JP2004262825A - Method for producing 2-oxazolidinones - Google Patents
Method for producing 2-oxazolidinones Download PDFInfo
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- JP2004262825A JP2004262825A JP2003054458A JP2003054458A JP2004262825A JP 2004262825 A JP2004262825 A JP 2004262825A JP 2003054458 A JP2003054458 A JP 2003054458A JP 2003054458 A JP2003054458 A JP 2003054458A JP 2004262825 A JP2004262825 A JP 2004262825A
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- oxazolidinones
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Abstract
Description
【０００１】
【発明の属する技術分野】
この出願の発明は、２−オキサゾリジノン類の製造方法に関するものである。さらに詳しくは、この出願の発明は、キラル補助剤をはじめとして、有機合成反応用の試薬や、医薬、農薬、化粧料等の原料もしくは中間体等として有用な２−オキサゾリジノン類の簡便で環境調和型の新しい製造方法に関するものである。
【０００２】
【従来の技術】
従来より、２−オキサゾリジノン類は、キラル補助剤をはじめとして各種の有機合成に有用なことが知られている化合物群である。
【０００３】
この２−オキサゾリジノン類の製造については、アミノアルコールを出発物質とする方法として、ホスゲンから合成される炭酸ジメチルとの反応や、一酸化炭素による酸化的カルボニル反応等が知られているが、従来では、毒性の高いホスゲンや一酸化炭素という反応剤の使用や高い反応温度条件を必要としている場合が多い。
【０００４】
ホスゲンや一酸化炭素という毒性の高い反応剤に代えて二酸化炭素を用い、その存在下でアジリジンの開環反応による合成法も報告されている。しかし、この場合には、反応剤としてのハライド塩の添加を必要としている。
【０００５】
このため、より毒性が低く、しかもハライド塩のような反応剤を使用せずに、環境調和型の合成法としてより効率的に２−オキサゾリジノン類の製造を可能にする方法の実現は望まれていた。また、２−オキサゾリジノン類として各種の利用が可能とされる修飾誘導体の合成をも可能とする方法が望まれてもいた。
【０００６】
【発明が解決しようとする課題】
そこで、この出願の発明は、上記のような従来の問題点を解決し、効率の良い炭素資源としての二酸化炭素に着目し、この二酸化炭素を用いることによって、より毒性が低く、しかもハライド塩のような反応剤を使用せずに、環境調和型の合成法としてより効率的に２−オキサゾリジノン類の製造を可能にする方法を提供し、また、２−オキサゾリジノン類として各種の利用が可能とされる修飾誘導体の合成をも可能とする方法を提供することを課題としている。
【０００７】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、第１には、次式
【０００８】
【化３】
で表わされるアミノメチルアレン類を遷移金属触媒の存在下に二酸化炭素と反応させ、次式
【０００９】
【化４】
で表わされる２−オキサゾリジノン類を製造することを特徴とする２−オキサゾリジノン類の製造方法を提供する。
【００１０】
そして、この出願の発明は、上記方法について、第２には、二酸化炭素の加圧下で反応させることを特徴とする２−オキサゾリジノン類の製造方法を、第３には、１．０ＭＰａ以上の加圧下で反応させることを特徴とする２−オキサゾリジノン類の製造方法を、第４には、超臨界二酸化炭素下で反応させることを特徴とする２−オキサゾリジノン類の製造方法を提供し、第５には、遷移金属触媒は、第８族〜第１０族金属もしくはその化合物のうちの１種以上であることを特徴とする２−オキサゾリジノン類の製造方法を提供する。
【００１１】
【発明の実施の形態】
この出願の発明は上記のとおりの特徴をもつものであるが、以下にその実施の形態について説明する。
【００１２】
この出願の発明の２−オキサゾリジノン類の製造方法における出発物質の一つは、前記の式（１）で表わされるようにアミノメチルアレン類である。この化合物では、前記の符号Ｒ１〜Ｒ６のいずれもが、同一または別異に、水素原子または置換基を有してもよい炭化水素基を示している。この場合の炭化水素基は、鎖状または環状で、飽和もしくは不飽和の各種のものであってよく、アルキル基、アルケニル基等の脂肪族基、シクロアルキル基、シクロアルキルアルキル基等の脂環式基、フェニル基、トリル基等のアリール基、あるいは異種原子を含む複素環基等の各種のものであってよい。
【００１３】
また、これらの炭化水素基は、この出願の発明に寄与する限り、各種の置換基、たとえばアルコキシ基、エステル基、ニトロ基、シアノ基等を有していてもよい。
【００１４】
反応基質としての前記式（１）で表わされるアミノメチルアレン類について、これを具体的に例示すると、たとえば、Ｎ−メチルアミノメチルアレン、Ｎ−エアミノメチルアレン、Ｎ−プロピルアミノメチルアレン類、Ｎ−ベンジルアミノメチルアレンをはじめとするＮ−アルキルアミノメチルアレンやアミノメチルアレン、アレン上にアルキル、フェニル置換基を導入した化合物を挙げることができる。
【００１５】
前記の式（１）で表わされるアミノメチルアレン類は、この出願の発明においては二酸化炭素と反応される。この際の反応は、二酸化炭素の加圧下に行うことが望ましい。
【００１６】
二酸化炭素の圧力を向上させると生成物の収率が増加し、特に超臨界二酸化炭素下（１５．０ＭＰａ、５０℃）で、たとえば７０％以上に達することが確認されている。二酸化炭素の圧力が１．０ＭＰａ未満では二酸化炭素が反応に関与しない生成物である３−ピロリンの副生が増加する傾向にある。このため、実際的には、１．０ＭＰａ以上とすることが好ましい。超臨界二酸化炭素下ではアミンからのカルバミン酸生成が有利になり、反応効率が向上したものと考えられる。
【００１７】
そして、この出願の発明では、上記の反応に遷移金属触媒を用いることを特徴としてもいる。この場合の遷移金属触媒としては、パラジウム、ルテニウム、ロジウム、イリジウム、ニッケル、白金などの後周期遷移金属またはその化合物を好適に用いることができるが、特にパラジウムが触媒として有効である。なかでも、化合物としての酢酸パラジウムや塩化パラジウムのような有機酸塩や無機酸塩、そして、ジクロロビス（アセトニトリル）パラジウム（ＩＩ）錯体、ジクロロビス（ホスファイト）パラジウム（ＩＩ）錯体、ジクロロビス（ホスフィン）パラジウム（ＩＩ）錯体、ジベンジリデンアセトンパラジウム（Ｏ）錯体、テトラキス（ホスファイト）パラジウム（Ｏ）錯体などの様々なＰｄ（Ｏ）およびＰｄ（ＩＩ）錯体を好適に用いることができる。特に酢酸パラジウムが触媒前駆体としてもっとも活性が高いことも確認されている。
【００１８】
反応基質としての前記のアミノメチルアレン類と触媒との使用割合は、モル比として、一般的には、基質／触媒＝５０〜５００の範囲もしくはその近傍を目安とすることができる。
【００１９】
超臨界二酸化炭素のみを媒体としもよいが、この出願の発明においては、有機溶媒、たとえばトルエン、ジクロロメタン、ＴＨＦ等を溶媒として添加することが有効である。
【００２０】
この出願の発明の方法においては、無毒の二酸化炭素カルボニル源とする反応であり、従来法よりも使用する化学物質の安全性に配慮し、反応に伴う廃棄物を最小限に抑えた環境負荷低減プロセスが実現される。
【００２１】
また、ファインケミカルズをはじめとする各種合成中間体等として有用な前記式（２）で表わされる２−オキサゾリジノン類の製造法として重要となり、生成物の５位のビニル基をさらに修飾、変換することができる点に大きな魅力がある。
【００２２】
そこで以下に実施例を示し、さらに詳しく説明する。もちろん、以下の例によって発明が限定されることはない。
【００２３】
【実施例】
オートクレーブ中に、トルエン（１．５ｍＬ）、酢酸パラジウム（２．２ｍｇ、１．０×１０−２ｍｍｏｌ）、Ｎ−メチルアミノメチルアレン（１２４．７ｍｇ、１．５ｍｍｏｌ）を導入し、二酸化炭素を圧入（０．２５．０ＭＰａ）したのち、室温−１００℃で攪拌する。５０℃の二酸化炭素の超臨界状態で、所定の反応時間（１５時間）後、反応容器を冷却し、二酸化炭素を放出した。通常の分離操作により、３−メチル−５−ビニル−２−オキサゾリジノンが収率７３％（１３８．１ｍｇ、１．０９ｍｍｏｌ）で得られた。
【００２４】
【発明の効果】
以上詳しく説明したとおり、この出願の発明によって、より毒性が低く、しかもハライド塩のような反応剤を使用せずに、環境調和型の合成法としてより効率的に２−オキサゾリジノン類の製造を可能にする方法が提供され、また、２−オキサゾリジノン類として各種の利用が可能とされる修飾誘導体の合成をも可能とする方法が提供される。[0001]
TECHNICAL FIELD OF THE INVENTION
The invention of this application relates to a method for producing 2-oxazolidinones. More specifically, the invention of this application relates to a simple and environmentally friendly 2-oxazolidinone useful as a chiral auxiliary, a reagent for an organic synthesis reaction, a raw material or an intermediate of a pharmaceutical, an agricultural chemical, a cosmetic or the like. It relates to a new method of manufacturing a mold.
[0002]
[Prior art]
Conventionally, 2-oxazolidinones are a group of compounds known to be useful for various organic syntheses, including chiral auxiliaries.
[0003]
Regarding the production of the 2-oxazolidinones, as a method using amino alcohol as a starting material, a reaction with dimethyl carbonate synthesized from phosgene, an oxidative carbonyl reaction with carbon monoxide, and the like are known. Often, the use of highly toxic reagents such as phosgene and carbon monoxide and high reaction temperature conditions are required.
[0004]
A synthetic method has been reported in which carbon dioxide is used instead of highly toxic reagents such as phosgene and carbon monoxide, and a ring opening reaction of aziridine is used in the presence of carbon dioxide. However, in this case, it is necessary to add a halide salt as a reactant.
[0005]
For this reason, it is desired to realize a method capable of producing 2-oxazolidinones more efficiently as an environmentally friendly synthesis method without using a reactant such as a halide salt and having a lower toxicity. Was. In addition, a method that enables the synthesis of a modified derivative that can be used in various ways as 2-oxazolidinones has been desired.
[0006]
[Problems to be solved by the invention]
Therefore, the invention of this application solves the conventional problems as described above, and focuses on carbon dioxide as an efficient carbon resource, and by using this carbon dioxide, the toxicity is lower and the halide salt The present invention provides a method that enables more efficient production of 2-oxazolidinones as an environmentally friendly synthesis method without using such a reactant, and various uses as 2-oxazolidinones are possible. It is an object of the present invention to provide a method capable of synthesizing a modified derivative.
[0007]
[Means for Solving the Problems]
The invention of this application solves the above-mentioned problems, and firstly, the following formula:
Embedded image
Is reacted with carbon dioxide in the presence of a transition metal catalyst to obtain the following formula:
Embedded image
A process for producing 2-oxazolidinones represented by the formula:
[0010]
The invention of this application relates to the above method, secondly, a method for producing 2-oxazolidinones characterized by reacting under pressure of carbon dioxide, and thirdly, a method for producing a 2-oxazolidinone compound having a pressure of 1.0 MPa or more. Fourth, a method for producing 2-oxazolidinones characterized by reacting under pressure, fourthly, a method for producing 2-oxazolidinones characterized by reacting under supercritical carbon dioxide, and fifthly, Provides a method for producing 2-oxazolidinones, wherein the transition metal catalyst is at least one of Group 8 to Group 10 metals or compounds thereof.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
The invention of this application has the features as described above, and embodiments thereof will be described below.
[0012]
One of the starting materials in the method for producing 2-oxazolidinones of the invention of this application is an aminomethylarene as represented by the above formula (1). In this compound, any of the above-mentioned symbols R 1 to R 6 is the same or different and represents a hydrogen atom or a hydrocarbon group which may have a substituent. The hydrocarbon group in this case may be chain or cyclic, saturated or unsaturated, and may be an aliphatic group such as an alkyl group or an alkenyl group, or an alicyclic group such as a cycloalkyl group or a cycloalkylalkyl group. Various groups such as an aryl group such as a formula group, a phenyl group and a tolyl group, or a heterocyclic group containing a hetero atom may be used.
[0013]
Further, these hydrocarbon groups may have various substituents, for example, an alkoxy group, an ester group, a nitro group, a cyano group, and the like, as long as they contribute to the invention of this application.
[0014]
Specific examples of the aminomethylallene represented by the above formula (1) as a reaction substrate include, for example, N-methylaminomethylarene, N-eaminomethylarene, N-propylaminomethylarene, Examples include N-alkylaminomethylarene such as N-benzylaminomethylarene, aminomethylarene, and compounds in which an alkyl or phenyl substituent is introduced on allene.
[0015]
The aminomethylallene represented by the above formula (1) is reacted with carbon dioxide in the invention of this application. The reaction at this time is desirably performed under pressure of carbon dioxide.
[0016]
It has been confirmed that when the pressure of carbon dioxide is increased, the yield of the product increases, and particularly reaches 70% or more under supercritical carbon dioxide (15.0 MPa, 50 ° C.). If the pressure of carbon dioxide is less than 1.0 MPa, the by-product of 3-pyrroline, which is a product in which carbon dioxide does not participate in the reaction, tends to increase. For this reason, it is practically preferable to set the pressure to 1.0 MPa or more. It is considered that the formation of carbamic acid from the amine was advantageous under supercritical carbon dioxide, and the reaction efficiency was improved.
[0017]
The invention of this application is also characterized in that a transition metal catalyst is used in the above reaction. As the transition metal catalyst in this case, a late transition metal such as palladium, ruthenium, rhodium, iridium, nickel, platinum or a compound thereof can be suitably used, and palladium is particularly effective as a catalyst. Among them, organic and inorganic acid salts such as palladium acetate and palladium chloride as compounds, and dichlorobis (acetonitrile) palladium (II) complex, dichlorobis (phosphite) palladium (II) complex, dichlorobis (phosphine) palladium Various Pd (O) and Pd (II) complexes such as a (II) complex, a dibenzylideneacetone palladium (O) complex, and a tetrakis (phosphite) palladium (O) complex can be suitably used. In particular, it has been confirmed that palladium acetate has the highest activity as a catalyst precursor.
[0018]
In general, the molar ratio of the above-mentioned aminomethylallenes and the catalyst used as a reaction substrate may be in the range of substrate / catalyst = 50 to 500 or in the vicinity thereof.
[0019]
Although only supercritical carbon dioxide may be used as a medium, in the invention of this application, it is effective to add an organic solvent such as toluene, dichloromethane, THF or the like as a solvent.
[0020]
In the method of the invention of this application, the reaction is a non-toxic carbon dioxide carbonyl source, and the safety of chemical substances used is considered more than in the conventional method, and the environmental burden is reduced by minimizing the waste accompanying the reaction. The process is realized.
[0021]
Further, it becomes important as a method for producing 2-oxazolidinones represented by the formula (2), which is useful as various synthetic intermediates including fine chemicals, and it is possible to further modify and convert the 5-position vinyl group of the product. There is great attraction in what you can do.
[0022]
Therefore, an embodiment will be shown below and will be described in more detail. Of course, the invention is not limited by the following examples.
[0023]
【Example】
Into the autoclave, toluene (1.5 mL), palladium acetate (2.2 mg, 1.0 × 10−2 mmol), and N-methylaminomethylarene (124.7 mg, 1.5 mmol) were introduced, and carbon dioxide was injected. (0.25.0 MPa), and then the mixture is stirred at room temperature to -100 ° C. After a predetermined reaction time (15 hours) in a supercritical state of carbon dioxide at 50 ° C., the reaction vessel was cooled to release carbon dioxide. By a usual separation operation, 3-methyl-5-vinyl-2-oxazolidinone was obtained in a yield of 73% (138.1 mg, 1.09 mmol).
[0024]
【The invention's effect】
As described in detail above, the invention of the present application makes it possible to produce 2-oxazolidinones more efficiently as an environmentally friendly synthesis method without using a reactant such as a halide salt, with less toxicity. And a method for synthesizing a modified derivative that can be used in various ways as 2-oxazolidinones.
Claims (5)
で表わされるアミノメチルアレン類を遷移金属触媒の存在下に二酸化炭素と反応させ、次式（２）
で表わされる２−オキサゾリジノン類を製造することを特徴とする２−オキサゾリジノン類の製造方法。The following equation (1)
Is reacted with carbon dioxide in the presence of a transition metal catalyst to give the following formula (2)
A method for producing 2-oxazolidinones, which comprises producing 2-oxazolidinones represented by the formula:
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003054458A JP4268424B2 (en) | 2003-02-28 | 2003-02-28 | Method for producing 2-oxazolidinones |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003054458A JP4268424B2 (en) | 2003-02-28 | 2003-02-28 | Method for producing 2-oxazolidinones |
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| Publication Number | Publication Date |
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| JP2004262825A true JP2004262825A (en) | 2004-09-24 |
| JP4268424B2 JP4268424B2 (en) | 2009-05-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013053267A (en) * | 2011-09-06 | 2013-03-21 | Kuraray Co Ltd | Modified vinyl alcohol-based polymer, modified vinyl ester-based polymer and methods for producing them |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013053267A (en) * | 2011-09-06 | 2013-03-21 | Kuraray Co Ltd | Modified vinyl alcohol-based polymer, modified vinyl ester-based polymer and methods for producing them |
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| JP4268424B2 (en) | 2009-05-27 |
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