CN105085163A - Synthesis method of 2-bromo-9,9-diphenylfluorene - Google Patents
Synthesis method of 2-bromo-9,9-diphenylfluorene Download PDFInfo
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Abstract
The invention provides a synthesis method of 2-bromo-9,9-diphenylfluorene and belongs to the technical field of organic synthesis. The synthesis method comprises steps as follows: (1), after 2-bromo-9-phenyl-fluorene-9-ol and benzene are mixed, reaction gas is introduced for a reaction at the temperature of 61-66 DEG C while the components are stirred, the temperature is increased and backflow is performed after gas introduction is finished, and water is separated while backflow is performed; (2), a catalyst is added in 0.5-1 h after a system obtained from the step (1) is cooled, the temperature is increased to 35-50 DEG C, and the mixture reacts for 3.5-5 h; (3), 2-bromo-9,9-diphenylfluorene is obtained through separation and purification. The synthesis method of 2-bromo-9,9-diphenylfluorene is low in cost, especially when hydrogen chloride and hydrogen bromide are utilized; with the adoption of an aluminum trichloride anhydrous and ferric chloride anhydrous mixed catalysis mode, the catalysis effect is good, the reaction time is short, and the yield is high; the operation is simple, the process is reliable, and scale-up is facilitated.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to the synthetic method of bromo-9, the 9-diphenylfluorene of 2-.
Background technology
Electroluminescent organic material is as a kind of novel organic semi-conductor material, due to advantages such as its luminous efficiency are high, device making technics is simple, have potential commercial application value in the field such as photodiode, solar cell, wherein compound of fluorene class is a kind of desirable material.Fluorenes and derivative thereof are owing to containing larger conjugated system in molecule, there is again rigid plane biphenyl structural, wider energy gap, higher luminous efficiency, structure be easy to the characteristics such as modification, make it be widely used in the field such as electroluminescent material, solar cell material.
(JournalofOrganicChemistry, 75 (12) such as Chang, ShunLi, 4004-4013,2010) proposing with trifluoromethanesulfonic acid is dewatering agent, with 2-bromo-9-phenyl-fluorenes-9-alcohol and benzene for reaction raw materials prepares the method for bromo-9, the 9-diphenylfluorene of 2-.It is lower to there is yield in this method, and aftertreatment difficulty and trifluoromethanesulfonic acid costliness cause the problems such as cost is higher.
Summary of the invention
The object of the invention is to provide a kind of 2-synthetic method of bromo-9,9-diphenylfluorene.
Based on above-mentioned purpose, the present invention takes following technical scheme: the synthetic method of bromo-9, the 9-diphenylfluorene of 2-, comprises the following steps:
(1) by after bromo-for 2-9-phenyl-fluorenes-9-alcohol and benzene mixing, be warming up to 61 ~ 66 DEG C, pass into enough reaction gases while stirring, temperature rising reflux after ventilation, (after ventilation, temperature rising reflux continues reaction for some time to separate moisture while backflow, separate moisture while backflow, reaction can be impelled to carry out more abundant); The mol ratio of the bromo-9-phenyl-fluorenes-9-alcohol of described 2-and benzene is 1:10 ~ 18; Described reaction gas is hydrogenchloride, hydrogen bromide or hydrogen iodide; (2) step (1) gained system is cooled to 15 ~ 25 DEG C, adds catalyzer in batches, finish in 0.5 ~ 1h, system is warming up to 35 ~ 50 DEG C, stopped reaction after reaction 3.5 ~ 5h; Described catalyzer is the mixture of aluminum trichloride (anhydrous) and FERRIC CHLORIDE ANHYDROUS, and the mol ratio of described 2-bromo-9-phenyl-fluorenes-9-alcohol, aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS is 1:1 ~ 1.2:0.1 ~ 0.3; (3) separating-purifying, obtains bromo-9, the 9-diphenylfluorene of 2-.The halogenating reaction of what step (1) was carried out the is bromo-9-phenyl-fluorenes-9-alcohol of 2-and reaction gas, in venting process, the existing bromo-9-phenyl of a large amount of 2--fluorenes-9-alcohol participates in reaction, residue non-reacted parts then continues reaction in temperature rising reflux process, and the enough object of reaction gas is then that 2-bromo-9-phenyl-fluorenes-9-alcohol is completely converted.In practice, tlc analysis (TLC), gas-chromatography (GC) or high performance liquid chromatography (HPLC) method can be adopted to judge reaction process.When step (2) adds catalyzer, system can heat release, and the temperature therefore adding catalyst precursor system is unsuitable too high, should control between 15 ~ 25 DEG C.
In described step (1), return time is 1 ~ 2h.
In described step (2), catalyzer adds in three batches, and the weight ratio added for three times is 3:2:1.Adopt the mode in batches added more effectively can control the temperature of reacting, avoid by product to generate.
In described step (3), separating-purifying is operating as: in step (2) gained system, add frozen water, isolates organic phase and add alkali lye to neutralize it, then with solvent extraction, isolate bromo-9, the 9-diphenylfluorene of target product 2-.
Mol ratio 20 ~ the 25:1 of the add-on of described frozen water and 2-bromo-9-phenyl-fluorenes-9-alcohol.
Extraction solvent is ethyl acetate.
Described alkali lye is saturated sodium bicarbonate or sodium carbonate solution.
Reaction mechanism of the present invention is shown in following formula:
。
In step (1), benzene add the technical superiority of depositing both ways: on the one hand, because 2-bromo-9-phenyl-fluorenes-9-alcohol is as reaction raw materials, itself is too sticky, belong to spawn, directly pass into reaction gas to be difficult to realize, adding of benzene, dilution can be played, dissolve the effect of raw material, make ventilatory response smooth; On the other hand, the reaction in step (1) is the existence of balanced reaction, benzene, is equivalent to carry out keeping away water " protection " to product, prevents product to be hydrolyzed to a certain extent; Benzene is also the starting raw material of reaction in step (2) simultaneously, now selects benzene to make solvent, also can omit the operation of follow-up removal solvent.
In step (2), in the selection of catalyzer, the present invention selects the mixture of aluminum trichloride (anhydrous) and FERRIC CHLORIDE ANHYDROUS as mixed catalyst.Experiment confirms, when adopting mixed catalyst, catalytic effect is better than being used alone aluminum trichloride (anhydrous), but the consumption of FERRIC CHLORIDE ANHYDROUS can not be too much, crosses and can produce by product at most, the selectivity of target product is reduced.In addition, the temperature of reaction in step (2) controls to be 35 ~ 50 DEG C, instead of adopts the mode of back flow reaction, and its object is also to prevent temperature too high, causes side reaction.
To sum up, compared with prior art, its beneficial effect reached is this synthetic method:
1) of the present invention with low cost, when especially using hydrogenchloride and hydrogen bromide;
2) adopt the mode of aluminum trichloride (anhydrous) and FERRIC CHLORIDE ANHYDROUS mixed catalytic, excellent catalytic effect, compared with single catalyst, its catalysis after product yield improves 1.5 ~ 1.6 times;
3) simple to operate, process, is applicable to amplifying.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of the product that embodiment 1 obtains;
Fig. 2 is the enlarged view being positioned at phenyl ring region in Fig. 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
embodiment 1
The synthetic method of bromo-9, the 9-diphenylfluorene of 2-, comprises the following steps:
(1) by bromo-for 10mmol2-9-phenyl-fluorenes-9-alcohol and the mixing of 100mmol benzene, 61 DEG C are warming up under stirring, pass into hydrogen chloride gas, until TLC monitoring disappears substantially to raw material point (2-bromo-9-phenyl-fluorenes-9-alcohol), after ventilation, reaction system is warming up to reflux temperature, backflow 1h, while backflow, utilizes water trap to separate moisture in system;
(2) system is cooled to 17 ± 2 DEG C, in 0.5h, adds catalyzer in batches, finish, terminate after being warming up to 35 DEG C of reaction 3.5h; Wherein catalyzer is made up of 10mmol aluminum trichloride (anhydrous) and 1mmol FERRIC CHLORIDE ANHYDROUS, and catalyzer adds in three batches, and the weight ratio added for three times is 3:2:1;
(3) separating-purifying obtains bromo-9, the 9-diphenylfluorene of 2-, and separating-purifying is operating as: reaction terminates backward system and adds 200mmol frozen water; Layering, it is neutral that organic phase saturated sodium bicarbonate is neutralized to pH, adds extraction into ethyl acetate, obtains white solid powder product, yield 87.3% after extract is concentrated.
embodiment 2
The synthetic method of bromo-9, the 9-diphenylfluorene of 2-, comprises the following steps:
(1) by bromo-for 10mmol2-9-phenyl-fluorenes-9-alcohol and the mixing of 180mmol benzene, 66 DEG C are warming up under stirring, pass into hydrogen iodide gas, until TLC monitoring disappears substantially to raw material point, after ventilation, reaction system is warming up to reflux temperature, and backflow 1.5h terminates, and utilizes water trap to separate moisture in system while backflow;
(2) system is cooled to 18 ± 2 DEG C, in 0.5h, adds catalyzer in batches, finish, terminate after being warming up to 50 DEG C of reaction 4.5h; Wherein catalyzer is made up of 12mmol aluminum trichloride (anhydrous) and 3mmol FERRIC CHLORIDE ANHYDROUS, and catalyzer adds in three batches, and the weight ratio added for three times is 3:2:1;
(3) separating-purifying obtains bromo-9, the 9-diphenylfluorene of 2-, and separating-purifying is operating as: reaction terminates backward system and adds 220mmol frozen water; Layering, it is neutral that organic phase saturated sodium carbonate is neutralized to pH, adds extraction into ethyl acetate, obtains white solid powder product, yield 92.7% after extract is concentrated.
embodiment 3
The synthetic method of bromo-9, the 9-diphenylfluorene of 2-, comprises the following steps:
(1) by bromo-for 10mmol2-9-phenyl-fluorenes-9-alcohol and the mixing of 170mmol benzene, 64 DEG C are warming up under stirring, pass into enough bromize hydrogen gas, until TLC monitoring disappears substantially to raw material point, after ventilation, reaction system is warming up to reflux temperature, and backflow 2h terminates, and utilizes water trap to separate moisture in system while backflow;
(2) system is cooled to 20 ± 2 DEG C, in 1h, adds catalyzer in batches, finish, terminate after being warming up to 45 DEG C of reaction 5h; Wherein catalyzer is made up of 12mmol aluminum trichloride (anhydrous) and 3mmol FERRIC CHLORIDE ANHYDROUS, and catalyzer adds in three batches, and the weight ratio added for three times is 3:2:1;
(3) separating-purifying obtains bromo-9, the 9-diphenylfluorene of 2-, and separating-purifying is operating as: reaction terminates backward system and adds 240mmol frozen water; Layering, it is neutral that organic phase saturated sodium bicarbonate is neutralized to pH, adds extraction into ethyl acetate, obtains white solid powder product, yield 95.1% after extract is concentrated.
embodiment 4
The synthetic method of bromo-9, the 9-diphenylfluorene of 2-, comprises the following steps:
(1) by bromo-for 10mmol2-9-phenyl-fluorenes-9-alcohol and the mixing of 100mmol benzene, 62 DEG C are warming up under stirring, pass into enough hydrogen chloride gas, until TLC monitoring disappears substantially to raw material point, after ventilation, reaction system is warming up to reflux temperature, and backflow 1.5h terminates, and utilizes water trap to separate moisture in system while backflow;
(2) system is cooled to 23 ± 2 DEG C, in 0.5h, adds catalyzer in batches, finish, terminate after being warming up to 40 DEG C of reaction 4h; Wherein catalyzer is made up of 11.5mmol aluminum trichloride (anhydrous) and 2mmol FERRIC CHLORIDE ANHYDROUS, and catalyzer adds in three batches, and the weight ratio added for three times is 3:2:1;
(3) separating-purifying obtains bromo-9, the 9-diphenylfluorene of 2-, and separating-purifying is operating as: reaction terminates backward system and adds 250mmol frozen water; Layering, it is neutral that organic phase saturated sodium bicarbonate is neutralized to pH, adds extraction into ethyl acetate, obtains white solid powder product, yield 89.5% after extract is concentrated.
analysis of test results
The product obtained to embodiment 1 carries out nucleus magnetic hydrogen spectrum test, record collection of illustrative plates as depicted in figs. 1 and 2, wherein, Fig. 2 is Fig. 1 meta phenyl ring regional enlarged drawing, clearlyer can find out hydrogen atom kind and sum from Fig. 2, hydrogen atom all concentrates on phenyl ring region, meets the feature of target product, can confirm that products obtained therefrom is bromo-9, the 9-diphenylfluorene of 2-; The product that other embodiments obtain is detected equally, all confirms that products obtained therefrom is target product.
In addition, test the fusing point of embodiment 1-4 products obtained therefrom, result shows, its melting range is all at 218.5 ~ 219.9 DEG C, and the melting point values 219 ~ 220 DEG C of bromo-9, the 9-diphenylfluorene of the 2-provided with document is suitable, confirms that products obtained therefrom is target product further.
comparative example A
In this comparative example, bromo-for 10mmol2-9-phenyl-fluorenes-9-alcohol and 100mmol benzene are mixed and 200ml concentrated hydrochloric acid (12mol/L), 50 ~ 62 DEG C of stirring reactions, until TLC monitoring disappears substantially to raw material point, after layering extraction, drying and concentration, obtain intermediate product.Again be dissolved in by this intermediate product in 100ml benzene, subsequent step carries out with reference to the step (2) in embodiment 4 and (3), finally obtains white solid powder product, yield 45.7%.
comparative example B
In this comparative example, change concentrated hydrochloric acid into Hydrogen bromide, other same comparative example As.Finally obtain white solid powder product, yield 50.1%.
comparative example C
In this comparative example, change concentrated hydrochloric acid into hydroiodic acid HI, other same comparative example As.Finally obtain white solid powder product, yield 46.3%.
comparative example D
In this comparative example, system is cooled to 20 ~ 25 DEG C, in 0.5h, adds 12 ~ 13mmol aluminum trichloride (anhydrous) according to the amount of 3:2:1 in batches, finish, be warming up to 40 DEG C of reactions; Terminate after TLC detection reaction 6h, other finally arrive white solid powder product with embodiment 4, yield 55.2%.
comparative example E
In this comparative example, system is cooled to 20 ~ 25 DEG C, adds 12 ~ 13mmol FERRIC CHLORIDE ANHYDROUS in batches, finish in 0.5h according to the amount of 3:2:1, temperature is to 40 DEG C of reactions; Terminate after TLC detection reaction 5h, other finally obtain white solid powder product with embodiment 4, yield 59.2%.
Reaction gas is changed into the simultaneous test that corresponding acid solution and hydrochloric acid, Hydrogen bromide and hydroiodic acid HI carry out by comparative example A, B, C, the yield of the final product that the yield of the final product obtained after reaction and embodiment 4 obtain, when reactant employing passes into the mode of reaction gas, make halogenating reaction more thorough, yield is higher, and its yield can bring up to 2 times that adopt acid solution nearly.
Comparative example D, E are the contrast experiments carried out after changing the mixed catalyst of embodiment 4 into single catalyst, the yield of the final product that the yield of the final product obtained after reaction and embodiment 4 obtain, when adopting mixed catalyst, product yield is higher, and its yield can bring up to 1.5 ~ 1.6 times of single catalyst.
Claims (7)
- The synthetic method of bromo-9, the 9-diphenylfluorene of 1.2-, is characterized in that, comprise the following steps:(1) by after bromo-for 2-9-phenyl-fluorenes-9-alcohol and benzene mixing, be warming up to 61 ~ 66 DEG C, pass into enough reaction gases while stirring, temperature rising reflux after ventilation, separates moisture while backflow; The mol ratio of the bromo-9-phenyl-fluorenes-9-alcohol of described 2-and benzene is 1:10 ~ 18; Described reaction gas is hydrogenchloride, hydrogen bromide or hydrogen iodide;(2) step (1) gained system is cooled to 15 ~ 25 DEG C, adds catalyzer in batches, finish in 0.5 ~ 1h, system is warming up to 35 ~ 50 DEG C, stopped reaction after reaction 3.5 ~ 5h; Described catalyzer is the mixture of aluminum trichloride (anhydrous) and FERRIC CHLORIDE ANHYDROUS, and the mol ratio of described 2-bromo-9-phenyl-fluorenes-9-alcohol, aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS is 1:1 ~ 1.2:0.1 ~ 0.3;(3) separating-purifying, obtains bromo-9, the 9-diphenylfluorene of 2-.
- 2. the synthetic method of bromo-9, the 9-diphenylfluorene of 2-as claimed in claim 1, it is characterized in that, in described step (1), return time is 1 ~ 2h.
- 3. the synthetic method of bromo-9, the 9-diphenylfluorene of 2-as claimed in claim 1, it is characterized in that, in described step (2), catalyzer adds in three batches, and the weight ratio added for three times is 3:2:1.
- 4. 2-bromo-9 as claimed in claim 1, the synthetic method of 9-diphenylfluorene, it is characterized in that, in described step (3), separating-purifying is operating as: in step (2) gained system, add frozen water, isolate organic phase and add alkali lye and neutralize it, then with solvent extraction, isolate bromo-9, the 9-diphenylfluorene of target product 2-.
- 5. the synthetic method of bromo-9, the 9-diphenylfluorene of 2-as claimed in claim 4, is characterized in that, the mol ratio 20 ~ 25:1 of the add-on of described frozen water and 2-bromo-9-phenyl-fluorenes-9-alcohol.
- 6. the synthetic method of bromo-9, the 9-diphenylfluorene of 2-as claimed in claim 4, it is characterized in that, extraction solvent is ethyl acetate.
- 7. the synthetic method of bromo-9, the 9-diphenylfluorene of 2-as claimed in claim 4, it is characterized in that, described alkali lye is saturated sodium bicarbonate or sodium carbonate solution.
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Cited By (3)
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| CN109665938A (en) * | 2018-12-18 | 2019-04-23 | 河南省科学院化学研究所有限公司 | A kind of -9 ' of bromo- 9- methyl of 4--phenyl fluorenes production method |
| CN113149809A (en) * | 2021-04-09 | 2021-07-23 | 河南省科学院化学研究所有限公司 | 9- ([1, 1' -biphenyl ] -3-yl) -9-phenyl-2-bromofluorene and synthesis method thereof |
| CN114044733A (en) * | 2021-11-28 | 2022-02-15 | 中唯炼焦技术国家工程研究中心有限责任公司 | Method for efficiently synthesizing 2-bromo-9,9-diphenylfluorene by metal catalysis |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109665938A (en) * | 2018-12-18 | 2019-04-23 | 河南省科学院化学研究所有限公司 | A kind of -9 ' of bromo- 9- methyl of 4--phenyl fluorenes production method |
| CN113149809A (en) * | 2021-04-09 | 2021-07-23 | 河南省科学院化学研究所有限公司 | 9- ([1, 1' -biphenyl ] -3-yl) -9-phenyl-2-bromofluorene and synthesis method thereof |
| CN114044733A (en) * | 2021-11-28 | 2022-02-15 | 中唯炼焦技术国家工程研究中心有限责任公司 | Method for efficiently synthesizing 2-bromo-9,9-diphenylfluorene by metal catalysis |
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