JP4023922B2 - Method for producing high purity 1,3-dialkyl-2-imidazolidinone - Google Patents
Method for producing high purity 1,3-dialkyl-2-imidazolidinone Download PDFInfo
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- JP4023922B2 JP4023922B2 JP23312498A JP23312498A JP4023922B2 JP 4023922 B2 JP4023922 B2 JP 4023922B2 JP 23312498 A JP23312498 A JP 23312498A JP 23312498 A JP23312498 A JP 23312498A JP 4023922 B2 JP4023922 B2 JP 4023922B2
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- dialkyl
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- imidazolidinone
- dmi
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- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 43
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004821 distillation Methods 0.000 description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 239000004202 carbamide Substances 0.000 description 12
- 150000002466 imines Chemical group 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- KSESOTWVQYBRLJ-UHFFFAOYSA-N 1,3-dimethylimidazolidin-2-imine Chemical compound CN1CCN(C)C1=N KSESOTWVQYBRLJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000004063 acid-resistant material Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MFIGJRRHGZYPDD-UHFFFAOYSA-N n,n'-di(propan-2-yl)ethane-1,2-diamine Chemical compound CC(C)NCCNC(C)C MFIGJRRHGZYPDD-UHFFFAOYSA-N 0.000 description 1
- YRGVKPIUZUOJSJ-UHFFFAOYSA-N n,n'-dibutylethane-1,2-diamine Chemical compound CCCCNCCNCCCC YRGVKPIUZUOJSJ-UHFFFAOYSA-N 0.000 description 1
- VATUKUMHBXZSCD-UHFFFAOYSA-N n,n'-dipropylethane-1,2-diamine Chemical compound CCCNCCNCCC VATUKUMHBXZSCD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は１，３−ジアルキル−２−イミダゾリジノンの製造方法に関する。 さらに詳しくは、Ｎ，Ｎ’−ジアルキルエチレンジアミンと尿素との反応により１，３−ジアルキル−２−イミダゾリジノンを製造する方法に関する。
１，３−ジアルキル−２−イミダゾリジノンは極性の高い非プロトン性溶媒であり、一般的な非プロトン性極性溶媒と比べて酸、アルカリに対して極めて安定であり、且つ各種の無機、有機化合物に対して強い溶解力をもつことから、医薬、農薬、染料、顔料等の合成溶媒、電子部品、モールド等の洗浄剤、高分子化合物の重合溶媒等として極めて有用な物質である。
【０００２】
【従来の技術及び発明が解決しようとする課題】
従来、１，３−ジアルキル−２−イミダゾリジノンを製造する方法として、Ｎ，Ｎ’−ジアルキルエチレンジアミンと尿素より製造する方法が知られている。例えば、本発明者等は高収率で１，３−ジアルキル−２−イミダジリジノンを得る方法として、極性溶媒中耐圧容器下に１８０℃以上で反応させる方法（特公平０８−００５８６７号公報）、これを改良して初期反応を１４０℃以下で反応させ、引き続き１８０℃以上で反応させる方法（特公平０６−０６５６６５号公報）、さらに改良して常圧下初期反応を１４０℃以下で反応させ、引き続き１８０℃以上でＮ，Ｎ’−ジアルキルエチレンジアミンを添加しながら反応させる方法（特公平０６−０６５６６６号公報）等を提案した。
【０００３】
しかし、これらの方法によると反応時に１，３−ジアルキル−２−イミダゾリジノンに対し０．５〜数％の１，３−ジアルキル−２−イミダゾリジンイミンが副生する。このものは１，３−ジアルキル−２−イミダゾリジノンと沸点が近似しているため、蒸留分離の際、精密な非常に高段の蒸留塔を必要とし、また還流比を大きくした精留を実施しない限り、完全に分離することは困難であり、多大なコストを要する等の欠点を有していた。
また、この副生物を含有する１，３−ジアルキル−２−イミダゾリジノンを溶媒として使用すると、主反応が阻害される。例えば、アラミドの製造溶媒として使用するとポリマーの重合阻害を起こす等の問題が生じる。
そこで、本発明者等は更に検討を重ね、反応過程に於いて１，３−ジアルキル−２−イミダゾリジンイミン副生量を０．１ｗｔ％に抑制する１，３−ジアルキル−２−イミダゾリジノンの製造法を見出し開示した（特開平１０−１０１６５１号公報）。しかしながら、一度副生した１，３−ジアルキル−２−イミダゾリジンイミンを検出限界以下迄除去する方法は、未だ知られていなかった。
【０００４】
従って、Ｎ，Ｎ’−ジアルキルエチレンジアミンと尿素より得られた１，３−ジアルキル−２−イミダゾリジノンより、高収率でいかに容易に１，３−ジアルキル−２−イミダゾリジンイミンを除去するかが重要な課題であった。
【０００５】
【課題を解決するための手段】
本発明者等は課題に対し鋭意検討を重ねた結果、副生物である１，３−ジアルキル−２−イミダゾリジンイミンを含有する１，３−ジアルキル−２−イミダゾリジノンに酸を添加後蒸留することにより、極めて高純度で、且つ高収率で１，３−ジアルキル−２−イミダゾリジノンが得られることを見出し本発明を完成するに至った。
【０００６】
即ち、本発明は以下に示すものである。
▲１▼一般式（１）、
【０００７】
【化４】
【０００８】
で表されるＮ，Ｎ’−ジアルキルエチレンジアミンと尿素との反応により一般式（２）、
【０００９】
【化５】
【００１０】
で表される１，３−ジアルキル−２−イミダゾリジノンを製造するに際し、得られた反応液に酸を添加し、蒸留することにより、一般式（３）、
【００１１】
【化６】
【００１２】
で表される１，３−ジアルキル−２−イミダゾリジンイミンを除去することを特徴とする１，３−ジアルキル−２−イミダゾリジノンの製造方法。
▲２▼酸がイソシアヌル酸である▲１▼記載の方法。
▲３▼Ｒが炭素数１〜４のアルキル基である▲１▼〜▲２▼記載の方法。
【００１３】
【発明の実施の形態】
本発明の代表的な態様は、Ｎ，Ｎ’−ジアルキルエチレンジアミンと尿素との反応により粗製の１，３−ジアルキル−２−イミダゾリジノンを得る工程（以下、反応工程と略記する。）、これに酸を添加し、反応で副生した１，３−ジアルキル−２−イミダゾリジンイミンを処理する工程（以下、処理工程と略記する。）、引き続き蒸留により精製１，３−ジアルキル−２−イミダゾリジノンを得る工程（以下、蒸留工程と略記する。）で構成される。
本発明の反応工程の態様は、本発明者等が提案した▲１▼特公平０８−５８６７号公報、▲２▼特公平０６−０６５６６５号公報及び▲３▼特公平０６−０６５６６６号公報等記載の方法に準拠すればよい。具体的には、▲１▼オートクレーブ中にＮ，Ｎ’−ジメチルエチレンジアミン１モル、尿素１モル及び１，３−ジメチル−２−イミダゾリジノンを仕込み、２１０℃で３時間反応する方法、▲２▼▲１▼と同仕込みで１２０℃で８時間反応させ、引き続き２１０℃で３時間反応する方法、▲３▼Ｎ，Ｎ’−ジメチルエチレンジアミン０．５モル、尿素１モル及び１，３−ジメチル−２−イミダゾリジノンを仕込み、１２０℃で２時間反応し、２００℃迄昇温後Ｎ，Ｎ’−ジメチルエチレンジアミン０．５モルを滴下しながら同温度〜２１０℃で１時間反応する方法等がある。但し、本態様は一例であり限定するものではない。
【００１４】
本発明の反応工程で用いる前記一般式（１）で表されるＮ，Ｎ’−ジアルキルエチレンジアミンとしては所望する１，３−ジアルキル−２−イミダゾリジノンに相応するＮ，Ｎ’−ジアルキルエチレンジアミンを適宣選定すればよく、Ｎ，Ｎ’−ジメチルエチレンジアミン、Ｎ，Ｎ’−ジエチルエチレンジアミン、Ｎ，Ｎ’−ジプロピルエチレンジアミン、Ｎ，Ｎ’−ジイソプロピルエチレンジアミン、Ｎ，Ｎ’−ジブチルエチレンジアミンなどが挙げられる。これらのＮ，Ｎ’−ジアルキルエチレンジアミンは、相応するモノアルキルアミンとエチレンジクロライド、エチレンブロマイド等のエチレンジハライドとの反応により容易に得ることができる。
【００１５】
本発明の反応工程で用いる溶媒としては非プロトン性極性溶媒を使用するのが好ましい。例えば、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ’−ジメチルホルムアミド、Ｎ，Ｎ’−ジメチルアセトアミド、テトラメチル尿素、ジメチルスルホキシド、ヘキサメチルホスホルアミド、スルホラン、ジオキサン等が用いられる。また、使用する溶媒の沸点が低い場合は過大な設備が必要となるため、１８０℃以上の沸点を有する溶媒が好ましく、特に溶媒分離の煩雑さを避ける意味から反応により自製した所望の１，３−ジアルキル−２−イミダゾリジノンを自溶媒とするのが最適である。
【００１６】
本発明の反応工程に於ける温度は１８０℃以上であれば特に問題はないが、好ましくは２００〜２６０℃である。この範囲内では好適な反応が行われる。また、反応初期を１４０℃以下で行い、中間体として１，１’−ジアルキル−１，１’−ジアルキレンジビスウレアを製造後、前記温度まで昇温して反応を行っても良い。
【００１７】
本発明の反応工程に於いて添加するＮ，Ｎ’−ジアルキルエチレンジアミンと尿素の量比は通常、１．０：０．５〜１．０：２．０のモル比で選ばれる。ただし、この際、Ｎ，Ｎ’−ジアルキルエチレンジアミンに対し等モル以上の尿素を使用すると尿素由来の副生物が多量生成し精製工程の負荷が大きくなり、また、等モル未満ではＮ，Ｎ’−ジアルキルエチレンジアミンが残存し収率の低下をもたらす。従って最適には１．０：１．０〜１．０：１．２の間が好ましい。
【００１８】
本発明の処理工程としては、反応で得られた粗製の１，３−ジアルキル−２−イミダゾリジノンに酸を添加し加熱混合処理する方法、或いは、一旦蒸留し同様の処理を行う方法等があるが、後者の場合はさらなる分離工程を必要とし、また、エネルギーコストの面からも不利な方法であり、前者が好ましい。
【００１９】
本発明に於ける酸とは硫酸、塩酸、燐酸等の鉱酸、シュウ酸、安息香酸等のカルボン酸類等を用いることができるが、最適にはイソシアヌル酸である。イソシアヌル酸は反応工程においても一部副生するので、、異種の酸を用いるより品質上安定した製品の供給が可能となる。また、鉱酸を用いる場合は耐酸性の材質が必要になり、設備費が増大する。
【００２０】
本発明の処理工程に於ける酸の使用量は粗製の１，３−ジアルキル−２−イミダゾリジノン中に含有する１，３−ジアルキル−２−イミダゾリジンイミンに対し当量以上である。好適には１．０〜２．０当量である。
【００２１】
本発明の処理工程に於ける処理温度は特に限定されないが、イソシアヌル酸を使用する場合は１７０℃以下で処理することが好ましい。これ以上の温度で処理すると、処理によって生じた１，３−ジアルキル−２−イミダゾリジンイミンとイソシアヌル酸との錯体が分解することにより処理が無駄となる。最適には１００℃〜１５０℃の範囲である。処理時間は１時間もあれば充分である。
【００２２】
本発明の蒸留工程に於ける蒸留時の釜内温度は特に限定されないが、イソシアヌル酸を使用する場合は１７０℃以下になるよう減圧下で行うことが好ましい。処理工程の酸としてイソシアヌル酸を使用した場合、釜内温度を１７０℃以上にすると処理工程と同様、１，３−ジアルキル−２−イミダゾリジンイミンとイソシアヌル酸との分解が生じる。
また、本発明に於ける処理工程と蒸留工程は特に分離する必要もなく、酸存在下蒸留を行ってもよい。
【００２３】
本発明の具体的態様としては、非プロトン性極性溶媒中でＮ，Ｎ’−ジアルキルエチレンジアミンと尿素との反応により得られた粗製の１，３−ジアルキル−２−イミダゾリジノンに酸を添加し、引き続き減圧下で蒸留することにより、容易に１，３−ジアルキル−２−イミダゾリジノンを取り出すことができる。
【００２４】
【実施例】
以下、本発明を実施例および比較例により、具体的に説明する。
分析はガスクロマトグラフにより行った。尚、１，３−ジアルキル−２−イミダゾリジンイミンの検出限界は１０ｐｐｍである。
【００２５】
実施例１
０．５リットルのオートクレーブにＮ，Ｎ’−ジメチルエチレンジアミン８８．１ｇ（１．０モル）、尿素６０．１ｇ及び溶媒として１，３−ジメチル−２−イミダゾリジノン（以下、ＤＭＩと略記する。）１００．０ｇを仕込んだ。反応温度２１０℃迄約３０分で昇温し、引き続きその温度で３時間反応させた。
反応終了後分析すると、ＤＭＩに対して１，３−ジメチル−２−イミダゾリジンイミン（以下、イミン体と略記する。）が０．８％検出された。この反応液にイソシアヌル酸２．０ｇを添加し、１４０〜１５０℃で１時間加熱攪拌した。
引き続き、理論段数３段相当の蒸留塔で還流比１とし２０ｍｍＨｇの条件下で蒸留を行い、１０９〜１１１℃のＤＭＩ畄分１９２．０ｇを得た。
得られたＤＭＩ純度は９９．９５％であり、イミン体は不検出であった。反応に仕込んだＤＭＩ量を差し引いて求めたＤＭＩ収率は８０．５％であった。
【００２６】
実施例２
実施例１と同様の反応器及び仕込み量とし、１２０℃で８時間反応させた。さらに２１０℃迄３０分で昇温し、その温度で３時間反応させた。
反応終了後分析すると、ＤＭＩに対してイミン体が１．２％検出された。この反応液にイソシアヌル酸３．５ｇを添加し、１２０〜１３０℃で１時間加熱攪拌した。
引き続き、実施例１と同条件下で蒸留を行いＤＭＩ畄分２０８．１ｇを得た。得られたＤＭＩ純度は９９．９８％であり、イミン体は不検出であった。反応に仕込んだＤＭＩ量を差し引いて求めたＤＭＩ収率は９４．７％であった。
【００２７】
実施例３
還流冷却器、温度計及び攪拌翼を備えた０．３リットルのガラス製フラスコ中にＮ，Ｎ’−ジメチルエチレンジアミン４４．１ｇ（０．５モル）、尿素６０．１ｇ（１．０モル）及び溶媒としてＤＭＩ１００．０ｇを仕込んだ。１２０℃で２時間反応後２００℃迄昇温し、さらに２００〜２１０℃を保ちながら滴下ロートでＮ，Ｎ’−ジメチルエチレンジアミン４４．１ｇ（０．５モル）を２時間かけて滴下した。さらに同温度で１時間反応した。
反応終了後分析すると、ＤＭＩに対してイミン体が１．５％検出された。この反応液にイソシアヌル酸４．０ｇを添加し、１２０〜１３０℃で１時間加熱攪拌した。
引き続き、実施例１と同条件下で蒸留を行いＤＭＩ畄分２１０．８ｇを得た。得られたＤＭＩ純度は９９．９７％であり、イミン体は不検出であった。反応に仕込んだＤＭＩを差し引いて求めたＤＭＩ収率は９７．０％であった。
【００２８】
実施例４
実施例３で得られた反応液に硫酸２．８ｇを添加し、１００〜１１０℃で１時間加熱攪拌した。
引き続き、実施例１と同条件下で蒸留を行いＤＭＩ畄分２１０．０ｇを得た。得られたＤＭＩ純度は９９．９７％であり、イミン体は不検出であった。反応に仕込んだＤＭＩを差し引いて求めたＤＭＩ収率は９６．３％であった。
【００２９】
比較例１
実施例３で得られた反応液を用い、イソシアヌル酸処理を行わなかった以外は実施例１と同条件下で蒸留を行いＤＭＩ畄分２１１．５ｇを得た。得られたＤＭＩ純度は９９．５１％であり、イミン体を０．４５％含有していた（ＤＭＩ収率９６．８％）。
【００３０】
比較例２
実施例３で得られた反応液を用い、理論段数３０段の蒸留塔で還流比１０とし２０ｍｍＨｇの条件下で蒸留を行いＤＭＩ畄分２０５．０ｇを得た。得られたＤＭＩ純度は９９．８５％であり、イミン体を０．１２％含有していた（ＤＭＩ収率９１．７％）。
【００３１】
【発明の効果】
本発明によって、極めて効率的に、高収率且つ極めて高純度での１，３−ジアルキル−２−イミダゾリジノンの工業的製造が可能となった。
即ち、本発明の範囲外である比較例１〜２ではイミン体の除去が不十分であり、満足な品質のＤＭＩは得られない。これに対し、本発明は実施例１〜４に示す通り、比較例と比べ高純度の１，３−ジアルキル−２−イミダゾリジノンを容易に効率よく、且つ高収率で得られることは明白であり、本発明の意義は大きい。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing 1,3-dialkyl-2-imidazolidinone. More specifically, the present invention relates to a method for producing 1,3-dialkyl-2-imidazolidinone by reacting N, N′-dialkylethylenediamine with urea.
1,3-dialkyl-2-imidazolidinone is a highly polar aprotic solvent, and is extremely stable against acids and alkalis compared to general aprotic polar solvents, and various inorganic and organic solvents. Since it has a strong dissolving power for compounds, it is a very useful substance as a synthetic solvent for pharmaceuticals, agricultural chemicals, dyes, pigments and the like, a cleaning agent for electronic parts and molds, a polymerization solvent for polymer compounds, and the like.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, as a method for producing 1,3-dialkyl-2-imidazolidinone, a method for producing N, N′-dialkylethylenediamine and urea is known. For example, as a method for obtaining 1,3-dialkyl-2-imidaziridinone in a high yield, the present inventors made a reaction at 180 ° C. or higher in a pressure-resistant vessel in a polar solvent (Japanese Patent Publication No. 08-005867), The initial reaction is carried out at 140 ° C. or lower and the reaction is continued at 180 ° C. or higher (Japanese Patent Publication No. 06-066565), and the initial reaction under normal pressure is reacted at 140 ° C. or lower, followed by 180 ° C. A method of reacting while adding N, N′-dialkylethylenediamine at a temperature higher than or equal to 0 ° C. (Japanese Patent Publication No. 06-0665666) has been proposed.
[0003]
However, according to these methods, 0.5 to several percent of 1,3-dialkyl-2-imidazolidineimine is by-produced with respect to 1,3-dialkyl-2-imidazolidinone during the reaction. Since this has a boiling point close to that of 1,3-dialkyl-2-imidazolidinone, it requires a very high-precision distillation column for distillation separation, and rectification with a large reflux ratio is required. Unless it implemented, it was difficult to isolate | separate completely and had the faults, such as requiring great cost.
Further, when 1,3-dialkyl-2-imidazolidinone containing this by-product is used as a solvent, the main reaction is inhibited. For example, when used as a production solvent for aramid, problems such as polymerization inhibition of the polymer occur.
Therefore, the present inventors have further studied, and 1,3-dialkyl-2-imidazolidinone which suppresses the amount of 1,3-dialkyl-2-imidazolidineimine by-product to 0.1 wt% in the reaction process. The manufacturing method was discovered and disclosed (Japanese Patent Laid-Open No. 10-101651). However, a method for removing 1,3-dialkyl-2-imidazolidineimine once by-produced to the detection limit or less has not been known yet.
[0004]
Therefore, how easily 1,3-dialkyl-2-imidazolidineimine can be removed in a high yield from 1,3-dialkyl-2-imidazolidinone obtained from N, N′-dialkylethylenediamine and urea. Was an important issue.
[0005]
[Means for Solving the Problems]
As a result of intensive studies on the problem, the present inventors have added an acid to 1,3-dialkyl-2-imidazolidinone containing 1,3-dialkyl-2-imidazolidineimine, which is a by-product, and then distilled it. As a result, it was found that 1,3-dialkyl-2-imidazolidinone was obtained with extremely high purity and high yield, and the present invention was completed.
[0006]
That is, the present invention is as follows.
(1) General formula (1),
[0007]
[Formula 4]
[0008]
By the reaction of N, N′-dialkylethylenediamine represented by the formula (2),
[0009]
[Chemical formula 5]
[0010]
In the production of 1,3-dialkyl-2-imidazolidinone represented by the following general formula (3), an acid is added to the reaction solution and distilled.
[0011]
[Chemical 6]
[0012]
A method for producing 1,3-dialkyl-2-imidazolidinone, comprising removing 1,3-dialkyl-2-imidazolidineimine represented by the formula:
(2) The method according to (1), wherein the acid is isocyanuric acid.
(3) The method according to (1) to (2), wherein R is an alkyl group having 1 to 4 carbon atoms.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
A typical embodiment of the present invention is a step of obtaining crude 1,3-dialkyl-2-imidazolidinone by reaction of N, N′-dialkylethylenediamine and urea (hereinafter abbreviated as “reaction step”). A step of treating 1,3-dialkyl-2-imidazolidineimine produced as a by-product in the reaction by adding an acid to the reaction (hereinafter abbreviated as a treatment step), followed by purification by distillation, 1,3-dialkyl-2-imidazolid It comprises a step of obtaining lysinone (hereinafter abbreviated as a distillation step).
The aspect of the reaction process of the present invention is described in (1) Japanese Patent Publication No. 08-5867, (2) Japanese Patent Publication No. 06-066565 and (3) Japanese Patent Publication No. 06-066566 proposed by the present inventors. It is sufficient to comply with the method. Specifically, (1) A method in which 1 mol of N, N′-dimethylethylenediamine, 1 mol of urea and 1,3-dimethyl-2-imidazolidinone are charged in an autoclave and reacted at 210 ° C. for 3 hours, (2) (2) A method of reacting at 120 ° C. for 8 hours with the same preparation as in (1), followed by reaction at 210 ° C. for 3 hours, (3) N, N′-dimethylethylenediamine 0.5 mol, urea 1 mol and 1,3-dimethyl 2-Imidazolidinone was charged, reacted at 120 ° C. for 2 hours, heated to 200 ° C., and reacted dropwise at the same temperature to 210 ° C. for 1 hour while adding 0.5 mol of N, N′-dimethylethylenediamine dropwise. There is. However, this aspect is an example and is not limited.
[0014]
As the N, N′-dialkylethylenediamine represented by the general formula (1) used in the reaction step of the present invention, N, N′-dialkylethylenediamine corresponding to the desired 1,3-dialkyl-2-imidazolidinone is used. Appropriate selection may be made, such as N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-dipropylethylenediamine, N, N′-diisopropylethylenediamine, N, N′-dibutylethylenediamine, and the like. It is done. These N, N′-dialkylethylenediamines can be easily obtained by reacting the corresponding monoalkylamines with ethylene dihalides such as ethylene dichloride and ethylene bromide.
[0015]
As the solvent used in the reaction step of the present invention, an aprotic polar solvent is preferably used. For example, N-methyl-2-pyrrolidone, N, N′-dimethylformamide, N, N′-dimethylacetamide, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, dioxane and the like are used. In addition, when the boiling point of the solvent to be used is low, excessive equipment is required. Therefore, a solvent having a boiling point of 180 ° C. or higher is preferable. In particular, the desired 1,3 produced by reaction from the viewpoint of avoiding complicated solvent separation. It is optimal to use -dialkyl-2-imidazolidinone as an autosolvent.
[0016]
The temperature in the reaction step of the present invention is not particularly limited as long as it is 180 ° C. or higher, but is preferably 200 to 260 ° C. Within this range, a suitable reaction takes place. Alternatively, the reaction may be performed at an initial temperature of 140 ° C. or lower to produce 1,1′-dialkyl-1,1′-dialkylenedibisurea as an intermediate, and then the reaction may be performed by raising the temperature to the above temperature.
[0017]
The amount ratio of N, N′-dialkylethylenediamine and urea added in the reaction step of the present invention is usually selected at a molar ratio of 1.0: 0.5 to 1.0: 2.0. However, in this case, if equimolar or more of urea is used with respect to N, N′-dialkylethylenediamine, a large amount of urea-derived by-products are produced, increasing the load of the purification process, and if less than equimolar, N, N′— Dialkylethylenediamine remains, resulting in a decrease in yield. Therefore, it is preferably between 1.0: 1.0 and 1.0: 1.2.
[0018]
The treatment step of the present invention includes a method of adding an acid to the crude 1,3-dialkyl-2-imidazolidinone obtained by the reaction and heating and mixing, or a method of once distilling and performing the same treatment. However, the latter case requires a further separation step and is disadvantageous in terms of energy cost, and the former is preferable.
[0019]
The acid in the present invention may be a mineral acid such as sulfuric acid, hydrochloric acid or phosphoric acid, or a carboxylic acid such as oxalic acid or benzoic acid, and is most preferably isocyanuric acid. Since isocyanuric acid is partially produced as a by-product in the reaction process, it is possible to supply a more stable product in terms of quality than using different acids. Moreover, when using a mineral acid, an acid-resistant material is needed, and installation cost increases.
[0020]
The amount of acid used in the treatment step of the present invention is equal to or greater than the equivalent of 1,3-dialkyl-2-imidazolidineimine contained in the crude 1,3-dialkyl-2-imidazolidinone. Preferably it is 1.0-2.0 equivalent.
[0021]
The treatment temperature in the treatment step of the present invention is not particularly limited, but when isocyanuric acid is used, it is preferably treated at 170 ° C. or lower. When the treatment is performed at a temperature higher than this, the treatment is wasted because the complex of 1,3-dialkyl-2-imidazolidineimine and isocyanuric acid generated by the treatment is decomposed. Optimally, it is in the range of 100 ° C to 150 ° C. A processing time of one hour is sufficient.
[0022]
The temperature in the kettle at the time of distillation in the distillation step of the present invention is not particularly limited, but when isocyanuric acid is used, it is preferably carried out under reduced pressure so as to be 170 ° C. or lower. When isocyanuric acid is used as the acid in the treatment step, decomposition of 1,3-dialkyl-2-imidazolidineimine and isocyanuric acid occurs as in the treatment step when the temperature in the kettle is set to 170 ° C. or higher.
Further, the treatment step and the distillation step in the present invention are not particularly required to be separated, and the distillation may be performed in the presence of an acid.
[0023]
As a specific embodiment of the present invention, an acid is added to crude 1,3-dialkyl-2-imidazolidinone obtained by the reaction of N, N′-dialkylethylenediamine and urea in an aprotic polar solvent. Subsequently, 1,3-dialkyl-2-imidazolidinone can be easily taken out by distillation under reduced pressure.
[0024]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
Analysis was performed by gas chromatography. The detection limit of 1,3-dialkyl-2-imidazolidineimine is 10 ppm.
[0025]
Example 1
In a 0.5 liter autoclave, 88.1 g (1.0 mol) of N, N′-dimethylethylenediamine, 60.1 g of urea and 1,3-dimethyl-2-imidazolidinone (hereinafter abbreviated as DMI) as a solvent are used. ) 100.0 g was charged. The reaction temperature was raised to 210 ° C. in about 30 minutes, and the reaction was continued at that temperature for 3 hours.
Upon analysis after the completion of the reaction, 0.8% of 1,3-dimethyl-2-imidazolidineimine (hereinafter abbreviated as imine form) was detected with respect to DMI. To this reaction solution, 2.0 g of isocyanuric acid was added, and the mixture was heated and stirred at 140 to 150 ° C. for 1 hour.
Subsequently, distillation was carried out under a condition of 20 mmHg with a reflux ratio of 1 in a distillation column corresponding to 3 theoretical plates to obtain 192.0 g of DMI fraction of 109 to 111 ° C.
The DMI purity obtained was 99.95%, and no imine was detected. The DMI yield obtained by subtracting the amount of DMI charged into the reaction was 80.5%.
[0026]
Example 2
The same reactor and charge as in Example 1 were used, and the reaction was carried out at 120 ° C. for 8 hours. The temperature was further raised to 210 ° C. in 30 minutes, and the reaction was carried out at that temperature for 3 hours.
When analyzed after the completion of the reaction, 1.2% imine was detected relative to DMI. To this reaction liquid, 3.5 g of isocyanuric acid was added, and the mixture was heated and stirred at 120 to 130 ° C. for 1 hour.
Subsequently, distillation was performed under the same conditions as in Example 1 to obtain 208.1 g of DMI fraction. The obtained DMI purity was 99.98%, and imine was not detected. The DMI yield obtained by subtracting the amount of DMI charged into the reaction was 94.7%.
[0027]
Example 3
In a 0.3 liter glass flask equipped with a reflux condenser, a thermometer and a stirring blade, 44.1 g (0.5 mol) of N, N′-dimethylethylenediamine, 60.1 g (1.0 mol) of urea and As a solvent, 100.0 g of DMI was charged. After reacting at 120 ° C. for 2 hours, the temperature was raised to 200 ° C., and 44.1 g (0.5 mol) of N, N′-dimethylethylenediamine was added dropwise over 2 hours with a dropping funnel while maintaining 200 to 210 ° C. Furthermore, it reacted at the same temperature for 1 hour.
When analyzed after the completion of the reaction, 1.5% imine was detected relative to DMI. 4.0 g of isocyanuric acid was added to this reaction solution, and the mixture was heated and stirred at 120 to 130 ° C. for 1 hour.
Subsequently, distillation was performed under the same conditions as in Example 1 to obtain 210.8 g of DMI fraction. The DMI purity obtained was 99.97%, and no imine was detected. The DMI yield obtained by subtracting the DMI charged in the reaction was 97.0%.
[0028]
Example 4
To the reaction solution obtained in Example 3, 2.8 g of sulfuric acid was added, and the mixture was heated and stirred at 100 to 110 ° C. for 1 hour.
Subsequently, distillation was performed under the same conditions as in Example 1 to obtain 210.0 g of DMI fraction. The DMI purity obtained was 99.97%, and no imine was detected. The DMI yield obtained by subtracting the DMI charged into the reaction was 96.3%.
[0029]
Comparative Example 1
Distillation was performed under the same conditions as in Example 1 except that the isocyanuric acid treatment was not performed using the reaction solution obtained in Example 3, to obtain 211.5 g of DMI fraction. The purity of the obtained DMI was 99.51% and contained 0.45% of an imine (DMI yield 96.8%).
[0030]
Comparative Example 2
Using the reaction solution obtained in Example 3, the distillation was carried out in a distillation column having a theoretical plate number of 30 and a reflux ratio of 10 to obtain a DMI fraction of 205.0 g under a condition of 20 mmHg. The obtained DMI purity was 99.85% and contained 0.12% imine (DMI yield 91.7%).
[0031]
【The invention's effect】
The present invention has enabled the industrial production of 1,3-dialkyl-2-imidazolidinone in a very efficient, high yield and extremely high purity.
That is, in Comparative Examples 1 and 2 that are outside the scope of the present invention, imine is not sufficiently removed, and satisfactory quality DMI cannot be obtained. On the other hand, as shown in Examples 1 to 4, the present invention clearly shows that 1,3-dialkyl-2-imidazolidinone having a high purity can be easily and efficiently obtained in a high yield as compared with the comparative example. Therefore, the significance of the present invention is great.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP23312498A JP4023922B2 (en) | 1998-08-19 | 1998-08-19 | Method for producing high purity 1,3-dialkyl-2-imidazolidinone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23312498A JP4023922B2 (en) | 1998-08-19 | 1998-08-19 | Method for producing high purity 1,3-dialkyl-2-imidazolidinone |
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