JP2004217526A - Method for producing 2-aminotropone - Google Patents
Method for producing 2-aminotropone Download PDFInfo
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- JP2004217526A JP2004217526A JP2003003003A JP2003003003A JP2004217526A JP 2004217526 A JP2004217526 A JP 2004217526A JP 2003003003 A JP2003003003 A JP 2003003003A JP 2003003003 A JP2003003003 A JP 2003003003A JP 2004217526 A JP2004217526 A JP 2004217526A
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- Prior art keywords
- aminotropone
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- tropolone
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、アンモニア水中で一段階でトロポロンから2−アミノトロポンを製造する方法に関する。
2−アミノトロポンは、ゲル化剤、医薬品,レーザー吸収色素,液晶素子,電子写真感光体等の光学記録材料,有機伝導体,触媒配位子,染料,キレート試薬等として有用なトロポン誘導体の合成原料である,
【0002】
【従来の技術】
2−アミノトロポンは、トロポンとヒドラジンとの反応により合成され、合成された2−アミノトロポンはアルカリ分解してトロポロンを製造する中間体として利用されていた。しかしながら、2−アミノトロポンおよびその誘導体は、特に、抗炎症剤などの医薬品合成中間体、有機低分子ゲル化剤など各種ファインケミカルズの重要な合成中間体であり、その簡便かつ工業的生産に適した製造方法が要望されている。前記2−アミノトロポンの製造方法は、危険な試薬であるヒドラジンが用いられること、また、比較的扱いやすい試薬を用いたものとして利用されている汎用されている2−アミノトロポンの製造方法は、トロポロンから2段階の工程を経て製造する方法であり、製造方法のより合理化が必要である。
【0003】
【特許文献1】
特公昭29−623号公報、特許請求の範囲、2頁(3)
【特許文献2】
特公昭32−5924号公報、特許請求の範囲、実施例1,3
【非特許文献1】
J. Am. Chem. Soc., 74, 5688 (1952);
【非特許文献2】
J. Am. Chem. Soc., 74, 5683 (1952);
【非特許文献3】
J. Am. Chem. Soc., 73, 828 (1951);
【0004】
特許文献1には、アンモニア水を用いて、置換トロポン類を原料として置換2−アミノトロポンを製造する方法であり、2−アミノトロポンの製造については、トロポロンから2−アミノトロポンを製造する方法は記載されておらず、トロポロンのアルキルエーテル体である2−メトキシトロポンにアンモニアを反応させ、2段階で2−アミノトロポンを得る方法(反応式3)に言及しているにすぎない。特許文献2には、トロポン類にアンモニア類を反応させてアミノトロポンを製造する方法が記載されている(実施例3)がトロポン類は不安定であり、アンモニアは融点がマイナス77.7℃、沸点がマイナス33.4℃であり、毒性,刺激性を有し、ヒドラジン(実施例1)は刺激性などの毒性を有し,熱,火気,酸化剤や鉄さびなどの金属酸化物と反応すると激しく爆発するなど取り扱いが困難な薬剤を使用するという問題がある。
また、非特許文献1〜3には、それぞれ、トロポロンから2−(p−トルエンスルホニルオキシ)トロポンを作り、これをアミノ化してアミノトロポン類を合成する方法(非特許文献1)、トロポロンから2−クロロトロポンを作り、これをアミノ化してアミノトロポン類を合成する方法(非特許文献2)、およびトロポロンから2−メトキシトロポンを作り、これをアミノ化してアミノトロポン類を合成する方法(非特許文献3)が記載されているが、これらは2段工程による2−アミノトロポンの製造方法である。
【0005】
以上のように、トロポロンから直接2−アミノトロポンを製造する例はない。2−アミノトロポンはアルカリや酸で加水分解するため、短時間で高い純度の2−アミノトロポンを得ることのできる製造法を開発する必要がある。
【0006】
【発明が解決しようとする課題】
本発明の課題は、前記従来技術の持つ問題点を取り除いた、新規な2−アミノトロポンを合成する方法を提供することである。そのためには、前記2−アミノトロポンの特性を考慮した製造条件、すなわち加水分解を受けない安定な製造条件を見出す必要がある。前記条件を満足する製造方法を見出すべく、トロポンを原料とする、1工程で安定的に2−アミノトロポンを合成する方法を見出すべく鋭意検討する中で、アミノ化にアンモニアを利用し、前記2−アミノトロポンの特性を考慮した製造条件を見出すべく、多くの試行錯誤をする中で、トロポンのアミノ化の反応媒体としてアンモニア水溶液を用い、耐圧容器を用いてアンモニアの飛散を防ぐ密閉下に、前記反応媒体を加熱し、アミノ化反応を試みる中で、前記反応を生成する2−アミノトロポンの分解なしに2−アミノトロポンを製造できる条件を見出し、前記課題を解決することができた。
【0007】
【課題を解決するための手段】
本発明は、トロポロンをアンモニア水からなる反応媒体中で、反応媒体を加熱し、反応原料および2−アミノトロポンの分解しない時間で、式1の工程により反応が進行する条件で反応させ一段階で2−アミノトロポンを生成させることを特徴とする2−アミノトロポンの製造方法である。
【0008】
【化2】
【0009】
好ましくは、反応工程の反応条件が、加熱温度を100℃以上300℃以下とし、反応時間を原料および生成物が分解することがない1時間以上の時間として進行させることを特徴とする前記2−アミノトロポンの製造方法であり、より好ましくは、反応媒体のアンモニア水の濃度が1%〜35%であることを特徴とする前記各2−アミノトロポンの製造方法である。
【0010】
【本発明の実施の態様】
本発明をより詳細に説明する。
A.本発明の特徴は基本的には、反応媒体のアンモニア水溶液の条件、反応温度、従って、前記アンモニア水溶液の濃度と反応温度に対応する反応圧力下で、所定時間反応させることである。
本発明の特徴は、非常に単純であるが、トロポロンから2−アミノトロポンを簡易な方法により製造できる条件があることを見出したことである。
B.本発明の特徴の、アンモニア水溶液の濃度の条件は限定されないが、特に好ましくは1%〜35%の水溶液である。
C.本発明の製造工程において、反応温度は少なくとも100℃であり、最高温度は、所望の反応を、所望の条件で進行すれば良く、反応スケールを考えれば、前記反応溶媒の条件を考慮しつつ、また、反応時間を考慮して決定しうる。
【0011】
【実施例】
以下、実施例により本発明を具体的に説明するが、この例示により本発明が限定的に解釈されるものではない。
【0012】
実施例1
トロポロン12.21g(0.100mol)と28%アンモニア水(50mL)を耐圧容器中,1時間160〜180℃で加熱した。放冷後,クロロホルム250mLで3回抽出し,抽出液に無水硫酸ナトリウムを加えて乾燥後,乾燥剤をろ別した。抽出液は濃縮して2−アミノトロポン12.05g(0.0995mol、純度99%以上)を得た。
生成物の特性;
黄色結晶,融点、106−107℃
1H−NMRスペクトル(CDCl3、400MHz、δ/ppm)
6.01(2H,brs)、6.74(1H,dd,J=9.5,9.4Hz)、6.86(1H,d,J=10.2Hz)、7.14(1H,ddd,J=10.2,9.5,1.4Hz)、7.20(1H,d,J=11.4Hz)、7.28(1H,ddd,J=11.4,9.4,1.4Hz)
この結果から,トロポロンから直接2−アミノトロポンが高純度且つ高収率で得られたことが分かった。
アミノトロポンはアルカリや酸で加水分解することが知られているが、本発明の条件によれば、耐圧アンプル中のアンモニア水反応媒体を用いると、従来の技術からの考えからは、加熱するという加水分解する条件にも関わらず、2−アミノトロポン安定に製造することができたことは、全く驚くべきことであった。反応媒体のアンモニア水はアルカリである。
【0013】
実施例2
トロポロン1.21g(0.01mol)と28%アンモニア水(5mL)を耐圧容器中、表1に記載した条件で加熱した。放冷後,クロロホルム25mLで3回抽出し,抽出液に無水硫酸ナトリウムを加えて乾燥後,乾燥剤をろ別した。抽出液は濃縮して2−アミノトロポンを得た。生成物の収率、融点、純度を表1に示した。
【0014】
【表1】
【0015】
前記のことから、原料および生成物が分解することがない時間は反応温度との相関する条件であり、要はアンモニア水を、密閉条件で所望の濃度に維持して、加熱下に反応を進行させることが重要である。
【0016】
実施例3
トロポロン0.121g〜1.21g(0.001mol〜0.01mol)と1%〜35%のアンモニア水(5mL〜10mL)を表2に記載した条件で、耐圧容器中、180℃で加熱した。放冷後,クロロホルム25mLで3回抽出し,抽出液に無水硫酸ナトリウムを加えて乾燥後,乾燥剤をろ別した。抽出液は濃縮して2−アミノトロポンを得た。生成物の収率、融点、純度を表2に示した。
【0017】
【表2】
【0018】
【発明の効果】
以上述べたように、本発明によれば,工業的な製造が困難であった2−アミノトロポンをトロポロンとアンモニア水から一段階で、かつ、短時間で高純度の2−アミノトロポンを高収率で製造することができる工業的工程の設計が容易な方法を提供できた、という優れた効果がもたすものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing 2-aminotropone from tropolone in aqueous ammonia in one step.
2-Aminotropone is a raw material for synthesizing tropone derivatives useful as gelling agents, pharmaceuticals, laser absorbing dyes, liquid crystal devices, optical recording materials such as electrophotographic photoreceptors, organic conductors, catalyst ligands, dyes, chelating reagents, etc. Is,
[0002]
[Prior art]
2-Aminotropone has been synthesized by the reaction of tropone with hydrazine, and the synthesized 2-aminotropone has been used as an intermediate for alkaline decomposition to produce tropolone. However, 2-aminotropone and its derivatives are important intermediates for the synthesis of various fine chemicals, especially pharmaceutical intermediates such as anti-inflammatory agents and organic low molecular gelling agents, and their production is simple and suitable for industrial production. There is a need for a method. The method for producing 2-aminotropone is that hydrazine, which is a dangerous reagent, is used, and the method for producing 2-aminotropone, which is widely used as a relatively easy-to-use reagent, is tropolone. This is a method of manufacturing through a two-step process, and it is necessary to further rationalize the manufacturing method.
[0003]
[Patent Document 1]
Japanese Patent Publication No. 29-623, claims, page 2 (3)
[Patent Document 2]
Japanese Patent Publication No. 32-5924, Claims, Examples 1, 3
[Non-patent document 1]
J. Am. Chem. Soc. , 74, 5688 (1952);
[Non-patent document 2]
J. Am. Chem. Soc. , 74, 5683 (1952);
[Non-Patent Document 3]
J. Am. Chem. Soc. , 73, 828 (1951);
[0004]
Patent Literature 1 discloses a method for producing a substituted 2-aminotropone using substituted tropones as a raw material by using aqueous ammonia. A method for producing 2-aminotropone from tropolone is described for producing 2-aminotropone. It merely mentions a method (reaction formula 3) of reacting 2-methoxytropone, which is an alkyl ether of tropolone, with ammonia to obtain 2-aminotropone in two steps. Patent Document 2 discloses a method for producing aminotropone by reacting tropones with ammonia (Example 3), but tropones are unstable, and ammonia has a melting point of minus 77.7 ° C and a boiling point of Has a toxicity of 33.4 ° C. and is toxic and irritating, and hydrazine (Example 1) has toxic properties such as irritating properties, and violently reacts with heat, fire, oxidizing agents and metal oxides such as iron rust. There is a problem of using a drug that is difficult to handle such as exploding.
In addition, Non-Patent Documents 1 to 3 disclose a method of preparing 2- (p-toluenesulfonyloxy) tropone from tropolone and aminating the same to synthesize aminotropones (Non-Patent Document 1), A method of preparing chlorotropone and aminating it to synthesize aminotropones (Non-Patent Document 2), and a method of preparing 2-methoxytropone from tropolone and aminating it to synthesize aminotropones (Non-Patent Document 3) These are two-step processes for producing 2-aminotropone.
[0005]
As described above, there is no example of producing 2-aminotropone directly from tropolone. Since 2-aminotropone is hydrolyzed with an alkali or an acid, it is necessary to develop a production method capable of obtaining high-purity 2-aminotropone in a short time.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for synthesizing a novel 2-aminotropone that eliminates the above-mentioned problems of the prior art. For this purpose, it is necessary to find production conditions in consideration of the characteristics of the 2-aminotropone, that is, stable production conditions that are not subject to hydrolysis. In order to find a production method that satisfies the above-mentioned conditions, while diligently studying to find a method of stably synthesizing 2-aminotropone using tropone as a raw material, ammonia was used for amination, In order to find the production conditions in consideration of the characteristics of aminotropone, in many trials and errors, using an aqueous ammonia solution as a reaction medium for amination of tropone, using a pressure-resistant container, and sealing the reaction under sealed conditions to prevent ammonia from scattering. By heating the medium and attempting an amination reaction, the present inventors have found conditions under which 2-aminotropone can be produced without decomposing 2-aminotropone, which produces the reaction, and have solved the problem.
[0007]
[Means for Solving the Problems]
In the present invention, tropolone is heated in a reaction medium composed of aqueous ammonia under a condition in which the reaction proceeds by the process of the formula 1 in a time period in which the reaction raw material and 2-aminotropone are not decomposed in a reaction medium consisting of two steps. -A method for producing 2-aminotropone, characterized by producing aminotropone.
[0008]
Embedded image
[0009]
Preferably, the reaction conditions of the reaction step are such that the heating temperature is 100 ° C. or more and 300 ° C. or less, and the reaction time is 1 hour or more in which the raw materials and products are not decomposed. It is a method for producing aminotropone, more preferably the method for producing each of the above-mentioned 2-aminotropones, wherein the concentration of aqueous ammonia in the reaction medium is 1% to 35%.
[0010]
[Embodiment of the present invention]
The present invention will be described in more detail.
A. The feature of the present invention is basically that the reaction is carried out for a predetermined time under the conditions and the reaction temperature of the aqueous ammonia solution of the reaction medium, that is, the reaction pressure corresponding to the concentration of the aqueous ammonia solution and the reaction temperature.
A feature of the present invention is that, although very simple, it has been found that there are conditions under which 2-aminotropone can be produced from tropolone by a simple method.
B. Although the condition of the concentration of the aqueous ammonia solution, which is a feature of the present invention, is not limited, an aqueous solution of 1% to 35% is particularly preferable.
C. In the production process of the present invention, the reaction temperature is at least 100 ° C., the maximum temperature, the desired reaction may be allowed to proceed under desired conditions, considering the reaction scale, considering the conditions of the reaction solvent, In addition, it can be determined in consideration of the reaction time.
[0011]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
[0012]
Example 1
12.21 g (0.100 mol) of tropolone and 28% aqueous ammonia (50 mL) were heated at 160 to 180 ° C. for 1 hour in a pressure vessel. After allowing to cool, the mixture was extracted three times with 250 mL of chloroform. The extract was dried over anhydrous sodium sulfate, and the desiccant was filtered off. The extract was concentrated to obtain 12.05 g (0.0995 mol, purity 99% or more) of 2-aminotropone.
Product properties;
Yellow crystal, melting point, 106-107 ° C
1 H-NMR spectrum (CDCl 3 , 400 MHz, δ / ppm)
6.01 (2H, brs), 6.74 (1H, dd, J = 9.5, 9.4 Hz), 6.86 (1H, d, J = 10.2 Hz), 7.14 (1H, ddd) , J = 10.2, 9.5, 1.4 Hz), 7.20 (1H, d, J = 11.4 Hz), 7.28 (1H, ddd, J = 11.4, 9.4, 1) .4Hz)
From this result, it was found that 2-aminotropone was directly obtained from tropolone in high purity and high yield.
Aminotropone is known to be hydrolyzed by an alkali or an acid. However, according to the conditions of the present invention, when an ammonia water reaction medium in a pressure-resistant ampoule is used, from the viewpoint of the prior art, it is considered that the hydrolysis requires heating. It was completely surprising that 2-aminotropone could be produced stably despite the decomposition conditions. The aqueous ammonia in the reaction medium is alkaline.
[0013]
Example 2
1.21 g (0.01 mol) of tropolone and 28% aqueous ammonia (5 mL) were heated in a pressure vessel under the conditions described in Table 1. After cooling, the mixture was extracted three times with 25 mL of chloroform. The extract was dried over anhydrous sodium sulfate, and the desiccant was filtered off. The extract was concentrated to obtain 2-aminotropone. The yield, melting point and purity of the product are shown in Table 1.
[0014]
[Table 1]
[0015]
From the above, the time during which the raw material and the product are not decomposed is a condition correlated with the reaction temperature.In short, the ammonia water is maintained at a desired concentration under closed conditions, and the reaction proceeds under heating. It is important that
[0016]
Example 3
0.121 g to 1.21 g (0.001 mol to 0.01 mol) of tropolone and 1% to 35% aqueous ammonia (5 mL to 10 mL) were heated at 180 ° C. in a pressure vessel under the conditions described in Table 2. After cooling, the mixture was extracted three times with 25 mL of chloroform. The extract was dried over anhydrous sodium sulfate, and the desiccant was filtered off. The extract was concentrated to obtain 2-aminotropone. The yield, melting point and purity of the product are shown in Table 2.
[0017]
[Table 2]
[0018]
【The invention's effect】
As described above, according to the present invention, 2-aminotropone, which had been difficult to produce industrially, was prepared from tropolone and aqueous ammonia in one step, and 2-aminotropone of high purity was obtained in a short time in a high yield. This has an excellent effect of providing a method for easily designing an industrial process that can be manufactured.
Claims (3)
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2093269A1 (en) * | 2006-12-14 | 2009-08-26 | Asahi Kasei Chemicals Corporation | Photobase generator and photocurable resin composition |
JP2010116370A (en) * | 2008-11-14 | 2010-05-27 | Asahi Kasei E-Materials Corp | Method for producing 2-aminotropones |
JP2010254593A (en) * | 2009-04-22 | 2010-11-11 | Asahi Kasei E-Materials Corp | Method for producing 2-aminotropone derivative |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2093269A1 (en) * | 2006-12-14 | 2009-08-26 | Asahi Kasei Chemicals Corporation | Photobase generator and photocurable resin composition |
EP2093269A4 (en) * | 2006-12-14 | 2011-03-30 | Asahi Kasei Chemicals Corp | Photobase generator and photocurable resin composition |
US8137892B2 (en) | 2006-12-14 | 2012-03-20 | Asahi Kasei Chemicals Corporation | Photobase generator and photocurable resin composition |
JP2010116370A (en) * | 2008-11-14 | 2010-05-27 | Asahi Kasei E-Materials Corp | Method for producing 2-aminotropones |
JP2010254593A (en) * | 2009-04-22 | 2010-11-11 | Asahi Kasei E-Materials Corp | Method for producing 2-aminotropone derivative |
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