Method for co-production of adamantane and exo-tetrahydrodicyclopentadiene

Abstract

The invention relates to a method for co-production of adamantane and exo-tetrahydrodicyclopentadiene, which comprises the following steps: taking bridge-type tetrahydrodicyclopentadiene as a raw material, taking anhydrous aluminum trichloride as a catalyst, adding a solvent into the anhydrous aluminum trichloride, and uniformly mixing; according to the liquid holdup of the dynamic tubular reactor, continuous feeding is carried out to prepare exo-tetrahydrodicyclopentadiene: the material feeding speed is controlled to control the reaction time to be 0.5-1 h; preparing adamantane: controlling the material feeding speed to control the reaction time to be 2-3 hours; the hanging tetrahydrodicyclopentadiene post-treatment process comprises the following steps: after reaction liquid is discharged from a discharge port, adding 1m / m of water for washing, adjusting the pH value to 7, then separating the liquid, desolventizing an organic phase, and distilling and purifying to obtain hanging tetrahydrodicyclopentadiene; and an adamantane post-treatment process: after the reaction liquid is discharged from a discharge port, keeping the temperature at 75-80 DEG C, adding 1m / m of water for washing, adjusting the pH value to be 7, separating the liquid, and desolventizing an organic phase to obtain an adamantane crude product, adding the adamantane crude product into a hanging liquid according to the proportion of 1m / m for crystallization, slowly cooling to 0-5 DEG C, filtering after crystallization, adding 0.5 m / m of water for leaching, and drying a filter cake to obtain the pure adamantane.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for co-producing adamantane and hanging tetrahydrodicyclopentadiene. BACKGROUND

[0002] Adamantane, molecular formula C10H16, its carbon skeleton structure is equivalent to a unit cell in the diamond lattice network, hence the name adamantane. Adamantane is colorless crystals, mainly used for the synthesis of anticancer, antitumor and other special drugs, etc. It can also be used to prepare high-grade lubricants, photographic photosensitive materials surfactants, pesticides, catalysts, etc. The hydrogen on the bridgehead carbon atoms (i.e. 1,3,5,7) of adamantane is easy to undergo substitution reaction. For example, adamantane reacts with excess bromine to form 1-bromo adamantane; reacts with nitrogen dioxide at 175℃ to form 1-nitro adamantane; oxidized with chromium trioxide and acetic acid to form 1-adamantanol. Its derivatives can be used as drugs, for example, 1-ammonium adamantane hydrochloride and 1-adamantyl ethylamine hydrochloride can prevent and treat influenza caused by A2 virus.

[0003] Adamantane is used for the synthesis of adamantane derivatives, which are widely used in the preparation of various special drugs such as antitumor, negative hydrogen ion transfer agent, lubricating material, modified film material, new type of photoelectric material, carrier, etc.

[0004] Chinese patent publication No. CN101229990A discloses a two-step one-cycle method for producing adamantane. The patent introduces a method for producing adamantane, which uses bridged dicyclopentadiene as raw material and aluminum chloride as catalyst to generate hanging dicyclopentadiene, then adds a small amount of aluminum chloride to the hanging dicyclopentadiene to generate crude adamantane, and after crystallization, washing and impurity removal, pure adamantane is obtained. This method is a two-step method for preparing adamantane, although the amount of aluminum chloride used is reduced, but the amount of adamantane produced each time is limited, for example, when the reaction temperature is 50-100℃ and the concentration of adamantane in the reaction reaches 1-30%, the reaction is terminated and the post-treatment is carried out, the efficiency of industrial production is not high.

[0005] Chinese patent publication No. CN117342921A discloses a method for preparing adamantane from dicyclopentadiene, which comprises: loading traditional hydrogenation catalyst in the upper section of a fixed bed reactor, separating the middle section with inert material quartz sand, and loading isomerization catalyst in the lower section, then mixing dicyclopentadiene and reaction solvent uniformly and adding them into the fixed bed reactor, through hydrogenation in the upper section and isomerization in the lower section, dicyclopentadiene is continuously converted into adamantane. The industrial operability of this process is not good. SUMMARY

[0006] The present application improves the above-mentioned prior art, that is, the technical problem to be solved by the present application is to provide a method for co-producing adamantane and hanging tetrahydrodicyclopentadiene.

[0007] In order to achieve the above object, the technical scheme adopted by the present application is as follows: A method for co-producing adamantane and hanging type tetrahydrodicyclopentadiene, the method comprises the following steps: Step (1): taking bridge type tetrahydrodicyclopentadiene as raw material, taking anhydrous aluminum chloride as catalyst, adding a solvent into the anhydrous aluminum chloride, and stirring to mix uniformly; Step (2): according to the liquid holdup of the dynamic tubular reactor, continuously feeding, wherein the hanging type tetrahydrodicyclopentadiene is prepared: controlling the material feeding speed to control the reaction time to be 0.5-1h; the adamantane is prepared: controlling the material feeding speed to control the reaction time to be 2-3h; Step (3): hanging type tetrahydrodicyclopentadiene post-processing procedure: after the reaction liquid comes out from the discharge port, 1m / m water is added for washing, sodium bicarbonate is added to adjust pH=7, then the organic phase is separated and distilled to purify the hanging type tetrahydrodicyclopentadiene; adamantane post-processing procedure: after the reaction liquid comes out from the discharge port, it is kept at 75-80℃, 1m / m water is added for washing, sodium bicarbonate is added to adjust pH=7, then the organic phase is separated and distilled to obtain the crude adamantane, which is added into the hanging type at a proportion of 1m / m for crystallization, slowly cooled to 0-5℃, filtered after crystallization, 0.5m / m water is added for washing, and the filter cake is dried to obtain the pure adamantane.

[0008] Further, in step (1), the raw material and the catalyst solution are respectively fed from the first feeding port and the second feeding port of the dynamic tubular reactor.

[0009] Further, the first feeding port and the second feeding port of the dynamic tubular reactor are on the same horizontal line on both sides.

[0010] Further, in step (2), the feeding ratio of bridge type tetrahydrodicyclopentadiene to aluminum chloride is controlled to be 1:0.15-0.2, the reaction temperature is controlled to be 25-45℃, and the hanging type tetrahydrodicyclopentadiene is controlled to be generated. Further, in step (2), the feeding ratio of bridge type tetrahydrodicyclopentadiene to aluminum chloride is controlled to be 1:0.4-0.6, the reaction temperature is controlled to be 70-100℃, and the hanging type tetrahydrodicyclopentadiene is controlled to be generated.

[0011] Further, in step (1), the solvent added into the anhydrous aluminum chloride is dichloromethane, dichloroethane, carbon tetrachloride, n-heptane or n-hexane, etc., and the solvent dosage is 1m / m of the weight of the anhydrous aluminum chloride.

[0012] Further, in step (1), the bridge type tetrahydrodicyclopentadiene is kept at 75-80℃ to control its feeding in a molten state.

[0013] Furthermore, in the post-processing step of hanging tetrahydrodicyclopentadiene in step (3), the vacuum degree is controlled at 90 kPa to 100 kPa, and the receiving top temperature is 70°C to 80°C to distill into hanging tetrahydrodicyclopentadiene.

[0014] Furthermore, in the adamantane post-treatment process in step (3), the filtrate is used as the mother liquor for the next batch of adamantane crude crystallization.

[0015] Compared with the prior art, the present invention has the following advantages: the synthesis method of the present invention is simple and the process conditions are not harsh, it causes less environmental pollution, and the output of hanging tetrahydrodicyclopentadiene or adamantane can be adjusted according to market conditions. It has a higher yield than the prior art and minimizes the complexity and cost related to the process steps, making it suitable for industrial production. Detailed Implementation

[0016] The present invention will now be described in further detail with reference to specific embodiments.

[0017] In the description of this invention, it should be understood that the terms "longitudinal", "lateral", "up", "down", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicating orientation or positional relationships, are only for the convenience of describing this invention, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention.

[0018] This invention discloses a method for the co-production of pendant tetrahydrodicyclopentadiene from adamantane, the method comprising the following steps: Step (1): Using bridged tetrahydrodicyclopentadiene as raw material and anhydrous aluminum trichloride as catalyst, solvent is added to anhydrous aluminum trichloride and stirred until uniform; the raw material and catalyst solution are fed into the first feed port and the second feed port of the dynamic tubular reactor, respectively. Step (2): Based on the liquid holdup of the dynamic tubular reactor, the feed is continuously fed. For the preparation of hanging tetrahydrodicyclopentadiene: the feed rate is controlled to control the reaction time to 0.5-1h (i.e., the time from feed to discharge is 0.5-1h); for the preparation of adamantane: the feed rate is controlled to control the reaction time to 2-3h (i.e., the time from feed to discharge is 2-3h). Step (3): Post-processing of hanging tetrahydrodicyclopentadiene: After the reaction solution comes out of the outlet, add 1 m / m (with the bridge tetrahydrodicyclopentadiene as 1) of water for washing, add sodium bicarbonate to adjust the pH to 7, then separate the liquid and remove the organic phase. After desolventizing, distill to purify the hanging tetrahydrodicyclopentadiene. The vacuum degree is controlled at 90 kPa to 100 kPa, and the receiving top temperature is 70℃ to 80℃. The distillation fraction is the hanging tetrahydrodicyclopentadiene. Post-processing of adamantane: After the reaction solution comes out of the outlet, keep it at 75-80℃, add 1 m / m (with bridge tetrahydrodicyclopentadiene as 1) water for washing, add sodium bicarbonate to adjust pH=7, then separate the liquid and extract the organic phase. After desolvation, crude adamantane is obtained. Add it to the hanging container at a ratio of 1 m / m (crude product: hanging container) for crystallization. Slowly cool to 0-5℃, filter after crystallization, add 0.5 m / m water for rinsing, and dry the filter cake to obtain pure adamantane.

[0019] Specifically, the first and second feed inlets of the dynamic tubular reactor are on the same horizontal line on both sides.

[0020] In one scheme, in step (2), the amount of anhydrous aluminum trichloride is controlled to be 0.15-0.2 eq (with bridged tetrahydrodicyclopentadiene as 1), that is, the feed ratio of bridged tetrahydrodicyclopentadiene to aluminum trichloride is controlled to be 1:0.15~0.2, the reaction temperature is 25-45℃, and the hanging tetrahydrodicyclopentadiene is generated.

[0021] In another scheme, in step (2), the amount of anhydrous aluminum trichloride is controlled to be 0.4-0.6 eq (with bridged tetrahydrodicyclopentadiene as 1), that is, the feed ratio of bridged tetrahydrodicyclopentadiene to aluminum trichloride is controlled to be 1:0.4-0.6, the reaction temperature is 70-100℃, and the hanging tetrahydrodicyclopentadiene is generated.

[0022] Specifically, in step (1), the solvent added to the anhydrous aluminum chloride is dichloromethane, dichloroethane, carbon tetrachloride, n-heptane or n-hexane, etc., and the amount of solvent used is 1 m / m of the weight of the anhydrous aluminum chloride.

[0023] Specifically, in step (1), the bridge-type tetrahydrodicyclopentadiene is kept at 75-80℃ and fed in a molten state.

[0024] Specifically, in step (1), after adding solvent to anhydrous aluminum trichloride, the mixture is kept under stirring and fed using a pump, such as a peristaltic pump or other suitable feed pump. The peristaltic pump must use a fluorinated rubber tube that is resistant to acid corrosion.

[0025] Specifically, in the adamantane post-processing step (3), the filtrate is used as the mother liquor for the next batch of adamantane crude crystallization.

[0026] The following examples use a dynamic tubular reactor with a liquid holdup of 1L as an example. Example 1 Preparation of hanging tetrahydrodicyclopentadiene Prepare 1362.3g of bridged tetrahydrodicyclopentadiene and maintain the temperature at 75-80℃ to make it liquid. Prepare 200g of anhydrous aluminum trichloride and add 200g of dichloromethane, stirring for later use. Control the feed equivalence ratio of bridged tetrahydrodicyclopentadiene to aluminum trichloride at 1:0.15, the reaction temperature at 25-35℃, and the material discharge time from feed to discharge at 1 hour. After the reaction liquid is completely discharged, add the reaction liquid to 1362.3g of water, stir and wash, add sodium bicarbonate to adjust the pH to 7, let stand and separate the liquids. After desolvation of the organic phase, distillation is performed under vacuum of 90kPa-100kPa and receiving top temperature of 70℃-80℃. The distillate is 1158g of hanging tetrahydrodicyclopentadiene (yield 85%, purity 98.7%).

[0027] Example 2 Preparation of hanging tetrahydrodicyclopentadiene Prepare 1362.3g of bridged tetrahydrodicyclopentadiene and maintain the temperature at 75-80℃ to make it liquid. Prepare 267g of anhydrous aluminum trichloride and add it to 267g of dichloroethane and stir. Control the feed equivalence ratio of bridged tetrahydrodicyclopentadiene to aluminum trichloride at 1:0.2, the reaction temperature at 35-45℃, and the material time from feed to discharge at 0.5h. After the reaction liquid is completely discharged, add the reaction liquid to 1362.3g of water and stir and wash. Add sodium bicarbonate to adjust the pH to 7, let it stand and separate the liquids. After desolvation of the organic phase, distill it under a vacuum of 90kPa-100kPa and a receiving top temperature of 70℃-80℃. The distillate is 10623g of hanging tetrahydrodicyclopentadiene (yield 78%, purity 99.2%).

[0028] Example 3 Preparation of hanging tetrahydrodicyclopentadiene Prepare 1362.3g of bridged tetrahydrodicyclopentadiene and maintain the temperature at 75-80℃ to make it liquid. Prepare 240g of anhydrous aluminum trichloride and add it to 240g of dichloroethane, stirring. Control the feed equivalence ratio of bridged tetrahydrodicyclopentadiene to aluminum trichloride at 1:0.18, the reaction temperature at 35-45℃, and the material discharge time at 0.5h. After the reaction liquid has completely discharged, add the reaction liquid to 1362.3g of water and stir to wash. Add sodium bicarbonate to adjust the pH to 7, allow to stand and separate the liquids. After desolvation of the organic phase, distillation is performed under vacuum of 90kPa-100kPa and a receiving top temperature of 70℃-80℃. The distillate is 1131g of hanging tetrahydrodicyclopentadiene (yield 83%, purity 98.3%).

[0029] Example 4 Preparation of adamantane Prepare 1362.3g of bridged tetrahydrodicyclopentadiene and maintain the temperature at 75-80℃ to make it liquid. Prepare 534g of anhydrous aluminum trichloride and add 534g of cyclohexane with stirring. Control the feed equivalence ratio of bridged tetrahydrodicyclopentadiene to aluminum trichloride at 1:0.4, the reaction temperature at 90-100℃, and the material time from feed to discharge at 3 hours. After the reaction liquid is completely discharged, maintain the temperature at 75-80℃, add 1362.3g of water and stir and wash. Add sodium bicarbonate to adjust the pH to 7, then separate the liquid. After desolvation of the organic phase, crude adamantane is obtained. Take a batch of hanging container as the crystallization mother liquor and add crude adamantane to it at a ratio of 1m / m (crude product: hanging container) for crystallization. Slowly cool to 0-5℃, filter after crystallization, add 681g of water to rinse, and dry the filter cake to obtain 722g of pure adamantane (yield 53%, purity 99.5%).

[0030] The mother liquor for crystallization contained 5.1% adamantane, so the next batch of crude adamantane was used for crystallization.

[0031] Example 5 Preparation of adamantane Prepare 1362.3g of bridged tetrahydrodicyclopentadiene and maintain the temperature at 75-80℃ to make it liquid. Prepare 667g of anhydrous aluminum trichloride and add 667g of n-heptane, stirring for later use. Control the feed equivalence ratio of bridged tetrahydrodicyclopentadiene to aluminum trichloride at 1:0.5, the reaction temperature at 80-90℃, and the material time from feed to discharge at 3 hours. After the reaction liquid is completely discharged, maintain the temperature at 75-80℃, add 1362.3g of water, stir and wash, add sodium bicarbonate to adjust the pH to 7, then separate the liquid and extract the organic phase to obtain crude adamantane. Take a batch of hanging containers as the mother liquor for crystallization. Add crude adamantane to it at a ratio of 1 m / m (crude product: hanging container) for crystallization. Slowly cool down to 0-5℃. After crystallization, filter and rinse with 681g of water. After drying the filter cake, 640.3g of pure adamantane is obtained (yield 47%, purity 99.7%).

[0032] The mother liquor for crystallization contained 5.7% adamantane, so the next batch of crude adamantane was used for crystallization.

[0033] Example 6 Preparation of adamantane Prepare 1362.3g of bridged tetrahydrodicyclopentadiene and maintain the temperature at 75-80℃ to make it liquid. Prepare 800g of anhydrous aluminum trichloride and add 800g of carbon tetrachloride, stirring for later use. Control the feed equivalent ratio of bridged tetrahydrodicyclopentadiene to aluminum trichloride at 1:0.6, the reaction temperature at 70-80℃, and the material time from feed to discharge at 2 hours. After the reaction liquid is completely discharged, maintain the temperature at 75-80℃, add 1362.3g of water, stir and wash, add sodium bicarbonate to adjust the pH to 7, and then separate the liquid. After desolvation of the organic phase, crude adamantane is obtained. Take a batch of hanging container as the crystallization mother liquor, add crude adamantane to it at a ratio of 1m / m (crude product: hanging container) for crystallization, slowly cool to 0-5℃, filter after crystallization, add 681g of water to rinse, and dry the filter cake to obtain 613g of pure adamantane (yield 45%, purity 99.7%).

[0034] The mother liquor for crystallization contained 4.7% adamantane, so the next batch of crude adamantane was used for crystallization.

[0035] Example 7 Crystallization mother liquor reuse Following any of the above-described embodiments 4-6, crude adamantane was obtained. A batch of crystallization mother liquor was reused, and crude adamantane was added to it at a ratio of 1 m / m (crude product: hanging type) for crystallization. The temperature was slowly lowered to 0-5°C. After crystallization, the mixture was filtered, and 681 g of water was added for rinsing. After drying the filter cake, 749 g of pure adamantane was obtained (yield 55%, purity 99.2%).

[0036] The mother liquor for crystallization contained 7.8% adamantane, so the next batch of crude adamantane was used for crystallization.

[0037] This invention provides a method for the continuous production of adamantane and co-production of tetrahydrodicyclopentadiene, which can be adjusted to produce tetrahydrodicyclopentadiene or adamantane according to market conditions. This method is simple, has undemanding process conditions, and causes minimal environmental pollution. Compared to existing technologies, it offers higher yields, avoids some of the drawbacks associated with existing methods, and minimizes the complexity and cost associated with process steps, making it suitable for industrial production.

[0038] If this invention discloses or relates to components or structural parts that are fixedly connected to each other, then, unless otherwise stated, a fixed connection can be understood as: a fixed connection that can be detached (e.g., using bolts or screws), or a fixed connection that cannot be detached (e.g., riveting, welding). Of course, a fixed connection can also be replaced by an integral structure (e.g., manufactured in one piece using a casting process) (except where it is obviously impossible to use an integral molding process).

[0039] In addition, unless otherwise stated, the terms used in any of the technical solutions disclosed in this invention to indicate positional relationships or shapes include states or shapes that are similar to, close to, or approximate with those states or shapes.

[0040] Any component provided by this invention can be assembled from multiple individual components or can be a single component manufactured by a one-piece molding process.

[0041] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications can still be made to the specific implementation of the present invention or equivalent substitutions can be made to some technical features without departing from the spirit of the technical solutions of the present invention, and all such modifications and substitutions should be covered within the scope of the technical solutions claimed in the present invention.

Claims

1. A process for the co-production of adamantane and exo-tetrahydrodicyclopentadiene, characterized by: The method comprises the following steps: Step (1): taking bridged tetrahydrodicyclopentadiene as raw material, adding a solvent to anhydrous aluminum chloride, and stirring to mix uniformly, with anhydrous aluminum chloride as catalyst; Step (2): according to the liquid holdup of the dynamic tubular reactor, continuously feeding to prepare the hanging tetrahydrodicyclopentadiene: controlling the material feeding speed to control the reaction time to be 0.5-1h; preparing the adamantane: controlling the material feeding speed to control the reaction time to be 2-3h; Step (3): hanging tetrahydrodicyclopentadiene post-treatment process: after the reaction liquid comes out of the discharge port, 1m / m water is added for washing, sodium bicarbonate is added to adjust pH to 7, then the organic phase is separated and distilled to purify the hanging tetrahydrodicyclopentadiene; adamantane post-treatment process: after the reaction liquid comes out of the discharge port, it is kept at 75-80℃, 1m / m water is added for washing, sodium bicarbonate is added to adjust pH to 7, then the organic phase is separated, and the obtained crude adamantane is added to the hanging type at a proportion of 1m / m for crystallization, slowly cooled to 0-5℃, filtered after crystallization, 0.5m / m water is added for washing, and the filter cake is dried to obtain pure adamantane.

2. The process for co-production of adamantane and quadricyclane according to claim 1, characterized by that: In step (1), the raw material and the catalyst solution are respectively fed from the first feeding port and the second feeding port of the dynamic tubular reactor.

3. The process for co-production of adamantane and quadricyclane according to claim 2, characterized in that: The first feeding port and the second feeding port of the dynamic tubular reactor are on the same horizontal line on both sides.

4. The process for co-production of adamantane and quadricyclane according to claim 1, characterized in that: In step (2), the feeding ratio of bridged tetrahydrodicyclopentadiene to aluminum chloride is controlled to be 1:0.15-0.2, the reaction temperature is controlled to be 25-45℃, and the hanging tetrahydrodicyclopentadiene is controlled to be generated.

5. The method of claim 1, wherein the adamantane co-production of the hanging type tetrahydrodicyclopentadiene is characterized by: In step (2), the feeding ratio of bridged tetrahydrodicyclopentadiene to aluminum chloride is controlled to be 1:0.4-0.6, the reaction temperature is controlled to be 70-100℃, and the hanging tetrahydrodicyclopentadiene is controlled to be generated.

6. The method of claim 1, wherein the adamantane co-production of the hanging type tetrahydrodicyclopentadiene is characterized by: In step (1), the solvent added to the anhydrous aluminum chloride is dichloromethane, dichloroethane, carbon tetrachloride, n-heptane or n-hexane, etc., and the solvent amount is 1m / m of the weight of the anhydrous aluminum chloride.

7. The method of claim 1, wherein the adamantane co-production of the hanging type tetrahydrodicyclopentadiene is characterized by: In step (1), the bridged tetrahydrodicyclopentadiene is kept at 75-80℃ to control its feeding state to be molten.

8. The method of claim 1, wherein the adamantane co-production of the hanging type tetrahydrodicyclopentadiene is characterized by: In step (3), in the hanging tetrahydrodicyclopentadiene post-treatment process, the vacuum degree is controlled to be 90kpa-100kpa, and the receiving top temperature is controlled to be 70℃-80℃, and the fraction is the hanging tetrahydrodicyclopentadiene.

9. The method of claim 1, wherein the adamantane co-production of the hanging type tetrahydrodicyclopentadiene is characterized by: In step (3), in the adamantane post-treatment process, the filtrate is used as the crystallization mother liquor to continue to be used for crystallization of the next batch of crude adamantane.