CN106883254A - A kind of heterocycle boracic aromatic compound containing multi-substituent and its synthetic method and purposes - Google Patents
A kind of heterocycle boracic aromatic compound containing multi-substituent and its synthetic method and purposes Download PDFInfo
- Publication number
- CN106883254A CN106883254A CN201710070873.3A CN201710070873A CN106883254A CN 106883254 A CN106883254 A CN 106883254A CN 201710070873 A CN201710070873 A CN 201710070873A CN 106883254 A CN106883254 A CN 106883254A
- Authority
- CN
- China
- Prior art keywords
- thiophene
- heterocycle
- dried
- double
- thioethers
- 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
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The present invention relates to a kind of heterocycle boracic aromatic compound containing multi-substituent and its synthetic method and useWherein, R group is Mes groups or Tips groups, R1R2R3R4It is respectively halogen group, C0‑30Alkane, alkene, alkynes, alcohol, aldehyde, acid, alkoxy, alkyl tin reagent, alkyl silica reagent etc., heterocycle can be that thiophene, pyridine, pyrroles, furans, thiazole etc. contain heteroatomic polycyclic aromatic hydrocarbon.
Description
Technical field
The present invention relates to many aromatic heterocyclic organic compounds of boracic and its synthetic method, synthetic method is related to electrophilic taking
Generation, nucleophilic displacement of fluorine, Stille coupling reactions, metallization reaction and catalytic reaction etc..
Background technology
In recent years, will be in the different organic chemistry structures of major element boron, sulphur, phosphorus, silicon, gallium, germanium, arsenic, selenium, tellurium insertion
Synthesize the important channel of organic pi-electron conjugated material.In these conventional major elements, boracic polycyclic aromatic hydrocarbon is due to one
Individual empty p tracks, it is easier to receive lone pair electrons, with unique photoelectricity physical property, therefore the research of this kind of compound with
Development receives the concern of researchers.Organic photoelectrical material essentially consists in the π electricity of its organic molecule for the response in outfield
The polarization of son, thus increase or decrease the quantity and delocalization scope of pi-electron in organic molecule system all can be to the energy of molecule
Level and photoelectricity physical property produce important influence, and will in Heteroatom doping to polycyclic aromatic hydrocarbons (PAH) be regulation polycyclic aromatic hydrocarbons (PAH) light
A kind of very effective method of electric physical property.By a SP in aromatic conjugated system2The carbon atom of hydridization is replaced as miscellaneous
Atom can not only change the physical property of polycyclic aromatic hydrocarbons (PAH), it is also possible to effective change its chemical property.
2013, Wang research groups developed a kind of polycyclic fragrance for having synthesized boron N doping with photochemical method
Compound (Lu, J.；Ko,S.；Walters,N.R.；Kang,Y.；Sauriol,F.；Wang,
S.Angew.Chem.Int.Ed.2013,52,4544-4548).In the same year, Feng and Zhang is small to be combined into a series of boron nitrogen
The poly-ring aromatic compoundses containing thiophene of doping；What is more important they also using such compound as blue light-emitting assemble
OLED (Wang, X.；Zhang,F.；Liu,J.；Tang,R.；Fu,Y.；Wu,D.；Xu,Q.；Zhuang,X.；He,G.；
Feng,X.Org.Lett.2013,15,5714-5717).2016, Feng groups were reacted using double electrophilic boronation
Conjugation aromatic hydrocarbons (Wang, the X. of a series of boron N doping containing middle thiophene unit are synthesized；Zhang,F.；Gao,J.；
Fu,Y.；Zhao,W.；Tang,R.；Zhang,W.；Zhuang,X.；Feng,X.J.Org.Chem.2015,80,10127-
10133).The Pei groups of Peking University are made that in the photoelectric material research of the boron N doping containing thiophene unit in recent years
Outstanding work.2013, Pei is small to be combined into the polycyclic aromatic compounds containing thiphene ring of boron N doping, and assembles
The electronic device of the first poly-ring aromatic compoundses based on boron N doping, the hole mobility of device may be up to 0.15cm2V-1S-1(Wang,X.；Lin,H.；Lei,T.；Yang,D.；Zhuang,F.；Wang,J.；Yuan S.；Pei,
J.Angew.Chem.Int.Ed.2013,52,3117-3120).To introducing different alkyl chains on the thiophene of the compound, and
The different alkyl chain of systematic research.Research finds that different alkyl chains do not influence on the electronic property of its aromatic hydrocarbons skeleton,
But have a great impact (Wang, X. to its solid state properties；Zhuang,F.；Zhou,X.；Yang,D.；Wang,J.；Pei,
J.J.Mater.Chem.C.2014,2,8152-8161.).Pei groups also using polycyclic aromatic hydrocarbon its as monomer, be polymerized
Polymer is arrived, and has been polymerized device (Wang, X. that thing assembles organic field effect tube；Zhuang,F.；Wang,
J.；Pei,J.Chem.Commun.2015,51,17532-17535).Then, small being combined into of Pei includes " super benzene "
Boron N doping polycyclic aromatic compounds (Wang, X.；Zhuang,F.；Wang,R.；Wang,X.；Cao,X.；Wang,J.；
Pei, J.J.Am.Chem.Soc.2014,136,3764-3767.), it is up to the hole mobility of its electronic device for assembling
0.23cm2V-1S-1., small conjugation aromatic hydrocarbons (Wang, the X. for being combined into the boron N doping simultaneously containing carbazole and thiophene of Pei in 2015；
Yang,D.；Zhuang,F.；Liu,J.；Wang,J.；Pei, J.Chem.Eur.J.2015,21,8867-8873.), and to it
The function dough in later stage is carried out.
Relative to flourishing for boron azacyclo-, boron atom and other heteroatomic development phases for being conjugated aromatic hydrocarbons are contained simultaneously
To slow.Equally have a pair of lone pair electrons with nitrogen-atoms is oxygen atom, sulphur atom and phosphorus atoms.Dewar is early in last generation
Record the sixties, developed sulphur boron doped luxuriant and rich with fragrance class compound (Davis, F.A.；Dewar,
M.J.S.J.Am.Chem.Soc.1968,90,3511).When 2011, it is miscellaneous that Ashe groups have developed the first monocyclic sulphur boron
PAH, system research its property (Rohr, A.D.；Holl,M.M.B.；Kampf,J.W.；Ashe III,
A.J.S.Organometallics 2011,30,3689-3700.), DFT calculating researchs indicate sulphur boron heterocycle also certain
Armaticity.Additionally, Kawashima groups also report the conjugation aromatic hydrocarbons for having synthesized boron and other hetero atoms (phosphorus, sulphur, selenium, oxygen, nitrogen)
(Kobayashi,J.；Kato,K.；Agou,T.；Kawashima,T.Chem.Asian,J.2009,4,42-49).2013,
Piers groups also report contains thiophene unit borosilicate heterocyclic compound (Mercier, L.G.；Piers,W.E.；
Harrington,R.W.；Clegg,W.Organometallics 2013,32,6820-6826).
In sum, it is polycyclic for what the research of the polycyclic aromatic hydrocarbon of boron N doping was concentrated mainly on that boron nitrogen-atoms is joined directly together
Aromatic compound, the research for the non-immediate connected poly-ring aromatic compoundses of boron nitrogen key is considerably less.Sulphur boron, phosphorus boron or oxygen boron are mixed
Miscellaneous compound is few, due to the limitation of its synthetic method, rarely reports the influence to its photoelectricity physical property,
Research to the later stage function dough of the boracic polycyclic aromatic hydrocarbons compound of Heteroatom doping is just less, therefore further grinds
Study carefully hetero atom and be in influence and its application of the diverse location to the photoelectricity physical property of compound with extensive hair with boron atom
Exhibition prospect.
The content of the invention
Present invention aim at, there is provided a class chemical constitution it is novel, including boron-containing multi-element heterocyclic aromatic compounds, while carrying
For the design synthetic method of the compound and application, to be luminous organic material, organic solar batteries, organic photoelectrical material
Contributed Deng field.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of heterocycle boracic aromatic compound containing multi-substituent, the structural formula of the compound is：
R group is Mes groups or Tips groups, R1R2R3R4It is respectively halogen group, C0-30Alkane, alkene, alkynes, alcohol,
Aldehyde, acid, alkoxy, alkyl tin reagent, alkyl silica reagent etc., heterocycle can be thiophene, pyridine, pyrroles, furans, thiazole etc. containing miscellaneous
The polycyclic aromatic hydrocarbon of atom.
A kind of synthetic method of the heterocycle boracic aromatic compound containing multi-substituent, including following synthetic route and step
Suddenly：
1) synthesis of the double thiophene thioethers of compound 3,3 '：3 bromo thiophene is weighed in N2Dried second is added under protective condition
Ether makes it fully dissolve, and be transferred to -78 DEG C stirring 30 minutes after, in N2N-BuLi is dropwise slowly added dropwise under protection, is kept
Temperature and after stirring 30 minutes, is slowly added to double benzene sulfonyl thioethers, reacts 2 hours, is slowly increased to room temperature, is stirred overnight；Second
My god, mixture adds water and is quenched, filtering, after filter cake is repeatedly washed through ether, merging filtrate, and add water extraction, and organic layer merges, and is used in combination
Anhydrous magnesium sulfate is dried, filtering, is spin-dried for, and 100-120 DEG C of vacuum distillation obtains yellow oily compound 3,3 ' double thiophene thioethers；
2) synthesis of DTTB 1：Weigh Compound 3,3 ' double thiophene thioethers add ether fully to dissolve, mixture is placed in-
3 DEG C are stirred 30 minutes, are slowly added dropwise n-BuLi, are stirred 1 hour at that same temperature, and reaction system is heated to 40 DEG C
Backflow 1 hour, is then cooled to room temperature, is slowly added to a meter ylboronic acid dimethyl ester, is stirred overnight at room temperature, and mixture adds water and is quenched,
Ethyl acetate is extracted, and organic phase merges, plus anhydrous magnesium sulfate is dried, filtering, is spin-dried for solvent, separating-purifying target product, crude product
It is purified to obtain white solid product 1.
A kind of synthetic method of the heterocycle boracic aromatic compound containing multi-substituent, including following synthetic route and step
Suddenly：
1) synthesis of the double thiophene thioethers of compound 3,3 '-two bromo- 2,2 ':3 bromo thiophene is weighed in N2Protection is lower to add toluene
Fully dissolving, -78 DEG C are stirred 30 minutes, in N2Protection is lower to be slowly dropwise added dropwise LDA, after keeping temperature is stirred 30 minutes, slowly
Double benzene sulfonyl thioethers are added, same temperature is stirred 2 hours, is then slowly increased to room temperature, is stirred overnight, and is added water and is quenched, and is filtered,
Filter cake is added water extraction after repeatedly being washed through ether, and organic phase merges, plus anhydrous magnesium sulfate is dried, filtering, is spin-dried for solvent, and separation is carried
Pure target product, crude product is purified to obtain white solid product 3,3 '-two bromo- 2,2 ' double thiophene thioethers.
2) synthesis of DTTB 2:Weigh Compound 3,3 '-two bromo- 2,2 ' double thiophene thioethers, in N2Protection is lower to add ether
It is set fully to dissolve, reaction system is transferred into -78 DEG C stirs 30 minutes, at that same temperature, is slowly added dropwise positive fourth
Base lithium, after stirring 1 hour, mixture is slowly increased to 10 DEG C, is then slowly added into a meter ylboronic acid dimethyl ester, and reaction system gradually rises
To room temperature, it is stirred overnight；Second day, add water and be quenched, ethyl acetate extraction, organic phase merges, add anhydrous magnesium sulfate to dry, mistake
Filter, removes solvent, and separating-purifying target product, crude product obtains white solid product 2 through silica gel column chromatography purification.
A kind of purposes of the heterocycle boracic aromatic compound containing multi-substituent, sets for solar cell, electroluminescent
It is prepared by standby, sensor.
The beneficial effects of the invention are as follows：The present invention causes that reaction raw materials valency is low and is easy to get, reacts using improved synthetic method
Process avoids using toxic reagent, and synthetic method is simple and easy to apply, compound Organic Light Emitting Diode, organic solar batteries,
The fields such as organic field effect tube, organic laser, organic sensor, molecular switch, bio-imaging and Mycotoxin identification have
It is widely used.
Brief description of the drawings
Fig. 1 is the X-ray monocrystalline figures of products obtained therefrom 1 and 2 in present example.
Fig. 2 is that DTTB 1 adds UV absorption (left figure) and fluorescent emission (right figure) before and after F- to compose in the embodiment of the present invention
Figure.
Specific embodiment
Following instance helps to understand the present invention, but is not limited to present disclosure.
Synthesis of DTTB 1:
Untill up to now, the synthesis and test of part of compounds have been completed.Specific synthetic method is as follows：
The synthetic route of DTTB 1
The synthesis of the double thiophene thioethers of compound 3,3 '：3 bromo thiophene (8.15g, 50.00mmol, 1.00equiv) is weighed to exist
N2Added under protective condition in the bottle with two necks of 250ml, add dried ether 50ml it is fully dissolved, and be transferred to -78
DEG C stirring 30 minutes after, be dropwise slowly added dropwise n-BuLi (1.6M in hexane, 50.00mmol, 1.00equiv) in -78
DEG C reaction system.Whole reaction system is needed in N2Carried out under protection.After -78 DEG C are stirred 30 minutes, in N2It is slowly added under protection
Double benzene sulfonyl thioethers (7.70g, 24.50mmol, 0.49equiv), react 2 hours, are slowly increased to room temperature, are stirred overnight.Second
My god, mixture adds water and is quenched, filtering, after filter cake is repeatedly washed through ether, merging filtrate, and add water extraction three times, and organic layer merges,
And dried with anhydrous magnesium sulfate, filtering is spin-dried for.100-120 DEG C of vacuum distillation obtains the double thiophenes of yellow oily compound 3,3 '
Fen thioether (3.46g, yield 71%).
1H NMR(400MHz,CDCl3):δ6.99(dd,J1=1.2Hz, J2=5.2Hz, 2H, Ar), 7.19 (dd, J1=
1.2Hz,J2=3.2Hz, 2H, Ar), 7.33 (dd, J1=3.2Hz, J2=5.2Hz, 2H, Ar)
The synthesis of DTTB 1：The double thiophene thioethers (2.23g, 11.22mmol, 1.00equiv) of Weigh Compound 3,3 ' add
In 250ml eggplants type bottle, N2Under protective condition, the ether for adding 70ml dried fully dissolves.Mixture is placed in -3 DEG C of stirrings
30 minutes, n-BuLi (2.5M in hexane, 23.56mmol, 2.10equiv) was slowly added dropwise in reaction system,
Stirred 1 hour at a temperature of identical, reaction system is heated to 40 DEG C and flows back 1 hour, is then cooled to room temperature, is slowly added to meter Ji
Trimethyl borate (2.35mg, 12.24mmol, 1.10equiv) is stirred overnight at room temperature in reaction system, and mixture adds water and is quenched,
Ethyl acetate is extracted three times, and organic phase merges, plus anhydrous magnesium sulfate is dried, filtering, and solvent is spin-dried for Rotary Evaporators, uses post color
Spectrometry separating-purifying target product, mobile phase：Petroleum ether (PE), crude product obtains white solid product 1 through silica gel column chromatography purification
(1.76g, yield=48%).
1H NMR(400MHz,CDCl3):δ2.08(s,6H,CH3),2.38(s,3H,CH3),6.93(s,2H,Ar),7.56
(d, J=5.2Hz, 2H, Ar), 8.00 (d, J=5.2Hz, 2H, Ar)
Synthesis of DTTB 2:
The synthetic route of DTTB 2
The synthesis of the double thiophene thioethers of compound 3,3 '-two bromo- 2,2 ':Weigh Compound 3 bromo thiophene (1.63g,
10.00mmol, 1.00equiv) in 250ml bottle with two necks, in N2The lower toluene for adding 20ml dried of protection fully dissolves, will
Reaction system is transferred to -78 DEG C and stirs 30 minutes.In N2Protection is lower slow be dropwise added dropwise LDA (2.0M in THF,
10.00mmol, 1.00equiv), after -78 DEG C of stirrings 30 minutes, be slowly added to double benzene sulfonyl thioethers (1.54g, 4.90mmol,
0.49equiv).Same temperature is stirred 2 hours, is then slowly increased to room temperature, is stirred overnight, and is added water and is quenched.Filtering, filter cake warp
Ether is added water after repeatedly washing and extracts three times, and organic phase merges, plus anhydrous magnesium sulfate is dried, filtering, is spin-dried for Rotary Evaporators
Solvent, with column chromatography separating-purifying target product, mobile phase：Petroleum ether (PE), crude product obtains white through silica gel column chromatography purification
The double thiophene thioether 1.47g of color solid product 3,3 '-two bromo- 2,2 ', yield=83%.Nuclear-magnetism and the data in literature one reported for work
Cause.
1H NMR(400MHz,CDCl3):δ 6.99 (d, J=5.6Hz, 2H, Ar), 7.34 (d, J=5.6Hz, 2H, Ar)
The synthesis of DTTB 2:The double thiophene thioethers of Weigh Compound 3,3 '-two bromo- 2,2 ' (2.02g, 5.67mmol,
1.00equiv) in the reaction bulb of addition 250ml, in N2The lower addition 50ml ether of protection makes it fully dissolve, and reaction system is turned
- 78 DEG C are moved to stir 30 minutes.At that same temperature, be slowly added dropwise n-BuLi (2.5M in hexane,
12.00mmol, 2.11equiv), after stirring 1 hour, mixture is slowly increased to 10 DEG C, is then slowly added into a meter ylboronic acid diformazan
Ester (1.32g, 6.87mmol, 1.21equiv), reaction system is gradually increased to room temperature, is stirred overnight.Second day, add water and be quenched, second
Acetoacetic ester is extracted three times, and organic phase merges, and adds anhydrous magnesium sulfate to dry, and filtering removes solvent with Rotary Evaporators, uses post color
Spectrometry separating-purifying target product, mobile phase：Petroleum ether (PE), crude product obtains white solid product through silica gel column chromatography purification
2757mg, yield=41%.
1H NMR(400MHz,CDCl3):δ2.00(s,6H,CH3),2.37(s,3H,CH3),6.91(s,2H,Ar),
7.28 (d, J=5.2Hz, 2H, Ar), 7.37 (d, J=5.2Hz, 2H, Ar)
Fig. 1 is the X-ray monocrystalline figures of above example 1 and 2, and two compounds are tied again in dichloromethane and n-hexane
Crystalline substance is obtained.
The synthetic route of 1c
The synthesis of 1c:In N2Under protection, N, N, N are weighed ', N '-tetramethylethylenediamine (TMEDA) (81mg, 0.70mmol,
2.33equiv) squeeze into 25ml reaction tubes, add 3ml tetrahydrofurans fully to dissolve.Reaction system is transferred to -78 DEG C of stirrings
After 30 minutes, n-BuLi (1.6M in hexane, 0.42mL, 0.67mmol, 2.23equiv) is dropwise added dropwise in reactant
System, compound 1 (100mg, 0.30mmol, 1.00equiv) is dissolved in 0.5ml tetrahydrofurans, and slowly squeezes into reaction system,
Reacted 2 hours under the conditions of this, (0.15ml, 1.94mmol, 6.46equiv continue to react 2 hours, mixing to add excessive DMF
Thing is slowly increased to room temperature, is stirred overnight.Second day, add water and be quenched, ethyl acetate (3 × 20ml) is extracted three times, anhydrous magnesium sulfate
Dry, filtering removes solvent, with column chromatography separating-purifying target product, mobile phase：Petroleum ether：Ethyl acetate (PE：EA=
10：1), crude product is purified through silica gel column chromatography and is recrystallized to give yellow solid 1c 48mg with dichloromethane/n-hexane, and yield=
42%.
1H NMR(400MHz,CDCl3):δ2.05(s,6H,CH3),2.38(s,3H,CH3),6.94(s,2H,Ar),8.20
(s,2H,Ar),10.13(s,2H,CHO).
The synthetic route of 2c
The synthesis of 2c:In N2Under protection, N, N, N are weighed ', N '-tetramethylethylenediamine (TMEDA) (81mg, 0.70mmol,
2.33equiv) squeeze into 25ml reaction tubes, add 3ml tetrahydrofurans fully to dissolve.Reaction system is transferred to -78 DEG C of stirrings
After 30 minutes, n-BuLi (1.6M in hexane, 0.42mL, 0.67mmol, 2.23equiv) is dropwise added dropwise in reactant
System, compound 2 (100mg, 0.30mmol, 1.00equiv) is dissolved in 0.5ml tetrahydrofurans, and slowly squeezes into reaction system,
Reacted 2 hours under the conditions of this, add excessive DMF (0.15ml, 1.94mmol, 6.46equiv) to continue to react 2 hours, mixing
Thing is slowly increased to room temperature, is stirred overnight.Second day, add water and be quenched, ethyl acetate (3 × 20ml) is extracted three times, anhydrous magnesium sulfate
Dry, filtering removes solvent, with column chromatography separating-purifying target product, mobile phase：Petroleum ether：Ethyl acetate (PE：EA=
20：1), crude product is purified through silica gel column chromatography and is recrystallized to give yellow solid 2c 33mg with dichloromethane/n-hexane, and yield=
28%.
1H NMR(400MHz,CDCl3):δ2.02(s,6H,CH3),2.40(s,3H,CH3),6.97(s,2H,Ar),7.95
(s,2H,Ar),9.92(s,2H,CHO).
In order to further study the photoelectricity physical property of such compound, we have carried out ultraviolet suction to such compound
Receive, fluorescent emission is tested, electrochemical properties are tested and single crystal diffraction structural characterization.
Potential application citing 1 based on the compounds of this invention：Dye-sensitized cell
The synthesis of the dye-sensitized cell based on molecule of the present invention
The design route with DTTB 1 as raw material, by adding sulphur atom side in highly basic n-BuLi substituted thiophene molecule
Hydrogen, further with I2There is electrophilic substitution reaction in simple substance, the armaticity of compound is then improved by Stille coupling reactions.
Halogen can also further occur electrophilic substitution reaction generation aldehyde radical simultaneously, and aldol reaction further occurs under base catalysis
OSC-1 target products are obtained, OSC-1 can further make battery, widely should had in terms of DSSC
Use prospect.
Potential application citing 2 based on the compounds of this invention：Fluorine ion sensing device.
The action principle of the fluorine ion sensing device based on molecule of the present invention
With the key function characteristic that the complexing power of fluorine ion is detection trivalent boron.We have found that adding the excessive tetrabutyl
Ammonium fluoride is to can cause 1 UV absorption spectrogram and fluorescent emission spectrogram drastically to change in the solution of DTTB 1.Due to adding
The TBAF of amount, causes the absorbing wavelength band of DTTB 1 to be suppressed completely.Meanwhile, launch wavelength is also wholly absent.These phenomenons are clear
Show to Chu, the lewis acidity of boron atom remains in that constant in DTTB 1.It is that DTTB 1 adds F referring to accompanying drawing 2-It is front and rear
UV absorption (left figure) and fluorescent emission (right figure) spectrogram.
It should be noted that the foregoing is only the preferred embodiment of the present invention, the present invention is only explained, not thereby limited
System the scope of the claims of the present invention.It is only obvious to belonging to the technology of the present invention design to change, equally in present invention protection model
Within enclosing.
Claims (4)
1. a kind of heterocycle boracic aromatic compound containing multi-substituent, its general structure is following formula, R group be Mes groups or
Tips groups, R1R2R3R4It is respectively halogen group, C0-30Alkane, alkene, alkynes, alcohol, aldehyde, acid, alkoxy, alkyl tin reagent,
Alkyl silica reagent etc., heterocycle can be that thiophene, pyridine, pyrroles, furans, thiazole etc. contain heteroatomic polycyclic aromatic hydrocarbon.
X=N, P, S, O, Si, Sn.
2. the synthetic method of the heterocycle boracic aromatic compound containing multi-substituent described in a kind of claim 1, it is characterized in that：
Including following synthetic route and step：
1) synthesis of the double thiophene thioethers of compound 3,3 '：3 bromo thiophene is weighed in N2Dried ether is added under protective condition to be made
It fully dissolves, and be transferred to -78 DEG C stirring 30 minutes after, in N2N-BuLi, keeping temperature are dropwise slowly added dropwise under protection
And after stirring 30 minutes, double benzene sulfonyl thioethers are slowly added to, and react 2 hours, room temperature is slowly increased to, it is stirred overnight；Second day, mix
Compound adds water and is quenched, filtering, after filter cake is repeatedly washed through ether, merging filtrate, and add water extraction, organic layer merging, and with anhydrous
Magnesium sulfate is dried, filtering, is spin-dried for, and 100-120 DEG C of vacuum distillation obtains yellow oily compound 3,3 ' double thiophene thioethers；
2) synthesis of DTTB 1：Weigh Compound 4 adds ether fully to dissolve, and mixture is placed in into -3 DEG C stirs 30 minutes, delays
Slowly n-BuLi is added dropwise over, is stirred 1 hour at that same temperature, reaction system is heated to 40 DEG C and flows back 1 hour, Ran Houleng
But room temperature is arrived, a meter ylboronic acid dimethyl ester is slowly added to, is stirred overnight at room temperature, mixture adds water and is quenched, ethyl acetate extraction is organic
Mutually merge, plus anhydrous magnesium sulfate is dried, filtering, is spin-dried for solvent, separating-purifying target product, crude product is purified to obtain white solid
The double compounds of thiophene 1,4- sulphur boron heterocycle 1 of product.
3. the synthetic method of the heterocycle boracic aromatic compound containing multi-substituent described in a kind of claim 1, it is characterized in that：
Including following synthetic route and step：
1) synthesis of the double thiophene thioethers of compound 3,3 '-two bromo- 2,2 ':3 bromo thiophene is weighed in N2Protection is lower to add toluene abundant
Dissolving, -78 DEG C are stirred 30 minutes, in N2Protection is lower to be slowly dropwise added dropwise LDA, after keeping temperature is stirred 30 minutes, is slowly added to
Double benzene sulfonyl thioethers, same temperature is stirred 2 hours, is then slowly increased to room temperature, is stirred overnight, and is added water and is quenched, and is filtered, filter cake
Added water extraction after repeatedly being washed through ether, and organic phase merges, plus anhydrous magnesium sulfate is dried, filtering, is spin-dried for solvent, separating-purifying mesh
Mark product, the purified white solid that obtains of crude product produces 3,3 '-two bromo- 2,2 ' double thiophene thioethers.
2) synthesis of DTTB 2:Weigh Compound 5, in N2The lower addition ether of protection makes it fully dissolve, and reaction system is shifted
Stirred 30 minutes to -78 DEG C, at that same temperature, be slowly added dropwise n-BuLi, after stirring 1 hour, mixture is slow
10 DEG C are risen to, a meter ylboronic acid dimethyl ester is then slowly added into, reaction system is gradually increased to room temperature, is stirred overnight；Second day, add water
It is quenched, ethyl acetate extraction, organic phase merges, adds anhydrous magnesium sulfate to dry, filtering removes solvent, and separating-purifying target is produced
Thing, crude product obtains the double thiophene Isosorbide-5-Nitrae-compounds of sulphur boron heterocycle 2 of white solid product through silica gel column chromatography purification.
4. the purposes of the heterocycle boracic aromatic compound containing multi-substituent described in a kind of claim 1, for solar-electricity
It is prepared by pond, electroluminescence device, sensor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710070873.3A CN106883254A (en) | 2017-02-09 | 2017-02-09 | A kind of heterocycle boracic aromatic compound containing multi-substituent and its synthetic method and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710070873.3A CN106883254A (en) | 2017-02-09 | 2017-02-09 | A kind of heterocycle boracic aromatic compound containing multi-substituent and its synthetic method and purposes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106883254A true CN106883254A (en) | 2017-06-23 |
Family
ID=59178934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710070873.3A Pending CN106883254A (en) | 2017-02-09 | 2017-02-09 | A kind of heterocycle boracic aromatic compound containing multi-substituent and its synthetic method and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106883254A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200530282A (en) * | 2004-01-28 | 2005-09-16 | Idemitsu Kosan Co | Transition metal compound and useful as a component of the catalyst for olefin polymerization |
-
2017
- 2017-02-09 CN CN201710070873.3A patent/CN106883254A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200530282A (en) * | 2004-01-28 | 2005-09-16 | Idemitsu Kosan Co | Transition metal compound and useful as a component of the catalyst for olefin polymerization |
Non-Patent Citations (3)
| Title |
|---|
| LAUREN G. MERCIER ET AL: "Benzo[b]thiophene-Fused Boron and Silicon Ladder Acenes", 《ORGANOMETALLICS》 * |
| OECHSLE, PETER ET AL: "Concise Synthesis of Dithiophene Derivatives by a Palladium- Catalyzed Multiple C-S Cross Coupling/Cyclization Sequence", 《ADVANCED SYNTHESIS & CATALYSIS》 * |
| YAN, YANAN ET AL: "Thiophene-Fused 1,4-Thiaborins: Synthesis, Structures and Properties", 《ASIAN JOURNAL OF ORGANIC CHEMISTRY》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Su et al. | 9-Borafluorenes: synthesis, properties, and reactivity | |
| CN107652304B (en) | A kind of non-fullerene acceptor material of condensed ring and the preparation method and application thereof | |
| CN105017302B (en) | Bis- (S, S- dioxo-dibenzothiophenes) and 5-membered ring compounds and the preparation method and application thereof | |
| Heiskanen et al. | Synthesis of benzothiadiazole derivatives by applying C–C cross-couplings | |
| 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 | |
| CN104004165B (en) | Electron donor polymer and application thereof containing S, S-dioxo-dibenzothiophene unit | |
| JP5425338B2 (en) | Copolymer containing anthracene and pearselenol, its production method and its application | |
| CN109748925A (en) | The aromatic condensed ring structure unit and its synthetic method and application that a kind of alkoxy replaces | |
| CN104530105A (en) | Benzothiadiazole or benzodithiophene-bridged bis-boron-dipyrrolemethene (BODIPY) derivative organic dye and preparation method thereof | |
| CN109970768A (en) | Based on ten unitary condensed ring plane kernel D (A-Ar) of carbazole2Type organic photoelectric compound and preparation method and application | |
| CN106977528B (en) | The organic dyestuff of the thiophene containing three Thienopyrroles-and its application in dye-sensitized solar cells | |
| WO2015013656A2 (en) | Thieno-containing compounds and processes and uses thereof | |
| CN105820316B (en) | Hetero atom replaces naphthalimide polymer semiconductor and the preparation method and application thereof | |
| CN104610178A (en) | Preparation method of iodine atom-substituted bis-fluorophenyl heterocyclic conjugated monomer | |
| CN103113557B (en) | Phenanthro[1,10,9,8-cdefg]carbazolyl copolymer as well as preparation method and application thereof | |
| CN106632438B (en) | A kind of A- π-D- π-A type BODIPY derivatives and preparation method thereof based on acetenyl bridging | |
| CN108912315A (en) | A kind of benzo pair thiophene derivant class organic solar batteries two dimension donor materials and preparation method thereof that chlorine atom is modified | |
| CN103145524B (en) | Anthracene derivative and preparation method and application thereof | |
| CN106883254A (en) | A kind of heterocycle boracic aromatic compound containing multi-substituent and its synthetic method and purposes | |
| CN110256460A (en) | A kind of efficient small organic molecule acceptor material and its preparation method and application | |
| CN104761706A (en) | Diketopyrrolopyrrole and thieno[3,2-b]thiophene polymer as well as preparation method and application of diketopyrrolopyrrole and thieno[3,2-b]thiophene polymer | |
| CN113620927B (en) | Thienyl benzene derivative, preparation method and application thereof, donor material and preparation method thereof | |
| CN111423464B (en) | Siloxane-based substituted aromatic condensed ring and preparation method and application thereof | |
| CN109880065B (en) | Conjugated polymer containing trifluoromethyl as well as preparation method and application thereof | |
| CN103880834A (en) | Organic solar cell material and preparation method 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170623 |
|
| WD01 | Invention patent application deemed withdrawn after publication |