CN108530262A - A kind of synthetic method of 2- bromines fluorenes - Google Patents
A kind of synthetic method of 2- bromines fluorenes Download PDFInfo
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- CN108530262A CN108530262A CN201810616414.5A CN201810616414A CN108530262A CN 108530262 A CN108530262 A CN 108530262A CN 201810616414 A CN201810616414 A CN 201810616414A CN 108530262 A CN108530262 A CN 108530262A
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- fluorenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic methods of 2 bromine fluorenes, this method is to be heated to reflux 1 1.5h after mixing fluorenes with hydrobromic acid, dibrominated triphenylphosphine and catalyst, it is cooled to 25 35 DEG C later, add C5H6Br2N2O2, stir evenly 3 5h of rear insulation reaction, reaction solution carries out the separation of water phase and organic phase and obtains 2 bromine fluorenes successively through drying, filtering, concentration, recrystallization after organic phase washing after standing.The 2 bromine fluorenes yields and purity of this method synthesis are high, and reaction condition is mild, easy to operate, and the used time is few, can industrialized production, raw material availability is high, environmentally protective.
Description
Technical field
The invention belongs to technical field of organic synthesis, in particular to a kind of synthetic method of 2- bromines fluorenes.
Background technology
Fluorenes is one of separation product of coal tar, widely used, cheap, and derivative is as important fine chemistry
Product raw material can be used for the fields such as medicine, pesticide, dyestuff, plastics and functional high molecule material.2- bromine fluorenes is one of fluorene derivative,
The synthesis that can be used for medicine and OLED material, especially modifies 9 of 2- bromine fluorenes, can be used for synthesizing various with uniqueness
The material of photoelectric property, therefore be of great significance to the research of its synthetic method.
N at present, domestic and foreign literature report 2- bromine fluorenes synthesis mainly using fluorenes as raw material, in the organic solvents such as chloroform with
Bromine reaction obtains 2- bromine fluorenes, but such operation is complicated, and low yield, reactant isolate and purify difficulty, therefore are difficult simultaneous
Care for high-purity and high yield.In order to further increase purity, patent CN106866350A《A kind of preparation side of high-purity 2- bromine fluorenes
Method》It is 2- aminofluorenes and hydrobromic acid to change reaction, prepares 2- bromine fluorenes as raw material, purity is significantly improved.
Invention content
The purpose of the present invention is preparing 2- bromine fluorenes yields and the low deficiency of purity by raw material of fluorenes for existing, one kind is provided
New using fluorenes as the method for Material synthesis 2- bromine fluorenes, this method reaction condition is mild, and obtained 2- bromine fluorenes yield is high, while purity
Reach 99.6% or more.
In order to achieve the object of the present invention, by a large number of experiments research and unremitting effort, following technical solution is finally obtained：
A kind of synthetic method of 2- bromines fluorenes, this method comprises the following steps：Fluorenes and hydrobromic acid, dibrominated triphenylphosphine and catalyst are mixed
It is heated to reflux 1-1.5h after conjunction, is cooled to 25-35 DEG C later, adds C5H6Br2N2O2, stirs evenly rear insulation reaction 3-5h, instead
The separation of water phase and organic phase is carried out after answering liquid to stand to obtain successively through drying, filtering, concentration, recrystallization after organic phase washing
2- bromine fluorenes.
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein the molar ratio of the fluorenes and hydrobromic acid is 1：(1-
1.5), a concentration of 20-48wt% of hydrobromic acid.
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein fluorenes and the molar ratio of dibrominated triphenylphosphine are 1：
(0.3-0.5)。
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein the molar ratio of the C5H6Br2N2O2 and fluorenes is (1.5-
3)：1.
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein the catalyst is benzoyl peroxide, benzoyl peroxide
The molar ratio of formyl and fluorenes is (0.05-0.10)：1.
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein it is 60-70 DEG C to be heated to reflux temperature.
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein in the separation process of water phase and organic phase, by what is obtained
Water phase is extracted 1-2 times with dichloromethane, and the organic phase being obtained by extraction is merged.
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein organic phase are washed 3-4 times.
Preferably, the drying of the synthetic method of 2- bromines fluorenes as described above, wherein organic phase refers to being carried out using anhydrous sodium sulfate
It is dry.
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein carrying out recrystallization processing using alcoholic solvent.
Preferably, the synthetic method of 2- bromines fluorenes as described above, wherein the alcoholic solvent is methanol or ethyl alcohol.
The present invention compared with the existing technology, has the following technical effect that and progressive：
(1) 2- bromines fluorenes yield reaches 87.61-91.35%, and product purity reaches 99.6% or more after recrystallization；
(2) reaction condition of the present invention is mild, easy to operate, and the used time is few, can industrialized production；
(3) raw material availability is high, environmentally protective.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described with reference to embodiment, the following example is only used for
Illustrate the present invention, and should not be regarded as limiting protection scope of the present invention.In addition, particular technique operating procedure is not specified in embodiment
Or condition person, carried out according to technology or condition described in document in the art or according to product description.Examination used
Production firm person is not specified in agent or instrument, and being can be with conventional products that are commercially available
The synthesis of embodiment 12- bromine fluorenes：
Step (1)：The hydrogen of 30g fluorenes (0.18mol), 36.42g mass fractions 40wt% are added in 500ml three-necked flasks
Bromic acid, 22.8g dibrominateds triphenylphosphine, 2.18g benzoyl peroxides stir, are heated to 60 DEG C of back flow reaction 1h；
Step (2)：After step (1), three-necked flask is cooled to 30 DEG C, 77.2g C5H6Br2N2O2s are added, stir evenly
Insulation reaction 3h afterwards；
Step (3)：Step (2) is cooled to room temperature after reaction, and reaction solution is stood, and will be stood liquid and is carried out water phase and have
Machine is separated, and obtains water phase and organic phase, is extracted 2 times to water phase dichloromethane, adds after the organic phase being obtained by extraction is merged
Enter in the organic phase obtained to standing separation, is dried, filtered, concentrated with anhydrous sodium sulfate after being washed 3 times to organic phase, it will
Product after concentration is recrystallized by ethyl alcohol, and is dried in vacuo, and white plates 2- bromine fluorenes is obtained.
The 2- bromine fluorenes yields obtained after drying are 87.61%, gas chromatographic purity 99.70%.Carry out nuclear magnetic resonance (inspection
Survey condition：400MHz, DMSO-d6) exist without 2,7- dibromo fluorenes impurity peaks in product.
The synthesis of embodiment 22- bromine fluorenes：
Step (1)：The hydrogen bromine of 30g fluorenes (0.18mol), 42.5g mass fractions 40wt% are added in 500ml three-necked flasks
Acid, 32g dibrominateds triphenylphosphine, 3.10g benzoyl peroxides, stir, are heated to 65 DEG C of back flow reaction 1.5h；
Step (2)：After step (1), three-necked flask is cooled to 25 DEG C, 125.0g C5H6Br2N2O2s are added, stirring is equal
Insulation reaction 4h after even；
Step (3)：Step (2) is cooled to room temperature after reaction, and reaction solution is stood, and will be stood liquid and is carried out water phase and have
Machine is separated, and obtains water phase and organic phase, is extracted 2 times to water phase dichloromethane, adds after the organic phase being obtained by extraction is merged
Enter in the organic phase obtained to standing separation, is dried, filtered, concentrated with anhydrous sodium sulfate after being washed 3 times to organic phase, it will
Product after concentration is recrystallized by ethyl alcohol, and is dried in vacuo, and white plates 2- bromine fluorenes is obtained.
The 2- bromine fluorenes yields obtained after drying are 91.35%, gas chromatographic purity 99.65%.Carry out nuclear magnetic resonance (inspection
Survey condition：400MHz, DMSO-d6) exist without 2,7- dibromo fluorenes impurity peaks in product.
The synthesis of embodiment 32- bromine fluorenes：
Step (1)：The hydrogen bromine of 30g fluorenes (0.18mol), 46.4g mass fractions 47wt% are added in 500ml three-necked flasks
Acid, 37.98g dibrominateds triphenylphosphine, 4.36g benzoyl peroxides, stir, are heated to 70 DEG C of back flow reaction 1h；
Step (2)：After step (1), three-necked flask is cooled to 35 DEG C, 154.3g C5H6Br2N2O2s are added, stirring is equal
Insulation reaction 5h after even；
Step (3)：Step (2) is cooled to room temperature after reaction, and reaction solution is stood, and will be stood liquid and is carried out water phase and have
Machine is separated, and obtains water phase and organic phase, is extracted 2 times to water phase dichloromethane, adds after the organic phase being obtained by extraction is merged
Enter in the organic phase obtained to standing separation, is dried, filtered, concentrated with anhydrous sodium sulfate after being washed 4 times to organic phase, it will
Product after concentration is recrystallized by ethyl alcohol, and is dried in vacuo, and white plates 2- bromine fluorenes is obtained.
The 2- bromine fluorenes yields obtained after drying are 89.27%, gas chromatographic purity 99.60%.Carry out nuclear magnetic resonance (inspection
Survey condition：400MHz, DMSO-d6) exist without 2,7- dibromo fluorenes impurity peaks in product.
Comparative example 1 (no dibrominated triphenylphosphine)
On the basis of embodiment 1, other processes and parameter constant, difference is in is added without dibrominated three in step (1)
Phenylphosphine, while being added and bromine mole in dibrominated triphenylphosphine on the basis of 77.2g C5H6Br2N2O2s are added in step (2)
Equal C5H6Br2N2O2, finally obtained products collection efficiency are only 54.6%, and product carries out nuclear magnetic resonance (testing conditions：
400MHz, DMSO-d6) there are 2,7- dibromo fluorenes impurity peaks.
Comparative example 2 (no C5H6Br2N2O2)
On the basis of embodiment 1, without step (2) in building-up process, 36.42g mass fractions are added in step (1)
On the basis of the hydrobromic acid of 40wt%, the hydrogen bromine of the 40wt% equal with bromine molal quantity in C5H6Br2N2O2 in step (2) is added
Acid, and it is 4h to extend return time, and finally obtained products collection efficiency is 36.4%, detects product, finds wherein to exist not anti-
The fluorenes answered.
Comparative example 3 (replaces benzoyl peroxide with cuprous oxide)
On the basis of embodiment 1, the cuprous oxide of benzoyl peroxide equivalent is replaced, while anti-in step (3)
Filter processing is first passed through before answering liquid to stand removes cuprous oxide.
Finally obtained products collection efficiency is 76.3%, gas chromatographic purity 99.4%.
Claims (10)
1. a kind of synthetic method of 2- bromines fluorenes, which is characterized in that this method includes：By fluorenes and hydrobromic acid, dibrominated triphenylphosphine
It is heated to reflux 1-1.5h after being mixed with catalyst, 25-35 DEG C is cooled to later, adds C5H6Br2N2O2, kept the temperature after stirring evenly
React 3-5h, reaction solution stand after carry out water phase and organic phase separation, organic phase washing after successively through drying, filtering, concentration,
Recrystallization, obtains 2- bromine fluorenes.
2. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that the molar ratio of the fluorenes and hydrobromic acid is 1：
(1-1.5), a concentration of 20-50wt% of hydrobromic acid.
3. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that the molar ratio of fluorenes and dibrominated triphenylphosphine
It is 1：(0.3-0.5).
4. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that the molar ratio of the C5H6Br2N2O2 and fluorenes is
(1.5-3)：1.
5. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that the catalyst is benzoyl peroxide,
The molar ratio of benzoyl peroxide and fluorenes is (0.05-0.10)：1.
6. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that it is 60-70 DEG C to be heated to reflux temperature.
7. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that in the separation process of water phase and organic phase,
Obtained water phase dichloromethane is extracted 1-2 times, the organic phase being obtained by extraction is merged.
8. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that organic phase is washed 3-4 times.
9. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that organic phase drying refers to using anhydrous slufuric acid
Sodium is dried.
10. the synthetic method of 2- bromines fluorenes according to claim 1, which is characterized in that carry out recrystallization processing using alcoholic solvent.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284796B1 (en) * | 1998-08-06 | 2001-09-04 | Abbott Laboratories | Ukokinase inhibitors |
| US6555682B1 (en) * | 2002-06-13 | 2003-04-29 | The United States Of America As Represented By The Secretary Of The Air Force | Two-photon responsive chromophores containing electron accepting cores |
| WO2004022539A1 (en) * | 2002-09-09 | 2004-03-18 | Astrazeneca Ab | Naphthyl ether compounds and their use |
| US6730793B1 (en) * | 2002-06-13 | 2004-05-04 | The United States Of America As Represented By The Secretary Of The Air Force | Two-photon responsive chromophores containing electron accepting core units |
| WO2004099192A2 (en) * | 2003-04-30 | 2004-11-18 | The Institutes Of Pharmaceutical Discovery, Llc | Heterocycle substituted carboxylic acids as inhibitors of protein tyrosine phosphatase-1b |
| CN101481292A (en) * | 2009-02-25 | 2009-07-15 | 濮阳惠成化工有限公司 | Preparation of 2-bromofluorenone |
| CN104211677A (en) * | 2013-05-30 | 2014-12-17 | 浙江九洲药业股份有限公司 | Preparation method of anti hepatitis C drug intermediate |
| CN104387222A (en) * | 2014-09-29 | 2015-03-04 | 山东大学 | Highly condensed ring [6]helicene compounds based on fluorene and naphthalene and synthetic method thereof |
| CN105198697A (en) * | 2015-06-02 | 2015-12-30 | 湖北和昌新材料科技股份有限公司 | Synthetic method for 2-bromofluorene derivatives |
| CN106866350A (en) * | 2017-04-01 | 2017-06-20 | 河北美星化工有限公司 | A kind of preparation method of the bromine fluorenes of high-purity 2 |
| CN107043452A (en) * | 2017-03-23 | 2017-08-15 | 华南理工大学 | A kind of conjugated polymer based on diaryl-amine group and preparation method and application |
| CN107879908A (en) * | 2017-11-14 | 2018-04-06 | 安徽诺全药业有限公司 | A kind of Lei Dipawei key intermediates and preparation method thereof |
| CN107954990A (en) * | 2017-11-14 | 2018-04-24 | 安徽诺全药业有限公司 | A kind of preparation method of Lei Dipawei |
-
2018
- 2018-06-15 CN CN201810616414.5A patent/CN108530262A/en not_active Withdrawn
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6284796B1 (en) * | 1998-08-06 | 2001-09-04 | Abbott Laboratories | Ukokinase inhibitors |
| US6555682B1 (en) * | 2002-06-13 | 2003-04-29 | The United States Of America As Represented By The Secretary Of The Air Force | Two-photon responsive chromophores containing electron accepting cores |
| US6730793B1 (en) * | 2002-06-13 | 2004-05-04 | The United States Of America As Represented By The Secretary Of The Air Force | Two-photon responsive chromophores containing electron accepting core units |
| WO2004022539A1 (en) * | 2002-09-09 | 2004-03-18 | Astrazeneca Ab | Naphthyl ether compounds and their use |
| WO2004099192A2 (en) * | 2003-04-30 | 2004-11-18 | The Institutes Of Pharmaceutical Discovery, Llc | Heterocycle substituted carboxylic acids as inhibitors of protein tyrosine phosphatase-1b |
| CN101481292A (en) * | 2009-02-25 | 2009-07-15 | 濮阳惠成化工有限公司 | Preparation of 2-bromofluorenone |
| CN104211677A (en) * | 2013-05-30 | 2014-12-17 | 浙江九洲药业股份有限公司 | Preparation method of anti hepatitis C drug intermediate |
| CN104387222A (en) * | 2014-09-29 | 2015-03-04 | 山东大学 | Highly condensed ring [6]helicene compounds based on fluorene and naphthalene and synthetic method thereof |
| CN105198697A (en) * | 2015-06-02 | 2015-12-30 | 湖北和昌新材料科技股份有限公司 | Synthetic method for 2-bromofluorene derivatives |
| CN107043452A (en) * | 2017-03-23 | 2017-08-15 | 华南理工大学 | A kind of conjugated polymer based on diaryl-amine group and preparation method and application |
| CN106866350A (en) * | 2017-04-01 | 2017-06-20 | 河北美星化工有限公司 | A kind of preparation method of the bromine fluorenes of high-purity 2 |
| CN107879908A (en) * | 2017-11-14 | 2018-04-06 | 安徽诺全药业有限公司 | A kind of Lei Dipawei key intermediates and preparation method thereof |
| CN107954990A (en) * | 2017-11-14 | 2018-04-24 | 安徽诺全药业有限公司 | A kind of preparation method of Lei Dipawei |
Non-Patent Citations (14)
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