JP3069677B2 - Method for producing organic carboxylic acid ester compound - Google Patents
Method for producing organic carboxylic acid ester compoundInfo
- Publication number
- JP3069677B2 JP3069677B2 JP8196067A JP19606796A JP3069677B2 JP 3069677 B2 JP3069677 B2 JP 3069677B2 JP 8196067 A JP8196067 A JP 8196067A JP 19606796 A JP19606796 A JP 19606796A JP 3069677 B2 JP3069677 B2 JP 3069677B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- organic carboxylic
- reaction
- acid ester
- ester compound
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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、有機カルボン酸エ
ステル化合物の効率的な製造方法に関する。The present invention relates to a method for efficiently producing an organic carboxylic acid ester compound.
【０００２】[0002]
【従来の技術】従来、エステル類の脱水縮合反応による
合成は、原料を触媒の存在下で、蒸気加熱装置、燃焼加
熱装置、電熱ヒーターなどの加熱装置を用いて加熱し、
所定の温度で脱水縮合させる方法が一般的に知られてい
る。従来の方法は、複雑な構成の容器や、水分離器、凝
縮器、特別の加熱装置などの設置が必要となる。2. Description of the Related Art Conventionally, in the synthesis of esters by a dehydration condensation reaction, a raw material is heated in the presence of a catalyst using a heating device such as a steam heating device, a combustion heating device, or an electric heater.
A method of performing dehydration condensation at a predetermined temperature is generally known. The conventional method requires installation of a vessel having a complicated configuration, a water separator, a condenser, a special heating device, and the like.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、脱水
縮合反応の反応速度を高め、短時間で合成を完了させる
ことができる有機カルボン酸エステル化合物の製造方法
を提供することにある。また、本発明の目的は、反応系
に特別の水分離器、凝縮器、加熱装置などを設置するこ
とを不要とした、あるいはその設置を簡略化しうる、有
機カルボン酸エステル化合物の製造方法を提供すること
である。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an organic carboxylic acid ester compound which can increase the reaction rate of a dehydration condensation reaction and complete the synthesis in a short time. Further, an object of the present invention is to provide a method for producing an organic carboxylic acid ester compound, which eliminates the need for installing a special water separator, a condenser, a heating device and the like in a reaction system, or can simplify the installation. It is to be.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の従
来の方法の欠点を克服し、簡便、かつ、効率的に有機カ
ルボン酸エステル化合物を製造しうる方法を提供するた
め鋭意検討を重ねた結果、反応を有機塩基性化合物の存
在下マイクロ波加熱下に行わせること、及溶剤の存在下
に行うことによりその目的を達成しうることを見い出
し、この知見に基づき本発明をなすに至った。すなわ
ち、本発明は、化学量論量のモル比の有機カルボン酸と
アルコール類を反応させて脱水縮合反応を行うに当た
り、触媒として有機カルボン酸１モルに対して０．３〜
０．５モルの有機塩基性物質の存在下、マイクロ波加熱
下に行い有機カルボン酸エステル化合物を製造する有機
カルボン酸エステルの製造方法、この有機カルボン酸と
アルコール類との脱水縮合反応を溶剤の存在下に行う有
機カルボン酸エステル化合物の製造方法を提供するもの
である。本発明においてマイクロ波加熱とは、周波数の
高い電波であるマイクロ波を物にあてて加熱する加熱方
法である。マイクロ波の発生のためにマグネトロンが用
いられる。このようなマイクロ波加熱を行う装置として
は、具体的には電子レンジがある。Means for Solving the Problems The present inventors have made intensive studies to overcome the drawbacks of the above-mentioned conventional methods and to provide a method for easily and efficiently producing an organic carboxylic acid ester compound. As a result of overlapping, it was found that the reaction was carried out under microwave heating in the presence of an organic basic compound, and that the object could be achieved by carrying out the reaction in the presence of a solvent. Reached. That is, in the present invention, when a stoichiometric amount of an organic carboxylic acid is reacted with an alcohol in a molar ratio to perform a dehydration condensation reaction, the catalyst is used in an amount of 0.3 to 1 mol per mol of the organic carboxylic acid.
Microwave heating in the presence of 0.5 mol of organic basic substance
It provides a process for producing an organic carboxylic acid ester compound to carry out a method of manufacturing an organic carboxylic acid ester to produce an organic carboxylic acid ester compound is performed under the dehydration condensation reaction of the organic carboxylic acids with alcohols in the presence of a solvent It is. In the present invention, microwave heating is a heating method in which microwaves, which are radio waves having a high frequency, are applied to objects to heat them. A magnetron is used for microwave generation. As a device for performing such microwave heating, a microwave oven is specifically used.
【０００５】[0005]
【発明の実施の形態】本発明の反応は、有機カルボン酸
とアルコール類を反応させ、有機カルボン酸エステル化
合物を製造する方法である。この反応で用いられる有機
カルボン酸は、ケンプ酸、フタル酸、シクロヘキサンカ
ルボン酸、安息香酸、１，２−シクロヘキサンジカルボ
ン酸などである。DETAILED DESCRIPTION OF THE INVENTION The reaction of the present invention is a method for producing an organic carboxylic acid ester compound by reacting an organic carboxylic acid with an alcohol. Organic carboxylic acids used in this reaction include kempic acid, phthalic acid, cyclohexanecarboxylic acid, benzoic acid, 1,2-cyclohexanedicarboxylic acid and the like.
【０００６】また、アルコール類としては、ベンジルア
ルコール、ｐ−ｔｅｒｔ−ブチルベンジルアルコール、
フェネチルアルコール、フェニルプロピルアルコール、
ヒドロキシメチルアントラセンなどのアラルキルアルコ
ール、ヘキサノール、ヘプタノール、オクタノール、デ
カノールなどのアルキルアルコールがあげられる。本発
明では有機カルボン酸は、遊離のカルボン酸をそのまま
で用いて、その目的を達成しうることに特徴がある。The alcohols include benzyl alcohol, p-tert-butylbenzyl alcohol,
Phenethyl alcohol, phenylpropyl alcohol,
Examples include aralkyl alcohols such as hydroxymethylanthracene and alkyl alcohols such as hexanol, heptanol, octanol and decanol. The present invention is characterized in that an organic carboxylic acid can achieve its purpose by using a free carboxylic acid as it is.
【０００７】本発明の反応において反応成分の反応モル
比は、化学量論量のモル比が最も好ましく、この割合の
ものが用いられる。In the reaction of the present invention, the reaction molar ratio of the reaction components is most preferably a stoichiometric molar ratio, and this ratio is used.
【０００８】本発明の反応は、有機塩基性化合物の存在
下で行うことが好ましい。有機塩基性化合物は触媒作用
を有するものであり、有機塩基性化合物としては、イミ
ダゾール、トリエチルアミン、Ｎ−メチルイミダゾー
ル、ｐ−ジメチルアミノピリジン、Ｎ−メチルモルホリ
ンなどであり、これらの中で環状含窒素ヘテロ環化合物
が好ましい。この触媒の使用量は、有機カルボン酸成分
１モルに対し、０．３〜０．５モルの比で用いられる。The reaction of the present invention is preferably performed in the presence of an organic basic compound. The organic basic compound has a catalytic action, and examples of the organic basic compound include imidazole, triethylamine, N-methylimidazole, p-dimethylaminopyridine, and N-methylmorpholine. Heterocyclic compounds are preferred. The catalyst is used in an amount of 0.3 to 0.5 mol per 1 mol of the organic carboxylic acid component.
【０００９】本発明において反応を無溶媒又は溶媒中の
いずれの条件で行ってもよい。溶媒を用いて行う場合
は、溶媒としては、ジメチルホルムアミド（ＤＭＦ）、
ｏ−ジクロロベンゼン、クロロベンゼン、ｐ−クロロフ
ルオロベンゼン、１，２−ジエトキシエタンなどの、反
応により生成する水を吸収し、双極子モーメントが高い
ことにより照射マイクロ波を熱エネルギーに変換する溶
媒である。本発明では溶媒を用いる場合でも、非常に少
量でよく反応原料の混合物を滴下した溶媒で湿らせる程
度で実施できる。本発明は反応原料を不均一混合物の状
態で省溶媒又は無溶媒で実施しうる製造方法である。In the present invention, the reaction may be carried out without solvent or in a solvent. When using a solvent, dimethylformamide (DMF),
Solvents such as o-dichlorobenzene, chlorobenzene, p-chlorofluorobenzene, and 1,2-diethoxyethane that absorb water produced by the reaction and convert irradiation microwaves into heat energy due to their high dipole moment. is there. In the present invention, even when a solvent is used, the reaction can be carried out in a very small amount and only to the extent that the mixture of the reaction raw materials is wetted with the dropped solvent. The present invention is a production method capable of carrying out a reaction raw material in a heterogeneous mixture state with or without a solvent.
【００１０】本発明の反応は、マイクロ波加熱下に行
う。加熱時間は仕込量、マイクロ波加熱装置のワット数
などの条件によって異なるが、２００〜５００ワットで
通常０．５〜１０分間、好ましくは２〜３分である。マ
イクロ波の周波数は、通常２０００〜３０００ＭＨｚで
ある。本発明においてマイクロ波加熱とは、周波数の高
い電波であるマイクロ波を物にあてて加熱する加熱方法
である。マイクロ波の発生のためにマグネトロンが用い
られる。このようなマイクロ波加熱を行う装置として
は、具体的には電子レンジがある。[0010] The reaction of the present invention is carried out under microwave heating. The heating time varies depending on conditions such as the charged amount and the wattage of the microwave heating device, but is usually 200 to 500 watts, usually 0.5 to 10 minutes, preferably 2 to 3 minutes. The frequency of the microwave is usually 2000 to 3000 MHz. In the present invention, microwave heating is a heating method in which microwaves, which are radio waves having a high frequency, are applied to objects to heat them. A magnetron is used for microwave generation. As a device for performing such microwave heating, a microwave oven is specifically used.
【００１１】[0011]
【実施例】次に、本発明を実施例に基づいてさらに詳細
に説明する。Next, the present invention will be described in more detail with reference to examples.
【００１２】実施例１（安息香酸ベンジルの製造） １２×１２０ｍｍパイレックス製試験管に、安息香酸６
４ｍｇ（０．５２ミリモル）、ベンジルアルコール１８
ｍｌ（０．１７ミリモル）、イミダゾール１１ｍｇ
（０．１７ミリモル）を入れた。この混合物を電子レン
ジの低出力２００Ｗで５分間照射した。数分間室温で冷
却した後、反応混合物を０．７５ｍｌのクロロホルムで
希釈し、プロトンＮＭＲ測定のためＮＭＲ試験管に移
す。ＮＭＲスペクトルの解析の結果、単一生成物として
安息香酸ベンジルが２７％の収率で得られた。生成物の
収率はエステルのベンジル位のＮＭＲシグナル（５．３
６ｐｐｍ；シングレット）の積分値から算出した。Example 1 (Production of Benzyl Benzoate) A 12 × 120 mm Pyrex test tube was charged with benzoic acid 6
4 mg (0.52 mmol), benzyl alcohol 18
ml (0.17 mmol), 11 mg of imidazole
(0.17 mmol). The mixture was irradiated at a low power of 200 W of a microwave oven for 5 minutes. After cooling at room temperature for several minutes, the reaction mixture is diluted with 0.75 ml of chloroform and transferred to an NMR tube for proton NMR measurement. As a result of NMR spectrum analysis, benzyl benzoate was obtained as a single product in a yield of 27%. The product yield was determined by NMR signal at the benzyl position of the ester (5.3).
6 ppm; singlet).
【００１３】実施例２（フタル酸モノベンジルエステル
の製造） １２×１２０ｍｍパイレックス製試験管に、フタル酸２
８ｍｇ（０．１７ミリモル）、ベンジルアルコール１８
ｍｌ（０．１７ミリモル）、イミダゾール１１ｍｇ
（０．１７ミリモル）を入れた。この混合物を電子レン
ジの低出力２００Ｗで５分間照射した。数分間室温で冷
却した後、反応混合物を０．７５ｍｌの重クロロホルム
で希釈し、プロトンＮＭＲ測定のためＮＭＲ試験管に移
す。ＮＭＲスペクトルの解析の結果、フタル酸モノベン
ジルエステルが７３％の収率で得られた。生成物の収率
はエステルのベンジル位のＮＭＲシグナル（５．３５ｐ
ｐｍ；シングレット）の積分値から算出した。Example 2 (Production of monobenzyl phthalate) Phthalic acid 2 was placed in a 12 × 120 mm Pyrex test tube.
8 mg (0.17 mmol), benzyl alcohol 18
ml (0.17 mmol), 11 mg of imidazole
(0.17 mmol). The mixture was irradiated at a low power of 200 W of a microwave oven for 5 minutes. After cooling at room temperature for several minutes, the reaction mixture is diluted with 0.75 ml of deuterated chloroform and transferred to an NMR tube for proton NMR measurement. As a result of NMR spectrum analysis, monobenzyl phthalate was obtained in a yield of 73%. The product yield was determined by NMR signal at the benzyl position of the ester (5.35 p.
pm; singlet).
【００１４】[0014]
【発明の効果】本発明の方法によれば、反応系に特別の
水分離器、凝縮器、加熱装置などを設置することを不要
とし、あるいはそれらの設置を簡略化することができ、
しかも、脱水縮合反応の反応速度を高め、短時間で有機
カルボン酸エステル化合物を製造することができる。According to the method of the present invention, it is not necessary to install a special water separator, a condenser, a heating device and the like in the reaction system, or the installation can be simplified.
Moreover, the reaction rate of the dehydration condensation reaction can be increased, and the organic carboxylic acid ester compound can be produced in a short time.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−7740（ＪＰ，Ａ) 特開 平７−330667（ＪＰ，Ａ) 日本化学会編、「第４版実験化学講座 22有機合成▲ＩＶ▼」、丸善株式会社、 平成４年11月30日発行、第43〜54頁 (58)調査した分野(Int.Cl.7，ＤＢ名) C07B 43/06 C07B 41/12 C07C 67/08 C07C 69/80 C07C 231/02 C07C 233/65 C07B 61/00 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-56-7740 (JP, A) JP-A-7-330667 (JP, A) Edited by The Chemical Society of Japan, “4th Edition Experimental Chemistry Course, 22 Organic Synthesis ▲ IV ▼ ", Maruzen Co., Ltd., issued on November 30, 1992, pp. 43-54 (58) Fields investigated (Int. Cl. 7 , DB name) C07B 43/06 C07B 41/12 C07C 67/08 C07C 69/80 C07C 231/02 C07C 233/65 C07B 61/00
Claims (2)
ルコール類を反応させて脱水縮合反応を行うに当たり、
触媒として有機カルボン酸１モルに対して０．３〜０．
５モル量の有機塩基性物質の存在下に、マイクロ波加熱
して行い有機カルボン酸エステル化合物を製造すること
を特徴とする有機カルボン酸エステルの製造方法。1. A reaction in which a stoichiometric molar ratio of an organic carboxylic acid and an alcohol are reacted to carry out a dehydration condensation reaction.
As a catalyst, 0.3 to 0.
Microwave heating in the presence of 5 moles of organic basic substance
And producing an organic carboxylic acid ester compound.
ル類との脱水縮合反応を溶剤の存在下に行うことを特徴
とする有機カルボン酸エステル化合物の製造方法。2. A method for producing an organic carboxylic acid ester compound, wherein the dehydration condensation reaction between the organic carboxylic acid and an alcohol according to claim 1 is carried out in the presence of a solvent.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8196067A JP3069677B2 (en) | 1996-07-25 | 1996-07-25 | Method for producing organic carboxylic acid ester compound |
| JP28745198A JP3586707B2 (en) | 1996-07-25 | 1998-10-09 | Method for producing acid amide or acid imide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8196067A JP3069677B2 (en) | 1996-07-25 | 1996-07-25 | Method for producing organic carboxylic acid ester compound |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28745198A Division JP3586707B2 (en) | 1996-07-25 | 1998-10-09 | Method for producing acid amide or acid imide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1036294A JPH1036294A (en) | 1998-02-10 |
| JP3069677B2 true JP3069677B2 (en) | 2000-07-24 |
Family
ID=16351653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8196067A Expired - Lifetime JP3069677B2 (en) | 1996-07-25 | 1996-07-25 | Method for producing organic carboxylic acid ester compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3069677B2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2764603B1 (en) * | 1997-06-11 | 1999-07-30 | Oreal | PROCESS FOR THE PREPARATION OF CERAMID-LIKE COMPOUNDS |
| CN1188211C (en) * | 1999-05-26 | 2005-02-09 | 个人化学第一乌普萨拉有限公司 | Preparation and use of ionic liquids in microwave-assisted chemical transformation |
| FR2833260B1 (en) * | 2001-12-12 | 2004-02-27 | Usines Chimiques D Ivry La Bat | PROCESS FOR THE PREPARATION OF AN ESTER BY HEATING, USING A MICROWAVE FIELD, OF A HETEROGENEOUS MIXTURE OF ACID AND ALCOHOL |
| CU23224A1 (en) * | 2002-11-26 | 2007-08-30 | Cnic Ct Nac Investigaciones | PROCEDURE FOR THE PREPARATION OF DENDRONES AND DENDRIMEROS WITH IETROCYCLES SUB-STRUCTURES OF IMINOETHERS AND DERIVED BY NON-CLASSIC ROUTES AND UNDER MICROWAVE |
| MY143828A (en) * | 2004-06-17 | 2011-07-15 | Malaysian Palm Oil Board | A process for the production of fatty acid amides |
| JP2006232676A (en) * | 2005-02-22 | 2006-09-07 | Wakayama Prefecture | Method for producing calixarenes |
| JP2007126450A (en) * | 2005-10-04 | 2007-05-24 | Tokyo Electric Power Co Inc:The | Method for synthesizing etbe by microwave |
| JP4905849B2 (en) * | 2006-04-07 | 2012-03-28 | 東京電力株式会社 | Synthesis method of dimethyl ether using microwave |
| DE102006047617B4 (en) * | 2006-10-09 | 2008-11-27 | Clariant International Limited | Process for the preparation of basic (meth) acrylamides |
| DE102006047619B4 (en) * | 2006-10-09 | 2008-11-13 | Clariant International Limited | Process for the preparation of basic fatty acid amides |
| DE102006047620B4 (en) * | 2006-10-09 | 2008-11-27 | Clariant International Limited | Process for the preparation of tertiary amides of alkylphenylcarboxylic acids |
| DE102009031058A1 (en) * | 2009-06-30 | 2011-01-27 | Clariant International Ltd. | Continuous process for the preparation of amides of aromatic carboxylic acids |
| JP2011084526A (en) * | 2009-10-16 | 2011-04-28 | Kansai Univ | Method for producing dehydration condensation compound |
| JP6853136B2 (en) * | 2017-08-01 | 2021-03-31 | ユニマテック株式会社 | Method for producing polyfluoroalkyl alcohol and its carboxylic acid ester |
| CN115466193A (en) * | 2022-10-14 | 2022-12-13 | 禾大西普化学（四川）有限公司 | Method for preparing long-chain fatty acid amide by microwave method |
-
1996
- 1996-07-25 JP JP8196067A patent/JP3069677B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 日本化学会編、「第４版実験化学講座２２有機合成▲ＩＶ▼」、丸善株式会社、平成４年１１月３０日発行、第４３〜５４頁 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1036294A (en) | 1998-02-10 |
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