CN105198697A - Synthetic method for 2-bromofluorene derivatives - Google Patents
Synthetic method for 2-bromofluorene derivatives Download PDFInfo
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- CN105198697A CN105198697A CN201510295551.XA CN201510295551A CN105198697A CN 105198697 A CN105198697 A CN 105198697A CN 201510295551 A CN201510295551 A CN 201510295551A CN 105198697 A CN105198697 A CN 105198697A
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Abstract
The invention provides a synthetic method for 2-bromofluorene derivatives. The synthetic method includes the following steps: hybrid reaction of fluorene or derivatives thereof, quaternary ammonium salt, sodium bromate and hydrobromic acid is carried out; extraction is performed through dichloromethane to obtain organic phase; then the organic phase is washed, dried, filtered and concentrated through anhydrous sodium sulfate, and finally, recrystallization is performed, and 2-bromofluorene derivatives disclosed by the invention can be obtained. The synthetic method for 2-bromofluorene derivatives, provided by the invention has the advantages that the operation method is simple, required equipment for reaction is simple, the reaction condition is gentle, and the conversion efficiency is high; the defects in the conventional synthetic method for 2-bromofluorene derivatives that the conversion efficiency is low, the reaction is complicated and the reaction efficiency is low are avoided.
Description
Technical field
The present invention relates to the field of chemical synthesis, be specifically related to a kind of synthetic method of 2-bromine fluorene derivatives.
Background technology
Since last century the eighties, electroluminescent organic material (OLED) develops rapidly.OLED technique of display has self luminous characteristic, adopts very thin coating of organic material and glass substrate, when have electric current by time, these organic materialss will be luminous, and OLED display screen curtain visible angle is large, and can save electric energy.2-bromine fluorenes and derivative thereof are as a kind of important organic photoelectrical material intermediate, it is widely used in the synthesis and preparation of the materials such as dyestuff, photoconductive material, luminescence, simultaneously, with 2-bromine fluorenes for raw material, its No. 9 positions are modified, introduce different substituting groups, the material with unique photoelectric properties can be synthesized.
At present, method about synthesis 2-bromine fluorene derivatives mainly contains following several: people's reports such as MunetoshiNakamura in 2013 with fluorenes and N-bromo-succinimide (NBS) for raw material, propylene carbonate is that the 2-bromine fluorenes productive rate of solvent synthesis is only 53% [JournalofPolymerScience, PartA:Polymerchemistry2013,51,4945 – 4956], other productive rates carrying out bromo-reaction with NBS are also general lower.Liu Changchun in 2008 report with fluorenes and benzyl trimethyl tribromide ammonium (BTMATBr
3) be raw material, methylene dichloride and methyl alcohol are solvent, although the 2-bromine fluorenes productive rate of synthesis can reach more than 90% [Liu Changchun. chemistry world, 2008,49 (8): 481 ~ 483], this method is also considered to up to the present synthesize 2-bromine fluorenes the best way.But, BTMATBr
3will be synthesized by benzyltrimethylammonium bromide, step is more, and quaternary ammonium salt consumption is large, with methylene dichloride and methyl alcohol as solvent, causes production cost high.In addition, other carries out, in the method for bromo, having use Br to the derivative of fluorenes
2carry out [Eur.Pat.Appl., 1298117, the 02Apr2003] of bromo, the toxicity of bromine is large, and reacts wayward, and by product is more.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide that a kind of working method is simple, reaction required equipment is simple and the synthetic method of the 2-bromine fluorene derivatives that reaction conditions is gentle, transformation efficiency is high, existing 2-bromine fluorene derivatives transformation efficiency be low to solve, reaction complexity and the low defect of reaction efficiency.
For achieving the above object, the synthetic method of a kind of 2-bromine fluorene derivatives of the present invention, is characterized in that: it comprises following step,
1) get one, two mouthfuls of flasks, in flask, add fluorenes or derivatives thereof, quaternary ammonium salt, sodium bromate, wherein fluorenes or derivatives thereof: quaternary ammonium salt: the mol ratio of sodium bromate is 1:0.05-0.5:0.2-0.4;
2) in flask, load onto thermometer and constant pressure funnel, add methylene dichloride and water in flask, wherein methylene dichloride and water volume ratio are 1:1.5;
3) under atmospheric pressure state, be uniformly mixed, and make dissolution of solid to the liquid in flask, control temperature of reaction system is 0-30 DEG C;
4) drip Hydrogen bromide by constant pressure funnel in the flask in step 3, after dropwising, at room temperature continue to stir 20min-3h, the fluorenes wherein in Hydrogen bromide and step 1 or its
The mol ratio of derivative is 2-4:1; Wherein, its reactive chemistry formula is:
R in formula
1, R
2independently be expressed as-H ,-Me ,-Et ,-Ph ,-PhCH separately
2;
5) reaction solution in step 4 is left standstill, standing liquid is carried out aqueous phase and is separated with organic phase, obtain aqueous phase and organic phase;
6) by the aqueous phase dichloromethane extraction that obtains in step 5 once, extract the organic phase in aqueous phase, then the organic phase obtained in the organic phase obtained and step 4 is merged, and the organic phase after merging is washed three times;
7) the organic phase anhydrous sodium sulphate got in step 6 is carried out drying, filtration, concentrated, and by the product after concentrated, carry out recrystallization by ethanol, vacuum-drying.
On the basis of such scheme preferably, described drying temperature is 60 DEG C.
On the basis of such scheme preferably, in described step 4, churning time is 1h.
Compared with prior art, its beneficial effect is in the present invention: the synthetic method of a kind of 2-bromine fluorene derivatives of the present invention, and its synthetic method is simple to operate, and whole reaction is all carried out in same reactor, be one pot reaction, required equipment is simple, and the reaction times is short, reaction conditions is gentle, raw material availability is high, environmental protection, and the selectivity producing single bromo fluorene derivatives is high, productive rate is high, is easy to industrialization and produces in a large number.
Embodiment
By describe in detail the present invention technology contents, structural attitude, reached object and effect, hereby exemplify embodiment below and be described in detail.
Embodiment 1
1) one, two mouthfuls of flasks that volume is 100ML are got, by adding 5g fluorenes, 0.34g benzyltrimethylammonium bromide, 0.9g sodium bromate in one of them bottleneck of flask;
2) in flask, load onto thermometer and constant pressure funnel, another bottleneck added in flask through flask by constant pressure funnel adds 34.5mL water, 23mL methylene dichloride in flask;
3) under atmospheric pressure state, be uniformly mixed, and make dissolution of solid to the liquid in flask, controlling temperature of reaction system is 30 DEG C;
4) drip by constant pressure funnel the Hydrogen bromide 8.8mL that weight percent is 40% in the flask in step 3, after dropwising, at room temperature continue to stir 2h, wherein, its reactive chemistry formula is:
5) reaction solution in step 4 is left standstill, standing liquid is carried out aqueous phase and is separated with organic phase, obtain aqueous phase and organic phase;
6) by step 5 obtain aqueous phase with dichloromethane extraction once, then will in its and step 4 obtain organic phase merge, and by merging after organic phase wash three times;
7) the organic phase anhydrous sodium sulphate got in step 6 is carried out drying, filtration, concentrated, and by the product after concentrated, carry out recrystallization by ethanol, vacuum-drying.
After drying, the 2-bromine fluorenes productive rate of acquisition is 60%, wherein, and the 2-bromine fluorenes content after dry by high performance liquid chromatography HPLC detecting step 7 in material, its purity 90%, product appearance: white solid powder.
Example 2
1) one, two mouthfuls of flasks that volume is 100ML are got, by adding 5g fluorenes, 4.16g benzyl triethyl ammonium bromide, 1.8g sodium bromate in one of them bottleneck of flask;
2) in flask, load onto thermometer and constant pressure funnel, another bottleneck added in flask through flask by constant pressure funnel adds 34.5mL water, 23mL methylene dichloride in flask;
3) under atmospheric pressure state, be uniformly mixed, and make dissolution of solid to the liquid in flask, controlling temperature of reaction system is 25 DEG C;
4) drip by constant pressure funnel the Hydrogen bromide 17.6mL that weight percent is 40% in the flask in step 3, after dropwising, at room temperature continue to stir 2h, wherein, its reactive chemistry formula is:
5) reaction solution in step 4 is left standstill, standing liquid is carried out aqueous phase and is separated with organic phase, obtain aqueous phase and organic phase;
6) by step 5 obtain aqueous phase with dichloromethane extraction once, then will in its and step 4 obtain organic phase merge, and by merging after organic phase wash three times;
7) the organic phase anhydrous sodium sulphate got in step 6 is carried out drying, filtration, concentrated, and by the product after concentrated, carry out recrystallization by ethanol, at 60 DEG C, carry out vacuum-drying.
After drying, the 2-bromine fluorenes productive rate of acquisition is 65%, wherein, and the 2-bromine fluorenes content after dry by high performance liquid chromatography HPLC detecting step 7 in material, its purity 90%, product appearance: white solid powder.
Example 3
1) one, two mouthfuls of flasks that volume is 100ML are got, by adding 5g9 in one of them bottleneck of flask, 9-dimethyl fluorene, 0.35g benzyl triethyl ammonium bromide, 0.77g sodium bromate;
2) in flask, load onto thermometer and constant pressure funnel, another bottleneck added in flask through flask by constant pressure funnel adds 34.5mL water, 23mL methylene dichloride in flask;
3) under atmospheric pressure state, be uniformly mixed, and make dissolution of solid to the liquid in flask, controlling temperature of reaction system is 10 DEG C;
4) drip by constant pressure funnel the Hydrogen bromide 7.5mL that weight percent is 40% in the flask in step 3, after dropwising, at room temperature continue to stir 1.5h; Wherein, its reactive chemistry formula is:
R in formula
1, R
2independently be expressed as-Me separately;
5) reaction solution in step 4 is left standstill, standing liquid is carried out aqueous phase and is separated with organic phase, obtain aqueous phase and organic phase;
6) by step 5 obtain aqueous phase with dichloromethane extraction once, then will in its and step 4 obtain organic phase merge, and by merging after organic phase wash three times;
7) the organic phase anhydrous sodium sulphate got in step 6 is carried out drying, filtration, concentrated, and by the product after concentrated, carry out recrystallization by ethanol, at 60 DEG C, carry out vacuum-drying.
After drying, 9,9-dimethyl-2-bromine fluorenes productive rates of acquisition are 73%, wherein, and 9,9-dimethyl-2-bromine fluorenes content after dry by high performance liquid chromatography HPLC detecting step 7 in material, its purity 90%, product appearance: white solid powder.
Example 4
1) one, two mouthfuls of flasks that volume is 100ML are got, by adding 5g fluorenes, 2.6g Tetrabutyl amonium bromide, 1.35g sodium bromate in one of them bottleneck of flask;
2) in flask, load onto thermometer and constant pressure funnel, another bottleneck added in flask through flask by constant pressure funnel adds 34.5mL water, 23mL methylene dichloride in flask;
3) under atmospheric pressure state, be uniformly mixed, and make dissolution of solid to the liquid in flask, controlling temperature of reaction system is 0 DEG C;
4) drip by constant pressure funnel the Hydrogen bromide 13.2mL that weight percent is 40% in the flask in step 3, after dropwising, at room temperature continue to stir 1.5h, wherein, its reactive chemistry formula is:
5) reaction solution in step 4 is left standstill, standing liquid is carried out aqueous phase and is separated with organic phase, obtain aqueous phase and organic phase;
6) by step 5 obtain aqueous phase with dichloromethane extraction once, then will in its and step 4 obtain organic phase merge, and by merging after organic phase wash three times;
7) the organic phase anhydrous sodium sulphate got in step 6 is carried out drying, filtration, concentrated, and by the product after concentrated, carry out recrystallization by ethanol, at 60 DEG C, carry out vacuum-drying.
After drying, the 2-bromine fluorenes productive rate of acquisition is 86%, wherein, and the 2-bromine fluorenes content after dry by high performance liquid chromatography HPLC detecting step 7 in material, its purity 94%, product appearance: white solid powder.
Example 5
1) get one, two mouthfuls of flasks that volume is 100ML, by adding 5g fluorenes in one of them bottleneck of flask, 2.8g Tetrabutyl amonium bromide, weight percent be 40% Hydrogen bromide 13mL;
2) in flask, load onto thermometer and constant pressure funnel, another bottleneck added in flask through flask by constant pressure funnel adds 34.5mL water, 23mL methylene dichloride in flask;
3) under atmospheric pressure state, be uniformly mixed, and make dissolution of solid to the liquid in flask, controlling temperature of reaction system is 5 DEG C;
4) add 1.5g sodium bromate in the flask in step 3, at room temperature continue to stir 2h, wherein, its reactive chemistry formula is
5) reaction solution in step 4 is left standstill, standing liquid is carried out aqueous phase and is separated with organic phase, obtain aqueous phase and organic phase;
6) by step 5 obtain aqueous phase with dichloromethane extraction once, then will in its and step 4 obtain organic phase merge, and by merging after organic phase wash three times;
7) the organic phase anhydrous sodium sulphate got in step 6 is carried out drying, filtration, concentrated, and by the product after concentrated, carry out recrystallization by ethanol, vacuum-drying.
After drying, the 2-bromine fluorenes productive rate of acquisition is 79%, wherein, and the 2-bromine fluorenes content after dry by high performance liquid chromatography HPLC detecting step 7 in material, its purity 94%, product appearance: white solid powder.
In sum, be only the preferred embodiment of the present invention, do not limit protection scope of the present invention with this, all equivalence changes done according to the scope of the claims of the present invention and description with modify, be all within scope that patent of the present invention contains.
Claims (3)
1. a synthetic method for 2-bromine fluorene derivatives, is characterized in that: it comprises following step,
1) get one, two mouthfuls of flasks, in flask, add fluorenes or derivatives thereof, quaternary ammonium salt, sodium bromate, wherein fluorenes or derivatives thereof: quaternary ammonium salt: the mol ratio of sodium bromate is 1:0.05-0.5:0.2-0.4;
2) in flask, load onto thermometer and constant pressure funnel, add methylene dichloride and water in flask, wherein methylene dichloride and water volume ratio are 1:1.5;
3) under atmospheric pressure state, be uniformly mixed, and make dissolution of solid to the liquid in flask, control temperature of reaction system is 0-30 DEG C;
4) drip Hydrogen bromide by constant pressure funnel in the flask in step 3, after dropwising, at room temperature continue to stir 20min-3h, the mol ratio of the fluorenes or derivatives thereof wherein in Hydrogen bromide and step 1 is 2-4:1, and wherein, its reactive chemistry formula is:
R in formula
1, R
2independently be expressed as-H ,-Me ,-Et ,-Ph ,-PhCH separately
2;
5) reaction solution in step 4 is left standstill, standing liquid is carried out aqueous phase and is separated with organic phase, obtain aqueous phase and organic phase;
6) by the aqueous phase dichloromethane extraction that obtains in step 5 once, extract the organic phase in aqueous phase, then the organic phase obtained in the organic phase obtained and step 4 is merged, and the organic phase after merging is washed three times;
7) the organic phase anhydrous sodium sulphate got in step 6 is carried out drying, filtration, concentrated, and by the product after concentrated, carry out recrystallization by ethanol, vacuum-drying.
2. the synthetic method of a kind of 2-bromine fluorene derivatives as claimed in claim 1, is characterized in that: described drying temperature is 60 degrees Celsius.
3. the synthetic method of a kind of 2-bromine fluorene derivatives as claimed in claim 1, is characterized in that: in described step 4, churning time is 1h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530262A (en) * | 2018-06-15 | 2018-09-14 | 贾红琴 | A kind of synthetic method of 2- bromines fluorenes |
| CN114890980A (en) * | 2022-05-16 | 2022-08-12 | 内蒙古大学 | Preparation method of ionic type thiafluorene derivative |
-
2015
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Non-Patent Citations (2)
| Title |
|---|
| 李强等: "2-溴芴的合成研究", 《精细化工中间体》 * |
| 肖树秀: "液溴替代物在绿色有机合成中的应用", 《中国优秀硕士学位论文全文数据库(电子期刊)工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530262A (en) * | 2018-06-15 | 2018-09-14 | 贾红琴 | A kind of synthetic method of 2- bromines fluorenes |
| CN114890980A (en) * | 2022-05-16 | 2022-08-12 | 内蒙古大学 | Preparation method of ionic type thiafluorene derivative |
| CN114890980B (en) * | 2022-05-16 | 2024-02-13 | 内蒙古大学 | Process for preparing ionic thiafluorene derivatives |
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