JPH04202681A - Production of n,n,n',n'-tetrakis(p-dialkylaminophenyl)-p-benzoquinonebis(imonium perchlorate) - Google Patents
Production of n,n,n',n'-tetrakis(p-dialkylaminophenyl)-p-benzoquinonebis(imonium perchlorate)Info
- Publication number
- JPH04202681A JPH04202681A JP2329817A JP32981790A JPH04202681A JP H04202681 A JPH04202681 A JP H04202681A JP 2329817 A JP2329817 A JP 2329817A JP 32981790 A JP32981790 A JP 32981790A JP H04202681 A JPH04202681 A JP H04202681A
- Authority
- JP
- Japan
- Prior art keywords
- perchlorate
- tetrakis
- dialkylaminophenyl
- amine
- current
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 15
- 150000001412 amines Chemical class 0.000 abstract description 14
- 239000006096 absorbing agent Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000000725 suspension Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 abstract description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- -1 silver hexafluoroantimonate Chemical compound 0.000 description 15
- 238000005868 electrolysis reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- IXGNPUSUVRTQGW-UHFFFAOYSA-M sodium;perchlorate;hydrate Chemical compound O.[Na+].[O-]Cl(=O)(=O)=O IXGNPUSUVRTQGW-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 101100207324 Arabidopsis thaliana TPPD gene Proteins 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- JPDUPGAVXNALOL-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetraphenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 JPDUPGAVXNALOL-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000863861 Xerodes Species 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 210000002837 heart atrium Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は赤外線吸収剤として有用なＮ、Ｎ、Ｎ’。[Detailed description of the invention] (Industrial application field) The present invention uses N, N, and N' useful as infrared absorbers.
Ｎ′−テトラキス（ｐ−ジアルキルアミノフェニル）−
ｐ−ベンゾキノンビス（イモニウム過塩素酸塩）の電解
酸化による製造方法に関する。N'-tetrakis(p-dialkylaminophenyl)-
The present invention relates to a method for producing p-benzoquinone bis(immonium perchlorate) by electrolytic oxidation.
（従来の技術）
Ｎ、Ｎ、Ｎ′、Ｎ″−テトラキス（ｐ−ジアルキルアミ
ノフェニル）−ｐ−フェニレンシアミンは、下記一般式
（Ｉ）（式中、Ｒはアルキル基を表す、）・・・（＋）
で表され、この化合物のアミニウム塩またはジイモニウ
ム塩は、赤外線吸収剤として有用であり、ヘキサフルオ
ロアンチモン酸銀または通塩素酸銀等の適当な酸の銀塩
を一般式（Ｎで表されるアミンと反応させる化学酸化法
によって製造される（特公昭４３−２５３３５号公報、
特公昭４５−１３３２６号公報）。しかし、この方法で
製造したものは、金属状銀が目的生成物中に微量混入す
ることがあり、このため赤外線吸収剤としての品質低下
をきたすという問題かあ）ノ、更に高価な銀塩を使用す
るため、製造コストがかさむという問題点があった。(Prior art) N,N,N',N''-tetrakis(p-dialkylaminophenyl)-p-phenylenecyamine has the following general formula (I) (wherein R represents an alkyl group). ... (+), and the aminium or diimonium salts of this compound are useful as infrared absorbers, and the silver salts of appropriate acids, such as silver hexafluoroantimonate or silver perchlorate, can be expressed by the general formula (N It is produced by a chemical oxidation method in which it is reacted with an amine represented by (Japanese Patent Publication No. 43-25335,
(Special Publication No. 45-13326). However, products produced using this method have the problem that a trace amount of metallic silver may be mixed into the target product, resulting in a decline in quality as an infrared absorber. There was a problem in that the manufacturing cost was high due to the use of this method.
電解酸化により製造する方法も提案されており、特公昭
４６−５８１０号公報には、Ｎ、Ｎ、Ｎ′、Ｎ゛−テト
ラフェニル−ｐ−フェニレンジアミン、ヘキサフルオロ
アンチモン酸アトリウムおよびアセトンからなる溶液を
陽極液に、ヘキサフルオロアンチモン酸ナトリウムおよ
びアセトンからなる溶液を陰極液に用い、隔膜を有する
電解槽中て電解酸化することによって、Ｎ、 Ｎ、 Ｎ
’、 Ｎ’−テトラフェニル−ｐ−ベンゾキノンビス（
イモニウムヘキサフルオロアンチモン酸塩）を得る方法
が開示されている。しかし、この方法は無機酸のアル刀
り金属塩を使用するために、陰極にこれらの金属状物が
付着し、このため抵抗値の増大を招き、生産効率を下げ
る欠点がある。また、隔膜電解槽を使用するため、無隔
膜のものと比較して複雑な装置を用いなければならない
という問題点がある。A method of manufacturing by electrolytic oxidation has also been proposed, and Japanese Patent Publication No. 46-5810 describes a solution consisting of N, N, N', N'-tetraphenyl-p-phenylenediamine, atrium hexafluoroantimonate, and acetone. By electrolytically oxidizing N, N,
', N'-tetraphenyl-p-benzoquinone bis(
A method for obtaining imonium hexafluoroantimonate) is disclosed. However, since this method uses an alkali metal salt of an inorganic acid, these metal-like substances adhere to the cathode, leading to an increase in resistance value and a drawback of lowering production efficiency. Furthermore, since a diaphragm electrolytic cell is used, there is a problem in that a more complicated device must be used than in a case without a diaphragm.
上記欠点を解決するため、無機酸のアルカリ金属塩の代
わりに、例えばヘキサフルオロアンチモジ酸および過塩
素酸等の無機酸あるいはそのアンモニウム塩を用いる方
法（特開昭６１−６９９９１号公報、特開昭６１−２４
６３９１号公報）、あるいは、反応液中に水、アルコー
ル等のプロトン源を共存させる方法（特開昭６３−２９
０２８８号公報）により、陰極への金属状物の付着を防
止する方法が提案されている。これらの方法は有用であ
るが、一般式（１）で表わされる化合物のアミニウム塩
を製造することを目的とするものであり、本発明の目的
物であるジイモニウム塩に関する記載はない。In order to solve the above drawbacks, a method using inorganic acids such as hexafluoroantimodic acid and perchloric acid or their ammonium salts instead of alkali metal salts of inorganic acids (JP-A No. 61-69991, JP-A No. 61-69991, 1986-24
6391), or a method in which a proton source such as water or alcohol is allowed to coexist in the reaction solution (Japanese Unexamined Patent Publication No. 63-29
Japanese Patent Publication No. 0288) proposes a method for preventing metal-like substances from adhering to the cathode. Although these methods are useful, they are aimed at producing the aminium salt of the compound represented by the general formula (1), and there is no description regarding the diimonium salt, which is the object of the present invention.
（発明が解決しようとする課題）
本発明は前記の従来の問題点を解決するためになされた
ものであり、Ｎ、Ｎ、Ｎ’、Ｎ”−テトラキス（ｐ−ジ
アルキルアミノフェニル）−ｐ−ベンゾキノンビス（イ
モニウム過塩素酸塩）を無隔膜電解槽を用い電解酸化法
により効率よく生産する方法を提供することを目的とす
る。(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned problems of the conventional art, and includes N,N,N',N''-tetrakis(p-dialkylaminophenyl)-p- The purpose of the present invention is to provide a method for efficiently producing benzoquinone bis(immonium perchlorate) by an electrolytic oxidation method using a membraneless electrolytic cell.
（課題を解決するための手段）
本発明者すは前記のような問題点を解決すべく検討を重
ねた結果、本発明を完成した。(Means for Solving the Problems) The present inventors have completed the present invention as a result of repeated studies to solve the above-mentioned problems.
即ち、本発明は一般式（１）
％式％（）
（式中、Ｒはアルキル基を表す。）で表わされるアミン
を、過塩素酸またはその塩の存在下、無隔膜電解槽中で
電解酸化することを特徴とする一般式（ｎ）
・・・（Ｕ）
（式中、Ｒはアルキル基を表す。）で表わされるＮ、Ｎ
、Ｎ’、Ｎ’−テトラキス（ｐ−ジアルキルアミノフェ
ニル）−ｐ−ベンゾキノンビス（イモニウム過塩素酸塩
）の製造方法である。That is, the present invention provides an amine represented by the general formula (1) % formula % (in the formula, R represents an alkyl group) in a non-diaphragm electrolytic cell in the presence of perchloric acid or a salt thereof. General formula (n) ... (U) (in the formula, R represents an alkyl group), which is characterized by oxidation, N, N
, N',N'-tetrakis(p-dialkylaminophenyl)-p-benzoquinone bis(immonium perchlorate).
本発明で原料として用いる一般式ＣＩ）で表わされるア
ミンは、例えば特公昭４５−１３３２６号公報等に記載
されている方法によって製造される。The amine represented by the general formula CI) used as a raw material in the present invention is produced, for example, by the method described in Japanese Patent Publication No. 13326/1983.
すなわち、ｐ−フェニレンシアミンとｐ−ニトロクロロ
ベンゼンとを炭酸カリウムの存在下で反応させ、Ｎ、
Ｎ、 Ｎ′、 Ｘ“−テトラキス（ｐ−ニトロフェニル
）−ｐ−フエニしンシアミンを得る。これをパラジウム
／カーボンを触媒として水添することによってＮ、 Ｎ
、 Ｎ ’ 、 Ｎ ’−テトラキス（ｐ−アミノフ
ェニル）−ｐ−フェニレンジアミンを製造する。That is, p-phenylenecyamine and p-nitrochlorobenzene are reacted in the presence of potassium carbonate, and N,
N, N',
, N', N'-tetrakis(p-aminophenyl)-p-phenylenediamine is produced.
更に、これを炭酸カリウムの存在下でｎ−アルキルヨー
シトと反応せしめると一般式（Ｉ）で表わされるアミン
が得られる。Further, by reacting this with n-alkyl ioside in the presence of potassium carbonate, an amine represented by general formula (I) is obtained.
一般式（Ｉ）および一般式（ＩＩ）中のＲとしては、メ
チル、エチル、プロピル、ブチル、ヘキシルおよびオク
チル等の直鎖または分岐鎖状のアルキル基を挙げること
ができる。Examples of R in the general formulas (I) and (II) include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and octyl.
本発明で使用する過塩素酸またはその塩としては、過塩
素酸ナトリウム、過塩素酸カリウム、過塩素酸リチウム
等を挙げることができ、その使用量は一般式（Ｉ）のア
ミンの量に対して２〜ｌｏ倍モルである。Examples of the perchloric acid or its salt used in the present invention include sodium perchlorate, potassium perchlorate, lithium perchlorate, etc., and the amount used is relative to the amount of the amine of general formula (I). It is 2 to 1 times mole.
本発明の目的物であるＮ、Ｎ、Ｎ’、Ｎ’−テトラキス
（ｐ−ジアルキルアミノフェニル）−ｐ−ヘンゾキノン
ビス（イモニウム過塩素酸塩）は、前記一般式（１）の
アミンと過塩素酸またはその塩とを溶剤に溶解または懸
濁させ、例えばヒーカー等の無隔膜槽に仕込み、あるい
は、複数の電極室を有するフィルタープレス型電解槽の
場合には、各電極室に溶液あるいは懸濁液を循環させな
がら通電し、電解酸化する二とにより得ることができる
。N,N,N',N'-tetrakis(p-dialkylaminophenyl)-p-henzoquinone bis(immonium perchlorate), which is the object of the present invention, is produced by combining the amine of the general formula (1) with perchloric acid. or its salt is dissolved or suspended in a solvent and charged into a non-diaphragm tank such as a heater, or in the case of a filter press type electrolytic tank having multiple electrode chambers, a solution or suspension is placed in each electrode chamber. It can be obtained by electrolytically oxidizing it by applying electricity while circulating it.
電解酸化時に用いる溶媒としては、原料としての一般式
（１）のアミンまたは目的物である一般式（１１）のビ
ス（イモニウム過塩素酸塩）を溶解し、かつ、安定に存
在せしめる有機溶剤であればよく、例λば、酢酸エチル
、酢酸メチル、アセトニトリル、クロロホルム、ジクロ
ロメタン、メタノールおよびアセトン等を挙げることが
でき、これらを犀独または混合して用いることができる
。また、電解中に電極に付着物か生成することを抑制し
、液抵抗を下げる目的で、前記有機溶媒に少量の水を添
加することができる。有機溶剤の使用量は、原料である
アミンに対して、重量比で２〜１００倍であり、水を添
加する場合には、有機溶剤に対して、重量比で０，００
５〜０．１倍である。The solvent used during electrolytic oxidation is an organic solvent that dissolves the amine of general formula (1) as a raw material or the bis(immonium perchlorate) of general formula (11) as a target product and allows it to exist stably. Examples of such solvents include ethyl acetate, methyl acetate, acetonitrile, chloroform, dichloromethane, methanol, and acetone, which may be used alone or in combination. Further, a small amount of water can be added to the organic solvent for the purpose of suppressing the formation of deposits on the electrodes during electrolysis and lowering the liquid resistance. The amount of organic solvent used is 2 to 100 times the weight ratio of the amine as a raw material, and when water is added, the amount of organic solvent used is 0.00 times the weight ratio of the organic solvent.
It is 5 to 0.1 times.
本発明の電解酸化に使用する電極（陰極および陽極）は
一般に使用されているものであればよく、例λば白金、
白金メツキチタン、チタンおよびカーボン電極等を埜げ
ることができる。The electrodes (cathode and anode) used in the electrolytic oxidation of the present invention may be any commonly used electrodes, such as platinum,
Platinum-plated titanium, titanium, carbon electrodes, etc. can be used.
本発明の電解酸化においては、通電量が理論通電量の５
０％を超えた付近から、定電流電解法においては徐々に
摺電圧の上昇が、定電圧電解法においては徐々に電流密
度の低下が見られる。In the electrolytic oxidation of the present invention, the amount of current applied is 5 of the theoretical amount of current applied.
From around 0%, the sliding voltage gradually increases in the constant current electrolysis method, and the current density gradually decreases in the constant voltage electrolysis method.
本発明の電解条件は極間距離、撹拌または循環速度、液
濃度等により異なり一概に定めることはできないが、例
えば、極間距離を１ｃｍとした場合、摺電圧は１〜３ｖ
とすることが好ましく、この時電流密度は、通常、０．
１〜２Ａ／ｄｍ’となる。極間距離が１ｃｍの場合に、
前記電圧範囲を越えた場合にも、原料アミンの濃度が約
４重量％（通常１〜２％程度）以下の低濃度であれば、
本発明の目的物であるビスイモニウム塩は生成するか、
それ以上の高濃度になると、理論通電量（２Ｆ／ｍｏｌ
）以上通電しても、一般式（１）のアミンのアミニウム
塩が生成するのみて、本発明の目的物であるビスイモニ
ウム塩は得られない。しかし、１バッチ当りの収量をあ
げることは工業的に極めて重要なことであるので、摺電
圧を前記電圧範囲に制御し、原料アミノの濃度をできる
たけ高濃度にして電解を行うことか好ましい。また、極
間距離を１ｃｍとした場合に、前記電圧範囲を下回ると
電解に長時間を要し、好ましくない。The electrolysis conditions of the present invention vary depending on the inter-electrode distance, stirring or circulation speed, liquid concentration, etc., and cannot be determined unconditionally, but for example, when the inter-electrode distance is 1 cm, the sliding voltage is 1 to 3 V.
It is preferable to set the current density at this time to 0.
1 to 2 A/dm'. When the distance between poles is 1cm,
Even when the voltage exceeds the above range, if the concentration of the raw amine is as low as about 4% by weight (usually about 1 to 2%),
Is the bisimonium salt that is the object of the present invention produced?
If the concentration is higher than that, the theoretical current flow amount (2F/mol
) Even if the current is applied above, only the aminium salt of the amine of general formula (1) is produced, but the bisimmonium salt which is the object of the present invention cannot be obtained. However, since it is extremely important industrially to increase the yield per batch, it is preferable to control the sliding voltage within the above voltage range and conduct electrolysis with the concentration of the raw material amino as high as possible. Further, when the distance between the electrodes is 1 cm, if the voltage is lower than the above range, the electrolysis takes a long time, which is not preferable.
従って、定電圧電解法においては、極間距離に応じて特
定される槽電圧範囲内に電圧を設定し、また、定電流電
解法においても極間距離に応して特定される槽電圧範囲
内に入るよう電流密度を設定し、更に、その槽電圧範囲
を維持するよう電流密度を適宜変化（通常、低下させる
）させながら摺電圧を制御し、電解することが好ましい
。Therefore, in constant voltage electrolysis, the voltage is set within the cell voltage range specified according to the distance between the electrodes, and in constant current electrolysis, the voltage is set within the cell voltage range specified according to the distance between the electrodes. It is preferable to electrolyze by setting the current density so that the current density falls within the cell voltage range, and controlling the sliding voltage while appropriately changing (usually lowering) the current density so as to maintain the cell voltage range.
電解温度は、通常、０〜４０°Ｃてあり、好ましくは２
０〜３０’Ｃ程度である。通常、電解温度が５０〜６０
℃程度になると、目的物を得ることが困難になるが、理
論通電量の５〜５０％を５０〜６０℃の温度で通電した
後、２０〜３０’Ｃの温度で更に理論通電量の７０〜１
４５％を通電する電解酸化法により目的物を得ることが
できる。このような通電法は、原料アミンの濃度が高い
場合にも溶液状態で電解反応を行うことができ、特に工
業的生産に適すると考えられるフィルタープレス型電解
槽な用いた場合での電解槽内での目づまりによるトラブ
ルを防止することかでき、有利である。The electrolysis temperature is usually 0 to 40°C, preferably 2°C.
It is about 0 to 30'C. Usually, the electrolysis temperature is 50-60
It becomes difficult to obtain the desired product when the temperature reaches about 100°C, but after applying 5 to 50% of the theoretical amount of current at a temperature of 50 to 60°C, an additional 70% of the theoretical amount of current is applied at a temperature of 20 to 30'C. ~1
The desired product can be obtained by an electrolytic oxidation method in which 45% current is applied. This energization method allows electrolytic reactions to be carried out in solution even when the raw material amine has a high concentration, and is particularly suitable for industrial production when using a filter press type electrolytic cell. This is advantageous because it can prevent troubles caused by clogging.
（実 施 例）
以下、実施例により本発明を更に詳細に説明するが、本
発明はこれらの例に限定されるものでない。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例］ 容量１００ｍ１の無隔膜電解槽に、Ｎ、Ｎ、Ｎ’。Example] N, N, N' in a diaphragmless electrolytic cell with a capacity of 100 m1.
Ｎ′−テトラキス（ｐ−シーｎ−ブチルアミノフェニル
）−ｐ−フェニレンシアミン（以下、ＴＰＰＤと略す）
５．５２ｇ （６ミリモル）、過塩素酸ナトリウム１
水和物５．０６ｇ （３６ミリモル）、酢酸エチル５０
ｇ、アセトニトリル２５ｇおよび水］ｇを仕込み懸濁液
を得た。この懸Ｉｆｉ液中に白金被覆チタン電極（日本
カーリット（株）製、商品名、エクセロードＡ、１．５
ｃｍＸ２，８ｃｍ）２枚を挿入して極間距離をＩｃｍと
し、室温において撹拌しながら初期電圧を２．ＩＶに設
定した。N'-tetrakis(p-cy n-butylaminophenyl)-p-phenylenecyamine (hereinafter abbreviated as TPPD)
5.52 g (6 mmol), sodium perchlorate 1
Hydrate 5.06g (36 mmol), ethyl acetate 50
g, 25 g of acetonitrile, and water] to obtain a suspension. Platinum-coated titanium electrode (manufactured by Nippon Carlit Co., Ltd., trade name, Exerode A, 1.5
cm x 2.8 cm) were inserted, the distance between the electrodes was set to I cm, and the initial voltage was set to 2.5 cm while stirring at room temperature. It was set to IV.
この時の電流密度は１．５Ａ／ｄｍ’であった。を解の
進行に伴い摺電圧は徐々に上昇し、２．８ｖになった時
点で、再び摺電圧が２．１＼・′になるように電流密度
を設定し直したく通電終了時には、０．３Ａ／ｃ１ｍ’
まで低下させた）。この操作を繰返し、１３８８クーロ
ン（理論通電量の１２０％）を通電した。The current density at this time was 1.5 A/dm'. As the solution progresses, the sliding voltage gradually increases, and when it reaches 2.8V, we want to reset the current density so that the sliding voltage becomes 2.1\' again. 3A/c1m'
). This operation was repeated to apply a current of 1388 coulombs (120% of the theoretical current amount).
通電終了後、反応液を水洗、濃縮し、ｎ−ヘキサンを添
加して析出した結晶を濾別乾燥し、Ｎ。After energization, the reaction solution was washed with water, concentrated, and added with n-hexane. The precipitated crystals were filtered and dried.
Ｎ、Ｎ″、Ｎ′−テトラキス（ｐ−ジ−ｎ−ブチルアミ
ノフェニル）−ｐ−ベンゾキノンビス（イモニウム過塩
素酸塩）５．２ｇ（収率７７％）を得た。5.2 g (yield 77%) of N,N'',N'-tetrakis(p-di-n-butylaminophenyl)-p-benzoquinone bis(immonium perchlorate) was obtained.
このもののアセトン中で測定したλｍａｘは１１０７５
ｎであった。The λmax of this product measured in acetone is 11075
It was n.
実施例２
実施例１と同様にして得た懸濁液を６０”Ｃに加温し内
容物を溶解させた。使用＠榛および極間距離を実施例１
と同一とし、摺電圧を２．０〜２．３Ｖに維持し、２０
０クーロン（理論通電量の１７％〕通電した。その後、
室温まで冷却し、更に１１８８クーロン（理論通電量の
１０３％）を通電した。その間、電流密度を１．５〜０
．３Ａ／ｄｍ′まで変化させた。通電終了後、反応液を
水中に投入し、析出した結晶を濾別乾燥し、Ｎ、Ｎ。Example 2 A suspension obtained in the same manner as in Example 1 was heated to 60"C to dissolve the contents. Use @Han and distance between poles as in Example 1.
is the same as that, the sliding voltage is maintained at 2.0 to 2.3V, and 20
0 coulombs (17% of the theoretical energization amount) was applied. After that,
It was cooled to room temperature, and a current of 1188 coulombs (103% of the theoretical current amount) was applied. Meanwhile, the current density is 1.5 to 0.
．． It was varied up to 3A/dm'. After energization, the reaction solution was poured into water, and the precipitated crystals were filtered and dried, and then washed with N and N.
Ｎ’、Ｎ’−テトラキス（ｐ−ジ−ｎ−ブチルアミノフ
ェニル）−ｐ−ベンゾキノンビス（イモニウム過塩素酸
塩）６．２ｇ （収率９２％）を得た。このもののアセ
トン中で測定したλｍａｘは１１０７５ｎであった。6.2 g (yield: 92%) of N',N'-tetrakis(p-di-n-butylaminophenyl)-p-benzoquinone bis(immonium perchlorate) was obtained. The λmax of this product measured in acetone was 11075n.
実施例３
０．６Ａ／ｄｍ″の電流密度で定電流電解（摺電圧は１
、６７’）’ ラ２ 、２ Ｖ ｉ：上昇）し、＋２
７４／７−ロン（理論通電量の１１０％）通電した以外
はすべて実施例】と同様に電解酸化を行い、Ｎ 、 Ｎ
、 Ｎ ’Ｎ ＋−テトラキス（ｐ−ジ−ｎ−ブチル
アミノフェニル）−ｐ−ヘンゾキノンビス（イモニウム
過塩素酸塩）６．１ｇ（収率９１％）を得た。このもの
のアセトン中で測定した２ｍ ａ ｘは１１０７５ｎて
あった。Example 3 Constant current electrolysis at a current density of 0.6 A/dm'' (sliding voltage is 1
, 67')' La 2 , 2 V i: rise) and +2
74/7-Electrolytic oxidation was carried out in the same manner as in [Example] except that current was applied at 110% of the theoretical energization amount, and N, N
, 6.1 g (yield 91%) of N'N+-tetrakis(p-di-n-butylaminophenyl)-p-henzoquinone bis(immonium perchlorate) was obtained. The 2 m a x measured in acetone was 11075 n.
比較例１
摺電圧を３．６〜３．１＼に維持し、電流密度を４．５
〜０．４９Ａ／ｄｍ″に変化させた以外はすべて実施例
１と同様に電解酸化を行った。その結果、本発明の目的
物であるビスイモニウム塩は得られず、ゴＰＰＤのアミ
ニウム塩、すなわちＮ。Comparative Example 1 The sliding voltage was maintained at 3.6 to 3.1\, and the current density was 4.5
Electrolytic oxidation was carried out in the same manner as in Example 1 except that the temperature was changed to ~0.49 A/dm''.As a result, the bisimmonium salt which is the object of the present invention was not obtained, but the aminium salt of GoPPD, i.e. N.
Ｎ、Ｎ’、Ｎ’−テトラキス（ｐ−シーｎ−ブチルアミ
ノフェニル〕−ｐ−フェニレンシアミン過塩素酸アンモ
ニウムが得られた。このもののアセトン中で測定したλ
ｍａｘは９５１ｎｍであった。Ammonium N,N',N'-tetrakis(p-cy n-butylaminophenyl)-p-phenylenecyamine perchlorate was obtained.
max was 951 nm.
実施例４
水を添加せず、過塩素酸ナトリウム１水和物の代りに６
０％過塩素酸水溶液６．０３ｇ （３６ミリモル）を使
用し、電流密度を０．６Ａ／ｄｍ’の定電流とし、摺電
圧を２．７〜２．２〜に維持した以外はすべて実施例１
と同様に電解酸化を行い、Ｎ、Ｎ、Ｎ’、Ｎ’−テトラ
キス（ｐ−ジーｎ−プチルアミノフェニル）−ｐ−ベン
ゾキノンビス（イモニウム過塩素酸塩）３．９ｇ（収率
５８％）を得た。Example 4 6 without adding water and instead of sodium perchlorate monohydrate
All examples except that 6.03 g (36 mmol) of 0% perchloric acid aqueous solution was used, the current density was set to a constant current of 0.6 A/dm', and the sliding voltage was maintained at 2.7 to 2.2. 1
Electrolytic oxidation was carried out in the same manner as above to obtain 3.9 g (yield 58%) of N,N,N',N'-tetrakis(p-di-n-butylaminophenyl)-p-benzoquinone bis(immonium perchlorate). I got it.
このもののアセトン中で測定したλｍａｘは１１０７５
ｎであった。The λmax of this product measured in acetone is 11075
It was n.
実施例５
ＴＰＰＤ７３．４ｇ （７９，６ミリモル）、過塩素酸
ナトリウム１水和物６７．３ ｇ （４７，９ミリモル
）、酢酸エチル６６５ｇ、アセトニトリル３３３ｇおよ
び水１３ｇを容量２Ｑのビーカーに仕込み、５５℃に加
温し電解液を調製した。Example 5 73.4 g (79.6 mmol) of TPPD, 67.3 g (47.9 mmol) of sodium perchlorate monohydrate, 665 g of ethyl acetate, 333 g of acetonitrile, and 13 g of water were placed in a beaker with a capacity of 2Q, and The electrolyte solution was prepared by heating to ℃.
両面に白金被覆を施したチタンを極（日本カーリット（
株）製、商品名 工クセロードＡ、１０ｃｍＸ１０ｃｍ
）の両面を、厚さ１ｃｍのガスケットを介して２枚の防
接（エクセロードＡ）で挾み込み、２室を構成したフィ
ルタープレス型電解槽の各電棲室に、先に調製した電解
液を循環させ、５５℃で３０００クーロン（理論通電量
の２０％）、その後室温で１８４００クーロン（理論通
電量の１２０％）を通電した。その間、摺電圧を２．１
〜２．４■に維持し、電流密度を１．８〜０．６Ａ／
ｄ ｍ″まで変化させた。通電終了後、実施例１と同様
に処理し、Ｎ 、 Ｎ 、 Ｎ ’ 、 Ｎ ’−テト
ラキス（ｐ−シーｎ−ブチルアミノフェニル）−ｐ−ベ
ンゾキノンビス（イモニウム過塩素酸塩）７５ｇ（１１
２率８４％）を得た。Titanium with platinum coating on both sides (Japan Carlit)
Co., Ltd., product name: Kuserod A, 10cmX10cm
) was sandwiched between two shields (Exerode A) via a 1 cm thick gasket, and the previously prepared electrolytic solution was placed in each electrolytic chamber of a filter press type electrolytic cell consisting of two chambers. The liquid was circulated, and a current of 3,000 coulombs (20% of the theoretical current amount) was applied at 55° C., and then a current of 18,400 coulombs (120% of the theoretical current amount) was applied at room temperature. During that time, increase the sliding voltage to 2.1
~2.4■, current density 1.8~0.6A/
After energization, the process was carried out in the same manner as in Example 1, and N, N, N', N'-tetrakis(p-cy n-butylaminophenyl)-p-benzoquinone bis(immonium filtrate) chlorate) 75g (11
2 rate of 84%) was obtained.
このもののアセトン中で測定したλｍａｘは］０７５ｎ
ｍであった。The λmax of this product measured in acetone is ]075n
It was m.
実施例６ 容量１００ｍ１の無隔膜電解槽に、Ｎ、Ｎ、Ｎ’。Example 6 N, N, N' in a diaphragmless electrolytic cell with a capacity of 100 m1.
Ｎｏ−テトラキス（ｐ−ジエチルアミノフェニル）−ｐ
−フェニレンシアミン４．１８ｇ（６ミリモル）、過塩
素酸ナトリウム１水和物５．０６ｇ （３６ミリモル）
、酢酸エチル５０ｇ、アセトニトリル２５ｇおよび水１
ｇを仕込んだ。ここに白金被覆チタン電極（日本カーリ
ット（株）製、商品名工クセロードＡ、１．５ｃｍｘ２
．８ｃｍ）２枚を挿入して極間距離を１ｃｍとし、摺電
圧を２．ＯＶに設定して定電圧電解し、室温において撹
拌しながら１２７４クーロン（理論通電量の１１０％）
を通電した。この間、電流密度はｌ 、 ３ Ａ ／
ｄ ｍ″から０．６Ａ／ｄｍ’まで低下した。No-tetrakis(p-diethylaminophenyl)-p
- 4.18 g (6 mmol) of phenylenecyamine, 5.06 g (36 mmol) of sodium perchlorate monohydrate
, ethyl acetate 50g, acetonitrile 25g and water 1
I prepared g. Here, a platinum-coated titanium electrode (manufactured by Nippon Carlit Co., Ltd., trade name: Xerode A, 1.5 cm x 2
．． 8cm) were inserted, the distance between the poles was 1cm, and the sliding voltage was set to 2. Electrolyze at constant voltage with the setting set to OV, and add 1274 coulombs (110% of the theoretical amount of current) while stirring at room temperature.
energized. During this time, the current density is l, 3 A/
d m'' to 0.6 A/dm'.
通電終了後、反応液を水洗、濃縮し、ｎ−ヘキサジを添
加して析出した結晶を濾別乾燥し、＼。After energization, the reaction solution was washed with water, concentrated, n-hexadiene was added, and the precipitated crystals were filtered and dried.
へ゛、Ｎ’、Ｎ’−テトラキス（ｐ−ジエチルアミノフ
ェニル）−ｐ−ベンゾキノンビス（イモニウム過塩素酸
塩）４．５ｇ（収率８４％）を得た。4.5 g (yield: 84%) of H,N',N'-tetrakis(p-diethylaminophenyl)-p-benzoquinone bis(immonium perchlorate) was obtained.
（発明の効果）
本発明の方法によって、Ｎ、Ｎ、Ｎ’、？Ｘ’Ｘチーラ
キス（ｐ−ジアルキルアミノフェニル）−ｐ−ベンゾキ
ノンビス（イモニウム過塩素酸塩）を効率良＜′＃！造
できるようになった。(Effect of the invention) By the method of the invention, N, N, N', ? X'X Thirakis (p-dialkylaminophenyl)-p-benzoquinone bis(immonium perchlorate) with high efficiency<'#! It is now possible to build.
特許出願人 日本カーリット株式会社Patent applicant Nippon Carlit Co., Ltd.
Claims (1)
を、過塩素酸またはその塩の存在下、無隔膜電解槽中で
電解酸化することを特徴とする一般式（II） ▲数式、化学式、表等があります▼・・・（II） （式中、Ｒはアルキル基を表す。）で表わされるＮ，Ｎ
，Ｎ’，Ｎ’−テトラキス（ｐ−ジアルキルアミノフェ
ニル）−ｐ−ベンゾキノンビス（イモニウム過塩素酸塩
）の製造方法。 ２、槽電圧を制御して電解酸化することを特徴とする請
求項１記載のＮ，Ｎ，Ｎ’，Ｎ’−テトラキス（ｐ−ジ
アルキルアミノフェニル）−ｐ−ベンゾキノンビス（イ
モニウム過塩素酸塩）の製造方法。 ３、理論通電量の５〜５０％を５０〜６０℃の温度で通
電した後、２０〜３０℃の温度で更に理論通電量の７０
〜１４５％を通電して電解酸化することを特徴とする請
求項１または２記載のＮ，Ｎ，Ｎ’，Ｎ−テトラキス（
ｐ−ジアルキルアミノフェニル）−ｐ−ベンゾキノンビ
ス（イモニウム過塩素酸塩）の製造方法。[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R represents an alkyl group). General formula (II) characterized by electrolytic oxidation in a non-diaphragm electrolytic cell in the presence of a salt thereof ▲Mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R is an alkyl group ) is represented by N, N
, N',N'-tetrakis(p-dialkylaminophenyl)-p-benzoquinone bis(immonium perchlorate). 2. The N,N,N',N'-tetrakis(p-dialkylaminophenyl)-p-benzoquinone bis(immonium perchlorate) according to claim 1, wherein the electrolytic oxidation is carried out by controlling the cell voltage. ) manufacturing method. 3. After applying 5 to 50% of the theoretical amount of current at a temperature of 50 to 60°C, further 70% of the theoretical amount of current applied at a temperature of 20 to 30°C.
N,N,N',N-tetrakis(
A method for producing p-dialkylaminophenyl)-p-benzoquinone bis(immonium perchlorate).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2329817A JP2965679B2 (en) | 1990-11-30 | 1990-11-30 | Method for producing N, N, N ', N'-tetrakis (p-dialkylaminophenyl) -p-benzoquinonebis (immonium perchlorate) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2329817A JP2965679B2 (en) | 1990-11-30 | 1990-11-30 | Method for producing N, N, N ', N'-tetrakis (p-dialkylaminophenyl) -p-benzoquinonebis (immonium perchlorate) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04202681A true JPH04202681A (en) | 1992-07-23 |
| JP2965679B2 JP2965679B2 (en) | 1999-10-18 |
Family
ID=18225565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2329817A Expired - Lifetime JP2965679B2 (en) | 1990-11-30 | 1990-11-30 | Method for producing N, N, N ', N'-tetrakis (p-dialkylaminophenyl) -p-benzoquinonebis (immonium perchlorate) |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2965679B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998051661A1 (en) * | 1997-05-14 | 1998-11-19 | Nippon Kayaku Kabushiki Kaisha | Aminium compounds and optical recording media containing the same |
| JP2007092060A (en) * | 2005-09-05 | 2007-04-12 | Fujifilm Corp | Method for producing near-infrared-absorbing colorant compound |
-
1990
- 1990-11-30 JP JP2329817A patent/JP2965679B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998051661A1 (en) * | 1997-05-14 | 1998-11-19 | Nippon Kayaku Kabushiki Kaisha | Aminium compounds and optical recording media containing the same |
| GB2340833A (en) * | 1997-05-14 | 2000-03-01 | Nippon Kayaku Kk | Aminium compounds and optical recording media containing the same |
| US6214435B1 (en) | 1997-05-14 | 2001-04-10 | Nippon Kayaku Kabushiki Kaisha | Aminium compounds and optical information recording media containing the same |
| GB2340833B (en) * | 1997-05-14 | 2001-06-13 | Nippon Kayaku Kk | Aminium compounds and optical recording media containing the same |
| JP2007092060A (en) * | 2005-09-05 | 2007-04-12 | Fujifilm Corp | Method for producing near-infrared-absorbing colorant compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2965679B2 (en) | 1999-10-18 |
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