JPH03261747A - Quaternary ammonium salt and production thereof - Google Patents
Quaternary ammonium salt and production thereofInfo
- Publication number
- JPH03261747A JPH03261747A JP2060800A JP6080090A JPH03261747A JP H03261747 A JPH03261747 A JP H03261747A JP 2060800 A JP2060800 A JP 2060800A JP 6080090 A JP6080090 A JP 6080090A JP H03261747 A JPH03261747 A JP H03261747A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- parts
- thiocyanate
- quaternary ammonium
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 title description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 14
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- DBYIPBJRDWQOHF-UHFFFAOYSA-M benzyl(triethyl)azanium;thiocyanate Chemical compound [S-]C#N.CC[N+](CC)(CC)CC1=CC=CC=C1 DBYIPBJRDWQOHF-UHFFFAOYSA-M 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 21
- ABNDFSOIUFLJAH-UHFFFAOYSA-N benzyl thiocyanate Chemical compound N#CSCC1=CC=CC=C1 ABNDFSOIUFLJAH-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- -1 hydrogen halides Chemical class 0.000 description 4
- VYHVQEYOFIYNJP-UHFFFAOYSA-N methyl thiocyanate Chemical compound CSC#N VYHVQEYOFIYNJP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- CBLPYIDSEWYRSF-UHFFFAOYSA-M benzyl(tributyl)azanium;thiocyanate Chemical compound [S-]C#N.CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 CBLPYIDSEWYRSF-UHFFFAOYSA-M 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- ALNHPAMBWQAKJO-UHFFFAOYSA-M trimethyl(phenyl)azanium;thiocyanate Chemical compound [S-]C#N.C[N+](C)(C)C1=CC=CC=C1 ALNHPAMBWQAKJO-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規な第四級アンモニウム塩であるところの、
第四級アンモニウムチオシアン酸塩とその製造方法に関
するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is a novel quaternary ammonium salt,
This invention relates to quaternary ammonium thiocyanate and its production method.
〔従来技術と発明が解決しようとする問題点〕従来アン
モニウムイオンの４個の水素原子をすべて有機基で置換
した構造の第四級アンモニウム塩は陽イオン界面活性剤
などとしての機能を有するものが多く、その用途は殺菌
剤、相間移動触媒、帯電防止剤、均染剤、乳化破壊剤、
分散剤などの多岐にわたって工業的に多数使用されてい
る。しかし、これらの第四級アンモニウム塩はいずれも
ハロゲン化水素などの塩であり、チオシアン酸塩類の合
成についてはその例を聞かない。[Prior art and problems to be solved by the invention] Conventionally, quaternary ammonium salts with a structure in which all four hydrogen atoms of the ammonium ion are replaced with organic groups have functions such as cationic surfactants. Many of its uses include disinfectants, phase transfer catalysts, antistatic agents, leveling agents, demulsifiers,
It is widely used industrially in a wide variety of applications such as dispersants. However, all of these quaternary ammonium salts are salts of hydrogen halides, etc., and no examples have been heard of the synthesis of thiocyanates.
本発明はかかる現状を鑑みて為されたもので、陽イオン
界面活性剤などとしての優れた機能を有する有用な該化
合物を、安価な原料を用い、１段階の反応より、収率良
く製造する方法について鋭意検討を重ねたところ、第四
級アンモニウムのチオシアン酸塩とその製造方法を見出
し、本発明を完成するに至った。即ち、本発明は
一般式
％式％（２）
（式中、Ｒ１はアルキル基またはアラルキル基である。The present invention has been made in view of the current situation, and aims to produce this useful compound having excellent functions as a cationic surfactant, etc., in high yield through a one-step reaction using inexpensive raw materials. As a result of extensive research into the method, the inventors discovered a quaternary ammonium thiocyanate and a method for producing the same, thereby completing the present invention. That is, the present invention is based on the general formula % (2) (wherein R1 is an alkyl group or an aralkyl group).
）で示されるチオシアネートを
Ｒ１
Ｒ２−Ｎ−Ｒ，（３）
（式中Ｒ２、Ｒ，、Ｒ，はアルキル基、アラルキル基ま
たはアリール基であり、Ｒ，、Ｒ，、Ｒ４は下図の様に
互いに結合して環を形成していてもよい、）で示される
第三級アミンと共に常圧または高圧下に反応させること
を特徴とする
一般式
（式中、Ｒよはアルキル基またはアラルキル基であり、
Ｒ，、Ｒ，、Ｒ，はアルキル基、アラルキル基またはア
リール基である。Ｒ２、Ｒ１、Ｒ４は下図の様に互いに
結合して環を形成していてもよい６）２
で表わされる第四級アンモニウムのチオシアン酸塩を提
供するものである。) thiocyanate represented by R1 R2-N-R, (3) (wherein R2, R,, R, is an alkyl group, aralkyl group, or aryl group, and R,, R,, R4 are as shown in the figure below) The general formula (where R is an alkyl group or an aralkyl group) is reacted under normal pressure or high pressure with a tertiary amine represented by (which may be bonded to each other to form a ring). can be,
R,, R,, R, are an alkyl group, an aralkyl group or an aryl group. R2, R1, and R4 may be bonded to each other to form a ring as shown in the figure below to provide a quaternary ammonium thiocyanate represented by 6)2.
本発明の方法において原料として用いる一般式（２）で
示されるチオシアネート並びに−紋穴（３）で示される
第三級アミンは何れも容易に得られるものであり、Ｒい
Ｒ２、Ｒ３、Ｒ４の種類を選択することにより容易に目
的とする置換基を導玉！する事ができる。The thiocyanate represented by the general formula (2) and the tertiary amine represented by the formula (3) used as raw materials in the method of the present invention are both easily obtainable, and R2, R3, and R4 are easily obtained. Easily find the desired substituent by selecting the type! I can do that.
チオシアネートの置換基Ｒ工はアルキル基としてはメチ
ル、エチル、プロピル基などが、アラルキル基としては
ベンジル基などがあげられる。また、第三級アミンの置
換基Ｒ２、Ｒ，、Ｒ，はアルキル基としてはメチル、エ
チル、プロピル、ブチル、オクチル、ドデシル基など、
Ｒ２、Ｒ３が結合している例としてピペリジノ、ピロリ
ジノ、ピロリル基などが、アラルキル基としてはベンジ
ル基などが、アリール基としてはフェニール基などが、
またＲ２、Ｒ，、Ｒ，が環状に結合している第三級アミ
ンの例としてピリジン、ピリミジン、キノリン、イソキ
ノリンなどがあげられる。Examples of the alkyl group of the substituent R of thiocyanate include methyl, ethyl, propyl, etc., and examples of the aralkyl group include benzyl. In addition, the substituents R2, R,, R, of the tertiary amine are alkyl groups such as methyl, ethyl, propyl, butyl, octyl, dodecyl groups, etc.
Examples of R2 and R3 bonded include piperidino, pyrrolidino, and pyrrolyl groups, aralkyl groups such as benzyl groups, and aryl groups such as phenyl groups.
Further, examples of tertiary amines in which R2, R, , R, are cyclically bonded include pyridine, pyrimidine, quinoline, and isoquinoline.
本反応は原料の第三級アミンの置換基Ｒ２、Ｒ１゜Ｒ４
が低級アルキル基、例えばメチル、エチルなどの場合は
常圧下でも反応し、ある程度の収率を得ることが出来る
が、Ｉｆ置換基よりバルキーなものになると、第四級ア
ンモニウムのチオシアン酸塩の収率は著しく減少する。This reaction is performed using substituents R2, R1゜R4 of the tertiary amine as a raw material.
If it is a lower alkyl group, such as methyl or ethyl, the reaction will occur even under normal pressure, and a certain level of yield can be obtained, but if it is bulkier than the If substituent, the yield of quaternary ammonium thiocyanate will be low. rate is significantly reduced.
この問題を解決するためには、この反応が著しい圧力依
存性を有するＪ覗塩を利用り、Ｅｉ応やよ、ｌ１、行う
、が望よしい、この手法により常圧付近では全く得られ
ない第四級アンモニウムのチオシアン酸塩類を優れた収
率で得ることが出来る。In order to solve this problem, it is desirable to conduct the Ei reaction by using J-salt, which has a remarkable pressure dependence. Quaternary ammonium thiocyanates can be obtained in excellent yields.
本発明の方法において一方の原料であるところの第三級
アミンは反応溶媒としても機能するが。The tertiary amine, which is one of the raw materials in the method of the present invention, also functions as a reaction solvent.
原料が溶解しない場合には適当な溶媒、例えば。If the raw materials are not soluble, a suitable solvent, e.g.
ベンゼン、トルエン、塩化メチレン、などを用いて反応
を行なうことが可能である。The reaction can be carried out using benzene, toluene, methylene chloride, etc.
チオシアネートと第三級アミンとの使用割合は、化学量
論的なモル比は１：ｌであるが、通常はモル比１：１Ｏ
−１０＝１の範囲で選択される。The stoichiometric molar ratio of thiocyanate and tertiary amine is 1:1, but the molar ratio is usually 1:1O.
Selected in the range -10=1.
本発明の反応は常圧または加圧下でおこなわれる０本反
応は原料の第三級アミンの置換基Ｒ２゜Ｒ，、Ｒ４が低
級アルキル基であるものについては常圧でも反応するが
、優れた収率を得るためには反応をより高圧で行うこと
が好ましく、第三級アミンがバルキーな置換基を有する
ものは、高圧下でなければ反応は進行しない、一般に反
応圧力は１〜９０００気圧の間で選択される０反応温度
は副反応をさける意味では、２０〜１６０℃の温度の採
用が望ましい。The reaction of the present invention is carried out under normal pressure or increased pressure.In the case where the substituents R2゜R, R4 of the raw material tertiary amine are lower alkyl groups, the reaction can be carried out under normal pressure. In order to obtain a good yield, it is preferable to carry out the reaction at a higher pressure.If the tertiary amine has a bulky substituent, the reaction will not proceed unless under high pressure.Generally, the reaction pressure is 1 to 9000 atm. In order to avoid side reactions, it is desirable to adopt a temperature of 20 to 160° C. as the reaction temperature selected between the above.
本発明によって得られる第四級アンモニウムのチオシア
ン酸塩は新規化合物であり、界面活性剤、触媒、医薬お
よびそれらの中間体としての利用が期待できる。従って
本発明は工業的にも利用価値の高いものである。The quaternary ammonium thiocyanate obtained by the present invention is a new compound and can be expected to be used as surfactants, catalysts, medicines, and intermediates thereof. Therefore, the present invention has high utility value industrially.
次に本発明を実施例によりさらに詳細に説明する。各実
施例中に示す部は重量部をあられし、また、収率に関す
る％は原料のチオシアネートについての理論収率である
。Next, the present invention will be explained in more detail with reference to Examples. The parts shown in each example are parts by weight, and the % regarding yield is the theoretical yield for the raw material thiocyanate.
実施例１
ベンジルチオシアネート４．８部とトリエチルアミン５
．工部（モル比１：１．５．以下の実施例についても同
様）とをベンゼン１５．１部と共に封管中で２気圧、１
００℃に２０時間保持した。Example 1 4.8 parts of benzyl thiocyanate and 5 parts of triethylamine
．． (mol ratio 1:1.5; the same applies to the following examples) in a sealed tube with 15.1 parts of benzene at 2 atm.
The temperature was kept at 00°C for 20 hours.
反応時間経過後冷却開封して内容物をベンゼンで洗い出
し、生成した白色の結晶を更にテトラヒドロフランで再
結晶精製し、目的とするベンジル−トリエチルアンモニ
ウムのチオシアン酸塩を３゜１部（収率：３９％）得た
。After the reaction time has elapsed, the package is cooled and opened, and the contents are washed out with benzene. The produced white crystals are further purified by recrystallization with tetrahydrofuran to obtain 3.1 parts of the desired benzyl-triethylammonium thiocyanate (yield: 39 %)Obtained.
実施例２
ベンジルチオシアネート５．０部とトリエチルアミン５
．０部とをベンゼン１３．５部と共にテフロン製カプセ
ル中に封入し高圧反応管中に収納して約１８００気圧に
加圧した後１反応管を加熱して温度をｌ００℃に昇温し
、さらに圧力を加えて２０００気圧とし２０時間保持し
た。２０時間経過後、反応管を室温まで冷却してから圧
力を常圧とし、カプセルを開封して内容物を実施例１と
同様の手法で分離精製し目的とするベンジルトリエチル
アンモニウムのチオシアン酸塩を６．２部（収率ニア４
％）得た。Example 2 5.0 parts of benzyl thiocyanate and 5 parts of triethylamine
．． 0 part and 13.5 parts of benzene were sealed in a Teflon capsule, stored in a high-pressure reaction tube, and pressurized to about 1800 atm, then heated 1 reaction tube to raise the temperature to 100 ° C. Pressure was increased to 2000 atmospheres and maintained for 20 hours. After 20 hours, the reaction tube was cooled to room temperature, the pressure was brought to normal pressure, the capsule was opened, and the contents were separated and purified in the same manner as in Example 1 to obtain the desired benzyltriethylammonium thiocyanate. 6.2 parts (yield near 4
%)Obtained.
実施例３
メチルチオシアネート３．５部とトリエチルアミン７．
１部とをベンゼン１４．９部と共に封管中で２気圧、１
００℃に２０時間保持した１反応時藺経過後冷却開封し
て内容物を実施例１と同様の手法で分離精製し、目的と
するメチルトリエチルアンモニウムのチオシアン酸塩を
７．１部（収率ニア１％）得た。Example 3 3.5 parts of methyl thiocyanate and 7 parts of triethylamine.
1 part and 14.9 parts of benzene in a sealed tube at 2 atm and 1
After one reaction period of 20 hours at 00°C, the package was cooled and opened, and the contents were separated and purified in the same manner as in Example 1 to obtain 7.1 parts of the desired thiocyanate of methyltriethylammonium (yield Near 1%) was obtained.
実施例４
ベンジルチオシアネート４．０部とトリｎ−プロピルア
ミン５．７３部とをベンゼン１５．０部と共に実施例１
と同様の手順封管中で２気圧、１００℃に２０時間保持
した６反応後実施例１と同様の手法で分離精製し、目的
とするベンジルトリｎ−プロピルアンモニウムのチオシ
アン酸塩を１．５部（収率：３８％）得た。Example 4 4.0 parts of benzyl thiocyanate and 5.73 parts of tri-n-propylamine were combined with 15.0 parts of benzene in Example 1.
After 6 reactions, which were carried out in a sealed tube at 2 atm and maintained at 100°C for 20 hours, it was separated and purified in the same manner as in Example 1 to obtain 1.5 parts of the desired benzyltri-n-propylammonium thiocyanate. (Yield: 38%).
実施例５
ベンジルチオシアネート６．０部とトリｎ−プロピルア
ミン８．７部をベンゼン１Ｏ１１部と共に実施例２と同
様の手順で４０００気圧、１００’Ｃに２０時間保持し
た１反応後実施例１と同様の手法で分離精製し、目的と
するベンジルトリｎ−プロピルアンモニウムのチオシア
ン酸塩を１１．４部（収率：９７％）を得た。Example 5 After 1 reaction in which 6.0 parts of benzyl thiocyanate and 8.7 parts of tri-n-propylamine were held at 4000 atm and 100'C for 20 hours in the same manner as in Example 2 with 11 parts of benzene 1O, the reaction mixture of Example 1 and Separation and purification was performed in the same manner to obtain 11.4 parts (yield: 97%) of the desired benzyltri-n-propylammonium thiocyanate.
辷９偏例６
ペンジルチオシアネート４．０部とトリｎ−ブチルアミ
ン７．５部をベンゼンエ３．１部と共に実施例２と同様
の手順で２０００気圧、１００”Ｃに２０時間保持した
１反応後実施例１と同様の手法で分離精製し、目的とす
るベンジルトリｎ−ブチルアンモニウムのチオシアン酸
塩を１．５部（収率：１７％）を得た。Partial Example 6 After 1 reaction in which 4.0 parts of pendyl thiocyanate and 7.5 parts of tri-n-butylamine were held at 2000 atmospheres and 100"C for 20 hours in the same manner as in Example 2 with 3.1 parts of benzene. Separation and purification was performed in the same manner as in Example 1 to obtain 1.5 parts (yield: 17%) of the desired benzyltri-n-butylammonium thiocyanate.
実施例７
ペンジルチオシアネート５．２部とトリｎ−ブチルアミ
ン９．４部をベンゼン１５．７部と共に実施例２と同様
の手順で４０００気圧、１００”Ｃに２０時間保持した
１反応後実施例１と同様の手法で分離精製し、目的とす
るベンジルトリｎ−ブチルアンモニウムのチオシアン酸
塩を４．７部（収率：４１％）を得た。Example 7 Example after one reaction in which 5.2 parts of pendyl thiocyanate and 9.4 parts of tri-n-butylamine were held at 4000 atm and 100"C for 20 hours in the same manner as in Example 2, together with 15.7 parts of benzene. The product was separated and purified in the same manner as in 1 to obtain 4.7 parts (yield: 41%) of the desired benzyltri-n-butylammonium thiocyanate.
実施例８
メチルチオシアネート４．１部とピリジン６．６部とを
ベンゼン１４．０部と共に封管中で２気圧。Example 8 4.1 parts of methyl thiocyanate and 6.6 parts of pyridine were mixed with 14.0 parts of benzene in a sealed tube at 2 atm.
１００℃に２０時間保持した１反応時間経過後冷６封し
て内容物を実施例工と同様の手法で分離精製し、目的と
するＮ−メチルビリジウムのチオシアン酸塩を３．３部
（収率：３９％）得た。After 1 reaction time, which was maintained at 100°C for 20 hours, the contents were separated and purified in the same manner as in the example. Yield: 39%) was obtained.
実施例９
メチルチオシアネート４．２部とピリジン６．５部をベ
ンゼン１５．１部と共に実施例２と同様の手順で２００
０気圧、１００℃に２０時間保持した１反応後実施例１
と同様の手法で分離精製し。Example 9 4.2 parts of methyl thiocyanate and 6.5 parts of pyridine were mixed with 15.1 parts of benzene in the same manner as in Example 2 for 200
Example 1 after 1 reaction held at 0 atm and 100°C for 20 hours
Separate and purify using the same method.
目的とするＮ−メチルピリジウムのチオシアン酸塩を８
．８部（収率：９０％）を得た。The desired N-methylpyridium thiocyanate is 8
．． 8 parts (yield: 90%) were obtained.
実施例１０
ベンジルチオシアネート６．０部とピリジン４゜８部と
をベンゼン１３．７部と共に封管中で２気圧、１００℃
に２０時間保持した２反応時間経過後冷却開封して内容
物を実施例１と同様の手法で分離精製し、目的とするＮ
−ベンジルピリジウムのチオシアン酸塩を５．５部（収
率：６０％）得た。Example 10 6.0 parts of benzyl thiocyanate and 4.8 parts of pyridine were heated together with 13.7 parts of benzene in a sealed tube at 2 atm and 100°C.
After 20 hours of reaction time, the container was cooled and opened, and the contents were separated and purified in the same manner as in Example 1.
- 5.5 parts (yield: 60%) of benzylpyridium thiocyanate were obtained.
実施例１１
ベンジルチオシアネート６．０部とピリジン４゜８亀を
ベンゼン１５．０部と共に実施例２と同様の手順で２０
００気圧、１００’Ｃに２０時間保持した１反応後実施
例１と同様の手法で分離精製し。Example 11 6.0 parts of benzyl thiocyanate and 4.8 parts of pyridine were mixed with 15.0 parts of benzene in the same manner as in Example 2.
After one reaction held at 100'C and 00atm for 20 hours, it was separated and purified in the same manner as in Example 1.
目的とするＮ−ベンジルピリジウムのチオシアン酸塩を
９．１部（収率：９６％）を得た。9.1 parts (yield: 96%) of the target thiocyanate of N-benzylpyridium was obtained.
実施例１２
メチルチオシアネート５．１部とＮ、Ｎ−ジメチルアニ
リン１２．５部をベンゼン１６．５部と共に実施Ｍ２と
同様の手順で６０００気圧、１００℃に２０時間保持し
た０反応後実施例１と同様の手法で分離精製し、目的と
するトリメチルフェニルアンモニウムのチオシアン酸塩
を４．０部（収率：１９％）を得た。Example 12 After 0 reaction in which 5.1 parts of methylthiocyanate and 12.5 parts of N,N-dimethylaniline were held at 6000 atm and 100°C for 20 hours in the same procedure as in Example M2 with 16.5 parts of benzene Example 1 The product was separated and purified in the same manner as above to obtain 4.0 parts (yield: 19%) of the target trimethylphenylammonium thiocyanate.
実施例１３Example 13
Claims (2)
、Ｒ＿２、Ｒ＿３、Ｒ＿４はアルキル基、アラルキル基
またはアリール基である、Ｒ＿２、Ｒ＿３、Ｒ＿４は下
図の様に互いに結合して環を形成していてもよい。）▲
数式、化学式、表等があります▼ で表わされる第四級アンモニウムのチオシアン酸塩。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R_1 is an alkyl group or an aralkyl group, R_2, R_3, R_4 are an alkyl group, an aralkyl group, or an aryl group, R_2 , R_3, and R_4 may be combined with each other to form a ring as shown in the figure below.)▲
There are mathematical formulas, chemical formulas, tables, etc. Quaternary ammonium thiocyanate represented by ▼.
。）で示されるチオシアネートを ▲数式、化学式、表等があります▼（３） （式中Ｒ＿２、Ｒ＿３、Ｒ＿４はアルキル基、アラルキ
ル基またはアリール基であり、Ｒ＿２、Ｒ＿３、Ｒ＿４
は下図の様に互いに結合して環を形成していてもよい。 ）▲数式、化学式、表等があります▼ で示される第三級アミンと共に常圧または高圧下に反応
させることを特徴とする。 一般式 ▲数式、化学式、表等があります▼（１） （式中、Ｒ＿１はアルキル基またはアラルキル基であり
、Ｒ＿２、Ｒ＿３、Ｒ＿４はアルキル基、アラルキル基
またはアリール基である、Ｒ＿２、Ｒ＿３、Ｒ＿４は下
図の様に互いに結合して環を形成していてもよい。）▲
数式、化学式、表等があります▼ で表わされる第四級アンモニウムのチオシアン酸塩の製
造方法。(2) Thiocyanate represented by the general formula R_1SCN (2) (In the formula, R_1 is an alkyl group or an aralkyl group.) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, R_2, R_3, R_4 is an alkyl group, an aralkyl group, or an aryl group, and R_2, R_3, R_4
may be combined with each other to form a ring as shown in the figure below. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ It is characterized by being reacted with a tertiary amine shown by under normal pressure or high pressure. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (1) (In the formula, R_1 is an alkyl group or an aralkyl group, R_2, R_3, R_4 are an alkyl group, an aralkyl group, or an aryl group, R_2, R_3, R_4 may be bonded to each other to form a ring as shown in the figure below.)▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ A method for producing quaternary ammonium thiocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2060800A JPH0761988B2 (en) | 1990-03-12 | 1990-03-12 | Method for producing quaternary ammonium salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2060800A JPH0761988B2 (en) | 1990-03-12 | 1990-03-12 | Method for producing quaternary ammonium salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03261747A true JPH03261747A (en) | 1991-11-21 |
| JPH0761988B2 JPH0761988B2 (en) | 1995-07-05 |
Family
ID=13152762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2060800A Expired - Lifetime JPH0761988B2 (en) | 1990-03-12 | 1990-03-12 | Method for producing quaternary ammonium salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0761988B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885965A (en) * | 1991-11-01 | 1999-03-23 | Periodontix, Inc. | Anti-fungal D-amino acid histatin-based peptides |
| US5912230A (en) * | 1991-11-01 | 1999-06-15 | Periodontix, Inc. | Anti-fungal and anti-bacterial histatin-based peptides |
| JP2009013295A (en) * | 2007-07-05 | 2009-01-22 | Koei Chem Co Ltd | Ammonium salt and antistatic resin composition containing the same |
| DE102010064044A1 (en) | 2010-01-08 | 2011-07-14 | Basf Se, 67063 | Preparing imidazolium salt, useful as solvents, electrolytes and catalysts and in field of electrochemistry, comprises alkylating an imidazole derivative with an alkyl thiocyanate compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50149623A (en) * | 1974-05-24 | 1975-11-29 | ||
| JPH02108652A (en) * | 1988-10-18 | 1990-04-20 | Asahi Chem Ind Co Ltd | Treatment of quaternary onium salt |
-
1990
- 1990-03-12 JP JP2060800A patent/JPH0761988B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50149623A (en) * | 1974-05-24 | 1975-11-29 | ||
| JPH02108652A (en) * | 1988-10-18 | 1990-04-20 | Asahi Chem Ind Co Ltd | Treatment of quaternary onium salt |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885965A (en) * | 1991-11-01 | 1999-03-23 | Periodontix, Inc. | Anti-fungal D-amino acid histatin-based peptides |
| US5912230A (en) * | 1991-11-01 | 1999-06-15 | Periodontix, Inc. | Anti-fungal and anti-bacterial histatin-based peptides |
| JP2009013295A (en) * | 2007-07-05 | 2009-01-22 | Koei Chem Co Ltd | Ammonium salt and antistatic resin composition containing the same |
| DE102010064044A1 (en) | 2010-01-08 | 2011-07-14 | Basf Se, 67063 | Preparing imidazolium salt, useful as solvents, electrolytes and catalysts and in field of electrochemistry, comprises alkylating an imidazole derivative with an alkyl thiocyanate compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0761988B2 (en) | 1995-07-05 |
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