JPH0466223B2 - - Google Patents
Info
- Publication number
- JPH0466223B2 JPH0466223B2 JP59052952A JP5295284A JPH0466223B2 JP H0466223 B2 JPH0466223 B2 JP H0466223B2 JP 59052952 A JP59052952 A JP 59052952A JP 5295284 A JP5295284 A JP 5295284A JP H0466223 B2 JPH0466223 B2 JP H0466223B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- halogenated
- dichloro
- formula
- nitrobenzoic acid
- 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 - Lifetime
Links
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 10
- 150000005338 nitrobenzoic acids Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000006114 decarboxylation reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- -1 2,3,4-trichloro-6-nitrobenzoic acid Chemical compound 0.000 description 8
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 8
- 125000001153 fluoro group Chemical class F* 0.000 description 5
- 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 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 235000003270 potassium fluoride Nutrition 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture 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
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- MTBYTWZDRVOMBR-UHFFFAOYSA-N 1,2,3,4-tetrachloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C(Cl)=C1Cl MTBYTWZDRVOMBR-UHFFFAOYSA-N 0.000 description 1
- BGKIECJVXXHLDP-UHFFFAOYSA-N 1,2,3-trichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1Cl BGKIECJVXXHLDP-UHFFFAOYSA-N 0.000 description 1
- HHLCSFGOTLUREE-UHFFFAOYSA-N 1,2,3-trichloro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(Cl)C(Cl)=C1 HHLCSFGOTLUREE-UHFFFAOYSA-N 0.000 description 1
- 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
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- OWALCRQILZGQDH-UHFFFAOYSA-N 1,3-dichloro-2,4-difluoro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=C(F)C(Cl)=C1F OWALCRQILZGQDH-UHFFFAOYSA-N 0.000 description 1
- YJUUZFWMKJBVFJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-4-one Chemical compound CN1CN(C)C(=O)C1 YJUUZFWMKJBVFJ-UHFFFAOYSA-N 0.000 description 1
- XNJAYQHWXYJBBD-UHFFFAOYSA-N 1,4-difluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(F)=CC=C1F XNJAYQHWXYJBBD-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
- RJXOVESYJFXCGI-UHFFFAOYSA-N 2,4-difluoro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1F RJXOVESYJFXCGI-UHFFFAOYSA-N 0.000 description 1
- DPHCXXYPSYMICK-UHFFFAOYSA-N 2-chloro-1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(Cl)=C1 DPHCXXYPSYMICK-UHFFFAOYSA-N 0.000 description 1
- KSLPTAKLPKUBES-UHFFFAOYSA-N 3,4,5-trichloro-2-nitrobenzoic acid Chemical compound ClC=1C(=C(C(=C(C(=O)O)C1)[N+](=O)[O-])Cl)Cl KSLPTAKLPKUBES-UHFFFAOYSA-N 0.000 description 1
- ZWJZUUYLXVXJSF-UHFFFAOYSA-N 3,4-dichloro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C(Cl)=C1[N+]([O-])=O ZWJZUUYLXVXJSF-UHFFFAOYSA-N 0.000 description 1
- LKMJMYZOEGSMDN-UHFFFAOYSA-N 3,5-dichloro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(Cl)=CC(Cl)=C1[N+]([O-])=O LKMJMYZOEGSMDN-UHFFFAOYSA-N 0.000 description 1
- ZBEWIPTYUHHZIS-UHFFFAOYSA-N 3,5-difluoro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=CC(F)=C1[N+]([O-])=O ZBEWIPTYUHHZIS-UHFFFAOYSA-N 0.000 description 1
- TVKAWNFBYDPGGW-UHFFFAOYSA-N 3,6-difluoro-2-nitrobenzoic acid Chemical compound OC(=O)C1=C(F)C=CC(F)=C1[N+]([O-])=O TVKAWNFBYDPGGW-UHFFFAOYSA-N 0.000 description 1
- SUHYJVCHLDIPIY-UHFFFAOYSA-N 4,5-dichloro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(Cl)=C(Cl)C=C1[N+]([O-])=O SUHYJVCHLDIPIY-UHFFFAOYSA-N 0.000 description 1
- QWRNVDWDFCINEY-UHFFFAOYSA-N 4-bromo-2-chloro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1Cl QWRNVDWDFCINEY-UHFFFAOYSA-N 0.000 description 1
- GGTQVIUWLUDQKR-UHFFFAOYSA-N 4-chloro-5-fluoro-2-nitrobenzoic acid Chemical compound OC(=O)C1=CC(F)=C(Cl)C=C1[N+]([O-])=O GGTQVIUWLUDQKR-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000911 decarboxylating effect Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000000126 substance 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
- 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】
本発明は、一般式
（式中X1，X2，X3及びX4は水素原子もしくは
ハロゲン原子を表し、各々が同一又は異なつてい
てもよく、３者又は４者が同時に水素原子である
ことはない。）
で示されるハロゲン化ニトロベンゼン類の製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula (In the formula, X 1 , X 2 , X 3 and X 4 represent hydrogen atoms or halogen atoms, and each may be the same or different, and three or four of them cannot be hydrogen atoms at the same time.) The present invention relates to a method for producing halogenated nitrobenzenes shown in the following.
前記一般式（）で示されるハロゲン化ニトロ
ベンゼン類、例えば２，４−ジクロロ−３−フル
オロニトロベンゼン、３，５−ジクロロ−２，４
−ジフルオロニトロベンゼンは、抗菌剤として知
られているピリド〔１，２，３−de〕〔１，４〕
ベンゾオキサジン誘導体（特開昭57−46986号公
報）等の製造中間体として有用であり、工業的な
製造方法が望まれている。 Halogenated nitrobenzenes represented by the general formula (), such as 2,4-dichloro-3-fluoronitrobenzene, 3,5-dichloro-2,4
-Difluoronitrobenzene is a pyrido[1,2,3-de][1,4] which is known as an antibacterial agent.
It is useful as an intermediate in the production of benzoxazine derivatives (Japanese Unexamined Patent Publication No. 57-46986), and an industrial production method is desired.
従来、前記一般式（）で示されるハロゲン化
ニトロベンゼン類の選択的製造法としては、銅粉
又は酸化銅の存在下キノリン中で加熱脱炭酸反応
させる方法が知られている。（ケミカル・アブス
トラクト第74巻64020記載）しかしながら上記方
法では収率が最高60％と低く、前記一般式（）
で示されるハロゲン化ニトロベンゼン類の工業的
製造方法としては十分なものでなかつた。 Conventionally, as a method for selectively producing halogenated nitrobenzenes represented by the general formula (), a method is known in which a heating decarboxylation reaction is carried out in quinoline in the presence of copper powder or copper oxide. (Chemical Abstracts Vol. 74, 64020) However, the above method has a low yield of 60% at most, and the general formula ()
This method was not sufficient as an industrial production method for the halogenated nitrobenzenes shown in the following.
本発明者らはこの様な現状に鑑み、前記一般式
（）で示されるハロゲン化ニトロベンゼン類の
工業的製造方法を提供すべく鋭意研究を重ねた結
果、意外にも有機溶媒として非プロトン性極性溶
媒を、触媒としてフツ素塩をそれぞれ選択使用し
これらの存在下ハロゲン化ニトロ安息香酸類を加
熱脱炭酸反応させることにより、従来の問題点を
解決し得ることを認め本発明を完成するに至つ
た。 In view of the current situation, the present inventors have conducted intensive research to provide an industrial method for producing halogenated nitrobenzenes represented by the general formula (). The present inventors recognized that the problems of the prior art could be solved by selectively using a solvent and a fluorine salt as a catalyst and subjecting halogenated nitrobenzoic acids to a thermal decarboxylation reaction in the presence of these, leading to the completion of the present invention. .
すなわち本発明は有機溶媒中、一般式
（式中X1，X2，X3及びX4は水素原子もしくは
ハロゲン原子を表し、各々が同一又は異なつてい
てもよく、３者又は４者が同時に水素原子である
ことはない。）
で示されるハロゲン化ニトロ安息香酸類を加熱脱
炭酸反応させて、一般式
（式中X1，X2，X3及びX4は前記と同様の意味
を表す。）
で示されるハロゲン化ニトロベンゼン類を製造す
る方法において、有機溶媒として非プロトン性極
性溶媒を、触媒としてフツ素塩を使用することを
特徴とする前記一般式（）で示されるハロゲン
化ニトロベンゼン類の製造方法である。 That is, the present invention provides the method for preparing the general formula in an organic solvent. (In the formula, X 1 , X 2 , X 3 and X 4 represent hydrogen atoms or halogen atoms, and each may be the same or different, and three or four of them cannot be hydrogen atoms at the same time.) By subjecting the halogenated nitrobenzoic acids represented by the formula to a heating decarboxylation reaction, the general formula (In the formula, X 1 , X 2 , X 3 and This is a method for producing halogenated nitrobenzenes represented by the general formula (), characterized in that a basic salt is used.
本発明において原料として使用するハロゲン化
ニトロ安息香酸類は一般式（）で示される化合
物であり、例えば３，４−ジクロロ−２−ニトロ
安息香酸、３，５−ジクロロ−２−ニトロ安息香
酸、４，５−ジクロロ−２−ニトロ安息香酸、
３，４，５−トリクロロ−２−ニトロ安息香酸、
２，３，４−トリクロロ−６−ニトロ安息香酸、
２，３，４，５−テトラクロロ−６−ニトロ安息
香酸、３，５−ジクロロ−４−フルオロ−２−ニ
トロ安息香酸、３，５−ジフルオロ−２−ニトロ
安息香酸、５−ブロモ−３−クロロ−２−ニトロ
安息香酸、３，６−ジフルオロ−２−ニトロ安息
香酸、４−クロロ−５−フルオロ−２−ニトロ安
息香酸、２，４−ジクロロ−３−ブロモ−６−ニ
トロ安息香酸、３，５−ジフルオロ−４，６−ジ
クロロ−２−ニトロ安息香酸等を挙げることがで
きる。 The halogenated nitrobenzoic acids used as raw materials in the present invention are compounds represented by the general formula (), such as 3,4-dichloro-2-nitrobenzoic acid, 3,5-dichloro-2-nitrobenzoic acid, 4 , 5-dichloro-2-nitrobenzoic acid,
3,4,5-trichloro-2-nitrobenzoic acid,
2,3,4-trichloro-6-nitrobenzoic acid,
2,3,4,5-tetrachloro-6-nitrobenzoic acid, 3,5-dichloro-4-fluoro-2-nitrobenzoic acid, 3,5-difluoro-2-nitrobenzoic acid, 5-bromo-3 -Chloro-2-nitrobenzoic acid, 3,6-difluoro-2-nitrobenzoic acid, 4-chloro-5-fluoro-2-nitrobenzoic acid, 2,4-dichloro-3-bromo-6-nitrobenzoic acid , 3,5-difluoro-4,6-dichloro-2-nitrobenzoic acid and the like.
本発明の方法において使用するフツ素塩として
は、例えばフツ化セシウム、フツ化カリウム、フ
ツ化ナトリウム、フツ化リチウム、テトラメチル
アンモニウムフルオライド、フツ化アンモニウム
等が挙げられる。なかでも無水フツ化カリウムの
使用が好ましい。尚、触媒として銅、酸化銅、臭
化銅等のフツ素塩以外のものを使用した場合は目
的とする化合物を充分に得ることはできない。 Examples of the fluorine salt used in the method of the present invention include cesium fluoride, potassium fluoride, sodium fluoride, lithium fluoride, tetramethylammonium fluoride, and ammonium fluoride. Among them, it is preferable to use anhydrous potassium fluoride. Note that if a catalyst other than a fluorine salt such as copper, copper oxide, or copper bromide is used, the desired compound cannot be sufficiently obtained.
また、非プロトン性極性溶媒としてはジメチル
ホルムアミド、ジメチルスルホキシド、ジメチル
アセトアミド、ジグライム、スルホラン、１，３
−ジメチル−２−イミダゾリノン、ジメチルスル
ホン、ニトロベンゼン等が挙げられる。尚、キノ
リン、キシレン等の非プロトン性極性溶媒以外の
溶媒を用いた場合は目的の化合物が得られない。 In addition, examples of aprotic polar solvents include dimethylformamide, dimethylsulfoxide, dimethylacetamide, diglyme, sulfolane, 1,3
-dimethyl-2-imidazolinone, dimethylsulfone, nitrobenzene and the like. Note that if a solvent other than an aprotic polar solvent such as quinoline or xylene is used, the desired compound cannot be obtained.
本発明においてハロゲン化ニトロ安息香酸類を
脱炭酸反応させ得られるハロゲン化ニトロベンゼ
ン類は、一般式（）で示される化合物であり、
例えば２，３−ジクロロニトロベンゼン、２，４
−ジクロロニトロベンゼン、３，４−ジクロロニ
トロベンゼン、２，３，４−トリクロロニトロベ
ンゼン、３，４，５−トリクロロニトロベンゼ
ン、２，３，４，５−テトラクロロニトロベンゼ
ン、２，４−ジクロロ−３−フルオロニトロベン
ゼン、２，４−ジフルオロニトロベンゼン、２−
クロロ−４−ブロモニトロベンゼン、２，５−ジ
フルオロニトロベンゼン、３−クロロ−４−フル
オロニトロベンゼン、３，５−ジクロロ−５−ブ
ロモニトロベンゼン、２，４−ジフルオロ−３，
５−ジクロロニトロベンゼン等を挙げることがで
きる。 In the present invention, halogenated nitrobenzenes obtained by decarboxylating halogenated nitrobenzoic acids are compounds represented by the general formula (),
For example, 2,3-dichloronitrobenzene, 2,4
-dichloronitrobenzene, 3,4-dichloronitrobenzene, 2,3,4-trichloronitrobenzene, 3,4,5-trichloronitrobenzene, 2,3,4,5-tetrachloronitrobenzene, 2,4-dichloro-3-fluoro Nitrobenzene, 2,4-difluoronitrobenzene, 2-
Chloro-4-bromonitrobenzene, 2,5-difluoronitrobenzene, 3-chloro-4-fluoronitrobenzene, 3,5-dichloro-5-bromonitrobenzene, 2,4-difluoro-3,
Examples include 5-dichloronitrobenzene.
本発明の方法は非プロトン性極性溶媒、一般式
（）で示されるハロゲン化ニトロ安息香酸類及
びハロゲン化ニトロ安息香酸１モル当り0.1〜0.8
モルのフツ素塩を混合し、100〜200℃好ましくは
130〜180℃で１〜５時間加熱撹拌し脱炭酸反応さ
せることによつて行なわれる。得られた反応物は
氷水中に注下した後、濾過又は抽出、濃縮、蒸留
等の常法により後処理することにより一般式
（）で示されるハロゲン化ニトロベンゼンが高
純度、高収率で得られる。このように本発明の方
法は、有機溶媒として非プロトン性極性溶媒を、
触媒としてフツ素塩を使用することにより、従来
の方法に比べ収率よくハロゲン化ニトロベンゼン
類が得られ、工業的にも効果の高い方法である。 The method of the present invention uses an aprotic polar solvent, a halogenated nitrobenzoic acid represented by the general formula (), and 0.1 to 0.8 halogenated nitrobenzoic acids per mole of the halogenated nitrobenzoic acid.
Mix moles of fluorine salt, preferably at 100-200℃
The decarboxylation reaction is carried out by heating and stirring at 130 to 180°C for 1 to 5 hours. The obtained reaction product is poured into ice water and then post-treated by conventional methods such as filtration, extraction, concentration, and distillation to obtain halogenated nitrobenzene represented by the general formula () with high purity and high yield. It will be done. In this way, the method of the present invention uses an aprotic polar solvent as an organic solvent,
By using a fluorine salt as a catalyst, halogenated nitrobenzenes can be obtained in higher yield than conventional methods, and this method is industrially highly effective.
以下実施例により本発明をさらに具体的に説明
する。 The present invention will be explained in more detail with reference to Examples below.
実施例 １
１４径フラスコにジメチルホルムアミド540
mlと無水フツ化カリウム4.45ｇ（0.077mol）を加
え、135〜140℃に昇温し、３，５−ジクロロ−４
−フルオロ−２−ニトロ安息香酸97.4ｇ
（0.383mol）を加え、同温で2.5時間撹拌下反応さ
せた。反応終了後、反応混合物を室温まで冷却し
た後氷水中にあけ抽出、濃縮しついでこれを蒸留
し、沸点113〜116℃／10mmＨｇの２，４−ジクロ
ロ−３−フルオロニトロベンゼン71.2ｇを得た。
収率は88.5％であつた。n20 D；1.5690）
実施例 ２
ジメチルホルムアミドの代わりにスルホランを
用い、180℃で1.5時間反応させた以外は実施例１
と同様に行つたところ、２，４−ジクロロ−３−
フルオロニトロベンゼン67.5ｇを得た。収率は
84.0％であつた。Example 1 Dimethylformamide 540 in a 14 diameter flask
ml and 4.45 g (0.077 mol) of anhydrous potassium fluoride were added, the temperature was raised to 135-140°C, and 3,5-dichloro-4
-Fluoro-2-nitrobenzoic acid 97.4g
(0.383 mol) was added, and the mixture was reacted at the same temperature for 2.5 hours with stirring. After the reaction was completed, the reaction mixture was cooled to room temperature, poured into ice water, extracted, concentrated, and then distilled to obtain 71.2 g of 2,4-dichloro-3-fluoronitrobenzene having a boiling point of 113-116°C/10 mmHg.
The yield was 88.5%. n 20 D ; 1.5690) Example 2 Example 1 except that sulfolane was used instead of dimethylformamide and the reaction was performed at 180°C for 1.5 hours.
When carried out in the same manner as above, 2,4-dichloro-3-
67.5 g of fluoronitrobenzene was obtained. The yield is
It was 84.0%.
比較例 １
ジメチルホルムアミドの代わりにキシレンを用
いた以外は、実施例１と同様に行つたところ反応
は進行せず、目的とする２，４−ジクロロ−３−
フルオロニトロベンゼンは得られなかつた。Comparative Example 1 The same procedure as in Example 1 was carried out except that xylene was used instead of dimethylformamide, but the reaction did not proceed and the target 2,4-dichloro-3-
No fluoronitrobenzene was obtained.
比較例 ２
無水フツ化カリウムを除いた以外は実施例１と
同様に行つたところ、反応は進行せず目的とする
２，４−ジクロロ−３−フルオロニトロベンゼン
は得られなかつた。Comparative Example 2 The same procedure as in Example 1 was carried out except that anhydrous potassium fluoride was omitted, but the reaction did not proceed and the desired 2,4-dichloro-3-fluoronitrobenzene was not obtained.
Claims (1)
ハロゲン原子を表し、各々が同一又は異なつてい
てもよく、３者又は４者が同時に水素原子である
ことはない。） で示されるハロゲン化ニトロ安息香酸類を加熱脱
炭酸反応させて、一般式 （式中X1，X2，X3及びX4は前記と同様の意味
を表す。） で示されるハロゲン化ニトロベンゼン類を製造す
る方法において、有機溶媒として非プロトン性極
性溶媒を、触媒としてフツ素塩を使用することを
特徴とする前記一般式（）で示されるハロゲン
化ニトロベンゼン類の製造方法。[Claims] 1. In an organic solvent, the general formula (In the formula, X 1 , X 2 , X 3 and X 4 represent hydrogen atoms or halogen atoms, and each may be the same or different, and three or four of them cannot be hydrogen atoms at the same time.) By subjecting the halogenated nitrobenzoic acids represented by the formula to a heating decarboxylation reaction, the general formula (In the formula, X 1 , X 2 , X 3 and 1. A method for producing halogenated nitrobenzenes represented by the general formula (), characterized in that a basic salt is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59052952A JPS60197640A (en) | 1984-03-19 | 1984-03-19 | Preparation of halogenated nitrobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59052952A JPS60197640A (en) | 1984-03-19 | 1984-03-19 | Preparation of halogenated nitrobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60197640A JPS60197640A (en) | 1985-10-07 |
| JPH0466223B2 true JPH0466223B2 (en) | 1992-10-22 |
Family
ID=12929211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59052952A Granted JPS60197640A (en) | 1984-03-19 | 1984-03-19 | Preparation of halogenated nitrobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60197640A (en) |
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|---|---|---|---|---|
| EP3597648B1 (en) * | 2017-03-14 | 2023-06-07 | Daiichi Sankyo Company, Limited | METHOD FOR PRODUCING 3, 6-DISUBSTITUTED IMIDAZO[1, 2-b]PYRIDAZINE DERIVATIVE |
| CN109467509B (en) * | 2017-09-08 | 2021-09-24 | 联化科技股份有限公司 | Preparation method of substituted nitrobenzene compounds |
-
1984
- 1984-03-19 JP JP59052952A patent/JPS60197640A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60197640A (en) | 1985-10-07 |
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