CN104610178B - A kind of preparation method of the double fluorine benzheterocycle conjugative monomers of iodine atom substitution - Google Patents
A kind of preparation method of the double fluorine benzheterocycle conjugative monomers of iodine atom substitution Download PDFInfo
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- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
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- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
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- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
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Abstract
The present invention relates to a kind of preparation method of double fluorine benzheterocycle conjugative monomers of iodine atom substitution.The preparation method is that the compound with double fluorine benzheterocycle conjugated structures reacts with lithium diisopropylamine first, and elemental iodine is then added in reaction system, finally introduces iodine atom on the phenyl ring of double fluorine benzheterocycle conjugate units.This method avoids, using hazardous agents such as oleums, improving the security of combined coefficient and experimental implementation, and yield is much higher than traditional iodate method, is convenient for large-scale preparation production.
Description
Technical field
The invention belongs to Fine Organic Chemical technical field, specially a kind of double fluorine benzheterocycle conjugation of iodine atom substitution are single
The preparation method of body.
Background technology
With the development in epoch, the mankind are increasing to the demand of the energy, but the traditional resource such as oil, coal is eventually withered
Exhaust, this just allows development and utilization of the people to new energy to feel urgent all the more.And solar energy is because its is universal, harmless, permanent
Advantage always turn into numerous scientist's research and utilizations object, wherein in a manner of photoelectric conversion using solar energy solar cell into
For one of research emphasis.Silica-based solar cell is to develop most permanent and the most ripe technology, is had been commercialized at present, monocrystalline silicon
The Laboratory efficiencies of battery have reached 25.0%.But the sky high cost of silica-based solar cell, highly energy-consuming, production pollution are big etc.
Fatal defects, which result in it and can not realize for a long time, to be widely applied.Then, have low cost, large area, flexibility, it is frivolous,
The advantages that solution processable [Materials Today, 17 (2014) 11-15；The Journal of Physical
Chemistry Letters, 2 (2011) 3102-3113] polymer solar cells turn into the new primary study pair of scientists
As.Over more than 20 years, researcher is by synthesizing a large amount of organic donors with acceptor material and battery device being continued to optimize, mesh
The Laboratory efficiencies of preceding single polymer layer organic photovoltaic cell reached 10.36% [NatureCommunnications, 5
(2014) 5293], there is wide and bright application prospect.
In numerous photoelectric materials, containing diazosulfide, the photoelectric material of benzotriazole unit organic electroluminescent,
It has been widely used in the material such as organic photovoltaic cell and organic field effect tube.With diazosulfide and benzo
Triazole is compared, if the hydrogen on 5 on its phenyl ring and 6 carbon atoms is substituted by into fluorine atom mainly following 3 advantages：(1) it is same
When reduce highest occupied molecular orbital(HOMO) energy level (HOMO) and the lowest unocccupied molecular orbital energy level (LUMO) of polymer, and to light
Somewhat having for band gap is learned a little to increase；(2) ionization energy of the polymer of fluoro is reduced, with fullerene derivate PCBM
Charge transfer effciency in Blending Processes is improved；(3) fluorinated polymer all has smooth in solution or film
Conformation of the main chain, make that its accumulation under film is more regular, and its absorption coefficient is improved, especially the long wave in absorption spectrum
Long region [Journal of American Chemistry Society, 2012,134,14932-14944].
For a long time, iodine atom is introduced on double fluorine diazosulfides or BTA, it usually needs use oleum
Generation [Angew.Chem.Int.Ed.2011,50,2995-2998] is reacted at 60 DEG C with elemental iodine.Oleum belongs to easy
The control reagent of poison is made, in use, if exposure is in atmosphere, the sulfur trioxide (SO evaporated3) with air in
Vapor forms sulfuric acid droplets, and potential safety hazard is caused to experiment operator.The preparation method of the present invention then first uses diisopropyl
Base lithium amide (LDA) reacts with hydrogen atom on double fluorobenzene and the phenyl ring of heterocyclic units, is then added in reaction system single
Matter iodine, so as to introduce iodine atom on the phenyl ring of double fluorine benzheterocycles.Compared with conventional method, this method have course of reaction without
Oleum etc. need to be used easily to make malicious hazardous agents, experimental implementation is safe and reliable, and the advantages that substantially increase synthesis yield, can
Prepare with scale for iodinated monomer.
The content of the invention
It is an object of the invention to overcome the shortcomings of the prior art, there is provided a kind of reliable iodine atom of safe operation takes
The synthetic method of generation double fluorine benzheterocycle conjugative monomers.This double fluorine benzheterocycle conjugative monomers of iodine atom substitution can pass through gold
Category catalyzed coupling reaction is coupled (or polymerization) with the aromatic ring group of other conjugation, formed to-receptor structure or donor-by
The small molecule or polymer of body-donor structure.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of double fluorine benzheterocycle conjugative monomers of iodine atom substitution, it comprises the following steps：Diisopropyl
Base lithium amide (LDA) first with the atomic reaction of hydrogen on double fluorobenzene and heterocyclic units (1) phenyl ring, then adds single in reaction system
Matter iodine, so as to introduce iodine atom, i.e. product (2 or 3) on double fluorine benzheterocycle conjugate unit phenyl ring；Reaction equation is
Wherein, Ar groups are the conjugated structure of armaticity, have following structural formula：
R is hydrogen, the alkyl of 1-30 carbon number or wherein one or more carbon atoms by oxygen atom, alkenyl, alkynyl, virtue
Base, hydroxyl, amino, carbonyl, carboxyl, nitro, phenyl, thienyl substitution, or hydrogen atom are substituted with halogen atoms.
Further specific implementation ground, the preparation method of double fluorine benzheterocycle conjugative monomers of the iodine atom substitution include：
Under anhydrous, anaerobic atmosphere of inert gases, diisopropylamine is dissolved in anhydrous organic solvent, and temperature is reduced to-
78 DEG C, n-BuLi is slowly added dropwise into wherein, stirring reaction generates lithium diisopropylamine (LDA)；The double fluorobenzene of reactant are simultaneously
Heterocycle conjugate unit is dissolved in anhydrous organic solvent, is added dropwise in LDA, the double fluorine benzheterocycle conjugate units of reactant and LDA
Equivalent proportion determined by target product；After stirring reaction, the iodine of anhydrous organic solvent will be dissolved in, is disposably added dropwise to,
The equivalent proportion of iodine is determined by target product；After simple substance iodine solution is added dropwise, it is warmed to room temperature naturally, stirring reaction is overnight；
Target product is double fluorine benzheterocycle conjugative monomers of diiodo- substitution, then double fluorine Benzoheterocyclic compounds：Lithium diisopropylamine：
The equivalent proportioning of elemental iodine should be 1:2:2.3；If target product is double fluorine benzheterocycle conjugative monomers of single iodine substitution, double fluorine
Benzoheterocyclic compounds：Lithium diisopropylamine：The equivalent proportioning of elemental iodine should be 1:1:1.15.
The organic solvent is tetrahydrofuran, ether, n-hexane, dichloromethane, chloroform, one kind in toluene.
Compared with existing technology, the advantage of the invention is that：
For course of reaction without using easily system poison, the hazardous agents such as oleum, experimental implementation is safe and reliable, and greatly improves
Synthesis yield, be advantageous to prepare with scale production.
Embodiment
It is described further below in conjunction with implementation of the example to the present invention, but implementation and the protection not limited to this of the present invention,
It is that those skilled in the art can refer to prior art and realize if there is not specified part below.
Shown in the following reaction equation of syntheti c route of the double fluorine benzheterocycle conjugative monomers of iodine atom substitution of following instance：Pass through
Methodology of organic synthesis synthesis double fluorine benzheterocycle (Ar) compounds 1 under the conditions of low-temperature anhydrous with lithium diisopropylamine
(LDA) react, elemental iodine is then added in reaction system, finally introduces iodine atom on double fluorine benzheterocycles, i.e. diiodo- takes
For monomer (2) or single iodine substituted monomer (3).
(1) preparation of lithium diisopropylamine (LDA)：Under blanket of nitrogen, the tetrahydrochysene of 0.1g/mL diisopropylamines (1.1 equivalent)
Tetrahydrofuran solution is cooled to -78 DEG C, and the n-BuLi (2.5mol/L hexane solutions) of 1 equivalent is slowly added dropwise to solution, drips
- 78 DEG C are maintained at after finishing to react 1 hour.
(2) iodination reaction：The substrate (double fluorine benzheterocycle conjugated compounds) of 1.0 equivalents is made into anhydrous organic solvent
0.1g/L solution, is then gradually added drop-wise in LDA, is reacted 1 hour at -78 DEG C；2.3 equivalents (are prepared diiodo- and substitute list
Body 2) or elemental iodine and the anhydrous organic solvent of 1.15 equivalents (preparing single iodine substituted monomer 3) be made into 0.06g/L solution, and will
In its direct dropwise reaction system, system is warmed to room temperature naturally, is stirred overnight.
(3) post-process：Reaction solution is poured into the aqueous solution of sodium hydrogensulfite and stirred, elemental iodine is removed, and use dichloro
Methane, chloroform etc. extract to the solvent of product favorable solubility, take organic layer, and washed with saturated sodium-chloride water solution
Wash, anhydrous magnesium sulfate is dried, and filtering, is evaporated under reduced pressure and is removed solvent, and obtained crude product is purified by recrystallization or column chromatography.
By specific example, the invention will be further described again below.
Embodiment 1
The preparation of fluoro- 2H- benzos [d] [1,2,3] triazole of the iodo- 2- dodecyls -5,6 two of 4,7- bis-
Synthetic route is as follows：
In 250mL long-neck there-necked flasks, under argon atmospher, add diisopropylamine (1.73g, 17.03mmol, 2.2 equivalent) with
30mL tetrahydrofurans, -78 DEG C are cooled to, n-BuLi (15.48mmol, 6.2mL, 2.5mol/L, equivalent) is added dropwise, finishes, instead
Answer 1 hour, then by fluoro- 2H- benzos [d] [1,2, the 3] triazole (2.5g, 7.74mmol, 1 equivalent) of 2- dodecyls -5,6 two with
25mL tetrahydrofuran wiring solution-forming, is gradually gradually added dropwise to reaction solution, finishes, and reacts 40 minutes, then iodine is added dropwise thereto
Tetrahydrofuran solution (4.52g, 17.8mmol, 2.3 equivalent, 75mL tetrahydrofurans), is finished, and after stirring 15 minutes, is placed in room temperature,
It is stirred overnight.Post processing：Add sodium sulfite stirring and remove iodine, be subsequently poured into water, dichloromethane extraction, saturated sodium-chloride water
Solution is washed, and anhydrous magnesium sulfate is dried.Post is crossed with petroleum ether and dichloromethane mixed solvent, the product of oily liquids is obtained, is long placed in
For solid, 3.7g (yields：84%).Proton nmr spectra：(CDCl3)δ(ppm)4.75–4.71(m,2H),2.17–2.06(m,
2H), 1.42-1.18 (m, 18H), 0.87 (t, 3H) carbon-13 nmr spectras：(CDCl3)δ(ppm)152.44,152.30,
150.76,150.62,140.79,140.77,140.75,122.36,122.29,121.11,120.90,57.47,31.95,
30.17,29.65,29.63,29.52,29.39,29.37,29.00,26.51,22.73,14 .16. mass spectrums：Calculated value:
575.01；Measured value：576.0.
Embodiment 2
The preparation of iodo- 5,6 difluoro benzo [d] [1,2,5] thiadiazoles of 4,7- bis-
In 250mL long-neck there-necked flasks, under argon atmospher, add diisopropylamine (3.9g, 15.3mmol, 2.2 equivalent) with
30mL tetrahydrofurans, -78 DEG C are cooled to, n-BuLi (34.8mmol, 14.0mL, 2.5mol/L, 2 equivalent) is added dropwise, finishes, instead
Answer 1 hour, then by 5,6 difluoro benzo [d] [1,2,5] thiadiazoles (3g, 17.4mmol, 1 equivalent) and 30mL tetrahydrofuran
Wiring solution-forming, gradually gradually it is added dropwise, finishes to reaction solution, react 40 minutes, then the tetrahydrofuran solution of iodine is added dropwise thereto
(10.16g, 40.02mmol, 2.3 equivalent, 170mL tetrahydrofurans), is finished, and after stirring 15 minutes, is placed in room temperature, is stirred overnight.
Post processing：Add sodium sulfite stirring and remove iodine, be subsequently poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, nothing
Water magnesium sulfate is dried.Vacuum distillation is gone out solvent, the mixed solvent recrystallization of obtained solid ethanol and toluene, is obtained yellowish
Color solid 6.5g (yields：88%).Mass spectrum：Calculated value:423.78；Measured value：424.60. elementary analysis：Calculated value：C,
17.00%；N, 6.61%；S, 7.56%；Measured value：C, 16.82%；N, 6.22%；S, 7.13%.
Embodiment 3
The preparation of double (4- (octyloxy) phenyl) quinoxalines of 5,8- bis- iodo- 6,7 two fluoro- 2,3-
In 100mL long-neck there-necked flasks, under argon atmospher, add diisopropylamine (0.78g, 7.66mmol, 2.2 equivalent) with
10mL tetrahydrofurans, -78 DEG C are cooled to, n-BuLi (6.96mmol, 2.8mL, 2.5mol/L, 2 equivalent) is added dropwise, finishes, instead
Answer 1 hour, then by double (4- (octyloxy) phenyl) quinoxalines (2.0g, 3.48mmol, 1 equivalent) of 6,7 two fluoro- 2,3- and 20mL
Tetrahydrofuran wiring solution-forming, be gradually gradually added dropwise, finish to reaction solution, react 40 minutes, then thereto be added dropwise iodine tetrahydrochysene
Tetrahydrofuran solution (2.04g, 8.00mmol, 2.3 equivalent, 35mL tetrahydrofurans), is finished, and after stirring 15 minutes, is placed in room temperature, is stirred
Overnight.Post processing：Add sodium sulfite stirring and remove iodine, be subsequently poured into water, dichloromethane extraction, saturated sodium-chloride water solution
Wash, anhydrous magnesium sulfate is dried.Post is crossed with petroleum ether and dichloromethane mixed solvent, obtains 2.3g solid (yields：80%).Matter
Spectrum：Calculated value:826.13；Measured value：827.04. elementary analysis：Calculated value：C, 52.31%；H, 5.12%；N, 3.39%；It is real
Measured value：C, 51.63%；H, 4.98%；N, 3.12%.
Embodiment 4
The preparation of iodo- 2,7- dioctyls dibenzo [a, the c] azophenlyene of the fluoro- 10,13- bis- of 11,12- bis-
In 250mL long-neck there-necked flasks, under argon atmospher, add diisopropylamine (0.66g, 6.51mmol, 2.2 equivalent) with
10mL tetrahydrofurans, -78 DEG C are cooled to, n-BuLi (5.92mmol, 2.37mL, 2.5mol/L, 2 equivalent) is added dropwise, finishes, instead
Answer 1 hour, then by fluoro- 2,7- dioctyls dibenzo [a, the c] azophenlyene (1.6g, 2.96mmol, 1 equivalent) of 11,12- bis- and 25mL
Tetrahydrofuran wiring solution-forming, gradually gradually it is added dropwise, finishes to reaction solution, react 40 minutes, then the tetrahydrochysene furan of iodine is added dropwise thereto
Mutter solution (1.73g, 6.81mmol, 2.3 equivalent, 30mL tetrahydrofurans), after stirring 15 minutes, be placed in room temperature, be stirred overnight.Afterwards
Processing：Add sodium sulfite stirring and remove iodine, be subsequently poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous
Magnesium sulfate is dried.Post, 1.9g (yields are crossed with petroleum ether and dichloromethane mixed solvent：82%).Mass spectrum：Calculated value:792.12；
Measured value：792.96. elementary analysis：Calculated value：C, 54.56%；H, 5.09%；N, 3.53%；Measured value：：C, 52.43%；
H, 4.97%；N, 3.37%；
Embodiment 5
The preparation of iodo- 5,6 difluoro benzo [d] [1,2,5] the selenium diazole of 4,7- bis-
In 250mL long-neck there-necked flasks, under argon atmospher, add diisopropylamine (2.94g, 29.04mmol, 2.2 equivalent) with
30mL tetrahydrofurans, -78 DEG C are cooled to, n-BuLi (26.4mmol, 10.6mL, 2.5mol/L, 2 equivalent) is added dropwise, finishes, instead
Answer 1 hour, then by 5,6 difluoro benzo [d] [1,2,5] selenium diazole (2.9g, 13.2mmol, 1 equivalent) and 30mL tetrahydrochysene furan
Mutter wiring solution-forming, be gradually gradually added dropwise, finish to reaction solution, react 40 minutes, then the tetrahydrofuran solution of iodine is added dropwise thereto
(7.7g, 30.3mmol, 2.3 equivalent, 130mL tetrahydrofurans), is finished, and after stirring 15 minutes, is placed in room temperature, is stirred overnight.Afterwards
Processing：Add sodium sulfite stirring and remove iodine, be subsequently poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous
Magnesium sulfate is dried.Vacuum distillation is gone out solvent, obtained solid re-crystallizing in ethyl acetate, obtains yellow solid 5.1g (yields：
82%).Mass spectrum：Calculated value:471.73；Measured value：472.62. elementary analysis：Calculated value：C,15.31；N,5.95；Measured value：
C, 15.17%；N, 5.62%.
Embodiment 6
The preparation of the fluoro- 2,3- dimethyl-quinoxalines of the iodo- 6,7- bis- of 5,8- bis-
In 250mL long-neck there-necked flasks, under argon atmospher, add diisopropylamine (1.39g, 13.64mmol, 2.2 equivalent) with
15mL tetrahydrofurans, -78 DEG C are cooled to, n-BuLi (12.4mmol, 5mL, 2.5mol/L, 2 equivalent) is added dropwise, finishes, reaction 1
Hour, then fluoro- 2, the 3- dimethyl-quinoxalines (1.2g, 6.2mmol, 1 equivalent) of 6,7- bis- and 15mL tetrahydrofuran are made into
Solution, be gradually gradually added dropwise, finish to reaction solution, react 40 minutes, then thereto be added dropwise iodine tetrahydrofuran solution (3.6g,
14.3mmol, 2.3 equivalents, 60mL tetrahydrofurans), finish, after stirring 15 minutes, be placed in room temperature, be stirred overnight.Post processing：Add
Enter sodium sulfite stirring and remove iodine, be subsequently poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate
Dry.Vacuum distillation is gone out solvent, the mixed solvent recrystallization of obtained solid ethanol and toluene, obtains faint yellow solid
2.3g (yields：76%).Mass spectrum：Calculated value:445.86；Measured value：446.90. elementary analysis：Calculated value：C, 26.93%；H,
1.36%；N, 6.28%；Measured value：C, 26.77%；H, 1.22%；N, 6.09%.
Embodiment 7
The preparation of fluoro- 2H- benzos [d] [1,2,3] triazole of the iodo- 2- dodecyls -5,6 two of 4-
In 250mL long-neck there-necked flasks, under argon atmospher, add diisopropylamine (0.7g, 6.82mmol.1.1 equivalent) with
15mL tetrahydrofurans, -78 DEG C are cooled to, n-BuLi (6.2mmol, 2.5mL, 2.5mol/L, 1 equivalent) is added dropwise, finishes, reacted
1 hour, then by fluoro- 2H- benzos [d] [1,2, the 3] triazole (2g, 6.2mmol, 1 equivalent) of 2- dodecyls -5,6 two and 15mL
Tetrahydrofuran wiring solution-forming, be gradually gradually added dropwise, finish to reaction solution, react 40 minutes, then thereto be added dropwise iodine tetrahydrochysene
Tetrahydrofuran solution (1.8g, 7.12mmol, 1.15 equivalent, 30mL tetrahydrofurans), is finished, and after stirring 15 minutes, is placed in room temperature, is stirred
Overnight.Post processing：Add sodium sulfite stirring and remove iodine, be subsequently poured into water, dichloromethane extraction, saturated sodium-chloride water solution
Wash, anhydrous magnesium sulfate is dried.Post is crossed with petroleum ether and dichloromethane mixed solvent, obtains the compound of oily liquids, 2.3g (productions
Rate：83%).Mass spectrum：Calculated value:449.11；Measured value：449.97. elementary analysis：Calculated value：C, 48.12%；H, 5.83%；
N, 9.35%；Measured value：C, 47.97%；H, 5.68%；N, 9.22%.
Embodiment 8
The preparation of iodo- 5,6 difluoro benzo [d] [1,2,5] thiadiazoles of 4-
In 100mL long-neck there-necked flasks, under argon atmospher, add diisopropylamine (0.65g, 6.38mmol, 1.1 equivalent) with
10mL tetrahydrofurans, -78 DEG C are cooled to, n-BuLi (5.8mmol, 2.4mL, 2.5mol/L, 1 equivalent) is added dropwise, finishes, reacted
1 hour, then the tetrahydrofuran of 5,6 difluoro benzo [d] [1,2,5] thiadiazoles (1g, 5.8mmol, 1 equivalent) and 10mL is made into
Solution, be gradually gradually added dropwise, finish to reaction solution, react 40 minutes, then thereto be added dropwise iodine tetrahydrofuran solution (1.7g,
6.7mmol, 1.15 equivalents, 30mL tetrahydrofurans), finish, after stirring 15 minutes, be placed in room temperature, be stirred overnight.Post processing：Add
Enter sodium sulfite stirring and remove iodine, be subsequently poured into water, dichloromethane extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate
Dry.Vacuum distillation is gone out solvent, the mixed solvent recrystallization of obtained solid ethanol and toluene, obtains solid 1.4g (productions
Rate：80%).Mass spectrum：Calculated value:297.89；Measured value：298.67. elementary analysis：Calculated value：C, 24.18%；H, 0.34%；
N, 9.40%；S, 10.76%；Measured value：C, 23.92%；H, 0.26%；N, 9.14%；S, 10.48%.
Claims (3)
1. a kind of preparation method of double fluorine benzheterocycle conjugative monomers of iodine atom substitution, it is characterised in that comprise the following steps：
Lithium diisopropylamine first with the atomic reaction of hydrogen on double fluorobenzene and the phenyl ring of heterocyclic units 1, then adds single in reaction system
Matter iodine, so as to introduce double fluorine benzheterocycles of iodine atom, the i.e. substitution of the diiodo- of product 2 on double fluorine benzheterocycle conjugate unit phenyl ring
Conjugative monomer or double fluorine benzheterocycle conjugative monomers of 3 single iodine of product substitution；Reaction equation is
Wherein, Ar groups are the conjugated structure of armaticity, have one of following structural formula：
2. the preparation method of double fluorine benzheterocycle conjugative monomers of iodine atom substitution according to claim 1, its feature exist
In specifically including：
Under anhydrous, anaerobic atmosphere of inert gases, diisopropylamine is dissolved in anhydrous organic solvent, and temperature is reduced to -78 DEG C,
N-BuLi is slowly added dropwise into wherein, stirring reaction generates lithium diisopropylamine；Simultaneously heterocyclic units 1 are molten for the double fluorobenzene of reactant
Solution is added dropwise in lithium diisopropylamine in anhydrous organic solvent, the double fluorobenzene of reactant and heterocyclic units 1 and diisopropyl ammonia
The equivalent proportion of base lithium is determined by target product；After stirring reaction, the iodine of anhydrous organic solvent will be dissolved in, it is disposable to be added dropwise
Enter, the equivalent proportion of iodine is determined by target product；After simple substance iodine solution is added dropwise, it is warmed to room temperature naturally, stirring reaction mistake
Night；Target product is double fluorine benzheterocycle conjugative monomers of diiodo- substitution, then double fluorobenzene and heterocyclic units 1：Diisopropylaminoethyl
Lithium：The equivalent proportioning of elemental iodine should be 1:2:2.3；If target product is double fluorine benzheterocycle conjugative monomers of single iodine substitution,
Double fluorobenzene and heterocyclic units 1：Lithium diisopropylamine：The equivalent proportioning of elemental iodine should be 1:1:1.15.
3. the preparation method of double fluorine benzheterocycle conjugative monomers of iodine atom substitution according to claim 2, its feature exist
In the organic solvent be tetrahydrofuran, ether, n-hexane, dichloromethane, chloroform, one kind in toluene.
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| CN105777666A (en) * | 2016-03-27 | 2016-07-20 | 华南理工大学 | Preparation method of iodine atom-substituted methylic fluorobenzene and heterocyclic compound |
| KR102357223B1 (en) * | 2016-04-08 | 2022-02-03 | 메르크 파텐트 게엠베하 | Intermediates and Procedures for Synthesis of Functional Substances |
| CN108264516A (en) * | 2016-12-30 | 2018-07-10 | 深圳市星源材质科技股份有限公司 | A kind of preparation method and application of the conjugated molecule based on fluoro diazosulfide |
| CN112321512A (en) * | 2020-11-25 | 2021-02-05 | 上海吉奉生物科技有限公司 | Synthesis method of 4, 5-diiodo-1H-imidazole |
| CN114560871B (en) * | 2021-04-19 | 2023-04-07 | 中国科学院大学 | Synthesis method of selective substituted functionalized dithienyl imide luminescent material |
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| CN103396379A (en) * | 2013-07-11 | 2013-11-20 | 华南理工大学 | 5, 6-difluoro-benzothiazole and preparation method thereof |
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