JPS62292761A - Production of 2-imidazolidinones - Google Patents
Production of 2-imidazolidinonesInfo
- Publication number
- JPS62292761A JPS62292761A JP61134888A JP13488886A JPS62292761A JP S62292761 A JPS62292761 A JP S62292761A JP 61134888 A JP61134888 A JP 61134888A JP 13488886 A JP13488886 A JP 13488886A JP S62292761 A JPS62292761 A JP S62292761A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- reaction
- urea
- diamines
- imidazolidinone
- 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.)
- Granted
Links
- 150000008625 2-imidazolidinones Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 150000004985 diamines Chemical class 0.000 claims abstract description 49
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000004202 carbamide Substances 0.000 claims abstract description 48
- 239000002798 polar solvent Substances 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 abstract description 24
- RDHNFSNXWLWMIX-UHFFFAOYSA-N 1-n,2-n-dimethylpropane-1,2-diamine Chemical compound CNCC(C)NC RDHNFSNXWLWMIX-UHFFFAOYSA-N 0.000 abstract description 9
- JJNFHWKVZWAKEB-UHFFFAOYSA-N 1,3,4-trimethylimidazolidin-2-one Chemical compound CC1CN(C)C(=O)N1C JJNFHWKVZWAKEB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 polyvinylalconyl Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- LBGFTWMHLSYQLV-UHFFFAOYSA-N 1,3-diethyl-4-methylimidazolidin-2-one Chemical compound CCN1CC(C)N(CC)C1=O LBGFTWMHLSYQLV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 150000008624 imidazolidinones Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000002699 waste material Substances 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- JTPZTKBRUCILQD-UHFFFAOYSA-N 1-methylimidazolidin-2-one Chemical compound CN1CCNC1=O JTPZTKBRUCILQD-UHFFFAOYSA-N 0.000 description 1
- RRQHLOZQFPWDCA-UHFFFAOYSA-N 1-n,1-n-dimethylpropane-1,2-diamine Chemical compound CC(N)CN(C)C RRQHLOZQFPWDCA-UHFFFAOYSA-N 0.000 description 1
- VECZPMZNUKYYOJ-UHFFFAOYSA-N 1-n,2-n-diethylpropane-1,2-diamine Chemical compound CCNCC(C)NCC VECZPMZNUKYYOJ-UHFFFAOYSA-N 0.000 description 1
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 1
- AAYQLESQZODDLQ-UHFFFAOYSA-N 2-n,3-n,2-trimethylbutane-2,3-diamine Chemical compound CNC(C)C(C)(C)NC AAYQLESQZODDLQ-UHFFFAOYSA-N 0.000 description 1
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ODUIXUGXPFKQLG-QWRGUYRKSA-N [2-(4-chloro-2-fluoroanilino)-5-methyl-1,3-thiazol-4-yl]-[(2s,3s)-2,3-dimethylpiperidin-1-yl]methanone Chemical compound C[C@H]1[C@@H](C)CCCN1C(=O)C1=C(C)SC(NC=2C(=CC(Cl)=CC=2)F)=N1 ODUIXUGXPFKQLG-QWRGUYRKSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- OFCCYDUUBNUJIB-UHFFFAOYSA-N n,n-diethylcarbamoyl chloride Chemical compound CCN(CC)C(Cl)=O OFCCYDUUBNUJIB-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、式CI)
(娑中−Rは低級アルキル基であるa R1−R2+P
及びR+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
れるジアミン類とウレアとの反応によ(式中、R,R;
l、R2,R3及びR4は、式(I)(7) R、R1
、Fu、R3及びR4と同じ。)で示さnる2J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] [Industrial Application Field] The present invention relates to the formula CI) (a R1-R2+P in which -R is a lower alkyl group)
and R+ are hydrogen atoms or lower alkyl groups, at least one of which is a lower alkyl group. ) by the reaction of diamines represented by the formula with urea (where R, R;
l, R2, R3 and R4 are formula (I) (7) R, R1
, Fu, same as R3 and R4. ) The present invention relates to a method for producing 2J imidazolidinones represented by n.
上記式(n)で示される2−イミダゾリジノン類は、非
プロトン性極性溶媒や医薬・農薬の中間体として有用な
物質である。特にポリアミド類、ポリ塩化ビニル、ポリ
ビニルアルコニル、ポリスチレン、ポリウレタン、フェ
ノール樹脂などの高分子化合物に優れた溶媒であり、ま
た多くの無機化合物を容易に溶解し、各種の特徴ある有
機反応の溶媒として用いられる。The 2-imidazolidinones represented by the above formula (n) are useful substances as aprotic polar solvents and intermediates for pharmaceuticals and agricultural chemicals. In particular, it is an excellent solvent for polymeric compounds such as polyamides, polyvinyl chloride, polyvinylalconyl, polystyrene, polyurethane, and phenolic resins.It also easily dissolves many inorganic compounds, and can be used as a solvent for various unique organic reactions. used.
上記式(n)で示される2−イミダゾリジノン類の製造
方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
反応させて収率75チで得る方法〔リービッヒス アナ
ーレン デア ケミ−(Liebig; Ann、
der Chem−) 、 726巻、97頁(リヘλ
ンー2−オンを水素添加する方法〔リービツヒス アナ
ーレン デア ケミ−(Liebig 、 Ann
@der Chem、 ) 726巻、97頁(19
69)) 、N、N’−ジメチル−1−1,2−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〔米国特許 2398283号(1943)
)などが知られている。Several methods for producing 2-imidazolidinones represented by the above formula (n) have been proposed. For example, 1,3.4-
For trimethyl-2-imidazolidinone, N,
A method of reacting N'-dimethyl-1,2-propanediamine with urea to obtain a yield of 75 cm [Liebig; Ann.
der Chem-), vol. 726, p. 97 (Lihe λ
Method for hydrogenating 2-ones [Liebig, Ann der Chemie]
@der Chem, ) volume 726, page 97 (19
69)) Method of reacting N,N'-dimethyl-1-1,2-propanediamine with diethylcarbamyl chloride [US Pat. No. 2,398,283 (1943)]
) etc. are known.
前述のようにジアミン類とウレアとで2−イミダゾリジ
ノン類を得る方法は公知であるが、反応マスの操作性と
収率向上のため、ウレア1モルに対して、ジアミン類を
1.5モルと過剰に用いている。As mentioned above, the method of obtaining 2-imidazolidinones using diamines and urea is known, but in order to improve the operability of the reaction mass and the yield, 1.5% of the diamines are added to 1 mole of urea. It is used in mole excess.
過剰2アミン類は高価なため、反応マスより回収しなく
てはいけない。また収率は75チであり。Excess diamines are expensive and must be recovered from the reaction mass. The yield was 75 cm.
工業的製法としては尚満足すべきものではなかった。As an industrial manufacturing method, it was still unsatisfactory.
本発明は、上記式(I)で示されるジアミン類とウレア
とを反応させ、収率よく上記式(n)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 production method for obtaining 2-imidazolidinones represented by the above formula (n) in good yield by reacting diamines represented by the above formula (I) with urea. .
本発明者等は、上記式〇)で示されるジアミン類とウレ
アとを反応させ、上記式CI[)で示される2−イミダ
ゾリジノン類を得るにあたり安価で、収率が高く、操作
性も良好な工業的製法を鋭意検討し、以下のような知見
を得、本発明に達した。The present inventors reacted the diamines represented by the above formula 〇) with urea to obtain 2-imidazolidinones represented by the above formula CI[) at low cost, in high yield, and with good operability. After intensive research into a good industrial manufacturing method, the following knowledge was obtained and the present invention was achieved.
(1)、極性溶媒の存在下180℃以上で反応させると
、高収率で2−イミダゾリジノン類が得られることをみ
いだした。(1) It has been found that 2-imidazolidinones can be obtained in high yield when the reaction is carried out at 180° C. or higher in the presence of a polar solvent.
通常、ジアミン類とウレアとの反応では、2−イミダゾ
リジノン類が生成する前に、ジアミンのウレア中間体が
生成する。この中間体は、多くの場合、非極性溶媒に対
して溶解度が小さく系外へ析出する。しかし、この中間
体は溶解状態で180℃以上でないと2−イミダゾリジ
ノンへの閉環反応は極めて遅い。この理由より、ウレア
中間体の溶解度の大きい極性溶媒下、180″C以下で
ジアミン類とウレアを反応させると2−イミダゾリジノ
ン類が高収率で得られることがわかった。Usually, in the reaction between diamines and urea, a urea intermediate of the diamine is produced before 2-imidazolidinones are produced. This intermediate often has low solubility in nonpolar solvents and precipitates out of the system. However, unless this intermediate is in a dissolved state at 180°C or higher, the ring-closing reaction to form 2-imidazolidinone is extremely slow. For this reason, it has been found that 2-imidazolidinones can be obtained in high yield when diamines and urea are reacted at 180"C or less in a polar solvent in which the urea intermediate has a high solubility.
(2)、さらに、ジアミン類とウレアとの極性溶媒下の
反応においては、ジアミン類のウレア中間体が生成する
までは140.”C以下で反応させ、その後180″C
以上で反応させればさらに収率の上がることを見いだし
た。(2) Furthermore, in the reaction of diamines and urea in a polar solvent, the reaction time is 140. React at 180"C or lower, then at 180"C
It was found that the yield could be further increased if the reaction was carried out in the above manner.
ジアミン類とウレアとの照性溶媒下での反応ではウレア
中間体が生成するまでの初期反応は特に180℃以上の
温度は必要としない。100°C以下では反応は遅くな
るが、100°C付近から140°C以下で十分に反応
は進行する。180″C以上ではウレア自体の熱分解の
ため、ウレアのロスが生じる。このため、2段上昇反応
法の方がウレアが無駄なく反応に供されることがわかっ
た。In the reaction of diamines and urea in a luminescent solvent, a temperature of 180° C. or higher is not particularly required for the initial reaction until the urea intermediate is produced. At temperatures below 100°C, the reaction slows down, but the reaction progresses satisfactorily between around 100°C and below 140°C. At temperatures above 180''C, urea itself is thermally decomposed, resulting in a loss of urea.For this reason, it has been found that the two-stage ascending reaction method allows urea to be subjected to the reaction without waste.
ジアミン類のウレア中間体の反応終点はアンモニア発生
の終了で容易に判断される。この2段昇温法では、ジア
ミン類及びウレアがともに無駄なく使用されるので、ジ
アミン類及びウレアとも特に過剰に用いる必要はなく、
ジアミン類/ウレアの仕込みモル比は0.6〜1.2に
なるようにすればよい。好ましくは、はぼ等モルになる
ように仕込めばよい。ジアミン類を過剰に仕込めば、高
価なジアミンを回収する操作が追加される。また、ウレ
アを過剰に仕込めばウレア熱分解物であるシアヌル酸等
の固体不純物が反応系に残り、煩雑な固液分離操作が追
加される。The end point of the reaction of the urea intermediate of diamines is easily determined by the completion of ammonia generation. In this two-stage heating method, both diamines and urea are used without waste, so there is no need to use excessive amounts of either diamines or urea.
The molar ratio of diamines/urea may be 0.6 to 1.2. Preferably, they may be prepared in approximately equimolar amounts. If too much diamine is added, an additional operation is required to recover the expensive diamine. Furthermore, if urea is charged in excess, solid impurities such as cyanuric acid, which is a thermal decomposition product of urea, remain in the reaction system, adding to the complicated solid-liquid separation operation.
(3)、また、本発明者らはさらに工業的製法として検
討を深め、以下の発明もみいだした。(3) In addition, the present inventors further investigated the method as an industrial production method and discovered the following invention.
上記2段昇温法を採用すると、140°C以下の初期反
応は問題ないものの、多くの場合ジアミン類の沸点が1
80℃以下であるので、昇温して180℃以上の反応を
行なう場合、未反応ジアミン類が残存するため、常圧で
180°C以上で反応することが困難であり、オートク
レーブ使用等の加圧下で反応しなければならない。When the above two-stage heating method is adopted, there is no problem with the initial reaction below 140°C, but in many cases the boiling point of diamines is 1.
Since the temperature is 80°C or lower, if the temperature is raised to carry out the reaction at 180°C or higher, unreacted diamines will remain, making it difficult to carry out the reaction at normal pressure at 180°C or higher. Must react under pressure.
これを避けるため本発明者らは、反応当初に極比溶媒存
在下にジアミン類/ウレアの仕込みモル比がほぼV2に
なるように仕込み、初期反応のウレア中間体の生成が完
結するまでは140°C以下で反応させ、引き続きtS
O℃以上で、全体のジアミン類/ウレアのモル比がほぼ
2/2になるようにジアミン類を添加しながら反応させ
る酪
ことによって、常決でも高収率で2−イミダゾリジノン
類が得られることを見いだした。In order to avoid this, the present inventors charged diamines/urea in the presence of a polar solvent at the beginning of the reaction so that the molar ratio of diamines/urea was approximately V2. React below °C and continue with tS
2-imidazolidinones can be obtained in high yield even under normal conditions by reacting at 0°C or higher while adding diamines so that the overall molar ratio of diamines/urea is approximately 2/2. I found that it can be done.
この理由は、反応当初にジアミン類に対してウレアを約
2倍モル仕込んで反応させるので、初期反応で生成する
ウレア中間体は、はぼ完全に不揮発生のジアミン類のジ
ウレア化物になっており、原料ジアミン類が残存しない
ので、常圧でも180°C以上の昇温が可能となるから
である。したがってこの方法によれば、溶媒の沸点が1
80℃以上であれば全反応を通じて常圧下で反応できる
。また、180°C以上で添加されるジアミン類は有効
に反応に供され、一括仕込みで2段昇温法で反応させる
方法にくらべて、収率的にも何ら遜色はないこともわか
った。The reason for this is that at the beginning of the reaction, approximately twice the molar amount of urea is charged to the diamines, so the urea intermediate produced in the initial reaction is almost completely a non-volatile diurea compound of the diamines. This is because, since no raw material diamines remain, it is possible to raise the temperature to 180°C or more even at normal pressure. Therefore, according to this method, the boiling point of the solvent is 1
If the temperature is 80° C. or higher, the entire reaction can be carried out under normal pressure. It was also found that the diamines added at 180°C or higher are effectively subjected to the reaction, and that there is no inferiority in terms of yield compared to a method in which the reaction is carried out in a two-stage temperature raising method using bulk charging.
本発明方法において使用される溶媒としては、炭化水素
及びハロゲン化炭化水素などのように非極性溶媒は適さ
ず、極性溶媒を使用する。As the solvent used in the method of the present invention, nonpolar solvents such as hydrocarbons and halogenated hydrocarbons are not suitable, but polar solvents are used.
好ましい溶媒としては、 N、N’−ジメチルホルムア
ミド、NI−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、メチルイソブチルケトン、ニトロベンゼ
ン、テトラヒドロフラン、ジオキサン、等の非プロトン
性極性溶媒が使用できる。また沸点が低い場合、過大な
耐圧装置が必要となるため、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性を避ける目的
から、反応で生成する2−イミダゾリジノン類が最も良
い。Preferred solvents include aprotic polar solvents such as N,N'-dimethylformamide, NI-dimethylacetamide, tetramethylurea, dimethyl sulfoxide, hexamethylphosphoramide, sulfolane, methyl isobutyl ketone, nitrobenzene, tetrahydrofuran, and dioxane. can be used. In addition, if the boiling point is low, an excessively large pressure-resistant device is required, so a solvent with a boiling point of 180°C or higher is preferable. In particular, for the purpose of avoiding the complexity of solvent separation, 2-imidazolidinones produced by the reaction are the most suitable. good.
本発明に用いられる上記式(1)で示される原料ジアミ
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
どである。The raw material diamines represented by the above formula (1) used in the present invention include N,N'-dimethyl-1,2-propanediamine, N,N-2-trimethyl-2,3-butanediamine, and N,N'-dimethyl-1,2-propanediamine. '-diethyl-1,2-propanediamine and the like.
本発明で得られる上記式(n)で示される2−イミダゾ
リジノン類は、上述のジアミン類を用いて得られる相応
する2−イミダゾリジノン類であり、1.3.4−1−
ツメチル−2−イミダゾリジノン、 1.3.4,4.
5 +1−ペンタメチル−2−イミダゾリジ/ン、1.
3−ジエチル−4−メチル−2−イミダゾリジノンなど
である。The 2-imidazolidinones represented by the above formula (n) obtained in the present invention are the corresponding 2-imidazolidinones obtained using the above-mentioned diamines, and are 1.3.4-1-
trimethyl-2-imidazolidinone, 1.3.4,4.
5 +1-pentamethyl-2-imidazolidine, 1.
3-diethyl-4-methyl-2-imidazolidinone and the like.
本発明方法の好ましい通常の態様を述べれば、加圧下の
場合、温度計及び機械的撹拌機を備えたオートクレーブ
に、原料ジアミン類、ウレア、極性溶媒を仕込み、18
0℃以上に昇温しで反応させる。180°C以上であれ
ば特に限定されないが、300℃以上での実施では加熱
方法及びエネルギーコストの面で問題がある。2段昇温
反応をする時は、予め140°C以下で反応後、再昇温
して180°C以上で反応させる。常圧でジアミン類を
添加する方法では、還流冷却器、温度計1滴下ロート及
び機械的撹拌機を備えた反応器器中に、ジアミン類、ウ
レア、極性溶媒を仕込み、140°C以下でアンモニア
の発生が終了するまで反応させ、その後、180°C以
上に昇温して滴下ロートよりジアミン類を添加させなが
ら反応させる。反応終了液は、蒸留等により2−イミダ
ゾリジノン類を取出すことができる。特に生成する2−
イミダゾリジノン類を溶媒とした場合、蒸留時溶媒との
分離の必要がなく、極めて簡素化されたプロセスとなる
。To describe a preferred and ordinary embodiment of the method of the present invention, under pressure, raw material diamines, urea, and a polar solvent are charged into an autoclave equipped with a thermometer and a mechanical stirrer, and the
The reaction is carried out by raising the temperature to 0°C or higher. There is no particular limitation as long as the temperature is 180°C or higher, but if the temperature is 300°C or higher, there are problems in terms of heating method and energy cost. When carrying out a two-stage temperature raising reaction, the reaction is carried out at 140°C or lower, and then the temperature is raised again to carry out the reaction at 180°C or higher. In the method of adding diamines at normal pressure, diamines, urea, and a polar solvent are placed in a reactor equipped with a reflux condenser, a dropping funnel with a thermometer, and a mechanical stirrer, and ammonia is added at 140°C or below. The reaction is allowed to proceed until the generation of is completed, and then the temperature is raised to 180° C. or higher, and the reaction is allowed to proceed while adding diamines from the dropping funnel. 2-imidazolidinones can be extracted from the reaction-completed liquid by distillation or the like. Especially the 2-
When imidazolidinones are used as a solvent, there is no need for separation from the solvent during distillation, resulting in an extremely simplified process.
本発明のジアミン類とウレアとの反応で2−イミダゾリ
ジノン類を得るに際し、極性溶媒の存在下に180°C
以上の温度で反応させることにより、従来法にくらべて
高価なジアミン類を過剰に用いることなく、操作性良好
で、高収率で目的物が得られる。特に反応を2段階の温
度勾配を設けて実施すれば収率が向上し、しかもその際
初期反応時に仕込まれるジアミン類をウレアに対してほ
ぼ1/2モルにして、後段反応でほぼ当モルとなるよう
累積添加して反応させれば常圧下で実施できる。When obtaining 2-imidazolidinones by the reaction of the diamines and urea of the present invention, the reaction temperature is 180°C in the presence of a polar solvent.
By performing the reaction at the above temperature, the desired product can be obtained in high yield with good operability without using an excessive amount of expensive diamines compared to conventional methods. In particular, if the reaction is carried out with a two-step temperature gradient, the yield will be improved.Moreover, in this case, the amount of diamines charged in the initial reaction is reduced to approximately 1/2 mole relative to urea, and the amount of diamines charged in the initial reaction is reduced to approximately 1/2 mole relative to the urea. The reaction can be carried out under normal pressure by cumulatively adding and reacting so that the reaction is carried out.
以下に実施例を挙げ、さらに詳細に説明する。 Examples will be given below to explain in more detail.
実施例−1 500m/のステンレス製オートクレーブに、N。Example-1 N in a 500m/stainless steel autoclave.
N′−ジメチル−1,2−プロパンジアミン102.2
g(1,00モル)、ウレア60.1g(1,ooモル
)及び1,3゜4−トリメチル−2−イミダゾリジノン
100gを仕込んだ。反応温度210°Cまで、約30
分で昇温し、その温度で3時間反応させた。N'-dimethyl-1,2-propanediamine 102.2
(1,00 mol), 60.1 g (1,00 mol) of urea, and 100 g of 1,3°4-trimethyl-2-imidazolidinone. Up to reaction temperature 210°C, approx.
The temperature was raised in minutes, and the reaction was continued at that temperature for 3 hours.
反応終了後、ガスクロマトグラフィーにより1゜3.4
−1−ジメチル−2−’−イミダゾリジノンを定量した
。生成収率は853係であった。この反応マスを減圧蒸
留してl、 3.4−トリメチル−2−イミダゾリジノ
ン(沸点133〜135°c/20torrの留分)2
026Fを得た。After the reaction was completed, the temperature was determined to be 1°3.4 by gas chromatography.
-1-dimethyl-2-'-imidazolidinone was quantified. The production yield was 853. This reaction mass was distilled under reduced pressure to obtain 3.4-trimethyl-2-imidazolidinone (a fraction with a boiling point of 133-135°C/20 torr)2.
026F was obtained.
実施例−2
原料の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130.3.9 (1,flf’1モル)を使用
し、また溶媒として1,3.4−)−ツメチル−2−イ
ミダゾリジノンの代りに、1.3.4.4.・5−ペン
タメチル−2−イミダゾリジノン100gを使用した以
外は実施例1と同様に反応させ分析した。その結果、l
、 :’(、4゜4.5−ペンタメチル−2−イミダゾ
リジノンの生成収率は84.7係であった。Example-2 Instead of the raw material N,N'-dimethyl-1,2-propanediamine, N,N;2-trimethyl-2,3-butanediamine 130.3.9 (1,flf'1 mol) and using 1.3.4.4. and instead of 1,3.4-)-tumethyl-2-imidazolidinone as solvent. - Reaction and analysis were carried out in the same manner as in Example 1, except that 100 g of 5-pentamethyl-2-imidazolidinone was used. As a result, l
, :'(, 4° The production yield of 4.5-pentamethyl-2-imidazolidinone was 84.7%.
実施例−3
原料のN、N′−ジメチル−1,2−プロパンジアミン
の代りに、N、NI=ジエチル−1,2−プロパンジア
ミン130.3.9(1,n(1モレ)を使用し、また
溶媒として1,3.4−トリメチル−2−イミダゾリジ
ノン−の代りに、1,3−ジエチル−4−メチル−2−
イミダゾリジノン100gを使用した以外は実施例1と
同様に反応させ、分析した。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8
33係であった。Example-3 Instead of the raw material N,N'-dimethyl-1,2-propanediamine, N,NI=diethyl-1,2-propanediamine 130.3.9 (1,n (1 mole) was used) In addition, 1,3-diethyl-4-methyl-2- was used instead of 1,3,4-trimethyl-2-imidazolidinone as a solvent.
The reaction and analysis were conducted in the same manner as in Example 1 except that 100 g of imidazolidinone was used. As a result, the production yield of 1,3-diethyl-4-methyl-2-imidazolidinone was 8
I was in Section 33.
実施例4〜10
溶媒の1.3.4− トリメチル−2−イミダゾリジノ
ンの代りに表1に示す各種溶媒100.9を用いた以外
実施例−1と同様に反応させ、分析した。Examples 4 to 10 The reaction and analysis were carried out in the same manner as in Example 1, except that various solvents shown in Table 1 100.9 were used instead of 1.3.4-trimethyl-2-imidazolidinone as the solvent.
それぞれの溶媒での生成収率を表−1に示した。The production yields for each solvent are shown in Table 1.
表 1
4 トルエン a15
1.2−ジクロルエタン 23.76 エチ
レングリコール 6α37 イソプロピ
ルアルコール 71.98 メチルイ
ソブチルケトン 83.59 N−メ
チル−2−ピロリドン 86.1rn
NN−ジメチルアセトアミド 82.8実施例−
11
500mlのステンレス製オートクレーブに、N、N’
−ジメチル−1,2−プロパンジアミン102.2.?
(100モル)、ウレア6.0.1g(1,011モル
)及び1,3゜4−トリメチル−2−イミダゾリジノン
1oo9を仕込んだ。昇温して、反応温度120’Cで
8時間反応させた。引き続き210″Cまで昇温しで、
3時間反応させた。Table 1 4 Toluene a15
1.2-Dichloroethane 23.76 Ethylene glycol 6α37 Isopropyl alcohol 71.98 Methyl isobutyl ketone 83.59 N-methyl-2-pyrrolidone 86.1rn
NN-dimethylacetamide 82.8 Example-
11 In a 500ml stainless steel autoclave, N, N'
-dimethyl-1,2-propanediamine 102.2. ?
(100 mol), 6.0.1 g (1,011 mol) of urea, and 109 ml of 1,3°4-trimethyl-2-imidazolidinone were charged. The temperature was raised and the reaction was carried out at a reaction temperature of 120'C for 8 hours. Continue to raise the temperature to 210″C,
The reaction was allowed to proceed for 3 hours.
反応終了後、ガスクロマトグラフィーにより1゜3.4
−トリメチル−2−イミダゾリジノンを定量した。1.
3.4−トリメチル−2−イミダゾリジノンの生成収率
は94.9 %であった。After the reaction was completed, the temperature was determined to be 1°3.4 by gas chromatography.
-Trimethyl-2-imidazolidinone was quantified. 1.
The yield of 3.4-trimethyl-2-imidazolidinone was 94.9%.
実施例−12
原料の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1303.9(1,00モレ)を使用し、溶媒と
して1,3,44hリメチルー2−イミダゾリジノンの
代りに1.3.4.4.5−ペンタメチル−2−イミダ
ゾリジノン100Iを使用した以外は実施例−11と同
様に反応させ、分析した。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
93.3係であった。Example-12 N,N',2-trimethyl-2,3-butanediamine 1303.9 (1,00 mole) was used instead of the raw material N,N-dimethyl-1,2-propanediamine, The reaction was carried out in the same manner as in Example 11, except that 1.3.4.4.5-pentamethyl-2-imidazolidinone 100I was used instead of 1,3,44h-limethyl-2-imidazolidinone as a solvent, and analysis was carried out. did. As a result, 1, 3.4.4.
The production yield of 5-pentamethyl-2-imidazolidinone was 93.3%.
実施列13〜16
溶媒の1.3.4−トリメチル−2−イミダゾリジノン
の代りに表2に示す各種溶媒100gを用いた以外実施
例11と同様に反応させ、分析した。それぞれの溶媒で
の1.3.4−トリメチル−2−イミダゾリジノンの生
成収率を表 2に示した。 表 2
16 N、N−ジメチルアセトアミド
95.2実施列−17
還流冷却器、温度計1滴下ロート及び撹拌機を91゜備
えた3 00 mlのガラス製フラスコ中にN、N’−
ジメチル−1,2−プロパンジアミン51.1g(0,
50モル)、ウレア60゜1#(1,00モル)及び1
,3.4− )ツメチル−2−イミダゾリジノン100
9を仕込んだ。滴下ロートにはN、NI−ジメチル−1
,2−プロパンジアミン51.IJ(0,50−E/し
)を用意した。Examples 13 to 16 The reaction and analysis were carried out in the same manner as in Example 11, except that 100 g of the various solvents shown in Table 2 were used instead of 1,3,4-trimethyl-2-imidazolidinone as the solvent. Table 2 shows the production yield of 1.3.4-trimethyl-2-imidazolidinone in each solvent. Table 2 16 N,N-dimethylacetamide
95.2 Example 17 In a 300 ml glass flask equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer at 91°, N, N'
Dimethyl-1,2-propanediamine 51.1g (0,
50 mol), urea 60° 1# (1,00 mol) and 1
, 3.4-) methyl-2-imidazolidinone 100
I prepared 9. In the dropping funnel, N, NI-dimethyl-1
,2-propanediamine51. IJ (0,50-E/shi) was prepared.
120°Cに昇温し反応させた。反応の進行とともにN
H3ガスが発生し、約2時聞役NH3ガスの発生が停止
した。引き続き210″Cまで昇温した。The temperature was raised to 120°C to cause a reaction. As the reaction progresses, N
H3 gas was generated, and the generation of NH3 gas stopped for about 2 hours. The temperature was subsequently raised to 210''C.
200°C付近から滴下ロートより、N、N’−ジメチ
ル−1,2−プロパンジアミンを約2時間かけて滴下し
た。その後1時間同温度で反応させた。N,N'-dimethyl-1,2-propanediamine was added dropwise from the dropping funnel at around 200°C over about 2 hours. Thereafter, the mixture was allowed to react at the same temperature for 1 hour.
反応終了マスをガスクロマトグラフィーにより1.3.
4−トリメチル−2−イミダゾリジノンを定量した。そ
の結果生成収率は、96.2%であった。The reaction completed mass was analyzed by gas chromatography in 1.3.
4-Trimethyl-2-imidazolidinone was quantified. As a result, the production yield was 96.2%.
この反応マスを減圧蒸留して、1,3.4=−)−ツメ
チル−2−イミダゾリジノン(沸点133〜135°C
/20torrの留分)215.4gを得た。This reaction mass was distilled under reduced pressure to obtain 1,3.4=-)-tmethyl-2-imidazolidinone (boiling point 133-135°C).
/20 torr fraction) 215.4 g was obtained.
実施列−18
[4のN、N’−ジメチル−1,2−プロパンジアミン
の代りに、N、N:2− )−ツメチル−2,3−ブタ
ンジアミン65.19(0,50モル)を仕込むととも
に、滴下ロートにN、 N: 2−トリメチル−2,3
−プタンン/ンの代りに1.3.4.4.5−ペンタメ
チル−2−イミダゾリジノン1oo9を使用し、その池
は実施例17と同様に反応させ、分析した。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95.4%であった。Example row-18 [In place of N,N'-dimethyl-1,2-propanediamine in 4, 65.19 (0.50 mol) of N,N:2-)-trimethyl-2,3-butanediamine was added. At the same time, add N, N: 2-trimethyl-2,3 to the dropping funnel.
1.3.4.4.5-Pentamethyl-2-imidazolidinone 1oo9 was used instead of -butane/n, and the pond was reacted and analyzed as in Example 17. the result,
The production yield of 1.3.4.4.5-pentamethyl-2-imidazolidinone was 95.4%.
実施例−19
原料のN、NI−ジメチル−1,2−プロパンジアミン
の代りに、 N、N’−ジエチル−1,2−プロパンジ
アミン65.1g(0,50モル)を反応フラスコに仕
込むとともに滴下ロートにN、N’−ジエチル−1,2
−プロパンジアミン65.1 # (0,50モル)を
用意した。Example-19 Instead of the raw material N,NI-dimethyl-1,2-propanediamine, 65.1 g (0.50 mol) of N,N'-diethyl-1,2-propanediamine was charged into the reaction flask. Add N,N'-diethyl-1,2 to the dropping funnel.
-Propanediamine 65.1 # (0.50 mol) was prepared.
また、溶媒として1.3.4−)−ツメチル−2−イミ
ダゾリジフ20代りに1.3−ジエチル−4−メチル−
2−イミダゾリジノン100J+を仕込み、その池は実
施例17と同様に反応させ、分析した。In addition, as a solvent, 1.3-diethyl-4-methyl-
100 J+ of 2-imidazolidinone was charged, and the pond was reacted and analyzed in the same manner as in Example 17.
その結果、l 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93.5%であった。As a result, the production yield of l 1,3-diethyl-4-methyl-2-imidazolidinone was 93.5%.
実施例20〜24
溶媒の1.3.4−トリメチル−2−イミダゾリジノン
の代りに表3に示す各種溶媒100.9を用いた以外は
、実施例−17と同様に反応させ分析した。それぞれの
溶媒での1.3.4−)−ツメチル−2−イミダゾリジ
ノンの生成収率を表2に示した。Examples 20 to 24 The reaction and analysis were carried out in the same manner as in Example 17, except that various solvents 100.9 shown in Table 3 were used instead of 1.3.4-trimethyl-2-imidazolidinone as the solvent. Table 2 shows the production yield of 1.3.4-)-tumethyl-2-imidazolidinone in each solvent.
表 3
20 テトラリン 4321 1
−クロロナフタリン 13−222 ジ
エチレングリコール 52.923 ヘ
キサメチルホスホルアミド 96・。Table 3 20 Tetralin 4321 1
-Chloronaphthalene 13-222 Diethylene glycol 52.923 Hexamethylphosphoramide 96.
Claims (6)
R^3及びR^4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ウレアとの反応により、式
(II) ▲数式、化学式、表等があります▼(II) (式中、R、R^1、R^2、R^3及びR^4は、式
( I )のR、R^1、R^2、R^3及びR^4と同
じ。)で示される2−イミダゾリジノン類を得るに際し
、極性溶媒の存在下180℃以上で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) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a lower alkyl group. R^1, R^2,
R^3 and R^4 are hydrogen atoms or lower alkyl groups, and at least one of them is a lower alkyl group. ) Due to the reaction between diamines and urea, the formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R, R^1, R^2, R^3 and R^ 4 is the same as R, R^1, R^2, R^3, and R^4 of formula (I). 1. A method for producing 2-imidazolidinones, which comprises reacting with:
学式、表等があります▼(II) (式中、R、R^1、R^2、R^3及びR^4は、式
( I )のR、R^1、R^2、R^3及びR^4と同
じ。)で示される2−イミダゾリジノン類である特許請
求の範囲第(1)項記載の方法。(2) Polar solvent is generated by reaction Formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R, R^1, R^2, R^3 and R^4 are , the same as R, R^1, R^2, R^3 and R^4 of formula (I).) The method according to claim (1), which is a 2-imidazolidinone represented by .
R^3及びR^4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ウレアとの反応により、式(
II) ▲数式、化学式、表等があります▼(II) (式中、R、R^1、R^2、R^3及びR^4は、式
( I )のR、R^1、R^2、R^3及びR^4と同
じ。)で示される2−イミダゾリジノン類を得るに際し
、極性溶媒の存在下に、ジアミン類/ウレアの仕込みモ
ル比が0.6〜1.2になるように仕込み、初期反応の
ウレア中間体の生成が完結するまでは140℃以下で反
応させ、引続き180℃以上に昇温して反応させること
を特徴とする2−イミダゾリジノン類の製造方法。(3) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a lower alkyl group. R^1, R^2,
R^3 and R^4 are hydrogen atoms or lower alkyl groups, and at least one of them is a lower alkyl group. ) The reaction between the diamines represented by the formula and urea results in the formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R, R^1, R^2, R^3 and R^4 are R, R^1, R of formula (I) When obtaining 2-imidazolidinones represented by ^2, R^3 and R^4), the molar ratio of diamines/urea charged is 0.6 to 1.2 in the presence of a polar solvent. Production of 2-imidazolidinones, characterized in that the reaction is carried out at 140°C or lower until the formation of the urea intermediate in the initial reaction is completed, and then the reaction is carried out by raising the temperature to 180°C or higher. Method.
学式、表等があります▼(II) (式中、R、R^1、R^2、R^3及びR^4は、式
( I )のR、R^1、R^2、R^3及びR^4と同
じ。)で示される2−イミダゾリジノン類である特許請
求の範囲第(3)項記載の方法(4) The polar solvent is produced by the reaction formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R, R^1, R^2, R^3 and R^4 are , the same as R, R^1, R^2, R^3 and R^4 of formula (I).) The method according to claim (3), which is a 2-imidazolidinone represented by
R^3及びR^4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ウレアとの反応により、式(
II) ▲数式、化学式、表等があります▼(II) (式中、R、R^1、R^2、R^3及びR^4は、式
( I )のR、R^1、R^2、R^3及びR^4と同
じ。)で示される2−イミダゾリジノン類を得るに際し
、極性溶媒の存在下にジアミン類/ウレアの仕込みモル
比がほぼ1/2になるように仕込み、初期反応のウレア
中間体の生成が完結するまでは140℃以下で反応させ
、引き続き180℃以上に昇温して全体のジアミン類/
ウレアのモル比がほぼ2/2になるようにジアミン類を
添加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。(5) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a lower alkyl group. R^1, R^2,
R^3 and R^4 are hydrogen atoms or lower alkyl groups, and at least one of them is a lower alkyl group. ) The reaction between the diamines represented by the formula and urea results in the formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R, R^1, R^2, R^3 and R^4 are R, R^1, R of formula (I) When obtaining the 2-imidazolidinones represented by ^2, R^3 and R^4), the molar ratio of diamines/urea was adjusted to approximately 1/2 in the presence of a polar solvent. The reaction is carried out at 140°C or lower until the formation of the urea intermediate in the initial reaction is completed, and then the temperature is raised to 180°C or higher to control the total diamines/
A method for producing 2-imidazolidinones, which comprises reacting while adding diamines so that the molar ratio of urea is approximately 2/2.
学式、表等があります▼(II) (式中、R、R^1、R^2、R^3及びR^4は、式
( I )のR、R^1、R^2、R^3及R^4と同じ
。)で示される2−イミダゾリジノン類である特許請求
の範囲第(5)項記載の方法。(6) Polar solvent is generated by the reaction Formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R, R^1, R^2, R^3 and R^4 are , the same as R, R^1, R^2, R^3 and R^4 of formula (I).) The method according to claim (5), wherein .
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61134888A JPH07103109B2 (en) | 1986-06-12 | 1986-06-12 | Method for producing 2-imidazolidinones |
US07/053,387 US4900820A (en) | 1986-06-12 | 1987-05-22 | Process for producing cyclic ureas |
IN405/MAS/87A IN165075B (en) | 1986-06-12 | 1987-06-02 | |
CA000538549A CA1286291C (en) | 1986-06-12 | 1987-06-02 | Process for producing cyclic ureas |
EP87108021A EP0249136A3 (en) | 1986-06-12 | 1987-06-03 | Process for producing cyclic ureas |
KR1019870005829A KR890003809B1 (en) | 1986-06-12 | 1987-06-09 | Process for preparation of cyclic urea |
IN74/MAS/89A IN167610B (en) | 1986-06-12 | 1989-01-27 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61134888A JPH07103109B2 (en) | 1986-06-12 | 1986-06-12 | Method for producing 2-imidazolidinones |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6289703A Division JP2702425B2 (en) | 1994-11-24 | 1994-11-24 | Method for producing 2-imidazolidinones |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62292761A true JPS62292761A (en) | 1987-12-19 |
JPH07103109B2 JPH07103109B2 (en) | 1995-11-08 |
Family
ID=15138856
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61134888A Expired - Lifetime JPH07103109B2 (en) | 1986-06-12 | 1986-06-12 | Method for producing 2-imidazolidinones |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH07103109B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007100047A1 (en) * | 2006-03-02 | 2007-09-07 | Ube Industries, Ltd. | Method for producing 2-imidazolidinone compound and 4,5-dialkoxy-2-imidazolidinone compound |
-
1986
- 1986-06-12 JP JP61134888A patent/JPH07103109B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007100047A1 (en) * | 2006-03-02 | 2007-09-07 | Ube Industries, Ltd. | Method for producing 2-imidazolidinone compound and 4,5-dialkoxy-2-imidazolidinone compound |
Also Published As
Publication number | Publication date |
---|---|
JPH07103109B2 (en) | 1995-11-08 |
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