JP2014172890A - Piperazine derivative - Google Patents
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- JP2014172890A JP2014172890A JP2013049105A JP2013049105A JP2014172890A JP 2014172890 A JP2014172890 A JP 2014172890A JP 2013049105 A JP2013049105 A JP 2013049105A JP 2013049105 A JP2013049105 A JP 2013049105A JP 2014172890 A JP2014172890 A JP 2014172890A
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- 150000004885 piperazines Chemical class 0.000 title claims abstract description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 27
- 238000004061 bleaching Methods 0.000 claims abstract description 23
- 125000001424 substituent group Chemical group 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 13
- 239000007844 bleaching agent Substances 0.000 claims abstract description 11
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 14
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 13
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229940066771 systemic antihistamines piperazine derivative Drugs 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 239000003599 detergent Substances 0.000 abstract description 5
- 239000000975 dye Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000003712 decolorant Substances 0.000 abstract 1
- 238000004042 decolorization Methods 0.000 abstract 1
- -1 Cyclic amine compounds Chemical class 0.000 description 36
- 150000001875 compounds Chemical class 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000004193 piperazinyl group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000118 hair dye Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PZLVDANNEUMUAQ-UHFFFAOYSA-N 1-[4-[2-hydroxy-3-(8-methylnonoxy)propyl]piperazin-1-yl]-3-(8-methylnonoxy)propan-2-ol Chemical compound CC(C)CCCCCCCOCC(O)CN1CCN(CC(O)COCCCCCCCC(C)C)CC1 PZLVDANNEUMUAQ-UHFFFAOYSA-N 0.000 description 2
- NYCIGCZGEBDPDJ-UHFFFAOYSA-N 1-dodecoxy-3-[4-(3-dodecoxy-2-hydroxypropyl)piperazin-1-yl]propan-2-ol Chemical compound CCCCCCCCCCCCOCC(O)CN1CCN(CC(O)COCCCCCCCCCCCC)CC1 NYCIGCZGEBDPDJ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000004076 pulp bleaching Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)*N(CC1)CCN1I Chemical compound CC(C)*N(CC1)CCN1I 0.000 description 1
- 241000222290 Cladosporium Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001168730 Simo Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
本発明は、新規ピペラジン誘導体に関する。 The present invention relates to a novel piperazine derivative.
環状アミン化合物は、衣料用洗剤、カビ取り剤、パルプ漂白、染毛剤など、過酸化水素を酸化剤として用いる漂白（剤）においてその漂白効果を向上させることが知られている（特許文献１、２）。 Cyclic amine compounds are known to improve the bleaching effect in bleaching agents that use hydrogen peroxide as an oxidizing agent, such as garment detergents, mold removers, pulp bleaches, and hair dyes (Patent Document 1). 2).
しかしながら、この化合物を漂白剤や脱色剤として用いる場合、機能設計、すなわち、漂白力の強さや持続性を所望のレベルに調節する必要がある。また、漂白剤や脱色剤においては、酸化剤、アルカリ剤等の添加剤と併用されることが多いので、それらの添加剤との適合性、すなわち均一に配合でき、長期間安定であることも要求される。従って、これらの機能設計自由度、配合自由度の観点から、さらなる新規な環状アミン化合物の開発が望まれる。 However, when this compound is used as a bleaching or bleaching agent, it is necessary to adjust the functional design, that is, the strength and sustainability of the bleaching power to a desired level. In addition, bleaching agents and bleaching agents are often used in combination with additives such as oxidizing agents and alkali agents, so that they are compatible with these additives, that is, can be blended uniformly and stable for a long time. Required. Therefore, further development of a novel cyclic amine compound is desired from the viewpoints of these functional design freedom and compounding freedom.
そこで、本発明は、衣料用洗剤、カビとり剤、パルプの漂白、染毛剤など、過酸化水素を酸化剤として用いる漂白剤や脱色剤において、その漂白効果や脱色効果を向上でき、かつ安定に配合可能な新規なピペラジン誘導体を提供する。 Therefore, the present invention can improve the bleaching effect and the decoloring effect in a bleaching agent and a decoloring agent using hydrogen peroxide as an oxidizing agent, such as a detergent for clothes, a mold removing agent, a bleaching of a pulp, a hair dye, and the like. A novel piperazine derivative that can be blended in the present invention is provided.
本発明者らは、ピペラジンの所定の位置に水酸基を有する特定の基を導入した新規ピペラジン誘導体が、上記要求を満たすものであることを見出した。 The present inventors have found that a novel piperazine derivative in which a specific group having a hydroxyl group is introduced at a predetermined position of piperazine satisfies the above requirements.
すなわち、本発明は、下記一般式（１）で表されるピペラジン誘導体（以下、「本発明のピペラジン誘導体」ということがある。）に関する。 That is, the present invention relates to a piperazine derivative represented by the following general formula (1) (hereinafter sometimes referred to as “the piperazine derivative of the present invention”).
［式（１）中、Ｒ1及びＲ2は、それぞれ独立して、水素原子、又は下記一般式（２）で表される置換基を示す。ただし、Ｒ1及びＲ2は、同時に水素原子にはならない。ｋは０又は１以上、８以下の整数である。Ｒ3は、それぞれ独立して、置換基を有していてもよい炭素数１以上、２４以下の脂肪族炭化水素基、又は置換基を有していてもよい炭素数５以上、１２以下の芳香族炭化水素基を示す。］ [In Formula (1), R 1 and R 2 each independently represent a hydrogen atom or a substituent represented by the following General Formula (2). However, R 1 and R 2 are not simultaneously hydrogen atoms. k is 0 or an integer of 1 or more and 8 or less. R 3 each independently has an optionally substituted aliphatic hydrocarbon group having 1 to 24 carbon atoms, or an optionally substituted carbon atom having 5 to 12 carbon atoms. An aromatic hydrocarbon group is shown. ]
［式（２）中、Ｒ4及びＲ5は、それぞれ独立して、水素原子、又は−ＣＨ2ＯＲ6を示す。ただし、Ｒ4及びＲ5は、同時に水素原子にはならない。Ｒ6は、炭素数１０以上、３０以下の炭化水素基、下記式（３）で表される基（以下、基（３）という）、又は式（４）で表される基（以下、基（４）という）を示す。基（３）及び基（４）の酸素原子は、それぞれ、水素原子と結合しているか、又は他の基（３）もしくは基（４）の炭素原子と結合している。］ [In formula (2), R 4 and R 5 each independently represent a hydrogen atom or —CH 2 OR 6 . However, R 4 and R 5 are not hydrogen atoms at the same time. R 6 is a hydrocarbon group having 10 to 30 carbon atoms, a group represented by the following formula (3) (hereinafter referred to as group (3)), or a group represented by the formula (4) (hereinafter referred to as group). (Referred to as (4)). The oxygen atoms of the group (3) and the group (4) are each bonded to a hydrogen atom, or bonded to the carbon atom of the other group (3) or the group (4). ]
また、本発明は、前記ピペラジン誘導体を含む漂白剤組成物（以下、「本発明の漂白剤組成物」ということがある。）に関する。 The present invention also relates to a bleaching composition containing the piperazine derivative (hereinafter sometimes referred to as “the bleaching composition of the present invention”).
本発明により新規なピペラジン誘導体が提供される。本発明のピペラジン誘導体によれば、衣料用洗剤、カビとり剤、パルプの漂白、染毛剤など、過酸化水素を酸化剤として用いる漂白剤や脱色剤において、その漂白効果や脱色効果を向上させることができる。また、本発明は、原料の入手容易性やアルカリ条件下での安定性が期待できる。本発明の漂白剤組成物によれば、優れた漂白効果を発現することができる。 The present invention provides a novel piperazine derivative. According to the piperazine derivative of the present invention, bleaching and decoloring effects using hydrogen peroxide as an oxidizing agent, such as clothes detergents, mold removers, pulp bleaching, hair dyes, etc., are improved. be able to. Further, the present invention can be expected to be readily available for raw materials and stable under alkaline conditions. According to the bleach composition of the present invention, an excellent bleaching effect can be exhibited.
本発明のピペラジン誘導体は、前記一般式（１）で表される。本発明の新規ピペラジン誘導体が、過酸化水素を用いた漂白処理や脱色処理において、優れた漂白または脱色効果を発揮する理由は明らかではないが、ピペラジンの所定の位置に水酸基を有する特定の基を導入することで、漂白対象分子への吸着性が向上する、又はピペラジン誘導体の水溶性が向上するためであると考えられる。 The piperazine derivative of the present invention is represented by the general formula (1). Although the reason why the novel piperazine derivative of the present invention exhibits an excellent bleaching or decoloring effect in bleaching or decoloring treatment using hydrogen peroxide is not clear, a specific group having a hydroxyl group at a predetermined position of piperazine It is considered that the introduction improves the adsorptivity to the molecule to be bleached or improves the water solubility of the piperazine derivative.
一般式（１）において、Ｒ1及びＲ2は、それぞれ独立して、水素原子、又は下記一般式（２）で表わされる置換基を示し、Ｒ1及びＲ2は、同時に水素原子にはならない。すなわち、Ｒ1、Ｒ2の一方又は両方が、下記一般式（２）で表される基である。 In the general formula (1), R 1 and R 2 each independently represent a hydrogen atom or a substituent represented by the following general formula (2), and R 1 and R 2 do not simultaneously become a hydrogen atom. . That is, one or both of R 1 and R 2 is a group represented by the following general formula (2).
［式（２）中、Ｒ4及びＲ5は、それぞれ独立して、水素原子、又は−ＣＨ2ＯＲ6を示す。ただし、Ｒ4及びＲ5は、同時に水素原子にはならない。Ｒ6は、炭素数１０以上、３０以下の炭化水素基、下記式（３）で表される基（以下、基（３）という）、又は式（４）で表される基（以下、基（４）という）を示す。基（３）及び基（４）の酸素原子は、それぞれ、水素原子と結合しているか、又は他の基（３）もしくは基（４）の炭素原子と結合している。］
一般式（２）の置換基について、Ｒ4及びＲ5となり得る基として、−ＣＨ2ＯＲ6が挙げられる。Ｒ6は、炭素数１０以上、３０以下の炭化水素基、基（３）、又は基（４）である。Ｒ6のうち、炭化水素基の炭素数は、１８以下が好ましい。該炭化水素基としては、脂肪族炭化水素基、芳香族炭化水素基が挙げられる。脂肪族炭化水素基は、直鎖又は分岐鎖炭化水素基が挙げられる。直鎖又は分岐鎖炭化水素基は、アルキル基、アルケニル基が挙げられ、アルキル基が好ましい。アルキル基としては、炭素数１１以上、更に１２以上、そして、３０以下、更に１８以下の直鎖アルキル基、及び炭素数１０以上、そして、３０以下、更に１８以下の分岐鎖アルキル基が挙げられる。アルキル基としては、デシル基、イソデシル基、ドデシル基、テトラデシル基、ステアリル基、及びイソステアリル基から選ばれる基が挙げられ、更にイソデシル基、ドデシル基、テトラデシル基、及びイソステアリル基から選ばれる基が好ましい。また、Ｒ6の炭化水素基、例えば、アルキル基は、水酸基、アミノ基などの置換基を有していてもよい。一般式（２）中のＲ6は、炭素数１１以上、更に１２以上、３０以下の直鎖アルキル基、及び炭素数１０以上、３０以下の分岐鎖アルキル基から選ばれる基であることが好ましい。 With respect to the substituent of the general formula (2), examples of the group that can be R 4 and R 5 include —CH 2 OR 6 . R 6 is a hydrocarbon group having 10 or more and 30 or less carbon atoms, a group (3), or a group (4). Of R 6 , the hydrocarbon group preferably has 18 or less carbon atoms. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group. Examples of the linear or branched hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferable. Examples of the alkyl group include a linear alkyl group having 11 or more, 12 or more, and 30 or less, and 18 or less, and a branched alkyl group having 10 or more, 30 or less, and 18 or less. . Examples of the alkyl group include a group selected from a decyl group, an isodecyl group, a dodecyl group, a tetradecyl group, a stearyl group, and an isostearyl group, and further a group selected from an isodecyl group, a dodecyl group, a tetradecyl group, and an isostearyl group. Is preferred. Further, the hydrocarbon group of R 6 , for example, an alkyl group, may have a substituent such as a hydroxyl group or an amino group. R 6 in the general formula (2) is preferably a group selected from a linear alkyl group having 11 or more, 12 or more and 30 or less carbon atoms, and a branched alkyl group having 10 or more and 30 or less carbon atoms. .
ピペラジン環の炭素原子は全て水素原子と結合してもよく、１個以上、８個以下のＲ3を置換基として有していてもよい。ｋは０又は１以上、８以下の整数である。ｋは、０、１又は２、更に０又は１、更に０が好ましい。また、一般式（１）中、Ｒ3は、ｋが１以上の場合にピペラジン環の炭素原子に結合する１つ以上の置換基であり、それぞれ独立して置換基を有しても良い炭素数１以上、２４以下の脂肪族炭化水素基、又は置換基を有していてもよい炭素数５以上、１２以下の芳香族炭化水素基である。 All the carbon atoms of the piperazine ring may be bonded to a hydrogen atom, and may have 1 or more and 8 or less R 3 as a substituent. k is 0 or an integer of 1 or more and 8 or less. k is preferably 0, 1 or 2, more preferably 0 or 1, and further preferably 0. In the general formula (1), R 3 is one or more substituents bonded to the carbon atom of the piperazine ring when k is 1 or more, and each of them may independently have a substituent. It is an aliphatic hydrocarbon group having 1 to 24 carbon atoms, or an aromatic hydrocarbon group having 5 to 12 carbon atoms that may have a substituent.
Ｒ3のうち、置換基を有しても良い脂肪族炭化水素基の炭素数は、２４以下、更に１８以下、更に１２以下が好ましい。直鎖又は分岐鎖炭化水素基は、アルキル基、アルケニル基が挙げられ、アルキル基が好ましい。アルキル基としては、炭素数１以上、そして、１８以下、更に１２以下の直鎖アルキル基、炭素数３以上、そして、１８以下、更に１２以下の分岐鎖アルキル基が挙げられる。アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−デシル基、ｉｓｏ−デシル基、及びｎ−ドデシル基、２−エチルヘキシル基から選ばれる１種以上の基が挙げられる。また、アルキル基は置換基を有するアルキル基であってもよい。該脂肪族炭化水素基が有していてもよい置換基としては、ハロゲン原子、水酸基、アミノ基が挙げられる。置換基を有する脂肪族炭化水素基としては、２−ヒドロキシエチル基、３−ヒドロキシプロピル基、２−メトキシエチル基、３−メトキシプロピル基、２−（ジメチルアミノ）エチル基、３−（ジメチルアミノ）プロピル基等が挙げられる。 Of R 3, the aliphatic hydrocarbon group which may have a substituent preferably has 24 or less, more preferably 18 or less, and still more preferably 12 or less. Examples of the linear or branched hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferable. Examples of the alkyl group include straight chain alkyl groups having 1 or more and 18 or less, and 12 or less, and branched alkyl groups having 3 or more and 18 or less, and further 12 or less. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n One or more groups selected from a -decyl group, an iso-decyl group, an n-dodecyl group, and a 2-ethylhexyl group may be mentioned. The alkyl group may be an alkyl group having a substituent. Examples of the substituent that the aliphatic hydrocarbon group may have include a halogen atom, a hydroxyl group, and an amino group. Examples of the aliphatic hydrocarbon group having a substituent include 2-hydroxyethyl group, 3-hydroxypropyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2- (dimethylamino) ethyl group, and 3- (dimethylamino). ) Propyl group and the like.
また、Ｒ3のうち、置換基を有していてもよい炭素数５以上、１２以下の芳香族炭化水素基としては、置換基を有していてもよいフェニル基、更に、フェニル基、置換基を有するフェニル基が挙げられる。該芳香族炭化水素基が有していてもよい置換基としては、ハロゲン、水酸基、炭素数１以上、２４以下の炭化水素基が挙げられる。炭素数１以上、２４以下の炭化水素基としては、アルキル基、アルケニル基が挙げられる。 Moreover, among R 3 , the aromatic hydrocarbon group having 5 to 12 carbon atoms which may have a substituent includes a phenyl group which may have a substituent, a phenyl group, and a substituted group. And a phenyl group having a group. Examples of the substituent that the aromatic hydrocarbon group may have include a halogen, a hydroxyl group, and a hydrocarbon group having 1 to 24 carbon atoms. Examples of the hydrocarbon group having 1 to 24 carbon atoms include an alkyl group and an alkenyl group.
Ｒ3は、漂白性能向上の観点から、炭素数１以上、２４以下の脂肪族炭化水素基が好ましく、炭素数１以上、１２以下の脂肪族炭化水素基がより好ましく、炭素数１以上、１２以下のアルキル基が更に好ましい。 R 3 is preferably an aliphatic hydrocarbon group having 1 to 24 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 12 carbon atoms from the viewpoint of improving bleaching performance. The following alkyl groups are more preferred.
漂白性能向上の観点から、本発明のピペラジン誘導体としては、一般式（１）において、Ｒ1及びＲ2が一般式（２）で表される置換基であり、一般式（２）において、Ｒ4及びＲ5の一方が水素原子、他方が−ＣＨ2ＯＲ6である化合物が好ましく、更に一般式（１）において、Ｒ1及びＲ2が一般式（２）で表される置換基であり、ｋが０、１又は２であり、ｋが１又は２の場合は、Ｒ3がそれぞれ独立して炭素数１以上、１２以下の炭化水素基であり、一般式（２）において、Ｒ4及びＲ5の一方が水素原子、他方が−ＣＨ2ＯＲ6である化合物が好ましい。 From the viewpoint of improving the bleaching performance, the piperazine derivative of the present invention includes R 1 and R 2 in the general formula (1) as substituents represented by the general formula (2). In the general formula (2), R 1 A compound in which one of 4 and R 5 is a hydrogen atom and the other is —CH 2 OR 6 is preferable. In the general formula (1), R 1 and R 2 are substituents represented by the general formula (2). , K is 0, 1 or 2, and when k is 1 or 2, each R 3 is independently a hydrocarbon group having 1 to 12 carbon atoms, and in the general formula (2), R 4 And a compound in which one of R 5 is a hydrogen atom and the other is —CH 2 OR 6 is preferred.
本発明のピペラジン誘導体の好ましい態様を例示する。
（Ｉ）一般式（１）中、Ｒ1及びＲ2の両方が一般式（２）で表される基である化合物
（II）一般式（１）中、ｋが０、１又は２であり、ｋが１又は２の場合は、Ｒ3がそれぞれ独立して炭素数１以上、２４以下の脂肪族炭化水素基である、好ましくは炭素数１以上、１２以下の脂肪族炭化水素基である、より好ましくはメチル基である、さらにより好ましくはｋが０である化合物
（III）一般式（２）中、Ｒ4及びＲ5の一方が水素原子、他方が−ＣＨ2ＯＲ6である化合物
（IV）一般式（２）の−ＣＨ2ＯＲ6中、Ｒ6が炭素数１１以上、更に１２以上、３０以下の直鎖アルキル基、又は炭素数１０以上、３０以下の分岐鎖アルキル基であり、より好ましくはイソデシル基、ドデシル基、テトラデシル基、及びイソステアリル基から選ばれる基である化合物
（Ｖ）上記（Ｉ）〜（IV）の２つ以上の態様を満たす化合物
The preferable aspect of the piperazine derivative of this invention is illustrated.
(I) In general formula (1), both R 1 and R 2 are groups represented by general formula (2) (II) In general formula (1), k is 0, 1 or 2 , K is 1 or 2, each R 3 is independently an aliphatic hydrocarbon group having 1 to 24 carbon atoms, preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms. More preferably a methyl group, still more preferably k is 0 (III) a compound in which one of R 4 and R 5 is a hydrogen atom and the other is —CH 2 OR 6 in general formula (2) (IV) In —CH 2 OR 6 of the general formula (2), R 6 is a linear alkyl group having 11 or more, 12 or more and 30 or less carbon atoms, or a branched alkyl group having 10 or more and 30 or less carbon atoms. More preferably a group selected from an isodecyl group, a dodecyl group, a tetradecyl group, and an isostearyl group. That compound (V) above (I) compound that satisfies two or more aspects of ~ (IV)
本発明のピペラジン誘導体の具体例としては、以下の化合物を挙げることができる。なお、アルキル基を有する化合物においては、アルキル基は異性体（直鎖、分岐鎖）も含む。また、これらの化合物番号は、後述の実施例で用いた化合物の番号と一致する。 Specific examples of the piperazine derivative of the present invention include the following compounds. In the compound having an alkyl group, the alkyl group includes isomers (straight chain and branched chain). Moreover, these compound numbers correspond with the compound numbers used in Examples described later.
式中、「Ｃ12」は炭素数１２のアルキル基（ドデシル基）、「ｉＤ」はイソデシル基を意味する。 In the formula, “C 12 ” means an alkyl group having 12 carbon atoms (dodecyl group), and “iD” means an isodecyl group.
本発明のピペラジン誘導体の製造方法は、特に限定されないが、例えば、下記一般式（１’）で表されるピペラジン化合物と下記一般式（２’）で表されるグリシジルエーテル化合物とを、一般式（１）を満たす条件となるように用いて、反応させる（以下、方法１という）ことで製造することができる。よって、本発明は、下記一般式（１’）で表されるピペラジン化合物と下記一般式（２’）で表されるグリシジルエーテル化合物とを反応させて得られるピペラジン誘導体を提供する。また、本発明は、下記一般式（１’）で表されるピペラジン化合物と下記一般式（２’）で表されるグリシジルエーテル化合物とを反応させる、一般式（１）で表されるピペラジン誘導体の製造方法を提供する。 Although the manufacturing method of the piperazine derivative of the present invention is not particularly limited, for example, a piperazine compound represented by the following general formula (1 ′) and a glycidyl ether compound represented by the following general formula (2 ′) It can be produced by reacting (hereinafter referred to as method 1) using the conditions satisfying (1). Therefore, the present invention provides a piperazine derivative obtained by reacting a piperazine compound represented by the following general formula (1 ') with a glycidyl ether compound represented by the following general formula (2'). In addition, the present invention provides a piperazine derivative represented by the general formula (1) in which a piperazine compound represented by the following general formula (1 ′) and a glycidyl ether compound represented by the following general formula (2 ′) are reacted. A manufacturing method is provided.
［式（１’）中、Ｒ3及びｋは一般式（１）と同じである。また、式（２’）中、Ｒ6は一般式（２）と同じである。］ [In the formula (1 ′), R 3 and k are the same as those in the general formula (1). In the formula (2 ′), R 6 is the same as in the general formula (2). ]
方法１では、一般式（２）中、Ｒ4及びＲ5の一方が水素原子であり、他方が−ＣＨ2ＯＲ6である化合物が製造される。 In the method 1, a compound in which one of R 4 and R 5 is a hydrogen atom and the other is —CH 2 OR 6 in the general formula (2) is produced.
反応原料の一つである一般式（１’）で表されるピペラジン化合物は、例えば非特許文献、Tetrahedron Letter 2005年、４６号、７９２１頁に記載の方法で合成することができる。 The piperazine compound represented by the general formula (1 '), which is one of the reaction raw materials, can be synthesized by the method described in Non-Patent Document, Tetrahedron Letter 2005, No. 46, page 7921, for example.
方法１における反応温度は、反応させるグリシジルエーテル化合物の反応性により適宜設定することができるが、通常−２０℃以上、２００℃以下である。反応時発熱を伴う場合は、−２０℃以上、０℃以下で反応することが好ましい。反応が進行しづらい場合には、８０℃以上、２００℃以下で反応することが好ましい。 The reaction temperature in Method 1 can be appropriately set depending on the reactivity of the glycidyl ether compound to be reacted, but is usually -20 ° C or higher and 200 ° C or lower. When accompanied by exotherm during the reaction, the reaction is preferably performed at -20 ° C or higher and 0 ° C or lower. When the reaction is difficult to proceed, it is preferable to react at 80 ° C. or higher and 200 ° C. or lower.
方法１に用いる溶媒としては、反応条件下安定でかつ蒸留等の操作により生成物から分離できるものであれば、特に限定はされない。使用されうる溶媒しては、例えば、脂肪族炭化水素化合物、芳香族炭化水素化合物、ハロゲン化炭化水素化合物、エーテル化合物、アミド化合物、スルホキシド化合物等が挙げられる。なお、溶媒を用いずに反応を行ってもよく、反応後の精製工程の負荷の観点から、前記溶媒の使用量は、式（１’）のピペラジン化合物に対して５０００質量％以下、更に２０００質量％以下、更に１０００質量％以下が好ましい。 The solvent used in Method 1 is not particularly limited as long as it is stable under the reaction conditions and can be separated from the product by an operation such as distillation. Examples of the solvent that can be used include aliphatic hydrocarbon compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ether compounds, amide compounds, sulfoxide compounds, and the like. In addition, you may react without using a solvent, and from the viewpoint of the load of the refinement | purification process after reaction, the usage-amount of the said solvent is 5000 mass% or less with respect to the piperazine compound of Formula (1 '), and also 2000 It is preferably not more than mass%, more preferably not more than 1000 mass%.
方法１では、酸性及び塩基性の均一系触媒もしくは酸性及び塩基性の固体触媒を使用することができるが、反応後の精製工程の負荷低減の観点からは、無触媒で反応を行うことが好ましい。 In Method 1, acidic and basic homogeneous catalysts or acidic and basic solid catalysts can be used, but from the viewpoint of reducing the load of the purification step after the reaction, it is preferable to carry out the reaction without a catalyst. .
前記の反応に用いる酸触媒としては、アルキル硫酸、ｐ−トルエンスルホン酸等のアルキルスルホン酸やアリールスルホン酸、リン酸、トルフルオロメタンスルホン酸、フッ化水素、ＳＯ3、ホウ酸、過塩素酸、ルイス酸（例えばホウ素、アルミニウム、鉄、チタン、スズ、亜鉛、スカンジウム、ランタン等のハロゲン化物やスルホン酸塩）、スルホン酸基を有する酸性イオン交換樹脂、ヘテロポリ酸及びその塩（例えば、Ｈ4ＳｉＭｏ12Ｏ40、Ｈ3ＰＭｏ12Ｏ40、Ｈ3ＰＷ12Ｏ40）、ゼオライト、などを挙げることができる。 Examples of the acid catalyst used in the reaction include alkyl sulfonic acids such as alkyl sulfuric acid and p-toluene sulfonic acid, aryl sulfonic acids, phosphoric acid, trifluoromethane sulfonic acid, hydrogen fluoride, SO 3 , boric acid, and perchloric acid. Lewis acids (for example, halides and sulfonates such as boron, aluminum, iron, titanium, tin, zinc, scandium, and lanthanum), acidic ion exchange resins having a sulfonic acid group, heteropolyacids and salts thereof (for example, H 4) SiMo 12 O 40, H 3 PMo 12 O 40, H 3 PW 12 O 40), zeolite, and the like.
塩基触媒としては、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、水素化ナトリウム、ナトリウムメトキサイド等のアルカリ金属又はアルカリ土類金属の水酸化物、炭酸塩、水素化物、アルコキサイド等が挙げられる。 Examples of the base catalyst include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydride, sodium methoxide, and other alkali metal or alkaline earth metal hydroxides, carbonates, Examples thereof include hydrides and alkoxides.
使用する触媒の量としては、一般式（１’）で表されるピペラジン化合物に対して、０．００１質量％以上、更に０．０１質量％以上、更に０．１質量％以上が好ましく、そして、３０質量％以下、更に２０質量％以下、更に１０質量％が好ましい。 The amount of the catalyst used is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.1% by mass or more with respect to the piperazine compound represented by the general formula (1 ′). 30% by mass or less, further 20% by mass or less, and further preferably 10% by mass.
本発明のピペラジン誘導体の好ましい用途については、医薬、農薬等の合成中間体や衣料用洗剤、カビとり剤、パルプの漂白、染毛剤など、過酸化水素を酸化剤として用いる漂白剤や脱色剤において、その漂白効果や脱色効果を向上させる基剤として利用することができる。本発明により、本発明のピペラジン誘導体を含む漂白剤組成物が提供される。また、本発明により、本発明のピペラジン誘導体及び過酸化水素又は水中で過酸化水素を放出する化合物を含む漂白剤組成物が提供される。 Regarding the preferred use of the piperazine derivative of the present invention, bleaching agents and bleaching agents that use hydrogen peroxide as an oxidizing agent, such as synthetic intermediates such as pharmaceuticals and agricultural chemicals, detergents for clothes, mildew removing agents, pulp bleaching, hair dyeing agents, etc. Can be used as a base for improving the bleaching effect and decoloring effect. According to the present invention, a bleaching composition comprising the piperazine derivative of the present invention is provided. The present invention also provides a bleach composition comprising the piperazine derivative of the present invention and hydrogen peroxide or a compound that releases hydrogen peroxide in water.
◎ＮＭＲ測定条件
・ＮＭＲ装置：Ｍｅｒｃｕｒｙ４００ＢＢ（４００ＭＨｚ、Ｖａｒｉａｎ社製）
・観測幅：６４１０．３Ｈｚ
・データポイント：６４Ｋ
・パルス幅：４５マイクロ秒
・パルス遅延時間：１０秒
・積算：１６回
・測定温度：室温（２５℃）
・溶媒：重クロロホルム
◎ NMR measurement conditions / NMR apparatus: Mercury 400BB (400 MHz, manufactured by Varian)
-Observation width: 6410.3 Hz
・ Data point: 64K
・ Pulse width: 45 microseconds ・ Pulse delay time: 10 seconds ・ Integration: 16 times ・ Measurement temperature: Room temperature (25 ° C.)
・ Solvent: Deuterated chloroform
◎ガスクロマトグラフィー（ＧＣ）測定条件
化合物１、２は、エタノール溶液とし、ＧＣにより、下記条件で測定した。
・装置： ＨＰ６８５０ Ｓｅｒｉｅｓ（ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ社製）
・カラム：Ａｇｉｌｅｎｔ Ｊ＆Ｗ ＤＢ１−ＨＴ（Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製、内径０．２５ｍｍ、長さ１５ｍ、膜厚０．１ｍ）
・キャリアガス：Ｈｅ、１．０ｍＬ／分
・注入口温度：３００℃
・検出：ＦＩＤ方式、３００℃
・カラム温度条件：１００℃で２分保持した後、１０℃／分で昇温し、３５０℃で８分保持した。
◎ Gas Chromatography (GC) Measurement Conditions Compounds 1 and 2 were ethanol solutions and measured by GC under the following conditions.
・ Device: HP6850 Series (made by HEWLETT PACKARD)
Column: Agilent J & W DB1-HT (manufactured by Agilent Technologies, ID 0.25 mm, length 15 m, film thickness 0.1 m)
Carrier gas: He, 1.0 mL / min Injection port temperature: 300 ° C
・ Detection: FID method, 300 ° C
Column temperature condition: held at 100 ° C. for 2 minutes, then heated at 10 ° C./minute and held at 350 ° C. for 8 minutes.
◎ガスクロマトグラフィー質量分析（ＧＣ／ＭＳ）測定条件
化合物１、２は、エタノール溶液とし、ＧＣ／ＭＳにより、下記条件で測定した。
・ＧＣ装置： ＧＣ−２０１０ Ｓｅｒｉｅｓ（島津サイエンス社製）
・カラム：ＲＥＳＴＥＫ Ｒｘｉ−１ｍｓ（島津ジーエルシー社製、内径０．２５ｍｍ、長さ３０ｍ、膜厚０．２５μｍ）
・キャリアガス：Ｈｅ、１．０ｍＬ／分
・注入口温度：３５０℃
・検出：ＦＩＤ方式、３５０℃
・カラム温度条件：５０℃で２分保持した後、１０℃／分で昇温し、３３０℃で１０分保持した。
・ＭＳ装置： ＱＰ−２０１０ｐｌｕｓ Ｓｅｒｉｅｓ（島津サイエンス社製）
・イオン源種類：ＮＣＩ
・イオン源温度：２００℃
・インターフェス温度：３００℃
・イオン化モード：ＳＣＩ
◎ Gas Chromatography Mass Spectrometry (GC / MS) Measurement Conditions Compounds 1 and 2 were ethanol solutions and measured by GC / MS under the following conditions.
・ GC device: GC-2010 Series (Shimadzu Science)
Column: RESTEK Rxi-1 ms (manufactured by Shimadzu LLC, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)
・ Carrier gas: He, 1.0 mL / min ・ Inlet temperature: 350 ° C.
・ Detection: FID method, 350 ° C
Column temperature condition: After holding at 50 ° C. for 2 minutes, the temperature was raised at 10 ° C./minute and held at 330 ° C. for 10 minutes.
・ MS equipment: QP-2010plus Series (manufactured by Shimadzu Science)
・ Ion source type: NCI
-Ion source temperature: 200 ° C
・ Interface temperature: 300 ℃
・ Ionization mode: SCI
実施例１＜N,N'-ビス（３−ドデシルオキシ−２−ヒドロキシプロピル）ピペラジンの合成＞
ピペラジン化合物〔一般式（１’）中のＲ3が水素原子である化合物〕0.309ｇ（3.58ｍｍｏｌ）とエポキシ化合物〔一般式（２’）中のＲ6がドデシル基である化合物〕1.737ｇ（7.16ｍｍｏｌ）を反応容器にて混合した後、ホットプレートスターラー（Reacti-Therm Heating/Stirring Module、PIEACE社製）を用いて120℃に昇温し、12時間維持した。反応終了後、2.046ｇの白色固体としてN,N'-ビス（３−ドデシルオキシ−２−ヒドロキシプロピル）ピペラジン〔一般式（１）中のＲ1、Ｒ2が、それぞれ一般式（２）で表される基であり、ｋが０であり、式（２）中のＲ4が水素原子であり、Ｒ5が−ＣＨ2ＯＲ6で表される基であり、Ｒ6がドデシル基である化合物、以下、化合物１という〕を得た（ＧＣ純度９６％）。
Example 1 <Synthesis of N, N'-bis (3-dodecyloxy-2-hydroxypropyl) piperazine>
Piperazine compound [compound in which R 3 in general formula (1 ′) is a hydrogen atom] 0.309 g (3.58 mmol) and an epoxy compound [compound in which R 6 in general formula (2 ′) is a dodecyl group] 1.737 g ( 7.16 mmol) was mixed in a reaction vessel, heated to 120 ° C. using a hot plate stirrer (Reacti-Therm Heating / Stirring Module, manufactured by PIEACE) and maintained for 12 hours. After completion of the reaction, N, N′-bis (3-dodecyloxy-2-hydroxypropyl) piperazine as a white solid of 2.046 g [R 1 and R 2 in the general formula (1) are each represented by the general formula (2) And k is 0, R 4 in the formula (2) is a hydrogen atom, R 5 is a group represented by —CH 2 OR 6 , and R 6 is a dodecyl group. Compound, hereinafter referred to as Compound 1] (GC purity 96%).
・1Ｈ−ＮＭＲ
δ 0.88 (t 6H), 1.26 (s 36H), 1.54-1.61 (m 4H), 2.35-2.48 (m 8H), 2.66 (s 4H), 3.38-3.47 (m 8H), 3.84-3.90 (m 2H)
・1 H-NMR
δ 0.88 (t 6H), 1.26 (s 36H), 1.54-1.61 (m 4H), 2.35-2.48 (m 8H), 2.66 (s 4H), 3.38-3.47 (m 8H), 3.84-3.90 (m 2H)
・ＭＳ
Retention time: 26.883
Calculated for C34H71N2O4 + [M+H]+ 571.5
Found 571
・ MS
Retention time: 26.883
Calculated for C 34 H 71 N 2 O 4 + [M + H] + 571.5
Found 571
実施例２＜N,N'-ビス（３−イソデシルオキシ−２−ヒドロキシプロピル）ピペラジンの合成＞
ピペラジン化合物〔一般式（４）中のＲ3が水素原子である化合物〕0.344ｇ（3.99ｍｍｏｌ）とエポキシ化合物〔一般式（２’）中のＲ6がイソデシル基である化合物〕1.717ｇ（8.00ｍｍｏｌ）を反応容器にて混合した後、ホットプレートスターラー（Reacti-Therm Heating/Stirring Module、PIEACE社製）を用いて120℃に昇温し、12時間維持した。反応終了後、2.061ｇの無色液体としてN,N'-ビス（３−イソデシルオキシ−２−ヒドロキシプロピル）ピペラジン〔一般式（１）中のＲ1、Ｒ2が、それぞれ一般式（２）で表される基であり、ｋが０であり、式（２）中のＲ4が水素原子であり、Ｒ5が−ＣＨ2ＯＲ6で表される基であり、Ｒ6がイソデシル基である化合物、以下、化合物２という〕を得た（ＧＣ純度９４％）。
Example 2 <Synthesis of N, N'-bis (3-isodecyloxy-2-hydroxypropyl) piperazine>
Piperazine compound [compound in which R 3 in general formula (4) is a hydrogen atom] 0.344 g (3.99 mmol) and epoxy compound [compound in which R 6 in general formula (2 ′) is an isodecyl group] 1.717 g (8.00) mmol) was mixed in a reaction vessel, and then heated to 120 ° C. using a hot plate stirrer (Reacti-Therm Heating / Stirring Module, manufactured by PIEACE) and maintained for 12 hours. After completion of the reaction, 2.061 g of a colorless liquid is obtained as N, N′-bis (3-isodecyloxy-2-hydroxypropyl) piperazine [in the general formula (1), R 1 and R 2 are each represented by the general formula (2) Wherein k is 0, R 4 in formula (2) is a hydrogen atom, R 5 is a group represented by —CH 2 OR 6 , and R 6 is an isodecyl group. A certain compound, hereinafter referred to as Compound 2] was obtained (GC purity 94%).
・1Ｈ−ＮＭＲ
δ 0.73-0.88 (m 18H), 1.08-1.64 (m 20H), 2.37-2.49 (m 8H), 2.66 (s 4H), 3.38-3.49 (m 8H), 3.85-3.88 (m 2H)
・1 H-NMR
δ 0.73-0.88 (m 18H), 1.08-1.64 (m 20H), 2.37-2.49 (m 8H), 2.66 (s 4H), 3.38-3.49 (m 8H), 3.85-3.88 (m 2H)
・ＭＳ
Retention time: 28.217
Calculated for C30H63N2O4 + [M+H]+ 515.5
Found 516
・ MS
Retention time: 28.217
Calculated for C 30 H 63 N 2 O 4 + [M + H] + 515.5
Found 516
試験例１
表１に示す組成のＡ液及びＢ液を調製し、両者を等量（体積比１：１）混合し、酸化性組成物であるカビ取り剤組成物を得た〔（Ｃ）成分の含有量は過酸化水素としての量である。〕。Ａ液とＢ液は、硫酸及び／又は水酸化ナトリウムを用いてｐＨを調整した。この組成物を使用し、下記のカビ汚れ洗浄試験を実施した。その結果を下記表１に示す。なお、Ａ液とＢ液を等量混合した組成物のｐＨ（２０℃）は、何れも１２．０であった。また、Ａ液とＢ液を等量混合した直後の組成物中の各成分の含有量は、表１中の数値（質量％）の１／２となる。なお、各試験例の（Ａ）成分の含有量が同モル濃度となるように、（Ａ）成分の質量濃度を調整している。
Test example 1
Liquid A and liquid B having the composition shown in Table 1 were prepared, and both were mixed in an equal amount (volume ratio 1: 1) to obtain a fungicide removing composition which was an oxidizing composition [Containment of component (C) The amount is the amount as hydrogen peroxide. ]. A liquid and B liquid adjusted pH using a sulfuric acid and / or sodium hydroxide. Using this composition, the following mold stain cleaning test was conducted. The results are shown in Table 1 below. In addition, pH (20 degreeC) of the composition which mixed A liquid and B liquid equally was all 12.0. In addition, the content of each component in the composition immediately after mixing A liquid and B liquid in equal amounts is 1/2 of the numerical value (mass%) in Table 1. In addition, the mass concentration of (A) component is adjusted so that content of (A) component of each test example may become the same molar concentration.
＜カビ汚れ洗浄試験＞
クラドスポリウム（Cladosporium）属細菌を素焼きタイルに接種し、温度３０℃、湿度１００％ＲＨで６０日間培養したものをカビ発生タイルとし、漂白性能を比較した。
<Must stain cleaning test>
Bleaching performance was compared by inoculating unglazed tiles with bacteria of the genus Cladosporium and culturing for 60 days at a temperature of 30 ° C. and a humidity of 100% RH as mold generating tiles.
カビ発生タイルに上記カビ取り剤組成物を２０μｌ滴下し、直径約１ｃｍとし、２５℃で２０分放置後、水洗、風乾した後、色差計（日本電色工業製ＳＥ６０００）を用いて明度（Ｌ）値を測定し、次式により漂白率を算出した。この漂白率の１０％（１０ポイント）以上の相違は、漂白効果に有意な差があることを当業者が認識できるものである。 20 μl of the above mold removing composition was dropped onto the mold generating tile, the diameter was about 1 cm, left at 25 ° C. for 20 minutes, washed with water, air-dried, and lightness (L) using a color difference meter (SE6000 manufactured by Nippon Denshoku Industries). ) Value was measured, and the bleaching rate was calculated by the following formula. Those skilled in the art can recognize that a difference of 10% (10 points) or more in the bleaching rate has a significant difference in the bleaching effect.
表１の結果から、（Ｂ）成分と（Ｃ）成分と（Ｄ）成分の併用系に（Ａ）成分を用いることで、漂白率が大幅に向上することがわかる。 From the results in Table 1, it can be seen that the bleaching rate is greatly improved by using the component (A) in the combined system of the component (B), the component (C) and the component (D).
Claims (5)
［式（１）中、Ｒ1及びＲ2は、それぞれ独立して、水素原子、又は下記一般式（２）で表される置換基を示す。ただし、Ｒ1及びＲ2は、同時に水素原子にはならない。ｋは０又は１以上、８以下の整数である。Ｒ3は、それぞれ独立して、置換基を有していてもよい炭素数１以上、２４以下の脂肪族炭化水素基、又は置換基を有していてもよい炭素数５以上、１２以下の芳香族炭化水素基を示す。］
［式（２）中、Ｒ4及びＲ5は、それぞれ独立して、水素原子、又は−ＣＨ2ＯＲ6を示す。ただし、Ｒ4及びＲ5は、同時に水素原子にはならない。Ｒ6は、炭素数１０以上、３０以下の炭化水素基、下記式（３）で表される基（以下、基（３）という）、又は式（４）で表される基（以下、基（４）という）を示す。基（３）及び基（４）の酸素原子は、それぞれ、水素原子と結合しているか、又は他の基（３）もしくは基（４）の炭素原子と結合している。］
[In Formula (1), R 1 and R 2 each independently represent a hydrogen atom or a substituent represented by the following General Formula (2). However, R 1 and R 2 are not simultaneously hydrogen atoms. k is 0 or an integer of 1 or more and 8 or less. R 3 each independently has an optionally substituted aliphatic hydrocarbon group having 1 to 24 carbon atoms, or an optionally substituted carbon atom having 5 to 12 carbon atoms. An aromatic hydrocarbon group is shown. ]
[In formula (2), R 4 and R 5 each independently represent a hydrogen atom or —CH 2 OR 6 . However, R 4 and R 5 are not hydrogen atoms at the same time. R 6 is a hydrocarbon group having 10 to 30 carbon atoms, a group represented by the following formula (3) (hereinafter referred to as group (3)), or a group represented by the formula (4) (hereinafter referred to as group). (Referred to as (4)). The oxygen atoms of the group (3) and the group (4) are each bonded to a hydrogen atom, or bonded to the carbon atom of the other group (3) or the group (4). ]
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| JP2017039772A (en) * | 2016-11-01 | 2017-02-23 | 花王株式会社 | Homopiperazine derivative |
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