JP2672012B2 - Method for producing 1-chloro-3,4-difluorobenzene - Google Patents
Method for producing 1-chloro-3,4-difluorobenzeneInfo
- Publication number
- JP2672012B2 JP2672012B2 JP1104655A JP10465589A JP2672012B2 JP 2672012 B2 JP2672012 B2 JP 2672012B2 JP 1104655 A JP1104655 A JP 1104655A JP 10465589 A JP10465589 A JP 10465589A JP 2672012 B2 JP2672012 B2 JP 2672012B2
- Authority
- JP
- Japan
- Prior art keywords
- difluorobenzene
- chloro
- orthodifluorobenzene
- mixture
- dichloro
- 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
- OPQMRQYYRSTBME-UHFFFAOYSA-N 4-chloro-1,2-difluorobenzene Chemical compound FC1=CC=C(Cl)C=C1F OPQMRQYYRSTBME-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 13
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- YXELWOSSWQYFEF-UHFFFAOYSA-N 1,2-dichloro-4,5-difluorobenzene Chemical compound FC1=CC(Cl)=C(Cl)C=C1F YXELWOSSWQYFEF-UHFFFAOYSA-N 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- IUSXJNYNOFNTHP-UHFFFAOYSA-N 1,5-dichloro-2,3-difluorobenzene Chemical compound FC1=CC(Cl)=CC(Cl)=C1F IUSXJNYNOFNTHP-UHFFFAOYSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- ZBNCSBMIRFHJEL-UHFFFAOYSA-N 1-chloro-2,3-difluorobenzene Chemical compound FC1=CC=CC(Cl)=C1F ZBNCSBMIRFHJEL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AXNUZKSSQHTNPZ-UHFFFAOYSA-N 3,4-difluoroaniline Chemical compound NC1=CC=C(F)C(F)=C1 AXNUZKSSQHTNPZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- HXQWFROUEVBXFE-UHFFFAOYSA-N 1,2-dichloro-3,4-difluorobenzene Chemical class FC1=CC=C(Cl)C(Cl)=C1F HXQWFROUEVBXFE-UHFFFAOYSA-N 0.000 description 1
- RUBQQRMAWLSCCJ-UHFFFAOYSA-N 1,2-difluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(F)=C1 RUBQQRMAWLSCCJ-UHFFFAOYSA-N 0.000 description 1
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 1
- AJCSNHQKXUSMMY-UHFFFAOYSA-N 1-chloro-2,4-difluorobenzene Chemical compound FC1=CC=C(Cl)C(F)=C1 AJCSNHQKXUSMMY-UHFFFAOYSA-N 0.000 description 1
- RJCGZNCCVKIBHO-UHFFFAOYSA-N 1-chloro-4-fluorobenzene Chemical compound FC1=CC=C(Cl)C=C1 RJCGZNCCVKIBHO-UHFFFAOYSA-N 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- 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】 ［産業上の利用分野］ 本発明は医農薬等の中間体として有用な１−クロロ−
3,4−ジフルオロベンゼンを工業的に簡便に製造する方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is 1-chloro-, which is useful as an intermediate for medicines and agricultural chemicals.
The present invention relates to a method for industrially and conveniently producing 3,4-difluorobenzene.
［従来の技術］ 従来、１−クロロ−3,4−ジフルオロベンゼンの製法
としては、3,4−ジフルオロアニリンのサンドマイヤー
反応によって70％の収率で得る方法が最良の方法と考え
られている。〔G.C.Finger氏ら、J.Am.Chem.Socy81,94
（1959）〕。しかしながら、出発原料の3,4−ジフルオ
ロアニリンは人手しにくい化合物であり、例えば、オル
トジフルオロベンゼンをニトロ化し、3,4−ジフルオロ
ニトロベンゼンとした後に、接触還元して得る方法等
〔A.F.Helin氏ら、J.Am.Chem.Socy〕73,5884（1951）〕
が知られている。[Prior Art] Conventionally, as a method for producing 1-chloro-3,4-difluorobenzene, a method of obtaining a yield of 70% by Sandmeyer reaction of 3,4-difluoroaniline is considered to be the best method. . [GCFinger et al, J.Am.Chem.Socy 81, 94
(1959)]. However, the starting material 3,4-difluoroaniline is a compound that is difficult to handle, and for example, a method of nitrating orthodifluorobenzene to obtain 3,4-difluoronitrobenzene and then catalytically reducing the same (AF Helin et al., J.Am.Chem.Socy] 73 , 5884 (1951)]
It has been known.
又、1,2,4−トリクロロベンゼンをオートクレーブ
中、フッ化カリウム及びフッ化セシウムと反応させる
と、１−クロロ−3,4−ジフルオロベンゼンが混合物と
して低収率で得られている〔R.H.Shiley氏ら、J.Fluori
ne.Chemy２,19（1972/73）〕が、主生成物の１−クロロ
−2,4−ジフルオロベンゼンや１−クロロ−４−フルオ
ロベンゼンから単離するのは困難である。Also, when 1,2,4-trichlorobenzene is reacted with potassium fluoride and cesium fluoride in an autoclave, 1-chloro-3,4-difluorobenzene is obtained as a mixture in low yield [RH Shiley Et al., J. Fluori
ne.Chemy 2 , 19 (1972/73)] is difficult to isolate from the main products 1-chloro-2,4-difluorobenzene and 1-chloro-4-fluorobenzene.
このような従来法は工程が長かったり、単離の困難さ
等の問題があり、工業的に有利とは云えなかった。Such conventional methods are not industrially advantageous because they have problems such as long steps and difficulty in isolation.
［発明が解決しようとする課題］ 本発明の目的は、従来技術が有していた前述の欠点を
解消しようとするものである。[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned drawbacks of the prior art.
［課題を解決するための手段］ 本発明は従来法に比べ、工業的に安価で簡便に１−ク
ロロ−3,4−ジフルオロベンゼンを提供するものであ
り、特定の金属又は金属化合物の存在下、オルトジフル
オロベンゼンを塩素で塩素化することを特徴とする１−
クロロ−3,4−ジフルオロベンゼンの製造方法に関する
ものである。[Means for Solving the Problems] The present invention provides 1-chloro-3,4-difluorobenzene in an industrially inexpensive and simple manner as compared with the conventional method, and in the presence of a specific metal or metal compound. , Ortho-difluorobenzene is chlorinated with chlorine 1-
The present invention relates to a method for producing chloro-3,4-difluorobenzene.
本発明者らはオルトジフルオロベンゼンの直接塩素化
について、鋭意研究をした結果、鉄、アンチモン、およ
びアルミニウムから選ばれる金属又は金属化合物の存在
下に塩素とオルトジフルベンゼンを反応させることによ
り、１−クロロ−2,3−ジフルオロベンゼン及びジクロ
ロ−3,4−ジフルオロベンゼン類の副生が抑制されるこ
とを見い出し、本発明を完成させた。As a result of earnest research on direct chlorination of orthodifluorobenzene, the present inventors have shown that by reacting chlorine and orthodiflubenzene in the presence of a metal or a metal compound selected from iron, antimony, and aluminum, 1- The present invention has been completed by finding that by-products of chloro-2,3-difluorobenzene and dichloro-3,4-difluorobenzenes are suppressed.
本発明製造方法によれば、入手し易い原料から容易に
高純度の１−クロロ−3,4−ジフルオロベンゼンを製造
することができる。According to the production method of the present invention, highly pure 1-chloro-3,4-difluorobenzene can be easily produced from readily available raw materials.
本発明の方法における鉄、もしくは鉄化合物として
は、鉄、塩化第１鉄、塩化第２鉄、酸化第１鉄、酸化第
２鉄、水酸化第１鉄、水酸化第２鉄が用いられるが、こ
れらのうち、好ましいのは、鉄、塩化第１鉄、塩化第２
鉄である。As the iron or iron compound in the method of the present invention, iron, ferrous chloride, ferric chloride, ferrous oxide, ferric oxide, ferrous hydroxide, ferric hydroxide are used. Of these, preferred are iron, ferrous chloride, and ferric chloride.
It is iron.
アンチモンもしくはアンチモン化合物としては、アン
チモン、三塩化アンチモン、五塩化アンチモン、三酸化
アンチモン、五酸化アンチモン、アンチモンオキシクロ
リド等が用いられるが、これらのうち好ましいのは五塩
化アンチモンである。As the antimony or antimony compound, antimony, antimony trichloride, antimony pentachloride, antimony trioxide, antimony pentaoxide, antimony oxychloride and the like are used, and of these, antimony pentachloride is preferable.
アルミニウムもしくはアルミニウム化合物としては、
塩化アルミニウムが好ましい。As aluminum or aluminum compound,
Aluminum chloride is preferred.
その使用量はオルトジフルオロベンゼンに対して0.01
〜3.0wt％が好ましく、特に好ましくは、0.01〜1.0wt％
である。The amount used is 0.01 with respect to orthodifluorobenzene.
~ 3.0wt% is preferable, 0.01 ~ 1.0wt% is particularly preferable.
It is.
本発明の塩素化反応の温度、時間、あるいはオルトジ
フルオロベンゼンに対する塩素の量等の反応条件は適
宜、最適な条件を選定すればよいが、およそ20〜80℃の
温度１〜５時間の反応時間、及びオルトジルフオロベン
ゼンに対する塩素の量を0.2〜1.0倍モルとして実施し得
る。本発明における塩素化反応は、通常無溶媒で行う
が、溶媒中でも実施し得る。好ましい溶媒としては、塩
化メチレン、クロロホルム、四塩化炭素である。The reaction conditions such as the temperature and time of the chlorination reaction of the present invention or the amount of chlorine with respect to orthodifluorobenzene may be appropriately selected, but the temperature is about 20 to 80 ° C. and the reaction time is 1 to 5 hours. , And the amount of chlorine with respect to orthosylfluorobenzene can be carried out at 0.2 to 1.0 times mol. The chlorination reaction in the present invention is usually carried out without a solvent, but it can also be carried out in a solvent. Preferred solvents are methylene chloride, chloroform and carbon tetrachloride.
オルトジフルオロベンゼンの塩素による塩素化によっ
て得られる１−クロロ−3,4−ジフルオロベンゼンを含
む反応生成物は通常の後処理及び蒸留をすることによっ
て、目的とする１−クロロ−3,4−ジフルオロベンゼン
を収率よく、高純度で得ることができる。The reaction product containing 1-chloro-3,4-difluorobenzene obtained by chlorination of orthodifluorobenzene with chlorine is subjected to usual post-treatment and distillation to obtain the desired 1-chloro-3,4-difluorobenzene. Benzene can be obtained in high yield and high purity.
以下に本発明の実施例について、さらに具体的に説明
する。Hereinafter, examples of the present invention will be described more specifically.
［実施例］ 実施例１ 撹拌機、還流冷却器、温度計、及びガス吹き込み管を
つけた300ml4つ口フラスコ中に、オルトジフルオロベン
ゼン200g（1.75モル）及び塩化第２鉄2.0gを仕込み、40
〜45℃で、塩素ガス51.1g/hr（0.72モル/hr）を１時間4
5分（1.26モル）吹き込んで反応させた。反応終了後、
冷却し、反応混合物を５％水酸化ナトリウム水溶液100m
lで洗浄し、次に水100mlで洗浄した。[Examples] Example 1 200 g (1.75 mol) of ortho-difluorobenzene and 2.0 g of ferric chloride were charged into a 300 ml four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas blowing tube.
Chlorine gas 51.1g / hr (0.72mol / hr) at ~ 45 ℃ for 1 hour 4
It was made to react by bubbling for 5 minutes (1.26 mol). After the reaction,
After cooling, the reaction mixture is 100m in 5% aqueous sodium hydroxide solution.
It was washed with l and then with 100 ml of water.
分液した有機層235gをガスクロマトグラフィーによっ
て分析すると、これは、オルトジフルオロベンゼン27.9
％、１−クロロ−3,4−ジフルオロベンゼン66.8％、１
−クロロ−2,3−ジフルオロベンゼン2.3％、1,2−ジク
ロロ−4,5−ジフルオロベンゼン2.5％及び1.3−ジクロ
ロ−4,5−ジフルオロベンゼン0.4％からなる混合物であ
った。When 235 g of the separated organic layer was analyzed by gas chromatography, it was found that orthodifluorobenzene was 27.9 g.
%, 1-chloro-3,4-difluorobenzene 66.8%, 1
It was a mixture of 2.3% of -chloro-2,3-difluorobenzene, 2.5% of 1,2-dichloro-4,5-difluorobenzene and 0.4% of 1.3-dichloro-4,5-difluorobenzene.
この混合物をディクソンパッキングを充填した精留塔
を用いて常圧蒸留すると、オルトジフルオロベンゼン6
5.0が回収されるとともに、１−クロロ−3,4−ジフルオ
ロベンゼン158g（純度98.3％）が得られた。bp.127〜９
℃。This mixture was subjected to atmospheric distillation using a rectification column packed with Dickson packing to obtain orthodifluorobenzene 6
5.0 was recovered and 158 g of 1-chloro-3,4-difluorobenzene (purity 98.3%) was obtained. bp.127 ~ 9
° C.
消費されたオルトジフルオロベンゼンに対する収率は
90％であった。The yield based on orthodifluorobenzene consumed is
90%.
実施例２ 実施例１と同様にして、オルトジフルオロベンゼン20
0g（1.75モル）及び塩化第２鉄2.0gの混合物中に40〜45
℃で塩素ガス49.7g/hr（0.7モル/hr）を２時間30分（1.
75モル）吹き込んで反応させ、同様の後処理後、247gの
有機層が得られた。これはガスクロマトグラフィー分析
より、オルトジフルオロベンゼン8.3％、１−クロロ−
3,4−ジフルオロベンゼン80.4％、１−クロロ−2,3−ジ
フルオロベンゼン2.4％、1,2−ジクロロ−4,5−ジフル
オロベンゼン7.2％、及び1,3−ジクロロ−4,5−ジフル
オロベンゼン1.8％からなる混合物であった。Example 2 In the same manner as in Example 1, orthodifluorobenzene 20
40-45 in a mixture of 0 g (1.75 mol) and 2.0 g ferric chloride
Chlorine gas 49.7g / hr (0.7mol / hr) for 2 hours 30 minutes (1.
(75 mol) was reacted by blowing in, and after the same post-treatment, 247 g of an organic layer was obtained. This was found by gas chromatography analysis to be orthodifluorobenzene 8.3%, 1-chloro-
3,4-Difluorobenzene 80.4%, 1-chloro-2,3-difluorobenzene 2.4%, 1,2-dichloro-4,5-difluorobenzene 7.2%, and 1,3-dichloro-4,5-difluorobenzene It was a mixture consisting of 1.8%.
これを精留すると、オルトジフルオロベンゼン20.0g
が回収されるとともに、１−クロロ−3,4−ジフルオロ
ベンゼンが199g（純度97.8％）得られた。消費されたオ
ルトジフルオロベンゼンに対する収率は80.4％であっ
た。When this is rectified, 20.0 g of orthodifluorobenzene is obtained.
Was recovered and 199 g (purity 97.8%) of 1-chloro-3,4-difluorobenzene was obtained. The yield based on the consumed orthodifluorobenzene was 80.4%.
実施例３ 実施例１と同様にして、オルトジフルオロベンゼン20
0g（1.75モル）及び塩化第２鉄2.0gの混合物中に70〜75
℃で塩素ガス58.0g/hr（0.817モル/hr）を１時間30分
（1.23モル）吹き込んで反応させ、同様の後処理後、23
2gの有機層が得られた。これはガスクロマトグラフィー
分析より、オルトジフルオロベンゼン24.3％、１−クロ
ロ−3,4−ジフルオロベンゼン69.6％、１−クロロ−2,3
−ジフルオロベンゼン2.2％、1,2−ジクロロ−4,5−ジ
フルオロベンゼン3.0％、及び1,3−ジクロロ−4,5−ジ
フルオロベンゼン0.9％からなる混合物であった。Example 3 In the same manner as in Example 1, orthodifluorobenzene 20
70-75 in a mixture of 0 g (1.75 mol) and 2.0 g ferric chloride
After injecting chlorine gas 58.0g / hr (0.817mol / hr) for 1 hour and 30 minutes (1.23mol) at ℃ for reaction, after similar post-treatment, 23
2 g of organic layer was obtained. This was found by gas chromatography analysis to be ortho-difluorobenzene 24.3%, 1-chloro-3,4-difluorobenzene 69.6%, 1-chloro-2,3
-A mixture of 2.2% difluorobenzene, 3.0% 1,2-dichloro-4,5-difluorobenzene and 0.9% 1,3-dichloro-4,5-difluorobenzene.
これを精留すると、オルトジフルオロベンゼン55gが
回収されるとともに、１−クロロ−3,4−ジフルオロベ
ンゼンが164g（純度98.2％）得られた。消費されたオル
トジフルオロベンゼンに対する収率は86.8％であった。When this was rectified, 55 g of ortho-difluorobenzene was recovered and 164 g (purity 98.2%) of 1-chloro-3,4-difluorobenzene was obtained. The yield based on the consumed orthodifluorobenzene was 86.8%.
実施例４ 実施例１と同様にして、オルトジフルオロベンゼン20
0g（1.75モル）及び塩化第２鉄2.0gの混合物中に70〜75
℃で塩素ガス82.4g/hr（1.16モル/hr）を１時間30分
（1.74モル）吹き込んで反応させ、同様の後処理後、23
9gの有機層が得られた。これはガスクロマトグラフィー
分析より、オルトジフルオロベンゼン10.3％、１−クロ
ロ−3,4−ジフルオロベンゼン78.0％、１−クロロ−2,3
−ジフルオロベンゼン2.2％、1,2−ジクロロ−4,5−ジ
フルオロベンゼン7.4％、及び1,3−ジクロロ−4,5−ジ
フルオロベンゼン1.7％からなる混合物であった。Example 4 In the same manner as in Example 1, orthodifluorobenzene 20
70-75 in a mixture of 0 g (1.75 mol) and 2.0 g ferric chloride
After blowing chlorine gas 82.4g / hr (1.16mol / hr) for 1 hour and 30 minutes (1.74mol) at ℃ for reaction, after the same post-treatment, 23
9 g of organic layer was obtained. This was found by gas chromatography analysis to be orthodifluorobenzene 10.3%, 1-chloro-3,4-difluorobenzene 78.0%, 1-chloro-2,3.
-A mixture of 2.2% difluorobenzene, 7.4% 1,2-dichloro-4,5-difluorobenzene and 1.7% 1,3-dichloro-4,5-difluorobenzene.
これを精留すると、オルトジフルオロベンゼン24.0g
が回収されるとともに、１−クロロ−3,4−ジフルオロ
ベンゼンが186g（純度97.9％）得られた。消費されたオ
ルトジフルオロベンゼンに対する収率は81％であった。When this is rectified, 24.0 g of ortho-difluorobenzene
Was recovered, and 186 g (purity 97.9%) of 1-chloro-3,4-difluorobenzene was obtained. The yield based on the orthodifluorobenzene consumed was 81%.
実施例５ 実施例１と同様に、オルトジフルオロベンゼン100g
（0.876モル）、四塩化炭素100ml、及び塩化第２鉄1.0g
の混合物中に60℃で塩素ガス29.8g/hr（0.42モル/hr）
を２時間（0.84モル）吹き込んで反応させ、同様の後処
理後、四塩化炭素溶液が266g得られた。ガスクロマトグ
ラフィーの四塩化炭素を除くピークを分析すると、これ
はオルトジルフオロベンゼン15.0％、１−クロロ−3,4
−ジフルオロベンゼン75.9％、１−クロロ−2,3−ジフ
ルオロベンゼン1.4％、1,2−ジクロロ−4,5−ジフルオ
ロベンゼン5.3％、及び1,3−ジクロロ−4,5−ジフルオ
ロベンゼン2.4％からなる混合物であった。Example 5 As in Example 1, 100 g of ortho-difluorobenzene
(0.876 mol), carbon tetrachloride 100 ml, and ferric chloride 1.0 g
29.8g / hr (0.42mol / hr) chlorine gas in a mixture of 60 ℃
Was blown in for 2 hours (0.84 mol) to react, and after the same post-treatment, 266 g of a carbon tetrachloride solution was obtained. Gas chromatographic peaks except carbon tetrachloride were analyzed and found to be 15.0% ortho-difluorobenzene and 1-chloro-3,4
-From difluorobenzene 75.9%, 1-chloro-2,3-difluorobenzene 1.4%, 1,2-dichloro-4,5-difluorobenzene 5.3%, and 1,3-dichloro-4,5-difluorobenzene 2.4% It was a mixture.
これを精留すると１−クロロ−3,4−ジフルオロベン
ゼンが94.0g（純度98.8％）得られた。オルトジフルオ
ロベンゼンの留分及び回収された四塩化炭素中に含まれ
るオルトジフルオロベンゼンの合計量は18.5gであっ
た。従って、消費されたオルトジフルオロベンゼンに対
する収率は88.6％であった。When this was rectified, 94.0 g (purity 98.8%) of 1-chloro-3,4-difluorobenzene was obtained. The total amount of orthodifluorobenzene contained in the fraction of orthodifluorobenzene and the recovered carbon tetrachloride was 18.5 g. Therefore, the yield based on the consumed orthodifluorobenzene was 88.6%.
実施例６ 実施例１と同様にして、オルトジフルオロベンゼン20
0g（1.75モル）、及び塩化アルミニウム3.5gの混合物中
に50℃で塩素ガス44.7g/hr（0.63モル/hr）を２時間
（1.26モル）吹き込んで反応させ、同様の後処理後、22
0gの有機層が得られた。これはガスクロマトグラフィー
分析より、オルトジフルオロベンゼン37.3％、１−クロ
ロ−3,4−ジフルオロベンゼン57.3％、１−クロロ−2,3
−ジフルオロベンゼン0.4％、1,2−ジクロロ−4,5−ジ
フルオロベンゼン2.9％、及び1,3−ジクロロ−4,5−ジ
フルオロベンゼン2.1％からなる混合物であった。Example 6 In the same manner as in Example 1, orthodifluorobenzene 20
Chlorine gas 44.7 g / hr (0.63 mol / hr) was blown into a mixture of 0 g (1.75 mol) and 3.5 g of aluminum chloride at 50 ° C. for 2 hours (1.26 mol) to react, and after the same post-treatment, 22
0 g of organic layer was obtained. This was found by gas chromatography analysis to be ortho-difluorobenzene 37.3%, 1-chloro-3,4-difluorobenzene 57.3%, 1-chloro-2,3.
-A mixture of 0.4% difluorobenzene, 2.9% 1,2-dichloro-4,5-difluorobenzene and 2.1% 1,3-dichloro-4,5-difluorobenzene.
これを精留すると、オルトジフルオロベンゼン80gが
回収されるとともに、１−クロロ−3,4−ジフルオロベ
ンゼンが127g（純度98.4％）得られた。消費されたオル
トジフルオロベンゼンに対する収率は81％であった。When this was rectified, 80 g of ortho-difluorobenzene was recovered and 127 g of 1-chloro-3,4-difluorobenzene (purity 98.4%) was obtained. The yield based on the orthodifluorobenzene consumed was 81%.
［発明の効果］ 本発明方法に従えば、オルトジフルオロベンゼンから
１段の反応で、医農薬中間体として有用な１−クロロ−
3,4−ジフルオロベンゼンが、高収率で純度良く得られ
る。[Effect of the Invention] According to the method of the present invention, 1-chloro-, which is useful as an intermediate for medicines and agricultural chemicals, is a one-step reaction from orthodifluorobenzene.
3,4-Difluorobenzene can be obtained in high yield and high purity.
Claims (2)
選ばれる金属又はその金属化合物の存在下にオルトジフ
ルオロベンゼンを塩素で塩素化することを特徴とする１
−クロロ−3,4−ジフルオロベンゼンの製造方法。1. Orthodifluorobenzene is chlorinated with chlorine in the presence of a metal selected from iron, antimony, and aluminum or a metal compound thereof.
-Method for producing chloro-3,4-difluorobenzene.
量が0.2〜1.0倍モルである請求項１に記載の製造方法。2. The production method according to claim 1, wherein the amount of chlorine is 0.2 to 1.0 times the molar amount of orthodifluorobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1104655A JP2672012B2 (en) | 1989-04-26 | 1989-04-26 | Method for producing 1-chloro-3,4-difluorobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1104655A JP2672012B2 (en) | 1989-04-26 | 1989-04-26 | Method for producing 1-chloro-3,4-difluorobenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02286636A JPH02286636A (en) | 1990-11-26 |
| JP2672012B2 true JP2672012B2 (en) | 1997-11-05 |
Family
ID=14386477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1104655A Expired - Lifetime JP2672012B2 (en) | 1989-04-26 | 1989-04-26 | Method for producing 1-chloro-3,4-difluorobenzene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2672012B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI991329A1 (en) * | 1999-06-15 | 2000-12-15 | Enichem Spa | PROCEDURE FOR THE PREPARATION OF TETRAFLUOROALOGENOBENZENI |
| US9573881B2 (en) | 2012-12-25 | 2017-02-21 | Nippon Soda Co., Ltd. | Halogenated aniline and method for producing same |
-
1989
- 1989-04-26 JP JP1104655A patent/JP2672012B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02286636A (en) | 1990-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5241111A (en) | Processes for producing 5-fluorobenzoic acids and their intermediates | |
| EP0180057B1 (en) | Process for the preparation of halo aromatic compounds | |
| CA2113530C (en) | Process for the preparation of polyhalogenated benzotrichlorides and benzoyl chlorides and new trihalogeno-benzotrichlorides and -benzoyl chlorides | |
| EP0077853B1 (en) | Novel trifluoromethyl benzal chlorides and process for the preparation thereof | |
| JPH01301636A (en) | Production of 1,2,2,2-tetrafluoroethyl difluoromethyl ether | |
| JP2672012B2 (en) | Method for producing 1-chloro-3,4-difluorobenzene | |
| US5478963A (en) | 2,3-difluoro-6-nitrobenzonitrile and 2-chloro-5,6-difluorobenzonitrile-(2,3-difluoro-6-chlorobenzonitrile), process for their preparation and their use for the preparation of 2,3,6-trifluorobenzoic acid | |
| JP2793090B2 (en) | Method for producing bromopentafluorobenzene | |
| JPH0616613A (en) | 2-chloro-4,5-difluorobenzonitrile and its preparation | |
| US5792892A (en) | Processes for preparing aromatic, bromine-containing compounds, novel bromine-containing compounds, and their use as intermediate products in the synthesis of active agents | |
| EP0307481A1 (en) | Process for preparing 3-chloro-4-fluoronitrobenzene | |
| EP0038223B1 (en) | Process for the preparation of trifluoromethylbenzoyl halides | |
| US4952719A (en) | Process for the preparation of halo aromatic compounds | |
| JP2556357B2 (en) | Method for producing 3,5-di-tert-butyl-2,6-dichlorotoluene | |
| JPH0676343B2 (en) | Novel method for producing fluorinated aromatic compounds | |
| JP3040863B2 (en) | Method for producing 1-chloro-3,4-difluorobenzene | |
| JP5649288B2 (en) | Method for producing phthalic dichloride compound and catalyst used in the production method | |
| JPH07165638A (en) | New fluorobenzotrichloride compound | |
| JP2000212104A (en) | Method for producing bis (trifluoromethyl) monobromobenzene | |
| JPH0474340B2 (en) | ||
| JP3057146B2 (en) | Method for producing 2-halogeno-4,5-difluorobenzoyl fluorides | |
| JPH11189566A (en) | Method for producing fluoroalkylcarboxylic acid | |
| JP3531039B2 (en) | 1,4-difluorobenzene derivative | |
| JPH11255680A (en) | Production of benzene nuclear chlorine-substituted compound | |
| JPH07206777A (en) | Production of high-purity alkyl fluorobenzoate at high yield |