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WO2024185877A1 - Trifluoroacetic acid ester production method - Google Patents

Trifluoroacetic acid ester production method Download PDF

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Publication number
WO2024185877A1
WO2024185877A1 PCT/JP2024/008974 JP2024008974W WO2024185877A1 WO 2024185877 A1 WO2024185877 A1 WO 2024185877A1 JP 2024008974 W JP2024008974 W JP 2024008974W WO 2024185877 A1 WO2024185877 A1 WO 2024185877A1
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Prior art keywords
trifluoroacetic acid
cof
carbon atoms
acid ester
lower alcohol
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PCT/JP2024/008974
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French (fr)
Japanese (ja)
Inventor
達也 大塚
崇 金村
匡美 井本
征司 田窪
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ダイキン工業株式会社
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Publication of WO2024185877A1 publication Critical patent/WO2024185877A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/63—Halogen-containing esters of saturated acids

Definitions

  • This disclosure relates to a method for producing trifluoroacetic esters.
  • Trifluoroacetic acid esters have traditionally been used as raw materials for pharmaceuticals and agrochemicals, and their importance is expected to continue to grow in the future.
  • Known methods for producing trifluoroacetic acid esters include reacting CF 3 COF with ethanol in the presence of potassium fluoride, as disclosed in Patent Documents 1 and 2.
  • a method using an amine instead of potassium fluoride, as disclosed in Patent Document 3 is also known.
  • the objective of this disclosure is to find a method for producing trifluoroacetic acid that does not use amines or potassium fluoride and that can purify trifluoroacetic acid using a simple method such as distillation.
  • the present inventors have found that by adding an excess amount of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms, it is possible to obtain a trifluoroacetic acid ester by simply distilling the reaction product without using additives such as amines or potassium fluoride. Based on this finding, the present inventors have conducted further research and have completed the present disclosure.
  • Item 1 A method for producing a trifluoroacetic ester, comprising the steps of: A method for producing a trifluoroacetic acid ester, comprising a reaction step of adding equimolar or more of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF.
  • Item 2. Item 2. The method according to item 1, wherein in the reaction step, CF 3 COF is added in a molar ratio of 1 to 3 moles per mole of the lower alcohol having 1 to 4 carbon atoms.
  • Item 3. Item 3.
  • the method for producing trifluoroacetic esters according to the present disclosure described above makes it possible to purify trifluoroacetic acid without using amines or potassium fluoride, and by simply carrying out a simple operation such as distillation on the reaction product.
  • the method for producing a trifluoroacetic ester according to the present disclosure includes a reaction step of adding equimolar or more of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic ester and HF.
  • lower alcohols having 1 to 4 carbon atoms can be used as the lower alcohol, with no particular limitations. However, since ethyl trifluoroacetate is particularly useful as the target compound, it is preferable to use ethanol.
  • CF 3 COF is added to the lower alcohol having 1 to 4 carbon atoms in an amount equal to or greater than the lower alcohol having 1 to 4 carbon atoms, that is, CF 3 COF is added at a ratio of 1 mole or more per mole of the lower alcohol having 1 to 4 carbon atoms. If CF 3 COF is not added in an amount equal to or greater than the lower alcohol having 1 to 4 carbon atoms, the lower alcohol having 1 to 4 carbon atoms will be mixed in the obtained reaction product, and the process of purifying the final target trifluoroacetic acid ester cannot be simplified.
  • an azeotropic composition such as a lower alcohol having 1 to 4 carbon atoms/trifluoroacetic acid ester, water/trifluoroacetic acid ester/lower alcohol having 1 to 4 carbon atoms, or lower alcohol having 1 to 4 carbon atoms/HF is produced as a product, it becomes difficult to separate the trifluoroacetic acid ester.
  • CF 3 COF is added at a ratio of 1 mole or more per mole of the lower alcohol having 1 to 4 carbon atoms, preferably at a ratio exceeding 1 mole, more preferably at a ratio of 1.02 moles or more, and even more preferably at a ratio of 1.05 moles or more.
  • the upper limit for the amount of CF 3 COF added is preferably a ratio of 3 moles per mole of the lower alcohol having 1 to 4 carbon atoms, more preferably a ratio of 1.5 moles, and even more preferably a ratio of 1.2 moles.
  • the temperature conditions in the reaction process in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF are preferably -20°C or higher, more preferably 0°C or higher, and even more preferably 10°C or higher, in order to suppress dissolution of CF 3 COF in the reaction crude and to prevent an excessive amount of recycling during distillation.
  • the temperature conditions in the reaction process in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF are preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower, in order to suppress corrosion of the reaction equipment and to avoid increasing the reaction pressure.
  • the reaction in the reaction step of adding CF 3 COF to a lower alcohol having 1 to 4 carbon atoms to obtain trifluoroacetic acid ester and HF is preferably carried out under a sealed condition in order to reduce the loss of reaction products and raw materials. In this case, it is preferable not to add nitrogen or argon, etc., since this causes a decrease in the recovery rate of CF 3 COF.
  • the reaction pressure can be reduced or increased depending on the reaction temperature, but is preferably set to minus 0.05 MPaG or more, more preferably 0.0 MPaG or more, and even more preferably 0.1 MPaG or more, in order to increase the reaction rate.
  • the reaction pressure in the reaction process in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF is preferably 1.5 MPaG or less, more preferably 1.0 MPaG or less, and even more preferably 0.8 MPaG or less, for reasons of preventing leakage (safety).
  • the reaction time in the reaction step in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF is preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 3 hours or more, in order to keep the temperature stable (by gradual heating).
  • the reaction time is preferably 24 hours or less, more preferably 20 hours or less, and even more preferably 16 hours or less, in consideration of improving productivity.
  • a reaction product obtained by adding equimolar or more of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms can be purified to give a highly pure trifluoroacetic acid ester.
  • the purification method in the purification step can be any known purification method and is not particularly limited. However, it is preferable to carry out purification by distillation because it is a simple method.
  • the present disclosure discloses a composition
  • a composition comprising a trifluoroacetic acid ester, HF, and CF 3 COF, the CF 3 COF content being 0.1 to 30 wt %.
  • the content of CF 3 COF contained in the composition of the present disclosure is 0.1 mass % or more, preferably 0.2 mass % or more, and more preferably 0.5 mass % or more, based on 100 mass % of the composition of the present disclosure.
  • the content of CF 3 COF contained in the composition of the present disclosure is 30 mass % or less, preferably 10 mass % or less, and more preferably 5 mass % or less, based on 100 mass % of the composition of the present disclosure.
  • the content of trifluoroacetic acid ester is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more, based on 100% by mass of the composition of the present disclosure.
  • the content of trifluoroacetic acid ester is preferably 90% by mass or less, more preferably 89% by mass or less, and even more preferably 88% by mass or less, based on 100% by mass of the composition of the present disclosure.
  • the HF content is preferably 10% by mass or more, more preferably 11% by mass or more, and even more preferably 12% by mass or more, based on 100% by mass of the composition of the present disclosure.
  • the HF content is preferably 15% by mass or less, more preferably 14% by mass or less, and even more preferably 13% by mass or less, based on 100% by mass of the composition of the present disclosure.
  • composition of the present disclosure can be obtained by adding CF 3 COF in an equimolar amount or more to a lower alcohol having 1 to 4 carbon atoms.
  • composition of the present disclosure may contain at least one selected from the group consisting of trifluoroacetic acid, toluene, and water, within a range that does not impair the effects and purpose of the composition.
  • Example 1 204g (4.43mol) of ethanol (containing 0.2% water) was charged into a 1L stainless steel autoclave, and while heating and stirring at 60°C, 585g (5.04mol) of CF3COF was charged at a constant flow rate to react. The reaction pressure finally reached 0.6MPaG. After the reaction, the reaction mixture was charged into a rectification column and rectified under normal pressure. After recovering CF3COF with a low boiling point and extracting the HF fraction with a boiling point of 20°C, 580g of high-purity ethyl trifluoroacetate was recovered (yield 92%).
  • Example 2 As shown in Table 1 below, Examples 2 to 6 were carried out in a manner similar to Example 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a trifluoroacetic acid production method with which it is possible to refine trifluoroacetic acid with, for example, a simple method such as distillation, without using an amine or potassium fluoride. This trifluoroacetic acid ester production method comprises a reaction step for obtaining HF and trifluoroacetic acid ester by adding, to a lower alcohol having 1-4 carbon atoms, CF3COF at an equimolar amount or more.

Description

トリフルオロ酢酸エステルの製造方法Method for producing trifluoroacetic acid esters
　本開示は、トリフルオロ酢酸エステルの製造方法に関する。 This disclosure relates to a method for producing trifluoroacetic esters.
　トリフルオロ酢酸エステルは、従来より医農薬の原料として活用されており、今後もその重要は高まるものと考えられる。 Trifluoroacetic acid esters have traditionally been used as raw materials for pharmaceuticals and agrochemicals, and their importance is expected to continue to grow in the future.
　トリフルオロ酢酸エステルの製造方法として、特許文献１及び２に開示されるような、ＣＦ３ＣＯＦをフッ化カリウムの存在下、エタノールと反応させる方法が公知である。それ以外にも、特許文献３に開示されるような上記フッ化カリウムの替わりにアミンを使用する方法も公知である。 Known methods for producing trifluoroacetic acid esters include reacting CF 3 COF with ethanol in the presence of potassium fluoride, as disclosed in Patent Documents 1 and 2. In addition, a method using an amine instead of potassium fluoride, as disclosed in Patent Document 3, is also known.
中国特許出願公開第１０４４０２７１４号明細書Chinese Patent Publication No. 104402714 中国特許出願公開第１０４３７０７３０号明細書Chinese Patent Publication No. 104370730 中国特許出願公開第１０２３５１６９４号明細書Chinese Patent Publication No. 102351694
　上記のような事情に鑑み、本開示の目的とするところは、アミン又はフッ化カリウムを使用することなく、且つ、例えば蒸留のような簡便な方法でトリフルオロ酢酸を精製可能な、トリフルオロ酢酸の製造方法を見出すことにある。 In view of the above circumstances, the objective of this disclosure is to find a method for producing trifluoroacetic acid that does not use amines or potassium fluoride and that can purify trifluoroacetic acid using a simple method such as distillation.
　本発明者らは上記課題を解決すべく鋭意研究を重ねた結果、炭素数１～４の低級アルコールに対し、過剰量のＣＦ３ＣＯＦを添加することにより、アミンやフッ化カリウムといった添加剤を使用することなく、且つ、反応後生成物を蒸留するだけでトリフルオロ酢酸エステルを得ることができることを見出した。本発明者らは、かかる知見に基づきさらに研究を重ね、本開示を完成するに至った。 As a result of intensive research aimed at solving the above problems, the present inventors have found that by adding an excess amount of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms, it is possible to obtain a trifluoroacetic acid ester by simply distilling the reaction product without using additives such as amines or potassium fluoride. Based on this finding, the present inventors have conducted further research and have completed the present disclosure.
　即ち、本開示は、以下のトリフルオロ酢酸エステルの製造方法を提供する。
項１．
　トリフルオロ酢酸エステルの製造方法であって、
　炭素数１～４の低級アルコールに対し、ＣＦ３ＣＯＦを等モル以上添加することにより、トリフルオロ酢酸エステル及びＨＦを得る反応工程を有する、トリフルオロ酢酸エステルの製造方法。
項２．
　前記反応工程において、炭素数１～４の低級アルコール１モルに対し、ＣＦ３ＣＯＦを１～３モルのモル比で添加する、項１に記載の製造方法。
項３．
　前記炭素数１～４の低級アルコールはエタノールである、項１又は２の製造方法。
項４．
　トリフルオロ酢酸エステルと、ＨＦと、ＣＦ３ＣＯＦとを含み、ＣＦ３ＣＯＦの含有量は０．１～３０質量％である、組成物。 That is, the present disclosure provides the following method for producing a trifluoroacetic ester.
Item 1.
1. A method for producing a trifluoroacetic ester, comprising the steps of:
A method for producing a trifluoroacetic acid ester, comprising a reaction step of adding equimolar or more of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF.
Item 2.
Item 2. The method according to item 1, wherein in the reaction step, CF 3 COF is added in a molar ratio of 1 to 3 moles per mole of the lower alcohol having 1 to 4 carbon atoms.
Item 3.
Item 3. The method of claim 1 or 2, wherein the lower alcohol having 1 to 4 carbon atoms is ethanol.
Item 4.
A composition comprising a trifluoroacetic acid ester, HF, and CF 3 COF, the CF 3 COF content being 0.1 to 30 mass %.
　以上にしてなる本開示に係るトリフルオロ酢酸エステルの製造方法によれば、アミン又はフッ化カリウムを使用することなく、且つ、反応生成物に対して蒸留のような簡便な操作を実施するだけでトリフルオロ酢酸を精製することが可能である。 The method for producing trifluoroacetic esters according to the present disclosure described above makes it possible to purify trifluoroacetic acid without using amines or potassium fluoride, and by simply carrying out a simple operation such as distillation on the reaction product.
　本明細書において、「含有」は、「含む（comprise）」、「実質的にのみからなる（consist essentially of）」、及び「のみからなる（consist of）」のいずれも包含する概念である。また、本明細書において、数値範囲を「Ａ～Ｂ」で示す場合、Ａ以上Ｂ以下を意味する。 In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist of." Furthermore, in this specification, when a numerical range is indicated as "A to B," it means greater than or equal to A and less than or equal to B.
　本開示のトリフルオロ酢酸エステルの製造方法は、炭素数１～４の低級アルコールに対し、ＣＦ３ＣＯＦを等モル以上添加することにより、トリフルオロ酢酸エステル及びＨＦを得る反応工程を有する。 The method for producing a trifluoroacetic ester according to the present disclosure includes a reaction step of adding equimolar or more of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic ester and HF.
　炭素数１～４の低級アルコールとしては、公知のものを広く使用することができ、特に限定はない。ただし、目的とする化合物としてはトリフルオロ酢酸エチルの有用性が特に高いため、エタノールを使用することが好ましい。 　A wide variety of known lower alcohols having 1 to 4 carbon atoms can be used as the lower alcohol, with no particular limitations. However, since ethyl trifluoroacetate is particularly useful as the target compound, it is preferable to use ethanol.
　ＣＦ３ＣＯＦは、炭素数１～４の低級アルコールに対し、該炭素数１～４の低級アルコールと等モル以上添加、つまり、炭素数１～４の低級アルコール１モルに対してＣＦ３ＣＯＦを１モル以上の比率で添加する。ＣＦ３ＣＯＦを炭素数１～４の低級アルコールに対して等モル以上添加しない場合、得られる反応生成物内に炭素数１～４の低級アルコールが混在することとなり、最終目的物であるトリフルオロ酢酸エステルを精製する工程を簡略化することができない。生成物として炭素数１～４の低級アルコール／トリフルオロ酢酸エステル、水／トリフルオロ酢酸エステル／炭素数１～４の低級アルコール、炭素数１～４の低級アルコール／ＨＦ等の共沸組成物が生成してしまうと、トリフルオロ酢酸エステルの分離が困難となる。 CF 3 COF is added to the lower alcohol having 1 to 4 carbon atoms in an amount equal to or greater than the lower alcohol having 1 to 4 carbon atoms, that is, CF 3 COF is added at a ratio of 1 mole or more per mole of the lower alcohol having 1 to 4 carbon atoms. If CF 3 COF is not added in an amount equal to or greater than the lower alcohol having 1 to 4 carbon atoms, the lower alcohol having 1 to 4 carbon atoms will be mixed in the obtained reaction product, and the process of purifying the final target trifluoroacetic acid ester cannot be simplified. If an azeotropic composition such as a lower alcohol having 1 to 4 carbon atoms/trifluoroacetic acid ester, water/trifluoroacetic acid ester/lower alcohol having 1 to 4 carbon atoms, or lower alcohol having 1 to 4 carbon atoms/HF is produced as a product, it becomes difficult to separate the trifluoroacetic acid ester.
　上記の通り、ＣＦ３ＣＯＦは炭素数１～４の低級アルコール１モルに対して１モル以上の比率で添加し、１モルを超える比率で添加することが好ましく、１．０２モル以上の比率で添加することがより好ましく、１．０５モル以上の比率で添加することがさらに好ましい。ＣＦ３ＣＯＦを添加する上限としては、原料であるＣＦ３ＣＯＦを回収するロスを回避するため、炭素数１～４の低級アルコール１モルに対して３モルの比率であることが好ましく、１．５モルの比率であることがより好ましく、１．２モルの比率であることがさらに好ましい。 As described above, CF 3 COF is added at a ratio of 1 mole or more per mole of the lower alcohol having 1 to 4 carbon atoms, preferably at a ratio exceeding 1 mole, more preferably at a ratio of 1.02 moles or more, and even more preferably at a ratio of 1.05 moles or more. In order to avoid loss in recovering the raw material CF 3 COF, the upper limit for the amount of CF 3 COF added is preferably a ratio of 3 moles per mole of the lower alcohol having 1 to 4 carbon atoms, more preferably a ratio of 1.5 moles, and even more preferably a ratio of 1.2 moles.
　炭素数１～４の低級アルコールにＣＦ３ＣＯＦを添加してトリフルオロ酢酸エステル及びＨＦを得る反応工程における温度条件は、ＣＦ３ＣＯＦが反応粗体に溶解することを抑制し、蒸留時におけるリサイクル量が過度とならないようにするために、－２０℃以上とすることが好ましく、０℃以上とすることがより好ましく、１０℃以上とすることがさらに好ましい。 The temperature conditions in the reaction process in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF are preferably -20°C or higher, more preferably 0°C or higher, and even more preferably 10°C or higher, in order to suppress dissolution of CF 3 COF in the reaction crude and to prevent an excessive amount of recycling during distillation.
　また、炭素数１～４の低級アルコールにＣＦ３ＣＯＦを添加してトリフルオロ酢酸エステル及びＨＦを得る反応工程における温度条件は、反応機器への腐食を抑制し、また、反応圧力を高めないようにするために、１００℃以下とすることが好ましく、９５℃以下とすることがより好ましく、９０℃以下とすることがさらに好ましい。 Furthermore, the temperature conditions in the reaction process in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF are preferably 100° C. or lower, more preferably 95° C. or lower, and even more preferably 90° C. or lower, in order to suppress corrosion of the reaction equipment and to avoid increasing the reaction pressure.
　炭素数１～４の低級アルコールにＣＦ３ＣＯＦを添加してトリフルオロ酢酸エステル及びＨＦを得る反応工程における反応は、反応生成物及び原料のロスを低減するため、密閉下に行うことが好ましい。この際、窒素又はアルゴン等の添加はＣＦ３ＣＯＦの回収率の低下原因となるので行わないことが好ましい。反応圧力は反応温度により減圧にも加圧にもなりうるが、反応速度を速くするという理由からマイナス０．０５ＭＰａＧ以上とすることが好ましく、０．０ＭＰａＧ以上とすることがより好ましく、０．１ＭＰａＧ以上とすることがさらに好ましい。 The reaction in the reaction step of adding CF 3 COF to a lower alcohol having 1 to 4 carbon atoms to obtain trifluoroacetic acid ester and HF is preferably carried out under a sealed condition in order to reduce the loss of reaction products and raw materials. In this case, it is preferable not to add nitrogen or argon, etc., since this causes a decrease in the recovery rate of CF 3 COF. The reaction pressure can be reduced or increased depending on the reaction temperature, but is preferably set to minus 0.05 MPaG or more, more preferably 0.0 MPaG or more, and even more preferably 0.1 MPaG or more, in order to increase the reaction rate.
　炭素数１～４の低級アルコールにＣＦ３ＣＯＦを添加してトリフルオロ酢酸エステル及びＨＦを得る反応工程における反応圧力は、漏洩防止(安全性)という理由から、１．５ＭＰａＧ以下とすることが好ましく、１．０ＭＰａＧ以下とすることがより好ましく、０．８ＭＰａＧ以下とすることがさらに好ましい。 The reaction pressure in the reaction process in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF is preferably 1.5 MPaG or less, more preferably 1.0 MPaG or less, and even more preferably 0.8 MPaG or less, for reasons of preventing leakage (safety).
　炭素数１～４の低級アルコールにＣＦ３ＣＯＦを添加してトリフルオロ酢酸エステル及びＨＦを得る反応工程における反応時間は、温度を安定に保つ(徐熱)ために、１時間以上とすることが好ましく、２時間以上とすることがより好ましく、３時間以上とすることがさらに好ましい。 The reaction time in the reaction step in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF is preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 3 hours or more, in order to keep the temperature stable (by gradual heating).
　炭素数１～４の低級アルコールにＣＦ３ＣＯＦを添加してトリフルオロ酢酸エステル及びＨＦを得る反応工程における反応時間は、生産性向上を考慮し、２４時間以下とすることが好ましく、２０時間以下とすることがより好ましく、１６時間以下とすることがさらに好ましい。 In the reaction step in which CF 3 COF is added to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic acid ester and HF, the reaction time is preferably 24 hours or less, more preferably 20 hours or less, and even more preferably 16 hours or less, in consideration of improving productivity.
　炭素数１～４の低級アルコールに対し、ＣＦ３ＣＯＦを等モル以上添加することにより得られる反応生成物を、精製工程を経て純度の高いトリフルオロ酢酸エステルを得ることができる。 A reaction product obtained by adding equimolar or more of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms can be purified to give a highly pure trifluoroacetic acid ester.
　精製工程における精製方法は、公知の精製方法を広く採用することが可能であり、特に限定はない。但し、簡便な方法であることから、蒸留により精製を実施することが好ましい。 The purification method in the purification step can be any known purification method and is not particularly limited. However, it is preferable to carry out purification by distillation because it is a simple method.
　本開示は、トリフルオロ酢酸エステルと、ＨＦと、ＣＦ３ＣＯＦとを含み、ＣＦ３ＣＯＦの含有量は０．１～３０質量％である組成物を開示する。 The present disclosure discloses a composition comprising a trifluoroacetic acid ester, HF, and CF 3 COF, the CF 3 COF content being 0.1 to 30 wt %.
　本開示の組成物中に含まれるＣＦ３ＣＯＦの含有量は、本開示の組成物１００質量％中に０．１質量％以上であり、０．２質量％以上であることが好ましく、０．５質量％以上であることがより好ましい。 The content of CF 3 COF contained in the composition of the present disclosure is 0.1 mass % or more, preferably 0.2 mass % or more, and more preferably 0.5 mass % or more, based on 100 mass % of the composition of the present disclosure.
　一方、本開示の組成物中に含まれるＣＦ３ＣＯＦの含有量は、本開示の組成物１００質量％中に３０質量％以下であり、１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。 On the other hand, the content of CF 3 COF contained in the composition of the present disclosure is 30 mass % or less, preferably 10 mass % or less, and more preferably 5 mass % or less, based on 100 mass % of the composition of the present disclosure.
　トリフルオロ酢酸エステルの含有量は、本開示の組成物１００質量％中に７０質量％以上であることが好ましく、７５質量％以上であることがより好ましく、８０質量％以上であることがさらに好ましい。 The content of trifluoroacetic acid ester is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more, based on 100% by mass of the composition of the present disclosure.
　一方、トリフルオロ酢酸エステルの含有量は、本開示の組成物１００質量％中に９０質量％以下であることが好ましく、８９質量％以下であることがより好ましく、８８質量％以下であることがさらに好ましい。 On the other hand, the content of trifluoroacetic acid ester is preferably 90% by mass or less, more preferably 89% by mass or less, and even more preferably 88% by mass or less, based on 100% by mass of the composition of the present disclosure.
　ＨＦの含有量は、本開示の組成物１００質量％中に１０質量％以上であることが好ましく、１１質量％以上であることがより好ましく、１２質量％以上であることがさらに好ましい。 The HF content is preferably 10% by mass or more, more preferably 11% by mass or more, and even more preferably 12% by mass or more, based on 100% by mass of the composition of the present disclosure.
　一方、ＨＦの含有量は、本開示の組成物１００質量％中に１５質量％以下であることが好ましく、１４質量％以下であることがより好ましく、１３質量％以下であることがさらに好ましい。 On the other hand, the HF content is preferably 15% by mass or less, more preferably 14% by mass or less, and even more preferably 13% by mass or less, based on 100% by mass of the composition of the present disclosure.
　本開示の組成物は、炭素数１～４の低級アルコールに対し、ＣＦ３ＣＯＦを等モル以上添加することにより得ることができる。 The composition of the present disclosure can be obtained by adding CF 3 COF in an equimolar amount or more to a lower alcohol having 1 to 4 carbon atoms.
　本開示の組成物は、その効果及び目的を阻害しない範囲内で、トリフルオロ酢酸、トルエン、及び水、からなる群より選択される少なくとも一種を含んでもよい。 The composition of the present disclosure may contain at least one selected from the group consisting of trifluoroacetic acid, toluene, and water, within a range that does not impair the effects and purpose of the composition.
　以上、本開示の実施形態について説明したが、本開示はこうした例に何ら限定されるものではなく、本開示の要旨を逸脱しない範囲において種々なる形態で実施し得ることは勿論である。 The above describes embodiments of the present disclosure, but the present disclosure is in no way limited to these examples, and can of course be embodied in various forms without departing from the gist of the present disclosure.
　以下、実施例に基づき、本開示の実施形態をより具体的に説明するが、本開示がこれらに限定されるものではない。 The following provides a more detailed explanation of the embodiments of the present disclosure based on examples, but the present disclosure is not limited to these.
（実施例１）
　１Ｌのステンレスオートクレーブにエタノール204g　4.43mol　(水分：0.2%含む）を仕込み、60℃に加熱攪拌しながら、CF3COF　585g　5.04molを一定流量で仕込みながら反応させた。反応圧力は最終的に0.6MPaGになった。反応後、反応混合物を精留塔に仕込み常圧下に精留を行った。低沸点のCF3COFを回収、沸点20℃のHF留分を抜き出したのち、高純度のトリフルオロ酢酸エチル　580ｇを回収した(収率92％）。 Example 1
204g (4.43mol) of ethanol (containing 0.2% water) was charged into a 1L stainless steel autoclave, and while heating and stirring at 60°C, 585g (5.04mol) of CF3COF was charged at a constant flow rate to react. The reaction pressure finally reached 0.6MPaG. After the reaction, the reaction mixture was charged into a rectification column and rectified under normal pressure. After recovering CF3COF with a low boiling point and extracting the HF fraction with a boiling point of 20°C, 580g of high-purity ethyl trifluoroacetate was recovered (yield 92%).
（実施例２～６）
　下記表１の通り、実施例１に準じた方法で実施例２～６を行った。 (Examples 2 to 6)
As shown in Table 1 below, Examples 2 to 6 were carried out in a manner similar to Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
（比較例１）
　１Ｌのステンレスオートクレーブにエタノール204g　4.435mol　(水分：0.2%含む）を仕込み、60℃に加熱攪拌しながら、CF3COF　250g　2.16molを一定流量で仕込みながら反応させた。反応圧力は最終的に大気圧になった。反応後、反応混合物を精留塔に仕込み常圧下に精留を行った。エタノールとトリフルオロ酢酸エチルとの共沸組成物が形成され、精留にて分離できず、トリフルオロ酢酸エチルを得ることは出来なかった。 (Comparative Example 1)
204g (4.435mol) of ethanol (containing 0.2% moisture) was charged into a 1L stainless steel autoclave, and while heating and stirring at 60°C, 250g (2.16mol) of CF3COF was charged at a constant flow rate to cause a reaction. The reaction pressure finally reached atmospheric pressure. After the reaction, the reaction mixture was charged into a rectification column and rectified under normal pressure. An azeotropic composition of ethanol and ethyl trifluoroacetate was formed, which could not be separated by rectification, and ethyl trifluoroacetate could not be obtained.
　下記表２に示す通り、各実施例では得られる組成物中のアルコールを排除することができたが、比較例１では上記の通りエタノールとトリフルオロ酢酸エチルとの共沸組成物が形成された。 As shown in Table 2 below, in each Example, the alcohol in the resulting composition could be eliminated, but in Comparative Example 1, an azeotropic composition of ethanol and ethyl trifluoroacetate was formed as described above.
Figure JPOXMLDOC01-appb-T000002
  
Figure JPOXMLDOC01-appb-T000002
  

Claims (4)

  1. 　トリフルオロ酢酸エステルの製造方法であって、
    　炭素数１～４の低級アルコールに対し、ＣＦ３ＣＯＦを等モル以上添加することにより、トリフルオロ酢酸エステル及びＨＦを得る反応工程を有する、トリフルオロ酢酸エステルの製造方法。     1. A method for producing a trifluoroacetic ester, comprising the steps of:
    A method for producing a trifluoroacetic ester, comprising a reaction step of adding equimolar or more of CF 3 COF to a lower alcohol having 1 to 4 carbon atoms to obtain a trifluoroacetic ester and HF.
  2. 　前記反応工程において、炭素数１～４の低級アルコール１モルに対し、ＣＦ３ＣＯＦを１～３モルのモル比で添加する、請求項１に記載の製造方法。 2. The method according to claim 1, wherein in the reaction step, CF 3 COF is added in a molar ratio of 1 to 3 moles per mole of the lower alcohol having 1 to 4 carbon atoms.
  3. 　前記炭素数１～４の低級アルコールはエタノールである、請求項１又は２の製造方法。 The method of claim 1 or 2, wherein the lower alcohol having 1 to 4 carbon atoms is ethanol.
  4. 　トリフルオロ酢酸エステルと、ＨＦと、ＣＦ３ＣＯＦとを含み、ＣＦ３ＣＯＦの含有量は０．１～３０質量％である、組成物。
          A composition comprising a trifluoroacetic acid ester, HF, and CF 3 COF, the CF 3 COF content being 0.1 to 30 mass %.
PCT/JP2024/008974 2023-03-09 2024-03-08 Trifluoroacetic acid ester production method WO2024185877A1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6236344A (en) * 1985-07-19 1987-02-17 アウシモント、ソチエタ、ペル、アツイオ−ニ Manufacture of trifluoroacetic acid alkyl

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6236344A (en) * 1985-07-19 1987-02-17 アウシモント、ソチエタ、ペル、アツイオ−ニ Manufacture of trifluoroacetic acid alkyl

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MAJID A. J, SHREEVE M: "Fluorinated Esters Stable to Fluoride Ion", THE JOURNAL OF ORGANIC CHEMISTRY., vol. 38, no. 23, 1 November 1973 (1973-11-01), pages 4028 - 4031, XP093207630, DOI: 10.1021/jo00987a016 *

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