CN114591148A - Method for synthesizing bisphenol fluorene based on microreactor - Google Patents
Method for synthesizing bisphenol fluorene based on microreactor Download PDFInfo
- Publication number
- CN114591148A CN114591148A CN202210358061.XA CN202210358061A CN114591148A CN 114591148 A CN114591148 A CN 114591148A CN 202210358061 A CN202210358061 A CN 202210358061A CN 114591148 A CN114591148 A CN 114591148A
- Authority
- CN
- China
- Prior art keywords
- bisphenol fluorene
- microreactor
- acid
- reaction
- synthesizing
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for synthesizing bisphenol fluorene based on a microreactor, which forms a set of process capable of preparing bisphenol fluorene compounds at kilogram level, and generates bisphenol fluorene by adopting continuous cyclization cascade reaction of fluorenone and phenol; the method comprises the steps of introducing materials of fluorenone derivatives and phenol derivatives into a microreactor in proportion, and synthesizing polysubstituted or polyfunctional bisphenol fluorene aromatic hydrocarbon in the microreactor in one step through a coupling reaction, wherein the process is stable and has no amplification effect.
Description
Technical Field
The invention belongs to the field of fine synthesis, and particularly relates to a method for synthesizing bisphenol fluorene based on a microreactor.
Background
Bisphenol fluorene is a bisphenol compound containing a Cardo ring skeleton structure and is an important monomer or modifier for synthesizing condensation products such as fluorenyl epoxy resin, fluorenyl benzoxazine resin, acrylate resin, polyester resin, polycarbonate, epoxy resin, polyester or polyether and the like. The fluorenyl epoxy resin has excellent comprehensive properties such as humidity resistance, dielectric property, mechanical property, chemical resistance and the like, and has become an important monomer and modifier in the aspects of high-performance matrix resin materials, electronic packaging materials, high-temperature-resistant adhesives, high-temperature-resistant coatings and the like, and the bisphenol fluorene disclosed by the invention is a compound containing the following chemical structural units:
the bisphenol fluorene synthesis method is a one-pot method to prepare bisphenol fluorene so far, and the sulfuric acid method is a traditional bisphenol fluorene production method, and adopts a single kettle to carry out intermittent production, and has the biggest characteristics of simple flow, convenient operation, no phenol recovery, and repeated washing by adopting methanol and water to remove concentrated sulfuric acid and excessive phenol, so that a large amount of phenol-containing waste water and waste acid containing organic matters are generated, serious harm is caused to the environment, the treatment is difficult, and the consumption of phenol and sulfuric acid is increased; the hydrogen chloride method has the defects of complex production process, more equipment, strong corrosion of hydrogen chloride, serious corrosion to the equipment and need of expensive corrosion-resistant materials for the whole device; the sulfydryl sulfonic acid method is a method for preparing bisphenol fluorene by taking sulfydryl sulfonic acid as a catalyst, and the catalyst is expensive and is suitable for small-amount reaction.
Disclosure of Invention
In the research of the synthesis process of the spirofluorene oxaen microreactor, the subject group finds that the yield of bisphenol fluorene aromatic hydrocarbon as an impurity component in the production process of spirofluorene oxaen can be amplified by regulating and controlling the control conditions such as the molar ratio, the temperature and the like of raw materials, and higher yield and purity can be obtained, so that the defects of the preparation method for industrially producing bisphenol fluorene in the prior art are overcome, the invention provides a method for synthesizing bisphenol fluorene based on the microreactor, a process for preparing bisphenol fluorene compounds at kilogram level is formed, and the bisphenol fluorene is generated by adopting the continuous cyclization cascade reaction of fluorenone and phenol; the materials of fluorenone derivatives and phenol derivatives are proportionally introduced into the microreactor, and the polysubstituted or polyfunctional bisphenol fluorene is synthesized in one step in the microreactor through a coupling reaction, and the process is stable and has no amplification effect.
The technical scheme adopted by the invention is as follows:
a method for synthesizing bisphenol fluorene based on a microreactor, as shown in fig. 1, the method comprises the following steps:
the method comprises the following steps: adding a fluorenone derivative and a phenol derivative into an organic solvent to prepare a strand of material, and adding an acid catalyst into the organic solvent to prepare a strand of material;
step two: preheating the two materials respectively, and then introducing the two materials into the microreactor at the flow speed of 10-50 ml/min respectively;
step three: and mixing the two materials in a microreactor to form a reaction mixed solution, reacting the reaction mixed solution for 40-120 minutes at 80-130 ℃, and in the reaction, specifically, synthesizing multi-substituted or multi-functionalized bisphenol fluorene in one step by a cyclization reaction of a fluorenone derivative and a phenol derivative under the catalysis of acid.
Step four: and after the reaction mixed solution reacts for 40-120 minutes until the monitoring substrate of the thin layer chromatography almost disappears, recrystallizing the crude product to obtain the target product bisphenol fluorene aromatic hydrocarbon 3.
Wherein, the structural general formula of the fluorenone derivative in the first step is as follows:
wherein R is1、R2The aromatic hydrocarbon derivatives are the same or different, and specifically are hydrogen, halogen, aromatic hydrocarbon derivatives, condensed ring aromatic hydrocarbons and the like, wherein the aromatic hydrocarbon derivatives are any one of benzene, naphthalene and anthracene; preferably, in the general structural formula of the fluorenone derivative 1, the preferred structure of the fluorenone derivative is one of the following structures:
wherein the range of the phenol derivatives in the step one is phenol, para-substituted phenol, meta-substituted phenol and various substituted 1-naphthol; preferably, the preferred structure of the phenolic derivative is one of the following:
preferably, the solvent in the first step is one or more of 1, 2-dichloroethane, dimethyl sulfoxide, chlorobenzene, 1, 2-dichlorobenzene, nitrobenzene, nitromethane, acetonitrile, trichloromethane, carbon tetrachloride or bromobenzene or dibromobenzene;
preferably, in the first step, the feeding molar ratio of the fluorenone derivative, the phenolic derivative and the acid catalyst is 1: (6-10): (3-6), the concentration of the fluorenone derivative, the phenol derivative and the acid catalyst is not more than 2mol/L, and the micro-reactor is blocked when the concentration is more than 2 mol/L.
Preferably, the acid catalyst is any one or combination of acetic acid, hydrochloric acid, hydrobromic acid, periodic acid, methane sulfonic acid, concentrated sulfuric acid, trifluoromethanesulfonic acid, Eton's reagent or trifluoroacetic acid hydrofluoric acid-antimony pentafluoride.
Preferably, the reaction temperature of the reaction mixed solution in the third step is 90-120 ℃.
Preferably, as shown in fig. 2, the specific steps of recrystallizing the crude product to obtain the target product bisphenol fluorene aromatic hydrocarbon in step four include: mixing the crude product solution with a saturated alkali solution until a white flocculent product appears; filtering the white flocculent product to obtain a crude product; dissolving the crude product in an ethanol solution to obtain an ethanol solution of the crude product; slowly adding the ethanol solution of the crude product into ice water, and continuously stirring to separate out a white product; the white product is filtered and dried to obtain a pure product and the bisphenol fluorene, and the purification mode can improve the purity of the product and reduce the environmental hazard caused by excessive phenol generated in the recrystallization process; distilling under reduced pressure to remove the solvent, and recrystallizing at 20-25 deg.C with saturated alkali solution and ethanol to obtain bisphenol fluorene aromatic hydrocarbon with high purity.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a simple and efficient synthesis method for synthesizing bisphenol fluorene in a micro reaction, which is characterized in that fluorenone derivatives and phenol derivatives are used as reaction substrates, and the bisphenol fluorene with flexible substituent groups or multiple functional groups is synthesized in one step through a cationic relay cascade reaction under the catalysis of a small amount of acid; a series of monomer materials with bisphenol fluorene structural units are synthesized based on a microreactor, and the monomer materials can further synthesize functional polymer materials, so that the materials have wide development potential in the field of comprehensive properties such as dielectric property, mechanical property, chemical resistance and the like.
Compared with the one-pot method of the traditional method, the method for synthesizing bisphenol fluorene based on the microreactor provided by the invention greatly shortens the reaction time from 8 hours to 90 minutes, improves the production efficiency, successfully prepares the bisphenol fluorene products in kilogram level, develops a synthesis process without amplification effect in the whole process, has no difference with the yield obtained by gram level preparation, can realize 82% of yield, and can be directly applied to a ton-level continuous flow reactor for industrial production;
the method for synthesizing bisphenol fluorene based on the microreactor provided by the invention has the advantages of easily available raw materials, simple operation, low cost, high yield and wider substrate range;
the method for synthesizing bisphenol fluorene based on the microreactor, provided by the invention, can be used for quickly and flexibly designing the required molecular building blocks and organic semiconductor precursors according to the selection of specific phenol, is suitable for small-scale synthesis in a laboratory, is easy to realize industrial production, and has a great development prospect.
Drawings
FIG. 1 is a flow chart of a method for synthesizing bisphenol fluorene based on a microreactor according to the invention;
FIG. 2 is a schematic diagram of the recrystallization operation of the crude product according to step four of the present invention;
FIG. 3 is a hydrogen spectrum of the product of example 2;
FIG. 4 is a hydrogen spectrum of the product of example 4;
FIG. 5 is a hydrogen spectrum of the product of example 7.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
The preparation method comprises the following steps of preparing bisphenol fluorene with a structural formula shown as the following formula, namely bisphenol fluorene 3a for short, by using fluorenone and 1-naphthol as raw materials, and providing specific preparation processes under different reaction conditions, namely the preparation processes of the following examples 1-3;
example 1
Dissolving methanesulfonic acid in 2100ml of 1, 2-chlorobenzene to prepare a methanesulfonic acid-1, 2-dichlorobenzene solution as a strand of material; dissolving fluorenone 1a (700.3g, 4.178mol) and phenol 2a (2357,6g, 25.07mol) in 2100ml of 1,2 chlorobenzene solvent to serve as another material, feeding the two materials into a first module and a second module of a microchannel reaction system respectively at a flow rate of 20ml/min to preheat to 80 ℃, then converging in a third reaction module to start reaction, wherein the reaction temperature is 80 ℃, the pressure of the third reaction module is controlled to be 0.3bar by adopting a backpressure valve in the reaction process shown in figure 1, and the backpressure is carried out when the reaction solvent reaches a boiling point, and the reaction time is 80 min. The fluorenone conversion rate is 82 percent, and bisphenol fluorene 3a (1 kg, 74 percent) with higher purity can be obtained by using 1000mL of saturated sodium hydroxide alkali solution and 200mL of ethanol for recrystallization at 20 ℃; the reaction path of this example is as follows:
example 2
1603.03g (16.7mol) of methanesulfonic acid is dissolved in 2100ml of 1, 2-chlorobenzene to prepare a methanesulfonic acid-1, 2-dichlorobenzene solution as a strand of material; dissolving fluorenone 1a (700.3g, 4.178mol) and phenol 2a (2357,6g, 25.07mol) in 2100ml of 1,2 chlorobenzene solvent to serve as another material, and feeding the two materials into a first module and a second module of the microchannel reaction system respectively at a flow rate of 20ml/minPreheating to 90 ℃, then converging in a third reaction module to start reaction, wherein the reaction temperature is 90 ℃, a backpressure valve is adopted in the reaction process to control the pressure of the third reaction module to be 0.3bar, and when the reaction solvent reaches the boiling point, back pressure is carried out for 40 min. The fluorenone conversion rate is 90 percent, and bisphenol fluorene 3a (1 kg, 82 percent) with higher purity can be obtained by using 1000mL of saturated sodium hydroxide alkali solution and 200mL of ethanol for recrystallization at the temperature of 20 ℃.1H NMR(400MHz,CDCl3)δ7.770–7.725(d,2H),7.369–7.324(t,J＝1.2Hz,6H),7.067–7.038(dd,J＝8.1Hz,2.4Hz,4H),6.677–6.638(t,J＝13.2Hz,4H),HRMS:m/z calcd forC25H16O2349.4; 349.4, shown in FIG. 3, is the hydrogen spectrum of bisphenol fluorene 3a obtained in this example; the reaction pathway of this example is as follows:
example 3
1603.03g (16.7mol) of methanesulfonic acid is dissolved in 2100ml of 1, 2-chlorobenzene to prepare a methanesulfonic acid-1, 2-dichlorobenzene solution as a strand of material; dissolving fluorenone 1a (700.3g, 4.178mol) and phenol 2a (2357,6g, 25.07mol) in 2100ml of 1,2 chlorobenzene solvent to serve as another material, feeding the two materials into a first module and a second module of a microchannel reaction system at a flow rate of 20ml/min respectively to preheat to 140 ℃, then merging the two materials in a third reaction module to start reaction, wherein the reaction temperature is 140 ℃, a back pressure valve is adopted in the reaction process shown in figure 1 to control the pressure of the third reaction module to be 0.3bar, back pressure is carried out when the reaction solvent reaches a boiling point, and a pipeline is blocked after the reaction time is 40min, but the preparation result is that the fluorenone is completely converted, which indicates that the excessive preparation temperature can cause. The reaction path of this example is as follows:
the method comprises the following steps of preparing bisphenol fluorene shown in the structural formula shown in the specification, namely bisphenol fluorene 3b for short, by using fluorenone and p-bromophenol as raw materials, and providing specific preparation processes under different reaction conditions, namely the following examples 4-6;
example 4
2296.18g (15.3mol) of trifluoromethanesulfonic acid is dissolved in 2500ml of 1, 2-dichloroethane to prepare trifluoromethanesulfonic acid-1, 2-dichlorobenzene solution as a strand of material; dissolving 2, 7-dibromofluorenone 1a (890.07g,5.1mol) and p-bromophenol 2b (4896g, 30.6mol) in 2500ml of 1, 2-dichlorobenzene solvent to form another material, feeding the two materials into a microchannel reaction system at a flow rate of 40ml/min, feeding the two materials into a first module and a second module of the microchannel reaction system at a flow rate of 20ml/min respectively, preheating to 90 ℃, then converging in a third reaction module to start reaction, controlling the pressure of the third reaction module by using a back pressure valve in the reaction process shown in figure 1, and carrying out back pressure when the reaction solvent reaches a boiling point, wherein the reaction time is 50min, the reaction temperature is 90 ℃, and the fluorenone conversion rate is 60%. Thin layer chromatography monitoring of the starting material reflects essentially complete. The solvent was removed by distillation under reduced pressure, and bisphenol fluorene 3b (1 kg, 35%) with high purity was obtained by recrystallization at 20 ℃ using 1000mL of saturated sodium hydroxide alkali solution and 200mL of ethanol.1H NMR(400MHz,CDCl3)δδ7.770–7.725(d,2H),7.369–7.324(t,J＝1.2Hz,6H),7.25–7.21(m,2H),7.13–7.11(d,J＝7.6Hz,2H),6.92–6.89(dd,J＝8.4Hz,J＝2Hz,2H),6.27–6.25(d,J＝8.4Hz,2H).HRMS:m/z calcd for C25H14Br2O2509.948; 509.946 for found; as shown in fig. 4, is a hydrogen spectrum of the bisphenol fluorene 3b product obtained in this example; the reaction path of this example is as follows:
example 5
2296.18g (15.3mol) of trifluoromethanesulfonic acid was dissolved in 2500ml of 1, 2-dichloroethane to prepare a solutionTrifluoromethanesulfonic acid-1, 2-dichlorobenzene solution as a strand of material; dissolving 2, 7-dibromofluorenone 1a (890.07g,5.1mol) and p-bromophenol 2b (4896g, 30.6mol) in 2500ml of 1, 2-dichlorobenzene solvent to form another material, feeding the two materials into a microchannel reaction system at a flow rate of 40ml/min, feeding the two materials into a first module and a second module of the microchannel reaction system at a flow rate of 20ml/min respectively, preheating to 90 ℃, then converging in a third reaction module to start reaction, controlling the pressure of the third reaction module by using a back pressure valve in the reaction process shown in figure 1, carrying out back pressure when the reaction solvent reaches a boiling point, wherein the reaction time is 100min, the reaction temperature is 90 ℃, and the conversion rate of fluorenone is 40%. The thin layer chromatography monitoring of the starting material did not reflect completion. The solvent was removed by distillation under the reduced pressure, and bisphenol fluorene 3b (400g, 35%) with high purity was obtained by recrystallization at 20 ℃ using 1000mL of saturated sodium hydroxide alkali solution and 200mL of ethanol.1HNMR(400MHz,CDCl3)δδ7.770–7.725(d,2H),7.369–7.324(t,J＝1.2Hz,6H),7.25–7.21(m,2H),7.13–7.11(d,J＝7.6Hz,2H),6.92–6.89(dd,J＝8.4Hz,J＝2Hz,2H),6.27–6.25(d,J＝8.4Hz,2H).HRMS:m/z calcd for C25H14Br2O2509.948; found is 509.946; the reaction path of this example is as follows:
example 6
2296.18g (15.3mol) of trifluoromethanesulfonic acid is dissolved in 2500ml of 1, 2-dichloroethane to prepare trifluoromethanesulfonic acid-1, 2-dichlorobenzene solution as a strand of material; dissolving 2, 7-dibromofluorenone 1a (890.07g,5.1mol) and p-bromophenol 2b (4896g, 30.6mol) in 2500ml of 1, 2-dichlorobenzene solvent to form another material, feeding the two materials into a microchannel reaction system at a flow rate of 40ml/min, feeding the two materials into a first module and a second module of the microchannel reaction system at a flow rate of 20ml/min respectively for preheating to 135 ℃, then converging in a third reaction module for starting reaction, controlling the pressure of the third reaction module by using a back pressure valve in the reaction process shown in figure 1, and carrying out back pressure when the reaction solvent reaches the boiling pointThe reaction time is 40min, the reaction temperature is 135 ℃, and the conversion rate of the fluorenone is 40 percent. Thin layer chromatography monitoring of the starting material was complete. The solvent is removed by reduced pressure distillation to generate tar-like substances, and the tar-like substances are recrystallized by using 1000mL of saturated alkali solution and 200mL of ethanol at 20 ℃ to obtain bisphenol fluorene aromatic hydrocarbon 3b (500g, 35%) with higher purity.1H NMR(400MHz,CDCl3)δδ7.770–7.725(d,2H),7.369–7.324(t,J＝1.2Hz,6H),7.25–7.21(m,2H),7.13–7.11(d,J＝7.6Hz,2H),6.92–6.89(dd,J＝8.4Hz,J＝2Hz,2H),6.27–6.25(d,J＝8.4Hz,2H).HRMS:m/z calcd for C25H14Br2O2509.948; 509.946 for found; the reaction path of this example is as follows:
bisphenol fluorene with the structural formula shown below, hereinafter referred to as bisphenol fluorene 3c, is prepared by using fluorenone and p-bromophenol as raw materials, and specific preparation processes under different reaction conditions are provided, as in example 7 below.
Example 7
956.76g (11.825mol) of hydrobromic acid is dissolved in 2365ml of 1, 2-dimethyl sulfoxide to prepare a hydrobromic acid-dimethyl sulfoxide solution which is used as a strand of material; dissolving 2, 7-dibromofluorenone 1b (1500.08g, 4.73mol) and phenol 2c (2668.86g, 28.38mol) in 2365ml of dimethyl sulfoxide solvent to obtain another stream, feeding the two streams of materials into a microchannel reaction system at a flow rate of 50ml/min, feeding the two streams of materials into a first module and a second module of the microchannel reaction system at a flow rate of 25ml/min respectively, preheating to 120 ℃, then converging in a third reaction module to start reaction, staying for 120min, controlling the pressure of the third reaction module to be 0.5 kg by using a back pressure valve in the reaction process shown in figure 1, and carrying out back pressure when the reaction solvent reaches a boiling point, wherein the conversion rate of the 2, 7-dibromofluorenone is 70%. Distilling under reduced pressure to remove solvent, and using saturated sodium hydroxide alkali solutionRecrystallizing 1000mL of the bisphenol fluorene 3c and 200mL of ethanol at 20 ℃ to obtain the bisphenol fluorene 3c with higher purity (1 kg, 39%).1H NMR(400MHz,CDCl3)δ7.770–7.725(d,2H),7.64–7.62(d,J＝8。4Hz,2H),7.51–7.49(dd,J＝8.4,6.4Hz,2H),7.26(s,2H),7.24–7.24(d,J＝3.64H),6.85–6.81(m,4H),HRMS:m/z calcd for C32H12N2O2Br2509.948; 509.946 for found; as shown in fig. 5, the product is a hydrogen spectrum of bisphenol fluorene 3a obtained in this example;
Claims (10)
1. a method for synthesizing bisphenol fluorene based on a microreactor is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: adding a fluorenone derivative and a phenol derivative into an organic solvent to prepare a strand of material, and adding an acid catalyst into the organic solvent to prepare a strand of material;
step two: preheating the two materials respectively, and then introducing the two materials into the microreactor at the flow speed of 10-50 ml/min respectively;
step three: mixing the two materials in a microreactor to form a reaction mixed solution, reacting the reaction mixed solution for 40-120 minutes at 80-130 ℃, and in the reaction, specifically, synthesizing polysubstituted or polyfunctionalized bisphenol fluorene aromatic hydrocarbon in one step by a cyclization reaction of a fluorenone derivative and a phenol derivative under the catalysis of acid;
step four: after the reaction mixed solution reacts for 40-120 minutes until thin-layer chromatography is carried out, and after the substrate almost disappears, recrystallizing the crude product to obtain a target product bisphenol fluorene aromatic hydrocarbon;
wherein, the general structural formula of the fluorenone derivative in the step one is as follows:
wherein R is1、R2The same or different, specifically is any one of hydrogen, halogen, aromatic hydrocarbon derivatives and fused ring aromatic hydrocarbons, wherein the aromatic hydrocarbon derivatives comprise: benzene, naphthalene and anthracene compounds;
wherein, the phenolic derivative in the first step comprises: phenol, para-substituted phenol, meta-substituted phenol, various substituted 1-naphthols.
2. The method for synthesizing bisphenol fluorene based on microreactor according to claim 1, wherein: the fluorenone derivative is any one of the following structures:
3. the method for synthesizing bisphenol fluorene based on microreactor as claimed in claim 1, wherein: the phenolic derivative is any one of the following structures:
4. the method for synthesizing bisphenol fluorene based on microreactor as claimed in claim 1, wherein: step one, the solvent is one or a combination of more of 1, 2-dichloroethane, dimethyl sulfoxide, chlorobenzene, 1, 2-dichlorobenzene, nitrobenzene, nitromethane, acetonitrile, trichloromethane, carbon tetrachloride or bromobenzene or dibromobenzene.
5. The method for synthesizing bisphenol fluorene based on microreactor as claimed in claim 1, wherein: step one, the feeding molar ratio of the fluorenone derivative, the phenol derivative and the acid catalyst is 1: (6-10): (3-6).
6. The method for synthesizing bisphenol fluorene based on microreactor as claimed in claim 1, wherein: the concentrations of the fluorenone derivative, the phenol derivative and the acid catalyst in the first step are not more than 2 mol/L.
7. The method for synthesizing bisphenol fluorene based on microreactor according to claim 1, wherein: the acid catalyst is any one or combination of acetic acid, hydrochloric acid, hydrobromic acid, periodic acid, methane sulfonic acid, concentrated sulfuric acid, trifluoromethanesulfonic acid, Eton's reagent or trifluoroacetic acid hydrofluoric acid-antimony pentafluoride.
8. The method for synthesizing bisphenol fluorene based on microreactor as claimed in claim 1, wherein: in the third step, the reaction temperature of the reaction mixed liquid is 90-120 ℃.
9. The method for synthesizing bisphenol fluorene based on microreactor as claimed in claim 1, wherein: step four, the recrystallization process of the crude product specifically comprises the following steps: mixing the crude product solution and a saturated alkali solution together until a white flocculent product appears; filtering the white flocculent product to obtain a crude product; dissolving the crude product in an ethanol solution to obtain an ethanol solution of the crude product; slowly adding the ethanol solution of the crude product into ice water, and continuously stirring to separate out a white product; and carrying out suction filtration and drying on the white product to obtain a pure product.
10. The method for synthesizing bisphenol fluorene based on microreactor as claimed in claim 9, wherein: the saturated alkali solution is a saturated sodium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210358061.XA CN114591148A (en) | 2022-04-07 | 2022-04-07 | Method for synthesizing bisphenol fluorene based on microreactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210358061.XA CN114591148A (en) | 2022-04-07 | 2022-04-07 | Method for synthesizing bisphenol fluorene based on microreactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114591148A true CN114591148A (en) | 2022-06-07 |
Family
ID=81812194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210358061.XA Pending CN114591148A (en) | 2022-04-07 | 2022-04-07 | Method for synthesizing bisphenol fluorene based on microreactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114591148A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117384006A (en) * | 2023-12-08 | 2024-01-12 | 寿光市诚信盐业有限公司 | Preparation method of bromobenzene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795970A (en) * | 2012-07-11 | 2012-11-28 | 常州大学 | Clean, environmentally-friendly and economical bisphenol fluorene synthesizing method |
| WO2019243529A1 (en) * | 2018-06-20 | 2019-12-26 | Centre National De La Recherche Scientifique | Polymer electrolyte comprising at least one organic solvent and at least one aromatic ionomer and uses thereof |
| CN113292529A (en) * | 2021-06-22 | 2021-08-24 | 南京邮电大学 | Method for synthesizing spirofluorene xanthene based on microreactor |
| CN113512177A (en) * | 2021-03-30 | 2021-10-19 | 广州万物物联科技有限公司 | Red light polymer and preparation method thereof |
-
2022
- 2022-04-07 CN CN202210358061.XA patent/CN114591148A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795970A (en) * | 2012-07-11 | 2012-11-28 | 常州大学 | Clean, environmentally-friendly and economical bisphenol fluorene synthesizing method |
| WO2019243529A1 (en) * | 2018-06-20 | 2019-12-26 | Centre National De La Recherche Scientifique | Polymer electrolyte comprising at least one organic solvent and at least one aromatic ionomer and uses thereof |
| CN113512177A (en) * | 2021-03-30 | 2021-10-19 | 广州万物物联科技有限公司 | Red light polymer and preparation method thereof |
| CN113292529A (en) * | 2021-06-22 | 2021-08-24 | 南京邮电大学 | Method for synthesizing spirofluorene xanthene based on microreactor |
Non-Patent Citations (1)
| Title |
|---|
| 肖瑞华主编: "《微流体溶剂萃取技术》", 华东理工大学出版社, pages: 314 - 315 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117384006A (en) * | 2023-12-08 | 2024-01-12 | 寿光市诚信盐业有限公司 | Preparation method of bromobenzene |
| CN117384006B (en) * | 2023-12-08 | 2024-04-19 | 寿光市诚信盐业有限公司 | Preparation method of bromobenzene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109894153B (en) | Preparation and application of nitrogen heterocyclic carbene covalent organic framework material supported palladium catalyst | |
| CN111704555B (en) | Method for synthesizing 4-methoxy-2-nitroaniline by adopting continuous flow reactor | |
| CN108047107B (en) | The preparation method of diphenyl disenenide ether compound | |
| CN112142574B (en) | Synthesis method of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene | |
| CN114591148A (en) | Method for synthesizing bisphenol fluorene based on microreactor | |
| CN114380675A (en) | Method for synthesizing aryl phenol by reaction of halogenated aromatic hydrocarbon and phenol compound induced by visible light | |
| CN105924450B (en) | Synthesis method of azafluorene spiro-aromatic hydrocarbon | |
| CN114349674A (en) | Thiourea compound and preparation method thereof | |
| CN111978219B (en) | Method for synthesizing diaryl thioether compound by manganese-oxygen molecular sieve doped with copper catalyst | |
| CN111440207B (en) | Cuprous complex, preparation method thereof and application thereof in synthesis of 3-indolyl thioether | |
| CN109651151B (en) | Polysubstituted phenanthrene derivative and preparation method thereof | |
| CN109503547B (en) | Process for preparing benzodithiolane derivatives | |
| CN113292529A (en) | Method for synthesizing spirofluorene xanthene based on microreactor | |
| CN113443950B (en) | Method for reducing carbonyl into methylene under illumination | |
| CN108276261A (en) | Catalytic molecular oxygen aoxidizes the method for preparing 2- bromine Fluorenones in a kind of water phase | |
| CN105693475A (en) | Technology method for utilizing solid acid H2SO4-SiO2 for catalyzing and preparing bisphenol | |
| CN109761759A (en) | A kind of brominated method of high regioselectivity of phenol compound | |
| CN112679521B (en) | Method for synthesizing mild azaspiro tricyclic framework molecule | |
| CN114516817A (en) | Chemical intermediate and preparation method thereof | |
| CN1986509A (en) | Bisphenol fluorene synthesizing process catalyzed with solid supported heteropolyacid | |
| CN111393338A (en) | Dorphityl-d3Medicine and its preparing method | |
| CN111675591A (en) | Synthetic method of benzophenanthrene compound | |
| CN110452097B (en) | Preparation method of 1-hydroxypyrene | |
| CN110437113B (en) | Synthesis method of 4-benzenesulfonylbenzoic acid | |
| CN111039920B (en) | Chiral tetraphenylethylene and synthesis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |