CN107056595B - Preparation method of 3-bromofluorenone - Google Patents
Preparation method of 3-bromofluorenone Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of fluorene compounds, and particularly relates to a preparation method of 3-bromofluorenone, which comprises the following steps: A. oximation reaction: adding fluorenone and methoxylamine hydrochloride into a solvent, carrying out oximation reaction, and carrying out reaction quenching treatment to obtain fluorenone methoxyxime; B. bromination reaction: adding a catalyst, bromine and the fluorenone methoxy oxime obtained in the step A into a solvent, and carrying out reaction quenching treatment to obtain a brominated product; C. and (3) hydrolysis reaction: and B, adding the brominated product obtained in the step B into a solvent, and carrying out hydrolysis reaction at 50-100 ℃ to obtain the 3-bromofluorenone.
Description
Technical Field
The invention belongs to the technical field of preparation of fluorene compounds, and particularly relates to a preparation method of 3-bromofluorenone.
Background
The fluorene compounds are used as electroluminescent materials with rigid plane biphenyl structure, and have attracted attention due to the characteristics of wide energy gap, high luminous efficiency and the like, and the fluorenone derivatives are widely applied to organic photoconductor (OLED) devices as electron transport materials. The halogenated fluorenone compound is introduced into the molecule with the electroluminescent characteristic, and has important significance for improving the thermal stability and the spectral stability of the molecule; the substituted aryl Schiff base compound of the halogenated fluorenone has photochromic performance; and the halogenated fluorenone compound is an important multifunctional intermediate. The most representative of these compounds is 3-bromofluorenone.
The preparation method of the compound is more, and the common preparation methods mainly comprise the following steps:
1. in 2010, Tetrahedron Letters, 51(37),4894-4897, phenanthrenequinone is used as a raw material, and 3-bromofluorenone is obtained by bromination with bromine, hydrolysis and rearrangement with potassium hydroxide, and oxidation with potassium permanganate. The disadvantages of this process are the slow rearrangement reaction, the low yields and the difficulty in obtaining high purity products. The reaction route is as follows:
2. 1935 the Journal of the American Chemical Society, Volume 57,2443-2446, generated diazo-reaction with 2-amino-4-bromoacetophenone to generate diazonium salt, followed by ring closure reaction to obtain 3-bromofluorenone. The method has the defects of high price, difficult obtainment, low yield and the like of raw materials, so that the use of the method is limited, the purification difficulty is high, and the obtained product can hardly meet the requirements of organic photoelectric materials. The reaction route is as follows:
3. chinese patent CN105294415 adopts 2-bromo-4-nitrobenzoic acid methyl ester as starting material, and prepares general formula 3-bromofluorenone through Suzuki reaction, reduction reaction, diazotization reaction and ring closure reaction. The method has the defects that the reaction route is too long, diazotization is involved, the safety is poor, the purification difficulty of the obtained product is high, and the requirements of organic photoelectric materials are difficult to meet. The reaction route is as follows:
disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of 3-bromofluorenone, which is simple and low in cost, and the obtained 3-bromofluorenone has high yield and purity, mild reaction conditions and is suitable for industrial production.
The technical scheme for solving the technical problems is as follows: a preparation method of 3-bromofluorenone comprises the following steps:
A. oximation reaction: adding fluorenone and methoxylamine hydrochloride into a solvent, carrying out oximation reaction, and carrying out reaction quenching treatment to obtain fluorenone methoxyxime;
B. bromination reaction: adding a catalyst, bromine and the fluorenone methoxy oxime obtained in the step A into a solvent, and carrying out reaction quenching treatment to obtain a brominated product;
C. and (3) hydrolysis reaction: and D, adding the brominated product obtained in the step B into a solvent, and carrying out hydrolysis reaction at 50-100 ℃ to obtain the 3-bromofluorenone.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in step a, the solvent is methanol and/or ethanol.
Further, in the step B, the solvent is one or a mixture of any of dichloromethane, chloroform and dichloroethane.
Further, in the step C, the solvent is hydrochloric acid with the mass concentration of 20-35%, and the molar ratio of the hydrochloric acid to the fluorenone in the step A is (1.0-1.2): 1.
further, in the step A, the reaction temperature is controlled to be 40-100 ℃, and the reaction time is controlled to be 2-5 h.
Further, in the step B, the reaction temperature is controlled to be 30-60 ℃, and the reaction time is controlled to be 2-5 h.
Further, in the step C, the reaction time is controlled to be 2-5 h.
Further, in the step A, the molar ratio of the fluorenone to the methoxylamine hydrochloride is 20: (20-22).
Further, in the step B, the catalyst is aluminum trichloride, and the molar ratio of the aluminum trichloride to the fluorenone methoxy oxime in the step A is (0.05-0.1): 1.
further, in step B, the molar ratio of the bromine to the fluorenone methoxy oxime in step A is (0.9-1.0): 1.
the 3-bromofluorenone is prepared by the preparation method, and the reaction route is as follows:
the invention has the beneficial effects that:
(1) the invention provides a preparation method of 3-bromofluorenone, which has the advantages of cheap and easily-obtained raw materials, mild reaction conditions, simple and safe operation, environmental protection and high efficiency.
(2) The 3-bromofluorenone prepared by the method has high reaction yield, the total yield can reach 70%, the cost is low, the purity is high, the GC purity can reach 99.9%, and the dibromide is less than 100ppm, so that the application of organic photoelectric materials such as OLED and the like is met.
(3) The preparation method is simple, the raw materials are cheap and easy to obtain, the market prospect is wide, and the method is suitable for industrial production.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
Preparation of fluorenone methoxy oxime: 36.0g (200mmol) of fluorenone, 17.5g (210mmol) of methoxylamine hydrochloride and 13g (122mmol) of sodium carbonate are dissolved in 250mL of methanol solution, the temperature is raised to 60-65 ℃, and the reaction is stirred for 3.0 hrs. And cooling to room temperature, adding 100g and 200g of chloroform into the reaction system, layering, washing an organic phase by 100mL of water, drying by anhydrous sodium sulfate, and removing the solvent in vacuum to obtain 41.6g of a fluorenone methoxy oxime crude product, wherein the yield is 99.52%, and the fluorenone methoxy oxime crude product is directly used in the next step without purification.
Preparation of 3-bromofluorenone methoxyoxime: 21.0g (100mmol) of fluorenone methoxyoxime and 1g (7.5mmol) of aluminum trichloride were added to 200g of dichloroethane, nitrogen was sufficiently replaced, and a mixture of bromodichloroethane (15.9g (100mmol) of bromine +100g of dichloroethane) was added dropwise at 50 ℃. Dropwise adding for about 1hr, after the reaction is finished, 100mL of saturated sodium bisulfite aqueous solution, layering, washing with water, and drying with organic phase anhydrous sodium sulfate to obtain the 3-bromofluorenone methoxy oxime dichloroethane solution, wherein the yield is 100 percent without purification and is directly used in the next step.
Preparation of 3-bromofluorenone: adding the 3-bromofluorenone methoxy oxime dichloroethane solution into 100g of 25% diluted hydrochloric acid, stirring and hydrolyzing at 70 ℃, tracking the reaction progress by TLC, and finishing the reaction for about 3 hrs. Layering, washing, drying an organic phase by using anhydrous sodium sulfate, removing a solvent to obtain a crude product of the 3-bromofluorenone, recrystallizing the toluene-ethanol mixed solution twice to obtain a bright yellow needle-shaped refined product of the 3-bromofluorenone, wherein the purity of the product by GC is 99.90 percent, the dibromo-compound content is less than 100ppm, and the yield is 69.88 percent.
The detection data of the 3-bromofluorenone prepared in this example are as follows:
GC-MS (ESI): 258, calculated value 257.97.
1H-NMR(400MHz,DMSO-d6)δ
(ppm):7.76(d,2H),7.50-7.65(m,2H),7.32(m,2H)。
13C-NMR(100MHZ,DMSO-d6)δ
(ppm):192.4,146.3,144.1,139.4,138.4,133.2,133.0,130.3,127.4,127.2。
Example 2
Preparation of fluorenone methoxy oxime: 36.0g (200mmol) of fluorenone, 16.7g (200mmol) of methoxylamine hydrochloride and 11.7g (110mmol) of sodium carbonate are dissolved in 250mL of methanol solution, the temperature is raised to 60-65 ℃, and the reaction is stirred for 3.0 hrs. And cooling to room temperature, adding 100g and 200g of chloroform into the reaction system, layering, washing an organic phase by 100mL of water, drying by anhydrous sodium sulfate, and removing the solvent in vacuum to obtain 41.4g of a fluorenone methoxy oxime crude product, wherein the yield is 99.04%, and the fluorenone methoxy oxime crude product is directly used in the next step without purification.
Preparation of 3-bromofluorenone methoxyoxime: 21.0g (100mmol) of fluorenone methoxyoxime and 0.7g (5mmol) of aluminum trichloride were added to 200g of dichloroethane, nitrogen was sufficiently replaced, and a mixture of bromodichloroethane (14.3g (90mmol) of bromine +100g of dichloroethane) was added dropwise at 60 ℃. Dropwise adding for about 1hr, after the reaction is finished, 100mL of saturated sodium bisulfite aqueous solution, layering, washing with water, and drying with organic phase anhydrous sodium sulfate to obtain the 3-bromofluorenone methoxy oxime dichloroethane solution, wherein the yield is 100 percent without purification and is directly used in the next step.
Preparation of 3-bromofluorenone: adding the 3-bromofluorenone methoxy oxime dichloroethane solution into 100g of 25% diluted hydrochloric acid, stirring and hydrolyzing at 60 ℃, tracking the reaction progress by TLC, and finishing the reaction for about 3 hrs. Layering, washing, drying an organic phase by using anhydrous sodium sulfate, removing a solvent to obtain a crude product of the 3-bromofluorenone, recrystallizing the toluene-ethanol mixed solution twice to obtain 17.0g of a bright yellow needle-shaped refined product of the 3-bromofluorenone, wherein the GC purity is 99.93 percent, the dibromo-compound content is less than 100ppm, and the yield is 65.63 percent.
The detection data of the 3-bromofluorenone prepared in this example are as follows:
GC-MS (ESI): 258, calculated value 257.97.
1H-NMR(400MHz,DMSO-d6)δ
(ppm):7.76(d,2H),7.50-7.65(m,2H),7.32(m,2H)。
13C-NMR(100MHZ,DMSO-d6)δ
(ppm):192.4,146.3,144.1,139.4,138.4,133.2,133.0,130.3,127.4,127.2。
Example 3
Preparation of fluorenone methoxy oxime: 36.0g (200mmol) of fluorenone, 18.4g (220mmol) of methoxylamine hydrochloride and 13g (122mmol) of sodium carbonate are dissolved in 250mL of ethanol solution, the temperature is raised to 70-75 ℃, and the reaction is stirred for 3.0 hrs. And cooling to room temperature, adding 100g and 200g of chloroform into the reaction system, layering, washing an organic phase by 100mL of water, drying by anhydrous sodium sulfate, and removing the solvent in vacuum to obtain 41.8g of a fluorenone methoxy oxime crude product, wherein the yield is 100%, and the fluorenone methoxy oxime crude product is directly used in the next step without purification.
Preparation of 3-bromofluorenone methoxyoxime: 21.0g (100mmol) of fluorenone methoxyoxime and 1.3g (10mmol) of aluminum trichloride were added to 200g of dichloroethane, nitrogen was sufficiently replaced, and a mixture of bromodichloroethane (15.2g (95mmol) of bromine +100g of dichloroethane) was added dropwise at 40 ℃. Dropwise adding for about 1hr, after the reaction is finished, 100mL of saturated sodium bisulfite aqueous solution, layering, washing with water, and drying with organic phase anhydrous sodium sulfate to obtain the 3-bromofluorenone methoxy oxime dichloroethane solution, wherein the yield is 100 percent without purification and is directly used in the next step.
Preparation of 3-bromofluorenone: adding the 3-bromofluorenone methoxy oxime dichloroethane solution into 100g of 25% diluted hydrochloric acid, stirring and hydrolyzing at 70 ℃, tracking the reaction progress by TLC, and finishing the reaction for about 3 hrs. Layering, washing, drying an organic phase by using anhydrous sodium sulfate, removing a solvent to obtain a crude product of the 3-bromofluorenone, recrystallizing the toluene-ethanol mixed solution twice to obtain 17.8g of a bright yellow needle-shaped refined product of the 3-bromofluorenone, wherein the GC purity is 99.91 percent, the dibromo-compound content is less than 100ppm, and the yield is 68.72 percent.
The detection data of the 3-bromofluorenone prepared in this example are as follows:
GC-MS (ESI): 258, calculated value 257.97.
1H-NMR(400MHz,DMSO-d6)δ
(ppm):7.76(d,2H),7.50-7.65(m,2H),7.32(m,2H)。
13C-NMR(100MHZ,DMSO-d6)δ
(ppm):192.4,146.3,144.1,139.4,138.4,133.2,133.0,130.3,127.4,127.2。
Example 4
Preparation of fluorenone methoxy oxime: 36.0g (200mmol) of fluorenone, 17.5g (210mmol) of methoxylamine hydrochloride and 16.5g (120mmol) of potassium carbonate were dissolved in 250mL of an ethanol solution, and the reaction was stirred at 70 to 75 ℃ for 3.0 hrs. And cooling to room temperature, adding 100g and 200g of chloroform into the reaction system, layering, washing an organic phase by 100mL of water, drying by anhydrous sodium sulfate, and removing the solvent in vacuum to obtain 41.6g of a fluorenone methoxy oxime crude product, wherein the yield is 99.52%, and the fluorenone methoxy oxime crude product is directly used in the next step without purification.
Preparation of 3-bromofluorenone methoxyoxime: 21.0g (100mmol) of fluorenone methoxyoxime and 1g (7.5mmol) of aluminum trichloride were added to 200g of dichloroethane, nitrogen was sufficiently replaced, and a mixture of bromodichloroethane (14.7g (92mmol) of bromine +100g of dichloroethane) was added dropwise at 50 ℃. Dropwise adding for about 1hr, after the reaction is finished, 100mL of saturated sodium bisulfite aqueous solution, layering, washing with water, and drying with organic phase anhydrous sodium sulfate to obtain the 3-bromofluorenone methoxy oxime dichloroethane solution, wherein the yield is 100 percent without purification and is directly used in the next step.
Preparation of 3-bromofluorenone: adding the 3-bromofluorenone methoxy oxime dichloroethane solution into 100g of 25% diluted hydrochloric acid, stirring and hydrolyzing at 70 ℃, tracking the reaction progress by TLC, and finishing the reaction for about 3 hrs. Layering, washing, drying an organic phase by using anhydrous sodium sulfate, removing a solvent to obtain a crude product of the 3-bromofluorenone, recrystallizing the toluene-ethanol mixed solution twice to obtain 17.2g of a bright yellow needle-shaped refined product of the 3-bromofluorenone, wherein the GC purity is 99.92%, the dibromo-compound content is less than 100ppm, and the yield is 66.41%.
The detection data of the 3-bromofluorenone prepared in this example are as follows:
GC-MS (ESI): 258, calculated value 257.97.
1H-NMR(400MHz,DMSO-d6)δ
(ppm):7.76(d,2H),7.50-7.65(m,2H),7.32(m,2H)。
13C-NMR(100MHZ,DMSO-d6)δ
(ppm):192.4,146.3,144.1,139.4,138.4,133.2,133.0,130.3,127.4,127.2。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of 3-bromofluorenone is characterized by comprising the following steps:
A. oximation reaction: adding fluorenone and methoxylamine hydrochloride into a solvent, carrying out oximation reaction, and carrying out reaction quenching treatment to obtain fluorenone methoxyxime;
B. bromination reaction: adding a catalyst, bromine and the fluorenone methoxy oxime obtained in the step A into a solvent, and carrying out reaction quenching treatment to obtain a brominated product;
C. and (3) hydrolysis reaction: adding the bromo product obtained in the step B into a solvent, and carrying out hydrolysis reaction at 50-100 ℃ to obtain 3-bromofluorenone;
in the step B, the catalyst is aluminum trichloride, and the molar ratio of the aluminum trichloride to the fluorenone methoxy oxime in the step A is (0.05-0.1): 1.
2. the method for preparing 3-bromofluorenone according to claim 1, wherein the solvent in step a is one or more of methanol and/or ethanol.
3. The method for preparing 3-bromofluorenone according to claim 1, wherein in the step B, the solvent is one or a mixture of dichloromethane, chloroform and dichloroethane.
4. The method for preparing 3-bromofluorenone according to claim 1, wherein in step C, the solvent is hydrochloric acid with a mass concentration of 20-35%, and the molar ratio of the hydrochloric acid to the fluorenone in step a is (1.0-1.2): 1.
5. the method for preparing 3-bromofluorenone according to claim 1, wherein in the step A, the reaction temperature is controlled to be 40-100 ℃ and the reaction time is controlled to be 2-5 h.
6. The method for preparing 3-bromofluorenone according to claim 1, wherein in the step B, the reaction temperature is controlled to be 30-60 ℃ and the reaction time is controlled to be 2-5 h.
7. The method for preparing 3-bromofluorenone according to claim 1, wherein the reaction time in step C is controlled to be 2-5 h.
8. The method for preparing 3-bromofluorenone according to claim 1, wherein in the step A, the molar ratio of fluorenone to methoxylamine hydrochloride is 20: (20-22).
9. The method for preparing 3-bromofluorenone according to claim 1, wherein in step B, the molar ratio of bromine to fluorenone methoxy oxime in step A is (0.9-1.0): 1.
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| CN105294415A (en) * | 2015-09-11 | 2016-02-03 | 烟台九目化学制品有限公司 | Preparation method of 3-halogenated fluorenone compound |
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| 2-溴芴酮的合成;张鑫;《精细化工》;20081031;第25卷(第10期);1034-1036 * |
| Carbazole Compounds as Host Materials for Triplet Emitters;Klemens Brunner;《JACS ARTICLES》;20040423;第126卷(第19期);6035-6042 * |
| Pd-Catalyzed Multiple C-H Functionalization to Construct Biologically;Thirunavukkarasu, Vedhagiri S;《Chemistry - A European Journal》;20111231;第17卷(第52期);14723-14726 * |
| Preparation of various Schiff"s bases of 9-fluorenone and its biological application;Venkatesan, Kirithivasan;《Journal of Chemical and Pharmaceutical Research》;20121231;第4卷(第10期);4477-4483 * |
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