JPH049361A - Production of amidoamine-type compound - Google Patents
Production of amidoamine-type compoundInfo
- Publication number
- JPH049361A JPH049361A JP11154890A JP11154890A JPH049361A JP H049361 A JPH049361 A JP H049361A JP 11154890 A JP11154890 A JP 11154890A JP 11154890 A JP11154890 A JP 11154890A JP H049361 A JPH049361 A JP H049361A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- reaction
- type compound
- imidazoline
- inorganic salt
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims abstract 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 239000004094 surface-active agent Substances 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000007142 ring opening reaction Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 206010040880 Skin irritation Diseases 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 230000036556 skin irritation Effects 0.000 abstract description 2
- 231100000475 skin irritation Toxicity 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 abstract 2
- QNDGQRJVVZJMJO-UHFFFAOYSA-N 2-(2-undecyl-4,5-dihydroimidazol-1-yl)ethanol Chemical compound CCCCCCCCCCCC1=NCCN1CCO QNDGQRJVVZJMJO-UHFFFAOYSA-N 0.000 abstract 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 125000002636 imidazolinyl group Chemical group 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- 150000003511 tertiary amides Chemical class 0.000 description 13
- 150000001242 acetic acid derivatives Chemical class 0.000 description 8
- 150000003334 secondary amides Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- -1 1-hydroxyethyl-2-heptadecyl Chemical group 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PIINGYXNCHTJTF-UHFFFAOYSA-N 2-(2-azaniumylethylamino)acetate Chemical compound NCCNCC(O)=O PIINGYXNCHTJTF-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- KDPAWGWELVVRCH-UHFFFAOYSA-N bromoacetic acid Chemical compound OC(=O)CBr KDPAWGWELVVRCH-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
Landscapes
- Detergent Compositions (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〕
本発明は両性界面活性剤として有用なアミドアミン型化
合物の効率的な製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an efficient method for producing amidoamine type compounds useful as amphoteric surfactants.
〔従来の技術及び発明が解決しようとする課題〕近年、
洗浄剤などに用いられる界面活性剤には、安全性が高く
、眼や皮膚に対し低刺激であること、生分解性が良好で
あることが要望されている。これらの要望を満たす界面
活性剤の一つとして、イミダシリン型両性界面活性剤が
ある。イミダシリン型両性界面活性剤は、優れた起泡力
・洗浄力に加え、眼や皮膚に対しても刺激が極めて低い
ことから、近年低刺激性シャンプーなどの主要成分又は
添加剤としてその使用量が増大している。[Problems to be solved by conventional techniques and inventions] In recent years,
Surfactants used in detergents and the like are required to be highly safe, have low irritation to the eyes and skin, and have good biodegradability. One of the surfactants that meet these demands is an imidacillin type amphoteric surfactant. Imidacillin-type amphoteric surfactants have excellent foaming and cleansing power, and are extremely non-irritating to the eyes and skin. It is increasing.
イミダシリン型界面活性剤は、長い間イミダシリン骨格
を有するものと考えられてきたが、最近の研究によって
イミダシリン環が開裂した一般式（１）で表わされる３
級アミド型化合物及び一般式（ＩＩ）で表わされる２級
アミド型化合物の混合物であることが明らかになった。Imidacillin-type surfactants have long been thought to have an imidacillin skeleton, but recent research has revealed that the imidacillin-type surfactants are 3
It was revealed that the compound was a mixture of a secondary amide type compound and a secondary amide type compound represented by general formula (II).
〔式中、Ｒは炭素数７〜２３の直鎮又は分岐鎖のアルキ
ル、アルケニル、ヒドロキシアルキル又はアラルキル基
を示し、賛は水素原子、アルカリ金属原子、アンモニウ
ム基又はアルカノールアミンの陽イオン残基を示す〕
このような界面活性剤は、今日でも旧来の習慣からイミ
ダシリン型界面活性剤と呼称されているが、本明細書で
は正しい構造式に基いて「アミドアミン型界面活性剤」
と称する。[In the formula, R represents a straight or branched alkyl, alkenyl, hydroxyalkyl, or aralkyl group having 7 to 23 carbon atoms, and R represents a hydrogen atom, an alkali metal atom, an ammonium group, or a cationic residue of an alkanolamine. ] Such surfactants are still called imidacillin-type surfactants due to old custom, but in this specification, based on the correct structural formula, they are referred to as "amidoamine-type surfactants."
It is called.
３級アミド型化合物（Ｉ＞は、２級アミド型化合物（Ｉ
［）に比べ、粘度が低く取り扱いが容易であり、眼や皮
膚に対する刺激性が低いという特徴があり、界面活性剤
としてより有用である。A tertiary amide type compound (I> is a secondary amide type compound (I)
Compared to [), it has a lower viscosity, is easier to handle, and is less irritating to the eyes and skin, making it more useful as a surfactant.
ところで、アミドアミン型界面活性剤は、一般に２−ア
ルキル（又は２−アルケニル）イミダシリン、その開溝
化合物又はそれらの混合物にモノハロゲン化酢酸又はそ
の塩を反応させることによって製造されているが、この
方法では前記３級アミド型化合物（１）と２級アミド型
化合物（ＩＩ）の含有率をコントロールし、化合物（’
Ｉ）を高選択的に製造することは不可能であった。また
、特開昭６１−１４３３４７号公報においては、２−ア
ルキルイミダシリンとモノハロゲン化酢酸塩との反応に
際し、反応液のｐＨを７ないし１２の間の所望値になる
ように調整し、かつ反応中、反応液のｐＨを前記調整値
の近傍に保持することにより、３級アミド型化合物（Ｉ
）が選択的に得られると報告されている。By the way, amidoamine type surfactants are generally produced by reacting 2-alkyl (or 2-alkenyl) imidacillin, its open-groove compound, or a mixture thereof with monohalogenated acetic acid or a salt thereof, but this method Then, by controlling the content of the tertiary amide type compound (1) and the secondary amide type compound (II), the compound ('
It was not possible to produce I) with high selectivity. Furthermore, in JP-A-61-143347, the pH of the reaction solution is adjusted to a desired value between 7 and 12 during the reaction of 2-alkylimidacillin and monohalogenated acetate, During the reaction, by maintaining the pH of the reaction solution near the above-mentioned adjusted value, the tertiary amide type compound (I
) has been reported to be selectively obtained.
しかしながら、本発明者らがこの発明を追試し、その生
成物について高速液体クロマトグラフィー（以下、）Ｉ
ＰＬＣと略称する）を用いて詳細に組成分析を行った結
果、生成物は３級アミド型化合物（４）と２級アミド型
化合物（ＩＩ）の混合物であり、しかもその比率はＨＰ
ＬＣの面積比で５０１５０程度であった。さらにこの方
法は、反応中反応液のｐＨを一定の範囲にコントロール
する必要があり、工業的に実施するには操作が煩雑であ
った。However, the present inventors tried this invention again, and the product was subjected to high performance liquid chromatography (hereinafter referred to as I).
As a result of detailed composition analysis using PLC (abbreviated as PLC), the product was a mixture of tertiary amide type compound (4) and secondary amide type compound (II), and the ratio was as high as HP
The LC area ratio was about 50,150. Furthermore, in this method, it is necessary to control the pH of the reaction solution during the reaction within a certain range, and the operation is complicated for industrial implementation.
従って、界面活性剤として有用な３級アミド型化合物（
Ｉ）を、工業的に適用できる簡便な操作で選択的に製造
する方法の開発が望まれていた。Therefore, tertiary amide type compounds (
It has been desired to develop a method for selectively producing I) by a simple operation that is industrially applicable.
かかる現状において、本発明者らは鋭意研究した結果、
イミダシリンとモノハロゲン化酢酸との反応を、特定の
無機塩の存在下に行えば、選択的に３級アミド型化合物
が得られることを見出し、本発明を完成するに至った。Under such current circumstances, as a result of intensive research by the present inventors,
The present inventors have discovered that a tertiary amide type compound can be selectively obtained by reacting imidacillin with monohalogenated acetic acid in the presence of a specific inorganic salt, and have completed the present invention.
本発明は次の反応式で示される。The present invention is shown by the following reaction formula.
Ｃ２Ｈ，０）Ｉ
（Ｉ［［） （ＩＶ）（Ｉ）
〔式中、Ｘはハロゲン原子を示し、Ｚはアルカリ金属原
子を示し、Ｒ及びＭは前記と同じ意味を有する〕
すなわち、本発明は式２Ｈ３Ｄ３、Ｚ２Ｓ２Ｏ，又はＺ
ＰＨ２０ｉ （式中、Ｚはアルカリ金属原子を示す）で
表わされる無機塩（以下、単に「無機塩」という）の存
在下、イミダシリン（Ｉ［Ｉ）にモノハロゲン化酢酸又
はその塩を反応させることを特徴とする、アミドアミン
型化合物（１）の製造方法である。C2H,0)I (I[[) (IV)(I) [In the formula, X represents a halogen atom, Z represents an alkali metal atom, and R and M have the same meanings as above] That is, the present invention is the formula 2H3D3, Z2S2O, or Z
Reacting imidacillin (I [I) with monohalogenated acetic acid or a salt thereof in the presence of an inorganic salt (hereinafter simply referred to as "inorganic salt") represented by PH20i (wherein Z represents an alkali metal atom). This is a method for producing amidoamine type compound (1), characterized by:
原料の一つであるイミダシリン（Ｉ［Ｉ）としては、例
えば１−ヒドロキシエチル−２−ココイルイミダシリン
、１−ヒドロキシエチル−２−ウンデシルイミダシリン
、１−ヒドロキシエチル−２−ヘプタデシルイミダシリ
ン等を挙げることができる。Examples of imidacilline (I[I), which is one of the raw materials, include 1-hydroxyethyl-2-cocoyl imidacilline, 1-hydroxyethyl-2-undecylimidacilline, and 1-hydroxyethyl-2-heptadecyl. Examples include imidacillin.
また、モノハロゲン化酢酸（ＩＶ）又はその塩としては
、モノクロロ酢酸、モノブロモ酢酸又はこれらのナトリ
ウム塩、カリウム塩、アンモニウム塩、アルカノールア
ミン塩等が挙げられる。Examples of the monohalogenated acetic acid (IV) or its salt include monochloroacetic acid, monobromoacetic acid, or their sodium salts, potassium salts, ammonium salts, and alkanolamine salts.
本発明に用いられる無機塩の具体例としては、Ｎａ）Ｉ
ＳＯ，、Ｎａ２５ｚ［］ｓ 、 ＮａＰＨ２０ｚ
、 Ｋ）１３口３ 、 ＬＳｚＯｓ、ＫＰ）＋２０２
等が挙げられる。これらの無機塩は単独でも、２種以上
を混合して用いてもよい。かかる無機塩の添加量は、全
仕込み量に対し３００ｐｐｍ以上、特に５００ｐｐｍ以
上が好ましい。３００ｐｐｍ未満では充分な添加効果が
得られず、一方多い場合は特に反応上問題はないがコス
ト的に不利になり好ましくない。従って、特に好ましい
添加量は５００〜５．０００ｐｐｍ程度である。これら
無機塩は、イミダシリンの開環反応時及びモノハロゲン
化酢酸とイミダシリンとの反応時の両方に存在する必要
がある。従って、無機塩は反応系に最初から添加するの
が好ましく、イミダシリンの開環反応の途中で添加して
も充分な添加効果を奏さず、反応終了後添加しても何ら
効果は期待できない。Specific examples of inorganic salts used in the present invention include Na)I
SO,, Na25z[]s, NaPH20z
, K) 13 mouths 3, LSzOs, KP) +202
etc. These inorganic salts may be used alone or in combination of two or more. The amount of the inorganic salt added is preferably 300 ppm or more, particularly 500 ppm or more based on the total amount charged. If the amount is less than 300 ppm, a sufficient addition effect cannot be obtained, while if it is more than 300 ppm, there will be no particular problem in terms of reaction, but it will be disadvantageous in terms of cost, which is not preferable. Therefore, a particularly preferable addition amount is about 500 to 5,000 ppm. These inorganic salts need to be present both during the ring-opening reaction of imidacilline and during the reaction of monohalogenated acetic acid with imidacilline. Therefore, it is preferable to add the inorganic salt to the reaction system from the beginning; adding it during the ring-opening reaction of imidacillin will not produce a sufficient effect, and adding it after the reaction has ended will not produce any effect.
なお、本発明においては、イミダシリン環の開裂反応を
促進させるたｔｌ例えば水酸化す） ＩＪウム、水酸化
カリウム、炭酸ナトリウム等のアルカリを添加するのが
好ましい。In the present invention, it is preferable to add an alkali such as hydroxide, potassium hydroxide, or sodium carbonate to promote the cleavage reaction of the imidacillin ring.
本発明方法の好ましい反応手順は例えば、次の如くであ
る。まず、イミダシリン（■）、イミダシリン環の開環
に必要な最低量のアルカリ水溶液及び無機塩を添加し昇
温する。８０〜９０℃の温度で約１時間反応した後、予
約調製したモノクロロ酢酸塩水溶液を少なくとも２モル
、好ましくは２〜３モル仕込み、５０〜１００℃、好ま
しくは６０〜８０℃で攪拌しながら反応させ、続いて反
応が完結する様に適当量のアルカリ水溶液を滴下する。A preferred reaction procedure for the method of the present invention is, for example, as follows. First, imidacillin (■), the minimum amount of alkali aqueous solution and inorganic salt necessary for ring opening of the imidacillin ring are added, and the temperature is raised. After reacting at a temperature of 80 to 90°C for about 1 hour, at least 2 mol, preferably 2 to 3 mol of the previously prepared monochloroacetate aqueous solution is charged, and the reaction is carried out at 50 to 100°C, preferably 60 to 80°C with stirring. Then, an appropriate amount of alkaline aqueous solution is added dropwise to complete the reaction.
反応温度は４０℃以下では原料のイミダシリン（ＩＩＩ
）が溶解しにくく、また両性化反応速度が遅くなる。ま
た１００℃以上では生成物の着色及び分解が激しくなる
ので好ましくない。When the reaction temperature is below 40°C, the raw material imidacilline (III
) is difficult to dissolve, and the amphoteric reaction rate is slow. Moreover, if the temperature exceeds 100°C, the coloring and decomposition of the product will become severe, which is not preferable.
なお、本反応は水のみの系でもよいが、目的に応じアル
コール等の溶媒を加えても問題ない。Note that this reaction may be carried out in a water-only system, but a solvent such as alcohol may also be added depending on the purpose.
上述の反応によれば反応液中に３級アミド型アミドアミ
ン化合物（１）が主生成物として存在するので、これを
単離することもできるが、界面活性剤として使用する場
合、反応液から化合物（Ｉ）を何ら単離することなく反
応液をそのまま洗浄剤組成物等に配合することもできる
。またアミドアミン化合物＜Ｉ）は通常、アルカリ金属
塩として生産されるが、必要に応じてアルカリ金属を水
素原子、アンモニウム基、アルカノールアミンの陽イオ
ン残基へ交換したうえで使用することもできる。According to the above reaction, the tertiary amide type amidoamine compound (1) exists as the main product in the reaction solution, so it can be isolated, but when used as a surfactant, the compound can be isolated from the reaction solution. The reaction solution can also be directly blended into a detergent composition, etc., without isolating (I) at all. Further, the amidoamine compound <I) is usually produced as an alkali metal salt, but if necessary, the alkali metal can be exchanged with a hydrogen atom, an ammonium group, or a cationic residue of an alkanolamine before use.
次に本発明を実施例を挙げて説明するが、本発明はこれ
らによって限定されるものではない。Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.
参考例
攪拌機、温度計、還流冷却器、及び圧力計を備えた１１
容４ツロフラスコにラウリン酸２００ｇ（１モル）と了
ミノエチルエタノールアミン１３５、２ｇ （１，３モ
ル、以下ＡＢ巳Ａと略記）とを仕込んだ。還流冷却器に
８０℃の温水を通しながら、上記混合物を攪拌し１４０
℃へ加熱した。その後反応圧力を１時間かけて４００ｍ
ｍＨｇに設定し２時間反応させアミド化を行った。Reference example 11 equipped with a stirrer, thermometer, reflux condenser, and pressure gauge
A 4-volume flask was charged with 200 g (1 mole) of lauric acid and 135.2 g (1.3 mole, hereinafter abbreviated as AB) of minoethylethanolamine. The above mixture was stirred while passing warm water at 80°C through a reflux condenser.
Heated to ℃. After that, the reaction pressure was increased to 400 m for 1 hour.
Amidation was carried out by setting mHg and reacting for 2 hours.
次に反応温度を２００℃、圧力を２００ｍｍ１１ｇまで
１．５時間かけて設定し、この条件で１時間熟成を行っ
た。さらに圧力を１０ｍｍＨｇまで約２時間かけて下げ
、この条件で２時間反応を行い過剰のＡＲＥＡを除去し
た。この間、生成水及び＾Ｂ［’Ａの蒸気はドライアイ
ス／メタノール冷却トラップに捕集した。Next, the reaction temperature was set to 200° C. and the pressure was set to 200 mm and 11 g over 1.5 hours, and aging was performed under these conditions for 1 hour. The pressure was further lowered to 10 mmHg over about 2 hours, and the reaction was carried out under these conditions for 2 hours to remove excess AREA. During this time, the produced water and ^B['A vapor were collected in a dry ice/methanol cooling trap.
この様にして、１−ヒドロキシエチル−２−ウンデシル
イミダシリンを得た。以下の実施例はすべてこの方法で
製造して得られたものを使用した。In this way, 1-hydroxyethyl-2-undecylimidacillin was obtained. All of the following examples used products produced by this method.
実施例１
攪拌機、冷却管、滴下漏斗、温度計を付した４ツロフラ
スコに、上記参考例で得られた１−ヒドワキシエチル−
２−ウンデシルイミダシリン２６８ｇ（１モル）、水９
０ｇ及び水酸化ナトリウム２ｇ及びＮａＨ３Ｏ５３ｇを
入れ、攪拌しながら８０℃まで加熱し、そのままの温度
で約２時間攪拌を続はイミダシリン環の開環を行った。Example 1 1-Hydowoxyethyl- obtained in the above reference example was placed in a 4-tubular flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer.
2-undecylimidacilline 268g (1 mol), water 9
0g of sodium hydroxide, 2g of sodium hydroxide, and 53g of NaH3O were added, heated to 80°C with stirring, and stirred at that temperature for about 2 hours, followed by opening of the imidacillin ring.
ここに、別に調製したモノクロロ酢酸ナトリウム２３３
ｇ（２モル）と水６６２ｇの溶液を仕込んだ。Here, separately prepared sodium monochloroacetate 233
(2 mol) and 662 g of water were charged.
次に溶液の温度を７０〜８０℃に保ちながら、４０％水
酸化ナトリウム２００ｇを約３時間かけて滴下した。Next, while maintaining the temperature of the solution at 70 to 80°C, 200 g of 40% sodium hydroxide was added dropwise over about 3 hours.
滴下終了後さらに７０〜８０℃の温度で４時間熟成を行
った。続いて加熱を停止し反応混合物を冷却した。この
様にして得られた化合物をＨＰＬＣにより詳細に分析し
た。その結果、３級アミド型であるＮ−ラウロイル−Ｎ
−（２−ヒドロキシエチル）−Ｎ’ Ｎ’ −ビス（
ナトリウムカルボキシメチル）エチレンジアミンと２級
アミド型であるＮ−ラウロイルーＮ’−（２−ヒドロキ
シエチル）−Ｎ′−ナトリウムカルボキシメチルエチレ
ンジアミンのＨＰＬＣでの面積比は９０／１０であった
。また、Ｂ型粘度計で粘度を測定（２５℃）したところ
、約５０ｃｐであった。After the dropwise addition was completed, aging was further carried out at a temperature of 70 to 80°C for 4 hours. Subsequently, heating was stopped and the reaction mixture was cooled. The compound thus obtained was analyzed in detail by HPLC. As a result, the tertiary amide type N-lauroyl-N
-(2-hydroxyethyl)-N'N' -bis(
The area ratio of sodium carboxymethyl)ethylenediamine and secondary amide type N-lauroyl N'-(2-hydroxyethyl)-N'-sodium carboxymethylethylenediamine was 90/10 by HPLC. Further, when the viscosity was measured using a B-type viscometer (25° C.), it was approximately 50 cp.
実施例２
実施例１のＮａＨ３Ｏ５の代わりにＮａ２５Ｊｓ ３
ｇを用いた。３級アミド型化合物／２級Ｔミド型化合物
の比率は９３／７であった。粘度は約４０ｃｐであった
。Example 2 Na25Js 3 instead of NaH3O5 in Example 1
g was used. The ratio of tertiary amide type compound/secondary T amide type compound was 93/7. The viscosity was approximately 40 cp.
実施例３
実施例１のＮａＨ３Ｏ５の代わりにＮａＰＩｌｚＯ２３
ｇを用いた。３級アミド型化合物７２級アミド型化合物
の比率は８５／１５であった。粘度は約６０ｃｐであっ
た。Example 3 NaPIlzO23 instead of NaH3O5 in Example 1
g was used. The ratio of the tertiary amide type compound to the 72nd class amide type compound was 85/15. The viscosity was approximately 60 cp.
比較例１
実施例１のＮａＨＳＯａを添加せずに反応を同一条件で
行った。３級アミド型化合物／２級アミド型化合物の比
率は５／９５であった。粘度は約１００．０００ｃｐで
あった。Comparative Example 1 A reaction was carried out under the same conditions as in Example 1 without adding NaHSOa. The ratio of tertiary amide type compound/secondary amide type compound was 5/95. The viscosity was approximately 100.000 cp.
比較例２
特開昭６１−１４３３４７号の方法に準じ次の如く反応
を行った。Comparative Example 2 A reaction was carried out as follows according to the method of JP-A-61-143347.
実施例１で用いた反応容器に、モノクロロ酢酸ナトリウ
ム２３３ｇ（２モル）、水６６２ｇ及び１−ヒドロキシ
エチル−２−ウンデシルイミダシリン２６８ｇ（１モル
）を仕込み、攪拌しながら温度を７０℃まで昇温し、こ
の溶液に４０％水酸化ナトリウム２００ｇを約４時間か
け温度を保持しながら、ｐＨが７〜１２に保たれる様に
滴下した。滴下終了後同じ温度で約１時間熟成を行った
。この様にして得られた化合物を分析したところ３級ア
ミド型化合物／２級アミド型化合物の）ＩＰＬｃでの面
積比率は５０１５０であった。また粘度は約５００ｃｐ
であった。233 g (2 mol) of sodium monochloroacetate, 662 g of water, and 268 g (1 mol) of 1-hydroxyethyl-2-undecylimidacillin were placed in the reaction vessel used in Example 1, and the temperature was raised to 70°C while stirring. The temperature was raised, and 200 g of 40% sodium hydroxide was added dropwise to this solution over about 4 hours while maintaining the temperature so that the pH was maintained at 7 to 12. After completion of the dropwise addition, aging was carried out at the same temperature for about 1 hour. When the compound thus obtained was analyzed, the area ratio (of tertiary amide type compound/secondary amide type compound) in IPLc was 50,150. Also, the viscosity is about 500 cp
Met.
本発明によれば、従来製造が極めて困難であった低粘度
で皮膚刺激性が弱い界面活性剤として有用な３級アミド
型のアミドアミン化合物が、簡便な操作でしかも低コス
トで選択的に製造できるようになった。According to the present invention, tertiary amide type amidoamine compounds, which are useful as surfactants with low viscosity and weak skin irritation, which have been extremely difficult to produce in the past, can be selectively produced with simple operations and at low cost. It became so.
以上that's all
Claims (1)
２Ｏ＿２（式中、Ｚはアルカリ金属原子を示す）で表わ
される無機塩の存在下、一般式（III） ▲数式、化学式、表等があります▼（III） 〔式中、Ｒは炭素数７〜２３の直鎖又は分岐鎖のアルキ
ル、アルケニル、ヒドロキシアルキル又はアラルキル基
を示す〕 で表わされるイミダゾリンに次の一般式 （IV） Ｘ−ＣＨ＿２ＣＯＯＨ（IV） 〔式中、Ｘはハロゲン原子を示す〕 で表わされるモノハロゲン化酢酸又はその塩を反応させ
ることを特徴とする、一般式 （ I ） ▲数式、化学式、表等があります▼（ I ） 〔式中、Ｒは前記と同じ意味を示し、Ｍは水素原子、ア
ルカリ金属原子、アンモニウム基又はアルカノールアミ
ンの陽イオン残基を示す〕 で表わされるアミドアミン型化合物の製造方法。[Claims] 1. Formula ZHSO_3, Z_2S_2O_5 or ZPH_
In the presence of an inorganic salt represented by 2O_2 (in the formula, Z represents an alkali metal atom), the general formula (III) ▲There are numerical formulas, chemical formulas, tables, etc.▼(III) [In the formula, R has 7 to 7 carbon atoms] 23 straight chain or branched alkyl, alkenyl, hydroxyalkyl or aralkyl group] to the imidazoline represented by the following general formula (IV) X-CH_2COOH (IV) [wherein, X represents a halogen atom] General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R has the same meaning as above, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a cationic residue of an alkanolamine.] A method for producing an amidoamine type compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11154890A JP2780126B2 (en) | 1990-04-26 | 1990-04-26 | Method for producing amidoamine type compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11154890A JP2780126B2 (en) | 1990-04-26 | 1990-04-26 | Method for producing amidoamine type compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH049361A true JPH049361A (en) | 1992-01-14 |
| JP2780126B2 JP2780126B2 (en) | 1998-07-30 |
Family
ID=14564176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11154890A Expired - Lifetime JP2780126B2 (en) | 1990-04-26 | 1990-04-26 | Method for producing amidoamine type compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2780126B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2760453A1 (en) * | 1997-02-21 | 1998-09-11 | Kao Corp | PROCESS FOR PRODUCING AMIDO GROUP (S) SURFACTANTS |
-
1990
- 1990-04-26 JP JP11154890A patent/JP2780126B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2760453A1 (en) * | 1997-02-21 | 1998-09-11 | Kao Corp | PROCESS FOR PRODUCING AMIDO GROUP (S) SURFACTANTS |
| ES2142266A1 (en) * | 1997-02-21 | 2000-04-01 | Kao Corp | Preparation of Amino-group containing surfactants |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2780126B2 (en) | 1998-07-30 |
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