Preparation method of 1-bromoadamantane
By using liquid bromine as both reactant and solvent at ambient temperature and pressure, controlling the reaction temperature, and treating bromine with a dispersant, the problems of high temperature, long cycle, and low purity in the preparation of 1-bromoadamantane were solved, achieving a safe, environmentally friendly, and efficient production process.
Patent Information
- Application Number
- CN202511140650.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-15
- Publication Date
- 2025-12-12
AI Technical Summary
The existing process for preparing 1-bromoadamantane has problems such as high reaction temperature, long cycle time, high safety risk, environmental unfriendliness, low purity and serious loss of bromine.
At room temperature and pressure, liquid bromine is used as the reactant and solvent. The reaction temperature is controlled at 40-50°C. Adamantane is added and the reaction is maintained for 3-4 hours. The residual bromine is treated with a bromine dispersant such as hydrobromic acid, hydroiodic acid, phosphoric acid or sulfuric acid. The product is then separated and dried.
It significantly shortens reaction time, increases yield efficiency, reduces safety risks, reduces bromine consumption, increases product purity to over 99.5%, and lowers production costs.
Smart Images
Figure CN121107942A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a preparation technology of an organic compound, in particular to a preparation method of 1-bromoadamantane. BACKGROUND
[0002] 1-bromoadamantane is a bromine-substituted product of adamantane, white crystalline powder, insoluble in water, soluble in organic solvents, and is an intermediate for synthesizing hydrochloric acid adamantylamine. It is an organic chemical product, and is an important fine chemical product, and can be used as a key intermediate for preparing medicinal compounds. The existing industrialized preparation process of 1-bromoadamantane is as follows: at normal temperature and pressure, adamantane is added into a reaction kettle, and 1.2 times the weight of adamantane of bromine is added, the reaction kettle is heated to 90℃±5℃, and after the reaction is completed, the temperature is increased to 120℃±5℃, most of the bromine is distilled out, and the residual bromine is removed by adding sodium pyrosulfite aqueous solution into the reaction kettle due to the water-insoluble property of bromoadamantane, and then 1-bromoadamantane is obtained by filtering and drying.
[0003] The above method for preparing 1-bromoadamantane has the following disadvantages: ① because the reaction for preparing bromoadamantane from adamantane and bromine is a reversible reaction, bromine is a liquid at normal temperature, and the boiling point is only 58.76℃, and it is easy to volatilize, in order to ensure that the concentration of bromine is high enough to make the reaction proceed smoothly, a condensation reflux method is used to make bromine return to the reaction kettle, which has high safety risk and energy consumption; ② after the reaction is completed, a large amount of bromine remains, and sodium pyrosulfite solution needs to be added for debromination, because there is too much residual bromine, a large amount of sodium pyrosulfite solution needs to be added, which causes a large amount of waste salt and a large amount of waste water, is not friendly to the environment, and has high production cost; ③ the required temperature during the reaction is as high as 90℃±5℃, and the time needs to be maintained for 12-18 hours, which has high temperature, long period, and large energy consumption, and has many side reactions, and the purity of 1-bromoadamantane product is low; ④ because the reaction temperature is high and the duration is long, the boiling point of bromine is much lower than the reaction temperature, the loss of bromine is large, and the environmental pollution is serious. SUMMARY
[0004] In order to overcome the problems in the background art, the purpose of the present application is to provide a preparation method of 1-bromoadamantane, which has short reaction period, lower reaction temperature, high one-time yield, small safety risk, and is more friendly to the environment.
[0005] In order to achieve the above purpose, the present application realizes the technical scheme as follows:
[0006] At normal temperature and pressure, 40% to 50% of liquid bromine in the reaction kettle is added, and adamantane is added at a speed of 800 kg / hour, the total amount of adamantane is controlled to be 1:2 of the mass of liquid bromine, the temperature is controlled to be 40 to 50 DEG C, after the addition of adamantane is completed, the temperature is kept at 40 to 50 DEG C for 3 to 4 hours, sampling is taken, when the content of adamantane is less than 0.5%, the reaction is stopped, most of the excess bromine is distilled off, a bromine dispersant is added after stirring for 30 minutes, the residual bromine is separated, the 1-bromoadamantane is washed and dried to obtain 1-bromoadamantane product. The chemical reaction formula is:
[0007] The beneficial effects of the present application are:
[0008] (1) The technical scheme of the present application greatly reduces the safety risk, mainly reflected in that the reaction temperature of the original industrialization scheme is 90 DEG C to 5 DEG C or even higher, the heating amount in the reaction kettle is large, the distillation speed of bromine in the reaction process is fast, the reaction kettle bears high pressure, and leakage is easy to occur; and the reaction temperature of the present application is controlled at 40 to 50 DEG C, and no elemental bromine escapes from the reaction kettle during the reaction.
[0009] (2) In the present application, liquid bromine is both a reactant and a solvent, and no other solvent is added, so the cost advantage is more obvious.
[0010] (3) The reaction in the present application is more moderate than the traditional process, so the single-kettle feeding amount is doubled, and the single-kettle production capacity is improved by more than one time.
[0011] (4) After optimization of the reaction conditions, the purity of the obtained 1-bromoadamantane is more than 99.5%.
[0012] (5) Since a dispersant is used to remove excess bromine, the consumption of bromine is low, the yield of 1-bromoadamantane is more than 99%, and the operation is simple. BRIEF DESCRIPTION OF DRAWINGS
[0013] Figure 1 The chromatogram of 1-bromoadamantane of the present application.
[0014] Figure 2 The chromatogram of 1-bromoadamantane prepared by the process commonly used in the present industrialization device mentioned in the background art.
[0015] Figure 3 The chemical reaction formula of adamantane and liquid bromine of the present application. DETAILED DESCRIPTION
[0016] Example 1, the present application is a preparation method of 1-bromoadamantane, comprising the following steps, the following are in mass percentage:
[0017] (1) At normal temperature and pressure, 40% to 50% of liquid bromine in the reaction kettle is added, and adamantane is added at a speed of 800 kg / hour, the total amount of adamantane is controlled to be 1:2 of the mass of liquid bromine, the temperature is controlled to be 40 to 50 DEG C, after the addition of adamantane is completed, the temperature is kept at 40 to 50 DEG C for 3 to 4 hours, sampling is taken, when the content of adamantane is less than 0.5%, the reaction is stopped, most of the excess bromine is distilled off, a bromine dispersant is added after stirring for 30 minutes, the residual bromine is separated, the 1-bromoadamantane is washed and dried to obtain 1-bromoadamantane product. The chemical reaction formula is:
[0018] (2) At normal temperature, add adamantane at a speed of 800 kg / h, control the total amount of adamantane to be 6000 kg, and control the temperature to be 40-50 DEG C.
[0019] (3) After the addition of adamantane is completed, keep the temperature at 40-50 DEG C for 3-4 hours, and stop the reaction when the content of adamantane is less than 0.5%.
[0020] (4) Raise the temperature of the reactor to 70 DEG C to distill the residual bromine.
[0021] (5) Add 2000 kg of hydrobromic acid with a concentration of 30% and stir for 30 minutes, separate the liquid, rinse the 1-bromoadamantane, dry, and test the purity of 1-bromoadamantane to be more than 98.5%, and obtain 9250 kg of 1-bromoadamantane product.
[0022] The present application utilizes the characteristics that bromine is both a reactant and a solvent, increases the addition amount of bromine, successfully reduces the reaction temperature, accelerates the reaction rate, greatly shortens the reaction time, and significantly improves the yield efficiency; utilizes the characteristics that hydrobromic acid can well dissolve bromine but not 1-bromoadamantane, well removes the residual bromine in the reaction system, and the acidic system is not easy to produce side reactions in the presence of water, so that the purity of the product is more than 98.5%.
[0023] Example 2, the present application is a preparation method of 1-bromoadamantane, comprising the following steps, the following are in percentage by mass:
[0024] (1) At normal temperature and pressure, add liquid bromine 15000 kg into a 10000 L reactor.
[0025] (2) At normal temperature, add adamantane at a speed of 800 kg / h, control the total amount of adamantane to be 7600 kg, and control the temperature to be 40-50 DEG C.
[0026] (3) After the addition of adamantane is completed, keep the temperature at 40-50 DEG C for 3-4 hours, and stop the reaction when the content of adamantane is less than 0.5%.
[0027] (4) Raise the temperature of the reactor to 70 DEG C to distill the residual bromine.
[0028] (5) Add 2000 kg of hydrobromic acid with a concentration of 30% and stir for 30 minutes, separate the liquid, rinse the 1-bromoadamantane, dry, and test the purity of 1-bromoadamantane to be more than 99%, and obtain 11800 kg of 1-bromoadamantane product.
[0029] The present application utilizes the characteristics that bromine is both a reactant and a solvent, increases the bromine dosage, smoothly reduces the reaction temperature, accelerates the reaction rate, greatly shortens the whole reaction time, and significantly improves the yield efficiency; utilizes the characteristics that hydrobromic acid can well dissolve bromine but not 1-bromoadamantane, well removes the residual bromine in the reaction system, 1-bromoadamantane is not easy to produce side reactions in the acidic system with water, and makes the product purity reach more than 99%.
[0030] Example 3, the present application is a preparation method of 1-bromoadamantane, comprising the following steps, the following are mass percentages:
[0031] (1) 15000 kg of liquid bromine is added into a 10000 L reaction kettle at normal temperature and pressure.
[0032] (2) At normal temperature, adamantane is added at a speed of 800 kg / h, the total amount of adamantane is controlled to be 7200 kg, and the temperature is controlled to be 40-50 DEG C.
[0033] (3) After the addition of adamantane is completed, the temperature is kept at 40-50 DEG C for 3-4 hours, and the reaction is stopped when the content of adamantane is less than 0.5%.
[0034] (4) The temperature of the reaction kettle is increased to 70 DEG C, and the residual bromine is distilled.
[0035] (5) 2000 kg of hydrobromic acid with a concentration of 30% is added and stirred for 30 minutes, the liquid is separated, 1-bromoadamantane is washed, dried, and the purity of 1-bromoadamantane is more than 99.5% after sampling and testing, and 11200 kg of 1-bromoadamantane product is obtained.
[0036] The present application utilizes the characteristics that bromine is both a reactant and a solvent, increases the bromine dosage, smoothly reduces the reaction temperature, accelerates the reaction rate, greatly shortens the whole reaction time, and significantly improves the yield efficiency; utilizes the characteristics that hydrobromic acid can well dissolve bromine but not 1-bromoadamantane, well removes the residual bromine in the reaction system, 1-bromoadamantane is not easy to produce side reactions in the acidic system with water, and makes the product purity reach more than 99.5%.
[0037] Example 4, the present application is a preparation method of 1-bromoadamantane, comprising the following steps, the following are mass percentages:
[0038] (1) 16000 kg of liquid bromine is added into a 10000 L reaction kettle at normal temperature and pressure.
[0039] (2) At normal temperature, adamantane is added at a speed of 800 kg / h, the total amount of adamantane is controlled to be 7500 kg, and the temperature is controlled to be 40-50 DEG C.
[0040] (3) After the addition of adamantane, the temperature is kept at 40-50℃ for 3-4 hours, and sampling is conducted. When the content of adamantane is less than 0.5%, the reaction is stopped.
[0041] (4) The temperature of the reactor is increased to 70℃, and the residual bromine is distilled.
[0042] (5) 2000kg of 30% hydrobromic acid is added and stirred for 30 minutes. After the liquid is separated, the 1-bromoadamantane is washed and dried. Sampling shows that the purity of 1-bromoadamantane is more than 99.7%, and 11800kg of 1-bromoadamantane product is obtained.
[0043] The present application takes advantage of the characteristics that bromine is both a reactant and a solvent, increases the amount of bromine, successfully reduces the reaction temperature, and accelerates the reaction rate, so that the whole reaction time is greatly shortened, and the production efficiency is significantly improved. The present application takes advantage of the characteristics that hydrobromic acid can well dissolve bromine but not 1-bromoadamantane, and the residual bromine in the reaction system is well removed. In the presence of water, the acidic system is not easy to produce side reactions, so that the purity of the product is more than 99.7%.
[0044] Example 5, the present application is a preparation method of 1-bromoadamantane, which comprises the following steps, the following are in mass percentage:
[0045] (1) At normal temperature and pressure, 16000kg of liquid bromine is added to a 10000L reactor.
[0046] (2) At normal temperature, adamantane is added at a speed of 800kg / h, and the total amount of adamantane is controlled to be 7500kg, and the temperature is controlled to be 40-50℃.
[0047] (3) After the addition of adamantane, the temperature is kept at 40-50℃ for 3-4 hours, and sampling is conducted. When the content of adamantane is less than 0.5%, the reaction is stopped.
[0048] (4) The temperature of the reactor is increased to 70℃, and the residual bromine is distilled.
[0049] (5) 3500kg of 47% hydroiodic acid is added and stirred for 30 minutes. After the liquid is separated, the 1-bromoadamantane is washed and dried. Sampling shows that the purity of 1-bromoadamantane is more than 97.2%, and 11600kg of 1-bromoadamantane product is obtained.
[0050] The present application utilizes the characteristics that bromine is both a reactant and a solvent, increases the bromine dosage, smoothly reduces the reaction temperature, accelerates the reaction rate, greatly shortens the whole reaction time, and significantly improves the yield efficiency; utilizes the characteristics that hydroiodic acid can well dissolve bromine but not 1-bromoadamantane, well removes the residual bromine in the reaction system, 1-bromoadamantane is not easy to produce side reactions in the acidic system with water, and the product purity reaches above 97.2%.
[0051] Example 6, the present application is a preparation method of 1-bromoadamantane, comprising the following steps, the following are mass percentages:
[0052] (1) 12000 kg of liquid bromine is added into a 10000 L reaction kettle at normal temperature and pressure.
[0053] (2) At normal temperature, adamantane is added at a speed of 800 kg / h, the total amount of adamantane is controlled to be 6000 kg, and the temperature is controlled to be 40-50 DEG C.
[0054] (3) After the addition of adamantane is completed, the temperature is kept at 40-50 DEG C for 3-4 hours, and the reaction is stopped when the content of adamantane is less than 0.5%.
[0055] (4) The temperature of the reaction kettle is increased to 70 DEG C, and the residual bromine is distilled.
[0056] (5) 2500 kg of 30% phosphoric acid is added and stirred for 30 minutes, the liquid is separated, 1-bromoadamantane is washed, dried, and the purity of 1-bromoadamantane is above 96.7% after sampling and testing, and 9380 kg of 1-bromoadamantane product is obtained.
[0057] The present application utilizes the characteristics that bromine is both a reactant and a solvent, increases the bromine dosage, smoothly reduces the reaction temperature, accelerates the reaction rate, greatly shortens the whole reaction time, and significantly improves the yield efficiency; utilizes the characteristics that hydroiodic acid can well dissolve bromine but not 1-bromoadamantane, well removes the residual bromine in the reaction system, 1-bromoadamantane is not easy to produce side reactions in the acidic system with water, and the product purity reaches above 96.7%.
[0058] Example 7, the present application is a preparation method of 1-bromoadamantane, comprising the following steps, the following are mass percentages:
[0059] (1) 12000 kg of liquid bromine is added into a 10000 L reaction kettle at normal temperature and pressure.
[0060] (2) At normal temperature, adamantane is added at a speed of 800 kg / h, the total amount of adamantane is controlled to be 6000 kg, and the temperature is controlled to be 40-50 DEG C.
[0061] (3) After the adamantane is added, the temperature is kept at 40-50℃ for 3-4 hours, and sampling is tested. When the content of adamantane is less than 0.5%, the reaction is stopped.
[0062] (4) The temperature of the reactor is increased to 70℃, and the residual bromine is distilled.
[0063] (5) 2500kg of 75% sulfuric acid is added and stirred for 30 minutes. After the liquid is separated, the 1-bromoadamantane is washed, dried, and sampling is tested. The purity of the 1-bromoadamantane is more than 95.3%, and 9290kg of 1-bromoadamantane product is obtained.
[0064] The present application takes advantage of the characteristics that bromine is both a reactant and a solvent. After increasing the amount of bromine, the reaction temperature is successfully reduced, and the reaction rate is accelerated, so that the whole reaction time is greatly shortened, and the yield efficiency is significantly improved. The present application takes advantage of the characteristics that hydrobromic acid can well dissolve bromine but not 1-bromoadamantane, so that the residual bromine in the reaction system is well removed. In the presence of water, the 1-bromoadamantane is not easy to produce side reactions in an acidic system, so that the purity of the product is more than 95.3%.
[0065] Finally, as can be seen from the following table data comparison, the preferred scheme is to use hydrobromic acid as a bromine dispersant to obtain high yield and high purity 1-bromoadamantane.
[0066]
[0067] The above is only part of the preferred examples of the present application, and any skilled person in the art can modify the above-described technical solutions or modify them into equivalent technical solutions. Therefore, the corresponding simple modifications or equivalent transformations according to the technical solutions of the present application are all within the scope of protection claimed by the present application.
[0068] The legend is a gas chromatogram, and the chromatographic conditions are as follows: SE-30 cross-linked column with a length of 50m, an inner diameter of 0.32mm, and a liquid film thickness of 0.5um. Initial temperature: 80℃, holding time: 5min; first-order temperature rising rate: 8℃ / min, first-order final temperature: 150℃, holding time: 1min; second-order temperature rising rate: 30℃ / min, second-order final temperature: 250℃, holding time: 20min. The workstation lock time is 2min. The gasification chamber temperature is 280℃, and the detection chamber temperature is 290℃.
[0069] Figure 1 In the table, serial numbers 1-6 represent the order of each component in the chromatogram according to the retention time in the 1-bromoadamantane sample, and the fourth component is the main product 1-bromoadamantane. Figure 2In the table, serial numbers 1-9 represent the order of each component in the chromatogram according to the retention time of the 1-bromoadamantane sample, and the 6th component is the main product 1-bromoadamantane.
Claims
1. A method for preparing 1-bromoadamantane, characterized in that: Using adamantane and liquid bromine as raw materials, under normal pressure, at a reaction temperature of 40-50℃, and for 3-4 hours, bromine dispersant was added, and after solid-liquid separation and simple rinsing, 1-bromoadamantane was obtained.
2. The method for preparing 1-bromoadamantane according to claim 1, characterized in that: The steps and process for adding ingredients are as follows: (1) Add liquid bromine into the reactor at room temperature and pressure. The volume of liquid bromine added can be 40% to 50% of the reactor volume. (2) At room temperature, add adamantane at a rate of 800 kg / h, control the total amount of adamantane to be 1:2 of the mass ratio of liquid bromine, and control the temperature to be 40-50℃; (3) After the adamantane is added, the temperature is maintained at 40-50℃ for 3-4 hours. Samples are taken for testing. When the adamantane content is less than 0.5%, the reaction is stopped and the excess bromine is distilled off. (4) After adding bromine dispersant, stir for 30 minutes to separate the residual bromine. Rinse and dry 1-bromoadamantane to obtain 1-bromoadamantane product.
3. The method for preparing 1-bromoadamantane according to claim 2, characterized in that: In steps (1) and (2), the total amount of material added is 65% to 75% of the total volume of the reactor.
4. The method for preparing 1-bromoadamantane according to claim 2, characterized in that: The dispersant in step (4) is one or more of hydrobromic acid, hydroiodic acid, sulfuric acid or phosphoric acid.