.
Shown in this formula III, the general structure of compound is as follows:
(formula III)
In described formula III general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl, preferable methyl.
The method of compound shown in the above-mentioned formula III of preparation provided by the invention, under the condition that comprises the steps: to exist at Platinic chloride, by compound shown in formula II with alkynyl aniline is reacted in organic solvent, react the complete compound shown in described formula III that obtains;
(formula II)
In described formula II general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl, preferable methyl; Described organic solvent is selected from least one in toluene, tetrahydrofuran (THF) and methylene dichloride, preferably toluene; Compound shown in described Platinic chloride, formula II and be 1 * 10 to the mol ratio of alkynyl aniline
-6-5 * 10
-6: 1-1.1: 1-1.1, preferably 2 * 10
-6: 1: 1; In described reactions steps, temperature is 20-110 ℃, preferably 110 ℃; Time is 1-24 hour, preferably 24 hours.
In addition, the application of polymkeric substance shown in the formula I that the invention described above provides in chemical detection or biological detecting method, also belongs to protection scope of the present invention.The method of polymkeric substance in chemistry or biological detection shown in the formula I of the invention described above protection, specifically can be: with deionized water, water-soluble polymers provided by the invention is made into the dilute solution of 6mg/L; The dilute solution of the material to be detected of different concns is joined by liquid-transfering gun in the dilute solution of this polymkeric substance of 10ml, measure polymkeric substance and the fluorescence intensity of mixing solutions of material to be detected and the fluorescence intensity of the dilute solution of polymkeric substance itself.
The present invention adopts easy free-radical polymerized method, and 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene is incorporated on the side chain of water-soluble polymers, gives this polymkeric substance good dispersed and high fluorescence intensity in the aqueous solution.This polymkeric substance is carried out to structural characterization, and measure its luminosity, known this polymkeric substance has good luminescent properties, and powerful luminous efficiency will greatly improve the sensitivity detecting, and for detecting trace substance, provides the foundation; And this polymkeric substance can be dissolved in the water, some specific group or material are had to good fluorescent quenching or enhancement effect of fluorescence, the water miscible realization of polymkeric substance, can improve widely sensing range, from micromolecular inorganic metal ion, to macromolecular protein or DNA fragmentation, can in the aqueous solution, realize testing goal.And this base polymer main chain has larger conformational freedom, be conducive to fully interact with thing to be detected.Therefore, the water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene provided by the invention is in the chemical/biological context of detection prospect that will have a very wide range of applications.
Accompanying drawing explanation
Fig. 1 is the aqueous solutions of polymers of the embodiment 1 synthesized fluorescence spectrum under 365nm wavelength excites.
Fig. 2 is the fluorescent quenching effect of embodiment 6 bronze medals (II) ionic concn to aqueous solutions of polymers.
Fig. 3 is the fluorescence intensity of aqueous solutions of polymers in embodiment 7 and the relation of bovine serum albumin concentration.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.M in following embodiment in the water-soluble polymers structural formula of gained based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene and the numerical value of n are all to measure and obtain according to conventional GPC method.
1-methyl isophthalic acid shown in embodiment 1, formula III-(4-amino) phenyl-2,3,4,5-tetraphenyl-silicon heterocyclic pentylene synthetic
Under nitrogen atmosphere by 240mg (0.6mmol) 1-methyl-2,3,4,5-tetraphenyl-silicon heterocyclic pentylene is dissolved in 20ml toluene, and (mole dosage of this Chlorine in Solution platinic acid is 1.2 * 10 to the aqueous isopropanol of alkynyl aniline and 20uL Platinic chloride to add successively 70mg (0.6mmol)
-6mmol), 110 ℃ of heating 24 hours, react complete, after question response liquid cooling but, on Rotary Evaporators, concentrate and use silica gel column chromatogram separating purification (volume ratio of petrol ether/ethyl acetate is 3/1 drip washing), product is further used normal hexane/tetrahydrofuran (THF) mixed solvent recrystallization, obtain the solid thing of 259mg yellow-green colour, yield is 84%.
The nuclear-magnetism of this product and high resolution mass spectrum detected result are as follows:
1HNMR(400MHz，acetone-d
6，ppm)δ7.24(d，2H，J＝8)，7.10～7.00(m，17H)，6.89～6.86(m，4H)，6.62(d，2H，J＝8)，6.30(d，IH，J＝19)，4.90(s，2H)，0.61(s，3H).?
13CNMR(400MHz，acetone-d
6，ppm)δ155.612，150.352，149.815，141.731，140,625，140.028，130.687，129.752，128.912，128.694，128.550，128.318，127.845，127.122，126.527，126.435，114.818，114.693，-5.886.HRMS(EI)：Calcd?for?C
37H
31SiN：517.2226.Found：517.2231。
From above-mentioned detected result, this yellow-green colour solid matter is shown in formula III provided by the invention, to contain 2,3,4 of amino replacement, 5-tetraphenyl-silicon heterocyclic pentylene, and its structural formula is suc as formula shown in V:
(formula V)
Synthetic containing the comonomer of 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene shown in embodiment 2, formula IV
934.7mg (1.81mmol) embodiment 1 is prepared to gained 1-methyl isophthalic acid-(4-is amino) phenyl-2, 3, 4, 5-tetraphenyl-silicon heterocyclic pentylene is dissolved in 20ml toluene, add successively 579.2mg (2.8mmol) dicyclohexylcarbodiimide, 13.5mg (0.11mmol) DMAP and 0.5mL (7.3mmol) vinylformic acid, at 25 ℃ of room temperatures, stir and react for 14 hours, filter after completion of the reaction insolubles, filtrate is concentrated rear also with silica gel column chromatogram separating purification (volume ratio of petrol ether/ethyl acetate is 3/1 drip washing) on Rotary Evaporators, product is further used ethyl alcohol recrystallization, obtain 663.8mg yellow-green colour crystal, yield is 65%.
The nuclear-magnetism of this product and high resolution mass spectrum detected result are as follows:
1HNMR(400MHz，acetone-d
6，ppm)δ9.38(s，1H)，7.73(d，2H，J＝8)，7.48(d，2H，J＝8)，7.19(d，1H，J＝19)，7.11～7.03(m，16H)，6.89～6.84(m，4H)，6.63(d，1H，J＝19)，6.44(m，1H)，6.34(d，1H)，5.71(d，1H)，0.65(s，3H)；
13CNMR(400MHz，acetone-d
6，ppm)δ163.993，156.055，148.739，141.424，140.697，140.527，140.004，134.357，132.728，130.731，129.801，128.783，128.369，128.183，127.229，126.566，120.768，120.254，-6.009；HRMS(EI)：Calcd?for?C
40H
33NOSi：571.2331.Found：571.2337.
From above-mentioned detected result, this yellow-green colour crystal is shown in formula IV provided by the invention, to contain the compound of 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene, and its structural formula is suc as formula shown in VI:
(formula VI)
Synthesizing of embodiment 3, the water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene
Prepared by 28.6mg (0.05mmol) embodiment 2 to gained under nitrogen atmosphere containing 2, 3, 4, the comonomer compounds of 5-tetraphenyl-silicon heterocyclic pentylene is dissolved in to be used in the nitrogen bubble 10mL tetrahydrofuran (THF) of 1 hour in advance, then add 137 μ L (2mmol) water-soluble monomer vinylformic acid, after stirring, add again 1.6mg (0.01mmol) radical initiator Diisopropyl azodicarboxylate, reaction solution stirring reaction at 70 ℃ obtains polymers soln after 24 hours, this polymers soln is filtered after sedimentation in normal hexane, filter cake with normal hexane washing for several times, the vacuum-drying at 60 ℃ of gained solid, obtain 124.3mg yellow-green colour pressed powder, yield is 72%.
The detected result of this product is as follows:
IR:3190cm
-1, 2955cm
-1, 1714cm
-1, 1557cm
-1, 1451cm
-1, 1407cm
-1; 1254cm
-1, 1179cm
-1, 803cm
-1, 700cm
-1.
1hNMR (400MHz, acetone-d
6, ppm) δ 12.34 (s), 8.0～6.64 (m), 2.22 (s), 1.76～1.17 (m), 0.61 (s). and number-average molecular weight is 1100, and molecular weight distribution width is 3.18.
As from the foregoing, this product is the water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene shown in formula I provided by the invention, and wherein, m and n are respectively 1 and 53.
Synthesizing of water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene shown in embodiment 4, formula I
Prepared by embodiment 2 to gained 28.6mg (0.05mmol) under nitrogen atmosphere containing 2, 3, 4, the comonomer compounds of 5-tetraphenyl-silicon heterocyclic pentylene is dissolved in to be used in the nitrogen bubble 10ml tetrahydrofuran (THF) of 1 hour in advance, then add 342 μ L (5mmol) water-soluble monomer vinylformic acid, after being stirred, mixed solution adds again 1.6mg (0.01mmol) radical initiator Diisopropyl azodicarboxylate, reaction solution stirs 24 hours to obtain polymers soln at 70 ℃, this polymers soln is filtered after sedimentation in normal hexane, filter cake with normal hexane washing for several times, the vacuum-drying at 60 ℃ of gained solid, obtain 320.0mg yellow-green colour pressed powder, yield is 82%.
The detected result of this product is as follows:
IR:3190cm
-1, 2955cm
-1, 1714cm
-1, 1557cm
-1, 1451cm
-1, 1407cm
-1; 1254cm
-1, 1179cm
-1, 803cm
-1, 700cm
-1.
1hNMR (400MHz, acetone-d
6, ppm) δ 12.25 (s), 8.0～6.64 (m), 2.22 (s), 1.76～1.17 (m), 0.61 (s). and number-average molecular weight is 1100, and molecular weight distribution width is 1.81.
As from the foregoing, this product is the water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene shown in formula I provided by the invention, and wherein, m and n are respectively 1 and 144.
Synthesizing of water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene shown in embodiment 5, formula I
Prepared by embodiment 2 to gained 28.6mg (0.05mmol) under nitrogen atmosphere containing 2, 3, 4, the comonomer compounds of 5-tetraphenyl-silicon heterocyclic pentylene is dissolved in to be used in the nitrogen bubble 10ml tetrahydrofuran (THF) of 1 hour in advance, then add 452.6mg (4mmol) water-soluble monomer NIPA, after stirring, add again 2.5mg (0.015mmol) radical initiator Diisopropyl azodicarboxylate, reaction solution stirs 24 hours to obtain polymers soln at 70 ℃, this polymers soln is filtered after sedimentation in normal hexane, filter cake with normal hexane washing for several times, the vacuum-drying at 80 ℃ of gained solid, obtain 384.7mg yellow-green colour pressed powder, yield is 80%.
The detected result of this product is as follows:
IR:3306cm
-1, 3077cm
-1, 2973cm
-1, 2934cm
-1, 2876cm
-1, 1649cm
-1, 1544cm
-1, 1460cm
-1, 1387cm
-1; 1368cm
-1, 1173cm
-1, 1131cm
-1.
1hNMR (400MHz, acetone-d
6, ppm) δ 8.0～6.64 (m), 3.85 (s), 2.34～1.70 (m), 1.70～1.18 (m), 1.04 (m), 0.61 (s). and number-average molecular weight is 2200, and molecular weight distribution width is 1.68.
As from the foregoing, this product is the water-soluble polymers based on 2,3,4,5-tetraphenyl-silicon heterocyclic pentylene shown in formula I provided by the invention, and wherein, m and n are respectively 1 and 48.
Embodiment 6
Embodiment 3 is prepared to gained water-soluble polymers and be dissolved in deionized water, be made into the dilute solution that concentration is 6mg/L.In 10ml dilute polymer, add respectively 1.7 * 10
-8mol/L, 3.4 * 10
-8mol/L, 5.1 * 10
-8mol/L, 6.8 * 10
-8mol/L, 10.2 * 10
-8mol/L, 13.6 * 10
-8mol/L, 17 * 10
-8mol/L, 20.4 * 10
-8mol/L, 23.8 * 10
-8the cupric bromide aqueous solution of mol/L, the fluorescence intensity I of the fluorescence intensity I of more whole mixed solution system and dilute polymer itself
0relative size, the cancellation effect of research copper (II) ion pair polymerization thing fluorescence, acquired results as shown in Figure 2.As shown in Figure 2, this polymkeric substance has very high sensitivity, to the detection of copper (II) ionic concn, can be low to moderate 10
-8mol/L.
Embodiment 7
Embodiment 3 is prepared to resulting polymers and be dissolved in deionized water, be made into the dilute solution that concentration is 6mg/L.Toward the phosphate buffer solution (pH value is 7.4) that adds the bovine serum albumin of different concns (0uM, 0.08uM, 0.16uM, 0.24uM, 0.32uM, 0.4uM, 0.48uM, 0.56uM and 0.64uM) in the dilute solution of this polymkeric substance of 10ml, study the fluorescence intensity of whole mixed solution system and the relation of bovine serum albumin concentration, as shown in Figure 3.As seen from the figure, the fluorescence intensity of mixed system increases with the increase (0～0.48 μ M) of bovine serum albumin concentration, can be used for the detection of biomolecules concentration.
Claims (18)
1. polymkeric substance shown in formula I,
In described formula I general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl; R
2for hydroxyl, amino or sec.-propyl amido; R
3for hydrogen atom or methyl; M and n are the integer of 1-200.
2. polymkeric substance according to claim 1, is characterized in that: in described formula I general structure, and R
1for methyl; R
2for hydroxyl; M and n are the integer of 1-50.
3. a method of preparing polymkeric substance described in claim 1 or 2, under the condition that comprises the steps: to exist at radical initiator, compound shown in formula IV is carried out to copolyreaction with water-soluble monomer in organic solvent, react the complete polymkeric substance described in claim 1 or 2 that obtains;
In described formula IV general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl;
Described water-soluble monomer is vinylformic acid, methacrylic acid, acrylamide or NIPA.
4. method according to claim 3, is characterized in that: in described formula IV general structure, and R
1for methyl.
5. according to the method described in claim 3 or 4, it is characterized in that: described organic solvent is selected from least one in toluene, tetrahydrofuran (THF) and methylene dichloride; Described radical initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; Shown in described radical initiator, described formula IV, the mol ratio of compound and water-soluble monomer is 0.1-0.3:1-1.1:1-100; In described copolyreaction step, temperature is 20-80 ℃; Time is 1-24 hour.
6. method according to claim 5, is characterized in that: described organic solvent is selected from tetrahydrofuran (THF); Shown in described radical initiator, described formula IV, the mol ratio of compound and water-soluble monomer is 0.2:1:40; In described copolyreaction step, temperature is 70 ℃; Time is 24 hours.
7. the application of polymkeric substance in chemical detection or biological detecting method described in claim 1 or 2.
8. compound shown in formula IV;
In described formula IV general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl.
9. compound according to claim 8, is characterized in that: in described formula IV general structure, and R
1for methyl.
10. a method of preparing compound described in claim 8 or 9, comprise the steps: under the condition of dicyclohexylcarbodiimide and DMAP existence, compound shown in formula III is reacted with vinylformic acid in organic solvent, react the complete compound described in claim 8 or 9 that obtains;
In described formula III general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl.
11. methods according to claim 10, is characterized in that: in described formula III general structure, and R
1for methyl.
12. according to the method described in claim 10 or 11, it is characterized in that: described organic solvent is selected from least one in toluene, tetrahydrofuran (THF) and methylene dichloride;
Shown in described dicyclohexylcarbodiimide, DMAP, described formula III, compound and acrylic acid mol ratio are 1-3:0.01-0.1:1-1.2:1-10;
In described reactions steps, temperature is 20-80 ℃; Time is 1-20 hour.
13. methods according to claim 12, is characterized in that: described organic solvent is selected from toluene;
Shown in described dicyclohexylcarbodiimide, DMAP, described formula III, compound and acrylic acid mol ratio are 1.5:0.06:1:4;
In described reactions steps, temperature is 25 ℃; Time is 14 hours.
Compound shown in 14. formula IIIs,
In described formula III general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl.
15. compounds according to claim 14, is characterized in that: in described formula III general structure, and R
1for methyl.
16. 1 kinds of methods of preparing compound described in claims 14 or 15, under the condition that comprises the steps: to exist at Platinic chloride, by compound shown in formula II with alkynyl aniline is reacted in organic solvent, react the complete compound described in claims 14 or 15 that obtains;
In described formula II general structure, R
1for carbonatoms be 1-6 alkyl, cyclohexyl, phenyl or p-methylphenyl.
17. methods according to claim 16, is characterized in that: in described formula II general structure, and R
1for methyl; Described organic solvent is selected from least one in toluene, tetrahydrofuran (THF) and methylene dichloride; Compound shown in described Platinic chloride, formula II and be 1 * 10 to the mol ratio of alkynyl aniline
-6-5 * 10
-6: 1-1.1:1-1.1; In described reactions steps, temperature is 20-110 ℃; Time is 1-24 hour.
18. methods according to claim 17, is characterized in that: described organic solvent is toluene; Compound shown in described Platinic chloride, formula II and be 2 * 10 to the mol ratio of alkynyl aniline
-6: 1:1; In described reactions steps, temperature is 110 ℃; Time is 24 hours.
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Non-Patent Citations (4)
| Title |
|---|
| Functionalized Siloles: Versatile Synthesis, Aggregation-Induced Emission, and Sensory and Device Applications;Zhen Li et al.;《Adv. Funct. Mater.》;20090211;第19卷;905-917 * |
| Synthesis of Functionalized 2,3,4,5-Tetraphenylsilole Derivatives Through Hydrosilylation and Their Crystal;Yunsheng Zhang et al.;《Synthetic Communications》;20120409;2171-2180 * |
| Yunsheng Zhang et al..Synthesis of Functionalized 2,3,4,5-Tetraphenylsilole Derivatives Through Hydrosilylation and Their Crystal.《Synthetic Communications》.2012,2171-2180. |
| Zhen Li et al..Functionalized Siloles: Versatile Synthesis, Aggregation-Induced Emission, and Sensory and Device Applications.《Adv. Funct. Mater.》.2009,第19卷905-917. |
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