JPH0825987B2 - Process for producing 2-chloro-4-fluoro-5-nitrobenzenesulfonyl chloride - Google Patents
Process for producing 2-chloro-4-fluoro-5-nitrobenzenesulfonyl chlorideInfo
- Publication number
- JPH0825987B2 JPH0825987B2 JP32551387A JP32551387A JPH0825987B2 JP H0825987 B2 JPH0825987 B2 JP H0825987B2 JP 32551387 A JP32551387 A JP 32551387A JP 32551387 A JP32551387 A JP 32551387A JP H0825987 B2 JPH0825987 B2 JP H0825987B2
- Authority
- JP
- Japan
- Prior art keywords
- chloro
- fluoro
- producing
- nitrobenzenesulfonyl chloride
- present
- 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
- QQYXMCLSCRSLQP-UHFFFAOYSA-N 2-chloro-4-fluoro-5-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC(S(Cl)(=O)=O)=C(Cl)C=C1F QQYXMCLSCRSLQP-UHFFFAOYSA-N 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 5
- PTCPUGKKWNMITF-UHFFFAOYSA-N 4-chloro-2-fluoro-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1F PTCPUGKKWNMITF-UHFFFAOYSA-N 0.000 claims description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 4
- RZBYHILVAYXNPG-UHFFFAOYSA-N 5-amino-2-chloro-4-fluorobenzenethiol Chemical compound NC1=CC(S)=C(Cl)C=C1F RZBYHILVAYXNPG-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- KUAPPJSILOMQPC-UHFFFAOYSA-N 2-chloro-4-fluorobenzenethiol Chemical compound FC1=CC=C(S)C(Cl)=C1 KUAPPJSILOMQPC-UHFFFAOYSA-N 0.000 description 1
- MWWNNNAOGWPTQY-UHFFFAOYSA-N 3-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(S(Cl)(=O)=O)=C1 MWWNNNAOGWPTQY-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- 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、除草剤の中間体として有用な５−アミノ−
２−クロル−４−フルオロチオフェノールの新規な製造
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to 5-amino-, which is useful as an intermediate for herbicides.
The present invention relates to a novel method for producing 2-chloro-4-fluorothiophenol.
５−アミノ−２−クロル−４−フルオロチオフェノー
ル（III）の既知の合成法としては次の２つの方法があ
る。There are the following two methods as known synthesis methods of 5-amino-2-chloro-4-fluorothiophenol (III).
（１）EP-152890とEP-126419の組み合せ； 収率についての記載はない。(1) Combination of EP-152890 and EP-126419; There is no description about the yield.
（２）U.S.P.4613675; 収率についての記載はない。(2) USP4613675; There is no description about the yield.
本発明の目的は、効率よく、５−アミノ−２−クロル
−４−フルオロチオフェノール（III）を製造する方法
を提供することである。An object of the present invention is to provide a method for efficiently producing 5-amino-2-chloro-4-fluorothiophenol (III).
本発明は、 （１）２−クロル−４−フルオロ−５−ニトロベンゼン
スルホニルクロライド（II）。The present invention includes (1) 2-chloro-4-fluoro-5-nitrobenzenesulfonyl chloride (II).
（２）４−クロル−２−フルオロニトロベンゼン（１）
とクロルスルホン酸とを反応させることを特徴とする２
−クロル−４−フルオロ−５−ニトロベンゼンスルホニ
ルクロライド（II）の製造法である。また、得られた２
−クロル−４−フルオロ−５−ニトロベンゼンスルホニ
ルクロライド（II）は、還元することにより、除草剤中
間体として有用な５−アミノ−２−クロル−４−フルオ
ロチオフェノール（III）に誘導することができる。(2) 4-chloro-2-fluoronitrobenzene (1)
Characterized in that it reacts with chlorosulfonic acid 2
-A method for producing chloro-4-fluoro-5-nitrobenzenesulfonyl chloride (II). Also obtained 2
-Chloro-4-fluoro-5-nitrobenzenesulfonyl chloride (II) can be reduced to give 5-amino-2-chloro-4-fluorothiophenol (III) useful as a herbicide intermediate. it can.
本発明を反応式で示すと以下のとおりである。 The reaction scheme of the present invention is as follows.
本発明で用いられる原料の４−クロル−２−フルオロ
ニトロベンゼン（Ｉ）は2,4−ジクロルニトロベンゼン
より得られる。（本発明者らは同日付で、改良された
（Ｉ）の製造法を出願した。） 本発明のクロルスルホン化工程は、溶媒として、クロ
ロホルム、四塩化炭素等の不活性溶媒中あるいは、無溶
媒で温度は室温以上、好ましくは100〜130℃で行われ
る。クロルスルホン酸の使用量は、（Ｉ）の２倍モル以
上、好ましくは２倍モル〜10倍モルである。このクロル
スルホン化工程で得られる化合物（II）は文献未記載の
新規化合物である。 The starting material 4-chloro-2-fluoronitrobenzene (I) used in the present invention is obtained from 2,4-dichloronitrobenzene. (The present inventors applied for an improved production method of (I) on the same date.) In the chlorosulfonation step of the present invention, a solvent is used in an inert solvent such as chloroform or carbon tetrachloride, or without any solvent. The temperature of the solvent is room temperature or higher, preferably 100 to 130 ° C. The amount of chlorosulfonic acid used is 2 times or more, preferably 2 times to 10 times the mol of (I). The compound (II) obtained in this chlorosulfonation step is a novel compound not described in the literature.
還元工程は、塩化第１スズと塩酸、スズと塩酸、亜鉛
と硫酸等の還元剤を用い、温度は、室温から100℃で行
われる。In the reducing step, reducing agents such as stannous chloride and hydrochloric acid, tin and hydrochloric acid, zinc and sulfuric acid are used, and the temperature is from room temperature to 100 ° C.
次に実施例を挙げ本発明を更に詳細に説明する。 Next, the present invention will be described in more detail with reference to examples.
実施例１ ０℃に冷却したクロルスルホン酸18g中に攪拌下、４
−クロル−２−フルオロニトロベンゼン5gを加えた。室
温にて30分間、次いで120〜130℃で３時間攪拌した。反
応液は冷却後、氷200g中に注ぎ、酢酸エチル300mlで抽
出した。抽出液を飽和食塩水で洗浄後、硫酸マグネシウ
ムで乾燥、減圧下に溶媒を留去し、6.1gの２−クロル−
５−ニトロ−４フルオロベンゼンスルホニルクロライド
を得た。融点63〜４℃。Example 1 4g with stirring in 18g of chlorosulfonic acid cooled to 0 ° C
-Chlor-2-fluoronitrobenzene 5g was added. The mixture was stirred at room temperature for 30 minutes and then at 120 to 130 ° C for 3 hours. The reaction mixture was cooled, poured into 200 g of ice, and extracted with 300 ml of ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, the solvent was evaporated under reduced pressure, and 6.1 g of 2-chloro-
5-Nitro-4fluorobenzenesulfonyl chloride was obtained. Melting point 63-4 [deg.] C.
参考例 濃塩酸28mlと塩化第一スズ26.6gからなる溶液に攪拌
下０℃にて２−クロル−５−ニトロ−４−フルオロベン
ゼンスルホニルクロライド6gを加えた。同温度で10分間
攪拌後、冷却浴を取り除き、発熱下に1.5時間攪拌し
た。反応液に濃塩酸20mlを加え、しばらく攪拌後、結晶
を濾取した。Reference Example To a solution consisting of 28 ml of concentrated hydrochloric acid and 26.6 g of stannous chloride, 6 g of 2-chloro-5-nitro-4-fluorobenzenesulfonyl chloride was added at 0 ° C with stirring. After stirring at the same temperature for 10 minutes, the cooling bath was removed, and the mixture was stirred with heat generation for 1.5 hours. 20 ml of concentrated hydrochloric acid was added to the reaction liquid, and after stirring for a while, crystals were collected by filtration.
この結晶を酢酸エチル及び水各々100mlからなる溶液に
加え、炭酸水素ナトリウムで中和した。不溶物を濾別
後、有機層を水洗、乾燥、減圧下に溶媒を留去して2.5g
の５−アミノ−２−クロル−４−フルオロチオフェノー
ルを得た。構造はNMRで同定した。The crystals were added to a solution containing 100 ml of ethyl acetate and 100 ml of water, respectively, and neutralized with sodium hydrogen carbonate. After separating the insoluble matter by filtration, the organic layer was washed with water, dried, and the solvent was distilled off under reduced pressure to give 2.5 g.
5-amino-2-chloro-4-fluorothiophenol was obtained. The structure was identified by NMR.
本発明では、新規化合物２−クロル−４−フルオロ−
５−ニトロベンゼンスルホニルクロライド（II）を経由
することにより５−アミノ−２−クロル−４−フルオロ
チオフェノール（III）が少い工程数で収率良く得られ
る。In the present invention, the novel compound 2-chloro-4-fluoro-
By passing through 5-nitrobenzenesulfonyl chloride (II), 5-amino-2-chloro-4-fluorothiophenol (III) can be obtained with a small number of steps and a good yield.
化合物（III）は特開昭62-181283などに記載された除草
活性を有する化合物中間原料として有用である。Compound (III) is useful as an intermediate raw material for compounds having herbicidal activity described in JP-A-62-181283 and the like.
Claims (2)
ンゼンスルホニルクロライド。1. 2-Chloro-4-fluoro-5-nitrobenzenesulfonyl chloride.
とクロルスルホン酸とを反応させることを特徴とする２
−クロル−４−フルオロ−５−ニトロベンゼンスルホニ
ルクロライドの製造法。2. A method in which 4-chloro-2-fluoronitrobenzene and chlorosulfonic acid are reacted with each other.
-Process for producing chloro-4-fluoro-5-nitrobenzenesulfonyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32551387A JPH0825987B2 (en) | 1987-12-24 | 1987-12-24 | Process for producing 2-chloro-4-fluoro-5-nitrobenzenesulfonyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32551387A JPH0825987B2 (en) | 1987-12-24 | 1987-12-24 | Process for producing 2-chloro-4-fluoro-5-nitrobenzenesulfonyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01168662A JPH01168662A (en) | 1989-07-04 |
| JPH0825987B2 true JPH0825987B2 (en) | 1996-03-13 |
Family
ID=18177717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32551387A Expired - Lifetime JPH0825987B2 (en) | 1987-12-24 | 1987-12-24 | Process for producing 2-chloro-4-fluoro-5-nitrobenzenesulfonyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0825987B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5498798B2 (en) * | 2007-11-30 | 2014-05-21 | イハラケミカル工業株式会社 | Method for producing 3-mercaptoaniline compound |
-
1987
- 1987-12-24 JP JP32551387A patent/JPH0825987B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01168662A (en) | 1989-07-04 |
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