JPH0613470B2 - 5-Amino-2-chlorophenylthioacetic acid and process for producing the same - Google Patents
5-Amino-2-chlorophenylthioacetic acid and process for producing the sameInfo
- Publication number
- JPH0613470B2 JPH0613470B2 JP365685A JP365685A JPH0613470B2 JP H0613470 B2 JPH0613470 B2 JP H0613470B2 JP 365685 A JP365685 A JP 365685A JP 365685 A JP365685 A JP 365685A JP H0613470 B2 JPH0613470 B2 JP H0613470B2
- Authority
- JP
- Japan
- Prior art keywords
- amino
- producing
- acid
- same
- chlorophenylthioacetic acid
- 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
Landscapes
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】 本発明は、５−アミノ−２−クロロフェニルチオ酢酸
（以下、本発明化合物と記す。）およびその製造法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 5-amino-2-chlorophenylthioacetic acid (hereinafter referred to as the compound of the present invention) and a method for producing the same.
本発明化合物を、３，４，５，６−テトラヒドロフタル
酸無水物と反応させた後、一般式 Ｒ−ＯＨ 〔Ｉ〕 〔式中、Ｒは低級アルキル基、低級ハロアルキル基また
は低級シクロアルキル基を表わす。〕 で示されるアルコール類と反応させることによって製造
することができる一般式 〔式中、Ｒは前記と同じ意味を表わす。〕 で示されるテトラヒドロフタルイミド誘導体は、ダイ
ズ、トウモロコシ、コムギ、イネ等の主要作物に対して
問題となる薬害を示さず、且つ、多くの雑草に対して充
分な除草効力を有する（特開昭６０−５４３６２号）。After reacting the compound of the present invention with 3,4,5,6-tetrahydrophthalic anhydride, the compound of the general formula R-OH [I] [wherein R is a lower alkyl group, a lower haloalkyl group or a lower cycloalkyl group] Represents ] A general formula which can be produced by reacting with an alcohol represented by [In the formula, R represents the same meaning as described above. ] The tetrahydrophthalimide derivative represented by the following does not show a harmful phytotoxicity to major crops such as soybean, corn, wheat and rice, and has a sufficient herbicidal effect against many weeds (Japanese Patent Laid-Open No. Sho 60-60). -54362).
本発明化合物は、標準的には、５−アミノ−２−クロロ
ベンゼンチオールと一般式 Ｘ−CH2COOH 〔III〕 〔式中、Ｘは塩素原子、臭素原子または沃素原子を表わ
す。〕 で示されるハロ酢酸とを、溶媒中、塩基の存在下、０℃
〜１００℃、好ましくは室温（２０℃）〜６０℃で、瞬
時〜５時間反応させ、次いで濃塩酸等にて酸性にするこ
とによって製造することができる。The compound of the present invention is typically 5-amino-2-chlorobenzenethiol and the general formula X-CH 2 COOH [III] [wherein X represents a chlorine atom, a bromine atom or an iodine atom]. ] With haloacetic acid represented by
It can be produced by reacting at -100 ° C, preferably at room temperature (20 ° C) to 60 ° C for a moment to 5 hours and then acidifying with concentrated hydrochloric acid or the like.
塩基としては、水酸化ナトリウム、水酸化カリウム、炭
酸カリウム、水素化ナトリウム等あげられる。Examples of the base include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride and the like.
溶媒としては、水、Ｎ，Ｎ−ジメチルホルムアミド、ジ
メチルスルホキシド等があげられる。但し、塩基とし
て、水素化ナトリウムを用いる場合には、水は用いな
い。Examples of the solvent include water, N, N-dimethylformamide, dimethyl sulfoxide and the like. However, when sodium hydride is used as the base, water is not used.
反応に供される試剤の量は、５−アミノ−２−クロロベ
ンゼンチオール１当量に対して、ハロ酢酸〔III〕は1.0
〜2.0当量、塩基は２〜５当量である。The amount of the reagent used in the reaction is 1.0 equivalent of haloacetic acid [III] with respect to 1 equivalent of 5-amino-2-chlorobenzenethiol.
-2.0 equivalents, and the base is 2-5 equivalents.
反応終了後の反応液は、必要に応じ、水を加え、有機溶
媒抽出および濃縮等の通常の後処理を行い、必要ならば
クロマトグラフィー、再結晶等の操作により、精製する
ことによって、目的の本発明化合物を得ることができ
る。If necessary, the reaction solution after completion of the reaction is subjected to usual post-treatments such as addition of water, extraction with an organic solvent and concentration, and if necessary, purification by operations such as chromatography and recrystallization to obtain the desired compound. The compound of the present invention can be obtained.
なお、原料化合物である５−アミノ−２−クロロベンゼ
ンチオールは、以下の方法により製造することができ
る。すなわち、２−クロロ−５−ニトロベンゼンスルホ
ニルクロリドと、これに対して６〜２０当量、好ましく
は６〜１２当量の塩化第一錫、亜鉛等の金属還元剤と
を、溶媒中、４０℃〜１０５℃、好ましくは８０℃〜１
０５℃で、瞬時〜１０時間反応させることによって製造
することができる。溶媒としては、塩化第一錫の場合は
塩酸、亜鉛の場合は塩酸もしくは希塩酸があげられる。The starting compound, 5-amino-2-chlorobenzenethiol, can be produced by the following method. That is, 2-chloro-5-nitrobenzenesulfonyl chloride and 6 to 20 equivalents, preferably 6 to 12 equivalents, of a metal reducing agent such as stannous chloride or zinc are used in a solvent at 40 ° C to 105 ° C. ℃, preferably 80 ℃ ~ 1
It can be produced by reacting at 05 ° C for an instant to 10 hours. Examples of the solvent include hydrochloric acid in the case of stannous chloride and hydrochloric acid or dilute hydrochloric acid in the case of zinc.
また、原料化号物である２−クロロ−５−ニトロベンゼ
ンスルホニルクロリドは、Ｐ．Ｆｉｓｃｈｅｒ，Ｃｈｅ
ｍ． Ｂｅｒ．，２４， ３１９４（１８９１）に記載
されている公知化合物である。In addition, 2-chloro-5-nitrobenzenesulfonyl chloride, which is a raw material compound, is described in P. Fischer, Che
m. Ber. , 24 , 3194 (1891).
次に、本発明を製造例および参考例でされに詳しく説明
する。Next, the present invention will be described in detail with reference to production examples and reference examples.
製造例 ５−アミノ−２−クロロベンゼンチオール13.0ｇ、１０
％水酸化ナトリウム水溶液８７ml、ブロモ酢酸12.1ｇを
懸濁させ、90℃で１時間加熱した。反応混合物が冷えて
から、濃塩酸でpH＝４とし、酢酸エチルで抽出した。抽
出液を水洗、濃縮し、残渣をエーテルより結晶させ、５
−アミノ−２−クロロフェニルチオ酢酸11.0ｇを得た。Production Example 5-amino-2-chlorobenzenethiol 13.0 g, 10
87% aqueous sodium hydroxide solution and 12.1 g of bromoacetic acid were suspended and heated at 90 ° C. for 1 hour. After the reaction mixture had cooled, the pH was adjusted to 4 with concentrated hydrochloric acid and extracted with ethyl acetate. The extract was washed with water and concentrated, and the residue was crystallized from ether, and
11.0 g of -amino-2-chlorophenylthioacetic acid was obtained.
m.p.１５２〜１５４℃ 参考例 無水塩化第一錫１６１ｇを濃塩酸１６０mlに溶かし、０
℃で徐々に２−クロロ−５−ニトロベンゼンスルホニル
クロリド３４ｇを加えた。その後、昇温し、１００℃で
１５分間加熱した。反応混合物が冷えてから濃塩酸２４
０mlを加え、析出した結晶を取した。この結晶を重曹
水で中和し、酢酸エチルで抽出した。抽出液を乾燥、濃
縮し、５−アミノ−２−クロロベンゼンチオール２１ｇ
を得た。mp152-154 ° C. Reference example Dissolve 161 g of anhydrous stannous chloride in 160 ml of concentrated hydrochloric acid, and
34 g of 2-chloro-5-nitrobenzenesulphonyl chloride was slowly added at 0 ° C. After that, the temperature was raised and heated at 100 ° C. for 15 minutes. After the reaction mixture has cooled, concentrated hydrochloric acid 24
0 ml was added and the precipitated crystals were collected. The crystals were neutralized with aqueous sodium hydrogen carbonate and extracted with ethyl acetate. The extract is dried and concentrated to give 21 g of 5-amino-2-chlorobenzenethiol.
Got
NMR(CDCl3+D6-DMSO)δppm4.0(3H,br,s,NH2 、SH)、6.3〜6.
7(2H,m)、6.8〜7.1(1H,m) NMR (CDCl 3 + D 6 -DMSO ) δppm4.0 (3H, br, s, N H 2, S H), 6.3~6.
7 (2H, m), 6.8 to 7.1 (1H, m)
Claims (2)
と一般式 Ｘ−CH2COOH 〔式中、Ｘは塩素原子、臭素原子または沃素原子を表わ
す。〕 で示されるハロ酢酸とを反応させた後、酸性にすること
を特徴とする５−アミノ−２−クロロフェニルチオ酢酸
の製造法。2. Amino-2-chlorobenzenethiol and the general formula X-CH 2 COOH [wherein X represents a chlorine atom, a bromine atom or an iodine atom]. ] The method for producing 5-amino-2-chlorophenylthioacetic acid, characterized by reacting with haloacetic acid represented by
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP365685A JPH0613470B2 (en) | 1985-01-11 | 1985-01-11 | 5-Amino-2-chlorophenylthioacetic acid and process for producing the same |
| US06/817,667 US4902832A (en) | 1983-08-31 | 1986-01-10 | 2-Substituted phenyl-4,5,6,7-tetrahydro-2H-isoindole-1,3-diones, and their production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP365685A JPH0613470B2 (en) | 1985-01-11 | 1985-01-11 | 5-Amino-2-chlorophenylthioacetic acid and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61161255A JPS61161255A (en) | 1986-07-21 |
| JPH0613470B2 true JPH0613470B2 (en) | 1994-02-23 |
Family
ID=11563509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP365685A Expired - Lifetime JPH0613470B2 (en) | 1983-08-31 | 1985-01-11 | 5-Amino-2-chlorophenylthioacetic acid and process for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0613470B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4879647B2 (en) * | 2006-05-10 | 2012-02-22 | 出光ユニテック株式会社 | Container with lid |
-
1985
- 1985-01-11 JP JP365685A patent/JPH0613470B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61161255A (en) | 1986-07-21 |
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