JPS6366156A - Molecular compound and production thereof - Google Patents
Molecular compound and production thereofInfo
- Publication number
- JPS6366156A JPS6366156A JP20958886A JP20958886A JPS6366156A JP S6366156 A JPS6366156 A JP S6366156A JP 20958886 A JP20958886 A JP 20958886A JP 20958886 A JP20958886 A JP 20958886A JP S6366156 A JPS6366156 A JP S6366156A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- methanol
- isomer
- molecular compound
- reaction product
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 153
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 24
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000004009 herbicide Substances 0.000 abstract description 3
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 229940126062 Compound A Drugs 0.000 description 42
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 42
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 239000007795 chemical reaction product Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 16
- 238000006396 nitration reaction Methods 0.000 description 15
- 239000013078 crystal Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- -1 Alkali metal salts Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
化合物〔〔〔２−ニトロ−５−（２’−クロロ−４′−
トリフロロメチルフェノキシ）−α−メトキシメチルベ
ンジリデン〕アミノ〕オキシ〕−酢酸やそのエステル、
アルカリ金属塩等は、除草剤として有用なものであり、
その除草効果、製造方法及び物性に関しては、特開昭６
１−１４０５４６号公報に詳細に開示されている。Detailed Description of the Invention "Industrial Application Field" Compound [[[2-nitro-5-(2'-chloro-4'-
trifluoromethylphenoxy)-α-methoxymethylbenzylidene]amino]oxy]-acetic acid and its esters,
Alkali metal salts etc. are useful as herbicides,
Regarding its herbicidal effect, manufacturing method, and physical properties, please refer to JP-A No. 6
It is disclosed in detail in Japanese Patent No. 1-140546.
製造法に関しては、例えば、化合物ｒ ｒ ｒ ３−（
２’−クロロ−４′−トリフロロメチルフェノキシ）−
α−メトキシメチルベンジリデン】アミノ〕オキシ〕−
酢酸
をモノニトロ化して、化・金物Ａを得る方法が示されて
いる。か〜る製造方法はかなり効率のよい方法ではある
が、各種異性体、例えは、（ＣＣ２−ニトロ−３−（２
’−クロロ−４′−トリフロロメチルフェノキシ）−α
−メトキシメチルベンジリデン〕アミノ〕オキシ〕−酢
酸ヤｃ ＣＣ４−＝ドロー ３− （２’−クロロ−４
′−トリフロロメチルフェノキシ）−α−メトキシメチ
ルベンジリデン〕アミノ〕オキシ〕−酢酸等も同時に副
生ずる。またその他の化合物Ａの合成法を採用しても、
副生物が生成することは避けがたい。Regarding the manufacturing method, for example, the compound r r r 3-(
2'-chloro-4'-trifluoromethylphenoxy)-
α-methoxymethylbenzylidene]amino]oxy]-
A method for obtaining chemical compound A by mononitrating acetic acid is shown. Although this production method is quite efficient, various isomers, for example (CC2-nitro-3-(2
'-Chloro-4'-trifluoromethylphenoxy)-α
-methoxymethylbenzylidene]amino]oxy]-acetic acid CC4-=draw 3- (2'-chloro-4
'-trifluoromethylphenoxy)-α-methoxymethylbenzylidene]amino]oxy]-acetic acid and the like are also produced as by-products. Also, even if other synthetic methods for compound A are adopted,
It is inevitable that by-products will be produced.
以上の様にして得た副生物を含有する化合物Ａあるいは
その誘導体を、ｎ製せずに除草剤として使用することも
考えられるが、これら副生物による、散布圃場における
生態系への不必要な作用も想定される。従って、予め化
合物Ａから副生物を極力除去しておくなら、惹起される
かもしれない副生物に基づく予想外の様々な事態を事前
に回避しうろことどなり、分離・ｉ農法の開発が必要と
なる。It is possible to use Compound A or its derivatives containing the by-products obtained as described above as herbicides without manufacturing them, but these by-products may cause unnecessary damage to the ecosystem in the field where they are sprayed. Effects are also expected. Therefore, if by-products are removed from Compound A as much as possible in advance, various unexpected situations caused by by-products that may be caused can be avoided in advance, and the development of separation and i-farming methods will be necessary. Become.
「従来の技術」
従来、化合物Ｂの類のニトロ化反応においては副生物の
生成は避げ、がたい走め、ニトロ化反応生成混合物中よ
り再結晶法により、目的物の大部分を結晶として、分離
ｙｎＩｇすることが試みられてきている。そこで、例え
ば化合物Ｂのモノニトロ化反応により得られた化合物Ａ
を含む反応生成混合物から、効率よく化合物Ａを再結晶
化する方法を検討した。しかし、適切な再結晶用溶媒は
見い出し得す、再結晶法を化合□物Ａの分離ｎ！製表法
して採用することは困難であった。``Prior art'' Conventionally, in the nitration reaction of compound B, the production of by-products was avoided, and most of the target compound was converted into crystals by a recrystallization method from the nitration reaction product mixture. , attempts have been made to isolate ynIg. Therefore, for example, compound A obtained by mononitration reaction of compound B
We investigated a method for efficiently recrystallizing Compound A from a reaction product mixture containing. However, a suitable recrystallization solvent can be found, and the recrystallization method can be used to separate compound □ compound A n! It was difficult to create a table and use it.
「発明が解決しようとする問題点」
前述した化合物Ｂをモノニトロ化する方法や、その他の
合成方法で得た化合物Ａ’ｋｆむ反応生成混合物より、
効率よく化合物Ａを分離精製する方法を提案することが
望まれる。"Problems to be Solved by the Invention" From the reaction product mixture of compound A'kf obtained by the above-mentioned method of mononitrating compound B or other synthetic methods,
It is desired to propose a method for efficiently separating and purifying compound A.
「問題点を解決するだめの手段」
再結晶法に代る効率のよい方法を探索ｔ、た際、化合物
ＡにはＥ−異性体と２−異性体が存在するが、このうち
、前者はメタノールとモル比はｙｌ：１の分子化合物を
形成することを見いだした。``A means to solve the problem'' When searching for an efficient method to replace the recrystallization method, it was discovered that compound A has an E-isomer and a 2-isomer, of which the former is It was found that a molecular compound with a molar ratio of yl:1 was formed with methanol.
更に、該分子化合物がメタノールにａ＃である特徴を発
見した。従って、濾別により、メタノール等を除去する
方法を組合せ、化合物ＡのＥ−異性体をメタノールとの
分子化合物として、分離精製する方法を完成するに至っ
た。Furthermore, we discovered that the molecular compound is a# in methanol. Therefore, by combining the method of removing methanol and the like by filtration, we have completed a method for separating and purifying the E-isomer of compound A as a molecular compound with methanol.
すなわちこの発明は、
（１） Ｅ−〔〔（２−ニトロ−５−（２’−クロロ−
４′−トリフルオロメチルフェノキシ）−α−メトキシ
メチルベンジリデン〕アミノ〕オキシ〕−酢酸とメタノ
ールとからなる分子化合物、および、（２）ｒｒｒ２−
二トロー５−（’２’−クロロー４′−トリフルオロメ
チルフェノキシ）−α−メトキシメチルベンジリデン〕
アミノ〕オキシ〕−酢酸とメタノールを接触させ、得ら
れる混合物中からメタノールを濾別除去するＥ−ｒｃｃ
２−ニトロ−５−（２’−りａｏ−ｄ’−１，リフルオ
ロメチルフェノキシ）−α−メトキシメチルベンジリデ
ン〕アミノ〕オキシ］−酢酸とメタノールとからなる分
子化合物の製造法である。That is, this invention provides: (1) E-[[(2-nitro-5-(2'-chloro-
a molecular compound consisting of 4'-trifluoromethylphenoxy)-α-methoxymethylbenzylidene]amino]oxy]-acetic acid and methanol, and (2) rrr2-
Nitro-5-('2'-chloro-4'-trifluoromethylphenoxy)-α-methoxymethylbenzylidene]
E-rcc in which methanol is removed by filtration from the resulting mixture by bringing amino]oxy]-acetic acid into contact with methanol
This is a method for producing a molecular compound consisting of 2-nitro-5-(2'-riao-d'-1, lifluoromethylphenoxy)-α-methoxymethylbenzylidene]amino]oxy]-acetic acid and methanol.
以下に、本発明の分子化合物の製造法を詳しく述べる。The method for producing the molecular compound of the present invention will be described in detail below.
例えば、化合物Ｂを常法により一５℃乃至常温もしくは
４０℃−ト、硫酸と硝酸とからなる混酸で、ニトロ化［
、た後、氷水に反応生成混合物を添加し、適当な水不溶
の溶剤で抽出した化合物Ａを含むニトロ化反応生成混合
物からなる有機層を減圧下に処理し溶剤を除去する。次
いで、得られたニトロ化反応生成混合物にメタノールを
添加、攪拌すると、メタノールと化合物ＡのＥ−異性体
が、メタノール難溶の分子化合物を形成するが、これは
固体として懸濁し析出するので、濾過により容易に分離
取得される。For example, compound B is nitrated by a conventional method at -5°C to room temperature or at 40°C with a mixed acid consisting of sulfuric acid and nitric acid.
After that, the reaction product mixture is added to ice water, and the organic layer consisting of the nitration reaction product mixture containing compound A extracted with a suitable water-insoluble solvent is treated under reduced pressure to remove the solvent. Next, when methanol is added to the obtained nitration reaction product mixture and stirred, methanol and the E-isomer of compound A form a molecular compound that is poorly soluble in methanol, but this is suspended and precipitated as a solid. Easily separated and obtained by filtration.
この際、化合物Ａの元−異性体以外は、大部分メタノー
ルに溶解しているが、化合物゛Ａの２−異性体の一部は
、上記分子化合物に随伴して、分離される。したがって
、本発明の分子化合物に微量の２−異性体が含まれる場
合は、本発明の範囲内である。At this time, most of compounds other than the original isomer of compound A are dissolved in methanol, but a part of the 2-isomer of compound A is separated along with the above molecular compound. Therefore, if the molecular compound of the present invention contains trace amounts of the 2-isomer, it is within the scope of the present invention.
上記のニトロ化反応生成混合物に、メタノールを添加す
る前に、ニトロ化反応の際に用いられた硫酸や未反応硝
酸は水洗、中和などにより十分に除去されねばならない
。これは、鉱酸の混入が、メタノール共存下、化合物Ａ
のメチルニスデル生成を促進し、もはやメタノールとの
分子化合物が形成されないためである。Before adding methanol to the above-mentioned nitration reaction product mixture, sulfuric acid and unreacted nitric acid used in the nitration reaction must be sufficiently removed by washing with water, neutralization, etc. This is because the contamination of mineral acid caused Compound A to react in the coexistence of methanol.
This is because it promotes the formation of methyl nisdel and no longer forms a molecular compound with methanol.
また、例え、これら鉱酸類の混入が考えられない場合で
も、化合物Ａを含む反応生成混合物とメタノールが高温
で接触することは、やはりメチルエステルの生成を促し
、上述した理由により、分離精製効率が著しく低くなる
か、不可能となるため、避けねばならない。それ故、メ
タノールと化合物Ａｉ含む反応生成混合物の接触は、メ
チルエステル化反応が進行し難い条件下で、例えば、常
温（２５℃）以下短時間内になされることが望ましい。Furthermore, even if the contamination of these mineral acids is not considered, the contact between the reaction product mixture containing Compound A and methanol at high temperature will still promote the production of methyl ester, and for the reasons mentioned above, the separation and purification efficiency will be reduced. This should be avoided as it will be significantly lower or even impossible. Therefore, the contact between methanol and the reaction product mixture containing the compound Ai is desirably carried out under conditions in which the methyl esterification reaction is difficult to proceed, for example, within a short period of time below room temperature (25° C.).
次に、化合物Ａｉ含む反応生成混合物とメタノールの接
触は、前者に後者を添加しても、後者に前者を添加して
もよい。Next, the reaction product mixture containing compound Ai and methanol may be brought into contact by adding the latter to the former, or by adding the former to the latter.
この際、メタノールは必ずしも高純度のものである必要
はなく、前記分子化合物の形成とその固体発生が達成さ
れ〜ばよ（、例えばメタノールと水の混合溶液も使用し
うる。この場合、メタノールと水の割合は、化合物Ａを
含む反応生成混合物中の副生物を溶解しさるまでの水含
有量に制限されることとなり、化合物ＡＱ含む反応生成
混合物の絶対量とその中の副生物の含有量に応じ、メタ
ノール水の濃度と量が決定される。At this time, the methanol does not necessarily have to be of high purity, as long as the formation of the molecular compound and its solid generation are achieved (for example, a mixed solution of methanol and water may also be used. In this case, methanol and The proportion of water is limited to the water content that dissolves the by-products in the reaction product mixture containing compound A, and the absolute amount of the reaction product mixture containing compound AQ and the content of by-products therein. The concentration and amount of methanol water are determined accordingly.
また、化合物ＡのＥ−異性体とメタノールとからなる分
子化合物はメタノールに難溶とはいっても常温で４優前
後の溶解度を有することから、過剰のメタノールの使用
は、前記分子化合物の溶解量を増加し、固体として分離
する目的を達成しないこととなるので、必要量以上のメ
タノールの使用は避けるべきである。Furthermore, although the molecular compound consisting of the E-isomer of compound A and methanol is poorly soluble in methanol, it has a solubility of around 4 at room temperature. The use of methanol in excess of the required amount should be avoided, as this will increase the amount of methanol and defeat the purpose of separating it as a solid.
上述した操作を行なえば、通常容易に化合物ＡのＥ−異
性体とメタノールとからなる分子化合物が、固体として
発生してくるが、稀に固体発生の遅い場合がある。この
場合、冷却■、たり、種晶の添加により、固体の生成を
早めることが出来る。If the above-mentioned operation is carried out, a molecular compound consisting of the E-isomer of compound A and methanol will normally be easily generated as a solid, but in rare cases, the solid generation may be slow. In this case, solid formation can be accelerated by cooling or adding seed crystals.
以上の様にして得られた化合物ＡのＥ−異性体とメタ、
ノールとからなる分子化合物を、減圧下要時間処理する
か１、有機溶剤に溶解し、減圧下に使用した有機溶剤と
メタノールを留去することにより、化合物Ａが高純度で
回収しうる。E-isomer and meta of compound A obtained as above,
Compound A can be recovered in high purity by treating a molecular compound consisting of alcohol for a required time under reduced pressure or by dissolving it in an organic solvent and distilling off the used organic solvent and methanol under reduced pressure.
ところで、化合物Ａは、Ｅ−異性体のみならず、メタノ
・−ル中に溶解している２−異性体も有用であり、回収
することが望まれる。しかるに、かかるオキシム化合物
は、既に塩酸等による異性化方法が提案されており（例
えば、Ｊｏｕｒｎａｌ ｏｆＯｒｇａｎ−１ｏ Ｃｈｅ
ｍｌｓｔｒｙ ３５．３５４６（１９７，０）やＵＳＦ
４１５．８０１５参照）、これらの方法を本発明と組合
せることにより、化合物Ａの回収車を向上させ得る。即
ち、化合物Ａの２−異性体を濃硫酸で処理することによ
り、Ｅ−異性体とし、次いで本発明の方法により、化合
物ＡのＥ−異性体とメタノールとからなる分子化合物と
して回収しうる。By the way, not only the E-isomer of Compound A but also the 2-isomer dissolved in methanol is useful, and it is desirable to recover it. However, isomerization methods using hydrochloric acid and the like have already been proposed for such oxime compounds (for example, Journal of Organ-1o Che.
mlstry 35.3546 (197,0) and USF
415.8015), these methods can be combined with the present invention to improve Compound A recovery vehicles. That is, by treating the 2-isomer of Compound A with concentrated sulfuric acid, the E-isomer can be recovered, and then by the method of the present invention, it can be recovered as a molecular compound consisting of the E-isomer of Compound A and methanol.
「発明の効果」
化、合物Ｂをモノニトロ化して化合物Ａを合成する方法
やその他の方法で得た化合物Ａを含む反応生成混合物を
メタノールと接触させて、メタノール溶液中に懸濁して
いる固体を濾別するという、簡単な操作で、化合物Ａの
Ｅ−異性体をそのメタノールとからなる高い純度の分子
化合物と・して回収し得る。"Effect of the invention" A reaction product mixture containing compound A obtained by a method of synthesizing compound A by mononitration of compound B or other methods is brought into contact with methanol to produce a solid suspended in a methanol solution. The E-isomer of compound A can be recovered as a highly pure molecular compound consisting of methanol and methanol by a simple operation of filtering the E-isomer.
更に、該分子化合物をそのま−１あるいは溶剤に溶解後
、減圧下にメタノール、あるいはメタノールと溶剤を除
去することにより、純度の高い化合物Ａを効率よく取得
し得る。Furthermore, highly pure Compound A can be efficiently obtained by removing methanol or methanol and the solvent under reduced pressure after dissolving the molecular compound as it is or in a solvent.
以下に実施例をもって本発明を説明する。 ゛実施例１
゜
容量５Ｑｍの滴下ロート、温度計、乾燥用塩化カルシウ
ム管をとりつけた２００１１１三ロフラスコに、ジクロ
ロメタン１００ｙを添加し、ついで化合物Ｂ（Ｚ−異性
体９３％、、１ｌｆ−異性体６％からなる混合物）２０
．９．９１−加え、回転子で攪拌して均一溶液とした。The present invention will be explained below with reference to Examples.゛Example 1
゜To a 200111 three-neck flask equipped with a dropping funnel with a capacity of 5 Qm, a thermometer, and a calcium chloride tube for drying, 100 y of dichloromethane was added, and then compound B (a mixture consisting of 93% of the Z-isomer, 6% of the 1lf-isomer) was added. )20
．． 9.91-Add and stir with a rotor to make a homogeneous solution.
氷水と食塩からなる寒剤で外部より冷却し、０℃になっ
た時点で滴下ロート中に仕込んだ７０％硝酸５．０５．
＃と９５係硫酸５３．５，１７とからなる混酸を滴下し
た。滴下中、反応系内は、回転子による強力な攪拌によ
り口±２℃に制御された。は父１５分以内に滴下が終了
するが、なお３０分間０℃下、撹拌をつづけた。It was cooled externally with a cryogen consisting of ice water and salt, and when the temperature reached 0°C, 70% nitric acid (5.05%) was charged into the dropping funnel.
A mixed acid consisting of # and 95% sulfuric acid 53.5,17% was added dropwise. During the dropwise addition, the inside of the reaction system was controlled at ±2° C. by strong stirring using a rotor. The dropwise addition was completed within 15 minutes, but stirring was continued for 30 minutes at 0°C.
次いで５００ｇの氷水に反応液全投入し、更にジクロロ
メタン２００．９を添加し、鉱酸を水層に、化合物Ｂの
ニトロ化反応生成混合物をジクロロメタン層に分配し、
分液後、ジクロロメタン層を５００１１の水で２回洗滌
した。次いでジクロロメタン層を１００μの無水硫酸ナ
トリウムで乾燥後、ジクロロメタンを留去し、淡黄色の
粘稠なニトロ化反応生成混合物２６．０．９を得た。Next, the entire reaction solution was poured into 500 g of ice water, 200.9 g of dichloromethane was added, and the mineral acid was distributed into the aqueous layer, and the nitration reaction product mixture of compound B was distributed into the dichloromethane layer.
After separation, the dichloromethane layer was washed twice with 50011 water. Next, the dichloromethane layer was dried over 100 μm of anhydrous sodium sulfate, and then dichloromethane was distilled off to obtain a pale yellow viscous nitration reaction product mixture 26.0.9.
液体クロマトグラフで分析したところ、化合物Ｂの転化
率は９９．５ ％、化合物ＡのＥ−異性体の収率５２．
１係同じくｚ−異性体収車２８．０係であった。As analyzed by liquid chromatography, the conversion rate of compound B was 99.5%, and the yield of the E-isomer of compound A was 52.5%.
Section 1 also had a z-isomer collection vehicle of 28.0.
このようにｔ２て得られたニトロ化反応生成混合物のう
ち２５．９９に等重量のメタノールを加え、２５℃下、
該ニトロ化反応生成物のあめ状物質がなくなるまで攪拌
した。この間、化合物ＡのＥ −異性体はメタノールと
分子化合物を形成し、大部分が固体として液中に懸濁し
ておりこの固体は濾過操作により分離回収された。得た
固体は１３．０．９で、化合物ＡのＥ−異性体を８３．
４１、化合物Ａの２−異性体を９．１１４含有し、残り
の大部分はメタノールであった。この結晶５μをとり出
し、８０ｇの冷メタノールで洗滌し、２−異性体を殆ん
ど含まない結晶１ｇを得た。An equal weight of methanol was added to 25.99% of the nitration reaction product mixture obtained at t2, and at 25°C,
The mixture was stirred until the nitration reaction product disappeared. During this time, the E-isomer of compound A formed a molecular compound with methanol, most of which was suspended in the liquid as a solid, and this solid was separated and recovered by a filtration operation. The solid obtained was 13.0.9 and the E-isomer of Compound A was 83.0.9.
It contained 9.114 2-isomers of Compound A, with most of the remainder being methanol. 5μ of this crystal was taken out and washed with 80g of cold methanol to obtain 1g of crystal containing almost no 2-isomer.
元素分析の結果は次のとうり。（）内は計算値である。The results of elemental analysis are as follows. Values in parentheses are calculated values.
０ ４６．２係（４６，１係）
Ｈ３，５９優（３，６７係）
Ｎ ５．６５４（５，６６憾）
また、融点測定を試みたが、１１４〜１１９℃で分解し
た。0 46.2 Section (46.1 Section) H3,59 Excellent (3,67 Section) N 5.654 (5,66 Sorry) Melting point measurement was also attempted, but it decomposed at 114-119°C.
実施例２゜
上記実施例１にて得られた濾液であるメタノール溶液を
減圧下に処理し、１１．０／ｙ’のニトロ化反応生成物
を回収した。液体クロマトグラフで分析したところ、化
合物ＡのＥ−異性体１．［Ｊ ９．９、同じくｚ−異性
体５．４６／／が含有されていた。Example 2 The methanol solution, which is the filtrate obtained in Example 1 above, was treated under reduced pressure to recover a nitration reaction product of 11.0/y'. Analysis by liquid chromatography revealed E-isomer 1 of compound A. [J 9.9, also containing 5.46// of the z-isomer.
回収した１１．０／／のうち１０．１６’を、５０．９
のジクロロメタンに溶解し、更に９５憾硫酸２３．９を
添加［７，６０分間室温下に攪拌し異性化後、２００ｇ
の氷水に投入した。抽出効率を高めるため、更に１００
．９のジクロロメタンを加え、化合物Ｂのニトロ化反応
生成混合物を分配せしめた。10.16' of the collected 11.0// is 50.9
was dissolved in dichloromethane, and further added 23.9 g of 95 sulfuric acid [After isomerization by stirring at room temperature for 7.60 minutes, 200 g
was placed in ice water. To increase extraction efficiency, add 100 more
．． 9 of dichloromethane was added to partition the Compound B nitration reaction product mixture.
以下、実施例１と同様にして、ジクロロメタンと水を除
去した化合物Ｂのニトロ化反応生成混合物１０．５．９
を回収し、た。液体クロマトグラフにより分析した結果
、化合物ＡのＥ−異性体３．８０．９、同じくｚ−異性
体１．８４．９が含有されていた。Hereinafter, in the same manner as in Example 1, dichloromethane and water were removed, and nitration reaction product mixture 10.5.9 of compound B was prepared.
I collected it and took it. Analysis by liquid chromatography revealed that Compound A contained 3.80.9 of the E-isomer and 1.84.9 of the Z-isomer.
この回収物のうち１０．４．ｆに１２Ｉのメタノールを
加え２５℃下、回収物のあめ状物質が消失するまで、攪
拌し、実施例１で得た化合物ＡのＥ−異性体とメタノー
ルとからなる分子化合物０．１μを種晶として添加した
。得られた懸濁液を濾過し、３．６６．９の結晶を液体
クロマトグラフ及びガラクロマトグラフにより分析した
ところ、化合物ＡのＥ−異性体３．２０．９、同じくｚ
−異性体０．１３９を含有ｌ７、残りは大部分はメタノ
ールであった。Of this recovered material, 10.4. 12I methanol was added to f and stirred at 25°C until the candy-like substance in the recovered material disappeared, and 0.1μ of a molecular compound consisting of the E-isomer of compound A obtained in Example 1 and methanol was added. It was added as crystals. The obtained suspension was filtered, and crystals of 3.66.9 were analyzed by liquid chromatography and gala chromatography, and it was found that E-isomer 3.20.9 of compound A, also z
- 17 containing 0.139 isomers, the remainder being mostly methanol.
実施例３゜
実施例２にて得られたｉ＊ａを減圧下に濃縮［１，６，
７９のニトロ化反応生成物を巨１収した。液体クロマト
グラフで分析したところ、化合物ＡのＫ −異性体０．
５４．９、同じくｚ−異性体１．３７．９が含有されて
いた。回収した６、７ 、？ ｅ、３０μのジクロロメ
タンに溶解し、更に９５４ｍ酸ｉ ４ｇ’６添加、攪拌
し、室温下６０分間異性化を行なった。Example 3゜I*a obtained in Example 2 was concentrated under reduced pressure [1,6,
A large amount of nitration reaction product of 79 was obtained. Analysis by liquid chromatography revealed that the K-isomer of compound A was 0.
54.9, also containing the z-isomer 1.37.9. Collected 6, 7,? e, dissolved in 30μ of dichloromethane, further added 4g'6 of 954m acid, stirred, and isomerized at room temperature for 60 minutes.
以下、実施例２における氷水への投入以降の操作を繰り
返し、異性体の変換を行なった化合物Ｂのニトロ化反応
生成混合物６．１．！？’を得た。メタノール８Ｅを加
え、２５℃で、回収物のあめ状物質が消失するまで攪拌
ｌ−１実施例２にて用いたと同じ稲晶０．１ｇを添加ｌ
−た。得られた懸濁猷を濾過し、化合物ＡのＥ−異性体
０．６８ ／；／、同じ＜２−異性体０．０２ Ｅ、そ
の他からなる結晶０．８０μを得た０
参考例
実施例２にて得られた化合物ＡのＥ−異性体３．２０．
９同じくｚ−異性体０．１６μ及びメタノールを含む結
晶３．６６ 、！ｉ’を１０１の酢酸エチルに溶解後、
２５℃で減圧下（最終到達圧力２ ｘ＊Ｈｇ ）に処理
した処、メタノールを含有しない化合物ＡのＥ−異性体
３．２０．９と２−異性体０．１３．９その他からなる
結晶３．４４ 、！ｉ＋を得た。Hereinafter, the nitration reaction product mixture 6.1 of Compound B, which was obtained by repeating the operations after pouring into ice water in Example 2 and converting the isomer, is as follows. ! ? got '. Add methanol 8E and stir at 25°C until the candy-like substance of the recovered material disappears.1-1 Add 0.1 g of the same rice crystals used in Example 2.
-ta. The obtained suspension was filtered to obtain 0.80μ of crystals consisting of 0.68/;/ of the E-isomer of compound A, 0.02E of the same <2-isomer, and others. E-isomer of compound A obtained in 3.20.
9 Also crystals containing 0.16 μ of the z-isomer and methanol 3.66,! After dissolving i' in 101 ethyl acetate,
When treated at 25° C. under reduced pressure (final ultimate pressure 2 x * Hg), crystal 3 consisting of E-isomer 3.20.9, 2-isomer 0.13.9 and others of compound A containing no methanol was obtained. .44,! I got i+.
Claims (2)
′−トリフルオロメチルフェノキシ）−α−メトキシメ
チルベンジリデン〕アミノ〕オキシ〕−酢酸とメタノー
ルとからなる分子化合物。(1) E-[[[2-nitro-5-(2'-chloro-4
A molecular compound consisting of acetic acid and methanol.
トリフルオロメチルフェノキシ）−α−メトキシメチル
ベンジリデン〕アミノ〕オキシ〕−酢酸とメタノールを
接触させ、得られる混合物中からメタノールを濾別除去
するＥ−〔〔〔２−ニトロ−５−（２′−クロロ−４′
−トリフルオロメチルフェノキシ）−α−メトキシメチ
ルベンジリデン〕アミノ〕オキシ〕−酢酸とメタノール
とからなる分子化合物の製造法。(2) [[[2-nitro-5-(2'-chloro-4'-
E-[[[[2-nitro-5-(2'- Chloro-4'
-trifluoromethylphenoxy)-α-methoxymethylbenzylidene]amino]oxy]-acetic acid and methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20958886A JPS6366156A (en) | 1986-09-08 | 1986-09-08 | Molecular compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20958886A JPS6366156A (en) | 1986-09-08 | 1986-09-08 | Molecular compound and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6366156A true JPS6366156A (en) | 1988-03-24 |
Family
ID=16575317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20958886A Pending JPS6366156A (en) | 1986-09-08 | 1986-09-08 | Molecular compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6366156A (en) |
-
1986
- 1986-09-08 JP JP20958886A patent/JPS6366156A/en active Pending
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