JPH0155253B2 - - Google Patents
Info
- Publication number
- JPH0155253B2 JPH0155253B2 JP59101669A JP10166984A JPH0155253B2 JP H0155253 B2 JPH0155253 B2 JP H0155253B2 JP 59101669 A JP59101669 A JP 59101669A JP 10166984 A JP10166984 A JP 10166984A JP H0155253 B2 JPH0155253 B2 JP H0155253B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- aromatic
- mol
- chloro
- chlorine
- 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
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- -1 aromatic nitro compound Chemical class 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 150000004714 phosphonium salts Chemical group 0.000 claims description 5
- 229910004013 NO 2 Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical group [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 claims description 3
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- JORVCRLRRRRLFI-UHFFFAOYSA-N 1,3-dichloro-2-fluorobenzene Chemical compound FC1=C(Cl)C=CC=C1Cl JORVCRLRRRRLFI-UHFFFAOYSA-N 0.000 description 4
- ZBNCSBMIRFHJEL-UHFFFAOYSA-N 1-chloro-2,3-difluorobenzene Chemical compound FC1=CC=CC(Cl)=C1F ZBNCSBMIRFHJEL-UHFFFAOYSA-N 0.000 description 4
- RBAHXNSORRGCQA-UHFFFAOYSA-N 1-chloro-2-fluoro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1F RBAHXNSORRGCQA-UHFFFAOYSA-N 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 1
- OFQRRFRIDGZHSC-UHFFFAOYSA-N 1-chloro-2,3-difluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(F)=C1F OFQRRFRIDGZHSC-UHFFFAOYSA-N 0.000 description 1
- 208000018380 Chemical injury Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、芳香族ニトロ化合物から芳香族フツ
素化合物を得る方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for obtaining aromatic fluorine compounds from aromatic nitro compounds.
１−クロロ−２−フルオロ−３−ニトロベンゼ
ンのような芳香族ニトロ化合物から１−クロロ−
２，３−ジフルオロベンゼンのような芳香族フツ
素化合物を得る方法には、下記反応式で表される
方法が知られている。 from aromatic nitro compounds such as 1-chloro-2-fluoro-3-nitrobenzene to 1-chloro-
A method represented by the following reaction formula is known as a method for obtaining an aromatic fluorine compound such as 2,3-difluorobenzene.
しかしながら、中間生成物のジアゾニウム塩は
毒性が極めて高く、取り扱い作業者に対する薬傷
が問題である。又は、ジアゾニウム塩は水分に対
して不安定で、室温で簡単に分解し、HFが発生
するため取り扱いが不便である。さらにジアゾニ
ウム塩を熱分解する際、有毒ガスのBF3が発生
し、工業化は困難である等、従来法には種々の欠
点を有している。 However, the intermediate product diazonium salt is extremely toxic and causes chemical injuries to workers who handle it. Alternatively, diazonium salts are unstable to moisture and easily decompose at room temperature, generating HF, making them inconvenient to handle. Furthermore, when diazonium salts are thermally decomposed, toxic gas BF 3 is generated, making industrialization difficult, and other conventional methods have various drawbacks.
本発明者等は、１−クロロ−２−フルオロ−３
−ニトロベンゼンのような芳香族ニトロ化合物か
ら工業的に有利に、１−クロロ−２，３−ジフル
オロベンゼンのような芳香族フツ素化合物を得る
方法を見い出すべく研究を重ねた結果、ここに作
業環境上問題がないとともに、工程数が短縮した
優れた方法を完成し、提案するに至つた。すなわ
ち、本発明は下記一般式（）で表わされる芳香
族ニトロ化合物のニトロ基を塩素ガスにより塩素
置換し、次いで第４級ホスホニウム塩の存在下に
金属フルオライドと反応させ、下記一般式（）
で表される芳香族フツ素化合物を得ることを特徴
とする芳香族フツ素化合物の製造方法に関するも
のである。 The inventors have discovered that 1-chloro-2-fluoro-3
- As a result of repeated research to find an industrially advantageous method for obtaining aromatic fluorine compounds such as 1-chloro-2,3-difluorobenzene from aromatic nitro compounds such as nitrobenzene, we have developed a working environment. We have completed and proposed an excellent method that does not cause any problems and reduces the number of steps. That is, the present invention replaces the nitro group of an aromatic nitro compound represented by the following general formula () with chlorine gas, and then reacts it with a metal fluoride in the presence of a quaternary phosphonium salt to obtain the following general formula ().
The present invention relates to a method for producing an aromatic fluorine compound, which is characterized in that the aromatic fluorine compound is obtained.
（式中、Ｘ、ＹはそれぞれCl、Br、Ｆ又はＨ、
但しＸ、Ｙ共にＨは除く。 (In the formula, X and Y are respectively Cl, Br, F or H,
However, H is excluded for both X and Y.
R1、R2、R3、R4、R5、R6はそれぞれCl、Br、
Ｆ、NO2、CN、CF3又はＨを示す）。 R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are respectively Cl, Br,
F, NO 2 , CN, CF 3 or H).
本発明における芳香族ニトロ化合物は、前記一
般式（）で表され、少なくとも１個のCl、Br、
Ｆ等のハロゲン原子を同時に有する化合物であ
る。さらに、これらのニトロ基及びハロゲン原子
が、芳香核の隣接する炭素に結合している個所が
少なくとも１個所あるものである。一方、得られ
る芳香族フツ素化合物は前記一般式（）で表わ
される。一般式（）及び（）におけるＸ、Ｙ
はそれぞれCl、Br、Ｆ又はＨであり、XYが共に
Ｈ以外の組み合せを含むものである。又、R1、
R2、R3はそれぞれCl、Br、Ｆ、NO2、CN、CF3
又はＨであり、これら１種〜３種の組み合せであ
る。又、R4、R5、R6もそれぞれCl、Br、Ｆ、
NO2、CN、CF3又はＨであり、これら１種〜３
種の組み合せである。 The aromatic nitro compound in the present invention is represented by the general formula () and contains at least one of Cl, Br,
It is a compound that also contains a halogen atom such as F. Furthermore, there is at least one location where these nitro groups and halogen atoms are bonded to adjacent carbon atoms of the aromatic nucleus. On the other hand, the aromatic fluorine compound obtained is represented by the general formula (). X, Y in general formulas () and ()
are Cl, Br, F or H, respectively, and both XY include a combination other than H. Also, R 1 ,
R 2 and R 3 are Cl, Br, F, NO 2 , CN, and CF 3 respectively
or H, and a combination of one to three of these. Moreover, R 4 , R 5 and R 6 are also Cl, Br, F,
NO 2 , CN, CF 3 or H, one to three of these
It is a combination of species.
本発明方法を表す反応式は、例えば出発原料と
して１−クロロ−２−フルオロ−３−ニトロベン
ゼンを用いた場合、下記のようになり１−クロロ
−２，３−ジフルオロニトロベンゼンが得られ
る。 For example, when 1-chloro-2-fluoro-3-nitrobenzene is used as a starting material, the reaction formula representing the method of the present invention is as shown below, and 1-chloro-2,3-difluoronitrobenzene is obtained.
ニトロ基の塩素置換反応は、液相又は気相流通
系で行ない、液相系では溶媒存在下でも無溶媒で
もよく、溶媒を用いる場合は、塩素化パラフイ
ン、クロロトリフルオロエチレン低重合体、テト
ラブロモエタン等のハロゲン系溶媒が好ましい。
塩素ガス（Cl2）の使用量は、芳香族ニトロ化合
物中の塩素置換すべきニトロ基が塩素に置換する
ために必要な反応理論量の0.2〜10倍、好ましく
は1.0〜５倍が適当である。反応温度は150〜350
℃、反応圧力は常圧〜100Kg/cm2、反応時間は２〜
30時間が適当である。 The chlorine substitution reaction of nitro groups is carried out in a liquid phase or gas phase flow system. In a liquid phase system, it may be in the presence of a solvent or without a solvent. When a solvent is used, chlorinated paraffin, chlorotrifluoroethylene low polymer, tetrafluoroethylene, etc. Halogenated solvents such as bromoethane are preferred.
The appropriate amount of chlorine gas (Cl 2 ) to be used is 0.2 to 10 times, preferably 1.0 to 5 times, the theoretical reaction amount necessary for the nitro group in the aromatic nitro compound to be replaced with chlorine. be. Reaction temperature is 150-350
℃, reaction pressure is normal pressure ~ 100Kg/cm 2 , reaction time is 2 ~
30 hours is appropriate.
次に、下記一般式（）で表される第４級ホス
ホニウム塩の存在下に金属フルオライドにより塩
素基の弗素置換反応を行ない、目的化合物の芳香
族フツ素化合物を得ることができる。 Next, the chlorine group is subjected to a fluorine substitution reaction using a metal fluoride in the presence of a quaternary phosphonium salt represented by the following general formula () to obtain an aromatic fluorine compound as the target compound.
（式中、A1、A2、A3、A4は同一もしくは異なる
アルキル基、又は同一もしくは異なるアリール
基、又はこれらのアルキル基とアリール基の組み
合せを示す。ＢはCl又はBrを示す。）
金属フルオライドとしては、KF、RbF、CsF
等が好ましく、その使用量は弗素置換すべきCl基
が弗素に置換するために必要な反応理論量の１〜
10倍、好ましくは１〜２倍が適当である。相間移
動触媒の添加量は、フツ素化すべき原料に対して
１〜200mol％好ましくは５〜100mol％の範囲か
ら選定すればよい。弗素置換反応の反応温度は
150〜300℃好ましくは200〜250℃、反応圧力は１
〜10Kg/cm2、反応時間は２〜30時間が適当である。
反応温度が200℃以上の場合には、前記（）で
表される相間移動触媒は分解する可能性があるた
め、前記（）で表される第４級ホスホニウム塩
を用いることが好ましい。特に好ましい例は、テ
トラフエニルホスホニウムクロライド又はテトラ
フエニルホスホニウムブロマイドである。反応
は、スルホラン、ジメチルホルムアミド、ジメチ
ルスルホキサイド、Ｎ−メチルピロリドン等の非
プロトン性極性溶媒中で行なつてもよいが、副反
応が起りにくいことから、無溶媒が好ましい。 (In the formula, A 1 , A 2 , A 3 , and A 4 represent the same or different alkyl groups, the same or different aryl groups, or a combination of these alkyl groups and aryl groups. B represents Cl or Br. ) Metal fluorides include KF, RbF, and CsF.
etc., and the amount used is 1 to 1 of the theoretical reaction amount necessary for the Cl group to be replaced with fluorine to be replaced with fluorine.
10 times, preferably 1 to 2 times is appropriate. The amount of the phase transfer catalyst added may be selected from the range of 1 to 200 mol%, preferably 5 to 100 mol%, based on the raw material to be fluorinated. The reaction temperature of the fluorine substitution reaction is
150-300℃, preferably 200-250℃, reaction pressure is 1
~10Kg/cm 2 and reaction time of 2 to 30 hours is appropriate.
When the reaction temperature is 200° C. or higher, the phase transfer catalyst represented by () above may decompose, so it is preferable to use a quaternary phosphonium salt represented by () above. Particularly preferred examples are tetraphenylphosphonium chloride or tetraphenylphosphonium bromide. The reaction may be carried out in an aprotic polar solvent such as sulfolane, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, etc., but solvent-free solvents are preferred since side reactions are less likely to occur.
本発明方法に従えば、含フツ素医農薬中間体の
原料として有用な１−クロロ−２，３−ジフルオ
ロベンゼン等の芳香族フツ素化合物を工業的に有
利に得ることができる。以下、本発明の実施例に
ついてさらに具体的に説明する。 According to the method of the present invention, aromatic fluorine compounds such as 1-chloro-2,3-difluorobenzene, which are useful as raw materials for fluorine-containing pharmaceutical and agricultural intermediates, can be industrially advantageously obtained. Examples of the present invention will be described in more detail below.
実施例 １
（塩素化工程）
200c.c.容量の円筒状ガラス製反応器に１−クロ
ロ−２−フルオロ−３−ニトロベンゼンを100g
（0.570モル）を入れ、175℃に加熱した。そこに
塩素6g／hr（0.085モル／hr）を吹き込み、14時間
反応させた。反応終了後、ガスクロマトグラフイ
ーにより分析した処、原料の反応率85％、１，３
−ジクロロ−２−フルオロベンゼンへの選択率94
％であつた。Example 1 (Chlorination step) 100 g of 1-chloro-2-fluoro-3-nitrobenzene was placed in a cylindrical glass reactor with a capacity of 200 c.c.
(0.570 mol) and heated to 175°C. 6 g/hr (0.085 mol/hr) of chlorine was blown into it and the reaction was allowed to proceed for 14 hours. After the reaction was completed, analysis by gas chromatography showed that the reaction rate of the raw materials was 85%, 1,3
-Selectivity to dichloro-2-fluorobenzene94
It was %.
（フツ素化工程）
200c.c.容量のSUS−316製オートクレーブにテ
トラフエニルホスホニウムクロライド27.3g
（0.0728モル）とスプレイ乾燥KF28.2g（0.485モ
ル）及び前記塩素化工程で得た１，３−ジクロロ
−２−フルオロベンゼン100g（0.606モル）を加
え、撹拌下、220℃で10時間反応させた。冷却後、
反応液を分析した処、原料の反応率51.0％、１−
クロロ−２，３−ジフルオロベンゼンへの選択率
82％、１，２，３，−トリフルオロベンゼンへの
選択率14％であつた。 (Fluorination process) 27.3 g of tetraphenylphosphonium chloride was placed in a SUS-316 autoclave with a capacity of 200 c.c.
(0.0728 mol), 28.2 g (0.485 mol) of spray-dried KF, and 100 g (0.606 mol) of 1,3-dichloro-2-fluorobenzene obtained in the chlorination step were added, and the mixture was reacted with stirring at 220°C for 10 hours. Ta. After cooling,
Analysis of the reaction solution revealed that the reaction rate of the raw materials was 51.0%, 1-
Selectivity to chloro-2,3-difluorobenzene
The selectivity to 1,2,3-trifluorobenzene was 14%.
実施例 ２
（塩素化工程）
200c.c.容量のハステロイＣ製オートクレーブに
１−クロロ−２−フルオロ−３−ニトロベンゼン
を40g（0.22モル）と塩素12.4g／hr（0.175モル）を
仕込み、190℃で８時間反応させた。反応液の分
析を行なつた処、原料の反応率74.3％、１，３−
ジクロロ−２−フルオロベンゼンへの選択率62％
であつた。Example 2 (Chlorination step) A Hastelloy C autoclave with a capacity of 200 c.c. was charged with 40 g (0.22 mol) of 1-chloro-2-fluoro-3-nitrobenzene and 12.4 g/hr (0.175 mol) of chlorine. The reaction was carried out at ℃ for 8 hours. Analysis of the reaction solution revealed that the reaction rate of the raw materials was 74.3%, 1,3-
Selectivity to dichloro-2-fluorobenzene 62%
It was hot.
（フツ素化工程）
200c.c.容量のSUS−316製オートクレーブに、
テトラブチルホスホニウムブロマイド22.2g
（0.0654モル）とスプレイ乾燥KF25.3g（0.436モ
ル）及び前記塩素化工程で得た１，３−ジクロロ
−２−フルオロベンゼン90g（0.545モル）を加え、
撹拌下、235℃で10時間反応させた。冷却後、反
応液を分析した処、原料の反応率35.0％、１−ク
ロロ−２，３−ジフルオロベンゼンへの選択率71
％であつた。 (Fluorination process) In a SUS-316 autoclave with a capacity of 200c.c.
Tetrabutylphosphonium bromide 22.2g
(0.0654 mol), 25.3 g (0.436 mol) of spray-dried KF and 90 g (0.545 mol) of 1,3-dichloro-2-fluorobenzene obtained in the chlorination step,
The reaction was carried out at 235° C. for 10 hours while stirring. After cooling, the reaction solution was analyzed, and the reaction rate of the raw material was 35.0%, and the selectivity to 1-chloro-2,3-difluorobenzene was 71.
It was %.
比較例 １
200c.c.容量のSUS−316製オートクレーブにス
プレイ乾燥KF42.3g（0.728モル）及び実施例２の
塩素化工程で得た１，３−ジクロロ−２−フルオ
ロベンゼン60g（0.364モル）を加え、撹拌下、450
℃で10時間反応させた。冷却後、反応液を分析し
た処、原料の反応率45.0％、１−クロロ−２，３
−ジフルオロベンゼンへの選択率28.5％であつ
た。Comparative Example 1 Spray-dried 42.3 g (0.728 mol) of KF and 60 g (0.364 mol) of 1,3-dichloro-2-fluorobenzene obtained in the chlorination process of Example 2 in a SUS-316 autoclave with a capacity of 200 c.c. and under stirring, 450
The reaction was carried out at ℃ for 10 hours. After cooling, the reaction solution was analyzed and found that the reaction rate of the raw material was 45.0%, 1-chloro-2,3
-The selectivity to difluorobenzene was 28.5%.
Claims (1)
化合物のニトロ基を塩素ガスにより塩素置換し、
次いで第４級ホスホニウム塩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
れる芳香族フツ素化合物を得ることを特徴とする
芳香族フツ素化合物の製造方法。 （式中、Ｘ、ＹはそれぞれCl、Br、Ｆ又はＨ、
但しＸ、Ｙ共にＨは除く。 R1、R2、R3、R4、R5、R6はそれぞれCl、Br、
Ｆ、NO2、CN、CF3又はＨを示す）。 ２ 第４級ホスホニウム塩がテトラフエニルホス
ホニウムクロライド又はテトラフエニルホスホニ
ウムブロマイドである特許請求の範囲第１項記載
の芳香族フツ素化合物の製造方法。[Claims] 1. The nitro group of an aromatic nitro compound represented by the following general formula () is replaced with chlorine using chlorine gas,
A method for producing an aromatic fluorine compound, which comprises then reacting it with a metal fluoride in the presence of a quaternary phosphonium salt to obtain an aromatic fluorine compound represented by the following general formula (). (In the formula, X and Y are respectively Cl, Br, F or H,
However, H is excluded for both X and Y. R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are respectively Cl, Br,
F, NO 2 , CN, CF 3 or H). 2. The method for producing an aromatic fluorine compound according to claim 1, wherein the quaternary phosphonium salt is tetraphenylphosphonium chloride or tetraphenylphosphonium bromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59101669A JPS60246326A (en) | 1984-05-22 | 1984-05-22 | Preparation of aromatic fluorine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59101669A JPS60246326A (en) | 1984-05-22 | 1984-05-22 | Preparation of aromatic fluorine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60246326A JPS60246326A (en) | 1985-12-06 |
| JPH0155253B2 true JPH0155253B2 (en) | 1989-11-22 |
Family
ID=14306772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59101669A Granted JPS60246326A (en) | 1984-05-22 | 1984-05-22 | Preparation of aromatic fluorine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60246326A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2577567B2 (en) * | 1987-07-07 | 1997-02-05 | イハラケミカル工業株式会社 | Method for producing aromatic fluorine compound |
| US5208394A (en) * | 1988-08-26 | 1993-05-04 | Asahi Glass Company Ltd. | Process for producing chlorofluorobenzenes |
| CN110498730B (en) * | 2019-08-13 | 2021-12-03 | 浙江吉泰新材料股份有限公司 | Synthetic method of 1,2, 4-trifluorobenzene |
-
1984
- 1984-05-22 JP JP59101669A patent/JPS60246326A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60246326A (en) | 1985-12-06 |
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