JPS6216946B2 - - Google Patents
Info
- Publication number
- JPS6216946B2 JPS6216946B2 JP3867783A JP3867783A JPS6216946B2 JP S6216946 B2 JPS6216946 B2 JP S6216946B2 JP 3867783 A JP3867783 A JP 3867783A JP 3867783 A JP3867783 A JP 3867783A JP S6216946 B2 JPS6216946 B2 JP S6216946B2
- Authority
- JP
- Japan
- Prior art keywords
- perfluoro
- formula
- group
- ring
- sulfuric acid
- 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.)
- Expired
Links
- -1 perfluoro Chemical group 0.000 claims description 21
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- XAMXPQOUNJEDLT-UHFFFAOYSA-N 1,2,2,3,3,4,4,5,5,6,6,7,7-tridecafluoroazepane Chemical group FN1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F XAMXPQOUNJEDLT-UHFFFAOYSA-N 0.000 claims description 2
- VCEAGMYKGZNUFL-UHFFFAOYSA-N 1,2,2,3,3,4,4,5,5,6,6-undecafluoropiperidine Chemical group FN1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F VCEAGMYKGZNUFL-UHFFFAOYSA-N 0.000 claims description 2
- IMJJOJJRJLJSTL-UHFFFAOYSA-N 1,2,2,3,3,4,4,5,5-nonafluoropyrrolidine Chemical group FN1C(F)(F)C(F)(F)C(F)(F)C1(F)F IMJJOJJRJLJSTL-UHFFFAOYSA-N 0.000 claims description 2
- BJBXQQZMELYVMD-UHFFFAOYSA-N 2,2,3,3,4,5,5,6,6-nonafluoromorpholine Chemical group FN1C(F)(F)C(F)(F)OC(F)(F)C1(F)F BJBXQQZMELYVMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000005460 perfluorocycloalkyl group Chemical group 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 7
- 229940074994 mercuric sulfate Drugs 0.000 description 7
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- JHHFDZGMTGZWGV-UHFFFAOYSA-N 3,3,4,4,5,5-hexafluoro-1-(1,1,2,2,2-pentafluoroethyl)pyrrolidin-2-one Chemical compound FC(F)(F)C(F)(F)N1C(=O)C(F)(F)C(F)(F)C1(F)F JHHFDZGMTGZWGV-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- UMGCTGRNIYHTCR-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoro-1-(1,1,2,2,2-pentafluoroethyl)pyrrolidine Chemical compound FC(F)(F)C(F)(F)N1C(F)(F)C(F)(F)C(F)(F)C1(F)F UMGCTGRNIYHTCR-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XYPGJVPVOPBFMI-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6-decafluoro-1-(1,1,2,2,3,3,3-heptafluoropropyl)piperidine Chemical compound FC(F)(F)C(F)(F)C(F)(F)N1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F XYPGJVPVOPBFMI-UHFFFAOYSA-N 0.000 description 2
- PPIFMJXJHBIWAY-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoro-1-(1,1,2,2,3,3,4,4,5,5,5-undecafluoropentyl)pyrrolidine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)N1C(F)(F)C(F)(F)C(F)(F)C1(F)F PPIFMJXJHBIWAY-UHFFFAOYSA-N 0.000 description 2
- DBPOMYFTYONHGA-UHFFFAOYSA-N 2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2,3,3,4,4,5,5-nonafluorocyclopentyl)morpholine Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C1(F)N1C(F)(F)C(F)(F)OC(F)(F)C1(F)F DBPOMYFTYONHGA-UHFFFAOYSA-N 0.000 description 2
- FDWFLVJNJYRHIU-UHFFFAOYSA-N 3-morpholin-4-ylpropane-1-sulfonyl fluoride Chemical compound FS(=O)(=O)CCCN1CCOCC1 FDWFLVJNJYRHIU-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- CYMKDLLKXWRAMC-UHFFFAOYSA-N 2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2,3,3,4,4,5,5,6,6-undecafluorocyclohexyl)morpholine Chemical compound FC1(F)C(F)(F)OC(F)(F)C(F)(F)N1C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F CYMKDLLKXWRAMC-UHFFFAOYSA-N 0.000 description 1
- PQMAKJUXOOVROI-UHFFFAOYSA-N 2,2,3,3,5,5,6,6-octafluoro-4-(trifluoromethyl)morpholine Chemical compound FC(F)(F)N1C(F)(F)C(F)(F)OC(F)(F)C1(F)F PQMAKJUXOOVROI-UHFFFAOYSA-N 0.000 description 1
- FURGEISYRKIUMX-UHFFFAOYSA-N 2,2,5,5,6,6-hexafluoro-4-(trifluoromethyl)morpholin-3-one Chemical compound FC(F)(F)N1C(=O)C(F)(F)OC(F)(F)C1(F)F FURGEISYRKIUMX-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical class FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical class FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Hydrogenated Pyridines (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pyrrole Compounds (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
Description
本発明は各種の合成反応中間体として有用なペ
ルフルオロラクタム類の製造方法に関し、さらに
詳しくは、ペルフルオロ(N−アルキル基置換環
状アミン)類と発煙硫酸とを加熱反応させてペル
フルオロラクタム類を製造する方法に関するもの
である。
ペルフルオロラクタム類は分子内に活性なカル
ボニル基を有しているため、極めて反応性に富
み、さらに有用な物質を製造するための中間体と
して極めて重要な化合物であり、例えば機能性高
分子膜の出発物質などとして注目されている。
従来、ペルフルオロラクタムとしては、ペルフ
ルオロ(N−メチル−3−オキソモルホリン)の
みが知られており、このものはペルフルオロ(N
−メチルモルホリン)と無水硫酸との反応で合成
したα−フルオロスルフアト化合物を加水分解す
ることによつて得られている〔米国特許第
3956293号明細書)。
前記反応の出発物質として用いられるペルフル
オロ(N−メチルモルホリン)のようなペルフル
オロ第三級アミン類は、一般に熱的かつ化学的に
安定であつて、このものを用いた化学反応の例は
少なく、例えば前記の反応以外に、無水塩化アル
ミニウムとの反応〔S.A.Mazalov and S.V.
Sokolov、Zh.Obshch.Khim.、36(7)、1330
(1966);CA 65、16851h〕が知られているにす
ぎない。
本発明者は、ペルフルオロ(N−アルキル基置
換環状アミン)類と発煙硫酸との反応について鋭
意研究を重ねた結果、意外にもペルフルオロラク
タム類を一段階で収率よく製造しうることを見出
し、本発明を完成するに至つた。
すなわち、本発明は、一般式
〔式中のAは
The present invention relates to a method for producing perfluorolactams useful as various synthetic reaction intermediates, and more specifically, perfluorolactams are produced by heating and reacting perfluoro (N-alkyl group-substituted cyclic amines) with fuming sulfuric acid. It is about the method. Perfluorolactams have an active carbonyl group in their molecules, making them highly reactive and extremely important compounds as intermediates for producing more useful substances, such as the production of functional polymer membranes. It is attracting attention as a starting material. Conventionally, only perfluoro(N-methyl-3-oxomorpholine) is known as perfluorolactam;
-Methylmorpholine) and sulfuric anhydride [U.S. Patent No.
3956293 specification). Perfluoro tertiary amines such as perfluoro(N-methylmorpholine) used as starting materials for the above reaction are generally thermally and chemically stable, and there are few examples of chemical reactions using them. For example, in addition to the above-mentioned reactions, reactions with anhydrous aluminum chloride [SA Mazalov and SV
Sokolov, Zh.Obshch.Khim., 36(7), 1330
(1966); CA 65, 16851h] is only known. As a result of extensive research into the reaction between perfluoro (N-alkyl group-substituted cyclic amines) and fuming sulfuric acid, the present inventors have unexpectedly discovered that perfluorolactams can be produced in a single step with good yield. The present invention has now been completed. That is, the present invention provides the general formula [A in the formula is
【式】と共にペルフルオロピ
ロリジン環、ペルフルオロピペリジン環、ペルフ
ルオロヘキサメチレンイミン環又はペルフルオロ
モルホリン環を形成する二価の基であり、Rはハ
ロゲン原子、SO2F基、ペルフルオロジアルキル
アミノ基又はA divalent group that forms a perfluoropyrrolidine ring, a perfluoropiperidine ring, a perfluorohexamethyleneimine ring, or a perfluoromorpholine ring together with [Formula], and R is a halogen atom, an SO 2 F group, a perfluorodialkylamino group, or
【式】基(ただしAは前記と
同じ)、nは1〜5の整数であり、またRと−
(CF2)n−とは一緒になつてペルフルオロシク
ロアルキル環を形成することもできる〕
で表わされるペルフルオロ(N−アルキル基置換
環状アミン)類と発煙硫酸とを加熱反応させるこ
とを特徴とする、一般式
(式中のA、R及びnは前記と同じ意味をもつ)
で表わされるペルフルオロラクタム類の製造方法
を提供するものである。
〔式中のAは−(CF2)2−、−(CF2)3−、−(CF2)4
−又は−CF2OCF2−基、Rfはペルフルオロシク
ロペンチル基、ペルフルオロシクロヘキシル基、
−Co1F2o1+1(ただしn1=1〜9)、[Formula] group (A is the same as above), n is an integer of 1 to 5, and R and -
(CF 2 )n- can also be combined with N- to form a perfluorocycloalkyl ring] and is characterized by heating and reacting perfluoro (N-alkyl group-substituted cyclic amine) with fuming sulfuric acid. , general formula (In the formula, A, R and n have the same meanings as above.) A method for producing perfluorolactams represented by the following is provided. [A in the formula is −(CF 2 ) 2 −, −(CF 2 ) 3 −, −(CF 2 ) 4
- or -CF 2 OCF 2 - group, Rf is a perfluorocyclopentyl group, a perfluorocyclohexyl group,
−C o1 F 2o1+1 (however, n 1 = 1 to 9),
【式】(ただしn2=1〜 6)、[Formula] (where n 2 = 1 to 6),
【式】(ただしn3=1〜 6)、[Formula] (where n 3 = 1 to 6),
【式】(ただしn4=1〜 6)、[Formula] (where n 4 = 1 to 6),
【式】(ただしm=2〜5)
又はω位にCl、−SO2F若しくは−SF5をもつ炭素
数1〜5のペルフルオロアルキル基である)
本発明方法において原料として用いるペルフル
オロ(N−アルキル基置換環状アミン)類は、一
般式()
(式中のA、R及びnは前記と同じ意味をもつ)
で表わされる化合物であり、具体例としてその一
部を示すと、ペルフルオロ(N−エチルピロリジ
ン)、ペルフルオロ(N−プロピルピペリジン)、
ペルフルオロ(N−2−クロロエチルモルホリ
ン)、ペルフルオロ(1・2−ビスピロリジノエ
タン)、ペルフルオロ(N−ジエチルアミノエチ
ルピロリジン)、ペルフルオロ(3−モルホリノ
プロパンスルホニルフルオリド)、ペルフルオロ
(N−アミルピロリジン)、ペルフルオロ(N−シ
クロペンチルモルホリン)、ペルフルオロ(N−
シクロヘキシルモルホリン)などが挙げられる。
本発明方法においては、前記のペルフルオロ
(N−アルキル基置換環状アミン)類と好ましく
は過剰量の10〜60重量%濃度の発煙硫酸とを通常
100〜200℃の温度範囲で1〜100時間反応させる
ことによつて、一般式()
(式中のA、R及びnは前記と同じ意味をもつ)
で表わされるペルフルオロラクタム類が好収率で
得られる。この反応において、触媒量の硫酸第2
水銀を添加することにより、目的物のペルフルオ
ロラクタム類の収率を若干向上させることができ
る。消費されたペルフルオロ(N−アルキル基置
換環状アミン)類に対するペルフルオロラクタム
類の収率は、モル基準で通常20〜90%の範囲であ
る。
本発明方法においては、反応終了後、大部分の
ペルフルオロラクタム類は未反応のペルフルオロ
環状アミン類とともに上層となつて、下層の硫酸
層と分離するため、生成物と発煙硫酸との分離は
極めて容易である。また、少量のペルフルオロラ
クタム類が硫酸層に溶解しているが、これは、例
えばペルフルオロアミン、ペルフルオロエーテ
ル、ペルフルオロカーボンあるいは1・1・2−
トリクロロトリフルオロエタンなどのフツ素系溶
媒で抽出することにより回収可能である。さらに
原料のペルフルオロ環状アミン類と生成物のペル
フルオロラクタム類の分離は、例えば蒸留、分取
ガスクロマトグラフイーなどの方法によつて行う
ことができる。
本発明方法によつて得られるペルフルオロラク
タム類は室温では空気中で発煙する液体であり、
活性なカルボニル基を有しているため極めて反応
性に富む化合物であつて、例えば機能的高分子膜
の原料、界面活性剤の原料として重要である。
次に実施例によつて本発明をさらに詳細に説明
する。
実施例 1
容量が約17mlのパイレツクスアンプル中に、ペ
ルフルオロ(N−エチルピロリジン)1.72g
(5.20mmol)、30%発煙硫酸5.8g及び触媒量の硫
酸第2水銀を仕込み、170℃の温度で23時間加熱
した。反応後、透明なフルオロカーボン層(1.26
g)を下層の硫酸層と分離し、これをガスクロマ
トグラフイー、赤外吸収スペクトル、19F核磁気
共鳴スペクトルなどで分析したところ、この中に
ペルフルオロ(N−エチル−2−オキソピロリジ
ン)がガスクロピーク面積比で73.3%含まれてい
た。ペルフルオロ(N−エチル−2−オキソピロ
リジン)の収率は消費された原料を基にすると
71.5%であつた。精製したペルフルオロ(N−エ
チル−2−オキソピロリジン)の沸点は69.0〜
70.5℃で、n20 Dは1.2895であつた。
実施例 2
容量が95mlのモネルシリンダー中にペルフルオ
ロ(N−エチルピロリジン)49.5g(0.149モ
ル)と30%発煙硫酸46.8gを仕込み、170℃の温
度で23時間加熱した。反応後、実施例1と同じよ
うに処理してフルオロカーボン層21.7gを得た。
さらに下層の硫酸層を25mlの1・1・2−トリク
ロロトリフルオロエタンで抽出し、抽出液を分析
したところ、10.9gのペルフルオロ(N−エチル
−2−オキソピロリジン)が得られた。両者から
の生成物を併せると、ペルフルオロ(N−エチル
−2−オキソピロリジン)の収率は65.3%であつ
た。
実施例 3
実施例1と同じようにパイレツクスアンプル中
で、ペルフルオロ(N−プロピルピペリジン)
1.80g(4.16mmol)と30%発煙硫酸5.2gを微量
の硫酸第2水銀の存在下、170℃の温度で25時間
反応させた。生成物を実施例1と同じように分
離、分析を行つたところ、ペルフルオロ(N−プ
ロピル−2−オキソピペリジン)(b.p.109.5℃、
n20 D1.2959)が45.5%の収率で得られた。
実施例 4
ペルフルオロ(N−2−クロロエチルモルホリ
ン)1.80g(4.51mmol)及び30%発煙硫酸4.8g
を、微量の硫酸第2水銀の存在下、145℃の温度
で24時間反応させた。反応生成物を実施例1と同
じように分離して、分析を行つたところ、ペルフ
ルオロ(N−2−クロロエチル−3−オキソモル
ホリン)(b.p.106.5〜107.0℃、n20 D1.3212)が
58.7%の収率で得られた。
実施例 5
ペルフルオロ(1・2−ビスピロリジノエタ
ン)1.89g(3.27mmol)と30%発煙硫酸5.3g
を、触媒量の硫酸第2水銀の存在下、170℃で24
時間反応させた。反応生成物を実施例1と同じよ
うに分離し、分析を行つたところ、ペルフルオロ
(N−ピロリジノエチル−2−オキソピロリジ
ン)(b.p.176.5〜177.0、n20 D1.3168)が27.6%の
収率で、またペルフルオロ(1・2−ビス−2−
オキソピロリジノエタン)(b.p.185.0〜185.5)が
48.3%の収率で得られた。
実施例 6
ペルフルオロ(N−ジエチルアミノエチルピロ
リジン)1.90g(3.36mmol)と30%の発煙硫酸
5.2gを触媒量の硫酸第2水銀の存在下、170℃の
温度で48時間反応させた。生成物を実施例1と同
じように分離し、分析を行つたところ、ペルフル
オロ(N−ジエチルアミノエチル−2−オキソピ
ロリジン)(b.p.159.5℃、n20 D1.3073)が52.7%
の収率で得られた。
実施例 7
ペルフルオロ(3−モルホリノプロパンスルホ
ニルフルオリド)1.90g(4.10mmol)と30%発
煙硫酸5.2gを、触媒量の硫酸第2水銀の存在
下、170℃の温度で24時間反応させた。生成物を
実施例1と同じように分離して、分析したとこ
ろ、ペルフルオロ〔3−(3−オキソモルホリ
ノ)プロパンスルホニルフルオリド〕(b.p.157.0
〜157.3℃、n20 D1.3278)が62.0%の収率で得られ
た。
実施例 8
ペルフルオロ(N−アミルピロリジン)1.83g
(3.79mmol)と30%発煙硫酸4.9gを、170℃の温
度で24時間反応させた。生成物を実施例1と同じ
ように分離して、分析したところ、ペルフルオロ
(N−アミル−2−オキソピロリジン)(b.
p.133.5〜134.0℃)が73.8%の収率で得られた。
実施例 9
ペルフルオロ(N−シクロペンチルモルホリ
ン)1.93g(4.19mmol)と30%発煙硫酸5.0g
を、触媒量の硫酸第2水銀の存在下、170℃で24
時間反応させた。生成物を実施例1と同じように
分離して分析したところ、ペルフルオロ(N−シ
クロペンチル−3−オキソモルホリン)(b.
p.139.5〜139.8℃、n20 D1.3174)が79.5%の収率で
得られた。[Formula] (where m = 2 to 5) or a perfluoroalkyl group having 1 to 5 carbon atoms having Cl, -SO 2 F or -SF 5 at the ω position) Perfluoro(N- Alkyl group-substituted cyclic amines) have the general formula () (A, R and n in the formula have the same meanings as above) Some specific examples include perfluoro(N-ethylpyrrolidine), perfluoro(N-propylpiperidine),
Perfluoro(N-2-chloroethylmorpholine), perfluoro(1,2-bispyrrolidinoethane), perfluoro(N-diethylaminoethylpyrrolidine), perfluoro(3-morpholinopropanesulfonylfluoride), perfluoro(N-amylpyrrolidine) , perfluoro(N-cyclopentylmorpholine), perfluoro(N-
cyclohexylmorpholine), etc. In the method of the present invention, the perfluoro(N-alkyl group-substituted cyclic amines) and preferably an excess of fuming sulfuric acid at a concentration of 10 to 60% by weight are usually used.
By reacting at a temperature range of 100-200℃ for 1-100 hours, the general formula () (A, R and n in the formula have the same meanings as above) A perfluorolactam represented by the following is obtained in good yield. In this reaction, a catalytic amount of sulfuric acid
By adding mercury, the yield of the target perfluorolactam can be slightly improved. The yield of perfluorolactams based on the consumed perfluoro(N-alkyl group-substituted cyclic amine) is usually in the range of 20 to 90% on a molar basis. In the method of the present invention, after the reaction is completed, most of the perfluorolactams form an upper layer together with unreacted perfluorocyclic amines and are separated from the lower sulfuric acid layer, so it is extremely easy to separate the product from the fuming sulfuric acid. It is. In addition, a small amount of perfluorolactams are dissolved in the sulfuric acid layer, which may be caused by, for example, perfluoroamines, perfluoroethers, perfluorocarbons, or 1,1,2-
It can be recovered by extraction with a fluorine-based solvent such as trichlorotrifluoroethane. Furthermore, the separation of perfluorocyclic amines as raw materials and perfluorolactams as products can be carried out, for example, by methods such as distillation and preparative gas chromatography. The perfluorolactams obtained by the method of the present invention are liquids that emit smoke in the air at room temperature,
Because it has an active carbonyl group, it is an extremely reactive compound, and is important as a raw material for functional polymer membranes and surfactants, for example. Next, the present invention will be explained in more detail with reference to Examples. Example 1 1.72 g perfluoro(N-ethylpyrrolidine) in a Pyrex ampoule with a volume of approximately 17 ml.
(5.20 mmol), 5.8 g of 30% fuming sulfuric acid, and a catalytic amount of mercuric sulfate were charged and heated at a temperature of 170° C. for 23 hours. After the reaction, a transparent fluorocarbon layer (1.26
g) was separated from the lower sulfuric acid layer and analyzed by gas chromatography, infrared absorption spectroscopy, 19 F nuclear magnetic resonance spectroscopy, etc., and it was found that perfluoro(N-ethyl-2-oxopyrrolidine) was present in the gas chromatography. It contained 73.3% in terms of peak area ratio. The yield of perfluoro(N-ethyl-2-oxopyrrolidine) is based on the raw material consumed.
It was 71.5%. The boiling point of purified perfluoro(N-ethyl-2-oxopyrrolidine) is 69.0~
At 70.5°C , n20D was 1.2895. Example 2 49.5 g (0.149 mol) of perfluoro(N-ethylpyrrolidine) and 46.8 g of 30% oleum were placed in a Monel cylinder having a capacity of 95 ml, and heated at 170° C. for 23 hours. After the reaction, the same treatment as in Example 1 was carried out to obtain 21.7 g of a fluorocarbon layer.
Further, the lower sulfuric acid layer was extracted with 25 ml of 1,1,2-trichlorotrifluoroethane, and the extract was analyzed, and 10.9 g of perfluoro(N-ethyl-2-oxopyrrolidine) was obtained. When the products from both were combined, the yield of perfluoro(N-ethyl-2-oxopyrrolidine) was 65.3%. Example 3 Perfluoro(N-propylpiperidine) was prepared in a Pyrex ampoule as in Example 1.
1.80 g (4.16 mmol) and 5.2 g of 30% oleum were reacted at a temperature of 170° C. for 25 hours in the presence of a trace amount of mercuric sulfate. The product was separated and analyzed in the same manner as in Example 1, and it was found that perfluoro(N-propyl-2-oxopiperidine) (bp 109.5°C,
n 20 D 1.2959) was obtained in a yield of 45.5%. Example 4 Perfluoro(N-2-chloroethylmorpholine) 1.80 g (4.51 mmol) and 30% oleum 4.8 g
were reacted for 24 hours at a temperature of 145° C. in the presence of a trace amount of mercuric sulfate. The reaction product was separated and analyzed in the same manner as in Example 1, and it was found that perfluoro(N-2-chloroethyl-3-oxomorpholine) (bp 106.5-107.0°C, n 20 D 1.3212)
Obtained with a yield of 58.7%. Example 5 1.89 g (3.27 mmol) of perfluoro(1,2-bispyrrolidinoethane) and 5.3 g of 30% fuming sulfuric acid
24 at 170°C in the presence of a catalytic amount of mercuric sulfate.
Allowed time to react. The reaction product was separated and analyzed in the same manner as in Example 1, and perfluoro(N-pyrrolidinoethyl-2-oxopyrrolidine) (bp 176.5-177.0, n 20 D 1.3168) was found in a yield of 27.6%. perfluoro(1,2-bis-2-
Oxopyrrolidinoethane) (bp185.0-185.5)
Obtained with a yield of 48.3%. Example 6 1.90 g (3.36 mmol) of perfluoro(N-diethylaminoethylpyrrolidine) and 30% fuming sulfuric acid
5.2 g were reacted for 48 hours at a temperature of 170° C. in the presence of a catalytic amount of mercuric sulfate. The product was separated and analyzed in the same manner as in Example 1, and it was found that perfluoro(N-diethylaminoethyl-2-oxopyrrolidine) (bp 159.5°C, n 20 D 1.3073) was 52.7%.
was obtained in a yield of . Example 7 1.90 g (4.10 mmol) of perfluoro(3-morpholinopropanesulfonyl fluoride) and 5.2 g of 30% oleum were reacted at a temperature of 170° C. for 24 hours in the presence of a catalytic amount of mercuric sulfate. The product was isolated and analyzed in the same manner as in Example 1, and was found to be perfluoro[3-(3-oxomorpholino)propanesulfonyl fluoride] (bp157.0
˜157.3° C., n 20 D 1.3278) was obtained in a yield of 62.0%. Example 8 Perfluoro(N-amylpyrrolidine) 1.83g
(3.79 mmol) and 4.9 g of 30% oleum were reacted at a temperature of 170° C. for 24 hours. The product was isolated and analyzed as in Example 1 and found to be perfluoro(N-amyl-2-oxopyrrolidine) (b.
p.133.5-134.0°C) was obtained in a yield of 73.8%. Example 9 1.93 g (4.19 mmol) of perfluoro(N-cyclopentylmorpholine) and 5.0 g of 30% fuming sulfuric acid
24 at 170°C in the presence of a catalytic amount of mercuric sulfate.
Allowed time to react. The product was isolated and analyzed as in Example 1 and found to be perfluoro(N-cyclopentyl-3-oxomorpholine) (b.
p.139.5-139.8°C, n20D 1.3174 ) was obtained in a yield of 79.5%.
Claims (1)
ルオロヘキサメチレンイミン環又はペルフルオロ
モルホリン環を形成する二価の基であり、Rはハ
ロゲン原子、SO2F基、ペルフルオロジアルキル
アミノ基又は【式】基(ただしAは前記と 同じ)、nは1〜5の整数であり、またRと−
(CF2)n−とは一緒になつてペルフルオロシク
ロアルキル環を形成することもできる〕 で表わされるペルフルオロ(N−アルキル基置換
環状アミン)類と発煙硫酸とを加熱反応させるこ
とを特徴とする、一般式 (式中のA、R及びnは前記と同じ意味をもつ) で表わされるペルフルオロラクタム類の製造方
法。[Claims] 1. General formula [In the formula, A is a divalent group that forms a perfluoropyrrolidine ring, perfluoropiperidine ring, perfluorohexamethyleneimine ring, or perfluoromorpholine ring together with [formula], and R is a halogen atom, SO 2 F group, perfluorodialkylamino group or [Formula] group (where A is the same as above), n is an integer of 1 to 5, and R and -
(CF 2 )n- can also be combined with N- to form a perfluorocycloalkyl ring] and is characterized by heating and reacting perfluoro (N-alkyl group-substituted cyclic amine) with fuming sulfuric acid. , general formula (A, R and n in the formula have the same meanings as above) A method for producing perfluorolactams represented by the following.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3867783A JPS59164772A (en) | 1983-03-09 | 1983-03-09 | Preparation of perfluorolactams |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3867783A JPS59164772A (en) | 1983-03-09 | 1983-03-09 | Preparation of perfluorolactams |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59164772A JPS59164772A (en) | 1984-09-17 |
JPS6216946B2 true JPS6216946B2 (en) | 1987-04-15 |
Family
ID=12531902
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3867783A Granted JPS59164772A (en) | 1983-03-09 | 1983-03-09 | Preparation of perfluorolactams |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59164772A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62178569A (en) * | 1986-01-31 | 1987-08-05 | Agency Of Ind Science & Technol | Perfluorobicyclolactam compound and production thereof |
JPS63208572A (en) * | 1987-02-24 | 1988-08-30 | Daikin Ind Ltd | Perfluoro nitrogen-containing cyclic compound and production thereof |
-
1983
- 1983-03-09 JP JP3867783A patent/JPS59164772A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS59164772A (en) | 1984-09-17 |
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