JPH0667910B2 - Method for producing 2-imidazolidinones - Google Patents
Method for producing 2-imidazolidinonesInfo
- Publication number
- JPH0667910B2 JPH0667910B2 JP10777186A JP10777186A JPH0667910B2 JP H0667910 B2 JPH0667910 B2 JP H0667910B2 JP 10777186 A JP10777186 A JP 10777186A JP 10777186 A JP10777186 A JP 10777186A JP H0667910 B2 JPH0667910 B2 JP H0667910B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- phosgene
- reaction
- alkyl group
- imidazolidinones
- 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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、式(I) (式中、Rは低級アルキル基である。R1,R2,R3
及びR4は水素原子または低級アルキル基であり、その
うち少なくとも1個は低級アルキル基である。)で示さ
れるジアミン類とホスゲンを用いて式(II) (式中、R,R1,R2,R3,及びR4は、式(I)の
R,R1,R2,R3及びR4と同じ。)で示される2
−イミダゾリジノン類を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides compounds of formula (I) (In the formula, R is a lower alkyl group. R 1 , R 2 , R 3
And R 4 is a hydrogen atom or a lower alkyl group, at least one of which is a lower alkyl group. ) Using diamines and phosgene represented by the formula (II) 2 (wherein, R, R 1, R 2, R 3, and R 4 are the same. And R of formula (I), R 1, R 2, R 3 and R 4) represented by
-A method for producing imidazolidinones.
上記式(II)で示される2−イミダゾリジノン類は医薬・
農薬の中間体や非プロトン性極性溶媒として有用な物質
である。The 2-imidazolidinones represented by the above formula (II) are pharmaceuticals.
It is a useful substance as an intermediate for agrochemicals and as an aprotic polar solvent.
上記式(II)で示される2−イミダゾリジノン類の製造法
はいくつか提案されている。例えば、1,3,4−トリ
メチル−2−イミダゾリジノンについては、N,N′−
ジメチル−1,2−プロパンジアミンとウレアを反応さ
せる方法、1,3,4−トリメチル−4−イミダゾリン
−2オンを水素添加する方法、N,N′−ジメチル−
1,2−プロパンジアミンとジエチルカルバミルクロラ
イドを反応させる方法が提案されている。Several methods for producing 2-imidazolidinones represented by the above formula (II) have been proposed. For example, for 1,3,4-trimethyl-2-imidazolidinone, N, N'-
Method of reacting dimethyl-1,2-propanediamine and urea, method of hydrogenating 1,3,4-trimethyl-4-imidazolin-2-one, N, N'-dimethyl-
A method of reacting 1,2-propanediamine with diethylcarbamyl chloride has been proposed.
また、上記式(I)で示されるジアミン類とホスゲンとを
反応させて上記式(II)で示される2−イミダゾリジノン
類を得る方法は知られていないが、N,N′−ジメチル
−1,2−エタンジアミンとホスゲンをトルエン溶媒中
で反応させて、式(II)の類似化合物である1,3−ジメ
チル−2−イミダゾリジノンを13%の収率で得る方法
〔ジヤーナル オブ ザ ケミカル ソサイヤテイ
(J.Chem.Soc.),1947,315頁〕は知られている。し
かしながら本発明者らは同様にしてN,N′−ジメチル
−1,2−プロパンジアミンとホスゲンをトルエン溶媒
中で反応させたが、1,3,4−トリメチル−2−イミ
ダゾリジノンの生成収率は20%にも満たなかった。Further, a method of reacting a diamine represented by the above formula (I) with phosgene to obtain a 2-imidazolidinone represented by the above formula (II) is not known, but N, N'-dimethyl- A method of reacting 1,2-ethanediamine and phosgene in a toluene solvent to obtain 1,3-dimethyl-2-imidazolidinone, which is a similar compound of formula (II), in a yield of 13%. Chemical Society (J. Chem. Soc.), 1947, p. 315] is known. However, the present inventors have similarly reacted N, N′-dimethyl-1,2-propanediamine with phosgene in a toluene solvent, but the production yield of 1,3,4-trimethyl-2-imidazolidinone was The rate was less than 20%.
前述のように前記式(I)で示されるジアミン類とホスゲ
ンを反応させて前記式(II)で示される2−オキサゾリジ
ノン類を工業的に満足のいく収率で得る方法は知られて
いなかった。As described above, a method of reacting the diamines represented by the formula (I) with phosgene to obtain the 2-oxazolidinones represented by the formula (II) in an industrially satisfactory yield has not been known. .
本発明は、前記式(I)で示されるジアミン類とホスゲン
を反応させ、収率よくしかも安価に前記式(II)で示され
る2−イミダゾリジノン類が得られる工業的製法を提供
するものである。The present invention provides an industrial process for reacting a diamine represented by the formula (I) with phosgene to obtain a 2-imidazolidinone represented by the formula (II) in good yield and at low cost. Is.
本発明者らは、前記式(I)で示されるジアミン類とホス
ゲンを用いた前記式(II)で示される2−イミダゾリジノ
ン類の工業的製造方法を鋭意検討し以下の知見を得た。The present inventors earnestly studied the industrial production method of the 2-imidazolidinones represented by the formula (II) using the diamines represented by the formula (I) and phosgene, and obtained the following findings. .
通常、ホスゲンを使用する反応は極力水の存在しない条
件下に実施され、さらにホスゲンはアルカリ性水溶液中
にて容易に加水分解されることが知られており、そのた
め大過剰量のホスゲンが必要となるであろうことが予想
された。しかし意外にも、ジアミン類とホスゲンとの反
応においてはホスゲンはその化学量論量の1.0〜1.5倍で
充分であることが判明し、かつ、水及び脱塩酸剤を存在
させておくことにより、2−イミダゾリジノン類の収率
は、従来法より飛躍的に向上することがわかった。さら
に、その際水存在下に脱塩酸剤によって反応時にPHを一
定範囲、すなわち、3.0〜10.0に維持すればさらに飛躍
的に収率が向上することがわかり、本発明に達したもの
である。Usually, the reaction using phosgene is carried out in the absence of water as much as possible, and it is known that phosgene is easily hydrolyzed in an alkaline aqueous solution, which requires a large excess of phosgene. It was expected. However, surprisingly, it was found that 1.0 to 1.5 times the stoichiometric amount of phosgene is sufficient in the reaction between diamines and phosgene, and by the presence of water and a dehydrochlorinating agent, It was found that the yield of 2-imidazolidinones was dramatically improved as compared with the conventional method. Further, it was found that the yield can be further improved dramatically by maintaining the pH in a certain range during the reaction in the presence of water by the dehydrochlorinating agent, that is, 3.0 to 10.0, and the present invention has been achieved.
本発明方法では、水が実質的に存在している状態、すな
わち、水媒体中で反応が実施されるので、ホスゲン化反
応により副生する塩酸により逐次生成するジアミン類の
塩酸塩は、反応時に系外に析出することなく、水に溶解
されるので、均一状態で反応は実施できる。その為、反
応時のPHの管理も極めて容易に実施することができる。In the method of the present invention, since water is substantially present, that is, the reaction is carried out in an aqueous medium, the diamine hydrochloride successively produced by hydrochloric acid by-produced by the phosgenation reaction is Since it is dissolved in water without being precipitated outside the system, the reaction can be carried out in a homogeneous state. Therefore, management of PH during the reaction can be carried out very easily.
また、反応時に脱塩酸剤を併用するので、脱塩酸剤が副
生塩酸のキヤツチに効率よく作用するだけでなく、特に
PHを3.0〜10.0の範囲に維持しながら反応を行なうと、
従来の技術では予想もできない程の高収率で目的生成物
が得られる。その理由はジアミン類のホスゲン化によっ
て最初に生成するジアミン類のモノカルバミルクロライ
ドが、分子内還化する時、PHを管理しておくことによ
り、分子間反応による副生物及びジアミン類のジカルバ
ミルクロライド等の副生物を抑制することができる為と
考えられる。In addition, since a dehydrochlorinating agent is also used during the reaction, the dehydrochlorinating agent not only acts efficiently on the by-product hydrochloric acid cache, but also
When the reaction is carried out while maintaining the pH in the range of 3.0 to 10.0,
The target product is obtained in a high yield that cannot be predicted by the conventional techniques. The reason is that when the monocarbamyl chloride of diamine, which is first formed by phosgenation of diamine, undergoes intramolecular reduction, PH is controlled so that by-products due to intermolecular reaction and dicarbamide of diamine are generated. This is probably because byproducts such as milk loride can be suppressed.
本発明において、前記式(I)で示される原料のジアミン
類は、N,N′−ジメチル−1,2−プロパンジアミ
ン、N,N′,2−トリメチル−2,3−ブタンジアミ
ン、N,N′−ジエチル−1,2−プロパンジアミンな
どであり、これらのジアミン類は、相応するアルキルハ
ライドと相応するアルキルアミンによって容易に得るこ
とができる。In the present invention, the raw material diamines represented by the formula (I) are N, N′-dimethyl-1,2-propanediamine, N, N ′, 2-trimethyl-2,3-butanediamine, N, N'-diethyl-1,2-propanediamine and the like can be easily obtained by using the corresponding alkyl halide and the corresponding alkylamine.
本発明においては、これらのジアミン類を原料として、
相応する前記式(II)で示される1,3,4−トリメチル
−2−イミダゾリジノン、1,3,4,4,5−ペンタ
メチル−2−イミダゾリジノン、1,3−ジエチル−4
−メチル−2−イミダゾリジノンなどの2−イミダゾリ
ジノン類が得られる。In the present invention, using these diamines as raw materials,
1,3,4-Trimethyl-2-imidazolidinone, 1,3,4,5,5-pentamethyl-2-imidazolidinone represented by the corresponding formula (II), 1,3-diethyl-4
2-Imidazolidinones are obtained, such as methyl-2-imidazolidinone.
本発明においては、ジアミン類は直接ホスゲン化させる
か、塩酸塩にしてホスゲンとの反応に供せられる。In the present invention, diamines are directly phosgenated or converted into a hydrochloride to be used in the reaction with phosgene.
しかしながら、反応をpH3.0〜10.0に維持しながら実施
する方法では、反応当初より塩酸塩として仕込むのが有
利である。However, in the method in which the reaction is carried out while maintaining the pH at 3.0 to 10.0, it is advantageous to charge it as the hydrochloride from the beginning of the reaction.
ジアミン類の塩酸塩として使用する場合は、塩酸を当量
用いてジアミン類二塩酸塩として仕込めば、反応当初の
PHは約3程度となり、得られた二塩酸塩をホスゲン化反
応させても反応速度は極めて遅い。When using it as the diamine hydrochloride, if hydrochloric acid is used as the diamine dihydrochloride in an equivalent amount, the
The pH is about 3, and the reaction rate is extremely slow even when the obtained dihydrochloride is subjected to a phosgenation reaction.
従って、塩酸塩として使用する場合は塩酸を当量以下反
応させた一塩酸塩付近で反応させるのが好ましく、二塩
酸塩を最初から仕込む場合は脱塩酸剤で予め脱塩酸して
PHを3以上とした後、ホスゲン化反応を行うのがよい。Therefore, when used as the hydrochloride, it is preferable to react in the vicinity of the monohydrochloride obtained by reacting hydrochloric acid with an equivalent amount or less, and when the dihydrochloride is charged from the beginning, dehydrochlorination is performed beforehand with a dehydrochlorinating agent.
It is advisable to carry out the phosgenation reaction after adjusting the pH to 3 or more.
また、ジアミン類をそのまま仕込んで反応させる場合
は、反応当初のPHは11以上となり、ホスゲン化反応前
に予め塩酸を加えておき、PHを10以下にして行なうの
がよい。When the diamines are charged as they are and reacted, the PH at the beginning of the reaction is 11 or more, and hydrochloric acid is preferably added in advance before the phosgenation reaction so that the PH is 10 or less.
本発明に用いられる水は、実質的に存在している必要が
あり、予め反応器中に入れておいてもよいし、脱塩酸剤
と一緒に、たとえばアルカリ金属化合物の水溶液として
滴下装入してもよい。使用する水の量は特に限定されな
いが、均一反応が維持できる程度の充分な量が好まし
く、ジアミン類に対して、0.5〜50重量倍、好ましく
は5〜30重量倍がよい。The water used in the present invention needs to be substantially present, and may be placed in the reactor in advance, or may be added dropwise together with the dehydrochlorinating agent, for example, as an aqueous solution of an alkali metal compound. May be. The amount of water used is not particularly limited, but is preferably an amount sufficient to maintain a uniform reaction, and is preferably 0.5 to 50 times by weight, preferably 5 to 30 times by weight, based on the diamine.
また本発明で用いられる脱塩酸剤は、水酸化ナトリウ
ム,水酸化カリウム,炭酸ナトリウム,炭酸カリウムの
ようなアルカリ金属化合物、またはトリメチルアミン,
トリエチルアミンのような脂肪族第三級アミン、ジメチ
ルアニリン,ジエチルアニリンのような芳香族第三級ア
ミン、ピリジン,メチルピリジン,ピラジンのような複
素環式第三級アミンなどのような第三級アミンが好適で
ある。もし、脱塩酸剤を使用しなければ、原料自体が副
生塩酸のキヤツチ剤となり、それ以上反応を進めること
は困難となる。The dehydrochlorinating agent used in the present invention is an alkali metal compound such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, or trimethylamine,
Aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline and diethylaniline, and tertiary amines such as heterocyclic tertiary amines such as pyridine, methylpyridine and pyrazine. Is preferred. If the dehydrochlorinating agent is not used, the raw material itself becomes a by-product hydrochloric acid cleaning agent, and it becomes difficult to proceed the reaction any further.
本発明における反応温度は特に限定されないが好ましく
は0〜70℃で行なう。The reaction temperature in the present invention is not particularly limited, but is preferably 0 to 70 ° C.
本発明で用いられる脱塩酸剤量は、反応時のPH領域によ
り異るが、たとえば中性付近の領域で反応させる場合
は、副生する塩酸及び仕込み時に消費される塩酸量に合
わせて適宜決められ、またホスゲン量は、ジアミン類に
対して化学量論量の1.0〜1.5倍、即ち、ジアミン類に対
して1.0〜1.5倍モルで充分である。The amount of the dehydrochlorinating agent used in the present invention varies depending on the PH region during the reaction, but, for example, when the reaction is performed in the neutral region, it is appropriately determined according to the amount of hydrochloric acid produced as a by-product and the amount of hydrochloric acid consumed during charging. It is sufficient that the amount of phosgene is 1.0 to 1.5 times the stoichiometric amount with respect to the diamine, that is, 1.0 to 1.5 times with respect to the diamine.
本発明方法の通常の好ましい態様は次のようになる。A typical preferred embodiment of the method of the invention is as follows.
ホスゲン吹き込み管,滴下ロート,PH測定用電極,温度
計,還流冷却器及び攪拌機を備えた反応器中に、水及び
ジアミン類を加える。そのまま反応を開始してもよい
が、好ましくは塩酸を加えて仕込み液のPHを3〜10程
度にする。この液を適当な温度下に攪拌しながらホスゲ
ンをホスゲン吹き込み管より導入すると同時に脱塩酸剤
を滴下ロートより滴下する。これにより反応液のPHを3.
0〜10.0、好ましくは5.0〜8.0に維持する。吹き込み及
び滴下終了後、窒素により未反応ホスゲンをパージし、
抽出及び/もしくは蒸留等の常法により目的生成物を取
り出す。Water and diamines are added to a reactor equipped with a phosgene blowing tube, a dropping funnel, a PH measuring electrode, a thermometer, a reflux condenser and a stirrer. The reaction may be started as it is, but preferably, hydrochloric acid is added to adjust the pH of the charged solution to about 3 to 10. While stirring this solution at an appropriate temperature, phosgene is introduced from a phosgene blowing tube, and at the same time, a dehydrochlorinating agent is dropped from a dropping funnel. As a result, the pH of the reaction solution is 3.
It is maintained at 0 to 10.0, preferably 5.0 to 8.0. After blowing and dropping, purge unreacted phosgene with nitrogen,
The target product is taken out by a conventional method such as extraction and / or distillation.
本発明は、ジアミン類とホスゲンを反応するに当り、ホ
スゲン使用量はジアミン類に対して1.0〜1.5倍モルでよ
く、使用溶媒は水であり、また生成収率は高収率である
ので安価に2−イミダゾリジノン類を得ることができ
る。In the present invention, in reacting diamines and phosgene, the amount of phosgene used may be 1.0 to 1.5 times the molar amount of diamines, the solvent used is water, and the production yield is high, so it is inexpensive. It is possible to obtain 2-imidazolidinones.
以下に実施例及び比較例を示す。 Examples and comparative examples are shown below.
実施例1 ホスゲン吹き込み管,滴下ロート,温度計,還流冷却器
及び攪拌機を備えた300mガラス製フラスコに水1
00m、N,N′−ジメチル−1,2−プロパンジア
ミン20.4g(0.20モル)を入れ、一方滴下ロート中に2
0%水酸化ナトリウム水溶液84.0g(0.40モル)を用意
した。フラスコ内温を20℃に維持し、攪拌しながらホ
スゲンをホスゲン吹き込み管を通じて10g/hrで2時
間吹き込んだ。同時に20%水酸化ナトリウム水溶液を
滴下ロートより2時間かけて滴下した。吹き込み及び滴
下終了後、20℃で1時間熟成した。この反応マスをサ
ンプリングしてガスクロマトグラフイにより、1,3,
4−トリメチル−2−イミダゾリジノンの定量を行なっ
た。生成収率は78.9%であった。Example 1 A 300 m glass flask equipped with a phosgene blow-in tube, a dropping funnel, a thermometer, a reflux condenser and a stirrer was charged with water 1
00m, 20.4 g (0.20 mol) of N, N'-dimethyl-1,2-propanediamine was added, while 2 in the dropping funnel.
84.0 g (0.40 mol) of 0% sodium hydroxide aqueous solution was prepared. The internal temperature of the flask was maintained at 20 ° C., and phosgene was blown through the phosgene blowing tube at 10 g / hr for 2 hours while stirring. At the same time, a 20% aqueous sodium hydroxide solution was added dropwise from the dropping funnel over 2 hours. After completion of blowing and dropping, the mixture was aged at 20 ° C. for 1 hour. This reaction mass was sampled and analyzed by gas chromatography, 1, 3,
Quantitation of 4-trimethyl-2-imidazolidinone was performed. The production yield was 78.9%.
実施例2 N,N′−ジメチル−1,2−プロパンジアミンの代り
に、N,N′,2−トリメチル−2,3−ブタンジアミ
ン26.1g(0.20モル)を使用した以外実施例1と同様に
反応させ、分析を行なった。その結果、1,3,4,
4,5−ペンタメチル−2−イミダゾリジノンの生成収
率は、76.7%であった。Example 2 Same as Example 1 except that 26.1 g (0.20 mol) of N, N ′, 2-trimethyl-2,3-butanediamine was used instead of N, N′-dimethyl-1,2-propanediamine. And analyzed. As a result, 1, 3, 4,
The production yield of 4,5-pentamethyl-2-imidazolidinone was 76.7%.
実施例3 N,N′−ジメチル−1,2−プロパンジアミンの代り
に、N,N′−ジメチル−1,2−プロパンジアミン2
6.1g(0.20モル)を使用した以外実施例1と同様に反
応させ、分析を行なった。その結果、1,3−ジエチル
−4−メチル−2−イミダゾリジノンの生成収率は77.3
%であった。Example 3 Instead of N, N'-dimethyl-1,2-propanediamine, N, N'-dimethyl-1,2-propanediamine 2
The reaction and analysis were carried out in the same manner as in Example 1 except that 6.1 g (0.20 mol) was used. As a result, the yield of 1,3-diethyl-4-methyl-2-imidazolidinone was 77.3.
%Met.
実施例4 20%水酸化ナトリウム水溶液の代りにトリエチルアミ
ン40.5g(0.40モル)を使用した以外実施例1と同様に
反応させ、分析を行なった。1,3,4−トリメチル−
2−イミダゾリジノンの生成収率は71.4%であった。Example 4 The reaction and analysis were performed in the same manner as in Example 1 except that 40.5 g (0.40 mol) of triethylamine was used instead of the 20% aqueous sodium hydroxide solution. 1,3,4-trimethyl-
The production yield of 2-imidazolidinone was 71.4%.
実施例5 ホスゲン吹き込み管,滴下ロート,PH測定用電極,温度
計,還流冷却器及び攪拌機を備えた500mガラス製
フラスコに水100m、N,N′−ジメチル−1,2
−プロパンジアミン20.4g(0.20モル)及び36%塩酸
30.4g(0.30モル)を装入した。Example 5 A 500 m glass flask equipped with a phosgene blowing tube, a dropping funnel, an electrode for PH measurement, a thermometer, a reflux condenser and a stirrer was used, and 100 m of water and N, N'-dimethyl-1,2 were used.
-Propanediamine 20.4 g (0.20 mol) and 36% hydrochloric acid
30.4 g (0.30 mol) were charged.
一方、滴下ロート中に20%水酸化ナトリウム水溶液16
8.0g(0.80モル)を用意した。冷却しながら反応温度
を20℃に維持し、攪拌下にホスゲンを10g/hrで2
時間吹き込んだ。同時に、水酸化ナトリウム水溶液を2
時間かけて反応後のPHを7.0±0.3に管理しながら滴下し
た。On the other hand, 16% 20% aqueous sodium hydroxide solution was added to the dropping funnel.
8.0 g (0.80 mol) was prepared. The reaction temperature was maintained at 20 ° C. while cooling, and phosgene was added at 10 g / hr under stirring to 2
I breathed time. At the same time, add 2 parts of sodium hydroxide solution.
The pH after the reaction was dropped over a period of time while controlling it to 7.0 ± 0.3.
吹き込み及び滴下終了後、窒素20/分で20分間系
内をパージした。After completion of blowing and dropping, the system was purged with nitrogen at 20 / min for 20 minutes.
この反応マスをサンプリングして、ガスクロマトグラフ
イーにより,1,3,4−トリメチル−2−イミダゾリ
ジノンの定量を行なった。生成収率は91.3%であった。
反応終了後に49%水酸化ナトリウム水溶液を加えて、
アルカリ性にした後、1,2−ジクロロエタン150g
/回で2回抽出し、油層を分離後蒸留して、1,3,4
−トリメチル−2−イミダゾリジノン(沸点133〜1
35℃/20torrの留分)21.8gを得た。The reaction mass was sampled, and 1,3,4-trimethyl-2-imidazolidinone was quantified by gas chromatography. The production yield was 91.3%.
After completion of the reaction, add 49% sodium hydroxide aqueous solution,
After making alkaline, 150 g of 1,2-dichloroethane
/ 2 times, and the oil layer is separated and distilled to give 1,3,4
-Trimethyl-2-imidazolidinone (boiling point 133-1
21.8 g of a 35 ° C./20 torr fraction) was obtained.
比較例1 ホスゲン吹き込み管,温度計,還流冷却器及び攪拌機を
備えた300mガラス製フラスコにトルエン100m
、N,N′−ジメチル−1,2−プロパンジアミン2
0.4g(0.20モル)を装入した。フラスコ内温を20℃
に維持し、攪拌しながらホスゲンをホスゲン吹き込み管
を通じて10g/hrで2時間吹き込み、同温度で1時間
熟成した。この反応マスをサンプリングしてガスクロマ
トグラフイーにより、1,3,4−トリメチル−2−イ
ミダゾリジノンの定量を行なった。生成収率は18.3%で
あった。Comparative Example 1 To a 300 m glass flask equipped with a phosgene blowing tube, a thermometer, a reflux condenser and a stirrer, 100 m of toluene was added.
, N, N'-dimethyl-1,2-propanediamine 2
0.4 g (0.20 mol) was charged. Flask internal temperature 20 ℃
Phosgene was blown through the phosgene blowing tube at 10 g / hr for 2 hours with stirring, and the mixture was aged at the same temperature for 1 hour. This reaction mass was sampled, and 1,3,4-trimethyl-2-imidazolidinone was quantified by gas chromatography. The production yield was 18.3%.
Claims (5)
及びR4は、水素原子または低級アルキル基であり、そ
のうち少なくとも1個は低級アルキル基である。)で示
されるジアミン類とホスゲンとの反応により、式(II) (式中、R,R1,R2,R3,及びR4は、式(I)の
R,R1,R2,R3,及びR4と同じ。)で示される
2−イミダゾリジノン類を得るに際し、実質的に水及び
脱塩酸剤の存在下に反応させることを特徴とする2−イ
ミダゾリジノン類の製造方法。1. A formula (I) (In the formula, R is a lower alkyl group. R 1 , R 2 , R 3
And R 4 is a hydrogen atom or a lower alkyl group, at least one of which is a lower alkyl group. ) Is reacted with phosgene to give a compound of formula (II) (Wherein, R, R 1, R 2 , R 3, and R 4, R of formula (I), R 1, R 2, R 3, and the same. As R 4) 2-Imidazoriji represented by A method for producing 2-imidazolidinones, which comprises reacting in the presence of water and a dehydrochlorinating agent to obtain the nonones.
及びR4は水素原子または低級アルキル基であり、その
うち少なくとも1個は低級アルキル基である。)で示さ
れるジアミン類及び/またはその塩酸塩とホスゲンとの
反応により式(II) (式中、R,R1,R2,R3及びR4は、式(I)の
R,R1,R2,R3及びR4と同じ。)で示される2
−イミダゾリジノン類を得るに際し、水溶媒中で脱塩酸
剤により、PHを3.0〜10.0に維持しながら反応させるこ
とを特徴とする2−イミダゾリジノン類の製造方法。2. Formula (I) (In the formula, R is a lower alkyl group. R 1 , R 2 , R 3
And R 4 is a hydrogen atom or a lower alkyl group, at least one of which is a lower alkyl group. ) By reacting a diamine and / or its hydrochloride salt with phosgene. (Wherein, R, R 1, R 2, R 3 and R 4, the formula (R in I), the same as R 1, R 2, R 3 and R 4.) 2 represented by
-A method for producing 2-imidazolidinones, which comprises reacting in an aqueous solvent with a dehydrochlorinating agent while maintaining PH at 3.0 to 10.0 when obtaining the imidazolidinones.
(2)項記載の方法。3. A claim for maintaining PH at 5.0 to 8.0.
The method described in (2).
請求の範囲第(1)項または第(2)項記載の方法。4. The method according to claim (1) or (2), wherein the dehydrochlorination agent is an alkali metal compound.
範囲第(1)項または第(2)項記載の方法。5. The method according to claim (1) or (2), wherein the dehydrochlorination agent is a tertiary amine.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10777186A JPH0667910B2 (en) | 1986-05-13 | 1986-05-13 | Method for producing 2-imidazolidinones |
CA000536415A CA1283101C (en) | 1986-05-06 | 1987-05-05 | Process for producing cyclic ureas |
EP87106457A EP0248220A3 (en) | 1986-05-06 | 1987-05-05 | Process for producing cyclic ureas |
BR8702314A BR8702314A (en) | 1986-05-06 | 1987-05-06 | CYCLIC UREA PROCESS |
KR1019870004394A KR890003808B1 (en) | 1986-05-06 | 1987-05-06 | Process for preparation of cyclic ureas |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10777186A JPH0667910B2 (en) | 1986-05-13 | 1986-05-13 | Method for producing 2-imidazolidinones |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62265269A JPS62265269A (en) | 1987-11-18 |
JPH0667910B2 true JPH0667910B2 (en) | 1994-08-31 |
Family
ID=14467595
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10777186A Expired - Lifetime JPH0667910B2 (en) | 1986-05-06 | 1986-05-13 | Method for producing 2-imidazolidinones |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0667910B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11093166B2 (en) | 2014-04-17 | 2021-08-17 | Samsung Electronics Co., Ltd. | Memory system and method of operating the same |
-
1986
- 1986-05-13 JP JP10777186A patent/JPH0667910B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11093166B2 (en) | 2014-04-17 | 2021-08-17 | Samsung Electronics Co., Ltd. | Memory system and method of operating the same |
Also Published As
Publication number | Publication date |
---|---|
JPS62265269A (en) | 1987-11-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0183076B1 (en) | Process for producing 1,3-dimethyl-2-imidazolidinone | |
JPH0667910B2 (en) | Method for producing 2-imidazolidinones | |
JPS5829296B2 (en) | Method for producing monomethylhydrazine | |
JP2515326B2 (en) | Method for producing tetrahydro-2 (1H) -pyrimidinones | |
JPH0588227B2 (en) | ||
EP0244810B1 (en) | Process for producing 2-oxazolidinones | |
US4652671A (en) | Process for the preparation of dichloroisonitrilocarboxylic acid esters | |
CA2234132A1 (en) | Process to chloroketoamines using carbamates | |
JP2001026576A (en) | Production of n-alkoxy(alkenoxy) (or aryloxy)carbonyl isothiocyanates and their derivatives | |
JP3412246B2 (en) | Method for producing 2-halogeno-1-alkene derivative | |
JPH0667909B2 (en) | Method for producing 2-imidazolidinone | |
JPH09323973A (en) | Production of amide-based compound or its salt | |
JPH0564142B2 (en) | ||
JPH0667908B2 (en) | Method for producing 1,3-dialkyl-2-imidazolidinone | |
JPH0759568B2 (en) | Method for producing hexahydro-2H-1,3-diazepin-2-ones | |
JP3007610B2 (en) | Method for producing cyanoformate ester | |
JPH0353298B2 (en) | ||
JP3184745B2 (en) | Bisurea compound and method for producing the same | |
JPH05255238A (en) | Production of cysteamine compounds | |
JP3155909B2 (en) | Method for producing 1,3-dialkyl-2-imidazolidinones | |
JP2000212152A (en) | Production of n-substituted glycinonitrile | |
KR19980032426A (en) | Amine production method | |
JPH0684340B2 (en) | Formamidine formate | |
JPH1087596A (en) | Synthesis of alkylamidine hydrochloride | |
JPH07157465A (en) | Production of n-substituted-1-methylthio-2-nitroetheneamines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EXPY | Cancellation because of completion of term |