JPH03107489A - Production of xanthene dye by electrolysis - Google Patents
Production of xanthene dye by electrolysisInfo
- Publication number
- JPH03107489A JPH03107489A JP1242296A JP24229689A JPH03107489A JP H03107489 A JPH03107489 A JP H03107489A JP 1242296 A JP1242296 A JP 1242296A JP 24229689 A JP24229689 A JP 24229689A JP H03107489 A JPH03107489 A JP H03107489A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- xanthene dye
- dye
- acid
- reaction
- 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
- 239000001018 xanthene dye Substances 0.000 title abstract 4
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000005868 electrolysis reaction Methods 0.000 title description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 150000001768 cations Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000005185 salting out Methods 0.000 abstract description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229940075420 xanthine Drugs 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- QTWZICCBKBYHDM-UHFFFAOYSA-N leucomethylene blue Chemical compound C1=C(N(C)C)C=C2SC3=CC(N(C)C)=CC=C3NC2=C1 QTWZICCBKBYHDM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 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
- JIRHAGAOHOYLNO-UHFFFAOYSA-N (3-cyclopentyloxy-4-methoxyphenyl)methanol Chemical compound COC1=CC=C(CO)C=C1OC1CCCC1 JIRHAGAOHOYLNO-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- IOOMXAQUNPWDLL-UHFFFAOYSA-N 2-[6-(diethylamino)-3-(diethyliminiumyl)-3h-xanthen-9-yl]-5-sulfobenzene-1-sulfonate Chemical compound C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S(O)(=O)=O)C=C1S([O-])(=O)=O IOOMXAQUNPWDLL-UHFFFAOYSA-N 0.000 description 1
- MNURPFVONZPVLA-UHFFFAOYSA-N 2-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1Cl MNURPFVONZPVLA-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は染料の製造法に関する。さらに詳しくはキサン
チン系染料のロイコ体を電解酸化することにより、相当
するキサンチン系染料を製造する方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing dyes. More specifically, the present invention relates to a method for producing a corresponding xanthine dye by electrolytically oxidizing a leuco form of a xanthine dye.
従来の技術
従来、キサンチン系染料の合成法においては例工ば、ス
ルホローダミンＢエキストラ（Ｃ，Ｉ。BACKGROUND OF THE INVENTION Conventionally, in the synthesis of xanthine dyes, for example, sulforhodamine B extra (C, I) has been used.
１’＆４５１００ ）は「新染料化学」細１）豊著、技
報堂ｐ７９０によると、そのロイコ体を重クロム酸ナト
リウムで酸化して、所望する染料に変換している。また
、カラーインデックス（Ｔｈｅ ５ｏｃｉｅｔｙｏｆ
Ｄｙｅｒｓ ａｎｄ Ｃｏｌｏｕｒｉｓｔ編第３版４巻
ｐ、４４１９）には塩化第２鉄で酸化することが記載さ
れている。1'& 45100), ``New Dye Chemical'', 1) by Yutaka, Gihodo, p. 790, the leuco compound is oxidized with sodium dichromate to convert it into the desired dye. In addition, the color index (The 5ociety of
Dyers and Colourist, 3rd edition, Vol. 4, p. 4419) describes oxidation with ferric chloride.
一方、キサンチン系染料と同じカーボニウム構造を有す
るトリフェニルメタン系の染料合成に電解反応が応用さ
れている。On the other hand, electrolytic reactions have been applied to the synthesis of triphenylmethane dyes, which have the same carbonium structure as xanthine dyes.
特開昭５４−１３（１４８１，６１−２３８９９２，６
３５３２８２ではスルホン酸基含有のトリフェニルメタ
ン染料のロイコ体を電解酸化し、相当する染料を得てい
る。Japanese Unexamined Patent Publication No. 54-13 (1481, 61-238992, 6
In No. 353282, the corresponding dye was obtained by electrolytically oxidizing the leuco form of a triphenylmethane dye containing a sulfonic acid group.
発明が解決しようとする課題
前記した如くキサンチン系染料の合成においては金属系
酸化剤を用いる方法が行われているが、金属系酸化剤を
使う方法は反応後、低原子さらに重クロム酸ナトリウム
を使用する場合には、その毒性から敢扱いに充分な注意
が要求される。Problems to be Solved by the Invention As mentioned above, a method using a metal oxidizing agent is used in the synthesis of xanthine dyes. When used, due to its toxicity, sufficient care must be taken when handling it.
本発明者は工業的に重要なキサンチン系染料を製造する
にあたり、上記問題点のない製法を確立すべく種々検討
を行った。その結果、電解酸化反応により効率よく、相
当するロイコ体からキサンチン系染料の合成が可能であ
ることを見出し本発明を完成するに至った。In producing industrially important xanthine dyes, the present inventor conducted various studies in order to establish a production method that does not have the above-mentioned problems. As a result, they discovered that xanthine dyes can be efficiently synthesized from the corresponding leuco dyes by electrolytic oxidation reaction, and have completed the present invention.
課題を解決するための手段
１コ
本発明狐式（１）〔式（１）中、Ｒ１１Ｒ２は低級アル
キル基を、Ｙは水素原子又はスルホン酸基を、Ｘはカチ
オンをそれぞれ意味する。〕で示される化合物を電解酸
化することを特徴とする式（２）〔式（２）中、Ｒ□、
Ｒ２，Ｙ及びＸは式（１）におけるのと同じ意味を表す
。〕で示されるキサンチン系染料
式（１） 式（２）
の製造法に関するものである。以下、本発明の詳細な説
明する。Means for Solving the Problems 1 This Invention Formula (1) [In formula (1), R11R2 represents a lower alkyl group, Y represents a hydrogen atom or a sulfonic acid group, and X represents a cation. ] [In formula (2), R□,
R2, Y and X have the same meanings as in formula (1). The present invention relates to a method for producing xanthine dyes represented by formulas (1) and (2). The present invention will be explained in detail below.
本発明において式（１）で示される化合物の具体例とし
ては、
５−
などが挙げられるが、これらの中で特に好ましいものは
、下記式によって示されるものである。Specific examples of the compound represented by formula (1) in the present invention include 5- and the like, but particularly preferred among these are those represented by the following formula.
また、前記した化合物のスルホン酸基は塩を形成してい
ても良く、それらの塩の中では特にＬｉ、 Ｎａ、 Ｋ
、 ＮＨ４の塩が好ましい。In addition, the sulfonic acid group of the above-mentioned compound may form a salt, and among these salts, especially Li, Na, K
, NH4 salts are preferred.
支持塩としては無機酸、有機酸あるいはそれらの塩が用
いられ、その具体例としては硫酸、リン酸、塩酸、臭化
水素酸、過塩素酸、硝酸、四フッ化ホウ酸、ベンゼンス
ルホン酸、ｐ−トルエンスルホン酸、ｏ−トルエンスル
ホン酸、キシレンスルホン酸、ベンゼンジスルホン酸、
キ６−
シレンジスルホン酸、ナフタリンスルホン酸、エチルベ
ンゼンスルホン酸、クロルベンゼンスルホン酸等及びこ
れらのアルカリ金属塩、アルカリ土類塩、アンモニウム
塩等が挙げられるがこれらに限定されるものでない。反
応溶媒としては水が好ましいが、メタノール、エタノー
ル１ｓｏ−プロピルアルコールのような低級アルコール
、ＤＭＳＯ、ＤＭＦ 、ピリジンのような非プロトン性
の極性溶媒等を併用、あるいはそのまま用いることも可
能である。またその使用量は基質の３〜３０倍が望まし
い。反応液のｐＨは基質の溶解性と収率の点から通常ｐ
ｌ−１４〜１２に調整して行われるが、好ましくはｐＩ
−Ｉ ５〜１０が良い。Inorganic acids, organic acids, or their salts are used as the supporting salt, and specific examples include sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, perchloric acid, nitric acid, tetrafluoroboric acid, benzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, xylene sulfonic acid, benzenedisulfonic acid,
Examples include, but are not limited to, 6-silenedisulfonic acid, naphthalenesulfonic acid, ethylbenzenesulfonic acid, chlorobenzenesulfonic acid, and their alkali metal salts, alkaline earth salts, and ammonium salts. Water is preferred as the reaction solvent, but lower alcohols such as methanol, ethanol, and so-propyl alcohol, aprotic polar solvents such as DMSO, DMF, and pyridine, and the like may be used in combination or as they are. The amount used is preferably 3 to 30 times that of the substrate. The pH of the reaction solution is usually determined from the viewpoint of substrate solubility and yield.
It is carried out by adjusting the pI to 1-14 to 12, but preferably pI
-I 5-10 is good.
ｐＨ調整に使用される塩基としてはアルカリ金属アルカ
リ土類金属の水酸化物、炭酸塩、アンモニウム塩等が用
いられるが、特に水酸化ナトリウム、水酸化カリウム、
炭酸ナトリウム、炭酸水素ナトリウム等が好ましい。ま
た酸としては前記したもの等が用いられ、好ましくは硫
酸、塩酸である。本電解反応は通常室温で行われるが、
これに制限されるものではない。電解に必要とされる電
気量は２〜３ Ｆ／ｍｏ＋であるが、反応を行うにあた
ってはＨＰＬＣ（高速液体クロマトグラフィー）等によ
り反応を追跡し、必要量の電気を流すことによって行わ
れる。As the base used for pH adjustment, alkali metal alkaline earth metal hydroxides, carbonates, ammonium salts, etc. are used, and in particular, sodium hydroxide, potassium hydroxide,
Sodium carbonate, sodium hydrogen carbonate, etc. are preferred. As the acid, those mentioned above can be used, and sulfuric acid and hydrochloric acid are preferable. This electrolytic reaction is usually carried out at room temperature,
It is not limited to this. The amount of electricity required for electrolysis is 2 to 3 F/mo+, and the reaction is carried out by tracking the reaction using HPLC (high performance liquid chromatography) or the like and flowing the required amount of electricity.
また、本電解反応は電流密度１〜２００ ｍＡ／ｃｍ２
゜望ましくは５〜５０ｍＡ／ｃｍ２で行われる。In addition, this electrolytic reaction is conducted at a current density of 1 to 200 mA/cm2.
゜It is preferably carried out at 5 to 50 mA/cm2.
本発明で使用する電解槽は、陽陰極分離型あるいは非分
離型のもので、特に高収率を得るために分離型のものが
良い。隔膜材料としては、イオン交換膜、アスベスト、
素焼板、多孔質高分子膜などを用いることが可能である
が、好ましくはイオン交換膜である。その具体例として
はＮａｆｉｏｎ ３２４ （］）ｕｐｏｎｔ社）、セレ
ミオンＣＭＶ及びＡＭＶ （旭ガラス株式会社）、ＴＯ
８ＦＬＥＸ、 ５Ｆ−３４（東ソー株式会社）などが挙
げられる。電極材料については、陰極は通常のものを供
することが出来、陽極は耐腐食性をそなえたものが望ま
れる。例えば、白金、金、炭素、酸化鉛ＤＳＡ、ニッケ
ル及び白金、金等をコーティングしたチタン電極等が陰
極又は陽極として用いられるが、これらに限定されるも
のではない。The electrolytic cell used in the present invention may be an anode/cathode separated type or a non-separated type, and a separated type is particularly preferred in order to obtain a high yield. Diaphragm materials include ion exchange membranes, asbestos,
Although it is possible to use a clay plate, a porous polymer membrane, etc., an ion exchange membrane is preferable. Specific examples include Nafion 324 (upont), Selemion CMV and AMV (Asahi Glass Co., Ltd.), TO
Examples include 8FLEX and 5F-34 (Tosoh Corporation). Regarding the electrode materials, the cathode can be made of ordinary materials, and the anode is preferably corrosion-resistant. For example, a titanium electrode coated with platinum, gold, carbon, lead oxide DSA, nickel, platinum, gold, etc. can be used as the cathode or anode, but is not limited thereto.
電解反応終了後、目的物は通常溶解状態であるが、常法
により反応液から分離出来る。即ち、例えば酸性下、塩
析により目的物を結晶化した後、濾過することで高純度
の染料が得られる。After the electrolytic reaction is completed, the target substance is usually in a dissolved state, but it can be separated from the reaction solution by a conventional method. That is, for example, a highly pure dye can be obtained by crystallizing the target product by salting out under acidic conditions and then filtering it.
実施例 実施例により本発明を更に具体的に説明する。Example The present invention will be explained in more detail with reference to Examples.
実施例１゜
陰イオン交換膜（ＴＯ８ＦＬＥＸ ＤＦ−３４，東ソー
株式会社製）により陽、陰極室を隔離されたＨ型セルの
陽極室に、下記式（３）によって示される化合物０．６
００ｇ、水１５ｇ、２０重量％水酸化ナトリウム水溶液
約０．２ｇを入れ、一方陰極室に水１５ｇ、２０重量％
水酸化ナトリウム水溶液０．４０ｇを入れた。撹拌し陽
極液は均一溶液とした。陽極及び陰極として、１．５
ｃｍＸ ２ ｃｍの白金板を付し２８〜３３℃において
、４０ｍＡ（端子間電圧約８〜９Ｖ）の電気を１時間３
９分（２，３Ｆ／ｍｏｌ ）流した。この間陽極液のｐ
Ｈは９−
アルカリ側に変化したため、１０重量％塩酸水溶液でｐ
Ｈ８〜１０に調整した。電解終了後反応、液を分析した
ところ、収率９５％で下記式（４）（λｍａｘ ｃ＊）
−５６５ｎｍ ）によって示されるキサンチン染料が
得られた。Example 1゜0.6 of the compound represented by the following formula (3) was placed in the anode chamber of an H-type cell in which the anode and cathode chambers were separated by an anion exchange membrane (TO8FLEX DF-34, manufactured by Tosoh Corporation).
00g, 15g of water, and about 0.2g of a 20% by weight aqueous sodium hydroxide solution, and on the other hand, 15g of water, 20% by weight were placed in the cathode chamber.
0.40 g of sodium hydroxide aqueous solution was added. The anolyte was stirred to make a homogeneous solution. As anode and cathode, 1.5
Attach a platinum plate measuring 2cm x 2cm and apply electricity at 40mA (approximately 8 to 9V between terminals) for 1 hour at 28 to 33℃.
It was allowed to flow for 9 minutes (2,3 F/mol). During this time, the anolyte p
Since H changed to 9-alkaline side, p
Adjusted to H8-10. When the reaction and solution were analyzed after the completion of electrolysis, the following formula (4) (λmax c*) was obtained with a yield of 95%.
-565 nm) was obtained.
（３）
（４）
実施例２゜
式（５）で示される化合物を実施例１と同様に処理し、
式（６）で示される染料を収率９０％で得た。(3) (4) Example 2゜The compound represented by formula (5) was treated in the same manner as in Example 1,
The dye represented by formula (6) was obtained in a yield of 90%.
０−
発明の効果
電解反応により重クロム酸のような金属酸化剤を用いる
ことなく、相当するロイコ体がらキサンチン系染料の製
造が可能となった。0- Effects of the Invention Through electrolytic reaction, it has become possible to produce xanthine dyes from the corresponding leuco compound without using metal oxidizing agents such as dichromic acid.
Claims (1)
、Ｙは水素原子又はスルホン酸基を、Ｘはカチオンをそ
れぞれ意味する） で示される化合物を電解酸化することを特徴とする式（
２） ▲数式、化学式、表等があります▼（２） （式（２）においてＲ＿１、Ｒ＿２、Ｙ及びＸは式（１
）におけるのと同じ意味を示す）で示されるキサンテン
系染料の製造法[Claims] 1. Formula (1) ▲Mathematical formulas, chemical formulas, tables, etc.▼(1) (In formula (1), R_1 and R_2 are lower alkyl groups, Y is a hydrogen atom or a sulfonic acid group, X means a cation) The formula (
2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In formula (2), R_1, R_2, Y and
) has the same meaning as in ))
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1242296A JPH03107489A (en) | 1989-09-20 | 1989-09-20 | Production of xanthene dye by electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1242296A JPH03107489A (en) | 1989-09-20 | 1989-09-20 | Production of xanthene dye by electrolysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03107489A true JPH03107489A (en) | 1991-05-07 |
Family
ID=17087128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1242296A Pending JPH03107489A (en) | 1989-09-20 | 1989-09-20 | Production of xanthene dye by electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03107489A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160015251A (en) | 2013-05-31 | 2016-02-12 | 동우 화인켐 주식회사 | Compound and colored curable resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61238992A (en) * | 1985-04-13 | 1986-10-24 | バスフ アクチェン ゲゼルシャフト | Production of sulfonic acid group-containing diaminotriphenylmethane dye |
-
1989
- 1989-09-20 JP JP1242296A patent/JPH03107489A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61238992A (en) * | 1985-04-13 | 1986-10-24 | バスフ アクチェン ゲゼルシャフト | Production of sulfonic acid group-containing diaminotriphenylmethane dye |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160015251A (en) | 2013-05-31 | 2016-02-12 | 동우 화인켐 주식회사 | Compound and colored curable resin composition |
| KR20200110824A (en) | 2013-05-31 | 2020-09-25 | 동우 화인켐 주식회사 | Compound and colored curable resin composition |
| KR20200111285A (en) | 2013-05-31 | 2020-09-28 | 동우 화인켐 주식회사 | Compound and colored curable resin composition |
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