JP2006225296A - Method for producing trans-1,1,2,2,3,4-hexafluorocyclobutane - Google Patents

Method for producing trans-1,1,2,2,3,4-hexafluorocyclobutane Download PDF

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JP2006225296A
JP2006225296A JP2005039382A JP2005039382A JP2006225296A JP 2006225296 A JP2006225296 A JP 2006225296A JP 2005039382 A JP2005039382 A JP 2005039382A JP 2005039382 A JP2005039382 A JP 2005039382A JP 2006225296 A JP2006225296 A JP 2006225296A
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hexafluorocyclobutane
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tetrafluorocyclobutene
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JP4691702B2 (en
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Junji Mizukado
潤治 水門
Masanori Tamura
正則 田村
Akira Sekiya
章 関屋
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National Institute of Advanced Industrial Science and Technology AIST
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing trans-1,1,2,2,3,4-hexafluorocyclobutane in good efficiency by using an inexpensive raw material suitable for mass-production. <P>SOLUTION: The method for producing the trans-1,1,2,2,3,4-hexafluorocyclobutane represented by chemical formula (2) involves fluorinating 3,3,4,4-tetrafluorocyclobutene represented by chemical formula (1) with fluorine gas or a fluoride of a high-valence metal. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、本発明は、冷媒、洗浄剤、発泡剤の他、医薬、農薬、フッ素系高分子等の中間体としても有用な含フッ素化合物の製造方法に関する。   The present invention relates to a method for producing a fluorine-containing compound useful as an intermediate for drugs, agricultural chemicals, fluoropolymers, etc., in addition to refrigerants, cleaning agents, and foaming agents.

含フッ素化合物は高分子材料、冷媒、洗浄剤、発泡剤、医薬、農薬等、工業的に幅広く用いられている。特に、炭素、フッ素、水素原子から構成されるハイドロフルオロカーボン（HFC）はフロン代替物質として、冷媒、発泡剤、洗浄剤等の用途が非常に期待されている。本発明で対象とするトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンは、冷媒としての用途が期待されている（特許文献１）。
トランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの製造法として、1,2-ジクロロ-ヘキサフルオロシクロブタンの還元反応とトリフルオロエチレンの2量化反応の２つの方法が知られている。
前者の方法は還元剤として水素化リチウムアルミニウム、トリブチルスズヒドリドを用いるが、いずれの還元剤も反応性が非常に高いことから大量生産に適さず、これらの反応によるトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの収率も40%程度と低いことが知られている。（非特許文献１、非特許文献２）
従来のトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの製造方法は、次の化学式で示されている（非特許文献１）。
しかし、LiAlH4が工業生産に不向き。収率、選択性も低い。
さらに、
しかし、Bu3SnHが工業生産に不向きで、毒性があるという問題点が残されているうえ、収率、選択性も低い。
さらに、
という方法においてもトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの収率は10%以下と非常に低い（非特許文献１）。 Fluorine-containing compounds are widely used industrially for polymer materials, refrigerants, cleaning agents, foaming agents, pharmaceuticals, agricultural chemicals and the like. In particular, hydrofluorocarbons (HFCs) composed of carbon, fluorine, and hydrogen atoms are expected to be used as refrigerants, foaming agents, cleaning agents, etc. as substitutes for fluorocarbons. The trans-1,1,2,2,3,4-hexafluorocyclobutane targeted in the present invention is expected to be used as a refrigerant (Patent Document 1).
There are two known methods for producing trans-1,1,2,2,3,4-hexafluorocyclobutane: 1,2-dichloro-hexafluorocyclobutane reduction and trifluoroethylene dimerization. Yes.
The former method uses lithium aluminum hydride and tributyltin hydride as the reducing agent, but none of the reducing agents are suitable for mass production because of their very high reactivity, and trans-1,1,2,2 due to these reactions. The yield of 3,4-hexafluorocyclobutane is known to be as low as about 40%. (Non-patent document 1, Non-patent document 2)
A conventional method for producing trans-1,1,2,2,3,4-hexafluorocyclobutane is represented by the following chemical formula (Non-patent Document 1).
However, LiAlH 4 is not suitable for industrial production. Yield and selectivity are also low.
further,
However, Bu 3 SnH is unsuitable for industrial production and has the problem that it is toxic, and the yield and selectivity are low.
further,
Even in this method, the yield of trans-1,1,2,2,3,4-hexafluorocyclobutane is as low as 10% or less (Non-patent Document 1).

特開平０５−７８６５２号公報JP 05-78652 A J. Chem. Soc., 3198 (1961)J. Chem. Soc., 3198 (1961) J. Fluorine Chem., 71, 59 (1995)J. Fluorine Chem., 71, 59 (1995)

本発明は、上記のような従来技術の問題点を克服するためになされたものであって、大量生産に適した安価な原料を用いて、効率良くトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンを製造する方法を提供する。   The present invention has been made to overcome the above-described problems of the prior art, and efficiently uses transformer-1,1,2,2,3 using inexpensive raw materials suitable for mass production. A method for producing 4-hexafluorocyclobutane is provided.

本発明者は前記課題を解決すべく鋭意研究を重ねた結果、3,3,4,4-テトラフルオロシクロブテンとフッ素又は高原子価金属フッ化物との反応により、効率良くトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンが得られることを見出し、本発明を完成するに至った。
すなわち、本発明は、
下記化学式（１）
で表わされる3,3,4,4-テトラフルオロシクロブテンを、フッ素ガス又は高原子価金属フッ化物でフッ素化することを特徴とする下記化学式（２）
で表わされるトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの製造方法である。
また、本発明のトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの製造方法では、高原子価金属フッ化物としてCoF3、MnF3 から選ばれる化合物を用い、その使用量は3,3,4,4-テトラフルオロシクロブテンに対して０．１〜１０当量であることが好ましい。 As a result of intensive studies to solve the above problems, the present inventor has efficiently obtained trans-1,1 by the reaction of 3,3,4,4-tetrafluorocyclobutene and fluorine or a high-valent metal fluoride. , 2,2,3,4-hexafluorocyclobutane was found, and the present invention was completed.
That is, the present invention
The following chemical formula (1)
3,3,4,4-tetrafluorocyclobutene represented by the following formula (2), characterized by fluorinating with fluorine gas or high-valent metal fluoride
Is a process for producing trans-1,1,2,2,3,4-hexafluorocyclobutane represented by the formula:
In the method for producing trans-1,1,2,2,3,4-hexafluorocyclobutane of the present invention, a compound selected from CoF 3 and MnF 3 is used as the high-valent metal fluoride, and the amount used is The amount is preferably 0.1 to 10 equivalents relative to 3,3,4,4-tetrafluorocyclobutene.

本発明のプロセスによるトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタン製造方法の長所として考えられる点は以下の通りである。
１）CoF3、MnF3は、従来の合成ルートのLiAlH4やBu3SnHと比較して工業生産向き。
２）従来法より、原料コストの面で有利である。
３）プロセストータルで考えて、目的物の収率が報告例より高い。 The possible advantages of the method for producing trans-1,1,2,2,3,4-hexafluorocyclobutane by the process of the present invention are as follows.
1) CoF 3 and MnF 3 are more suitable for industrial production than the conventional synthetic routes LiAlH 4 and Bu 3 SnH.
2) It is more advantageous in terms of raw material costs than the conventional method.
3) Considering the total process, the yield of the target product is higher than reported examples.

本発明で使用する高原子価金属フッ化物として、３フッ化コバルト、２フッ化銀から選ばれる化合物などを挙げることができるが、本発明者らが実施した結果、特に3フッ化コバルト、3フッ化マンガンが好適であることを見出している。その使用量は通常、3,3,4,4-テトラフルオロシクロブテンに対して０．１〜１０当量、好ましくは、１〜５当量である。
反応温度は、使用する高原子価金属フッ化物の種類により異なるが、あまり低すぎる場合は反応速度が遅くなり、あまり高すぎる場合はトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの選択性が低下するため、通常０℃〜５００℃、好ましくは３０℃〜３００℃、更に好ましくは５０℃〜２００℃の範囲とするのがよい。 Examples of the high-valent metal fluoride used in the present invention include compounds selected from cobalt trifluoride and silver fluoride. As a result of the present inventors' implementation, cobalt trifluoride, 3 We have found that manganese fluoride is preferred. The amount used is usually 0.1 to 10 equivalents, preferably 1 to 5 equivalents, relative to 3,3,4,4-tetrafluorocyclobutene.
The reaction temperature depends on the type of high-valent metal fluoride used, but if it is too low, the reaction rate will be slow, and if it is too high, trans-1,1,2,2,3,4-hexafluoro Since the selectivity of cyclobutane is lowered, the temperature is usually 0 ° C to 500 ° C, preferably 30 ° C to 300 ° C, more preferably 50 ° C to 200 ° C.

反応時間は、反応温度等により異なるが、通常０．０１〜５００時間、好ましくは０．１〜５０時間の範囲である。
本反応は、溶媒を使用することなく実施することができるが、溶媒を用いて実施することも可能である。しかし、高原子価金属フッ化物は溶媒中の炭素−水素結合の水素をフッ素化する能力があるため、反応生成物の精製、高原子価金属フッ化物の使用量の増加等を考慮すると溶媒を使用しない方が好ましい。
また、本発明の反応はバッチ式に限らず、フロー式でも行うことができる。 Although reaction time changes with reaction temperature etc., it is 0.01 to 500 hours normally, Preferably it is the range of 0.1 to 50 hours.
This reaction can be carried out without using a solvent, but can also be carried out using a solvent. However, since high-valent metal fluoride has the ability to fluorinate hydrogen of carbon-hydrogen bonds in the solvent, considering the purification of reaction products, the increase in the amount of high-valent metal fluoride used, etc. It is preferable not to use it.
In addition, the reaction of the present invention is not limited to a batch method, and can be performed by a flow method.

内容量50 mlのステンレス製圧力反応器を乾燥させた後、3フッ化マンガン1.12ｇを秤量した。反応容器を液体窒素で冷やしながら系内を脱気した後、真空ラインを用いて3,3,4,4-テトラフルオロシクロブテン126mgを導入した。反応器を100℃に保ち24時間攪拌した。反応により得られた粗生成物を真空ラインにより精製し、1H-NMR、19F-NMRで分析した結果、反応により目的とするトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタン92 mg (収率56%)を得ることができた。 After drying a stainless steel pressure reactor having an internal volume of 50 ml, 1.12 g of manganese trifluoride was weighed. The system was deaerated while cooling the reaction vessel with liquid nitrogen, and then 126 mg of 3,3,4,4-tetrafluorocyclobutene was introduced using a vacuum line. The reactor was kept at 100 ° C. and stirred for 24 hours. The crude product obtained by the reaction was purified by a vacuum line and analyzed by 1 H-NMR and 19 F-NMR. As a result, the target trans-1,1,2,2,3,4-hexafluoro was determined by the reaction. It was possible to obtain 92 mg of cyclobutane (yield 56%).

実施例１と同様に、3フッ化マンガンと3,3,4,4-テトラフルオロシクロブテンの反応を150℃、1時間行った。実施例１と同様に分析を行った結果、反応により目的とするトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタン97 mg (収率59%)を得ることができた。   In the same manner as in Example 1, the reaction of manganese trifluoride and 3,3,4,4-tetrafluorocyclobutene was carried out at 150 ° C. for 1 hour. As a result of analyzing in the same manner as in Example 1, 97 mg (yield 59%) of the desired trans-1,1,2,2,3,4-hexafluorocyclobutane could be obtained by the reaction.

3フッ化マンガンの代わりに3フッ化コバルト1.16ｇを用い、実施例１と同様に3,3,4,4-テトラフルオロシクロブテンとの反応を100℃、24時間行った。実施例１と同様に分析を行った結果、反応により目的とするトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタン90 mg (収率55%)を得ることができた。   Using 1.16 g of cobalt trifluoride instead of manganese trifluoride, the reaction with 3,3,4,4-tetrafluorocyclobutene was carried out at 100 ° C. for 24 hours in the same manner as in Example 1. As a result of analysis in the same manner as in Example 1, 90 mg (yield 55%) of the desired trans-1,1,2,2,3,4-hexafluorocyclobutane could be obtained by the reaction.

実施例３と同様に３フッ化コバルトと3,3,4,4-テトラフルオロシクロブテンの反応を150℃、1時間行った。実施例１と同様に分析を行った結果、反応により目的とするトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタン87mg (収率53%)を得ることができた。   As in Example 3, the reaction of cobalt trifluoride and 3,3,4,4-tetrafluorocyclobutene was carried out at 150 ° C. for 1 hour. As a result of analysis in the same manner as in Example 1, 87 mg (yield 53%) of the desired trans-1,1,2,2,3,4-hexafluorocyclobutane could be obtained by the reaction.

本発明の反応式は、次式で示され、3,3,4,4-テトラフルオロシクロブテン１をフッ素化して目的生成物のトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタン２を得る。
The reaction formula of the present invention is represented by the following formula, and 3,3,4,4-tetrafluorocyclobutene 1 is fluorinated to give the desired product, trans-1,1,2,2,3,4-hexafluoro Cyclobutane 2 is obtained.

比較例１
3フッ化マンガンの代わりに２フッ化銀1.46ｇを用い、実施例１と同様に3,3,4,4-テトラフルオロシクロブテンとの反応を100℃、１時間行った。実施例１と同様に分析を行った結果、3,3,4,4-テトラフルオロシクロブテンは検出されず、目的とするトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタン13mg (収率8%)を得た。
比較例２
3フッ化マンガンの代わりに4フッ化カリウムコバルト1.74ｇを用い、実施例１と同様に3,3,4,4-テトラフルオロシクロブテンとの反応を250℃、１時間行った。実施例１と同様に分析を行った結果、3,3,4,4-テトラフルオロシクロブテン 83 mg (66%)を回収したものの、目的とするトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンを得ることは出来なかった。

比較例３
3フッ化マンガンの代わりに4フッ化セリウム2.16ｇを用い、実施例１と同様に3,3,4,4-テトラフルオロシクロブテンとの反応を250℃、１時間行った。実施例１と同様に分析を行った結果、3,3,4,4-テトラフルオロシクロブテン 112mg (89%)を回収したものの、目的とするトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンを得ることは出来なかった。 Comparative Example 1
1.46 g of silver difluoride was used instead of manganese trifluoride, and the reaction with 3,3,4,4-tetrafluorocyclobutene was carried out at 100 ° C. for 1 hour in the same manner as in Example 1. As a result of analysis in the same manner as in Example 1, 3,3,4,4-tetrafluorocyclobutene was not detected, and the desired trans-1,1,2,2,3,4-hexafluorocyclobutane was 13 mg. (Yield 8%) was obtained.
Comparative Example 2
Using 1.74 g of potassium cobalt tetrafluoride instead of manganese trifluoride, the reaction with 3,3,4,4-tetrafluorocyclobutene was carried out at 250 ° C. for 1 hour in the same manner as in Example 1. As a result of analyzing in the same manner as in Example 1, 83 mg (66%) of 3,3,4,4-tetrafluorocyclobutene was recovered, but the desired trans-1,1,2,2,3, 4-Hexafluorocyclobutane could not be obtained.

Comparative Example 3
Using 2.16 g of cerium tetrafluoride instead of manganese trifluoride, the reaction with 3,3,4,4-tetrafluorocyclobutene was carried out at 250 ° C. for 1 hour in the same manner as in Example 1. As a result of analysis in the same manner as in Example 1, 112 mg (89%) of 3,3,4,4-tetrafluorocyclobutene was recovered, but the desired trans-1,1,2,2,3,4 -Hexafluorocyclobutane could not be obtained.

行ったトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの製造の具体例の全てを、実施例、比較例を含めて表１に示す。
All the specific examples of the production of trans-1,1,2,2,3,4-hexafluorocyclobutane performed are shown in Table 1, including Examples and Comparative Examples.

本発明によれば、前記化学式（１）で表される3,3,4,4-テトラフルオロシクロブテンと高原子価金属フッ化物を反応させることを特徴とする前記化学式（２）で表されるトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンを効率よく得ることができ、冷媒、洗浄剤、発泡剤の他、医薬、農薬、フッ素系高分子等の中間体としても有用な含フッ素化合物を安価に提供することが出来る。
According to the present invention, 3,3,4,4-tetrafluorocyclobutene represented by the chemical formula (1) is reacted with a high-valent metal fluoride. Trans-1,1,2,2,3,4-hexafluorocyclobutane can be efficiently obtained, and it can be used as an intermediate for pharmaceuticals, agricultural chemicals, fluoropolymers, in addition to refrigerants, detergents and foaming agents. Useful fluorine-containing compounds can be provided at low cost.

Claims (2)

下記化学式（１）
で表わされる3,3,4,4-テトラフルオロシクロブテンを、フッ素ガス又は高原子価金属フッ化物でフッ素化することを特徴とする下記化学式（２）
で表わされるトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの製造方法。 The following chemical formula (1)
3,3,4,4-tetrafluorocyclobutene represented by the following formula (2), characterized by fluorinating with fluorine gas or high-valent metal fluoride
A process for producing trans-1,1,2,2,3,4-hexafluorocyclobutane represented by the formula: 高原子価金属フッ化物がCoF3 、MnF3
から選ばれる化合物であり、その使用量が3,3,4,4-テトラフルオロシクロブテンに対して０．１〜１０当量である請求項1に記載したトランス-1,1,2,2,3,4-ヘキサフルオロシクロブタンの製造方法。
High-valent metal fluoride is CoF 3 , MnF 3
The trans-1,1,2,2, wherein the amount used is 0.1 to 10 equivalents with respect to 3,3,4,4-tetrafluorocyclobutene. A method for producing 3,4-hexafluorocyclobutane.
JP2005039382A 2005-02-16 2005-02-16 Process for producing trans-1,1,2,2,3,4-hexafluorocyclobutane Expired - Fee Related JP4691702B2 (en)

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JP2007106726A (en) * 2005-10-17 2007-04-26 National Institute Of Advanced Industrial & Technology Method for producing 1,1,2,2,3-pentafluorocyclobutane
JP2008037807A (en) * 2006-08-07 2008-02-21 National Institute Of Advanced Industrial & Technology 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane and method for producing the same
JP2008239552A (en) * 2007-03-28 2008-10-09 National Institute Of Advanced Industrial & Technology Fluorine-containing cyclic compound and method for producing the same
JP2015533029A (en) * 2012-10-30 2015-11-16 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Fluorocarbon molecules for high aspect ratio oxide etching

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JP2003261477A (en) * 1993-08-27 2003-09-16 Daikin Ind Ltd Method for producing (z)-1,2,3,3,4,4-hexafluorocyclobutane

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JP2007106726A (en) * 2005-10-17 2007-04-26 National Institute Of Advanced Industrial & Technology Method for producing 1,1,2,2,3-pentafluorocyclobutane
JP2008037807A (en) * 2006-08-07 2008-02-21 National Institute Of Advanced Industrial & Technology 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane and method for producing the same
JP2008239552A (en) * 2007-03-28 2008-10-09 National Institute Of Advanced Industrial & Technology Fluorine-containing cyclic compound and method for producing the same
JP2015533029A (en) * 2012-10-30 2015-11-16 レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード Fluorocarbon molecules for high aspect ratio oxide etching

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