CN106674229A - Bithiophenepyrrolopyrroledionyl conjugated small molecule and preparation method thereof - Google Patents
Bithiophenepyrrolopyrroledionyl conjugated small molecule and preparation method thereof Download PDFInfo
- Publication number
- CN106674229A CN106674229A CN201611186113.0A CN201611186113A CN106674229A CN 106674229 A CN106674229 A CN 106674229A CN 201611186113 A CN201611186113 A CN 201611186113A CN 106674229 A CN106674229 A CN 106674229A
- Authority
- CN
- China
- Prior art keywords
- small molecule
- pyrroledione
- preparation
- thiophene pyrrole
- organic
- 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
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a bithiophenepyrrolopyrroledionyl conjugated small molecule and a preparation method thereof, relates to the field of synthesis of organic conjugated small molecules, and in particular relates to a D-A-D type organic conjugated small molecule based on a bithiophenepyrrolopyrroledionyl ditin monomer and 2-bromo-N-9-(2-ethyl hexyl) carbazole and preparation thereof. The synthesized novel organic conjugated small molecule has a relatively wide absorption range which covers the whole visible light region, and meanwhile, the novel organic conjugated small molecule has good solubleness in a common organic solvent and can be applied to the organic photovoltaic field as an optical absorption material.
Description
Technical field
The present invention relates to organic conjugate small molecule synthesis field, is related to a kind of new organic conjugate small molecule and its synthesis side
Method.
Background technology
Organic conjugate small molecule not only has the advantages that lightweight, low cost and the organic semiconducting materials such as flexible are intrinsic
Outward, also there is to be easy to purification, structure, reproducible is determined, in organic photovoltaic devices and organic field effect tube
Obtain extensively application.At present, most of organic conjugate small molecules be based on donor (Donor, D) and receptor (Acceptor, A) it
Between the mutual push-and-pull action of electronics regulating and controlling its optical absorption ranges.In numerous receptor units, pyrrolo-pyrrole-dione (DPP)
Unit has good coplanarity and stronger electron-withdrawing power, is widely used for synthesizing organic conjugate as receptor unit
Small molecule, its optical absorption ranges can reach near-infrared region.But due to intramolecular and intermolecular there is too strong push-and-pull electricity
Son effect makes its optical absorption ranges narrower；On the other hand, too strong push-and-pull electronic action can also reduce the dissolving of target product
Property, weaken the film forming ability of target product.Therefore, design and synthesize the new organic conjugate small molecule material of high comprehensive performance
Have very important significance to improving organic photovoltaic devices performance.According to former document report, introduce between D-A units
π units (herein referring to Dithiophene group) can be effectively improved the optical absorption ranges of conjugation small molecule；Meanwhile, by changing little point
Alkyl side chain in son can be used to adjust the film forming ability of small molecule.The present invention synthesized it is a kind of it is new based on carbazole be to
Body, di- thiophene pyrrole and pyrroledione have the organic conjugate small molecule of wider absorption region for the D-A-D types of receptor, can be with
It is used for organic photovoltaic devices.
The content of the invention
It is an object of the invention to provide a kind of solution processable is little with the D-A-D type organic conjugates compared with wide absorption region
Molecule and preparation method thereof.
The present invention is achieved by the following technical solutions：
Di- thiophene pyrrole and pyrroledione base conjugation small molecule, described conjugation small molecule is based on di- thiophene pyrrole
And the D-A-D molded breadths of the double tin compounds of pyrroledione and the bromo- N-9- of 2- (2- ethylhexyls) carbazole absorb conjugation small molecule.It is described
Conjugation small molecule structural formula be：
The preparation method of a kind of di- thiophene pyrrole and pyrroledione base conjugation small molecule, is carried out as steps described below：With
Di- thiophene pyrrole and pyrroledione pair tin compound and the bromo- N-9- of 2- (2- ethylhexyls) carbazole compound are raw material, with three
(dibenzalacetone) two palladium is catalyst, under three (o-methyl-phenyl -) phosphorus are for the system of part, using Shi Dile (Stille)
Cross-coupling reaction obtains described organic conjugate small molecule.
Described cross-coupling reaction temperature is 81-115 DEG C.
The described cross-coupling reaction time is 24-72 hours.
Described di- thiophene pyrrole and pyrroledione double tin compound, the bromo- N-9- of 2- (2- ethylhexyls) carbazole chemical combination
Thing, three (dibenzalacetone) two palladium, the consumption mol ratio of three (o-methyl-phenyl -) phosphorus are 1:2:0.06:0.12.
It is an advantage of the invention that：The present invention relates to the D-A-D type organic conjugate small molecules of synthesis have preferable copline
Structure, while with wide absorption region, covering whole visible region；, to promote deliquescent alkyl chain, belonging to can for side chain
The conjugation micromolecular compound of solution processing.
Description of the drawings
Fig. 1 is based on di- thiophene pyrrole and the double tin compounds of pyrroledione and the bromo- N-9- of 2- (2- ethylhexyls) carbazole
The synthesis path schematic diagram of the organic conjugate small molecule of compound；
Fig. 2 is the synthesis path schematic diagram of di- thiophene pyrrole and the double tin compounds of pyrroledione；
Fig. 3 is the synthesis path schematic diagram of the bromo- N-9- of 2- (2- ethylhexyls) carbazole compound；
Fig. 4 is the uv-visible absorption spectroscopy figure of the organic conjugate small molecule of solution processable.
Specific embodiment
Embodiments of the invention are elaborated below in conjunction with the accompanying drawings：The present embodiment is with technical solution of the present invention as front
Put and implemented, combine detailed embodiment and specific operating process, but protection scope of the present invention is not limited to down
The embodiment stated.
As shown in figure 1, the present invention is with the double tin compounds of di- thiophene pyrrole and pyrroledione and 2- bromo- N-9- (2- ethyls
Hexyl) carbazole compound copolymerization under the conditions of Stille cross-coupling reactions, by silica gel chromatography column purification obtains target product.
The wide conjugation small molecule that absorbs of the solution processable of the present invention has following structure：
The preparation method of each compound is illustrated, it is as follows：
The synthesis path schematic diagram of di- thiophene pyrrole and the double tin compounds of pyrroledione is as shown in Fig. 2 preparation method ginseng
Examine document report (Dyes and Pigments, 2016,126,173-178).Compound has following structure：
The synthesis path schematic diagram of the bromo- N-9- of 2- (2- ethylhexyls) carbazole compound is as shown in figure 3, preparation method reference
Document report (Synthesis, 2005,10,1619-1624).Compound has following structure：
Embodiment 1, synthesizes organic conjugate small molecule
The synthesis path of conjugation small molecule is as shown in figure 1, concretely comprise the following steps：Under argon protection, by di- thiophene pyrrole
And the double tin compound (200mg, 0.197mmol) of pyrroledione and the bromo- N-9- of 2- (2- ethylhexyls) carbazole compound (141mg,
0.394mmol), the palladium of catalyst three (dibenzalacetone) two ((10.8mg, 6mol%), part three (o-methyl-phenyl -) phosphorus
(7.2mg, 12mol%), dry toluene (15mL) is added in reaction bulb.Reaction unit, evacuation 30 minutes, punching are freezed with liquid nitrogen
Enter argon, repeat this operation three times.After being slowly warmed up to backflow, react 48 hours, reactant liquor is cooled to into room temperature.By mixture
It is poured into water and is extracted with dichloromethane.Wash organic layer with water, overnight, vacuum evaporating solvent is obtained Jing anhydrous sodium sulfate dryings
To crude product.Crude product passes through silica gel column chromatography column purification, using normal hexane and dichloromethane (1:1, v/v) mixed solvent conduct
Eluant, obtains violet solid 195.5mg (yields：80%).
Embodiment 2, synthesis compound di- thiophene pyrrole and the double tin compounds of pyrroledione
The synthesis path of di- thiophene pyrrole and the double tin compounds of pyrroledione is as shown in Fig. 2 concretely comprise the following steps：In drying
100mL there-necked flasks in add 18mL anhydrous tetrahydro furans and 1.6mL diisopropylamine.Reaction system is freezed with liquid nitrogen, is taken out
Vacuum 15 minutes, pours argon, and this operation is in triplicate.Again reaction system is dropped to into -78 DEG C, be added dropwise over 4.8mL normal-butyls
Lithium (11.44mmol, 2.4M hexane solution), is kept for -78 DEG C after one hour by temperature, is slowly warmed up to -15 DEG C.By fresh system
Standby diisopropylamino lithium (LDA) be added dropwise to be reduced to -78 DEG C of di- thiophene pyrrole and pyrroledione (916.4mg,
Anhydrous tetrahydro furan (THF) solution 1.33mmol), system maintained -78 DEG C after two hours, is slowly warmed up to -20 DEG C and ties up
Hold 3 hours.The temperature of reaction system is cooled to into once again -78 DEG C, 4.7mL trimethyl ammonia chloride solution of tin is rapidly joined
(tetrahydrofuran solution of 4.7mmol, 1M).Mixture is warming up to into room temperature, is stirred overnight under argon protection.Reactant is used
50mL deionized water Jin Hang temper goes out, and then deionized water, dichloromethane are extracted three times.Organic extraction solution washed with water three
It is secondary, then with anhydrous sodium sulfate drying overnight.After sucking filtration, vacuum drying obtains darkviolet solid (1.06g, yield 94%).
Embodiment 3, bromo- N-9- (2- ethylhexyls) carbazoles of synthesis 2-
In equipped with 12ml acetone three mouthfuls of reaction bulbs, then the 2- bromo carbazoles of 492.2mg (2.00mmol) are dissolved in
Order addition 224.4mg (4.00mmol) powdered potassium hydroxide (KOH), 772.48mg (4.00mmol) 2- ethyl hexyl bromides,
33.33mg phase transfer catalyst 4-butyl ammonium hydrogen sulfate.Reactant mixture is heated slowly to into backflow, is reacted 12 hours.Will be anti-
Answer liquid to be as cold as after room temperature, extracted with dichloromethane, overnight, vacuum evaporating solvent obtains crude product to Jing anhydrous sodium sulfate dryings.Slightly
Product passes through silica gel column chromatography column purification, using normal hexane and ethyl acetate (10:1, v/v) mixed solvent is obtained as eluant
To colourless oil liquid 628.51mg (yields：88%).
Fig. 4 gives the absorption spectrum of organic conjugate small molecule, and its absorption region covers whole visible region.
In sum, new organic conjugate small molecule according to the present invention has preferable coplanar structure, and with good
Dissolubility well and optical absorption ability, can be applied to organic photovoltaic field as optical absorbing material.
Claims (5)
1. di- thiophene pyrrole and pyrroledione base conjugation small molecule, it is characterised in that structural formula is：
2. above-mentioned di- thiophene pyrrole and pyrroledione base are conjugated the preparation method of small molecule, it is characterised in that as steps described below
Carry out：With the double tin compounds of di- thiophene pyrrole and pyrroledione and the bromo- N-9- of 2- (2- ethylhexyls) carbazole compounds for original
Material, with three (dibenzalacetone) two palladium as catalyst, under three (o-methyl-phenyl -) phosphorus are for the system of part, using Shi Dile
(Stille) cross-coupling reaction obtains described organic conjugate small molecule.
3. di- thiophene pyrrole according to claim 1 and pyrroledione base are conjugated the preparation method of small molecule, its feature
Cross-coupling reaction temperature described in being is 81-115 DEG C.
4. di- thiophene pyrrole according to claim 1 and pyrroledione base are conjugated the preparation method of small molecule, its feature
It is 24-72 hours the described cross-coupling reaction time to be.
5. di- thiophene pyrrole according to claim 1 and pyrroledione base are conjugated the preparation method of small molecule, its feature
Be described di- thiophene pyrrole and the double tin compounds of pyrroledione, the bromo- N-9- of 2- (2- ethylhexyls) carbazole compound, three
(dibenzalacetone) two palladium, the consumption mol ratio of three (o-methyl-phenyl -) phosphorus are 1:2:0.06:0.12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611186113.0A CN106674229A (en) | 2016-12-21 | 2016-12-21 | Bithiophenepyrrolopyrroledionyl conjugated small molecule and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611186113.0A CN106674229A (en) | 2016-12-21 | 2016-12-21 | Bithiophenepyrrolopyrroledionyl conjugated small molecule and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106674229A true CN106674229A (en) | 2017-05-17 |
Family
ID=58869895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611186113.0A Pending CN106674229A (en) | 2016-12-21 | 2016-12-21 | Bithiophenepyrrolopyrroledionyl conjugated small molecule and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674229A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108745413A (en) * | 2018-06-02 | 2018-11-06 | 盐城师范学院 | Application of a kind of quinoid structure compound in Visible Light Induced Photocatalytic bisphenol-A |
| CN108837844A (en) * | 2018-06-02 | 2018-11-20 | 盐城师范学院 | Application of a kind of quinoid structure compound in Visible Light Induced Photocatalytic imidacloprid |
| CN116444541A (en) * | 2023-04-25 | 2023-07-18 | 上海大学 | Pyrrolo-pyrrole-dione bridged macrocyclic compound, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889016A (en) * | 2007-10-09 | 2010-11-17 | 巴斯夫欧洲公司 | Pyrrolopyrrole derivatives, its preparation and purposes |
-
2016
- 2016-12-21 CN CN201611186113.0A patent/CN106674229A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101889016A (en) * | 2007-10-09 | 2010-11-17 | 巴斯夫欧洲公司 | Pyrrolopyrrole derivatives, its preparation and purposes |
Non-Patent Citations (3)
| Title |
|---|
| HUIJING ZHANG，等: "Diketopyrrolopyrrole based small molecules with near infrared absorption for solution processed organic solar cells", 《DYES AND PIGMENTS》 * |
| MERVE AKBAYRAK，等: "Synthesis and electrochemical polymerization of diketopyrrolopyrrole based donor–acceptor–donor monomers containing 3,6- and 2,7-linked carbazoles", 《POLYMER CHEMISTRY》 * |
| 孙丽，等: "一种新型吡咯并吡咯二酮衍生物的设计与合成", 《精细化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108745413A (en) * | 2018-06-02 | 2018-11-06 | 盐城师范学院 | Application of a kind of quinoid structure compound in Visible Light Induced Photocatalytic bisphenol-A |
| CN108837844A (en) * | 2018-06-02 | 2018-11-20 | 盐城师范学院 | Application of a kind of quinoid structure compound in Visible Light Induced Photocatalytic imidacloprid |
| CN108837844B (en) * | 2018-06-02 | 2023-01-24 | 盐城师范学院 | Application of quinoid structure compound in visible light degradation of imidacloprid |
| CN116444541A (en) * | 2023-04-25 | 2023-07-18 | 上海大学 | Pyrrolo-pyrrole-dione bridged macrocyclic compound, and preparation method and application thereof |
| CN116444541B (en) * | 2023-04-25 | 2024-05-31 | 上海大学 | Pyrrolo-pyrrole-dione bridged macrocyclic compound, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106243329B (en) | One kind being based on S, and S- dioxydibenze thiophthene derivative replaces conjugated polymer luminescent material and the preparation method and application thereof to receptor type | |
| CN101712674B (en) | Alkyl substituted-S,S-dioxo-dibenzothiophene monomer, preparation method and polymer thereof | |
| CN106674229A (en) | Bithiophenepyrrolopyrroledionyl conjugated small molecule and preparation method thereof | |
| CN105175691B (en) | Conjugated polymer semi-conducting material, preparation and its high-efficiency polymer solar cell application of the one kind based on thieno (hetero) aryl indole unit | |
| CN103435782B (en) | Organic semiconducting materials containing 9,9 '-difluorenylene and derivant thereof and preparation method thereof and application | |
| EP2927258B1 (en) | Benzodithiophene based copolymer containing thieno [3,4-b]thiophene units and preparing method and applications thereof | |
| CN105753851B (en) | Tetrafluoride Benzoquinoxalines compound and tetrafluoride Benzoquinoxalines based polyalcohol and its preparation method and application | |
| CN101875716A (en) | Block conjugated polymer, preparation method thereof and use thereof | |
| CN109438351B (en) | Preparation method of pentazocine intermediate | |
| WO2013056355A1 (en) | Preparation of high molecular weight polymers 8y direct arylation and heteroarylation | |
| CN103554139B (en) | Thiophene condensed 2,1,3-benzoxadiazole derivative and polymer thereof | |
| CN108864137A (en) | Receptor compound, preparation method and application thereof, and photovoltaic cell containing receptor compound | |
| CN113429383A (en) | Non-fullerene acceptor material, preparation method and application thereof | |
| CN109517142B (en) | Star-shaped D-A structure conjugated molecule based on tri-indeno five-membered aromatic heterocycle, and preparation method and application thereof | |
| CN109912662B (en) | Solution-processable dendritic iridium complex electroluminescent material and synthesis method thereof | |
| CN103360397B (en) | Dithienyl pyrrolo-pyrrole-dione-naphthyl conjugate derivative and its preparation method and application | |
| CN110776621A (en) | D-pi-A type polymer containing quinoline-based fused ring unit and preparation method and application thereof | |
| CN110343064B (en) | Synthesis method of [60] fullerene-tetrahydrocyclopenta [2,3-b ] indole derivative | |
| EP2927257A1 (en) | Benzodithiophene based copolymer containing pyridino [2,1,3]thiadiazole units and preparing method and applications thereof | |
| CN109456348A (en) | A kind of 2,6- diacetylene trimeric indenyl BODIPY class near infrared fluorescent dye and preparation method thereof | |
| CN101891670A (en) | 4, 5-ethylene-2, 7-disubstituted carbazole and preparation method thereof | |
| CN110669002B (en) | Synthetic method of 2-fluoro-3-hydroxypyridine-4-carboxylic acid | |
| 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) | |
| CN106632438A (en) | Ethynyl bridging based A-phi-D-phi-A type BODIPY derivative and preparation method thereof | |
| CN110776620B (en) | D-pi-A polymer containing S, S-dioxo-dibenzothiophene derivative unit and preparation method and application thereof |
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: 20170517 |
|
| RJ01 | Rejection of invention patent application after publication |