JPH0489468A - Novel betaine compound, its production and surfactant containing the same - Google Patents
Novel betaine compound, its production and surfactant containing the sameInfo
- Publication number
- JPH0489468A JPH0489468A JP20096790A JP20096790A JPH0489468A JP H0489468 A JPH0489468 A JP H0489468A JP 20096790 A JP20096790 A JP 20096790A JP 20096790 A JP20096790 A JP 20096790A JP H0489468 A JPH0489468 A JP H0489468A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- group
- general formula
- represented
- 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.)
- Pending
Links
- -1 betaine compound Chemical class 0.000 title claims abstract description 32
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229960003237 betaine Drugs 0.000 title claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000005526 alkyl sulfate group Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 5
- 210000004209 hair Anatomy 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- NARVIWMVBMUEOG-UHFFFAOYSA-N 2-Hydroxy-propylene Natural products CC(O)=C NARVIWMVBMUEOG-UHFFFAOYSA-N 0.000 description 4
- 206010040880 Skin irritation Diseases 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 231100000475 skin irritation Toxicity 0.000 description 4
- 230000036556 skin irritation Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007794 irritation Effects 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 description 3
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- PIINGYXNCHTJTF-UHFFFAOYSA-N 2-(2-azaniumylethylamino)acetate Chemical compound NCCNCC(O)=O PIINGYXNCHTJTF-UHFFFAOYSA-N 0.000 description 1
- OQFSYHWITGFERZ-UHFFFAOYSA-N 2-bromoethanesulfonic acid Chemical compound OS(=O)(=O)CCBr OQFSYHWITGFERZ-UHFFFAOYSA-N 0.000 description 1
- LIFHMKCDDVTICL-UHFFFAOYSA-N 6-(chloromethyl)phenanthridine Chemical compound C1=CC=C2C(CCl)=NC3=CC=CC=C3C2=C1 LIFHMKCDDVTICL-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 102220474557 Connector enhancer of kinase suppressor of ras 1_C12S_mutation Human genes 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000004164 Wax ester Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 210000004761 scalp Anatomy 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は新規なベタイン化合物及びその製造方法に関す
るものである。更に詳細には、皮膚に対して温和な作用
を有し、しかも優れた起泡力、洗浄力を有する頭髪又は
身体洗浄用界面活性剤として有用な新規ベタイン化合物
及びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel betaine compound and a method for producing the same. More specifically, the present invention relates to a novel betaine compound useful as a surfactant for hair or body cleansing, which has a mild effect on the skin and has excellent foaming and detergent powers, and a method for producing the same.
〔従来の技術及び発明が解決しようとする課題］近年、
洗浄剤などに使用される界面活性剤は、界面活性能の他
に生分解性、安全性、眼や皮膚に対する低刺激性などの
緒特性に優れているものが要望されている。これらの要
求を満たす界面活性剤としてアシル化アミノ酸型界面活
性剤やイミダシリン型界面活性剤が広く使用されるよう
になってきた。[Problems to be solved by conventional techniques and inventions] In recent years,
Surfactants used in detergents and the like are required to have excellent surfactant properties as well as other properties such as biodegradability, safety, and low irritation to the eyes and skin. Acylated amino acid type surfactants and imidacilline type surfactants have come to be widely used as surfactants that meet these requirements.
しかしこれらの界面活性剤は一般的に、安全性等に優れ
る反面、界面活性能として特に重要である起泡力、洗浄
力が劣る為に、それ自体シャンプー等の成分として単独
で用いられることは少なく、アルキルエーテルサルフェ
ート、アルキルサルフェート等のアニオン型界面活性剤
との併用が一般的である。However, although these surfactants generally have excellent safety, they have poor foaming power and cleaning power, which are particularly important as surfactant properties, so they cannot be used alone as ingredients in shampoos, etc. Generally, it is used in combination with anionic surfactants such as alkyl ether sulfates and alkyl sulfates.
かかるアニオン型界面活性剤は皮膚に対する刺激性が強
い為に、皮膚を荒らす恐れがある。Such anionic surfactants are highly irritating to the skin and may cause skin irritation.
この為、起泡力、洗浄力に優れ、且つ、安全性の高い活
性剤の出現が強く望まれている。For this reason, there is a strong desire for an active agent that has excellent foaming power and detergency, and is highly safe.
本発明者らは上記現状に鑑み、頭髪・身体洗浄用として
洗浄力、起泡力に優れ、且つ安全性の高い界面活性剤を
得るべく鋭意検討を行った結果、本発明の目的に合致す
る新規ベタイン化合物を見出し、本発明を完成させるに
至った。In view of the above-mentioned current situation, the present inventors conducted intensive studies to obtain a surfactant that has excellent detergency and foaming power for hair and body washing, and is highly safe. We have discovered a new betaine compound and completed the present invention.
即ち本発明は、−形成（１）
〔式中、Ｒ１は直鎖又は分岐鎖の炭素数８〜２２のアル
キル基、アルケニル基又はヒドロキシアルキル基、Ｘは
Ｈ又はヒドロキシル基、Ｒ２−Ｒ４はそれぞれ炭素数１
〜４のアルキル基、Ｙは−ｃｌｈｃＨ（ＯＨ）Ｃ１２Ｓ
Ｏ３又は−（ＣＨ２）Ｚ〜５Ｓ０３を示す。ｎはＯ又は
１〜５の整数を示し、ｎ＝１の場合はＸ＝）ｌ又はヒド
ロキシル基を示し、ｎ＝ｏ、２，３，４．５の場合はＸ
＝Ｈを示す。〕で表される新規なヘタイン化合物とその
製造方法及びそれを含有する界面活性剤を提供するもの
である。That is, the present invention provides - formation (1) [wherein R1 is a linear or branched alkyl group having 8 to 22 carbon atoms, an alkenyl group or a hydroxyalkyl group, X is H or a hydroxyl group, and R2-R4 are each Carbon number 1
~4 alkyl group, Y is -clhcH(OH)C12S
Indicates O3 or -(CH2)Z~5S03. n represents O or an integer from 1 to 5; when n = 1, X = ) l or a hydroxyl group; when n = o, 2, 3, 4.5, X
= indicates H. The present invention provides a novel hetain compound represented by the following formula, a method for producing the same, and a surfactant containing the same.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
前記−形成（１）で表されるヘタイン化合物に関する報
告は従来の文献、特許等になく、かかる本発明のヘタイ
ン化合物は新規である。There is no report regarding the hetain compound represented by the above-mentioned -formation (1) in conventional literature, patents, etc., and the hetain compound of the present invention is novel.
上記−形成（１）で表される本発明のヘタイン化合物は
、次の２つの製造方法〈１〉又は〈２〉にて製造するこ
とができる。The hetain compound of the present invention represented by -formation (1) above can be produced by the following two production methods <1> or <2>.
製造方法く１〉
「アミノ化」
一般式（２）
％式％（２）
〔式中、Ｒ１は前記の意味を有する。〕で表される第一
級アルコールとアクリロニトリルを塩基性触媒の存在下
に反応させてエーテルニトリルを形成させた後、水素化
触媒の存在下に水素化を行い、−形成（３）
％式％（３）
〔式中、「は前記の意味を有する。〕
で表されるエーテルアミンを得、かかるエーテルアミン
に対して一般式（４）
％式％
〔式中、Ｚはハロゲン原子、ＡはＯＨ、ハロゲン原子又
は炭素数１〜４のアルキル硫酸基を示し、Ｘ、 Ｒ”〜
Ｒ’、 ｎは前記と同じ意味を有する。］
で表される化合物を１〜３倍モル用いて反応させて、−
形成（５）
％式％
〔式中、Ｒ’＋Ｘ、Ｒ”〜Ｒ’＋Ａ、ｎは前記と同し意
味を有する。〕
で表される化合物を生成せしめる。Production method 1>"Amination" General formula (2) % formula % (2) [In the formula, R1 has the above-mentioned meaning. ] is reacted with acrylonitrile in the presence of a basic catalyst to form ethernitrile, and then hydrogenated in the presence of a hydrogenation catalyst to form - (3) % formula % (3) [In the formula, "has the above-mentioned meaning.] To obtain an ether amine represented by the following, the general formula (4) % formula % [In the formula, Z is a halogen atom and A is OH, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms;
R' and n have the same meanings as above. ] A compound represented by is reacted using 1 to 3 times the mole, and -
Formation (5) A compound represented by the formula % [wherein R'+X, R'' to R'+A, and n have the same meanings as above] is produced.
「ベタイン化」
次いで前記−形成（５）で表される化合物と、−形成（
６）
％式％（６）
〔式中、Ｚは前記と同じ意味を有し、旧よアルカリ金属
を示す。〕
で表される３−ハロー２−ヒドロキシプロピレンスルホ
ン酸の金属塩を、前記−形成（５）で表される化合物に
対して１〜３倍モル用いて反応せしめるか、又は前記−
形成（５）で表される化合物と、−形成（７）
Ｚ（ＣＨｚ）ｚ〜ＳＳＯ，Ｍ （７）
［式中、Ｚ及び旧よ前記と同じ意味を有する。］で表さ
れるハロアルキレンスルホン酸の金属塩を、前記−形成
（５）で表される化合物に対して１〜３倍モル用いて反
応せしめることにより前記−形成（１）で表されるヘタ
イン化合物を製造することができる。"Betaination" Next, the compound represented by -formation (5) and -formation (
6) % formula % (6) [In the formula, Z has the same meaning as above and represents an alkali metal as in the former. ] The metal salt of 3-halo 2-hydroxypropylene sulfonic acid represented by is reacted in an amount of 1 to 3 times the mole of the compound represented by -formation (5), or the -
A compound represented by formation (5) and -formation (7) Z(CHz)z~SSO,M (7)
[In the formula, Z and old have the same meanings as above. ] By reacting a metal salt of haloalkylene sulfonic acid represented by 1 to 3 times the molar amount of the compound represented by -formation (5), hetaine represented by -formation (1) above can be obtained. compounds can be manufactured.
本発明の反応例を式で具体的に示せば以下の様である。A reaction example of the present invention is specifically shown below using a formula.
ＣＨ。CH.
ｅ θ
Ｒ’０ＣＨ２ＣＨ２ＣＨ２ＮＨ２＋ ＣＩＣＨ２ＣＨ
ＣＨ２−Ｎ−ＣＨ３Ｃ１（３）
０）Ｉ ＣＨｚ（４゛）
ＯＨＣＨ３
（５′）
（式中、Ｒ１は前記と同じ意味を有する。）エーテルア
ミンと前記−形成（４）で表される化合物（化合物（４
）と略記する）との反応は、通常化合物（４）の水溶液
にエーテルアミンを滴下した後に、ｐＨを８〜１２に保
つことが好ましく、その為に水酸化ナトリウム、水酸化
カリウム等のアルカリ溶液を必要に応じて反応溶液中に
仕込むことが行われる。反応時、反応系のｐＨを前記範
囲に維持するのは、エーテルアミンと化合物（４）とを
反応させる為である。それには反応速度の点でｐＨ８以
上のアルカリ側であることが好ましく、またｐＨ１２を
超えると化合物（４）の加水分解を起こすので好ましく
ない。e θ R'0CH2CH2CH2NH2+ CICH2CH
CH2-N-CH3C1 (3)
0) I CHz (4゛) OHCH3 (5') (In the formula, R1 has the same meaning as above.) Ether amine and the compound represented by the above-formation (4) (Compound (4)
) is usually carried out by dropping the ether amine into an aqueous solution of compound (4), and then keeping the pH at 8 to 12. For this purpose, an alkaline solution such as sodium hydroxide or potassium hydroxide is added to the reaction solution as necessary. The reason for maintaining the pH of the reaction system within the above range during the reaction is to allow the ether amine to react with the compound (4). For this purpose, an alkaline pH of 8 or more is preferable from the viewpoint of reaction rate, and a pH of over 12 is not preferable because it causes hydrolysis of compound (4).
反応は、常温でも進行するが、温度が高いほど反応は速
くなる。しかし、温度、ｐＨが高いと化合物（４）の加
水分解が促進される為、１００°Ｃ以下、好ましくは９
０゛Ｃ以下である。The reaction proceeds even at room temperature, but the higher the temperature, the faster the reaction. However, if the temperature and pH are high, the hydrolysis of compound (4) will be accelerated, so the temperature should be lower than 100°C, preferably 9°C.
It is below 0°C.
本発明方法において、化合物（４）とエーテルアミンと
のモル比は、通常１／１〜３／１であり、好ましくは１
．１／１〜１．５／１である。この範囲より化合物（４
）が少ない場合は反応率が低下し、この範囲より化合物
（４）が多い場合には化合物（４）又は化合物（４）の
加水分解物が反応混合物中に多（残存するので好ましく
ない。In the method of the present invention, the molar ratio of compound (4) and ether amine is usually 1/1 to 3/1, preferably 1/1 to 3/1.
．． It is 1/1 to 1.5/1. From this range, the compound (4
) If the amount of compound (4) is less than this range, the reaction rate will decrease, and if the amount of compound (4) is more than this range, a large amount of compound (4) or a hydrolyzate of compound (4) will remain in the reaction mixture, which is not preferable.
エーテルアミンと化合物（４）との反応終点は、反応液
中のエーテルアミン残量を高速液体クロマトグラフィー
を用いて分析することにより確認することができるので
、反応が終了したならば、続いて予め調整しておいた一
般式（６）又は（７）で示される化合物（以下化合物（
６） 、 （７）と略記する）の水溶液を滴下してベタ
イン化を行う。その後、前述のアルカリ水溶液をｐＨ８
〜１２、好ましくはｐＨ９〜１１になるように仕込み、
その間、温度は５０〜１００″Ｃ１好ましくは７０〜９
０°Ｃに保つ。温度が５０°Ｃ以下ではヘタイン化の速
度が遅く、又１００°Ｃ以上では化合物（６）又は（７
）の加水分解が促進される。The end point of the reaction between ether amine and compound (4) can be confirmed by analyzing the remaining amount of ether amine in the reaction solution using high performance liquid chromatography. The prepared compound represented by general formula (6) or (7) (hereinafter referred to as compound (
6), (abbreviated as (7)) is added dropwise to convert into betaine. Then, add the above alkaline aqueous solution to pH 8.
~ 12, preferably pH 9 ~ 11,
Meanwhile, the temperature is 50~100''C1 preferably 70~9
Keep at 0°C. When the temperature is below 50°C, the rate of hetainization is slow, and when the temperature is above 100°C, compound (6) or (7)
) hydrolysis is promoted.
本発明方法において化合物（６）又は（７）と前記ベタ
イン化合物前駆体である一般式（５）で示される化合物
（以下化合物（５）と略記する）とのモル比は、通常１
／１〜３／１であり、好ましくは１．１／１〜１．５／
１である。この範囲より化合物（６）又は（７）が少な
い場合は反応率が低下し、この範囲より化合物（６）又
は（７）が多い場合は化合物（６）又は（７）、あるい
は化合物（６）又は（７）の加水分解物が反応混合物中
に多く残存するので好ましくない。In the method of the present invention, the molar ratio between compound (6) or (7) and the compound represented by general formula (5) (hereinafter abbreviated as compound (5)), which is the betaine compound precursor, is usually 1.
/1 to 3/1, preferably 1.1/1 to 1.5/
It is 1. When the amount of compound (6) or (7) is less than this range, the reaction rate decreases, and when the amount of compound (6) or (7) is more than this range, compound (6) or (7) or compound (6) Otherwise, a large amount of the hydrolyzate of (7) remains in the reaction mixture, which is not preferable.
本発明方法におけるアミノ化の反応時間は、適用された
温度、ｐ）ｌによって異なるが、一般的にはｌ乃至１２
時間を要する。また後段のベタイン化の反応時間も同様
に適用された温度、ｐＨによって異なるが、一般的には
１乃至１２時間を要する。The reaction time for amination in the process of the invention varies depending on the applied temperature, p)l, but is generally between l and 12
It takes time. Further, the reaction time for betaination in the latter stage also varies depending on the applied temperature and pH, but generally takes 1 to 12 hours.
本発明方法における反応溶液は、水溶液、又は水溶液と
エタノール、イソプロビルアルコ−ル等の低級アルコー
ルや、１，３−プロパンジオール、プロピレングリコー
ル等のジオール類との混合溶液の何れでも差し支えない
。The reaction solution in the method of the present invention may be either an aqueous solution or a mixed solution of an aqueous solution and a lower alcohol such as ethanol or isopropyl alcohol, or a diol such as 1,3-propanediol or propylene glycol.
製造方法〈２〉
「アミノ化」
前記−形成（２）で表される第一級アルコールとアクリ
ロニトリルを塩基性触媒の存在下に反応させてエーテル
ニトリルを形成させた後、水素化触媒の存在下に水素化
を行い、前記−形成（３）で表されるエーテルアミンを
得、かかるエーテルアミンと、−形成（８）〔式中、Ｒ
２〜Ｒ’、Ａは前記の意味を有する。〕で表されるグリ
シジルトリアルキルアンモニウム塩とを反応させて、−
ｉ式（９）
％式％（９）
〔式中、Ｒ１，ＲＺ〜Ｒ’、Ａは前記の意味を有する。Production method <2>"Amination" After reacting the primary alcohol represented by -formation (2) above with acrylonitrile in the presence of a basic catalyst to form ethernitrile, in the presence of a hydrogenation catalyst is hydrogenated to obtain an ether amine represented by the above -formation (3), and this ether amine and -formation (8) [wherein R
2-R', A have the above meanings. ] by reacting with a glycidyl trialkylammonium salt represented by -
i Formula (9) % Formula % (9) [In the formula, R1, RZ to R', and A have the above-mentioned meanings.
〕で示される化合物を得る。] is obtained.
次いで、上記製造方法〈１〉で記載したのと同一条件で
ヘタイン化を行い、−形成（１０）〔式中、Ｒ’、 Ｒ
２〜Ｒ’、Ｙは前記の意味を有する。〕で表されるヘタ
イン化合物を得る。Next, hetainization was carried out under the same conditions as described in the above production method <1> to form -formation (10) [wherein R', R
2-R', Y have the above meanings. ] is obtained.
本製造方法を式で具体的に示せば以下の様である。This manufacturing method can be concretely expressed by the following formula.
Ｒ”ＯＨ＋ ＣＨｚ ＝ ＣＨＣＮ−→Ｒ０ＣＨｚＣｔ
ｈＣＮＨ０
−ｎ Ｒ’ＯＣＨ，ＣＨ２ＣＨ２ＮＨ’２ｚ
（８゛）
ＯＨＣＨ３
（５“）
０■
ＣＨ
（１゛）
（式中、Ｒ１は前記と同じ意味を有する）−形成（８）
で示されるグリシジルトリアルキルアンモニウム塩（以
下化合物（８）と略記する）とエーテルアミンとの反応
において、化合物（８）とエーテルアミンとのモル比は
１／１〜３／１である。モル比がこの範囲を下廻る場合
は反応率が低下し、又モル比がこの範囲を超える場合に
は反応混合物中に化合物（８）又は化合物（８）の加水
分解物が多く残存するので好ましくない。又反応温度は
３０〜１２０°Ｃ１好ましくは５０〜９０°Ｃである。R”OH+ CHz = CHCN-→R0CHzCt
hCNH0 -n R'OCH, CH2CH2NH'2z (8゛) OHCH3 (5") 0■ CH (1゛) (wherein R1 has the same meaning as above) - Formation (8)
In the reaction of the glycidyl trialkylammonium salt represented by (hereinafter abbreviated as compound (8)) and ether amine, the molar ratio of compound (8) to ether amine is 1/1 to 3/1. When the molar ratio is below this range, the reaction rate decreases, and when the molar ratio exceeds this range, a large amount of compound (8) or a hydrolyzate of compound (8) remains in the reaction mixture, which is preferable. do not have. The reaction temperature is 30 to 120°C, preferably 50 to 90°C.
反応温度がこの範囲を下廻る場合は反応速度が遅く、こ
の範囲を超える場合には着色等が起こるので好ましくな
い。エーテルアミンと化合物（８）との反応は、反応性
を確保し、一定の反応を進行させる為には、適当量のア
ルカリ水溶液を仕込みｐＨを８〜１２に維持することが
好ましい。ｐｌ＋がこの範囲未満の場合は反応速度が遅
くなり、この範囲を超える場合は副生成物が多く生成し
収率が低下する。When the reaction temperature is below this range, the reaction rate is slow, and when it exceeds this range, coloring etc. occur, which is not preferable. In the reaction between the ether amine and the compound (8), in order to ensure reactivity and allow the reaction to proceed to a certain level, it is preferable to prepare an appropriate amount of aqueous alkaline solution and maintain the pH at 8 to 12. If pl+ is less than this range, the reaction rate will be slow, and if it exceeds this range, many by-products will be produced and the yield will be reduced.
又本製造方法く２〉においてベタイン化の条件は製造方
法く１〉に記載した通りである。In addition, in the present production method 2>, the conditions for betaineization are as described in the production method 1>.
本発明の反応はすべて空気中で行っても良いし、不活性
ガス雰囲気中で行っても良いが、着色等の点で不活性ガ
ス雰囲気下が好ましい。All reactions of the present invention may be carried out in air or in an inert gas atmosphere, but an inert gas atmosphere is preferable from the viewpoint of coloring and the like.
本発明に用いられる前記−形成（２）で表される脂肪族
第一級アルコールとしては、例えばオクチルアルコール
、デシルアルコール、ドデシルアルコール、テトラデシ
ルアルコール、ヘキサデシルアルコール、オレイルアル
コール、ベヘニルアルコール、イソステアリルアルコー
ル、ヤシ脂肪族アルコール等を挙げることが出来る。Examples of the aliphatic primary alcohol represented by the above-mentioned formula (2) used in the present invention include octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, oleyl alcohol, behenyl alcohol, and isostearyl alcohol. , coconut aliphatic alcohol, and the like.
本発明方法によって取得された前記−形成（１）で表さ
れるベタイン化合物は界面活性を有し、かかる化合物を
主成分とした界面活性剤は起泡力、洗浄力に優れ、且つ
低刺激性である為に頭髪洗浄用基剤としてのみでなく、
身体洗浄用基剤としても供することができる。The betaine compound represented by -formation (1) obtained by the method of the present invention has surface activity, and a surfactant containing such a compound as a main component has excellent foaming power and detergency, and is low irritation. Because of this, it can be used not only as a base for hair washing, but also as a hair washing base.
It can also be used as a base for body cleansing.
〔実施例］
次に、本発明を実施例に基づいて詳細に説明するが、本
発明の範囲はこれらによって限定されるものではない。[Example] Next, the present invention will be described in detail based on Examples, but the scope of the present invention is not limited by these.
実施例１
アミノ 入 （５）のム
撹拌機、冷却管、温度計、滴下ロートを備えた１１容−
４ツロフラスコに、ドデシルアルコール（１１８６）
１８６ｇと水酸化カリウム（１５６，１）３．４ｇを仕
込んだ。その後、上記混合物を攪拌しながら１００°Ｃ
へ加熱し、この温度を保持しながら反応系を減圧（３０
ｍｍＨｇ）にし、水酸化カリウムが溶解するのを確認し
た後に温度を６０゛Ｃまで低下させ、窒素にて常圧に戻
した。次にアクリロニトリル（ＭＷ ５３．１）５３ｇ
を６０°Ｃ近傍に温度を保持しながら約１時間かけて滴
下した後、１時間熟成を行った。後に上記反応物を取り
出し、全量を１１のオートクレーブに、１０％カセイソ
ーダ水溶液５ｇ、ラネーＮｉ触媒１．５ｇと共に仕込ん
だ。その後、水素を導入し、圧力を２５ａ ｔｍに維持
する様に圧力弁を調整し、攪拌しながら温度を１３０°
Ｃへ加熱し、この温度を保持しながら３時間反応を行い
冷却した。次に反応混合物を濾過した後に蒸留を行い、
Ｎ−（３−ドブシロキシプロピル）アミン２００ｇを得
た。Example 1 An 11-volume container equipped with an amino stirrer, a cooling tube, a thermometer, and a dropping funnel (5).
4 Dodecyl alcohol (1186) in a flask
186 g and 3.4 g of potassium hydroxide (156,1) were charged. Thereafter, the above mixture was heated to 100°C while stirring.
While maintaining this temperature, reduce the pressure of the reaction system (30
mmHg), and after confirming that potassium hydroxide had dissolved, the temperature was lowered to 60°C, and the pressure was returned to normal pressure with nitrogen. Next, 53g of acrylonitrile (MW 53.1)
was added dropwise over about 1 hour while maintaining the temperature at around 60°C, and then aged for 1 hour. Afterwards, the reaction product was taken out and the entire amount was charged into a No. 11 autoclave together with 5 g of a 10% caustic soda aqueous solution and 1.5 g of Raney Ni catalyst. After that, hydrogen was introduced, the pressure valve was adjusted to maintain the pressure at 25 atm, and the temperature was increased to 130° while stirring.
The reaction mixture was heated to C.C., and the reaction was carried out for 3 hours while maintaining this temperature, and then cooled. The reaction mixture is then filtered and then distilled.
200 g of N-(3-dobusyloxypropyl)amine was obtained.
得られたＮ−（３−ドブシロキシプロピル）アミン２０
０ｇ（０，８２モル）を撹拌機、冷却管、滴下ロートを
備えた１１容−４ツロフラスコに、イオン交換水２００
ｇ、エタノール１００ ｇと共に仕込んだ。その後、
上記混合物を攪拌しなから７５°Ｃへ加熱した。次に、
上記温度を保持しながら、ｐＨ電極を液中に挿入し、４
０％水酸化ナトリウム水溶液を滴下しｐＨを１０とした
。次に、３クロロ−２−ヒドロキシプロピルトリメチル
アンモニウムクロライド（ＭＷ １８８）の５０％水溶
液３０９ｇを２時間で滴下した。この間、ｐＨ１０を維
持する為、４０％水酸化ナトリウムを適宜滴下した。Obtained N-(3-dobusyloxypropyl)amine 20
0 g (0.82 mol) was added to an 11-volume -4 tube flask equipped with a stirrer, cooling tube, and dropping funnel, and 200 g (0.82 mol) of ion-exchanged water was added.
g and 100 g of ethanol. after that,
The mixture was heated to 75°C without stirring. next,
While maintaining the above temperature, insert the pH electrode into the liquid and
A 0% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 10. Next, 309 g of a 50% aqueous solution of 3chloro-2-hydroxypropyltrimethylammonium chloride (MW 188) was added dropwise over 2 hours. During this time, 40% sodium hydroxide was appropriately added dropwise to maintain the pH at 10.
３−クロロ−２−ヒドロキシプロピルトリメチルアンモ
ニウムクロライドの滴下が終了した後、ｐＨ１ｏを維持
しながら加温と攪拌を継続し、１時間毎に高速液体クロ
マトグラフィーにてＮ−（３ドデシロキシブロピル）ア
ミンの残量を確認した。After the dropwise addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, heating and stirring were continued while maintaining pH 1o, and N-(3dodecyloxypropyl ) The remaining amount of amine was confirmed.
３−クロロ−２−ヒドロキシプロピルトリメチルアンモ
ニウムクロライドの滴下が終了した６時間後にＮ−（３
−ドブシロキシプロピル）アミンの系内濃度が１％にな
り、次の工程であるベタイン化へ進んだ。Six hours after the dropwise addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, N-(3
When the concentration of amine (-dobusyloxypropyl) in the system reached 1%, the process proceeded to the next step, betaination.
ベタイン 入 （１）の入
次に、上記混合物を８０°Ｃへ加温した後、予め調整し
ておいた３−クロロ−２−ヒドロキシプロピレンスルホ
ン酸ソーダ（ＭＷ １９６．５）の３０％水溶液５３７
ｇを２時間で滴下した。この間、ｐＨ１０を維持する為
、４０％アルカリ水溶液を適宜滴下した。ｐＨ１０を維
持し、加温、攪拌を継続しながら、高速液体クロマトグ
ラフィーにてベタイン前駆体化合物（５）の系内濃度が
１％になるまで反応を行った後、反応を終了した。Betaine Addition (1) Next, after heating the above mixture to 80°C, 537 ml of a 30% aqueous solution of sodium 3-chloro-2-hydroxypropylenesulfonate (MW 196.5) prepared in advance was added.
g was added dropwise over 2 hours. During this time, a 40% alkaline aqueous solution was appropriately added dropwise to maintain the pH at 10. While maintaining pH 10 and continuing heating and stirring, the reaction was carried out by high performance liquid chromatography until the concentration of betaine precursor compound (5) in the system reached 1%, and then the reaction was terminated.
この反応液を電気透析装置を用いて精製した後、一部を
蒸発乾固し、ＩＲ分析、質量分析により前記−形成（１
）の化合物、Ｎ−（３−Ｆデシロキシプロピル）−Ｎ−
（３−）サメチルアンモニオ−２−ヒドロキシプロピル
）アミノ２−ヒドロキシプロピレンスルホネート（下記
構造式を有する）が得られた。After this reaction solution was purified using an electrodialyzer, a portion was evaporated to dryness, and the -formation (1
) compound, N-(3-F decyloxypropyl)-N-
(3-)Samethylammonio-2-hydroxypropyl)amino 2-hydroxypropylene sulfonate (having the following structural formula) was obtained.
ＯＨＣ１（３
Ｃ＋ ２Ｈ２５０（ＣＨ２） ３−Ｎ−ＣＨ２ＣＨＣＨ
２−Ｎ−ＣＨ３＜ＩＲ分析〉
１２００ｃｍ−’ （８，３３μ）においてスルホン酸
イオン特有の強い吸収が認められた。OHC1(3 C+ 2H250(CH2) 3-N-CH2CHCH
2-N-CH3 <IR analysis> Strong absorption peculiar to sulfonic acid ions was observed at 1200 cm-' (8,33μ).
〈質量分析〉
装 置；日本電子昧製 ５Ｘ−１０２型質量分析型
測定条件；導入方法 直接
：イオン化法 Ｆ Ａ Ｂ （Ｆａｓｔ ＡｔｏｍＢｏ
ｍｂｅｒｄｍｅｎｔ）
分析結果；フラグメント
イオンの分子量
主要ピーク３本が認められ、４９７は団＋１）の親イオ
ンピークであり、上記構造のベタイン化合物であること
を確認した。<Mass spectrometry> Equipment: 5X-102 mass spectrometry type manufactured by JEOL Ltd. Measurement conditions: Introduction method Direct: Ionization method F A B (Fast AtomBo
mberdment) Analysis results: Three main molecular weight peaks of fragment ions were observed, and 497 was the parent ion peak of group +1), confirming that it was a betaine compound with the above structure.
実施例２
原料アルコールとしてドデシルアルコールの代わりにテ
トラデシルアルコールを用いる以外は実施例１と同様に
行い、取得された化合物は下記の構造を有するものであ
ることを実施例１と同様の方法で確認した。Example 2 The same procedure as in Example 1 was carried out except that tetradecyl alcohol was used instead of dodecyl alcohol as the raw material alcohol, and it was confirmed in the same manner as in Example 1 that the obtained compound had the following structure. did.
ＯＨＣＨ：Ｉ
Ｃｌ４Ｈ２９０（ＣＨ２）３−Ｎ−ＣＨ２ＣＨＣＨ２−
Ｎ−ＣＨ３ＨｚＣＨ３
ＩＯ−ＣＨ−ＣＨ２ＳＯ３゜
実施例３
ベタイン化の原料として、３−クロロ−２−ヒドロキシ
プロピレンスルホン酸ソーダの代ｔ）りに２−ブロモエ
タンスルホン酸ソータヲ用いる以外は実施例１と同様の
条件で行った。取得された化合物は下記の構造を有する
ものであることを確認した。OHCH:I Cl4H290(CH2)3-N-CH2CHCH2-
N-CH3HzCH3 IO-CH-CH2SO3゜Example 3 Same as Example 1 except that 2-bromoethanesulfonic acid sorta was used instead of 3-chloro-2-hydroxypropylenesulfonic acid sodium t) as the raw material for betaination. It was conducted under the following conditions. It was confirmed that the obtained compound had the following structure.
ＯＨＣＨ３
ＣＩ ２ＨｚｓＯ（ＣＨｚ）ｚ−Ｎ−ＣＨｚＣＨＣＨｚ
−Ｎ−ＣＩ（３ＣＨ，ＣＨ３
ＣＨ２−５Ｏ，。OHCH3 CI 2HzsO(CHz)z-N-CHzCHCHz
-N-CI(3CH, CH3 CH2-5O,.
Ｉ Ｒ３、′
＜ＩＲ分析〉
１２００ｃｍ−’ （８，３３ｕ ）においてスルホン
酸イオン特有の強い吸収が認められた。IR3,'<IRanalysis> Strong absorption peculiar to sulfonic acid ions was observed at 1200 cm-' (8,33u).
く質量分析〉 実施例１と同様の条件で行った。Mass spectrometry It was carried out under the same conditions as in Example 1.
親イオンピークである４６７（Ｍ＋１）が認められ、上
記構造のベタイン化合物であることを確認した。A parent ion peak of 467 (M+1) was observed, confirming that it was a betaine compound with the above structure.
試験例
実施例１〜３で得られた本発明のヘタイン化合物、及び
対照化合物として、従来皮膚に対して極めて温和である
ことが知られている化合物（下記対照化合物１及び２）
と、従来起泡力が優れていることが知られている化合物
（下記対照化合物３）について、皮膚刺激性、起泡力、
洗浄力を下記方法により試験した。Test Examples The hetain compounds of the present invention obtained in Examples 1 to 3, and as control compounds, compounds conventionally known to be extremely mild to the skin (control compounds 1 and 2 below)
The skin irritation, foaming power,
The detergency was tested by the following method.
その結果を第１表に示す。The results are shown in Table 1.
〈対照化合物〉
対照化合物１：
用研■製ソフタゾリンＣＨ（Ｎ−ココイル−Ｎ゛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）
対照化合物２：
用研■製アラノンＡＬＥ （Ｎ−ラウロイル−Ｎメチル
−β−アラニンナトリウム）
対照化合物３：
花王■製エマールＴＤ （ラウリル硫酸トリエタノール
アミン）
〈試験方法〉
・皮膚刺激性の試験方法
皮膚刺激性の試験方法としては、ヒトに対する２４時間
閉鎖貼付試験を行った。即ち、２０人の被検者に界面活
性剤を有効分として０．２％の水溶液０．１１ＩＩＩｌ
をしみ込ませたパッチテスト用絆創膏を２４時間貼付し
、貼付除去後２４時間後に刺激性を判定した。判定結果
ははっきりした紅斑を示したものを陽性とし、その陽性
率で示した。<Control compounds> Control compound 1: Softazoline CH (N-cocoyl-N'hydroxyethyl N'-sodium carboxymethylethylenediamine) manufactured by Yoken ■ Control compound 2: Alanone ALE (N-lauroyl-N methyl-β manufactured by Yoken ■) - Sodium alanine) Control compound 3: Emar TD manufactured by Kao ■ (triethanolamine lauryl sulfate) <Test method> - Test method for skin irritation As a test method for skin irritation, a 24-hour closed patch test was conducted on humans. . That is, 0.11III1 of a 0.2% aqueous solution containing a surfactant as an active ingredient was administered to 20 subjects.
A patch test bandage impregnated with was applied for 24 hours, and irritation was determined 24 hours after removal. The test result was determined to be positive if it showed clear erythema, and was expressed as a positive rate.
・起泡力
界面活性剤有効分として最終濃度０．２％となるよう４
°Ｄ）ｌ硬水で希釈し、反転攪拌法により測定した。測
定はラノリン０．３％添加、４０°Ｃで行い、結果は泡
量（−）で示した。・Foaming power Surfactant active ingredient so that the final concentration is 0.2%4
°D) l Diluted with hard water and measured by inversion stirring method. The measurement was carried out at 40°C with the addition of 0.3% lanolin, and the results were expressed as foam volume (-).
・洗浄力試験
５ｃｍＸ５ｃｎ＋のウールモスリン布にカーボンブラッ
ク２％を含む頭皮脂とほぼ同組成の汚しくハラフィン１
２％、ワックスエステル２１％、トリグリセリド２６％
、高級脂肪酸３２％、コレステロール５％、モノグリセ
リド２％）ヲ均一に塗布し、乾燥させる。この汚染布を
活性剤有効分０．６％、ｐｕ ７．０．４°ＤＨの洗浄
剤液５００−が入った約１０００ｄのステンレス製シリ
ンダー中に入れ、４０°Ｃの恒温槽中で６分間振盪し、
汚染布を流水中でよくすすぎ、乾燥させた後に反射率を
測定する。次式によって洗浄率を求める。・Cleaning power test 5cm x 5cn+ wool muslin cloth containing 2% carbon black and Dirty Halafin 1, which has almost the same composition as scalp oil.
2%, wax esters 21%, triglycerides 26%
, higher fatty acids 32%, cholesterol 5%, and monoglycerides 2%) were applied uniformly and dried. This contaminated cloth was placed in a stainless steel cylinder of approximately 1000 d containing 500 mm of detergent solution with active agent active content of 0.6% and PU of 7.0.4° DH, and placed in a constant temperature bath at 40° C. for 6 minutes. Shake;
Rinse the contaminated cloth thoroughly under running water and measure the reflectance after drying. Determine the cleaning rate using the following formula.
洗浄率（％） 第 １ 表Cleaning rate (%) Chapter 1 Table
Claims (1)
ルキル基、アルケニル基又はヒドロキシアルキル基、Ｘ
はＨ又はヒドロキシル基、Ｒ＾２〜Ｒ＾４はそれぞれ炭
素数１〜４のアルキル基、Ｙは−ＣＨ＿２ＣＨ（ＯＨ）
ＣＨ＿２ＳＯ＿３又は−（ＣＨ＿２）＿２＿〜＿５ＳＯ
＿３を示す。ｎは０又は１〜５の整数を示し、ｎ＝１の
場合はＸ＝Ｈ又はヒドロキシル基を示し、ｎ＝０、２、
３、４、５の場合はＸ＝Ｈを示す。〕で表されるベタイ
ン化合物。 ２、一般式（２） Ｒ＾１ＯＨ（２） 〔式中、Ｒ＾１は直鎖又は分岐鎖の炭素数８〜２２のア
ルキル基、アルケニル基又はヒドロキシアルキル基を示
す。〕 で表される脂肪族第一級アルコールとアクリロニトリル
を反応させた後に水素化を行い、一般式（３） Ｒ＾１ＯＣＨ＿２ＣＨ＿２ＣＨ＿２ＮＨ＿２（３）〔式
中、Ｒ＾１は前記と同様の意味を示す。〕で表されるエ
ーテルアミンを生成せしめ、次いでこのエーテルアミン
と、一般式（４） ▲数式、化学式、表等があります▼（４） 〔式中、Ｚはハロゲン原子、ＸはＨ又はヒドロキシル基
、Ｒ＾２〜Ｒ＾４はそれぞれ炭素数１〜４のアルキル基
、ＡはＯＨ、ハロゲン原子又は炭素数１〜４のアルキル
硫酸基を示す。ｎは０又は１〜５の整数を示し、ｎ＝１
の場合はＸ＝Ｈ又はヒドロキシル基を示し、ｎ＝０、２
、３、４、５の場合はＸ＝Ｈを示す。〕 で表される化合物とを反応させて、一般式（５）▲数式
、化学式、表等があります▼（５） 〔式中、Ｒ＾１、Ｘ、Ｒ＾２〜Ｒ＾４、Ａ、ｎは前記と
同じ意味を有する。〕 で示される化合物を生成せしめ、次いでこの化合物と一
般式（６） ＺＣＨ＿２ＣＨ（ＯＨ）ＣＨ＿２ＳＯ＿３Ｍ（６）〔式
中、Ｚは前記と同じ意味を有し、Ｍはアルカリ金属を示
す。〕 で表される３−ハロ−２−ヒドロキシプロピレンスルホ
ン酸の金属塩を反応せしめるか、又は一般式（７） Ｚ（ＣＨ＿２）＿２＿〜＿５ＳＯ＿３Ｍ（７）〔式中、
Ｚ及びＭは前記と同じ意味を有する。〕で表されるハロ
アルキレンスルホン酸の金属塩を反応せしめることを特
徴とする請求項１記載のベタイン化合物の製造方法。 ３、一般式（２） Ｒ＾１ＯＨ（２） 〔式中、Ｒ＾１は直鎖又は分岐鎖の炭素数８〜２２のア
ルキル基、アルケニル基又はヒドロキシアルキル基を示
す。〕 で表される脂肪族第一級アルコールとアクリロニトリル
を反応させた後に水素化を行い、一般式（３） Ｒ＾１ＯＣＨ＿２ＣＨ＿２ＣＨ＿２ＮＨ＿２（３）（式
中、Ｒ＾１は前記と同様の意味を示す。〕で表されるエ
ーテルアミンを生成せしめ、次いでこのエーテルアミン
と、一般式（８） ▲数式、化学式、表等があります▼（８） 〔式中、Ｒ＾２〜Ｒ＾４はそれぞれ炭素数１〜４のアル
キル基、ＡはＯＨ、ハロゲン原子又は炭素数１〜４のア
ルキル硫酸基を示す。〕 で表されるグリシジルトリアルキルアンモニウム塩とを
反応させて、一般式（９） ▲数式、化学式、表等があります▼（９） 〔式中、Ｒ＾１、Ｒ＾２〜Ｒ＾４、Ａは前記と同様の意
味を有する。〕 で示される化合物を生成せしめ、次いでこの化合物と、
一般式（６） ＺＣＨ＿２ＣＨ（ＯＨ）ＣＨ＿２ＳＯ＿３Ｍ（６）〔式
中、Ｚはハロゲン原子、Ｍはアルカリ金属を示す。〕 で表される３−ハロ−２−ヒドロキシプロピレンスルホ
ン酸の金属塩を反応せしめるか、又は一般式（７） Ｚ（ＣＨ＿２）＿２＿〜＿５ＳＯ＿３Ｍ（７）〔式中、
Ｚ及びＭは前記と同じ意味を有する。〕で表されるハロ
アルキレンスルホン酸の金属塩を反応せしめることを特
徴とする一般式（１０）▲数式、化学式、表等がありま
す▼（１０） 〔式中、Ｒ＾１、Ｒ＾２、Ｒ＾３、Ｒ＾４は前記と同じ
意味を有し、Ｙは−ＣＨ＿２ＣＨ（ＯＨ）ＣＨ＿２ＳＯ
＿３又は−（ＣＨ＿２）＿２＿〜＿５ＳＯ＿３を示す。 〕 で表されるベタイン化合物の製造方法。 ４、請求項１記載のベタイン化合物を含有する界面活性
剤。[Claims] 1. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 is a linear or branched alkyl group having 8 to 22 carbon atoms, alkenyl group or hydroxyalkyl group,
is H or a hydroxyl group, R^2 to R^4 are each an alkyl group having 1 to 4 carbon atoms, and Y is -CH_2CH(OH)
CH_2SO_3 or -(CH_2)_2_~_5SO
_3 is shown. n represents 0 or an integer of 1 to 5; when n = 1, X = H or a hydroxyl group; n = 0, 2,
3, 4, and 5 indicate X=H. ] A betaine compound represented by 2. General Formula (2) R^1OH (2) [In the formula, R^1 represents a linear or branched C8-C22 alkyl group, alkenyl group, or hydroxyalkyl group. ] After reacting the aliphatic primary alcohol represented by the following with acrylonitrile, hydrogenation is performed to obtain the general formula (3) R^1OCH_2CH_2CH_2NH_2 (3) [wherein R^1 has the same meaning as above. [In the formula, Z is a halogen atom, and X is a H or hydroxyl group]. , R^2 to R^4 each represent an alkyl group having 1 to 4 carbon atoms, and A represents OH, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms. n represents 0 or an integer from 1 to 5, n=1
In the case of X=H or a hydroxyl group, n=0, 2
, 3, 4, and 5 indicate X=H. ] By reacting with a compound represented by the general formula (5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (5) n has the same meaning as above. ] This compound is then combined with the general formula (6) ZCH_2CH(OH)CH_2SO_3M(6) [wherein Z has the same meaning as above and M represents an alkali metal. [In the formula,
Z and M have the same meanings as above. 2. The method for producing a betaine compound according to claim 1, wherein a metal salt of a haloalkylene sulfonic acid represented by the following formula is reacted. 3. General Formula (2) R^1OH (2) [In the formula, R^1 represents a linear or branched C8-C22 alkyl group, alkenyl group, or hydroxyalkyl group. ] After reacting the aliphatic primary alcohol represented by the following with acrylonitrile, hydrogenation is performed to obtain the general formula (3) R^1OCH_2CH_2CH_2NH_2(3) (wherein R^1 has the same meaning as above. [In the formula, R^2 to R^4 each represent the number of carbon atoms]. 1 to 4 alkyl group, A represents OH, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms.] By reacting with a glycidyl trialkylammonium salt represented by the general formula (9) ▲ Formula, There are chemical formulas, tables, etc. ▼ (9) [In the formula, R^1, R^2 to R^4, and A have the same meanings as above.] A compound represented by is produced, and then this compound and
General formula (6) ZCH_2CH(OH)CH_2SO_3M(6) [In the formula, Z represents a halogen atom and M represents an alkali metal. [In the formula,
Z and M have the same meanings as above. General formula (10) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (10) [In the formula, R^1, R^2, R^3 and R^4 have the same meanings as above, and Y is -CH_2CH(OH)CH_2SO
Indicates _3 or -(CH_2)_2_~_5SO_3. ] A method for producing a betaine compound represented by: 4. A surfactant containing the betaine compound according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20096790A JPH0489468A (en) | 1990-07-27 | 1990-07-27 | Novel betaine compound, its production and surfactant containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20096790A JPH0489468A (en) | 1990-07-27 | 1990-07-27 | Novel betaine compound, its production and surfactant containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0489468A true JPH0489468A (en) | 1992-03-23 |
Family
ID=16433297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20096790A Pending JPH0489468A (en) | 1990-07-27 | 1990-07-27 | Novel betaine compound, its production and surfactant containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0489468A (en) |
-
1990
- 1990-07-27 JP JP20096790A patent/JPH0489468A/en active Pending
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