JPH04193845A - Production of alpha-hydroxyisobutyric acid - Google Patents
Production of alpha-hydroxyisobutyric acidInfo
- Publication number
- JPH04193845A JPH04193845A JP2324957A JP32495790A JPH04193845A JP H04193845 A JPH04193845 A JP H04193845A JP 2324957 A JP2324957 A JP 2324957A JP 32495790 A JP32495790 A JP 32495790A JP H04193845 A JPH04193845 A JP H04193845A
- Authority
- JP
- Japan
- Prior art keywords
- acetone cyanohydrin
- water
- acid
- reaction
- hydrogen chloride
- 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
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 title claims abstract description 18
- NGEWQZIDQIYUNV-UHFFFAOYSA-N L-valinic acid Natural products CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 125000000973 dialkylether group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 150000001983 dialkylethers Chemical class 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 5
- 230000007062 hydrolysis Effects 0.000 abstract 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- DRYMMXUBDRJPDS-UHFFFAOYSA-N 2-hydroxy-2-methylpropanamide Chemical compound CC(C)(O)C(N)=O DRYMMXUBDRJPDS-UHFFFAOYSA-N 0.000 description 1
- 101150111329 ACE-1 gene Proteins 0.000 description 1
- 241000948268 Meda Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- KQSVYGBEQZFKKN-UHFFFAOYSA-N propan-2-one cyanide Chemical compound [C-]#N.CC(=O)C KQSVYGBEQZFKKN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はアセ１〜ンシアンヒドリンからα−ヒドロキシ
イソ酪酸を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing α-hydroxyisobutyric acid from acetyl-cyanhydrin.
（従来の技術）
アセトンシアンヒドリンを鉱酸で加水分解してα−ヒド
ロキシイソ酪酸を製造する方法は古くから知られている
（米国特許第２２２９８９７号公報、イギリス化学会誌
１９３０年２３２５頁、Ｃｈｅｍ、 Ｂｅｒ、 ７２巻
８００頁（１９３９年））。(Prior Art) A method for producing α-hydroxyisobutyric acid by hydrolyzing acetone cyanohydrin with a mineral acid has been known for a long time (US Pat. No. 2,229,897, Journal of the British Chemical Society, 1930, p. 2325, Chem. , Ber, vol. 72, p. 800 (1939)).
特に硫酸加水分解による製法は、その後改良され特公昭
６３−６１９３２号公報に記載のように、アセトンシア
ンヒドリン、硫酸及び水を、アセトンシアンヒドリンに
対する水のモル比０．２〜１．０、アセトンシアンヒド
リンに対する硫酸のモル比０．５〜２．０の条件下反応
させた後、水を加え加水分解する方法として知られてい
る。しかし、この方法は、反応開始時に共存させうる水
の量がアセトンシアンヒドリンに対して０．２〜１．０
と少量で狭い範囲に制限されており、反応系が高粘度に
なる欠点を有し、さらに、硫酸処理を一定時間行った後
でないと、水を加えて加水分解できないため反応を２段
階に分けて行わなければならないといった工程上の問題
をも有していた。In particular, the production method using sulfuric acid hydrolysis was later improved, and as described in Japanese Patent Publication No. 63-61932, acetone cyanohydrin, sulfuric acid and water were mixed in a molar ratio of 0.2 to 1.0. , is known as a method in which the reaction is carried out under conditions where the molar ratio of sulfuric acid to acetone cyanohydrin is 0.5 to 2.0, and then water is added to hydrolyze the reaction. However, in this method, the amount of water that can be allowed to coexist at the start of the reaction is 0.2 to 1.0 relative to acetone cyanohydrin.
The reaction system is limited to a small amount and narrow range, and has the drawback that the reaction system becomes highly viscous.Furthermore, the reaction can be divided into two stages because it cannot be hydrolyzed by adding water until after the sulfuric acid treatment has been carried out for a certain period of time. There were also problems with the process, such as having to carry out the process using
（発明が解決しようとする課題）
したがって、本発明は、かかる欠点を解消し、アセトン
シアンヒドリンからα−ビトロキシイソ酪酸を効率的に
得る方法を提供することを目的とする。(Problems to be Solved by the Invention) Therefore, an object of the present invention is to eliminate such drawbacks and provide a method for efficiently obtaining α-bitroxyisobutyric acid from acetone cyanohydrin.
（課題を解決するめだの手段）
本発明者等は、上記目的を達成すべく種々検討した結果
、塩酸加水分解法を改良することにより、α−ヒドロキ
シ、イソ酪、酸が効率的に製造できることを見出し、本
発明を完成した。(Meda's Means for Solving the Problem) As a result of various studies to achieve the above object, the present inventors have discovered that α-hydroxy, isobutyric acid, and acid can be efficiently produced by improving the hydrochloric acid hydrolysis method. They discovered this and completed the present invention.
即ち、本発明は、アセトンシアンヒドリンを塩酸で加水
分解するに際し、アセトンシアンヒドリン、塩化水素及
び水を、アセ１〜ンシアンヒドリンに対する塩化水素の
モル比１．０〜１．５、アセトンシアンヒドリンに対す
る水のモル比３．６〜５．４の条件下で６５〜９５℃に
加熱することを特徴とするα−ヒドロキシイソ醋酸の製
造法である。That is, in the present invention, when acetone cyanohydrin is hydrolyzed with hydrochloric acid, acetone cyanhydrin, hydrogen chloride, and water are mixed at a molar ratio of hydrogen chloride to acetone cyanohydrin of 1.0 to 1.5, and acetone cyanhydrin, hydrogen chloride, and water. This is a method for producing α-hydroxyisoacetic acid, which is characterized by heating at 65 to 95°C under conditions where the molar ratio of water to phosphorus is 3.6 to 5.4.
以慴、本発明の詳細な説明する。The present invention will now be described in detail.
本発明において、アセトンシアンヒドリンに対する塩化
水素のモル比は１．０〜１．５、好ましくは１．０５〜
１．４であり、またアセトンシアンヒドリンに対する水
のモル比は３．６〜５．４、好まし、くば３．８〜５．
０である。この塩化水素のモル比と水のモル比を満足し
ろるように濃塩酸と水を利用することができる。アセ１
〜ンシアンヒドリンに対する□塩化水素のモル比力月、
０未滴の場合や１．５を超える場合、およびアセトンシ
アンヒドリンに対する水のモル比が３．６未満の場合や
５．４を超える場合には、アセトンシアンヒドリンの分
解反応等の副反応の生起や加水分解反応の未完結等によ
り収率低下につながり好ましくない。１また、水のモル
比が５．４を超える場合には生成物を単離する場合の損
失にもつながり好ましくない。In the present invention, the molar ratio of hydrogen chloride to acetone cyanohydrin is 1.0 to 1.5, preferably 1.05 to 1.5.
1.4, and the molar ratio of water to acetone cyanohydrin is 3.6 to 5.4, preferably 3.8 to 5.
It is 0. Concentrated hydrochloric acid and water can be used so as to satisfy the molar ratio of hydrogen chloride to water. Ace1
~ molar specific force of hydrogen chloride to cyanohydrin,
If the molar ratio of water to acetone cyanohydrin is less than 3.6 or more than 5.4, side effects such as decomposition reactions of acetone cyanohydrin may occur. This is undesirable because it leads to a decrease in yield due to the occurrence of a reaction or incomplete completion of a hydrolysis reaction. 1 Furthermore, if the molar ratio of water exceeds 5.4, this is not preferable as it may lead to loss when isolating the product.
本発明の反応で用いられる温度ば６５〜９５℃で、好ま
しくは７５〜９０℃である。また反応時の圧力は特に制
限はなく、常圧下であっても加圧下であってもよく、１
〜３時間の反応時間で行うことができる。反応温度が６
５℃未満の場合には、加水分解反応の未完結のためα−
ヒドロキシイソ酪酸アミドが副生しやずく、反応温度が
９５℃を超える場合には生成したα−ヒドロキシイソ酪
酸が重合しポリエステルを副生じやすく好ましくない。The temperature used in the reaction of the present invention is 65-95°C, preferably 75-90°C. Moreover, the pressure during the reaction is not particularly limited, and may be under normal pressure or under increased pressure.
It can be carried out with a reaction time of ~3 hours. reaction temperature is 6
If the temperature is less than 5℃, the hydrolysis reaction is incomplete and α-
Hydroxyisobutyric acid amide is produced as a by-product, and if the reaction temperature exceeds 95°C, the produced α-hydroxyisobutyric acid tends to polymerize and produce polyester as a by-product, which is not preferable.
アセトンシアンヒドリン、塩化水素および水の混合方法
は特に制限することばなく、塩化水素と水、または濃塩
酸と水から調整した塩酸中ヘアセトンシアンヒドリンを
添加する方法であっても、アセトンシアンヒドリン中へ
塩化水素と水、または濃塩酸と水を添加する方法であっ
てもさしつかえない。There are no particular restrictions on the method of mixing acetone cyanohydrin, hydrogen chloride, and water. A method of adding hydrogen chloride and water or concentrated hydrochloric acid and water to hydrin may also be used.
本発明の反応形式としては、特に制限はなく回分式合成
、連続式合成いずれの場合でも可能である。また反応器
としては外部ジャケット付の撹拌機を持つ槽壁反応器が
好ましいが、ジャケット付ラインミキサー、スクリュー
式撹拌機の背型反応器であってもさしつかえない。本発
明の反応においては溶媒は特に必要ないが、反応に不活
性な溶媒を加えることはさしつかえない。The reaction format of the present invention is not particularly limited, and either batch synthesis or continuous synthesis is possible. Further, as the reactor, a tank wall reactor having an external jacketed stirrer is preferred, but a jacketed line mixer or a back type reactor with a screw type stirrer may also be used. Although a solvent is not particularly required in the reaction of the present invention, an inert solvent may be added to the reaction.
反応終了後生成物は、メタクリル酸、メタクリル酸エス
テル、これらと炭化水素類との混合物、エーテル類、ケ
トン類からなる群より選ばれた有機抽出剤を、反応混合
物の容量に対して２倍容量以上、より好ましくは４〜１
０倍容量を用い、２〜４回反応液から抽出することによ
り９５％程度以」二の好収率で単離できる。得られるα
−ヒドロキシイソ醋酸の純度および単離収率は、有機抽
出溶剤として好ましくはシアルギルエーテル、より好ま
しくはイソプロピルエーテルを加え抽出する場合に向上
し、さらに着色のない生成物が得られる。このようにし
て得られたα−ヒドロキシイソ酪酸は、そのまま工業原
料としてメタクリル酸やメタクリル酸エステルの合成原
料や医農薬合成中間体として利用可能であるが、必要に
応じて再結晶等により精製することができる。After the completion of the reaction, the product is treated with an organic extractant selected from the group consisting of methacrylic acid, methacrylic esters, mixtures of these with hydrocarbons, ethers, and ketones in a volume twice the volume of the reaction mixture. or more, preferably 4 to 1
By extracting from the reaction solution 2 to 4 times using 0 times the volume, isolation can be achieved with a yield of about 95% or more. α obtained
The purity and isolated yield of -hydroxyisoacetic acid are improved when the organic extraction solvent is preferably sialygyl ether, more preferably isopropyl ether. The α-hydroxyisobutyric acid obtained in this way can be used as an industrial raw material as it is, as a raw material for the synthesis of methacrylic acid and methacrylic acid esters, or as an intermediate for the synthesis of pharmaceuticals and agricultural chemicals, but if necessary, it can be purified by recrystallization etc. be able to.
（実施例） 次に本発明を実施例により、さらに詳しく説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
２００ ｍｌの４つ目フラスコに、３６％塩酸２３．０
ｇを入れ、撹拌しながらアセトンシアンヒドリン１７、
Ｏｇを滴下した。滴下終了後フラスコ内温を８０〜９
０℃に昇温し、２時間撹拌して反応を終了した。冷却後
イソプロピルエーテル１００戚で４回反応混合物を抽出
した。抽出相を減圧上濃縮し、白色結晶のα−ヒドロキ
シイソ酪酸２０．２ ｇ（収率９７％）を得た。Example 1 In a fourth 200 ml flask, add 23.0 ml of 36% hydrochloric acid.
Add acetone cyanohydrin 17, while stirring.
Og was added dropwise. After dropping, the internal temperature of the flask is 80-9.
The reaction was completed by raising the temperature to 0°C and stirring for 2 hours. After cooling, the reaction mixture was extracted four times with 100% isopropyl ether. The extracted phase was concentrated under reduced pressure to obtain 20.2 g (yield 97%) of white crystalline α-hydroxyisobutyric acid.
実施例 ２
２００戚の４つロフラスコに、３６％塩酸２３．０ｇと
水３．３ｇを入れ、アセトンシアンヒドリン１７、 Ｏ
ｇを滴下した。実施例１と同様に処理し２０．０ｇ（収
率９６％）のα−ヒドロキシイソ醋酸を得た。Example 2 Put 23.0 g of 36% hydrochloric acid and 3.3 g of water into a 200-grade four-bottle flask, and add 17.0 g of acetone cyanohydrin.
g was added dropwise. It was treated in the same manner as in Example 1 to obtain 20.0 g (yield 96%) of α-hydroxyisoacetic acid.
実施例 ３
２００ ｍｌ、０４つロフラスコに、３６％塩酸２３．
０ｇを入れ、撹拌しながらアセトンシアンヒドリン１７
、０ ｇを滴下した。滴下終了後フラスコ内温を８０〜
９０℃に昇温し、２時間撹拌して反応を終了した。冷却
後メチルイソブチルケトン１００ ｍｐ。Example 3 Into a 200 ml, 0.4 flask, add 23% of 36% hydrochloric acid.
Add 0g of acetone cyanohydrin 17 while stirring.
, 0 g was added dropwise. After dropping, the internal temperature of the flask is 80~
The reaction was completed by raising the temperature to 90°C and stirring for 2 hours. After cooling, 100 mp of methyl isobutyl ketone.
で４回反応混合物を抽出した。抽出相を減圧下濃縮し、
黄土色結晶のα−ヒドロキシイソ酪酸１９．８ｇ（収率
９５％）を得た。The reaction mixture was extracted four times. The extract phase was concentrated under reduced pressure,
19.8 g (yield 95%) of ocher-colored crystals of α-hydroxyisobutyric acid were obtained.
比較例 １
２００滅の４つ目フラスコに、３６％塩酸２３．０ｇと
水１５．０ ｇを入れ、撹拌しながらアセトンシアンヒ
ドリンＩ ７． Ｏｇを滴下した。実施例１と同様に処
理したところ、得られたα−ヒドロキシイソ酪酸は１３
．１ｇ（収率６３％）であった。Comparative Example 1 Put 23.0 g of 36% hydrochloric acid and 15.0 g of water into a fourth 200 ml flask, and add acetone cyanohydrin I while stirring.7. Og was added dropwise. When treated in the same manner as in Example 1, the obtained α-hydroxyisobutyric acid was 13
．． 1 g (yield 63%).
比較例 ２
２００ ｍｆｌの４つロフラスコに、３６％塩酸２３．
０ｇを入れ、撹拌しながらアセトンシアンヒドリン１７
、 Ｏｇをフラスコ内温５５℃以下に保ち滴下した。サ
ラに５０〜５５℃で５時間撹拌を続けた後、イソプロピ
ルエーテル１００ｍ１で４回反応混合物を抽出した。抽
出相を減圧上濃縮し、得られたα−ヒドロキシイソ酪酸
は１６．２ｇ（収率７８％）であった。Comparative Example 2 Into a 200 mfl four-bottle flask, 23% of 36% hydrochloric acid was added.
Add 0g of acetone cyanohydrin 17 while stirring.
, Og was added dropwise while keeping the internal temperature of the flask below 55°C. After continued stirring at 50-55° C. for 5 hours, the reaction mixture was extracted four times with 100 ml of isopropyl ether. The extract phase was concentrated under reduced pressure, and 16.2 g (yield 78%) of α-hydroxyisobutyric acid was obtained.
比較例 ３
２００ ｍｌの４つ目フラスコに、３６％塩酸４４．６
ｇを入れ、撹拌しながらアセトンシアンヒトＩＪ ７１
７、０ ｇを滴下した。実施例１と同様に処理したとこ
ろ、得られたα−ヒドロキシイソ醋酸は１４．２ｇ（収
率６８％）であった。Comparative Example 3 In a fourth 200 ml flask, add 44.6% of 36% hydrochloric acid.
Add acetone cyanide IJ 71 while stirring.
7.0 g was added dropwise. When treated in the same manner as in Example 1, the amount of α-hydroxyisoacetic acid obtained was 14.2 g (yield 68%).
（発明の効果）
以上述べてきたように、本発明は、特定割合のアセトン
シアンヒドリン、塩化水素及び水を特定範囲の温度条件
で反応させる方法又は反応後有機抽出溶剤で抽出する方
法であるから、反応系が高粘度となることもなく、また
−段階の反応であるのでヒドロキシイソ酪酸を効率的に
製造することができ有用である。特に有機抽出溶剤がジ
アルキルエーテルである場合には、α−ヒドロキシイソ
酪酸の純度および単離収率が向上するとともに着色のな
いα−ヒドロキシイソ酪酸が得られるので、そのままメ
タクリル酸エステル等の合成原料、医農薬合成中間体と
して利用てきα−ヒドロキシイソ酪酸を製造する方法と
して好適である。(Effects of the Invention) As described above, the present invention provides a method of reacting acetone cyanohydrin, hydrogen chloride, and water in a specific ratio under a specific range of temperature conditions, or a method of extracting with an organic extraction solvent after the reaction. Therefore, the reaction system does not become highly viscous, and since it is a one-step reaction, hydroxyisobutyric acid can be efficiently produced, which is useful. In particular, when the organic extraction solvent is a dialkyl ether, the purity and isolation yield of α-hydroxyisobutyric acid improves, and α-hydroxyisobutyric acid without coloration can be obtained, so it can be used as a raw material for synthesis of methacrylic acid esters, etc. This method is suitable as a method for producing α-hydroxyisobutyric acid, which can be used as an intermediate for the synthesis of pharmaceuticals and agricultural chemicals.
出願人 株式会社 り ラ し 代理人 弁理士 木 多 堅Applicant: Rirashi Co., Ltd. Agent: Patent attorney Ken Kita
Claims (1)
し、アセトンシアンヒドリン、塩化水素及び水を、アセ
トンシアンヒドリンに対する塩化水素のモル比１．０〜
１．５、アセトンシアンヒドリンに対する水のモル比３
．６〜５．４の条件下、６５〜９５℃に加熱することを
特徴とするα−ヒドロキシイソ酪酸の製造法。 ２ アセトンシアンヒドリンを塩酸で加水分解するに際
し、アセトンシアンヒドリン、塩化水素及び水を、アセ
トンシアンヒドリンに対する塩化水素のモル比１．０〜
１．５、アセトンシアンヒドリンに対する水のモル比３
．６〜５．４の条件下、６５〜９５℃に加熱した後、有
機抽出溶剤を加え、α−ヒドロキシイソ酪酸を抽剤相に
抽出することを特徴とするα−ヒドロキシイソ酪酸の製
造法。 ３ 有機抽出溶剤が、ジアルキルエーテルである請求項
２記載の製造法。[Claims] 1. When hydrolyzing acetone cyanohydrin with hydrochloric acid, acetone cyanohydrin, hydrogen chloride, and water are mixed at a molar ratio of hydrogen chloride to acetone cyanhydrin of 1.0 to 1.0.
1.5, molar ratio of water to acetone cyanohydrin 3
．． A method for producing α-hydroxyisobutyric acid, which comprises heating to 65 to 95°C under the conditions of 6 to 5.4. 2 When hydrolyzing acetone cyanohydrin with hydrochloric acid, acetone cyanohydrin, hydrogen chloride, and water are mixed at a molar ratio of hydrogen chloride to acetone cyanohydrin of 1.0 to 1.0.
1.5, molar ratio of water to acetone cyanohydrin 3
．． A method for producing α-hydroxyisobutyric acid, which comprises heating to 65 to 95°C under the conditions of 6 to 5.4, adding an organic extraction solvent, and extracting α-hydroxyisobutyric acid into an extractant phase. 3. The manufacturing method according to claim 2, wherein the organic extraction solvent is a dialkyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2324957A JP2909198B2 (en) | 1990-11-26 | 1990-11-26 | Production method of α-hydroxyisobutyric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2324957A JP2909198B2 (en) | 1990-11-26 | 1990-11-26 | Production method of α-hydroxyisobutyric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04193845A true JPH04193845A (en) | 1992-07-13 |
| JP2909198B2 JP2909198B2 (en) | 1999-06-23 |
Family
ID=18171518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2324957A Expired - Fee Related JP2909198B2 (en) | 1990-11-26 | 1990-11-26 | Production method of α-hydroxyisobutyric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2909198B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6864389B2 (en) | 2000-06-02 | 2005-03-08 | Nippon Shokubai Co., Ltd. | Method for producing α-hydroxycarboxylic acid |
| JP2007522156A (en) * | 2004-02-11 | 2007-08-09 | レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Process for producing α-hydroxycarboxylic acids and esters thereof |
| JP2007223993A (en) * | 2006-02-27 | 2007-09-06 | Mitsubishi Rayon Co Ltd | Method for producing optically active mandelic acid or its derivative |
| DE102007011706A1 (en) | 2007-03-08 | 2008-09-11 | Evonik Röhm Gmbh | Continuous preparation of alpha-hydroxycarboxylic ester comprises reacting reactants of alpha-hydroxycarbamide with alcohol, feeding the reactant into a pressure reactor and depleting the product mixture in alcohol and ammonia |
| DE102007050284A1 (en) | 2007-10-18 | 2009-04-23 | Evonik Röhm Gmbh | Process for amidation of nitriles in the presence of sulfuric acid |
| DE102011081256A1 (en) | 2011-08-19 | 2013-02-21 | Evonik Röhm Gmbh | Process for the preparation of alpha-hydroxycarboxylic acid esters |
| CN110963915A (en) * | 2019-11-13 | 2020-04-07 | 上海星酶生物科技有限公司 | Preparation process of 2-acetoxy isobutyryl bromide |
| WO2022084032A1 (en) | 2020-10-23 | 2022-04-28 | Röhm Gmbh | Optimized process for synthesizing alkyl methacrylate by reducing unwanted byproducts |
| WO2022084274A1 (en) | 2020-10-23 | 2022-04-28 | Röhm Gmbh | Optimized process for synthesizing methacrylic acid (maa) and/or alkyl methacrylate by reducing unwanted byproducts |
-
1990
- 1990-11-26 JP JP2324957A patent/JP2909198B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6864389B2 (en) | 2000-06-02 | 2005-03-08 | Nippon Shokubai Co., Ltd. | Method for producing α-hydroxycarboxylic acid |
| JP2007522156A (en) * | 2004-02-11 | 2007-08-09 | レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Process for producing α-hydroxycarboxylic acids and esters thereof |
| JP2007223993A (en) * | 2006-02-27 | 2007-09-06 | Mitsubishi Rayon Co Ltd | Method for producing optically active mandelic acid or its derivative |
| DE102007011706A1 (en) | 2007-03-08 | 2008-09-11 | Evonik Röhm Gmbh | Continuous preparation of alpha-hydroxycarboxylic ester comprises reacting reactants of alpha-hydroxycarbamide with alcohol, feeding the reactant into a pressure reactor and depleting the product mixture in alcohol and ammonia |
| DE102007050284A1 (en) | 2007-10-18 | 2009-04-23 | Evonik Röhm Gmbh | Process for amidation of nitriles in the presence of sulfuric acid |
| DE102011081256A1 (en) | 2011-08-19 | 2013-02-21 | Evonik Röhm Gmbh | Process for the preparation of alpha-hydroxycarboxylic acid esters |
| CN110963915A (en) * | 2019-11-13 | 2020-04-07 | 上海星酶生物科技有限公司 | Preparation process of 2-acetoxy isobutyryl bromide |
| WO2022084032A1 (en) | 2020-10-23 | 2022-04-28 | Röhm Gmbh | Optimized process for synthesizing alkyl methacrylate by reducing unwanted byproducts |
| WO2022084274A1 (en) | 2020-10-23 | 2022-04-28 | Röhm Gmbh | Optimized process for synthesizing methacrylic acid (maa) and/or alkyl methacrylate by reducing unwanted byproducts |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2909198B2 (en) | 1999-06-23 |
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