JPS59206393A - Preparation of s-methylphosphorodichloridothioate - Google Patents
Preparation of s-methylphosphorodichloridothioateInfo
- Publication number
- JPS59206393A JPS59206393A JP8231083A JP8231083A JPS59206393A JP S59206393 A JPS59206393 A JP S59206393A JP 8231083 A JP8231083 A JP 8231083A JP 8231083 A JP8231083 A JP 8231083A JP S59206393 A JPS59206393 A JP S59206393A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- methyl compound
- catalyst
- compound
- toluene
- 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
Abstract
Description
【発明の詳細な説明】
本発明は式
で示される８−メチル ホスホロジクロリドチオエート
（以下、８−メチル体と称す。）の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 8-methyl phosphorodichloride thioate (hereinafter referred to as 8-methyl compound) represented by the formula.
Ｓ−メチル体はたとえば有機リン化合物系農薬で殺虫剤
の有効成分である式
で示される０−エチル Ｓ−イソブチル ８−メチル
ジチオリン酸エステルなどの製造中間体として用いられ
る。The S-methyl compound is, for example, an organic phosphorus compound pesticide, which is an active ingredient of an insecticide, and is represented by the formula 0-ethyl S-isobutyl 8-methyl.
Used as an intermediate in the production of dithiophosphoric acid esters, etc.
Ｓ−メチル体の製造法としては、たとえば式で示される
Ｏ−メチル ホスホロジクロリドチオエート（以下、０
−メチル体と称す。〕を異性化する方法があり、具体的
には無溶媒下、１００〜１１０℃の温度範囲で熱異性化
する方法（Ｊｏｕｒｎａｌ ｆｉｆｒｐｒａｋｔｉｓｃ
ｈｅ Ｃｈｅｒｎｉｅ ４ Ｒｅ１ｈｅＢａｎｄ １２
（１９６０） ）および光異性化する方法（Ａｇｒ
ｉｃ、 Ｂｉｏｌ、 Ｃｈｅｍ、 ４６１９８５ （１
９８２） ）が知られている。しかし、これらの方法は
反応制御が困難であること、収率が低いことおよびコス
トが高いことなどの欠点があり、工業的に充分な方法と
はいえない。As a method for producing the S-methyl compound, for example, O-methyl phosphorodichloride thioate (hereinafter referred to as 0
-It is called the methyl form. ], specifically, thermal isomerization in the temperature range of 100 to 110°C without a solvent (Journal fifrpraktisc).
he Chernie 4 Re1heBand 12
(1960) ) and a method for photoisomerization (Agr
ic, Biol, Chem, 461985 (1
982) ) is known. However, these methods have drawbacks such as difficulty in reaction control, low yield, and high cost, and cannot be said to be industrially sufficient methods.
このような状況の下で、本発明者らは８−メチル体の製
造法について鋭意検討を重ねた結果、触媒および不活性
希釈剤にＯ−メチル体を添加して異性化することにより
低温で反応を進めることができ、Ｓ−メチル体を高収率
で製造できることを見い出し、本発明を完成するに至っ
た。Under these circumstances, the inventors of the present invention have conducted intensive studies on a method for producing the 8-methyl compound, and found that it is possible to produce the 8-methyl compound at low temperatures by adding the O-methyl compound to the catalyst and inert diluent and isomerizing it. It was discovered that the reaction could proceed and the S-methyl compound could be produced in high yield, and the present invention was completed.
次に本発明製造法について詳細に述べる。Next, the manufacturing method of the present invention will be described in detail.
本発明製造法は不活性希釈剤に触媒を加え、低温でＯ−
メチル体を滴下し、異性化を行なう。The production method of the present invention involves adding a catalyst to an inert diluent and producing O-
The methyl compound is added dropwise to perform isomerization.
滴下する方法を採ることにより反応制御が容易になる。Adopting the dropwise addition method facilitates reaction control.
このようにして異性化反応を行ない、Ｓ−メチル体を高
収率で得ることができる。In this manner, the isomerization reaction is carried out, and the S-methyl compound can be obtained in high yield.
さらに本発明製造法について詳細に述べる。Furthermore, the manufacturing method of the present invention will be described in detail.
本発明製造法における原料である０−メチル体は硫塩化
リンとメタノールとの反応により容易に得られる。The 0-methyl compound, which is a raw material in the production method of the present invention, can be easily obtained by reacting phosphorus sulfide with methanol.
本発明において用いられる触媒としては、テトラ−ｎ−
ブチルアンモニウムプロミド、ベンジルトリエチルアン
モニウムクロリド等の第４級アンモニウム、ベンジルト
リフェニルホスホニウムクロリド、トリフェニルメチル
ホスホニウムプロミド等の第４級ホスホニウム塩、トリ
エチルアミン、Ｎ、Ｎ−ジエチルアニリン等の第８級ア
芝ンなどが挙げられる。触媒量はＯ−メチル体に対して
０．５〜ｌＯモルチ、好ましくは１〜４モルチである。The catalyst used in the present invention is tetra-n-
Quaternary ammonium salts such as butylammonium bromide and benzyltriethylammonium chloride; quaternary phosphonium salts such as benzyltriphenylphosphonium chloride and triphenylmethylphosphonium bromide; Examples include grass. The amount of the catalyst is 0.5 to 10 molty, preferably 1 to 4 molty based on the O-methyl form.
不活性希釈剤としてはベンゼン、トルエン、キシレン等
の芳香族炭化水素、四塩化炭素、パークロルエチレン、
クロルベンゼン等のハロゲン化炭化水素、アセトン、メ
チルイソブチルケトン等のケトン、ジエチルエーテル、
ジイソプロピルエーテル等のエーテルなどが挙げられ、
その量は０−メチル体に対して重量比で０．２〜５．０
１好ましくは０．５〜２．０である。反応温度は２０〜
９，０℃、好ましくは４０〜６０℃である。０−メチル
体の滴下時間は０．５〜１時間であり、熟成時間は１〜
１０時間である。Inert diluents include aromatic hydrocarbons such as benzene, toluene, and xylene, carbon tetrachloride, perchloroethylene,
Halogenated hydrocarbons such as chlorobenzene, ketones such as acetone and methyl isobutyl ketone, diethyl ether,
Examples include ethers such as diisopropyl ether,
The amount is 0.2 to 5.0 in weight ratio to 0-methyl form.
1 is preferably 0.5 to 2.0. The reaction temperature is 20~
The temperature is 9.0°C, preferably 40-60°C. The dropping time of the 0-methyl compound is 0.5 to 1 hour, and the aging time is 1 to 1 hour.
It is 10 hours.
このようにして役られた８−メチル体は蒸留により単離
することができるが、反応液を濃縮し、そのまま製造中
間体として用いることも可能である。The 8-methyl compound thus used can be isolated by distillation, but it is also possible to concentrate the reaction solution and use it as it is as a production intermediate.
次に実施例を示す。Next, examples will be shown.
実施例１
トルエン２０．００ Ｐにテトラ−ｎ−ブチルアンモニ
ウムプロミド０．６０ ＬｉＦを加え、攪拌下に０−メ
チル体２０．００Ｆ！−を６０℃で１時間を要して滴下
した。さらに同温で８時間攪拌１７たのち、減圧下にト
ルエンを留去し、蒸留−を行なって８−メチル体１５．
６９９−を得た。Example 1 0.60 LiF of tetra-n-butylammonium bromide was added to 20.00 P of toluene, and while stirring, 0-methyl form 20.00 F! - was added dropwise at 60°C over 1 hour. After further stirring for 8 hours at the same temperature (17), toluene was distilled off under reduced pressure and distillation was performed to obtain the 8-methyl compound 15.
699- was obtained.
ｂ、ｐ、５２℃／６ｍ１坪
収率 ７８．５％
実施例２
トルエン１５．００Ｐにトリエチルアミン０．６０５’
を加え、攪拌下にＯ−メチル体８０．００！ｉＪ−を４
θ℃で０．５時間を要して滴下・した。さらに同温で５
時間攪拌したのち、実施例１と同様にしてＳ−メチル体
２８．７ｆ３Ｆを得た。b, p, 52°C/6m1 tsubo Yield 78.5% Example 2 15.00P of toluene and 0.605' of triethylamine
was added, and while stirring, O-methyl compound 80.00! iJ-4
The dropwise addition took 0.5 hours at θ°C. Furthermore, at the same temperature, 5
After stirring for a period of time, the S-methyl compound 28.7f3F was obtained in the same manner as in Example 1.
収率 ７９，１％
実施例８
四塩化炭素２０．００Ｐにトリエチルアミン０４ｏｆを
加え、攪拌下にＯ−メチル体ａｏ、ｏｏｙを５０℃で０
．５時間を要して滴下した。さらに同温で３時間攪拌し
たのち、実施例１と同様にしてＳ−メチル体１６．３ｏ
ｆ！−を得た。Yield 79.1% Example 8 Triethylamine 04of was added to 20.00P of carbon tetrachloride, and O-methyl compounds ao and ooy were dissolved at 50°C with stirring.
．． The dropwise addition took 5 hours. After further stirring for 3 hours at the same temperature, 16.3 o of S-methyl compound was prepared in the same manner as in Example 1.
f! I got -.
収率 ８１．５チ
実施例４
トルエン１５．００ｙ−にトリエチルアミン０、４０９
−をトルエン５．００Ｐに溶かした溶液およヒＯ −
） チル体２０ｏｏ７を６０℃で０、 ５時間を要して
同時滴下した。さらに同温で２時間攪拌したのち、実施
例Ｉと同様にしてＳ−メチル体１６．１１Ｐを得た。Yield 81.5y Example 4 Toluene 15.00y- to triethylamine 0.409y
A solution of − dissolved in 5.00P of toluene and H O −
) Chilled product 20oo7 was simultaneously dropped at 60°C over 0.5 hours. After further stirring at the same temperature for 2 hours, the S-methyl compound 16.11P was obtained in the same manner as in Example I.
収率 ８０．６％
実施例５
メチルイソブチルケトン１５０．００９−にトリエチル
アミン８．００５’を加え、攪拌下にＯ−メチル体１５
０．００ｙ−を５θ℃で１時間を要して滴下した。さら
に同温度で８時間攪拌したのち、実施例１と同様にして
Ｓ−メチル体１号０．８７５４を得た。Yield 80.6% Example 5 Triethylamine 8.005' was added to methyl isobutyl ketone 150.009-, and O-methyl compound 15 was added with stirring.
0.00y- was added dropwise at 5θ°C over 1 hour. After further stirring at the same temperature for 8 hours, S-methyl compound No. 1 0.8754 was obtained in the same manner as in Example 1.
収率 ８０．６％Yield 80.6%
Claims (2)
を触媒および不活性希釈剤の存在下に２０〜９０℃の温
度範囲で異性化することを特徴オ とするＳ−メチル ホスホロジクロリドチオエートの製
造法。(1) A method for producing S-methyl phosphorodichloride thioate, which comprises isomerizing O-methyl phosphorodichloride thioate in the presence of a catalyst and an inert diluent at a temperature range of 20 to 90°C. .
囲第１項に記載の製造法・。(2) The manufacturing method according to claim 1, wherein the temperature range is 40 to 60°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8231083A JPS59206393A (en) | 1983-05-10 | 1983-05-10 | Preparation of s-methylphosphorodichloridothioate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8231083A JPS59206393A (en) | 1983-05-10 | 1983-05-10 | Preparation of s-methylphosphorodichloridothioate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59206393A true JPS59206393A (en) | 1984-11-22 |
Family
ID=13770982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8231083A Pending JPS59206393A (en) | 1983-05-10 | 1983-05-10 | Preparation of s-methylphosphorodichloridothioate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59206393A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0219770A1 (en) * | 1985-10-17 | 1987-04-29 | Ishihara Sangyo Kaisha, Ltd. | Process for preparing a S-substituted phosphorochloridothiolate |
-
1983
- 1983-05-10 JP JP8231083A patent/JPS59206393A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0219770A1 (en) * | 1985-10-17 | 1987-04-29 | Ishihara Sangyo Kaisha, Ltd. | Process for preparing a S-substituted phosphorochloridothiolate |
| US4736050A (en) * | 1985-10-17 | 1988-04-05 | Ishihara Sangyo Kaisha Ltd. | Process for preparing a S-substituted phosphoro-chloridothiolate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Phillion et al. | Synthesis and reactivity of diethyl phosphonomethyltriflate | |
| JPH0257077B2 (en) | ||
| JPS59206393A (en) | Preparation of s-methylphosphorodichloridothioate | |
| KR840000891B1 (en) | Unsymmetrical thiophosphonate insecticides and mematocides | |
| US4470933A (en) | Preparation of S-brom-dithiophosphoric, dithiophosphonic and dithiophosphinic acid derivatives | |
| SU847894A3 (en) | Insectoacaricidonematocidic agent | |
| US4582825A (en) | 2-(substituted phenyl)-3-chloro-2-butene thio phosphates as insecticides | |
| EP0107163B1 (en) | Dihalovinylphenyl-phosphoric-acid esters, process for their preparation and their use as pesticides | |
| US4562279A (en) | Herbicidal N-substituted-5-(substituted-phenoxy)-2-substituted benzoic acid sulphonamides | |
| CA1213604A (en) | Organophosphate derivatives, intermediates for production thereof, processes for producing said derivatives and intermediates, and insecticidal, miticidal or nematocidal agent | |
| Blair et al. | Insecticide Screening, Synthesis and Insecticide Activity of Methyl 2, 4, 5-Trichlorophenyl Phosphoramidates | |
| JPS597195A (en) | Thiol phosphoric acid ester, manufacture and use | |
| US4132542A (en) | Organic(thio) phosphoric acid ester compounds and herbicidal compositions | |
| US3159665A (en) | Omicron-alkylmercaptoalkyl and omicron-arylmercaptoalkyl omicron-alkyl phosphoramidothioates | |
| SU1558919A1 (en) | Method of obtaining dichloranhydrides of alkenylphosphoric acids | |
| US3794700A (en) | Process for the preparation of methylthionophosphonates | |
| CA1298848C (en) | Process and intermediates for preparing phosphinous acid derivatives | |
| JPS6366840B2 (en) | ||
| SU466242A1 (en) | Method for preparing dithiol phosphoric acid esters | |
| US4059697A (en) | N-(Substituted)aminocarbonyl O,S-dialkyl phosphoramido(di)thioates and method of controlling arthropods | |
| US3666839A (en) | Oximinophosphonodithioates | |
| US4000269A (en) | S-(α-substituted-arylmethylthio, -arylmethylsulfinyl, and -arylmethylsulfonyl)methyl phosphorus esters used as insecticides | |
| SU1067004A1 (en) | Process for preparing 1-chloro-2-alkoxyvinylphosphonic anhydrides | |
| US4320126A (en) | Triazinyl-organophosphorus esters | |
| US5298500A (en) | Pesticidal O,S-dialkyl-O-[4-(1-alkoxy-2,2,2-trifluoroethyl)phenyl]phosphoro(di) thioate derivatives |