JPS5844661B2 - Isocyanthane 3-Isoxazolyl ester - Google Patents
Isocyanthane 3-Isoxazolyl esterInfo
- Publication number
- JPS5844661B2 JPS5844661B2 JP751569A JP156975A JPS5844661B2 JP S5844661 B2 JPS5844661 B2 JP S5844661B2 JP 751569 A JP751569 A JP 751569A JP 156975 A JP156975 A JP 156975A JP S5844661 B2 JPS5844661 B2 JP S5844661B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- phosgene
- isoxazolyl
- isocyanthane
- hydrogen chloride
- 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
Links
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
【発明の詳細な説明】
本発明は一般式
〔式中、Ｒは水素、アルキル基またはフェニル基を表わ
す。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula [wherein R represents hydrogen, an alkyl group or a phenyl group].
〕で示されるイソシアン酸３−イソオキサシリルエステ
ルの製造法に関する。] The present invention relates to a method for producing isocyanic acid 3-isoxasilyle ester.
上記目的物質（Ｉ）は塩化水素の存在下一般式〔式中、
Ｒは前記と同意義を有する。In the presence of hydrogen chloride, the above target substance (I) is synthesized by the general formula [wherein,
R has the same meaning as above.
〕で示される３−インオキサプリルアミンにホスゲンを
反応させることにより得られる。] It can be obtained by reacting 3-ynoxaprylamine represented by phosgene with phosgene.
上記定義について説明を補足すれは、アルキル基として
は、メチル、エチル、プロピル、イソプロピル、ブチル
、イソブナル、ｔ−ブチル、シクロプロピル、シクロブ
チル、シクロヘキシルなどが例示される。To supplement the above definition, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobunal, t-butyl, cyclopropyl, cyclobutyl, cyclohexyl, and the like.
従来この種の反応はへテロ環とくにインオキサゾール類
については全く知られていない。Conventionally, this type of reaction has not been known at all for heterocycles, especially inoxazoles.
本発明者はホスケン法によるイソシアン酸３−インオキ
サシリルエステル（Ｉ）の合成を試みたが、収率が極め
て低いことを確認した（参考側参照）。The present inventor attempted to synthesize isocyanate 3-ynoxasilyle ester (I) by the Hoscene method, but confirmed that the yield was extremely low (see reference side).
そこでこの反応を塩化水素の存在下に実施すると高収率
で反応が進行することを見出し、本発明方法を完或した
。Therefore, it was discovered that the reaction proceeds in high yield when this reaction is carried out in the presence of hydrogen chloride, and the method of the present invention has been completed.
本発明方法は塩化水素の存在下ホスゲンを使用し、不活
性溶媒（例えば、ベンセン、トルエン、キシレン、ジメ
チルホルムアミド、塩化メチレン、ジクロルエタン）中
室部下または加熱丁に実施すればよい。The method of the invention may be carried out using phosgene in the presence of hydrogen chloride in an inert solvent (eg, benzene, toluene, xylene, dimethylformamide, methylene chloride, dichloroethane) or in a heated oven.
原料物質である３−インオキサシリルアミン（ＩＩ）は
対応する３−インオキサゾールカルボン酸エステル（油
から導かれる：
〔式中、Ｒは前記と同意義を有する。The raw material 3-ynoxasilylamine (II) is derived from the corresponding 3-ynoxazole carboxylic acid ester (oil): [wherein R has the same meaning as above].
〕Ｃｅｏｇ−日本特許第２５６，２３４号〕。[Ceog-Japanese Patent No. 256,234].
かくして得られるイソシアン酸エステル（Ｉ）は新規物
質であり、除草作用、殺藻作用、殺虫作用を示す３−イ
ソオキサシリル尿素誘導体の合成中間体として有用であ
る。The thus obtained isocyanate ester (I) is a new substance and is useful as a synthetic intermediate for 3-isoxacylylurea derivatives that exhibit herbicidal, algicidal and insecticidal effects.
例えば、インシアン酸５−ｔ−ブチル−３−イソオキサ
シリルエステルにジノチルアミンを反応させると優れた
除草活性を示す１，１−ジメチル−３−（５−１−ブチ
ル−３−イソオキサゾリル）尿素（一般名イソウロン）
が得られる〔日本特許第１，０１２，４８８号〕。For example, 1,1-dimethyl-3-(5-1-butyl-3-isoxazolyl)urea (general name isouron)
is obtained [Japanese Patent No. 1,012,488].
以下に本発明方法の実施例を示す。Examples of the method of the present invention are shown below.
実施例 １
３−アミノ−５−メチルイソオキサゾール４．９１ｇを
トルエン２２０ｍ１に溶解し、室温下に塩化水素ガスを
３０分間導入し、１時間２０分そのままかきまぜる。Example 1 4.91 g of 3-amino-5-methylisoxazole was dissolved in 220 ml of toluene, hydrogen chloride gas was introduced at room temperature for 30 minutes, and the mixture was stirred for 1 hour and 20 minutes.
減圧下に過剰の塩化水素ガスを除き、トルエン１８０Ｔ
Ｌｌを追加し、５０〜７０℃にてホスゲンガスを３，５
時間吹込む。Remove excess hydrogen chloride gas under reduced pressure and add toluene 180T
Add Ll and add 3.5 liters of phosgene gas at 50-70°C.
Inject time.
室温下に一夜放置し、浴温４０〜４５°Ｃにて溶媒を減
圧留去し、黄色結晶としてイソシアン酸５−メチル−３
−イソオキサシリルエステル６．７４９を得る。After standing at room temperature overnight, the solvent was distilled off under reduced pressure at a bath temperature of 40 to 45°C, and 5-methyl-3 isocyanate was obtained as yellow crystals.
-isoxasilyle ester 6.749 is obtained.
本品を減圧昇華により精製し、融点１９０〜１９１℃（
分解）の無色結晶６．１４ｇを得る。This product was purified by vacuum sublimation, with a melting point of 190-191℃ (
6.14 g of colorless crystals of decomposition) are obtained.
収率９８．９％。実施例 ２〜６
下記の原料物質（ＩＩ）を使用し、実施例１と同様に反
応を行い、はぼ同様の収率で対応する目的物質（Ｉ）を
得る：
注）表中の略号は下記の意義を有する二
Ｅｔ（エチル基）、１−Ｐｒ（イソプロピル基）、ｔ
−Ｂ ｕ （第三ブチル基）、ｃ−Ｐｒ（シクロプロピ
ル基）、Ｐｈ（フェニル基）、ｍｐ（融点）。Yield 98.9%. Examples 2 to 6 Using the following starting material (II), the reaction is carried out in the same manner as in Example 1, and the corresponding target substance (I) is obtained with a similar yield: Note) Abbreviations in the table are 2Et (ethyl group), 1-Pr (isopropyl group), t with the following meanings
-Bu (tertiary butyl group), c-Pr (cyclopropyl group), Ph (phenyl group), mp (melting point).
実施例 ６
３−アミノ−５−ｔ−プチルイソオギサゾール２１．０
３ｇ（０，１５モル）を乾燥トルエン６００ｍ１に溶解
し、室温下塩化水素ガスを２０分間導入し、１時間３０
分そのままかきまぜる。Example 6 3-Amino-5-t-butyl isoogisazole 21.0
3 g (0.15 mol) was dissolved in 600 ml of dry toluene, hydrogen chloride gas was introduced at room temperature for 20 minutes, and the mixture was heated for 1 hour 30 minutes.
Stir for a minute.
減圧下に過剰の塩化水素ガスを留去する。Excess hydrogen chloride gas is distilled off under reduced pressure.
かきまぜつつ反応液にホスゲン２２．２６．？（０，２
２５モル）を導入し、５０〜６０℃にて３時間かきませ
る。Add phosgene to the reaction solution while stirring 22.26. ? (0,2
25 mol) and stirred at 50-60°C for 3 hours.
さらにホスゲン７、４２ 、！ｉ’ （０，０７５モル
）を導入し、５０〜７０℃で１時間かきませ、室温１に
一夜放置する。Furthermore, phosgene 7,42,! i' (0,075 mol) is introduced, stirred at 50-70°C for 1 hour, and left at room temperature 1 overnight.
反応液を浴温４０〜４５℃にて減圧濃縮し、イソシアン
酸５−１−ブチル−３−イソオキサシリルエステル２３
．９６ｇを得る。The reaction solution was concentrated under reduced pressure at a bath temperature of 40 to 45°C to obtain 5-1-butyl-3-isoxasilyle isocyanate 23.
．． Obtain 96g.
本品をベンゼンより再結晶すると、融点１６１．０〜１
６２．０℃のプリズム晶となる。When this product is recrystallized from benzene, the melting point is 161.0-1.
It becomes a prismatic crystal with a temperature of 62.0°C.
収率９６．１３％。参考例
３−アミノ−５−１−ブチルイソオキサゾール２１．０
３ｇ（０，１５モル）を乾燥トルエン６００１ｎｌに溶
解し、室温丁にかきまぜつつホスゲン２２．２６ｇ（０
，２２５モル）を導入し、５０〜６０℃にて３時間かき
まぜる。Yield 96.13%. Reference example 3-Amino-5-1-butyl isoxazole 21.0
3 g (0.15 mol) of phosgene was dissolved in 6001 nl of dry toluene and 22.26 g (0.1 mol) of phosgene was dissolved with stirring at room temperature.
, 225 mol) and stirred at 50 to 60°C for 3 hours.
さらにホスゲン７．４２ｇ（０，０７５モル）を導入し
、５０〜７０℃で１時間かきまぜ、室温丁に一夜放置す
る。Further, 7.42 g (0,075 mol) of phosgene was introduced, stirred at 50 to 70°C for 1 hour, and left overnight at room temperature.
反応液を浴温４０〜４５℃にて減圧濃縮し、イソシアン
酸５− ｔ−ブチル−３−イソオキサシリルエステル１
５．４９ｇを得る。The reaction solution was concentrated under reduced pressure at a bath temperature of 40 to 45°C to obtain 5-t-butyl-3-isoxacylyl isocyanate 1.
Obtain 5.49g.
本旨をベンゼンより再結晶すると、融点１６１．０〜１
６２．０℃のプリズム晶となる。When the substance is recrystallized from benzene, the melting point is 161.0-1
It becomes a prismatic crystal with a temperature of 62.0°C.
Claims (1)
応させることを％徴とする一般式 １式中、Ｒは前記と同意義を有する。 〕で示されるイソシアン酸３−インオキサシリルエステ
ルの製造法。[Claims] 1 Presence of hydrogen chloride T General formula [In the formula, R represents hydrogen or a group. ] In the general formula 1, which represents the reaction of 3-ynoxacylylamine represented by an alkyl group or phenyl with phosgene, R has the same meaning as defined above. ] A method for producing isocyanic acid 3-ynoxasilyle ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP751569A JPS5844661B2 (en) | 1974-12-24 | 1974-12-24 | Isocyanthane 3-Isoxazolyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP751569A JPS5844661B2 (en) | 1974-12-24 | 1974-12-24 | Isocyanthane 3-Isoxazolyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5175064A JPS5175064A (en) | 1976-06-29 |
| JPS5844661B2 true JPS5844661B2 (en) | 1983-10-04 |
Family
ID=11505143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP751569A Expired JPS5844661B2 (en) | 1974-12-24 | 1974-12-24 | Isocyanthane 3-Isoxazolyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5844661B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394510A (en) * | 1981-02-02 | 1983-07-19 | Eli Lilly And Company | Process for preparing an isoxazolylurea |
-
1974
- 1974-12-24 JP JP751569A patent/JPS5844661B2/en not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| ORGANIC PUNCTIONAL GROUP PREPARATIONS 2=1971US * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5175064A (en) | 1976-06-29 |
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