JPH08198842A - Production of disulfide derivative - Google Patents
Production of disulfide derivativeInfo
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- JPH08198842A JPH08198842A JP939995A JP939995A JPH08198842A JP H08198842 A JPH08198842 A JP H08198842A JP 939995 A JP939995 A JP 939995A JP 939995 A JP939995 A JP 939995A JP H08198842 A JPH08198842 A JP H08198842A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、農薬、特に殺菌剤の有
効成分化合物の中間体として有用なジフェニルジスルフ
ィド誘導体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diphenyl disulfide derivative useful as an intermediate for active ingredients of agricultural chemicals, especially fungicides.
【０００２】[0002]
【従来の技術および課題】これまで種々の殺菌剤が開発
されてきているが、その効力、薬害や耐性菌の出現等で
必ずしも満足するべきものではなく、植物病害に対して
更に有用な農園芸用殺菌剤の開発が要望されている。BACKGROUND OF THE INVENTION Various fungicides have been developed so far, but their efficacy, phytotoxicity, emergence of resistant strains, etc. are not always satisfactory, and they are more useful for plant diseases. There is a demand for the development of a germicide for use.
【０００３】[0003]
【課題を解決するための手段】本発明は、特開平５−３
２６６２号公報、特開平６−６５２３７号公報に記載さ
れている優れた殺菌活性を有する化合物の中間体として
有用な新規なジフェニルジスルフィド誘導体を提供する
ものである。The present invention is disclosed in JP-A-5-3.
The present invention provides a novel diphenyl disulfide derivative useful as an intermediate for the compounds having excellent bactericidal activity described in JP-A No. 2662 and JP-A No. 6-65237.
【０００４】すなわち、本発明は、式（１）：That is, the present invention uses the formula (1):
【０００５】[0005]
【化２】 Embedded image
【０００６】〔式中、Ｒは、炭素数１〜３のアルキル基
を表し、Ａは、ＮＯ2 、ＮＨ2 またはＦ原子を表す。〕
で表されるジフェニルジスルフィド誘導体であり、特
に、Ｒがメチル基である請求項１記載のジフェニルジス
ルフィド誘導体であり、さらに、ＡがＦ原子である請求
項１記載のジフェニルジスルフィド誘導体に関するもの
である。[In the formula, R represents an alkyl group having 1 to 3 carbon atoms, and A represents NO 2 , NH 2 or F atom. ]
The present invention relates to the diphenyl disulfide derivative represented by the formula (1), particularly R is a methyl group, the diphenyl disulfide derivative according to claim 1, and A is an F atom.
【０００７】本発明において、上記式（１）中の置換基
Ｒは、炭素数１〜３のアルキル基であるが、具体的には
例えば、メチル基、エチル基、ｎ−プロピル基もしくは
ｉ−プロピル基が挙げられる。次に、式（１）で表され
る本発明化合物の具体例を第１表に示す。In the present invention, the substituent R in the above formula (1) is an alkyl group having 1 to 3 carbon atoms, and specifically, for example, a methyl group, an ethyl group, an n-propyl group or an i-group. A propyl group is mentioned. Next, Table 1 shows specific examples of the compound of the present invention represented by the formula (1).
【０００８】[0008]
【表１】第１表 ──────────────────────── 化合物No． Ｒ Ａ ──────────────────────── １−１ ＣＨ3 ＮＯ2 １−２ ＣＨ3 ＮＨ2 １−３ ＣＨ3 Ｆ １−４ Ｃ2 Ｈ5 Ｆ １−５ ｎ−Ｃ3 Ｈ7 Ｆ １−６ ｉ−Ｃ3 Ｈ7 Ｆ ────────────────────────[Table 1] Table 1 ──────────────────────── Compound No. RA ──────────────────────── 1-1 CH 3 NO 2 1-2 CH 3 NH 2 1-3 CH 3 F 1-4C 2 H 5 F 1-5 n-C 3 H 7 F 1-6 i-C 3 H 7 F ─────────────────────────
【０００９】次に本発明化合物の製造法を反応スキーム
で示し、以下に説明する。Next, a method for producing the compound of the present invention is shown in a reaction scheme and described below.
【００１０】[0010]
【化３】 Embedded image
【００１１】（反応式Ａ）で示される反応において、ベ
ンゼンスルホニルクロライド誘導体（２）を溶媒中、過
剰のヒドラジン水化物とを室温で反応させた後、過剰の
濃塩酸を加え、触媒存在下、さらに加熱することによ
り、還元を行い本発明化合物であるジフェニルジスルフ
ィド誘導体（１）を合成することができる。溶媒として
は、例えば、メタノール、エタノール、プロパノール等
のアルコール類が挙げられる。ヒドラジン水化物は過剰
量必要であるが２〜４当量が好しい。In the reaction represented by (Reaction formula A), the benzenesulfonyl chloride derivative (2) is reacted with excess hydrazine hydrate in a solvent at room temperature, and then excess concentrated hydrochloric acid is added, in the presence of a catalyst. By further heating, the compound can be reduced to synthesize the diphenyl disulfide derivative (1) which is the compound of the present invention. Examples of the solvent include alcohols such as methanol, ethanol and propanol. An excess amount of hydrazine hydrate is necessary, but 2 to 4 equivalents is preferable.
【００１２】過剰量の塩酸としては、６〜１０当量が必
要である。触媒としては、ヨウ素、ヨウ化水素酸、ヨウ
化カリウム、ヨウ化ナトリウム等を用いることができ
る。また、反応温度は０℃から溶媒の沸点の間で行うこ
とができる。この還元反応としては、特開昭５８−１９
４８５５号公報記載の方法やオーガニックシンセシス
（Org. Synth.)４０巻、８０頁、１９６０年に記載の方
法等を用いることができる。As an excess amount of hydrochloric acid, 6 to 10 equivalents are required. As the catalyst, iodine, hydroiodic acid, potassium iodide, sodium iodide or the like can be used. The reaction temperature may be 0 ° C to the boiling point of the solvent. This reduction reaction is described in JP-A-58-19.
The method described in Japanese Patent No. 4855, the method described in Organic Synthesis (Org. Synth.) 40, 80, 1960 and the like can be used.
【００１３】（反応式Ｂ）で示される反応において、本
発明化合物（３）に溶媒中、過剰のヒドラジン水化物を
加え、触媒や添加剤存在下、加熱することにより、ニト
ロ基を還元することにより、本発明化合物であるジフェ
ニルジスルフィド誘導体（４）を合成することができ
る。溶媒としては、メタノール、エタノール等のアルコ
ール類が挙げられる。過剰のヒドラジン水化物としては
４〜６当量が適当である。触媒としては、塩化鉄（III)
が用いられる。添加剤としては、活性炭やグラファイト
が用いられる。添加剤の量は、化合物（３）に対して５
から１５０重量％用いることができる。In the reaction represented by (Reaction formula B), an excess hydrazine hydrate is added to the compound (3) of the present invention in a solvent and heated in the presence of a catalyst or an additive to reduce the nitro group. Thus, the diphenyl disulfide derivative (4) which is the compound of the present invention can be synthesized. Examples of the solvent include alcohols such as methanol and ethanol. An excess of 4 to 6 equivalents of hydrazine hydrate is suitable. As a catalyst, iron (III) chloride
Is used. Activated carbon or graphite is used as the additive. The amount of the additive is 5 with respect to the compound (3).
To 150% by weight can be used.
【００１４】（反応式Ｃ）で示される反応において、本
発明化合物（４）を過剰のフッ化水素酸と溶媒中、亜硝
酸付与剤を作用させてジアゾ化し、引き続き加熱分解す
ることにより、フッ素化が起こり、本発明化合物であ
る、ジフェニルジスルフィド誘導体（５）を合成するこ
とができる。過剰のフッ化水素酸としては、５〜５０当
量、好ましくは、１０〜２０当量である。In the reaction represented by (Reaction formula C), the compound (4) of the present invention is treated with a nitrite-providing agent in an excess of hydrofluoric acid and a solvent to form a diazo compound, which is then thermally decomposed to give fluorine. Then, the diphenyl disulfide derivative (5), which is the compound of the present invention, can be synthesized. The excess hydrofluoric acid is 5 to 50 equivalents, preferably 10 to 20 equivalents.
【００１５】溶媒としては、ベンゼン、トルエン、キシ
レン等の芳香族炭化水素や、ジクロロメタン、クロロホ
ルム、１，２−ジクロロエタン等のハロゲン化炭化水素
が挙げられる。亜硝酸付与剤としては、化合物（４）の
２〜３当量を−５０〜２０℃、通常−３０〜５℃に冷却
しながら加える。ジアゾ化終了後、反応液をそのまま加
熱し、相当するジアゾニウム塩の加熱分解に必要な温度
まで加熱し、除々に分解させる。Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane. As the nitrous acid-providing agent, 2 to 3 equivalents of the compound (4) are added while cooling to -50 to 20 ° C, usually -30 to 5 ° C. After the completion of the diazotization, the reaction solution is heated as it is, to the temperature necessary for the thermal decomposition of the corresponding diazonium salt, and gradually decomposed.
【００１６】このジアゾ化経由のフッ素化反応として
は、特開昭６３−６６１３２号公報、特開平３−２３２
８２９号公報、シンセテックコミュニケーション（Synt
h, Communications)１７巻、６８５頁、１９８７年、特
開昭６１−６３６２７号公報の記載の方法によっても行
うことができる。以下、本発明を実施例によってさらに
詳細に説明するが、本発明はこれらによって限定される
ものではない。The fluorination reaction via the diazotization is described in JP-A-63-66132 and JP-A-3-232.
No. 829, Synthetic Communication (Synt
h, Communications) 17, p. 685, 1987, and the method described in JP-A-61-63627. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
【００１７】[0017]
【００１８】〔実施例１〕 ビス（３−ニトロ−４−メチルフェニル）ジスルフィド
（本発明化合物No. １−１）の合成 ３−ニトロ−４−メチルベンゼンスルホニルクロライド
３５．０ｇ（１４８mmol）を３００mlのエタノールに溶
解し、０〜１５℃でヒドラジン一水和物２２．０ｇを加
え、室温で１時間攪拌した。これに濃塩酸１００mlと触
媒として、５１％のヨウ化水素酸５mlを加え、加熱還流
攪拌を３時間行った。減圧濃縮後、水を加え、クロロホ
ルムで抽出した。５％水酸化ナトリウム水溶液、チオ硫
酸ナトリウム水溶液、及び水で洗浄し、無水硫酸ナトリ
ウムで乾燥した。ろ過後、減圧濃縮すると、本発明化合
物No. １−１が淡茶色結晶として２２．２ｇ得られた。
（収率８９％） 融点８４〜８６℃Example 1 Synthesis of Bis (3-nitro-4-methylphenyl) disulfide (Invention Compound No. 1-1) 3-Nitro-4-methylbenzenesulfonyl chloride (35.0 g, 148 mmol) in 300 ml Dissolved in ethanol, 22.0 g of hydrazine monohydrate was added at 0 to 15 ° C., and the mixture was stirred at room temperature for 1 hour. To this, 100 ml of concentrated hydrochloric acid and 5 ml of 51% hydroiodic acid as a catalyst were added, and the mixture was heated and refluxed with stirring for 3 hours. After concentration under reduced pressure, water was added and the mixture was extracted with chloroform. It was washed with a 5% aqueous sodium hydroxide solution, an aqueous sodium thiosulfate solution, and water, and dried over anhydrous sodium sulfate. After filtration and concentration under reduced pressure, 22.2 g of the present compound No. 1-1 was obtained as light brown crystals.
(Yield 89%) Melting point 84-86 ° C
【００１９】〔実施例２〕 ビス（３−フルオロ−４−メチルフェニル）ジスルフィ
ド（本発明化合物No.１−３）の合成 ３−フルオロ−４−メチルベンゼンスルホニルクロライ
ド１９．０ｇ（０．０９１mol)をｎ−プロパノール１２
０mlに溶解し、氷冷下、ヒドラジン一水和物１４．４ｇ
（０．２９mol)を滴下して加えた。３０℃で１時間攪拌
後、濃塩酸１８mlを加え、さらに触媒としてヨウ化カリ
ウム０．８ｇを加え、加熱還流攪拌を３時間行った。反
応液を冷却後、減圧濃縮し、水を加えてクロロホルムで
抽出した。飽和炭酸水素ナトリウム水溶液で洗浄し、チ
オ硫酸ナトリウム水溶液で洗浄し、水洗いを行った後、
無水硫酸ナトリウムで乾燥した。ろ過後、減圧濃縮し
て、本発明化合物No. １−３を淡黄色結晶として１１．
５ｇ得た。（収率８９％） 融点５３〜５４℃Example 2 Synthesis of Bis (3-fluoro-4-methylphenyl) disulfide (Invention Compound No. 1-3) 3-Fluoro-4-methylbenzenesulfonyl chloride 19.0 g (0.091 mol) To n-propanol 12
Dissolve in 0 ml and under ice cooling, 14.4 g of hydrazine monohydrate
(0.29 mol) was added dropwise. After stirring at 30 ° C. for 1 hour, 18 ml of concentrated hydrochloric acid was added, 0.8 g of potassium iodide was further added as a catalyst, and the mixture was heated under reflux with stirring for 3 hours. The reaction mixture was cooled, concentrated under reduced pressure, water was added, and the mixture was extracted with chloroform. After washing with a saturated sodium hydrogen carbonate aqueous solution, a sodium thiosulfate aqueous solution, and washing with water,
It was dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to give Compound No. 1-3 of the present invention as pale yellow crystals.
5 g was obtained. (Yield 89%) Melting point 53-54 ° C
【００２０】〔実施例３〕 ビス（３−アミノ−４−メチルフェニル）ジスルフィド
（本発明化合物No. １−２）の合成 ビス（３−ニトロ−４−メチルフェニル）ジスルフィド
（本発明化合物No. １−１）３．０ｇ（８．９mmol）の
６０mlメタノール溶液に、活性炭０．３ｇと塩化鉄（II
I)６水和物０．１２ｇを加え、１０分間加熱還流した。
そこにヒドラジン一水和物１．８ｇとメタノール１２ml
の混合溶液を加えて、７時間加熱還流した。反応液を冷
却後、セライトろ過し、ろ液を減圧濃縮した。そこに、
５％水酸化ナトリウム水溶液を加え、アルカリ性にした
後、ジクロロメタンで抽出し、水洗い後、無水硫酸ナト
リウムで乾燥した。ろ過後減圧濃縮することにより、本
発明化合物No. １−２を暗赤色結晶として２．４６ｇ得
た。（収率９９％）融点７６〜７９℃Example 3 Synthesis of Bis (3-amino-4-methylphenyl) disulfide (Invention Compound No. 1-2) Bis (3-nitro-4-methylphenyl) disulfide (Invention Compound No. 1-2) 1-1) To a solution of 3.0 g (8.9 mmol) of 60 ml in methanol, 0.3 g of activated carbon and iron chloride (II
0.12 g of I) hexahydrate was added, and the mixture was heated under reflux for 10 minutes.
There, 1.8 g of hydrazine monohydrate and 12 ml of methanol
Was added and the mixture was heated under reflux for 7 hours. The reaction solution was cooled, filtered through Celite, and the filtrate was concentrated under reduced pressure. there,
A 5% aqueous sodium hydroxide solution was added to make the mixture alkaline, extracted with dichloromethane, washed with water, and dried over anhydrous sodium sulfate. After filtration and concentration under reduced pressure, 2.46 g of the present compound No. 1-2 was obtained as dark red crystals. (Yield 99%) Melting point 76-79 ° C
【００２１】〔実施例４〕 ビス（３−フルオロ−４−メチルフェニル）ジスルフィ
ド（本発明化合物No.１−３）の合成 ５５％フッ化水素酸２０mlにビス（３−アミノ−４−メ
チルフェニル）ジスルフィド（本発明化合物No. １−
２）３．０ｇ（１０．９mmol）を加え、さらにトルエン
２０mlを加え、−１０℃に冷却する。その混合液に亜硝
酸ナトリウム１．５５ｇ（２２．４mmol）を少しずつ加
えた。その後室温で１時間、６０℃で２時間さらに８０
℃で１時間加熱した。冷却後、酢酸エチルで抽出し、水
洗い後、無水硫酸ナトリウムで乾燥した。ろ過後、減圧
濃縮し、残渣をカラムクロマトグラフィーで精製するこ
とにより、本発明化合物No. １−３の淡黄色結晶を２．
１ｇ得た。（収率７９％） 融点５３〜５４℃ 次に、本発明化合物の農薬中間体を原料として、殺菌剤
有効成分化合物の製造例を以下に示す。Example 4 Synthesis of bis (3-fluoro-4-methylphenyl) disulfide (inventive compound No. 1-3) Bis (3-amino-4-methylphenyl) was added to 20 ml of 55% hydrofluoric acid. ) Disulfide (Compound of the present invention No. 1-
2) Add 3.0 g (10.9 mmol), add 20 ml of toluene, and cool to -10 ° C. To the mixture was added sodium nitrite (1.55 g, 22.4 mmol) little by little. Then at room temperature for 1 hour, at 60 ° C for 2 hours and then 80
Heated at ° C for 1 hour. After cooling, the mixture was extracted with ethyl acetate, washed with water, and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography to give pale yellow crystals of the present compound No. 1-3 as 2.
1 g was obtained. (Yield 79%) Melting point 53 to 54 [deg.] C. Next, a production example of a fungicide active ingredient compound using the agricultural chemical intermediate of the compound of the present invention as a raw material is shown below.
【００２２】〔製造例〕 ３−クロロ−４−（３−フルオロ−４−メチルフェニル
チオ）−１−メチル−５−（２−ピリミジルアミノ）ピ
ラゾールの合成 四塩化炭素５mlの溶液を水冷し、塩素ガスを吹き込みを
開始した。そこにビス（３−フルオロ−４−メチルフェ
ニル）ジスルフィド（本発明化合物No. １−３）３．０
ｇ（１０．６mmol）の四塩化炭素８mlの混合溶液を滴下
した。さらに室温下、塩素ガスを３０分吹き込んだ。次
に窒素ガスを吹き込み、過剰の塩素ガスを追い出し、溶
媒を減圧留去し、３−フルオロ−４−メチルフェニルス
ルフェニルクロライドを３．７２ｇ得た。この３−フル
オロ−４−メチルフェニルスルフェニルクロライド３．
７２ｇを、３−クロロ−１−メチル−５−（２−ピリミ
ジルアミノ）ピラゾール４．０ｇ（１９．１mmol）の無
水クロロホルム５０mlの混合溶液に１０℃で加えた。[Production Example] Synthesis of 3-chloro-4- (3-fluoro-4-methylphenylthio) -1-methyl-5- (2-pyrimidylamino) pyrazole A solution of 5 ml of carbon tetrachloride was cooled with water and chlorine was added. Bubbling of gas started. There, bis (3-fluoro-4-methylphenyl) disulfide (present compound No. 1-3) 3.0
A mixed solution of g (10.6 mmol) of carbon tetrachloride (8 ml) was added dropwise. Further, at room temperature, chlorine gas was blown in for 30 minutes. Then, nitrogen gas was blown in to remove excess chlorine gas, and the solvent was distilled off under reduced pressure to obtain 3.72 g of 3-fluoro-4-methylphenylsulfenyl chloride. This 3-fluoro-4-methylphenylsulfenyl chloride 3.
72 g was added at 10 ° C. to a mixed solution of 4.0 g (19.1 mmol) of 3-chloro-1-methyl-5- (2-pyrimidylamino) pyrazole in 50 ml of anhydrous chloroform.
【００２３】室温で３時間攪拌した後、飽和炭酸ナトリ
ウム水溶液を１５ml加え、さらに３０分攪拌した。クロ
ロホルム抽出し、水洗い後、無水硫酸ナトリウムで乾燥
した。ろ過後、減圧濃縮したところ結晶が得られた。結
晶をエタノールで洗浄し、乾燥することにより、淡灰色
の結晶として、３−クロロ−４−（３−フルオロ−４−
メチルフェニルチオ）−１−メチル−５−（２−ピリミ
ジルアミノ）ピラゾールが、４．８ｇ（収率７２％）得
られた。融点１７８〜１７９℃ この化合物は、特開平６−６５２３７号公報の明細書中
の実施例化合物No. １６８として記載されており、それ
は、殺菌剤として使用することができる。After stirring at room temperature for 3 hours, 15 ml of saturated sodium carbonate aqueous solution was added, and the mixture was further stirred for 30 minutes. It was extracted with chloroform, washed with water, and dried over anhydrous sodium sulfate. After filtration, concentration under reduced pressure gave crystals. The crystals were washed with ethanol and dried to give 3-chloro-4- (3-fluoro-4-) as light gray crystals.
4.8 g (yield 72%) of methylphenylthio) -1-methyl-5- (2-pyrimidylamino) pyrazole was obtained. Melting point 178-179 [deg.] C. This compound is described as Example Compound No. 168 in the specification of JP-A-6-65237, and it can be used as a bactericide.
【００２４】[0024]
【発明の効果】本発明化合物は新規であり、農薬、特に
優れた殺菌剤の中間体として有用である。INDUSTRIAL APPLICABILITY The compound of the present invention is novel and useful as an intermediate for agricultural chemicals, particularly excellent fungicides.
Claims (4)
は、ＮＯ2 、ＮＨ2 またはＦ原子を表す。〕で表される
ジフェニルジスルフィド誘導体。1. Formula (1): [In the formula, R represents an alkyl group having 1 to 3 carbon atoms, and
Represents a NO 2 , NH 2 or F atom. ] The diphenyl disulfide derivative represented by these.
フェニルジスルフィド誘導体。2. The diphenyl disulfide derivative according to claim 1, wherein R is a methyl group.
ェニルジスルフィド誘導体。3. The diphenyl disulfide derivative according to claim 1, wherein A is an F atom.
請求項１記載のジフェニルジスルフィド誘導体。4. The diphenyl disulfide derivative according to claim 1, wherein R is a methyl group and A is an F atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP939995A JPH08198842A (en) | 1995-01-25 | 1995-01-25 | Production of disulfide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP939995A JPH08198842A (en) | 1995-01-25 | 1995-01-25 | Production of disulfide derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08198842A true JPH08198842A (en) | 1996-08-06 |
Family
ID=11719351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP939995A Pending JPH08198842A (en) | 1995-01-25 | 1995-01-25 | Production of disulfide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08198842A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014090913A1 (en) * | 2012-12-12 | 2014-06-19 | Bayer Cropscience Ag | Method for producing bis(3-aminophenyl)disulfides and 3-aminothiols |
-
1995
- 1995-01-25 JP JP939995A patent/JPH08198842A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014090913A1 (en) * | 2012-12-12 | 2014-06-19 | Bayer Cropscience Ag | Method for producing bis(3-aminophenyl)disulfides and 3-aminothiols |
| KR20150092197A (en) * | 2012-12-12 | 2015-08-12 | 바이엘 크롭사이언스 아게 | Method for producing bis(3-aminophenyl)disulfides and 3-aminothiols |
| JP2015537053A (en) * | 2012-12-12 | 2015-12-24 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | Process for producing bis (3-aminophenyl) disulfides and 3-aminothiols |
| 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 |
| US10053421B2 (en) | 2012-12-12 | 2018-08-21 | Bayer Cropscience Ag | Method for producing bis(3-aminophenyl)disulfides and 3-aminothiols |
| CN108640863A (en) * | 2012-12-12 | 2018-10-12 | 拜尔农作物科学股份公司 | The method for preparing bis- (3- aminophenyls) disulphide and 3- amineothiots |
| US10239831B2 (en) | 2012-12-12 | 2019-03-26 | Bayer Cropscience Ag | Method for producing bis(3-aminophenyl)disulfides and 3-aminothiols |
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