JPH0466472B2 - - Google Patents
Info
- Publication number
- JPH0466472B2 JPH0466472B2 JP60055520A JP5552085A JPH0466472B2 JP H0466472 B2 JPH0466472 B2 JP H0466472B2 JP 60055520 A JP60055520 A JP 60055520A JP 5552085 A JP5552085 A JP 5552085A JP H0466472 B2 JPH0466472 B2 JP H0466472B2
- Authority
- JP
- Japan
- Prior art keywords
- amino acid
- acid
- dehydroabiethyl
- salt
- dehydroabietic
- 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.)
- Expired - Lifetime
Links
- 235000001014 amino acid Nutrition 0.000 claims description 30
- 150000001413 amino acids Chemical class 0.000 claims description 23
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 8
- 229960003080 taurine Drugs 0.000 claims description 7
- 150000001447 alkali salts Chemical class 0.000 claims description 5
- 235000008206 alpha-amino acids Nutrition 0.000 claims description 5
- 150000001371 alpha-amino acids Chemical class 0.000 claims description 2
- 229940024606 amino acid Drugs 0.000 description 29
- 235000002639 sodium chloride Nutrition 0.000 description 16
- QUUCYKKMFLJLFS-UHFFFAOYSA-N Dehydroabietan Natural products CC1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 QUUCYKKMFLJLFS-UHFFFAOYSA-N 0.000 description 11
- NFWKVWVWBFBAOV-UHFFFAOYSA-N Dehydroabietic acid Natural products OC(=O)C1(C)CCCC2(C)C3=CC=C(C(C)C)C=C3CCC21 NFWKVWVWBFBAOV-UHFFFAOYSA-N 0.000 description 11
- NFWKVWVWBFBAOV-MISYRCLQSA-N dehydroabietic acid Chemical compound OC(=O)[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 NFWKVWVWBFBAOV-MISYRCLQSA-N 0.000 description 11
- 229940118781 dehydroabietic acid Drugs 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- -1 alkali metal salts Chemical class 0.000 description 10
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 9
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 6
- 229960002989 glutamic acid Drugs 0.000 description 5
- 239000008233 hard water Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 4
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229960005261 aspartic acid Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QDGAVODICPCDMU-UHFFFAOYSA-N 2-amino-3-[3-[bis(2-chloroethyl)amino]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(N(CCCl)CCCl)=C1 QDGAVODICPCDMU-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- 108010077895 Sarcosine Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940043230 sarcosine Drugs 0.000 description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N serine Chemical compound OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 2
- IFGCUJZIWBUILZ-UHFFFAOYSA-N sodium 2-[[2-[[hydroxy-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyphosphoryl]amino]-4-methylpentanoyl]amino]-3-(1H-indol-3-yl)propanoic acid Chemical compound [Na+].C=1NC2=CC=CC=C2C=1CC(C(O)=O)NC(=O)C(CC(C)C)NP(O)(=O)OC1OC(C)C(O)C(O)C1O IFGCUJZIWBUILZ-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229960004295 valine Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- ZEZSZCSSTDPVDM-DKWTVANSSA-M sodium;(2s)-2-aminopropanoate Chemical compound [Na+].C[C@H](N)C([O-])=O ZEZSZCSSTDPVDM-DKWTVANSSA-M 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
産業上の利用分野
本発明は、デヒドロアビエチルアミノ酸又はそ
の塩に関するものであり、当該物質及びその製造
方法に関するものである。
本発明におけるデヒドロアビエチルアミノ酸
は、デヒドロアビエチン酸とαアミノ酸又はタウ
リンとのアミドであり、その塩は、前記αアミノ
酸又はタウリンの成分中の酸基のアルカリ塩であ
る。而してそのアルカリ塩は、界面活性剤として
使用することができ、また前記アミドは、アルカ
リ塩を得るための中間物質としての用途を有して
いる。
従来の技術
従来ロジン系の界面活性剤としては、ガムロジ
ンやトール油ロジン等のロジンのアルカリ金属塩
が知られている。
発明が解決しようとする問題点
しかしながらこれらの界面活性剤においては、
硬水に対する効果が低く、沈澱物を作つたり濁つ
たりすることがあつた。
本発明はかかる事情に鑑みなされたものであつ
て、硬水に対して溶解し易く、硬水に使用した場
合に界面活性の効果の高いロジン系の界面活性剤
として有用な、新規な物質を提供することを目的
とするものである。
問題点を解決する手段
而して本発明の物質は、一般構造式
（式中Ｘはαアミノ酸若しくはタウリン又はそれ
らのアルカリ塩の残基を表わす。）で表わされる
ものである。
本発明におけるアミノ酸残基としては、グリシ
ン、Ｄ，Ｌ−α−アラニン、Ｌ−バリン、Ｌ−フ
エニルアラニン、ザルコシン、Ｄ，Ｌ−セリン、
Ｄ，Ｌ−メチオニン、Ｌ−トリプトフアン、Ｌ−
アスパラギン酸、Ｌ−グルタミン酸等のαアミノ
酸及び、含流アミノ酸であるタウリンの残基が挙
げられる。
本発明のデヒドロアビエチルアミノ酸又はその
塩は、デヒドロアビエチン酸クロライドにアルカ
リの存在下でアミノ酸を反応させることにより、
デヒドロアビエチルアミノ酸のアルカリ塩を得る
ことができ、またそれを加水分解することによ
り、デヒドロアビエチルアミノ酸が得られる。
デヒドロアビエチン酸は、ロジンの主成分であ
るアビエチン酸を脱水素して得られるものであ
り、デヒドロアビエチン酸クロライドは、このデ
ヒドロアビエチン酸に塩化チオニルを作用させて
得られる。
作 用
本発明の方法により、アミノ酸中のカルボン酸
又はスルホン酸が反応雰囲気中のアルカリと反応
して塩を生じ、前記デヒドロアビエチン酸クロラ
イドのクロロカルボニル基に、前記アミノ酸塩に
おけるアミノ基が反応してアミド結合を生じ、デ
ヒドロアビエチルアミノ酸塩が得られる。またこ
のデヒドロアビエチルアミノ酸塩を酸で加水分解
することにより、デヒドロアビエチルアミノ酸が
得られる。
デヒドロアビエチルアミノ酸は、再度アルカリ
を作用させることにより、塩を生じる。
本発明のデヒドロアビエチルアミノ酸塩は、親
油性の骨格を有し、その一部に親水性のカルボン
酸塩又はスルホン酸塩を有しているので、良好な
界面活性剤として作用する。
発明の効果
本発明のデヒドロアビエチルアミノ酸塩は、硬
水にも良好に溶解して沈澱や濁りを生じることが
なく、良好な界面活性効果を有し、優れた気泡性
を有している。
実施例
アミノ酸として、グリシン、Ｄ，Ｌ−α−アラ
ニン、Ｌ−バリン、Ｌ−フエニルアラニン、ザル
コシン、Ｄ，Ｌ−セリン、Ｄ，Ｌ−メチオニン、
Ｌ−トリプトフアン、Ｌ−アスパラギン酸、Ｌ−
グルタミン酸及びタウリンを使用して、以下に述
べる操作によるデヒドロアビエチルアミノ酸を合
成した。
まずデヒドロアビエチン酸からデヒドロアビエ
チン酸クロライドを合成した。純度90％のデヒド
ロアビエチン酸50ｇをトルエンに溶解して、塩化
チオニル29ｇを加え、80〜85℃で撹拌しながら２
時間反応させた。反応が終了した後、溶媒及び残
余の塩化チオニルを溜去した。次いで得られた生
成物をエーテルに溶解して水洗し、さらに0.2N
−か性ソーダ水溶液で洗浄した。次いで洗液が中
性になるまで水洗し、さらに飽和食塩水で洗浄
し、無水硫酸ナトリウムで乾燥し、溶媒を溜去し
て精製デヒドロアビエチン酸クロライドを得た。
次に、このデヒドロアビエチン酸クロライドと
アミノ酸とを反応させた。水20mlとアセトン10ml
との混合溶媒中に、前記各アミノ酸（試薬特級）
0.0144モルを分散した後、6N−か性ソーダ水溶
液5.86ml（アミノ酸がＬ−グルタミン酸又はＬ−
アスパラギン酸である場合には、8.06ml）を加え
て、均一に溶解する。
次いでこの溶液に、前記デヒドロアビエチン酸
クロライド５ｇをアセトン10mlに溶解した溶液
を、氷冷下（１〜３℃）に約10分をかけて滴下す
る。そして氷冷下２時間撹拌を続け、次いで室温
にまで昇温する。溶液に析出物がある場合には、
滴量の水／アセトン混合溶媒を加えて希釈し、溶
解する。
室温で１時間撹拌した後、6N−塩酸を約６ml
（アミノ酸がＬ−グルタミン酸又はＬ−アスパラ
ギン酸である場合には、約８ml）添加して、PHが
約１の塩酸酸性とし、塩を加水分解して反応を終
了する。
得られたデヒドロアビエチルアミノ酸溶液を精
製する。
アミノ酸がアミノカルボン酸である場合には、
先ず溶媒中のアセトンを減圧溜去し、エーテル抽
出をして水層を除去する。さらに水洗した後重炭
酸ナトリウム飽和水溶液で抽出し、エーテル層を
除去する。
6N−塩酸を加えてPHを約１として残余の塩を
加水分解する。さらにエーテルで抽出して水層を
除去し、水洗した後、無水硫酸ナトリウムで乾燥
し、エーテルを減圧溜去して、精製デヒドロアビ
エチルアミノ酸を得る。
アミノ酸がアミノスルホン酸である場合（タウ
リン）には、先ず溶媒中のアセトンを減圧溜去
し、アンバーライトIRA−45で中和し、食塩で塩
析する。沈澱を遠心分離によつて回収し、その沈
澱をエチルアルコールに溶解する。
無水硫酸ナトリウムで乾燥した後、不溶物を濾
過して除去し、エチルアルコールを減圧溜去し、
精製デヒドロアビエチルアミノ酸を得る。
得られたデヒドロアビエチルアミノ酸の特性を
表１に示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to dehydroabiethyl amino acid or a salt thereof, and relates to the substance and a method for producing the same. The dehydroabiethyl amino acid in the present invention is an amide of dehydroabietic acid and an α-amino acid or taurine, and its salt is an alkali salt of the acid group in the α-amino acid or taurine component. The alkali salts can thus be used as surfactants, and the amides have utility as intermediates for obtaining the alkali salts. BACKGROUND ART Conventionally, as rosin-based surfactants, alkali metal salts of rosins such as gum rosin and tall oil rosin are known. Problems to be solved by the invention However, in these surfactants,
It was less effective against hard water and could form sediment or become cloudy. The present invention has been made in view of the above circumstances, and provides a novel substance that is easily soluble in hard water and useful as a rosin-based surfactant that has high surface activity when used in hard water. The purpose is to Means for Solving the Problems The substance of the present invention has the general structural formula (In the formula, X represents a residue of an α-amino acid, taurine, or an alkali salt thereof.) Amino acid residues in the present invention include glycine, D,L-α-alanine, L-valine, L-phenylalanine, sarcosine, D,L-serine,
D, L-methionine, L-tryptophan, L-
Examples include residues of α-amino acids such as aspartic acid and L-glutamic acid, and taurine, which is a hydrophilic amino acid. The dehydroabiethyl amino acid or salt thereof of the present invention can be obtained by reacting dehydroabietyl chloride with an amino acid in the presence of an alkali.
An alkaline salt of dehydroabiethyl amino acid can be obtained, and dehydroabiethyl amino acid can be obtained by hydrolyzing it. Dehydroabietic acid is obtained by dehydrogenating abietic acid, which is the main component of rosin, and dehydroabietic acid chloride is obtained by reacting thionyl chloride with this dehydroabietic acid. Effect: According to the method of the present invention, the carboxylic acid or sulfonic acid in the amino acid reacts with an alkali in the reaction atmosphere to produce a salt, and the amino group in the amino acid salt reacts with the chlorocarbonyl group of the dehydroabietic acid chloride. An amide bond is formed to obtain a dehydroabiethyl amino acid salt. Furthermore, dehydroabiethyl amino acid can be obtained by hydrolyzing this dehydroabiethyl amino acid salt with an acid. Dehydroabiethyl amino acid produces a salt by reacting with an alkali again. The dehydroabiethyl amino acid salt of the present invention has a lipophilic skeleton and contains a hydrophilic carboxylate or sulfonate in a part thereof, so that it acts as a good surfactant. Effects of the Invention The dehydroabiethyl amino acid salt of the present invention dissolves well in hard water without causing precipitation or turbidity, has a good surfactant effect, and has excellent foaming properties. Examples Amino acids include glycine, D,L-alpha-alanine, L-valine, L-phenylalanine, sarcosine, D,L-serine, D,L-methionine,
L-tryptophan, L-aspartic acid, L-
Dehydroabiethyl amino acid was synthesized using glutamic acid and taurine by the procedure described below. First, dehydroabietic acid chloride was synthesized from dehydroabietic acid. Dissolve 50 g of dehydroabietic acid with a purity of 90% in toluene, add 29 g of thionyl chloride, and stir at 80 to 85°C for 2 hours.
Allowed time to react. After the reaction was completed, the solvent and remaining thionyl chloride were distilled off. The resulting product was then dissolved in ether, washed with water, and further diluted with 0.2N
- Washed with caustic soda aqueous solution. Next, the mixture was washed with water until the washing solution became neutral, further washed with saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain purified dehydroabietic acid chloride. Next, this dehydroabietic acid chloride and an amino acid were reacted. 20ml water and 10ml acetone
Each of the above amino acids (reagent special grade) in a mixed solvent with
After dispersing 0.0144 mol, 5.86 ml of 6N caustic soda aqueous solution (amino acid L-glutamic acid or L-glutamic acid)
If it is aspartic acid, add 8.06 ml) and dissolve it uniformly. Next, a solution prepared by dissolving 5 g of the dehydroabietic acid chloride in 10 ml of acetone is added dropwise to this solution over about 10 minutes under ice cooling (1 to 3°C). Stirring was continued for 2 hours under ice cooling, and then the temperature was raised to room temperature. If there is a precipitate in the solution,
Add dropwise amount of water/acetone mixed solvent to dilute and dissolve. After stirring at room temperature for 1 hour, add approximately 6 ml of 6N-hydrochloric acid.
(When the amino acid is L-glutamic acid or L-aspartic acid, about 8 ml) is added to make the solution acidic with hydrochloric acid with a pH of about 1, and the salt is hydrolyzed to complete the reaction. The obtained dehydroabiethyl amino acid solution is purified. If the amino acid is an aminocarboxylic acid,
First, the acetone in the solvent is distilled off under reduced pressure, and the aqueous layer is removed by ether extraction. After further washing with water, the mixture is extracted with a saturated aqueous solution of sodium bicarbonate, and the ether layer is removed. Add 6N hydrochloric acid to adjust the pH to about 1 and hydrolyze the remaining salt. Further, the aqueous layer is extracted with ether, washed with water, dried over anhydrous sodium sulfate, and the ether is distilled off under reduced pressure to obtain purified dehydroabiethyl amino acid. When the amino acid is aminosulfonic acid (taurine), first, acetone in the solvent is distilled off under reduced pressure, neutralized with Amberlite IRA-45, and salted out with common salt. The precipitate is collected by centrifugation and dissolved in ethyl alcohol. After drying with anhydrous sodium sulfate, insoluble materials were removed by filtration, and ethyl alcohol was distilled off under reduced pressure.
Purified dehydroabiethyl amino acid is obtained. Table 1 shows the properties of the obtained dehydroabiethyl amino acid.
【表】
次にデヒドロアビエチルアミノ酸塩の界面活性
剤としての性質を調べる。
Ｎ−デヒドロアビエチル−グリシン−ナトリウ
ム塩、Ｎ−デヒドロアビエチル−Ｄ，Ｌ−アラニ
ン−ナトリウム塩、Ｎ−デヒドロアビエチル−Ｌ
−グルタミン酸−ナトリウム塩及びＮ−デヒドロ
アビエチル−タウリン−ナトリルム塩の、各デヒ
ドロアビエチルアミノ酸塩について試験した。ま
た比較例として、ガムロジンのナトリウム塩につ
いても試験した。
各試料の0.2％水溶液10mlと、塩化カルシウム
を水に溶解した50ppm及び300ppmの硬水10mlと
を混合し、濁り及び沈澱物の程度を調べた。
試験の結果は表２の通りであつた。[Table] Next, the properties of dehydroabiethyl amino acid salt as a surfactant will be investigated. N-dehydroabiethyl-glycine-sodium salt, N-dehydroabiethyl-D,L-alanine-sodium salt, N-dehydroabiethyl-L
- Each dehydroabiethyl amino acid salt of glutamic acid-sodium salt and N-dehydroabiethyl-taurine-sodium salt was tested. As a comparative example, a sodium salt of gum rosin was also tested. 10 ml of a 0.2% aqueous solution of each sample was mixed with 10 ml of 50 ppm and 300 ppm hard water containing calcium chloride dissolved in water, and the degree of turbidity and precipitate was examined. The test results are shown in Table 2.
【表】【table】
Claims (1)
らのアルカリ塩の残基を表わす。） で表わされるデヒドロアビエチルアミノ酸又はそ
の塩。[Claims] 1. General structural formula (In the formula, X represents a residue of an α-amino acid, taurine, or an alkali salt thereof.) A dehydroabiethyl amino acid or a salt thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60055520A JPS61212547A (en) | 1985-03-18 | 1985-03-18 | Dehydroabiethylamino acid, salt thereof, and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60055520A JPS61212547A (en) | 1985-03-18 | 1985-03-18 | Dehydroabiethylamino acid, salt thereof, and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61212547A JPS61212547A (en) | 1986-09-20 |
| JPH0466472B2 true JPH0466472B2 (en) | 1992-10-23 |
Family
ID=13000980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60055520A Granted JPS61212547A (en) | 1985-03-18 | 1985-03-18 | Dehydroabiethylamino acid, salt thereof, and production thereof |
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| Country | Link |
|---|---|
| JP (1) | JPS61212547A (en) |
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| WO2016051013A1 (en) * | 2014-10-02 | 2016-04-07 | University Of Helsinki | Abietane-type diterpenoids |
| US20200239412A1 (en) | 2017-09-29 | 2020-07-30 | Fredrik Elinder | New derivates of dhaa with electrostatic tuning |
| CN109608357B (en) * | 2019-01-08 | 2019-10-29 | 牡丹江医学院 | A kind of medical compounds that treating stomatitis and composition and preparation method thereof |
| CN110404472B (en) * | 2019-08-09 | 2020-09-01 | 福州大学 | Rosin-based Gemini surfactant and preparation method thereof |
| CN115260046B (en) * | 2022-08-22 | 2023-06-27 | 贵州大学 | Rosin acid ester compound and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS522910A (en) * | 1975-06-24 | 1977-01-11 | Senyo Kiko Kk | Mono rail car |
| JPS522911A (en) * | 1975-06-24 | 1977-01-11 | Senyo Kiko Kk | Mono rail car |
| JPS5212709A (en) * | 1975-07-17 | 1977-01-31 | Unit Rig & Equip | Excavation loading machine |
| JPS5640150A (en) * | 1979-09-11 | 1981-04-16 | Akira Washida | Stepping health instrument |
-
1985
- 1985-03-18 JP JP60055520A patent/JPS61212547A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS522910A (en) * | 1975-06-24 | 1977-01-11 | Senyo Kiko Kk | Mono rail car |
| JPS522911A (en) * | 1975-06-24 | 1977-01-11 | Senyo Kiko Kk | Mono rail car |
| JPS5212709A (en) * | 1975-07-17 | 1977-01-31 | Unit Rig & Equip | Excavation loading machine |
| JPS5640150A (en) * | 1979-09-11 | 1981-04-16 | Akira Washida | Stepping health instrument |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61212547A (en) | 1986-09-20 |
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