JP2000226392A - Production of tris(perfluoroalkylsulfonyl)methide salt - Google Patents
Production of tris(perfluoroalkylsulfonyl)methide saltInfo
- Publication number
- JP2000226392A JP2000226392A JP11026286A JP2628699A JP2000226392A JP 2000226392 A JP2000226392 A JP 2000226392A JP 11026286 A JP11026286 A JP 11026286A JP 2628699 A JP2628699 A JP 2628699A JP 2000226392 A JP2000226392 A JP 2000226392A
- Authority
- JP
- Japan
- Prior art keywords
- perfluoroalkylsulfonyl
- tris
- alkali metal
- methide
- methide salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ルイス酸触媒およ
び有機イオン電導体として有用な物質である一般式
（Ｉ）で示されるトリス（パーフルオロアルキルスルホ
ニル）メチド塩の製造法に関するものである。The present invention relates to a method for producing a tris (perfluoroalkylsulfonyl) methide salt represented by the general formula (I), which is a substance useful as a Lewis acid catalyst and an organic ion conductor.
【０００２】[0002]
【従来の技術】トリス（パーフルオロアルキルスルホニ
ル）メチド塩は、ルイス酸触媒や有機イオン電導体とし
て有機合成および電気材料分野において有用な物質であ
る。これまでに提案されているトリス（パーフルオロア
ルキルスルホニル）メチド塩の製法としては、例えば、 下記の如く、メチルマグネシウムハライド（グリニャ
ー試薬）とパーフルオロアルキルスルホニルハライドと
の反応によりビス（パーフルオロアルキルスルホニル）
メタンを一旦合成した後、再び前記グリニャー試薬およ
びパーフルオロアルキルスルホニルハライドと反応させ
てトリス（パーフルオロアルキルスルホニル）メタンを
合成し、更にアルカリ金属化合物と反応させる方法（Ｗ
Ｏ92／02966,Inorg.Chem., 1988,27,2135.,J.Chem.So
c.Faraday Trans.,1993,89,355 等） 3CH3MgX + 2RfSO2X + HX → (RfSO2)2CH2 + 2CH4 + 3Mg
X2 (RfSO2)2CH2 + 2CH3MgX + RfSO2X + HX→ (RfSO2)3CH +
2CH4 + 2MgX2 (RfSO2)3CH + MOR → (RfSO2)3CM + ROH ［式中、X はハロゲン、 Rf はパーフルオロアルキル
基、M はアルカリ金属陽イオン、R は水素またはメチル
基を表す。］ 上記ビス（パーフルオロアルキルスルホニル）メタン
をアルカリ金属塩に変換した後、塩基存在下でフルオロ
アルキルスルホニルハライドと反応してトリス（パーフ
ルオロアルキルスルホニル）メタン化合物を合成し、さ
らにアルカリ金属化合物と反応させる方法（ＵＳＰ5446
134 等） (RfSO2)2CH2 + MOR → (RfSO2)2CHM + ROH (RfSO2)2CHM + RfSO2X + Et3N → (RfSO2)3CHNEt3 + MX (RfSO2)3CHNEt3 + M2PO4 → (RfSO2)3CM + M(Et3NH)PO4 ［式中、 Rf, M, R, X は前記定義の通りである。］等
が知られている。しかしながら、上記およびの方法
は、いずれも非常に多くの工程を必要とする上に高価な
グリニャー試薬を多量に使用することから、工業的な製
法ではない。以上のように、トリス（パーフルオロアル
キルスルホニル）メチド塩の実用的な合成法について
は、満足のいく方法が見当たらないのが実情である。2. Description of the Related Art Tris (perfluoroalkylsulfonyl) methide salts are useful in the field of organic synthesis and electric materials as Lewis acid catalysts and organic ionic conductors. Methods for producing tris (perfluoroalkylsulfonyl) methide salts that have been proposed so far include, for example, bis (perfluoroalkylsulfonyl) method by reacting methylmagnesium halide (Grignard reagent) with perfluoroalkylsulfonyl halide as described below. )
A method of once synthesizing methane, reacting again with the above Grignard reagent and perfluoroalkylsulfonyl halide to synthesize tris (perfluoroalkylsulfonyl) methane, and further reacting with an alkali metal compound (W
O92 / 02966, Inorg. Chem., 1988, 27, 2135., J. Chem. So
c.Faraday Trans., 1993,89,355 etc.) 3CH 3 MgX + 2R f SO 2 X + HX → (R f SO 2 ) 2 CH 2 + 2CH 4 + 3Mg
X 2 (R f SO 2 ) 2 CH 2 + 2CH 3 MgX + R f SO 2 X + HX → (R f SO 2 ) 3 CH +
2CH 4 + 2MgX 2 (R f SO 2 ) 3 CH + MOR → (R f SO 2 ) 3 CM + ROH wherein X is a halogen, R f is a perfluoroalkyl group, M is an alkali metal cation, R Represents hydrogen or a methyl group. After converting the above bis (perfluoroalkylsulfonyl) methane into an alkali metal salt, it reacts with a fluoroalkylsulfonyl halide in the presence of a base to synthesize a tris (perfluoroalkylsulfonyl) methane compound, and further reacts with the alkali metal compound. Method (USP5446
134 etc.) (R f SO 2 ) 2 CH 2 + MOR → (R f SO 2 ) 2 CHM + ROH (R f SO 2 ) 2 CHM + R f SO 2 X + Et 3 N → (R f SO 2 ) 3 CHNEt 3 + MX (R f SO 2 ) 3 CHNEt 3 + M 2 PO 4 → (R f SO 2 ) 3 CM + M (Et 3 NH) PO 4 (where R f , M, R, and X are As defined above. ] Etc. are known. However, each of the above methods is not an industrial production method because it requires a large number of steps and uses a large amount of an expensive Grignard reagent. As described above, no satisfactory method has been found for a practical method for synthesizing a tris (perfluoroalkylsulfonyl) methide salt.
【０００３】[0003]
【発明が解決しようとする課題】従って本発明の目的
は、上記およびの方法による問題点を解決し、トリ
ス（パーフルオロアルキルスルホニル）メチド塩の簡便
な工業的製法を提供するものである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems and to provide a simple industrial process for producing tris (perfluoroalkylsulfonyl) methide salts.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記目的
を達成するため鋭意検討した結果、メチド化剤としてア
ルカリ金属メタンを用いることによりトリス（パーフル
オロアルキルスルホニル）メチド塩の簡便な製造法を見
い出した。本発明によれば、パーフルオロアルキルスル
ホニルハライドとアルカリ金属メタンからなる混合物を
有機溶媒中で反応させることにより、一工程でトリス
（パーフルオロアルキルスルホニル）メチド塩を製造す
ることができる。即ち、本発明は、一般式（II）： RfSO2X …（II） 〔式中、X はハロゲンを表す。 Rf は炭素数１から６ま
での直鎖または分岐状のパーフルオロアルキル基を表
す。〕で示されるパーフルオロアルキルスルホニルハラ
イドと、一般式（III）： MCH3 …（III） 〔式中、M はアルカリ金属陽イオンを表す。〕で示され
るアルカリ金属メタンからなる混合物を有機溶媒中で反
応させることにより、一般式（Ｉ）： (RfSO2)3CM …（Ｉ） 〔式中、 Rf およびM は前記定義の通りである。〕で表
されるトリス（パーフルオロアルキルスルホニル）メチ
ド塩を製造する方法である。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have succeeded in producing a tris (perfluoroalkylsulfonyl) methide salt easily by using an alkali metal methane as a methidating agent. I found a law. According to the present invention, tris (perfluoroalkylsulfonyl) methide salt can be produced in one step by reacting a mixture of perfluoroalkylsulfonyl halide and alkali metal methane in an organic solvent. That is, the present invention provides a compound represented by the general formula (II): R f SO 2 X (II) wherein X represents a halogen. R f represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms. And a general formula (III): MCH 3 ... (III) wherein M represents an alkali metal cation. A mixture of an alkali metal methane represented by the following general formula (I): (R f SO 2 ) 3 CM (I) wherein R f and M are as defined above. It is on the street. The method for producing a tris (perfluoroalkylsulfonyl) methide salt represented by the formula:
【０００５】[0005]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明において化合物（Ｉ）の製造に用いられる有機溶
媒としては、（II）および（III）が可溶で、反応工程
中で原料及び生成物と反応しない不活性溶媒が好まし
く、例えば、ジエチルエーテル、テトラヒドロフラン、
ジオキサン等のエーテル類が好適なものとして挙げられ
るが、これらに限定されるものではない。上記反応は−
70℃から 150℃の温度範囲で行うことが可能であり、最
適には、30℃から 100℃の温度範囲が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, the organic solvent used for the production of compound (I) is preferably an inert solvent in which (II) and (III) are soluble and do not react with the starting materials and products in the reaction step. , Tetrahydrofuran,
Suitable examples include ethers such as dioxane, but are not limited thereto. The above reaction is-
It is possible to work in a temperature range from 70 ° C to 150 ° C, and optimally a temperature range from 30 ° C to 100 ° C.
【０００６】本発明の反応式は、次のように示される。 3RfSO2X + 4MCH3 → (RfSO2)3CM + 3LiX + 3CH3 ［式中、 Rf は炭素数１から６までの直鎖または分岐状
のパーフルオロアルキル基であり、好ましくはCF3 、C2
F5、C3F7、C4F9である。X はハロゲン、M はアルカリ金
属陽イオンであり、好ましくはLi+ 、Na+ 、K + であ
る。］上記 Rf としてはCF3 、C2F5、C3F7、C4F9が好ま
しく、またM としてはLi+ 、Na+ 、K + が好ましい。The reaction formula of the present invention is shown as follows. 3R f SO 2 X + 4MCH 3 → (R f SO 2 ) 3 CM + 3LiX + 3CH 3 [wherein, R f is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and is preferable. Is CF 3 , C 2
F 5, a C 3 F 7, C 4 F 9. X is a halogen and M is an alkali metal cation, preferably Li + , Na + , and K + . R f is preferably CF 3 , C 2 F 5 , C 3 F 7 , or C 4 F 9 , and M is preferably Li + , Na + , or K + .
【０００７】[0007]
【実施例】以下に実施例により本発明を更に詳細に説明
するが、本発明はこれらの実施例に限定されるものでは
ない。 実施例１［リチウムトリス（トリフルオロメタンスルホ
ニル）メチドの製造］ コンデンサーを付した500mL 三口フラスコを窒素置換し
た後、1.4Mメチルリチウム／エーテル溶液300mL を仕込
み、ドライアイス／エタノール浴上−55℃に冷却した。
激しく攪拌しながら、トリフルオロメタンスルホニルク
ロライド53ｇを滴下した。その後、徐々に昇温し、沸騰
還流下で７時間反応を行なった。室温まで放冷した後、
冷却しながら５％塩酸を加え十分攪拌を行なった。晶析
した塩化リチウムおよび水酸化リチウムを濾別した。濾
液は、エーテルで抽出した後、飽和食塩水で洗浄した。
有機層は、無水硫酸マグネシウムを加え１時間乾燥した
後、孔径 0.2μm のメンブランフィルター（日本ミリポ
ール社製）により減圧濾過した。濾液は、減圧下溶媒を
留去した後、トルエンを加えて共沸脱水を行った。得ら
れた結晶を 150℃で72時間乾燥を行った結果、リチウム
トリス（トリフルオロメタンスルホニル）メチド：(CF3
SO2)3CLi 13.5g（収率31％）を得た。得られた物質の物
性値は以下の通りであった。 融点： 268℃13 Ｃ−ＮＭＲ（CD3CN ，δ）：123.3, 119.119 Ｆ−ＮＭＲ（CD3CN ，δ）：−77.5(S) ＩＲ（ｋＢｒ，cm-1）：3500, 1645, 1377, 1202, 112
4, 983, 769, 668, 625,, 576, 506, 445, 417, 406 実施例２ 200mL ステンレス製オートクレーブを窒素置換した後、
1.4Mメチルリチウム／エーテル溶液 100mLを仕込み、ド
ライアイス／エタノール浴上−75℃に冷却した。これに
トリフルオロメタンスルホニルクロライド20ｇを添加し
た。その後徐々に昇温し、90℃、8.5 kg／cm2 で24時間
反応を行なった。実施例１と同様の処理を行なった結
果、リチウムトリス（トリフルオロメタンスルホニル）
メチド 8.1ｇ（収率56％）を得た。 実施例３ トリフルオロメタンスルホニルフルオライドを使用し、
実施例２と同様の条件で反応を行なった結果、リチウム
トリス（トリフルオロメタンスルホニル）メチドを得
た。収率は、42％であった。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 [Production of lithium tris (trifluoromethanesulfonyl) methide] After a 500 mL three-necked flask equipped with a condenser was purged with nitrogen, 300 mL of a 1.4 M methyllithium / ether solution was charged, and cooled to −55 ° C. on a dry ice / ethanol bath. did.
With vigorous stirring, 53 g of trifluoromethanesulfonyl chloride was added dropwise. Thereafter, the temperature was gradually raised, and the reaction was carried out under boiling reflux for 7 hours. After cooling to room temperature,
While cooling, 5% hydrochloric acid was added and sufficiently stirred. The crystallized lithium chloride and lithium hydroxide were separated by filtration. The filtrate was extracted with ether and washed with saturated saline.
The organic layer was added with anhydrous magnesium sulfate, dried for 1 hour, and then filtered under reduced pressure through a membrane filter having a pore size of 0.2 μm (manufactured by Nippon Millipol). After evaporating the solvent under reduced pressure, the filtrate was subjected to azeotropic dehydration by adding toluene. The obtained crystals were dried at 150 ° C. for 72 hours. As a result, lithium tris (trifluoromethanesulfonyl) methide: (CF 3
13.5 g (31% yield) of SO 2 ) 3 CLi were obtained. The physical properties of the obtained substance were as follows. Melting point: 268 ° C. 13 C-NMR (CD 3 CN, δ): 123.3, 119.1 19 F-NMR (CD 3 CN, δ): −77.5 (S) IR (kBr, cm −1 ): 3500, 1645, 1377 , 1202, 112
4, 983, 769, 668, 625 ,, 576, 506, 445, 417, 406 Example 2 After replacing a 200 mL stainless steel autoclave with nitrogen,
100 mL of a 1.4 M methyllithium / ether solution was charged and cooled to −75 ° C. on a dry ice / ethanol bath. To this was added 20 g of trifluoromethanesulfonyl chloride. Thereafter, the temperature was gradually raised, and the reaction was carried out at 90 ° C. and 8.5 kg / cm 2 for 24 hours. As a result of performing the same treatment as in Example 1, lithium tris (trifluoromethanesulfonyl)
8.1 g of methide (56% yield) was obtained. Example 3 Using trifluoromethanesulfonyl fluoride,
The reaction was carried out under the same conditions as in Example 2 to obtain lithium tris (trifluoromethanesulfonyl) methide. Yield was 42%.
Claims (1)
のパーフルオロアルキル基、M はアルカリ金属陽イオン
を表す。〕で表されるトリス（パーフルオロアルキルス
ルホニル）メチド塩の製造法であって、一般式（II）： RfSO2X …（II） 〔式中、X はハロゲンを表す。 Rf は前記定義の通りで
ある。〕で示されるパーフルオロアルキルスルホニルハ
ライドと、一般式（III）： MCH3 …（III） 〔式中、M は前記定義の通りである。〕で示されるアル
カリ金属メタンからなる混合物を有機溶媒中で反応させ
ることを特徴とするトリス（パーフルオロアルキルスル
ホニル）メチド塩の製造方法。1. A compound of the general formula (I): (R f SO 2 ) 3 CM (I) wherein R f is a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and M is Represents an alkali metal cation. A method for producing a tris (perfluoroalkylsulfonyl) methide salt represented by the general formula (II): R f SO 2 X ... (II) wherein X represents a halogen. R f is as defined above. And a general formula (III): MCH 3 ... (III) wherein M is as defined above. A method for producing a tris (perfluoroalkylsulfonyl) methide salt, comprising reacting a mixture comprising alkali metal methane represented by the formula (1) in an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02628699A JP4077103B2 (en) | 1999-02-03 | 1999-02-03 | Method for producing tris (perfluoroalkylsulfonyl) methide salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02628699A JP4077103B2 (en) | 1999-02-03 | 1999-02-03 | Method for producing tris (perfluoroalkylsulfonyl) methide salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000226392A true JP2000226392A (en) | 2000-08-15 |
| JP4077103B2 JP4077103B2 (en) | 2008-04-16 |
Family
ID=12189067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02628699A Expired - Lifetime JP4077103B2 (en) | 1999-02-03 | 1999-02-03 | Method for producing tris (perfluoroalkylsulfonyl) methide salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4077103B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008075672A1 (en) | 2006-12-20 | 2008-06-26 | Central Glass Company, Limited | Method for producing tris(perfluoroalkanesulfonyl)methide acid salt |
| CN115557862A (en) * | 2022-10-25 | 2023-01-03 | 广州天赐高新材料股份有限公司 | Preparation method of tris (perfluoroalkyl sulfonyl) methane and lithium salt thereof |
-
1999
- 1999-02-03 JP JP02628699A patent/JP4077103B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008075672A1 (en) | 2006-12-20 | 2008-06-26 | Central Glass Company, Limited | Method for producing tris(perfluoroalkanesulfonyl)methide acid salt |
| KR101030639B1 (en) | 2006-12-20 | 2011-04-20 | 샌트랄 글래스 컴퍼니 리미티드 | Method for producing trisperfluoroalkanesulfonylmethide acid salt |
| US8304580B2 (en) | 2006-12-20 | 2012-11-06 | Central Glass Company, Limited | Method for producing tris(perfluoroalkanesulfonyl)methide acid salt |
| CN115557862A (en) * | 2022-10-25 | 2023-01-03 | 广州天赐高新材料股份有限公司 | Preparation method of tris (perfluoroalkyl sulfonyl) methane and lithium salt thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4077103B2 (en) | 2008-04-16 |
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