JPH0643383B2 - Cyclohexanedione derivative - Google Patents
Cyclohexanedione derivativeInfo
- Publication number
- JPH0643383B2 JPH0643383B2 JP60214751A JP21475185A JPH0643383B2 JP H0643383 B2 JPH0643383 B2 JP H0643383B2 JP 60214751 A JP60214751 A JP 60214751A JP 21475185 A JP21475185 A JP 21475185A JP H0643383 B2 JPH0643383 B2 JP H0643383B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- alkyl group
- compound represented
- lower alkyl
- 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
- Heterocyclic Compounds Containing Sulfur Atoms (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】 〔産業上の利用分野〕 本発明は除草剤として有用なシクロヘキサンジオン誘導
体に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cyclohexanedione derivative useful as a herbicide.
シクロヘキサンジオン誘導体が優れた除草活性を示すこ
とは広く知られており、またそれらの塩としてナトリウ
ム塩、カルシウム塩、銅塩等も公知である。（特開昭54
-46749、特開昭57-206674） 〔発明が解決しようとする問題点〕 前記公知化合物のうち、シクロヘキサン環の５位に硫黄
原子を含む置換基、例えば２−エチルチオプロピル基等
のアルキルチオアルキル基や３−チアニル基等の含イオ
ウ複素環基を有する化合物の前記公知の塩は結晶化せず
ガラス状物質となるため、工業的取扱いが非常に困難で
あった。本発明者等は種々の農薬製剤を開発するため、
安定で結晶性のよい化合物について種々検討した。It is widely known that cyclohexanedione derivatives show excellent herbicidal activity, and as their salts, sodium salts, calcium salts, copper salts and the like are also known. (JP-A-54
-46749, JP-A-57-206674) [Problems to be Solved by the Invention] Among the above-mentioned known compounds, a substituent containing a sulfur atom at the 5-position of the cyclohexane ring, for example, an alkylthioalkyl such as a 2-ethylthiopropyl group. The known salt of a compound having a sulfur-containing heterocyclic group such as a group or a 3-thianyl group does not crystallize and becomes a glassy substance, which is very difficult to handle industrially. Since the present inventors develop various agricultural chemical formulations,
Various studies were conducted on stable compounds having good crystallinity.
本発明者等は前記目的にそって種々検討した結果、硫黄
原子を含む置換基を有する化合物もリチウム塩にするこ
とにより、非常に安定な結晶として容易に得られること
を見い出した。As a result of various studies based on the above objects, the present inventors have found that a compound having a substituent containing a sulfur atom can be easily obtained as a very stable crystal by using a lithium salt.
即ち、本発明は一般式 （式中、R1は低級アルキル基を、R2は低級アルキル基又
はハロゲン原子で置換されていてもよい低級アルケニル
基を、Ｒ３は低級アルキルチオ低級アルキル基または３
−チアニル基を示す。）で表される化合物である。That is, the present invention has the general formula (In the formula, R 1 is a lower alkyl group, R 2 is a lower alkyl group or a lower alkenyl group which may be substituted with a halogen atom, and R 3 is a lower alkylthio lower alkyl group or 3
-Cyanyl group is shown. ) Is a compound represented by.
本発明化合物を製造するにあたっては、一般式 （式中、R1、R2及びR3は前記と同じ意味を示す。）で表
される化合物と水酸化リチウム、炭酸リチウム等のリチ
ウム塩とを反応させる。In producing the compound of the present invention, the general formula (Wherein R 1 , R 2 and R 3 have the same meanings as described above) and a lithium salt such as lithium hydroxide or lithium carbonate is reacted.
反応は通常、有機溶媒−水系中、０℃から用いる溶媒の
沸点まで、好ましくは室温付近で10分から数時間行われ
る。用いられる有機溶媒としては、アセトン、メチルイ
ソブチルケトン(MIBK)、ベンゼン、トルエン、キシレ
ン、ハロゲン化炭化水素等一般の不活性溶媒が挙げられ
るが後処理等を考慮するとＭＩＢＫ、トルエン等水難溶
性溶媒を用いるのが好ましい。The reaction is usually carried out in an organic solvent-water system from 0 ° C to the boiling point of the solvent used, preferably at around room temperature for 10 minutes to several hours. Examples of the organic solvent to be used include general inert solvents such as acetone, methyl isobutyl ketone (MIBK), benzene, toluene, xylene, halogenated hydrocarbons, etc. In consideration of post-treatment, etc., MIBK, toluene and other poorly water-soluble solvents are used. It is preferably used.
一般式〔II〕で表される化合物とリチウム塩とのモル数
は一般式〔II〕で表される化合物１モルに対し、リチウ
ム塩95〜105モル％、好ましくは等モル前後である。The number of moles of the compound represented by the general formula [II] and the lithium salt is 95 to 105 mol%, preferably around equimolar, to 1 mol of the compound represented by the general formula [II].
反応終了後は蒸留あるいは共沸脱水等により水を除去
し、析出した結晶を濾過することにより目的物をほぼ定
量的に得ることができる。こうして得られた結晶は非常
に純度のよいものであるが、もし必要ならば適当な溶媒
で再結晶することにより精製が可能である。After the reaction is completed, water is removed by distillation or azeotropic dehydration, and the precipitated crystals are filtered to obtain the desired product almost quantitatively. The crystals thus obtained are of very high purity, but if necessary can be purified by recrystallisation in a suitable solvent.
得られた化合物の構造はＩＲスペクトル、ＮＭＲスペク
トル等のスペクトルデータから決定した。The structure of the obtained compound was determined from spectral data such as IR spectrum and NMR spectrum.
なお、一般式〔Ｉ〕で表される化合物はＥ体、Ｚ体２種
類の異性体が存在し、また一般式〔II〕で表される原料
化合物は下記に示す互変異性体がさらにそれぞれの異性
体にはＥ体、Ｚ体２種類の異性体が存在する。The compound represented by the general formula [I] has two kinds of isomers, E isomer and Z isomer, and the starting compound represented by the general formula [II] further has tautomers shown below. There are two kinds of isomers of E isomer and Z isomer.
〔実施例〕 次に実施例を挙げ、本発明を更に詳細に説明する。 EXAMPLES Next, the present invention will be described in more detail with reference to examples.
実施例１．２−〔１−（エトキシイミノ）ブチル〕−５
−（２−エチルチオプロピル）−３−ヒドロキシ−２−
シクロヘキセン−１−オン リチウム塩（化合物番号１）： （ａ） ２−ブチリル−５−（２−エチルチオプロピル）−３−
ヒドロキシ−２−シクロヘキセン−１−オンの77％トル
エン溶液370.7gに51.5％エトキシアミン水溶液136.4gを
室温で加え、同温度で１時間攪拌し、引き続き50℃で６
時間攪拌した。反応終了後冷却し、トルエン280mlを加
え、濃塩酸でpH１にし、30分攪拌した。分液後、有機層
に5.75％水酸化リチウム水溶液415gを室温で加え、同温
度で30分攪拌した。分液後、水層を濃縮して55％溶液と
した後ＭＩＢＫ800mlを加え、共沸脱水した。析出した
結晶を濾別、乾燥し、目的物317.2g(95.1%)を得た。d.
p.222〜223℃ （ｂ） ２−〔１−（エトキシイミノ）ブチル〕−５−（２−エ
チルチオプロピル）−３−ヒドロキシ−２−シクロヘキ
セン−１−オン98.2gをトルエン300mlに溶解し、これに
水酸化リチウム１水塩12.6gを加え、室温で２時間攪拌
し、引き続き還流下で１時間攪拌した。反応終了後、共
沸脱水を行い、析出した結晶を濾別、乾燥して目的物9
9.4g(97.5%)を得た。d.p.222〜223℃ 上記実施例を含め、同様にして得られた本発明化合物の
代表例を第１表に示す。Example 1.2- [1- (Ethoxyimino) butyl] -5
-(2-Ethylthiopropyl) -3-hydroxy-2-
Cyclohexen-1-one lithium salt (Compound No. 1): (a) 2-butyryl-5- (2-ethylthiopropyl) -3-
To 370.7 g of 77% toluene solution of hydroxy-2-cyclohexen-1-one, 136.4 g of 51.5% ethoxyamine aqueous solution was added at room temperature, and the mixture was stirred at the same temperature for 1 hour, and then at 50 ° C. for 6 hours.
Stir for hours. After completion of the reaction, the mixture was cooled, 280 ml of toluene was added, the pH was adjusted to 1 with concentrated hydrochloric acid, and the mixture was stirred for 30 minutes. After separation, 415 g of a 5.75% aqueous lithium hydroxide solution was added to the organic layer at room temperature, and the mixture was stirred at the same temperature for 30 minutes. After liquid separation, the aqueous layer was concentrated to a 55% solution, 800 ml of MIBK was added, and azeotropic dehydration was performed. The precipitated crystals were separated by filtration and dried to obtain 317.2 g (95.1%) of the desired product. d.
p.222-223 ℃ (b) 2- [1- (Ethoxyimino) butyl] -5- (2-ethylthiopropyl) -3-hydroxy-2-cyclohexen-1-one (98.2 g) was dissolved in 300 ml of toluene, and lithium hydroxide monohydrate was added to the solution. 12.6 g was added, and the mixture was stirred at room temperature for 2 hours and then under reflux for 1 hour. After completion of the reaction, azeotropic dehydration was performed, and the precipitated crystals were separated by filtration and dried to obtain the desired product 9
Obtained 9.4 g (97.5%). dp222 to 223 ° C Table 1 shows representative examples of the compounds of the present invention obtained in the same manner as in the above Examples.
〔発明の効果〕 本発明化合物は工業的に容易に得られ、しかも結晶性に
優れているため、一般式〔II〕で示されるフリーの化合
物では製剤化が困難な、例えば水溶剤が容易に得られる
等農薬としてさらに幅広い使用が期待できる。 [Effect of the invention] The compound of the present invention is industrially easily obtained, and because it is excellent in crystallinity, it is difficult to formulate a free compound represented by the general formula [II], for example, an aqueous solvent is easily used. Further widespread use as a pesticide can be expected.
Claims (1)
基又は、ハロゲン原子で置換されていてもよい低級アル
ケニル基を、Ｒ３は低級アルキルチオ低級アルキル基又
は３−チアニル基を示す。）で表される化合物。1. A general formula (In the formula, R 1 represents a lower alkyl group, R 2 represents a lower alkyl group or a lower alkenyl group which may be substituted with a halogen atom, and R 3 represents a lower alkylthio lower alkyl group or a 3-thianyl group. ) The compound represented by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60214751A JPH0643383B2 (en) | 1985-09-30 | 1985-09-30 | Cyclohexanedione derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60214751A JPH0643383B2 (en) | 1985-09-30 | 1985-09-30 | Cyclohexanedione derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6289653A JPS6289653A (en) | 1987-04-24 |
| JPH0643383B2 true JPH0643383B2 (en) | 1994-06-08 |
Family
ID=16660969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60214751A Expired - Lifetime JPH0643383B2 (en) | 1985-09-30 | 1985-09-30 | Cyclohexanedione derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643383B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19545212A1 (en) * | 1995-12-05 | 1997-06-12 | Basf Ag | Cyclohexenone oxime ether metal salts |
| TR200101763T2 (en) * | 1998-12-15 | 2001-11-21 | Basf Ag. | Cyclohexenoximeter (glyphosate / glufosinate) suspension concentrates. |
| CN111423346B (en) * | 2020-05-21 | 2022-05-03 | 首建科技有限公司 | Preparation method of clethodim lithium salt standard sample |
| CN116283685A (en) * | 2022-12-21 | 2023-06-23 | 宁夏格瑞精细化工有限公司 | Synthesis method of clethodim lithium salt standard sample |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53144548A (en) * | 1977-05-23 | 1978-12-15 | Nippon Soda Co Ltd | Cyclohexane derivatives, process for their preparation and herbicides contaning the same |
| JPS5668660A (en) * | 1979-11-07 | 1981-06-09 | Nippon Soda Co Ltd | Preparation of oxime derivative |
-
1985
- 1985-09-30 JP JP60214751A patent/JPH0643383B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6289653A (en) | 1987-04-24 |
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