CN114804994A - Method for preparing substituted aryl fluorene and derivatives thereof - Google Patents
Method for preparing substituted aryl fluorene and derivatives thereof Download PDFInfo
- Publication number
- CN114804994A CN114804994A CN202111281543.1A CN202111281543A CN114804994A CN 114804994 A CN114804994 A CN 114804994A CN 202111281543 A CN202111281543 A CN 202111281543A CN 114804994 A CN114804994 A CN 114804994A
- Authority
- CN
- China
- Prior art keywords
- substituted
- hour
- arylfluorenes
- hydrochloric acid
- preparation
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing substituted aryl fluorene and derivatives thereof, which comprises the steps of firstly adding tetrahydrofuran and 2-bromobiphenyl into a reactor, then stirring for 1 hour at-70 ℃, then adding sec-butyl lithium, then adding substituted aryl ketone, quenching and filtering with diluted hydrochloric acid to obtain a solid, washing with petroleum ether to obtain a high-purity intermediate S1, adding the intermediate S1, glacial acetic acid and diluted hydrochloric acid into the reactor, reacting for 4 hours at 80 ℃, cooling, and filtering to obtain a high-purity product. The invention has the advantages that: simple reaction, easy operation, high yield, simple post-treatment and less waste water.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for preparing substituted aryl fluorene and derivatives thereof.
Background
Due to the special structure of fluorene and its derivatives, they have various applications, such as synthetic drugs, organic electro-luminescent materials, polymer materials, organic flexible materials, etc., and different active groups are introduced into the 9-position of the mechanism, so that they have different applications and better performance in different fields.
Disclosure of Invention
The technical problem to be solved by the invention is to solve the problems and provide a method for preparing substituted aryl fluorene and derivatives thereof, which has the advantages of simple reaction, easy operation, high yield, simple post-treatment, less waste water and environmental protection.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a method for preparing substituted aryl fluorene and its derivative with general structural formula
a1, sequentially adding dry tetrahydrofuran and 2-bromobiphenyl into a first reactor, cooling to-70 ℃, dropwise adding sec-butyl lithium, reacting for 0.5 hour, adding substituted aryl ketone, reacting for 1 hour, heating to-40 ℃, adding diluted hydrochloric acid for quenching, and boiling with petroleum ether to obtain a high-purity intermediate S1;
a2, adding the intermediate S1, glacial acetic acid and hydrochloric acid into a second reactor, reacting for 4 hours at 80 ℃, cooling, and performing suction filtration to obtain a high-purity product, namely substituted aryl fluorene and a derivative thereof;
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are respectively and independently hydrogen, alkyl, halogen, cyano, nitro and carboxyl, wherein the alkyl is C1-C40.
Further, the alkyl is C1-C5.
Further, the solvent is one of diethyl ether, 2-methyltetrahydrofuran and tetrahydrofuran.
Further, the solvent is tetrahydrofuran, and its equivalent is 10 equivalents.
Further, the reaction temperature in the step A1 was-70 ℃.
Further, dilute hydrochloric acid is added in the step A1 for quenching, then, suction filtration is carried out, fixation is obtained, and the solid is boiled and washed by petroleum ether.
Further, the solvent selected in the step a2 is one of glacial acetic acid, N-dimethylformamide and ethanol.
Further, the dehydrating agent selected in the step (2) is one of hydrochloric acid, polyphosphoric acid, sodium phosphite and sulfuric acid.
Further, the structure mainly comprises the following structures:
after adopting the structure, the invention has the following advantages: the reaction is simple and easy to operate, the yield is high, the post-treatment is simple, the waste water is less, the purity is high, the yield is good, and more efficient organic electronic and luminescent materials are obtained.
Detailed Description
The present invention is described in further detail below.
The preparation method of the substituted aryl fluorene and the derivative thereof comprises the following synthetic routes:
the method comprises the following steps:
a1, sequentially adding dry tetrahydrofuran and 2-bromobiphenyl into a first reactor, cooling to-70 ℃, dropwise adding sec-butyl lithium, reacting for 0.5 hour, adding substituted aryl ketone, reacting for 1 hour, heating to-40 ℃, adding diluted hydrochloric acid for quenching, and boiling with petroleum ether to obtain a high-purity intermediate S1.
And A2, adding S1, glacial acetic acid and hydrochloric acid into the second reactor, reacting for 4 hours at 80 ℃, cooling, and performing suction filtration to obtain high-purity products of the substituted aryl fluorene and the derivatives thereof.
The preparation method of the invention can adopt the conventional available means in the field to meet the requirement of realizing the reaction process, and the reaction conditions of each step, such as reaction temperature, solvent selection, product separation and the like, can be prepared.
In order to further improve the quality of the preparation route and better achieve the aim of the invention, the invention optimizes the specific conditions of the preparation method as follows:
the solvent used in step A1 is one of diethyl ether, 2-methyl tetrahydrofuran and tetrahydrofuran, preferably tetrahydrofuran, and its equivalent is 10 equivalents.
The reaction temperature selected in step A1 was-70 ℃.
The sec-butyl lithium selected in the step A1 is a lithium reagent, such as n-butyl lithium, sec-butyl lithium, 6-methylsilylaminolithium, diisopropylaminolithium, preferably sec-butyl lithium, and its equivalent is 1.5.
The treatment method in the step A1 comprises the steps of quenching with dilute hydrochloric acid, then cooling, carrying out suction filtration, and finally boiling and washing with petroleum ether.
The solvent used in step A2 is one of glacial acetic acid, N-dimethylformamide and ethanol, and the phosphoric acid is preferably glacial acetic acid with 8 equivalents.
The dehydrating agent selected in the step A2 is one of hydrochloric acid, polyphosphoric acid, sodium phosphite and sulfuric acid, and hydrochloric acid is preferred.
When the invention is implemented, the invention comprises two steps:
b1, adding dry tetrahydrofuran into the reactor, then adding 2-bromobiphenyl, cooling to-70 ℃, dropwise adding sec-butyl lithium, reacting for 0.5 hour, then adding substituted aryl ketone, reacting for 1 hour, heating to-40 ℃, then adding diluted hydrochloric acid for quenching, carrying out suction filtration, and boiling and washing with petroleum ether to obtain the high-purity intermediate S1.
B2, adding S1, glacial acetic acid and hydrochloric acid into the reactor, reacting for 4 hours at 80 ℃, then cooling, and carrying out suction filtration to obtain high-purity products of the substituted aryl fluorene and the derivatives thereof.
The structure mainly comprises the following structures:
the following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The basic raw materials used in the invention are all conventional commercial products.
The first embodiment is as follows:
c1.1, introducing nitrogen, adding 400ml of dry tetrahydrofuran into a 1L glass three-neck flask, then adding 40g of 2-bromobenzene, cooling to-70 ℃, slowly dropwise adding 196ml of sec-butyl lithium, preserving heat for one hour, then adding 31g of benzophenone, and reacting for 1 hour;
c1.2, post-treatment: heating to-40 ℃, adding 200ml of dilute hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, then performing suction filtration, and washing the solid with 1L of petroleum ether to obtain an intermediate L1 with the HPLC content of 99%, wherein the mass of the intermediate is 49.69g, and the yield is 87%;
c2.1, adding 49.69g/L1, 400ml of glacial acetic acid and 100ml of hydrochloric acid into a 1L glass kettle, heating to 130 ℃ and reacting for 1 hour;
c2.2, post-treatment: the temperature is reduced to 30 ℃, a suction filter funnel is used for suction filtration under the condition of negative pressure to obtain a crude product, then 100g of sodium carbonate aqueous solution is used for washing once, and then 200ml of n-hexane is used for washing once to obtain the product 43.27g of HPLC (high performance liquid chromatography) ═ 99.04%, and the yield is 92%.
Example two:
d1.1, adding 400ml of dry tetrahydrofuran into a 1L glass three-neck flask under the condition of introducing nitrogen, then adding 40g of 2-bromobenzene, cooling to-70 ℃, slowly dropwise adding 102ml of n-butyl lithium, preserving heat for one hour, then adding 36g of bis (3-methylphenyl) ketone, and reacting for 1 hour;
d1.2, post-treatment: heating to-40 ℃, adding 200ml of diluted hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, then performing suction filtration, and washing the solid with 1L of petroleum ether to obtain an intermediate L2 with the content of 99% by HPLC, wherein the mass of the intermediate is 47.65g, and the yield is 77%;
d2.1, adding 47.65g/L2, 400ml glacial acetic acid and 100ml hydrochloric acid into a 1L glass kettle, heating to 130 ℃ and reacting for 1 hour;
d2.2, post-treatment: the temperature was reduced to 30 ℃, and the crude product was filtered through a suction filter funnel under negative pressure to give a crude product, which was washed once with 100g of an aqueous sodium carbonate solution and once with 200ml of n-hexane to give 41.45g of HPLC 99.00% yield 87%.
Example three:
e1.1, adding 400ml of dry tetrahydrofuran into a 1L glass three-neck flask under the condition of introducing nitrogen, then adding 40g of 2-bromobiphenyl, cooling to-70 ℃, slowly dropwise adding 102ml of n-butyl lithium, preserving heat for one hour, then adding 33g of 4-methylbenzophenone, and reacting for 1 hour;
e1.2, post-treatment: heating to-40 ℃, adding 200ml of diluted hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, then performing suction filtration, and washing the solid with 1L of petroleum ether to obtain an intermediate L3 with the content of 99% by HPLC, wherein the yield is 79% when the mass is 47.01 g;
e2.1, adding 47.01g/L3, 400ml of glacial acetic acid and 100ml of hydrochloric acid into a 1L glass kettle, heating to 140 ℃ and reacting for 1 hour;
e2.2, post-treatment: the temperature was reduced to 30 ℃, and the crude product was obtained by suction filtration with a suction filtration funnel under negative pressure, washed once with 100g of an aqueous sodium carbonate solution and once with 200ml of n-hexane to obtain 36.12g of HPLC 99.01%, yield 81%.
Example four:
f1.1, introducing nitrogen, adding 400ml of dry diethyl ether into a 1L glass three-neck flask, then adding 40g of 2-bromobiphenyl, cooling to-70 ℃, slowly dropwise adding 102ml of lithium diisopropylamide, preserving heat for one hour, then adding 45g of bis (4-isopropylphenyl) ketone, and reacting for 1 hour;
f1.1, post-treatment: heating to-40 ℃, adding 200ml of diluted hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, carrying out suction filtration, washing a solid with 1L of petroleum ether to obtain an intermediate L4 with the content of 99% by HPLC, wherein the yield is 48% when the mass is 34.27 g;
f2.1, adding 34.27g/L4, 400ml of glacial acetic acid and 100ml of hydrochloric acid into a 1L glass kettle, heating to 130 ℃ and reacting for 1 hour;
f1.2, post-treatment: the temperature was reduced to 30 ℃, and the crude product was obtained by suction filtration with a suction filtration funnel under negative pressure, washed once with 100g of an aqueous sodium carbonate solution and then once with 200ml of n-hexane to obtain 24.93g of HPLC 99.00% with a yield of 76%.
Example five:
g1.1, adding 400ml of dry 2-methyltetrahydrofuran into a 1L glass three-neck flask under the condition of introducing nitrogen, then adding 40G of 2-bromobiphenyl, cooling to-70 ℃, slowly dropwise adding 196ml of sec-butyl lithium, preserving heat for one hour, then adding 42.67G of bis (4-chlorophenyl) ketone, and reacting for 1 hour;
g1.2, post-treatment: heating to-40 ℃, adding 200ml of diluted hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, then performing suction filtration, and washing the solid with 1L of petroleum ether to obtain an intermediate L5 with the content of 99% by HPLC, wherein the yield is 78% when the mass is 53.70 g;
g2.1, adding 53.70G/L5, 400ml of absolute ethyl alcohol and 100ml of hydrochloric acid into a 1L glass kettle, heating to 130 ℃ and reacting for 1 hour;
g2.2, post-treatment: the temperature was reduced to 30 ℃, and the crude product was obtained by suction filtration with a suction filtration funnel under negative pressure, washed once with 100g of an aqueous sodium carbonate solution and once with 200ml of n-hexane to obtain 32.84g of HPLC 99.00% yield 64%.
Example six:
h1.1, adding 400ml of dry 2-methyltetrahydrofuran into a 1L glass three-neck flask under the condition of introducing nitrogen, then adding 40g of 2-bromobiphenyl, cooling to-70 ℃, slowly dropwise adding 102ml of n-butyl lithium, preserving heat for one hour, then adding 44.37g of 4-bromobenzophenone, and reacting for 1 hour;
h1.1, post-treatment: heating to-40 ℃, adding 200ml of diluted hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, then performing suction filtration, and washing the solid with 1L of petroleum ether to obtain an intermediate L6 with the content of 99% by HPLC, wherein the mass is 47.97g, and the yield is 68%;
h2.1, adding 47.97g/L6, 400ml N, N-dimethylformamide and 100 ml/sodium phosphite into a 1L glass kettle, heating to 120 ℃ and reacting for 1 hour;
h2.2, post-treatment: the temperature was reduced to 30 ℃, and the crude product was obtained by suction filtration with a suction filtration funnel under negative pressure, washed once with 100g of an aqueous sodium carbonate solution and once with 200ml of n-hexane to obtain 25.24g of HPLC 99.00% with a yield of 55%.
Example seven:
i1.1, adding 400ml of dry tetrahydrofuran into a 1L glass three-neck flask under the condition of introducing nitrogen, then adding 40g of 2-bromobiphenyl, cooling to-70 ℃, slowly dropwise adding 196ml of sec-butyl lithium, preserving heat for one hour, then adding 44.37g of 2-bromobenzophenone, and reacting for 1 hour;
i1.2, post-treatment: heating to-40 ℃, adding 200ml of diluted hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, carrying out suction filtration, washing a solid with 1L of petroleum ether to obtain an intermediate L7 with the content of 99% by HPLC, wherein the yield is 91% when the mass is 64.20 g;
i2.1, adding 64.20g/L7, 400ml phosphoric acid and 50ml polyphosphoric acid into a 1L glass kettle, heating to 130 ℃ and reacting for 1 hour;
i2.2, post-treatment: the temperature was reduced to 30 ℃, and the crude product was obtained by suction filtration with a suction filtration funnel under negative pressure, washed once with 100g of an aqueous sodium carbonate solution and then once with 200ml of n-hexane to obtain 43.61g of HPLC 99.00%, yield 71%.
Example eight:
j1.1, adding 400ml of dry tetrahydrofuran into a 1L glass three-neck flask under the condition of introducing nitrogen, then adding 40g of 2-bromobiphenyl, cooling to-70 ℃, slowly dropwise adding 196ml of sec-butyl lithium, preserving heat for one hour, then adding 50.32g of 3-chloro-4-bromobenzophenone, and reacting for 1 hour;
j1.2, post-treatment: heating to-40 ℃, adding 200ml of diluted hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, carrying out suction filtration, washing a solid with 1L of petroleum ether to obtain an intermediate L8 with the content of 99% by HPLC, wherein the yield is 72% when the mass is 55.08 g;
j2.1, adding 55.08g/L8, 400ml of glacial acetic acid and 50ml of sulfuric acid into a 1L glass kettle, heating to 110 ℃ and reacting for 1 hour;
j2.2, post-treatment: the temperature was reduced to 30 ℃, and the crude product was obtained by suction filtration with a suction filtration funnel under negative pressure, washed once with 100g of an aqueous sodium carbonate solution and once with 200ml of n-hexane to obtain 32.25g of HPLC 99.00% with a yield of 61%.
Example nine:
k1.1, adding 400ml of dry 2-methyltetrahydrofuran into a 1L glass three-neck flask under the condition of introducing nitrogen, then adding 40g of 2-bromobiphenyl, cooling to-70 ℃, slowly dropwise adding 196ml of sec-butyl lithium, preserving heat for one hour, then adding 33.49g of 4-aminobenzophenone, and reacting for 1 hour;
k1.2 aftertreatment: heating to-40 ℃, adding 200ml of diluted hydrochloric acid with the concentration of 1mol/L for quenching, stirring for one hour, carrying out suction filtration, washing a solid with 1L of petroleum ether to obtain an intermediate L9 with the content of 99 percent of HPLC, wherein the mass is 33.99g, and the yield is 62 percent;
k2.1 adding 33.99g/L9, 400ml glacial acetic acid and 200ml hydrochloric acid into a 1L glass kettle, heating to 130 ℃ and reacting for 1 hour;
k2.2 aftertreatment: the temperature was reduced to 30 ℃, and the crude product was obtained by suction filtration with a suction filtration funnel under negative pressure, washed once with 300g of an aqueous sodium carbonate solution and then once with 200ml of n-hexane to obtain 21.41g of a product with an HPLC of 99.00% yield of 61%.
Example ten:
l1.1, introducing nitrogen, adding 400ml of dry tetrahydrofuran into a 1L glass three-neck flask, then adding 40g of 2-bromobiphenyl, cooling to-70 ℃, slowly dropwise adding 196ml of sec-butyl lithium, preserving heat for one hour, then adding 38.59g of 3-nitrobenzophenone, and reacting for 1 hour;
l1.2, post-treatment: heating to-40 deg.C, adding 200ml of 1mol/L diluted hydrochloric acid, quenching, stirring for one hour, filtering, washing the solid with 1L petroleum ether to obtain intermediate L10 with HPLC content of 99%, with mass of 38.21g and yield of 59%
L2.1, adding 38.21g/L10, 400ml glacial acetic acid and 100ml hydrochloric acid into a 1L glass kettle, heating to 130 ℃ and reacting for 1 hour;
l2.2, post-treatment: the temperature was reduced to 30 ℃, and the crude product was obtained by suction filtration with a suction filtration funnel under negative pressure, washed once with 100g of an aqueous sodium carbonate solution and once with 200ml of n-hexane to obtain 28.03g of HPLC ═ 99.00% yield of 77%.
The present invention and its embodiments have been described above, but the description is not limited thereto, and the actual structure is not limited thereto. It should be understood that those skilled in the art should understand that they can easily make various changes, substitutions and alterations herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A method for preparing substituted aryl fluorene and its derivatives is characterized in that: the general structure is
a1, sequentially adding dry tetrahydrofuran and 2-bromobiphenyl into a first reactor, cooling to-70 ℃, dropwise adding sec-butyl lithium, reacting for 0.5 hour, adding substituted aryl ketone, reacting for 1 hour, heating to-40 ℃, adding diluted hydrochloric acid for quenching, and boiling with petroleum ether to obtain a high-purity intermediate S1;
a2, adding the intermediate S1, glacial acetic acid and hydrochloric acid into a second reactor, reacting for 4 hours at 80 ℃, cooling, and performing suction filtration to obtain a high-purity product, namely substituted aryl fluorene and a derivative thereof;
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are respectively and independently hydrogen, alkyl, halogen, cyano, nitro and carboxyl, wherein the alkyl is C1-C40.
2. A process for the preparation of substituted arylfluorenes and their derivatives according to claim 1, characterized in that: the alkyl is C1-C5.
3. A process for the preparation of substituted arylfluorenes and their derivatives according to claim 1, characterized in that: the solvent is one of diethyl ether, 2-methyltetrahydrofuran and tetrahydrofuran.
4. A process for the preparation of substituted arylfluorenes and their derivatives according to claim 3, characterized in that: the solvent is tetrahydrofuran, which has an equivalent of 10.
5. A process for the preparation of substituted arylfluorenes and their derivatives according to claim 1, characterized in that: the reaction temperature in step A1 was-70 ℃.
6. A process for the preparation of substituted arylfluorenes and their derivatives according to claim 1, characterized in that: and D, adding dilute hydrochloric acid to quench in the step A1, then carrying out suction filtration to obtain a fixed solid, and boiling and washing the solid with petroleum ether.
7. A process for the preparation of substituted arylfluorenes and their derivatives according to claim 1, characterized in that: the solvent selected in the step A2 is one of glacial acetic acid, N-dimethylformamide and ethanol.
8. A process for the preparation of substituted arylfluorenes and their derivatives according to claim 1, characterized in that: the dehydrating agent selected in the step (2) is one of hydrochloric acid, polyphosphoric acid, sodium phosphite and sulfuric acid.
9. A process for the preparation of substituted arylfluorenes and their derivatives according to claim 1, characterized in that: the structure mainly comprises the following structures:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111281543.1A CN114804994A (en) | 2021-11-01 | 2021-11-01 | Method for preparing substituted aryl fluorene and derivatives thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111281543.1A CN114804994A (en) | 2021-11-01 | 2021-11-01 | Method for preparing substituted aryl fluorene and derivatives thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114804994A true CN114804994A (en) | 2022-07-29 |
Family
ID=82526125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111281543.1A Pending CN114804994A (en) | 2021-11-01 | 2021-11-01 | Method for preparing substituted aryl fluorene and derivatives thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114804994A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643381A (en) * | 2009-07-24 | 2010-02-10 | 南京邮电大学 | Diarylfluorene intermediate preparation method |
| CN102942444A (en) * | 2012-11-09 | 2013-02-27 | 烟台海川化学制品有限公司 | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene |
| CN103420785A (en) * | 2012-12-05 | 2013-12-04 | 烟台九目化学制品有限公司 | Preparation method of 9, 9'-(4-halogen phenyl) fluorene derivative |
| CN111960953A (en) * | 2020-08-26 | 2020-11-20 | 长春海谱润斯科技有限公司 | Arylamine compound containing fluorene and organic electroluminescent device thereof |
| CN112375001A (en) * | 2020-12-02 | 2021-02-19 | 吉林奥来德光电材料股份有限公司 | Luminescent material based on fluorene arylamine compound, preparation method thereof and organic electroluminescent device |
| CN113490673A (en) * | 2019-02-28 | 2021-10-08 | 住友化学株式会社 | Metal complex and composition comprising the same |
-
2021
- 2021-11-01 CN CN202111281543.1A patent/CN114804994A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643381A (en) * | 2009-07-24 | 2010-02-10 | 南京邮电大学 | Diarylfluorene intermediate preparation method |
| CN102942444A (en) * | 2012-11-09 | 2013-02-27 | 烟台海川化学制品有限公司 | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene |
| CN103420785A (en) * | 2012-12-05 | 2013-12-04 | 烟台九目化学制品有限公司 | Preparation method of 9, 9'-(4-halogen phenyl) fluorene derivative |
| CN113490673A (en) * | 2019-02-28 | 2021-10-08 | 住友化学株式会社 | Metal complex and composition comprising the same |
| CN111960953A (en) * | 2020-08-26 | 2020-11-20 | 长春海谱润斯科技有限公司 | Arylamine compound containing fluorene and organic electroluminescent device thereof |
| CN112375001A (en) * | 2020-12-02 | 2021-02-19 | 吉林奥来德光电材料股份有限公司 | Luminescent material based on fluorene arylamine compound, preparation method thereof and organic electroluminescent device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112679420B (en) | Preparation method of 2,5-dibromopyridine | |
| CN112174989B (en) | Preparation method of clenbuterol | |
| CN108129258B (en) | Synthesis process of 4-bromo-4' -propylbiphenyl | |
| CN110066240B (en) | Synthesis method of nitrendipine | |
| CN114804994A (en) | Method for preparing substituted aryl fluorene and derivatives thereof | |
| CN108752218B (en) | Route for preparing dolutegravir key intermediate 2, 4-difluorobenzylamine | |
| CN111170953A (en) | Process for preparing diazacyclooctane intermediates and diazacyclooctanes | |
| CN112266360B (en) | Synthesis method of high-purity histamine dihydrochloride | |
| CN110156676B (en) | 3, 4-dihydroquinoline-2 (1H) -ketone derivative and preparation method and application thereof | |
| CN116836107B (en) | Carbazol eight-membered ring large conjugated structure OLED material and preparation method thereof | |
| CN113620977B (en) | Synthesis method of thiazolopyrimidinone acetic acid | |
| CN113372200B (en) | Preparation method of 2-bromo-6-fluoroanisole | |
| CN114920635B (en) | Preparation method of 4-hydroxy-1-indenone | |
| CN114181237B (en) | Synthesis method of 1-isopropyl pyrazole-5-boric acid pinacol ester | |
| CN111825688B (en) | Preparation method of 6-tert-butyl-3 ', 3', 3-trimethylpyrano [3,2-a ] carbazole | |
| CN111848423B (en) | Preparation method of tert-butyl 3-oxocyclobutylcarbamate | |
| CN108276305B (en) | Mild method for preparing Sudan red I structural analogue | |
| CN116478114A (en) | Synthesis method of 2, 3',4' -biphenyl tetracarboxylic dianhydride | |
| CN116715675A (en) | Synthetic method of isopsoralen | |
| CN116375570A (en) | Method for preparing dimethyl curcumin | |
| CN117843455A (en) | Preparation method of cannabidiol | |
| CN116574108A (en) | Synthesis method of psoralen | |
| CN116903549A (en) | Synthesis method of quinoxalinone compound | |
| CN112321621A (en) | Preparation method of 3-chlorobenzene boric acid | |
| CN116836085A (en) | Synthesis method of 2-cyano-4, 4-dialkoxy alkyl butyrate |
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 |