TW200306980A - Process for the preparation of monohydroperfluoroalkanes, bis(perfluoroalkyl) phosphinates and perfluoroalkylphosphonates - Google Patents

Process for the preparation of monohydroperfluoroalkanes, bis(perfluoroalkyl) phosphinates and perfluoroalkylphosphonates Download PDF

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TW200306980A
TW200306980A TW092108540A TW92108540A TW200306980A TW 200306980 A TW200306980 A TW 200306980A TW 092108540 A TW092108540 A TW 092108540A TW 92108540 A TW92108540 A TW 92108540A TW 200306980 A TW200306980 A TW 200306980A
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hydroxide
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TWI328010B (en
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Nikolai Ignatyev
Michael Weiden
Urs Welz-Biermann
Udo Heider
Peter Sartori
Willner Helge
Kucheryna Andriy
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Merck Patent Gmbh
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Abstract

The present invention relates to a process for the preparation of mono-hydroperfluoroalkanes, bis(perfluoroalkyl)phosphinates and perfluoroalkyl-phosphonates which comprises at least the treatment of at least one perfluoroalkylphosphorane with at least one base in a suitable reaction medium.

Description

200306980 玖、發明說明： 【發明所屬之技術領域】 本發明係關於一種製備單氫全氟烷化物，雙（全氟烷基） 亞膦酸鹽及全氟烷基膦酸鹽之方法，其包括在一種適合反 應介質内至少一進行以至少一種驗處理至少一種全氟燒基 磷烷之步騾。 【先前技術】 已知單氫全氟烷化物有一段時間了，且已發現其在各種 領域上具有廣泛用途，特別為可作為臭氧親和性致冷劑 (WO 01/40400， WO 01/23494， WO 01/23491， WO 99/36485， WO 98/08913)，作為清潔劑（WO 01/32323)，作 為微電子領域之蝕刻劑組份（US 2001/0005637， US 6228775)，滅火劑應用（WO 01/05468，Combust· Flame，121， No. 3 (2000)，第 471-487 頁，CN 1218702)，作為發泡體中之 發泡劑（US 6225365，WO 01/18098)及聚合物材料與有效麻 醉劑之製備（Anesth. Analg (N.Y·)，79，No· 2(1994)，第 245-251 頁，Τ· Hudlicky等人，J. of Fluorine Chem.，59，No. 1(1992)，第 9-14 頁）。 在商業上很容易以噸規模製備部份這些單氫全氟烷烴’ 例如，五氟乙烷，通常係藉由氯化烴之催化氫氟化反應進 行該製法（WO 01/77048， EP 1052235)。該方法之缺點為首 先存在有於相當高溫下使用氟化氫所產生之危險。而且’ 該方法需要特殊觸媒，其必需事先藉由比較複雜的方法製 成。該方法的另一項缺點為使用氣製備該氯化烴之方法在 84146 -6- 200306980 生態上仍有爭議，且該製備支出會進一步增加。最後，製 備該五氟乙烷之已知方法並不很適用於製備長鏈單氫全氟 燒烴，例如，一氫九氟丁燒。 而且，已知有一些其它方法，其中係使用下述特殊氟化 劑製備五氟乙纟克’這些特殊氟化劑包括，例如，BrF3(R· A. Devis，J. Org. Chem. 32(1967)，第 3478 頁），XeF2(JP 2000/1 19201) ’ SF4(G· Siegemund，Liebigs Ann. Chem·，1979, 弟 1280 頁，E.R. Bissell，J· 〇f 〇rganic chem·，29，（1964)第 1591)，SbF5(G.G· Belenkii等人，Ιζν· Akad. Nauk SSSR，Ser. Khim·，1972，第 983 頁，Chem· Abstr. 77(1972) 75296，A.F· Ermolov 等人，Zh Org· Khim·，17(1981)，第 2239 頁，J.〇rg. Chem. USSR (Engl. Translation)，17 (1981)，第 199 頁，US 2426172)，MoF6(L.D· Shustov等人，Zh.Obshch. Khim·，53 (1983)，第 103 頁，J· Gen_ Chem· USSR (Engl· translation)，53 (1983)，第 85 頁）及 CoF3(US 6162955)。 然而，上述方法並沒有受到工業上的重視，因為該個別 起始化合物及該氟化劑本身很昂貴。 反之，已知只有少數幾種可用以製備長鏈單氫全氟烷烴 之方法。 根據一種取早的方法’可藉由強驗（例如，乙氧基納）處 理’使全氟化幾酸之鹽（J.D· LaZerte等人，j· Am. Chem. Soc·， 75 (1953)，第 4525 頁；R.N. Haszeldine，j· chem· Soc. 1953, 第 1548 頁）或對應酉旨（E· Bergman，J· 〇rg chem.，23 (1958)， 第476頁）進行去羧基化反應以製備該單全敦燒烴。 84146 -7 - 200306980 根據另一種方法，可藉由以水性鹼處理全氟化酮（其在該 羰基之碳原子上具有三氟甲基）以製備單氫全氟烷烴（LV.200306980 (1) Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for preparing a monohydroperfluoroalkylate, a bis (perfluoroalkyl) phosphinate, and a perfluoroalkylphosphonate, including: At least one step of treating at least one perfluoroalkanylphosphine in at least one test in a suitable reaction medium is performed. [Prior art] Monohydroperfluoroalkanes have been known for some time and have been found to have a wide range of uses in various fields, especially as ozone-friendly refrigerants (WO 01/40400, WO 01/23494, WO 01/23491, WO 99/36485, WO 98/08913), as a cleaning agent (WO 01/32323), as an etchant component in the field of microelectronics (US 2001/0005637, US 6228775), fire extinguishing agent application (WO 01/05468, Combust · Flame, 121, No. 3 (2000), pages 471-487, CN 1218702), as foaming agent in foams (US 6225365, WO 01/18098) and polymer materials and Preparation of Effective Anesthetics (Anesth. Analg (NY ·), 79, No. 2 (1994), pages 245-251, T. Hudlicky et al., J. of Fluorine Chem., 59, No. 1 (1992), P. 9-14). Commercially, it is easy to produce some of these monohydroperfluoroalkanes on a ton scale. For example, pentafluoroethane is usually produced by catalyzed hydrofluorination of chlorinated hydrocarbons (WO 01/77048, EP 1052235). . The disadvantage of this method is first that there is the danger of using hydrogen fluoride at relatively high temperatures. Moreover, this method requires a special catalyst, which must be made by a more complicated method in advance. Another disadvantage of this method is that the method of using gas to prepare the chlorinated hydrocarbon is still ecologically controversial at 84146 -6- 200306980, and the preparation expenditure will further increase. Finally, the known method for preparing the pentafluoroethane is not very suitable for the production of long-chain monohydroperfluorocarbons, such as monohydroninefluorobutane. Moreover, there are other known methods in which pentafluoroacetam is prepared using the following special fluorinating agents. These special fluorinating agents include, for example, BrF3 (R. A. Devis, J. Org. Chem. 32 ( 1967), p. 3478), XeF2 (JP 2000/1 19201) 'SF4 (G. Siegemund, Liebys Ann. Chem., 1979, p. 1280, ER Bissell, J. 〇f 〇rganic chem., 29, ( (1964) p. 1591), SbF5 (GG Belenkii et al., Ινν Akad. Nauk SSSR, Ser. Khim., 1972, p. 983, Chem. Abstr. 77 (1972) 75296, AF Ermolov et al., Zh Org Khim., 17 (1981), p. 2239, J. Org. Chem. USSR (Engl. Translation), 17 (1981), p. 199, US 2426172), MoF6 (LD Shustov et al., Zh. Obshch. Khim., 53 (1983), p. 103, J. Gen. Chem. USSR (Engl. Translation), 53 (1983), p. 85) and CoF3 (US 6162955). However, the above-mentioned method has not received industrial attention because the individual starting compounds and the fluorinating agent are expensive by themselves. In contrast, only a few methods are known which can be used to prepare long-chain monohydroperfluoroalkanes. According to an early method, the salt of perfluorinated citric acid can be treated by strong tests (eg, ethoxylated sodium) (JD. LaZerte et al., J. Am. Chem. Soc., 75 (1953) , P. 4525; RN Haszeldine, j. Chem. Soc. 1953, p. 1548) or the corresponding purpose (E. Bergman, J. Org chem., 23 (1958), p. 476) for decarboxylation To prepare the mono-quadurcal hydrocarbon. 84146 -7-200306980 According to another method, a monohydroperfluoroalkane (LV. LV) can be prepared by treating a perfluorinated ketone (which has a trifluoromethyl group on the carbon atom of the carbonyl group) with an aqueous base.

Saloutina等人，Izv· Akad· Nauk SSSR，Ser Khim·，1984，第 5 期，第1114-1116頁，€}^111.入68化.101 (1984) 210504兀）。該方 法之缺點亦為必需使用昂貴的起始物質及高溫。 此外’尚可於鬲溫下藉由呈氣相之氫（歐洲專利EP 632 001)使用各種還原劑（例如，鋅灰）在甲醇（τ· Hudlicky等人，J. ofFlU〇rineChem.，59，第以月^的])，第9-14頁），甲氧基鈉 / (J· L. Howell等人，J. 〇f Fluorine Chem·，72，第 1期（1995)， / 第 61-68 頁）中，藉助於該複合物[TaCp2(C2H4)H](pHpussel \J 等人，P〇lyhedron π，第 7期（1^^)，第 1037-1043 頁）使全氟 丁基碘進行還原反應製成該—九氟丁烷。 ;、:、而這些方法之缺點同樣為必需先使用該起始化合物 全氟丁基碘進行反應，但是該全氟丁基碘只能藉由比較昂 貴的製法製成。 【發明内容】 Q此，本發明目的為提供一種可以以簡單並費用不高的 万法製備良好產率的單氫全氟垸烴。較佳應該以高純度得 到该早氫全氟垸烴。本發明另一目標為製備雙（全氟燒基） 亞膦酸鹽及全氟烷基膦酸鹽。 【實施方式】 已藉由根據本發明製備該通式CnHF2n+1 (其中，較佳 為—η — 4)之單氫全氟烷烴，雙（全氟烷基）亞膦酸鹽及全氟烷 基膦酸鹽之方法逵成# B p . 連成咸目^，琢万法包括一種適合反應介 84146 200306980 質内，至少進行以至少一種鹼處理至少一種全氟烷基磷烷 之步驟。 根據本發明’ ^各情況中，可以使用_種全氟垸基魏 或一或更夕種全氟燒基鱗烷之混合物進行根據本發明製備 該單氫全氟燒烴之方法。 可藉由熟悉本技藝者已知之習用方法製備根據本發明該 方法所使用之該全氟烷基磷烷。 如 V· Ya· Semenil 等人在 Zh 〇bschch· Khim，55,第 ^期 (1985)，第 2716_2720 頁中所述，及 Ν· Ignative 在 j· 〇f Fluorme Chem·，103 (2〇〇〇)，第 57_61 頁中所述及 w〇 00/21969所述，可較佳藉由適合起始化合物之電化學氟化反 應，製備該全氟烷基磷烷。這些資料之對應說明文併於本 文供參考並可視為本揭示内容的一部份。 在根據本發明方法之一項較佳具體實例中，可利用至少 一種以下通式I之全氟烷基磷烷 (CnF2n+l)mPF5-mSaloutina et al., Izv. Akad. Nauk SSSR, Ser Khim., 1984, No. 5, pp. 1114-1116, ^ 111. Into Chem. 101 (1984) 210504). The disadvantages of this method are also the need to use expensive starting materials and high temperatures. In addition, it is still possible to use various reducing agents (for example, zinc ash) in methanol (τ · Hudlicky et al., J. of Flourine Chem., 59, by hydrogen in the gas phase (European patent EP 632 001) at high temperature. []], Pp. 9-14), sodium methoxide / (J. L. Howell et al., J. Of Fluorine Chem., 72, Issue 1 (1995), / 61- 68), the compound [TaCp2 (C2H4) H] (pHpussel \ J et al., Pollyhedron π, No. 7 (1 ^^), pp. 1037-1043) was used to make perfluorobutyl iodide The reduction reaction is made into the nonafluorobutane. The disadvantage of these methods is that the starting compound perfluorobutyl iodide must be used for the reaction, but the perfluorobutyl iodide can only be made by a relatively expensive method. [Summary of the Invention] Accordingly, the object of the present invention is to provide a monohydroperfluorofluorene that can be produced in a good yield in a simple and inexpensive way. The early hydrogen perfluorofluorene should preferably be obtained in high purity. Another object of the present invention is to prepare bis (perfluorocarbon) phosphinates and perfluoroalkylphosphonates. [Embodiment] Monohydroperfluoroalkanes, bis (perfluoroalkyl) phosphinates and perfluoroalkanes of the general formula CnHF2n + 1 (of which, preferably -η-4) have been prepared according to the present invention The method of base phosphonates is converted to #B p. The sulfamate method includes a step suitable for treating at least one perfluoroalkylphosphorane with at least one base within a reaction medium 84146 200306980. In each case according to the present invention, a method of preparing the monohydroperfluorocarbon burning hydrocarbon according to the present invention may be performed using a mixture of one kind of perfluorofluorenylwei or one or more kinds of perfluorocarbon-based leptane. The perfluoroalkylphosphanes used in the method according to the present invention can be prepared by conventional methods known to those skilled in the art. As described by V. Ya · Semenil et al. In Zhöbschch · Khim, 55, Issue ^ (1985), pp. 2716_2720, and N. Ignative in j. Fluor Chem., 103 (2000). ), As described on pages 57_61 and WO00 / 21969, the perfluoroalkylphosphorane can be prepared preferably by an electrochemical fluorination reaction suitable for the starting compound. The corresponding explanatory texts of these materials are incorporated herein by reference and can be regarded as part of this disclosure. In a preferred embodiment of the method according to the invention, at least one perfluoroalkylphosphorane (CnF2n + l) mPF5-m of the following general formula I may be used

I 其中lSnS8，較佳為，且於各情況中，1，2或3。 更特佳之全氟燒基磷燒化合物為選自由二敦三（五敦乙 基）磷烷，二氟三（正-九氟丁基）磷烷，二氟三（正-七氟丙基） 鱗烷及三氟雙（正-九氟丁基）磷烷所組成之群組。 於各情況中，較佳僅使用一種鹼，根據本發明該方法處 理該全氟磷烷化合物（群）。然而，當然在根據本發明該方法 中亦可使用2或更多種驗之混合物。亦可以以該對應媒合物 84146 200306980 <型式（較佳該對應水合物型式，或熟悉本技藝者已知之習 合加合物型式）使用個別鹼。 在根據本發明该製備單氫全氟燒烴之方法之另一項較佳 具把貝例中，通常使用一種鹼（a)，較佳為一種無機鹼化）或 有機鹼（C)。該無機鹼（b)較佳選自由鹼金屬氫氧化物及鹼土 至屬氣氧化物所組成之群組。 在根據本發明該方法中，若使用鹼金屬氫氧化物作為鹼 (b)，則其較佳選自由氫氧化鋰，氫氧化鋰單水合物，氫氧 化鈉及氫氧化鉀所組成之群組。 在根據本發明該方法中，若使用鹼土金屬氫氧化物作為 鹼（b) ’則其較佳選自由氫氧化鋇，氫氧化鋇八水合物及氳 氧化鈣所組成之群組。 同樣可較佳使用一種有機鹼（c)或有機金屬化合物進行根 據本發明製備單氫全氟烷烴之方法。該鹼（c)可較佳選自以 下所組成之群組··烷基銨氫氧化物，芳基銨氫氧化物，烷 基芳基銨氫氧化物，烷基鱗氫氧化物，芳基鱗氫氧化物， 烷基芳基鳞氫氧化物，烷基胺，芳基胺，烷基芳基胺，烷 基膦，芳基膦及烷基芳基膦。 較佳有機金屬化合物可選自以下所組成之群組··金屬烷 氧化物（較佳為鹼金屬烷氧化物”金屬芳基氧化物，金屬烷 基硫氧化物，金屬芳基硫氧化物，烷基金屬化合物，芳基 金屬化合物及格里納（Grignard)試劑。 备上述驗種類當中一種包含一個垸基，則其可較佳本1 至4個碳原子。若該對應鹼含有2或更多個烷基，則於各情 84146 -10- 200306980 況中，這些烷基可相同或不同，較佳為相同烷基。 ―若上述驗種類當中-種含有一個芳基，則其可較佳為未 經取代或至少經單基取代之苯基。 在根據本發明該方法中，若使用驗金屬燒氧化物作用 鹼J其可較佳付生自鈉，且可較佳具有1至3個碳原子。 、，用於根據本發明方法之反應介質為熟悉本技藝者已知 、用反底」1貝，但其限制條件為這些反應介質不會與該 個別鹼或所得到該個別單氫全氟烷烴產生不可逆化學反 應。 所在根據本發明万法之另—項較佳具體實例中，該反應介 貝為欠右必要可以與一或多種有機溶劑混合，根據本發 ^ L括雙相系統，例如，水及煙之混合物。 、同樣可較佳使用一或多#有機溶劑進行根據本發明製備 該單氫全氟垸烴之方法，其中若使用至少2種溶劑，則若必 要，則可以呈雙相系統之型式。 通用於根據本發明方法之有機溶劑（於各情況中，其可單 獨或與彼此呈任何所要組合型式，若必要，與可以與 )可軚佳選自由醇類，醚類，醯基醯胺類，亞颯類， ^如類及烴類所組成之群組。 較佳醇類為此等在該燒基部份具有⑴個碳原子之醇。 類可較佳選自由甲醇，乙醇，異丙醇及至少2種這此 述醇類之混合物所組成之群組。 7根據本發明大·、、表M , / 乂有目才和的方式（例如，在該反應時藉 溫度及/或壓力’或藉由該全氟燒基魏對驗之莫耳比） 84146 -11- 200306980 控制自所使用該個別全氟烷基磷烷(群)所形成該單氫全氟 烷烴之數量及該其它反應產物之種類。 藉由參數之選擇，可以，例如，特則&、λ 符別自於各情況中所使 用之該二氟三全氟烷基磷烷内切除1， 味丄2或3個全氟烷基。 一旦自該個別二氟三全氟烷基磷烷銘 外冼私除一個全氟烷基 時，除了該所要單氩全氟烷烴外，亦可姓 Τ Τ特別形成該對應雙 (全氟燒基）亞膦酸鹽。 -旦自該個別二氟三全氟垸基錢移除兩個全氟燒基 時’除了孩所要單氫全氟燒烴外，亦可特別形成該對應全 氟烷基膦酸鹽。 應磷 酸鹽 若自該個別二氟三全氟燒基磷垸移除全部3個全氣燒基 時’除了該所要單氫全氟垸烴外’亦可特別得到該對 熟悉本技藝者可藉由簡單的預備實驗衫該相應單氫全 狀垸烴所要組合之最佳參數之個別選擇，其用量及該個別 其它反應產物。 右例如_思自所使用該個別二氟全氟燒基磷燒移除 :個全氟㈣’則可較佳至IGGt之溫度下及二款 二全氟燒基磷⑥對驗之莫耳當量比為1 : 3下進行根據本發 明該方法。 右例如，有意自所使用該個別二氟全氟垸基磷垸移除 兩個全氟乾基’則可較佳於5(TC至15CTC之溫度下及二氟三 全歧基磷烷對鹼之莫耳當量比為i : 4下進行根據本發明 該方法。 84146 -12- 200306980 個八㈣ 氟全氣燒基磷燒移除3 個王乳认基，則可較佳於丨〇〇。〇至25(^之冰 广 全氟烷基磷烷對鹼之莫耳 /皿又下及一貺二 該方法。 莫耳Η比為^下進行根據本發明 化藉由熟悉本技藝者已知之習用方法離析及純 化精由根據本發明該方法所製成之該單氣 =易揮發之化合物，則可藉由，例如，在i或;個:盤 =態氮絲冰冷㈣―其自該反應混 八=:=由熟悉本技藝者已知之習用方法(例如，藉由 刀：厂法或經由適當溶劑萃取)進行其它反 何離析及純化步驟。 右该全氟燒基磷垸與一個無機驗⑻反應，則可直 析後使用酸（較佳使用硫酸），使所形成該雙（全氟燒基）亞膊 奴鹽及全氟垸基膦酸鹽轉化成該對雙（全氟㈣）亞騰酸及 全氣燒基鱗酸。 — "、藉由中和反應（較佳使用有機驗⑷)使以此種方法得到 之該雙（全氟〶基）亞膦酸及全氟燒基膦酸轉化成該鹽。 /由適合驗類之選擇，可較佳製成該局部垸化及全燒化 鉍，鱗’鈮，吡錠’噠肼，嘧啶，吡畊，咪唑，吡唑 唑，噚唑及三峻鹽。 比車乂特佳者為製備具有一種選自以下所組成之 離子之鹽類。 ％ 84146 -13- 200306980 R1I wherein lSnS8 is preferably, and in each case 1, 2, or 3. A more preferred perfluorocarbon-based phosphorus compound is selected from the group consisting of ditrimethylene (pentaethyl) phosphane, difluorotris (n-nonafluorobutyl) phosphane, and difluorotris (n-heptafluoropropyl). A group of leptane and trifluorobis (n-nonafluorobutyl) phosphine. In each case, it is preferred to use only one base, and the perfluorophosphorane compound (group) is processed according to the method of the present invention. However, it is of course also possible to use 2 or more test mixtures in the method according to the invention. It is also possible to use individual bases in the corresponding vehicle 84146 200306980 < type (preferably the corresponding hydrate type, or a conventional adduct type known to those skilled in the art). In another preferred example of the method for preparing a monohydroperfluorocarbon burner according to the present invention, a base (a), preferably an inorganic alkalinization) or an organic base (C) is generally used. The inorganic base (b) is preferably selected from the group consisting of an alkali metal hydroxide and an alkaline earth to a gaseous oxide. In the method according to the present invention, if an alkali metal hydroxide is used as the base (b), it is preferably selected from the group consisting of lithium hydroxide, lithium hydroxide monohydrate, sodium hydroxide, and potassium hydroxide. . In the method according to the present invention, if an alkaline earth metal hydroxide is used as the base (b) ', it is preferably selected from the group consisting of barium hydroxide, barium hydroxide octahydrate and osmium calcium oxide. It is likewise preferable to carry out the method for producing a monohydroperfluoroalkane according to the present invention using an organic base (c) or an organometallic compound. The base (c) may preferably be selected from the group consisting of: alkyl ammonium hydroxide, aryl ammonium hydroxide, alkyl aryl ammonium hydroxide, alkyl scale hydroxide, aryl Scale hydroxide, alkylaryl scale hydroxide, alkylamine, arylamine, alkylarylamine, alkylphosphine, arylphosphine and alkylarylphosphine. Preferred organometallic compounds may be selected from the group consisting of: metal alkoxides (preferably alkali metal alkoxides), metal aryl oxides, metal alkyl sulfide oxides, metal aryl sulfide oxides, Alkyl metal compounds, aryl metal compounds and Grignard reagents. If one of the above-mentioned test types contains a fluorenyl group, it may preferably have 1 to 4 carbon atoms. If the corresponding base contains 2 or more Alkyl groups, in each case 84146 -10- 200306980, these alkyl groups may be the same or different, preferably the same alkyl group.-If one of the above-mentioned test types contains an aryl group, it may be preferably Unsubstituted or at least mono-substituted phenyl. In the method according to the present invention, if a metal test oxide is used as the base J, it may be better derived from sodium, and may preferably have 1 to 3 carbons. Atoms. The reaction medium used in the method according to the present invention is known to those skilled in the art and used inversely, but the limitation is that these reaction media will not interact with the individual base or the individual monohydrogen obtained. Haloalkane produces irreversible chemical reaction In another preferred embodiment of the method according to the present invention, the reaction medium is not necessary and can be mixed with one or more organic solvents. According to the present invention, a two-phase system is included, for example, a mixture of water and smoke The method for preparing the monohydroperfluorofluorene according to the present invention can also be preferably performed using one or more # organic solvents, and if at least two solvents are used, if necessary, it can be in the form of a two-phase system. The organic solvents in the method according to the present invention (in each case, they can be in any desired combination with each other, and if necessary, can be combined with) can be selected from alcohols, ethers, fluorenylamines, Subgroups, such as groups and hydrocarbons. Preferred alcohols are alcohols having at least one carbon atom in the alkyl moiety. The group may preferably be selected from the group consisting of methanol, ethanol, and isopropanol. And a group consisting of a mixture of at least two of these alcohols. 7 According to the present invention, Table M, / 乂 has a purposeful way (for example, by temperature and / or pressure during the reaction ' Or by using the perfluorinated carbon-based Wei Moerbi) 84146 -11- 200306980 Controls the amount of the monohydroperfluoroalkane formed from the individual perfluoroalkylphosphorane (group) used and the type of the other reaction products. By selecting the parameters, you can, for example, the special &, Λ is distinguished from the difluorotriperfluoroalkylphosphorane used in each case by cutting off 1, miso 2 or 3 perfluoroalkyl groups. Once from the individual difluorotriperfluoroalkyl phosphorus In addition to a perfluoroalkyl group, besides the desired monoargon perfluoroalkane, the alkane name can also form the corresponding bis (perfluoroalkyl) phosphinate in particular.-Once from the individual two Fluorotriperfluorofluorene can remove two perfluoroalkyl radicals, in addition to the monohydroperfluorocarbon hydrocarbons required by children, and the corresponding perfluoroalkyl phosphonates can also be formed in particular. Fluorotriperfluorinated phosphorophosphonium can be used to remove all 3 all-gas-fired radicals 'except for the required monohydroperfluorofluorinated hydrocarbon', which can be obtained in particular by those skilled in the art by simply preparing experimental shirts. The individual choices of the best parameters to be combined for the monohydrogenated fluorene, their amounts and the individual other reaction products. For example, _Si is removed from the individual difluoroperfluorocarbon based phosphorous used: a perfluorinated fluorene 'can be better to the temperature of IGGt and two diperfluorocarbon based phosphoric acid ⑥ Moore equivalent The method according to the invention is carried out at a ratio of 1: 3. For example, if you intentionally remove two perfluoro dry radicals from the individual difluoroperfluorofluorenylphosphonium used, then it may be better than 5 (TC to 15CTC and difluorotriperamidophosphorane to alkali The method according to the present invention is performed at a molar equivalent ratio of i: 4. 84146 -12- 200306980 octafluorofluorine-based phosphoric acid is used to remove 3 royal milk recognition groups, which may be better than 丨 〇〇. This method is based on the molar ratio of perfluoroalkylphosphine to alkali and the molar ratio of alkali to alkali. The molar ratio is determined according to the present invention and is known to those skilled in the art. Isolation and purification of conventional methods The single gas = volatile compound made by the method of the present invention can be used, for example, at i or; Mixed eight =: = Other isolation and purification steps are performed by conventional methods known to those skilled in the art (for example, by a knife: factory method or extraction by a suitable solvent). The perfluorinated phosphorophosphonium and an inorganic test For the tritium reaction, an acid (preferably sulfuric acid) can be used after direct analysis, so that the formed bis (perfluorocarbon) alkyl salt and perfluorine are formed. The base phosphonate is converted into the pair of bis (perfluorofluorene) phosphinic acid and the all-gas-fired linolenic acid. — &Quot; The neutralization reaction (preferably using organic testing) makes the obtained in this way. Bis (perfluorofluorenyl) phosphinic acid and perfluoroalkenylphosphonic acid are converted into the salt./Choose from localized and fully calcined bismuth, scale'niobium, pyridine from the choice of suitable test types. Tablets of pyridazine, pyrimidine, pyrimidine, imidazole, pyrazolazole, oxazole and sammonium salt. Those who are better than carpenterol are for the preparation of salts with an ion selected from the group consisting of:% 84146 -13- 200306980 R1

其中R1至R5可相同或不同，其可視需要藉由單键或雙鍵直 接彼此鍵結，且其各（獨立或一起）如下定義： H， -鹵素’其中該鹵素並不會直接與N鍵結， -烷基（匕至^)，其可部份或完全經由其它基團取代，較佳 為 F ， Cl ， N(CnF(2n+1.x)Hx)2 ， 〇(CnF(2n+㈤Ηχ)， s〇2(CnF(2n+1_x)Hx)，cnF(2n+1_x)Hx，其中 ι<η<6且 〇<χ<2η+1。 直接或離析後，使該全氟烷基磷烷與無機鹼（b)之反應進 行鹽互換作用後形成該鹽，則亦可得到這些鹽。 可以使用芳基-，烷基-或烷基芳基_銨或-銹鹽進行該鹽互 換作用。較佳者為使用六氟磷酸鹽，四氟硼酸鹽，六氟坤 酸鹽，硫酸鹽，氟化物，氣化物或溴化物。 84146 -14- 200306980 方法進行以此種方法得 可以以熟悉本技藝者已知之習用 到之該鹽類之加工。 根據本發明製備單氫全氟垸烴之方法可以簡單，及可靠 地製備很高產率之這些化合物。更詳細地說，可以以費用 不向的万法製備該可作為起始化合物之全氟燒基㈣。 根據本發明該方法所得到該副產物（例如，該雙（全說垸基） 亞膦酸鹽及全氟燒基膦酸鹽）最好本身為尤其適於製備該 相應雙（全氟虎基）亞膦酸及全氟燒基膦酸之珍貴原料，因此 可經濟上地利用，使用適合驗進行中和反應可製備適於作 為離子液體，表面活化劑或相轉移催化劑。 、=它優點為可以使藉由根據本發明該方法進行之該反應 :壤境：擊減至很低，而且其對於藉由根據本發明該方法 製備孩單氫全氟烷烴之製造成本有正面影響。 ，匕外’可以於其製備後立即得到高純度：該個別單氫全 亂烷烴，亦即，不需要複雜純化步騾。 【實施方式】 參考以下各實例說明本發明。這些實例僅提供以解釋本 务月並非限制本發明的一般概念。 實例 實例1 1〇·40克（ι85·4毫莫耳）氫氧化钾溶解在燒瓶之别立方 a刀水中，於-5 C浴溫下冷卻所形成該溶液。接著以丨5分 叙，精由滴液漏斗添加25.53克（59 9毫莫耳）二氣三（五氣乙 基）&烷，並攪拌。接著使該反應混合物達至室溫。在2個 84146 -15- 200306980 後續收集器中收集藉由二氟三（五氟乙基）磷烷之鹼性水解 所形成該氣態五氟乙烷，並以液體氮冷卻各該收集器。在 孩已冷卻收集器内得到沸點為之6·67克固體五氟乙 燒。孩值相當於 L. Conte 等人在 J. Fluor. Chem.，38 (1988)， 第319-326頁中所述之值。 根據於這些條件下自該二氟三（五氟乙基）磷烷所移除之 五氟乙基，該五氟乙烷之產率為92.8%。 該燒瓶内之反應混合物尚含雙（五氟乙基）亞膦酸鉀 ((C2F5)2P(〇)〇k)及氟化鉀之溶液。為了離析該雙（五氟乙基） 亞膦酸鉀，首先使用幾滴氟化氫水溶液中和該過量氫氧化 鉀，並於減壓下移除該水。於120帕減壓及1〇(rCs溫下使 所形成該固體殘留物乾燥兩小時。 使用150jl方公分之甲醇自該乾燥殘留物萃取雙（五氟乙 基）亞膦酸鉀。接著於120 pa減壓蒸餾該甲醇，並乾燥該雙 (五氟乙基）亞膦酸鉀。以所使用該二氟三（五氟乙基）磷烷為 基準計’該產率為19.0克，相當於932〇/〇。 可藉由及19F-NMR光譜學表示該五氟乙烷之特徵，並 藉由F-及P-NMR光譜學表示該雙（五氟乙基）亞膦酸鉀之 特徵。 五氟乙烷 使用Bmker WP 80 SY分光計於8(λ1 MHz(就lH而言）及 75.4 MHz(就19F而言）頻率與_7〇〇c溫度下記錄該lH_及 19f-nmr光譜。據此，利用薄壁5毫米nmr管（其具丙酮_〇6 膜作為外鎖及tms或caj溶解在該丙酮_D6膜内，作為外 84146 -16- 200306980 參考物）内之FEP(氟乙烯聚合物）。 iH-NMR光譜： (丙酮-06膜，該膜中之參考物TMS，δ，ppm) 5.80 tq; 2Jh,f=52.3 Hz; 3JHjF=2.1 Hz 19f-nmr光譜： (丙酮-D6膜’該膜中之參考物cci3F，δ，ppm) -86.54 s (CF3); - 1 38.55 d (CHF2); 2JH,F=52.5 Hz 所得到該資料相當於M.D. Bartberger等人在Tetrahedron， 53，弟 29 期（1997)，弟 9857-9880 頁及 Ν· Ignative 等人在 ActaWherein R1 to R5 may be the same or different, they may be directly bonded to each other through a single bond or a double bond, and each of them (independently or together) is defined as follows: H, -halogen 'wherein the halogen is not directly bonded to the N bond -An alkyl group (from 1 to ^), which may be partially or completely substituted by other groups, preferably F, Cl, N (CnF (2n + 1.x) Hx) 2, 〇 (CnF (2n + ㈤Ηχ), s〇2 (CnF (2n + 1_x) Hx), cnF (2n + 1_x) Hx, where ι < η < 6 and 〇 < χ < 2η + 1. The perfluoroalkane is made directly or after isolation. These salts can also be obtained after the salt interchange reaction between the reaction of the base phosphane and the inorganic base (b). These salts can also be obtained by using aryl-, alkyl- or alkylaryl-ammonium or -rust salts. Interchange effect. It is better to use hexafluorophosphate, tetrafluoroborate, hexafluoroquinate, sulfate, fluoride, gaseous or bromide. 84146 -14- 200306980 method Those skilled in the art are familiar with the processing of such salts. The method for preparing monohydroperfluorofluorene according to the present invention can be simple and reliable to produce these compounds in high yields. In more detail, the perfluorinated fluorene that can be used as a starting compound can be prepared in a cost-effective manner. The by-products obtained according to the method of the present invention (for example, the bis (all-fluorenyl) group) Phosphonates and perfluoroalkanyl phosphonates) are preferably precious raw materials which are especially suitable for preparing the corresponding bis (perfluoroorthyl) phosphinic acid and perfluoroalkanyl phosphonic acid, and therefore can be economically used, The neutralization reaction can be performed using a suitable test to prepare a suitable as an ionic liquid, a surfactant or a phase transfer catalyst. It has the advantage that the reaction performed by the method according to the present invention can be performed: Moreover, it has a positive impact on the manufacturing cost of preparing monohydroperfluoroalkanes by the method according to the present invention. In addition, it can obtain high purity immediately after its preparation: the individual monohydroperfluoroalkanes, that is, No complicated purification steps are required. [Embodiments] The following examples are used to illustrate the present invention. These examples are provided only to explain that this month does not limit the general concept of the present invention. Examples Example 1 10 · 40 g (85 · 4 mmol) Ear) Potassium hydroxide was dissolved in a cubic a knife water in the flask, and the resulting solution was cooled at a bath temperature of -5 C. Then, in 5 minutes, 25.53 grams (59 9 millimoles) was added from the dropping funnel. Digastris (pentaethyl) & alkane, and stirred. The reaction mixture was then allowed to reach room temperature. Collected in two 84146 -15- 200306980 subsequent collectors by difluorotris (pentafluoroethyl) The gaseous pentafluoroethane was formed by alkaline hydrolysis of phosphine, and each of the collectors was cooled with liquid nitrogen. In the cooled collector, a boiling point of 6.67 grams of solid pentafluoroethane was obtained. The equivalent of a child is equivalent to The values described by L. Conte et al., J. Fluor. Chem., 38 (1988), pages 319-326. Based on the pentafluoroethyl removed from the difluorotris (pentafluoroethyl) phosphine under these conditions, the yield of the pentafluoroethane was 92.8%. The reaction mixture in the flask still contained a solution of potassium bis (pentafluoroethyl) phosphinate ((C2F5) 2P (0) OK) and potassium fluoride. To isolate the potassium bis (pentafluoroethyl) phosphinate, the excess potassium hydroxide was first neutralized with a few drops of aqueous hydrogen fluoride solution, and the water was removed under reduced pressure. The solid residue formed was dried for two hours at a reduced pressure of 120 Pa and a temperature of 10 ° C. Potassium bis (pentafluoroethyl) phosphinate was extracted from the dried residue using 150 μl of cm 3 methanol. Then at 120 The methanol was distilled under reduced pressure, and the potassium bis (pentafluoroethyl) phosphinate was dried. Based on the difluorotris (pentafluoroethyl) phosphorane used, the yield was 19.0 g, which is equivalent to 932 //. The characteristics of the pentafluoroethane can be expressed by 19F-NMR spectroscopy, and the characteristics of the potassium bis (pentafluoroethyl) phosphinate can be expressed by F- and P-NMR spectroscopy. Pentafluoroethane was recorded using a Bmker WP 80 SY spectrometer at a frequency of 8 (λ1 MHz (for 1H) and 75.4 MHz (for 19F)) and a temperature of 700 ° C. Accordingly, the FEP (fluoroethylene) in a thin-walled 5 mm nmr tube (which has an acetone_〇6 film as an outer lock and tms or caj dissolved in the acetone_D6 film as an outer 84146 -16-200306980 reference) Polymer) iH-NMR spectrum: (acetone-06 film, reference TMS, δ, ppm in this film) 5.80 tq; 2Jh, f = 52.3 Hz; 3JHjF = 2.1 Hz 19f-nmr spectrum: (acetone-D6 membrane References in this film cci3F, δ, ppm) -86.54 s (CF3);-1 38.55 d (CHF2); 2JH, F = 52.5 Hz The data obtained is equivalent to MD Bartberger et al. In Tetrahedron, 53, brother 29 Issue (1997), pp. 9557-9880 and N. Ignative et al. In Acta

Chem· Scand. 53，第 12 期（1999)，第 1110-1116 頁中所述之 值。 雙（五氟乙基）亞膦酸4甲（（C2f5)2P(〇)〇k) 使用Bmker Avance 300分光計，於282 4 MHz(就19F而言） 及121.5?^112(就31?而言）之頻率下記錄該1917-及31?-；^]^光 譜。 19F-NMR 光譜： (溶劑丙酮-D6，内參考物CC13F，δ，ppm) -80.38 m (CF3); -125.12 dm (CHF2); 2jpf=67.3 Hz 31p-nmr 光譜： (落劑丙酮-D6 ’在D2〇内，參考物85重量度H3p〇4，δ，ppm) 0·72 quin; 2Jp，f=67.2 Hz 實例2 : 使5.99克（142.8¾莫耳）氫氧化鋰單水合物溶解在燒杯内 之15 0三方公分水中’並於_ 1 〇浴溫下冷卻所形成該溶 84146 -17- 200306980 液接著以15分鐘藉由滴液漏斗添加19 3〇克（45·3毫莫耳） 二氟三（五氟乙基）磷垸，並攪拌。接著使該反應混合物達至 室溫。在兩個後續收集器内收集藉由該二氟三(五氟乙基) 魏水解所形成該氣態五氟乙燒，使各該收集器經液體氮 冷卻。在該已冷卻收集器内得到如固體之4_95克五氟乙烷。 以於這些條件下自該二氟三（五氟乙基）磷烷所移除之五氟 乙基為基準計，該五氟乙烷之產率為912%。 该燒瓶内 < 反應混合物尚含雙（五氟乙基）亞膦酸鋰 ((C2H5)2P(0)0Ll)及氟化鋰之溶液。為了離析該雙（五氟乙基） 亞膦酸J里，首先使用幾滴氟化氫水溶液中和該過量氫氧化 鋰，濾出该氟化鋰沉澱物，於減壓下移除該水。於丨2〇帕減 壓及100 C浴溫下使所形成雙（五氟乙基）亞膦酸鋰之白色固 體乾燥2小時。 得到13.1克含約2重量％氟化鋰之雙（五氟乙基）亞膦酸 鋰，以所使用該二氟三（五氟乙基）磷烷為基準計，其相當於 93.7%產率。 藉由1H-及19F-NMR光譜學表示該五氟乙烷之特徵，並藉 由19F-及31P-NMR光譜學表示該雙（五氟乙基）亞膦酸魏之特 徵。 測定五氟乙燒之化學位移，其值相當於實例1所示之值。 雙（五氟乙基）亞膦酸鋰 使用 Bruker Avance 300分光計，於282.4 MHz(就 19F而言） 及121·5 MHz(就31P而言）之頻率下記錄該19F-及31P-NMR光 84146 -18- 200306980 19f-nmr光譜： (溶劑丙酮①6，内參考物ecu，s，ppm) -80-32 m(CF3); -125.08 dm (CHF2)；2jp)F=72.6 Hz 31p-nmr 光譜： (溶劑丙酮-D6,在丙酮_D0内，參考物85重量％1131>〇4_15重 量 ％D2〇，δ，ppm) 0.27 quin; 2JP,F=72.7 Hz 實例3 : 使4·1克（73·1耄莫耳）氫氧化鉀溶解在燒瓶内之15〇立方公 分水中，並於0 C浴溫下冷卻所形成該溶液。接著以3分鐘 藉由滴液漏斗添加16.87克（23·2毫莫耳）二氟三（正_九氟丁 基）磷烷，並攪拌。接著使該反應混合物達至室溫，於該溫 度下攪拌8小時’接著再使其回流8小時。在一個後續收集 器内收集藉由孩二氟三（正-九氟丁基）磷烷水解所形成該氣 態1Η-九氟-正-丁烷，使該收集器經乾冰冷卻。 在该已冷卻收集器内得到3 ·63克彿點為14。〇之液態1Η·* 正-五氟丁燒。 以於這些條件下自該二氟三（正-九氟丁基）磷烷移除之正 -九氟丁基為基準計，該1H-正-九氟丁基之產率為71.2%。 自同樣餘留在該燒瓶内之該黏性殘留物分離餘留在該燒 瓶内之溶液，並使用鹽酸中和。為了離析該雙（正_九亂丁基） 亞膦酸鉀，於減壓下移除該水。於120帕減壓及1〇〇 浴溫 下使所形成該固體殘留物乾燥2小時。接著以3份各5 〇立方 公分之甲醇萃取該乾燥殘留物，合併各該餾份，接著於125 84146 -19- 200306980 帕減壓下蒸餾出該甲醇，並乾燥該固體殘留物。該雙（正_ 九氟丁基）亞膦酸鉀之產率為7.88克，以所使用該二氟三（正 -九氟丁基）磷烷為基準，其產率相當於62.9%。 可藉由及19F-NMR光譜學表示該1H-正-九氟丁烷之特 倣，並藉由19F-及31P-NMR光譜學表示該雙（正-九氟丁垸）亞 膦酸卸之特徵。 1H-九氟丁烷 使用Bmkei* WP 80 SY分光計，於80.1 MHz(就1Η而言）及 75.4 MHz(就19F而言）頻率下，記錄該1η-及19F-NMR光譜。 據此，利用薄壁5毫米NMR管（其具丙酮-D6膜作為外鎖，及 TMS或CChF溶解在該丙酮_d6膜内作為外參考物）内之 FEP(氟乙烯聚合物）管。 h-NMR光譜： (丙酉同-Ds膜’该膜内之參考物TMS，δ，ppm) 6·14 tt; 2JH F=52.0 Hz; 3JH F=5.0 Hz 19F-NMR光譜： (丙酮46膜，該膜内之CC13F，δ，ppm) 81.31 t (CF3)； -127.93 m (CF2)； -131.06 m (CF2); -137.92 dm (CF〗)；2Jh ρ=52·0 Hz 所得到該值等於T. Hudlicky等人在J. 〇f Fluorine Chem·， 59，第1期（1992)，第9-14頁中該文獻公告中所揭示該值。 雙（正-九氟丁烷）亞膦酸鉀Chem. Scand. 53, Issue 12 (1999), pages 1110-1116. Bis (pentafluoroethyl) phosphinic acid 4methyl ((C2f5) 2P (〇) 〇k) using a Bmker Avance 300 spectrometer at 282 4 MHz (for 19F) and 121.5? 112 (for 31? And The frequencies of the 1917- and 31?-; ^] ^ Spectra were recorded at a frequency of ??). 19F-NMR spectrum: (solvent acetone-D6, internal reference CC13F, δ, ppm) -80.38 m (CF3); -125.12 dm (CHF2); 2jpf = 67.3 Hz 31p-nmr spectrum: (falling agent acetone-D6 ' Within D2O, reference weight 85 H3po4, δ, ppm) 0.72 quin; 2Jp, f = 67.2 Hz Example 2: 5.99 g (142.8¾ mole) of lithium hydroxide monohydrate was dissolved in a beaker The solution was formed within 150 cubic centimeters of water and cooled at -10 bath temperature to form the solvent 84146 -17- 200306980, and then 19 30 g (45 · 3 mmol) was added through a dropping funnel over 15 minutes. Fluorotris (pentafluoroethyl) phosphonium phosphonium and stir. The reaction mixture was then allowed to reach room temperature. The gaseous pentafluoroethane formed by the difluorotris (pentafluoroethyl) hydrolysis was collected in two subsequent collectors, and each of the collectors was cooled by liquid nitrogen. 4 to 95 g of pentafluoroethane was obtained as a solid in the cooled collector. Based on the pentafluoroethyl removed from the difluorotris (pentafluoroethyl) phosphine under these conditions, the yield of the pentafluoroethane was 912%. The reaction mixture in the flask also contained a solution of lithium bis (pentafluoroethyl) phosphinate ((C2H5) 2P (0) 0Ll) and lithium fluoride. To isolate the bis (pentafluoroethyl) phosphinic acid J, the excess lithium hydroxide was first neutralized with a few drops of aqueous hydrogen fluoride solution, the lithium fluoride precipitate was filtered off, and the water was removed under reduced pressure. The formed white solid of lithium bis (pentafluoroethyl) phosphinate was dried under a pressure of 20 Pa and a bath temperature of 100 C for 2 hours. 13.1 g of lithium bis (pentafluoroethyl) phosphinate containing about 2% by weight of lithium fluoride was obtained. Based on the difluorotris (pentafluoroethyl) phosphorane used, it was equivalent to a yield of 93.7%. . The characteristics of the pentafluoroethane are expressed by 1H- and 19F-NMR spectroscopy, and the characteristics of the bis (pentafluoroethyl) phosphinic acid are expressed by 19F- and 31P-NMR spectroscopy. The chemical shift of pentafluoroethane was measured, and its value was equivalent to that shown in Example 1. The lithium bis (pentafluoroethyl) phosphinate was recorded using the Bruker Avance 300 spectrometer at 282.4 MHz (for 19F) and 121.5 MHz (for 31P). 84146 -18- 200306980 19f-nmr spectrum: (solvent acetone①6, internal reference ecu, s, ppm) -80-32 m (CF3); -125.08 dm (CHF2); 2jp) F = 72.6 Hz 31p-nmr spectrum : (Solvent acetone-D6, within acetone_D0, reference 85% by weight 1131> 〇4_15% by weight D20, δ, ppm) 0.27 quin; 2JP, F = 72.7 Hz Example 3: Make 4.1 · g (73 · 1 mol) potassium hydroxide was dissolved in 150 cubic centimeters of water in the flask, and the resulting solution was cooled at a bath temperature of 0 C. Then, 16.87 g (23.2 mmol) of difluorotri (n-nonafluorobutyl) phosphine was added through a dropping funnel over 3 minutes, and stirred. The reaction mixture was then allowed to reach room temperature, stirred at that temperature for 8 hours' and then allowed to reflux for another 8 hours. The gaseous 1Η-nonafluoro-n-butane formed by the hydrolysis of hexafluoro (n-nonafluorobutyl) phosphorane was collected in a subsequent collector, and the collector was cooled on dry ice. In this cooled collector, 3.63 grams of Buddha points were obtained. 〇The liquid 1Η · * n-pentafluorobutane. Based on the n-nonafluorobutyl removed from the difluorotris (n-nonafluorobutyl) phosphine under these conditions, the yield of the 1H-n-nonafluorobutyl was 71.2%. The solution remaining in the flask was separated from the viscous residue also remaining in the flask, and neutralized with hydrochloric acid. In order to isolate the potassium bis (n-nonabutyl) phosphinate, the water was removed under reduced pressure. The solid residue formed was dried under reduced pressure of 120 Pa and 100 bath temperature for 2 hours. The dried residue was then extracted with 3 parts of 50 cm 3 of methanol, the fractions were combined, and then the methanol was distilled off under reduced pressure at 125 84146 -19- 200306980 Pa, and the solid residue was dried. The yield of the potassium bis (n-nonafluorobutyl) phosphinate was 7.88 g. Based on the difluorotri (n-nonafluorobutyl) phosphine used, the yield was equivalent to 62.9%. The special imitation of 1H-n-nonafluorobutane can be expressed by 19F-NMR spectroscopy, and the bis (n-nonafluorobutane) phosphinic acid can be expressed by 19F- and 31P-NMR spectroscopy. feature. 1H-Ninefluorobutane The Bmkei * WP 80 SY spectrometer was used to record the 1η- and 19F-NMR spectra at 80.1 MHz (for 1 就) and 75.4 MHz (for 19F). Accordingly, a FEP (fluoroethylene polymer) tube in a thin-walled 5 mm NMR tube (with an acetone-D6 film as an external lock, and TMS or CChF dissolved in the acetone_d6 film as an external reference) was used. h-NMR spectrum: (Proton-Ds film 'reference material TMS, δ, ppm in this film) 6 · 14 tt; 2JH F = 52.0 Hz; 3JH F = 5.0 Hz 19F-NMR spectrum: (acetone 46 film , CC13F, δ, ppm in the film 81.31 t (CF3); -127.93 m (CF2); -131.06 m (CF2); -137.92 dm (CF〗); 2Jh ρ = 52 · 0 Hz Equal to the value disclosed in the publication by T. Hudlicky et al., J. Of Fluorine Chem., 59, No. 1 (1992), pages 9-14. Potassium bis (n-nonafluorobutane) phosphinate

使用 Bruker Avance 300分光計，於282·4 MHz(就 i9F而言） 及121.5 MHz(就31P而言）之頻率下，記錄該i9F-及31p-NMR 84146 -20- 200306980 光譜。 19F-NMR光譜： (溶劑 D20，在 D20 中參考物 cf3COOH=76.53 ppm，δ，ppm) -82.69 tt (CF3); -122.33 m (CF2); -123.31 dm (CF2); -127.46 tm (CF2); 2JH，F=79.5; 4JF F=9.6 Hz; 4JF，F=12.0 Hz;JF，F=1.5 Hz 31P-NMR 光譜： (溶劑D20 ’内參考物85重量％仏？〇4，ppm) 4.81 quin; 2JPjF=78.9 Hz 實例4 : 使7.0克（124.8毫莫耳）氫氧化鉀溶解在燒瓶内之10立方 公分水中，於70-80°C浴溫下溫熱所形成該溶液。接著以20 分鐘藉由滴液漏斗添加12.18克（16.8毫莫耳）二氟三（正-九 氟丁基）磷烷，並攪拌。然後於15〇t：浴溫下溫熱該反應混 合物，並於該溫度下再攪拌2小時。 在一個後續收集器内收集藉由該二氟三（正-九氟丁基）磷 烷水解所形成該氣態1H-正-九氟丁烷，使該收集器經乾冰 冷卻。 在該已冷卻收集器中得到6.12克液體1H-正·九氟丁烷。以 於這些條件下，自該二氟三（正-九氟丁基）磷烷所移除之這 兩個正-九氟丁烷為基準計，該1H-正-九氟丁烷之產率為 82.9% 〇 使殘留在該燒瓶内之該殘留物溶解在50立方公分水中， 並使用氟化氫水溶液中和該過量氫氧化鉀。 為了離析該（正-九氟丁基）膦酸二钾，於減壓下移除該 84146 -21 - 200306980 水。於120帕減壓及100°C浴溫下使所形成該固體殘留物乾 2小時。接著使用2份各5 0立方公分之甲醇自該乾燥殘留 物萃取該（正-九氟丁基）膦酸二_C4F9p(0)(0K)2 ,合併該餾 份’並蒸餾該甲醇。接著於125帕減壓下乾燥該固體殘留 物。該（正-九氟丁基）膦酸二鉀之產率為5 〇克，以所使用該 二氟三（正-九氟丁基）磷烷為基準計，其產率為79·2%。 · 可藉由及19F-NMR光譜學表示該_九氟丁烷之特 ， 徵，並藉由19F-及31P-NMR光譜學表示該（正_九氟丁烷）膦酸 〇 二鉀之特徵。 測定該1H-正-九氟丁基之化學位移，其相當於實例3所示 之值。 (正·九氟丁烷）膦酸二鉀c4f9p(o)(ok)2 使用 Bmker Avance 300分光計，於282.4 MHz(就19F而言） 及121.5 MHz(就31P而言）之頻率下記錄該i9Fj3ip_NMR光 譜。 19F-NMR光譜：Using a Bruker Avance 300 spectrometer, the i9F- and 31p-NMR 84146 -20- 200306980 spectra were recorded at frequencies of 282.4 MHz (for i9F) and 121.5 MHz (for 31P). 19F-NMR spectrum: (solvent D20, reference cf3COOH in D20 = 76.53 ppm, δ, ppm) -82.69 tt (CF3); -122.33 m (CF2); -123.31 dm (CF2); -127.46 tm (CF2) 2JH, F = 79.5; 4JF F = 9.6 Hz; 4JF, F = 12.0 Hz; JF, F = 1.5 Hz 31P-NMR spectrum: (solvent D20 'internal reference 85% by weight 仏? 〇4, ppm) 4.81 quin 2JPjF = 78.9 Hz Example 4: 7.0 g (124.8 mmol) of potassium hydroxide was dissolved in 10 cubic centimeters of water in a flask, and the solution was formed by warming at a bath temperature of 70-80 ° C. Then, 12.18 g (16.8 mmol) of difluorotris (n-nonafluorobutyl) phosphine was added through a dropping funnel over 20 minutes, and stirred. The reaction mixture was then warmed at 150 ° C: bath temperature and stirred for another 2 hours at this temperature. The gaseous 1H-n-nonafluorobutane formed by hydrolysis of the difluorotris (n-nonafluorobutyl) phosphine was collected in a subsequent collector, and the collector was cooled by dry ice. 6.12 g of liquid 1H-n-nonafluorobutane was obtained in the cooled collector. Based on the two n-nonafluorobutanes removed from the difluorotris (n-nonafluorobutyl) phosphine under these conditions, the yield of the 1H-n-nonafluorobutane It was 82.9%. The residue remaining in the flask was dissolved in 50 cubic centimeters of water, and the excess potassium hydroxide was neutralized with an aqueous hydrogen fluoride solution. To isolate the dipotassium (n-nonafluorobutyl) phosphonate, the 84146 -21-200306980 water was removed under reduced pressure. The solid residue formed was dried at a reduced pressure of 120 Pa and a bath temperature of 100 ° C for 2 hours. The (n-nonafluorobutyl) phosphonic acid di_C4F9p (0) (0K) 2 was then extracted from the dry residue using 2 parts of 50 cm³ of methanol each, the fractions' were combined and the methanol was distilled. The solid residue was then dried under reduced pressure of 125 Pa. The yield of di (n-nonafluorobutyl) phosphonic acid potassium was 50 g. Based on the difluorotri (n-nonafluorobutyl) phosphine used, the yield was 79.2%. . · The characteristics of this nonafluorobutane can be expressed by 19F-NMR spectroscopy, and the characteristics of the (n-nonafluorobutane) phosphonic acid potassium dipotassium can be expressed by 19F- and 31P-NMR spectroscopy. . The chemical shift of 1H-n-nonafluorobutyl was measured, and it corresponds to the value shown in Example 3. (N-Ninefluorobutane) dipotassium c4f9p (o) (ok) 2 Using a Bmker Avance 300 spectrometer, record this at 282.4 MHz (for 19F) and 121.5 MHz (for 31P) i9Fj3ip_NMR spectrum. 19F-NMR spectrum:

C (落劑D20,在D2〇中之參考物CF3COOH=76 53 ppm，δ，ppm) -81.64 tt (CF3); -121.94 m (CF2)； -122.86 dm (CF2); -126.66 tm (CF2); 2Jp,f=68.9 Hz; 4Jf>f=9.6 Hz; 4Jf,f=13.4 Hz;Jff=3.9 Hz。 31P-NMR 光譜： (浴劑D20 ’在D20中參考物85重量％H3P〇4，δ，ppm) 4.00 tt; 2Jp>f=68.8 Hz; 3JPjF=3.4 Hz 實例5 : 84146 -22- 200306980 使8.0克（190.5愛莫耳）氫氧化麵單水合物懸浮在燒瓶内之 乂方a刀水中，並於7〇_8(rc浴溫下溫熱所形成該懸浮 液。接著以30分鐘藉由滴液漏斗添加2121克（29·2毫莫耳） 二氟三（正-九氟丁基）磷烷，並攪拌。然後使該反應混合物 μ熱至1 50 C浴溫，並於該溫度下再攪拌2小時。 在一個後續收集器内收集藉由該二氟三（正·九氟丁基）磷 烷水解所形成該氣態1Η-正-九氟-丁烷，使該收集器經乾冰 冷卻。 在孩已冷卻收集器内得到7·24克液體1沁正_九氟丁烷。以 於這些條件下自該二氟三（正-九氟丁基）磷烷所移除之這兩 種正-九氟丁基為基準計，該lH—正-九氟丁烷之產率為 56.3% 〇 使殘留於該燒瓶内之殘留物溶解於5〇立方公分之水中， 使用氟化氫水溶液中和該過量氫氧化鋰，並濾出所形成該 氟化鍾沉澱物。為了離析該（正-九氟丁基）膦酸二鋰 C4F9P(〇)(〇Li)2，於減壓下移除該水。於丨2〇帕減壓及 浴溫下使所形成白色固體乾燥2小時。得到8.0克（正-九氟丁 基）膦酸二鋰，以所使用該二氟三（正-九氟丁基）磷烷為基 準’其產率相當於87.8%。 可藉由及19F-NMR光譜學表示該1H-正-九氟丁燒之特 徵，並藉由19F-及31P-NMR光譜學表示該雙（正-九氟丁烷）膦 酸二鉀之特徵。 測定該1H-正-九氟丁烷之化學位移，其相當於實例3所示 之值。 84146 -23- 200306980 正-九氟丁基膦酸二鋰 使用 Bruker Avance 300分光計，於282.4 MHz(就 19F而言） 及121.5 MHz(就31P而言）之頻率下記錄該i9f-及31p_NMR光 譜。 19F-NMR光譜： (落劑 D〗〇 ’ 在 D20 中之參考物 CF3COOH=76.53 ppm，δ，ppm) -81.85 tt (CF3); -122.03 m (CF2); -123.06 dm (CF2); -126.79 tm (CF2); Jp，f = 70.1 Hz; 4Jff=9.5 Hz; 4Jf，f=14.2 Hz;Jf，f=3.9 Hz (溶劑丙酮-D6，内參考物CC13F，δ，ppm) -80.92 m (CFS); -120.66 m (CF2); -122.70 dm (CF2)； -125.62 tm (CF2); 2Jp，f=78.6 Hz; 4Jff=9.9 Hz; 4Jf，f=14.5 Hz; Jf，f=3.2 Hz 31p-nmr 光譜： (落劑D2〇 ’在D20内，參考物85重量0/〇H3p〇4，δ，ppm) 3·81 tt; 2JP F=70.1 Hz; 3JP，F=3.3 Hz (〉谷劑丙@同-〇6，在丙酮_D6中，參考物85重量％h3p〇4-15% 〇2〇，δ，ppm) -0.28 t; 2JP F=78.1 Hz 實例6 : 使10.24克（182.5毫莫耳）氫氧化鉀溶解在燒瓶内之10立方 公分水中，並於65-7〇°c浴溫下溫熱所形成該溶液。接著以 60分鐘藉由滴液漏斗添加18 7〇克（43·9毫莫耳）二氟三（五氟 乙基）鱗燒，並攪拌。接著於120t浴溫下溫熱該反應混合 84146 -24- 200306980 物，並於該溫度下再攪拌1小時。 在一個後續收集器内收集藉由二氟三（五氟乙基）磷烷水 解所形成該氣態五氟乙烷’使該收集器經液體氮冷卻。 在該已冷卻收集器内得到9.99克固體五氟乙烷。以於這 些條件下自該二氟三（五氟乙基）磷烷所移除之這兩種五氟 乙基為基準計，該五氟乙烷之產率為94 8〇/。。 使殘留在該燒瓶内之殘留物溶解在4〇立方公分水中，並 使用幾滴氟化氫水落液中和該過量氫氧化_。 為了離析該五氟乙基膦酸二卸，於減壓下移除該水。於 120帕減壓及1 〇〇°c浴溫下使所形成該固體乾燥丨小時。接著 使用兩份各50立方公分之甲醇自該固體殘留物萃取該五氣 乙基膦酸二鈉，合併該餾份，濾出該甲醇，並於12〇帕減壓 下乾燥所形成該殘留物。 得到16.54克五氟乙基膦酸二鉀二（氟化卸） (C2F5P(〇)(〇K)2>2KF，以所使用該二敦三（五氟乙基）鱗烷為 基準’其產率相當於96.1%。 可藉由及19F-NMR光譜學表示該五氟乙燒之特徵，並 藉由19f-及31P-NMR光譜學表示該五氟乙基膦酸二鉀二（說 化鉀）之特徵。 測定該五氟乙烷之化學位移，其相當於實例1所述之值。 五氟乙基膦酸二钾二（氟化鉀） 19F-NMR光譜： (溶劑 D2〇，在 D2〇内，參考物 CF3c〇〇H=76.53 ppm，δ，ppm) ’·86 t (CF3); -125.91 q (CF2); -122.70 s (2KF); 2JP，产68.4 Ηζ· 84146 -25- 200306980 3 J F,F= 1.6 Hz 31P-NMR 光譜： (溶劑D2〇，在D2〇内，參考物85重量％1*13?04，δ，ppm) 3 · 17 t; 2 J p F=6 8 · 4 Η z 實例7 : 使8.50克（151.5毫莫耳）氫氧化钾溶解在燒瓶内之心^立方 公分水中，並於70-80°C浴溫下溫熱所形成該溶液。接著以 90分鐘藉由滴液漏斗添加15 77克（37 〇毫莫耳）二氟三（五氟 乙基）磷烷，並攪拌。 在一個後續收集器内收集藉由該二氟三（五氟乙基）磷烷 K解所形成该氣怨五氟乙燒，並使該收集器液體氮經冷卻。 在該已冷卻收集器内得到8·30克固體五氟乙烷。以於這 些條件下自該二氟三（五氟乙基）磷烷所移除之這兩種五氟 乙基為基準計，該五氟乙烷之產率為93.4%。 測定該五氟乙烷之化學位移，其相當於實例1所述之值。 實例8 : 使6.23克（111·〇毫莫耳）氫氧化鉀溶解在燒瓶内之1218克 乙醇/水混合物（1 : 1重量份數）内，並於55-6〇。(：浴溫下溫熱 所形成該溶液。接著以45分鐘藉由滴液漏斗添加丨丨43克 (26.8毫莫耳）二氟三（五氟乙基）磷烷，並攪拌，且於肋它下 使该反應混合物加熱1 〇分鐘。 在一個後續收集器内收集藉由該二氟三（五氟乙基）磷烷 水解所形成該氣態五氟乙烷，並使該收集器經液體氮冷卻。 在該已冷卻收集器中得到5.23克固體五氟乙烷。以於這 84146 -26- 200306980 ,牛下自μ—氟二（五氟乙基）磷烷所移除這兩種五氣乙 基為基準計，該五氟乙燒之產率為81.3%。 測定該五氟（乙燒士仆與^ 化予位移，其相當於實例1所述之值。 實例9 : 、1 /皿下以1小時藉由滴液漏斗添加13.46克（31·6毫莫 耳）二氟三（五氟乙基）磷烷至96.5克（131.丨毫莫耳）2〇重量％ 四乙基氫氧化鈉水溶液内，並攪拌。 操作時，觀察該反應混合物之溫熱。 接著太80 C下使该反應混合物加熱3〇分鐘。在一個後續 收集器内收集藉由該二氟三（五氟乙基）鱗燒水解所形成該 氣悲五氟乙烷，並使該收集器經由液體氮冷卻。 在該已冷卻收集器内得到7.49克固體五氟乙烷。以所移 除這兩種五氟乙基為基準計，該五氟乙烷之產率為98.8%。 測足該五氟乙烷之化學位移，其相當於實例1所述之值。 利用旋轉蒸發器蒸發殘留在該燒瓶内之溶液，於120帕減 壓及100°C溫度下乾燥所形成固體，得到24·67克白色結晶狀 [(C2H5)4N]2[C2F5P03].2[(C2H5)4N]F.8H20。 可藉由咕-，19F-，31P-NMR光譜學及元素分析表示該 [(C2H5)4N]2[C2F5P〇3>2[(C2H5)4N]F.8H20之特徵。 利用Bruker Avance 300分光計於282.4 MHz(就19F而言）及 121.5 MHz(就31P而言）頻率記錄該19F-，及31P-NMR光譜。 19f-nmr 光譜： (溶劑乙腈-D3，參考物CC13F，δ，ppm) -79.41 dt (CF3); -126.74 dq (CF2); -111.74 (2F-); 2JP，F=54.〇 Hz; 84146 -27- 200306980 3JPF=1.1 Hz; 3JF，F=l.〇 Hz W-NMR光譜： (溶劑乙腈-D3，參考物TMS，δ，ppm) 1.21 tm (CH3); 3.28 q (CH2); 3JH,H-7.3 Hz 在該H2〇分子與該溶劑之氘之間進行質子交換； 31p-nmr 光譜： (溶劑乙赌-r>3，在乙腊令中，參考物以重量％H3P〇4_15〇/〇 D2〇，δ，ppm) Ί.77 t; 2JP)F=54.2 Hz 元素分析： C34H96F5N4〇llP之計算值：c: 47 31%; H: u 21%; N: 6 49〇/〇 實測值：C: 47.37%; H: 10.80%; N·· 6.4〇% 實例10 : 使50.38克（159.7¾莫耳）氫氧化鋇人水合物懸浮在燒瓶内 jioo立方公分水中，並於65_7(rCs溫下溫熱所形成該懸 洋液。接著以30分鐘藉由滴液漏斗添加22 68克（53 2毫莫耳） 氟一（五氟乙基）磷烷，並攪摔。然後使該反應混合物溫熱 至！5〇。(：，並於該溫度下攪拌2小時。 在一個後續收集器内收集藉由該二氟三（五氟乙基）磷烷 解所开y成違氣悲五乳乙燒，並使該收集器經乾冰冷卻。 丘在該已冷卻收集器内得到1〇〇〇克液體五氟乙烷。以於這 仏件下自泫一氟二（五氟乙基）磷烷所移除這兩種五氟乙 基為基準計，該五氟乙烷之產率為78.3%。 使殘留在該燒瓶内之殘留物溶解在5〇立方公分之水中， 84146 -28- 200306980 並使用氟化氫水溶液中和。濾出所形成該氟化鋇沉殿物。 為了離析该五氣乙基鱗酸鎖’於減壓下移除該水。於12〇 帕減壓及100°C浴溫下使所形成白色固體乾燥1小時。得到 10.6克含約2重量％氟化鋇之五氟膦酸鋇[(c2F5P(〇)〇2)pa]， 以所使用該二氟三（五氟乙基）磷烷為基準計，其相當於 59.2%產率。 可藉由及19F—NMR光譜學表示該五氟乙烷之特徵，並 藉由F及P-NMR光谱學表示該五氟^膦酸鋇之特徵。 測定該五氟乙燒之化學位移，其相當於實例1所述之值。 五氟乙基膦酸鋇C (D20, reference CF3COOH in D2〇 = 76 53 ppm, δ, ppm) -81.64 tt (CF3); -121.94 m (CF2); -122.86 dm (CF2); -126.66 tm (CF2) 2Jp, f = 68.9 Hz; 4Jf > f = 9.6 Hz; 4Jf, f = 13.4 Hz; Jff = 3.9 Hz. 31P-NMR spectrum: (bath D20 'in D20 reference 85% by weight H3P04, δ, ppm) 4.00 tt; 2Jp > f = 68.8 Hz; 3JPjF = 3.4 Hz Example 5: 84146 -22- 200306980 make 8.0 Gram (190.5 Emole) hydroxide surface monohydrate was suspended in the square a knife water in the flask, and the suspension was warmed at 70-8 (rc bath temperature. The solution was then dropped by 30 minutes. A liquid funnel was charged with 2121 g (29.2 mmol) of difluorotris (n-nonafluorobutyl) phosphine and stirred. The reaction mixture was then μ warmed to a bath temperature of 150 C, and at this temperature, Stir for 2 hours. Collect the gaseous 1Η-n-nonafluoro-butane formed by hydrolysis of the difluorotris (n-nonafluorobutyl) phosphine in a subsequent collector, and cool the collector on dry ice. In the cooled collector, 7.24 grams of liquid 1-n-n-fluorofluorobutane was obtained. Under these conditions, the two n-fluorotris (n-nonafluorobutyl) phosphoranes were removed -Ninefluorobutyl as a basis, the yield of 1H-n-nonafluorobutane was 56.3%. The residue remaining in the flask was dissolved in 50 cubic centimeters of water, and hydrogen fluoride was used. The solution neutralized the excess lithium hydroxide and filtered off the precipitate formed from the fluorinated bell. In order to isolate the (n-nonafluorobutyl) phosphonic acid dilithium C4F9P (0) (〇Li) 2, it was moved under reduced pressure. The water was removed. The white solid formed was dried under reduced pressure of 20 Pa and bath temperature for 2 hours. 8.0 g of (n-nonafluorobutyl) phosphonic acid lithium was obtained, and the difluorotri (n- Nonafluorobutyl) phosphine is used as a benchmark, and its yield is equivalent to 87.8%. The characteristics of 1H-n-nonafluorobutane can be expressed by 19F-NMR spectroscopy, and by 19F- and 31P-NMR spectroscopy. It shows the characteristics of the dipotassium bis (n-nonafluorobutane) phosphonate. The chemical shift of the 1H-n-nonafluorobutane was measured, which is equivalent to the value shown in Example 3. 84146 -23- 200306980 The i9f- and 31p_NMR spectra were recorded at a frequency of 282.4 MHz (for 19F) and 121.5 MHz (for 31P) using a lithium lithium nonafluorobutylphosphonic acid spectrometer. 19F-NMR spectrum: ( Falling agent D 〖〇 'Reference in D20 CF3COOH = 76.53 ppm, δ, ppm) -81.85 tt (CF3); -122.03 m (CF2); -123.06 dm (CF2); -126.79 tm (CF2); Jp , F = 70.1 Hz; 4Jff = 9.5 Hz; 4Jf, f = 14.2 Hz; Jf, f = 3.9 Hz (solvent acetone-D6, internal reference CC13F, δ, ppm) -80.92 m (CFS); -120.66 m (CF2);- 122.70 dm (CF2); -125.62 tm (CF2); 2Jp, f = 78.6 Hz; 4Jff = 9.9 Hz; 4Jf, f = 14.5 Hz; Jf, f = 3.2 Hz 31p-nmr Spectra: (dropping agent D2〇 ′ 在Within D20, reference weight is 85 / 0H3p4, δ, ppm) 3.81 tt; 2JP F = 70.1 Hz; 3JP, F = 3.3 Hz (> cereal propyl @ 同 -〇6, in acetone_D6 , Reference 85% by weight h3p04-15% 020, δ, ppm) -0.28 t; 2JP F = 78.1 Hz Example 6: Dissolve 10.24 g (182.5 mmol) of potassium hydroxide in the flask The solution was formed in 10 cubic centimeters of water and warmed at a bath temperature of 65-70 ° C. Then, 1870 g (43.9 mmol) of difluorotris (pentafluoroethyl) was added through a dropping funnel over 60 minutes and stirred. The reaction mixture was then warmed at a bath temperature of 120t to mix 84146-24-200306980, and stirred at this temperature for another hour. The gaseous pentafluoroethane 'formed by the hydrolysis of difluorotris (pentafluoroethyl) phosphorane is collected in a subsequent collector, and the collector is cooled by liquid nitrogen. 9.99 grams of solid pentafluoroethane was obtained in the cooled collector. Based on the two pentafluoroethyl groups removed from the difluorotris (pentafluoroethyl) phosphine under these conditions, the yield of the pentafluoroethane was 94 8 /. . The residue remaining in the flask was dissolved in 40 cubic centimeters of water, and the excess hydroxide was neutralized with a few drops of hydrogen fluoride solution. In order to isolate the pentafluoroethylphosphonic acid, the water was removed under reduced pressure. The solid formed was dried at a reduced pressure of 120 Pa and a bath temperature of 100 ° C for one hour. The pentagas ethylphosphonic acid disodium is then extracted from the solid residue using two 50 cm3 methanol portions, the fractions are combined, the methanol is filtered off, and the residue formed is dried under reduced pressure at 120 Pa. . 16.54 g of dipotassium pentafluoroethylphosphonic acid di (fluorinated) were obtained (C2F5P (〇) (〇K) 2> 2KF, based on the ditown tris (pentafluoroethyl) squalane used as a benchmark, its production The rate is equivalent to 96.1%. The characteristics of the pentafluoroethyl benzene can be expressed by 19F-NMR spectroscopy, and the dipotassium pentafluoroethylphosphonic acid can be expressed by 19f- and 31P-NMR spectroscopy. ). The chemical shift of this pentafluoroethane was measured, which corresponds to the value described in Example 1. Dipotassium pentafluoroethylphosphonate (potassium fluoride) 19F-NMR spectrum: (solvent D20, at D2 Within 〇, reference CF3c 〇H = 76.53 ppm, δ, ppm) '· 86 t (CF3); -125.91 q (CF2); -122.70 s (2KF); 2JP, produced 68.4 Η ζ · 84146 -25- 200306980 3 JF, F = 1.6 Hz 31P-NMR spectrum: (solvent D20, within D20, reference 85% by weight 1 * 13? 04, δ, ppm) 3 · 17 t; 2 J p F = 6 8 · 4 Η z Example 7: 8.50 grams (151.5 millimoles) of potassium hydroxide was dissolved in the heart of the flask ^ cubic centimeters of water, and the solution was warmed at a bath temperature of 70-80 ° C. Then 90 minutes Add 15 77 g (37 mM) difluorotrifluoro via a dropping funnel Pentafluoroethyl) phosphorane, and stirred. The gaseous pentafluoroethane formed by the decomposition of the difluorotris (pentafluoroethyl) phosphorane K was collected in a subsequent collector, and the collector was liquid Nitrogen was cooled. 8.30 grams of solid pentafluoroethane was obtained in the cooled collector. Under these conditions, the two pentafluoroethanes were removed from the difluorotris (pentafluoroethyl) phosphine. Based on the basis, the yield of the pentafluoroethane was 93.4%. The chemical shift of the pentafluoroethane was measured, which corresponds to the value described in Example 1. Example 8: 6.23 g (111.0 mmol) ) Potassium hydroxide was dissolved in 1218 g of ethanol / water mixture (1: 1 parts by weight) in a flask, and the solution was warmed at 55-60. (: Bath temperature was formed. Then by 45 minutes by The dropping funnel was charged with 43 grams (26.8 millimoles) of difluorotris (pentafluoroethyl) phosphine and stirred, and the reaction mixture was heated under the ribs for 10 minutes. Collected in a subsequent collector The gaseous pentafluoroethane is formed by hydrolysis of the difluorotris (pentafluoroethyl) phosphorane, and the collector is cooled by liquid nitrogen. 5.23 grams of solid pentafluoroethane was obtained in the cooled collector. Based on these 84146 -26- 200306980, the two pentafluoroethyl groups removed from μ-fluorobis (pentafluoroethyl) phosphine were used as a benchmark. Based on this, the yield of pentafluoroethane was 81.3%. The pentafluoro (acetonitrile) was measured, which was equivalent to the value described in Example 1. Example 9: Add 13.46 grams (31.6 millimoles) of difluorotris (pentafluoroethyl) phosphine to 96.5 grams (131. 丨 millimoles) through a dropping funnel for 1 hour under a dish. 0% by weight of tetraethyl sodium hydroxide aqueous solution and stirred. During operation, observe the warming of the reaction mixture. The reaction mixture was then heated at 80 C for 30 minutes. The gaseous pentafluoroethane formed by the hydrolysis of the difluorotris (pentafluoroethyl) scale is collected in a subsequent collector, and the collector is cooled by liquid nitrogen. In the cooled collector, 7.49 grams of solid pentafluoroethane was obtained. Based on the two pentafluoroethyl groups removed, the yield of the pentafluoroethane was 98.8%. The chemical shift of the pentafluoroethane was measured, which corresponds to the value described in Example 1. The solution remaining in the flask was evaporated by a rotary evaporator, and the solid formed was dried at a reduced pressure of 120 Pa and a temperature of 100 ° C to obtain 24.67 g of white crystal [(C2H5) 4N] 2 [C2F5P03] .2 [ (C2H5) 4N] F.8H20. The characteristics of the [(C2H5) 4N] 2 [C2F5P〇3> 2 [(C2H5) 4N] F.8H20 can be expressed by Go-, 19F-, 31P-NMR spectroscopy and elemental analysis. The 19F-, and 31P-NMR spectra were recorded using a Bruker Avance 300 spectrometer at 282.4 MHz (for 19F) and 121.5 MHz (for 31P) frequencies. 19f-nmr spectrum: (solvent acetonitrile-D3, reference CC13F, δ, ppm) -79.41 dt (CF3); -126.74 dq (CF2); -111.74 (2F-); 2JP, F = 54.〇Hz; 84146 -27- 200306980 3JPF = 1.1 Hz; 3JF, F = 1.0Hz W-NMR spectrum: (solvent acetonitrile-D3, reference TMS, δ, ppm) 1.21 tm (CH3); 3.28 q (CH2); 3JH, H-7.3 Hz performs a proton exchange between the H2O molecule and the deuterium of the solvent; 31p-nmr spectrum: (solvent E-r-r> 3, in the ethyl acetate, the reference is in weight% H3P04_15〇 / 〇D2〇, δ, ppm) Ί.77 t; 2JP) F = 54.2 Hz Elemental analysis: Calculated value for C34H96F5N4〇llP: c: 47 31%; H: u 21%; N: 6 49〇 / 〇Measured value : C: 47.37%; H: 10.80%; N · 6.40% Example 10: 50.38 g (159.7¾ mole) of barium hydroxide human hydrate was suspended in a jioo cubic centimeter of water in a flask, and the temperature was 65-7 (rCs temperature) The suspended ocean liquid was warmed. Then 22 68 g (53 2 mmol) of fluoro- (pentafluoroethyl) phosphine was added through a dropping funnel over 30 minutes and stirred. The reaction mixture was then allowed to stir. Warm to! 50. (:, and stir at this temperature for 2 hours. In a subsequent harvest Collected in the container by the difluorotris (pentafluoroethyl) phosphorane decomposition, the pentamidine was burned, and the collector was cooled by dry ice. Qiu got 1 in the cooled collector. 〇〇g liquid pentafluoroethane. Based on the two pentafluoroethyl groups removed from the monofluorobis (pentafluoroethyl) phosphane in this case, the yield of the pentafluoroethane 78.3%. The residue remaining in the flask was dissolved in 50 cubic centimeters of water, 84146 -28- 200306980 and neutralized with an aqueous hydrogen fluoride solution. The formed barium fluoride sink was filtered off. In order to isolate the five gases The water was removed under reduced pressure. The white solid formed was dried for 1 hour at a reduced pressure of 120 Pa and a bath temperature of 100 ° C. 10.6 g of five containing about 2% by weight of barium fluoride was obtained. Barium fluorophosphonate [(c2F5P (0) 〇2) pa], based on the difluorotris (pentafluoroethyl) phosphorane used, is equivalent to a 59.2% yield. 19F-NMR Spectroscopy shows the characteristics of the pentafluoroethane, and F and P-NMR spectroscopy shows the characteristics of the barium pentafluoro ^ phosphonate. The chemical shift of the pentafluoroethane was measured, and its phase Equivalent to the value described in Example 1. Barium pentafluoroethylphosphonate

利用 Bmker Avance 300分光計，於282.4 MHz(就 19F而言） 及121.5 MHz(就31P而言）頻率下記錄該i9F_，ιΉ_及3ip-NMR 光譜。 19f-nmr光譜： (/谷 M D2O ’ 在 D20 内’參考物 CF3COOH=76.53 ppm，δ，ppm) -81.99 td (CF3)； -126.25 dq (CF2); 31p-nmr 光譜： (落劑D20 ’在D2〇内，參考物85重量％Η3ρ〇4·15% d2〇，δ， Ppm) 2.88 t; 2Jp,f=70.3 Hz 實例11 : 使16.70克（52·9毫莫耳）氫氧化鋇八水合物懸浮在燒瓶内 之20 方公分水中，並於7〇_8〇。〇浴溫下溫熱所形成該懸浮 夜。接著以30分鐘藉由滴液漏斗添加17.79克（24.5毫莫耳） 84146 -29- 200306980 二氟三（正，九氟丁基）磷烷，並攪拌。然後於120°C浴溫下溫 熱該反應混合物，並於該溫度下攪拌1小時。 可以在一個後續收集器内收集藉由該二氟三（正-九氟丁 基）磷烷水解所形成該氣態1H-正-九氟-丁烷，並使該收集器 經液體氮冷卻。 在該已冷卻收集器内得到7·72克液體1H-正-九氟丁烷。以 於這些條件下自該二氟三（正-九氟丁基）磷烷所移除之這兩 種正-九氟丁基為基準計，該1Η-正-九氟丁烷之產率為 71.6%。 使殘留物於該燒瓶内之殘留物溶解於5〇立方公分之水 中，並使用氟化氫水溶液中和。濾出所形成該氟化鋇沉澱 物。 為了離析該正-九氣丁基膦酸鋇，於減磨下移除該水。於 120 Pa減壓及l〇〇°C浴溫下使所形成白色固體乾燥丨小時。得 到7.0克含約2重量。/〇氟化鋇之正·九氟丁基膦酸鋇 ([n-C4F9P(〇)〇2]Ba)，以所使用該二氟三（五氟乙基）磷烷為 基準，其相當於64.87%產率。 可藉由咕-及19f-nmR光譜學表示該1H_正-九氟丁烷之特 徵，並藉由19F-及31P-NMR光譜學表示該正_九氟丁基膦酸鋇 之特徵。 測定該1H-正-九氟丁烷之化學位移，其相當於實例3所示 之值。 正-九氟丁基膦酸鋇 19F-NMR 光譜： 84146 -30- 200306980 (溶劑D20，在D2〇内， -81.77 tt (CF3); -122.29 tm (CF2); 2JP)F=75.8 Hz; 參考物 CF3C00H=76.53 ppm，δ , ppm) 9 m (CF2)； -123.66 dtm (CF2)； -126.76 7 · 4 了Using a Bmker Avance 300 spectrometer, the i9F_, ιΉ_ and 3ip-NMR spectra were recorded at 282.4 MHz (for 19F) and 121.5 MHz (for 31P) frequencies. 19f-nmr spectrum: (/ valley M D2O 'in D20' reference CF3COOH = 76.53 ppm, δ, ppm) -81.99 td (CF3); -126.25 dq (CF2); 31p-nmr spectrum: (dropping agent D20 ' Within D2O, reference 85% by weight (3po4 · 15% d2, δ, Ppm) 2.88 t; 2Jp, f = 70.3 Hz Example 11: 16.70 g (52.9 millimoles) of barium hydroxide eight The hydrate was suspended in 20 cm² of water in the flask, and dried at 70-8. The suspension was warmed up at a bath temperature. Then, 17.79 g (24.5 millimoles) of 84146 -29- 200306980 difluorotris (n-nonafluorobutyl) phosphine was added through a dropping funnel over 30 minutes, and stirred. The reaction mixture was then warmed at a bath temperature of 120 ° C and stirred at this temperature for 1 hour. The gaseous 1H-n-nonafluoro-butane formed by hydrolysis of the difluorotris (n-nonafluorobutyl) phosphane can be collected in a subsequent collector, and the collector can be cooled by liquid nitrogen. 7.72 g of liquid 1H-n-nonafluorobutane was obtained in the cooled collector. Based on the two types of n-nonafluorobutyl removed from the difluorotris (n-nonafluorobutyl) phosphine under these conditions, the yield of 1Η-n-nonafluorobutane is 71.6%. The residue in the flask was dissolved in 50 cm 3 of water and neutralized with an aqueous hydrogen fluoride solution. The formed barium fluoride precipitate was filtered off. In order to isolate the n-n-airbarium butylphosphonate, the water was removed under reduced friction. The white solid formed was dried at a reduced pressure of 120 Pa and a bath temperature of 100 ° C for one hour. 7.0 g was obtained containing about 2 weight. The barium n-fluorofluorophosphonate ([n-C4F9P (〇) 〇2] Ba) of barium fluoride is based on the difluorotris (pentafluoroethyl) phosphorane used, which is equivalent to 64.87% yield. The characteristics of the 1H-n-nonafluorobutane can be expressed by Go- and 19f-nmR spectroscopy, and the characteristics of the barium n-nonafluorobutylphosphonate can be expressed by 19F- and 31P-NMR spectroscopy. When the chemical shift of 1H-n-nonafluorobutane was measured, it corresponds to the value shown in Example 3. 19F-NMR spectrum of barium n-nonafluorobutylphosphonate: 84146 -30- 200306980 (solvent D20, within D20, -81.77 tt (CF3); -122.29 tm (CF2); 2JP) F = 75.8 Hz; reference CF3C00H = 76.53 ppm, δ, ppm) 9 m (CF2); -123.66 dtm (CF2); -126.76 7 · 4

Hz; 4JF)F=13.8 Hz; Jf,f=3.6 P-NMR光譜：Hz; 4JF) F = 13.8 Hz; Jf, f = 3.6 P-NMR spectrum:

厶 ZZ JP，F=/0.i HZ 實例12 : 將10.32克（183.9¾莫耳）氫氧化鉀及2〇立方公分水導入容 1為100 乂方公分之壓熱器内。使該壓熱器冷卻至， 並添加9.70克（22.8毫莫耳）二氟三（五氟乙基）磷烷。然後關 閉该壓熱器，並於200_210°C下借助於油浴加熱8小時。接 著使泫壓熱斋達至室溫’並使該壓熱器之出口與已經過液 體氮冷卻之冷收集器連接。得到7·57克純五氟乙烷，以於這 些條件下自所使用該二氟三（五氟乙基）磷烷移除之這3種五 氟乙基為基準計，其相當於92.2%產率。 測定該五氟乙烷之化學位移，其相當於實例1所述之值。 實例1 3 : 將51 ·0克氫氧化鉀及5〇立方公分水導入容量為350立方 公分之壓熱器内。使該壓熱器冷卻至_3()1，並添加三氟雙 (正-九氟丁基）磷烷（60莫耳％)及二氟三（正-九氟丁基）磷烷 (40莫耳％)之混合物95.9克。然後關閉該壓熱器，並於200-2l〇°C下’借助於油浴加熱丨8小時。接著使該壓熱器達至室 溫’並使該壓熱器之出口與已經過乾冰冷卻之冷收集器連 84146 -31 - 200306980 接。 得到68.0克純1H-九氟-正-丁烷，以於這些條件下自所使 用該三氟雙（正-九氟丁基）磷烷及二氟三（正-九氟丁基）磷烷 移除之這兩種正-九氟丁基為基準計，其相當於95.2%產率。 可藉由1H-及19F-NMR光譜學表示該1H-九氟-正-丁烷之 特徵。 測定該1H-九氟-正-丁烷之化學位移，其相當於實例1所 示之值。 貫例14 · 雙（五氟乙基）亞膦酸 將4.09克（12.0毫莫耳）雙（五氟乙基）亞膦酸鉀及8.71克 (88.9毫莫耳）100%硫酸H2S04導入蒸餾瓶内，並於減壓（400 帕）及90-120 °C油浴溫下蒸餾所形成該雙（五氟乙基）亞膦 酸。得到3.25克透明無色之雙（五氟乙基）亞膦酸液體， (C2F5)P(0)0H，其相當於89·5%產率。 已發現该化學位移之值相當於T· Mahmood在Inorganic厶 ZZ JP, F = / 0.i HZ Example 12: 10.32 grams (183.9¾ mol) of potassium hydroxide and 20 cubic centimeters of water were introduced into an autoclave with a capacity of 100 centimeters. The autoclave was cooled to and 9.70 g (22.8 mmol) of difluorotris (pentafluoroethyl) phosphine was added. The autoclave was then closed and heated at 200-210 ° C for 8 hours by means of an oil bath. The autoclave is then brought to room temperature 'and the outlet of the autoclave is connected to a cold collector which has been cooled with liquid nitrogen. 7.57 g of pure pentafluoroethane was obtained. Based on the three pentafluoroethyl groups removed from the difluorotris (pentafluoroethyl) phosphorane used under these conditions, it was equivalent to 92.2% Yield. The chemical shift of this pentafluoroethane was measured, which was equivalent to the value described in Example 1. Example 13: 51.0 g of potassium hydroxide and 50 cubic centimeters of water were introduced into an autoclave with a capacity of 350 cubic centimeters. The autoclave was cooled to _3 () 1, and trifluorobis (n-nonafluorobutyl) phosphine (60 mole%) and difluorotris (n-nonafluorobutyl) phosphine (40 Mole%) mixture 95.9 g. The autoclave was then closed and heated at 200-2l ° C for 8 hours by means of an oil bath. The autoclave is then brought to room temperature 'and the outlet of the autoclave is connected to a cold collector that has been cooled by dry ice 84146 -31-200306980. 68.0 g of pure 1H-nonafluoro-n-butane were obtained, under these conditions the trifluorobis (n-nonafluorobutyl) phosphine and difluorotris (n-nonafluorobutyl) phosphine were used. With the two n-nonafluorobutyl groups removed as a basis, this corresponds to a 95.2% yield. The characteristics of the 1H-nonafluoro-n-butane can be expressed by 1H- and 19F-NMR spectroscopy. The chemical shift of 1H-nonafluoro-n-butane was measured, and it corresponds to the value shown in Example 1. Example 14 · Bis (pentafluoroethyl) phosphinic acid introduced 4.09 g (12.0 mmol) of potassium bis (pentafluoroethyl) phosphinate and 8.71 g (88.9 mmol) of 100% sulfuric acid H2S04 into a distillation flask The bis (pentafluoroethyl) phosphinic acid was formed by distillation under reduced pressure (400 Pa) and an oil bath temperature of 90-120 ° C. This gave 3.25 g of a transparent, colorless bis (pentafluoroethyl) phosphinic acid liquid, (C2F5) P (0) 0H, which corresponds to a yield of 89.5%. It has been found that the value of this chemical shift is equivalent to that of T. Mahmood in Inorganic

Chemistry，25(1986)，第3128-3131頁之公告中所揭示之值。 實例1 5 : 添加1.0克（10.2毫莫耳）100%硫酸h2s〇4至3 ·42克（10.2毫 莫耳）五氟乙基膦酸鋇之5〇立方公分水攪掉溶液内。形成一 種硫酸鋇沉澱物，藉由過濾法使其分離。於減壓下使所形 成濾出物完全蒸發，並於125帕及loot：油浴溫下再乾燥ό小 時。得到1 ·75克咼黏性五氟乙基亞膦酸液體（C2F5)p(〇)(〇H)2 ，其相當於83.8%產率。 84146 -32- 200306980 19F-NMR光譜： (溶劑：乙腈-D3，參考物CC13F，δ，ppm) -81.03 t (CF3); -126.74 dq (CF2); J2p，f=89.4 Hz; J3f，f=1.6 Hz h-NMR光譜： (溶劑：乙腈-D3，參考物TMS，δ，ppm) 11.26 br.s (OH) 31P-NMR 光譜： (溶劑：乙腈-D3 ;參考物：在乙腈_d3内，85重量％H3P〇4-15 重量％ d2〇） -3·40 t; J p，f=89.6 Hz 〇 這些數值相當於Τ· Mahmood及J· M. Shreeve在InorgChemistry, 25 (1986), values disclosed in Announcements on pages 3128-3131. Example 15: 1.0 g (10.2 mmol) of 100% sulfuric acid h2s04 to 3.42 g (10.2 mmol) of barium pentafluoroethylphosphonate in 50 cm³ of water was added to stir the solution. A precipitate of barium sulfate was formed and separated by filtration. The formed filtrate was completely evaporated under reduced pressure, and dried at 125 Pa and the temperature of the oil bath for another hour. 1.75 g of viscous pentafluoroethyl phosphinic acid liquid (C2F5) p (〇) (〇H) 2 was obtained, which corresponds to a yield of 83.8%. 84146 -32- 200306980 19F-NMR spectrum: (solvent: acetonitrile-D3, reference CC13F, δ, ppm) -81.03 t (CF3); -126.74 dq (CF2); J2p, f = 89.4 Hz; J3f, f = 1.6 Hz h-NMR spectrum: (solvent: acetonitrile-D3, reference TMS, δ, ppm) 11.26 br.s (OH) 31P-NMR spectrum: (solvent: acetonitrile-D3; reference: in acetonitrile_d3, 85% by weight H3P〇4-15% by weight d2〇)-3.40 t; J p, f = 89.6 Hz 〇 These values are equivalent to T. Mahmood and J. M. Shreeve in Inorg

Chem·，25(1986)，第3128-3131頁之文獻公告中所揭示之 值。 實例16 : 於室溫下緩慢添加（並攪拌）3.015克2〇重量％水性四乙基 氫氧化銨中和0.492克（2.46毫莫耳）如實例15所製成五氟乙 基亞膦酸之10立方公分水溶液。於減壓下蒸發該水，並於 120帕減壓及50 C浴溫下使所形成殘留物乾燥2小時。 得到1.115克雙（四乙基銨）五氟乙基膦酸鹽白色固體。以 所使用該五氟乙基膦酸為基準計，該產率為99 〇%。 可藉由19F-，31P-及1H-NMR光譜學表示雙（四丁基銨）五氟 乙基膦酸鹽之特徵： 19f-nmr 光譜： (落劑：乙腈-D3 ;參考物：cci3f): 84146 -33- 200306980 -79.49 s (CF3); -122.10 d (CF2); J2p，f=54.6 Hz。 iH-NMR光譜，ppm : (溶劑：乙腈-D3 ;參考物：丁“3): 1.20 tm (12H，4CH3); 3·29 q (8H，4CH2); J3h，h=7.3 Hz。 31P-NMR光譜，ppm : (溶劑：乙腈-D3 ;參考物：85% H3P04): -2.28 t; J2p，f=54.9 Hz 〇 實例1 7 : 於室溫下緩慢添加（並攪拌）2 0重量％水性四乙基氫氧化 銨中和（pH=7)如實例15所述自3·73克（8.57毫莫耳）九氟·正· 丁基膦酸鋇及0.839克1〇〇重量％硫酸製成之九氟-正·丁基腾 酸之20立方公分水溶液。於減壓下蒸發該水，並於ι2〇帕減 壓及60°C浴溫下使所形成殘留物乾燥2小時。 得到4·59克雙（四丁基銨）九氟·正·丁基膦酸鹽固體。以所 使用該九氟-正-丁基膦酸鋇為基準計，該產率為96.0%。 可藉由19F-，31Ρ-及1H_NMR光譜學表示雙（四乙基銨）九氟 -正-丁基膦酸鹽之特徵： 19F-NMR光譜，ppm : (溶劑：乙腈-D3 ;參考物：CC13F): -80.37 tt (CF3); -119.57 m (CF2); 119.72 dm (CF2)； -124.80 m (CF2); J2p，f=55.6 Hz; J3F F=4.3 Hz; J4F F=9.5 Hz。 W-NMR光譜，ppm ·· (溶劑：乙腈-D3 ;參考物：TMS): 1.23 tm (12H，4CH3); 3·27 q (8H，4CH2); J3h，h=7.4 Hz。 84146 -34- 200306980 P-NMR光譜，ppm : (落劑：乙腈_D3 ;參考物：85% H3P〇4): -2.06 t; J2P F=56.5 Hz。 實例1 8 : 使1·43克如實例15所述製成之該五氟乙基膦酸溶解在15 立方公分水中，並於室溫下緩慢添加（並攪拌）1()重量％水性 氫氧化鉀使其中和（ρΗ=7)。於室溫下添加2.09克（11.9毫莫 耳）1 -乙基-3 -甲基氯化咪唑之3立方公分水溶液至所形成五 氟乙基膦酸二鉀水溶液内，並攪拌。於減壓下蒸發該水， 並於120帕減壓及60°C浴溫下使所形成殘留物乾燥丨小時。 接著添加10立方公分異丙醇至該殘留物内，並濾出白色沉 澱物，然後經5立方公分異丙醇洗滌兩次。於減壓下蒸餾該 異丙醇，並於1.4 Pa減壓及8(rC浴溫下使所形成殘留物乾燥 1 · 5小時。 仔到2.56克二（1-乙基-3_甲基咪唑）五氟乙基膦酸鹽油狀 液體。以所使用該五氟乙基膦酸為基準計，該產率為85〇%。 可藉由19F-，31卩-及111七1^11光譜學表示二（1_乙基_3_甲基 咪唑）五氟乙基膦酸鹽之特徵： 19F_NMR光譜，ppm : (溶劑：乙腈-D3 ;參考物：cci3f): -79·68 s (CF3); -123.22 d (CF2); J2P F=57.9 Hz。 iH-NMR光譜，ppm ·· (落劑··乙腊-D3 ;參考物：TMS): 1.38 t (3H，CH3); 3.94 s (3H，CH3); 4.29 q (2H，CH2); 7·70 s 84146 -35- 200306980 (1H); 7.75 s (1H); 1〇 82 s (1H); & h=7 2 沿。 31p-nmr光譜，ppm : (洛劑·乙腈七3 ;參考物：85% H3p〇4): -1·28 t; J2p，f=57.4 Hz。 實例1 9 : 於室溫下緩慢添加（並㈣）14.86克約40重量％水性四丁 基氫氧化鳞中和（ΡΗ=7)2·4克（12·0毫莫耳）如實例15所述製 成（五II乙基膦酸之13立彳公分水溶液。於減壓下蒸發該 水，並於1.4帕減壓及70艺浴溫下使所形成殘留物乾燥2小 時。 得到7.95克鬲黏性液體，其可緩慢晶化呈雙（四丁基鳞） 五氟乙基膦酸鹽之白色固體型式。以所使用該五氟乙基膦 酸為基準計’該產率為92.4%。該溶點為76-79°C。 可藉由19F-，31P-及1H-NMR光譜學表示雙（四丁基鱗）五氟 乙基膦酸鹽（[(C4H9)4P+]2C2F5P(〇)〇22-)之特徵·· 19F-NMR光譜，ppm : (溶劑：乙腈-Da ;參考物：CC13F) ·· -79.39 s (CF3)； -121.98 d (CF2)； J2P,F=54.2 Hz 〇 i-NMR光譜，ppm : (溶劑··乙腈-D3 ;參考物：TMS): 0·93 t (12H，4CH3)，1_45 m (16H，8CH2); 2·37 m (8H，4C；H2)· J3h，h=7.1 Hz。 31P-NMR光譜，ppm : (溶劑：乙腈-D3 ;參考物：85% h3P04): -1.84 t (IP); 32.73 m (2P)； j2p f=54.6 Hz 〇 84146 -36-Chem., 25 (1986), values disclosed in document publications on pages 3128-3131. Example 16: Slowly add (and stir) 3.015 g of 20% by weight aqueous tetraethylammonium hydroxide at room temperature to neutralize 0.492 g (2.46 mmol) of the pentafluoroethyl phosphinic acid prepared in Example 15 10 cubic centimeters in water. The water was evaporated under reduced pressure, and the resulting residue was dried at a reduced pressure of 120 Pa and a bath temperature of 50 C for 2 hours. 1.115 g of bis (tetraethylammonium) pentafluoroethylphosphonate were obtained as a white solid. Based on the pentafluoroethylphosphonic acid used, the yield was 99.0%. The characteristics of bis (tetrabutylammonium) pentafluoroethylphosphonate can be expressed by 19F-, 31P- and 1H-NMR spectroscopy: 19f-nmr Spectrum: (dropping agent: acetonitrile-D3; reference: cci3f) : 84146 -33- 200306980 -79.49 s (CF3); -122.10 d (CF2); J2p, f = 54.6 Hz. iH-NMR spectrum, ppm: (solvent: acetonitrile-D3; reference: D3): 1.20 tm (12H, 4CH3); 3.29 q (8H, 4CH2); J3h, h = 7.3 Hz. 31P-NMR Spectrum, ppm: (solvent: acetonitrile-D3; reference: 85% H3P04): -2.28 t; J2p, f = 54.9 Hz 〇Example 17: Slowly add (and stir) 20% by weight of water at room temperature. Ethyl ammonium hydroxide neutralized (pH = 7) was prepared from 3.73 g (8.57 mmol) of barium nonafluoro-n-butylphosphonate and 0.839 g of 100% by weight sulfuric acid as described in Example 15. A solution of nonafluoro-n-butyltenic acid in 20 cubic centimeters. The water was evaporated under reduced pressure, and the resulting residue was dried under reduced pressure of 20 Pa and a bath temperature of 60 ° C for 2 hours. 4.59 g (Tetrabutylammonium) nonafluoro-n-butylphosphonate solid. Based on the barium nonafluoro-n-butylphosphonate used, the yield was 96.0%. 19F-, 31P -And 1H_NMR spectroscopy shows the characteristics of bis (tetraethylammonium) nonafluoro-n-butylphosphonate: 19F-NMR spectrum, ppm: (solvent: acetonitrile-D3; reference: CC13F): -80.37 tt ( CF3); -119.57 m (CF2); 119.72 dm (CF2); -124.80 m (CF2); J2p, f = 5 5.6 Hz; J3F F = 4.3 Hz; J4F F = 9.5 Hz. W-NMR spectrum, ppm · (solvent: acetonitrile-D3; reference: TMS): 1.23 tm (12H, 4CH3); 3.27 q (8H , 4CH2); J3h, h = 7.4 Hz. 84146 -34- 200306980 P-NMR spectrum, ppm: (dropping agent: acetonitrile_D3; reference: 85% H3P〇4): -2.06 t; J2P F = 56.5 Hz Example 18: 1.43 g of the pentafluoroethylphosphonic acid prepared as described in Example 15 was dissolved in 15 cubic centimeters of water, and 1 ()% by weight of aqueous hydrogen was slowly added (and stirred) at room temperature. It was neutralized with potassium oxide (ρΗ = 7). At room temperature, 2.09 g (11.9 mmol) of 1-ethyl-3 -methylimidazole in a 3 cm aqueous solution was added to the formed pentafluoroethylphosphonic acid. It was stirred in a dipotassium aqueous solution. The water was evaporated under reduced pressure, and the resulting residue was dried at a reduced pressure of 120 Pa and a bath temperature of 60 ° C for one hour. Then, 10 cubic centimeters of isopropanol was added to the residue. Inside, and the white precipitate was filtered off, and then washed twice with 5 cubic centimeters of isopropanol. The isopropanol was distilled under reduced pressure, and the formed residue was dried at a reduced pressure of 1.4 Pa and a bath temperature of 8 (rC). 1 · 5 hours. To 2.56 g of bis (1-ethyl-3_methylimidazole) pentafluoroethylphosphonate oily liquid. Based on the pentafluoroethylphosphonic acid used, the yield was 85%. The characteristics of bis (1_ethyl_3_methylimidazole) pentafluoroethylphosphonate can be expressed by 19F-, 31 卩-and 111 VII 1 ^ 11 spectroscopy: 19F_NMR spectrum, ppm: (solvent: acetonitrile -D3; Reference: cci3f): -79 · 68 s (CF3); -123.22 d (CF2); J2P F = 57.9 Hz. iH-NMR spectrum, ppm ···························· Reference: TMS: 1.38 t (3H, CH3); 3.94 s (3H, CH3); 4.29 q (2H, CH2); 7 · 70 s 84146 -35- 200306980 (1H); 7.75 s (1H); 1082 s (1H); & h = 7 2 edge. 31p-nmr spectrum, ppm: (Lotion · acetonitrile 7 3; reference: 85% H3po4): -1 · 28 t; J2p, f = 57.4 Hz. Example 19: At room temperature, slowly add (86) 14.86 g of about 40% by weight of aqueous tetrabutyl hydroxide scale to neutralize (P = 7) 2.4 g (12.0 mmol) as in Example 15. The solution was prepared as a 13-cm aqueous solution of pentaII ethylphosphonic acid. The water was evaporated under reduced pressure, and the resulting residue was dried at a reduced pressure of 1.4 Pa and a bath temperature of 70 ° C for 2 hours. 7.95 g of tincture was obtained A viscous liquid that can slowly crystallize into a white solid form of bis (tetrabutylscale) pentafluoroethylphosphonate. Based on the pentafluoroethylphosphonic acid used, the yield is 92.4%. The melting point is 76-79 ° C. Bis (tetrabutylscale) pentafluoroethylphosphonate ([(C4H9) 4P +] 2C2F5P (〇) can be expressed by 19F-, 31P- and 1H-NMR spectroscopy. 〇22-) Features 19F-NMR spectrum, ppm: (solvent: acetonitrile-Da; reference: CC13F)--79.39 s (CF3); -121.98 d (CF2); J2P, F = 54.2 Hz i-NMR spectrum, ppm: (solvent ·· acetonitrile-D3; reference: TMS): 0 · 93 t (12H, 4CH3), 1-45 m (16H, 8CH2); 2.37 m (8H, 4C; H2) · J3h, h = 7.1 Hz. 31P-NMR spectrum, ppm: (solvent: acetonitrile-D3; reference: 85% h3P04): -1. 84 t (IP); 32.73 m (2P); j2p f = 54.6 Hz 〇 84146 -36-

Claims (1)

200306980 拾、申請專利範圍： 種I備單氫全氟烷化物，雙（全氟烷基）亞膦酸鹽及全氟 烷基膦酸鹽之方法，其包括在適合之反應介質内以至少一 種鹼及若必要，一種酸至少進行至少一種全氟烷基磷烷之 處理。 2.根據申請專利範圍第1項之製備單氫全氟燒化物之方 法，其特徵為在適合之溶劑内，使至少一種全氟烷基磷烷 與至少一種鹼（a)或一種有機金屬化合物反應。 根據申β專利範圍第】項之製備雙（全氣燒基）亞騰酸鹽及 全氣燒基膦酸鹽之方法，其特徵為在適合之溶劑中使至少 -種全氟垸基魏與至少—種無機驗⑻反應，除了單氣 全氟燒化物之外，可藉由鹽互換離析後，或直接使所形成 之雙（全氟燒基）亞膦酸鹽及全氣燒基腾酸鹽轉化成對應 <雙（全氟燒基）亞膦酸及全氟燒基亞膦酸，或其後經酸 (較佳為硫酸）處理’ ^其後藉由中和反應（較佳使用有機 鹼（C))得到該等鹽。 4.根據申請專利範圍第1項之方法，其特徵為所使用之全氟 基磷垸為通式I化合物 V^n^2n+l)mPF5.m 其中1^8’較佳為Bng，且於各情況中，爪為工，2或] 5.根據中請專利範圍第1項之方法，其特徵為該全㈣基 燒係選自由二氟三（五氟乙基）磷燒，二氟三（正-九氟丁』 磷反，二氟三（正-七氟丙基）磷垸及三氣雙（正-九氣丁』 铸烷所組成之群組。 84146 200306980 6.根據令請專利範圍第2或3項之方法，其特徵為所使用之驗 (a)或（C)為至少一種有機鹼。 7·根據申請專利範圍第6項之方法，其特徵為該有機驗（群) :選自以下所组成之群组：燒基氫氧化按，芳基氣氧化 二t基万基氫氧化按，垸基氫氧化鳞，芳基氫氧化鱗， 2基万基氫氧化鱗，燒基胺，芳基胺，燒基芳基胺，燒基 膦，芳基膦及烷基芳基膦。 據申明專利知圍第2 4 3項之方法，其特徵為使用至少 一種無機驗（a)或（b)。 根據申印專利範圍第8項之方法，其特徵為該無機驗（群） 係選自由驗金屬氫氧化物及驗土金屬氫氧化物所組成之 群組。 根據申巧專利範圍第9項之方法，其特徵為該驗金屬氣氧 ，物選自由氫氧_，氫氧⑽單水合物，氫氧化鋼及氫 氧化鉀所組成之群組。 ，據申Μ專職gj第9項之方法，其特徵為該驗土金屬氮 氧化物選自由氫氧化鋇，氫氧化鋇八水合物及氮氧化轉所 組成之群組。 2據申叫專利範圍第2項之方法，其特徵為該有機金屬化 物坟自以下所組成之群組：金屬烷氧化物，較佳為鹼金 屬烷虱化物；金屬芳氧化物；金屬烷基硫氧化物；金屬芳 基硫氧化物，烷基金屬化合物，芳基金屬化合物及格里納 (GHgnard)試劑。 根據申叫專利範圍第1項之方法，其特徵為該反應介質為 ^右必要可以與一或多種有機溶劑混合。 84146 200306980 14· $據申請專利範圍第1項之方法，其特徵為所使用該反應 介質為一或多種有機溶劑。 15·=中請專利範圍第13或14項之方法，其特徵為該有機 /谷劑選自由醇類，醚類，醯基醯胺類，亞砜類，颯類，腈 類及烴類所組成之群組。 16·根據申請專利範圍第15項之方法，其特徵為該醇之燒基 #份具有1至4個碳原子，且較佳選自由甲醇，乙醇，異 丙醇及至少兩種這些醇類之混合物所組成之群組。 Π·—種全氟烷基膦酸鹽及雙（全氟烷基）亞膦酸鹽，其係選自 以下所組成之群組：部份烷化及全烷化銨，鱗，锍，吡啶， 噠畊，嘧啶，吡畊，咪唑，吡唑，嘍唑，嘮畊及三唑鹽。 18·根據申請專利範圍第17項之全氟烷基膦酸鹽及雙（全氟 烷基）亞膦酸鹽，其具有一個選自以下所組成之群組之陽200306980 Patent application scope: A method for preparing a monohydroperfluoroalkane, a bis (perfluoroalkyl) phosphinate, and a perfluoroalkyl phosphonate, which includes at least one kind in a suitable reaction medium. The base and, if necessary, at least one perfluoroalkylphosphorane are treated with an acid. 2. A method for preparing a monohydroperfluorocarbon compound according to item 1 of the scope of the patent application, characterized in that at least one perfluoroalkylphosphorane and at least one base (a) or an organometallic compound are mixed in a suitable solvent reaction. The method for preparing bis (full-gas-fired-based) arsenite and full-gas-fired-based phosphonate according to the item in the scope of the patent of [beta], which is characterized in that at least one kind of perfluorofluorenyl-Wei and At least one kind of inorganic tritium reaction, in addition to single gas perfluorinated compounds, can be separated by salt exchange, or the formed bis (perfluorocarbon) phosphinate and full gas alkylated acid can be directly made. The salt is converted to the corresponding < bis (perfluoroalkynyl) phosphinic acid and perfluoroalkynyl phosphinic acid, or it is subsequently treated with an acid (preferably sulfuric acid) '^ followed by a neutralization reaction (preferably used The organic base (C)) gives these salts. 4. The method according to item 1 of the scope of patent application, characterized in that the perfluorophosphonium phosphonium used is a compound of the general formula I V ^ n ^ 2n + l) mPF5.m, where 1 ^ 8 'is preferably Bng, and In each case, the claw is a work, 2 or] 5. The method according to item 1 of the patent application, characterized in that the all-fluorene-based fire is selected from the group consisting of difluorotris (pentafluoroethyl) phosphorus and difluoro A group consisting of tris (n-n-fluorobutane) phosphorus trans, difluorotris (n-heptafluoropropyl) phosphonium phosphonium and tris (bi-nine-fluorobutane) castane. 84146 200306980 6. According to the order please The method of item 2 or 3 of the patent scope is characterized in that the test (a) or (C) used is at least one organic base. 7. The method of item 6 in the scope of the patent application is characterized by the organic test (group) ): Selected from the group consisting of: calcined hydrogen hydroxide, aryl gas oxidized di-tyl vanadium hydroxide, fluorenyl hydroxide scale, aryl hydroxide scale, 2-base vanadium hydroxide scale, Benzylamine, arylamine, arylarylamine, phenylphosphine, arylphosphine, and alkylarylphosphine. According to the method disclosed in the patent claim No. 23, it is characterized by using at least one inorganic (A) or (b). The method according to item 8 of the scope of the patent application, characterized in that the inorganic test (group) is selected from the group consisting of a metal test and a soil metal hydroxide. The method of item 9 of Shenqiao's patent scope is characterized in that the metal gas oxygen is selected from the group consisting of hydroxide, hydroxide monohydrate, steel hydroxide and potassium hydroxide. The method of item 9 of the full-time gj, characterized in that the soil test metal nitrogen oxide is selected from the group consisting of barium hydroxide, barium hydroxide octahydrate, and nitrogen oxidation conversion. 2 It is claimed in item 2 of the patent scope The method is characterized in that the organometallic compound is selected from the group consisting of: a metal alkoxide, preferably an alkali metal alkoxide; a metal aryl oxide; a metal alkyl sulfur oxide; a metal aryl sulfur oxide , Metal alkyl compounds, aryl metal compounds and GHgnard reagents. According to the method of claim 1 of the patent scope, it is characterized in that the reaction medium is necessary and can be mixed with one or more organic solvents. 84146 200306980 14 · According to The method according to claim 1 is characterized in that the reaction medium used is one or more organic solvents. 15 · = The method in claim 13 or 14 is characterized in that the organic / cereal is selected from alcohol Group, ethers, fluorenyl amines, sulfoxides, sulfoniums, nitriles, and hydrocarbons. 16. According to the method of claim 15 in the scope of patent application, which is characterized by the burning group of the alcohol # Has 1 to 4 carbon atoms, and is preferably selected from the group consisting of methanol, ethanol, isopropanol, and a mixture of at least two of these alcohols. Π · -perfluoroalkylphosphonates and bis ( Perfluoroalkyl) phosphinates, which are selected from the group consisting of partially alkylated and fully alkylated ammonium, scales, pyrene, pyridine, pyridamine, pyrimidine, pyridine, imidazole, pyrazole, Triazole, tritium and triazole salts. 18. Perfluoroalkylphosphonate and bis (perfluoroalkyl) phosphinate according to item 17 of the scope of the patent application, which have a positive electrode selected from the group consisting of 84146 200306980 其中R1至R5可相同或不同，且可視需要藉由一個單鍵 或雙鍵直接彼此鍵結，且各獨立或一起如下定義： -H， -鹵素，其中該鹵素並未直接與N鍵結， -燒基（Ci至Cs)，其可部份或完全藉由其它基團取代， 該其它基團較佳為 F，Cl，N(CnF(2n+1-x)Hx)2，CKCnFpwwHd ，S〇2(CnF(2n+ i-x)Hx)，CnF(2n+卜X)HX’ 其中 1 <n<6且 〇<χ<2η+1。 19· 一種根據申請專利範圍第丨7或1 8項之全氟烷基膦酸鹽及 雙（全氟烷基）亞膦酸鹽作為離子液體之用途。 2〇· —種根據申請專利範圍第17或18項之全氟烷基膦酸鹽及 雙（全氟烷基）亞膦酸鹽作為相轉移觸媒或表面活化劑之 用途。 84146 4- 200306980 柒、指定代表圖： (一) 本案指定代表圖為：第（ ）圖。 (二) 本代表圖之元件代表符號簡單說明： 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學式： (CnF 2n+l)mf>F 5-m I 8414684146 200306980 wherein R1 to R5 may be the same or different, and may be directly bonded to each other through a single bond or a double bond, and each is independently or together defined as follows: -H, -halogen, wherein the halogen is not directly bonded to the N bond -(Ci to Cs), which may be partially or completely substituted by other groups, the other groups are preferably F, Cl, N (CnF (2n + 1-x) Hx) 2, CKCnFpwwHd , So2 (CnF (2n + ix) Hx), CnF (2n + Bu X) HX ', where 1 < n < 6 and 0 < χ < 2η + 1. 19. Use of a perfluoroalkylphosphonate and a bis (perfluoroalkyl) phosphinate as an ionic liquid according to the scope of application patent No. 7 or 18. 20. The use of perfluoroalkylphosphonates and bis (perfluoroalkyl) phosphinates as phase transfer catalysts or surfactants according to item 17 or 18 of the scope of the patent application. 84146 4- 200306980 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) Brief description of the element representative symbols of this representative diagram: 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: (CnF 2n + l) mf > F 5-m I 84146
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