JPH02286636A - Production of 1-chloro-3,4-difluorobenzene - Google Patents
Production of 1-chloro-3,4-difluorobenzeneInfo
- Publication number
- JPH02286636A JPH02286636A JP10465589A JP10465589A JPH02286636A JP H02286636 A JPH02286636 A JP H02286636A JP 10465589 A JP10465589 A JP 10465589A JP 10465589 A JP10465589 A JP 10465589A JP H02286636 A JPH02286636 A JP H02286636A
- Authority
- JP
- Japan
- Prior art keywords
- difluorobenzene
- chloro
- orthodifluorobenzene
- raw material
- mol
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- OPQMRQYYRSTBME-UHFFFAOYSA-N 4-chloro-1,2-difluorobenzene Chemical compound FC1=CC=C(Cl)C=C1F OPQMRQYYRSTBME-UHFFFAOYSA-N 0.000 title description 14
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000005660 chlorination reaction Methods 0.000 abstract description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 abstract description 3
- 229960002089 ferrous chloride Drugs 0.000 abstract description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 2
- 239000000575 pesticide Substances 0.000 abstract 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- YXELWOSSWQYFEF-UHFFFAOYSA-N 1,2-dichloro-4,5-difluorobenzene Chemical compound FC1=CC(Cl)=C(Cl)C=C1F YXELWOSSWQYFEF-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- IUSXJNYNOFNTHP-UHFFFAOYSA-N 1,5-dichloro-2,3-difluorobenzene Chemical compound FC1=CC(Cl)=CC(Cl)=C1F IUSXJNYNOFNTHP-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
- 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
- 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
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 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
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 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
- RJCGZNCCVKIBHO-UHFFFAOYSA-N 1-chloro-4-fluorobenzene Chemical compound FC1=CC=C(Cl)C=C1 RJCGZNCCVKIBHO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 150000001463 antimony compounds Chemical class 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
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- XEKAUTDWPYQNFU-UHFFFAOYSA-N chlorane Chemical compound Cl.Cl.Cl XEKAUTDWPYQNFU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 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
- 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
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 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)
Abstract
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の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 Application Field] The present invention provides 1-chloro-3, which is useful as an intermediate for medicines and agricultural chemicals.
The present invention relates to a method for industrially and easily producing 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、ＣＦｉｎｇｅｒ氏ら、Ｊ、Ａｍ
、Ｃｈｅｍ、５ｏｃｙ ８１．９４［１９５９）］ 。[Prior Art] Conventionally, the best method for producing 1-chloro-3,4-difluorobenzene is considered to be the Sandmeyer reaction of 3,4-difluoroaniline with a yield of 70%. . [G, CFinger et al., J, Am
, Chem, 5ocy 81.94 [1959)].
しかしながら、出発原料の３．４−ジフルオロアニリン
は入手しに（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。However, the starting material 3,4-difluoroaniline is a compound that is difficult to obtain. F,
Helin et al., J.
Ａｍ、Ｃｈｅｍ、５ｏｃｙ ７３，５８８４ｆ１９５１
）］が知られている。Am, Chem, 5ocy 73,5884f1951
)]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，５ｈｉｌｅｙ氏
ら、Ｊ、Ｆｌｕｏｒｉｎｅ、Ｃｈｅｍｙ２ 。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 [R, H, 5hiley et al., J, Fluorine, 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。19 +1972/73)] is difficult to isolate from the main products 1-chloro-2°4-difluorobenzene and 1-chloro-4-fluorobenzene.
このように従来法は工程が長かったり、単離の困難さ等
問題点が多く、工業的に有利とは云えなかった。As described above, the conventional method has many problems such as long steps and difficulty in isolation, and cannot be said to be industrially advantageous.
［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 overcome 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ｌ−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 Problem] The present invention provides 1-chloro-3,4-difluorobenzene industrially at a lower cost and more easily than conventional methods. , relates to a method for producing l-chloro3,4-difluorobenzene, which is characterized by chlorinating orthodifluorobenzene with chlorine.
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、特定の鉄、アンチモン、
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
、転化率を調節することにより、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。The present inventors have conducted intensive research on the direct chlorination of orthodifluorobenzene, and have found that certain iron, antimony,
By adjusting the conversion rate in the presence of a metal or metal compound selected from aluminum, 1-chloro-2,3-
It was discovered that the by-products of difluorobenzene and dichloro-3,4-difluorobenzenes were suppressed, and the present invention was completed.
本発明製造方法によれば、人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 raw materials that are easy to handle.
本発明の方法に於て用いられる鉄、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。Iron or iron compounds used in the method of the present invention include iron, ferrous chloride, ferric chloride, ferrous oxide, ferric oxide, ferrous hydroxide, and ferric hydroxide. Among these, preferred are iron, ferrous chloride, and ferric chloride.
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 antimony or an antimony compound, antimony, antimony trichloride, antimony pentachloride, antimony trioxide, antimony pentoxide, antimony oxychloride, etc. are used, and among these, antimony pentachloride is preferred.
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 an 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０．０
１〜３．Ｏｗｔ％、好ましくは、０．０１〜１．０ｗｔ
％である。The amount used is 0.0 relative to orthodifluorobenzene.
1-3. Owt%, preferably 0.01-1.0wt
%.
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ガスのモル比等の反応条件
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０．２〜１．
０のモル比で実施し得る。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 temperature, time, and molar ratio of chlorine gas to ortho-difluorobenzene for the chlorination reaction of the present invention may be appropriately selected, but approximately
A reaction time of 1 to 5 hours at a temperature of 80°C, and a reaction time of 0.2 to 1.
It can be carried out with a molar ratio of 0. The chlorination reaction in the present invention is usually carried out without a solvent, but 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ｌ−クロロ−３，４−ジフルオロベンゼンは通
常の後処理及び蒸留によって、目的とするｌ−クロロ−
３，４−ジフルオロベンゼンが収率よく、高純度で得る
ことができる。l-chloro-3,4-difluorobenzene obtained by chlorination of orthodifluorobenzene with chlorine can be converted to the desired l-chloro-3,4-difluorobenzene through conventional post-treatment and distillation.
3,4-difluorobenzene can be obtained in good yield and with 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。Examples of the present invention will be described in more detail below.
［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３００ｎ＋４２４つロフラスコ中に、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／ｈｒｌを１時間４５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Ｌｏｏ
ｍβで洗浄し、次に水１００ｍ℃で洗浄した。[Examples] Example 1 In a 300n + 424 flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas blowing tube, 200 g (1.75 mol) of orthodifluorobenzene and chloride dichloride were added.
2.0g of iron was charged, and chlorine gas was heated to 51.0g at 40-45°C.
1 g/hr (0.72 mol/hrl for 1 hour 45 minutes (
1.26 mol) was blown into the reactor to cause a reaction. After completion of the reaction, the reaction mixture was cooled and diluted with a 5% aqueous sodium hydroxide solution.
Washed with mβ and then water at 100 m°C.
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２
７．９％、■−クロロー３．４−ジフルオロベンゼン６
６．８％、■−クロロー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２．６％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 2
7.9%, ■-chloro3,4-difluorobenzene6
6.8%, ■-chloro2.3-difluorobenzene2
．． 3%, 1,2-dichloro-4,5-difluorobenzene 2.6% and 1,3-dichloro-4,5-difluorobenzene 0.4%.
この混合物をデイクソンバッキングを充填した精留塔を
用いて常圧蒸留すると、才ルトジフルオロベンゼン６５
０ｇが回収されるとともに、ｌ−クロロ−３，４−ジフ
ルオロベンセンが１５８ｇ（純度９８．３％）が得られ
た。ｂｐ、 １２７〜９℃。When this mixture was distilled at atmospheric pressure using a rectification column packed with Dickson backing, it yielded 65% difluorobenzene.
0 g was recovered, and 158 g (purity 98.3%) of l-chloro-3,4-difluorobenzene was obtained. bp, 127-9°C.
消費されたオルトジフルオロベンセンに対する収率は９
０％であった。The yield based on consumed orthodifluorobenzene is 9
It was 0%.
実施例２
実施例１と同様にして、オルトジフルオロベンセン２０
０ｇ （１，７５干ル）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（１７５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
ルトジフルオロヘンセン８．３％、１−クロロ−３，４
−ジフルオロベンセン８０．４％、ｌ−クロロ−２，３
−ジフルオロベンセン２，４％。Example 2 In the same manner as in Example 1, orthodifluorobenzene 20
Chlorine gas 49.7 g/hr (0
, 7 mol/hr) was blown into the solution for 2 hours and 30 minutes (175 mol), and after the same post-treatment, 247 g of an organic layer was obtained. Gas chromatography analysis revealed that 8.3% orthodifluorohensen, 1-chloro-3,4
-difluorobenzene 80.4%, l-chloro-2,3
-difluorobenzene 2.4%.
１．２−ジクロロ−４，５−ジフルオロベンセン７２％
、及び１．３−ジクロロ−４，５−ジフルオロベンゼン
１８％からなる混合物であった。1,2-dichloro-4,5-difluorobenzene 72%
, and 18% of 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２００ｇ
回収とともに、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。これは消
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, 200g of orthodifluorobenzene is obtained.
Upon recovery, 199 g of 1-chloro-3,4-difluorobenzene (purity 97.8%) was obtained. This means that the yield based on the consumed orthodifluorobenzene is 80
．． It was 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゜Ｏｇの混合
物中に７０〜７５℃で塩素ガス５８．０ｇ／ｈｒ ｆＯ
，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、２３２ｇ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
0g (1,75 mol) and 2°Og of ferric chloride at 70-75°C with chlorine gas 58.0g/hr fO
, 817 mol/hr) was blown into the solution for 1 hour and 30 minutes (1.23 mol), and after the same post-treatment, 232 g of an organic layer was obtained. Gas chromatography analysis revealed that 24.3% orthodifluorobenzene, 1 chloro-
3,4-difluorobenzene 69.6%, 1chloro-2
, 3-difluorobenzene 2.2%, 1,2-dichloro-4,5-difluorobenzene 3.0%, and 1.3-
It was a mixture consisting of 0.9% 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回
収とともに、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 orthodifluorobenzene was recovered and 164 g of 1-chloro-3,4-difluorobenzene (purity 98.2%) was obtained. The yield based on 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、２３９ｇ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１Ｏ６３％、ｌ−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
82.4 g/hr (1,75 mol) of chlorine gas at 70-75°C in a mixture of 1,75 mol) and 2,0 g ferric chloride.
16 mol/hr) was blown into the solution for 1 hour and 30 minutes (1.74 mol), and after the same post-treatment, 239 g of an organic layer was obtained. This is from gas chromatography analysis.
Orthodifluorobenzene 1O63%, l-chloro-3
, 4-difluorobenzene 78.0%, 1-chloro-2
, 3-difluorobenzene 2.2%, 1,2-dichloro-4,5-difluorobenzene 7.4%, and 1.3-
It was a mixture consisting of 1.7% dichloro-4,5-difluorobenzene.
これを精留すると、オルトジフルオロベンゼン２４．０
ｇ回収とともに、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, orthodifluorobenzene 24.0
With the recovery of 186 g of 1-chloro-3,4-difluorobenzene (purity 97.9%). The yield based on consumed orthodifluorobenzene 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１００＋ｎＪ２、及
び塩化第２鉄１．０ｇの混合物中に６０°Ｃ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
ラフィー分析より、四塩化炭素のピークを除去すると、
オルトジフルオロベンゼン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 Same as Example 1, 100 g of orthodifluorobenzene
(0,876 mol), 100+nJ2 of carbon tetrachloride, and 1.0 g of ferric chloride at 60°C at 29.8 g/hr (0,42 mol/hr) of chlorine gas (0,84 After the same after-treatment, 266 g of carbon tetrachloride solution was obtained. When the carbon tetrachloride peak is removed from gas chromatography analysis,
Orthodifluorobenzene 15.0%, 1-chloro-3
, 4-difluorobenzene 75.9%, 1-chloro-2
, 3-difluorobenzene 1.4%, 1,2-dichloro-4,5-difluorobenzene 5.3%, and 1.3-
It was a mixture consisting of 2.4% dichloro-4,5 difluorobenzene.
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 of 1-chloro-3,4-difluorobenzene (purity 98.8%) was obtained. The total amount of orthodifluorobenzene contained in the orthodifluorobenzene fraction and recovered carbon tetrachloride is 18.5 g.
Met. Therefore, the yield based on 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３．５
ｇ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、２２０ｇ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％、■−クロロー２．３
−ジフルオロベンゼン０．４％、１２−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
0 g (1,75 mol), and aluminum chloride 3.5
44.7 g/hr (0
, 63 mol/hr) was blown into the solution for 2 hours (1.26 mol), and after the same post-treatment, 220 g of an organic layer was obtained. Gas chromatography analysis revealed that 37.3% orthodifluorobenzene, 1-chloro-3,4
-difluorobenzene 57.3%, ■-Chloro 2.3
-difluorobenzene 0.4%, 12-dichloro-4,
It was a mixture consisting of 2.9% of 5-difluorobenzene and 2.1% of 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回
収とともに、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。これは消費
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 orthodifluorobenzene was recovered and 127 g of 1-chloro-3,4-difluorobenzene (purity 98.4%) was obtained. This is a yield of 81% based on consumed orthodifluorobenzene.
Met.
［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
In the step reaction, 1-chloro-3, which is useful as a pharmaceutical and agricultural intermediate,
,4-difluorobenzene can be obtained in high yield and with good purity.
Claims (2)
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) 1-chloro-3,4 characterized by chlorinating orthodifluorobenzene in the presence of a metal selected from iron, antimony, and aluminum or a metal compound thereof
- A method for producing difluorobenzene.
２〜１．０当量の塩素を用いる請求項１に記載の製造方
法。(2) 0.0 molar ratio to orthodifluorobenzene.
2. The method according to claim 1, wherein 2 to 1.0 equivalents of chlorine are used.
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 true JPH02286636A (en) | 1990-11-26 |
| JP2672012B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003502299A (en) * | 1999-06-15 | 2003-01-21 | エニーケム・ソシエタ・ペル・アチオニ | Preparation of tetrafluorohalogenbenzene |
| WO2014103947A1 (en) * | 2012-12-25 | 2014-07-03 | 日本曹達株式会社 | Halogenated aniline and method for producing same |
-
1989
- 1989-04-26 JP JP1104655A patent/JP2672012B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003502299A (en) * | 1999-06-15 | 2003-01-21 | エニーケム・ソシエタ・ペル・アチオニ | Preparation of tetrafluorohalogenbenzene |
| JP4749638B2 (en) * | 1999-06-15 | 2011-08-17 | エニーケム・ソシエタ・ペル・アチオニ | Production of tetrafluorohalogenbenzene |
| WO2014103947A1 (en) * | 2012-12-25 | 2014-07-03 | 日本曹達株式会社 | Halogenated aniline and method for producing same |
| KR20150085082A (en) * | 2012-12-25 | 2015-07-22 | 닛뽕소다 가부시키가이샤 | Halogenated aniline and method for producing same |
| CN104884424A (en) * | 2012-12-25 | 2015-09-02 | 日本曹达株式会社 | Halogenated aniline and method for producing same |
| JP5965499B2 (en) * | 2012-12-25 | 2016-08-03 | 日本曹達株式会社 | Halogenated aniline and process for producing the same |
| EP2940002A4 (en) * | 2012-12-25 | 2016-08-31 | Nippon Soda Co | Halogenated aniline and method for producing same |
| US9573881B2 (en) | 2012-12-25 | 2017-02-21 | Nippon Soda Co., Ltd. | Halogenated aniline and method for producing same |
| US9758468B2 (en) | 2012-12-25 | 2017-09-12 | Nippon Soda Co., Ltd. | Halogenated aniline and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2672012B2 (en) | 1997-11-05 |
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