JPH04279595A - Production of n-phosphonomethylglycine - Google Patents
Production of n-phosphonomethylglycineInfo
- Publication number
- JPH04279595A JPH04279595A JP6402691A JP6402691A JPH04279595A JP H04279595 A JPH04279595 A JP H04279595A JP 6402691 A JP6402691 A JP 6402691A JP 6402691 A JP6402691 A JP 6402691A JP H04279595 A JPH04279595 A JP H04279595A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- phosphonomethylglycine
- aminomethylphosphonic acid
- reaction
- glycolonitrile
- 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
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 claims abstract description 33
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 5
- MGRVRXRGTBOSHW-UHFFFAOYSA-N (aminomethyl)phosphonic acid Chemical compound NCP(O)(O)=O MGRVRXRGTBOSHW-UHFFFAOYSA-N 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- OBESRABRARNZJB-UHFFFAOYSA-N aminomethanesulfonic acid Chemical compound NCS(O)(=O)=O OBESRABRARNZJB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004009 herbicide Substances 0.000 abstract description 3
- 230000002363 herbicidal effect Effects 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- -1 diethyl bromide malonate Chemical compound 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003054 catalyst 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
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、除草剤として有用なＮ
−ホスホノメチルグリシンの新規な製造方法に関する。[Industrial Application Field] The present invention relates to N, which is useful as a herbicide.
-Regarding a novel method for producing phosphonomethylglycine.
【０００２】0002
【従来の技術】Ｎ−ホスホノメチルグリシンおよびその
農薬として有効なその塩類は、生物的に分解され、また
少量の使用で除草剤として有効な化合物であり、広く使
用されている。Ｎ−ホスホノメチルグリシンの製造方法
は多数知られているが、本発明に関連する技術として、
原料にアミノメチルホスホン酸を使用するＮ−ホスホノ
メチルグリシンの製造方法もいくつか知られている。BACKGROUND OF THE INVENTION N-phosphonomethylglycine and its salts, which are effective as pesticides, are biodegradable compounds and are effective as herbicides when used in small amounts, and are widely used. Although many methods for producing N-phosphonomethylglycine are known, the following techniques are related to the present invention:
Some methods for producing N-phosphonomethylglycine using aminomethylphosphonic acid as a raw material are also known.
【０００３】例えば、グリオキザール水溶液中にアミノ
メチルホスホン酸を４０〜４５℃で添加したのち加熱す
る方法（特開昭 ６２−６１９９２ 号）、同じくアミ
ノメチルホスホン酸とグリオキザールを原料として二酸
化硫黄の存在下に反応させる方法（欧州特許第 ８１４
５９号および米国特許第 ４３６９１４２号）、アミノ
メチルホスホン酸とグリオキシル酸を反応させた後にパ
ラジウム触媒の存在下で水素還元する方法（欧州特許第
１８６６４８ 号）、アミノメチルホスホン酸とクロ
ロ酢酸を水酸化ナトリウムなどの酸受容体の存在下に８
０〜１２０℃程度に加熱する方法（ポーランド特許第
１２０７５９ 号およびスペイン特許第 ５０４４７９
号）、アミノメチルホスホン酸と臭化マロン酸ジエチ
ルをアルカリ性条件下で反応させた後、硫酸酸性下で加
水分解する方法（スペイン特許第 ５４５４５６ 号）
が知られているが、これらの方法は取り扱いにくい気体
を使用したり、反応操作が繁雑であったり、反応の収率
が充分でなかったり、必ずしも満足なものとはいえない
。For example, a method in which aminomethylphosphonic acid is added to an aqueous glyoxal solution at 40 to 45°C and then heated (Japanese Patent Application Laid-Open No. 62-61992), and a method in which aminomethylphosphonic acid and glyoxal are similarly used as raw materials and reacted in the presence of sulfur dioxide. (European Patent No. 814)
59 and U.S. Pat. No. 4,369,142), a method of reacting aminomethylphosphonic acid and glyoxylic acid and then reducing it with hydrogen in the presence of a palladium catalyst (European Patent No. 186,648), a method of reacting aminomethylphosphonic acid and chloroacetic acid with sodium hydroxide, etc. In the presence of acid receptors of 8
Method of heating to about 0 to 120℃ (Polish patent no.
No. 120759 and Spanish Patent No. 504479
(Spanish Patent No. 545456), a method in which aminomethylphosphonic acid and diethyl bromide malonate are reacted under alkaline conditions and then hydrolyzed under acidic sulfuric acid.
However, these methods are not necessarily satisfactory, as they use gases that are difficult to handle, the reaction operations are complicated, and the reaction yield is not sufficient.
【０００４】さらに、米国特許第 ４２２１５８３号に
はアミノメチルホスホン酸とアミノメチルホスホン酸の
モノ塩を形成するのに必要なアルカリの存在下でホルム
アルデヒドを反応させ、アミノメチルホスホン酸をＮ−
メチロール体とした後、ｐＨ７〜１０の間でシアン化カ
リウムを反応させるＮ−ホスホノメチルグリシノニトリ
ル、あるいはそのモノ塩の製造方法が開示されている。
また、同特許中には、その方法で合成されたＮ−ホスホ
ノメチルグリシノニトリルを加水分解することによりＮ
−ホスホノメチルグリシンが得られることが記載されて
いる。しかし、同特許の実施例の記載によれば、Ｎ−ホ
スホノメチルグリシノニトリルは最も収率良く得られた
場合でも６６％と低く、しかもアミノメチルホスホン酸
の転化率を上げるためには、アミノメチルホスホン酸に
対して、２．４倍モルという大過剰のシアン化カリウム
が必要である。また、Ｎ−ホスホノメチルグリシノニト
リルの加水分解の収率も、実施例によれば最高でも９０
％であるから、アミノメチルホスホン酸を基準とするＮ
−ホスホノメチルグリシンの収率は６０％程度となる。Furthermore, in US Pat. No. 4,221,583, aminomethylphosphonic acid is reacted with formaldehyde in the presence of an alkali necessary to form a monosalt of aminomethylphosphonic acid, and aminomethylphosphonic acid is converted into N-
A method for producing N-phosphonomethylglycinonitrile or a monosalt thereof is disclosed, in which the methylol compound is reacted with potassium cyanide at a pH of 7 to 10. In addition, in the same patent, N-phosphonomethylglycinonitrile synthesized by the method is hydrolyzed to produce N-
- It is stated that phosphonomethylglycine is obtained. However, according to the examples in the same patent, N-phosphonomethylglycinonitrile is as low as 66% even when obtained with the highest yield, and in order to increase the conversion rate of aminomethylphosphonic acid, it is necessary to A large excess of potassium cyanide of 2.4 times the mole relative to methylphosphonic acid is required. Furthermore, according to the examples, the yield of hydrolysis of N-phosphonomethylglycinonitrile is at most 90%.
%, N based on aminomethylphosphonic acid
-The yield of phosphonomethylglycine is about 60%.
【０００５】[0005]
【発明が解決しようとする課題】この発明の目的は、ア
ミノメチルスルホン酸を原料に使用して、操作が容易で
収率に優れたＮ−ホスホノメチルグリシンの製造方法を
提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide a method for producing N-phosphonomethylglycine that is easy to operate and has an excellent yield using aminomethylsulfonic acid as a raw material. .
【０００６】[0006]
【課題を解決するための手段】本発明者らは、アミノメ
チルホスホン酸を使用するＮ−ホスホノメチルグリシン
の製造方法について種々検討を重ねた結果、アミノメチ
ルホスホン酸とグリコロニトリルとを、アミノメチルホ
スホン酸がジアルカリ金属塩となり得る量のアルカリ金
属水酸化物を加えて反応させ、その後加水分解を行なう
にあたり、生成するカルボン酸を中和するのに充分な量
のアルカリ金属水酸化物を使用することによって、極め
て高収率でＮ−ホスホノメチルグリシンが得られること
を見出し、本発明を完成した。[Means for Solving the Problems] As a result of various studies on the production method of N-phosphonomethylglycine using aminomethylphosphonic acid, the present inventors have developed a method for producing N-phosphonomethylglycine using aminomethylphosphonic acid and glycolonitrile. Adding and reacting an amount of alkali metal hydroxide that can turn the acid into a dialkali metal salt, and then performing hydrolysis, using an amount of alkali metal hydroxide sufficient to neutralize the carboxylic acid produced. It was discovered that N-phosphonomethylglycine could be obtained in extremely high yield by the method, and the present invention was completed.
【０００７】すなわち、本発明はアミノメチルホスホン
酸とグリコロニトリルをアルカリ金属水酸化物の存在下
、６０℃以下の温度で反応させた後、生成するカルボン
酸を中和するのに充分な量のアルカリ金属水酸化物をさ
らに加えて加水分解することを特徴とするＮ−ホスホノ
メチルグリシンの製造方法を提供したものである。That is, the present invention involves reacting aminomethylphosphonic acid and glycolonitrile in the presence of an alkali metal hydroxide at a temperature of 60° C. or lower, and then reacting a sufficient amount to neutralize the resulting carboxylic acid. The present invention provides a method for producing N-phosphonomethylglycine, which comprises further adding an alkali metal hydroxide for hydrolysis.
【０００８】本発明についてさらに詳細に説明すれば、
アミノメチルホスホン酸とグリコロニトリルとの反応に
おいてアルカリ金属水酸化物を加えるのは、アミノメチ
ルホスホン酸が、アミノ基とホスホノ基を同一分子内に
持つ両性化合物であること、およびアミノメチルホスホ
ン酸とグリコロニトリルが反応するためにはアミノメチ
ルホスホン酸のアミノ基がイオンの形になっていないこ
とが必要だからである。 すなわち、アミノメチルホ
スホン酸の２個の酸性を示す水酸基のうち少なくとも一
方がアルカリ金属水酸化物で中和されていない時には、
一般の両性化合物に見られるようにアミノメチルホスホ
ン酸のアミノ基の一部あるいはほとんどすべてがイオン
の形のいわゆる両性イオンとなり、グリコロニトリルと
は反応しない。このことからわかるように、アルカリ金
属はアミノメチルホスホン酸に対して、２倍モル以上の
アルカリ金属水酸化物が加えられることが望ましい。ア
ルカリ金属のアミノメチルホスホン酸に対するモル比の
値はそれほど厳密なものではないが、アルカリ金属水酸
化物を過剰に加え、実質的に遊離のアルカリ金属水酸化
物が大量に存在すると、グリコロニトリルの分解により
収率の低下を招き、またアルカリ金属水酸化物が少ない
場合には上に述べた理由からアミノメチルホスホン酸の
反応性が落ち、やはり収率の低下を招く。従って、アル
カリ金属水酸化物はアミノメチルホスホン酸に対して２
倍モルを基準に０．５ モル程度増減した１．５ 〜２
．５ 倍モルの範囲、さらに望ましくは１．８ 〜２．
２ 倍モルの範囲で加えることが好ましい。なお、ここ
で使用するアルカリ金属水酸化物としては水酸化ナトリ
ウム、水酸化カリウムが好ましい。[0008] To explain the present invention in more detail,
The reason why an alkali metal hydroxide is added in the reaction between aminomethylphosphonic acid and glycolonitrile is that aminomethylphosphonic acid is an amphoteric compound having an amino group and a phosphono group in the same molecule, and the reaction between aminomethylphosphonic acid and glycolonitrile This is because the amino group of aminomethylphosphonic acid must not be in the form of an ion in order for the nitrile to react. That is, when at least one of the two acidic hydroxyl groups of aminomethylphosphonic acid is not neutralized with an alkali metal hydroxide,
As seen in general amphoteric compounds, some or almost all of the amino groups of aminomethylphosphonic acid form in the form of ions, so-called zwitterions, and do not react with glycolonitrile. As can be seen from this, it is desirable that the alkali metal hydroxide be added in an amount of twice or more moles or more relative to the aminomethylphosphonic acid. Although the value of the molar ratio of alkali metal to aminomethylphosphonic acid is not very critical, adding an excess of alkali metal hydroxide and the presence of a large amount of essentially free alkali metal hydroxide will result in a Decomposition causes a decrease in yield, and if the alkali metal hydroxide is small, the reactivity of aminomethylphosphonic acid decreases for the reasons stated above, which also causes a decrease in yield. Therefore, the alkali metal hydroxide is 2
1.5 to 2, which is an increase or decrease of about 0.5 mol based on twice the mol.
．． The range is 5 times the mole, more preferably 1.8 to 2.
It is preferable to add it in a 2-fold molar range. In addition, as the alkali metal hydroxide used here, sodium hydroxide and potassium hydroxide are preferable.
【０００９】反応に供するグリコロニトリルの量につい
ては、上に述べたアルカリ金属水酸化物とアミノメチル
ホスホン酸に関する量的な関係の範囲内であれば、理論
量、すなわちアミノメチルホスホン酸に対して等モルが
望ましい。この値もそれほど厳密なものではないが、ア
ミノメチルホスホン酸に対してグリコロニトリルが多い
場合には過剰量のグリコロニトリルが副反応の原因とな
り、少ない場合には比較的高価なアミノメチルホスホン
酸が未反応のまま残るので、共に避けることが望ましい
。このような理由から、グリコロニトリルはアミノメチ
ルホスホン酸に対して等モルを基準に０．５ モル程度
増減した０．５ 〜１．５ 倍モルの範囲、さらに望ま
しくは０．８ 〜１．２ 倍モルの範囲で反応に供され
ることが好ましい。
反応液のｐＨは原料仕込み濃度および反応温度によって
変化するので一概には言えないが、上記の条件下で反応
が行われた場合、反応液のｐＨは１０．５以上となる。The amount of glycolonitrile to be subjected to the reaction is within the range of the above-mentioned quantitative relationship between the alkali metal hydroxide and aminomethylphosphonic acid. Moles are preferred. This value is also not very strict, but if there is a large amount of glycolonitrile compared to aminomethylphosphonic acid, the excess amount of glycolonitrile will cause side reactions, and if there is less glycolonitrile, the relatively expensive aminomethylphosphonic acid will be used. Since it remains unreacted, it is desirable to avoid both. For this reason, glycolonitrile is used in a range of 0.5 to 1.5 times the mole of aminomethylphosphonic acid, which is an increase or decrease of about 0.5 mole based on equimole, and more preferably 0.8 to 1.2 times the molar amount. It is preferred that the reaction be carried out in twice the molar amount. Although the pH of the reaction solution varies depending on the raw material concentration and the reaction temperature, it cannot be generalized, but when the reaction is carried out under the above conditions, the pH of the reaction solution will be 10.5 or more.
【００１０】反応の方式にはとくに制限はないが、通常
はアミノメチルホスソン酸とアルカリ金属水酸化物の撹
拌混合水溶液に、グリコロニトリルの水溶液を滴下した
後、さらに撹拌を続けて反応を完結させる。アミノメチ
ルホスホン酸とグリコロニトリルの反応温度は６０℃以
下が望ましい。温度が高すぎる場合は副反応を生じ、収
率が低下する。一方、余り低い温度では反応が遅くなる
ので、通常は０〜６０℃、好ましくは１０〜４０℃が適
当である。また、反応に要する時間は温度によって異な
るが３０分〜３時間程度である。[0010] Although there are no particular restrictions on the reaction method, the reaction is usually carried out by dropping an aqueous solution of glycolonitrile into a stirred mixed aqueous solution of aminomethyl phosphosonic acid and an alkali metal hydroxide, and then continuing to stir the mixture. complete it. The reaction temperature of aminomethylphosphonic acid and glycolonitrile is preferably 60°C or lower. If the temperature is too high, side reactions will occur and the yield will decrease. On the other hand, if the temperature is too low, the reaction will be slow, so a temperature of usually 0 to 60°C, preferably 10 to 40°C is appropriate. Further, the time required for the reaction varies depending on the temperature, but is approximately 30 minutes to 3 hours.
【００１１】加水分解時に加えられるアルカリ金属水酸
化物の量は加水分解により生成するカルボン酸を中和す
るのに充分な量である必要がある。アルカリ金属水酸化
物が少ない場合には加水分解が進行しないし、また、過
剰に加えると、生成物であるＮ−ホスホノメチルグリシ
ンの酸析による単離の際に塩の生成量が多くなるため避
けることが望ましい。この加水分解反応の温度は特に制
限はないが通常は６０℃から反応液の沸点までの範囲で
行なわれる。反応時間は温度によるが通常は１〜３時間
程度である。なお、反応を反応液の沸点以下で行なう場
合には、加水分解反応により生成するアンモニアを除去
するため、反応終了前に少なくとも一度反応液を煮沸す
ることが望ましい。The amount of alkali metal hydroxide added during hydrolysis must be sufficient to neutralize the carboxylic acid produced by hydrolysis. If the amount of alkali metal hydroxide is small, hydrolysis will not proceed, and if it is added in excess, a large amount of salt will be produced when the product N-phosphonomethylglycine is isolated by acid precipitation. Therefore, it is desirable to avoid it. The temperature of this hydrolysis reaction is not particularly limited, but it is usually carried out within a range from 60°C to the boiling point of the reaction solution. The reaction time depends on the temperature, but is usually about 1 to 3 hours. In addition, when the reaction is carried out below the boiling point of the reaction liquid, it is desirable to boil the reaction liquid at least once before the end of the reaction in order to remove ammonia produced by the hydrolysis reaction.
【００１２】かくして得られる反応液中から、場合によ
っては反応液を適宜希釈あるいは濃縮した後、Ｎ−ホス
ホノメチルグリシンを酸析によって容易に単離すること
ができる。あるいは、例えばイオン交換樹脂のような他
の常法の手段を単独で、あるいは併用して単離精製する
ことができるし、再結晶によってさらに精製することも
できる。From the reaction solution thus obtained, N-phosphonomethylglycine can be easily isolated by acid precipitation after appropriately diluting or concentrating the reaction solution as the case may be. Alternatively, other conventional methods such as ion exchange resin can be used alone or in combination for isolation and purification, and further purification can be performed by recrystallization.
【００１３】[0013]
【発明の効果】前述の条件でアミノメチルホスホン酸と
グリコロニトリルを反応させる本発明の方法によれば、
容易な操作で高収率でＮ−ホスホノメチルグリシンを得
ることができる。すなわち、アミノメチルホスホン酸と
グリコロニトリルの転化率はいずれも９５％以上となり
、Ｎ−ホスホノメチルグリシンへの選択率も９５％以上
に達する。[Effects of the Invention] According to the method of the present invention in which aminomethylphosphonic acid and glycolonitrile are reacted under the above-mentioned conditions,
N-phosphonomethylglycine can be obtained in high yield with easy operations. That is, the conversion rates of aminomethylphosphonic acid and glycolonitrile both reach 95% or more, and the selectivity to N-phosphonomethylglycine also reaches 95% or more.
【００１４】従来技術の項で説明した米国特許第 ４２
２１５８３号明細書の実施例には、アミノメチルホスホ
ン酸とホルムアルデヒドを、アミノメチルホスホン酸に
対して１．３ 倍モルの水酸化ナトリウムの存在下反応
させてアミノメチルホスホン酸のＮ−メチロール体とし
た後、塩酸水溶液でｐＨを８〜９に保ちながらアミノメ
チルホスホン酸に対し１．１ 倍モルのシアン化カリウ
ムを加える方法でのアミノメチルホスホン酸の転化率が
８０％である旨記載されているが、この方法に比較して
、アミノメチルホスホン酸のＮ−メチロール体を経過せ
ずグリコロニトリルを使用する本発明方法の有利なこと
は明らかである。
さらに、前記米国特許に記載されているようなｐＨ８〜
９の反応条件では系内に存在する未反応のホルムアルデ
ヒドとシアン化ナトリウムからグリコロニトリルが生成
していたとしても、先述のような理由でアミノメチルホ
スホン酸との反応は起きていないことは明らかであるか
ら、アミノメチルホスホン酸とグリコロニトリルを反応
が進行するのに充分な条件下で、すなわちアミノメチル
ホスホン酸に対して１．５ 〜２．５ 倍モルのアルカ
リ金属水酸化物を加え、ｐＨ１０．５以上という条件下
で、グリコロニトリルをアミノメチルホスホン酸と反応
させるという本発明の方法は前記米国特許の記載からは
予測できないユニークな方法であると言える。US Pat. No. 42, discussed in the prior art section
In the example of No. 21583, aminomethylphosphonic acid and formaldehyde are reacted in the presence of sodium hydroxide in an amount 1.3 times the molar amount of aminomethylphosphonic acid to form the N-methylol form of aminomethylphosphonic acid. It is stated that the conversion rate of aminomethylphosphonic acid is 80% by adding 1.1 times the mole of potassium cyanide to aminomethylphosphonic acid while keeping the pH at 8 to 9 with an aqueous hydrochloric acid solution. Therefore, it is clear that the method of the present invention, which uses glycolonitrile without passing through the N-methylol form of aminomethylphosphonic acid, is advantageous. Furthermore, pH 8~ as described in the above-mentioned US patent
Even if glycolonitrile was produced from the unreacted formaldehyde and sodium cyanide present in the system under the reaction conditions of 9, it is clear that no reaction with aminomethylphosphonic acid occurred for the reasons mentioned above. Therefore, aminomethylphosphonic acid and glycolonitrile were mixed under conditions sufficient for the reaction to proceed, that is, 1.5 to 2.5 times the mole of alkali metal hydroxide to aminomethylphosphonic acid was added, and the pH was adjusted to 10. The method of the present invention, in which glycolonitrile is reacted with aminomethylphosphonic acid under conditions of 5 or more, can be said to be a unique method that could not be predicted from the description in the above-mentioned US patent.
【００１５】[0015]
【実施例】以下、本発明によるＮ−ホスホノメチルグリ
シンの製造方法について代表的な例を示し具体的に説明
する。ただし、これらは本発明についての理解を容易に
するための例示であり、本発明はこれのみに限定されな
いのは勿論のこと、これによって何ら限定的に解釈され
るものでなはい。EXAMPLES The method for producing N-phosphonomethylglycine according to the present invention will be specifically explained below by showing typical examples. However, these are examples to facilitate understanding of the present invention, and the present invention is of course not limited to these examples, and should not be construed as being limited in any way.
【００１６】実施例１
２００ｍｌの４ツ口フラスコに撹拌機、温度計、滴下ロ
ートおよび還流凝縮機をとりつけた。５０ｇの水、１６
．７ｇの４８％水酸化ナトリウム水溶液（２００ｍｍｏ
ｌ）、１１．１ｇのアミノメチルホスホン酸（１００ｍ
ｍｏｌ）の混合液を入れ、撹拌した。この時のｐＨ（ｐ
Ｈ７の緩衝液で２０℃において較正したｐＨメーターで
測定した。以下同じ）は１３．１であった。反応器を氷
水中で冷却し反応液を５℃以下に保ちながら１４．３ｇ
の４０％グリコロニトリル溶液（１００ｍｍｏｌ）を３
０分かけて滴下した。滴下終了後、５℃以下で３０分、
室温に戻して１時間撹拌した。
この時のｐＨは１１．０であった。次いで、８．４ ｇ
の４８％水酸化ナトリウム水溶液（１００ｍｍｏｌ）を
加え、２時間加熱還流させた。反応終了後の液をＨＰＬ
Ｃで分析したところ、Ｎ−ホスホノメチルグリシンを９
４ｍｍｏｌ含んでいた。反応収率は原料アミノメチルホ
スホン酸およびグリコロニトリルに対して９４％であっ
た。反応液を濃塩酸によりｐＨ２まで中和した後、一晩
放置しＮ−ホスホノメチルグリシンを晶出させた。晶出
したＮ−ホスホノメチルグリシンをろ別した。水洗、乾
燥後の重量は１３．４ｇであり、ＨＰＬＣから求めた純
度は９８％であった。
原料アミノメチルホスホン酸およびグリコロニトリルか
らの収率は７８％であった。Example 1 A 200 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. 50g water, 16
．． 7g of 48% aqueous sodium hydroxide solution (200mmol
l), 11.1 g of aminomethylphosphonic acid (100 m
mol) was added and stirred. The pH at this time (p
Measurements were made with a pH meter calibrated at 20° C. with a buffer of H7. ) was 13.1. 14.3g while cooling the reactor in ice water and keeping the reaction liquid below 5℃.
40% glycolonitrile solution (100 mmol) of
It was added dropwise over 0 minutes. After dropping, keep at 5℃ or below for 30 minutes.
The mixture was returned to room temperature and stirred for 1 hour. The pH at this time was 11.0. Then 8.4 g
A 48% aqueous sodium hydroxide solution (100 mmol) was added thereto, and the mixture was heated under reflux for 2 hours. After the reaction is completed, the liquid is subjected to HPL.
When analyzed by C, N-phosphonomethylglycine was 9
It contained 4 mmol. The reaction yield was 94% based on the raw materials aminomethylphosphonic acid and glycolonitrile. After the reaction solution was neutralized to pH 2 with concentrated hydrochloric acid, it was left to stand overnight to crystallize N-phosphonomethylglycine. The crystallized N-phosphonomethylglycine was filtered off. The weight after washing with water and drying was 13.4 g, and the purity determined by HPLC was 98%. The yield from the raw materials aminomethylphosphonic acid and glycolonitrile was 78%.
【００１７】実施例２
グリコロニトリル滴下時の反応液の温度を２０℃前後に
保ち、滴下終了後、２０℃前後で１時間撹拌した以外は
実施例１と同様に行なった。反応終了後の液をＨＰＬＣ
で分析したところ、Ｎ−ホスホノメチルグリシンの反応
収率は原料アミノメチルホスホン酸およびグリコロニト
リルに対して９５％であった。Example 2 The same procedure as in Example 1 was carried out, except that the temperature of the reaction solution during the dropwise addition of glycolonitrile was maintained at around 20°C, and after the dropwise addition was completed, the mixture was stirred at around 20°C for 1 hour. HPLC the liquid after the reaction
As a result of analysis, the reaction yield of N-phosphonomethylglycine was 95% based on the starting materials aminomethylphosphonic acid and glycolonitrile.
【００１８】実施例３
グリコロニトリル滴下時の反応液の温度を６０℃前後に
保ち、滴下終了後、６０℃前後で１時間撹拌した以外は
実施例１と同様に行った。反応終了後の液をＨＰＬＣで
分析したところ、Ｎ−ホスホノメチルグリシンの反応収
率は原料アミノメチルホスホン酸およびグリコロニトリ
ルに対して７２％であった。Example 3 The same procedure as in Example 1 was carried out, except that the temperature of the reaction solution during the dropwise addition of glycolonitrile was maintained at around 60°C, and after the dropwise addition was completed, the mixture was stirred at around 60°C for 1 hour. When the liquid after the reaction was analyzed by HPLC, the reaction yield of N-phosphonomethylglycine was 72% based on the starting materials aminomethylphosphonic acid and glycolonitrile.
【００１９】実施例４
実施例１と同様の装置に、５０ｇの水、８．４ ｇの４
８％水酸化ナトリウム水溶液（１００ｍｍｏｌ）、１１
．１ｇのアミノメチルホスホン酸（１００ｍｍｏｌ）の
混合液を入れ、撹拌した。この時のｐＨは９．７ であ
った。反応液を氷水中で冷却し反応液を５℃以下に保ち
ながら１４．３ｇの４０％グリコロニトリル水溶液（１
００ｍｍｏｌ）を３０分かけて滴下した。滴下終了後、
５℃以下で３０分、室温に戻して１時間撹拌した。この
時のｐＨは９．５ であった。ＨＰＬＣで分析したとこ
ろ原料アミノメチルホスホン酸およびグリコロニトリル
の転化率は５％以下であった。Example 4 In an apparatus similar to Example 1, 50 g of water, 8.4 g of 4
8% aqueous sodium hydroxide solution (100 mmol), 11
．． A mixed solution of 1 g of aminomethylphosphonic acid (100 mmol) was added and stirred. The pH at this time was 9.7. Cool the reaction solution in ice water and add 14.3 g of 40% glycolonitrile aqueous solution (1
00 mmol) was added dropwise over 30 minutes. After the dripping is finished,
The mixture was stirred at 5° C. or lower for 30 minutes, then returned to room temperature and stirred for 1 hour. The pH at this time was 9.5. Analysis by HPLC showed that the conversion rate of the raw materials aminomethylphosphonic acid and glycolonitrile was 5% or less.
【００２０】次にこの反応液を２０℃に保ちながら８．
４ ｇの４８％水酸化ナトリウム水溶液を１５分かけて
滴下した。滴下終了後のｐＨは１１．２であった。その
まま２０℃で１時間撹拌した。この反応液をＨＰＬＣで
分析したところ、原料アミノメチルホスホン酸およびグ
リコロニトリルの転化率は９５％以上であった。次いで
、８．４ ｇの４８％水酸化ナトリウム水溶液（１００
ｍｍｏｌ）を加え、２時間加熱還流した。反応終了後の
液をＨＰＬＣで分析したところ、Ｎ−ホスホノメチルグ
リシンの反応収率は原料アミノメチルホスホン酸および
グリコロニトリルに対して９１％であった。Next, while keeping this reaction solution at 20°C, 8.
4 g of 48% aqueous sodium hydroxide solution was added dropwise over 15 minutes. The pH after the completion of the dropwise addition was 11.2. The mixture was stirred at 20° C. for 1 hour. When this reaction solution was analyzed by HPLC, the conversion rate of the raw material aminomethylphosphonic acid and glycolonitrile was 95% or more. Then, 8.4 g of 48% aqueous sodium hydroxide solution (100
mmol) and heated under reflux for 2 hours. When the liquid after the reaction was analyzed by HPLC, the reaction yield of N-phosphonomethylglycine was 91% based on the starting materials aminomethylphosphonic acid and glycolonitrile.
Claims (4)
トリルをアルカリ金属水酸化物の存在下６０℃以下の温
度で反応させた後、生成するカルボン酸を中和するのに
充分な量のアルカリ金属水酸化物をさらに加えて加水分
解することを特徴とするＮ−ホスホノメチルグリシンの
製造方法。Claim 1: After reacting aminomethylphosphonic acid and glycolonitrile in the presence of an alkali metal hydroxide at a temperature of 60° C. or lower, a sufficient amount of alkali metal hydroxide to neutralize the resulting carboxylic acid. A method for producing N-phosphonomethylglycine, which comprises further adding a substance and performing hydrolysis.
トリルの反応をｐＨ１０．５以上で行なう請求項１に記
載のＮ−ホスホノメチルグリシンの製造方法。2. The method for producing N-phosphonomethylglycine according to claim 1, wherein the reaction of aminomethylphosphonic acid and glycolonitrile is carried out at a pH of 10.5 or higher.
ルホスホン酸に対して０．５ 〜１．５ 倍モルのグリ
コロニトリルを、アミノメチルホスホン酸に対して１．
５〜２．５ 倍モルのアルカリ金属水酸化物の存在下に
反応させる請求項１に記載のＮ−ホスホノメチルグリシ
ンの製造方法。3. Aminomethylphosphonic acid and glycolonitrile in an amount of 0.5 to 1.5 times the mole of aminomethylphosphonic acid, and 1.
2. The method for producing N-phosphonomethylglycine according to claim 1, wherein the reaction is carried out in the presence of 5 to 2.5 times the mole of alkali metal hydroxide.
ウムまたは水酸化カリウムである請求項１、２または３
に記載のＮ−ホスホノメチルグリシンの製造方法。[Claim 4] Claim 1, 2 or 3, wherein the alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
The method for producing N-phosphonomethylglycine described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3064026A JP2533006B2 (en) | 1991-03-05 | 1991-03-05 | Method for producing N-phosphonomethylglycine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3064026A JP2533006B2 (en) | 1991-03-05 | 1991-03-05 | Method for producing N-phosphonomethylglycine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04279595A true JPH04279595A (en) | 1992-10-05 |
| JP2533006B2 JP2533006B2 (en) | 1996-09-11 |
Family
ID=13246219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3064026A Expired - Lifetime JP2533006B2 (en) | 1991-03-05 | 1991-03-05 | Method for producing N-phosphonomethylglycine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2533006B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996001264A1 (en) * | 1994-07-01 | 1996-01-18 | Showa Denko K.K. | Process for producing phosphonic acid derivative |
| EP0806428A1 (en) * | 1994-11-09 | 1997-11-12 | Showa Denko Kabushiki Kaisha | Method for isolating N-phosphonomethylglycine |
| EP0816369A1 (en) * | 1996-06-21 | 1998-01-07 | Showa Denko Kabushiki Kaisha | Method for producing N-phosphonomethylglycine |
-
1991
- 1991-03-05 JP JP3064026A patent/JP2533006B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996001264A1 (en) * | 1994-07-01 | 1996-01-18 | Showa Denko K.K. | Process for producing phosphonic acid derivative |
| US5679844A (en) * | 1994-07-01 | 1997-10-21 | Showa Denko K.K. | Manufacturing method for phosphonic acid derivatives |
| EP0806428A1 (en) * | 1994-11-09 | 1997-11-12 | Showa Denko Kabushiki Kaisha | Method for isolating N-phosphonomethylglycine |
| EP0816369A1 (en) * | 1996-06-21 | 1998-01-07 | Showa Denko Kabushiki Kaisha | Method for producing N-phosphonomethylglycine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2533006B2 (en) | 1996-09-11 |
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