JP3284238B2 - Method for producing oxazolidone - Google Patents
Method for producing oxazolidoneInfo
- Publication number
- JP3284238B2 JP3284238B2 JP2000018694A JP2000018694A JP3284238B2 JP 3284238 B2 JP3284238 B2 JP 3284238B2 JP 2000018694 A JP2000018694 A JP 2000018694A JP 2000018694 A JP2000018694 A JP 2000018694A JP 3284238 B2 JP3284238 B2 JP 3284238B2
- Authority
- JP
- Japan
- Prior art keywords
- oxazolidone
- carbon dioxide
- present
- tin compound
- mmol
- 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.)
- Expired - Lifetime
Links
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 18
- 150000003606 tin compounds Chemical class 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000002169 ethanolamines Chemical class 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 4
- 150000001414 amino alcohols Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- -1 dialkyltin oxide Chemical class 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical class O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 2
- YLRLKOUKACPPHU-UHFFFAOYSA-N 3-ethyl-1,3-oxazolidin-2-id-4-one Chemical compound C(C)N1[CH-]OCC1=O YLRLKOUKACPPHU-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 229940125681 anticonvulsant agent Drugs 0.000 description 2
- 239000001961 anticonvulsive agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- RIBJLXBLWQKWLO-UHFFFAOYSA-N diphenylstiborylbenzene Chemical compound C=1C=CC=CC=1[Sb](C=1C=CC=CC=1)(=O)C1=CC=CC=C1 RIBJLXBLWQKWLO-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical group CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明はオキサゾリドンの製
造方法に関するものであり、更に詳細には二酸化炭素と
アミノアルコールを反応させてオキサゾリドンを製造す
る方法の改良に関するものである。The present invention relates to a method for producing oxazolidone, and more particularly, to an improvement in a method for producing oxazolidone by reacting carbon dioxide with an amino alcohol.
【０００２】[0002]
【従来の技術】抗けいれん剤などの医薬品合成原料、合
成中間体や農薬、あるいは高機能液晶材料合成中間体等
として有用なオキサゾリドンはエタノールアミンとホス
ゲン或いは炭酸ガスから合成することができるが、ホス
ゲンはきわめて毒性の高いガスであり、製造や取り扱い
に注意を要するという問題がある。2. Description of the Related Art Oxazolidones useful as raw materials for the synthesis of pharmaceuticals such as anticonvulsants, synthetic intermediates and agricultural chemicals, or synthetic intermediates for high-performance liquid crystal materials can be synthesized from ethanolamine and phosgene or carbon dioxide. Is an extremely toxic gas, and has a problem that care must be taken during manufacture and handling.
【０００３】これに対し、二酸化炭素は安価で豊富に存
在する原料ガスであり、取り扱いに際して危険が少ない
ため、オキサゾリドンの合成用原料ガスとして有利に使
用される。[0003] On the other hand, carbon dioxide is an inexpensive and abundant raw material gas, and has little danger in handling. Therefore, carbon dioxide is advantageously used as a raw material gas for the synthesis of oxazolidone.
【０００４】[0004]
【発明が解決しようとする課題】この二酸化炭素とアミ
ノアルコールを原料とするオキサゾリドンの製造方法と
しては、触媒としてアンチモン化合物を使用する方法等
などが知られている(H.Matsuda, A. Baba, R. Nomura,
M. Kori, and S Ogawa, Ind. Eng. Chem. Prod.Res. De
v., 24, 239(1985)。As a method for producing oxazolidone using carbon dioxide and amino alcohol as raw materials, a method using an antimony compound as a catalyst and the like are known (H. Matsuda, A. Baba, R. Nomura,
M. Kori, and S Ogawa, Ind. Eng. Chem. Prod. Res. De
v., 24, 239 (1985).
【０００５】しかし、この方法では、原料アミノアルコ
ールの選択自由度が制約され、そのアルキル鎖上に置換
基を持たないエタノールアミンなどを使用した場合には
目的とするオキサゾリドンががほとんど生成しないとい
う問題がある。本発明は、上記の状況に鑑みて行われた
ものであり、その目的は二酸化炭素を一原料として、た
とえそのアルキル鎖上に置換基を持たないアミノアルコ
ールを用いても効率よくオキサゾリドンを製造する方法
を提供することにある。However, in this method, the degree of freedom in selecting the starting amino alcohol is limited, and when ethanolamine or the like having no substituent on the alkyl chain is used, the target oxazolidone is hardly produced. There is. The present invention has been made in view of the above circumstances, and its purpose is to produce oxazolidone efficiently even using carbon dioxide as a raw material, even if an amino alcohol having no substituent on its alkyl chain is used. It is to provide a method.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意検討した結果、エタノールアミン誘導
体と二酸化炭素との反応触媒としてスズ化合物を用いれ
ば上記課題が解決できることを見出し本発明を完成する
に至った。すなわち、本発明によれば、二酸化炭素と下
記一般式（Ｉ）で示されるエタノールアミン誘導体とを
スズ化合物触媒の存在下で反応させることを特徴とする
下記一般式（ＩＩ）で示されるオキサゾリドンの製造方
法が提供される。 The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that ethanolamine-derived
The present inventors have found that the use of a tin compound as a catalyst for reacting a substance with carbon dioxide can solve the above-mentioned problems, and have completed the present invention. That is, according to the present invention, carbon dioxide and
And an ethanolamine derivative represented by the general formula (I)
Characterized by reacting in the presence of a tin compound catalyst
Method for producing oxazolidone represented by the following general formula (II)
A law is provided.
【化３】 （式中、Ｒ１〜Ｒ５は水素原子、アルキル基又はアリー
ル基を示す。）Embedded image (In the formula, R 1 to R 5 represent a hydrogen atom, an alkyl group, or an aryl group.)
【化４】 （式中、Ｒ１〜Ｒ５は水素原子、アルキル基又はアリー
ル基を示す。）Embedded image (In the formula, R 1 to R 5 represent a hydrogen atom, an alkyl group, or an aryl group.)
【０００７】本発明で使用する原料エタノールアミン誘
導体は上記一般式（Ｉ）で示される。上記一般式（Ｉ）
における、Ｒ １ 〜Ｒ ５ のアルキル基としては、メチル
基、エチル基、プロピル基、ブチル基などが、アルール
基としては、置換若しくは無置換のフェニル基、置換若
しくは無置換のナフチル基等が挙げられ、この場合の置
換としは、メチル基、エチル基、プロピル基、ブチル基
などのアルキル基等が挙げられる。 [0007] The starting material ethanolamine used in the present invention
The conductor is represented by the general formula (I). The above general formula (I)
In the above, the alkyl group for R 1 to R 5 is methyl
Group, ethyl group, propyl group, butyl group, etc.
Examples of the group include a substituted or unsubstituted phenyl group,
Or an unsubstituted naphthyl group.
In other words, methyl, ethyl, propyl, butyl
And the like.
【０００８】本発明の上記エタノールアミン誘導体と炭
酸ガスからのオキサゾリドンの合成反応式は以下のよう
に表すことができる。The reaction formula for the synthesis of oxazolidone from the above-mentioned ethanolamine derivative and carbon dioxide gas of the present invention can be represented as follows.
【化５】 Embedded image
【０００９】また、本発明で使用する上記スズ化合物は
特に限定されず、有機スズ化合物、無機スズ化合物の何
れも使用可能である。このような有機スズ化合物の具体
例としては、例えば、ジアルキルスズオキシド、アルキ
ルスズアシレート、アルキルスズアルコキシド、アルキ
ルスズハライドなどのアルキルスズ化合物を例示するこ
とができる。無機スズ化合物としては、ハロゲン化ス
ズ、酸化スズ、金属スズ粉末等が挙げられる。本発明で
好ましく使用されるスズ化合物は有機スズ化合物であ
り、特にアルキルスズオキシドの使用が望ましい。スズ
化合物触媒のの使用量は特に制約されないが、原料アル
カノールアミンに対して１／１０００から１／１０重量
部、好ましくは１／１００から１／２０重量部である。
スズ化合物の使用量があまりにも少ないと反応が進行せ
ず、またあまりにも多いと副反応物の生成量が増大する
ため、目的とするオキサゾリドンの収率が低下するので
望ましくない。The above-mentioned tin compound used in the present invention is not particularly limited, and any of an organic tin compound and an inorganic tin compound can be used. Specific examples of such an organotin compound include, for example, alkyltin compounds such as dialkyltin oxide, alkyltin acylate, alkyltin alkoxide, and alkyltin halide. Examples of the inorganic tin compound include tin halide, tin oxide, and metal tin powder. The tin compound preferably used in the present invention is an organic tin compound, and it is particularly preferable to use an alkyl tin oxide. The amount of the tin compound catalyst used is not particularly limited, but is 1/1000 to 1/10 parts by weight, preferably 1/100 to 1/20 parts by weight, based on the starting alkanolamine.
If the amount of the tin compound used is too small, the reaction does not proceed, and if the amount is too large, the amount of by-products increases and the yield of the desired oxazolidone decreases, which is not desirable.
【００１０】本発明方法によれば、上記エタノールアミ
ン誘導体と触媒の混合物の溶液を炭酸ガス雰囲気下にか
き混ぜるか、または靜置することによって相当するオキ
サゾリドンを生成させることができる。According to the present invention method, the ethanol ami
The corresponding oxazolidone can be formed by stirring or leaving the solution of the mixture of the thiol derivative and the catalyst under a carbon dioxide atmosphere.
【００１１】このオキサゾリドンの生成反応は大気圧の
炭酸ガス雰囲気下でも進行するが、好ましくは１気圧以
上好ましくは２０〜６０気圧の加圧下で行うのが望まし
い。また、反応温度は特に制約はないが、５０〜２２０
℃、好ましくは１６０〜２００℃で行われる。The oxazolidone formation reaction proceeds even under a carbon dioxide gas atmosphere at atmospheric pressure, but is preferably carried out under a pressure of 1 atm or more, preferably 20 to 60 atm. The reaction temperature is not particularly limited.
C., preferably at 160-200.degree.
【００１２】本発明の実施にあたってはオキサゾリドン
の収率を高めるために溶媒の使用が好ましい。溶媒とし
ては、１−メチル−２−ピロリドン（ＮＭＰ）、アセト
ニトリル、テトラヒドロフラン、ジメチルホルムアミ
ド、ジメチルスルホキシドなどのような有機極性溶媒も
しくはこれら有機極性溶媒を二種類以上混合したものが
用いられるが、１−メチル−２−ピロリドン（ＮＭＰ）
の使用が特に好ましい。In practicing the present invention, it is preferable to use a solvent in order to increase the yield of oxazolidone. As the solvent, an organic polar solvent such as 1-methyl-2-pyrrolidone (NMP), acetonitrile, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, or a mixture of two or more of these organic polar solvents is used. Methyl-2-pyrrolidone (NMP)
The use of is especially preferred.
【００１３】本発明によれば、上記反応終了後、所望と
するオキサゾリドンの他に種々の副生成物が得られる
が、蒸留法、分別結晶法、クロマトグラフィーなど公知
の分離手段を併用することにより、該混合物から目的と
するオキサゾリドンを純度よく精製することができる。According to the present invention, various by-products can be obtained in addition to the desired oxazolidone after the completion of the above-mentioned reaction. However, by using known separation means such as distillation, fractional crystallization, and chromatography, The desired oxazolidone can be purified from the mixture with high purity.
【００１４】[0014]
【実施例】以下に、本発明を実施例によりさらに詳細に
説明するが、これは代表的例示を示すためのものであ
り、本発明を制限する趣旨ではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which are for the purpose of showing typical examples, and are not intended to limit the present invention.
【００１５】実施例１〜４ ５０ｍＬ容のオートクレーブ中に、２−メチルアミノエ
タノール（１０ｍｍｏｌ）、溶媒（１−メチル−２−ピ
ロリドン）（ＮＭＰ）(８ｍＬ）およびジ−ｎ−ブチル
スズオキシド（０〜０．４ｍｍｏｌ）を表１記載の要領
で仕込み、二酸化炭素５０気圧を室温で圧入した後、所
定温度で１６時間反応を行った。これらの反応で得られ
た生成物を、ガスクロマトグラフィーにより定量分析し
た。その結果を表１に示すExamples 1-4 In a 50 mL autoclave, 2-methylaminoethanol (10 mmol), solvent (1-methyl-2-pyrrolidone) (NMP) (8 mL) and di-n-butyltin oxide (0 to 10 mL) were added. 0.4 mmol) was charged as described in Table 1, 50 atm of carbon dioxide was injected at room temperature, and the reaction was carried out at a predetermined temperature for 16 hours. The products obtained in these reactions were quantitatively analyzed by gas chromatography. The results are shown in Table 1.
【００１６】比較例１ 実施例１において、スズ化合物触媒を添加しない以外は
実施例１と同様に反応を行った。その結果を表１に示
す。Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that the tin compound catalyst was not added. Table 1 shows the results.
【００１７】比較例２ ５０ｍＬ容のオートクレーブ中に、２−メチルアミノエ
タノール（２０ｍｍｏｌ）、ベンゼン(５ｍＬ）、モレ
キュラーシーブ（１．２ｇ）、およびトリフェニルアン
チモンオキシド（２ｍｍｏｌ）を仕込み、二酸化炭素加
圧（５０気圧）下、１６０℃で６時間反応させた。その
結果を表１に示す。なお、この比較例２は、文献（H. M
atsuda, A. Baba, R. Nomura, M. Kori, and S Ogawa,
Ind. Eng.Chem. Prod. Res. Dev., 24, 239(1985).）か
らの値である。COMPARATIVE EXAMPLE 2 In a 50 mL autoclave, 2-methylaminoethanol (20 mmol), benzene (5 mL), molecular sieve (1.2 g), and triphenylantimony oxide (2 mmol) were charged and pressurized with carbon dioxide. The reaction was carried out at 160 ° C. under (50 atm) for 6 hours. Table 1 shows the results. This comparative example 2 is described in the literature (H. M.
atsuda, A. Baba, R. Nomura, M. Kori, and S Ogawa,
Ind. Eng. Chem. Prod. Res. Dev., 24, 239 (1985).).
【００１８】実施例１〜４および比較例１、２の反応条
件および結果を表１にまとめて示す。生成物は、Ｎ−メ
チルオキサゾリドンである。The reaction conditions and results of Examples 1 to 4 and Comparative Examples 1 and 2 are summarized in Table 1. The product is N-methyloxazolidone.
【００１９】[0019]
【表１】 [Table 1]
【００２０】実施例５ ５０ｍＬ容のオートクレーブ中に、エタノールアミン
（１０ｍｍｏｌ）、ＮＭＰ(８ｍＬ）およびジ−ｎ−ブ
チルスズオキシド（１．０ｍｍｏｌ）を仕込み、二酸化
炭素５０気圧を室温で圧入した後、１８０℃で１６時間
反応を行った。生成したオキサゾリドンをガスクロマト
グラフィーにより定量分析した。オキサゾリドンの収率
は５３％であった。Example 5 Ethanolamine (10 mmol), NMP (8 mL) and di-n-butyltin oxide (1.0 mmol) were charged into a 50 mL autoclave, and 50 atm of carbon dioxide was injected at room temperature. Reaction was carried out at 16 ° C. for 16 hours. The produced oxazolidone was quantitatively analyzed by gas chromatography. The yield of oxazolidone was 53%.
【００２１】比較例３ ５０ｍＬ容のオートクレーブ中に、エタノールアミン
（２０ｍｍｏｌ）、ベンゼン(５ｍＬ）、モレキュラー
シーブ（１ｇ）、およびトリフェニルアンチモンオキシ
ド（２ｍｍｏｌ）を仕込み、二酸化炭素加圧（５０気
圧）下、１６０℃で６時間反応させた。生成したオキサ
ゾリドンをガスクロマトグラフィーにより定量分析した
ところ、オキサゾリドンがｔｒａｃｅ量しか生成してい
ないことが確認された。なお、比較例３は、文献（H. M
atsuda, A. Baba, R. Nomura, M. Kori, and S. Ogawa,
Ind. Eng. Chem. Prod. Res. Dev., 24, 239(1985).）
からの値である。Comparative Example 3 Ethanolamine (20 mmol), benzene (5 mL), molecular sieve (1 g), and triphenylantimony oxide (2 mmol) were charged into a 50 mL autoclave, and the mixture was heated under carbon dioxide pressure (50 atm). At 160 ° C. for 6 hours. When the generated oxazolidone was quantitatively analyzed by gas chromatography, it was confirmed that only trace amount of oxazolidone was generated. Comparative Example 3 is described in the literature (HM
atsuda, A. Baba, R. Nomura, M. Kori, and S. Ogawa,
Ind. Eng. Chem. Prod. Res. Dev., 24, 239 (1985).)
Is the value from.
【００２２】実施例６ ５０ｍＬ容のオートクレーブ中に、２−エチルアミノエ
タノール（１０ｍｍｏｌ）、ＮＭＰ(８ｍＬ）およびジ
−ｎ−ブチルスズオキシド（１．０ｍｍｏｌ）を仕込
み、二酸化炭素５０気圧を室温で圧入した後、１８０℃
で１６時間反応を行った。生成したＮ−エチルオキサゾ
リドンはガスクロマトグラフィーにより定量分析した。
Ｎ−エチルオキサゾリドンの収率は７６％であった。Example 6 In a 50 mL autoclave, 2-ethylaminoethanol (10 mmol), NMP (8 mL) and di-n-butyltin oxide (1.0 mmol) were charged, and 50 atm of carbon dioxide was injected at room temperature. After, 180 ° C
For 16 hours. The produced N-ethyloxazolidone was quantitatively analyzed by gas chromatography.
The yield of N-ethyloxazolidone was 76%.
【００２３】[0023]
【発明の効果】本発明の方法によれば、安価で無害な二
酸化炭素を用いて、抗けいれん剤などの医薬品合成原
料、合成中間体や農薬、あるいは高機能液晶材料合成中
間体等として有用なオキサゾリドン誘導体を高収率で製
造することができる。また本発明方法によれば、たとえ
そのアルキル鎖上に置換基を持たないエタノールアミン
を用いても効率よくオキサゾリドンを製造することがで
きる。According to the method of the present invention, inexpensive and harmless carbon dioxide is useful as a raw material for synthesis of pharmaceuticals such as anticonvulsants, synthetic intermediates and agricultural chemicals, or synthetic intermediates for high-performance liquid crystal materials. Oxazolidone derivatives can be produced in high yield. According to the method of the present invention, oxazolidone can be efficiently produced even if ethanolamine having no substituent on its alkyl chain is used.
Claims (2)
るエタノールアミン誘導体とをスズ化合物触媒の存在下
で反応させることを特徴とする下記一般式（ＩＩ）で示
されるオキサゾリドンの製造方法。 【化１】 （式中、Ｒ１〜Ｒ５は水素原子、アルキル基又はアリー
ル基を示す。） 【化２】 （式中、Ｒ１〜Ｒ５は水素原子、アルキル基又はアリー
ル基を示す。）1. A compound represented by the following general formula (I) and carbon dioxide :
Ethanolamine derivative in the presence of a tin compound catalyst
Represented by the following general formula (II),
A method for producing oxazolidone. Embedded image (In the formula, R 1 to R 5 represent a hydrogen atom, an alkyl group or an aryl group.) (In the formula, R 1 to R 5 represent a hydrogen atom, an alkyl group, or an aryl group.)
とを特徴とする請求項１のオキサゾリドンの製造方法。2. The method for producing oxazolidone according to claim 1, wherein the tin compound is an alkyltin compound.
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|---|---|---|---|
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