CN106674262B - A kind of fullerene -- glimmering triplet photosensitive molecular of fluorine boron and preparation method thereof - Google Patents
A kind of fullerene -- glimmering triplet photosensitive molecular of fluorine boron and preparation method thereof Download PDFInfo
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Abstract
A kind of glimmering triplet photosensitive molecular of fullerene fluorine boron and preparation method thereof is related to functional organic molecule design and synthesis technical field.Fullerene pyrroles cycle compound and fluorine boron fluormetric are not connected to by amido bond on two acid anhydrides of acid anhydride, and one end of bridged bond is connected in the positions meso of the N atoms and fluorine boron fluormetric of fullerene pyrroles's ring structure respectively, form a C2Symmetrical linear molecule.The present invention will link together with glimmering compared with the acid anhydride and fluorine boron absorbed by force with Spin transition unit fullerene in visible region, form linear molecule, it not only makes up the photosensitive chemoattractant molecule of traditional triplet and absorbs weak weakness in visible region, the shortcomings of generating full light absorption, and other triplet photosensitive molecular photosensitizing effects can be overcome unstable.It can be applied to triplet photosensitizer and bury in oblivion the fields such as upper conversion in photocatalysis organic reaction, photovoltaic cell, photodynamic therapy (PDT), photopolymerization, fluorescent molecular probe, triplet triplet.
Description
Technical field
The present invention relates to functional organic molecule design and synthesis technical fields, are specifically related to a kind of fullerene -- fluorine boron
Glimmering triplet photosensitive molecular and preparation method thereof.
Background technology
Triplet photosensitizer is made in photocatalysis organic reaction, photovoltaic cell, photodynamic therapy (PDT), photo polymerization
With, convert on fluorescent molecular probe, T-T annihilation etc. and to have a wide range of applications, therefore become grind in recent years
The hot spot studied carefully.Traditional triplet photosensitizer is some typical transition metal composites, such as Pt (II), Ir (III), Ru
(II) complex.Although this kind of photosensitive chemoattractant molecule of triplet has efficient intersystem crossing efficiency, they are in visual field
Molar extinction coefficient is smaller, and the service life of triplet excited state is also very short, and price is relatively high, thus limits their application.
In recent years, the organic compound containing the heavy atoms such as iodine or bromine is also developed as triplet photosensitizer.But this kind of triplet
Photosensitive chemoattractant molecule requires the presence for having the heavy atoms such as iodine or bromine, to realize intersystem crossing, generates photosensitizing efficiency, therefore, it is difficult into
Row is further derivative.The third triplet photosensitizer is free from the organic molecules such as porphyrin and the benzophenone of heavy atom.It removes
Outside Porphyrin Molecule, this kind of photosensitive chemoattractant molecule is limited to ultra-violet (UV) band greatly between the absorption region of light, visible light cannot be carried out
It captures well.And the mechanism of these molecules generation intersystem crossing is different from, and the intersystem crossing property of molecule is difficult to control,
It can be disappeared due to artificially derivative, lose sensitization effect.Therefore, the photosensitive chemoattractant molecule of Development of Novel triplet is one has very much
Meaning and challenging project.
Fullerene (mainly C60) due to low excitation state, good photo and thermal stability, high intersystem crossing efficiency
And high triplet yield (close to 1), and compared with the photosensitive chemoattractant molecule of transition metal, C60With excellent honest and clean, the no dirt of price
The advantages that dye, therefore C60It is an ideal Spin transition unit.But due to C60It is very weak in the absorption of visible region, only exist
There is a very weak absorption in 700nm, therefore itself is not an ideal the photosensitive chemoattractant molecule of triplet.If can be
C60On be connected to visible region have higher absorptivity chromophore, as light capture feeler, so that it may to greatly increase body
It is the absorption to visible light.
Zhao Jian chapters seminar exists《Chemical Communications》(Liu,Y.；Zhao,J.Chem.Commun.
(Camb) it is reported in 2012,48,3751) by C60The positions bay of PDI are connected to, C as shown below has been synthesized60- PDI points
Son, they have found that the system is extraordinary photosensitive chemoattractant molecule, and sensitization effect is got well than methylene blue in the market, Ke Yihe
The best organic dyestuff tetraphenylporphyrin (TPP) of sensitization effect matches in excellence or beauty at present.
They also reported a series of BODIPY and C60Connected system (Huang, D.；Zhao,J.；Wu,W.；Yi,X.；
Yang,P.；Ma,J.Asian J.Org.Chem.2012,1,264；Huang,L.；Cui,X.；Therrien,B.；Zhao,
J.Chem.Eur.J.2013,19,17472；Huang,L.；Zhao,J.Chem.Commun.2013,49,3751；Wu,W.；
Zhao,J.；Sun,J.；Guo S.J.Org.Chem.2012,77,5305；Huang,L.；Yu,X.；Wu,W.；Zhao,
J.Org.Lett., 2012,14,2594), C is utilized60Spin transition effect, these molecules alter between being also effectively
More, triplet excited state is generated, photosensitizing efficiency is generated.
But in the above molecule, capture group is all based on a chromophore, therefore these photosensitive chemoattractant molecules are visible
Light area only there are one relatively narrow absorption band, can only covering visible light spectrum a very little range, this to using the excitation of full light (such as
Sunlight) light-catalyzed reaction etc. be unfavorable.Therefore, it is necessary to explore it is with full light absorption, without heavy atom and have
Photosensitive chemoattractant molecule of triplet of controllable intersystem crossing property and preparation method thereof.
Invention content
In order to overcome drawbacks described above present in existing triplet photosensitive molecular, one of the objects of the present invention is to provide one
Kind fullerene -- the glimmering triplet photosensitive molecular of fluorine boron, it can both make up traditional triplet photosensitizer and inhaled in visible region
The shortcomings of receiving weak disadvantage, generate full light absorption, and other triplet photosensitive molecular photosensitizing effects can be overcome unstable.
To realize the purpose, present invention employs following technical schemes：
A kind of fullerene -- the glimmering triplet photosensitive molecular of fluorine boron, general formula of molecular structure are as follows：
R is selected from the alkyl that carbon atom number is 1~12 in general formula；
R in general formula1And R2Selected from from substitution aryl or heterocyclic aryl, carbon atom number be 2~5 alkyl, H, Cl, Br,
I、-OR3Or SR3, wherein R3Selected from H, substituted aryl or heterocyclic aryl, the alkyl that carbon atom number is 2~6；
X is in general formulaCarbon atom number
Alkyl ,-CH for 2~122R4CH2NHCH2R5CH2-、-CH2R6CH2OCH2R7CH2-、-CH2R8CH2OCH2R9CH2, wherein Z is
The alkynyl that carbon atom number is 2 or 4, R4、R5、R6、R7、R8And R9The alkyl for being 2~8 for alkenyl, alkynyl or carbon atom number；
Y is in general formulaWherein Z is carbon
The alkynyl that atomicity is 2 or 4.
Fullerene pyrroles cycle compound and fluorine boron fluormetric are not connected to by amido bond on two acid anhydrides of acid anhydride in above formula,
And one end of bridged bond is connected in the positions meso of the N atoms and fluorine boron fluormetric of fullerene pyrroles's ring structure respectively, forms one
C2Symmetrical linear molecule.
Another object of the present invention is to provide a kind of fullerenes -- the preparation method of the glimmering triplet photosensitive molecular of fluorine boron,
To realize the purpose, present invention employs following technical schemes：
Fullerene -- the preparation method of the glimmering triplet photosensitive molecular of fluorine boron, preparation route be：
It in turn includes the following steps：
Step is 1.：Diamines 1 and di-tert-butyl dicarbonate, that is, Boc2O occurs substitution reaction and prepares with unilateral Boc protecting groups
The molar ratio of compound 2,1 and di-tert-butyl dicarbonate be 0.8~1.2：0.8~1.2, reaction temperature is room temperature, when reaction
Between be 12~36h；
Step is 2.：Compound 2 occurs substitution reaction with alkyl bromoacetate under the catalytic action of Anhydrous potassium carbonate and prepares
The molar ratio of compound 3, compound 2, Anhydrous potassium carbonate and alkyl bromoacetate is 0.8~1.2：1.2~2.0：0.8~1.2,
Reaction temperature is room temperature, the reaction time is 10~for 24 hours；
Step is 3.：Compound 3, fullerene and acetaldehyde acid alkyl ester occur Prato and react prepare compound 4, compound 3,
The molar ratio of fullerene and acetaldehyde acid alkyl ester is 1.8~2.2：0.8~1.2：1.6~12, reaction temperature is 140~160 DEG C,
Reaction time is 0.5~5h；
Step is 4.：Compound 4 removes Boc protecting groups prepare compound 5 in chloroform-trifluoroacetic acid dicyandiamide solution, reaction
Temperature is room temperature, and the reaction time is 0.5~5h；
Step is 5.：With nitroaryl aldehyde 7 condensation reaction occurs under the catalysis of trifluoroacetic acid for substituted pyrroles 6, recycles
Dichlorocyanobenzoquinone dehydrogenation finally adds triethylamine neutralization, and boron trifluoride ether coordination is used in combination to prepare the fluorine containing nitro
The molar ratio of the glimmering compound 8 of boron, nitroaryl aldehyde, substituted pyrroles and trifluoroacetic acid is 0.8~1.2：1.6~2.4：0.3~
0.5, reaction temperature is room temperature, the reaction time is 8~for 24 hours；The molar ratio of nitroaryl aldehyde and dichlorocyanobenzoquinone be 0.8~
1.2：0.8~1.2, reaction temperature is room temperature, and the reaction time is 4~10h；Nitroaryl aldehyde, triethylamine and boron trifluoride ether
Molar ratio be 0.8~1.2：36~55：38~57, reaction temperature be 0~30 DEG C, the reaction time be 12~for 24 hours；
Step is 6.：The glimmering compound of nitro fluorine boron 8 utilizes the catalysis of Pd/C in absolute ethyl alcohol, selects NH2NH2·H2O is restored
Prepare the glimmering compound 9 of amino fluorine boron, compound 8, Pd/C and NH2NH2·H2The molar ratio of O is 0.8~1.2：0.2~0.4：6.6
~10, reaction temperature is 80~100 DEG C, is reacted for 1~5h of time；
Step is 7.：Under Catalyzed by Imidazole with acid anhydride 10 amidation process prepare compound occurs for the glimmering compound 9 of amino fluorine boron
11, the molar ratio of compound 9, compound 10 and imidazoles is 0.8~1.2：1.0~1.8：10~15, reaction temperature is 70~90
DEG C, the reaction time is 24~32h；
Step is 8.：Compound 5 occurs amidation process with compound 11 under Catalyzed by Imidazole and prepares target product P i.e. fowler
The molar ratio of alkene -- the glimmering functional molecular of fluorine boron, compound 5, compound 11 and imidazoles is 1.6~2.4：0.8~1.2：10~
15, reaction temperature is 70~90 DEG C, and the reaction time is 24~32h.
As of the invention, fullerene -- the preparation method of the glimmering triplet photosensitive molecular of fluorine boron is further improved：
1. concrete operations are the step：First by diamines 1 with 1：15~25 (g：ML it) is dissolved in Isosorbide-5-Nitrae-dioxane,
5~40min is stirred under protection of argon gas；Again by Boc2O is with 1：4~6 (g：ML it) is dissolved in Isosorbide-5-Nitrae-dioxane, is dripped with constant pressure
Liquid funnel is slowly added drop-wise in biphenyl amine aqueous solution；Reaction is stirred at room temperature in mixed liquor, is tracked using thin-layer chromatography, until mesh
The content for marking product is more than 80%, stops reaction；After the completion of reaction, rotation crosses post separation except the solvent in system, crude product, collects
Second colour band finally concentrates, is dried in vacuo to have unilateral boc-protected compound 2.
2. concrete operations are the step：Take compound 2 with 1：1.5~2.5 (g：ML it) is dissolved in DMF, then adds again
Anhydrous K2CO3；Reaction mixture first leads to argon gas at room temperature protects 5~40min, and alkyl bromoacetate, which is then promptly added, is
BrCH2CO2R continues logical 5~20min argon gas, reaction bulb is sealed；Reaction mixture puts and is stirred at room temperature 10~for 24 hours, it utilizes
Thin-layer chromatography tracks, and waits for that raw material point disappears substantially, DMF is removed under reduced pressure, then mixture is crossed post separation, obtains compound 3.
3. concrete operations are the step：By fullerene, that is, C60With 1：50~55 (g：ML it) is dissolved in o-dichlorohenzene, and
Compound 3 is added；Reaction mixture at room temperature, leads to argon gas and protects 20~80min, be then by acetaldehyde acid alkyl ester
HCOCO2R is added, and continues logical 5~20min argon gas, reaction mixture is put into and is previously heated in 140~160 DEG C of oil bath pan
Reaction；When the amount residue 30%~40% of fullerene, stop reaction；Then it is evaporated under reduced pressure, by the adjacent dichloro in reaction system
Benzene removes；Reaction mixture is dissolved with carbon disulfide, and pillar layer separation is used in combination, and first using carbon disulfide as eluant, eluent, removal is not
Reacted C60, then use big polar eluent instead again, obtain compound 4.
4. concrete operations are the step：By compound 4 with 1：110~130 (g：ML it) is dissolved in chloroform, reaction solution exists
Under the protection of argon gas, 5~20min is stirred at room temperature, is then added with 1：15~25 (g：ML it is) trifluoroacetic acid of proportional quantities,
0.5~5h of reaction is stirred at room temperature in reaction solution, is tracked using thin-layer chromatography, after 4 raw material point of compound completely disappears, stops
Reaction；Solvent is spin-dried for, silicagel column is used in combination to filter, obtains brown color compound 5.
5. concrete operations are the step：By compound 6 with 1：120~150 (g：ML it) is dissolved in anhydrous tetrahydro furan,
It adds compound 7 and tempestuously leads to argon gas 30 minutes, trifluoroacetic acid is promptly added, reaction mixture continues in argon gas
In the presence of, it is stirred at room temperature 8~for 24 hours, until TLC plates show 7 disappearance；DDQ and anhydrous tetrahydro furan is slowly added dropwise
Mixed liquor is with 1：12~15 (g：ML), continue 4~10h of stirring；Reaction solution is transferred under condition of ice bath, slow with constant pressure funnel
Et is slowly added3N after stirring 5min, then is slowly added into BF3.OEt2；Continue stirring 12~for 24 hours at room temperature, stops reaction；
After reaction solution dichloromethane and water extract three times repeatedly, it is dried overnight with anhydrous sodium sulfate；After being spin-dried for solvent, with column chromatography point
From obtaining the solid product 8 of crocus.
6. concrete operations are the step：By compound 8 with 1：150~200 (g：ML it) is dissolved in absolute ethyl alcohol, then adds
Enter NH2NH2·H2O and Pd/C；Reaction mixture is under conditions of argon gas, at 80~100 DEG C, 1~5h is reacted, until TLC is shown
Until 8 completely disappear；After equal reaction solutions are cooled to room temperature, filtering removes catalyst；After solvent is spin-dried for, with dichloromethane weight
New dissolving, crosses post separation, obtains crocus solid 9.
7. concrete operations are the step：By compound 9 with 1：400~500 (g：ML it) is dissolved in chloroform, adding
Object 10 and imidazoles are closed, reaction mixture first leads to 5~20min of argon gas, is then placed on again and is previously heated to 70~90 at room temperature
DEG C oil bath pan in react；It is tracked using thin-layer chromatography, waits for that the consumption substantially of compound 9 is complete, stop reaction, reaction solution is cooled to
It after room temperature, is extracted with chloroform and water, organic phase is dried with anhydrous sodium sulfate, and then rotation removes solvent, isolated dark red with TLC plates
Color product 11.
8. concrete operations are the step：By compound 11 with 1：300~400 (g：ML it) is dissolved in chloroform, adds
Compound 5 and imidazoles, reaction mixture first lead to 5~20min of argon gas, are then placed on again and are previously heated to 70~90 at room temperature
DEG C oil bath pan in react；It is tracked using thin-layer chromatography, waits for that the consumption substantially of compound 11 is complete, stop reaction, reaction solution cooling
It to room temperature, is extracted with chloroform and water, organic phase is dried with anhydrous sodium sulfate, is then revolved except solvent is obtained with pillar layer separation
Kermesinus target product P.
Compared with prior art, beneficial effects of the present invention are shown：
1), the present invention will have and Spin transition glimmering compared with the acid anhydride and fluorine boron that absorb by force by rationally designing in visible region
Unit fullerene links together, and forms linear molecule, not only makes up the photosensitive chemoattractant molecule of traditional triplet and is absorbed in visible region
Weak weakness generates full light absorption, and the shortcomings of other triplet photosensitive molecular photosensitizing effects can be overcome unstable.
It is 2), of the invention that fullerene -- the glimmering triplet photosensitive molecular of fluorine boron can generate stronger photosensitizing efficiency.
3), the fullerene -- it is organic in photocatalysis that the glimmering triplet photosensitive molecular of fluorine boron can be applied to triplet photosensitizer
Reaction, photovoltaic cell, photodynamic therapy (PDT), photopolymerization, fluorescent molecular probe, on T-T annihilation
The fields such as conversion.
Description of the drawings
Fig. 1 is fullerene -- the preparation route figure of the glimmering triplet photosensitive molecular of fluorine boron.
Fig. 2 is a kind of fullerene -- the glimmering triplet photosensitive molecular P1 of fluorine boron prepared by embodiment1H NMR。
Fig. 3 is a kind of fullerene -- the glimmering triplet photosensitive molecular P1 of fluorine boron prepared by embodiment13C NMR。
Specific implementation mode
The present embodiment is by a kind of fullerene -- for the glimmering triplet photosensitive molecular P1 of fluorine boron, in conjunction with preparation route figure (Fig. 1
It is shown) introduce its structure and specific preparation method.
Step is 1.
It takes 8.4mmol benzidine 1-1 to be dissolved in Isosorbide-5-Nitrae-dioxane of 30mL first, stirs under protection of argon gas
30min.Again by 8.4mmol di-tert-butyl dicarbonates, that is, Boc2O is dissolved in Isosorbide-5-Nitrae-dioxane of 10mL, is leaked with constant pressure addition
Bucket is slowly added drop-wise in biphenyl amine aqueous solution, entire that process control is added dropwise within 30min.Mixed liquor is stirred at room temperature instead
It answers, is tracked using thin-layer chromatography, the content of target product is more than 80% after 24 hours, stops reaction.Rotation removes the solvent in system,
Crude product crosses post separation, with petroleum ether：Ethyl acetate=4：1(V：V it) is used as eluent, collects second colour band, finally concentration,
It is dried in vacuo to obtain compound 2-1s (85%) of the 2.02g with unilateral Boc protecting groups.
Step is 2.
It takes 2.6mmol compounds 2-1 to be put into 25mL single port bottles, and is dissolved to the DMF of 1.5mL, then added again
4.5mmol anhydrous K2CO3.Reaction mixture first leads to argon gas at room temperature protects 30min, and bromoacetate is then promptly added
That is BrCH2CO2Et continues logical 10min argon gas, reaction bulb is sealed.Reaction mixture, which is put, to be stirred at room temperature, and thin layer color is utilized
Spectrum tracking, raw material point disappears substantially after 11 hours, DMF is removed under reduced pressure, then mixture is crossed post separation, obtains compound 0.66g
3-1 (68%).
Step is 3.
By 0.44mmol compound 3-1 and 0.22mmol fullerenes C60It is dissolved in the o-dichlorohenzene of 8mL.Reaction mixture
At room temperature, lead to argon gas and protect 60min, then by glyoxylic acid ethyl ester, that is, HCOCO2Et is added, and continues logical 10min argon gas, will be anti-
It answers mixture to be put into be previously heated to react in 150 DEG C of oil bath pan.The amount residue 30%~40% of fullerene after 1.5h stops
Reaction.Then it is evaporated under reduced pressure, the o-dichlorohenzene in reaction system is removed.Reaction mixture is dissolved with carbon disulfide, and column is used in combination
Chromatographic isolation, first using carbon disulfide as eluant, eluent, the complete C of removal unreacted60, then use big polar eluent instead again, obtain
To the 4-1 (the boc-protected miscellaneous 5-membered ring compounds of fullerene N-, 35%) of compound 86.9mg.
Step is 4.
0.09mmol compounds 4-1 is taken to be dissolved in the chloroform of 12mL, reaction solution stirs at room temperature under the protection of argon gas
10min to be mixed, the trifluoroacetic acid of 2mL is then added, reaction solution is stirred at room temperature reaction, is tracked using thin-layer chromatography, after 1.5h,
Compound 4-1 is completely disappeared, and stops reaction.Solvent is spin-dried for, silicagel column is used in combination to filter, obtains brown color compound 87.6mg's
5-1 (the miscellaneous 5-membered ring compounds of fullerene N- containing amino active group, 95%).
Step is 5.
It is anhydrous that the paranitrobenzaldehyde 7-1 of 2,4- the dimethyl pyrroles 6-1 and 3.0mmol of 7.6mmol are dissolved in 100mL
It in tetrahydrofuran (THF), is stirred at room temperature, and tempestuously leads to argon gas 30min, with the air in removing system.Then fast
2 drop trifluoroacetic acids are added dropwise fastly, reaction mixture continues in the presence of argon, to be stirred at room temperature 12 hours, until TLC plates are aobvious
Until showing that paranitrobenzaldehyde disappears.The DDQ of 1 times of equivalent is dissolved in the THF of 10mL, is then slowly added drop-wise to above-mentioned anti-
It answers in mixed liquor.Continue after stirring 4h, reaction solution is transferred under condition of ice bath.It is slowly added 18mL's with constant pressure funnel
Et3N after stirring 5min, then is slowly added into the BF of 19mL3.OEt2.Continue at room temperature after stirring 12h, stops reaction.Reaction
After liquid dichloromethane and water extract three times repeatedly, it is dried overnight with anhydrous sodium sulfate.After being spin-dried for solvent, with pillar layer separation,
With dichloromethane and petroleum ether 2：1 is used as eluent, the solid 8-1 (61%) of isolated 0.5g crocus.
Step is 6.
By the NH of the compound 8-1,0.1mL of 85.5mg2NH2·H2The absolute ethyl alcohol of O and 17mL, is placed in two-mouth bottle,
It is stirred under conditions of argon gas.Then the Pd/C of 9.2mg is added as catalyst.Reaction mixture flows back under conditions of argon gas
4h, until TLC shows that raw material completely disappears.After equal reaction solutions are cooled to room temperature, filtering removes catalyst.Solvent is revolved
It after dry, is re-dissolved with dichloromethane, crosses post separation and obtain the crocus solid 9-1 (91%) of 74.3mg.
Step is 7.
The chloroform of the imidazoles of 10, the 86.0mg of the compound 9-1,144.6mg of 30.3mg and 15mL are added the two of 25mL
In mouth bottle.Reaction mixture first leads to argon gas 10min at room temperature, is then placed on and is previously heated in 80 DEG C of oil bath pan instead again
It answers.Reaction is tracked with TLC plates, and after 28h, compound 9-1 is consumed completely substantially.After reaction solution is cooled to room temperature, with chloroform and water
Extraction.Organic phase is dried with anhydrous sodium sulfate.After solvent being removed with Rotary Evaporators rotation, mixture dichloromethane dissolving, in order to subtract
Few absorption, is detached using TLC plates, with DCM：PE=3：2 be solvent, the kermesinus product 11-1 of isolated 76.46mg
(65%).
Step is 8.
By the 11-1 of 28.3mg, the imidazoles of fullerene pyrrole ring the product 5-1,142.9mg containing amino of 42.92mg with
And the chloroform of 10mL is added in the two-mouth bottle of 25mL.Reaction mixture first leads to argon gas 10min at room temperature, is then placed on again in advance
It is heated to react in 80 DEG C of oil bath pan.Reaction with TLC plates track, for 24 hours after, compound 11-1 is consumed completely substantially.Reaction solution
After being cooled to room temperature, extracted with chloroform and water.Organic phase is dried with anhydrous sodium sulfate.After removing solvent with Rotary Evaporators rotation, mix
The dissolving of object dichloromethane is closed, with pillar layer separation, with DCM：PE=2：1 is solvent, isolated kermesinus product P1
(29.76mg, 63%).
Target product P1's prepared by above-described embodiment1H NMR,13C NMR distinguish as shown in Figure 2,3, this point of experiment test
The mass spectrometric data of son：M/z=2362.6989 (C89H80BF2N4O8, M+)。
The structural formula of target product P1 is as follows：
To those skilled in the art, with the different choosings of R, X, Y in target product P (general structure is as follows) general formula
Select, it will prepare the fullerene of several different structure -- the glimmering triplet photosensitive molecular of fluorine boron,
Example 1 (fullerene -- the glimmering triplet photosensitive molecular P2 of fluorine boron)：
In general formula, R is methyl, and X isY isR1For methyl, R2For ethyl.
Example 2 (fullerene -- the glimmering triplet photosensitive molecular P3 of fluorine boron)：
In general formula, R is isopropyl, and X is-CH2(CH2)6CH2, Y isR1For methoxyl group, R2For
Ethyl.
Example 3 (fullerene -- the glimmering triplet photosensitive molecular P4 of fluorine boron)：
In general formula, R is dodecyl, and X is-CH2CH2O(CH2)2OCH2CH2, Y isR1For ethyl, R2For Cl.
Example 4 (fullerene -- the glimmering triplet photosensitive molecular P5 of fluorine boron)：
In general formula, R is normal-butyl, and X and Y areR1For ethyl, R2For H.
Example 5 (fullerene -- the glimmering triplet photosensitive molecular P6 of fluorine boron)：
In general formula, R is n-propyl, and X isY isR1For
Toluene, R2For methyl.
Above-mentioned different fullerene -- the glimmering triplet photosensitive molecular (P2-P6) of fluorine boron, preparation method and reaction mechanism
More identical with P1, this is no longer going to repeat them.
Claims (1)
1. a kind of fullerene -- the preparation method of the glimmering triplet photosensitive molecular of fluorine boron, it is characterised in that：Preparation route is：
It in turn includes the following steps：
Step is 1.：Diamines 1 and di-tert-butyl dicarbonate, that is, Boc2O occurs substitution reaction and prepares the chemical combination with unilateral Boc protecting groups
The molar ratio of object 2,1 and di-tert-butyl dicarbonate is 0.8~1.2：0.8~1.2, reaction temperature is room temperature, reaction time 12
~36h；
First by diamines 1 with 1：15~25 (g：ML it) is dissolved in Isosorbide-5-Nitrae-dioxane, stirs 5~40min under protection of argon gas；
Again by Boc2O is with 1：4~6 (g：ML it) is dissolved in Isosorbide-5-Nitrae-dioxane, benzidine is slowly added drop-wise to constant pressure funnel
In solution；Reaction is stirred at room temperature in mixed liquor, is tracked using thin-layer chromatography, until target product content be more than 80%, stop
Only react；After the completion of reaction, except the solvent in system, crude product crosses post separation for rotation, collects second colour band, finally concentrates, is true
It is empty dry that there is unilateral boc-protected compound 2；
Step is 2.：Compound 2 occurs substitution reaction with alkyl bromoacetate under the catalytic action of Anhydrous potassium carbonate and prepares chemical combination
The molar ratio of object 3, compound 2, Anhydrous potassium carbonate and alkyl bromoacetate is 0.8~1.2：1.2~2.0：0.8~1.2, reaction
Temperature is room temperature, the reaction time is 10~for 24 hours；
Take compound 2 with 1：1.5~2.5 (g：ML it) is dissolved in DMF, then adds anhydrous K again2CO3；Reaction mixture is in room temperature
The lower argon gas that first leads to protects 5~40min, and alkyl bromoacetate, that is, BrCH is then promptly added2CO2R continues logical 5~20min argons
Gas seals reaction bulb；Reaction mixture puts and is stirred at room temperature 10~for 24 hours, it is tracked using thin-layer chromatography, waits for that raw material point is basic
It disappears, DMF is removed under reduced pressure, then mixture is crossed into post separation, obtains compound 3；
Step is 3.：Compound 3, fullerene occur Prato with acetaldehyde acid alkyl ester and react prepare compound 4, compound 3, fowler
The molar ratio of alkene and acetaldehyde acid alkyl ester is 1.8~2.2：0.8~1.2：1.6~12, reaction temperature is 140~160 DEG C, reaction
Time is 0.5~5h；
By fullerene, that is, C60With 1：50~55 (g：ML it) is dissolved in o-dichlorohenzene, and compound 3 is added；Reaction mixture is in room
Under temperature, leads to argon gas and protect 20~80min, then by acetaldehyde acid alkyl ester, that is, HCOCO2R is added, and continues logical 5~20min argon gas,
Reaction mixture is put into and is previously heated to react in 140~160 DEG C of oil bath pan；Wait for the amount residue 30%~40% of fullerene
When, stop reaction；Then it is evaporated under reduced pressure, the o-dichlorohenzene in reaction system is removed；Reaction mixture is dissolved with carbon disulfide,
Pillar layer separation is used in combination, first using carbon disulfide as eluant, eluent, the complete C of removal unreacted60, then use big polar elution instead again
Agent obtains compound 4；
Step is 4.：Compound 4 removes Boc protecting groups prepare compound 5, reaction temperature in chloroform-trifluoroacetic acid dicyandiamide solution
For room temperature, the reaction time is 0.5~5h；
By compound 4 with 1：110~130 (g：ML it) is dissolved in chloroform, reaction solution stirs at room temperature under the protection of argon gas
Then 5~20min is added with 1：15~25 (g：ML it is) trifluoroacetic acid of proportional quantities, reaction 0.5 is stirred at room temperature in reaction solution
~5h, is tracked using thin-layer chromatography, after 4 raw material point of compound completely disappears, stops reaction；Solvent is spin-dried for, silica gel is used in combination
Column filters, and obtains brown color compound 5；
Step is 5.：With nitroaryl aldehyde 7 condensation reaction occurs under the catalysis of trifluoroacetic acid for substituted pyrroles 6, recycles dichloro
Dicyano benzoquinone dehydrogenation finally adds triethylamine neutralization, is used in combination boron trifluoride ether coordination to prepare the fluorine boron containing nitro glimmering
The molar ratio of compound 8, nitroaryl aldehyde, substituted pyrroles and trifluoroacetic acid is 0.8~1.2：1.6~2.4：0.3~0.5,
Reaction temperature is room temperature, the reaction time is 8~for 24 hours；The molar ratio of nitroaryl aldehyde and dichlorocyanobenzoquinone is 0.8~1.2：
0.8~1.2, reaction temperature is room temperature, and the reaction time is 4~10h；Nitroaryl aldehyde, triethylamine and boron trifluoride ether are rubbed
You are than being 0.8~1.2：36~55：38~57, reaction temperature be 0~30 DEG C, the reaction time be 12~for 24 hours；
By compound 6 with 1：120~150 (g：ML it) is dissolved in anhydrous tetrahydro furan, adds compound 7 and tempestuously leads to
Argon gas 30 minutes, is promptly added trifluoroacetic acid, and reaction mixture continues in the presence of argon, to be stirred at room temperature 8~for 24 hours,
Until TLC plates show 7 disappearance；The mixed liquor of DDQ and anhydrous tetrahydro furan is slowly added dropwise with 1：12~15 (g：ML), after
4~10h of continuous stirring；Reaction solution is transferred under condition of ice bath, and Et is slowly added with constant pressure funnel3N, after stirring 5min,
It is slowly added into BF again3.OEt2；Continue stirring 12~for 24 hours at room temperature, stops reaction；Reaction solution dichloromethane and water are repeatedly
After extraction three times, it is dried overnight with anhydrous sodium sulfate；After being spin-dried for solvent, with pillar layer separation, the solid product of crocus is obtained
8；
Step is 6.：The glimmering compound of nitro fluorine boron 8 utilizes the catalysis of Pd/C in absolute ethyl alcohol, selects NH2NH2·H2It is prepared by O reduction
The glimmering compound 9 of amino fluorine boron, compound 8, Pd/C and NH2NH2·H2The molar ratio of O is 0.8~1.2：0.2~0.4：6.6~
10, reaction temperature is 80~100 DEG C, is reacted for 1~5h of time；
By compound 8 with 1：150~200 (g：ML it) is dissolved in absolute ethyl alcohol, adds NH2NH2·H2O and Pd/C；Reaction is mixed
Close object under conditions of argon gas, at 80~100 DEG C, react 1~5h, until TLC show 8 completely disappear until；Deng reaction liquid cooling
But to after room temperature, filtering removes catalyst；It after solvent is spin-dried for, is re-dissolved with dichloromethane, crosses post separation, obtain orange
Color solid 9；
Step is 7.：Under Catalyzed by Imidazole with acid anhydride 10 amidation process prepare compound 11 occurs for the glimmering compound 9 of amino fluorine boron, changes
The molar ratio for closing object 9, compound 10 and imidazoles is 0.8~1.2：1.0~1.8：10~15, reaction temperature is 70~90 DEG C, instead
It is 24~32h between seasonable；
By compound 9 with 1：400~500 (g：ML it) is dissolved in chloroform, adds compound 10 and imidazoles, reaction mixture
First lead to 5~20min of argon gas at room temperature, is then placed on again and is previously heated to react in 70~90 DEG C of oil bath pan；Utilize thin layer
Chromatogram tracking waits for that the consumption substantially of compound 9 is complete, stops reaction, after reaction solution is cooled to room temperature, is extracted, had with chloroform and water
Machine is mutually dried with anhydrous sodium sulfate, and then rotation removes solvent, with the isolated kermesinus product of TLC plates 11；
Step is 8.：Compound 5 occurs amidation process with compound 11 under Catalyzed by Imidazole and prepares target product P i.e. fullerene-
The molar ratio of the glimmering functional molecular of fluorine boron, compound 5, compound 11 and imidazoles is 1.6~2.4：0.8~1.2：10~15, instead
It is 70~90 DEG C to answer temperature, and the reaction time is 24~32h；
By compound 11 with 1：300~400 (g：ML it) is dissolved in chloroform, adds compound 5 and imidazoles, reaction mixture
First lead to 5~20min of argon gas at room temperature, is then placed on again and is previously heated to react in 70~90 DEG C of oil bath pan；Utilize thin layer
Chromatogram tracking waits for that the consumption substantially of compound 11 is complete, stops reaction, after reaction solution is cooled to room temperature, is extracted, had with chloroform and water
Machine is mutually dried with anhydrous sodium sulfate, is then revolved except solvent obtains kermesinus target product P with pillar layer separation.
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