JPH04124159A - Production of aromatic fluorine compound - Google Patents
Production of aromatic fluorine compoundInfo
- Publication number
- JPH04124159A JPH04124159A JP2242524A JP24252490A JPH04124159A JP H04124159 A JPH04124159 A JP H04124159A JP 2242524 A JP2242524 A JP 2242524A JP 24252490 A JP24252490 A JP 24252490A JP H04124159 A JPH04124159 A JP H04124159A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- compounds
- hydrofluoric acid
- electron
- basic compound
- 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.)
- Granted
Links
- -1 aromatic fluorine compound Chemical class 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000007514 bases Chemical class 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000003682 fluorination reaction Methods 0.000 abstract description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000012025 fluorinating agent Substances 0.000 description 5
- 239000011698 potassium fluoride Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical group [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 2
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 description 1
- CPKWWONSNNHLAN-UHFFFAOYSA-N 1,3-dichloro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1Cl CPKWWONSNNHLAN-UHFFFAOYSA-N 0.000 description 1
- JSEVUBOYVADSHX-UHFFFAOYSA-N 1,3-dichloro-2-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(F)=C1Cl JSEVUBOYVADSHX-UHFFFAOYSA-N 0.000 description 1
- VITSNECNFNNVQB-UHFFFAOYSA-N 1,3-dichloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=C(Cl)C=CC=C1Cl VITSNECNFNNVQB-UHFFFAOYSA-N 0.000 description 1
- RZKKOBGFCAHLCZ-UHFFFAOYSA-N 1,4-dichloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC=C1Cl RZKKOBGFCAHLCZ-UHFFFAOYSA-N 0.000 description 1
- VLVNHMVSVDVAOA-UHFFFAOYSA-N 1,5-dichloro-2-nitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=C(Cl)C=C1Cl VLVNHMVSVDVAOA-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- GFJKASVFAWFUNI-UHFFFAOYSA-N 1-chloro-3,5-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC([N+]([O-])=O)=C1 GFJKASVFAWFUNI-UHFFFAOYSA-N 0.000 description 1
- HQROXDLWVGFPDE-UHFFFAOYSA-N 1-chloro-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(C(F)(F)F)=C1 HQROXDLWVGFPDE-UHFFFAOYSA-N 0.000 description 1
- QUIMTLZDMCNYGY-UHFFFAOYSA-N 2,4-dichloro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1Cl QUIMTLZDMCNYGY-UHFFFAOYSA-N 0.000 description 1
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 1
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- GJNGXPDXRVXSEH-UHFFFAOYSA-N 4-chlorobenzonitrile Chemical compound ClC1=CC=C(C#N)C=C1 GJNGXPDXRVXSEH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical class SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- PFZCOWLKXHIVII-UHFFFAOYSA-N pyridin-1-ium-1-amine Chemical class N[N+]1=CC=CC=C1 PFZCOWLKXHIVII-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は芳香族フッ素化合物の有利な製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an advantageous method for producing aromatic fluorine compounds.
フッ素化合物は優れた薬理活性や生理活性を有するため
に医薬や農薬としての利用が横棒的に試みられており、
芳香族フッ素化合物はその中間体として注目されている
。本発明は芳香族フッ素化合物を容易に且つ安価に製造
する方法に関する。Because fluorine compounds have excellent pharmacological and physiological activities, attempts have been made to use them as medicines and agricultural chemicals.
Aromatic fluorine compounds are attracting attention as intermediates. The present invention relates to a method for easily and inexpensively producing aromatic fluorine compounds.
芳香族フッ素化合物の製造方法は従来広く研究されてお
り、例えば、タロロニトロベンゼン誘導体を非プロトン
性極性溶液中でＫＦ等の金属フッ化物によってフッ素化
する方法などが知られている。またその改良方法として
特開昭６０−２３７０５１号には活性ハロゲン含有化合
物の存在下でＫＦ等によってフッ素化する方法が開示さ
れている。また特開平１−２１０４０３号にはハロゲン
化芳香族化合物をＫＦ等によってフッ素化する際に触媒
としてボリマー固定化アミノピリジニウム塩誘導体を用
いる方法が記載されている。しかしこれらの方法は何れ
も高価な触媒の使用が不可欠であり工業的に不利である
。Methods for producing aromatic fluorine compounds have been widely studied in the past, and for example, a method is known in which a talolonitrobenzene derivative is fluorinated with a metal fluoride such as KF in an aprotic polar solution. As an improved method, JP-A-60-237051 discloses a method of fluorination using KF or the like in the presence of an active halogen-containing compound. Further, JP-A-1-210403 describes a method in which a polymer-immobilized aminopyridinium salt derivative is used as a catalyst when fluorinating a halogenated aromatic compound with KF or the like. However, all of these methods require the use of expensive catalysts and are industrially disadvantageous.
またＫＦ以外のフッ素化剤を用いた方法も試みられてい
るが、これらの方法はオートクレーブを使用する高温高
圧の反応であって、更に高価な触媒やフッ素化剤を使用
するものが多〈実施し離い。Methods using fluorinating agents other than KF have also been attempted, but these methods involve high-temperature, high-pressure reactions using autoclaves, and many use more expensive catalysts and fluorinating agents. Away.
一方、工業的に入手し易く最も安価で一般的なフッ素化
剤である無水フッ酸を用いてフッ素化する方法は殆ど検
討されていない。On the other hand, a method of fluorination using anhydrous hydrofluoric acid, which is the most inexpensive and common fluorinating agent that is industrially easily available, has hardly been studied.
本発明者等は最も安価なフッ素化剤である無水フッ酸を
用い収率よく芳香族フッ素化合物を製造する方法の検討
を重ねた結果、ニトロ基に代表される電子吸引性の置換
基により活性化されたハロゲンを有する芳香族化合物に
対して塩基性化合物とくにトリエチルアミン、ピリジン
、γ−コリジンに代表されるアミン化合物と無水フッ酸
を併用すれば容易にフッ素化反応が進行することを見出
した。As a result of repeated studies on a method for producing aromatic fluorine compounds with good yield using anhydrous hydrofluoric acid, which is the cheapest fluorinating agent, the present inventors found that We have found that the fluorination reaction of an aromatic compound containing a halogen can easily proceed by using a basic compound, particularly an amine compound such as triethylamine, pyridine, or γ-collidine, in combination with anhydrous hydrofluoric acid.
本発明は上記知見に基づき、芳香族フッ素化合物を収率
よく経済的に製造できる方法を提供することを目的とす
る。Based on the above findings, the present invention aims to provide a method for economically producing aromatic fluorine compounds with good yield.
本発明によれば、一般式（１）
（式中、Ｘは塩素または臭素であり、Ｒ１，Ｒ２゜Ｒ３
，Ｒ４およびＲ５は各々独立に水素、塩素、臭素または
電子吸引性基であって、Ｒ１，Ｒ３またはＲ５のうち少
なくとも１つは電子吸引性基である。）
で表されるハロゲン化芳香族化合物を塩基性化合物の存
在下で無水フッ酸と反応させてフッ素化し芳香族フッ素
化合物を製造することを特徴とする方法が提供される。According to the present invention, the general formula (1) (wherein, X is chlorine or bromine, R1, R2゜R3
, R4 and R5 are each independently hydrogen, chlorine, bromine or an electron-withdrawing group, and at least one of R1, R3 or R5 is an electron-withdrawing group. ) is reacted with anhydrous hydrofluoric acid in the presence of a basic compound to fluorinate the halogenated aromatic compound to produce an aromatic fluorine compound.
さらに、上記製造方法であって、電子吸引性基がニトロ
基である製造方法および塩基性化合物がアミン化合物で
ある製造方法が提供される。Furthermore, the above-mentioned manufacturing method is provided, in which the electron-withdrawing group is a nitro group, and in which the basic compound is an amine compound.
本発明の方法はニトロ基に代表される電子吸引性の置換
基により活性化されたハロゲンを有する芳香族化合物を
出発物質として用いる。具体的には、２−クロロニトロ
ベンゼン、４−クロロニトロベンゼン、２，４−ジクロ
ロニトロベンゼン、２，６−シニトロクロロベンゼン、
２，４．６−ドリニトロクロロベンゼン、２．６−ジ
クロロニトロベンゼン、２，３−ジクロロニトロベンゼ
ン、２．５−ジクロロニトロベンゼン、３，５−ジニト
ロ−２，４−ジクロロベンゼン、２，４．５−トリニト
ロ−３，５−ジクロロベンゼン、２，４−ジクロロ−５
−トリフルオロメチルニトロベンゼン、２．４−ジクロ
ロ−３−フルオロニトロベンゼン、３，５−ジニトロ−
クロロベンゼン、２−クロロベンゾニトリル、４−クロ
ロベンゾニトリル、２，６−ジクロロベンゾニトリル、
４−クロロ−３−トリフルオロメチルニトロベンゼン、
２−クロロペンゾトリフルオリド、４−クロローペンゾ
トリフルオリドなどが用いられるが、これらに限定され
ない。The method of the present invention uses a halogen-containing aromatic compound activated by an electron-withdrawing substituent represented by a nitro group as a starting material. Specifically, 2-chloronitrobenzene, 4-chloronitrobenzene, 2,4-dichloronitrobenzene, 2,6-cynitrochlorobenzene,
2,4.6-Dolinitrochlorobenzene, 2,6-dichloronitrobenzene, 2,3-dichloronitrobenzene, 2,5-dichloronitrobenzene, 3,5-dinitro-2,4-dichlorobenzene, 2,4.5- Trinitro-3,5-dichlorobenzene, 2,4-dichloro-5
-trifluoromethylnitrobenzene, 2,4-dichloro-3-fluoronitrobenzene, 3,5-dinitro-
Chlorobenzene, 2-chlorobenzonitrile, 4-chlorobenzonitrile, 2,6-dichlorobenzonitrile,
4-chloro-3-trifluoromethylnitrobenzene,
2-chloropenzotrifluoride, 4-chloropenzotrifluoride, and the like are used, but are not limited thereto.
また本発明の方法で用いられる塩基性化合物としてはフ
ッ酸と錯体を形成する化合物が用いられる。具体的には
、エーテル化合物、ケトン化合物、アルデヒド化合物、
エステル化合物、アルコール化合物、カルボン酸化合物
、水、チオエーテル化合物、チオケトン化合物、チオア
ルデヒド化合物、チオエステル化合物、チオール化合物
、スルホオキシド化合物、スルホン化合物、アミン化合
物、アミド化合物、Ｎ−オキシド化合物、ニトリル化合
物、イソニトリル化合物、ホスフィン化合物、ホスファ
イト化合物、ホスフェート化合物などが用いられる。こ
れらの化合物のなかでアミン化合物が最も好ましい。特
に塩素とニトロ基がオルト位置に隣接し副反応が起き易
い場合には、塩基性化合物としてγ−コリジンを用いる
と副反応が殆ど起こらずに塩素をフッ素にハロゲン交換
することができ、芳香族フッ素化合物を高収率で得るこ
とができる。Further, as the basic compound used in the method of the present invention, a compound that forms a complex with hydrofluoric acid is used. Specifically, ether compounds, ketone compounds, aldehyde compounds,
Ester compounds, alcohol compounds, carboxylic acid compounds, water, thioether compounds, thioketone compounds, thioaldehyde compounds, thioester compounds, thiol compounds, sulfoxide compounds, sulfone compounds, amine compounds, amide compounds, N-oxide compounds, nitrile compounds, isonitriles compounds, phosphine compounds, phosphite compounds, phosphate compounds, etc. are used. Among these compounds, amine compounds are most preferred. In particular, when chlorine and nitro groups are adjacent to the ortho position and side reactions are likely to occur, using γ-collidine as a basic compound allows halogen exchange of chlorine to fluorine with almost no side reactions. Fluorine compounds can be obtained in high yield.
本発明方法の反応温度は、０〜２５０℃、好ましくは２
０〜２００℃である。反応温度が０℃より低いと反応の
進行が極端に遅いので好ましくない。また塩基性化合物
はフッ酸と錯体を形成しているが２５０℃を超えると錯
体ないし出発物質が系外に流出し、塩基性化合物を添加
する効果が失われるので好ましくない。The reaction temperature of the method of the present invention is 0 to 250°C, preferably 250°C.
The temperature is 0 to 200°C. If the reaction temperature is lower than 0°C, the progress of the reaction will be extremely slow, which is not preferable. Furthermore, the basic compound forms a complex with hydrofluoric acid, but if the temperature exceeds 250°C, the complex or starting material will flow out of the system, which is not preferable since the effect of adding the basic compound will be lost.
また無水フッ酸に対する出発原料の量は０．５〜７５ｍ
ｏ１％好ましくは１〜５０ｍｏ１％である。反応時間は
適宜定められるが０．５〜２４時間、好ましくは１〜１
５時間である。圧力は大気圧でもよく加圧してもよいが
、何れの場合も発生した塩化水素ないし臭化水素は速や
かに系外に抜き出すことが必要である。In addition, the amount of starting material for anhydrous hydrofluoric acid is 0.5 to 75 m
o1% preferably 1 to 50 mo1%. The reaction time is determined as appropriate, but is 0.5 to 24 hours, preferably 1 to 1 hour.
It is 5 hours. The pressure may be atmospheric pressure or pressurized, but in either case it is necessary to quickly extract the generated hydrogen chloride or hydrogen bromide from the system.
また上記塩基性化合物の最適添加量は出発物質の種類お
よび濃度によって適宜定められる。Further, the optimum amount of the basic compound to be added is appropriately determined depending on the type and concentration of the starting material.
ハロゲン交換反応に消費されたフッ酸、或いは蒸発した
フッ酸は間欠的または連続的に補給する。The hydrofluoric acid consumed in the halogen exchange reaction or the evaporated hydrofluoric acid is replenished intermittently or continuously.
この場合、蒸発したフッ酸をコンデンサーを経て冷却回
収し再利用しても良い。また反応進行中にフッ酸と出発
原料を連続的に供給し同時に沸点差を利用して生成物を
蒸留し系外に追出し回収することにより連続的な製造を
実施できる。反応終了後にエーテル等の適当な溶媒によ
って生成物を抽出分離し、或いは沸点差を利用して生成
物と塩基性化合物を分離し、分離した塩基性化合物のフ
ッ酸溶液を再利用することもできる。In this case, the evaporated hydrofluoric acid may be cooled and recovered through a condenser and reused. Furthermore, continuous production can be carried out by continuously supplying hydrofluoric acid and starting materials during the progress of the reaction, and at the same time distilling the product by utilizing the difference in boiling points and expelling it from the system and recovering it. After the reaction is completed, the product can be extracted and separated using a suitable solvent such as ether, or the product and the basic compound can be separated using the difference in boiling point, and the hydrofluoric acid solution of the separated basic compound can be reused. .
本発明の方法において、上記一般式（１）のハロゲン化
芳香族化合物は、塩素または臭素の結合位置に対してオ
ルト位および／またはパラ位に少なくとも１つの電子吸
引性基を有するので、結合している塩素また臭素が活性
化され、添加された塩基性化合物とフッ酸とによって形
成された錯体の活性なＦ−と上記塩素または臭素とがハ
ロゲン交換を行い、あるいは更にその他の基がフッ素と
置換し、出発原料のハロゲン化芳香族化合物にフッ素が
少なくとも１つ置換した芳香族フッ素化合物が生成され
る。In the method of the present invention, the halogenated aromatic compound of general formula (1) has at least one electron-withdrawing group at the ortho position and/or para position relative to the bonding position of chlorine or bromine, so that it is not bonded. chlorine or bromine is activated, and the active F- of the complex formed by the added basic compound and hydrofluoric acid undergoes halogen exchange with the chlorine or bromine, or other groups An aromatic fluorine compound in which at least one fluorine is substituted for the halogenated aromatic compound as a starting material is produced.
本発明の製造方法によれば、従来殆ど検討されていな無
水フッ酸を用い、高収率で芳香族フッ素化合物を製造す
ることができる。無水フッ酸は工業的に最も入手し易い
安価なフッ素化剤であり、従って本発明の方法は工業的
実施に適する。According to the production method of the present invention, aromatic fluorine compounds can be produced in high yield using anhydrous hydrofluoric acid, which has not been studied in the past. Anhydrous hydrofluoric acid is the most industrially available and inexpensive fluorinating agent, and therefore the method of the present invention is suitable for industrial implementation.
また、本発明の方法は副反応が殆ど生じない利点があり
、反応系の管理が容易であり実施し易い。Furthermore, the method of the present invention has the advantage that almost no side reactions occur, and the reaction system is easy to manage and easy to implement.
更に反応時間を長くすることにより収率を一層高めるこ
とができる。その他、本発明の方法は無水フッ酸を用い
るので、フッ化カリウムなどを用いる従来方法と異なり
、カリウムなどの不純物混入の問題が無く純度の高い製
品が得られる。Furthermore, the yield can be further increased by lengthening the reaction time. In addition, since the method of the present invention uses anhydrous hydrofluoric acid, unlike the conventional method using potassium fluoride, there is no problem of contamination with impurities such as potassium, and a highly pure product can be obtained.
実施例
０℃に冷却した１００ ｍｌのテフロン製反応容器に無
水フッ酸を１００ミＩＪモル入れ、攪拌しなから２，４
−ジニトロ−クロロベンゼン１０ミリモルと塩基性化合
物としてγ−コリジン１０ミリモルを徐々に加えた後、
反応容器を１５０℃のオイルパスに移し加熱しながら１
０時間反応させた。反応時に発生した塩化水素は反応容
器上蓋の細管を通じて大気中に放出した。反応中に無水
フッ酸（ガス状）を７５０ミＩＪモル連続的に追加した
。反応後冷却し、内容物を水中に入れエーテルで抽出し
た。抽出液を飽和食塩水で洗浄し、重曹で中和した後に
上層を分離し、上層のエーテル層を硫酸マグネシウムで
脱水して生成物を得た。Example 100 mmol of anhydrous hydrofluoric acid was placed in a 100 ml Teflon reaction vessel cooled to 0°C, and 2.4 ml of anhydrous hydrofluoric acid was added without stirring.
-After gradually adding 10 mmol of dinitro-chlorobenzene and 10 mmol of γ-collidine as a basic compound,
Transfer the reaction container to a 150℃ oil path and heat it for 1
The reaction was allowed to proceed for 0 hours. Hydrogen chloride generated during the reaction was released into the atmosphere through a thin tube in the upper lid of the reaction vessel. During the reaction, 750 mmol of anhydrous hydrofluoric acid (gaseous) was continuously added. After the reaction was cooled, the contents were poured into water and extracted with ether. After washing the extract with saturated brine and neutralizing with sodium bicarbonate, the upper layer was separated, and the upper ether layer was dehydrated with magnesium sulfate to obtain a product.
ガスクロマトグラフで生成物を分析したところ２゜４−
ジニトロフルオロベンゼンであることカ確！召された。When the product was analyzed using a gas chromatograph, it was found to be 2゜4-
Confirm that it is dinitrofluorobenzene! I was called.
また収率は６６％であった。なお、未反応の２．４−ジ
ニトロクロロベンゼンが２３％残留したが副反応は生じ
なかった。Moreover, the yield was 66%. Although 23% of unreacted 2,4-dinitrochlorobenzene remained, no side reactions occurred.
比較例
γ−コリジンを用いない他は実施例と同様にフッ素化を
行なった。得られた２、４−ジニトロフルオロベンゼン
の収率は１％で残りの９５％は未反応であった。Comparative Example Fluorination was carried out in the same manner as in the example except that γ-collidine was not used. The yield of the obtained 2,4-dinitrofluorobenzene was 1%, and the remaining 95% was unreacted.
特許出願人 株式会社トーケムプロダクン代理人 弁
理士松井政広（外１名）Patent applicant Tochem Product Co., Ltd. Agent Masahiro Matsui (1 other person)
Claims (3)
を塩基性化合物の存在下で無水フッ酸と反応させてフッ
素化し芳香族フッ素化合物を製造することを特徴とする
方法。 ▲数式、化学式、表等があります▼（１） （式中、Ｘは塩素または臭素であり、Ｒ１，Ｒ２，Ｒ３
，Ｒ４およびＲ５は各々独立に水素、塩素、臭素または
電子吸引性基であって、Ｒ１，Ｒ３またはＲ５のうち少
なくとも１つは電子吸引性基である。）(1) A method characterized by producing an aromatic fluorine compound by reacting a halogenated aromatic compound represented by general formula (1) with anhydrous hydrofluoric acid in the presence of a basic compound to fluorinate it. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, X is chlorine or bromine, R1, R2, R3
, R4 and R5 are each independently hydrogen, chlorine, bromine or an electron-withdrawing group, and at least one of R1, R3 or R5 is an electron-withdrawing group. )
方法。(2) The manufacturing method according to claim 1, wherein the electron-withdrawing group is a nitro group.
たは第２請求項の製造方法。(3) The manufacturing method according to claim 1 or 2, wherein the basic compound is an amine compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2242524A JP2923682B2 (en) | 1990-09-14 | 1990-09-14 | Method for producing aromatic fluorine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2242524A JP2923682B2 (en) | 1990-09-14 | 1990-09-14 | Method for producing aromatic fluorine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04124159A true JPH04124159A (en) | 1992-04-24 |
| JP2923682B2 JP2923682B2 (en) | 1999-07-26 |
Family
ID=17090395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2242524A Expired - Lifetime JP2923682B2 (en) | 1990-09-14 | 1990-09-14 | Method for producing aromatic fluorine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2923682B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3696156A1 (en) | 2019-02-15 | 2020-08-19 | Fujian Yongjing Technology Co., Ltd. | New process for the manufacture of fluoroaryl compounds and derivatives |
-
1990
- 1990-09-14 JP JP2242524A patent/JP2923682B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3696156A1 (en) | 2019-02-15 | 2020-08-19 | Fujian Yongjing Technology Co., Ltd. | New process for the manufacture of fluoroaryl compounds and derivatives |
| US11420917B2 (en) | 2019-02-15 | 2022-08-23 | Fujian Yongjing Technology Co., Ltd. | Process for the manufacture of fluoroaryl compounds and derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2923682B2 (en) | 1999-07-26 |
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