JP2013032344A - Process for production of 2-adamantanone - Google Patents
Process for production of 2-adamantanone Download PDFInfo
- Publication number
- JP2013032344A JP2013032344A JP2012146243A JP2012146243A JP2013032344A JP 2013032344 A JP2013032344 A JP 2013032344A JP 2012146243 A JP2012146243 A JP 2012146243A JP 2012146243 A JP2012146243 A JP 2012146243A JP 2013032344 A JP2013032344 A JP 2013032344A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- reaction
- adamantanone
- adamantane
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、２−アダマンタノンの製造方法に関する。 The present invention relates to a method for producing 2-adamantanone.
アダマンタンは、ダイヤモンド構造単位と同じ構造を有する対称性の高いカゴ型化合物として知られ、（１）分子の歪みエネルギーが少なく、熱安定性に優れ、（２）炭素密度が大きいため脂溶性が大きく、（３）昇華性があるにもかかわらず、臭いが少ない等の特徴を有する。
アダマンタンは、１９８０年代からは医薬品分野においてパーキンソン氏病治療薬、インフルエンザ治療薬原料として注目されていたが、近年アダマンタン誘導体の有する耐熱性や透明性等の特性が、半導体製造用フォトレジスト、磁気記録媒体、光ファイバー、光学レンズ、光ディスク基板原料等の光学材料；耐熱性プラスティック、塗料、接着剤等の機能性材料；化粧品等の分野で注目され、その用途が増大しつつある。また、医薬分野においても抗癌剤、脳機能改善、神経性疾患、抗ウイルス剤原料としての需要が増大してきている。
Adamantane is known as a highly symmetrical cage compound having the same structure as the diamond structural unit. (1) Low molecular strain energy, excellent thermal stability, and (2) High carbon solubility due to high carbon density (3) Despite the sublimation property, it has a feature such as little odor.
Adamantane has been attracting attention as a raw material for treating Parkinson's disease and influenza in the pharmaceutical field since the 1980s. In recent years, adamantane derivatives have characteristics such as heat resistance and transparency, which are used in semiconductor manufacturing photoresists and magnetic recording. Optical materials such as media, optical fibers, optical lenses, and optical disk substrate materials; functional materials such as heat-resistant plastics, paints, and adhesives; In the pharmaceutical field, the demand for anticancer agents, brain function improvement, neurological diseases, and antiviral materials is increasing.
炭化水素化合物を酸化してアルコールやケトンに変換する技術は炭素資源の有効活用の観点から、工業的にも非常に重要な技術である。
２−アダマンタノンを選択的に製造する技術としては濃硫酸中で製造する方法が公知である。例えばSchlatmannは１−アダマンタノールを濃硫酸中、３０℃で１２時間加熱保持することにより、７２％の収率で２−アダマンタノンが得られることを報告している（非特許文献１）。また、アダマンタンを濃硫酸により酸化した後、水蒸気蒸留により精製することで４７〜４８％の収率でアダマンタノンが得られることも知られている（非特許文献２）。
The technology for oxidizing hydrocarbon compounds and converting them into alcohols and ketones is a very important technology from the viewpoint of effective utilization of carbon resources.
As a technique for selectively producing 2-adamantanone, a method for producing it in concentrated sulfuric acid is known. For example, Schlatmann reports that 2-adamantanone can be obtained in a yield of 72% by heating and maintaining 1-adamantanol in concentrated sulfuric acid at 30 ° C. for 12 hours (Non-patent Document 1). It is also known that adamantane is obtained in a yield of 47 to 48% by oxidizing adamantane with concentrated sulfuric acid and then purifying by steam distillation (Non-patent Document 2).
上記技術の改良法として、反応を２段階又は３段階で昇温して実施する方法が提案されている（特許文献１及び２）。しかし、これらの方法はアダマンタノンの収率は向上する（最高で収率９０％）ものの、反応速度が遅く、その収率を得るためには非常に長時間（３０ｈ以上）反応させる必要があるという問題点があった。
また、硫酸ナトリウム等の無機塩（特許文献３）、五酸化リン等の乾燥剤（特許文献４）、ヨウ素等ハロゲン単体あるいはヨウ化カリウム等のハロゲン化金属（特許文献５）を反応系に添加する方法も提案されている。しかし、これらの方法はアダマンタノン収率は向上する（特許文献４で最高収率９３％）ものの、特許文献３では反応速度が遅く、非常に長時間（３０ｈ以上）反応させる必要がある。また特許文献４及び５では添加物を含んだ廃硫酸の処理が困難であり、工業的な利用は難しかった。
上記の他、酸素存在下で超音波を利用する方法も提案されているが（特許文献６）、設備に多大な費用を必要とし、工業的な実施は困難であった。
As an improved method of the above technique, a method of carrying out the reaction by raising the temperature in two or three stages has been proposed (Patent Documents 1 and 2). However, although these methods improve the yield of adamantanone (maximum yield of 90%), the reaction rate is slow, and it is necessary to carry out the reaction for a very long time (30 hours or more) in order to obtain the yield. There was a problem.
Also, an inorganic salt such as sodium sulfate (Patent Document 3), a desiccant such as phosphorus pentoxide (Patent Document 4), a halogen alone such as iodine, or a metal halide such as potassium iodide (Patent Document 5) is added to the reaction system. A method to do this has also been proposed. However, these methods improve the adamantanone yield (maximum yield of 93% in Patent Document 4), but in Patent Document 3, the reaction rate is slow and it is necessary to carry out the reaction for a very long time (30 hours or more). Further, in Patent Documents 4 and 5, it is difficult to treat waste sulfuric acid containing additives, and industrial utilization is difficult.
In addition to the above, a method using ultrasonic waves in the presence of oxygen has also been proposed (Patent Document 6), but it requires a large amount of equipment and is difficult to implement industrially.
２−アダマンタノンの選択的製造において、硫酸は酸化剤かつ触媒として機能し、反応速度及び選択率は、硫酸濃度が大きく影響する。反応に伴い硫酸が消費されて希薄化することで反応速度が低下するが、この点を補うため反応中に三酸化硫黄又は発煙硫酸を添加し、硫酸濃度の低下を抑制する方法が提案されている（特許文献７、８及び９）。これら方法により反応速度は向上するが、選択性及び収率は工業的に充分といえなかった。
また、特許文献１−９は、全て硫酸濃度を９５％以上としており、硫酸濃度が９５％未満の希薄な濃度では反応速度が低下し、短時間で高収率に反応を完結させることは困難であった。このような硫酸希薄濃度での反応を行うには、原料として１−アダマンタノールを用いる必要があり、アダマンタンには適さないことが知られている（特許文献１０）。
２−アダマンタノンの選択的製造を１，２−ジクロロエタン等のハロゲン化アルカン溶媒を添加して行った場合には、原料アダマンタンの昇華が抑制されるだけでなく反応速度が促進され、２−アダマンタノンの収率が顕著に増加することが知られている（特許文献１１）。この方法では９５〜９８％の高濃度の硫酸を用い、６０℃、８ｈで最高収率６８ｍｏｌ％が得られており、反応時間は充分に短縮されたが、工業的に実施するには更なる反応収率の改良が望まれていた。
In the selective production of 2-adamantanone, sulfuric acid functions as an oxidizing agent and a catalyst, and the reaction rate and selectivity are greatly influenced by the sulfuric acid concentration. The reaction rate is reduced by diluting the sulfuric acid consumed in the reaction. To compensate for this, a method has been proposed to suppress the decrease in sulfuric acid concentration by adding sulfur trioxide or fuming sulfuric acid during the reaction. (Patent Documents 7, 8 and 9). Although the reaction rate is improved by these methods, the selectivity and yield are not industrially sufficient.
In Patent Documents 1-9, the sulfuric acid concentration is 95% or more, and the reaction rate decreases at a dilute concentration of sulfuric acid concentration of less than 95%, and it is difficult to complete the reaction in a high yield in a short time. Met. In order to perform such a reaction at a dilute concentration of sulfuric acid, it is necessary to use 1-adamantanol as a raw material, which is known to be unsuitable for adamantane (Patent Document 10).
When selective production of 2-adamantanone is carried out by adding a halogenated alkane solvent such as 1,2-dichloroethane, not only the sublimation of the raw material adamantane is suppressed, but also the reaction rate is promoted. It is known that the yield of Tanone increases significantly (Patent Document 11). In this method, sulfuric acid with a high concentration of 95 to 98% was used, and the maximum yield of 68 mol% was obtained at 60 ° C. for 8 hours, and the reaction time was sufficiently shortened. Improvement of reaction yield has been desired.
上述したように硫酸を用いた２−アダマンタノンの選択的製造では、反応速度は短いが重質分が副生して収率が低い、又は収率は高いが反応時間が非常に長く生産性が低い、のどちらであった。従って、例えば反応が２４ｈ以内に完結できる迅速さを有し、例えば８０〜９０ｍｏｌ％の高収率であって、反応液を加水分解して溶媒で抽出する通常の後処理で２−アダマンタノンを回収できる製造方法が求められていた。また、製品又は廃硫酸に混入する可能性のある添加物が不要で、環境負荷が低く、廃硫酸等の廃棄物を最小限とできる高い生産性を有する２−アダマンタノンの選択的製造方法が求められていた。 As described above, in the selective production of 2-adamantanone using sulfuric acid, the reaction rate is short but the heavy component is a by-product and the yield is low, or the yield is high, but the reaction time is very long and the productivity is high. Was lower. Thus, for example, the reaction can be completed quickly within 24 hours, for example, in a high yield of 80 to 90 mol%, and 2-adamantanone can be obtained by usual post-treatment in which the reaction solution is hydrolyzed and extracted with a solvent. There was a need for a recoverable manufacturing method. In addition, there is a selective production method of 2-adamantanone that does not require an additive that may be mixed into a product or waste sulfuric acid, has low environmental impact, and has high productivity that can minimize waste such as waste sulfuric acid. It was sought after.
本発明の目的は、工業的に実施可能な程度に簡便で、反応を短時間で完結でき、且つ高い生産性を有する２−アダマンタノンの製造方法を提供することである。 An object of the present invention is to provide a method for producing 2-adamantanone that is as simple as industrially feasible, can complete the reaction in a short time, and has high productivity.
２−アダマンタノンの硫酸酸化反応は、従来、９６％以上の高い硫酸濃度かつ６０℃以下の比較的低い反応温度で検討されてきたが、本発明者らは鋭意研究した結果、２つの一級炭素のそれぞれに少なくとも１つのハロゲン原子が結合している炭素数２〜５のハロゲン化アルカン（例えば１，２−ジクロロエタン又は１，１，２，２−テトラクロロエタン）を溶媒として添加した場合には、アダマンタンの硫酸酸化を行うには不適当と考えられてきた希薄な硫酸濃度（９０〜９５重量％）において、反応温度７０〜９０℃の領域で特異的に高い収率が得られることを見出した。本条件で反応中に発煙硫酸及び／又は硫酸を滴下して反応開始時の硫酸濃度を超過することなく維持することにより、短時間で反応を完結させることができ、且つ高収率で２−アダマンタノンを得ることができる。 The sulfuric acid oxidation reaction of 2-adamantanone has been conventionally studied at a high sulfuric acid concentration of 96% or higher and a relatively low reaction temperature of 60 ° C. or lower. However, as a result of intensive studies, the present inventors have studied two primary carbons. When a halogenated alkane having 2 to 5 carbon atoms (for example, 1,2-dichloroethane or 1,1,2,2-tetrachloroethane) having at least one halogen atom bonded thereto is added as a solvent, It has been found that a particularly high yield can be obtained in a reaction temperature range of 70 to 90 ° C. at a dilute sulfuric acid concentration (90 to 95% by weight), which has been considered inappropriate for the oxidation of adamantane. . By dropping fuming sulfuric acid and / or sulfuric acid during the reaction under this condition and maintaining the sulfuric acid concentration at the start of the reaction without exceeding it, the reaction can be completed in a short time and in a high yield. Adamantanone can be obtained.
本発明によれば、以下の２−アダマンタノンの製造方法が提供される。
１．２つの一級炭素のそれぞれに少なくとも１つのハロゲン原子が結合している炭素数２〜５のハロゲン化アルカンの存在下で、濃度が９０〜９５重量％である硫酸を用いて、アダマンタンを７０〜９０℃で酸化する２−アダマンタノンの製造方法であって、
酸化中に三酸化硫黄ガス及び／又は発煙硫酸を逐次添加して、反応系内の全硫酸量（使用した硫酸、三酸化硫黄及び発煙硫酸のそれぞれの重量を１００％硫酸に換算した重量の合計）と前記アダマンタンの重量との比（硫酸／アダマンタン）を６〜１２とし、硫酸濃度を９０〜９５重量％に維持する２−アダマンタノンの製造方法。
２．硫酸濃度が９１〜９４重量％である１に記載の２−アダマンタノンの製造方法。
３．ハロゲン化アルカンが１，２−ジクロロエタン又は１，１，２，２−テトラクロロエタンである１又は２に記載の２−アダマンタノンの製造方法。
According to the present invention, the following method for producing 2-adamantanone is provided.
1. Using a sulfuric acid having a concentration of 90 to 95% by weight in the presence of a halogenated alkane having 2 to 5 carbon atoms in which at least one halogen atom is bonded to each of the primary carbons, adamantane is converted to 70 A process for producing 2-adamantanone that oxidizes at ~ 90 ° C, comprising:
Sulfur trioxide gas and / or fuming sulfuric acid are sequentially added during oxidation, and the total amount of sulfuric acid in the reaction system (the total weight of each sulfuric acid, sulfur trioxide and fuming sulfuric acid converted to 100% sulfuric acid) ) And the weight of the adamantane (sulfuric acid / adamantane) is 6 to 12, and the sulfuric acid concentration is maintained at 90 to 95% by weight.
2. 2. The method for producing 2-adamantanone according to 1, wherein the sulfuric acid concentration is 91 to 94% by weight.
3. The method for producing 2-adamantanone according to 1 or 2, wherein the alkane halide is 1,2-dichloroethane or 1,1,2,2-tetrachloroethane.
本発明によれば、工業的に実施可能な程度に簡便で、反応を短時間で完結でき、且つ高い生産性を有する２−アダマンタノンの製造方法が提供できる。 According to the present invention, it is possible to provide a method for producing 2-adamantanone that is as simple as industrially feasible, can complete the reaction in a short time, and has high productivity.
本発明の２−アダマンタノンの製造方法は、２つの一級炭素のそれぞれに少なくとも１つのハロゲン原子が結合している炭素数２〜５のハロゲン化アルカンの存在下で、濃度が９０〜９５重量％である硫酸を用いて、アダマンタンを７０〜９０℃で酸化する２−アダマンタノンの製造方法であって、酸化中に三酸化硫黄ガス及び／又は発煙硫酸を逐次添加して、反応系内の全硫酸量（使用した硫酸、三酸化硫黄及び発煙硫酸のそれぞれの重量を１００％硫酸に換算した重量の合計）と前記アダマンタンの重量との比（硫酸／アダマンタン）を６〜１２とし、硫酸濃度を９０〜９５重量％に維持する。
本発明の製造方法では、特に反応温度を７０〜９０℃とし、酸化中に三酸化硫黄ガス及び／又は発煙硫酸を逐次添加することで、反応を短時間で完結でき、且つ高収率で２−アダマンタノンを製造することができる。
The method for producing 2-adamantanone of the present invention has a concentration of 90 to 95% by weight in the presence of a halogenated alkane having 2 to 5 carbon atoms in which at least one halogen atom is bonded to each of two primary carbons. A method for producing 2-adamantanone in which adamantane is oxidized at 70 to 90 ° C. using sulfuric acid, wherein sulfur trioxide gas and / or fuming sulfuric acid is sequentially added during the oxidation, The ratio (sulfuric acid / adamantane) of the amount of sulfuric acid (the total weight of each of sulfuric acid, sulfur trioxide and fuming sulfuric acid used converted to 100% sulfuric acid) and the weight of the adamantane was 6-12, and the sulfuric acid concentration was Maintain 90-95 wt%.
In the production method of the present invention, in particular, the reaction temperature is set to 70 to 90 ° C., and sulfur trioxide gas and / or fuming sulfuric acid is sequentially added during the oxidation, whereby the reaction can be completed in a short time and at a high yield of 2 -Adamantanone can be produced.
２つの一級炭素のそれぞれに少なくとも１つのハロゲン原子が結合している炭素数２〜５のハロゲン化アルカン（以下、単にハロゲン化アルカンという場合がある）は溶媒として機能する。ハロゲン化アルカンを使用しない場合、反応速度の低下、原料アダマンタンの昇華、重質物の増加による収率の低下が生じるおそれがある。
２つの一級炭素のそれぞれに少なくとも１つのハロゲン原子が結合している炭素数２〜５のハロゲン化アルカンは、好ましくは炭素数２〜３のハロゲン化アルカンであり、より好ましくは炭素数２〜３の塩素化アルカンである。
A halogenated alkane having 2 to 5 carbon atoms in which at least one halogen atom is bonded to each of the two primary carbons (hereinafter sometimes simply referred to as a halogenated alkane) functions as a solvent. When a halogenated alkane is not used, there is a possibility that the reaction rate is lowered, the raw material adamantane is sublimated, and the yield is lowered due to an increase in heavy substances.
The halogenated alkane having 2 to 5 carbon atoms in which at least one halogen atom is bonded to each of the two primary carbons is preferably a halogenated alkane having 2 to 3 carbon atoms, more preferably 2 to 3 carbon atoms. Chlorinated alkanes.
上記ハロゲン化アルカンの具体例としては、１，２−ジクロロエタン、１，１，２−トリクロロエタン、１，１，２，２−テトラクロロエタン、１，１，１，２−テトラクロロエタン、１，３−ジクロロプロパン、１，２，３−トリクロロプロパン、１，２−ジブロモエタン、１，１，２，２−テトラブロモエタン、２−ブロモ−１−クロロエタン等が挙げられ、好ましくは１，２−ジクロロエタン、１，１，２−トリクロロエタン、１，１，２，２−テトラクロロエタン、１，３−ジクロロプロパン、１，２，３−トリクロロプロパンであり、より好ましくは１，２−ジクロロエタン及び１，１，２，２−テトラクロロエタンである。
上記ハロゲン化アルカンは、１種単独で使用してもよく、２種以上を混合して用いてもよい。
Specific examples of the halogenated alkane include 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane, 1,3- Examples include dichloropropane, 1,2,3-trichloropropane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 2-bromo-1-chloroethane, and the like, preferably 1,2-dichloroethane. 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,3-dichloropropane, 1,2,3-trichloropropane, more preferably 1,2-dichloroethane and 1,1 2,2-tetrachloroethane.
The said halogenated alkane may be used individually by 1 type, and may mix and use 2 or more types.
ハロゲン化アルカンの使用量は、アダマンタン１重量部に対し、例えば０．５〜１００重量部であり、好ましくは０．５〜１０重量部であり、より好ましくは１．０〜１０重量部である。
ハロゲン化アルカンの使用量が、アダマンタン１重量部に対して０．５重量部未満の場合、２−アダマンタノンの収率が低下するおそれがある。一方、ハロゲン化アルカンの使用量が、アダマンタン１重量部に対して１００重量部超の場合、反応器への仕込み量が増大するために生産効率が悪化するおそれがある。
The amount of the halogenated alkane used is, for example, 0.5 to 100 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1.0 to 10 parts by weight with respect to 1 part by weight of adamantane. .
When the amount of halogenated alkane used is less than 0.5 parts by weight based on 1 part by weight of adamantane, the yield of 2-adamantanone may be reduced. On the other hand, when the amount of halogenated alkane used is more than 100 parts by weight with respect to 1 part by weight of adamantane, the charging amount to the reactor increases, so that production efficiency may be deteriorated.
アダマンタンの酸化に用いる硫酸（水溶液）は濃度が９０〜９５重量％であり、好ましくは９１〜９４重量％である。
硫酸濃度が、それぞれ９０重量％未満又は９５重量％超である場合、副生する重質分が増加して選択率が下がり、収率が低下するおそれがある。
The sulfuric acid (aqueous solution) used for the oxidation of adamantane has a concentration of 90 to 95% by weight, preferably 91 to 94% by weight.
When the sulfuric acid concentration is less than 90% by weight or more than 95% by weight, respectively, there is a possibility that heavy by-products increase and the selectivity decreases, resulting in a decrease in yield.
アダマンタンを硫酸で酸化する際の反応温度は７０〜９０℃である。
反応温度が７０℃未満の場合、反応速度が下がって生産効率が低下するおそれがある。一方、反応温度が９０℃超の場合、副生する重質分が増加し、且つ選択率が下がるおそれがある。
また、酸化反応の反応時間は、用いる硫酸の濃度及び反応温度によって異なるが、通常１２〜４８時間である。
The reaction temperature when oxidizing adamantane with sulfuric acid is 70 to 90 ° C.
When reaction temperature is less than 70 degreeC, there exists a possibility that reaction rate may fall and production efficiency may fall. On the other hand, when the reaction temperature is higher than 90 ° C., the by-product heavy component is increased and the selectivity may be lowered.
The reaction time for the oxidation reaction is usually 12 to 48 hours, although it varies depending on the concentration of sulfuric acid used and the reaction temperature.
本発明の２−アダマンタノンの製造方法では、硫酸によるアダマンタンの酸化中、三酸化硫黄ガス及び／又は発煙硫酸を逐次添加して、反応液中の硫酸濃度を、反応開始時にアダマンタンの酸化に用いた硫酸（水溶液）の濃度に維持する。即ち、反応液中の硫酸濃度を、９０〜９５重量％、好ましくは９１〜９４重量％に維持する。
逐次添加する三酸化硫黄ガス及び／又は発煙硫酸の三酸化硫黄濃度は特に限定されず、発煙硫酸については工業的に用いられる１０〜６５重量％の発煙硫酸が使用でき、三酸化硫黄ガスについては１００％ガス又は窒素等で適宜希釈したガスを使用できる。
尚、発煙硫酸の濃度は、三酸化硫黄と硫酸の混合物中の三酸化硫黄の重量％を意味する。
In the method for producing 2-adamantanone of the present invention, during oxidation of adamantane with sulfuric acid, sulfur trioxide gas and / or fuming sulfuric acid is sequentially added, and the sulfuric acid concentration in the reaction solution is used for oxidation of adamantane at the start of the reaction. Maintain the concentration of sulfuric acid (aqueous solution). That is, the sulfuric acid concentration in the reaction solution is maintained at 90 to 95% by weight, preferably 91 to 94% by weight.
The sulfur trioxide concentration of sulfur trioxide gas and / or fuming sulfuric acid to be added sequentially is not particularly limited. For fuming sulfuric acid, 10 to 65 wt% fuming sulfuric acid used industrially can be used, and for sulfur trioxide gas, A gas appropriately diluted with 100% gas or nitrogen can be used.
The concentration of fuming sulfuric acid means the weight percentage of sulfur trioxide in the mixture of sulfur trioxide and sulfuric acid.
逐次添加する三酸化硫黄ガス及び／又は発煙硫酸の添加量は、反応が１００％進行した場合に、反応終了時の反応液中の硫酸濃度が、反応開始時の反応液中の硫酸濃度と同じになるように計算して求めた量にすればよい。反応系内の全硫酸量とアダマンタンの重量との比（硫酸／アダマンタン）が６〜１２になるようにし、後処理時の釜効率の向上を考慮して、好ましくは６〜８になるようにする。
上記全硫酸量とは、アダマンタンの酸化に使用する硫酸、並びに反応中に添加する三酸化硫黄ガス及び発煙硫酸のそれぞれの重量を１００％硫酸に換算した重量の合計を意味する。
例えばアダマンタン１００ｇと９３％硫酸４４０ｇを仕込み、２５％発煙硫酸３７０ｇを逐次添加した場合、反応系内の全硫酸量（反応に用いた硫酸量）＝０．９３×４４０＋０．２５×３７０×９８／８０＋０．７５×３７０＝８００ｇであり、反応系内の全硫酸量とアダマンタンの重量比（硫酸／アダマンタン）＝８００／１００＝８となる。
全硫酸量が上記より多い場合（反応系内の全硫酸量とアダマンタンの重量比が１２より大きい場合）であっても反応性に変化はなく、全硫酸量が上記より少ない場合（反応系内の全硫酸量とアダマンタンの重量比が６より小さい場合）は反応速度が低下するおそれがある。
The amount of sulfur trioxide gas and / or fuming sulfuric acid added sequentially is the same as the sulfuric acid concentration in the reaction solution at the start of the reaction when the reaction proceeds 100%. What is necessary is just to make it the quantity calculated | required so that it may become. The ratio of the total amount of sulfuric acid in the reaction system to the weight of adamantane (sulfuric acid / adamantane) should be 6-12, and preferably 6-8, taking into account the improvement of the pot efficiency during post-treatment. To do.
The total amount of sulfuric acid means the sum of the weights of sulfuric acid used for oxidation of adamantane, and the respective weights of sulfur trioxide gas and fuming sulfuric acid added during the reaction, converted to 100% sulfuric acid.
For example, when 100 g of adamantane and 440 g of 93% sulfuric acid are added and 370 g of 25% fuming sulfuric acid are sequentially added, the total amount of sulfuric acid in the reaction system (the amount of sulfuric acid used in the reaction) = 0.93 × 440 + 0.25 × 370 × 98 / 80 + 0.75 × 370 = 800 g, and the weight ratio of total sulfuric acid in the reaction system to adamantane (sulfuric acid / adamantane) = 800/100 = 8.
There is no change in reactivity even when the total sulfuric acid amount is higher than the above (when the weight ratio of the total sulfuric acid amount to the adamantane in the reaction system is greater than 12), and the total sulfuric acid amount is lower than the above (within the reaction system) If the weight ratio of total sulfuric acid to adamantane is less than 6), the reaction rate may decrease.
三酸化硫黄ガス及び／又は発煙硫酸は、例えば、反応終了時に上記添加量を添加し切るように逐次添加する。三酸化硫黄ガス及び／又は発煙硫酸を一括で添加した場合、硫酸濃度が一時的に高くなり過ぎてしまい、収率が逆に低下するおそれがある。 For example, sulfur trioxide gas and / or fuming sulfuric acid are sequentially added so that the above-mentioned addition amount is completely added at the end of the reaction. When sulfur trioxide gas and / or fuming sulfuric acid is added all at once, the sulfuric acid concentration temporarily becomes excessively high, and the yield may decrease.
本発明の製造方法においては、酸化反応中に亜硫酸ガスが発生するため、通常、反応は常圧で行われるが、減圧、加圧のいずれの状態でも反応を実施することができる。
本発明の製造方法に使用可能な反応装置としては、十分な撹拌が可能で、発煙硫酸の滴下又はＳＯ３ガスの吹込みが可能で、且つ硫酸、ハロゲン化アルカン等に耐える材質を使用した装置であれば何ら制限はないが、通常、ガラスライニングされた装置が用いられる。
In the production method of the present invention, since sulfurous acid gas is generated during the oxidation reaction, the reaction is usually carried out at normal pressure, but the reaction can be carried out in either reduced pressure or pressurized state.
As a reaction apparatus that can be used in the production method of the present invention, an apparatus using a material that can sufficiently stir, can drop fuming sulfuric acid or blow SO 3 gas, and can withstand sulfuric acid, halogenated alkane, and the like. If there is no limitation, a glass-lined apparatus is usually used.
本発明の製造方法は、通常、反応容器に所定量のアダマンタン、所定量の所定の濃度に調製した硫酸、所定量のハロゲン化アルカンを仕込み、反応条件を設定して、三酸化硫黄ガス及び／又は発煙硫酸を逐次添加して反応を行う。
反応終了後の反応液からの２−アダマンタノンの単離方法としては、特に制限はないが、例えば、反応液を氷中に投入し、中和後、析出した結晶を溶媒により抽出し、次いで洗浄、溶媒留去及び乾燥を行う方法；反応液を氷中に投入し、中和後、析出した結晶を溶媒により抽出し、次いで水蒸気蒸留等により精製する方法；反応液を氷中に投入し、中和後、析出した結晶をろ過及び遠心分離する方法等が挙げられる。
In the production method of the present invention, a predetermined amount of adamantane, a predetermined amount of sulfuric acid prepared to a predetermined concentration and a predetermined amount of halogenated alkane are usually charged in a reaction vessel, reaction conditions are set, sulfur trioxide gas and / or Alternatively, the reaction is performed by sequentially adding fuming sulfuric acid.
The method for isolating 2-adamantanone from the reaction solution after completion of the reaction is not particularly limited. For example, the reaction solution is put into ice, neutralized, and then the precipitated crystals are extracted with a solvent, and then extracted. A method of washing, distilling off the solvent and drying; a method in which the reaction solution is put into ice, neutralized, and then the precipitated crystals are extracted with a solvent, and then purified by steam distillation; the reaction solution is put in ice And a method of filtering and centrifuging the precipitated crystals after neutralization.
上記抽出溶媒としては、反応に使用するハロゲン化アルカンと同一のハロゲン化アルカンを使用することができ、具体例としては、１，２−ジクロロエタン、１，１，２−トリクロロエタン、１，１，２，２−テトラクロロエタン、１，１，１，２−テトラクロロエタン、１，３−ジクロロプロパン、１，２，３−トリクロロプロパン、１，２−ジブロモエタン、１，１，２，２−テトラブロモエタン、２−ブロモ−１−クロロエタン等が挙げられる。
このようにして得られた２−アダマンタノンは、必要により、クロマトグラフィ、再結晶、減圧蒸留、水蒸気蒸留又は昇華精製等の方法で精製してもよい。
As the extraction solvent, the same halogenated alkane as the halogenated alkane used in the reaction can be used. Specific examples include 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2 , 2-tetrachloroethane, 1,1,1,2-tetrachloroethane, 1,3-dichloropropane, 1,2,3-trichloropropane, 1,2-dibromoethane, 1,1,2,2-tetrabromo Examples include ethane and 2-bromo-1-chloroethane.
The 2-adamantanone thus obtained may be purified by a method such as chromatography, recrystallization, vacuum distillation, steam distillation or sublimation purification, if necessary.
実施例１
２Ｌの四口フラスコにアダマンタン１５０ｇ、９３重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、２５重量％発煙硫酸５５５ｇを２４ｈかけて滴下することで硫酸濃度を９３重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液１０２０ｇを加え、仕込んだ硫酸及び発煙硫酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Example 1
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 93% by weight sulfuric acid, and 225 g of 1,2-dichloroethane, and a Dimroth condenser tube, a thermocouple sheath tube, a dropping funnel, and a stirring blade were attached. The temperature was raised to 80 ° C. with stirring, and 555 g of 25 wt% fuming sulfuric acid was added dropwise over 24 hours to carry out the reaction while maintaining the sulfuric acid concentration at 93 wt%.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 1020 g of 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged sulfuric acid and fuming sulfuric acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
比較例１
１，２−ジクロロエタンを添加しなかった他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Comparative Example 1
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that 1,2-dichloroethane was not added. The results are shown in Table 1.
比較例２
２５重量％発煙硫酸を添加しなかった他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Comparative Example 2
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that 25 wt% fuming sulfuric acid was not added. The results are shown in Table 1.
比較例３
２Ｌの四口フラスコに９３重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、さらに２５％発煙硫酸５５５ｇを一括で添加し、その後にアダマンタン１５０ｇを添加した。ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付け、攪拌しながら８０℃まで昇温して２４時間反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液１０２０ｇを加え、仕込んだ酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Comparative Example 3
A 2 L four-necked flask was charged with 660 g of 93% by weight sulfuric acid and 225 g of 1,2-dichloroethane, 555 g of 25% fuming sulfuric acid was added all at once, and then 150 g of adamantane was added. A Dimroth condenser tube, a thermocouple sheath tube, a dropping funnel, and a stirring blade were attached, and the temperature was raised to 80 ° C. while stirring and the reaction was performed for 24 hours.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 1020 g of a 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
実施例２
２Ｌの四口フラスコにアダマンタン１５０ｇ、９２重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、２５重量％発煙硫酸５２５ｇを２４ｈかけて滴下することで硫酸濃度を９２重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液９８８ｇを加え、仕込んだ酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Example 2
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 92% by weight sulfuric acid, and 225 g of 1,2-dichloroethane, and a Dimroth condenser, a thermocouple sheath, a dropping funnel, and a stirring blade were attached. The temperature was raised to 80 ° C. with stirring, and 525 g of 25 wt% fuming sulfuric acid was added dropwise over 24 h to carry out the reaction while maintaining the sulfuric acid concentration at 92 wt%.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 988 g of 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
実施例３
反応時間（発煙硫酸滴下時間）を３６ｈとした他は実施例２と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Example 3
2-adamantanone was produced and evaluated in the same manner as in Example 2 except that the reaction time (fuming sulfuric acid dropping time) was 36 h. The results are shown in Table 1.
実施例４
２Ｌの四口フラスコにアダマンタン１５０ｇ、９１重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、２５重量％発煙硫酸５０３ｇを２４ｈかけて滴下することで硫酸濃度を９１重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液９６２ｇを加え、仕込んだ酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Example 4
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 91% by weight sulfuric acid, and 225 g of 1,2-dichloroethane, and a Dimroth condenser tube, a thermocouple sheath tube, a dropping funnel, and a stirring blade were attached. The temperature was raised to 80 ° C. with stirring, and 503 g of 25 wt% fuming sulfuric acid was added dropwise over 24 hours to carry out the reaction while maintaining the sulfuric acid concentration at 91 wt%.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 962 g of 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
実施例５
反応時間（発煙硫酸滴下時間）を４８ｈとした他は実施例４と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Example 5
2-adamantanone was produced and evaluated in the same manner as in Example 4 except that the reaction time (fuming sulfuric acid dropping time) was 48 h. The results are shown in Table 1.
実施例６
２Ｌの四口フラスコにアダマンタン１５０ｇ、９４重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、２５重量％発煙硫酸５９３ｇを２４ｈかけて滴下することで硫酸濃度を９４重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液１０６０ｇを加え、仕込んだ酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Example 6
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 94% by weight sulfuric acid, and 225 g of 1,2-dichloroethane, and a Dimroth condenser, a thermocouple sheath, a dropping funnel, and a stirring blade were attached. The temperature was raised to 80 ° C. with stirring, and 593 g of 25 wt% fuming sulfuric acid was added dropwise over 24 hours to carry out the reaction while maintaining the sulfuric acid concentration at 94 wt%.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 1060 g of 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
実施例７
２Ｌの四口フラスコにアダマンタン１５０ｇ、９５重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、２５重量％発煙硫酸６３０ｇを２４ｈかけて滴下することで硫酸濃度を９５重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液１０９９ｇを加え、仕込んだ硫酸及び発煙硫酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Example 7
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 95% by weight sulfuric acid and 225 g of 1,2-dichloroethane, and a Dimroth condenser tube, a thermocouple sheath tube, a dropping funnel, and a stirring blade were attached. The temperature was raised to 80 ° C. with stirring, and 630 g of 25 wt% fuming sulfuric acid was added dropwise over 24 hours to carry out the reaction while maintaining the sulfuric acid concentration at 95 wt%.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 1099 g of 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged sulfuric acid and fuming sulfuric acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
比較例４
２Ｌの四口フラスコにアダマンタン１５０ｇ、９６重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、２５重量％発煙硫酸８２５ｇを２４ｈかけて滴下することで硫酸濃度を９６重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液１２８０ｇを加え、仕込んだ硫酸及び発煙硫酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Comparative Example 4
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 96 wt% sulfuric acid and 225 g of 1,2-dichloroethane, and fitted with a Dimroth condenser, thermocouple sheath, dropping funnel and stirring blade. The temperature was raised to 80 ° C. with stirring, and 825 g of 25 wt% fuming sulfuric acid was added dropwise over 24 hours to carry out the reaction while maintaining the sulfuric acid concentration at 96 wt%.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 1280 g of 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged sulfuric acid and fuming sulfuric acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
比較例５
２Ｌの四口フラスコにアダマンタン１５０ｇ、９８重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、２５重量％発煙硫酸８２５ｇを２４ｈかけて滴下することで硫酸濃度を９８重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液１２９１ｇを加え、仕込んだ硫酸及び発煙硫酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Comparative Example 5
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 98% by weight sulfuric acid, and 225 g of 1,2-dichloroethane, and a Dimroth condenser tube, a thermocouple sheath tube, a dropping funnel, and a stirring blade were attached. The temperature was raised to 80 ° C. with stirring, and 825 g of 25 wt% fuming sulfuric acid was added dropwise over 24 h to carry out the reaction while maintaining the sulfuric acid concentration at 98 wt%.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 1291 g of 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged sulfuric acid and fuming sulfuric acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
比較例６
２Ｌの四口フラスコにアダマンタン１５０ｇ、８５重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、２５重量％発煙硫酸４０１ｇを２４ｈかけて滴下することで硫酸濃度を８５重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液８３７ｇを加え、仕込んだ硫酸及び発煙硫酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Comparative Example 6
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 85 wt% sulfuric acid, and 225 g of 1,2-dichloroethane, and a Dimroth condenser tube, a thermocouple sheath tube, a dropping funnel, and a stirring blade were attached. The temperature was raised to 80 ° C. with stirring, and 401 g of 25 wt% fuming sulfuric acid was added dropwise over 24 h to carry out the reaction while maintaining the sulfuric acid concentration at 85 wt%.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 837 g of a 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged sulfuric acid and fuming sulfuric acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
実施例８
２Ｌの四口フラスコにアダマンタン１５０ｇ、９３重量％硫酸６６０ｇ及び１，２−ジクロロエタン２２５ｇを仕込み、ジムロート冷却管及び熱電対鞘管、滴下ロート、攪拌翼を取り付けた。攪拌しながら８０℃まで昇温し、ＳＯ３ガス２１７ｇを窒素で５０％に希釈した混合ガスを２４ｈかけて反応液中に吹き込み、硫酸濃度を９３重量％に維持した状態で反応を行った。
反応終了後、氷水６５０ｇに反応液をあけ、トルエン６００ｇを加えた後、冷却しながら４８重量％ＮａＯＨ水溶液７４８ｇを加え、仕込んだ硫酸及び発煙硫酸の半量を中和した。トルエン抽出液をガスクロマトグラフィで分析し、２−アダマンタノンの収量等を評価した。結果を表１に示す。
Example 8
A 2 L four-necked flask was charged with 150 g of adamantane, 660 g of 93% by weight sulfuric acid, and 225 g of 1,2-dichloroethane, and a Dimroth condenser tube, a thermocouple sheath tube, a dropping funnel, and a stirring blade were attached. While stirring, the temperature was raised to 80 ° C., and a mixed gas obtained by diluting 217 g of SO 3 gas to 50% with nitrogen was blown into the reaction solution over 24 hours, and the reaction was carried out while maintaining the sulfuric acid concentration at 93% by weight.
After completion of the reaction, the reaction solution was poured into 650 g of ice water, 600 g of toluene was added, and 748 g of 48 wt% NaOH aqueous solution was added while cooling to neutralize half of the charged sulfuric acid and fuming sulfuric acid. The toluene extract was analyzed by gas chromatography to evaluate the yield of 2-adamantanone and the like. The results are shown in Table 1.
実施例９
反応温度を７０℃とした他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Example 9
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that the reaction temperature was 70 ° C. The results are shown in Table 1.
実施例１０
反応時間（発煙硫酸滴下時間）を４８ｈとした以外は実施例９と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Example 10
2-adamantanone was produced and evaluated in the same manner as in Example 9 except that the reaction time (fuming sulfuric acid dropping time) was 48 h. The results are shown in Table 1.
実施例１１
１，２−ジクロロエタンの代わりに１，１，２，２−テトラクロロエタン２２５ｇを仕込んだ他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Example 11
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that 225 g of 1,1,2,2-tetrachloroethane was used instead of 1,2-dichloroethane. The results are shown in Table 1.
実施例１２
反応温度を９０℃とし、反応時間（発煙硫酸滴下時間）を１２ｈとした他は実施例１１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Example 12
2-adamantanone was produced and evaluated in the same manner as in Example 11 except that the reaction temperature was 90 ° C. and the reaction time (fuming sulfuric acid dropping time) was 12 h. The results are shown in Table 1.
比較例７
反応温度を１００℃とし、反応時間（発煙硫酸滴下時間）を４ｈとした他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Comparative Example 7
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that the reaction temperature was 100 ° C. and the reaction time (fuming sulfuric acid dropping time) was 4 h. The results are shown in Table 1.
比較例８
反応温度を６０℃とした他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Comparative Example 8
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that the reaction temperature was 60 ° C. The results are shown in Table 1.
実施例１３
９３重量％硫酸の仕込み量を１２００ｇとし、４８％ＮａＯＨ水溶液の添加量を１４５０ｇとした他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Example 13
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that the amount of 93% by weight sulfuric acid was 1200 g and the amount of 48% NaOH aqueous solution was 1450 g. The results are shown in Table 1.
実施例１４
９３重量％硫酸の仕込み量を４００ｇとし、４８％ＮａＯＨ水溶液の添加量を８１５ｇとした他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Example 14
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that the amount of 93% by weight sulfuric acid was 400 g and the amount of 48% NaOH aqueous solution was 815 g. The results are shown in Table 1.
比較例９
９３重量％硫酸の仕込み量を２１０ｇとし、４８％ＮａＯＨ水溶液の添加量を６６０ｇとした他は実施例１と同様にして２−アダマンタノンを製造し、評価した。結果を表１に示す。
Comparative Example 9
2-adamantanone was produced and evaluated in the same manner as in Example 1 except that the amount of 93% by weight sulfuric acid was 210 g and the amount of 48% NaOH aqueous solution was 660 g. The results are shown in Table 1.
比較例１０
２００ｍｌのフラスコにアダマンタンを１７ｇ、９６重量％硫酸を１８４ｇ（１００ｍｌ）入れ、６５℃で１２時間加熱攪拌した。加熱撹拌の間、反応開始後２時間から１０時間まで２５％発煙硫酸を添加速度９．６２５ｇ／ｈ（３０ｍｍｏｌ−ＳＯ３／ｈ）で７７ｇ（ＳＯ３として２４０ｍｍｏｌ）滴下した。放冷後、２００ｍｌの氷に反応混合物をあけ、エーテル２００ｍｌで２回抽出した。エーテル層を飽和食塩水２００ｍｌで２回洗浄した後、無水硫酸マグネシウムで乾燥し、エーテルを減圧下留去して２−アダマンタノンを製造した。結果を表１に示す。
Comparative Example 10
A 200 ml flask was charged with 17 g of adamantane and 184 g (100 ml) of 96 wt% sulfuric acid, and the mixture was heated and stirred at 65 ° C. for 12 hours. During heating and stirring, 77 g (240 mmol as SO 3 ) was added dropwise at a rate of addition of 9.625 g / h (30 mmol-SO 3 / h) of 25% fuming sulfuric acid from 2 hours to 10 hours after the start of the reaction. After allowing to cool, the reaction mixture was poured into 200 ml of ice and extracted twice with 200 ml of ether. The ether layer was washed twice with 200 ml of saturated brine and then dried over anhydrous magnesium sulfate, and ether was distilled off under reduced pressure to produce 2-adamantanone. The results are shown in Table 1.
表１において、ＡＤＭはアダマンタンを意味し、ＡＤＯとは２−アダマンタノンを意味する。また、硫酸量及び全硫酸量は、いずれも１００％Ｈ２ＳＯ４換算重量である。硫酸量は、アダマンタンの酸化に使用する硫酸の量である。
「硫酸濃度」とは、「反応液全体に含まれる硫酸重量」／「反応液全体に含まれる硫酸重量＋反応液全体に含まれる水の重量」×100＝「硫酸濃度」として計算される。
In Table 1, ADM means adamantane, and ADO means 2-adamantanone. Further, the amount of sulfuric acid and the total amount of sulfuric acid are both 100% H 2 SO 4 equivalent weight. The amount of sulfuric acid is the amount of sulfuric acid used to oxidize adamantane.
The “sulfuric acid concentration” is calculated as “the weight of sulfuric acid contained in the whole reaction solution” / “the weight of sulfuric acid contained in the whole reaction solution + the weight of water contained in the whole reaction solution” × 100 = “sulfuric acid concentration”.
本発明の製造方法により得られる２−アダマンタノンは、医農薬原料、産業用原料の重要な中間体である。 2-adamantanone obtained by the production method of the present invention is an important intermediate of raw materials for medicines and agricultural chemicals and industrial materials.
Claims (3)
酸化中に三酸化硫黄ガス及び／又は発煙硫酸を逐次添加して、反応系内の全硫酸量（使用した硫酸、三酸化硫黄及び発煙硫酸のそれぞれの重量を１００％硫酸に換算した重量の合計）と前記アダマンタンの重量との比（硫酸／アダマンタン）を６〜１２とし、硫酸濃度を９０〜９５重量％で維持する２−アダマンタノンの製造方法。 In the presence of a halogenated alkane having 2 to 5 carbon atoms in which at least one halogen atom is bonded to each of two primary carbons, sulfuric acid having a concentration of 90 to 95% by weight is used to convert adamantane to 70 to 90%. A process for producing 2-adamantanone that oxidizes at 0 ° C.,
Sulfur trioxide gas and / or fuming sulfuric acid are sequentially added during oxidation, and the total amount of sulfuric acid in the reaction system (the total weight of each sulfuric acid, sulfur trioxide and fuming sulfuric acid converted to 100% sulfuric acid) ) And the weight of the adamantane (sulfuric acid / adamantane) is 6 to 12, and the sulfuric acid concentration is maintained at 90 to 95% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012146243A JP5892879B2 (en) | 2011-07-01 | 2012-06-29 | 2-Adamantanone production method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011147570 | 2011-07-01 | ||
| JP2011147570 | 2011-07-01 | ||
| JP2012146243A JP5892879B2 (en) | 2011-07-01 | 2012-06-29 | 2-Adamantanone production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013032344A true JP2013032344A (en) | 2013-02-14 |
| JP5892879B2 JP5892879B2 (en) | 2016-03-23 |
Family
ID=47397238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012146243A Active JP5892879B2 (en) | 2011-07-01 | 2012-06-29 | 2-Adamantanone production method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5892879B2 (en) |
| CN (1) | CN102850199A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233644B (en) * | 2020-03-10 | 2023-02-17 | 四川众邦新材料股份有限公司 | Synthesis and extraction method of adamantanone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003212810A (en) * | 2002-01-16 | 2003-07-30 | Mitsubishi Gas Chem Co Inc | Method for producing adamantanone |
| JP2005089329A (en) * | 2003-09-12 | 2005-04-07 | Tokuyama Corp | Manufacturing method of 2-adamantanone |
| JP2008280315A (en) * | 2007-05-14 | 2008-11-20 | Idemitsu Kosan Co Ltd | Method for producing 2-adamantanone |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1185191C (en) * | 2000-04-28 | 2005-01-19 | 德山株式会社 | Process for preparation of alicyclic ketones and alkyl-substituted alicyclic esters |
| JP2005097201A (en) * | 2003-09-26 | 2005-04-14 | Tokuyama Corp | Method for producing alicyclic ketone compound |
-
2012
- 2012-06-29 JP JP2012146243A patent/JP5892879B2/en active Active
- 2012-06-29 CN CN2012102201913A patent/CN102850199A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003212810A (en) * | 2002-01-16 | 2003-07-30 | Mitsubishi Gas Chem Co Inc | Method for producing adamantanone |
| JP2005089329A (en) * | 2003-09-12 | 2005-04-07 | Tokuyama Corp | Manufacturing method of 2-adamantanone |
| JP2008280315A (en) * | 2007-05-14 | 2008-11-20 | Idemitsu Kosan Co Ltd | Method for producing 2-adamantanone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102850199A (en) | 2013-01-02 |
| JP5892879B2 (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5892879B2 (en) | 2-Adamantanone production method | |
| CN109942459B (en) | Method for synthesizing 3-difluoromethyl-3-acrylonitrile compounds | |
| JP2006104200A (en) | Synthesis of pentafluorosulfanylnaphthalene | |
| JPWO2006006414A1 (en) | 2-Adamantanone production method | |
| CN104496940A (en) | Method for preparing BCR-ABL inhibitor intermediate | |
| JP2012254943A (en) | Method for producing polychloropropene | |
| JP4995633B2 (en) | 2-Adamantanone production method | |
| CN101585783B (en) | Preparing method of ortho-nitrobenzonitrile series compound | |
| JP2009155280A (en) | METHOD FOR PRODUCING gamma-BUTYROLACTONE COMPOUND | |
| JP5826964B1 (en) | Method for producing pyridine-3-sulfonyl chloride | |
| JP2015063501A (en) | NOVEL HYPERVALENT IODINE COMPOUND HAVING 5-X(X=F,Cl,Br)-1,2-BENZIODOXOL-3-(1H)-ON PART | |
| JP5598533B2 (en) | Process for producing iodinated aromatic compounds | |
| JP5129782B2 (en) | Method for producing adamantanols | |
| JP4038657B2 (en) | Method for producing adamantanone | |
| CN113735785A (en) | Preparation method of 3, 6-dichloropyrazine-2-carbonitrile | |
| JP5197106B2 (en) | Method for producing halogenated phthalic acid compound | |
| JP2014208604A (en) | Method for manufacturing an aromatic acyl compound | |
| CN103626673B (en) | A kind of perfluoroalkyl aromatic hydroxylamine compound and preparation method thereof | |
| JP5647783B2 (en) | Solvent for radical reaction consisting of fluorine-containing compounds | |
| JP7227711B2 (en) | Method for producing 2-(2-haloethyl)-1,3-dioxolane | |
| JP2010159223A (en) | Method for producing iodine compound | |
| JP6024410B2 (en) | Method for producing hydroxyadamantane polycarboxylic acid compound | |
| JP2009079009A (en) | Method for producing biphenyl-2,3,2',3'-tetracarboxylic acid | |
| JPWO2003062187A1 (en) | Method for producing 2,5-bis (trifluoromethyl) nitrobenzene | |
| JP2016169165A (en) | Method for producing 2,6-difluorobenzoylformate compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20140710 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150209 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150624 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150717 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150910 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160203 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160223 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5892879 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |