JPS61233652A - Production of 3,3'-dinitrodiphenyl ether - Google Patents

Production of 3,3'-dinitrodiphenyl ether

Info

Publication number
JPS61233652A
JPS61233652A JP60073464A JP7346485A JPS61233652A JP S61233652 A JPS61233652 A JP S61233652A JP 60073464 A JP60073464 A JP 60073464A JP 7346485 A JP7346485 A JP 7346485A JP S61233652 A JPS61233652 A JP S61233652A
Authority
JP
Japan
Prior art keywords
nitrite
bromonitrobenzene
ether
dinitrodiphenyl ether
self
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
JP60073464A
Other languages
Japanese (ja)
Inventor
Yukihiro Yoshikawa
幸宏 吉川
Keisaburo Yamaguchi
桂三郎 山口
Kenichi Sugimoto
賢一 杉本
Yoshimitsu Tanabe
良満 田辺
Teruhiro Yamaguchi
彰宏 山口
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.)
Mitsui Toatsu Chemicals Inc
Original Assignee
Mitsui Toatsu Chemicals Inc
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 Mitsui Toatsu Chemicals Inc filed Critical Mitsui Toatsu Chemicals Inc
Priority to JP60073464A priority Critical patent/JPS61233652A/en
Publication of JPS61233652A publication Critical patent/JPS61233652A/en
Pending legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements 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 safely and industrially the titled compound useful as a raw material for agricultural chemicals, medicines, etc., at a low cost, by self- condensing m-bromonitrobenzene in the presence of a nitrite in an aprotic polar solvent. CONSTITUTION:m-Bromonitrobenzene is self-condensed in the presence of a nitrite in an aprotic polar solvent to give 3,3'-dinitrodiphenyl ether. The above- mentioned nitrite is potassium nitrite, sodium nitrite, etc., and used in a molar amount of 1-5 times based on the raw material m-bromonitrobenzene. The solvent for the reaction is 1,3-dimethyl-2-imidazolidinone, etc. Bromine ions formed as a by-product can be readily separated and recovered as a metal bromide by the above-mentioned method.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は6,6′−ジニトロジフェニルエーテルの製造
方法に関する。
DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing 6,6'-dinitrodiphenyl ether.

更に詳しくは、m−ブロモニトロベンゼンを亜硝酸塩の
存在下、非プロトン性極性溶媒中で自己縮合縮合ことを
特徴とする6、3′−ジニトロジフェニルエーテルの製
造方法に関する。
More specifically, the present invention relates to a method for producing 6,3'-dinitrodiphenyl ether, which comprises self-condensing m-bromonitrobenzene in an aprotic polar solvent in the presence of nitrite.

6.3′−ジニトロジフェニルエーテルは農医薬原料と
なるほか、ポリアミド、ポリアミドイミド、ポリイミド
の原料である6、3′−ジアミノジフェニルエーテルの
中間体として重要な化合物である。
6.3'-Dinitrodiphenyl ether is an important compound as an intermediate for 6,3'-diaminodiphenyl ether, which is a raw material for agrochemicals and medicines, and is a raw material for polyamide, polyamideimide, and polyimide.

(従来の技術) 3.3′−ジニトロジフェニルエーテルは、従来、m−
ニトロフェノールとm−ブロモニトロベンセンのUl 
1mann・エーテル合成反応により製造する方法が知
られている(富田ら、薬学雑誌、75゜1080(19
55);弁用ら、jbid、 79.273(1959
) ; J、P、Cr1tchleyら、J、Poly
m、Sci 、、 PartA−1、10,1793)
(Prior art) 3.3'-dinitrodiphenyl ether has conventionally been m-
Ul of nitrophenol and m-bromonitrobenzene
A method for producing ether by a 1 mann ether synthesis reaction is known (Tomita et al., Pharmaceutical Journal, 75° 1080 (19
55); Benyo et al., jbid, 79.273 (1959
) ; J, P, Crltchley et al., J, Poly
m, Sci, Part A-1, 10, 1793)
.

しかしながら、これらの方法は収率が低かったり、爆発
の危険性を伴うなどの欠点を有し、更には工業的に実施
する上で原料のm−ニトロフェノールが高価で、工業的
に入手が容易でないということが最大の問題点である。
However, these methods have drawbacks such as low yields and the risk of explosion, and furthermore, the raw material m-nitrophenol is expensive and difficult to obtain industrially. The biggest problem is that it is not.

(発明が解決しようとする問題点) このような従来技術の問題点は、m−ブロモニトロベン
ゼンを自己縮合縮合させることが可能であれば、3.3
’−ジニトロジフェニルエーテルヲ安価に製造できる。
(Problems to be Solved by the Invention) The problems of the prior art are that if m-bromonitrobenzene can be self-condensed, 3.3
'-dinitrodiphenyl ether can be produced at low cost.

すでに、芳香族ニトロ化合物および芳香族ハライドを亜
硝酸塩または塩基を用いて自己縮合し、三量化したエー
テルを製造する方法は従来知られている。例えば、■p
−クロロニトロゼイン亜硝酸ナトリウムをN−メチルピ
ロリドン中で作用させて4,4′−ジニトロジフェニル
エーテルヲ製造する方法、および同一条件下にp−ニト
ロベンゾニトリルおよびp−クロロベンゾニトリルより
4,4′−ジシアノジフェニルエーテルを製造する方法
(Get、0ffen、、 2,037,781 )、
■0−二!・ロフルオロベンゼンに炭酸水素カリウムを
N、N−ジメチルアセトアミド中、相間移動触媒の存在
下に作用させて2,2′−ジニトロジフェニルエーテル
を製造する方法(J、Org、Chem、、 49 、
1125(1984) )、■4−ニトローN−メチル
フタルイミドまたは4−フルオロ−N−メチルフタルイ
ミドに非プロトン性極性溶媒中、亜硝酸カリウムを作用
させて、4.4′−オキシビス(N−メチルフタルイミ
ド)を製造する方法(J、Org Chem、、 42
3431(1977))などが知られている。しかしな
がら、これらはいずれも0−またはp−位に電子吸引性
基を有する活性化された芳香族ハライドおよび芳香族ニ
トロ化合物についての反応であり、m−ブロモニトロベ
ンゼンのように電子吸引性基を有するが活性化されてい
ないm−位のハロゲン基を有する芳香族ハライドの場合
に関しては、従来、まったく知られていない。
A method for producing a trimerized ether by self-condensing an aromatic nitro compound and an aromatic halide using a nitrite or a base is already known. For example, ■p
- Process for producing 4,4'-dinitrodiphenyl ether by reacting sodium chloronitrozein nitrite in N-methylpyrrolidone and 4,4' from p-nitrobenzonitrile and p-chlorobenzonitrile under the same conditions. - Method for producing dicyanodiphenyl ether (Get, Offen, 2,037,781),
■0-2! - A method for producing 2,2'-dinitrodiphenyl ether by reacting potassium hydrogen carbonate with lofluorobenzene in N,N-dimethylacetamide in the presence of a phase transfer catalyst (J, Org, Chem, 49,
1125 (1984)), ■ 4-Nitro-N-methylphthalimide or 4-fluoro-N-methylphthalimide was reacted with potassium nitrite in an aprotic polar solvent to form 4,4'-oxybis(N-methylphthalimide). (J, Org Chem, 42
3431 (1977)) are known. However, these are all reactions for activated aromatic halides and aromatic nitro compounds that have an electron-withdrawing group at the 0- or p-position, and such as m-bromonitrobenzene have an electron-withdrawing group. The case of an aromatic halide having a halogen group at the m-position which is not activated has not been known at all so far.

(問題を解決するための手段) 本発明者らは、乙、6′−ジニトロジフェニルエーテル
の安価でしかも工業的に実施し得る製造方法を提供しよ
うという目的で鋭意検討してきた。その結果、m−ブロ
モニトロベンゼンを特定の条件の下で自己縮合させるこ
とにより3,6′−ジニトロジフェニルエーテルが製造
できることを見出し、本発明を完成するに至った。
(Means for Solving the Problems) The present inventors have made extensive studies with the aim of providing a method for producing 6'-dinitrodiphenyl ether that is inexpensive and can be implemented industrially. As a result, they discovered that 3,6'-dinitrodiphenyl ether can be produced by self-condensing m-bromonitrobenzene under specific conditions, and have completed the present invention.

すなわち、本発明はm−ブロモニトロベンゼンを亜硝酸
塩の存在下、非プロトン性極性溶媒中で自己縮合反応さ
せることを特徴とする6、6′−ジニトロジフェニルエ
ーテルの製造方法である。
That is, the present invention is a method for producing 6,6'-dinitrodiphenyl ether, which is characterized by subjecting m-bromonitrobenzene to a self-condensation reaction in an aprotic polar solvent in the presence of nitrite.

本発明の方法で使用する亜硝酸塩は、亜硝酸カリウム、
亜硝酸ナトリウム、亜硝酸カルシウム、亜硝酸マグネシ
ウム、亜硝酸バリウム、亜硝酸リチウム、亜硝酸アンモ
ニウムが好ましく用いられ、その他金属の亜硝酸塩も使
用できる。
The nitrites used in the method of the present invention include potassium nitrite,
Sodium nitrite, calcium nitrite, magnesium nitrite, barium nitrite, lithium nitrite, and ammonium nitrite are preferably used, and nitrites of other metals can also be used.

これら亜硝酸塩の使用量は原料のm−ブロモニトロベン
ゼンに対し1〜5倍モルである。
The amount of these nitrites used is 1 to 5 times the mole of m-bromonitrobenzene as the raw material.

本発明の方法で使用する溶剤は、1,3−ジメチル−2
−イミダゾリジノン、ヘキサメチルホスホルアミドが好
ましく用いられ、N、N−ジメ、チルホルムアミド、N
、N−ジメチルアセトアミド中−メチルピロリドン、ジ
メチルスルホキシド、スルホラン等も使用される。これ
ら溶剤の使用量は特に限定はされないが、通常原料に対
して1〜15重量倍、好ましくは6〜10重量倍である
The solvent used in the method of the invention is 1,3-dimethyl-2
-imidazolidinone, hexamethylphosphoramide are preferably used, N,N-dime, thylformamide, N
, methylpyrrolidone in N-dimethylacetamide, dimethylsulfoxide, sulfolane, etc. are also used. The amount of these solvents used is not particularly limited, but is usually 1 to 15 times the weight of the raw materials, preferably 6 to 10 times the weight of the raw materials.

また、本発明の方法では、反応を促進するための触媒と
して銅系化合物またはクラウンエーテル、ポリエチレン
グリコール、四級アンモニウム塩、四級ホスホニウム塩
のような相間移動触媒を使用しても何ら差しつかえない
Further, in the method of the present invention, there is no problem in using a phase transfer catalyst such as a copper-based compound or a crown ether, polyethylene glycol, quaternary ammonium salt, or quaternary phosphonium salt as a catalyst to promote the reaction. .

反応温度は、通常、100〜240℃の範囲、好ましく
は140〜200℃の範囲である。
The reaction temperature is usually in the range of 100 to 240°C, preferably in the range of 140 to 200°C.

本発明の一般的な実施態様としては、亜硝酸塩を含む全
原料に場合によってはベンゼン、トルエン、キシレンま
たはクロルベンゼン等の共沸脱水溶剤を少量加え、脱水
させながら昇温して所定の温度で反応させる。反応の終
点は、薄層クロマトグラフィー、高速液体クロマトグラ
フィーまたはガスクロマトグラフィーにより原料の減少
を見ながら決定することができる。
In a general embodiment of the present invention, a small amount of an azeotropic dehydration solvent such as benzene, toluene, xylene or chlorobenzene is added to all the raw materials containing nitrite as the case may be, and the temperature is increased while dehydration is being carried out until a predetermined temperature is reached. Make it react. The end point of the reaction can be determined by thin layer chromatography, high performance liquid chromatography, or gas chromatography while observing the reduction of raw materials.

反応終了後、濃縮したのち、あるいはそのまま水等に排
出して、粗6,6′−ジニトロジフェニルエーテルを得
る。
After the reaction is completed, the crude 6,6'-dinitrodiphenyl ether is obtained by concentrating it or directly discharging it into water or the like.

このものは溶剤で容易に再結晶精製することができる。This product can be easily purified by recrystallization using a solvent.

(作用および効果) 本発明の方法によれば、m−ニトロフェノールを使用す
る必要なくして、亜硝酸塩によるm−ブロモニトロベン
ゼンの自己縮合反応により、3.3’−ジニトロジフェ
ニルエーテルを製造でき、しかも副生ずる臭素イオンは
金属臭化物として、容易に分離回収できるので、工業的
に安価で極めて優れた方法である。
(Functions and Effects) According to the method of the present invention, 3,3'-dinitrodiphenyl ether can be produced by the self-condensation reaction of m-bromonitrobenzene with nitrite without the need to use m-nitrophenol, and moreover, The produced bromine ions can be easily separated and recovered as metal bromides, so this is an industrially inexpensive and extremely excellent method.

=6− (実施例) 以下、本発明の方法を実施例により更に詳しく説明する
=6- (Example) Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.

実施例1 50m14日フラスコ中、m−ブロモニトロベンゼン1
0.1.9(0,05モル)を1,3−ジメチルイミダ
ゾリジノン35m1に溶解させ、亜硝酸ナトリウム6、
9 # (0,1モル)を加えて窒素ガス気流下に17
0〜180℃で20時間攪拌する。この反応液を200
m1の水に排出すると暗褐色固体が沈殿した。これを濾
過、乾燥後、ベンゼンで再結晶することによす5.5’
−ジニトロジフェニルエーテル2.69(収率40チ)
を得た。m、p、126〜128°C実施例2 溶剤としてヘキサメチルホスホアミドを用いた以外は実
施例1と全く同様の操作を行ない、3.3’−ジニトロ
ジフエニルエーテル3.09 (収率46%)を得た〇 実施例6 反応促進剤としてベンジルトリメチルアンモニウムクロ
リドを1g加えた以外は実施例1とまったく同様の操作
を行ない、3.3’−ジニトロジフェニルエーテル3.
5 # (収率56%)を得た。
Example 1 1 m-bromonitrobenzene in a 50 m 14 day flask
0.1.9 (0.05 mol) was dissolved in 35 ml of 1,3-dimethylimidazolidinone, and sodium nitrite 6,
9 # (0.1 mol) was added to 17 in a stream of nitrogen gas.
Stir at 0-180°C for 20 hours. Add this reaction solution to 200
Draining into 1 ml of water precipitated a dark brown solid. This is filtered, dried, and then recrystallized with benzene to give 5.5'
-Dinitrodiphenyl ether 2.69 (yield 40t)
I got it. m, p, 126-128°C Example 2 The same operation as in Example 1 was carried out except that hexamethylphosphoamide was used as the solvent, and 3.3'-dinitrodiphenyl ether 3.09 (yield 46 %) was obtained. Example 6 The same procedure as in Example 1 was carried out except that 1 g of benzyltrimethylammonium chloride was added as a reaction accelerator, and 3.3'-dinitrodiphenyl ether 3.
5# (yield 56%) was obtained.

Claims (1)

【特許請求の範囲】[Claims] 1)m−ブロモニトロベンゼンを亜硝酸塩の存在下、非
プロトン性極性溶媒中で自己縮合反応させることを特徴
とする3,3′−ジニトロジフェニルエーテルの製造方
法。
1) A method for producing 3,3'-dinitrodiphenyl ether, which comprises subjecting m-bromonitrobenzene to a self-condensation reaction in an aprotic polar solvent in the presence of nitrite.
JP60073464A 1985-04-09 1985-04-09 Production of 3,3'-dinitrodiphenyl ether Pending JPS61233652A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60073464A JPS61233652A (en) 1985-04-09 1985-04-09 Production of 3,3'-dinitrodiphenyl ether

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60073464A JPS61233652A (en) 1985-04-09 1985-04-09 Production of 3,3'-dinitrodiphenyl ether

Publications (1)

Publication Number Publication Date
JPS61233652A true JPS61233652A (en) 1986-10-17

Family

ID=13519005

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60073464A Pending JPS61233652A (en) 1985-04-09 1985-04-09 Production of 3,3'-dinitrodiphenyl ether

Country Status (1)

Country Link
JP (1) JPS61233652A (en)

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