JP2684749B2 - Bis- (4-fluoro-2-chlorophenyl) disulfide derivative - Google Patents
Bis- (4-fluoro-2-chlorophenyl) disulfide derivativeInfo
- Publication number
- JP2684749B2 JP2684749B2 JP1044066A JP4406689A JP2684749B2 JP 2684749 B2 JP2684749 B2 JP 2684749B2 JP 1044066 A JP1044066 A JP 1044066A JP 4406689 A JP4406689 A JP 4406689A JP 2684749 B2 JP2684749 B2 JP 2684749B2
- Authority
- JP
- Japan
- Prior art keywords
- fluoro
- compound
- bis
- chlorophenyl
- chloro
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
- C07C323/09—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
- C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
- C07C323/37—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to a carbon atom of a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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、特願昭63−154328号に記載されている選択
性除草剤の中間体として重要な、ビス−（４−フルオロ
−２−クロルフェニル）ジスルフィド誘導体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to bis- (4-fluoro-2-), which is important as an intermediate for the selective herbicides described in Japanese Patent Application No. 63-154328. Chlorphenyl) disulfide derivatives.
従来、スキーム（１）に示される化合物（Ｄ）、４−
クロロ−２−フルオロ−５−メルカプトアニリン（米国
特許第4,623,675号に記載されている公知化合物）は、
例えば特開昭60−248657号公報に記載されている５−
（Ｎ−アセチルアミン）−４−フルオロ−２−クロロベ
ンゼンチオールを脱アセチル化することにより合成でき
る。当該公報記載の合成方法は、５−（Ｎ−アセチルア
ミノ）−４−フルオロ−２−クロロベンゼンスルホニル
クロライドを還元して、５−（Ｎ−アセチルアミノ）−
４−フルオロ−２−クロロベンゼンチオールを得る方法
である。Conventionally, the compound (D) shown in the scheme (1), 4-
Chloro-2-fluoro-5-mercaptoaniline (known compound described in US Pat. No. 4,623,675) is
For example, the method described in JP-A-60-248657
It can be synthesized by deacetylating (N-acetylamine) -4-fluoro-2-chlorobenzenethiol. The synthesis method described in this publication reduces 5- (N-acetylamino) -4-fluoro-2-chlorobenzenesulfonyl chloride to give 5- (N-acetylamino)-.
This is a method for obtaining 4-fluoro-2-chlorobenzenethiol.
しかしながらこの合成ルートでは、スルホニルクロラ
イドを亜鉛、鉄などの還元剤を用いて、過剰の酸類とと
もに還元することにより対応するチオールへと導いてお
り、多量の還元剤を用い、反応後も多量の金属塩を副生
するなどし、必ずしも優れた反応とは言い難い。However, in this synthetic route, sulfonyl chloride is reduced to the corresponding thiol by reducing with a reducing agent such as zinc or iron to the corresponding thiol, and a large amount of reducing agent is used, and a large amount of metal is used even after the reaction. It is hard to say that it is an excellent reaction because it produces salt as a by-product.
本発明は、容易に入手できる原料から効率良く４−ク
ロロ−２−フルオロ−５−メルカプトアニリンを得る合
成方法および新規重要中間体を提供するものである。 The present invention provides a synthetic method for efficiently obtaining 4-chloro-2-fluoro-5-mercaptoaniline from easily available raw materials and a novel important intermediate.
次に、スキーム（１）に従い、本発明の合成方法を詳
述する。本発明では、２−クロロ−４−フルオロベンゼ
ンチオールを一般的な酸化剤例えば過酸化水素、ヨウ
素、空気、酸素、DMSO、次亜塩素酸水溶液等を用い、溶
媒中、例えばアルコール、水、アセトン、酢酸あるいは
それらの混合溶媒中で酸化することにより、化合物
（Ａ）すなわちビス−（４−フルオロ−２−クロロフェ
ニル）ジスルフィドを得る。また、２−クロロ−４−フ
ルオロアニリンをジアゾ化し二硫化ナトリウムと反応さ
せることによっても化合物（Ａ）を得ることができる。
次いで化合物（Ａ）を溶媒中、例えば、濃硫酸、希硫
酸、酢酸、水あるいは有機溶媒中で、ニトロ化剤、例え
ば濃硝酸、希硝酸、亜硝酸ナトリウム、亜硝酸イソアミ
ル等でニトロ化することにより化合物（Ｂ）すなわちビ
ス−（４−フルオロ−２−クロロ−５−ニトロフェニ
ル）ジスルフィドを得る。これを適当な還元剤例えば、
亜鉛、鉄、スズ等の金属と塩酸、硫酸、酢酸などの酸
で、あるいは水素とPd−カーボン、Pd−ブラックなどの
触媒と酸によって、あるいは硫化ナトリウム、硫化カリ
ウム等の硫化物によって、あるいはトリフェニルホスフ
ィンとアルコール又はジオキサン水溶液によって、ある
いはLiAlH4、NaBH4などを用いて還元することにより、
化合物（Ｃ）すなわちビス−（４−フルオロ−２−クロ
ロ−５−アミノフェニル）ジスルフィドを得る。これを
さらに常法により還元して、化合物（Ｄ）すなわち４−
クロロ−２−フルオロ−５−メルカプトアニリンを得る
ことが出来る。また還元条件及び資材量を調節すること
により化合物（Ｂ）から一段階の反応で化合物（Ｄ）を
得ることも可能である。Next, the synthetic method of the present invention will be described in detail according to the scheme (1). In the present invention, 2-chloro-4-fluorobenzenethiol is used as a general oxidant such as hydrogen peroxide, iodine, air, oxygen, DMSO, hypochlorous acid aqueous solution, etc., in a solvent such as alcohol, water, acetone. Compound (A), that is, bis- (4-fluoro-2-chlorophenyl) disulfide, is obtained by oxidation with acetic acid or acetic acid or a mixed solvent thereof. The compound (A) can also be obtained by diazotizing 2-chloro-4-fluoroaniline and reacting it with sodium disulfide.
Then, the compound (A) is nitrated with a nitrating agent such as concentrated nitric acid, diluted nitric acid, sodium nitrite, isoamyl nitrite in a solvent such as concentrated sulfuric acid, diluted sulfuric acid, acetic acid, water or an organic solvent. To obtain the compound (B), that is, bis- (4-fluoro-2-chloro-5-nitrophenyl) disulfide. This is a suitable reducing agent, for example
Metals such as zinc, iron and tin and acids such as hydrochloric acid, sulfuric acid and acetic acid, hydrogen and catalysts and acids such as Pd-carbon and Pd-black, or sulfides such as sodium sulfide and potassium sulfide, or tritium. Phenylphosphine and alcohol or dioxane aqueous solution, or by reducing with LiAlH 4 , NaBH 4, etc.,
Compound (C), bis- (4-fluoro-2-chloro-5-aminophenyl) disulfide, is obtained. This is further reduced by a conventional method to give compound (D), namely 4-
Chloro-2-fluoro-5-mercaptoaniline can be obtained. It is also possible to obtain the compound (D) from the compound (B) by a one-step reaction by adjusting the reducing conditions and the amount of materials.
このようにして得られた化合物（Ｄ）を塩基存在下、
ハロゲノ酢酸エステル類と反応させることにより化合物
（Ｅ）へと導くことが出来る。化合物（Ｅ）はさらにス
キーム（２）によって特願昭63−154328号に記載されて
いる化合物へ導くことができる。The compound (D) thus obtained, in the presence of a base,
The compound (E) can be obtained by reacting it with a halogenoacetic acid ester. The compound (E) can be further converted into the compound described in Japanese Patent Application No. 63-154328 by the scheme (2).
化合物（Ｇ）は畑地、水田用除草剤として低薬量で多
種の雑草に卓効があり、重要作物である小麦、大麦、大
豆、トウモロコシ、イネ等に対して薬害を及ぼさず、選
択的除草活性を示す化合物である。 Compound (G) is a herbicide for upland fields and paddy fields, which is effective in a wide variety of weeds in a low dose and has no phytotoxicity to important crops such as wheat, barley, soybean, corn, rice, etc. It is a compound showing activity.
以下に、本発明化合物の合成例を参考例として具体的
に述べる。Hereinafter, synthetic examples of the compound of the present invention will be specifically described as reference examples.
参考例−１ ビス−（２−クロロ−４−フルオロフェニル）ジスルフ
ィドの合成 濃塩酸19mlを０℃に冷却し、砕いた氷を20g加え、０
℃に保ちながら撹拌した。２−クロロ−４−フルオロア
ニリン9.5gをゆっくり加えたのち、４℃以下に保ちなが
ら亜硝酸ナトリウム4.75g、水16mlの溶液を滴下した。
この混合液を、40℃に加熱したキサントゲン酸エチルカ
リウム塩12.2g、水23mlの溶液に２時間かけて滴下し
た。滴下終了後、30分撹拌した。ジエチルエーテルで反
応溶液を２回抽出し、エーテル層を飽和炭酸水素ナトリ
ウム水溶液で洗浄、無水硫酸ナトリウムでの乾燥を経
て、溶媒を留去し、得られた残渣を95％エタノール65ml
に溶解し、加熱した。還流しはじめた時点で水酸化カリ
ウム（85％純度）10.5gを加え、３時間還流した。室温
まで冷却後、水を100ml加え、エーテルで抽出した。水
層を6N−H2SO4でpH2〜３に調節し、エーテルで抽出し
た。エーテル層を水で洗浄後、無水硫酸ナトリウムで乾
燥し、濃縮することにより目的化合物2.5gを得た。Reference Example-1 Synthesis of bis- (2-chloro-4-fluorophenyl) disulfide 19 ml of concentrated hydrochloric acid was cooled to 0 ° C., 20 g of crushed ice was added, and 0
The mixture was stirred while maintaining the temperature at ℃. After slowly adding 9.5 g of 2-chloro-4-fluoroaniline, a solution of 4.75 g of sodium nitrite and 16 ml of water was added dropwise while keeping the temperature at 4 ° C or lower.
This mixed solution was added dropwise to a solution of 12.2 g of potassium xanthate acid potassium salt and 23 ml of water heated at 40 ° C. over 2 hours. After the addition, the mixture was stirred for 30 minutes. The reaction solution was extracted twice with diethyl ether, the ether layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and the solvent was distilled off. The resulting residue was mixed with 95 ml of 95% ethanol (65 ml).
And was heated. When reflux started, 10.5 g of potassium hydroxide (85% purity) was added and refluxed for 3 hours. After cooling to room temperature, 100 ml of water was added and extracted with ether. The aqueous layer 6N-H 2 SO 4 was adjusted to pH 2-3, and extracted with ether. The ether layer was washed with water, dried over anhydrous sodium sulfate, and concentrated to obtain 2.5 g of the target compound.
融点 60〜63℃1 H−NMR（CDCl3） δ:6.66〜7.55（6H,m） 参考例−２ ビス−（２−クロロ−４−フルオロ−５−アミノフェニ
ル）ジスルフィドの合成 ビス−（２−クロロ−４−フルオロ−５−ニトロフェ
ニル）ジスルフィド1g、エチルアルコール20ml、酢酸0.
5ml、５％パラジウムカーボン0.1gの混合溶液を30℃に
保ち、激しく撹拌しながら、水素ガスを吸収させた。水
素ガス180mlを吸収したところで撹拌を止め、触媒を除
去し、反応溶液を５％水酸化ナトリウムでpH11に調整し
た。エタノールを留去し、反応溶液を酢酸エチルで抽出
した。これを炭酸水素ナトリウム水溶液、水で順次洗浄
し、無水硫酸ナトリウムで乾燥後、溶媒を減圧留去し
て、目的化合物0.7gを固体として得た。Melting point 60 to 63 ° C. 1 H-NMR (CDCl 3 ) δ: 6.66 to 7.55 (6H, m) Reference Example-2 Synthesis of bis- (2-chloro-4-fluoro-5-aminophenyl) disulfide Bis- (2-chloro-4-fluoro-5-nitrophenyl) disulfide 1 g, ethyl alcohol 20 ml, acetic acid 0.
A mixed solution of 5 ml and 5% palladium carbon 0.1 g was kept at 30 ° C., and hydrogen gas was absorbed with vigorous stirring. When 180 ml of hydrogen gas was absorbed, stirring was stopped, the catalyst was removed, and the reaction solution was adjusted to pH 11 with 5% sodium hydroxide. Ethanol was distilled off, and the reaction solution was extracted with ethyl acetate. This was washed successively with aqueous sodium hydrogen carbonate solution and water, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to give 0.7 g of the target compound as a solid.
融点 170〜172℃1 H−NMR（d6−DMSO） δ:5.33（4H,br s）,7.22（2H,d,J＝10Hz）,7.31（2H,
d,J＝9Hz）Melting point 170-172 ° C 1 H-NMR (d 6 -DMSO) δ: 5.33 (4H, br s), 7.22 (2H, d, J = 10Hz), 7.31 (2H,
d, J = 9Hz)
Claims (1)
す。】 で示される、ビス−（４−フルオロ−２−クロルフェニ
ル）ジスルフィド誘導体。(1) Formula (I) In the formula, R represents a hydrogen atom, a nitro group or an amino group. A bis- (4-fluoro-2-chlorophenyl) disulfide derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1044066A JP2684749B2 (en) | 1989-02-23 | 1989-02-23 | Bis- (4-fluoro-2-chlorophenyl) disulfide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1044066A JP2684749B2 (en) | 1989-02-23 | 1989-02-23 | Bis- (4-fluoro-2-chlorophenyl) disulfide derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02221254A JPH02221254A (en) | 1990-09-04 |
| JP2684749B2 true JP2684749B2 (en) | 1997-12-03 |
Family
ID=12681254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1044066A Expired - Fee Related JP2684749B2 (en) | 1989-02-23 | 1989-02-23 | Bis- (4-fluoro-2-chlorophenyl) disulfide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2684749B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850246A (en) * | 2012-07-10 | 2013-01-02 | 江西理工大学 | Method for introducing mercapto group into aniline derivative |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3172878B2 (en) * | 1990-12-27 | 2001-06-04 | イハラケミカル工業株式会社 | New disulfide compounds |
| TWI623520B (en) * | 2012-12-12 | 2018-05-11 | 德商拜耳作物科學股份有限公司 | Method for preparing bis(3-aminophenyl) disulphides and 3-aminothiols |
| CN115925597A (en) * | 2022-12-20 | 2023-04-07 | 黄冈鲁班药业股份有限公司 | Preparation method of bis (4-sulfophenyl) disulfide |
-
1989
- 1989-02-23 JP JP1044066A patent/JP2684749B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850246A (en) * | 2012-07-10 | 2013-01-02 | 江西理工大学 | Method for introducing mercapto group into aniline derivative |
| CN102850246B (en) * | 2012-07-10 | 2015-04-22 | 江西理工大学 | Method for introducing mercapto group into aniline derivative |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02221254A (en) | 1990-09-04 |
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