CN105016968B - A kind of synthetic method of 2 bromine, 9,9 diphenylfluorene - Google Patents
A kind of synthetic method of 2 bromine, 9,9 diphenylfluorene Download PDFInfo
- Publication number
- CN105016968B CN105016968B CN201510397459.4A CN201510397459A CN105016968B CN 105016968 B CN105016968 B CN 105016968B CN 201510397459 A CN201510397459 A CN 201510397459A CN 105016968 B CN105016968 B CN 105016968B
- Authority
- CN
- China
- Prior art keywords
- bromo
- liquid
- diphenylfluorenes
- synthetic method
- reaction
- 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.)
- Active
Links
- 238000010189 synthetic method Methods 0.000 title claims abstract description 18
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title abstract 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title abstract 4
- 229910052794 bromium Inorganic materials 0.000 title abstract 4
- BKQXUNGELBDWLS-UHFFFAOYSA-N 9,9-diphenylfluorene Chemical compound C1=CC=CC=C1C1(C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 BKQXUNGELBDWLS-UHFFFAOYSA-N 0.000 title abstract 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 54
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000010792 warming Methods 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NOJDQJYQJQZCGS-UHFFFAOYSA-N 2-bromo-9-phenyl-9h-fluorene Chemical class C=1C(Br)=CC=C(C2=CC=CC=C22)C=1C2C1=CC=CC=C1 NOJDQJYQJQZCGS-UHFFFAOYSA-N 0.000 claims description 7
- RNJVXIRLVMVUJD-UHFFFAOYSA-N 1-bromo-9-phenyl-9h-fluorene Chemical class C1=2C(Br)=CC=CC=2C2=CC=CC=C2C1C1=CC=CC=C1 RNJVXIRLVMVUJD-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- KABUIVXKHNWFSA-UHFFFAOYSA-N 1-bromo-9,9-diphenylfluorene Chemical class C1=2C(Br)=CC=CC=2C2=CC=CC=C2C1(C=1C=CC=CC=1)C1=CC=CC=C1 KABUIVXKHNWFSA-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- ZJQCOVBALALRCC-UHFFFAOYSA-N 9-phenyl-9h-fluorene Chemical class C1=CC=CC=C1C1C2=CC=CC=C2C2=CC=CC=C21 ZJQCOVBALALRCC-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000011403 purification operation Methods 0.000 claims 1
- PUFWGUZSDHANBX-UHFFFAOYSA-N 1-phenyl-9h-fluorene Chemical class C=12CC3=CC=CC=C3C2=CC=CC=1C1=CC=CC=C1 PUFWGUZSDHANBX-UHFFFAOYSA-N 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- 150000001555 benzenes Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003810 ethyl acetate extraction Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WNXNWOBGPRKOJF-UHFFFAOYSA-N 2-bromo-9,9-diphenylfluorene Chemical class C12=CC(Br)=CC=C2C2=CC=CC=C2C1(C=1C=CC=CC=1)C1=CC=CC=C1 WNXNWOBGPRKOJF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alchlor Chemical compound 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of 9,9 diphenylfluorene of 2 bromine, comprises the following steps：1）Trifluoroacetic acid, aluminum trichloride (anhydrous) and benzene are mixed to prepare into A liquid in molar ratio；2）2 bromine, 9 phenyl fluorenes, 9 alcohol and benzene are mixed to prepare into B liquid in molar ratio；3）Under gas shield, in proportion A liquid and B liquid are mixed while stirring, while control system temperature is less than 50 DEG C；4）65～75 DEG C are warming up to, 1～1.5h is reacted, trifluoroacetic acid is added, continue 2～4h of reaction；5）Separating-purifying, obtains 2 bromine, 9,9 diphenylfluorene.The synthetic method is simple to operate, and reaction condition is gentle, with higher yield and relatively low cost, with wide industrialization promotion prospect.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-.
Background technology
The fluorenes and its derivative conjugated system larger as intramolecular contains, has rigid plane biphenyl structural, wider again
Energy gap, higher luminous efficiency, the structure characteristic that is easy to modify etc. so as in electroluminescent material, solar cell material
It is widely used in field.
The dehydration of the tertiary alcohol and aromatic ring, document Journal of Organic Chemistry, 75 (12), 4004-
4013,2010th, Tetrahedron, 70 (25), 3847-3853,2014, CN101514161 and CN102516295 are carried respectively
TFMS, sulfuric acid, p-methyl benzenesulfonic acid and methanesulfonic acid are gone out as dehydrating agent.TFMS as dehydrating agent high cost,
But system multiphase, yield be not high；Using sulfuric acid as dehydrating agent, cost is relatively low, but accessory substance is more, and yield is relatively low；To first
Although benzene sulfonic acid and methanesulfonic acid cost are low compared with TFMS, heterogeneous reaction is there is also, affect reaction yield.
The content of the invention
Present invention aim at there is provided a kind of synthetic method of the bromo- 9,9- diphenylfluorenes of 2-.
Based on above-mentioned purpose, following technical scheme is this invention takes：A kind of synthesis side of the bromo- 9,9- diphenylfluorenes of 2-
Method, specifically includes following steps：
1）By trifluoroacetic acid, aluminum trichloride (anhydrous) and benzene according to 1：(0.1～0.15)：The mixed in molar ratio system of (10～18)
Obtain A liquid；
2）By 2- bromo- 9- phenyl-fluorenes -9- alcohol and benzene according to 1：The mixed in molar ratio of (7～10) is obtained B liquid；
3）Under gas shield, while stirring A liquid and B liquid are mixed, in B liquid in the bromo- 9- phenyl-fluorenes -9- alcohol of 2- and A liquid
The mol ratio of trifluoroacetic acid is 1：1～1.2；In mixed process, control system temperature is less than 50 DEG C；
4）65～75 DEG C of 1～1.5h of reaction are warming up to, then maintenance system temperature trifluoroacetic acid are added, is continued reaction 2
Terminate reaction after～4 h；The bromo- 9- phenyl-fluorenes -9- alcohol of 2- is 1 with the mol ratio of trifluoroacetic acid additional amount：0.3～0.5；
5）Separating-purifying, obtains bromo- 9, the 9- diphenylfluorenes of 2-.
The step 3）While stirring B drops are added in A liquid during mixing.Heat can be discharged in A, B liquid mixed process,
The now too fast rising of temperature can cause subsequent reactions uncontrollable, and easily make benzene feedstock volatilize.Therefore, can pass through to control B liquid
Add speed carry out temperature control, if necessary also can additional cryostat carry out cooling temperature control.
The benzene is dry benzene.
Step 3）Gas shield is carried out using argon gas or nitrogen.
The separating-purifying is operated：Reaction terminates backward system and adds frozen water, its objective is to make aluminum trichloride (anhydrous) from
Separate in organic phase, after layering, take the neutralization of organic addition alkali lye, then with solvent extraction, to concentrate out target product 2- bromo-
9,9- diphenylfluorenes.The addition of frozen water and the mol ratio 20～25 of the bromo- 9- phenyl of raw material 2--fluorenes -9- alcohol:1.
Extracted using ethyl acetate in the separating-purifying operation.
The alkali lye is saturated sodium bicarbonate or sodium carbonate.
The present invention synthetic reaction mechanism be：The bromo- 9- phenyl-fluorenes -9- alcohol of 2- and benzene are in trifluoroacetic acid and anhydrous tri-chlorination
Carry out reacting under aluminium collective effect prepared target product, the present invention be investigated TFMS, sulfuric acid, methanesulfonic acid, to toluene
Impact of the acid such as sulfonic acid to reaction system, is contrasted with trifluoroacetic acid, finds to find with reaction system not when adopting these sour
Can mix, substantially belong to interface two phase reaction, will certainly so affect the effect reacted；And when adopting trifluoroacetic acid, trifluoro
Acetic acid can be greatly improved reaction yield and product with system complete miscibility while adding the significant alchlor of catalytic effect
Thing purity, shortens the reaction time.Jing inventor's initial analysis, alchlor are applied in combination with trifluoroacetic acid and are obtained in that preferably
Effect, reason is probably：One side alchlor strengthens the acidity of trifluoroacetic acid, promotes the generation of dehydration；Separately
One side alchlor has the bromo- 9- phenyl-fluorenes -9- alcohol of the property of " Friedel-Crafts reaction ", i.e. 2- to act on forming tertiary carbon with alchlor
Cation, then carries out Friedel-Crafts reaction with phenyl ring again.
Secondly, the present invention is dividedly in some parts trifluoroacetic acid, can reach following technique effect：The larger amount of trifluoro of early investment
Acetic acid amount, can accelerate reaction rate, and target product and partial intermediate are obtained after reaction, now add trifluoroacetic acid, can
Promote intermediate product to be transformed into target product, so that reaction yield is improved, reduce accessory substance.
Again, the present invention in trifluoroacetic acid, alchlor, benzene and raw material 2- bromo- 9- phenyl-fluorenes -9- alcohol dosage Jing
Ji is appropriate, while higher yields are ensured, has efficiently controlled cost.
To sum up, the synthetic method is simple to operate, and reaction condition is gentle, with higher yield and relatively low cost, has
Wide industrialization promotion prospect.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of product obtained in embodiment 1；
Fig. 2 is Fig. 1 middle position phenyl ring regional enlarged drawings.
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）The dry benzene of 10 mmol trifluoroacetic acids, 1 mmol aluminum trichloride (anhydrous)s and 100 mmol is mixed in flask
It is even to obtain A liquid；
2）10 mmol 2- bromo- 9- phenyl-fluorenes -9- alcohol and 70 mmol dry benzenes are mixed into obtain B liquid；
3）Under argon gas protection, B drops are added in A liquid mix while stirring, the bromo- 9- phenyl of 2--fluorenes -9- alcohol in B liquid
Mol ratio with trifluoroacetic acid in A liquid is 1：1；In mixed process, control system temperature is less than 40 DEG C；
4）System is warming up to 65 DEG C, reacts 1 h；Then maintenance system temperature 3 mmol trifluoroacetic acids are added；Continue anti-
2h is answered to terminate reaction.
5）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 phase saturated sodium bicarbonate is neutralized to pH, adds ethyl acetate extraction, extract
White solid powder product, yield 91.5% are obtained after concentration
Embodiment 2
The synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-, comprises the following steps：
1）By in the dry benzene and flask of 10 mmol trifluoroacetic acids, 1.5 mmol aluminum trichloride (anhydrous)s and 150 mmol
Mix to obtain A liquid；
2）10 mmol 2- bromo- 9- phenyl-fluorenes -9- alcohol and 90 mmol dry benzenes are mixed into obtain B liquid；
3）Under argon gas protection, B drops are added in A liquid mix while stirring, the bromo- 9- phenyl of 2--fluorenes -9- alcohol in B liquid
Mol ratio with trifluoroacetic acid in A liquid is 1：1, in mixed process, control system temperature is less than 45 DEG C；
4）System is warming up to 75 DEG C, reacts 1.5 h；Then maintenance system temperature 5 mmol trifluoroacetic acids are added；Continue
Reaction 4h terminates reaction.
5）Separating-purifying obtains bromo- 9, the 9- diphenylfluorenes of 2-, and separating-purifying operation is：Reaction terminates backward system and adds
250 mmol frozen water；Layering, it is neutral that organic phase saturated sodium bicarbonate is neutralized to pH, adds ethyl acetate extraction, extract
White solid powder product, yield 98.6% are obtained after concentration.
Embodiment 3
The synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-, comprises the following steps：
1）By in the dry benzene and flask of 10 mmol trifluoroacetic acids, 1.2 mmol aluminum trichloride (anhydrous)s and 180 mmol
Mix to obtain A liquid；
2）10 mmol 2- bromo- 9- phenyl-fluorenes -9- alcohol and 100 mmol dry benzenes are mixed into obtain B liquid；
3）Under argon gas protection, B drops are added in A liquid mix while stirring, the bromo- 9- phenyl of 2--fluorenes -9- alcohol in B liquid
Mol ratio with trifluoroacetic acid in A liquid is 1：1, while control system temperature is less than 45 DEG C；
4）System is warming up to 70 DEG C, reacts 1.5 h；Then maintenance system temperature 5 mmol trifluoroacetic acids are added；Continue
Reaction 4h terminates reaction.
5）Separating-purifying obtains bromo- 9, the 9- diphenylfluorenes of 2-, and separating-purifying operation is：Reaction terminates backward system and adds
230 mmol frozen water；Layering, it is neutral that organic phase saturated sodium bicarbonate is neutralized to pH, adds ethyl acetate extraction, extract
White solid powder product, yield 97.1% are obtained after concentration.
Embodiment 4
The synthetic method of bromo- 9, the 9- diphenylfluorenes of 2-, comprises the following steps：
1）By the dry benzene and flask of 12 mmol trifluoroacetic acids, 1.44 mmol aluminum trichloride (anhydrous)s and 216 mmol
In mix to obtain A liquid；
2）10 mmol 2- bromo- 9- phenyl-fluorenes -9- alcohol and 120 mmol dry benzenes are mixed into obtain B liquid；
3）Under nitrogen protection, while stirring B drops are added in A liquid and are mixed, the bromo- 9- phenyl of 2--fluorenes -9- alcohol in B liquid
Mol ratio with trifluoroacetic acid in A liquid is 1：1.2；In mixed process, control system temperature is less than 50 DEG C；
4）System is warming up to 70 DEG C, reacts 1h；Then maintenance system temperature 5 mmol trifluoroacetic acids are added；Continue reaction
4h terminates reaction.
5）Separating-purifying obtains bromo- 9, the 9- diphenylfluorenes of 2-, and separating-purifying operation is：Reaction terminates backward system and adds
230 mmol frozen water；Layering, it is neutral that organic phase sodium carbonate is neutralized to pH, adds ethyl acetate extraction, after extract concentration
Obtain white solid powder product, yield 97.5%.
Embodiment 5
Nucleus magnetic hydrogen spectrum test is carried out to product obtained in embodiment 1, collection of illustrative plates such as Fig. 1 is measured, Fig. 2 is Fig. 1 middle position phenyl ring area
Domain enlarged drawing, can become apparent from finding out hydrogen atom species and sum, hydrogen atom all concentrates on phenyl ring region, meets target product
Feature, can confirm that products obtained therefrom is bromo- 9, the 9- diphenylfluorenes of 2-；The product that other embodiment is obtained equally is examined
Survey, confirm that products obtained therefrom is target product.
The fusing point of embodiment 1-4 products obtained therefrom is tested, as a result shows its fusing point at 216.5～217.9 DEG C, with document institute
219～220 DEG C of the melting point values of the bromo- 9,9- diphenylfluorenes of 2- of offer are quite.
Claims (7)
1. the synthetic method of bromo- 9, the 9- diphenylfluorenes of a kind of 2-, it is characterised in that specifically include following steps：
1）By trifluoroacetic acid, aluminum trichloride (anhydrous) and benzene according to 1：(0.1～0.15)：The mol ratio of (10～18) is mixed
Close and A liquid is obtained；
2）By 2- bromo- 9- phenyl-fluorenes -9- alcohol and benzene according to 1：The mixed in molar ratio of (7～10) is obtained B liquid；
3）Under gas shield, while stirring A liquid and B liquid are mixed, the bromo- 9- phenyl-fluorenes -9- alcohol of 2- and A in B liquid
In liquid, the mol ratio of trifluoroacetic acid is 1：1～1.2；In mixed process, control system temperature is less than 50 DEG C；The step
3）While stirring B drops are added in A liquid during mixing；
4）65～75 DEG C of 1～1.5h of reaction are warming up to, then maintenance system temperature trifluoroacetic acid are added, is continued reaction 2
Terminate reaction after～4 h；The bromo- 9- phenyl-fluorenes -9- alcohol of 2- is 1 with the mol ratio of trifluoroacetic acid additional amount：0.3～
0.5 ；
5）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 benzene is drying
Benzene.
3. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 1, it is characterised in that step 3）Using argon
Gas or nitrogen carry out gas shield.
4. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 1-3 is arbitrary, it is characterised in that described point
From purification operations it is：Reaction terminates backward system and adds frozen water, layering to take organic addition alkali lye neutralization, then with solvent extraction,
Concentrate out the bromo- 9,9- diphenylfluorenes of target product 2-.
5. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 4, it is characterised in that the addition of frozen water
The mol ratio 20～25 of 9- phenyl-fluorenes -9- alcohol bromo- with raw material 2-:1.
6. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 4, it is characterised in that the separating-purifying
Extracted using ethyl acetate in operation.
7. the synthetic method of bromo- 9, the 9- diphenylfluorenes of 2- as described in claim 4, it is characterised in that the alkali lye is full
With sodium acid carbonate or sodium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510397459.4A CN105016968B (en) | 2015-07-07 | 2015-07-07 | A kind of synthetic method of 2 bromine, 9,9 diphenylfluorene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510397459.4A CN105016968B (en) | 2015-07-07 | 2015-07-07 | A kind of synthetic method of 2 bromine, 9,9 diphenylfluorene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105016968A CN105016968A (en) | 2015-11-04 |
| CN105016968B true CN105016968B (en) | 2017-04-05 |
Family
ID=54407332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510397459.4A Active CN105016968B (en) | 2015-07-07 | 2015-07-07 | A kind of synthetic method of 2 bromine, 9,9 diphenylfluorene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105016968B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040072004A (en) * | 2003-02-07 | 2004-08-16 | 삼성에스디아이 주식회사 | Emitting compound for electroluminescence device and device using thereof |
| JP5103727B2 (en) * | 2005-11-16 | 2012-12-19 | 東ソー株式会社 | Fluorene compound and organic EL device using the same |
| JP5353186B2 (en) * | 2007-11-30 | 2013-11-27 | 住友化学株式会社 | Amine-based polymer compound and light emitting device using the same |
| KR100964223B1 (en) * | 2008-02-11 | 2010-06-17 | 삼성모바일디스플레이주식회사 | Organic light emitting device and flat panel display device having the same |
-
2015
- 2015-07-07 CN CN201510397459.4A patent/CN105016968B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105016968A (en) | 2015-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102875440B (en) | Preparation method of 3-(4-chlorobutyl)-5-cyanoindole | |
| CN106749139A (en) | One kind is polysubstituted to condense benzofuran derivative and preparation method thereof | |
| CN101318887B (en) | Method for preparing indene compounds | |
| Nagawade et al. | Zirconyl (IV) chloride-catalysed reaction of indoles: an expeditious synthesis of bis (indolyl) methanes | |
| CN105418421A (en) | Synthesizing method for 3-methoxyacrylate | |
| CN103570510A (en) | One-pot synthesis method for 5-bromo-2-chloro-4'-ethoxy diphenylmethane | |
| Bigdeli et al. | A series of 1, 8-dioxooctahydroxanthenes are prepared using trichloroisocyanuric acid | |
| CN105016968B (en) | A kind of synthetic method of 2 bromine, 9,9 diphenylfluorene | |
| CN104529935B (en) | Method for synthesizing ethyl 2-(3-aldehyde-4-isobutyloxyphenyl)-4-methylthiazole-5-formate | |
| CN101693649A (en) | Process for preparing 1.3.5-trimethoxybenzene | |
| CN108997299B (en) | Efficient long-life organic room-temperature phosphorescent material and preparation method thereof | |
| CN108821975B (en) | Hydrogenated phenanthrene derivative containing exocyclic double bond and preparation method thereof | |
| CN102992989A (en) | Synthesis method of beta-menadione | |
| CN114149380A (en) | Novel preparation method of 2-aryl benzoxazole series compounds | |
| CN106831802B (en) | A kind of synthetic method of four benzofuran compounds of spiral shell indoline | |
| CN103724320A (en) | Preparation method of 2-isopropyl thioxanthone | |
| CN104557637A (en) | Dehydration control method for synthesis of bisphenol S | |
| Terang et al. | Trimethylsilyl chloride assisted conjugate addition-elimination of organocopper reagents to 2-bis (methylthio) nitroethylene: An efficient and highly stereoselective synthesis of 2-methylthio-2-alkyl/aryl-1-nitroethylenes and their application for synthesis of nitroheterocycles | |
| CN108675972B (en) | Preparation method of amiodarone hydrochloride intermediate 2-butyl benzofuran | |
| CN107986970B (en) | A kind of polysubstituted aromatic hydrocarbon derivatives and preparation method thereof | |
| CN103319318A (en) | Recovering and recycling method of excessive methyl catechol in vanillin production process | |
| CN106431981A (en) | Hydroxy benzonitril preparation process | |
| Tang et al. | Silver (i)-catalyzed addition of pyridine-N-oxides to alkynes: a practical approach for N-alkenoxypyridinium salts | |
| Guerrero et al. | 1, 2-Dimethylimidazole (DMI) and microwaves in the alkylation of carboxylic acids and phenols with dimethyl and diethyl carbonates | |
| Eshghi et al. | Synthesis of new indolyl crown ethers catalyzed with ferric hydrogensulfate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |