JP2006063013A - Method for producing perfluoro cyclic ether - Google Patents
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Abstract
【課題】ペルフルオロ環状エーテルを高選択率で高収率に製造する方法を提供する。
【解決手段】Ｒ−ＸとＣＹ１Ｙ２＝ＣＹ３−Ｑ−ＯＨをラジカル発生剤および／または塩基性化合物の存在下に反応させて化合物（２）を得て、つぎに該化合物（２）を液相フッ素化反応させる化合物（１）の製造方法。ただし、Ｒはポリフルオロ１価有機基を、Ｘは塩素原子、臭素原子、またはヨウ素原子を、Ｙ１、Ｙ２、およびＹ３はそれぞれ独立に、水素原子、フッ素原子、または炭素原子に結合した水素原子を必須とする１価有機基を、Ｑは炭素原子に結合した水素原子を必須とする２価有機基を、ＲＦはＲと同一のペルフルオロ化された１価飽和有機基等を、ＹＦ１〜ＹＦ３はＹ１〜Ｙ３と同一またはＹ１〜Ｙ３がペルフルオロ化された基でありフッ素原子等を、ＱＦはＱがペルフルオロ化された２価有機基を、示す。
【化１】
【選択図】なし
A method for producing perfluoro cyclic ether with high selectivity and high yield is provided.
A compound (2) is obtained by reacting R—X and CY 1 Y 2 ═CY 3 —Q—OH in the presence of a radical generator and / or a basic compound, and then the compound (2). ) Is subjected to a liquid phase fluorination reaction. Where R is a polyfluoro monovalent organic group, X is a chlorine atom, bromine atom, or iodine atom, and Y 1 , Y 2 , and Y 3 are each independently bonded to a hydrogen atom, a fluorine atom, or a carbon atom. the monovalent organic group of hydrogen atoms required, Q is a divalent organic radical essentially containing hydrogen atoms bonded to carbon atoms, the R F is such a monovalent saturated organic group perfluorinated identical to R the Y F1 to Y F3 is a group Y 1 to Y 3 are the same as or Y 1 to Y 3 is perfluorinated fluorine atom, Q F is a divalent organic group Q is perfluorinated shows.
[Chemical 1]
[Selection figure] None
Description
本発明は、ペルフルオロ環状エーテルの製造方法に関する。 The present invention relates to a method for producing a perfluoro cyclic ether.
ペルフルオロ環状エーテル（たとえば、３Ｍ社製、商品名ＦＣ−７７）は、半導体用の洗浄剤、熱媒、溶媒等に用いられる有用な化合物である。 Perfluoro cyclic ether (for example, trade name FC-77 manufactured by 3M Co.) is a useful compound used for semiconductor cleaning agents, heating media, solvents, and the like.
ペルフルオロ環状エーテルの製造方法としては、フルオロオレフィンと環状アルコールを遊離基付加反応させて得た環状エーテルを３フッ化コバルトによりフッ素化する方法（特許文献１参照）、オクタン酸やオクタン酸フロリド等の直鎖状のカルボン酸類縁体を電解フッ素化法によりフッ素化する方法（特許文献２参照）、およびフッ素原子を含まない環状エーテルを液相フッ素化法によりフッ素化する方法（特許文献３参照）が知られている。 As a method for producing perfluoro cyclic ether, a method of fluorinating cyclic ether obtained by free radical addition reaction of fluoroolefin and cyclic alcohol with cobalt trifluoride (see Patent Document 1), octanoic acid, octanoic acid fluoride, etc. A method of fluorinating a linear carboxylic acid analog by an electrolytic fluorination method (see Patent Document 2) and a method of fluorinating a cyclic ether containing no fluorine atom by a liquid phase fluorination method (see Patent Document 3) It has been known.
特許文献１に記載の３フッ化コバルトによる方法は、２００℃以上の高温で気固反応を行う必要がある点、および３フッ化コバルトを反応の都度、調製する必要がある点から、工業的なペルフロオロ環状エーテルの製造方法には適さない。 The method using cobalt trifluoride described in Patent Document 1 is industrial because it requires a gas-solid reaction at a high temperature of 200 ° C. or higher, and it is necessary to prepare cobalt trifluoride for each reaction. It is not suitable for a method for producing a perfluorofluorocyclic ether.
特許文献２に記載の電解フッ素化法による方法は、得られる主生成物がペルフルオロカルボン酸フロリドであり、ペルフルオロ環状エーテルは主生成物として得られない。また電解フッ素化法は種々の副反応（たとえば異性化反応、分解反応等の反応。）を伴いペルフルオロ環状エーテルを高選択率に製造する方法には適さない。 In the method based on the electrolytic fluorination method described in Patent Document 2, the main product obtained is perfluorocarboxylic acid fluoride, and the perfluorocyclic ether cannot be obtained as the main product. Moreover, the electrolytic fluorination method involves various side reactions (for example, isomerization reaction, decomposition reaction, etc.) and is not suitable for a method for producing perfluoro cyclic ether with high selectivity.
特許文献３に記載の液相フッ素化による方法は、反応の制御が困難であり対応するペルフルオロ環状エーテルを高選択率に得ることができない。
したがって、任意の構造を有するペルフルオロ環状エーテルの高選択率で工業的な製造方法の開発が求められている。
In the method by liquid phase fluorination described in Patent Document 3, it is difficult to control the reaction, and the corresponding perfluoro cyclic ether cannot be obtained with high selectivity.
Therefore, development of an industrial manufacturing method with high selectivity of perfluoro cyclic ether having an arbitrary structure is required.
本発明は、前記の課題を解決するためになされたものであり、入手容易な化合物から得られる部分フッ素化された特定の環状エーテルを液相フッ素化反応させるペルフルオロ環状エーテルの製造方法の提供を目的とする。 The present invention has been made to solve the above-mentioned problems, and provides a method for producing a perfluorocyclic ether in which a specific partially fluorinated cyclic ether obtained from an easily available compound is subjected to a liquid phase fluorination reaction. Objective.
すなわち、本発明は以下の発明を提供する。
＜１＞下式（４）で表される化合物と下式（３）で表される化合物をラジカル発生剤および／または塩基性化合物の存在下に反応させて下式（２）で表される化合物を得て、つぎに該化合物を液相フッ素化反応させる下式（１）で表されるペルフルオロ環状エーテルの製造方法。
Ｒ−Ｘ （４）
ＣＹ１Ｙ２＝ＣＹ３−Ｑ−ＯＨ （３）
That is, the present invention provides the following inventions.
<1> A compound represented by the following formula (4) and a compound represented by the following formula (3) are reacted in the presence of a radical generator and / or a basic compound and represented by the following formula (2). A method for producing a perfluorocyclic ether represented by the following formula (1), wherein a compound is obtained and then the compound is subjected to a liquid phase fluorination reaction.
R-X (4)
CY 1 Y 2 = CY 3 -Q -OH (3)
ただし、式中の記号は以下の意味を示す。
Ｒは、ポリフルオロ１価有機基を示す。
Ｘは、塩素原子、臭素原子、またはヨウ素原子を示す。
Ｙ１、Ｙ２、およびＹ３は、それぞれ独立に、水素原子、フッ素原子、または炭素原子に結合した水素原子を必須とする１価有機基を示す。
Ｑは、炭素原子に結合した水素原子を必須とする２価有機基を示す。
ＲＦは、Ｒがフッ素化される基である場合はＲがペルフルオロ化された１価飽和有機基を、Ｒがペルフルオロ化された１価飽和有機基である場合はＲと同一の基を、示す。
ＹＦ１はＹ１に、ＹＦ２はＹ２に、ＹＦ３はＹ３に、それぞれ対応する基であり、Ｙ１〜Ｙ３が水素原子である場合のＹＦ１〜ＹＦ３はフッ素原子を、Ｙ１〜Ｙ３がフッ素原子である場合のＹＦ１〜ＹＦ３はフッ素原子を、Ｙ１〜Ｙ３が炭素原子に結合した水素原子を必須とする１価有機基である場合のＹＦ１〜ＹＦ３はペルフルオロ化された１価飽和有機基を、示す。
ＱＦは、Ｑがペルフルオロ化された２価飽和有機基を示す。
However, the symbols in the formulas have the following meanings.
R represents a polyfluoro monovalent organic group.
X represents a chlorine atom, a bromine atom, or an iodine atom.
Y 1 , Y 2 , and Y 3 each independently represent a monovalent organic group essentially comprising a hydrogen atom, a fluorine atom, or a hydrogen atom bonded to a carbon atom.
Q represents a divalent organic group in which a hydrogen atom bonded to a carbon atom is essential.
R F represents a monovalent saturated organic group in which R is a perfluorinated group when R is a group to be fluorinated, and the same group as R when R is a monovalent saturated organic group in which R is a perfluorinated group. Show.
Y F1 is a group corresponding to Y 1 , Y F2 is a group corresponding to Y 2 , Y F3 is a group corresponding to Y 3 , and when Y 1 to Y 3 are hydrogen atoms, Y F1 to Y F3 are fluorine atoms, Y F1 to Y when Y 1 to Y 3 is a fluorine atom F3 is a fluorine atom, Y 1 to Y 3 is Y F1 ~ if a monovalent organic radical containing, as essential hydrogen atoms bonded to carbon atoms Y F3 represents a perfluorinated monovalent saturated organic group.
Q F represents a divalent saturated organic group in which Q is perfluorinated.
＜２＞下式（４）で表される化合物と下式（３−１１）で表される化合物をラジカル発生剤および／または塩基性化合物の存在下に反応させて下式（２−１１）で表される化合物を得て、つぎに該化合物を液相フッ素化反応させる下式（１−１１）で表される化合物の製造方法（ただし、式中の記号は前記と同じ意味を示す。）。
Ｒ−Ｘ （４）
ＣＨ２＝ＣＨ（ＣＨ２）３ＯＨ （３−１１）
<2> A compound represented by the following formula (4) and a compound represented by the following formula (3-11) are reacted in the presence of a radical generator and / or a basic compound to formula (2-11) And then producing the compound represented by the following formula (1-11) in which the compound is subjected to a liquid phase fluorination reaction (wherein the symbols in the formula have the same meanings as described above). ).
R-X (4)
CH 2 = CH (CH 2) 3 OH (3-11)
＜３＞下式（４）で表される化合物と下式（３−１２）で表される化合物をラジカル発生剤および／または塩基性化合物の存在下に反応させて下式（２−１２）で表される化合物を得て、つぎに該化合物を液相フッ素化反応させる下式（１−１２）で表される化合物の製造方法（ただし、式中の記号は前記と同じ意味を示す。）。
Ｒ−Ｘ （４）
ＣＨ２＝ＣＨ（ＣＨ２）４ＯＨ （３−１２）
<3> A compound represented by the following formula (4) and a compound represented by the following formula (3-12) are reacted in the presence of a radical generator and / or a basic compound to formula (2-12) And then producing the compound represented by the following formula (1-12) in which the compound is subjected to a liquid phase fluorination reaction (wherein the symbols in the formula have the same meanings as described above). ).
R-X (4)
CH 2 = CH (CH 2) 4 OH (3-12)
本発明の製造方法によれば、入手容易な化合物から高選択率でペルフルオロ環状エーテルを製造できる。 According to the production method of the present invention, a perfluoro cyclic ether can be produced from an easily available compound with high selectivity.
本明細書において、式（１）で表される化合物を化合物（１）と記す。他の式で表される化合物も同様に記す。 In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
本発明において、「有機基」とは炭素原子を１つ以上含む基をいい、該基中に炭素−炭素結合が存在する場合、該結合は単結合であっても不飽和結合であってもよい。「飽和有機基」とは炭素−炭素結合が単結合のみからなる有機基をいう。
「ポリフルオロ化された有機基」とは、炭素原子に結合したフッ素原子を必須とする有機基をいう。
「ペルフルオロ化された飽和有機基」とは、炭素原子に結合した水素原子がフッ素原子で置換され、かつ炭素−炭素不飽和結合の実質的に全てにフッ素原子が付加した基、すなわち炭素原子に結合した水素原子を含まず、かつ炭素−炭素不飽和結合を含まない有機基をいう。
In the present invention, the “organic group” means a group containing one or more carbon atoms. When a carbon-carbon bond is present in the group, the bond may be a single bond or an unsaturated bond. Good. A “saturated organic group” refers to an organic group in which the carbon-carbon bond consists only of a single bond.
“Polyfluorinated organic group” refers to an organic group essentially comprising a fluorine atom bonded to a carbon atom.
A “perfluorinated saturated organic group” is a group in which a hydrogen atom bonded to a carbon atom is replaced with a fluorine atom, and a fluorine atom is added to substantially all of the carbon-carbon unsaturated bonds, ie, a carbon atom. An organic group that does not contain a bonded hydrogen atom and does not contain a carbon-carbon unsaturated bond.
まず本発明における化合物（４）、化合物（３）、化合物（２）、および化合物（１）の好ましい態様を説明する。
Ｒは、フッ素化される基であっても、フッ素化されない基であってもよく、後者の基が好ましい。
Ｒがフッ素化される基である場合、炭素原子に結合した水素原子（以下、Ｃ−Ｈと記す。）および／または炭素−炭素不飽和結合を有するポリフルオロ１価有機基が好ましい。フッ素化される基としては、アルキル基、シクロアルキル基、およびシクロアルキルアルキル基から選ばれる基、ならびに該選ばれる基の炭素−炭素結合間にエーテル性酸素原子の１個以上が挿入された基におけるＣ−Ｈの一部がフッ素化された基であるのが好ましい。
First, preferred embodiments of the compound (4), the compound (3), the compound (2), and the compound (1) in the present invention will be described.
R may be a fluorinated group or a non-fluorinated group, and the latter group is preferred.
When R is a group to be fluorinated, a polyfluoro monovalent organic group having a hydrogen atom bonded to a carbon atom (hereinafter referred to as C—H) and / or a carbon-carbon unsaturated bond is preferable. Examples of the group to be fluorinated include a group selected from an alkyl group, a cycloalkyl group, and a cycloalkylalkyl group, and a group in which one or more etheric oxygen atoms are inserted between carbon-carbon bonds of the selected group. It is preferable that a part of C—H in is a fluorinated group.
Ｒがフッ素化されない基である場合には、ペルフルオロ１価飽和有機基が好ましく、ペルフルオロアルキル基、ペルフルオロシクロアルキル基、およびペルフルオロ（シクロアルキルアルキル）基から選ばれる基、ならびに該選ばれる基の炭素−炭素結合間にエーテル性酸素原子の１個以上が挿入された基が特に好ましい。
またＲの炭素数は、１〜１０が好ましく、３〜８が特に好ましい。Ｒの構造は、直鎖状、分岐状、および環状が挙げられる。
When R is a non-fluorinated group, a perfluoromonovalent saturated organic group is preferred, a group selected from a perfluoroalkyl group, a perfluorocycloalkyl group, and a perfluoro (cycloalkylalkyl) group, and a carbon of the selected group A group in which one or more etheric oxygen atoms are inserted between carbon bonds is particularly preferred.
Moreover, 1-10 are preferable and, as for carbon number of R, 3-8 are especially preferable. Examples of the structure of R include linear, branched, and cyclic.
Ｒがフッ素化されない基である場合の例としては、つぎの基が挙げられる。
直鎖状のペルフルオロアルキル基であるＲの例。
ＣＦ３−、ＣＦ３ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２−。
Examples of the case where R is a group that is not fluorinated include the following groups.
An example of R which is a linear perfluoroalkyl group.
CF 3 -, CF 3 CF 2 -, CF 3 CF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 -.
分岐状のペルフルオロアルキル基であるＲの例。
（ＣＦ３）２ＣＦ−、（ＣＦ３）２ＣＦＣＦ２−、（ＣＦ３）２ＣＦＣＦ２ＣＦ２−、（ＣＦ３）２ＣＦＣＦ（ＣＦ３）−、（ＣＦ３）２ＣＦＣＦ（ＣＦ３）ＣＦ２−、（ＣＦ３）２ＣＦＣＦ２ＣＦ（ＣＦ３）−、ＣＦ３ＣＦ２ＣＦ（ＣＦ３）−、ＣＦ３ＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ（ＣＦ２ＣＦ３）−、（ＣＦ３）３Ｃ−、（ＣＦ３）３ＣＣＦ２−、（ＣＦ３）２Ｃ（ＣＦ２ＣＦ３）−、ＣＦ３Ｃ（ＣＦ２ＣＦ３）２−。
An example of R which is a branched perfluoroalkyl group.
(CF 3 ) 2 CF-, (CF 3 ) 2 CFCF 2- , (CF 3 ) 2 CFCF 2 CF 2- , (CF 3 ) 2 CFCF (CF 3 )-, (CF 3 ) 2 CFCF (CF 3 ) CF 2- , (CF 3 ) 2 CFCF 2 CF (CF 3 )-, CF 3 CF 2 CF (CF 3 )-, CF 3 CF 2 CF (CF 3 ) CF 2 CF 2- , CF 3 CF 2 CF ( CF 2 CF 3) -, ( CF 3) 3 C -, (CF 3) 3 CCF 2 -, (CF 3) 2 C (CF 2 CF 3) -, CF 3 C (CF 2 CF 3) 2 -.
ペルフルオロシクロアルキル基またはペルフルオロ（シクロアルキルアルキル）基であるＲの例。 An example of R which is a perfluorocycloalkyl group or a perfluoro (cycloalkylalkyl) group.
直鎖状のエーテル性酸素原子を含むペルフルオロアルキル基であるＲの例。
ＣＦ３ＯＣＦ２−、ＣＦ３ＣＦ２ＯＣＦ２−、ＣＦ３ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２−。
An example of R which is a perfluoroalkyl group containing a linear etheric oxygen atom.
CF 3 OCF 2 -, CF 3 CF 2 OCF 2 -, CF 3 OCF 2 CF 2 -, CF 3 CF 2 OCF 2 CF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2- , CF 3 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2- , CF 3 CF 2 CF 2 OCF 2- , CF 3 CF 2 CF 2 CF 2 OCF 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 OCF 2 -, CF 3 CF 2 CF 2 OCF CF 2 -, CF 3 CF 2 CF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 OCF 2 CF 2 OCF 2 -, CF 3 CF 2 CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 OCF 2 -, CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2- , CF 3 CF 2 CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2- , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2- , CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 -.
分岐状のエーテル性酸素原子を含むペルフルオロアルキル基であるＲの例。
ＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）−、ＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２−、ＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）−、ＣＦ３ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２−。
An example of R which is a perfluoroalkyl group containing a branched etheric oxygen atom.
CF 3 CF 2 CF 2 OCF ( CF 3) -, CF 3 CF 2 CF 2 OCF (CF 3) CF 2 -, CF 3 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 -, CF 3 CF 2 CF 2 OCF (CF 3) CF 2 OCF (CF 3) -, CF 3 CF 2 CF 2 OCF (CF 3) CF 2 OCF (CF 3) CF 2 -.
エーテル性酸素原子を含むペルフルオロシクロアルキル基またはエーテル性酸素原子を含むペルフルオロ（シクロアルキルアルキル）基であるＲの例。 An example of R which is a perfluorocycloalkyl group containing an etheric oxygen atom or a perfluoro (cycloalkylalkyl) group containing an etheric oxygen atom.
Ｒがフッ素化される基である場合の例としては、前記Ｒの具体例において、フッ素原子の１個以上を水素原子に置換した基が挙げられる。 Examples of the group in which R is a group to be fluorinated include a group in which one or more fluorine atoms in the specific example of R are substituted with hydrogen atoms.
Ｘは、臭素原子またはヨウ素原子が好ましく、ヨウ素原子が特に好ましい。 X is preferably a bromine atom or an iodine atom, particularly preferably an iodine atom.
Ｙ１、Ｙ２、およびＹ３は、水素原子が好ましい。Ｙ１〜Ｙ３がＣ−Ｈを必須とする１価有機基である場合、Ｙ１〜Ｙ３はアルキル基が好ましく、炭素数１〜６のアルキル基が特に好ましく、メチル基またはエチル基がとりわけ好ましい。 Y 1 , Y 2 , and Y 3 are preferably hydrogen atoms. When Y 1 to Y 3 is a monovalent organic group essentially comprising C—H, Y 1 to Y 3 is preferably an alkyl group, particularly preferably an alkyl group having 1 to 6 carbon atoms, and a methyl group or an ethyl group being Especially preferred.
Ｑは、アルキレン基または炭素−炭素結合間にエーテル性酸素原子が挿入されたアルキレン基が好ましく、アルキレン基が特に好ましく、炭素数２〜８のアルキレン基がとりわけ好ましい。Ｑの構造は、直鎖状、分岐状、および環状が挙げられ、直鎖状が好ましい。 Q is preferably an alkylene group or an alkylene group having an etheric oxygen atom inserted between carbon-carbon bonds, particularly preferably an alkylene group, and particularly preferably an alkylene group having 2 to 8 carbon atoms. Examples of the structure of Q include linear, branched and cyclic structures, and a linear structure is preferable.
ＲＦは、Ｒがペルフルオロ化された基、またはＲと同一の基であるペルフルオロ化された１価飽和有機基であり、後者の基が好ましい。ＲＦがペルフルオロ化された１価飽和有機基である場合のＲとＲＦは同一の基であり、ＲＦの具体例としてはＲがフッ素化されない基である場合の例と同じである。またＲＦの炭素数は、１〜１０が好ましく、３〜８が特に好ましい。ＲＦの構造は、直鎖状、分岐状、環状が挙げられる。 R F is a perfluorinated monovalent saturated organic group in which R is a perfluorinated group or the same group as R, and the latter group is preferred. R and R F where R F is a monovalent saturated organic group perfluorinated are the same group, as specific examples of R F is the same as example of a group R is not fluorinated. The number of carbon atoms in R F is 1 to 10 preferably 3 to 8 is particularly preferred. Examples of the structure of R F include linear, branched, and cyclic.
ＱＦは、Ｑがペルフルオロ化された基であり、ペルフルオロアルキレン基または炭素−炭素結合間にエーテル性酸素原子が挿入されたペルフルオロアルキレン基が好ましく、ペルフルオロアルキレン基が特に好ましく、炭素数２〜８のペルフルオロアルキレン基がとりわけ好ましい。ＱＦの構造は、直鎖状、分岐状、および環状が挙げられ、直鎖状が好ましい。 Q F is a group in which Q is perfluorinated, and is preferably a perfluoroalkylene group or a perfluoroalkylene group having an etheric oxygen atom inserted between carbon-carbon bonds, more preferably a perfluoroalkylene group, and 2 to 8 carbon atoms. Especially preferred are perfluoroalkylene groups. Structure of Q F is a linear, branched, and cyclic and the like, and is preferably linear.
化合物（４）としては、Ｒが炭素数３〜８のペルフルオロアルキル基であり、Ｘがヨウ素原子である化合物が好ましい。 As the compound (4), a compound in which R is a C 3-8 perfluoroalkyl group and X is an iodine atom is preferable.
化合物（３）としては、下記化合物（３−１）が好ましく、下記化合物（３−１１）および下記化合物（３−１２）が特に好ましい。ただし、ｎは２〜８の整数を示す。
ＣＨ２＝ＣＨ（ＣＨ２）ｎＯＨ （３−１）
ＣＨ２＝ＣＨ（ＣＨ２）３ＯＨ （３−１１）
ＣＨ２＝ＣＨ（ＣＨ２）４ＯＨ （３−１２）。
As the compound (3), the following compound (3-1) is preferable, and the following compound (3-11) and the following compound (3-12) are particularly preferable. However, n shows the integer of 2-8.
CH 2 = CH (CH 2) n OH (3-1)
CH 2 = CH (CH 2) 3 OH (3-11)
CH 2 = CH (CH 2) 4 OH (3-12).
化合物（２）としては、下記化合物（２−１）が好ましく、下記化合物（２−１１）および下記化合物（２−１２）が特に好ましい。ただし、Ｒおよびｎは、前記と同じ意味を示す。 As the compound (2), the following compound (2-1) is preferable, and the following compound (2-11) and the following compound (2-12) are particularly preferable. However, R and n have the same meaning as described above.
化合物（１）としては、下記化合物（１−１）が好ましく、下記化合物（１−１１）および下記化合物（１−１２）が特に好ましい。ただし、ＲＦおよびｎは、前記と同じ意味を示す。 As the compound (1), the following compound (1-1) is preferable, and the following compound (1-11) and the following compound (1-12) are particularly preferable. However, R F and n have the same meaning as described above.
つぎに、本発明の製造方法における各反応を説明する。
化合物（４）と化合物（３）の反応は、Ｊｏｕｒｎａｌ ｏｆ Ｆｌｕｏｒｉｎｅ Ｃｈｅｍｉｓｔｒｙ，５６（１９９２），２８５〜２９３に記載の方法にしたがって実施するのが好ましい。
Next, each reaction in the production method of the present invention will be described.
The reaction between the compound (4) and the compound (3) is preferably carried out according to the method described in Journal of Fluorine Chemistry, 56 (1992), 285-293.
反応は、ラジカル発生剤および塩基性化合物の存在下に行うのが好ましい。
ラジカル発生剤は化合物（４）に対して、０．００５〜０．０５倍モルを用いるのが好ましい。ラジカル発生剤としては、ジイソプロピルパーオキシジカーボネート、ベンゾイルパーオキシド等の有機過酸化物、およびアゾビスイソブチロニトリル等の有機アゾ化合物が好ましい。
塩基性化合物は化合物（４）に対して、０．２〜０．６倍モルを用いるのが好ましい。塩基性化合物としては、トリエチルアミン、ピリジン、２，６−ジメチルピリジン等の液状の塩基性化合物、および炭酸カリウム等の固体状の塩基性化合物が好ましい。
The reaction is preferably performed in the presence of a radical generator and a basic compound.
The radical generator is preferably used in an amount of 0.005 to 0.05 moles compared to the compound (4). As the radical generator, organic peroxides such as diisopropyl peroxydicarbonate and benzoyl peroxide, and organic azo compounds such as azobisisobutyronitrile are preferable.
The basic compound is preferably used in an amount of 0.2 to 0.6 moles compared to the compound (4). The basic compound is preferably a liquid basic compound such as triethylamine, pyridine, or 2,6-dimethylpyridine, and a solid basic compound such as potassium carbonate.
化合物（３）は化合物（４）に対して、１〜１０倍モルを用いるのが好ましく、反応収率の観点から２〜６倍モルを用いるのが特に好ましい。 The compound (3) is preferably used in an amount of 1 to 10 times by mole relative to the compound (4), and particularly preferably 2 to 6 times by mole from the viewpoint of the reaction yield.
反応の温度は、特に限定されず、ラジカル発生剤を用いる場合、ラジカル発生剤の１０時間半減期の温度を下限とし、該温度から３０℃高い温度（好ましくは１０℃高い温度）を上限とするのが好ましい。反応の圧力は、特に限定されない。反応の時間は、１時間〜２４時間が好ましい。 The temperature of the reaction is not particularly limited, and when a radical generator is used, the temperature of the radical generator is 10 hours half-life lower limit, and 30 ° C higher than this temperature (preferably 10 ° C higher temperature) is the upper limit. Is preferred. The reaction pressure is not particularly limited. The reaction time is preferably 1 to 24 hours.
また反応は、反応収率の観点から、溶媒の存在下に行うのが好ましい。溶媒としては、化合物（４）と化合物（３）の反応において不活性な溶媒から選択され、化合物（４）および化合物（３）の溶解性に優れた溶媒が好ましい。 The reaction is preferably performed in the presence of a solvent from the viewpoint of reaction yield. The solvent is preferably selected from solvents that are inert in the reaction of the compound (4) and the compound (3) and excellent in solubility of the compound (4) and the compound (3).
化合物（２）の液相フッ素化反応は、本出願人らによる国際公開００／５６６９４号パンフレット等に記載の方法にしたがって実施するのが好ましい。化合物（２）のフッ素原子含有量は、４０〜７５質量％が好ましく、該フッ素含有量となるようにＲの構造を選択するのが好ましい。また化合物（２）の分子量は、２００〜１０００が好ましく、２５０〜５００が特に好ましい。化合物（２）のフッ素原子含有量と分子量が、前記範囲である場合、後述の液相フッ素化反応の選択率と収率が特に高くなる。 The liquid phase fluorination reaction of the compound (2) is preferably carried out according to the method described in International Publication 00/56694 pamphlet and the like by the present applicants. The fluorine atom content of the compound (2) is preferably 40 to 75% by mass, and the R structure is preferably selected so as to achieve the fluorine content. Moreover, 200-1000 are preferable and, as for the molecular weight of a compound (2), 250-500 are especially preferable. When the fluorine atom content and molecular weight of the compound (2) are within the above ranges, the selectivity and yield of the liquid phase fluorination reaction described later are particularly high.
本発明の製造方法により得られる化合物（１）は、半導体用の洗浄剤、熱媒、溶媒等にとして有用な化合物である。 The compound (1) obtained by the production method of the present invention is a useful compound as a cleaning agent for semiconductors, a heat medium, a solvent and the like.
以下、実施例により本発明を具体的に説明するが、本発明はこれに限定されない。
また、ジクロロペンタフルオロプロパンをＲ−２２５、１，１，２−トリクロロ−１，２，２−トリフルオロエタンをＲ−１１３、テトラメチルシランをＴＭＳと記す。圧力は特に記載しない限りゲージ圧で記す。ガスクロマトグラフィをＧＣ、ガスクロマトグラフィ質量分析をＧＣ−ＭＳと記す。また、ＧＣのピーク面積比より求めた純度をＧＣ純度、収率をＧＣ収率と記す。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this.
Further, dichloropentafluoropropane is referred to as R-225, 1,1,2-trichloro-1,2,2-trifluoroethane as R-113, and tetramethylsilane as TMS. Unless otherwise stated, the pressure is indicated by gauge pressure. Gas chromatography is referred to as GC, and gas chromatography mass spectrometry is referred to as GC-MS. The purity determined from the GC peak area ratio is referred to as GC purity, and the yield is referred to as GC yield.
［例１］化合物（２−１１ａ）の製造例
撹拌機、ジムロート冷却器の備えた反応器（内容積２００ｍＬ、ガラス製）に、ＣＦ３ＣＦ２ＣＦ２ＣＦ２Ｉ（１０８．４ｇ）、ＣＨ２＝ＣＨ（ＣＨ２）３ＯＨ（９．０ｇ）、２，６−ジメチルピリジン（１３．４ｇ）、および２，２−アゾビスイソブチロニトリル（０．５ｇ）を投入して撹拌した。続いて反応器の内温を８０℃に加熱して３時間、還流させた。
Example 1 Production Example of Compound (2-11a) A reactor equipped with a stirrer and a Dimroth condenser (inner volume 200 mL, made of glass) was charged with CF 3 CF 2 CF 2 CF 2 I (108.4 g), CH 2 = CH (CH 2) 3 OH (9.0g), 2,6- dimethyl-pyridine (13.4 g), and 2,2-azo-bis-isobutyronitrile was stirred by introducing a nitrile (0.5 g). Subsequently, the internal temperature of the reactor was heated to 80 ° C. and refluxed for 3 hours.
つぎに反応器を２５℃に冷却しＲ−２２５（１００ｇ）を加えて得た反応器内溶液を、蒸留水（１００ｇ）、５質量％の酢酸水溶液（１００ｇ）、８質量％の重曹水溶液（１００ｍＬ）で順次、洗浄した。さらに反応器内溶液を蒸留水（１００ｇ）で２回洗浄してから、硫酸マグネシウム（５ｇ）で脱水し、Ｒ−２２５と未反応のＣＦ３ＣＦ２ＣＦ２ＣＦ２Ｉを留去して反応粗液を得た。 Next, the reactor was cooled to 25 ° C. and R-225 (100 g) was added to obtain a solution in the reactor. Distilled water (100 g), 5 mass% acetic acid aqueous solution (100 g), 8 mass% sodium bicarbonate aqueous solution ( (100 mL). Further, the solution in the reactor was washed twice with distilled water (100 g), then dehydrated with magnesium sulfate (5 g), and R-225 and unreacted CF 3 CF 2 CF 2 CF 2 I were distilled off to react. A crude liquid was obtained.
反応粗液を大気圧下で蒸留して、留分（１６．９ｇ、１６２℃）を得た。留分をＧＣ、１９Ｆ−ＮＭＲ、および１Ｈ−ＮＭＲによる分析した結果、化合物（２−１１ａ）の生成を確認した（ＧＣ純度９９．７％、ＧＣ収率５３．２％）。 The reaction crude liquid was distilled under atmospheric pressure to obtain a fraction (16.9 g, 162 ° C.). As a result of analyzing the fraction by GC, 19 F-NMR, and 1 H-NMR, it was confirmed that the compound (2-11a) was formed (GC purity 99.7%, GC yield 53.2%).
［例２］化合物（１−１１ａ）の製造例
オートクレーブ（内容積５００ｍＬ、ニッケル製）に、Ｒ−１１３（３１２ｇ）を加えた後に撹拌して２５℃に保持した。オートクレーブガス出口には、２０℃に保持した冷却器、ＮａＦペレット充填層、および−１０℃に保持した冷却器を直列に設置した。また−１０℃に保持した冷却器からは凝集した液をオートクレーブに戻すための液体返送ラインを設置した。オートクレーブに窒素ガスを２５％で１時間吹き込んだ後、窒素ガスで２０体積％に希釈したフッ素ガス（以下、２０％フッ素ガスと記す。）を２５℃で流速１１．８４Ｌ／ｈで１時間吹き込んだ。つぎに２０％希釈フッ素ガスを同じ流速で吹き込みながら、例１で得た留分（６ｇ）をＲ−１１３（１２０ｇ）に溶解した溶液を３．６時間かけてオートクレーブに注入した。
Example 2 Production Example of Compound (1-11a) After adding R-113 (312 g) to an autoclave (internal volume: 500 mL, made of nickel), the mixture was stirred and kept at 25 ° C. At the autoclave gas outlet, a cooler maintained at 20 ° C., a packed bed of NaF pellets, and a cooler maintained at −10 ° C. were installed in series. In addition, a liquid return line for returning the agglomerated liquid to the autoclave was installed from the cooler maintained at −10 ° C. After nitrogen gas was blown into the autoclave at 25% for 1 hour, fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter referred to as 20% fluorine gas) was blown at 25 ° C for 1 hour at a flow rate of 11.84 L / h. It is. Next, a 20% diluted fluorine gas was blown at the same flow rate, and a solution obtained by dissolving the fraction (6 g) obtained in Example 1 in R-113 (120 g) was poured into the autoclave over 3.6 hours.
つぎに、２０％希釈フッ素ガスを同じ流速で吹き込み、かつ反応器圧力を０．１５ＭＰａ（ゲージ圧）に保持しながら、ベンゼン濃度が０．０１ｇ／ｍＬのＲ−１１３溶液を２５℃から４０℃にまで加熱しながら９ｍＬ注入し、オートクレーブのベンゼン溶液注入口を閉めた。 Next, an R-113 solution having a benzene concentration of 0.01 g / mL was added at 25 ° C. to 40 ° C. while blowing 20% diluted fluorine gas at the same flow rate and maintaining the reactor pressure at 0.15 MPa (gauge pressure). 9 mL was injected while heating up to 1, and the benzene solution inlet of the autoclave was closed.
さらに２０％希釈フッ素ガスを同じ流速で吹き込みながら１時間、撹拌を続けた。つぎに、反応器内圧力を大気圧にして、窒素ガスを１時間吹き込んだ。オートクレーブ内容物を１９Ｆ−ＮＭＲで分析した結果、下記化合物（１−１１ａ）の生成を確認した。ＧＣ分析より選択率は７９％であった。 Further, stirring was continued for 1 hour while blowing 20% diluted fluorine gas at the same flow rate. Next, the pressure in the reactor was set to atmospheric pressure, and nitrogen gas was blown in for 1 hour. As a result of analyzing the contents of the autoclave by 19 F-NMR, it was confirmed that the following compound (1-11a) was produced. From GC analysis, the selectivity was 79%.
本発明により、入手容易な化合物からペルフルオロ環状エーテルを高選択率で工業的に製造方法する方法が提供される。
The present invention provides a method for industrially producing a perfluoro cyclic ether with high selectivity from an easily available compound.
Claims (3)
Ｒ−Ｘ （４）
ＣＹ１Ｙ２＝ＣＹ３−Ｑ−ＯＨ （３）
Ｒは、ポリフルオロ１価有機基を示す。
Ｘは、塩素原子、臭素原子、またはヨウ素原子を示す。
Ｙ１、Ｙ２、およびＹ３は、それぞれ独立に、水素原子、フッ素原子、または炭素原子に結合した水素原子を必須とする１価有機基を示す。
Ｑは、炭素原子に結合した水素原子を必須とする２価有機基を示す。
ＲＦは、Ｒがフッ素化される基である場合はＲがペルフルオロ化された１価飽和有機基を、Ｒがペルフルオロ化された１価飽和有機基である場合はＲと同一の基を、示す。
ＹＦ１はＹ１に、ＹＦ２はＹ２に、ＹＦ３はＹ３に、それぞれ対応する基であり、Ｙ１〜Ｙ３が水素原子である場合のＹＦ１〜ＹＦ３はフッ素原子を、Ｙ１〜Ｙ３がフッ素原子である場合のＹＦ１〜ＹＦ３はフッ素原子を、Ｙ１〜Ｙ３が炭素原子に結合した水素原子を必須とする１価有機基である場合のＹＦ１〜ＹＦ３はペルフルオロ化された１価飽和有機基を、示す。
ＱＦは、Ｑがペルフルオロ化された２価飽和有機基を示す。 The compound represented by the following formula (2) is obtained by reacting the compound represented by the following formula (4) with the compound represented by the following formula (3) in the presence of a radical generator and / or a basic compound. Next, the method for producing a perfluoro cyclic ether represented by the following formula (1), wherein the compound is subjected to a liquid phase fluorination reaction.
R-X (4)
CY 1 Y 2 = CY 3 -Q -OH (3)
R represents a polyfluoro monovalent organic group.
X represents a chlorine atom, a bromine atom, or an iodine atom.
Y 1 , Y 2 , and Y 3 each independently represent a monovalent organic group essentially comprising a hydrogen atom, a fluorine atom, or a hydrogen atom bonded to a carbon atom.
Q represents a divalent organic group in which a hydrogen atom bonded to a carbon atom is essential.
R F represents a monovalent saturated organic group in which R is a perfluorinated group when R is a group to be fluorinated, and the same group as R when R is a monovalent saturated organic group in which R is a perfluorinated group. Show.
Y F1 is a group corresponding to Y 1 , Y F2 is a group corresponding to Y 2 , Y F3 is a group corresponding to Y 3 , and when Y 1 to Y 3 are hydrogen atoms, Y F1 to Y F3 are fluorine atoms, Y F1 to Y when Y 1 to Y 3 is a fluorine atom F3 is a fluorine atom, Y 1 to Y 3 is Y F1 ~ if a monovalent organic radical containing, as essential hydrogen atoms bonded to carbon atoms Y F3 represents a perfluorinated monovalent saturated organic group.
Q F represents a divalent saturated organic group in which Q is perfluorinated.
Ｒ−Ｘ （４）
ＣＨ２＝ＣＨ（ＣＨ２）３ＯＨ （３−１１）
Ｒは、ポリフルオロ１価有機基を示す。
Ｘは、塩素原子、臭素原子、またはヨウ素原子を示す。
ＲＦは、Ｒがフッ素化される基である場合はＲがペルフルオロ化された１価飽和有機基を、Ｒがペルフルオロ化された１価飽和有機基である場合はＲと同一の基を示す。 A compound represented by the following formula (4) and a compound represented by the following formula (3-11) are reacted in the presence of a radical generator and / or a basic compound, and represented by the following formula (2-11). A method for producing a compound represented by the following formula (1-11), which comprises subjecting the compound to a liquid phase fluorination reaction.
R-X (4)
CH 2 = CH (CH 2) 3 OH (3-11)
R represents a polyfluoro monovalent organic group.
X represents a chlorine atom, a bromine atom, or an iodine atom.
R F represents a monovalent saturated organic group in which R is perfluorinated when R is a group to be fluorinated, and represents the same group as R when R is a monovalent saturated organic group in which R is perfluorinated. .
Ｒ−Ｘ （４）
ＣＨ２＝ＣＨ（ＣＨ２）４ＯＨ （３−１２）
Ｒは、ポリフルオロ１価有機基を示す。
Ｘは、塩素原子、臭素原子、またはヨウ素原子を示す。
ＲＦは、Ｒがフッ素化される基である場合はＲがペルフルオロ化された１価飽和有機基を、Ｒがペルフルオロ化された１価飽和有機基である場合はＲと同一の基を示す。
A compound represented by the following formula (4) and a compound represented by the following formula (3-12) are reacted in the presence of a radical generator and / or a basic compound, and represented by the following formula (2-12). A method for producing a compound represented by the following formula (1-12), wherein the compound is subjected to a liquid phase fluorination reaction.
R-X (4)
CH 2 = CH (CH 2) 4 OH (3-12)
R represents a polyfluoro monovalent organic group.
X represents a chlorine atom, a bromine atom, or an iodine atom.
R F represents a monovalent saturated organic group in which R is perfluorinated when R is a group to be fluorinated, and represents the same group as R when R is a monovalent saturated organic group in which R is perfluorinated. .
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| JP2004247109A JP2006063013A (en) | 2004-08-26 | 2004-08-26 | Method for producing perfluoro cyclic ether |
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| JP2004247109A JP2006063013A (en) | 2004-08-26 | 2004-08-26 | Method for producing perfluoro cyclic ether |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB718318A (en) * | 1952-06-24 | 1954-11-10 | Minnesota Mining & Mfg | Improvements in or relating to process of preparing cyclic fluoroalkylene oxide compounds and the cyclic fluoroalkylene oxide compounds resulting from said process |
| JPS60500498A (en) * | 1983-01-20 | 1985-04-11 | エレクトリシィティ アソシェーション サービシィズ リミテッド | Method for producing fluorinated ether |
| JPH04500520A (en) * | 1988-09-28 | 1992-01-30 | エクスフルアー・リサーチ・コーポレーシヨン | Liquid phase fluorine replacement |
| WO2000056694A1 (en) * | 1999-03-23 | 2000-09-28 | Asahi Glass Company, Limited | Process for producing fluorine compound through liquid-phase fluorination |
| WO2004050649A1 (en) * | 2002-12-04 | 2004-06-17 | Asahi Glass Company, Limited | Perfluoro five-membered ring compound |
-
2004
- 2004-08-26 JP JP2004247109A patent/JP2006063013A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB718318A (en) * | 1952-06-24 | 1954-11-10 | Minnesota Mining & Mfg | Improvements in or relating to process of preparing cyclic fluoroalkylene oxide compounds and the cyclic fluoroalkylene oxide compounds resulting from said process |
| JPS60500498A (en) * | 1983-01-20 | 1985-04-11 | エレクトリシィティ アソシェーション サービシィズ リミテッド | Method for producing fluorinated ether |
| JPH04500520A (en) * | 1988-09-28 | 1992-01-30 | エクスフルアー・リサーチ・コーポレーシヨン | Liquid phase fluorine replacement |
| WO2000056694A1 (en) * | 1999-03-23 | 2000-09-28 | Asahi Glass Company, Limited | Process for producing fluorine compound through liquid-phase fluorination |
| WO2004050649A1 (en) * | 2002-12-04 | 2004-06-17 | Asahi Glass Company, Limited | Perfluoro five-membered ring compound |
Non-Patent Citations (1)
| Title |
|---|
| JPN6010043443, Ｇｒｅｉｎｅｒ， Ｊ． ｅｔ ａｌ．, ""Ａｄｄｉｔｉｏｎ ｏｆ ｐｅｒｆｌｕｏｒｏａｌｋｙｌ ｉｏｄｉｄｅｓ ｔｏ ４−ｐｅｎｔｅｎｏｌ ａｎｄ ｉｔｓ ｄｅｒｉｖａｔｉｖｅｓ： ｏｎｅ−ｐｏｔ ｐｒｅｐａｒａｔｉｏｎ ｏｆ ２−［（Ｆ−", Ｊｏｕｒｎａｌ ｏｆ Ｆｌｕｏｒｉｎｅ Ｃｈｅｍｉｓｔｒｙ, 1992, Ｖｏｌ．５６， Ｎｏ．３, ｐ．２８５−２９３ * |
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