JP2004099487A - Method for producing aminoalkylsulfonic acid salt - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply and efficiently producing an aminoalkylsulfonic acid salt on an industrial scale. <P>SOLUTION: The method for producing the aminoalkylsulfonic acid salt represented by general formula [3] (R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group; R<SP>3</SP>and R<SP>4</SP>are each independently a hydrogen atom or a lower alkyl group; T<SB>1</SB>is an alkylene group; M is an alkali metal atom or an ammonium ion; n is 0 or 1) comprises reacting an amine represented by general formula [1] with an alkylenesulfonic acid salt represented by general formula [2]. <P>COPYRIGHT: (C)2004,JPO

Description

【００１０】
（式中、Ｒ^１及びＲ^２は夫々独立して、水素原子、アルキル基、アリール基又はアラルキル基を表し、Ｔ_１はアルキレン基を表し、ｎは０又は１を表す。）で示されるアミン類と一般式［２］
【００１１】
【化５】

【００１２】
（式中、Ｒ^３及びＲ^４は夫々独立して、水素原子又は低級アルキル基を表し、Ｍはアルカリ金属原子又はアンモニウムイオンを表す。）で示されるアルキレンスルホン酸塩を反応させることを特徴とする、一般式［３］
【００１３】
【化６】

【００１４】
（式中、Ｒ^１〜Ｒ^４、Ｔ_１、Ｍ及びｎは前記に同じ。）で示されるアミノアルキルスルホン酸塩の製造法、の発明である。
【００１５】
即ち、発明者等は上記目的を達成すべく鋭意研究を重ねた結果、上記一般式［１］で示されるアミン類と一般式［２］で示されるアルキレンスルホン酸塩を反応させることにより、一般式［３］で示されるアミノアルキルスルホン酸塩を簡便且つ効率よく工業的に製造し得ることを見出し、本発明を完成するに至った。
【００１６】
一般式［１］及び［３］に於いて、Ｒ^１及びＲ^２で示されるアルキル基としては、直鎖状、分枝状或いは環状の何れでもよく、通常炭素数１〜１２、好ましくは１〜６、より好ましくは１〜３のものが挙げられ、具体的には、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ｓｅｃ−ペンチル基、ｔｅｒｔ−ペンチル基、ネオペンチル基、ｎ−ヘキシル基、イソヘキシル基、ｓｅｃ−ヘキシル基、ｔｅｒｔ−ヘキシル基、ネオヘキシル基、ｎ−ヘプチル基、イソヘプチル基、ｓｅｃ−ヘプチル基、ｔｅｒｔ−ヘプチル基、ネオヘプチル基、ｎ−オクチル基、イソオクチル基、ｓｅｃ−オクチル基、ｔｅｒｔ−オクチル基、ネオオクチル基、ｎ−ノニル基、イソノニル基、ｓｅｃ−ノニル基、ｔｅｒｔ−ノニル基、ネオノニル基、ｎ−デシル基、イソデシル基、ｓｅｃ−デシル基、ｔｅｒｔ−デシル基、ネオデシル基、ｎ−ウンデシル基、イソウンデシル基、ｓｅｃ−ウンデシル基、ｔｅｒｔ−ウンデシル基、ネオウンデシル基、ｎ−ドデシル基、イソドデシル基、ｓｅｃ−ドデシル基、ｔｅｒｔ−ドデシル基、ネオドデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基等が挙げられ、中でもメチル基が好ましい。
【００１７】
Ｒ^１及びＲ^２で示されるアリール基としては、通常６〜１０のものが挙げられ、具体的には、例えばフェニル基、ナフチル基等が挙げられ、中でもフェニル基が好ましい。
【００１８】
Ｒ^１及びＲ^２で示されるアラルキル基としては、通常炭素数７〜９のものが挙げられ、具体的には、例えばベンジル基、フェネチル基、フェニルプロピル基等が挙げられ、中でもベンジル基が好ましい。
【００１９】
Ｔ_１で示されるアルキレン基としては、直鎖状、分枝状或いは環状の何れでもよく、通常炭素数１〜１２、好ましくは１〜６、より好ましくは１〜３のものが挙げられ、具体的には、例えばメチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ブチレン基、２−メチルプロピレン基、ペンタメチレン基、ペンチレン基、２−メチルテトラメチレン基、２，２−ジメチルトリメチレン基、２−エチルトリメチレン基、ヘキサメチレン基、ヘキシレン基、２−メチルペンタメチレン基、３−メチルペンタメチレン基、ヘプタメチレン基、ヘプチレン基、オクタメチレン基、オクチレン基、２−エチルへキシレン基、ノナメチレン基、ノニレン基、デカメチレン基、デシレン基、ヘンデカメチレン基、ドデカメチレン基、シクロプロピレン基、シクロペンチレン基、シクロヘキシレン基、シクロヘプチレン基、シクロオクチレン基、シクロノニレン基、シクロデシレン基等が挙げられ、中でもエチレン基が好ましい。
【００２０】
また、一般式［１］及び［３］に於けるＲ^１及びＲ^２は、一方が水素原子であり他方がアルキル基であるもの、または共にアルキル基であるものが好ましい。
【００２１】
一般式［２］に於いて、Ｒ^３及びＲ^４で示される低級アルキル基は、直鎖状、分枝状或いは環状の何れでもよく、通常炭素数１〜６、好ましくは１〜３のものが挙げられ、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ｓｅｃ−ペンチル基、ｔｅｒｔ−ペンチル基、ネオペンチル基、ｎ−ヘキシル基、イソヘキシル基、ｓｅｃ−ヘキシル基、ｔｅｒｔ−ヘキシル基、ネオヘキシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられ、中でもメチル基が好ましい。
【００２２】
Ｍで示されるアルカリ金属原子としては、例えばリチウム原子、ナトリウム原子、カリウム原子、ルビジウム原子等が挙げられ、中でもナトリウム原子、カリウム原子が好ましい。
【００２３】
また、一般式［２］に於けるＲ^３及びＲ^４は、共に水素原子であるものが好ましい。
【００２４】
一般式［１］で示されるアミン類の好ましい具体例としては、例えばアンモニア、例えばメチルアミン、エチルアミン等のモノアミン類、例えばＮ，Ｎ’−ジメチルメチレンジアミン、Ｎ，Ｎ’−ジメチルエチレンジアミン等のジアミン類等が挙げられ、中でもメチルアミン、Ｎ，Ｎ’−ジメチルエチレンジアミンが好ましい。
【００２５】
一般式［２］で示されるアルキレンスルホン酸塩の具体例としては、例えばビニルスルホン酸アルカリ金属塩（例えばリチウム塩、ナトリウム塩、カリウム塩、ルビジウム塩、セシウム塩等。）、ビニルスルホン酸アンモニウム塩等が挙げられ、中でもビニルスルホン酸ナトリウム塩、ビニルスルホン酸カリウム塩が好ましく、就中、ビニルスルホン酸ナトリウム塩がより好ましい。
【００２６】
一般式［３］で示されるアミノアルキルスルホン酸塩の好ましい具体例としては、モノアミン類の例示としては、例えばタウリン、Ｎ−メチルタウリン、Ｎ−エチルタウリン等のアルカリ金属塩（例えばリチウム塩、ナトリウム塩、カリウム塩、ルビジウム塩、セシウム塩等。）、アンモニウム塩等が挙げられ、ジアミン類の例示としては、例えばＮ，Ｎ’−ジメチルメチレンジアミノ−１，１’−ビス（エタンスルホン酸）、Ｎ，Ｎ’−ジメチルエチレンジアミノ−２，２’−ビス（エタンスルホン酸）等の二アルカリ金属塩（例えばリチウム塩、ナトリウム塩、カリウム塩、ルビジウム塩、セシウム塩等。）、二アンモニウム塩等が挙げられ、中でも、例えばＮ−メチルタウリンナトリウム塩、Ｎ−メチルタウリンカリウム塩等のモノアミン類、例えばＮ，Ｎ’−ジメチルエチレンジアミノ−２，２’−ビス（エタンスルホン酸）二ナトリウム、Ｎ，Ｎ’−ジメチルエチレンジアミノ−２，２’−ビス（エタンスルホン酸）二カリウム等のジアミン類が好ましく、就中、Ｎ−メチルタウリンナトリウム塩、Ｎ，Ｎ’−ジメチルエチレンジアミノ−２，２’−ビス（エタンスルホン酸）二ナトリウム等がより好ましい。
【００２７】
一般式［１］で示されるアミン類及び一般式［２］で示されるアルキレンスルホン酸塩は、市販品を用いても、常法により適宜製造したものを用いてもよい。
【００２８】
反応溶媒としては、例えばメタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール等のアルコール類、例えばアセトン、エチルメチルケトン等のケトン類、例えばＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミド類、例えばテトラヒドロフラン、ジオキサン、水等が挙げられる。これらの溶媒は夫々単独で用いても、二種以上適宜組み合わせて用いてもよい。
【００２９】
一般式［２］で示されるアルキレンスルホン酸塩の使用量は、使用する一般式［１］で示されるアミン類の種類によっても異なるが、一般式［１］で示されるアミン類１モルに対して、通常０．６〜４０倍モル、好ましくは１．０〜２．４倍モルである。
【００３０】
反応温度は、通常０〜２００℃、好ましくは５０〜１００℃である。また、例えばヘリウムガス、窒素ガス、アルゴンガス等の不活性ガス等を用いて反応系に圧力を加えることにより反応温度を上昇させてもよい。この場合、加える圧力は、大きすぎても反応効率は高くならないため、通常１〜１００ｋｇ／ｃｍ^２、好ましくは２〜１０ｋｇ／ｃｍ^２である。
【００３１】
反応時間は、反応温度、使用するアミン類及びアルキレンスルホン酸塩の種類、反応溶媒、これらの濃度等の反応条件により異なるが、通常５分〜１０時間である。
【００３２】
本発明の製造法により得られた一般式［３］で示されるアミノアルキルスルホン酸塩は、例えば下記方法により対応するアミノアルキルスルホン酸を製造し、晶析処理を行った後、適当な水酸化アルカリ金属類（例えば水酸化ナトリウム、水酸化カリウム等。）で処理すれば、対応するアミノアルキルスルホン酸塩が高純度で得られる。
【００３３】
対応するアミノアルキルスルホン酸を製造するには、下記方法が挙げられる。
【００３４】
即ち、例えば一般式［３］で示されるアミノアルキルスルホン酸塩のうち、ｎ＝０であるもの（以下、１量体と略記する。）の場合は、当該１量体の水溶液を濃縮し、これに水溶性有機溶媒（例えばメタノール、エタノール、酢酸、プロピオン酸、ジメチルホルムアミド等。）及び有機酸（例えば酢酸等）を添加し２０〜３０℃で撹拌反応させる。反応終了後、反応液を−５〜−１０℃で１時間静置させ、結晶を熟成させた後、得られた晶析物を洗浄、減圧乾燥させることにより対応するアミノアルキルスルホン酸が得られる。
【００３５】
また、当該アミノアルキルスルホン酸塩のうち、ｎ＝１であるもの（以下、２量体と略記する。）の場合は、当該２量体の水溶液に、有機酸又は鉱酸（例えば塩酸、硫酸等。）を添加し２０〜３０℃で撹拌反応させる。反応終了後、反応液を０〜３０℃で１時間静置させ、結晶を熟成させた後、得られた晶析物を洗浄、減圧乾燥させることにより対応するアミノアルキルスルホン酸が得られる。
【００３６】
このようにして得られたアミノアルキルスルホン酸は、水酸化アルカリ金属類（例えば水酸化ナトリウム、水酸化カリウム等）を溶解させたアルコール（例えばエタノール等。）溶液中に添加され、２５〜３０℃で１時間撹拌反応させる。反応終了後、得られた晶析物を濾取し、洗浄、減圧乾燥させることにより、一般式［３］で示されるアミノアルキルスルホン酸塩をその溶液状態若しくは晶析物として得られる。
【００３７】
反応後の後処理等は、この分野に於いて通常行われる後処理法に準じて行えばよい。
【００３８】
本発明の、一般式［３］で示されるアミノアルキルスルホン酸塩の製造法は、従来法が有していた、高温高圧条件下で反応を行うためコストがかかり且つ危険が伴うという欠点を有することなく、安全に、経済的且つ高収率に一般式［３］で示されるアミノアルキルスルホン酸塩を工業的に製造し得る。
【００３９】
以上、実施例を挙げて本発明を詳細に説明するが、本発明はこれらにより限定されるものではない。
【００４０】
【実施例】
実施例１．　Ｎ−メチルタウリンの合成
２５％ビニルスルホン酸ナトリウム塩水溶液　１００．０ｇ（１９２ｍｍｏｌ）及び４０％メチルアミン水溶液　１６．４ｇ（２１１ｍｍｏｌ）をステンレス製オートクレーブに添加し、１００±５℃で３時間撹拌反応させた。反応終了後、水を減圧濃縮し、メタノール　１２０ｍＬ及び酢酸　１２．１ｇ（２０１ｍｍｏｌ）を加え、２０〜３０℃で１時間撹拌反応させた。反応終了後、反応液を−１０℃に冷却して同温度で１時間撹拌させた後、結晶を濾取、減圧乾燥し、目的物　２２．７ｇを白色結晶として得た（収率８５％）。
【００４１】
実施例２．　Ｎ，Ｎ’−ジメチルエチレンジアミノ−２，２’−ビス（エタンスルホン酸）二ナトリウムの合成
２５％ビニルスルホン酸ナトリウム塩水溶液　６０２．２ｇ（１．１６ｍｏｌ）中にＮ，Ｎ’−ジメチルエチレンジアミン（三井化学（株）社製）　５１．０ｇ（０．５８ｍｏｌ）を添加し、還流下１００〜１０５℃で４時間撹拌反応させた。反応終了後、反応液を冷却し、濃硫酸　５６．８ｇ（０．５８ｍｏｌ）を添加し２０〜３０℃で１時間晶析させた。結晶を濾取、減圧乾燥しＮ，Ｎ’−ジメチルエチレンジアミノ−２，２’−ビス（エタンスルホン酸）　１６７．３ｇを白色結晶として得た（収率９５．０％）。
【００４２】
次いで、水酸化ナトリウム　４６．３ｇ（１．１６ｍｏｌ）をエタノール　１０００ｍＬに溶解した溶液に、得られたＮ，Ｎ’−ジメチルエチレンジアミノ−２，２’−ビス（エタンスルホン酸）　１６７．３ｇ（０．５５ｍｏｌ）を溶解させ、２５〜３０℃で１時間撹拌反応させた。結晶を濾取、減圧乾燥し目的物　１８９．４ｇを白色結晶として得た（収率９４．０％）。
【００４３】
実施例３．　Ｎ，Ｎ’−ジメチルエチレンジアミノ−２，２’−ビス（エタンスルホン酸）二カリウム
水酸化ナトリウム　４６．３ｇ（１．１６ｍｏｌ）の代わりに水酸化カリウム　６４．９ｇ（１．１６ｍｏｌ）を用いた以外、実施例２と同様の操作を行い、目的物　２０７．０ｇを白色結晶として得た（収率９４．０％）。
【００４４】
【発明の効果】本発明のアミノアルキルスルホン酸塩の製造法は、従来法が有していた、例えばメチルアミンを高温高圧で反応させる必要があるため工業的規模で製造するには高価な装置を必要とする等の問題点を有することなく、簡便且つ効率よく工業的にアミノアルキルスルホン酸塩を製造し得る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for easily and economically producing an aminoalkyl sulfonate on an industrial scale.
[0002]
[Prior art]
Aminoalkyl sulfonates are known as intermediate materials such as skin cleansing agents such as soap and shampoo, pharmaceutical raw materials, surfactants, pH buffers and the like.
[0003]
As a method for synthesizing monoamines of aminoalkyl sulfonate, for example, (1) a method of reacting sodium isethionate with methylamine at 270 to 290 ° C. and 200 atm (for example, Patent Document 1, Patent Document 2, Patent Document 3) And (2) reacting sodium chloroethylsulfonate with methylamine, and then reacting the obtained aminoethanesulfonate with sodium hydroxide (for example, see Patent Document 4). ing. However, these methods have a problem that, since it is necessary to react methylamine at a high temperature and a high pressure, production on an industrial scale requires expensive equipment and the like, and the operation becomes complicated.
[0004]
As a method for synthesizing diamines of aminoalkyl sulfonate, for example, N-methyltaurine sodium salt and 1,2-dichloroethane are reacted in the presence of magnesium hydroxide to give N, N′-dimethylethylenediamino-2, A method for producing N, N'-dimethylethylenediamino-2,2'-bis (ethanesulfonic acid) by producing 2'-bis (ethanesulfonic acid) disodium and then reacting it with sulfuric acid ( For example, see Patent Document 5). However, these methods require, for example, a large amount of magnesium hydroxide to control side reactions, the need to add sodium hydroxide over time while adjusting the pH during the reaction, and the use of multiple reagents. And so on.
[0005]
Under such circumstances, development of a method for industrially producing an aminoalkyl sulfonate simply and efficiently is desired.
[0006]
[Patent Document 1]
German Patent No. 1122540 (pages 3-4, 13)
[Patent Document 2]
U.S. Pat. No. 1932907 (page 2)
[Patent Document 3]
U.S. Patent No. 1999614 (page 2)
[Patent Document 4]
JP-A-6-345717 (pages 2-4)
[Patent Document 5]
WO 96/35662 (No. 3, pp. 73-74)
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation, and has as its object to provide a method capable of easily and efficiently producing an aminoalkyl sulfonate on an industrial scale.
[0008]
[Means for Solving the Problems]
The present invention has been made for the purpose of solving the above problems, and has a general formula [1]
[0009]
Embedded image

[0010]
(Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, T ₁ represents an alkylene group, and n represents 0 or 1). And general formula [2]
[0011]
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[0012]
(Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or a lower alkyl group, and M represents an alkali metal atom or an ammonium ion). General formula [3]
[0013]
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[0014]
(Wherein R ^{1 to} R ⁴ , T ₁ , M and n are the same as described above).
[0015]
That is, the inventors have conducted intensive studies to achieve the above object, and as a result, by reacting the amines represented by the general formula [1] with the alkylene sulfonate represented by the general formula [2], The present inventors have found that the aminoalkyl sulfonate represented by the formula [3] can be easily and efficiently industrially produced, and have completed the present invention.
[0016]
In the general formulas [1] and [3], the alkyl group represented by R ¹ and R ² may be any of linear, branched or cyclic, and usually has 1 to 12 carbon atoms, preferably 1 to 2 carbon atoms. To 6, more preferably 1 to 3, and specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- Butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, n-heptyl group, Isoheptyl group, sec-heptyl group, tert-heptyl group, neoheptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group Group, neooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, n-undecyl Group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl Group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group and the like, and among them, a methyl group is preferable.
[0017]
As the aryl group represented by R ¹ and R ² , usually 6 to 10 are mentioned, and specifically, for example, a phenyl group, a naphthyl group and the like are preferable, and a phenyl group is particularly preferable.
[0018]
The aralkyl group represented by R ¹ and R ² is usually an aralkyl group having 7 to 9 carbon atoms, specifically, for example, a benzyl group, a phenethyl group, a phenylpropyl group and the like, among which a benzyl group is preferable. .
[0019]
The alkylene group represented by T ₁ may be linear, branched or cyclic, and usually has 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Specifically, for example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, butylene group, 2-methylpropylene group, pentamethylene group, pentylene group, 2-methyltetramethylene group, 2,2-dimethyltrimethylene group Methylene group, 2-ethyltrimethylene group, hexamethylene group, hexylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, heptamethylene group, heptylene group, octamethylene group, octylene group, 2-ethylhexylene Group, nonamethylene group, nonylene group, decamethylene group, decylene group, handecamethylene group, dodecamethylene group, Examples thereof include a cyclopropylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group and the like, and among them, an ethylene group is preferable.
[0020]
In addition, one of R ¹ and R ² in the general formulas [1] and [3] is preferably a hydrogen atom and the other is an alkyl group, or both are preferably an alkyl group.
[0021]
In the general formula [2], the lower alkyl group represented by R ³ and R ⁴ may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. preferable.
[0022]
Examples of the alkali metal atom represented by M include a lithium atom, a sodium atom, a potassium atom, and a rubidium atom, and among them, a sodium atom and a potassium atom are preferable.
[0023]
Further, it is preferable that R ³ and R ⁴ in the general formula [2] are both hydrogen atoms.
[0024]
Preferred specific examples of the amine represented by the general formula [1] include, for example, ammonia, monoamines such as methylamine and ethylamine, and diamines such as N, N′-dimethylmethylenediamine and N, N′-dimethylethylenediamine. And the like, among which methylamine and N, N'-dimethylethylenediamine are preferred.
[0025]
Specific examples of the alkylene sulfonate represented by the general formula [2] include, for example, alkali metal salts of vinyl sulfonic acid (eg, lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, etc.), and ammonium vinyl sulfonate. And the like. Among them, vinyl sulfonic acid sodium salt and vinyl sulfonic acid potassium salt are preferable, and particularly, vinyl sulfonic acid sodium salt is more preferable.
[0026]
Preferred specific examples of the aminoalkyl sulfonate represented by the general formula [3] include monoamines, for example, alkali metal salts such as taurine, N-methyltaurine, and N-ethyltaurine (eg, lithium salt, sodium salt). Salts, potassium salts, rubidium salts, cesium salts, etc.), ammonium salts and the like. Examples of diamines include N, N′-dimethylmethylenediamino-1,1′-bis (ethanesulfonic acid), and the like. Dialkali metal salts such as N, N'-dimethylethylenediamino-2,2'-bis (ethanesulfonic acid) (eg, lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, etc.), diammonium salt, etc. And monoamines such as N-methyltaurine sodium salt and N-methyltaurine potassium salt, among others. For example, diamines such as disodium N, N'-dimethylethylenediamino-2,2'-bis (ethanesulfonic acid) and dipotassium N, N'-dimethylethylenediamino-2,2'-bis (ethanesulfonic acid) Are preferable, and N-methyltaurine sodium salt, N, N'-dimethylethylenediamino-2,2'-bis (ethanesulfonic acid) disodium and the like are more preferable.
[0027]
As the amines represented by the general formula [1] and the alkylene sulfonate represented by the general formula [2], commercially available products or those appropriately produced by a conventional method may be used.
[0028]
Examples of the reaction solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, for example, ketones such as acetone and ethyl methyl ketone, for example, N, N-dimethylformamide, N, N- Amides such as dimethylacetamide, for example, tetrahydrofuran, dioxane, water and the like can be mentioned. These solvents may be used alone or in combination of two or more.
[0029]
The amount of the alkylene sulfonate represented by the general formula [2] varies depending on the kind of the amine represented by the general formula [1] to be used, but is based on 1 mol of the amine represented by the general formula [1]. Thus, it is usually 0.6 to 40 times mol, preferably 1.0 to 2.4 times mol.
[0030]
The reaction temperature is usually 0 to 200 ° C, preferably 50 to 100 ° C. The reaction temperature may be increased by applying pressure to the reaction system using an inert gas such as helium gas, nitrogen gas, or argon gas. In this case, pressure applied, since too large not reaction efficiency is high, usually 1 to 100 kg / cm ^2, preferably 2 to 10 kg / cm ^2.
[0031]
The reaction time varies depending on the reaction conditions such as the reaction temperature, the type of amines and alkylene sulfonates used, the reaction solvent, and the concentration thereof, but is usually 5 minutes to 10 hours.
[0032]
The aminoalkylsulfonic acid salt represented by the general formula [3] obtained by the production method of the present invention can be prepared by, for example, producing the corresponding aminoalkylsulfonic acid by the following method, subjecting it to crystallization treatment, When treated with an alkali metal (for example, sodium hydroxide, potassium hydroxide, etc.), the corresponding aminoalkyl sulfonate can be obtained with high purity.
[0033]
The following method can be used to produce the corresponding aminoalkylsulfonic acid.
[0034]
That is, for example, in the case of an aminoalkyl sulfonate represented by the general formula [3], wherein n = 0 (hereinafter abbreviated as a monomer), an aqueous solution of the monomer is concentrated, A water-soluble organic solvent (e.g., methanol, ethanol, acetic acid, propionic acid, dimethylformamide, etc.) and an organic acid (e.g., acetic acid, etc.) are added thereto, and the mixture is stirred and reacted at 20 to 30C. After completion of the reaction, the reaction solution is allowed to stand at −5 to −10 ° C. for 1 hour, and after aging the crystals, the obtained crystallized product is washed and dried under reduced pressure to obtain the corresponding aminoalkylsulfonic acid. .
[0035]
In the case of the aminoalkyl sulfonate wherein n = 1 (hereinafter abbreviated as dimer), an organic acid or a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) is added to the aqueous solution of the dimer. And the like, and the mixture is stirred and reacted at 20 to 30 ° C. After completion of the reaction, the reaction solution is allowed to stand at 0 to 30 ° C. for 1 hour to mature the crystals, and the obtained crystallized product is washed and dried under reduced pressure to obtain the corresponding aminoalkylsulfonic acid.
[0036]
The aminoalkylsulfonic acid thus obtained is added to a solution of an alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide, etc.) in an alcohol (eg, ethanol, etc.) solution, and the temperature is 25 to 30 ° C. For 1 hour. After completion of the reaction, the obtained crystallized product is collected by filtration, washed and dried under reduced pressure to obtain the aminoalkylsulfonic acid salt represented by the general formula [3] in a solution state or as a crystallized product.
[0037]
Post-treatment after the reaction may be carried out according to a post-treatment method generally used in this field.
[0038]
The method for producing an aminoalkylsulfonate represented by the general formula [3] of the present invention has a disadvantage that the reaction is carried out under high-temperature and high-pressure conditions, which is expensive and involves risks, which the conventional method has. Without this, the aminoalkyl sulfonate represented by the general formula [3] can be industrially produced safely, economically and in high yield.
[0039]
As described above, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
[0040]
【Example】
Embodiment 1 FIG. Synthesis of N-methyltaurine 100.0 g (192 mmol) of a 25% aqueous solution of sodium vinyl sulfonic acid and 16.4 g (211 mmol) of a 40% aqueous solution of methylamine were added to a stainless steel autoclave, and the mixture was stirred and reacted at 100 ± 5 ° C. for 3 hours. Was. After completion of the reaction, water was concentrated under reduced pressure, 120 mL of methanol and 12.1 g (201 mmol) of acetic acid were added, and the mixture was stirred and reacted at 20 to 30 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to −10 ° C. and stirred at the same temperature for 1 hour, and then the crystals were collected by filtration and dried under reduced pressure to obtain 22.7 g of the desired product as white crystals (85% yield). .
[0041]
Embodiment 2. FIG. Synthesis of disodium N, N'-dimethylethylenediamino-2,2'-bis (ethanesulfonic acid) 25% vinylsulfonic acid sodium salt aqueous solution 602.2 g (1.16 mol) in N, N'-dimethylethylenediamine (602.2 g) 51.0 g (0.58 mol) of Mitsui Chemicals, Inc. was added, and the mixture was stirred and reacted at 100 to 105 ° C. for 4 hours under reflux. After completion of the reaction, the reaction solution was cooled, 56.8 g (0.58 mol) of concentrated sulfuric acid was added, and the mixture was crystallized at 20 to 30 ° C. for 1 hour. The crystals were collected by filtration and dried under reduced pressure to obtain 167.3 g of N, N'-dimethylethylenediamino-2,2'-bis (ethanesulfonic acid) as white crystals (yield 95.0%).
[0042]
Next, 167.3 g of the obtained N, N′-dimethylethylenediamino-2,2′-bis (ethanesulfonic acid) was dissolved in a solution of 46.3 g (1.16 mol) of sodium hydroxide in 1000 mL of ethanol. .55 mol) and reacted under stirring at 25-30 ° C. for 1 hour. The crystals were collected by filtration and dried under reduced pressure to obtain 189.4 g of the desired product as white crystals (yield 94.0%).
[0043]
Embodiment 3 FIG. N, N'-dimethylethylenediamino-2,2'-bis (ethanesulfonic acid) dipotassium sodium hydroxide 64.9 g (1.16 mol) was used instead of 46.3 g (1.16 mol) of sodium hydroxide. Except for this, the same operation as in Example 2 was performed to obtain 207.0 g of the desired product as white crystals (yield 94.0%).
[0044]
According to the method for producing an aminoalkylsulfonate of the present invention, it is necessary to react methylamine at a high temperature and a high pressure. It is possible to industrially and easily produce an aminoalkyl sulfonate industrially without problems such as the need for

Claims (11)

General formula [1]

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, T ₁ represents an alkylene group, and n represents 0 or 1). And general formula [2]

(Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or a lower alkyl group, and M represents an alkali metal atom or an ammonium ion). General formula [3]

(Wherein, R ^{1 to} R ⁴ , T ₁ , M, and n are the same as described above). The method according to claim 1, wherein n is 0. 3. The production method according to claim 2, wherein ^one of R ¹ and R ² is a hydrogen atom, and the other is an alkyl group. The production method according to claim 1, wherein n is 1. The method according to claim 4, wherein R ¹ and R ² are alkyl groups. The production method according to claim 4, wherein the alkylene group represented by T1 has ₁ to 3 carbon atoms. Lower alkyl group represented by R ³ and R ⁴ are of 1 to 3 carbon atoms, Process according to claim 1. The production method according to claim 1, wherein the alkali metal atom represented by M is a sodium atom. The method according to claim 8, wherein the alkylene sulfonate represented by the general formula [2] is sodium vinyl sulfonate. The method according to claim 2, wherein the amine represented by the general formula [1] is N-methylamine, and the aminoalkyl sulfonate represented by the general formula [3] is N-methyltaurine sodium salt. The amine represented by the general formula [1] is N, N'-dimethylethylenediamine, and the aminoalkylsulfonate represented by the general formula [3] is N, N'-dimethylethylenediamino-2,2'-bis. The production method according to claim 4, which is disodium (ethanesulfonic acid).