CN115894146A - Synthetic method of 3-bromo-1-phenylnaphthalene - Google Patents
Synthetic method of 3-bromo-1-phenylnaphthalene Download PDFInfo
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Abstract
The application relates to the field of chemical synthesis, and particularly discloses a synthetic method of 3-bromo-1-phenylnaphthalene. The synthesis method comprises the following steps: preparing a bromobenzene format reagent by taking bromobenzene as a raw material; reacting the 1-tetralone with bromobenzene format reagent to generate a mixture of 1-phenyl-1-hydroxyl tetralin and 1-phenyl-3, 4-dihydronaphthalene; the mixture of 1-phenyl-1-hydroxyl tetrahydronaphthalene and 1-phenyl-3, 4-dihydronaphthalene and N-bromosuccinimide are subjected to bromination reaction in the presence of an initiator to generate 3-bromo-1-phenylnaphthalene. The synthesis method of the 3-bromo-1-phenylnaphthalene has the advantages of low cost, short route, simplicity in operation, and high product yield and purity.
Description
Technical Field
The application relates to the field of chemical synthesis, in particular to a synthetic method of 3-bromo-1-phenylnaphthalene.
Background
3-bromo-1-phenylnaphthalene is an intermediate for preparing liquid crystal display materials. An Organic Light Emitting Diode (OLED) is a device for generating electroluminescence by using a multi-layer organic thin film structure, and can be divided into a small molecule OLED and a high molecule OLED according to light emitting materials, and 3-bromo-1-phenylnaphthalene is one of important raw materials for preparing the small molecule OLED. 3-bromo-1-phenylnaphthalene is an ideal OLED host material due to the characteristics of high hole and high electron mobility.
Currently, a method for synthesizing 3-bromo-1-phenylnaphthalene exists: brominating 1-phenyl-4-naphthylamine by N-bromosuccinimide to generate 1-phenyl-3-bromo-4-naphthylamine, and diazotizing and reducing the 1-phenyl-3-bromo-4-naphthylamine to obtain 3-bromo-1-phenylnaphthalene. The 1-phenyl-4-naphthylamine in the synthesis method is obtained by palladium-catalyzed coupling of 1-bromo-4-naphthylamine or by reduction of 1-phenylnaphthalene after nitration, and the two methods have very high cost, so that the raw materials are very expensive. In addition, the diazotization reduction process in the second step is dangerous, has large pollution, low yield and high cost.
Therefore, based on the current situation of the current 3-bromo-1-phenylnaphthalene synthesis method, the research on the 3-bromo-1-phenylnaphthalene synthesis method which is low in cost, simple to operate, high in yield and high in purity is of great significance.
Disclosure of Invention
In order to reduce the preparation cost and the operation difficulty of the 1-bromo-4-phenylnaphthalene and effectively improve the yield and the purity of the product, the application provides a synthetic method of the 3-bromo-1-phenylnaphthalene.
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
preparing a bromobenzene-format reagent by taking bromobenzene as a raw material;
reacting the 1-tetralone with bromobenzene format reagent to generate a mixture of 1-phenyl-1-hydroxyl tetralin and 1-phenyl-3, 4-dihydronaphthalene;
the mixture of 1-phenyl-1-hydroxyl tetrahydronaphthalene and 1-phenyl-3, 4-dihydronaphthalene and N-bromosuccinimide are subjected to bromination reaction in the presence of an initiator to generate 3-bromo-1-phenylnaphthalene.
By adopting the technical scheme, 1-tetralone reacts with bromobenzene format reagent, after the reaction is carried out for a period of time, the results of a dot plate test and a gas chromatography-mass spectrometer test show that 1-phenyl-1-hydroxy tetralin and part of unreacted 1-tetralone exist in the system, and part of 1-phenyl-1-hydroxy tetralin is dehydrated to generate 1-phenyl-3, 4-dihydronaphthalene, so that the intermediate product obtained after the reaction is the mixture of 1-phenyl-1-hydroxy tetralin and 1-phenyl-3, 4-dihydronaphthalene. Then the intermediate product and N-bromosuccinimide are subjected to bromination reaction in the presence of an initiator, and finally the 1-phenyl-1-hydroxy tetrahydronaphthalene and the 1-phenyl-3, 4-dihydronaphthalene are both reacted to generate the 3-bromo-1-phenylnaphthalene. The synthesis method has the advantages of low cost, short route, simple operation, high product yield and purity, and the final product 3-bromo-1-phenylnaphthalene has the yield of 69.3-74.9% and the purity of 97.9-98.6%.
Preferably, the molar ratio of bromobenzene to 1-tetralone is (1.125-1.250): 1.
Preferably, the molar ratio of bromobenzene to 1-tetralone is 1.250.
By adopting the technical scheme, in the synthesis process of the 3-bromo-1-phenylnaphthalene, when the molar ratio of bromobenzene to 1-tetralone is 1.250; and the yield and the purity of the final product 3-bromo-1-phenylnaphthalene are relatively good, the yield can reach 74.2%, and the purity can reach 98.6%.
Preferably, the reaction temperature of the 1-tetralone and the bromobenzene format reagent is not higher than 60 ℃.
By adopting the technical scheme, the correct synthesis reaction is ensured, so that the 3-bromine-1-phenylnaphthalene is successfully synthesized.
Preferably, the solvent of the bromination reaction is trichloromethane, and the weight ratio of the mixture of the 1-phenyl-1-hydroxytetrahydronaphthalene and the 1-phenyl-3, 4-dihydronaphthalene to the trichloromethane in the bromination reaction is 1 (9-11).
Preferably, the molar ratio of the mixture of 1-phenyl-1-hydroxytetrahydronaphthalene and 1-phenyl-3, 4-dihydronaphthalene to N-bromosuccinimide in the bromination reaction is 1.
Preferably, the initiator of the bromination reaction is azobisisobutyronitrile, and the weight ratio of the mixture of the 1-phenyl-1-hydroxytetrahydronaphthalene and the 1-phenyl-3, 4-dihydronaphthalene to the azobisisobutyronitrile in the bromination reaction is 1 (0.045-0.073).
Preferably, the bromination reaction time is 15 to 20 hours.
In summary, the present application has at least the following beneficial effects:
the synthesis method has the advantages of easily obtained raw materials, low cost, short route, simple operation and mild reaction process, can successfully synthesize the 3-bromo-1-phenylnaphthalene, and has the yield of 69.3-74.9% and the purity of 97.9-98.6%.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 3-bromo-1-phenylnaphthalene in example 1 of the present application.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
The raw materials used in the examples of the present application are commercially available except for the specific ones.
Examples
Example 1
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, adding 50mL of tetrahydrofuran and 8g (50 mmol) of bromobenzene into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dropping device and a reflux device, introducing nitrogen, starting stirring, adding 12g (500 mmol) of magnesium chips, adding 1g of dibromoethane, keeping reflux after initiating, dropping a tetrahydrofuran solution of the bromobenzene in a reflux state, wherein the tetrahydrofuran solution of the bromobenzene is obtained by dissolving 71g (450 mmol) of bromobenzene in 200mL of tetrahydrofuran, and continuously refluxing for 2 hours after dropping is finished to obtain a bromobenzene format reagent;
s2, cooling the obtained substance in the S1 to 50 ℃, dropwise adding 58.5g (400 mmol) of 1-tetralone, controlling the temperature to be not more than 60 ℃, refluxing for 2 hours after dropwise adding (through a spot plate test (using petroleum ether as a developing agent) and a gas chromatography-mass spectrometer test result, wherein a small amount of 1-tetralone does not react, and a part of 1-phenyl-1-hydroxytetralin is dehydrated to generate 1-phenyl-3, 4-dihydronaphthalene), cooling the obtained ice water to 5 ℃, dropwise adding dilute sulfuric acid with the mass concentration of 10% to the pH =5, keeping the temperature to be not higher than 35 ℃, decomposing unreacted bromobenzene-type reagents into benzene and magnesium bromide, separating, extracting a water phase by using ethyl acetate, combining an organic phase, and removing the ethyl acetate and the benzene in a rotary drying manner to obtain 81.6g of an intermediate product (a mixture of the 1-phenyl-1-hydroxytetralin and the 1-phenyl-3, 4-dihydronaphthalene), and the yield of the intermediate product is 91.1;
s3, adding 50mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dropping device and a refluxing device, introducing nitrogen and starting stirring, heating to reflux, dropping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of S2 and 0.5g of azobisisobutyronitrile into 50mL of trichloromethane, continuing refluxing reaction for 16h after dropping, washing 1 time with 100mL of pure water after finishing the reaction, separating, washing 1 time with 100mL of saturated salt water, separating, drying an organic phase with 10g of sodium sulfate, filtering, spin-drying the filtrate to obtain 4g of a crude 3-bromo-1-phenylnaphthalene product, distilling the crude 3-bromo-1-phenylnaphthalene under reduced pressure, drying with petroleum ether to obtain 10.5g of white powder (3-bromo-1-phenylnaphthalene), yield 74.2%, purity 98.6%, melting point 65.8 ℃ and hydrogen spectrum shown in figure 1.
Example 2
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, adding 50mL of tetrahydrofuran and 8g (50 mmol) of bromobenzene into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dropping device and a reflux device, introducing nitrogen and starting stirring, adding 10.8g (450 mmol) of magnesium chips, adding 1g of dibromoethane, keeping reflux after initiating, dropping a tetrahydrofuran solution of bromobenzene in a reflux state, wherein the tetrahydrofuran solution of bromobenzene is obtained by dissolving 62.8g (400 mmol) of bromobenzene in 200mL of tetrahydrofuran, and continuously refluxing for 2 hours after dropping is finished to obtain a bromobenzene format reagent;
s2, cooling the obtained substance in the S1 to 50 ℃, dropwise adding 58.5g (400 mmol) of 1-tetralone, controlling the temperature to be not more than 60 ℃, refluxing for 2 hours after dropwise adding (through a spot plate test (using petroleum ether as a developing agent) and a gas chromatography-mass spectrometer test result, wherein a small amount of 1-tetralone does not react, and a part of 1-phenyl-1-hydroxytetralin is dehydrated to generate 1-phenyl-3, 4-dihydronaphthalene), cooling the obtained ice water to 5 ℃, dropwise adding dilute sulfuric acid with the mass concentration of 10% to the pH =5, keeping the temperature to be not higher than 35 ℃, decomposing unreacted bromobenzene-type reagents into benzene and magnesium bromide, separating, extracting a water phase by using ethyl acetate, combining an organic phase, and removing the ethyl acetate and the benzene in a rotary drying manner to obtain 81.2g of an intermediate product (a mixture of the 1-phenyl-1-hydroxytetralin and the 1-phenyl-3, 4-dihydronaphthalene), and the yield of the intermediate product is 90.6%;
s3, adding 50mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of S2 and 0.5g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 16 hours after dripping, washing 1 time by 100mL of pure water after finishing reaction, separating liquid, washing 1 time by 100mL of saturated salt water, separating liquid, drying an organic phase by 10g of sodium sulfate, filtering, spin-drying filtrate to obtain a 3-bromo-1-phenylnaphthalene crude product, pulping the 3-bromo-1-phenylnaphthalene crude product after reduced pressure distillation by using petroleum ether, and drying to obtain 10.3g of white powder (3-bromo-1-phenylnaphthalene), the yield is 72.8%, the purity is 98.2%, and the melting point is 65.3 ℃.
Example 3
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, adding 50mL of tetrahydrofuran and 8g (50 mmol) of bromobenzene into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dropping device and a reflux device, introducing nitrogen and starting stirring, adding 12g (500 mmol) of magnesium chips, adding 1g of dibromoethane, keeping reflux after initiation, dropping a tetrahydrofuran solution of bromobenzene in a reflux state, wherein the tetrahydrofuran solution of bromobenzene is obtained by dissolving 55g (350 mmol) of bromobenzene in 200mL of tetrahydrofuran, and continuously refluxing for 2 hours after dropping to obtain a bromobenzene format reagent;
s2, cooling the obtained substance in the S1 to 50 ℃, dropwise adding 58.5g (400 mmol) of 1-tetralone, controlling the temperature to be not more than 60 ℃, refluxing for 2 hours after dropwise adding (through a spot plate test (using petroleum ether as a developing agent) and a gas chromatography-mass spectrometer test result, wherein a small amount of 1-tetralone does not react, and a part of 1-phenyl-1-hydroxytetralin is dehydrated to generate 1-phenyl-3, 4-dihydronaphthalene), cooling the obtained ice water to 5 ℃, dropwise adding dilute sulfuric acid with the mass concentration of 10% to the pH =5, keeping the temperature to be not higher than 35 ℃, decomposing unreacted bromobenzene-type reagents into benzene and magnesium bromide, separating, extracting a water phase by using ethyl acetate, combining an organic phase, and removing the ethyl acetate and the benzene in a rotary drying manner to obtain 79.4g of an intermediate product (a mixture of the 1-phenyl-1-hydroxytetralin and the 1-phenyl-3, 4-dihydronaphthalene), wherein the yield of the intermediate product is 88.6%;
s3, adding 50mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of S2 and 0.5g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 16 hours after dripping, washing 1 time by using 100mL of pure water after finishing reaction, separating liquid, washing 1 time by using 100mL of saturated salt water, separating liquid, drying an organic phase by using 10g of sodium sulfate, filtering, spin-drying filtrate to obtain a 3-bromo-1-phenylnaphthalene crude product, pulping the 3-bromo-1-phenylnaphthalene crude product after reduced pressure distillation by using petroleum ether, and drying to obtain 9.8g of white powder (3-bromo-1-phenylnaphthalene), the yield is 69.3%, the purity is 97.9%, and the melting point is 65.0 ℃.
Example 4
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, taking 11g of the intermediate product obtained in the step S2 in the example 1 for the example;
s2, adding 60mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of the intermediate product and 0.5g of azobisisobutyronitrile into 60mL of trichloromethane, continuing reflux reaction for 16 hours after finishing dripping, washing 1 time with 100mL of pure water after finishing the reaction, separating liquid, washing 1 time with 100mL of saturated salt water, separating liquid, drying an organic phase with 10g of sodium sulfate, filtering, spin-drying filtrate to obtain a crude product of 3-bromo-1-phenylnaphthalene, pulping the crude product of 3-bromo-1-phenylnaphthalene with petroleum ether after reduced pressure distillation, and drying to obtain 10.4g of white powder (3-bromo-1-phenylnaphthalene), the yield is 73.5%, the purity is 98.3%, and the melting point is 65.4 ℃.
Example 5
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, taking 11g of the intermediate product obtained in the step S2 in the example 1 for the example;
s2, adding 50mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of the intermediate product and 0.6g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 16 hours after finishing dripping, washing 1 time with 100mL of pure water after finishing the reaction, separating liquid, washing 1 time with 100mL of saturated salt water, separating liquid, drying an organic phase with 10g of sodium sulfate, filtering, spin-drying a filtrate to obtain a crude product of 3-bromo-1-phenylnaphthalene, pulping the crude product of 3-bromo-1-phenylnaphthalene with petroleum ether after reduced pressure distillation, and drying to obtain 10.6g of white powder (3-bromo-1-phenylnaphthalene), the yield is 74.9%, the purity is 98.3%, and the melting point is 65.5 ℃.
Example 6
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, taking 11g of the intermediate product obtained in the step S2 in the example 1 for the example;
s2, adding 50mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of the intermediate product and 0.8g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 16 hours after finishing dripping, washing 1 time with 100mL of pure water after finishing the reaction, separating liquid, washing 1 time with 100mL of saturated salt water, separating liquid, drying an organic phase with 10g of sodium sulfate, filtering, spin-drying a filtrate to obtain a crude product of 3-bromo-1-phenylnaphthalene, pulping the crude product of 3-bromo-1-phenylnaphthalene with petroleum ether after reduced pressure distillation, and drying to obtain 10.4g of white powder (3-bromo-1-phenylnaphthalene), the yield is 73.5%, the purity is 98.4%, and the melting point is 65.6 ℃.
Example 7
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, taking 11g of the intermediate product obtained in the step S2 in the example 1 for the example;
s2, adding 50mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of S2 and 0.5g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 15 hours after dripping, washing 1 time by 100mL of pure water after finishing reaction, separating liquid, washing 1 time by 100mL of saturated salt water, separating liquid, drying an organic phase by 10g of sodium sulfate, filtering, spin-drying filtrate to obtain a 3-bromo-1-phenylnaphthalene crude product, pulping the 3-bromo-1-phenylnaphthalene crude product after reduced pressure distillation by using petroleum ether, and drying to obtain 10.2g of white powder (3-bromo-1-phenylnaphthalene), the yield is 72.1%, the purity is 98.1%, and the melting point is 65.1 ℃.
Example 8
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, taking 11g of the intermediate product obtained in the step S2 in the example 1 for the example;
s2, adding 50mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of S2 and 0.5g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 20 hours after dripping, washing 1 time by using 100mL of pure water after finishing reaction, separating liquid, washing 1 time by using 100mL of saturated salt water, separating liquid, drying an organic phase by using 10g of sodium sulfate, filtering, spin-drying filtrate to obtain a 3-bromo-1-phenylnaphthalene crude product, pulping the 3-bromo-1-phenylnaphthalene crude product after reduced pressure distillation by using petroleum ether, and drying to obtain white powder (3-bromo-1-phenylnaphthalene) with yield of 72.8%, purity of 98.1% and melting point of 65.0 ℃.
Example 9
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, taking 11g of the intermediate product obtained in the step S2 in the example 1 for the example;
s2, adding 50mL of trichloromethane and 17.8g (100 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of S2 and 0.5g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 16 hours after dripping, washing 1 time with 100mL of pure water after finishing reaction, separating liquid, washing 1 time with 100mL of saturated saline solution, separating liquid, drying an organic phase with 10g of sodium sulfate, filtering, spin-drying filtrate to obtain a crude product of 3-bromo-1-phenylnaphthalene, pulping the crude product of 3-bromo-1-phenylnaphthalene by using petroleum ether after vacuum distillation, and drying to obtain 10.2g of white powder (3-bromo-1-phenylnaphthalene), the yield is 72.1%, the purity is 98.2%, and the melting point is 13.3 ℃.
Example 10
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, 11g of the intermediate product obtained in step S2 of example 1 was taken for this example;
s2, adding 50mL of trichloromethane and 21.4g (120 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of S2 and 0.5g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 16 hours after dripping, washing 1 time by 100mL of pure water after finishing reaction, separating liquid, washing 1 time by 100mL of saturated saline solution, separating liquid, drying an organic phase by 10g of sodium sulfate, filtering, spin-drying filtrate to obtain a crude product of 3-bromo-1-phenylnaphthalene, pulping by using petroleum ether after vacuum distillation, and drying to obtain 10.3g of white powder (3-bromo-1-phenylnaphthalene), the yield is 8.8%, the purity is 98.4%, and the melting point is 17.7 ℃.
Example 11
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, adding 50mL of tetrahydrofuran and 8g (50 mmol) of bromobenzene into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dropping device and a reflux device, introducing nitrogen and starting stirring, adding 12g (500 mmol) of magnesium chips, adding 1g of dibromoethane, keeping reflux after initiation, dropping a tetrahydrofuran solution of bromobenzene in a reflux state, wherein the tetrahydrofuran solution of bromobenzene is obtained by dissolving 71g (450 mmol) of bromobenzene in 200mL of tetrahydrofuran, and continuously refluxing for 2 hours after dropping to obtain a bromobenzene format reagent;
s2, cooling the obtained substance in the S1 to 50 ℃, dropwise adding 58.5g (400 mmol) of 1-tetralone, controlling the temperature to be not more than 70 ℃, refluxing for 2 hours after dropwise adding (through a spot plate test (using petroleum ether as a developing agent) and a gas chromatography-mass spectrometer test result, wherein a small amount of 1-tetralone does not react, and a part of 1-phenyl-1-hydroxytetralin is dehydrated to generate 1-phenyl-3, 4-dihydronaphthalene), cooling the obtained ice water to 5 ℃, dropwise adding dilute sulfuric acid with the mass concentration of 10% to the pH =5, keeping the temperature to be not higher than 35 ℃, decomposing unreacted bromobenzene-type reagents into benzene and magnesium bromide, separating, extracting a water phase by using ethyl acetate, combining an organic phase, and removing the ethyl acetate and the benzene in a rotary drying manner to obtain 81.0g of an intermediate product (a mixture of the 1-phenyl-1-hydroxytetralin and the 1-phenyl-3, 4-dihydronaphthalene), wherein the yield of the intermediate product is 90.4%;
s3, adding 50mL of trichloromethane and 19.6g (110 mmol) of N-bromosuccinimide into a four-neck flask provided with a nitrogen guide pipe, a thermometer, a stirrer, a dripping device and a reflux device, introducing nitrogen and starting stirring, heating to reflux, dripping a trichloromethane solution of an intermediate product, wherein the trichloromethane solution of the intermediate product is obtained by dissolving 11g (about 50 mmol) of S2 and 0.5g of azobisisobutyronitrile into 50mL of trichloromethane, continuing reflux reaction for 16 hours after dripping, washing 1 time by 100mL of pure water after finishing reaction, separating liquid, washing 1 time by 100mL of saturated saline solution, separating liquid, drying an organic phase by 10g of sodium sulfate, filtering, spin-drying filtrate to obtain a crude product of 3-bromo-1-phenylnaphthalene, pulping by using petroleum ether after vacuum distillation, and drying to obtain 10.0g of white powder (3-bromo-1-phenylnaphthalene), the yield is 70.7%, the purity is 98.0%, and the melting point is 165.1 ℃.
Comparative example
Comparative example 1
A synthetic method of 3-bromo-1-phenylnaphthalene comprises the following steps:
s1, adding 42g (192 mmol) of 1-phenyl-4-naphthylamine into a round-bottom flask, adding 300mL of dimethylformamide into the flask, stirring and mixing, dropwise adding N-bromosuccinimide dimethylformamide solution into the mixture at 0 ℃, wherein the N-bromosuccinimide dimethylformamide solution is obtained by dissolving 34.1g (192 mmol) of N-bromosuccinimide into 120mL of dimethylformamide solution, stirring and reacting at room temperature (25 ℃) for 12 hours after dropwise adding is finished, pouring the obtained product into 1000mL of pure water after the reaction is finished, filtering, collecting filter residues, purifying and drying to obtain 36g of 1-phenyl-3-bromo-4-naphthylamine with the yield of 63%;
s2, 36g (121 mmol) of 1-phenyl-3-bromo-4-naphthylamine obtained in S1 is placed in a round-bottom flask, 540mL of tetrahydrofuran is added into the flask, stirring and mixing are carried out, 159.4g (2.415 mol) of hypophosphorous acid and 25g (362 mmol) of sodium nitrate are added dropwise into the mixture at 0 ℃, stirring is carried out for 4h, the mixture is heated to room temperature (25 ℃) and then stirred for reaction for 12h, dichloromethane and water are added after the reaction is finished, the pH of the mixture is adjusted to 10 by using 2mol/L of sodium hydroxide solution, an organic layer is extracted, and purification and drying are carried out, so that 8g of 3-bromo-1-phenylnaphthalene is obtained, and the yield is 53%.
As can be seen from comparing the synthesis methods of example 1 and comparative example 1, compared with the synthesis method described in example 1, the 1-phenyl-4-naphthylamine used as the raw material in comparative example 1 is obtained by palladium-catalyzed coupling of 1-bromo-4-naphthylamine or by nitration and reduction of 1-phenylnaphthalene, both methods have very high cost, which results in higher cost of the raw material in comparative example 1, and the step S2 in comparative example 1 is a diazotization reduction reaction, which has higher requirements on reaction conditions and lower yield of only 53%, while the reaction route in example 1 has the advantages of simple and easily available raw materials, simple operation and high yield of 74.2%.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A synthetic method of 3-bromo-1-phenylnaphthalene is characterized by comprising the following steps:
preparing a bromobenzene-format reagent by taking bromobenzene as a raw material;
reacting the 1-tetralone with bromobenzene format reagent to generate a mixture of 1-phenyl-1-hydroxyl tetralin and 1-phenyl-3, 4-dihydronaphthalene;
the mixture of 1-phenyl-1-hydroxyl tetrahydronaphthalene and 1-phenyl-3, 4-dihydronaphthalene and N-bromosuccinimide react with each other in the presence of an initiator to generate 3-bromo-1-phenylnaphthalene.
2. The method for synthesizing 3-bromo-1-phenylnaphthalene according to claim 1, wherein the molar ratio of bromobenzene to 1-tetralone is (1.125-1.250): 1.
3. The method for synthesizing 3-bromo-1-phenylnaphthalene according to claim 2, wherein the molar ratio of bromobenzene to 1-tetralone is 1.250.
4. The method for synthesizing 3-bromo-1-phenylnaphthalene according to claim 1, wherein the reaction temperature of 1-tetralone and bromobenzene format reagent is not higher than 60 ℃.
5. The method for synthesizing 3-bromo-1-phenylnaphthalene according to claim 1, wherein the solvent used in the bromination reaction is chloroform, and the weight ratio of the mixture of 1-phenyl-1-hydroxytetrahydronaphthalene and 1-phenyl-3, 4-dihydronaphthalene to chloroform in the bromination reaction is 1 (9-11).
6. The method of claim 1, wherein the bromination is conducted in a molar ratio of a mixture of 1-phenyl-1-hydroxytetrahydronaphthalene and 1-phenyl-3, 4-dihydronaphthalene to N-bromosuccinimide of 1.
7. The method for synthesizing 3-bromo-1-phenylnaphthalene according to claim 1, wherein the initiator of the bromination reaction is azobisisobutyronitrile, and the weight ratio of the mixture of 1-phenyl-1-hydroxytetralin and 1-phenyl-3, 4-dihydronaphthalene to azobisisobutyronitrile in the bromination reaction is 1 (0.045-0.073).
8. The method of claim 1, wherein the bromination is carried out for 15 to 20 hours.
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