CN105131642A - Organic dye and preparation method thereof, and dye sensitized solar cell - Google Patents

Organic dye and preparation method thereof, and dye sensitized solar cell Download PDF

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CN105131642A
CN105131642A CN201510514088.3A CN201510514088A CN105131642A CN 105131642 A CN105131642 A CN 105131642A CN 201510514088 A CN201510514088 A CN 201510514088A CN 105131642 A CN105131642 A CN 105131642A
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formula
alkyl
compound
reaction
alkoxyl group
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CN105131642B (en
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王鹏
张敏
姚朝阳
吴恒
王二峰
王俊婷
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Changzhou Institute Of Energy Storage Materials & Devices
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Changchun Institute of Applied Chemistry of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention belongs to the technical field of solar cells, and especially relates to an organic dye and a preparation method thereof, and a dye sensitized solar cell. The organic dye provided by the invention has a structure represented by the formula (I), wherein in the formula (I), R1 is H, C1-C36 hydrocarbyl or C1-C36 alkoxy substituted hydrocarbyl; R2, R'2, R3, R'3 and R4 are independently selected from C1-C36 hydrocarbyl or C1-C36 alkoxy substituted hydrocarbyl; X is a substituent having the structure represented by the formula (a) or the formula (b); in the formula (a), y1 and y2 are independently 0 or 1; R5 and R6 are independently selected from H, F, C1-C36 hydrocarbyl or C1-C36 alkoxy substituted hydrocarbyl; R7 is a substituent having the structure represented by the formula (c); -Q-COOH is the formula (c); and in the formula (c), Q is phenylene, naphthylene or phenanthrylene. The organic dye shows wider absorption spectra and higher degree of solar energy utilization, thereby significantly improving the photoelectric conversion efficiency of the dye sensitized solar cell.

Description

A kind of organic dye and preparation method thereof and dye-sensitized solar cells
Technical field
The invention belongs to technical field of solar cells, particularly relate to a kind of organic dye and preparation method thereof and dye-sensitized solar cells.
Background technology
Solar cell effectively can absorb sun power, and convert it into the semiconducter device of electric energy.Dye-sensitized solar cells, as the important one in solar cell, has obtained the extensive concern in the world.As far back as 1991, the three core ruthenium dye RuL that the people such as Amadelli reported by study group 2(μ-(CN) Ru (CN) L ' 2) 2(L=2,2 '-dipyridyl-4,4 '-dicarboxylic acid, L '=2,2 '-dipyridyl), as sensitizing agent, is adsorbed on the high quality TiO that they develop with great concentration for many years 2nano-crystal thin-film makes device, obtains the photoelectric transformation efficiency of under simulated solar irradiation 7.1%, established the Research foundation of dye-sensitized solar cells.Compared with traditional inorganic semiconductor solar cell, the low cost of manufacture of dye-sensitized solar cells, various colors, lighter in weight, can fold, curling thus be widely used in daily life.
Dye-sensitized solar cells is usually by transparent base layer, conductive layer, semi-conductor micro-nano particle layer, organic dye layer, hole transport layer with form electrode, and wherein, organic dye layer is the core of dye-sensitized solar cells.Organic dye layer is made up of photosensitivity organic dye usually, but due to the absorption spectrum of current photosensitivity organic dye narrow, lower to Solar use degree, cause the photoelectric transformation efficiency of existing dye-sensitized solar cells lower.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of organic dye and preparation method thereof and dye-sensitized solar cells, using organic dye provided by the invention as the dye-sensitized solar cells of organic dye layer material, there is higher photoelectric transformation efficiency.
The invention provides a kind of organic dye, there is structure shown in formula (I):
In formula (I), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces;
X is the substituting group of formula (a) or formula (b) structure:
In formula (a), y 1and y 2be independently 0 or 1; R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 7substituting group for formula (c) structure :-Q-COOH formula (c); In formula (c), Q is phenylene, naphthylidene or phenanthrylene.
Preferably, described R 1for H, C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces.
Preferably, described R 1substituting group for formula (d) structure:
In formula (d), R 8for C 1~ C 16alkoxyl group.
Preferably, described R 2, R ' 2, R 3and R ' 3substituting group independently selected from formula (e) structure:
In formula (e), R ' 8for C 1~ C 16alkyl.
Preferably, described R 4for C 2~ C 18alkyl.
Preferably, in formula (a), R 5and R 6independently selected from H, F, C 2~ C 18alkyl or C 2~ C 18the alkyl that alkoxyl group replaces.
Preferably, described organic dye has formula (II) or formula (III) structure:
The invention provides a kind of preparation method of organic dye, comprise the following steps:
The prodrug esters with formula (IV) structure is hydrolyzed, and obtains the organic dye with formula (I) structure;
Or
The prodrug esters with formula (VI) structure is hydrolyzed, and obtains the organic dye with formula (I) structure;
Or
The compound with formula (VII) structure and the compound condensation with formula (VIII) structure react, and obtain the organic dye with formula (I) structure;
In formula (I), formula (IV), formula (VI) and formula (VII), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces;
In formula (I), X is the substituting group of formula (a) or formula (b) structure:
In formula (a), y 1and y 2be independently 0 or 1, R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 7substituting group for formula (c) structure :-Q-COOH formula (c); In formula (c), Q is phenylene, naphthylidene or phenanthrylene;
In formula (IV) and formula (VI), R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c '); Formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl.
Preferably, the prodrug esters described in formula (IV) structure is prepared in accordance with the following methods:
The described halogenated compound with formula (A-0) structure carries out linked reaction with the compound with formula (A-01) structure, obtains the prodrug esters with formula (IV) structure;
In formula (A-0), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, Z is Br or I;
In formula (A-01), R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; Z is Br or I; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c '); Formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl;
The described prodrug esters with formula (VI) structure is prepared in accordance with the following methods:
The described tin with formula (B-1) structure carries out linked reaction for compound and the compound with formula (B-2) structure, obtains the prodrug esters with formula (VI) structure;
In formula (B-1), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; A 1, A 2and A 3separately be selected from C 1~ C 10alkyl;
In formula (B-2), R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; Z is Br or I; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl;
The described compound with formula (VII) structure is prepared in accordance with the following methods:
Described formylation reagent carries out formylation reaction with the compound with formula (A-1) structure, obtains the compound with formula (VII) structure.
The invention provides a kind of dye-sensitized solar cells, the organic dye that the organic dye layer of described dye-sensitized solar cells is made up of the organic dye described in technique scheme or is obtained by the preparation method described in technique scheme is made.
Compared with prior art, the invention provides a kind of organic dye and preparation method thereof and dye-sensitized solar cells.Organic dye provided by the invention has formula (I) structure, in formula (I), and R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; X is the substituting group of formula (a) or formula (b) structure; In formula (a), y 1and y 2be independently 0 or 1; R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 7substituting group for formula (c) structure :-Q-COOH formula (c); In formula (c), Q is phenylene, naphthylidene or phenanthrylene.The invention provides the organic dye that one has formula (I) structure, this organic dye regulates the 3-D solid structure of dye molecule with the side modification group of large steric hindrance, and structure end is aided with the agent structure of carboxylic acid as grafting unit composition dye molecule of replacement simultaneously.Owing to having special molecular structure, make this organic dye show wider absorption spectrum and higher Solar use degree, and then significantly promote the photoelectric transformation efficiency of dye-sensitized solar cells.Experimental result shows, the photoelectric transformation efficiency of the dye-sensitized solar cells adopting organic dye provided by the invention to prepare is greater than 11%, belongs to the current leading level in the world.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of organic dye, there is structure shown in formula (I):
In formula (I), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces;
X is the substituting group of formula (a) or formula (b) structure:
In formula (a), y 1and y 2be independently 0 or 1, R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 7substituting group for formula (c) structure :-Q-COOH formula (c); In formula (c), Q is phenylene, naphthylidene or phenanthrylene.
The invention provides the organic dye that one has formula (I) structure.In formula (I), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; In an embodiment provided by the invention, R 1for H, C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces; In another embodiment provided by the invention, R 1substituting group for formula (d) structure:
In formula (d), R 8for C 1~ C 16alkoxyl group, is specially: methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, undecane oxygen base, dodecyloxy, tridecane oxygen base, tetradecyloxyaniline, pentadecane oxygen base or n-Hexadecane oxygen base.In an embodiment provided by the invention, R 8one in following structure substituting group:
-O-C 2H 5、-O-C 3H 7、-O-C 4H 9、-O-C 5H 11、-O-C 6H 13、-O-C 7H 15、-O-C 8H 17、-O-C 9H 19、-O-C 10H 21、
In the present invention, in formula (I), R 2, R ' 2, R 3and R ' 3independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; In an embodiment provided by the invention, R 2, R ' 2, R 3and R ' 3independently selected from C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces; In another embodiment provided by the invention, R 2, R ' 2, R 3and R ' 3independently selected from C 2~ C 18alkyl or C 2~ C 18the alkyl that alkoxyl group replaces; In other embodiments provided by the invention, R 2, R ' 2, R 3and R ' 3substituting group independently selected from formula (e) structure:
In formula (e), R ' 8for C 1~ C 16alkyl, is specially: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.In the present invention, described R 2, R ' 2, R 3and R ' 3in R ' 8can be identical, also can be different.
In the present invention, in formula (I), R 4for C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; In an embodiment provided by the invention, R 4for C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces; In another embodiment provided by the invention, R 4for C 2~ C 18alkyl or C 2~ C 18the alkyl that alkoxyl group replaces; In other embodiments provided by the invention, R 4for C 1~ C 36alkyl; In other embodiments provided by the invention, R 4for C 2~ C 18alkyl; In other embodiments provided by the invention, R 4for ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl; In other embodiments provided by the invention, R 4one in following structure substituting group:
In the present invention, in formula (I), X is the substituting group of formula (a) or formula (b) structure:
In formula (a), y 1and y 2be independently 0 or 1.R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; In an embodiment provided by the invention, R 5and R 6independently selected from H, F, C 1~ C 18alkyl or C 1~ C 18the alkyl that alkoxyl group replaces; In another embodiment provided by the invention, R 5and R 6independently selected from H, F, C 1~ C 18alkyl or C 1~ C 18alkoxyl group.
In formula (a), R 7substituting group for formula (c) structure :-Q-COOH formula (c); In formula (c), Q is phenylene, naphthylidene or phenanthrylene.In an embodiment provided by the invention, R 7one in following structure substituting group:
In an embodiment provided by the invention, described in there is formula (I) structure organic dye there is formula (II) or formula (III) structure:
The invention provides the organic dye that one has formula (I) structure, this organic dye regulates the 3-D solid structure of dye molecule with the side modification group of large steric hindrance, and structure end is aided with the agent structure of carboxylic acid as grafting unit composition dye molecule of replacement simultaneously.Owing to having special structure, make this organic dye show wider absorption spectrum and higher Solar use degree, and then significantly promote the photoelectric transformation efficiency of dye-sensitized solar cells.
In preferred implementation provided by the invention, described organic dye with two Sai fen Bing Pi and carbazole and diazosulfide for electron donor-acceptor (EDA) unit, show the Solar use degree of wider absorption spectrum and Geng Gao, and then significantly promote the photoelectric transformation efficiency of dye-sensitized solar cells.
Experimental result shows, the photoelectric transformation efficiency of the dye-sensitized solar cells adopting organic dye provided by the invention to prepare is greater than 11%, belongs to the current leading level in the world.
The invention provides a kind of preparation method of organic dye, comprise the following steps:
The prodrug esters with formula (IV) structure is hydrolyzed, and obtains the organic dye with formula (I) structure;
Or
The prodrug esters with formula (VI) structure is hydrolyzed, and obtains the organic dye with formula (I) structure;
Or
The described compound with formula (VII) structure reacts with the compound condensation with formula (VIII) structure, obtains the organic dye with formula (I) structure;
In formula (I), formula (IV), formula (VI) and formula (VII), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces;
In formula (I), X is the substituting group of formula (a) or formula (b) structure:
In formula (a), y 1and y 2be independently 0 or 1, R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 7substituting group for formula (c) structure :-Q-COOH formula (c); In formula (c), Q is phenylene, naphthylidene or phenanthrylene;
In formula (IV) and formula (VI), R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl.
In the present invention, provide the method that three kinds are prepared the organic dye with formula (I) structure, described in there is formula (I) structure organic dye can be prepared according to following steps:
The prodrug esters with formula (IV) structure is hydrolyzed, and obtains the organic dye with formula (I) structure.
Have in the method for the organic dye of formula (I) structure in above-mentioned preparation provided by the invention, direct the prodrug esters with formula (IV) structure to be hydrolyzed, can obtain the organic dye with formula (I) structure, this process is specially:
First there is described in prodrug esters elder generation and basic cpd and the solvent of formula (IV) structure, carry out alkaline hydrolysis.Wherein, the prodrug esters structure with formula (IV) structure is as follows:
In formula (IV), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl.
The present invention is not particularly limited the described source with the prodrug esters of formula (IV) structure, preferably prepares in accordance with the following methods:
The halogenated compound with formula (A-0) structure and the compound with formula (A-01) structure carry out linked reaction, obtain having formula (IV) structure prodrug esters.
In above-mentioned preparation method provided by the invention, directly the described halogenated compound with formula (A-0) structure is carried out linked reaction with the compound with formula (A-01) structure, can obtain the prodrug esters with formula (IV) structure, this process is specially:
There is the halogenated compound of formula (A-0) structure by described and there is the compound of formula (A-01) structure, carrying out linked reaction.Wherein, the halogenated compound structure described in formula (A-0) structure is as follows:
In formula (A-0), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, Z is Br or I.The present invention is not particularly limited the described halogenated compound source with formula (A-0) structure, preferably prepares in accordance with the following methods:
Halogenating agent carries out halogenating reaction with the compound with formula (A-1) structure, obtains the halogenated compound with formula (A-0) structure;
In formula (A-1), R 1h, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces.
Above-mentionedly have in the preparation method of the halogenated compound of formula (A-0) structure provided by the invention, first by halogenating agent and the compound with formula (A-1) structure, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-1) structure, preferably prepares in accordance with the following methods:
The compound with formula (A-2) structure carries out intramolecular cyclization reaction under an acidic catalyst condition, obtains the compound with formula (A-1) structure;
In formula (A-2), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces.
Above-mentionedly have in the preparation method of the compound of formula (A-1) structure provided by the invention, direct the compound with formula (A-2) structure is carried out intramolecular cyclization reaction under an acidic catalyst condition, can obtain the compound with formula (A-1) structure, this process is specially:
The compound first will with formula (A-2) structure mixes with an acidic catalyst, reacts.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-2) structure, preferably prepares in accordance with the following methods:
The compound with formula (A-3) structure reacts with the compound of the compound with formula (A-4-I) structure and formula (A-4-II) structure, obtains the compound with formula (A-2) structure;
In formula (A-3), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 11for C 1~ C 10alkyl; R 2, R ' 2and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 11for C 1~ C 10alkyl;
R 3-Mg-Z formula (A-4-I); R' 3-Mg-Z formula (A-4-II);
In formula (A-4-I) and formula (A-4-II), Z is Br or I; R 3and R ' 3independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces.
Above-mentionedly have in the preparation method of the compound of formula (A-2) structure provided by the invention, first by there is the compound of formula (A-3) structure and there is the compound of formula (A-4-I) structure and the compound of formula (A-4-II) structure, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-3) structure, preferably prepares in accordance with the following methods:
The compound with formula (A-5) structure and the compound with formula (A-6) structure react, and obtain the compound with formula (A-3) structure;
In formula (A-5), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2and R 4independently selected from H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; Z is Br or I;
In formula (A-6), R 11for C 1~ C 10alkyl.
Above-mentionedly have in the preparation method of the compound of formula (A-3) structure provided by the invention, direct the compound with formula (A-5) structure and the compound with formula (A-6) structure to be reacted, can obtain the compound with formula (A-3) structure, this process is specially:
First by there is the compound of formula (A-5) structure and there is the compound of formula (A-6) structure, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-5) structure, preferably prepares in accordance with the following methods:
Compound and the halogenating agent with formula (A-7) structure react, and obtain the halogenated compound with formula (A-5) structure;
In formula (A-7), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2and R 4independently selected from H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces.
Above-mentionedly have in the preparation method of the compound of formula (A-5) structure provided by the invention, direct the compound and halogenating agent with formula (A-7) structure to be reacted, can obtain the halogenated compound with formula (A-5) structure, this process is specially:
The compound first will with formula (A-7) structure mixes with halogenating agent, reacts.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-7) structure, preferably prepares in accordance with the following methods:
The compound with formula (A-8) structure and the compound with formula (A-9) structure carry out linked reaction, obtain the compound with formula (A-7) structure;
In formula (A-8), R 2, R ' 2and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; A 1, A 2and A 3separately be selected from C 1~ C 10alkyl;
R 1-Z formula (A-9);
In formula (A-9), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; Z is Br or I.
Above-mentionedly have in the preparation method of the compound of formula (A-7) structure provided by the invention, direct the compound with formula (A-8) structure and the compound with formula (A-9) structure are carried out linked reaction, can obtain the compound with formula (A-7) structure, this process is specially:
First by there is the compound of formula (A-8) structure and there is the compound of formula (A-9) structure, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-8) structure, preferably prepares in accordance with the following methods:
Compound and the lithiumation agent with formula (A-10) structure are reacted, and obtain lithiation liquid; Described lithiation liquid and tin agent are reacted, and obtain the compound with formula (A-8) structure;
In formula (A-10), R 2, R ' 2and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces.
Above-mentionedly have in the preparation method of the compound of formula (A-8) structure provided by the invention, first the described compound with formula (A-10) structure is mixed with lithiumation agent, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-10) structure, preferably prepares in accordance with the following methods:
The described compound with formula (A-11) structure carries out intramolecular cyclization reaction under an acidic catalyst condition, obtains the compound with formula (A-10) structure;
In formula (A-11), R 2, R ' 2and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces.
Above-mentionedly have in the preparation method of the compound of formula (A-10) structure provided by the invention, direct the compound with formula (A-11) structure is carried out intramolecular cyclization reaction under an acidic catalyst condition, can obtain the compound with formula (A-10) structure, this process is specially:
The compound first will with formula (A-11) structure mixes with an acidic catalyst, reacts.Wherein, the source described in the present invention is many with the compound of formula (A-11) structure is not particularly limited, and preferably prepares in accordance with the following methods:
The described compound with formula (A-12) structure reacts with the compound of the compound and formula (A-13-II) structure with formula (A-13-I) structure, obtains the compound with formula (A-11) structure;
In formula (A-12), R 4for C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, R 10for C 1~ C 10alkyl;
R 2-Mg-Z formula (A-13-I); R' 2-Mg-Z formula (A-13-II);
In formula (A-13-I) and formula (A-13-II), Z is Br or I; R 2and R ' 2independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces.
Above-mentionedly have in the preparation method of the compound of formula (A-11) structure provided by the invention, direct the compound of the compound with formula (A-12) structure with the compound and formula (A-13-II) structure with formula (A-13-I) structure to be reacted, can obtain the compound with formula (A-11) structure, this process is specially:
By there is the compound of formula (A-12) structure and there is the compound of formula (A-13-I) structure and the compound of formula (A-13-II) structure, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-12) structure, preferably prepares in accordance with the following methods:
The compound with formula (A-14) structure and the compound with formula (A-15) structure react, and obtain the compound with formula (A-12) structure;
In formula (A-14), R 4for C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, Z is Br or I;
In formula (A-15), R 10for C 1~ C 10alkyl.
Above-mentionedly have in the preparation method of the compound of formula (A-12) structure provided by the invention, direct the compound with formula (A-14) structure and the compound with formula (A-15) structure to be reacted, can obtain the compound with formula (A-12) structure, this process is specially:
By there is the compound of formula (A-14) structure and there is the compound of formula (A-15) structure, react.Wherein, the structure described in the compound of formula (A-14) structure is as follows:
In formula (A-14), Z is Br or I; R 4for C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, is preferably C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces, is more preferably C 2~ C 18alkyl or C 2~ C 18the alkyl that alkoxyl group replaces, most preferably is C 2~ C 18alkyl, is the most preferably ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.In an embodiment provided by the invention, R 4one in following structure substituting group:
In an embodiment provided by the invention, described in there is formula (A-14) structure compound be specially formula (A-14-a) structure:
In the present invention, the described source with the compound of formula (A-14) structure is not particularly limited, can commercial goods be selected, also can obtain according to document (Y.Li, Z.Wang, Org.Lett.2009,11,1386.) synthesis.
The described structure with the compound of formula (A-15) structure is as follows:
In formula (A-15), R 10for C 1~ C 10alkyl, is preferably C 1~ C 5alkyl, is specially-CH 3,-C 2h 5,-C 3h 7,-C 4h 9or-C 5h 11.
In an embodiment provided by the invention, described in there is formula (A-15) structure compound be specially 3-carboxylic acid, ethyl ester thiophene, its structure is such as formula shown in (A-15-a):
In the present invention, the described source with the compound of formula (A-15) structure is not particularly limited, selects commercial goods.
Described have the compound of formula (A-14) structure and have in the compound reaction process of formula (A-15) structure, the described compound with formula (A-14) structure is preferably 1:0.5 ~ 2 with the mol ratio of the compound with formula (A-15) structure, is more preferably 1:1 ~ 1.1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably toluene.Described reaction is preferably carried out in the presence of a catalyst, and described catalyzer is preferably Pd (OAc) 2, PCy 3hBF 4, PivOH and K 2cO 3in one or more, be more preferably Pd (OAc) 2, PCy 3hBF 4, PivOH and K 2cO 3.Pd (OAc) in described catalyzer 2, PCy 3hBF 4, PivOH and K 2cO 3mass ratio be preferably 30 ~ 50:90 ~ 120:70 ~ 100:500 ~ 600.Described catalyzer is preferably 500 ~ 700 (mg): 3 ~ 4 (mmol) with the amount ratio of the compound with formula (A-14) structure.Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The mode of described reaction is preferably back flow reaction.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-12) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (A-12) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably toluene and/or sherwood oil, is more preferably toluene and sherwood oil that volume ratio is 1:1.
In the present invention, the described compound with formula (A-12) structure with have in the compound of formula (A-13-I) structure and the compound reaction process of formula (A-13-II) structure, described in there is formula (A-13-I) and formula (A-13-II) structure compound there is following structure:
R 2-Mg-Z formula (A-13-I); R' 2-Mg-Z formula (A-13-II);
In formula (A-13-I) and formula (A-13-II), Z is Br or I; R 2and R ' 2independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, preferably from C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces, more preferably from C 2~ C 18alkyl or C 2~ C 18the alkyl that alkoxyl group replaces, most preferably from the substituting group of formula (e) structure:
In formula (e), R ' 8for C 1~ C 16alkyl, is specially: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.In the present invention, described R 2and R ' 2in R ' 8can be identical, also can be different.
In an embodiment provided by the invention, described in there is formula (A-13-I) and formula (A-13-II) structure compound be hexyl benzene magnesium bromide, its structure is such as formula shown in (A-13-a):
In the present invention, the described source with the compound of formula (A-13-I) and formula (A-13-II) structure is not particularly limited, selects commercial goods.
In the present invention, described have the compound of formula (A-12) structure and have in the compound of formula (A-13-I) structure and the compound reaction process of formula (A-13-II) structure, the integral molar quantity of the described compound with (A-13-I) structure and the compound with formula (A-13-II) structure is preferably 5 ~ 20:1 with the mol ratio of the compound with formula (A-12) structure, is more preferably 8 ~ 12:1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably tetrahydrofuran (THF).Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.In the present invention, preferably first the compound with (A-12) structure and the compound with formula (A-13-I) and formula (A-13-II) structure are dissolved by organic solution respectively respectively, and then the solution after dissolving is mixed, react.The temperature of described reaction is preferably 80 ~ 100 DEG C, is more preferably 90 ~ 95 DEG C.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-11) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product through cancellation, extraction, drying and after concentrating, obtains the compound with formula (A-11) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate.
In the present invention, described in have in the compound of formula (A-11) structure and the process of an acidic catalyst hybrid reaction, described an acidic catalyst is preferably sulfonic acid type catalyzer, and the model of described sulfonic acid type catalyzer is preferably Amberlyst-15.Described catalyzer and the raw material described in preparation with the compound of formula (A-11) structure, the amount ratio namely with the compound of formula (A-12) structure is preferably 1 (g): 0.5 ~ 3 (mmol), is more preferably 1 (g): 1 ~ 2 (mmol).Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably toluene.Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The preferred back flow reaction of mode of described reaction.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-10) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (A-10) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably sherwood oil.
In the present invention, described in there is formula (A-10) structure compound and lithiumation agent hybrid reaction process in, described lithiumation agent is preferably butyllithium, is more preferably n-Butyl Lithium.Described lithiumation agent is preferably 0.5 ~ 2:1 with the mol ratio of the compound with formula (A-10) structure, is more preferably 1 ~ 1.2:1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably tetrahydrofuran (THF).Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The temperature of described reaction is preferably-60 ~-90 DEG C, is more preferably-78 ~-80 DEG C.The time of described reaction is preferably 0.5 ~ 2h, is more preferably 1 ~ 2h.After reaction terminates, obtain lithiation liquid.Described lithiation liquid mixes with tin agent, reacts.Wherein, described tin agent is preferably trialkyl tin halides, and its structure is as follows:
In above formula, A 1, A 2and A 3separately be selected from C 1~ C 10alkyl, preferably from C 1~ C 3alkyl; Z ' is Cl or Br.
In an embodiment provided by the invention, described tin agent is specially trimethyltin chloride, and its structure is as follows:
In described lithiation liquid and tin agent hybrid reaction process, described tin agent and the mol ratio 0.5 ~ 2:1 of compound with formula (A-10) structure, be more preferably 1 ~ 1.2:1.Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The temperature of described reaction is preferably room temperature.The time of described reaction is preferably 8 ~ 20h, is more preferably 10 ~ 15h.After reaction terminates, obtain the solution containing reaction product.The described solution containing reaction product, through aftertreatment, obtains the compound with formula (A-8) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product through cancellation, extraction, drying and after concentrating, obtains the compound with formula (A-8) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate.
In the present invention, described in there is formula (A-8) structure compound with have in the compound reaction process of formula (A-9) structure, described in there is formula (A-9) structure compound there is following structure:
R 1-Z formula (A-9);
In formula (A-9), Z is Br or I; R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, is preferably H, C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces, is more preferably the substituting group of formula (d) structure:
In formula (d), R 8for C 1~ C 16alkoxyl group, is specially: methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, undecane oxygen base, dodecyloxy, tridecane oxygen base, tetradecyloxyaniline, pentadecane oxygen base or n-Hexadecane oxygen base.In an embodiment provided by the invention, R 8one in following structure substituting group:
-O-C 2H 5、-O-C 3H 7、-O-C 4H 9、-O-C 5H 11、-O-C 6H 13、-O-C 7H 15、-O-C 8H 17、-O-C 9H 19、-O-C 10H 21、
In an embodiment provided by the invention, the described compound with formula (A-9) structure is specially 4-oxyethyl group iodobenzene or 4-(2-hexyl oxygen in last of the ten Heavenly stems base) iodobenzene, wherein, the structure of 4-oxyethyl group iodobenzene is such as formula shown in (A-9-a), and the structure of 4-(2-hexyl oxygen in last of the ten Heavenly stems base) iodobenzene is such as formula shown in (A-9-b):
The present invention is not particularly limited the described source with the compound of formula (A-9) structure, selects commercial goods.
In the present invention, described have the compound of formula (A-8) structure and have in the compound reaction process of formula (A-9) structure, the compound of described formula (A-9) structure and the raw material of preparation formula (A-8) structural compounds, the mol ratio namely with the compound of formula (A-10) structure is preferably 0.5 ~ 3:1, be more preferably 1 ~ 2.5:1, most preferably be 2 ~ 2.5:1.Described reaction is preferably carried out in the presence of a catalyst, and described catalyzer is preferably Pd (PPh 3) 2cl 2.The raw material of described catalyzer and preparation formula (A-8) structural compounds, the amount ratio namely with the compound of formula (A-10) structure is preferably 30 ~ 50 (mg): 1 ~ 2 (mmol), is more preferably 40 ~ 50 (mg): 1 ~ 1.2 (mmol).Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably toluene.Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The preferred back flow reaction of mode of described reaction.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-7) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (A-7) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably toluene and/or sherwood oil, is more preferably toluene and sherwood oil that volume ratio is 1:10.
In the present invention, the compound described in formula (A-7) structure can also be prepared in accordance with the following methods:
The compound with formula (A-8 ') structure carries out linked reaction with the compound with formula (A-9) structure, obtains the compound with formula (A-7) structure;
Formula (A-8 ') in, R 2, R ' 2and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces.
Above-mentionedly have in the preparation method of the compound of formula (A-7) structure provided by the invention, direct the compound with formula (A-8 ') structure is carried out linked reaction with the compound with formula (A-9) structure, can obtain the compound with formula (A-7) structure, this process is specially:
First by there is the compound of formula (A-8 ') structure and there is the compound of formula (A-9) structure, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-8 ') structure, preferably prepares in accordance with the following methods:
Compound and the lithiumation agent with formula (A-10) structure are reacted, and obtain having the compound of formula (A-8 ') structure.
Above-mentionedly have in the preparation method of the compound of formula (A-8 ') structure provided by the invention, direct will have formula (A-10) structure compound and lithiumation agent react, can obtain having the compound of formula (A-8 ') structure, this process is specially:
First the described compound with formula (A-10) structure is mixed with lithiumation agent, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (A-10) structure, preferably prepares in accordance with the following methods:
The compound will with formula (A-10) structure mixes with lithiumation agent, reacts.Wherein, described lithiumation agent is preferably butyllithium, is more preferably n-Butyl Lithium.Described lithiumation agent is preferably 0.5 ~ 2:1 with the mol ratio of the compound with formula (A-10) structure, is more preferably 1 ~ 1.2:1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably tetrahydrofuran (THF).Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The temperature of described reaction is preferably-60 ~-90 DEG C, is more preferably-78 ~-80 DEG C.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains having the compound of formula (A-8 ') structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product, successively through cancellation, extraction, drying and after concentrating, obtains having the compound of formula (A-8 ') structure.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate.
In the present invention, the described compound with formula (A-8 ') structure with have in the compound reaction process of formula (A-9) structure, the raw material of the compound of described formula (A-9) structure and preparation formula (A-8 ') structural compounds, the mol ratio namely with the compound of formula (A-10) structure is preferably 0.5 ~ 3:1, be more preferably 1 ~ 2.5:1, most preferably be 2 ~ 2.5:1.Described reaction is preferably carried out in the presence of a catalyst, and described catalyzer is preferably Pd (PPh 3) 2cl 2.The raw material of described catalyzer and preparation formula (A-8 ') structural compounds, the amount ratio namely with the compound of formula (A-10) structure is preferably 30 ~ 50 (mg): 1 ~ 2 (mmol), is more preferably 40 ~ 50 (mg): 1 ~ 1.2 (mmol).Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably toluene.Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The preferred back flow reaction of mode of described reaction.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-7) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (A-7) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably toluene and/or sherwood oil, is more preferably toluene and sherwood oil that volume ratio is 1:10.
In the present invention, described in there is formula (A-7) structure compound and halogenating agent hybrid reaction process in, described halogenating agent is preferably N-bromo-succinimide.The mol ratio of the described compound and halogenating agent with formula (A-7) structure is preferably 1:1 ~ 2, is more preferably 1:1.4 ~ 1.6.Preferably in organic solvent, described organic solvent is preferably tetrahydrofuran (THF) in described reaction.The temperature of described reaction is preferably-10 ~ 10 DEG C, is more preferably-5 ~ 5 DEG C.The time of described reaction is preferably 0.5 ~ 5h, is more preferably 1 ~ 2h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-5) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product through cancellation, extraction, drying and after concentrating, obtains the compound with formula (A-5) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate.
In the present invention, described in there is formula (A-5) structure compound with have in the compound reaction process of formula (A-6) structure, described in there is formula (A-6) structure compound there is following structure:
In formula (A-6), R 11for C 1~ C 10alkyl, is preferably C 1~ C 5alkyl, is specially-CH 3,-C 2h 5,-C 3h 7,-C 4h 9or-C 5h 11.
In an embodiment provided by the invention, described in there is formula (A-6) structure compound be specially 3-carboxylate methyl ester thiophene, its structure is such as formula shown in (A-6-a):
In the present invention, the described source with the compound of formula (A-6) structure is not particularly limited, selects commercial goods.
In the present invention, described have the compound of formula (A-5) structure and have in the compound reaction process of formula (A-6) structure, described there is formula (A-6) structure compound and preparation formula (A-5) structural compounds raw material used, the mol ratio namely with the compound of formula (A-7) structure is preferably 0.5 ~ 2:1, is more preferably 1 ~ 1.2:1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably toluene.Described reaction is preferably carried out in the presence of a catalyst, and described catalyzer is preferably Pd (OAc) 2, PCy 3hBF 4, PivOH and K 2cO 3in one or more, be more preferably Pd (OAc) 2, PCy 3hBF 4, PivOH and K 2cO 3.Pd (OAc) in described catalyzer 2, PCy 3hBF 4, PivOH and K 2cO 3mass ratio be preferably 5 ~ 10:20 ~ 30:10 ~ 25:100 ~ 200.Described catalyzer and preparation formula (A-5) structural compounds raw material used, the amount ratio namely with the compound of formula (A-7) structure is preferably 150 ~ 200 (mg): 0.6 ~ 1 (mmol).Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.Carry out under the preferred reflux conditions of described reaction.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-3) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (A-3) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably toluene and/or sherwood oil, is more preferably toluene and sherwood oil that volume ratio is 1:1.
In the present invention, in the process that the compound of the compound with formula (A-3) structure and the compound with formula (A-4-I) structure and formula (A-4-II) structure is reacted, described in there is formula (A-4-I) and formula (A-4-II) structure compound there is following structure:
R 3-Mg-Z formula (A-4-I); R' 3-Mg-Z formula (A-4-II);
In formula (A-4-I) and formula (A-4-II), Z is Br or I; R 3and R ' 3independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, preferably from C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces, more preferably from C 2~ C 18alkyl or C 2~ C 18the alkyl that alkoxyl group replaces, most preferably from the substituting group of formula (e) structure:
In formula (e), R ' 8for C 1~ C 16alkyl, is specially: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.In the present invention, described R 3and R ' 3in R ' 8can be identical, also can be different.
In an embodiment provided by the invention, described in there is formula (A-4-I) and formula (A-4-II) structure compound be hexyl benzene magnesium bromide.
In the present invention, the described source with the compound of formula (A-4-I) and formula (A-4-II) structure is not particularly limited, selects commercial goods.
Described have the compound of formula (A-3) structure and have in the compound of formula (A-4-I) structure and the compound reaction process of formula (A-4-II) structure, the integral molar quantity of the described compound with (A-4-I) structure and the compound with formula (A-4-II) structure is preferably 5 ~ 20:1 with the mol ratio of the compound with formula (A-3) structure, is more preferably 8 ~ 12:1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably tetrahydrofuran (THF).Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.In the present invention, preferably first the compound with (A-3) structure and the compound organic solution with formula (A-4-I) and formula (A-4-II) structure are dissolved respectively, and then the solution after dissolving is mixed, react.The temperature of described reaction is preferably 80 ~ 100 DEG C, is more preferably 90 ~ 95 DEG C.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-2) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product through cancellation, extraction, drying and after concentrating, obtains the compound with formula (A-2) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate.
In the present invention, described in have in the compound of formula (A-2) structure and the process of an acidic catalyst hybrid reaction, described an acidic catalyst is preferably sulfonic acid type catalyzer, and the model of described sulfonic acid type catalyzer is preferably Amberlyst-15.Described catalyzer and preparation have the raw material of the compound of formula (A-2) structure, the amount ratio namely with the compound of formula (A-3) structure is preferably 1 (g): 0.5 ~ 3 (mmol), is more preferably 1 (g): 0.8 ~ 1.2 (mmol).Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably toluene.Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The preferred back flow reaction of mode of described reaction.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (A-1) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (A-1) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably sherwood oil.
In the present invention, in the process that described halogenating agent and the compound with formula (A-1) structure are reacted, described halogenating agent is preferably N-bromo-succinimide.The mol ratio of the compound of described halogenating agent and formula (A-1) structure is preferably 1.1 ~ 1.5:1, is more preferably 1.1 ~ 1.2:1.The temperature of described reaction is preferably-10 ~ 10 DEG C, is more preferably-5 ~ 5 DEG C.The time of described reaction is preferably 0.5 ~ 5h, is more preferably 1 ~ 2h.。After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the halogenated compound with formula (A-0) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (A-0) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate.
In the present invention, described in the halogenated compound with formula (A-0) structure and the compound with formula (A-01) the structure process of reacting, described in there is formula (A-01) structure compound there is following structure:
In formula (A-01), y 2be 0 or 1, R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, preferably from H, F, C 1~ C 18alkyl or C 1~ C 18the alkyl that alkoxyl group replaces, more preferably from R 5and R 6independently selected from H, F, C 1~ C 18alkyl or C 1~ C 18alkoxyl group.
In formula (A-01), R ' 7substituting group for formula (c ') structure: formula (c '); Formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl, is preferably C 3~ C 6alkyl; In an embodiment provided by the invention, R ' 7one in following structure substituting group:
In an embodiment provided by the invention, described in there is formula (A-01) structure compound be specially formula (A-01-a) structure or formula (A-01-b) structure:
The present invention is not particularly limited the described source with the compound of formula (A-01) structure, adopts and well known to a person skilled in the art method preparation or adopt this commercial goods.
In the present invention, in the process that the described halogenated compound with formula (A-0) structure and the compound with formula (A-01) structure are reacted, described have the compound of formula (A-0) structure and have in the compound reaction process of formula (A-01) structure, the described compound with formula (A-0) structure is preferably 1:0.5 ~ 2 with the mol ratio of the compound with formula (A-01) structure, is more preferably 1:1.5 ~ 2.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably Isosorbide-5-Nitrae-dioxane.Described reaction is preferably carried out in the presence of a catalyst, and described catalyzer is preferably Pd 2(dba) 3and tri-butyl phosphine.Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The type of described linked reaction is preferably Sonogashira linked reaction.The temperature of described reaction is preferably 80 ~ 120 DEG C, is more preferably 90 ~ 110 DEG C.The time of described reaction is preferably 3 ~ 10h, is more preferably 5 ~ 6h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the prodrug esters with formula (IV) structure.
In the present invention, described in there is formula (IV) structure prodrug esters first carry out in the process of alkaline hydrolysis with basic cpd and solvent, described basic cpd is preferably potassium hydroxide and/or sodium hydroxide.The raw material that described basic cpd is used with the described prodrug esters of preparation, the mol ratio namely with the compound of formula (A-0) structure is preferably 2 ~ 20:1, is more preferably 3 ~ 7:1.Described solvent is preferably water and organic solvent, and described organic solvent is preferably tetrahydrofuran (THF).The temperature of described alkaline hydrolysis is preferably 60 ~ 90 DEG C, is more preferably 70 ~ 80 DEG C.The time of shown alkaline hydrolysis is preferably 3 ~ 8h, is more preferably 5 ~ 6h.After alkaline hydrolysis terminates, obtain the salt that prodrug esters is corresponding.
After obtaining salt corresponding to described prodrug esters, the salt that described prodrug esters is corresponding mixes with acid, carries out replacement(metathesis)reaction.Described acid is preferably phosphoric acid.The raw material that the salt that described phosphoric acid is corresponding with preparing prodrug esters is used, the mol ratio namely with the compound of formula (A-0) structure is preferably 2 ~ 20:1, is more preferably 6 ~ 10:1.After reaction terminates, obtain the solution containing reaction product.The described solution containing reaction product carries out aftertreatment, obtains the organic dye with formula (I) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the organic dye with formula (I) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably trichloromethane and/or methyl alcohol, is more preferably trichloromethane and methyl alcohol that volume ratio is 1:20.
In the present invention, the organic dye described in formula (I) structure can also be prepared according to following steps:
The prodrug esters with formula (VI) structure is hydrolyzed, and obtains the organic dye with formula (I) structure.
Have in the method for the organic dye of formula (I) structure in above-mentioned preparation provided by the invention, direct the prodrug esters with formula (VI) structure to be hydrolyzed, can obtain the organic dye with formula (I) structure, this process is specially:
First there is described in prodrug esters elder generation and basic cpd and the solvent of formula (VI) structure, carry out alkaline hydrolysis.Wherein, the prodrug esters structure with formula (VI) structure is as follows:
In formula (VI), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl.
The present invention is not particularly limited the described source with the prodrug esters of formula (VI) structure, preferably prepares in accordance with the following methods:
The described tin with formula (B-1) structure carries out linked reaction for compound and the compound with formula (B-2) structure, obtains the prodrug esters with formula (VI) structure;
In formula (B-1), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; A 1, A 2and A 3separately be selected from C 1~ C 10alkyl;
In formula (B-2), R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; Z is Br or I; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl.
Above-mentionedly have in the preparation method of the prodrug esters of formula (VI) structure provided by the invention, direct the tin with formula (B-1) structure is carried out linked reaction for compound and the compound with formula (B-2) structure, can obtain the prodrug esters with formula (VI) structure, this process is specially:
The tin with formula (B-1) structure, for compound and the compound with formula (B-2) structure, reacts.Wherein, the present invention is not particularly limited the source of the described tin with formula (B-1) structure for compound, preferably prepares in accordance with the following methods:
First by lithiumation agent and the compound with formula (A-1) structure, lithiation is carried out.Wherein, described lithiumation agent is preferably butyllithium, is more preferably n-Butyl Lithium.Described lithiumation agent is preferably 0.5 ~ 2:1 with the mol ratio of the compound with formula (A-1) structure, is more preferably 1.2 ~ 1.6:1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably tetrahydrofuran (THF).Described reaction is preferably carried out in inert gas atmosphere, and described rare gas element is preferably argon gas.The temperature of described reaction is preferably-60 ~-90 DEG C, is more preferably-78 ~-80 DEG C.The time of described reaction is preferably 0.5 ~ 2h, is more preferably 1 ~ 2h.After reaction terminates, obtain lithiation liquid.Described lithiation liquid mixes with tin agent, reacts.Wherein, described tin agent is preferably trialkyl tin halides, and its structure is as follows:
Wherein, A 1, A 2and A 3separately be selected from C 1~ C 10alkyl, preferably from C 1~ C 3alkyl; Z ' is Cl or Br.In an embodiment provided by the invention, described tin agent is specially trimethyltin chloride.
In described lithiation liquid and tin agent hybrid reaction process, described tin agent and the mol ratio 0.5 ~ 2:1 of compound with formula (A-1) structure, be more preferably 1.2 ~ 1.6:1.State reaction preferably to carry out in inert gas atmosphere, described rare gas element is preferably argon gas.The temperature of described reaction is preferably room temperature.The time of described reaction is preferably 8 ~ 20h, is more preferably 10 ~ 15h.After reaction terminates, obtain the solution containing reaction product.The described solution containing reaction product, through aftertreatment, obtains having the tin of formula (B-1) structure for compound.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product, successively through cancellation, extraction, drying and after concentrating, obtains having the tin of formula (B-1) structure for compound.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate.
In the present invention, described in there is formula (B-1) structure the tin process of reacting for compound and the compound with formula (B-2) structure in, described in there is formula (B-2) structure compound there is following structure:
In formula (B-2), Z is Br or I; y 2be 0 or 1; R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, preferably from H, F, C 1~ C 18alkyl or C 1~ C 18the alkyl that alkoxyl group replaces, more preferably from H, F, C 1~ C 18alkyl or C 1~ C 18alkoxyl group.
In formula (B-2), R ' 7substituting group for formula (c ') structure: formula (c '); Formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl, is preferably C 3~ C 6alkyl; In an embodiment provided by the invention, R ' 7one in following structure substituting group:
In an embodiment provided by the invention, described in there is formula (B-2) structure compound be specially formula (B-2-a) structure, formula (B-2-b) structure, formula (B-2-c) structure or formula (B-2-d) structure:
In the present invention, the described source with the compound of formula (B-2) structure is not particularly limited, can is commercial goods, also can prepares according to following steps:
There is the compound of formula (B-3) structure and there is the compound of formula (B-4) structure, carrying out condensation reaction, obtain the compound with formula (B-2) structure.Wherein, the compound described in formula (B-3) structure has following structure:
In formula (B-3), y 2be 0 or 1; R ' 7with R ' in (B-2) 7refer to identical, do not repeat them here.In an embodiment provided by the invention, described in there is formula (B-3) structure compound be specially formula (B-3-a) structure, formula (B-3-b) structure, formula (B-3-c) structure or formula (B-3-d) structure:
In the present invention, being not particularly limited the described source with the compound of formula (B-3) structure, can be commercial goods, also can according to document (R.H.Pawle, V.EastmanandS.W.Thomas, J.Mater.Chem., 2011,21,14041) synthesis obtains.
The described compound with formula (B-4) structure has following structure:
In formula (B-4), Z, R 5and R 6with Z, R in (B-2) 5and R 6refer to identical, do not repeat them here.In an embodiment provided by the invention, described in there is formula (B-4) structure compound be specially formula (B-4-a) structure or formula (B-4-b) structure:
In the present invention, being not particularly limited the described source with the compound of formula (B-4) structure, can be commercial goods, also can prepare according to mode well known to those skilled in the art.
Described have the compound of formula (B-3) structure and have in the process of compound reaction of formula (B-4) structure, the described compound with formula (B-3) structure is preferably 1:0.5 ~ 2 with the mol ratio of the compound with formula (B-4) structure, is more preferably 1:1 ~ 1.1.Described reaction is preferably carried out in the presence of a catalyst, and described catalyzer is preferably Pd (PPh 3) 2cl 2, triphenylphosphine, one or more in cuprous iodide and diisopropylamine, be more preferably Pd (PPh 3) 2cl 2, triphenylphosphine, cuprous iodide and diisopropylamine.Pd (PPh in catalyzer 3) 2cl 2, triphenylphosphine, cuprous iodide and diisopropylamine mass ratio be preferably 60 ~ 70:40 ~ 50:10 ~ 20:2 ~ 3.Described catalyzer is preferably with the amount ratio of the compound with formula (B-3) structure: 4 ~ 5 (mmol): 100 ~ 150 (mg).Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably toluene.The temperature of described reaction is preferably 70 ~ 90 DEG C.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (B-2) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (B-2) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably chloroform and/or sherwood oil, is more preferably chloroform and sherwood oil that volume ratio is 3:1.
The described tin with formula (B-1) structure for compound with have in the compound reaction process of formula (B-2) structure, described there is formula (B-2) structure compound and preparation there is the raw material of formula (B-1) structure tin for compound, the mol ratio namely with the compound of formula (A-1) structure is preferably 0.5 ~ 2:1, is more preferably 1.5 ~ 2:1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably toluene.Described reaction is preferably carried out in the presence of a catalyst, and described catalyzer is preferably Pd (PPh 3) 2cl 2.Described catalyzer and preparation have the raw material of formula (B-1) structure tin for compound, the amount ratio namely with the compound of formula (A-1) structure is preferably 20 ~ 60 (mg): 0.4 ~ 0.5 (mmol), is more preferably 30 ~ 40 (mg): 0.4 ~ 0.5 (mmol).The preferred back flow reaction of mode of described reaction.The time of described reaction is preferably 10 ~ 24h, is more preferably 12 ~ 16h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the prodrug esters with formula (VI) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the prodrug esters with formula (VI) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably toluene and/or sherwood oil, is more preferably toluene and sherwood oil that volume ratio is 2:1.
In the present invention, described in there is formula (VI) structure prodrug esters first carry out in the process of alkaline hydrolysis with basic cpd and solvent, described basic cpd is preferably potassium hydroxide and/or sodium hydroxide.The raw material that described basic cpd is used with the described prodrug esters of preparation, the mol ratio namely with the compound of formula (A-1) structure is preferably 2 ~ 20:1, is more preferably 3 ~ 7:1.Described solvent is preferably water and organic solvent, and described organic solvent is preferably tetrahydrofuran (THF).The temperature of described alkaline hydrolysis is preferably 60 ~ 90 DEG C, is more preferably 70 ~ 80 DEG C.The time of shown alkaline hydrolysis is preferably 3 ~ 8h, is more preferably 5 ~ 6h.After alkaline hydrolysis terminates, obtain the salt that prodrug esters is corresponding.
After obtaining salt corresponding to described prodrug esters, the salt that described prodrug esters is corresponding mixes with acid, carries out replacement(metathesis)reaction.Described acid is preferably phosphoric acid.The raw material that the salt that described phosphoric acid is corresponding with preparing prodrug esters is used, the mol ratio namely with the compound of formula (A-1) structure is preferably 2 ~ 20:1, is more preferably 6 ~ 10:1.After reaction terminates, obtain the solution containing reaction product.The described solution containing reaction product carries out aftertreatment, obtains the organic dye with formula (I) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the organic dye with formula (I) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably trichloromethane and/or methyl alcohol, is more preferably trichloromethane and methyl alcohol that volume ratio is 1:20.
In the present invention, the organic dye described in formula (I) structure can also be prepared according to following steps:
The described compound with formula (VII) structure reacts with the compound condensation with formula (VIII) structure, obtains the organic dye with formula (I) structure.
Above-mentionedly have in the preparation method of the organic dye of formula (I) structure provided by the invention, direct the compound with formula (VII) structure and the compound condensation with formula (VIII) structure to be reacted, can obtain the organic dye with formula (I) structure, this process is specially:
By there is the compound of formula (VII) structure and there is the compound of formula (VIII) structure, react.Wherein, the present invention is not particularly limited the described source with the compound of formula (VII) structure, preferably prepares in accordance with the following methods:
Described formylation reagent carries out formylation reaction with the compound with formula (A-1) structure, obtains the compound with formula (VII) structure.
Above-mentionedly have in the preparation method of the compound of formula (VII) structure provided by the invention, first by formylation reagent and the compound with formula (A-1) structure, carry out formylation reaction.Wherein, described formylation reagent is preferably DMF and/or phosphorus oxychloride, is more preferably DMF and phosphorus oxychloride.The mol ratio of the compound of described DMF, phosphorus oxychloride and formula (A-1) structure is preferably 10 ~ 5:1.3 ~ 1.6:1, is more preferably 8 ~ 6:1.4 ~ 1.5:1.Described formylation reaction temperature is preferably-10 ~ 10 DEG C, is more preferably-5 ~ 5 DEG C.The time of described formylation reaction is preferably 1 ~ 12h, is more preferably 6 ~ 8h.After reaction terminates, obtain the solution containing reaction product.Aftertreatment is carried out to the described solution containing reaction product, obtains the compound with formula (VII) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the compound with formula (VII) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably toluene and/or sherwood oil, is more preferably toluene and sherwood oil that volume ratio is 1:1.
In the present invention, described in the compound with formula (VII) structure and the compound with formula (VIII) the structure process of reacting, described in there is formula (VIII) structure compound there is following structure:
In the process that the described compound with formula (VII) structure and the compound with formula (VIII) structure are reacted, the described compound with formula (VII) structure is preferably 10 ~ 5:1 with the mol ratio of the compound with formula (VIII) structure, is more preferably 8 ~ 6:1.Described reaction is preferably carried out in organic solvent, and described organic solvent is preferably trichloromethane.Described reaction is preferably carried out in the presence of a catalyst, and described catalyzer is preferably amine acetate.The mol ratio of the compound of described catalyzer and formula (VII) structure is preferably 4 ~ 2:1, is more preferably 3 ~ 2:1.The temperature of described reaction is preferably 60 ~ 80 DEG C, is more preferably 70 ~ 75 DEG C.The time of described reaction is preferably 8 ~ 12h, is more preferably 9 ~ 10h.After reaction terminates, the solution containing reaction product obtained carries out aftertreatment, obtains the organic dye with formula (I) structure.
In the present invention, the process that the above-mentioned solution containing reaction product carries out aftertreatment is specially: the solution containing reaction product after cancellation, extraction, drying, concentrated and column chromatography, obtains the organic dye with formula (I) structure successively.The quencher that described cancellation uses is preferably water; The extraction agent of described extraction is preferably chloroform; The siccative of described drying is preferably anhydrous sodium sulphate; The developping agent of described column chromatography is preferably trichloromethane and/or methyl alcohol, is more preferably trichloromethane and methyl alcohol that volume ratio is 1:20.
Adopt method provided by the invention to obtain to have the organic dye of formula (I) structure, the dye-sensitized solar cells photoelectric transformation efficiency adopting this organic dye to prepare is higher.Preparation method's abundant raw material source provided by the invention, cost are lower, and preparation process is simple, and product yield is high, and industrial production prospect is better.
The invention provides a kind of dye-sensitized solar cells, the organic dye that the organic dye layer of described dye-sensitized solar cells is made up of the organic dye described in technique scheme or is obtained by the preparation method described in technique scheme is made.
The organic dye layer organic dye by mentioned earlier of dye-sensitized solar cells provided by the invention is made.
Dye-sensitized solar cells provided by the invention comprises: the first and second relative transparent base layer; Conductive layer, light absorbing zone, hole transport layer and to electrode; In the middle of described first and second transparent base layer, described conductive layer, light absorbing zone, hole transport layer are connected in turn with to electrode; Described light absorbing zone comprises semi-conductor micro-nano particle layer and organic dye layer, and described semi-conductor micro-nano particle layer is connected with conductive layer, and described organic dye layer is connected with hole transport layer; Wherein, described organic dye layer organic dye is by mentioned earlier made.
In the present invention, except organic dye layer, transparent base layer, conductive layer and light absorbing zone etc. are the component parts of dye-sensitized solar cells well known to those skilled in the art.The preparation method of the present invention to described dye-sensitized solar cells there is no particular determination, can be prepared according to method well known to those skilled in the art, as according to document (EnergyEnviron.Sci., 2010,3,1924) organic dye sensitized solar cell is prepared, as long as its organic dye layer is above-mentioned organic dye.
Preferably, the present invention is by the TiO of sintering on FTO conductive glass 2nano structure membrane soaks in the solution of described organic dye, after taking out film, will cover the glass electrode hot melt ring sealing of Platinum Nanoparticles, and is finally injected into by ionogen in the gap of two electrodes, namely constitute dye-sensitized solar cells.
Wherein, the solvent of described organic dye solution is preferably the mixing solutions of ethanol and chloroform, and the volume ratio of described ethanol and chloroform is preferably (2 ~ 3): 1; The concentration of the solution of described organic dye is preferably 50 μm of ol/L ~ 200 μm ol/L; The time of described immersion is preferably 8 hours ~ 20 hours, and the temperature of described immersion is preferably room temperature.
After obtaining dye-sensitized solar cells, the present invention is at 100mWcm -2under simulation AM1.5G sunlight, Performance Detection is carried out to the dye-sensitized solar cells of preparation.Result shows, the power conversion power of the dye-sensitized solar cells prepared to adopt organic dye provided by the invention reaches as high as 12%, has higher photoelectric transformation efficiency.
In order to understand the application further, below in conjunction with embodiment, organic dye with new type electron donor that the application provides and preparation method thereof, dye-sensitized solar cells are described particularly.In following examples, compound 1 obtains according to document (R.H.Pawle, V.EastmanandS.W.Thomas, J.Mater.Chem., 2011,21,14041) synthesis; Compound 3 obtains according to document (Y.Li, Z.Wang, Org.Lett.2009,11,1386.) synthesis.
Embodiment 1
Reaction scheme is shown below:
The synthesis of 1.1 intermediates 2
In three neck round-bottomed flasks, by 850 milligrams of compounds, 1,1.49 gram of 4,7-dibromo diazosulfide, 63 milligrams of Pd (PPh 3) 2cl 2, 48 milligrams of triphenylphosphines, 17 milligrams of cuprous iodides, 2 milliliters of diisopropylamines are dissolved in 10 milliliters of toluene, are warming up to 80 DEG C under argon shield, stir lower reaction and spend the night.
After reaction terminates, reaction system is cooled to room temperature, adds 40 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, use chloroform/sherwood oil (boiling point 60-90 DEG C) 3/1 as developping agent column chromatography again, obtain 1.45 grams of intermediates 2, purity is 97%, and yield is 83%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, mass spectrometry results to the intermediate 2 obtained: 415.01 ([M+H].Results of elemental analyses: C, 54.94%; H, 3.65%; N, 6.74%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,CDCl 3)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)。
13CNMR(100MHz,CDCl 3)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。
The synthesis of 1.2 intermediates 4
In three neck round-bottomed flasks, 1.76 g of compound 3 are dissolved in 40 milliliters of toluene, in argon shield downhill reaction system, add 500 milligrams of 3-carboxylic acid, ethyl ester thiophene, 30 milligrams of Pd (OAc) 2, 90 milligrams of PCy 3hBF 4, 70 milligrams of PivOH and 500 milligram K 2cO 3, be warming up to backflow, stir lower reaction and spend the night.
After reaction terminates, reaction system is cooled to room temperature, adds 40 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, use toluene/sherwood oil (volume ratio is 1/1) as developping agent column chromatography again, obtain 1.12 grams of intermediates 4, purity is 98%, and yield is 56%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, mass spectrometry results to the intermediate 4 obtained: 644.23 ([M+H] +).Results of elemental analyses: C, 80.21%; H, 7.67%; N, 2.18%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,CDCl 3)δ:8.67(d,J＝7.4Hz,1H),8.66(d,J＝7.3Hz,1H),8.14(d,J＝8.0Hz,1H),7.93(d,J＝8.8Hz,1H),7.87–7.80(m,3H),7.78–7.74(m,3H),7.43(d,J＝5.4Hz,1H),4.53(d,J＝7.3Hz,2H),3.95(q,J＝7.0Hz,2H),2.29–2.27(m,1H),1.38–1.30(m,9H),1.21–1.19(m,15H),0.87–0.81(m,6H),0.49(t,J＝7.1Hz,3H)。
13CNMR(100MHz,CDCl 3)δ:163.53,149.77,132.88,131.53,131.34,130.56,130.51,129.80,128.92,128.89,128.09,125.26,124.92,124.87,124.80,124.61,124.50,124.34,123.89,121.10,121.01,117.95,117.47,115.55,113.68,60.35,50.28,40.14,32.03,31.99,31.96,30.10,29.80,29.69,29.43,26.65,22.82,22.78,14.29,14.23,13.56。
The synthesis of 1.3 intermediates 5
In flame-dried three neck round-bottomed flasks; 1.00 grams of intermediates 4 are dissolved in 20 milliliters of tetrahydrofuran (THF)s; under argon shield, add 7.76 milliliters to hexyl benzene bromide solution (tetrahydrofuran solution of 2M), reaction system is warming up to 90 DEG C and reaction is spent the night.
After reaction terminates, reaction system is cooled to 0 DEG C, add 20 ml waters, the mixed solution chloroform extraction obtained three times, merges organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, the crude product brown viscous liquid obtained without separation, directly due to the next step.
In three neck round-bottomed flasks of drying, intermediate obtained for upper step reaction is dissolved in 30 milliliters of toluene, add 1.00 grams of solid acid catalyst Amberlyst15, under argon shield, be warming up to backflow react, and reaction is spent the night.
After reaction terminates, reaction system is cooled to room temperature, adds 20 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, with sherwood oil (boiling point 60-90 DEG C) as developping agent column chromatography, obtain 1.23 grams of intermediates 5, purity is 97%, and yield is 90%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, high resolution mass spectrum mass spectrometry results: 903.57767 to the intermediate 5 obtained.Results of elemental analyses: C, 86.32%; H, 8.58%; N, 1.55%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d 8)δ:8.57(d,J＝8.0Hz,1H),8.56(d,J＝8.0Hz,1H),8.02(d,J＝8.0Hz,1H),7.97(s,1H),7.80(d,J＝8.7Hz,1H),7.75(d,J＝8.8Hz,1H),7.73–7.69(m,1H),7.62(d,J＝8.1Hz,1H),7.22–7.19(m,5H),7.04(d,J＝8.0Hz,4H),6.89(d,J＝5.1Hz,1H),4.59(d,J＝7.1Hz,2H),2.54(t,J＝7.6Hz,4H),2.33–2.30(m,1H),1.61–1.55(m,4H),1.44–1.40(m,6H),1.35–1.26(m,12H),1.23–1.20(m,14H),0.88–0.85(m,6H),0.82–0.79(m,6H)。
13CNMR(100MHz,THF-d 8)δ:147.30,145.07,142.24,141.58,137.74,133.72,133.49,131.61,131.20,130.69,130.20,129.27,128.73,127.86,127.02,125.70,125.65,125.54,125.03,124.40,123.97,123.21,122.77,121.31,118.81,118.23,114.54,106.96,59.20,50.63,41.00,36.49,32.97,32.94,32.85,32.80,32.64,31.04,30.74,30.65,30.38,30.26,27.56,23.66,23.63,14.59,14.57。
The synthesis of 1.4 intermediates 6:
1.00 grams of intermediates 5 are added in dry round-bottomed flask, then add 20 milliliters of anhydrous tetrahydro furans, by reaction system low temperature to-78 DEG C, under argon shield, drip 0.83 milliliter of n-Butyl Lithium (1.6 mol/L).Keep low-temp reaction 1 hour, then in reaction system, add 264 milligrams of trimethyltin chlorides, rise to stirring at room temperature and react 12 hours.
After reaction terminates, in reaction system, add 40 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, gained organotin crude product is directly used in lower step linked reaction.
In the Schlenk reaction flask of drying, above-mentioned intermediate, 589 milligrams of compound 4-oxyethyl group iodobenzenes are dissolved in 30 milliliters of toluene, under argon shield, add catalyzer 47 milligrams of Pd (PPh 3) 2cl 2, reaction system is warming up to backflow and reacts, and reaction is spent the night.
After reaction terminates, reaction system is cooled to room temperature, adds 20 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, with toluene/sherwood oil (volume ratio 1/10) as developping agent column chromatography, obtain 0.85 gram of intermediate 6, purity is 97%, and yield is 75%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, mass spectrometry results to the intermediate 6 obtained: 1023.64 ([M +]).Results of elemental analyses: C, 85.58%; H, 8.36%; N, 1.37%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,CDCl 3)δ:8.59(br,2H),8.03(s,1H),7.77-7.70(m,4H),7.50(br,2H),7.43-7.41(m,5H),7.19(d,J＝9.9Hz,4H),7.12(s,1H),6.87(d,J＝8.5Hz,2H),4.11-4.03(m,4H),2.66-2.63(m,4H),2.15(br,1H),1.69-1.63(m,4H),1.48-1.45(m,4H),1.41-1.35(m,18H),1.31-1.26(m,17H),0.95-0.93(m,6H),0.92-0.90(m,6H)。
13CNMR(100MHz,CDCl 3)δ:158.57,146.41,144.80,141.15,140.88,135.62,132.34,130.12,129.85,128.96,128.07,127.23,126.77,125.25,124.49,123.91,123.06,121.85,120.34,117.67,117.01,114.73,113.01,105.63,63.60,49.66,39.84,35.67,32.01,31.85,31.44,30.05,29.73,29.45,29.32,26.61,22.78,22.73,14.93,14.23。
The synthesis of 1.5 intermediates 7
0.85 gram of intermediate 6 is dissolved in 10 milliliters of tetrahydrofuran (THF)s, under ice bath, adds 223 milligrams of N-bromo-succinimides.After ice bath reacts 2 hours, add 20 ml water cancellation reactions.The mixed solution chloroform extraction obtained three times, merges organic phase, organic phase anhydrous sodium sulfate drying, and cross and filter siccative, concentrated filtrate, gained bromo crude product is directly used in lower step linked reaction.
In three neck round-bottomed flasks, above-mentioned bromination product is dissolved in 40 milliliters of toluene, in argon shield downhill reaction system, adds 134 milligrams of 3-carboxylate methyl ester thiophene, 8 milligrams of Pd (OAc) 2, 24 milligrams of PCy 3hBF 4, 19 milligrams of PivOH and 134 milligram K 2cO 3, be warming up to backflow, stir lower reaction and spend the night.
After reaction terminates, reaction system is cooled to room temperature, adds 40 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, use toluene/sherwood oil (volume ratio is 1/1) as developping agent column chromatography again, obtain 0.54 gram of intermediate 7, purity is 98%, and yield is 56%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, mass spectrometry results to the intermediate 7 obtained: 1164.68 ([M+H] +).Results of elemental analyses: C, 81.46%; H, 7.71%; N, 1.20%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,CDCl 3)δ:8.64(d,J＝8.1Hz,1H),8.61(d,J＝7.4Hz,1H),7.89-7.86(m,2H),7.81(s,1H),7.78-7.73(m,3H),7.49(d,J＝8.5Hz,2H),7.43(d,J＝5.4Hz,1H),7.38(d,J＝8.2Hz,4H),7.17(d,J＝8.2Hz,4H),7.10(s,1H),6.88(d,J＝8.6Hz,2H),4.40(d,J＝6.7Hz,2H),4.06(q,J＝6.8Hz,2H),3.45(s,3H),2.65-2.61(m,4H),2.31(br,1H),1.68-1.62(m,4H),1.51-1.42(m,12H),1.38-1.34(m,12H),1.29(br,15H),0.95-0.91(m,6H),0.90-0.87(m,6H)。
13CNMR(100MHz,CDCl 3)δ:163.87,158.70,150.17,146.08,145.39,141.54,141.26,140.98,135.40,133.32,131.91,130.62,130.43,129.85,128.81,127.89,127.20,127.09,126.90,125.40,125.09,124.61,124.26,123.91,123.49,122.95,122.33,120.69,118.62,117.22,115.63,114.82,105.67,63.68,58.22,51.50,50.05,40.00,35.71,32.08,32.04,31.91,31.48,30.16,29.78,29.51,29.36,26.61,22.82,22.78,14.98,14.28。
The synthesis of 1.6 intermediates 8
In flame-dried three neck round-bottomed flasks; 0.54 gram of intermediate 7 is dissolved in 20 milliliters of tetrahydrofuran (THF)s; under argon shield, add 2.51 milliliters to hexyl benzene bromide solution (tetrahydrofuran solution of 2M), reaction system is warming up to 90 DEG C and reaction is spent the night.
After reaction terminates, reaction system is cooled to 0 DEG C, add 20 ml waters, the mixed solution chloroform extraction obtained three times, merges organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, the crude product brown viscous liquid obtained without separation, directly due to the next step.
In three neck round-bottomed flasks of drying, intermediate obtained for upper step reaction is dissolved in 30 milliliters of toluene, add 0.50 gram of solid acid catalyst Amberlyst15, under argon shield, be warming up to backflow react, and reaction is spent the night.
After reaction terminates, reaction system is cooled to room temperature, adds 20 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, with sherwood oil (boiling point 60-90 DEG C) as developping agent column chromatography, obtain 601 milligrams of intermediates 8, purity is 97%, and yield is 90%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, mass spectrometry results to the intermediate 8 obtained: 1438.87 ([M+H] +).Results of elemental analyses: C, 85.12%; H, 8.33%; N, 0.97%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d 8)δ:8.45(d,J＝8.0Hz,2H),7.79(br,2H),7.57-7.55(m,2H),7.44-7.42(m,2H),7.28(d,J＝7.4Hz.4H),7.19(d,J＝7.8Hz,4H),7.14(s,1H),7.12-7.05(m,9H),6.90-6.88(d,J＝5.1Hz,1H),6.83(d,J＝8.4Hz,2H),4.39(br,2H),4.00(q,J＝6.8Hz,2H),2.55(br,8H),2.30(br,1H),1.58(br,8H),1.36-1.26(m,44H),1.19(br,6H),0.87(br,13H),0.80(br,6H)。
13CNMR(100MHz,THF-d 8)δ:159.91,147.29,146.14,144.96,142.12,141.87,141.59,141.55,137.88,136.39,134.01,133.92,131.42,130.79,130.72,129.02,128.80,128.72,128.01,127.51,126.84,126.06,124.70,124.66,124.07,123.31,122.57,118.72,118.61,115.53,106.84,106.56,64.24,59.19,50.51,40.83,36.52,33.21,32.84,32.62,31.11,30.79,30.74,30.47,30.29,27.48,23.74,23.64,15.31,14.60。
The synthesis of 1.7 target product formula II
600 milligrams of intermediates 8 are added in dry round-bottomed flask, then add 20 milliliters of anhydrous tetrahydro furans, by reaction system low temperature to-78 DEG C, under argon shield, drip 0.40 milliliter of n-Butyl Lithium (1.6 mol/L).Keep low-temp reaction 1 hour, then in reaction system, add 125 milligrams of trimethyltin chlorides, rise to stirring at room temperature and react 12 hours.
After reaction terminates, in reaction system, add 40 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, gained organotin crude product is directly used in lower step linked reaction.
In the Schlenk reaction flask of drying, by above-mentioned tin product, 345 milligrams of compounds 2 and 40 milligrams of Pd (PPh 3) 2cl 2be dissolved in 20 milliliters of toluene, under argon shield, reaction system is warming up to backflow and reacts, and reaction is spent the night.
After reaction terminates, reaction system is cooled to room temperature, add 20 ml waters, the mixed solution chloroform extraction obtained three times, merges organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, with toluene/sherwood oil (volume ratio 2/1) as developping agent column chromatography, obtains dyestuff former butyl ester compound.
In three neck round-bottomed flasks, above-mentioned butyl ester compound is dissolved in the mixed solvent of 15 milliliters of tetrahydrofuran (THF)s and 5 ml waters, in reaction system, adds 167 milligrams of potassium hydroxide, be warming up to 80 DEG C, stirring reaction 5 hours.
After reaction terminates, reaction system is cooled to room temperature, adds 20 milliliters of phosphate aqueous solutions (0.2 mol/L), the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, with trichloromethane/methyl alcohol (volume ratio 1/20) as developping agent column chromatography, obtain 587 milligrams of target product formula II, purity is 98%, and yield is 82%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization to the target product formula II obtained, high resolution mass spectrum analytical results: 1716.89166.Results of elemental analyses: C, 81.82%; H, 7.34%, N, 2.45%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d 8)δ:8.67(d,J＝5.8Hz,2H),8.35(s,1H),8.13(br,2H),7.83-7.77(m,4H),7.55(br,9H),7.30(br,8H),7.07(s,1H),6.92-6.87(m,2H),6.51(s,1H),6.36(br,2H),6.15(br,2H),3.87(br,2H),2.64(br,8H),2.08(br,1H),1.69-1.64(m,6H),1.34-1.14(m,48H),1.02-0.75(m,25H)。
13CNMR(100MHz,THF-d 8)δ:158.53,155.97,151.90,147.86,146.34,145.83,142.83,142.54,141.92,141.87,139.92,137.78,136.16,134.78,134.73,134.07,133.84,132.45,131.00,130.83,129.06,128.74,128.56,128.47,128.09,127.34,126.63,126.41,125.76,125.21,124.94,124.49,124.43,124.29,124.16,122.84,122.68,118.82,117.89,114.37,114.02,107.98,106.52,95.85,90.07,63.76,59.01,49.75,40.48,36.60,33.01,32.83,32.64,32.47,31.17,30.79,30.50,30.31,27.01,23.73,23.62,15.38,14.56。
Experimental result shows, the present invention has prepared the organic dye with formula (II) structure.
Embodiment 2
Reaction scheme is shown below:
The synthesis of 2.1 intermediates 9:
1.00 grams of intermediates 5 (embodiment obtains) are added in dry round-bottomed flask; then 20 milliliters of anhydrous tetrahydro furans are added; by reaction system low temperature to-78 DEG C, under argon shield, drip 0.83 milliliter of n-Butyl Lithium (1.6 mol/L).Keep low-temp reaction 1 hour, then in reaction system, add 264 milligrams of trimethyltin chlorides, rise to stirring at room temperature and react 12 hours.
After reaction terminates, in reaction system, add 40 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, gained organotin crude product is directly used in lower step linked reaction.
In the Schlenk reaction flask of drying, above-mentioned intermediate, 933 milligrams of compound 4-(2-hexyl oxygen in last of the ten Heavenly stems base) iodobenzenes are dissolved in 30 milliliters of toluene, under argon shield, add catalyzer 47 milligrams of Pd (PPh 3) 2cl 2, reaction system is warming up to backflow and reacts, and reaction is spent the night.
After reaction terminates, reaction system is cooled to room temperature, adds 20 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, with toluene/sherwood oil (volume ratio 1/10) as developping agent column chromatography, obtain 1.04 grams of intermediates 9, purity is 97%, and yield is 77%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, mass spectrometry results to the intermediate 9 obtained: 1219.85 ([M +]).Results of elemental analyses: C, 85.59%; H, 9.33%; N, 1.15%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d 8)δ:8.59-8.57(m,2H),8.05(d,J＝8.0Hz,1H),7.96(s,1H),7.84(d,J＝8.8Hz,2H),7.79(d,J＝8.8Hz,2H),7.75-7.71(m,1H),7.60(d,J＝8.1Hz,1H),7.51(d,J＝8.8Hz,2H),7.27(d,J＝8.4Hz,4H),7.12(s,1H),7.07(d,J＝8.4Hz,4H),6.88(d,J＝8.8Hz,2H),4.64(d,J＝7.2Hz,2H),3.89(d,J＝5.6Hz,2H),2.55(t,J＝7.7Hz,4H),2.46(s,1H),1.60-1.56(m,4H),1.47-1.44(m,6H),1.38-1.30(m,42H),1.26-1.25(m,9H),1.21-1.19(m,6H),0.91-0.85(m,12H),0.82-0.79(m,6H)。
13CNMR(100MHz,THF-d 8)δ:160.36,147.30,146.20,142.17,142.02,141.61,136.22,133.77,133.65,131.25,130.77,130.26,129.25,128.79,128.06,127.97,127.53,126.19,125.71,125.68,125.58,124.99,124.37,123.90,122.79,121.31,118.90,118.17,115.71,114.57,106.66,71.76,59.18,50.70,40.99,39.25,36.52,33.04,33.00,32.85,32.64,32.51,31.17,31.09,30.84,30.79,30.72,30.70,30.46,30.43,30.30,27.98,27.96,27.55,14.61,14.57。
The synthesis of 2.2 intermediates 10:
1.00 grams of intermediates 9 are dissolved in 10 milliliters of tetrahydrofuran (THF)s, under ice bath, add 220 milligrams of N-bromo-succinimides.After ice bath reacts 2 hours, add 20 ml water cancellation reactions.The mixed solution chloroform extraction obtained three times, merges organic phase, organic phase anhydrous sodium sulfate drying, and cross and filter siccative, concentrated filtrate, gained bromo crude product is directly used in lower step linked reaction.
In three neck round-bottomed flasks, above-mentioned bromination product is dissolved in 40 milliliters of toluene, in argon shield downhill reaction system, adds 134 milligrams of 3-carboxylate methyl ester thiophene, 8 milligrams of Pd (OAc) 2, 24 milligrams of PCy 3hBF 4, 19 milligrams of PivOH and 134 milligram K 2cO 3, be warming up to backflow, stir lower reaction and spend the night.
After reaction terminates, reaction system is cooled to room temperature, adds 40 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, use toluene/sherwood oil (volume ratio is 1/1) as developping agent column chromatography again, obtain 614 milligrams of intermediates 10, purity is 97%, and yield is 55%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, mass spectrometry results to the intermediate 10 obtained: 1361.85 ([M+H] +).Results of elemental analyses: C, 82.09%; H, 8.64%; N, 1.02%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d 8)δ:8.62-8.58(m,2H),7.88-7.85(m,2H),7.79(d,J＝8.2Hz,1H),7.69-7.65(m,3H),7.51(d,J＝4.6Hz,1H),7.41-7.34(m,6H),7.13-7.10(m,5H),6.82(d,J＝7.8Hz,2H),4.33(br,2H),3.86(d,J＝4.7Hz,2H),3.36(s,3H),2.58-2.55(m,4H),2.25(br,1H),1.78(br,1H),1.61-1.56(m,4H),1.52-1.30(m,46H),1.21(br,14H),0.91-0.85(m,12H),0.83-0.80(m,6H)。
13CNMR(100MHz,THF-d 8)δ:163.82,160.24,150.60,147.27,146.43,142.41,141.63,136.12,134.17,132.95,131.81,131.30,130.80,130.50,129.92,129.18,128.85,128.48,128.12,127.89,127.59,127.47,126.10,125.81,125.58,125.16,124.81,124.35,123.89,123.12,121.42,119.28,118.03,116.94,115.56,106.62,71.71,59.19,51.46,50.45,40.87,39.22,36.54,33.01,32.93,32.84,32.60,32.51,31.18,31.08,30.85,30.74,30.67,30.46,30.29,27.98,27.37,23.73,23.64,14.67。
The synthesis of 2.3 intermediates 11:
In flame-dried three neck round-bottomed flasks; 600 milligrams of intermediates 10 are dissolved in 20 milliliters of tetrahydrofuran (THF)s; under argon shield, add 2.51 milliliters to hexyl benzene bromide solution (tetrahydrofuran solution of 2M), reaction system is warming up to 90 DEG C and reaction is spent the night.
After reaction terminates, reaction system is cooled to 0 DEG C, add 20 ml waters, the mixed solution chloroform extraction obtained three times, merges organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, the crude product brown viscous liquid obtained without separation, directly due to the next step.
In three neck round-bottomed flasks of drying, intermediate obtained for upper step reaction is dissolved in 30 milliliters of toluene, add 0.50 gram of solid acid catalyst Amberlyst15, under argon shield, be warming up to backflow react, and reaction is spent the night.
After reaction terminates, reaction system is cooled to room temperature, adds 20 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, with sherwood oil (boiling point 60-90 DEG C) as developping agent column chromatography, obtain 655 milligrams of intermediates 11, purity is 97%, and yield is 91%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization, mass spectrometry results to the intermediate 11 obtained: 1636.18 ([M+H] +).Results of elemental analyses: C, 85.20%; H, 9.04%; N, 0.87%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d 8)δ:8.42-8.40(m,2H),7.67-7.65(m,2H),7.57-7.55(m,2H),7.38(d,J＝8.4Hz,2H),7.32(d,J＝8.1Hz,4H),7.22(d,J＝8.0Hz,4H),7.14-7.06(m,9H),7.03(d,J＝5.0Hz,1H),6.89(d,J＝5.1Hz,1H),6.83(d,J＝8.5Hz,2H),4.16(br,2H),3.86(d,J＝4.9Hz,2H),2.59-2.54(m,8H),2.20(br,1H),1.79(br,1H),1.60-1.59(m,8H),1.52-1.49(m,2H),1.33-1.29(m,54H),1.24-1.19(m,16H),0.92-0.90(m,6H),0.89-0.86(m,12H),0.82-0.79(m,6H)。
13CNMR(100MHz,THF-d 8)δ:160.15,147.36,146.03,144.82,142.18,141.78,141.56,137.97,136.49,133.90,133.78,131.53,131.26,130.77,130.14,130.04,129.50,128.96,128.62,128.01,127.38,126.79,124.62,124.09,123.36,123.22,122.46,121.83,118.59,118.48,116.28,115.83,115.50,115.17,114.73,106.79,106.50,73.04,71.65,59.17,50.45,40.74,40.21,39.85,39.25,38.63,37.94,37.62,36.88,36.56,34.19,34.06,33.86,32.03,32.85,32.63,31.73,31.12,30.77,30.31,30.04,29.61,29.11,28.00,27.42,23.75,23.66,22.47,14.55,14.09。
The synthesis of 2.4 target product formula IIIs
600 milligrams of compounds 11 are added in dry round-bottomed flask, then add 20 milliliters of anhydrous tetrahydro furans, by reaction system low temperature to-78 DEG C, under argon shield, drip 0.40 milliliter of n-Butyl Lithium (1.6 mol/L).Keep low-temp reaction 1 hour, then in reaction system, add 125 milligrams of trimethyltin chlorides, rise to stirring at room temperature and react 12 hours.
After reaction terminates, in reaction system, add 40 ml waters, the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, gained organotin crude product is directly used in lower step linked reaction.
In the Schlenk reaction flask of drying, by above-mentioned tin product, 227 milligrams of compounds 2 and 26 milligrams of Pd (PPh 3) 2cl 2be dissolved in 20 milliliters of toluene, under argon shield, reaction system is warming up to backflow and reacts, and reaction is spent the night.
After reaction terminates, reaction system is cooled to room temperature, add 20 ml waters, the mixed solution chloroform extraction obtained three times, merges organic phase, organic phase anhydrous sodium sulfate drying, cross and filter siccative, concentrated filtrate, with toluene/sherwood oil (volume ratio 2/1) as developping agent column chromatography, obtains dyestuff former butyl ester compound.
In three neck round-bottomed flasks, above-mentioned butyl ester compound is dissolved in the mixed solvent of 15 milliliters of tetrahydrofuran (THF)s and 5 ml waters, in reaction system, adds 140 milligrams of potassium hydroxide, be warming up to 80 DEG C, stirring reaction 5 hours.
After reaction terminates, reaction system is cooled to room temperature, adds 20 milliliters of phosphate aqueous solutions (0.2 mol/L), the mixed solution chloroform extraction obtained three times, merge organic phase, organic phase anhydrous sodium sulfate drying, crosses and filters siccative, concentrated filtrate, with trichloromethane/methyl alcohol (volume ratio 1/20) as developping agent column chromatography, obtain 561 milligrams of target product formula IIIs, purity is 98%, and yield is 80%.
Nucleus magnetic resonance, mass spectroscopy and elemental microanalysis method is adopted to carry out structural characterization to the target product formula III obtained, high resolution mass spectrum analytical results: 1913.11076.Results of elemental analyses: C, 82.21%; H, 8.06%, N, 2.20%.Nucleus magnetic resonance characterization data is as follows:
1HNMR(400MHz,THF-d 8)δ:8.69(d,J＝8.1Hz,1H),8.68(d,J＝8.1Hz,1H),8.42(s,1H),8.14(d,J＝7.9Hz,2H),7.85-7.81(m,2H),7.77(d,J＝8.1Hz,2H),7.58-7.56(m,9H),7.31(br,8H),6.99(s,1H),6.92(s,1H),6.86(s,1H),6.38(br,3H),6.17(br,2H),3.74(br,2H),2.65(br,8H),2.47(br,2H),1.82(br,1H),1.65(br,8H),1.49(br,6H),1.39-1.29(m,30H),1.30-1.25(m,16H),1.15(br,14H),1.02(br,3H),0.96-0.92(m,10H),0.82-0.81(m,12H),0.77-0.76(m,6H)。
13CNMR(100MHz,THF-d 8)δ:167.25,158.68,155.98,151.86,147.95,146.49,145.73,142.74,142.58,141.93,141.88,139.79,137.93,136.24,134.93,134.13,133.82,133.42,132.46,131.97,131.04,131.01,130.83,130.70,129.09,128.93,128.70,128.60,128.47,128.06,127.36,126.49,126.28,125.77,125.30,125.00,124.44,124.33,124.19,122.86,122.66,118.83,117.82,114.36,113.93,107.96,106.62,95.80,90.20,71.15,59.02,59.00,49.72,40.47,39.39,36.62,33.10,33.08,33.01,32.85,32.74,32.64,32.47,31.34,31.17,30.99,30.84,30.79,30.57,30.50,30.33,30.30,28.15,28.11,27.00,23.82,23.77,23.74,23.63,14.70,14.67,14.63,14.60,14.58。
Experimental result shows, the present invention has prepared the organic dye with formula (III) structure.
Embodiment 3
According to literature method (EnergyEnviron.Sci., 2010,3,1924) the organic dye sensitized solar cell prepared, concrete steps are: ethanol/chloroform (volume ratio 3:2) solution organic dye obtained for embodiment 1 ~ 2 being mixed with 150 micromoles per liter.Then by the TiO through 500 DEG C of sintering 2structure duplicature electrode soaks 12 hours in dye solution, takes out electrode, will cover the glass electrode hot melt ring sealing of Platinum Nanoparticles, and is finally injected into by ionogen in the gap of two electrodes, namely constitute dye-sensitized solar cells.
At 100mWcm -2under simulation AM1.5G sunlight, (method for testing performance of solar cell refers to EnergyEnviron.Sci. to carry out Performance Detection to the dye-sensitized solar cells of preparation, 2010,3,1924), test result, in table 1, as shown in Table 1, has higher photoelectric transformation efficiency with organic dye sensitized solar cell prepared by organic dye provided by the invention.
The performance test results of the dye-sensitized solar cells that table 1 embodiment of the present invention 1 ~ 2 provides
As seen from the above embodiment, the invention provides a class novel organic dye.Such organic dye respectively with two Sai fen Bing Pi and carbazole and diazosulfide for electron donor-acceptor (EDA) unit, form the chromophoric group of such dyestuff.The 3-D solid structure of dye molecule is regulated with the side modification group of large steric hindrance.Dye termination is aided with the agent structure of carboxylic acid as grafting unit composition dye molecule of replacement simultaneously.Experimental result shows, such dyestuff can effectively utilize near infrared sunlight, the short-circuit current density of remarkable boost device thus promote the electricity conversion of dye-sensitized solar cells.Adopt dye-sensitized solar cells prepared by organic dye provided by the invention, photoelectric transformation efficiency can reach 12.3%, belongs to the current leading level in the world.Organic dye novel structure provided by the invention, abundant raw material source, cost are lower, and industrial production prospect is better.Further, the preparation method of organic dye provided by the invention is the route of comparatively brief introduction, convenience and high yield.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (10)

1. an organic dye, has structure shown in formula (I):
In formula (I), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces;
X is the substituting group of formula (a) or formula (b) structure:
In formula (a), y 1and y 2be independently 0 or 1; R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 7substituting group for formula (c) structure :-Q-COOH formula (c); In formula (c), Q is phenylene, naphthylidene or phenanthrylene.
2. organic dye according to claim 1, is characterized in that, described R 1for H, C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 2~ C 24alkyl or C 2~ C 24the alkyl that alkoxyl group replaces.
3. organic dye according to claim 2, is characterized in that, described R 1substituting group for formula (d) structure:
In formula (d), R 8for C 1~ C 16alkoxyl group.
4. organic dye according to claim 2, is characterized in that, described R 2, R ' 2, R 3and R ' 3substituting group independently selected from formula (e) structure:
In formula (e), R ' 8for C 1~ C 16alkyl.
5. organic dye according to claim 2, is characterized in that, described R 4for C 2~ C 18alkyl.
6. organic dye according to claim 1, is characterized in that, in formula (a), and R 5and R 6independently selected from H, F, C 2~ C 18alkyl or C 2~ C 18the alkyl that alkoxyl group replaces.
7. organic dye according to claim 1, is characterized in that, described organic dye has formula (II) or formula (III) structure:
8. a preparation method for organic dye, comprises the following steps:
The prodrug esters with formula (IV) structure is hydrolyzed, and obtains the organic dye with formula (I) structure;
Or
The prodrug esters with formula (VI) structure is hydrolyzed, and obtains the organic dye with formula (I) structure;
Or
The compound with formula (VII) structure and the compound condensation with formula (VIII) structure react, and obtain the organic dye with formula (I) structure;
In formula (I), formula (IV), formula (VI) and formula (VII), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces;
In formula (I), X is the substituting group of formula (a) or formula (b) structure:
In formula (a), y 1and y 2be independently 0 or 1, R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 7substituting group for formula (c) structure :-Q-COOH formula (c); In formula (c), Q is phenylene, naphthylidene or phenanthrylene;
In formula (IV) and formula (VI), R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl.
9. preparation method according to claim 8, is characterized in that, described in there is formula (IV) structure prodrug esters prepare in accordance with the following methods:
The described halogenated compound with formula (A-0) structure carries out linked reaction with the compound with formula (A-01) structure, obtains the prodrug esters with formula (IV) structure;
In formula (A-0), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces, Z is Br or I;
In formula (A-01), R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; Z is Br or I; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl;
The described prodrug esters with formula (VI) structure is prepared in accordance with the following methods:
The described tin with formula (B-1) structure carries out linked reaction for compound and the compound with formula (B-2) structure, obtains the prodrug esters with formula (VI) structure;
In formula (B-1), R 1for H, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; R 2, R ' 2, R 3, R ' 3and R 4independently selected from C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; A 1, A 2and A 3separately be selected from C 1~ C 10alkyl;
In formula (B-2), R 5and R 6independently selected from H, F, C 1~ C 36alkyl or C 1~ C 36the alkyl that alkoxyl group replaces; Z is Br or I; y 2be 0 or 1; R ' 7substituting group for formula (c ') structure: formula (c ') in, Q is phenylene, naphthylidene or phenanthrylene, R 9for C 1~ C 10alkyl;
The described compound with formula (VII) structure is prepared in accordance with the following methods:
Described formylation reagent carries out formylation reaction with the compound with formula (A-1) structure, obtains the compound with formula (VII) structure.
10. a dye-sensitized solar cells, the organic dye that the organic dye layer of described dye-sensitized solar cells is made up of the organic dye in claim 1 ~ 7 described in any one or preparation method according to any one of claim 8 ~ 9 obtains is made.
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