JPS5859959A - Aminosulfonic acid, its preparation and catalyst - Google Patents
Aminosulfonic acid, its preparation and catalystInfo
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- JPS5859959A JPS5859959A JP56159310A JP15931081A JPS5859959A JP S5859959 A JPS5859959 A JP S5859959A JP 56159310 A JP56159310 A JP 56159310A JP 15931081 A JP15931081 A JP 15931081A JP S5859959 A JPS5859959 A JP S5859959A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は新規なるアミノスルホン酸化合物、その製法な
らびに該化合物からなるインシアナート基の反応触媒に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel aminosulfonic acid compound, a method for producing the same, and a reaction catalyst for an incyanato group formed from the compound.
分子内に酸性基と塩基性基を有する両性化合物は、酸性
物質に対しては塩基の、また塩基性物質に対しては酸の
作用を示す興味深い化合物であるが、酸性基としてカル
ボキシル基を、また塩基性基としてアミノ基を有するも
のＫついては、アミノ酸、タンパク質、両性高分子化合
物など、比較的研究が進んでいるものの酸性基としてス
ルホン酸基を、塩基性基としてアミン基を有する化合物
に関しては、染料中間体としての各種芳香族化合物以外
殆んど研究されておらず、わずかに、アミドスルホン酸
、タウリン等が知られているにすぎない現況である。Amphoteric compounds that have an acidic group and a basic group in their molecules are interesting compounds that exhibit the effects of a base on acidic substances and an acidic effect on basic substances. Regarding compounds that have an amino group as a basic group, research has been relatively advanced, such as amino acids, proteins, amphoteric polymer compounds, etc. However, regarding compounds that have a sulfonic acid group as an acidic group and an amine group as a basic group, At present, little research has been conducted other than various aromatic compounds as dye intermediates, and only a few compounds such as amidosulfonic acid and taurine are known.
本発明者らは、脂肪族系のアミノスルホン酸化合物につ
いての一連の研究結果、本発明をなすに至った。The present inventors have completed the present invention as a result of a series of studies on aliphatic aminosulfonic acid compounds.
即ち、本発明においては、下記一般式（１）％式％（）
で表わさｎる新規化合物が提供せられる。式中、拓及び
島は夫々Ｈあるいは炭素原子数１〜１８のアルキル基を
表わし、またＲ３とＲ１はそれらの結合されている窒素
原子とでモルホリン核、ピペリジン核を作り、Ｒｓは炭
素原子数１〜６のアルキレン基であり、Ｒ４はＨあるい
は炭素原子数１〜４のアルキル基を表わす。That is, the present invention provides a novel compound represented by the following general formula (1). In the formula, Taku and Shima each represent H or an alkyl group having 1 to 18 carbon atoms, R3 and R1 form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded, and Rs represents the number of carbon atoms. It is an alkylene group having 1 to 6 carbon atoms, and R4 represents H or an alkyl group having 1 to 4 carbon atoms.
本発明の化合物は、次のようにして製造せられる。すな
わち、
（ａ）法
下記式（ＩＩ）
ＣＨ，＝ ＣＨ−ＳＯ，Ｎａ （ＩＩ ）で
示すれるビニルスルホン酸ナトリウムと式（１）％式％
（）
〔式中Ｒ，、Ｒ１、Ｒ８及びＲ４は前述の通り。〕で示
されるジアミン化合物とを反応させて、式（Ｖ）
Ｒ６
１Ｎ−Ｒ，−Ｎ−６Ｈ−ＣＨ＊５Ｏ−Ｎａ （’Ｖ）
Ｒ，／
のスルホン酸ナトリウム誘導体を得、これを遊離の酸に
導く方法。あるいは
（ｂ）法
式（ＩＶ）
ｃＨ，＝ ＣＨ−８０，Ｒ（■）
〔式中Ｒは、炭素原子数１〜４のアルキル基〕で示され
るビニルスルホン酸エステルと式（ＩＩＩ）１・＼Ｎ
−Ｒ，−ＮＨＲ，（ＩＩＩ）Ｒ，／
〔式中ｎ、、Ｒ，、Ｒｓ及びＲ１は前述の通り。〕で示
されるジアミン化合物を反応させて、式（）
％式％（）
〔式中Ｒ１、島、Ｒ１、Ｒ４及びＲは前述の通り。〕で
示されるスルホン酸エステル化合物となし、これを加水
分解する方法により、一般式（１）で示される化合物を
得ることができる。The compound of the present invention is produced as follows. That is, (a) method Sodium vinylsulfonate represented by the following formula (II) CH, = CH-SO, Na (II) and formula (1) % formula %
() [In the formula, R,, R1, R8 and R4 are as described above. ] to react with a diamine compound represented by the formula (V) R6 1N-R, -N-6H-CH*5O-Na ('V)
A method for obtaining a sodium sulfonate derivative of R,/ and converting it into a free acid. Alternatively, (b) a vinyl sulfonic acid ester represented by the formula (IV) cH,=CH-80,R(■) [in the formula, R is an alkyl group having 1 to 4 carbon atoms] and the formula (III) 1.\ N
-R, -NHR, (III)R, / [In the formula, n, , R, , Rs and R1 are as described above. ] A diamine compound represented by the formula () % formula % () [wherein R1, island, R1, R4 and R are as described above. ] The compound represented by the general formula (1) can be obtained by a method of preparing a sulfonic acid ester compound represented by the formula (1) and hydrolyzing it.
ビニルスルホン酸ナトリウム（ＩＩ）とジアミン化合物
（１）の反応及びビニルスルホン酸エステル（ｍＶ）と
ジアミン化合物（Ｉ）の反応は、好ましくは適当な不活
性溶媒、例えば水、アルコール、エチレングリコールモ
ノアルキルエーテル、クロルメチレン吟の１種または２
種以上の混液に、上記ジアミン化合物（ＩＩＩ）をとか
し、ビニルスルホン酸ナトリウム（ＩＩ）、あるいはビ
ニルスルホン酸エステル（ｍＶ）の溶液を滴下するか、
あるいけ、直接反応容器内にこれら反応原料と溶媒を仕
込み、０〜１５０℃の温度で１０分〜４８時間攪拌混合
することにより実施せられる。The reaction of sodium vinyl sulfonate (II) and diamine compound (1) and the reaction of vinyl sulfonic acid ester (mV) and diamine compound (I) are preferably carried out in a suitable inert solvent, such as water, alcohol, ethylene glycol monoalkyl One or two of ether and chlormethylene gin
Dissolve the diamine compound (III) and dropwise add a solution of sodium vinyl sulfonate (II) or vinyl sulfonic acid ester (mV) to a mixed solution of at least one species, or
Alternatively, the reaction can be carried out by directly charging these reaction materials and a solvent into a reaction vessel and stirring and mixing at a temperature of 0 to 150°C for 10 minutes to 48 hours.
これら式（ｎ）、（ＩＩＩ）及び（ＩＩ／）で表わされ
る原料化合物は、いずれも市場で入手可能なものであり
、また式（Ｉｌｌ）で表わされるジアミン化合物のある
種のものは市販ジアミン化合物のアルキル化により容易
に合成せられる。式（Ｉ［［）で表わされるジアミン化
合物の代表例として、ジアミノメタン、エチレンジアミ
ン、１，３−プロピレンジアミン、１．６−へキサメチ
レンジアミン、Ｎ−メチルアミノプロピルアミン、Ｎ、
Ｎ、Ｎ’−トリメチルエチレンジアミン、Ｎ、Ｎ−ジメ
チルアミンプロヒルアミン、Ｎ、Ｎ’−ジメチルへキサ
メチレンジアミン、Ｎ、Ｎ−ジメチル−Ｎ′−ブチルエ
チレンジアミン、Ｎ、Ｎ−ジメチルアミノ−Ｎ’−エチ
ルエチレンジアミン、１，４−ジアミノブタン、Ｎ、Ｎ
／−ジエチルプロピレンジアミン、２−アミノ−５−ジ
エチルアミノペンタン、Ｎ。These raw material compounds represented by formulas (n), (III) and (II/) are all commercially available, and some of the diamine compounds represented by formula (Ill) are commercially available diamine compounds. It can be easily synthesized by alkylation of compounds. Representative examples of diamine compounds represented by formula (I[[) include diaminomethane, ethylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, N-methylaminopropylamine, N,
N,N'-trimethylethylenediamine, N,N-dimethylamineproylamine, N,N'-dimethylhexamethylenediamine, N,N-dimethyl-N'-butylethylenediamine, N,N-dimethylamino-N' -ethylethylenediamine, 1,4-diaminobutane, N,N
/-diethylpropylene diamine, 2-amino-5-diethylaminopentane, N.
Ｎ、Ｎ’−トリプロピルテトラメチレンジアミン、Ｎ’
−イア１０ビル−２−メチル−１，２−フｏ ノζンジ
アミン、Ｎ−イソプロピルエチレンジアミン、Ｎ、Ｎ−
ジブチルアミノプロビルアミン、ラウリルアミノブチル
アミン、Ｎ−ラウリル−Ｎ′−メチルエチレンジアミン
、ステアリルアミノプロピルアミン、Ｎ−アミノプロピ
ルモルホリン、Ｎ−アミノへキシルモルホリン、Ｎ−ア
ミノエチルモルホリン、Ｎ−アミノエチルピペリジン等
があげられる。N, N'-tripropyltetramethylenediamine, N'
-ia-10vir-2-methyl-1,2-phono-diamine, N-isopropylethylenediamine, N,N-
Dibutylaminopropylamine, lauryl aminobutylamine, N-lauryl-N'-methylethylenediamine, stearyl aminopropylamine, N-aminopropylmorpholine, N-aminohexylmorpholine, N-aminoethylmorpholine, N-aminoethylpiperidine, etc. can be given.
かくして、得られる式（Ｖ）
４
駄Ｎ Ｒｓ Ｎ−６ＨＩＣＨ１８ＵＳＮａ （Ｖ）Ｚ
で表わされるスルホン酸ナトリウム化合物は、例えば水
に溶解し、計算量の塩酸を加える通常の中和手段により
式（Ｉ）で表わされる遊離の酸に導かれ、また式（■）
４
１・＼Ｎ−Ｒ，−Ｎ−ＣＨ，ＣＨ，ＳＯ，Ｒ（Ｖｌ）Ｒ
，／
で表わされるスルホン酸エステル化合物は、通常の加水
分解手段により同じく式（１）の遊離酸に変えられ、濃
縮、脱塩、再結晶、溶媒抽出などの手法を組合せ、単離
、精製することができる。The resulting sodium sulfonate compound of the formula (V) 4 NRs N-6HICH18USNa (V)Z can thus be converted into a compound of the formula (I) by conventional neutralization means, e.g. by dissolving it in water and adding a calculated amount of hydrochloric acid. It is also led to a free acid represented by the formula (■) 4 1.
The sulfonic acid ester compound represented by , / is converted into the free acid of formula (1) by ordinary hydrolysis means, and is isolated and purified using a combination of techniques such as concentration, desalting, recrystallization, and solvent extraction. be able to.
上記のようにｌ〜て製造される代表的な本発明化合物の
ナトリウム塩のＮＭＲスペクトルを第１表に示す。Table 1 shows the NMR spectra of typical sodium salts of the compounds of the present invention prepared as described above.
−５２１，−
２２
次に本発明化合物の製造法をより具体的に実施例によっ
て示す。なお、部は「重量部」である。-521, -22 Next, the method for producing the compound of the present invention will be described in more detail with reference to Examples. Note that parts are "parts by weight."
実施例 ｌ
Ｎ−３−（Ｎ’、 Ｎ’−ジメチルアミノ）プロビルタ
ウリ／ （化合物 ／Ｉ６β）攪拌器
をそなえた反応器にジメチルアミンプロピルアミン３０
６部を入れ室温下でビニルスルホン酸ナトリウムの２５
嘩水溶液１０４０部を攪拌下に滴下した。次いで１７時
間加熱還流し、放冷後、反応溶液を減圧下に濃縮し、か
っ色油秋物を得た。Example l N-3-(N', N'-dimethylamino)provirtauri/ (compound /I6β) Dimethylamine propylamine 30 was added to a reactor equipped with a stirrer.
6 parts of sodium vinyl sulfonate at room temperature.
1040 parts of an aqueous solution was added dropwise while stirring. Next, the mixture was heated under reflux for 17 hours, and after being allowed to cool, the reaction solution was concentrated under reduced pressure to obtain a brown oil.
反応が１００部進行したことをＮＭＲで確認した。It was confirmed by NMR that 100 parts of the reaction had proceeded.
このものにアセトン４ｔを加え、よく攪拌したのち白色
沈澱を遠心濾過した。この操作を２回くり返し、過ＩＪ
Ｋ用いたジメチルアミノプロピルアミンを抽出除去した
。得られた、Ｎ −３−（Ｎ’、 Ｎ’−ジメチルアミ
ノ）プロピルタウリンナトリウムの白色沈澱を減圧下に
乾燥したのち純水５３０部にとかし潰塩酸５３０−を加
え中和した。中和液を減圧濃縮し、メタノール７００部
を加え不溶の塩化ナトリウムを炉別した。ｐ液を減圧濃
縮、乾燥し、得られた淡黄色固体をクロロホルム１００
０部にとかしたのち遠心分離で不溶性の不純物を除き、
クロロホルム溶液から溶媒を減圧留去して白色固体のＮ
−３−（Ｎ’、 Ｎ’−ジメチルアミノ）プロビルタウ
リ７３７０部を得た。After adding 4 tons of acetone to this and stirring well, the white precipitate was centrifugally filtered. Repeat this operation twice, and
Dimethylaminopropylamine using K was extracted and removed. The obtained white precipitate of sodium N-3-(N', N'-dimethylamino)propyl taurate was dried under reduced pressure, and then neutralized by adding 530 parts of crushed hydrochloric acid to 530 parts of pure water. The neutralized solution was concentrated under reduced pressure, and 700 parts of methanol was added to remove insoluble sodium chloride. The p solution was concentrated under reduced pressure and dried, and the resulting pale yellow solid was dissolved in chloroform at 100%
After dissolving to 0 parts, remove insoluble impurities by centrifugation.
The solvent was distilled off under reduced pressure from the chloroform solution to form a white solid N.
7370 parts of -3-(N', N'-dimethylamino)provirtauri were obtained.
ＮＭＲスペクトル（Ｄ、０）： δ１，９３ （２Ｈ
，ｄｄｄ。NMR spectrum (D, 0): δ1,93 (2H
,ddd.
−ＣＨ，Ｃ捗ＣＨ，−） 。-CH, C progress CH, -).
Ｚ８４５ （６Ｈ，Ｓ。Z845 (6H, S.
Ｃ小）、１７６〜３０４ （２Ｈ，ｍ、 （ＣＨ，）、Ｎ −ＣＨ，） 、 ３．０４〜 λ４４（６Ｈ，ｍ。C small), 176-304 (2H, m, (CH,), N -CH,), 3.04~ λ44 (6H, m.
−ＣＨ，−Ｎ−ＣＨ，Ｃ）！、８０Ｊ（）なお、同様に
して化合物ム１〜２２が製造された。-CH, -N-CH,C)! , 80J () Compounds 1 to 22 were produced in the same manner.
実施例 ２
Ｎ−３−（Ｎ’、 Ｎ’−ジメチルアミノ）プロピルタ
ウリン （化合物 Ａ６）攪拌器をそ
なえた反応器内にジメチルアミノプロピルアミン１０．
２部とメタノール１００部を入し、氷水で冷却した。こ
の溶液にビニルスルホン酸メチルエステル１２２部をメ
タノール１００部にとかした溶液を０℃で滴下した。滴
下後、３０分間攪拌したのち、メタノールを低温でゆっ
くり蒸発させ、次にエタノール処理し、Ｎ −３−（Ｎ
’、 Ｎ’−ジメチルアミン）プロピルタウリンの白色
固体を得た。このものは、実施例１によって得られた化
合物とＮＭＲ−スペク）７５が一致した。Example 2 N-3-(N', N'-dimethylamino)propyl taurine (Compound A6) 10% dimethylaminopropylamine in a reactor equipped with a stirrer.
2 parts and 100 parts of methanol were added, and the mixture was cooled with ice water. A solution of 122 parts of vinyl sulfonic acid methyl ester dissolved in 100 parts of methanol was added dropwise to this solution at 0°C. After the dropwise addition, after stirring for 30 minutes, methanol was slowly evaporated at low temperature, and then treated with ethanol to form N -3-(N
A white solid of propyltaurine (', N'-dimethylamine) was obtained. The NMR spectra (75) of this compound matched those of the compound obtained in Example 1.
なお、同様の方法で化合物ム５〜１６．２０．２１．２
２が製造された。In addition, compounds M5 to 16.20.21.2 were prepared in the same manner.
2 were manufactured.
本発明の化合物は酸性基としてスルホン酸基をまた、塩
基性基として２つのアミノ基をもつ両性化合物である。The compound of the present invention is an amphoteric compound having a sulfonic acid group as an acidic group and two amino groups as basic groups.
そのイオン構造は環境に応じ変化し、例えばアミノスル
ホン酸溶液のｐＨを制御要因として、
の如く変化する。したがって環境制御により多様な反応
性、界面特性、電気化学的特性、生物化学的特性を発揮
する。The ionic structure changes depending on the environment, for example, with the pH of the aminosulfonic acid solution as a controlling factor. Therefore, by controlling the environment, it exhibits diverse reactivity, interfacial properties, electrochemical properties, and biochemical properties.
本発明の化合物は一般に常温で吸湿性の固体であり、水
にもまた各種有機溶媒にも可溶性である特徴をもつ。The compounds of the present invention are generally hygroscopic solids at room temperature, and are characterized by being soluble in water and various organic solvents.
本発明者らは、この両性化合物がアミン基とスルホン酸
基の特徴的官能基を有するところからＮＣＯ基に対して
も何らかの相互作用的親和力をもつ筈であるし、また、
従来のアミノ酸などと異なり、有機溶媒に可溶性である
ことから、水分に対し激しい挙動を示す、イソシアナー
ト化合物の反応に安全かつ直接的に作用を及ぼしうるで
あろうと考え、研究を続けた結果、本発明化合物がイソ
シアナート化合物と活性水素を有する化合物との反応、
ならびに、インシアナートの重付加反応に触媒作用を示
すことを見出した。すなわち、本発明化合物をベンゼン
四塩化炭素、ジオキサン、エーテル、トルエン、ＤＭＳ
ＯｌＴＨＦ等、反応系に陽子を放出しえない中性溶媒に
とかし、イソシアナートと活性水素を有する化合物、例
えばヒドロキシル基含有化合物とのウレタン結合生成反
応、あるいは、インシアナート化合物の多重化反応に触
媒量で存在させる場合に、それぞれ反応速度を増大させ
、触媒作用を示すことが見出された。The present inventors believe that since this amphoteric compound has characteristic functional groups of an amine group and a sulfonic acid group, it should have some kind of interactive affinity for the NCO group, and also,
Unlike conventional amino acids, it is soluble in organic solvents, so we thought that it would be able to safely and directly affect the reaction of isocyanate compounds, which behave violently when exposed to moisture.As a result of our continued research, we found that Reaction of the compound of the present invention with an isocyanate compound and a compound having active hydrogen,
It was also found that it exhibits a catalytic effect on the polyaddition reaction of incyanate. That is, the compound of the present invention is mixed with benzene carbon tetrachloride, dioxane, ether, toluene, DMS.
It is dissolved in a neutral solvent that cannot release protons into the reaction system, such as OlTHF, and used in a catalytic amount for the urethane bond formation reaction between isocyanate and a compound having active hydrogen, such as a hydroxyl group-containing compound, or the multiplexing reaction of incyanate compounds. It has been found that when present, each increases the reaction rate and exhibits catalytic action.
かかるアミノスルホン酸化合物のインシアナート基の反
応触媒作用は、従来全く知られておらず、有機溶媒に可
溶性である点とあいまってイソシアナート基を有する化
合物の重合、付加、縮合反応に多様な展開が期待される
ものである。The reaction catalytic action of the inocyanate group of such aminosulfonic acid compounds has not been known at all, and combined with the fact that they are soluble in organic solvents, a variety of developments have been made in the polymerization, addition, and condensation reactions of compounds having isocyanate groups. This is to be expected.
本発明化合物の触媒作用について以下、実施例により説
明する。The catalytic action of the compounds of the present invention will be explained below with reference to Examples.
実施例 ３
インシアナートＫＬ−２４４４（ＨＭＤＩのインシアヌ
レート）５．０４部に０．３１５部のＮ−３−（Ｎ’、
Ｎ’−ジメチルアミノ）プロピルタウリンを加えＤＭ８
０／キシレン（＝１１５）の混合溶媒＆７６部に溶かし
、イソシアナート溶液を調製した。この溶液にｎ−ヘキ
シルアルコール３．０６部のＤＭＳＯ／キシレン（＝１
１５）１１．０６部の溶液を加え、よくかきまぜた。こ
の混合溶液を０．０２５部液体セルに満たし加熱セル中
で１００℃に保ち、ＩＲ−スペクトルで、２２７０６Ｒ
−”（ν８００ ）での吸光度減少の経時変化を測定し
た。Example 3 0.315 parts of N-3-(N',
Add N'-dimethylamino)propyl taurine and DM8
An isocyanate solution was prepared by dissolving it in 76 parts of a mixed solvent of 0/xylene (=115). Add 3.06 parts of n-hexyl alcohol to this solution in DMSO/xylene (=1
15) 11.06 parts of the solution was added and stirred well. A liquid cell was filled with 0.025 parts of this mixed solution and kept at 100°C in a heating cell.
-" (v800), the change in absorbance over time was measured.
測定結果から反応次数は１次、反応速度定数は、１．２
６就−１であった。From the measurement results, the reaction order is 1st order, and the reaction rate constant is 1.2.
It was 6-1.
同様に測定し、Ｎ−３−（Ｎ’、 Ｎ’−ジメチルアミ
ノ）プロピルタウリンを加えない場合には、反応次数は
２次、反応速度定数は２．１９１ ｍｏｌ”−” ５ｅ
ｅ−’であった。In the same measurement, when N-3-(N', N'-dimethylamino)propyl taurine was not added, the reaction order was 2nd order and the reaction rate constant was 2.191 mol"-" 5e
It was e-'.
以上の結果から、Ｎ−３−（Ｎ’、 Ｎ’−ジメチルア
ミノ）プロピルタウリンを加えると、反応は、インシア
ナートの濃度にのみ依存する１次反応となり、触媒作用
を示すことが明らかになった。From the above results, it is clear that when N-3-(N', N'-dimethylamino)propyl taurine is added, the reaction becomes a first-order reaction that depends only on the concentration of incyanate and exhibits catalytic action. .
実施例 ４ フェニルインシアナートの３量化反応
窒素導入管、マグネチックスターラー、滴下ロート、温
度針を備えた２００−の３ツロフラスコに５０ｆのフェ
ニルイソシアナートのアセトニトリル溶液（濃度１ ｍ
ｏｌ ｋｇ−” ）を入れ、窒素気流中攪拌下、Ｎ−３
−（Ｎ’、 Ｎ’−ジメチルアミノ）プロピルタウリン
のクロロホルム溶液５０？（濃度０．０５ ｍｏｌ ｋ
ｇ＝ ）を一度に加えた。２０〜２２℃で約２０時間攪
拌したのち、析出した３量体トリフェニルインシアヌレ
ー）４．３４Ｆ（７３％＞をＦ取した。３量体はアセト
ニトリルから再結晶してｍｐ２８１５〜２８１０℃の無
色プリズム晶となる。（文献値”ｍｐ ２８１℃）。Example 4 Trimerization reaction of phenyl isocyanate A 50 f solution of phenyl isocyanate in acetonitrile (concentration 1 m
ol kg-”) and stirred in a nitrogen stream, N-3
-(N', N'-dimethylamino)propyl taurine in chloroform solution 50? (Concentration 0.05 mol k
g= ) was added all at once. After stirring at 20-22°C for about 20 hours, the precipitated trimer (triphenyl incyanurate) 4.34F (73%) was recovered. It becomes a colorless prismatic crystal. (Reference value: mp 281°C).
ＩＲスペクトル（ＫＢｒ）： １７００５１’ （ν。IR spectrum (KBr): 170051' (ν.
。）、（文献値引７００ ｔｓ−’ ）。. ), (literature discount 700 ts-').
以上の結果から、Ｎ−３−（Ｎ’、 Ｎ’−ジメチルア
ミノ）プロピルタウリンのイソシアナート３量化触媒作
用を示すことが明らかになった。From the above results, it was revealed that N-3-(N', N'-dimethylamino)propyl taurine exhibits isocyanate trimerization catalytic action.
秦Ｊ、 Ｅ、 Ｋｒｅｓｔａ、 Ｃ，Ｓ、 ５ｈｅｎ、
Ｋ、 Ｃ，ｐｒｉｓｃｈ。Hata J, E, Kresta, C,S, 5hen,
K.C.prisch.
Ｍａｋｒｏｍｏｌ、Ｃｈｅｍ、、 １７８．２４９５
（１９７７）Makromol, Chem, 178.2495
(1977)
第１図は本発明にかかる代表的化合物Ｎ−３（Ｎ／、
Ｎ／−ジメチルアミノ）プロビルタウリ５
２６−
ンＮａ塩のＮＭＲスペクトルを示す。
特許出願代理人
弁理士伊藤武雄FIG. 1 shows a representative compound N-3 (N/,
Figure 2 shows an NMR spectrum of N/-dimethylamino)provirtaurin 526-ene Na salt. Patent application agent Takeo Ito
Claims (1)
アルキル基を表わし、また島とＲ８はそれらの結合され
ている窒素原子とで、モルホリン核、ピペリジン核を作
り、Ｒ８は炭素原子数１〜６のアルキレン基であり、Ｒ
４はＨあるいは炭素原子数１〜４のアルキル基を表わす
。〕で表わされるアミノスルホン酸化合物。 （２）式（１）の化合物が Ｎ−アミノメチルタウリン である％Ｗｆ請求の範囲第１項記載の化合物。 （３）式（１）の化合物が Ｎ−２−アミノエチルタウリン である特許請求の範囲第１項記載の化合物。 （４）式（１）の化合物が Ｎ−３−アミノプロピルタウリン である特許請求の範囲第１項記載の化合物。 （５）式（１）の化合物が Ｎ−６−アミンへキシルタウリン である特許請求の範囲第１項記載の化合物。 （６）式（１）の化合物が Ｎ−３−（メチルアミン）プロピルタウリン である特許請求の範囲第１項記載の化合物。 （７）式（１）の化合物が Ｎ−３−（Ｎ’、Ｎ’−ジメチルアミノ）プロピルタウ
リン である特許請求の範囲第１項記載の化合物。 （８）式（１）の化合物が Ｎ−３−（Ｎ’、Ｎ’−ジメチルアミノ）エテル−Ｎ−
メチルタウリン である特許請求の範囲第１項記載の化合物。 （９） 式（１）の化合物が Ｎ−６−（Ｎ’−メチルアミノ）へキシル−Ｎ−エチル
タウリン である特許請求の範囲第１項記載の化合物。 αＱ 式（１）の化合物が Ｎ−２−（Ｎ’、Ｎ’−ジメチルアミノ）エチル−Ｎ
−ｎ−ブチルタウリン である特許請求の範囲第１項記載の化合物。 （ロ）式（１）の化合物が Ｎ−２−（Ｎ’、Ｎ’−ジメチルアミノ）エチル−Ｎ−
エチルタウリン である特許請求の範囲第１項記載の化合物。 （２）式（１）の化合物が Ｎ−３−（Ｎ’−二チルアミノ）プロビル−Ｎ−エチル
タウリン である特許請求の範囲第１項記載の化合物。 （至）式（Ｉ）の化合物が Ｎ−４−（Ｎ’、Ｎ’−ジエチルアミノ）−１−メチル
ブチルタウリン である特許請求の範囲第１項記載の化合物。 （ロ）式（Ｉ）の化合物が Ｎ−４−（Ｎ’、Ｎ’−ジプロピルアミノ）ブチル−Ｎ
−プロピルタウリン である特許請求の範囲第１項記載の化合物。 （へ）式（１）の化合物が Ｎ−２−（Ｎ’−イソグロビルアミン）エチルタウリン である特許請求の範囲第１項記載の化合物。 （イ）式（Ｉ）の化合物が Ｎ−２−（Ｎ’−イソグロピルアミン）−１゜ｌ−ジメ
チルエチルタウリン である特許請求の範囲第１項記載の化合物。 α力 式（Ｉ）の化合物が Ｎ−３−（Ｎ’、Ｎ’−ジプチルアミノ）プロピルタウ
リン である特許請求の範囲第１項記載の化合物。 （至）式（１）の化合物が Ｎ−４−（Ｎ’−ドデシルアミノ）ブチルタウリン である特許請求の範囲第１項記載の化合物。 （２）式（Ｉ）の化合物が Ｎ−２−（Ｎ’−ドデシルアミノ）エチル−Ｎ−メチル
タウリン である特許請求の範囲第１項記載の化合物。 （転）式（Ｉ）の化合物が Ｎ−３−（Ｎ’−ステアリルアミノ）プロピルタウリン である特許請求の範囲第１項記載の化合物。 （２）式（１）の化合物が Ｎ−３−モルホリノプロピルタウリン である特許請求の範囲第１項記載の化合物。 （２）式（Ｉ）の化合物が Ｎ−６−モルホリノへキシルタウリン である特許請求の範囲第１項記載の化合物。 に）式（１）の化合物が Ｎ−２−ピペリジノエチルタウリン である特許請求の範囲第１項記載の化合物。 一式（Ｉｆ） ＣＨ，＝ ＣＨ−ＳＯ，Ｎａ （旧のビニルス
ルホン酸ナトリウムと、 式（ＩＩＩ）拓＼Ｎ−Ｒ，−
Ｎ）□Ｒ，（ＩＩＩ） Ｒｔ／ 〔式中Ｒ１およびＲ１は夫々Ｈまたは炭素原子数１〜１
８のアルキル基を表わし、また、Ｒ１とＲ３けそれらの
結合されている窒素原子とでモルホリン核、ピペリジン
核を作り、Ｒ１は炭素原子数１〜６のアルキレン基であ
り、Ｒ４はＨあるいは炭素原子数１〜４のアルキル基を
表わす。〕で表わされるジアミン化合物を反応させ、得
られたアミノスルホン酸ナトリウム塩を遊離の酸に導く
ことを特徴とする 式（Ｉ） ４ 佑＼Ｎ−Ｒ，−Ｎ−ＣＨ，ＣＨ，ＳＯ，Ｈ（１）Ｒ，／ 〔式中Ｒ，，Ｒ，、Ｒ，及びＲ６は前述の通り。〕で表
わされるアミノスルホン酸化合物の製造方法。 （ハ）式（ＩＶ） ＣＨ，＝ＣＨ−８Ｏ，Ｒ（ＩＶ） 〔式中Ｒは炭素原子数１〜４のアルキル基を表わす。〕 のビニルスルホン酸ニステルト、 式（ＩＩＩ）弘Ｎ
−Ｒ，−ＮＨＲ，（ＩＩ） Ｒ，／ 〔式中Ｒ１及びＲ８は夫々、Ｈあるいけ炭素原子数１〜
１８のアルキル基を表わし、また、Ｒ１とＲ３はそれら
の結合されている窒素原子とでモルホリン核、ピペリジ
／核を作り、Ｒ１は炭素原子数１〜６のアルキレン基で
あり、Ｒ４はＨあるいは炭素原子数１〜４のアルキル基
を表わす。〕で示されるジアミン化合物を反応させ、得
られたアミノスルホン酸エステルを加水分解することを
特徴とする 式（Ｉ） ４ ”’Ｎ−Ｒ，−Ｎ−ＣＨ，ＣＨ，８０，Ｈ（１）Ｒ，／ 〔式中Ｒ，、Ｒ，、Ｒ１、Ｒ４は前述の通り。〕で表わ
されるアミノスルホン酸化合物の製造方法。 一式（１） ％式％（１） 〔式中Ｒ０及びＲ１は夫々、Ｈあるいは炭素原子数１〜
１８のアルキル基を表わし、また、Ｒ１と島はそれらの
結合されている窒素原子とでモルホリン核、ピペリジン
核を作り、Ｒ１は炭素原子数１〜６のアルキレフ基であ
り、Ｒ４はＨあるいは炭素原子数１〜４のアルキルを表
わす。〕で表わされるアミノスルホン酸化合物からなる
イソシアナート基の反応触媒。[Claims] (+) <(I) R. Taku\N-R, -N-CH, CH, SO, H (1) R, / C In the formula, R1 and R each represent H or an alkyl group having 1 to 18 carbon atoms, and the island and R8 represent their to form a morpholine nucleus or piperidine nucleus, R8 is an alkylene group having 1 to 6 carbon atoms, and R
4 represents H or an alkyl group having 1 to 4 carbon atoms. ] An aminosulfonic acid compound represented by (2) The compound according to claim 1, wherein the compound of formula (1) is N-aminomethyltaurine. (3) The compound according to claim 1, wherein the compound of formula (1) is N-2-aminoethyltaurine. (4) The compound according to claim 1, wherein the compound of formula (1) is N-3-aminopropyltaurine. (5) The compound according to claim 1, wherein the compound of formula (1) is N-6-aminehexyltaurine. (6) The compound according to claim 1, wherein the compound of formula (1) is N-3-(methylamine)propyl taurine. (7) The compound according to claim 1, wherein the compound of formula (1) is N-3-(N', N'-dimethylamino)propyl taurine. (8) The compound of formula (1) is N-3-(N',N'-dimethylamino)ether-N-
The compound according to claim 1, which is methyltaurine. (9) The compound according to claim 1, wherein the compound of formula (1) is N-6-(N'-methylamino)hexyl-N-ethyltaurine. αQ The compound of formula (1) is N-2-(N',N'-dimethylamino)ethyl-N
The compound according to claim 1, which is -n-butyltaurine. (b) The compound of formula (1) is N-2-(N',N'-dimethylamino)ethyl-N-
The compound according to claim 1, which is ethyltaurine. (2) The compound according to claim 1, wherein the compound of formula (1) is N-3-(N'-ditylamino)propyl-N-ethyltaurine. (to) The compound according to claim 1, wherein the compound of formula (I) is N-4-(N', N'-diethylamino)-1-methylbutyltaurine. (b) The compound of formula (I) is N-4-(N',N'-dipropylamino)butyl-N
- The compound according to claim 1, which is propyl taurine. (f) The compound according to claim 1, wherein the compound of formula (1) is N-2-(N'-isoglobylamine)ethyltaurine. (a) The compound according to claim 1, wherein the compound of formula (I) is N-2-(N'-isogropylamine)-1°l-dimethylethyltaurine. α Force The compound according to claim 1, wherein the compound of formula (I) is N-3-(N', N'-diptylamino)propyl taurine. (to) The compound according to claim 1, wherein the compound of formula (1) is N-4-(N'-dodecylamino)butyltaurine. (2) The compound according to claim 1, wherein the compound of formula (I) is N-2-(N'-dodecylamino)ethyl-N-methyltaurine. 2. The compound according to claim 1, wherein the compound of formula (I) is N-3-(N'-stearylamino)propyl taurine. (2) The compound according to claim 1, wherein the compound of formula (1) is N-3-morpholinopropyltaurine. (2) The compound according to claim 1, wherein the compound of formula (I) is N-6-morpholinohexyltaurine. 2) The compound according to claim 1, wherein the compound of formula (1) is N-2-piperidinoethyltaurine. Formula (If) CH,=CH-SO,Na (old sodium vinyl sulfonate and formula (III) Taku\N-R,-
N)□R, (III) Rt/ [In the formula, R1 and R1 are each H or 1 to 1 carbon atoms
8 represents an alkyl group, and R1 and R3 and the nitrogen atoms to which they are bonded form a morpholine nucleus or piperidine nucleus, R1 is an alkylene group having 1 to 6 carbon atoms, and R4 is H or a carbon atom. Represents an alkyl group having 1 to 4 atoms. ] Formula (I) 4 休＼N-R, -N-CH, CH, SO, H (1) R, / [In the formula, R,, R,, R, and R6 are as described above. ] A method for producing an aminosulfonic acid compound represented by (iii) Formula (IV) CH,=CH-8O,R(IV) [In the formula, R represents an alkyl group having 1 to 4 carbon atoms. ] Vinyl sulfonic acid nistert, formula (III) HiroN
-R, -NHR, (II) R, / [In the formula, R1 and R8 are each H or the number of carbon atoms 1 to
18 alkyl group, and R1 and R3 form a morpholine nucleus or piperidine nucleus with their bonded nitrogen atoms, R1 is an alkylene group having 1 to 6 carbon atoms, and R4 is H or Represents an alkyl group having 1 to 4 carbon atoms. Formula (I) 4''N-R,-N-CH,CH,80,H (1), which is characterized by reacting a diamine compound represented by the formula and hydrolyzing the obtained aminosulfonic acid ester. A method for producing an aminosulfonic acid compound represented by R, / [in the formula, R,, R,, R1, and R4 are as described above]. Formula (1) % Formula % (1) [In the formula, R0 and R1 are each , H or number of carbon atoms 1~
R1 represents an alkyl group of 18, and R1 and the island form a morpholine nucleus or piperidine nucleus with the nitrogen atom to which they are bonded, R1 is an alkylev group having 1 to 6 carbon atoms, and R4 is H or a carbon atom. Represents alkyl having 1 to 4 atoms. ] An isocyanate group reaction catalyst consisting of an aminosulfonic acid compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56159310A JPS5859959A (en) | 1981-10-05 | 1981-10-05 | Aminosulfonic acid, its preparation and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56159310A JPS5859959A (en) | 1981-10-05 | 1981-10-05 | Aminosulfonic acid, its preparation and catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5859959A true JPS5859959A (en) | 1983-04-09 |
| JPS6222979B2 JPS6222979B2 (en) | 1987-05-20 |
Family
ID=15691000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56159310A Granted JPS5859959A (en) | 1981-10-05 | 1981-10-05 | Aminosulfonic acid, its preparation and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5859959A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5177256A (en) * | 1990-02-27 | 1993-01-05 | Kao Corporation | Betaine compound and detergent composition |
| JPH0526623U (en) * | 1991-09-20 | 1993-04-06 | セイレイ工業株式会社 | A sled device used together with a wood carrier |
| US5262563A (en) * | 1989-07-25 | 1993-11-16 | Fuji Photo Film Co., Ltd. | Process for producing sulfoalkyl-substituted hydroxylamines |
| WO2008105138A1 (en) * | 2007-02-27 | 2008-09-04 | Mitsui Chemicals, Inc. | Polymerization catalyst for polythiourethane optical material, polymerizable composition containing the catalyst, optical material obtained from the composition, and method for producing the optical material |
| CN107935892A (en) * | 2017-11-24 | 2018-04-20 | 万华化学集团股份有限公司 | A kind of method for preparing ethylenediamine base ethyl sulfonic acid sodium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4962418A (en) * | 1972-09-06 | 1974-06-17 |
-
1981
- 1981-10-05 JP JP56159310A patent/JPS5859959A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4962418A (en) * | 1972-09-06 | 1974-06-17 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5262563A (en) * | 1989-07-25 | 1993-11-16 | Fuji Photo Film Co., Ltd. | Process for producing sulfoalkyl-substituted hydroxylamines |
| US5177256A (en) * | 1990-02-27 | 1993-01-05 | Kao Corporation | Betaine compound and detergent composition |
| JPH0526623U (en) * | 1991-09-20 | 1993-04-06 | セイレイ工業株式会社 | A sled device used together with a wood carrier |
| WO2008105138A1 (en) * | 2007-02-27 | 2008-09-04 | Mitsui Chemicals, Inc. | Polymerization catalyst for polythiourethane optical material, polymerizable composition containing the catalyst, optical material obtained from the composition, and method for producing the optical material |
| JP5254201B2 (en) * | 2007-02-27 | 2013-08-07 | 三井化学株式会社 | Polymerization catalyst for polythiourethane optical material, polymerizable composition containing the same, optical material obtained therefrom, and method for producing the same |
| US8586694B2 (en) | 2007-02-27 | 2013-11-19 | Mitsui Chemicals, Inc. | Polymerization catalyst for polythiourethane-based optical material, polymerizable composition containing the catalyst, optical material obtained from the composition, and method for preparing the optical material |
| CN107935892A (en) * | 2017-11-24 | 2018-04-20 | 万华化学集团股份有限公司 | A kind of method for preparing ethylenediamine base ethyl sulfonic acid sodium |
| CN107935892B (en) * | 2017-11-24 | 2020-06-02 | 万华化学集团股份有限公司 | Method for preparing ethylenediamine ethanesulfonic acid sodium salt |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6222979B2 (en) | 1987-05-20 |
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