JP5818073B2 - Process for producing O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate - Google Patents
Process for producing O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate Download PDFInfo
- Publication number
- JP5818073B2 JP5818073B2 JP2011156572A JP2011156572A JP5818073B2 JP 5818073 B2 JP5818073 B2 JP 5818073B2 JP 2011156572 A JP2011156572 A JP 2011156572A JP 2011156572 A JP2011156572 A JP 2011156572A JP 5818073 B2 JP5818073 B2 JP 5818073B2
- Authority
- JP
- Japan
- Prior art keywords
- ethyl
- cyanoimino
- propyl
- mol
- phosphonothioate
- 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.)
- Active
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、殺虫、殺ダニ、殺線虫、殺土壌害虫剤の活性成分として有用なＯ−エチル Ｓ−ｎ−プロピル (E)-[２-(シアノイミノ)-３-エチルイミダゾリジン-１-イル]ホスホノチオアート（一般名：イミシアホス(imicyafos)）の工業的に有利な製造方法に関する。 The present invention relates to O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidine-1-] useful as an active ingredient of insecticides, acaricides, nematicides and soil pesticides. [Il] phosphonothioate (generic name: imicyafos)
従来、イミシアホスの製造方法については、不活性溶媒及び塩基性物質の存在下に２−(シアノイミノ)−１−エチルイミダゾリジン（以下、CEIM）と、Ｏ−エチル-Ｓ−ｎ−プロピルホスホロクロリドチオアート（以下、OESP）とを反応させてイミシアホスを製造する方法が記載され公知である（特許文献１）。
上記従来技術においては、塩基性物質として、ｎ−ブチルリチウム、ｔ−ブチルリチウム、フェニルリチウムなどの有機リチウム化合物；水素化ナトリウム、水素化カリウム、金属ナトリウム、水酸化ナトリウム、水酸化カリウムなどの無機塩基；ナトリウムメトキシド、ナトリウムエトキシド、カリウムｔ−ブトキシドなどのアルコキシド類；トリエチルアミン、ピリジンなどの有機塩基などが列挙されているものの、具体的な製造例（合成例２）では、水素化ナトリウムが使用されているに過ぎない。 In the above prior art, as the basic substance, organic lithium compounds such as n-butyllithium, t-butyllithium and phenyllithium; inorganics such as sodium hydride, potassium hydride, sodium metal, sodium hydroxide and potassium hydroxide Alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; organic bases such as triethylamine and pyridine are listed. In a specific production example (Synthesis Example 2), sodium hydride is used. It is only used.
しかしながら、水素化ナトリウムは、高価でかつ反応時に水素ガスも発生するなどその取扱いに危険がともなう。しかも、溶媒に均一に溶融、分散させる必要があって操作が煩雑であり、生産性が低下するなど問題があり、工業的に有利なものとは言えない。また、シリカゲルカラムクロマトグラフィーを用いた精製などは工業的な精製法としては依然として改良が求められていた。 However, sodium hydride is expensive and has a risk in handling such as generation of hydrogen gas during the reaction. In addition, it is necessary to uniformly melt and disperse in a solvent, and the operation is complicated, and there are problems such as a decrease in productivity, which cannot be said to be industrially advantageous. Further, purification using silica gel column chromatography and the like has still been required as an industrial purification method.
従って、本発明は、工業的に非常に有利に生産でき、かつ高純度、高収率でイミシアホスを製造できる方法を提供することにある。 Accordingly, an object of the present invention is to provide a method capable of producing industrially very advantageously and producing imisiaphos with high purity and high yield.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、不活性溶媒及び塩基性物質の存在下、２−(シアノイミノ)−１−エチルイミダゾリジン（CEIM）と、Ｏ−エチル−Ｓ−ｎ−プロピルホスホロクロリドチオアート（OESP）とを反応させてイミシアホスを製造する方法において、反応において使用される塩基として、従来使用されてきた塩基と異なる、特定のアルカリ金属水酸化物、アルカリ土類金属水酸化物又は金属アルコキシドを使用することにより、上記課題を達成できることを見出し、本発明に到達したものである。 As a result of intensive studies to solve the above problems, the present inventors have found that 2- (cyanoimino) -1-ethylimidazolidine (CEIM) and O-ethyl-in the presence of an inert solvent and a basic substance. In a method of producing imiciaphos by reacting with Sn-propyl phosphorochloride thioate (OESP), a specific alkali metal hydroxide different from a conventionally used base as a base used in the reaction, The inventors have found that the above problems can be achieved by using an alkaline earth metal hydroxide or metal alkoxide, and have reached the present invention.
即ち、本発明は、不活性溶媒及び塩基性物質の存在下、２−(シアノイミノ)−１−エチルイミダゾリジン（CEIM）と、Ｏ−エチル-Ｓ−ｎ−プロピルホスホロクロリドチオアート（OESP）とを反応させてＯ−エチル Ｓ−ｎ−プロピル (E)−[２−(シアノイミノ)−３−エチルイミダゾリジン−１−イル]ホスホノチオアートを製造する方法において、塩基性物質としてアルカリ金属水酸化物、アルカリ土類金属水酸化物又は金属アルコキシドを用いることを特徴とする、Ｏ−エチル Ｓ−ｎ−プロピル (E)−[２−(シアノイミノ)−３−エチルイミダゾリジン−１−イル]ホスホノチオアートの製造方法に関するものである。 That is, the present invention relates to 2- (cyanoimino) -1-ethylimidazolidine (CEIM) and O-ethyl-Sn-propyl phosphorochloride thioate (OESP) in the presence of an inert solvent and a basic substance. In the production of O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate by reacting with O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl], characterized by using an oxide, an alkaline earth metal hydroxide or a metal alkoxide The present invention relates to a method for producing phosphonothioate.
以下、本発明について詳細に説明する。
本発明方法において使用するアルカリ金属水酸化物、アルカリ土類金属水酸化物又は金属アルコキシドとしては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、ナトリウムメトキシド、ナトリウムエトキシド、カリウムエトキシド、カリウムｔ−ブトキシドなどが挙げられるが、望ましくは水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、ナトリウムエトキシドやカリウムエトキシド、より望ましくは水酸化ナトリウム、ナトリウムメトキシドである。
Hereinafter, the present invention will be described in detail.
Examples of the alkali metal hydroxide, alkaline earth metal hydroxide or metal alkoxide used in the method of the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium methoxide. Sodium ethoxide, potassium ethoxide, potassium t-butoxide, etc., preferably sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide or potassium ethoxide, more preferably sodium hydroxide, sodium methoxy. It is.
不活性溶媒としては、本発明の反応の進行に対して実質的に影響を与えないものであり、特に限定されるものではなく、各種の不活性溶媒、例えば、ベンゼンや、トルエン、キシレン、クロロベンゼンなどの各種芳香族炭化水素類、塩化メチレンや、クロロホルム、ジクロロエタン、シクロヘキサンなどの各種環状又は非環状脂肪族炭化水素類、ジオキサンや、ジエチルエーテル、メチルエチルエーテル、テトラヒドロフランなどの各種エーテル類などが好適に挙げられる。特に好ましい不活性溶媒は、トルエン、ジクロロエタン、テトラヒドロフランなどであり、最も好ましいのは、トルエンである。 The inert solvent does not substantially affect the progress of the reaction of the present invention and is not particularly limited. Various inert solvents such as benzene, toluene, xylene, and chlorobenzene are used. Preferred are various aromatic hydrocarbons such as methylene chloride, various cyclic or acyclic aliphatic hydrocarbons such as chloroform, dichloroethane, and cyclohexane, dioxane, and various ethers such as diethyl ether, methyl ethyl ether, and tetrahydrofuran. It is mentioned in. Particularly preferred inert solvents are toluene, dichloroethane, tetrahydrofuran and the like, and most preferred is toluene.
本発明では、CEIMは、OESP １モルに対して、少なくとも0.8〜2.0モル、好ましくは、0.9〜1.4モルで使用される。一方、本発明では、CEIMの使用量の上限値は特に限定されるものではないが、反応操作や、循環操作などの工業的実施面を考慮して適切な値が決定される。塩基性物質の使用量は、反応条件の相違により一概に規定できないが、通常、CEIM １モルに対して、0.9〜1.5モル、好ましくは、0.95〜1.2モルであり、同様に不活性溶媒の使用量は、通常、CEIM 100重量部に対して、それぞれ100〜3000質量部、好ましくは、200〜1500質量部である。 In the present invention, CEIM is used in an amount of at least 0.8 to 2.0 mol, preferably 0.9 to 1.4 mol, relative to 1 mol of OESP. On the other hand, in the present invention, the upper limit value of the amount of CEIM used is not particularly limited, but an appropriate value is determined in consideration of industrial implementation aspects such as reaction operation and circulation operation. The amount of basic substance to be used cannot be generally specified due to the difference in reaction conditions, but is usually 0.9 to 1.5 mol, preferably 0.95 to 1.2 mol with respect to 1 mol of CEIM. The amount is usually 100 to 3000 parts by mass, preferably 200 to 1500 parts by mass, with respect to 100 parts by mass of CEIM.
本発明の反応において、テトラ−ｎ−ブチルホスホニウムブロマイド、トリフェニルデシルホスホニウムアイオダイド、トリブチルヘキサデシルホスホニウムブロマイドなどのホスホニウム塩、ベンジルトリブチルアンモニウムクロライド、テトラブチルアンモニウムブロマイド、トリオクチルアンモニウムクロライドなどのアンモニウム塩などの相間移動触媒や、1,8−ジアザビシクロ〔5,4,0〕−７−ウンデセン、1,4−ジアザビシクロ〔2,2,2〕オクタン、キヌクリジン塩酸塩、３−キヌクリジノン塩酸塩、３−キヌクリジノールなどの塩基性触媒をCEIM １モルに対し、例えば、0.01〜3.0モル添加したり、１２-クラウン-４、１５-クラウン-５又は１８-クラウン-６などをCEIM １モルに対し、0.0005〜0.1モル添加すると、反応速度が高まり、目的のイミシアホスの生成率が高まることがある。 In the reaction of the present invention, phosphonium salts such as tetra-n-butylphosphonium bromide, triphenyldecylphosphonium iodide, tributylhexadecylphosphonium bromide, ammonium salts such as benzyltributylammonium chloride, tetrabutylammonium bromide, trioctylammonium chloride, etc. Phase transfer catalysts, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,4-diazabicyclo [2,2,2] octane, quinuclidine hydrochloride, 3-quinuclidinone hydrochloride, 3-quinuclidinol For example, 0.01 to 3.0 mol of a basic catalyst such as 12-crown-4, 15-crown-5, or 18-crown-6 is added to 0.005 to 0.1 mol of 1 mol of CEIM. When added in moles, the reaction rate increases and the target There is that the generation rate of Shiahosu increases.
本発明の反応は反応条件の相違により一概に規定できないが、反応温度−50℃〜＋100℃、好ましくは、−20℃〜＋40℃で、普通0.5〜48時間、好ましくは、１〜20時間であることが適当である。反応生成物は、一般に水と混合されて溶媒相と水相とに分液され溶媒相を水洗した後溶媒を留去すれば目的のイミシアホスが取得できる。本発明方法によれば目的のイミシアホスは高純度でかつ高収率で製造することができる。
次に本発明の実施例を記載する。
Although the reaction of the present invention cannot be defined unconditionally due to the difference in reaction conditions, the reaction temperature is −50 ° C. to + 100 ° C., preferably −20 ° C. to + 40 ° C., usually 0.5 to 48 hours, preferably 1 to 20 hours. It is appropriate to be. The reaction product is generally mixed with water and separated into a solvent phase and an aqueous phase. The solvent phase is washed with water and then the solvent is distilled off to obtain the desired imisiaphos. According to the method of the present invention, the target imisiaphos can be produced with high purity and high yield.
Next, examples of the present invention will be described.
実施例１
99％水酸化ナトリウム10.15g（0.254モル）をトルエン250mlに懸濁させ、２−(シアノイミノ)−１−エチルイミダゾリジン（CEIM）35.58g（0.258モル）を室温で撹拌しながら加えた。加熱還流1.5時間行い、ディンスタークトラップで水4.5mlを留去した。さらに還流しながらトルエン２００ｍｌを留去した。その後100ｍｌのトルエンを加え-15℃に冷却した溶液へ、85.1％のＯ−エチル-Ｓ−ｎ−プロピルホスホロクロリドチオアート（OESP）のトルエン溶液59.53g（0.250モル）を30分間で滴下した。滴下後-１０℃で約１時間、-１０℃〜0℃で1時間撹拌、0℃〜20℃で3時間撹拌して反応させた。反応終了後、反応液を水100mlで洗浄した後、溶媒を留去して油状のＯ−エチル Ｓ−ｎ−プロピル (E)−[２−(シアノイミノ)−３−エチルイミダゾリジン−１−イル]ホスホノチオアート 生成物７６.０gを得た（収率99.9％）。この生成物はHPLCによる分析の結果、純度95.0％であった。
Example 1
99.15 g (0.254 mol) of 99% sodium hydroxide was suspended in 250 ml of toluene, and 35.58 g (0.258 mol) of 2- (cyanoimino) -1-ethylimidazolidine (CEIM) was added at room temperature with stirring. The mixture was heated and refluxed for 1.5 hours, and 4.5 ml of water was distilled off using a Din Stark trap. Further, 200 ml of toluene was distilled off while refluxing. Thereafter, 59.53 g (0.250 mol) of a toluene solution of 85.1% O-ethyl-Sn-propyl phosphorochloride thioate (OESP) was dropped into the solution which was added with 100 ml of toluene and cooled to -15 ° C. over 30 minutes. . After the dropwise addition, the reaction was carried out by stirring at -10 ° C for about 1 hour, at -10 ° C to 0 ° C for 1 hour, and at 0 ° C to 20 ° C for 3 hours. After completion of the reaction, the reaction solution was washed with 100 ml of water, and then the solvent was distilled off to give oily O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl. ] 76.0 g of phosphonothioate product was obtained (99.9% yield). As a result of analysis by HPLC, this product was 95.0% pure.
実施例２
２８％ナトリウムメトキシドのメタノール溶液48.23g（0.250モル）に２−(シアノイミノ)−１−エチルイミダゾリジン（CEIM）35.58g（0.258モル）を室温で撹拌しながら加えた。その後トルエン80mlを加え、加温してメタノールとトルエンを減圧留去した。さらにトルエン５０ｍｌを加えた後、加熱減圧留去してメタノールを完全に除いた。その後150ｍｌのトルエンを加え-15℃に冷却した溶液へ、85.1％のＯ−エチル-Ｓ−ｎ−プロピルホスホロクロリドチオアート（OESP）のトルエン溶液59.53g（0.250モル）を30分間で滴下した。滴下後-１０℃で約１時間、-１０℃〜0℃で1時間撹拌、0℃〜20℃で3時間撹拌して反応させた。反応終了後、反応液を水70mlで洗浄した後、溶媒を留去して油状のＯ−エチル Ｓ−ｎ−プロピル (E)−[２−(シアノイミノ)−３−エチルイミダゾリジン−１−イル]ホスホノチオアート 生成物７５.０gを得た（収率９８．６％）。この生成物はHPLCによる分析の結果、純度94.0％であった。
Example 2
To 48.23 g (0.250 mol) of 28% sodium methoxide in methanol was added 35.58 g (0.258 mol) of 2- (cyanoimino) -1-ethylimidazolidine (CEIM) at room temperature with stirring. Thereafter, 80 ml of toluene was added and heated to distill off methanol and toluene under reduced pressure. Further, 50 ml of toluene was added, and the methanol was removed by heating under reduced pressure. Thereafter, 59.53 g (0.250 mol) of a toluene solution of 85.1% O-ethyl-Sn-propyl phosphorochloride thioate (OESP) was dropped into the solution which was added 150 ml of toluene and cooled to -15 ° C. over 30 minutes. . After the dropwise addition, the reaction was carried out by stirring at -10 ° C for about 1 hour, at -10 ° C to 0 ° C for 1 hour, and at 0 ° C to 20 ° C for 3 hours. After completion of the reaction, the reaction solution was washed with 70 ml of water, and then the solvent was distilled off to give oily O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl. ] 75.0 g of the phosphonothioate product was obtained (yield 98.6%). As a result of analysis by HPLC, this product was 94.0% pure.
比較参考例１ （特公平７−３９４３０に記載の合成例２に準じた方法）
Ｏ−エチル-Ｓ−ｎ−プロピル（３−エチル−２−シアノイミノ−１−イミダゾリジニル）ホスホノチオレート（化合物番号４）（イミシアホス）の製造
６０％水素化ナトリウム0.４４ｇ（0.0011モル）及びＮ，Ｎ−ジメチルホルムアミド５０mlの混合物に２−(シアノイミノ)−１−エチルイミダゾリジン（CEIM）1.３８ｇ（0.0010モル）を徐々に添加した。しばらくしてＯ−エチル-Ｓ−ｎ−プロピルホスホロクロリドチオアート（OESP）の８８.２％トルエン溶液２.７６ｇ（0.0012モル）を徐々に滴下した。滴下終了後、反応液を氷水へ投入し、クロロホルムで抽出した。クロロホルム層を水洗後、無水硫酸マグネシウムで乾燥し、クロロホルムを減圧留去後、シリカゲルカラムクロマトグラフィー（溶媒＝クロロホルム：メタノール＝９７：３）を用いて精製して油状の表題化合物1.５０ｇ（収率４９．３％）を得た。
Comparative Reference Example 1 (Method according to Synthesis Example 2 described in JP-B-7-39430)
Preparation of O-ethyl-Sn-propyl (3-ethyl-2-cyanoimino-1-imidazolidinyl) phosphonothiolate (Compound No. 4) (Imisiaphos) 60% sodium hydride 0.44 g (0.0011 mol) and N, To a mixture of 50 ml of N-dimethylformamide, 1.38 g (0.0010 mol) of 2- (cyanoimino) -1-ethylimidazolidine (CEIM) was gradually added. After a while, 2.76 g (0.0012 mol) of an 88.2% toluene solution of O-ethyl-Sn-propyl phosphorochloride thioate (OESP) was gradually added dropwise. After completion of the dropping, the reaction solution was poured into ice water and extracted with chloroform. The chloroform layer was washed with water and dried over anhydrous magnesium sulfate. Chloroform was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography (solvent = chloroform: methanol = 97: 3) to give 1.50 g (yield) of the title compound as an oil. (Rate 49.3%) was obtained.
本発明によれば、２−(シアノイミノ)−１−エチルイミダゾリジン（CEIM）と、Ｏ−エチル-Ｓ−ｎ−プロピルホスホロクロリドチオアート（OESP）とを反応させて目的物Ｏ−エチル Ｓ−ｎ−プロピル (E)−[２−(シアノイミノ)−３−エチルイミダゾリジン−１−イル]ホスホノチオアート（イミシアホス）を製造する方法において、塩基性物質としてアルカリ金属水酸化物、アルカリ土類金属水酸化物又は金属アルコキシドを使用することにより、目的物であるイミシアホスを高純度及び収率で製造でき、工業的実施面で従来法に比し有利である。 According to the present invention, 2- (cyanoimino) -1-ethylimidazolidine (CEIM) is reacted with O-ethyl-Sn-propyl phosphorochloride thioate (OESP) to obtain the target product O-ethyl S. In a method for producing -n-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate (imiciaphos), alkali metal hydroxide, alkaline earth as basic substance By using a metal hydroxide or metal alkoxide, the target product, imiciaphos, can be produced with high purity and yield, which is advantageous in industrial implementation compared to conventional methods.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011156572A JP5818073B2 (en) | 2011-07-15 | 2011-07-15 | Process for producing O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011156572A JP5818073B2 (en) | 2011-07-15 | 2011-07-15 | Process for producing O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013023445A JP2013023445A (en) | 2013-02-04 |
| JP5818073B2 true JP5818073B2 (en) | 2015-11-18 |
Family
ID=47782179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011156572A Active JP5818073B2 (en) | 2011-07-15 | 2011-07-15 | Process for producing O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5818073B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2771882B2 (en) * | 1990-03-09 | 1998-07-02 | 石原産業株式会社 | Process for producing S, O-dialkyl (2-oxo-3-thiazolidinyl) phosphonothiolate |
| JPH0739430B2 (en) * | 1990-07-06 | 1995-05-01 | アグロカネショウ株式会社 | Organophosphorus compound, method for producing the same and insecticide, acaricide, nematicide containing the compound |
| DE4132492A1 (en) * | 1991-09-30 | 1993-04-01 | Bayer Ag | PHOSPHORYLATED DIAZACYCLOAL CHANE |
| JPH10109994A (en) * | 1996-10-03 | 1998-04-28 | Sumitomo Chem Co Ltd | Production of amidothiophosphate derivative |
-
2011
- 2011-07-15 JP JP2011156572A patent/JP5818073B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013023445A (en) | 2013-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2011047501A1 (en) | 2,4,6- or 2,6-alkoxyphenyl dialkylphosphine, tetrafluoroborate, preparation method and use thereof | |
| DK2670751T3 (en) | PROCEDURES FOR MANUFACTURING HIV BINDING INHIBITOR PRODUCT CONNECTION AND INTERMEDIATES | |
| JP2012153691A (en) | Optically active ammonium salt compound and production intermediate thereof | |
| CN106674264A (en) | Synthetic method for (2,2,2-trifluoroethoxyl) phenylboronic acid compounds | |
| WO2005063780A1 (en) | Process for the preparation of pyridine derivatives | |
| Koech et al. | Enantioselective total and formal syntheses of paroxetine (PAXIL) via phosphine-catalyzed enone α-arylation using arylbismuth (V) reagents: a regiochemical complement to Heck arylation | |
| JP5818073B2 (en) | Process for producing O-ethyl Sn-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate | |
| JP2019147829A (en) | 5-(trifluoromethyl)pyrimidine derivative and manufacturing method therefor | |
| JP2009215214A (en) | METHOD FOR PRODUCING alpha-AMINOPHOSPHONIC ACID ESTER DERIVATIVE | |
| US20130005992A1 (en) | Method for producing optically active n-monoalkyl-3-hydroxy-3-arylpropylamine compound | |
| JP5001144B2 (en) | Process for producing 2-isopropenyl-5-methyl-4-hexen-1-yl 3-methyl-2-butenoate | |
| JP6257115B2 (en) | Method for producing 3-alkylthio-2-bromopyridine | |
| CN110139853B (en) | Process for the preparation of pesticidal compounds | |
| US20090292135A1 (en) | Organometal benzenephosphonate coupling agents | |
| JP5639376B2 (en) | Borate compounds | |
| CN114409706B (en) | Preparation method of phenyl hydrogen phosphonate and intermediate thereof | |
| TWI772349B (en) | Processes for the preparation of pesticidal compounds | |
| JP2005255561A (en) | Multi-substituted pyrimidine and method for selectively producing the same | |
| JP6235932B2 (en) | Method for producing 2-cyanophenylboronic acid derivative | |
| CN104395326B (en) | The manufacture method of two substituted boracic acid derivants and new two substituted boracic acids derivant | |
| JP5296109B2 (en) | Novel biphenyl compounds having reactive groups | |
| JP6262079B2 (en) | 4- (2,2,2-trifluoroethoxy) -5- (trifluoromethyl) pyrimidine derivative and method for producing the same | |
| KR101560818B1 (en) | Process for the preparation of benzofuran derivatives | |
| JP2004137165A (en) | Method for producing nitrogen-containing heterocyclic compound | |
| JP4507398B2 (en) | Method for synthesizing 3-halomethyloxetane compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140424 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150114 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150115 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150313 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150902 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150916 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5818073 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |