JPS6326747B2 - - Google Patents
Info
- Publication number
- JPS6326747B2 JPS6326747B2 JP6758980A JP6758980A JPS6326747B2 JP S6326747 B2 JPS6326747 B2 JP S6326747B2 JP 6758980 A JP6758980 A JP 6758980A JP 6758980 A JP6758980 A JP 6758980A JP S6326747 B2 JPS6326747 B2 JP S6326747B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium
- temperature
- alkali
- selectivity
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003513 alkali Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000003518 caustics Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical class OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 7
- -1 N-cyanomethylaminoacetic acid alkali salt Chemical class 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- HAXVIVNBOQIMTE-UHFFFAOYSA-L disodium;2-(carboxylatomethylamino)acetate Chemical compound [Na+].[Na+].[O-]C(=O)CNCC([O-])=O HAXVIVNBOQIMTE-UHFFFAOYSA-L 0.000 description 9
- QGLKBDIZFCYGIX-UHFFFAOYSA-N N-(cyanomethyl)glycine Chemical compound OC(=O)CNCC#N QGLKBDIZFCYGIX-UHFFFAOYSA-N 0.000 description 8
- 150000001447 alkali salts Chemical class 0.000 description 8
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 5
- ZGSLLEXPYOIJLB-UHFFFAOYSA-M sodium;2-(cyanomethylamino)acetate Chemical compound [Na+].[O-]C(=O)CNCC#N ZGSLLEXPYOIJLB-UHFFFAOYSA-M 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006215 cyanomethylation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ZAWGLAXBGYSUHN-UHFFFAOYSA-M sodium;2-[bis(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CC([O-])=O ZAWGLAXBGYSUHN-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、イミノジ酢酸アルカリ塩の製造法に
関し、詳しくはＮ−シアノメチルアミノ酢酸アル
カリ塩を苛性アルカリの存在下で加水分解させる
ことにより、イミノジ酢酸アルカリ塩を製造する
方法に関する。
イミノジ酢酸は、キレート作用を持つ化合物と
しての用途のほか種々の有機薬品製造用原料とし
て有用であり、従来、アミノ酢酸ナトリウムを青
化ナトリウム及び、ホルムアルデヒドによつてカ
ルボキシメチル化する方法、或いはアミノ酢酸ナ
トリウムを当量のグリコロニトリルによつてシア
ノメチル化し、Ｎ−シアノメチルアミノ酢酸ナト
リウムを生成させ、次いで得られたＮ−シアノメ
チルアミノ酢酸ナトリウムを苛性アルカリの20〜
50重量％水溶液を添加して60℃乃至沸点の範囲で
加水分解する方法が知られている。
しかしながら、前者の方法では、アミノ酢酸ナ
トリウムのカルボキシメチル化反応が進行すると
同時に、アンモニアが副生し、このアンモニアは
未反応の青化ナトリウムやホルムアルデヒドと反
応して、あらたに、アミノ酢酸ナトリウムを生成
する。
また、生成したイミノジ酢酸ナトリウムが更に
反応して、ニトリロトリ酢酸ナトリウムを生成す
る反応も併行し、結局、生成物はアミノ酢酸ナト
リウム、イミノジ酢酸ナトリウム及び、ニトリロ
トリ酢酸ナトリウムの混合物となるので、イミノ
ジ酢酸ナトリウムの生成率すなわち選択率が非常
に低くなる。
この前者の方法にくらべて後者の方法は、より
高い選択率で目的物のイミノジ酢酸ナトリウムが
得られるが、いまだ、充分に満足すべきものでは
ない。すなわち、アミノ酢酸ナトリウムをグリコ
ロニトリルによりシアノメチル化する工程の成績
は選択率、収率ともにほぼ極限に達しているが、
後段の加水分解工程を従来の反応条件で実施した
場合は、なお、不満足な選択率しか得られない。
本発明者等は、イミノジ酢酸アルカリ塩を高選
択率で製造する方法について種々検討し、本発明
を完成した。
すなわち、本発明は、Ｎ−シアノメチルアミノ
酢酸アルカリ塩を苛性アルカリで加水分解してイ
ミノジ酢酸アルカリ塩を製造するにあたり、Ｎ−
シアノメチルアミノ酢酸アルカリ塩と苛性アルカ
リとの混合水溶液を、あらかじめ60℃未満の温度
に少くとも５分間保持し、次いで60℃乃至沸点の
温度に加熱することにより、該加水分解を行うこ
とを特徴とするイミノジ酢酸アルカリ塩の製造法
を骨子とするものである。
本発明の方法について更に詳細に説明すれば、
本発明に用いるＮ−シアノメチルアミノ酢酸アル
カリ塩は、例えば、前述のように、アミノ酢酸ナ
トリウムをグリコロニトリルでシアノメチル化す
る方法によつて製造できる。この方法によつて得
られる生成物は水溶液として得られるため、この
水溶液を本発明の反応に供することができる。ま
たその他の方法で製造したものをも使用すること
ができる。
本発明に使用するＮ−シアノメチルアミノ酢酸
アルカリ塩水溶液の濃度は、必ずしも制限はない
が通常５〜50重量％程度であることが好ましい。
このＮ−シアノメチルアミノ酢酸アルカリ塩を
加水分解するために使用する苛性アルカリとして
は、通常、水酸化ナトリウム又は水酸化カリウム
を挙げることができる。その使用量は、Ｎ−シア
ノメチルアミノ酢酸アルカリ塩に対してモル比で
1.1〜1.5倍程度であればよい。
本発明の実施にあたり、Ｎ−シアノメチルアミ
ノ酢酸アルカリ塩と苛性アルカリとの混合水溶液
を、あらかじめ60℃未満の温度に少くとも５分間
保持する際、Ｎ−シアノメチルアミノ酢酸アルカ
リ塩水溶液に撹拌下、苛性アルカリ水溶液を添加
混合すると、添加と共に急激な発熱があつて昇温
するため、この際には、苛性アルカリの添加速度
を調節する方法、あるいはそれとともに冷却を行
なう等によつて反応液の温度を60℃未満に維持す
ればよい。
次に加水分解反応の温度と選択率との関係につ
き実験に基づいて詳細に説明する。
アミノ酢酸ナトリウムとグリコロニトリルとの
当モル混合物の15重量％水溶液を45℃で30分間撹
拌反応させてシアノメチル化し、得られた生成物
に下記表−１に示された温度で1.1モル比の15重
量％水酸化ナトリウム（Ｎ−シアノメチルアミノ
酢酸ナトリウムに対して1.1モル）水溶液を添加
して、表−１に示した温度（第１表に保持温度と
記す）に15分間保持したのち、液温を100℃に上
げて５時間反応させた。得られた反応液を分析し
た結果を表−１及び第１図に示す。
The present invention relates to a method for producing an alkali salt of iminodiacetate, and more particularly to a method for producing an alkali salt of iminodiacetate by hydrolyzing an alkali salt of N-cyanomethylaminoacetate in the presence of a caustic alkali. Iminodiacetic acid is useful not only as a compound with a chelating effect but also as a raw material for producing various organic drugs. Sodium is cyanomethylated with an equivalent amount of glycolonitrile to form sodium N-cyanomethylaminoacetate, and the resulting sodium N-cyanomethylaminoacetate is then dissolved in a caustic alkali solution containing
A method is known in which a 50% by weight aqueous solution is added and hydrolyzed at a temperature ranging from 60°C to the boiling point. However, in the former method, as the carboxymethylation reaction of sodium aminoacetate progresses, ammonia is produced as a by-product, and this ammonia reacts with unreacted sodium cyanide and formaldehyde to newly generate sodium aminoacetate. do. In addition, the produced sodium iminodiacetate further reacts to produce sodium nitrilotriacetate, and in the end, the product becomes a mixture of sodium aminoacetate, sodium iminodiacetate, and sodium nitrilotriacetate. The production rate, that is, the selectivity, becomes very low. Compared to the former method, the latter method yields the target product, sodium iminodiacetate, with a higher selectivity, but is still not fully satisfactory. In other words, the results of the process of cyanomethylating sodium aminoacetate with glycolonitrile have reached almost the limit in both selectivity and yield.
If the subsequent hydrolysis step is carried out under conventional reaction conditions, an unsatisfactory selectivity is still obtained. The present inventors conducted various studies on methods for producing alkali iminodiacetic acid salts with high selectivity, and completed the present invention. That is, the present invention provides a method for producing an alkali salt of iminodiacetic acid by hydrolyzing an alkali salt of N-cyanomethylaminoacetic acid with a caustic alkali.
The hydrolysis is carried out by holding an aqueous mixed solution of an alkali cyanomethylaminoacetic acid salt and a caustic alkali at a temperature below 60°C for at least 5 minutes, and then heating it to a temperature between 60°C and the boiling point. This method is based on a method for producing an alkali salt of iminodiacetic acid. To explain the method of the present invention in more detail,
The alkali salt of N-cyanomethylaminoacetate used in the present invention can be produced, for example, by the method of cyanomethylating sodium aminoacetate with glycolonitrile, as described above. Since the product obtained by this method is obtained as an aqueous solution, this aqueous solution can be subjected to the reaction of the present invention. Moreover, those produced by other methods can also be used. The concentration of the aqueous N-cyanomethylaminoacetic acid alkali salt solution used in the present invention is not necessarily limited, but it is usually preferably about 5 to 50% by weight. The caustic alkali used to hydrolyze this alkali salt of N-cyanomethylaminoacetic acid can usually include sodium hydroxide or potassium hydroxide. The amount used is in molar ratio to N-cyanomethylaminoacetic acid alkali salt.
It is sufficient if it is about 1.1 to 1.5 times. In carrying out the present invention, when a mixed aqueous solution of an alkali N-cyanomethylaminoacetic acid salt and a caustic alkali is kept at a temperature below 60°C for at least 5 minutes, the aqueous solution of an alkali N-cyanomethylaminoacetic acid salt is added to the aqueous solution of an alkali N-cyanomethylaminoacetic acid under stirring. When a caustic alkali aqueous solution is added and mixed, a rapid heat generation occurs and the temperature rises as the solution is added, so in this case, the reaction solution should be controlled by adjusting the addition rate of the caustic alkali or cooling at the same time. The temperature should be maintained below 60°C. Next, the relationship between the temperature and selectivity of the hydrolysis reaction will be explained in detail based on experiments. A 15% by weight aqueous solution of an equimolar mixture of sodium aminoacetate and glycolonitrile was stirred and reacted at 45°C for 30 minutes to undergo cyanomethylation, and the resulting product was reacted with a 1.1 molar ratio at the temperature shown in Table 1 below. After adding a 15% by weight aqueous solution of sodium hydroxide (1.1 mol based on sodium N-cyanomethylaminoacetate) and maintaining the temperature shown in Table 1 (denoted as holding temperature in Table 1) for 15 minutes, The liquid temperature was raised to 100°C and the reaction was carried out for 5 hours. The results of analyzing the obtained reaction solution are shown in Table 1 and FIG.
【表】
第１図中横軸はあらかじめ保持する温度を表わ
し、縦軸は選択率（wt％）を表わし、曲線１は
イミノジ酢酸ナトリウムの選択率を、曲線２はニ
トリロトリ酢酸ナトリウムの選択率を、曲線３は
アミノ酢酸ナトリウムの選択率を表わす。
表−１及び第１図から、あらかじめ保持する温
度が60℃より高い場合は、イミノジ酢酸ナトリウ
ムへの選択率が急激に低下し、不純物、特にニト
リロトリ酢酸ナトリウムへの選択率が上昇するの
に対し、60℃未満、特に50℃以下の場合ではイミ
ノジ酢酸ナトリウムへの選択率が90重量％と高い
ことが理解される。
したがつて本発明方法では、加水分解反応に際
し、あらかじめ温度を60℃未満、特に好ましくは
20℃〜50℃に保持する必要がある。
上記温度にあらかじめ保持する時間は、反応温
度によつて多少相違し、例えば50℃では５分間、
30℃では15分間程度で充分であるが少なくとも５
分間以上とする必要がある。５分間以下の場合に
は、高選択率が得られない。
本発明方法では、上記のあらかじめ60℃未満の
温度に少くとも５分間保持した後、従来方法にお
いておこなわれている、60℃乃至沸点の温度で数
時間加水分解を行ない反応を完結させればよい。
以下に本発明を実施例によりさらに詳細に説明
する。
実施例１〜３及び比較例１〜３
Ｎ−シアノメチルアミノ酢酸ナトリウムの製造
撹拌機、温度計、滴下ロートおよび還流凝縮器
を有する500mlの四ツ口フラスコに、水189ｇに溶
解したアミノ酢酸ナトリウム48.5ｇ（0.5モル）
水溶液を仕込み、この水溶液に上記滴下ロートか
らグリコロニトリル57ｇの50％水溶液を加え、45
℃30分間撹拌し、Ｎ−シアノメチルアミノ酢酸ナ
トリウム水溶液を得た。
イミノジ酢酸ナトリウムの製造
上記で得られたＮ−シアノメチルアミノ酢酸ナ
トリウム水溶液を、氷水浴中で表−２に示す温度
に調整し、これに該温度を保持するように160ｇ
の水酸化ナトリウム（0.6モル）の15重量％水溶
液を、新らしく設置した滴下ロートから徐々に加
え、表−２に示した時間該温度に保持し、次いで
浴温を上昇させて反応液温度100℃に保持して反
応を終了した。この反応中上記撹拌機により反応
液を撹拌した。
反応結果を表−２に示した。[Table] In Figure 1, the horizontal axis represents the pre-maintained temperature, the vertical axis represents the selectivity (wt%), curve 1 represents the selectivity of sodium iminodiacetate, and curve 2 represents the selectivity of sodium nitrilotriacetate. , curve 3 represents the selectivity of sodium aminoacetate. From Table 1 and Figure 1, when the pre-maintained temperature is higher than 60℃, the selectivity to sodium iminodiacetate decreases rapidly, while the selectivity to impurities, especially sodium nitrilotriacetate, increases. It is understood that when the temperature is below 60°C, especially below 50°C, the selectivity to sodium iminodiacetate is as high as 90% by weight. Therefore, in the method of the present invention, the temperature is lower than 60°C, particularly preferably, in advance during the hydrolysis reaction.
It is necessary to maintain the temperature between 20℃ and 50℃. The time to maintain the above temperature in advance varies somewhat depending on the reaction temperature, for example, 5 minutes at 50°C,
At 30℃, 15 minutes is sufficient, but at least 5 minutes
Must be at least 1 minute. If the time is less than 5 minutes, high selectivity cannot be obtained. In the method of the present invention, after holding the above-mentioned temperature below 60°C for at least 5 minutes, the reaction can be completed by performing hydrolysis for several hours at a temperature of 60°C to the boiling point, which is carried out in the conventional method. . The present invention will be explained in more detail below using examples. Examples 1 to 3 and Comparative Examples 1 to 3 Production of sodium N-cyanomethylaminoacetate Sodium aminoacetate dissolved in 189 g of water in a 500 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser. 48.5g (0.5 mole)
Prepare an aqueous solution, add a 50% aqueous solution of 57 g of glycolonitrile to this aqueous solution from the above dropping funnel,
The mixture was stirred for 30 minutes at °C to obtain an aqueous solution of sodium N-cyanomethylaminoacetate. Production of sodium iminodiacetate The aqueous solution of sodium N-cyanomethylaminoacetate obtained above was adjusted to the temperature shown in Table 2 in an ice water bath, and 160 g
A 15% by weight aqueous solution of sodium hydroxide (0.6 mol) was gradually added from a newly installed dropping funnel, maintained at the temperature for the time shown in Table 2, and then the bath temperature was raised until the reaction solution temperature was 100%. The reaction was completed by maintaining the temperature at °C. During this reaction, the reaction solution was stirred using the above-mentioned stirrer. The reaction results are shown in Table-2.
【表】
本発明方法に対する比較のために、あらかじめ
保持する温度及び時間を従来法の温度及び時間で
行い、得られた結果を表−２にあわせて記載し
た。
表−２から本発明方法により、あらかじめ60℃
未満に少くとも５分間保持することにより、イミ
ノジ酢酸ナトリウムの選択率が89.3重量％以上と
いう高率で得られることが明らかである。[Table] For comparison with the method of the present invention, the temperature and time of holding in advance were carried out using the conventional method, and the obtained results are shown in Table 2. From Table 2, it can be seen that by the method of the present invention, 60℃
It is clear that a high selectivity of sodium iminodiacetate of 89.3% by weight or more can be obtained by holding the sample for at least 5 minutes.
第１図は、選択率曲線を示す図である。
１……イミノジ酢酸ナトリウムの選択率を示す
曲線、２……ニトリロ酢酸ナトリウムの選択率を
示す曲線、３……アミノ酢酸ナトリウムの選択率
を示す曲線。
FIG. 1 is a diagram showing a selectivity curve. 1...Curve showing the selectivity of sodium iminodiacetate, 2...Curve showing the selectivity of sodium nitriloacetate, 3...Curve showing the selectivity of sodium aminoacetate.
Claims (1)
性アルカリで加水分解してイミノジ酢酸アルカリ
塩を製造するにあたり、Ｎ−シアノメチルアミノ
酢酸アルカリ塩と苛性アルカリとの混合水溶液
を、あらかじめ60℃未満の温度に少くとも５分間
保持し、次いで60℃乃至沸点の温度に加熱するこ
とにより、該加水分解を行うことを特徴とするイ
ミノジ酢酸アルカリ塩の製造法。1. When hydrolyzing N-cyanomethylaminoacetic acid alkali salt with caustic alkali to produce iminodiacetic acid alkali salt, a mixed aqueous solution of N-cyanomethylaminoacetic acid alkali salt and caustic alkali is heated to a temperature below 60°C in advance. A method for producing an alkali iminodiacetic acid salt, characterized in that the hydrolysis is carried out by holding for at least 5 minutes and then heating to a temperature of 60° C. to the boiling point.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6758980A JPS56164150A (en) | 1980-05-21 | 1980-05-21 | Preparation of alkali salt of iminodiacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6758980A JPS56164150A (en) | 1980-05-21 | 1980-05-21 | Preparation of alkali salt of iminodiacetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56164150A JPS56164150A (en) | 1981-12-17 |
| JPS6326747B2 true JPS6326747B2 (en) | 1988-05-31 |
Family
ID=13349244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6758980A Granted JPS56164150A (en) | 1980-05-21 | 1980-05-21 | Preparation of alkali salt of iminodiacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56164150A (en) |
-
1980
- 1980-05-21 JP JP6758980A patent/JPS56164150A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56164150A (en) | 1981-12-17 |
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