JP2012025697A - Method for producing difluoroacetate ester - Google Patents

Method for producing difluoroacetate ester Download PDF

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JP2012025697A
JP2012025697A JP2010165852A JP2010165852A JP2012025697A JP 2012025697 A JP2012025697 A JP 2012025697A JP 2010165852 A JP2010165852 A JP 2010165852A JP 2010165852 A JP2010165852 A JP 2010165852A JP 2012025697 A JP2012025697 A JP 2012025697A
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producing
acid
hcf
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difluoroacetate
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Daisuke Asada
大介 浅田
Tatsuya Otsuka
達也 大塚
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Daikin Industries Ltd
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters

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Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a difluoroacetate ester at a high selectivity while formation of by-products are suppressed.SOLUTION: The method for producing a difluoroacetate ester represented by formula: HCFCOOR (wherein R denotes a lower alkyl group) includes bringing 1,1,2,2-tetrafluoroethyl alkyl ether represented by formula HCFCFOR (wherein R is the same in the above) into contact with an acid catalyst in the presence of an oxide and a lower alcohol.

Description

本発明は、ジフルオロ酢酸エステルの製造方法に関する。   The present invention relates to a method for producing a difluoroacetic acid ester.

ジフルオロ酢酸エチル（HCF2CO2Et）は医薬、農薬等の中間体として非常に重要な化合物である。 Ethyl difluoroacetate (HCF 2 CO 2 Et) is a very important compound as an intermediate for pharmaceuticals, agricultural chemicals and the like.

ジフルオロ酢酸エチルの合成法としては、下記反応式に従って、まず、四フッ化エチレン（TFE）とエタノールを反応させて1,1,2,2-テトラフルオロエチルエチルエーテルを調製し、次に、得られたエーテルに、酸素供給源として二酸化ケイ素の存在下、濃硫酸を作用させて酸加水分解反応を行う方法が知られている（非特許文献１参照）。
TFE + EtOH + KOH → HCF2CF2OEt
HCF2CF2OEt + 1/2SiO2+ H2SO4 → HCF2CO2Et + 1/2SiF4
この方法では、HFやフッ化物の固体を発生することなくジフルオロ酢酸エチルを製造することが可能であるが、ジフルオロ酢酸等の副生物が生成し易く、目的とするジフルオロ酢酸エチルの選択率が低いという欠点がある。 In order to synthesize ethyl difluoroacetate, according to the following reaction formula, first, 1,1,2,2-tetrafluoroethyl ethyl ether was prepared by reacting ethylene tetrafluoride (TFE) with ethanol. A method is known in which acid hydrolysis reaction is carried out by allowing concentrated sulfuric acid to act on the obtained ether in the presence of silicon dioxide as an oxygen supply source (see Non-Patent Document 1).
TFE + EtOH + KOH → HCF 2 CF 2 OEt
HCF 2 CF 2 OEt + 1 / 2SiO 2 + H 2 SO 4 → HCF 2 CO 2 Et + 1 / 2SiF 4
In this method, it is possible to produce ethyl difluoroacetate without generating HF or fluoride solids, but byproducts such as difluoroacetic acid are easily generated, and the selectivity of the target ethyl difluoroacetate is low. There is a drawback.

J. Amer. Chem. Soc., 1950, 72, 1860J. Amer. Chem. Soc., 1950, 72, 1860

本発明は上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、副生物の生成を抑制して、高い選択率でジフルオロ酢酸エステルを製造できる方法を提供することである。 The present invention has been made in view of the current state of the prior art described above, and its main purpose is to provide a method capable of producing difluoroacetic acid esters with high selectivity while suppressing the formation of by-products. .

本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、1,1,2,2-テトラフルオロエチルアルキルエーテルを原料としてジフルオロ酢酸エステルを製造する際に、酸素供給源として酸化物とアルコールの存在下に、酸触媒を作用させる方法によれば、副生物の生成を抑制して、高い選択率で目的とするジフルオロ酢酸エステルを製造できることを見出し、ここに本発明を完成するに至った。   The present inventor has intensively studied to achieve the above-described object. As a result, according to the method in which an acid catalyst is allowed to act in the presence of an oxide and an alcohol as an oxygen supply source when producing a difluoroacetic acid ester using 1,1,2,2-tetrafluoroethyl alkyl ether as a raw material. The inventors have found that the desired difluoroacetate can be produced with high selectivity while suppressing the formation of by-products, and the present invention has been completed here.

即ち、本発明は、下記のジフルオロ酢酸エステルの製造方法を提供するものである。
項１. 酸化物及び低級アルコールの存在下において、一般式：HCF2CF2OR（式中、Rは、低級アルキル基を示す）で表される1,1,2,2-テトラフルオロエチルアルキルエーテルを酸触媒に接触させることを特徴とする、一般式：HCF2COOR（式中、Rは上記に同じ）で表されるジフルオロ酢酸エステルの製造方法。
項２. 酸化物が、SiO2及びAl2O3からなる群から選ばれた少なくとも一種の成分を含むものである上記項１に記載のジフルオロ酢酸エステルの製造方法。
項３． 低級アルコールが、エタノール及びメタノールからなる群から選ばれた少なくとも一種である上記項１又は２に記載のジフルオロ酢酸エステルの製造方法。
項４． 酸触媒が、硫酸、p-トルエンスルホン酸、メタンスルホン酸及び三フッ化ホウ素からなる群から選ばれた少なくとも一種である上記項１〜３のいずれか一項に記載のジフルオロ酢酸エステルの製造方法
以下、本発明のジフルオロ酢酸エステルの製造方法について具体的に説明する。 That is, this invention provides the manufacturing method of the following difluoroacetate ester.
Item 1. 1,1,2,2-tetrafluoroethylalkyl represented by the general formula: HCF 2 CF 2 OR (wherein R represents a lower alkyl group) in the presence of an oxide and a lower alcohol A method for producing a difluoroacetic acid ester represented by the general formula: HCF 2 COOR (wherein R is the same as above), which comprises contacting ether with an acid catalyst.
Item 2. The method for producing a difluoroacetic acid ester according to Item 1, wherein the oxide contains at least one component selected from the group consisting of SiO 2 and Al 2 O 3 .
Item 3. Item 3. The method for producing a difluoroacetic acid ester according to Item 1 or 2, wherein the lower alcohol is at least one selected from the group consisting of ethanol and methanol.
Item 4. Item 4. The method for producing a difluoroacetic acid ester according to any one of Items 1 to 3, wherein the acid catalyst is at least one selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and boron trifluoride. Hereafter, the manufacturing method of the difluoroacetic acid ester of this invention is demonstrated concretely.

原料化合物
本発明では、原料としては、一般式：HCF2CF2OR（式中、Rは、低級アルキル基を示す）で表される1,1,2,2-テトラフルオロエチルアルキルエーテルを用いる。 Raw Material Compound In the present invention, 1,1,2,2-tetrafluoroethyl alkyl ether represented by the general formula: HCF 2 CF 2 OR (wherein R represents a lower alkyl group) is used as the raw material. .

上記一般式において、Ｒで表される低級アルキル基としては、炭素数１〜４の直鎖状又は分岐鎖状のアルキル基を挙げることができる。具体的には、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔｅｒｔ−ブチル、ｓｅｃ−ブチルシル基等を例示できる。   In the above general formula, examples of the lower alkyl group represented by R include linear or branched alkyl groups having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butylsil group and the like.

上記一般式で表される1,1,2,2-テトラフルオロエチルアルキルエーテルは公知化合物であり、例えば、下記反応式に従って、四フッ化エチレンとエタノールを反応させることによって得ることができる。   1,1,2,2-Tetrafluoroethyl alkyl ether represented by the above general formula is a known compound and can be obtained, for example, by reacting ethylene tetrafluoride and ethanol according to the following reaction formula.

CF2=CF2 + ROH + KOH → HCF2CF2OR
ジフルオロ酢酸エステルの製造方法
本発明のジフルオロ酢酸エステルの製造方法では、上記した一般式：HCF2CF2OR（式中、Rは、低級アルキル基を示す）で表される1,1,2,2-テトラフルオロエチルアルキルエーテルを、酸化物及び低級アルコールの存在下において、酸触媒に接触させることが必要である。 CF 2 = CF 2 + ROH + KOH → HCF 2 CF 2 OR
Production method of difluoroacetate ester In the production method of difluoroacetate ester of the present invention, 1,1,2, represented by the general formula: HCF 2 CF 2 OR (wherein R represents a lower alkyl group) It is necessary to contact 2-tetrafluoroethyl alkyl ether with an acid catalyst in the presence of an oxide and a lower alcohol.

上記反応に用いる酸化物としては、SiO2及びAl2O3からなる群から選ばれた少なくとも一種の成分を含む酸化物を用いることが好ましい。該酸化物において、SiO2及びAl2O3からなる群から選ばれた少なくとも一種の成分の含有量は、特に限定的ではないが、通常、酸化物中に８０重量％程度以上含まれていることが好ましい。 As the oxide used in the above reaction, an oxide containing at least one component selected from the group consisting of SiO 2 and Al 2 O 3 is preferably used. In the oxide, the content of at least one component selected from the group consisting of SiO 2 and Al 2 O 3 is not particularly limited, but is usually about 80% by weight or more in the oxide. It is preferable.

この様な酸化物の具体例としては、シリカゲル、珪石、ガラス、石英、海砂、セライト、アルミナ等を例示できる。特に、シリカゲル、珪石粉末などが好ましい。これらの酸化物は、通常、溶存水分として水を含むか、或いは、表面に水酸基を有するものであり、これらによって、1,1,2,2-テトラフルオロエチルアルキルエーテルの分解反応が進行するものと推測される。   Specific examples of such oxides include silica gel, silica, glass, quartz, sea sand, celite, and alumina. In particular, silica gel, silica powder and the like are preferable. These oxides usually contain water as dissolved water or have hydroxyl groups on the surface, and the decomposition reaction of 1,1,2,2-tetrafluoroethyl alkyl ether proceeds by these. It is guessed.

上記した酸化物の内で、特に、SiO2を含む酸化物を用いる場合には、1,1,2,2-テトラフルオロエチルアルキルエーテルの加水分解反応によって生じたHFが、系内でSiO2と反応することにより水とSiF4となり、SiF4は気体であるために系外に除去され、水は次の反応に利用され、その結果、HFやフッ化物の固体を発生することなくジフルオロ酢酸エチルを製造することができる。 Among the oxides described above, particularly when an oxide containing SiO 2 is used, HF generated by the hydrolysis reaction of 1,1,2,2-tetrafluoroethyl alkyl ether is converted into SiO 2 in the system. Reacts with water to form SiF 4 and is removed from the system because SiF 4 is a gas, and water is used in the next reaction, resulting in difluoroacetic acid without generating HF or fluoride solids. Ethyl can be produced.

使用する酸化物の形状については、特に限定はないが、良好な反応性とするために、粒径1μm〜2mm程度の粉末として用いることが好ましい。   The shape of the oxide to be used is not particularly limited, but it is preferably used as a powder having a particle size of about 1 μm to 2 mm in order to obtain good reactivity.

酸化物の使用量については、特に限定的ではないが、通常、1,1,2,2-テトラフルオロエチルアルキルエーテル１モルに対して、0.5〜1.5モル程度とすることが好ましい。   The amount of oxide used is not particularly limited, but it is usually preferably about 0.5 to 1.5 moles per mole of 1,1,2,2-tetrafluoroethyl alkyl ether.

低級アルコールとしては、特に限定的ではないが、炭素数１〜４程度のアルコールが好ましく、特に、エタノール及びメタノールが好ましい。   The lower alcohol is not particularly limited, but an alcohol having about 1 to 4 carbon atoms is preferable, and ethanol and methanol are particularly preferable.

低級アルコールの使用量は、原料として用いる1,1,2,2-テトラフルオロエチルアルキルエーテル１モルに対して０．０３〜０．５モル程度とすることが好ましく、０．０５〜０．２モル程度とすることがより好ましい。   The amount of the lower alcohol used is preferably about 0.03 to 0.5 mol per mol of 1,1,2,2-tetrafluoroethyl alkyl ether used as a raw material, More preferably, it is about a mole.

酸触媒としては、酸加水分解反応に対して活性を有する物質であれば特に制限されない。この様な酸触媒の具体例としては、硫酸、p-トルエンスルホン酸、メタンスルホン酸、三フッ化ホウ素等を例示できる。   The acid catalyst is not particularly limited as long as it is a substance having activity for acid hydrolysis reaction. Specific examples of such an acid catalyst include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, boron trifluoride and the like.

酸触媒の使用量は、原料として用いる1,1,2,2-テトラフルオロエチルアルキルエーテル１モルに対して０．０１〜１モル程度とすることが好ましく、０．０５〜０．３モル程度とすることがより好ましい。   The amount of the acid catalyst used is preferably about 0.01 to 1 mol, and about 0.05 to 0.3 mol with respect to 1 mol of 1,1,2,2-tetrafluoroethyl alkyl ether used as a raw material. More preferably.

本発明のジフルオロ酢酸エステルの製造方法では、具体的な反応方法については特に限定はなく、原料として用いるジフルオロ酢酸エステルと酸化物、低級アルコール及び酸触媒とが同時に接触できる方法であればよい。例えば、1,1,2,2-テトラフルオロエチルアルキルエーテル、酸化物及び低級アルコールを含む反応容器中に酸触媒を滴下する方法等を適用できる。   In the method for producing difluoroacetic acid ester of the present invention, the specific reaction method is not particularly limited as long as the difluoroacetic acid ester used as a raw material and the oxide, lower alcohol and acid catalyst can be contacted at the same time. For example, a method of dropping an acid catalyst into a reaction vessel containing 1,1,2,2-tetrafluoroethyl alkyl ether, an oxide and a lower alcohol can be applied.

反応温度については、室温〜２００℃程度とすることが好ましく、８０〜１５０℃程度とすることがより好ましい。   About reaction temperature, it is preferable to set it as room temperature-about 200 degreeC, and it is more preferable to set it as about 80-150 degreeC.

反応時の雰囲気については、特に限定はないが、過剰の水分は好ましくないため、大気圧で反応を行う場合は、通常、乾燥空気や窒素もしくは不活性ガス雰囲気中等で反応を行うことが好ましい。   The atmosphere during the reaction is not particularly limited, but excessive moisture is not preferable. Therefore, when the reaction is performed at atmospheric pressure, it is usually preferable to perform the reaction in a dry air, nitrogen or inert gas atmosphere.

反応時の圧力については、特に限定はないが、SiO2を含む酸化物を用いて密閉容器中で反応を行う場合には、反応の進行に伴ってSiF4ガスが発生し、これにより容器内の圧力が上昇する。この場合、必要に応じて、発生したSiF4ガスを系外に除去すればよい。 There is no particular limitation on the pressure during the reaction, but when the reaction is performed in an airtight container using an oxide containing SiO 2 , SiF 4 gas is generated as the reaction proceeds, which The pressure increases. In this case, the generated SiF 4 gas may be removed from the system as necessary.

反応時間は、通常、3時間〜48時間程度である。   The reaction time is usually about 3 to 48 hours.

上記した方法によれば、高い選択率で目的とする一般式：HCF2COOR（式中、Rは上記に同じ）で表されるジフルオロ酢酸エステルを得ることができる。 According to the method described above, a difluoroacetic acid ester represented by the target general formula: HCF 2 COOR (wherein R is the same as above) can be obtained with high selectivity.

得られた粗生成物は、常法に従って、必要に応じてろ過・洗浄・抽出などの操作の後、蒸留等の方法で分離精製することができる。   The obtained crude product can be separated and purified by a method such as distillation after an operation such as filtration, washing or extraction, if necessary, according to a conventional method.

上記した方法で得られるジフルオロ酢酸エステルは、医薬、農薬等の中間体として有用性の高い物質である。   The difluoroacetate obtained by the above method is a highly useful substance as an intermediate for pharmaceuticals, agricultural chemicals and the like.

本発明の方法によれば、高い選択率で目的とするジフルオロ酢酸エステルを得ることができる。従って、本発明方法は、低コストでジフルオロ酢酸エステルを製造できる点において、工業的に有利な方法である。   According to the method of the present invention, a target difluoroacetic acid ester can be obtained with high selectivity. Therefore, the method of the present invention is an industrially advantageous method in that difluoroacetate can be produced at low cost.

以下、実施例を挙げて本発明を更に詳細に説明する。   Hereinafter, the present invention will be described in more detail with reference to examples.

実施例１
HCF2CF2OEt + 1/2SiO2 +H2SO4(cat.) → HCF2CO2Et + 1/2SiF4
マグネチックスターラーバーを入れた100mlのSUS製オートクレーブに1,1,2,2-テトラフルオロエチルエチルエーテル（HCF2CF2OEt）（9.0g, 61.6mmol）、珪砂粉末（2.22g, 36.9mmol）及びエタノール（0.28g, 6.2mmol）を仕込み、濃硫酸（0.60g, 6.2mmol）を滴下した。オートクレーブの蓋を閉めて、100℃のオイルバスに浸漬して24時間攪拌した。オートクレーブ内の圧力は、0.8MPaGに上昇した。
次いで、オートクレーブのバルブを少しずつ開け、SiF4ガスを10%HF水溶液に流すことにより処理した。 Example 1
HCF 2 CF 2 OEt + 1 / 2SiO 2 + H 2 SO 4 (cat.) → HCF 2 CO 2 Et + 1 / 2SiF 4
1,1,2,2-tetrafluoroethyl ethyl ether (HCF 2 CF 2 OEt) (9.0 g, 61.6 mmol), silica sand powder (2.22 g, 36.9 mmol) in a 100 ml SUS autoclave with a magnetic stir bar And ethanol (0.28 g, 6.2 mmol) were added, and concentrated sulfuric acid (0.60 g, 6.2 mmol) was added dropwise. The lid of the autoclave was closed and immersed in a 100 ° C. oil bath and stirred for 24 hours. The pressure in the autoclave increased to 0.8 MPaG.
Subsequently, the autoclave valve was opened little by little, and the treatment was performed by flowing SiF 4 gas into a 10% HF aqueous solution.

オートクレーブの蓋を開けた後、内容物をテトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体（PFA）からなる容器に移すことによって、褐色の反応混合物を10.3g得た。   After opening the lid of the autoclave, the contents were transferred to a container made of tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) to obtain 10.3 g of a brown reaction mixture.

この反応液の組成を19F-NMRで分析したところ、原料転化率は99.4%、HCF2CO2Et（ジフルオロ酢酸エチル）:HCF2CO2H（ジフルオロ酢酸（カルボン酸塩を含む））=93:7（モル比）であった。また、19F-NMR上でHFは確認できなかった。 When the composition of this reaction solution was analyzed by 19 F-NMR, the raw material conversion was 99.4%, HCF 2 CO 2 Et (ethyl difluoroacetate): HCF 2 CO 2 H (difluoroacetic acid (including carboxylate)) = 93: 7 (molar ratio). Moreover, HF was not confirmed on 19 F-NMR.

比較例１
エタノールを添加することなく、それ以外は実施例１と同様にしてジフルオロ酢酸エチルを製造した。 Comparative Example 1
Ethyl difluoroacetate was produced in the same manner as in Example 1 except that ethanol was not added.

原料転化率は１００％であったが、生成物におけるジフルオロ酢酸エチルの選択率は、８３％であり、実施例１と比較して、副生物であるジフルオロ酢酸等を多量に含むものであった。   Although the raw material conversion rate was 100%, the selectivity of ethyl difluoroacetate in the product was 83%, which contained a large amount of difluoroacetic acid as a by-product as compared with Example 1. .

この様な酸化物の具体例としては、シリカゲル、珪石、珪砂粉末、ガラス、石英、海砂、セライト、アルミナ等を例示できる。特に、シリカゲル、珪石粉末などが好ましい。これらの酸化物は、通常、溶存水分として水を含むか、或いは、表面に水酸基を有するものであり、これらによって、1,1,2,2-テトラフルオロエチルアルキルエーテルの分解反応が進行するものと推測される。 Specific examples of such oxides include silica gel, silica, silica sand powder, glass, quartz, sea sand, celite, and alumina. In particular, silica gel, silica powder and the like are preferable. These oxides usually contain water as dissolved water or have hydroxyl groups on the surface, and the decomposition reaction of 1,1,2,2-tetrafluoroethyl alkyl ether proceeds by these. It is guessed.

Claims (4)

酸化物及び低級アルコールの存在下において、一般式：HCF2CF2OR（式中、Rは、低級アルキル基を示す）で表される1,1,2,2-テトラフルオロエチルアルキルエーテルを酸触媒に接触させることを特徴とする、一般式：HCF2COOR（式中、Rは上記に同じ）で表されるジフルオロ酢酸エステルの製造方法。 In the presence of an oxide and a lower alcohol, 1,1,2,2-tetrafluoroethyl alkyl ether represented by the general formula: HCF 2 CF 2 OR (wherein R represents a lower alkyl group) is converted to an acid. A method for producing a difluoroacetic acid ester represented by the general formula: HCF 2 COOR (wherein R is the same as above), which is brought into contact with a catalyst. 酸化物が、SiO2及びAl2O3からなる群から選ばれた少なくとも一種の成分を含むものである請求項１に記載のジフルオロ酢酸エステルの製造方法。 The method for producing a difluoroacetic acid ester according to claim 1, wherein the oxide contains at least one component selected from the group consisting of SiO 2 and Al 2 O 3 . 低級アルコールが、エタノール及びメタノールからなる群から選ばれた少なくとも一種である請求項１又は２に記載のジフルオロ酢酸エステルの製造方法。 The method for producing a difluoroacetic acid ester according to claim 1 or 2, wherein the lower alcohol is at least one selected from the group consisting of ethanol and methanol. 酸触媒が、硫酸、p-トルエンスルホン酸、メタンスルホン酸及び三フッ化ホウ素からなる群から選ばれた少なくとも一種である請求項１〜３のいずれか一項に記載のジフルオロ酢酸エステルの製造方法。 The method for producing a difluoroacetic acid ester according to any one of claims 1 to 3, wherein the acid catalyst is at least one selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, and boron trifluoride. .
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