JPS5837395B2 - Method for producing N,N-disubstituted-p-phenylenediamine derivative - Google Patents
Method for producing N,N-disubstituted-p-phenylenediamine derivativeInfo
- Publication number
- JPS5837395B2 JPS5837395B2 JP56008348A JP834881A JPS5837395B2 JP S5837395 B2 JPS5837395 B2 JP S5837395B2 JP 56008348 A JP56008348 A JP 56008348A JP 834881 A JP834881 A JP 834881A JP S5837395 B2 JPS5837395 B2 JP S5837395B2
- Authority
- JP
- Japan
- Prior art keywords
- disubstituted
- producing
- nitrosoaniline
- phenylenediamine
- cathode
- 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
Links
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】
本発明は、N,N−ジ置換一p−ニトロソアニリン誘導
体を還元してN,N−ジ置換一p−フエニレンジアミン
誘導体を効率良く製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for efficiently producing N,N-disubstituted p-phenylenediamine derivatives by reducing N,N-disubstituted p-nitrosoaniline derivatives.
N.N−ジ置換−p−フエニレンジアミン誘導体は、染
料の中間体、感光材料、写真薬品などとして有用な化合
物であるが、その合成法としては、従来N,N−ジアル
キルーp−ニトロソアニリンを多量の金属と鉱酸を用い
て還元する方法が一般的に行われている。N. N-disubstituted-p-phenylenediamine derivatives are compounds useful as dye intermediates, light-sensitive materials, photographic chemicals, etc., but their synthesis method has conventionally involved using a large amount of N,N-dialkyl-p-nitrosoaniline. A method of reduction using metals and mineral acids is commonly used.
しかし、この方法によると還元反応の排出液に金属塩が
含まれ、それを除去するのに繁雑な操作を必要とすると
いう欠点があった。However, this method has the drawback that the waste liquid from the reduction reaction contains metal salts and requires complicated operations to remove them.
本発明者らは、このような従来法の欠点を克服したN,
N−ジ置換−p−フエニレンジアミン誘導体の製造方法
を開発するため鋭意研究を重ねた結果、N,N−ジ置換
一p−ニトロソアニリン誘導体を電解還元することによ
り効率良<N,Nジ置換−p−フエニレンジアミンを製
造し得ることを見出し、この知見に基づいて本発明を完
戒するに至った。The present inventors have developed N, which overcomes the drawbacks of such conventional methods.
As a result of intensive research to develop a method for producing N-disubstituted p-phenylenediamine derivatives, we found that an efficient method for producing N,N-disubstituted p-nitrosoaniline derivatives was achieved by electrolytic reduction of N,N-disubstituted p-nitrosoaniline derivatives. It was discovered that substituted p-phenylenediamine could be produced, and based on this knowledge, the present invention was completed.
すなわち本発明は、一般式
(式中のR1及びR2はメチル、エチル、プロビル、ヒ
ドロキシメチル、ヒドロキシエチル及びヒドロキシプロ
ビル基からなる群から選ばれ、R3は、水素メチル及び
エチル基からなる群から選ばれるものである)
で表わされるN,N−ジ置換一p−ニトロソアニリン誘
導体を還元するに当り、水又はアルコール媒体中におい
て硫酸を支持電解質として電解還元を行うことを特徴と
する、一般式
(式中のRl , R2及びR3は前記と同じ意味をも
つ)で表わされるN,N−ジ置換一p−フエニレンジア
ミン誘導体の製造方法を提供するものである。That is, the present invention provides a general formula (wherein R1 and R2 are selected from the group consisting of methyl, ethyl, probyl, hydroxymethyl, hydroxyethyl and hydroxyprobyl groups, and R3 is selected from the group consisting of hydrogen methyl and ethyl groups) In reducing the N,N-disubstituted p-nitrosoaniline derivative represented by The present invention provides a method for producing an N,N-disubstituted mono-p-phenylenediamine derivative represented by the formula (wherein R1, R2, and R3 have the same meanings as above).
本発明方法は、隔膜を有する電解槽に支持電解質として
の硫酸を含む水あるいはアルコール(メタノール、エタ
ノール、プロパノールなどの低級アルコール)を媒体と
して装入し、陰極室に原料のN,N−ジ置換−p−ニト
ロソアニリン誘導体を加え、電位あるいは電流を規制し
ながら電解還元を行うことによって実施できる。In the method of the present invention, water or alcohol (lower alcohols such as methanol, ethanol, propanol, etc.) containing sulfuric acid as a supporting electrolyte is charged as a medium into an electrolytic cell having a diaphragm, and the N,N-displacement of the raw material is charged into the cathode chamber. This can be carried out by adding a -p-nitrosoaniline derivative and performing electrolytic reduction while regulating the potential or current.
この際、支持電解質としての硫酸の濃度は0、65〜1
0%がよい。At this time, the concentration of sulfuric acid as a supporting electrolyte is 0.65-1
0% is good.
本発明方法における電極としては、陰極には、銅、ニッ
ケル、ステンレス鋼、鉄、亜鉛、アルミニウム、モネル
合金、鉛、白金、炭素、真ちゅうなどが用いられる。As the electrode in the method of the present invention, copper, nickel, stainless steel, iron, zinc, aluminum, Monel alloy, lead, platinum, carbon, brass, etc. are used for the cathode.
また、陽極としては、炭素、鉛、白金などが用いられる
。Furthermore, carbon, lead, platinum, etc. are used as the anode.
参照電極としては、標準甘コウ電極、銀一塩化銀電極な
どが用いられる。As the reference electrode, a standard silver electrode, a silver monochloride electrode, or the like is used.
出発原料のN,N−ジ置換−p−ニトロソアニリン誘導
体の陰極室における濃度は通常0.3〜1.2%である
。The concentration of the starting material N,N-disubstituted p-nitrosoaniline derivative in the cathode chamber is usually 0.3 to 1.2%.
定電位電解における陰極への印加電圧は、還元波を示す
電位よりも0.1〜0,5vマイナス側が良い。The voltage applied to the cathode in constant potential electrolysis is preferably 0.1 to 0.5 V more negative than the potential that shows a reduction wave.
印加電圧が上記範囲よりプラス側の場合は、反応が十分
に進行せず、よりマイナス側の場合はエネルギー効率が
低下する。If the applied voltage is on the positive side of the above range, the reaction will not proceed sufficiently, and if it is more on the negative side, the energy efficiency will decrease.
定電流電解における電流密度は、0.001〜o. 0
2 A/iが適当である。The current density in constant current electrolysis is 0.001 to o. 0
2 A/i is appropriate.
電流密度が小さすぎる場合は反応時間が長くなり、大き
すぎる場合は副生物などのため選択率が低下する。If the current density is too small, the reaction time becomes long, and if it is too large, the selectivity decreases due to by-products.
通電量は、基質に対し、3.5〜6ファラデー/モルの
範囲である。The amount of current applied is in the range of 3.5 to 6 faradays/mol relative to the substrate.
反応温度は通常10〜40℃の範囲で行われる。The reaction temperature is usually in the range of 10 to 40°C.
本発明方法において電解還元反応の結果生じたN,N−
ジ置換−p−フエニレンジアミン誘導体は陰極液を常法
によって濃縮することにより、硫酸塩として分離できる
。N,N- produced as a result of the electrolytic reduction reaction in the method of the present invention
The disubstituted p-phenylenediamine derivative can be separated as a sulfate salt by concentrating the catholyte using a conventional method.
本発明方法によれば、比較的簡単な操作でN,N−ジ置
換−p−フエニレンジアミン誘導体を好収率かつ高純度
で得ることができる。According to the method of the present invention, N,N-disubstituted-p-phenylenediamine derivatives can be obtained in good yield and with high purity through relatively simple operations.
次に本発明を実施例に基づきさらに詳細に説明する。Next, the present invention will be explained in more detail based on examples.
実施例 1
10%硫酸水躊液50771lを装入した電解槽の、陰
極室に、N,N−ジメチルーp−ニトロソアニリン0.
15gを加え、銅板を陰極、炭素板を陽極とし、飽和甘
コウ電極を参照電極として、室温でよくかくはんしなが
ら、参照電極に対し一〇,65■の電圧を陰極に加え、
463クーロン通電して定電位電解還元を行った。Example 1 0.0% N,N-dimethyl-p-nitrosoaniline was added to the cathode chamber of an electrolytic cell charged with 50,771 liters of a 10% sulfuric acid aqueous solution.
15g was added, the copper plate was used as the cathode, the carbon plate was used as the anode, and the saturated sweetened electrode was used as the reference electrode.While stirring well at room temperature, a voltage of 10.65μ was applied to the cathode relative to the reference electrode.
Constant potential electrolytic reduction was performed by applying a current of 463 coulombs.
電解終了後陰極液を0.5N亜硝酸ナトリウム規定液で
ジアゾ滴定を行った結果、N,N−ジメチルーpニフエ
ニレンジアミンが収率80%で生成していることがわか
った。After the electrolysis was completed, the catholyte was subjected to diazo titration with a 0.5N normal sodium nitrite solution, and it was found that N,N-dimethyl-pniphenylenediamine was produced in a yield of 80%.
実施例 2
10%硫酸水醇液50TLlを装入した電解槽の、陰極
室に、N一エチルーN−ヒドロキシエチルーp−ニトロ
ソアニリン0.381を加え、銅板を陰極、白金板を陽
極として、室温でよくかくはんしながら、電流密度O.
OO5A/Cnlで772クーロン通電して定電流電解
還元を行った。Example 2 0.381 of N-ethyl-N-hydroxyethyl-p-nitrosoaniline was added to the cathode chamber of an electrolytic cell charged with 50 TL of 10% sulfuric acid aqueous solution, and the copper plate was used as the cathode and the platinum plate was used as the anode. While stirring well at room temperature, increase the current density to O.
Constant current electrolytic reduction was performed by applying a current of 772 coulombs using OO5A/Cnl.
陰極液を0.5N亜硝酸ナトリウム規定液でジアゾ滴定
を行った結果、N一エチルーN−ヒドロキシエチルーp
−フエニレンジアミンが収率83%で生威していること
が認められた。As a result of diazo titration of the catholyte with 0.5N sodium nitrite normal solution, N-ethyl-N-hydroxyethyl-p
- Phenylenediamine was found to be viable with a yield of 83%.
実施例 3
10%硫酸水溶液71ILlとメタノール1 0 0d
とを装入した電解槽の、陰極室に、N,N−ジメチルー
p−ニトロソアニリン0.3gを加え、ステンレス鋼板
を陰極、炭素板を陽極として、室温でよくかくはんしな
がら電流密度0.0 0 5 A/fflで772クー
ロン通電して定電流電解還元を行った。Example 3 10% sulfuric acid aqueous solution 71IL and methanol 100d
0.3 g of N,N-dimethyl-p-nitrosoaniline was added to the cathode chamber of the electrolytic cell charged with the above, and the stainless steel plate was used as the cathode and the carbon plate was used as the anode, and the current density was 0.0 while stirring well at room temperature. Constant current electrolytic reduction was carried out by applying a current of 772 coulombs at 0 5 A/ffl.
陰極液を0.5N亜硝酸ナl− IJウム規定液でジア
ゾ滴定を行った結果、N,N−ジメチルーp−フエニレ
ンジアミンが収率75%で生成していることが認められ
た。As a result of diazo titration of the catholyte with a 0.5N sodium nitrite normal solution, it was found that N,N-dimethyl-p-phenylenediamine was produced in a yield of 75%.
Claims (1)
ドロキシメチル、ヒドロキシエチル及びヒドロキシプロ
ビル基からなる群から選ばれ、R3は水素、メチル及び
エチル基からなる群から選はれるものである) !表わされるN,N−ジ置換−p−ニトロソアニリン誘
導体を還元するに当り、水又はアルコール媒体中におい
て硫酸を支持電解質として電解還元を行うことを特徴と
する、一般式 (式中のRl , R2及びR3は前記と同じ意未をも
つ)で表わされるN,N−ジ置換−p−フエニレンジア
ミン誘導体の製造方法。[Claims] 1 General formula (wherein R1 and R2 are selected from the group consisting of methyl, ethyl, probyl, hydroxymethyl, hydroxyethyl and hydroxyprobyl groups, and R3 is hydrogen, methyl and ethyl groups) (selected from the group)! In reducing the N,N-disubstituted-p-nitrosoaniline derivative represented by the general formula (Rl , R2 and R3 have the same meaning as above).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56008348A JPS5837395B2 (en) | 1981-01-21 | 1981-01-21 | Method for producing N,N-disubstituted-p-phenylenediamine derivative |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56008348A JPS5837395B2 (en) | 1981-01-21 | 1981-01-21 | Method for producing N,N-disubstituted-p-phenylenediamine derivative |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57123983A JPS57123983A (en) | 1982-08-02 |
JPS5837395B2 true JPS5837395B2 (en) | 1983-08-16 |
Family
ID=11690708
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56008348A Expired JPS5837395B2 (en) | 1981-01-21 | 1981-01-21 | Method for producing N,N-disubstituted-p-phenylenediamine derivative |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5837395B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60152797U (en) * | 1984-03-19 | 1985-10-11 | 三和シヤツタ−工業株式会社 | Horizontal pipe shutter |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4003194A1 (en) * | 1990-02-03 | 1991-08-08 | Boehringer Mannheim Gmbh | Electrochemical determn. of analytes - using oxido-reductase and substance of being reduced, which is re-oxidised on the electrode |
CN116103681B (en) * | 2023-02-02 | 2023-07-07 | 北京化工大学 | Copper-based monoatomic catalyst and preparation method thereof |
-
1981
- 1981-01-21 JP JP56008348A patent/JPS5837395B2/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60152797U (en) * | 1984-03-19 | 1985-10-11 | 三和シヤツタ−工業株式会社 | Horizontal pipe shutter |
Also Published As
Publication number | Publication date |
---|---|
JPS57123983A (en) | 1982-08-02 |
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