JPH0745452B2 - Method for producing aqueous acetoacetamide solution - Google Patents
Method for producing aqueous acetoacetamide solutionInfo
- Publication number
- JPH0745452B2 JPH0745452B2 JP28789786A JP28789786A JPH0745452B2 JP H0745452 B2 JPH0745452 B2 JP H0745452B2 JP 28789786 A JP28789786 A JP 28789786A JP 28789786 A JP28789786 A JP 28789786A JP H0745452 B2 JPH0745452 B2 JP H0745452B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- acetoacetamide
- aqueous
- diketene
- reaction
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は医薬、農薬、色素等の各種薬品を製造するため
の中間原料として有用なアセトアセトアミド類水溶液の
製造法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing an aqueous acetoacetamide solution useful as an intermediate raw material for producing various chemicals such as medicines, agricultural chemicals, and dyes.
（従来技術） ジケテンとアンモニア水溶液又は脂肪族第一級又は第二
級アミン水溶液とを反応させアセトアセトアミド類水溶
液を得る事は公知である。例えば特公昭58-30295におい
ては、生成したアセトアセトアミドの分解を防止するた
めに該反応をpH8〜10で行う事が記載されている。(Prior Art) It is known to obtain an aqueous acetoacetamide solution by reacting diketene with an aqueous ammonia solution or an aqueous aliphatic primary or secondary amine solution. For example, Japanese Examined Patent Publication (Kokoku) No. 58-30295 discloses that the reaction is carried out at a pH of 8 to 10 in order to prevent decomposition of the produced acetoacetamide.
（発明が解決しようとする問題点） 本発明者は前記のpH8〜10での反応について検討した結
果、pH8〜10の反応では、生成したアセトアセトアミド
類の分解よりも二量体が相当量副生し、このために、ア
セトアセトアミド類の収率の低下、あるいは品質の低下
を持たらし、更にこれが経時安定性にも悪影響を及すと
いう問題点のあることを見い出した。(Problems to be Solved by the Invention) As a result of examining the reaction at the above pH 8 to 10, the present inventor found that in the reaction at pH 8 to 10, the dimer was a considerable amount of by-products rather than the decomposition of the produced acetoacetamide. Therefore, it has been found that there is a problem that the yield of acetoacetamide or the quality thereof deteriorates due to this, and this also adversely affects the stability over time.
本発明の目的はこのような二量体の副生を抑制し、効率
よく高品質のアセトアセトアミド類水溶液を製造する方
法を提供するものである。An object of the present invention is to provide a method for suppressing the by-product of such a dimer and efficiently producing a high-quality acetoacetamide aqueous solution.
（問題点を解決するための手段） 本発明はジケテンとアンモニア水溶液又は脂肪族第一級
又は第二級アミン水溶液とを反応させアセトアセトアミ
ド類水溶液を製造するにあたり、反応液中のpH値を５〜
７に維持しながら反応させることを特徴とするアセトア
セトアミド類水溶液の製造方法である。(Means for Solving Problems) In the present invention, when a diketene is reacted with an aqueous ammonia solution or an aqueous aliphatic primary or secondary amine solution to produce an aqueous acetoacetamide solution, the pH value in the reaction solution is adjusted to 5%. ~
The method for producing an aqueous acetoacetamide solution is characterized in that the reaction is carried out while maintaining 7.
本発明の反応は、Ｎ−メチル−アセトアセトアミドの場
合を例にとれば、以下の式で示される。Taking the case of N-methyl-acetoacetamide as an example, the reaction of the present invention is represented by the following formula.
本発明の脂肪族第一級又は第二級アミンには通常Ｃ1〜
Ｃ6程度のアミンが好適に使用される。 The aliphatic primary or secondary amine of the present invention usually has C 1-
An amine having a C 6 level is preferably used.
又、これらアミンの水溶液濃度は、目的とするアセトア
セトアミド水溶液の濃度あるいは反応の制御の面から適
宜選択することができるが通常10〜60wt％程度で使用さ
れる。The aqueous solution concentration of these amines can be appropriately selected from the viewpoint of the concentration of the desired aqueous acetoacetamide solution or the control of the reaction, but it is usually used at about 10 to 60 wt%.
アセトアセトアミド類の具体例としては、アセトアセト
アミド、Ｎ−メチル−アセトアセトアミド、N,N−ジメ
チルアセトアミド、Ｎ−エチルアセトアセトアミド、N,
N−ジエチルアセトアセトアミド等が挙げられる。Specific examples of acetoacetamides include acetoacetamide, N-methyl-acetoacetamide, N, N-dimethylacetamide, N-ethylacetoacetamide, N,
N-diethylacetoacetamide and the like can be mentioned.
本発明において、反応液中のpHを５〜７、好ましくは5.
5〜6.5に維持する方法としては、酢酸等の添加により調
節することも可能であるが、反応成分であるジケテンと
アミンの仕込みモル比をコントロールすることによって
調節することが好ましい。In the present invention, the pH of the reaction solution is 5 to 7, preferably 5.
As a method of maintaining 5 to 6.5, it can be adjusted by adding acetic acid or the like, but it is preferably adjusted by controlling the charged molar ratio of the reaction components diketene and amine.
即ち、仕込みのアミンに対し、ジケテンを若干過剰に仕
込む事により、反応液のpHを５〜７に調製することがで
きる。That is, the pH of the reaction solution can be adjusted to 5 to 7 by charging diketene in a slight excess with respect to the charged amine.
なお、アミンとジケテンの反応器への仕込みは所定のモ
ル比で同時に連続的あるいは間欠的に添加されることが
好ましいが、pH調整が可能な範囲であれば同時仕込であ
る必要はない。The amine and the diketene are preferably charged in a reactor at a predetermined molar ratio continuously or intermittently at the same time, but simultaneous charging is not necessary as long as the pH can be adjusted.
又、仕込のモル比は反応液のpHを測定しながら微調整す
ることにより更に十分に制御することができる。Further, the molar ratio of the charge can be more sufficiently controlled by finely adjusting it while measuring the pH of the reaction solution.
本発明の方法において反応開始にあたっては、前もって
調製されたアセトアセトアミド類の水溶液をあらかじめ
反応器に加えておく事が撹拌の容易さ、温度調節等反応
の制御の面から好ましい。In starting the reaction in the method of the present invention, it is preferable to add an aqueous solution of acetoacetamide prepared in advance to the reactor in advance from the viewpoints of easiness of stirring and control of reaction such as temperature adjustment.
本発明は通常20〜60℃程度で実施される。60℃以上では
二量体の副生増加、原料アミンの損失増加等により好ま
しくない。The present invention is usually carried out at about 20-60 ° C. When the temperature is 60 ° C or higher, it is not preferable because the dimer is increased as a by-product and the loss of the raw material amine is increased.
若干過剰に仕込まれたジケテンはアセトンと炭酸ガスに
分解する。これらは品質の安定性等に特に悪影響を及す
ものではないが反応終了後、減圧単蒸留等により除去し
ておく事がドラム貯蔵の場合等に好ましい。The diketene charged in a slight excess decomposes into acetone and carbon dioxide. These do not particularly adversely affect the stability of quality and the like, but it is preferable to remove them by vacuum distillation or the like after completion of the reaction in the case of drum storage.
（発明の効果） 本発明の方法により、二量体の副生率が著るしく減少
し、ジケテンの使用率が向上するとともに高品質のアセ
トアセトアミド類水溶液が得られるようになった。(Effect of the Invention) By the method of the present invention, the by-product rate of dimers is remarkably reduced, the usage rate of diketene is improved, and a high-quality acetoacetamide aqueous solution can be obtained.
又、得られたアセトアセトアミド類は、40℃で３ケ月間
放置しても当初存在していたアセトアセトアミド類の含
量低下は非常に小さく経時安定性の高いものであった。Further, the obtained acetoacetamide had a very small decrease in the content of the acetoacetamide which was initially present even after standing at 40 ° C. for 3 months, and had high stability over time.
（実施例） 以下、本発明を実施例比較例により更に具体的に説明す
る。(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
なお、％はいづれも重量パーセントを表す。In addition, each% represents weight percent.
比較例１ 温度計,pH計及びミクロフイダーを備えた撹拌機付き1I
セパラブルフラスコに65％のＮ−メチル−アセトアセト
アミド水溶液100.0gを張り込み、50℃に加熱し、撹拌と
冷却とを行いつつ、ジケテン254.2g（3.02モル）と40％
モノメチルアミン278.7g（3.59モル）をミクロフイダー
でpH9.9〜10.0及び温度を48〜52℃に調節しながら同時
添加する。（ジケテン／モノメチルアミンのモル比は0.
84）添加終了後、副生したアセトンと炭酸ガスを減圧蒸
留で除去した。Comparative Example 1 1I equipped with a stirrer equipped with a thermometer, a pH meter, and a microfuser
A separable flask was charged with 100.0 g of a 65% aqueous solution of N-methyl-acetoacetamide, heated to 50 ° C., and stirred and cooled to give 254.2 g (3.02 mol) of diketene and 40% of diketene.
278.7 g (3.59 mol) of monomethylamine are added at the same time while adjusting the pH to 9.9 to 10.0 and the temperature to 48 to 52 ° C. with a micro feeder. (The molar ratio of diketene / monomethylamine is 0.
84) After the addition was completed, acetone and carbon dioxide produced as by-products were removed by vacuum distillation.
得られた反応液をガスクロマトグラフィーにより分析し
た結果、Ｎ−メチル−アセトアセトアミド（以下MAAMと
いう）水溶液のMAAM濃度は64.3％であり、副生物である
二量体の濃度は8.0％であった。As a result of analyzing the obtained reaction solution by gas chromatography, the N-methyl-acetoacetamide (hereinafter referred to as MAAM) aqueous solution had a MAAM concentration of 64.3% and a by-product dimer concentration of 8.0%. .
比較例２ ジケテン375.7g（4.47モル）、40％モノメチルアミン35
4.1g（4.56モル）を使用し（ジケテン／モノメチルアミ
ンのモル比は0.98）、pH8.0〜8.1に調整した他は比較例
１と同様の実験を行った。得られたMAAM水溶液のMAAM濃
度は65.4％であり、二量体の濃度は1.1％であった。Comparative Example 2 375.7 g (4.47 mol) of diketene, 40% monomethylamine 35
The same experiment as in Comparative Example 1 was carried out except that 4.1 g (4.56 mol) was used (the diketene / monomethylamine molar ratio was 0.98) and the pH was adjusted to 8.0 to 8.1. The MAAM concentration of the obtained MAAM aqueous solution was 65.4%, and the concentration of the dimer was 1.1%.
実施例１ ジケテン398.7g（4.74モル）、40％モノメチルアミン35
4.1g（4.56モル）を使用し（ジケテン／モノメチルアミ
ンのモル比は1.04）、pH6.9〜7.0に調整した他は比較例
１と同様の実験を行った。Example 1 398.7 g (4.74 mol) of diketene, 40% monomethylamine 35
The same experiment as in Comparative Example 1 was performed except that 4.1 g (4.56 mol) was used (the diketene / monomethylamine molar ratio was 1.04) and the pH was adjusted to 6.9 to 7.0.
得られたMAAM水溶液のMAAM濃度は66.1％であり、二量体
の濃度は0.26％であった。The MAAM concentration of the obtained MAAM aqueous solution was 66.1%, and the concentration of the dimer was 0.26%.
実施例２ ジケテン419.9g（4.99モル）、40％モノメチルアミン34
2.9g（4.42モル）を使用し（ジケテン／モノメチルアミ
ンのモル比は1.13）、pH5.6〜5.8に調整した他は比較例
１と同様の実験を行った。Example 2 419.9 g (4.99 mol) of diketene, 40% monomethylamine 34
The same experiment as in Comparative Example 1 was carried out except that 2.9 g (4.42 mol) was used (the diketene / monomethylamine molar ratio was 1.13) and the pH was adjusted to 5.6 to 5.8.
得られたMAAM水溶液のMAAM濃度は66.3％であり二量体の
濃度は0.12％であった。The MAAM concentration of the obtained MAAM aqueous solution was 66.3%, and the concentration of the dimer was 0.12%.
実施例３ 実施例１と同様の仕込比率、pH調整、反応温度で第１図
に示した装置で反応を連続的に行った。Example 3 The reaction was continuously carried out in the same apparatus as in Example 1 with the same charge ratio, pH adjustment and reaction temperature as shown in FIG.
得られたMAAM水溶液の品質は実施例１と殆んど同じであ
った。The quality of the obtained MAAM aqueous solution was almost the same as in Example 1.
（経時安定性の測定） 比較例２及び実施例２で得られたMAAM水溶液をガラス製
のアンプルに封入し、40℃で放置したときのMAAM含量の
変化を測定した。(Measurement of stability over time) The MAAM aqueous solutions obtained in Comparative Example 2 and Example 2 were enclosed in glass ampoules, and changes in MAAM content when left at 40 ° C were measured.
【図面の簡単な説明】 第１図は実施例３で使用したMAAM水溶液製造装置の概略
図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a MAAM aqueous solution production apparatus used in Example 3.
Claims (1)
一級又は第二級アミン水溶液とを反応させアセトアセト
アミド水溶液を製造するにあたり、反応液中のpH値を５
〜７に維持しながら反応させることを特徴とするアセト
アセトアミド類水溶液の製造方法1. When a diketene is reacted with an aqueous ammonia solution or an aqueous aliphatic primary or secondary amine solution to produce an aqueous acetoacetamide solution, the pH value in the reaction solution is adjusted to 5%.
Method for producing an aqueous acetoacetamide solution characterized by reacting while maintaining
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28789786A JPH0745452B2 (en) | 1986-12-03 | 1986-12-03 | Method for producing aqueous acetoacetamide solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28789786A JPH0745452B2 (en) | 1986-12-03 | 1986-12-03 | Method for producing aqueous acetoacetamide solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63141950A JPS63141950A (en) | 1988-06-14 |
| JPH0745452B2 true JPH0745452B2 (en) | 1995-05-17 |
Family
ID=17723127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28789786A Expired - Lifetime JPH0745452B2 (en) | 1986-12-03 | 1986-12-03 | Method for producing aqueous acetoacetamide solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745452B2 (en) |
-
1986
- 1986-12-03 JP JP28789786A patent/JPH0745452B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63141950A (en) | 1988-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH06172277A (en) | Manufacturing of ethylenediamine tri acetic acid | |
| JPH05500500A (en) | Method for preparing 2,4,6-triiodo-5-amino-N-alkylisophthalamide acid and 2,4,6-triiodo-5-aminoisophthalamide compound | |
| JPH0745452B2 (en) | Method for producing aqueous acetoacetamide solution | |
| US1581621A (en) | Production of amide acid sulphates from nitriles | |
| JPH10158238A (en) | Production of n-methyl-2-pyrrolidone | |
| US11046705B1 (en) | Method for preparing etodolac methyl ester | |
| US4322551A (en) | Process for preparing aromatic amide antioxidants | |
| KR101141389B1 (en) | Process for the production of dtpa-bis anhydride | |
| JP2642466B2 (en) | Method for producing aminoacetonitrile | |
| JP3011493B2 (en) | Method for producing 4-alkyl-3-thiosemicarbazide | |
| JPH029851A (en) | Synthesis of secondary formamide | |
| JP3503842B2 (en) | Method for producing alkanolamide | |
| JPS5811867B2 (en) | Method for producing 5,5-dimethyl-4-phenyloxazolidin-2-one derivative | |
| JP4092739B2 (en) | Novel process for producing azoester compounds | |
| DE3872136T2 (en) | METHOD FOR PRODUCING DICHLORBERSTEINSAUREDIALKYLESTER. | |
| JP3412246B2 (en) | Method for producing 2-halogeno-1-alkene derivative | |
| SU727634A1 (en) | Method of preparing n-(2-aza-2-nitroalkyl) amides | |
| JPS63122652A (en) | Production of n-alkylalkylenediamine | |
| JP2582889B2 (en) | Production method of high-purity aminosulfenyl chloride | |
| JPH0759570B2 (en) | Method for producing 2-oxazolidinones | |
| JPS60112771A (en) | Preparation of isonicotinic acid anilide derivative | |
| JP2824781B2 (en) | Method for producing N, N'-bis- (2-hydroxyethyl) -piperazine | |
| KR940011527B1 (en) | Improve method diarkyl propanedi imidate dihydrohalaide | |
| SU649707A1 (en) | Method of obtaining n-(2-aza-2-nitroalkyl)-n-alkylamides | |
| JP2526413B2 (en) | Alkylenediphenyldisulfonylfluoride and method for synthesizing the same |