JP2016523233A - Method for preparing halogenated carboxylic acid anhydride - Google Patents
Method for preparing halogenated carboxylic acid anhydride Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 title abstract description 7
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 16
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- -1 H 2 SO 4 Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000000356 contaminant Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本発明は、ハロゲン化カルボン酸無水物の調製のための方法、例えば、トリフルオロ酢酸無水物の調製のための方法に関する。調製は、ハロゲン化カルボン酸、例えば、トリフルオロ酢酸を、硫酸、発煙硫酸及び／又は二硫酸と反応させることにより達成される。【選択図】なしThe present invention relates to a process for the preparation of halogenated carboxylic anhydrides, for example a process for the preparation of trifluoroacetic anhydride. The preparation is accomplished by reacting a halogenated carboxylic acid such as trifluoroacetic acid with sulfuric acid, fuming sulfuric acid and / or disulfuric acid. [Selection figure] None
Description
本発明は、本出願の全内容があらゆる目的のために参照により本明細書に組み込まれる、欧州特許出願第１３１７０８６８．７号に対する優先権を主張するものであって、ハロゲン化カルボン酸無水物の調製方法、より詳細にはハロゲン化カルボン酸を硫酸、発煙硫酸及び／又は二硫酸と反応させることによるハロゲン化カルボン酸無水物の調製方法に関する。 The present invention claims priority to European Patent Application No. 131708688.7, the entire contents of which are incorporated herein by reference for all purposes, More particularly, the present invention relates to a method for preparing a halogenated carboxylic acid anhydride by reacting a halogenated carboxylic acid with sulfuric acid, fuming sulfuric acid and / or disulfuric acid.
トリフルオロ酢酸のようなハロゲン化カルボン酸無水物は、医薬品および農薬産業における様々な製品の製造のための貴重な試薬である。 Halogenated carboxylic anhydrides such as trifluoroacetic acid are valuable reagents for the manufacture of various products in the pharmaceutical and agrochemical industries.
トリフルオロ酢酸と無水リン酸との反応によりトリフルオロ酢酸無水物を調製することは公知である。（Ｈｕｄｌｉｃｋｙ，Ｃｈｅｍｉｓｔｒｙ ｏｆ Ｏｒｇａｎｉｃ Ｆｌｕｏｒｉｎｅ Ｃｏｍｐｏｕｎｄｓ，１９７６，ｐ．７２６）。そこに記載された方法は、無水リン酸が固体であり、かつ反応物質及び／又は生成物とアマルガムを形成する傾向があるので工業生産に不利である。 It is known to prepare trifluoroacetic anhydride by reaction of trifluoroacetic acid with phosphoric anhydride. (Hudlicky, Chemistry of Organic Fluorine Compounds, 1976, p. 726). The process described therein is disadvantageous for industrial production because phosphoric anhydride is solid and tends to form amalgam with reactants and / or products.
したがって、今や、本発明は、ハロゲン化カルボン酸無水物の製造のための改善された方法を可能にする。本発明の目的は、生成物の改善された収率及び／又は純度を可能にするハロゲン化カルボン酸無水物の製造のための方法を提供することである。さらに、本発明の目的は、より経済的及び／若しくはより環境に優しい廃棄物、並びに／又は不要な副生成物プロファイルを有する方法、例えば、廃棄物及び／又は副生成物が、その方法の生成物からより容易に分離され、及び／又はより毒性が少なく及び／又は環境に対してより害の少ない方法を提供することである。さらに、本発明の目的は、例えば、より低い純度の反応物質を用いるように、より安価及び／若しくはより容易に入手できる反応物質、並びに／又は試薬から出発する方法を提供することである。 Thus, the present invention now enables an improved process for the production of halogenated carboxylic acid anhydrides. The object of the present invention is to provide a process for the production of halogenated carboxylic acid anhydrides which allows an improved yield and / or purity of the product. Furthermore, it is an object of the present invention to provide a process with more economical and / or more environmentally friendly waste and / or unwanted by-product profiles, for example waste and / or by-products produced in the process To provide a method that is more easily separated from objects and / or less toxic and / or less harmful to the environment. Furthermore, it is an object of the present invention to provide a method that starts with cheaper and / or more readily available reactants and / or reagents, such as using lower purity reactants.
これらの及び他の目的は、本発明の方法により達成される。 These and other objects are achieved by the method of the present invention.
したがって、本発明の第１の実施態様は、一般構造（Ｉ）：ＨａｌＲ２Ｃ（Ｏ）−Ｏ−Ｃ（Ｏ）ＣＲ２Ｈａｌ（式中、Ｈａｌは、Ｆ、Ｃｌ及びＢｒからなる群から選択され；Ｒは、Ｈ、Ｆ、Ｃｌ、Ｂｒ、アルキル及びアリールからなる群から独立して選択される）の化合物の調製のための方法であって、一般構造（ＩＩ）：ＨａｌＲ２Ｃ（Ｏ）−ＯＨ（式中、ＨａｌおよびＲは、上記のとおり定義される）の化合物を、硫酸、発煙硫酸及び／又は二硫酸と反応させる工程を含む方法である。 Accordingly, a first embodiment of the invention is a general structure (I): HalR2C (O) -OC (O) CR2Hal wherein Hal is selected from the group consisting of F, Cl and Br; R Is independently selected from the group consisting of H, F, Cl, Br, alkyl, and aryl), and is a general structure (II): HalR 2 C (O) —OH (formula In which Hal and R are defined as above) with sulfuric acid, fuming sulfuric acid and / or disulfuric acid.
「硫酸（sulfuric acid）」という用語は、純粋な硫酸、Ｈ２ＳＯ４、及びその水溶液を意味することが意図される。好ましくは、本発明により用いられる硫酸は、７０ｗｔ％以上の濃度、より好ましくは９０ｗｔ％以上の濃度を有し、最も好ましくは、濃硫酸が用いられ、これは、約９８ｗｔ％の濃度を有する。 The term “sulfuric acid” is intended to mean pure sulfuric acid, H 2 SO 4, and aqueous solutions thereof. Preferably, the sulfuric acid used according to the present invention has a concentration of 70 wt% or more, more preferably 90 wt% or more, most preferably concentrated sulfuric acid is used, which has a concentration of about 98 wt%.
「発煙硫酸（oleum）」という用語は、Ｈ２ＳＯ４とＳＯ３の混合物を意味することが意図される。発煙硫酸の濃度は、ｗｔ％ＳＯ３（Ｘ％発煙硫酸と呼ばれる）又はｗｔ％Ｈ２ＳＯ４のいずれかで表される。例えば、６５％発煙硫酸は、１１４．６ｗｔ％Ｈ２ＳＯ４を指す。発煙硫酸中のＳＯ３の百分率も、遊離ＳＯ３と称される。したがって、６５％発煙硫酸は、６５ｗｔ％の遊離ＳＯ３を含有する。 The term “oleum” is intended to mean a mixture of H 2 SO 4 and SO 3. The concentration of fuming sulfuric acid is expressed in either wt% SO3 (referred to as X% fuming sulfuric acid) or wt% H2SO4. For example, 65% fuming sulfuric acid refers to 114.6 wt% H2SO4. The percentage of SO3 in the fuming sulfuric acid is also referred to as free SO3. Thus, 65% fuming sulfuric acid contains 65 wt% free SO3.
「二硫酸（dissulfuric acid）」という用語は、Ｈ２Ｓ２Ｏ７を意味することが意図される。 The term “dissulfuric acid” is intended to mean H 2 S 2 O 7.
「アルキル（alkyl）」という用語は、特にＣ１―Ｃ６アルキルなどの、飽和炭化水素系基の任意選択的に置換された鎖を意味することが意図される。一例として、メチル、エチル、プロピル、イソプロピル、ブチル、ｔ−ブチル、ペンチル、イソペンチル及びヘキシルが挙げられてもよい。 The term “alkyl” is intended to mean an optionally substituted chain of a saturated hydrocarbon-based group, in particular C1-C6 alkyl. As an example may be mentioned methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, isopentyl and hexyl.
「アリール（aryl）」という用語は、特にＣ６―Ｃ１０芳香族核、特にフェニル又はナフチルなどの芳香族核に由来する任意選択的に置換された基を意味することが意図される。 The term “aryl” is intended to mean an optionally substituted group derived in particular from a C6-C10 aromatic nucleus, in particular an aromatic nucleus such as phenyl or naphthyl.
好ましい実施態様において、Ｈａｌはフッ素である。より好ましくは、一般構造（Ｉ）の化合物は、トリフルオロ酢酸無水物であり、及び一般構造（ＩＩ）の化合物は、トリフルオロ酢酸である。 In a preferred embodiment, Hal is fluorine. More preferably, the compound of general structure (I) is trifluoroacetic anhydride and the compound of general structure (II) is trifluoroacetic acid.
本発明の別の実施態様は、酢酸、酢酸塩又はそれらの混合物を、硫酸、発煙硫酸及び／又は二硫酸と反応させて、酢酸無水物を形成することである。酢酸塩の有用な例には、酢酸ナトリウム、酢酸カリウム、酢酸カルシウム、酢酸リチウム、酢酸マグネシウム、又はそれらの任意の混合物が含まれる。酢酸塩及び／又は酢酸は、無溶媒形態で、又は溶媒中の溶液として、好ましくは水溶液として用いられ得る。 Another embodiment of the invention is to react acetic acid, acetate salt or mixtures thereof with sulfuric acid, fuming sulfuric acid and / or disulfuric acid to form acetic anhydride. Useful examples of acetate include sodium acetate, potassium acetate, calcium acetate, lithium acetate, magnesium acetate, or any mixture thereof. The acetate and / or acetic acid can be used in a solvent-free form or as a solution in a solvent, preferably as an aqueous solution.
別の好ましい実施態様では、一般構造（ＩＩ）の化合物は、発煙硫酸、好ましくは５から９５ｗｔ％までの遊離ＳＯ３、より好ましくは２５から８０ｗｔ％までの遊離ＳＯ３、最も好ましくは５０から７０ｗｔ％までの遊離ＳＯ３、特には６５ｗｔ％遊離ＳＯ３を含有する発煙硫酸と反応させる。 In another preferred embodiment, the compound of general structure (II) comprises fuming sulfuric acid, preferably 5 to 95 wt% free SO3, more preferably 25 to 80 wt% free SO3, most preferably 50 to 70 wt%. The reaction is carried out with fuming sulfuric acid containing, in particular, 65 wt% free SO3.
別の好ましい実施態様において、ハロゲン化カルボン酸は、反応の化学量論に対してモル過剰で存在する。ハロゲン化カルボン酸の総量は、好ましくは化学量論の１．０５から２倍、より好ましくは化学量論の１．０５から１．１０倍である。 In another preferred embodiment, the halogenated carboxylic acid is present in a molar excess relative to the stoichiometry of the reaction. The total amount of halogenated carboxylic acid is preferably 1.05 to 2 times the stoichiometry, more preferably 1.05 to 1.10 times the stoichiometry.
好適には、反応は、高温で行なわれ、ここで、反応混合物の内部温度は、生成物の沸点以上である。好ましくは、反応は、５０から１５０℃、好ましくは７０から１１５℃の、反応混合物中の温度で行われる。反応混合物の温度は、反応容器における内部温度を指す。 Suitably the reaction is carried out at an elevated temperature, wherein the internal temperature of the reaction mixture is above the boiling point of the product. Preferably the reaction is carried out at a temperature in the reaction mixture of 50 to 150 ° C, preferably 70 to 115 ° C. The temperature of the reaction mixture refers to the internal temperature in the reaction vessel.
別の好ましい実施態様では、生成物は、蒸留により反応混合物から除去され、より好ましくは、蒸留は、充填カラムを用いて行なわれる。充填カラムは、例えば、ラシヒリングにより、好適に充填される。また好ましくは、蒸留は、生成物が反応混合物から除去される速度を制御するために還流凝縮器を用いて行なわれる。 In another preferred embodiment, the product is removed from the reaction mixture by distillation, more preferably the distillation is performed using a packed column. The packed column is preferably packed, for example, by Raschig ring. Also preferably, the distillation is performed using a reflux condenser to control the rate at which product is removed from the reaction mixture.
別の好ましい実施態様では、反応は、少なくとも部分的にセラミックライニング及び／又はガラスライニングされている反応容器で行なわれる。好適には、セラミックライニングを有する連続撹拌ファウドラー容器が用いられ得る。また好ましくは、反応は、ニッケル及び／又はモリブデンを含有する合金から少なくとも部分的に作られている反応容器で行なわれる。好適な合金の例には、ハステロイＢ、ハステロイＢ−２、又はハステロイＢ−３が含まれる。 In another preferred embodiment, the reaction is carried out in a reaction vessel that is at least partially ceramic-lined and / or glass-lined. Preferably, a continuous stirred fouler vessel with a ceramic lining can be used. Also preferably, the reaction is carried out in a reaction vessel made at least in part from an alloy containing nickel and / or molybdenum. Examples of suitable alloys include Hastelloy B, Hastelloy B-2, or Hastelloy B-3.
本発明による方法のさらなる利点は、高純度のハロゲン化カルボン酸無水物が、より低い純度の反応物質、すなわち、ハロゲン化カルボン酸が使用される場合でさえも、高収率で生成され得ることである。例えば、前の反応からの未反応ハロゲン化カルボン酸及び汚染物質を含有するテーリング留分（ｔａｉｌｉｎｇ ｆｒａｃｔｉｏｎ）は、本発明の方法に使用され得る。したがって、再生利用ハロゲン化カルボン酸は、本発明の方法に用いられ得る。したがって、好ましい実施態様では、反応に使用されるハロゲン化カルボン酸は、９８％以下の純度、より好ましくは９５％未満の純度、さらにより好ましくは９０％未満の純度を有する。あるいは、反応に使用されるハロゲン化カルボン酸は、５０％から９８％まで、より好ましくは５０％から９５％まで、さらにより好ましくは５０％から９０％までの純度を有する。別の好ましい実施態様では、この方法に用いられるハロゲン化カルボン酸は、前の反応工程からの少なくとも１種の生成物、少なくとも１種の試薬、少なくとも１種の溶媒及び／又は少なくとも１種の副生成物も含有する混合物中に含まれる。 A further advantage of the process according to the invention is that high purity halogenated carboxylic acid anhydrides can be produced in high yield even when lower purity reactants, i.e. halogenated carboxylic acids are used. It is. For example, a tailing fraction containing unreacted halogenated carboxylic acid and contaminants from the previous reaction can be used in the process of the present invention. Thus, recycled halogenated carboxylic acids can be used in the process of the present invention. Thus, in a preferred embodiment, the halogenated carboxylic acid used in the reaction has a purity of 98% or less, more preferably less than 95%, even more preferably less than 90%. Alternatively, the halogenated carboxylic acid used in the reaction has a purity of 50% to 98%, more preferably 50% to 95%, even more preferably 50% to 90%. In another preferred embodiment, the halogenated carboxylic acid used in the process comprises at least one product, at least one reagent, at least one solvent and / or at least one by-product from the previous reaction step. It is contained in a mixture that also contains the product.
参照により本明細書に組み込まれる特許、特許出願、及び刊行物のいずれかの開示が用語を不明瞭にさせ得る程度まで本出願の記載と矛盾する場合、本記載が優先するものとする。 In the event that the disclosure of any patent, patent application, and publication incorporated by reference into this specification contradicts the description of this application to the extent that the term may be obscured, this description shall control.
本発明はここで、それを限定することを意図することなく、実施例でさらに説明される。 The invention will now be further described in the examples, without intending to limit it.
トリフルオロ酢酸無水物の生成
１０ｍｍのガラス製ラシヒリングで充填された２．５ｍの充填カラム及び凝縮器を備えた、１１５ｌのセラミックライニングファウドラー撹拌容器に、７０．５ｋｇのトリフルオロ酢酸、続いて、１９．１ｌの６５％発煙硫酸、すなわち、６５ｗｔ％遊離ＳＯ３を有する発煙硫酸を充填した。その後、ファウドラー容器を油浴により１３０℃の温度に加熱した。生成物を７．４ｋｇ／時の速度で蒸留により除去し、ＰＥライニング金属ドラム中に向けて送出した。蒸留の間、反応混合物の温度は、７８℃から９６℃に徐々に変化した。トリフルオロ酢酸無水物の収量は、６４．９ｋｇ（９９％）であった。生成物の純度は、＞９９．９ ％であった。さらに、他の特定されない副生成物と並んで、トリフルオロ酢酸無水物及びトリフロオロ酢酸を含有した７．８ｋｇのテーリング留分を得た。この第２の留分は、その後のバッチの反応混合物に供することができる。
Production of trifluoroacetic anhydride A 115 liter ceramic lined fiddler stirred vessel equipped with a 2.5 m packed column and condenser packed with 10 mm glass Raschig rings was charged with 70.5 kg trifluoroacetic acid, followed by 19.1 l of 65% fuming sulfuric acid, ie fuming sulfuric acid having 65 wt% free SO3, was charged. Thereafter, the Faudler container was heated to a temperature of 130 ° C. with an oil bath. The product was removed by distillation at a rate of 7.4 kg / hr and delivered into a PE-lined metal drum. During the distillation, the temperature of the reaction mixture gradually changed from 78 ° C to 96 ° C. The yield of trifluoroacetic anhydride was 64.9 kg (99%). The purity of the product was> 99.9%. Furthermore, along with other unspecified by-products, a 7.8 kg tailing fraction containing trifluoroacetic anhydride and trifluoroacetic acid was obtained. This second fraction can be subjected to a subsequent batch of reaction mixture.
Claims (15)
ＨａｌＲ２Ｃ（Ｏ）−Ｏ−Ｃ（Ｏ）ＣＲ２Ｈａｌ （Ｉ）
（式中、Ｈａｌは、Ｆ、ＣｌおよびＢｒからなる群から選択され；
Ｒは、Ｈ、Ｆ、Ｃｌ、Ｂｒ、アルキルおよびアリールからなる群から独立して選択される）
の化合物の調製方法であって、
一般構造（ＩＩ）
ＨａｌＲ２Ｃ（Ｏ）−ＯＨ （ＩＩ）
（式中、ＨａｌおよびＲは、上記に定義される）
の化合物を、
硫酸、発煙硫酸及び／又は二硫酸と反応させる工程を含む、方法。 General structure (I)
HalR 2 C (O) —O—C (O) CR 2 Hal (I)
Wherein Hal is selected from the group consisting of F, Cl and Br;
R is independently selected from the group consisting of H, F, Cl, Br, alkyl and aryl)
A method for preparing a compound of
General structure (II)
HalR 2 C (O) -OH ( II)
(Where Hal and R are defined above)
A compound of
A process comprising reacting with sulfuric acid, fuming sulfuric acid and / or disulfuric acid.
ＨａｌＲ２Ｃ（Ｏ）−ＯＨ （ＩＩ）
の化合物が、９８％以下の純度、より好ましくは９５％未満の純度、さらにより好ましくは９０％未満の純度を有する、請求項１から１２のいずれか一項に記載の方法。 The general structure (II) used in the method
HalR 2 C (O) -OH ( II)
13. The method of any one of claims 1 to 12, wherein the compound has a purity of 98% or less, more preferably less than 95%, and even more preferably less than 90%.
ＨａｌＲ２Ｃ（Ｏ）−ＯＨ （ＩＩ）
の化合物が、再生原料である、請求項１から１３のいずれか一項に記載の方法。 The general structure (II) used in the method
HalR 2 C (O) -OH ( II)
The method according to any one of claims 1 to 13, wherein the compound is a regenerated raw material.
ＨａｌＲ２Ｃ（Ｏ）−ＯＨ （ＩＩ）
の化合物が、前の反応工程からの少なくとも１種の生成物、少なくとも１種の試薬、少なくとも１種の溶媒及び／又は少なくとも１種の副生成物も含有する混合物中に含まれる、請求項１から１４のいずれか一項に記載の方法。
General structure (II)
HalR 2 C (O) -OH ( II)
The compound of claim 1 is included in a mixture that also contains at least one product from the previous reaction step, at least one reagent, at least one solvent and / or at least one by-product. The method according to any one of 1 to 14.
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| US3678081A (en) | 1969-10-23 | 1972-07-18 | Gen Electric | Oxidation of hydroxylated aromatic compositions |
| DE2124173A1 (en) * | 1971-05-15 | 1972-11-30 | Farbwerke Hoechst AG, vormals Mei ster Lucius & Bruning, 6000 Frankfurt | 4 Carboxy 2 sulfobenzoesaure anhydnd and process for its Her position |
| CN101108797B (en) * | 2007-08-03 | 2010-04-14 | 申厚宝 | Technique of manufacturing trifluoro acetic anhydride |
| CN102675080B (en) * | 2012-05-28 | 2014-06-04 | 南京爱可德夫科技开发有限公司 | Preparation method of low-carbon chain symmetric anhydride |
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