JPH0526876B2 - - Google Patents
Info
- Publication number
- JPH0526876B2 JPH0526876B2 JP60087453A JP8745385A JPH0526876B2 JP H0526876 B2 JPH0526876 B2 JP H0526876B2 JP 60087453 A JP60087453 A JP 60087453A JP 8745385 A JP8745385 A JP 8745385A JP H0526876 B2 JPH0526876 B2 JP H0526876B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- tetrakis
- silver
- phenylenediamine
- electrolytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- MBAKFIZHTUAVJN-UHFFFAOYSA-I hexafluoroantimony(1-);hydron Chemical compound F.F[Sb](F)(F)(F)F MBAKFIZHTUAVJN-UHFFFAOYSA-I 0.000 claims description 3
- 239000003495 polar organic solvent Substances 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- -1 silver hexafluoroantimonate Chemical compound 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical class CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical class NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- GVNSFLFOZIYBPH-UHFFFAOYSA-N 1-n,1-n-dibutyl-4-n-[4-[4-(dibutylamino)-n-[4-(dibutylamino)phenyl]anilino]phenyl]-4-n-[4-(dibutylamino)phenyl]benzene-1,4-diamine Chemical compound C1=CC(N(CCCC)CCCC)=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC(=CC=1)N(CCCC)CCCC)C=1C=CC(=CC=1)N(CCCC)CCCC)C1=CC=C(N(CCCC)CCCC)C=C1 GVNSFLFOZIYBPH-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- TXSCFCYZNFQPEQ-UHFFFAOYSA-N 4-n-[4-[4-(dihexylamino)-n-[4-(dihexylamino)phenyl]anilino]phenyl]-4-n-[4-(dihexylamino)phenyl]-1-n,1-n-dihexylbenzene-1,4-diamine Chemical compound C1=CC(N(CCCCCC)CCCCCC)=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC(=CC=1)N(CCCCCC)CCCCCC)C=1C=CC(=CC=1)N(CCCCCC)CCCCCC)C1=CC=C(N(CCCCCC)CCCCCC)C=C1 TXSCFCYZNFQPEQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は電解酸化法によるアミニウム塩の製法
に関する。更に詳しくは電解酸化法によるＮ，
Ｎ，N′，N′−テトラキス（ｐ−ジアルキルアミ
ノフエニル）−ｐ−フエニレンジアミン類のアミ
ニウム塩の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing aminium salts by electrolytic oxidation. More specifically, N by electrolytic oxidation method,
The present invention relates to a method for producing aminium salts of N,N',N'-tetrakis(p-dialkylaminophenyl)-p-phenylenediamines.
従来の技術
Ｎ，Ｎ，N′，N′−テトラキス（ｐ−ジアルキ
ルアミノフエニル）−ｐ−フエニレンジアミン類
のアミニウム塩は赤外領域に強い吸収を示すので
赤外線吸収剤として多用されている。Prior Art Aminium salts of N,N,N',N'-tetrakis(p-dialkylaminophenyl)-p-phenylenediamines exhibit strong absorption in the infrared region, and are therefore frequently used as infrared absorbers. .
Ｎ，Ｎ，N′，N′−テトラキス（ｐ−ジアルキ
ルアミノフエニル）−ｐ−フエニレンジアミン類
のアミニウム塩は一般的にはヘキサフロロアンチ
モン酸銀又は過塩素酸を用いて銀の酸化力を利用
する化学的酸化法で製造されている。例えば特公
昭43−25335にはヘキサフロロアンチモン酸銀を
用いるＮ，Ｎ，N′，N′−テトキラス（ｐ−ジア
ルキルアミノフエニル）−ｐ−フエニレンジアミ
ン類の製法の記載がある。 Aminium salts of N,N,N',N'-tetrakis(p-dialkylaminophenyl)-p-phenylenediamines are generally prepared using silver hexafluoroantimonate or perchloric acid to reduce the oxidizing power of silver. It is manufactured using a chemical oxidation method using For example, Japanese Patent Publication No. 43-25335 describes a method for producing N,N,N',N'-tetochilas(p-dialkylaminophenyl)-p-phenylenediamines using silver hexafluoroantimonate.
なお特公昭46−5810には電解酸化法によるＮ，
Ｎ，N′，N′−テトラフエニル−ｐ−Ｐ−フエニ
ル−ベンゾキノンビスイモニウムヘキサフルオロ
アンチモン酸ナトリウムの製法の記載があるが
Ｎ，Ｎ，N′，N′−テトラキス（ｐ−ジアルキル
アミノフエニル）−ｐ−フエニレンジアミン類の
アミニウム塩の製法に関する記載はない。又同方
法による場合は使用するヘキサフルオロアンチモ
ン酸ナトリウムが還元されて金属状ナトリウムが
陰極に付着して生産効率を下げるという欠点があ
る。 In addition, in the special publication 1986-5810, N, by electrolytic oxidation method,
N,N',N'-tetrakis(p-dialkylaminophenyl) )-There is no description regarding the method for producing aminium salts of p-phenylenediamines. Furthermore, when using the same method, there is a drawback that the sodium hexafluoroantimonate used is reduced and metallic sodium adheres to the cathode, reducing production efficiency.
発明が解決しようとする問題点
銀の化合物を使用する前記したような化学的方
法においては高価な銀化合物の使用を必要とする
ので製造コストが必然的に高価になる。又、反応
の結果、生成する金属銀は過等の操作で取り除
くことが必要であり、生産性低下の原因となる。
さらには製品中に微量でも銀が混入すると赤外線
吸収剤としての品質低下を招くので金属銀が製品
中に混入しないように特別な配慮が必要である。
なお金属塩を用いる電解法は陰極への金属析出が
生じ生産効率の低下はさけられない。Problems to be Solved by the Invention The above-mentioned chemical method using a silver compound requires the use of an expensive silver compound, and therefore the manufacturing cost is inevitably high. Furthermore, it is necessary to remove metallic silver produced as a result of the reaction by excessive operations, which causes a decrease in productivity.
Furthermore, if even a small amount of silver is mixed into the product, the quality of the product as an infrared absorber will deteriorate, so special care must be taken to prevent metallic silver from being mixed into the product.
In addition, in the electrolytic method using a metal salt, metal precipitation occurs on the cathode, and a decrease in production efficiency cannot be avoided.
問題点を解決する為の手段
Ｎ，Ｎ，N′，N′−テトラキス（ｐ−ジアルキ
ルアミノ）−ｐ−フエニレンジアミン類のアミニ
ウム塩を製造するにあたつて前記したような欠点
のない製法を見出すべく鋭意研究を重ねた結果本
発明を完成させた。即ち本発明は式(1)で
（式(1)中R1〜8はアルキル基を示す）
で表わされる化合物を隔膜を有する電解槽を用い
極性有機溶媒中ヘキサフロロアンチモン酸又は過
塩素酸の存在下電解酸化することを特徴とする式
(2)
（式(2)R1〜8はアルキル基、ＡはSbF6、ClO4を示
す。）
で表わされるアミニウム塩の製法を提供するもの
である。Means for Solving the Problems: A process for producing aminium salts of N,N,N',N'-tetrakis(p-dialkylamino)-p-phenylenediamines that does not have the above-mentioned drawbacks. The present invention has been completed as a result of intensive research to find out. That is, in the present invention, the formula (1) (In formula (1), R 1 to 8 represent an alkyl group) is electrolytically oxidized in the presence of hexafluoroantimonic acid or perchloric acid in a polar organic solvent using an electrolytic cell having a diaphragm. formula to
(2) (Formula (2) R 1 to 8 are alkyl groups, and A represents SbF 6 or ClO 4 ).
本発明において原料として用いられる式(1)で示
されるアミン類の具体的な例としては、次のもの
が挙げられる。 Specific examples of the amines represented by formula (1) used as raw materials in the present invention include the following.
又本発明の方法で使用される極性有機溶剤とし
てはDMFが最も好ましいがメタノール、エタノ
ール、ブタノール、プロパノール、イソプロパノ
ール等のアルコール類、アセトン、メチルイソブ
チルケトン、メチルエチルケトン等のケトン類の
他にメチルセロソルブ、エチルセロソルブ、
DMSO、ジメチルアセトアミド、Ｎ−メチルピ
ロリドン、ピリジン、或はそれらの混合物が使用
出来る。その使用量は反応基質に対して１〜50倍
（重量比）である。又それらの溶媒は少量の水を
含んでいてもよい。電解槽は隔膜で陽極と陰極を
隔離した２室型のものが使用される、隔膜材料と
しては半融ガラス、石綿、素焼板、「ナフイオン」
（イオン交換樹脂膜、Dupont社製）「セレミオン」
（イオン交換樹脂膜、旭ガラス製）等が使用され
る。電極材料は陽極としては、炭素、白金、白金
メツキされたもの（例えばチタンに白金メツキし
たもの）金、「DSE」（酸化ルテニウム系電極、
ペルメレツクス電極株式会社製）等であり、陰極
としては白金、白金メツキしたもの（例えばチタ
ンに白金メツキしたもの）、銀、鉛、銅、鉄、ニ
ツケル、ステンレス鋼等が使用される。 The polar organic solvent used in the method of the present invention is most preferably DMF, but alcohols such as methanol, ethanol, butanol, propanol, and isopropanol, ketones such as acetone, methyl isobutyl ketone, and methyl ethyl ketone, as well as methyl cellosolve, ethyl cellosolve,
DMSO, dimethylacetamide, N-methylpyrrolidone, pyridine, or mixtures thereof can be used. The amount used is 1 to 50 times (weight ratio) the amount of the reaction substrate. These solvents may also contain small amounts of water. The electrolytic cell used is a two-chamber type in which the anode and cathode are separated by a diaphragm.The diaphragm materials include smelt glass, asbestos, terracotta, and "nafion".
(Ion exchange resin membrane, manufactured by Dupont) "Celemion"
(ion exchange resin membrane, manufactured by Asahi Glass), etc. are used. Electrode materials for the anode include carbon, platinum, platinum plated (for example, titanium plated with platinum), gold, "DSE" (ruthenium oxide based electrode,
(manufactured by Permerex Electrode Co., Ltd.), and platinum, platinum-plated material (for example, titanium plated with platinum), silver, lead, copper, iron, nickel, stainless steel, etc. are used as the cathode.
電解酸化は任意の電流密度で行われるが好まし
くは５ｍＡ／cm2〜100ｍＡ／cm2が良い。電解温度
は使用する有機溶剤によつても異なるが０〜50℃
で行うのが好ましい。通常使用する溶媒の沸点よ
り低い温度で行われる。電解酸化に必要とされる
電気量は理論量（1F／mol）で良いが薄層クロマ
トグラフイー等で反応をチエツクし必要に応じて
加減する。電解槽は電解反応中に電解系を均一に
するため適度な液流を与えるための撹拌装置を設
けたものが好ましい。ヘキサフロロアンチモン酸
は、６水和物が入手しやすく好んで使用されるが
水溶液でもかまわない。その使用量は反応基質に
対して１〜30倍モルである。又過塩素酸は取り扱
いの点より低濃度の水溶液として用いられ、その
使用量は反応基質に対して１〜30倍モルである。 Electrolytic oxidation may be carried out at any current density, preferably 5 mA/cm 2 to 100 mA/cm 2 . The electrolysis temperature varies depending on the organic solvent used, but is 0 to 50℃.
It is preferable to do so. It is usually carried out at a temperature below the boiling point of the solvent used. The amount of electricity required for electrolytic oxidation may be the theoretical amount (1F/mol), but the reaction should be checked using thin layer chromatography or the like and adjusted as necessary. The electrolytic cell is preferably equipped with a stirring device to provide an appropriate flow of liquid in order to make the electrolytic system uniform during the electrolytic reaction. Hexafluoroantimonic acid is preferably used as a hexahydrate because it is readily available, but an aqueous solution may also be used. The amount used is 1 to 30 times the amount of the reaction substrate. In addition, perchloric acid is used in the form of a low concentration aqueous solution from the viewpoint of handling, and the amount used is 1 to 30 times the mole of the reaction substrate.
本発明の方法によつて化学的方法におけるよう
な製品中への銀の混入のおそれのない式(2)で表わ
されるアミニウム塩を効率よく得ることができ
る。 By the method of the present invention, it is possible to efficiently obtain an aminium salt represented by formula (2) without the risk of contamination of silver into the product as is the case with chemical methods.
実施例
以下実施例により本発明を更に詳細に説明す
る。EXAMPLES The present invention will be explained in more detail with reference to Examples below.
実施例 １
グラスフイルターにより陽極室と陰極室に隔離
されたＨ型セルの陽極室にDMF45ml、ヘキサフ
ロロアンチモン酸の６水和物４ml（0.0145モル）
Ｎ，Ｎ，N′，N′−テトラキス（ｐ−ジｎ−ヘキ
シルアミノフエニル）−ｐ−フエニレンジアミン
2.29ｇ（0.002モル）陰極室にDMF45mlヘキサフ
ロロアンチモン酸の６水和物４mlを加え、次に
1.5×２cmの白金板を陽、陰極両室に設ける。温
度38℃端子間電圧36〜38Vで撹拌下に電流値50ｍ
Ａで203クーロンの電気量を流し電解酸化した。
その後炭酸ナトリウム２ｇを加え２分間撹拌した
後水５mlを滴下し過、水洗、乾燥することによ
つて2.54ｇ（収率92％）の緑色結晶を得た。本品
はヘキサフロロアンチモン酸銀を用いて合成した
標品と赤外吸収波形が完全に一致し（λmax950n
ｍ、アセトン）次の構造を有することが確かめら
れた。Example 1 45 ml of DMF and 4 ml (0.0145 mol) of hexafluoroantimonic acid hexahydrate were placed in the anode chamber of an H-type cell separated by a glass filter into an anode chamber and a cathode chamber.
N,N,N',N'-tetrakis(p-di-n-hexylaminophenyl)-p-phenylenediamine
Add 2.29 g (0.002 mol) of DMF (45 ml) and 4 ml of hexafluoroantimonic acid hexahydrate to the cathode chamber, then
A 1.5 x 2 cm platinum plate is installed in both the anode and cathode chambers. Temperature: 38℃, voltage between terminals: 36 to 38V, current value: 50m while stirring
Electrolytic oxidation was carried out by flowing electricity of 203 coulombs at A.
Thereafter, 2 g of sodium carbonate was added, and after stirring for 2 minutes, 5 ml of water was added dropwise, filtered, washed with water, and dried to obtain 2.54 g (yield: 92%) of green crystals. The infrared absorption waveform of this product completely matches that of the standard product synthesized using silver hexafluoroantimonate (λmax950n
m, acetone) was confirmed to have the following structure.
実施例 ２
実施例１でＮ，Ｎ，N′，N′−テトラキス（ｐ
−ジ−ｎ−ヘキシルアミノフエニル）−ｐ−フエ
ニレンジアミンの代わりにＮ，Ｎ，N′，N′−テ
トラキス（ｐ−ジ−ｎ−ブチルアミノフエニル）
−ｐ−フエニレンジアミンを用い、同様に電解酸
化を行下記構造式の緑色結晶を収率89％で得た。
本品はλmax950nｍ（アセトン中）m.p.125〜133
℃であつた。 Example 2 In Example 1, N,N,N',N'-tetrakis (p
N,N,N',N'-tetrakis(p-di-n-butylaminophenyl) instead of -di-n-hexylaminophenyl)-p-phenylenediamine
Electrolytic oxidation was carried out in the same manner using -p-phenylenediamine to obtain green crystals having the following structural formula in a yield of 89%.
This product is λmax950nm (in acetone) mp125-133
It was warm at ℃.
実施例 ３
実施例１と同じ装置を用いて、Ｎ，Ｎ，N′，
N′−テトラキス（ｐ−ジ−ｎ−ブチルアミノフ
エニル）−ｐ−フエニレンジアミン1.84ｇ（0.002
モル）DMF45ml、60％HClO4（0.024モル）４ｇ
を陽極室に加える。陰極室にはDMF45mlと60％
HClO44ｇを加え35℃40ｍＡで192クーロンの電
気量を流した。 Example 3 Using the same equipment as in Example 1, N, N, N',
N'-tetrakis(p-di-n-butylaminophenyl)-p-phenylenediamine 1.84g (0.002
mol) DMF 45 ml, 60% HClO 4 (0.024 mol) 4 g
is added to the anode chamber. DMF 45ml and 60% in the cathode chamber
4 g of HClO 4 was added and 192 coulombs of electricity was applied at 35° C. and 40 mA.
その後炭酸ナトリウム２ｇを加え５分間撹拌し
た後、水５mlを加え過、水洗、乾燥することで
下記構造式の緑色結晶1.80ｇ（収率88.3％）を得
た。本品はλmax950nｍ（アセトン）m.p.152〜
７℃であつた。 Thereafter, 2 g of sodium carbonate was added and the mixture was stirred for 5 minutes, then 5 ml of water was added, filtered, washed with water, and dried to obtain 1.80 g of green crystals (yield: 88.3%) having the following structural formula. This product has a wavelength of λmax950nm (acetone) mp152~
It was 7℃.
実施例 ４
実施例１においてＮ，Ｎ，N′，N′−テトラキ
ス（ｐ−ジ−ｎ−ヘキシルアミノフエニル）−ｐ
−フエニレンジアミン2.29ｇの代わりにＮ，Ｎ，
N′，N′−テトラキス（ｐ−ジ−ｎ−オクチルア
ミノフエニル）−ｐ−フエニレンジアミン2.74ｇ
を用いて実施例１と同様に電解酸化を行い次の化
合物を収率89％（λmax950nｍ、アセトン）でえ
た。 Example 4 In Example 1, N,N,N',N'-tetrakis(p-di-n-hexylaminophenyl)-p
-N, N, instead of 2.29 g of phenylenediamine
N',N'-tetrakis(p-di-n-octylaminophenyl)-p-phenylenediamine 2.74g
Electrolytic oxidation was carried out in the same manner as in Example 1 using the following compound, and the following compound was obtained in a yield of 89% (λmax 950 nm, acetone).
実施例 ５
実施例１においてＮ，Ｎ，N′，N′−テトラキ
ス（ｐ−ジ−ｎ−ヘキシルアミノフエニル（ｐ−
フエニレンジアミン2.29ｇの代わりにＮ，Ｎ，
N′，N′−テトラキス（ｐ−ジメチルアミノフエ
ニル）−ｐ−フエニレンジアミン1.17ｇを用いて
実施例１と同様に電解酸化を行い次の化合物を収
率88.5％（λmax950nｍアセトン）で得た。 Example 5 In Example 1, N,N,N',N'-tetrakis (p-di-n-hexylaminophenyl (p-
N, N, instead of 2.29g of phenylenediamine
Electrolytic oxidation was performed in the same manner as in Example 1 using 1.17 g of N',N'-tetrakis(p-dimethylaminophenyl)-p-phenylenediamine to obtain the following compound in a yield of 88.5% (λmax 950nm acetone). Ta.
「発明の効果」
本発明の方法によつて銀の混入のないＮ，Ｎ，
N′，N′−テトラキス（ｐ−ジアルキルアミノ）−
ｐ−フエニレンジアミンのアミニウム塩を効率よ
く製造することが出来る。 "Effect of the invention" By the method of the present invention, N, N, and
N′,N′-tetrakis(p-dialkylamino)-
Aminium salts of p-phenylenediamine can be efficiently produced.
Claims (1)
極性有機溶媒中、ヘキサフロロアンチモン酸又は
過塩素酸の存在下電解酸化することを特徴とする
式(2) ２ 式 （式(2)中ＡはSbF6 -又はClO4 -を示す。R1〜8は式
(1)と同じ意味を表わす） で表わされるアミニウム塩の製法。[Claims] 1 Formula (1) (In formula (1), R 1 to 8 represent an alkyl group) is electrolytically oxidized in a polar organic solvent in the presence of hexafluoroantimonic acid or perchloric acid using an electrolytic cell having a diaphragm. Equation (2) 2 Equation (A in formula (2) represents SbF 6 - or ClO 4 - . R 1 to 8 are formula
(same meaning as (1))
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60087453A JPS61246391A (en) | 1985-04-25 | 1985-04-25 | Production of aminium salt of n,n,n',n'-tetrakis(p-dialkylaminophenyl)-p-phenylenediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60087453A JPS61246391A (en) | 1985-04-25 | 1985-04-25 | Production of aminium salt of n,n,n',n'-tetrakis(p-dialkylaminophenyl)-p-phenylenediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61246391A JPS61246391A (en) | 1986-11-01 |
| JPH0526876B2 true JPH0526876B2 (en) | 1993-04-19 |
Family
ID=13915276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60087453A Granted JPS61246391A (en) | 1985-04-25 | 1985-04-25 | Production of aminium salt of n,n,n',n'-tetrakis(p-dialkylaminophenyl)-p-phenylenediamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61246391A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06956B2 (en) * | 1987-05-22 | 1994-01-05 | 帝国化学産業株式会社 | Process for producing N, N, N ', N'-tetrakis (p-dialkylaminophenyl) -p-phenylenediamine aminium salt |
| US5436011A (en) * | 1993-04-16 | 1995-07-25 | Bristol-Myers Squibb Company | Solid pharmaceutical dosage form and a method for reducing abrasion |
| US7473802B2 (en) | 2005-09-05 | 2009-01-06 | Fujifilm Corporation | Method of producing near-infrared absorbing dye compound |
| JP2007070476A (en) | 2005-09-07 | 2007-03-22 | Fujifilm Corp | Method for preparing near infrared ray absorption coloring matter compound |
| CN114242318A (en) * | 2019-06-20 | 2022-03-25 | 广西纵览线缆集团有限公司 | Heat insulation composite cable |
| CN114316416B (en) * | 2019-06-20 | 2023-03-21 | 广西纵览线缆集团有限公司 | Low-smoke halogen-free flame-retardant low-voltage cable |
-
1985
- 1985-04-25 JP JP60087453A patent/JPS61246391A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61246391A (en) | 1986-11-01 |
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