JPS5859950A - Preparation of diphenylamines - Google Patents

Preparation of diphenylamines

Info

Publication number
JPS5859950A
JPS5859950A JP56158057A JP15805781A JPS5859950A JP S5859950 A JPS5859950 A JP S5859950A JP 56158057 A JP56158057 A JP 56158057A JP 15805781 A JP15805781 A JP 15805781A JP S5859950 A JPS5859950 A JP S5859950A
Authority
JP
Japan
Prior art keywords
formula
compound shown
compound
ethyl
acid binder
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
Application number
JP56158057A
Other languages
Japanese (ja)
Inventor
Haruki Niimoto
昭樹 新本
Tatsuya Numa
達也 沼
Masaharu Nomura
正治 野村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Priority to JP56158057A priority Critical patent/JPS5859950A/en
Publication of JPS5859950A publication Critical patent/JPS5859950A/en
Pending legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate for a dyestuff of pressure-sensitive copying paper inexpensively in high purity, by reacting an acylaminophenol with dichlorobenzene or trichlorobenzene in the presence of both an acid binder and a copper catalyst, followed by hydrolysis. CONSTITUTION:A compound shown by the formulaI(R1 is methyl or ethyl; R2 is H, ethyl, propyl, butyl, or phenyl) is reacted with a compound shown by the formula II (n is 1 or 2) in the presence of an acid binder (e.g., magnesium oxide) and a copper catalyst (e.g., cupric oxide) to give a compound shown by the formula III, which is hydrolyzed to give the desired compound shown by the formula IV. The reaction is carried out at 150-250 deg.C for 24-40hr, the amount of the copper catalyst used is 0.1-1.0mol, preferably 0.3-0.5mol based on the compound shown by the formulaI, and the amount of the acid binder is 0.8- 1.4mol based on the compound shown by the formulaI.

Description

【発明の詳細な説明】 本発明は （１）式 ％式％（） （式中Ｒ１はメチル又はエチルを表わす。Ｒ２ハ水素、
エチル、プロピル、ブチル又はフェニルを表わす。） で表わされる化合物を酸結合剤及び銅触媒の存在下式 ％式％ （式中ｎは１又は２を表わす。） で表わされる化合物と反応させることを特徴（式中Ｆｔ
ｌｌ＆Ｉｎは前記と同じもやを意味する。） で表わされる化合物の製造法及び （２）式 ％式％（） （式中Ｒ１はメチル又はエチルを表わす。Ｒ２ハ水素、
エチル、プロピル、ブチル、又ハフェニルを表わす。） で表わされる化合物を酸結合剤及び銅触媒の（式中ｎは
１又１ｌ−１１２ｔ−表わす。）で表わされる化合物と
反応させ式 （式中Ｒ１，Ｒ２，ｎは前記と同じものを意味する。） で表わされる化合物を得、ついで式［相］の化合物を加
水分解することを特徴とする式 ０式％ （式中Ｒ，，ｎは前記と同じものを意味する。）で表わ
される化合物の製造法に関する。式■のジフェニルアミ
ン化合物は感熱紙及び感圧復写紙用色素の中間体として
特に有用な化合物であり式［相］の化合物は式■の化合
物の原料として重要なものである。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on (1) the formula % formula % () (in the formula, R1 represents methyl or ethyl; R2 represents hydrogen;
Represents ethyl, propyl, butyl or phenyl. ) in the presence of an acid binder and a copper catalyst with a compound represented by formula % (wherein n represents 1 or 2) (wherein Ft
ll&In means the same haze as above. ) and (2) formula % formula % () (in the formula, R1 represents methyl or ethyl; R2 represents hydrogen;
Represents ethyl, propyl, butyl, or haphenyl. ) is reacted with an acid binder and a copper catalyst (in the formula, n represents 1 or 1l-112t-) to form a compound represented by the formula (in the formula, R1, R2, and n have the same meanings as above). ) is obtained, and then the compound of formula [phase] is hydrolyzed. Concerning a method for producing a compound. The diphenylamine compound of formula (1) is particularly useful as an intermediate for dyes for thermal paper and pressure-sensitive copying paper, and the compound of formula [phase] is important as a raw material for the compound of formula (2).

特開昭４９−３４５２６号公報によれば式■の化合物は
下記の方法によって製造されてい（上記式中Ｒ１はメチ
ル又はエチルｆ　、Ｒｔは１又は２を表わす。） しかしながら、上記製造法は。According to JP-A No. 49-34526, the compound of formula (1) is produced by the following method (in the above formula, R1 represents methyl or ethyl f, and Rt represents 1 or 2).

■　原料である式■の臭素化物は高価でかつ一般に入手
困難である。(2) The brominated compound of formula (2), which is a raw material, is expensive and generally difficult to obtain.

■　得られた式■の生成物は、臭素体と塩素体の混合物
であり、純品が得にくい。(2) The obtained product of formula (2) is a mixture of bromine and chloride, and it is difficult to obtain a pure product.

という欠点を有している。従って、上記製造法は式ので
表わされるジフェニルアミン化合物を純度よく、工業的
に安価に得る方法として適当でない。It has the following drawbacks. Therefore, the above production method is not suitable as a method for obtaining the diphenylamine compound represented by the formula with high purity and at low cost industrially.

ところで、従来よりベンゼン核の塩素は臭素よりも反応
性がはるかに劣るとされている。By the way, it has been conventionally believed that the reactivity of chlorine in the benzene nucleus is much lower than that of bromine.

しかし本発明者は式（２）の塩素化合物が意外にも式（
Ｉ）の化合物と充分に反応することを見出した。そして
本発明により臭素化合物Ｍに替る原料として、工業的に
安価で人手も容易な弐■のジクロルベンゼン類及びトリ
クロルベンゼン類を用いて１式■で表わされるジフェニ
ルアミン化合物が安価で純度良く得られることを見出し
た。However, the present inventor discovered that the chlorine compound of formula (2) was unexpectedly expressed by the formula (
It has been found that it reacts satisfactorily with the compound I). According to the present invention, the diphenylamine compound represented by Formula 1 (1) can be obtained at low cost and with high purity by using dichlorobenzenes and trichlorobenzenes (2), which are industrially inexpensive and easy to use, as raw materials to replace bromine compound M. I discovered that.

次に本発明を以下に説明する。Next, the present invention will be explained below.

先ず式（Ｉ）のアシルアミノフェノール化合物を酸結合
剤と銅触媒の存在下、式（社）の化合物と共に好ましく
は１５０〜２５０Ｃで２４〜４０時間加熱することによ
り６０％以上の収率で式（ト）のジフェニルアミンが７
％　ラれる。この反応で銅触媒としては、銅粉、又は酸
化第２銅、酢酸第２銅等の２価の銅塩が望ましく、その
量は式（Ｉ）の化合物に対して、０．１〜１．０倍モル
、特に０．３〜０．５倍モルが好ましく・。First, an acylaminophenol compound of formula (I) is heated with a compound of formula (Company) in the presence of an acid binder and a copper catalyst, preferably at 150 to 250 C for 24 to 40 hours, to obtain the formula with a yield of 60% or more. The diphenylamine in (g) is 7
% Rareru. In this reaction, the copper catalyst is preferably copper powder or a divalent copper salt such as cupric oxide or cupric acetate, and the amount thereof is 0.1 to 1. 0 times mole, especially 0.3 to 0.5 times mole is preferable.

又酸結合剤としては５例えば酸化マグネシウム、炭酸カ
リウム、炭酸ナトリウムなどが好ましく、式（Ｉ）の化
合物１モルに対し０．８〜１．４モル使用することが好
ましい。上記反応は溶媒を用いずに反応を行うことがで
きるが溶媒と゛して、例えばＮ−メチルピロリドン、ヘ
キサメチルホスフォルアミドなどの極性有機溶剤を用い
て行うこともできる。更に式［相］の化合物を水酸化カ
リウム、水酸化ナトリウ仏、炭酸ソーダ等のアルカリと
水又はアルコール中還流することにより、略々定量的に
加水分解されて式■で表わされるジフェニルアミン化合
物が得られる。As the acid binder, for example, magnesium oxide, potassium carbonate, sodium carbonate, etc. are preferable, and it is preferable to use 0.8 to 1.4 mol per mol of the compound of formula (I). The above reaction can be carried out without using a solvent, but it can also be carried out using a polar organic solvent such as N-methylpyrrolidone or hexamethylphosphoramide. Furthermore, by refluxing the compound of formula [phase] with an alkali such as potassium hydroxide, sodium hydroxide, or soda carbonate in water or alcohol, it is almost quantitatively hydrolyzed to obtain a diphenylamine compound represented by formula (2). It will be done.

また化合物側は弐■の化合物を単離することなく、反応
混合物のまま加水分解を行い式■の化合物を得ることが
出来る。On the compound side, the reaction mixture can be hydrolyzed to obtain the compound of formula (2) without isolating the compound (2).

以下に実施例により本発明を説明する。The present invention will be explained below with reference to Examples.

実施例１゜ Ｎ−ホルミル−ｐ−アニンジン９．　Ｉ　Ｐ、　酸化マ
グネシウム４．８１、銅粉１．６Ｐ−０−ジクロルベン
ゼン９４．５Ｓｌ’ｔ４０時間還流する。冷却後銅粉及
び酸化マグネシウム′ｆ：濾過する。ｐ液を真空蒸し 留して′、Ｎ−ホルミル−２−クロロ−４′−メトキシ
ジフェニルアミン１１．１７？（７１％）ヲ得る。Example 1゜N-formyl-p-aningine9. IP, magnesium oxide 4.81, copper powder 1.6P-0-dichlorobenzene 94.5Sl't Reflux for 40 hours. After cooling, the copper powder and magnesium oxide'f are filtered. Vacuum distillation of the p-liquid yields 'N-formyl-2-chloro-4'-methoxydiphenylamine 11.17? (71%) I get it.

（ｂ、ｐ、　１６９−１７４　ｃＡｍｍＨｇ）実施例２
．。(b, p, 169-174 cAmmHg) Example 2
．． .

Ｎ−ホルミル−ｐ−アニシジン９．１ｐ−酸化マグネシ
ウム４．８ｊ／、銅粉１゜６１．０−ジンｏ　／ｌ／ベ
ンゼン９４．５Ｆを４０時間還流する。次いで、エタノ
ール２０ｍ１−水酸化カリウム４．８％’ｉ加えて５時
間還流して加水分解する。エタノールを留去後、銅粉、
酸化マグネシウムｋ濾過した後、減圧蒸留シて１，２−
クロロ−４′−メトキシジフェニルアミン９．４１を得
る。（６７％）黄色固体す、ｐ。N-formyl-p-anisidine 9.1p-magnesium oxide 4.8j/l, copper powder 1°61.0-zine o/l/benzene 94.5F are refluxed for 40 hours. Next, 20ml of ethanol and 4.8%'i of potassium hydroxide were added and refluxed for 5 hours for hydrolysis. After distilling off the ethanol, copper powder,
After filtering magnesium oxide, it was distilled under reduced pressure.
9.41 of chloro-4'-methoxydiphenylamine is obtained. (67%) Yellow solid, p.

１５５−５８　Ｃ／　３．　ｍｍＨｇ 実施例３゜ Ｎ−バレリル−ｐ−アニシジン１２．４Ｆ！−１炭酸カ
リウム８，４？、銅粉１，６１、ｐ−ジクロルペ／セフ
９４．５　ｔｆ：　３５時間還流する。次いでエタノー
ル２０ｍ１．水酸化カリウム４，８１を加えて５時間還
流して加水分解する。エタノールを留去後。155-58 C/3. mmHg Example 3゜N-valeryl-p-anisidine 12.4F! -1 potassium carbonate 8,4? , copper powder 1,61, p-dichlorpe/ceph 94.5 tf: Reflux for 35 hours. Next, add 20 ml of ethanol. Add 4.81 g of potassium hydroxide and reflux for 5 hours for hydrolysis. After distilling off the ethanol.

銅粉、炭酸カリウムを濾過した後、減圧蒸留して。After filtering the copper powder and potassium carbonate, distill it under reduced pressure.

４−クロル−４１−メトキシジフェニルアミン９．８１
を得る。（７０％）、黄色固体、ｂ、ｐ、　１４８−１
５３　Ｃ／３　＋ｌｌｍＨｇ 以下実施例３と同様にして、下表に示されるジフェニル
アミン誘導体を得た。4-chloro-41-methoxydiphenylamine 9.81
get. (70%), yellow solid, b, p, 148-1
53 C/3 +llmHg Diphenylamine derivatives shown in the table below were obtained in the same manner as in Example 3.

Claims (2)

【特許請求の範囲】[Claims] （１）式 ％式％（） （式中Ｒ１はメチル又はエチルを表わす。Ｒ２は水素、
エチル、プロピル、ブチル、又はフェニルを表わす。） で表わされる化合物を酸結合剤及び銅触媒の存在下 式 （式中ｎは１又は２を表わす。） で表わされる化合物と反応させることを特徴（式中也、
Ｒ２，ｎは前記と同じものを意味する。） で表わされる化合物の製造法(1) Formula % Formula % () (In the formula, R1 represents methyl or ethyl. R2 is hydrogen,
Represents ethyl, propyl, butyl, or phenyl. ) is reacted with a compound represented by the formula (in the formula, n represents 1 or 2) in the presence of an acid binder and a copper catalyst (in the formula:
R2,n means the same as above. ) Method for producing a compound represented by （２）式 ％式％（） （式中Ｒｉはメチル又はエチルを表わす。Ｒ２は水素、
エチル、プロピル、ブチル又はフェニルを表わす。） で表わされる化合物を酸結合剤及び銅触媒の（式中ｎは
１又は２を表わす。） で表わされる化合物と反応させ式 （式中Ｒ＋　＃　＆　Ｉ　ｎは前記と同じものを意味す
る。） で表わされる化合物を得、ついで式［相］の化合物を加
水分解することを特徴とする特 （式中Ｒ，，ｎは前記と同じものを意味する。）で表わ
されイし合物の製造法。(2) Formula % Formula % () (In the formula, Ri represents methyl or ethyl. R2 is hydrogen,
Represents ethyl, propyl, butyl or phenyl. ) A compound represented by the formula (wherein n represents 1 or 2) is reacted with an acid binder and a copper catalyst (wherein n represents 1 or 2) to form a compound represented by the formula (wherein R + # & I n has the same meaning as above). ), and then hydrolyzing the compound of the formula [phase] (wherein R, , n have the same meanings as above). manufacturing method.
JP56158057A 1981-10-06 1981-10-06 Preparation of diphenylamines Pending JPS5859950A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP56158057A JPS5859950A (en) 1981-10-06 1981-10-06 Preparation of diphenylamines

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP56158057A JPS5859950A (en) 1981-10-06 1981-10-06 Preparation of diphenylamines

Publications (1)

Publication Number Publication Date
JPS5859950A true JPS5859950A (en) 1983-04-09

Family

ID=15663347

Family Applications (1)

Application Number Title Priority Date Filing Date
JP56158057A Pending JPS5859950A (en) 1981-10-06 1981-10-06 Preparation of diphenylamines

Country Status (1)

Country Link
JP (1) JPS5859950A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104628585A (en) * 2015-02-13 2015-05-20 山东道可化学有限公司 Preparation method of diphenylamine or nucleus-substituted derivative thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104628585A (en) * 2015-02-13 2015-05-20 山东道可化学有限公司 Preparation method of diphenylamine or nucleus-substituted derivative thereof

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