CN105153735B - A kind of dye photoactivation agent and its preparation method and application - Google Patents

A kind of dye photoactivation agent and its preparation method and application Download PDF

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CN105153735B
CN105153735B CN201510514059.7A CN201510514059A CN105153735B CN 105153735 B CN105153735 B CN 105153735B CN 201510514059 A CN201510514059 A CN 201510514059A CN 105153735 B CN105153735 B CN 105153735B
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CN105153735A (en
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王鹏
张敏
吴恒
薛中原
姚朝阳
王俊婷
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention belongs to technical field of solar batteries, more particularly to a kind of dye photoactivation agent and its preparation method and application.The dye photoactivation agent that the present invention is provided has formula (I) structure；In formula (I), A is the substituent with formula (a) or formula (b) structure；E is the substituent with formula (c) or formula (d) structure；Wherein, R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R2、R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；X, y are each independently 0 or 1.Test result indicates that, the photoelectric transformation efficiency of DSSC prepared by the dye photoactivation agent provided using the present invention reaches as high as 13%, belongs to the current leading level in the world.

Description

A kind of dye photoactivation agent and its preparation method and application
Technical field
The invention belongs to technical field of solar batteries, more particularly to a kind of dye photoactivation agent and preparation method thereof and should With.
Background technology
Solar cell is can effectively to absorb solar energy, and converts it into the semiconductor devices of electric energy.Dye sensitization Solar cell has obtained the extensive concern in the world as important one kind in solar cell.Early in 1991,Grind Study carefully the three core ruthenium dye RuL that group reported Amadelli et al.2(μ-(CN)Ru(CN)L′2)2(L=2,2 '-bipyridyl -4, 4 '-dicarboxylic acids, L '=2,2 '-bipyridyl) as sensitizer, adsorb the high-quality TiO developed with great concentration for many years at them2Nano-crystal is thin Device is made on film, obtains under simulated solar irradiation 7.1% photoelectric transformation efficiency, has established DSSC Research foundation.Compared with traditional inorganic semiconductor solar cell, the manufacturing cost of DSSC is low, color Abundant, lighter in weight, it can fold, crimp so as to be widely applied in daily life.
DSSC is generally by transparent base layer, conductive layer, semiconductor micro-nano particle layer, dye coating, sky Cave transport layer and to electrode constitute, wherein, dye coating is the core of DSSC.Dye coating is generally by dyestuff light Sensitizer is made, but because the absorption spectrum of current dye photoactivation agent is narrow, it is relatively low to Solar use degree, cause existing dyestuff The photoelectric transformation efficiency of sensitization solar battery is relatively low.
The content of the invention
In view of this, it is an object of the invention to provide a kind of dye photoactivation agent and preparation method thereof and dye sensitization too Positive energy battery, has higher using the dye photoactivation agent that the present invention is provided as the DSSC of dye layer material Photoelectric transformation efficiency.
The invention provides a kind of dye photoactivation agent, with structure shown in formula (I)：
In formula (I), A is the substituent with formula (a) or formula (b) structure；E is the substitution with formula (c) or formula (d) structure Base；
Wherein, R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R2、 R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R6And R7Separately Selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；X, y are each independently 0 or 1.
It is preferred that, the R1、R’1And R3Separately it is selected from H, C2~C24Alkyl or C2~C24The hydrocarbon of alkoxy substitution Base；R2、R’2、R4、R5And R '5Separately it is selected from C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution；R6And R7Respectively Independently selected from H, F, C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution.
It is preferred that, the R1And R '1For C2~C24Alkoxy.
It is preferred that, the R2、R’2And R4Separately it is selected from C2~C24Alkyl.
It is preferred that, the R3For the substituent with formula (e) structure：
In formula (e), R8For C1~C18Alkoxy.
It is preferred that, the R5And R '5Separately it is selected from the substituent with formula (f) structure：
In formula (f), R9For C1~C18Alkyl.
It is preferred that, the dye photoactivation agent has formula (II)~structure shown in formula (XI)：
The invention provides a kind of preparation method of dye photoactivation agent, comprise the following steps：
Prodrug esters with formula (I-1) structure are hydrolyzed, and obtain the dye photoactivation agent with formula (I) structure；
In formula (I-1) and formula (I), A is the substituent with formula (a) or formula (b) structure；E is with formula (c) or formula (d) The substituent of structure；
Wherein, R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R2、 R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R6And R7Separately Selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R10For C1~C10Alkyl；X, y are each independently 0 or 1.
It is preferred that, the prodrug esters with formula (I-1) structure are prepared in accordance with the following methods：
Compound with formula (I-2) structure is reacted with the compound with formula (I-3) structure, is obtained with formula (I-1) prodrug esters of structure；
Or
Compound with formula (I-4) structure is reacted with the compound with formula (I-5) structure, is obtained with formula (I-1) prodrug esters of structure；
In formula (I-2)~formula (I-5), A is the substituent with formula (a) or formula (b) structure；R6And R7Separately select From H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R10For C1~C10Alkyl；X, y are each independently 0 or 1；Z is Halogen.
The invention provides a kind of DSSC, the dye coating of the DSSC is by upper The dye photoactivation agent described in technical scheme is stated to be made or the dyestuff light as made from the preparation method described in above-mentioned technical proposal Sensitizer is made.
Compared with prior art, the invention provides a kind of dye photoactivation agent and preparation method thereof and the dye sensitization sun Can battery.The dye photoactivation agent that the present invention is provided has formula (I) structure；In formula (I), A is with formula (a) or formula (b) structure Substituent；E is the substituent with formula (c) or formula (d) structure；Wherein, R1、R’1And R3Separately it is selected from H, C1~C36 Alkyl or C1~C36The alkyl of alkoxy substitution；R2、R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36 The alkyl of alkoxy substitution；R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；X, Y is each independently 0 or 1.The invention provides a kind of dye photoactivation agent with formula (I) structure, the dye photoactivation agent by In with special molecular structure, the dye photoactivation agent is set to show wider absorption spectrum and higher Solar use Degree, and then it is obviously improved the electricity conversion of DSSC.Test result indicates that, provided using the present invention The photoelectric transformation efficiency of DSSC prepared by dye photoactivation agent reaches as high as 13%, and category is leading in the world at present Level.
Embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment Only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model that the present invention is protected Enclose.
The invention provides a kind of dye photoactivation agent, with structure shown in formula (I)：
In formula (I), A is the substituent with formula (a) or formula (b) structure；E is the substitution with formula (c) or formula (d) structure Base；
Wherein, R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R2、 R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R6And R7Separately Selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；X, y are each independently 0 or 1.
The dye photoactivation agent that the present invention is provided has formula (I) structure：
Wherein, A is the substituent with formula (a) or formula (b) structure：
In formula (a), R1And R '1Separately it is selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；At this Invent in the one embodiment provided, R1And R '1Separately it is selected from H, C2~C24Alkyl or C2~C24The hydrocarbon of alkoxy substitution Base；In another embodiment that the present invention is provided, R1And R '1Separately it is selected from H, C2~C24Alkyl or C2~C24Alcoxyl Base；In the other embodiment that the present invention is provided, R1And R '1Separately it is selected from C2~C24Alkoxy；There is provided in the present invention In other embodiment, R1And R '1Separately it is selected from C2~C12Alkoxy；In the other embodiment that the present invention is provided, R1With R’1Separately it is selected from ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, epoxide in heptan, octyloxy, nonyl epoxide, last of the ten Heavenly stems oxygen Base, hendecane epoxide or dodecyloxy；In the other embodiment that the present invention is provided, R1And R '1It is separately following knot One kind in structure substituent：
——O——C2H5、——O——C3H7、——O——C4H9、——O——C5H11、——O—— C6H13、——O——C7H15、——O——C8H17、——O——C9H19With --- O --- C10H21。
In formula (a), R2And R '2Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；In this hair In one embodiment of bright offer, R2And R '2Separately it is selected from C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution； In another embodiment that the present invention is provided, R2And R '2Separately it is selected from C2~C24Alkyl or C2~C24Alkoxy； In the other embodiment that the present invention is provided, R2And R '2Separately it is selected from C2~C24Alkyl；Other realities provided in the present invention Apply in example, R2And R '2Separately it is selected from C2~C12Alkyl；In the other embodiment that the present invention is provided, R2And R '2Respectively Independently selected from ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl； In the other embodiment that the present invention is provided, R2And R '2It is separately one kind in following structure substituent：
——C2H5、——C3H7、——C4H9、——C5H11、——C6H13、——C7H15、C8H17、——C9H19 With --- C10H21。
In formula (b), R3For H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；The reality provided in the present invention Apply in example, R3For H, C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution；In another embodiment that the present invention is provided, R3For the substituent with formula (e) structure：
In formula (e), R8For C1~C18Alkoxy, be specially：Methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, oneself Epoxide, epoxide in heptan, octyloxy, nonyl epoxide, decyloxy, hendecane epoxide, dodecyloxy, tridecane epoxide, tetradecyloxyaniline, Pentadecane epoxide, hexadecane epoxide, heptadecane epoxide or octadecane epoxide.In one embodiment that the present invention is provided, R8For One kind in following structure substituent：
——O——C2H5、——O——C3H7、——O——C4H9、——O——C5H11、——O—— C6H13、——O——C7H15、——O——C8H17、——O——C9H19、——O——C10H21、
In formula (b), R4For C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；The implementation provided in the present invention In example, R4For C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution；In another embodiment that the present invention is provided, R4For C2~C24Alkyl or C2~C24Alkoxy；In the other embodiment that the present invention is provided, R4For C2~C24Alkyl；Carried in the present invention In the other embodiment of confession, R4For C2~C18Alkyl；In the other embodiment that the present invention is provided, R4For ethyl, propyl group, butyl, Amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, ten Six alkyl, heptadecyl or octadecyl；In the other embodiment that the present invention is provided, R4For one in following structure substituent Kind：
In formula (b), R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；In this hair In one embodiment of bright offer, R5And R '5Separately it is selected from C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution； In another embodiment that the present invention is provided, R5And R '5Separately it is selected from the substituent with formula (f) structure：
In formula (f), R9For C1~C18Alkyl, be specially：It is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, pungent Base, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl or Octadecyl；In one embodiment that the present invention is provided, R9It independently is one kind in following structure substituent：
——C2H5、——C3H7、——C4H9、——C5H11、——C6H13、——C7H15、C8H17、——C9H19 With --- C10H21。
In formula (I), x, y is each independently 0 or 1.R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36Alkane The alkyl of epoxide substitution；In one embodiment that the present invention is provided, R6And R7Independently selected from H, F, C2~C24Alkyl or C2~ C24The alkyl of alkoxy substitution；In another embodiment that the present invention is provided, R6And R7Independently selected from H, F, C2~C12Hydrocarbon Base or C2~C12The alkyl of alkoxy substitution；In the other embodiment that the present invention is provided, R6And R7Independently selected from H, F, C2~ C12Alkyl or C2~C12Alkoxy.
In the present invention, in formula (I), E is the substituent with formula (c) or formula (d) structure：
In one embodiment that the present invention is provided, the dye photoactivation agent with formula (I) structure has formula (II) Structure shown in~formula (XI)：
The invention provides a kind of dye photoactivation agent with formula (I) structure, the dye photoactivation agent is due to spy Different molecular structure, makes the dye photoactivation agent show wider absorption spectrum and higher Solar use degree, Jin Erxian Write the photoelectric transformation efficiency of lifting DSSC.Test result indicates that, such dyestuff can effectively utilize the sun Light, is obviously improved the short-circuit current density of device to lift the photoelectric transformation efficiency of DSSC.Using this The agent of class dye photoactivation prepare DSSC highest photoelectric transformation efficiency up to 13%, be the current world most High efficiency.
The invention provides a kind of preparation method of dye photoactivation agent, comprise the following steps：
Prodrug esters with formula (I-1) structure are hydrolyzed, and obtain the dye photoactivation agent with formula (I) structure；
In formula (I-1) and formula (I), A is the substituent with formula (a) or formula (b) structure；E is with formula (c) or formula (d) The substituent of structure；
Wherein, R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R2、 R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R6And R7Separately Selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R10For C1~C10Alkyl；X, y are each independently 0 or 1.
In the preparation method that the present invention is provided, directly the prodrug esters with formula (I-1) structure are hydrolyzed, you can To the dye photoactivation agent with formula (I) structure, the process is specially：
The prodrug esters that will have formula (I-1) structure first are mixed with alkali compounds and solvent, carry out basic hydrolysis.Its In, the prodrug esters with formula (I-1) structure have following structure：
In formula (I-1), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution； R10For C1~C10Alkyl；X, y are each independently 0 or 1；A is the substituent with formula (a) or formula (b) structure；E is with formula (c) Or the substituent of formula (d) structure；
In formula (a) and formula (b), R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~C36Alkoxy replaces Alkyl；R2、R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；
The source of the prodrug esters with formula (I-1) structure is not particularly limited the present invention, can be according to lower section It is prepared by method：
Compound with formula (I-2) structure is reacted with the compound with formula (I-3) structure, is obtained with formula (I-1) prodrug esters of structure；
In formula (I-2) and formula (I-3), A is the substituent with formula (a) or formula (b) structure；R6And R7Separately select From H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R10For C1~C10Alkyl；Y is 0 or 1；Z is halogen.
In the preparation method for the above-mentioned prodrug esters with formula (I-1) structure that the present invention is provided, will directly have formula (I- 2) compound of structure is reacted with the compound with formula (I-3) structure, you can obtain the precursor with formula (I-1) structure Ester, the process is specially：
The compound with formula (I-2) structure is mixed with the compound with formula (I-3) structure, reacted.Wherein, The compound with formula (I-2) structure is specially formula (I-2-1) or formula (I-2-2) structure：
In formula (I-2-1) and formula (I-2-2), R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~C36Alkane The alkyl of epoxide substitution；R2、R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The hydrocarbon of alkoxy substitution Base；Z is halogen, preferably Cl, Br or I.
The source of the compound with formula (I-2-1) or formula (I-2-2) structure is not particularly limited the present invention, institute The compound with formula (I-2-1) structure is stated preferably to prepare in accordance with the following methods：
Compound with formula (I-4-1) structure is reacted with halogenating agent, obtains the chemical combination with formula (I-2-1) structure Thing；
In formula (I-4-1), R1And R '1Separately it is selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution； R2And R '2Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution.
In the preparation method for the above-mentioned compound with formula (I-2-1) structure that the present invention is provided, will directly have formula (I-4-1) compound of structure is reacted with halogenating agent, you can obtain the compound with formula (I-2-1) structure, the process Specially：
The compound that will have formula (I-4-1) structure first is mixed with halogenating agent, is reacted.Wherein, it is described that there is formula (I-4-1) structure of the compound of structure is as follows：
In formula (I-4-1), R1And R '1Separately it is selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution, It preferably is selected from H, C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution, more preferably from H, C2~C24Alkyl or C2~C24Alcoxyl Base, most preferably from C2~C24Alkoxy, preferably the most is selected from C2~C12Alkoxy.In one embodiment that the present invention is provided, R1 And R '1Separately it is selected from ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, epoxide in heptan, octyloxy, nonyl epoxide, the last of the ten Heavenly stems Epoxide, hendecane epoxide or dodecyloxy；In another embodiment that the present invention is provided, R1And R '1Separately for such as One kind in lower structure substituent：——O——C2H5、——O——C3H7、——O——C4H9、——O—— C5H11、——O——C6H13、——O——C7H15、——O——C8H17、——O——C9H19With --- O --- C10H21。
In formula (I-4-1), R2And R '2Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution, it is excellent Selected from C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution, more preferably from C2~C24Alkyl or C2~C24Alkoxy, it is optimal Selected from C2~C24Alkyl, preferably the most is selected from C2~C12Alkyl.In one embodiment that the present invention is provided, R2And R '2Independently Ground is selected from ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl or dodecyl；In this hair In another embodiment of bright offer, R2And R '2It is separately one kind in following structure substituent：——C2H5、—— C3H7、——C4H9、——C5H11、——C6H13、——C7H15、C8H17、——C9H19With --- C10H21。
In one embodiment that the present invention is provided, the compound with formula (I-4-1) structure is specially formula (I-4- 1-a) structure, formula (I-4-1-b) structure or formula (I-4-1-c) structure：
In the present invention, the source of the compound with (I-4-1) structure is not particularly limited, city can be used Commodity are sold, can also be according to document (M.Zhang, Y.Wang, M.Xu, W.Ma, R.Li, P.Wang, Energy Environ.Sci., 2013,6,2944) synthesize.
In the present invention, during the compound with formula (I-4-1) structure and halogenating agent hybrid reaction, the halogen Agent is preferably N- bromo-succinimides (NBS).The mol ratio of the compound and halogenating agent with formula (I-4-1) structure Preferably 1：0.5~2, more preferably 1:1~1.5, most preferably 1：1.2~1.3.The reaction is preferably entered in organic solvent OK, the organic solvent is preferably tetrahydrofuran.The reaction is carried out preferably in inert gas atmosphere, and the inert gas is excellent Elect argon gas as.The temperature of the reaction is preferably room temperature.The time of shown reaction is preferably 0.5~3h, more preferably 0.5~ 1.5h.After reaction terminates, the solution containing reaction product is obtained.The solution containing reaction product is post-processed, obtained To the compound with formula (I-2-1) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, dry and concentration after, obtain the compound with formula (I-2-1) structure.Described be quenched makes Quencher is preferably water；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably anhydrous slufuric acid Sodium.
In the present invention, the compound with formula (I-2-2) structure is preferably prepared in accordance with the following methods：
Compound with formula (I-4-2) structure is reacted with halogenating agent, obtains the chemical combination with formula (I-2-2) structure Thing；
In formula (I-4-2), R3Selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R4、R5And R '5Respectively Independently selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution.
In the preparation method for the above-mentioned compound with formula (I-2-2) structure that the present invention is provided, will directly have formula (I-4-2) compound of structure is reacted with halogenating agent, you can obtain the compound with formula (I-2-2) structure, the process Specially：
The compound that will have formula (I-4-2) structure first is mixed with halogenating agent, is reacted.Wherein, it is described that there is formula (I-4-2) structure of the compound of structure is as follows：
In formula (I-4-2), R3Selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R4、R5And R '5Respectively Independently selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution..
In the present invention, the source of the compound with formula (I-4-2) structure is not particularly limited, preferably according to It is prepared by following methods：
Compound with formula (I-5.1) structure carries out intramolecular cyclization reaction under the conditions of acidic catalyst, is had There is the compound of formula (I-4-2) structure；
In formula (I-5.1), R3Selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R4、R5And R '5Respectively Independently selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution.
In the preparation method for the above-mentioned compound with formula (I-4-2) structure that the present invention is provided, will directly have formula (I-5.1) compound of structure carries out intramolecular cyclization reaction under the conditions of acidic catalyst, you can obtain with formula (I-4-2) The compound of structure, the process is specially：
The compound that will have formula (I-5.1) structure first is mixed with acidic catalyst, is reacted.Wherein, it is of the invention The source of the compound with formula (I-5.1) structure is not particularly limited, preferably prepared in accordance with the following methods：
The compound with formula (I-6) structure and compound and formula (I-7-2) structure with formula (I-7-1) structure Compound reacted, obtain the compound with formula (I-5.1) structure；
In formula (I-6), R3Selected from H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution, R4Selected from C1~C36Alkyl Or C1~C36The alkyl of alkoxy substitution；R11For C1~C10Alkyl.
R5--- Mg-Z formulas (I-7-1)；R'5--- Mg-Z formulas (I-7-2)；
In formula (I-7-1) and formula (I-7-2), Z is halogen, preferably Br or I；R5And R '5Independently selected from C1~C36Alkyl Or C1~C36The alkyl of alkoxy substitution.
In the preparation method for the above-mentioned compound with formula (I-5.1) structure that the present invention is provided, will directly have formula (I-6) compound of structure is reacted with compound and the compound of formula (I-7-2) structure with formula (I-7-1) structure, The compound with formula (I-6) structure can be obtained, the process is specially：
By the compound with formula (I-6) structure and compound and formula (I-7-2) structure with formula (I-7-1) structure Compound is mixed, and is reacted.Wherein, the compound with formula (I-6) structure has following structure：
In formula (I-6), R3For H, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution, preferably R3For H, C2~C24 Alkyl or C2~C24The alkyl of alkoxy substitution, the more preferably substituent with formula (e) structure：
In formula (e), R8For C1~C18Alkoxy, be specially：Methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, oneself Epoxide, epoxide in heptan, octyloxy, nonyl epoxide, decyloxy, hendecane epoxide, dodecyloxy, tridecane epoxide, tetradecyloxyaniline, Pentadecane epoxide, hexadecane epoxide, heptadecane epoxide or octadecane epoxide.In one embodiment that the present invention is provided, R8For One kind in following structure substituent：——O-C2H5、——O-C3H7、——O-C4H9、——O-C5H11、——O- C6H13、——O-C7H15、——O-C8H17、——O-C9H19、——O-C10H21、
In formula (I-6), R4For C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution, preferably C2~C24Alkyl or C2 ~C24The alkyl of alkoxy substitution, more preferably C2~C24Alkyl or C2~C24Alkoxy, most preferably C2~C24Alkyl, the most Preferably C2~C18Alkyl.In one embodiment that the present invention is provided, R4For ethyl, propyl group, butyl, amyl group, hexyl, heptan Base, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, 17 Alkyl or octadecyl；In another embodiment that the present invention is provided, R4For one kind in following structure substituent：
In formula (I-6), R11For C1~C10Alkyl, be specially：——CH3、——C2H5、——C3H7、——C4H9、—— C5H11、——C6H13、——C7H15、C8H17、——C9H19Or --- C10H21。
In one embodiment that the present invention is provided, the compound with formula (I-6) structure is specially to have formula (I- 6-a) the compound of structure：
In the present invention, the source of the compound with formula (I-6) structure is not particularly limited, city can be selected Sell commodity, can also according to document (Zhaoyang.Yao, Min Zhang, Renzhi Li, Lin Yang, Yongna Qiao, Peng Wang Angew.Chem.Int.Ed.2015,54,5994) synthesis obtain.
In the present invention, the compound with formula (I-6) structure and compound and formula with formula (I-7-1) structure (I-7-2) during the compound hybrid reaction of structure, the compound tool with formula (I-7-1) and formula (I-7-2) structure There is following structure：
R5--- Mg-Z formulas (I-7-1)；R'5--- Mg-Z formulas (I-7-2)；
In formula (I-7-1) and formula (I-7-2), Z is halogen, preferably Br or I；R5And R '5Separately it is selected from C1~C36 Alkyl or C1~C36The alkyl of alkoxy substitution, preferably is selected from C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution, more preferably For the substituent with formula (f) structure：
In formula (f), R9For C1~C18Alkyl, be specially：It is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, pungent Base, nonyl, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl or Octadecyl；In one embodiment that the present invention is provided, R9It independently is one kind in following structure substituent：—— C2H5、——C3H7、——C4H9、——C5H11、——C6H13、——C7H15、C8H17、——C9H19With --- C10H21。
In one embodiment that the present invention is provided, the compound with formula (I-7-1) and formula (I-7-2) structure is equal For to hexyl benzene magnesium bromide, its structure such as formula (I-7-a) is shown：
In the present invention, the source of the compound with formula (I-7-1) and formula (I-7-2) structure is not limited especially It is fixed, from commercial goods.
In the present invention, the compound with formula (I-6) structure and compound and formula with formula (I-7-1) structure (I-7-2) during the compound hybrid reaction of structure, the compound with (I-7-1) structure and with formula (I-7-2) The integral molar quantity of the compound of structure is preferably 5~20 with having the mol ratio of the compound of formula (I-6) structure：1, more preferably 8~12：1.The reaction is preferably carried out in organic solvent, and the organic solvent is preferably tetrahydrofuran.The reaction is preferred Carried out in inert gas atmosphere, the inert gas is preferably argon gas.In the present invention, it is preferred to will first have (I-6) respectively The compound of structure and compound with formula (I-7-1) and formula (I-7-2) structure are dissolved with organic solution respectively, Ran Houzai Solution after dissolving is mixed, reacted.The temperature of the reaction is preferably 80~100 DEG C, more preferably 90~95 DEG C.Institute The time for stating reaction is preferably 10~24h, more preferably 12~16h.After reaction terminates, the solution containing reaction product is obtained. The solution containing reaction product is post-processed, the compound with formula (I-5.1) structure is obtained.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, dry and concentration after, obtain the compound with formula (I-5.1) structure.Described be quenched makes Quencher is preferably water；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably anhydrous slufuric acid Sodium.
In the present invention, during the compound with formula (I-5.1) structure and acidic catalyst hybrid reaction, The acidic catalyst is preferably sulfonic acid type catalyst, and the model of the sulfonic acid type catalyst is preferably Amberlyst-15.Institute Catalyst is stated with preparing the raw material of the compound with formula (I-5.1) structure, i.e., the compound with formula (I-6) structure Amount ratio is preferably 1 (g)：0.5~3 (mmol), more preferably 1 (g)：0.9~1.1 (mmol).The reaction is preferably organic Carried out in solvent, the organic solvent is preferably toluene.The reaction is carried out preferably in inert gas atmosphere, the indifferent gas Body is preferably argon gas.The preferred back flow reaction of mode of the reaction.The time of the reaction is preferably 10~24h, more preferably 12~16h.After reaction terminates, the solution containing reaction product is obtained.The solution containing reaction product is post-processed, Obtain the compound with formula (I-4-2) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, drying, concentrating and column chromatography after, obtain the compound with formula (I-4-2) structure.Institute State and the quencher used preferably water is quenched；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably Anhydrous sodium sulfate；The solvent of the column chromatography is preferably petroleum ether.
In the present invention, during the compound with formula (I-4-2) structure and halogenating agent hybrid reaction, the halogen Agent is preferably N- bromo-succinimides (NBS).The mol ratio of the compound and halogenating agent with formula (I-4-2) structure Preferably 1：0.5~2, more preferably 1:1~1.5, most preferably 1：1.2~1.3.The reaction is preferably entered in organic solvent OK, the organic solvent is preferably tetrahydrofuran.The reaction is carried out preferably in inert gas atmosphere, and the inert gas is excellent Elect argon gas as.The temperature of the reaction is preferably room temperature.The time of shown reaction is preferably 0.5~3h, more preferably 0.5~ 1.5h.After reaction terminates, the solution containing reaction product is obtained.The solution containing reaction product is post-processed, obtained To the compound with formula (I-2-2) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, dry and concentration after, obtain the compound with formula (I-2-2) structure.Described be quenched makes Quencher is preferably water；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably anhydrous slufuric acid Sodium.
In the present invention, the compound with formula (I-2) structure is mixed instead with the compound with formula (I-3) structure During answering, the compound with formula (I-3) structure has formula (I-3-1) or formula (I-3-2) structure：
In formula (I-3-1) and formula (I-3-2), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36Alcoxyl The alkyl of base substitution；R10For C1~C10Alkyl；Y is 0 or 1.
In the present invention, the compound with formula (I-3-1) structure is specially the change with formula (I-3-1-1) structure Compound or the compound with formula (I-3-1-2) structure：
In formula (I-3-1-1), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The hydrocarbon of alkoxy substitution Base, preferably is selected from H, F, C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution, more preferably from H, F, C2~C12Alkyl or C2~ C12The alkyl of alkoxy substitution, most preferably from H, F, C2~C12Alkyl or C2~C12Alkoxy.R10For C1~C10Alkyl, specifically For：——CH3、——C2H5、——C3H7、——C4H9、——C5H11、——C6H13、——C7H15、C8H17、——C9H19 Or --- C10H21。
In one embodiment that the present invention is provided, the compound with formula (I-3-1-1) structure is specially to have (I-3-1-1-a) compound of structure：
The source of compound with formula (I-3-1-1) structure is not particularly limited the present invention, can use commercially available business Product, can also according to document (L.Yang, Y.Ren, Z.Yao, C.Yan, W.Ma, P.Wang, J.Phys.Chem.C 2015, 119,980.) synthesis obtain.
In formula (I-3-1-2), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The hydrocarbon of alkoxy substitution Base, R10For C1~C10Alkyl.The source of compound with formula (I-3-1-2) structure is not particularly limited the present invention, preferably Prepare in accordance with the following methods：
The compound with formula (I-8) structure is reacted with the compound with formula (I-9) structure first, had There is the compound of formula (I-10) structure；Then the compound of formula (I-10) structure and tetrabutyl ammonium fluoride described will carry out anti- Should, obtain the compound with formula (I-3-1-2) structure；
In formula (I-8), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution, R10For C1~C10Alkyl, Z is halogen, preferably Br or I.
In formula (I-9), R12、R13And R14Separately it is selected from C1~C10Alkyl；
In the preparation method for the above-mentioned compound with formula (I-3-1-2) structure that the present invention is provided, will have first The compound of formula (I-8) structure is mixed with the compound with formula (I-9) structure, is reacted.Wherein, the present invention is to the tool The source for having the compound of formula (I-8) structure is not particularly limited, and can use commercial goods, can also make in accordance with the following methods It is standby：
Compound with formula (I-11) structure is reacted with the compound with formula (I-12) structure, is obtained with formula (I-8) compound of structure；
In formula (I-11), R10For C1~C10Alkyl；
In formula (I-12), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution, Z is halogen, preferably Br or I.
In the preparation method for the above-mentioned compound with formula (I-8) structure that the present invention is provided, will directly have formula (I- 11) compound of structure is reacted with the compound with formula (I-12) structure, you can obtain the change with formula (I-8) structure Compound, the process is specially：
The compound with formula (I-11) structure is mixed with the compound with formula (I-12) structure first, carried out anti- Should.Wherein, the compound with formula (I-11) structure has following structure：
In formula (I-11), R10For C1~C10Alkyl, be specially：——CH3、——C2H5、——C3H7、—— C4H9、——C5H11、——C6H13、——C7H15、C8H17、——C9H19Or --- C10H21。
In one embodiment that the present invention is provided, the compound with formula (I-11) structure is specially formula (I-11- A), formula (I-11-b) or formula (I-11-c) structure：
The source of the compound with formula (I-11) structure is not particularly limited the present invention, can use commercially available business Product, it would however also be possible to employ prepared by method well known in the art.
In the present invention, the compound with formula (I-11) structure is mixed with the compound with formula (I-12) structure During reaction, the compound with formula (I-12) structure has following structure：
In formula (I-12), Z is halogen, preferably Br or I；R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1 ~C36The alkyl of alkoxy substitution, preferably is selected from H, F, C2~C24Alkyl or C2~C24Alkoxy substitution alkyl, more preferably from H, F、C2~C12Alkyl or C2~C12The alkyl of alkoxy substitution, most preferably from H, F, C2~C12Alkyl or C2~C12Alkoxy.
In one embodiment that the present invention is provided, the compound with formula (I-12) structure is specially 4,7- dibromos Diazosulfide, its structure is as follows：
The source of the compound with formula (I-12) structure is not particularly limited the present invention, can use commercially available business Product, it would however also be possible to employ prepared by method well known in the art.
In the present invention, the compound with formula (I-11) structure is mixed with the compound with formula (I-12) structure During reaction, the mol ratio of the compound with formula (I-11) structure and the compound with formula (I-12) structure is excellent Elect 1 as：0.5~2, more preferably 1：1~1.2.The reaction is preferably carried out in the presence of a catalyst, and the catalyst is preferably Pd(PPh3)2Cl2, triphenylphosphine, the one or more in cuprous iodide and diisopropylamine, more preferably Pd (PPh3)2Cl2、 Triphenylphosphine, cuprous iodide and diisopropylamine.Pd (PPh in catalyst3)2Cl2, triphenylphosphine, cuprous iodide and diisopropyl The mass ratio of amine is preferably 60~70：40~50：10~20：2~3.The catalyst and the chemical combination with formula (I-11) structure The amount ratio of thing is preferably：4~5 (mmol)：100~150 (mg).The reaction is preferably carried out in organic solvent, described to have Machine solvent is preferably toluene.The temperature of the reaction is preferably 70~90 DEG C.The time of the reaction is preferably 10~24h, more Preferably 12~16h.After reaction terminates, the solution containing reaction product is obtained.The solution containing reaction product is carried out Post processing, obtains the compound with formula (I-8) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, drying, concentrating and column chromatography after, obtain the compound with formula (I-8) structure.It is described The quencher used preferably water is quenched；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably nothing Aqueous sodium persulfate；The solvent of the column chromatography is preferably chloroform and/or petroleum ether, and more preferably volume ratio is 3:1 chloroform and Petroleum ether.
In the present invention, the compound with formula (I-8) structure is mixed instead with the compound with formula (I-9) structure During answering, the compound with formula (I-9) structure has following structure：
In formula (I-9), R12、R13And R14Separately it is selected from C1~C10Alkyl, be specially：Methyl, ethyl, propyl group, fourth Base, amyl group, hexyl, heptyl, octyl group, nonyl or decyl.
In one embodiment that the present invention is provided, the compound with formula (I-9) structure is specially triisopropyl Silicon substrate acetylene or trimethyl silicane ethyl-acetylene, shown in the structure such as formula (I-9-a) of the triisopropylsilyl acetylene, the trimethyl Shown in the structure of silicon substrate acetylene such as formula (I-9-b)：
The source of the compound with formula (I-9) structure is not particularly limited the present invention, can use commercially available business Product, can also be prepared according to method well known to those skilled in the art.
In the present invention, the compound with formula (I-8) structure is mixed instead with the compound with formula (I-9) structure During answering, the mol ratio of the compound with formula (I-8) structure and the compound with formula (I-9) structure is preferably 1： 1~10, more preferably 1：2~4.The reaction is preferably carried out in the presence of a catalyst, and the catalyst is preferably Pd (PPh3)2Cl2, triphenylphosphine, the one or more in cuprous iodide and diisopropylamine, more preferably Pd (PPh3)2Cl2, triphenylphosphine, Cuprous iodide and diisopropylamine.Pd (PPh in catalyst3)2Cl2, triphenylphosphine, the quality of cuprous iodide and diisopropylamine Than being preferably 30~40：20~30：5~15：2~3.The catalyst and the amount ratio of the compound with formula (I-10) structure Preferably：2~3 (mmol)：60~80 (mg).The reaction is preferably carried out in organic solvent, and the organic solvent is preferably Toluene.The temperature of the reaction is preferably 70~90 DEG C.The time of the reaction is preferably 10~24h, more preferably 12~ 16h.After reaction terminates, the solution containing reaction product is obtained.The solution containing reaction product is post-processed, obtained Compound with formula (I-10) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, dry and concentration after, obtain the compound with formula (I-10) structure.Described be quenched makes Quencher is preferably water；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably anhydrous slufuric acid Sodium.
The compound with formula (I-10) structure is obtained, the compound with formula (I-10) structure is fluorinated with the tetrabutyl Ammonia is mixed, and is reacted.Wherein, raw material of the tetrabutyl ammonium fluoride with preparing the compound with formula (I-10) structure, i.e., The mol ratio of compound with formula (I-8) structure is preferably 2~20：1, more preferably 5~10：1.The reaction is preferably having Carried out in machine solvent, the organic solvent is preferably dichloromethane.The temperature of the reaction is preferably room temperature.The reaction when Between be preferably 10~24h, more preferably 12~16h.After reaction terminates, the solution containing reaction product is obtained.Contain to described The solution of reaction product is post-processed, and obtains the compound with formula (I-3-1-2) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, drying, concentrating and column chromatography after, obtain the compound with formula (I-3-1-2) structure. It is described that the quencher used preferably water is quenched；The extractant of the extraction is preferably chloroform；The drier of the drying is preferred For anhydrous sodium sulfate；The solvent of the column chromatography is preferably chloroform and/or petroleum ether, and more preferably volume ratio is 3:1 chlorine Imitative and petroleum ether.
In the present invention, the compound with formula (I-2) structure is mixed instead with the compound with formula (I-3) structure During answering, the compound with formula (I-3) structure has formula (I-3-1) or formula (I-3-2) structure.Wherein, the tool The compound for having formula (I-3-2) structure is specially to have the compound of formula (I-3-2-1) structure or with formula (I-3-2-2) structure Compound：
In formula (I-3-2-1) and formula (I-3-2-2), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36 The alkyl of alkoxy substitution, preferably is selected from H, F, C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution, more preferably from H, F, C2 ~C12Alkyl or C2~C12The alkyl of alkoxy substitution, most preferably from H, F, C2~C12Alkyl or C2~C12Alkoxy.R10For C1 ~C10Alkyl, be specially：——CH3、——C2H5、——C3H7、——C4H9、——C5H11、——C6H13、——C7H15、 C8H17、——C9H19Or --- C10H21。
The source of compound with formula (I-3-2-1) and formula (I-3-2-2) structure is not particularly limited the present invention, can To use commercial goods, it can also be prepared according to method well known to those skilled in the art.
In the present invention, the compound with formula (I-2) structure is mixed instead with the compound with formula (I-3) structure During answering, the raw material of the compound of compound and preparation with formula (I-2) structure with formula (I-3) structure, i.e., with formula (I-4-1) mol ratio of compound or the compound with formula (I-4-2) is preferably 0.5~3：1, more preferably 1~2：1, Most preferably 1.4~1.6：1.The reaction is preferably carried out in organic solvent, and the organic solvent is preferably dioxane.Institute State reaction preferably to carry out in the presence of a catalyst, the catalyst is preferably Pd2(dba)3、P(t-Bu)3And Cs2CO3It is middle a kind of or It is a variety of, more preferably Pd2(dba)3、P(t-Bu)3And Cs2CO3.Pd in the catalyst2(dba)3、P(t-Bu)3And Cs2CO3's Amount ratio is preferably 5~20 (mg)：0.01~0.1 (mL)：30~100 (mg), more preferably 8~12 (mg)：0.02~0.03 (mL)：60~80 (mg).Pd in the catalyst2(dba)3Raw material with preparing the compound with formula (I-2) structure, i.e., The amount ratio of compound with formula (I-4-1) or the compound with formula (I-4-2) is preferably 8~12 (mg)：1(mmol). The reaction is carried out preferably in inert gas atmosphere, and the inert gas is preferably argon gas.The mode of the reaction is preferably Back flow reaction.The time of shown reaction is preferably 10~24h, more preferably 12~16h.After reaction terminates, obtain containing reaction The solution of product.The solution containing reaction product is post-processed, the prodrug esters with formula (I-1) structure are obtained.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, drying, concentrating and column chromatography after, obtain the prodrug esters with formula (I-1) structure.It is described The quencher used preferably water is quenched；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably nothing Aqueous sodium persulfate；The solvent of the column chromatography is preferably toluene and/or petroleum ether, and more preferably volume ratio is 2:1 toluene and Petroleum ether.
In the present invention, the prodrug esters with formula (I-1) structure can also be prepared in accordance with the following methods：
Compound with formula (I-4) structure is reacted with the compound with formula (I-5) structure, is obtained with formula (I-1) prodrug esters of structure；
A --- H formulas (I-4)；
In formula (I-4) and formula (I-5), A is the substituent with formula (a) or formula (b) structure；R6And R7Separately select From H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R10For C1~C10Alkyl；Y is 0 or 1；Z is halogen.
In the preparation method for the above-mentioned prodrug esters with formula (I-1) structure that the present invention is provided, will directly have formula (I- 4) compound of structure is reacted with the compound with formula (I-5) structure, you can obtain the precursor with formula (I-1) structure Ester, the process is specially：
To have the compound of formula (I-4) structure and lithiumation agent to react first, and obtain lithiation liquid；The lithiation Liquid reacts with tin agent, obtains the compound with formula (I-13) structure；
In formula (I-13), J1、J2And J3Separately it is selected from C1~C10Alkyl；A is with formula (a) or formula (b) structure Substituent；
In formula (a) and formula (b), wherein, R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~C36Alkoxy Substituted alkyl；R2、R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution.
In the preparation method for the above-mentioned compound with formula (I-13) structure that the present invention is provided, there will be formula first (I-4) compound of structure is mixed with lithiumation agent, is reacted.Wherein, the compound with formula (I-4) structure has formula Or formula (I-4-2) structure (I-4-1)：
In formula (I-4-1) and formula (I-4-2), wherein, R1、R’1And R3Separately it is selected from H, C1~C36Alkyl or C1~ C36The alkyl of alkoxy substitution；R2、R’2、R4、R5And R '5Separately it is selected from C1~C36Alkyl or C1~C36Alkoxy replaces Alkyl.
The concrete structure of the compound with formula (I-4-1) or formula (I-4-2) structure and source are hereinbefore Introduce, will not be repeated here.The lithiumation agent is preferably butyl lithium, more preferably n-BuLi.The lithiumation agent is with having formula (I-4) mol ratio of the compound of structure is preferably 0.5~2：1, more preferably 1.4~1.6：1.The reaction is preferably organic Carried out in solvent, the organic solvent is preferably tetrahydrofuran.The reaction is carried out preferably in inert gas atmosphere, described lazy Property gas is preferably argon gas.The temperature of the reaction is preferably -60~-90 DEG C, more preferably -78~-80 DEG C.The reaction Time is preferably 0.5~2h, more preferably 1~2h.After reaction terminates, lithiation liquid is obtained.The lithiation liquid and tin Agent is mixed, and is reacted.Wherein, the tin agent is preferably trialkyl tin halides, and its structure is as follows：
In above formula, J1、J2And J3Separately it is selected from C1~C10Alkyl, preferably be selected from C1~C3Alkyl；Z is halogen, Preferably Cl, Br or I.
In one embodiment that the present invention is provided, the tin agent is specially trimethyltin chloride, the following institute of its structure Show：
During the lithiation liquid and tin agent hybrid reaction, the tin agent and the change with formula (I-4) structure The mol ratio 0.5~2 of compound：1, more preferably 1.4~1.6：1.The reaction is carried out preferably in inert gas atmosphere, described Inert gas is preferably argon gas.The temperature of the reaction is preferably room temperature.The time of the reaction is preferably 8~20h, more preferably For 10~15h.After reaction terminates, the solution containing reaction product is obtained.The solution containing reaction product passes through post processing, Obtain the compound with formula (I-13) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, dry and concentration after, obtain the compound with formula (I-13) structure.Described be quenched makes Quencher is preferably water；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably anhydrous slufuric acid Sodium.
Obtain after the compound with formula (I-13) structure, described there will be the compound of formula (I-13) structure and with formula (I-5) the compound mixing of structure, is reacted.Wherein, the compound with formula (I-5) structure has formula (I-5-1) Or formula (I-5-2) structure：
In formula (I-5-1) and formula (I-5-2), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36Alcoxyl The alkyl of base substitution；R10For C1~C10Alkyl；Z is halogen, preferably Cl, Br or I；Y is 0 or 1.In the present invention, the tool The compound for having formula (I-5-1) structure is specially the compound of (I-5-1-a) structure or the compound of (I-5-1-b) structure：
In formula (I-5-1-a), Z is halogen, preferably Cl, Br or I；R6And R7Separately it is selected from H, F, C1~C36Hydrocarbon Base or C1~C36The alkyl of alkoxy substitution, preferably is selected from H, F, C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution, it is more excellent Selected from H, F, C2~C12Alkyl or C2~C12The alkyl of alkoxy substitution, most preferably from H, F, C2~C12Alkyl or C2~C12Alcoxyl Base；R10For C1~C10Alkyl, be specially：——CH3、——C2H5、——C3H7、——C4H9、——C5H11、—— C6H13、——C7H15、C8H17、——C9H19Or --- C10H21。
The source of the compound with (I-5-1-a) structure is not particularly limited the present invention, can use commercially available Commodity, can also be prepared according to method well known to those skilled in the art.
In formula (I-5-1-b), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The hydrocarbon of alkoxy substitution Base, R10For C1~C10Alkyl, Z is halogen, preferably Cl, Br or I.In the present invention, the chemical combination of formula (I-5-1-b) structure Thing is identical with the structure of the compound of above-mentioned formula (I-8) structure, will not be repeated here.
In the present invention, the compound with formula (I-5-2) structure be specially (I-5-2-a) structure compound or (I-5-2-b) compound of structure：
In formula (I-5-2-a) and formula (I-5-2-b), R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36 The alkyl of alkoxy substitution；R10For C1~C10Alkyl；Z is halogen, preferably Cl, Br or I.The present invention has formula (I- to described 5-2-a) source of the compound of structure and the compound with formula (I-5-2-b) structure is not particularly limited, and can select city Commodity are sold, can also be prepared according to method well known to those skilled in the art.
In the present invention, the compound with formula (I-5-2-a) structure is preferably prepared in accordance with the following methods：
Compound with formula (I-14) structure is reacted with the compound with formula (I-12) structure, is obtained with formula (I- 5-2-a) the compound of structure；
In formula (I-14), R10For C1~C10Alkyl.
In the preparation method for the above-mentioned compound with formula (I-5-2-a) structure that the present invention is provided, will directly have The compound of formula (I-14) structure is reacted with the compound with formula (I-12) structure, you can obtain tying with formula (I-5-2-a) The compound of structure, the process is specially：
The compound with formula (I-14) structure is mixed with the compound with formula (I-12) structure first, carried out anti- Should.Wherein, the compound with formula (I-14) structure has following structure：
In formula (I-14), R10For C1~C10Alkyl, be specially：——CH3、——C2H5、——C3H7、—— C4H9、——C5H11、——C6H13、——C7H15、C8H17、——C9H19Or --- C10H21。
In one embodiment that the present invention is provided, the compound with formula (I-14) structure is specially 2- carboxylic acid second Ester thiophene, its structure is as follows：
The source of the compound with formula (I-14) structure is not particularly limited the present invention, can use commercially available business Product, can also be prepared according to method well known to those skilled in the art.
In the present invention, the compound with formula (I-14) structure is mixed with the compound with formula (I-12) structure In course of reaction, the mol ratio of the compound with formula (I-14) structure and the compound with formula (I-12) structure is preferred For 1：0.5~2, more preferably 1：1~1.1.The reaction is preferably carried out in organic solvent, and the organic solvent is preferably first Benzene.The reaction is preferably carried out in the presence of a catalyst, and the catalyst is preferably Pd (OAc)2、PCy3·HBF4, PivOH and K2CO3Middle one or more, more preferably Pd (OAc)2、PCy3·HBF4, PivOH and K2CO3.Pd (OAc) in the catalyst2、 PCy3·HBF4, PivOH and K2CO3Mass ratio be preferably 40~50：130~160：90~110：680~720.The catalysis Agent is preferably 20~50 (mg) with having the amount ratio of the compound of formula (I-14) structure：0.5 (mmol), more preferably 900~ 1100(mg)：3~3.5 (mmol).The reaction is carried out preferably in inert gas atmosphere, and the inert gas is preferably argon Gas.The mode of the reaction is preferably back flow reaction.The time of shown reaction is preferably 10~24h, more preferably 12~16h. After reaction terminates, the solution containing reaction product is obtained.The solution containing reaction product is post-processed, had The compound of formula (I-5-2-a) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, drying, concentrating and column chromatography after, obtain the compound with formula (I-5-2-a) structure. It is described that the quencher used preferably water is quenched；The extractant of the extraction is preferably chloroform；The drier of the drying is preferred For anhydrous sodium sulfate；The solvent of the column chromatography is preferably chloroform and/or petroleum ether, and more preferably volume ratio is 3:1 chlorine Imitative and petroleum ether.
In the present invention, the compound with formula (I-5-2-b) structure is preferably prepared in accordance with the following methods：
Compound with formula (I-15) structure is reacted with the compound with formula (I-12) structure, is obtained with formula (I- 5-2-b) the compound of structure；
In formula (I-15), R10For C1~C10Alkyl.
In the preparation method for the above-mentioned compound with formula (I-5-2-b) structure that the present invention is provided, will directly have The compound of formula (I-15) structure is reacted with the compound with formula (I-12) structure, you can obtain tying with formula (I-5-2-b) The compound of structure, the process is specially：
The compound with formula (I-15) structure is mixed with the compound with formula (I-12) structure first, carried out anti- Should.Wherein, the compound with formula (I-15) structure has following structure：
In formula (I-15), R10For C1~C10Alkyl, be specially：——CH3、——C2H5、——C3H7、—— C4H9、——C5H11、——C6H13、——C7H15、C8H17、——C9H19Or --- C10H21。
In one embodiment that the present invention is provided, the compound with formula (I-15) structure is specially to have formula (I-15-a) compound of structure：
The source of the compound with formula (I-15) structure is not particularly limited the present invention, can use commercially available business Product, can also be prepared according to method well known to those skilled in the art.
In the present invention, the compound with formula (I-15) structure is mixed with the compound with formula (I-12) structure In course of reaction, the mol ratio of the compound with formula (I-15) structure and the compound with formula (I-12) structure is preferred For 1：0.5~2, more preferably 1：0.9~1.1.The reaction is preferably carried out in organic solvent, and the organic solvent is preferably Toluene.The reaction is preferably carried out in the presence of a catalyst, and the catalyst is preferably Pd (PPh3)2Cl2, triphenylphosphine, iodate It is one or more in cuprous and diisopropylamine, more preferably Pd (PPh3)2Cl2, triphenylphosphine, cuprous iodide and diisopropyl Amine.Pd (PPh in the catalyst3)2Cl2, triphenylphosphine, the amount ratio of cuprous iodide and diisopropylamine be preferably 60~70 (mg)：40~50 (mg)：10~20 (mg)：1.5~2.5 (mL).Pd (PPh in the catalyst3)2Cl2With with formula (I- 15) amount ratio of the compound of structure is preferably 60~70 (mg)：5 (mmol), more preferably 60~65 (mg)：5(mmol).Institute State reaction to carry out preferably in inert gas atmosphere, the inert gas is preferably argon gas.The temperature of the reaction is preferably 70 ~90 DEG C.The time of shown reaction is preferably 10~24h, more preferably 12~16h.After reaction terminates, obtain containing reaction production The solution of thing.The solution containing reaction product is post-processed, the compound with formula (I-5-2-b) structure is obtained.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, drying, concentrating and column chromatography after, obtain the compound with formula (I-5-2-b) structure. It is described that the quencher used preferably water is quenched；The extractant of the extraction is preferably chloroform；The drier of the drying is preferred For anhydrous sodium sulfate；The solvent of the column chromatography is preferably toluene and/or petroleum ether, and more preferably volume ratio is 3:1 first Benzene and petroleum ether.
In the present invention, the compound with formula (I-13) structure and the compound mixing with formula (I-5) structure During reaction, the compound of formula (I-5) structure and the raw material of formula (I-13) structural compounds, i.e., with formula (I-4) mol ratio of the compound of structure is preferably 0.5~3：1, more preferably 1~2：1, most preferably 1.4~1.6：1.Institute State reaction preferably to carry out in the presence of a catalyst, the catalyst is preferably Pd (PPh3)2Cl2.The catalyst and formula (I-13) raw material of structural compounds, i.e., the amount ratio of the compound with formula (I-4) structure is preferably 30~50 (mg)：1~2 (mmol), more preferably 40~50 (mg)：1~1.1 (mmol).The reaction is preferably carried out in organic solvent, described organic Solvent is preferably toluene.The reaction is carried out preferably in inert gas atmosphere, and the inert gas is preferably argon gas.It is described anti- The preferred back flow reaction of mode answered.The time of the reaction is preferably 10~24h, more preferably 12~16h.After reaction terminates, Obtain the solution containing reaction product.The solution containing reaction product is post-processed, obtained with formula (I-1) structure Prodrug esters.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, drying, concentrating and column chromatography after, obtain the prodrug esters with formula (I-1) structure.It is described The quencher used preferably water is quenched；The extractant of the extraction is preferably chloroform；The drier of the drying is preferably nothing Aqueous sodium persulfate；The solvent of the column chromatography is preferably toluene and/or petroleum ether, and more preferably volume ratio is 2:1 toluene and Petroleum ether.
In the present invention, the prodrug esters with formula (I-1) structure are mixed with alkali compounds and solvent is hydrolyzed During, the alkali compounds is preferably potassium hydroxide and/or sodium hydroxide.The alkali compounds and prepare it is described before Raw material used in body ester, i.e., the mol ratio of the compound with formula (I-2) or (I-4) structure is preferably 1~10：1, more preferably 2~4：1.The solvent is preferably water and organic solvent, and the organic solvent is preferably tetrahydrofuran.The temperature of the basic hydrolysis Degree is preferably 60~90 DEG C, more preferably 70~80 DEG C.The time of shown basic hydrolysis is preferably 3~8h, more preferably 5~ 6h.After basic hydrolysis terminates, the corresponding salt of prodrug esters is obtained.
Obtain after the corresponding salt of the prodrug esters, the corresponding salt of the prodrug esters mix with acid, progress metathesis reaction. The acid is preferably phosphoric acid.Raw material used in phosphoric acid salt corresponding with preparing prodrug esters, i.e., with formula (I-2) or (I-4) The mol ratio of the compound of structure is preferably 2~10：1, more preferably 3~5：1.After reaction terminates, obtain containing reaction product Solution.The solution containing reaction product is post-processed, and obtains the dye photoactivation agent with formula (I) structure.
In the present invention, the process that the above-mentioned solution containing reaction product is post-processed is specially：Contain reaction product Solution sequentially pass through be quenched, extract, drying, concentrating and column chromatography after, obtain the dye photoactivation agent with formula (I) structure. It is described that the quencher used preferably water is quenched；The extractant of the extraction is preferably chloroform；The drier of the drying is preferred For anhydrous sodium sulfate；The solvent of the column chromatography is preferably chloroform and/or methanol, and more preferably volume ratio is 1:20 Chloroform and methanol.
The light-sensitive coloring agent with formula (I) structure can be made in the method provided using the present invention, using the light-sensitive coloring agent system The photoelectric transformation efficiency of standby DSSC is higher.Preparation method raw material sources that the present invention is provided are abundant, into This is relatively low, and preparation process is simple, and product yield is high, and industrial production prospect is preferable.
The invention provides a kind of DSSC, the dye coating of the DSSC is by upper The dye photoactivation agent described in technical scheme is stated to be made or the dyestuff light as made from the preparation method described in above-mentioned technical proposal Sensitizer is made.
The dye photoactivation agent of the dye coating for the DSSC that the present invention is provided by mentioned earlier is made.
The DSSC that the present invention is provided includes：The first and second relative transparent base layers；Conductive layer, Light absorbing layer, hole transport layer and to electrode；In the middle of first and second transparent base layer, the conductive layer, light absorbs Layer, hole transport layer and electrode is sequentially connected with；The light absorbing layer includes semiconductor micro-nano particle layer and dye coating, described half Conductor micro-nano particle layer is connected with conductive layer, and the dye coating is connected with hole transport layer；Wherein, the dye coating is by institute above The dye photoactivation agent stated is made.
In the present invention, except dye coating, transparent base layer, conductive layer and light absorbing layer etc. are those skilled in the art The component parts of well known DSSC.Preparation method of the invention to the DSSC is simultaneously It is not particularly limited, can be prepared according to method well known to those skilled in the art, such as according to document (Energy Environ.Sci., organic dye sensitized solar cell 2010,3,1924) is prepared, as long as its dye coating is above-mentioned dyestuff light Sensitizer.
It is preferred that, the TiO that the present invention will be sintered on FTO electro-conductive glass2Nano structure membrane is in the dye photoactivation Soak, taken out after film in the solution of agent, the glass electrode for covering Platinum Nanoparticles is sealed with hot melt ring, finally electrolyte is injected Into the gap of two electrodes, that is, constitute DSSC.
Wherein, the solvent of the dye photoactivation agent solution is preferably the mixed solution of ethanol and chlorobenzene, the ethanol and The volume ratio of chlorobenzene is preferably (6~9)：1；The concentration of the solution of the dye photoactivation agent is preferably the μ of 50 μm of ol/L~200 mol/L；The time of the immersion is preferably 8 hours~20 hours, and the temperature of the immersion is preferably room temperature.
Obtain after DSSC, the present invention is in 100mWcm-2Simulate under AM1.5G sunshines, to preparing DSSC carry out performance detection.As a result show, prepared by the dye photoactivation agent provided with the present invention has The highest electricity conversion of machine DSSC, up to 13%, is current world's peak efficiency.
For a further understanding of the application, the dye with new type electron donor provided with reference to embodiment the application Material photosensitizer and preparation method thereof, DSSC are specifically described.In following examples, compound 4, 4- acetylenylbenzenes butyl formate, 5- acetenyl -2- carboxylic acid, ethyl esters thiophene, 2- carboxylic acid, ethyl ester thiophene, 4,7- dibromo diazosulfides It is purchased from lark prestige Reagent Company.Compound 8 and compound 14 according to document (M.Zhang, Y.Wang, M.Xu, W.Ma, R.Li, P.Wang, Energy Environ.Sci., 2013,6,2944) synthesis；Compound 10 according to document (L.Yang, Y.Ren, Z.Yao, C.Yan, W.Ma, P.Wang, J.Phys.Chem.C 2015,119,980.) synthesis obtain；Compound 11 is according to document (Zhaoyang.Yao,Min Zhang,Renzhi Li,Lin Yang,Yongna Qiao,Peng Wang Angew.Chem.Int.Ed.2015,54,5994) synthesis is obtained.
Embodiment 1
Reaction scheme is shown below：
The synthesis of 1.1 intermediates 2
In three neck round bottom, by 850 milligrams of compounds, 1,1.49 grams of 4,7- dibromo diazosulfides, 63 milligrams of Pd (PPh3)2Cl2, 48 milligrams of triphenylphosphines, 17 milligrams of cuprous iodides, 2 milliliters of diisopropylamines are dissolved in 10 milliliters of toluene, argon 80 DEG C are warming up under gas shielded, the lower reaction of stirring is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 40 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate filtrate, then with chloroform/petroleum ether (60-90 DEG C of boiling point) 3/1 obtains 1.45 grams of intermediates 2 as solvent column chromatography, and purity is 97%, and yield is 83%.
Structural characterization, mass spectral analysis are carried out to obtained intermediate 2 using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method As a result：415.01([M+H].Elementary analysis result：C, 54.94%；H, 3.65%；N, 6.74%.Nuclear magnetic resonance characterize data is such as Under：
1H NMR(400MHz,CDCl3)δ:8.05 (d, J=8.0Hz, 2H), 7.84 (d, J=8.0Hz, 1H), 7.71- 7.67 (m, 3H), 4.34 (t, J=6.6Hz, 2H), 1.80-1.73 (m, 2H), 1.53-1.44 (m, 2H), 0.99 (t, J= 7.4Hz,3H)。
13C NMR(100MHz,CDCl3)δ:166.10,154.18,153.25,133.28,132.06,131.95, 130.80,129.67,126.98,116.28,115.47,95.95,87.24,65.27,30.88,19.40,13.89。
1.2 the synthesis of intermediate 3
In three neck round bottom, by 1.00 g of compound, 2,1.32 grams of triisopropyl acetenyl silicon, 35 milligrams of Pd (PPh3)2Cl2, 27 milligrams of triphenylphosphines, 10 milligrams of cuprous iodides, 2 milliliters of diisopropylamines are dissolved in 10 milliliters of toluene, argon 80 DEG C are warming up under gas shielded, the lower reaction of stirring is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 40 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, obtained crude product dissolving In 50 milliliters of dichloromethane, 5.41 grams of tetrabutyl ammonium fluorides are added, are stirred overnight at room temperature, after reaction terminates, add 40 millis Water is risen, obtained mixed liquor is extracted three times with chloroform, merges organic phase, and organic phase anhydrous sodium sulfate drying is filtered to remove dry Drying prescription, concentrates filtrate, then obtain 0.71 gram of centre as solvent column chromatography with chloroform/petroleum ether (60-90 DEG C of boiling point) 3/1 Body 3, purity is 97%, and yield is 82%.
Structural characterization, mass spectral analysis are carried out to obtained intermediate 3 using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method As a result：361.08([M+H]+).Elementary analysis result：C, 69.99%；H, 4.48%；N, 7.76%.Nuclear magnetic resonance characterize data It is as follows：
1H NMR(400MHz,CDCl3)δ:8.06 (d, J=8.0Hz, 2H), 7.78 (s, 2H), 7.71 (d, J=8.1Hz, 2H), 4.34 (t, J=6.6Hz, 2H), 3.69 (s, 1H), 1.80-1.73 (m, 2H), 1.53-1.44 (m, 2H), 0.99 (t, J= 7.3Hz,3H)。
13C NMR(100MHz,CDCl3)δ:165.96,154.53,154.11,133.42,132.52,131.92, 130.74,129.58,126.85,117.57,116.36,96.74,87.59,85.44,79.18,65.18,30.80,19.32, 13.82。
The synthesis of 1.3 intermediates 5
In three neck round bottom, by 910 milligrams of compounds, 4,1.49 grams of 4,7- dibromo diazosulfides, 63 milligrams of Pd (PPh3)2Cl2, 48 milligrams of triphenylphosphines, 17 milligrams of cuprous iodides, 2 milliliters of diisopropylamines are dissolved in 10 milliliters of toluene, argon 80 DEG C are warming up under gas shielded, the lower reaction of stirring is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 40 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, again with toluene/petroleum ether (60-90 DEG C of boiling point) 3/1 obtains 1.63 grams of intermediates 5 as solvent column chromatography, and purity is 97%, and yield is 82%.
Structural characterization, mass spectral analysis are carried out to obtained intermediate 5 using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method As a result：392.93([M+H]+).Elementary analysis result：C, 45.81%；H, 2.31%；N, 7.12%.Nuclear magnetic resonance characterize data It is as follows：
1H NMR(400MHz,CDCl3)δ:7.81 (d, J=7.6Hz, 1H), 7.68 (d, J=3.8Hz, 1H), 7.63 (d, J =7.6Hz, 1H), 7.33 (d, J=3.8Hz, 1H), 4.34 (q, J=7.1Hz, 2H), 1.36 (t, J=7.1Hz, 3H).
13C NMR(100MHz,CDCl3)δ:161.63,153.93,153.28,133.45,133.25,132.09, 128.72,115.83,90.59,89.28,77.23,76.91,14.49。
The synthesis of 1.4 intermediates 7
In three neck round bottom, 530 milligrams of compounds 6 are dissolved in 40 milliliters of toluene, to reaction under argon gas protection 1.00 grams of 4,7- dibromo diazosulfides, 45 milligrams of Pd (OAc) are added in system2, 151 milligrams of PCy3HBF4, 104 milligrams of PivOH With 705 milligrams of K2CO3, backflow is warming up to, the lower reaction of stirring is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 40 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate filtrate, then with chloroform/petroleum ether (volume ratio is 3/1) obtains 878 milligrams of intermediates 7 as solvent column chromatography, and purity is 97%, and yield is 70%.
Structural characterization, mass spectral analysis are carried out to obtained intermediate 4 using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method As a result：368.93([M+H]+).Elementary analysis result：C, 42.26%；H, 2.47%；N, 7.58%.Nuclear magnetic resonance characterize data It is as follows：
1H NMR(400MHz,CDCl3)δ:7.97-793 (m, 1H), 7.82-7.78 (m, 2H), 7.71 (d, J=7.7Hz, 1H), 4.36 (q, J=7.0Hz, 2H), 1.38 (t, J=7.1Hz, 3H).
13C NMR(100MHz,CDCl3)δ:162.16,153.80,152.62,144.54,134.80,133.80, 132.14,127.90,126.69,126.17,114.15,61.39,14.38。
1.5 target product II synthesis
800 milligrams of compounds 8 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to -78 DEG C, 0.94 milliliter of n-BuLi (1.6 mol/L) is added dropwise under argon gas protection.Keep low-temp reaction 1 Hour, 299 milligrams of trimethyltin chlorides are then added into reaction system, stirring reaction are warmed to room temperature 12 hours.
After reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, is associated with Machine phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, and gained organotin crude product is directly used in In lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned tin product, 621 milligrams of compounds 2 and 40 milligrams of Pd (PPh3)2Cl2It is dissolved in 20 milliliters of toluene, reaction system is warming up to backflow and reacted under argon gas protection, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former butyl ester compound.
In three neck round bottom, above-mentioned butyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 167 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 875 milligrams of target product Formula II, purity For 98%, yield is 82%.
Structural characterization is carried out to obtained target product Formula II using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method, it is high Resolution Mass Spectrometry analysis result：1067.47632.Elementary analysis result：C, 74.21%；H, 6.92%；N, 3.95%.Nuclear magnetic resonance Characterize data is as follows：
1H NMR(400MHz,THF-d8)δ:8.27 (s, 1H), 8.06 (d, J=5.2Hz, 2H), 7.95 (d, J=7.4Hz, 1H), 7.84 (d, J=7.4Hz, 1H), 7.70 (d, J=7.8Hz, 2H), 7.46 (d, J=8.1Hz, 2H), 7.27 (s, 1H), 7.03 (d, J=8.2Hz, 4H), 6.89 (d, J=8.2Hz, 2H), 6.84 (d, J=8.2Hz, 4H), 3.94 (t, J=5.7Hz, 4H),2.01-2.00(m,4H),1.78-1.72(m,4H),1.37-1.36(m,10H),1.17(s,12H),1.09-1.08 (br,4H),0.92(br,8H),0.8(br,6H)。
13C NMR(100MHz,THF-d8)δ:165.63,159.97,157.76,155.50,154.90,151.06, 147.98,146.55,140.21,140.03,138.56,133.86,132.81,130.90,128.68,126.66,126.02, 125.28,122.49,120.01,115.86,114.65,112.72,94.43,88.16,67.39,53.72,37.61, 31.21,29.35,28.94,25.37,22.14,13.02,12.99。
Test result indicates that, the present invention has prepared the dye photoactivation agent with Formula II structure.
1.6 target product V synthesis
800 milligrams of compounds 8 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to -78 DEG C, 0.94 milliliter of n-BuLi (1.6 mol/L) is added dropwise under argon gas protection.Keep low-temp reaction 1 Hour, 299 milligrams of trimethyltin chlorides are then added into reaction system, stirring reaction are warmed to room temperature 12 hours.
After reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, is associated with Machine phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, and gained organotin crude product is directly used in In lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned tin product, 552 milligrams of compounds 7 and 40 milligrams of Pd (PPh3)2Cl2It is dissolved in 20 milliliters of toluene, reaction system is warming up to backflow and reacted under argon gas protection, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former ethyl ester compound.
In three neck round bottom, above-mentioned ethyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 839 milligrams of target product Formula V, purity For 98%, yield is 80%.
Structural characterization, high score are carried out to obtained target product Formula V using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method Distinguish mass spectrometry results：1049.43274.Elementary analysis result：C, 70.89%；H, 6.81%；N, 4.00%.Nuclear magnetic resonance table Levy data as follows：
1H NMR(400MHz,THF-d8)δ:8.26 (s, 1H), 8.11 (d, J=3.8Hz, 1H), 8.07 (d, J=7.7Hz, 1H), 7.97 (d, J=7.6Hz, 1H), 7.78 (d, J=3.9Hz, 1H), 7.45 (d, J=8.6Hz, 2H), 7.27 (s, 1H), 7.03 (d, J=8.8Hz, 4H), 6.89 (d, J=8.6Hz, 2H), 6.84 (d, J=8.8Hz, 4H), 3.94 (t, J=6.4Hz, 4H),2.02-2.00(m,4H),1.80-1.77(m,4H),1.51-1.46(m,4H),1.38-1.36(m,6H),1.29(br, 4H),1.20-1.18(m,10H),1.08(br,4H),0.94-0.91(m,6H),0.81-0.78(m,6H)。
13C NMR(100MHz,THF-d8)δ:148.89,146.81,144.76,142.50,139.11,138.71, 134.99,133.32,132.04,127.06,126.66,125.74,121.42,120.94,119.82,113.74,113.37, 113.24,113.01,112.07,109.14,107.06,102.89,191.65,54.40,40.73,24.61,18.22, 16.36,15.96,12.38。
Test result indicates that, the present invention has prepared the dye photoactivation agent with Formula V structure.
1.7 target product VI synthesis
800 milligrams of compounds 8 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to -78 DEG C, 0.94 milliliter of n-BuLi (1.6 mol/L) is added dropwise under argon gas protection.Keep low-temp reaction 1 Hour, 299 milligrams of trimethyltin chlorides are then added into reaction system, stirring reaction are warmed to room temperature 12 hours.
After reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, is associated with Machine phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, and gained organotin crude product is directly used in In lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned tin product, 588 milligrams of compounds 5 and 40 milligrams of Pd (PPh3)2Cl2It is dissolved in 20 milliliters of toluene, reaction system is warming up to backflow and reacted under argon gas protection, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former ethyl ester compound.
In three neck round bottom, above-mentioned ethyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 870 milligrams of target product Formula IV, purity For 98%, yield is 81%.
Structural characterization is carried out to obtained target product Formula IV using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method, it is high Resolution Mass Spectrometry analysis result：1073.43274.Elementary analysis result：C, 71.54%；H, 6.66%；N, 3.91%.Nuclear magnetic resonance Characterize data is as follows：
1H NMR(400MHz,THF-d8)δ:8.27 (s, 1H), 7.96 (d, J=7.6Hz, 1H), 7.84 (d, J=7.6Hz, 1H), 7.68 (d, J=4.6Hz, 1H), 7.46 (d, J=8.6Hz, 2H), 7.39 (d, J=3.8Hz, 1H), 7.27 (s, 1H), 7.03 (d, J=8.8Hz, 4H), 6.89 (d, J=8.7Hz, 2H), 6.84 (d, J=9.0Hz, 4H), 3.94 (t, J=6.4Hz, 4H),2.01-2.00(m,4H),1.80-1.75(m,4H),1.51-1.47(m,4H),1.37-1.36(m,6H),1.29(br, 4H),1.20-1.17(m,10H),1.08-1.07(m,4H),0.94-0.91(m,6H),0.81-0.78(m,6H)。
13C NMR(100MHz,THF-d8)δ:158.57,156.30,154.04,153.14,149.54,146.57, 145.15,138.96,138.56,137.03,132.37,131.29,131,06,130.84,127.43,123.81,120.98, 118.53,114.40,89.90,86.14,65.93,52.25,36.14,29.74,29.73,27.87,27.78,27.47, 23.90,23.00,20.68,20.66,11.53。
Test result indicates that, the present invention has prepared the dye photoactivation agent with Formula IV structure.
1.9 target product III synthesis
800 milligrams of compounds 8 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to 0 DEG C, 225 milligrams of NBS tetrahydrofuran solution (5 milliliters) is added dropwise.Room temperature reaction 1 hour, after reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, merges organic phase, the anhydrous sulphur of organic phase Sour sodium is dried, and is filtered to remove drier, concentrates filtrate, and gained bromination product 9 is directly used in lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned bromination product 9,504 milligrams of compounds 10,11 milligrams of Pd2 (dba)3, 0.02 milliliter of P (t-Bu)3, 68 milligrams of Cs2CO3It is dissolved in 20 milliliters of dioxane, the reactant under argon gas protection System is warming up to backflow and reacted, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former butyl ester compound.
In three neck round bottom, above-mentioned butyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 480 milligrams of target product formula IIIs, pure Spend for 98%, yield is 45%.
Structural characterization is carried out to obtained target product formula III using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method, it is high Resolution Mass Spectrometry analysis result：1067.47632.Elementary analysis result：C, 74.76%；H, 6.73%；N, 3.85%.Nuclear magnetic resonance Characterize data is as follows：
1H NMR(400MHz,THF-d8)δ:8.17(br,4H),7.92-7.89(m,2H),7.47-7.39(m,3H), 7.26 (s, 1H), 7.07 (d, J=8.6Hz, 2H), 7.02 (d, J=8.6Hz, 2H), 6.90-6.88 (m, 2H), 6.84 (d, J= 8.8Hz,4H),3.94(br,4H),1.96-1.95(m,4H),1.78-1.76(m,4H),1.49(br,4H),1.37(br, 6H),1.29(br,6H),1.18(br,8H),1.03(br,4H),0.92(br,6H),0.81-0.71(m,6H)。
13C NMR(100MHz,THF-d8)δ:160.84,156.78,156.45,155.86,155.54,155.27, 154.02,153.60,148.75,148.13,146.36,139.99,139.63,139.16,134.47,133.24,132.30, 130.46,129,29,128.82,127.36,125.77,120.65,119.93,118.40,115.78,115.52,114.75, 114.66,102.36,95.61,92.55,91.91,90.44,87.48,67.40,55.81,53.67,37.47,35.58, 31.09,29.32,29.26,29.10,28.94,25.37,22.16,13.01。
Test result indicates that, the present invention has prepared the dye photoactivation agent with formula III structure.
1.10 target product IV synthesis
800 milligrams of compounds 8 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to 0 DEG C, 225 milligrams of NBS tetrahydrofuran solution (5 milliliters) is added dropwise.Room temperature reaction 1 hour, after reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, merges organic phase, the anhydrous sulphur of organic phase Sour sodium is dried, and is filtered to remove drier, concentrates filtrate, and gained bromination product 9 is directly used in lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned bromination product 9,540 milligrams of compounds 3,11 milligrams of Pd2 (dba)3, 0.02 milliliter of P (t-Bu)3, 68 milligrams of Cs2CO3It is dissolved in 20 milliliters of dioxane, the reactant under argon gas protection System is warming up to backflow and reacted, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former butyl ester compound.
In three neck round bottom, above-mentioned butyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 916 milligrams of target product formula IVs, purity For 98%, yield is 84%.
Structural characterization is carried out to obtained target product formula IV using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method, it is high Resolution Mass Spectrometry analysis result：1091.47632.Elementary analysis result：74.76%；H, 6.73%；N, 3.85%.Nuclear magnetic resonance table Levy data as follows：
1H NMR(400MHz,THF-d8)δ:8.07 (d, J=8.1Hz, 2H), 7.87-7.85 (m, 1H), 7.81-7.77 (m, 1H), 7.71 (d, J=7.9Hz, 2H), 7.48 (d, J=8.7Hz, 1H), 7.44 (d, J=8.7Hz, 1H), 7.41 (d, J= 10.1Hz, 1H), 7.26 (s, 1H), 7.07 (d, J=6.4Hz, 2H), 7.02 (d, J=8.9Hz, 2H), 6.91-6.83 (m, 6H),3.96-3.92(m,4H),1.96-1.95(m,4H),1.80-1.75(m,4H),1.53-1.45(m,4H),1.40-1.34 (m,8H),1.29(br,4H),1.18(br,10H),1.04-1.00(m,2H),0.92-0.91(m,6H),0.83-0.82(br, 6H)。
13C NMR(100MHz,THF-d8)δ:160.84,156.78,156.45,155.86,155.54,155.27, 154.02,153.60,148.75,148.13,146.36,139.99,139.63,139.16,134.47,133.24,132.30, 130.46,129,29,128.82,127.36,125.77,120.65,119.93,118.40,115.78,115.52,114.75, 114.66,102.36,95.61,92.55,91.91,90.44,87.48,67.40,55.81,53.67,37.47,35.58, 31.09,29.32,29.26,29.10,28.94,25.37,22.16,13.01。
Test result indicates that, the present invention has prepared the dye photoactivation agent with formula IV structure.
Embodiment 2
Reaction scheme is shown below：
The synthesis of 2.1 intermediates 12
In through flame-dried three neck round bottom, 1.94 grams of intermediates 11 are dissolved in 20 milliliters of tetrahydrofurans, 10 milliliters are added under argon gas protection to hexyl benzene bromide solution (2M tetrahydrofuran solution), reaction system is warming up to 90 DEG C And reaction is stayed overnight.
After reaction terminates, reaction system is cooled to 0 DEG C, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, obtained crude product brown Thick liquid is without separation, due directly to the next step.
In dry three neck round bottom, upper step is reacted into obtained intermediate and is dissolved in 30 milliliters of toluene, is added 2.00 grams of solid acid catalyst Amberlyst 15, are warming up to flow back under argon gas protection and are reacted, and reaction is stayed overnight.Reaction After end, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor is extracted three times with chloroform, is merged organic Phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, exhibition is used as with petroleum ether (60-90 DEG C of boiling point) Agent column chromatography is opened, 2.17 grams of intermediates 12 are obtained, purity is 98%, and yield is 90%.
Structural characterization, high-resolution are carried out to obtained intermediate 12 using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method Mass spectrum mass spectrometry results：1219.85429.Elementary analysis result：C, 85.58%, H, 9.34%；N, 1.56%.Nuclear magnetic resonance Characterize data is as follows：
1H NMR(400MHz,THF-d8)δ:8.60 (d, J=2.6Hz, 1H), 8.58 (d, J=3.4Hz, 1H), 8.07 (d, J=8.2Hz, 1H), 8.01 (s, 1H), 7.75 (s, 1H), 7.70-7.63 (m, 2H), 7.59 (d, J=8.3Hz, 2H), 7.22- 7.20 (m, 5H), 7.09 (d, J=8.4Hz, 2H), 7.05-7.03 (m, 4H), 6.89 (d, J=5.2Hz, 1H), 4.65 (d, J= 7.0Hz, 2H), 3.98 (d, J=5.3Hz, 2H), 2.56-2.52 (m, 4H), 2.37 (br, 1H), 1.87 (br, 1H), 1.59- 1.54(m,6H),1.50-1.43(m,12H),1.36-1.30(m,33H),1.23-1.19(m,17H),0.93-0.91(m, 6H),0.89-0.85(m,6H),0.80-0.78(m,6H)。
13C NMR(100MHz,THF-d8)δ:160.02,147.32,145.04,142.22,141.57,138.44, 137.77,135.31,133.83,133.53,132.16,131.64,131.48,130.71,129.41,129.35,128.74, 127.92,126.91,125.86,125.46,125.08,124.92,123.98,123.17,122.81,121.55,118.35, 118.09,115.35,115.09,106.97,71.70,59.23,50.58,40.94,39.36,36.51,33.07,33.05, 32.99,32.96,32.86,32.75,32.64,31.24,31.10,30.91,30.78,30.69,30.51,30.42, 30.28,28.05,28.03,27.51,27.48,23.78,23.75,23.69,23.67,23.64,14.66,14.65, 14.63,14.61,14.59。
2.2 target product VII synthesis
1.22 g of compound 12 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to -78 DEG C, 0.94 milliliter of n-BuLi (1.6 mol/L) is added dropwise under argon gas protection.Keep low-temp reaction 1 Hour, 299 milligrams of trimethyltin chlorides are then added into reaction system, stirring reaction are warmed to room temperature 12 hours.
After reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, is associated with Machine phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, and gained organotin crude product is directly used in In lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned tin product, 585 milligrams of compounds 14 and 40 milligrams of Pd (PPh3)2Cl2It is dissolved in 20 milliliters of toluene, reaction system is warming up to backflow and reacted under argon gas protection, and reacts Night.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former ethyl ester compound.
In three neck round bottom, above-mentioned ethyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 1.26 grams of target product Formula VII, purity For 98%, yield is 85%.
Structural characterization is carried out to obtained target product Formula VII using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method, it is high Resolution Mass Spectrometry analysis result：1474.87264.Elementary analysis result：C, 81.42%；H, 8.13%；N, 2.85%.Nuclear magnetic resonance Characterize data is as follows：
1H NMR (400MHz, THF-d8)δ:8.65 (d, J=8.0Hz, 1H), 8.64 (d, J=7.2Hz, 1H), 8.13- 8.12 (m, 3H), 8.09 (d, J=8.2Hz, 1H), 7.99 (d, J=8.2Hz, 2H), 7.79 (d, J=6.6Hz, 2H), 7.73- 7.69 (m, 1H), 7.55-7.51 (m, 5H), 7.47 (d, J=7.5Hz, 1H), 7.41 (d, J=8.2Hz, 2H), 7.33 (s, 1H), 7.22 (d, J=8.2Hz, 4H), 7.04 (d, J=8.3Hz, 2H), 3.98 (d, J=5.0Hz, 2H), 3.86 (br, 2H), 2.61 (t, J=7.4Hz, 4H), 2.05-2.03 (m, 1H), 1.88-1.87 (m, 1H), 1.64-1.60 (m, 6H), 1.52-1.47 (m, 6H), 1.38-1.26 (m, 30H), 1.14 (br, 20H), 0.95-0.91 (m, 6H), 0.85-0.83 (m, 6H), 0.79- 0.75(m,6H)。
13C NMR(100MHz,THF-d8)δ:175.83,167.70,159.92,154.21,153.24,147.74, 145.75,142.07,142.03,141.84,140.22,138.44,137.12,135.07,133.70,133.38,132.34, 132.21,131.34,131.16,131.02,130.68,130.63,129.90,129.49,129.23,129.04,128.11, 127.51,126.18,125.74,125.37,124.70,123.97,122.84,121.60,118.43,117.74,115.28, 114.77,107.51,71.73,59.21,50.22,40.42,39.37,36.60,36.40,33.09,33.07,33.02, 32.99,32.90,32.84,32.66,32.59,31.27,31.06,30.93,30.89,30.87,30.80,30.72, 30.64,30.53,30.45,30.33,28.19,28.08,28.05,27.32,27.29,26.59,23.80,23.77, 23.70,23.64,14.72,14.70,14.65,14.63,14.60。
Test result indicates that, the present invention has prepared the dye photoactivation agent with Formula VII structure.
2.3 target product VIII synthesis
1.22 g of compound 12 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to -78 DEG C, 0.94 milliliter of n-BuLi (1.6 mol/L) is added dropwise under argon gas protection.Keep low-temp reaction 1 Hour, 299 milligrams of trimethyltin chlorides are then added into reaction system, stirring reaction are warmed to room temperature 12 hours.
After reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, is associated with Machine phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, and gained organotin crude product is directly used in In lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned tin product, 621 milligrams of compounds 2 and 40 milligrams of Pd (PPh3)2Cl2It is dissolved in 20 milliliters of toluene, reaction system is warming up to backflow and reacted under argon gas protection, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former ethyl ester compound.
In three neck round bottom, above-mentioned ethyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 1.23 grams of target product Formula VIII, pure Spend for 98%, yield is 82%.
Structural characterization is carried out to obtained target product Formula VIII using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method, High resolution mass spectrum analysis result：1498.87264.Elementary analysis result：C, 81.72%；H, 8.00%；N, 2.80%.Nuclear-magnetism is total to Characterize data of shaking is as follows：
1H NMR(400MH,THF-d8)δ:8.65 (d, J=7.9Hz, 2H), 8.12-8.08 (m, 2H), 8.05-8.04 (m, 3H), 7.77-7.62 (m, 6H), 7.53 (d, J=8.4Hz, 2H), 7.47-7.38 (m, 5H), 7.14 (d, J=8.4Hz, 4H), 7.08 (d, J=8.5Hz, 2H), 4.43 (d, J=5.7Hz, 2H), 3.99 (d, J=5.4Hz, 2H), 2.58 (t, J=7.4Hz, 4H),2.08-2.01(m,1H),1.88-1.85(m,1H),1.64-1.56(m,6H),1.51-1.16(m,58H),0.93- 0.90(m,6H),0.85-0.83(m,6H),0.79-0.76(m,6H)。
13C NMR(100MHz,THF-d8)δ:167.17,160.01,152.56,147.48,146.08,141.84, 140.96,138.86,136.65,135.14,133.54,132.80,132.20,131.35,130.73,129.54,128.97, 128.43,128.17,125.50,125.36,125.01,124.75,123.95,122.87,121.70,118.82,117.94, 115.32,115.01,107.70,96.18,89.61,71.72,59.13,50.53,40.73,40.59,39.36,36.56, 36.35,33.06,32.98,32.85,32.66,31.11,30.68,30.31,28.04,27.41,23.74,23.67, 14.59。
Test result indicates that, the present invention has prepared the dye photoactivation agent with Formula VIII structure.
2.4 target product IX synthesis
1.22 g of compound 12 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to -78 DEG C, 0.94 milliliter of n-BuLi (1.6 mol/L) is added dropwise under argon gas protection.Keep low-temp reaction 1 Hour, 299 milligrams of trimethyltin chlorides are then added into reaction system, stirring reaction are warmed to room temperature 12 hours.
After reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, is associated with Machine phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, and gained organotin crude product is directly used in In lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned tin product, 552 milligrams of compounds 7 and 40 milligrams of Pd (PPh3)2Cl2It is dissolved in 20 milliliters of toluene, reaction system is warming up to backflow and reacted under argon gas protection, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former ethyl ester compound.
In three neck round bottom, above-mentioned ethyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 1.23 grams of target product Formula IX, purity For 98%, yield is 82%.
Structural characterization is carried out to obtained target product Formula IX using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method, it is high Resolution Mass Spectrometry analysis result：1480.82906.Elementary analysis result：C, 79.47%；H, 7.96%；N, 2.84%.Nuclear magnetic resonance Characterize data is as follows：
1H NMR (400MHz, THF-d8)δ:8.67-8.64 (m, 2H), 8.09-8.06 (m, 2H), 7.87 (d, J= 3.8Hz, 1H), 7.89 (d, J=8.0Hz, 1H), 7.99 (d, J=8.2Hz, 2H), 7.73-7.69 (m, 3H), 7.57-7.53 (m, 5H), 7.38-7.34 (m, 3H), 7.25 (d, J=8.1Hz, 5H), 7.03 (d, J=8.5Hz, 2H), 3.99 (d, J= 5.3Hz, 2H), 3.74 (br, 2H), 2.62 (t, J=7.5Hz, 4H), 2.02-2.01 (m, 1H), 1.89-1.87 (m, 1H), 1.67-1.60 (m, 6H), 1.51-1.46 (m, 6H), 1.38-1.34 (m, 20H), 1.29-1.26 (m, 12H), 1.14 (br, 20H),0.96-0.91(m,6H),0.85-0.81(m,6H),0.78-0.75(m,6H)。
13C NMR(100MHz,THF-d8)δ:163.53,159.91,152.78,147.79,146.22,145.77, 142.02,141.89,140.48,138.40,137.01,135.94,135.04,134.28,133.30,132.22,130.69, 129.07,128.09,126.92,125.70,124.62,123.92,122.80,121.56,118.37,117.62,115.25, 114.67,107.53,71.73,59.19,50.16,40.35,39.38,36.62,33.09,32.99,32.90,32.85, 32.68,32.66,32.59,31.27,31.05,30.94,31.05,30.94,30.81,30.71,30.65,30.54, 30.46,30.35,28.07,27.30,23.80,23.77,23.69,23.65,14.69,14.62,14.59。
Test result indicates that, the present invention has prepared the dye photoactivation agent with Formula IX structure.
The synthesis of 2.5 target product Xs
1.22 g of compound 12 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to -78 DEG C, 0.94 milliliter of n-BuLi (1.6 mol/L) is added dropwise under argon gas protection.Keep low-temp reaction 1 Hour, 299 milligrams of trimethyltin chlorides are then added into reaction system, stirring reaction are warmed to room temperature 12 hours.
After reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, is associated with Machine phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrates filtrate, and gained organotin crude product is directly used in In lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned tin product, 588 milligrams of compounds 5 and 40 milligrams of Pd (PPh3)2Cl2It is dissolved in 20 milliliters of toluene, reaction system is warming up to backflow and reacted under argon gas protection, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former ethyl ester compound.
In three neck round bottom, above-mentioned ethyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 1.29 grams of target product Formula X, purity is 98%, yield is 86%.
Structural characterization, high score are carried out to obtained target product Formula X using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method Distinguish mass spectrometry results：1504.82906.Elementary analysis result：C, 79.79%；H, 7.83%；N, 2.79%.Nuclear magnetic resonance table Levy data as follows：
1H NMR (400MHz, THF-d8)δ:8.65-8.63 (m, 2H), 8.12 (s, 1H), 8.09 (d, J=8.2Hz, 1H), 7.92 (s, 1H), 7.72 (t, J=7.9Hz, 2H), 7.68-7.67 (m, 1H), 7.61 (d, J=7.5Hz, 1H), 7.57 (d, J= 7.6Hz, 1H), 7.48-7.43 (m, 7H), 7.35 (d, J=3.8Hz, 1H), 7.17 (d, J=8.2Hz, 4H), 7.06 (d, J= 8.4Hz, 2H), 4.19 (d, J=4.8Hz, 2H), 3.98 (d, J=5.3Hz, 2H), 2.59 (t, J=7.5Hz, 4H), 2.19- 2.18(m,1H),1.88-1.86(m,1H),1.72(br,4H),1.63-1.57(m,6H),1.50-1.44(m,6H),1.37- 1.29(m,36H),1.19-1.15(m,12H),0.93-0.90(m,6H),0.86-0.83(m,6H),0.79-0.75(m,6H)。
13C NMR(100MHz,THF-d8)δ:162.65,159.99,155.68,152.36,147.56,146.03, 141.85,141.11,138.73,137.26,136.64,135.10,134.07,133.92,133.81,133.45,132.94, 132.20,131.32,130.93,129.98,129.27,129.00,128.82,128.17,126.05,125.75,125.39, 124.79,124.70,123.94,122.86,121.69,118.72,117.80,115.30,114.87,114.25,107.71, 92.93,89.38,71.72,59.12,50.42,40.60,39.37,36.57,33.08,32.99,32.95,32.85, 32.66,31.26,31.09,30.92,30.80,30.67,30.52,30.44,30.33,28.06,27.39,23.79, 23.77,23.70,23.65,14.66,14.63,14.58。
Test result indicates that, the present invention has prepared the dye photoactivation agent with Formula X structure.
2.6 target product X I synthesis
1.22 g of compound 12 are added in dry round-bottomed flask, 20 milliliters of anhydrous tetrahydro furans are then added, will be anti- System low temperature is answered to 0 DEG C, 225 milligrams of NBS tetrahydrofuran solution (5 milliliters) is added dropwise.Room temperature reaction 1 hour, after reaction terminates, 40 milliliters of water are added into reaction system, obtained mixed liquor is extracted three times with chloroform, merges organic phase, the anhydrous sulphur of organic phase Sour sodium is dried, and is filtered to remove drier, concentrates filtrate, and gained bromination product 13 is directly used in lower step coupling reaction.
In dry Schlenk reaction bulbs, by above-mentioned bromination product 13,504 milligrams of compounds 10,11 milligrams of Pd2 (dba)3, 0.02 milliliter of P (t-Bu)3, 68 milligrams of Cs2CO3It is dissolved in 20 milliliters of dioxane, the reactant under argon gas protection System is warming up to backflow and reacted, and reaction is stayed overnight.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of water are added, obtained mixed liquor extracts three with chloroform It is secondary, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, filtrate is concentrated, with toluene/petroleum ether (body 2/1) product compares as solvent column chromatography, obtains dyestuff former butyl ester compound.
In three neck round bottom, above-mentioned butyl ester compound is dissolved in the mixing of 15 milliliters of tetrahydrofurans and 5 milliliters of water In solvent, 157 milligrams of potassium hydroxide are added into reaction system, 80 DEG C, stirring reaction 5 hours are warming up to.
After reaction terminates, reaction system is cooled to room temperature, 20 milliliters of phosphate aqueous solutions (0.2 mol/L) is added, obtains Mixed liquor extracted three times with chloroform, merge organic phase, organic phase anhydrous sodium sulfate drying is filtered to remove drier, concentrate Filtrate, with chloroform/methanol (volume ratio 1/20) as solvent column chromatography, obtains 1.12 grams of target product Formula X I, purity For 98%, yield is 75%.
Structural characterization is carried out to obtained target product Formula X I using nuclear magnetic resonance, mass spectral analysis and elemental microanalysis method, it is high Resolution Mass Spectrometry analysis result：1498.87264.Elementary analysis result：C, 81.72%；H, 8.00%；N, 2.80%.Nuclear magnetic resonance Characterize data is as follows：
1H NMR(400MHz,THF-d8)δ:8.59 (d, J=8.0Hz, 2H), 8.14 (d, J=8.5Hz, 2H), 8.09- 8.06 (m, 3H), 7.97 (s, 1H), 7.75 (d, J=7.4Hz, 1H), 7.71-7.65 (m, 4H), 7.56 (d, J=8.5Hz, 2H), 7.31-7.29 (m, 5H), 7.13 (d, J=8.4Hz, 4H), 7.09 (d, J=8.6Hz, 2H), 4.59 (d, J=6.9Hz, 2H), 3.98 (d, J=5.4Hz, 2H), 2.58 (t, J=7.6Hz, 4H), 2.04-2.01 (m, 1H), 1.87-1.85 (m, 1H), 1.61-1.55(m,6H),1.51-1.41(m,12H),1.36-1.29(m,40H),1.23-1.19(m,16H),0.95-0.91 (m,6H),0.88-0.84(m,6H),0.82-0.78(m,6H)。
13C NMR(100MHz,THF-d8)δ:175.18,167.61,160.06,156.00,153.93,147.09, 145.39,141.92,141.89,141.51,141.05,139.08,137.56,135.13,134.27,133.82,133.37, 132.84,132.16,131.82,130.79,130.70,130.08,129.54,129.30,129.08,129.00,128.11, 125.74,125.69,125.58,125.35,124.73,123.96,122.90,121.84,120.16,119.10,117.87, 117.42,115.35,115.02,107.83,92.04,91.46,71.70,59.14,50.66,40.93,39.35,36.55, 36.37,33.07,33.05,33.03,32.99,32.86,32.76,32.65,31.24,31.13,30.91,30.88, 30.83,30.79,30.78,30.70,30.64,30.51,30.40,30.32,28.19,28.05,28.03,27.49, 26.59,23.78,23.75,23.73,23.67,23.64,14.66,14.64,14.60。
Test result indicates that, the present invention has prepared the dye photoactivation agent with Formula X I structures.
Embodiment 3
The dye photoactivation agent sensitization prepared according to literature method (Energy Environ.Sci., 2010,3,1924) is too Positive energy battery, is concretely comprised the following steps：Dye photoactivation agent made from embodiment 1~2 is configured to ethanol/chlorine of 150 micromoles per liters Benzene (volume ratio 8：2) solution.Then by the TiO through 500 DEG C of sintering2It is small that structure bilayer membrane electrode soaks 12 in dye solution When, electrode is taken out, the glass electrode for covering Platinum Nanoparticles is sealed with hot melt ring, electrolyte is finally injected into the seam of two electrodes In gap, that is, constitute DSSC.
In 100mWcm-2Simulate under AM1.5G sunshines, performance inspection is carried out to the DSSC of preparation Survey, (method for testing performance of solar cell refers to Energy Environ.Sci., 2010,3,1924) test result is shown in Table 1, As shown in Table 1, organic dye sensitized solar cell prepared by the dye photoactivation agent provided with the present invention has higher light Photoelectric transformation efficiency.
The performance test results for the DSSC that the embodiment of the present invention 1~2 of table 1 is provided
As seen from the above embodiment, the invention provides a series of dye photoactivation agent, the dye photoactivation agent is by difference Receptor unit and donor monomer it is built-up, energy level is various, and spatial distribution is different.Wherein described receptor unit is by benzene, thiophene, Diazosulfide, three key units are arranged in a combination, cheap, and raw material sources enrich.The distribution of such receptor unit energy level is more Sample.Test result indicates that, such dye photoactivation agent can effectively utilize sunshine, be obviously improved the short-circuit current density of device So as to lift the electricity conversion of DSSC.Using such dye photoactivation agent prepare dye sensitization too Positive energy battery peak efficiency, up to 13%, is current world's peak efficiency.Dye photoactivation agent structure that the present invention is provided is novel, Raw material sources are abundant, cost is relatively low, and industrial production prospect is preferable.Also, the preparation for the dye photoactivation agent that the present invention is provided Method is more succinct, convenient and high yield route.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (8)

1. a kind of dye photoactivation agent, with structure shown in formula (I)：
In formula (I), A is the substituent with formula (a) structure；E is the substituent with formula (c) structure；X is 0；Y is 1；
Or, A is the substituent with formula (a) structure；E is the substituent with formula (d) structure；X is 0；Y is 0 or 1；
Or, A is the substituent with formula (b) structure；E is the substituent with formula (c) structure；X is 0；Y is 0 or 1；
Or, A is the substituent with formula (b) structure；E is the substituent with formula (d) structure；X is 0；Y is 1；
Wherein, R1And R '1Separately it is selected from H, C2~C24Alkyl or C2~C24Alkoxy；R3Selected from H, C1~C36Alkyl or C1 ~C36The alkyl of alkoxy substitution；R2、R’2And R4Separately it is selected from C1~C36Alkyl or C1~C36The hydrocarbon of alkoxy substitution Base；R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R5And R '5Independently Ground is selected from the substituent with formula (f) structure：
In formula (f), R9For C1~C18Alkyl.
2. dye photoactivation agent according to claim 1, it is characterised in that R3Selected from H, C2~C24Alkyl or C2~C24Alkane The alkyl of epoxide substitution；R2、R’2And R4Separately it is selected from C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution；R6With R7Separately it is selected from H, F, C2~C24Alkyl or C2~C24The alkyl of alkoxy substitution.
3. dye photoactivation agent according to claim 2, it is characterised in that the R2、R’2And R4Separately it is selected from C2 ~C24Alkyl.
4. dye photoactivation agent according to claim 2, it is characterised in that the R3For the substitution with formula (e) structure Base：
In formula (e), R8For C1~C18Alkoxy.
5. dye photoactivation agent according to claim 1, it is characterised in that the dye photoactivation agent have formula (II), Formula (V), formula (VI), formula (VII), formula (VIII) or structure shown in formula (X)：
6. a kind of preparation method of dye photoactivation agent, comprises the following steps：
Prodrug esters with formula (I-1) structure are hydrolyzed, and obtain the dye photoactivation agent with formula (I) structure；
In formula (I-1) and formula (I), A is the substituent with formula (a) structure；E is the substituent with formula (c) structure；X is 0；y For 1；
Or, A is the substituent with formula (a) structure；E is the substituent with formula (d) structure；X is 0；Y is 0 or 1；
Or, A is the substituent with formula (b) structure；E is the substituent with formula (c) structure；X is 0；Y is 0 or 1；
Or, A is the substituent with formula (b) structure；E is the substituent with formula (d) structure；X is 0；Y is 1；
Wherein, R1And R '1Separately it is selected from H, C2~C24Alkyl or C2~C24Alkoxy；R3Selected from H, C1~C36Alkyl or C1 ~C36The alkyl of alkoxy substitution；R2、R’2And R4Separately it is selected from C1~C36Alkyl or C1~C36The hydrocarbon of alkoxy substitution Base；R6And R7Separately it is selected from H, F, C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R10For C1~C10Alkyl； R5And R '5Separately it is selected from the substituent with formula (f) structure：
In formula (f), R9For C1~C18Alkyl.
7. preparation method according to claim 6, it is characterised in that the prodrug esters with formula (I-1) structure according to It is prepared by following methods：
Compound with formula (I-2) structure is reacted with the compound with formula (I-3) structure, is obtained with formula (I-1) The prodrug esters of structure；
Or
Compound with formula (I-4) structure is reacted with the compound with formula (I-5) structure, is obtained with formula (I-1) The prodrug esters of structure；
A-Z formulas (I-2)；
A-H formulas (I-4)；
In formula (I-2)~formula (I-5), A is the substituent with formula (a) or formula (b) structure；R6And R7Separately selected from H, F、C1~C36Alkyl or C1~C36The alkyl of alkoxy substitution；R10For C1~C10Alkyl；Y is each independently 0 or 1；Z is halogen.
8. a kind of DSSC, the dye coating of the DSSC is appointed in Claims 1 to 5 Dye photoactivation agent described in meaning one is made or contaminated as made from the preparation method any one of claim 6~7 Material photosensitizer is made.
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CN103834190A (en) * 2013-12-09 2014-06-04 中国科学院长春应用化学研究所 Benzothiadiazole-cyanocinnamic acid receptor-containing organic dye and its use in dye-sensitized solar cell
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