JPS62215557A - Production of isobutylideneaminoxyacetic acid - Google Patents
Production of isobutylideneaminoxyacetic acidInfo
- Publication number
- JPS62215557A JPS62215557A JP5705186A JP5705186A JPS62215557A JP S62215557 A JPS62215557 A JP S62215557A JP 5705186 A JP5705186 A JP 5705186A JP 5705186 A JP5705186 A JP 5705186A JP S62215557 A JPS62215557 A JP S62215557A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- alkali
- reaction
- methyl ethyl
- ethyl ketoxime
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- WPMNGDWICHSRRJ-UHFFFAOYSA-N 2-(2-methylpropylideneamino)oxyacetic acid Chemical compound CC(C)C=NOCC(O)=O WPMNGDWICHSRRJ-UHFFFAOYSA-N 0.000 title description 2
- 239000003513 alkali Substances 0.000 claims abstract description 27
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 claims abstract 3
- -1 isobutylidene aminooxyacetic acid Chemical compound 0.000 claims description 14
- 239000000243 solution Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 abstract description 3
- 229940106681 chloroacetic acid Drugs 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000001242 acetic acid derivatives Chemical class 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- NQRKYASMKDDGHT-UHFFFAOYSA-N (aminooxy)acetic acid Chemical compound NOCC(O)=O NQRKYASMKDDGHT-UHFFFAOYSA-N 0.000 description 5
- SOWBFZRMHSNYGE-UHFFFAOYSA-N Monoamide-Oxalic acid Natural products NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000052 vinegar Substances 0.000 description 4
- 235000021419 vinegar Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003799 water insoluble solvent Substances 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）発明の目的
〔産業上の利用分野〕
本発明は医薬、＆薬その他の有用物質の製造を目的とす
る有機合成の中間体として有用な、イソブチリデンアミ
ノオキシ酢酸の製造方法に関するものである。Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention provides isobutylidene amino which is useful as an intermediate in organic synthesis for the purpose of producing medicines, medicines and other useful substances. The present invention relates to a method for producing oxyacetic acid.
イノブチリデンアミノオキシ酢酸の製造方法に関しては
ほとんど検討されておらず、わずかにアミノオキシ酢酸
とメチルエチルケトンの反応による製造方法のみが報告
されているにすぎｅ ｎａｔ、１９５７〜１９５Ｂ
、４ 、ｐｌ ６３〜Ｂ２ ）。There has been little research into the production method of inobutylidene aminooxyacetic acid, and only a production method using the reaction of aminooxyacetic acid and methyl ethyl ketone has been reported.
, 4, pl 63-B2).
イソブチリデンアミノオキシ酢酸は通常、その加水分解
により農薬、医薬、有機合成の中間体としてより有用な
アミノオキシ酢酸を目的物として得るだめの原料として
製造されろつしかるに前記文献によるいわば古典的な製
法は、この目的物であるアミノオキシＩ！１−酸を出発
原料として使用しているのであるから、現在要求されて
いる簡便で経済的なイソブチリデンアミノオキシ酢酸の
製造方法としては、まりだ（不適当である。Isobutylidene aminooxyacetic acid is usually produced as a raw material to obtain aminooxyacetic acid, which is more useful as an intermediate for agricultural chemicals, medicines, and organic synthesis, by hydrolysis. The manufacturing method is to produce the desired product, aminooxy I! Since 1-acid is used as a starting material, it is inappropriate as a simple and economical method for producing isobutylidene aminooxyacetic acid, which is currently required.
（ロ） 発明の構成
〔問題を解決するための手段〕
本発明は、メチルエチルケトオキシムとハロゲン化酢酸
を、アルカリの存在下に反応させろことにより、上記問
題を解決したものであり。(B) Structure of the Invention [Means for Solving the Problems] The present invention solves the above problems by reacting methyl ethyl ketoxime and halogenated acetic acid in the presence of an alkali.
本発明の方法により、経済的にしかも容易に。Economically and easily by the method of the present invention.
各種中間体として有用なイソプチリデンアミノオキシ酢
酸を製造することが可能である。It is possible to produce isoptylidene aminooxyacetic acid, which is useful as a variety of intermediates.
本発明のイソブチリデンアミノオキシ酢酸の製造方法に
おける反応は１次式の如くあられすことができる１
Ｃ＝ＮＵＪ９Ｈ，Ｃ０ＯＨ・・・・・・（１）（上式中
Ｘはハロゲン、Ｍはアルカリをあられす、）
一般にハロゲン化酢酸はアルカリと反応すると中和反応
がおこり、アルカリが更に存在するとハロゲン原子とア
ルカリの反応が起こる。アルカリとして水酸化ナトリウ
ムを用いた場合には以下のよう番こなる。The reaction in the method for producing isobutylidene aminooxyacetic acid of the present invention can occur as shown in the linear equation 1 C=NUJ9H,C0OH (1) (in the above formula, X is halogen, M is In general, when halogenated acetic acid reacts with an alkali, a neutralization reaction occurs, and when an alkali is present, a reaction between the halogen atom and the alkali occurs. When sodium hydroxide is used as the alkali, the sequence is as follows.
ＣＨ，ＸＣ０ＯＨ＋ＮａＯＨ−ＣＨ，ＸＣＯＯＮａ＋Ｈ
ｔ ０−（２１又ケトオキシムは酸性、アルカリ性の両
性な示し。CH,XCOOH+NaOH−CH,XCOONa+H
t 0-(21 Ketoximes are both acidic and alkaline amphoteric.
例えばメチルエチルケトオキシムに対しアルカリとして
水酸化ナトリウムを用いると
の如くメチルエチルケトオキシムのナトリウム塩が反応
中間体として生成するといわれている。For example, when sodium hydroxide is used as an alkali for methyl ethyl ketoxime, the sodium salt of methyl ethyl ketoxime is said to be produced as a reaction intermediate.
本発明の製法における反応機構については不明であるが
、上記に例示した水酸化す） ＋７ウムを用いる反応で
は、（２）式における／１０ゲン化酢酸ナトリウムと（
４）式で生成するといわれるメチルエチルケトオキシム
のナトリウム塩との脱ハロゲン化ナトリウム反応によっ
て、インブチリデンアミノオキシｆ！ｎ酸ナトリウムが
生成するものと思われる。Although the reaction mechanism in the production method of the present invention is unknown, in the reaction using 7 um hydroxide as exemplified above, sodium acetate /10 in formula (2) and (
4) Imbutylidene aminooxy f! is produced by a sodium dehalogenation reaction with the sodium salt of methyl ethyl ketoxime which is said to be produced by the formula. It is thought that sodium n-acid is produced.
本発明で主原料として使用するメチルエチルケトオキシ
ムは１通常メチルエチルケトンとヒドロキシルアミン鉱
酸塩から容易に得られ、工業的に大量に製造されており
、安価に入手可能である。もう一方の主原料であるハロ
ゲン化酢酸としては、ブロモ酢酸、クロロ酢酸、フルオ
ロ酢酸およびヨード酢酸のいずれもが使用可能であるが
、入手容易性と経済性を考えると、クロロ酢酸またはブ
ロモ酢酸が好ましい。Methyl ethyl ketoxime used as a main raw material in the present invention is usually easily obtained from methyl ethyl ketone and hydroxylamine mineral salt, is industrially produced in large quantities, and is available at low cost. Bromoacetic acid, chloroacetic acid, fluoroacetic acid, and iodoacetic acid can all be used as the other main raw material, halogenated acetic acid. preferable.
反応系に存在させるべきアルカリ化剤としては。As an alkalizing agent that should be present in the reaction system.
ナトリウム、カリウムなどのアルカリ金属の水用可能で
あるが、 ｆ＆解性および反応性から水酸化ナトリウム
または水酸化カリウムがより好ましい。Water containing alkali metals such as sodium and potassium can be used, but sodium hydroxide or potassium hydroxide is more preferable from the viewpoint of f & decomposition and reactivity.
反応はハロゲン化酢ｃＲナアルカリで式＋２１の如く中
和することから開始する。この中和は、ハロゲン化酢ｆ
Ｒ１ｔ水に浴解してアルカ１３ ’に直接またはアルカ
リ水浴液として添加する方法が反応性の面から望ましい
が、逆でも充分可能である。The reaction is started by neutralizing with halogenated vinegar cR Na-alkali as shown in formula +21. This neutralization is performed using halogenated vinegar f
From the viewpoint of reactivity, it is desirable to dissolve the compound in R1t water and add it to the alkali 13' either directly or as an alkaline water bath solution, but the reverse is also possible.
この反応においてハロゲン化酢酸に対するアルカリの使
用量は、化学量論量で充分である。アルカＩＪ Ｙ過剰
に存在させると、ノ・ロゲン化酢酸から生じるヒドロキ
シ酢酸アルカリの二値化によってグリコール酸アルカリ
を生成するおそれがある。本反応は、一般的な酸とアル
カリの中和反応であるため１反応熱（中和熱）の除去が
必要であり、これは常法により行なえば良い。In this reaction, a stoichiometric amount of alkali is sufficient for the halogenated acetic acid. If the alkali IJY is present in excess, there is a possibility that an alkali glycolate may be produced by binarization of the alkali hydroxyacetate generated from the rogenated acetic acid. Since this reaction is a general neutralization reaction between an acid and an alkali, it is necessary to remove the heat of reaction (heat of neutralization), and this may be carried out by a conventional method.
上記の如くして得られたハロゲン化酢酸アルカリ水溶液
にメチルエチルケトオキシムおよびアルカリを加える。Methyl ethyl ketoxime and an alkali are added to the aqueous alkali halogenated acetate solution obtained as above.
ここで添加するメチルエチルケトオキシムは、ハロゲン
化酢酸アルカリに対して等当量以下、更に好ましくは当
量の８０〜９５％である。このようにすることは、メチ
ルエチルケトオキシムの反応率を向上させろために効果
的である。アルカリの第２回目の添加量は、中和反応に
用いたアルカリと等量以上であることが望ましい。好適
なアルカリ添加量は。The amount of methyl ethyl ketoxime added here is equal to or less than the equivalent amount to the halogenated alkali acetate, and more preferably 80 to 95% of the equivalent amount. This is effective for improving the reaction rate of methyl ethyl ketoxime. The amount of alkali added in the second time is desirably equal to or more than the amount of alkali used in the neutralization reaction. What is the appropriate amount of alkali to be added?
ハロゲン化酢酸をそのハロゲン原子の離脱によってメチ
ルエチルケトオキシムと反応させるに必要な化学量論量
またはそれ以上であり１反応はアルカリ添加量の多い方
が速やかに進行し、アルカリ添加量の上限に格別の制限
はないが。This is the stoichiometric amount or more required to react halogenated acetic acid with methyl ethyl ketoxime through the elimination of its halogen atom, and the reaction proceeds more quickly when the amount of alkali added is large. Although there is no limit.
不必要に過剰のアルカリを添加すると、得られろ反応液
Ｑ）中和に多量の酸を要し不経済なので。If excessive alkali is added unnecessarily, a large amount of acid will be required for neutralization of the resulting reaction solution Q), which is uneconomical.
や〜過剰の程度とするのがよい。It is best to set it to a moderate to excessive degree.
反応系へは所望により水なさらに追加できるが。Water can be further added to the reaction system if desired.
この水とメチルエチルケトオキシムおよびアルカリの添
加順序は、基本的にはいずれを先にしても反応に何ら悪
影響を及ぼさないが、メチルエチルケトオキシムな最初
に添加するのが望ましい。The order in which water, methyl ethyl ketoxime and alkali are added basically does not adversely affect the reaction no matter which one is added first, but it is preferable to add methyl ethyl ketoxime first.
反応温度は、好ましくない副反応１例えば分解。The reaction temperature is controlled by undesirable side reactions such as decomposition.
シアノ化合物の生成などを避けるために、４０℃以下さ
らに好ましくは３０℃以下に保つのがが１反応液全体な
長時間高温で加熱すると、反応液がかっ色ないし黒色に
着色し１反応収率が低下するため、あらかじめ８０〜１
２０℃に加熱した細長い反応管を用い、この管内に反応
液を、線速度０．５〜５ ｍ ／ ｓｅｃ程度の短時間
で通過させるのが好ましい。In order to avoid the formation of cyano compounds, it is best to keep the entire reaction solution at 40°C or below, more preferably 30°C or below.If the entire reaction solution is heated at high temperatures for a long period of time, the reaction solution will turn brown or black and the reaction yield will decrease. 80 to 1 in advance to reduce
It is preferable to use a long and narrow reaction tube heated to 20° C. and allow the reaction solution to pass through the tube at a linear velocity of about 0.5 to 5 m/sec for a short time.
反応に溶媒として使用する水は、ハロゲン化酢シーロゲ
ン化酢酸アルカリ及びイソブチリデンアミノオキシ酢酸
アルカリ等が溶解して均−系を形成するに足る量で充分
であり、その量は主原料として反応系に供給されるハロ
ゲン化酢酸を基準にすると、その１重量部に対し１〜１
０重量部、さらに好ましくは２〜５重量部である。The amount of water used as a solvent in the reaction is sufficient to dissolve the halogenated acetic acid, the silogenated alkali acetate, the alkali isobutylidene aminooxyacetate, etc., and form a homogeneous system. Based on the halogenated acetic acid supplied to the system, 1 to 1 part by weight of the halogenated acetic acid
The amount is preferably 0 parts by weight, more preferably 2 to 5 parts by weight.
水が１重量部より少いと原料及び反応生成物が浴解し難
く、また水ｆｔ１０重量部以上使用すると、後の工程で
目的物であるインブチリデンアミノオキシ酢酸をたとえ
ば抽出法により分離するための水不溶性溶剤を多量に使
用する必要が生じるので、経済的でない。If the amount of water is less than 1 part by weight, the raw materials and reaction products will be difficult to dissolve in the bath, and if more than 10 parts by weight of water is used, the target product, imbutylidene aminooxyacetic acid, will be separated in a later step, for example, by an extraction method. Since it is necessary to use a large amount of water-insoluble solvent, it is not economical.
反応終了後水不溶性溶剤例えばジエチルエーテル等によ
り未反応メチルエチルケトオキシムな抽出分離する。得
られた未反応メチルエチルケトオキシムを含む溶剤溶液
は、常法例えば蒸留により溶剤を除去した後１回収メチ
ルエチルケトオキシムとして反応に再使用することも可
能である。After the reaction is completed, unreacted methyl ethyl ketoxime is extracted and separated using a water-insoluble solvent such as diethyl ether. The obtained solvent solution containing unreacted methyl ethyl ketoxime can be reused in the reaction as recovered methyl ethyl ketoxime after removing the solvent by a conventional method such as distillation.
未反応メチルエチルケトオキシムを抽出除去した後の水
溶液は、イソブチリデンアミノオキシ酸ｌｌ！２’にそ
のアルカリ塩として含んでおり、これを含む水溶液を塩
酸等の酸で酸性とすることにより、該アルカリ塩をイソ
ブチリデンアミノオキシ酢酸とするうこの時１反応醪媒
として使用する水の量により、インブチリデンアミノオ
キシ酢Ｐｉ１１！８ｅ油状物として水と分離することが
可能であり、またその全量な水溶液として得ることも可
能である。イソブチリデンアミノオキシ酢酸が油状で水
と二層分離している場合にけ１通常の分液操作により水
と分離して目的物を得る。The aqueous solution after extracting and removing unreacted methyl ethyl ketoxime is isobutylidene aminooxy acid ll! 2' is contained as its alkali salt, and by making the aqueous solution containing this acidic with an acid such as hydrochloric acid, the alkali salt is converted to isobutylidene aminooxyacetic acid. Depending on the amount of imbutylidene aminooxy vinegar Pi11!8e, it is possible to separate it from water as an oily substance, or it is also possible to obtain the entire amount as an aqueous solution. When isobutylidene aminooxyacetic acid is oily and separates into two layers from water, it is separated from water by a normal liquid separation operation to obtain the desired product.
さらに分液した水層なジエチルエーテル等で抽出し、ジ
エチルエーテルを留去することにより。Further, the separated aqueous layer is extracted with diethyl ether, etc., and the diethyl ether is distilled off.
水静解分として残留している目的物を得ることもできる
。イソブチリデンアミノオキシ酢酸が全量水に溶解して
いる場合には、水不活性溶剤例えばジエチルエーテル等
で抽出し、溶剤な留去して、イソブチリデンアミノオキ
シ酢酸を得る。It is also possible to obtain the target product remaining as hydrostatic decomposition. When the entire amount of isobutylidene aminooxyacetic acid is dissolved in water, it is extracted with a water-inert solvent such as diethyl ether, and the solvent is distilled off to obtain isobutylideneaminooxyacetic acid.
実施例１゜
クロロ酢酸１０４部（重量部、以下同じ）を氷水３００
部に溶解し、攪拌下に、温度が２０℃以下になるように
外部から冷却しながら濃度４８重ｔ％の水酸化ナトリウ
ム水溶液９２部を添加し、中和反応な実施した。得られ
た反応液にメチルエチルケトオキシム８７部、濃度４８
重ｔ％の水酸化す） １３ウム９２部および水５３部を
攪拌下に２０℃で添加し、２４時間反応させた。Example 1 104 parts of chloroacetic acid (parts by weight, the same applies hereinafter) was added to 300 parts of ice water.
92 parts of an aqueous sodium hydroxide solution having a concentration of 48 wt % was added to the mixture under stirring and externally cooled to a temperature of 20° C. or lower to carry out a neutralization reaction. 87 parts of methyl ethyl ketoxime, concentration 48
92 parts of 13 um (by weight t%) of hydroxide and 53 parts of water were added at 20° C. with stirring, and the mixture was reacted for 24 hours.
２４時間後の反応液中の未反応メチルエチルケトオキシ
ムを分析した結果、メチルエチルケトオキシムの反応率
は８０％であった。得られた反応液Ｙ、１回あたり１０
０部のジエチルエーテルで３回抽出し１分液した水溶液
な濃度３５重ｔ％の塩酸で２０℃以下で醒性にし、１回
あたり５００部のジエチルエーテルで６回抽出した。As a result of analyzing unreacted methyl ethyl ketoxime in the reaction solution after 24 hours, the reaction rate of methyl ethyl ketoxime was 80%. Obtained reaction solution Y, 10 per time
The mixture was extracted 3 times with 0 parts of diethyl ether, separated into 1 liquid, quenched at below 20°C with an aqueous solution of hydrochloric acid having a concentration of 35% by weight, and extracted 6 times with 500 parts of diethyl ether each time.
得られたエーテル溶液から常圧下にジエチルエーテルを
留去し、無色の液体１００部を得た。Diethyl ether was distilled off from the resulting ether solution under normal pressure to obtain 100 parts of a colorless liquid.
この液体を中和滴定、赤外吸収およびＮ Ｍ Ｉｔで分
析した結果、イソブチリデンアミノオキシ酢ｄｆｔ８７
重量％含有しており、メチルエチルケトオキシムに対す
る収率は６０％であった。As a result of analyzing this liquid by neutralization titration, infrared absorption, and N M It, it was found that isobutylidene aminooxy vinegar dft87
The yield was 60% based on methyl ethyl ketoxime.
実施例２ の水酸化ナトリウム水溶液２２０部で中和した。Example 2 The mixture was neutralized with 220 parts of an aqueous sodium hydroxide solution.
これにメチルエチルケトオキシム１７０部、濃度４０重
ｔ％の水酸化す） １７ウム水溶液２２０ｇｆｔ温度１
５℃に保持すぺ（冷却しながら同時に添加し、１５℃で
攪拌を継続した。１０時間後にジエチルエーテル６００
部で未反応メチルエチルケトオキシムを除去した後１０
度３５重１ｔ％の塩酸でｐＨ２とし、ジエチルエーテル
１０００部で抽出することにより、イソブチリデンアミ
ノオキシ酢酸のジエチルエーテル溶液を得た。ジエチル
エーテルを除去した結果、無色常温液体のイソブチリデ
ンアミノオキシ酢酸１７５部な得た。メチルエチルケト
オキシムに対する収率は６１．８％であった。To this, add 170 parts of methyl ethyl ketoxime, hydroxide at a concentration of 40 wt%) 17um aqueous solution 220 gft, temperature 1
The temperature was maintained at 5°C (added at the same time while cooling, and stirring was continued at 15°C. After 10 hours, diethyl ether 600%
After removing unreacted methyl ethyl ketoxime in 10 parts
The pH was adjusted to 2 with 35% by weight and 1t% hydrochloric acid, and the solution was extracted with 1000 parts of diethyl ether to obtain a solution of isobutylidene aminooxyacetic acid in diethyl ether. As a result of removing diethyl ether, 175 parts of isobutylidene aminooxyacetic acid was obtained as a colorless room temperature liquid. The yield based on methyl ethyl ketoxime was 61.8%.
（ハ）発明の効果
本発明］こよれば一医薬、農薬、有機合成等の１１月１
η体として有用なイソブチリデンアミノオキシ酢酸を、
安価な原料を用い、工業的に大ｔ１乙容易にかつ経済的
に製造することが可能である。(c) Effects of the invention This invention] November 1, 2017, for pharmaceuticals, agricultural chemicals, organic synthesis, etc.
Isobutylidene aminooxyacetic acid, which is useful as the η form,
It is possible to industrially manufacture large t1 easily and economically using inexpensive raw materials.
Claims (1)
カリの存在下に反応させることを特徴とするイソブチリ
デンアミノオキシ酢酸の製造方法。1. A method for producing isobutylidene aminooxyacetic acid, which comprises reacting methyl ethyl ketoxime and halogenated acetic acid in the presence of an alkali.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5705186A JPS62215557A (en) | 1986-03-17 | 1986-03-17 | Production of isobutylideneaminoxyacetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5705186A JPS62215557A (en) | 1986-03-17 | 1986-03-17 | Production of isobutylideneaminoxyacetic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62215557A true JPS62215557A (en) | 1987-09-22 |
Family
ID=13044646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5705186A Pending JPS62215557A (en) | 1986-03-17 | 1986-03-17 | Production of isobutylideneaminoxyacetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62215557A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995001952A1 (en) * | 1993-07-07 | 1995-01-19 | The Gillette Company | Process for synthesizing o-substituted oxime compounds and conversion to the corresponding o-substituted hydroxylamine |
-
1986
- 1986-03-17 JP JP5705186A patent/JPS62215557A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995001952A1 (en) * | 1993-07-07 | 1995-01-19 | The Gillette Company | Process for synthesizing o-substituted oxime compounds and conversion to the corresponding o-substituted hydroxylamine |
| US5393921A (en) * | 1993-07-07 | 1995-02-28 | The Gillette Company | Process for synthesizing O-substituted oxime compounds and conversion to the corresponding O-substituted hydroxylamine |
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