CN108864142A - A kind of novel method for synthesizing of ITIC derivative - Google Patents
A kind of novel method for synthesizing of ITIC derivative Download PDFInfo
- Publication number
- CN108864142A CN108864142A CN201810839640.XA CN201810839640A CN108864142A CN 108864142 A CN108864142 A CN 108864142A CN 201810839640 A CN201810839640 A CN 201810839640A CN 108864142 A CN108864142 A CN 108864142A
- Authority
- CN
- China
- Prior art keywords
- derivative
- itic
- synthesizing
- novel method
- idtt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
Abstract
The present invention provides a kind of novel method for synthesizing of ITIC derivative, includes the following steps：Step 1 takes a clean flask, and appropriate IDTT-DM-CHO is dissolved in chloroformic solution；INCN derivative is added into step 1 gained mixed liquor for step 2, and a certain amount of pyridine is slowly added dropwise, and is bubbled 20-30min with nitrogen；Step 3 seals the mixed liquor being bubbled, and solvent is spin-dried for obtaining crude product by 80 DEG C of reflux 12-14h；Methylene chloride dissolution is added into crude product for step 4, adds silica gel to be spin-dried for, is separated with column chromatography, then wash separation product with methanol, obtains ITIC derivative.The method of the present invention uses one kettle way, and experimental implementation process is simple, and side reaction is less, and more thoroughly, crude product purity is high, purification process is simple, and solvent consumption is smaller, the theory of composite green chemistry for extent of reaction ratio.
Description
Technical field
The invention belongs to organic photovoltaic field of semiconductor materials, and in particular to a kind of novel synthesis side of ITIC derivative
Method.
Background technique
In recent years, as population problem is increasingly serious, environmental problem becomes increasingly conspicuous, and fossil energy is increasingly exhausted, exploitation and
Become the hot spot that material and energy field are studied using novel renewable energy.Solar energy is inexhaustible to become me
Only choosing.Organic solar batteries are since with light weight, low manufacture cost, preparation process be simple, device flexibility
It is good and can large area preparation the advantages that, become research hotspot in recent years.The type layer of organic semiconducting materials goes out not in recent years
Thoroughly, wherein the compound system as composed by electron donor material and electron acceptor material bulk heterojunction type photoelectric material development compared with
It is rapid.
ITIC (a kind of most widely used at present non-fullerene system acceptor material, product number CAS：2099010-
84-9) as a kind of novel electron acceptor material, there is fairly good chemical stability and thermal stability, structure it is symmetrical
Property and the thick aroma system of rigidity the delocalization of electronics can be improved, charge mobility can be improved in intermolecular active force, thus makes
It is with excellent photoelectric properties.
Tang has been firstly introduced the concept of electron donor and electron acceptor within 1986, and is prepared for the solar energy of double-layer structure
Battery has obtained battery device of the energy conversion efficiency (PCE) 1% or so, has opened the gate of organic solar batteries.
2015, Zhan et al. for matrix, and repaired it with the IDTT organic semiconductor small molecule of conjugated backbone (have rigid)
Decorations, have designed and synthesized novel non-fullerene acceptor material ITIC.As a kind of excellent acceptor material, ITIC and donor material
PTB7-TH (a kind of common organic photovoltaic semiconductors donor high molecular material, CAS：It 1469791-66-9) is blended and is prepared for too
Positive energy battery device, has been increased to 7.52% for PCE, while the research neck that one for also opening organic solar batteries is completely new
Domain.2016, equally using ITIC as acceptor material, with PBDB-T (most common organic photovoltaic semiconductor donor macromolecule
Material, CAS：It is 1415929-08-4) solar battery prepared by donor material, is further increased to PCE
11.22%.
By the study found that with the ITIC small molecule receptor that INCN (2- cyano indan-1-one) blocks, in visible light region
Inside there are stronger absorption and broader absorption region, and its thermal stability of the device being prepared and chemical stability are all very
Good, photoelectric properties are excellent.In the photoelectric material of this system, have a good application prospect.
It is had been reported that in document before and uses ethyl alcohol for solvent, is directly added into triethylamine and flows back 14 hours and prepare
The method of ITIC.Although this synthetic method uses ethyl alcohol for solvent, and can smoothly obtain purpose product, the method is obtained
The products collection efficiency arrived is lower, and side reaction is more, causes post processor complicated, solvent-oil ratio is larger, and yield is not high.
The method of the present invention proposed adoption chloroform is solvent, provides alkaline environment with pyridine instead of triethylamine.Due to IDTT-DM-
CHO (2- methyl replaces IDTT) and INCN (2- cyano indan-1-one) derivative dissolubility in chloroform are preferable, have reacted
Entirely, side reaction is less, and solvent was directly spin-dried for column after reaction, with DCM (methylene chloride) for eluant, eluent, and with methanol is
Detergent washing can be obtained by the higher product of purity.This method post-processing is simple, the yield of obtained final product ITIC
Higher, solvent consumption is small, and low energy consumption, meets the theory of Green Chemistry.
Summary of the invention
In view of the problems of the existing technology, the technical solution that the present invention uses to solve problems of the prior art
It is as follows：
A kind of novel method for synthesizing of ITIC derivative, which is characterized in that include the following steps：
Step 1 takes a clean flask, and appropriate IDTT-DM-CHO is dissolved in chloroformic solution；
INCN derivative is added into step 1 gained mixed liquor for step 2, and a certain amount of pyridine is slowly added dropwise, with nitrogen drum
Steep 20-30min；
Step 3 seals the mixed liquor being bubbled, and solvent is spin-dried for obtaining crude product by 80 DEG C of reflux 12-14h；
Methylene chloride dissolution is added into crude product for step 4, adds silica gel to be spin-dried for, is separated with column chromatography, then uses methanol
Separation product is washed, ITIC derivative is obtained.
In the step 1 and step 2, with molar ratio computing, IDTT-DM-CHO:INCN derivative:Pyridine=1:4:52.
It is 0.0050g/ml-0.0060g/ml that the IDTT-DM-CHO is dissolved in the concentration in chloroformic solution in step 1,
The concentration that INCN derivative is dissolved in mixed liquor described in step 2 is 0.020g/ml-0.0240g/ml.
The temperature that IDTT-DM-CHO, INCN derivative, pyridine three mix in the step 2 is 25 DEG C, after mixing completely
Back flow reaction temperature is 80 DEG C, reaction time 14h.
The entire reaction process of this method carries out in nitrogen environment, must not contact with oxygen.
The invention has the advantages that：
1, the method for the present invention uses one kettle way, and experimental implementation process is simple, and side reaction is less, reaction yield and product purity
More original method increases, and although uses ethyl alcohol and triethylamine compared to the method recorded in pertinent literature, but react not
Thoroughly, side reaction is more, leads to post-reaction treatment trouble, and the method for the present invention substantially increases production efficiency and product quality；
2, the crude product purity that the method for the present invention is tested is higher, and purification process is convenient, reports and records with pertinent literature
Compared using ethyl alcohol with the method for triethylamine, this method use chloroform make solvent, with pyridine provide alkaline environment, reaction interval
Spend ratio more thoroughly, crude product purity is high, purification process is simple, and solvent consumption is smaller, the theory of composite green chemistry.
Detailed description of the invention
Fig. 1 is 1 products therefrom IDMIC hydrogen nuclear magnetic resonance spectrogram of the embodiment of the present invention；
Fig. 2 is the embodiment of the present invention 2 products therefrom IDMIC-4Cl (chlorination IDMIC) hydrogen nuclear magnetic resonance spectrogram；
Fig. 3 is 3 products therefrom IDMIC-4F of the embodiment of the present invention (fluorination IDMIC) hydrogen nuclear magnetic resonance spectrogram.
Three groups of embodiments use test equipment be：NMR VARIANMercury Plus400 type, test condition：
500MHz。
Specific embodiment
Below with reference to the embodiments and with reference to the accompanying drawing the technical solutions of the present invention will be further described：
Embodiment 1
200mg IDTT-DM-CHO, 35ml chloroform are added in a clean 100ml twoport flask, stirs ten minutes
Dissolve it sufficiently.INCN (182mg) is added into above-mentioned solution, pyridine (1.000ml) is slowly added dropwise, is bubbled with nitrogen
30min, sealing, observes that reaction solution becomes pico- blueing from peony at this time.Flask is placed in oil bath pan, is heated to 80 DEG C
Flow back 14h, and after reaction, reaction solution is blue.Solvent is spin-dried for, after adding DCM to dissolve plus silica gel was spin-dried for column.It will be spin-dried for
To product wash to obtain final product IDMIC with methanol, yield is 83.11% (235mg).
As shown in Figure 1, by the final product hydrogen nuclear magnetic resonance spectrogram it is found that product structure has seven class chemical environments different
Hydrogen, be located at 8.86 (2H), 8.68 (2H), 8.19 (2H), 7.90 (2H), 7.77-7.64 (7H), 7.13-7.02 (13H),
2.23 (24H) ppm are the intrinsic properties of molecule, for product of the present invention because the number of different hydrogen atoms is related with molecular structure
Molecule for, since molecular structure is symmetrical, different hydrogen atoms interacts, generate chemical shift, finally show 7 kinds not
Same hydrogen atom, the number at the peak of appearance are consistent with the spectrogram reported with pertinent literature, it is seen that the compound is correct.
Embodiment 2
200mg IDTT-DM-CHO, 35ml chloroform are added in a clean 100ml twoport flask, stirs ten minutes
Dissolve it sufficiently.INCN-2Cl (chlorination 2- cyano indan-1-one) (250mg) is added into above-mentioned solution, pyrrole is slowly added dropwise
Pyridine (1.000ml) is bubbled 30min with nitrogen, and sealing observes that reaction solution becomes pico- blueing from peony at this time.By flask
It is placed in oil bath pan, is heated to 80 DEG C of reflux 14h.After reaction, reaction solution is in blue-green.Solvent is spin-dried for, DCM is added to dissolve
Afterwards plus silica gel was spin-dried for column.The product being spin-dried for is washed to obtain final product IDMIC-4Cl, yield 82.47% with methanol
(260mg)。
As shown in Fig. 2, by the final product hydrogen nuclear magnetic resonance spectrogram it is found that product structure has nine class chemical environments different
Hydrogen, be located at 8.87 (2H), 8.76 (2H), 8.20 (2H), 7.93 (2H), 7.65 (2H), 7.07 (8H), 7.01 (4H),
2.23 (6H), 2.22 (6H) ppm, because having accessed chlorine atom, molecular structure symmetry is changed product in the present embodiment,
The number at the peak of appearance is consistent with spectrogram reported in the literature, it is seen that the compound is correct.
Embodiment 3
200mg IDTT-DM-CHO, 35ml chloroform are added in a clean 100ml twoport flask, stirs ten minutes
Dissolve it sufficiently.INCN-2F (fluorination 2- cyano indan-1-one) (216mg) is added into above-mentioned solution, pyridine is slowly added dropwise
(1.000ml) is bubbled 30min with nitrogen, and sealing observes that reaction solution becomes pico- blueing from peony at this time.Flask is set
In oil bath pan, it is heated to 80 DEG C of reflux 14h.After reaction, reaction solution is blue.Solvent is spin-dried for, is added after adding DCM to dissolve
Silica gel was spin-dried for column.The product being spin-dried for is washed to obtain final product IDMIC-4F, yield 83.40% with methanol
(250mg)。
As shown in figure 3, the hydrogen that the structure has nine class chemical environments different, since there are overlap problems for part hydrogen, so hydrogen
Spectrum illustrates only the other hydrogen of seven types above, is located at 8.85 (2H), 8.53 (2H), 8.20 (2H), 7.66 (4H), 7.08
(8H), 7.03 (4H), 2.24 (24H) ppm, because having accessed fluorine atom, molecular structure symmetry occurs product in the present embodiment
Variation, the number at the peak of appearance are consistent with spectrogram reported in the literature, it is seen that the compound is correct.
Protection scope of the present invention is not limited to the above embodiments, it is clear that those skilled in the art can be to this hair
It is bright to carry out various changes and deformation without departing from scope and spirit of the present invention.If these changes and deformation belong to power of the present invention
In the range of benefit requirement and its equivalent technologies, then including the intent of the present invention also includes these changes and deforms.
Claims (5)
1. a kind of novel method for synthesizing of ITIC derivative, which is characterized in that include the following steps：
Step 1 takes a clean flask, and appropriate IDTT-DM-CHO is dissolved in chloroformic solution；
INCN derivative is added into step 1 gained mixed liquor for step 2, and a certain amount of pyridine is slowly added dropwise, is bubbled with nitrogen
20-30min；
Step 3 seals the mixed liquor being bubbled, and solvent is spin-dried for obtaining crude product by 80 DEG C of reflux 12-14h；
Methylene chloride dissolution is added into crude product for step 4, adds silica gel to be spin-dried for, is separated with column chromatography, is then washed with methanol
Separation product obtains ITIC derivative.
2. a kind of novel method for synthesizing of ITIC derivative as described in claim 1, it is characterised in that：The step 1 and step
In rapid 2, with molar ratio computing, IDTT-DM-CHO:INCN derivative:Pyridine=1:4:52.
3. a kind of novel method for synthesizing of ITIC derivative as described in claim 1, it is characterised in that：The IDTT-DM-
It is 0.0050g/ml-0.0060g/ml that CHO is dissolved in the concentration in chloroformic solution in step 1, and INCN derivative is dissolved in step 2
The concentration of the mixed liquor is 0.020g/ml-0.0240g/ml.
4. a kind of novel method for synthesizing of ITIC derivative as described in claim 1, it is characterised in that：In the step 2
The temperature that IDTT-DM-CHO, INCN derivative, pyridine three mix is 25 DEG C, and back flow reaction temperature is 80 DEG C after mixing completely,
Reaction time is 14h.
5. a kind of novel method for synthesizing of ITIC derivative as described in claim 1, it is characterised in that：This method is entirely reacted
Process carries out in nitrogen environment, must not contact with oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810839640.XA CN108864142A (en) | 2018-07-27 | 2018-07-27 | A kind of novel method for synthesizing of ITIC derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810839640.XA CN108864142A (en) | 2018-07-27 | 2018-07-27 | A kind of novel method for synthesizing of ITIC derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108864142A true CN108864142A (en) | 2018-11-23 |
Family
ID=64305979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810839640.XA Pending CN108864142A (en) | 2018-07-27 | 2018-07-27 | A kind of novel method for synthesizing of ITIC derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108864142A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875617A (en) * | 2019-05-01 | 2020-11-03 | 香港科技大学 | Thiophene end groups of non-fullerene acceptors for electronic and photonic applications |
| CN114591349A (en) * | 2022-03-07 | 2022-06-07 | 中国科学院上海微系统与信息技术研究所 | Fluorescent compound, application thereof and detection method of trimethylamine gas |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130020739A (en) * | 2011-08-17 | 2013-02-27 | 한국과학기술연구원 | Donor-bridge-acceptor type organic semiconductors for solar cells |
| CN105315298A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules |
| CN106467547A (en) * | 2016-08-30 | 2017-03-01 | 苏州大学 | A kind of non-fullerene solaode acceptor material based on many condensed ring class and its preparation method and application |
| CN106543201A (en) * | 2016-11-01 | 2017-03-29 | 西安近代化学研究所 | A kind of A D A type conjugated molecules based on replacement indeno thiophene condensed ring unit and preparation method thereof |
| CN107286179A (en) * | 2017-07-06 | 2017-10-24 | 武汉理工大学 | A kind of novel method for synthesizing of IDTT derivatives |
| WO2018014163A1 (en) * | 2016-07-18 | 2018-01-25 | South University Of Science And Technology Of China | Donor-acceptor polymer with 4-alkoxyl thiophene as conjugated side chain and composition having the same |
| WO2018103496A1 (en) * | 2016-12-07 | 2018-06-14 | 北京大学 | Polycyclic conjugated macromolecule and preparation method and application of same |
| CN108250222A (en) * | 2018-01-30 | 2018-07-06 | 常州大学 | (D-A) based on benzene thiophene -4,8- diketonen+1The synthesis and application of D type oligomer photovoltaic donor materials |
-
2018
- 2018-07-27 CN CN201810839640.XA patent/CN108864142A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130020739A (en) * | 2011-08-17 | 2013-02-27 | 한국과학기술연구원 | Donor-bridge-acceptor type organic semiconductors for solar cells |
| CN105315298A (en) * | 2014-08-04 | 2016-02-10 | 中国科学院化学研究所 | A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules |
| WO2018014163A1 (en) * | 2016-07-18 | 2018-01-25 | South University Of Science And Technology Of China | Donor-acceptor polymer with 4-alkoxyl thiophene as conjugated side chain and composition having the same |
| CN106467547A (en) * | 2016-08-30 | 2017-03-01 | 苏州大学 | A kind of non-fullerene solaode acceptor material based on many condensed ring class and its preparation method and application |
| CN106543201A (en) * | 2016-11-01 | 2017-03-29 | 西安近代化学研究所 | A kind of A D A type conjugated molecules based on replacement indeno thiophene condensed ring unit and preparation method thereof |
| WO2018103496A1 (en) * | 2016-12-07 | 2018-06-14 | 北京大学 | Polycyclic conjugated macromolecule and preparation method and application of same |
| CN107286179A (en) * | 2017-07-06 | 2017-10-24 | 武汉理工大学 | A kind of novel method for synthesizing of IDTT derivatives |
| CN108250222A (en) * | 2018-01-30 | 2018-07-06 | 常州大学 | (D-A) based on benzene thiophene -4,8- diketonen+1The synthesis and application of D type oligomer photovoltaic donor materials |
Non-Patent Citations (3)
| Title |
|---|
| CAI’E ZHANG ET AL.: "Effect of Non-fullerene Acceptors’ Side Chains on the Morphology and Photovoltaic Performance of Organic Solar Cells", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| XIAOJUN LI ET AL.: "Synthesis and Photovoltaic Properties of a Series of Narrow Bandgap Organic Semiconductor Acceptors with Their Absorption Edge Reaching 900 nm", 《CHEMISTRY OF MATERIALS》 * |
| 段林瑞: "基于苯并二噻吩和二（噻吩并[3,2-b]吡啶）并苯的D-A型小分子和聚合物的合成及光伏性能研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875617A (en) * | 2019-05-01 | 2020-11-03 | 香港科技大学 | Thiophene end groups of non-fullerene acceptors for electronic and photonic applications |
| US11535631B2 (en) | 2019-05-01 | 2022-12-27 | The Hong Kong University Of Science And Technology | Thiophene end groups of non-fullerene acceptors for electronic and photonic applications |
| CN114591349A (en) * | 2022-03-07 | 2022-06-07 | 中国科学院上海微系统与信息技术研究所 | Fluorescent compound, application thereof and detection method of trimethylamine gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4576494B2 (en) | Photosensitizing dye | |
| CN109694464A (en) | A kind of N-shaped organic semiconducting materials and its preparation method and application | |
| CN107652304B (en) | A kind of non-fullerene acceptor material of condensed ring and the preparation method and application thereof | |
| CN101665563B (en) | Donor-acceptor conjugated polymer and application thereof in solar cells | |
| CN106748832B (en) | Hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells | |
| CN108864142A (en) | A kind of novel method for synthesizing of ITIC derivative | |
| Wu et al. | Novel 4, 4′-bis (alkylphenyl/alkyloxyphenyl)-2, 2′-bithiophene bridged cyclic thiourea functionalized triphenylamine sensitizers for efficient dye-sensitized solar cells | |
| CN108658994A (en) | A kind of porphyrin organic molecule acceptor material and the preparation method and application thereof | |
| CN110028654A (en) | Based on naphthalimide-selenophen derivative organic n-type semi-conductor polymer material and the preparation method and application thereof | |
| CN108976249B (en) | Preparation method of cycloindene corrole-fullerene star-shaped compound | |
| CN110423486A (en) | Triphen amine organic dyestuff and its synthetic method | |
| KR101828012B1 (en) | Conjugated polymer for organic solar cell and manufacturing method thereof | |
| CN108659002A (en) | The conjugation small molecule electron-acceptor material and preparation method thereof in active layer is blended in polymer solar battery | |
| CN109956955A (en) | Star-like D-A structure conjugated molecule and its preparation method and application based on benzo three (the double five yuan of heteroaromatics of cyclopenta) | |
| CN102584655B (en) | Coronene compound containing thioether in lateral chain and preparation method thereof | |
| CN116375732A (en) | Non-fullerene acceptor material and preparation method and application thereof | |
| CN110256460A (en) | A kind of efficient small organic molecule acceptor material and its preparation method and application | |
| CN104744666B (en) | Segment type polymeric material of conjugated chain containing more piece and its preparation method and application | |
| CN109824691A (en) | Liquid-crystal compounds and its preparation based on cyclopentadiene 1,4-Dithiapentalene -4- ketone | |
| Liu et al. | Tuning terminal units to improve the photovoltaic performance of small molecules based on a large planar fused-ring core in solution-processed organic solar cells | |
| CN112592464B (en) | Two-dimensional conjugated 2-chlorophenyl fluorene copolymer photovoltaic material, preparation method and application | |
| CN105153182B (en) | A kind of Dihydrobenzofuranes C of 5 alkyl 2,360Fullerene double adduct and its production and use | |
| CN111171046B (en) | Doping-free hole transport material based on tetrathienopyrrole and synthetic method and application thereof | |
| Wang et al. | D-(π-A) 3 type low bandgap star-shaped fused-ring electron acceptor with alkoxy-substituted thiophene as π-bridge | |
| KR101499476B1 (en) | Porphyrin Derivatives, Organic Dye Sensitizers Containing The Same for Highly Efficient Dye-sensitized Solar Cells And Dye-sensitized Solar Cells Containing The Same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181123 |
|
| RJ01 | Rejection of invention patent application after publication |