JPS6350339B2 - - Google Patents

Info

Publication number
JPS6350339B2
JPS6350339B2 JP59090200A JP9020084A JPS6350339B2 JP S6350339 B2 JPS6350339 B2 JP S6350339B2 JP 59090200 A JP59090200 A JP 59090200A JP 9020084 A JP9020084 A JP 9020084A JP S6350339 B2 JPS6350339 B2 JP S6350339B2
Authority
JP
Japan
Prior art keywords
reaction
derivative
fluoronitrobenzene
chloronitrobenzene
active halogen
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
Application number
JP59090200A
Other languages
Japanese (ja)
Other versions
JPS60237051A (en
Inventor
Seisaku Kumai
Takashi Seki
Hitoshi Matsuo
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.)
AGC Inc
Original Assignee
Asahi Glass 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 Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP59090200A priority Critical patent/JPS60237051A/en
Publication of JPS60237051A publication Critical patent/JPS60237051A/en
Publication of JPS6350339B2 publication Critical patent/JPS6350339B2/ja
Granted 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)

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は、活性ハロゲン含有化合物の存在下
に、クロロニトロベンゼン誘導体を金属フルオラ
イドによりF化し、2−フルオロニトロベンゼン
誘導体を得る方法に関する。 クロロニトロベンゼン誘導体を、ジメチルスル
ホキサイド(DMSO)等の非プロトン性極性溶
媒中で、弗化カリウム等の金属フルオライドと反
応させフルオロニトロベンゼン誘導体を得る際、
塩素がニトロ基のオルト位にある場合は、パラ位
にある場合に比べ、フツ素化反応収率が低いこと
が知られている。 塩素とニトロ基がオルト位に隣接した場合、ニ
トロ基が脱離し易く、ニトロ基が脱離すると
KNO2が生成し、KNO2やその分解物であるK2O
がフツ素化反応に悪影響を及ぼすため、収率が低
いと考えられている。すなわち、K2Oは原料及び
生成物と反応し、カリウムフエノキサイド誘導体
を与え、このカリウムフエノキサイド誘導体はさ
らに原料及び生成物と反応し、ジフエニルエーテ
ルタイプの生成物を与え、収率低下となると考え
られている。 本発明者等は、このような副反応を抑制し好収
率でクロロニトロベンゼン誘導体からフルオロニ
トロベンゼン誘導体を得る方法について、鋭意研
究を積み重ねたところ、活性ハロゲン含有化合物
の存在下にフツ素化反応を行なうことが効果的で
あることを見い出すに至つた。すなわち本発明は
下記一般式()で表わされるクロロニトロベン
ゼン誘導体を、非プロトン性極性溶媒中で活性ハ
ロゲン含有化合物の存在下に金属フルオライドと
反応させ、下記一般式()で表わされる2−フ
ルオロニトロベンゼン誘導体を得ることを特徴と
する2−フルオロニトロベンゼン誘導体の製造方
法に関するものである。 (式中、X1はCl又はH、X2はF又はH、Y、Z
はCl、NO2、又はHを示す。) 本発明におけるクロロニトロベンゼン誘導体
は、前記一般式()で表わされ、オルト位に隣
接した塩素とニトロ基を少なくとも1個所有する
化合物である。前記一般式()で表わされフル
オロニトロベンゼン誘導体は、クロロニトロベン
ゼン誘導体におけるニトロ基に隣接した塩素が弗
素に置換した化合物であり、具体的な反応例は以
下の通りである。
The present invention relates to a method for obtaining a 2-fluoronitrobenzene derivative by converting a chloronitrobenzene derivative to F with a metal fluoride in the presence of an active halogen-containing compound. When reacting a chloronitrobenzene derivative with a metal fluoride such as potassium fluoride in an aprotic polar solvent such as dimethyl sulfoxide (DMSO) to obtain a fluoronitrobenzene derivative,
It is known that when chlorine is at the ortho position of the nitro group, the fluorination reaction yield is lower than when it is at the para position. When chlorine and a nitro group are adjacent to each other at the ortho position, the nitro group is likely to leave, and when the nitro group leaves,
KNO 2 is generated, KNO 2 and its decomposition product K 2 O
is thought to have a negative effect on the fluorination reaction, resulting in low yields. That is, K 2 O reacts with the raw material and product to give a potassium phenoxide derivative, which further reacts with the raw material and product to give a diphenyl ether type product, and the yield It is thought that there will be a decline. The present inventors have conducted intensive research on a method for suppressing such side reactions and obtaining fluoronitrobenzene derivatives from chloronitrobenzene derivatives in good yields, and have found that a fluorination reaction is carried out in the presence of an active halogen-containing compound. I have come to find that doing so is effective. That is, the present invention reacts a chloronitrobenzene derivative represented by the following general formula () with a metal fluoride in an aprotic polar solvent in the presence of an active halogen-containing compound to obtain 2-fluoronitrobenzene represented by the following general formula (). The present invention relates to a method for producing a 2-fluoronitrobenzene derivative, which is characterized in that the derivative is obtained. (In the formula, X 1 is Cl or H, X 2 is F or H, Y, Z
represents Cl, NO 2 or H. ) The chloronitrobenzene derivative in the present invention is a compound represented by the above general formula () and having at least one chlorine and nitro group adjacent to the ortho position. The fluoronitrobenzene derivative represented by the general formula () is a compound in which the chlorine adjacent to the nitro group in the chloronitrobenzene derivative is replaced with fluorine, and specific reaction examples are as follows.

【表】【table】

【表】【table】

【表】 反応溶媒である非プロトン性極性溶媒として
は、例えばアセトニトリル、ジメチルホルムアミ
ド、ジメチルスルホキサイド、スルホラン、N−
メチル−2−ピロリドン、N−シクロヘキシル−
2−ピロリドン、ヘキサメチルホスホルトリアミ
ド、1,3−ジメチル−2−イミダゾリジノン等
が挙げられ、特にスルホラン、ジメチルスルホキ
サイドが好ましい。溶媒の使用量は特に限定され
ないが、出発原料のクロロニトロベンゼン誘導体
に対して重量部で0.2〜20倍量好ましくは1〜5
倍量が適当である。弗素化剤としての金属フルオ
ライドとしては、KF、RbF、CsF等が好ましく、
その使用量はクロロニトロベンゼン誘導体中の弗
素置換すべき塩素基が弗素に置換するために必要
な反応理論量及び活性ハロゲン含有化合物が弗素
化されるのに必要な反応理論量の0.5倍〜10倍、
好ましくは1.1〜2倍が適当である。 ニトロ基に対してオルト位に隣接する塩素の弗
素置換反応を促進し、かつ副反応を抑制するため
に、活性ハロゲン含有化合物の存在は効果的であ
る。好ましい活性ハロゲン含有化合物は、下記一
般式()〜()で表される化合物を挙げるこ
とができ、特にフタル酸クロライドが好ましい。 RCOA ………() RSO2A ………() (但し、式中Rはアルキル基、AはCl、Br、F
等のハロゲン原子) 活性ハロゲン含有化合物の添加量は、出発原料
のクロロニトロベンゼン誘導体100重量部に対し
1〜100重量部、好ましくは5〜40重量部の範囲
から選定すればよい。 本発明の反応温度、時間あるいは圧力等の反応
条件は適宜最適な条件を選定すればよいが、およ
そ100〜250℃の温度、1〜20時間の反応時間及び
1〜10Kg/cm2の圧力で実施し得る。本発明に従え
ば、農医薬中間体の原料として有用な2−フルオ
ロニトロベンゼン誘導体を好収率で得ることがで
きる。 以下、本発明の実施例について、さらに具体的
に説明する。 実施例 1 200c.c.のガラス製反応器に、2−クロロニトロ
ベンゼン31.5g、乾燥KF23.2g、フタル酸クロ
ライド8.1g、およびスルホラン80c.c.を入れ、210
℃で10時間反応させた。反応液をガスクロマトグ
ラフイで分析した処、原料の反応率85%、2−フ
ルオロニトロベンゼンへの選択率87%であつた。 比較例 1 フタル酸クロライドを添加しないこと以外、実
施例1と同様の条件で反応を行なつた処、原料の
反応率89%、2−フルオロニトロベンゼンへの選
択率61%であつた。 実施例 2 200c.c.のガラス製反応器に、2,3−ジクロロ
ニトロベンゼン38.4g、乾燥KF23.2g、フタル
酸クロライド8.1g、およびスルホラン80c.c.を入
れ、190℃で11時間反応させた。反応液をガスク
ロマトグラフイで分析した処、原料の反応率84
%、3−クロロ−2−フルオロニトロベンゼンへ
の選択率88%であつた。 比較例 2 フタル酸クロライドを添加しないこと以外、実
施例1と同様の条件で反応を行なつた処、原料の
反応率87%、3−クロロ−2−フルオロニトロベ
ンゼンへの選択率58%であつた。 実施例 3〜6 実施例2と同様な条件でフタル酸クロライドの
代りに種々の活性ハロゲン含有化合物を加えて反
応を行なつた結果を下表に示す。
[Table] Examples of aprotic polar solvents used as reaction solvents include acetonitrile, dimethylformamide, dimethyl sulfoxide, sulfolane, N-
Methyl-2-pyrrolidone, N-cyclohexyl-
Examples include 2-pyrrolidone, hexamethylphosphortriamide, 1,3-dimethyl-2-imidazolidinone, and particularly preferred are sulfolane and dimethylsulfoxide. The amount of the solvent used is not particularly limited, but is preferably 0.2 to 20 parts by weight, preferably 1 to 5 parts by weight, relative to the starting material chloronitrobenzene derivative.
Double the amount is appropriate. As the metal fluoride as a fluorinating agent, KF, RbF, CsF, etc. are preferable.
The amount used is 0.5 to 10 times the theoretical reaction amount necessary for the chlorine group to be replaced with fluorine in the chloronitrobenzene derivative and the reaction theoretical amount necessary for the active halogen-containing compound to be fluorinated. ,
Preferably, 1.1 to 2 times is appropriate. The presence of an active halogen-containing compound is effective in promoting the fluorine substitution reaction of chlorine adjacent to the ortho position to the nitro group and suppressing side reactions. Preferred active halogen-containing compounds include compounds represented by the following general formulas () to (), with phthaloyl chloride being particularly preferred. RCOA ………() RSO 2 A ………() (However, in the formula, R is an alkyl group, A is Cl, Br, F
The amount of the active halogen-containing compound to be added may be selected from the range of 1 to 100 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the chloronitrobenzene derivative as the starting material. The reaction conditions of the present invention, such as reaction temperature, time, and pressure, may be selected as appropriate, but a temperature of approximately 100 to 250°C, a reaction time of 1 to 20 hours, and a pressure of 1 to 10 Kg/cm 2 are suitable. It can be implemented. According to the present invention, a 2-fluoronitrobenzene derivative useful as a raw material for agricultural and pharmaceutical intermediates can be obtained in good yield. Examples of the present invention will be described in more detail below. Example 1 31.5 g of 2-chloronitrobenzene, 23.2 g of dry KF, 8.1 g of phthaloyl chloride, and 80 c.c. of sulfolane were placed in a 200 c.c. glass reactor.
The reaction was carried out at ℃ for 10 hours. Analysis of the reaction solution by gas chromatography showed that the reaction rate of the raw materials was 85% and the selectivity to 2-fluoronitrobenzene was 87%. Comparative Example 1 A reaction was carried out under the same conditions as in Example 1 except that phthalyl chloride was not added, and the reaction rate of the raw material was 89% and the selectivity to 2-fluoronitrobenzene was 61%. Example 2 38.4 g of 2,3-dichloronitrobenzene, 23.2 g of dry KF, 8.1 g of phthaloyl chloride, and 80 c.c. of sulfolane were placed in a 200 c.c. glass reactor and reacted at 190°C for 11 hours. Ta. When the reaction solution was analyzed by gas chromatography, the reaction rate of the raw materials was 84.
%, and the selectivity to 3-chloro-2-fluoronitrobenzene was 88%. Comparative Example 2 A reaction was carried out under the same conditions as in Example 1 except that phthalyl chloride was not added, and the reaction rate of the raw material was 87%, the selectivity to 3-chloro-2-fluoronitrobenzene was 58%, and Ta. Examples 3 to 6 Reactions were carried out under the same conditions as in Example 2 except that various active halogen-containing compounds were added in place of phthalyl chloride. The results are shown in the table below.

【表】【table】

【表】 実施例 7 200c.c.のガラス製反応器に、2,5−ジクロロ
ニトロベンゼン38.4g、乾燥KF23.2g、フタル
酸クロライドを10g、およびジメチルスルホキシ
ド80c.c.を入れ、190℃で10時間反応させた。反応
液を分析した処、原料の反応率78%、5−クロロ
−2−フルオロニトロベンゼンへの選択率86%で
あつた。 実施例 8 200c.c.のガラス製反応器に、1−クロロ−2,
4−ジニトロベンゼン30.4g、乾燥KF21g、フ
タル酸クロライド6g、およびスルホラン80c.c.を
入れ、180℃で10時間反応させた。反応液を分析
した処、1−フルオロ−2,4−ジニトロベンゼ
ンの収率95%であつた。
[Table] Example 7 38.4 g of 2,5-dichloronitrobenzene, 23.2 g of dry KF, 10 g of phthalic acid chloride, and 80 c.c. of dimethyl sulfoxide were placed in a 200 c.c. glass reactor, and the mixture was heated at 190°C. The reaction was allowed to proceed for 10 hours. Analysis of the reaction solution revealed that the reaction rate of the raw materials was 78% and the selectivity to 5-chloro-2-fluoronitrobenzene was 86%. Example 8 In a 200 c.c. glass reactor, 1-chloro-2,
30.4 g of 4-dinitrobenzene, 21 g of dry KF, 6 g of phthaloyl chloride, and 80 c.c. of sulfolane were added and reacted at 180°C for 10 hours. Analysis of the reaction solution revealed that the yield of 1-fluoro-2,4-dinitrobenzene was 95%.

Claims (1)

【特許請求の範囲】 1 下記一般式()で表わされるクロロニトロ
ベンゼン誘導体を、非プロトン性極性溶媒中で、
活性ハロゲン含有化合物の存在下に、金属フルオ
ライドと反応させ、下記一般式()で表わされ
る2−フルオロニトロベンゼン誘導体を得ること
を特徴とする2−フルオロニトロベンゼン誘導体
の製造方法。 (式中、X1はCl又はH、X2はF又はH、Y、Z
はCl、NO2、又はHを示す。)
[Claims] 1. A chloronitrobenzene derivative represented by the following general formula () in an aprotic polar solvent,
A method for producing a 2-fluoronitrobenzene derivative, which comprises reacting with a metal fluoride in the presence of an active halogen-containing compound to obtain a 2-fluoronitrobenzene derivative represented by the following general formula (). (In the formula, X 1 is Cl or H, X 2 is F or H, Y, Z
represents Cl, NO 2 or H. )
JP59090200A 1984-05-08 1984-05-08 Preparation of 2-fluoronitrobenzene derivative Granted JPS60237051A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59090200A JPS60237051A (en) 1984-05-08 1984-05-08 Preparation of 2-fluoronitrobenzene derivative

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59090200A JPS60237051A (en) 1984-05-08 1984-05-08 Preparation of 2-fluoronitrobenzene derivative

Publications (2)

Publication Number Publication Date
JPS60237051A JPS60237051A (en) 1985-11-25
JPS6350339B2 true JPS6350339B2 (en) 1988-10-07

Family

ID=13991840

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59090200A Granted JPS60237051A (en) 1984-05-08 1984-05-08 Preparation of 2-fluoronitrobenzene derivative

Country Status (1)

Country Link
JP (1) JPS60237051A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3032883U (en) * 1996-06-26 1997-01-17 淳 高島 Portable night light with fragrance function

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0676343B2 (en) * 1984-06-20 1994-09-28 株式会社トーケムプロダクツ Novel method for producing fluorinated aromatic compounds
JP7123958B2 (en) 2019-02-15 2022-08-23 福建永晶科技股▲ふん▼有限公司 New production method for fluoroaryl compounds and their derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3032883U (en) * 1996-06-26 1997-01-17 淳 高島 Portable night light with fragrance function

Also Published As

Publication number Publication date
JPS60237051A (en) 1985-11-25

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