JPS63284148A - Production of quaternary ammonium inorganic acid salt - Google Patents

Production of quaternary ammonium inorganic acid salt

Info

Publication number
JPS63284148A
JPS63284148A JP62117380A JP11738087A JPS63284148A JP S63284148 A JPS63284148 A JP S63284148A JP 62117380 A JP62117380 A JP 62117380A JP 11738087 A JP11738087 A JP 11738087A JP S63284148 A JPS63284148 A JP S63284148A
Authority
JP
Japan
Prior art keywords
inorganic acid
quaternary ammonium
solvent
reaction
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP62117380A
Other languages
Japanese (ja)
Other versions
JPH07116113B2 (en
Inventor
Shoichiro Mori
森 彰一郎
Kazuhiko Ida
和彦 井田
Makoto Ue
誠 宇恵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Petrochemical Co Ltd
Original Assignee
Mitsubishi Petrochemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Petrochemical Co Ltd filed Critical Mitsubishi Petrochemical Co Ltd
Priority to JP62117380A priority Critical patent/JPH07116113B2/en
Priority to US07/192,524 priority patent/US4892944A/en
Priority to DE8888107735T priority patent/DE3868138D1/en
Priority to EP88107735A priority patent/EP0291074B1/en
Publication of JPS63284148A publication Critical patent/JPS63284148A/en
Publication of JPH07116113B2 publication Critical patent/JPH07116113B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

PURPOSE:To obtain the titled compound useful as a phase-transfer catalyst, etc., in high efficiency and purity in two steps, by reacting a tertiary amine with a carbonic acid diester and reacting the resultant quaternary ammonium carbonate with an inorganic acid while discharging produced CO2 gas from the system. CONSTITUTION:A tertiary amine of formula I (R1-R3 are hydrocarbon residue of tertiary amine) e.g. triethylamine is made to react with a carbonic acid diester of formula II such as dimethyl carbonate in a solvent such as methanol or in the absence of solvent at 20-200 deg.C. The resultant quaternary ammonium carbonate of formula III, etc., is made to react with an inorganic acid of formula HX (X is conjugated residue of inorganic acid) in a solvent or in the absence of solvent while removing the generated CO2 gas from the system under reduced pressure or by blasting an inert gas into the reaction system. If necessary, the reaction product is purified e.g. by recrystallization using a proper solvent to obtain the objective compound of formula IV, etc., having solid phase and high purity and useful as an electrolyte for aqueous or organic electrolytic solution, various additives, chemicals, etc.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、三級アミンと炭酸ジエステルと反応させるこ
とにより、対応する四級アンモニウム炭酸塩とし、さら
にこれに無機酸を混合して脱炭酸することにより四級ア
ンモニウム無機酸塩を製造する方法に関する。
[Detailed Description of the Invention] [Industrial Application Field] The present invention involves reacting a tertiary amine with a carbonic acid diester to obtain a corresponding quaternary ammonium carbonate, which is then mixed with an inorganic acid to decarboxylate it. The present invention relates to a method for producing a quaternary ammonium inorganic acid salt.

本発明の方法で得られる四級アンモニウム無機酸塩は、
相関移動触媒などの各種触媒、・水系及び有機系の電解
液のための電解質、各種の添加物、薬品として幅広い分
野で使用される有用な有機化合物である。
The quaternary ammonium inorganic acid salt obtained by the method of the present invention is
It is a useful organic compound that is used in a wide range of fields as various catalysts such as phase transfer catalysts, electrolytes for aqueous and organic electrolytes, various additives, and chemicals.

C従来の技術〕 四級アンモニウム塩の合成方法としては、一般に、三級
アミン類をアルキルハライド、ジアルキル硫酸などで加
熱下で四級化する方法が採用されている。又、陰イオン
種を種々に変化させた四級アンモニウム塩を製造する場
合には、通常四級アンモニウムハライド(塩化物、臭化
物、ヨウ化物)の陰イオン交換による方法が採用されて
いる0例えば、下記に示すような反応式に従って、四級
アンモニウム臭化物を四級アンモニウム水酸化物に転換
したのち(反応1a)無機酸によって中和処理する方法
(反応1b)、四級アンモニウム臭化物を無機酸と反応
させ、対応する無機酸塩が不溶な溶媒を選定することに
より析出分離する方法(反応2)、四級アンモニウム臭
化物と無機酸のアルカリ金属塩とを反応させ、無機酸塩
を析出または抽出により得る方法(反応3)、さ・らに
は四級アンモニウム臭化物と無機酸の銀塩を反応させて
臭化線を析出させてが液から目的物を得る方法(反応4
)などを例示することができる。
C. Prior Art] As a method for synthesizing quaternary ammonium salts, a method is generally employed in which tertiary amines are quaternized with an alkyl halide, dialkyl sulfate, etc. under heating. In addition, when producing quaternary ammonium salts with various anion species, a method using anion exchange of quaternary ammonium halides (chloride, bromide, iodide) is usually adopted. According to the reaction formula shown below, quaternary ammonium bromide is converted to quaternary ammonium hydroxide (reaction 1a), and then neutralized with an inorganic acid (reaction 1b), the quaternary ammonium bromide is reacted with an inorganic acid. method (reaction 2), in which quaternary ammonium bromide and an alkali metal salt of an inorganic acid are reacted, and an inorganic acid salt is obtained by precipitation or extraction. Method (Reaction 3), and a method of reacting quaternary ammonium bromide with a silver salt of an inorganic acid to precipitate bromide rays to obtain the desired product from the solution (Reaction 4)
), etc. can be exemplified.

R4NeOHe−+  R4NeOH”       
(反応1a)R4N”O8e+HΦA”−+R4N@A
”+IhO(反応1b)R4NqDBre+H@Ae−
+R,N@Ae↓+HBr  (反応2)R,NΦBr
e+Na’AeRJ@Ae+NaBr  (反応3)R
n、NeDBre+AgeAe−+Ra、NeAe+A
gBr↓(反応4)反応1aによる四級アンモニウム水
酸化物の製造法としては、適当な溶媒に溶がした四級ア
ンモニウム臭化物を四級アンモニウム水酸化物型のイオ
ン交換樹脂と反応させる方法、四級アンモニウム臭化物
を液状媒体中でアルカリ金属水酸化物と反応させる方法
、電気化学的方法により臭素イオンをBr、とじて分離
し、水酸化物を得る方法、さらには銀化合物を用いる方
法などが知られている。
R4NeOHe−+ R4NeOH”
(Reaction 1a) R4N"O8e+HΦA"-+R4N@A
”+IhO (reaction 1b) R4NqDBre+H@Ae-
+R,N@Ae↓+HBr (Reaction 2) R,NΦBr
e+Na'AeRJ@Ae+NaBr (Reaction 3) R
n, NeDBre+AgeAe-+Ra, NeAe+A
gBr↓ (Reaction 4) Methods for producing quaternary ammonium hydroxide by reaction 1a include a method in which quaternary ammonium bromide dissolved in a suitable solvent is reacted with a quaternary ammonium hydroxide type ion exchange resin; A method of reacting class ammonium bromide with an alkali metal hydroxide in a liquid medium, a method of separating bromide ions into Br by an electrochemical method to obtain a hydroxide, and a method of using a silver compound are known. It is being

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

しかしながら、反応1aによるいずれの方法も四級アン
モニウム水酸化物の製法として高価な方法であり、又一
般に四級アンモニウム水酸化物中の臭素イオンを完全に
除くことは困難であるので、反応1bによる中和生成物
の純度に問題を生ずることが多い、また、反応2および
3の方法においては、目的とする四級アンモニウム無機
酸塩中の臭素イオンの除去はかなり困難であり、高純度
の四級アンモニウム無機酸塩を得る製造法としては不適
当である。反応4に基づく方法は定量的な反応を行わせ
る方法としては好ましいものと考えられるが、原料とな
る無機酸の銀塩がきわめて高価であり、工業的に採用で
きる方法とは言い難い。
However, any method using Reaction 1a is an expensive method for producing quaternary ammonium hydroxide, and it is generally difficult to completely remove the bromide ions in quaternary ammonium hydroxide, so Reaction 1b is used. This often causes problems with the purity of the neutralized product, and in the methods of Reactions 2 and 3, it is quite difficult to remove bromide ions from the target quaternary ammonium inorganic acid salts. This method is unsuitable as a production method for obtaining grade ammonium inorganic acid salts. Although the method based on Reaction 4 is considered to be preferable as a method for carrying out a quantitative reaction, the silver salt of an inorganic acid used as a raw material is extremely expensive, and it is difficult to say that it is a method that can be adopted industrially.

以上、四級アンモニウム臭化物を一例とて述べたが、他
のハライド、硫酸塩などを用いた場合も同様であり、一
般に効率的かつ高純度で種々の陰イオン交換した塩を作
る方法は知られていない。
The above description uses quaternary ammonium bromide as an example, but the same is true when using other halides, sulfates, etc., and there are generally no known methods for producing various anion-exchanged salts efficiently and with high purity. Not yet.

〔問題点を解決するための手段〕[Means for solving problems]

本発明者らは、従来の方法に較べて効率的な生産が可能
となり、かつ目的生成物の純度を高める工業的製法に関
する新しい技術を確立し、本発明に到達したものである
The present inventors have established a new technology for an industrial manufacturing method that enables more efficient production than conventional methods and improves the purity of the desired product, and has thus arrived at the present invention.

すなわち、本発明は、四級アンモニウムの無機酸塩を製
造する方法において、 (al  三級アミンを炭酸ジエステルと反応させるこ
とにより、対応する四級アンモニウム炭酸塩を製造する
工程 山) さらに、生成してくる四級アンモニウム炭酸塩を
無機酸と混合して炭酸ガスを系外に除去せしめて対応す
る無機酸塩を製造する工程の2段階の工程を経ることを
特徴とする四級アンモニウム無機酸塩の製造方法を提案
するものである。
That is, the present invention provides a method for producing an inorganic acid salt of quaternary ammonium, (a process step for producing a corresponding quaternary ammonium carbonate by reacting an al tertiary amine with a carbonic acid diester), which further comprises: The quaternary ammonium inorganic acid salt is characterized in that it undergoes a two-step process of mixing a quaternary ammonium carbonate with an inorganic acid and removing carbon dioxide gas from the system to produce the corresponding inorganic acid salt. This paper proposes a method for manufacturing.

〔発明の詳細な説明〕[Detailed description of the invention]

本発明の原料となる三級アミンとしては、トリメチルア
ミン、トリエチルアミン、エチルジメチルアミン、トリ
ーn−プロピルアミン、トリーn−ブチルアミン、トリ
ーn−オクチルアミン、ジエチル−1−プロピルアミン
、N、N、N ’ 、N ’−テトラメチルエチレンジ
アミンなどの脂肪族アミン類、N−メチルピロリジン、
N−エチルピロリジン、N−メチルピペリジン、N−エ
チルピペリジン、N−n−ブチルピペリジン、N−メチ
ルへキサメチレンイミン、N−エチルへキサメチレンイ
ミン、N−メチルモルホリン、N−ブチルモルホリン、
N、N’−ジメチルピペラジン、N、N ’−ジエチル
ピペラジン、1,5−ジアザビシクロ(4,3゜0〕−
5−ノネン、1.8−ジアザビシクロ(5,4゜0〕−
7−ウンデセンなどの脂環式アミン類、ピリジン、4−
ジメチルアミノピリジン、ピコリン類、N−メチルイミ
ダゾール、N−メチルベンズイミダゾール、キノリン、
4.4′−ジピリジルなどの含窒素へテロ環芳香族類な
どを挙げることができる。
Tertiary amines that can be used as raw materials for the present invention include trimethylamine, triethylamine, ethyldimethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-octylamine, diethyl-1-propylamine, N, N, N' , aliphatic amines such as N'-tetramethylethylenediamine, N-methylpyrrolidine,
N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-n-butylpiperidine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, N-methylmorpholine, N-butylmorpholine,
N,N'-dimethylpiperazine, N,N'-diethylpiperazine, 1,5-diazabicyclo(4,3°0)-
5-Nonene, 1,8-diazabicyclo(5,4゜0〕-
Alicyclic amines such as 7-undecene, pyridine, 4-
Dimethylaminopyridine, picolines, N-methylimidazole, N-methylbenzimidazole, quinoline,
Examples include nitrogen-containing heterocyclic aromatics such as 4.4'-dipyridyl.

炭酸ジエステルとしては炭酸ジメチル、炭酸エチルメチ
ル、炭酸ジエチル、炭酸ジプロピルなどを挙げることが
できるが、炭酸ジメチルなどのようにアルキル基の炭素
数が少ない方が四級化反応が速やかに進行し好ましい。
Examples of diester carbonates include dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, dipropyl carbonate, etc., but it is preferred that the alkyl group has fewer carbon atoms, such as dimethyl carbonate, because the quaternization reaction proceeds more quickly.

無機酸としては、特に制約はないが、炭酸に比較し強酸
なものほど陰イオンへの交換は速く完結する。又、炭酸
に較べて弱い酸でも平衡を少しずつずらせながら行うこ
とで時間をかければ陰イオン交換は達成される。これら
の無機酸の具体的な例として、肝r HCL HBr+
旧、 HNO31HzSO<。
There are no particular restrictions on the inorganic acid, but the stronger the acid compared to carbonic acid, the faster the exchange into anions will be completed. Furthermore, anion exchange can be achieved even with an acid weaker than carbonic acid if it is carried out while gradually shifting the equilibrium and takes time. Specific examples of these inorganic acids include liverr HCL HBr+
Old, HNO31HzSO<.

H+PO+、 HJOa、 HC104,HBFI H
PF6.HSbFa。
H+PO+, HJOa, HC104, HBFI H
PF6. HSbFa.

HASF、、、 HOS02G / 、 HOSOzF
IHzCrOa、HzStOb*)IMnO4+ HR
eOa、 HzSeOa+ H5CNなどを挙げること
ができる。
HASF,,,HOS02G/,HOSOzF
IHzCrOa, HzStOb*)IMnO4+ HR
Examples include eOa, HzSeOa+ H5CN, and the like.

第1工程である四級化反応は三級アミンと炭酸ジエステ
ルとのモル比で0.2〜5、より好ましくは0.3〜3
とし、溶媒の存在下又は非存在下、反応温度20〜20
0℃、より好ましくは30〜160℃で実施される。通
常三級アミンが四級化物に充分転化したところで、未反
応のアミンもしくは炭酸ジエステルを、溶媒を用いた場
合には溶媒とともに留去したのち、あるいは必要に応じ
て適当な有機溶媒で再結晶して、第2工程に送られる。
In the first step, the quaternization reaction, the molar ratio of tertiary amine and diester carbonate is 0.2 to 5, more preferably 0.3 to 3.
and in the presence or absence of a solvent, the reaction temperature is 20-20
It is carried out at 0°C, more preferably at 30-160°C. Usually, once the tertiary amine has been sufficiently converted to the quaternized product, the unreacted amine or diester carbonate is distilled off together with the solvent if a solvent is used, or if necessary, recrystallized from an appropriate organic solvent. Then, it is sent to the second process.

第2工程では、通常、四級アンモニウム炭酸塩に量論値
又は小過剰量の無機酸を溶媒存在下又は非存在下に滴下
し、発生する炭酸ガスを減圧下又は不活性ガスを反応系
に吹き込むことで除去する。
In the second step, usually, a stoichiometric value or a small excess amount of inorganic acid is added dropwise to the quaternary ammonium carbonate in the presence or absence of a solvent, and the generated carbon dioxide is removed under reduced pressure or an inert gas is introduced into the reaction system. Remove by blowing.

この際、起る反応は炭酸ジメチルを原料とした場合、次
式で表わされる。
At this time, the reaction that occurs is expressed by the following formula when dimethyl carbonate is used as the raw material.

(第1工程)  R+RzR3N + MezCO3−
R+RJJeN@0C−OMe(第2工程) R+Rz
R3MeN”C−OMe + HX−RIR2R3Me
N’Y’+ MeOH+ COz  t (式中、RIR1R3は三級アミンの炭化水素残基、X
は無機酸の共役塩基を示す、) 反応後、副生アルコール及び溶媒を用いた場合には溶媒
とを留去したのち得られる固体が目的の四級アンモニウ
ム無機酸塩である。必要に応じて適当な溶媒により再結
晶などで高純度なものを得ることができる。
(First step) R+RzR3N + MezCO3−
R+RJJeN@0C-OMe (2nd process) R+Rz
R3MeN"C-OMe + HX-RIR2R3Me
N'Y'+ MeOH+ COz t (wherein, RIR1R3 is a hydrocarbon residue of a tertiary amine,
represents the conjugate base of the inorganic acid.) After the reaction, the by-product alcohol and the solvent are distilled off when the solvent is used, and the solid obtained is the target quaternary ammonium inorganic acid salt. If necessary, a highly pure product can be obtained by recrystallization using an appropriate solvent.

又、炭酸イオンを完全に除くために量論値より少し過剰
な無機酸を使用した場合には、過剰の無機酸を再結晶な
どの処理によって除くことができる。
Further, when an inorganic acid is used in an amount slightly in excess of the stoichiometric value in order to completely remove carbonate ions, the excess inorganic acid can be removed by a treatment such as recrystallization.

〔発明の効果〕〔Effect of the invention〕

本発明の方法によれば、効率的に各種の四級アンモニウ
ム無機酸塩を製造することが可能であるが、同時に目的
とする塩を高純度で得ることができる点も本発明の大き
な特徴である。
According to the method of the present invention, it is possible to efficiently produce various quaternary ammonium inorganic acid salts, and at the same time, a major feature of the present invention is that the desired salt can be obtained with high purity. be.

〔実施例〕〔Example〕

以下、実施例により本発明をさらに具体的に説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.

実施例−1 (第1工程) 攪拌式オートクレーブに炭酸ジメチル17.8 g、ト
リエチルアミン20.0 g及び溶媒としてメタノール
20.0 gを充填し、反応温度115℃、反応圧力5
.0kg/cJGで12時間反応した。反応後オートク
レーブを冷却し、反応液を取り出してガスクロマトグラ
フで分析したところ、トリエチルアミンの転化率は94
.6%であり、未反応物及び溶媒を留去したのちの固体
収量は34.0 gであった(理論値の89.9%)0
元素分析並びにH−NMRなどからこのものはトリエチ
ルメチルアンモニウムメチルカーボネートであることが
確認された。
Example-1 (1st step) A stirring autoclave was filled with 17.8 g of dimethyl carbonate, 20.0 g of triethylamine, and 20.0 g of methanol as a solvent, and the reaction temperature was 115°C and the reaction pressure was 5.
.. The reaction was carried out at 0 kg/cJG for 12 hours. After the reaction, the autoclave was cooled and the reaction solution was taken out and analyzed by gas chromatography, and the conversion rate of triethylamine was 94.
.. 6%, and the solid yield after distilling off unreacted substances and solvent was 34.0 g (89.9% of the theoretical value).
This product was confirmed to be triethylmethylammonium methyl carbonate by elemental analysis and H-NMR.

(第2工程) 得られたトリエチルメチルアンモニウムメチルカーボネ
ート10.0 gを水15gに溶解させ、60%HCI
t Oe水溶液8.8gを徐々に添加した。添加と同時
に激しく炭酸ガスが発生した。より完全に炭酸ガスを除
去するために40℃/ 20 mHgで2時間脱気し、
イオンクロマトグラフィーにより炭酸イオンが20pp
m以下であることを確認後、水を留去した。残渣を9.
5gのEtOHから再結晶して過塩素酸トリエチルメチ
ルアンモニウム10.4 g(トリエチルアミンに対し
82.7%収率)を得た。
(Second step) 10.0 g of the obtained triethylmethylammonium methyl carbonate was dissolved in 15 g of water, and 60% HCI
8.8 g of t Oe aqueous solution was gradually added. At the same time as the addition, carbon dioxide gas was generated violently. Degas at 40°C/20 mHg for 2 hours to remove carbon dioxide gas more completely.
Carbonate ions are 20pp by ion chromatography.
After confirming that the water was below m, water was distilled off. 9. Residue.
Recrystallization from 5 g of EtOH gave 10.4 g of triethylmethylammonium perchlorate (82.7% yield based on triethylamine).

実施例−2 (第1工程) 攪拌式オートクレーブに炭酸ジメチル68.8g。Example-2 (1st step) 68.8 g of dimethyl carbonate in a stirred autoclave.

N−メチルピロリジン65.0 g及び溶媒としてメタ
ノール60.0 gを充填し、反応温度120℃、反応
圧力3kg/dGで6時間反応した0反応後、オートク
レーブを冷却し、反応液を取り出してガスクロマトグラ
フで分析したところ、N−メチルピロリジンの転化率は
98.1%であった。未反応物及び溶媒を留去したとこ
ろ130°、6 gの固体が回収された(理論値の97
.6%)、元素分析並びにH−NMRなどから、この固
体はN、N−ジメチルピロリジニウムメチルカーボネー
トであることが確認された。
Filled with 65.0 g of N-methylpyrrolidine and 60.0 g of methanol as a solvent, the autoclave was reacted for 6 hours at a reaction temperature of 120°C and a reaction pressure of 3 kg/dG. After the reaction, the autoclave was cooled, and the reaction solution was taken out and subjected to gas chromatography. When analyzed by tograph, the conversion rate of N-methylpyrrolidine was 98.1%. When unreacted substances and solvent were distilled off at 130°, 6 g of solid was recovered (theoretical value of 97
.. 6%), elemental analysis and H-NMR, it was confirmed that this solid was N,N-dimethylpyrrolidinium methyl carbonate.

(第2工程) 得られたN、N−ジメチルピロリジニウムメチルカーボ
ネート10.0 gと42%HBF4水溶液12.9g
を用いた他は実施例1 (第2工程)と同様にして高純
度のジメチルピロリジニウムテトラフルオロボレート1
0.1g(N−メチルピロリジンに対し92.4%収率
)を得た。
(Second step) 10.0 g of the obtained N,N-dimethylpyrrolidinium methyl carbonate and 12.9 g of 42% HBF4 aqueous solution
Highly purified dimethylpyrrolidinium tetrafluoroborate 1 was prepared in the same manner as in Example 1 (second step) except that
0.1 g (92.4% yield based on N-methylpyrrolidine) was obtained.

実施例−3 実施例2(第1工程)において得られたN、N −ジメ
チルピロリジニウムメチルカーボネート10.0gに乾
燥窒素雰囲気下、l5O3F 5.7 gを徐々に添加
し、50℃15鶴Hgで炭酸ガスを除いて、フルオロ硫
酸ジメチルピロリジニウム10.8g(N−メチルピロ
リジンに対し92.7%収率)を得た。
Example 3 5.7 g of 15O3F was gradually added to 10.0 g of N,N-dimethylpyrrolidinium methyl carbonate obtained in Example 2 (first step) under a dry nitrogen atmosphere, and heated at 50°C for 15 minutes. Carbon dioxide gas was removed with Hg to obtain 10.8 g of dimethylpyrrolidinium fluorosulfate (92.7% yield based on N-methylpyrrolidine).

実施例−4 (第1工程) 原料として炭酸ジメチル8.8g、とリジン10.0g
5溶媒としてメタノール10.0 gを使用した以外は
実施例−1と同様の反応を行って、16.8 gの固体
を得た(理論収率の78.5%)。元素分析、H−NM
Rなどから、この固体はN−メチルピリジニウムメチル
カーボネートであることが確認された。
Example-4 (1st step) 8.8 g of dimethyl carbonate and 10.0 g of lysine as raw materials
5 The same reaction as in Example 1 was carried out except that 10.0 g of methanol was used as the solvent, and 16.8 g of solid was obtained (78.5% of the theoretical yield). Elemental analysis, H-NM
It was confirmed from R etc. that this solid was N-methylpyridinium methyl carbonate.

(第2工程) N−メチルピリジニウムメチルカーボネート10、0 
gと60%HC1099,9gを使用した以外は実施例
1と同様の操作を行って過塩素酸N−メチルビリジニウ
ム10.8g(ピリジンに対し74.3%収率)を得た
(Second step) N-methylpyridinium methyl carbonate 10,0
The same operation as in Example 1 was performed except that 1099.9 g of 60% HC was used to obtain 10.8 g of N-methylpyridinium perchlorate (74.3% yield based on pyridine).

実施例−5 (第1工程) 原料として炭酸ジメチル17.0g、1.5−ジアザビ
シクロ(4,3,0) −5−ノネン10. Ogを使
用した以外は実施例−1と同様な反応を行つたとこる1
 2.6 gの粘性液体を得た(論理収率72.8%)
0元素分析、’H−NMR,MSなどから、この粘性液
体は1−メチル−1−アゾニア−5−アザビシクロ(4
,3,0) −5−ノネンメチルカーボネートであるこ
とが確認された。
Example-5 (1st step) 17.0 g of dimethyl carbonate and 10.0 g of 1.5-diazabicyclo(4,3,0)-5-nonene as raw materials. The same reaction as in Example 1 was carried out except that Og was used.1
Obtained 2.6 g of viscous liquid (theoretical yield 72.8%)
From elemental analysis, 'H-NMR, MS, etc., this viscous liquid was found to be 1-methyl-1-azonia-5-azabicyclo (4
,3,0)-5-nonene methyl carbonate.

(第2工程) 1−メチル−1−アゾニア−5−アザビシクロ(4,3
,0) −5−ノネンメチルカーボネート8.0gと4
0%HBF47.4 gを使用した以外は実施例−1と
同様の操作を行って1−メチル−1−アゾニア−5−ア
ザビシクロ(4,3,0) −5−ノネンテトラフルオ
ロボレート8.2g(1,5−ジアザビシクロ(4,3
,0) −5−ノネンに対し70.8%収率)を得た。
(Second step) 1-methyl-1-azonia-5-azabicyclo(4,3
,0) -5-nonene methyl carbonate 8.0g and 4
The same operation as in Example 1 was performed except that 47.4 g of 0% HBF was used to obtain 8.2 g of 1-methyl-1-azonia-5-azabicyclo(4,3,0)-5-nonenetetrafluoroborate. (1,5-diazabicyclo(4,3
, 0) -70.8% yield based on -5-nonene).

Claims (1)

【特許請求の範囲】 四級アンモニウム無機酸塩を製造する方法において、 (a)三級アミンを炭酸ジエステルと反応させ対応する
四級アンモニウム炭酸塩を製造する工程 (b)生成した四級アンモニウム炭酸塩を無機酸と混合
して炭酸ガスを系外に除去せしめて対応する無機酸塩を
製造する工程 の2段階の工程を経ることを特徴とする四級アンモニウ
ム無機酸塩の製造方法。
[Scope of Claims] A method for producing a quaternary ammonium inorganic acid salt, comprising: (a) a step of producing a corresponding quaternary ammonium carbonate by reacting a tertiary amine with a carbonic acid diester; (b) a step of producing a quaternary ammonium carbonate produced; A method for producing a quaternary ammonium inorganic acid salt, comprising a two-step process of mixing a salt with an inorganic acid and removing carbon dioxide from the system to produce a corresponding inorganic acid salt.
JP62117380A 1987-05-13 1987-05-14 Method for producing quaternary ammonium inorganic acid salt Expired - Fee Related JPH07116113B2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP62117380A JPH07116113B2 (en) 1987-05-14 1987-05-14 Method for producing quaternary ammonium inorganic acid salt
US07/192,524 US4892944A (en) 1987-05-13 1988-05-11 Process for producing quaternary salts
DE8888107735T DE3868138D1 (en) 1987-05-13 1988-05-13 METHOD FOR PRODUCING QUATERNAUS SALTS.
EP88107735A EP0291074B1 (en) 1987-05-13 1988-05-13 Process for producing quaternary salts

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP62117380A JPH07116113B2 (en) 1987-05-14 1987-05-14 Method for producing quaternary ammonium inorganic acid salt

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP35644696A Division JP3145049B2 (en) 1996-12-26 1996-12-26 Electrolyte for electrolyte

Publications (2)

Publication Number Publication Date
JPS63284148A true JPS63284148A (en) 1988-11-21
JPH07116113B2 JPH07116113B2 (en) 1995-12-13

Family

ID=14710217

Family Applications (1)

Application Number Title Priority Date Filing Date
JP62117380A Expired - Fee Related JPH07116113B2 (en) 1987-05-13 1987-05-14 Method for producing quaternary ammonium inorganic acid salt

Country Status (1)

Country Link
JP (1) JPH07116113B2 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63280045A (en) * 1987-05-13 1988-11-17 Mitsubishi Petrochem Co Ltd Production of organic acid salt of quaternary ammonium
JP2003515573A (en) * 1999-12-01 2003-05-07 ザ クイーンズ ユニバーシティ オブ ベルファスト Ambient temperature ionic liquid
WO2006090657A1 (en) * 2005-02-23 2006-08-31 Mitsubishi Gas Chemical Company, Inc. Process for producing boron tetrafluoride, boron tetrafluoride produced by said process, electrolysis solution for electric double layer capacitor using said boron tetrafluoride, and process for producing said electrolysis solution
US7645434B2 (en) 2003-02-14 2010-01-12 Merck Patent Gmbh Salts comprising cyanoborate anions
JP2010116349A (en) * 2008-11-13 2010-05-27 Tosoh Corp New n,n,n-trimethyl-1-adamantane ammonium methyl carbonate
JP2010138087A (en) * 2008-12-10 2010-06-24 Tosoh Corp Method for producing n,n,n-trialkyladamantane ammonium alkyl carbonate
JP2010254535A (en) * 2009-04-28 2010-11-11 Tosoh Corp Structure-directing agent for zeolite production
JP2013249308A (en) * 2013-08-12 2013-12-12 Tosoh Corp Method for producing new n,n,n-trimethyl-1-adamantaneammonium methyl carbonate

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635100A (en) * 1949-11-15 1953-04-14 Du Pont Monoquaternary ammonium carbonates and their preparation
US3257233A (en) * 1963-04-08 1966-06-21 Gen Mills Inc Textile fabric treated with ditertiary amine obtained from a secondary amine and polyoxyethylene glycol and the quaternary obtained therefrom
US3652564A (en) * 1969-12-01 1972-03-28 Syntex Corp 5-alkyl-1 6-fused cycloalkylene-tetrahydro-1 5-diazine salts
JPS4855231A (en) * 1972-07-25 1973-08-03
US4102863A (en) * 1976-11-24 1978-07-25 Ppg Industries, Inc. Cationic electrodeposition using aqueous dispersions of quaternary ammonium carbonate-containing polymers
JPS5634753A (en) * 1979-08-30 1981-04-07 Hitachi Chem Co Ltd Polyurethane resin composition
JPS5728019A (en) * 1980-07-29 1982-02-15 Sanyo Chem Ind Ltd Preparation of glycol diether
JPS6038332A (en) * 1983-07-20 1985-02-27 ユニオン・キヤンプ・コーポレイシヨン Halogen hydrogenation of conjugate diene
JPS61170588A (en) * 1985-01-25 1986-08-01 Tama Kagaku Kogyo Kk Production of quaternary ammonium hydroxide
JPS63280045A (en) * 1987-05-13 1988-11-17 Mitsubishi Petrochem Co Ltd Production of organic acid salt of quaternary ammonium

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2635100A (en) * 1949-11-15 1953-04-14 Du Pont Monoquaternary ammonium carbonates and their preparation
US3257233A (en) * 1963-04-08 1966-06-21 Gen Mills Inc Textile fabric treated with ditertiary amine obtained from a secondary amine and polyoxyethylene glycol and the quaternary obtained therefrom
US3652564A (en) * 1969-12-01 1972-03-28 Syntex Corp 5-alkyl-1 6-fused cycloalkylene-tetrahydro-1 5-diazine salts
JPS4855231A (en) * 1972-07-25 1973-08-03
US4102863A (en) * 1976-11-24 1978-07-25 Ppg Industries, Inc. Cationic electrodeposition using aqueous dispersions of quaternary ammonium carbonate-containing polymers
JPS5634753A (en) * 1979-08-30 1981-04-07 Hitachi Chem Co Ltd Polyurethane resin composition
JPS5728019A (en) * 1980-07-29 1982-02-15 Sanyo Chem Ind Ltd Preparation of glycol diether
JPS6038332A (en) * 1983-07-20 1985-02-27 ユニオン・キヤンプ・コーポレイシヨン Halogen hydrogenation of conjugate diene
JPS61170588A (en) * 1985-01-25 1986-08-01 Tama Kagaku Kogyo Kk Production of quaternary ammonium hydroxide
JPS63280045A (en) * 1987-05-13 1988-11-17 Mitsubishi Petrochem Co Ltd Production of organic acid salt of quaternary ammonium

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63280045A (en) * 1987-05-13 1988-11-17 Mitsubishi Petrochem Co Ltd Production of organic acid salt of quaternary ammonium
JP2003515573A (en) * 1999-12-01 2003-05-07 ザ クイーンズ ユニバーシティ オブ ベルファスト Ambient temperature ionic liquid
US7645434B2 (en) 2003-02-14 2010-01-12 Merck Patent Gmbh Salts comprising cyanoborate anions
WO2006090657A1 (en) * 2005-02-23 2006-08-31 Mitsubishi Gas Chemical Company, Inc. Process for producing boron tetrafluoride, boron tetrafluoride produced by said process, electrolysis solution for electric double layer capacitor using said boron tetrafluoride, and process for producing said electrolysis solution
JP5029353B2 (en) * 2005-02-23 2012-09-19 三菱瓦斯化学株式会社 Method for producing boron tetrafluoride salt, boron tetrafluoride salt obtained by the method, electrolytic solution for electric double layer capacitor using the same, and method for producing the same
JP2010116349A (en) * 2008-11-13 2010-05-27 Tosoh Corp New n,n,n-trimethyl-1-adamantane ammonium methyl carbonate
JP2010138087A (en) * 2008-12-10 2010-06-24 Tosoh Corp Method for producing n,n,n-trialkyladamantane ammonium alkyl carbonate
JP2010254535A (en) * 2009-04-28 2010-11-11 Tosoh Corp Structure-directing agent for zeolite production
JP2013249308A (en) * 2013-08-12 2013-12-12 Tosoh Corp Method for producing new n,n,n-trimethyl-1-adamantaneammonium methyl carbonate

Also Published As

Publication number Publication date
JPH07116113B2 (en) 1995-12-13

Similar Documents

Publication Publication Date Title
EP1254889B1 (en) Process for the preparation of quaternary ammonium salts of hydroxycarboxylic acids and quaternary ammonium salts of inorganic acids
EP0291074A2 (en) Process for producing quaternary salts
JPS63284148A (en) Production of quaternary ammonium inorganic acid salt
US4065475A (en) Process for preparing CIS-epoxysuccinic acid salts of high purity
JPS61249956A (en) Manufacture of imino ether and novel imino ether having arylsubstituent
CN110590734A (en) Method for synthesizing 2-methyl-4H-benzo [ d ] [1,3] oxathiacyclohexadiene-4-one
JPH0348654A (en) Compound of sulfonium compound
JPS63290890A (en) Production of quaternary phosphonium salt of inorganic acid
JP3145049B2 (en) Electrolyte for electrolyte
JP3821977B2 (en) Method for producing quaternary alkyl ammonium salt
US5847205A (en) Method for producing homocystine
JP2001187779A (en) Method for producing 2-hydroxy-4-methylthiobutanoic acid
JP2001247306A (en) Method for synthesizing ionic metal complex and method for purifying the same
US4551324A (en) Preparation from hydroxylammonium sulfate of other hydroxylammonium salts via alcoholic hydroxylamine
US10882806B2 (en) Processes for preparing 4-methyl-5-nonanone and 4-methyl-5-nonanol
KR920006418B1 (en) Process for the preparation of 1-(2-tetrahydrofuryl)-s-fluorouracil
JPH1017553A (en) Production of n-alkyl-n&#39;-methylimidazolinium inorganic acid salt
CN115260103B (en) Preparation method of 4,5-dihalogen-1- (difluoromethyl) -1H-imidazole
JPS6330454A (en) Anionic exchange of quaternary ammonium salt
JPH02124856A (en) Method and apparatus for producing 1,3-diaminopropanol-2
MXPA02007060A (en) Method for producing heterocyclic compounds.
KR101114893B1 (en) - Process for preparing pyridine-substituted amino ketal derivatives
JPH0830047B2 (en) Method for producing quaternary ammonium organic acid salt
JPS6317060B2 (en)
JPS60104048A (en) Manufacture of tertiary amine

Legal Events

Date Code Title Description
LAPS Cancellation because of no payment of annual fees