CN105085163B - Synthesis method of 2-bromo-9,9-diphenylfluorene - Google Patents
Synthesis method of 2-bromo-9,9-diphenylfluorene Download PDFInfo
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- CN105085163B CN105085163B CN201510561569.XA CN201510561569A CN105085163B CN 105085163 B CN105085163 B CN 105085163B CN 201510561569 A CN201510561569 A CN 201510561569A CN 105085163 B CN105085163 B CN 105085163B
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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, and in particular to the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-.
Background technology
Electroluminescent organic material as a kind of novel organic semi-conductor material, as its luminous efficiency is high, element manufacturing
The advantages of process is simple, there are potential commercial application value, wherein fluorenes class chemical combination in fields such as light emitting diode, solaodes
Thing is a kind of preferable material.The fluorenes and its derivant conjugated system larger as intramolecular contains, joins with rigid plane again
Benzene structure, wider energy gap, higher luminous efficiency, structure are easy to the characteristics such as modification so as in electroluminescent material, solar energy
The fields such as battery material are widely used.
Chang, Shun Li etc. (Journal of Organic Chemistry, 75 (12), 4004-4013,2010) is carried
Go out with trifluoromethanesulfonic acid as dehydrant, bromo- 9, the 9- hexichol of 2- has been prepared as reaction raw materials with the bromo- 9- phenyl-fluorenes -9- alcohol of 2- and benzene
The method of base fluorenes.There is the problems such as yield is relatively low, and post processing difficulty causes relatively costly with trifluoromethanesulfonic acid costliness in the method.
The content of the invention
Present invention aim at providing a kind of 2- synthetic methods of bromo- 9,9- diphenylfluorenes.
Based on above-mentioned purpose, the present invention is adopted the following technical scheme that：The synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-, including
Following steps：
（1）After by 2- bromo- 9- phenyl-fluorenes -9- alcohol and benzene mixing, 61～66 DEG C are warming up to, are passed through while stirring enough anti-
Should gas, ventilation finish rear temperature rising reflux, moisture is separated while backflow（When ventilation finishes rear temperature rising reflux and continues one section of reaction
Between, moisture is separated while backflow, reaction can be promoted to carry out more abundant）；The bromo- 9- phenyl-fluorenes -9- alcohol of the 2- and benzene
Mol ratio is 1:10～18；The reaction gas is hydrogen chloride, hydrogen bromide or hydrogen iodide；（2）By step（1）Gained system is cooled to
15～25 DEG C, catalyst is dividedly in some parts in 0.5～1h, is finished, system is warming up to 35～50 DEG C, stop after 3.5～5h of reaction
Reaction；The catalyst is the mixture of aluminum trichloride (anhydrous) and anhydrous ferric trichloride, the bromo- 9- phenyl-fluorenes -9- alcohol of the 2-,
Aluminum trichloride (anhydrous), the mol ratio of anhydrous ferric trichloride are 1:1～1.2:0.1～0.3；（3）Separating-purifying, obtains 2- bromo- 9,
9- diphenylfluorenes.Step（1）What is carried out is the halogenation of the bromo- 9- phenyl-fluorenes -9- alcohol of 2- and reaction gas, in venting process
There is the bromo- 9- phenyl of a large amount of 2--fluorenes -9- alcohol to participate in reaction, remaining non-reacted parts then continue reaction during temperature rising reflux, instead
Should the enough purposes of gas be then the bromo- 9- phenyl of 2--fluorenes -9- alcohol is completely converted.In practice, tlc analysis can be adopted
（TLC）, gas chromatogram（GC）Or high performance liquid chromatography（HPLC）Method is judging reaction process.Step（2）Body when adding catalyst
System can heat release, therefore add the temperature of catalyst precarsor system unsuitable too high, preferably control between 15～25 DEG C.
The step（1）In, return time is 1～2h.
The step（2）In, catalyst is added in three batches, and the weight ratio of three additions is 3:2:1.Using what is be dividedly in some parts
Mode can more effectively control the temperature of reaction, it is to avoid by-product is generated.
The step（3）In, separating-purifying operation is：To step（2）Frozen water is added in gained system, organic faciess are isolated
And plus alkali liquor neutralize it, then with solvent extraction, isolate bromo- 9, the 9- diphenylfluorenes of target product 2-.
The addition of the frozen water and the mol ratio 20～25 of the bromo- 9- phenyl of 2--fluorenes -9- alcohol:1.
Extractant is ethyl acetate.
The alkali liquor is saturated sodium bicarbonate or sodium carbonate liquor.
The reaction mechanism mechanism of reaction of the present invention sees below formula：
。
Step（1）In, there is both sides technical advantage in the addition of benzene：On the one hand, due to the bromo- 9- phenyl of 2--fluorenes -9- alcohol
Used as reaction raw materials, itself is excessively sticky, belongs to spawn, is passed directly into reaction gas and is difficult to, and the addition of benzene is then
Dilution, dissolving raw material can be played a part of so that ventilatory response is smooth；On the other hand, step（1）In reaction
For balancing response, the presence of benzene, carry out keeping away water " protection " equivalent to product, prevented product that water occurs to a certain extent
Solution；Benzene is also step simultaneously（2）The initiation material of middle reaction, now makees solvent from benzene, can also omit follow-up removal solvent
Operation.
Step（2）In, in the selection of catalyst, the present invention selects the mixing of aluminum trichloride (anhydrous) and anhydrous ferric trichloride
Thing is used as mixed catalyst.It is experimentally confirmed that when adopting mixed catalyst, catalytic effect is than being used alone aluminum trichloride (anhydrous)
It is good, but the consumption of anhydrous ferric trichloride can not be excessive, crosses and can at most produce by-product, reduces the selectivity of target product.Separately
Outward, step（2）The temperature control of middle reaction is 35～50 DEG C, rather than by the way of back flow reaction, its purpose also for
Prevent temperature too high, cause side reaction.
To sum up, compared with prior art, what which reached has the beneficial effect that the synthetic method：
1）The present invention's is with low cost, when especially using hydrogen chloride and hydrogen bromide；
2）By the way of aluminum trichloride (anhydrous) and anhydrous ferric trichloride mixed catalytic, excellent catalytic effect, with single catalysis
Agent is compared, and after its catalysis, product yield improves 1.5～1.6 times；
3）Simple to operate, process is adapted to amplify.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of product obtained in embodiment 1；
Fig. 2 is the enlarged drawing that phenyl ring region is located in Fig. 1.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
The synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-, comprises the following steps：
（1）10 mmol 2- bromo- 9- phenyl-fluorenes -9- alcohol and 100mmol benzene are mixed, 61 DEG C is warming up under stirring, is passed through
Hydrogen chloride gas, until TLC is monitored to raw material point（The bromo- 9- phenyl of 2--fluorenes -9- alcohol）It is basic to disappear, after ventilation is finished, will reaction
System is warming up to reflux temperature, and flow back 1h, separates the moisture in system while backflow using water knockout drum；
（2）System is cooled to into 17 ± 2 DEG C, catalyst is dividedly in some parts in 0.5h, is finished, be warming up to 35 DEG C of reaction 3.5h
After terminate；Wherein catalyst is made up of 10mmol aluminum trichloride (anhydrous)s and 1mmol anhydrous ferric trichlorides, and catalyst adds in three batches
Complete, the weight ratio of three additions is 3:2:1；
（3）Separating-purifying obtains bromo- 9, the 9- diphenylfluorenes of 2-, and separating-purifying operation is：Reaction terminates backward system and adds
200 mmol frozen water；Layering, it is neutral that organic faciess saturated sodium bicarbonate is neutralized to pH, adds ethyl acetate extraction, extract
White solid powder product, yield 87.3% are obtained after concentration.
Embodiment 2
The synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-, comprises the following steps：
（1）10 mmol 2- bromo- 9- phenyl-fluorenes -9- alcohol and 180mmol benzene are mixed, 66 DEG C is warming up under stirring, is passed through
Reaction system until TLC is monitored to raw material point and disappeared substantially, after ventilation is finished, is warming up to reflux temperature, is returned by iodate hydrogen
Flow 1.5 h to terminate, the moisture in system while backflow, is separated using water knockout drum；
（2）System is cooled to into 18 ± 2 DEG C, catalyst is dividedly in some parts in 0.5h, is finished, be warming up to 50 DEG C of reaction 4.5h
After terminate；Wherein catalyst is made up of 12mmol aluminum trichloride (anhydrous)s and 3mmol anhydrous ferric trichlorides, and catalyst adds in three batches
Complete, the weight ratio of three additions is 3:2:1；
（3）Separating-purifying obtains bromo- 9, the 9- diphenylfluorenes of 2-, and separating-purifying operation is：Reaction terminates backward system and adds
220 mmol frozen water；Layering, it is neutral that organic faciess saturated sodium carbonate is neutralized to pH, adds ethyl acetate extraction, and extract is dense
White solid powder product, yield 92.7% are obtained after contracting.
Embodiment 3
The synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-, comprises the following steps：
（1）10 mmol 2- bromo- 9- phenyl-fluorenes -9- alcohol and 170mmol benzene are mixed, 64 DEG C is warming up under stirring, is passed through
Reaction system, until TLC is monitored to raw material point and disappeared substantially, after ventilation is finished, is warming up to backflow temperature by enough bromination hydrogen
Degree, 2 h of backflow terminate, and separate the moisture in system while backflow using water knockout drum；
（2）System is cooled to into 20 ± 2 DEG C, catalyst is dividedly in some parts in 1h, is finished, tie after being warming up to 45 DEG C of reaction 5h
Beam；Wherein catalyst is made up of 12mmol aluminum trichloride (anhydrous)s and 3mmol anhydrous ferric trichlorides, and catalyst is added in three batches, and three
The weight ratio of secondary addition is 3:2:1；
（3）Separating-purifying obtains bromo- 9, the 9- diphenylfluorenes of 2-, and separating-purifying operation is：Reaction terminates backward system and adds
240 mmol frozen water；Layering, it is neutral that organic faciess saturated sodium bicarbonate is neutralized to pH, adds ethyl acetate extraction, extract
White solid powder product, yield 95.1% are obtained after concentration.
Embodiment 4
The synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-, comprises the following steps：
（1）10 mmol 2- bromo- 9- phenyl-fluorenes -9- alcohol and 100mmol benzene are mixed, 62 DEG C is warming up under stirring, is passed through
Reaction system, until TLC is monitored to raw material point and disappeared substantially, after ventilation is finished, is warming up to backflow temperature by enough hydrogen chloride gas
Degree, backflow 1.5h terminate, and separate the moisture in system while backflow using water knockout drum；
（2）System is cooled to into 23 ± 2 DEG C, catalyst is dividedly in some parts in 0.5h, is finished, after being warming up to 40 DEG C of reaction 4h
Terminate；Wherein catalyst is made up of 11.5mmol aluminum trichloride (anhydrous)s and 2mmol anhydrous ferric trichlorides, and catalyst adds in three batches
Complete, the weight ratio of three additions is 3:2:1；
（3）Separating-purifying obtains bromo- 9, the 9- diphenylfluorenes of 2-, and separating-purifying operation is：Reaction terminates backward system and adds
250mmol frozen water；Layering, it is neutral that organic faciess saturated sodium bicarbonate is neutralized to pH, adds ethyl acetate extraction, and extract is dense
White solid powder product, yield 89.5% are obtained after contracting.
Analysis of test results
Nucleus magnetic hydrogen spectrum test is carried out to product obtained in embodiment 1, collection of illustrative plates is measured as depicted in figs. 1 and 2, wherein, Fig. 2 is
Fig. 1 middle position phenyl ring regional enlarged drawings, can become apparent from finding out hydrogen atom species and sum, hydrogen atom all concentrates on benzene from Fig. 2
Ring region, meets the feature of target product, can confirm that products obtained therefrom is bromo- 9, the 9- diphenylfluorenes of 2-；To other embodiment
The product for obtaining equally is detected that confirmation products obtained therefrom is target product.
In addition, testing to the fusing point of embodiment 1-4 products obtained therefrom, as a result show, its melting range 218.5～
It is 219.9 DEG C, suitable with 219～220 DEG C of the melting point values of bromo- 9, the 9- diphenylfluorenes of 2- provided by document, it is further characterized by gained
Product is target product.
Comparative example A
In this comparative example, 10 mmol 2- bromo- 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 is monitored to raw material point and disappeared substantially, through layering extraction, dry and dense
After contracting is processed, intermediate product is obtained.The intermediate product is redissolved in 100ml benzene, subsequent step is with reference to the step in embodiment 4
Suddenly（2）With（3）Carry out, finally obtain white solid powder product, yield 45.7%.
Comparative example B
In this comparative example, concentrated hydrochloric acid is changed into hydrobromic acid, other same comparative example As.White solid powder product is finally obtained,
50.1 % of yield.
Comparative example C
In this comparative example, concentrated hydrochloric acid is changed into hydroiodic acid, other same comparative example As.White solid powder product is finally obtained,
46.3 % of yield.
Comparative example D
In this comparative example, system is cooled to into 20～25 DEG C, according to 3 in the 0.5h:2:1 amount is dividedly in some parts 12～
13mmol aluminum trichloride (anhydrous)s, finish, and are warming up to 40 DEG C of reactions；Terminate after TLC detection 6 h of reaction, other with embodiment 4, most
White solid powder product, yield 55.2% are arrived afterwards.
Comparative example E
In this comparative example, system is cooled to into 20～25 DEG C, according to 3 in the 0.5h:2:1 amount is dividedly in some parts 12～
13mmol anhydrous ferric trichlorides, finish, and temperature is reacted to 40 DEG C；Terminate after TLC detection reaction 5h, other are finally obtained with embodiment 4
To white solid powder product, yield 59.2%.
Comparative example A, B, C are to change reaction gas into contrast that corresponding acid solution i.e. hydrochloric acid, hydrobromic acid and hydroiodic acid are carried out
Test, the yield of the final product that the yield of the final product obtained from after reaction is obtained with embodiment 4 are can be seen that when reaction
Thing is when being passed through by the way of reaction gas so that halogenating reaction is more thorough, and yield is higher, and its yield can bring up to molten using acid
Nearly 2 times of liquid.
Comparative example D, E is that the mixed catalyst of embodiment 4 is changed into the contrast experiment carried out after single catalyst, from reaction
When the yield of the final product that the yield of the final product for obtaining afterwards is obtained with embodiment 4 is can be seen that using mixed catalyst,
Product yield is higher, and its yield can bring up to 1.5～1.6 times of single catalyst.
Claims (6)
- The synthetic method of bromo- 9, the 9- diphenylfluorenes of 1.2-, it is characterised in that comprise the following steps：（1）After by 2- bromo- 9- phenyl-fluorenes -9- alcohol and benzene mixing, 61～66 DEG C are warming up to, are passed through while stirring enough Reaction gas, ventilation finish rear temperature rising reflux, and moisture is separated while backflow；The bromo- 9- phenyl-fluorenes -9- alcohol of the 2- and benzene Mol ratio be 1:10～18；The reaction gas is hydrogen chloride, hydrogen bromide or hydrogen iodide；（2）By step（1）Gained system is cooled to 15～25 DEG C, is dividedly in some parts catalyst, finishes in 0.5～1h, body System is warming up to 35～50 DEG C, stopped reaction after 3.5～5h of reaction；The catalyst is aluminum trichloride (anhydrous) and anhydrous three The mixture of iron chloride, the bromo- 9- phenyl-fluorenes -9- alcohol of the 2-, aluminum trichloride (anhydrous), the mol ratio of anhydrous ferric trichloride For 1:1～1.2:0.1～0.3；The step（2）In, catalyst is added in three batches, and the weight ratio of three additions is 3:2: 1；（3）Separating-purifying, obtains bromo- 9, the 9- diphenylfluorenes of 2-.
- 2. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 1, it is characterised in that the step（1） In, return time is 1～2h.
- 3. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 1, it is characterised in that the step（3） In, separating-purifying operation is：To step（2）Frozen water is added in gained system, organic faciess is isolated and is added alkali liquor to neutralize it, then With solvent extraction, isolate the bromo- 9,9- diphenylfluorenes of target product 2-.
- 4. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 3, it is characterised in that the frozen water plus Enter the mol ratio 20～25 of amount and the bromo- 9- phenyl of 2--fluorenes -9- alcohol:1.
- 5. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 3, it is characterised in that extractant is second Acetoacetic ester.
- 6. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 3, it is characterised in that the alkali liquor is full With sodium bicarbonate or sodium carbonate liquor.
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| 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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