JP2007008903A - Method for oxidizing alkanes or cycloalkanes - Google Patents
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Abstract
【課題】 環境破壊物質を排出せず効率よいアルカン類又はシクロアルカン類の酸化方法を提供する。
【解決手段】 アルカン類又はシクロアルカン類を、二酸化炭素の存在下、水及び酸素の超臨界反応により酸化する、アルカン類又はシクロアルカン類の酸化方法。本酸化反応によりアルコールおよび／またはケトン化合物が得られ、特に２−アダマンタノンの合成に有利である。
【選択図】 なしPROBLEM TO BE SOLVED: To provide an efficient method for oxidizing alkanes or cycloalkanes without discharging environmentally destructive substances.
A method for oxidizing alkanes or cycloalkanes in which alkanes or cycloalkanes are oxidized by a supercritical reaction of water and oxygen in the presence of carbon dioxide. This oxidation reaction yields an alcohol and / or ketone compound, which is particularly advantageous for the synthesis of 2-adamantanone.
[Selection figure] None
Description
本発明は、アルカン類又はシクロアルカン類の酸化方法に関する。 The present invention relates to a method for oxidizing alkanes or cycloalkanes.
近年医薬品、フォトレジスト等の分野で注目を浴びつつあるアダマンタン誘導体の出発物質として２−アダマンタノンが脚光を浴びつつある。 In recent years, 2-adamantanone is in the spotlight as a starting material for adamantane derivatives, which are attracting attention in the fields of pharmaceuticals, photoresists and the like in recent years.
２−アダマンタノンを得る方法として、アダマンタンの水和・酸化反応が挙げられる。一般に炭化水素化合物の水和・酸化反応には硫酸、硝酸による酸化反応等種々の手法が有るが、アダマンタンの水和・酸化には硫酸法等が唯一の工業的製造方法として確立されている（特許文献１）。
しかし、硫酸法では２−アダマンタノンの収率が低い上に、反応中にＳＯ２が発生し、反応後はその全量を中和するため処理コストの負担が大きく環境負荷も高い大量の硫酸ピッチが発生するという問題があった。
As a method for obtaining 2-adamantanone, hydration / oxidation reaction of adamantane can be mentioned. In general, there are various methods such as oxidation reaction with sulfuric acid and nitric acid for the hydration / oxidation reaction of hydrocarbon compounds, but the sulfuric acid method has been established as the only industrial production method for the hydration / oxidation of adamantane ( Patent Document 1).
However, in the sulfuric acid method, the yield of 2-adamantanone is low and SO 2 is generated during the reaction. After the reaction, the total amount is neutralized. There was a problem that occurred.
ｔ−ブチルハイドロパーオキサイドを酸化剤として種々の金属錯体を触媒とする方法（非特許文献１等）や、過酸化水素を酸化剤として鉄化合物等を酸化剤とする方法（非特許文献２）も提案されているが、酸化剤が高価な上、反応の制御が困難であり爆発の危険性があるという問題があった。 A method using t-butyl hydroperoxide as an oxidizing agent and various metal complexes as catalysts (Non-patent Document 1 and the like), and a method using hydrogen peroxide as an oxidizing agent and an iron compound and the like as an oxidizing agent (Non-Patent Document 2) However, there are problems that the oxidizing agent is expensive and the reaction is difficult to control and there is a risk of explosion.
また、触媒を用いて２−アダマンタノンを合成した例（特許文献２，３）も提案されているが合成後に触媒の分離工程を要するという問題があった。
本発明の目的は、環境破壊物質を排出せず効率よいアルカン類又はシクロアルカン類の酸化方法を提供することである。 An object of the present invention is to provide an efficient method for oxidizing alkanes or cycloalkanes without discharging environmentally destructive substances.
本発明によれば、以下のアルカン類又はシクロアルカン類の酸化方法が提供される。
１．アルカン類又はシクロアルカン類を、二酸化炭素の存在下、水及び酸素の超臨界反応により酸化する、アルカン類又はシクロアルカン類の酸化方法。
２．前記アルカン類又はシクロアルカン類がアダマンタンである1記載のアルカン類又はシクロアルカン類の酸化方法。
３．反応温度が２００〜３３０℃である１又は２記載のアルカン類又はシクロアルカン類の酸化方法。
According to the present invention, the following method for oxidizing alkanes or cycloalkanes is provided.
1. A method for oxidizing alkanes or cycloalkanes, wherein alkanes or cycloalkanes are oxidized by a supercritical reaction of water and oxygen in the presence of carbon dioxide.
2. 2. The method for oxidizing an alkane or cycloalkane according to 1, wherein the alkane or cycloalkane is adamantane.
3. The method for oxidizing alkanes or cycloalkanes according to 1 or 2, wherein the reaction temperature is 200 to 330 ° C.
本発明によれば、環境破壊物質を排出せず効率よいアルカン類又はシクロアルカン類の酸化方法が提供できる。 According to the present invention, it is possible to provide an efficient method for oxidizing alkanes or cycloalkanes without discharging environmentally destructive substances.
本発明は、二酸化炭素の存在下、水及び酸素の超臨界反応によりアルカン類又はシクロアルカン類を酸化することを特徴とする。本発明によりアルカン類又はシクロアルカン類のアルコール体及びケトン体が得られる。 The present invention is characterized in that alkanes or cycloalkanes are oxidized by a supercritical reaction of water and oxygen in the presence of carbon dioxide. According to the present invention, alcohols and ketones of alkanes or cycloalkanes can be obtained.
原料となるアルカン類又はシクロアルカン類として、例えば、アダマンタンが使用できるが、これに限定されない。例えば、炭素数５〜１５のアルカン、炭素数５〜１５のアルキル置換又は未置換のシクロアルカン、環が１〜５個のシクロアルカン等を使用することができる。 For example, adamantane can be used as the raw material alkane or cycloalkane, but is not limited thereto. For example, an alkane having 5 to 15 carbon atoms, an alkyl-substituted or unsubstituted cycloalkane having 5 to 15 carbon atoms, a cycloalkane having 1 to 5 rings, and the like can be used.
ここで、「水及び酸素の超臨界反応」とは水熱酸化反応をいう。
水熱酸化反応は、通常水を超臨界水（３７４．２℃以上かつ２２．１ＭＰａ以上）又は亜臨界水の状態で行う反応である。このとき酸素は酸化剤として作用する。水熱酸化反応を利用して、アルカン類又はシクロアルカン類からケトン、アルコール等のこれらの酸化物を得ることができる。
Here, the “supercritical reaction of water and oxygen” refers to a hydrothermal oxidation reaction.
The hydrothermal oxidation reaction is usually a reaction in which water is supercritical water (374.2 ° C. or higher and 22.1 MPa or higher) or subcritical water. At this time, oxygen acts as an oxidizing agent. These oxides such as ketones and alcohols can be obtained from alkanes or cycloalkanes by utilizing a hydrothermal oxidation reaction.
本発明の製造方法は、二酸化炭素を存在下で水熱酸化反応を行うことを特徴とする。二酸化炭素は通常行われる水熱酸化反応よりも温和な条件（３１．１℃以上かつ７．４８ＭＰａ以上）で超臨界流体（超臨界二酸化炭素）になる。二酸化炭素存在下では水熱酸化反応が通常行われる反応条件よりも温和な条件で反応が進行し、かつ反応速度が速いためケトン、アルコール等を効率よく得ることができる。 The production method of the present invention is characterized in that a hydrothermal oxidation reaction is performed in the presence of carbon dioxide. Carbon dioxide becomes a supercritical fluid (supercritical carbon dioxide) under milder conditions (31.1 ° C. or more and 7.48 MPa or more) than the usual hydrothermal oxidation reaction. In the presence of carbon dioxide, the reaction proceeds under milder conditions than those under which the hydrothermal oxidation reaction is normally performed, and the reaction rate is fast, so that ketones, alcohols and the like can be obtained efficiently.
本発明の酸化方法で使用するのは、水、酸素及び二酸化炭素なので、硫酸法のように環境負荷がかかる物質は発生せず、また触媒を用いる方法のように触媒を回収する作業が不要となる。 Since the oxidation method of the present invention uses water, oxygen, and carbon dioxide, no substances that impose environmental burdens like the sulfuric acid method are generated, and there is no need to recover the catalyst as in the method using a catalyst. Become.
反応で使用する水の量は、原料であるアルカン類又はシクロアルカン類に対して通常１０倍〜１００倍(重量）である。 The amount of water used in the reaction is usually 10 to 100 times (weight) with respect to the raw material alkane or cycloalkane.
反応で使用する酸素及び二酸化炭素の量は、特に限定されないが、原料であるアルカン類又はシクロアルカン類に対して大過剰であればよい。 The amount of oxygen and carbon dioxide used in the reaction is not particularly limited as long as it is in a large excess relative to the raw material alkane or cycloalkane.
反応条件として、圧力は通常７．５ＭＰａ以上である。７．５ＭＰａ未満だと二酸化炭素が超臨界流体にならず反応が進行しない恐れがある。圧力は設定する反応温度において上記要件を満たしていればよい。反応温度は、反応物であるアルカン類又はシクロアルカン類に応じて設定することができる。 As reaction conditions, the pressure is usually 7.5 MPa or more. If it is less than 7.5 MPa, carbon dioxide does not become a supercritical fluid and the reaction may not proceed. The pressure should just satisfy the said requirements in the reaction temperature to set. The reaction temperature can be set according to the alkane or cycloalkane that is the reactant.
好ましくは、反応温度は２００〜３３０℃である。反応温度が２００℃未満だとアルカン類又はシクロアルカン類の転化率が十分でない場合があり、反応温度が３３０℃を超えると副生する重質分が増え、アルコール及びケトンの選択率が下がる場合がある。 Preferably, the reaction temperature is 200-330 ° C. When the reaction temperature is less than 200 ° C, the conversion rate of alkanes or cycloalkanes may not be sufficient, and when the reaction temperature exceeds 330 ° C, the heavy by-product increases and the selectivity for alcohol and ketone decreases. There is.
アダマンタン、１−アダマンタノール、２−アダマンタノール及び２−アダマンタノンは反応場においては下記式の平衡関係にある。
以下、実施例において本発明を詳細に説明するが、本発明はこれに限定されることはない。
実施例１
容量３．５ｍｌのステンレス製のオートクレーブに、アダマンタン（出光石油化学（株）製）０．０２０ｇ、水０．７５ｍｌを入れた後、蓋をして真空ポンプで内部の空気を脱気した。次に、オートクレーブに付けた枝管から酸素及び二酸化炭素からなる混合ガス（酸素５０ｖｏｌ％、二酸化炭素５０ｖｏｌ％）を導入し、オートクレーブ内の内圧が４ＭＰａとなるようにした。次に、オートクレーブを、溶融塩バスを用いて３００℃に昇温し、この温度を保ちながら３０分反応させた。オートクレーブを溶融塩バスから取り出し、室温まで冷却後、オートクレーブの蓋を開け生成物を取り出した。
得られた生成物の成分についてガスクロマトグラフィーにて分析した。アダマンタン、１−アダマンタノール、２−アダマンタノール及び２−アダマンタノンにそれぞれ由来するピークのピーク面積から、各化合物の生成物全体に対する含有率を求め、アダマンタン１００に対する各々の比率を求めた。
〔アダマンタンの転化率（％）〕
＝〔１−アダマンタノールの含有率（％）〕＋〔２−アダマンタノールの含有率（％）〕＋〔２−アダマンタノンの含有率（％）〕
結果を表１に示す。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this.
Example 1
0.020 g of adamantane (manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.75 ml of water were put into a stainless steel autoclave having a capacity of 3.5 ml. Next, a mixed gas composed of oxygen and carbon dioxide (oxygen 50 vol%, carbon dioxide 50 vol%) was introduced from a branch pipe attached to the autoclave so that the internal pressure in the autoclave was 4 MPa. Next, the autoclave was heated to 300 ° C. using a molten salt bath and reacted for 30 minutes while maintaining this temperature. The autoclave was taken out of the molten salt bath, cooled to room temperature, the autoclave lid was opened, and the product was taken out.
The components of the obtained product were analyzed by gas chromatography. From the peak areas of peaks derived from adamantane, 1-adamantanol, 2-adamantanol and 2-adamantanone, the content of each compound relative to the entire product was determined, and the ratio of each compound to adamantane 100 was determined.
[Conversion rate of adamantane (%)]
= [1-adamantanol content (%)] + [2-adamantanol content (%)] + [2-adamantanone content (%)]
The results are shown in Table 1.
実施例２
昇温温度を２５０℃にすることを除いては、実施例１と同様にして反応を行った。得られた生成物について実施例１と同様に分析した。結果を表１に示す。
Example 2
The reaction was performed in the same manner as in Example 1 except that the temperature elevation temperature was 250 ° C. The obtained product was analyzed in the same manner as in Example 1. The results are shown in Table 1.
実施例３
昇温温度を３５０℃にすることを除いては、実施例１と同様にして反応を行った。得られた生成物について実施例１と同様に分析した。結果を表１に示す。
Example 3
The reaction was conducted in the same manner as in Example 1 except that the temperature elevation temperature was 350 ° C. The obtained product was analyzed in the same manner as in Example 1. The results are shown in Table 1.
比較例１
オートクレーブに導入するガスを酸素とすること以外は、実施例１と同様にして反応を行った。得られた生成物について実施例１と同様に分析した。結果を表１に示す。
Comparative Example 1
The reaction was performed in the same manner as in Example 1 except that oxygen was used as the gas introduced into the autoclave. The obtained product was analyzed in the same manner as in Example 1. The results are shown in Table 1.
比較例２
オートクレーブに導入するガスを二酸化炭素とすること以外は、実施例１と同様にして反応を行った。得られた生成物について実施例１と同様に分析した。結果を表１に示す。
Comparative Example 2
The reaction was performed in the same manner as in Example 1 except that the gas introduced into the autoclave was carbon dioxide. The obtained product was analyzed in the same manner as in Example 1. The results are shown in Table 1.
比較例３
オートクレーブに導入するガスをアルゴンガスとし、オートクレーブの内圧を常圧にすること以外は、実施例１と同様にして反応を行った。得られた生成物について実施例１と同様に分析した。結果を表１に示す。
Comparative Example 3
The reaction was performed in the same manner as in Example 1 except that the gas introduced into the autoclave was argon gas and the internal pressure of the autoclave was set to normal pressure. The obtained product was analyzed in the same manner as in Example 1. The results are shown in Table 1.
比較例４
オートクレーブの蓋を閉めた後、脱気処理及び加圧処理せず、常圧の空気の状態にしたことを除いては実施例１と同様にして反応を行った。得られた生成物について実施例１と同様に分析した。結果を表１に示す。
Comparative Example 4
After closing the autoclave lid, the reaction was carried out in the same manner as in Example 1 except that the deaeration treatment and the pressurization treatment were not carried out and the air was brought to the normal pressure. The obtained product was analyzed in the same manner as in Example 1. The results are shown in Table 1.
本発明の酸化方法は、アルカン類又はシクロアルカン類を酸化する方法として利用することができる。本発明で得られる２−アダマンタノンは層間絶縁膜、半導体フォトレジスト等に使用される。 The oxidation method of the present invention can be used as a method for oxidizing alkanes or cycloalkanes. The 2-adamantanone obtained in the present invention is used for an interlayer insulating film, a semiconductor photoresist and the like.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100818430B1 (en) * | 2001-02-27 | 2008-04-01 | 마츠시타 덴끼 산교 가부시키가이샤 | Fuel cell generation system |
| JP2009155299A (en) * | 2007-12-27 | 2009-07-16 | National Institute Of Advanced Industrial & Technology | Method for synthesizing aromatic substituted aliphatic cyclic ketone compounds |
-
2005
- 2005-07-04 JP JP2005194973A patent/JP2007008903A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100818430B1 (en) * | 2001-02-27 | 2008-04-01 | 마츠시타 덴끼 산교 가부시키가이샤 | Fuel cell generation system |
| JP2009155299A (en) * | 2007-12-27 | 2009-07-16 | National Institute Of Advanced Industrial & Technology | Method for synthesizing aromatic substituted aliphatic cyclic ketone compounds |
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